CHAPTERWISE

TOPICWISE
ENGINEERING ENTRANCES

SOLVED
PAPERS
2019-2005
CHEMISTRY
A Master Collection of Exams Questions to Practice for
JEE MAIN &ADVANCED2020
 CHAPTERWISE
TOPICWISE
ENGINEERING ENTRANCES

SOLVED
PAPERS
2019-2005
CHEMISTRY
A Master Collection of Exams Questions to Practice for
JEE MAIN & ADVANCED 2020

With ♥ from ꕯ 𝛼𝑚 𝞠𝙧⚈

Author
Purnima Sharma

*arihant
ARIHANT PRAKASHAN (Series), MEERUT
>:Carihant
ARIHANT PRAKASHAN (SERIES), MEERUT
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PREFACE
Once you have an idea of what you are going to be asked in a test, you are more
comfortable to tackle it, and your performance in the test improves dramatically.
Once you know the importance of different chapters and topics from the syllabi
for a exam by going through chapterwise and topical segregation of previous
years' questions, you can strategically plan out your preparation for the exam by
allotting your time accordingly for the chapters or the topics of the chapters.

This book Chapterwise & Topicwise Engineering Entrances Solved Papers

Chemistry has Previous Years' Engineering Entrance Questions with their Solutions
to fulfill the above mentioned needs of understanding the nature & pattern of
questions being asked in JEE Main & Advanced and other Engineering Entrances.

The Salient Features of the Book are

• It covers all the questions with explanations from year 2005 to 2019 for all
engineering entrance exams in India (both National as well as Regional).
• Chapterwise division and topical categorisation has been done keeping in mind
the syllabi of various engineering entrance exams and NCERTTextbooks
• Questions of all engineering entrances are grouped according to the year.
• Extreme care is taken, while solving the questions and compiling their
explanations for their accuracy.

We hope that the book will be of utmost help to you in your studies, and propel
you to success in the engineering entrance exams. Suggestions for further
improvement are welcome.

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CONTENTS
IPART I ] Based on Class Xl th NCERT
1. Some Basic Concepts of Chemistry 1-18 6. Thermodynamics 119-153
Measurements in Chemistr y Basic Con cepts ofThermodynamics
Laws of Chemical Combinations and Mole Internal En ergy (I" Law of Thermodynamics)
Concept and Hess's Law
Atomic, Molecular and Equivalent Masses Enthalpies; Types and Their Calculations, Heat
Percentage Composition Capacity of the System
Stoichiometry and Stoichiometric Calculations Entropy, Gibb s' Energy and Spontan eity
nd
(ll and Ill"' Law ofThermodynamics),
2. Structure of Atom 19-42
Ellingham's Diagram
Sub-atomic Particles
Atomic Models 7. Equilibrium 154-200
Modern Struct ure of an Atom Equilib riu m Constants an d Their Units
Quantum Number s Factors Affectin g Equilibria (Le-Chatelier 's
Filli ng of Orbit als in an Atom Principle)
Degree of Dissociation, Acids and Bases pH
3. Classification of Elements and Value and Related Terms
Periodicity in Properties 43-57
Common Ion Effect, Ionic Product of Water an d
Classsification of Elements and Nomenclature
Solubility Product
of Element s with Atomic Numbers> 100
Buffer Solution, Salt Hy d rolysis and Acid-Base
Periodic Trends in Properties of Elements
Titr at ions
4. Chemical Bonding and
Molecular Structure 58-99 8. Redox Reactions 201-211
Ionic, Covalent and Coordinat e Bon d Redox Reactions (Oxidation Number and
Including their Property Balancing)
Re sonting Structure and Polarity of Bond s 9. Hydrogen 212-220
Valence Shell Electron Pair Repulsion (VSEPR) Position of Hydrogen in the Periodic Table,
Theor y, Valence Bon d Theory (VBT), Preparation and Propert ies of Dihydrogen
Hybridisation
Hydrides, Water, Hydrogen Peroxide (H,O,) an d
Hydrogen Bonding, Intermolecular Forces an d Heavy Water (D, O)
Metallic Bond
Molecular Orbital Theory t 0. s-Block Elements 221-234
Group 1 Elements - Alkali Metals
S. States of Matter 100-118
Group 2 Elements - Alkalin e Earth Metals
Gas Laws and Id eal Gas Equation
Kinetic Molecu lar Theory of Gases and t t . p-Block Elements 235-249
Molecular Speeds Group 13 Elements
Behaviour of Real Gases and Vander Walls' Group 14 Elements
Equations (Including Liquefaction of Gases)
Liq uid State
12. Organic Chemistry: Some Basic 13. Hydrocarbons 304-338
Principles and Techniques 250-303 Preparation of Aliphatic Hydrocarbons
Classification and Nomenclature of Organic Properties of Aliphatic Hydrocarbons
Compounds Aromaticity, Structure of Benzene and Aromatic
Fission of Bonds and Electron Displacement Hydrocarb on s
Effects Cyc:loalkan es and Cycloalken es
Reaction Intermediates Petroleum; (raking, Kn ocking and Coaltar
Isom erism Distillat ion
Methods of Purification of Organic Compounds
14. Environmental Chemistry 339-344
Qualitative and Quant itative Analysis of
Atmospheric Pollution
Organic Compounds
Water Pollution
Typ es of Organic Reactions

[ PART 11] Based on Class Xll th NCERT

15. The Solid State 345-358 19. Surface Chemistry 450-466
General Properties and Classification of Solids Adsorption
Cryst al Lattices and Unit Cells, Number of Catalyst and Catalysis
Atoms i n a Unit Cell
Colloids and Emulsions
Closed-Packed Structure, Packing Efficiency
Calculations Involving Unit Cell Dimensions 20. Nuclear Chemistry 467-483
Imperfections in Solids and their Electrical and Nucleus : Con stitution and Stability
Magnetic Properties Radioactivity and Effect of Emission
(Group Displacement Law)
16. Solutions 359-390
Radioactive Disintegration Series an d Rate of
Types of Solutions and Methods of Expressing
Radioactive Decay
Concentration
Artifi cial Transmutations an d Nuclear Reaction s
Vapour Pressure of Solutions Raoult's Law
Applications of Radioactivity
Colligative Properties
Abnormal Molar Masses 21. p-Block Elements 484-514
Distribut ion Law Group 15 Elements

17. Electrochemistry 391-421 Group 16 Elements

Conductance of Electrolytic Solutions
Electrolytic Cells and Elect rolysis
Electrochemical Cells, Galvanic Cells, Nernst
Equation
Batteries
Corrosion
18. Chemical Kinetics
Rat e of a Chemical Reaction
Factors Influencing Rate of a Reaction and
Integrated Rate Equations
Temperature Dependence of the Rate of a
Reaction and Collision Theory of Ch emical
Reactions
Group 17 Elements
Group 18 Elements
22. The d-and f-Block Elements 515-535
Transition Elements an d their Compounds
Inner-Tran sition Elements
23. Coordination Compounds 536-568
422-449
General Terms
Nomenclature and Isomerism
Bonding in Coordination Compounds
Bonding in Metal Carbonyls
Stability of Coordination Compounds
24. Haloalkanes and Haloarenes 569-590 28. Biomolecules 696-719
Methods of Prepar ation of Alkyl Halides Carbohydrates
Properties of Alkyl Halides Proteins and Enzymes
Preparation and Properties of Aryl Halides Nucleic, Acids, (DNA, RNA) and Protein Synthesis
Polyhalogen Compounds Lip id s, Vitamin s, Hormones an d Pigments

25. Alcohols, Phenols and Ethers 591 -624 29. Polymers 720-733
Preparation of Alcohols Polymers: Its Classification and M odes of
Prop er ties of Alcohols Polym erisation

Preparation, Properties and Uses of Ph enols Polymers of Commercial Importance

Ethers 30. Chemistry in Everyday Life 734-744

26. Aldehydes, Ketones and
Carboxylic Acids
Preparation of Aldehydes and Ketones
Chemicals in Medicines
Chemicals in Food and Ph eromon es
625-672
Chemicals as Dy es and Cosmetics

Prop erties of Carb onyl Compounds Cleansing Ag ents

Carb oxylic Acids, Preparation and Properties Rocket Propellants

Derivatives of Carboxylic Acids 31 . Analytical Chemistry 745-753

27. Nitrogen Containing Compounds 673-695
Preparation and Properties of Nitro Com pounds
Preparation and Properties of Cyanides and
lsocyan id es
Preparation and Properties of Amino
Compounds
Preparation and Properties of Diazon ium Salts
Preliminary Test
Wet Test for Acidic Radicals
Wet Test for Basic Rad icals
32. General Principles and Processes
of Isolation of Elements 754-764
Occurrence and Isolat ion of Metals
Principles Involved in Metallurgy and Extraction
Schemes of Certain Metal

Questions Asked in JEE Main 2015 765-771

Solved Papers 2016 (JEE Main, BITSAT, AP EAMCET, TS EAMCET, GGSIPU) 1-29
Solved Papers 2017 (JEE Main & Advanced, BITSAT, VIT & WB JEE) 1-36
Solved Papers 2018 (JEE Main & Advanced, BITSAT & WB JEE) 1-45
Solved Papers 2019 (JEE Main & Advanced, BITSAT & WB JEE) 1-45
Some Basic Concepts
of Chemistry
QUICK REVIEW
Chemistry is that branch ofscience which deals with the study Atomic Mass
of composition, properties and interaction of matter. Atomic mass is defined as a number that expresses as to how
Precision refers to the closeness of set of values obtained by many times an atom of the element is heavier than 1112th of
12
identical measurement while accuracy, refers to the the mass of carbon atom ( C). Therefore,
closeness of a single measurement to its true value.
. average mass of an atom
Atom1c mass = - - - - - - - - --
Significant Figures
_!_ x mass of an atom of C12
• The total number of digits in the number is called the 12
number of significant figmes . Average atomic mass (If an element exists in two
• All digits are significant except zero at the begining of the isotopic forms having atomic masses 'a' and 'b' in the ratio
number. m:n)
• The zeroes to the right of the decimal point are significant. _ (mxa)+(nxb)
m+n
Units for Measurement
• CGS system Length (centin1etre), mass (gram), time Gram Atomic Mass (GAM) Atomic mass ofan element
(second). when expressed in gram.
Number of gram atoms
• MKS system Length (metre), mass (kilogram), time
(second). _ mass of an element (g)
• SI system The SI system has 7 basic units from which all GAM
other units are derived called derived units. Mass of one atom of an element (g)
• Element combined to form compounds in accordance to GAM
=----
the following five basic laws - called the laws of chemical 6.02x 1023
combinations. These are
(i) Law of conservation of mass Molecular Mass
(ii) Law of definite proportion Molecular mass is defined as the sum of atomic masses of the
(iii) Law of multiple proportion elements present in a molecule. Thus, it is obtained by
(iv) Gay-Lussac's law of gaseous volumes multiplying the atomic mass ofeach element by the number of
its atoms and then adding them together, e.g.
(v) Avogadro's law
molecular mass of methane can be calculated as
• According to modem Dalton's atomic theory, atom is no
longer considered to be indivisible as it is made up of CH 4 = Ix atomic mass ofC+ 4 x atomic mass of H
electrons, protons and neutrons. =( 12.0 llu) +4( 1.008 u). = 16.043u
2I Chapterwise & Topicwise Engineering Entrances Solved Papers
• Gram Molecular Mass (GMM) Molecular mass of an
element or compound when expressed in gram.
mass of substance (g )
Number of gram molecules = - - - - - - - -
GMM
Gram molar volume = volume of 1 mole of any gas at
STP = 22.4L
. o f a gas at NTP = -
Dens1ty molecular
---- mass
-~ in grams
--
22400 mL
Number of atoms in a substance
23
= number of GMM x 6.02 x 10 x atomicity
• Equivalent Mass and its Determination
We can determine the equivalent mass follow :
(1') E qwva
. 1ent mass o f an e Iement = -
atomic
-- mass
-
valency
') E . f .d molecular mass
( iz qu1va1ent mass o an act = . .
bas1c1ty
... . molecular mass
(m) Eqwvalent mass of a base = . .
acidity
( iv) Equivalent mass of a salt
formula mass
=-------------
total positive or negative charge of salt
( v) Equivalent mass of an oxidising agent
formula mass
total change in oxidation number
Equivalent mass of common oxidising agent changes with
the medium of the reaction.
Methods of Determination of Equivalent Mass
(i) Oxide formation method
. mass of metal x 8
Eqwvalent mass of metal= - - - - - -
mass of 0 2
mass of metal
= x5~0
volume of 0 2 at STP (in mL)
(ii) Metal displacement method
mass of metal added ( w 1 )
mass of metal displaced ( w 2 )
equivalent mass of metal added (£1 )
equivalent mass of metal displaced (£1 )
(iii) Neutralisation method (for acids and bases)
Equivalent mass ofacid or base= _ t_v - ( where, w is
VxN
the mass ofacid or base (in g), Vis the volume of base
or acid in litre required for neutralisation and N is
normality of base or acid.
(iv) Double decomposition method
AB+CD~ ADt + CB
Mass of compotmd AB
Mass of compmmd AD
Equivalent mass of A+ Equivalent mass of B
Equivalent mass of A + Equivalent mass of D
• Percentage Composition and Molecular Formula
mass of element
Percentage of element = - - - - - - x 100
molecular mass
Molecular fo1mula = n x empirical formula
_ molecular formula mass )
w here, n - - - - - - - - - -
( empirical formula mass
Mole Concept
(i) Number of moles = weight (g ~ = M x V (L)
molecular weight
volume (L)
= - - - - at NTP only for gases.
22.4
. . weight (g ) x 1000
(ii) Number of m1lhmoles = - - - - - -
molecular weight
= molarity x V(mL)
(iii) Number of equivalents
weight (g) .
= . . = normahty x V(L)
eqwvalent weight
(iv) Number of milli equivalents
weight(g)xl000 . V(' mL)
= - - - - - - = norma11ty x m
equivalent weight
Stoichiometry of Reactions in Solutions
Strength of solution = amount of substance in g L- 1
Strength of solution = amount of substance in g mo! L- 1
Strength ofsolution = normality x equivalent weight ofsolute
= molarity x molecular weight of solute
Stoichiometry It is the quantitative study of reactants
and product in a chemical reaction.
Per cent yield The per cent yield of the reaction is given
by
. Id actual yield of the product
P er cent y1e = - -~ - - -~ - - -x 100
theoretical yield of product
• Limiting reagent It is the reagent that is entirely
consumed, when a reaction goes to completion.
If masses of two or more reactants are given, the amount of
products formed depends upon the amount of limiting
reagent.
 Topic 1
Measurements in Chemistry
2010 2007
1. A student performs a titration with different burettes and 3. Which one of the following set of units represents the
finds titre values of25.2 mL, 25.25 mL, and 25.0 mL. The smallest and largest amount of energy respectively ?
number of significant figures in the average titre value is (a) J and erg [Kerala CEE]
(a) 1 (b) 2 (c) 3 (d) 4 [IIT JEE] (b) erg and cal
(c) cal and eV
2008 ( d) L-atm and J
2. The co1Tectly repo1ted answer of the adilition of4 .523, 2.3 and (e) eV and L-atm
6.24 will have significant figures [ManipalJ
(a) two (b) three (c) four (d) five

Topic 2
Laws of Chemical Combinations and Mole Concept
2014 2010
1. The system that contains the maximum number of atoms is 5. One mole of CO 2 contains [Manipal]
(a) 4.25 g ofNH3 (b) 8 g ofO2 [WB JEE] (a) 3 g atoms of CO2
(c) 2g ofH2 (d) 4 g of He (b) 18.1 x 1023 molecules of CO 2
23
2013 (c) 6.02 x 10 atoms ofO
23
( d) 6.02 x 10 atoms of C
2. Number of molecules in 1 L of water is close to CBITSATJ
6. Which has the highest weight ? [Manipall
(a)_____!!_ X 1023 (b) 55.5 X 6.023 X 1023
22.4 (a) 1 m 3 of water
6 023 (b) A normal adult man
(c) · x 1023 (d) 18 x 6.023 x 1023
23.4 (c) 10 L of Hg
(d) All have same weight
2012 7. 1 L oxygen gas at STP will weigh [JCECE]
3. The total number of electrons in 18 mL of water ( density = 1g (a) 1.43 g (b) 2.24 g (c) 11.2 g (d) 22.4 g
mL- 1) is [KCETJ
(a) 6.02x 10 25 (b) 6.02x 10 24 2009
8. Which of the following contains greatest number of
(c) 6.02x 18x 1023 (d) 6.02x 1023
oxygen atoms? [UPSEEJ

2011 (a) 1 g ofO

(b) 1 g of 0 2
4. Arrange the following in the order of increasing mass. (c) 1 gofO3
(Atomic mass ofO = 16, Cu= 63, N = 14) ( d) All have the same number of atoms
I. One atom of oxygen.
II One atom of nitrogen. 2008
III. 1 x 10- to mole of oxygen. 9. The number of hydrogen atoms present in 25.6 g of
sucrose (C12 H 22 O 11 ) which has a molar mass of
IV. 1 x 10- 10 mole of copper
342.3 g is [VITEEE]
(a) II < I < III < IV (b) I < II < III < IV [Kerala CEEJ 23 23
(a) 22 X 10 (b) 9.91 X 10
( c) III < II < IV < I (d) IV < II < III < I
(c) 11 X 10 23 (d) 44 X 1023
(e) II < IV < I < III
4I Chapterwise & Topicwise Engineering Entrances Solved Papers

10. The number of fonnula units of calcium fluoride, CaF2 22. The maximum number of molecules are present in
present in 146.4 g of CaF2 (the molar mass of CaF2 is (a) 15 L ofH 2 gas at STP [UPSEEJ
78.08 g/mol) is [VITEEE] (b) 5 L ofN 2 gas at STP
( a) 1.129 X 1024 CaF2 {b) 1.146 X l 0 24 CaF2 (c) 0.5 g ofH 2 gas
(c)7.808x 1024 CaF2 (d) l.877x 1024 CaF2 (d) 10 g of 0 2 gas
23. Assertion (A) Equal moles of different substances
11. Mass of0.1 mole of methane is [KCET] contain same number of constituent particles.
(a)lg (b)16g (c)l.6g (d)0.lg Reason (R) Equal weights of different substances
12. 80 g of oxygen contains as many atoms as in [KCET] contain the same number of constituent particles.
The correct answer is [EAMCETJ
(a) 80 g of hydrogen (b) 1 g of hydrogen
( c) 10 g of hydrogen (d) 5 g of hydrogen (a) Both A and R are correct and R is the correct
explanation of A
13. 0.1 mole of a carbohydrate with empirical formula CH 20
(b) Both A and R are correct but R is not the correct
contains 1 g of hydrogen. What is its molecular formula? explanation of A
(a) C5H10Os (b) C 6H 12O 6 [Kerala CEE] ( c) A is correct, but R is incoITect
(c) C 4H 8 O 4 (d) C3H6O3 ( d) A is incorrect, but R is co1Tect
(e) C2 H 4 0 2 24. The value of amu is which of the following ? [Guj CETJ
14. Number of atoms of He in 100 u of He (atomic weight of 24
(a) 1.57 x 10- kg 24
(b) 1.66 x 10- kg
He is 4) are [BCECE] 23
(c) 1.99 X 10- kg (d) 1.66 x 10- 27 kg
0025 ~100
(c) 50 (d) l00x 6x 10- 23 2006
25. How many moles of magnesium phosphate, Mg 3(PO4h
2007 will contain 0.25 mole of oxygen atoms ? [AIEEEJ
15. The number of gram molecules of chlorine in 6. 02 x 1025 (a) 0.02 (b) 3.125 X 10- 2
hydrogen chloride molecules is [KCET]
(c) 1.25 X 10- 2 (d) 2.5 X 10- 2
(a) 10 (b) 100 (c) 50 (d) 5 3
26. The mass of 112cm ofCH4 gas at STP is [BITSATJ
16. Which one of the following has maximum number of
atoms of oxygen ? [KCET] (a)0.16g (b)0.8g (c)0.08g (d) 1.6 g
( a) 2 g of carbon monoxide (b) 2 g of carbon dioxide 27. The total number ofprotons in 10 g ofcalcium carbonate is
( c) 2 g of sulphur dioxide (d) 2 g of water (No = 6 . 023 X 1023 ) [WB JEE]

17. Gram molecular volume of oxygen at STP is [KCET] 24 24

(a) 3.01 X 10 (b) 4 .06x 10
24 24
(a) 3200 cm3 (b) 5600 cm 3 (c) 2.0l x 10 (d) 3.02x 10
(c) 22400cm3 (d) 11200cm3
28. The mass of 1 mole of electrons is [UPSEE]
18. Which has maxinmm number of atoms ? [WBJEE]
(a) 9.1 x 10- 23 g (b) 1.008mg
(a) 24 g ofC (b) 56 g of Fe
(c) 0.55mg (d) 9.1 x 10- 27 g
(c)26gofAI (d) 108 g of Ag
19. Which of the following has the smallest number of 29. Which of the following is correct for
molecules ? [WB JEE] C(graphite) + 0 2 (g) ~ CO 2, Heat = - 348kJ?
(a) 0.1 mole of CO2 gas (a) Heat absorbed [OJEEJ
(b) 11.2 L of CO2 gas at STP (b) Mass of product > Mass of reactant
(c) 22 g of CO 2 gas (c) Mass of product < Mass ofreactant
( d) 22.4 x 103 mL of CO 2 gas at STP ( d) Mass of product = Mass of reactant
30. A signature, written in carbon pencil weighs 1 mg. What is
20. 4.6 x 1022 atoms of an element weigh 13.8 g. The atomic
the number of carbon atoms present in the signature ?
weight of that element is [WB JEE]
(a) 5.02 X 1023 (b) 5.02 X 1020 [RPET]
(a) 290 (b) 180 (c) 34.4 (d) 10.4
(c) 6.02x 1020 (d) 0.502x 1020
21. Law of constant composition is same as the law of
(a) conservation of mass [WB JEE] 31. How many moles of Al 2(SO4 h would be in 50 g of the
(b) conservation of energy substance ? [Jam.ia Millia Islamia]
(c) multiple proportion (a) 0.083 mol (b) 0 .952 mol
( d) definite proportion (c) 0.481 mol (d) 0 .140 mo!
 Some Basic Concepts of Chemistry I5
2005
32. The number of molecules of CO2 present in 44 g 33. 2 g of 0 2 at 0°C and 760 mm of Hg pressure has volume
of CO2 is CBCECEJ (a) 1.4 L (b) 2.8 L [BCECEJ
23 (c) 11.2 L (d) 22.4 L
(a) 6.0x 10
(b) 3 X 10
23
34. Number of atoms in 560 g ofFe (atomic mass 56 g mo1- 1)
23 is [Jamia Millia Islamia]
(c) 12x 10
10 (a) twice that of70 g N (b) half that of 20 g H
(d) 3x 10
( c) Both are correct ( d) None of the above

Topic 3
Atomic, Molecular and Equivalent Masses
2013
1. The equivalent mass of Fe in FeO is [OJEEJ 8. If the molecular weight ofNa 2 S 2 O 3 and 12 are M 1 and
(a) 56 (b) 28 M 2 respectively, then what will be the equivalent weight of
(c) 36 (d) 18.66 Na 2 S2 O 3 and 12 in the following reaction?
2. 0.56 g of a gas occupies 280cm 3
at NTP, then its 2S 2 0~- + 12 ~ S4 0~- + 2r [WBJEEJ
molecular mass is [OJEEJ (a)M1 ,M2 (b)M1 ,M2 /2
(a) 4.8 (b) 44.8 (c) 2 (d) 22.4 (c)2M1 ,M2 (d)M1 ,2M2

2012 2010
3. A compound has the molecular formula, X 4 0 6 . If 10 g of 9. The equivalent weight ofKMnO 4 for acid solution is
X 4 0 6 has 5.72 g X, then calculate atomic mass of X. (a)79 (b) 52.16 [Manipal]
(c) 158 (d) 31.6
(a) 32 u (b) 64u [ManipalJ
(c) 67 u (d) 98u 2009
4. The equivalent mass of a certain bivalent metal is 20. The 10. Given, that the abundances of isotopes 54 Fe, 56 Fe and
molecular mass of its anhydrous chloride is [KCETJ Fe are 5%, 90% and 5%, respectively, the atomic mass
57
(a) 111 (b) 55.5 of Fe is [IIT JEEJ
(c) 75.5 (d) 91 (a) 55.85 (b) 55.95 (c) 55.75 (d) 56.05
5. The equivalent weight of K 2 Cr2 O 7 in acidic medium is 11. A bivalent metal has an equivalent mass of 32. The
expressed in terms of its molecular weight (M) as molecular mass of the metal nitrate is [ManipalJ
(a) M (b) M [WB JEE] (a) 182 (b) 168 (c) 192 (d) 188
3 4
(c) M (d) M 2008
6 7 12. The percentage of an element M is 53 in its oxide of
molecular formula M 2 0 3 . Its atomic mass is about
2011
(a)45 (b)9 (c) l 8 [KeralaCEEJ
6. In the disproportionation reaction, (d) 36 (e) 27
3HCIO3 ~ HC1O 4 + C l 2 + 202 + H 2 O, 13. An unknown element forms an oxide. What will be the
the equivalent mass of the oxidising agent is (molar mass equivalent weight of the element if the oxygen content is
ofHClO3 = 84.45) [Ke rala CEEJ 20% by weight ? [WB JEEJ
(a) 16.89 (b)32.22 (c)84.45 (d)28.15 (a) 16 (b) 32 (c) 8 (d) 64
(e) 29.7
14. An alkaloid contains 17.28% ofnitrogen and it's molecular
7. 2 g of metal carbonate is neutralised completely by 100 mL mass is I 62. The number of nitrogen atoms present in one
of0.1 N HCL The equivalent weight ofmetal carbonate is molecule of alkaloid is [Guj CETJ
(a) 50 (b) 100 [WBJEEJ (a)5 (b)4 (c)3 (d)2
(c) 150 (d) 200
6I Chapterwise & Topicwise Engineering Entrances Solved Papers

15. Of two ox.ides of iron, the first contained 22% and the 23. For the reaction,
second contained 30% of oxygen by weight. The ratio of Na 2 CO3 + 2HCI~ 2NaCI + H 2 O+ CO 2
weights of iron in the two ox.ides that combine with the
Equivalent weight ofNa 2 CO 3 is [AMUJ
same weight of oxygen, is [J&K CET]
M (d) M
(a) 3 : 2 (b) 2 : 1 (c) 1 : 2 ( d) 1 : 1 (a) (b) M (c) 2M
2 4
16. 1.520 g of hydroxide ofa metal on ignition gave 0.995 g of
ox.ide. The equivalent weight of metal is [BCECE] 24. A gas is found to have a fom1ula [CO]x. Its vapour density
(a) 1.52 (b) 0.995 is 70, the x is [BCECE]
(c) 190 (d) 9 (a) 3.0 (b) 3.5 (c) 5.0 (d) 6.5
17. The formula mass of Mohr's salt is 392. The iron present in 2006
it, is oxidised by KMnO 4 in acidic medium. The equivalent
25. 4 g ofcopper was dissolved in concentrated nitric acid. The
mass of Mohr's salt is [Jamia Millia Islamia]
copper nitrate solution on strong heating gave 5 g of its
(a) 392 (b)3 1.6 oxide. The equivalent weight of copper is [AMUJ
(c) 278 (d) 156
(a) 23 (b) 32
2007 (c) 12 (d) 20
18. Camphor is often used in molecular mass determination 26. KMnO 4 (mo!. wt. = 158) oxidises oxalic acid in acidic
because [Manipal] medium to CO 2 and water as follows
(a) it is readily available 5C2 0 t + 2MnO4 + 16H+
(b) it has a very high cryoscopic constant
~ I0CO 2 + 2Mn 2 + + 8H2 O
(c) it is volatile
(d) it is solvent for organic substances What is the equivalent weight of KMnO 4 ? [J&K CETJ
19. What is the equivalent weight of SnC1 2 in the following (a) 158 (b) 31.6
reaction, (c) 39.5 (d) 79
SnC1 2 + Cl 2 ~ SnC1 4 [KCET] 27. In the equation, H 2 S+ 2HNO 3 ~ 2H 2 O+ 2NO2 + S
(a) 95 (b) 45 The equivalent weight of hydrogen sulphide is [BCECEJ
(c) 60 (d) 30 (a) 18 (b) 68
20. If molecular weight of KMnO4 is M, then its equivalent (c) 34 (d) 17
weight in acidic medium would be [WB JEE] 2005
(a)M (b)M (c)M (d)M 28. If we consider that_!_ , in place of_!_ , mass of carbon atom
2 5 3 6 12
21. 74.5 g ofametallic chloride contains 35.5 g ofchlorine, the is taken to be the relative atomic mass unit, the mass of one
equivalent weight of the metal is [WB JEE] mole of a substance will [AIEEEJ
(a) 19.5 (b) 35.5 (a) be a function of the molecular mass or the substance
(c) 39 (d) 78.0 (b) remain unchanged
22. 3 g of an ox.ide of a metal is converted to chloride ( c) increase two fold
( d) decrease twice
completely and it yielded 5 g of chloride. The equivalent
weight of the metal is [OJEE] 29. The equivalent weight of a certain trivalent element is 20.
(a) 33.25 (b) 3.325 Molecular weight of its oxide is CRPETJ
(c) 12 (d) 20 (a) 152 (b) 56 (c) 168 (d) 68
 Topic 4
Percentage Composition
2010
1. An organic compound on analysis was found to contain The molecular fo1mula of hydrocarbon is [Kerala CEE]
10.06% carbon, 0.84% hydrogen and 89.10% chlorine. What (a) C5 H4 (b) C10 H8
will be the empirical fom1ula of the substance? [MP PET]
(c) C1sH12 (d) C20H16
(a) CH2Cl 2 (b) CHC13 {c) CC1 4 (d) CH3 CI
(e)C1s H20
2008 5. A compound contains 69.5% oxygen and 30.5% nitrogen
2. If two compounds have the same empirical formula but and its molecular weight is 92. The formula of the
ilifferent molecular formulae, they must have CRPET] compound is [DCE]
(a) different percentage composition (a) N2O (b) NO 2
(b) different molecular weights (c) N 2 0 4 (d) N 2 0 5
(c) same viscosity
(d) same vapour density 2006
3. In a compound C, H and N are present in 9 : l : 3.5 by 6. The empirical formula of a compound is CH2. One mole
weight. If molecular weight of the compound is 108, then of this compound has a mass of 42 g. Its molecular formula
the molecular formula of the compound is [BCECE] is [Manipal]
(a) C2H6 N2 (b) C3 H4 N (c) C6 H 8 N2 (d) C9 H12N3
2007 7. An organic compound has an empirical formula (CH 2O),
4. An aromatic hydrocarbon with empirical formula, C5 H 4 on its vapour density is 45. The molecular formula of the
treatment with concentrated H2SO4 gave a monosulphonic compound is [Manipal]
acid. 0.104 g of the acid required 10 mL of~ NaOH for (a) CH 2 0 (b) C2 H 5 0
20 (c) C2 H 2 0 (d) C3 H 6 0 3
complete neutralisation.

Topic 5
Stoichiometry and Stoichiometric Calculations
2014
1. 10 g of sample of mixture ofCaC1 2 and NaCl is treated to 4. A 5.82 g silver coin is ilissolved in nitric acid. When
precipitate all the calcium as CaCO3 . This CaCO3 is soilium chloride is added to the solution, all the silver is
heated to convert all the Ca to CaO and the final mass of precipitated as AgCl. The AgCl precipitate weighs 7.20 g.
CaO is 1.62 g. The per cent by mass of CaCI 2 in the The percentage of silver in the coin is [AMU]
original mixture is [BITSAT] (a) 60.3% (b) 80%
(a) 32.1% (b) 16.2% (c) 21.8% (d) 12.0% (c)93.1% (d)70%
2. 2.76 g ofsilver carbonate on being strongly heated yields a
residue weighing [VITE EE]
2013
5. If 20 g of CaCO3 is treated with 100 mL of 20% HCl
(a)3.54g (b)3.0g (c)l.36g (d)2.16g
solution, the amount of CO 2 produced is [Manipal]
3. For the reaction represented by the equation,
(a) 22.4 L (b) 8.80 g (c) 4.40 g (d) 2.24 L
ex4 + 202 ~ co2 + 2X20
9.0 g ofCX 4 completely reacts with 1.74 g ofoxygen. The 2012
approxin1ate molar mass of X will be [Manip al] 6. 5 moles ofBa(OHh are treated with excess of CO2. How
(a)20 (b)40 much BaCO3 will be formed? CBITSAT]
(c) 60 (d) 80 (a) 39.4 g (b) 197 g (c) 591 g (d) 985 g
8I Chapterwise & Topicwise Engineering Entrances Solved Papers

7. 20 mL of methane is completely burnt using 50 mL of 14. Acidified KMnO 4 oxidises oxalic acid to CO 2 . What is the
oxygen. The volume of the gas left after cooling at room volume (in litres) of 10-4 M KMnO4 required to
temperature is [KCET] completely oxidise 0. 5 L of I 0- 2 M oxalic acid in acidic
(a) 40 mL (b) 60 mL medium ? [BITSAT]
(c) 30 mL (d) 80 mL (a) 125 (b) 1250 (c) 200 (d) 20
15. Match the following Column I and Column IT.
2011
8. The mass of potassium dichromate crystals required to Column I Column II (At STP)
oxidise 750 cm 3 of0.6 M Mohr's salt solution is (Given, I. 0.224 L CO 2
molar mass : potassium dichrornate = 294, A. I0gCaCO3 ti.
decomposition
Mohr's salt= 392) [AIEEEJ
B. 1.06 g Na 2CO3 Excess HCI 1 2. 4.48 L CO2
(a) 0.49 g (b) 0.45 g (c) 22.05 g (d) 2 .2 g
9. Stoichiometric ratio ofsodium dihydrogen orthophosphate 3. 0.448 L CO 2
C. 2 4 g C Excess 0 2
and sodium hydrogen orthophosphate required for · Combustion
synthesis of Na 5 P3 0 10 is [Guj CETJ 4. 2.24 L CO2
( a) 1.5 : 3 (b) 3 : 1.5 (c) 1 : 1 ( d) 2 : 3 D. 0.56gCO Excess0 2
Combustton
2010 5. 22.4 L CO2
10. A mixture of CaCI 2 and NaCl weigh ing 4.44 g is treated
with sodium carbonate solution to precipitate all the Ca 2+ Codes [BITSAT, AMU, EAMCET]
ions as calcium carbonate. The calcium carbonate so A B C D A B C D
obtained is heated strongly to get 0.56 g of CaO. The (a) 4 I 2 3 (b) 5 I 2 3
percentage of NaCl in the mixture (atomic mass ofCa = 40) (c) 4 1 3 2 (d) 1 4 2 3
is [KCET] 16. The ratio of amounts of H 2 S needed to precipitate all the
(a) 75 (b) 30.6 (c) 25 (d) 69.4 metal ions from 100 mL of 1 M AgNO 3 and 100 mL of
CuSO4 , will be [Manipal]
2009 (a)l:1 (b)l:2
11. An aqueous solution containing 6.5 g of NaCl of 90% (c) 2: I (d) None of these
purity was subjected to electrolysis. After the complete
17. For the reaction, Fe 2 O 3 + 3CO~ 2Fe + 3CO2 , the
electrolysis, the solution was evaporated to get solid
volume ofcarbon monoxide required to reduce one mole of
NaOH. The volume of 1 M acetic acid required to
fen-ic oxide is [KCETJ
neutralise NaOH obtained above is [Manipal]
(a) 22.4dm3 (b) 44.8dm 3
(a) I 000 cm 3 (b) 2000 cm 3 3
( c) I 00 cm 3 ( d) 200 cm
3 (c) 67.2dm (d) l l.2dm 3

12. Excess of carbon dioxide is passed through 50 mL of0.5 M
calcium hydroxide solution. After the completion of the
reaction, the solution was evaporated to dryness. The solid
calcium carbonate was completely neutralised with 0.1 N
hydrochloric acid. The volume of hydrochloric acid
required is ( atomic mass of calcium = 40) [Manip al]
(a) 300 cm 3 {b) 200 cm 3
(c) 500 cm 3 (d) 400 cm 3
2008
13. Amount of oxalic acid present in a solution can be
determined by its titration with KMnO4 solution in the
presence of H2 SO4 . The titration gives unsatisfactory
result when carried out in the presence ofHCl because HCI
(a) gets oxidised by oxalic acid to chlorine [AIEEEJ
(b) furnishes H+ ions in addition to those from oxalic
acid
18. M nO 4 ions are reduced in acidic condition to Mn 2+ ions
whereas, they are reduced in neutral condition to MnO 2 .
The oxidation of 25 mL of a solution X containing
Fe 2+ ions required in acidic condition 20 mL of a solution
Y containing MnO 4 ions. What volume of solution Y
would be re9iuired to oxidise 25 mL of a solution X
containing Fe + ions in neutral condition? [Ke rala CEE]
(a) 11.4 mL (b) 12 .0 mL (c) 33.3 mL
(d) 35.0 mL (e) 25.0 mL
19. Sodium nitrate on reduction with Zn in presence ofNaOH
solution produces NH 3 . Mass of sodium nitrate absorbing
1 mole of electron will be [WB JEE]
(a) 7.750 (b) 10.625
(c) 8.000 (d) 9.875
20. 1 mole of methylamine on reaction with nitrous acid gives
at NTP [WB JEE]

(c) reduces permanganate to Mn 2+ (a) 1.0 L of nitrogen (b) 22.4 L of nitrogen

( d) oxidises oxalic acid to carbon dioxide and water (c) 11.2 L ofnitrogen (d) 5.6 L of nitrogen
 Some Basic Concepts of Chemistry I9
21. The stoichiometry of the following reaction is 27. What amount of bromine will be required to convert 2 g of
K 2 S 2 O 8 (aq) + 2KI(aq)~ 2K 2 SO 4 (aq)+ I 2 (aq) phenol into 2, 4, 6-tribromophenol ? CUPSEEJ
(a) 2: 2 {b) I : 1 [J&KCET] (a) 20.44 g (b) 6.00 g
(c) I : 2 (d) 2 : l (c)4.00g (d) l 0.22g
22. The decomposition of a certain mass of CaCO3 gave 28. When 10 g of90% pure limestone is heated completely, the
3 volume (in litres) of CO2 is liberated at STP is CRPETJ
I l. 2dm of CO 2 gas at STP. The mass of KOH required
(a) 22.4 (b) 2.24
to completely neutralise the gas is [Jamia Millia Islamia] (c) 20. 16 (d) 2.016
(a)56g (b)28g
(c)42g (d)20g 2006
29. The volume of oxygen necessary for the complete
2007
combustion of 20 L of propane is [WBJEE]
23. Consider a titration of potassium dichromate solution with
(a)40L (b)60 L
acidified Mohr's salt solution using diphenylarnine as
(c) 80 L (d) 100 L
indicator. The number of moles of Mohr's salt required per
mole of dichromate is [HT JEE] 30. The enthalpy of combustion of methane at 25°C is 890 kl
The heat liberated when 3.2 g of methane is bwnt in air is
(a) 3 (b) 4
(a) 445 kJ (b) 278 kJ [AMUJ
(c) 5 (d) 6
(c) - 890kJ (d) l 78 kJ
24. In the reaction, 31. What is the weight of oxygen that is required for the
2Al(s) + 6HCl(aq) ~ 2AI 3+ (aq) complete combustion of2.8 kg of ethylene? CBCECE]
+ 6Cl- (aq) + 3H2 (g) (a) 9.6 kg (b) 96.0 kg
(c) 6.4 kg (d) 2.8 kg
[AIEEE]
32. Sodium bicarbonate on heating decomposes to form
(a) 6L HCl(aq) is consumed for every 3 L H2 (g)
produced sodium carbonate, CO2 and water. If0.2 moles of sodium
(b) 33.6LH2 (g) is produced regardless of temperature bicarbonate is completely decomposed, how many moles
and pressure for every mole of Al that reacts of sodium carbonate is formed ? [J&K CETJ
(c) 67.2L H2 (g )at STP is produced for every mole of Al (a) 0.1 (b) 0.2 (c) 0.05 (d) 0.025
that reacts
(d) I 1.2 L H2 (g) at STP is produced for every mole of 2005
HCl(aq)consumed 33. 100 g of CaCO3 is treated with I L of 1 N HCI. What
25. Air contains 20% 0 2 by volume. How much volume of air would be the weight of CO2 liberated after the completion
will be required for 100 cc of acetylene ? [DCEJ of the reaction? [Kerala CEEJ
(a) 500 cc {b) 1064 cc (a)55g (b) ll g (c)22g (d)33g
(c) 212.8 cc (d) 1250 cc (e) 44 g
26. 2 g of mixture of CO and CO 2 on reaction with excess 34. x grams of calcium carbonate was completely bwnt in air.
12 0 5 produced 2.54 g ofl 2 . What would be the mass% of The weight of the solid residue formed is 28 g. What is the
CO2 in the original mixture ? [WB JEE] value of x (in grams)? [EAMCETJ
(a)60 (b)30 (a)44 (b)200
(c) 70 (d) 35 (c) 150 (d) 50
 Answers
TOPICl Measurements in Chemistry
1. (c) 2. (b) 3. (e)
TOPIC2 Laws of Chemical Combinations and Mole Concept
1. (c) 2. (b) 3. (b) 4. (a) 5. (d) 6. (a) 7. (a) 8. (d) 9. (b) 10. (a)
11. (c) 12. (d) 13. (a) 14. (a) 15. (b) 16. (d) 17. (c) 18. (a) 19. (a) 20. (b)
21. (d) 22. (a) 23. (c) 24. (d) 25. (b) 26. (c) 27. (a) 28. (c) 29. (d) 30. (d)
31. (d) 32. (a) 33. (a) 34. (c)
TOPIC3 Atomic, Molecular and Equivalent Masses
1. (b) 2. (b) 3. (a) 4. (a) 5. (c) 6. (a) 7. (d) 8. (b) 9. (d) 10. (b)
11. (d) 12. (e) 13. (b) 14. (d) 15. (a) 16. (d) 17. (a) 18. (c) 19. (a) 20. (c)
21. (c) 22. (a) 23. (a) 24. (c) 25. (b) 26. (b) 27. (d) 28. (b) 29. (c)
TOPIC4 Percentage Composition
1. (b) 2. (b) 3. (c) 4. (c) 5. (c) 6. (a) 7. (d)
TOPICS Stoichiometry and Stoichiometric Calculations
1. (a) 2. (d) 3. (d) 4. (c) 5. (b) 6. (d) 7. (c) 8. (c) 9. (b) 10. (a)
11. (c) 12. (c) 13. (c) 14. (d) 15. (a) 16. (b) 17. (c) 18. (c) 19. (b) 20. (b)
21. (c) 22. (b) 23. (d) 24. (d) 25. (d) 26. (b) 27. (d) 28. (d) 29. (d) 30. (d)
31. (a) 32. (a) 33. (c) 34. (d)

Explanations
Topic 1 Me asurement s in Ch emistry
25.2 + 25.25 + 25.0 75.45
1. Average va Iue = - - - - - - - Numberofatoms in2gof H 2 =~xNA x2=2NA
3 3 2
= 25.15= 25.2 mL
Number of significant figure is 3.
Number of atoms in 4 g of He = i4 x NA x I = NA
2. 4.523 + 2.3 + 6.24 = 13.063. As 2.3 has least number of Thus, 2 g ofH 2 contains the maximum number of atoms among
decimal places, i.e. one, therefore sum should be reported to one the given.
decimal place only. After rounding off, reported sum= 13.1 which
2. I mole of water means 18 g of water which means 6.023 x I 023
has three significant figures.
molecules
3. Smallest and largest amount ofenergy respectively eV and L-atm.
I L of water means 1000 g
I eV = 1.6 x 10- 19 J
Number of moles of water in 1000 g of water = lOOO mol
I L-atm = I 01.325 J 18
= lOOO x6.023 x 1023 molecules
Topic 2 Laws of Chemical 18
Combinations and Mole = 55.5 x 6.023 x 1023 molecules
Concept 3. In 18 mL, number of moles ofH2O
mass = massofH2O
1. Number of atoms = - - - - x NA x number of atoms in I
molar mass molecular mass
mole
= density x volume = I x 18 = 1 mol
where, NA =Avogadro's number
molecular mass 18
Number of atoms in 4.25 g ofNH3
4.25 ·: Number of molecules of H 2O in I mot = 6.022 x I 023 and
=- XNA X4=NA
17 Number of electrons in I molecule ofHzO = I x 2 + 8 = I 0
Number of atoms in 8 g of Number of electrons in I mole ofH2O= 6.022 x 1023 x 10

02 = -8 X NA X
NA
2 =- = 6.022 X 1024
32 2
 Some Basic Concepts of Chemistry I 11

4. I. Mass of one atom of oxygen = 16 2.66 x Io-23 g Number of formula units of CaF2 in 146.4 g of CaF2
6.022 X 1023 = number of moles x 6.022 x 1023
14 = J.875 X 6.022 X 1023 = J J.29 X 1023
II. Mass ofone atom of nitrogen = 2.32 x 10-23 g
6.022 X 1023 = 1.129 x 1024 CaF2
III. Mass of I x I 0- 10 mole of oxygen = 16 x 10- 10 g
11. Mass of I mole of methane (CH4 ) = 16 g
IV. Mass ofl x 10- 10 mole of copper= 63 x 10- 10g
Mass of 0.1 mole of methane= 16 x 0.1 g = 1.6 g
Hence, masses of atoms in increasing order 80
12. Number of moles of oxygen molecules = -
II < I < III < IV 32
5. One mole of CO 2 contains 6.02 x 1023 atoms of carbon and 80
Number of atoms of oxygen = - x N O x 2 = 5 x N 0
6.023 x 1023 molecules of oxygen. 32
6. (a) Density of water = I g cm- 3 Number of moles in 5 g of hydrogen molecules = 2-
2
Volume of water= I m 3 = 106 cm3
Number of atoms in 5 g of hydrogen = %x N O x 2 = SN 0
Mass= volume x density= I cf cm 3 x I g cm-3
6 Hence, the number of atoms in 80 g of oxygen is equal to the
6 10
= 10 g= - kg= 1000 kg number of atoms in 5 g of hydrogen.
103
13. ·: 0.1 mole of carbohydrate contains = I g of hydrogen
(b) Mass of normal adult man= 65 kg
(c) Density of Hg = 13.6 g cm-3 I mole of carbohydrate contains = _!_ = IOg of hydrogen
Volume ofHg= JO L = 10 x 1000 cm 3 0.1
Hence, its molecular formula = C5H 100 5•
Mass of Hg= 13.6 x 10 x 1000
= 136000 g = 136 kg 14. ·: 4 u = I He-atom
Mass of I m 3 water is highest. I
I u = - He-atom
4
7. Given, volume ofO2 = 1L IX 100
Hence, I 00 u = - - - = 25 atoms
22.4 L ofO2 at STP = 32g 4
32 15. Number of gram molecules of chlorine
IL ofO2 at STP =- - g =1.43 g
22.4 (As gram molecules =NA, w here NA is Avogadro's number)
8. Number of atoms= moles x NA x atomicity 6.02 X 1025 = I 00
Here, NA= Avogadro's number 6.02 X 1023
(a) Number of oxygen atoms in I g of 0
16. Number of oxygen atoms in 2 g of CO = 2 x 6.022 x I 023 x I
= _J__ XNX I =~ 28
16 A ]6
(b) Number of oxygen atoms in I g of 0 2 Number of oxygen atoms in 2 g of CO2 = 2 x 6.022 x 1023 x 2
44
I ~
= - XNAX2= -
32 16 Number of oxygen atoms in 2 g of SO 2 = 2 x 6.022 x 1023 x 2
( c) Number of oxygen atoms in I g of 0 3 64
I NA Number of oxygen atoms in 2 g of HzO = 2 x 6.022 x 10 23 x I
= 48 X~ X3= )6 18
Hence, all have the same number of oxygen atoms. Hence, 2 g ofH2O has maximum number of atoms of oxygen.
mass of sucrose (in gram) 17. Gram molecular volume of oxygen at STP is 22.4 or22400 cm 3.
9. M o Ie o f sucrose= - - - - - -~ ~- ~
molecular weight of sucrose 18. Number of atoms in 24 g of C
25 6 24
= · = 0.0747882 = X 6.02 X 1023 = 2 X 6.02 X 1023
342.3 12
Formula of sucrose = C 12H 22O 11
Number of atoms in 56 g of Fe
Number ofH-atoms in I mole of sucrose= 22x 6.023 x 1023
56
Number of H-atoms in 0.0747882 mole of sucrose = X 6.02 X 1023 = 6.02 X 1023
23 23
56
= 22 X 6.023 X 10 X 0.074788= 9.9 X 10 Number of atoms in 26 g of Al
10. Mass ofCaF2 = 146.4 g 26
= X 6.02 X 1023 "" 6.02 X 1023
Molecular weight of CaF2 = 78.08 g/ mol 27
weight Number of atoms in I 08 g of Ag
Moles of CaF2 = - - - - - -
molecular weight 3
= J0 X 6.02 X 1023 = 6.02 X 1023
146 108
= .4 = 1.875 mol :. 24 g ofC has maximum number of atoms.
78.08
12 I Chapterwise & Topicwise Engineering Entrances Solved Papers

19. (a) Number of moles of CO 2 = 0.1 mole

11.2
(b) Number of moles of CO 2 = - - = 0.5 mole 26. ·: Mass of 22400 cm 3 of CH 4 at STP = 16 g
22.4 16
:. Mass of 1 cm 3 ofCH4 at STP = - - g
22 22400
( c) Number of moles of CO 2 = - = 0.5 mole
44 16
: . Mass of 112 cm 3 ofCH4 at STP = - - x 112 = 0.08 g
22.4 X 103 22400
(d) Number of moles of CO 2 = - - - - = 1 mole
22400 27. We know that, protons in I mole CaCO 3
Equal number of moles have equal number of molecules. =atomic number ofcalcium + atomic number of carbon+ 3 (atomic
Hence, the smallest number of molecules of CO2 is in number of oxygen)= 20 + 6 + 3(8) = 50
0.1 mole of CO2•
i.e. Number of protons in I 00 g of CaCO3 = 50 x 6.023 x 1023
20. 4.6 x I 022 atoms of element weigh = 13. 8 g . 10 X 50 23
: . Number of protons m 10 g ofCaCO 3 = x 6.023 x 10
Hence, 6.02 x 1023 atoms will weigh 100
23 24
13.8 X 6.02 X 10 = _ = 3.01 X 10
180 6 (molar
4.6x 1022 g 28. One mole of electrons= 6.023 x 1023 electrons
mass)
Mass of one electron = 9. I x 10-23 g
21. According to law of constant composition, "a chemical Mass of one mole of electrons
compound is always found to be made up of the same elements
= 6.023 X 1023 X 9.1 X 10-28 g
combined together in the same proportions by weights''.
4
This law is same as law of definite proportions. = 5.48 x 10- g = 0.548 mg "' 0.55 mg
22. In 15 L of H 2 gas at STP, the number of molecules 29. C(graphite) + O 2 (g)~ CO2; Aff = - 348 kJ
12g 32g 44g
23 In the above reaction, heat is evolved and mass of product is equal
6.023x10 xl = 4 _
5
x 23
033 10
22.4 to mass of reactant.
30. ·: Number of atoms present in 12 g of carbon = 6.023 x 1023
In 5 L of N 2 gas at STP, the number of molecules
Number of atoms present in 1 mg carbon
23
23 6. 023 10 X 1 = _502 X I 020
X
6.023 X IO X 5 = 1.344 X l023 0
12 X 1000
22.4
In 0.5 g of H 2 gas, the number of molecules 3 1. Number of moles= ___
mas
_ s_ _
23 molecular mass
6.023 X 10 X 0.5 = 1. X l023
505 Given, mass of Alz(SO4 ) 3 = 50 g
2
Molecular mass of Al 2 (SO4 h = 342 g
In IO g of 0 2 gas, the number of molecules
23 50
6.023 X 10 X 10 23 : . Moles of Ali(SO4 ) 3 = - = 0.14 mol
1.882 X 10 342
32
Hence, maximum molecules are present in 15 L of H 2 at STP. 32. 1 mole = molecular mass in gram = 6.02 x I0 23 molecules
Given, mass of CO2 = 44 g
23. Equal moles of different substances contain same number of
Molecular mass of CO 2 = 12 + 16 x 2 = 44
constituent particles but equal weights of different substances
do not contain the same number of constituent particles. : . Number of molecules in 44 g of CO2 = 6.02 x 1023
24. amu represents atomic mass unit. It is used in place of unified 33. Given, mass of 0 2 = 2 g at 0°C and 760 mm of Hg
mass unit.
32 g of 0 2 ""' 22.4 L at STP
1 u = 1 Avogram = I Aston = I Dalton 22.4
1 2 g of 0 2 == - - X 2 = I .4 L
I u = - x mass ofC-12 atom 32
12 560
23
34. Moles ofFe = = 10
= __!__ X 1.9924 X 10- g 56
12 70
Moles ofN = - = 5
= 1.66 X 10-24 g = 1.66 X 10-27 kg 14
20
25. 8 moles ofO-atoms are present in 1 mole ofMg3 (PO4 )z. Moles ofH = = 20
1
Hence, 0.25 moles ofO-atoms will be present in _!_ x 0.25 mole Equal number of moles have equal nu mber of atoms.
8 Hence, number of atoms in 560 g of Fe is twice that of70 g ofN and
is half that of20 g ofH.
Topic 3 Atomic, Molecular and Equivalent Masses
1. Equivalent weight of Fe 9. In acidic medium, following reaction takes place.
molecular weight of Fe 8H+ + Se- + MnO4 ~ Mn 2 + + 4H2O
number of positive valencies of cations
Equivalent weight of KMnO4 in acidic medium
Molecular weight of Fe = 56 = molecular weight ofKMnO 4 ~ = _
31 6
Valency of Fe= + 2 in FeO, FeO(Fe2+O 2- ) 5 5
. . 56 10. Average atomic weight
then, eqmvalent weight = - = 28
2 54 X 5 + 56 X 90 + 57 X 5 SS. S
9
2. We know that, I mole or 1 g molecule of a gas occupies 22.4 Lor 100
22400 cc atNTP. 11. Atomic mass of the metal = 32 x 2 = 64
·: 280 cm 3 volume at NTP occupies = 0.56 g of gas
Formula of metal nitrate =M (NO 3 h
: . 22400 cm3 volume at NTP will occupy :. Molecular mass= 64 + 28 + 96 = 188
6 12. Percentage of e lement Min M 2 O 3 = 53
= O.S X 22400 = 44.8 g
280 Let the atomic mass of M = x
3. Let the atomic mass of X be 'a', then molecular weight of Mass of Min MP 3 = 2x
X 40 6 = (4a + 96) Total atomic mass of M 20 3 = 2x + 16 x 3 = 2x + 48
·: (4a + 96)g X 40 6 contains X = 4 a g Percentage of an element
. 4a X 10 = mass of an element in a compound x
10 g xp6 contains X = - - - = 5.72 100
4a+ 96 total mass of compound
22.88a + 549. 12 = 40a 2x
53 = - - - x 100, 53(2x + 48) = 200x, x = 27
17.12a= 549.12a, a= 32.07u 2x+ 48
4. Atomic weight of metal = equivalent weight x valency 13. Given that, oxygen contents in element oxide is 20% by weight.
= 20 X 2 = 40 Hence, element content in element oxide is 80% by weight.
Molecular formula of metal chloride= MCl2 Then, equivalent weight of unknown element
Molecular mass of MCl 2 = 40 + 2 x 35.5 = 111 g mo1- 1
= 80 X 8
+6 20
5. In acidic medium, K 2 Cr2 0 7 ~ Cr 3+
. . molecular weight :. Equivalent weight of unknown element = 32
Equivalent weight of K2Cr2O 7 = . . .
change m oxidation state of Cr 14. Let I00 g alkaloid contains nitrogen= 17.28 g
M M : .162 g alkaloid w ill contain nitrogen
= --- = -
2(6 - 3) 6 17.28 X 162 = 27_ "" 28
100 g 9g g
+5 +7 0
6. 3HCIO3 ~ H C1O4 + Cl 2 + 202 + H 2O
Atomicweightofnitrogen= 14
. molar mass So, number of atoms of nitrogen present in one molecule of
Equivalent mass ofHCIO 3 = - - - - - - - - - -
change in oxidation number 28
alkaloid= =2
34 5 14
= .4 = 16.89
(5-0) 15. Oxide I Oxide II
I00x 0. 1 %of0 22 30
7. Number of gram equivalents ofHCI 0.0 1
1000 % ofFe 78 70
Number of gram equivalents of HCI = number of gram 22
Moles of oxygen = - = 1375
equivalents of metal carbonate 16
2 78
Therefore, mass of 1 g equivalent of carbonate salt =- - = 200 g Moles of iron= = 1.392
0.01 56
(As mass of metal carbonate = 2 g)
Ratio ofFe and O in it will be 1 : I.
Equivalent mass of metal carbonate = 200 g
Therefore, formula of first oxide is FeO.
8. Change in ox idation number= 0.5 · 2 = 1
According to this formula,
22 parts ot O = I atom of 0
and 78 parts of Fe= 1 atom of Fe
1 70
Change in oxidation number = I X2 = 2 Thus, 70 parts of iron= x = 0.897 atoms of iron
78
Equivalent mass ofNa 2S2O 3 = M , = M 1 I x30
1 and 30 parts of oxygen = - - = I. 36 atoms of oxygen
22
2
Equivalent mass of I 2 = ~ Ratio ofFe and O in second oxide= 0.897: 1.36 = I : 1.5 or2: 3
14 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Hence, formula w ill be FeiO 3• Ifwe multiply the first formula of 23. Na 2CO 3 + 2HCI- 2NaCI + H 2O + CO 2
oxide by 3, then we get F~O 3. So, for the same weight of
oxygen, the ratio of weights of iron will be 3 : 2 (as for In the above reaction, equivalent weight of Na 2CO 3 is M
2
(Ft:iO 3 : Fe3O 3).
because 2 moles ofNa+ being transferred per mole ofNa 2CO 3
£hydroxide
16. 24. Given, vapour density = 70
£metal + Eo_
Molecular weight= 2 x vapour density= 2 x 70 = 140
0.995 E (CO)x = (12 + l 6)x = (28)x
E + 8 or metal =9
£metal + l7 motal (28)x = 140
17. Mohr's salt is (NH4 )iSO4 · FeSO4 · 6H 2O X = 140 = 5
The equation of Mohr's salt with Fe in acidic medium is 28
2 2 Formula is (CO)5.
5Fe + + MnO4 + 8W- 5Fe3+ + Mn + + 4H2O
Total change in oxidation number of iron 25. Weight of copper oxide = 5 g
=(+ 3)-(+ 2)=+ 1 Weight of copper taken= 4 g
So, equivalent weight of Mohr's salt :.Weight of oxygen in copper oxide = 5 - 4 = 1g
molecular weight of Mohr's salt :. Weight of copper reacted with 1 g of 0 2 = 4 g
1 :. Weight of copper which would react with 8 g of
4x8
= 392 = 392 02 = - - = 32g
1 1
Hence, equivalent weight of copper= 32
18. Camphor is used in molecular mass determination due to volatile
nature. The method is called Rast's camphor method. Camphor +7 2
acts as a solid solvent w hich is volatile, hence can be removed 26. 5C20~- + 2MnO4 + 16W- I0CO2 + 2Mn + + 8H2O
easily. . . h molecular weight
Eqmva1ent we1g t = - - - - - - - - - -
19. SnCl 2 + Cl 2 - SnC14 change in oxidation number
190 71
Let £ 1 is the equivalent weight of SnCl 2. = ~ = 31.6
5
190
Then = __.2_!__ 27. Increase in oxidation state= 2
' E1 35.5
Increases in oxidation state = 2
£ 1 =95
20. MnO4 + 8H+ + 5e-- Mn 2+ + 4 Hp ~ 0
H2S + 2HNO3 ~ 2H2O + 2NO2 + S
Gain of electrons = 5
Molecular weight= M
Hence, the equivalent weight of
. . h molecular weight M
Equ,va1ent we1g t = =- H S= molecular weight
gain of electrons 5 2
change in oxidation number
21. Equivalent weight of the metal
weight of metal x _ =~= 17
35 5 2
weight of chlorine
(74.5 - 35.5) X 35.5 28. If_!_ in place of_!_, mass of carbon atom is taken to be the relative
39 6, 12
35.5 atomic mass unit, the mass of one mole of a substance will be
_ Weight of metal oxide remain unchanged.
22
Weight of metal chloride 29. Atomic weight of element,
Equivalent weight of metal + Equivalent
M = equivalent weight x valency
weight of oxide
= 20 X 3= 60
Equivalent weight of metal + Equivalent
weight of chloride Molecular formula of its oxide= M 2O 3
3 £+8 Hence, molecular weight of oxide
5 E+ 35.5 = 2 X 60 + 3 X 16
E = 33.25 =120 + 48=168
Topic 4 Percentage Composition
1. 6. Weight of empirical formula,
Atomic Simpler
Element % age Molar ratio CH2 = 12+ (Ix 2)= 12+ 2= 14
mass molar ratio
Mass of one mole of the compound= its molecular weight = 42
C 10.06% 12 10.06 = 0.84 0.84 = I
molecular weight
12 0.84 11 =- - - - - - ~ - -
empirical formula weight
H 0.84% I 0.84 = 0.84 0.84 =I
I 0.84 = 42 = 3
Cl 89.10% 35.5 14
89.10 = 2.5 ~=3
35.5 0.84 :. Molecular formula= (empirical formula) x n
= (CH 2) x 3 = C3H6
Thus, the empirical formula of the substance is CHCl 3. 7. Molecular weight= 2 x vapour density
2. Since, the molecular formula is n times the empirical formula, = 2 X 45 = 90
therefore, different compounds having the same empirical
Empirical formula weight= 12 + 2 + 16 = 30
formula must have different molecular weights.
molecular weight
3. n= - - - - - - - -
Elements C H N empirical fonnula weight
Ratio by weight 9 I 3.5 = 90 = 3
Molar ratio 9/12 = 0.75 1/1 = I 3.5 I 14 = 0.2 5 30
:. Molecular formula of the compound
Simpler molar 0.75 = _ 1_ =4 0.25 = I = (CHPh = C3f\;O3
3
ratio 0.25 0.25 0.25
Topic 5 Stoichiometry and
So, empirical formula = C3H 4N Stoichiometric Calculations
molecular weight 1. Weight of sample= 10 g
where, n=--------
empirical formula weight Let weight of CaCl 2 = xg
108 CaC1 2 -➔ CaCO 3 -➔ CaO
n= - =2
54 I mol lmo l lmol
X X X
Molecular formula= (C3H 4N)i = ¼H8 N 2 mol mol 56 mol
111 100
4. An aromatic hydrocarbon (empirical formula C 5H 4 ) 1 62
Mole of Cao = ·
+ H2SO4 -➔ Monosulphonic acid 56
~ - ).62 ⇒ X = 3.21 g
·: 0.104 g of monosulphonic acid required IO mL of~ NaOH for 111 56
20 3.2 1
complete neutralisation ⇒ %ofCaCl 2 = - X 100= 32.1 %
10
O.I04 = _'.._ xlOxl0-3
I
equivalent weight 20 2. Ag2 CO3 ~ 2Ag + CO2 + - 0 2
. . 0.104x2 276g 216g 2
Equivalent weight = = 208
10-3 As 276 g of Ag2CO3 will give= 2 16 gof Ag
Empirical formula weight = 5 x 12 + 4 x 1 = 64 So, 2.76 g of Ag2CO3 will give
208 2.76 X 2 16 = _
n= = 3.25 "" 3 2 16
64 276 g
The molecular formula of hydrocarbon wi ll be C 15H 12 3. CX4 + 202 -➔ CO2 + 2X2O
5. I mol 2mol
Element % age Molar ratio Simpler molar ratio
= 2 X 32 g= 64 g
N 30.5 30.5/14 = 2.18 I 1.74 g 0 2 reacts with CX4 = 9.0 g
0 69.5 69.5/16 = 4.34 2 9 0 64
64 gO2 wi ll react with CX4 = · x = 33 1
1.74
Empirical formula = NO 2
Molecular mass of CX4 = 331 or 331 = 12 + 4x
Empirical formula weight = 46 ⇒
92 33 2
n= - =2
X = l - l = 79.8 "" 80
46 4
Molecular formula= (NOi) 2 = NP4 where, x = molar mass of X.
16 I Chapterwise & Topicwise Engineering Entrances Solved Papers
4. Silver solution in l mol CaO = I mol CaCl 2
Ag + HNO 3 + NaCl - AgCI = 108 + 35.5 = 143.5 0.56 Ca
Atomic mass of Ag= 108 g 56
=
- - mol O 0.01 molCaCl 2

Weight of Ag= 5.82 g = 0.0 1 x 111 g CaCl2

·: 143 .5 g AgCl is obtained from Ag= I 08 g = 1.11 g CaC1 2
:. 7.20 g AgCI will be obtained from Ag Thus, in the mixture, weight of
108 X 7.20 = .4[ NaCl= 4.44- 1.1 1= 3.33 g
5 8
143.5 g 3.33
:. Percentage of NaCl = - - x I 00 = 75%
Weight of Ag taken= 5.82 4.44
5 18 11. Weight of pure NaCl = 6.5 x 0.9= 5.85 g
% purity= .4 x I 00 = 93.09%
5.82 5 85
Number of equivalence ofNaCI = · = 0.1
5. CaCO3 + 2HCI - CaCl2 + CO 2 + H 2O 58.5
100g ?Jg 44g Number of equivalence ofNaOH obtained = 0.1
l 00 mL of20% HCI solution= 20 mol HCI Volume of 1 M acetic acid required for the neutralisation of
Here, CaCO3 is the limiting reactant. NaOH = O. l x IOOO = 100 cm 3
l 00 g of CaCO3 gives 44 g CO2 I
:. 20 g ofCaCO3 will give CO 2 = ~ x 20= 8.80 g of CO2 12. Number ofmillimoles ofCa(OH)z = 50 x 0.5 = 25
100 Number ofmillimoles ofCaCO3 = 25
6. Ba(OH)i + CO2 BaCO3 + Hp
-➔ Number of miIii equivalents of CaCO3= 50
·: 5 mo les ofBa(OH)z = 5 moles ofBaCO3 : .Volume of0.1 N HCI =2Q = 500 cm 3
Mass ofBaCO3 = moles of BaCO3 x molecular mass of 0.1
BaCO3 = 5 x 197 = 985 g 13. Titration of oxalic acid by KMnO4 in the presence of HCI gives
7. unsatisfactory result because HCI is a better reducing agent than
Initially 20ml 50ml 0
oxalic acid and HC I reduces preferably MnO4 to Mn 2+.
After burning 0 (50-40) ~ 10mL 20 mL 14. KMnO4 reacts with oxalic acid according to the following
:. Volume of gas left after cooling equation.
2
= 10 mL 0 2 + 20 mL CO2 = 30 mL 2MnO4 + 5C20~- + 16-W - 2Mn + + 10CO2 + 8H 2O
. molecular mass
H p(g)will be condensed to H 2O(/) after cooling. Eqmvalent mass ofKMnO4 = - - - - -
7- 2
8. Mohr's salt is FeSO4 · (NH4 ) 2SO4 · 6H2O N Y-Mno 4 = 5 X molarity = 5 x 10-4
Only oxidisable part is Fe2+.
• f C 2- molecular mass molecular mass
[Fe2+ - Fe3+ + e-]x 6 Eqmva1ent mass o 20 4 = - - - - - = - - - - -
2(4 - 3) 2
Cr2O~- + 14H+ + 6e- - 2 C r3+ + 7Hp 2
NVJ.0 2- = 2 x molarity = 2 x 10-
6Fe2+ + Cr2 O~- + 14H+ - 6Fe3+ + 2Cr 3+ + mp 4

N1V1=N2V2
Millimoles ofFe2+ = 750 x 0.6 = 450 5 X 10-4 X V1 = 2 X 10-2 X 0.5
450 2
Moles ofFe2+ = = 0.450 mol V = 2 X I 0- X 0.5 = 20 L
1000 1 5 X 10-4
6 mot Fe2+ = I mol Cr2O~-
15. A. CaCO3 ~ .. CaO + CO
0.450 mol Fe2+ = 0.450 = 0.075 mol Cr,O72- 100 g decompos1110n
224
i
6 -
·: 100 g CaCO3 on decomposition gives= 22.4 L CO 2
= 0,075 X 294 g=22.05g :. 10 g CaCO3 on decomposition will give
9. 2Na 2HPO4 + NaH2PO4 + 2(NH 2) 2CO 22.4 x IO L CO = 2.24 L CO
100 2 2
- Na5P3O10 + 4NH3 + 2CO2
Hence, the stoichiometric ratio of sodium dihydrogen B. Na2CO3 Excess HCI 2NaCI + H2O+ CO2
orthophosphate and sodium hydrogen orthophosphate is 106 g 22.4 L
2 : l or 3 : 1.5
I 06 g Na 2CO3 gives= 22.4 L CO2
10. CaCO3 ~ CaO + CO 2 1.06 g Na 2CO3 will give CO 2
I mol I mol 22
= .4x I.06 L CO 2 = 0.224 L CO 2
CaCl 2 + Na 2CO 3 - CaCO3 + 2NaCI 106
I mol I mol
 Some Basic Concepts of Chemistry I 17
From Eq. (i) and Eq. (ii)
C. C E:ss 02 CO2
12 g co ust1on 224 L 100M =3MxV
12 g carbon on combustion gives= 22.4 L CO2 V = IOO = 33.3mL
2.4 g carbon on combustion will give 3
22.4 X 2.4 L CO 19. Required equation is given below:
2
12 Zn + 2OH-- ZnOi- + 2H+ + 2e-
= 2 x 2.24 L CO2 = 4.48L CO2
NO3 + 8H+ + 8e-- OH- + 2Hp + NH3
D. 2CO Excess 02 2CO From the above equation,
2(12+ I~ combustion 2x224\ ·: 8 moles of electrons are absorbed by 85 g of NaNO 3
56g
56 g carbon monoxide on combustion gives 85
:. I mole of electron will be absorbed by g of
= 2 X 22.4 L CO2 8
0.56 g carbon monoxide on combustion will give NaNO3 = 10.625 g
2 22 20. CH 3- NH2 + HNO2 -
x .4 x 0 ·56 L co2 = 0.448 L co, CH 3OH + N 2 + HzO
56 - l mole of methylamine gives l mole ofN2
Hence,A- 4,B - l ,C- 2andD - 3. i.e. 22.4 L of nitrogen at NTP.
16. l 00 mL of l M AgNO 3 =
0.1 mol AgNO 3 21. K 2SiO8 (aq) + 2KI(aq) - 2K2SO4(aq) + I i(aq)
100 mL of l M CuSO 4 = 0. 1 mol CuSO 4 In this reaction one mole of K 2Sz08 reacts with 2 mo les of KI,
2AgNO 3 + H2S - Ag2S + 2HNO3 hence the stoichiometry of this reaction is I : 2.
2mol I mot
0. 1 mo! 0.05 mo! 22. Weight of 11.2 dm 3 of CO2 gas at STP = 44/2 = 22 g
CuSO4 + H 2S - CuS + H 2SO 4 KOH + CO2- KHCO3
I mo! I mo! 56 g 44 g
a I mot 01 mot
Mass of KOH required for complete neutralisation of22 g
:. Ratio of the amounts ofH 2S needed= 0.05 : 0.1 = I : 2 56
CO 2 is = x 22 = 28 g
17. Fez0 3 + 3CO - 2Fe + 3CO2 44
1 mot 3mol
23. 6Fe2+ + Crp~- + 14H+ - 6Fe3+ + 2Cr3+ + 7Hz0
Volume of l mole carbon monoxide= 22.4 L (at STP)
+6
l mole of ferric oxide is reduced by 3 moles of CO Cr2o~-- Cr 3+ change in oxidation state, i.e. x factor= 6
= 3 x 22.4 L of CO= 67.2 dm3 of CO Mohr's salt, FeSO 4 · (NH4 )iSO4 · 6H2O
18. In acidic medium, MnO 4 is reduced to Mn 2+ Oxidation, Fe2+- Fe3+ change in oxidation state, i.e. x factor
+7
MnO4- M n +
2
=I
Mole ratio is reverse of x-factor ratio. Therefore, one mole of
Change in oxidation number = 7 - 2 = 5 dichromate required= 6 moles of Mohr's salt.
Solution X Solution Y
24. 2Al(s)+ 6HCl(aq)- 2Al3+(aq) + 6Ci-(aq) + 3H2(g)
N 1Vi = N2V2
3 x 22.4 L H 2(g) at STP is produced by 6 moles ofHCl (aq).
For Fe2+ For MnO 4
Hence, 11.2 L H 2 (g) at STP is produced by I mole of
N x 25 = SM x V [·: For MnO4, N = 5 Min acidic medium] HCl(aq).
25N = SM x 20(V= 20 mL) 25. 2C2H 2 + 502- 4CO 2 + 2Hp
25N= I00M ...(i) 2cc 5cc
100cc 250cc
In neutral medium, MnO4 is reduced to MnO 2
+7 +4 Hence, air will be needed = l OO x 250= 1250 cc
MnO4- MnO 2 20
Change in oxidation number = 7 - 4 = 3 26. SCO + Iz05 - 5CO2 + 12
Solution X Solution Y I mole ofl2 = I mole oflzO~ = 5 moles of CO
N 1V1 = NzV2 Hence, mole of CO= 5 x ~ = 0.05
For Fe2 + For Mn04 254
(As mass ofl2 = 2.54 g and molar mass ofl2 = 254)
25xN = 3M XV
Mass of CO= 0.05 x 28 = I .4 g
[·: For MnO4, N = 3M in neutral medium] Mass of CO2 = 2 - 1.4 = 0.6 g
25N = 3M XV ...(ii) Massoo
o/c f CO -- 0.6 X 100 -- 30
2 2
18 I Chapterwise & Topicwise Engineering Entrances Solved Papers

27 0 rn, ------> s,'¢rs,+ 3HB,

CH4 + 202-
16g
CO2 + 2H2O + 890 kJ

:. 16 g CH 4 bu rns in air to liberate = 890 kJ of heat

:. 3.2 g CH 4 will liberate=

890 3 2
x · = 178 kJ of heat
16
Br
31. C2H 4 + 302 - 2CO2 + 2H 2O
Molecular weight of C6H 5OH = 94 28 g 96 g
Atomic weight of Br= 80 ·:The weight of oxygen required for complete combustion of28 g
of ethylene = 96 g
Amount of Br utilised 6x80= 480g
:. Weight of oxygen required for combustion of2.8 kg ethylene
·: 94 g of C-i;H 5 OH reacts with 480 g of bromine. 96x2.8xl000k = _ k
480 2 96
:. 2 g ofC6Hp H will react with = x = 10.2g 28 X 1000 g g
94
28. Amount of pure limestone (CaCO3 ) is 10 g of90% sample 32. 2NaHCO 3 ~ Na 2CO 3 + H 2O + CO2
2 m:,l I m:,l
90
=- X10=9g ·: 2 moles NaHCO3 on decomposition gives= 1mole Na 2CO3
100 :.0.2 mole NaHCO 3 on decomposition will give
t!. I
CaCO 3 - CaO + CO2 = - x 0.2 = 0.1 mol Na 2CO 3
100 g 22.4 L 2
I 00 g of limestone gives 22.4 L of CO 2 at STP t!.
9 g of limestone will give 33. CaCO 3 + 2HC1 - CaCl2 + HzO + CO2
22.4 IOOg 2x36.5g 44g
= - - X 9 = 2.0 16 L CO2 I L of I N HCI means= 36.S g HCI
100
Here, HCI is limiting reagent. Therefore, it reacts with SO g
29. Combustion of propane takes place as follows CaCO 3 and produces 22 g CO2.
C3H 8 + 502 - 3CO2 + 4Hz0
Propane Oxygen
t!.
34. CaCO 3 (s) - CaO(s) + CO2 (g)
·: 1 L of propane required S L of oxygen for combustion. IOOg 56g

:. 20 L of propane required oxygen = S x 20 = I 00 L ·: 56 g CaO is obtained from= 100 g CaCO 3

28
30. The combustion of methane can be represented by the following :. 28 g CaO is obtained from= IOO x = SO g CaCO 3
equation S6
:. Value of x (amount of CaCO3) = 50 g
2
Structure of Atom
QUICK REVIEW
Sub Atomic Particles
• Some important features of the three fundamental pa1ticles • Isotones have ilifferent mass number (A) as well as
(i) The charge on an electron is - 1. 602x 10- 19 Cand its different atomic number (Z) but have same number of
mass was found to be 9.11 x I 0- 28 g . neutrons.
(ii) The specific charge (elm ratio) of an electron is • Isoiliaphers have same isotopic number.
l.76x10 8 Clg • Relationship between velocity (c), wavelength (A),
(iii) Mass of 1 mole of electron is nearly 0.55 mg. frequency (v) and wave number (v).
(iv) Charge on one mole of electron is "' 96500 C or 1F. (a) C = VA,
1
(v) Mass of a proton is found to be l.675x 10- 24 g. (b) v= -
19 1\.
(vi) Charge on a proton is +1602x 10- C
(c)v = v l c
(vii) The specific charge (elm) ratio of proton is
where, c is the velocity in ms -l , v is the frequency in s- 1
9.58x 10-4 Cl g .
and A is wavelength in m.
(viii) Neutron is slightly heavier than proton. Its mass is • Relationship between energy (E), frequency ( v) and
found to be l.675x 10-4 Cl g. wavelength (A).
(ix) Specific charge of a neutron is zero. he
E = hvor E = -
• Positrons are positive counter part of the electrons. A.
34
Neutrinos and antineutrinos are the particles of small mass where, his planck's constant, h = 6.62 x 10- Js.
and zero charge. pi mesons andµ mesons are the particles
• Energy of electron in unielectron atomic system.
having a mass intermeiliate between that of the electron
and proton. Mesons may be positively, negatively charged E = - 131222 kJ mol-1
n 2
or neutral. n
• Radius of nucleus is of the order of I. 5x 10- 13 cm to _ - 2.11x10- 18 z 2 _
or E 11 -
2
1 atom 1
13 n
6 . 5x10- cm.
39 3
(i) Volume of the nucleus is about 10- cm . (volume of or E n = -- - 13.5 z2 V -1
2
. e atom
15 n
the nucleus is) I0- times that of an atom.
(ii) Density of the nucleus is of the order of 10 14 g cm -3 . • The number of spectral lines in the spectrum when the
electron comes from nth level to the ground level
Different Types of Atomic species _ n(n- 1)
• Isotopes have same atomic number (Z) but different mass 2
number (A).
• The intensities of spectral lines decrease with increase in
• Isotopes have same mass number (A) but ilifferent atomic the value of n for example, the intensity of first Lyman line
number (Z). (2 ➔ I) is greater than second line (3 ➔ 1).
20 I Chapterwise & Topicwise Engineering Entrances Solved Papers

• Energy of quantum emitted when electron drops from Value of l 0 I 2 3 4

n1 n1 Type of s p d f g
orbital
1 1 2 1
M = 1312Z [ - - - -- ] kJ mol" Shape of Spherical Dumbbel Double Complex Complex
n2 n2
I 2 orbital I dumbbell
2
• Frequency, v = RZ [ - \ - --\-] Magnetic Quantum Number (m)
n1 n2
15
• It represents the orientation of orbitals in the external magnetic
where, R = 3.289x 10 s-1 field. In other words, it represents the number of orbitals of a
• Wave number, particular type. It can have any value from -1 to + 1 including
2 zero, for each value of/.
v = R'Z [-\- - - \ -]
• The number of orbitals belonging from an orbit is equal to the
n1 n1
1
orbit number.
where, R '= 109678cm-
• Each orbital of an orbit in single electron system have exactly
• Radius of nth orbit, equal energy, i.e. ns = np = nd = nf = ...
2 10
n x0.529x 10- m • Each orbital of an orbit in a multi electron system have nearly
rn = ____ z____
equal but slightly different energy. Their energy increases with
the increase in / value. i.e.
• Velocity of nth orbit,
ns < np < nd < nf <...
2.188xl06 xz _1
vn = ms • The orbital angular momentum of electron is given by
n
.J l(l + 1).}!_
21t
• Number of revolutions in nth orbit = ~
21t"f11
Spin Quantum Number (s)
Quantum Numbers • It was proposed by Goldschmidt and Uhlenbeck. It represents
• According to de-Broglie, all the moving material the rotation of electron about its own axis dur ing its
objects possess wave like characteristics. revolution round the nucleus. it can have the values + 1/ 2 or
34 -1 / 2, which normally represents clockwise and anticlockwise
;\, =}!___ where, h = 6.626x 10- Js, m = mass (in kg) spin, respectively.
mv
v = velocity (mis). • For one electron system, the energy of orbital depends only on
• Heisenberg's uncertainty principle. It is impossible 18 the number of nodes, i.e. on and not on/or m . It means in
determine momentum and position of a sub-atomic -atoms or ion energy levels of orbitals in a shell are same

particle precisely and simultaneously Lix-Lip ~ }!__

41t
where, Lix = uncertainty in position, Lip = uncertainty in
momentum.
• The wave function \j/ represents an orbital where as \j/ 2
signifies the probability of finding electron in that
region for \j/ 2 = 0 the probability for finding electron is
zero.
Principal Quantum Number (n)
It represents the orbit from which the electron is
belonging. It can have the integer val ues 1, 2, 3, .... .
With the help of n, we may determine the distance of
electron from nucleus, speed of electron, its energy, etc.
• Magnetic moment, (spin only) µ= .Jn (n + 2) BM
where, n is the number of unpaired electrons. Unit of magnetic
moment is BM.
• The electrons in a poly electronic atom are placed one by one
in order of increasing energy level (aufbau principle). The
subshell with lower values of (n + /) possesses lower energy
level. If (n + I ) for two orbitals is same, the one with lower
values possesses lower energy level and should be filled first.
Spin Multiplicity
S = 2s + 1 (s = magnitude of sum of total spin quantum numbers
of electron present).
• The p lane and point at which zero electron density exists
(\j/ 2 = 0) is known as nodal plane or nodal point.

Azimuthal or Subsidiary or Angular Momentum
Quantum Number (/)
It represents the type of orbital from which electron is
belonging and the shape of the orbital. It can have any
value from 0, 1, 2, ... to (n - 1) for each value of n.
• An orbital with quantum nun1ber n and / possesses angular
nodes = n - I - 1 and radial nodes = L
where, n = principal quantum number
I = azimuthal quantum number
Thus, total number of nodes in an orbital = (n - 1)
 Topic 1
Sub-Atomic Particles
2012
1. The triad of the nuclei that is isotonic, is [ManipalJ 11. Which of the following make up an isotonic triad ?
(a) 6 cl4' 7N14' 9F19 {b) 6 cl4' 7N15' 9F17 [Kerala CEE]

(c) 7 d4' 7N14' 9Fl7 (d) 6 cl2' 7N14 •9 F'9 (a) 78Ge
32 , 77As
33 , 74Ga
31
2. Which of the following are iso-electronic? [OJEEJ ( c) 233 U 232Tb 239pu
92 ,90 ,94
(a) Li and Be+ (b) H- and He+
(c) He and H (d) Be+ and H e 14C
() 16 1sN
6 , s0, 7

3. An elements [OJEE] 12. The number of electrons and neutrons ofan element is 18 and
(a) is one type of atom 20, respectively. Its mass number is CWB JEE]
(b) is two or more types of atom (a) 2 (b) 17 (c) 37 (d) 38
(c) has constant boiling point 13. Which one of the following ions is not isoelectronic with
( d) has constant melting point 0 2-7 [Jamia Millia Islamia]
2010 (a)Ti+ (b)Na+ (c)F- (d) N 3-
4. Which has the highest elm ratio ? [Manipal]
2006
(a) He 2+ (b) H+ (c) He+ (d) D+
14. Which one of the following sets of ions represents a
2009 collection of isoelectronic species ? [AIEEEJ

5. Increasing order (lowest first) for the values of elm for (a) K+, Cl- , Ca 2+, Sc3+ (b) Ba 2+, Sr 2+, K +, s 2-
electron (e), proton (p ), neutron (n) and a-particles is (c) N3-, O2- , F - , S2- (d)Li+, Na+,Mg 2+,Ca 2+
[Indraprastha CET, CG PET]
15. Ca 2+ is isoelectronic with [Manipal]
(a)e,p,n,a (b) n, a,p, e
(c) n,p, e, a (d) n,p, a, e (a) Na+ (b) Ar (c) Mg 2+ (d) Kr
16. The lightest particle is [Manipal]
2008
(a) a -particle (b) positron
6. The electronic configuration of a dipositive ion M 2+ is (c) proton (d) neutron
2, 8, 14 and its mass number is 56. The number of
17. How many neutrons are present in tritium nucleus?
neutrons present is [Manipal]
(a) 2 (b) 3 CWB JEEJ
(a) 32 (b) 42 (c) 30 (d) 34
40 (c) 1 (d) 0
7. An isobar of 20 Ca is [MHTCET]
40 18. Which one of the following has unit positive charge and 1 u
( a) 18 Ar (b) 20Ca3s mass? [WB JEE]
(c) 20Ca 42 (d) ,sAr38 (a) Electron (b) Neutron
8. The nucleus of an atom contains [MPPET] (c) Proton ( d) None of these

(a) proton and electron 19. N uclear theory of the atom was put forward by [AMU]

(b) neutron and electron (a) Rutherford (b) Aston

(c) proton and neutron (c) Neils Bohr (d) J J Thomson
( d) proton, neutron and electron 20. Which particle contains 2 neutrons and l proton ?
9. lsoelectronic pair among the following is (a) 1 H2 (b) He 4 [Guj CET]
2
[UPSEE] 3 2
( C) 1 T ( d) 1 D
(a) Ca and K (b) Ar and Ca 2+
(c) K and Ca 2+ (d) Arand K 2005
2007 21. Number of neutron in C12 is [BCECE]
1O. Mg 2+ is isoelectronic with [KCET] (a) 6 (b)7 (c) 8 (d) 9
(a) Cu + 2
(b) Zn + 2 22. An isotone of j~ Ge is [DCE]
(c) Na+ (d) Ca 2+ (a) j~ Ge (b) jj As (c) j~ Se (d) j: Sc
 Topic 2
Atomic Models
2014 2012
1. Which of the following relation is incorrect regarding 8. The kinetic energy of an electron in the second Bohr orbit
Bohr's theory? [BITSAT] of a hydrogen atom is [a 0 is Bohr radius] IIIT JEE]

( a) Velocity of electron oc ..!. (a) h2 ? (b) h2

11
41t 2 ma0 l61t 2 ma5
(b) Frequency of revolution oc _ l_
112 (c) h2 (d) h2
(c) Radius oforbit oc 11 Z
2 ma5
321t 2 641t 2 ma5

(d) Force on electron oc

1 9. If the radius ofH is 0.54 A, then what will be the radius of
4 Li 2 +? [BITSAT]
11 3

2. The emission spectrum of hydrogen discovered first and (a) 0.17 A (b) 0 .36 A (c) 0.53 A (d) 1.59° A
the region of the electromagnetic spectrum in which it
belongs, respectively are [WB JEE]
2011
10. The work function ( <!>)of some metals are listed below. The
(a) Lyman, ultraviolet (b) Lyman, visible
(c) Balmer, utraviolet (d) Balmer, visible number of metals which will show photoelectric effect
when light of 300 nm wavelength falls on the metal is
3. The Balmer series in atomic hydrogen is observed in the
following spectral region IAMUJ Metal Li Na K Mg Cu Ag Fe Pt w
(a) infrared (b) ultraviolet <j>(eV) 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75
(c) visible (d) far IR
4. Energy of an electron is given [IITJEE]

E = - 2.179x 10- 1(::) 18

(a) 2 (b) 4 (c) 6
11. A gas absorbs photon of 355 nm and emits at two
(d) 8

wavelengths. If one of the emission is at 680 nm, the other

Wavelength of light required to excite an electron in an is at [AIEEE]
hydrogen atom from level 11 = l to 11 = 2 will be
(a) 1035 nm (b) 325 nm
(h = 6.62 x 10- 34 Js and c = 3.0 x 108 ms - I )[JEE Mains] (c) 743 nm (d) 518 bm
(a) 1.214 x 10- 7 m (b) 2.816x 10- 7 m 12. The frequency of light emitted for the transition n = 4 to
7 7 11 = 2 of He+ is equal to the transition in H atom
(c)6.500xl0- m (d)8.500x10- m
co1Tesponding to which of the following? IAIEEEJ
2013 (a)n = 3to11 = l (b)11 = 2to11 = l
5. The transition of electron in H atom that will emit (c)n =3 to11 =2 (d)11=4to11=3
maximum energy is [Manipal] 13. Which transition in the hydrogen atomic spectrum will
(a) 11 3 ➔ 11 2 (b) 11 4 ➔ 11 3 have the same wavelength as the transition, 11 = 4 to n = 2
(c) 11 5 ➔ 11 4 (d) 11 4 ➔ 11 5 of He+ spectrum? [Kerala CEE]

6. Which of the following is not true in Rutherford's nuclear (a)n = 4ton = 3 (b)11 = 3to11 = 2
model of atom [MHT CETJ (c)11 =4to11=2 (d)11=3to11=l
(e)n = 2to11 = l
(a) Protons and neutrons are present inside the nucleus
(b) Volume of nucleus is very small as compared to the 14. The energy of an electron in first Bohr orbit of H-atom is
volume of an atom - 13 . 6 e V. The possible energy value of electron in the
( c) The number of protons and neutrons are always equal excited state of Li 2+ is IWB JEE]
( d) The number ofelectrons and protons are always equal (a) -122.4 eV (b) 30. 6 eV
7. When the electrons ofhydrogen atom return toLshell from (c)-30. 6eV (d) 13 . 6 eV
shells of higher energy, we get a series of lines in the 15. The electronic transitions from n = 2 to n = 1will produce
spectrum. This series is called [KCETJ shortest wavelength in (where, n = principal quantum
(a) Balmer series (b) Lyman series state) IWB JEE]
(c) Brackett series (d) Paschen series (a) Li. 2 + (b)He+ (c)H (d)H+
 Structure of Atom I 23
2010 25. An electronic transition in hydrogen atom results in the
16. The energy required to break one mole of Cl-Cl bonds in formation of H0 line of hydrogen in Lyman series, the
1
Cl 2 is 242 kJ mol- • The longest wavelength of light energies associated with the electron in each of the orbits
capable of breaking a single Cl-Cl bond is [AIEEEJ involved in the transition (in kcal rnol - t) are
[BITSAT, AMU, EAMCET]
(a) 594 nm (b) 640 nm
(c) 700 nm (d) 494 nm (a) - 313.6, - 34.84 (b) - 313.6, - 78.4
(c) - 78.4, - 34.84 (d) - 78.4, - 19.6
17. Ionisation energy of He+ is 19 . 6x 10- 18 J atom- 1 • The
energy of the first stationary state (n = I) of Li 2+ is 26. Deflection back of a few particles on hitting thin foil of
(a) 4 . 41 X 10- 16 J atom- 1 [AIEEE] gold shows that [Manipall
(b) - 4. 4l x 10- 17 Jatom- 1 (a) nucleus is heavy
(c) - 2 . 2 x 10- 15 Jatom- 1 (b) nucleus is small
(d) 8 . 82x 10- 17 Jatom- 1 (c) Both (a) and (b)
(d) lectrons create hinderance in the movement of
18. The radius of the first Bohr orbit of hydrogen atom is
a-particles
0.529A. The radius of the third orbit of H+ will be
27. Time period of a wave is 5 x 10- 3 s, what is the
(a) 8.46 A (b) 0.705 A [Manipal]
frequency ? CUPSEEJ
(c) 1.59 A (d)4.76A
(a)5x10- 3 s - 1 (b)2x102 s - 1
19. The wave number of the spectral line in the emission (c)23x 103 s - 1 (d)5 x 102 s - '
spectrum ofhydrogen will be equal to~ times the Rydberg's 28. An electron from one Bohr stationary orbit can go to next
9
higher orbit [UPSEEJ
constant, if the electron jumps from [KCETJ
(a) by emission of electromagnetic radiation
(a)n = 3ton = l (b)n = lO ton =l (b) by absorption of any electromagnetic radiation
(c)n = 9ton = l (d)n = 2ton = l (c) by absorption of electromagnetic radiation of
20. The ratio of the difference in energy between the first and particular frequency
the second Bohr orbit to that between the second and the (d) without emission or absorption of electromagnetic
third Bohr orbit is [RPETJ radiation
wI
2
~ I
3
~~
9
oon5 29. Splitting of spectrum lines in magnetic field is CUPSEEJ
(a) Stark effect
21. The wave number of the first line in the Lyman series in (b) Raman effect
hydrogen spectrum is [Punjab CETJ (c) Zeeman effect
(a) 72755.5 cm - 1 (b) 109678 cm - 1 (d) Rutherford effect
(c) 82258.5 cm - t (d) 65473.6 cm - t 30. The scientist who proposed the atomic model based on the
quantisation of energy for the first time is [J&K CETJ
2009 (a) Max Planck (b) Niels Bohr
22. The number of photons emitted per second by a 60 W (c) de-Broglie (d) Heisenberg
source of monochromatic light of wavelength 663 nm is 31. What is the lowest energy of the spectral line emitted by
(h = 6. 63 X 10- 34 Js) [Kerala CEE] the hydrogen atom in the Lyman se1ies ?
(a) 4 x 10- 20 (b) 1.54 x 1020
(c) 3x 10- 20 (d) 2x 1020 (h = Planck' s constant, c = velocity oflight,R = Rydberg's
(e) 1X 10- 2o constant). [DCEJ
23. Bohr's radius of 2nd orbit of Be 3+ is equal to that of (a) 5hcR (b) 4hcR (c) 3hcR (d) 7hcR
[Indraprastha CET, CGPETJ 36 3 4 144
(a) 4 th orbit of hydrogen (b) 2 nd orbit of He+
rd
(c)3 orbitof Li +
2 st
(d)I orbit ofhydrogen 2007
32. The frequency of radiation emitted when the electron falls
2008 from n = 4 to n = 1 in a hydrogen atom will be (given,
1
24. The ionisation enthalpy of hydrogen atom is ionisation energy of H=2.1 8xJ0- 18 J atom- and
I. 312 x 106 J mol - 1 • The energy required to excite the h = 6. 625 X 10-
34
J s) [Manipal]
electron in the atom from n 1 = 1 to n 2 = 2 is [AIEEEJ 15 1
(a) 1.54 x 10 s- (b) 1.03 x 10 s- 1
15
(a) 8.51 x 105 J rnol- 1 (b) 6.56 X 105 J mol- 1 (c)3.08x1015 s - 1 (d)2.00xl015 s - 1
(c) 7 .56 x 105 J mol- 1 (d) 9.84 x 105 J rnol- 1
24 I Chapterwise & Topicwise Engineering Entrances Solved Papers

33. Which diagram best represents the appearance of the line 42. The number of waves in an orbit are [BITSAT]
spectrum of atomic hydrogen in the visible region ? 2
(a)n (b)n
[Kerala CEE] (c)n - 1 (d)n - 2
Increasing wave length 43. Bohr model can explain [Manipal]
(a) the solar spectrum
(a) (b) the spectrum of hydrogen molecule
I I 1111 I I I
(c) spectrum of any atom or ion containing one electron
(b) only
I I I I I I 11
(d) the spectrum of hydrogen atom only
(c) 44. Zeeman effect refers to the
11 I I I I [Manipal]
(a) splitting up of the lines in an emission spectrum in the
(d) presence of an external electrostatic field
I I I I I
(b) random scattering of light by colloidal particles
(e) ( c) splitting up of the lines in an emission spectrum in a
1111 I I I I I 1111
magnetic field
(d) emission of electrons from metals when light falls
34. The ionisation energy of hydrogen atom is 13.6 eV. What upon them
will be the ionisation energy of He+ ? [WB JEE]
45. The energy of hydrogen atom in its ground state is
(a) 13.6 eV (b) 54.4 eV - 13.6eV. The energy of the level corresponding to the
(c) 122.4eV (d)Zero quantum number n = 5 is [MHT CETJ
35. The wavelength of the radiation emitted, when in a (a)-5.4eV (b) - 0 .54 eV
hydrogen atom electron falls from infinity to stationary (c) - 2 . 72eV (d) - 0.85eV
state 1, would be (Rydberg constant = 1. 097 x 107 m- 1) 46. If the energy difference between the ground state of an
(a) 91 nm (b) 192 nm [UPSEE] atom and its excited state is 4.4 x l 0-4 J, the wavelength of
(c)406nm (d)9.lx10- 8 nm photon required to produce the transition [UPSEEJ
(a)2.26x10- 12 m (b) l.13 x l0- 12 m
36. The energy of second Bohr orbit of the hydrogen atom is
- 328 kJ mol-
1
; hence the energy of fourth Bohr orbit (c) 4 .52x 10- 16 m (d) 4 .52x 10- 12 01
would be [UPSEE]
47. The energy of a photon is 3 x 10- 12 ergs. What is its
1 1
(a) - 4l kJ rnol - (b) - 1312kJmol- wavelength in nm ?
(c) - 164 kJ rno1- 1 (d) - 82kJ mo1- 1
(h = 6 . 62 x 10- 27 ergs, c = 3 x 1010 emfs) [EAMCET]
37. The wavelength of a spectral line emitted by hydrogen
(a) 662 (b) 1324
atom in the Lyman series is Ji_ cm What is the value of (c) 66.2 (d) 6.62
15R
48. What is the energy (in eV) required to excite the electron
n 2 ? (R = Rydberg constant) [EAMCET]
from n = l ton = 2 state in hydrogen atom ?
(a) 2 (b)3 (c) 4 (d)l (n = principal quantum number) [J&K CET]
38. The value of Rydberg constant is [J&K CET] (a) 13.6 (b) 3.4 (c) 17.0 (d) 10.2
1 1
(a) 109678cm- (b) 109876cm- 49. Energy of photon of visible light is [DCE]
1 1
(c) 108769cm- (d) 108976cm-
(a) l eV (b) l MeV (c) l eV (d) l keV
39. The wavelength of a spectral line in Lyman series, when 50. For a Bohr atom angular momentum M of the electron is
electron jumps back from 2nd orbit, is [J&K CET] (n = 0, 1, 2, .... ) [Jamia Millia Islamia]
(a) 1162 A (b) 1216 A (c) 1362 A (d) 1176 A 2 2 2 2
(a) nh (b) n h (c) .Jnh (d) nh
40. The energy ratio of a photon of wavelength 3000 A and
4n 4n 4n 2n
6000 A is [BCECE]
(a)l:l (b)2:l (c) l :2 (d)l:4 2005
51. The velocity of electron in first orbit of H-atom as
2006 compared to the velocity of light is [BITSAT]
41. According to Bohr's theory, the angular momentum of an I l
electron in 5th orbit is [AIEEEJ (a) - th (b) - th
10 100
(a) 25!!._ (b) LO!!_ (c) 10!!._ (d) 2 .5!!._ l
(c) - th (d) same
1t 1t 1t 1t
1000
 Structure of Atom I 25
52. Stark effect refers to the [MPPET] 57. Magnitude of kinetic energy in an orbit is equal to
(a) splitting up of the lines in an emission spectrum in the (a) halfofthe potential energy [BCECEJ
presence of an external electrostatic field (b) twice of the potential energy
(b) random scattering of light by colloidal particles (c) one fowth of the potential energy
( c) splitting up of the lines in an emission spectrum in a ( d) None of the above
magnetic field
58. The H-spectrum show [DCE]
(d) emission of electrons from metals when light falls upon
them (a) Heisenberg's uncertainty principle
53. The relationship between the energy £ 1 of the radiation with a (b) diffraction
( c) polarisation
wavelength 8000 A and the energy £ 2 of the radiation with a
( d) presence of quantised energy level
wavelength 16000 A is [Kerala CEE)
59. Which of the following statements does not form a part
(a) £ 1 = 6£2 (b) E1 = 2E2
of Bohr's model of hydrogen atom? [DCEJ
(c) £ 1 = 4£2 (d) £ 1 = 1/2£2
(e)E1 = £ 2 (a) Energy of the electrons in the orbit is quantised
(b) The electron in the orbit nearest the nucleus has the
54. Rutherford's experiment on the scattering of a-particles
lowest energy
showed for the ftrst time that the atom has [UPSEEJ
(c) Electrons revolve in different orbits around the
(a) electrons (b) protons (c) nucleus (d) neutrons nucleus
55. The energy of the electron in fast Bohr's orbit is - 13. 6eV ( d) The position and velocity of the electrons in the
The energy of the electron in its ftrst excited state is orbit cannot be determined simultaneously
(a) - 3.4eV (b) - 27.8eV [OJEEJ 60. Energy ofH-atom in the ground state is - 13. 6eV, hence
energy in the second excited state is
(c) - 6.8eV (d) - 10. 2eV
[Jamia Millia Islamia]
56. Angular momentum of an electron in the n th orbit of (a)-6.8eV (b)- 3. 4eV
hydrogen atom is given by [RPETJ (c) - l.5leV (d) - 4 . 53eV
(a) nh (b) nh (c) 21t (d)~
21t nh 2nh

Topic 3
Modern Structure of Atom
2014 2012
1. As per de-Broglie's formula a macroscopic particle of mass 4. Which of the following does not represent the
100 g and moving a velocity of 100 cm s - 1 will have a mathematical expression for the Heisenberg uncertainty
wavelength of [WB JEE] principle? [WB JEE]
29
(a) 6.6 x 10- cm (a) &- !).p~ h/(41t) (b) &- !).v~ h / (41tm)
(b) 6.6 x 10- 3o cm (c)M·M~h/ (41t) (d)!).£-&~h/ (41t)
(c) 6.6 x 10- 31 cm
(d) 6.6 x 10- 32 cm 2011
2. The energy rejuired to remove an electron from metal X is 5. Calculate the velocity of an electron having wavelen~th
2
E = 3.31 x 10- 0 J.
Calculate the maximum wavelength of of 0. 15 nm Mass of an electron is 9. 109 x 10- g.
27
light that can photo eject an electron from metal X (h = 6. 626 X 10- erg-s). [Guj CET]
1
(a) 6.01 x 10- 6 m (b) 3.01 x 10- 3 m [AMU]
8
(a) 2 .062x 10- cm-s - (b) 2 .062x 10- 15 cm-s - 1
(c)5.0lxl0- m 6
(d)Noneofthese (c) 4 .84x 108 cm-s - 1 (d) 2 .062x 10- 9 cm-s - 1
3. Energy of one mole of photons of radiation whose frequency
14 2010
is 5 X 10 Hz is [J&K CET]
1
6. If helium atom and hydrogen molecule are moving with
(a) 199.51 kJ mol- the same velocity, their wavelength ratio will be
1
(b) 189.51 kJ mol-
1 (a) 4 : 1 (b) 1: 2 [MPPET]
(c) 198.51 kJ mo1-
(d) 188.51 kJmol- 1 (c) 2 : 1 (d) 1 : 4
26 I Chapterwise & Topicwise Engineering Entrances Solved Papers

7. A particle having a mass of 1.0 mg has a velocity of 3600 15. A cricket ball of 0.5 kg is moving with a velocity of
km/h. Calculate the wavelength of the particle. 100 mis. The wavelength associated with its motion is
(h = 6. 626 x 10- 27 erg-s) [Guj CET] (a) 0.0 1 cm (b) 6.6 x 10- 34 m [Guj CETJ
35
(a) 6.626x 10- 28 cm (b) 6 .626x 10- 29 cm (c) I. 32 x 10- m (d) 6.6 x 10- 28 m
(c) 6.626x 10- 30 cm (d) 6.626x 10- 31 cm 16. The de-Broglie wavelength of a tennis ball of mass 60 g
moving with a velocity of 10 m/s is approximately
2009 (Planck's constant, h = 6. 63 x 10- 34 Js) [MP PET]
8. In an atom, an electron is moving with a speed of 600 mis WlWDm ~1~ m 1

with an accuracy of 0 .005%. Certainity with which the (c) 10- 16 m (d) 10- 25 m
position of the electron can be located is (h = 6. 6 x 10- 34
kg m 2 s - 1 , mass of electron, e111 = 9.1 x 10- 31 kg) 2007
(a) l.52x 10-4 m (b) 5.I0 x 10- 3 m [AIEEEJ 17. A body of mass 10 mg is moving with a velocity of
1
3 3 100 ms - • The wavelength of de-Broglie wave associated
(c) l.92x 10- m (d) 3.84 x 10- m
with it would be (h = 6 . 63 X l 0- 34 J s) [KCET]
9. Calculate the wavelength (in nanometer) associated with a
(a) 6.63 x 10- 35 m (b) 6.63 x 10- 34 m
proton moving at I. 0 x 103 ms - I (Mass of proton 31
(c) 6.63 x 10- m (d) 6.63 x 10- 37 m
= 1.67 x 10- 27 kg and h = 6 . 63 x 10- 34 Js) [AIEEE]
(a) 0.032 nm (b) 0.40 nm 2006
(c) 2.5 nm (d) 14.0 nm 18. Uncertainty in the position of an electron
10. A body of mass x kg is moving with a velocity ofl 00 ms - 1 . (mass = 9.1 x 10- 31 kg)moving with a velocity 300ms - 1 ,
Its de-Broglie wavelength is 6. 62 x l 0- 35 m. Hence, x is accurate upon 0 . 00 l % will be (h = 6. 63 x 10- 34 Js)
(h = 6. 62 X 10- 34 Js) [Manipal]
(a) 19.2x 10- 2 m (b) 5.76x 10- 2 m [AIEEEJ
(a) 0.1kg (b) 0.25 kg (c) 0.15 kg (d) 0.2 kg (c) 1.93 x 10- 2 m (d) 3.84 x 10- 2 m
11. Which of the following is the correct form ofSchrodinger 19. The probability of finding the electron in the orbital is
wave equation ? [Guj CET]
(a) 100% (b) 90-95% [BITSAT]
a2 \jf d 2 \jf a2 \jf + -
(a) - + - + -
2
81t m
- (E-V)\jf = 0 ( c) 70-80% ( d) 50-60%
ox o y o z h
2 2 2 2
20. What is the frequency of photon whose momentum is
a 2 az 8
".12 2 1.1 X 10- 23 kg ms -z ? [MP PET]
(b) __y + ~ + __y + ~ (E - V) \jf = 0
ox oy oz h 2
2 2 2 (a) 5x 1016 Hz
(b) 5 X 1017 Hz
o\j/ 2 o\j/ 2 a'l' 2 8n 2 m
(c) - + - + - + - 2- (E - V)'I' = 0 (c) 0. 5 x 1018 Hz
ox oy oz h
2 2 2
(d) 5 x 1018 Hz
2 ".12 a2
a 8 2 2 21. Wave nature of electrons was demonstrated by [WB JEE]
(d)__y+ ~ + __y+~(E-V)'I' = 0
ax 2
oy 2
oz 2
h
2
(a) Schrodinger
(b) de-Broglie
12. A particle moving with a velocity l 06 mis will have ( c) D avisson and Garmer
de-Broglie wavelength nearly, (d) H eisenberg
27 34
(given, m = 6. 62 x 10- kg, h = 6. 62 x 10- J-s)
22. The uncertainties in the velocities of two particles A and B
[lndraprastha CET]
are 0.05 and 0.02 ms - l respectively. The mass of Bis five
(a) 10- 9 m (b) 10- 13 m (c) 10- 19 m (d) l A times to that of mass A. What is the ratio of uncertainties

2008 (
~BA ) in their positions ?
13. The velocities of two particles A and B are 0.05 and [EAMCETJ
1
0.02ms - respectively. The mass of Bis five times the (a) 2 (b) 0.25
mass of A . The ratio of their de-Broglie's wavelength is (c) 4 (d) 1
[BITSAT, AMU, EAMCET] 23. An electron is moving in Bohr's fourth orbit. Its de-Broglie
(a) 2 : 1 (b) l :4 (c) l : l (d)4: l wavelength is A. What is the circumference of the fourth
orbit? [EAMCET]
14. Which of the following expressions gives the de-Broglie
2
relationship ? [WB JEE] (a) i (b)2A.
(a) p = !!_ (b) A=!!_ (c) A= !!.__ (d) Am =~
mv mv mp p (c) 4A
 Structure of Atom I 27
24. What accelerating potential is needed to produce an 26. The uncertainty in the momentwn of an electron is
electron beam with an effective wavelength of0.090 A? 1.0 x 10- 5 kg ms- 1. The uncertainty in its position will be
4 2
(a) l.86x 10 eV (b) l.86x 10 eV[Guj CETJ 28
(a) 1.50 x 10- m (b) 1.05 x 10- m
26
[DCE]
4 2
(c) 2.86x 10 eV (d) 2.86x 10 eV (c) 5.27 x 10- 3o m (d) 5.25 x 10- 28 m
25. Which of the following is Heisenberg uncertainty 27. Uncertainty in position of a particle of 25 g in space is
principle ? [BCECEJ 10- 5 m. Hence, uncertainty in velocity (ms _, ) is
h
(a) l!..x·!lp~ - ·
h
(b) l!..x·!lp = - (Planck's constant h = 6.6 x 10- 34 Js)
4n 4n [Jamia Millia lslamia]
h
(c) l!..x· !lp ~ ~ (d) l!..x·!lp< - (a) 2.l x 10- 28 (b) 2.1 X 10- 34
4n 4n (c) 0.5 X 10- 34 (d) 5.0x 10- 24

Topic 4
Quantum Numbers
2014
1. In an atom, the total number of electrons having quantwn 2013
nwnbers n = 4, Im1 I= l and ms = - l / 2is [JEE Advanced] 7. For a /-orbital the values ofmare [KCETJ
W3 ~2 W6 009 (a) - 1, 0, + 1
2. The correct set of four quantwn mm1ber for the valence (b) 0, + 1, + 2, + 3
electrons ofrubidiwn atom (Z = 37) is [JEE Mains] (c) - 2, - 1, 0, + l, + 2
1 1 (d) - 3, - 2, - 1, 0, + I, + 2, + 3
(a) 5,0, 0,+ - (b) 5,1,0, +- 8. The magnetic quantun1 nwnber ford-orbital is given by
2 2
I 1 (a) 2 (b) 0, ± 1, ± 2 [OJEEJ
(c)5,l, 1, + - (d)5,0,1+ -
2 2 (c) 0, 1, 2 (d) 5
3. Which of the following sets of quantwn nwnbers could
represent the last electron added to complete the electron
2012
configuration for a ground state atom of Br (Z = 35) 9. Which of the followin g sets of quantum number is
according to the Autbau principle n : l; m1 ; ms [Manipal] restricted? [MPPET]
(a)4;0;0;-l/2 (b)4; l ;l;- 1/ 2 (a) n = 3, l = I, m = + 2 (b) n = 3, / = 1, m = 0
(c)3;1;1; - l/2 (d)4; 1;2;+1/ 2 (c) n = 3, l = I, m = + 1 (d) m = 3, / = 1, m = - 1
4. The statement that is not correct is [KCETJ l 0. Impossible orbital among the following is [KCET]
(a) Angular quantum number signifies the shape of the (a)3/ (b)2p (c)4d (d) 2s
orbital 11. Which of the following orbitals bas zero probability of
(b) Energies ofstationary states in hydrogen like atoms is finding the electron in the xy-plane? [AMUJ
inversely propo1tional to the square of the principal
(a)Px (b)p 2 (c)dyz (d)dx2 _y2
quantum nun1ber
(c) Total number ofnodes for 3s-orbital is three 2011
(d) The radius of the first orbit of He+ is half that oftbe
12. The maximum number of electrons that can have principal
first orbit hydrogen atom
quantum number, n = 3 and spin quantwn nwnber,
5. In an atom the order of increasing energy ofelectrons with 1 .
m = - - IS [IITJEE]
quantun1 nwnbers s 2'
I. n = 4, I= I II. n = 4 , I= 0
(a) 3 (b) 5 (c) 7 (d) 9
III. n = 3, / = 2 and IV. n = 3, I= 1 is [WB JEE]
13. Which one of the following sets of quantum numbers
(a) III < I < IV < II (b) II < IV < I < III
represents the highest energy level in an atom? [KCETJ
(c) I < III < II < IV (d) IV < II < III < I
(a) n = 4, l = 0, m = 0, s =+ II 2
6. The total number of orbitals associated with the principal
(b) n = 3, l = 1, m = l, s = + 1/ 2
quantun1 nwnber n = 3 is [EAMCETJ
(c) n = 3, / = 2, m = -2, s =+II 2
W9 ~s W5 001 (d) n = 3, l = 0, m = 0, s = + 112
28 I Chapterwise & Topicwise Engineering Entrances Solved Papers

14. Which of the following is correct for nwnber of electrons, 2007

nwnber of orbitals and type of orbitals respectively in 24. Which of the following sets of quantum numbers
n-orbit ? [Guj CET] represents the highest energy of an atom ? [AIEEE]
(a) 4, 4 and 8 (b) 4, 8 and 16 (a) n = 3, I = l, m = l, s = + l / 2
(c) 32, 16 and 4 (d) 4, 16 and 32 (b) n = 3, l = 2, m = 1, s = + 112
(c) n = 4, I = 0, m = 0, s = + 1/2
2010 (d) n = 3, l = 0, m = 0,s = + l / 2
15. The set ofquantum numbers for the outermost electron for 25. The orbital angular momentum of an electron in 2s orbital
copper in its ground state is [KCET]
is CWBJEEJ
1 1
(a) 4, 1, l,+ - (b)3,2,2, +- (a)+ _!__ !!_ (b) zero (c) !!_ (d) ✓2!!_
2 2 22n 2n 2n
1 1
(c) 4, 0, 0, +- (d) 4, 2, 2, +- 26. The orbital angular momentum of an electron in 3s-orbital
2 2
is [AMUJ
16. If the quantum nwnbers for the 5th electron in carbon l h h l h
atoms are 2, 1, 1, + 1/2, then for the 6th electron, these (a) - ·- (b) - (c) - ·- (d) zero
22n 2n 32n
values would be [RPETJ
1 1 27. The number of electrons accommodated in an orbit with
(a) 2, 1, 0, - - (b) 2, 0, 1, + - principal quantum number 2, is [J&K CETJ
2 2
1 1 (a) 2 (b) 6 (c) 10 (d) 8
(c)2,l,1,- - (d)2,l,-l,+ -
2 2 28. Which of the following is not possible ? [BCECEJ
(a) n = 2, l = 1, m = 0 (b) n = 2, I = 0, m = -1
2009 (c) n = 3, I = 0, m = 0 (d) n = 3, I = 1, m = - l
17. Which of the following sets ofquantwn numbers is correct ? 29. The orbital angular momentum of an electron in a
(a) n = 5, I= 4, m = 0, s = + 1/ 2 [UPSEE] d-orbital is [DCEJ
(b) n = 3, I = 3, m = + 3, s = + 1/ 2 (a) ✓6!!_ (b) -fil!_
( c) n = 6, I = 0, m = + l, s = - JI 2 2n 2n
(d) n = 4, I = 2, m = + 2, s = 0
(c) !!__ (d) 2h
2n 2n
2008
30. Which of the following sets ofquantum numbers is correct
18. The nodes present in 3p--orbitals are [Manipal]
for an electron in 4 f-orbital ?
(a) one spherical, one planar (b) two spherical [Jamia Millia Islamia]
( c) two planar (d) one planar
1
19. When the azimuthal quantum number bas the value of 2, (a) n = 4 , I = 3, m = + 4 , s = + -
2
the number of orbitals possible are [KCET] l
w1 ~s ~3 ooo (b)n = 4,l = 4,m =- 4,s =- -
2
20. What is the maximum number of electrons in an atom that 1
(c)n=4,l=3,m=+ l,s = + -
can have the following quantum numbers n = 4 , m1 = + l? 2
(a)4 (b) 15 1
[Guj CET] (d) n = 3, l = 2, m = - 2, s = + -
(c) 3 (d) 6 2
21. Which one of the following is the set of correct quantum
numbers of an electron in 3d orbital ? [J&K CET]
2006
31. Which combinations of quantum numbers n , l, m ands for
(a) n = 3, I = 0, m = 0, s = - 1/ 2
the electron in an atom does not provide a permissible
(b) n = 2, I = 3, m = 0, s = + 1/ 2
solution of the wave equation? [Manipal]
( c) n = 3, I= 1, m = 0, s = - 112
(d) n = 3, I = 2, m = l, s = + 1/ 2 (a)3,2, 1,1/ 2 (b)3, l,1, - 1/2
22. Electron density in the yz plane of3d orbital is ( c) 3, 3, 1, - 1/ 2 ( d) 3, 2, - 2, 1/ 2
X
2 -y2

(a) zero (b) 0.50 [J&K CETJ 32. The orbital angular momentum of an electron revolving in
(c) 0.75 (d) 0.90 a p -orbital is [Kerala CEE]

23. The values of four quantum numbers of valence electron of (a) zero (b) - h- (c) !!_ (d) _!_!!_
an element are n = 4, I= 0, m = 0 and s = + 1/ 2 The -fin 2n 2 2n
element is [DCE] h
(a) K (b) Ti (c) Na (d) Sc (e) 2-fiir,
 Structure of Atom I 29
33. Which one of the following set of quantum numbers is (a) (IV) and (V) (b) (III) and (IV)
not possible for electron in the ground state of an atom (c) (II) and (III) (d) (I) and (IT)
with atomic number 19? [Kerala CEE] 37. Which of the following statements in relation to the hydrogen
(a) n = 2, l = 0, rn = 0 (b) n = 2, l = I, rn = 0 atom is correct ? [AIEEEJ
(c) n = 3, l = 1, m = - I (d) n = 3, l = 2, m = + 2 (a) 3s, 3p and 3d-orbitals all have the same energy
(e) n = 4, I = 0, m = 0 (b) 3s and 3p-orbitals are oflower energy than 3d-orbital
34. The number of 2p-electrons having spin quantum (c) 3p-orbital is lower in energy than 3d-orbital
number s = - 112 are [AMUJ (d) 3s-orbital is lower in energy than 3p-orbital
(a)6 (b)0 (c)2 (d)3 38. An electron with values 4, 3, - 2 and+ 1/2 for the set of four
35. Non-directional orbital is [BCECE] quantum numbers n, I, m1 and ms, respectively, belongs to
(a)4p (b)4d (d) 4/ (d) 3s (a) 4s orbital (b) 4 p orbital [AMUJ
(c) 4d orbital (d) 4 f orbital
2005
39. The total number of orbitals possible for p1incipal quantum
36. In a multi-electron atom, which of the following orbitals number n is [J&K CETJ
described by the three quantum numbers will have the 2 2
(a) n (b) n (c) 2n (d) 2n
same energy in the absence of magnetic and electric
fields? 40. Which of the following is non-pemlissible ? [DCEJ
I. n = 1, I= 0, m =0 TT. n = 2, / = 0, m = 0 (a)n = 4,l = 3,m = 0 (b)n = 4,l = 2,m =I
Ill.n = 2, I= I, m = I TV. n = 3, / = 2, m = I (c)n = 4,l = 4, m = l (d)n = 4,l = 0,m = 0
V. n = 3, / = 2, m = 0 [AIEEE]

Topic 5
F,illing of Orbitals in Atom
2014
1. The electronic configuration of Cu is [WBJEE] 5. Which of the following species have the same number of
(a) [Ne) 3s 2 , 3p 6 , 3d 9 , 4s 2 electrons in its outennost as well as penultimate shell
2 10
(b) [Ne) 3s , 3p 6 , 3d , 4s
1 (a)CI- (b)0 2 - [Manipall
2 3 2 (c)Na+ (d)Mg 2 +
(c)[Ne) 3s , 3p , 3d , 4s , 4 p 6
6

(d) [Ne) 3s 2 , 3p 6 , 3d 5 , 4s 2 , 4p 4 6. Which one of the following has a magnetic moment of

1.75 BM? [KCETJ
2013 (a) y 3+ (b) Cr 3 +
2. How many electrons in 19 K haven= 3; I= 0 (c)Fe 3 + (d) Ti 3 +
(a) l (b) 2 [Manipall 7. Which of the following laws will represent the pairing of
(c) 4 (d) 3 electron in a subshell after each orbital is filled with one
electron? [OJEEJ
2012
(a) Pauli's exclusion principle
3. The electrons identified by quantum numbers n and / (b) Hund's rule
(l)n=4,l=l (2)n=4,l=0 (c) Heisenberg's uncertainty principle
(3) n = 3, / = 3 (4) n = 3, /= I (d) Hess law
can be placed in order of increasing energy as[AIEEEJ
(a) (3) < (4) < (2) < (1) (b) (4) < (2) < (3) < (1)
2011
(c) (2) < (4) < (1) < (3) (d) (1) < (3) < (2) < (4) 8. The representation of the ground state electronic configuration
4. For the valency electron in copper, the four quantum of He by box - diagram as It ti
is wrong because it violates
[WBJEE ]
numbers are [Manipall
(a) Heisenberg's uncertainty principle
(a) n = 4, I= 0, m = 0, s = II 2
(b) Bohr's quantization theory of angular momenta
(b) n = 4, l = 0, m = + 2, s = II 2
(c) Pauli exclusion principle
(c) n = 4, I= I, m = + 2, s = 112
(d) Hund's rule
(d) n = 4, l = 1, m = 0, s = 1/ 2
30 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2010
9. The number of unpaired electrons in Fe 3+ ion is 18. Which is not in accordance to Autbau principle? [BCECE]
(a) 3 (b) 1 [MP PET] 2s 2p 2s 2p
(c) 5 (d) 2 <a) Cill I1~ 11 11I (b) Cill I1~ 11~ 11I
10. What does the electronic configuration Js 2 , 2s 2 , 2p 5 , 3s 1 2s 2p 2P
2s
indicate? [Guj CET]
(a) Ground state of fluor ine (c) DJ 11~11 I 1I ( d) [ill 111111 I
(b) Excited state of fluor ine
19. The total number of electrons present in all the' s' orbitals,
(c) Excited state of neon
all the 'p' orbitals and all the 'd' orbitals ofcesium ion are
( d) Excited state of the ion o; respec6vely [DCE]
11. The electronic configuration of element with atomic (a) 8, 26, 10 (b) 10, 24, 20
nwnber 24 is [JCECE] (c) 8, 22, 24 (d) 12, 20, 22
2 2 4 2
(a) ls ,2s22p 6 ,3s 3p 6 3d ,4s
2 2 2 10 2007
(b) ls , 2s 2p 6 , 3s 3p 6 3d
2 6 6 6 20. The atomic number of Ni and Cu are 28 and 29
(c) ls ,2s22p ,3s23p 3d respec6vely. The electronic configuration
(d) ls2 , 2s2 2 p 6 , 3s2 3p 6 3d 5 ,4s I
Js 2 2s2 2p 6 3s2 3p 6 3dl0 represents [JamiaMillialslamia]

2009 (a)Cu + (b)Cu 2 + (c)Ni 2 + (d)Ni

12. The electrons, iden6fied by quantum numbers n and /, 21. Cr has electronic configuration as [BITSAT]
2 6 4 1 2 6 5 1
I. n = 3; I = 2 II. n = 5; l = 0 (a)3s 3p 3d 4s (b)3s 3p 3d 4s
III. n = 4; l = I IV. n = 4; I = 2 (c) 3s2 3p 6 3d 6 (d) None of these
V. n = 4; l = 0
Can be placed in order of increasing energy, as 22. Among the following series of transition metal ions, the one
[Kerala CEE] in which all metal ions have 3d 2 electronic configura6on is
(a) I < V < III < IV < II (b) I < V < III < II < IV (At. no. Ti = 22, V = 23, Cr= 24 and Mn = 25) [Manipal]
(c) V < I < III < II < IV (d) V < I < II < III < IV (a) Ti 3 +, V2 + , Cr3 + , Mn 4 + (b) T i+ , y4+, Cr 6 +, Mn 7 +
(e) V < I < IV < III < II (c) Ti 4 +, V3 + , Cr 2 +, Mn 3 +(d) Ti 2 + , V 3 +, Cr 4 + , Mn s+
13. The electronic configuration of the oxide ion is much most
similar to the electronic configuration of the [UPSEE] 23. The number of d-electrons retained in Fe 2 +
(atomic number Fe= 26) ions is [MPPET]
T. sulphide ion TT. nitride ion
Ill. oxygen atom IV. nitrogen atom (a)3 (b)4 (c)5 (d) 6

14. What is the atomic rrwnber of the element with M 2+ ion 24. The electronic configuration ofCr 3 + is [KCET]
4 2 3 0
having electronic configura6on [Ar] 3d 8 ? [Guj CET] (a) [Ar] 3d 4s (b) [Ar] 3d 4s
(a) 25 (b) 28 (c) 27 (d) 26 (c)[Ar] 3d 2 4s1 (d)[Ar] 3d 5 4s 1

2008 25. Identify the least stable ion amongst the following
(a) Li- (b)Be- CWBJEE]
15. Which of the following has the maximum number of
unpaired ' d' electrons ? [KCET] (c) B- (d) C
(a)Zn 2 + (b)Fe 2 + (c)Ni 3 + (d)Cu+ 26. The maximum number of sublevels, orbitals and electrons
10 1
in N-shell of an atom are respectively [EAMCET]
16. [Ar] 3d , 4s electronic configuration belongs to
(a) 4, 12, 32 (b) 4, 16, 30
(a) Ti (b) Tl [MP PET] (c) 4, 16, 32 (d) 4, 32, 64
(c) Cu (d) V 27. The highest number of unpaired electrons are in [DCEJ
2
17. What is the electronic configuration of Mn +7 [BCECE] (a) Fe
(a) [Ne] 3d 5 , 4s 0 (b) [Ar] 3d 5 , 4s 2 (b) Fe 2 +
(c) [Ar] 3d ,4s
5 0 5
(d) [Ne] 3d ,4s
2 (c) Fe 3 +
(d) All have equal number of unpaired electrons
 Structure of Atom I 31
2006
28. According to Autbau principle, the correct order of energy 32. The atomic numbers of elements X, Y and Z are 19, 21
of3d, 4s and 4p-orbitals is [J&K CETJ and 25 respectively. The number of electrons present in
(a) 4 p < 3d < 4s (b) 4s < 4 p < 3d the M-shell of these elements follow the order
(c)4s<3d<4p (d)3d<4s<4p (a)Z>X>Y (b)X>Y>Z [EAMCETJ
29. The stability of ferric ion is due to [BCECEJ (c)Z>Y>X (d)Y>Z>X
(a) half filled /-orbitals 33. Electronic configuration of deuterium atom is
(b) half filled d-orbitals (a)ls 1 (b)2s
2
[J &K CETJ
(c) completely filled /-orbitals 1 2
(d) completely filled d-orbitals (c) 2s (d) ls
34. A p-orbital in a given shell can accommodate upto
2005 (a) four electrons [BCECEJ
30. Which an10ng the following species have the san1e number (b) two electrons with parallel spin
of electrons in its outermost as well as penultinlate shell ? (c) six electrons
(a)Mg 2 + (b)0 2 - [Manipal] (d) two electrons with opposite spin
(c) F- (d) Ca 2 + 35. Electrons will first enter into the set of quantum numbers
31. The valence shell electronic configuration of Cr 2 + ion is n = 5, l = 0 or n = 3, l = 2 [DCEJ

(a) 4s 0 3d 4 (b) 4s 2 3d 2 [OJEEJ (a) n = 5, l = 0 (b) both possible

(c)4s23d 0 (d)3p 6 4s
2 (c) n = 3, l = 2 (d) data insufficient

Answers
TOPIC 1 Sub-Atomic Particles
1. (b) 2. (a) 3. (a) 4. (b) 5. (b) 6. (c) 7. (a) 8. (c) 9. (b) 10. (c)
11. (e) 12. (d) 13. (a) 14. (a) 15. (b) 16. (b) 17. (a) 18. (c) 19. (a) 20. (c)
21 . (a) 22. (b)
TOPIC2 Atomic Models
1. (c) 2. (d) 3. (c) 4. (a) 5. (b) 6. (c) 7. (a) 8. (c) 9. (a) 10. (b)
11. (c) 12. (b) 13. (e) 14. (c) 15. (a) 16. (d) 17. (b) 18. (d) 19. (a) 20. (d)
21 . (c) 22. (d) 23. (d) 24. (d) 25. (b) 26. (c) 27. (b) 28. (c) 29. (c) 30. (b)
31 . (c) 32. (c) 33. (c) 34. (b) 35. (a) 36. (d) 37. (c) 38. (a) 39. (b) 40. (b)
41 . (d) 42. (b) 43. (c) 44. (c) 45. (b) 46. (d) 47. (a) 48. (d) 49. (a) 50. (d)
51 . (b) 52. (a) 53. (b) 54. (c) 55. (a) 56. (a) 57. (a) 58. (d) 59. (d) 60. (c)
TOPIC3 Modern Structure of Atom
1. (c) 2. (a) 3. (a) 4. (d) 5. (c) 6. (b) 7. (b) 8. (c) 9. (b) 10. (a)
11. (b) 12. (b) 13. (a) 14. (b) 15. (c) 16. (a) 17. (c) 18. (c) 19. (b) 20. (d)
21 . (b) 22. (a) 23. (c) 24. (a) 25. (a) 26. (c) 27. (a)
TOPIC4 Quantum Numbers
1. (a) 2. (a) 3. (b) 4. (d) 5. (d) 6. (d) 7. (d) 8. (b) 9. (a) 10. (a)
11. (b) 12. (d) 13. (c) 14. (c) 15. (c) 16. (d) 17. (a) 18. (a) 19. (b) 20. (d)
21 . (d) 22. (a) 23. (a) 24. (b) 25. (b) 26. (d) 27. (d) 28. (b) 29. (a) 30. (c)
31 . (c) 32. (b) 33. (d) 34. (d) 35. (d) 36. (a) 37. (a) 38. (d) 39. (b) 40. (c)
TOPIC5 Filling of Orbitals in Atom
1. (b) 2. (b) 3. (b) 4. (a) 5. (a) 6. (d) 7. (b) 8. (c) 9. (c) 10. (d)
 Explanations
Topic 1 Sub-Atomic Particles
1. Isotonic species have same number of neutrons 6. Number of electrons in M 2 + = 24
So, number of neutrons in :. Number of electrons in M = 26
14
6C = 14 - 6 = 8 i.e. atomic number (Z) = 26
14 Mass number (A) = 56
7N =14-7=7
19 :. Number of neutrons= A - Z = 56- 26 = 30
9F = 19-9=10
15 7. Isobars have same atomic mass but different atomic number. Thus,
7N = 15-7=8
the isobar of 20 Ca 40 is 18 Ar 40 .
17
9F =17-9=8
8. Nucleus of an atom is small in size but carries the entire mass
6 c 12 = 12 - 6 = 6 i.e. contains all the neutrons and protons.
1 15 17
Hence, 6 C 4, 7N , 9F are isotonic 9. Ar and Ca 2 + are isoelectronic species as they have same number of
electrons, i.e. 18.
2. The species containing the same number of electrons are called
isoelectronic species 10. Isoelectronic species have same number of electron. Mg2+ and Na+
(a) Number of e- in Li = 3 both have IO electrons hence, they are isoelectronic species.
Number of e- in Be+ = 4 - I= 3 11. J4 C, ~60 , fN = isotonic triad
(b) Number of e- in H- = I+ I = 2 Isotone = same number of neutron.
Number of e- in He+ = 2 - I= I All species contain 8 neutrons.
(c) Number of e- in He= 2 12. The mass number = atomic number + munber of neutron
Number of e- in H = I Atomic number = number of proton = number of electron
(for an atom) So, mass number= 18 + 20 = 38
(d) Number of e- in Be+ = 4 - I= 3
2
Number of e- in H = I 13. 80 - has 10 electrons. 22 Ti+ has 21 electrons.
Hence, Li and Be+ are isoelectronic. 14. Isoelectronic means having same number of electrons.
3. An element is a pure chemical substance distinguished by its K+, c1-, Ca 2+, Sc3 + (all are having 18 electrons).
atomic number, which is the number of protons in its atomic 15. Ca 2+ (2, 8, 8) and Ar (2, 8, 8) contain equal number ( 18) of
nucleus. electrons, hence they are isoelectronic.
4. elm ratio for He2+ = 2 14 16. Positron is as heavy as an electron. Hence, positron is lightest particle.
elm ratio for H+ = I / l 17. Tritium is the isotope of hydrogen. Its composition is as follows
elm ratio for He+ = l I 4 I electron, I proton and 2 neutrons.
elm ratio for o + = I / 2 18. The proton has unit positive charge(+ 1.602 x w- 19 C) and its mass
Hence, the elm is highest for hydrogen ion. is 1.007 u (1.677 x 10- 27 kg).
e 1.6 X 10-!9 19. Rutherford showed the existence of nucleus in an atom by his
5. - for electron (e) = a-particles scattering experiment. He postulated that every atom has
m 9.1 X 10-28
a small central part which has positive charge and almost all the
8
= 1.758 X 10 mass of atom (i.e. nucleus consists of protons and neutrons).
19
e 1.6 X 10- 20. Tritium contains 2 neutrons and I proton.
- for proton (p)
m 1.672 X I 0-24 21. Number of neutron= atomic mass - atomic number.
= 9.56 X 10
4 For C 12 Number of neutron= 12 - 6 = 6

e 0 22. The isotones are a species which have equal number of neutrons.
- for neutron (n) = 24
0
m l.675x IO- Number of neutrons is ji Ge= 77 - 32 = 45
e . 2xl6xl0- 19 Number of neutrons in jj As = 77 - 33 = 44
- for a-particle= = 0.5 x I 05
m 4 x 1.6x 10- 24 Number of neutrons ~Se = 77 - 34 = 43
Hence, the increasing order of!._ is as Number of neutrons j~Sc = 76 - 36 = 40
m
Number of neutrons in j~Ge = 76 - 32 = 44
n<a<p<e
Hence, nAs is isotone of j~Ge.
Topic 2 Atomic Models
1. Radius of orbit is directly proportional to ratio of square of he he
10. Energy of photon= - J = - eV
principal quantum number and atomic number A eA
6.625 X 10-34 X 3 X 108
i.e, Radius oforbit °" n' a0 (a0 = 0.529A: A= 10-8 cm)
z 300 X 10-9 X 1.602 X 10-19
. _ n 2 X 0.529 X 10- 8 =4.14eV
F or H -atom, ,11 - ------ cm
z For photoelectric effect to occur, energy of incident photons must
2. In 1885, Balmer for the first time showed that the wave numbers be greater than work functions of metal. Hence, only Li, Na, K
of spectral lines present in the visible region in hydrogen and Mg have work fi.mctions less than 4.14 V.
spectrum are given by 11. Energy values are always additive.
v (cm- 1
= 109677 ( ~ - ~) £,oral = E1 + E2

l.
)
(2) n he he he
- =- +- 1
Here, n = 3, 4, 5...
Thus, Balmer spectrum of hydrogen was discovered first and it
lies in the visible region.
/\, A1 A2
1
- =- +-
/\, A1 A2
I I E -½-
3. Balmer series in atomic hydrogen is observed in visible region.
Note Lyman series lies in UV region and Paschen series lies in IR
-
1
355
=-
+-
680
I
A2
I
I f'
region and bracket and others lies in far IR region.
A2 = 742 .77 tun .,743 nm
4. M = 2.179 x 10- 18 (_!_ - _!_) = he
12 22 A, , h _ 2Jt 2mZ24e k 2r 1 I 7
2 _179 X IO- 18 (_!_ __!_) = 6.62 X 10- 34 X 3.0 X 108
12.
r. _
· = - v- h2 lnf - 1~ J
12 22 A, ·: electron falls from nz-level to n 1-level.
:. A "" l.214 x10- m 1 :. In He+ for the n2 = 4 to n1 = 2 transition

5. The difference between the energies of adjacent energy levels

+
u(He )=constant(4)L
r 1 - 1 1J
22 42
decreases on moving from the nucleus.
6. The sum of protons and neutrons give the mass number.
The number of neutrons and protons are not equal.
= constant x 4 rl~ lj=i constant
16 4
7. The lines in the spectrum are called Balmer series.
8. According to Bohr's model,
u (H) = constant (I) 2 - 2
lit 112
l I lj
if 1

mvr= -
nh
2n = constant
r 1 -,J
xl- 11

,i2h2
nf n:;
⇒ (mv)2= - -
4Jt2,.2 (a) For n2 = 3 and 111 = I, u (H) = constant
r1 - 11j
L
I 2 ,i2h2
1 9
KE= - mv = - - - ...(i) 8
2 81t 2r 2m = - constan
9
* -43 x constant
Also Bohr's radius for H-atom is r = n 2 17o
On substituting the value of' I in Eq. (i), we get (b) For '½ = 2 and n 1 = I, u (H) = constant x L
I r - I lj
1 4
h2
KE = , 2 when, n = 2 3
= - x constant= u (He+)
81t 2n-t1om 4
h2 I 2 r1 11
KE= 2
81t (2) aom
2,
13. i = z . RH ln~ - nJ j
h2
2
For He+ _!_ = 22 · R
'A H
rl_!_ - __!___lj
32n ~m 22 42
9. The radius of hydrogen atom= 0.53 A 3 3
=4 X - = -
2 16 4
3 Li + ion also has only one electron but it has 3 protons in
nucleus, hence its electron feels three times more attraction from For H,
1
i
2
= 1 . RH
r1 -l2r4
Lt2 ll 3
nucleus in comparison to hydrogen atom. Thus, the radius of
2 0 53 Hence, for hydrogen n = 2 to n =I.]
3 Li + w ill be · = 0.17 A.
3
34 I Chapterwise & Topicwise Engineering Entrances Solved Papers

II 4
3 6
14. £ 11 = E~ x22 = - l · x 9=-30.6eV E2 - E3 = 13 12 x Z
2r
l36SlJ ...(ii)

(for the excited state, n = 2 and for Li 2+ ion, 2 = 3) From Eqs. (i) and (ii)
1
15. - =2 ·RH
2 rl2-2j
1 11 E1 - E2 = 3 x 36 = 27
l 111 ,iz E2-E3 4x5 5

⇒ _!_). = (2)2 · RH {I- _ 1 rl 1 11 1

I
_!_} = l RH2 2
4 4
21. Apply Rydberg formula, v = - =RH 2 -
l 111
2111, J cm-
I For the first line in Lyman series, n 1 = I and '½ = 2.
:. l cx:2
2 109678 3
So v = 109678 lr_!_ __!__] x 82258.5cm- 1
Hence for shortest )., 2 must be maximum, which is for Li 2+. , 12 22 4
3 nhe
242
16. Energy required to break for one Cl 2 molecule x I0 J 22. Energy, E = -
).
NA
34 8
he he x Js- t = nx6.63 x 10- Jsx 3 x 10 m
E=- or l= - 60 I
A E 663 X 10-9 m
6.626 X 10-34 X 3 X 108 X 6.02X 1023 r·: Power = -energy
. - j
l
242 X 10 3
l time
= 494 X 1 o-9 m = 494 nm 60 X I X 663
n= - - -~ 34~ - -~8
X I 0- 9
2 X 1020
17. IE=-£1 6.63 X 10- X 3 X 10

E 1 for He+ =-19. 6 x 10- 18 J atom- 1

2
23. Bohr radius for nth orbit= 0.53 A x !!_
(E1)He• _ (ZHl)2 - 19. 6 X 10-18 4
z
w here, Z = atomic number
(£1\; 2+ - (ZLi 2+ )2 (£1 \; 2+ 9 23
53
:. Bohr radius of 2nd orbit ofBe3+ = 0. x ( ) = 0.53 A
18 4
·'+) = -
or E 1 (L1- -19.
-6-X- 10-- =- 4 .41 x I0-17 J atom -
9 X- I
4 0 53
(d) Bohr radius of 1st orbit ofH · x (l)2 = 0.53 A
18. According to Bo hr model, radius of hydrogen atom I
2
Hence, Bohr's radius of 2nd orbit ofBe 3+ is equal to that of first
(,.) = 0.529 X n A
II z orbit of hydrogen.
(where, n= number of orbit, 2 = atomic mm1ber) 24. Ionisation entha lpy of hydrogen atom is 1.3 12 x Icf' J mot- 1. It
0 529 32 suggests that the energy of electron in the ground state (first orbit)
13 = · x ( ) 4.76 I A"' 4.76A
I is-l.312x l if'Jmol- 1.
19. Wave number of spectral line in emission spectrum of hydrogen,
M. = £ 2 Ei = ( -1 .31; x l cf')-(- 1.31~ x lcf')
- (2I -21)
v =RH
n1 nz
...(i)
_

= 9.84 x 105 J mo1-1

2

-
Given V = -8 RH 25. Energy of an electron in nth orbit, E11 =
9 n2h2
On putting the value of v in Eq. (i), we get
On substituting the values of k, m , eand h, we get
~ - (_!__ __!__) ⇒ ~ - _ I_ - _!__ 18 2
2.172 X 10- Z J -I
9 nf I~ 9 ( 1)2 I~ E11 = - 2 atom
n
2
~-I =- _!___!_ = _!_ 13 11.82 kJ mol-1
9 1~ ' 3 ll2 or
fl2

Iii= 3 3 13.5222
or =- 2 kcal mol-1 [·: I kcal = 4.1 84 kJ]
Hence, electron jumps from 111, = 3 to 111 = 1 11

20. E 1 -E2 =13 12xZ

2 r 1 1 1J
l"i2- For H-atom, Z = I
22 For Lyman series, n 1 = I, n2 = 2

E 1 - E2 = 13 I 2 X z
2
lr43lJ ...(i) . .
Energy of electron 111 n 1 orbit= -
313.52x(l)2
(I)
2
kcal mo!
-I

E 2 -E3 =13 12xZ

2
lr221 - 321 7J = - 313.52 kcal mol-
1

"' - 313.6 kcal mo1- 1

 Structure of Atom I 35
. . 313.52 X (1)2 -I
=-2.18x10- 18 x lr~ _ _!_lj
Energy of electron m 112 orbit= - kcal mol 42 12
(2)2
313.52 k I
=- - - ca mo,-1 /',.E = hv = - 2.18 x 10-18 x-_!2
4 16
= - 78.38 kcal mo1-1 = + 2.0437 x 10-18 J atom- 1

26. Deflection back shows that the nucleus is heavy but of only a few till 2.0437 x 10- 18 J atom -t
v= - =- - - - - ~34- - -
particles shows that nucleus is small. h 6.625 X l0- Js
l
27. Frequency (n) = - - - - - - = 3.08 x 1015 s- 1 atom- 1
Time period (T)
33. Line spectnun of atomic hydrogen in the visible region.
Here, T = 5 x 10-3 s
n= I 0.2 X 103 = 2 X 102 s-1 II I I
5 X 10-3 2
34. Ionisation energy of He+ = 13.6 x Z eV
28. According to Bohr's atomic model, if energy is supplied to an = 13.6 X (2)2 eV
electron it may jump from a lower energy level to higher energy
level. Energy is absorbed in the form of quanta (or photon). = 13.6 x 4 eV = 54.4 eV
till=hv
where, v is the frequency.
1
35. - =
A
_
VH = RH l-rnf1 --, 1J 1~
According to above postulate an electron from one Bohr
l
stationary orbit can go to next higher orbit by the absorption of =l.097xl0 Lf - 002I lJ
l
electromagnetic radiation of particular frequency.
29. Stark effect The splitting of spectral lines under the influence A. = l m = 9 .11 x l 0-8 m
of electric field is called Stark effect. 1.097 x 107
Raman effect When light of frequency v0 is scattered by = 91.1 x 10-9 m = 91.l nm (1 nm= 10-9 m)
molecules of a substance which have a v ibrational frequency of ., 91 nm
v1, the scattered light when analysed spectroscopically has lines
36. The energy of second Bohr orbit of hydrogen atom (E2) is
of frequency v where v = v0 ± v0
- 328 kJ mo1- 1 because
Zeeman effect The splitting of spectral lines under the
influence of magnetic field is called Zeeman effect.
Rutherford effect According to Rutherford on the
_
E2 - - 713 12kJ mo1_1
bombardment of the atoms by high speed a particles, the centre of E = _ 13 12 kJ mol-1
the atom scatters the a-particles. n 2
n
30. N iels Bohr utilised the concepts of quantisation of energy If 11 = 4
(proposed by Max planck) first time to give a new model of atom. 1312
E4 = - - kJ mol-1 = - 82 kJ mo1- 1
31. We know that, M
r 1 - , 1j
= he· Rl
42
-

211
21
12 1 . 1 r 1 1 1sR
37. For Lyman sen es, - = Rl2 - 2J ⇒ - = Rl2
1 1 r -2j
11
For lowest energy, of the spectral line in Lyman series, A. I n2 16 1 11 2
n1 = I, n2 = 2.
r -- J 1sR _ r~ - 11 ⇒ .!2 = ,~ - 1
Hence, /',.E = he·
1
RL-11
2
12 2
16R -l---;;rJ 16 I~

I Sni = 1611i - 16
⇒
11?=16 ⇒ ni=4
32. Ionisation energy of H = 2.18 x 10- 18 J atom -t 38. The value of Rydberg constant is I 09678 cm-t.

lrnf - nJ 1j
E 1(Energy of ! st orbit ofH-atom) 1 1 1
= - 2.18 x 10- 18 J atom- 1 39. i = RH
18
_ - 2.18 X 10- J -I
En - , atom For Lyman series, 111 = I, 11z = 2
n-
_!_ = I 0967 / _ 1_ _ _ l_ l = I 09678 x 3
z = I for H-atom
till= E4 - £ 1
A. l(1)2 2
(2) J 4
A. = 1216A
- 2.18 X 10- 18 - 2.18 X 10-18
36 I Chapterwise & Topicwise Engineering Entrances Solved Papers

40. A- 1 = 3000A, 11. 2 = 6000A 51. Velocity ofan electron in first orbit ofH atom is
8
E _ he _ he 2. 1847 X 10 -1
u = - - - - - ems
I - ~ - 3000 I
1
E _he_ he Hence, it is - - th as compared to the velocity of light.
2 - ll.2 - 6000 100
52. Splitting of spectra l lines under the influence of an external
he
electrostatic field is called Stark effect.
E1 _ 3000 _
- - -- - -- X-- - -
he 6000 _ 2
he
£2 _!!!:_ 3000 he 1 53. E = - , hand c for both cases are same so,
A,
6000
£ 1 = 11. 2 = 16000
£ 1 : £ 2 = 2: I
£ 2 11. 1 8000
41. Angular momenn,m of an electron
nh 54. Rutherford's scattering experiment for the first time showed the
mvr = - (n is orbit number) presence of positively charged nucleus at the centre of atom.
21t
. Stl1 orb'1t= -Sh = -
2.5h 55. For first excited state n = 2
111 -
21t 1t E =E'
n 112
42. The number of waves in an orbit = n.
43. Bohr's theory is applicable to unielectron atom or ion only. (where, £ 1 = energy of first Bohr's orbit)

44. Zeeman effect is splitting up oftlle lines ofan emission spectnun E = - l 3 ·6 = - 3.4 eV
2 (2)2
in a magnetic fie ld.
1 6 56. According to Bohr, an electron can move only in those orbits in
45. Energy of e- in the ntll orbit of atom = - ; · eV/ atom
11 which its angular momentum is a simple multiple of_!!_, i.e. equal
Given, 11 = 5 21t
13 6 to -nh ( h . .
w ere, 11 1s an 111teger)
E5 = - ~ =- · = - 0. 54 eV/atom 21t
(5)2 25
he . . .
57. K111et1c energy 111 an orbit= -
. -
ze2 . .. (i)
46. M=hv= - 81t£0r
A-
34 . . . ze2
A- = ~ = 6.62 X 10- X 3 X 10
8
Potential energy 111 an orbit= - - ...(ii)
14 4nE0r
M 4.4 X 10-
On comparing Eqs. (i) and (ii), we get
12
= 4.52x 10- m
KE=_!_ PE
47. E = 3 x 10- 12 ergs A- = ? 2
h = 6.62 X I 0- 27 ergs 58. Hydrogen spectrum is an emission spectrum. It shows the
presence of quantized energy levels in hydrogen atom.
e= 3 x 1010 cms- 1 E = he
A, 59. According to Bohr's model of hydrogen atom, the energy of
27 10 electrons in the orbit is quantised, the electron in the orbit nearest
X l0- 12 = 6.62 X 10- X 3 X 10 to nucleus has lowest energy and electrons revolve in different
3
A, orbits around the nucleus. Whereas according to Heisenberg's
27 10 uncertainty principle position and velocity of the electrons in tlle
A-= 6.62 X 10- X 3 X 10
3 X 10-IZ orbit cannot be determined simultaneously.

= 6.62 x 10-5 cm= 662 x 10-7 cm 60. En = - I

3
11
;6 eV
9
= 662 x 10- m = 662 nm
For second excited state 11 = 3,
2 2 E3=- 13.6=- l.5 leV
48. M = 13.62 (~ - ~) = 13.6 x (1) (~ - ~) 9
n 1 '½ I 2

= 13.6 ( 1 - ¾) = 13.6x¾ = 10.2 eV Topic 3 Modern Structure of Atom

1. According to de-Broglie wavelength, A- = __!!_
49. A- for visible light is in tlle range of 400 to 780 nm. mv
E = he_ 1
Given, m = I 00 g, v = I 00 cm s-
A,
Thus, it is in the range of I electron volt (eV). and h =6.6 x 10- 34 J-s = 6.6 x 10- 27 erg-s
nh On substituting valu es, we get
SO. Angular momenn,m of electrons = mvr = -
21t ' 6.6x10- 21 66 10-31
/\. = - - - - = . x cm
100 X 100
 Structure of Atom I 37
he h h
2. Energy E = T 10. A. = - ⇒ m = -x;
mv
34 8
or A.= he= 6.626x 10- x 3 x 10 = _ x -6m 6.62 X 10-34
20
6 01 10 0. 1 kg
E 3.31 x 10- 6.62X 10-35 X 100
3. ·: Energy of 1 photon, E = hv 11. Schrodinger wave equation is
: . Energy of 1 mole of photon, E' = NAhv a a'-\jf +___y+
2
___y+ a 8, 2
n -m (E - V) \jf =0
14
= 6.022 X 1023 X 6.626 X 10- 34 X 5 X 10 ax 2
aJ az2 h2
= 199.508 x 103J mo1- 1 = 199.51 kJ mo1- 1
12. de-Broglie wavelength, A. = !!:_ = _!}_ [·: momentum p = mv]
4. From Heisenberg uncertainty principle p mv
34
t...x-t-J>?. -
h
...(i) ⇒ A. 6.62 X 10- J -S l0-13 m
41t 6.62x 10-27 x Hf> kg m /s
h
/1,y · mlw ?. - 13. Given, velocity of particle A= 0.05 ms- '
47t
h Velocity ofparticle B = 0.02 ms- 1
D.x ·ti.v?. - - .. . (ii)
4mn Let the mass of particle A = x
This principle is also applicable for pairs like energy time :. The mass of particle B = 5.x
(M · ti.t) and angular moment-angle (t..ro- ti.0) along w ith de-Broglie's equation is A. = _!}___
position-momennun (& · ti.P). mv
Thus, 11,£ . ti.t ?. _!}_ ... (iii) .
For particle A , '11,A = - - h- ...(i)
47t x X 0.05
h h 6.626 X 10-27
5. A.= - ⇒ v= - For particle B, A. 8 = h ...(ii)
mv mA. 9.109x10-28 x0. 15x10- 7 Sx x 0.02
= 4.84x 108 cms- 1 From Eqs. (i) and (ii),
6. According to de-Broglie, A.A= 5.xx0.02):,1-=~ or 2:1
A.9 XX 0.05 A.9 1
h A. llltt 2 VH
A.= - · or ---':k.=- - x- 2
mv A.H 2 mHe VHe 14. The de-Broglie relation is,
h
Given, A.= -
VH2 =vHe mv
A. He 2 VHe
--= - X - =-
I where, A. = de-Broglie wavelength
A.tt2 4 Vtte 2 h = Planck's constant
m = mass of particle
7. A.= _!}___
mv v = velocity of particle
Here, v = 3600 km/h = I 0 5 cm/s 15. From de-Broglie equation,
3
Ill = I. 0 mg= 10- g A. = _!}_ = 6.6 X I 0-34 = 1.32 X I 0-35 m
27 mv 0.5 X 100
A. _ 6.626 X 10- _ l0-29
- 10-3 x 105 - 6 .626 x cm h
16. A.= -
mv
8. By Heisenberg's uncertainty principle 6.63 X 10-34 6.63xlo- 34 ,,, 6 X 10- 34 ,,, I0-33
h
Dx·mti.v = - 60 X 10-3 X 10 6x l 0- 1 6x 10-1
41t
1
ti.v = 0.005% or 600 mis 17. m = 10 mg= 10 x 10-<i kg, v = 100 ms-
34
600 X 0.005 0.03 A. = _!}_ = 6.63 X 10-
100 mv 10 X 10-6 X 100
34
D.x X 9.1 X 10-3! X 0.03 = 6 ·6 X l0- = 6.63 X 10-3t m
4 X 3.14 11
18. & · ti.v ?. - -
/1,y = 6.6 X 10-34 = 1.92 X 10-3 m 4mn
4 X 10-3!
3.1 4 X 0.03 X 9.1 X 6.63 X 10-34
D.x = - - - - - - - - - - - - - - -
34 4 X 3.14 X 9. 1 X 10-3! X 300 X 0.001 X 10-2
9_ A. = _!}_ ⇒ Ill = }!___ = 6.63 X 10-
2
mv A.V 1.67x 10-27 X 1 X 103 = 0.01933 = 1.93 X 10- m
= 3.97 x 10-10 m "" 0.40 nm 19. The probability of finding the electron in the orbital is 90-95%.
38 I Chapterwise & Topicwise Engineering Entrances Solved Papers

20. According to de-Broglie, 10 10-5 > 6.62 X 10-34

r c1
• A
.• uXX. X _----
, h 4 X 3.)4
,.,=p Lv=iJ
Llx?. 6.62 X 10-34 ?. 5.27 X 10-30 m
Now, V = exp, V = 3 X 108 X 1.1 X 10-23 = 5.0 X 10'8 Hz 4 x 3.14 x I.O x 10-5
h 6.6x 10-34 h
27. Llx·Llv?. - -
21. Wave-nature of electrons was first demonstrated by de-Broglie's 41t1n
who gave following equation for the wavelength of electrons A 6.62 X 10-34
ux?. - - - - - - - 3- - - 2.I Ox 10-23 m
"- =}!_ 4 X 3.14 X 25 X 10- X 10-S
mv
22. According to Heisenberg principal, Topic 4 Qu antum Numbers
h
Llx X m X Ll v =- 1. This problem is based on concept of quantum number.
47t
where, Llx = uncertainty in position Follow the following steps to solve this problem.
m = mass of particle Write all possible orbitals having combination of same principle,
Ll v = uncertainty in velocity
azimuthal, magnetic and spin quantum number.
According to the question, Then count the all possible electrons having given set of quantum
h numbers. For n = 4, the total number of possible orbitals are
LlxA x m x 0.05 = - ...(i) 4s 4p 4d 4f
41t

!'i.x 8 x Sm x 0.02 = -
h
... (ii)
~ ll - 1 1 ° 1+ 111- 2 1- 1 1 ° l+ 1 l+ 2 ll - 3 l - 2 l - 1 I O l+ 1 l+ 2 l+ 3 I
41t
Accoding to question Im,I= 1, i.e there are two possible value of
Eq. (i) divided by Eq. (ii), then 111 1, i.e + I and - 1 and one orbital can contain maximum two
LlxA X m X 0.05 = I ⇒ !'i. xA =
Llx8 x Sm x 0.02 Ll x 8
2 electrons one having s =+ .!. and other having s = - 1/2
2
23. According to Bohr's concept, an electron always move in the So, total number of orbital having {lm,I = l} = 6
orbit with angular momentum (mvr) equal to nh/ 21t Total number of electrons having {lm11= l} and m, = - I / 2 = 3
nh 11 ( h) nA 2. Given atomic number of Rb, Z =37
mvr= 21t ⇒ r= 21t. mv r= 21t
Thus, its electronic configuration is [Kr] 5s 1. Since the last
rlfrom de- Broglie equation, A, = l!.__Jl electron or valence electron enter in 5s subshell.
mv
So, the quantum number are n = 5, l = 0 (for s obital)
for fourth orbit (n = 4), r = 2A. is 2m· = 4A.
1t m=O
Circumference of 41t orbit= 4A. 1 1
(:. m = + l to - /), s =+ - or - -
2 2
24. '= h
,._ · ===, KE=_!!___
✓2m(KE) 2
2A. m 3. The valence shell configuration is 4s24 p5 and for the last electron
n = 4, l = 1
(6.626 X 10- 34)2 = 2.98 X 10-15 J
I 1
2 X (0.090 X 20-I0)2 X 9.1 X l 0-31 m = - I O or + I s = + - or - -
' ' 2 2
AceeIeratmg . I = 2.98 x 10- 15 e V = I .86 x 104 eV
. potent1a I
1.6 X 10-19 Hence, 4, I, 1, -
2
25. It is impossible to determine simultaneously the exact position 4. ·:Total number of nodes= n - I
and momentum of moving particle like electron, proton, neutron.
:. For 3s orbital nodes= 3 - 1 = 2 (for 3s, n = 3)
h
LlxX.llp?. - 5. The increasing order of energy can be calculate from (n + l) rule.
41t
If two orbitals have same value of (n + l), the orbital with lower
where, /'J.x = uncertainty in position
value of n w ill be filled first.
Ll p = uncertainty in momentum
(i) For n = 4, l = I, (n + l) = 4 + 1 = 5
26. According to Heisenberg principal, (it) Forn=4,l=O,(n+ /)=4+ 0=0
h (iii) For n = 3, l = 2, (n + l) = 3 + 2 = 5
/'J.x X Llp ?. -
41t (iv) Forn = 3, l = 1, (n + I)= 3 + I= 4
where /'J.x = uncertainty in position Therefore correct order
Ll p = uncertainty in momentum (IV) < (IT) < (ITI) < (I)
= 1.0 x 10-5 kg ms-• 6. When n = 3, total number of orbitals
=2n+1=2x3+1=7
 Structure of Atom I 39
7. The possible values of m for f orbital are, 14. For N-shell, n = 4
- 3, - 2, - I,. 0, + I,+ 2, + 3 I = 0, I, 2, 3
8. Azimuthal quantum number/ ford orbitals is 2. (subshell) s p d f
9. For n = 3, I = 0, 1, 2 and for / = 1, m = - 1,0, + I orbitals I 3 5 7
Thus, (m = 3, I= I, m = + 2) set is not possible. Hence, total subshells = 4, number of orbitals= 16 and
number of electrons = 32 .
10. According to Bohr Bury's scheme
15. The electronic configuration of the Cu atom is
Maximum number of e- in 3rd orbital = 2n2 = 2(3)2 = 18 10 1
29 Cu =[Ar]3d 4s
Maximum number of e- in s-subshell = 2
Since, the outermost shell is 4s, thus outermost electron is in it.
p-subshell = 6, d-subshell = I 0, /-subshell = 14 I 1
For4s, n=4,l=0,m=0,s=+ -
Therefore, I 8e- present in 3rd orbital enter ins, pand d subshell. 2
Thereafter there is no e- available for /-subshell that's why 3 f 16. 6 c = 1s2, 2s2, 2/
subshell is not possible. For 6th electron; n = 2,/ = l,m = - I
So, the value of magnetic quanttun munber is - / to + /, then - 2 I
ands=+ -
to+ 2, i.e. - 2, - 1, 0, + I,+ 2 2
11 . Shape of given orbitals may be drawn as 17. When, n = 5, I= 0, I , 2, 3 or 4 and m = - 4 to+ 4
z
y :. n = 5, I= 4, m = 0, s =+..!..is a correct set of quantum
2
X
numbers.
18. Number of spherical nodes in 3p-orbitals = 3 - 1- I= I
There is one planar node in all p-orbitals
(a) Px (b)P, 19. Given, azimuthal quantum number(/)= 2
z
Ntunber of orbitals= (2/ + I)= (2 x 2 + I)= 4 + I = 5
20. n = 4, m1 = + I
m1 = + I shows the p-subshell, the maximum munber of electron
will be six.
21. For 3d-orbital, n = 3
(c) dy, (c) d.,,2_ y2 Ford-orbital, / = 2 and m = - 2, - 1, 0, + I, + 2
I
It is clear from tthe above shapes, p, orbitals has zero probability s=±-
2
of finding the electron in the xy-plane.
:. The correct set for 3d-orbital is
12. When n = 3, I= 0, I, 2 i.e. there are 3s, 3p and 3d-orbitals. If all
I
these orbitals are completely occupied as n=3 1=2 m= l s=+ -
' ' ' 2
3s 3p 3d 22. Electron density of 3d , orbital in yz plane is zero.
.r - y 2
OIJ 11~11~11~11 1~ 11~11~ 11~11~ I 23. Four quanttun munbers are n = 4, I= 0, m = 0, s = + l / 2
Total 18 electrons, 9 electrons withs=+..!.. and 9 w iths= - ..!.._ n = 4 indicates that the valence electron is present in 4th shell (4th
2 2 period), I = 0 indicates that the valence e lectron is present in
I s-subshell. m = 0 indicates that the valence electron is present in
13. (a) fl =4, I= 0, m= 0,s = + - ➔ 4senergy level.
2 orbital of s-subshell. s = + I/ 2 indicates that the spining of
1 electron in orbital is clockwise. So, from the above discussion it is
(b) n = 3, I= I, m= + I, s = + - ➔ 3penergy level. 1 1
2 clear that valence electron is present in 4s subshell as 4s • s
1 indicates that the element is present in IA group. So, the element
(c) n = 3, I= 2, m= - 2, s = + - ➔ 3d energy level. present in 4th period and IA group is potassium (K).
2
1 24. According to Aufbau principal the energy of orbital depend upon
(d) n = 3, I= 0, m= 0, s = + - ➔ 3s energy level. n+ /value.
2
According to Aufbau principle, the energy of orbitals 25. Orbital angular momentum = ./i(i+rj ·..!!....
(other than H-atom) depend upon (n + I) value.
27t
for 2s-orbital, I = 0
(n + I) for 3d = 3 + 2 = 5
Hence, fl + I = 5 maximum. .-.Orbital angular momentum= ✓O (0 + I)..!!....= zero
27t
So, it is highest energy level (in the given options).
40 I Chapterwise & Topicwise Engineering Entrances Solved Papers

26. The orbital angular momentum = _!!_✓l(l + I) 35. s-subshe ll has only one orbital and that is spherical, hence,
27t s-orbitals are non-directional.
For 3s-electron, l = 0 Hence, when fl= 3, then l = 3 does not exist.
: .Orbital angular momentum 36. (I) Is (II) 2s (III) 2 p
h ~ (IV) 3d (V) 3d
= - --,0(0+ l)=0(zero)
27t In the absence of any field, 3d in (IV) and (V) will be of equal
27. The number of electrons= 2n2 energy.
where, n = principal quantum number. 1
37. Hydrogen atom is in ls , state and these 3s, 3p and 3d-orbitals
For n = 2 w ill have same energy w.r.t. ls-orbital.
Number of electrons = 2 (2)2 = 8 38. The value of' n' and'/' equal to 4 and 3 respectively, corresponds
28. (a) n = 2, I= l, m = 0, it is possible to 4 /-orbital, hence the electron will belong to 4 /-orbital.
39. Total number of orbitals for principal quantum number n is equal
(b) n = 2, I = 0, m = - i it is not possible because, if I = 0, m must
to ,i2.
be 0. The value of m totally depends upon the value of l
(m = - l to + /). 40. According to rules for quantum munber the possible values of
n, I, m ands are
(c) n = 3, / = 0, m = - 0, it is possible.
fl = 1 to oo any whole number
(d) n = 3, /=I, m = - 1, it is possible
I = 0 to (n - I) for every value of fl
. ~ h
29. Orbital angular momentum (L) = --,l(I + 1)- m = - l to zero to + l for every value of/
21t 1 I
ford-orbital, I= 2 s = - or- -
2 2
(L)= ✓2(2+ I)_!!_= ✓6h (a) n = 4 , I= 3, m =0
27t 27t
All the values are according to rules.
30. Any sub-orbit is represented as nl such that n is the principal
(b) n = 4, I= 2, m =I
quantum number (in the form of values) and I is the azimuthal
quantum number (its name). All the values are according to rules.
Value of/< n, I: 0 I 2 3 4 (c) n = 4, I= 4, m = 1
s pd f g ·:The value of /can have maximum (n - l)value i.e. 3 in this case.
Value of m : - I, ........ 0, ........ + l :. This set of quantum numbers is non-permissible.
I I (d) n=4,l=0,m=0
Value of s : + - or - -
2 2 A ll the values are according to rules.
Thus, for 4 f : n = 4, I = 3, m = any va lue between - 3 to + 3 Choice (a), (b) and (d) are permissible.
31. When n = 3, number of values of/ are Oto (n - I) i.e. 0, I, 2.
. ~h
Topic 5 Filling of Orbitals in Atom
32. 0 rb1tal angular momentum = --,l(l + 1)-
21t 1. U sing inert gas, the configuration of Cu can also be represented as
10 1
For ~orbital, I = I Cu 29 = [Ne]3s2, 3/, 3d , 4s .
~ h ✓2h
.
: . Orbital angular momentum = v I (I+ 1) - = - - =
21t 21t
h
-v 21t
= 2. 19K = [Ar] 4 s I n = 3, / = 0 i.e. 3s contains 2 electrons
3. n l 11/ (suborbit) n+ l
2
33. K(Z = 19): ts2, 2s22p6, 3s 3p6, 4s 1
4 I 4p 5
In the ground state the value of l can be either zero or one. Hence,
the set (d) of quantum numbers i.e. (n = 3, l = 2, m = + 2) is not 4 0 4s 4
possible in the ground state. 3 2 3d 5
34. For2~subshell, 3 I 3p 4
n=2,l= 1,m=
Higher the value of(n + /),higher the energy. Tf(n + /)are same,
suborbit with lower value of n has lower energy.
Thus, 3p < 4s < 3d < 4 p
(4) < (2) < (3) < (1)
4. 29 Cu = 2, 8, 18, I
2 2 10 1
= ts2, 2s 2/, 3s 3/ 3d , 4s
1
Quantum munbers for 4s electron are
Hence, number of e- withs= _ _!_ is 3. I
2 n= 4, I= 0, m = 0,s = + -
2
 Structure of Atom I 41
10 2
5. Configuration of the given species are 15. Zn(30)= (Ar ]3d ,4s
c1- = 2, 8, 8 Zn 2 + = [Ar]3d 10 [no unpaired electron]
2
0 - = 2, 8 Fe(26) = [Ar]3tf, 4s2
Na+= 2, 8 Fe2 + =[Ar]3tf
Mg + 2
= 2, 8
Thus, Cl- has same electrons in outermost as well as
3d ol 1~ Ull!lLlJ [four unpaired electrons]

penu ltimate shell. Ni (28) = [Ar ]3d8, 4s 2

6. Magnetic moment, µ = ✓n (n + 2) BM Ni3+ = [Ar]3d7
where, n = number ofupaired electrons

Outermost electronic Number of Magnetic moment

3
d
7
I1~ I1~1111111 [three upaired electrons]

Ion
configuration upaired e- (BM) Cu(29) = [Ar]3d 10 , 4s 1
y3+ 3d2 = 11 2 ✓2 (2 + 2) = 2.82 Cu+ =[Ar]3d 10 [no unpaired electron]
10 1
16. [Ar]3d ,4s (atomic number 29) electronic configuration
Cr3 + 3
3d = 111 3 ✓3 (3 + 2) = 3.87
belongs to copper.
Fe3+ 3d5 = 11111 5 ✓ 5(5+2)=5.91 17. Electronic configuration ofMn (25) is

Ti 3 + 1
1s2, 2s2, 2µ6, 3s2, 3µ6, 4s2, 3d5
3d = 1 I .JTTl+25=1.73
:. Electronic configuration of Mn 2 + is
7. According to Hund's rule of maximum multiplicity, during filling ls2 ,2s2 ,2p6 ,3s2 , 3p6 ,3d5
of electrons in a subshell, pairing of electron cannot take place
Mn 2 + = [Ar ]3d5 , 4s0
untill there is any empty orbital available.
5 0
8. According to Pauli Exclusion Principle, in any orbital, maximmn 3d 4s
two electrons can exist, having opposite spin. =[Ar] I 1111111111 □
9. The electronic configuration of Fe atom is
18. Aufbau principle states that in the ground state of an atom, t11e
Fe (26) = [Ar] 3d6 4s2, Fe3+ = (Ar] 3d5 4s0
orbital w ith lower energy is filled up first before the filling of the
orbitals with a higher energy commences. Increasing order of
11111111111 energy of various orbitals is Is, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s,
five unpaired electrons
... etc.
10. The atomic number of neon is 10.
Therefore,
GS Ne[IO]: ts2, 2s2, 2µ6
1
[I] 1-~~1-1~l-1~1 ts not obeyed by Aufbau principle. Without
~I
ES Ne[ IO] : Js2, 2s2, 2p5 ,3s
Hence, Js2, 2s2, 2p5 , 3s 1 electronic configuration indicates the fully filling ofs-subshell electrons cannot enter in p -subshell in
ground state of atom.
excited state of neon.
19. The atomic nmnber of cesimn is 55. The electronic configuration
11. The electronic configuration of element with atomic number 24 is
of cesium atom is
ts2 2s2 2p6 3s2 3p6 3d 5 4s 1 2 10 10 1
55 Cs = Js2, 2s 2p6, 3s23p6, 4s2, 3d 4p6, 5s2,4d , 5p6, 6s
[since, exactly half-filled orbitals are more stable than nearly The electronic configuration of cesium ion will be
half-filled orbita ls]
cs+ = Js2, 2s 2 2p6, 3s23p63d10 , 4 s 2 4p64d 10 , 5s 2 5p6, 6s0
12. H igher the value of (n + I), higher will be the energy of electron.
So, the total nmnber of s-electrons = I 0, the total number of
If value of (n + I) is same for any two or more electrons, the
p-electrons = 24, the total number of d-electrons = 20
electron with higher value of n, has higher energy. Hence, the
correct order of energy is 20. Electronic configuration of
2
V< I < III < TI < IV 28 Ni = ls , 2s22p6, 3s2 3p63d8 , 4s2
2 2 2
·: (n + I) 4 5 5 5 6 N i + = Js2, 2s 2p6, 3s 3/3d8 , 4s0
13. Species having the same number of electrons as in oxide ion, has 2 2
= ls , 2s22p6, 3s 3p63d 10, 4s 1
29 Cu
the same electroni c configuration as oxide ion. 0 2- or NJ--both
species have same number of electrons ( IO electrons). cu+ = ls 2 , 2s22p6, 3s2 3p63d 10, 4s 0

14. EC of M = (Ar] 4s23d8 So, the given configuration is of Cu+.

2
ECofM + =[Ar]4s 3d 0 8 21. Cr(24) = ls 2 , 2s2, 2µ6, 3s2, 3p6, 3d5 , 4s 1

Total electrons= 28 = atomic number

42 I Chapterwise & Topicwise Engineering Entrances Solved Papers

22. Ti 2+ = Ii, 2i2/, 3i3/3d2,4s0 3

29. Fe + ion has the following configuration
y 3
+ = ls2, 2s22/, 3s23/, 3d , 4s 2 0
Fe3+ = ls2, 2s 2 2µ6, 3s23µ63d 5
Cr4+ = Is 2·2s2 2µ6, 3s23p2 3d2,4s0 Hence, ferric ion is quite stable due to half-filled d-orbitals.
Mn 5 + = ls2, 2s2 2p6, 3s2 3µ63d2,4s 0 30. 20 Ca= 2, 8, 8, 2
2
[Ar J3d64s2, Fe2 + (24 electrons)= [Ar J3d64s 0 Ca + = 2, 8, 8
23. 26Fe=
1 Hence, Ca 2 + has 8 e lectrons each in outermost and penultimate
24. Cr(24):[Ar ]3d5 4s , Cr 3+ :[Ar]3d3 4s 0
shell.
25. u- = is2 , 2i (in it all subshells are saturated so it is stable) 31. The ground state configuration of chromium is
Be- = 1s2, 2s 2 , 2p' (very much less stable) 5
24 Cr = [Ar]3d 4s
1

2 2 2 4 0
B- = ls , 2s2, 2p (less stable) 24 Cr + = [Ar ]3d 4s
c- = ls2 , 2s2, 2p3
(stable due to presence of half-filled 2p-subshell) 32. Symbols K L M N
26. For' N' shell 19X = 2 8 8 1
·: The munber of shell (n) = 4 21Y = 2 8 9 2
: .The number of sublevels or subshell (/) = 4 2sZ = 2 8 13 2
The number of orbitals
Hence, the order of munber of electrons in M shell is
=n2 =4 2 =16
Z>Y>X
and the number of electrons
33. Deuterium is an isotope of hydrogen. Its atomic number is one.
= 2,/ = 2 X 4 2 = 32 Hence, its electronic configuration is
27. Fe(26) = Is2, 2s22p6, 3s23/3d6, 4s2 1D2: Is'.
3d6 means I1~ 11111111I 34. A p-orbital has 3 dumb Ies (i.e. Px, Py and p,) and each dumb le can
accommodate maximum of2 electrons. So, maximum number of
Hence, it has 4 unpaired electrons. electrons in p-orbital is 6.
Fe2 + = Ii, 2s22p6, 3s23/3d6, 4s 0 35. According to Autbau principle, electrons enter into orbitals
:. It also has 4 unpaired electrons. according to their energy. The electron first enters into orbital
Fe3 + = is 2 , 2s2 2µ6, 3s23µ63d 5 , 4s0 having lesser value of (11 + /). If the value of 11 + I is same for two
orbitals, then the electron will first enter into orbital having lesser
3ds means 1111111111 I value of 11.
For one orbital
Hence, it has 5 unpaired electrons.
11 = 5, I= 0 :. n + I= 5 + 0 = 5
28. According to Autbau principle, as electron enters the orbital of For other, 11 = 3, I= 2 :. fl + I= 3 + 2 = 5
lowest energy first and subsequent electrons are filled in the order
·:Bothof the orbitals have same value for n + I.
of increasing energies. The relative energies of various orbital in
increasing order are :. Electron will enter into orbital having lower value of n.
Electron will enter into fl= 3, I= 2 orbital.
Is, 2s, 2p, 3s, 3p, 4s, 3d, 4p, Ss, 4d, Sp, 6s, 4 f, Sd, 6p, ?s
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Classification of Elements
and Periodicity in Properties
QUICK REVIEW
Several attempts have been made to classify elements by
various scientists and their numerous efforts finally led to the
development of periodic law and periodic table
The earlier attempts made to classify elements are as follows
Dobereiner's Triads
Dobereiner identified some groups of three elements (triads)
having similarity in physical and chemical properties. He also
noticed that atomic mass of middle element was arithmetic
mean of other two elements. e.g. Li, Na, K, Cl, Br, I etc.
Newland's Law of Octaves
Newland arranged the elements in order of their increasing
atomic weights in such a manner that the eighth element
starting from a given one is a kind of repetition of the first.
(like the eighth note of musical scale).
Lother Meyer's Graph
Lother Meyer used physical properties such as melting point,
boiling point, atomic volume etc, to relate similarities among
particular set of elements.
For e.g. when atomic volume of elements are plotted against
atomic mass, the similar elements were found to occupy
similar positions in the graph.
Mendeleev's Periodic Table
Mendeleev a1Tanged 63 elements known at that time in order
of increasing atomic weight on the basis of his famous
periodic law. Periodic Law-The physical and chemical
properties of the elements are periodic function of their
atomic weights).
(i) He placed elements having similar nature in the same
group with respect to atomic weight.
(ii) At some places the order of atomic weight was changed in
order to justify the physical and chemical nature of
elements.
(iii) Some places were left vacant for new elements which
were not discovered at that tin1e.
Moseley's Modern Periodic Law
The physical and chemical properties ofelements are periodic
function of their atomic number.
Long Form of Periodic Table
(i) It contains 7 periods (horizontal rows) and 18 groups
(vertical columns).
(ii) The number of period denotes the number of outem1ost
shell of that element. 1st period is very short period
contains two elements. 2nd and 3rd periods are short
periods contain eight elements each.
4th and 5th periods are long periods contain eighteen
elements each. 6th period contains 32 elements (very
long period) and 7th period is incomplete.
(iii) Elements of group 1 are called alkali metals. Elements of
group 2 are called alkaline earth metals. Elements of
group 1 and 2 constitute s-block elements. These are
highly reactive soft metals.
(iv) Elements of group 13 to 18 constitute p -block. p -block
elements include metals, non-metals and a few metalloids.
(v) Elements of group 3 to 12 constitute d-block elements.
d-block elements are transition metals. These elements
show variable oxidation states, paramagnetism, form
coloured complex ions and possess catalytic activity.
(vi) The elements of two horizontal rows placed at the bottom
of the periodic table are called / -block elements. These
are also known as inner transition elements (Lanthanides
and actinides).
44 I Chapterwise & Topicwise Engineering Entrances Solved Papers
General Electronic Configurations
6 because of increase in the effective nuclear charge on
(i) Inertgases(exceptHe)ns2np •
(ii) Representative elements (sand p-block elements)
1 2
ns tons np 6 .
(iii) Transition elements (d-block elements)
(n - l)d1- 1ons1 - 2_
Ionisation Energy
(iv) Inner transition elements (/-block elements)
(n - 2)/1 - t4 (n - l)do - t ns 2 •
(v) The reason of periodicity is the periodic repetition of
outer configuration of the elements at regular intervals.
HJPAC Nomenclature
IUP AC nomenclature for the elements having atomic number
more than 100.
• The names are derived by using roots for the three digits in
the atomic nwnber of the element and adding the
ending-iu m.
Electron Gain Enthalpy
• The roots for the numbers are as follows
Number O 2 3 4 5 6 7 8 9
Root nil un bi tri quad pent hex hept oct en
The symbol for the element is made by first letters from the
roots which make up name.
Diagonal Relationship
Elements of second period exhibit similarity in properties by
the elements of third row p laced diagonally to them due to
identical ionic radius and polarising power. For e.g. Li and
Mg, Be and Al, B and Si etc.
• Anomalous properties of second period elements First
elements of group I, 2 and group 13 to 17 (B to F) differs in
many respect from other members of their group. This is
due to their small size, high electronegativity and
non-availability of d-electrons.
• Periodic trends in properties of elements periodic
properties such as atomic size, melting and boiling point,
ionisation energy, electron affinity, electronegativity,
metallic character, nature of oxides, reducing character etc,
show a variation with change in atomic number.
Atomic Radius
(i) In general van der Waals' radius is greater than covalent
radius of an atom.
(ii) On moving across the period, the effective nuclear charge
increases an d thus atomic radius decreases.
(iii) On moving down the group atomic radius increases with
increase in value ofn (Principal quantum number).
The radius of anion is always greater than its neutral atom
due to decrease in effective nuclear charge.
The radius ofcation is always smaller than its neutral atom,
electrons left and decreases in the number of orbits for
most of the cases.
(iv) The size of isoelectronic species decreases with increase
in the nuclear charge (atomic number).
On moving across the period from left to right ionisation
energy increases with decrease in atomic radius.
However, there are some exceptions to the general trend for
e.g. IE of elements of group 2 is greater than group 3 due to
2
stable ns configuration. Similarly, IE of elements of group
15 is greater than IE of group 16 because exactly half-filled
orbitals possess extra stability.
On moving down the group ionisation energy decreases with
increase in atomic radius.
On moving across a period from left to right, electron gain
enthalpy increases. However, the electron gain enthalpy of
elements of group 2, 15 and 18 are against the expected trend.
These variations are due to stable configurations of exactly
half-filled orbitals or completely filled orbitals.
(i) On moving down the group, the magnitude of electron
gain enthalpy decreases due to increase in size.
(ii) The halogens have the highest electron affinity values in
a given period.
(iii) The electron gain enthalpy of the elements group 2 {II A)
and group 15 (VA) is positive. It is due to the presence of
outer fully-filled s-orbitals is group 2 and half-filled in
group 15 and thus, these atoms do not have the tendency
to accept an electron.
(iv) The electron gain enthalpy of the elements of third
period are higher than that of the elements of second
period.
It is due to small radius and high electron density in the
outem1ost orbit of second period elements.
The small size signifies limited capacity to release
energy, while high electron density signifies greater
repulsive forces which extra electron experience while it
is to be added.
e.g. the magnitude of electron gain enthalpy of fluorine
(element of second period) is unexpectedly less than
chlorine (elements of third period) due to stronger inter
electronic repulsions to the incoming electron in
relatively compact 2p-subshell.
(v) The electron gain enthalpy of gaseous anion is always
positive.
(vi) In general, greater the magnitude of electron gain
enthalpy, greater is the oxidising power.
 Classification of Elements and Periodicity in Properties I 45
Electronegativity where,
It is the power ofan element to attract the shared pair of electrons X A - X 8 = electronegativity difference between two
between two covalently bonded atoms. atoms A and B.
(i) On moving from left to right in a period electronegativity E A- B EA - A, and E 8 _ 8 are the bond energies of the
increases with decrease in size. molecules AB, A 2 ands; respectively.
(ii) On moving down the group, electronegativity decreases. IE+ A
(iii) The most electronegative elements is fluorine. (ii) Mulliken scale X = e
2
The least electronegative elements is Cs and Fr. However, where, X = electronegativity
for noble gases its value is taken as zero. IE= ionisation energy
Ae = electron affiniy
Measurement of Electro negativity
Electronegativity of different elements is calculated on ~ Decreases (across the period)
different scales as : l Basic nature of oxide
(i) Pauling scale The calculations are done with the help of Increases (down the group)
bond energies used in the formula
X A - Xn = 0.208.Ji.

Topic 1
Classification of Elements and Nomenclature
of Elements with Atomic Numbers > 100
2010
1. Number of elements presents in the fifth period of periodic 6. The general electronic configuration of the transition
table is [JCECEJ elements is [MHT CETJ
(a) 32 (b)lO (c) 18 (d) 8 (a) (n - l)d 1o, (n + I)s 2
2. The element with the electronic configuration as (b) (n - I )dl - to' (n + l)sl - 2
10 3
[Ar]3d 4s24p represents a [JCECEJ (c) (n - l)dt - to, np6, ns2
(a) metal (b) non-metal (d)(n - l)d 1 - 10 , ns1 - 2
(c) metalloid (d) transition element
7. An element with atomic number 21 is a [KCETJ
2009 (a) halogen (b) representative element
3. The elements present in the core of earth are collectively (c) transition element (d) alkali metal
known as [Kerala CEEJ 8. The electronic configuration,
2 2 2
(a) lithophiles (b) nucleophiles Is , 2s 2p 6 , 3s 3p 6 3d 9 represents a [WB JEE]
(c) chalcophiles (d) siderophiles
(a) metal atom (b) non-metal atom
(e) atmophiles
(c) non-metallic anion (d) metallic cation
4. The element with atomic number 117 if discovered would be
9. Differentiating electron in inner transition elements
placed in [AMU]
enters the ...... orbital. [J&K CETJ
(a) noble gas family (b) alkali family
(a)s (b)p (c)d (d)f
(c) alkaline earth family (d) halogen family

2008 2007
10. In the periodic table metals usually used as catalyst
5. The discovery of which of the following group of elements
belong to [KCET]
gave death blow to the Newland's law of octaves?
(a) Inert gases (b) Alkaline earths [Manipall
(a) / -block (b) d-block
(c) p-block (d) s-block
(c) Rare earths (d) Actinides
46 I Chapterwise & Topicwise Engineering Entrances Solved Papers

11. Which of the following statements is wrong? [AMU] 14. What is the name of element with atomic number 105?
(a) Metals are more than non-metals (a) Kurchatovium (b) Dubnium [WB JEE]
(b) There are only few metalloids (c) Nobelium (d) Holmium
(c) Hydrogen can be placed with alkali metals as well as 15. Which pair has both members from the same period of
with halogen in periodic Table pe1iodic table? [BCECE]
(d) Non-metals are more than metals
(a) Cl, Br (b) Ca, Cl (c) Na, Ca (d) Na, Cl
2006
2005
12. Which of the following electronic configuration represents
16. The only non-metal which is liquid at ordinary temperature
noble gas? [WB JEE]
6 5
is [UPSEE]
(a) ns2np (b) ns2np
4
(a) Hg (b) Br2
(c) ns2np (d) ns2np 3 (c) NH 3 (d) None of these
13. Which of the following element is metalloid? [WB JEE] 17. The element with atomic number 36 belongs to ...... block
(a)Bi (b)Sn in the periodic table. [Guj CET]
(c) Ge (d) C WP ~ s ~f ~d

Topic 2
Periodic Trends in Properties of Elements and Atomic Radius
2014
1. The first ionisation potential of Na, Mg and Si are 7. The electron affinity of Be is almost similar to that of
respectively 496, 737 and 786 kJ mol- 1 . The ionisation (a) Li (b) B [Manipal]
potential of Al will be closer to [AMU] (c) Na (d) Ne
1 1
(a) 760 kJ mol - (b) 575 kJ mol - 8. Smallest among these species is [KCET]
(c) 801 kJ mo1 - 1 (d) 4 19 kJ mo1- 1 (a) lithium (b) lithium ion
2. The increasing order of the atomic radius of Si, S, Na, Mg, (c) hydrogen (d) helium
Al is [EAMCET] 9. Which among the following bas the highest ionisation
(a) S < Si < Al < Mg < Na potential? CKCETJ
(b) Na < Al < Mg < S < Si (a) B (b) Li
(c) Na < Mg < Si < Al < S (c) Ne (d) F
(d) Na < Mg < Al < Si < S
10. Order of electron affinity of F, Cl, Br and I is [OJEEJ
3. Which of the following sets has the atoms and/or ions in the
(a)F < Cl > Br > I (b)F > Cl > Br > I
correct order of increasing size? [IPU CET]
(c) F < Cl < Br < I (d) F > Cl < Br > I
(a) Ne< F- < 0 2- (b) Br- < c1- < F-
(c) Na+ < Mg 2+ < Al 3+ (d) P < S < Cl 2012
11. The increasing order of the ionic radius of the given
4. Ionisation energy and electron affinity are defined at
isoelectronic species is [AIEEEJ
(a) enthalpy (b) spontaneity [J&K CET]
(c) equilibrium (d) absolute zero (a) Cl- < Ca 2+ < K+ < s2- (b) s2- <Cl- < Ca 2+ < K+
(c) Ca 2+ < K + < C l- < S 2- ( d) K + < S 2- < Ca 2+ < Cl-
2013
12. Which of the following have the largest ionic size?
5. The first ionisation potential of Na is 5.1 eV. The value of
(a) F- (b) 0 2- [BITSAT]
electron gain enthalpy of Na+ will be [JEE Mains]
(c)Na+ (d)Mg 2+
(a) - 2.55eV (b) - 5.l eV
(c)- 10.2eV (d) + 2.55eV 13. Beryllium shows diagonal relationship with [Manipall
6. The correct order of electronegativity ofN, 0 , F and P is (a) B (b) Mg (c) Al (d) Na
[Manipal] 14. The correct order of ionisation energy ofC, N, 0 and Fis
(a) F > N > P > 0 (b)F > O > P > N (a) C < N < 0 < F (b) C < 0 < N < F CKCETJ
(c)F > O > N > P (d)N > O > F > P (c) F < 0 < N < C (d) F < N < C < 0
 Classification of Elements and Periodicity in Properties I 47
15. Which of the following is not a pe1iodic property? 25. In which one ofthe following pairs the radius of the second
(a) Atomic mass {b) Atomic volume [OJEEJ species is greater than that of the first? [ManipalJ
(c) Covalent radius (d) Electronegativity (a) Na, Mg (b) 0 2- , N 3-
16. The strongest base of the following is [AMUJ (c) Li+ , Be2+ (d)Ba 2 + ,Sr2 +
(a) NaOH (b) KOH (c) LiOH (d) CsOH 26. The ionisation potential order for which set is correct?
17. The correct order of acidic strength is [AMUJ (a) Cs < Li < K (b) Cs < Li > B [ManipalJ
(a)K 20 > Ca0 > Mg0 (b)C02 > N 20 5 > S03 ( c) Li > K > Cs ( d) B > Li < K
(c)Na 20 > MgO > Al 20 3
(d)Cl 20 7 > S02 > P4 0 10 27. What is the correct decreasing order of ionic radiius of
following ions?
2011
N 3- , 0 2- ' F- , N a + , Mg 2+ [MPPET]
18. Which of the following statements is wrong? [AIEEEJ
(a) N 3 - > 0 2- > p- > Mg 2+ > Na+
(a) The stability ofhydrides increases from NH 3 to BiH 3
in group 15 of the periodic table (b)N 3- > 0 2- > F- >Na+ > Mg 2+
(b) Nitrogen cannot fom1 dn- pn bond ( c) N 3 - > 0 2- > Mg 2+ > Na+ > F-
( c) Single N-N bond is weaker than the single P-P ( d) Na+ > F- > 0 2- > Mg 2+ >N3-
bond
(d) N 2 0 4 has two resonance structure. 28. Generally, the first ionisation energy increases along a
pe1iod. But there are some exceptions. One which is not an
19. Which one of the following orders presents the correct
sequence of the increasing basic nature of the given exception is CKCETJ
ox.ides? [AIEEE] (a) N and O (b) Na and Mg
(c) Mg and A l (d) Be and B
(a) Al 20 3 < MgO< Na 20< K 20
(b) MgO< K 20< Al 20 3 < Na 20 29. The correct order of decreasing first ionisation energy is
(c) Na 2 0< K 20< MgO < Al 20 3 (a)C > B > Be> Li (b)C > B e> B > Li CRPETJ
(d) K 20< Na 20< Al 20 3 < MgO (c)B > C > Be> Li (d) Be > Li > B > C
20. The number of naturally occurring p-block elements that 30. The property of attracting electrons by the halogen atoms
are diamagnetic are [KCETJ in a molecuJe is caJled [JCECEJ
(a) 18 (b) 6 (c) 5 (d) 7 (a) ionisation potential (b) e lectron affinity
( c) electronegativity (d) electronic attraction
21. Be and Al exhibit diagonal relationship. Which of the
following statements about them is/are not true? 2009
T. Both react with HCI to liberate H2.
31. In which of the following arrangements, the sequence is
IT. They are made passive by HNO3 •
not strictly according to the property written against it?
Ill. Their carbides gives acetylene on treatment with water.
TV. Their oxides are amphoteric. [Kerala CEEJ (a) CO 2 < Si02 < Sn02 < Pb02 : increasing oxidising
power [AIEEEJ
( a) III and rv (b) I and III
(c) Only I (d) II and III (b) HF < HCI < HBr < HI: increasing acid strength
(e) Only III (c) NH 3 > PH 3 < AsH 3 < SbH3 : increasing basic
strength
22. The correct decreasing order of first ionisation enthalpies
(d) B < C < 0 < N: increas ing first ionisation enthalpy
of five elements of the second period is [Ke ral a CEEJ
32. The set representing the correct order of ionic radius is
( a) Be > B > C > N > F (b) N > F > C > B > Be
(c)F > N > C > Be > B (d)N > F > B > C > Be (a) Li+> Be 2+ >Na+ > Mg 2+ [AIEEEJ
(e) F > C > N > B > Be 2
(b) Na+ > Li + > Mg + > Be + 2

23. Which one of the following has the lowest ionisation (c) Li 2+ >Na+ >Mg 2+ > Be 2+
energy? [WB JEE] (d)Mg 2+ > Be 2+ >Li+ >Na+
2 2 2 2 1
(a) Is 2s 2p 6 (b) Is 2s 2p 6 3s 33. The oxide of an element whose electronic configuration is
(c) 1s22s22ps (d) Is22s2 2p3 ls2 ,.,h2 2 6 3
'~ • p ' sI .
IS [Manipal]

2010 (a) neutral (b) amphoteric (c) basic (d) acidic

24. Among the following, the number of elements showing 34. The order of stability of metal oxides is [Manipal]
only one non-zero oxidation state is 0 , Cl, F, N, P, Sn, Tl, (a) Al 20 3 < MgO< Fe 2 0 3 < Cr20 3
Na, Ti [IIT JEE] (b) Cr2 0 3 < MgO< A1 2 0 3 < Fe 20 3
(a)l (b)2 (c) Fe 20 3 < Cr20 3 < Al 20 3 < MgO
(c)3 (d)4 (d) Fe 2 0 3 < Al 20 3 < Cr2 0 3 < MgO
48 I Chapterwise & Topicwise Engineering Entrances Solved Papers

35. The pair of elements having approximately equal ( c) Greater interelectron repulsion between two
ionisation potential is [UPSEE] electrons in the same p-orbital counter balances the
increase in effective nuclear charge on moving from
(a) Al, Ga (b) Al, Si (c) Al, Mg (d) Al, B
nitrogen to oxygen
36. Which of the following oxides is most acidic in nature? (d) Greater effective nuclear charge of oxygen than
(a) BeO (b) MgO [AMU]
nitrogen
(c) Cao (d) BaO (e) Higher electronegativity of oxygen than nitrogen
37. Which is not the correct order for the stated property? 44. Match the following columns. [Kerala CEE]
(a) Ba > Sr > Mg; atomic radius [DCE]
Column I Column JI
(b) F > 0 > N; first ionisation enthalpy
A. He I. High electron affinity
(c) Cl > F > I; electron affinity
(d) 0 > Se > Te; electronegativity B. Cl 2. Most electropositive element
c. Ca 3. Strongest reducing agent
2008 D. Li 4. Highest ionisation energy
38. The atomic numbers of elements A, B, C and D are
Z - 1, Z, Z + 1 and Z + 2, respectively. If B is a noble gas, Codes
choose the correct answer from the following statements. A B C D A B C D
I. A has hig her electron affinity. (a) 3 1 2 4 (b)4 3 2 1
II. C exists in +2 oxidation state. (c) 2 4 1 3 (d) 1 2 3 4
III. D is an alkaline earth metal. [BITSAT] (e) 4 1 2 3
(a) I and II (b) II and III 45. In a given shell the order of screening effect is [WB JEE]
(c) I and III (d) I, II and III (a)s>p>d>f (b)s>p>J>d
39. If the electronegativity difference between two atoms (c)f>d>p>s (d)s<p<d<f
A and Bis 2.0, then the percentage of covalent character in 46. The electronic configurations of four elements are given
the molecule is [Manipal] below. Arrange these elements in the correct order of the
(a) 54% (b) 46% {c) 23% (d) 72% magnitude (without sign) of their electron affinity.
I. 2s22p5 II. 3s23p5
40. Which one of the following statements is false?
[MPPET] III. 2s22/ IV. 3s23/
(a) The electron affinity of chlorine is less than that of Select the correct answer using the codes given below
fluorine (a) I < TI < IV < III [Guj CETJ
(b) The electronegativity of fluorine is more than that of
(b) TI < I < IV < III
chlorine
(c) I < III < IV < II
( c) The electron affinity of bromine is less than that of
(d) TII < IV< I < II
chlorine
( d) The electronegativity of chlorine is more than that of 47. The electronic configuration of the atom having maximum
bromine difference in first and second ionisation energies is
2 2 6 1
41. The correct order in which the first ionisation potential (a) l s , 2s , 2p , 3s [Guj CET]
2 2 2
increases is [KCET] (b) I s , 2s , 2p 6 , 3s
(a) Na < K < Be {b)K < Na < Be (c) ls 2 , 2s 2 , 2p 1
(c)K< Be < Na (d)Be < Na < K (d) l s
2
, 2s
2
, 2p 6 , 3s
2
, 3p1
42. The electronic configuration ofthe element with maximum
48. The element with the lowest ionisation potential is
electron affinity is [Kerala CEE]
(a)Na (b)K [J&K CET]
(a) ls2, 2s2' 2p3 (b) ls2 ' 2s2 '2ps (c) Rb (d) Cs
(c) 1s-' ,2s-' , 2p 6 , 3s 2 , 3p 5 (d)1s-' , 2s-' ,2p 6 ,3s2 ,3p 3 49. Which of the following metal oxides is most basic?
(e) ls 2 , 2s 2 , 2p 6 , 3s 1 (a) ZnO (b) Al 2 O 3 [J&K CET]
43. The first ionisation energy of oxygen is less than that of (c) As 2 0 3 (d) K 2 0
nitrogen. Which of the following is the correct reason for 50. Difference between S and S 2- as S 2- has [BCECE]
this observation? [Ke rala CEE]
(a) larger radii and larger size
(a) Lesser effective nuclear charge of oxygen than (b) smaller radii and larger size
nitrogen ( c) larger radii and smaller size
(b) Lesser atomic size of oxygen than nitrogen (d) smaller radii and smaller size
 Classification of Elements and Periodicity in Properties I 49
51. Highest electron affinity among the following is [BCECE] 63. The element having highest electron affinity is [BCECEJ
( a) fluorine (b) chlorine (c) sulphur ( d) xenon (a) bromine (b) iodine
52. Increase in atomic size down the group is due to [BCECE] ( c) fluorine ( d) chlorine
(a) increase in number of electrons 64. Which one of the following ions has the highest value of
(b) increase in number of protons and neutrons ionic radius ? [Jamia Millia Islamia]
(c) increase in number of protons (a) Li+ (b) B 3+ (c) 0 2- (d) F-
( d) increase in number of protons, neutrons and electrons
65. The correct order of size of iodine species is [DCE]
53. In the following, the element with the highest ionisation
(a) I> Y- > I+ (b) Y- > I > I+
energy is [Jamia Millia Islamia]
2 3 (c) I+ > I> Y- (d) Y- > I+ > I
(a) [Ne] 3s , 3/ (b) [Ne] 3s2, 3p
(c) [Ne] 3s
2
, 3p 2 (d) [Ne] 3s 2 , 3p4 2006
1
54. The electron affinity values (in kJ mol - ) ofthree halogens 66. The increasing order of first ionisation enthalpies of the
X , Y and Z are respectively -349, - 333 and -325. Then, elements B , P, S and F (lowest first) is [AIEEEJ
X, Y and Z respectively, are [DCEJ (a) F < S < P < B (b) P < S < B < F
(a) F2 , Cl 2 and Br2 (b) Cl 2 , F2 and Br2 (c) B < P < S < F (d)B < S < P < F
(c) Cl 2 , Br2 and F2 (d) Br2 , Cl 2 and F2 67. Following statements regarding the periodic trends of
chemical reactivity to the alkali metals and the halogens
2007 are given. Which of these statements gives the correct
55. Which of the following is an amphoteric oxide? picture? [AIEEE]
(a) SO3 {b) MgO [MHT CET] (a) The reactivity decreases in the alkali metals but
(c)Al 2 0 3 {d)P4 0 10 increases in the halogens with increase in atomic
56. Which one of the following is an amphoteric oxide? number down the group
(b) In both the alkali metals and the halogens the
(a) ZnO (b) Na 2 O [MPPET]
chemical reactivity decreases with increase in atomic
(c) SO2 (d) B 2 O 3 number down the group
57. The first ionisation potential ofNa, Mg, Al and Si are in the ( c) Chemical reactivity increases with increase in atomic
order [WB JEE] number down the group in both the alkali metals and
(a) Na < Mg > Al < Si (b)Na > Mg > Al < Si halogens
(c)Na < Mg < Al > Si (d)Na > Mg > Al < Si (d) In alkali metals the reactivity increases b ut in the
halogens it decreases with increase in atomic number
58. Which element has highest electronegativity? [WB JEE] down the group
(a)F (b)He 68. Which is chemically most active non-metal? [Manipal]
(c) Ne (d) Na
(a) S (b) 0 2 (c) F2 (d) N 2
59. Which of the following oxides doesn't react with both of an
acid and alkali, is? [WB JEE] 69. One mole of magnesium in the vapour state absorbed 1200
kJmo1- 1 of energy. If the first and second ionisation
(a) ZnO (b) SnO 2 (c) Al 2 O 3 (d) BeO
energies of Mg are 750 and 1450 kJmol - 1 respectively, the
60. Ionic radius is [UPSEE]
final composition of the mixture is [Kerala CEE]
(a) inversely proportional to effective nuclear charge
(a) 3 1% Mg + + 69% Mg 2+ (b) 69% Mg + + 3 1% Mg 2+
(b) inversely proportional to square of effective nuclear
charge (c) 86% Mg + + 14% Mg 2 + (d) 14% Mg+ + 86% Mg 2 +
(c) directly proportional to effective nuclear charge (e) 13% Mg + + 87% Mg 2 +
(d) directly proportional to square of effective nuclear
charge 70. The successive ionisation energy values for an element X
are given below.
61. Which one of the following arrangements represents the
I. 1st ionisation energy = 410 kJ mol-1
correct order ofelectron gain enthalpy (with negative sign) 1
of the given atomic species ? [UPSEE] TI. 2nd ionisation energy = 820 kJ mol-
(a)Cl < F < S < O (b)O < S < F < Cl ITT. 3rd ionisation energy = 11 00 kJ mo1-1
(c)S < O < Cl < F (d)F < Cl < O < S IV. 4th ionisation energy= 1500 kJ mo1- 1
62. The electronic configuration of most electronegative V. 5th ionisation energy= 3200 kJ mo1- 1
elements is [BCECE]
Find out the number of valence electron for the atom X .
(a)' 1s2 , 2s2 , 2p s (b) 1s2 , 2s2 ' 2p4 ' 3st
(a) 4 (b) 3 (c) 5 [Kerala CEE]
c Is 2 , 2s 2 , 2p 6 ,3s I , 3p 5 (d )Is 2 , 2s 2 , 2p 6 ,3s 2 ,3p 5
() (d) 2 (e) 1
50 I Chapterwise & Topicwise Engineering Entrances Solved Papers

71. Which of the following element shows maximum valency? 82. Ionisation potential for a noble gas is [BCECE]
( a) Carbon (b) Barium [WB JEE] (a) maximum in a period
(c) Nitrogen (d) Sulphur (b) minimum in a period
( c) either minimum or maximum
72. Which of the following elements never show positive ( d) constant
oxidation number? [WB JEE]
83. Strongest oxidising agent among halogen is [BCECEJ
(a) 0 (b) Fe (c) Ga (d) F
(a) I 2 (b) Br2 (c) C l 2 (d) F2
73. Which of the following is a false statement? [WBJEE]
84. Atomic radii ofF and Ne, in A, are given by [BCECEJ
(a) Fluorine is more electronegative than chlorine
(b) Nitrogen has greater IE than oxygen (a) 0.72, 0 .7 1 (b) 0.72, 1 .6
(c) Lithium is amphoteric (c) 1.6, 1.58 (d) 0.7 1, 0.72
( d) Chlorine is an oxidising agent 85. Which of the following has largest ionic radius?[BCECEJ
74. The first ionisation potential is maximum for [WB JEE] (a)Cs+ (b)Li+ (c)Na+ (d)K+
(a) B (b) N
(c) 0 (d) Be
2005
86. Which one of the following oxides is an1photetic in
75. Which among the following elements have lowest value of
character? [AIEEE]
IE 1? [WB JEE]
(a) SnO2 (b) SiO 2 (c) CO2 (d) CaO
(a)Pb (b)Sn
(c) Si (d) C 87. In which of the following arrangements the order is not
according to the property indicated against it? [AIEEEJ
76. The elements with atomic numbers 9, 17, 35, 53, 85 are all
(a) Li < Na < K < Rb increasing metallic radit1s
(a) noble gases (b) halogens [AMUJ
(b) I < Br < F < Cl increasing electron gain enthaly (with
(c) heavy metals (d) light metals negative sign)
77. Observe the following statements. ( c) B < C < N < 0 increasing first ionisation enthalphy
I. The physical and chemical properties of e lements are ( d) Al 3+ < Mg 2 + < Na+ < F- increasing ionic size
periodic functions of their electronic configuration. 2
88. Among Na +, Na, Mg and Mg +, the largest particle is
II. Electronegativity of fluorine is less than the
2
electronegativity of chlorine. (a)Mg + (b)Mg [KCET]
III. Electropositive nature decreases from top to bottom in a (c) Na (d) Na+
group.
89. The order of first ionisation energies of the elements Li,
The correct answer is [EAMCET] Be, B, Na is [Kerala CEE]
(a) I, II and III (b) Only I (a)Li > Be > B > Na (b)Be > B > Li > Na
(c) I and II (d) II and III (c)Na > Li > B > Be (d)Be > Li > B > Na
78. Which one of the following has maxinrnm ionisation (e)B > Be > Li > Na
potential? [Guj CET] 90. Which is the correct order of electronegativity?[UPSEEJ
(a) K (b) Be (c) Na (d) Mg (a)F > N < O > C (b)F > N > O > C
79. Pauling's equation for dete1mining the electronegativity of (c)F > N > O < C (d)F < N < O=C
an element, is [J&K CETJ 91. Ionisation energy in group 1-A varies in the decreasing
(a) XA - Xs = 0.20g,,/j; (b) XA + Xs = 0.20g,,/j; order as [OJEEJ

(c) XA - X 8 = 0 .208t'1.2 (d) XA - X 8 = .f"i. (a) Li > Na > K > Cs (b) Na > Li > K > Cs
(c)Li > Cs > K > Na (d)K > Cs > Na > Li
where, X A , X 8 =electronegativity values ofelements A and
92. Identify the correct order in which the covalent radius of
B, t'1. = represents polarity of A-B bond. the following elements increases
80. The ionic radius (A) of C4- and 0 2
- respectively, are I. Ti II. Ca III. Sc CEAMCETJ
2.60 and 1.40. The ionic radius of the isoelectronic ion N 3- (a) I, II and III (b) III, II and I
would be [J&K CETJ (c) II, I and III (d) I, III and II
(a)2.6 (b) 1.71 93. The correct order of electron affinity is [J&K CETJ
(c) 1 .4 (d) 0.95
(a)B < C < O > N (b)B > C > N > O
81. Electron affinity is positive, when [BCECE] (c)O > C > B > N (d)O < C < B < N
(a) 0 changes into o - 94. The set representing the correct order of first ionisation
(b) o - changes into O 2- energy is [DCEJ
( c) 0 changes into o + (a)K > Na > Li (b)Be > Mg > Ca
(d) electron affinity is always negative (c) B > C > N (d) Ge > Si > C
 Answers
TOPICl Classification of Elements and Nomenclature of Elements with Atomic Number > 10 0
1. (c) 2. (c) 3. (d) 4. (d) 5. (a) 6. (d) 7. (c) 8. (d) 9. (d) 10. (b)
11 . (d) 12. (a) 13. (c) 14. (b) 15. (d) 16. (b) 17. (a)
TOPIC2 Periodic Trends in Properties of Elements
1. (b) 2. (a) 3. (a) 4. (a) 5. (b) 6. (c) 7. (d) 8. (c) 9. (c) 10. (a)
11 . (c) 12. (b) 13. (c) 14. (b) 15. (a) 16. (d) 17. (d) 18. (a) 19. (a) 20. (c)
21 . (e) 22. (c) 23. (b) 24. (b) 25. (b) 26. (c) 27. (b) 28. (b) 29. (b) 30. (c)
31 . (c) 32. (b) 33. (c) 34. (c) 35. (a) 36. (a) 37. (b) 38. (c) 39. (b) 40. (a)
41 . (b) 42. (c) 43. (c) 44. (e) 45. (a) 46. (d) 47. (a) 48. (d) 49. (d) 50. (a)
51 . (b) 52. (a) 53. (b) 54. (b) 55. (c) 56. (a) 57. (a) 58. (a) 59. (d) 60. (a)
61 . (b) 62. (a) 63. (d) 64. (c) 65. (b) 66. (d) 67. (d) 68. (c) 69. (b) 70. (a)
71 . (d) 72. (d) 73. (c) 74. (b) 75. (b) 76. (b) 77. (b) 78. (b) 79. (a) 80. (b)
81 . (b) 82. (a) 83. (d) 84. (b) 85. (a) 86. (a) 87. (c) 88. (c) 89. (b) 90. (a)
91 . (a) 92. (d) 93. (a) 94. (b)

Explanations
Topic 1 Classification of Elements and Nomenclature of Elements with
Atomic Numbers > 100
1. The fifth period starts from rubidium (37) and ends with xenon (54).
The last electron enters in 5s, 4d or 5µ-orbitals. T herefore, the fifth
period has (2 + 10 + 6) 18 elements.
2. Electronic configuration reveals that the p-orbital of the element is
not complete. Therefore, it is a p-block element. Moreover, the
atomic number of the element is 33(As). Therefore, it is a metalloid.
3. The elements present in the earth's core are collectively called
siderophiles. These are found in their native state. These elements
generally have a low reactivity and exhibit an affinity to fonn
metallic bonds. e.g. Pt, Ru, Pd, Ir, Os etc.
1
4. 117 =[Rn]5/ 4, 6d 10 , 7s2, 7/.
Since, the last electron enters in p-orbital, it w ill be a p-block
element and its group number = 5 + 2 = 7 (VIIA).
So, the element would be the placed in halogen family.
5. With the discovery of inert gases (group zero in Mendeleev's
periodic table), the law of octaves lost its original significance
since, it was now the ninth element which had properties similar to
the first one.
6. In d-block elements, the differentiating electron, i.e. the last
electron enters in the d-subshell their general electronic
configuration is (n- 1) d 1- 10, ns 1- 2•
7. The electronic configuration of element with atomic number 21 is
1
ls2, 2s2, 2µ6, 3s2, 3µ6, 4s2, 3d •
Since, this element contains partly filled d-orbital, so it is a d-block
element. d-block elements are also known as transition elements.
8. Electronic configuration of Cu is ls2 , 2s2, 2µ6, 3s2 , 3µ6, 4s 1, 3d 10 and
electronic configuration of Cu 2+ is 1s2,2s2 ,2µ6,3s 2 ,3p6, 3d9.
Hence, the given configuration represents metallic cation.
9. In inner transition elements, the differentiating electron enters
intof-orbitals of the anti-penultimate (inner to penultimate) i.e.
(n - 2) shell. Therefore, these elements are also known as
/-block elements.
10. In the periodic table, metals usually used as catalysts belong to
d-block as they show vari able as oxidation staters. e.g. N i, Pt
etc.
11. Non-metals are more than metals is the wrong statement.
12. Noble gases have fully filled valence shell electronic
configuration. Therefore, it represents m/np6.
13. Boron (B), Si, Ge, As, Sb, Te and At are the metalloid elements.
Bismuth (Bi) and tin (Sn) are metals while carbon (C) is
non-metal.
14. The element w ith atomic number 105 is Dnbnium. In TTJPAC
nomenclanire, it is known as Un-nil-pentiun.
15. The elements with same number of shells belongs to same
period. Sodium and chlorine are in same period.
11Na = 2, 8, I ⇒ 17 CI = 2, 8, 7
Both have 3-shells, hence they both are placed in 3rd period of
periodic table.
16. (!) Br2 is the only non-metal which is liquid at room
temperanire.
(ii) Hg is metal which is liquid at room temperature.
(iii) NH 3 is gas at room temperature.
17. The electronic configuration of element w ith atomic number 36,
is
= ls2 , 2s2 , 2µ6, 3s2, 3µ6, 3d 10, 4s2, 4µ6
As the last electron is present in p-subshell, hence the element
will be placed in p-block of the periodic table.
Topic 2 Periodic Trends in Properties of Elements
1. Ionisation potential depends upon the effective nuclear charge
which increases as we move along a period from left to right
and hence, ionisation potential increases from left to right
along a period but in case of elements having stable
(completely or half filled) shells, the ionisation potential is
more as compared to the element having non-stable
configuration.
The electronic configuration of the given elements is
11 Na = [Ne] 3s
1
12Mg = [Ne] 3s2 (s-shell completely filled)
13Al = [Ne] 3s2, 3/
= [Ne] 3s2, 3/
14 Si
Thus, the order of ionisation potential will be
Na < Al < Mg < Si
496 <? < 737 < 786
This suggests the TP of Al must lie in between 496 and 737. Thus,
its TP should be 575 kJ mol- 1•
2. Atomic radius is inversely proportional to effective nuclear
charge. As we move from left to right in a period, effective
nuclea r charge increases. Due to this atomic radius decreases.
Thus, correct order of atomic radius of 3rd period elements is
S < Si < Al < Mg < Na.
3. Before solving this, we should know certain facts regarding size
of elements and ions.
(i) In a periodic table, on going from left to right in a period,
the atomic radius of the elements decrease w hile on going
down a group of the periodic table, the atomic radius of
elements increases.
(ii) Cations are smaller than their parent atoms while anions are
larger than their parent atoms.
(iii) For isoelectronic species, as in case of Ne, F- and 0 2-, they
belongs to same period. So, according to mle (i) the atomic
size should follow the order O > F > Ne. But here O and F
are present in the form of their anions, i.e. 0 2- and F-.
And according to mle (ii) anions and larger than their
parent atoms. So, on the basis of both the m ies the correct
increasing size of atoms and/or ions is Ne< F- < 0 2- .
N ote In case of Br-, c 1-, F- the correct order wi ll be
F- <Cl-< Br- as they belong to same group.
In case of Na+, Mg2+ and Al 3+ the correct order will be
Al3+ <Mg2+ <Na+
This is because for isoelectronic species,
Jonie radius "" - - - - - -
atomic number
In case of P, S, Cl the correct order will be Cl < S <Pas
they belong to same period.
4. Ionisation energy and electron affinity both are change in energy.
So, these are defined at enthalpy.
5. Loss of electron from Na atom is represented as
Na ~ Na+ +e-,IE=5.leV (i)
Gain or addition of e- to Na+ ion is represented as
Na+ + e- ~ Na (ii)
As the reaction (ii) is reverse of (i) reaction, therefore, the
electron gain enthalpy of Na+ is reverse of ionisation energy.
Thus, t:,.H(egJ = -5.l eV
6. The electronegativity increases on moving from left to right in a
period and decreases on moving downward in a group. Hence, the
order of electronegativity is as
F> 0> N>P.
7. The electron affinity ofBe is almost similar to that ofNe because
Be has (fully-filled s -subshells and hence, stable configuration.
Thus, due to such stable configuration Be do not have the
tendency to accept the electron just like Ne.
8. The smallest species is hydrogen. It is the lightest known element.
9. Ionisation energy is the energy required to pull an electron from
the valence shell. But if the valence shell is fully-filled, it is
difficult to remove an electron from a fully-filled orbitals and for
which a large amount of energy in required. As neon being an
inert gas has fully-filled orbitals (valence shell), thus in order to
remove an electron a large amount of energy is needed. Hence,
highest ionisation potential.
1O. Though electron affinity decreases down the group, but, chlorine
has the highest electron affinity among halogens. While, fluorine
has lower value of electron affinity than chlorine. It is due to its
small atomic size and high electron density, the incoming
electron experience greater force of repulsion and results in less
e- affinity. Thus, the correct order of their electron affinity is
F <Cl> Br> I
11. The size of isoelectronic species decreases with increase in
nuclear charge (i.e. number of protons).
Number of protons Ca 2+ < K+ < C ,- < 2-. s
20 19 17 16
12. Number of e- in F- = 9 + I = I 0
Number of e- in 0 2- = 8 + 2 = I 0
Numberofe- in Na+= 11- 1= 10
Number of e- in Mg2+ = 12 - 2 = 10
Since, F-, 0 2-, Na+ ,Mg2 + are isoelectronic and the size of
isoelectronic species decreases with increase in nuclear charge
(i.e. number of protons). Hence, correct order of size is
0 2- > F- > Na+ > Mg2+.
13. The elements of II period shows similar properties as the
elements of ITT period, which are diagonally placed to them. This
is known as diagonal relationship.
TT Period : Li Be B C N
\ \ \\
ITT Period : Na Mg Al Si P
14. On moving from left to right in a period, ionisation energy
increases but ionisation energy ofO is lesser than N. This is due
to the presence of half-filled p-orbitals in N. Thus, correct order
of ionisation energy of C, N, 0, F, is C < 0 < N < F
15. In periodic table, after certain regular intervals, some properties are
repeated. These properties are known as periodic properties. e.g.
atomic volume, ionic and covalent radius, ionisation enthalpy,
electron affinity etc. Atomic mass is not a periodic property.
 Classification of Elements and Periodicity in Properties
16. Since, basicity increases from top to bottom in a group, therefore
order of basicity will be
LiOH < NaOH <KOH< CsOH
17. Since, acidity of oxide increases on moving from left to right in a
period and decreases on moving from top to bottom, the correct order
of acidic strength is
Clp7 > S02 > P40JO.
18. Thermal stability of the hydrides decreases as we go down the group
in periodic table for group 15 (N-family).
BiH 3 < SbH 3 < AsH 3 < PH 3 < NH 3
Least stable Most stable
M - H - 255 247 322 39 1
Bond -energy
kJ mol - 1
19. Oxides
Basic 1 Decreases in a period
Increases in a
group
The basic nature of metal oxides decreases along a period, while it
increases down the group.
The correct order of basic nanire of oxides
Al 2 0 3 < MgO <Nap< Kp.
20. When all the e lectrons of the elements are paired, then the element is
said to be diamagnetic in nature. In p-block elements only noble gases
(group 18 elements) has paired electrons due to fully-filled shells,
thus, these are diamagnetic in nanire, Ne, Ar, Kr, Xe and Rn belongs
to group 18, thus, these are diamagnetic in nature.
21. Carbides of Be and Al gives methane when treated with water.
Be2C + 2H p ~ CH4 + 2Be0
Al 4C 3 + 6H20 - 3CH4 + 2Alp 3
22. In general ionisation energy increases as we move from left to right in
a period. It is due to the increase in effective nuclear charge. IE 1 ofBe
and N is high due to stable configuration. Hence, the correct order is
as follows F > N > C > Be > B.
23. Alkali metals has only one valence electron which is easy to remove,
hence, they have lowest ionisation energy. Among the given
configuration, only ls 2 ,2s2,2µ6,3s 1 contains one valence electron in
their 3s-orbital, thus it belongs to alkali metals group and hence, it has
lowest ionisation energy.
24. F is the most electronegative element which cannot loose electron to
other, so it exhibits only-I state. Na is alkali metal which can loose
only one electron, so exhibits only + 1 state.
2
25. 0 - and N 3- both are isoelectronic but differ in the charge possessed
by them. As the negative charge increase, the electrons are held less
and less tightly by the nucleus, therefore ionic radius increases.
Hence, ionic radius ofN 3- is greater than 0 2-.
In a period from left to right atomic radius decreases thus, atomic
radius of Na > Mg (Li+ > Be2+) as positive charge increases size
2
decreases . In a group on moving downwards it increases thus, Ba • >
Sr 2+ .
26. The ionisation potential decreases down the group (due to increases in
size of atom) and increases in a period from left to right (due to
decrease in atomic size).
As, Li , K and Cs belongs to same group, thus, the correct order of
their IP is Li > K > Cs.
I 53
27. All the given species N 3-, 0 2- ,F- , Na+, Mg2+ contains
same number of electrons. Thus, these are isoelectronic in
nature.
. rad"ms °" - - -1- - -
Tome
atomic number
Ion N 3- 0 2- F - Na+ Mg2+
Atomic number 7 8 9 11 12
Thus, ionic radius would have the following order
NJ-> 0 2 - > F- >Na+> Mg2+.
28. Na belongs to IA group and Mg belongs to TIA group. On
moving form left to right in a period, first ionisation energy
increases, thus IE of Mg is greater than the IE of Na. IE
order Mg > N a .
29. Ionisation energy increases in a period from left to right.
But IE 1 of Be is greater than B due to its stable
2
configuration(ls , 2s\
Hence, the order of decreasing IE 1 is C > Be> B > Li.
30. The property of attracting electrons by an atom in a molecule
is called elctronegativity. However, electron affinity is the
amount of energy liberated when an electron is added to an
isolated gaseous atom.
31. The correct increasing basic strength
SbH 3 < AsH 3 < PH 3 < NH3.
NH3 is the most basic because of its small size, the electron
density of electron pair is concentrated over small region. As
the size increases, the electron density gets diffused over a
large surface area and hence, the ability to donate the
electron pair (basicity) decreases.
32. The ionic radius in general increases on moving top to
bottom and further decreases moving from left to right. So,
the correct order is
Na+ > u+ > Mg2+ > Be2+.
0.95 A 0.68 A 0.65A
1
33. Na(l I): ls2, 2s2, 2µ6, 3s
It is an alkali metal. Alkali metal oxides are basic in nanire.
34. The order of stability metal oxides is as
Fep 3 < Crp 3 < Al 20 3 < MgO.
35. Ionisation energy increases w ith decrease in atomic size and
decrease in shielding effect. The d-electrons in Ga shield the
nuclear charge less effectively than the s and p electrons.
Hence, the outer electron is held fairly strongly by the
nucleus. Consequently, ionisation energy slightly increases
inspite of the increase in atomic size from Al to Ga. Hence,
Al (IE 577) and Ga(IE = 578) have approximately equal
ionisation potential (or ionisation energy).
36. BeO is most acidic in nanire amongst the given choices
because acidity of oxides decreases w ith increases in
electropositive character of central atom.
37. On moving along a period, ionisation enthalpy increases.
Thus, the order of ionisation enthalpy should be as follow
F>O>N.
But N has half-filled strncnire, therefore its electr onic
configuration is more stable than 0, that's w hy its ionisation
enthalpy is higher than 0 . Thus, the correct order of IE is
F>N>O.
54 I Chapterwise & Topicwise Engineering Entrances Solved Papers
38. Given, atomic number of element B = Z
(since, Bis a noble gas, so belong to zero group)
Atomic number of element A= Z - 1 (i.e. halogens)
Atomic number of element C = Z + 1 (i.e. group IA)
Atomic number of elements D = Z + 2 (i.e. group II A)
So, element A must be a halogen, i.e. it has a highest electron
affinity and element C must be an alkali metal and exist in + I
oxidation state and element D must be an alkaline earth metal
w ith +2 oxidation state.
39. According to Hannay and Smith equation
:.Per cent ionic character
= 16 (xA -x8 ) + 3.5 (xA -x8 )2
where,xA andx8 are the electronegativities of the atoms A and B,
respectively.
: . Per cent ionic character= 16(2) + 3.5 (2)2
=32+ 14=46%
40. The electron affinity offluorine is lower than that of chlorine due
to the very small size of fluorine in which negative charge is
highly concentrated and repels the incoming electron, thereby
reducing the force of attraction of nucleus towards the adding
electron and hence, decreasing the electron affinity.
Thus, chlorine has highest value of electron affinity.
41. The first ionisation potential generally increases in a period from
left to right and decreases in a group from up to down. Thus, the
correct order of first ionisation potential is
K<Na<Be.
42. Generally electron affinity increases in a period and decreases in
a group but due to smaller size and high electron density on
fluorine atom, it experience high interelectronic repulsions. Thus,
F- ion is less stable in comparison to c1- ion. Hence, electron
affinity is highest for chlorine. Its electronic configuration is
5
17 CI = ls2, 2s2, 2µ6, 3s2, 3p .
43. The electronic configuration of nitrogen is
1N = ts2, 2s1, 2/
Half-tilled-orbitals
Due to presence of half-filled p-orbital, (more stable) a large
amount of energy is required to remove an electron from
nitrogen. Hence, first ionisation energy of nitrogen is greater than
that of oxygen. The electronic configuration of oxygen is
80 = ts2, 2s2, 2p4
2p
4
[1] 1 11 1
Greater repulsion
The od1er reason for ilie greater IP of nitrogen is that in oxygen,
there is a greater interelectronic repulsion between the electrons
present in the same p-orbital which counter balance the increase
in effective nuclear charge from nitrogen to oxygen.
44. 1. For noble gases (e.g. He), ionisation energy is highest due to
their completely filled electronic configuration.
2. Generally electron affinity increases in a period (from IA to
VII A group) and decreases in a group but electron affinity is
highest for chlorine (Cl) (due to smaller size and high
electron density of fluorine).
3. Electropositive character generally decreases in a period
(from left to right) and increases in a group (on moving down),
thus Ca is the most electropositive element among the given.
4. The ionisation energy is lowest for Li, so it can lose electrons
very easily, thus it behaves as a strongest reducing agent.
Hence, on the basis of above facts, the correct matches are
A ➔ 4 B ➔ l,C ➔ 2, D ➔ 3.
45. The relative extent to which the various orbitals penetrate the
electron clouds of other orbitals is s > p > d > f. Electron will
experience the greatest effective nuclear charge when it is in
s-orbital, than in a p-orbital and so on. Ionisation energy
increases with an increase in penetration power and thus, the
order of screening effect is s > p > d > f.
46. Electron affinity is defined as 'the energy released when an extra
electron is added to neutral gaseous atom'.
In general, electron affinity decreases w ith the increase in the size
of atom, since nuclear attraction decrease down a group. The
value of electron affinity increase as we move along a period
since the size of atoms decrease in a period. Further, electron
affinity for the elements of third period are higher than these of
second period due to their small size and high electron density
and thus, added electron experience large inter electronic
repulsion resulting in release of lower amount of energy and
hence lower electron affinity values.
The increasing order of electron affinity is
2s 2 , 2p4 < 3s2, 3p4 < 2s 2 , 2p5 < 3s2, 3p5.
47. Ionisation energy defined as the energy required to remove an
electron from the outermost orbit of an isolated gaseous atom in
its ground state.
Na(! I)= ts2, 2s2, 2/, 3s 1
Na ~ Na+ + [ (First IE)
Na+ ~ Na2+ + e- (Second TE)
First TE is lower and second IE is very higher, because removal of
an electron from Na+ is very difficult.
48. The ionisation energy of an elements depends upon its size as
1
IEoc - - - - -
size of atom
i.e. smaller the atom, larger will be the ionisation energy. All the
given elements belongs to the same group (alkali metals,
group I). On moving down the group, size of the atom increases
therefore, ionisation energy / potential decreases down the group.
Cs being the second last member of the group has largest atomic
size than Na, K and Rb, thus, possesses lowest ionisation
potential. Hence, among d1e given elements, the elements with
lowest ionisation potential is Cs.
49. The basic character of metal oxides decreases from left to right in
a period due to decrease in electropositive character which in turn
decreases the polarity of bond as well as the inter nuclear distance
between d1e oxygen and metal atom. Therefore, alkali metal
oxides are most basic and halogen oxide (oxygen halides) are
most acidic. So, KP is most basic metal oxide.
s
50. Difference between Sand 2- is larger radii and larger size ofS2-.
As the radii of the anion is always larger than the atomic radii of
its parent atom. In an anion as electron or electrons are added to
the neutral atom, the nuclear charge acts on more electrons, so
that each electron is held less tightly and thereby, the electron
cloud expands.
 Classification of Elements and Periodicity in Properties I 55
51. Electron affinity is defined as, 'the energy released when an extra 59. BeO is basic oxide and reacts only with an acid to form the salt
electron is added to a neutral gaseous atom.' while ZnO, SnO 2 and Al 2O 3 are amphoteric oxides which are
Electron affinity of F = 332.6 kJ/ mol react with acid and base both.
Electron affinity of Cl = 348.5 kJ/ mol 1
Electron affinity of S = 200.7 kJ/ mol 60. Ionic radius oc - -
Zeff
Electron affinity of O = 140.9 kJ/mol
Highest electron affinity among fluorine, chlori ne, sulphur and Zeff = effective nuclear charge
oxygen, is of chlorine. This Zeff is calculated as follows
The low value of electron affinity of fluorine than chlorine is Zeff = Z - screening constant (cr)
probably due to small size offluorine atom, i.e. electron density is The value of screening constant is based upon the number of
high which hinders the addition of an extra electron. electrons in valence shell as well as in penultimate shells.
52. In a given group, atomic size increases due to addition of extra 61. The correct order of electron gain enthalpy
shell w hich outweighs the effect of increased nuclear charge. (electron affinity) is O < S < F < Cl
Number ofshells increases with addition ofextra electrons.
Hence, increase in atomic size down the group is due to increase
Element O S F Cl
in number of electrons. Electron affinity 1.48 2.07 3.45 3.6 1
in eV
53. [Ne] 3s2 3p3
62. Electronegative elements has a large tendency to accept an
[II 1111111 electron to form an anion.
Elements having half-filled or fully-filled orbitals are more (a) The elements with electronic configuration ls 2 ,2s 2 ,2p5 has
stable. Hence, much energy is required to remove an electron 7 valence electrons, thus it has a capacity to accept an
from the ou termost orbit. So, [Ne] 3s2 , 3p3 has highest ionisation electron, therefore, it is electronegative.
energy. (b) The given configuration, Is 2 , 2s2 , 2p4 , 3s I is not correct.
54. The electron affinity (in kJ/mol) (c) The given configuration Is 2 , 2s 2 , 2p6, 3 p 5 is not correct.
Fluorine= 332.6
(d) The elements with electronic configuration Ls 2 , 2s2, 2p6,
Chlorine = 348.5 3s2, 3/ has 7 valence electrons, thus it is also an
Bromine = 324.7 electronegative element.
Iodine= 295.5 But, smaller the size, greater will be electronegativity.
Chlorine has highest electron affinity value, so according to Since, element in choice (a) is smaller in size it will be more
question the correct order of electron affinity will be electronegative than (d). In choice (a) the atomic number of
Cl 2 > F2 > Br2. elements is 9 which is of fluorine and it is the most
electronegative elements of the periodic table.
55. Al 2O 3 behaves as an amphoteric oxide.
Al2O 3 + 6HCI ~ 2A1Cl 3 + 3H2O 63. Halogens have highest electron affinity in the periodic table and it
decreases down the group. Chlorine has highest electron affini ty
Alp3 + 2NaOH ~ 2NaA1O2 + Hp and fluorine has lower electron affinity than chlorine due to its
small size and repulsion between electrons present in it and added
56. ZnO can react w ith acid and base both.
electron. The order of electron affinity is
ZnO + 2HC1 - ZnCl 2 + Hp
F <Cl > Br > I
ZnO + 2NaOH - Na 2ZnO2 + Hp
64. All the ions belong to same period thus for them cations will be
57. F irst ionisation energy increases from left to right across a 2
smaller than anions. Now, 0 - and F- are isoelectronic and
period, but Mg has extra stability than Al, due to fully-fi lled
,~ oc I / Z. Thus, ionic radius of 0 2- (Z = 8) > p- (Z = 9).
3s-orbi tals.
11 Na = 1s2, 2s2, 2p6, 3s
1 65. The size of an anion is larger than its corresponding neutral atom
and the size of cation is smaller than its corresponding neutral
2
12Mg= Is2, 2s2, 2/, 3s atom. Hence, the order of the size of iodine species is as
= Is2, 2s2 , 2/, 3s2, 3p 1 I- > I>T +.
13 AI
2 2 66. Examine the positions in periodic table.
14 Si = ls2, 2s , 2p6, 3s2, 3p
BCNOF
The correct orde r of first ionisation potential is
p s
Na < Mg > Al < Si
Ionisation enthalpies decreases down the group and increases
58. Electronegativity The tendency of an atom in a compound to along a period. However, phosphoms possesses stable half-filled
attract a pair of bonded electrons toward itself is known as configuration, thus it has high ionisation enthalpy than S.
electronegativity of the atom. Fluorine is most electronegative
Hence, order is B < S < P < F.
element because of smaller size and greater tendency to gain
electron.
56 I Chapterwise & Topicwise Engineering Entrances Solved Papers
67. In alkali metals, reactivity increases down the group as
electropositivity increases but for halogens reactivity decreases
down the group as molecular stability of halogens increases.
68. F2 is most reactive due to
(i) highest electronegativity.
(ii) low bond dissociation energy.
( iii) high heat of hydration of F- ion.
69. Mg - Ml;E=750kJ
Remaining energy= 1200 - 750 = 450 kJ
Energy needed to convert I mole of Mg+ to Mg2+ = 1450
2 Hence, the order of ionic radius is
The percentage of number of moles ofMg + produced
I Ionic radii (A) 2.60
= - - X 450= 0.3 1= 31%
1450
: . The percentage number of moles of Mg+ produced
= 1- 0.31= 0.69= 69%
70. The ionisation energy values for the removal of valence
electrons in comparison to remove electrons from inner shell is
very high.
In the given values, there is a biggest jump between IE4 and IE5 .
Hence, there are four valence electrons for the atom X.
71 . Sulphur belongs to VT group of periodic table thus, it has
6 valence electron and hence, it has maximum valency.
72. F luorine is the most electronegative element in the periodic table,
so it never shows positive oxidation state.
73. Lithium is basic in nature and hence, it is not amphoteric.
74. Ionisation potential generally increases in a period from left to
right but IE 1 ofN is greater than that of 0. It is due to the more
stable (half-filled orbitals) configurations ofN.
75. The values for ionisation potential or energy of given elements
E lements C Si Ge Tin (Sn) Lead (Pb)
IE (kJmol- 1) 1086 786 76 1 708 715
As seen from the above values, ionisation energy of tin (Sn) is less
than that of lead (Pb) because due to the presence of 4 / electrons
which screen the nucleus more effectively than 6p electrons
causing the effective nuclear charge to be very high. Hence, Sn has
the lowest value of IE 1, among all the given elements.
76. The elements with atomic number 9, 17, 35, 53 and 85 are
respectively F, Cl, Br, I and At. These are VII A group elements
which are also known as halogens (which means originating from
sea). T hese also have 7 electrons in their valence s hell
(i.e. ns2 n/), e.g.
= ls2 , 2s2, 2p5
9F
17Cl = ls 2 , 2s2, 2µ6, 3s2, 3p5
77. (a) T he physical and chemical properties of e lements are periodic
functions of their electronic configuration. This is the correct
statement.
(b) Electronegativity of fluorine is greater than that of chlorine.
Thus, given statements (b) is incorrect.
(c) Electropositive nature of elements increases from top to
bottom in a group.
Hence, given statements (c) is also incorrect.
78. The ionisation potential increases in a period on moving left to
right while in a group it is decreases on moving from top to
bottom. Hence, Be has maximum ionisation potential.
79. Pauling scale is based upon the excess bond energies. Pauling
equation for determining the electronegativity of an element is
XA - Xa = 0.208--M
where, X A, X 8 = electronegativity values of element A and B,
6. = polarity of A - B bond.
80. C4-, NJ- and 0 2- are isoelectronic species. The ionic radius of
isoelectronic species decreases with increase the nuclear charge.
Species C4- > NJ- > O 2-
1.71 1.40
81. Electron affinity is the energy change, when an electron is added.
When o- changes into 0 2- the electron affmity is positive, i.e.
change is endothermic. The reason is that o- repels the incoming
electron due to similar charge hence, it needs energy to accept the
electron. Hence, electron affinity is positive.
82. Ionisation potential is the energy required by an atom to lose their
valence electron. Noble gases have stable configuration due to
fully-filled orbitals, thus, large amount energy is required to
remove a valence electron and their ionisation potential is high.
83. Fluorine ha.s maximum reduction electrode potential
(E0 _ ) = 2.87 V, hence it is easily reduced into F- and
F/F
consequent Iy F .1s the best ox1'd'1smg
. agent.
2
84. Atomic radii decrease in a period from left to right, hence
fluorine has a very less atomic radii (covalent atomic radii
= 0.72 A). But inert gases (like Ne) are monoatomic gases,
hence their covalent atomic radii cannot be found out. In fact,
their calculated atomic radii is the van der Waals' radii, which is
found almost double to covalent radii, hence the van der Waals'
radius of neon (Ne) is about 1.60 A.
85. Atomic and ionic radii increase from top to bottom in a group
due to the inclusion of another shell at every step. Hence, Cs+
ion w ill be the largest among given IA group ions
(Na+, Li+and K+).
86. A species is amphoteric if it is soluble in acid (behaves as a base)
as well as in base (behaves as an acid.)
SnO 2 + 4HCI - SnC1 4 + 2Hp
Basic Acid
SnO2 + 2NaOH ~ Na 2SnOJ + H 2O
Acid Basic
87. (a) Metallic radius increases in a group from top to bottom.
Thus, Li < Na < K < Rb is true.
(b) Electron gain of enthalpy of Cl> F and decreases along a
group. Thus, I < Br < F < Cl is tme.
(c) Ionisation enthalpy increases along a period left to right but
due to presence of half-filled orbital in N, ionisation
enthalpy ofN > 0.
Thus B < C < N < 0 is incorrect.
(d) For isoelectronic species, ionic size oe - -.- - - -
atonuc number
Thus, ionic size order, AI J+ < Mg2+ < Na+ < p - is correct.
 Classification of Elements and Periodicity in Properties I 57
88. Reason being, as we move in period atomic radii decreases from As d-orbital have diffused shape, hence their electron shields
left to right due to increase of effective nuclear charge. nuclear charge up to lesser extent. Hence, due to increase in
So, Na is larger in size than Mg and a neutral atom is larger than effective nuclear charge (Zerr) atomic size decrease, in the
its positive ion. following order
Ca > Sc > Ti
89. Ionisation energies increase in a period on moving left to right
while it decreases in a group on moving downward. The IE of Be 93. Electron affinity generally increases in a period from left to right
is greater than B due to completely filled s-orbital. because size decreases and nuclear charge increases. But the
Hence, the order ofJE is as Be > B > Li > Na. electron affinity of nitrogen is very low due to extra stability of
90. Element F O N C half-filled 2p -orbital.
Electronegativity 4.0 3.5 3.1 2.5 Hence, the order of electron affinity is
So, correct order of electronegativity B < C < O > N.
F>O>N>C m F>N<O>C 94. Ionisation energy is the amount of energy required to take out
most loosely bonded electron from an isolated gaseous atom.
91. Atomic size increases as we move from top to down in a group,
In a group when we move from top to bottom, ionisation
therefore the amount of energy required for ejection of an
energy decreases due to increase in size. In a period while
electron from atom decreases, i.e. ionisation energy decreases.
moving from left to right ionisation energy increase due to
Hence, the correct order of IE 1 is
increase in size.
Li > Na > K > Cs.
2
So, Be > Mg > Ca (since, it is the order of increasing ionisation
92. 20 Ca= (Ar)4s energy when we move from top to bottom in group II A).
2
2 1Sc= (Ar) 4s , 3d 1

22 Ti = (Ar] 4s 2 , 3d2
Chemical Bonding and
Molecular Structure
QUICK REVIEW
Chemical Bond
• Atoms combine with one another in a number of ways such
as by transference of electrons (ionic bond) or by sharing of
electrons (covalent bond) to form a large number of
molecules. Nature of bond formed between two atoms
depends upon electropositive and electronegative character
of bonded atoms.
• Electropositive element + electronegative element - ionic
bond.
• Electronegative element + electronegative element -
covalent bond.
• Electropositive element+ electropositive element - metallic
bond.
Note Ionic bond is non-directional in nature while covalent and
coordinate bonds are directional in nature.
Properties of Ionic Compounds
Ionic compounds have high melting and boiling points and
these are soluble in polar solvents such as water. For dissolution
of ionic solid in water, hydration energy must be higher than
lattice energy. PbSO 4 , BaSO4 , CaCO3 , PbS, AgBr, AgCl,
Agl, CaF2 etc, are almost insoluble in water as their hydration
energy is less than lattice energy.
Fajan 's Rule
No bond is l 00% ionic in nature. It has some percentage of
covalent character. According to Fajan's rule, the
magnitude of covalent character in the ionic bond depends
upon the extent of polarisation caused by cation.
Smaller the size of cation, large is its polarising, power,
similarly larger the anion, more will be its polarisability.
Properties of Covalent Compounds
• Covalent molecules have lower melting and boiling
points due to relatively weaker forces of attraction. But
giant covalent molecules such as silica, diamond etc. are
very hard and have high melting and boiling points.
Covalent compounds are insulators of electricity but
graphite conducts electricity even in solid state due to
presence of mobile 1t-electrons.
• All single covalent bonds are sigma (cr) bonds while
m ultiple bonds contain one sigma bond only, the other
bonds are pi {1t)bonds.
More is the number of bonds between two atoms, the
shorter is the bond length. Bond length decreases with
the increase in s-character (sp 3 > sp 2 > sp ).
 Chemical Bonding and Molecular Structure I 59
Formal Charge • Prediction of hybridisation; H = _!. (number of valence
• Formal charge = (Total number of valence electrons in the 2
free atom) - [(Total number of lone pair electrons) + 1/ 2 electrons in central atom)+ (number of monovalent atoms
(Total number of bond pair electrons).] surrounding central atom) - (charge on ion with sign)
• The below table shows prediction of different
Polar Covalent Bond (Ionic Character) hybridisation, as:
• Percentage ionic character of a covalent bond (depending Hybridisation
H Spatial arrangement
upon electronegativity difference)
2. sp Linear
=16(xA -x8 )+3 .5(xA -x8 ) 2
3. sl Trigonal planar
where, x A and x 8 are electronegativities of atom A and B, 4. sp3 Tetrahedral
respectively. 2
4. dsp Square planar
• Percentage of ionic character
Experimental value of dipole moment 5. sp3dordsp3 Trigonal bipyramidal
= - ~ - - - - - - - - = - - - - - - x 100 2 2
Theoretical value of dipole moment 6. s/d ord s/ Octahedral
• Resonance: It is a hypothetical phenomenon. When all the 7. sp3d 3 Pentagonal bipyramidal
properties of a molecule cannot be explained by a single
structural formula, then such molecules are represented by • Hybrid orbitals follow Hund 's rnle and Pauli 's principle.
many structural formulas that are canonical structures or • In sp 2 hybridisation the d-orbital involved is d 2 • In
X -y2
contributing or resonating structural representating a single
dps 3 or sp 3 d hybridisation the d-orbital involved are d •
compound. z2
3 2 2 3
• It is observed due to delocalization of JC-electrons. In sp d or d sp hybridisation the d-orbitals involved
are d 2 2 and d 2 .
X -y Z
Dipole Moment
• Dipole moment is a vector quantity. Non-polar diatomic H-Bonding
molecules have a zero dipole moment while polar diatomic • For hydrogen bonding, the molecule must posses a higher
molecules possess dipole moments. electronegative atom such as F, 0 or N, directly linked to
• In case of polyatomic molecules, molecules with regular hydrogen atom.
geometry possess a zero dipole moment while molecules • Intermolecular H-bonding (such as in NH3 , HF, H 2 0etc.)
with irregular geometry possess a definite dipole moment. increases the boiling point of the compound and also its
• NH 3 and NF3 both the molecules have pyramidal shape solubility in water.
with a lone pair of electrons but the resultant dipole • Intramolecular H-bonding (such as in o-chlorophenol,
moment ofNH3 is greater than NF3 . o-nitrophenol, o-hydroxy benzoic acid etc.) decreases the
• Usually cis-isomers have higher dipole moment than the boiling point of the compound and also its solubility in
trans-isomers. water.
• In general, ortho-isomer have highest dipole moment and • Order of strength ofH-bonding; H .... F > H .. .. 0 > H .. .. N
para-isomer (having same substituents) have zero dipole
moment. Intermolecular Forces
The forces between molecules are intem10lecular forces.
VSEPR Theory These forces originate from the different types of interactions
• The VSEPR model is used for predicting the geometrical such as dipole-dipole interactions, ion-dipole interactions,
shapes of molecules. ion-induced dipole interactions and dispersion forces.
• According to this model, molecular geometry is
determined by repulsions between lone pairs and lone
Mettalic Character
pairs, Ione pairs and bond pairs, bond pairs and bond pairs • Metals are good conductors of electricity due to presence
(Ip - lp > lp - bp > bp - bp} of mobile e lectrons. Electrical conductivity of metals
decreases with increases in temperature.
Hybridisation • Bright lustre of metals is due to oscillating electrons.
• Hybridisation is a hypothetical phenomenon. It is • Malleability and ductility of metals is due to the
introduced to explain shapes of molecules and bonding non-directional nature of metallic bond and mobile nature
parameters such as bond angle, strength of bonds. of valence electrons.
60 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Band Model
• In metals, the valence band may be half-filled or there may be overlapping between the valence band and conduction band. Free
electrons present in metals easily move into vacant bands.
• In semiconductors, the energy gap is very small. Electrical conductivity of semiconductors increases as the temperature
increases because some electrons move from valence band to conduction band.

Molecular Orbital Theory

• The molecular orbital theory describes bonding in te1ms of the combination and arrangement of atomic orbitals to form
molecular orbitals.
• The number of molecular orbitals are always equal to the number of atomic orbitals from which they are formed.
• Bonding molecular orbitals are lower in energy than the individual atomic orbitals while antibonding molecular orbitals have
more energy than the individual atomic orbitals.
• Sequence of energy levels of molecular orbitals for Li 2 , Be2 , B 2 and N 2 is

crls<cr°ls<cr2s<cr*2s<(1t2px =1t 2py ~<0"2pz <(;2Px = ;2py )<o2pz

• Sequence of energy levels of molecular orbitals for 0 2 and F2 is

cr ls< ols< cr 2s< o2s< cr 2pz, < (1t2Px = 1t2py )< (;2Px = ; 2py )<o 2pz
• Bond order (B.O.) = -1 (Nb - Na ) , where Nb and Na are number of electrons in bonding and the anti-bonding orbitals,
2
respectively.
• A positive bond order means a stable molecule while a negative or zero bond order means an unstable molecule.
I
• Bond order"" - - - -
Bond length
• Bond order "" Bond dissociation energy and stability.
• Isoelectronic sp ecies having same number of electrons have same bond order.

Topic 1
Ionic, Covalent and Coordinate Bonds Including
Their Property
2014 2012
1. Which one of the following has longest covalent bond 4. Ionic solids are generally [MPPET]
distance? [EAMCET] (a) good conductor of electricity
(a) C-C (b) C-H (c) C-N (d) C-O (b) soft
(c) volatile
2013 (d) brittle
2. Which of the following is a non-directional bond? 5. Which one of the following contains ionic, covalent and
(a) Covalent bond [Manipal] coordinate bonds? [KCET]
(b) Metallic bond (a) NaCl (b) NaCN
(c) Coordinate bond (c) NaNC (d) NaOH
(d) All are directional
6. Which of the followng forms stable coordinate bonds?
3. NH 3 and BF3 form an adduct readily because they form
(a) NH3 , H 2 0 [OJEE]
(a) a coordinate bond [KCET] (b) NH 3 , BF3
(b) a hydrogen bond
(c) NaOH, HCl
(c) an ionic bond
(d) a covalent bond (d) BF3 , BC13
 Chemical Bonding and Molecular Structure I 61
7. An elements has 8 electrons in its last shell which of the 17. Sodium chloride is soluble in water but not in benzene
following is correct? [OJEEJ because [AMUJ
(a) It will lost electrons (a) 11Hhdydration < 11Hlattice energy in water and
(b) It will gain electrons 11H hdydration > t,,.Hlattice energy in benzene
(c) It neither gain nor lose electrons (b) 11Hhdydration > 11Hlattice energy in water and
(d) None of the above /1H hdydration < /1Hlattice energy in benzene
8. The polarising power of the following anions, N 3- , 0 2 - (C) 11Hhdydration = 11Hlattice energy in water and
and F- , follow the order [AMU] /1H hdydration < /1Hlattice energy in benzene
3 2 ( d) 11HHdydration < 11H lattice energy in water and
(a) N - > F- > 0 -
11HHdydration = 11Hlattice energy in benzene
(b) 0 2 - > N 3- > F- -
2
(c) 0 - > F- > N 3- 18. For NH2 , the best three-dimensional view is [DCE]
(d) N 3 - > 0 2- > F-

2011
9. Among the following the maximum covalent character is
shown by the compound [AIEEEJ
H

818
(a) FeCl 2 (b) SnC1 2
(c) A1Cl 3 (d) MgCl 2
10. In the following electron-dot structure, --calculate the
(c)
8 e,,$-H
N'-
~H (d)
H
..
formal charge from left to right nitrogen atom, [WB JEE]
N=N= N 2009
(a)-1,-1,+ 1 (b) -1, + 1, -1 19. Oxidising power of chlorine in aqueous solution can be
(c) + l, - 1,-1 (d) + 1, - 1, + 1 determined by the parameters indicated below.

2010 ,.. EA ffO

11. The valueofnin themolecularforrnulaBenA12 Si 6 0 18 is

,.. hyd ff O
(a)l (b)2 (c)3 (d)4 [IITJEEJ
12. Which one of the following has a coordinate bond? The energy involved in the conversion of..!. Cl 2 (g) to
(a) NH4 Cl (b) AIC13 [RPETJ 2
(c) NaCl (d) Cl 2 Cl- (aq) (Using the data)
t,,.dissH
0
c 12 = 240 kJ n101-1
2009
t,,. EA H° Cl = - 349 kJ mo1- 1
13. Among the following, the compound that contains ionic, 1
covalent and coordinate linkage is [ManipalJ
t,,. hydH 0 = - 381 kJ mol- will be [AIEEEJ
(a) NH 3 (b) NH4 Cl (a)+ 152 kJ mo1-1 (b) - 610 kJ mo1-1
(c) NaCl (d) CaO (c)-850kJmol-t (d)+120kJmol-1
14. When a metal atom combines with a non-metal atom, the
20. If Na+ ion is larger than Mg 2+ ion and s 2- is larger than
non-metal atom will [UPSEEJ
Cl- ion, which of the following will be least soluble in
(a) lose electrons and decrease in size
(b) lose electrons and increase in size water? [Manipal]
( c) gain electrons and decrease in size (a) Sodium chloride (b) Sodium sulphide
(d) gain electrons and increase in size ( c) Magnesium chloride (d) Magnesium sulphide
15. Which of the following when dissolved in water forms a 21. Consider the Born-Haber cycle for the formation of an
solution, i.e. non-conducting? ionic compound given below and identify the compound

J~
[UPSEEJ
(a) Chile saltpetre (b) Potash alum (Z) fom1ed.
(c) Green vitriol (d) Ethyl alcohol
M(s) t.Hi M(g) t.H 2 M+(g)
16. Which combination of atoms can form a polar covalent
bond? [UPSEEJ
[ _21 X 2(g) t.H3 X(g) t.H4 x - (g) z
[KCET]
(a) Hand H (b) Hand Br (a)M+ x- (b)M+ x -(s)
(c) N and N (d) Na and Br
(c)MX (d)M+ x -(g)
62 I Chapterwise & Topicwise Engineering Entrances Solved Papers

22. Which metal has a greater tendency to form metal oxide ? 31. A coordinate bond is a dative covalent bond. Which of the
(a) Cr (b) Fe [KCET] below is true ? [VITEEE]
(c) Al (d) Ca (a) Three atom form bond by sharing their electrons
23. The lattice enthalpy and hydration enthalpy of four (b) Two atoms form bond by sharing their electrons
compounds are given below ( c) Two atoms form bond and one of them provides both
electrons
Lattice enthalpy Hydration enthalpy (d) Two atoms form bond by sharing electrons obtained
Compound (in kJ mol- 1) (in kJ mo1- 1) from third atom.
p 3 2. During the formation of a chemical bond [KCET]
+780 - 920
(a) electron-electron repulsion becomes more than
Q + 1012 - 812 thenucleus-electron repulsion attraction
R + 828 - 878 (b) energy of the system does not change
( c) energy increases
s + 652 - 600
( d) energy decreases
The pair of compounds which is soluble in water is
(a) P and Q (b) Q and R [Kerala CEE]
2006
(c)RansS (d)QandS 33. A compound contains X, Y and Z atoms. The oxidation
(e)P and R states of X , Y and Z are +2, + 2 and - 2 , respectively. The
possible fommla of the compound is [BITSAT]
24. Born-Haber cycle may be used to calculate [UPSEE]
(a) XYZ2 (b) Y2 (-XZ3 h
(a) electronegativity (b) mass number
( c) oxidation number (d) electron affinity (c) X 3 (Y4 Z)z (d) X 3 (Y24 ) 3
25. Which of the following is a favourable factor for cation 34. AB is an ionic solid. The ionic radii of A+ and are s-
formation ? [UPSEE] respectively re and r0 • Lattice energy of AB is proportional
to [EAMCET]
(a) Low ionisation potential(b) High electron affinity
(c) High electonegativity (d) Small atomic size (a) re (b) (re + ra) (c) ra (d) I
26. The nature of the bond in diamond is [J&K CETJ ra re (re +ra)
(a) ionic (b) covalent 35. The number of electrons in the valence shell of sulphur in
( c) metallic (d) coordinate covalent SF6 is [Jamia Millia Islamia]
27. Valueofxinpotashalum, (a) 12 (b) 10 (c) 8 (d) 11
K2S04 · Alx (S04 ) 3 • 24H20is [BCECE] 36. Lattice energy of a solid increases, if
(a)4 {b)I (a) size of ions is small [Jamia Millia Islamia]
(c) 2 (d) None of these (b) charges of ions are small
28. Which of the following has lowest boiling point? [DCE] (c) ions are neutral
(a) NaCl (b) CuCl (d) None of the above
(c) CuCl 2 (d) CsCI
2005
29. Which of the following represents the Lewis structure of
37. Lattice energy of an ionic compound depends upon
N 2 molecule? [Jamia Millia Islamia]
(a) charge on the ion and size of the ion [AIEEE]
X X XX X XX X
(a) xN= N (b) N- N (b) packing of ions only
X X X
(c) size of the ion only
XX XX XX XX
(c)x N x_N x (d) X N= N X
(d) charge on the ion only
X X XX X X XX XX X
38. Which of the following silver salts is insoluble in water?
(a) AgCl04 (b) Ag 2S04 [BITSATl
2007
(c) AgF (d) AgN0 3
30. The charge/size ratio of a cation determines its polarising
39. Which of the following has covalent bond? [Manipall
power. Which one of the following sequences represents
the increasing order of the polarising power of the cationic (a)Na 2S (b)AJCI 3
· K + , C a 2+ , Mg 2+ , Be2+ ? (c) NaH (d) MgC12
species, [AIEEEJ
40. C - Cl bond is stronger than C - I bond, because
(a) Mg 2+ < Be 2+ < K+ < Ca 2+
(a) C- Cl bond is more ionic than C - I [MHT CETJ
(b)Be 2+ < K + < Ca 2+ < Mg 2+
(b) C - Cl bond is polar covalent bond
(c) K + < Ca 2+ < Mg 2+ < Be2+ ( c) C- Cl bond is more covalent than C - I
(d) Ca 2+ < Mg 2+ < Be 2+ < K + ( d) C - Cl bond length is longer than C- I
 Chemical Bonding and Molecular Structure I 63
41. An atom of an element A has three electrons in its 42. Allene (C 3 H 4 )contains [UPSEE]
outermost orbit and that of B has six electrons in its (a) one double bond, one triple bond and one single bond
outermost orbit. The formula of the compound between
(b) one triple and two double bonds
these two will be [KCET]
(c) two triple and one double bond
(a) A 3 B 6 (b) A 2 B 3 (c) A 3 B 2 (d) A 2 B ( d) two double and four single bond

Topi c 2
Resonating Structures and Polarity of Bonds
2012
1. A diatomic molecule has a dipole moment of 1.2 D. If its The correct curve is [DCE]
bond distance of 1.0 A, what fraction of an electronic (a)A (b)B (c)C (d) D
charge, e, exist on each atom? [BITSAT]
(a) 25% of e (b) 50% of e
2008
(c) 60% of e (d) 75% of e 7. The bond length ofHCI molecule is 1.275 A and its dipole
moment is 1.03 D. The ionic character of the molecule (in
2010 per cent) (charge of the electron= 4.8 x 10-10 esu) is
2. The molecule which has zero moment is [JCECEJ (a) 100 (b) 67.3 [BITSAT]
(a) CH3 CI (b) NF3 (c) BF3 (d) Cl02 (c) 33.66 (d) 16.83

2009 8. The bond angle and dipole moment of water respectively,

are [OJEEJ
3. The correct stability order of the following resonance
(a) 109.5°, 1.84 D (b) 107.5°, 1.56 D
structure is
+ - + - (c) 104.5°, 1.84 D ( d) 102.5°, 1.56 D
H 2 C=N=N H 2 C-N=N 9. Which one of the following is a non-polar molecule?
I II
- + - + (a) CCl 4 (b) CHC1 3 [J&K CET]
H2 C-N=N H 2 C-N=N
IJJ IV [IITJEE] (c) CH 2 Cl 2 (d) CH 3 C l
(a) I > II > IV > III (b) I > III > II > IV 10. C-C bond order in benzene is [BCECEJ
( c) II > I > III > IV (d) III >I > IV > II (a) l (b)2
4. Which substance has the greatest ionic character? (c) between 1 and 2 (d) None of these
(a) C l 2 0 (b) NCl 3 [UPSEE] 2007
(c) PbC12 (d) BaCl 2 11. The dipole moment of HBr is 1.6 x 1 o-3o cm and
5. IfH-X bond length is 2.00 A and H-X bond has dipole interatomic spacing is l A. The percentage ionic character
moment 5 .12 x 1o-3o cm, the percentage of ionic character of HBr is [UPSEEJ
in the molecule will be [lndraprastha CET, CG PET] (a) 7 (b) 10 (c) 15 (d) 27
(a) 10% (b) 16% (c) 18% (d) 20% 12. Dipole moment is shown by [Manipal]
6. For AB bond, if per cent ionic character is plotted against (a) cis- 1, 2-dichloro ethene
electronegativity difference (XA - X 8 ), the shape of the (b) trans-1, 2-dichloro ethene
curve would look like ( c) trans- I 2-dichloro-2 pentene
10 (d) B oth (a) and (c)

2006
13. Consider the following halogen containing compounds
(A) CHCI3 (B) CC1 4
(C) CH 2 CI 2 (D) CH3 CI

(E) c1-@-c1
64 I Chapterwise & Topicwise Engineering Entrances Solved Papers

The compounds with a net zero dipole moment are + •• +

: N = N-Q: N= O= N [DCE]
(a) Band E (b) Only C [Kerala CEE]
(c) C and D only (d) A and D (TIT) (IV)
(e) Only B (a) I and II (b) I and m
14. The molecule having largest dipole moment among the (c) I, II and III (d) All of these
following is [WB JEE]
2005
(a) CHI 3 (b) CH4
16. If the molecule of HCl were totally polar, the expected
(c) CHCl 3 (d) CC1 4
value of dipole moment is 6.12 D (debye), but the
15. Which of the following are possible resonating structure of experimental value of dipole moment was 1.03 D.
N 2 O? Calculate the percentage ionic character [Kerala CEEJ
•• +
: ~ -N = O: (a) 17 (b) 83 (c) 50
(I) (II)
(d) zero (e) 90

Topic 3
Valence Shell Electron Pair Repulsion (VSEPR)
Theory, Valence Bond Theory (VBT), Hybridisation
2014
l. The number of valence shell bonding electrons to be 8. In which of the following pairs the two species are not
distributed in the Lewis electron dot model for HNNN is isostructural? [AIEEEJ
W6 ~10 Gffl~~ (a) CO~- and NO3 (b) PCl: and SiCl 4
(c) 11 (d) 16 ( c) PF3 and BrF5 ( d) AlFJ- and SF6
2013 9. Which of the following order of bond angles is correct?
2. The total number of lone pairs of electrons in melamine is (a) BF3 <NF3 < PF3 <ClF3 [ManipalJ
(a) 4 (b) 7 [JEE Advanced] (b) BF3 < NF3 < PF3 > ClF3
(c)6 (d)9 (c) CIF3 < PF3 <NF3 < BF3
( d) BF3 "' NF3 < PF3 < ClF3
3. The numer of n-bonds in
[KCET]
10. The percentage of p -character of the hybrid orbitals in
CH 2 = CH-CH= CH-C= CH is
(a)2 (b)5 (c)4 (d) 3 graphite and diamond are respecitvely, [KCETJ
(a) 50 and 75 (b) 67 and 75
4. A lone pair of electrons in an atom in1plies [KCET]
(c) 33 and 75 (d) 33 and 25
(a) a pair of valence electrons not involved in bonding
11. The state of hybridisation of the central atom and the
(b) a pair of electrons involved in bonding
( c) a pair of electrons number of lone pairs over the central atom in POCI 3 are
2
( d) a pair of valence electrons (a) sp, 0 (b) sp , 0 [WB JEE]
3
(c) sp , 0 (d) dsp 2 , 1
5. What type of hydridisation takes place in the N atom of
N H3 ? [OJEEJ
2 3 2
2011
(a) sp (b) sp (c) dsp (d) sp
12. The hybridisation of orbitals ofN atom in NO3- ,No; and
2013 NH; arerespectively [A.IEEE]

6. The shape of XeO2 F2 molecule is 2 3 2 3

[IITJEE] (a) sp, sp , sp (b) sp ,sp,sp
(a) trigonal bipyramidal (c)sp,sp 3 ,sp 2 (d)sp 2 ,sp3,sp
(b) square planar 13. The structure ofIF7 is [AIEEE]
( c) tetrahedral
(d) see-saw (a) square pyramid
(b) trigonal bipyramid
7. The molecule having smallest bond angle is [A.IEEE] ( c) octahedral
(a) NC1 3 (b) AsC13 (c) SbCl 3 (d) PC1 3 ( d) pentagonal bipyramid
 Chemical Bonding and Molecular Structure I 65
14. Which ofthe following has maximum number oflone pairs 25. Which one of the following conversions involve change in
associated with Xe ? CAIEEEJ both hybridisation and shape? CKCETJ
(a) XeO 3 (b) XeF4 (c) XeF6 (d) XeF2 (a) CH4 ~ C2H 6 (b) NH 3 ~ NH;
15. The number of types of bonds between two carbon atoms (c) BF3 ~ BF4 (d)H 2 O ~ H3 O+
in calcium carbide is [AIEEEJ 2
26. Which of the following has sp hybridisation? CRPETJ
( a) one sigma(cr) two pi(1t)
(b) one sigma(cr)one pi(1t) (a) C2 H 6 (b) C 2 H 4
(c) two sigma{cr)one pi(n) (c) BeC12 (d) C 2 H2
(d) two sigma(cr)two pi(1t) 27. The AsF5 molecule is trigonal bipyramidal. The hybrid
16. The sp 3 d 2 hybridisation of central atom of a molecule orbitals used by the As atoms for bonding are [JCECEJ
would lead to [WB JEE] (a) dx2 -y2 , d 2 2 ,s, Px, Py (b) d_'<Y ,s, Px, Pz
(a) square planar geometry (c)S,Px,P y ,Pz,dz2 (d)d_.2 _Y2,S,p_.,py
(b) tetrahedral geometry 28. The enolic fom1 of acetone contains [Punjab CETJ
(c) trigonal bipyramidal geometry
(a) 9 sigma bonds, 1 pi bond and 2 lone pairs
( d) octahedral geometry (b) 8 sigma bonds, 2 pi bond and 2 lone pairs
17. Hybridisation ofC 2 and C 3 of (c) 10 sigma bonds, l pi bond and l Ione pair
l 2 3 4 5 ( d) 9 sigma bonds, 2 pi bond and l lone pair
H 3 C-CH=C=CH-CH3 are [WBJEE]
29. A a-bonded molecule MX 3 is T-shaped. The number
(a)sp,sp 3 (b)sp 2 ,sp (c)sp 2 ,sp 2 (d) sp,sp
non-bonding pairs of electron is [Punjab CETJ
18. Number of non-bonding electron pair on Xe in (a) 0
XeF6 , XeF4 and XeF2 respectively will be [Guj CETJ (b) 2
(a)6,4,2 (b)l,2,3 (c)3,2, 1 (d)0,3,2 (c) 1
19. The number of sigma (cr) and pi (1t) covalent bonds ( d) can be predicted only if atomic number ofMis known
respectively in benzene nitrile are [Guj CETJ 30. The hybrid state of S in SO3 is similar to that of
(a) 5, 13 (b) 15, 3 (c) 13, 5 (d) 16, 2 (a) C in C 2 H 2 (b) C in C 2 H 4 [Punjab CETJ
20. Hybridisation shown by carbon and oxygen of -OH (c) C in CH4 (d) C in CO 2
group in phenol are respectively [Guj CETJ
2009
(b) sp 3 ,sp 3
2 2
(a) sp ,sp
31. A covalent molecule AB3 has pyramidal structure. The
(c) sp, sp
2
(d) sp
2
, sp 3 number of lone pair and bond pair of electrons in the
molecule are respectively. [Manipal]
2010
002~2 ~0~4 ~3~1 w1~3
21. Based on VSEPR theory, the number of 90 degree
32. In which of the following species, all the three types of
F- Br- F angles in BrF5 is [IIT JEE]
hybrid carbons are present ? [Kerala CEEJ
ooo ~1 ~2 W3 (a) CH 2 =C=CH2
22. The species having pyramidal shape is [IITJEE] (b) CH 3 -CH =CH-CH;
(a) SO3 (b) BrF3 (c) Sio~- (d) OSF2 (c) CH 3 - C=C-CH;
23. In which reaction, the hybridisation on the central atom (d) CH 3 -CH=CH-CH 2
2 3
changes from sp to sp ? [MP PET] (e) CH 2 =CH-CH=CH 2
(a) NH 3 + H+ ~ NH; 33. The shape ofXeF4 molecule and hybridisation of xenon in it
(b) BF3 + F- ~ BF4 are [Kerala CEE]
(a) tetrahedral and sp 3
2
(c) H 2 O + H+ ~ H 3 O+ (b) square planar and dsp
(d) C2 H 2 + 2H2 ~ C 2 H 6 (c) square planar and sp 3d (d) octahedral and sp 3d 2
2

24. How manycr and 1t-bonds are present in given compound? ( e) octahedral and d 2 sp 3
[MPPET]
34. Which one of the following linear structure?
Ph-CH= C-C2Hs T. f:i' IT. NO2 ITT. ½
I IV. S02 V. N3
CH3
(a) I, II and III (b)IandV [OJEE]
(a) 19cr and 4n-bonds (b) 22cr and 41t-bonds
(c) II, III and IV ( d) All of these
( c) 25 cr and 41t-bonds (d) 26cr and 41t-bonds
66 I Chapterwise & Topicwise Engineering Entrances Solved Papers

35. In XeF6 , oxidation state and state of hybridisation of Xe 2008

and shape of the molecule are, respectively [AMU] 45. Which one of the following is a correct set?
(a) + 6, sp 3 d 3 , distorted octahedral 3
(a) H 2 O, sp , angular [BITSAT, AMU, EAMCET]
(b) +4, sp 3 d2, square p lanar (b) BC13 ,sp 3 , angular
( c) + 6, sp 3 , pyramidal (c) NH!, dsp 2 , square planar
3 2
(d) + 6, sp d , square pyramidal ( d) CH 4 , dsp 2 , tetrahedral
36. Which of the following species is non-linear? [AMU] 46. The number of sigma and pi bonds in peroxodisu1phuric
(a) IC12 (b) 13 (c) N 3 (d) ClO2 acid are respectively [BITSAT, EAMCET]

37. The state of hybridisation ofS in SF4 is (a) 9 and 4 (b) 11 and 4 (c) 4 and 8 (d) 4 and 9
[AMU]
47. The compound in which the number of drc-prc bonds are
(a) sp 3 and has a lone pair of electron
(b) sp 2 and has tetrahedral structure equal to those present in ClO4 [BITSAT, AMU, EAMCET]
3 (a) XeF4 (b) XeO 3 (c) XeO4 (d) XeF6
(c) sp d and has a trigonal bipyramidal structure
(d) sp 3 d 2 and has an octahedral structure 48. The i{O\bond angle in H 2 0 is 104. 5°. This fact can
38. The bond angle and percentage of d-character in SF6 are be best explained with the help of [MP PET]
(a) 120°, 20% (b) 90°, 33% CAMUJ (a) valence shell electron pair I repulsion (VSEPR) theory
(b) molecular orbital theory
(c) 109°, 25% (d) 90°, 25%
(c) presence of hydrogen bond
39. In which of the following pair both molecules do not (d) electronegativity difference between hydrogen and
possess same type ofhybtidisation? oxygen atoms
[lndraprastha CET, CG PET} 49. Which of the following groups all do not have sp 3 d
(a) CH4 and H 2 O (b) PC! 5 and SF4 hybridisation? [MP PET]
(c) SF6 and XeF4 (d) BCl 3 and NCl 3
(a) ClF3 , IF3 , XeF; (b)IC1 2, ClF2 , 13
40. I. H-C- H angle in CH4
(c) CIF3 , BrF3 , IF3 (d) PCl 3 , AsC13 , PF5
II. CI- B-CI angle in BCl 3
III. F- I-F angle in IF7 in a plane 50. The actual geometry ofNO2 is [MP PET]

IV. I- I- I angle in 13 (a) planar (b) linear

(c) V -shape (d) tetrahedral
Increasing order of above bond angles is
51. Match the following columns.
[lndraprastha CET, CG PET}
(a) I < II < III < IV (b) II < I < III < IV Column I Column II
(c) III < I < II < IV (d) IV < II < I < III (Molecule/ion) (Type of hybridisation)
41. SF2 , SF4 and SF6 have the hybridisations at sulphur atom A. NH+ I. s/d3
4
respectively, as [DCE]
B. PCl 5 2. sp3d
(a) sp 2 , sp 3 , sp 2 d 2 (b) sp 3 , sp 3 , sp 3 d 2
C. SF6 3. sp3
(c)sp 3 ,sp 3 d,sp 3 d 2
2
(d)sp 3 ,spd ,d 2 sp 3
D. IF1 4. s/d2
42. In pyrophosphoric acid, H 4 P2 O 7 , number of cr and
dre - pre bonds are respectively [DCE] Codes [MPPET]
( a) 8 and 2 (b) 6 and 2 A B C D A B C D
(c) 12 and O (d) 12 and 2 (a) 3 2 4 1 (b) 1 2 3 4
(c) 2 3 1 4 (d) 4 1 2 3
43. Two type FXF angles are present in which of the following
molecules? (X = S, Xe, C) [DCEJ 52. The C- 0- H bond angle in ethanol is nearly [UPSEE]
(a) SF4 (b) XeF4 (a) 90° (b) 104° (c) 120° (d) 180°
(c) SF6 (d) CF4 53. The bond angle is smallest in [UPSEE]
44. In which pair of species, both species do have the sin1ilar (a)H 2 O (b)H 2 S
geometry? [DCE] (c) BeC12 (d) N 2 O
(a) CO2 , SO 2 (b) NH1 , BH3 54. How many re-bonds are present in naphthalene? [UPSEE]
(c) co~- , so~- (d) so!- , c10; (a) 4 (b) 5 (c) 6 (d)7
 Chemical Bonding and Molecular Structure I 67
55. Valence bond theory of metallic bond was given by 63. Cl - P- Cl bond angles in PCI 5 molecule are [BCECE]
(a) Dalton (b) Drude! [UPSEEJ (a) 120° and 90° (b) 60° and 90°
(c) Fajan (d) Pauling (c) 60° and 120° (d) 1200 and 30°
56. C - Cbond length is maximum in [UPSEE] 64. The bond angle in AsH 3 is greater than that in [DCEJ
(a) diamond (b) graphite (a) NH3 (b) H 2 O (c) BCl 3 (d) None of these
( c) naphthalene (d) fullerene
57. Bond angles ofNH 3 , PH 3 , AsH 3 and SbH3 is in the order
2007
65. The percentage of p-character in the orbitals forming P- P
(a) PH 3 > AsH 3 > SbH 3 > NH 3 [OJEEJ
(b) SbH3 > AsH 3 > PH 3 > NH3 bonds in P4 is [IIT JEE]
(c) SbH3 > AsH3 > NH3 > PH 3 (a) 25 (b) 33 (c) 50 (d) 75
(d) NH3 > PH 3 > AsH3 > SbH 3 66. In TeC1 4 , the central atom tellurium involves [VITEEE]
58. Shape and hybridisation ofIF5 respectively are [OJEE] (a) sp 3 hybridisation (b) sp 3 d hybridisation
2 2
(a) trigonal bipyramidal, sp 3 d (c) sp 3 d hybridisation (d) dsp hybridisation
(b) sea-saw, sp 3 d 67. In a regular octahedral molecule, MX 6 the number of
( c) square pyramidal, sp 3 d 2 X - M - X bonds at 180° is [Manipal]
(d) pentagonal pyramidal, sp 3 d 3 (a) three (b) two (c) six (c) four
59. Match the compounds in the colwnn I with that in column IL 68. H 2 0 is dipolar, whereas BeF2 is not. It is because
[Manipal]
Column I Column II
(a) the electronegativity ofF is greater than that ofO
A. Xe03 1. Planar triangular
(b) H 2 O involves hydrogen bonding whereas BeF2 is a
B. XeOF4 2. T-shape discrete molecule
c. BO;- 3. Trigonal pyramid ( c) H 2 0 is linear and BeF2 is angular
( d) H 2 0 is angular and BeF2 is linear
D. CTF3 4. Square pyramid
69. In BrF3 molecule, the lone pairs occupy equatorial
E. r; (aq) 5. Linear
positions to minimise [ManipaIJ
6. Bent
(a) lone pair-bond pair repulsion only
Codes [Guj CETJ (b) bond pair-bond pair repulsion only
B (c) lone pair-lone pair repulsion and lone pair-bond pair
A C D E
(a) 1 4 3 2 5 repulsion
(d) lone pair-lone pair repulsion only
(b) 2 4 1 3 4
(c) 3 4 1 2 4 70. Among the following, the pair in which the two species are
(d) 4 4 1 2 5 not isostructural, is [UPSEE, Manipall
60. According of VSEPR theory the repulsion between (a) SiF4 and SF4 (b) 103 and XeO 3
different pair (lone or bond) of electrons obey the order (c) BH 4 and NH! (d) PF; and SF6
Codes [J&K CETJ
71. Structure of ammonia is [MHT CET]
(a) lp - bp> Ip - Ip> bp - bp
(a) pyramidal (b) tetrahedral
(b) Ip - bp > bp - bp > Ip - Ip
( c) trigonal ( d) trigonal pyramidal
( c) Ip - Ip> Ip - bp > bp - bp
(d) bp - bp > Ip - Ip> Ip - bp 72. Geometry ofSiOt anion is [MHTCET]
61. Which one of the following is a correct set with respect to (a) tetrahedral (b) trigonal
molecule, hybridisation and shape ? [BCECEJ ( c) trihedral ( d) pentagonal

(a) BeC12 ,sp

2
, linear 73. The pair of species having identical shapes for molecules
2 of both species is [MP PETJ
(b) BeC1 2 ,sp , triangular planar
2 (a) CF4 , SF4 (b) XeF2 , CO 2
( c) BC! 3 , sp , triangular p lanar
(c) BF3 , PCl 3 (d) PF5 , IF5
(d) BC1 3 ,sp 3 , tetrahedral
74. In acetylene molecule between the carbon atoms there are
62. The compound in which underlined carbon uses only its (a) three pi bonds [KCETJ
sp 3 hybrid orbitals for bond formation is [BCECE] (b) one sigma and two pi bonds
(b) CH3 !:_;ONH2 ( c) two sigma and one pi bonds
(a)CH 3 ~OOH
( d) three sigma bonds
(c) CH 3 ~H 2 OH (d) CH2 CH= CH 2
68 I Chapterwise & Topicwise Engineering Entrances Solved Papers

75. Match the following columns. 83. Structure ofXeF; ion is [AMUJ

Column I Column II (a) trigonal bipyramidal (b) square pyramidal

A. PC1 5 1. Linear ( c) octahedral ( d) pentagonal
B. IF1 2. Pyramidal 84. Hybridisation of oxygen in diethyl ether is [EAMCETJ
2
c. H 3O+ 3. Trigonal bipyramidal (a)sp (b)sp (c)sp
3
(d)sp 3 d
D. ClO2 4. Tetrahedral 85. Which of the following is not tetrahedral ? [EAMCETJ
E. 5. Pentagonal bipyramidal
NH! (a) BF4 (b) NH! (c) cot (d) s01-
6. Angular
86. The hybridisation of the ipso-carbon dichlorobenzene is
Codes [Kerala CEEJ (a) sp hybridised [J&K CETJ
2
A B C D E (b) sp hybridised
(a) 3 5 2 1 4 (c) sp 2 d hybridised
(b) 3 5 4 1 2
(d) sp 3 hybridised
(c) 3 5 6 1 2
(d) 3 5 2 6 4 87. The bond length between C - C bond in sp 2 hybridised
(e) 3 5 2 4 1 molecule is [BCECEJ
76. Which one of the following compounds has sp 2 (a) 1.2 A (b) 1.39 A
hybridisation? [WBJEEJ (c) 1.33 A (d) 1.54 A
(a) CO2 (b) SO2 88. The planar structure of BF3 can be explained by the fact
(c) N 2 O (d) CO that BF3 is [BCECE]
77. Numberoflonepair(s)inXeOF4 is/are [WBJEEJ (a) sp hybridised
2
(a)0 (b)l (c)2 (d) 3 (b) sp hybridised
3
78. BC13 is a planar molecule, while NC1 3 is pyramidal, (c) sp hybridised
because [WB JEE] ( d) sp 3d hybridised
(a) N - Cl bond is more covalent than B - Cl bond 89. The hybridisation state of central atom in PCl 5 is [DCEJ
(b) nitrogen atom is smaller than boron atom
(c) B - Cl bond is more polar than N- Cl bond (a)sp 3 d (b)sp 3 d 2 (c)sp 3 (d)d 2 sp 3
(d) BC1 3 has no lone pair of electrons but NC1 3 has a 90. The maximum number of 90° angles between bond
lone pair of electrons pair-bond pair of electrons is observed in
79. Which one of the following compounds has the smallest (a) ds1/ hybridisation [Jamia Millia Islamia]
bond angle in its molecule ? [UPSEEJ (b) sp 3 d hybridisation
(a) SO2 (b) H 2 O (c) SH 2 (d) NH 3 2
(c) dsp hybridisation
(d) sp 3 d hybridisation
80. The molecular shapes ofSF4 , CF4 and XeF4 are [UPSEEJ 2

(a) different with 1, 0 and 2 lone pairs of electrons on the

central atom, respectively 2006
(b) different with 0, l and 2 lone pairs of electrons on the 91. In which of the following molecules/ions all the bonds are
central atom, respectively not equal ? [AIEEEJ
( c) the same with 1, 1 and 1 lone pair of electrons on the
(a) SF4 (b) SiF4 (c) XeF4 (d) BF4
central atoms, respectively
(d) the same with 2, 0 and 1 lone pairs of electrons on the 92. Amongst the following, the molecule that is linear is
central atom, respectively (a) SO 2 (b) CO 2 [ManipaJJ
81. The shape ofClF3 is [OJEEJ (c) ClO 2 (d) NO 2
(a) distorted T-shape (b) pyramidal 93. The compound 1, 2-butadiene has [Manipal]
( c) tetrahedral (d) trigonal planar (a) sp, sp 2 and sp 3 hybridised carbon atoms
2
82. N 2 O is isoelectronic to CO 2 and N;- . Which of the (b) only sp hybridised carbon atoms
following is the structure ofN 2 O? [OJEEJ (c) only sp hybridised carbon atoms
2
(a) -r{Nb (b) N-0--N (d) both sp and sp hybridised carbon atoms
94. The C- H bond distance is the longest in [Manipal]
(a) C2 H 6 (b) C2 H 2
(c) N-N-0(d)
(c) C2 H2 Br2 (d) C2 H4
 Chemical Bonding and Molecular Structure I 69
95. In methane the bond angle is [Manip al] 104. The correct sequence of hybridisation of methane, ethene
(a) 180° {b) 90° and acetylene is [WB JEE]
2 3 2 3
(c) 109° (d) 120° (a) sp,sp ,sp (b) sp , sp ,sp
2 2
96. The hybrid state ofsulphur in SO3 molecule is [Manipall (c)sp 3 ,sp ' sp (d) sp 3 ,sp,sp
3 3 3 2 2
(a) sp d (b) sp (c) sp d (d) sp 105. AU bond angles are exactly equal to 109° 28' in [UPSEE]
97. Which of the following is isostructural with CO 2? (a) methyl chloride (b) iodoform
(a) N2O (b) NO2 [MHT CET] ( c) chloroform ( d) carbon tetrachloride
(c)N 2O 5 (d)NO 106. The number of cr and n-bonds in a molecule of acetonitrile
are respectively [UPSEE]
98. How many electron pairs are present in valence shell of
oxygen in water molecule ? [MP PET] (a)2,5 (b)3,4
( a) 4 (b) l {c) 2 ( d) 3
(c)4,3 (d)5,2
107. A molecule (X)has
99. In which of the following compound sp 2 hybridisation is
I. fom sigma bonds formed by the overlap ofsp2 ands-orbitals
absent ? [MP PET]
TI. one sigma bond formed by sp2 and sp2 orbitals and
(a) CH2 = CH - CH= CH 2
(b) CH = C - CH 2- CH3 ITT. one 7t bond formed by Px and p, orbitals. Which of the
(c) CH2 - CH=CH2 following is X? [EAMCET]
(d) CH 2 = CH- CH2 - CH 3 (a) C2 H 6 (b) C 2 H 3Cl (c) C 2 H 2 Cl 2 (d) C 2H 4
100. In ] -butene number ofcr-bonds is [MPPET] 108. The number of sigma and pi (1t) bonds present in benzene
(a) 8 (b) 10 (c) 11 (d) 12 respectively are [EAMCETJ
101. Consider th e following compounds (a) 12, 6 (b) 6, 6 (c) 6, 12 (d) 12, 3
I. chloroethene II. benzene 109. Which of the following molecule in its valence shell has
III. 1, 3-butadiene IV. I, 3, 5-hexatriene three bond pairs ofelectrons and one lone pair ofelctrons ?
AU the carbon atoms are sp 2 hybridised in [Kerala CEEJ
(a) NH3 (b) H2O [J &K CETJ
(a) I, III and IV (b) I and II
(c) BF3 (d) CO 2
(c) I, Il and IV (d) III and IV
(e) I, II, III and IV 110. Which of the following set ofproperties belong to PCl 5 ?
102. Consider the following molecules or ions [J &K CET]
I. H20 II. NH! III. so~- (a) sp 3
, tetrahedral, 4 valence shell pairs of electrons
3
IV. ClO4 V. NH3 (b) sp d, trigonal bipyramidal, 5 valence shell pairs of
3
sp hybridisation is involved in the formation of electrons
( c) sp 3 d 2 , octahedral, 6 valence she! II pairs ofelectrons
(a) I, II and V (b) I and II [Kerala CEE]
(c) Only II (d) I, II, III and IV ( d) sp 3 d , square planar, 4 valence shell pairs ofelectrons
(e) I, II, III, IV and V 111. The shape of sulphate ion is [BCECE]
103. Match Column I and Column II and pick out correct (a) square planar (b) trigonal
matching codes from the given choices. (c) trigonal p lanar (d) tetrahedral
Column I Column JI 112. CO2 is isostructural with [DCE]
(Compound) (Strncnrre)
(a) C2 H 2 (b) SnCl 2
A. CIF3 I. Square planar (c) NO 2 (d) MgCl 2
B. PC1 5 2. Tetrahedral
c. IF5 3. Trigonal bipyramidal
2005
D. CC14 4. Square pyramidal 113. Which species has the maximum number of lone pair of
E. XeF4 5. T-shaped
electrons on the central atom ? [ITT JEE]
(a)[CI0 3] (b) XeF4 (c) SF4 (d) [I3]
Codes [Ke ral a CEE]
114. InP4 O 10 the [BITSATJ
A B C D E
(a) 5 4 3 2 1 (a) second bond in P = 0 is formed by p1t-d1t back
(b) 5 3 4 2 1 bonding
(c) 5 3 4 1 2 (b) P = 0 bond is formed by pn-pn bonding
(d) 4 3 5 2 1 ( c) P = 0 bond is fo1med d1t-d1t bonding
(e) 3 4 1 5 2 ( d) P = 0 bond is formed by d1t-d1t- 30' back bonrung
70 I Chapterwise & Topicwise Engineering Entrances Solved Papers
115. Which of the following molecules bas pyramidal shape? 124. The pair having similar geometry is [J&K CETJ
[Manipal] (a) PCl 3 ,NH+4 (b)BeCl 2 ,H2 O
(a) PCI;. (b) SO3 (c) CH4 , CCl 4 (d) IF5 , PF5
(c) CO3- (d) NO3
125. The d-orbital involved in sp 3 d-hybridisation is
116. Amongst the following, the molecule that is linear is (a)dx2- y2 (b)d.xy [J&KCET]
[MPPET]
(c)d
z
2 (d)dzx
(a) SO2 (b) BeH2 (c) ClO 2 (d) NO 2
126. Which of the following is planar? [J&K CETJ
117. How manycr and n-bonds are present in toluene?
(a) XeF2 (b) XeO 3 F
(a) 3n + 8cr (b) 31t + l0cr [Kerela CEEJ (c) XeO2 F2 (d) XeF4
(c) 3n + 15cr (d) 61t + 3cr 127. How many bonds are there in? [DCEJ
(e) 61t + 6cr
118. Which one of the following molecules has the smallest
bond angle?
(a) NH 3 (b) PH3
[Kerala CEE]
(c) H 2 O
egr-
(d) H 2 Se (e) H 2 S (a)l4cr,81t (b)l8cr,81t (c)l9cr,41t (d) l 4cr,21t
3
119. sp d hybridisation results in [UPSEEJ 128. Pair of species having identical shapes for molecules is
(a) CF4 , SF4 (b) BF3 , PC1 3 [DCEJ
(a) a square planar molecule
(b) an octahedron molecule (c)XeF2 , CO2 (d)PF5 , IF7
(c) a trigonal bipyramidal molecule 129. Bond angle ofl 09°28' is found in [JamiaMillialslamia]
(d) a tetrahedron molecule a, a,
(a) NH 3 (b) H 2 O (c) CH5 (d) NH 4
120. Hybridisation of central atom in NF3 is [OJEE]
2 2 130. Hybridisation of the underline atom changes in
(a) sp 3 (b) sp (c) sp (d) dsp
(a) ~H 3 changes to AlH4 [Jamia Millia Islamia]
121. Which of the following is a linear molecule? [EAMCET] (b) H 2 Q changes to H 3 O+
(a) BeCl2 (b) H 2 O (c) SO 2 (d) CH4
(c) ~ 3 changes to NH;
122. Which of the following is correct? [EAMCET]
(d) in all cases
(a) The number of electrons present in the valence shell
131. The number of lone pairs of Xe in XeF2 , XeF4 and XeF6
ofS in SF6 is 12
(b) The rates of ionic reactions are very slow respectively are [Jamia Millia Islamia]
(c) According to VSEPR theory, SnCl 2 is a linear (a)3,2, l (b)2,4, 6 (c) l ,2,3 (d)6,4,2
molecule 132. A square planar complex is formed by hybridisation of the
(d) The correct order of ability to form ionic compounds following atomic orbitals [Jamia Millia Islamial
among Na+ , Mg 2+ and Al 3+ is Al 3 + > Mg 2 + > Na+
(a)s,px,P y ,Pz (b)s,px,P y, Pz,d
123. The percentage s-character of the hybrid orbitals in (c)d,S,Px , P y (d)s,Px, Py, p,,d,d
methane, ethene and ethyne are respectively [Guj CET] 133. Number ofP- 0bonds in P4 0 10 is [Jamia Millia lslamia]
(a) 25, 33, 50 (b) 25, 50, 75 (a) 17 (b) 16 (c) 15 (d) 6
(c) 50, 75, 100 (d) 10, 20, 40

Topic 4
Hydrogen Bonding, Intermolecular Forces and Metallic Bond
2014
1. Hydrogen bonding plays a central role in the following 2. Which of the following hydrogen bonds are strongest in
phenomena [JEE Advanced] vapour phase? [VITEEEJ
(a) ice floats in water (a) HF ...... HF (b) HF ..... .HCI
(b) higher Lewis basicity of primary amines than tertiary (c) HCI. ..... HCI (d) HF ...... Hl
amines in aqueous solutions 3. How many hydrogen bonded water molecule (s) are
(c) formic acid is more acidic than acetic acid associated in CuSO4 · 5H2 O [AMUJ
(d) dimerisation of acetic acid in benzene W5 ~ 1 ~4 W3
 Chemical Bonding and Molecular Structure I 71
4. The molecular interactions responsible for hydrogen l O. The low density of ice compared to water is due to
bonding in HF [EAMCET] (a) induced dipole-induced dipole interactions [JCECEJ
(a) ion-induced dipole (b) dipole-dipole (b) dipole-induced dipole interactions
(c) dipole-induced dipole (d) ion-dipole ( c) hydrogen bonding interactions
( d) dipole-dipole interactions
5. Cl 2 0 is a yellowish-red gas at room temperature.
The strongest intennolecular forces present of Cl 2 0 are 2009
(a) dipole-dipole forces [IPUCETJ
11. Hydration of different ions in aqueous solution is an
(b) London forces
example of [Ke rala CEE]
( c) hydrogen bonds
( d) covalent bonds (a) ion-induced dipole interaction
(b) dipole-dipole interaction
2013 (c) dipole-induced dipole interaction
6. Hydrogen bonding is maximum in [KCET] (d) attractive dispersion forces between atoms
(e) ion-dipole interaction
(a) ethyl chloride (b) triethyl amine
(c) ethanol (d) diethyl ether 12. Which of the following compounds would have the highest
boiling point ? [UPSEEJ
2011 (a) CH 3 CH2 CH 2 CH 3 (b) CH 3 NH 2
7. lntramolecular hydrogen bond is present in [Ke rala CEE] (c) CH 3 0H (d) CH 2 F2
(a) water (b) o-nitrophenol 13. Which of the following has strongest hydrogen bonding?
(c) p-nitrophenol (d) methylamine (a) Ethylamine (b) Ammonia [Manipal]
(e) ethanol
(c) Ethyl alcohol (d) D iethyl ether
8. Which of the following compound has maximwn
14. The maximum number of hydrogen bonds that a molecule
volatility? [WB JEE]
of water can have is [KCETJ

(a) (b) 6
~COOH
2008
(a) 1
(c) 3
(b) 2
(d) 4

l 5. Malleability and ductility of metals can be accounted due to

(a) the presence ofelectrostatic force [KCETJ
COOH
(b) the crystalline stmcture in metal
( c) the capacity of layers of metal ions to slide over the
XOH / COOH other
(c) [QJ (d) the interaction of electrons w ith metal ions in the
lattice
16. Unusually high boiling point of water is result of
2010 (a) intermolecular hydrogen bonding [WB JEE]
9. Out of the compounds below the vapour pressure of(B)at (b) intramolecular hydrogen bonding
( c) both intra and inter molecular hydrogen bonding
a particular temperature is [KCET]
(d) high specific heat

J;
17. Glycerol is more viscous than ethanol due to [UPSEEJ

©YN0 2 (a) high molecular weight

~
(A)
(a) higher than that of (A)
(b) lower than that of (A)
( c) higher or lower than ( A ) , depending on the size of
the vessel
( d) same as that of (A)
(b) high boiling point
(c) many hydrogen bonds per molecule
(d) Fajan's rule
18. Oxygen and sulphur both are the member of same group in
(B) Periodic Table but H 2 0 is liquid while H 2 Sis gas because
(a) molecular weight of water is more [UPSEEJ
(b) electronegativity of sulphur is more
(c) H2 S is weak acid
(d) water molecules are having strong hydrogen bonds
between them
72 I Chapterwise & Topicwise Engineering Entrances Solved Papers

19. Hydrogen bond is strongest in The increasing order of boiling points of above mentioned
[Jamia Millia Islamia, Punjab CET] alcohols is [ IIT JEE]
(a) S-H ···O (b) 0-H···S (a) I < II < ill< IV (b)I< II < IV<ill
(c)F-H ···F (d)O-H···N (c) IV < I < II < Ill (d) IV < II < I < ill
25. Among the following mixtures, dipole-dipole as the major
2007 interaction, is present in [AIEEEJ
20. Which is the most volatile compound? [BITSATJ
(a) benzene and ethanol
(a) HI (b) HCI (c) HBr (d)HF (b) acetonitrile and acetone
21. The comparatively high boiling point of HF is due to ( c) KCI and water
(a) high reactivity of fluorine [MHT CETJ ( d) benzene and carbon tetrachloride
(b) small size of hydrogen atom 26. Metals are good conductors of electricity becasue they
( c) formation of hydrogen bonds and consequent contain CUPSEEJ
association
( d) high IE of fluroine (a) ionic bonds
(b) a network structure
22. NH3 has much higher boiling point than PH3 because ( c) very few valence electrons
(a) NH 3 has larger molecular weight [WB JEE] ( d) free electrons
(b) NH 3 undergoes umbrella inversion 2 7. Which molecule has hydrogen bonding? [Guj CETJ
(c) NH 3 forms hydrogen bond
(a) CH4 (b) CH 3 COOH
(d) NH 3 contains ionic bonds whereas PH 3 contains
covalent bonds (c) GeH4 (d) H2 Te

23. Which compound is soluble in water? [AMU] 2005

(a) CS 2 (b) C 2 H 5 OH 28. H-bond is not present in [BCECEJ
(c) CC1 4 (d) CHC1 3
(a) water (b) glycerol
2006 ( c) hydrogen fluoride (d) hydrogen sulphide

24. I. 1, 2-dihydroxy benzene 29. Metallic lusture is explained by [DCE]

II. 1, 3-dihydroxy benzene (a) diffusion of metal ions

(b) osci Ilati on of loose electrons
III. I , 4-dihydroxy benzene (c) excitation of free protons
IV. Hydroxy benzene (d) existence of bee lattice

Topic 5
Molecular Orbital Theory
2014
1. Assuming 2s-2p mixing is not operative, the paramagnetic
species among the following is [JEE Advanced]
C. 3. p-drc bonding
(a)Be 2 (b)B2
(c) C 2 (d) N 2
2. Match the following columns, with the correct answer
using the code given below the columns. [JEE Advanced] D. 4. d-d o- bonding

A. I. p-d 1t anti bonding

Column I Column JI
A. I. p-d n-antibonding

B.

6~ 2. d-d cr bonding
B.
C.
D.
2.
3.
4.
d-d o- bonding
p-d 1t bonding
d-d cr antibonding
 Chemical Bonding and Molecular Structure I 73
Codes [JEE Advanced] 14. The paramagnetic behaviour ofB2 is due to the presence of
A B C D A B C D (a) two unpaired electrons in 1t b MO [WB JEE]
(a) 2 1 3 4 (b) 4 3 1 2 (b) two unpaired electrons in 1t * MO
(c) 2 3 1 4 (d) 4 1 3 2 ( c) two unpaired electrons in cr * MO
3. Order ofspecies CF+ , CF and CF- according to increasing (d) two unpaired electrons in cr b MO
C- F bond length [Manip al] 15. As per molecular orbital theory, which can't exist in stable
state? [OJEEJ
(a) CF+< CF< CF- (b) CF+< CF- < CF
(c) CF- < CF< CF+ (d) CF< CF- < CF+
4. An atomic orbital has two angular nodes and one radial
node. It is a [Manipal] 2012
(a) 2p orbital (b) 3p orbital 16. Which of the following is diamagnetic? [Manipal]
( c) 3d orbital (d) 4d orbital
(a) H 2 (b) H 2 (c) H! (d) He!
5. The number of angular and radial nodes of 4s orbital
respectively are [KCET] 2011
(a) 3, 1 (b) 1, 2 (c) 0,3 (d) 2, 1
17. When 0 2 is converted into o; [KCET]
6. In case ofheteronuclear diatom of the type AB, where A is
(a) both paramagnetic character and bond order increase
more electronegative than B, bonding molecular orbital
(b) bond order decreases
resembles the character of A more than that of B . The ( c) paramagnetic character increases
statement [WB JEE] ( d) paramagnetic character decreases and the bond order
(a) is false increases
(b) is true 18. Which of the following is not correct with respect to bond
(c) cannot be evaluated since data is not sufficient
length of the species ? [Ke rala CEEJ
(d) is true only for certain systems
(a) C 2 >C~- (b) B! > B 2 (c) Li;> Li 2
7. Which of the following stability order is correct [AMU]
(d) Nl > N 2 (e) 0 2 > 0 2
(a)O~- > 0 2 > 0 2 > O! (b)O! > 0 2 > 0 2 > Ot
( c) o; > 02 < o;- > o t cd) 02 > o ; > o~- > o ;- 19. Which one of the following is paramagnetic? [WB JEE]
(a) N 2 (b) NO
s. K0 2 exhibits paramagnetic behaviour. This is due to the (c) CO (d) 0 3
paramagnetic nature of [EAMCET]
(a) KO- (b) K+ (c) 0 2 (d) 0 2010
2
20. Assuming that Hund's rule is violated, the bond order and
2013 magnetic nature of the diatomic molecule B 2 is [IIT JEE]
9. In which of the following pairs of molecules/ions both the (a) 1 and diamagnetic
species are not likely to exist? [JEE Mains] (b) 0 and diamagnetic
( c) 1 and paramagnetic
(a) H! , He~- (b) H 2, He~- (c) H!, He 2 (d) H 2, He~+
( d) 0 and paramagnetic
10. Which one of the following molecules is spected to exhibit 21. The bond order in NO is 2.5 while that in NO+ is 3. Which
diamagnetic behaviour? [JEE Mains] of the following statements is tme for these two species ?
(a) C2 (b) N 2 (c) 0 2 (d) S 2 (a) Bond length in NO+ is greater than in NO [Manipall
11. Stability of the species Li 2 , Li 2 and Li! increases in the (b) B ond length in NO is greater than in NO+
order of [JEE Mains] (c) Bond length in NO+ is equal to in NO
( d) Bond length is unpredictable
(a) Li 2 < Li! < Li 2 (b) Li 2 < Li! < Li 2
22. In a homonuclear molecule which of the following set of
(c)Li 2 < Li 2 < Li! (d) Li 2 < Li 2 < Li!
orbitals is degenerate? [Manipal]
12. The bond order in the superoxide ion (0 2) is [Mainp al]
(a)cr2sandcrls (b);2Px andn2py
(a)2.5 (b) 2 (c) 1.5 (d) 1 (c)n2p_. andcr2pz (d)cr2pz andn:2px
13. Oxygen molecules contains [KCET]
23. Which species has the highest bond order ? [MP PET]
(a) no unpaired electron (b) one unpaired electron
( c) two unpaired electrons (d) three unpaired electrons
(a) 0 2 (b) o~-
(e) four unpaired electrons (c) N 2 (d) Both 0 2 and ot
74 I Chapterwise & Topicwise Engineering Entrances Solved Papers
24. Peroxide ion 2008
I. has five completely filled antibonding molecular orbitals 32. Which one of the following constitutes a group of the
II. is diamagnetic isoelectronic species? [AIEEE]
III. has bond order one
(a) C~-, 0 2, CO, NO (b) NO+, C~-, CW, N 2
IV. is isoelectronic with neon
(c) CW, N 2 , O~-, co1- (d) N 2 , 0 2, NO+ , CO
Which one of these is correct? [KCET]
(a) II and III (b) I, II and II
(c) I, II and III (d) I and IV
33. The number of nodal planes present in cr s -antibonding
orbitals is CKCET]
25. Given are 0 2 , o;, o~+ and o~-, respectively. Find the
(a) 1 (b) 2 (c) 0 (d) 3
correct increasing bond order [Guj CET]
34. Rb0 2 is Co.JEE]
(a)0 2 < O~- < O~+ < o; (b)0~- <0 2 < o ; < O~+
(a) peroxide and paramagnetic
(c)O~- < 0 2 < o ; < O~- (d)O; < O~- < 0 2 < O~+ (b) peroxide and diamagnetic
26. The relationship between the dissociation energy of N 2 (c) superoxide and paramagnetic
(d) superoxide and diamagnetic
and N; is [Punjab CET]
35. From the molecular orbital theory, one can show that the
(a) dissociation energy of N 2 = dissociation energy of bond order in F2 molecule as [J&K CET]
N; (a)2 (b) l
(b) dissociation energy of N 2 can either be lower or (c) 3 (d) 4
higher than the dissociation energy of N;
36. The correct order of bond order value among the following
(c) dissociation energy of N 2 > dissociation energy of
is
N; I. NO- II. NO+ III. NO
(d) dissociation energy of N; > dissociation energy of IV. No2+ V. No2- [Guj CET]
N2 (a) I < IV < III < II < V (b) IV= II < I < V < III
(c) V < I < IV = III < II (d) II < III < IV < I < V
2009
27. Using Molecular Orbital Theory predict which of the 2007
following species has the shortest bond length? [AIEEE] 37. The species having bond order different from that in CO
(a) o~+ (b) o ; (c) 0 2 (d) o~- is [IIT JEE]

28. Among the followin g species, identify the pair having (a) NO- (b) NO+ (c) CN- (d) N 2
same bond order CN- , 0 2, NO+ and CN+[Ke rala CEE] 38. Among the following, the paramagnetic compound is
(a) CN- and 0 2 (b) 0 2 and NO+ (a)Na 2 0 2 (b)0 3 [IITJEE]
(c) CN- and NO+ (d) CN- and CN+ (c) N 2 0 (d) K02
(e) NO+ and CN+ 39. In which of the following ionisation processes, the bond
29. The calculated bond order in 0 2 ion is [UPSEE] order has increased and the magnetic behaviour has
changed? [AIEEE]
(a) 1 (b) 1.5
(c) 2 (d) 2.5 (a) C2 ~ c ; (b) NO~ NO+
30. In forming (i) N 2 ➔ N; and (ii) 0 2 ➔ o; the electrons (c) 0 2 ~ o; (d) N 2 ~ N;
respectively are removed from [DCE] 40. Which of the following species exhibits the diamagnetic
(n: (n
(a) 2py or 1t 2Px) and 2pY or 1t 2px) behaviour? [AIEEE]
(b) (1t 2py or 7t 2Px )and (?:t 2py or~ 2px ) (a) o~- (b) o; (c) 0 2 (d) NO
(c)(7;2py or~2px )and(n2py or1t 2Px)
41. The isoelectronic pair is [BITSAT]
(d) (n2p y orn2px )and (1t 2py or1t 2px )
(a) Cl 2 0, IC1 2 (b) Cl 2, Cl0 2
31. Which is the correct statement about cr and 1t molecular
(c) IF; , I3 (d) Cl02, ClF;
orbitals ? Statements are [DCE]
I. 1t-bonding orbitals are ungerade 42. For a stable molecule, the value of bond order must be
II. 1t-antibonding orbitals are ungerade (a) there is no relationship between stability and bond
III. cr-antibonding orbitals are gerade order [KCET]
(a) Only I (b) Only II and III (b) zero
(c) Only III (d) Only II (c) positive
(d) negative
 Chemical Bonding and Molecular Structure I 75
43. The number of antibonding electron pairs in o~- 51. Molecular orbital theory was given by [WB JEE]
molecular ion on the basis of molecular orbital theory is (a) Kossel (b) Mosley (c) Mulliken (d) Werner
(Atomic number ofO is 8.) [KCET] 52. Which of the following is isoelectronic with CO2 ?
005 ~4 ~3 002 (a) NO 2 (b) NO [UPSEE]
44. Which of the following is paramagnetic with bond order (c) N 2 0 (d) N 2 0 4
0.5? [Ke rala CEE] 53. The bond order ofN1 is [UPSEE]
(a) F2 (b) H; (c) N 2 (a) 1.5 (b) 3.0 (c) 2.5 (d) 2.0
(d) 0 2 (e) B2 54. o~• has a bond order of [Guj CET]
45. N 2 accept electron and convert into N;, where this electron (a)l (b)2 (c) 3 (d) 4
goes? [DCE] 55. According to bond order concept the correct order of
(a) Antibonding 1t-molecular orbital stability of 0 2 , o ; and 0 2 is [J&K CET]
(b) Bonding 7t-molecular orbital
(a) 0 2 > o ; > 0 2 (b) 0 2 > 0 2 > o ;
(c) cr-bonding molecular oribital
(d) cr-antibonding molecular orbital ( c) 0 2 > o; > o ; ( d) o ; > 0 2 > 0 2
46. The formation of energy bonds in solids are in accordance 56. Which of the following is having highest bond length?
with [DCE] (a) NO- (b) NO+ [DCE]
(a) Heisenberg's uncertainty principle (c) CN- (d) CN+
(b) Bohr's theory
(c) Ohm's law 2005
(d) R utherford's atomic model
57. Which one of the following species is diamagnetic in
2006 nature? [AIEEE]

47. Which of the following molecules/ions does not contain (a) H 2 (b) H; (c) H 2 (d) He;
unpaired electrons ? [AIEEE] 58. Of the following sets which one does not contain
(a) o~- (b) B 2 (c) N; (d) 0 2 isoelectronic species? [AIEEE]

48. Which of the following species has a bond order other than (a) Bo~-, co~-, NO3 (b) sO 32- ' co32- , No-3
3? [BITSAT] (C) cN- , N 2, c~- ( d) Po~- ' so~- ' CIO;j
(a)CO (b)C~ 59. The molecular electronic configuration ofBe 2 is
(c) NO+ (d) o; 2
(a) crls cr ls2cr2s2 cr 2p 2 [BITSAT]
49. The sequence that correctly describes the relative bond
(b) KKcr2s 2
strength pertaining to oxygen molecule and its cation or 2 2
(c) crls cr ls cr2s cr 2s
2 2
anion is [Ke rala CEE]
(d) None of the above
(a) o~- ,> 0 2 > 0 2 > o ; (b) 0 2 > o ; > 0 2 > o~-
60. The electronic configuration
( c) o; > 0 2 > o~- > 0 2 cd) o; > 0 2 > 0 2 > o ~-
(crls) 2 (cr 1s)2 (cr2s) 2 (cr 2s)2 (cr2Px ) 2
( e) 02 > 0:2 > o~- > o ;
50. The bond order of o; is the same as in (1t2py )2(1t2p, )2(n2py )2(n2p, ) 1 can be assigned
[WB JEE]
[AMU]
(a) N; (b) c~
(c) CO (d) NO+
(b) o; (d) o~-
 Answers
TOPICl Ionic, Covalent and Coordinate Bonds Including their Property
1. (a) 2. (b) 3. (a) 4. (a) 5. (c) 6. (b) 7. (c) 8. (d) 9. (c) 10. (b)
11. (c) 12. (a) 13. (b) 14. (d) 15. (d) 16. (b) 17. (b) 18. (a) 19. (b) 20. (d)
21. (b) 22. (d) 23. (e) 24. (d) 25. (a) 26. (b) 27. (c) 28. (c) 29. (a) 30. (c)
31. (c) 32. (d) 33. (a) 34. (d) 35. (a) 36. (a) 37. (a) 38. (b) 39. (b) 40. (a)
41. (b) 42. (d)
TOPIC2 Resonating Structures and Polarity of Bonds
1. (a) 2. (c) 3. (b) 4. (d) 5. (b) 6. (c) 7. (d) 8. (c) 9. (a) 10. (c)
11. (b) 12. (d) 13. (a) 14. (c) 15. (b) 16. (a)
TOPIC3 Valence Shell Electron Pair Repulsion (VSEPR) Theory, Valence Bond Theory (VBD Hybridisation
1. (b) 2. (c) 3. (c) 4. (a) 5. (b) 6. (d) 7. (c) 8. (c) 9. (c) 10. (b)
11. (c) 12. (b) 13. (d) 14. (d) 15. (a) 16. (d) 17. (b) 18. (b) 19. (c) 20. (d)
21. (a) 22. (d) 23. (b) 24. (c) 25. (c) 26. (b) 27. (c) 28. (a) 29. (b) 30. (b)
31. (d) 32. (c) 33. (c) 34. (b) 35. (a) 36. (d) 37. (c) 38. (b) 39. (d) 40. (c)
41. (c) 42. (d) 43. (a) 44. (d) 45. (a) 46. (b) 47. (b) 48. (a) 49. (d) 50. (c)
51. (a) 52. (b) 53. (b) 54. (b) 55. (d) 56. (a) 57. (d) 58. (c) 59. (c) 60. (c)
61. (c) 62. (c) 63. (a) 64. (d) 65. (d) 66. (b) 67. (a) 68. (d) 69. (c) 70. (a)
71. (a) 72. (a) 73. (b) 74. (b) 75. (d) 76. (b) 77. (b) 78. (d) 79. (c) 80. (a)
81. (a) 82. (c) 83. (b) 84. (c) 85. (c) 86. (b) 87. (b) 88. (b} 89. (a) 90. (d)
91. (a) 92. (b) 93. (a) 94. (a) 95. (c) 96. (d) 97. (a) 98. (a) 99. (b) 100. (c)
101. (e) 102. (e) 103. (b) 104. (c) 105. (d) 106. (d) 107. (d) 108. (d) 109. (a) 110. (b)
111. (d) 112. (a) 113. (d) 114. (c) 115. (a) 116. (b} 117. (c) 118. (d) 119. (c) 120. (a)
121. (a) 122. (a) 123. (a) 124. (c) 125. (c) 126. (a) 127. (c) 128. (c) 129. (d) 130. (a)
131. (a) 132. (c) 133. (b)
TOPIC4 Hydrogen Bonding, Intermolecular Forces and Metallic Bond
1. (a,b,d) 2. (a) 3. (b) 4. (b) 5. (a) 6. (c) 7. (b) 8. (c) 9. (a) 10. (c)
11 . (c) 12. (c) 13. (c) 14. (d) 15. (c) 16. (a) 17. (c) 18. (d) 19. (c) 20. (b)
21 . (c) 22. (c) 23. (b) 24. (c) 25. (b) 26. (d) 27. (b) 28. (d) 29. (b)
me!C..5. Molecular Orbital Theory
1. (b) 2. (c) 3. (a) 4. (d) 5. (c) 6. (b) 7. (b) 8. (d) 9. (c) 10. (a,b}
11. (b) 12. (c) 13. (c) 14. (a) 15. (d) 16. (b) 17. (d) 18. (e) 19. (b) 20. (a)
21. (b) 22. (b) 23. (c) 24. (a) 25. (b) 26. (c) 27. (a) 28. (c) 29. (b) 30. (c)
31. (a) 32. (b) 33. (a) 34. (c) 35. (b) 36. (c) 37. (a) 38. (d) 39. (b) 40. (a)
41. (d) 42. (c) 43. (b) 44. (b) 45. (a) 46. (b) 47. (a) 48. (d) 49. (d) 50. (a)
51. (c) 52. (c) 53. (c) 54. (c) 55. (d) 56. (a) 57. (c) 58. (b) 59. (c) 60. (c)
 Explanations
Topic 1 Ionic, Covalent and Coordinate Bonds Including Their Property
1. The average distance between the centre of nuclei of the two 7. Acording to electronic theory of valency, element having 8
bonded atoms in a molecule is known as bond length.It depends electrons in last shell, has stable configuration. Therefore, it wi ll
upon the size of atoms, hybridisation, steric effect, resonance etc. neither gain nor lose electrons.
Usually bond length of polar bond is smaller as compared to a 8. Since, polarising power increases with the size of anion, thus the
non-polar bond. Therefore, C- C bond length is longest among order wi ll be
given options. N3- > 0 2- > p-
2. Coordinate and covalent-bonds are both directional in nature
9. In all the given compounds, anion is same (Cl-), hence polarising
because these bonds arises due to electrostatic attraction between
power is decided by size and charge of cation.
the nuclear core and shared electron pairs.These electrons are
localised and the orbitals involved in bonding oriented at a fired Al 3+ w ith maximum charge and smallest size has maximum
angle and direction polarising power, hence AIC1 3 is maximum covalent.
Whereas, metallic bonds are non-directional in nature because . I
10. Formal charge = Number of electrons m valence shell - (- x
these bonds involves the force of attraction between the fixed 2
atomic kernels (positive cores of metals) and the mobile electron numbers of electrons as bond pair + numbers of electrons as lone
cloud within a metal lattice and it has no definite direction. pair)
3. Coordinate bond is a special type of covalent bond in which
shared electron pair is donated by one atom (e- rich species called
donor) and shared by both the atoms (the other atom being called ForN 1 andN3
acceptor electron deficient species). For e.g. NH3 (e-rich species)
forms and adduct readily w ith BF3 (e-deficient species), through
Formal charge= 5 - ( 1 + 4) = 5 - (6) = - I

coordinate bonding. For N2 = s-(¾ o) X 8+ = 5 - 4 =+I

.. . ..
H : F:
.. .. ..
H : F:
11. For Be11 Al 2Si60 18

H
.
H: N : + B •• F : -H•• N •• ➔ B
H :N:
: F:
2n + 6 + 24 - 36 = 0
n.=3
or
12. NH4CI is formed by NH! and Cl ion. The ammonium ion i.e.
H F
I I NH! involves coordinate bond between NH3 and H+ ion.
H-N - B- F
I I
H F
4. Ionic solid sare crystalline, hard and brittle in nature. Because of
the presence of free ions, these are good conductor of electricity
but only in aqueous solution or molten state.
5. NaNC contains ionic, covalent and coordinate bonds which can While AlCl 3 and NaCl involves ionic and Cl 2 involves covalent
be represented as: bonding.
Coordinate bond
13. NH4Cl contains ionic, covalent and coordinate linkage.
Na ionic bondt-T: ~ :c:
• Covalent bond
r H ]+
Na+[N~Cf
6. NH3 and BF3 have stable coordinate bond due to the presence of
lone pair of electrons on N and electron deficiency on B atom.
lH-r-H c,-

14. Metals and non-metals combine to complete their octet.

H F H F
Since, non-metals have lack of electrons, in order to complete
I I I I their octet, they gain electrons, consequently, the size of
H-N : + B- F - H-N - B- F
non-metal atom will increase.
I I 1 I
H F H F Metal + Non-metal - Electrovalent bond
(Na+) (Ci-) NaCl
78 I Chapterwise & Topicwise Engineering Entrances Solved Papers
15. Chile saltpetre (NaN03 ), potash a lum 23. The solubility of a compound mainly depend upon its hydration
energy.
(K2S0 4 -Al 2 (S04 h · 24H 2 0) and green vitriol (FeS04 · 7Hi0) are
ionic compounds. They produce ions in their aqueous solutions, If the hydration energy of a compound is greater than from its
so they are conducting in nature. Ethyl alcohol, C 2H 50H being lattice enthalpy, then its is soluble in water. Thus, for solubility
covalent in nature, does not produce any ion in aqueous solution. hydration enthalpy > lattice enthalpy
Hence, it is non-conducting in nature. For compounds P and Re hydration enthalpy exceeds the lattice
16. When there is less difference in electronegativities of two atoms enthalpy, so they are soluble in water.
and large difference in their size, polar covalent bond forms. 24. According to Born-Haber cycle the enthalpy of formation (tillf)
H and Br : small difference in electronegativities and large of an ionic compound may be given as
difference in size. Hence, form polar covalent bond. I
tillf=S+
Na and Br : large difference in electronegativities , hence polar 2D + l+E+U
electrovalent bond is formed. where, I = Ionisation energy
17. For a compound to be soluble, the hydration energy must be S = Sublimation energy
greater than the lattice energy. Since, NaCl is soluble in water but E = Electron affinity
insoluble in benzene due to, D = Dissociation energy
tillhydration > fiH1attice energy inwater U = Lattice energy of compound
and tillhydration < tilllattice energy in benz.ene
-
Born-Haber's cycle is used to determine the lattice energy of
18. Structure ofNH 2 is as follows the compound. It also may be used to calculate electron affinity
of an element.
25. Low ionisation potential indicates that element can easily lose
electron to form cation.
26. Diamond has a three-dimensional structure in w hich a large
number of carbon atoms are arranged tetrahedrally by covalent
19. _!_ Cl 2 (g)~ Ci-(aq) bonds. It is an allotropic form of carbon.
2
27. Potash alum is a double salt.
till =..!..wdiss (Cl2)+ WEA Cl+ whyd(Ci-) Potash alum, K 2S04 · Al_,(S0 4 h · 24Hp (given)
2
240 Ions Al S04
= - 349- 381
Valency + 3 -2
2
= - 610 kJ mol- 1 Therefore, Al 2 (S04 ) 3 is a compotmd of Al 3+ and so~--
20. Higher the lattice energy lower the solubility. Out of the four On comparing, x = 2
combinations possible, the latt.ice energy of MgS (bi-bivalent Hence, formula of potash alum is
ionic solid) is higher than those ofNa 2S, MgCl 2 (uni-bivalent or = K 2S0 4 · Al 2 (S0 4 ) 3 · 24H20
bi-univalent ionic solids) and NaCl (uni-univalent ionic solids).
Hence, MgS is the least soluble. 28. According to Fajan's rule, as the size of cation decreases, its
2
polarising power increases. Hence, Cu + polarise Cl- ions more
21. The Born-Haber cycle takes place as follows
than Cu+. Therefore , CuCl 2 has more covalent character and
I lit H hence, its boiling point is less.
M(s) 2 X2(g) - -~ M+x-(s)
29. Lewis structure ofN 2 molecule is
!ilfsub l j ½ !ilfdw

M(g) X(g)

+ rnj-e- I e- (EA) -U
(Lattice entha lpy)
x -(g) 30. Higher the charge/size ratio, more is the polarising power.
K + < Ca 2+ < Mg2+ < Be2+

31. A coordinate bond is a dative covalent bond in which two atoms

Hence, Z is M+ x-(s)
22. Greater the stability ofoxide, greater is the ease of its formation.
Generally ionic oxides are more stable than covalent oxides and
among the given metals only Ca form ionic oxide. Hence, Ca has
greater tendency to form oxide.
form bond and one of them provides both electrons.
X:+Y -➔ X :YorX ~ Y
32. During the formation of chemical bond energy decreases.
33. Valencies of X, Yand Z is +2, + 2 and - 2 respectively so, they
will form a compound hav ing of formula XYZ2•
 Chemical Bonding and Molecular Structure I 79
34. The lattice becomes stronger (i.e. the lattice energy U becomes Topic 2 Resonating Structures and
more negative), as r the interionic distance decreases. U is
. 11
proport1ona to -
Polarity of Bonds
")- dipole moment _ 1.2D
r 1. Cl1arge (u - -
1 d 1.0 x 10-8 cm
or U<>< - - -
(,;, + ,;,) 18
(o) = 1.2 x 10- esu · cm
35. S has 6 electrons in its valence shell and it shares 6 electrons with 1.0 x 10-8 cm
6 fluorine atoms.
= 1.2 x 10- 10 esu
: . In SF6, S has 12 electrons in its valence shell
F F In a polar molecule, the total ionic charge is 4.8 x I0- 10 esu.
X
. .X Thus, the fraction of electronic charge, e is
Fx • S • xF 1.2 X Io-10 esu = 0.25 e = 25% of e
4.8 x 10- 10 esu/e
X X
F F 2. The molecules having distorted geometry have dipole moment
36. According to Bom-lande equation and those having regular geometry have zero dipole moment.
U = NAMz+z- i? (1-1 ) ·:NH3 , CH3CI and Cl0 2 have distorted geometry, thus, they have
a net dipole moment, while BF3 has regular triangular planar
41tt0 r0 n
geometry.
where, U is lattice energy
Hence, the dipole moment ofBF3 is zero.
rnode is interionic distance
3. I has maximum covalent bond and negative charge on
U<>< - - - - - - - electronegative nitrogen, most stable. ITT has more covalent bond
interionic distance
than both II and IV, TTI is second most stable.
: .Ions should be of small size to have high lattice energy.
Between II and IV, II is more stable since it has negative charge
37. Greater the charge, smaller the radius, greater the polarising on nitrogen while IV has negative charge on carbon atom.
power and thus greater the covalent nature. This leads to increase
4. Lower the covalent character, higher wi ll be ionic character.
in lattice energy. I
38. The solubility of a compound depends upon its hydration Covalent character "" - - - - - "" size of anion
size of cation
enthalpy. I f hydration enthalpy exceeds the lattice enthalpy than (according to Fajan 's rule)
it is soluble in water. For Ag2S0 4, hydration enthalpy is lower
Cl 20, contains 0 2
-, NC1 3 contains N3-, PbCl 2 contains Pb2+
than lattice enthalpy, so it is insoluble in water.
and BaCl 2 contains Ba 2+.
39. We know that, All+ cation is smaller than Na+ (because of greater
nuclea r charge). According to Fajan's rule, small cation polarise Hence, the order of covalent character is
anion upto greater extent. Hence, Al 3+ polarise c1- ions a to NCl 3 > Cl 20 > PbCl 2 > BaCl 2
greater extent, therefore, AIC1 3 has covalent bond (character) : .BaCl 2 has the greatest ionic character.
between Al and Cl atoms.
5. Calculated dipole moment,
40. C---CI bond is more ionic than C-I bond because of the greater µcal = 2.0 X 10-IO m X 1.6 X 10-19 C
difference in electronegativities of C and Cl as compared to that
of carbon and iodine. Therefore, C---Cl bond is stronger than = 3.2x 10-29 C-m.
C-I bond.
Percentage of ionic character= µ.,,'P x 100
41. A has three electrons in its outermost orbit, its valency is 3. µcal
B has six electrons in its outermost orbit, its valency is 2
5.12 X 10-29 X 100 = 16%
Element A B
3.2 X 10- 29
Valency 3 2
Formula of the compound = A2B 3 6. Per cent ionic character is given by percent of ionic character.
42. Allene (C3H4 ) can be represented as: = 16 (XA - Xs) + 3.5 (XA - Xsi
H H From the above relation, it is clear that as soon as (XA - X 8 )
I I increases, % ionic character will also increase. Therefore, curve
H- C=C=C- H C shows a correct path.
It has 2 double and 4 single bonds.
80 I Chapterwise & Topicwise Engineering Entrances Solved Papers

7. Given, Percentage of ionic character in HBr

Observed dipole moment = 1.03 D Dipole moment of HBr x
100
Bond length ofHCI molecule, d = 1. 275 A interspacing distance x q
= 1.275 x 10- 8 cm 1.6 X I 0-30 X I 00
Charge of electron, e- = 4. 8 x 10- 10 esu 1.6 X 10- 19 X 10- IO
Percentage ionic character = ? = 10- 3o X 1029 X 100
Theoretical value of dipole moment = ex d = 10- t X 100
= 4.8 x 10- 10 x 1.275 x 10-8 esu. cm
= 0.1 X 100= 10%
=6.12x 10- 18 esu-cm 12. Molecules in trans-I, 2-dichloroethene are symmetrical, hence
= 6.12 D no dipole moment.
Percentage ionic character
___ O_b_se_rv
_e_d_ d1~
· p_o_le_m
_ orne
_ n_t_ _ xl00 13. CC1 4 andcompound c 1 - @ - c 1 haszerodipolemoment
Theoretical value of dipole moment due to their symmetrical stmcnrre.
3
= l.0 xl00=16.83% 14. CCl 4 and CH 4 has zero moment due to their symmetrical
6.12
strucn1re while CHCl 3 is more polar than CIB 3 due to greater
8. The best strucnire ofwater molecule can be represented as: electronegativity of Cl than I. Hence, CHCI 3 has largest dipole
moment among the given molecules.
·o·
15. The molecule of N 20 is linear as would be expected for a
H~H triatomic molecule with 16 outer shell electrons. Its resonance

In water molecule, the H-0-H bond angle is 104.5° and

dipole moment is 1.84 D.
strucn1re is

~ : N=N=H :
..
The bond angle ofH 20 is lower than 109.28' due to the presence
of two lone pair of electrons on the oxygen atom. 16. Percentage ionic character
= Experimental value of DM x
9. The molecule in which the bond dipoles of all the bonds are 100
cancel out by each other, is called non-polar e.g., CCl 4 • Theoretical value of OM
In CC1 4, there is a large d ifference between the electronegativities 3
= J. 0 X 100= 17%
ofC and Cl but all the four C- Cl bond dipoles cancel each other, 6.12
hence it is a non-polar molecule.
Topic 3 Valene Shell Electron Pair
Repulsion (VSEPR) Theory,
Valence Bond Theory
(VBT), Hybridisation
1. HNNN is hydrazoic acid (HN3). Its Lewis electron-dot stmcture
is
µ ,e,ultant = µ2 + µ3 + µ4 + + +
µnett =µI - µ,e,ultant H- N=N= N : (-----t H- NssN- ~ -:
µnett =0
Hence, CCl 4 is non-polar. The number of valence shell bonding electrons wit be double of
the munber of bonds. So, the number of valence-shell bonding
10. Number of bonds between two atoms is called bond order.
electrons are IO as total five bonds are formed in the
Resonating structures of benzene are electron-dot stmctme
2. Melamine is a heterocyclic compound.
•• N ••
HN-( )-'Nffi
2

: . In benzene, the carbon-carbon bond is between the double and :N N:

single bond due to the resonance, so its bond order is 1.5. i.e. ~ /
between I and 2. :NH2
11. Charge of e- = 1.6 x 10- 19
Each nitrogen atom has one lone pair.
Dipole moment ofHBr = 1.6 x 10- 30cm
Thus, in all six lone pairs.
10
Interatomic spacing = I A= 1 x I 0- m
 Chemical Bonding and Molecular Structure I 81
3. The number ofn bonds in I
9. Bond angle ox - - - - - - - ox - - - - - - -
CH ,=CH- CH=CH- C=C number of lone pairs size of central atom
-l l l
ht l1t

4. A lone pair of electrons in an atom implies a pair of valence

F
I
Q Q F
I
electrons not involved in bonding. F- Cl - F p N B
/'-._........._F \
d~
/
\........._F /
5. In NH3, the N atom bond contains one lone pair of electrons and F F F F F F
three bond pairs in its va lence shell. So, it shows s/
2 lone pair (Ip) I-Ip 1-lp 0-lp
hybridization.
(T- shape) (pyramidal) (pyramidal) (trigonal planar)
6. In XeO 2F2, the bonding arrangement around the central atom Xe
is But size ofN < size of P,
Thus, Bond angle ofN > P
O: = : Xe := : O
Hence, the correct order is:
/\_
F• F• CIF3 < PF3 < NF3 < BF3
4cr-bonds + I Ip= 5 10. In graphite, C-atom is sp2-hy bridised.
Hybridisation of Xe= s/d 2
p-character = - x I 00 "' 67%
sp3d hybridisation corresponds to trigonal bipyramidal 3
geometry. Also, in trigonal bipyramidal geometry, lone pairs Again, in diamond, C-atom is s/ hy bridised.
remains present on equ atorial positions in order to give less 3
electronic repulsion. p-character = - x I 00 = 75%
4
F 11. 40' bonds in POCJ 3 ⇒ s/ hybridisation w ithout lone pair of
Remove I ~o electrons.
~ Xe~
lone pair 12.
I ~o
F
See-saw shape
Note According to Bent's rule, the more electronegative atoms +
must be present on axial position. Hence, F are kept on axial NO; (II) O=N=O
positions.

7.
Thus, the shape ofXeO 2F 2 molecule in see-saw shape.
Nl
p jGroup = 15
NO;(III) ~
H
rJ
/ [ ..........
H H
+

As Valence l
5
J
Sb Electrons = ' cr-bon
d
Lone pair
Unpaired
electron
Total
MCl 3 has sp3-hybridised M-element with one lone pair. lp-bp I. 3 X X 3 (s/)
repulsion decreases bond angle.
II. 2 X X 2 (sp)
However, the bond-pairs of electrons are much farther away from
the central atom than they are in NC13. T hus, lone-pair causes III. 4 X X 4 (sp3)
even greater distortion in PC1 3 , AsCl 3 and SbC13 •
13. Electronic configuration of
Thus, bond angle decreases from NCl 3 (maximum) to SbCl 3
(minimum). I in IF 7 is
5s 2 5p 5 5d0
8. - - - - - - - - - - - - - -
Species Structure I= [ill 11~1 1~1 11 ~I~I~I~
in ground state
cot, NO3 Triangular planar
A B C D E F G
Pct:, SiCl4

PF5
Tetrahedral

Trigonal bipyramidal
JF 7 = PJ DJ DJ DJ [ij ~
./
BrF5 Square pyramidal Inclined at 72° at 90° with
w ith on e each other ABCDEplane
AIFt, SF6 Octahedral seven sp3d3 hybrid orbitals
fonning cr-bonds w ith F-atoms,
82 I Chapterwise & Topicwise Engineering Entrances Solved Papers

F F 21. In BrF5 number of electron pairs= 6 (I lp + 5 bp)

'
'' F
l~ IF
90°'.
F ------- I :rn°
,,,

',,,',,,
FI F
/ " "'-
F
F So, the structure is supposed to be square pyramidal but will be
distorted because of additional l1rbp interaction.
F F Additional l1rbp interaction reduced the all bond angle and do
Pentagonal bipyramidal structure not let any angle to be 90°.
22. OSF2 has pyramidal shape
14.
Hybridisation of Lone pair on
Species Bonding pairs
Xe Xe

XeO3 s/ I 3
2
XeF4 sp3d 2 4
23. (a) NH3 + Jr - NH;
(3bp + 1/p (4bp =>sp3
XeF6 3 I
s/d 6 ""'sp3 hybridisation) hybridisation)

BF3 + F-

-
XeF2 sp3d 3 (Max.) 2 (b) - BF.i
(3bp =>sp2 hybridisation) (4bp=>sp 3 hybridisation)

15. CaC2 ~ Ca 2+ + c~- (c) Hp + H+ H 3O+

Carbide ion

-
(2bp+2/p (3bp+ 1/p
In carbide ion, two carbon atoms are joined by triple bond (It is => sp3 hybridisation) => sp 3 hybridisation)

isoelectronic with N 2) C== Cwith two 1t and one cr-bonds. (d) CH=CH + 2H2
sp sp
CH3- CH3
sp3 sp3
2
16. s/d hybridised molecule have octahedral geometry.
Hence, reaction given in option (b) involves the change of
1 2 3 4 5
hybridisation from s/ to s/.
17. CH3- f H=f=CH- CH 3
, 24. H H H H H
sp-

H
*~-c-{-7-H
sp
18. F F F
I t'.5' I ~FF IF
CC>xe CC>xe1/ CC>xe/ H H I H H
IQ I ~F H- C- H
F F F
F
I ""F I
XeF2 XeF6 H

-
XeF4 25 and 41t bonds
2-bond pair 6-bondpair
4-bond pair
3-lo ne pair I-lone pair 25. (a) CH4 CH3- CH3
2-lone pair 4bp+ Olp 4bp 4bp

-
Hybridisation sp 3 sp3 sp3
Hence, no ofnon-bonding electron pairs on Xe in XeF6 , XeF 4 and Structure tetrahedral tetrahedral
XeF 2 respectively will be I, 2 and 3. (b) NH3 NH+4
19. The stmcture of benzene nitrile is 3bp + lip 4bp
Hybridisation sp3 sp3

H H (c)
Structure pyramidal

BF3
3bp
Hybridisation sp2
- tetrahedral

BF4
4bp
sp3

-
H H Structrue tetrahedral
trigonal plannar

H (d) Hp H 3O+
2bp + 2/p 3bp + lip
Benzene nitrile contains I 3cr and S1t bonds. Hybridisation sp3 sp3
Structure angular pyramidal
20. In phenol each C atom is sp2 hybridised and O atom is sp3
hybridised. Thus, conversion of BF3 into BF4 involves change in both
hybridisation and shape.
 Chemical Bonding and Molecular Structure I 83
26. In C28<; (alkane), C is sp3 hybridised. (d) CH 3 - CH= CH- CH 2
spJ sp2 sp2 spJ
In C2H 4 (alkene), C is s/ hybridised.
In BeC1 2, Be is sp hybridised. (e) CH 2 =CH- CH= CH,
sp2 sp2 sp2 sp2-
In C2H 2 (alkyne), C is sp hybridised.
27. Since, the geometry of AsF5 molecule is trigonal bipyramidal, it is
Hence, in CH 3- C =
C- cH;, all the three types of hybrid
carbons are present.
sp3d hybridised. Thus, s, Px, PY' Pz and d; orbitals are utilised by
33. In XeF4, the central atom, Xe, has eight electrons in its outermost
As atom for bonding.
shell. Out of these four are used for forming four o-bonds with F
0 O- H and four remain as two lone pairs.
II I XeF4 ⇒ 4o bonds + 2 lone pairs
28. CH 3- C- CH3 ~ CH 2=C- C H 3
Acetone Enolic fonn ofacetone ⇒ 6 hybridised orbitals, i.e. sp3d2 hy bridisation
Since, two lone pairs of electrons are present, the geometry of
XeF4 becomes square planar from octahedral due to lp- lp
repulsion.

F~F
Xe
F . F
Hence, enolic form of acetone contains 9 sigma bonds, I pi bond
and two lone pairs. 34. 13 ion is made up of an I2 molecule with an r bonded to it by
29. The formula of MX3 shows the presence of 3o bonds. Since, it means of a coordinate bond in which I2 is lone pair acceptor
(Lewis acid) and I the lone pair donor (Lewis base).
has T-shape geometry, it must contain 2 lone pairs as
There are two bond pairs and three lone pairs in the outer shell of
central atom. To minimise the repulsive forces the three lone
pairs occupy the equatorial position.
The ion is therefore, linear in shape with a bond angle of exactly
~x 180°.
X
30.
Molecule Hybridisation
SO3 sp2
C2H2 sp
C2H4 sp2 12 + r ~ [I- If- I f
Lewis Lewis
CH4 sp3 acid base
CO 2 Sp Similarly, N 3 ion is also linear in shape.
35. In XeF6, the oxidation state of Xe is + 6. The shape ofXeF6 should
Hence, the hybrid state ofS in SO3 is similar to that ofC in C2H4.
be pentagonal bi pyramid due to sp3d 3 hybridisation but due to the
31. The pyramidal strncture of covalent molecule AB3 is as
presence of one lone pair at one trans position, its shape becomes
distorted octahedral.
F
l" I /F 5s Sp 5d
Number. of lone pair = I "j;?Xe"F [ill 11111111 1 11 11 1
distorted
Number. of bond pair = 3 octahedral xenon atom in third excited state
32. If there is four o-bonds, hybridisation is sl, if three o-bonds, shape

hybridisation is s/ and if two o-bonds, hybridisation is sp. 36. ICI;:, Ij", Nj" are linear but CIO 2 is angular due to sl
(a) CH2 = C = CH2 hybridisation of Cl atom.
sp2 sp sp2 :CJ:
(b) CH3 - CH = CH-CH;
spJ sp2 sp2 sp2
~~t
So, CIO 2 is non-linear.
(c) CH3 -C
spJ sp
= C-CWi
sp sp2
84 I Chapterwise & Topicwise Engineering Entrances Solved Papers

37. S in SF4 possesses trigonal bipyramidal stmcture with

hybridisation. S in ground state
sp3d 41. SF2 ⇒ Q
3s 3p 3d s
rn:J 11~1111I I~---~-~
I I F/ tD
F
S in excited state go ~ 11 I I I Total number = 4 ➔ sp3 hybridisation

electrons off-atoms electrons off-atoms F

sp3d hybridisation F- S
ID (See-saw)
Due to sp3d hybridisation, SF 4 has trigonal bipyramidal stmct:ure. l~F
Note But in actual, due to presence of one lone pair, it has
F
see-saw stmcture.
Total number= 5 ➔ sp3d hybridisation
38. SF6 has octahedral geometry, sp3d 2 hybridisation and bond angle
is 90°. SF6 ⇒ F

Ki77F F'-... 1/F

F/1'-...F
F
F~ Total number= 6 ➔ sp3d2 (octahedral) hybridisation
F
42. Draw bond stmcture and then count bonds.
Percentage of d-character
2 (no. of d - orbitals) x l00= 33%
6 (total hybridised orbitals)
So, SF6 are bond angle = 90°
and d-character = 33%.
39. BCI3 = 3 cr bonds + 0 lp of [ = 3 ⇒ sp2 hybridisation As P has vaccant d-orbitals. So, it has a tendency to form pn - dn
bonds. Thus, no of cr and dn - pn bonds are 120', 2dn-pn bonds.
NCl 3 = 30' bonds+ llpof e- = 4 ⇒ sp3 hybridisation
43. F.XF angles of two types are present in sp3d hybrid orbitals. Since,
40. (I)CH4 ⇒ SF4 shows sp3d hybridisation as follows, therefore, it exhibits two
different FXF angles.
F
I F
<Df(F
F
(II)BCl 3 ⇒
44. Species having same hybridisation show similar geometry.
SO~- : Hybridisation of S ➔ sp3
ClO4 : Hybridisation of Cl ➔ sp3
45.
Molecule bp + Ip Hybridisation Shape
H2O 2+ 2 sp3 Angular

(IV) li" ⇒ BCl 3 3+ 0 sp2 Trigonal Planar

Hence, the increasing order of bond angles is NH; 4+0 s/ Tetrahedral
(III) < (I) < (II) < (IV).
CH 4 4+0 sp3 Tetrahedral
 Chemical Bonding and Molecular Structure I 85
46. The stmcture ofperoxodisulphuric acid (H2SiO8 ) is Further the BeCl2 has linear stmcture, hence its bond angle is
180°. The N 2O molecule also has linear stmcture with bond
0 0 angle 180°.
nllcr crlln 180°
8
0
Mcr cr\
~o- cr o_g..-crs\~
cr O
Cl~ C l
+
0 - cr H H- cr 0
•• +
:N= N= O -
••
.. ..••
:N= N- o :
Hence, it contains 11 cr and 4n-bonds. 54. In a double bond(= ) one cr and one n-bond is present while in a
47. C1O4 and XeO 3 both contain 3dn - pn bonds. single bond(- ) only cr-bond is present.
o- The structure of the naphthalene is as

1
Cl ~
0 Y'~o In naphthalene five double bonds are present, hence 57t bonds are
0 present in naphthalene.

48. The ;,
0
-z bond angle in H 2O is I 04.5° due to the presence of
55. Valence bond theory (Resonance theory) of metallic bond was
given by Pauling ( 1937). According to this theory, the metallic
H H bonding is essentially covalent in origin and metallic stmcture
two lone pairs of electrons. This fact can be best explained with exhibits resonance of electro-pair bonds between each atom and
the help of valence shell electron pair repulsion (VSEPR) theory. its nearest neighbours. In other words, there is a resonance of a
large number of canonical forms.
49. PCl 3 and AsCl 3 have s/ hybridisation and PF5 has s/d
hybridisation. Hence, in group of PCl 3, AsCl 3 and PF5 all do not 56. The C-C bond length in s/
hybridisation is greater than s/
have s/d hybridisation.
hybridisation due to large size of p-orbitals.
In diamond s/ hybridised C-ato ms are present while in graphite,
50. NO2 has sp2 hybridisation. Its expected geometry is trigonal
planar but actual geometry is V-shape due to presence oflone pair
naphthalene and fnllerene s/
hybridised C-atoms are present,
of electrons. therefore the C-C bond length is maximum in diamond.
51. 57. According to VSEPR theory the bond angle decreases with
Molecule/ion Type of hybridisation increase in the size of the valence shell of the central atom
because electronegativity decreases. i.e. decreasing order of bond
A. NH: 3. spJ angles is
B. PCl 5 2. NH 3 > PH 3 > AsH3 > SbH3
s/d
58. In IF 5, I being less
C. SF6 4. sp3d2
electronegative is the central atom.
D. TF7 I. sp3d3 In I, no of valence electrons= 7
So, no of electrons shared = 45 (each by F-atom) +5 (I-atom)= IO
52. In ethanol the oxygen of - OH group is bonded to the sp3
:. Number of bond pairs= .!Q = 5
hybridised carbon by a sigma bond. The C--0--H bond angle in 2
ethanol is less than the tetrahedral angle (I 09°, 28') due to larger 7-5
repulsions between the lone pairs of oxygen. Hence, it is I 04° in Number of lone pairs = - - = I
2
ethanol.
Total no. of electron pairs = 5 + I = 6 = sp 3d 2 hydridisation
53. Bond angle depends on the strucn1re of molecule. If two
molecules have same structure, then bond angle is decided by the Thus, the shape of IF 5 with 5 bp and I .Ip is square pyramidal
electronegativity of central atom. Electronegativity of central 59. XeO 3 (s/ hy bridisation)
atom oc bond angle. = contain a lone pair
The bond angle of H 2S is less than H 2O because S is less = trigonal pyramidal shape
electronegative than H 2O.
XeOF4 (sp 3d hybridisation) = one lone pair
Hence, H 2O > H 2S
(104 .5° ) (92.2° ) = square pyramidal shape
BOt (sp2 hybridisation) = planar triangular
H
CIF3 (sp3d 2 hybridisation) = two lone pair= T shaped
I ·o·
CH3- C ~ H I; (s/d hybridisation) = 3 lone pair = linear
I 104°
H
86 I Chapterwise & Topicwise Engineering Entrances Solved Papers

60. According to valence shell e lectron pair repulsion (VSEPR) theory, 67. In octahedral structure i\1X6, the six hybrid orbitals (s/d 2 ) are
the order of repulsive interactions between various electrons is directed towards the corners of a regular octahedral with an
Ip - Ip > Ip - bp > bp - bp. angle of 90°. According to following structure of MX6 the
61. BeC1 2 has only two bond pair of electrons. So, its hybridisation is sp number of X - M - X bonds at 180° must be three.
and bond angle is 180°. Its geometry is linear. In BC! 3, there are three X
bond pair of electrons. So, its hybridisation is sp2 and bond angle is X ~-t--~X
120°. Its geometry is trigonal planar
0 0 M
II II
62. CH 3 - C- OH x ~-t--~x
sp2
H X

CH3 -
I
C- OH
68. The structure of H 20 is angular V-shape and has
sp3-hybridisation and bond angle is I 05°. Its dipole moment
1sp3
value is positive or more than zero.
H
·o·
63. Cl- P---Cl bond angles in PC1 5 molecule are 120° and 90°. PCI5, ~ Hereµ > 0 180°
having sp3d hybridised P atom (trigonal bipyramidal geometry) has H/ 104.5° ~ H F~ F
two types of bonds, axial and equatorial. The two types of bond have
But in BeF2, structure is linear due to sp-hybridisation (µ = 0)
different bond lengths I, 2, 3 are 4 equatorial bonds and 4, 5 are axial
bonds. Thus, due to µ > 0, Hp is dipolar and due to µ = 0, BeF2 is
non-polar.
69. In BrF3 molecule, Br is s/d hybrid, but geometry is T-shaped
due to distortion of geometry from trigonal-bipyramidal to
T-shaped by the involvement oflone pair-lone pair repulsion.
F
.-..______ 1

Br- F
••/ I
64. BCI 3 w ith sp 2 hybridisation has bond angle equal to 120° (trigonal F
planar). NH3 and H 20 have sp3 hybridisation but due to the presence Here, Ip - Ip repulsion = I
of lone pair of electrons, they have bond angle less than Ip - bp repulsion= 2
109.28' (NH3 - 107° , H 20 - 104.5° ), AsH3 (sp3 hybrid) has smaller
bp - bp repulsion = 2
bond angle than NH3 due to less electronegativity of As than N.
70. SiF4 and SF4 are not isostmcniral because SiF4 is tetrahedral
65. Phosphorus atom is sp3 hybridised in P4 usually. Therefore, due to sp3 hybridisation ofSi while SF4 is not tetrahedral but it
p-character 75%.
is distorted trigonal bipyramidal because in it S is sp3d
66. Number, of hybrid orbital = _!_ [Number. of e- in V-shell of atom + hybridised and has a lone pair of electron.
2
71. Structure of ammonia is pyramidal (Distorted from tetrahedral
Number. of monovalent atoms - charge on cation + charge on anion]
to pyramidal due to repulsion between lone pair and bond pair
of electrons).

9 N
Number of hybrid orbital 2 3 4 5 6 7
Type of hybridisation sp sp 2 sp 3 sp 3d sp3d 2 sp 3d 3
/ I"\ H
Hybridisation in TeC1 4 72. Silicate ion (SiOt-) is the basic structural unit of silicates.
. . I Silicates are metal derivatives of silicic acid. Jt has 4 bonded
Number. o f hybnd orbital = - [6 + 4 + 0 + OJ= 5
2 pair and 0 lone pair, hybridisation is s/,
so tetrahedral
Hence, TeCl 4 shows s/ d hybridisation. structure.

73. In CO2 , C-atom is sp-hybridised, thus it has linear structure.
In XeF2 , Xe is s/d hybridised with three lone-pairs of electrons
on equatorial position. This minimises repulsion, hence it has
also linear structure.
Chemical Bonding and Molecular Structure I 87
78. BCl 3 has trigonal planar structure due to 3 bond pairs in the
valence shell of boron whereas NCl 3 has distorted tetrahedral
structure due to one lone pair and three bond pair in the va lence
shell of nitrogen.

1 79. Bond
74. The structure of acetylene is H---C ° C-H. In acetylene, both
21t
Molecule Hybridisation Repulsion
angle
the C-atoms are sp hybridised. Hence, in acetylene molecule, SO 2 Ip. bp, bp - bp 119°
s/
there are one sigma and two pi bonds a re present between carbon
atoms. Hp sp3 Ip - Ip, bp - Ip, 104.5°
75. PCl 5= s/d (Trigonal pyramidal) bp-bp
IF7 = s/d3 (Pentagonal bipyramidal) SH2 sp3 - do-- 90°
H 3O+ = sp3 (Pyramidal) sp3 Ip - bp, bp - bp 107°
NH3
CIO2 = sp2 (Angular) bond length are shorter than single bond
due to resonance.
80. Hybridisation of Lone
NH; = s/ (Tetrahedral) Molecule Structure
central atom pair
76. Hybridisation can be find out by the use of following formula: F
I
H = - [V+Y-C+A] 1,,,.F
2 SF4 0 s '---
I F
sp3d One
Here, V =va lence shell electrons of the central atom
Y = number of monovalent atom F

C = total positive charge F

A = total negative charge
F-
I
C- F Zero
CF4 sp3
CO 2 SO 2 N2O CO
I
F
1
H = [4 +0]
1 I I
H= [6+0] H= [5+0-I] H= [4+0] \.::· -J
2 2 2 2
=2 =3 =2 =2 F-....._V,,,.F
2
=sp =sp2

Hence, SO 2 has sp 2 hy bridisation.

=sp =sp
XeF4
F /0. .'- -
X
F
s/d Two

77. The number of lone pair in XeOF4 is one (I). The structure of
XeOF4 is given as follows 81. The shape ofCIF3 is distorted T-shape due to the presence of two
lone pairs of electrons.
0
F""' 1 /
Xe
F
F/ (j~~p3tf2 hybridisation
F
5s Sp 5d
82. N 2O is isoelectronic w ith CO2 and N 3.
Xe atom in DI]
11~11~11~1l~~I~I~
ground state Hence, its structure is linear. as
Xe in excited DI] 1111111111 1111
state
In XeOF DI] I1
4 ~I1~I1~I I1~I1~I1~I 83. In XeF;, Xe atom has only seven e lectrons, i.e. ss2s/. Here, two
+-bond formation--+\ Sp electrons are promoted to Sd-sublevel. Then, 5s, three Sp and
two 5d orbitals hybridise to give six sp3d 2 hybrid orbitals in an
sp3J2 hybridisation lo ne pair octahedral geometry. Out of these five orbitals are singly
occupied which form sigma bonds with five F atoms. The sixth
hybrid orbital is occupied by a lone pair in trans position giving a
square pyramid structure.
88 I Chapterwise & Topicwise Engineering Entrances Solved Papers

84. In diethyl ether, oxygen undergoes

sl hybrid orbitals.
sl hybridisation forming four

85. In co~- ion the C-atom undergoes sp2- hybridisation. It has

triangular planar stmcture. While BF4, NH! and so~- have
tetrahedral structure.
F f> F JJT,oili,dotl

86. The position at which substituent is present, is called ipso-position. 92. Stmcnrre of CO2 is linear due to s1rhybridisation.
Cl (sp)
O=C=O
~ ;pso-can>on
93. I, 2-butandiene has the following stmcture.
H H H
I I I
Chlorobenzene H- C- C=C=C- H
lsp3 sp2 sp sp2
The hybridisation of ipso-carbon in chlorobenzene is sp2.
H
87. C---C bond length in sp2 hybrid molecule is= 1.39A. 94. Bond length depends upon their hybridisatoin
88. Boron has planar stmcnrre due to sp2 hybridisation. C- C > C=C > C = C
2s 2p sp3 > sp2 > sp
8
(G.S.)[II 11I I Thus, CH bond length is longest in C2H 2 .
95. In methane bond angle is 109°28'. Methane molecule is
(E.S.) [I] 1111I
8 tetrahedral in stmcture.
96. In SO3 molecule, S-atom remains sp2 hybrid, hence, it has
sp2-hybridisation
trigonal planar stmcn,re.
BF3 [I] I1~I1~I 0
sp2-hybridisation II
s
89. Number of hybrid orbitals for neutral atom = _!_ [Number of
2
~~0
0
valence electron in central atom + Number of monovalent atom]
5 5 97. CO2 is isostmctural with N 2O because both have linear strnctme.
Number of hybrid orbital = + = 5.
2
Hence, hybridisation is s/d.
90. sl d 2 hybridisation has octahedral stmcture such that fom hybrid 98. Water molecule has following strucnrre
orbitals are at 90°with respect to each other and others two at 90°
with first four. ·o·
91. SF4 has trigonal bipyramidal geometry but lone pair of electrons
H
/ ~H
repels the axial bond pair and decrease the bond angle to 173°.
F Therefore, there are 4 pairs of electrons (2 lone pairs and 2 bond
I/ F pairs) in the valence shell ofO-atom in water molecule.
Q>s, 99. CH = C-CH2-CH3
I 'F sp sp sp3 sp3
F
In butyne - 1, there is no carbon with sp2 hybridisation.
H H H H
la [a la la
100. H~C a C~C~C~H
la la
H H
F

F
~Xe/ I
V F
Square
101. CISH =CH2
sp spz
Oiloroethene
Oi
Number of cr bonds in I -butene are I I.

~
all carbon atoms ares/ hybridised

IF./. / /'----......._
I ----........F
planar benzene

,• • 1
,_✓
 Chemical Bonding and Molecular Structure I 89
CH 2 =CJ;I- CJ;l=CH 2 108. In benzene 12cr and 31t bonds are present. The structure of
sp2 sp sp sp2 benzene is
I, 3-butadiene

CH 2 =CH-CH =CH-CH = CH2

sp2 sp2 sp2 sp2 sp2 sp2
I, 3, 5-hexatriene

102. All molecules or ions i.e. Hp, NH;, so~-, ClO4and NH3 are
involved in sp3-hybridisation in their formation.

103. - - - - - - ~ - - - - - - - - - -
Column I Column IT
(Compow1t) (Strncture)
A. CIF 3 I. 5 109. NH 3 molecule in its valence shell has three bond pairs of
electrons and one lone pair of electrons. The shape of NH3
B. PC15 2. 3
molecule is pyramidal due to the presence of one lone pair
C. IF s 3. 4 electron. It hass/
hybridisation.
D. CC14 4. 2
E. XeF 4 5. f)
N
104. The correct sequence of hybridisation of methane, ethene and
ethyne is sp3, sp2 and sp. H/ I "'-H
H
105. In CCl4 , all bonds of carbon being identical, the molecule is a 3
regular tetrahedron.
110. PCl 5 molecule has sp d hybridisation. Its geometry is trigonal
bipyramidal and it has 5 valence shell pairs of electrons.
106.
H 111. Hybridisation of S in so~- is given by H = ..!_[6 + 0 + 2 ]
2
la a = 4 = s/ Thus, sulphate ion is tetrahedral in shape.
H- a aC-
l a C-21t N
H
Hence, number of cr and 1t-bond in acetonitrile are 5 and 2
respectively.
107. Structure of C2H 4 is

112. Structure ofC2H 2 is linear. H- C==C- H

Structure of CO2 is also linear. O =C=O
So, both are isostructural species.
113. In CIO3, Cl is central atom, it is sp3 hybrid and on it one lone pair
of electrons (free pair of electrons) is present.

Pyramidal shape
In XeF4, Xeis central atom and it is s/d 2 hybrid and on it two lone
pairs of electrons are present.
(Formation ofn-bond)

So, the compound (X) is C2H 4 •

Square planar
90 I Chapterwise & Topicwise Engineering Entrances Solved Papers
In SF4 , Sis central atom and s/d-hybridised and on it one lone 117.
pair of electrons is present.
F
F,___i
S- F

0~
Irregular tetrahedral
In I3, I is central atom and it is sp3d hybridised and on it three H
lone pair of electrons are present.
15cr and 31t-bonds are present in toluene.
118. Bond angles of
NH3 = 107°, H 2Se = 91.0°,
H 20 = 104.5°, H 2S= 92.2°
So, the H 2Se mo lecule has smallest bond angle.
119. sp3 hybridisation Tetrahedron molecule
Linear shape 2
dsp hybridisation Square planar molecule
114. In the strucnrre of P40 each phosphorus atom is covalently
10,
linked with three oxygen atoms and each oxygen atom is bonded s/d hybridisation Trigonal bipyramidal molecule
to two phosphorus atoms. Each phosphorus atom is also linked s/d2or d2s/ Octahedron molecule hybridisation
with an additional oxygen atom with the help of a coordinate
linkage by lone pair of electron present on P atom. 120. (o-bps + lps = 3 + I= 4)
:.Hybridisation= s/
In NF3 , N-atoms is s/-hybrid but due to
presence of a lone pair of electron, NF3 has
pyramidal strucnrre.
121. Cl- Be-Cl
In BeC12, Be is sp-hybridised, hence it has linear structure.
H
C
I
H/ 1"'-H
H
Angular Angular Tetrahedral
115. In PCl 3 molecule, phosphoms is sp3- hybridised but due to
presence of lone-pair of electron, it has pyramidal stmcnrre. 122. SF6 does not obey octet rule as in it S-atom has 12 electrons in its
valence shell.
Q F

Cl Cl Cl
p
,...... I........_
F
F•x~x•F or
~,~-f//F
I
s ,
f•X~X • F
116. BeH2 molecule is linear because it has sp-hy bridisacion. It has F F ~+ ~ F
bond angle 180°. H - Be- H F
 Chemical Bonding and Molecular Structure I 91
123. In methane, ethene and ethyne, the hybridisations are (d) PF5 and IF7
respectively sp3, sp2 and sp. Hence, % s-character will be F
sp3 = ~ X I00 = 25% F- P
1/ F
4
2 1 I "-F
Sp = - X 100 = 33% F
3
Trigonal bipyramidal Pentagonal bipyramidal
1
Sp= - X 100 = 50%
2 :. Both have different strucnire.
124. In both CH4 and CCl 4 , sp3 hybridisation is present and both have (e) XeF2 and CO2
tetrahedral geometry. F -Xe-F O=C=O
125. The d-orbital involved in sid-hybridisation is d;.
Linear Li near
126. XeF2 molecule contains two bond pairs and three lone pairs in the
·: Both have linear shape.
outer-shell of central atom and thus its hybridisation is sp3d but :. They have same structure.
to minimise the repulsive forces the three lone pairs occupy the
129. In NH; ion, N is sp3 hybridised therefore, bond angle in NH;
equatorial position and the molecule becomes linear shape.
(tetrahedral shape) is 109°28'.
F
130. In AlH3, Al is sp2 hybridised while in AlH4, Al issp3 hybridised.
131.
Hybridisation Lone pair on Bonding
Species
of Xe Xe pairs
XeF 2 sp3d 3 2

XeF 4 sp3d1 2 4
127.
XeF6 sp3d3 6

132. Square planar geometry has ds/- hybridisation, thus, it is formed

by the hybridisation of d,s, Px , Py atomic orbitals
133. There are 16 P-0 bonds in P4 0 10• [For structure refer to ans 122]

Topic 4 Hydrogen Bonding,

Intermolecular Forces and
Metallic Bond
l 9cr-bonds and 4n-bonds. 1. (a) Ice floats in water due to the low density of ice as compared to
water because of the presence of open cage like stmcnire
128. (a) CF4 and SF4
[formed by intermolecular H-bonding] in ice.
F (b) Higher Lewis basicity of primary amines than tertiary amines
I in aqueous solution can be explained by soluation effect
C through H-bonding. Amine gets protonated by accepting a
F/ I" F H+ ion from aqueous solution. The protonated amine forms
F with H 20 molecules and gets solvated. Hence, primary amine
Tetrahedral See-saw structure is more basic than tertiary amine in aqeous solution.
(s~ hybridisation) (s~d hybridisation) ,,,-H
: . Both have different stmcnire. ,O'---
H,, H
(b) BF3 and PCl 3 tt• +/ ,,,-H
R- NH2 ~ R - N - N --- 0
(from HzO) "- '-.. H

F H ,, ....-H
,0,,.
I Solvation by 3 water molecules '--- H
B tt+ +
F/ "-F R3N ~ R3NH
Trigonal planar Pyramidal structure R '--- + / H
(sp2 hybridsation) (sp3 hybridsation) R- N - H ---0
R/ '--- H
: .Both have different structure.
Solvation by l water molecule
92 I Chapterwise & Topicwise Engineering Entrances Solved Papers

(c) Dimerisation of acetic acid in benzene is due to

o--n
intermolecular H-bonding

H 3C - C
~ O ---H - O-........
-........0 - H --- 0-::7
c- CH3
o: N6+
j,
0
11 intramolecular
i ~ H-bonding
=h6 -
L H-bon ds
8. In ortho-hydroxy benzoic acid, intramolecular H-bonding takes
2. A molecule having largest electronegativity difference forms place between H-atom of hydroxy group and O-atom of carboxy
strong H-bonds and exists in a polymeric form in gaseous state. group, --COOH. As intramolecular H-bonding is weaker than
/F - H -...F intennolecular H-bonding, therefore, this bond breaks at a lower
temperature and hence, provides volatility to the molecule. Thus,
H I o-hydroxybenzoic acid has maximum volatility.
'- F ---· H - F---
.H
a°-_H&+
3. In CuSO4 four water molecules are bonded to Cu 2 + ion through ~ 6+ ~ intramolecular H-bonding
coordinate bonds and the remaining one H 2O molecule bonded to ~ C = 06 -
so~- ion and two H zO molecules through H-bonding Hence, I
among S molecules ofH 2 O only one H 2O molecule is involved in OH
H-bonding o-hydroxy benzoic acid (salicylic acid]

H H 9. In (A)para-nitro phenol intermolecular (between two molecules)

I I H-bonding exists while in (B) ortho-nitrophenol, intramolecular
H- O O - H ·-- __...-- H ---O-........ __...,.o-
-.,.Cu.,-- 0 S H-bonding exists.
H- 0,;, "o- H / .......... H ---0------ '-..o- Because of the presence ofintramolecular H-bonding, the boiling
1 I point of (B) is lower as compared to (A) and thus, (B) is more
H H volatile, i.e. has higher vapour pressure as compared to (A).
4. Hydrogen bond is simply dipole-dipole attraction within 10. Hydrogen bonding interactions are responsible for the low
oppositely partially charged end. In HF molecule, density of ice as compared to water.
electronegativity difference is remarkable, due to which it 11. During hydration of ions in aqueous solution, there exists an
behaves as a dipole. In the gaseous state several HF molecules attractive force between ions and water molecules, which are
polymerises through H-bonding. polar in nature and acts as dipole. So, hydration of ions in aqueous
o 6+ solution is an example of ion-dipole interaction.
6+ ,-F - H. 6- 12. Among the given, only CHpH and CH3NH 2 are able to form
H' '•F
f/
',, H
"'~
F/ H· bonding
H-bonds, but H-bonding in CH3OH is strong due to high
electronegativity of O-atom. Hence, CH 3OH has the highest
~-........F --- Tj_/ o boiling point.
o 6 13. Ethyl alcohol forms stronger H-bonds than ethylamine or
5. In Cl 2O, oxygen is more electronegative than C l-atom due to ammonia due to greater electronegativity of oxygen than nitrogen
atom. Diethyl ether, however, does not form H-bonds since, it
which a dipole exists within a Cl zO molecule. Further, it is a polar
does not have a H-atom attached to O-atom.
molecule as it has permanent dipole moment.
14. One water molecule is joined to four water molecules-two with
0-
__...,.o-........ H-atoms and other two w ith O-atoms. Thus, the maximu m
CI6+ CI6+ number of hydrogen bonds that a molecule of water can have is
four as shown below :
Due to the presence of a dipole among Cl 2O molecule, the Ho+
positive end of one molecule (dipole) attracts the negative end of
other molecule (other dipole). o+ Io-
Thus, dipole-dipole interactions exists between CI 2O molecules.
H- o
i
Hence, strongest intermolecular forces present in Cl 2O are o+ i o- o+
dipole-dipole forces.
6. Hydrogen bonding is maximum in C2H 5OH (ethanol). o+H
H)5---t/~"'
~
- ~---5(HH o+
7. When H-bonding takes place within a single molecule, this type
o+ "-
o-0-Ho+
of H-bonding is called intramolecular H-bonding. In
o-nitrophenol, H-atom of hydroxyl group is linked to O-atom of 15. Malleability and ductility of metals is due to this sliding capacity
N itro group through H-bonds leading to the formation of a of the delocalised electrons.
ring- like structure.
 Chemical Bonding and Molecular Structure I 93
16. Due to presence of intermoleculatr hydrogen bonding in H 20, its As intermolecular H-bonded compounds have higher boiling
molecules are associated with each other which results unusual points than those of intramolecular H-bonded. Thus, the correct
hig h boiling point of water. order would be
17. Glycerol and ethanol both have intermolecular hydrogen bonding IV<I< II < III
but in glycerol (CH20H ·CHOR · CH20 H) hydrogen bonds per 25. - - - - - - - - - - - - - , - - - - - - - - - -
molecule is more than ethanol (C2H 5 0H) due to the presence of Molecules Interaction
three 0-H groups. It increases attraction between the molecules
and hence, glycerol is more viscous than ethanol. Benzene and ethanol Dispersion force
18. Both O and S belong to the same group but Hp is a liquid while Acetonitrile and acetone Dipole-dipole
H 2S is a gas. This can be explained on the basis of KCI and water Ion-dipole
electronegativity. In water due to the high electronegativity of
oxygen, strong hydrogen bonds are formed. As a result the Benzene and carbon tetrachloride Dispersion (London) force
molecules ofH20 get associated together, hence water exists as a 26. Metals are good conductor of electricity because they contain
liquid at room temperanire. On the other hand, the free electrons.
electronegativity of S is less and therefore, hydrogen bonding in
H 2S is almost negligible. As a result of which molecules ofH2S 27. CH 3COOH dimerises in gaseous state due to H-bonding.
are not associated and H 2S exists as a gas at room temperature. 28. Hydrogen bond is formed between molecules of compounds
19. When hydrogen forms hydrogen bonding with fluorine it will be having 0, F and N with H.
strongest H-bonding because fluorine is most electronegative CHzOH
element. I
H-0- H CHOR
20. Boiling point of HF is highest due to H-bonding. For other (a) I
halogen acids boiling point increases forces with increase in the CHzOH
size of halogen atom because van der Waals increases down the glycerol
group. Thus, the order would be: HCI < HBr < HI. Therefore, (b)
most volatile (with lower boiling point) is HCI. H-F H- S -H
hydrogen fluoride hydrogen sulphide
21. Intermolecular hydrogen bonding is found in H- Fn due to (c) (d)
higher electronegativity of fluorine atoms. Due to this ·: H 2S does not have 0 , For N.
H-bonding, many H-F molecules remains associated with one
another. This intermolecular H-bonding is found to be .·. It does not form hydrogen bond.
responsible for high b.p. of HF. 29. The metals have low ionization energy. In a piece of metal many
free electrons are found which move from one atom to other.
···H - F···H -P. ··H -F· ··
! The presence of mobile electrons or osscillation of loose
Hydrogen bonding
electrons are responsible for metallic lusture.
22. Boiling point of ammonia (NH 3) is much higher than phosphine
(PH 3) . It is due to extensive hydrogen bonding found in Topic 5 Molecular Orbital Theory
ammonia.
1. The molecules which contain unpaired electrons are said to be
H H H paramagnetic in natrue whereas species with paired electrons are
I I I said to be diamagnetic in nature. The molecular orbital
N-H· ··N- H·· N- H con figuration of given molecules are:
I I I
H H H Be 2 (8) ➔ ots20* 1s2 o2s20*2s2 [diamagnetic]
Intermolecular
hydrogen bonding Bz(I 0) ➔ o ts2o • ls2o2s o • 2.s2n2p;1t 2py
2 1
[paramagnetic]
, . , 2•?? 2
23. Ethyl alcohol (C2H 50 H) is soluble in water due to H-bonding. Cz(l 2) ➔ o ts -o ls-o2.s o 2s-n2p;n2pY [diamagnetic]
&- 6+
H - 0:-----H- 0: N 2 (14) ➔ ols2 crls2o2.s 2o*2s21t2p_;n2p;o2p; [diamagnetic]
I I 2. Plan This problem includes basic concept of bonding. It can be
HsCi HsCi solved by using the concept of molecular orbital theory.
Hydrogen bonding
Any orbital has two phase + ve and - ve. In the following
24. Normally, the compounds with large molecular mass boils at a diagram + ve phase is shown by darkening the lobes and - ve by
higher temperature. Thus, the compound IV will have a without darkening the lobes.
least-boi ling point. In remaining isomeric dihydroxy benzenes,
When two same phase overlap with each other it forms bonding
compounds. III, II and I will involve H-bonding. II and III will
molecular orbital otherwise antibonding.
form strong molecular H-bonds while I involve intramolecular
H-bonds.
94 I Chapterwise & Topicwise Engineering Entrances Solved Papers

I
, - +vephase Bond length°" - - - -
Bond order

LJ- -ve phase

Hence, the order of bond length in given series is CF+ <CF< CF-.

4. Two angular nodes are found ind-orbitals. Also for ad-orbital to have one
radial node it must be 4d.
+ + [·: Num ber of radial nodes = n. - I - I]
l l S. Angular nodes = /
~ ~ For 4s orbital, / = 0
Radial nodes = n - I - I
r
Bonding MO
f
Anti-bonding MO
r=4-0- 1=3
Hence, the nwnber of angular and radial nodes of 4s orbitals are 0 and 3
Axial overlapping leads to the formation of cr-bond and respectively.
sideways overlapping leads to the formation of1t-bond. 6. The given statement is true as electron are shi fted more towards the more
electronegative atom.
~ cr-bond
7. Higher the bond order of a molecule, more is the stability of molecular
species.
1t-bond Molecular orbital configuration and bond order of the given species are as
follows:
0 22- (8 + 8 + 2 = 18) = crls2' cr * t s2 ' cr2s2 ' cr * 2s2 ' cr2pz2' n2px2 "'n2pY2 '
On the basis of above two concepts correct matching 1t * 2p; "' 1t * 2p;
can be done as shown below:
Bond order = Nb - Na = I O- 8 = I
2 2
P. --+- d-d cr bonding In, 0 2 (8 + 8 + I = 17), there is one e- less in anti bonding molecular
orbital than Oi-.
1 7
Bond order = Nb - N ° = O - = 1.5
2 2
Q. p-d 1t bonding
--+-
In 0 2(8 + 8 = 16), 3e- are less in anti bonding molecular orbital than o~--
1
Bond order = Nb - N ° = O- 6 = 2
2 2
o; (8 + 8 - I = 15), 3e- 1 less in anti bonding molecular orbital than o~--
R. --+- p-d 1t anti-bonding
Bond order=Nb-Na =IO-S=2.5
2 2
Thus, the order of bond order and stability of given species is
s. --+- d-d cr anti-bonding o~ > 0 2 > 0 2 > o~--
s. In K02, oxygen exists as 0 2 ion. Its molecular orbital electronic
configuration is as follows
:.P ➔ 2,Q ➔ 3, R ➔ I, S➔ 4
0 2 = cr ts2, crls 2 , cr2s2, cr2s2, cr2p;
Hence, (c) is the correct option.
3. The molecular orbital electronic configuration of 1t 2 P.2"'2 2 • 2 2 •21
1t Py, 1t Px "' 1t Py
2 2 2
CF(15e) is crls2, crls cr2s cr2s cr2p; Due to presence of I unpaired electron in anti bonding molecu lar orbital, it
is paramagnetic in behaviour.
1t 2 Px2 "' 1t 22•21
Py, 1t Px 9. Species having zero or negative bond order do not exist.
10- 5 H~+ (I+ I - 2 = 0) = crt s 0
Bond order (BO) = - - = 2.5
2
Bond order= 0
In CF+ there is one electron less in antibonding MO
10-4 Hei (2 + 2 = 4) = crts2, crts2
therefore, BO = - - = 3
2 2 2
Bond order= Nb - N ° - =0
In CF- , there is one electron more in antibonding MO 2 2
10- 6
therefore, BO = - - = 2 So, both Ht and Hei do not exist.
2
 Chemical Bonding and Molecular Structure I 95
2 • ? 2 • 2 2 2 2-2
10. C2 (6 + 6 = 12) = crls , O' Js-, cr2s , cr2s , rc2p_, "" n2py :. Bond order= - - = 0
2
Since, all the e lectrons are paired, it is a dimagnetic species. Since, bond order for Hei molecules is zero therefore,
2• 2 2• 2 2 2 2 according to MO theory, it can ' t exist in stable state.
N 2 (7 + 7 = 14) = crls , crls , cr2s ,cr2s , rc2p, "" n2py , cr2p,
16. Diamagnetic species have all electrons paired, whereas
It is also a diamagnetic species because of the absence of unpaired paramagnetic species have unpaired electrons.
electrons. 2
H 2 = crls
0 2 (8 + 8 = 16) = crls 2 , o l s2, cr2s2, o2s2, Number of unpaired electron = 0 ⇒ diamagnetic
2 2 2 * I * I 1
0'2p, , n2px "" n2py rt 2Px "" rt 2py H2 = cr!s2, O' * ls
Number of unpaired electron= I ⇒ paramagnetic
Similarly, S2 would have one unpaired e- as O and S belongs to same
1
group. Thus, due to the presence of two unpaired electrons 0 2 and Si H ! = crls
both are paramagnetic molecules. Number of unpaired electron= I ⇒ paramagnetic

11. Li 2 (3 + 3 = 6) = crls2, crls , cr2s

2 2 He; = crls2 , cr * Js 1
Number of unpaired electron = I ⇒ paramagnetic
4 2
Bond order = Nb - N ° = - = I
2• 2 2• 2 2 2 2
2 2 17. 0 2 = crls , O' l s ,0'2s ,O' 2s ,0'2p, ,n2px = n2py,
2 2 1
Lii (3 + 3 - I = 5) = crls , crls , cr2s rt• 2Pt=
I • 2 I
rt Py-
3-2 1
Bond order= - - = - = 0.5 In o;, one electron is removed from antibonding MO of
2 2
0 2.
2 2 1
Li:1 (3 + 3 + I = 7) = crls , cr ls2, cr2s o2s , BO for 0 2 = 2 and for o; = 2.5
4-3 I Therefore, paramagnetism decreases, BO increases.
Bond order= - - = - = 0.5
2 2 18. (a) The molecular orbital configuration of
Stability order is Li2 > u; > Li2 C2 = crls
2•
,O'
2 2• 22
ls ,0'2s ,O' 2s , rep.= n2py,0"2p,
2 °

(because Li2has more number of electrons in antibonding orbitals

4
which destabilises the species) B.O. = S- = i=2
2 2
12. 0
- _
2
2• 2 2 * 2
- 0' ls crls ,cr2s ,cr2s ,cr2p, ,rt2px=rt2py,rt2px - rt2py
2 2_ 2 * 2 _ • I
In c;-, 2e- are more in bonding MO, thus
1 7
Bond order= Nb - N ° O- = = J.5 2 B.O.= 10-4 =~=3
2 2 2 2 2
13. In oxygen molecules, 0 2 (8 + 8 = 16) Since, B.O. oe - - - -
Bond length
C2 > c~-
? 2 • I • I
rt2p; "" rt2py, rt 2p_, "" rt 2py Thus, trne
2
Thus, it contains two unpaired electrons. (b) B2 = crls ,cr• Js2 ,cr2s2,cr' 2s2,rc2px' = n2pj
14. B 2 = 5 + 5 = !0e- = crls2, cr * Js2, cr2s2, cr *2s2, rc2p; "" rc2p~ 6 4
BO= - =3_=1
2 2
Due to the presence of two unpaired electrons in re-bonding orbitals,
In B; ,le-is less in bonding MO
B 2 shows paramagnetic behaviour.
2 5 4
15. H 2 = crls BO= - = _.!_ = 0.5
2 2
N -N O 2-0
: . Bond order = b = --= I Thus, B; > B 2
2 2
2 2
Hi = crls
1 (c) Li 2 = crls2,cr'Js ,cr2s
1-0 4-2 2
: . Bond order = - - = 0.5 BO= - - = - = 1
2 2 2
H;: = crls2, O' * ls
1 In u;, le- is less in bonding MO, thus
2-1
: . Bond order = - - = 0.5 u+ ⇒ BO= 3 - 2
= .!._ =0.5
2 2 2
Hei = cr!s2, O' * l s
2 u; > u 2
96 I Chapterwise & Topicwise Engineering Entrances Solved Papers
24. Peroxide ion is o~-
N 2 = o- Is 2,o-• Is 2,o-.,,,,
,., .2 • ,.,. 2 2 2 2 2
'o- ;.,,· ,1t Px = 1t 2 Py,0- 2 P,
o~-(18) = o-ls2, cr 1s2, o-2s2, cr2s2, o-2p;
BO= 10-4 = 3
2 n2p; = 1t2p; , n2p; = 1t 2p;
In N;, le- is less in bonding MO, thus
Bond order = Nb - N ° = IO - 8 = I
+ 9-4 2 2
N 2 BO= - - =25
' 2 It contains four completely fi lled antibonding molecular
Thus, N; >N2 orbitals. Since, all the electrons are paired, o ~- is diamagnetic.
Peroxide ion is isoelectronic with argon, not with neon.
(e) 0 2 - o-ls ,o-ls ,o-2s ,o- 2s ,o-2p,2 ,1tpx2_
_ 2• 2 2 • 2
- 1t2py2
• L
25. Species 02 o; Oi+ o~-
1t 2p, = 1t• 2pyI
Bond order 2 2.5 3
BO= 10-6 = 2 Hence, the increasing bond order is as follows :
2
In 02 one e- is more in anti bonding MO, thus
ot
< 02 < o; < o~+
10 -7 3 26. (i) N 2 (14 electrons)= KK*, o-2s2,
0 2 BO=- - = - = LS • 2 2 2 2
' 2 2 o-2s , 1t2px "' 1t2py, o-2p,
Thus, 0 2 > 02 I I
Bond order= - (Nb - N O )= - (8 - 2) = 3
Hence, (e) is not correct. 2 2
19. NO is paramagnetic in nature. as it has I unpaired electron in (ii) N; ( 13 electrons)= KK*, o-2s2,
antibonding n2px orbital. NO = o-ls 2,o-•1s2,o-2s2,o-•2s2,o-2p;,
·2s 2 , 1t 2Px2 "' 1t 2Py,
2 0- 2P,1
1t 2 Px2 = 1t 2 Py,
2
1t•2Px1 = 1t•2Py1 0-
1
20. B 2 : Total electrons = JO Bond order = - (7 - 2) = 2.5
2
Configuration= o-ls2,cr ls2,o-2s2,cr2s2, 1t2p; = 1t2p~ Since, bond dissociation energy <X bond order. Hence, bond
IfHund's mle is violated, then dissociation energy ofN2 is greater than that of bond dissociation
energy ofN;_
o-ls 2' cr ls 2' o-2s2' cr2s 2' 1t2pX2 = 1t2py0
27. Higher the bond order, shorter the bond length. Thus, o ~+ has the
So, diamagnetic shortest bond length (BO = 3)
6-4
Bond order= - - = I Bond order of remaining species are:
2
Oi (2.5), 0 2 (1.5) and o~- (I)
21. Bond order <X - - - - BO of NO < BO of NO+ 28. Species having the same number of electrons, have same bond
bond length
order.
: .Bond length of NO is greater than the bond length of NO+.
Species Number of electrons
22. 1t2px and n2py or 7t 2px and 7t 2py orbitals have nearly equal rn- 6+ 7 + 1=14
energy and thus, are called degenerate orbitals. o-2 8+8+1= 17
23. Oi(l6) = o-ls 2, cr ls 2, o-2s 2 , cr 2s 2 , o-2µ;, NO+ 7 + 8- I= 14
CN+ 6 + 7 - I= 12
1t 2Px2 "' 1t 22•21 • 21
Py, 1t P, "' 1t Py,
Since, CN- and NO+ have same number of electrons, they have
BO =I0- 6 =2
2 same bond order, i.e. 3.

Ot(l 8) = o-ls2, cr ls2, o-2s2 , cr2s2, o-2p;, CN- or NO+ = 14 = o-ls2, crls2, o-2s2, cr2 s2,
2 2 2
0-2p,, 1t2px "' 1t2py
1t 2 Px2 "' 1t 22•22
Py, 1t Px "' 1t•22
Py
N - N0 10 - 4
Bond order = b - - =3
BO= 10- 8 = I 2
2
2
29. The MO electronic configuration of
N 2 (14) = o-ls2, cr ls2, o-2s2, cr2s2,
0 2 (8 + 8 + I = 17) = o-ls2, cr ls2, o-2s2, cr 2s2,
1t2p; "' 1t2p;, o-2p;
2 2 ·2Py1
0- 2P,, 1t 2Px "' 1t 2Py,
' 1t
*2 p;' "' 1t
BO= 10 -4 =3
2 Bond order = Nb - N ° = 1O - 7 = I. S
Thus, bond order is highest for N 2. 2 2
 Chemical Bonding and Molecular Structure I 97
(iii) NO (15) =
30. (i) Nz ➔ (crtd,(o td ,(cr2s)2, (o2s)2,(cr2p,)2 ,(7t2px)2
= (1t2py)2 crls 2· bts2, cr2s2, b2sZ.,
2 1t 2Px2 = 1t 2 Py,
O' 2P,, 2 1t •2PxI = 1t 2Py
•
2
Ni ➔ (crls) ,(o ls) ,(cr2s)2 ,(b 2s)2 ,(cr2p,)2,
2
10- 5
(1t2px)2 = (7t2py)l Bond order = - - = 2 .5
2
(ii) 0 2 ➔ (crls)2,(ols)2,(cr2s)2, (o 2s)2,(cr2p, )2, (1t2p.)2= (iv) NO 2+ (13)= crls 2, b ls2, cr2s2 , b 2s2 , cr2p; 1t2p; = n2p!
(1t2py)2 ,(n. 2Px) 1 = (rt 2py)1 9-4
Bond order = - - = 2.5
2
o; ➔ (crls)2,(ols)2.(cr2s)2,(b2s)2,(2p,)2
2 2
(v) NO - (17)= crJs2·, ols2, cr2s2, o2s
(1t2px)2 = (1t2py)2,(n 2Px)1= (x2p;)
2
O' 2P, , 1t
2Px2 = 1t 2Py,
2
1t•2Px2 = 1t•2 PyI
Since, 1t2px and 1t2py are nearly same in energy, the electrons can
be removed from (1t2py or 1t2px) and (n.2py orrt2px) 10- 7
Bond order = - - = 1.5
respectively. 2
31. According to the mo lecular orbital theory, 1t-bonding orbitals are The order of bond order is
ungerade. No 2- < No- < NO 2+ "'NO < NO+
32. Isoelectronic species have same number of electrons, (IV) (TTI) (II)
0') (I)
NO+, c~-, CN- and N 2• All have 14 electrons.
33. In an antibonding molecular orbital, most of the electron density is
located away from the space between the nuclei, as a result of
which there is a nodal plane (i.e. a plane at which the electron
density is zero) between the nuclei. - 2• 2 2• 2 2 2 2
Nodal plane NO (16)=<1ls ,crls ,cr2s ,cr2s ,<12p,, (1t2p, =1t2py),
• I
1t 2Px = 1t• 2pyI
BO=I0 - 6=2
2
s s s NO+ (14); BO = 3

34. RbO2means Rb+ and o ; , o; is the superoxide ion. CN- ( 14) ; BO = 3

N 2 (14); BO = 3
0 2(17) = crts2, CJ Is2, cr2s2, cr2s2, cr2p;, Hence, bond order of NO- is different from that of CO.
1t 2Px2 "'1t 22•22 •21
Py,1t Px "' 1t Py 38. For KO 2 , 0 2 has one unpaired electron so, it is paramagnetic.
As it contains one unpaired electron, thus paramagnetic in nature. 0 2(17) = crts2,crls2, cr2s2, cr2s2·, cr2p;
35. According to molecular orbital theory,
(7t 2p; = 1t2p;), 7t 2p; = 1t·2p1
Fz(IS) = crts2, crts2, cr2s2, cr2s2 cr2p;, 1t2p;
39. NO -----t NO+
? • , • ,
"'1t2p;, 1t 2p;,"' 1t 2p; (NOt Total e- = 14
N -NO 10-8
: .Bond order in F2 = b =--= 1 O' 1s 2•12
,O' s ,O' 22•22
s ,O' s ,1t 22
Px =1t 22
Py, O' 22
P,
2 2
36. (i) NO(16)accordingtoMOT. Diamagnetic
10-4
Bond order= - - = 3
O' Is 2,O'• , s 2 ,O' 2s 2,O'•2s 2,O'2 P,,
2
1t 2Px2 = 1t 2Py,
2 1t
* 2 PxI = 1t
• 2 I
Py 2
Bond order (NO) Total e- = 15
bonding electrons - antibonding electrons ,•' -, • 2 2 2 2• I • I
crls- ,O" is- ,cr2s-,cr2s , cr2p, , n2px, 1t2py, 1t 2p. or 1t 2py
2
Paramagnetic
= 10 -6=2 10- 5
2 Bond order = - - = 2 .5
2 2 2 2 2 2 2
(ii) NO+(t4) =crls , cr•ts , cr2s , cr'2s2, 1t2p.t =1t2pY' cr2pz
Electron is taken away from non-bonding molecular orbital
10-4 that's why bond order increases.
Bond order = - - = 3
2
98 I Chapterwise & Topicwise Engineering Entrances Solved Papers

40. The correct option is o~- . This species has 18 electrons, which are Bond order of peroxide ion (O~- ) = 1
filled in such a way that all molecular orbitals are fully filled, so Hence, the order of bond strength is as
diamagnetic. o; > 0 2 > o;: > o ~-
crls2,; t s2,cr2s 2,;2s2,cr2p;, rc2p; = rc2p;,;2p; = ;2p;
50. o; (15[) = KK• (cr2s)2 (cr2 s)2
41. Cl 20 = 42 electrons
(cr2p,)2, (rc2py)2 = (n2px)2
IC1 2 = 88 electrons
(rc.2py) 1 = (rc.2px)0
Cl2 = 35 electrons
1
IF{ = 70 electrons Hence, bond order= - (10- 5) = 2.5
2
I; = 160 electrons
N; (l 3e- ) = KK• (cr2s)2 (cr 2s)2
CI02 = 33 electrons 1
(n2py)2 = (rc2px)2 ,(cr2p,)
CI02 = 34 electrons
1
CIF{ = 34 electrons Hence, bond order= - (9 - 4) = 2.5
2
CI02 and CIF{ contain 34 electrons each hence, they are 51. Molecular orbital theory was given by Mulliken.
isoelectronic.
52. Isoelectronic species are those species which have equal
42. Bond order °" Stability. Hence, for a stable molecule the value of number of electrons. Hence, CO2 is isoelectronic w ith N 20.
bond order must be positive. When bond order is zero the molecule
Number of electron in CO2 = 22
w ill not exist.
Number of electron in N 20 = 22
43. The electronic configuration of o~- ion is
53. Molecular orbital configuration ofN; is
0 22- = crls2•
, cr ls2,cr2s2•
, cr2s2, cr2p,2 re 22
p, = re 22•22 •22
Py, re Px = 1t p> N; =(crls)2, (cr ls)2 ,(cr2s)2,(cr2s)2
Hence, number of antibonding electron pairs in o~- molecular ion (n2p_j = (n2py)2,(cr2p, )
1

are four.
Bond order= Nb - N ° =
9 - 4 = 2.5
44. tt; = crls2 (According to molecular orbital theory) 2 2
bonding electrons - anti bonding electrons 1
Bond order= - - - - - - - - - - - - - - = - = 0.5 54. 0 ~+ has 14 electrons. Its electronic configuration is as
2 2 + 2 • 2 2 •2 2 222
0 2 =crl s ,cr ls ,cr2s ,cr 2s ,n2py=1t2Px,cr p,
H; is paramagnetic due to the presence of one unpaired electron.
Nb -N0 10 -4
45. N 2 molecule has 14 electrons. The molecular orbital electronic Bond order= =--= 3
2 2
configuration of the molecule is as
55. Bond order°" stability
N 2 = KK (cr2s)2(cr• 2s)2(rc2px)2 = (n2py)2(cr2p,)2
Species Bond order
N; ion is formed when N 2 accept an electron hence, it has 15 2.5
electrons. The molecular o rbital electronic configuration of the
2.0
molecule is as
1.5
N 2 = KK (cr2s)2 (cr• 2s)2 (1t2px)2(rc2py)2 (cr2p,)2 (ic 2pj
Hence, the order of stability is o; > 0 2 > 0 2
Hence, this electron goes to antibonding re molecular orbital. I
56. Bond length °" - - - -
46. Energy bonds in solids are formed in accordance with Bohr's theory. Bond order
47. o ~- (Total number of electrons= 18)
NO- = l 6e- = crls2, cr ls2, cr2s2, cr2s2,cr2p;
crls2,cr
• l s 2, cr2s2, cr2s
• 2,cr2p,,
2 n2p,2_ 2 • 2µ_.2_•2
- rc2py,rc - n Py2 2 2 I •2 I
1t2Px = n2py, 1t2Px = re Py
48. CO, CN- and NO+ all the three species have 14 electrons. BO = Nb - Na = 10 - 6 = = 2 i
According to MOT 2 2 2
Similarly, BO of NO+ w ill be calculated as
crls 2, crls 2, cr2s 2,cr2s 2,cr2p;, (rc2p; = rc2p;)
NO+= 14e-
10-4
Bond order= - - = 3 4
2 BO= l0 - =3
2
Similarly, bond order for o; = 2.5
CN- = 14[, B0 =3
49. Bond order of oxygen molecule = 2
9 4
Bond order of oxygen mo lecule ion = 2.5 CN+ = 13e- , BO = - =2.5
2
Bond order of superoxide ion (0 2)= 1.5
Bond order is least for No- . So, its bond length is highest.
 Chemical Bonding and Molecular Structure I 99
57. A species is said to be diamagnetic ifit has all electrons paired.
MO electronic Magnetic
Species Electrons
configuration behaviour

ff2 3 1 Paramagnetic
crls2 cr ls
H+ 1
2
I crls Paramagnetic

H2 2 crls2 Diamagnetic

He;: 3
crls2cris
1 Paramagnetic

58. Species Electron in Electrons in Charge gained Total

central element other element

BO~ 5 3 X 8 = 24 3 32

co~- 6 3 X 8 = 24 2 32

NO3 7 3x8=24 I 32

so~- 16 3 X 8 = 24 + 2 42

cw 6 7 I 14

N2 7 7 0 14

c~- 6 6 + 2 14

Pot

so!-
I~ 15

16
(\j 4

4
X

X
8 = 32

8 = 32
+ 3

+ 2
I

~
50

50

CIO4 17 4 X 8 = 32 + 1 50

Thus, (b) sot-, CO~- , NO3 are not isoelectronic.

2
59. Bez = (8 electrons) crls2 cr ls2cr2s2 cr 2s
60. The molecular orbital electronic configuration.
(cr Is)2 ( cr Is )2(cr2s )2(er 2s )2(o-2 pj

(1t2py)2(1t2p, )2(rr, 2py)2(rr, 2p, ) 1

Total electrons= 17
Hence, this configuration belongs to 0 2(17e- ) ion.
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States of Matter
QUICK REVIEW
• Matter exists in three states namely solid, liquid and gas. • Ideal gas equation, pV = nRT, R is known as universal
• State of matter is the result of combined effect of gas constant or molar gas constant.
intennolecular forces and thermal energy. Values of R = 0.0821 L atm K- 1 rno1- 1
• In the gaseous state of a substance, the intermolecular
= 8.314x 107 ergs K - 1rno1- 1
spaces are the maximum and intermolecular forces are the
minimum. = 8.314 JK- 1 mol- 1
= l.987 ("" 2) cal K- 1mo1- 1
Gas Laws . pV pV
• The gases exhibit uniformity in their behaviour. These are • General gas equation, - 1 1
- =~
Ti T2
governed by gas laws.
I • Graham's law of diffusion, rate of ruffusion of a
• Boyle's law, Vex: - or pV = constant gas,
p
(at constant p and 1)
or P, Vi = pzV2
V

~ =✓::
• Charles' law, Vex: Tor - = constant (at constant p and 1)
T =~

• Rate of diffusion, rcx: _k (at constant T)

or __!?!_ = _____!!!_(·:V =
d 1I; d 2 T2
m) or d 7; = d T
d
1 1 2
or !l_=.E!__ ✓M2
r2 P1 Mi
where, m = mass, d = density, T = temperature,
p = pressure and V = volume
Also, ~= ✓M2
n2 Mi
• Pressure-Temperature law, p ex: Tor p = constant
!!_ = ✓M2
T
Further
or.E!_ = P2 12 M1
Ti Tz
• Avogadro's law , Vex: n or V = kn where, / 1 and 12 are length travelled by gas I and gas 2,
respectively.
where, n = number of moles of the gas
• Molecular mass of a gas = 2 x Vapour density
V = volume of the gas
k = proportionality constant Dalton's Law of Partial Pressures
Since, l mol = 6.022 x 1023 molecules = NA molecules • P = Pi + P2 + P3 + · · ·
where, NA = Avogadro's number where, p 1 , p 2 , . •. are partial pressures of components of
gases.
n ex: N or Vex: number of moles of gas
 States of Matter I 101
Partial pressure = Total pressure x Its mole fraction • Z = I for an ideal gas at all the conditions. The values of Z
(Dalton's law is valid for gases which do not react exhibits both positive (Z> I) and negative deviations
chemically). (Z < I) from unity.
Partial pressure of water vapours in moist gas is referred as • For H 2 and He gases, pV> RT, i.e. Z> I or
aqueous tension. V111 > 22.4 Lat NTP (V111 is actual molar volume of gas).
P dry gas = P moist gas - P water vapour • All gases have Z"' I at low pressure. At intermediate
= p moist gas - aqueous tension pressure and 273 K , some gases such as CH 4 , NH3 , CO,
etc., have Z < I and at high pressure, all gases have Z> I.
• Molar mass and density : d = pM
RT • An increase in temperature shows a decrease in deviation
from ideal gas behaviour, i.e. p Vapproaches RT with rise in
Kinetic Gas Equation temperature of Z approaches unity.
I 2
• pV =- mNu • Boyle temperature is the characteristic temperature of the
3 gas at which it obeys ideal gas nature. Below this
(where, m = mass of each molecule, N = total number of temperature, the value of Z at first decreases, approaches a
molecules, u = rms velocity) minimum and then increases as the pressure is increased
I continuously. Deviation from ideality is studied by plotting
For one mole of gas, pV = - Mu 2 a graph between compressibility factor ( Z) and pressure (p).
3
Z = P V or Z = Molar volume of real gas at STP )
as m x N = molecular mass (M)
( nRT Molar volume of ideal gas at STP
Root Mean Square Velocity of the Gas It is seen that
u =)3pV
rms M tI N
2/
,-H2

or
3
) : or ff t-
a:
-!:.
~
-
~., -_-:-----
/
. , / ___ __
-' C~~--- ·He
CO2

Most probable velocity, ump = )2:; N

11

. uav = ✓8RT
Average ve1oc1ty, 1CM
I
- - - - - p (atm) - - - --+
Deviation of gases from ideality
Relationship between velocities,

Urms : Uav : ump = ✓3 : J! :✓2 van der Waals' Equation

• Two faulty assumptions of kinetic theory due to which real
= 1.2248 : 1.1284 : I gases deviate from ideal behaviour are as follows:
Urms = 1.2248 Ump (i) The actual volume occupied by particles of gas is
Uav = 1.1284 Ump negligible as compared to the total volume of the gas.
urms = 1.0854 uav (ii) The forces of attraction or repulsion between the
particles of gas are negligible.
Kinetic Energy of Gas The modified gas equation or van der Waals' of state.
3
KE =
2
kT,
(p +; 2
2
) (V - nb) = nRT (forn moles ofgas)
where, k = _!!__ is known as Boltzmann constant.
No where, a and b are pressure correction and volume
correction, respectively. Units ofa are atm L2 mo1- 2 or
Deviations from Ideal Gas behaviour atm m 6 mo1-2 orNm 4 mo1.- 2
T he deviations from ideal gas behaviour are expressed in
Units of bare L mol- 1 or m 3 mol- 1
.
terms of compressibility factor (Z).
pV pV • Critical constants Critical temperature (Tc ) is the
Z =-=- (for I mole) maximum temperature at which a gas can be liquified.
nRT RT
102 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Critical pressure (pc )is the minimum pressure which is required to liquify a gas. Critical volume (Ve ) is the volume of one mole
of gas which is occupied at critical temperature and critical pressure . In terms of van der Waals' constants a and b,
8a a
Tc = 27Rb 'Pc = 27bz ,Ve = 3b

• Liquid state Vapour pressure, smface tension and viscosity are some of the typical physical properties of liquids that arise
due to two competing forces, the molecular interaction and them1al energy. Variation of vapour pressure with temperature is
given by Clausius-Clapeyron equation.
Mi
l vap A
og p =- 2.303RT +
• Surface tension It decreases when substances such as soaps, detergents are dissolved in a liquid. Rise in temperature also
decreases surface tension.
• Viscosity It is defined as the resistance ofa liquid to flow. Usually, viscosity ofa liquid decreases with the rise in temperature.

Topic 1
Gas Laws and Ideal Gas Equation
2014
Directions (Q. Nos. 1-2) Read the following information and 3. The ratio of masses of oxygen and nitrogen of a particular
answer the following questions. gaseous mixture is 1 : 4. The ratio is number of their
X and Y are two volatile liquids with molar weights of molecule is [JEE Mains]
1 1
10g rnol- and 40g mol- , respectively. Two cotton (a) 1 : 4 (b)7: 32 (c) 1 : 8 (d)3: 16
plugs, one soaked in X and the other soaked in Y, are 4. A gaseous mixture containing He, CH 4 and S02 was
simultaneously placed at the ends of a tube of length allowed to effuse through a fine hole, then find what molar
L = 24 cm, as shown in the figure. ratio of gases coming out initially? (Given mixture
The tube is filled with an inert gas at 1 atm pressure and a contains He, CH4 and S02 in 1 : 2 : 3 mole ratio).
temperature of300 K. Vapours ofX and Y react to form a
product which is first observed at a distance d cm from (a) ✓2:✓ 2:3 (b) 2 : 2: 3 [VITEEE]
the plug soaked in X Take X and Y to have equal (c) 4: 4: 3 (d) 1 : 1 : 3
molecular diameters and assume ideal behaviour for the 5. Density of carbon monoxide is maximum at [KCETJ
inert gas and the two vapours. [JEE Advanced]
(a) 2 atm and 600 K (b) 0.5 atm and 273 K
L=24 cm (c) 6 atm and 1092 K (d) 4 atrn and 500 K
' ' 'I 6. For one mole ofan ideal gas, the slope of V versus T curve
'' 'I at constant pressure of2 atm is XL mol- 1K - 1 . The value
I

' of the ideal uni versa] gas constant R in terms of Xis

Cotton wool Initial formation of
soaked inX the product
(a)XLatmmol- tK- 1 CWB JEEJ
1. The value of d (in cm) shown in the figure, as estimated (b) XL atmmol- ' K - 1
from Graham's law, is 2
(a) 8 (b) 12 (c) 16 (d) 20 (c) 2X L atmmol- tK- 1
2. The experimental value ofdis found to be smaller than the (d)2X atmL- 1 mol- 1K - 1
estimate obtained using Graham's law. This is due to
7. At a certain temperature, the time required for the complete
( a) larger mean free path for X as a compared to that of Y diffusion of200 mL ofH 2 gas is 30 min. The time required
(b) larger mean free path for Y as compared to that ofX for the complete diffusion of 50 mL of 0 2 gas at the same
( c) increased collision frequency of Y with the inert gas as
temperature will be [WB JEE]
compared to that of X with the inert gas
( d) increased collision frequency of X with the inert gas (a) 60 min (b) 30 min
as compared to that of Y with the inert gas (c) 45 min (d) 15 min
 States of Matter I 103
8. The ratio of rates of diffusion of gases X and Y is 1 : 5 and 16. In which one of the following does the given amount of
that of Y and Z is 1 : 6. The ratio of rates of diffusion of Z chlorine exert the least pressure in a vessel of capacity
3
and Xis [EAMCET] l dm at 273 K? [KCETJ
(a) 1 : 30 (b) 1 : 6 (a) 0.0355 g (b) 0 .071g
(c) 30 : 1 (d) 6 : 1 21
(c) 6.023 x 10 molecules (d) 0 .02 moles

2013 2009
9. The rate of diffosion of methane at a given temperature is 17. 0.5 mole of each of H 2 , S02 and CH 4 are kept in a
twice of a gas X The molar mass of the gas Xis [KCET]
container. A hole was made in the container. After 3 h the
(a) 64 (b) 32 (c) 16 (d) 8 order of partial pressures in the container will be
1O. If p, T, p and R represent pressure, temperature, density (a) Pso2 > PH2 > PCH4 [Manipal]
and universal gas constant respectively, then the molar
mass of the ideal gas is given by [OJEEl (b) Pso2 > PCH4 > PH2
(c) PH 2 > Pso2 > PCH4
(a) pRT (b) pT (c) ___E_ (d) RT
p pR pRT PP (d) PH 2 > PcH 4 > Pso2
18. 1O mL of oxygen and l O mL of hydrogen is kept at the
2012 same temperature and pressure, which is co1rect about
number of molecules? [OJEEJ
11. A gas is heated through 1°C in a closed vessel and so the
pressure increases by 0.4%. The initial temperature of the (a)No2>NH2 (b)No2<NH2
gas was [BITSAT] (c)No2 = NH2 (d)No2 = NH2
(a) -23° C (b) +23° C 19. Two vessels containing gases A and Bare interconnected
(c) 250°C (d) 523°C as shown in the figure. The stopper is opened, the gases are
allowed to mix homogeneously. The partial pressures ofA
12. The ratio of diffusion of hydrogen and helium gas is
and Bin the mixture will be, respectively. [GPETJ
(a) 1 : 1.4 (b) 1 : 1 [Manipal]
( c) 1.4 : 1 (d) 1 : 2 GasA

2011
13. To an evacuated vessel with movable piston under external (b) 9.6 and 4 atm
(a) 8 and 5 atm
pressure of 1 atm, 0 .1 mole of He and 1.0 mole of an
(c) 4 .8 and 2 atm ( d) 6.4 and 4 atm
unknown compound (vapour pressure 0.68 atm at 0°C) are
introduced. Considering the ideal gas behaviour, the total
volume (in litre) of the gases at 0°C is close to [IIT JEE]
2008
20. In order to increase the volume of a gas by 10%, the
(a)3 (b)5 (c)7 (d)9 pressure of the gas should be [KCETJ
14. When r, p and M represent rate of diffusion, pressure and
(a) increased by 10% (b) increased by 1%
molecular mass, respectively, then the ratio of the rates of
( c) decreased by 10% ( d) decreased by l %
diffusion (rA I r8 ) of two gases A and B, is given as
21. Diffusion of helium gas is four times faster, than [UPSEE]
(a) (PA I p 8 )1'2 (MA I M 8 ) [AIEEE]
(a) CO2 (b) S02 (c) N02 (d) 02
(b)(PA I Pn)(Mn I MA )1' 2 22. A 4 : 1 mixture of helium and methane is contained in
2 vessel at 1Obar pressure. Due to a hole in the vessel, the gas
( C) ( p A / p B )1' (MB /MA )
mixture leaks out. The composition ofmixture effusing out
(d)(pA I Pn)(MA 1Mn>1' 2 initially is [Guj CETJ
(a) 8: 1 (b) 8: 3 (c) 4: 1 (d) 1 : 1
2010 23. Identify the pair of gases that have equal rates of diffusion
15. Iflo- 4 dm 3 ofwaterisintroducedintoaldm3 flaskat300 (a) CO, NO (b) N20, CO [J &K CET]
K, how many moles of water are in the vapour phase when (c) N 20, CO 2 (d) CO2 , N02
equilibrium is established (given, vapour pressure of H2 0
1 1 24. If two molecules ofA and B having mass 100 kg and 64 kg
at 300 K is 3170 Pa, R = 8.314 JK- rnol- } [AIEEE] and rate ofdiffusion ofA is 12 x 10- 3 , then what will be the
(a) 5.56x 10- 6 mol (b) l.53x 10- 2 mol rate of diffusion of B? [BCECEJ
(c) 4.46x 10- 2 mol (d) l.27x 10- 3 mol (a) 15xl0- 3 (b)64xl0- 3 (c)5x10- 3 (d)46x10- 3
104 I Chapterwise & Topicwise Engineering Entrances Solved Papers
25. The density of a gas is 1.964 g dm- 3 at 273 Kand 76 cm 32. The density of 0 2 is 16 at NTP. At what temperature its
Hg. The gas is [Jamia Millia Islamia] density will be 14? Consider that the pressure remains
(a) CH4 (b) C 2 H 6 (c) CO2 (d) Xe constant, at [DCEJ
(a) 50°C (b) 39°c
2007 (c) 57°C (d) 43°C
26. Dalton's law of partial pressure is applicable to which one
of the following systems? [KCETJ 2006
(a) NH 3 + HCI (b) NO + 0 2 33. Which of the following is a Boyle plot at very low
(c) H 2 + Cl 2 (d) CO + H2 pressure? [BITSATJ
27. Which one of the following volume (V)- temperature (T)
plots represents the behaviour ofone mole ofan ideal gas at
one atmospheric pressure?

V(L)r:68L
373 K V(L) r : 8
[Kerala CEEJ

.6 K
373 L
(b) pVL
pVL
p

( a). 22.4
273 K
L (b) 22.4L
273 K
(d)
T(K) T(K)

V ( L ) r373
:0.6L p p
K V(L) ~
34. The molar volume of CO 2 is maximum at [BITSATJ
(c) 22.4 L d 22.4 L (a) NTP (b) 0°C and 2 .0 atm
273 K ()273K 14.2L
373 K (c) 127°C and l atm (d) 273°C and 2 atm
T(K) T(K) 35. Correct gas equation is [ManipaIJ

(e)~'.L~~
273 K 15.0 L
373 K
(a) Pt Tl = P2T2
Vi
(C) Pt Vt
P2V2
V2
= !j_
T2
(b) VtTz = V2Tt
Pt
(d) Vt V2
- = P1P2
T., T2
P2

T(K)
36. A gaseous mixture contains 56 g ofN2 , 44 g of CO 2 and
28. Dalton's law of partial pressure is not applicable to 16 g of CH 4 . The total pressure of mixture is 720 mm of
(a) 0 2 + 0 3 (b) CO + CO2 CWBJEEJ Hg. The partial pressure of methane is [WB JEE]
(c) NH 3 + HCI (d) I + 0 2 (a)75atm (b)l60atm (c)l80atm (d)215atm
29. A bubble of volume Vt is in the bottom of a pond at l 5°C 37. Calculate the total pressure in a 10.0 L cylinder which
and 1.5 atm pressure, When it comes at the surface, it contains 0.4 g heliwn, 1.6 g oxygen and 1.6 nitrogen at
observes a pressure of l atm at 25°C and have volume V2 , 27°C. [UPSEEJ

then V2 is equal to: [AMU]

(a) 0.492 atm (b) 49.2 atm
Vt (c) 4 .92 atm (d) 0 .0492 atm
(a) 15.5 (b)0. 155 38. 6.4 g of SO2 at 0°C and 0.99 atm pressure occupies a
(c) 155.0 (d) 1.55 volume of 2 .241 L. Predict which of the following is
30. A certain mass of a gas occupies a volume of 2 L at STP. C01Tect? [OJEE]
To what temperature the gas must be heated to double its (a) The gas is ideal
volume, keeping the pressure constant? [EAMCETJ (b) The gas is real with inte1molecular attraction
(a)l00K (b)273K ( c) The gas is real without intermolecular repulsion
(c) 273°C (d) 546°C (d) The gas is real with inte1molecular repulsion greater
than intermolecular attraction
31. Gas equation pV = nRT is obeyed by ideal gas in
39. The pressure and temperature of 4 dm3 of carbon dioxide
(a) adiabatic process CBCECEJ
gas are doubled, then the volume of carbon dioxide gas
(b) isothem1al process
would be [AMUJ
(c) Both (a) and (b) 3
( d) None of the above (a) 2dm3 (b) 3dm (c) 4dm 3 (d) 8dm3
 States of Matter I 105
40. The volume-temperature graphs ofa given mass ofan ideal 4 7. Charles' law is represented mathematically as [BITSAT]
gas at constant pressures are shown below. What is the
(a) V, = KV0 t (b) V1 = KVo
correct order of pressures?
t

i
V
(c) v, = V0 (1 + 2;3) (d) V1 = V0 ~J
(1 + 2
48. Which gas has the highest partial pressure atmosphere?
(a) CO2 (b) H2O [BITSAT]
(c) 0 2 (d) N 2
0 273 T(K}---+ [EAMCET] 49. In the equation ofstate ofan ideal gas pV = nRT,the value
of the universal gas constant would depend only on
(a) P, > p3 > P2 (b) Pt > P2 > P3
(a) the nature of the gas [KCET]
(c) P2 > P3 > Pt (d) P2 > Pt > P3
(b) the pressure of the gas
41. A gas ofunknown identity effuses at the rate 83.3 mLs _, in
( c) the units of the measurement
an effusion apparatus in which carbon dioxide effuses at
(d) None of the above
the rate of 102 mLs _, . Calculate molar mass of the
50. If the absolute temperature of a gas is doubled and the
unknown gas. [Guj CET]
pressure is reduced to one half, then the volume of the gas
(a) 6.597 g rnol- t (b) 65.97 g mol- 1 will [Kerala CEE]
(c) 3.650 g rnol- t (d) 36.50 g mol- 1 (a) remain unchanged (b) be doubled
42. A, Band Care ideal gases. Their molecular weights are 2, 4 (c) increase four fold (d) be halved
and 28, respectively. The rate of diffusion of these gases (e) be reduced to one-fourth
follow the order [J&K CET] 51. To what temperature must a neon gas sample be heated to
(a)C>A>B (b)C>B>A double its pressure, if the initial volume of gas at 75°C is
(c)A = B = C (d)A>B>C decreased by 15.0%? [Kerala CEE]
43. If both oxygen and helium gases are at the same (a) 319°C (b) 592°C (c) 128°C
temperature, the rate of diffusion of 0 2 is very close to (d) 60°C (e) 90°C
(a) 4 times that of He [BCECE] 52. If the temperature of 500 mL of air increases from 27°C to
(b) 2 times that of He 42°C under constant pressure, then the increases in volume
(c) 0.35 times that of He shall be [AMUJ
(d) 8 times that of He (a) 15 mL (b) 20 mL (c) 25 mL (d) 30 mL
44. 10 g each of CH4 and 0 2 are kept in cylinders of same 53. NH 3 and HCI gas are introduced simultaneously from the
volume under same temperature, give the pressure ratio of two ends of a long tube. A white ring of NH 4 Cl appears
two gases. [DCE] first [RPET]
(a)2 :1 (b)l:4 (a) nearer to the HCl end (b) at the centre of the tube
(c)2:3 (d)3:4 (c) throughout the tube (d) nearer to the NH3 end
54. Two gas cylinders having san1e capacity have been filled
2005 with 44 g of H2 and 44 g of CO2 respectively. If the
45. The ratio of th e rate of diffusion of helium and methane pressure in CO2 cylinder is 1 atrn at a particular
under identical condition of pressure and temperature will temperatw·e, then the pressure in the hydrogen cylinder at
be [IITJEE] the same temperature is [RPETJ
(a) 4 (b)0.2 (a) 2 atm (b) 1 atrn
(c) 2 (d) 0.5 (c) 22 atm (d) 44 atrn
46. Graham's law deals with the relation between [BITSAT] 55. For an ideal gas, number of mol per litre in terms of its
(a) pressure and volume pressure p, temperature T and gas constant R is
(b) density and rate of diffusion [Jamia Millia Islamia]
(c) rate of diffusion and volume (a) pT I R (b) pRT (c)p / RT (d)RT!p
(d) rate of diffusion and viscosity
 Topic 2
Kinetic Molecular Theory of Gases and
Molecular Speeds
2014 2009
1. Two gases X (molecular weight M x) and Y (molecular 7. At 400 K, the root mean square (rms) speed of a gas X
weight My; My > M x ) are at the same temperature Tin (molecular weight = 40) is equal to the most p robable
two different containers. Their root mean square velocities speed of gas Y at 60 K. The molecular weight of the gas Y
are C x and Cy, respectively. If the average kinetic is [IlTJEEJ
energies per molecule of two gases X and Y are Ex and E y w2 ~4 ~6 ~8
respectively, then which of the following relation(s) is/are 8. Therms velocity of molecules ofa gas ofdensity 4 kg m - 3
true? [WB JEE] and pressure 1.2 x 10 5 nm - 2 is [Manipall
(a)Ex>Ey (b) Cx > Cy (a) 300 ms - 1
(b) 900 ms- 1

(c)Ex = Ey = (3 / 2)RT (d)Ex = Ey = (3/2)k 8 T (c) 120 ms - ' (d) 600 ms - 1

9. Different gases at the same temperature have same
2013
(a) pressure [OJEEJ
2. For gaseous stage, if most probable speed is denoted by C*,
(b) number of moles
average speed by C and root square speed by C, then for a
(c) volume
large number of molecules, the ratios of these speeds are
( d) average kinetic energy
(a) C*: C :C = 1.225 : 1.128: 1 [JEE Main]
(b) C* :t :C = 1.128 : 1.1225: 1 2008
(c)C* :C :C = 1: 1.128: 1.225
10. What is the temperature at which the kinetic energy of
(d) C* :C :C= 1: 1.225: 1.128
0.3 mole of helium is equal to the kinetic energy of
3. At what temperature will the m1s velocity of S02 be the 0.4 mole of argon at 400 K? CBITSATJ
same as that of 0 2 at 303 K? [KCET] (a) 400 K (b) 873 K
(a) 403 K (b) 303 K (c) 606 K (d) 273 K (c) 533 K (d) 300 K
11. Therms velocity ofan ideal gas at constant pressure varies
2011 with density (d) as CWB JEE]
4. The molecular velocity of any gas is [AIEEE]
(a) _l (b) d (c) ✓if (d) d 2
(a) inversely proportional to the square root of ✓ii
temperature
(b) inversely proportional to absolute temperature 12. Which of the following represents total kinetic energy of
(c) directly proportional to square of temperature one mole of gas? [OJEEJ
(d) directly proportional to square root of temperature (a) l/ 2RT (b) 3/ 2RT
(c)(Cp-Cv)RT (d)2/ 3RT
2010 13. The average velocity (in cm/s) of hydrogen molecule at
5. The root mean square velocity of a gas is doubled when 27°C will be [DCEJ
temperature is [Manipal] (a) 19.3x 104 (b) 17.8x 104
(a) increased four times (c) 24.93x 109 (d) 17.8x 108
(b) increased two tim es
(c) reduced to half 2007
(d) reduced to one-fourth
14. One mole of oxygen at 273 Kand one mole of sulphur
6. For one mole of an ideal gas, increasing the temperature dioxide at 546 K are taken in two separate containers,
from l 0°C to 20°C [KCET] then [KCET]
(a) increases the average kinetic energy by two times (a) kinetic energy of0 2 > kinetic energy ofS02
(b) increases the rms value by ..fi times (b) kinetic energy of 0 2 < kinetic energy of S02
(c) increases the m1s velocity by two times (c) kinetic energy ofboth are equal
( d) increases both the average kinetic energy and rms (d) None of the above
velocity, but not significantly
 States of Matter I 107
15. The kinetic theory ofgases preclicts that total kinetic energy 2005
of a gaseous assembly depends on [OJEEJ
20. Which one of the following statements is not correct about
(a) pressure of the gas the effect of an increase in temperature on the clistribution
(b) temperature of the gas of molecular speeds in a gas? [AIEEEJ
( c) volwne of the gas
(a) The area under the clistribution curve remains the
( d) pressure, volume and temperature of the gas same as under the lower temperature
16. If temperature of 1 mole of gas is increased by (b) The clistribution becomes broader
50°C, then calculate the change in kinetic energy of the (c) The fraction of the molecules w ith the most probable
system. [AMUJ speed increases
(a) 623.25 J (b) 6.235 J (d) The most probable speed increases
(c) 623.5 J (d) 6235 .0 J 21. The rms speed of hydrogen is ✓ 7 times the rms speed of
17. At the same temperature, calculate the ratio of average nitrogen. If Tis the temperature of the gas, then [BITSATJ
velocity of S02 to CH4 . CAMUJ (a) TH2 = TN2 (b) TH2 > TN2
(a) 2 : 3 (b) 3 : 4 (c) 1 : 2 (d) 1 : 6 (c) TH2 < TN2 (d) TH2 = ,J7TN2
18. In two vessels of 1 L each at the same temperature 1 g of
H 2 and 1 g of CH4 are taken, for these [DCEJ 22. Kinetic energy of one mole of an ideal gas at 300 K (in kJ)
is [MP PET]
(a) V,ms values will be same
(b) kinetic energy per mole will be same (a) 3.74 (b) 348 (c) 34.8 (d) 3.48
( c) total kinetic energy will be same 23. Ratio of average to most probable velocity is [OJEEJ
( d) pressure will be same (a) 1.128 (b) 1.224
19. As the temperature is raised from 20°C to 40°C, the (c) 1.0 (d) 1.112
average kinetic energy of neon atoms changes by a factor 24. Based on kinetic theory of gases followin g laws can be
of which of the following? [Jamia Millia Islamia] proved [AMUJ
(a) 1/2 (b) .J313/ 293 (a) Boyle's law (b) Charles' law
(c)313/293 (d)2 (c) Avogadro's law (d) All of these

Topic 3
Behaviour of Real Gases and van der Waals' Equations
(Including Liquefaction of Gases)
2014
1. If Z is a compressibility factor, van der Waals' equation at
low pressure can be written as [JEE Main] 3. The compressibility factor (Z) of one mole of a van der
RT a Waals' gas ofnegligible 'a' value is [WB JEE]
(a) Z = 1+ - (b) Z = 1- -
pb VRT
(a) l (b) bp (c) l+ bp (d) 1- bp
(c)Z = I-pb (d) RT RT RT
RT
4. In the van der Waals' equation given below,
Z= l+ pb
RT [p + a(n ! V)2](V - nb) = nRT, the a (n ! V) 2 and - nb
2. Find the pressure ofa sample ofCC1 4 , if 1.0 mole occupies terms represent respectively, corrections for
[lndraprastha CET]
35 L at 77°C. Assume CC1 4 obeys the van der Waals
equation of state.
2
( a = 20 L mol -
2
atm and (a) derivations in the pressure and the temperature
1 (b) intermolecular attractive forces and molecular
b = 0.14 L mol- ) [ManipalJ volwnes
(a) 0.56 atrn (c) intermolecular attractive forces and inelastic
(b) 0 .572 atrn collisions
(c) 0.82 atm (d) intermolecular repulsive forces and high
temperatures
(d) 0 .807 atrn
108 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2013 2010
5. The temperature 30.98°C is called critical temperature (Tc ) l 0. The te1m that corrects for the attractive forces present in a
of carbon dioxide. The critical temperature is the [BITSATJ real gas in the van der Waal's equation is [HT JEE]
(a) lowest temperature at which liquid carbon dioxide is (a) nb
2 2
observed (b)n a ! V
(b) highest temperature at which gas carbon dioxide is (c)-(n 2 a!V 2 )
observed (d) - nb
(c) highest temperature at which solid carbon dioxide is
observed 11. Pressure exerted by l mole of methane in a 0.25 L
(d) highest temperature at which liquid carbon dioxide is container at 300 K using van der Waals' equation is
observed (given, a = 2.253 atm L2 mol- 2 ,b= 0.0428 L mol- 1 )
6. van der Waals' equation for n moles of a gas is [KCET] (a)82.82atm (b) l 52.5latm [Pb CETJ

(a) (P + :\a )<v - nb) = RT (c) 190.52 atm (d) 70.52 atm

2009
(b)(p+ ;~)(V - nb) = RT 12. When a sample of gas is compressed at constant
temperature from l 5 atm to 6 atm, its volume changes from
76 cm3 to 20.5 cm3 . Which of the following statements
(c)(p+ ; 2 )(V - b)=nRT
are possible explanations of this behaviour?
I. The gas behaves non-ideally .
°
(d)(p+ ~ 2 )(V-b) = RT TT. The gas dimerises.
ITT. The gas is absorbed into the vessel walls. [Kerala CEE]
(a) I, II and III (b) I and II only
2012 (c) II and III (d) Only I
7. For one mole of a van der Waals' gas when b = 0 and (e) Only III
T = 300 K, the pV versus 1/V plot is shown below. The 13. The temperature, at which a gas shows maximum ideal
value of the van der Waals' constant a (atm L mol- 2 ) is behaviour, is known as [lndrapras tha CET, CGP ET]

24.6
(a) Boyle's temperature
~ 23.1 (b) inversion temperature
\ 21 .6 I
_ _ _ _ _ _ _ l_ _ _ _
(c) critical temperature
E 20.1 I
(d) absolute temperature
I
E I
I
iii I
I
I
I
I
2008
I
I
I
14. A gas deviates from ideal behaviow· at a high pressure
because its molecules [KCETJ
0 2.0 3.0
1N (mol L- 1) (a) attract one another
[IITJEE] (b) show the Tyndal effect
(a) 1.0 (b) 4.5 (c) 1.5 (d) 3.0 (c) have kinetic energy
8. The compressibility factor for a real gas at high pressure is (d) are bound by covalent bonds
RT 15. Under which of the following conditions, van der Waals'
(a) l + - (b) l [AIEEE]
pb gas approaches ideal behaviour? [OJEEJ

(c) l + pb (d) 1- pb (a) Extremely low pressure

RT RT (b) Low temperatw·e
(c) High pressure
2011 (d) Low product ofp V
9. a and bare van der Waals' constants for gases. Chlorine is 16. The units of van der Waals' constants a, b respectively, are
more easily liquefied than ethane because [AIEEEJ (a) L atm 2 mol- t andmolL- 1 [J &K CET]
(a) a and b for Cl 2 > a and b for C2 H6
(b) L atm mol 2 and mo! L- 1
(b) a and b for Cl 2 < a and b for C2 H6 (c) L2 atmmol- 2 andmol- 1 L
(c) a for Cl 2 > a for C2 H 6 but b for Cl 2 > b for C2 H 6
(d) L-2atm- 1 mol- 1 and L mol- 2
(d) a for Cl 2 > a for C2 H 6 but b for Cl 2 < b for C2 H6
 States of Matter I 109

2007 2006
17. Positive deviation from ideal behaviour takes place because 19. The CO2 gas does not follow gaseous laws at all ranges of
of [WBJEE] pressure and temperature because [MIIT CETJ

(a) molecular interaction between atom and pV > l (a) it is triatomic gas
nRT (b) its internal energy is quite high
(c) there is attraction between its molecules
(b) molecular interaction between atom and p V < I (d) it solidify at low temperature
nRT
20. The compressibility factor of an ideal gas is [KCETJ
(c) finite size of atoms and P V > I
nRT (a) 1 (b) 2 (c) 4 (d) 0
(d) finite size of atoms and P V < I
nRT 2005
18. Which one, among the following, is the van der Waals' 21. Gases X, Y, Z,P andQhave the van der Waals' constants
equation, describing the behaviour of one mole of a real gas a and b (in CGS units) as shown below.
over wide ranges of temperature and pressure? [J&K CETJ
X y z p Q
(a) ( p + ; 2 ) (V - b) = RT(b)(p - : 2 )(V - b)= RT a 6 6 20 0.05 30
b 0.025 0.15 0.1 0.02 0.2
(c) (p + ..!!...._) (V - b) = R (d) (p +..!!...._) (V + b)= RT The gas with the highest critical temperature is
v2 T v2 (a) P (b) Q (c) Y [Ke rala CEE]
(d) Z (e) X

Topic 4
Liquid State

2014 2008
1. Which factors do not affect the vapour pressure ofa liquid at 5. Surface tension vanishes at [OJEE]
equilibrium? (a) boiling point (b) critical point
T. Intermolecular forces of attraction. (c) condensation point (d) triple point
IT. The volume of liquid present.
ITT. The temperanire of the liquid. [BITSAT]
6. Vapour pressure increases with increase in [OJEEJ
(a) concentration of solution containing non-volatile
(a) Only I (b) Only II (c) I and II (d) II and III
solute
(b) temperature upto boiling point
2012 (c) temperature upto triple point
2. Which of the following is correct at freezing point? [OJEEJ
(d) altitude of the concerned place of boiling
(a) Solid and liquid are in equilibrium
7. The following is a method to determine the swface tension
(b) Solid and liquid are not in equilibrium of liquids [J&K CET]
(c) Vapour pressure of liquid is greater than solid
(a) single capillary method (b) refractometric method
(d) None of the above
(c) polarimetric method (d) boiling point method
2009
3. Cooking is fast in a pressure cooker, because [ManipalJ 2006
(a) food particles are effectively smashed 8. Which of the following set of variables give a straight line
(b) water boils at higher temperature inside pressure with a negative slope when plotted?
cooker (p = vapour pressure, T = temperature in K) [EAMCETJ
(c) food is cooked at constant volume Y-axis X-axis
(d) loss of heat due to radiation is minimum (a) p T
4. Which of the following will increase with the increase in (b) log 10 p T
temperature? [UPSEEJ
(c) log 10 p II T
(a) Surface tension (b) Viscosity
(d) log 10 p log 10 1/ T
(c) Molality (d) Vapour pressure
110 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Answers
TOPICl Gas Laws and Ideal Gas Equation
1. (c) 2. (d) 3. (b) 4. (c) 5. (d) 6. (c) 7. (b) 8. (c) 9. (a) 10. (a)
11. (a) 12. (c) 13. (c) 14. (b) 15. (d) 16. (a) 17. (b) 18. (d) 19. (c) 20. (c)
21. (b) 22. (a) 23. (c) 24. (a) 25. (c) 26. (d) 27. (c) 28. (c) 29. (d) 30. (c)
31. (c) 32. (b) 33. (c) 34. (c) 35. (c) 36. (c) 37. (a) 38. (a) 39. (c) 40. (a)
41. (b) 42. (d) 43. (c) 44. (a) 45. (c) 46. (b) 47. (d) 48. (d) 49. (c) 50. (c)
51. (d) 52. (c) 53. (a) 54. (c) 55. (c)
TOPIC2 Kinetic Molecular Theory of Gases and Molecular Speeds
1. (b,d) 2. (c) 3. (c) 4. (d) 5. (a) 6. (d) 7. (b) 8. (a) 9. (d) 10. (c)
11. (a) 12. (b) 13. (b) 14. (b) 15. (b) 16. (a) 17. (c) 18. (b) 19. (c) 20. (c)
21. (c) 22. (a) 23. (a) 24. (d)
TOPIC 3 Behaviour of Real Gases and van der Waals' Equations (Including Liquefaction of Gases)
1. (b) 2. (d) 3. (c) 4. (b) 5. (d) 6. (a) 7. (c) 8. (c) 9. (d) 10. (b)
11. (a) 12. (d) 13. (a) 14. (a) 15. (a) 16. (c) 17. (c) 18. (a) 19. (c) 20. (a)
21. (b)
TOPIC4 Liquid State
1. (b) 2. (a) 3. (b) 4. (d) 5. (b) 6. (b) 7. (a) 8. (c)

Explanations
Topic 1 Gas Laws and Ideal Gas Equation
1. This problem can be solved by using the concept of Graham's law of MN 2 =molecular mass ofN2,
diffusion of gases according to which rate of diffusion of non-reactive gases n02 = number of moles of 0 2 and
under similar conditions of temperature and pressure are inversely
~
2
= number of moles ofN2
proportional to square root of their density.
Rate of diffusion rmo2 ] 28 I 28 7
-lmN
2
32 -4x 32 - 32
°" °" -;=======
..jDensity of gas ..jMolar weight of gas
4 r{He - I {16 - I
Let, the distance covered by Xis d, then distance covered by Yis 24 - d. • ,{CH4 - 2V4 - I
If ''x and 'rare the rate of diffusion of gases X and Y,
''x= _ d_. _ = {4o=2 ,{He =_!_ {64 =i
'r 24-d vw ,{ S02 3 V4 3
(': rate of diffusion °" distance travelled) So, ,{ He : ,(CH4 : ,(S02 = 4: 4 : 3
d = 48 - 2d ⇒ 3d = 48 ⇒ d = 16 cm
5. From ideal gas equation, d = pM
2. Colision frequency is the measurement of number of molecular collisions RT
taking place per second per unit volume of gas. As the collision frequency ·:Mand R are constant for a particular gas
increases, molecular size increases and hence, covered distance decreases
than the expected value. :. d °" f!_
T
Since, speed is higher for X as it has lower molecular weight than Y, so it
i.e.
produces more collisions per second, i.e. more collision frequency and
hence, covers lesser distance than that predicted by Graham's law. (i)f!_ = --2_ = 0.0033 (ii.,g =~= 0.00183
T 600 T 273
_ no2 = (mo)1(M02)
3 p 6 . p 4
11N2 (mN2)/(MN2) (iit) - = - = 0.00549 (1v) - = - = 0.0080
T 1092 T 500
where, m02 = given mass of 0 2, ·: p IT ratio in highest at 4 atm and 500 K.
'"N 2 = given mass ofN2,
: . Density of CO is maximum at this condition.
M 02 = molecular mass of 0 2,
 States of Matter I 111
6. Ideal gas equation is 10. If p , T, p and R represent pressure, temperature, density and
universal gas constant, then ideal gas equation
pV = nRT or V = nRT + C
p pV = nRT for n mole of gas
RT pV = RT for 1 mole of gas
or V= - + 0 (for 1 mol)
p M
We know that, M =V xp ⇒ V =-
When V versus Tis plotted, a straight line is obtained, slope of p
which is given by R I p. Thus,
Put the value of Vin gas equation p x M = RT
R R _, _,
Slope = - ⇒ X =- or R = 2X L atrn mol K pRT p
p 2 Then, molar mass of gas M = ~
7. According to Graham's law of diffusion, 11. Let, T1 = T ⇒ T2 = (T + I) and p 1 = p
I V 0.4p 100.4
Rate of diffusion, roe - - = -
JM t Pz = p + I 00 = p 100
(here, M = molecular mass, V = volume and t = time)
From
p,V, = pzVz
200 1 T1 T2
Thus, for H 2 gas, ...(i)
30 - ✓2 pV I00.4p V
⇒ - = --X --
50 I T 100 (T+I)
For 0 2 gas, - = --
t 52 IO0T + 100=100.4T ⇒ 0.4T=100
200
F rom E qs. ( 1.) and (.11') , we get - -X-t = 52
,-;; T = lOO = 250 K
30x50 -;2
0.4
Jl6 x30x 50
t= - - - - - = (250 - 273)°C = - 23° C
200
12. ._.-1!_ = ✓MHe = {I= .fj_ = 1.4
= 4 X 30 = 30 min ,.He MH ~2
4
:. rH : 'ifo = I .4 : I
8. From Graham's law of diffusion
13. Since, the external pressure is 1.0 atrn, the gas pressure is also
'x = _!_ ...(i) I.0 atm as piston is movable. Out of this 1.0 atrn partial pressure
ly 5 due to tmknown compound is 0.68 atm.
Therefore, partial pressure of He= 1.00- 0.68= 0.32 atm
ly = _!_ ...(ii) n(He)RT 0.1 x 0.082x 273 L
rz 6 V oume
I 7
p(He) 0.32
On multiply ing Eqs. (i) and (ii),
Volume of container = Volume of He.= 7 L
rx = - - = J_
lz 5X 6 30 14. Rate of diffusion, roe p
rz 30 I
- =- or ,2 : 'x = 30 : 1 roe JM
'x I
9. Relation between rate of diffusions and molar masses of the gases roe_!!_
Xand CH4 is JM
'x - ✓MCH4 For gas A, r
A~
oe _l!_,f_ ...(i)
rcH4 Mx
Let, the rate of diffusion of gas X = a ForgasB, 11 oe _l!JJ_ ...(ii)
B JM;
a -
2a -vli;
(K (·: CH4 = 12 + 4= 16) Dividing Eq. (i) by Eq.(ii), we get

_!_= ✓ 16
2 Mx

Mx=l6x4=64
So, the molar mass of gas Xis 64.
112 I Chapterwise & Topicwise Engineering Entrances Solved Papers
15. n= pV =3170x 10-3 = 1.27x 10-3 mo! 22. The rate of effusion of He and CH 4
RT 8.314x 300 1
He =~MCH4 = 06 = 2 : l
16. Ideal gas equation is pV = nRT rCH4 MHe V4
W11en V and Tare same, p oc n If 4 : 1 mixnire of He and CH4 contained in a vessel, then the
Thus, when number of moles, i.e. n is least, it w ill exert least composition of mixnire ofHe and CH4 effusing out initially is 8 : I.
pressure. 23. Rate of diffusion depends upon the molecular masses of gases.
(i) fl= ~ = 0.0355 = I X 10- 3 mo! Therefore, the gases which have equal molecular mass, have
mo!. wt. 33.5 equal rates of diffusion.
7
(ii) fl= 0.0 l = 2 X 10- 3 mo! !i= ~
.. .)
33.5
Number of molecu les
r2 VMi
(Ill 11 6.023 x 1021 = 0.0 1 mo! Molecular mass ofN 2O= 28+ 16= 44
NA 6.023 X 1023 Molecular mass of CO2 = 12 + 32 = 44
(iv) n = 0.02 mo! r
NzO = 1
Thus, 0.0355 g chlorine will exert the least pressure. 1
C02
.ffu . I
17. Rate of d1 s1on oc ----.======
.Jmolecular mass rNzO =rco2

: . Order of diffusion : H 2 > CH4 > SO 2 and amount left is in the 24. According to Graham's law of diffi.1sion
order SO 2 > CH4 > H2. Rate of diffusion (r) oc _h
Hence, order of partial pressure is Pso 2 > Pett 4 > Ptt 2 [asp oc n].
Molecular weight (M) = 2 x vapom density
18. From ideal gas equation, pV = flRT
Since, p, V and Tare same for both 0 2 and H 2, therefore their
munber of moles (n) are also equal. Hence, munber of molecules
MA = (
1
~O) kg/molecule

w ill be equal for 0 2 and H 2.

Ms = ( ~) kg/molecule
8 12
19. Moles of A, flA = PAVA = x =~
RT RT RT
rA = 12 X 10-3and rs = ?
PsVs 8 X 5 40
MolesofB, ns = - - = - - = -
RT RT RT -rA -~S
- - -ntS
- -
Total pressure x Total volume = (nA + ns) x RT rs dA MA
I 12 X 10- 3
p x (I 2 + 8) = - (96 + 40) RT
RT
p=6.8
: . Partial pressure of A = p x mole fraction of A =H£ = I~

= 6.8 X (-2§._/
RT
96 40
+ ) = 4.8 atm
RT
_12 x10- xl0_
3
_
rs- - - - - - - 15 x 10 3
8
: . Partial pressure of B = p x mole fraction of B 25. pV = flRT
96 40 w
= 6.8( ~ / + ) = 2 atm pV= - RT
RT RT M
20. According to Boyle's law, poc J_ ⇒ M=~RT ⇒ M=dRT
V V p p
Hence, in order to increase the volume of a gas by I 0%, the
3 3
pressure of the gas should be decreased by 10% . d = 1.946 g / dm = 1.964 x 10- glee
1 p = 76 cm Hg= I atm
21. Rate of diffusion of gas oc
.Jmolecular mass R = 0.0821 L atm K-1 11101-1 = 82. 1 cc atm K-1 11101- 1
Let, the molecular mass of other gas= x
T = 273 K
'He = 4 = ✓ Mx ⇒ 4= {M: M = 1.964 X I 0- 3 X 82.1 X 273
~ MHe V4 1
44

42 =Mx ⇒ M =64 The molecular weight of CO2 is 44.

4 X
So, the gas is CO2.
Thus, the gas is SO2.
 States of Matter I 113
26. When a mixture of two or more non-reacting gases are enclosed 35. Correct gas equation is p,V, = T,
in a container then the total pressure exerted by the gaseous PzV2 T2
mixture is equal to the stun of partial pressure of the components
56
in the mixture. 36. Number of moles ofN2 = - = 2
e.g. CO + H 2 are non-reacting gases. Hence, Dalton's law of 28
partial pressure is applicable to this system. 44
Number of moles of CO 2 = - = 1
44
27. V-Tplot representing the behaviour of 1 mole ofan ideal gas at 1
16
atm pressure. Volume of 1 mole of an ideal gas at 273 K and Number of moles of CH4 = - = 1
1 atm pressure is 22.4 L. 16
Volmne of 1 mole ofan ideal gas at 373 Kand I atm pressure will :. Total nmnber of moles = 2 + 1 + 1 = 4
be
Mole fraction ofCH4 = _!_
4
V = RT = 0.0821 x 373 3058 L
p 1 :. Partial pressure of CH 4 = mole fraction of CH4 x total pressure
1
28. Dalton's Jaw of partial pressure This law states that the total = - x 720 = 180 atm
pressure exerted by a mixture ofnon-reacting gases is equal to the 4
sum of partial pressure exerted by the individual gases. 0.4
37. Number o f moles o f He = - = 0.1
P = Pi + Pi + P3 .. · 4
Dalton's law of partial pressure follows by the mixture of Number of moles of oxygen=~= 0.05
non-reacting gas but NH 3 react w ith HCl gives NH 4Cl. 32
NH 3 + HCI ➔ NH4 Cl
Number of moles of nitrogen =~= 0.05
Hence, Dalton's law of partial pressure is not applicable to 28
NH3 + HCI. Total moles of the 10.0 L cylinder at 27°C
29. pV = nRT (Ideal gas equation) = 0. 1 + 0.05 + 0.05 = 0.2 mol

V = nRT ⇒ V1 = T1 x p 2 Pr = nRT = 0.2 X 0.082 X 300 0.4 atm

92
or
p V2 T2 Pi V 10
38. 6.4 g of S02 at 0°C and 0.99 atm pressure occupies a volume of
.!J_ = 273 + 15 X _ 1_ ⇒ .!J_ = 288 X _!_
V2 273 + 25 1.5 V2 298 1.5 2.24 L. It indicates that the gas is ideal.
.
39. G 1ven, P2 -- 2, Ti -- 2 , V -- 4 dm 3 , V: -- ?•
⇒ .!J_ =-1- Pi T,
1 2

V2 1.55
p,v, P2V2 vi P2 T,
From gas equation, - - = - - or - = - x -
Vz = 1.55 T1 T2 V2 P1 T2
v,
4 1
.!J_ = V2 - =2X - = 1
30. (Charles' law) V2 2
T1 T2
V2 =4 dm 3
--2_ = _i_ T, = 273 x 4 = 546 Kor 273°C
273 T2 - 2 40. The correct order of pressure is p 1 > P3 > Pi·
31. Ideal gas equation pV = nRT is obeyed by ideal gas in both
adiabatic process and isothermal process.
✓
41. _!i_ = M CO2
1co2 Mx
32. diT1 =dzT2
When p remains constant (in accordance to Charles' law) 83.3 = ✓Mco 2 = ✓ 44
102 M, Mx
d 1 = 16, d2 = 14, T1 = 273 Kand T2 =?
d 1T1 = dzT2 ⇒ 16x 273 = 14 x T2 M = 44x( 102)2
x 83.3
T2 =312K ⇒ T2 =3 12-273=39°C
33. The curve (c) represents a Boyle plot at very low pressure. = 65.97 g mol- 1

42. According to Graham's law ofdiffi.1sion roe~

34. pV = nRT
Hence, the order of rate of diffusion is
V = nRT
p Gases, A > B>C
Molecular weight 2 4 28
Hence, molar volume of CO2 is maximum at l 27°C and 1 atm.
114 I Chapterwise & Topicwise Engineering Entrances Solved Papers
43. According to Graham's law of diffusion 15 17
51. If V1 = I Vi = 1 - - =-
ro2 = ✓ MHe = {4 = 0.353
' 100 20
Mo2 '{32 Pi= 2Pt ⇒T 1 = 348, T2 = ?
'i-le
r02 = 0.353rHe
p,V1
Tl
=P2Vi
Ti
⇒ A - 2 x _ t_7_
348 - Pi 20 x Ti
44. pV = nRT
T2 = 60° C
V = same, R = constant, T = same p ex n
52. Given, V1 = 500 mL,T1 = 27 + 273 = 300 K
w .
or p oc - but w 1s same. Vi = ?, Ti = 42 + 273 = 315 K
M
From Charles' law V 1T2 = ViT1
1
So, pex M V = 500 X 315 = 525 mL
2
300
PcH4 = Mo2 = 32 =3. Hence, increase in volume= 525 - 500= 25 mL
Po2 McH4 16 53. White ring of NH4CI w ill appear nearer to the HCI end. The
45. By Graham's diffusion law, reason is that HCI (molecular weight= 36.5) is heavier than NH3

= ✓MCH4
(molecular weight= I).
rHe Hence, according to Graham's law of diffusion, the rate of
lt:H4 MHe diffusion ofNH3 will be higher than that ofHCI.
MCH4 = 12 + 4 = 16 ~ = g
M He = 4 li-Je = {16 = ~ = 2 12 VMi
rCH 4 V4 VI 54. Partial pressure oc Moles of a gas
Thus, the ratio of rate of diffusion of He and CH4 is 2. 1 44 / 44
Hence, f!J_ = ~ ⇒ - = ---
46. Graham's law of diffusion of gases Pi X2 Pi 44 / 2
44
¾=~=~
Thus, Graham's law of diffusion of gases related to density and
Pi = - = 22atm

55. Ideal gas equation, pV = nRT

2

rate of diffusion of gases.

If V=IL ⇒ n=J!.....
47. Charles obtained experimentally that at constant pressure for 1° C RT
increment/decrement in temperature of a gas, the volume
increase/decrease by a fraction of (
2
~J- Hence, the Topic 2 Kinetic Molecular Theory of
Gases and Molecular Speeds
mathematical expression for Charles' law is 1. Given, molecular weight of X = Mx
V
I
= Vo (1+ 273 _ t )· molecular weight of Y = My and My > Mx
Root mean square velocities = C x and Cy, respectively.
48. Mole fraction of nitrogen in air is greater than the given gases, as Average KE/molecule = Ex and Ey, respectively.
it is present in larger amount than other given gases in the We know that, root mean square velocity,
atmosphere. Thus, it has highest partial pressure in the
atmosphere.
49. In ideal gas equation the value of universal gas constant depends
C = P:: or C ex fl;
= ✓::
on the units of the measurement.
Numerical values of R, ~;
(i) 0.082 1 L atm K- 1 mo1- 1 Since My>Mx
(ii) 8.314 JK-1 mol- 1 Cx>Cy
(iii) 8.314 x 107 erg K- 1 mo1- 1 3 3
KE/molecules= - nRT ⇒ Ex* Er* - RT
I 2 2
50. For a gas, Pi v, = PiVi (where, T2 = 2T1, p2 =
T1 T2 2 Pi, Vi = ?) (as E, and EY are average KE/molecule).
3
Ex= Ey =
PiV, = .!_ Pi x V2 ⇒ V, = Vi
Further,
2 k8 T
T1 2 2T1 4 Hence, options (b) and (d) are correct.
V2 = 4V1
 States of Matter I 115
Root mean square (rms) velocity,
2. C * = Most probable speed=~
vrms = pRT ⇒ V(nns)t = ~ = ✓283 = 0 _98
C =Average speed = ✓8RT
- -- M v(m1S)2 VTz 293
1tM
Thus, both average kinetic energy and root mean square velocity
C = Mean square speed corrected as rms = ~ increase but not significantly when temperature is increased
from I0°C to 20°C.
C*:C:C=l:~)I 7. Vnn,=Vf11)S

= 1 : 1.128 : 1.225
Note In the given question, root square speed is given which should ~= ✓:(~) ⇒ ✓ 3 X 400 = ✓2 X 60
40 M(Y)
be root mean square speed.
M(Y) = 4
. 3RTso2
3. The RMS velocity of S02 us02 = - - -
8. v = {3p = /3 x 1.2 x 105 = 300 ms- I
3RT0
Mso2
= Vd V 4
The RMS velocity of 0 2 ''oz = ~ 9. From kinetic molecular theory of gases, different gases at the
02 same temperature have same average kinetic energy.
In case of S02 , T = 303 10. Number of moles of helium= 0.3
Molecular weight= 64 Number of moles of argon = 0.4
11s02 = ✓3R:: T We know that, KE = nRT

In case of S0 2, T = 303, M = 32, u02 = J¥ KE of helium = 0.3 x R x T

KE of argon= 0.4
According to the question,
x Rx 400
...(i)
...(ii)

3R X 303 3R X T
KE of helium= KE of argon
32 64
0.3 x R x T = 0.4 x R x 400
64
T = X 303 = 606 K
T = 533 K
32
4. Molecular velocity can be 11. Kinetic gas equation, for one mole gas is
1 2
. = PRT
Average ve Ioc1ty -- pV= - Mu
1tM 3
where, p = pressure of gas
. =
R oot mean square veIoc1ty ✓3RT
M V = volmne of gas

✓ 2:;-
M = molecular mass of gas
Most probable velocity =
u = root mean square velocity
In all the above, molecules velocity oc ✓
T
Mu2 = pV
3
5. V =PRT
M
nns

v,ms ""- ✓
T
u=t:: u=ff (d= ~)
: . At two different temperatures, If pressure is constant, then u ""- ~ .

::=~ 12. Total kinetic energy=

vd

I2 nRT
Given, ii
nns
= 2v
nns
.!.2 = fr
{T or _!_ = 2:_
4 T'
where, n = number of moles of gas
n= I
T' =4T 3
Then, KE = - RT
: . v,ms gets doubled, when the temperature is increased four times. 2

~ ⇒
6. Given, T1 = 273 + IO = 283 K
13. Average = T = (27 + 273) = 300 K
⇒ T2 = 273 + 20 = 293 K
3 Molecular mass of H 2 = 2 g mo1- 1
Average KE = kT
2 Average velocity (H 2 )
, - - - - - - -7- - -
⇒ KE 1 = 283 = 0 _96
KE2 293 8 x 8.314 x 10 x 300 = 17_ x 104 cm/s
8
3.14 X 2
116 I Chapterwise & Topicwise Engineering Entrances Solved Papers
14. KE =l RT ~ = ✓7
2
KEocT
v~ X tRTN2
MN2
(because rms speed of H 2 is ✓7 times therms speed ofN2)
KE0 2 = To2 = 273 = ..!_
TH 7 xTN
KE S02 Tso2 546 2 ⇒ _ = ---
2 2
2 28
KEso2 = 2KE02
TN2 = 2TH2or TH2 < TN2
KEso2 > KE02
15. The average kinetic energy of a gaseous assembly depends on 22. Kinetic energy (KE) = 2 RT
temperanire of the gas 2
3
KE=
KEO<: T
2 X 8.3 1X 300 J = 3.74 kJ
3
16. KE = - RT for I mole of gas
2 23. Average speed of gas molecules =
M
and t-..T = 50° C
3
t-..KE = - X 8.315x (50-0) Most probable speed of gas molecules= rm
VM
2
=2x 8.315x 50= 623.25 J vav : v"1> = ✓8RT : ✓2RT
2 rcM M

17. u.v O<:

I
./ii at constant temperature =I-! : ✓2 = 1.1 28: I
24. Boyle' s law, Charles' law and Avogadro's law can be proved on
Uav (S02) = ~MCH4 = fl6 = ..!_ the kinetic molecular theory of gases.
u.v (CH4) Mso2 V64 2

Uso2 :Uc"◄ = I: 2 Topic 3 Behaviour of Real Gases and

3
18. KE= - kT van der Waals' Equations
2 (Including Liquefaction of Gases)
where, k is constant. 1. To solve this problem, the stepwise approach is required, i.e.
Thus, it is clear that, KE does not depend upon the nature of
gas it only depends upon temperanire of the gas. If temperature (i) Write the van der Waals' equation, (P + ,:~) (V - b) = RT
remains same, then KE per mole will be same.
3 then apply the condition that at low pressure, volume become
19. Average KE =
2 RT I N 0 high,
i.~ V -b =V
(KE) O<: T
(ii) Now, calculate the value of compressibility factor (Z)
(KE)313 / (KE)293 -_ l_!2
293 Z = pV I RT
According to van der Waals' equation,
20. D istribution of molecules (N) with velocity (u) at two
temperanires T 1 and T2 (T2 > T1) is shown below. (P + ; 2) (V - b) = RT
At low pressure, (P + ; V= RT
2
)

1~ a
pV + - =RT
V
⇒ pV =RT- -
a
V
U----+
At both temperanrres, distribution of molecules w ith increase in Dividing both side by RT, pV = 1- _ a _
RT RTV
velocity first increases, reaches a maximum value and then
0
decreases. Thus, on increasing the temperanrre the fraction of the Z= 1- --
VRT
molecules with most probable speed increases.

21. u=t:: RT
2. Pressure, p = - - - 2
V-b
a
V
= 0.082 x 350 _ ~ = 0 _807 atm
35 - 0. 14 (35)2
 States of Matter I 117
3. van der Waals' equation is Thus, p(V -b)=RT ⇒ pV - pb=RT ⇒ pV =RT+ pb

(p + ; 2) (V - b) = RT (for I mole) :. Compressibility factor, Z = pV = (1 + pb)

RT RT

If a is negligible, p + -; "" p 9. van der Waals' constant a is due to force of attraction and b due to
V finite size of molecules. Thus, greater the value of a and smaller
p(V-b)=RT ⇒ pV-pb=RT the value of b, larger the liquefaction.
Thus, a(Cl 2 ) > a(C2H6) and b(Cl 2 ) < b(C2H6 ) .
or
10. In the van der Waals' equation
4. van der Waals' equation is
(p + 1
;:) (V - nb) = flRT
(p + ;:) (V - nb) = nRT
The pressllfe correction factor (n2a I V 2 ) accounts for
In this equation, n is number of moles of the gas, a and bare van intermolecular attraction in real gas.
der Waals' constant and their value depends on the characteristics 11. From van der Waals' equation,
of gases. According to kinetic molecular theory of gases, the gas
equation, i.e. pV = nRT was given for those gases having no
intermolecular attractions and molecular volumes. However, the
(p+ ;:)(V-nb)=RT

van der Waals' correction was developed for real gases in which 2 253
this was assumed that molecules in real gases have attractions as ( p + 0.25x
·
0.25
) (0.25- 0.0428) = 0.0821 X 300
well as volumes. Thus, van der Waals' corrections a and b were
introduced. (p + 36.048) (0.2072) = 24.63
Here, value of' a' is the measure of magnin1de of intermolecular p + 36.048 = 118.87
forces of attraction within the gas and is independent of
p = 118.87 - 36.048 = 82.82 atrn
temperanire and pressure and nb is the total volume occupied by
12. At constant temperature, for ideal gas, p 1V1 = pzV2
the molecules themselves.
5. Critical temperature of a gas is highest temperature at w hich For the given sample, 15 x 76 = 60 x 20.5
liquefication of the gas first occurs. The temperature 30.98°C is PtV, ~ P2V2
called critical temperanrre of carbon dioxide because this is the :. The gas behaves non-ideally. However, the gas neither
highest temperanire at which liquid carbon dioxide is observed. undergo dimerisation nor adsorbed into the vessel walls.
Above this temperature it is gas.
13. Boyle's temperanire is the temperature at which a real gas exhibit
6. The van der Waals' equation for fl molecules of gas is ideal behaviour for considerable range of pressure. It is related
rlp+v2
,?al
J(V -nb) = RT
with van der Waals' constant as
a
Ts= -
bR
Hence, a and bare van der Waals' constants.
14. At high pressure, the volume is decreased appreciably, so the
7. The van der Waals' equation of state is
attractive forces become large and the molecules are crowded
(p+ ;:) (V-nb)=nRT
together. Thus, pressure correction is necessary and the gas
deviates more from ideal behaviollf.
For one mole and when b = 0, the above equation condenses to 15. van der Waals' gas approaches ideal behaviollf at low pressure
and high temperature.
(p + Va) V = RT
2 ⇒ pV a
= RT - V ...(i)
16. van der Waals' equation is (p + ; :) (V - nb) = flRT
Eq. (i) is a straight equation between p Vand _!_ whose slope is -a.
V vz
Equating with slope of the straight Iine given in the graph Units of a = ~
n
-a=20.1 -21.6=- l. 5 ⇒ a= l. 5 atm x L2
3-2 2
mol
8. van der Waals' equation for one mole ofreal gas is
Units of b = V = ~ = mol- 1L
(p + ; 2 )(V-b)=RT fl mol

11. pV > I, the gas is less compressible than expected from ideal
When pressure is high p >> - ; nRT
V
behaviour due to finite size of atoms and shows positive
Such that (P + ; 2 ) "' p deviation.
118 I Chapterwise & Topicwise Engineering Entrances Solved Papers
18. The van der Waals' equation for n moles of a gas is (iii) As temperature increases, intermolecular force of attraction
rlp + v2
n al
2
J(V - nb) = nRT
decreases due to increase in the molecular collision, hence
vapour pressure increases on increasing temperature.
Thus, the correct choice is (b).
For one mole (n = I) 2. According to phase diagram, at freezing point, liquid state
(p+ ; 2) (V-b)=RT
remains in equilibriwn with solid state.
3. The boiling point is the temperature at which the vapour pressure
19. Real gases do not follow gas laws at all temperature and pressure becomes equal to the surrounding pressure. T he boiling point of a
conditions due to two wrong assumptions in kinetic molecular liquid can be increased by raising the external pressure.
theory of gases. The domestic pressure cooker work on this principle.
(i) The volume occupied by gas molecules is negligible. It is not The pressure inside the pressure cooker is maintained above one
true because gas molecules do occupy small volume. atmosphere and the liquid contained then would boil at a higher
(ii) The forces of attraction between gas molecules are zero. It is temperature than I 00° C, thus d1e food is cooked in a shorter time.
not true because attractive forces are present between 4. As the temperature rises, d1e kinetic energy of the molecules
molecules ofreal gases. increases. Due to which the molecules can leave the liquid
20. The compressibility factor (Z) of an ideal gas is one because surface easily. In other words, the vapour pressure increases.
However, surface tension and viscosity decrease with rise in
pV = nRT,(z = pV )· temperature. Molality is the ratio of moles of solute to weight of
nRT
solvent, hence it does not depend upon the temperature.
21. The value of van der Waal's constant 'a' increases in the same
order as the critical temperature. Here, the value of a is highest for 5. At critical point, the meniscus between the liquid and vapour
Q, hence gas Q has the highest critical temperature. disappears, thus the surface tension of liquid becomes zero.
6. Vapour pressure becomes identical as the atmospheric pressure at
Topic 4 Liquid State boiling point. If the liquid is heated beyond that only evaporation
I. Affect of three given statements on vapour pressure can be continues, vapour pressure does not rise further.
explained as 7. Single capillary method is used to determine surface tension of
(i) Intermolecular forces of attraction affects vapour pressure of liquids.
liquid at equilibrium as intermolecular attraction increases the 8. According to write as: Clausius-Clapeyron equation, if a graph is
vapour pressure decreases.
plotted between_!_ (taken on X-axis) and log 10 p (taken on Y-axis)
Hence, it affects vapour pressure. T
(ii) Volume of liquid present does not affect vapour pressure as a straight line with a negative slope is obtained.
vapour pressure in directly related to intermolecular force of
attraction of liquid at equilibriwn.
So, it does not affects vapour pressure ofliquid at equilibrium.
Thermodynamics
QUICK REVIEW
The branch of science dealing with different forms of energy
and their quantitative inter-relationships is known as
thermodynamics.
Macroscopic Properties
Arises due to bulk behaviour of matter. These are two types
(i) Extensive properties are the properties of the system
which depend upon the amount of substances in the
system. e.g. mass, volun1e, energy, enthalpy and work
etc.
(ii) Intensive properties are the properties of the system
which do not depend upon the amount of substance
present. Mass, volume, energy, enthalpy and work are
extensive properties while temperature, pressure,
viscosity, refractive index and specific heat are
intensive properties.
State Functions
• The fundamental prope1ties such as pressure, volume,
temperature, internal energy, entropy and Gibbs energy
etc. are known as state functions. State functions depend
only on the state of system and are independent of the path.
• The work and heat are not a state function, however (q - W)
is state function.
Work Done in Isothermal Irreversible Expansion
• Work done by a gas for isothermal irreversible expansion
from volume V1 to volume V2 against a constant external
pressure pis
W ;rr =-
p(V2 - V1 ) = - pt:,. V (l L atm = 101.3 J)
Note for isothermal irreversible compression, work done is
positive.
W;rr = p(V2 - V1 ) = + pt:,. V
Work Done in Isothermal Reversible Expansion of an
Ideal Gas
Pressure volume work done in an isothermal reversible
expansion
W rev = - 2. 303 nRT log V2 and W,ev = - 2. 303 nRT log 1?J_
~ P2
Internal Energy (!:,.U) The sum of all energies contained
in a system.
First Law of Thermodynamics
According to first law of thermodynamics, t:,.U = q + W,
where q is the heat absorbed by the system and Wis the work
done on the system.
Sign Conventions for 1'1.U, q and W
• If energy is absorbed by the system, t:,.U is positive
• If energy is released by the system, t:,.U is negative
• If work is done on the system, Wis positive
• If work is done by the system, W is negative
• If heat is absorbed by the system, q is positive
• If heat is released by the system, q is negative
Enthalpy of a System
• The total heat content of a system at constant pressure is
called enthalpy of the system.
• The change in enthalpy, Afi = t:,.U + p !:,.V
Afi = t:,.U + l':,.ng RT
• If l':,.ng = 0, then Afi = t:,.U.
• If l':,.ng > 0, then Afi> t:,.U and similarly if l':,.ng < 0 then
Afi< t:,.U.
• For exothermic reactions Afi is negative and for
endothe1mic reactions Afi is positive.
120 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Calculation of Enthalpy Change by Using • Trouton 's rule The ratio of enthalpy of vaporisation and
Calorimeter the normal boiling point of a liquid approximately equals
• 11H = Z x flT x MI rr~ where, Z is the heat capacity of 88 J/mol K.
calorimeter system, flT is change in temperature, M is 11H
~ " ' 88 J mo1- 1 K - 1
molecular mass of the substance and mis the amount of the Tb
substance.
• 11H = H products - H reactants Entropy
0 0
• Entropy is measure of degree of disorder or randomness of
• 11H0 reaction = I.11H1 (products) - I./1H/reactants)
the molecules of the system. It increases when temperature
• 11H reaction = I. bond energies of reactants - I. bond of the system increases.
energies of products • Entropy of all pure crystalline substances may be taken as
zero at absolute zero temperature
Hess's Law of Constant Heat Summation
flS = q rev
Law states that the total heat change (Aff) of a chemical T
reaction is the same whether the reaction takes place in one or
• flS system + llS StDToundings ~ 0 here sign = refers to reversible
more steps. process (equilibrium) and sign > refers to an irreversible
Af-1
A- ---+B process (spontaneous process).
m,\ 1~
C--+ D
• flS fusion = 11H fusion / TJ , llS vap = 11H vap / Tb
and llS sub = 11Hsub I T
M-lz
11H = 11Hi +l1Hz + l1H3 • flS = 2. 303nR log(;:)
Heat Capacity
• C= q
Tz - lj,
where q is the heat required to raise the • llS = 2.303nR log(:~ l
temperature from 1j to T2 . • Positive value of fl S shows spontaneous process while
negative value of fl S shows non-spontaneous process and
• Heat capacity at constant volume, Cv = [<)E]
aT v fl S = 0 represents an equilibrium state of a system.

• Heat capacity at constant pressure, C P = [<)H] Gibbs Energy

<)T P
• The maximum amount of energy available to a system
• For an ideal gas, C P - Cv = R where, R is the gas constant during a process that can be converted into useful work is
therefore C P > C v called free energy of Gibbs free energy of Gibbs energy.
CP !Cv = "f = l.66(formonoatomicgas) • flG = 11H - TllS (Gibb's-Helmholtz equation)
= l.40(for diatomic gas) = 1.30(for triatomic gas) 0 0 0
• flG = LG products - LG reactants
Dulong and Petit Law The product of specific heat and • If flG is negative, the process is spontaneous, if flG is
molar mass of any metallic element equals to positive, process is non-spontaneous and if flG is zero,
6.4 ca1/mol C. This law is applicable to solid elements only
0
process is in equilibrium .
except Be, B, C and Si. Specific heat x molar mass = 6.4 • flG = - 2303RT log K , where K is equilibrium constant.
• Clausius-Clapeyron equation; Efficiency of a fuel cell
2.303 log!!.__!_ = 11Hv (Tz- T, ) = total useful work x
100
P, R I; - Tz total heat given
where, 11Hv is the molar heat of vaporisation. Coupled reactions Many of the non-spontaneous
• Kirchhoff's equation (effect of temperature on heat of reactions (fl, G = + ve) can be made spontaneous by
reaction). coupling these reactions with other reactions which have
l1H2 -11H, very large negative values of Gibbs energy.
 Topic 1
Basic Concepts of Thermodynamics
2014 2012
1. An ideal gas in thennally insulated vessel at internal 6. A gas expands from a volume of 1m 3 to a volume of 2 m 3
pressure = p 1 , volume = V1 and absolute temperature = Ti against an external pressure of I 0 5 Nm- 2
. The work done
expands irreversibly against zero external pressure, as by the gas will be [KCETJ
shown in the diagram. [JEE Advanc ed] 2 2
(a) 10 kJ (b) 10 J
Pext. = 0 (c) 10 3 J (d) I 0 5 kJ
lrreversib le 7. A gas undergoes a thermodynamical process but the
Pext. = 0

- P2. V2. T2 - volume of the gas does not change. What is the nature of
this process ?
(a) Isothermal
(c) Isobaric
[OJEEJ
(b) Adiabatic
(d) Isochoric
' -Thermal insulation_/

The final internal pressure, volume and absolute 2010

temperature of the gas are p 2 , V2 and T2, respectively. For 8. An ideal gas expands in volume from 1 x 10- 3 m 3 to
this expansion
1 x 1o- 2 m 3 at 300 K against a constant pressure of
(a) q = 0 (b) T2 = T1 5 2
1 x 10 Nm- . The work done is CJCECE]
(c) P2V2 = P 1V1 {d) P2V2'Y = P1V?
(a) - 9001 (b) - 900kJ (c) 270kJ (d) 900kJ
2013
2009
Directions (Q. Nos. 2-3) A fixed mass mofa gas is subjected
9. An adiabatic process occurs in [AMUJ
to transformation ofstates from K to L to M to N and back to K as
shown in the figure. (a) open system (b) closed system
(c) isolated system (d) in all the given system

~ K□L
i;;
1O. Which one of the following is not a state function ?
(a) Enthalpy (b) Entropy [MP PET]
83 (c) Work (d) Free energy
a:
N M 11. We believe in the laws of thermodynamics because
Volume they are [J&K CET]
(a) theoretical
2. The succeeding operations that enable this transformation
(b) derived based on mathematical analysis
of states are [JEE Advanced]
( c) empirical and nobody disproved
(a) heating, cooling, heating, cooling
( d) mere statements
(b) cooling, heating, cooling, heating
(c) heating, cooling, cooling, heating 2008
( d) cooling, heating, heating, cooling 12. Which one of the following is an exothem1ic reaction?
3. The pair of isochoric processes among the transformation (a) N 2 (g) + 0 2 {g )+ 180. 8kJ ~ 2NO(g) [DCEJ
of states is [JEE Advanced]
(b) N 2 (g) + 3H 2 (g) - 92kJ ~ 2NH3 (g)
(a) KtoLandLtoM (b) Lto Mand N to K
(c) C(g) + H 2 O(g) ~ CO(g) + H2 (g) - 131.l kJ
( c) L to M and M to N (d) M to N and N to K
(d) C(graphite)+2S(s) ~ CS 2 (l) - 91.9kJ
4. The intensive property among these quantities is [KCET]
13. Which of the following taking p lace in the blast furnace is
(a) enthalpy (b) mass/volume
endothennic ? [Jamia Millia Islamia]
(c) mass (d) volwne
(a) CaCO3 ~ CaO + CO 2
5. A gas can expand from I00 mL to 250 mL under a constant (b) 2C + 0 2 ~ 2CO
pressure of2 attn. The work done by the gas is [OJEE]
(c) C + 0 2 ~ CO2
(a) 30.48 J (b) 25 J (c) 5 kJ (d) 16 J (d) Fe 2 O 3 + 3CO ~ 2Fe + 3CO2
122 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2007
14. The work done during the expansion of a gas from a 16. Which of the following is an intensive property? [KCETJ
volume of 4 dm 3 to 6 dm3 against a constant external (a) Temperature (b) Viscosity
pressure of 3 atm is [UPSEE, Manipall (c) Surface tension (d) All of these
(a) - 6 J (b) - 6081 17. Which is an extensive property? [KCET]
(c) + 304 J (d) - 304 J (a) Temperature
15. Which of the following is a path fonction? [MHT CETJ (b) Chemical potential
(a) Internal energy (b) Enthalpy (c) Gibb's free energy
(c) Work (d) Entropy (d) Molar volume

Topic 2
Internal Energy (1st Law of Thermodynamics) and Hess's Law
2014
1. A swimmer coming out from a pool is covered with a film (a) q = + 208 J, W = - 208 J
of water weighing about 18 g. Calculate the internal energy (b) q = - 208 J, W = - 208 J
of vaporisation at 100°C. (c) q = - 208 J, W = + 208 J
6 1
[L'. vapH for water at373 K = 40.66 kJ mol- ] (d) q = + 208 J, W = + 208 J
The correct option is [KCETJ 6. Hess's law states that [OJEEJ
(a) 35.67kJ mol- 1 (b) 37.56kJ mol- 1
(a) the standard enthalpy ofan overall reaction is the sum
(c) 36.57 kJ mol- 1
(d) 38.75 kJ mol- 1 of the enthalpy changes in individual reactions
(b) enthalpy of formation of a compound is same as the
2. The value of M for cooling 2 mole of an ideal enthalpy of decomposition of the compound into
monoatomic gas from 225°C to 125°C at constant pressure constituent elements, but with opposite sign
will be(given C P = 1R) [WBJEEJ
(c) at constant temperature the pressure of a gas is
inversely proportional to its volume
(d) the mass of a gas dissolved per litre of a solvent is
(a)250R (b) - 500R (c)500R (d) - 250R
proportional to the pressure of the gas in equilibrium
3. Given that C + 0 2 ~ CO2 ; M 0 = - x kJ with the solution.
2CO + 0 2 ~ 2CO2 ; M 0 = - y kl The heat of
formation of carbon monoxide will be [WB JEE] 2012
7. The reversible expansion of an ideal gas under adiabatic
(a)y - 2x (b)y+2x (c)2r - y (d)2x - y
2 2 and isothermal conditions is shown in the figure.
[IIT JEE]
4. At 25°C, for the combustion of 1 mole of liquid benzene,
the heat ofreaction at constant pressure is given by
15 p
C 6 H 6 (/) +- 0 2 (g) ~ 6CO2 (g)+ 3H2 O (/), (P2, V2, T'»
2 (p3, V3, T3)
(M = 780980cal)
V
Calculate the heat of reaction at constant volume [AMU]
Which of the following statement (s) is (are) correct?
(a) 780.086 kcal (b) - 780.086 kcal (a)J;=T2 (b)T3 >T1
(c) - 390.043 kcal (d) 390.043 kcal
(c) wiwthermal > Wadiabatic (d) L'. U iSl.lthermal > L'. Uadiabatic
2013 2011
5. A piston filled with 0.04 mole of an ideal gas expands 8. Based on the first law of thermodynamics, which one ofthe
reversibly from 50.0 mL to 375 mL at a constant following is correct ? [KCETJ
temperature of 37.0°C. As it does so, it absorbs 208 J of
(a) For an isochoric process= l1E = - Q
heat. The values of q and W for the process will be
(b) For an adiabatic process = l1E = - W
(R = 8.314 J/mol K, In 7.5 = 2.01) [JEE Mains] (c) For an isothermal process = Q = + W
(d) For a cyclic process = Q = - W
 Thermodynamics I 123
9. IfC(s)+ O 2 ( g ) ~ CO2 (g);!'1H = r and 17. A gas expands isothermally against a constant external
l pressure of 1 atm from a volume of 10dm3 to a volwne of
CO (g)+ - 0 2 ~ CO 2 (g); W =s, then the heat of
20dm3 • It absorbs 800 J of thermal energy from its
2
formation of CO is [MHTCET] surroundings. The !'1U is [BCECE]
(a) r+s (b) r - s (c) s- r (d) rs (a) - 3121 (b)+123J
( c) - 213 J ( d) + 231 J
2008
10. C(s)+O2 (g) ~ CO2 (g);W = - 94kcal 2006
2CO(g) + 0 2 ~ 2CO2 (g); W = - 135.2 kcal 18. An ideal gas is allowed to expand both reversibly and
i.tTeversibly ill an isolated system. If Ti is the mitial
The heat of formation of CO (g) is [UPSEEJ
temperatw·e and T1 is the final temperature, which of the
(a) - 26.4 kcal (b) 41.2 kcal following statements is correct ? [AIEEEJ
(c) 26.4 kcal (d) 229.2 kcal
(a) (Tl )irrev > (Tl )rev
11. Internal energy is sum of [BCECEJ (b) T1 > T; for reversible process but T1 = T; for
(a) kinetic energy and potential energy irreversible process
(b) all types of energy of the system (c) (Tl ),ev = (Tl ) irrev
(c) energy of internal system ( d) T1 = 1'; for both reversible and irreversible processes
(d) None of the above 19. A hypothetical reaction A➔ 2B, proceeds through
following sequence of steps
2007 (i) A~C;W = q
12. At 27° C one mole of an ideal gas is compressed (ii) C ~ D; w = V
isothermally and reversible from a pressure of 2 attn to
...) -1 D ~ B ; W = x
(m
10 attn. The value of !'1 E and q are ( R = 2 cal) [BITSATJ
2
(a) 0, - 965.84cal
Then, the heat of reaction is [BITSATJ
(b) - 965.84cal, - 865.58cal
(c) + 865.58cal, - 865.58cal (a) q - v+2x (b) q + v - 2x
(d) +965.84cal, + 865.58cal (c) q+v+2x (d) q + 2v - 2x

13. Hess's law is based on [MHTCET] 20. In a closed contamer, a liquid is stirred with a paddle to
increase the temperature. Which of the following is true?
(a) law of conservation of mass
(b) law of conservation of energy (a) M = W ::t: 0,q = 0 [MHT CETJ
(c) first law ofthem1odynamics (b) M = W = q ::t: 0
(d) None of the above ( c) M = 0, W = q ::t: 0
(d) W = 0, M = q ::t: 0
14. The internal energy changes when a system goes from state
A to B is 40 kJ/mol. If the system goes from A to B by a 21. Two moles of helium gas expanded isothermally and
reversible path and returns to state A by an i.tTeversible i.tTeversible at 27°C fom1 volume 1 dm 3 to 1 m 3 at constant
path, what would be the net change in internal energy ? pressure of 100 k Pa. Calculate the work done. [MHT CETJ
(a) 40 kJ {b) > 40 kJ [MP PET] (a) 99900 kJ (b) 99900 J
(c) < 40 kJ (d) Zero (c) 35464.65 kJ (d) 34465.65 J
15. Mark out the enthalpy of formation of carbon monoxide 22. In an isothermal process [MPPET]
(CO) (a) q = 0andM = 0 (b) q ::t: 0 and M = 0
Given, C(s) + _!_ 0 2 (g) ~ CO(g),
( c) q = 0 and M ,t: 0 (d) q ::t: 0 and !'1 E ::t: 0
2 23. The first law of thermodynan1ics is expressed as
W = - 39.3 kJ/rnol (a) q - W = !'1 E [Kerala CEE]
1 (b) f...E = q - W
CO(g) + 0 2 (g) ~ CO 2 (g 1 W = - 282.8 kJ/ mol
2 (c) q = M - W
[AMU, Jamia Millia Islamia] (d) W=q+!'1E
(a) 110.5 kJ/mol (b) 676.1 kJ/mol (e) None of the above
(c) 282.8 kJ/mol (d) 300.0 kJ/mol 24. Hess's law is used to calculate [Jamia Millia Islamia]
16. In an adiabatic process [OJEEJ (a) enthalpy ofreaction
(a) p-!'1V = 0 (b)q =+ W (b) entropy of reaction
( c) work done in reaction
(c) M = q (d) q = 0 ( d) All of these
124 I Chapterwise & Topicwise Engineering Entrances Solved Papers
25. When one mole of monoatomic ideal gas at TK undergoes (a) 41.8 kJ/mol (b) - 41.8 k:J/ mol
adiabatic change under a constant external pressure of (c) 72.8 kJ/mol (d) - 72.8 k:J/ mol
1 atm changes volume from 1 L to 2 L. The final 27. The temperature of the system decreases in an [KCETJ
temperature in Kelvin would be [IIT JEE] (a) adiabatic compression
T 2 (b) isothermal compression
(a) 213 (b) T + 3x 0.0821 ( c) isothermal expansion
2
2 ( d) adiabatic expansion
(c) T (d) T
3 X 0.082] 28. When two moles of hydrogen expands isothem1aJly
against a constant pressure of 1 atm, at 25° C from 15 L to
2005 50 L, the work done (in litre atrn) will be [AMUJ
26. The sublimation energy of 12 (s) is 57.3 kJ/mol and the (a) 17.5 (b) 35
enthalpy of fusion is 15.5 kJ/mol. The enthalpy of (c) 51.5 (d) 70
vaporisation of 12 is [BITSATJ

Topic 3
Enthalpies, Types and their Calculations, Heat
Capacity of the System
2014
1. For the complete combustion of ethanol, 5. On complete combustion, 0 .246 g of an organic compound
C 2 H 5 OH (/) + 302 (g) ~ 2CO 2 (g) + 3H2 0(l\ the gave 0.198 g of CO 2 and 0.1014 g of H2 0. The ratio of
amount of beat produced as measured in bomb calorimeter, carbon and hydrogen atoms in the compound is [AMUJ
1
is 1364.47 kJ mo!- at 25°C. Assuming ideality the (a) I : 3 (b) 1 : 2
enthalpy of combustion, t-,.Hc, for the reaction will be (c) 2: 5 (d) 2: 7
1 1
(R = 8.314JK- mol- ) [JEEMains] 6. For which of the following equations is the change in
(a) -1366.95kJmol- 1
(b) -1361.95kJmol- 1 enthalpy at 25°C and 1 atm equal to /'ili 0 1 of CH 2 0( /)
1 1 [IPUCET]
(c) -1460.50kJmol- (d) - 1350.50kJmol-
(a) C(g) + H 2 (g)+(V2) O 2 (g) ~ CH2 O(l)
2. The heat of combustion of sucrose, C 12 H 22 O 11 (s) at (b) C(s) + H 2 (g) + (l/ 2)O 2 (g) ~ CH 2 O(/)
1
constant volume is 1348.9 kcal mo! - at 25°C, then the (c) C(g) + 2H2 (g)+ O(g) ~ CH2 0(/)
heat of reaction at constant pressure when steam is (d) CO(g) + H 2 (g) ~ CH 2 0(/)
produced [BITSAT]
(a) - 1348.9 kcal
2013
(b) -1342.34 kcal 7. The standard enthalpies of formation of CO 2 (g ), H 2 0(/)
(c) + 1250kcal and glucose (s) at 25°C are - 400 kJ/ mol, - 300 kJ/ mol
(d) None of the above and - 1300 kJ/ mol, respectively. The standard enthalpy of
3. The standard molar beat of formation of ethane, CO 2 and combustion per gram of glucose at 25°C is
[JEE Adcanced]
water (l) are respectively - 21 .1 , - 94.1 and - 68.3 kcal.
The standard molar heat of combustion of ethane will be (a) + 2900 kJ (b) - 2900kJ
(c) - 16.llkJ (d) + 16.11 kJ
(a) - 372kcal (b) 162 kcal [VITEEEJ
(c) - 240kcal (d) 183.5 kcal 8. In order to decompose 9 g water 142.5 kJ heat is required.
Hence, the enthalpy of fom1ation of water is [KCETJ
4. The ratio of heats liberated at 298 K from the combustion
of one kg of coke and by burning water gas obtained from (a) -142.5 kJ (b) + 142.5 kJ
1kg ofcoke is (Assume coke to be 100% carbon). (Given : (c) - 285 kJ (d) + 285 kJ
enthalpies ofcombustion ofC, CO and H2 as 393.5 kJ, 285 9. The enthalpy of combustion of C 6 H 6 (/) is - 3250 kJ.
kJ, 285 kJ respectively all at 298 K) [KCETJ When 0.39 g of benzene is burnt in excess of oxygen in an
(a) 0.79: I (b) 0.69: I open vessel, the amount of heat liberated is [KCETJ
(c) 0.86: I (d) 0 .96: I (a) 16.25 J (b) 16.25 kJ (c) 32.5 J (d) 32.5 kJ
 Thermodynamics I 125
2012
10. A coffee cup calorimeter initially contains 125 g of water at 17. The amount of the heat released when 20 mL 0. 5 M NaOH
a temperature of 24.2°C. After adding 10.5 g of KBr, the is mixed with 100 mL 0.1 M HCI is x kl The heat of
temperature becomes 21 .1°C. The heat of solution is neutralisation is [WB JEE]
(a) 40 Ji g (b) 117Jlg [Manipal]
(a) - l00x kJ/ mol (b) - 50x kJ/ mol
(c) 167.7 Ji g {d) 420.05 Jig (c) + l00x kJ/ mol (d) + 50x kJ/ mol
11. Given, that,
2010
H 2 O(/) ~ H+ (aq)+ OH- (aq); Aff = 57.32 kJ
18. The bond energy (in kcal mo1- 1) of C-C single bond is
I approxin1ately
H 2 (g) + - 0 2 (g) ~ H 2 O(/); Aff = - 286.02 kJ [ITT JEE]
2 (a) I (b) 10 (c) 100 (d) 1000
Then, calculate the enthalpy of fonnation of OH- at 25°C. 19. The species which by definition has zero standard molar
(a) - 228.8 kJ {b) - 343.53 kJ [BITSAT] enthalpy of formation at 298 K is [ITT JEE]
(c) + 228.8 kJ (d) + 343.52 kJ (a) Br2 (g) (b) Cl 2 (g) (c) H 2 O(g) (d) CH 4 (g)
12. Calculate the amount of heat evolved when 500cm3 of 20. The standard enthalpy of formation of NH 3 is
0.1 MHClismixedwith200cm3 of0.2MNaOH. - 46.0 kJ mol-
1
If the enthalpy of formation of H 2
•
(a) 57.3 kJ (b) 2.865 kJ [BITSAT] from its atoms is - 436 kJ mol- 1 and that of N 2 is
(c) 2.292 kJ (d) 0.573 kJ - 712 kJ mol- 1 , the average bond enthalpy ofN-Hbond
13. A sample of liquid in a thermally insulated container is in NH3 is [AIEEEJ
stirred for 1 h by a mechanical attachment to a motor in the 1 1
(a) - 964 kJ mol- (b) + 352 kJ mol-
surroundings, which of the following thennodynarnic
1 1
quantity for the system is zero ? [AMU] (c) + 1056kJmol- (d) -1 102kJmol-
(a) Work (W) 21. In which of the following reactions, the enthalpy is the
(b) Change in internal energy (M) least ? [MP PET]
(c) Change in enthalpy (Aff) (a) CH 3 COOH+ Na0H ~ CH 3 COONa + H 2 O
(d) None of the above (b) HCl+NH 4 OH ~ NH4 Cl+H2 O
(c) HCI + NaOH ~ NaCl+ H 2 O
2011
(d) HCN + NH4 OH ~ NH4 CN+ H 2 O
14. The value of enthalpy change (Af-J) for the reaction
C 2 H 5 OH (/)+ 302 (g ) ➔ 2CO2 (g ) + 3H2 O(l),at 27°C is 22. The heat of neutralisation is highest for the reaction
between [JCE CE]
-1366· 5kJ mol- 1 • The value ofintemal energy change for
the above reaction at this temperature will be [AIEEE] (a) NH4 OH-CH3 COOH (b) HNO 3 -NH4 OH
(c) NaOH-CH 3 COOH (d) HCI-NaOH
(a) - 1371.5 kJ (b) - 1369.0kJ
(c) -1364.0kJ (d) -1361.SkJ 2009
15. Consider the reaction, 23. In a constant volume calorimeter, 3.5 g of a gas with
4NO2 (g) + O 2 (g) ~ 2N2 O 5 (g), L\ rH = -Ill KJ. molecular weight 28 was b urnt in excess oxygen at
If N2 0 5 ( s) is fonned instead of N 2 0 5 (g) in the above 298.0 K . The temperature of the calorimeter was found to
reaction, the L'1,H value will be (Given, Aff ofsublimation increase from 298.0 K to 298.45 K, due to the combustion
1
for N 2 O 5 is 54 kJ mol- ) [AIEEE] process. Given, that the heat capacity of the calorimeter is
1
2. 5 kJ K - , the numerical value for the enthalpy of
(a) - 165kJ {b) + 54kJ
(c) + 219kJ (d) - 219kJ combustion of the gas in kJ mo1- 1 is [ITT JEE]
(a) 7 (b) 9 (c) 0 (d) 8
16. Molar heat capacity of aluminium is 25 JK- 1 mo1- 1 • The
heat necessary to raise the temperature of 54 g of 24. The enthalpy of formation ofNH 3 is-46kJ mol - 1 • The
1
aluminium (Atomic mass 27 g mol- ) from 30°C to 50°C enthalpy change for the reaction
is [Ke rala CEE] 2NH3 (g ) ➔ N 2 (g )+ 3H2 (g) is [Manipal]
(a) 1.5kJ (b) 0.5 kJ (a) + 184 kJ (b) + 23 kJ
(c) l.0kJ (d) 2.5kJ (c) + 92 kJ (d) + 46 kJ
(e) 2.0kJ
126 I Chapterwise & Topicwise Engineering Entrances Solved Papers
25. When 0 . 2 g of 1-butanol was burnt in a suitable apparatus, 32. If f:..E is the heat of reaction for
the heat evolved was sufficient to raise the temperature of
C 2 H 5 OH(l)+ 3O2 (g) ~ 2CO2 (g) + 3H2 O(l)
200 g water by 5°C. The enthalpy of combustion of
1-butanol in kcal mol- 1 will be [Kerala CEE] at constant volume, then LVf (heat of reaction at constant
pressure), at constant temperature is [MHT CET]
(a) + 37 (b) + 370
(c) - 370 (d) - 740 (a) f:..H = f:..E + RT (b) f:..H = f:..E - RT
(e) - 14.8 (c) f:..H = f:..E - 2RT (d) f:..H = f:..E+2RT
26. How many joules of beat are absorbed when 70. O g of 33. Ifone mole of ammonia and one mole ofhydrogen chloride
water is completely vaporised at its boiling point ? are mixed in a closed container to form ammonium
( Lv = 2260 k:J/kg) [UPSEE] chloride gas, then [KCET]

(a) 23352 (b) 7000 (c) 15813 (d) 158200 (a) Aff> f:..U (b) LVf = f:..U
(c) LVf < f:..U (d) there is no relationship
5
27. C 2 H 2 + - 0 2 ~ 2CO 2 + H 2 O ; LVf = - 310kcal 34. Using the following thermochemical equations
2
C+O 2 ~ CO 2 ;Aff = -94kcal (i) S(rhombic)+~ 0 2 (g) ~ SO3 (g);
1 2
H 2 + - O 2 ~ H 2 O; Aff =- 68kcal LVf = - 2x kJ mo1-1
2
On the basis of the above equations, LVf1 (enthalpy of (ii) SO2 (g) + _!02 (g) ~ SO3 (g);
fom1ation) ofC 2 H 2 will be [Indraprashta CET, CGPET] 2
1
(a) - 148 kcal (b) + 54 kcal LVf = - y kl mo1-
(c) - 54 kcal (d) + 80 kcal Find out the heat of fom1ation of SO 2 (g) in kJ mol-1 .
28. For the reactions A ➔ B; LVf = + 24 kJ/mol and (a) (2x + y) (b) (x + y) [KeralaCEE]
B ➔ C; LVf = -18 kJ/mol, the decreasing order of
enthalpy of A, B, C follows the order [DCE] (c) ( : ) (d) (y - 2x) (e) (2x - y )
(a) A,B,C (b) B,C, A
(c) C,B,A (d) C,A,B 35. The heat of formations for CO2 (g ), H2 0 (l) and CH4 (g)
are - 400 kJ mo1-1, - 280 kJ mo1- 1 and - 70 kJ mo1-1
2008 1
respectively. The heat of combustion ofCH4 in kJ mo1- is
29. Calculate LVf in kJ for the following reaction
(a) 890 (b) - 160 [UPSEE]
C(g) + O 2 ( g ) ~ CO 2 (g)
(c) - 890 (d) - 90
Given that,
36. The bond dissociation energies of H2 , Cl 2 and HCl are
H 2 O(g) + C(g)~ CO(g)+ H2 (g); LVf = + 13lk:J
104, 58 and I 03 kcal mo1-1 respectively. The enthalpy of
1 fom1ation of HCl would be [Guj CET]
CO(g)+ - O 2 ( g ) ~ CO2 (g); Aff = - 282kJ
2
(a) - 22 kcal mo1-1 (b) - 44 kcal mo1- 1
1
H 2 (g) + - O 2 ( g ) ~ H 2 0(g); 6.. H = - 242 kJ (c) + 44 kcal mol-1 (d) + 22kcal mol-1
2
(a) - 393 (b) + 393 [BITSAT] 37. LVf for the reaction,
(c) + 655 (d) - 655 C(graphite) + 2H 2 ( g ) ~ CH 4 (g)at298 Kand l attn is
- 17900 cal. The M for the above conversion would be
30. The heat of combustion of solid benzoic acid at constant
volume is - 321. 30 kJ at 27° C . The heat ofcombustion at (a) - 17900cal (b) 17900 cal [J&K CET]
constant pressure is [Manipal] (c) 17304 cal (d) - 17304 cal
(a) - 321.30 - 300R (b) - 321.30 + 300 R 2007
(c) - 321.30-150R (d) - 321.30+ 900 R
38. Assuming that water vapour is an ideal gas, the internal
31. Which of the following reaction defines Aff~ ? [Manipal] energy change (6..U)when 1 mole of water is vaporised at 1
(a) C(diamond) + 0 2 (g) ~ CO2 (g) bar pressure and 100° C, (Given, molar enthalpy of
1 1 vaporisation of water at 1 bar and 373 K = 41 kJ mo1-1 and
(b) H2 (g)+ F2 (g)~ HF(g)
2 2 R = 8. 3 J n101- I K- 1 ) will be [AIEEE]
(c) N 2 (g)+ 3H2 ( g ) ~ 2NH 3 (g) (a) 4.100 kJ mol-
1
(b) 3.7904 k:J mol-
1
1
(d) CO(g)+- O 2 ( g ) ~ CO2 (g) (c) 37.904 kJ mo1- 1 (d) 4 1.00 kJ mo1- 1
2
 Thermodynamics I 127
39. Given, 2C + 202 (g) ~ 2CO2 (g ); /},ff= - 787 kJ 48. Calculate enthalpy for formation of ethylene from the
I following data [EAMCETJ
H2(g)+- O2(g) ~ H 2O(/); /},ff = - 286kJ
2 I. C(graphite)+ O2 (g) ~ CO2 (g);W = 393.5 kJ
1
II. H 2 (g)+ - O2 (g) ~ H2O(/); W= - 286.2kJ
2
III. C2H4 (g)+ 3O2 (g) ~ 2CO2 (g)+2H 2 0(/);
/},ff = - 1310kJ
W = - 1410.8kJ
The heat of formation of acetylene is [VITEEE]
(a) 54.1 kJ (b) 44.8 kJ (c) 51.4 kJ (d) 48.4 kJ
(a) - 1802 kJ (b) + 1802 kJ
49. The decreasing order of bond dissociation energies of
(c) + 237 kJ (d) - 800 kJ C-C, C-H and H-H bonds is [EAMCETJ
40. If the bond energies of H-H, Br- Br and H-Br are (a) H-H>---C-H >-C-C-
0

433, 192 and 364 kJ mol-1 respectively, then W for the (b) - C - C - > - C -H > H-H
reaction H2 (g) + Br2 (g) ~ 2HBr(g) is [Manipal] (c) - C -H > - C-C-> H-H
(a) - 26lkJ (b) + 103kJ (d) -C - C->H-H>- C- H -
(c) + 26lkJ (d) - 103kJ 50. Heat of combustion of carbon monoxide at constant
41. The bond energy is the energy required to [MHT CET] volume and at 17° C is - 67710 cal. The heat of
(a) dissociate one mole of the substance combustion at constant pressure is [J&K CET]
(b) dissociate bond in 1 kg of the substance (a) - 68000cal (b) - 67800cal
(c) break one mole of similar bonds (c) - 67050cal (d) + 68500cal
(d) break bonds in one mole of substance
2006
42. For the reaction, 2H 2(g) + 0 2 (g) ~ 2H 2O(g);
51. For N2 (g) + 3H2 (g) :.====! 2NH3 (g ), AH is equal to
W = - 573.2kJ
(a) M + 2RT (b) AE - 2RT [DCEJ
The heat of decomposition of water per mole is (c) AE+RT (d) AE - RT
(a) 286.6 kJ (b) 573.2 kJ [MHT CET]
52. A monoatornic ideal gas undergoes a process in which the
(c) - 28.66 kJ (d) zero
ratio of P to V at any instant is constant and equals to 1.
43. For an ideal gas, the heat of reaction at constant pressure What is the molar heat capacity of the gas? [IIT JEE]
and constant volume are related as [MHT CETJ
(a) 4R (b) 3R (c) 5R (d) O
(a) H + E = pV (b) E = H + pAV 2 2 2
(c) qP = qv + AnRT (d) None of these
53. The standard enthalpy of formation (W;) at 298 K for
44. If at 298 K the bond energies of C- H, C-C, C = C and
methane, CH4 (g), is - 78.4 kJ mo1- 1 . The additional
H- H bonds are respectively 414, 347, 615 and 435 kJ
mor', then value of enthalpy change for the reaction, information required to determine the average energy for
C- H bond formation would be [AIEEEJ
H2C= CH2(g)+H 2(g) ~ H 3 C- CH3 (g)
(a) the dissociation energy of H 2 and enthalpy of
at 298 K will be [UPSEE, MP PET] sublimation of carbon
(a) +250kJ (b) - 250kJ (c) + 125kJ (d) - 125kJ (b) latent heat of vaporisation of methane
45. The relation between Wand AU is [KCET] (c) the first four ionisation energies of carbon and
electron gain enthalpy of hydrogen
(a) W=AU+RT {b) W = AU - AnRT
(d) the dissociation energy of hydrogen molecule, H2
(c) W = AU +AnRT (d) AU = W + AnRT
54. The enthalpy changes for the following processes are listed
46. Consider the reaction, N 2 + 3H2 ~ 2NH3 carried out below.
at constant temperature and pressure. If Wand AU are the Cl 2 (g) = 2Cl(g ), 242.3 kJ mo1- 1
enthalpy and internal energy changes for the reaction, 12 (g) = 2l (g), 151.0 kJ n101- 1
which of the following expressions is true ? [UPSEE]
ICl (g) = I(g)+ Cl(g),21 1.3 kJ mo1-1
(a) W > AU(b) W < AU(c) W = AU(d) W = 0
12 (s) = 12 (g ), 62.76 kJ mol- 1
47. The enthalpies of combustion of carbon and carbon
monoxideare - 393.5and- 283kJmor1 respectively. The Given that the standard states for iodine and chlorine are
12 (s) and Cl 2 (g), the standard enthalpy of formation of
enthalpy of formation of carbon monoxide per mole is
ICl(g) is [AIEEEJ
(a) 110.5 kJ {b) 676.5 kJ [UPSEE] 1
(a) - 14.6kJmo1- (b) - 16.8kJ mol- l
(c) - 676.5 kJ (d) - 110.5 kJ (c) + 16.8kJmol- 1 (d) + 244.8kJ mol- 1
128 I Chapterwise & Topicwise Engineering Entrances Solved Papers
55. (AH - 1-,.U) for the fommtion of carbon monoxide (CO) 65. Identify the reaction for which AH :t= M [EAMCET]
1 1
from its elements at 298 K is (R = 8. 314 JK- m0 1- ) (a) S (rhombic)+ 0 2 (g) ~ SO2 (g)
[AIEEE] (b) N2(g)+ O 2 (g) ~ 2NO(g)
(a) - 1238.78 J moi-
1
(b) 1238.78 J mo1-1 (c) H2(g) + Cl 2 (g) ~ 2HCl(g)
1 1 l
(c) - 2477.57mo1- (d) 2477.57 J mol- (d) CO(g)+ - O 2 (g) ~ CO2 (g)
2
56. If heat of neutralisation ofHCN with NaOH is - 12.1 kJ
66. Among the following which is true forl mole ofliquid ?
and the heat of neutralisation of HCI by NaOH is
- 55.9 kJ/mol, then the energy of dissociation ofHCN is (a)Cp"'Cv (b)Cp - Cv = R [OJEEJ
(a) 43.8 kJ (b) - 43.8 kJ [Manipall (c) C P - Cv > R (d) C P < Cv
(c) - 68 kJ (d) 68 kJ 67. Which of the following indicates the heat ofreaction equal
to heat of formation ? [OJEEJ
57. The standard molar heat of formation of ethane, CO 2 and
(a) C(graphite) + O 2 (latm) ~ CO2 (latm)
water (/) are - 21.1, - 94. land - 68 . 3 kcal, respectively.
(b) C(diamond) + 0 2 (I atm) ~ CO 2 (2 atm)
The standard molar heat of combustion of ethane will be
(c) C(graphite) + O 2 (latm) ~ CO2 (2atm)
(a) - 372 kcal (b) 162 kcal [MIIT CETJ
(d) C(diamond) + 0 2 ( l atrn) ~ CO 2 (1 atm)
(c) - 240 kcal (d) 183.5 kcal
68. Calculate AH (in Joules) for, C (graphite) ~ C
58. Heat of neutralisation will be minimum for which of the (diamond), from the following data
following combination ? [MP PET]
C (graphite) + 0 2 (g) ~ CO2 (g ); AH = - 393.5 kJ
(a) NaOH+H 2SO4
C (diamond)+ 0 2 (g) ~ CO2 (g ); AH = - 395.4 kJ
(b) NH4 OH+ CH 3 COOH
[J &K CET]
(c) NaOH + HCl
(d) NaOH + CH 3 COOH (a) 1900 (b) - 788.9x 103
(c) 190000 (d) + 788.9x 103
59. Heat of formation of SO2 is - 298 kJ. What is the heat of
combustion of 4 g of S ? [MP PET] 69. In which of the following reactions, the heat liberated is
known as "heat of combustion" ? [J&K CETJ
(a) + 37 kJ (b) - 37.25 kJ
(c) + 298kJ (d) 18.6 kJ (a) H + (aq) + Oir (aq) ➔ H 2O(l)+ heat
60. The heats of combustion of carbon monoxide at constant (b) C (graphite) + .!_ 0 2 (g) ➔ CO(g) + heat
pressw-e and at constant volume at 27° C will differ from 2
one another by [UPSEEJ (c) CH 4 (g)+2O2 (g) ➔ CO 2 (g)+2H 2O(/)+heat
(a) 27 cal (b) 54 cal {c) 300 cal (d) 600 cal (d) H 2SO4 (aq)+ H 2O (l) ➔ H 2SO4 (aq) + heat
61. For the reaction, A (g) + 2B(g) ~ 2C (g) + 3D (g) 70. For CaCO3 (s) ~ CaO(s)+ CO 2 (g) at 927° C
AH = 176 kJ mol; then Mis CBCECEJ
the change of enthalpy at 27° C is 19 kcal. The value of M
is [UPSEEJ
(a) 180 kJ (b) 186.4 kJ
(c) 166.0 kJ (d) 160 kJ
(a) 21.2 kcal (b) 17.8 kcal (c) 18.4 kcal (d) 20.6 kcal
71. The H- H bond energy is 430 kJ mo1-1 and Cl - Cl bond
62. ln an isochoric process, AH for a system is equal to 1
energy is 240 kJ mol- , AH for HCI is - 90 kJ. The H-Cl
(a) p . t-,.V (b) pV [UPSEEJ
bond energy is about [BCECEJ
(c) E + p-t-,.V (d) t-,.E
1
(a) 180 kJ mo1-
63. When 50cm3 of0.2N H 2SO 4 is mixed with 50cm3 of
(b) 360kJmol-1
I N KOH, the heat liberated is [AMU, KCETJ
1
(a) ll.46kJ (b) 157.3kJ (c) 573kJ (d) 573J (c) 213 kJ mo1-
64. The enthalpy of reaction, (d) 425 kJ mo1-1
I 72. The AH~ for CO2 (g ), CO(g) and H 2 O(g) are
H2(g) + O2(g) ~ H 2O(g)isAH1 andthatof
2 - 393 . 5, - 110. 5 and - 241. 8 kJ/mol respectively. The
l standard enthalpy change (in kJ) for the reaction
H2(g) + O 2 (g) ~ H 2O(/)isAH2 . ~
2 CO2(g)+H2 (g) CO(g)+H2O(g)is
[Jamia Millia Islamia]
Then [AMU]
(a) 524.1 (b) 41.2
(a) AH1 < AH2 (b) AH1 + AH2 = 0 (d) - 4 1.2
(c) - 262.5
(c) AH1 > AH2 (d) AH1 = AH2
 Thermodynamics I 129
2006
73. For the following two reactions, 81. ~£0 of combustion of iso-butylene is - X kJ moZ-1 • The
(i) CH 4 (g) + 202 (g) ~ CO 2 (g) + 2H 2O; value of t'1H 0 is [Manipal]
0 0 0
t'1H = - 890.4kJ (a) = M (b) > M (c) = 0 (d) < M
(ii) 2Hg0(s) ~ 2Hg(/) + 0 2 (g ); t'1H + 181.6 kJ 82. Minimum work is obtained when 1 kg of ... gas expanded
under 500 kPa to 200 kPa pressure at 0°C. [MHT CET]
Which one of the following statements is correct ?
(a) chlorine (b) oxygen (c) nitrogen (d) methane
(a) Both of them are exothermic [BITSAT]
(b) Both of them are endothermic 83. EnthalpyofformationofHFandHCl are - 16l kJ and - 92
( c) (i) is exothermic and (ii) is endothermic kJ respectively. Which of the following statements is
(d) (i) is endothem1ic and (ii) is exothermic incorrect ? [MP PET]

74. A process is taking place at constant temperature and (a) HCl is more stable than HF
pressure. Then, [AMU]
(b) HF and HCl are exothermic compounds
(c) The affinity offluorine to hydrogen is greater than the
(a) t'1H = M (b) t'1H = TM affinity of chlorine to hydrogen
(c) t'1H = 0 (d) ~S = 0 (d) HF is more stable than HCl
75. Which is correct for an endothermic reaction ? [WB JEE] 84. A mixture of two moles of carbon monoxide and one mole
(a) ~ H is positive (b) ~ His negative of oxygen, in a closed vessel is ignited to convert the
(c) ~Eisnegative (d) ~ H = 0 carbon monoxide to carbon dioxide. If t'1H is the enthalpy
change and M is the change in internal energy, then
76. For the reaction, C (graphite) + ..!. 0 2 (g) ~ CO(g) at (a) t'1H> M CKCET]
2
298 K and 1 atm, t'1H = - 26. 4 kcal. What is M , if the (b) t'1H < M
molar volwne of graphite is 0.0053 L? (c) t'1H = M
[R = 0. 002 kcal mo1- 1K-1 ] ( d) the relationship depends on the capacity of the vessel
[Guj CET]
85. The cooling in refrigerator is due to CKCET]
(a) - 26.7 kcal (b) + 26.7 kcal
(c) - 52.4 kcal (d) + 52.4 kcal (a) reaction of the refrigerator gas
(b) expansion of ice
77. The value of ~E for combustion of 16 g of CH4 is
( c) the expansion of the gas in the refrigerator
- 885389 J at 298 K. The t'1H combustion for CH 4 in ( d) the work of the compressor
J rno1-1 at this temperature will be
86. What would be the heat released when an aqueous solution
(Given that,R = 8. 314 JK-1 mol- 1) containing 0.5 mole of HNO 3 is mixed with 0.3 mole of
OH- (enthalpy ofneutralisation is - 57.1 kJ)?
(a) - 55337 (b) - 880430
(c) - 885389 (d) - 890348 (a) 28.5 kJ (b) 17.1 kJ (c) 45.7 kJ [Ke ralaCEE]
(d) 1.7 kJ (e) 2.85 kJ
2005
87. IfS + 0 2 ~ SO 2;t'1H= - 298. 2kJ
78. If the bond dissociation energies of XY, X 2 and Y2
1
(all diatomic molecules) are in the ratio of 1: 1: 0 .5 and SO2 + - 02 ~ SO3; t'1H = - 98.7 kJ
1
t'1HI for the formation of XY is - 200 kJ mol- • The bond
2
SO3 + H2O ~ H 2SO4 ; t'1H = - 130.2 kJ
dissociation energy of X 2 will be [AIEEE]
1
(a) 400 kJ mol-
1
{b) 300 kJ mol-
1 H2 + - 02 ~ H 2O; t'1H = - 287.3 kJ
2
(c) 20 kJ mo1- 1 (d) None of these
Then, the enthalpy offormation of H 2SO4 at 298 K will be
79. For the reaction (at 1240 Kand 1 atm.) (a) - 814.4 kJ (b) + 320.5 kJ [OJEE]
CaCO3 ( s ) ~ CaO(s)+ CO 2 (g) (c) - 650.3 kJ (d) - 933.7 kJ
t'1H = 176 kJ/mol; M will be [BITSAT] 88. Given, 2Fe + ~ 0 2 ~ Fe 2O 3 ; t'1H =- 193.4 kJ;
(a) 160 kJ (b) 165.6 kJ 1 2
(c) 186.4 kJ (d) 180 kJ Mg + - O 2 ~ MgO; t'1H= - 140.2kJ;
2
80. For the gaseous reaction involving the complete What is the t'1H of the reaction ?
combustion of iso-butane [BITSAT]
3Mg + Fe 2O 3 ~ 3Mg0 + 2Fe [OJEE]
(a) t'1H = M (b) t'1H > M
(a) - 227.2 kJ (b) - 272.3 kJ
(c) t'1H < M (d) None of these
~ n 7.2 kJ ~)n2.3kJ
130 I Chapterwise & Topicwise Engineering Entrances Solved Papers
89. Which of the following is not co1Tect? [EAMCET] 92. The quantity of heat measured for a reaction in a bomb
(a) Dissolution of NH 4 Cl in excess of water is an calorimeter is equal to [J &K CETJ
endothermic process (a) D.G (b) AH (c) pD.V (d) M
(b) Neutralisation process is always exothermic
93. The beat of neutralisation of any strong acid and a strong
(c) The absolute value of enthalpy (H) can be base is nearly equal to [BCECEJ
determined experimentally
(d) The heat ofreaction at constant volume is denoted by (a) - 75.3 kJ (b) + 57.3 kJ (c) - 57.3 kJ (d) + 75.3 kJ
M 94. For the reaction, 2H 2 + 0 2 ~ 2H 2 O
90. Heat liberated with 100 mL of l N NaOH is neutralised by AH = - 571. Bond energy ofH- H = 435, 0 = 0 = 498,
300 mL of IN HCI [RPETI then calculate the average bond energy of O- H bond
(a) ll.56kJ (b) 5.73kJ (c) 22.92kJ (d) 17 .19kJ using the above data [DCEJ
91. The enthalpies of formation of Al 2 O 3 and Cr2 O 3 are (a) 484 (b) - 484 (c) 271 (d) - 271
- 15 96 kJ and - 1134 kJrespectivety. AH for the reaction, 95. Heat required to raise the temperature of I mole of a
2Al + Cr2 0 3 ~ 2Cr + Al 2 0 is [RPETI substance by 1° is called [Jamia Millia Islamia]
3
(a) - 2730 kJ (b) - 462 kJ (a) specific heat (b) molar beat capacity
(c) - 1365 kJ (d) + 2730 kJ (c) water equivalent (d) specific gravity

Topic 4
Entropy, Gibbs Energy and Spontaneity
(llnd and Ill rd Law of Thermodynami cs), Ellingham's Diagram
2014
1. For the process H 2 0(/) ~ H 2 O(g) (b) Carbon can be used to reduce any metal oxide at a
sufficiently high temperature
at T = 1000 Cand 1 atmosphere pressure, the con-ect choice
( c) Carbon reduces many ox.ides at elevated temperature
is [JEE Mains]
because D.G 0 vstemperature line has a negative slope
( a) M system > 0 and M surrounding > 0
(b) M system > 0 and D.S surrounding < 0
(d) t1S 0 [ C(s) +¾ 0 2 (g) ~ CO(g)]
( c) M system < 0 and M surrounding > 0
< D.S [C(s) + 02 (g)
0
~ CO(g )]
( d) Af system < 0 and D.S surrounding < 0
2. Consider th e following Ellingbam's diagram for carbon.
3. A substance is carried out through the following
transformations.
0 t:,.S1 t:,.S2
A------>- B _ ____,. C
- 100
-200 1
t':,.$41 ft':,.$3
t. -300 ,___ _✓
_ c + 202------>-CO D E

t:,.G -400 C +0 2------>- C02

-500 ! The equations D.S 1 + M 2 = D.S 3 + D.S 4 + D.S s
[Manipal]
-600
(a) is true only iftbe steps are ca1Tied out reversibly
-700
(b) is always true because entropy is a state ftmction
-800 ( c) may be true but need more informations on the
processes
710
500 1000 1500 2000 2500 ( d) is incorrect
T("C) 4. At 298 K the entropy of rhombic sulphur is 32.04 J/mol K
and that of monoclinic sulphur is 32.68 J/mol K. The heat
Which of the statement is incon-ect for the above
of their combustion are respectively - 298246 and
Ellinghan1's diagram? [BITSATJ 1
- 297948 J mo! - • D.G for the reactions;
(a) Upto 710°C, the reaction of formation of CO 2 is
energetically more favourable but above 7 10°C, the S rhombic ~ S monoclinic will be [Manipal]
formation of CO is preferred (a) 107.28 J (b) 10.728 J (c) 107.28 kJ(d) 10728 J
 Thermodynamics I 131
5. For an ideal binary liquid mixture [KCET]
(a) M (mix) = 0; t.G(mix) = 0 (a) Mx➔ z = Mx ➔ Y + My ➔ z [IITJEE]
(b) M (mix) = 0; M (rnix) < 0 (b) Wx ➔ Z = Wx ➔ Y + Wy ➔ z
(c) t.V(mix) = 0; t.G(,nix) > 0 (c) Wx ➔ Y ➔ Z = Wx ➔ Y
( d) M (rnix) > 0; t.G(mix) < 0 (d) t-Sx ➔ Y ➔ Z = t.Sx ➔ Y
6. For hydrogen-oxygen fuel cell at I atrn and 298 K 13. Using the data p rovided, calculate the multiple bond
1
H 2 (g) + - 0 2 (g) ~ H 2 0(/); t.G0 = - 240 kJ
1
energy (kJ mo!- )of a C =
Cbond C 2 H 2 • The energy is
1
2 (take the bond energy of a C-H bond as 350 kJ mol- )
0
£ for the cell is approximately, (Given F = 96500 C) [IIT JEE]
1
(a) 2.48 V (b) 1.24 V [WB JEE] 2C (s) + H2 (g) ~ C 2 H 2 (g); M = 225 kJ mol-
(c) 2.5 V (d) 1.26 V 2C(s) ~ 2C(g); M = 1410 kJ mol- 1

7. The enthalpy of vaporisation of a certain liquid at its

H 2 (g) ~ 2H(g);M = 330kJmol- 1
boiling point of 35°C is 24.64 kJ mol - 1 • The value of
change in entropy for the process is [WB JEE] (a) 1165 (b) 837 (c) 865 (d) 815
1 1 1 1
(a) 704 JK- mol- (b) 80 JK - mol- 2012
1 1
(c) 24.64Kr mo1- (d) 7 .04JK- 1mol- l 14. The incorrect expression an1ong the following is [AIEEEJ
8. For a spontaneous process, the correct statement (s) is (are) t.G
(a) system = - T
(a) (LlGsys1em h, P > 0 [WB JEE] M total
(b) (M system ) + ( M surrotmdings ) > 0 . VJ
(b) In 1sothe1mal process, W,eversible = - nRT ln -
(c) (t.Gsystem )r, p < 0 V;
(d) (t.Usystem )r, v > 0 (c) In K = M o - rt.So
9. The values of M and M of a certain reaction are RT
- 400 kJ mol- 1 and - 20 kJ moi- 1 K - 1 respectively. (d) K = e - 6.G IRT 0

The temperature below which the reaction is spontaneous,

15. One mole of ice is converted into water at 273 K.. The
is
entropies of H 2 0(s) and H 2 0(!) are 38.20 and
(a) 100 K (b) 20°C [WBJEE]
60.01 J mo!- 1 K - 1 respectively. The enthalpy change
(c) 20 K (d) 120°C
for the conversion is [Manipal]
10. The temperature ofKat which t.G = 0,for a given reaction (a) 3 kJ mol- 1
(b) 4 kJ mol- 1

withM = - 20.5 kJmol- 1 and M = - 50.0JK- 1 mol- 1 (c) 5 kJ mol-

1
(d) 6 kJ mol-
1

is [EAMCET]
16. Among the following for spontaneity of chemical reaction
(a) - 410 (b) 4 10 (c) 2.44 (d) - 2.44 there should be [MP PET]
2013 (a) decrease in entropy and increase in free energy
(b) decrease in entropy and free energy both
11. If t.Gfor a reaction is negative, you infer that the change is
(c) increase in entropy and decrease in free energy
[Ke rala CEE]
( d) increase in entropy and free energy both
(a) spontaneous (b) non-spontaneous
17. Which of the following processes is associated with
( c) reversible (d) irrevrsible
decrease in entropy ? [MP PET]
(e) equilibrium
(a) Vaporisation ofa mole of water into steam at its b.p.
12. For an ideal gas, consider only p-V work in going from an
(b) Dissociation of a mole of common salt in water at
initial state X to the final state Z. The final state Z can be 300K
reached by either of the two paths shown in the figure. ( c) Mixing of two partially miscible liqui ds
Which of the following choice (s) is (are) correct? ( d) Crystallisation of a salt from its saturated solution
18. Which of the following statements is true? [KCETJ
(a) The total entropy of the universe is continuously
decreasing
(b) The total energy of the universe is continuously
decreasing
V V
( c) The total energy of the universe remains constant
(Take t.S as change in entropy and Was work done.) (d) The total entropy of the universe remains constant
132 I Chapterwise & Topicwise Engineering Entrances Solved Papers
19. Identify the correct statement from the following in a 26. A plot of In k against ]_ (abscissa) is expected to be a
chemical reaction. [WB JEE] T
(a) The entropy always increases straight line with intercept on coordinate axis equal to
(b) The change in entropy along with suitable change in [WBJEE]
enthalpy decides the rate of reaction AfO !).S O llS 0
(c) - - (d) RxtiS 0
(c) The enthalpy always decreases (a) 2.303R (b) R R
( d) Both the enthalpy and the entropy remain constant
27. A container of I. 0 L capacity filled with I. 0 mole of ideal
20. For an isolated system, llU = 0, then [AMU]
gas is connected to an evacuated vessel of 9. 0 L. Calculate
(a) llS =0 change in entropy. (R = l.987cal) [Guj CETl
(b) llS<0 (a) 0.188cal•K- 1 mo1- 1
(b) 0.4576cal·K- 1 mo1- 1
(c) llS > 0 1 1 1 1
(c) 4.576cal ·K - mol- (d) 4 .366cal·K- mol-
( d) The values of llS cannot be predicted

2011 2010
21. The entropy change involved in the isothermal reversible 28. The Gibbs energy for the decomposition of A1 2O 3 at
expansion of2 moles ofan ideal gas from a volume of 500°C is as follows
10 dm3 to a volume of I 00 dm3at 27°C is
1 1
[AIEEEJ
1
~ Al2O3 ➔ _i Al+ 0 2 , llrG = + 966 kJ mo! - 1
(a) 38.3 J mol- K- (b)35.8Jmol - t K - 3 3
(c) 32.3 Jmol- 1 K - 1
(d) 42.3 J mol- 1K - 1 The potential difference needed for electrolytic reduction
0
of Al 20 3 at 500°C is at least [AIEEEJ
22. In view of the signs of llrG for the following reactions
(a) 4.5 V (b) 3.0 V (c) 2 .5 V (d) 5.0 V
PbO2 + Pb ~ 2PbO, ll r G 0 < 0, 29. For a particular reversible reaction at temperature T, /iH
SnO2 +Sn ~ 2SnO,llrG0 > 0, and llS were found to be both +ve. lfTe is the temperature
Which oxidation states are more characteristic for lead and at equilibrium, the reaction would be spontaneous when
tin ? [AIEEE] (a) Te> T (b) T> Te [AIEEEJ
(a) For lead+ 4, for tin+ 2 (c) Te is 5 times T (d) T = Te
(b) For lead + 2, for tin + 2 30. When ice melts into water, the entropy [Manipall
(c) For lead+ 4, for tin+ 4 (a) becomes zero (b) remains same
( d) For lead + 2, for tin + 4 ( c) decreases ( d) increases
23. For the reversible reaction, 31. If llG is negative, the reaction will be [MP PET]
~ C(g)+D(g); llG =- 350kJ,
0
A(s)+B(g) (a) at equilibrium (b) not possible
which one of the following statements is true ? [KCETJ (c) Both (a) and (b) (d) possible
(a) The reaction is thermodynamically non-feasible 32. Which one of the following is correct ? [JCECEJ
(b) The entropy change is negative (a) - llG = !iH - TllS (b) !iH = [llG - TllS]
(c) Equilibrium constant is greater than one I I
( d) The reaction should be instantaneous (c) Af =- [llG - /iH] (d) llS =- [/iH - llG]
T T
24. Carbon cannot reduce Fe 2O 3 to Feat a temperature below
33. During which phenomenon does entropy decrease ?
983 K because [KCETJ [Guj CET]
( a) free energy change for the formation of CO is more
(a) Crystallisation of sucrose from its solution
negative than that ofFe 2O 3
(b) Melting of ice
(b) CO is thermodynamically more stable than Fe 2O 3
(c) carbon has higher affinity towards oxygen than iron ( c) Sublimation of camphor
(d) iron has higher affinity towards oxygen than carbon ( d) Rusting of iron
25. The enthalpy of vaporisation of benzene is+35. 3 kJ/mol at 34. Which of the following reactions define llG;? [Guj CETJ
its boiling point of 80°C. The entropy change in (a) C(diamond) + 0 (g) ~ CO2 (g)
2
the transition of vapour to liquid at its boiling point is .... l l
(b) - H 2 (g)+ -F2 (g) ~ HF(g)
[in J mol- 1 K - 1] . [KCET] 2 2
(a) - 100 (b) +1 00 (c) H 4 P2 0 7 + H 2 0 ~ 2H3 PO4
(c) + 342 (d) - 342 I
( d) SO2 (g) + 0 2 (g) ~ SO3 (g)
2
 Thermodynamics I 133
35. What will be the temperature at which 42. For the reaction at 298 K. A (g) + B(g) ~ C(g)
1 1
11G = - 5. 2kJ mol- , Aff = 145. 6kJ mol- and M = -5 cal and !!..S = - 10 cal K - 1 [AMUJ
!!..S = 216 JK- 1 mol- 1 for a chemical reaction? (a) 11G= +2612cal (b) 11G= - 2612cal
(a) 650 K (b) 425°C [Punjab CE T] (c) 11G = +261.2 cal (d) None of these
(c) 525 K (d) 625°C 43. What will be the value of 11G for ice at 8°C temperature ?
(a) One (b) Negative [Guj CETJ
2009 (c) Positive (d) Zero
36. In a fuel cell methanol is used as fuel and oxygen gas is 44. A piece of ice kept at room temperature melts of its own.
used as an oxidiser. The reaction is This reaction is governed by which law ? [Guj CETJ
CH 3 0H(l) + ~ 0 2 (g) ➔ CO2 (g)+2H2 0(l). (a) Second law of thermodynamics
2 (b) First law of thermodynamics
At 298 K standard Gibb's energies of fo1mation for (c) Third law of thermodynamics
CH3 OH(/), H2 O(/)and CO2 (g )are-166. 2, -237.2and (d) Zeroth law of thermodynamics
- 394 .4 kJ mol- 1 respectively. If standard enthalpy of 45. For a chemical reaction, 11G will always be negative if
combustion of methanol is - 726kJ mo1- 1, efficiency ofthe (a) Aff and ns both are positive [DCEJ
fuel cell will be CAIEEEI
(b) Aff and T!!..S both are negative
(a) 80% (b) 87% (c) 90% (d) 97% (c) Aff is negative and T.-1S is positive
37. For the reaction H2 O(/) ~ H 2 O(g) at 373 Kand (d) Aff is positive and T!!..S is negative
I atm pressure [Manipal] 46. In which reaction there will be increase in entropy? [D CEJ
(a) Aff = 0 (b) M = 0 I
(a) Na(s) +H 2 0(l) ~NaOH(/) + - H 2 (g)
(c) Aff = T!!..S (d) Mf = 11£ 2
38. Given that dE = TdS - pdV and H = E + pV. Which one (b) Ag+ (aq)+ Cl- (aq) ~ AgCl(s)
of the following relations is true? [Kerala CEE] l
(c) H2 (g) +-O2 (g) ~ H2 0(/)
(a) dH = TdS +Vdp 2
(b) dH = SdT + Vdp (d) Cui+ (aq) + 4NH3(g) ~ [Cu(NH3 )4J2+ (aq)
(c) dH = - SdT +Vdp
47. 12 (s) ~ 12 (g ); Mf = + 40 kcal, 11S = 80 cal. The
( d) dH = dE + pdV
(e) dH = dE - TdS sublimation point ofl2 (s) will be [lndraprastha CETJ
39. The entropy of a perfectly crystalline material is zero at WIWC ~l~C ~2~C ~~~
0°C. This is statement of CUPSEE J 2008
(a) first law ofthem1odynamics 48. Standard entropy of X Y2 and XY3 are 60, 40 and
2,
(b) second law of thennodynamics 1 1
(c) third law of thermodynamics 50 JK- mo1- , respectively. For the reaction,
(d) law of conservation of energy I 3
- X 2 + - Y2 ~ XY3 , Mf = - 30kJ,
40. In any chemical reaction, a quantity that decrease to a 2 2
minimum is [UP S EE ] to be at equilibrium, the temperature will be [AIEE EJ
(a) free energy (b) entropy (a) 1250 K (b) 500 K (c) 750 K (d) 1000 K
(c) temperature (d) enthalpy 49. The free energy change for the following reactions are
41. 11G for the reaction Ag 2 O➔ 2Ag +-.!.02 at a certain given below
5
2 C 2 H 2 (g) + - 0 2 (g) ~ 2CO 2 (g)+ H2 0(/);
temperature is found to be -10.0kJ mo1- 1 , which one of 2 11G0 = - 1234 kJ
the following statements is correct at this temperature ? C(s) + 0 2 (g) ~ CO2 (g ); 11G = - 394 kJ
0

[OJEE] I
H 2 (g) + - 0 2 (g) ~ H2 O(!); 11G0 = - 237 kJ
(a) Silver oxide decomposes to give silver and oxygen 2
(b) Silver and oxygen combine to fo1m silver oxide What is the standard free energy change for the reaction
(c) The reaction is in equilibrium H 2 (g)+2C(s) ~ C 2 H 2 (g)? CBITSATJ
(d) The reaction can neither occur in the forward
direction nor in the backward direction (a) - 209kJ (b) - 2259 kJ
(c) + 2259 kJ (d) 209 kJ
134 I Chapterwise & Topicwise Engineering Entrances Solved Papers
50. The standard free energy change of a reaction is 59. For a reversible reaction,
tiG 0 = - 115kJ at 298 K. Calculate the equilibrium constant X(g)+ 3Y(g) ~ 2Z(g); Aff = - 40kJ, the standard
1 1
KP in logK P [R = 8.314 JK- mol- ] [VITEEEJ entropies of X, Y and Z are 60, 40 and 50 JK- 111101- 1
(a) 20.16 (b) 2.303 (c) 2.016 (d) 13.83 respectively. The temperature at which the above reaction
attains equilibrium is about [Jamia Millia IslamiaJ
51. If an endothermic reaction occurs spontaneously at
constant temperature (T) and pressure (p), then which of (a) 400 K (b) 500 K
the following is true ? [VITEEEJ (c) 273 K (d) 373 K
(a) tiG> 0 (b) Aff < 0 (c) tiS > 0 (d) !1S < 0 60. The latent heat of fusion of ice at 0° C is 80 cal/g. Entropy
52. A spontaneous process is one in which the system suffers change (tiS) accompanying the melting of 1 g of ice at
( a) no energy change [VITEEEJ 0° C would be (units cal/g/K) [J&K CETJ
(b) a lowering of free energy (a) 273 (b) 8.0
( c) a lowering of entropy (c) 0.9 (d) 0.293
( d) an increase in internal energy 61. Which one of the following is spontaneous at all
53. Which is the correct expression, that relates changes of temperatures ? [J&K CETJ
entropy with the change of pressure for an ideal gas at (a) H 2 (g) ~ 2H(atom);
constant temperature in the following ? [MP PETJ Aff0 = 436 kJ, tiS 0 = 90.7 e u
1 1
(a) !1S = nRT In J!..!. (b) tiS = T(p 2 - p1) (b) - N 2 (g )+- O 2 (g) ~ NO(g);
P2 2 2
(c) !1S = nR In l!..!. (d) S = 2.303 nRT In J!..!. Aff0 = 90.3 kJ, 1'1S 0 = 3.0eu
P2 P2 (c) 2NO 2 (g) ~ N 2 O 4 (g);
0 0
54. One mole of which of the following has the highest Af{ = - 56.0 kJ, tiS = - 17.7eU
entropy? [KCETJ 1
(d) H 2 O 2 (g) ~ H 2 O(/)+ - O 2 (g);
(a) Liquid nitrogen (b) Hydroge n gas 2
(c) Mercury (d) Diamond Aff0 = - 98.3 kJ, !1S O = 80.0 eu
55. When compared to tiG0 for the fom1ation of A1 2 0 62. The decomposition of lin1estone
3 , the
0
tiG for the formation of Cr2 0 3 is [KCETJ CaCO3 (g) ~ CaO(s) + CO 2 (g)
(a) higher (b) lower is non-spontaneous at 298 K. The Aff0 and tis O values for
(c) san1e (d) unpredicted the reaction are 76.0 kJ and 60 JK-1 respectively. At
56. For which reaction change of e ntropy will be positive? what temperature the decomposition becomes
(a) H2 (g) + l2 (g) ~ 2HI(g) [WB JEE] spontaneous? [Guj CETJ

(b) HCI(g)+ NH3 (g) ~ NH4 Cl(s) (a) At 1000 K

(c) NH 4 NO3 (s ) ~ N 2 0(g)+2H 2 O(g) (b) Below 500° C
(d) MgO(s) +H 2 (g) ~ Mg(s) + H 2 0(/) ( c) Between 500° C and 600° C
( d) Above 827° C
57. tiG 0 vs T plot in the Ellingham's diagram s lopes upwards
for the reactions [Jamia Millia Islamia] 2007
1 63. The value oflog Kc for a reaction
(a) Mg + - 0 2 ~ MgO
2
1 A ~ B is (Given, tirH0 298K = - 54.07 kJ mo1- 1 ,
(b) 2Ag + - 0 2 ~ Ag 2 O 1 1
2 ti,S 0 298 K = 10 JK- rnol - and
1 R = 8.314 JK- 1mol- 1
(c) C + - O 2 ~ CO
2 2303 X 8.314 X 298 = 5705) [IITJEEJ
1
(d) CO + - O 2 ~ CO2 (a) 5 (b) 10 (c) 95 (d) 100
2
64. For the process H 2 O(/)(l bar, 273 K) ~ H 2 O(g )(1
58. For a reaction to be spontaneous at all temperatures
bar, 273 K) the correct set of them10dynamic parameters is
[Jamia Millia Islamia ]
(a) tiG and Aff should be negative (a) tiG = 0, tiS = + ve [IIT JEE]
(b) tiG and Aff s hould be positive (b) tiG = 0,tiS = - ve
(c) tiG = tiS = 0 (c) tiG=+ve, tiS =0
(d) Aff < tiG (d) tiG = - ve, tis = + ve
 Thermodynamics I 135
65. Identify the correct statement regarding a spontaneous 74. In an irreversible process taking place at constant T and p
process. CAIEEEJ and in which only pressure-volume work is being done, the
(a) For a spontaneous process in an isolated system, the change in Gibbs free energy (dG) and change in entropy
change in entropy is positive (dS \ satisfy the crite1ia. [MP PET]
(b) Endothermic processes are never spontaneous (a) (dS )v,E < 0, (dG)r,P < 0
(c) Exothermic processes are always spontaneous
(b) (dS )v,E > 0, (dG)r,P < 0
( d) Lowering of energy in the reaction process is the only
(c) (dS )v,E = 0, (dG)r,P = 0
criterion for spontaneity
(d) (dS )v,E = 0, (dG)r,p > 0
66. In conversion of limestone to lime,
75. In equilibrium state the value of AG is [KCET]
CaCO3 (s) ~ CaO(s)+CO2 (g)
(a) zero
the values of M 0 and LlS 0 are+ 179.1 kJ mo1-1 and 160.2 (b) negative
J/K respectively at 298 K and 1 bar. Assuming that M 0 (c) positive
and AS 0 do not change with temperature, temperature (d) may be negative or positive
above which conversion of limestone to lime will be
76. Entropy of the universe is [KCET]
spontaneous is [AIEEEJ
(a) constant
(a) 1008K (b) 1200K (c) 845K (d) 11 18K
(b) zero
67. Gibb's free energy G, enthalpy H and entropy S are (c) continuously decreasing
interrelated as in CBITSATJ
(d) continuously increasing
(a) G = H + TS (b) G =H- TS
77. In which of the following process, maximum increase in
(c) G - TS = H (d) G = S= H
entropy is observed ? [KCETJ
68. When a solid melts reversibly [VITEEE]
(a) Melting of ice
(a) H decreases (b) G increases (b) Sublimation of naphthalene
( c) E decreases (d) S increases (c) Condensation of water
69. Enthalpy is equal to [VITEEE] ( d) Dissolution of salt in water

(a) T2 [o(G / T)] (b) - T2[&(G/ T)] 78. Considering the reaction,
C(s) + O 2 (g) ~ CO2 (g)+393.5kJ the signs of
OT P OT P
M, LlS and AG respectively are [KCET]
(c) T2[&(G/ T)]
OT v
(d) -T2[◊(G /
OT
T)] V
(a) +, - , - (b) -, +, + (c) - , - , - (d) - ,+, -
79. If AG= 46.06 kcal / mol, KP at 300 K is COJEEJ
70. Condition for spontaneity in an isothermal process is (a) (b) 10-23.03 (c) 10-so.12 (d) 10+33.33
10-33.33
(a) M + W < 0 (b) AG+ U < 0 [VITEEEJ
80. For a reversible reaction, A system + AS surrounding is [OJEE]
(c)M + U>0 (d)AG - U<0
71. Standard enthalpy and standard entropy changes for the (a) oo (b) zero (c) 1 (d) 2
1
oxidation ofammonia at 298 Kare - 382.64 kJ mo1- and 81. Which is a condition for spontaneous ? [OJEEJ
1 1
- 145.6 JK- rnol- , respectively. Standard Gibbs energy (a)AG<0 (b)AG = 0
change for the same reaction at 298 K is [Manipall ~)AG>0 ~)AG~0
1
(a) - 2221.1 kJ mol- (b) - 339.3 kJ rnol- 1 82. If M = - 25 kcal, T = 300 K and LlS = 9 cal, then the
1
(c) - 439.3 kJ rnol- (d) - 523.2 kJ mol- 1 reaction is [OJEEJ
72. Considering entropy (S) as a thermodynamic parameter (a) spontaneous (b) non-spontaneous
the criterion for the spontaneity of any process is (c) equilibrium state (d) None of these
(a) LlS system + LlS surroundings > 0 [Manipal] 83. All naturally occurring process, proceed in a direction,
which leads to [J&K CETJ
(b) LlS system - AS surro1111dings > 0
(c) LlS system> 0only (a) increase of enthalpy (b) increase of free energy
( d) LlS surroundings > 0 only ( c) decrease of free energy ( d) decrease of entropy
73. The correct relationship between free energy change in a 84. The free energy change AG= 0 when [J&K CET]
reaction and the corresponding equilibrium constantK c is (a) the reactants are completely consumed
[MPPET] (b) a catalyst is added
(a) AG = RTln K c (b) - AG = RT In K c ( c) the system is at equilibrium
(c) AG 0 = RT In K c (d) - AG 0 = RT In K c (d) the reactants are initially mixed
136 I Chapterwise & Topicwise Engineering Entrances Solved Papers
85. For a reaction Afl = (+3 kJ),~S = (+ l0J/ K) beyond 2005
which temperature this reaction will be spontaneous ? 93. For a spontaneous reaction the ~G, equilibrium constant
(a) 300 K (b) 200 K [DCEJ (K) and E 0 cell will be respectively, [AIEEE]
(c) 273 K (d) 373 K (a) - ve, > 1, - ve (b) - ve, < 1, - ve
(c) +ve,> 1, - ve (d) - ve, > l ,+ve
2006
94. A schematic plot of In K eq versus inverse of temperature
86. The direct conversion of A to B is difficult, hence it is
canied out by the following shown path for a reaction is shown below [AIEEEJ

C~D 6.01 /

:OlL,
t J,
A B
Given; ~s (A ➔ C) = 50 eu
1
1.5 x 103 2 x 103 -y(K- )
Afcc ➔ D) = 30eu
Af(B ➔ D) = 20eu The reaction must be
where eu is entropy unit, then ~ S (A ➔ B) is [IIT JEE] (a) highly spontaneous at ordinary temperature
(a) + lO0eu (b) + 60eu (c) - l00eu (d) - 60eu (b) one with negligible enthalpy change
87. In evaporation of water Ml and ~S are [IITJEE]
( c) endothermic
( d) exothem1ic
(a) + , + (b) +, - (c) - , - (d) - , +
95. Maximum entropy will be in which of the following ?
88. Which of the following is correct for the reaction
(a) Ice (b) Snow [ManipaIJ
Ml= + ve and Af = + ve? [BITSATJ
(c) Liquid water (d) Water vapours
(a) Spontaneous at high temperature
(b) Spontaneous at low temperature 96. For a system in equilibrium, ~G = 0 under conditions of
(c) Non-spontaneous at high temperature constant [KCETJ
(d) Non-spontaneous at all temperatures (a) temperature and pressure
(b) temperature and volume
89. For the reaction CO(g) + .!_ 0 2 (g) ~ CO 2 (g ), Ml (c) pressure and volume
2
and Af are - 283 kJ, - 87 JK- 1, respectively. It was ( d) energy and volume
intended to carry out this reaction at 1000, 1500, 3000 and 97. Molar heat of vaporisation of a liquid is 6 kJ mo1- 1• If the
3500 K. At which of these temperatures would this reaction entropy change is 16 J mo1- 1K- 1, the boiling point of the
be thermodynamically spontaneous? [Ke rala CEEJ liquid is [KCETJ
(a) 1500 and 3500 K (a) 375° C (b) 375 K (c) 273 K (d) 102° C
(b) 3000 and 3500 K
98. Ml and Af for a reaction are+ 30.558 kJ mol- 1 and 0.066
(c) 1000, 1500 and 3000 K 1 1
(d) 1500, 3000 and 3500 K kJ K- mol- at l atm pressure. The temperature at which
(e) At all the above temperatures free energy change is equal to zero and the nature of the
reaction below this temperature are [Kerala CEE]
90. For the reaction at 298 K
(a) 483 K, spontaneous
A(g) + B(g) ~ C(g) + D (g)
(b) 443 K, non-spontaneous
1
Ml0 = - 29.8 kcal, Af 0 = - 0.100 kcal K - (c) 443 K , spontaneous
What is the value of ~G0 ? [Guj CET] ( d) 463 K, non-spontaneous
(e) 463 K , spontaneous
(a) l (b) 0 (c) 2 (d) 4
99. The free energy for a reaction having Ml= 31400 cal,
91. What is the relation between E 0 and K? [Guj CET]
1 1
~S = 32calK- mol- atl000° Cis [OJEEJ
(a) Eo = 0.0591 logK 0 n
(b) E = - - logK (a) - 9336 cal (b) - 7386 cal
n 0 .0591
(c) - 1936 cal (d) + 9336 cal
(c) £ 0 = 2.303R log K (d) Eo = 2.303 RT log K
nF n 100. The enthalpy change for the transition of liquid water to
steam is 40.8 kJ per mol at 100° C. The entropy change for
92. What are the units of entropy ? [J&KCETJ
the process will be [AMUJ
(a) cal K (b) cal K- 1 (a) 0.408 JK- 1mol- 1
(b) 408 JK- 1 mol- 1
1
(c) cmK- (d) cm K (c) 109.4 JK- 1mol- 1
(d) 0.1094 JK- 1 mo! - 1
 Thermodynamics I 137
101. The entropy change for the reaction ( c) !>.H and ~S both are - ve
H2 (g) + Cl 2 (g ) ~ 2HCl(g) will be (d) !>.H is +ve, ~S is - ve
1 1
[Given that, S O (HCI) = 187 JK- mo!- 103. Consider the following reactions at 1100° C
1
S (H 2 ) = 131 JK- mo1- and
0 1 (I) 2C + 0 2 ~ 2CO, ~ G 0 = - 460 kJ mo1-1
S 0 (Cl 2 ) = 223 JK- 1 mo1- 1] (II) 2Zn + 0 2 ~ 2Zn0, ~G 0 = - 360kJ mol- 1
[AMU]

(a) 20 JK- 1 mo1-1 (b) - 20JK-1 mo1-1 Based on these, select co1Tect alternate.
(c) 167 JK- 1 mol- 1 (d) - 167 JK- 1mol- 1 [Jamia Millia Islamia]
(a) Zinc can be oxidised by CO
102. If an endothermic reaction is non-spontaneous at freezing
(b) Zinc oxide can be reduced by carbon
point of water and becomes feasible at its boiling point,
(c) Both are correct
then [DCE]
( d) None of the above is correct
(a) !>.His - ve, D.S is +ve
(b) !>.H and ~S both are +ve

Answers
TOPICl Basic Concepts ofThermodynamics
1. (a,b,c) 2. (c) 3. (b) 4. (b) 5. (a) 6. (a) 7. (d) 8. (a) 9. (c) 10. (c)
11. (d) 12. (b) 13. (a) 14. (b) 15. (c) 16. (d) 17. (c)

Ne!C1 Internal Energy (1st Law ofThermodynamics) and Hess's Law

1. (b) 2. (b) 3. (a) 4. (a) 5. (a) 6. (a) 7. (a,c,d) 8. (d) 9. (b) 10. (a)
11. (b) 12. (a) 13. (b) 14. (d) 15. (a) 16. (d) 17. (c) 18. (a) 19. (c) 20. (a)
21. (b) 22. (b) 23. (c) 24. (a) 25. (a) 26. (a) 27. (d) 28. (b)

Ne!C1 Enthalpies Types and their Calculations, Heat Capacity of the System
1. (a) 2. (b) 3. (a) 4. (b) 5. (c) 6. (b) 7. (c) 8. (c) 9. (b) 10. (c)
11. (a) 12. (c) 13. (d) 14. (c) 15. (d) 16. (c) 17. (a) 18. (c) 19. (b) 20. (b)
21 . (d) 22. (d) 23. (b) 24. (c) 25. (c) 26. (d) 27. (b) 28. (b) 29. (a) 30. (c)
31 . (b) 32. (b) 33. (c) 34. (d) 35. (c) 36. (a) 37. (d) 38. (c) 39. (c) 40. (d)
41 . (c) 42. (a) 43. (c) 44. (d) 45. (c) 46. (b) 47. (d) 48. (c) 49. (a) 50. (a)
51 . (b) 52. (a) 53. (a) 54. (c) 55. (b) 56. (a) 57. (a) 58. (b) 59. (b) 60. (c)
61 . (b) 62. (d) 63. (d) 64. (a) 65. (d) 66. (a) 67. (a) 68. (a) 69. (c) 70. (c)
71 . (d) 72. (b) 73. (c) 74. (a) 75. (a) 76. (a) 77. (b) 78. (d) 79. (b) 80. (b)
81 . (d) 82. (a) 83. (a) 84. (b) 85. (c) 86. (b) 87. (a) 88. (a) 89. (c) 90. (b)
91 . (b) 92. (d) 93. (c) 94. (a) 95. (b)

TOPIC4 Entropy, Gibbs Energy and Spontaneity (llnd and Illrd Law ofThermodynamics), Ellingham's Diagram
1. (b) 2. (d) 3. (b) 4. (a) 5. (d) 6. (b) 7. (b) 8. (b,c) 9. (c) 10. (b)
11. (a) 12. (a) 13. (d) 14. (c) 15. (d) 16. (c) 17. (d) 18. (c) 19. (b) 20. (c)
21 . (a) 22. (d) 23. (c) 24. (c) 25. (a) 26. (b) 27. (d) 28. (c) 29. (b) 30. (d)
31 . (d) 32. (d) 33. (a) 34. (b) 35. (b) 36. (d) 37. (c) 38. (a) 39. (c) 40. (a)
41. (a) 42. (d) 43. (c) 44. (a) 45. (c) 46. (a) 47. (c) 48. (c) 49. (d) 50. (a)
51. (c) 52. (b) 53. (c) 54. (b) 55. (a) 56. (c) 57. (c) 58. (a) 59. (b) 60. (d)
61. (d) 62. (d) 63. (b) 64. (a) 65. (a) 66. (d) 67. (b) 68. (d) 69. (b) 70. (a)
71 . (b) 72. (b) 73. (a) 74. (b) 75. (a) 76. (d) 77. (b) 78. (d) 79. (a) 80. (b)
81. (a) 82. (a) 83. (c) 84. (c) 85. (a) 86. (b) 87. (a) 88. (a) 89. (c) 90. (b)
91. (a) 92. (b) 93. (d) 94. (d) 95. (d) 96. (a) 97. (b) 98. (d) 99. (a) 100. (c)
101 . (a) 102. (b) 103. (b)
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 Explanations
Topic 1 Basic Concepts of Thermodynamics
1. Process is adiabatic because of the use of thermal insulation 12. The reactions in which products has lesser energy than reactants,
therefore, q = 0 then energy is released in the reaction and such reactions are
known as exothermic reactions, e.g.
Pext = 0; W = Pext ·AV = 0 X AV = 0
N2 + 3H 2 - 2NH3 + 92 kJ
Internal energy can be written as
In this equation energy is released, so, it is an example of
AU= q + W =0 exothermic reaction.
The change in internal energy of an ideal gas depends only on
13. Bond breaking process or decomposition processes are
temperanire and change in internal energy (AU) = 0 therefore,
endothermic process.
AT = 0 hence, process is isothermal and T2 = T1 and P2V2 = p 1V 1
14. Work done (W) = -Pext (V2 - V1)
(d) p2 VJ = p 1V? is incorrect, it is valid for adiabatic reversible
= - 3 x (6- 4) =-6 L atm= -6 x 101.32 J
process.
Hence, only (a), (b) and (c) are correct choices. (:.1 L atm = 101.32 J)

K- L At constant p, volume increases thus heating = - 607.92 "" 608 J

2
L- M At constant V, pressure decreases thus cooling 15. Internal energy, enthalpy and entropy are state fi.mctions but
· M - N At constant p, volume decreases thus cooling work and heat are path functions.
N - K At constant V, pressure increases thus heating
16. The properties of the system whose value is independent of the
3. L - Mand N - K at constant V so isochoric. amount of substance present in the system are called intensive
properties e.g. viscosity, surface tension, temperature, pressure etc.
4. The intensive property is mass/volume.
17. The property of the system whose value depends upon the amount
5. V1 = I00mL V2 = 250 mL
of substance present in the system is called extensive property.
Pressure, p = 2 atm Gibb's free energy is an extensive property.
Work done by the gas
W = pA V or p (V2 - V1) = 2 (250 - I 00) 10- 3
Topic 2 Internal Energy (1st Law of
3
Thermodynamics) and
= 2 x 150 x 10- = 0.3 atm L
Hess's Law
= 0.3x 101.328J
1. We can represent the process of evaporation as
= 30.3984 J "" 30.48 J
18 g H 2O(l) Vaporisation 18 g Hp(g)
6. W = pAV = 105 (2 - 1) = 105 J = 102 kJ
18
7. (d) For isochoric process, volmne of the system remains constant Number of moles in 18 g Hp(!)= g _ 1 = I mole
during each step of the process, i.e. dV = 0 18gmol
(a) Isothermal process occurs at constant temperanire. AvapU = Avap H 8 - pAV = AvapH 8 - Ang RT
(b) In adiabatic process, no exchange of heat takes place between
Assume steam behave as an ideal gas.
the system and its surroundings, i.e. dq = O
3
(c) In isobaric process, pressure of the system remains constant AvaP = (40.66)- (I) (8.314 x I o- ) (373)
during each step of the process, i.e. dp = 0
= 40.66- 3.10 = 37.56 kJ mol- 1
8. Work done due to change in volume against constant pressure,
5
W = - p(V2 -V1)= - I x 105 Nm- 2 (Ix 10-2 -1 x 10-3 )m 3 2. AH= - nCPAT = - 2 X R (225 - 125)
2
= - 900 Nm= - 900 J (1 Nm= 1 J) = - 5 R (100) = - 500 R
9. In an adiabatic process, no exchange of heat takes place between 3. Given, C + 0 2 - CO 2 ; AH 0 = - x kJ ... (i)
the system and surroundings, i.e. dQ = 0. Such a condition exists
2CO + 02 -
0
when the system is thermally isolated. 2CO2; AH = - y kJ ... (ii)

10. Macroscopic properties which determine the state ofa system are Required equation is C + 2.2 0 2 - CO, AH 0
1 =?
referred as state functions. The change in the state properties
depends only upon the initial and final state of the system. All On reversing eq. (ii), we get
thermodynamic functions are state functions except work and heat. 2CO2 - 2CO + 02; AH
0
2 = + y kJ .. . (iii)
11. Only the laws of thermodynamics are mere statements, so they, Dividing eq. (iii) by 2 gives
are believed. Many mathematical expression are derived on the
basis of these laws. CO2 - co+¾02; AH 3 = + 0
1 kJ ... (iv)
 Thermodynamics I 139
On adding eq. (i) and (iv), we get (required equation) (b) For adiabatic process, Q= 0
1 M=W
C + - 02 - CO; /iH
0
1 =W 0
+ !iH
0
3
2 (c) For isothermal process, !iT = 0 and M = 0

(
= - x+2
y) kJ =-y-2x
2- kJ
Q=-W
(d) For cyclic process, state functions like
4. /ill = !iU + !intf-T !iE= 0
(where, /ill = heat of reaction at constant pressure Q =-W
= heat of reaction at constant volume)
!iU 9. C(s)+ O 2(g) - CO2(g); /iH =r ...(i)
I
For the given reaction, ling = 6 - ~ = _ 2 = - 1.5 CO(g)+ CO2(g);W =s ...(ii)
2 2 2O 2(g) -
Ii U = /ill - !intf-T 1
C(s)+ CO(g); /ill=?
= 780980 + 1.5 X 2 X 298 2 O2(g) -
= 780980- 1490 = 78 1874"' 780.086 kcal Subtract Eq. (ii) from Eq. (i)
S. The process is isothermal expansion, hence C(s)+ O 2 (g) - CO 2 (g); /ill= r
1
Q =-W and M=O CO(g)+ O 2 (g) - C0 2 (g);liH=s
V, 2
W = - 2.303nRT log ....1
V1
1
375 C(s)+ CO(g); /ill = r - s
= - 2303 X 0.04 X 8.3 14 X 3 10 log -
50
= - 208 J 2O 2 (g) -
10. The heat of formation of CO is calculated by using Hess's law.
Q = + 208 J and W = - 208 J (expansion work) According to it, the total heat changes occurring during a
6. Hess's law states that the total heat change (/ill) accompanying a chemical reaction are independent of path.
chemical reaction is the same whether the reaction takes place in 2CO(g)+ O 2 (g) - 2CO2 (g); /ill=- 135.2 kcal
one or more steps. I 135.2
(1)CO 2 (g) - CO(g) + O2 (g); /ill = - - kcal
It means that heat of a reaction depends only on the initial 2 2
reactants and final products and not on intermediate products that (ii) C(s) + O2(g) - CO2 (g); /ill= - 94 kcal
may be formed.
Required equation
Now /ill= liH 1 + W 2 +W 3 1
Enthalpy change in a reaction is always constant and independent C(s) + - 0 2 (g) - CO(g); /ill=?
2
of the path followed.
Add Eqs. (I) and (II)
7. (a)Since, c hange of state (p1, V1 , T1)to (pz, V2, T2) is isothermal
1
therefore, T 1 = T2. C(s) + Oz(g) - CO(g); /ill= - 26.4 kcal
(b) Since, change of state (Pt, V1, T1)to (p3 , V3 , T3 ) is an adiabatic
2
expansion, it brings about cooling of gas, therefore, T3 < T1• 11. Every system having some quantity of matter, is associated with a
definite amount of energy. This energy is known as internal
(c) Work-done is the area under the curve of p-V diagram. As
energy. It is sum of many type of energies, such as translational
obvious from the given diagram, magnitude of area under the
energy, rotational energy, vibrational energy, electronic energy
isothermal curve is greater than the same under adiabatic
and bonding energy of the molecule.
curve, hence Wi,othermal > wadiabatic
Here only magnitude of work is being considered otherwise E= E,rans + E,ot + Evib + £bonding + Eclectronic

both works have negative sign. 12. Isothermally (at constant temperature) and reversible work.
(d) !iU = nC.j),.T W = 2.303 nRT log P2 = 2.303 X IX 2 X 300 log _!Q
In isothermal process, !iU = 0 as !iT = 0 Pt 2
In adiabatic process, = 2.303 X 600 X log 5 = 965.84
!iU = nC. (T3 - T1) < Oas T3 < T1• At constant temperature , M =O
fi U i,otherrml > fiU adiabatic ·
M =q + W, q = - W = - 965.84 cal
8. (a) For isochoric process, !iV = 0 13. Hess's law is based upon law of conservation of energy i.e., first
W = p!iV =0 law of thermodynamics.
M=Q 14. In a cyclic process, !iE = 0.
140 I Chapterwise & Topicwise Engineering Entrances Solved Papers
1 y-1
15. C(s)+ O 2(g) -----t CO(g) 25. TV y-t =constant_!_ = Vz [For monoatomic gas y = ~]
2 Tr,,.,1 ( V1) 3
This equation can be obtained by subtraction of
rLCO(g) + 2O2(g)
1 1 _!_ = (3-)(513-1) = i213) ⇒ T. = __!__
-----t CO2(g) J T.final 1 - i 21 3J
from [C(s) + O2 (g) -----t CO2 (g)] 26. According to Hess's law total heat changes during a chemical
reaction are independent of path of reaction.
Hence, 6H =(CO)= [ - 393.3 - (- 282.8)] kJ
1 Given,
= 110.5 kJ/mol
I2 (s) ➔ I2 (g), 6H1 = 57.3 kJ/mol ...(i)
16. In the adiabatic process no heat enters or leaves the system
Ii(s) ➔ I2 (/), W 2 = + 15.5 kJ/ mol ...(ii)
i.e. q = 0.

17. W =-s: pdV = - p(V2 - V1)

Required equation Ii(/) ➔ I2(g), W = ? subtract
Eq. (ii) from Eq. ( i)
W = - 1(20 - 10)= - 10dm 3atrn :. Ii(/) -----t I2 (g), 6H = 57.3 + (-15. 5)
1 1 = + 41.8 kJ/ mol
=_ dm 3 x 8.3 14 JK- mo1-
10 27. In adiabatic expansion work is done by the system so it w ill lose
0.0821 dm3K- 1mo1- 1
heat to the surrounding. Thus, temperature ofthe system decreases.
=- 10 131
28. p= latm
From, Ist law of thermodynamics
6V = (50- 15) = 35 L
6 U = q + W = 800 J + (- IO13 J) = - 213 J
W = -p• 6V= - I x 35=-35Latm
18. T/i,_..,.;bte > TJ_,,.1,1. it is an adiabatic expansion and W (rev) is
Hence, work done by the system on the surroundings is equal to
maximum. 35 L-atm.
19. According to Hess's law, the total heat changes occurring during
a chemical reaction are independent of path. Topic 3 Enthalpies Types and Their
Calculations, Heat Capacity
~ AH;; of the System
1. C2 Hs0H (I) + 3O2 (g) -----t 2CO 2(g) + 3H 2 O(/)
CvD
6 U =- 1364.47 kJ/ mol;
W=q + v+ 2x 6H = 6 U + 6 ngRT ⇒ 6ng = - I
20. 6E = q+W
1:-,.H = _ 1
364.47 + - I X 8.3 14 X 298
q=0 1000
(-: Temperature is to be increased, no heat should enter or leave [Here, value of R in unit of J must be converted into kJ]
the system) = - 1364.47 - 2.4776 = - 1366.95 kJ / mol
M=q +W=0+W or M=W 2. The combustion equation of sucrose is
W ;ta 0, q = 0 C 12H 2z0 11 (s)+ 12O 2(g) -----t 12CO 2(g)+ l!HzO(g)
21. W = - p6V Here, 6n = l2+11- 12=11
Given, p + 100 kPa = 105 Pa, As we know, W = M + 6nRT
3 3
V1 = ldm = 10- m3, V2 = 1 m 3 6 H = (- 1348.9 X 103 ) + 11 X 2 X 298

W = 105 X (I - 10- 3 ) J = - 1348900 + 6556 = - 1342344 cal = - 1342.344 Kcal

3. Given,
W = 999001
(i) 2C + 3H 2 -----t C2H6; 6H = - 21.1
22. For an isothermal process 6 T = 0 and 6 £ = 0 and q ;ta 0
(ii) C + 0 2 -----t CO2; W = - 94.1
23. The first law of thermodynamics can be expressed as:
(iii) H 2 + ..!_ 0 2 -----t H 2 O;W = - 68.3
M=q+ W 2
q=6E-W Eqs. 2 (ii)+ 3 (iii) - (i)
7
24. Hess's law states that enthalpy changes during in the process are Cif\ + - 0 2 -----t 2CO 2 + 3Hz0
independent of path. So, this law is used in calculating enthalpy 2
ofreaction. 6x = 2 (- 94.1) + 3 (- 68.3)- (- 21. 1)= - 372 kcal
 Thermodynamics I 141
. 1000 7. Affc° (Standard heat of combustion) is the standard enthalpy
4. Number of mo les m 1 kg coke= - - = 83.33 mol
12 change when one mole of the substance is completely oxidised.
(i) For the combustion of I kg of coke Also standard heat of formation (t:i.H'j) can be taken as the
C+ 02 - CO2; t:,H = 393.5 kJ standard of that substance.
Heat liberated from I mole coke= 393.5 kJ !:i.HJ (HzO)=- 300 kJ mol- 1
:. Heat liberated from 83.33 mole coke= (393.5 x 83.33) kJ H 0 'l)ucooo = Ml/ (glucose)= - 1300 kJ 11101- 1
(ii) For the burning of water gas
H 0 o2 = Aff/((O2) = 0.00
C + H 2O - CO+ H2
_______, CoH ,2O6(s) + 6Oz(g) - 6COz(g) + 6H2O(/)
Water gas
!:i.H/ (glucose)
CO + H2 + O2 - CO2 + H2O;
= 6 [t:i.HJ (CO 2 )+ AffJ (H2 0)
t:Jf = 285 + 285 = 570 kJ
-[t:J!J (CoH12O6) + 6AffJ(O2)l
:. Ratio of heat liberated from burning of water gas obtained from 1
I kg of coke = 6 [- 400 - 300] - [ - 1300+ 6 x O]= - 2900 kJ mol-
H 2 = (570 X 83.33) kJ Molar mass of C6H 1z06 = 180 g mol- 1
:. Required ratio= H 1 : H 2 = 393.5 : 570 = 0.69 : I Thus, standard heat of combustion of glucose per gram
12 weight of CO x I 00
5. Percentage of C = - x - - - - - - 2- - - - = -2900=- 16.l lkJ - 1
44 weight of oraganic compound 180 g

=_G, X 0.198X 100 = 2 1.95% 8. For the decomposition of9 g of water heat required= 142.5 kJ
44 0.246 We know that the molecular weight of
2 weight ofH 2O x 100 1
Percentage ofH = - x - - - - - ~ - - - - H 2O = 2+ 16= 18 g rnol-
18 weight of organic compound
Therefore, heat required for decomposition of 18 g of water
=2x 0.1014x 100 = 4 _57 %
18 0.246 = ~ X 142.5 = 285 kJ
9
Percentage of 0= (100 - 21.95 - 4.57) = 73.47 % Therefore, enthalpy of formation of water= - 285 kJ
21 95
Moles ofC = · = 1.83 9. The enthalpy of combustion of C6H6(l) = - 3250 kJ
12
By burning 78 g of C6H6 liberated heat= 3250 kJ
Atoms ofC = 1.83 x NA 1
[·:Mol. wt. of benzene= 12 x 6 + I x 6 = 78 g rnol- ]
4 57
Moles ofH = · = 4.57
I 9
On burning 0.39 g ofCoHi; liberated heat = 0.3 x 3250
78
Atoms ofH = 4.57 x NA
= 16.25kJ
73 7
Moles ofO = .4 = 4.59 10. t:Jf = mc!:i.T = (125+ 10.5)x 1 x 3.1= 420.05 cal
16
Atoms ofO = 4.59 x NA 420 05
Heat of solution= · cal / g= 40 cal / g= 167.7 J I g
10.5
Simplest ratio= C: H: 0 = 1.83 : 4.57: 4.59
= 1: 2.5 : 2.5 = 2: 5 : 5 (I cal=4.18J)

Thus, the ratio of atoms of carbon and hydrogen in the compound 11. Consider the formation of H 2O
is 2: 5 I
H 2(g) + - O 2(g) - H 2O(/), t:i.H =- 286.02 kJ
6. In option (a) and (c) carbon is in gaseous form which actually 2
does not exist. In option (d) the reaction is incorrect because CO 1
Aff, = Aff1 (HzO)- Affl H 2)-
and H 2 gases react to form methanol (CH 3OH) and not methanal
(HCHO).
2 AfflO2)
- 286.02 = t:i. f (H 2O) - 0
So, the correct option is (b).
:. AfflHzO) =- 286.020
Or an another way to solve this problem is that we know, standard
enthalpy change of formation of any reaction can be given as Now, consider the ionisation ofH2O
t:J! O(reaction)
. =Lt:J!O/(p,vducts) -:Et:J!Ofc,_,...,) H 2O(l) - H+ (aq)+ OW(aq); t:i.H = 57.32 kJ
And when a pure element is in the reference form, the standard t:i.H, = t:Jf1 (H+ aq) + t:i.Hf (OW aq)- t:i.H1 (HzO)
enthalpy of formation is zero. Here, all the reactants in the given
option (b) are in their reference form at standard conditions. 57.32 = 0 + Aff1 (OWaq) - (- 286.20)
0 0
Hence, Aff reaction = L Aff /(J>rr,,J..,tt;) - 0 or Aff1 (OW aq) = 57.32- 286.20=- 228.88 kJ
0 0
t:i.H ,eaction = lli .fcp,o1Jucts>
142 I Chapterwise & Topicwise Engineering Entrances Solved Papers
12. HCl + NaOH - NaCl + H 2O 22. Heat of neutralisation of strong acid by strong base is always
S00x 0.1 200x 0.2 greater than the heat of neutralisation of weak acid or weak base
Att = 0 because some energy is used to ionise weak acid or weak base.
' 1000 1000
(a) NH4 OH- CH3COOH weak base- weak acid
Number of mo les= 0.05 = 0.04
(b) HNO3 - NHpH strong acid- weak base
·: During neutralisation of 1 mole of NaOH by 1 mole of HCI,
heat evolved= 57.3 kJ (c) NaOH- CH 3COOH strong base- weak acid
: . To neutralised 0.05 moles ofHCI by 0.04 mole of (d) HCI- NaOH strong acid-strong base

NaOH= 57.3 x 0.04= 2.292 kJ ·: HCI is a strong acid and NaOH is a strong base.

13. For the system, work done is equal to change in energy. So, there :. Their heat of neutralisation will be highest among the given.
will be none of W, Mand AH will be zero. 23. The temperature rise is :
14. Relation between AH (enthalpy change) and M AT = T2 -T1 = 298.45 - 298 = 0.45 K
(internal energy change) is This indicates that heat produced from combustion of 3.5 g of
AH = M + AngRT compound rises temperature of calorimeter by 0.45 K.
where, A 11g = moles of gaseous products-moles of gaseous Heat produced = 0.45 K x 2.5 kJK- 1 = 1.125 kJ
reactants = - I
Heat produced from 28 g of compound (1 · 0 mol)
-1366.5 = M- l x8.314x 10-3 x300
= I. I 25 x 28 = 9 kJ
M = -1364.0 kJ mo1- 1 3.5
15. 4NO2(g) + 0 2 (g) ➔ 2N2O 5 (g); - I I 1 kJ 24. 2NH3 (g) ➔ N 2(g)+ 3H2(g)
2N 2O 5 (g) ➔ 2N2 O 5 (s); A, H = (-54 x 2) kJ AH,= -(2xenthalpyofformation ofNH3)= -(2x-46) = 92kJ
4NO 2(g)+ O2(g) ➔ 2N2O 5(s); AH= - 2 I9 kJ 25. Heat required to raise the temperanrre of200 g water by 5°C
AH of sublimation ofNP 5(s) is+ 54 kJ mo1- 1• = m.c.At= 200 x Ix 5 = 1000 cal= I kcal
Thus, for reverse process, it is -54 kJ mo1- 1• :. 0.2 g 1-butanol on burning liberates= 1 kcal heat
:. 74 g (I mo!) 1-butanol on burning will liberate
16. Q = nCAt 1
=- x74= 370
0·2
Q = 2 X 25 X 20 = 1000 J = 1.0 kJ
Since, the heat is liberated, AH = -370 kcal.
17. NaOH + HCl - NaCl + H 2O
26. Since d1e process involves phase change, heat absorbed,
20 x 0.5 I 00 x 0. 1 IO millimole produced Q = mass x latent heat of vaporisation
During formation of 10 millimole ofH2Othe heat released isx kl Given, mass= 70· 0 g = 0.07 kg
Therefore, heat of neutralisation is -100 x kJ/mol (heat released
hence negative).
L,, = 2260 kJ/kg
18. The bond energy of a C- C single bond is approximately Q = 0.07 x 2260 kJ = I 58.2 kJ = 158200 J.
100 kcal mo1- 1• 5
27. (D C2H 2 + - O 2 ➔ 2CO2 + H 2O; AH= -310kcal
2
19. AH; of elements in their standard state is taken to be zero. Cl2 is
(TT) C + 0 2 ➔ CO2; AH = -94 kcal
gas, Br2 is liquid and I2 is solid at room temperature.
I
. 1 3 o -1 (TTI) H 2 + 0 2 ➔ Hp; AH= -68 kcal
20. Given, - N,(g)+ - H,(g) ➔ NH 3 (g); AH1 = -46· 0 kJ mol
2 - 2 -
2
(Eq. (II) x 2) + Eq. TTI - Eq. (D gives
2H(g) ➔ H 2(g) ; AH;= -436 kJ mo1-
1

2C + H 2 - C2H 2;
2N(g) ➔ N 2 (g); AH;= -7 12kJ mo1- 1 AH= [{(-94 x2) + (-68)}-(-310)]= +54 kcal
Assuming Xis the bond energy of N- H bond (in kJ mol- 1) 28. A ➔ B , AH=+24kJ/mol ⇒ HB-HA= +24 ...(i)
1 3 B ➔ C, AH= -18kJ/ mol ⇒ Hc- H 8 = -18 ...(ii)
- x(- 712)+ - x (- 436)- 3X = - 46.0
2 2 ⇒ H 8 -Hc=+ 18
3X = 1056kJ mo 1- 1 From Eqs. (i) and (ii), we have
So, X = 352kJ mo 1-1 He- HA= 6
21. In neutra lisation reaction, when acid and base both are weak, a Hn>Hc> HA
large amount of heat is utilised to ionise them. Thus, for such
29. Given,
reactions, enthalpy of the reaction is least.
H 2O(g)+ C(g) - CO(g) + H 2(g);AH =+ 13lkJ ...(i)
Hence, enthalpy is least for
I
HCN + NH4OH - NH4CN + H 2O CO(g) + O2(g) ---t CO2(g);AH =-282kJ ...(ii)
2
 Thermodynamics I 143
1 35. .Mlreaction = "L.Mff product - ".£.Mlf reactant.
H 2 (g)+ ...(iii)
2O 2 (g) - Hp(g);.Mf= -242kJ
W 1 of a single element like 0 2, H 2 , Cl2 is considered equal to
C(g) + O 2 (g) - CO 2 (g);.Mf =? ... (iv) zero.
On adding Eqs (i), (ii) and (iii), we get Eq (iv) CH 4 + 202 - CO2 + 2H2O
H 2O(g) + C(g) - CO(g) + H 2(g); .Ml =+ 131 kJ .Mf,eaction =.Ml/CO2)+ 2.Mff · (H zO)
I
CO(g) + - O 2 (g) - CO2(g); .Ml= - 282 kJ - W 1 (CH4)- 2.Mf1 (O2 )
2
= - 400 + 2(-280)- (-70)- 0= - 890 kJ mo1- 1
I
H z(g) + LlH = -242 kJ
2Oz(g) - H 2O(g); 36. H 2 + Cl2 - 2HCI
4 2
C(g) + O2 (g) - CO2 (g) LlH = (131- 282- 242) kJ Enthalpy of formation ofHCI = (I0 + 58 ) - < x I03)
= - 393kJ 2
= 162- 206 = - 44 = - 22 kcal mol-1
2 2
15 - I 37. C(graphite) + 2H2 (g) - CH 4 (g); .Ml= - 17900 cal
t,,.n =n - 11 =7- - = -
g p r 2 2 LlE = ?, LlH = M + Lln/?-T
qP = q., + llng(RT)= - 321.30 + (-½) 300 R
where, Llng = nu mber of moles of gaseous products - number of
moles of gaseous reactants.
=1-2=- l
= -32 1.30-150R
31. w 1 is the enthalpy change when I mol of the substance is .Mf=LlE - lxRxT

formed from its elements in the standard state. Reaction (a) does LlE = - 17900 + 596
not represent w because standard state of carbon is graphite
1 LlE = - 17304 cal
and not diamond. 38. H 2O(l) - H 2O(g ~ Lln = I- 0 = I
32. We know that, .Ml = M + nRT
M = .Ml - LlnRT = 41 - I X 8.3 X 373 X I 0- 3
where, Lln = number of moles of gaseous products - number of
(R = 8.3 x 10- 3 )= 37.9 kJ mol- 1
moles of gaseous reactants = 2 - 3 = - I
So, .Ml = LlE - RT. 39. 2C(s)+ 2O 2 (g) - 2CO2 (g); .Ml= - 787 kJ ...(i)
33. NH3 (g) + HCl(g) - NH4Cl(g) I
Hz(g) +
I mol I mol I mol 2Oz(g) - H 2O(/);.Mf = - 286 kJ ...(ii)

LlH = LlU + Lln/?-T I

C2H 2 (g) + 2 O 2(g) - 2CO 2 (g)+ HzO(l)
Ll ng = Number of moles of product- number of moles of reactant 2
= 1- 2 =- I .Ml= - 1310 kJ ...(iii)
LlH = LlU - RT Add the Eqs. (i) and (ii) and subtract Eq. (iii) from them.
LlH < LlU 2C + H2 - C 2H 2 - 787 - 286 + 1310

34. Given, S(rh) + 2 O,(g) - SO 3 (g); 2C + H 2 - C 2H 2 -1073 + 1310

2 -
2C + H 2 - C 2H 2 + 237
!lH = - 2x kJ mo1- 1 ...(i) Hence, the heat of formation of acetylene is + 237 kJ.
I 1 40. For reaction,
SO2 (g)+ - O 2 (g) - SO 3 (g);llH = - y kJ mol- ...(ii)
2 H 2(g)+ B rig) - 2HBr(g) ;.Mf0 =?
S(s)+ O 2(g) - SO2(g); LlH =? On the basis of bond energies ofH2, Br2 and HBr, .Ml of above is
Subtract Eq. (ii) from Eq. (i) calculated as follows:
.Ml = - [2 x bond energy of HBr - (bond energy of H 2 - bond
S(rh)+202( g ) - SO3 (g);.Mf= - 2xkJmol- 1 ...(i) energy ofBrz)]
2
.Ml =-[2 X (364)-(433)- 192] kJ
1
SO2(g)+ ¾Oz(g) - SO3 (g);llH = - y kJ mol- ...(ii) = - [728- (625)] kJ = - 103 kJ

+ 41. The bond energy is the energy required to break one mole of
similar bonds.
S(rh) + (%-¾) O2( g ) - SO (g); .Ml= (- 2x+ y) kJ mol- 1
2 42. Heat of decomposition of water is
I + 573.2
H 2O(g) - H 2(g)+ O 2 (g); .Ml = - - = 286.6kJ/mol
S(rh) + O2(g) - SO2 (g); .Ml= (y- 2x) kJ mo1- 1 2 2
144 I Chapterwise & Topicwise Engineering Entrances Solved Papers
43. The heat of reaction for an ideal gas, at constant pressure and 52. The molar heat capacity for any process is given by a following
constant volume are related as R vr C
expression C = Cv + - - w hen P = constant and _!!_ = y
Aff = liE + linRT 1- y Cv
qp = qv + linRT Here, E.. = I i.e., Pv- = constant
1

44. CH 2 = CH 2 + H 2 - CH3 - CH3 V

3 R 3 R 4
liH = (BE)reactants -(BE)products C= - R + - - = - R+ - = - R
2 1- (- 1) 2 2 2
= 4(BE)e-H + (BE)c= C + (BE) H- H
- [6(BE)C-H + (BE)e-cl 53. Carbon is found in solid state. The state of substance affects the
enthalpy change.
=- 125 kl
C(s) - C(g) Sublimation
45. The re lationship between Aff and li U is Aff = liU + Ii nRT
and H 2(g) - 2H(g)dissociation are required for C-H bond.
46. Aff = liU + lin/?.T 1 1
54. I2 (s) + Cl 2(g) - ICl(g)
Aff = enthalpy change (at constant pressure) 2 2
liU = internal energy change 1r 1 1
Aff = l - liH (12) + - liHdiss (Cl2)+ - Affdiss
1
CI2)J- Aff1c1
(at constant volume) given reaction is exothermic 2 s--->g 2 2
ling = mole of gaseous products - gaseous reactants
=-ve = G x 62.76+ ½x 242.3 + ½x 151.0) - 211.3
Thus, Aff < liU = 228.03 - 2 11.3
47. I. C(s)+ Oi(g) - CO 2(g);Aff =-393.5 kJ Aff = 16.73
l 55. Aff - li U = lin~T
II. CO(g)+ - O2(g) - CO2(g);Aff=-283.0kJ
2
I and II gives = + _!_ X 8.314 X 298 = + 1238.78 J mot- I
2
l
III. C(s)+ O 2(g) - CO(g); Ml= - 110.5 kJ rLC(s)+ 1 O2(g) ➔ CO(g) fing=l - I J1
2 2 2 = 2J
This equation ITT also represents formation of I mole of CO and
thus enthalpy change is the heat of formation of CO (g). 56. Given, H+ + OW - H 2O; liH = - 55.9 kJ ...(i)
48. I. C + 0 2 - CO2; Aff = - 393 . 5 kJ HCN + OW - Hp + CN- ; 11H = - 12.1 kJ ...(ii)
I On reversing Eq. (i), we get
II. H2 + - 0 2 - Hp; Aff = -286.2 kJ
2 Hp -➔ H+ + OW; Aff = +55.9 kJ ...(iii)
III. C2H 4 + 302 2CO2 + 2H2O; Aff = - 1410.8 kJ
-
On adding Eq. (iii) to (ii) ,we get
Multiply the equations (I) and (II) by 2
IV. 2C + 20 2 - 2CO 2; liH = - 787.0 kJ HCN - H+ + CW;liH=+43.8 kJ
V. 2H 2 + 0 2 - 2H 2O; Aff = - 572.4 kJ 57. Aff,eaction = 'J:,Af{ of products - "i.Aff of reactants
Add the equations (IV) and (V) and then subtract (III) 11H1 C2H6 = -2 1. l kcal
2C + 2H 2 - C2H 4; Aff = 51.4 kJ liHf CO2 = - 94. l kcal
49. The decreasing order of bond dissociation energies of C-C, 11H1 H 2O= - 68.3 kcal
C-H and H - H bonds is as 7
C2~ +- 02 ➔ 2CO2 + 3Hp
H - H > - C - H >-C-C- 2
354 414 347 kJ/mol Affcont>ustion = [2Aff1 CO 2 + 311Hf H 2O]
I 7
50. CO(g)+ - O2 (g) -➔ C0 2 (g);Aff=liE+linRT
- [liH~2~ +
2 211Hfa2 ]
I
liH = - 67710 - - x 2 x 290 = - 68000 cal r 1 l
2 = [2x (- 94.l )+ 3 (- 68.3)]-L-2 1.l +
2 x (O)J
51. Aff = M + lin~T
= (-188.2-204.9)+ 21.l
For the reaction, N 2 (g) + 3H2 (g) ~ 2NH3(g) = - 393.1 + 21.1 = - 372 kcal
ling=2-4=-2
58. For strong acid strong base heat of neutralisation is 57 kJ mol- 1.
liH = liE + lin~T
For weak acid or base its value is less than this value. Hence, the
liH = liE + (-2)RT heat ofneutralisation will be minimtun for CH 3COOH + NH4OH.
Aff =M-2RT
 Thermodynamics I 145
59. S + 0 2 - SO2; 6-H = - 298 kJ 69. The amount of heat evolved or absorbed w hen 1 mole of the
substance is completely oxidised is called heat of combustion.
Heat of fonnation of SO2 is also the heat of combustion of
For example,
sulphur. Heat of combustion of 32 g S = - (298) kJ
CH4(g)+ 2O2(g) - CO2(g)+ 2H2O(/) + Heat
Therefore, heat of combustion of 4 g
4 70. CaCO 3 (s ) ~ CaO(s) + CO 2 (g) (6.ng = 1- 0 = I)
S = (- 298 ) X = - 37 .25 kJ
32 We know that,
I W=M + 6-ngRT
60. CO(g) +
2 Oi(g) - CO 2 (g)
176 =till+ 1 X 8.314 X 10- 3 X (273 + 927)
qP = q,, + 6-nRT till = 176 - 8.314 X 10- 3 X 1200= 176 - 9.97 = 166.03 kJ
1 I
6-n = I - I - = - - · R = 2 cal T = 300 K
2 2' ' 71. The formation of one mole of HCI can be represented as,
1 I
qp = q., + (-½) (2) (300) 2(H- H) + (Cl- Cl) -
2 H- Cl; W = - 90 kJ

Hence, for the reaction,

qp = q,, - 300
Heat evolved = heat evolved in bond fonnation
qp - qv = - 300 cal
- heat required for bond breaking
61. A(g) + 2B (g) - 2C(g) + 3D(g)
6.n=5 - 3=2 :. 90 kJ = [H-CI bond energy) - (¾ x 430 + ½x 240)
6-H = M + 6-nRT
:. (H-CI bond energy)= 90 + (215 + 120)= 425 kJ mo1- 1
19000=6.E+ 2x2x300 0 0
72. W = L(W products) - !:.(W reactants )
M= 17800cal = 17.8 cal
0
62. W =M + p6.V Given, W 1 CO2(g) = - 393.5 kJ/ mol
0

For isochoric process 6-V = 0

6.H r CO(g) = - 11 0.5 kJ / mot
0
W=M W 1 Hp(g) = - 241.8 kJ / mot
63. The number of gram-equivalents of CO2(g) + H 2 (g) - CO(g) + H 2O(g)
w o =[(Wor CO) + (WorHP)]
H2SO4 = 0.2 X _2Q_ = 1.0 X 10- 2
1000 - [(W 0 r CO2)+ (W 0 1 H 2)]
The number of gram-equivalents of KOH= 1 x _2Q_ = 5 x 10- 2 = ((-110.5) + (- 24 1.8)) - ((- 393.5) + (0))
1000 = - 110.5 - 241.8 + 393.5
We know that 57. 3 kJ heat is evolved when one gram-equivalent = - 352.3 + 393.5 = + 4 1.2 kJ
of strong acid (like H 2SO4) and one gram-equivalent of strong
73. For exothennic reaction, W = (-). For endothermic reaction,
base (like KOH) are neutralised. Here 1.0 x 10-2 gram-equivalent
of KOH hence, the heat evolved will be W= (+)
2 74. For an isothennal process, M = 0
= 57 .3 kJ X 1.0 X 10-
As the process is taking place at constant T and p hence, from
= 57 .3 X 103 X 10- 2 J = 573 J
equation, W =M + 6-p V
64. The enthalpy ofH2O(/) is less than that ofHp(g~ hence more we have, 6-H =0+ Ox V = 0
energy wi ll be released when H 2O(/) is formed, therefore Hence, for the process, W = M = 0
W1<W2. 75. For an endothermic reactions 6-H is positive because in
I endothermic reaction heat is always absorbed.
65. W * Mfor CO(g) +
2O2(g) - CO 2 (g)as6.ng;ta 0
76. C (graphite) + __!_ 0 2 (g) - CO(g) 6-n = I _ __!_ = __!_
66. For 1 mole of liquid CP = Cv. 2 g 2 2
67. The amount of heat evolved or absorbed in the fonnation of one W = 6-E + 6-ngRT
mole of product from its elements. So, the correct answer is 1
M=W-6.ngRT = - 26.4 - - X 0.002 X 298
C + 0 2 ( I atrn) - CO2 (I atm). 2
68. Cgraphite + O2(g) - CO2 (g);6.H = - 393.5 kJ ...(i) = - 26.7 kcal

...(ii)
77. W = 6-E + 6-nRT
Cdiamond + Oi{g) - CO2(g); 6-H = - 395.4 kJ
CH 4 (g) + 202 - CO 2(g) + 2Hp(g)
Cgraphite - Cd.1amond
W = - 393.5 - (- 395.4)= 1.9 kJ = 1900 J 6-H = - 885389 + 2 X 8.314 X298
= - 880433.856 .. -880430
146 I Chapterwise & Topicwise Engineering Entrances Solved Papers
78. Formation of XY is known as X 2 + Yi --4 2XY 84. 2CO(g) + O 2 (g) --4 2CO2(g); Ml = M + /1nRT
t:,H = (BE)x _ x + (BE)r _ r - 2(BE)x _ r /1n = Number of moles of gaseous product
If (BE) of X - Y =a - Number of moles of gaseous reactant
then (BE) of (X - X) = a /111 = 2 - 3 = - ~ Ml = M - RT

and (BE) of (Y - Y) = 1 Ml< M

85. This is based on Joule-Thomson effect and this is due to
Ml1 (X - Y) = - 200 kJ expansion of gas in the refrigerator.
a 86. 0.5 mol HNO3 = 0.5 mot H+ and 0.3 mol OW
- 400 (for 2 mol XY) =a+ - - 2a
2 0.5 W(aq) + 0. 3 OW (aq) --4 0.3 H 2O(/)
- 400 = - ~ and a = + 800 kJ (0.3 mole ofOir is neutralised by 0.3 mole of H+)
2
Ml= 0.3x 57.1= 17.1 kJ
The bond dissociation energy of X 2 = 800 kJ mol- 1•
87. Enthalpy of formation of H 2 SO 4 can be represented by the
79. Ml =M + /1nRT following equation
176 = M + 1 X 8.314 X 10- 3 X 1240 H 2 + S + 202 - - 4 H 2SO4 ...(i)

M= 176 - 10.309= 165.69kJ Given, S + 0 2 - - 4 SO2, Ml = - 298.2 kJ

CH3 I
SO2 + - 0 2 - - 4 SO 3 ,M/ = - 98.7 kJ
I 13 2
80. CH 3 - CH - CH3 + - 0 2 --4 4CO 2 + 5H2O
2 SO3 + Hp - - 4 H 2SO4 ,M/ = - 130.2 kJ
Ml =M+ /1nRT I
H2 + - 0 2 --4 H2O,/1H = - 287.3 kJ
/111 = mole of (gaseous products-gaseous reactants) 2

=+ ve On adding all the four equations, we get the equation (i), Hence,
Thus, M/ >M /1Hr = (-298.2)+ (- 98.7) + (- 130.2) + (- 287.3)
81. (CH3 )iC = CHi(g)+ 60i(g) - - 4 4C0i(g)+ 4H2O(/) =-814.4kJ
3
/1ng = 4 - 7 = - 3 (i.e. negative) 88. 2Fe + - 0 2 - - 4 Fep3;M/ = - 193.4 kJ ... (i)
2
We know that, Ml = llE + /1n~T= M - /1n~T
I
(·: /1ng = - ve) Mg + - O2 --4 MgO;MI = - 140.2kJ ...(ii)
2
/1H < /1£
On multiplying Eq. (ii) by (3) and subtracting Eq. (i), we get
82. Work obtained in isothermal 3
3Mg + - O 2 - - 4 3MgO;M/ =-420.6kJ
W = - 2.303 nRT log .!!.J. 2
P2 3
F~O 3 --4 2Fe + - 0 2; /1H = 193.4 kJ
Given, Pi= 500 kPa, p2 = 200 kPa 2
500 3Mg + FeiO3 --4 2Fe + 3Mg0;
(W) = - 2.303 nRT log - = - 2.303 nRT x 0.3980
200 Ml= (-420.6)+ ( 193.4)= - 227.2 kJ
So, minimum work will be o btained when number of moles (n) is 89. The absolute value of enthalpy cannot be determined, only the
minimum. change in enthalpy (Ml) during a process can be determined.
Moles of substances, mass = I kg = 1000 g 90. The molarity and normality are same in case ofNaOH and HCl
because the acidity and basicity of these are one and one
(a) Moles ofC1 2 = 1000 /7 1
respectively.
(b) Moles ofO2 = 1000 / 32
Since, number of moles= molarity x vohune (/)
(c) Moles ofN2 = 1000 / 28 . IOOx I
(d) Moles ofCH4 = 1000/16 :. Number. of moles ofNaOH solution= - - = 0.1
1000
·: Moles ofC1 2 are least. . 300x I
and number of moles ofHCl solutton = - - - = 0.3
So, minimum work is obtained when 1 kg of chlorine gas 1000
expands.
Hence, 0.1 mole NaOH is neutralised by 0.1 mole HCI. We know
83. HF is more stable than HCI. The reason is that in the formation of that heat of neutralisation of 1 mole HCl and 1 mole NaOH is 57.3
HF, more energy is produced. It means, HF has less energy than kJ. Hence, heat of neutralisation of 0.1 mol HCI and 0.1 mole
HCl and hence is more stable. NaOH w ill be= 57.3 x 0.1 = 5.73 kJ
 Thermodynamics I 147
91 . According to question, 2. Since, 1!,.G 0 = !!,.H 0 -T!!,.S 0
3 where, 1!,.G 0 = standard Gibbs' free energy of the reaction
2Al + - 0 2 - Alz0 3;1!,.H =- 1596kJ ...(i)
2
1!,.S O = standard entropy of the reaction
3
2Cr + - 0 2 - Cr2O 3; l!,.H = - 1134 kJ ...(ii) l!,.H O = standard enthalpy of the reaction
2
T = temperanire
Reversing Eq. (ii) and adding both reactions, we get
From, the above equation, it is clear that, 1!,.G 0 will be more
2AI + Crp3 - 2Cr + Alp3; l!,.H = - 462 kJ negative when l!,.S 0 is less negative (or 1!,.S 0 is high).
92. Heat of combustion is usually measured by placing a known mass
of a compound in a steel container called a constant volume bomb In the diagram, 1!,.G0 value for C + .!. 0 2 - CO is less
2
calorimeter.
negative, (lower) than that for C + 0 2 - CO2
M
/!,.E=CxMx -
m Therefore, l!,.S would be higher for C + _!_ 0 , -
0
CO
2 -
where, C = heat capacity of calorimeter, M = (ti - t1)
than that for C + 0 2 - CO 2.
,m = mass of substance taken and M = molar mass of
substance. Hence, M
0
[ C(s) + ¾O2(g) - CO(g)]
93. The heat of neutralisation of strong acid and strong base is
constant because it is in fact heat of formation of water by H+ and > M 0 [C(s) + O 2(g) - CO(g)]
OH- . Its value is a lmost equal to-57.3 kJ. 3. State functions do not depend upon path followed.
94. l!,.H(reaction) = L bond energies of reactant 4. Srhornbic - Smonoclinic
- L bond energies of products. 1!,.H = - 297948 - (- 298246) = 298 J
Given, 2H2 + 0 2 - 2H 2O; 1!,.H = - 571 t.S = 32.68 - 32.04 = 0.64
H- H = 435, 0 = 0 is 498, O - H is? 1!,.G = /!,.H -Tt.S = 298-298 x 0.64 = 107.28 J
1!,.H = (2 x BE of H 2 + BE of 0 2) - 2(BE ofHzO) S. For an ideal binary mixnire,
or - 571 = (2 x 435 + 498) - 2 x BE of H2O 1!,.Hmix = 0 ⇒ 1!,.Vmix = 0, 1!,.Gmix < 0 ⇒ 1!,.Smix > 0
or - 571 = 870 + 498 - 2 x BE of H2O 6. From 1!,.G 0 = - nFE0
or 2 BE of H 2O = 870 + 498 + 57 1= 1939 where n = number of moles of electrons transferred = 2
1939 F = 96500C
: . BE of! H, O molecule= - - = 969.5
- 2 1!,.G0 = - 240 kJ = - 240 x I000 J
969 5 Eo = - 240000 = I _24 V
: . BE of I O- H bond= ·
2 - 2 X 96500
(·: I H 2Omoleculehas2O-H bonds) . . (• ") enthalpy of vaporisation (l!,.H)
7. E ntropy o f vaporisation ~ = - - ~ - ~ - - - ~ ~
= 484.75 boiling point (in K)
95. Molar heat capacity Heat required to raise the temperature of Given, l!,.H = 24.64 kJ mot-
1
and
I mole of a substance by 1° C is called molar heat capacity.
boiling point= 35 + 273 = 308 K
Topic 4 Entropy, Gibb's Energy and 3 1
1!,.S = 24.64 x 10 J mol- = 80 JK_ 1 mol_ 1
Spontaneity (IInd and IIIrd 308K
Law of Thermodynamics), 8. For a process to be spontaneous,
Ellingham's Diagram 1!,.Ssystem + 1!,.Ssurrounding > 0
1. We know that total entropy change of universe is zero. (!!,.GS)"tem k,p < 0
At 100°C and I atmosphere pressure,
(1!,.Usy~em),-,v < 0
H 2O(/) ~ H 2O(g)
9. Given, l!,.H = - 400 kJ mol- 1
is at equilibrium
1!,.S = - 20 kJ mol- 1K- 1
For equilibrium, M 10ia1 = 0
and Afsystem + Msurrounding = 0
Gibbs Helmholtz equation is 1!,.G = l!,.H - ns
As we know during conversion ofliquid to gas entropy of system For a reaction to be spontaneous, 1!,.G must be less than 0,
increases, in a similar manner entropy of surrounding decreases. i.e. negative.
0 "?. 1!,.H -TM
1!,.Ssystem > 0 and Msur,ounding < 0
Hence, (b) is the correct choice. T M ~ 1!,.H ⇒ T ~ l!,.H ~ - 4 00 ~ 20 K
M -20
148 I Chapterwise & Topicwise Engineering Entrances Solved Papers
10. From Gibbs-Helmholtz reaction, Thus, (b) is true
t:,.G = t:,.H -T t:,.S ⇒ 0 =- 20.5x 103 -T x (- 50.0) (c) !':,.G 0 =W 0
- T!:,.S 0
0
3 t:,.G = - nRT In K = - RT In K for n = 1
T= - 20 -5 xl0 =4 10K
- 50.0 - RT In K = t:,.H 0
-Tt:,.S 0
!:,.Ho -T!':,.So)
11. If t:,.G is - ve, the process is spontaneous. In K=- (
RT
12. Entropy is a state function and change in entropy in cyclic process
is zero. Thus, (c) is incorrect
Therefore, (d) t:,.G 0 =- RT In K
!:,.GO
t:,.SX ➔ Y + t:,.SY➔ Z + t:,.SZ➔ X =0 lnK= - - -
- 1':,.Sz➔ x=Mx➔ r+ t:,.SY➔ Z
RT
K = e- aa•tRT
= Mx➔ Z
Analysis of options (b) and (c). Work is a non-state function, it Thus, (d) is also true
depends on the path followed. Wy➔ z = 0. Therefore, 15. ·: t:,.G = t:,.H -TM
Wx ➔ y➔ z = Wx ➔ r- Also, work is the area tmder the curve on Jr
V diagram. At equilibrium, t:,.G = 0
X y X,;..__ _ _Y t:,.H =TM
t:,.H = 273 X (60.01 - 38.20)
p~ 1 1
p_ =_WHY-+z/~ Z = 5954.13 J mol- = 5.954 kJ mo1-
I',·,~·,:·.:~·.:·,:·;,',:·,:·,:·:.:·,::1
,;· ·.:~~:·.:~:·.:~:·.:~~:·.:~',·.:1
L',::•,:•,:•;.•,:•,:•,::•,:•,:•,:•,•;,:1 16. From Gibbs-Helmholtz equation, t:,.G = t:,.H - Tt:,.S
V V For a spontaneous, reaction, t:,.G = - ve, and it is possible when
As shown above, Wx➔ r + Wy➔ z = Wx➔ r = W,¥➔ Y➔ z but not t:,.H = - ve, and t:,.S = + ve
equal to Wx➔ z· Thus, for a spontaneous reaction, there must be increase in
13. For calculation of C == C bond energy, we must first calculate entropy and decrease in free energy.
dissociation energy of C2H 2 as 17. On crystallisation of a salt from its saturated solution,
C2H 2(g) - 2C(g) + 2H(g) ... (i) randomness decreases, as a result, entropy decreases.
Using the given bond energies and enthalpies. 18. From the first law of d1ermodynamics, the total energy of the
tmiverse remains constant.
C2H2 (g) - 2C(s)+ H 2 (g) ;t:,.H =- 225 kJ ... (ii)
19. t:,.G(T,p) = t:,.H -Tt:,.S determine the existence ofa reaction.
2C(s) - 2C(g) ;W = 1410 kJ ... (iii)
H 2(g) - 2H(g); t:,.H = 330 kJ .. . (iv) 20. For an isolated system,
Adding Eq. (ii), (iii) and (iv) gives Eq. (i) TM=t:,.U+pt:,.V
⇒ C2H 2(g) - 2C(g)+2H(g);W= l 515kJ If t:,.U = 0
⇒ 15 15kJ=2x(C- H)BE+ (C==C)BE TM =pt:,.V
= 2 x 350 + (C == C) BE t:,.S = pt:,.V > 0
⇒ (C == C) BE= 1515- 700= 815 kJ / mo! T
14. t:,.G = t:,.H - TM 21. Entropy change for n moles of isothermal expansion of an ideal
gas from volume V 1 to volume V2 is
For a system, total entropy change is t:,.S101• 1
!':,.S = 2.303nR log V2 = 2.303 X 2 X 8.3 143 log l OO
t:,.Htotal =0 v, 10
!':,.Gsystcm =- Tt:,.Stotal
= 38.296 J mol- 1K- 1
!':,.Gsystcm = -T
22. PbO2 + Pb - 2PbO
t:,.Stotal
Oxidation state + 4 O +2
Thus, (a) is true.
Since, t:,.,G < 0, hence +2 state of lead is favourable.
0

(b) For isothermal reversible process, M = 0 By first law of

thermodynamics SnO 2 + Sn - 2SnO
t:,.E=q+W Oxidation state +4 0 +2
V! Since, 6,G > 0, it means forward reaction is not spontaneous.
0

w ,eversible = - q = - JV; p dV
2SnO - SnO 2 + Sn
VJ +2 +4 0
w ,eversible =- nRT In -
vi For this t:,.,0°< 0, thus +4 state of tin is favourable.
 Thermodynamics I 149
23. In the reversible reaction, 31. Negative value of AG (Gibb's free energy) shows that the process
A(s)+ B(g) ~ C(g) + D(g); AG 0 = -350kJ is possible (i.e spontaneous).
Since, the randomness increases (because solid is changing into 32. We know that,
gas), entropy will increase and thus, AS is positive. Reversible Gibb's free energy change, AG = AH - ns
reaction never undergo to completion (i.e. never be TAS =t.H-AG
instantaneous).
I
·: For the given reaction, 1";.G 0 = -350 kJ and we know that AS =r[t.H- AG ]
AG 0 = -RT log K
33. Entropy is a measure of randomness ofa system. The greater the
i.e. (equilibrimn constant) is greater than one. Moreover, the disorder in a system, the higher is the entropy. The solid state is
reaction is thermodynamically feasible. the state of lowest entropy (most ordered state) hence, duri ng the
24. Above 983 K, free energy change for the formation of CO2 is crystallisation ofsucrose from its solution, the entropy decreases.
more negative than that for ferric oxide. Thus, above this :. Liquid state changes into solid state.
temperanire, carbon has a higher affinity towards oxigen than
34. Standard Gibb's energy of formation (AG '} ) of a substance is
iron.
defined as the Gibb's energy change when one mole of the
25. Entropy change in the transition of the vapour to liquid, substance is formed from its elements in their standard states. The
1,
3 1 following reaction define AG
A S = Hcond = - 35.3 X I 0 J mol- = - I 00 JK-lmol-1
00nd I I
Tb (80 + 273)K - H, (g)+ - F2 (g) - - HF(g)
2 - 2
26. AG 0 = - RT lnK
35. ·: AG=t.H-ns ⇒ -5·2=145 -6-T(216/ 1000)
or, t.H 0 -TAS 0 = -RT lnK
-AHO ASO or T = 698 K = 425°C
or InK= - - + - - 1";.G
, RT R 36. Percentage efficiency of the fuel cell = - x I00
For endothermic t.H
j reaction The concerned reaction is :
mo
tan 0 = -
3
In K LiS0 R CH 3OH(/) + 0 2 (g) - - CO2 (g)+ 2H2O(/)
} R 2
AGr = AG1(CO2,g)+ 2AG1 (H2O, /)
1/T -
3
Comparing w ith y = m.x + c - 1";.GlCH3COOH ' /)- 2/';.GlO2, g)
. . AS 0
y intercept 1s - - = -394.4+ 2(-237.2)-(-166.2)-0= 702.6
R 702 6
27. At constant temperanrre Thus, percentage efficiency · x!00= 96.77
726
V
AS = n x 2.303 R log --1. 37. 1";.G =t.H-T·AS
vi For the reaction, Hp{/) ~ H 2O(g)
9
AS = I x 2.303 x 1.987 log - 1";.G = 0 (at equilibrium)
I
1 1 t.H =T·AS
AS= I x 2.303 x 1.987 x 0.9542= 4.366 cal · K- mol-
38. Given, dE = TdS - pdV ...(i)
2 4
28. - Al 2O 3 -- - Al+ 0 2 H =E+ pV ...(ii)
3 3
Differentiating Eq. (ii),
AG = + 966 kJ mo!- 1 = 966 x 103 J mol- 1
dH = dE+ pdV + Vdp ... (iii)
AG =-nFEcell
From Eqs. (i) and (iii), we get
3
966 x 10 = - 4 x96500xEcell dH =TdS+ Vdp
Ecell = 2.5V 39. Third law ofthermodyamics states d1at the entropy ofa perfectly
29. AG= /';.H-TAS crystalline substance is zero at 0°C.
At equilibriu m, 1";.G = 0 40. For a spontaneous chemical reaction, free energy must be
negative or in other words free energy is the quantity that
For a reaction to be spontaneous 1";.G should be negative, so T
decreases to a minimum in any chemical reaction.
should be greater than Te.
41. According to Gibbs-Helmholtz reaction,
30. Entropy is the measure of randomness. In liquids randomness is
more than solids. /';.G=/';.H-ns
: . W hen ice melts, randomness increases, (solid - - liquid) If for a reaction 1";.G is negative, the reaction must be spontaneous.
Hence, Agp decomposes into Ag and 0 2•
: . Entropy increases.
150 I Chapterwise & Topicwise Engineering Entrances Solved Papers
42. Given, M = -5 cal, /iS = - 10 cal K- 1 lo K _ 115000
glO P - 2.303 X 8.314 X 298
A(g) + B(g) - C(g)
Ml= M + !inRT = - 5-1 x 2-0 x 298 = - 601 log10 KP = 20.16
!iG = Ml -T!iS = - 601 - 298 x (- 10) = 2379cal 51. For endothennic reaction Ml is positive, i.e. Ml > 0.
So, none of the given option is correct. For a spontaneous process /iG is always negative and
43. The value of /iG for ice at 8° C temperature will be positive as at !iG = Ml - T!iS thus, to maintain the value of /iG negative. !iS
this temperature melting of ice is started. must be positive, i.e. !iS > 0.
52. A spontaneous process is one in w hich the system suffers a
44. When ice changes into water spontaneously at room temperature,
the randomness increases, so entropy increases, which is in lowering of free energy because /iG = - ve, for a spontaneous
accordance to the second law of thermodynamics. reaction.

45. Gibbs-Helmholtz equation is as follows :

53. In going from initial to final state, the entropy change, !iS for an
ideal gas is given by the following reactions
liG=MI-T!iS T. v;
From Gibbs-Helmholtz equation, it is clear that /iG will always liS = nCv In -1 + nR In -1
be negative, if Ml is negative and T!iS is positive.
r, v,
46. In reaction (a) Na (s ) reacts with H 2O(l) to give NaOH (l) and or !iS = nC In T2 + nR In !!J...
p r, Pi
_!_H2 (g). Since, the entropy of a gas is higher than that of liquid
2 But at constant temperature, /iS = nR In Vi
and the entropy ofliquid is higher than that ofsolid, therefore, the v,
change in entropy for this reaction increases. i.e. !iS = nR In !!J...
P2
47. I2(s) ,::::::::::': I2(g)
54. Entropy is the measure of degree of disorder (or randomness) ofa
!iG = liH -T!iS system. The greater the disorder in a system, the higher is the
At equilibrium, !iG = 0 and entropy. Hence, entropy is highest for hydrogen gas.
4 3 55. Between Al 2O 3 and Cr2O3, Al 2O 3 is more stable, so its ease of
T_ b = /iH = 0 X l 0 = 500 K = (500- 273)°C = 227°C
SU /iS 80 fonnation is high i.e. /iG 0 is negative or less than that ofCrp3.
1 3 Hence, !iG 0 ofCr2O 3 > liG 0 of Al 2O3
48. - X 2 + - Yz - XYj
2 2 56. Entropy is a measure of randomness of the system, so entropy ofa
/iS reaction = S products - S reactants substance in different physical states is in the order
Gas > liquid > solid
/iSreaction = 50 - (% X 40 + ¾X 60) = - 40 J mol- l
fiS = S product - S reactant
liG=MI -T!iS In option (c) solid is converted into gaseous state, so /iS will be
positive.
At equilibrium as /iG =0
57.
Ml =T!iS

⇒
T =Ml= 30 x 103 = 750 K
/iS 40

!iG 0 = - 1234 kJ
T~
II. C(s ) + O 2(g) - CO 2(g); liG = - 394 kJ 0

1 Reaction (I) Mg(s) + ..!..02 (g) - MgO(s)

IIT. H2(g) + - O2(g) - H2O(/); /iG 0 = - 237 kJ 2
2
Multiply the Eq. (II) by 2 and then add with Eq. (TTI) and subtract Reaction (II) CO(g) + ..!..0 2 (g) - CO2(g)
Eq. (D from the sum of (TI) and (III) 2

2C(s) + H 2(g) - C 2H 2(g) Reaction (III) C(s) + ..!..o2 (g) - CO(g)

2
!iG 0 = 2(-394) + (-237)- (- 1234)
/iG 0 versus, Tplot in the Ellingham's diagram slopes downwards
!iG 0 = 209 kJ for the reaction (l) and reaction (II). For reaction (ITT) /iG 0 versus
50. /iG 0 =- 115 x 103 J T in the diagram slopes upwards.
T = 298 K, R = 8.314 JK- 1 rnol- 1 58. /iG = Ml - T!iS
- !iG 0 = 2.303 RT log 10 KP For a reaction to be spontaneous /iG must be negative. If /iG and
Ml are negative, then reaction will be spontaneous at a ll
-(- 115 x 103)= 2.303x 8.314 x 298 log 10 KP temperature.
 Thermodynamics I 151
59. X(g) + 3Y (g) ~ 2 Z(g) 67. Gibb's free energy G, enthalpy Hand entropy Sare interrelated
asG = H - TS.
t,,$ = 2S (Z)- {S (X) + 3S (Y)}
0 0 0 0

= 2 X 50 - {60 + 3 X 40} 68. When a solid melts, its entropy (S) increases because on changes
= I 00 - I 80 = - 80 J K - 1mo1- 1 from solid to liquid disorder or randomness of molecules
increases.
Given, .Af/0 = - 40 kJ = - 40000 J
t-,.GO= .Af!O- Tt-,.S O 69. The Gibb's-Helmholtz equation is as G = H+ T(oG)
oT P
At equilibrium, t-,.G 0 = 0
.Af!O=T""-So . .d.mg above equatton
D1v1 . by T2 G =
2T
I
2T + -T -<JT
H (oG)
P

or T = t-,.HO= 40000 = SOO K

.
6S 0 80 This on rearrangement becomes lra(GoT/ T)lJ = - 2TH
P
.Af/ 80
60. t,,,S = ____!!!tl__ = - = 0.293 cal/g/K
trel T 273 H _ Tiracc I T)l
61 . For a spontaneous process, t-,.G must be negative. -- loT JP
t-,.G =6H - TM where, H = enthalpy.
: . For negative value of t-,.G at all temperatures, 70. The condition for spontaneity in an isothermal process is that t-,.G
.Afl = - ve should be negative.
t,,,S = + ve t-,.G=M + p-t-,.V
62. Reaction is non-spontaneous at 298 K (given). t-,.G = t-,.A + W (": W = p-t-,.V)
t-,.G 0 = .Af/0 - TM 0 = 76000 - 298 x 60 = 58 120 :. For spontaneity in an isothermal process :
t-,.G is positive so reaction is non-spontaneous (given). M+W<O
For spontaneous reaction, t-,.G must be negative at temperature 71. t-,.G = .Afl - TM
827°C i.e. 827 + 273=1100 K
Given that, .Af/ = - 382.64 kJ mol- 1
t-,.G = .Af/0 - TM 0 = 76000 - I 100 x 60
t-,.S = - 145.6 JK- 1 mo1- 1 = - 145.6x 10- 3 kJ K- 1
= - 10000
At 827° C, reaction will spontaneous. or t-,.G = - 382.64 - (298 x - 145.6 x I ◊-3 )
63. A ~ B = - 339.3 kJ mo!- 1
t-,.G 0
= t-,.H 0
- T6S 0
72. For spontaneous process, t-,.S must be positive. In reversible
t-,.G = - 2.303 RT log Kc
0 process
.Af!O- Tt-,.S O t-,.Ssystem + t-,.Ssurrounding = 0
log Kc = - 2.303 RT Hence, system is present in equilibrium
(i.e. it is not spontaneous process)
- 54.07 X 103 - 298 X 10 = - 57050 = I ◊
- 2.303 X 8.314 X 298 - 5705 While in irreversible process
t-,.Ssystem + t-,.Ssurrounding > 0
64. HzO(l) and HzO(g) both exist together at same temperature and
pressure, suggests the state of equilibrium. Hence, t-,.G = 0 and Hence, in the process M is positive.
conversion of liquid into gas increases disordemess, hence 73. The standard free energy change (t-,.G 0 ) is related to equilibrium
entropy, t,,,S = + ve. constant K as
65. In an isolated system where either mass and energy are not t-,.G 0 = - RT lnK = - 2303 RT logK
exchanged with surrounding for the spontaneous process, the 74. An irreversible process
change in entropy is positive.
spontaneous process
6
66. M= H (dS)VE (change in entropy)= + ve > 0
T
(dG}r .P (change in Gibb's free energy) - ve ⇒ < 0
t,,,S = 160.2 J/K
75. In equilibrium state the value of t-,.G is zero.
.Afl = 179.1 x 103 J/ mol
76. According to second law of thermodynamics, the entropy of the
103
T = 179. l x J / mo! = I I I 7 .97 K = 1118 K universe always increases in the course of every spontaneous
160.2 J/K (natural) change.
77. The order of entropy in solid, liquid and gas is
152 I Chapterwise & Topicwise Engineering Entrances Solved Papers
gas> liquid > solid = 50 + 30 - 20 = 60 eu
Hence, in su blimation of naphthalene, maximum increase in 87. Evaporation of water is an endothermic reaction. Hence, t::Jl
entropy is observed. value will be positive and when water changes to vapour,
78. t::Jl = - ve (combustion reaction) randomness increases. So, M value will also positive.

(spontaneous at all temperature) 88. T /';. S > /'iH for reaction to be spontaneous. When t::Jl = + ve and
M =+ve
M = + ve, the reaction will be spontaneous at high temperature.
/'iG =-ve (because reaction is spontaneous)
79. K = e - t;G/ RT = 1o - 6 G/ 2.303RT 89. ·: /'iG = t::Jl - T · M
p
For spontaneous reaction /'iG should be negative
K = I 0-46. 06/ I. 99x I o-3 x300X2. 303
p t::Jl = - 238 kJ,
K
p
= 10- 3133 M =- 87 JK- 1

80. For a reversible reaction M sys1em + Msurrounding = 0 Hence, reaction will be spontaneous when
t::Jl > T · /'iS. Therefore, at I 000, 1500 and 3000 K the reaction
81. For a spontaneous process the value of /'iG should be negative
would be spontaneous.
/'iG < 0.
90. ·: /'iG 0 = t::J/ 0 - T · M 0
=- 29.8 - 298 X (- 0. 1)
82. /'iG = t::Jl - T · M
=- 29.8 + 29.8 = 0
t::Jl = - 25 kcal = - 25000 cal
91. ·: /'iG = - n.FE 0
T = 300 K, M = 9 cal
/'iG 0 = - 2.303 RT log K
/'iG = - 25000 - 300 x 9 = - 25000 - 2700
/'iG = - 27700cal Eo = 2.303 RT log K
nF
The value of /'iG is negative hence, the reaction is spontaneous.
83. For a spontaneous or nan1rally occurring process, free energy At 298 K, Eo = 2.303 X 8. 314 X 298 log K
n x 96500
change is always negative, i.e. /'iG < 0.
o _ 0.0591 K
84. For a spontaneous process, /'iG < 0 E - - -1og
II
For non-spontaneous process, /'iG > 0
92. M = Qrev
At equilibrium, t:,.G = 0 T
85. /'iG = t:,.H - TM The unit of entropy is JK- 1 or cal K- 1•
For the spontaneous reaction the /'iG must be negative. 93. /'iG 0 = - 2. 303 RT log Keq,
t::Jl = + 3 kJ = + 3000 J, /'iS = + 10 J / K
/';.Go = - n.FE ocell
If T = 300 K, /'iG = 3000 - 300 x 10 = 0
If a cell reaction is spontaneous (proceeding in forward side), it
If T = 200 K, t:,.G = 3000 - 200 x IO= 1000 J means
If T = 273 K, /'iG = 3000 - 273 x IO= 270 J Keq > I and E 0 cell = + ve
If T = 373K, /'iG = 3000 - 373 x 10= - 730J Thus, /'iG 0 = - ve
Hence, beyond 300K temperanire the reaction will be 94. Variation of Keq with temperanire T is given by van' t Hoff
spontaneous. equation.
86. C ~ D t::JI O !)SO
i ! logK =- - - - + - - -
A B eq 2.303 RT 2.303 R
Given, M(A➔q = 50eu A B
M(C➔ D) = 30 eu Slope of the given line is positive indicating that term A is
/'iS(B➔ D) = 20 eu positive thus /'iH 0 is negative.
where, eu is entropy unit Thus, reaction is exothermic.
Therefore, 95. Entropy is the measure of randomness in the molecules.
M(,HB) = 1':,.S(A➔q + M(C➔ D) + 1':,.S(D➔ B) Randomness is maximum in case of gases. Hence, entropy is
maximmn for water vapours.
= 1':,.S(A➔q + 1':,.S(C➔ D) - 1':,.S(B➔ D)
 Thermodynamics I 153
96. For a system in equilibrium, l'lG = 0, when all the reactants and 11G = Ml - T - t::,S = 3 I 400 - 1273 x 32
products are in the standard state [at constant temperature and = 31400- 40736
pressure] and Kc = I.
= - 9336cal
97. t::,S = 16 J mo1- 1K- 1 Ml,,= 6 kJ mo1- 1
100. T = 100° C = 100 + 273 = 373 K
Tb = Ml vapour = 6 X 1000 = 375 K Aflv = 40.8 kJ = 40800 J
p t::,Svapour I6
t::,S = Aflv = 40800 = 109.4 JK- 'mol- 1
98. 11G = Ml - Tt::i.S T 373
where, Ml= 30.558 kJK- 1mol- 1 101. Hi(g) + C1 2 (g) - 2HCl(g)

t::i.S = 0.066 kJK- 1mo1- 1 M o= 1 sop - I soR

= 2x 187-(13 1 + 223)
11G = 0
= 374 - 354 = 20 JK- 1mol- 1
0 = !1H - Tt::i.S
l'lH = Tl'lS 102. For a reaction to be spontaneous l'lG must be negative.
According to re lationship of l'lG,
30.558=Tx 0.066
11G =Afl -T-t'lS
T = 463K If Ml and l'lS both are positive, then term T •t::,S will be greater
Reaction is non-spontaneous reason being than 11H at high temperature and consequently l'lG will be
11G = 0 negative at high temperanire. (boiling point of water) and
99. Given, Ml= 31400 cal reaction becomes feasible.
103. ZnO + c - Zn + CO
t::i.S = 32 cal K- 1mol- 1
!1G = -ve.
0

T = 1000 + 273 = 1273K

Hence, this is spontaneous.
11G =?
From Gibb's - Helmholtz equation
Equilibrium
QUICK REVIEW
A chemical equilibrium is a state at which the composition Types of Chemical Equilibrium
of a chemical system becomes constant under given set of (i) Homogeneous equilibrium When in an equilibrium
conditions. It is dynamic in nature, both forward and reaction, all the reactants and products are present in the
backward reactions are in progress with the same speed. same phase, (i.e. gaseous or liquid), it is called a
Presence of a catalyst does not affect the final state of the homogeneous equilibrium.
equilibrium. (ii) Heterogeneous equilibrium When in an equilibrium
Types of Equilibrium reaction, the reactants and the products are present in two
There are three types of equilibrium : or more than two phases, it is called a heterogeneous
(1) Physical equilibrium, equilibrium.
e.g. H 2 0(/) ~ H 2 0(g)
(ii) Chemical equilibrium,
Law of Mass Action
e.g. PC15 (g) ~ PCl 3 (g) + Cl 2 (g) • According to law of mass action, the rate of forward reaction is
directly proportional to the product of molar concentrations
(iii) Ionic equilibrium,
(active masses) of the reactants, i.e. each concentration term
e.g. CH 3 COOH ~ CH3 COO- + H +
raised to the power equal to the nwnber of times that reactant
Types of Process appear in the balanced equation.
• Reversible process Reaction in which the products aA + bB ~ cC + dD
of the reaction can react with one another under same According to law of mass action,
conditions of the reaction to give back the reactants is Rate of forward reaction, r1 oc [A]0 [Bl
called reversible process, e.g. formation of NH 3 ,
S03 etc., such process do not go to completion. Rate of backward reaction, r6 oc [ ct [Df
• Irreversible process Those reaction in which the Active mass of a gas or liquid is equal to its molar concentration
products formed do not react to give back the and the active mass of solids is constant and taken as unity. The
reactants, e.g. 2KC10 3 ~ 2KC1 + 302 rate of a reaction is proportional to the product of the active
Such process go to completion. masses of the reactants each raised to the power equal to its
coefficient as represented by the balanced chemical equation.
Law of Chemical Equilibrium
t
O.l aA +bB ~ cC + dD
1il
a:
[Ct[Df
Kc= - - - -
[A]° [B/
where, [A ], [B ], [C] and [D ] are molar concentrations of A,B, C
Time -+ and D at equilibrium and K c is the equilibrium constant.
 Equilibrium I 155
Equilibrium constant in terms of partial pressure where, C is the concentration in mol- 1L and V is the
c d
volume of solution in L having 1 mole of electrolyte for
K = Pc· pD
P a b weak monobasic acids,
PA. PB
where, p A , p 8 , Pc and p D are the partial pressures of CX, = ✓Kd =.JK V 0

J¥
A, B, C and D respectively at equilibrium.
KP and Kc have no units for a reaction when 1:-,.n = 0. For weak monoacidic bases, ex, = = .JK bV
• Relationship between KP and Kc
KP = Kc(RT)lln Relative Strengths of Two Weak Monobasic Acids
strength of acid HA 1 ~
(where, 1:-,.n = nproducts - n,eactants)
• Equilibrium constant in terms of mole fractions
= strength of acid HA 2 = v-iz:;
aA + bB ~ cC + dD
Arrhenius Concept of Acids and Bases
K = [Xct[xDt An acid is defined as a substance which contains
X [XA t[XB]b hydrogen and which when dissolved into water gives
K x depends upon temperature, pressure and volume. hydrogen ions H+.
A base is defined as a substance which contains hydroxyl
KP = K x ( p )lln (where, p is the external pressure)
groups and which when dissolved in water gives
Reaction Quotient (Q) hydroxyl ions (Off ).
It is the ratio of concentration tenns having the same form as Bronsted-Lowry Concept of Acids and Bases
equilibrium constant expression at each point in a reaction.
• An acid is defined as a substance which has the tendency
Q = Kc reaction is in equilibrium
to give a proton (H+ ) and a base is defined as a substance
Q< Kc reaction proceeds in forward direction
which has a tendency to accept a proton.
Q > Kc reaction proceeds in backward direction
• Conjugate acid-base pairs A conjugate pair of acid
and base differs by a proton only, i.e.
Factors Affecting Equilibrium
Conjugate acid~ Conjugate base + H+
The effect ofchange of concentration, pressure and temperature
Conjugate pair I
is predicted with the help ofa principle known as Le-Chatelier's
principle. Conjugate pair TT I
Le-Chatelier's Principle Acid 1+Basei Acid2+ Base 1
If a stress is applied to a reaction mixture at equilibrium, HCl + H2O ~ H3 o+ + CC
reaction occurs in that direction that relieves the stress.
On increasing concentration of reactants, reaction goes in a HCl + NH3 ~ NH4+ + Cl-
direction that tends to decrease concentration and
vice-versa. On increasing pressure (or decreasing volume), Ionic Product of Water and Dissociation Constant
reaction goes in a direction that tends to decrease pressure Ionic product of water may be defined as the product of
and vice-versa. On increasing temperature, reaction moves the molar concentration ofH3 o + ions and OH- ions ( H+
in a direction that tends to decrease the temperature. ions and OH- ions).
1:-,.n = + ve, increased pressure shifts equilibrium in backward
H2 O ~ H+ + OW
direction. 1:-,.n = - ve, increased pressure shifts equilibrium in
forward direction. 1:-,.n = 0, change in pressure has no effect. H2 O + H2 O ~ H 3 O+ + OW
Presence of catalyst increases the rates of forward and
K = [H3 O+][OH- ]
backward reaction with the same rate.
[H20]2
Ionisation of Weak Electrolytes: Ostwald's Dilution Law
For a weak electrolyte of the type AB, where, K is the dissociation constant of water.
2 [H 3 0 +][0H- ] = K [H 2 O]2 = K w
Dissociation constant, K = Ca = Ccx, (1- cx,
1- ex,
2
=1) where, Kw is called the ionic product of water.
K w = [H3 O+][OH- ]
ex, = {K" = -JKV
'le · Kw= 1.00x 10- 14 at 298 K
156 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Common Ion Effect Salt Hydrolysis
• The suppression in the dissociation ofa weak electro!yte by (i) For salts of weak acid and strong base
the addition ofa strong electrolyte having a common ion is
Hydrolysis constant (K h) = Kw
called common ion effect. Ka
• pH = - log [H3 o+ ], pOH = - log [Off]
pKw = pH + pOH = 14at 298K
Degree of hydrolysis (h) = J¥.
= ✓:a•~
pK a = - log Ka , pK b = - log Kb
pKa + pKb =pKw
Solubility Product I
pH = - [pKa + pK w + log C]
• The solubility product of a salt at a given temperature is 2 .
equal to the product of the concentration of its ions in the I
saturated solution, with each concentration te1m raised to = 7 + - [pK a + log C]
2
the power equal to the number of ions produced on
(ii) For salts of strong acid and weak base
dissociation of one mole of the substance. Solubility
product of a sparingly soluble salt AxBy is calculated as Hydrolysis constant ( K h ) = K w
AxBy ~ xA Y + + yBx - Kb
Ksp = [A Y+y ,[Bx - y
In an ionic reaction, precipitation takes place only if ionic
Degree of hydrolysis (h) = J¥.
product is greater than solubility product.
Henderson Equation
=✓K~~,C
1
pH of an acidic buffer pH = - [pK w - pK b - log C]
[salt] 2
PH=pK a =pKa + log -[acid]
- 1
= 7 - - [pK a + log C]
2
. [salt]
pH of a basic buffer pOH = pK b + log - - (iii) For salts of weak acid and weak base
[base] 2
K h
pH = 14- pOH Hydrolysis constant (K h) = w - --
K 0 ·K b 1-h 2
Buffer Capacity
Degree of hydrolysis (h) = ,JK; = r=zs:=_
It is defined as the number of moles of an acid or a base
required to be added to IL of the buffer solution, so as to
change its pH by one unit. 1
v~
pH= - [pK w + pK a - pK b]
,,,. . n 2
Buuer capacity = - -
~pH I
=7+ -2 [pKa. - pKb ]
Degree of Hydrolysis ( h)
Generally in salt hydrolysis,
The degree of hydrolysis of a salt is defined as the fraction
(percentage) of the total salt which is hydrolysed. K 0 = K b, pH = 7
h = number of moles of the salt hydrolysed
K a >Kb,pH< 7
Ka <Kb,pH> 7
total number of moles of the salt taken
 Topic 1
Equilibrium Constants and Their Units
2014
1. For the reaction, SO2 (g) + _! 0 2 (g) ~ SO3 (g) 7. The mixture of reactants and products in the equilibrium
2 state is called [J&K CET]
if,KP = Kc (RTY (a) chemical mixture (b) equilibrium mixture
(c) chemical equilibrium (d) dynamic equilibrium
where, the symbols have usual meaning, then the value ofx
is (assuming ideality) [JEE Mains] 2013
1
(a) - 1 (b) - - 8. The initial rate of hydrolysis of methyl acetate (lM) by a
2 weak acid (HA, l M) is 1/ 100th of that of a strong acid
1 (HX, 1 M), at 25°C. The K a HA is equal to
(c) - (d) l
2 (a) l X 10- 4 (b) 1 X 10- 5 [JEE Advanced]
2. The rate constant for forward reaction and backward ( c) l X 10- 6 ( d) 1 X 10- 3
reaction of hydrolysis of ester are l. l x 10- 2 and
9. KP and Kc are related as [KCET]
1.5 x 10- 3 per minute, respectively. Equilibrium constant
(a) KP = Kc (RT/'n (b) Kc = KP (RT)t,.,'
for the reaction [VITEEE]
(c) KP + K c = (Rrt ·
11
(d)Kc = KP
CH 3 COOC2 H 5 + H 2 O ~ CH 3 COOH + C 2 H 5 OHis (e)Kc·Kp = (RT) 11

(a) 33.7 (b) 7 .33

(c) 5.33 (d) 33.3 l 0. In the synthesis of ammonia
3. Equal moles of NO 2 (g) and NO (g) are to be placed in a N 2 (g) + 3H2 ~ 2NH3 (g)
container to produce N 2 O . When 100 mL ofN2 has reacted, the volume ofH2 which
According to the reaction, has also reacted and ammonia produced are CKCET]
NO 2 + N O ~ N 2 O + O 2 ,Kc = 0.914 (a) 300 mL H 2 and 200 mL NH 3
How many moles ofNO2 and NO be p laced in the 5.0 L (b) 300 mL H 2 and 300 mL N H 3
container to have an equilibrium concentration of N 2 0 to (c) 100 mL H 2 and 100 mL NH 3
be 0.05 M ? [Manipal] (d) 100 mL H 2 and 200 mL N H 3
(a) 0.511 (b) 0.1023 11. AquantityofPC1 5 washeatedina10dm 3 vesselat250°C
(c) 0.0526 (d) 0.2046 PCl 5 (g) ~ PCl3 (g) + Cl2 (g)
4. For the equilibrium reaction At equilibrium, the vessel contains 0.1 mole of PC1 5 and
CaCO3 (s) ~ CaO(s)+CO 2 (g), 0 .2 mole ofC1 2 • The equilibrium constant of the reaction
KP = l.64 atrn at 1000 K is [KCET]
50 g ofCaCO3 in a 10 L closed vessel is heated to 1000 K. (a) 0.05 (b) 0.02 (c) 0.025 (d) 0.04
Percentage of CaCO3 that remains unreacted at
1
equilibrium is [given, R = 0.082 L atrn K - mol- ]
1 2012
(a) 40 (b) 50 [KCET] 12. The equilibrium constant (Kc ) for the reaction
(c) 60 (d) 20 N 2 (g) + 0 2 (g) ~ 2NO(g) at temperature T, is
4
4 x 10- . The value of Kc for the reaction
5. The KP value for the reaction, H 2 + 12 ~ 2HI at
1 I
460°C is 49. If the initial pressure of both H 2 and 12 is NO (g) ~ - N 2 (g) + - 0 2 (g) at the same
2 2
0.5 atrn, then what will be the partial pressure of H 2 at
temperatw·e is [IlTJEE]
equilibrium ? [AMU]
2
(a) 0.02 (b) 2 .5 X 10
(a) 0.112 atrn (b) 0.123 atrn 4
(c) 0.113 atrn (d) 0.222 atrn (c)4xl0- (d) 50.0
6. In a reaction A + B ~ C + D, 40% ofB has reacted at 13. For 2NOBr (g) ~ 2NO(g) + Br2 (g ), at equilibrium
equilibrium, when 1 mole of A was heated with 1 mole of B
in a l OL closed vessel. Psr2 = p and p is the total pressure, the ratio KP will be
9 p
The value of Kc is [EAMCET]
(a) I / 3 (b) 1/ 9 [BITSAT]
(a) 0.44 (b) 0.18 (c) 0 .22 (d) 0.36 (c) l / 27 (d) 1/ 81
158 I Chapterwise & Topicwise Engineering Entrances Solved Papers
14. For the reaction, 2010
1 21. In aqueous solution, the ionisation constants for carbonic
2NO2 (g) + 02 ~ N 2O 5 (g)
2 acid are
11
if the equilibrium constant is KP, then the equilibrium K, = 4 .2x10- 7 and K2 = 4 .8x10-
constant for the reaction
Select the correct statement for a saturated 0 .034 M
2N2O5 (g) ~ 2N2O 4 + O 2 (g) solution of the carbonic acid. [AIEEEJ
would be [MPPET]
(a) The concentration of co~- is 0 .034 M
1
(a)K; (c) - (d) 2K P (b) The concentration of co~- is greater than that of
K2p
HCO3
15. The equilibrium constant of a reaction is 0.008 at 298 K. (c) The concentration ofH+ and HCO3 are
approximately equal
The standard free energy change of the reaction at the same
( d) The concentration of H+is double that of COj-
temperature is [KCET]
(a) - 11.96 kJ (b) - 5.43 kJ {c) - 8.46kJ (d) + 1 l.96kJ 22. NH4 HS(s) ~ NH 3 (g) + H 2S(g)
16. The correct order of equilibrium constant for the reactions In the above reaction, if the pressure at equilibrium and at
is 300 K is 100 atrn, then what will be the equilibrium
K1 constant KP ? [MP PET]
H 2 CO + H 2 O ~ H 2C(OH) 2 2 2
(a) 2500 atm (b) 50 atrn
K2 2 2
CH 3 CH 2CHO + H 2O ~ CH 3 CH2CH(OH)z (c) 100 atm (d) 200 atm .
K3 23. 4NH 3 + 502 ~ 4NO+ 6H 2 O
CH 3 COCH 3 + H 2 O ~ CH 3 C(OH) 2 CH 3 [AMU]
For the homogeneous reaction, the equilibrium constant
(a)K 1 >K2 >K 3 (b)K 1 <K2 <K 3 Kc has the units [RPET]
(c)K 1 >K3 >K 2 (d)K 1 <K 3 <K2 (a) cone. +io (b) conc.+ 1
(c) cone. _, (d) it is dimensionless
2011
17. A vessel at 1000 K contains CO 2 with a pressure of 24. A reversible chemical reaction is having two reactants in
0.5 atrn. Some of the CO 2 is converted into CO on the equilibrium. If the concentration of the reactants are
addition of graphite. If the total pressure at equilibrium is doubled, then the equilibrium constant will [JCECEJ
0. 8 atm, then the value of KP is [AIEEEJ (a) be doubled
(a) 1.8 atrn (b) 3 atm (b) become one-fourth
(c)0.3atm {d)0.18atrn (c) be halved
( d) remain the same
18. 4 moles of PC1 5 are heated in a closed 4dm3 container to
reach equilibrium at 400 K. At equilibrium, 50% of PCI 5 25. For which one of the following reactions KP = K c?
is dissociated. What is the value ofKc for the dissociation (a) PC15 ~ PC13 + Cl 2 [JCECEJ
of PCI5 into PCI 3 and Cl 2 at 400 K? [Kerala CEEJ (b)N2 + 02 ~ 2NO
(a) 0 .50 (b) 1.00 (c) 1.15 (c) N 2 + 3H2 ~ 2NH 3
(d) 0 .05 (e) 0.25 ( d) 2SO 3 ~ 2SO2 + 0 2
19. Consider the following gaseous equilibria with equilibrium
constants K I and K 2 , respectively.
2009
26. 5 moles of SO2 and 5 moles of 0 2 are allowed to react. At
SO 2 (g) + _! 0 2 (g) ~ SO3 (g) equilibrium, it was found that 60% ofSO 2 is used up. Ifthe
2
total pressure of the equilibrium mixture is 1 atrn, the
2SO 3 (g) ~ 2SO 2 (g) + O 2 (g)
pa1tial pressure of 0 2 is [Manipall
The equilibrium constants are related as [KCET, WB JEE]
(a) 0.82atm (b) 0.52atm
(a)2K 1 = Ki (b)K 12 =_l_ (c) 0.2 l atm (d) 0.4latm
K2
27. 2HI (g) ~ H 2 (g )+I2 (g)
2
(d)K 2 = - The equilibrium constant of the above reaction is 6.4 at
K,1 300 K. If 0.25 mole each of H 2 and 12 are added to the
20. Final pressure is higher than initial pressure of a container system at same temperature, then the equilibrium constant
filled with an ideal gas at constant temperature. What will will be [Manipal]
be the value of equilibrium constant? [Guj CET] (a) 6.4 (b) 0.8
(a) K = 1.0 (b) K = 10.0 (c) K > 1.0 (d) K < 1.0 (c) 3.2 (d) 1.6
 Equilibrium I 159
28. For PC! 5 ~ PC! 3 + Cl 2 , initial concentration of each 2008
reactant and product is I M. If K eq = 0· 4 1then [Manipal] 37. For the following three reactions I, II and m, equilibrium
(a) more PCl 3 will fom, (b) more Cl 2 will form constants are given
( c) more PC! 5 will fom, (d) no change I. CO (g) + HzO (g) ~ CO 2(g)+ Hi(g),K 1
29. Which of the following is not a physical equilibrium? TT. CH4(g) + H2O(g) ~ CO (g) + 3H2(g),K2
( a) Ice ~ Water [UPSEE] ITT. CH4(g) + 2H2O (g) ~ COi(g) + 4H2(g),K3
(b)I2 (s) ~ I 2 (g) Which of the following relations is correct? [AIEEEJ
(c) S(/) ~ S(g) (a)K1 jK-; = K 3 (b)K 2 K 3 = K 1
(d) 302 ~ 203
(c)K 3 = K 1K 2 (d)K 3KJ = Ki2
30. For an equilibrium reaction, if the value of Kc>> 1, then
the reaction favoured more towards [OJEE] 38. The equilibrium constants K Pi and K Pi for the reactions
( a) backward X ~ 2Y and Z ~ P + Q, respectively are in
(b) forward the ratio of I : 9. If the degree of dissociation of X and Z
( c) equilibrium will be obtained be equal, then the ratio of total pressure at these
(d) reaction will stop equilibria is [AIEEEJ
31. If the value ofKc for an equilibrium reaction isl 0-4, then (a)l:36 (b) l: l
the reaction is in [OJEE] ( c) l : 3 (d) I : 9
(a) backward direction (b) forward direction 39. In a 500 mL flask, the degree of dissociation of PCl 5 at
(c) equilibrium (d) reaction is not possible equilibrium is 40% and the initial amount is 5 moles. The
32. For a reaction at equilibrium, which of the following is value of equilibrium constant (in mol L-1) for the
correct? [OJEE] decomposition of PCl 5 is [BITSAT, AMU, EAMCET]
(a) Concentration ofreactant = Concentration of product (a) 2.33 (b) 2 .66
(b) Concentration ofreactant is always greater than that (c) 5.32 (d) 4.66
of product 40. Formaldehyde polymerises to fom1 glucose according to
( c) Rate offorward reaction = Rate of backward reaction the reaction, 6HCHO ~ C6 H 12 O 6 .
(d) Qc = k The theoretically computed equilibrium constant for this
33. Which of the following is a wrong statement about 22
reaction is found to be 6 x 10 . If I M solution of glucose
equilibrium state? [lndraprastha CET, CGPET]
dissociates according to the above equilibrium, the
( a) Rate offorward reaction = Rate of backward reaction concentration of formaldehyde in the solution will be
(b) Equilibrium is dynamic
(a) l.6x 10-2 M (b) l.6x 10-4 M [Manipall
( c) Catalysts increase the value of equilibrium constant
(d) Free energy change is zero (c) 1.6 x 10- 6 M (d) 1.6 x 10-s M
34. A+B ~ C+D 41. 1n chemical equilibrium, the value of !!n (number of
1n the above reaction, initially moles of A and Bare equal. molecules of products - number of molecules of reactants),
At equilibrium, moles of C are three times that of A. The is negative, then the relationship between KP and Kc will
equilibrium constant of the reaction will be be [MPPET]
[lndraprastha CET, CG PET] (a)Kp - Kc = 0 (b)Kp = Kc(RTtt.ng
(a) I (b) 3 (c) 4 (d) 9 1
(c)Kp = Kc(RTft.n (d)Kp = K
35. IfforN2 +3H 2 ~ 2NH3 ,Keq = l.6x 10- 5 ,thenthe C

value of Keq for the reaction NH 3 ~ .!. N2 + ~ H2 42. Three moles of PC! 5 , three moles of PC! 3 and two moles
2 2 of Cl 2 are taken in a closed vessel. If at equilibrium, the
will be [Indraprastha CET, CG PET] vessel has 1.5 moles of PCl 5 , the number of moles of PCl 3
(a) 6.25 (b) 25 (c) 250 (d) 500 present in it is CKCETJ
36. 3 moles of A and 4 moles of B are mixed together and (a) 5 (b) 3 (c) 6 (d) 4 .5
allowed to come into equilibrium according to the 43. 2Hl (g) ~ H 2 (g) + 12 (g) - Q kJ
following reaction.
3A (g) + 4B (g) ~ 2C (g) + 3D (g) For the above reaction, equilibrium constant depends upon
When equilibrium is reached, there is I mole of C. The (a) temperature CKCETJ
equilibrium extent of the reaction is [DCEJ (b) pressure
( c) catalyst
(a) 1/ 4 (b) 1/3 (c) 1/2 (d) I
(d) volume
160 I Chapterwise & Topicwise Engineering Entrances Solved Papers
44. 1.6 moles of PC! 5 (g) is placed in 4 dm 3 closed vessel. 51. At 600° C,K P for the following reaction is 1 atm.
When the temperature is raised to 500 K, it decomposes X(g) ~ Y(g)+ Z(g)
and at equilibrium, 1.2 moles ofPCl 5 (g) remains. What is
At equilibrium, 50% of X ( g) is dissociated. The total
the Kc value for the decomposition of PC! 5 (g) into
pressure of the equilibrium system is p atm. What is the
PC! 3 (g) and Cl 2 (g) at 500 K ? [Kerala CEE]
partial pressure (in atm) of X (g) at equilibtium? [DCEJ
(a) 0.013 (b) 0.050 (c) 0.033 (d) 0.067
(a) 1 (b) 4 (c) 2 (d) 0.5
(e) 0.045
1 52. 4 moles each of SO2 and 0 2 gases are allowed to react to
45. CO (g) + - 0 2 ( g ) ~ CO2 (g) For the above fom1 SO3 in a closed vessel. At equilibrium, 25% of 0 2 is
2
used up. The total number of moles of all the gases at
reaction in gaseous phase, the value ofKP I Kc is equilibriun1 is [Jamia Millia Islamia]
112 112
(a) (RT) {b) (RT)- [UPSEE] (a) 6.5 (b) 7.0 (c) 8.0 (d) 2.0
(c) (RT) (d) (RT)-t
2007
46. Ammonium carbonate decomposes as
53. For an equilibriun1 reaction, N 2 O 4 (g) ~ 2NO2 (g ),
NH 2 COONH4 (s) ~ 2 NH 3 (g) + CO2 (g) the concentrations of N 2 0 4 and NO2 at equilibrium are
For the reaction, KP = 2 .9 x 10-5 atm 3 . If we start with 4.8 x 10- 2 and 1.2 x 10- 2 mol/L, respectively. The value
1 mole of the compound, the total pressure at equilibrium
ofKc for the reaction is [AIEEE, MP PET]
would be [AMU, EAMCET]
(a) 3 x 10- 3 mol/L (b) 3.3 x 10-3 mol/L
(a) 0.766 atm (b) 0.0581 atm (c) 3 x 10- 1 mol/L (d) 3.3 x 10-1 mol/L
(c) 0.0388 atm (d) 0.0194 atm
47. The equilibrium constant (KP) for the decomposition of 54. Equivalent amounts of H 2 and 12 are heated in a closed
gaseous H2 0 as vessel till equilibrium is obtained. If 80% of the hydrogen
can be converted to HI, the valve ofKc at this temperature
H 2 O(g) ~ H 2 (g) +_!_ O 2 (g)
is [VITEEE]
2
is related to degree of dissociation (a) at a total pressure p (a) 64 (b) 16
is given by [Guj CET] (c) 0.25 (d) 4
a3 p112 55. For the reaction H2 (g) + 12 (g) ~ 2 HI (g ), the
(a)Kp = - - - - -
(1 + a) (2 + a)1
12 equilibriun1 constant KP changes with [VITEEEJ
a3 P312 (a) total pressure (b) catalyst
( c) the amount of HI and 12 ( d) temperature
(b)Kp = (1 - a)(2+a)112
56. A + B ~ C + D. If initially the concentration of both A
a312P2
(c)K = - - - - - and B are both equal but at equilibrium, concentration of D
P
2
{l - a){2 + a)1' will be twice of that of A, then what will be the equilibrium
a312 p1 12 constant of reaction? [Manipall
(d)K - - - - - - 4 1
P - (1 - a)(2+ a) 112 (a) - (b) 2_ (c) - (d) 4
9 4 9
48. In the reaction, H 2 ( g) + Cl 2 (g) ~ 2HC1 (g ),
57. The equilibrium constant for the reaction.
(a) K p * Kc (b) K p =Kc [J&K CET]
2NO 2 (g) ~ 2NO(g) + O 2 (g)is2xl0- 6 at 185°C
(c)Kp>Kc (d)Kp<Kc
Then the equilibrium constant for the reaction,
49. 1 mole of H 2 and 2 moles of 12 are taken initially in a 2 L
4NO(g) + 2O2 (g) ~ 4NO 2 (g) at the same
vessel. The number of moles of H2 at equilibrium is 0.2.
temperature would be [Kerala CEE]
Then, the number of moles of 12 and HI at equilibrium
respectively are [BCECEJ (a) 2.5 X 10-5 (b) 4 X 10- 12 (c) 2.5 X 1011
(a) 1.2, 1.6 (b) 1.8, 1.0 (d)2xl06 (e)5xl0 5
(c) 0.4, 2.4 (d) 0.8, 2 .0 58. A liquid is in equilibriun1 with its vapour at its boiling
50. On doubling p and V with constant temperature, the point. On the average, the molecules in two phases have
equilibrium constant will [BCECE] equal [WB JEE]

(a) remain constant (a) intermolecular forces

(b) become double (b) potential energy
(c) become one-fourth ( c) kinetic energy
( d) None of the above ( d) total energy
 Equilibrium I 161
59. In the reaction 3A + 2B ~ 2C, the equilibrium 66. For the reaction H 2 + 12 :.====! 2HI, the equilibrium
constant Kc is given by [WB JEE] concentration ofH 2 , 12 and Hl are 8.0, 3.0 and 28.0 mol/L,
3 respectively. The equilibrium constant is [BCECE]
(a)[3A]x[2B] (b)[A] x[B]
[C] [C] (a) 28.34 (b) 32.66 (c) 34.78 (d) 38.88
2
(c) [C] ' (d) [C] 2006
[A] 3 x [BJ- [3A][2B] 67. Ag + + NH 3 :.====! [Ag (NH3 )t ,K1 = 3.5 x 10- 3
60. N 2 and H 2 in l : 3 molar ratio are heated in a closed [Ag(NH 3 )t + NH 3 :.====![Ag(NH3 )it,
container having a catalyst. When the following K2 = l.7x 10- 3
equilibrium, N 2 (g) + 3H2 ( g) :.====! 2NH3 (g) is
attained, the total pressure is l O atm and mole fraction of Then the formation constant of[Ag(NH3 )z t is
6
NH3 is 0.60. The equilibrium constantK P for dissociation (a)6.08xl0- (b)6.08Xl0 6 [IIT
ofNH3 is [WB JEE] JEE]
2 2 9
(a) l.333atn1- (b) 0.75 atm (c)6.08x10- (d) None of these
2 2
(c) 0.75 atn1- (d) 1.333 atm 68. Phosphorus pentachloride dissociates as follows, in a
61. P4 (s) + 5O2 (g) :.====! P4 O 10 (s) closed reaction vessel,
What is the equilibrium expression for the above PCl 5 (g) :.====! PCl 3 (g)+Cl 2 (g)
reaction? [UPSEE] If total pressure at equilibrium of the reaction mixture is p
and degree of dissociation of PC! 5 is x, then the partial
(b) Kc = [P4010] pressure of PC13 will be [AIEEEJ
5[P4 ][02 ]
l (a) ( ~ ) p (b)(~)P (c)(~ ) P (d)(~ ) P
(d)Kc = - - x+J 1- x x- 1 1- x
[02 ]5
62. CO(g) + 0.50 2 (g) ~ CO 2 (g) 69. SO3 (g) :.====! SO2 (g) + _! 0 2 ( g)
2
For the above reaction KP I Kc is equal to [OJEE] The equilibrium constant for the above reaction is
Kc = 4.9 x 10-2 . The value of Kc for the reaction
(a) .Jiff (b) ~ (c) l (d) RT 2
vRT 2SO 2 (g) + 0 2 (g) :.====! 2SO3 (g) will be [AIEEEJ
63. Consider th e reactions (a) 416 (b) 2.40x 10-3
NO2 :.====! _!_ N 2 + O 2 ,K1 andN 2O 4 :.====! 2NO2 ,K2 (c)9.8x10- 2 (d)4.9x10- 2
2
70. l mole ofN2 O 4 (g )at 300 Kis kept in a closed container
Give the equilibrium constant for the fom1ation ofN2 O 4 under 1 atm. It is heated to 600 K when 20% by mass of
from N 2 and 0 2 . [AMU]
N 2O 4 (g ) decomposes to NO 2 (g ). The resultant pressure
(a) - 1- x _ l_ (b) - 1- (c) ✓ l (d) K2 is [BITSATJ
K~ K 2 K 1K 2 K 1K 2 K1 (a) 1.2 atn1 (b) 2.4 atm (c) 2.0 atm (d) 1.0 atm
64. The equilibrium constant for the reaction, 71. N 2 + 0 2 :.====! 2NO + Heat
In the above gaseous reversible reaction, if pressure is
SO2 (g) + _!_ 0 2 (g) :.====! SO3 (g) is 5 x 10- 2 atm. The
2 increased, then the equilibrium constant would be
equilibrium constant of the reaction (a) unchanged [ManipalJ
2SO3 (g) :.====! 2SO2 (g) + 0 2 (g) would be [EAMCET] (b) increased
(a) 100 atm (b) 200 atm (c) decreased
2 4
(c) 4 x 10 atn1 (d) 6.25 x 10 atm (d) sometimes increased, sometimes decreased
65. By applying law of mass action, the equilibrium constant K 72. Consider the following equilibrium in a closed container,
for the reaction [J& K CET] N 2 O 4 (g) :.====! 2NO2 (g)
At a fixed temperature, the volume of the reaction
HA + H 2O :.====! H 30 + +A-, is given as
container is halved. For this change, which of the following
(a)K= [HA][H2 O] (b)K=[H 3O+][A- ] statement holds true regarding the equilibrium constant
[H3O+ ][A - ] [HAHH2O] (KP) and degree of dissociation (CJ.)? [MHT CETJ

(c)K = [H3O+] [H 2 O] (d)K = [HA][A-] (a) Neither KP nor CJ. changes

[A- ][HA] [H 2 O] [H 3 O+] (b) Both KP and CJ. change
(c) KP changes but CJ. does not
162 I Chapterwise & Topicwise Engineering Entrances Solved Papers
(d) KP does not change but a changes 81. At a given temperature, the equilibrium constant for the
73. The equilibrium constant of a reaction is 300. If the reaction of
volume of reaction flask is tripled, then the equilibriurn PC1 5 ~ PC1 3 + Cl 2 is 2.4 x 10- 3 . At the same
constant is [MHT CET] temperature, the equilibrium constant for the reaction
(a) 300 (b) 600 (c) 900 (d) 100 PC1 3 (g) + Cl 2 (g) ~ PC1 5 (g)is
74. In the reaction, H 2 + 12 ~ 2HI [Jamia Millia Islamia]

In a 2 L flask, 0.4 mole of each H 2 and 12 are taken. At (a) 2.4 X 10-3 (b) - 2.4 x 10-3
equilibrium, 0.5 moles of HI are formed. What will be the (c) 4.2x 102 (d) 4.8 x 10-2
value of equilibtium constant Kc? [WB JEE]
82. Which of the following is correct for the reaction ?
(a) 20.2 (b) 25.4 N2 (g)+3H 2 (g) ~ 2NH3 (g)
(c)0.284 {d) 11.1 1
(a) KP = Kc [Jamia Millia Islamia]
75. Two moles of PCl 5 were heated in a closed vessel of 2 L.
(b)Kp<Kc
At equilibriurn, 40% ofpCl 5 is dissociated into PCl 3 and
(c)Kp>Kc
Cl 2 . The value of equilib1ium constant is [UPSEE]
(d) Pressure is required to predict the correlation
(a) 0.53 (b) 0.267
(c) 2.63 (d) 5.3 2005
76. The chemical equilibrium of a reversible reaction is not 83. For the reaction, [AIEEEJ
influenced by [AMU]
2NO 2 (g) ~ 2NO(g)+ O 2 (g)
(a) pressure (Kc = 1.8 x 10---Q at 184° C)
(b) catalyst
(c) concentration of the reactants (R = 0. 00831 kJ/mol K)
(d) temperature When KP and Kc are compared at 184° C, it is found that
77. 56 g of nitrogen and 8 g of hydrogen gas are heated in a (a) whether KP is greater than, less than or equal to Kc
closed vessel. At equilibrium, 34 g ofammonia are present. depends upon the total gas pressure
The equilibtium number of moles of nitrogen, hydrogen (b)Kp = Kc
and ammonia respectively are [AMU] (c) KP is less than Kc
(a)l,2,2 (b)2,2,1 (c)l,1,2 (d)2,1,2 (d) KP is greater than Kc
78. Which of the following is not a characteristic property of 84. An amount of solid NH4 HS is placed in a flask already
chemical equilibrium ? [EAMCET] containing ammonia gas at a certain temperature and
(a) Rate of forward reaction is equal to rate of backward 0.50 atrn pressure. Ammonium hydrogen sulphide
reaction at equilibriurn decomposes to yield NH 3 and H 2 S gases in the flask.
(b) After reaching the chemical equilibrium, the When the decomposition reaction reaches equilibrium,
concentrations of reactants and products remain the total pressure in the flask rises to 0.84 atm. The
unchanged with time equilibrium constant for NH4 HS decomposition at this
(c) For A (g) ~ B (g),Kc is 10-2 . If this reaction is temperature is [AIEEEJ
carried out in the presence of catalyst, the value of (a)0.11 (b)0.17 (c)0.18 (d)0.30
Kc decreases 85. In which of the following reactions is K P < K c ?
(d) After reaching the equilibrium, both forward and
(a) 12 (g) ~ 2l{g) [BITSAT]
backward reactions continue to take place
79. A monoprotic weak acid (HA) is ionised 5% in 0.1 M (b) 2BrCl(g) ~ Cl 2 (g) + Br2 (g)
(c) CO(g) + 3H2 (g) ~ CH 4 (g) + H 2 O(g)
aqueous solution. What is the equilibrium constant for its
(d) All of the above
ionisation ? [Guj CET]
HA(aq)+ H 2 0(/) ~ H 3 0+ (aq)+ A - (aq) 86. The change in pressure will not affect the equilibrium
4 3 constant for CBITSATJ
(a) 2.63 x 10 (b) 2.63 x 10
(a) N 2 + 3H2 ~ 2NH3 (b) PC1 5 ~ PC1 3 + Cl 2
(c)2.63xl0--4 (d)2.63xl0-3
(c) H2 + 12 ~ 2HI (d) All of these
80. The equilibrium reaction that is not influenced by volume 87. For a reaction H2 + 12 ~ 2HI at 721K, the value of
change at constant temperature is [J&K CET]
equilibriwn constant is 50. If0.5 mole each of H2 and 12 is
(a) H 2 (g)+ 12 (g) ~ 2HI (g) added to the system, then the value of equilibrium constant
(b)N2 (g) + 3H2 (g) ~ 2NH3 (g) will be [Manipal]
(c)N 2 O4 (g) ~ 2NO 2 (g) (a) 40 (b) 60 (c) 50 (d) 30
(d) 2NO(g)+ O 2 (g) ~ 2NO2 (g)
 Equilibrium I 163
88. 15 moles ofH 2 and 5.2 moles ofJ 2 are mixed and allowed 93. 2 moles of PCI 5 is heated in a closed vessel of2 L capacity.
to attain equilibrium at 500°C. At equilibrium, the When the equilibrium is attained 40% of it has been found to
concentration of HI is found to be 10 moles. The be dissociated. What is the value (in mol/dm 3 ) of Kc ?
equilibrium constant for the fo1mation of HI is [KCET] (a) 0.532 (b) 0.266 (c) 0.133 [Kerala CEE]
(a)50 (b)15 (d)0.174 (e)0.25
(c) 100 (d) 25
94. For the reaction,
89. If in the reaction N 2 0 4 ~ 2 NO 2 , x is that part of
H 2 (g) + CO 2 (g) ~ CO(g) + H 2 O(g), if the
N 2 O 4 which dissociates, then the number of molecules at initial concentration of [H2 ] = [CO 2 ] and x mol/L of
equilibrium will be [KCET] hydrogen is consumed at equilibrium, the con-ect
(a) l (b)3 (c) l +x (d)( l+ x)2 expression of KP is [OJEEJ
2 (1 )2 2 2
90. The rate at which a substance reacts depends on its [KCETJ (a) x 2 (b) +x 2 (c) x (d) ~
2
(a) atomic weight (b) atomic number (1 - x) (1 - x) (2+x) 1- x
(c) molecular weight (d) active mass 95. At 550 K, the value of Kc for the following reaction is
91. For the reaction, 4
10 mol- L
1
X(g)+ Y(g) ~ Z(g)
N 2 (g) + 0 2 (g) ~ 2NO(g ), the value of Kc at
800°C is 0.1. When the equilibrium concentration of both At equilibrium, it was observed that
the reactants is 0.5 mole, what is the value of KP at the [X] =_!. [Y] =_!.[Z]
same temperature ? [KCET] 2 2
(a) 0.5 (b) 0.1 (c) 0.01 (d) 0.025 What is the value (in mol L- 1) of [Z] at equilibrium?
92. A (g) + 3B (g) ~ 4C (g) (a) 2x 10-4 (b) 10-
4
[EAMCETJ

Initially, concentration of A is equal to that of B. The (c) 2x 104 (d) 104

equilibrium concentrations of A and C are equal. Kc is 96. 2Ag 2 O(s) ~ 4Ag (s)+O 2 (g)
equal to Partial pressure of 0 2 in the above reaction is [DCEJ
(a) 0.08 (b) 0.8 (c) 8 [Kerala CEE]
(d) 80 (e)l/8
(b) ,JK; (c) 3..jK; (d) 2K P

Topic 2
Factors Affecting Equilibria (Le-Chatel ier's Principle)
2014
1. In the reaction at constant volume (c) K is dependent on the pressure of CO 2 at given T
C(s) + CO 2 (g) ~ 2CO(g) (d) Aff is independent of the catalyst, if any
Argon gas is added which does not take part in the reaction, 3. In which of the following equilibrium systems, is the rate
choose the correct statement. [AMUJ of the backward reaction favoured by increase of
(a) The equilibrium constant is unchanged pressure? [KCETJ
(b) The equilibrium shifts in the forward direction (a) PC l 5 ~ PCI 3 + Cl 2
(c) The equilibrium shifts in the backward direction (b) 2SO2 + 0 2 ~ 2SO3
(d) The direction of equilibrium depends on the amount (c) N 2 + 3H 2 ~ 2NH3
of argon added (d)N2 + 0 2 ~ 2NO
4. In the lime kiln, the reaction [Kerala CEE]
2013
2. The thermal dissociation of equilibrium of CaCO3 (s) is CaCO3 (s) ~ CaO(s) + CO2 (g) goes to completion
because
studied under different conditions. [JEE Advanced] (a) of high temperature
CaCO3 (s) ~ CaO(s)+ CO2 (g) (b) CaO is more stable than CaCO3
For this equilibrium, the correct statement (s) is (are) (c) CO 2 escapes simultaneously
(a) Aff is dependent on T (d) Cao is not dissociated
(b) K is independent of the initial amount of CaCO3 (e) CO 2 is a gaseous product
164 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2012 2007
5. In a reversible chemical reaction at equilibriwn if the 13. Given the equilib1ium system
concentration of any one of the reactants is doubled, then NH4 CI(s) ~ NH; (aq) + Cl - (aq)
the equilibrium constant will [WB JEE]
(Mi = + 3.5 kcal/mo!)
(a) also be doubled (b) be halved What change will shift the equilibrium to the right?
(c) remain the same (d) become one-fourth (a) Decreasing the temperature [VITEEE]
(b) Increasing the temperature
2010 (c) Dissolving NaCl crystals in the equilibrium mixture
6. N 2 (g) + 3H2 (g) ~ 2NH 3 (g) (d) Dissolving NH4 N0 3 crystals in theequilibriurnmixture
In the reaction given above, the addition ofsmall amount of 14. Consider the reaction equilibrium,
an inert gas at constant pressure will shift the equilibrium 2S02 (g) + 02 (g) ~ 2S03 (g ); Af1° = - 198 kJ
towards which side? [MP PET]
On the basis of Le-Chatelier's principle, the condition
(a) LHS (Left Hand Side) (b) RHS (Right Hand Side) favourable for the forward reaction is [MP PET]
( c) Neither side (d) E ither side
(a) lowering of temperature as well as pressure
2009 (b) increasing temperature as well as pressure
( c) lowering the temperature and increasing the pressure
7. 2S02 + 0 2 ~ 2S0 3 + Heat.
( d) any value of temperature and pressure
The equilibrium reaction given above proceeds in forward
15. For the chemical reaction
direction by [OJEE]
3X(g)+ Y(g) ~ X 3 Y(g), the amount of X 3 Yat
(a) addition of0 2 (b) removal of0 2 equilibrium is affected by [WB JEE]
( c) addition of inert gas (d) cannot proceed
(a) temperature and pressure
2008 (b) temperature only
(c) pressure only
8. According to Le-Chatelier's principle, the addition of (d) temperature, pressure and catalyst
temperature to the following reaction [MP PET]
16. According to Le-Chatelier's principle, adding heat of a
CO 2 (g) + 2H 20(g) ~ CH4 (g) + 202 (g) solid and liquid in equilibrium will cause the CWB JEE]
will cause it to the right. This reaction is, therefore (a) amount of solid to decrease
(a) exothermic (b) unimolecular (b) amount of liquid to decrease
(c) endothermic (d) spontaneous ( c) temperature to rise
9. N 2 + 3H2 ~ 2NH3 + Heat. What is the effect of the ( d) temperature to fall
increasing oftemperature on the equilibrium ofthe reaction?
2006
(a) Equilibrium is shifted to the left [KCETJ
17. For the reaction,
(b) Equilibriun1 is shifted to the right
(c) Equilibrium is unaltered N 2 (g)+ 3H2 (g) ~ 2NH3 (g);
(d) Reaction rate does not change t::,.H = - 93.6 kJ mo1-1 , the concentration ofNH3
10. Formation ofS03 from S02 and 0 2 is favoured by at equilibrium can be increased by
(a) increase in pressure [OJEE]
I. lowering the temperan1re
TI. low pressure
(b) decrease in pressure
ITT. excess ofN2
( c) increase in temperature
IV. excess ofH 2
( d) decrease in temperature
The con-ect is/are [Kerala CEE]
11. What happens to the yield on application of high pressure
(a) II and IV (b) Only II
in the Haber's synthesis of ammonia? [J&K CET]
(c) I, II and III ( d) III and IV
( a) Increases (b) Decreases (e) I, III and IV
(c) Unaffected (d) Reaction stops
18. In the manufacturing of ammonia by Haber's process,
12. When hydrogen molecules decomposed into its atoms, N 2 (g) + 3H2 ~ 2NH3 (g)+92.3kJ
which condition gives maxinmm yield ofH-atom?
Which of the following condition is unfavourable? [AMU]
(a) High temperature and low pressure [BCECE]
(a) Increasing the temperature
(b) Low temperature and high pressw·e (b) Increasing the pressure
(c) High temperature and high pressure
( c) Reducing the temperature
( d) Low temperature and low pressure
(d) R emoving ammonia as it is formed
 Equilibrium I 165
2005 21. For the gaseous reaction, C 2 H 4 + H 2 ~ C 2 H 6 ;
1
19. The exothem1ic formation ofCIF3 is represented by the !-,JI = - 130 kJ mol- carried in a closed vessel, the equilibrium
concentration of C2 H 6 can definitely be increased by
equation
(a) increasing temperature and decreasing pressure [UPSEEJ
CI 2 (g) + 3F2 (g) ~ 2CIF3 (g );
!-,.H =- 329kJ
(b) decreasing temperature and increasing pressure
( c) increasing temperature and pressure both
Which of the following will increase the quantity of
(d) decreasing temperature and pressure both
CIF3 in an equilibriwn mixture of CI 2 , F2 and CIF3 ?
22. In a lime kiln, to get higher yield of CO2 , the measure that can
(a) Adding F2 [AIEEEJ
be taken is [RPETJ
(b) Increasing the volume of the container
(a) to remove CaO
( c) Removing Cl 2
( d) Increasing the temperatw·e (b) to add more CaCO 3
( c) to maintain high temperature
20. The gaseous reaction, [MPPE TJ
( d) to pump out CO 2
23. If pressure increases then its effect on given equilibrium
A +B ~ 2C + D+Q is most favoured at
(a) low temperature and high pressure 2NO(g) ~ N 2 (g)+O2 (g) is shift in CBCECEJ
(b) high temperature and high pressure (a) forward direction (b) backward direction
(c) high temperature and low pressure ( c) no effect ( d) None of the above
( d) low temperature and low pressure

Topi c 3
Degree of Dissociation, Acids and Bases
2014 2012
1. Which one of the following is the weakest acid? 6. In Lowry-Bronsted concept, H + donor is known as
(a) HF (b) HCl [ManipaIJ (a) acid (b) base [OJEEJ
(c) HBr (d) HI (c) Both (a) and (b) (d) None of these
2. Strongest conjugate base is [Manipal] 7. Which of the following acid is stronger than benzoic acid
(a) CIO- (b) ClO2 (c) ClO3 (d) Cl04 (K 8 = 6.3 X 10- 5 )? [AMUJ

3. Which of the following is the strongest base? (a) A (Ka = 1.67x 10- s)
[Manipal] (b) B (pKa = 6.0)
(c) C (pKa = 4.0)
(a)
Q (b)
0N
(d)D(K 0 =I.Oxl0- 5 )
8. For a diprotic acid, which of the following is true for 1st and
I 2nd ionisation constants (Ka I and K 02 )? [AMUJ
H (a)Ka1 =Ka2 (b)Kai >Ka2

0 0
(c)Ka2 >Kai (d) Ka2 ~Kai
(c) (d)
N 2011
I 9. What is the best description of the change that occurs when
H
Na 2 O(s) is dissolved in water? [AIEEEJ

2013 (a) Oxidation number of sodium decreases

(b) Oxide ion accepts sharing in a pair of electrons
4. What kind of molecule A1Cl 3 is? [OJEEJ ( c) Oxide ion donates a pair of electrons
(a) Bronsted acid (b) Lewis acid (d) Oxidation nwnber of oxygen increases
( c) Lewis base (d) Bronsted base 10. A weak monobasic acid is 1% ionised in O.1 M solution at
5. Which is a Lewis base? [OJEEJ 2S'C. The percentage of ionisation in its O. 025 M solution is
(a) B 2 H 6 (b) LiA1H 4 (a) 1 (b) 2 (c) 3 [Keral a CEE]
(c) A1H 3 (d) N H 3 (d) 4 (e) 5
166 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2010
11. Three reactions involving H 2 PO4 are given below 20. Which one of the following species acts as both Bronsted
I. H 3P04 + Hp ~ H 30+ + H 2P04 acid and base ? [MHT CET]
II. H 2P04 + H 20 ~ HPO~- + H30+ (a) H 2 PO2 (b) HPO; -
III. H 2P04 + OW ~ H 3P04 + 0 2- (c) HPO~ - (d) All of these
In which of the above does H 2 PO4 act as an acid? 21. Which of the following is a Lewis acid ? [MPPET]
(a) Only II (b) Both I and II [AIEEEJ (a) Cl- (b) H3 0 +
(c) Only III (d) Only I (c) PF3 (d) C 2 H 5 OH
12. Which is Lewis acid? [Manipal] 22. Amines behave as [KCET]
(d) H 2 O (a) Lewis acid (b) Lewis base
(c) aprotic acid (d) neutral compound
2009 23. For a concentrated solution ofa weak electrolyte AxBY of
13. At a certain temperature, the dissociation constants of concentration C, the degree of dissociation 'a.' is given as
4
formic acid and acetic acid are l.8xl0- and l.8x l0- 5 ,
[Kerala CEE]
respectively. The concentration of acetic acid solution in (a)a = .JKeq /C(x + y)
which the hydrogen ion has the same concentration as in (b) a = .JKeqCl (xy)
0.001 M fomlic acid solution is equal to [Kerala CEE]
(c) (1., = (Keq l ex+ y - l x-' y Y )1'(x + y)
(a) 0. 01M (b) 0. 001 M
(c) O. lM (d) 0. 0001M (d) a = (Keq / Cxy)
(e) 0.1010M (e) a = (Keq /CXY)
14. Diacidic base is [UPSEE]
24. Conjugate acid ofHF2 is
(a) CH2 (OH)i (b) Ca(OH)i (a) H+ (b) HF (c) F2
(c) CH3 CH(OH)i (d) All of these
15. Which of the following behaves as Lewis acid and not as 2007
Bronsted acid? [UPSEEJ
25. The first and second dissociation constants of an acid H 2A
(a) HCl (b) H 2 SO 4 (c) HSO3 (d) SO3 are 1. 0 x 10- 5 and 5. 0 x 10- 10 , respectively. The overall
16. Water is well known amphoprotic solvent. In which dissociation constant of the acid will be [AIEEEJ
chemical reaction, water is behaving as a base ? [UPSEEJ (a) 5.0x 10- 5 (b) 5.0x 10 15
(a) H 2 SO 4 + H 2 O ~ H 3 O+ + HSO 4 (c)S.0xI0- 15 (d)0.2xl05
(b) H 2 O + H 2 O ~ H 3 O+ + OH- 26. Conjugate base ofH 2 PO4 is
(c) H 2O + NH2 ~ NH 3 + OH- [BITSAT, Jamia Millia Islamia]
(d) H 2 O + NH 3 ~ NH:+ OH- (a) H 3 PO4 (b) P2 O 5 (c) PO~- (d) HPOi-
17. Which of the following is the weakest acid? [UPSEEJ 27. Which one of the following substances has the highest
(a) HCl (b) HF (c) H 2 SO 4 (d) HNO 3 proton affinity ? [MP PET]

18. According to hard and soft acid-base principle, a hard acid (a) H 2 O (b) H 2S (c) NH 3 (d) PH 3
(a) has low charge density [DCEJ 28. Which of the following is not a conjugate acid-base
pair? [EAMCET]
(b) shows preference for soft bases
(c) shows preference for donor atoms of low (a) HPO~-, PO~- (b) H2PO;j, HPoi-
electronegativity (c) H 3 PO 4 , H 2 PO4 (d) H 2PO4, P0~-
(d) is not polarisable
29. According to Bronsted and Lowry , the strength of an acid
2008 depends upon [J&K CETJ
19. Four species are listed below (a) the tendency to gain electrons
I. HC03 II. Hp+ (b) the tendency to loss protons
(c) the tendency to accept protons
III. Hso:; IV. HS03F
( d) the tendency to loss electrons
Which one of the following is the co1Tect sequence of their
30. The ionisation of strong electrolytes in acetic acid,
acid strength ? [AIEEEJ
compared to water, is [J&K CET]
(a) IV < II < III < I (b) II < III < I < IV
(a) weak, low (b) strong, more
(c) I < III < II < IV (d)III < I < IV < II
(c) medium, the same ( d) no ionisation, 100%
 Equilibrium I 167
31. An acid solution of 0.005 M has a pH of 5. The degree of 42. Which of the following is not a Lewis base ?
ionisation of acid is [BCECE] [Jamia Millia Islamia]
(a) 0.1 x 10-2 (b) 0.2 x 10-2 (c) 0.5 x 10--4 (d) 0.6 x 10~ (a) NH 3 (b) H 2 0
(c) A1Cl 3 (d) None of these
2006
32. An example of a Lewis acid is [Manipal]
2005
43. What is the conjugate base of OH- ? [AIEEE]
(a) MgC1 2 (b) SnC1 4 (c) AIC1 3 (d) NaCl
(a) 0 2- (b) o- (c) H 2 0 (d) 0 2
33. Conjugate acid of S 2 o~- is [MHTCET]
44. The values of dissociation constant of bases are given
(a) H 2 S 2 O 8 (b) H 2 SO 4 (c) HS 2 O8 (d) Hso:; below. Which is the weakest base? [MHT CETJ
34. CH 3 COOH is weaker acid than H 2 SO4 . It is due to (a) 1.8 X 10-5 (b) 4.8 X 10-IO
(a) more ionisation (b) less ionisation [WB JEE] (c) 7.2x 10- 11 (d) 7.07x 10-7
(c) covalent bond (d) electrovalent bond
45. The species among the following, which can act as an acid
3 5. Which of the following is a Lewis base ? [WB JEE]
and a base is [KCETJ
(a) NaOH (b) NH 3
(b) so~-
(c) BCI 3 (d) All of these
(d) Cl-
36. Which one of the following is not an amphoteric
substance ? [AMU] 46. Which molecule is an electron donor? [OJEE]
(a) HNO 3 (b) HCO3 (c) H 2 O (d) NH 3 (a) NH 3 (b) BF3
37. The conjugate acid ofNH 2 is (c) PF5 (d) AsF5
[Guj CET]
47. Which of these is a Lewis acid? [OJEEJ
(c) NH2 OH (d) NH 3
(a) AICl 3 (b) NC13
38. Ostwald's dilution law is applicable for [Guj CET] (c) HCl (d) ROR
(a) weak electrolyte 48. Among BMe3 , BF3 , BC1 3 and B2 H 6 , which one will be
(b) strong electrolyte
the best Lewis acid ? [UPSEEJ
(c) both weak and strong electrolyte
(d) non-electrolyte (a) BC13 (b) BMe3
(c) B2 H 6 (d) BF3
39. Which of the following is a Lewis acid?
49. Which of the following is not a Lewis acid ? [J &K CETJ
(a) AIC1 3 (b) Cl- (c) CO
(a) BF3 (b) AIC1 3 (c) SO2 (d) H 2 O
40. Ammge NH; , H 2 O, H 3 0 +, HF and Off in increasing
50. Which is a Lewis base? [BCECE]
order of acidic nature [BCECE]
(a) H 3 O+ < NH: < HF < OH- < H 2 O 12 +1 ~ 13
(b) NH!< HF< H 3 O + < H 2 O < OH- (b)I3
(c) Off < H 2 O <NH: < HF < H 3 O+ (d) None of these
2
(d) H 3 O+ > HF > H 2 O >NH:> Off 51. Metal ions like Ag+, Cu + etc., act as
(a) Bronsted acids [Jamia Millia Islamia]
41. A monoprotic acid in 1.00 M solution is 0.01% ionised. (b) Bronsted bases
The dissociation constant of this acid is [BCECE] (c) Lewis acids
(a) 1 x 10-8 (b) Ix 10--4 (c) Ix 10~ (d) Ix 10-5 (d) Lewis bases
 Topic 4
pH Value and Related Terms
2014
1. If200 mL ofa 0.031 molar solution of H 2 S0 4 are added 12. The pH of the solution obtained by mixing 100 mL of a
to 84 mLofa0. 150 M KOH solution, what is the value of solution of pH = 3 with 400 mL of a solution of pH = 4, is
pH of the resulting solution? [Manip al] (a) 7 - log 2 .8 (b) 4 - log 2.8 [KCETJ
(a) 12.4 (b) 1.7 (c) 2.2 (d) 10.9 (c) 5 - log 2 .8 (d) 3 - log 2.8
4 4
2. The pH ofl 0- M KOH solution will be [WB JEE] 13. A solution [H 3 o+] is 10- . The solution is [OJEEJ
(a) 4 (b) 11 (c) 10.5 (d) 10 (a) acidic (b) basic
3. What will be the pH of a solution formed by mixing 10 mL ( c) neutral ( d) amphoteric
N
of0.l M H 2 S04 and 10 mL of- KOH? [AMU] 2011
IO
14. An acid HA ionises as, HA ~ H+ +A _
(a) 11.40 (b) 8.64 (c) 1.00 (d) 7 .00
The pH of 1.0 M solution is 5. Its dissociation constant
4. How much is the pH of human blood? [J&KCET]
would be [AIEEEJ
(a) 5.2 (b) 8.3 (c) 6.3 (d) 7.4 10 8 5
(a)Ix10- (b)0.5 (c)5xI0- (d)lxI0-
5. The concentration of hydrogen ion in a sample of soft drink
is 3.8 x 1o- 3 M. What is its pH? [J&K CET]
15. 0.023 g of sodium metal is reacted with 100cm3 of water.
The pH of the resulting solution is [KCETJ
(a)3.84 (b)2.42 (c)4.44 (d)l.42
(a) 10 (b) 11 (c) 9 (d) 12
2013 16. pH value of which one of the following is not equal to
6. How many litres of water must be added to 1 L of an one? CKCETJ
aqueous solution of HCI with a pH of 1 to create an (a) 0.lM HN03
aqueous solution with pH of 2? [JEE Mains] (b) 0.05 M H 2 S04
(a)O.l L (b)0.9L (c) 0. lM CH 3 COOH
(c) 2.0 L (d) 9 .0 L (d) 50cm3 of0.4 M HCl + 50cm3 of0.2 M NaOH
7. By adding 20 mL of0. l N HCI to 20 mL of0.001 N KOH,
the pH of the obtained solution will be [KCET]
2010
17. The pH ofl 0- 10 M NaOH solution is nearest to
(a) 2 (b) 1.3 (c) 0 (d) 7
(a) - 4 (b) - 10 [Manipal]
2012 (c) 4 (d) 7
8. The pH of a 0.1 molar solution of the acid HQ is 3. The 18. The pH of a neutral water sample is 6 . 5. Then, the
value of the ionisation constant, Ka of the acid is temperature of water [Manipal]
(a) 3 X 10- 1 (b) 1 X 10- 3 [AIEEE] (a) is 25°C
5 7
(c) Ix 10- (d) Ix 10- (b) is more than 25°C
1
9. If Ka of HCN = 4 x 10- 10 , then the pH of 2.5 x 10- ( c) is less than 25°C
(d) can be more or less than 25°C
molar HCN ( aq) is [Manip al]
19. On mixing equal volumes of two buffer solutions of pH
(a) 1 (b) 2.5
(c) 4 (d) 5 value 3 and 5, the pH of the resultant solution will be

10. On adding which of the following, the pH of 20 mL of (a) 3.3 (b) 4.0 [MP PET]
(c) 4 .7 (d) 5.3
0.1 N HCl will not alter? [KCET]
(a) 20 mL of distilled water 20. The pH value of 0.00 l M aqueous solution of NaCl is
(b) I mL of0. l N NaOH (a) 7 (b) 4 [RPET]
(c) 500 mL ofHCl of pH = 1 ( c) 11 ( d) unpredictable
(d) l mLofl NHCI 21. A solution contains 10 mL of0.l N NaOH and 10 mL of
11. 5 mL of0.4 N NaOH is mixed with 20 mL of0.l N HCI. 0 .05 N H 2 S04 ,pH of this solution is [JCECEJ
The pH of the resulting solution will be [KCET] (a) less than 7 (b) 7
( c) zero ( d) greater than 7
007 ~8 ~5 006
 Equilibrium I 169
2009
M M M 32. pH ofa 0.0001 M HCI solution is [UPSEE]
22. 30 cc of- HCl, 20 cc of- HNO 3 and 40 cc of- NaOH
3 2 4 (a)4 .0 (b)2 .0
solutions are mixed and the volwne was made upto 1 dm 3 . (c) 6 .0 (d) 7 .0
The pH of the resulting solution is [Manipall
33. pH of an aqueous solution containing 10~ mol /L ofHCI is
008 ~2 ~l ~3
(a)8 (b)l0 [J&K CET]
23. 10- 6 M NaOH is diluted 100 times. The pH of the diluted (c) 6 .96 (d) 12
base is [Manipal]
34. Which of the following solutions will have pH = 9 at
(a) between 7 and 8 (b) between 5 and 6 298 K? [BCECE]
( c) between 6 and 7 (d) between 10 and 11
(a) 1 X 1o-9 M HCl solution
24. When 200 mL of aqueous solution of HCl (pH = 2) is
(b) 1 x 10-5 M NaOH solution
mixed with 300 mL of an aqueous solution of NaOH
(pH = 12) the pH of the resulting mixture is [Ke rala CEE] ( c) 1 X 1o-9 M KOH solution
(a) 10 (b) 2.7 (c) 4.0 (d) B oth (a) and (b)
(d) 11.3 (e) 2 35. 100 mL of0.015 M HCI solution is mixed with 100 mL of
25. An aqueous solution whose pH is zero will be called as 0.005 M HCI. What is the pH of the resultant solution?
(a) acidic (b) basic [AMU] (a) 2.5 (b) 1.5 [DCE]
(c) neutral (d) amphoteric (c) 2 (d) 1
8
26. The pH values of 0.1 M solution of HCl, CH 3 COOH, 3 6. The pH ofl 0- M HCl solution is [Jamia Millia Islamial
NH4 Cl and CH3 COONa will have the order (a) 8 (b) more than 8
[lndraprastha CET, CG PET] (c) between 6 and 7 (d) slightly more than 7
(a) HCI< CH3 COOH< NH4 Cl< CH3 COONa 2007
(b) CH 3 COONa< NH4 Cl< CH3 COOH < HCI
37. Hydroxyl ion concentration ofl 0-2 M HCl is [KCET]
(c) NH4 Cl< CH 3 COONa< CH3 COOH< HCI 1 3 12
(a) 1 x 10 mol dm- (b) 1 x 10- mol dm-3
( d) All will have same of pH value
(c) 1 x 10-1 mol dm-3 (d) 1 x 10-14 mol dm-3
27. A weak acid HX has dissociation constant l 0- 5 . The pH of
0.1 M solution ofthis acid will be 38. Calculate the pH of a solution in which hydrogen ion
[Indraprastha CET, CG PET] concentration is 0 .005 g-equi /L. [J&K CET]
(a) 2 (b)3 (c)4 (d)5 (a)2 .3 (b)2 .8 (c)2 .9 (d)2.6
28. Which of the following acids will have lowest value of 39. The approximately pH of0.005 molar sulphw·ic acid is
pK a? [lndraprastha CET, CG PET] (a) 0.005 (b) 2 [DCE]
(a) CH3 CH 2 COOH (b) CH3 CHCOOH (c) l (d) 0.01
I
Br 2006
(c) CH3 CHCOOH 40. Which solution has pH equal to 10? [Manipall
I 4
(a) 10- M KOH 10
(b) 10- M KOH
F
(c) 10-to M HCI (d) 10- 4 M HCl
2008 41. A 0.01 M ammonia solution is 5% ionised, its pH will be
29. 50 mL of H2 0 is added to 50 mL of 1 x 10-3 M barium (a)ll.80 (b) J0.69 [MHT CET]
hydroxide solution. What is the pH of the resulting (c) 7.22 (d) 12 .24
solution? [BITSAT, AMU, EAMCET]
42. 100 mL of0.01 M solution ofNaOH is diluted to l dm 3 .
(a)3.0 (b) 3.3 (c) 11.0 (d) 11.7
What is the pH of the diluted solution? [MP PET]
30. The pH of a 0.1 M solution ofNH4 OH (a) 12 (b) 11 (c) 2 (d) 3
(having Kb = 1.0 x 10-5 ) is equal to [MHTCET] 43. Calculate pOH of 0.001 M NH4 OH, when it is 1%
(a) l 0 (b)6 (c)ll (d) 12 dissociated in the solution. [MPPET]
31. The pH ofa solution obtained by mixing 50 mL of 1 N HCl (a) 5 (b) 2.96 (c) 9.04 (d) 11.4
and 30 mL of l N NaOH is (log 2.5 = 0.3979)
44. What will be the pH value of0.05M Ba (OHh solution?
(a)3.979 (b)0.602 1 (c)l2.042 [Ke ralaCEE]
(a) 12 (b) 13 [WB JEE]
(d) 1.2042 (e) 0.3979 (c) l (d) 12.96
170 I Chapterwise & Topicwise Engineering Entrances Solved Papers
45. The pH value of 1/1000 N KOH solution is [UPSEEI 50. Which of the following has highest pH ? [MP PET]
11
(a)3 (b)l0- {c)2 (d)l l (a) M KOH (b) M NaOH
46. The concentration ofoxalic acid is x mol L- 1. 40 mL of this 4 4
M M
solution reacts with 16 mL of 0.05 M acidified KMnO4 . (c) - NH4 OH (d) - Ca(OH)z
What is the pH of x M oxalic acid solution? (assume that 4 4
oxalic acid dissociates completely) [EAMCET] 51. 20 mL of0.5 N HCl and 35 mL of0. l N NaOH are mixed.
(a) 1.3 (b) 1.699 (c) I (d) 2 The resulting solution will CKCET]
47. What is the pH oflo-2 M H2SO4? [Guj CET]
(a) be neutral
(b) be basic
(a) 1.600 (b) 2 (c) 10- 2 (d) 1.6990 (c) turn phenolphthalein solution pink
48. HA is a weak acid. The pH of0.1 M HA solution is 2. What (d) turn methyl orange red
is the degree of dissociation (a) of HA ? [J&K CET] 52. The pH of an aqueous solution having hydroxide ion
5
(a) 0 .5 (b) 0.2 (c) 0.1 (d) 0.301 concentration as I x Io- is CJ & K CETJ

2005 (a) 5 (b) 9 (c) 4.5 (d) I 1

49. Hydrogen ion concentration in mol/L in a solution of 53. An aqueous solution of I M NaCl and 1 M HCl is
pH = 5.4 will be [AIEEE] (a) not a buffer but pH < 7 [Jamia Millia Islamia]
(a) 3.98x 10- 6 (b) 3.68x 10- 6 (b) not a buffer but pH> 7
(c) a buffer with pH< 7
(c) 3.88x 106 (d) 3.98x 108 (d) a buffer with pH> 7

Topic 5
Common Ion Effect, Ionic Product of Water
and Solubility Product
1. ThesolubilityproductofAg 2 CrO4 is32x 10- 12 . What is 5. Given theK sp expression. K sp = [A 3 + J2 [B 2 - ]
3
the concentration ofCr04 ions in that solution? [lndraprastha CET]
4
(a) 2 X 10- M (b) 16 X 10- 4 M (VITEEE] 3 2
(a)A 2 B 3 (s)¢::>3A + (aq) + 2B - (aq)
(c)8xl0- M 4 {d)8xl0- 8 M (b) A 2 B 3 (s) ¢::> 3A 3 + (aq)+ 3B 2- (aq)
2. What will be solubility product of Ca (OH)z if its (c) A 3 B 2 (s) ¢=> 3A 3 + (aq)+ 2B 2 - (aq )
solubility is ✓3? [AMU] (d)A 3 B 2 (s)¢=>2A 3 + (aq)+3B 2 - (aq)
(a) 3 (b) 3✓3 (c) 12✓3 (d) 27 6. The Ksp of Ag 2CrO 4 is 1.1 x 10- 12 at 298 K . The
3. If the ionic product of Ni (OH) 2 is I .9 x 10- 15 , then the solubility (in mol/L) of Ag 2CrO4 in a 0.1 M AgNO 3
molar solubility of Ni (OHh in I .0 M NaOH is solution is [JEE Advanced]
11 (b) 1.1 x 10- 10
(a) l.9x 10- 18 M [EAMCET] (a) 1.l x 10-
12
(b)l.9x10- 13 M (c) I.I x 10- (d) l.l x 10- 9
(c) l.9x 10- 15 M 7. If the solubility of PbBr2 in water is s mol/L, then what is
(d) l.9 x 10- 14 M
its K sp conside1ing 80% ionisation? [Manipall
4. Which of the following salts has the greatest molar
(a) 2.048S 2 (b) 2.048S 3 (c) 1.042S 3 (d) 3.042S 2
solubility in pure water? [Indraprastha CET]
(a) CaCO 3 (K sp = 8.7x 10- 9 ) 8. The solub ility product of a binary weak electrolyte is
45 4 x 10- 10 at 298 K. Its solubility (in mol dm- 3 ) at the
(b) CuS (Ksp = 8.5x 10- )
same temperature is CKCET]
(c) Ag 2 CO3 (Ksp = 6 .2x 10- 12 ) (a)4x10- 5 (b) 2x 10- 5
(d) Pb 9 I0 3 (Ksp = 2 .6 x 10- 13 ) (c) 8x 10- 10 (d) 16x 10- 20
 Equilibrium I 171
9. The solubility ofCaF2 is s mol/L. Then, solubility product 2010
is [OJEEJ 16. Solubility product of silver bromide is 5.0x 10- 13 • The
2 3 2 3 quantity of potassium bromide (molar mass taken as
(a) S (b) 4S {c) 4S (d) S
1
120 gmol- ) to be added to 1 L of0.05Msolution of silver
2011 nitrate to start the precipitation of AgBr is [AIEEEJ
10. Passing H 2 S gas into a mixture of Mn 2 +, Ni 2 +, Cu 2 + and (a) l.2 x 10- 10 g (b) l.2x 10- 9 g
Hg 2+ ions in an acidified aqueous solution precipitates (c) 6.2x 10- 5 g (d) 5.0x 10- 8 g
(a) CuS and HgS {b) MnS and CuS [IIT JEEJ 17. At25°C, thesolubilityproductofMg (OH)i is I.Ox 10- 11 •
(c) MnS and NiS (d) NiS and HgS
At which pH, will Mg 2 + ions start precipitating in the form
11. In IL saturated solution of AgCl [K sp(AgC2 = I.6x 10- 10 ],
of Mg ( OH) 2 from a solution of 0 .001 M Mg 2 +ions ?
0.1 mole of CuCl [K sp(CuCl) = 1.0x 10- ] is added. The
resultant concentration of Ag + in the solution isl .6x 10- x . (a) 9 (b) 10 [AIEEE]
The value ofxis [HT JEE] ( c) 11 ( d) 8
( a) 3 (b) 5 {c) 7 ( d) 9 18. The solubility of AgCl in 0. 2 M NaCl solution is
30
10
12. The Ksp for Cr (OHh is l.6x 10- . The molar solubility (Ksp of AgCl = l .20x 10- ) [Manipall
of this compound in water is [AIEEEJ
(a)6.0x10- I0
M (b)0.2M
10
(a) ~l.6x 10- 3o (b) V1.6x 10- 30 (c) l.2x 10- M (d) 0 .2x 10- 10 M
(c) V1.6x 10- 30 / 27 (d) l.6x 10- 30 /27 19. The expression for the solubility product of Ag 2 CO 3 will
13. H 2 Sisgassed into 1 dm3 of a solution containing 0.1 mole be [MPPET]
2 3 4
of Zn + and 0 . 0 I mole of Cu 2 + till the sulphide ion (a)Ksp =s (b)Ksp =4s (c)Ksp = 27s (d)Ksp =s
concentration reaches 8.lx 10- 19 mole. Which one of the
following statement is correct? 20. 1 dm3 solution containing 10- 5 moles each ofC l- ions and
(Ksp of ZnS and CuS are 3 x 10- 22 and 8 x 10- 36 , Cro~- ions is treated with 10- 4 moles of silver nitrate.
respectively) [KCETJ Which one of the following observations is made?
12 10
(a) Only ZnS precipitates (K5 PAg 2CrO4 = 4 X 10- ) (K5 PAgCl = lx 10- )
(b) Both CuS and ZnS precipitate (a) Precipitation does not occur [KCETJ
(c) Only CuS precipitates (b) Silver chromate gets precipitated first
(d) No precipitation occurs (c) Silver chloride gets precipitated first
14. The solubility product (K sp) of the following compounds (d) Both silver chromate and silver chloride start
precipitating simultaneously
are given at 25°C
21. The solubility product of Hg 2 12 is equal to [RPETJ
Compound K,p 2
(a)[Hg~+ ] [r ] (b)[Hg + ] [r]
AgCI 1.1x10- 10
(c)[Hg~+ ] [r ] 2 (d)[Hg 2+ ] [r ]2
Agl I.Ox 10-16
PbCrO4 4.0x 10-14 2009
12
Ag2CO3 8.0x 10- 22. Solid Ba (NO 3 h is gradually dissolved in a 1.0 x 10-4 M
2
Na 2 CO3 solution. At what concentration of Ba + will a
The most soluble and least soluble compounds are
(a) AgCl and PbCrO4 [Kerala CEEJ
precipitate begin to form? (K sp for BaCO3 = 5.l x 10- 9 )
(b) Agl and Ag 2 CO3 (a)4.lxl0- 5 M (b)5.lxl0- 5 M [AIEEEJ
7
(c) AgCl and Ag 2 CO3 (c)8.lxl0- 8 M (d)8.l x l0- M
( d) Ag 2 CO 3 and Agl 23. In qualitative analysis, in m group NH4Cl is added before
(e) Ag 2 CO 3 and PbCrO4
NH4OH because [UPSEEJ
15. The solubility of Ca 3 (PO4 h in water is y mole / L. Its
(a) to increase the concentration of NH; ions
solubility product is [WB JEE] (b) to increase the concentration of Cl - ions
(a) 6/ (b) 36/ ( c) to reduce the concentration of OH- ions
(c) 64/ (d) 108/ ( d) to increase the concentration of OH- ions
172 I Chapterwise & Topicwise Engineering Entrances Solved Papers
24. Approximate relationship between dissociation constant of
(a) between lO~to 10-7 M [Jamia Millia Islamia]
water (K) and ionic product of water (Kw) is [AMU]
(b) between 10-7 M to 10-8 M
(a)K w = K (b)Kw = 55.6xK (c)> 10-5 M
(c)Kw =I 8xK (d)Kw = l4xK
17
(d)< 10-8 M
25. IfK sp of Ag 2 Sis 10- , then the solubility of Ag 2 S in 0. IM
solution ofNa 2 Swill be [Indraprastha CET, CG PET] 34. The solubility of AgCl in 0.2 M NaCl is
(a) 10- 8
(b) 5x 10- 9
(c) 10- 15
(d) 10- 16 (K sp of AgCl = 1.8 X 10-IO) [DCE]
11 10
26. Which of the following has the highest value of solubility (a) 1.8x 10- M (b) 9x 10- M
product? [Indraprastha CET, CG PET] (c) 6.5x 10-12 M (d) 5.6x 10-11 M
(a) CuS (b) Bi 2 S 3 (c) CdS (d) ZnS
2007
27. The solubility product of iron (ID) hydroxide is 1.6x 10- 39 .
35. In a saturated solution of the sparingly soluble strong
IfXis the solubility of iron (III) hydroxide, then which one
electrolyte AglO 3 (molecular mass = 283) the equilibrium
of the following expressions can be used to calculate X ?
which sets in is
4 4
(a) Ksp = X (b) Ksp = 9X [DCE] AgI03 (s) :.====! Ag+(aq)+I03(aq)
3 4
(c)Ksp = 27X (d)Ksp = 27X
If, the solubility product constant K sp of AglO 3 at a given
temperatw·e is 1.0 x l 0~, then what is the mass of AgIO 3
2008 contained in 100 mL of its saturated solution? [AIEEEJ
28. Solubility product constant [K sp] of salts of types MX, (a) 28.3 X 10-2 g (b) 2.83 X 10-3 g
MX 2 and M 3 X at temperature T are 4.0x 10-8 ,
(c) 1.0x 10-7 g (d) 1.0x 10-4 g
3.2x 10- 14 and 2.7x 10-15 respectively. Solubilities
(mol, dm-3 ) of the salts at temperature T are in the order 36. The solubility of AgCI is l x 10- 5 mol/L. Its solubility in
(a) MX > MX 2 > M 3 X [IIT JEE] 0.1 molar sodium chloride solution is [MHT CETJ
(b)M 3 X > MX 2 >MX (a) 1x 10-10 (b)l x 10-5
(c)MX 2 > M 3 X > MX ( C) 1 X 10-9 ( d) 1 X 10--4
(d)MX> M 3 X> MX 2
1 37. The solubility product of a sparingly soluble salt AX2 is
29. Solubility of Ca(OH)z is a s mol L- • The solubility
3 .2 x 10-11 . Its solubility (in mol/L) is [Manipall
product (K sp) under the same condition is [MHT CET]
(a)5.6x10---{j (b)3.Ix10- 4
(d) s3
4 2
(a) 4s 3 (b) 3s (c) 4s
( C) 2 X 10- 4 ( d) 4 X 10- 4
30. Addition ofsodium acetate to 0.1 M acetic acid will cause
(a) increase in pH [WB JEE] 38. When ammonium chloride is added to ammonia solution,
(b) decrease in pH the pH of the resulting solution will be [MHT CETJ
( c) no change in pH (a) increased (b) seven
( d) ch ange in pH that cannot be predicted ( c) decreased ( d) unchanged
31. Solubility product ofMg(OH)zat ordinary temperature is 39. The solubility in water of a sparingly soluble salt AB2 is
1
1.96 x l 0-11 • pH of a saturated solution, of Mg(OH)z will 1.0 x 10-5 mol L- . Its solubility product number will be
be [WB JEE] (a) 4 x 10- 15 [UPSEE, MP PET]
(a) 10.53 (b) 8.47 (c) 6.94 (d) 3.47 (b) 4 X 10-IO
(c) 1X 10-15
32. An aqueous solution contains Ni 2 + , Co 2+ and Pb 2 + ions
(d) 1 X 10-IO
at equal concentrations. The solubility Eroduct ofNiS, PbS
and Cos in water at 25°C are l.4 X 10- 4, 3.4 X 10-28 and 3 40. Solubility of AgCI at 20°c is 1.435 x I 0-3 g/ L. The
x 10-26, respectively. Indicate which of these ions will be solubility product of AgCl is [WBJEE]
precipitated first and last when sulphide concentration is (a) 1X 10-5 (b) 1 X 10-IO
progressively increased from zero? [J&K CET]
(c) 1.435x 10-5 (d) 108x 10-3
(a) NiS and PbS (b) NiS and CoS
(c) CoS and NiS (d) PbS and NiS 41. At 30°C, the solubility of Ag 2 CO 3 (Ksp = 8x 10-12 )
would be greatest in I L of [WB JEE]
33. Solubility product of a salt AB is 1 x 10~ M 2 in a solution
in which the concentration of A+ ions is 10-3 M. The salt (a) 0.05 M Na 2 CO 3 (b) 0.05 M AgNO3
will precipitate when the concentration of ions is kept s- (c) pure water (d) 0.05 M NH 3
 Equilibrium I 173
42. TheKsp ofCa 3 (PO 4 his [OJEE] 52. The value of the ionic product of water depends [UPSEEJ

(a) [Ca 2+] [PO!- ]2 (b)[Ca 2+ ] 3 [PO!-] (a) on volume of water

(b) on temperature
(c) [Ca 2+] [PO!- ] (d)[Ca 2+] 3 [P0!-] 2 (c) changes by adding acid or alkali
43. If solubility of calcium hydroxide is ✓3, then its solubility (d) always remain constant
product will be [AMU] 53. Some chemists at ISRO wished to prepare a saturated
(a) 27 (b) 3 (c) 9 (d) 12✓3 solution of a silver compound and they wanted it to have
the highest concentration of silver ion possible. Which of
o-
44. The solubility product of BaCl 2 is 4 x 1 9 . Its solubility the following compounds, would they use?
(in mol/L) is [BCECEJ
Ksp (AgCl) = l.8x 10- io
(a) 4 x 10-3 (b) 4 x 10-9 (c) 1 x 10-3 (d) 1x 10-9
Ksp(AgBr) = 5.0x 10- 13
45. The molar solubility (in mo! L- 1) ofa sparingly soluble salt
MX 4 is 's'. The corresponding solubility product is K ,sp. Ksp(Ag 2 CrO4 ) = 2.4 x 10- 12 [BCECEJ
Sis given in terms of K sp by the relation (a) AgCl (b) AgBr
[Jamia Millia l slamia ] (c) Ag 2 Cr04 (d) None of these
114 114
(a) S = (K sp 1/ 28) (b) S = (128Ksp )
115 115 2005
(c) S = (256Ksp ) (d) S = (K sp / 256)
54. The solubility product of a salt having general formula
46. Solubility of Al(OH)J = s, K sp will be IDCEJ MX 2 , in water is 4 x lo- 2 . The concentration of M 2 +
(a)108S 3 (b)27S 3 ions in the aqueous solution of the salt is [AIEEEJ
(c)4S 4 (d)27S 4 (a) 4.0x 10- M10 (b) l.6x 10- M4
(c)I.0xl0- 4 M (d)2.0 x 10- 3
2006
55. At 90°C, pure water has H 3 o+ ion concentration of
47. The solubility of Agl in Nal solution is less than that in
6
pure water because [Manipal] 10- mo! / C I . The K IV at 90°C is [Manipal]
(a) the temperature of the solution decreases (a)l0- 6 (b)l0- 14
(b) solubility product of AgI is less than that ofNal (c) 10- 12 (d) Io- 8
(c) of common ion effect
56. A precipitate of AgCI is formed when equal volumes of the
(d) Agl forms complex with Nal
following are mixed.
48. The solubility of Pb(OHh in water is 6.7 x I o-6M. Its
[K sp for AgCI = 10- 1o] [KCET]
solubility in a buffer solution of pH = 8 would be
(a) 10- 4 M AgNO 3 and 10- 7 M HCI
(b) l.6x 10-3
2
(a) l.2x 10- [Manipal]
(b)J0- 5 MAgNO 3 and l 0- 6 MHCI
(c) l.6x 10- 2
(d) l.2x 10-3
(c) 10- 5 M AgNO 3 and 10- 4 M HCI
49. For which of the following sparingly soluble salt, the
(d) 10- 6 M AgNO 3 and 10- 6 M HCI
solubility (s )and solubility product (K sp )are related by the
113 57. The correct expression for the solubility product of
expressions = (K sp / 4 ) ? [KeralaCEEJ
Ca 3 (PO 4 his [OJEEJ
(a) BaSO4 (b) Ca 3 (PO 4 ) 2
(a) 108s 5 (b) 27 s 5
(c) Hg 2 Cl 2 (d) Ag 3PO 4
(e) CuS (c) 16s4 (d) 81s4
50. The solubility of Sb 2S 3 in water is 1.0 x 10-5 mo! / L at 58. On adding 0.1 M solution each of[Ag +], [Ba 2 +],[Ca 2 +]
298 K. What will be its solubility product ? [WB JEE] in a Na 2 SO4 solution, species first precipitated is
(a) 108x 10-25 (b) I.Ox 10-25 (KspBaSO4 = 10- 11 ,Ksp CaSO4 = 10- 6 ,
(c) 144 x 10-25 (d) 126x 10-24
Ksp AgSO4 =10- 5 ) [DCE]
51. The solubility of CaF2 is pure water is 2.3 x 10- 6 mo!
(a) Ag 2 SO4
dm- 3 . Its solubility product will be [UPSEEJ (b) BaSO4
(a)4.8x 10- 18 (b)48.66xl0- 18 (c) CaSO4
(c)4.9x l 0- 11 (d)48.66xl0- 15 (d) All of the above
 Topic 6
Buffer Solution, Salt Hydrolysis
and Acid-Base Titrations
2014
1. Calculate the pH at the equivalence point during the 9. A buffer solution is prepared by ID.1Xmg equal
titration of 0.1 M, 25 mL CH 3 COOH with 0.05 M NaOH concentration ofa weak base with its salt ofstrong acid.Kb
solution.[K 0 (CH 3 COOH) = l.8xl0- 5 ] [BITSAT] for the base is lo- 9 . pH of this buffer solution will be
(a) 9.63 (b) 8.63 (c) 10.63 (d) 11.63 (a) 9 (b) 4 (c) 5 (d) 13 [OJEE]
2. One mole of ammonia was completely absorbed in IL 2011
solution each of
10. A buffer solution contains 0 .1 mole of sodium acetate
I. I MHCI
dissolved in 1000cm3 of 0 .1 M acetic acid. To the above
II. I M CH3COOH and
buffer solution, 0.1 mole ofsodium acetate is further added
III. I M H2S0 4 at 298 K
and dissolved. The pH of the resulting buffer is CKCET]
The decreasing order for the pH of the resulting solution is
(given, Kb {NH3 ) = 4.74) [KCET] (a) pK 0 (b) pK 0 + 2
(c) pK 0 - log 2 (d) pK 0 + log 2
(a)II> III > I (b) I >II> III
(c) II > I > III (d) III > II > I 11. The pH of an aqueous solution of CH 3 COONa of
concentration C (M) is given by [WBJEE]
2013
l 1
3. pH of an acid buffer is given by [Manipal] (a) 7- pK0 - Iog C
2 2
(a)pH = pK 0 + log [sa~t] (b)pH =pK 0 -log [sa~t] l 1 1
[acid] [acid] (b) - pKw + - pKb +- loge
2 2 2
(c)pH = K 0 +log [sa~t] (d)Noneofthese 1 l 1
2pK w - 2 pK b - 2 log C
[acid] (c)
4. The pK a of a certain weak acid is 4.0. What should be the l 1 l
(d) - pK w + - pK a + - log C
[salt] to [acid] ratio if we have to prepare a buffer with 2 2 2
pH = 5 using the acid, and one of the salts ? [KCET]
(a) 10: 1 (b) 1 : 10 (c) 4: 5 (d) 5: 4 2010
12. Amongst the following, the total number of compounds
2012 whose aqueous solution turns red litmus paper blue is
5. In the titration ofNaOH and HCl, which of the following KCN K 2 SO4 (NH4 ) 2 C 2 O 4 NaCl
indicator will be used ? [BITSAT] Zn (NO 3 ) 2 FeCl 3 K 2 CO 3 NH 4 NO 3
(a) Methyl orange (b) Methyl red LiCN [IIT JEE]
(c) Both (a) and (b) (d) None of these WI ~2 ~3 W4
6. An acidic buffer solution could be prepared by mixing the 13. Which buffer solution comprising of the following has its
solutions of the following [MP PET] pH value greater than 7 ? [RPETJ
(a) sodium acetate and acetic acid (a) CH 3 COOH+CH3 COONa
(b) ammonium sulphate and sulphuric acid (b) HCOOH + HCOOK
(c) ammonium chloride and ammonium hydroxide (c) CH 3 COONH4
(d) sodium chloride and hydrochloric acid (d) NH4 OH+ NH 4 Cl
7. 20 mL 0.1 N acetic acid is mixed with 10 mL 0.1 N solution
ofNaOH. The pH of the resulting solution is
2009
(pK 0 ofacetic acid is 4.74) [WBJEE] 14. The dissociation constant of a substituted benzoic acid at
4
(a) 3.74 (b) 4.74 (c) 5 .74 (d) 6.74 25°C is I.Ox 10- . The pH of 0.Ql M solution of its
sodium salt is [IIT JEE]
8. A 100 mLof0.1 M solution ofammonium acetate is diluted
by adding 100 mL of water. The pH of the resulting W3 ~1 ~8 W6
solution will be (pK a of acetic acid is nearly equal to pK b 15. The buffering action of an acidic buffer is maximum when
ofNH 4 OH) [WB JEE] its pH is equal to [UPSEE]
(a) 4.9 (b) 5.0 (c) 7.0 (d) 10.0 (a) 5 (b) 7 (c) 1 (d) pK 0
 Equilibrium I 175
16. A strong acid is titrated with weak base. At equivalence 25. Assertion (A) The aqueous solution of CH 3 COONa is
point, pH will be [OJEEJ alkaline in nature.
(a)< 7 (b)> 7 Reason (R) Acetate ion undergoes anionic hydrolysis.
(c) = 0 (d) cannot predict CEAMCET]
17. Which of the following is not a buffer solution? (a) Both A and R are correct and R is the correct
[Indraprastha CET, CG PET] explanation of A
(a) 100 mL 0.1 M CH3 COOH + 50 mL 0.1 M (b) Both A and R are correct but R is not the correct
CH3 COONa explanation of A
(b) 100 mL 0-lM CH3 COOH+ 50 mL 0-lM NaOH (c) A is correct but R is not correct
(c) 50 mL 0.1 M CH3 COOH + 100 mL 0.1 M NaOH (d) A is not correct but R is correct
(d) 100 mL 0.1 M NH4 OH + 50 mL 0.1 M HCl 26. The aqueous solutions of HCOONa, C 6 H 5 NH3 CI and
18. For the titration of solution of oxalic acid and sodium KCN are respectively [Guj CET]
hydroxide, the suitable indicator is (a) acidic, acidic, basic (b) acidic, basic, neutral
[lndraprastha CET, CG PET]
(c) basic, neutral, neutral (d) basic, acidic, basic
(a) phenolphthalein (b) methyl orange
(c) any of these (d) None of these 2007
27. TbepKa ofa weak acid HA is4.5. ThepOHofanaqueous
2008
buffered solution of HA in which 50% of the acid ionised is
19. 2.5 mL of~ M weak monoacidic base (Kb = Ix 10- 12 at (a) 4.5 (b) 2.5 [AIEEE]
5
(c) 9.5 (d) 7.0
25°C) is titrated with 2 M HCI in water at 25°C. The
15 28. The rapid change of pH near the stoichiometric point of an
concentration of H+ at equivalence point is acid base titration is the basis of indicator detection. pH of
14 the solution is related to the ratio of the concentrations of
(Kw = 1 X 10- at 25°C) [IIT JEE]
13 the conjugate acid (Hin) and base (In - ) forms of the
(a) 3.7x 10- M (b) 3.2x 10- 7 M indicator given by the expression [Manipal]
(c)3.2xl0- 2 M (d) 2.7x 10- 2 M
(a) log [In - ] = pK1n - pH (b) log [Hin] = pK1n - pH
20. The pKa ofa weak acid, HA, is 4.80. The pK b ofa weak [Hln] [In - ]
base, BOH is 4.78. The pH ofan aqueous solution of the
corresponding salt, BA, will be [AIEEEJ (c) log [Hl n] = pH - pK1n (d) log [In - ] = pH - pK1n
[In - ] [Hln]
(a)9.58 (b)4.79
(c) 7.01 (d) 9.22 29. The hydrolysis of sodium carbonate involves the reaction
21. Which one of the following salts will produce an alkaline between [MIIT CET]
solution while dissolving in water? [MP PET] (a) sodium ion and water (b) Na+ and OH-
(a) NH4 Cl (b) Na 2 CO3 (c) co; - and water (d) co;- and H+
(c) NaNO 3 (d) Na 2 SO4
30. Which one of the following salts on being dissolved in
22. A buffer solution is prepared by mnong equal water gives pH > 7 at 25°C ? CKCETJ
concentration of acid (ionisation constant Ka ) and a salt. (a) KCN (b) KNO 3 (c) NH4 Cl (d) NH4 CN
The pH of buffer is [OJEEJ
31. In the titration of Na 2 CO 3 and HCl, the indicator used is
(a) pKa + 7 (b) 14 - pKa
(c) pKa (d) pKa+ I (a) methyl orange CWB JEE]
(b) methylene blue
23. Which is the best choice for weak base-strong acid (c) phenolphthalein
titration? [OJEEJ (d) litmus
(a) Methyl red (b) Litmus 32. Degree of hydrolysis ( h) ofa salt of weak acid and a strong
(c) Phenol red (d) Phenolphthalein base is given by [OJEEJ
24. A buffer solution is prepared by mixing 0.1, M ammonia
and 1.0 M ammonium chloride. At 298 K, the pK b of (a) h = jK;
NH4 OHis 5.0. The pH of the buffer is [UPSEEJ
(a) 10.0
(c) 6.0
(b) 9.0
(d) 8.0
(c) h =ft (d) None of these
176 I Chapterwise & Topicwise Engineering Entrances Solved Papers
33. What volwne ofM/ 10 NaOH added in 50 mL, M/ 10 acetic A buffer solution can be obtained by mixing equal volumes
acid solution to get a buffer solution having highest buffer of [J&K CET]
capacity ? [AMU] (a) CandD (b)A andB
(a) 50 mL (b) 25 mL ( c) A and C ( d) C and D
(c) 10 mL (d) 40 mL 41. A white substance having alkaline nature in solution is
34. Which one of the following salts give an acidic solution in (a) NaNO3 (b) NH 4 Cl [BCECEJ
water ? [EAMCET] (c) Na 2 CO 3 (d) Fe 2 O 3
(a) CH 3 COONa (b) NH4 Cl 42. A solution of FeCl 3 in water acts as acidic solution
(c) NaCl (d) CH3 COONH 4
due to [BCECEJ
2006 (a) hydrolysis ofFe 3+
35. The pH of a buffer solution contammg equal molal (b) acidic impurities
concentration of a weak base and its chloride (Kb for weak (c) dissociation
5 (d) ionisation
base = 2 X 10- ) is [MHT CET]
(a) 5 (b) 9 (c) 4.7 (d) 9.3 2005
36. Relation between hydrolysis constant and dissociation 43. 0.1 moleofCH 3 NH 2 (Kb = 5x10- 4 ) is mixedwith
constant are given. Which is the correct formula for 0.08 mole ofHCl and diluted to IL. What will be the H+
MgC1 2 ? [MP PET] concentration in the solution ? [IIT JEE]
(a) 8x 10- 2 M (b) 8x 10- 11 M
(a) K1, =~ w (b) Kh = Kw 11
a Kb (c) l.6x 10- M (d) 8x 10- 5 M

(c)K1,= Kw (d)K w =KKh 44. A buffer solutfon has equal volumes of0. 2 M NH 4 OH and
K a X Kb b 0.02 M NH4 CL The pKb of the base is 5. The pH is equal
37. Which one of the following pair shows buffer's solution? to [KCETJ
(a) NaCl + NaOH [WB JEE] (a) 10 (b) 9
(b) CH 3 COONa + C H3 COOH (c) 4 (d) 7
(c) CH 3 COOH + CH 3 COONH 4 45. Assertion (A) The pH ofa buffer solution containing equal
(d) H 2 SO4 + CuSO4 moles of acetic acid and sodium acetate is 4.8 (pK O of
38. Which of the following salt does not get hydrolysed in acetic acid is 4.8).
water ? [WB JEEI Reason (R) The ionic product of water at 25°C is I 0- 14
(a) KC1O4 (b) NH4 Cl mol 2 L- 2 . The correct answer is [EAMCETJ
(c) CH 3 COONa (d) None of these
(a) Both A and Rare true and R is the correct explanation
39. In a mixture of acetic acid and sodium acetate the ratio of of A.
concentration of the salt to the acid is increased ten times. (b) Both A and R are true and R is not the correct
Then, the pH of the solution [AMU] explanation of As.
(a) increases by one ( c) A is true but R is not true.
(b) decreases by one ( d) A is not true but R is trne.
( c) decreases ten fold 46. The compound whose 0.1 M solutions is basic, is [DCEJ
(d) increased ten fold (a) ammonium acetate
40. Consider the following solutions of equal concentrations (b) ammonium chloride
A = NH4CI B = CH 3 COONa (c) ammonium sulphate
C = NHpH D = CH3COOH (d) sodium acetate
 Answers
TOPICl Equilibrium Constants and Their Units
1. (b) 2. (b) 3. (a) 4. (c) 5. (a) 6. (a) 7. (b) 8. (a) 9. (a) 10. (a)
11. ( d) 12. (d) 13. (d ) 14. (c) 15. (d) 16. (a) 17. (a) 18. (a) 19. (b) 20. (d)
21. (c) 22. (a) 23. (c) 24. (d) 25. (b) 26. (d) 27. (a) 28. (c) 29. (d ) 30. (b)
31. (a) 32. (c) 33. (c) 34. (d) 35. (c) 36. (c) 37. (c) 38. (a) 39. (b) 40. (b)
41. (c) 42. (d) 43. (a) 44. (c) 45. (b) 46. (b) 47. (d) 48. (b) 49. (a) 50. (a)
51. (a) 52. (a) 53. (a) 54. (a) 55. (d) 56. (d) 57. (c) 58. (c) 59. (c) 60. (b)
61. (d ) 62. (b) 63. (a) 64. (c) 65. (b) 66. (b) 67. (a) 68. (a) 69. (a) 70. (b)
71. (a) 72. (d) 73. (a) 74. (d ) 75. (b) 76. (b) 77. (c) 78. (c) 79. (c) 80. (a)
81. (c) 82. (b) 83. (d) 84. (a) 85. (c) 86. (d) 87. (c) 88. (a) 89. (c) 90. (d)
91. (b) 92. ( C) 93. (b) 94. (a) 95. (a) 96. (a)
TOPIC2 Factors Affecting Equilibria (Le-Chatelier's Principle)
1. (a) 2. (a, b) 3. (a) 4. (c) 5. (c) 6. (a) 7. (a) 8. (c) 9. (a) 10. (a)
11. (a) 12. (a) 13. (b) 14. (c) 15. (a) 16. (a) 17. (e) 18. (a) 19. (a) 20. (d)
21. (b) 22. (d) 23. (c)
TOPIC3 Degree of Dissociation, Acids and Bases
1. (a) 2. (a) 3. (a) 4. (b) 5. (d) 6. (a) 7. (c) 8. (b) 9. (c) 10. (b)
11. (a) 12. (a) 13. (a) 14. (b) 15. (d) 16. (a) 17. (b) 18. (d) 19. (c) 20. (c)
21. (b) 22. (b) 23. (c) 24. (d) 25. (c) 26. (d) 27. (c) 28. (d) 29. (b) 30. (a)
31. (b) 32. (c) 33. (c) 34. (b) 35. (b) 36. (a) 37. (d) 38. (a) 39. (a) 40. (c)
41. (a) 42. (a) 43. (a) 44. (c) 45. (a) 46. (a) 47. (a) 48. (a) 49. (d) 50. (c)
51. (c)
TOPIC4 pH Value and Related Terms
1. (d) 2. (d) 3. (c) 4. (d) 5. (b) 6. (d) 7. (b) 8. (c) 9. (d) 10. (c)
11. (a) 12. (b) 13. (a) 14. (a) 15. (d) 16. (c) 17. (d) 18. (b) 19. (a) 20. (a)
21. (b) 22. (c) 23. (a) 24. (d) 25. (a) 26. (a) 27. (b) 28. (c) 29. (c) 30. (c)
31. (b) 32. (a) 33. (c) 34. (b) 35. (c) 36. (c) 37. (b) 38. (a) 39. (b) 40. (a)
41. (b) 42. (b) 43. (a) 44. (b) 45. (d) 46. (a) 47. (d) 48. (c) 49. (a) 50. (d)
51. (c) 52. (b) 53. (a)
TOPIC5 Common Ion Effect, Ionic Product of Water and Solubility Product
1. (a) 2. (c) 3. (c) 4. (c) 5. (d) 6. (b) 7. (b) 8. (b) 9. (b) 10. (a)
11. (c) 12. (c) 13. (b) 14. (d) 15. (d) 16. (b) 17. (b) 18. (a) 19. (b) 20. (c)
21. (c) 22. (b) 23. (c) 24. (b) 25. (b) 26. (d ) 27. (d) 28. (d) 29. (a) 30. (a)
31. (a) 32. (d) 33. (c) 34. (b) 35. (b) 36. (c) 37. (c) 38. (c) 39. (a) 40. (b)
41. (d ) 42. (d) 43. (d) 44. (c) 45. (d) 46. (d ) 47. (c) 48. (d) 49. (c) 50. (a)
51. (b) 52. (b) 53. (c) 54. (c) 55. (c) 56. (c) 57. (a) 58. (b)
TOPIC6 Buffer Solution, Salt Hydrolysis and Acid-Base Titrations
1. (b) 2. (c) 3. (a) 4. (a) 5. (c) 6. (a) 7. (b) 8. (c) 9. (c) 10. (d)
11. (d) 12. (c) 13. (d) 14. (c) 15. (d) 16. (a) 17. (c) 18. (a) 19. (d) 20. (c)
21. (b) 22. (c) 23. (a) 24. (d) 25. (a) 26. (d ) 27. (c) 28. (d) 29. (c) 30. (a)
31. (a) 32. (c) 33. (a) 34. (b) 35. (d) 36. (b) 37. (b) 38. (a) 39. (a) 40. (c)
41. (c) 42. (a) 43. (b) 44. (a) 45. (b) 46. (d)
 Explanations
Topic 1 Equilibrium Constants and Their Units
2
1. The re lationship between KP and Kc is given by:
⇒ (2 x) = 49 ⇒ ~ = 7
(0.5-x)2 0.5-x
KP = Kc (RT/"1g
where, ling = moles of gaseous products-moles of gaseous 3.5
⇒ 2x = 3.5 - 7x ⇒ 9x = 3.5 ⇒ X = - = 0.3888
reactant 9
On comparing the above relation with PH 2 = 0.5- 0.3888= 0. 1111
KP= Kc(RT)' 6. A+ B~C + D
At I= 0, 0 0
Value ofx is ling-
At equilibriwn, {I - 04) {I - 0.4) 0.4 0.4
Thus, for the given reaction
- 0 .6 --0.6
S0 2 (g) + ¾ 0 2 (g) ~ S03 (g) Kc= [C][D]= 0.4x 0.4 0.44
2 1 [A][B] 0.6 x 0.6
ling= 1-(t+¾)= 1-( ; )= t-%=-½ 7. The mixture of reactants and products in the equilibrium state is
-I called equilibrium mixture. This state of equilibrium is called
Thus, the value of x is - . chemical equilibrium and nature of this state is dynamic instead
2
of static.
2.
8. (Rate)tt,y = k[H+ ] HX
K _ Kf 1.1 x 10-2
7.33 (Rate)tt,y = 100 (Rate)HA Also, in strong acid,
c- Kb 1.5x 10-3
[W]=[HX ] =lM
3. Equi librium concentration of NP= 0 2 = 0.05 M
(Rate)HX [W lHX
Let the equilibrium concentration ofNO 2 and NO be x M. - - - = 100 = - - -
2 (Rate)HA [H+ ] HA [H+ ]HA
Kc= 0.9 14 = (O.O;) ⇒x = 0.0522 M
X
[ H+ ] - 1
Initial concentrations ofNO 2 and NO were 0.05 + x = 0.1022 M HA - 100
each. H A ~ H+ + A-
Hence, moles of each gas NO 2 and NO taken initially I 0 0
= 5 X 0.1022 = 0.511 (1 - x) X X

4. CaCO 3 (s) ~ CaO(s) + CO2 (g) X= 0.01

n [W ][A-] 0.01 X 0.01 = J.0I X 10_4
K P =Pco 2 = -V RT K = ~~~~
a [HA] 0.99
1.64 = .!!_ X 0.082 X 1000 9. Relation between KP and Kc is
10
l.64x l 0 02, KP = Kc (RT)flng
⇒
n 0.082 X 1000 . Where, ling = (moles of gaseous product) - (moles of gaseous
i.e. number of moles of CO2 = 0.2 reactants)
CaCO 3 ~ CaO + CO2 10. N 2 (g) + 3H2 (g) ~ 2NH 3 (g)
Initially, SOg=~=0.511101 0 The quantity ofN2 (g) reacted= 100 mL
100
At equilibrium, 05 - 02 0.2 11101 0.2 :. The quantity of H 2 (g) is three times = 300 mL and NH3
produced = 200 mL
: . Unreacted CaCO 3 = 0.5- 0.2 = 0.3 mol
03 11. The volume of vessel= 10 dm 3
and percentage of unreacted CaCO3 = · x 100= 60%
0.5 PCl 5 (g) ~ PC1 3 (g) + Cl 2 (g)
5. H2 + I2 --'- 2ffi At equilibritun, PCl 5 = .Q:.!. = 0.01 M
Initially 0.5 0.Satn, 0
10
At equilibrium (0.5- x) (0.5- x) atn, 2xatm The equilibrium constant,
= (pHl)2 K = [PC1 3 ] [ Cl2] = 0.02 x 0.02 = _
Kp (2x)2 =49 0 04
⇒
(0.5- x) (0.5 - x) c [PC1 5 ] 0.0 I
Ptt 2 "Pr 2
 Equilibrium I 179
12. Ni(g) + O 2 (g) --4 2NO(g) Pco 2 = 0.5 - 0.3 = 0.2 atm and Pco = 2p = 0.6 atm
2 2
Kc= [NO] =4x l0- 4 K p = Pco = 0.6x 0.6 = I . 8atm
[N2HO2l Pcoz 0.2
2NO(g) ---4 N 2(g) + O2(g) 18. PC1 5
K' _ _ l_ _ [N2 ][0 2 ] _ _ _~
4 4
10 Initial cone. 0 0
C - Kc - [NO]2 - 4 X 10- 4 4 4
2 2 2
Equilibrium cone.
I I 4 4 4
NO(g)
2 N 2(g) + 2 Oz(g)
---4
K = [PC1 3 ][Cl 2 ] 2x2x4 =..!.=o.5
112 2 [PC1 5 ] 4x4x2 2
Kc= [N2 ] [02 f = ~ = {JD4 = 100 = 50
[NO] V4 2
19. For the reaction, SO2 (g) + ..!_ O 2(g) ~ SO3(g)
13. 2NOBr(g)~ 2NO(g) + Br2(g) 2

p- (
2p p)
9 +9 =3
2p 2p
9
p_
9
Eqm·1·b.
1 rmm constant,
K =
1
[SO3]
112
...(i)
[SO2HO2l
For the reaction, 2SO 3(g) ~ 2SO 2 (g) + O 2 (g)
(¥Y(i) = !!__
(~r
2
andK = (pN0) x(ps,2) = Equilibrium constant, K = [S02 ]2 [0 2 ] ...(ii)
p (pNOB,)2 81 z [SO3]2
On squaring both sides in Eq. (i), we get
2
KP = __!___ Kz _ [SO3]
1 ...(iii)
p 81 - [S02 ]2[O2 ]
I On multiplying Eq. (ii) and (iii), we get
14. 2NO 2 + - 02 ~ N20s
2 2 I 2 I
K I x K 2 = I or K 2 = - 2 or K 1 = -
PNzOs K1 K2
KP = 2 112
(pNo 2 ) (Po 2 ) 20. If final pressure is higher than the initial pressure of contains
2N2Os ~ 2N2O4+ 02 filled with an ideal gas at constant temperature, then the value of
K < 1.0
K' = (pNz04)2 (pOz) = _I_
21. H 2CO 3 ~ H+ + HCO3; K 1 = 4.2 x 10-7
P (pNzOs)2 K; Hco;- ~ H+ + co~-; K 2 = 4.8 x 10-11 K 1 » K 2
[:. N 2 O4 is a dimer of NO2, therefore N 2O 4 = 2NO2 ]
[H+ ] = [HCO-] K = [H+ ][CO~-]
15. Standard free energy change, 3 2
0
[HCO3]
t.G = - 2.303 RT log Kc
So, [CO~-]= Ki= 4.8 x 10-t I
= - 2.303 X 8.3 14 X 298 X log 0.008
_____,,.
= - 2.303 X 8.314 X 298 X (- 2.097) 22. NH4HS (s) NH3(g) + H 2S (g)
= + 11965.16J=+ ll.96kJ Initially 0 0
At equilibriwn p p
K1
16. H 2CO + H 2O ~ H 2C(OH)i Given,
Kz
CH3CH2CHO + H2 O ~ CH3CH2CH(OH)2 p + p = I00atm ⇒ 2p = I00atm ⇒ p = 50atm
2
K3 KP= PNH 3 · PHzS = 50 x 50 = 2500atm
CH 3COCH3 + H 2O ~ CH 3C(OH)2 CH3
23. 4NH3 + 502 ~ 4NO + 6H2O
Due to steric effect, the order of equilibrium constants will be 2
K1>K2>K3 K _ [NO] [H2Of
c - [NH3]4[Oi)5
17. CO 2 (g) + C(s) ~ 2CO(g)
1
Initially 0.5 aim Hence, units of Kc= conc.C8•9)= cone. - .
At equilibrium. (0.5 - p) 2p atm
24. Equilibrium constant depends only upon the temperature, not
This is a case of heterogeneous equilibrium. upon the concentration of reactant. Thus, on doubling
C(s) being solid is not considered. concentration, equilibrium constant remains the same.
Total pressure of CO2 and CO gases. Pco 2 + Pco = Ptotal
0.5 - p + 2p = 0.8, p = 0.3 atm
180 I Chapterwise & Topicwise Engineering Entrances Solved Papers
25. KP = Kc(RT)ill! 34. A + B C+D
Initially I I 0 0
KP= Kc only when (RT)t;.,, = 0 At equilibrium O- 3x) O- 3x) 3x 3x
(a) PC1 5 ~ PC1 3 + Cl2 t,.n = nP - nR = 2-1 = I (given) At equilibrium, the remaining moles of A is x, because
t,.KP 'F-Kc 3x moles of C are produced.
(b) N 2 + 0 2 ~ 2N0 t,.n = 2-2 = 0 1
⇒ l -3x =x x= -
KP =Kc 4
(c) N 2 +3H 2 ~ 2NH3 t,.n=2-4=-2 . .b. K [C][D ] 3x·3x
E qm 11 num constant, c = - - - = - - -
KP 'F-Kc [A][B] (1-3x)2
(d) 2SO3 ~ 2SO 2 + 0 2 t,.n = 3 - 2 = I On putting the value of x, we get,
KP 'F-Kc I
9x -
26. 2SO2 (g) + O 2 (g) ~ 2SO 3(g)
K = 16 =2_=9
[nitially
At equilibrium
5 5
(5 - 3) = 2 (5 - 1.5) = 3.5
0
3 C (1-¾Y-¾ 1
pO 2 = mole fraction of 0 2 x total pressure
35. Given, N 2 + 3H 2 ~ 2 NH 3; Keq = 1.6 x 10-5
3.5 X 1
pO, = - - = 0.4latm
- 8.5 K = [NHJ12 = 1.6 X 10-5 ...(i)
27. The value of equi librium constant remains constant for a given eq [N2 ][H2]3
reaction at constant temperature. .
F or reaction, ____. -1 N 2 + -3 H 2
NH ..-----
3
2 2
28 _ Kc = [product], 0.4 l [product]
112 2
[ reactant] [ reactant] K' = [N2] [H2J3' ...(ii)
⇒ [product] = 0.41 x [reactant] eq [NH3]
⇒ [product] < [reactant] On squaring both sides, Eq. (ii) becomes
3
Therefore, reaction proceeds in backward direction, i.e. more PCl 5 (K' )2 = [N2J[H2] ...(iii)
w ill be formed. eq [NHJJ2
29. 3O2(g) ~ 2O3(g) On multiplying Eq. (i) and (ii), we get
0 2 and 0 3 are the allotropes of oxygen, i.e. have different Keq x (K~)2 =1
composition, so the equi librium exist between them is considered
5
as chemical equilibrium. I· 6 X 10- X (K~)2 = I

_ [product] .f K
30 ' K C - ' 1 C >> 1 K' = I 1000 = 250
[reactant] eq ✓1.6 X 10-5 4
⇒ [product] >> [reactant]
36. 3A + 4B ..-----
----"
2C + 3D
⇒ Reaction favoured more towards forward.
[C]2[D ] 3
31. From the value of Kc, the direction of the reaction may be predicted ⇒ K - ---- ...(i)
1 - [A ]3[B]4
as follows
Backward Kc Forward When moles of C = I, the equation becomes
~
~~
-
, ----+-
direction---direction -
1- ~
10-3
, ~v---
103
r-----....___ ]_ A + 2B
2
C + ]_ D
2
[C][D]312
Reaction Both reactants Reaction ⇒ K- ----
2 - [A ]312 [B ]2
...(ii)
proceeds and products proceeds to
hardly at all are at equilibrium completion On comparing Eq. (i) with Eq. (ii), we get
112
Since, for given reaction Kc = I 0-4, therefore the reaction proceeds Ki= K 1 or K 2 = (K 1)
in backward direction.
1 rmm extent= -I
H ence, eqm·1·b.
32. For a reaction at equilibrium, rate of forward reaction is equal to the 2
rate of backward reaction. 37. When two equations are added, their equilibrium constants are
33. Since, catalyst increases the rate of forward reaction as well as the multiplied. As equation III is obtained on adding equation I and
rate of backward reaction equally therefore, it does not affect the equation II,
equilibrium constant. so
 Equilibrium I 181
38. X ~ 2Y As the number of moles of products and reactants are equal, so
Initially 0 equilibrium constant is not affected by any change in pressure
At equilibriwn 1-x 2x and volume. Catalyst also does not affect the equilibrium
Total number of moles= I + x constant. It is an endothermic reaction, hence equilibrium
constant depends only upon the temperature.
r 2x i2 44. PCl 5 ~ PCl 3 + Cl 2
K = l ~·P1J = ~ _f!l_ Initially 1.6 0 0
(1 -x)·p (1 -x) (l + x) At equilibrium (1.6 - x) x x
Pl
I+ X ' Cone. at equilibrium (
1 .6
4
-x) X

4
X

4
Z ~ P+ Q Given, I .6 - x = 1.2 ⇒ x = 0 .4
Initially 0 0
At equilibrium I- x x x [PCls] = g ⇒ [PC13 ]= 0.
4
⇒ [C12 ] = 0.4
2
4 4 4
x Pl
Simi larly, K =-- --
Pi (1 - x) (1 +x)
2
Kp1 =_!_ = 4x ___f!J_ x (l+x) (1-x)
KP2 9 (1-x) (I+ x) p2 xx2
4xp
1= - I P1 I 0. 1 X 0. 1
So, -- ⇒ -=- equal Kc = 0.033
Pl 9 Pl 36 0.3
____,,.
39. ...----- 45. KP = Kc(RT)t.ng
Initially moles 5 0 0
where, ng = number of moles of gaseous products - number of
At equilibrium moles 5- 2 2
moles of gaseous reactants
3 2 2
I 1
5 4 CO(g) + O 2(g) - CO2(g) ⇒ ti.ng = 1- 1.5 = -
40%of5 = x 0 =2 2 2
100
V = 500 mL = 0. SL
2 2 K
- x- KP = Kc (RTf112, : =(RT)- 112
K _[PCIJlCl 2 ]_0.5 0.5
c- [PCl ] - 3
~ = 2.66 mol / L C
3x 0.5
5 46. NH2COONHis) ~ 2NH3 (g) + CO 2 (g)
0.5
At equilibrium if partial pressure of CO2 is p, then that ofNH3 2p
40. A very high value of K for the given equilibrium shows that 2 2 3 -5 3
dissociation of glucose to form HCHO is very-very small. Hence, Kp=fJNH3XPco2=(2p) Xp=4p ⇒ 2.9xl0 =4p
at equi librium, we can take, p 3 = 0.725 x 10-5 or p3 = 7.25 x 10-6
[Cc,H12O6]= IM 2
or p = 1.935 X 10-
K = [Ci;H1206 J, i.e. 6 x 1022 = I 2
[HCHOf [HCHOf Hence, total pressure p = 3p = 5.81 x 10- = 0.0581atm.
116 I
47. H2O(g) ----' H2(g)+
or [HCHO] = ( ~ ) = 1.6 x 10-4 M 2 O2(g)
6 X 10 Initially l O 0
Al equilibrium (I - ex) ex ex / 2
41. Relation between KP and Kc is KP = Kc(RT)t.ng (X (X
Total moles= (I - ex) + ex+ - = 1 + -
Here, ti.ng = number of moles of gaseous products - number of 2 2
moles ofgaseous reactants. Ifti.n is negative, then the relationship
between KP and Kc will be
1 Partial pressure ofH 2O = p [ l - ~]
KP= Kc (RT( "g l+ -
2
42.
Initially 3 mo l 3 mol 3 mol
At equilibrium (3 - x) mol (3 +x) mol (2 +x) mol Partial pressure ofH 2 = p [ exa]
3- x = 1.5 l+-
2
X = J.5
112
Number of mo les of PCl 3 = 3 + x = 3 + 1.5 = 4.5 . ( a /2 ) pH, .pO2
Partral pressure of 0 2 = p - - - ⇒ KP = -
I + cx / 2 pH2O
43. 2HI(g) ~ H 2 (g) + I2(g) ;-QkJ
(X3l2p'/ 2
ti.fig = number of moles of gaseous products - number of moles of
K = -----~
gaseous reactants = 2 - 2 = 0 P (I - a)(2 + a) 11 2
182 I Chapterwise & Topicwise Engineering Entrances Solved Papers
48. H i(g) + Cli(g) ~ 2HC1 (g) Note Variation of equilibrium constant w ith temperature can be
expressed as
We know that, KP =Kc· (RT)&rg
log K 2 = ~ T2 - T1 r 1
t1ng = number of moles of gaseous products - number of moles of
gaseous reactants
K, 2.303R r, · r2 l J
:. Ang =2- 2 =0 A+B~C+I
Thus, KP =Kc·(RT)° ⇒ Kµ=Kc
56. A+B~C+D
Initially 0 0
49. H2 + 12 ~ 2HI At equilibrium (.1 - x) (.1 - x) 2(.1 - x) 2(1 - x)
[nitially I mol 2 mol O Kc=[C][D ] = 2(1-x)x2(1-x)=
At equilibrium I- x 2-x 0- x 4
[ A ][ B] (1-x) (1-x)
0.2 1.2 1.6 ______.
57. 2NO2(g)
l -x ⇒ 0.2 ⇒ x= 0.8
Thus, munberofa moleofl2 = 2-x = 2-0.8=1.2
K = [NO]2 [02] = 2 x w-6
munber of moles of HI = 2x = 2 x 0.8 = 1.6 [NO2J2
50. At constant temperature pV = constant 4NO(g) + O 2(g) ~ 4NO 2(g)
On doubling p and V with constant T, the equilibrimn constant
K' = I [NO2 ]4
(K) wi ll remain constant. Pressure w ill never affect the value of
[NO]4 [02 ]2
(K)2
K. It may result in the shifting of equilibrimn, but not the value of
12 11
equilibrium constant. By doubling the volume, the concentration Equilibrium constant K' = 0.25 x I0 = 2.5 x 10
of both reactants and products evenly became half. Therefore, 58. In liquid~ Vapour equilibrium,
overall there is no change in equilibrium constant value (K).
The rate at which molecules escape from the liquid surface to
51. X(g) ______. Y(g) + Z(g) gaseous phase equals to rate at w hich molecules in the gas phase
[nitial moles 0 strike the surface and becomes the part ofliquid.
Moles at equilibrium 0.5 Hence, the molecules in the two phases have equal kinetic energy.
0.5
Partial pressure
s P 59. 3A + 2B - 2C
_ concentration of products [C]2
Total moles ⇒ 0.5 x3 ⇒ 1.5 Kc -
concentration of reactants

K = Py· Pz 60. N 2 (g) + 3H 2(g) ~ 2NH 3 (g)

⇒
p p Mole fraction ofNH3 (XNH 3 ) = 0.6
X
Mole fraction ofN2 and H2 = I - 0.6 = 0.4
p= 3atm Total number of mole of N 2 and H2 = 1+ 3 = 4
Partial pressure of X = f!_ = I = 1atrn 1 3
Then, XN2 = x 0.4 = 0.1, XH 2 = x 0.4 = 0.3
3 3 4 4
52. Partial pressure ofNi(pN ) = 0.1 x 10 = 1 atm
2
[nitially 4 4 0
Partial pressure of H i(pH 2 ) = 0.3 x 10 = 3 atm
At equilibrium 4(1-0.25) 4(1-0.25) 0.25 x 2
Partial pressure of NH 3 (pNH 3 ) = 0.6 x 10 = 6 atrn
Total number of moles at equilibrium
Dissociation of ammonia
= 4(1- 0.25) + 4(1- 0.25) + 0.5
2NH3 ~ N 2 + 3H2
= 4 - I + 4 - I + 0.5 = 6.5
53. According to law of mass action K = PN 2 x di 2 = l atrnx (3 atm}3 27 = _75 atm2
0
2 2 P P~H (6atm)2 36
[NOi)2 (1.2 x 10- ] 3
Kc= - - - = ~ - - ~ ~
[Np4] 4.8 X 10- 2 61. In the expression for equilibrium constant (KP or Kc) species in
solid state are not written, (i.e. their mo lar concentrations are
= 0.3 X 10- 2 = 3 X 10- 3mol / L taken as 1)
54. H2 + 12 2HI P4(S) + 5O2(g) ~ P4O1o(s)
I I 0 1
(I - 0.8) 2x 0.8 Thus, K -
(I -0.8) c- [Oi)5
= 0.2 = 1.6
1.6 X 1.6 62. CO(g) + 0.5O 2(g) - CO2 (g)
0.2 X 0.2 &lg = lip - nR = 1- J.5 = - 0.5
Kc=64 KP = Kc(RTi'°" = Kc(RTf 0 ·5
55. The equilibrium constant (Kp) changes only with the change in KP 1
temperan1re. Kc= ✓
RT
 Equilibrium I 183
63. Given,
... (iii)
NO2 ~ ]_ N 2 + 0 2, K 1 ••• (i)
2
From Eq. (i) and (ii)
N 2O 4 ~ 2NO2, K 2 •.. (ii)
K = K 1 X K 2 = 3.5 X 10- 3 X 1.7 X 10- 3
Required reaction
N 2 + 20 2 ~ N 2O 4 , K ... (iii) = 5.95 X 10--{i "" 6.08 X 10--{i

By multiplying Eq. (i) by 2 we get, 68. PCl 5 (g) ~ PCl 3(g) + Cl 2(g)
(J - x)
2NO2 ~ N 2 + 202, Kf
(iv) ... X X

Total number of moles at equilibrium

Now, Eq. (iii) is obtained by inverting Eq. (ii) and Eq. (iv) and by
= (1 - x) + x + x = 1 + x
adding them as.
Pro 3 =(- x
1+ X
)xp
__;. 69. Equilibrium constant for the reaction,
SO2(g) + ]_ 0 2 ~ SO3(g)
2
K - I
C - 4.9X J0- 2
1
64. SO2 + ~ and for 2SO2 + 0 2 ~ 2SO 3(g)
20 2 SO3
2
K _ [SO3 ]
Kc=( I
... (i) 2) =~=416.49 ,., 416
I - [SO2] [02]112 4.9 X J0- (4.9)2
2SO 3 ~ 2SO2 + 02 70.
2 Initially I mol 0
K _ [SO2] [02] ... (ii)
2- [SO3]2 At equilibrium 1- 0.20 0.40mol
Total moles= 1- 0.20 + 0.40 = l.20moles
From Eq. (i) and (ii)
pV = nRT
K _ _ l_ K - l
2- K2 2 - (5x10- 2)2 1 X V = 1 X R X 300 ...(i)
25x10-4
I
p X V = 1.2 X R X 600 ...(ii)
2
l00xl0 On dividing (ii) by (i)
4 x 102 atm
25 p= 2.4atm
__;.
Hp++ A - 71. When the number of moles of gaseous reactants and products is
[H O+] [ A- ] same, then equilibrium is not affected by pressure change and
K= - 3~ - - - hence, the equilibrium constant is unaffected.
[HA] [H20]
72. N 2O4 (g) ~ 2NO2(g)
66. Given, [H2 ]= 8.0 mol/L
Given, volume is halved
[I2 ] = 3.0 mol/L [HI]= 28mol/L K=? :. Pressure is doubled
H 2 + I2 ~ 2HI
:. Equilibrium w ill shift backward and degree of dissociation (a)
2
K = [HI] (28)2 = 28 X 28 = 32 _ will decreases.
66
[H2] [I2] (8) x (3) 24 KP is constant at constant temperature.
67. (i) Ag+ + NH3 ~ [Ag(NH3)] \ 73. The value of equilibrium constant is independent of volume of
container.
K, = 3.5 X 10- 3
:. Value of equilibrium constant wi ll remain same (300) if
(ii) [Ag (NH3)t + NH3 ~ [Ag (NH 3)zf volume of reaction flask is tripled.
K2 = 1.7 X 10- 3 74. H2 + 12 ~ 2HI
Initially 0.4 0.4 0
On the basis of above reaction,
At equilibriwn 0.4 - 0.25 = 0.15 0.4 - 0.25 = 0.15 0.50
K _ [Ag(NH 3)t 2
1 ... (i)
- [Ag+ ] [NH3] 0.50)
K - [HI]2 - ( - 2-
K - [Ag(NH3)zi+ . .. (ii) c - [H2 ] [I2] - (0-~5)(0-~5)
2 - [Ag(NH3)t [NH3 ]
For the formation of [Ag (NH 3)2 i+ = 0.5 X 0.5 = l J.J l
Ag+ + 2NH3 ~ [Ag(NH3)2t 0.15x 0.15
184 I Chapterwise & Topicwise Engineering Entrances Solved Papers
75. Degree of dissociation = 0.4 R= 0.00831 kJ mol - 1 K - 1
PCI _____.
KP = Kc (RT{'"g
5
a(l - x)
where, i'J.ng = (gaseous products - gaseous reactants)
a= 2, x = 0.4, V = 2 =3 -2= 1
[PCI ]=
2( 1 - 0.4) = 0.6 mol/L
5 KP= 1.8 X 10-6 X 0.0083 J X 457 = 6.836 X 10- 6
2
2x 0.4 Thus, KP >Kc
[PCl 3 ]=- - = 0.4 mol/L
2 84. NH4HS (s) _____. NH 3 (g) + H 2S (g)
2 Initially I 0.5 0
[Cl,]= x 0.4 = 0.4 mol/L
- 2 At equilibrium (I - x) (0.5 + x) X

Kc = [PCl 3 ] [Cl2 ) = 0.4 x 0.4 = 0 _267 Total pressure at equilibrium

[PCl 5 ] 0.6 = PNH3 + PH,s = 0.5 + X + X = 0.84
76. Catalyst affect both the forward and backward reactions upto x = 0.17 atm
same extent, hence it, overall does not affect the equilibrium Jwi 3 = 0.50 + 0.17 = 0.67 atm
state. However, it brings equilibrium state quickly. PHis = 0.17atm
77. N 2 + 3H 2 ~ 2NH3 KP= PNH3 · PH2S
Initially ~=2 .l!. = 4 since, n = weight = 0.67 x 0.17 = 0.1 139 atm
28 2 mol. mass _____.
.,--- 2 l(g)
At equilibrium (2 - x) (4- 3x) 2x = ~ = 2 mol,
mo! mol 17 i'l. ng = np - nR = 2 - I= 1
Hence, x = I mol Thus,KP >KcKp = Kc(RT)
Hence, number of moles ofN2 at equilibrium = 2 - I = I 2BrCl(g) ~ Cl 2 (g) + Br2 (g)
Number of moles of H 2 at equilibrium = 4 - 3 = I i'J. n =0
0
Number of moles ofNH 3 at equilibrium= 2 KP =Kc(RT)
78. There will be no effect on equilibrium constant (Kc) in presence KP =Kc
of catalyst. So, statement (c) is wrong CO(g) + 3H2 (g) ~ CH4 (g) + Hp(g)
79. i'J.n = 2-4 = -2
Initially 0.1 M 0 0 KP= Kc(RTf2
O.I _ 0. 1 X 5 0.1 X 5 0.1 X 5
Change +- -
100 100 100 KP <Kc
Equilibrium cone. 0.095 0.005 0.005 Hence, in the (iii) reaction, KP< Kc
K = (H30 + ] [ A- ] = 0.005 X 0.005 = 2 _63 X io-4. 86. The change in pressure will not affect the equilibrium constant.
c [HA ] 0.095 Equilibrium constant changes with change in temperan1re.
87. The equilibrium constant does not change when concentration of
80. H 2(g) + l2(g) ~ 2HI(g)
reactant is changed as the concentration of product also get
Here, 11ng= 2 - 2 = 0 changed accordingly.
Hence, this equilibrium reaction is not influenced by volume 88. H2 + 12 ~ 2HI
change at constant temperature. 15 5.2 0
81. Given, PCl 5 ~ PCl 3 + C1 2, K = 2.4 x 10-3 ( 15 - 5) (5.2 - 5) IO
Equilibrium constant
PCl3 + C l2 ~ PCl 5, K' = ? 2
(Kc) = (HI) = 10 x IO = 50
K' = _!_ = I = 4.2 x I 02 [H2 ] (12 ) I Ox 0.2
K 2.4 X 10- 3
_____.
.,---
82. N 2(g) + 3H2 (g) ~ 2NH 3 (g)
0 Before dissociation
i'J.n = flp - nR = 2 - 4 = - 2 1-x 2x After dissociation
Total number of moles at equilibrium
KP = Kc(RTr2or KP = Kc
(RT)2 =1-x+2x=l+x
90. According to law of mass action, at a given temperanire, the rate
_____. of reaction at a particular instant is proportional to the product of
active masses of the reactants at that instant raised to powers
which are numerically equal to the nmnber of their respective
Kc = 1· 8xl0-6
molecu les.
at I 84°C (= 457 K)
 Equilibrium I 185
91. Ni(g) + O 2 (g) ~ 2NO(g) Topic 2 Factors Affecting Equilibria
Kc= 0.1, KP = Kc(RT)t,. 11
(Le-Chatelier's Principle)
&1 = number of moles of gaseous products - number of moles of 1. Equilibrium constant depends only upon temperature, not on the
gaseous reactants concentration. Thus, it remains unchanged when an inert gas like
!!i.n=2 -2=0,l!i.n=0 argon is added. Further, argon is added at the constant volume,
KP= Kc= 0. 1 i.e. The relative molar concentration of the substance will not
change. Hence, the equilibrium position of the reaction remains
92. A(g) + 3B(g) ~ 4 C(g)
unaffected.
Initially I I 0
At equilibrium (I - x) (I - 3x) 4x 2. Heat of reaction is dependent on temperature (Kirchhoff's
equation) in heterogeneous system. Equilibrium constant is
According to the equation, I - x = 4x
independent on the molar concentration of solid species. Heat of
I reaction is not affected by catalyst. It only lowers activation energy.
x= -
5
CaCO3 (s) ~ CaO(s) + CO2 (g)
4
For above reaction, Kc= [C 1 By Kirchhoff's equation,
[A][B] 3 Af/ 0 2 (at T"JJ =Af/ 0 1 (at TJ + !!i.CP(T2 -T1)
4 0
(4x) Af/ varies with temperature.
(I - x) (I - 3x)3 Thus, (a) is correct. k = P co 2
4 k is dependent on pressure of CO2 but independent of molar
(4 x_!_) concentration of CaCO 3.
5
K = = 8.0 Thus, (b) and (c) are correct.
At a given temperature, addition of catalysts lowers the activation
C (1 - ¾)(1 -3x ¾r
energy but Af/ remain constant.
93. Number of mo les of PC1 5 dissociated at equilibrium Thus, (d) is also correct.
= 2 X 40/100 = 0.8
PC1 5 ~ PC1 3 + Cl 2 With catalyst
Initially 2 mo! 0 0 ----,,,,
At equilibrium (2-0.8) mo! 0.8 mo! 0.8 mo!
Cao +CO2
[PCl 5 ]=.!..:3_ =0.6M

I
2 E'e t!.Ho
08
[PCl 3 ] = [Cl2 ] = · = 0.4 M E'a < Ea
2 -~------~-
Kc= [PC1 3 ] [Cl 2 ] 0.4x 0.4 = 0. 266 M
[PClsJ 0.6
E0 = activation energy in the absence of catalyst
Thus, Kc= 0.266 mol/dm
3
[:. I M=moldm- 3] E;, = activation energy in the presence of catalyst
94. H 2 (g) + CO2 (g) CO(g) + H 2O(g) 3. According to Le-Chatelier's principle, if ling (change in of moles
Initial cone. I I 0 0 gaseous molecules) is greater than 0, i.e. positive, the increase in
At equilibrium (I - x) (I- x) X X pressure favours backward reaction.
PCl 5 ~ PCl3 + Cl 2
!!i.ng=2- l =l
Thus, for this reaction, the rate of backward reaction is favoured
X·X by increase of pressure.
(1 - x)(l - x) = (1-x)2 4. In the lime kiln, the reaction,
95. X(g) + Y(g) ~ Z(g) CaCO 3 (s) - CaO(s) + CO2 (g)
goes to completion because CO2 escapes simultaneously.
K _ _El_ or 104 =_El_
c - [X][Y] [X][Y] 5. Equilibrium constant is independent ofthe concentration ofreactants.
6. At constant pressure, the addition of an inert gas will increase the
[Z] = 104 [X][Y] = 104 x _!_ [Z][Z] volume of the system. Therefore, equilibrium will shift in a
2
direction to w hich there is increase in number of moles of gases.
I I
(Given, [ X]=2 [ Y]=2[Z]) For the given reaction, no. of moles increases in the backward
direction thus, equilibrium shift towards LHS.
[Z] = 2 x 10- 4 mol L- 1
7. According to Le-Chatelier's principle, equilibrium shift toward
96. 2Agp(s) ___,,_ 4Ag(s) + O 2 (g) forward direction by addition of reactant. Thus, addition of 0 2
shifts the equilibrium in forward direction.
(-: Ag and AgiO are solids)
186 I Chapterwise & Topicwise Engineering Entrances Solved Papers
8. CO2 (g) + 2Hp(g) - CH4 (g) + 2O2 (g) 19. Reaction is exothermic. By Le-Chatelier's principle, a reaction is
According to Le-Chatelier's principle, increase of temperature spontaneous in forward side (in the direction of formation of
shifts an endothermic reaction towards right. The addition of more CIF3). If F2 is added, temperature is lowered and CIF3 is
temperanire to the above reaction will cause it to right, hence it is removed.
an endothermic reaction (!iH = + ve} 20. The forward reaction is exothermic and an increase in volume is
9. N 2 + 3H 2 ~ 2NH3 + Heat taking place, Hence, according to Le-Chatelier's principle,
forward reaction will be favoured by low temperature and low
It is an exothermic reaction, so high temperature favours pressure.
backward reaction. Hence, equilibrium is shifted towards the left.
21. According to Le-Chatelier's pri nciple exothermic reactions are
10. 2SO 2 (g) + O 2 (g) ~ 2SO 3 (g) favourable at low temperanrre. The reaction in which mrrnber of
...._,__,
3 mol 2 mol moles decrease, are favourable at high pressure or low volume.
Formation of SO3 (sulphur trioxide) from SO 2 and 0 2 is C2H4 + H 2 ~ C2H6 ; l:!.H = -130 kJ mo1- 1
accompanied by decrease in volume. So, increase in pressure
·: The reaction is exothennic and number of moles of reactants
favours SO3 formation (also due to Le-Chatelier's principle).
are decreasing.
11 . Haber's process of synthesis of ammonia
·: The reaction rate is increased by decreasing temperanrre and
Fe,Mo
N 2 + 3H2 ~ 2NH 3 increasing pressure.
750K, 22. CaCO 3 (s) ~ CaO(s) + CO2 (g)
2000atm
Since, the number of molecules of gaseous products are less than The equilibrium constant for this reaction is given by K =[CO 2 ]
the number of molecules of gaseous reactants, thus, according to (as CaCO3 and CaO are solid).
Le-Chatelier's principle, high pressure favours the forward Hence, to get more CO2 , we need to pump out continuously the
reaction, i.e. more ammonia will be obtained. CO2 gas.
Electric arc
23. According to Le-Chatelier's principle, the reactions in which
12. H2 2H - I 04.5 kcal number of moles of reactants is equal to the number of moles of
Hydrogen 2000"C Atomic
molecule hydrogen products, is not affected by change in pressure.
The reaction is endothermic. For endothermic reaction, increase 2NO(g) ~ N 2 (g)+ O2(g)
in temperature shift the equilibrium in forward direction. To Moles of reactants = 2
proceed the reactant in forward direction, the pressure must be Moles of products = 2
low because for the above reaction, increase in pressure will
·: There is no change in number of moles of reactants and
favour backward reaction. So, for maximum yield, the conditions
products.
are high temperanrre and low pressure.
:. The reaction is not effected by change in pressme.
13. NHP(s) ~ NH; (aq) + c1- (aq); l:!.H = + 3.5 kcal/mo!
This is the endothermic reaction hence, increasing the Topic 3 Degree of Dissociation, Acids
temperanire will shift the equilibrium to the right.
and Bases
14. l:!.11 = - ve 1. The hydracids show a regular \{),crease in strength down a group
Takes place with decrease Takes place with evolution of because H-X KP =Kc (RT) ll _ For KP> Kc, ling should be
in number of moles or heat or increase in temperature, positive, i.e. ling is greater than zero. According to Le- Chatelier
pressme, hence increase in hence, decrease in temperanrre principle, the decrease in pressure shifts the equilibrium in that
pressme shifts equilibrium shifts this equilibrium in forward direction where the number of moles of gaseous molecules
in forward side. side. increases. Hence, the forward reaction is favoured by low
pressure, bond length increases which facilitate the removal of
15. Equilibrium is affected by temperan1re and pressure due to proton. Thus, the order would be HF< HCI <HBr < HI. Hence,
change in heat as well as c hange in volume of substances. HF is weakest acid.
16. Fusion of solid is an endothermic process, so addition of heat is 2. If acid is weak, its conjugate base will be strong. Greater the
favoured for the forward reaction (solid to melt), the amount of oxidation number of Cl, stronger the acid and thus, weaker the
solid decrease. conjugate base.
1
17. N 2 (g) + 3H 2 (g) ~ 2NH 3 (g); l:!.H = 93.6 kJ mol- HCIO HCIO2 HCIO3 HCIO4
+ I +3 +5 +7
This reaction is exothermic therefore the concentration of NH 3
can be increased by lowering the temperature, high pressme, Oxidation mrrnber of Cl and acid strength increases
(fin< 0) excess N 2 and H 2 .
Clo- CIO2 ClO3 CIO4
18. N 2 (g) + 2H 2 (g) ~ 2NH 3 (g) + 92.3 kJ
According to Le-Chatelier's principle, the favourable conditions (Conjugate base strength increases.)
for the forward reaction are : Hence, c 1O- is the strongest base.
(i) Low temperature (as the reaction is exothermic)
(ii) High pressure (volume is decreasing)
(iii) Constant removal of ammonia gas as it is formed.
 Equilibrium I 187

3. In O lone pair of ni trogen is not involved in resonance as

13. [H+) = Ka ·C
Given, [H+] HCOOH = [H+ l ett 3cooH
N Ka ·C = K:c·
I ⇒ 1.8 x 10-4 x 0.001 = 1.8 x 10- 5 x C'
H
well as it has less s-character than the nitrogen of pyridine, hence the C'=0.01 M
former is better electron donor.
14. When two - OH groups are attached w ith same carbon
4. In AICl 3, Al has an incomplete octet, thus, it is an electron deficient atoms, the compound is highly unstable and loses a water
molecule, so it acts as a Lewis acid. molecule,
5. According to Lewis, "a base is a species w hich can donate an electron e.g. CH z(OH)i ~ HCHO
Unstable 2
pair." In NH3, N has one lone pair of electron.
/ OH
Thus, NH3 is a Lewis base. CH3CH - --+ CH3CHO
"--oH - H20
6. According to Lowry-Bronsted concept of acid and bases, an acid is a
Ca(OH)2, being an ionic compound readily gives two hydroxyl
proton donor whereas a base is a proton acceptor.
ions when dissolved in water, hence it is a diacidic base.
7. ·: pKa =- logKa
Ca(OH)2 - Ca 2+ + 2OH-
:. pKa for benzoic acid= - log (6.3 x 10- 5 ) Diacidic base
= - log 6.3 - log 10- 5 15. Lewis acids have a tendency to accept electrons while
Bronsted acids have a tendency to donate proton.
= - 0.799 + 5 = 4.201
(a) pKa for A = - log (1.67 X 10- 8 ) (a) HCI - H+ + CI-
Bronsted acid
= - log 1.67- log 10- 8
(b) H 2SO4 - W + HSO4
= - 0.222 + 8 = 7.778 Bronsted acid
(b) pK0 for B = 6.0 (c) HSO3 - H+ + SO~-
Bronsted acid
(c) pKa for C = 4.0
• • 2-
5
(d) pKa for D = - log (1.0 x W- ) (d) s03 + :~ : - so~-
= - log 1.0 - log 10- 5 = O+ 5 = 5 r..ewis acid
For a stronger acid, pKa must be less. Therefore, acid C will be 16. According to Bronsted-Lowry concept, bases are the substance
stronger than benzoic acid. which have a tendency to accept a proton.
8. For a diprotic acid, further ionisation is difficult, therefore (a) H 2SO4 + H 2O - Hp+ + HSO4
Ka,> Kai Acid Base Conjugate Conjugate
acid base
9. Na 2O + H 2O - 2NaOH
Oxidation numberofNa +I +I (b) H 2O + H2O - H 3O+ + OH-
Oxygen -2 -2 -2 Acid Base Conjugate Conjugale
acid base
There is no change in oxidation number, so (a) and (d) are not trne.
This reaction shows amphoteric nature ofH2O
(b) is also not trne.
•• 2- (c) H 20+ NHz - NH3 + OW
:..o: + H- O- H- 2OH Acid Base Conjugate Conjugate
acid base
Oxide ion donates a pair of electrons, thus, changes to OH-. (d) Hp + NH3 -➔ NH! + OW
Acid Base Conjugate Conjugate
10. C 1<XT =C2<X~ acid base
0.1 X 12 = 0.025 X<Xi
17. Higher the tendency to give H+ ion, (i.e. to undergo
a~=4 ⇒ a=2 ionisation), stronger will be the acid or vice-versa.
11. Only in reaction (ii) H 2PO4, gives H+ to H 2O, thus, behaves as an HF has poor tendency to give if ion, hence it is the weakest
acid among the given.
acid.
The order of acidity of given acids is
12. Electron acceptors are Lewis acids. They are electron deficient
compounds. BF3 is Lewis acid because B has only 6 electrons in its H 2SO4 > HNO 3 > HCI > HF.
valence shell and it can accept electrons to complete its octet. NF3, 18. A hard acid has high charge density, shows preference for hard
Cl- and H 2O have lone pair of electrons. Thus, they are electron bases, i.e. for atoms of high electronegativity. Moreover, its
donors and Lewis bases. outer electrons are not easily distorted, i.e. it is non-polarisable.
188 I Chapterwise & Topicwise Engineering Entrances Solved Papers
19. Acidity order 26. Conjugate acid and base differs by a proton. Thus, the conjugate
0 base ofH 2PO4 is HPO/ -
II + H2PO4 + H 2O - H 3 O+ + HPOi-
H-O - S - F > H- O-H > Acid Conjugated base
II I
0 H 27. Proton affinity meane affinity for proton, i.e. basicity. NH3 has a

0 0 higher tendency to donate its lone pair of electrons present on N

II e II due to lower electronegativ ity ofN atom. In PH 3 Pis not suitable
H-O - S - O> H- O- c - o - as it has large size.
11 28. Acid 1 + Basei ~ Acid 2 + Base,
0
HPO~- + H 20 _),. H 3O+ + Po~-
(Conjugate anion decreases acidity)
-----'- H3O+ + RPO~-
20. HPO~- + H2 0 ~ H2P0 4 + Olr
HPOi- + H 2O ~ PO[ + H 3O+ H 3PO4 + H 2O ~ Hp + + H 2PO4

H 2PO2is a conjugate base ofH 3PO2 (a monobasic acid) and does 29. According to Bronsted and Lowry concept, a substance is known
not give H+, HPOj- is a conjugate base of H 2P0:3and does not as an acid ifit can donate a proton and as a base if it can accept a
proton.
ionise further, since H 3PO3 is a dibasic acid.
30. The ionisation of strong electrolytes in acetic acid, compared to
21. A Lewis acid is a substance, which can accept a pair of electrons,
water, is weak and low because acetic acid is a non-polar solvent.
e.g. H 3O+.
31. Acid, [H+ ] = 10-pH = 10-5
22. The substance which can donate a pair of electrons is called
[if ] =Ca
Lewis base.
[H+ ] actual ionisation lO- s = 0.2 X 10- 2
Amines contain lone pair of electron on nitrogen atom, so behave (X ⇒-- (X =- - - - - - -
as Lewis base. c ' molar concentration 0.005
23. The weak electrolyte AxBy dissociates as follows Note If % is asked then% ionisation
= 0.2 XI0-2 X 100 = 0.2%
AxBy ~ xA y+ + ySX-
32. AIC13 is a Lewis acid because it is e lectron deficient species. As
c O 0
Al has an incomplete octet.
C(I - Ot) xCOt yCOt
33. Base + H+ - Conjugate acid
where, ex = degree of dissociation
C = concentration
S2O~- + H+ - HSiO8

K = [Ay+ t rsx-v t
[xCa [yCcx V
:. HSz08 is conjugate acid of S2O~-
eq [AxBy ] C(l - cx) 34. The CH3 COOH is weaker acid than H 2SO4. The reason is that

xx ,Cxax, y'-CY. aY CH 3COOH is weakly ionised in comparison with H 2SO4.

K = ------- [·: 1- a = I] 35. The species which can donate a lone pair of electron, are called
eq C
Lewis base, e.g. NH 3,H2O, Cl- , etc.
Keq = f . yY-(XH y . ex+ y - 1
36. HNO3 (nitric acid) is generally not an amphoteric substance. It is
cxx+y = K•q a strong acid (proton-donating) though sometimes, in presence of
f . yY·Cx+ y - I stronger acid, it also acts as a base (e.g. in nitration of aromatic
compotmds, it acts as a base and accept proton from H 2SO4).
However, HCO3, H 2O and NH 3 frequently act both as an acid as
well as a base (i.e. amphoteric in nature).
37. Thus, the conjugate acid ofNI-fi is NH 3 .
24. When a base accepts a proton, then an acid is formed. This acid is Base + if - Conjugate acid
known as conjugated acid of that base.
e.g. NH3 + H+ ~ NH; NH3
Conjugate acid
Base Conjugate acid
38. Ostwald dilution law states that, "the degree of dissociation is
Thus, the conjugate acid of HF2 is H 2F2.
proportional to the square root of dilution for weak electrolytes.''
HF2 + H+ - H 2F2 Degree of dissociation of weak electrolytes increases with
Base Conj ugate acid dilution.
25. K = k1 X k2 = 1.0 X 10- 5
X 5.0 X 10 - 10
= 5 X 10- 15 Hence, ostwald's dilution law is applicable for weak electrolytes.
 Equilibrium I 189
39. According to Lewis acid, it is any species (molecule, radical or 49. According to Lewis, electron deficient species are called acids
ion) that can accept an electron pair to form a coordinate covalent while bases are the substances w hich have unshared pair of
bond. Thus, acid is an electron deficient species, e.g. BF3, AlCl 3, electrons and can donate the electron pair to the formation of
SO 3 and all cations, etc.
coordinate bond.Hence, H 2 0: is a Lewis base while Bf:i,AlC13
AlC1 3 + : c1 :- ~ Cl 3Al <- Cl :- or AlCI;1 and SO2 are Lewis acids.
Lewis acid Le~; base Adduct.. 50. Electron donors are Lewis base.
In the reaction 12 + r ~ I;,r donates a pair of electron and 12
40. Among the given species, correct order of increasing acidic
strength is accepts it to form 13.
mr < H2O < NH; < HF < H3O+ 51. Simple cations such as Ag+ , eu 2+, FeJ+ etc., can accept pairs of
OH- is basic, (i.e. it tends to gain a proton) and hence, it is least electrons and hence, are Lewis acids.
acidic. H 2O is neutral species. H 3O+ is most acidic as it can
readily lose a proton. Topic 4 pH Value and Related Terms
41. For weak electrolytes, according to Ostwald's dilution law 1. m mol ofW (initial)= 200 x 0.031 x 2 = 12.4
(X =-fKv
m mol of OW (initial)= 84 x 0. 15 = 12.6
Where, V = dilution of solution
Here, O'. = 0.01% = 0.0001 = 1 x 10- 4 m mol ofOH- (left) after neutralisation= 12.6-12.4 = 0.2
I
Now V = - = - = 1L
1 [Off] =__Q2 = 7 x 10- 4 M
fiooJ 284
' C 1.0
pOH = log (OW) ➔ - log (7 x 104)
K = O'. 2 = (1 X 10-4)2 = I X 10-8
a V I pOH = 3. l 5and pH = I 0.85
42. Lewis bases are electron rich compounds. : . pH= 14-pOH =14-3.15 = 10.85 = 10.9
2. 10- 4 MKOH = 10- 4 M Off
(i) NH 3 and H2 ~ are Lewis bases because they have lone pair of
We know that,
e lectrons.
[W] [Off l = 1 X 10- 14
(ii) AlC13 is a Lewis acid because it can accept electrons.
(W ]x 10- 4 = IX 10- 14
43. Conjugate base is formed by loss of H+.
OH- ~ 0 2- + H+ [W]= lxl0- 14 =lxto- lOM
2 IX 10- 4
0 - is the conjugate base of OH-.
44. For base BOH pH= - log [W ] = - log (1 x 10- 10) = 10
BOH ~ B+ + OW
3. M illiequivalent of H+ = IO x 0. 1 x 2 = 2
. . . [B+][Off]
D1ssoc1at1on constant Kb = - - - - Milliequivalent of Off = IO x _2... = 1
[ BOH] 10
: . Higher the value of Kb, more will be the dissociation of base Since, meq. of H+> meq. of OH-, thus, the resulting solution
and stronger will be base and vice-versa. should be acidic
: . Weakest base among given choices is having Kb = 7.2 x 10- 11. 2 1
Normality of solution= - = _!_ = 0.05 N
20 20
45. The species which can accept as well as donate H+ can act both as
an acid and a base. Mola1ity of the resulting solution
= 2 X 0.05 = 0.]
HSO4 + H+ H 2SO4
Base pH of the solution = - log [H+] = - log (0.1) = - log (Io- 1) = I
HSO4 so~- + 4. pH range of human blood (blood plasma) is 7.36 - 7.42
Acid
46. NH3 (ammonia) possess an unshared electron pair on N-atom 5. pH= - log[W ] = - log (3.8 x 10- 3)
hence, it can donate electron pair. Such species are called Lewis = - log 3.8- log 10- 3
bases. BF3 acts as a Lewis acid. While PF5 and AsF5 have
= - 0.5798 + 3 = 2.4202
incomplete octet with no lone pair of electrons.
6. pH= I
47. Lewis acids are those species which can accept a lone pair of
electron. BF3,AlCl 3,SnC14,FeC13 etc., are Lewis acids. NC1 3 and [W ] = 10- 1 = 0. I M pH = 2
ROR are Lewis bases. HCI is acid according to the concept of [H+] =l0- 2 =0.0IM
Arrhenius and Bronsted-Lowry.
For dilution ofHCl, M 1V 1 = M 2V2
48. (i) BF3 and BC13 are better Lewis acids than BMe3 and B 2H6 due 0.1 X 1 = 0.01 X V2
to - /-effect of Cl and F.
V2 = 10 L
(ii) Between BC13 and BF3,BC13 is better Lewis acid due to lesser
Volume of water to be added = (JO - I) L = 9 L
extent of prt - prr, back bonding in it.
190 I Chapterwise & Topicwise Engineering Entrances Solved Papers
7. We know that, 20 mL of0. I N HCI contains Concentration of solution, M 2 = I0--4M
[W ] =~ X 0.1 = 2 X Io- 3
mo!. V2 = 400 mL
1000 ⇒ Concentration of resulting solution
Simi larly, 20 mL of0.001 N KOH contains
M = M1V1 + M2V2 10-3 X 100 + 10- X 400
4
0.14
- 20 -5
[ 0 H ) = - - x0.001=2x l 0 mot V 1 + V2 100 + 400 500
1000
The [H+ ] in the mixture = 0.00028 = 2.8 X 10- 4
= (2 X 10- 3) - (2 X 10- 5) = 1.98 X 10- 3 [H+ )= 2.8 X 10- 4
3 :. pH of resulting solution = - log (H+ )= - log (2.8 x Io- 4 )
[W] = 1.98 x 10- = 4950 x 10- 5
40 X 10- 3 = - log 2.8 - log 10- 4 = 4 - log 2.8
pH = - log [W] = 5 - log 4950 13. ·: [H3O+ )= 10- 4
= 5 - 3.6964 = 1.3 :. pH = - log 10- 4 = 4
8. HQ - W + Q- [H+ ] = .jKC (by Ostwald's di lution law)
0 :. Solution will be acidic in nature.
[H+ ] = 10- pH = 10- 3 M (C = 0.1 M) 14. HA (a weak acid) ionises as
Thus, 10- 3 =.JK0 x0.I HA _____. H+ + A-
o 0
10-6 =K0 XO. I
(1 - 10-') 10- 5 I0- 5
Ka= 10-5 [A- ] = [H+ ] = 10- pH = 10-5 M
9. [H3O+ ] = .JK0 X C =.J4 X 10-IO X 25 X IQ-I K
[H+ )[A-)
= ~~~~ =
10-5 X 10-5 10-IO
= --
=~ = 10- 5M a [HA J (1 - 10-5) 1

pH= - log [H3O+ ] = lx10-10 M

15. 2Na + 2H2O - 2NaOH + H 2
pH=-log(I0- 5)=5
2mol 2mol 2 mol
1 O. Milliequivalents of 20 mL of 0.1 N HCI = N 1V1 = 20 x 0.1 = 2 0.023
For Na, number o f moles= - - = I o-3 mot
(a) pH of distilled water= 7 23
[H +] = 10- pH = 10- 1 M
For H 2O, number of moles = ~ = 4.46 x 10-3 mol
: . Milliequivalents = NV for HCI, N = M] 22400
= 10- 7 X 20 = 2.0 X 10- 6 nNa < nH 2O
(b) Milliequivalents ofNaOH = 0.1 x I = 0.1 Thus, Na is the limiting reagent and decide the amount ofNaOH
(c) pH ofHCI = I formed.
I mole Na gives NaOH = I mol
[W ]= W-1 = 0.1 M
Ix I0-3 mole of Na will give NaOH = I x I 0-3 mol
: . Milliequivalents = 0.1 x 500 = 50
n
(d) Milliequivalents ofHCI = 1 x I = I [OH- ] ⇒ NaOH

·: Milliequivalents of 500 mL ofHCI having pH = I, is more than volume

that of 20 mL of 0.1 N HCI, therefore adding this, pH of 0. 1 N V= I 00mL or 100cm3
HCI solution does not alter. . _ IX 10-3 X 1000
11 . Milliequivalents ofNaOH = N I V1 = 0.4 x 5 = 2 Concentration of[OH ] = - - - - - Ix 10-2
100
Milliequivalents ofHCI = N 2V2 = 0.1 x 2 = 2 pOH = - log [Off)= - log (I X 10-2) = 2
: . Milliequivalents of NaOH (base) = milliequivalents of HC I pH= 14 - 2 = 12
(acid)
16. Among the given, pH of0. I M CH3COOH is not equal to one as
: . Resulting solution will be neutral.
CH3COOH is a weak acid, thus, does not ionise completely.
: . Its pH= 7 10
17. Given, concentration ofNaOH = I 0- M
12. For solution I, pH = 3
NaOH - Na++ OH-
⇒ 10- 10 10- 10
10- 10
⇒ Concentration of solution, M 1 = 10- 3 M [Off]from NaOH = 10- 10 ⇒ [Off]from H 2O = 10- 7
V1 = I00mL Total [OH- ) in a solution of NaOH = 10- 7 + 10- 10

For solution II, pH= 4 ⇒ [H+ ) = I0- 4

= 10-7 (I+ 0· 001) = 10-7 ( JQQI) = 10-IOX 1001
1000
 Equilibrium I 191
pOH = - log [Off] [Off]= 0.2 x 10-2
10
= - log (1001 X 10- )= -3.004 + 10= 6.9996 10-14
[W ]= _ = 5 x 10- 12, pH= -log [H+]
pH +pOH =l4 0.2xl0 2
pH= 14- 6.9996= 7.0004 ::::7 pH =-log[5xl0-12], pH= l l.3
18. pH varies inversely with temperature. Thus, if the pH of neutral 25. pH = 0means[H+] = I o0 = 1 M. Hence, solution is strongly acidic.
water is 6. 5, the temperature of water is more than 25° C.
26. Strong acids have low pH value while strong bases have high pH
19. [H+ ] for the solution of pH 3 = I x 10- 3 value. Hence, the order of pH is
[H+ ] for the solution of pH 5 = I x 1o- 5 HCI < CH 3COOH < NH4 Cl < CH3COONa
Strong Weak Salt of weak base Salt of weak acid
Let V volumes of both the solutions are added, then concentration acid acid and strong acid and strong base
ofH+ in final mixture
1 X 10-3 XV+ IX 10-5 XV V(I X 10-3 +IX 10-5) 27. [H+ ]= ✓Ka x C = ,J10-5 x 0· 1 = ✓10-6 = 10-3
V+ V 2V pH = - log [W ]= - log 10-3 = 3

1.01 X 10-3 I
5.05 X 10-4 28. pKa oc -

2 Ka
pH of resultant solution = - log [H+ ]= - log (5.05 x Io- 4 ) Stronger the acid, higher the Ka value and lower the pKa value.
The order of acidity of given acids is as
= 3.29"' 3.3
20. Aqueous solution of NaCl salt of strong acid and strong base is TH3CHCOOH > CH31HCOOH
neutral. So, its pH value is 7. F Br
21. Given, for NaOH, V = 10 mL, N = 0.1 N [Due to more electronegative
F-atom attached to Cl-C-atom J
For H 2SO 4 ,V = I0mL,N =0.0SN
>FCH3C~COOH > CH 3C~COOH
Milliequivalents ofNaOH = IO x 0.1 = I [F-is attached to JH::-atom
Milliequivalents of H 2SO 4 = IO x 0.05 = 0.5 F which reduces acidity )
H 2SO 4 + 2NaOH ~ Na2SO4+ H 2O I
I equivalent 2 equivalents
Since, CH3CHCOOH is the strongest acid among the given, its
0.5equivalentofH2SO4 will react with I equivalentofNaOH pKa value will be lowest.
: . The pH of solution = 7 (neutral) 29. In water, barium hydroxide is hydrolysed as follows
22. Total milliequivalents ofH+ = 30x_! + 20x_! = 20 Ba (OHh ~ Ba 2+ + 20ft
3 2
Concentration, ofBa 2+ = Ix 10- 3 M
Total milliequivalents of Oft= 40x_!_ = 10
4 Concentration of [OH- ]= 2 x Ix 10- 3M = 2 x 10- 3M
Milliequivalents of H+ left= 20- IO = I0 [·: Ba(OH)z has 20W ions]
3
[H+ ]= _!_Q g ions/ dm = _! pOH = - log [OW ]= - log (2 x 10- 3 )= 2.69
90 9 pH + pOH= 14
pH=! pH= 14 - pOH=14 - 2.69= 11.3 "' 11.0
10
23. [OW ] in the diluted base =
10
= 10-8 7 30. [OW]= ✓Kb x C = -J1 x 10- 5 x 10- 1 = ✓10-6 = 10- 3
Kw = [H+ ] [OW] ⇒
Total [OIr]=l0-8 +[OIr ] ofwater=(I0- 8 + l0-7 )M
[H+ l = 10- 11
= 10-8 [1+ I0]M= 11 x W-8 M
Hence, pH = - log H+ = - log (Ix 10- 11 ) = 11
pOH = - log 11 x 10-8
= - log 11 + 8 log IO = 6.9586 (cone. of acid x its vol. )
. f . -(conc.ofbasexits volume)
pH = 14 - 6.9586= 7.0414 31. C oncentration o mixture= - - - - - - - - - -
total volume
24. Concentration ofHCI solution= Ix 10-2 N=N 1V1 - N 2V2 =50xl - 30x l
: . Millimoles ofHCl solution = 200 x I x 10-2 = 2 V1 + V2 50 + 30
Simi larly, millimoles ofNaOH solution 20
=
= _!_ = 0.25
= 300 X IX I 0- 2 = 3 80 4
Concentration of the resultant, i.e. [OH-] basic solution Since, HCl is in excess, so mixture is acidic and mixture contains
[H+ ] ion. Thus,
3- 2 - 1- =o.2x10-2
300+ 200 500 [H+ l = 0.25
192 I Chapterwise & Topicwise Engineering Entrances Solved Papers
pH= - log[H+ ]= - log (0.25] 41. Given, aqueous solution ofNH/ weak base) (C) = 0.0 1 M

= - log
2.5
= - [log2.5 - logl0] a = 5% = - -
5
[OW J= co:= 0.01 x ~ = 5 x 10- 4
10 100 100
= - (0.3979 - I) = 0.6021 pOH = - log [OW ] = - log (5 x 10-4)
32. pH = - log [H+] = 4 log 10 - log 5= 4 - 0.6989 = 3.3010
[H+] = 0.0001 =I x 10- 4 pH = 14 - pOH = 14 - 3.3010 = 10.6990

pH= - log(l x 10-4 ]=4 42. 100 mLof0.01 MNaOH solution is diluted to ldm 3, (i.e. 10 times
diluted hence, the resultant solution will be 0.001 M)
33. If the concentration of acid is less than I0- 7 , then the [OW]= 0.00 1 = 10-3
concentration of H+ present in water is not neglected. 10-14 10- 14
Total [H+ ] = [H+ ] from HCI + [H+ ] from H 2O [H+ ] = [Off i= 10-3 = 10- 11
= 10-8 + 10- 7 = 10- 7 ( I. I)= I.I x 10- 7 mol/ L 11
pH= - log [H+ ]= - log(I0- ] ⇒ pH = II
pH = - log [H+ ]= - log (I.I x 10-7 ) = 6.96
43. [OH- ] in NH pH solution = Co:
34. (a) pH of!0- 9 M HCI will be < 7
= 0.001 X _ I_ = I X 10- 5
(b) pOH oflo-5 MNaOH= - log[OW]= - log [ I x 10- 5 ] = 5 100
pH + pOH = 14 pOH= - log[OW ]
pH =l4 - 5=9 pOH = - log ( I X I o- 5 ] , pOH = 5
35. N = N 1V1 + N 2V2 (-: ForHClN =M) 44. I mole ofM Ba(OH)i solution contains 2 moles of [OH-] ions
V1 + V2
Thus, [OHf = 2x 0.05 = 0.10 M
= 0.015 X 100 + 0.005 X 100 = 1.5 + 0.5 = - !- = l0- 2
100+ 100 200 100 pOH = - log [OW ] ⇒ - log (0. 10) = I
Resulting solution is acidic in nature . pH = 14 - pOH = 14 - I = 13
Then, [H+ ] = 10- 2 45. Normality = molarity x valence factor
+ I I . N I
pH= - log [H ] = log - +- = log - 2 = 2 log 10 = 2 Molanty =- = - - -
[H l 10- VF I000 x 1
9
(c) pH of!0- M KOH will be slight ly greater than 7. :. Molarity of KOH, i.e. [KOH) = 0.00 IM
Thus, [Off ] = 0.001= l x l 0-3 M
36. From HiO, [H+ ] = I x 10- 7 M
pOH = - log [OW] = - log (Ix 10-3 ]
From HCI, [H+ l = IX I o- 8 M
= - log !- log 10-3 = 0 + 3 log 10= 3
Total [H+ ] = (I x10- 7 + I x 10- 8 ) M
pH + pOH= 14
= (1 X 10- 7 + 0. 1 X 10- 7 )M = I.I X 10- 7 M
pH= 14 - pOH = 14 - 3 = 11
pH= - log (I. I x 10- 7 ) = 6.9586
46. Let oxalic acid= x mol/ L
37. [H+ ] [Off] = I 0- 14 M 1V1 =M2V2
- 14 16x0.05 I I
10
(10- 2) [Off] = 10- 14 ⇒ [Off]= _2 = 10- 12 mol dm- 3 40 mLXx = 16 mL X 0.05,x = - - - = - , x = - M
10 40 50 50
38. pH = - log [W] = - log [ 0.005 ]= - log [ 5 x 10- 3] = 2.3 Now, convert molarity into normality
N x eq. wt. = M x mo!. wt. of oxalic acid
39. H 2SO4 ~ 2W + so~- I I
N X 45 =- X 90, N = -
(H2SO4]= 0.005 M 50 25
Since, H 2 SO4 re leases 2 H+ ions. This normality represents the hydrogen ion concentration.
[W ]=2 x 0.005 M =0.0 1 M So, (H+ ] =~
25
⇒ pH=- log[W]pH ⇒ -log[ff]
I
⇒ - log[! x 10- 2 ] pH ⇒ 2 pH= - log [W ] = log 25 = 1.3
4 4
40. [Off ]in 10- M KOH solution = 10- M 47. 10-2 M H 2SO4 = 2x 10- 2 N H 2SO4
(KOH is a strong electrolyte) [H+ J= 2 x I 2N o-
14
[H+ ] = ~ = l x l0- = l xl0- 10 M or pH=lO pH = - log (H+ ] = - log (2 x 10- 21
[OW ] 10- 4
= 2 - log 2 = 2 - 0.3010 = 1.6990
 Equilibrium I 193
48. ·: pH=2 Let the solubility of Ca(OH)z be S mol L- 1
Ksp = [Ca 2 + ] [Off] 2 = S · (2S)2 = 4S 3
2
[H+] = 10- , [H+ ] = C·a
10-2
10-2 =0.1 X(X,,(X, = - ,(), = 0.1 Given, solubility, S = .fS
0.1
On substituting value of S, we get
49. pH= 5.4 K'!iP = 4(.J3)3 = 4 X 3 .J3 = 12..J3
5.4=- log[W] ⇒ [W]=I0- 14
3. NaOH ~ Na+ + OH-
Antilog of 0.6 is "'4 c C

[H+ ] "' 4 x 10--6M Ni(OH)2 --'- Ni 2+ + 2OH-

X X X

50. pH of a solution oc [OH- ] M Ca(OH)z solution will give highest Total [OH- ] =x + C
4
K'!iP = [Ni 2+ ][Off ] 2 = x (x + C) 2 = x (x2 + 2Cx + C 2)
concentration of [OH- ]. Hence, it has highest pH.
2
51. (i) 20 mL of0.5 N HCI or K '!iP = xC (neglecting higher powers of x)
0.5 N ⇒ 1000
rnL of0.5 mole ofHCI X = K'!if) = 1.9 X 10-15 1.9 X 10-15 M
20 0 5
HCI present in 20 mL = x · = 1.0 x I 0- 2 C2 (1)2
1000
4. For CaCO 3, solubility can be calculated as
(ii)35 mLofO.l NNaOH 0. l N ⇒ l000mLof0.1 moleofNaOH
CaCO3 ~ 2+ ea co~-
⇒ NaOH present in 35 mL = 35 x O. l = 0.35 x 10- 2 s s
1000 2
Total volume= 20 + 35 = 55 mL Ksp = S·S = S ⇒ S = .jif;
⇒ Resulting mole in solution, = ✓8.7 X 10- 9 = 9.3 X 10- 5
(1.0 - 0.35) I 0-2 = 0.65 x 10- 2 mole HCI
For CuS, solubility can be calculated as
HCl =H+ + Cl- CuS ~ Cu 2 + + s2-
s s
[HCl] = [H+] + [Cl- ] 2
Ksv = S·S = S
55 mL contains 0.65 x 10- 2 mole ofIr ions
2 3
J000 mL = 0.65 X 10- X 10 = 6.5 s = .jif; = ✓8.5 x 10- 45 = ✓85 x 10- 46
55 55 = .f8s X 10- 23 = 9.2 1X 10- 23
pH= - log [H+ ] = - log (6.5/ 55)
For Ag2CO 3 solubility can be calculated as
= log55 - log 6.5 = 0.92 Ag2CO3 ~ 2Ag+ + co~-
Due to acidic nature of solution, the colour of phenolphthalein 2S s
becomes pink.
52. [Off] = 1 x 10- 5
K'!iP = (2S)2 · S = 4S 3, S = 4¥
pOH = - log [Off]= - log [l x 10- 5]
S = ~6.2 X410-12 = ~1.55 X 10- 12 = 1.1 5 X10-4
pOH = 5, pH + pOH= 14
pH= 14- pOH = 14 - 5, pH= 9 For existence of Pb9 IO3, there must be IO3 and Pb; present as
53. Aqueous solution of lM NaCl and IM HCl is not a buffer but constin.1ent ions but in real Pb; - exist as ion. When we match the
pH < 7. K sp value of iodate of lead, we found that compound must be
Pb(IO 3)i.
Topic 5 Common Ion Effect, Ionic Now, we can calculate solubility of compound as
Product of Water and Pb(IO 3)z ~ Pb+ + 2103
S 2S
Solubility Product 2 3
K '!if) = S · (2S) = 4S
1. Ag2CrO 4 ~ 2Ag+ + Cro;- ; Ksp = (2S)2 S = 4S 3

---f
2S s
S = K ) "3 = ( 32 X; 0- 12) 3 = 2 X 10- 4 M
11 S = 4¥ ~¥- = X 10-
13

(
= 3 260 X l0-15
4
2. In aqueous solution, Ca(OH)2 is represented as
Ca(OHh ~
2
Ca + + 2Off = 1/65X 10- 5 = 4.02 X 10- 5
S mol L- 1 Hence, maximum solubility has been observed for (c), i.e. Ag2CO 3.
194 I Chapterwise & Topicwise Engineering Entrances Solved Papers
5. For any stoichiometric reaction, suppose, S4 = J.6 X 10-30
AxB/s) <=> xAY+(aq) + y B' -(aq) 27
[A y+ f [Bx- v S = l.6x 10-30
4
K = "--~'----"-~
[AxBy] 27

The solubility product for the reaction is

2 2 1
13. [Zn + ][S -] = 10- x 8.1 x 10-19 = 8.1 x 10- 20
20
K [AxBy ]=Ksp = [A Y+ y [B-'-]Y Thus, ionic product of ZnS,(i.e.8. l x I 0- ) > Ksp of

For, x = 2 and y = 3 ZnS(3 x I 0-22 )

A2B3(S) <=> 2A 3+ (aq) + 3B 2 -(aq) [Cu 2+ ][s2-1 = 10- 2 X 8.1 X 10- 19 = 8.1 X 10-21

Ksp = [A 3+ )2 [B2-]3 Thus, ionic produce ofCuS, [i.e. 8.lx l 5-21) is greater than K ,p of
CuS ( 8 x 10-36 ) Hence, both ZnSand CuSwill precipitate.
6. In the presence of common ion (in this case Ag+ ion) solubility of
sparingly soluble salt decreases. 14. AgCI ~ Ag+ + c1-;Ksp = [Ag+ ][cl- ] =S 2
s s
Let solubility of Ag2Cr04 in the presence ofO.l M AgN03 =x
S = Ji<;; = 1.1 X 10-IO = 10-5
Ag2Cr04 ___,, 2Ag+ + Cro!-
2x X Similarly, S for Agl is 10-s, S for PbCr04 is 2 x 10- 7 and S for
AgN0 3 __,,, Ag++ N03 Ag2C03 is 1.26 x I 0-4.
0. 1 0. 1
Most soluble Ag2C03, least soluble Agl.
Total [Ag+]= (2l: + 0. 1) M
15. CaiP04)z (s) ~ 3Ca2 + (aq) + 2Po! - (aq)
o: O.IMasx«<O.lM [Cro; - ]=xM 3y 2y
2 3 2
Thus, 2
[Ag+ ] [CrO~-] = Ksp Ksp = [Ca + ] · [PO!- ] = (3 y)3 •(2y)2
= 27y3x4 y = 1O8y 5
12 2
(0.1)2 (x) = 1.1 X 10-
X = 1.1 X 10-
10 M 16. Ksp =[Ag+ ][Br-] = 5.Ox 10- 13
13
7. PbBr2 ~ Pb2+ + 2Br- 50 11
[Ag+ ] = 0.05 M , [Br- ] = · ;.~~- = I x 10- M
Initially I 0 0
After 80% (1 - 0.80) S 0.80 S 2 X 0.80 Moles ofKBr = 1 X 10-11 X 1 = I X 10- 11
ionisation = 0.20 S = 1.60 S
Weight ofKBr = IX 10-11 X 120 = 1.2 X 10-9 g
: . Solubility product, Ksp = [Pb2 +] [Br- j2
17. Mg(OH)i ~ Mg2 + + 20ff
= (O.8OS) (l .60S)2 = 2.O48S 3
Ksp = [Mg2+ ][Off ] 2
8. The solubility product of a binary weak electrolyte = 4 x Io- 10
Solubility= .j4 x 10- 10 = 2 x 10- 5 [OW]=~

9. CaF2 ~ Ca 2 + + 2F-
s 2S [Off]= I.Oxl0-11 =10- 4
[Ca2 + J = S, [F-] = 2S 0.001

Ksp = [Ca 2 + ][Fr2 = S (2S)2, Ksp = 4S3 pOH = 4 and pH = I 0

18. Given, concentration of NaCl= 0.2 M
10. In acidic medium, H 2S is very feebly ionised giving very small
Ksp(AgCI) = 1.20 x 10-10
concentration of sulphide ion for precipitation. T herefore, the
most insoluble salts CuS and HgS are precipitated only. Let the solubility of AgCI in NaCl = x
11. It is a case of simultaneous solubili ty of salts with a common ion. AgCI - Ag+ + Cl-
Here, solubility product ofCuCI is much greater than that of AgCI, x X X

it can be assumed that c1- in solution comes mainly from CuCI. Solubility NaCl - Na+ + Cl-
0.2 0.2 0.2
⇒ [Cl-J=.jKsp(CuCI) = 10- 3 M [Ag+ ] =xand [Cl-] =(x+ 0.2)
Now for AgCI : Ksp = 1.6 x 10-io = [Ag+ ][Cl-]= [Ag+ ] x 10- 3 Ksp(AgCI) = [Ag+ ][Cl- ]
⇒ [Ag+] =l.6xl0-7 ⇒ x=7
= x(x + 0.2) = x 2 + 0.2x
12. Let molar solubility of Cr(OH)3 = S mo! L- 1 2
Ksp = O.2x(x « I)
Cr(OHMs) ~ Cr 3 +(aq) + 30W (aq) 1.2 X 10-IO = O.2x
S 3S or
3
Ksp = 1.6 x 10- o = [Cr 3+ ][ Off = (S)(3S)3 = 27S
4
f X = 6 X 10-IO
 Equilibrium I 195
----->.
.,-------- 2Ag+ + co~- Ksp = [Ag+ ] 2 [S2-]= (2S)2(S + 0.1) = 4S 3 + 0.4S 2
2S s
K"' = [Ag+ J2 [Cot]= (2S)2- S ⇒ J0-17 = 0.4S 2 [·: Higher powers are neglected.]
S = 5 x 10-9 mol L- 1
3
K
"' -4S
- 26. Cu 2+, Bi 3+ and Cd 2+all belong to II group of qualitative analysis
20. For precipitation, while Zn 2+ belongs to IV group. The solubility product of
Ionic product> solubility product (Ksp) sulphides ofIV group radicals is higher as compared to that of the
For, Ag2CrO 4 II group radicals.
Ionic Product (IP)= [Ag+ J2 [CrO4] Hence, ZnS has the highest value of solubility product.
= (I0-4)2(10-5) = I0-13 27. The solubility product (Ksp) of a sparingly soluble salt at a given
temperature may be defined as the product of the molar
Ksp of Ag2CrO4 = 4 x I0- 12
concentrations of its ions each raised to the power equal to its
Here, Ksp > IP number of ions present in the equation representing the
Thus, no precipitate is obtained. dissociation of one molecule of the salt.
For AgCI, ionic product= [Ag+] [Cl-]= [10- 4 ][10- 5 ]= 10-9 Fe(OHh ~ Fe3+ + 3OW
X X 3X
Ksp (AgCI) = IX 10- io
Ksp = [Fe3+ ][OW f
Here, IP > Ksp
Ksp = X(3X)3 = 27X4
So, precipitate will form.
Thus, silver chloride gets precipitated first. 28. Salt Solubility product Solubility
21. Hg2 I2 ~ Hg~+ + 2r MX Sf = 4.0 X 10- 8 S1 = 2 X 10- 4
Ksp = [Hg;+ ][r-] 2 MXz 4S? = 3.2 X I0-14 S =2x10- 5
2

22. Ksp[BaCO 3] = [Ba + ][CO~-]2 M 3X 27Sj = 2.7 X 10- 15 S 3 = 1 x I0- 4

[Ba 2+ l =~ = 5.1 x I 0-
9 Thus, solubility order is MX > M 3 X > MX2.
[CO~-] lxl0-4 29. Ca(OH)z ~ Ca 2+ + 20W
[Ba 2+ ]= 5.1 X 10-5 M K"' = [Ca 2+ ] [OW ]2 = (S) (2S)2 = 4S3
23. NH4CI, being a strong electrolyte, dissociates as 30. Addition of sodium acetate in acetic acid solution, due to
common ion effect of acetate ion, the ionisation of acetic acid is
NH4CI - NH; + Cl-
supressed so concentration of [H+ ] decreases. Hence, pH of
and NH4OH as, solution increases.
NH4OH ~ N H; + Off 31. Mg(OH)z ~ Mg2+ + 20W
Weak electrol yte Corrmon ion S 2S
Due to the presence of common ion, the degree of dissociation of Ksp Mg(OH)z = [Mg2+ ] [OW ] 2
NH4OH decreases. Thus, less Off ions are produced which are
sufficient only for the precipitation of hydroxides of III group ⇒ Ksp Mg(OH)z = 4S 3
radicals and not of higher group radicals. 1.96 X 10- l I = 4S 3
24. D issociation constant
or S = [ 1.96: I 0- 11r3
H 20 ~ W + OW
[H+ ]=[OW]=l xl0- 7 M
or S = (4.9 X I0- 12)113
and [H,O]= lg/mL = 1000 gL-1 = IOOO mol L- 1 = 55.56 M
- 18 S = 1.69 X 10-4
[W ][OW] I0- 14
So, concentration of [OH- ]= 2S
K= - - - - = - - K,.. =lxl0-14
[H2O l 55.6 ' · [Off]= 3.38 x I0- 4
So, K,. = 55.6 x K ⇒ pOH =- log[Off]= - log[3.38 x 10-4]
25. Let the solubility of Ag2S is s. pOH = 3.471
Ag2S ~ 2Ag+ + s2 - pH= 14-pOH= 14 - 3.471
s 2S S pH= 10.529
Na2S , being a strong electrolyte, dissociates completely and 32. For precipitation, ionic product > solubility product
provides [S2 - ] = 0.1 M
:. The metal sulphide with lowest Ksp(PbS) will precipitate out
2
[Ag+]= S , [S -]= (S + 0.1) M first because its ionic product will exceed its K"' first and the
metal sulphide w ith highest Ksp(NiS) will precipitate out at last.
196 I Chapterwise & Topicwise Engineering Entrances Solved Papers
33. A salt is precipitated only when the product of ionic 3.2x10- 11 =4S 3 ⇒ S 3 =0.8xto- "=8xl0- 12
concentration is more than its solubility product.
Solubility= 2 x 10-4 mol/ L
Ksp = Ix 10~8
38. Due to common ion effect, rate of ionisation ofNH4OH decreases,
[A+ ] = JO- 3M
so lower [OH- ] is obtained. Hence, pH value decreases.
[ s- l = I x I o--s = t o-5M 39. AB, ~ A 2+ + 2B-
10-3 - S 2S
So, AB w ill be precipitated only when the concentration of[ B- ]is Ksp = [A 2+ ][ s- J2= (S)(2S)2 = 4S 3 = 4 (Ix 10- 5)3 = 4 x 10- 15
more than I o- 5M.
40. AgCt ~ Al + c 1-
34. Let the solubility of AgCI is S
Ksp =[Ag+ ] [Cl- ]
AgCI ~ Ag+ + Cl- 2
s s Ksp = S (S solubility in mol/L)
[Cl- ] from NaCl= 0.2
S= 1.435 X 10- Jg/L = I x 10-5 mol/ L
Concentration of c1- = S + 0.2 143.5
= S(S + 0.2)
Ksp 2
K sp = S = 10-6
1
0
I.8 x 10- = s 2 + 0.2s 41. Ag2CO3 ~ 2Ag+ + co~-
(S is very small as AgCI is sparingly soluble in water, thus, Due to the common ion effect, the solubility decreases, so the
S 2 «< I) solubility of Ag2CO 3would be greatest in IL of0.05 M NH3 due
10
1.8 X 10- = 0.2S to the absence of common ion either Ag+ or CO~- . Ag+ form
S = l.8x 10- 10 complex w ith NH3.
0.2 Ag++ 2NH3 ~ (Ag(NH3)2 i+
= 9.0x 10- 10 M 42. Ca 3(PO4 )i ~ 3Ca2+ + 2PO~-
Ksp = [Ca2+ ] 3 [POt ] 2
35. AglO3(s) ~ Ag+(aq)+ IO3 (aq)
Let solubility of AglO 3 be S 43. Ca(OH)2 ~ Ca 2+ + 2OW
S 2S
Ksp =[Ag+ ] [103]
Ksp =[S1[2S]2 (where, S= solubi lity)
1.0 X 10- 8 = S 2 or S = 1 X 10- 4 mol/L
4
Ksp = 4S 3, Ksp = 4·(✓3)3 = 12✓3
In I 000 mL, moles of AglO3 dissolved = 1 x I 0-
2
44. BaCl2 - Ba + + 2c1-
In I 00 mL, moles of Agl0 3 dissolved = 1 x I 0- 5
Let the solubility of BaC1 2 is x mol/L
Mass of AgIO 3 in 100 mL =Ix 10- 5 x 283 = 2.83 x 10-3 2+ - 2 2 2 3
Ksp=[Ba ][Cl ] =(x)x(2x) =xx4x =4x
5 10
36. Ksp of AgCI = (solubility of AgCl)2 = (1 x 10- )2 =Ix 10-
or solubility ofBaC1 2
Suppose, its solubility in 0.1 M NaCl is x mol/L 113
AgCt ~ A l + c1-
= (solubility prod;ct ofBaCl 2)
113
~
( 4 x 0-
9
) = 10-3 mol/ L
X x
NaCl ~ Na++ Cl+ 45. For the solute AxBy ~ xA + yB
0.1M 0. 1M
[Cl- ]=(x + 0. l )M Ksp =xxyy(s/+ Y
Ksp of AgCI =[Ag+ ][Cl- ]= x x (x + 0.1) M X4 ~ M4+ +4X-
10
Ix 10- =x2 + 0.lx x = I, y =4
1 5
Higher power of x are neglected Ksp = (4 )4(1) (S)5 = 256S
I X 10- 10 = 0.1 X
K ) 115
x= l x 10- 9 M s =( ~
256
37. A.X2 is ionised as follows
46. Al(OHh is a quaternary solute. It dissociates into At 3+ and OH-
AX2 as
s rm1 c 1 Al(OHMs) ~ Al 3+(aq)+ 3Off (aq)
Solubility product of A.X2
Let solubility of Al(OHh be. S hence,
(Ksp) = [A + ][X- ] = S x (2S)2 = 4S 3
2 2
Al(OHMs) ~ Al 3+(aq)+ 30ff (aq)
S 3S
Ksp of A.X2 = 3.2 x 10- 11
Ksp = [Al 3+ ] [Off f = (S) (3S)3 Ksp = 27S 4
 Equilibrium I 197
47. The solubility of Agl in NaI solution is less than that in pure water 56. A precipitate of AgCI is formed when equal volumes of Io- 5 M
because of common ion effect. AgNO 3 and 10- 4M HCI are mixed, because ionic product will be
48. Pb(OH)z ~ Pb2+ + 2OW 10- 9 which is greater than K,p(I0- 10 ). For the precipitation of an
electrolyte, it is necessary that the ionic product must exceed its
Ksr, = [Pb2+ ] [OW]2 = S x (2S)2 solubility product.
2
Ksp = 4S 3 = 4 x (6.7x !0~)3 = 1.20 x 10-15 57. Ca 3 (PO4)z = 3Ca + + 2PO~-
5 moll L 3S 2S
In a solution with pH = 8
Ksr, = [Ca 2+ ]3 [POt ]2 = (3S)3 (2S)2, Ksp = 108S 5
[H+ ] = W-8 and [OW ] = 10~
58. The compound which is having least solubility will be precipitated
1.20 x 10- 15 = [Pb:t] [10-6 ]2 first.
11
BaSO4 : Given, K"' = 10-
[Pb2+ ]
Let the solubility = x mol/L
49. HgzCI 2 ~ Hgi+ + 2Cl- BaSO4 ~ Ba 2+ + SO~-
s 2S x X

2 2
Ksp =[Hg~+] [CI-]2 = (S) (2S) Ksp =[Ba + ] [SO~- ]

K sp = 4S 3 or Ksp=xxx
K sp = x 2 or x = ~ =~
'IJ"sp

= 3.16 X I Q~ mol/L

50. Sb2S;i ~ 2 Sb + + 3 2 CaSO3 : Given, K"' = 10~

3S -
s mot/ L 2s JS
Let the solubility = x mol/L
Solubility product (Ksp) = [Sb +
3
J2 [S2- ] 3 CaSO4 ---4 Ca 2+ + so~-
2 5 5 25
= (2S) (3S)3 = 108 S = 108 X (1.0 X 10- )5 = 108 X 10-
Ksp = [Ca 2+] [Soi- ]
2
51. CaF2 ~ Ca + + 2F
S 2S or Ksr,=XXX
Ksp = S (2S)2 = 4S 3 K sp =x2

Ksp = 4 (2.3 x , o~)3 = 48.668 x 10- 18 (rnol dm- 3 )3 or X = JK;; =,ho~ = I X 10- 3 mo! /L
5
52. The value of the ionic product of water depends on temperature. Ag2SO4 : Given, K"' = 10-

53. For binary salts (like AgCI, AgBr). S = jif;; Let the solubility= x mol/L
Ag2SO4 ---4 2Ag+ + soi-
Solubility of AgCI = ✓1.8 X 10- 10 = 1.35 X 10-1 rnol/ L 2x X

Solubility of AgBr = .j5.0 x 10- 13 = 7. 1 x 10- 7 mol/L Ksr, = [Ag+ ] 2 [So~- ] or = (2x)2(x)
For, Ag2 Cr04, K"' = 4S
3
3~ ✓10-5
or K " spsp_ = - - = 10-2 mol/L
= 4x 3 or x = _'ii_
sp 4 4
:. SoIub ·1· fAg CO 2 .4-x -
~Ksr, = 3r- 10- 12
t tty o 2 r 4 = - - ·: BaSO 4 has least solubility.
4 4
15 5
:. It will precipitated first.
= ~600 X 10- = 8.44 X 10- mol/ L
As Ag2Cr04 has maximum solubility, it w ill give maximum Ag+ Topic 6 Buffer Solution, Salt
ions in solution. Hence, it will be used. Hydrolysis and Acid-Base
54. MX2 ~ M 2++ 2x- Titrations
s 2S
1. Since, at equivalence point (for acid) N IVi = N 2V2 (for base)
K"' =[M 2+ ][X- ] 2
:. Volume ofNaOH required to reach equivalence point
If solubility be S then
3
= 0. l x25 = 50 mL
Ksr, = (S)(2S)2 = 4S 0.05
4S 3 = 4 X 10- 12 :. Concentration of salt formed
millimoles of acid 25 x 0.1 0.1
S = 1x 10- 4
M = --- = -
total volume in mL 75 3
M 2+ = S = Ix 10-
4
M
[W ] = ✓Kwcx Ka=
14 5
Since, 10- X 1.8 X 10- X 3
55. Kw = [H+ ][OW ] 0.1
= c1 o~) x (Io~) ·: (H+ J= [ ow J = 10-12 pH= 8.63
198 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2. Acids which are weak in water will be highly acidic in NH 3 . 11. In case of hydrolysis ofsalt of weak acid and strong base, the pH
(a) HCI + NH 3 ~ NH4Cl . . b I 1 1
IS given y - pKW + - pKa + - loge
2 2 2
(b) CH 3COOH + NH 3 ~ CH3COONH4
(c) H2SO4 + NH3 ~ (NH4)i SO4 12. The aqueous solution ofKCN, K 2CO 3 and LiCN tum red litmus
:. Effect of ammonia is least in H 2SO4 and maximum in blue because of alkaline nature.
CH 3COOH. The anionic hydrolysis turns the solution alkaline.
: . Order of acidic strength of resulting solution is 13. NH4OH + NH4Cl is an example of basic buffer. Tts pH value is
(NH4 )i SO4 > NH4CI > CH3COONH4 greater than 7.
:. Order of pH of resulting solution is 14. The hydrolysis reaction of conjugate base of acid is
CH3COONH4 > NH 4Cl > (NH 4)iSO4 A- (aq) + H 2O - HO-+ HA
Hence, correct option is TI > T> TTI
K = Kw = 10-14 = 10-10
3. pH of an acid buffer is given by Henderson equation. h Ka 10-4
pH = - log Ka+ log [salt] Since, degree of hydrolysis is negligible;
[acid ]
[OWJ =.JK,.C =10-6,pOH =6
or pH= pKa + log [sa!t)
[acid) and hence, pH = 14 - 6 = 8
15. Buffer capacity of an acidic buffer is maximum w hen the ratio of
4. pKa of weak acid= 4.0
HA to [ is unity.
We know that pH= pKa + log [sa!t)
[acid] Since, pH of acidic buffer = pKa + log [A- ]
[HA)
[salt]
Here, pH = 5, pKa = 4, 5 = 4 + 1, log - _ - = I, For maximum buffer capacity, [A-) = [HA]
[acid)
:. pH= pKa.
[salt) = .!_Q 16. When a strong acid is titrated with weak base, solution will be
[acid] acidic in nature. Since,the pH of acidic solution is always less
5. In the titration ofstrong base with strong acid, we can use methyl than 7, therefore, pH ofthe given solution will also be less than 7.
orange, methy l red, phenolphthalein as indicator 17. Acidic buffer is a mixture of weak acid and its salt with strong
6. An acidic buffer solution can be prepared by mixing weak acid base. Similarly, basic buffer is a mixture of weak base and its salt
(e.g. CH3COOH)and its salt with strong base (e.g. CH 3COONa). with strong acid.
Hence, 50 mL 0. 1M CH 3COOH + I 00 mL 0. 1 M NaOH does not
7. CH 3COOH + NaOH - CH3COONa + H 2
constitute a buffer solution because in this case millimoles ofacid
Initially 20 X 0.1 10 X 0. 1
= 2 m mol = I 1nmol are less than that of strong base, which after reaction with strong
At time I I (2 - 1) = I mt00I (1 - 1) = 0 mmol I mmol base gives salt. Now, the solution contains only strong base and
From Henderson's equation, salt but no weak acid. Hence, no buffer is formed.

pH = pK + log [CH 3COONa] = 4.74 +log ~ = 4.74

18. Oxalic acid is a weak acid and sodium hydroxide is a strong base,
0
[CH 3COOH] 1 hence, phenolphthalein is used as a indicator. Methyl orange is
used as an indicator in case of a strong acid and weak base.
8. Ammonium acetate is a salt of weak acid and weak base. When
19. Weak monoacidic base, e.g. BOH is neutralised as follows
solutions of such salts is diluted, resulting pH of solution is
calculated from the following relationship BOH + HCl - BCI + H 2O
1 1 At equivalence point all BOH gets converted into salt and
pH=7+ pKa- PKb
2 2 remember, the concentration oflr (or pH of solution) is due to
hydrolysis of resultant salt (BCl, cationic, hydrolysis here)
pKa = pKb (Given)
B+ + H 2O _____. BOH + H +
pH of the solution = 7 C(I - h) Ch Ch
9. ·: pOH = pKb = - log Kb (·:[base]= [salt)) Volume ofHCl used up
:.pOH =pKb =-logl0- 9 =9 V =NbVb =2.5x2x l 5= 7 _5 mL
·: pH= 14 - pOH = 14 - 9 = 5
a Na 2X 5
10. Initially [CH 3COONa)= 0.1 mol [CH3 COOH] = 0.1 mol Concentration of salt
[BCI] cone. of base 2x 2. 5
when 0. 1 mol CH3COONa is added. I = 0.1
total volume 5(7.5+2.5) 10
[ CH3COONa] = 0.1 + 0 .1 = 0.2 mol 2
2 K _ Ch _ K,.,
pH= pK + log [salt]= pK + log 0.
a [acid] a 0.1
h- lh
-
- Kb
= pK0 + log 2 [CH3COOH] ⇒ 0.1 M (h should be estimated whether that can be neglected or not) on
calculating h = 0.27 (significant, not negligible)
[H+ ]=Ch = 0.1 x 0.27 = 2.7 x 10-2 M
 Equilibrium I 199
20. For salt of weak acid and weak base KCN + H 2O ~ KOH + HCN
I Strong base Weak acid
pH = - [log K0 + logKw - log Kb] (basic solution)
2
27. From the aqueous buffered solution of HA, 50% HA is ionised
I 1 1
= 2 PKa + 2 pKw - 2 pKb [HA]=[A- ]
I I Buffer solution of weak acid HA ➔ acidic buffer
= - X4.80+ 7- - X4.78 =7.01
2 2 pH= pK + log [A+]
0
21. Na2CO3 salt gives strong base and weak acid on dissolving in [HA]
water. Hence, it produces an alkaline solution. or pH=pK0 =4.5
Na 2CO3 + Hp - NaOH + H 2CO 3 pOH = pKW- pH
22. For buffer solution, str0ng base Weak acid
pOH= 14-4.5 =9.5
pH = pKa + log [sa_lt] 28. Acid indicators are generally weak acid. The dissociation of
[acid) indicator Hln takes place as follows
If concentration of salt= concentration of acid
i.e. [salt)= [acid)
Hence, pH = pK0 K =[H+ ][Jn- ] or [H+ ]=K [Hln]
In [Hin) In [In- ]
23. pH curve of strong acid with weak base is vertical over the pH
range of 4 to 7. pH = - log [H+ ]= - log (Kin [Hin])
[In)

= - log K + log [In- ] = pK + log [In - ]

In [Hin] In [Hin)

or log [In- ] = pH - pK
Volume of base ---+
[Hln) In

The indicator that shows colour change within this range is 29. Na 2CO3 + 2H2O ~ 2NaOH + H 2CO 3
suitable. Methyl red (pH range 4.4 to 6.5) is suitable indicator for or 2Na + + COi- + 2Hp ~ 2Na + + 2OIr + H 2CO 3
titration of weak base vs strong acid.
or COi- + 2Hp ~ 2OIr + H 2CO 3
24. From Henderson equation
[salt) It is anionic hydrolysis.
pOH = pKb + log - -
[base] 30. KCN is a salt of weak acid and strong base hence, on being
dissolved in water gives basic solution, i.e. pH > 7 at 25°C.
pH + pOH= 14
31. pH of the solution at the equivalence point is on the acidic side
pOH = 5.0 + log [I.OJ= 5 + log 10 = 5 + 1 due to dissolution of CO2 formed. A slight excess of strong acid
[0.1] lowers pH to 3.5 when methyl orange produces red colour.
pOH =6 32. For the salt of weak acid and strong base.
pH + pOH=14
⇒ pH + 6= 14 Kh =h C
2
or h = ~
⇒ pH= 14 - 6= 8
33. Buffer capacity of a buffer solution is maximum when the
25. CH3COONa + H 2O - CH 3COOH + NaOH concentration of the weak acid and its salt or weak base and its
The above process takes place in following steps salt are equal, i.e., for highest buffer capacity pH= pK0
lonisati~n For this [salt) = [acid]
CH3COONa _ ~ _ CH 3COO- + Na+ Therefore, volume would be 50 mL.
m aqueous solution Strong base
34. NH4Cl salt gives an acidic solution in water
CH3Coo- + H2O - CH3COOH + OH-
Acetate ion undergoes anionic hydrolysis and the resulting NH4Cl ~ NH; + c1-
solution is slightly basic due to excess of Oir ions. Hence, both H2O + H p ~ OIr+H3O-
assertion and reason are true and reason is the correct explanation
of assertion.
26. Aqueous solution of HCOONa,Ci;H5NH3Cl,KCN are basic,
acidic and basic in nature.
Weakly ionised Strongly ionised
HCOONa + H 2O ~ HCOOH + NaOH
\¼ak acid Strong base
(basic solution)
r salt 1J
35. For basic buffer, pOH = pKb + logl-
base
C6H 5NH3Cl(aq) ~ C6H 5NH2 + HCI
Weak base Strong acid Given, [salt]= [base] = 1
(acidic solution)
200 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Kb= 2 X 10- 5 43. CH3NH2 (base) on reaction with HCI (acid) to give a salt of weak
pOH = pKb = - log (2 X 10- 5
) base and strong acid as CH 3NH; CI-

= 5 - log 2 = 5 - 0.30 = 4.70 CH3NH2 + HCl - CH3NHt

At=O Olmol 008 mol
pH = 14 - pOH = 14 - 4.70 = 9.30
after reaction (0. I - U 08) = U 02 mol 0. 08
36. For a salt of weak base and strong acid like MgC1 2 the relation is So, it acts as basic buffer solution due to presence of base and salt
K in solution of I L.
as Kh = ___!!'_ [salt]
Kb pOH = - log10 Kb + log 10 - -
[base]
37. The buffer solutions are those solutions which resists the change
[CH3NH+ 3 Cl- ]
in its pH value on addition of small amount of a base or an acid. pOH = - log 10 Kb + log 10
CH 3COOH and CH3COONa solution is buffer solution because it [CH 3NH2 ]
is a solution of weak acid and its salt with strong base.
= - log10 5 x 10
-4
+ log10
ro.osl
L--J
38. Only salts of (weak acid + strong base) and (strong acid + weak 0.02
base) get hydrolysed. (i.e. show alkalinity or acidity in water).
= - log10 5 + 4 log10 10 + log 10
ro.os1
L--J
KCIO 4 a salt of strong acid and strong base, therefore, it does not
0.02
get hydrolysed in water.
= - 0.699 + 4 + 0.602 = 3.903
KC1O 4 _.,_ K+ + ClO 4
pH = 14 - pOH = 14 - 3.903
H 2O Olr + H+
= 10.097 = - log10 (H+ ]

1l 1l [H+ l = 8.0 X 10- 1 I

[salt]
KOH HC1O4 44. pOH = pKb + log - - (Henderson'sequation)
Strong Strong
base acid [base]
0.02 I
39. Mixture of acetic and sodium acetate is an acidic buffer. Hence, = 5 + log - = 5 + log - = 5 + (- I) = 4
from Henderson equation, 0.2 10
[salt] pH= 14 - pOH = 14 - 4 = 10
pH= pK0 + log - .-
[acid] 45. Both assertion and reason are trne statement but reason is not the
On increasing [salt] ten times of that of [acid], the pH will correct explanation of assertion. pH of a buffer solution is given
increase by one. by Henderson-Ha.selbalch equation.
[saltl
40. A solution with reserve acidity or basicity is known as buffer pH= pK0 + log - _-
solution. It is of two types: [actd)
(i) Acidic buffer solution A mixture of weak acid and its salt pH= pKa (when [salt]= [acid])
with strong base. 46. (a) CH3COONH4 + H 2O - CH3COOH + NH4OH
e.g. CH3COOH + CH 3COONa Arrun>nium acetate

(ii) Basic buffer solution A mixture of a weak base and its salt Although both (CH3COOH and NHpH) of them are weak
with strong acid. still CH3COOH is slightly more acidic.
e.g. NH4OH + NH4Cl :. Solution is acidic in nature.
41. Na2CO3, on hydrolysis gives alkaline solution as the solution (b) NH4CI + H 2O - NH4OH + HCI
An.mnium chloride Weak base Strong acid
contains strong base and weak acid.
:. Solution is acidic in nature.
Na2CO3 ZHiO 2NaOH+ H 2CO 3
(c) (NH4)2SO4 + H2O - 2NH4OH + H2SO4
White Strong base \'kak acid Amm:mium sulphate Weak base Strong base
42. FeCl3, on hydrolysis gives acidic solution due to the presence of
:. Solution is acidic in nanire.
strong acid (HCl) and weak base (Fe(OH)J) in the solution.
(d) CH 3COONa + H 2O - CH3COOH + NaOH
3 2 Sodium acetate Weak acid Strong base
Fe Cl 3 H o Fe(OH)3 + 3HC1
Weak base Strong acid :. Solution is basic in nature.
Hence, solution is acidic.
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Redox Reactions
QUICK REVIEW
Oxidation Redox Reactions
According to classical concepts, oxidation is defined as the • These reactions are the chemical reactions which involve
process that involve both oxidation as well as reduction simultaneously.
(i) Addition of oxygen Redox reactions are of two types-direct redox reactions
e.g. 2 Mg (s) + 0 2 (g) ~ 2 MgO (s) and indirect redox reactions.
All the combustion processes are examples of it, • Oxidising agent is a substance which can accept one or
e.g. combustion of methane to produce CO2 and more electrons or easily reduced.
water.
• Reducing agent is a substance which may lose one or more
CH4 (g) + 202 (g) ~ CO 2 (g) + 2H2 0(/) electrons easily or easily oxidised.
(ii) Addition of other electronegative elements e.g.
e.g . Mg(s)+ Cl 2 (g) ~ MgC12 (s) Oxidation or loss of e-
Electronegative
element
Zn + Cu2 +(aq)~ Cu(s) + Zn2+ (aq)
(iii) Removal of hydrogen
e.g . 2 H2 S (g) + 0 2 (g) ~ 2S(s) + 2H2 O(l) Reduction or gain of e-
2
(iv) Removal of other electropositive elements Here, Oxidising agent ➔ Cu +
e.g . 2K 4 [Fe(CN)6 ] (aq) + H 2 0 2 (aq) ~ Reducing agent ➔ Zn
2K 3 [Fe(CN)6 ] (aq) + 2KOH(aq) Oxidation Number
Reduction It is defined as the charge that an atom of the element has in its
ion or appear to have when p resent in the combined state with
Classical concepts define reduction as a process that involves other atoms.
(i) Removal of oxygen
/',. • Oxidation number of elements in their elementary state is
e.g . 2 HgO(s) ~ 2 Hg(l) + 0 2 (g) zero. In ionic hydrides, hydrogen has- !oxidation number.
(ii) Removal of other electronegative element Oxidation number of fluorine is always - l Oxidation
e.g. 2FeCI3 (aq) + H 2 (g) number of oxygen is - 2 in its compounds except

(iii) Addition of hydrogen

~ 2FeCl 2 (aq) + 2HCl(aq)
e.g. CH 2 = CH 2 (g) + H2 (g)
Ethene ~ CH -CH (g)
3 3
Ethane
(iv) Addition of other electropositive element
e.g. 2HgCI 2 (aq) + SnC1 2 (aq) ~
Hg 2 Cl 2 (s) + SnCl 4 (aq)
inperoxides (- l) and in superoxides (-¾). The oxidation
number of metals in amalgam and carbonyls is zero.
• The algebraic sum ofoxidation number ofall the atoms in a
compound must be zero. But in case of polyatomic ions, the
algebraic sum of all the oxidation numbers of atoms of the
polyatomic ion must be equal to the charge present on it.
202 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Oxidation number of an atom cannot be more than the agent. Half-reaction method is based on splitting the redox
number of electrons present in valence electrons. reaction into two half-reactions, oxidation half reaction
and reduction half-reaction.
Oxidation number of certain compounds
Oxidation
Oxidation Number Method
Compound Structure Following steps are used to balance a redox reactjon
number
0 +6 Step I Write the skeleton equation representing chemical
o" 11 /o change.
I/cr" I
0 +6 0 Step II Assign oxidation number to find out which atoms
are undergoing oxidation and reduction and write
0
separate equation for the atoms undergoing
11+6 oxidation and reduction.
H- O- S- 0- 0 - H +6
II Step III Find the change in oxidation number in each
0 equation. Make the change equal in both the
0 0 equation by multiplying with suitable integers.
II+ 6 II +6 Add both the equations.
H- O- S- 0 - 0 - S- O- H +6
II II Step IV Now balance those elements which are not
0 0 undergoing oxidation or reduction except H and
00+1 +land-I 0 . Then, balancing H and O with the help of
/ H20.
Ca"-
c1-1
Ion Electron Method or Half-Reaction Method
NOC! NO+Cl- +3 Following steps are used to balance a redox reaction:
0 0 Two S with
Step I Write down the redox reaction in ionic fom1.
+5 II o o II + 5 zero oxidation
NaO- ~- S-S-~ - ONa number and Step II Split the redox reaction into two half-reactions,
two with + 5 one for oxidation and other for reduction.
0 0 oxidation
number Step III Balance the number of atoms or ions undergoing
reduction and oxidation.
• Fractional oxidation number In certain compounds, Step IV Now add electrons on that side of reaction where
the oxidation number of a particular element is in fraction . they are deficient to equalise the charge on both
sides. Multiply if required by suitable number to
+2 0 +2
0
11 11 balance electron on both side ofreaction.
e.g.0= C=C=C=O; 0-S-S-S-S-0°
Carbon suboxide, C3 02 11 II S tep V Now add both the half-reaction and balance
0 0 atoms not undergoing reduction and oxidation
Telrathionate ion, S4 Q,2 - (except Hand 0). Now, balance Hand O with
help of water.
Though their actual oxidation states or number are whole
Balancing of H 20 can also be done as per the
number but an average of these is fractional. medium given.
• Disproportionation reaction It is the process in which (i) Acidic medium Add H 20 on that side of reaction
same substance act as an oxidising agent as well as
where oxygen are deficient and make double the number
reducing agent simultaneously.
- I - I -2 0 ofH+ on opposite side ofreaction.
e.g. H 2 0 2 +H 20 2 ~ 2H 2 0+02
(ii) Basic medium Add H 20 on that side of reaction
• Two methods, oxidation number method and ion electron where oxygen are excess and make double the number
method (half-reaction method) are used to balance chemical of OH- on opposite side of reaction.
equations for redox processes.

Oxidation number method is based on the change in the

oxidation number of reducing agent and the oxidising
 Redox Reactions I 203

2014
1. For the reaction, 9. In the redox reaction,
~ 5
r-+ C lOj" + H2SO4 ~ c1- + HSO:i + 12 MnO4 + 8H+ + 5Br- ~Mn 2 + +4H 2 O + - Br2
The correct statement(s) in the balanced equation is/are 2
[JEE Advanced] Which one is the reducing agent? [AMU]
(a) stoichiometric coefficient ofHSO4 is 6 2
(a) H + (b) MnO4 (c) Br- (d) Mn +
(b) iodide is oxidised
(c) sulphur is reduced l 0. Which one of the following oxidation states is not possible
( d) H 20 is one of the products in metal carbonyls? [AMU]

2. Hydrogen peroxide in its reaction with K.1O 4 and NH 2OH (a)+l (b)0 (c) - 1 (d)+2
respectively, is acting as a [JEE Advanc ed] 11. The oxidation state and covalency of Al in
(a) reducing agent, oxidising agent [AlCI (H2 O) 5 ]2 +respectively are [EAMCET]
(b) reducing agent, reducing agent
(a)+6,6 (b)+3,6 (c)+2,6 (d)+3,3
( c) oxidising agent, oxidising agent
( d) oxidising agent, reducing agent 12. What is the oxidation number of Pt in K [Pt NH 3 Cl 5 ] ?
3. In which of the following reactions, H 20 2 acts as a (a) 0 (b) + 1 [Ind.raprastha CET]
reducing agent? (c)+2 (d)+4
I. H 20 2 + 2H+ + 2e- ~ 2Hz0 13. The pem1anganate ion is an excellent oxidising agent in
II. H 20 2 - 2e- ~ 0 2 + 2H+ aqueous solutions. When the half-reaction,
III. H 20 2 - 2e- ~ 0 2 + 2ff MnO4 + H+ + e- ~ MnO2 + H 2O is balanced, the
IV. H 20 2 + 2H+ + 2[ ~ 02 + 2H20 [JEE Mains]
correct coefficients for the species involved are
[Ind.raprastha CET]
(a) I and II (b) III and IV (c) I and III ( d) II and III
(a) 1,4,4, 1,2 (b)l,4,2,1,2
4. The ratio of oxidation states of Cl in potassium chloride to (c) 1,4, 3, 1, 2 (d) 1,4, 1, 1, 2
that in potassium chlorate is [BITSAT]
14. A reagent which lowers the oxidation number of an
(a) + l/5 (b)-1/5 element in a given substance is known as [J & K CET]
(c) - 2/5 (d) + 3/ 5
(a) oxidising agent (b) reduction
5. In the reaction, 8Al + 3Fe3 O 4 ~ 4Al 2 O 3 + 9Fe
(c) reducing agent ( d) oxidation
the number of electrons transferred from the reductant to
15. In Br3 O 8 compound, oxidation number of bromine is
the oxidant is [VITEEE]
(a) 16/ 13 (b) 26/3 [J& K CET]
(a) 8 (b) 4
(c) 24/3 (d) 16/3
(c) 16 (d) 24
6. Out of the following redox reactions, 2013
I. NH4N03 ~ N 2 0 + 2Hz0 16. Consider the following reaction,
II. NH4N02 ~ N 2 + 2H 20 xMnO4 + yC 2 0;-
+zH+ ~xMn 2 +
z
+ 2yC02 + - H 2 O,
IIT. PCl 5 ~ PCl 3 + CI2 2
disproportionation is not shown in [Manipal] The value of x, y and z in the reaction respectively are
(a) I and II (b) II and III
(c) I and III (d) I, II and III (a) 5, 2 and 16 (b) 2, 5 and 8 [JEE Mains]
(c) 2, 5 and 16 (d)5, 2and 8
7. Which of the following species contain an element in an
17. In which of the following, oxidation number of chlorine is
oxidation state that is not a whole number? [Manipal]
+ 5? [Manipal]
(a) VO! - (b) Mn 2 0 3
(a) Cl- (b) CIO- (c) ClO2 (d) ClO3
(c) S4 0r (d) Cl 2 0 7
18. The coefficients ofl- , 10 3 and H+ in the redox reaction,
8. IfC12 is passed through hot aqueous NaOH, the products
formed have Cl in different oxidation states. These are 1- + 10 3 + H+ ~ 12 + H 2O
indicated as [WB JEE] in the balanced form, respectively are [Manipall
(a) - land+l (b) - land+ 5 (a)5,l , 6 (b)l,5, 6
(c) +land + 5 (d)- land+ 3 ( c) 6, 1, 5 (d) 5, 6, 1
204 I Chapterwise & Topicwise Engineering Entrances Solved Papers
19. The oxidation number and the electronic configw-ation of 29. For the reaction, NH 3 + OCI- ~ N 2 H 4 + Cl-
sulphur in H 2SO4 is [KCET] occurring in basic medium, the coefficient ofN 2H 4 in the
()
a + 41 2222632
;s,s,p,s balanced equation will be [RPET]
2 2 6 2 2 (a) 1 (b) 2 (c) 3 (d) 4
(b) + 2; l s , 2s , 2p , 3s , 3p
2 2 6 2 1
(c) + 3; l s , 2s , 2p , 3s , 3p 30. In the reaction, SO 2 + 2H2S ~ 3S + 2H 2O, the
(d) + 6; l s 2 , 2s2 , 2p 6 substance oxidised is [JCECE]

20. Oxidation state of oxygen in H 2O 2 is (b) SO2 (c) S (d) H 2 0

[OJEE]
(a) - I (b) + 2 (c) 1/ 2 (d)- 2 2009
31. Ceric ammonium sulphate and potassimn permanganate
2012 are used as oxidising agents in acidic medium for oxidation
21. Which order of compounds in according to the decreasing offenous ammonium sulphate to ferric sulphate. The ratio
order of the oxidation state of nitrogen? [IIT JEE] of number of moles of eerie ammonium sulphate required
(a) HN03 , NO, NH4 Cl, N 2 p er mole of ferrous ammonium sulphate to the number of
(b) HNO3 , NO, N 2 ,NH4 Cl moles ofKMnO4 required per mole offerrous ammonium
(c) HNO 3 , NO, NH4 Cl, N 2 sulphate, is [MHT CET]

(d) HNO3 , NH4 Cl, N 2 ,NO (a) 5.0 (b) 0.2 (c) 0.6 (d) 2.0
22. The oxidation number ofsulphur in H 2S 20 8 is [Manipal] 32. In the following reaction,
(a) + 2 (b)+4 (c)+6 (d) + 7 Mx+ + MnO;j ~ MO3 + Mn 2 + + l o2,
2
2011 If one mole ofMnO 4 oxidises 2.5 moles of Mx + then the
23. Reaction of Br2 with Na 2CO 3 in aqueous solution gives value of xis [Kerala CEE]
sodium bromide and sodium bromate with evolution of (a) 5 (b) 3 (c) 4
CO2 gas. The number of sodium bromide molecules (d) 2 (e) I
involved in the balanced chemical equation is [IIT JEE] 33. In acidic medium, Zn reduces nitrate ion to NH; ion
WI ~3 ~5 007 according to the reaction,
Zn + NO 3 ~ Zn 2+ + NH; + H 20 (unbalanced)
24. The difference in the oxidation numbers of the two types of
How many moles of HCl are required to reduce half a
sulphur atoms in Na 2S 4 0 6 is [IIT JEE]
mole ofNaNO 3 completely? Assume the availability of
(a) 4 (b)5 (c)6 (d)7 sufficient Zn. [Kerala CEE]
25. Oxidation states of the metal in the minerals haematite and (a) 5 (b) 4 (c) 3
magnetite, respectively, are [IIT JEE] (d) 2 (e)l
(a) II, III in haematite and III in magnetite 34. Which quantities are conserved in all redox reactions?
(b) II, III in haematite and II in magnetite
(a) Charge only [UPSEE]
(c) II in haematite and II, III in magnetite
(b) Mass only
(d) III in haematite and II, min magnetite
( c) Both charge and mass
26. ln the reaction, H 2S + H 20 2 ~ S + 2H 20 (d) Neither charge nor mass
(a) H 2S is an acid and H 2O 2 is a base [Kerala CEE]
2008
(b) H 2Sis a base and H 20 2 is an acid
(c) H 2S is an oxidising agent and H 2O 2 is a reducing 35. ln which of the following reactions, chlorine acts as an
agent oxidising agent ?
( d) H 2S is a reducing agent and H 20 2 is an oxidising I. CH3CHpH + Cl 2 - CH3CHO + HCI
agent TI. CH 3CHO + Cl 2 - CCl3 · CHO + HCI
Irv
(e) H 2Sis hydrolysed to S ITT. CH4 + Cl 2 - CH3Cl + HCI
27. The oxidation state ofFe in Fe 3 0 4 is [Manipal] The correct answer is [BITSAT,AMU]
(a) + 3 (b) 8/3 (c) + 6 (d) + 2 (a) Only I (b) Only II
28. State the oxidation number ofcarbonyl carbon in methanal (c) I and III ( d) I, II and III
and methanoic acid, respectively [Guj CET] 36. The oxidation number of oxygen in KO 3 , Na 20 2 is
( a) 0 and O (b) 0 and + 2 (a) 3, 2 (b) 1, 0 [VITEEE]
(c) + I and + 2 (d) + I and + 3 (C) 0, 1 (d)- 0.33, -1
 Redox Reactions I 205
37. The value of 'n' in the reaction, 47. The number of moles ofKMnO4 reduced by one mole of
Cr20~- + 14H+ +nFe + ~ 2Cr + +nFe3+ + 7H 2O
2 3 Kl in alkaline medium is [BCECEJ
(a) I (b) 5 (c) 1/2 (d) 1/5
will be [MPPET]
(a)2 (b)3 (c)6 (d)7 48. In the conversion ofBr2 to BrO3, the oxidation number of
38. When sulphur dioxide is passed in an acidified K 2Cr2O 7 Br changes from [Jamia Millia Islamial
solution, the oxidation state of sulphur is changed from (a)zeroto + 5 (b)+lto+5
( c) zero to - 3 ( d) + 2 to + 5
(a) + 4 to 0 (b) + 4 to + 2 [KCET]
(c) + 4to+6 {d)+6to+4 2007
39. Which one of the following reactions involves 49. Oxidation states of X, Y, Z are + 2, + 5 and
disproportionation ? [Kerala CEEJ - 2 respectively. Formula of the compound formed by
(a) 2H2 SO 4 + Cu~ CuSO4+ 2H2O + SO 2 these will be [BITSATJ
(b) As 2O 3 + 3H2 S ~ As 2 S 3 + 3H2 O (a) X 2yz6 (b) XY2Z6
(c) 2KOH + CI 2 ~ KCI + KOCI + H 2O (c) XY5 (d) X 3 Y24
(d) Ca 3 P2 + 6H 2O ~ 3Ca(OH)2 + 2PH3 50. Which is the best description of behaviour of bromine in
(e) 4NH 3 + 302 ~ 2N2 + 6H2O the reaction given below ?
40. In which of the following, the oxidation number of oxygen H 2O + Br2 ~ HBr + HOBr [Manipal]
has been arranged in increasing order ? [Kerala CEEJ (a) Proton acceptor only
(a) OF2 < KO2 < BaO2 < 0 3 (b) Both oxidised and reduced
(b) BaO2 < KO2 < 03 < OF2 (c) Oxidised only
(c) BaO2 < 0 3 < OF2 < KO2 (d) R educed only
(d) KO2 < OF2 < 0 3 < BaO2 51. In the ionic equation,
(e) OF2 < 0 3 < KO 2 < BaO2 BiO3 + 6H+ +xe- ~ Bi 3+ + 3H2 O
41. Among NH3 , HNO3 , NaN3 and Mg 3 N 2; the number of the value of xis [KCET]
molecules having nitrogen in negative oxidation state is (a) 6 (b) 2 (c) 4 (d)3
(a) I (b) 2 [UPSEEJ 52. Oxidation number of sulphur in Caro's acid is [WB JEE]
(c)3 (d)4 (a)+6 (b)+4 (c) + 8 (d)+7
42. In the equation, CrOt + SO~- ~ Cr(OH) 4 + SO~- 53. The oxidation state of Cr in chromium trioxide is
the oxidation number of Cr changes from [UPSEEJ (a)+ 3 (b) + 4 [J&KCET]
(a) + 6 to + 4 (b) + 6 to + 3 (c) + 8 to + 4 ( d) + 4 to + 3 (c) + 5 (d) + 6
43. The reaction, 54. The oxidation number of chromium in potassium
P4 + 3NaOH + 3H2O ~ 3NaH2PO2 + PH 3 dichromate is [BCECE]
is an example of [OJEEJ (a)+ 2 (b) + 4
(a) disproportionation reaction (c) + 6 (d) + 8
(b) neutralisation reaction
( c) double-decomposition reaction
2006
(d) pyrolytic reaction 55. Which of the following chemical reactions depicts the
oxidising behaviour ofH 2SO4? [AIEEEJ
44. Oxidation state of chromium in ?)cr(I is [OJEE] (a) 2HI + H 2 SO4 ~ 12 + SO2 + 2H 2O
o 11 o (b) Ca(OH)z + H 2SO 4 ~ CaSO4 + 2H 2O
0
(a)+I0 (b) + 6 (c) + 3 (d) + 2 (c) NaCl+ H 2 SO4 ~ NaHSO4 + HCI
(d) 2PCI 5 + H 2SO 4 ~ 2POCl 3 + 2HCI + SO2C l 2
45. The oxidation state of sulphur in sodium tetrathionate
(Na2S4O6 )is [J&KCET] 56. Oxidation state of sulphur in Na 2S 2O 3 and Na 2S 4O 6
(a) 2 (b) 0 (c) 2.5 (d) 3.5 {a) 4 and 6 (b) 3 and 5 [BITSAT]
(c) 2 and 2.5 (d) 6 and 6
46. During a redox titration involving a solution containing
Fe 2+ ions against MnO4 in the presence of excess of H+ 57. Oxidation number ofN in N 3 H (hydrazoic acid) is
ions, the number of electrons that gets transfe1red is (a)-1 / 3 (b) + 3 [Manipal]
(a) 6 {b) 5 [J&K CET]
(c) 0 (d) - 3
(c) 4 (d) 2
206 I Chapterwise & Topicwise Engineering Entrances Solved Papers
58. One mole of acidified K 2 Cr2 O7 on reaction with excess 65. The oxidation state ofl in IPO4 is [O,JEE]
Kl will liberate ....... mole(s) ofl 2 . [Kerala CEE] (a)+ l (b)+3 (c) + 5 (d) + 7
(a)6 (b)l (c)7 66. The oxidation number of xenon in XeOF2 is [J&K CET]
(d) 2 (e) 3 (a)zero (b)+2 (c) + 4 (d)+3
59. Which of the following reaction involves oxidation and 67. Oxidation numberofS in sot [BCECE]
reduction ? [WB JEE]
(a)+6 (b)+3
(a) NaBr + HCl ~ NaCl + HBr (c) + 2 (d) - 2
(b) HBr + AgNO3 ~ AgBr + HNO3
(c) H 2 + Br2 ~ 2HBr 68. Which one of the following is a redox reaction?
[Jamia Millia Islamia]
(d) Na 2 O + H 2 SO4 ~ Na 2 SO4 + H2 O
60. The oxidation states of iodine inHI04 , H3 lO 5 and H 5 lO 6 (a) NaCl + KNO 3 ~ NaNO 3 + KCl
respectively, are [UPSEE]
(b)CaC 2 O4 + 2HC1~ CaC12 + H2 C 2 O4
(c) Ca(OH)i + 2NH4 C l ~ CaC1 2 + 2NH3 + 2H 2 O
(a) +l, +3, + 7 (b) + 7, + 7, + 3
(c) + 7, + 7, + 7 (d) + 7,+ 5,+ 3 (d) 2K[Ag(CN) 2 ] + Zn~ 2Ag + K 2 [Zn(CN) 4 ]
61. In which of the following compounds, the oxidation 69. Which one of the following reaction is possible at anode?
nwnber of iodine is fractional ? [BCECE] (a) F2 + 2e- ~ 2F- [Jamia Millia Islamia]
(a) IF3 (b) IF5 (c) 13 (d) IF7
(b)2H+ + ..!. 0 2 + 2e- ~ H2 O
62. When K 2 Cr2 O7 is converted into K 2 CrO4 , the change in 2
oxidation number of chromium is [Jamia Millia Islamia] (c) 2Cr 3 + + 7H 2 O ~ Cr2 O~- + 14H+ + 6e-
(a) 0 (b) 5 (c) 7 (d) 9 (d) Fe 2+ ~ Fe 3 + + e-
70. Mno; is a good oxidising agent in different medium
2005
changing to
63. Which of the following acts as an oxidising as well as
MnO4 ➔ Mn 2 + ➔ Mno~- ➔ MnO 2 ➔ Mn2 0 3
reducing agent ? [Manipal]
Changes in oxidation number respectively are
(a) Na 2 O (b) Na 2 O2 (c) NaNO3 (d) NaNO 2
(a) 1, 3, 4, 5 [Jamia Millia Islamia]
64. What is the oxidation state of Pin Ba(H2 PO 2 h? (b)5,4, 3,2
(a) + l (b) + 2 [Manipal] (C) 5, 1, 3, 4
(c) + 3 (d)-1 (d)2,6, 4,3

Answers
1. (a,b,d) 2. (a) 3. (d) 4. (b) 5. (d) 6. (d) 7. (c) 8. (b) 9. (c) 10. (d)
11. (b) 12. ( d) 13. (c) 14. (a) 15. (d) 16. (c) 17. (d) 18. (a) 19. ( d) 20. (a)
21. (b) 22. (c) 23. (c) 24. (b) 25. (d) 26. (d) 27. (b) 28. (b) 29. (a) 30. (a)
31 . (a) 32. (b) 33. (a) 34. (a) 35. (d) 36. (d) 37. (c) 38. (c) 39. (c) 40. (b)
41 . (c) 42. (b) 43. (a) 44. (b) 45. (c) 46. (b) 47. (a) 48. (a) 49. (b) 50. (b)
51 . (b) 52. (a) 53. (a) 54. (c) 55. (a) 56. (c) 57. (a) 58. (e) 59. (c) 60. (c)
61 . (c) 62. (a) 63. (d) 64. (a) 65. (b) 66. (c) 67. (a) 68. (d) 69. (d) 70. (c)
 Explanations
-3 +5 +I
1. This problem includes concept of redox reaction. A redox 6. T. NH! N 0 3 ~ N 2 0 + 2H2O
reaction consists of oxidation half-cell reaction and reduction
half-cell reaction. It is a redox reaction but not a disproportionation reaction.
Since, different N-species are involved.
Write both half-cell reaction, i.e. oxidation half-cell reaction and
reduction half-cell reaction.Then, balance both the equations. -3 +3 I!. 0
II. NH4+NO2 ---=-t N 2 + 2H 2
Now, determine the correct value of stoichiometry of H 2SO4.
Same as I
Oxidation half-reaction, 2r- ----t I2 + 2e- ... (i) +5-1 I!. +3 - I 0
Here, r is converted into 12. III. P Cl 5 ~ P Cl3+ Cl2
T hus, it is also not a disproportionation reaction.
Oxidation munber ofl is increasing from - I to Ohence, this is a
type of oxidation reaction. 7. In S4oJ-, let 'x' be the oxidation number ofS.
Reduction half-reaction
6W + CIOj" + 6e- ----t c1- + 3Hp ... (ii)
4x - 12 = - 2 ⇒ x =.!.Q= 2.5
4
Hence, H 2O releases as a product. Hence, option (d) is correct. 8. If Cl 2 is passed through hot aqueous NaOH, it results in the
Multiplying Eq. (i) by 3 and adding in Eq. (ii)
formation of sodium chloride and sodimn chlorate as
6 r- + ClO3+ 6H+ ----t Cl-+ 312 + 3H2O
6NaOH + 3Cl 2 ----t 5NaCl + NaCIO 3 + 3Hi0
Hot
6 Y- + CIO3- + 6 H 2SO4----t Cl- +312 + 3H 2O+ 6HSO4.
In NaCl, let oxidation state of Cl be x,
Stoichiometric coefficient ofHSO4- is 6.
I + x = 0 or x = - I
2. This problem can be solved by using concept of oxidant and In NaCIO 3, let oxidation state of Cl be y,
reductant.
I + y + (- 2) 3 = 0
Oxidant Oxidant increases the oxidation number of the species
w ith which it is reacted. ⇒ y-5=0
Reductant Reductant decreases the oxidation number of the y =+ 5
species w ith which it is reacted. Increase in oxidation number, i.e. oxidation
9.
H 2O 2 reacts with KIO4 in the following manner +7 50
+7 +5 MnO4+ 8H+ + 5B, - Mn2+ + 4H 2O + - Br2
KIO4 + H2O2----t KIO3+ H2O + 02 Decrease in oxidation nurnber, 2
i.e. reduction
On reaction of KIO4 w ith H 2O 2 oxidation state ofl varies from
+ 7 to + 5, i.e. decreases. Thus, KIO4 gets reduced hence, H 2O 2 is Since, in this reaction Br- reduces MnO4 into Mn 2+ and itself
a reducing agent.
gets oxidised into Br2, so here it acts as the reducing agent.
H p 2 reacts with NH2OH , and gives following reaction,
- I +3 Note In a reaction, the species w hich undergoes oxidation,
NH2 OH + H 2O 2 ----t N2 0 3 + Hp + 0 2 generally acts as reducing agent.
In the above reaction, oxidation state ofN varies from - I to+ 3. 10. For the formation of 1t back bond (which is generally exist)
Here, oxidation number increases, hence H 2O 2 is acting as an between metal and the carbonyl carbon, the oxidation state of the
oxidising agent here. metal must be lower than + 2 .
3. Substance which releases electron is known as reducing agent. Thus,+ 2 oxidation state is not possible in metal carbonyls.
So, H 2O2 acts as reducing agent w hen it releases electrons. 11. [AJC l (H2O)5 ] 2 +
Here, in reaction II and III, H 2O 2 releases two electrons, hence,
Let oxidation state of Al be x,
reaction II and ITT represent reduction. In reaction I and IV, two
electrons are being added, so T and TV represent oxidation. x + (- 1) + 5(0) = + 2,
x=+3
4. Oxidation state of Cl in potassium chloride, i.e. KCl =- \ Covalency o f Cl = I , covalency of Hp = 5
Oxidation state of Cl in potassium chlorate, i.e. KC1O 3 = + 5
:. Total covalency = I + 5 = 6.
: . Ratio of oxidation state of Cl = -=-!
5 12. Oxidation number ofcentral metal ion can be calculated by using
0 B O 0
the concept that oxidation state of whole compound is always (0)
5. 8A l+ 3Fet 3O4- 4Alp 3 + 9Fe zero or equal to charge present on it as a w ho le.
Oxidation half-reaction Here, K [PtNHp 5) ~ K+ + [PtNH3CI 5 ) -
[2Al + 3H2O - Al 2O 3 + 6e- + 6H-)x4 Let, ox idation state of Pt is x
Reduction half-reaction x + I x O+ 5 x - 1 = - 1 (charge on whole compound)
[3Fe3O4 +Se-+ 8H+ ~ 3Fe+ 4Hp] x 3 x-5=- \ ⇒ x=5-1= + 4
So, 24 electrons transferred.
208 I Chapterwise & Topicwise Engineering Entrances Solved Papers

13. Here, balanced chemical equation is 19. The oxidation number of sulphur in H 2SO4 is
MnO4 + 4H+ + 3e- ------t MnO2 + 2H2O (2 X 1) + x + (4 X - 2) = 0
Balancing can be done by half-reaction method. 2 + X + (- 8) = 0
MnO4 ------t MnO2 x =8- 2 =+ 6
First of all, oxygen is required to be balanced. So, two moles of The electronic configuration of sulphur
water are added on product side. 16 S = 1s2, 2s2, 2p6, 3s2, 3p4
MnO4 ------t MnO 2 + 2Hz0 Electronic configuration ofS in H 2SO 4
Now, 4H+ is added on reactant side to balance H +. 16-6=10
MnO4+ 4H+ ------t MnO2 + 2H2O Hence, 1s2, 2s 2
, 2p6
In order to balance the charge, 3e- are added to reactant side
20. Oxidation state of oxygen in Hp 2 is - 1(- 1is the intermediate
MnO4 + 4H+ + 3e- ------t MnO 2 + 2H2O
oxidation state of oxygen).
Thus, the coefficients for the species involved are
21. Let oxidation number ofN be x
1,4, 3, 1, 2.
In HNO3 + I+ x + 3 (- 2) = 0 ⇒ x =+ 5
14. An oxidising agent decreases the oxidation number of an element
In NO x - 2=0 ⇒ x =+ 2
whereas, a reducing agent increases the oxidation number of an
element. x=O
Decrease in O.N. (reduction) x + 4-1=0 ⇒ x=-3
Thus, the order of oxidation states of nitrogen is
+2 +2 +I +4 HNO 3 >NO> N 2 > NH4Cl.
2HgCI2 + SnCI2 ~ HgCI2 + SnC14
Oxidising
agent
Reducing agent

Increase in O.N. (oxidation)

n
22. H- O- S- O- O- S- O- H
n
II II
15. Br30 8 0 0
Let, oxidation number of Br is x. ·:2 O-atoms are in peroxide linkage.
16
:.3x +8(-2)=0 or 3x=16 ⇒ x= - :. Their oxidation state = - I
3
and, oxidation state of remaining 6 O-atoms = - 2
16. The half-equations of the reaction are
Oxidation state ofH-atom = + I
MnO4 ------t Mn 2 + Let, oxidation state of S-atom = x
C2O!- ------t CO2 Si Si 06 02
The balanced half-equations are 2, + 2(+ I) + 6(- 2) + 2(- 1) = 0
MnO 4 + 8H+ + Se- ------t Mn 2 + + 4H2O 2,+2- 12-2=0
cp!- ------t 2CO2 + 2e- ⇒ x=+6
In equation, number of electrons, we get 23. Br2 is disproportionated in basic medium as
2MnO4+ 16H+ + I Oe- ------t 2Mn z+ + 8H 2O 3Br2 + 3Na 2CO 3 ------t SNaBr + NaBrO3 + 3CO2

scp/-------t 1oco2 + we- 24. Na 2S4O6 is a salt ofH2S4O6 which has the following structure
On adding both the equations, we get
0 0
2MnO4 + sept + 16H+ ------t 2Mn 2 +
16
+ 2x SCO 2 + - H2O
HO__!-
5
II
fl- S-S- II
o o
~TS- OH
2
0 0
Thus, x, yand z are 2, 5 and 16 respectively.
Two S with zero oxidation number and two S with + 5 oxidation
17. The oxidation number of Cl is+ 5 in CIO3 number.
x + 3 (- 2) = - I ⇒ x - 6 = - I Difference in oxidation number of two types of sulphur= 5.
x=- 1+ 6 ⇒ x=+S
18. The balanced equation is as 25. Haematite is Fez03, in which oxidation number of iron is III.
5r + I03+ 6H+ ------t 312 + 3Hp
Magnetite is Fep 4 which is infact a mixed oxide (FeO · FezO 3 )or
Hence, the coefficients ofr ,I03and H+ are 5, 1, 6, respectively. iron (II, III) oxide.
Hence, iron is present in both II and III oxidation state
 Redox Reactions I 209
26. 2 x le- (gain of e-) 0 Reduction - I

-2 - 1/ 0 \-2
Cl 2 - CH3 CHO+HCI
Oxidising agent
H 2S + H2O2 ~ S + 2H2O Removal of hydrogen
i.e. reduction
i. e. oxidation
2.,- (loss of e-)

H 2S - Oxidation, reducing agent. Oxidation Oxidising agent i.e.

(removal of H) reduction
H 2O 2- Reduction, oxidising agent.
0 -I
27. Let the oxidation state of Fe in F~O4 be x ITT. CH4 + Cl 2 ~ CH p + HCI
Oxidation Oxidising (Reduction)
3x + 4 x (- 2) = 0 or 3x - 8 = 0 agent

8 Hence, in all of the above reactions, chlorine acts as an oxidising

x= - agent.
3
28. Let the oxidation number of carbonyl carbon in methanal Nat) 2
(HCHO) and methanoic acid (HCOOH) is x and y, respectively.
Suppose ON of O = x Suppose ON of O = x
In HCHO, 2 (+ I)+ x + (- 2) = 0
+ I + 3x = 0 2xl+2x=0
2+x-2=0 ⇒ x=0 3x =- I 2+2x=0
In HCOOH, 2(+ I)+ y+ 2(-2)=0 x=-113 2x =-2
2+y-4=0 ⇒ y=+2 X =-0.33 X =- 2/ 2

29. 2NH3 + oCI- - N2H4 + c1- + H2O x=-1

I Reduction ! 37. Cr20~- + 14H+ + nFe 2+ - 2Cr3+ + nFe3+ + 7H 2 O

30 +4 -2
. SO 2 + 2H 2 S ~ 3S + 2H2O
0 Crp~- + 14H+ + 6e- - 2Cr3+ + 7H 2O (reduction) ... (i)
I Oxidation t Fe2+ - Fe3+ + e- (oxidation) .. . (ii)
: . H 2S is oxidised in this reaction. Eq. (ii) is multiplied by 6
31. Fe2 + + Ce4 + - Fe3+ + Ce3 + 6Fe2+ - 6Fe3+ + 6e-
5Fe2 + + MnO4 + 8Ir -➔ 5Fe3+ + Mn 2 + + 4Hz0 Thus, balanced equation is
Crp~- + 14H+ + 6Fe2+ - 2Cr 3+ + 6Fe3+ + 7H 2O
Moles of cerric ammonium sulphate _ I_ = _
50 Hence, the value of n is 6.
Moles of potasshun permanganate 1/ 5
38. Acidified K 2Cr2O 7 solution oxidises SO 2 into Cr2 (SO4 h
32. 25M"+ + MnO4- MO 3+ Mn 2+ + _!_ 0 2 + 4 +6
2
3SO2 + K 2Crp7 + H 2SO4 - ~SO4 + Cr2 (SO4 ) 3 + Hp
Hence, oxidation state of sulphur changes from + 4 to + 6.
(Decrease in
oxidation 39. The reactions, in which the same substance is oxidised as well as
nunber) reduced, are called disproportionation reactions.
Increase in oxidation munber of M from + x ➔ +5. Reduction
5 - X = + 2 ⇒ X = 5- 2 = 3 0 -1 +I
33. 4Zn + NO3 + I0H+ - 4Zn 2+ + NH; + 3Hp 2KOH + Cl2 ~ KCl + KOCI + H 2O
(net equation) Oxidation
2
4Zn + NO3 + I0HC I - 4Zn + + NH; + 5Cl2 + 3H2O In this reaction, the same substance, i.e. Cl 2 is oxidised as well as
reduced, so it is an example of disproportionation reaction.
I mole ofNO3 (orNaNO 3) is reduced by= 10 moles ofHCI
40. Let the oxidation number of oxygen in following compounds
_! mole ofNO3 will be reduced by= 10 x _!_ moles ofHCl bex.
2 2 In OF2, x + (- I) 2 = 0 ⇒ x =+ 2
= 5 moles ofHCI In KO2, + I + (x X 2) = 0 ⇒ 2x = - I ⇒ x = - 1I 2
34. Oxidation involves loss of electrons and reduction involves gain In Ba0 2, + 2 + (x x 2) = 0 ⇒ 2 x = - 2 ⇒ x = - I
of electrons. In 0 3 , oxidation number of oxygen is zero because oxidation
Hence, in case ofoxidation-reduction reactions (redox reactions), number of an element in free state or in any of its allotropic form
charge remains conserved. is always zero. T hus, the increasing order of oxidation number of
35. In a reaction, the reagent, which is reduced or remove hydrogen oxygen is
from the other reactant (reagent), is termed as oxidising agent. BaO2 < KO2 < 0 3 < OF2
-I - 1/ 2 0 -2
210 I Chapterwise & Topicwise Engineering Entrances Solved Papers
41. Let the oxidation number of nitrogen be x. 48. Bromine has zero oxidation state because it is in free state.
0
The oxidation state ofN in NH3 is x + 3 (+ I)= 0 Br2 - BrO3
x=-3 Let, the oxidation number of Br in Br03 be x .
The oxidation state ofN in HNO 3 is
x + (- 2 x 3) = - I ⇒ x + (- 6) = - I
I + x + 3 (- 2) = 0 ⇒ x =+ 5
The oxidation state ofN in NaN 3 is
x=+6-1=+5
So, oxidation munber changes from 0 to + 5.
+ I + 3x=0 ⇒ x=-1 13
The oxidation state ofN in Mg3N 2 is 49. The sum of oxidation states is always zero in neutral compound.
The oxidation state ofX, Y and Z are+ 2, + Sand- 2respectively.
3(+2) + 2x = 0 ⇒ 6 + 2x = 0
2x=-6 ⇒ x=-3
I. In X 2YZ6 2 x 2 + 5 + 6 (- 2) 0 *
TI. In XYzZ6 2 + 5 x 2 + 6 (- 2) = 0
Hence, three molecules (i.e. NH 3 , NaN3, Mg3N 2 ) having
nitrogen in negative oxidation state. ITT. In XY; 2+ 5 x 5 0 *
IV. In X 3YZ4 3 x 2 + 5 + 4 (- 2) * 0
42. CrO~- + SO~- - Cr(OH)4 + soi- Hence, the formula of the compolmd is XYzZ6 •
Let, the oxidation number of Cr be x in CrO~- . 0 +I -I
50. In reaction, H 2O + Br2 - HO Br + HBr
x+4(-2)=-2 ⇒ x=+6
and in Cr(OH)4, the oxidation number of Cr is y. The oxidation number of bromine increases from 0 to + I and
decreases from O to - i so due to this reason bromine is both
y+ 4(- 2) + 4(+1) = - 1 oxidised as well as reduced in the above reaction.
y-8+4=- ly =+3 51. BiO3 + 6H+ + 2e- - Bi 3+ + 3Hp ⇒ x = 2
Hence, oxidation number of Cr changes from + 6 to + 3 .
52. Caro's acid is H 2SO5. It has a peroxide lin kage. The structure of
43. Reduction (oxidation number decreases)
H 2SO 5 is as follows:
0 +I ~ -2
P 4 + 3NaOH + 3H 2O ~ 3NaH2 PO2 + PH3 0
Oxidation (oxidation number increases)
-2 II
H- O- ~- O- O- H
The reactions in which the same substance undergoes oxidation +I II -I -I +I
Paoxide linkage
as well as reduction, are called disproportionation reactions. 0
So, the above reaction is an example of disproportionation -2
reaction. Let, the oxidation state of S be x.
44. It is chromium peroxide. H 2SO 5 (one peroxide bond)
Let, the oxidation number of Cr be x. 2(+1) + x + 3 (- 2) + 2 (- I)= 0 ⇒ 2 +x-6-2= 0
c~+ + 0 2+ 0 2- + 0 2 = cr0 5 x-6=0 ⇒ x=+6
x+(-l)x2+(-2)xl+(-l)x 2=0 53. Let the oxidation state of Cr in Cr2O 3 be x.
x-6=0 ⇒ x=+6 2x + (- 2) 3 = 0
Hence, the oxidation state of Cr is + 6 . 2x-6 = 0 ⇒ 2x=+6 ⇒ x=+3
45. Let, the oxidation state of sulphur in Na 2S4O6 bex. 54. Let the oxidation number of Cr be x.
:. For K 2Cr2 O7
Na 2S4O6 ⇒ (+J)x2 + 4xx +(- 2)x6= 0
+ Ix 2 + 2 x + 7 (- 2) = 0
2+4x-12=0 ⇒ 4x- 10=0 ⇒ 4x= I0
2+2x-14=0 ⇒ 2x= l 2 ⇒ x=+6
10
x= - =2.5 -I +6 0 +4
4 55. 2 ffi + H 2 SO 4 - I2 + SO2 + 2Hp
2
46. MnO4 + 8H+ + Se- - Mn + + 4Hz0 H 2SO 4 - reduced to - SO2
2 3 Oxid ising
[Fe + - Fe + + e-]x 5 agent
2
MnO4 + 8H+ + 5Fe + - Mn2+ + 5Fe3 + + 4H 2O 56. Let the oxidation number of sulphur be x
: . Five electrons get transferred. Na 2SzO 3 2(+ 1) + 2x + 3(- 2)=0
+7 +6 2+2x-6=0 ⇒ x=+2
47. In alkaline medium, KMnO4 + OH- - K 2 MnO4
2 (+ I)+ 4 (x) + 6 (- 2) = 0
Change in oxidation number= 7 - 6= I
2+ 4x- 12=0 ⇒ 4x= +I0
Hence, moles of KI = moles ofKMnO4 .
⇒ X = +2.5
 Redox Reactions I 211
57. Let the oxidation number ofN bex :.Change in oxidation state of Cr is zero when it changes from
N 3H (hydrazoic ac id) K 2Crp 7 to K 2CrO4 .
3 X (x) + I = 0 ⇒ 3x + I = 0 63. NaNO2 (sodium nitrite) acts both as an oxidising as well as
⇒ X = -1/3 reducing agent because in it N-atom is in + 3 oxidation state
58. Cr2O/- + 14H+ + 6e- - 2Cr 3+ + 7H2O (intermediate oxidation state).
Oxidising property
(2r - 12 + 2e-)x 3
2NaNO 2 + 2KI + 2H 2SO4 - Na 2SO 4
Cr2O 7 i- + 14H+ + 6r - 2Cr 3+ + 7Hp + 312 + KzSO4 + 2NO + 2H 2O + 12
Hence, number of moles ofl2 produced = 3 Reducing property
Oxidation
59. H 2O2 + NaNO2 - NaNO 3 + H 2O
0 0 +I - I 64. Let oxidation state of P in Ba(H2PO 2) 2 be x,
H2 + Br2 ~ 2 H Br
I(+ 2) + 2 (2 (+ I) + x + 2 (- 2)) = 0
Reduction 2 + 2 (2 + X - 4) = 0 ⇒ 2 + 4 + 2~ - 8 = 0
Only this reaction involves oxidation and reduction. 2+2x-4=0 ⇒ 2x=2 ⇒ x=+I
60. The oxidation state of iodine in HlO4 is+ 7 as 65. Let oxidation state of I in IPO4 be x
I + x + 4 (- 2) = 0 x+(-3)=0 (PO;ion has charge equal to - 3)
x=+7 x= + 3
The oxidation state of iodine in H 3TO5 is+ 7 as 66. Let the oxidation number of Xe be x in XeOF2.
3 + X + 5(- 2) = 0 ⇒ X = + 7
X + (- 2) + 2 (-I)= 0 ⇒ X - 2- 2= 0 ⇒ X =+4
The oxidation state of iodine in H 5 lO6 is+ 7 as
5 + X + 6 (- 2) = 0 67. The sum of oxidation states of all elements in an ion is equal to
charge on it.
x=+7
⇒
Let the oxidation state of S in so~- be x
61. Oxidation number of iodine in given species is as follows
x + (- 2 x 4) = - 2 or x =+ 6
Oxidation number of iodine in TF3 = + 3
Oxidation number of iodine in Tj" = - 1/ 3 68. 2K[Ag(CN)z + Zn] ~ 2Ag + K[Zn2 (CN)4]

Oxidation number of iodine in TF5 = + 5 I Reduction I t f

Oxidation number of iodine in TF7 = + 7 Oxidation

62. Let, oxidation state of Cr in K 2Crp7 be x 69. Oxidation takes place at anode. (c) is not feasible, i.e. CrJ+ is not
oxidised to Cr2O~- under given conditions.
(+ IX 2) + 2x + (- 2 X 7) = 0
Hence, option (d) is correct.
or + 2 + 2x-14=0
70. MnO4= Mn=+ 7 ⇒ MnO~- = Mn=+ 6
x=+6
Let, oxidation state of Cr in K 2CrO4 is x MnO2 =Mn= + 4 ⇒ Mn 2O 3 =Mn= + 3
(+ 1x2)+x +(- 2x4)=0 ⇒ 2 + x-8=0 ⇒ x=+6 Hence, changes in oxidation number are 5, I, 3, 4.
Hydrogen
QUICK REVIEW
Hydrogen is the most abundant element in the universe, it is • There is a big difference in masses ofprotium and deuterium
the first element in the periodic table and is the lightest known as also that of deuterium and tritium. Due to this difference
element. in their masses, their rate of reaction, ionic mobility and
equilibrium constants are quite different. Such a difference
Unique Position of Hydrogen in the Periodic Table
in properties of isotopes is called isotopic effect.
The configuration of hydrogen (1 s 1 ) is responsible for its
• Ordinary H2 is an equilibrium mixture of ortho and para
dual nature, i.e. it resembles halogens as well as alkali hydrogen. In ortho hydrogen, spin of protons are in same
metals. However, in some properties, it differs from both direction. While in para hydrogen, spin of protons are in
the groups. opposite direction.
Resemblance with Alkali Metals Preparation of Hydrogen (Lab Method)
• Liberation at cathode: Like alkali metals, hydrogen is It is prepared by the action of di!. HCl on granulated zinc.
liberated at cathode. Zn + 2H+ ~ Zn 2+ + H2 i
From
e.g. 2HCl (aq) Electrolysis H 2 (g)+ Cl 2 (g) acid
(At cathode) (At anode)
It is prepared by action of aqueous alkali on zinc.
Zn + 2NaOH ~ Na 2 ZnO 2 + H2 I
2NaCI (/) Electrolysis
2Na (!) + Cl2 (g) Sodium zincate
{At cathode) (At anode)
• On commercial scale, hydrogen is manufactured by
Resemblance with Halogens electrolysis of water, by passing steam over hot coke at
• Hydrogen combines with metal to form salt and exhibits - 1 1000°C (Bosch process) by decomposition of steam by
oxidation state like halogen. heated Fe at 550-800°C (Lane's process) or from
e.g. 2Na+ H2 ~ 2Na+H- or 2NaH hydrocarbons.
Sodium hydride
C + H2O Ni/ lOOo·c ) CO+ H2
2Na+ Cl 2 ~ 2Na+ Cl- or NaCl Coke Steam
Sodium chloride
Catalyst//',
• Hydrogen is unique in behaviour and is therefore, best CO+ H 2+ H2 O - ~ - - CO2 + 2H2
placed separately in the periodic table. Water gas FeCr04 (Water gas shift reaction)

Isotopes of Hydrogen 3Fe + 4H2O ~ Fe 3 O4 + 4H 2 i ;W = 16.01 kJ

• Naturally occurring hydrogen exists in three isotopic • Certain metals like palladium, platinum, iron and cobalt,
forms, i.e. protium ( 1 H 1 ), deuterium ( 1 H 2 ) and tritium etc., adsorb huge quantity of hydrogen. This phenomenon
3
( 1 H or T). is known as occlusion of hydrogen.

Hydrides
Hydrides are the binary compounds of hydrogen with other
elements. On the basis of properties and type of bonding,
hydrides may be of four types:
(i) Ionic or saline hydrides are formed by alkali and
alkaline earth metals (except Be and Mg) and some
lanthanides. These are used as solid fuel and as a
reducing agent, e.g. LiH, NaH, CaH 2 , etc.
(ii) Covalent or molecular hydrides are formed mainly
by p-block elements and by electron deficient species
(B, Al), electron precise species (C, Si, Ge) and
electron rich species (0, N, F). These hydrides may be
electron deficient hydrides (e.g. BH3 , AlH 3 , etc.) or
electron precise hydrides (e.g. SiH 4 , GeH4 , etc.) or
electron rich hydrides (e.g. NH 3 , H 2 O, HF, etc.)
(iii) Metallic or interstitial hydrides are formed by d and
fblock metals and are usually non-stoichiometric, e.g.
CrH, etc.
(iv) In complex hydrides, H- acts as ligand and is attached
to central metal atom, e.g. LiAlH4 , BaBH4 , etc.
Heavy Water (D 2O)
Water
The unusual properties of water in condensed phase (liquid
and solid states) are due to the presence ofextensive hydrogen
bonding between water molecules. This leads to high freezing
point, high boiling point, high heat of vaporisation and high
heat of fusion in comparison to H 2 Sand H 2 Se.
Hard and Soft Water
Water that lathers with soap is called soft water, e.g. rain
water, distilled water, etc., and which that does not, is called
hard water, i.e. sea water, well water, etc.
Hydrogen Peroxide (H 20
• Temporary hardness of water is due to the presence of
bicarbonates of calcium and magnesium while permanent
hardness is due to the presence of soluble chlorides and
sulphates of calcium and magnesium.
• Complexing agents like sodium hexametaphosphate,
2 • It is mainly manufactured by the electrolysis of 50%
sodium tripolyphosphate, EDTA, etc., do not remove Ca +
or Mg 2+ ions from hard water. These complexing agents
simply make these ions ineffective.
Removal of Temporary Hardness
(i) By boiling
Ca (HCO 3 h ~ CaCO3 J.. + H2 O+ CO2 i
(ii) By adding lime (Clark's method)
Ca(HCO3 ) 2 + Ca(OH) 2 ~ 2 CaCO3 J.. + 2 H2 0
Removal of Permanent Hardness
(i) By using washing soda
MC1 2 + Na 2 CO3 ~ MC0 3 J.. + 2NaCl
(M = Mg, Ca)
Hydrogen I 213
(iz) Calgon's method (Addition of sodium) polymeta
phosphate (NaPO3 )x, i.e. sodium hexarnetaphosphate is
[Na 2 Na 4 (PO 3 )d
(iii) Ion exchange method or zeolite or pemmtit method
• Permutit or zeolite is the aluminosilicate of sodium. It is
used to remove hardness of water. It converts insoluble
salts ofCa 2 + and Mg 2 + into soluble zeolites. It exchanges
Ca 2+ and Mg 2+ ions with Na+ and water become soft.
Thus, exhausted permutit does not contain Na+ ions.
2NaZ(s) + M 2+ (aq) ~ MZ 2 (s) + 2Na + (aq)
(M = Mg,Ca)
When all the sodium of the permutit is used up, the
pemmtit is called exhausted. It can be regenerated by
passing 10% NaCl solution through it.
MZ2 (s) + 2NaCl(aq) ~ 2NaZ(s) + MC12 (aq)
Exhausted Regenerated
zeolite zeolite
It is extensively used as a moderator in nuclear reactor and in
exchange reactions for the study of reaction mechanism. It is
manufactured by the electrolytic enrichment of normal water.
• Heavy water gives all the reactions that are shown by
ordinary water but rate of these reactions is slower. This is
called isotonic effect.
e.g. CaC2 + 2D 2 O ~ Ca(OD)i + C 2 D 2
Calciwn Calciwn Deutero
carbide deutroxide acetylene
2)
• It is stored in paraffin wax coated glass, plastic or teflon
bottles. Small amounts of acid, acetanilide glycerol,
alcohol and H3 PO 4 may be used as stabilisers to check its
decomposition.
H2 SO4 which is done at 0° C using Pt as anode and
graphite as cathode. Here, perdisulphuric acid (H 2 S 2 0 8 ) is
formed at anode, which on hydrolysis gives H 2 O 2 •
• It is a strong oxidising agent in acidic as well as in basic
medium and also acts as reducing agent towards strong
oxidising agents in acidic as well as in basic medium.
• It is non-linear, non-planar molecule.
The - 0 - 0 - linkage is called peroxy linkage.
Strength of hydrogen peroxide
(i) Per cent strength = 17 / 56 x volume strength
(ii) Volume strength = 5.6xnormality
(iii) Volume strength= 11.2 xmolarity
 Topic 1
Position of Hydrogen in the Periodic Table,
Preparation and Properties of Dihydrogen
2014
1. The production of dihydrogen gas via water gas shift 5. Hydrogen is prepared on large scale for industrial use
. a [Indraprastha CET, CG PET]
reaction, CO(g) + H 2 O(g) ~ CO2 (g) + H 2 (g ).
Catalyst (a) by Zn + H 2 SO4 (b) by Al + NaOH
The CO 2 gas is removed by scmbbing with solution of (c) by Na + C 2 H 5 OH (d.) from water gas
(a) sodium arsenite (b) calcium oxide [AMUJ
(c) sodium phosphite (d) aluminium oxide 2008
6. In context with the industrial preparation of hydrogen from
2013 water gas (CO+ H2 ), which of the following is the con-ect
2. Very pure hydrogen (99.9) can be made by which of the statement? [AIEEEJ
following processes? [AIEEEJ (a) CO and H2 are fractionally separated using
(a) Reaction of methane with stean1 differences in their densities
(b) Mixing natural hydrocarbons of high molecular (b) CO is removed by absorption in aqueous Cu 2 Cl 2
weight solution
(c) Electrolysis of water (c) H2 is removed through occlusion with Pd
(d) Reaction of salts like hydrides with water (d.) CO is oxidised to CO2 with steam in the presence of a
catalyst followed by absorption of CO 2 in alkali
2010
3. Hydrogen molecule differs from chlorine molecule in the 2006
following respect. CRPETJ 7. The ortho and para hydrogen differ in respect of which of
(a) Hydrogen molecule is non-polar but chlorine the following? [WB JEEJ
molecule is polar (a) In the molecular weight
(b) Hydrogen molecule is polar while chlorine molecule (b) In the nature of spin of protons
is non-polar (c) In the nature of spin of electrons
(c) Hydrogen molecule can form intermolecular (d.) In the number of protons
hydrogen bonds but chlorine molecule does not
8. Adsorbed. hydrogen by palladium is known as [Guj CETJ
(d) Hydrogen molecule cannot participate in coordinate
bond formation but chlorine molecule can (a) nascent (b) atomic
(c) heavy (d.) occluded.
2009
4. The most abundant element in the universe is thought
2005
to be [UPSEEJ 9. Hydrogen is not obtained when Zn reacts with [J&K CETJ

(a) carbon (b) oxygen (a) cold water (b) hot NaOH solution
(c) hydrogen (d) nitrogen (c) dil. H2 SO4 (d.) dil. HCl
 Topic 2
Hydrides, Water, Hydrogen Peroxide
(H2 O 2 ) and Heavy Water (D 2 O)
2014 2009
1. Which one of the following is a covalent hydride? 10. The strength of 10 volume ofH 2O 2 solution is [AMUJ
(a) CaH2 {b) NaH [BITSAT] (a) IO g/L (b) 68 g/L
(c) BH3 (d) BeH2 (c) 60.70 g/L (d) 30.36 g/L
2. The volume strength of 1.5 N H 2 0 2 solution is [VITEEEJ l 1. In which of the following reactions, H 20 2 is acting as a
(a) 16.8 L (b) 8.4 L reducing agent? [AMU]
(c) 4.2 L (d) 5.2 L
(a) SO 2 + H 2O2 ~ H2SO4
3. Commercial sample of H 2O 2 is labeled as 10 V. Its % (b) 2KJ + H2 0 2 ~ 2KOH + 12
strength is nearly [WB JEE] (c) PbS + 4H 2O 2 ~ PbSO4 + 4H2O
(a) 3 (b) 6 {c) 9 (d) 12 (d) Ag 2O + H 2O 2 ~ 2Ag+ HzO + 02
4. Temporary hardness of water is removed in Clark's 2008
process by adding [EAMCET]
12. Which one of the following reactions represents the
(a) caustic (b) calgon oxidising property ofH2O2? [BITSAT, AMU, EAMCET]
(c) borax (d) lime
(a) 2KMnO 4 + 3H2SO4 + 5H2O 2 ~
2013 K 2 SO4 + 2MnSO 4 + 8H 2O + 502
5. Which of the following is responsible for the hardness of (b) 2K 3 [Fe(CN)6 ] + 2KOH + H 2O2 ~
water? [Manipal]
2K 4 [Fe(CN)6 ] + 2H2 O + 02
(a) CaHCO3 (b) CaC1 2 (c) PbO2 + H 2O 2 ~ PbO + H 2O+ 02
(c) Both (a) and (b) (d) None of these
(d) 2KJ + H 2SO 4 + H 2O 2 ~ K 2SO 4 + l 2 + 2HzO
6. When H 2O 2 is shaken with an acidified solution of
13. Which of the following statements is correct? Dielectric
K 2Cr20 7 in the presence of ether, the ethereal layer twns constant of H2 O2 [Manipal]
blue due to the formation of [WB JEE]
(a) increases with dilution (b) decreases with dilution
(a) Cr2O 3 (b) Crot ( c) is unaffected on dilution ( d) None of these
(c) Cr2 (SO) 3 (d) CrO5 14. In transforming 0.01 mole of PbS to PbSO4 , the volume of
7. Which of the following is not correct for D 2O? [OJEEJ IO volume H 2O2 required will be lWB JEE]
( a) Boiling point is higher than H 20 (a) 11.2 mL (b) 22.4 mL (c) 33.6 mL (d) 44.8 m L
(b) D 2Oreacts slowly than H 2O
15. Heavy water is represented as [UPSEEJ
(c) Viscosity is higher than H 2Oat 25°C 18
(d) Solubility of NaCl in it is more than H2O (a) H2 O (b) D2O
18
(c) D 2 O (d)H2Oat4°C
2011
16. Which one of the following is used for reviving the
8. The normality of30 volume H 20 2 is [WB JEE] exhausted 'permutit' ? [DCEJ
(a) 2.678 N (b) 5.336 N (c) 8.034 N (d) 6.685 N (a) HCl solution (b) IO% CaC'2 solution
(c) 10% MgC'2 solution (d) 10% NaCl solution
2010
17. Which of the following is not cotTect regarding the
9. Moist hydrogen peroxide cannot be dried over cone.
electrolytic preparation ofH2O 2 ? [DCEJ
H 2SO4 because [RPETJ
(a) Lead is used as cathode
(a) it can catch fire
(b) 50% H2SO4 is used
(b) it is reduced by H2SO 4
(c) Hydrogen is liberated at anode
( c) it is oxidised by H 2SO4
(d) Sulphuric acid undergoes oxidation
( d) it is decomposed by H2 SO4
216 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2007 2006
18. Which one of the following processes will produce hard 26. Calgon used as water softener is [BITSATJ
water ? [MP PET] (a)Na 2 [Na 4 (PO3 ) 6 ] (b)Na 2[Na 4 (PO3 ) 5 ]
(a) Saturation of water with CaCO3 (c)Na 4 [Na 2 (PO3 ) 6 ] (d)Noneofthese
(b) Saturation of water with MgCO3 27. The volume of oxygen liberated from 0.68 g ofH 2 O 2 is
(c) Saturation of water with CaSO4
(a) 112 mL (b) 224 mL [Manipal]
(d) Addition ofNa 2 SO4 to water
(c) 56 mL (d) 336 mL
19. Match the Column I with Column IL
28. H 2 0 2 is manufactured these days [Manipal]
Column I Column II (a) by the action ofH 2O 2 on BaO2
(Hydride) (Type of hydride) (b) by the action of H 2 0 2 on H 2 0 2
A. BeH2 I. Complex (c) by electrolysis of 50% H2 SO4
B. AsH3 2. Lewis acid (d) by burning hydrogen in excess of oxygen
C. B2H6 3. Interstitial 29. Ka. ofH 2 O2 isoftheorderof CMHTCET]
D. LaH3 4. Covalent (a) 10-1 2 (b) 10- 14 (c) 10- 16 (d) 10- 10
E. LiAlH4 5. Intermediate
30. Electrolysis ofX gives Yat anode. Vacuum distillation of Y
6. Tonic
gives H2O2 . The number ofperoxy (0- 0) bonds present
Codes [Ke rala CEE] in X and Y respectively are [EAMCETJ
A B C D E (a)l, l (b) l ,2
(a) 6 2 4 5 I (c) zero, 1 (d) zero, zero
(b) 6 2 4 3 I
31. What is formed when calcium carbide react with heavy
(c) 6 4 2 3 5
water? [DCEJ
(d) 6 4 2 3 I
(e) 5 4 2 3 I (a) C2 D2 (b) CaD2 (c) CaD2 O (d) CD 2
20. The hardness of water sample containing 0.002 mole of 32. Water possesses a high dielectric constant, therefore
magnesium sulphate dissolved in a litre of water is (a) it always contains ions [Jamia Millia Islamia]
expressed as [Kerala CEE] (b) it is universal solvent
(a) 20 ppm (b) 200 ppm (c) 2000 ppm (c) can dissolve covalent compounds
(d) 120 ppm (e) 240 ppm (d) can conduct electricity
21. Permanent hardness can be removed by adding [WB JEE]
2005
(a) Cl 2 (b) Na 2 CO3
33. The oxidation number of oxygen in hydrogen peroxide is
(c) Ca(OCl) Cl (d) K 2 CO3
(a) + l (b) - 1 [BITSAT]
22. Decomposition of H2 0 2 is prevented by [AMU] (c) + 2 (d) - 2
(a) KOH (b) MnO 2 34. Among CaH 2 , NH3 NaH and B2 H 6 , which are covalent
(c) acetanilide (d) oxalic acid hydride ? [OJEE]
23. Assertion (A) NaCl is less soluble in heavy water than in (a) NH 3 and B2H6 (b) NaH and CaH2
ordinary water. (c) NaH and NH 3 (d) CaH2and B2H 6
Reason (R) Dielectric constant of ordinary water is
35. Which one of the following reactions does not form
more than that of heavy water.
gaseous product ? [EAMCET]
(a) Both A and R are co1Tect and R is the correct
explanation of A (a) PbO2 + H2O2 ~
(b) Both A and R are correct but R is not the correct (b) Acidified KMnO4 + H2 O2 ~
explanation of A (c) PbS + H2 O2 ~
(c) A is correct but R is not correct (d) Cl 2 + H 2 O2 ~
(d) A is not correct but R is correct 36. The pH of a solution of H2 0 2 is 6.0. Some chloride gas is
24. Which of the following is an exan1ple of interstitial hydride? bubbled into this solution. Which of the following is
(a) NH3 (b) CH4 [EAMCET] correct ? [EAMCETJ
(c) ZnH 2 (d) H 2 O (a) The pH of resultant solution becomes 8.0
(b) Hydrogen gas is liberated from resultant solution
25. Which cannot be oxidised by H2 0 2 ? [BCECEJ
(c) The pH of resultant solution becomes less than 6.0
(a) Na 2SO3 (b) PbS and oxygen gas is liberated
(c) Kl (d) 0 3 (d) Cl 2 0 is formed in the resultant solution
 Hydrogen I 217
37. What is the volume of '20 volume H 2 0 2 ' required to get 39. Which is false about H 2 0 2 ? [DCE]
5000 cm3 of oxygen at STP ? [Guj CET] (a) Act as both oxidising and reducing agent
(a) 250 cm3 (b) 20 cm3 (c) 100 cm3 (d) 125 cm3 (b) Two OH bonds lie in the same plane
38. H 2 0 2 is formed by which of the following compounds? (c) Pale b lue liquid
(d) Can be oxidised by ozone
(a) Na 2 0 2 (b) NaOH [BCECE]
(c) Na 2 0 (d) K0 2

Answers
TOPICl Position of Hydrogen in the Periodic Table, Preparation and Properties of Dihydrogen
1. (a) 2. (d} 3. (d) 4. (c) 5. (d) 6. (d} 7. (b) 8. (d) 9. (a)
TOPIC2 Hydrides, Water, Hydrogen Peroxide (H2 O 2 ) and Heavy Water (D 2 O)
1. (c) 2. (b) 3. (a) 4. (d) 5. (c) 6. (d} 7. (d) 8. (b) 9. (d) 10. (d}
11. (d) 12. ( d) 13. (a) 14. (d) 15. (b) 16. ( d) 17. (c) 18. (c) 19. (e) 20. (b)
21. (b) 22. (c) 23. (a) 24. (c) 25. (d) 26. (a) 27. (b) 28. (c) 29. (a) 30. (c)
31. (a) 32. (b) 33. (b) 34. (a) 35. (c) 36. (c) 37. (a) 38. (a) 39. (b)

Explanations
Topic 1 P osition of Hydrogen in the Periodic Table, Preparation and
Properties of Dihydro gen
1. The production of dihydrogen gas can be increased by the CO2 is removed by washing 1mder pressure of25-30 atmospheres
reaction of carbon monoxide of the water gas (CO + H 2) with or by scrubbing with a solution of sodium arsenite or by
steam in the presence of iron chromate as catalyst at 673 K. absorption of CO 2 in KOH scale away industrial. The above,
Fe Cr04 process used for production ofH 2 is called Bosch process.
CO (g) + Hp(g) - ---. CO2(g)+ 2H2(g)
673 K 6. The CO formed during Bosch's process is oxidised to CO2 with
This reaction is called water gas shift reaction. steam in the presence ofa catalyst followed by absorption of CO 2
Here, the obtained carbon dioxide (CO2) is removed by scrubbing in alkali.
w ith a solution of sodium arsenite. CO + H2 + H 2O --➔ CO2 + 2H2
'---v--' Steam Catalyst I
2. Hydrides are instant source of hydrogen of higher purity. They Water gas ,,L, KOH

react with H 2O forming H 2 gas. KHC03

3 . Hydrogen molecule cannot participate in coordinate bond 7. The ortho and para hydrogen differ in the nature of spin of
formation because it does not possess any lone pair of protons. In ortho hydrogen, the spin of protons are in the same
electrons. direction, while in para hydrogen the spin of protons are in
opposite direction.
4. Hydrogen forms about 75% of the mass (total amount) of the
u niverse. Tt has been estimated that more than 90% of all atoms
in the universe a re H-atoms. While most of the remaining atoms
®'ortho<iJ ~~
para
are of He. The order of abundance of given elements in the (parallel spin) (anti-parallel spin)
universe is
H > O >C>N 8. Adsorbed hydrogen by palladium is known as occluded hydrogen.
9. Zinc does not react w ith cold water rather it reacts with steam to
5. Industrially, dihydrogen is prepared through the reaction of water produce H 2.
gas (or syn. gas, CO+ Hi) with steam in the presence of iron Zn+ H2O -➔ ZnO + H 2 i
chromate as a catalyst at 673 K. Steam
C(s) + H O(g) ➔ CO (g)+ H2 (g) It also reacts with alkali and acids to form salt and H2.
2
~o~CH;OO" C =:iheated Water gas or syn gas
Zn + 2NaOH -➔ Na 2 ZnO2 + H 2 i
FeCr04
CO(g)+ H 2 (g) + Hp(g) Zn+ 2HCl(dil.) -➔ ZnCl 2 + H2 i
673 K
Water gas
Zn+ H 2 SO 4 (dil.) -➔ ZnSO 4 + H 2 i
Topic 2 Hydrides, Water, Hydrogen Peroxide (H 2 0 2 ) and
Heavy Water (D20)
1. The compounds of hydrogen in which hydrogen is present as 5. Temporary hardness of water is due to the presence of
hydride ion are called hydrides. bicarbonates of calcium and magnesium while permanent
These can be classified into four groups hardness is due to the presence ofsoluble chlorides and sulphates
(i) Ionic hydrides-NaH, CaH2, LiH
of calcium and magnesium.
(formed by mostly s-block elements) 6. When cold H 2O2 is added to cold mixture ofK 2Cr2O 7 and cone.
H 2SO 4 (i.e. K 2 Crz07 in acidic medium) and the mixture is shaken
(ii) Covalent hydrides-B2H 6 , NH3 , SbH 3 in the presence of ether, the ethereal layer of the solution turns
(formed by p-block elements) blue due to the formation of blue perchromate (perchromate
(iii) Polynuclear hydrides- LiAIH4 , NaBH4 contains peroxide linkage), CrO 5 .
(iv) Interstitial hydrides are those in which hydrogen is trapped in K 2Cr2O7 + H 2SO4 ~ K 2SO4 + H 2Cr2O7
the interstitial spaces of transition metals.
H 2 Cr2O 7 + 4H2O2~ 2CrO 5 + 5H 2O
BH3 exists as a dimeric form of is a dimeric form ofBiT-\i as Blue
BH3 is covalently combined with another BH3 molecule to perchromate

form B 2H6 which contain 3 centre 2e- bond. Thus, Bzl\ is 7. D 2O gives all the reactions that are given by ordinary water but
e lectron deficient covalent hydride. with a slower rate. This is called isotopic effect. Hence, due to
isotopic effect, solubility ofNaCI is less in op.
2. Strength= normality x equivalent weight
8. Volume strength ofH 2O 2 = 5.6 x normality
= l.5x l 7 gL- 1= 25.5gL- t
30
30 = 5.6xN , N = - = 5.357 "" 5.336 N
As, 68 g of H 2O 2 at NTP gives 0 2 = 22400 mL 5.6
. 22400 9. Moist H 2 O 2 cannot be dried over cone. H 2SO4 because it is
:. 25.5 gofHz02 atNTP gives 0 2 = - - x25.5= 8400 mL
68 decomposed by H 2SO4.
But, 25.5 g ofH 2O is present in 1000 mL ofH 2O. 10. IOvolume ofH2O 2 means 1 mL ofH2O2 at NTP gives 10 mL of
Hence, I 000 mL ofH2O 2 solution will give 0 2 (at NTP) 0 2 gas.
2H 2O 2 ~ 2H2O + 02
= 8400 mL 2(2 + 32) = 68 g 22400 mL at NTP
8400 AtNTP,
:. I mL ofH,O2 solution will give 0 2 = = 8.4 mL
- 1000
·: 22400 mL ofO2 is obtained from = 68 g Hz0 2
Hence, the volume strength of 1.5 NH 2O2 is 8.4 L. 68 1
:. IO mL of 0, is obtained from= x O= 0.03035 g H 2O 2
3. '10 V Hz02' means I L of this solution will produces IO L 0 2 on - 22400
its decomposition at STP. I mL ofH2 O 2 solution contains= 0.03035 g H 2O 2
2H2O2 ~ 2H2O + 02 I00 mL ofH 2O 2 solution contains = 0.03035 x I 00= 3.05 g H 2O 2
2(2 + 32) ~68 g 22.4 Lat STP
:. Strength of IO volume
·: 22.4 L of 0 2 is obtained from = 68 g Hz02 H2O2 = 3.035 x 10 = 30.35 g I L
:. IOL of 0 2 will be obtained from=~ x 10 = 30.36 g H 2O2 11. H 2O2 is acting as a reducing agent in the reaction that involve
22.4 increase in the oxidation state of oxygen ofHz02 (i.e. in which
:.1000 mL of the given solution contains 30.36 g H 2O 2 and 100 H 2O2 is being oxidised).
mL of the given solution contains +I - I O - 2 0
Agp + HP2 -➔ 2Ag + H2O + 02
30.36x 100 _ HO
3 03
1000 g 2 2 Thus, H 2O 2 acts as as a reducing agent in the above reaction,
while in other reactions it acts as an oxidising agent by accepting
Thus,% strength ofH2O 2 is 3.03 (o: 3)
electron and itself gets reduced.
4. The temporary hardness of water is due to the presence of
12. The reaction in which H 2O 2 is reduced while the other reactant is
bicarbonates of Ca and Mg. This may be removed by Clark's
process. In this process, addition of calculated quantity of lime oxidised, represents the oxidising property ofH2O2.
causes precipitation of CaCO3 as
t Oxidation i
Ca(HCO3) 2 + Ca(OH)2 ~ 2CaCO3 ! +2Hz0 -I
2KI + H2S04 + H2O2 -
-I O
K 2SO4 + !2 + 2H 20
-2

and Mg(HCO 3)2 + 2Ca(OH)z ~ 2CaCO3 ! Oxidising Oxidation

agent
+ Mg(OH)2 + 2H2O 13. Dielectric constant ofH 2O 2 increases with dilution. It is 93.7 for
pure Hz02, 97 for 90% H 2O 2 and 120 for 65% Hz0 2.
 Hydrogen I 219
14. PbS + 4Hz0 2 - PbSO 4 + 4H2O 20. The hardness of water sample containing 0.002 mole of
From the above equation MgSO4 dissolved in I L ofwater can be determined as
Number of moles = mass/molecular mass
:. I mole ofPbS requires 4 moles ofH2O2 . Thus, 0.01 mole of PbS requires
0.04 moles of H 2O 2. Weight of 0.04 mot H 2O 2 = 1.36 g (w = moles x 0.002 =mass/120
molecular weight) 10 volume ofH 2O2 means, 1 mL of such solution ofH 2O2 mass =0.24g
on decomposition by heat produces IO mL of oxygen at NTP. 0.24 g mass ofMgSO4 dissolved in I L of water.
H 2O 2 decomposes as, 2H2O 2 - 2Hz0+ 0 2 As, 103 g ofH2O contains= 0.24g ofMgSO4
Thus I mL of IO volume Hz02 solution contains
68
= - - x IO g ofH 2O 2 = 0.030035 g ofH z02
0 24
:. 106 g ofH 2O contains= · ~
Hf' g ofMgSO 4
10
22400
= 0.24 x 103 g = 240 g of MgSO 4
·: 0.03035 g ofH2O2 is present in I mL of 10 volume H 2O2.
1 Thus, 106 gofwater contains= 240 g ofMgSO 4
:.1.36 g ofH 2 O 2 present in - -- x 1.36 mL = 44.81 mL of
0.03035 As, 120 g MgSO4 == 100 g of CaCO3
10 volume ofH 2O 2 . 100 X 24
:. 240gofMgSO4 = =200gofCaCO 3
15. Heavy water is the oxide of heavy hydrogen (deuterium), hence named 120
heavy water.It is represented by D 2O. It is used in nuclear reactor as Hence, hardness of H 2O = 200 ppm
moderator.
21. Permanent hardness is removed by precipitating
16. During the softening process, when hard water is treated with permutit C or carbonates of Ca2+ and Mg2+ by adding Na 2CO 3 to
zeolite (Na2 Al 2Si2O 8 · H 2O~ the cations present in hard water are hard water.
exchanged wid1 Na+ ions. CaC12 + Na 2CO 3 - CaCO 3 ! + 2NaCI
Na2 Z + MC1 2 [fromhardwater]~ MZ+ 2NaCl Containing chlorides of calcimn and magnesium.
~i/:: [Here, M = Ca or Mg] MgCl 2 + Na 2CO3 - MgCO 3 ! + 2NaCI
After sometime, the zeolite is completely converted into calcium and
22. Pure hydrogen peroxide is an unstable liquid and
magnesium salts. Eventually, the bed ceases to soften water, i.e. it gets
decomposes into water and oxygen either upon
exhausted.
standing or heating.
At this stage, the supply of hard water is stopped and the exhausted zeolite is
regenerated by treating the bed w ith a 10% NaCl solution (brine solution).
Ml= -196 .0 kJ
CaZ or MgZ + 2NaCI - Na 2Z + CaCl 2 or MgCl 2
(Exhausted Reclaimed To prevent decomposition of H 2O 2, phosphoric acid,
permuttt) zeolite acetanilide or glycerol are added. These act as
negative catalyst (stabilisers) for its decomposition.
17. H 2O 2 can be prepared by electrolysis of 50% H 2SO4. In this method,
hydrogen is liberated at cathode and per disulphuric acid (H2SzO 8 ) is formed 23. NaCl is less soluble in heavy water than in ordinary
at anode. water because dielectric constant of ordinary water
(i.e. 8 1) is more than that of heavy water ( i.e. 80).
H2SO4 ~ W + HSO4
24. ZnH 2 is an example of interstitial hydride w hile
At anode 2Hso-4 - H 2SzO8 + 2e- NH3 , CH 4 and H 2O are the examples of covalent
At cathode 2H+ + 2e- - 2H- H2 i hy dride.
25. Na 2SO 3 is oxidised by Hz02 to Na 2SO4
H 2SzO 8 + 2Hz0 - 2H2SO 4 + Hz02
PbS is oxidised by H 2O 2 to PbSO4
The H 2SzO8 on hydrolysis gives H 2O 2 which is separated by distillation
under reduced pressure, KI is oxidised by H z02 to I2
But 0 3 cannot be oxidised by Hz0 2 as it is reduced to
18. Alka line earth metal salts causes hardness of water which may be temporary
or permanent. The temporary hardness of water is caused by soluble Ca and 0 2 by Hz0 2
Mg hydrogen carbonates while calcium and magnesium soluble sulphates H 2O 2 + 0 3 - H 2O + 20 2
and chlorides cause permanent hardness.
In fact in the above reaction, both reduce each other.
19. Complex compounds do not give all their constituent ions when dissolved in
26. Calgon is chemically sodium hexametaphosphate,
water, e.g. [Cu (NH 3 ) 4 ] SO4, LiAIH4 . Lewis acid are electrons deficient
Nai[NaiPO 3\ ] .
species which gain electrons while forming a bond w ith Lewis bases, e.g.
B 2H6. Interstitial meta l hydrides or f-block hydrides are 27. 2H2 0 2 - 2H 20+ 02
non-stoichiometric, e.g. LaH 3, etc., where chemical composition is variable, 2 X 34 g 22400 mL
e.g. LaH2.s7 etc. ·: 68 g of Hz02 liberates 22400 mL 0 2
Intermediate hydride polymeric in nature, e.g. bond ionic nature of BeH2 in :. 0.68 g ofHz02 liberates
solid state changes to covalent by fonning a polymeric hydride. Covalent 0.68x 22400
hydrides are mainly formed by p-block elements, e.g. AsH 3• 224 mLO2
68
220 I Chapterwise & Topicwise Engineering Entrances Solved Papers
28. Electrolysis of 50% sulphuric acid is the commercial method for (iii) Polynuclear hydrides, e.g. LiAIH4, NaBH4, etc.
the preparation of hydrogen peroxide. (iv) Interstitial hydrides, in which hydrogen is trapped in the
H 2SO 4 - H+ + HSO4 interstitial spaces of transition metals.
35. Hydrogen peroxide oxidise lead sulphide into solid lead sulphate
At anode and water.
PbS + 4H2 O 2 -➔ PbSO 4 + 4H2O
At cathode While all the other given reactions produces 0 2 as a gaseous
by-product.
29. Hp 2 (hydrogen peroxide) is a corrosive volatile liquid. It is
slightly acidic in nature. Its Ka value is l.4x l o- 12, i.e. PbO2 + H2O2 - PbO + H2O + 02
approximately 10- 12. 2KMnO4 + 3H2SO4 + 5H2O2 -
30. A 30% solution of hydrogen peroxide can be obtained by the K 2SO4 + 2Mn SO4 + 8Hp + 502
electrolysis of 50% sulphuric acid followed by vacuum Cl2 + H2O2 - 2HC1 + 02
distillation. The first product of electrolysis is per disulphuric
acid (H2SzO8)which reacts with water during distillation to form 36. H 2O2 + Cl 2 ~ 2HC1 + 0 2
H2O2- HCl is formed by the reduction of chlorine by H 2O 2, hence pH
2H2SO4 - 2W + 2Hso:; forther decreases.

2HSO 4- H 2SzO8 + 2e- 37. '20 volume H 2O2 means that 1 mL of this H 2O 2 gives 20 mL
oxygen on decomposition at STP.
H2SzO8 + 2H2O - 2H 2SO4 + Hp 2
Hence, 5000 cm 3 0 2 will be obtained by= 5000/20= 250 cm 3
'X' is H 2SO4 and 'Y' is H 2SzO8. So, '.X'and 'Y'contains zero and
one peroxy bond respectively.
38. Na2O2 + H2SO4 Iceoold ) Na2SO4 + H2O2
31. Calcium carbide reacts with heavy water to give C2D 2 as
:. H 2O 2 is formed by reaction ofNap2 on di!. H 2SO4•
CaC2 + 2Dp - C2D 2 + Ca(OD)z
Calcium deutroxide 39. H 2O2 is pale blue liquid, it can be oxidised by ozone.
32. Due to its high dielectric constant and polar nature, water is an H 2O2 acts as both oxidising and reducing agent.
excellent solvent for polar and ionic substances. The value of dipole moment of H 2O 2 is 2.1 D which suggests it
Hence, water acts as a universal solvent. cannot be planar. In fact it has open book like stmcture.
33. Oxidation number of oxygen in hydrogen peroxide is - 1 as it The two 0 - H bonds lie in different planes.
contains peroxide linkage.
H- O- O- H
J, H
H 98.S pm
Peroxide linkage 950 pm 1145.8 pm
1147.S pm
34. Hydrides are binary compounds of hydrogen. These can be 0 ~ 1 11.5" o~o,- 90.2°

94.9' H 1o"i":?sH
classified in four groups viz,
(i) Ionic hydrides, e.g. NaH, CaH2, LiH, etc.
(ii) Covalent hydrides, e.g. B2~, NH3 , SbH3, etc. (a) H,O, structure in gas phase (b) H 2 O, structure in solid phase
s- Block Elements
QUICK REVIEW
The elements in which the last electron enters the outermost Atomic Chemical Properties
s-orbital are called s-block elements. s-orbital can have Reactivity Towards Air On combustion in excess of air,
maximum of two electrons, therefore they are comprised of lithium forms mainly the oxide (Li 2 0), sodium forms
only two groups (I and II). peroxide (Na 2 0 2 ) while potassium, rubidium and caesium
fom1 the superoxides. The increasing stability of peroxide or
Alkali Metals Group IA superoxide is due to the stabilisation oflarge anions by larger
This group consists of the elements lithium, sodium, cations through lattice energy effects. The alkali metal
potassium, rubidium, caesium and francium. These are hydroxides are the strongest of all bases.
collectively known as alkali metals. These are so called
because they form hydroxides on reaction with water which are Solution in Liquid Ammonia
strongly alkaline in nature. Francium is highly radioactive. All alkali metals when dissolved in liquid ammonia gives
Electronic Configuration deep blue solution which is paramagnetic and conducting
in nature.
The general electronic configuration of these elements is
[noble, gas] ns 1 and their ionisation enthalpies are M + (x + y)NH3 ~ [M (NH~ )xt + [e (NH 3 )yr
Ammoruated Ammoniated
considerably low. Alkali metals and their salts impart cation electron
characteristic colour to an oxidising flame.
It is the ammoniated electron (e - ) which is responsible for
Metal Li Na K Rb Cs the blue colour of the solution as they absorb the energy
Colour Crimson Yellow Violet Red Blue from visible region oflight and thus, imparts blue colour to
red violet the solution. The electrical conductiv ity is due to the
ammoniated cations as well as ammoniated electron. These
Atomic Physical Properties solutions are strong reducing agents due to the presence of
While going left to right (in periodic table) following free electrons. It reduces (i) metal hal ides to metals (ii) N 2 0
properties decrease: to N 2 (iii) 0 2 to 0 2 and then too~- .
(i) Atomic's ionic radii • Na is manufactured by the electrolysis of fused sodium
(ii) Metallic character chloride in the presence ofCaC1 2 and KF. They both lowers
(iii) Electropositive nature the melting point of electrolyte using graphite anode and
(iv) Density, melting point and boiling point iron cathode (Down process). To reduce the rigorousness of
sodium, it is amalgamated with mercury.
While going top to bottom (in periodic table) following
properties decrease : • Anomalous properties of lithium difference between
lithium and other alkali metals is mainly due to
(i) Ionisation energy
exceptionally smaller size of the Li atom, Li has the highest
(ii) Hydration enthalpy ionisation energy and electronegativ ity as compared to
(iii) Lattice energy other alkali metals.
222 I Chapterwise & Topicwise Engineering Entrances Solved Papers
• Lithium shows resemblance with magnesium, an element
of group II A . This resemblance is termed as diagonal
relationship.
Important Compounds of Sodium
Sodium hydroxide, NaOH (caustic soda) is obtained by
using NaCl as starting material by mercury cathode process
(Castner-Kellner cell).
(i) Caustic soda is used in Baeyer's process for cone. of
bauxite ore.
(ii) Sodium carbonate, Na 2 CO3 · lOH 2 O(washing soda) is
obtained by Solvay process. In this process brine
(NaCl), NH 3 and CO2 are used as raw materials.
(iii) Sodium bicarbonate (baking soda) is obtained as the
intermediate product in Solvay process.It is used as a
medicine to neutralise the acidity in the stomach and in
making effervescent drinks.
(v) Sodium thiosulphate, Na 2 S 2 O 3 · 5H2 O (hypo) is used
in photography as a fixing agent and as an antichlor to
remove excess of chlorine from bleached fabrics. It
also acts as a reducing agent and used in volumetric
estimation of iodine.
(iv) Microcosmic salt Na (NH4 )HPO 4 is used for detection
of coloured ions such as Cu 2+, Ni 2 +, etc.
(v) Sodium sulphate, Na 2 SO4 -10H 2 O is known as
Glauber's salt.
Important Compounds of Potassium
Potassium hydroxide (caustic potash) is manufactured by
electrolysis of KCl solution or by the action of lime on
potassium carbonate.
(i) Potassium carbonate (potash or pearl ash) is
manufactured by Le-blanc process or by Batch process
(magnesia process).
(ii) K 2 CO3 is used as a fusion mixture (mixture of
Na 2 CO 3 and K 2 CO3 in equimolar an1ount).
(iii) The alkaline solution of K 2 Hgl 4 is called Nessler's
reagent. It is used for the detection of NH! ion.
Alkaline Earth Metals Group II A
This group consists of elements beryllium, magnesium,
calcium, strontium, barium and radium. General electronic
configuration is [noble gas] ns 2 .
Atomic Physical Properties
(i) Hydration and lattice energies decreas with increase in
size of metal ions.
(ii) Decrease in hydration energy favours the ionic
mobility and ionic conductance of metal ions.
This is because smaller the size of ion, more highly it is
hydrated. Hence, its hydrated ionic radii will be large
and its ionic mobility is loss. Hence, ionic conductance
decreases in aqueous solution.
Size of hydration ion :
Li+> Na+ > K + > Rb+ > Cs+
Ionic mobility and conductance :
Li+ <Na+ <K+ <Rb+ <Cs+
Magnesium is extracted from sea water by Dow's process or
by electrolysis ofMgCli(35% MgC1 2 + 50% NaCl + 15%
CaCl 2 ). The mixture is electrolysed in presence of an inert
gas to protect it from reaction ofN2 , 0 2 and CO 2 present
in the air.
Atomic Chemical Properties
(i) Compounds of magnesium Magnesium sulphate,
MgSO4 · 7H 2 O is known as epsom salt.
(ii) A suspension of magnesium hydroxide in water called
milk of magnesia used as an antacid drug.
(iii) Magnesium chloride, MgCI 2 · 6H2 0 occurs in nature
as camallite (KCl-MgC12 -6H 2 O) and bischofite
(MgCl 2 · H 2 0). It is used for making Sorel 's cement
(MgCl 2 -5MgO·xH2 O}
Compounds of Calcium
(i) Calcium oxide (CaO) or quicklime or bmnt lime is
prepared by the decomposition of CaCO3 at 800° C
t,.
CaCO3 :.====! CaO + CO2
(ii) Ca(OHh is slaked lime, paste of lime in water is called
milk oflime while its clear filtrate is known as lime water.
(iii) Plaster of Paris (calcium sulphate hemihydrate),
2CaSO4 · H 2 O is obtained when gypsum is heated at
120°C.
393 K
2CaSO 4 -2H2 O ~ (CaSO 4 )i -H 2 O
G)Psum
Plaster of Paris
(iii) Anhydrous CaC12 is used as a drying agent in lab.
Biological Importance of Mg and Ca
• Mg and Ca play vital role in biological reactions. The
pigment chlorophyll which contains magnesium absorbs
s1mlight in plants.
2
• Calcium occurs in animal bones as phosphates. Ca + ions
involved in enzymatic systems, play role in regulating
muscle contraction, transmitting nervous pulses and act as
an agent of blood coagulation.
 Topic 1
Group 1 Elements-Alkali Metals
2014
1. Which sequence of reactions shows correct chemical 9. All the s-block elements of the periodic table and placed in
relation between sodium and its compounds? [VITEEEJ the groups [OJEEJ
HCl (aq) (a) IA and II A (b) III A and IV A
(a)Na + O 2 ~ Na 2O
(c) B subgroups (d) VA to VII A
NaCl ~ Na 2CO 3 ~ Na
2012
02 H20 CO2
(b) Na ~ Na 2 O ~ NaOH~ 10. Which of the following is known as Glauber's salt?
[Manipal, JCECEJ
Na 2CO 3 ~ Na
(a)Na 2 S 2 O 3 ·5H 2O (b) Na 2SO4 ·l 0H2O
(c)Na + H 2O ~ NaOH ~ (c) Na 2 CO 3 · 10H2O (d) Na(NH 4 )HPO4
002
11. Molten sodium chloride conducts electricity through the
NaCl Na 2CO 3 ~ N a following [MP PET]

CO2 (a) free electrons (b) free ions

(d)Na + H 2O ~ NaOH Na 2CO 3
(c) free molecules (d) free atoms
Electrolysis +
~ NaCl Na + Cl- 12. The reaction between sodium and water can be made less
(Molten)
vigorous by CKCETJ
2. A metallic oxide reacts with water to fonn its hydroxide, (a) adding a little alcohol
hydrogen peroxide and also liberates oxygen. The metallic (b) amalgamating sodium
oxide could be [EAMCETJ
(c) adding a little acetic acid
(a) Cao (b) KO 2 (c) Li 2 O (d) Na 2O 2 (d) lowering the temperature
3. What colour is imparted into the flame when lithium is 13. What happens when aluminium and zinc salts react with an
burnt? [J&K CETJ excess ofNaOH? [AMUJ
(a) Golden yellow (b) Brick red (a) White precipitate is fo1med
(c) Crimson red (d) Grassy green (b) White precipitate of both Zn and Al first formed
4. Lithium shows diagonal relationship with [J&K CETJ redissolved in excess ofNaOH
(c) White precipitate of AI redissolves but that of Zn
(a) sodium (b) magnesium
does not
(c) calcium (d) aluminimn
(d) White precipitate of Zn redissolves and that of Al
5. Sodium carbonate is manufactured by [J&K CETJ does not
(a) Castner-Kellner (b) Solvay process
(c) oxidation (d) transmission process
2011
14. The products obtained on heating LiNO 3 will be [AIEEEJ
2013 (a) LiNO2 + 0 2 (b) Li 2O+ NO2 + 0 2
6. In the reaction, NaOH + S ~ x + Na 2 S + H2 0, x is (c) Li 3 N +O 2 (d)Li 2O+OH+O2
(a) Na 2SO3 (b) Na 2 SO 4 [Manipal] 15. Which one of the following is true? [KCETJ
(c) Na 2 S2 0 3 (d) Na 2 S (a) NaOH is used in the concentration of bauxite ore
7. Which of the following alkali metal ions has lowest ionic (b) NaOH is a primary standard in volumetric
mobility in aqueous solution? [KCETJ analysis
(c) Manganous hydroxide is soluble in excess ofNaOH
(a) Rb+ (b)Cs+ (c)Li+ (d)Na+
solution
8. The ionic conductance of following cation in a given (d) NaOH solution does not react with Cl
concentration are in the order [OJEEJ
16. Which one of the following on hydrolysis, gives the
(a) Li+ < Na+ < K+ < Rb+ cotTesponding metallic hydroxide, H 2O 2 and 0 2 ?
(b) Li+ > Na+ > K+ > Rb+ (a) Li 2 0 (b) Na 2 0 2 [Kerala CEEJ
(c)Li+ < Na+ > K+ > Rb+ (c) NaO2 (d) Na 2 O
(d) Li+ = Na+ < K + <Rb+ (e) BeO
224 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2010
17. Which property of Na 2 S 2 O 3 makes it useful in 26. Sodium peroxide which is a yellow solid, when exposed to
photography? [Guj CET] air becomes white due to the formation of [Kerala CEE]
(a) Photochemical property (a) H 2 O 2 (b) Na 2 O
(b) Complex formation property (c) Na 2 Oand 0 3 (d) NaOH and Na 2 CO 3
( c) Oxidising agent (e) NaOH and H 2 O 2
( d) Reducing agent 27. When KI is added to acidified solution of sodium nitrite
18. Le-blanc process is employed in the manufacture of then [WB JEE]

(a) baking soda (b) washing soda [RPET] (a) NO gas is liberated and 12 is set free
( c) potash (d) plaster of Paris (b) N 2 gas is liberated and HI is produced
( c) N 2 0 gas is liberated and Ii is set free
2009 (d) N 2 gas is liberated and HOI is produced
19. The characteristic not related to alkali metal is [Manipal] 28. The element which on burning in air gives peroxide is
(a) high ionisation energy (a) lithium (b) sodium CUPSEE]
(b) their ions are isoelectronic with noble gases (c) rubidium (d) caesium
( c) low melting point 29. Microcosmic salt is [UPSEE]
(d) low electronegativity
(a) Na 4 P2 O 7 (b) Na (NH 4 )HPO 4
20. Which ofthe following properties oflithium does not show
(c) Na (NH3 )HPO4 ·4H2 O (d) MgNH 4 PO 4
diagonal relationship with magnesium?
30. Which one of the following will dissolve in water most
(a) Formation of Li+ ion [lndraprastha CET, CGPET]
readily? CUPSEE]
(b) Formation of Li 3 N
(a) 12 (b) BaCO3 (c) KF (d) Pbl2
(c) Solubility ofLiHCO3
(d) Thermal decomposition ofLi 2 CO 3 31. Which compound is used in photography? [UPSEE]
(a) Na 2 SO5 (b) Na 2 S 2 O 8
2008 (c) Na 2 S 2 O 6 (d) Na 2 S 2 O 3
21. Aqueous solution of Na 2 S 2 0 3 on reaction with Cl 2 gives 32. Sodium thiosulphate is a CUPSEE]
(a) Na 2 S 4 O 6 (b) NaHSO4 [IITJEE] (a) reducing agent (b) oxidising agent
(c) NaCl (d) NaOH ( c) complexing agent ( d) bleach ing agent
22. Which of the following statements are correct for alkali 33. A metal 'M'reacts withN 2 to giveacomp01md 'A' (M 3 N).
metal compounds? ' A' on heating at high temperature gives back 'M' and 'A'
I. Superoxides are paramagnetic in nanrre. on reacting with H 2 O gives a gas B. 'B' turns CuSO4
II. The basic strength of hydroxides increases the group. solution blue on passing through it. M and B can be
III. The conductivity of chlorides in their aqueous solutions (a) Al and NH 3 (b) Li and NH 3 [UPSEE]
decreases down the group.
(c) Na and NH 3 (d) Mg and NH 3
IV. The basic nanrre of carbonates in aqueous solutions is due to
cationic hydrolysis. [BITSAT, AMU, EAMCET] 34. A solution of sodium thiosulphate on addition of few
drops of ferric chloride gives violet colom due to the
(a) I, II, and III (b) I and II
formation of [UPSEE]
( c) II, III and IV (d) III and IV
(a)Na 2 S 4 O 6 (b)Fe 2 (SO4 )J
23. The most electropositive element in alkali metals, is
(c) Fe 2 (S 2 0 3 ) 3 (d) Fe 2 (S 2 O 3 h
(a) Na (b) K [MP PET]
35. Na 2 S 2 O 3 isreducedbyl 2 to Co.JEE]
(c) Rb (d) Cs
(a) Na 2 S (b) Na 2 SO4
24. Which of the following metals is extracted by the
(c) NaHSO 3 (d) Na 2 S 4 O 6
electrometallmgical method ? [MPPET]
(a) Fe {b) Cu 36. For which one of the following minerals, the composition
(c) Ni (d) Na given is incorrect? [Guj CETl

25. When carbon monoxide is passed over solid caustic soda (a) Glauber's salt - Na 2 SO4 · 10H 2 O
heated to 200°C, it forms [KCET] (b) Borax - Na 2 B 4 O 7 -7H2 O
(a) Na 2 CO 3 (b) NaHCO 3 (c) Carnallite - KC!· MgC1 2 · 6H 2 O
(c) HCOONa (d) CH 3 COONa (d) Soda ash- Na 2 CO 3
 s-Block Elements 1225

37. Which of the following is co1Tect? [DCE] 2006

(a) In the Castner's process of sodium extraction, NaCl 48. The ionic mobility of alkali metal ions in aqueous solution
is used as an electro! yte is maximum for [AIEEEJ
(b) Sodiu m reduces CO2 to carbon
( c) Mg reacts with cold water and liberate hydrogen gas.
( d) Magnalium is an alloy of Mg and Zn
49. When Na reacts with liquid NH3 the following substance is
38. One of the elements present in camallite shows flame
fom1ed [BITSAT]
colouration. The colour of the flame is [DCEJ
(a) orange (b) green (c) yellow (d) lilac (a) [Na (NH 3 )x r (b)[e{NH 3 )yr
39. Among the alkali metals caesium is the most reactive (c) NaNH2 (d) Na_. (NH 3 )y
because [Jamia Millia Islamia] 50. Pick out the statement (s) which is/are not correct about the
(a) its incomplete shell is nearest to the nucleus diagonal relationship of Li and Mg.
(b) it has a single electron in the valence shell T.Polarising powers of Li+ and Mg2+ are almost same.
( c) it is the heaviest alkali metal TI.Like Li, Mg decomposes water very fast.
( d) the outem1ost electron is more loosely bound than the ITT.LiCI and MgCl 2 are deliquescent.
outermost electron of the other alkali metals IV. Like Li, Mg does not form solid bicarbonates.
(a) I and II (b) II and III (c) Only II [Kerala CEEJ
2007
(d) Only I (e) II and IV
40. The ionic conductance is least for [BITSAT]
51. Which of the following dissolves in hot cone. NaOH
(a) Cs+ (b) Rb+ (c) K+ (d) Na+ solution? [WB JEE]
41. The carbonate that will not decompose on heating is (a) Fe (b) Zn (c) Cu (d) Ag
(a) Na 2CO 3 (b) CaCO3 (c) BaCO3 [Ke rala CEE] 52. KI and CuSO4 solution when mixed, give [WBJEE]
(d) SrCO3 (e) Li 2 CO3
(a) Cul2 + K2SO4
42. The starting material used in Solvay's process is (b) Cu 2 l 2 + K 2 SO4
(a) sodium sulphate (b) brine solution [WB JEE ] (c) K 2 SO4 + Cu 2 l 2 + 12
( c) carnallite (d) All of these (d) K 2SO4 + Cul2 + f2
43. In Down's method for the extraction of sodium, the 53. Baking powder contains [UPSEE]
melting point of the electrolyte is lowered by adding
(a) NaHCO 3 , Ca(H2PO2 h and starch
(a) potassium chloride [WB JEE]
(b) NaHCO3 , Ca(H 2 PO 2 h
(b) calciu m chloride
(c) NaHCO 3 and starch
(c) both calcium chloride and potassium fluoride
(d) NaHCO3
(d) potassium fluor ide only
54. The main product obtained when a solution of sodium
44. The solubility of alkali metal hydroxide is [OJEE]
carbonate reacts with mercuric chloride is [AMUJ
(a) L iOH < KOH < NaOH < RbOH < CsOH
(a) Hg(OH)z (b) Hg CO3 ·HgO
(b) LiOH < NaOH < KOH < RbOH < CsOH
(c) Hg CO 3 (d) Hg CO3 ·Hg (OH)z
(c) CsOH < RbOH < KOH < NaOH < LiOH
55. Which of the following reactions does not liberate gaseous
( d) None of the above
product? CEAMCETJ
45. Shine at freshly cut sodium is because of [AMU]
(a) AlCl 3 + NaOH ~
(a) du e to oscillation of free electrons
(b) NaOH + P (white) + H 2O ~
(b) due to weak metallic bonding
(c) du e to absorption of light in crystal lattice (c) Al+ NaOH ~
( d) due to presence of free valency at the surface (d) Zn+ NaOH ~
46. The fommla of the product formed, when sodium 56. Consider the following abbreviations for hydrated alkali
thiosulphate solution is added to silver bromide is ions.
(a) Ag 2 S 2O 3 (b) Ag 2S [EAMCET] X = [Li(H2O)nJ\ Y = [K(H 2O)nt; Z = [Cs (H2O),,t
(c) Na 3 [Ag(S 2O 3 h ] (d) Ag 3 [Na (S 2O 3 )2] What is the con-ect order of size of these hydrated alkali
47. The chemical formula offeldspar is [EAMCET] ions ? [J&K CET]
(a) KA1Si 3 0 8 (a) X> Y > Z
(b) Na 3 AlF6 (b)Z>Y>X
(c) NaAlO2 (c)X = Y = Z
(d) K2SO4 ·Al2 (SO4 h -4Al(OHh (d) Z> X> Y
226 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2005
57. Based on lattice energy and other considerations which one 62. Acidic solution of S 2 0~- is conve11ed to ... ... in the
of the following alkali metal chlorides is expected to have presence of 12 . [OJEE]
the highest melting point ? [AIEEE]
(a) S 4 O~- + 1- (b) SO~- + i-
(a) RbCI (b) KCl (c) NaCl (d) LiCl
(c) SO3 + 1- (d) S 4 O~- + 13
58. Solvay process is used for the manufacture of [BITSAT]
(a) NaOH (b) Na 2 CO 3 63. Sodium is heated in air at 300°C to form X. X absorbs
(c) NH 3 (d) NaCl CO2 and forms Na 2 CO3 and Y? Which of the following is
Y? [EAMCET]
59. On strong heating sodium bicarbonate changes into
(a) H2 (b) 0 2 (c) H 2 O 2 (d) 0 3
(a) sodium monoxide [Manipal]
(b) sodium hydroxide 64. Which of the following is not correct? [EAMCET]
(c) sodium carbonate (a) Iodine oxidises sodium thiosulphate to sodium
(d) sodium peroxide tetrathionate
(b) Sodium thiosulphate is soluble in water
60. Which one of the following statements is correct for all the
(c) Ozone is used to identify the presence of unsaturation
alkali metals? [Ke rala CEE]
in alkenes
(a) Their nitrates on heating give NO 2 and 0 2 (d) Sodium thiosulphate reacts with iodine to form
(b) Their carbonates decompose on heating to give CO2 sodium sulphate
and the metal oxide
65. Most powerful reducing agent is [BCECE]
(c) They react with oxygen to give mainly the oxide M 2 0
(d) They react with halogens to give the halides MX (a) Li (b) Na (c) Ca (d) Mg
(e) They react with nitrogen to give nitrides 66. KO 2 is used in space and submarines because it
61. The primary standard solution for the estimation of [Jamia Millia Islamia]
Na 2 S2 0 3 is [OJEE] (a) absorbs CO 2 and increases 0 2 concentration
(a) 12 solution (b) KMnO 4 (b) absorbs moisture
(c) K 2 Cr2 0 7 (d) oxalic acid (c) absorbs CO 2
(d) produces ozone

Topi c 2
Group 2 Elements-Alkaline Earth Metals
2014
1. The metal that cannot be obtained by electrolysis of an 4. Baking powder is more commonly used to make cakes or
aqueous solution of its salts is [JEE Main] bread 'rise'. FiHer in baking powder is [Manipal]
(a) Ag (b) Ca (a) NaHCO 3 (b) Ca (H 2 PO 4 h
(c) Cu (d) Cr (c) starch (d) NaAl(SO 4 h
2. Usually, CaCI2 is preferred over NaCl for cleaning snow 5. Which pair is different from the others? [Manipal]
on roads particulary in very cold countries. This is because (a) Li-Mg (b)B-Al
[BITSAT] (c)Na-K (d)Ca-Mg
(a) NaCl makes the road slippery but CaCI 2 does not 6. The species that is not hydrolysed in water is [KCET]
(b) CaC1 2 is hygroscopic but NaCl is not (a) P4 O 10 (b)BaO2 (c)Mg 3 N 2 (d)CaC2
(c) CaC1 2 is less soluble in H 2 Othan NaCl 7. Which of the following substances has the highest melting
(d) eutectic mixture of CaC1 2 / H 2 O freezes at - 55°C point? [Indraprastha CET]
while that ofNaCI/H 2 Ofreezes at- 18° C (a) CaO (b) BiC1 3 (c) KCl (d) ClO 2
3. The activity of alkaline earth metals as reducing agent
(a) decreases from Be to Ba [Manip al]
2012
(b) increases from Be to Ba 8. Which of the following on thermal decomposition yields
(c) increases from Be to Ca and decreases from Ca to Ba basic as well as acidic oxide? [AIEEEJ
( d) decreases from Be to Ca and increases from Ca to Ba (a) NaNO3 (b) KC1O 3 (c) CaCO3 (d) NH4 NO 3
 s-Block Elements I 227
2011
9. Which of the following represents the composition of 19. Chlorine reacts with ' X' to form bleaching powder. 'X' is
camallite mineral? [WB JEE] [OJEEJ
(a) K 2 O· Al 2O 3 · 6SiO2 (a) dry slaked lime (b) sodium hydroxide
(b) KN03 (c) acetone (d) chloral
(c) K 2 SO4 · MgSO4 ·MgC1 2 · 6H 2O
(d) KCl-MgC1 2 · 6H 2O
2008
20. Plaster of Paris on making paste with little water sets to
2010 hard mass due to formation of CUPSEEJ
10. Out offollowing which compound is used for preservation (a) CaSO4 (b) CaSO4 · V2 H 2 O
of wood? [MP PET] (c) CaSO 4 ·H2 O (d) CaSO4 · 2H 2 O
(a) NaCl (b) HgCl 2 (c) ZnC1 2 (d) CaC1 2 21. One mole of magnesium nitride on the reaction with an
11. Which ofthe following pairs ofsubstances would give same excess of water gives [UPSEEJ
gaseous product in reaction with water? [Ke rala CEEJ (a) one mole ofNH 3 (b) two moles ofNH 3
(a) Na and Na 2O 2 (b) Ca and CaH 2 (c) one mole ofHNO 3 (d) two moles ofHNO 3
( c) Ca and Cao (d) Ba and BaO2 22. Phosphine, acetylene and ammonia can be fom1ed by
(e) Ca and CaC2 treating water with [OJEEJ
12. Which of the following carbonates decomposes at lowest (a) Mg 2 P2 , Al 4 C 3 , Li 3 N (b) Ca 3 P2 , CaC 2 , Mg 3 N 2
temperature? [Indraprastha CET, CG PET] (c) Ca 3 P2 , CaC2 , CaCN 2 (d) Ca 3 P2 , Mg 2 C, NH4 NO 3
(a) MgCO 3 (b) CaCO3 23. Which of the following is not an ore of magnesium?
( c) SrCO3 ( d) BaCO 3 [Jam.ia Millia Islamia]
13. Which of the following metal carbonates decomposes on (a) Carnallite (b) Dolomite
heating? [RPET] (c) Calamine (d) Sea water
(a) MgCO 3 {b) Na 2 CO 3
(c) K 2 CO3 (d) Rb 2 CO 3 2007
24. Which one of the following substances is used in the
2009 laboratory for a fast drying of neutral gases? [BITSATJ
14. The salts of which alkaline earth metal are used in the form (a) Phosphorus pentoxide
of manure ? [MP PET] (b) Active charcoal
(a) Mg (b) Ca (c) Ba (d) Sr ( c) Anhydrous calcium chloride
15. Which pair of the following chlorides does not impart (d) Na 3 PO 4
colour to the flame ? [Ke rala CEEJ 25. Setting of plaster of Paris involves [BITSAT]
(a) BeC12 and CrC1 2 (b) BeC1 2 and MgC1 2 (a) oxidation with atmospheric oxygen
(c) CaC1 2 and BaC1 2 (d) BaC1 2 and SrC12 (b) combination with atmospheric CO2
(e) MgC1 2 and CaCl 2 ( c) dehydration
16. Which one of the following processes is used for the (d) hydration to yield another hydrate
manufacture of calcium? [WB JEE] 26. A compound X on heating gives a colourless gas. This
(a) Reduction ofCaO with carbon residue is dissolved in water to obtain Y . Excess CO2 is
(b) Reduction ofCaO with hydrogen bubbled through aqueous solution of Y when Z is formed.
( c) Electrolysis ofa mixture ofanhydrous CaCl 2 and KCI Z on gentle heating gives back X.
(d) Electrolysis of molten Ca(OH)z The Xis [WB JEE, Manipal]
17. The chemical which is used for plastering the broken bones (a) CaCO 3 (b) Ca (HCO 3 h
is [UPSEE] (c) Na 2 CO 3 (d) NaHCO 3
(a)(CaSO4 )z· H 2 O (b)MgSO4 · 7H 2 O
(c) FeSO4 · 7H 2 O (d) CuSO4 · 5H2O
2006
27. The solubilities of carbonates decrease down the
18. Which one of the following orders of stability is correct?
magnesium group due to decrease in [UPSEE, MP PET]
(a) MgCO 3 > CaCO3 > SrCO3 > BaCO3 [OJEEJ
(a) lattice energies of solids
(b) BaCO3 > SrCO 3 > CaCO3 > MgCO 3
(b) hydration energies of cations
( c) MgCO 3 > BaCO3 > SrCO 3 > CaCO3 ( c) interionic attraction
(d) CaCO3 > BaCO3 > MgCO 3 > SrCO 3 ( d) entropy of solution formation
228 I Chapterwise & Topicwise Engineering Entrances Solved Papers

28. The substance used in Holme's signal of the ship is a 40. The product obtained on fusion ofBaS04 and Na 2 C03 is
mixture of [MP PET]
(a) BaC03 (b) Bao [MP PET]
(a) CaC2 + Ca 3 P2 (b) Ca 3 (P04 ) 2 + Pb 3 0 4 (c) Ba(OH)i (d) BaHS04
(c) H 3 P04 + CaCl 2 (d) NH 3 + HOCl
41. CaCI 2 is used as [MPPET]
29. In curing cement plasters water is sprinkled from time to
(a) disinfectant (b) desiccating agent
time. This helps in [MP PET]
( c) medicine (d) None of these
(a) keeping it cool
(b) developing interlocking needle-like crystals of 42. Mixture ofMgCI 2 and MgO is called [UPSEE]
hydrated silicates (a) Portland cement (b) Sorel's cement
( c) hydrating sand and gravel mixed with cement ( c) double salt (d) None of these
(d) converting sand into silicic acid
43. Which of the following exists in polymeric fom1? [OJEE]
30. The substance not likely to contain CaC03 is [MP PET]
(a) A1Cl 3 (b) BeCl 2
(a) a marble statue (b) calcined gypsum (c) B 2 H 6 (d) SiC
( c) sea shells (d) dolomite 44. What are the metal ions present in camallite? [EAMCET]
31. Bleaching action of bleaching powder is due to the (a) Mg, K (b) Al, Na
liberation of [WBJEE] (c) Na, Mg (d) Zn, Mg
(d) Cl- 45. Which metal is present in chlorophyll? [Guj CET]

32. CaC2 + N 2 ~ A,productA is [UPSEE,OJEE] (a) Ca (b) Co (c) Zn (d)Mg

(a) CaCN2 (b) CaCN2 + C 46. Bleaching powder is obtained by treating chlorine with
(c) CaCN2 + N 2 (d) None of these (a) CaC03 (b) Ca(OHh [Guj CETJ
33. Among the following, which is insoluble in water? ( c) Cao (d) None of these
[EAMCET]
2005
(a) Sodium fluoride (b) Potassium fluoride
47. Milk of magnesia is used as [BITSAT]
(c) Beryllium fluoride (d) Magnesium fluoride
(a) antichlor (b) antacid
34. The chemical formula of plaster of Paris is [BCECEJ
(c) antiseptic (d) food preservative
(a) CaS04 · 1/ 2 H 2 0 (b) CaS0 4 · H 2 0
48. Ionic compound BaS04 is insoluble in water due to
(c) CaS04 · 2H 2 0 (d) CaS0 4 · 3H2 0
(a) high lattice energy [Manipal]
35. Beryllium and aluminium exhibit many properties which
are similar. But, the two elements differ in (b) low lattice energy
[Jamia Millia Islamia] (c) low hydration energy
(d) Both (b) and (c)
(a) exhibiting maximum covalency in compounds
(b) forming polymeric hydrides 49. Which of the following hydroxides is amphoteric in
( c) forming covalent halides nature? [AMU]
(d) exhibiting amphoteric nature in their oxides (a) Be(OH)z (b) Mg (OH)z
36. The difference of water molecules in gypsum and plaster of (c) Ca(OHh (d) Ba (OH) 2
Paris is [BITSAT] 50. In which of the following reaction, MgO is not formed?
(a) 5/ 2 (b) 2 (c) 1/ 2 (d) 1.!. (a) Mg + CO2 ~ [EAMCETI
2 (b) Mg + di!. HN03 ~
37. Which of the following is known as dead burnt plaster? (c) Mg+ N O ~
(a) Gyp sum [MHT CET] (d) Mg + B2 0 3 ~
(b) Plaster of Paris
(c) Anhydrite 51. In the presence of cobalt chloride, bleaching powder
(d) None of the above decomposes to form [DCE]
38. The decomposition temperature is maximum for (a) CaC03 and 0 3 (b) Cl02 and CaO
(a) MgC0 3 (b) CaC03 [MHT CET] (c) CI2 0and CaO (d) CaCI 2 and 0 2
(c) BaC03 (d) SrC03 52. A metal Mforms water soluble MS04 and inert MO. MO
39. Thomas slag is [MHTCET] in aqueous solution forms insoluble M(OH)i soluble in
(a) Ca 3 (P0 4 ) 2 -2H 2 0 (b) Ca 3 (P04 ) 2 · CaSi0 3 NaOH. Metal M is [Jamia Millia Islamia]
(c) MgSi0 3 (d) CaSi03 (a) Be (b) Mg (c) Ca (d) Si
 Answers
TOPICl Group 1 Elements-Alkali Metals
1. (d) 2. (b) 3. (c) 4. (b) 5. (b) 6. (c) 7. (c) 8. (a) 9. (a) 10. (b)
11. (b) 12. (b) 13. (b) 14. (b) 15. (a) 16. (b) 17. (b) 18. (c) 19. (a) 20. (a)
21. (b) 22. (b) 23. (d) 24. (d) 25. (c) 26. (d) 27. (a) 28. (b) 29. (b) 30. (c)
31. (d) 32. (a) 33. (b) 34. (c) 35. (d) 36. (b) 37. (b) 38. (d) 39. (d) 40. (d)
41. (a) 42. (b) 43. (c) 44. (b) 45. (a) 46. (c) 47. (a) 48. (b) 49. (b) 50. (c)
51 . (b) 52. (c) 53. (a) 54. (b) 55. (a) 56. (a) 57. (c) 58. (b) 59. (c) 60. (d)
61. (a) 62. (a) 63. (b) 64. (d) 65. (a) 66. (a)
TOPIC2 Group 2 Elements-Alkaline Earth Metals
1. (b) 2. (d) 3. (b) 4. (c) 5. (a) 6. (a) 7. (a) 8. (c) 9. (d) 10. ( d)
11. (b) 12. (a) 13. (a) 14. (b) 15. (b) 16. (c) 17. (a) 18. (b) 19. (a) 20. (d)
21. (b) 22. (c) 23. (c) 24. (c) 25. (d) 26. (a) 27. (b) 28. (a) 29. (b) 30. (b)
31. (c) 32. (b) 33. (d) 34. (a) 35. (a) 36. (d) 37. (c) 38. (c) 39. (b) 40. (a)
41. (b) 42. (b) 43. (b) 44. (a) 45. (d) 46. (b) 47. (b) 48. (d) 49. (a) 50. (b)
51 . (d) 52. (a)

Explanations
Topic 1 Group 1 Elements-Alkali Metals
1. 2Na + 2H2O - 2NaOH + H 2 i CaO + H 2O -Ca(OH)2
2NaOH + CO2 - Na2CO 3 + H 2O (it is used for the recovery ofNH3)
Na2CO3 + 2HC1 - 2NaCI + Hp + CO 2 2NH4CI + Ca(OH)z- CaCl 2 + 2NH3 + 2H2O
Electrolysis
(iit) 2NaHCO 3~ Na 2CO 3 + H 2O + CO2
NaCl
(Mollen)
------+
l-l
Na+ + cI-
+e - e- 6. Sulphur on heating witJ1 sodium hydroxide solution forms
sodium thiosulphate.
Na Cl
4S + 6NaOH ~ Na2SzO3 + 2Na 2S + 3H2O
2. Potassium superoxide reacts with water to form its hydroxide, Sodium thiosulphate
hydroperoxide and oxygen.
7. Smaller the size of cation, larger is their hydration energy, thus
2KO2 + 2Hp - 2KOH + H 2O 2 + 0 2
smaller is their molar ionic mobility and conductance.
3. S. N o Colour Cation Ionic size Li+ < Na+ < K+ <Rb+ < Cs+
(a) Golden yellow Na+ Hydration energy Li+ > Na+ > K+ > Rb+ > Cs+
Size o f hydrated ion Li+ > Na+ > K+ > Rb+ > Cs+
(b) Brick red Ca 2+ Mobility Li+ <Na+ <K+ <Rb+ <Cs+
(c) Crimson red Li+ Hence, among alkali metal ions, Cs+ has the highest and Li+ has
the lowest mobility in aqueous solution.
(d) Grassy green Cu 2+, BO~-, Ti 3-
8. Conductance of an ion in aqueous solution is dependent upon its
. . I
4. Lithium shows diagonal relationship with magnesium due to their hydrated size as. Tonic conductance "" - - - - - - - -
ionic size of hydrated ion
(i) comparable electronegativity (Li = 1.00 and Mg= 1.20)
(ii) small difference in radius of Li and Mg Thus, ionic conductance in aqueous solution increases in the
order Cs+ > Rb+ > K+ > Na+ > Li+. This is because the size of
(iii) high polarising power.
hydrated ion is minimum for Cs+ among hydrated alkali metal
5. Sodium carbonate is manufactured by Solvay ammonia process.
ions.
The raw materials used for this process are NaCl, NH 3 and
limestone (for COz). This process occurs in the following steps: 9. According to the modern periodic table, if the last electron of an
element enters in s-orbital, then element is known as s-block
A
(i) CaCO3- CaO + CO2 element.
CO2 + NH3 + H2 O - NH4 HCO3 Group I A has elements with ns 1 configuration and II A has
elements with ns2 configuration. Thus, all s-block elements are
(ii) NaCl + NH4HCO3 - NaHCO 3 + NH4Cl placed in group I A and II A.
230 I Chapterwise & Topicwise Engineering Entrances Solved Papers

10. Formula Name Furthur, the potassium sulphate is heated with coke which
reduces sulphate to sulphide and it self oxidised to CO2. In the last
(a) Na2$iO3 · SH2O Hypo step, potassium sulphide reacts with calcirnn carbonate to
(b) Na 2SO 4 · I0H2O Glauber's salt produce potassium carbonate and calcium sulphide. This mixture
(c) Na 2CO 3 · I 0HzO Washing soda is called black ash.
(d) Na(NH4 )HPO4 Microcosmic salt K2SO4 + 2C - K2S + 2CO2
K 2S + CaCO3 ---4 K 2CO3 + CaS
11. Sodium chloride in molten state, ionised into sodium and chloride
ions, which are electricity carrier. The potash was then separated from the black ash by washing it
with water.
NaCl ~Na++ Cl-
Note Le-blanc process was first used for soda ash (Na 2CO 3) but
12. With water, sodium is quite vigorous. To reduce its vigorousness, now it is used widely for all alkali carbonates especially for
it is amalgamated with mercury (Na-Hg amalgam). potash.
13. When NaOH reacts with salts of Al and Zn, they form white 19. Alkali metals have low ionisation energy. They possess
precipitate which dissolves in excess ofNaOH. minimtm1 value of ionisation energy in their period.
(i) A1Cl3 + 3NaOH - Al(OH)3J- + 3NaCI 20. Formation of Li+ (M+) ion is the property of first group
White ppt
Al(OH)3 + NaOH ---4 NaA1O2 + 2H 2O elements, i.e. alkali metals, not that of second group elements.
Sodiwnmeta Second group elements form M 2+ ions.
aluminate (soluble)
(ii) ZnSO4 + 2NaOH - Zn(OH)2 J, + Na2SO4 21. Sodium thiosulphate, Na2S2O3 gets oxidised by chlorine water.

Zn(OH)2 + 2NaOH - Na2ZnO2 + 2H2O Na2SzO3 + 4Cl 2 + 5H 2O - 2NaHSO4 + 8HCI

Sodium zincate
(soluble) 22. (I) The alkali metal superoxides contain 0 2 ion, which has an
unpaired electron, hence they are paramagnetic in nature.
14. LiNO 3, on heating gives a mixture ofNO2 and 0 2 while nitrates
(II) The basic character of alkali metal hydroxides increases on
of rest of alkali metals yields only oxygen. moving down the group.
2LiNO3 ~ LizO + 2NO 2 + ..!.02 (III) The conductivity of alkali metal chlorides in their aqueous
2 solution increases on mov ing down the group because in
aqueous solution alkali metal chlorides ionise to give alkali
metal ions. On moving down the group the size of alkali metal
ion increases, thus degree of hydration decreases, due to this
Nitrates other alka li metals also give same reaction.
reason their conductivity in aqueous solution increases on
15. Baeyer's process or concentration of bauxite ore- impure bauxite moving down the group.
is treated with NaOH with which it forms water soluble soditun Ionisation in
2
metaaluminate complex. (TV)M2CO 3 ~ 2M+ + CO3-
aq. solution
420 - 42SK
2NaA1O2 + 3H2O
Sodium meta
co~- + 2H2O ---4 H2CO3 + 2OW
aluminate Thus, basic nature of carbonates in aqueous solution is due to
Impurities such as FeiO3, TiO2 and silica are left behind. anionic hydrolysis.
Pure alumina is recovered from solution. 23. Electropositive character increases as we move down the group
NaAlO 2 + 2Hz0 ---4 Al(OH)3 + NaOH because of the increase in atomic size, atoms have more tendency
to lose electrons. Hence, Cs is the electropositive most element in
2Al(OH)3 ~ Alz0 3 + 2H2O
alkali metals.
16. Na2O 2 + 2Hz0 ---4 H 2O 2 + 2NaOH 24. Sodium metal is extracted by the electrometallurgical process
2H2O 2 NaOH ) 2H2O + 02 because it is highly reactive metal.
Water used during the reaction reacts with Na 2O2 to form NaOH 25. When carbon monoxide is passed over solid caustic soda at 200°C
which tends to decompose Hz02. and IO atrn, sodium formate is obtained.
2000
17. Sodium thiosulphate (Na2S2O 3) is useful in photography due to CO + NaOH C/lo atm HCOONa
Sodium formate
its complex formation property. It is used in photography as a
fixer since, as it dissolves unreacted silver halides. 26. Sodium peroxide reacts with moisture and CO 2 of air (when
AgBr+ 2Na 2SzO3- NaJlAg(SzO3)i]+ NaBr exposed to air) and becomes white due to the fonnation ofNaOH
Silver Sodiwn argento and Na 2CO 3.
bromide thi05Ulphate
2Na 2O2 + 2Hz0 - 4NaOH + 0 2
18. Le-blanc process is employed in the manufacnire of potash
[K2CO 3]. It was a Batch process in w hich potassium chloride was 2NaOH + CO2 - Na 2CO 3 + HzO
first heated with sulphuric acid to produce potassium sulphate 27. When KI is added to acidified solution of sodium nitrite NO gas is
and hydrogen chloride gas. liberated and 12 is set free.
2KCI + H 2SO4 - K 2SO4 + 2HCI 2r + 4W + 2NOz - 2NO + I2 + 2Hz0
 s-Block Elements I 231
28. Alka li metals on burning in air give monoxide, peroxide or This colour disappears quickly due to reduction offerric chloride
superoxide. by thiosulphate. This shifts the above equilibrium to the left.
2FeC1 3 + 2Na2SzO3 ---t 2FeC1 2 + Na2Sp6 + 2NaCI
Li forms monoxide 2Li + .!. 0 2 ---4 Li 2O
2 35. Na 2SzO 3 ~ 2Na+ + Si0~-
Na form peroxide as well as monoxide.
2SzOt + 12 ~ S4O;- + 21
2Na + 0 2 ---4 Naz02
i.e. 2Na 2SzO3 + I2 ~ Na 2S4O6 + 2Nal
1
2Na + - 0 2 ---4 Na 2O 36. Borax-Na 2B4O 7 · l0HzO.
2
K, Rb and Cs form superoxide. 37. Alkali metals are electropositive, hence they can reduce CO 2•
(M = K, Rb, Cs) + 0 2 ---4 M02 4Na + CO2 ~ 2Na 2O + C
29. Microcosmic salt is Na(NH4 )HPO4 . It is white crystalline solid. 38. The formula of carnallite is KC!· MgC1 2 · 6H 2O. In this formula
It is obtained when NH 4C l and Na 2 HPO4 are dissolved in hot only potassium gives colour golden-yellow (lilac) to flame,
water and cooled. w hereas magnesium does not give flame colouration.
NH4Cl+ Na}IPO4 ---4 Na(NH4 )HPO 4 + NaCl 39. Alkali metals have a tendency to lose the single valence electron
and form positive ion and gain inert gas configuration but in case
It is separated by fractional crystallisation. of caesium, the distance of the valence electron is maximum. So,
It is used for the detection of certain basic radicals w hich forms force of attraction by the nucleus is least, hence, from the nucleus.
coloured mixed phosphate with NaPO 3• This electron can be lost easily. Hence, it is a more reactive metal.
Na(NH 4)HPO4 ~ NaPO3 + NH3 + Hp 40. Due to small size of Na+, it is heavily hydrated and become large
NaPO 3 + CoO ---4 NaCo· PO4 molecule. Tonic conductance down the group in alkali metals.
Blue bead Order of ionic conductance is
30. All the alkali halides except lithium fluoride are freely soluble in Na+< K+ <Rb+> Cs+ .
water. I2 (non-polar) is least soluble in water. Group ITA 41. Na 2CO 3 will not decompose on heating.
carbonates (BaCO3) are insoluble in water. Pbl2 is sparingly
All alkali metal (TA group) carbonates (except Li 2CO 3) are highly
soluble in cold water but quite soluble in hot water. KF (most
stable and not decomposes on heating. Carbonates of alkaline
polar) is most readily soluble in water.
earth metals (IT A group) decompose into COz and metal oxide
31. Hypo or sodium thiosulphate (Na 2SzO3) is used in the fixing of more readily than group TA elements.
image. It dissolves unreacted AgBr but leaves metallic silver 42. When CO 2 gas is passed through a brine solution (28% NaCl)
unchanged. saturated with ammonia, it gives sodium bicarbonate which on
2Na 2SzO3 + AgBr ---4 Na 3[Ag(SzO 3 ) 2 ]+ NaBr drying and heating gives sodium carbonate.
Hypo Soluble
43. In Down is process, sodium is manufactured by the electrolysis of
32. The presence of excess of sulphur makes sodium thiosulphate a fused sodium chloride in the presence of CaCh and KF using
useful reducing agent. graphite anode and iron cathode.
2Na 2SzO 3 + 12 ---t Na 2S4O6 + 2Nal NaCl -----'- Na+ + c1-
This reaction is applied in volumetric estimation of iodine. In this Na++e- ---t Na (at cathode)
reaction, sodium thiosulphate acts as a reducing agent.
2c1- ---t CI2 + 2e- (at anode)
33. The formu la of 'A' is M 3N. It suggests that Mis a monovalent
CaC12 + KF lower the melting point from 1085 K to 850 K.
metal. Only lithium reacts with N 2 directly to form stable M 3N
compound. 44. The solu bility of alkali metal hydroxides increases from top to
Hence, a metal 'M' is lithium. The series of its reaction can be bottom.
represented as: Hence, the order of their solubility is as
6Li + N 2 ~ 2Li 3N Li OH < NaOH < KOH < RbOH < CsOH.
(M) (A) 45. Shining at freshly cut sodium is due to oscillation of free electrons.
Lithium nitride
46. When sodium thiosulphate solution is added to AgBr, then
Li 3N + 3H 2O ---4 3LiOH + NH3 sodium argentothiosulphate is obtained.
~) w AgBr+ 2Na 2S2O 3 ---4 Na 3[Ag(SzO 3) 2 ] + NaBr
CuSO4 + 4NH3 ---4 [Cu(NH 3)4 ]SO4 (Colourless)
(8) Blue solution Sodium argento thiosuJphate

Hence, Mand Bare Li and NH 3 respectively.
34. On addition of a few drops of ferric chloride to thiosulphate
solution, a violet colouration is obtained due to the formation of
ferric thiosulphate.
3Na2SzO3 + 2FeCl3 ~ Fez(SzO3)J + 6NaCl
Violet colour
47. The chemical formula of feldspar is KA1Si 3O 8 .
48. Lt is having largest hydrated ionic size while Rb+ is having
smallest. Smaller the hydrated ionic size, greater the mobility.
Thus, the ionic mobility of Rb+ ion in aqueous solution is
maximmn among the given metal ions.
232 I Chapterwise & Topicwise Engineering Entrances Solved Papers

49. Na + (x + y) NH3 - [Na(NH3), t + [ e(NH3)y r 63. The reaction is as follows

Sodium dissolves in liquid ammonia to produce deep blue colour 2Na+ 0 2 300cc Naz02
in solution. The blue coloured solution possesses high conducting Sodium peroxide (X)
power, strong reducing nature due to ammoniated electrons. The
cation is also solvated by ammonia. 2Na2O 2 + 2CO2 -- 2Na 2 CO 3 + 0 2 i
(l')
50. Lithium and magnesium show diagonal relationship. Some points
Sodium peroxide is used in the purification of air in submarines
of similarity are
because it combines w ith CO2 to give 0 2.
(i) Polarising power of Lt and Mg+ are almost same.
(ii) Like Li, Mg decomposes water very slowly. 64. 2Na 2SzO3 + 12 - Na2 S4O6 + 2Nal
Sodium
(iii) LiCI and MgCl 2 are deliquescent. tetrathionate

(iv) Like Li, Mg do not form solid bicarbonates.

65. Alkali metals are strongest reducing agent among elements of
51. Zn dissolves in cone. NaOH due to the formation of sodium periodic table. The reducing character decreases down the group.
zincate. :. Li is strongest reducing agent among Li, Na, Mg and Ca.
Zn + 2NaOH - Na 2ZnO2 + 2H2 O + 3NaCI
66. KO2 absorbs CO 2 and increases 0 2 concentration so, it is used in
52. 2KI + CuSO 4 - Cttl2 + K 2 SO4 space and submarines.
Unstable
2Cu 2I2 - Cu 2 I2 + 12 Topic 2 Group 2 Elements-Alkaline
Hence, solution contains Cu 2I2 , 12 and K 2SO4 .
Earth Metals
53. Baking powder contains NaHCOJ, Ca(H 2PO2 h and starch.
1. Higher the position of element in the electrochemical series more
54. Basic mercuric carbonate is obtained in this reaction. difficult is the reduction of its cations.
Na2 CO3 + 2HgCl 2 - - HgCO 3 · HgO + 2NaCI + Cl2 + CO 2 If Ca 2+ (aq) is electrolysed, water is reduced is preference to it.
55. When AICl 3 reacts with NaOH, it forms sodium meta aluminate Hence, it cannot be reduced electrolytically from their aqueous
(NaAIO2 ~ water and solid NaCl. Thus, this reaction does not give solution.
gaseous product. Ca 2+ (aq) + Hp - Ca 2+ + OH- + H 2 i
AICl 3 + 4NaOH - - NaAlO 2 + 2H2O + 3NaCI 2. A mixture of chemical compounds having a single c hemical
Sodiwnmeta
aluminatod composition, solidifies at a lower temperature than any other
(soluble) composition made up of the same ingredients. This mixture is
56. All al kali metal salts are soluble in water. The degree of hydration called eutectic mixture.
depends upon the size of the cation. Smaller the size of cation, Freezing point of eutectic mixture of NaCl/HP is only -18°C
greater is its charge density and hence, greater is its tendency to but the ambient temperature of very cold countries is much lower
w ithdraw electrons from molecules w hich are thus polarised. L t than - 18° C In such situations, NaCl w ill be ineffective. Thus, for
ion being smallest in size among alkali metal ions is the most such simations eutectic mixture CaCl 2/ H 2O is used because it has
extensively hydrated while Cs+ ion being the largest alkali metal freezing point of - 55° C which is much lower than NaCl.
ion is the least hydrated. T he size of hydrated alkali ions is as This mixture not only lowers the freezing point of ice but also
Lt > Na+> K+ > Rb+ > Cs+ produce an exothermic reaction that allows street snow or ice to
melt at lower temperature.
Hence, the correct order is X > Y > Z.
3. The activity of alkaline earth metals as reducing agent increases
57. As we go down in the group, ionic character increases hence,
from Be to Ba because the tendency to lose valence electrons
melting point of halides should increase but NaCl has the highest
readily increases down the group.
melting point (800°C) due to its high lattice energy.
4. An improved combination of baking powder contains about 40%
58. Solvay process is used for the manufacture of Na 2CO3.
starch, 30% NaHCO3, 20% NaAl(SO4 ) 2 and 10% Ca(H 2PO4 )z.
59. Sodium bicarbonate decomposes on strong heating and gives Here, starch being non-reactive acts as filler to improve their
sodium carbonate. consistency and stability.
2NaHCO3 ~ Na 2CO3 + CO2 + H2O 5. Li - Mg ➔ diagonal relationship.
60. Alkali metals react with halogen to give halides. They are B-AI, Na- Kand Ca- Mg ➔ belongs to same group.
normally represented by M+ x-. 6. Reactions of P4O 10 , Mg3N 2, CaCz and BaO2 with water can be
61. Standard solution of iodine is used to estimate Na2SzO3 (hypo) shown as:
solution. It is oxidised to sodium tetrathionate by iodine. P4 O 10 + 6Hz0 - 4H3PO 2
2Na 2SzO3 + 12 -- Na2S4O6 + 2Nal Mg3N 2 + 6H 2O - 3Mg(OH)z + 2NH 3
CaC2 + 2H2 O - Ca(OH)2 + CzH2
62. Thiosulphate (SzO~-) is oxidised to tetrathionate (S40;-) ion by
BaO2 + 2Hz0 - Ba(OH)2 + H 2O 2
iodine.
Hence, except P4O 10 all other given compounds hydrolysed by
water.
 s -Block Elements I 233
7. BiCl 3 and CIO 3 have covalent character. 17. (CaSO4 ) 2 · H 2O is plaster of Paris. Since, on adding water, it set
In CaO the electronegative difference is 11 - 3.4 1= + 2.44 into a hard mass due to the formation of gypsum, it is used for
In KCI the electronegative difference is 10.8 - 3.161= + 2.36 plastering the broken bones. So, that broken bones are set straight.
Since, electronegative difference in CaO is greater than KCI. I
(CaSO4 ) 2 ·HzO+ l- H 2 O - 2CaSO 4 ·2H2O
Hence, CaO shows more ionic character than KCI. 2 Hard mass
Thus, CaO has the highest melting point among the given options. 18. In II-A group, the stability of carbonates increase with the rise in
atomic number due to small size of the resulting oxide ion.
8. (a) NaNO 3 ~ 2NaNO 2 + 0 2
i.e. BeCO3 < MgCO 3 < CaCO3 < SrCO3 < BaCO3
(b) KCIO 3 ~ 2KCI + 302
19. Cl 2 + Ca(OH)2 - CaOCl2 + Hp
(c)CaCO 3 ~ CaO+ CO2 Slaked lime Bleaching powder
Basic Acidic Compound 'X' is dry slaked lime.
(d) NH4NO 3 ~ N 2O+ Hp 20. P laster of Paris is a white powder. It changes into a hard mass
9. Carnallite - KC!· MgCl 2 · 6H 2O called gypsum on mixing with water. There is a slight increase in
It is an ore of magnesium. volume during this process.
10. From the given compounds, CaCl 2 is used to preserve wood I I
CaSO4 ·- H 2 O + l - H 2O - CaSO4 ·2H 2 O + Heat
because it is a hygroscopic substance and thus, attracts so much 2 2 Gypsum
Plaster of Paris
water that u ltimately liquefaction occurs. Further, no such
substances are formed which may cause damage to the wood. 21. One mole of magnesium nitride on reaction with an excess of
However, NaCl is also used as a preservative but not for wood. water gives two moles of ammonia.

11. The given substances react with water in the following manner Mg3N2 + 6H2O - 3Mg(OHh + 2NH3
I~ 2~
Na+ Hp - NaOH + H 2 (g)
22. Ca 3P2 + 6H 2O ----4 3Ca(OHh + PH3 i
2Nap 2 + 2H 2O - 4NaOH + O2 (.g) + H 2(g) Phosphine
Ca+ H 2O - CaO+ H 2 CaC2 + 2Hp ----4 Ca(OH)2 + C2H 2 i
CaH2 + 2H2 O - Ca(OHh + 2H2 Acetylene

Cao+ H2O - Ca(OHh CaCN2 + 3H2O ----4 CaCO3 + 2NH 3 i

Amrronia
CaC2 + 2H2 O - Ca(OH)z + C2 H 2
23. Carnallite (KC! · MgC1 2 · 6H2O\ dolomite (MgCO3 · CaCO 3) and
Ba+ 2H 2 O - Ba(OH)2 + H 2 sea water are the ores of magnesium, calamine (ZnCO 3) is an ore
2 of zinc.
BaO2 + Hp - Ba + + 0 2 + Hp2
Hence, Ca and CaH 2 is the pair that gives same gaseous product 24. Anhydrous CaC1 2 is used for fast drying of neutral gases.
on reaction with water.
25. On hydration plaster of Paris, converts into gypsum. Thus, this
12. On moving down the second group, the thermal stability of process of hydration yields another hydrate.
alkaline earth metal carbonates increases. I 3
CaSO4 · H 2O + H 2O ----4 CaSO 4 · 2H2 O
Hence, MgCO3, being the carbonate of upper element, 2
Plaster of par is
2 Gypsum
decomposes at lowest temperature.
13. On heating, it decomposes with evolution of CO2. 26. CaCO 3 ~ CaO + CO2 i
Ii (X) Residue Colourless gas
MgCO 3 - MgO + CO2
CaO + Hp - Ca(OH)2
14. Salts of calcium are used in the form of manure, e.g. triple Residue (Y)
superphosphate of lime [Ca(H2 PO4 hH2 O] .
Ca(OH)2 + 2CO 2 - Ca(HCO3 )z
15. Among the alkaline earth metals, the size of beryllium and (Z)
magnesium metals is very small. Therefore, the electrons in these
Ca(HCO 3 )z ~ CaCO 3 - CO2 + H2 O
metals are bounded more strongly and are not excited by the (X)
energy of flame to higher energy states.
27. The solubilities of carbonates decreases down the magnesium
Hence, these metals or their salts do not impart any colour to the
group due to decrease in hydration energy because hydration
flame.
energy inversely proportional to ionic size. As the size
16. Calcium is obtained by electrolysis ofa fused mass ofCaCl2 and increases, hydration ent11alpy of metal ions decreases from
KCI at about 700°C in an electrolytic cell made of graphite anode Mg 2+ to Ba 2+ .
and iron cathode.
CaC1 2 ~ Ca2+ + 2Cl- 28. For making Holme's signal, a mixture of calcium carbide, CaC2
and calcium phosphide, Ca 3P2 is used. This mixture is placed in
At anode 2Cl- ----4 Cl 2 + 2e-
metallic containers. Two holes are made and container is thrown
2
At cathode Ca + + 2e- ----4 Ca into the sea.
234 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Water enters in the container and produces acetylene and
phosphine. The gaseous mixture catches fire because of
phosphine. The acetylene gives a bright luminous flame which
serves as a signal to the approaching ship.
29. When mixed with water, the cement forms a gelatinous mass
which sets to hard mass when three dimensional cross-links are
formed between Si - 0 - Si and Si - 0 - Al - chains.
Resulting in hydrated silicates. The reactions involved in the
setting of cement
(i) Hydration of 3CaO · Al 2 O 3 and 2 CaOSiO 2 forming colloidal
gel.
(ii) Hydrolysis of 3CaO · Alp3 and 3CaO · SiO2 forming
precipitates of Ca(OH 2 ) and Al(OH)3 .
Hence, while curing cement plasters water is sprinked from
time to time so that interlocking needle crystals of hydrated
silicates are developed and cement sets to hard mass.
30. Calcined gypsum does not contain CaCO 3.
31. Bleaching action of bleaching powder is due to liberation ofCl 2,
or reaction with dilute acids or even CO2 •
CaOCl2 + CO2 ~ CaCO3 + Cl 2
32. When calcimn carbide reacts with nitrogen at 1000°C, calcium
cyanamide and carbon is formed.
1000°c
CaCN2
Calcium cyanamide
Note The stability of alkaline earth metal carbonates can also be
explained in terms of polarising, power of their cations.
As the size of metal ion increases, its polarising power or
covalent character decreases. Hence, their ionic character
increases.
Thus, the stability of their metal carbonates increases.
39. Thomas slag or phosphatic slag is a mixture of calcium
phosphate and calcium silicate [Ca 3 (PO4 )i · CaSiO3 ] . It is used
as manure.
40. On fusion ofNa 2 CO3 and BaSO 4 barium carbonate is obtained
Na 2CO 3 + BaSO4 ~ BaCO3 + Na 2 SO4
41. CaC12 is used as desiccating agent as it is hygroscopic and
absorbs moisture from substances.
42. Mixture of MgCl 2 and MgO is called Sorel's cement. It is
MgCl 2 · 5MgO · x Hp.
43. BeCl2 exists in polymeric form as it can form polymeric covalent
hydrides.
44. Formula of camallite is KCI • MgCl 2 • 6H 2 O. So, camallite
contains Kand Mg.
45. Magnesium (Mg) metal is present in chlorophyll.
46. Bleaching powder is obtained by treating chlorine with slaked lime.
Ca(OH)2 + Cl2 ~ CaOCl2 + H 2 O
+C Slaked lime Bleaching
powder

33. The fluorides of alkaline earth metals except beryllium fluoride 47. Milk of magnesia (can aqueous suspension ofMg(OH)2) is used
are insoluble in water because of large values of their lattice as an antacid.
energy. Hence, magnesium fluoride is insoluble in water. 48. Solubility of alkaline earth metal sulphates depends upon the
34. Plaster of Paris, CaSO 4 . .! H2O, while gypsum CaSO4 · 2Hp. hydration energy and lattice energy of metal ions.
2 Since, hydration and lattice energy decreases from Be2+ to Ba 2+
35. Be (Z = 4) has maximum covalency of 4 while Al (Z = 13) has ion (as size increases). Thus, BaSO 4 is almost insoluble in water.
maximlUn covalency of 6. 49. Be (OH)2 has minimum basicity and has amphoteric character as
it dissolves both in acid and in alkali.
36. Formula of gypsum= CaSO4 · 2H2O
Be(OH2 ) + 2HCI ~ BeC1 2 + 2H 2O
Formula of plaster of Paris= CaSO 4 . .! Hp Be(OH2 ) + 2NaOH ~ Na 2BeO2 + 2H 2 O
2
50. Mg + 2HNO 3 ~ Mg(NO 3 ) 2 + H 2 i
Difference of water molecule= 2H2 0-_!_ H,O= 1.!H2 O Oil.
2 - 2
Hence, MgO is not formed in this reaction.
CaSO 4 CoCl2
Anhydrile or 51. 2CaOCl 2 ~ 2CaCl 2 + 0 2
Plast..- of Paris dead burnt plaster
In presence of CaCl 2 (which act as catalyst bleaching powder
The anhydrous CaSO4 is called dead burnt plaster because it does gives out oxgen).
not set like plaster of Paris when moistened with water.
52. Metal M is Be.
38. Greater the electropositive character, more will be stability and
Be + H 2O ~ Be (OH)z
high decomposition temperature. As the electropositive character
increases down the group, Be(OH)z + 2NaOH ~ Na 2Be 0 2 + 2H 2O
Soluble
: . Among given choices barium has highest electropositive
character and hence, highest decomposition temperature.
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11
p- Block Elements
QUICK REVIEW
Elements in which the last electron enters the p-orbital are
p-block elements. p-block includes groups from 13 to 18.
Elements of Group 13
• B, Al, Ga, In. and Tl are p-block elements. The general
valence shell configuration is ns 2 np 1 , thus common
oxidation states are +3 and +2.
• Atomic and ionic radius, metallic character, density,
melting and boiling point increases on moving down the
group. Their ionisation enthalpy and electronegativity do
not show a regular trend.
Chemical Properties
(i) With air M 2O3 type oxides are fonned. At high
temperanire, nitride are formed with N 2•
(ii) B remains unreactive with acids and bases whereas Al is
amphoteric.
(iii) Halides are of MX3 type. They are electron deficient
(Lewis acid). The order of acidic strength is
BF3 < BCl 3 < BBr3 < BT3. BF3 is weak Lewis acid because
of back donation of electrons from F atom. If central atom
is different, the order of acidic strength is
BCl 3 < AICl 3 < GaC1 3 < InCl 3. Hence, BFt cannot exist.
(iv) Hydroxides are of type M (OHh Basic nature increases
down the group. TI(OH)3 is a strong base like hydroxides
of alkali metals.
(v) Group 13 elements fonn covalent compounds when
anhydrous, but in aqueous give M 3+ ions (except boron)
due to high hydration energy.
Anomalous behaviour of boron It is due to its small
radius, high electron density, electronegativity and
non-availability ofd-orbitals. Due to diagonal relationship
with silicone, it shows similar properties like, it is a
non-metal, its chloride fumes in moist air, shows allotropy.
Compounds of Group 13
Borax is also called tincal or sodium tetraborate
decahydrate (Na 2 B4 O7 · I0H 2 O) .
2Ca 2 B6 O 11 + 3Na 2 CO3 + H 2 O ~ 3Na 2 B4 O7
+ 3CaCO3 + Ca(OH)i
Borax when treated with cone. HCI or H 2 SO4 , crystals of
boric acid are given. Borax gives coloured beads with
coloured salts due to the formation of metal metaborates.
Boric acid also called orthoboric acid H 3 BO3 or B(OH)3 .
Na2B 4O7 + 2HCI + 5Hp ~ 4B(OH)3 + 2NaCI
It is not a protonic acid, it acts as Lewis acid. Its reaction
with NaOH is reversible. To move in forward direction
polyhydroxy compound, like cis-1, 2-diol, glycerol etc., is
added. It is used in carrom boards because of its layered
structure (due to H-bonding).
H 3 BO3 + H2 O ~ B(OH)4 + H+
Diborane (B 2H 6 )
• It is prepared as:
Ether
4BF3 + 3 LiAJH4 ~ 2B 2 H 6 + 3LiF + 3 AlF3
• It has 4 terminal B-H bonds showing (2c- 2e- ) bonds
while 2 bridge B-H- B bonds show (3 c - 2e- ) bonds at
120° and 97° angle. It is also known as banana bonding.
• B3 N 3 H 6 is inorganic benzene or borazine, which is formed
when it reacts with ammonia. Both B and N are sp 2
hybridised.
• BCI3 does not form a dimer but AlCI 3 can form. Small size
boron cannot hold large size chlorine atom. BCI 3 and
AlCl 3 have bridged structure in solid phase. They are
electron deficient and behave as Lewis acid.
236 I Chapterwise & Topicwise Engineering Entrances Solved Papers
BC1 3 + 3H2O ~ H 3 BO3 +3HC1
Al2Cl6(s)+6 H2O ~ [Al(H2O)6] + + c 1- 3 causes increase in green house effect, i.e. decrease in
• Bauxite is an important ore of aluminium. Fe 2 0 3 and SiO2
are its main impurities removed by Baeyer's or Hall's
process and Serpeck's process, respectively. Aluminium is
ob tained by electrolysis of alumina dissolved in fused
cryolite, refin ed by Hoope's electrolytic process. When
bauxite ore is treated with cone. NaOH solution at 500 K
and 35 bar pressure, the filtrate contains NaAl(OH)4 .
• Potash alum dissolves in water to give an acidic solution of
H2 SO4 . Alums are used for tanning ofleather, coagulation
of blood, purification of water.
• Thermite reaction contains Fe 2O 3 and Al in the ratio of
I : 3 by volume. Due to great affinity ofaluminium towards
oxygen, it combines with oxygen.
• Nitride of Al is AIN, carbon cannot be used in the reduction
of Al 20 3 due to high enthalpy of formation of Al 20 3 .
• Duralumin is alloy of aluminium, is used in aircrafts.
Elements of Group 14
Carbon fami ly includes C, Si, Ge, Sn and Pb. The general
valence shell configuration is ns 2 , np2 .
• Ionisation enthalpy, electronegativity, melting and boiling
point decrease on moving down the group. Atomic and
ionic radius, metallic character and electropositivity
increases on moving down the group.
Chemical Properties
• With air, MO and M0 2 type oxides are formed. Acidic
character of oxides decreases down the group.
C, Si, Ge do not react with water. Sn reacts with steam to
produce H 2.
• With halogens, MX 4 and MX2 type halides are fom1ed.
Thermal stability decreases down the group.
• Tendency of catenation decreases on moving down the
group, i.e. C >> Si > Ge= Sn > Pb.
Allotropes of Carbon
Important allotropes of carbon are diamond, graphite and
fullerenes. Graphite has higher C- C bond order than
diamond. Graphite has higher conductivity than diamond.
Diamond is hard because all four bonds are with carbon.
• The mixture of CO + H2 is water gas and CO + N 2 is
producer gas.
• Solid CO2 is called dry ice. Increased content of CO 2
fertility and pH of water. Dry ice is used as a refrigerant
for ice cream and frozen food . Gaseous CO 2 is used to in
aerated soft drinks and as a fire extinguisher.
Silicon
• Silicon tetrafluoride SiF4 behaves as Lewis acid and can
accept lone pair of electron of ligand due to presence of
vacant d-orbitals in silicon. Silicon tetrachloride (SiC1 4 )
on hydrolysis gives silicic acid which on heating gives
silicon gel.
• Silicon dioxide also called silica (SiO 2) is found in quartz,
tridymite. When heated with carbon in an electric furnace,
it is reduced to SiC.
SiO2 + 3C ~ SiC + 2CO
SiC is carborundum or silicon carbide.
• SiO 2 is a covalent, three-dimensional network solid in
which each silicon atom is covalently bonded in a
tetrahedral manner to four oxygen atoms and each oxygen
atoms in tum covalently bonded to another Si atoms. Silica
is extensively used in transistors and optical instrument. It
is both gangue and acidic flux. Agate is SiO2 • Common
glass is Na 2 O· CaO• 6SiO 2.
• Silicones are organosilicone polymers having -R 2SiO
monomer and-O-Si-0-linkage. They are prepared
by hydrolysis of alkyl or aryl derivative ofSiC1 4 • Silicones
are hydrophobic in nature, used as sealant, greases,
electrical insulators and water proofing.
• Silicates are minerals of silicon. Silicate has SiO4 as basic
repeating unit. Pyrosilicate ion is Si 20~ . In cyclosilicate,
two oxygen atom of each Sio:,- tetrahedron are shared
with others and cyclic structure is obtained. Silicates in
which three oxygen atoms of[SiO4 ] 4 - are shared are sheet
silicates.
• Tin upon reaction with NaOH forms sodium stannite and
with cone. HNO 3 forms metastannic acid, e.g.
Sn + 2NaOH + 4H2O ~ Na 2 SnO3 + 2H 2
Sn + 4HNO 3 ~ H 2 SnO3 + 4NO2 + H 2O
Metastannic acid
• Solder is an alloy of tin and lead used in joining of in
electrical circuits.
 Topic 1
Group 13 Elements
2014
1. The correct statements for orthoboric acid is/are 6. Name of the alloy of aluminium which is used in aeroplane
[J EE Advanced] is [Kerala CEE]
(a) it behaves as a weak acid in water due to selfionisation (a) duralumin (b) bell metal
(b) acidity of its aqueous solution increases upon (c) y-alloy (gamma alloy) (d) aluminium bronze
addition of ethylene glycol (e) alumina
(c) it has a three-dimensional structure due to hydrogen
bonding 2012
(d) it is a weak electrolyte in water 7. Correct formula of aluminium nitride is [OJEE]
2. For the properties mentioned the correct trend for the (a) Al 2 N 2 (b) AlN 3 (c) AlN 2 (d) AlN
different species is in [KCET]
(a) strength as Lewis acid - BC! 3 > AlCl 3 > GaCl 3
2011
(b) inert pair effect - Al > Ga > In 8. Boron cannot form which one of the following anions?
(c) oxidising property - Al 3+ > In 3 + > Tl 3 + (a) BFJ- (b) BH;j [AIEEE]
(d) first ionisation enthalpy - B > Al > Tl (c) B (OH) 4 (d) BO2
3. Which one of the following correctly represents the
variation ofelectronegativity (EN) with atomic number (Z) 2010
of group 13 elements? [EAMCET] 9. Carbon cannot be used in the reduction of Al 2 0 3 because
(a) it is an expensive proposition [Manipal]

~
B Tl (b) the enthalpy of formation of CO 2 is more than that of
EN EN
Al 2 O 3
a Al (c) pure carbon is not easily available
(a) r n
(b)
r In
(d) the enthalpy of formation of Al 2 O 3 is too high

Tl 10. Tincal is [MP P ET]

Ga
- z - z (a)Na 2 CO 3 -I0H 2 O (b)NaNO 3
(c) Na 2 B4 O 7 · 10H2 O (d) NaCl
B 11. Inorganic benzene is [JCECEJ
Tl
EN EN (a) B 3 H 3 N 3 (b) BH 3 NH 3 (c) B 3 H 6 N 3 (d) H3 B 3 N 6

(c) r
V-
a
In
z
I (d)
r

4. Aluminium hydroxide, Al(OHh is insoluble in water, but

-z
Al
Ga
In
2009
12. In alumino thermic process, Al is used as
(a) reducing agent
(c) catalyst
(b) oxidising agent
(d) electrolyte
13. Which is a co1Tect statement about diborane structure?
[OJEEJ

dissolves readily in both acidic and basic solutions. Such (a) All HBH bond angles are equal [DCEJ
behaviour is characteristic of [Guj CET] (b) All H- B bond lengths are equal
(a) polyprotic behaviour (b) hydrophilic behaviour (c) It has two 3-centre-2 electron bonds
(c) a buffer (d) amphoteric behaviour (d) All hydrogen and boron atoms are in one plane
14. Bauxite ore is made up of Al 2 O 3 + SiO 2 + TiO 2
2013 + Fe 2 O 3 . This ore is treated with cone. NaOH solution at
5. Aluminium oxide is not reduced by chemical reactions 500 Kand 35 bar pressure for few hours and filtered hot. In
since [KCET] the filtrate the species present, are [DCEJ
(a) reducing agent contaminate (a) NaAl (OH)4
(b) the process pollute the environment (b) Na 2 T i(OH) 6
(c) aluminium oxide is highly stable (c) NaAl(OH) 4 and Na 2 SiO 3
(d) aluminium oxide is reactive (d) Na 2 SiO3
238 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2008
15. Which one of the following is the correct statement ? 26. Purification of alumina takes place by CBCECE]
(a) Boric acid is a protonic acid CAIEEE] (a) Bosch process (b) Hall's process
(b) Beryllium exhibits coordination number of six (c) Hoope's process (d) quartation process
(c) Chlorides of both beryllium and aluminium have 27. The chief impurity present in red bauxite is [DCEJ
b1idged chloride structures in solid phase
(d) B2 H 6 · 2NH 3 is known as inorganic benzene (a) SiO2 (b) Fe 2 O 3
(c) K 2 SO4 (d) NaF
16. Boron halides behave as Lewis acids because of their
.......... nature. [BITSAT, AMU, EAMCET] 28. An element 'X' which occurs in the first short period has
an outer electronic structure s2p • What is the formula and
1
(a) proton donor (b) covalent
(c) electron deficient (d) ionising acid-base character of its oxides? [DCE]

17. The ratio of Fe 2 O 3 and Al by weight in therrnite is (a) XO 3 , basic (b) X 2 0 3 , basic
(c) X 2 O 3 , acidic (d) X02 , acidic
(a) 1: 3 (b) 1: 2 [BITSAT]
29. Aluminium chloride exists as din1er, Al 2 Cl 6 in solid state
(c) 3: l (d) None of these
as well as in solution of non-polar solvents such as
18. Potash alum dissolves in water to give a/an [Manipal] benzene. When dissolved in water, it gives
(a) acidic solution ofH 2 SO4 (a) Al 3+ + 3Cl- [Jamia Millia Islamia]
(b) alkaline solution
(c) acidic solution ofHCI (b) [Al(H2 O) 6 ] 3 + + 3Cl-
(d) neutral solution (c) [A1(OH) 6 ] 3- + 3HCI
19. Aluminium metal is refined by [MP PET] (d) A1 2 0 3 + 6HCI
(a) Serpeck's process (b) Baeyer's process 2006
(c) Hall's process (d) Hoope's process
30. B(OHh + NaOH ~ NaBO2 + Na [B(OH) 4 ] + H 2 O
2007 How can this reaction is made to proceed in forward
20. Aluminium is obtained by [WB JEE] direction ? [ITT JEE]
(a) reducing A1 2 O 3 with coke (a) Addition of cis-1, 2-diol
(b) electrolysing A1 2 O 3 dissolved in Na 3 AlF6 (b) Addition of borax
(c) reducing A1 2 O 3 with chromium (c) Addition oftrans-1, 2-diol
(d) heating alumina with cryolite (d) Addition ofNa 2 HPO 4
21. Alums are used for [WBJEE] 31. Boric acid is used in carrom boards for smooth gliding of
(a) tanning of leather (b) coagulation of blood pawns because [Kerala CEE]
(c) purification of water (d) All of these (a) H3 BO3 molecules are loosely chemically bonded and
22. BCI 3 + H 2 0 ~ X, the products formed in the reaction hence soft
are CWBJEEJ
(b) its low density makes it fluffy
(c) it can be powdered to a very small grain size
(a) B 2 O 3 + HOC! (b) H 3 BO3 + HCI (d) it is chemically inert with the plywood
(c) B 2 H 6 + HCl (d) No reaction (e) H-bonding in H 3 BO3 gives it a layered structure
23. The mass of carbon anode consumed (giving only carbon 32. Which of the following is a use of alum ? CWB JEE]
dioxide) in production of270 kg of aluminium metal from
(a) Making explosives
bauxite by the Hall process is
(b) Bleaching clothes
(Atomic mass of Al = 27) CUPSEE] (c) Water softening
(a) 180 kg (b) 270 kg (c) 540 kg (d) 90 kg (d) All of the above
24. Which one of the following compounds, is not a protonic 33. In the electrolytic method of obtaining aluminium from
acid ? [UPSEE] purified bauxite, cryolite is added to the charge in order to
(a) SO(OH)i (b) SO2 (OH)2 (a) minimise the heat loss due to radiation [AMUJ
(c) B(OHh (d) PO(OH)} (b) protect aluminium produced from oxygen
(c) dissolve bauxite and render it conductor of electricity
25. The structure of diborane (B 2 H6 ) contains [UPSEE] (d) lower the melting point of bauxite
(a) four 2c - 2e- bonds and four 3c- 2e- bonds
34. Magnalium contains [Guj CETJ
(b) two 2c-2e- bonds and two 3c-3e- bonds
(c) two 2c - 2e- bonds and four 3c - 2e- bonds (a) Al + Mg (b) Mg + Cu
(d) four 2 c - 2e - bonds and two 3 c - 2e- bonds (c)Mg+ Fe (d) Mg + Ag
 p-block Elements I 239
35. Alum is added to muddy water because 40. The order of acidic strength of boron trihalides
(a) it acts as disinfectant [Jamia Millia Islamia] (a) BF3 < BC1 3 < BBr3 < B13 [Ke rala CEE, AMU]
(b) it results in coagulation of clay and sand (b) B13 < BBr3 < BC1 3 < BF3
(c) clay is soluble in alum, hence removes it (c) BC13 < BBr3 < B13 < BF3
( d) it makes water alkaline which is good for health (d) BBr3 < BC1 3 < BF3 < B13
(e) BF3 < B13 < BCl 3 < BBr3
2005 41. Observe the following statements regarding purification of
36. Heating an aqueous solution of aluminium chlotide to bauxite.
dryness will give [AIEEE]
I. During Hall's process, silica is removed as Si (vapour).
(a) A1(OH)CI 2 TT. Bauxite ore contaminated with F~O 3 is purified in
(b) A12O3 Baeyer's process.
(c) A1 2 Cl 6 ITT. During Serpeck's process, AIN is formed.
(d) A1Cl 3
The correct answer is [EAMCETJ
37. Aluminium reacts with caustic soda to form [Manipal]
(a) I, II and III (b) I and II
(a) aluminium hydroxide (b) aluminium oxide (c) I and III ( d) II and III
(c) sodium metaaluminate (d) sodium tetraaluminate
42. Muddy water can be purified through coagulation by using
38. In diborane the two H- B-H angles are nearly
(a) common salt (b) alums [J&K CET]
(a) 60°, 120° [Manipal] (c) sand (d) lime
(b) 97°, 120° 43. Purification of Al by electrolysis method is called
(c) 95°, 150°
(a) Hall's process (b) Baeyer process [BCECEJ
(d) 120°, 180°
(c) Ostwald process (d) Hoope's process
39. In Goldschmidt aluminothermic process, thermite contains
44. Aluminium is extracted by the electrolysis of
(a) 3 parts of A1 2 O 3 and 4 parts of Al [Guj CET, KCET]
(a) alumina [Jamia Millia IslamiaJ
(b) 3 parts of Fe 20 3 and 2 parts of Al
(b) bauxite
(c) 3 parts ofFe 2O 3 and I part of Al
(c) molten cryolite
(d) 1 part ofFe 2O 3 and I part of Al
( d) alumina mixed with molten cryolite

Topic 2
Group 14 Elements
2014 2012
1. Which one of the following elements reacts with steam? 4. With respect to graphite and diamond, which of the
(a) C (b) Ge [EAMCETJ statement(s) given is (are) correct? [IIT JEE]
(c) Si (d) Sn (a) Graphite is harder th an diamond
(b) Graph ite has higher electrical conductivity than
2013 diamond
2. The carbon based reduction method is not used for the (c) Graphite has higher thermal conductivity than
extraction of [JEE Advanced] diamond
(a) tin from SnO 2 ( d) Graphite has higher C-C bond order than diamond
(b) iron from Fe 2 O 3 5. CO2 goes to air, causes green house effect and gets
(c) aluminium from A1 2 O 3 dissolved in water. What will be its effect on soil fertility
(d) magnesium from MgCO3 , CaCO3 and pH of the water? [BITSATJ
3. Pyrosilicate ion is [Ke rala CEEJ (a) Increase (b) Decrease
(a) SiO~- (b) SiO~- ( c) Remain same (d) None of these
(c) Si 2 o:- (d) SiO3 6. Solder is an alloy of lead with [Manipal]
(d) Zn
(e) Si 2 0 ~- (a) Cu (b) Fe (c) Sn
240 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2010
7. Which type of silicate is shown in the given figure? 17. A fibrous mineral which can withstand red hot flan1es
without any damage is [Manipal]
(a) talc (b) glass wool
(c) soap stone (d) asbestos
18. Silica is a/an [Manipal]
(a) acidic flux only
(b) gangue only
(c) basic flux only
[Guj CET]
(d) Both gangue and acidic flux
(a) Orthosilicate (b) Pyrosilicate
19. Roasted tin stone ore after washing with water is known as
(c) Metasilicate (d) None of these
(a) block tin (b) white tin [Manipal]
8. Producer gas is the mixture of [JCECE]
(c) black tin (d) granulated tin
(a) CO+ N 2 (b) CO+ H 2
20. Quartz is an example of [MPPET]
(c) CO + water vapour (d) N 2 + CH 4
(a) chain silicate
2009 (b) sheet silicate
9. Dry ice is [UPSEE] (c) cyclic s ilicate
(d) three din1ensional network silicate
(a) solid H 2 0 (b) solid CO2
(c) solid N 2 0 4 (d) solid NH 3 21. The incon-ect statement/s among the following is/are
10. What product is formed on heating lead nitrate? [OJEE] I. NCl 5 does not exist while PCl 5 does.
TT. Lead prefers to form tetravalent compounds.
(a) PbO+ NO+ 0 2 (b) PbO+ N0 2 + 0 2
ITT. The three C--0 bonds are not equal in the carbonate ion.
(c) Pb+ N0 2 (d) PbO+ N 2
IV. Both o; and NO are paramagnetic. [Kerala CEE]
11. The basic stmctural unit in silicates is [AMU]
(a) I, III and IV (b) I and IV
(a) Si02 (b)[Si 2 0 7 ]2- (c) II and III (d) I and III
(c) SiO.t tetrahedron (d) [Si 2 0 5 ] 2- (e) IV Only
12. Buckminster-fullerene is a variety of [CGPET] 22. Which of the following oxides is amphoteric in character?
(a) boron (b) carbon (a) Sn02 (b) Si02 CUPSEEJ
(c) ammonia (d) fluorine (c) CO2 (d) CaO
13. In feldspar and zeolite, Si 4+ ions are replaced by which 23. In silica (Si02 ), each silicon atom is bonded to [UPSEEJ
ions? [Guj CET] (a) two oxygen atoms
(a) Ox ide ion (b) Hydroxide ion (b) four oxygen atoms
(c) Aluminium ion (d) Potassium ion (c) one silicon and two oxygen atoms
(d) one silicon and four oxygen atoms
2008 24. White lead is [UPSEEJ
14. Among the following substituted silanes, the one which (a) PbC03 · PbO (b) PbC03
will give rise to cross linked silicon polymer on (c) Pb(OH)z · 2PbC03 (d) PbS04 · PbO
hydrolysis is [AIEEE]
25. What is the number of free electrons present on each
(a) R 4 Si (b) RSiC1 3 carbon atom in graphite ? [DCEJ
(c) R 2 SiC12 (d) R 3 SiCl
WO ~3 W2 ~l
15. Identify Bin the following reaction,
H4Si04 iooooel A Carbon l B + CO 2007
- H~ t,. [BITSAT, AMU, EAMCET] 26. The stability of dihalides of Si, Ge, Sn and Pb increases
(a) corundum (b) quartz steadily in the sequence [AIEEEJ
(c) silica (d) carborundum (a) GeX2 < SiX2 < SnX2 < PbX2
16. Diamond is hard because [VITEEEJ (b) SiX2 < GeX2 < PbX2 < SnX2
(c) SiX2 < GeX2 < SnX2 < PbX2
(a) all the four valence electrons are bonded to each (d) PbX2 < SnX2 < GeX2 < SiX2
carbon atom by covalent bonds
(b) it is a giant molecule 27. Which glass has the highest percentage of lead? [BITSATJ
(c) it is made up of carbon atoms (a) Soda glass (b) Flint glass
(d) it cannot be burnt (c) Jena glass (d) Pyrex glass
 p-block Elements I 241
28. Which one of the following statements about the zeolites is 39. Which is likely to show inert-pair effect? [DCEJ
false ? [Manipall (a) K (b) Mg
(a) They are used as cation exchangers (c) Al (d) Pb
(b) They have open structure which enables them to take 40. In SiFJ- and SiCl ~- which one is known and why?
up small molecules
(c) Zeolites are alurninosilicates having three (a) SiFJ- because of small size off [DCEJ
dimensional network (b) SiFJ- because of large size off
(d) Some of the SiO!- units are replaced by AlO~- and (c) SiCI~- because of small size of Cl
AIOt ions in zeolites (d) SiCl~- because of large size of Cl
29. Which of the following does not contain silicon? 41. The soldiers of Napolean army while at Alps during
(a) Kaoline (b) Agate [MHT CETJ freezing winter suffered a serious problem as regards to the
(c) Ruby (d) Quartz tin buttons of their uniforms. White metallic tin buttons got
30. Carborundum is [MHTCET] converted to grey powder. This transformation is related to
[Jamia Millia Islamia]
(a) SiC (b) Al 2 0 3 · H 2 0
(c) Al 2 (SO4 ) 3 (d) AlC13 (a) a change in the crystalline structure of tin
(b) an interaction with nitrogen of the air at very low
31. Monosilane on coming in contact with air bums with a temperature
luminous flame producing v01tex rings. These rings (c) a change in the partial pressure of oxygen in the air
are of [MHT CETJ (d) an interaction with water vapour contained in the
(a) SiO2 (b) SiO (c) Si (d) H 2 SiO3 humid air
32. Graphite is a soft solid lubricant extremely difficult to melt.
The reason for this anomalous behaviour is that, graphite
2006
[UPSEE, KCET, MP PET] 42. A metal, M fo1ms chlorides in its + 2 and + 4 oxidation
states. Which of the following statements about these
(a) is a non-crystalline substance
chlorides is correct ? [AIEEEJ
(b) is an allotropic form of diamond
(c) bas molecules of variable molecular masses like (a) MCl 2 is more volati le than MCl 4
polymers (b) MCl 2 is more soluble in the anhydrous ethanol than
(d) bas carbon atoms arranged in large plates of rings of MCl 4
strongly bound carbon atoms with weak interplate (c) MCI 2 is more ionic than MCI 4
bonds (d) MCl 2 is more easily hydrolysed than MCl 4
33. Which of the following is used in making printer's ink, 43. The composition of the common glass is [Manipal]
shoe polish, black varnish and paint ? [WB JEE] (a) Na 2 O-CaO• 6SiO 2 (b) Na 2 O· Al 2 O 3 · SiO2
(a) Lamp black (b) Bone black (c) CaO-Al 2 O 3 -SiO2 (d) Na 2 O -CaO-6SiO2
(c) Carbon black (d) None of these 44. In the preparation of amorphous silicon, HF acid is used to
34. Moderate electrical conductivity is shown by [WB JEE] remove [MP PET, MHT CET]
(a) silica (b) graphite (a) Mg (b) SiO2
(c) diamond (d) carborundum (c) Si (d) None of these
35. CO is poisonous gas, antidote for CO poisoning is 45. Water gas is [WB JEE, MP PET]
(a) carborundw.n (b) carbogen [WB JEE] (a) CO + N 2 (b) CO + CO2 + CH 4
(c) carbonic acid (d) pure oxygen (c) CO 2 + N 2 (d) CO + H 2
36. An oxide of an element is a gas and dissolves in water to 46. The purest form of coal is [WBJEE]
give an acidic solution. The element belongs to (a) peat (b) anthracite
(a) II group (b) IV group [EAMCETJ (c) bituminous (d) lignite
(c) VIII group (d) zero group 47. Pb reacts with dilute HNO3 produces [UPSEE]
37. Calorific value of producer gas is low because of (a) NO (b) NH4 NO 3 (c) N 2 O 5 (d) NO2
(a) high per cent ofN 2 [EAMCETJ 48. Crystalline form of silica is called [UPSEE]
(b) low per cent of CO 2
(c) high per cent of CO (a) crystalline silicon (b) quartz
(d) low per cent ofN2 (c) rock (d) talc
38. Water glass is [BCECE]
49. Buclaninster fullerene is [UPSEEJ

(a) glass made of water (b) sodium silicate (a) pure graphite (b) C-60
(c) calcium formate (d) pyrex glass (c) diamond (d) C-90
242 I Chapterwise & Topicwise Engineering Entrances Solved Papers
50. Which of the following is used for making optical 58. When tin is treated with concentrated nitric acid
instruments ? [EAMCET] (a) it is converted into stannous nitrate [Manipal]
(a) Si02 (b) Si (c) SiH4 (d) SiC (b) it is converted into stannic nitrate
(c) it is converted into metastannic acid
51. One recently discovered allotrope of carbon (e.g. C 60 ) is
(d) it becomes passive
known as [Guj CET]
59. Formula for agate is [MHTCET]
(a) fluorine (b) fullerene
(c) flourene (d) freon (a) Na 2Si03 (b) K 20· Si02 · Al203
(c) Si02 (d) CaF2
52. Addition ofSnC12 to HgCl 2 gives precipitate [BCECE]
60. Which element is used for making a transistor? [MP PET]
(a) white turning to red (b) white turning to grey
(a) Sn (b) Sb (c) Si (d) Mg
(c) black turning to white (d) None of these
61. On controlled hydrolysis and condensation, R 3SiCl yields
53. Which gas is used in aerated water ? [BCECE]
(a) CO2 (b) S02 (a) R 3Si- O-SiR 3 [OJEEJ
(c) CO (d) Water vapours (b) (- R3Si- 0-SiR3- )n
54. The chemical formula of sindhur is [DCE] (c) R 3Si0H
R R
(a) PbO (b) Pb 30 4
(c) ZnO (d) SnCl 2
I I
(d) - Si- 0 - Si-
55.
l I
0 0
I I
- Si- 0 - Si-
l I
62. The tendency for catenation in group 14 elements varies in
the order [AMUJ

Silicate structure is unit of [DCE] (a) C» Si >Ge=Sn > Pb

(b) C« Si < Ge= Sn< Pb
(a)(Si4011 ),~n- (b) (Si201I )n2n-
(c) C» Si < Ge < Sn < Pb
(c) (Si 2 0 3 ) (d) (Si04 )- 4 (d) C » Si = Ge = Sn > Pb
63. The thermal stability of CF4 is [AMUJ
2005
(a) less than SiF4 (b) more than SiF4
56. Name of structure of silicates in which three oxygen atoms
4 (c) less than CCl 4 (d) less than SiC1 4
of[Si04 ] - are shared is urr JEE]
64. Which of the following is not correct ? [EAMCETJ
(a) pyrosilicate (b) sheet silicate
(c) linear chain silicate (d) three dimensional silicate (a) Si02 is used as acidic flux
(b) The distance between the layers in graphite is
57 . In silicon dioxide [AIEEEJ 3.35x 10- 3 cm
(a) there are double bonds between silicon and oxygen (c) Si02 reacts with Na 2C03 and liberates CO
atoms (d) The hybridisation ofC in graphite is sp 2
(b) silicon atom is bonded to two oxygen atoms
(c) each silicon atom is surrounded by two oxygen atoms 65. Carborundum is obtained when silica is heated at high
and each oxygen atom is bounded to two silicon atoms temperature with [DCEJ
(d) each silicon atom is surrounded by four oxygen (a) carbon (b) carbon monoxide
atoms and each oxygen atom is bounded to two (c) carbon dioxide (d) calcium carbonate
silicon atoms
 Answers
ill!C..1 Group 13 Elements
1. (b,d) 2. (a, d) 3. (d) 4. (d) 5. (c) 6. (a) 7. (d) 8. (a) 9. (d) 10. (c)
11. (c) 12. (a) 13. (c) 14. (a) 15. (c) 16. (c) 17. (c) 18. (a) 19. (d) 20. (b)
21 . (d) 22. (b) 23. (d) 24. (c) 25. (d) 26. (b) 27. (b) 28. (c) 29. (b) 30. (a)
31 . (e) 32. (c) 33. (d) 34. (a) 35. (b) 36. (b) 37. (c) 38. (b) 39. (c) 40. (a)
41 . (d) 42. (b) 43. (d) 44. (d)
TOPIC2 Group 14 Elements
1. (d) 2. (c,d) 3. (e) 4. (b,d) 5. (b) 6. (c) 7. (d) 8. (a) 9. (b) 10. (b)
11. (c) 12. (b) 13. (c) 14. (b) 15. (d) 16. (a) 17. (d) 18. (d) 19. (c) 20. (d)
21 . (c) 22. (a) 23. (b) 24. (c) 25. (d) 26. (c) 27. (b) 28. (d) 29. (c) 30. (a)
31 . (a) 32. (d) 33. (a) 34. (b) 35. (b) 36. (b) 37. (a) 38. (b) 39. (d) 40. (a)
41 . (a) 42. (c) 43. (a) 44. (b) 45. (d) 46. (b) 47. (a) 48. (b) 49. (b) 50. (a)
51 . (b) 52. (b) 53. (a) 54. (b) 55. (a) 56. (b) 57. (d) 58. (c) 59. (c) 60. (c)
61 . (a) 62. (a) 63. (b) 64. (c) 65. (a)

Explanations
Topic 1 Group 13 Elements
1. (a) It does not undergo self ionisation in water but accepts an (d) In water, the pK 0 value ofH 3B03 is 9.25
e lectron pair from water, so it behaves as weak monobasic acid. H 3B03 + Hp ~ B(OH)4 + W pK0 = 9.25
H 3B0 3 + H 20 ~ [B(OH)4 i- + W So, it is a weak electrolyte in water.
Hence, (a) is incorrect. 2. (a) Lewis acid is an electron pair acceptor. The Lewis
(b) When treated with 1,2-dihydroxy or polyhydroxy compounds acid strength decreases down the group because as the size
they form chelate (ring complex compound) which effectively of central metal increases, the interaction between the
remove [B(OH)4 rspecies from solution and thereby produce incoming electron pair and nucleus weakens. Thus, the
maximum number ofH 30 + or H+ ion is results in increase in given trend for strength of Lewis acid is
acidity. BC13 > AIC1 3 > GaCl 3•
Hence, (b) is correct. Hence, the option (a) is correct.
(c) Boric acid crystallises in a layer structure in which planar (b) Inert pair effect i.e. reluctance ofs-electrons to participate in
triangular B(OH)3 units are bonded together through hydrogen a reaction (i.e. bond formation) increases down the group.
bonds. Due to which lower oxidation states are much more
stable than higher oxidation states. Thus, the correct trend
would be:
Al< Ga< In.
Hence, option (b) is incorrect.
(c) The tendency to oxidise in lower oxidation states i.e.
oxidising property of M 3+ ions increases down the group.
Thus, the correct trend is: Al 3+ < In 3+ < TJ 3+.
Thus, option (c) is incorrect.
(d) On moving down in a group, first ionisation enthalpy
decreases. Therefore, order of first ionisation enthalpy for
group 13 elements is B >Al> Ga> Tl> In.
Thus, the option (d) is correct.
3. For group 13 elements, electronegativity decrease from B to Al.
The decrease in electronegativity from B to Al is due to
H H increased size of Al. The remaining three elements are more
electronegative than Al and their electronegativity increases
Structure of Boric acid
from Ga to T l.
Hence, (c) is incorrect.
244 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Thus, the correct order of electronegativity of group 13 H

elements are as follows. I
Element B Al Ga In Tl /c"-
H- c C- H
EN (at Pauling scale) 2.0 1.5 1.6 1.7 1.8
H-
IC C- II H
'/
rH
Borazole or Borazine Benzene

12. In alumino thermic process, aluminium is used as reducing agent.

3000°C
Alz0 3 + 2Fe+ 185 kcal
- z
13. In diborane, four terminal H-atoms along with two B-atoms lie in
4. Aluminium shows amphoteric behaviour, as it acts as a base and
one plane while two bridging hydrogens are present above
reacts with acids to form aluminium salts, while as an acid Oike and below this plane. The four terminal B- H bonds are regular
H 3AI03) it reacts with alkalies to give aluminates. 2 centr~2 electrons bonds w hile two bridge bonds are 3 centred-2
As a base (neutralising an acid) electrons bonds.
Al(OH)3 + 3HCI - AICl 3 + 3H 20

~~\{§)
Base Acid Salt
As an acid (neutralising a base)
Al(OH)3 + NaOH - Na[Al(OH)4 ] H- . . . . . . _ ~ / H
Acid Base Aluminate

5. Aluminium oxide is highly stable therefore, it is not oxidised

c§f;?!J"YJ H/ B ~ B '---H
by chemical reactions. H H H
6. Duralumin alloy (Cu + Al + Mn + Mg) of aluminium is used In B 2H6 , each B atom uses sp 3 hybrid orbital for bonding. Out of 4
in aeroplane, i.e. for aircraft parts.
sp3 hybrid orbitals one orbital is empty, i.e. without any e- (shown
7. Formula of aluminium nitride is AIN. by dotted lines). Thus, the involvement of one half-filled orbital of
8. Electronic configuration of B one B-atom with one empty orbitals of other B-atom and half filled
orbital ofH-atom results in 3 centred-2 electron bond which is an
1s 2 2s2 2p' electron deficient bridge bond. Such bond is also called banana
illJ illJ 11 I I I Ground state bond.
14. In bauxite ore, only Al 20 3 reacts with cone. NaOH and forms
2s' 2p2

[illt.__rn_11_1_1 i_t Excited state

sodium metaaluminate. While impurities being insoluble settle
down and the solution is filtered. The fi lterate contains only sodium
metaaluminate NaAI (OH)4.
Fourth lone pair is This further dissolves in water.
accomodated in 500 K
this empty orbital. Alz03 + 2H 20 + 2NaOH ~ 2NaA102 + 3H20
Maximum covalency ~ 4 35 bar

NaAl0 2 + 2H20 - NaAl(OH)4

Due to absence of 2d-orbital, maximtm1 covalency is four.
15. Chlorides of both beryllium and aluminium have bridged stmctures
Thus, BFt is not formed. Hence, (a) is not formed. in solid phase.
BH4 (BH 3 + ff), B(OH)4 (B(OH)3 + Off) and B02 are
formed.
9. The enthalpy offormation of Alz0 3 is very high and hence, it is
not possible to reduce it by carbon.
10. Naturally occurring cmde borax is called tincal. Thus, it is
chemically Na 2B40 7 · 10H20.
11 . Borazine, B 3Nl\ is also known as inorganic benzene due to its
resemblance in stmcture and properties with benzene.

16. According to Lewis, the compound which can accept a Ione pair of
electron, are called acids. Boron halides, being e lectron deficient
compounds, can accept Ione pair of electrons, so termed as Lewis
acids.
17. Thermite is the mixture ofFezO3 and Al. Due to greater affinity of
aluminiwn towards oxygen, it readily combines with oxygen.
Hence, Goldschmidt used Al to reduce metal oxides in extraction. In
thermite, the ratio of Fez0 3 and Al is taken 3 : I by weight.
FezO 3 + 2AI - 2Fe + Al 2O 3
(2x56+ 3x 16 = 160) (2 x 27 = 54)
p -block Elements I 245
27. The main impurity in red bauxite is ferrite (FezO 3) and the
main impurity in w hite bauxite is silica (SiO 2).
28. The outer electronic structure of 'X' is s2p', hence, element
'X' belongs to third group. It will be non-metal because it is
present in the first short period of third group. Its valency is + 3
because it belongs to third group.
Hence, formula of its oxide will be Xz0 3. The oxide will be
acidic in nature because it is oxide of non-metal.
29. AICI 3 is covalent but in water, it becomes ionic due to large
hydration energy of AI 3+.

18. Ki(SO 4)· Al 2 (SO 4 ) 3 · 24HzO - K 2SO4 + Al 2 (SO4) 3 + 24H2O AICI 3 + 6H2O ~ [Al(H2O~ ] 3+ + 3CI-
A1 2 (SO4)3 undergoes hydrolysis to give H2SO4 30. B(OH)3 + NaOH ~ NaBO2 + Na +[B(OH)4 ]- + H 2 O
Al2(SO4h + 6H2O - 2Al(OH)3 + 3H 2SO4
This reaction is reversible reaction because sodium
due to which aqueous solution of potash alum is acidic.
r
metaborate, Na+ [B(OH)4 formed by the reaction between
19. Aluminium metal is refined by Hoope's electrolytic process. B(OH)3 and NaOH gets hydrolysed to regenerate B(OH)J and
20. Aluminium is obtained by electrolysing alumina dissolved in NaOH.
cryolite (Na 3AIF6 )
Na+[B(OH)4 f Hydrolysis NaOH + B(OH)
4Na 3AIF6 ~ 12 Na+ + 4 A1 3+ + 12 F- 3
4AI3+ + 12e- - 4AI (at cathode) If some quantity of polyhydroxy compounds like cis-1, 2-diol,
catechol, glycerol etc. is added to the reaction mixture then the
12F- - 6 F2 + 12e- (at anode) B(OH)3 combines with such polyhydroxy compounds to give
2Alz03 + 6F2 - 4AJF3 + 302 chelated complex compound. Due to complex compound
formation, stability increases and due to higher stability of
21. Potash alum is used for tanning ofleather, as mordant in dyeing and
complex, reaction moves in forward direction.
calico printing, for sizing paper, as a styptic to stop bleeding and
purification of water. 31. Boric acid is used in carrom boards for smooth gliding of
pawns because H-bonding in H 3BO3 gives it a layered
22. BCI 3 + 3H2O - B(OH)3 + 3HCI structure.
Thus, the products are B(OHh or H 3BO3 and HCI.
32. Alums are used as water-softener. These are also used in
23. In Hall and Heroult process tanning of leather, as mordant in dyeing and to stop bleeding.
2Al 2O 3 - 4Al + 302 33. Cryolite (Na 3AJF6 ) is added to alumina for its electrolysis to
4C + 302 - 2CO 2 + 2CO i decrease its melting point and also to increase its conductivity.
2Alz03 + 4C - 4AI + 2CO 2 + 2CO 34. Magnalium is an alloy of Al (94.5%) and Mg (5.5%).
Only for removal of CO 2, following equation is possible
35. Ahun acts a.s coagulating agent, so it is used to purify water and
2Al 2O3 + 3C - 4Al + 3CO2 separate mud from it.
3 x l2 4x27
= 36g = 108g
36. Aqueous solution of AICI 3 contains hydrated AI 2C1 3 crystals
·: For I 08 g of Al , 36 g of C is required in above reaction. which on heating gives alumina.
: . For 270 x I0 3g of Al, required amount of C
Al 2C16 · 12Hz0~ Alz0 3 + 6HCI + 9Hz0
= ~ X 270 X 103 = 90 kg 37. Alwniniwn reacts with caustic soda to form sodiwn
108
metaalluninate.
24. B(OH)3 is not protonic acid because it does not give proton on
ionisation directly while it acts as Lewis acid due to a acceptance of 2AI + 2NaOH + 2H2O - 2NaAlO2 + 3H2 i
Sodium
OH- from water and forms a hydrated species. metaaluminate
B(OH)3 + Hp - [B(OH)4 + W r 38. In diborane, H-B-H (H-terminal) and H-B-H
25. B 2f\; has structure. (H-bridged) bond angles are 120° and 97° respectively.
Bridge
hydrogen
H -----------------

',,, , ' ~97

' ,, ./.1.'', ,.
26. Hall's process is used for purification of alumina. H --- ~ - -,-----------
Hoope's process is used for refining of alumina.
246 I Chapterwise & Topicwise Engineering Entrances Solved Papers
39. Goldschmidt in 1905 discovered a method for the reduction of
haematite (FeiO3 ) with aluminium metal. The process is known
as aluminothermic process, as in this process, large heat is
produced. Tn this, Fe2O 3 and aluminium are taken in 3 : 1ratio and
this mixture, known as thermite, is ignited to initiate the reaction,
when Fep3 is reduced to molten Fe.
2AI + Fe2O 3 - Al 2O3 + 2Fe + 3230 kJ
Molten
40. Boron trihalides are Lewis acid. The order of their acidic strength
is as
BF3 < BCl 3 < BBr3 < BT3
Tn the boron halides, a p1t -p1t back bonding arises due to empty
orbital of boron and filled orbitals of halogen.
9,
~>i----z
0 and one electron remain free giving electrical conductivity. Tn
This p1t -p1t back bonding has maximum effect in BF3 as the size
ofB and F-atoms are comparative. This effect decreases as the
size of halogen atom increases. Due to this effect, tendency of
accepting lone pair of electron of boron decreases, i.e. Lewis acid
character decreases.
41. Red bauxite which contains Fe2O 3 as the main impurity, is refined
eid1er by Baeyer's process or by Hall's process. White bauxite
containing SiO2 impurity is refined by Serpeck's method. Tn
Serpeck's method, following reactions take place
Al 2O3 · 2H2O + 3C + N 2 isoo·c 2AIN + 3CO + 2H2O
AIN + 3H2O - Al(OHh + NH 3
fl
2Al(OHh - Al2O 3 + 3Hp
42. Muddy water can be purified through coagulation by using
alums. Because alums contains Al3+ ions, drns, d1e negatively
charged colloidal particles of impurities get coagulated by Al 3+
ions and settle down. Pure water can be decanted off.
43. (a) Ostwald process It is used to manufacture HNO3 •
(b) Hoope's process Tt is the med10d used to purify aluminium.
Pure Al makes anode and impure aluminium makes cathode
in d1is reaction.
(c) Hall's process It is used to purify bauxite having no
specific impurity.
(d) Baeyer's process It is used to purify bauxite having chief
impurity of iron.
:. Hoope's process is correct answer.
44. Alumina is mixed w ith molten cryolite to lower its melting point
and to make it good conductor of electricity.
Topic 2 Group 14 Elements
1. C, Si and Ge do not react with water while Sn reacts with steam
and forms SnO 2 and H 2.
Sn (s) + 2H2O(g) - SnO 2 (g) + 2H 2 (g)
2. Al has greater affinity for oxygen hence oxide is not reduced by
carbon. MgO and CaO (fonned in the ca leination from carbonates)
are stable species and not reduced by carbon.
During smelting
SnO2 + C l300°Cl Sn + CO2
2Fep3 + 3C ~ 4Fe + 3CO2
3. Pyrosilicate ion is Sipt.
4. Diamond has a d1ree dimensional network structure, and hence is
a hard substance whereas graphite is soft due to layered structure.
In graphite, only d1ree valence electrons are involved in bonding
diamond, all the four valence electrons are covalently bonded
hence, insulator.
Diamond is better thennal conductor drnn graphite. Electrical
conductivity is due to avai lability of free electrons whi le thennal
conduction is due to transfer of thennal v ibrational energy from
one atom to another atom. A compact and precisely aligned
crystals like diamond thus, facilitate better movement of heat. In
graphite C- C bond acquire some double bond character, hence,
higher bond order than in diamond.
5. CO2 + H 2 O ~ H 2 CO 3 - H+ + HCO3
Here, [H+ ] increases hence, pH decreases due to which soil
fertility will also decrease.
6. Solder is an al loy of tin and lead. Tts melting point is quite low,
hence, it is very useftll in joining of ICs in various electrical
instruments.
7. When two oxygen of each Sio:- tetrahedron are shared with
others, cyclic or ring structures are obtained. These silicates are
known as cyclosilicates or cyclic silicates.
[Si6 O 18] 12- is an example of cyclosilicate. Tn this silicate six SiO3
discrete units are linked together.
8. Producer gas is a mixture of CO + N 2•
9. Solid CO2 sublimes directly to the vapour state (without
converting into liquid) at - 78°C under atmospheric pressure,
hence used as a refrigerant and called dry ice or cardice. It is used
to freeze metals, ice-cream and in laboratory as a coolant.
I':,.
10. 2Pb(NO3 h - 2PbO + 4NO 2 + 0 2
 p-block Elements I 247
11. The basic structural unit in silicates is Sio:- tetrahedron. In SiOt (iv) o; (8 + 8- I= 15) = NO(? + 8 = 15) crls2 , cr ls2, cr2s2,
unit, silicon atom is bonded to four oxide ions tetrahedrally. cr 2s2, cr2p;, 1t2p; ,.., 1t2p;, n: 2p~ NO (7 + 8 = 15)
Hence, both o; and NO contains one unpaired electron, so
12. A recently discovered family of carbon allotropes is Buckminster
fullerene. The most common fullerene has the fonnula C60 and paramagnetic.
contains hexagonal and pentagonal rings ofcarbon atoms. 22. A species is amphoteric ifit is soluble in acid (behaves as a base)
13. Generally, the ion exchange tendency of a material depends on as well as in base (behaves as an acid ).
the extent of isomorphous substitution in the tetrahedral SnO2 is an amphoteric oxide.
framework. Thus, the Si4+ ions of feldspar and zeolite are SnO 2 + 4HCI ~ SnCl4 + 2Hp
replaced by Al 3+ (aluminium ion). SnO2 + 2NaOH ~ Na2SnO 3 + H 2O
14. RSiCl 3 gives cross linked silicon polymer on hydrolysis. 23. In silica, silicon has large size, so the 3p -orbitals of Si does not
overlap effectively with 2p -orbitals of oxygen. Therefore, Si= 0
0 R 0 are not formed. The tetravalency ofSi is satisfied by the fonnation
ofSi---0 bonds, thus it is surrounded by four oxygen atoms.
I I I
---O - Si - O- Si - O- Si - R
I I I - Si - O - Si - O- Si -
0 0 0 j I I
I I I 0 0 0
--- R - Si - 0- Si - 0- Si - R I I I
I I I - Si - O - Si - O- Si -
0 R 0 n j I I
15. Orthosilicic acid (H4 SiO 4), on heating at high temperature, loses
0 0 0
two water molecules and gives silica (SiO 2 ) which on reduction
I I I
- Si - O - Si - O- Si -
with carbon gives carborundum (SiC) and CO.
j I I
H4Sl·o4 ~
IOOO"C S1·o2 ~
Jc ·c
S1 + 2 CQ
- 2H20 t,. Carborundum 24. Basic lead carbonate is generally known as white lead.
16. In diamond each carbon atom is linked to four other carbon atoms Formula of compound Name of the compound
by sigma bond. Each CJ C--C bond is fonned by the overlapping of PbCO3 -PbO Shannonite
sp3 hybrid orbitals of each carbon atom. Each carbon atom is PbCO 3 Cemssite
present at the centre of a regular tetrahedron. Each carbon atom is Pb(OH)2 · 2PbCO3 White lead
surrounded by four other carbon atoms present at the comers of a PbSO4 · PbO Lanarkite
regular tetrahedron. Structure of diamond is a rigid three 25. Graphite has a two dimensional structure. In this case, only three
dimensional network. This explains high density and hardness of of the four valence electrons of each carbon atom are involved in
diamond. bonding. Thus, each carbon atom makes use of sp2-hybrid
17. Asbestos can withstand red hot flames without any damage. orbitals.
Hence, the fourth valence of each carbon atom remains
18. When SiO 2 (silica) is present as earthly impurity in an ore, it is unsatisfied i.e. the fourth valence electron remains unpaired or
called gangue and when it is added to remove basic impurities free. This free electron can easily move from one carbon to
like CaO, FeO etc., it is called an acidic flux. another under the influence of applied potential. So, in strncture
19. Tin stone after roasting and washing is called black tin. of graphite only one electron is free on each carbon atom.
20. Quartz is an example of three dimensional network of (SiO 2 ),, 26. Due to inert pair effect, the stability of+ 2 oxidation state increases
silicate. as we move down this group.
21. (i) In nitrogen d-orbitals are absent, so it does not form NCl 5. :. SiX2 < GeX2 < SnX2 < PbX2
Thus, NCl 5 does not exist but PCl 5 does. 27. Flint glass or lead glass has composition of
(ii) Pb2+ is more stable than Pb4+, due to inert pair effect. Thus, K 2O · PbO · 6SiO2
lead prefers to form divalent compounds. It is used in making electric bulb and optical instruments.
(iii) In carbonate ion (CO~-)all the three C---0 bonds are identical 28. Zeolites are aluminosilicates having three dimensional open
due to resonance. strucnire in which four or six membered rings predominates.
Thus, due to open chain strncture, they have cavities and can take
up water and other small molecules.
29. Ruby is mineral of ahuninium i.e. Al2O 3. It does not contain
silicon.
248 I Chapterwise & Topicwise Engineering Entrances Solved Papers
30. When silica is heated with carbon in electric furnace, it is reduced
to carbomndum or silicon carbide.
SiO2 + 3C - SiC + 2CO
31. Monosilane (e.g. SiH 4) on coming in contact with air burns with a
luminous flame producing vortex ring. These rings are of silica.
SiH 4 + 202 - SiO 2 + 2H 2O
32. C-atoms form covalently bonded plates (layers). Layers are
bonded weakly together, that's w hy one layer can slide over other
cause lubricants and cannot be melted easily as large number of
atoms being bonded strongly in the layer form big entity.
33. Lamp black is used for all these purposes. Carbon black is used in
making tyres. Bone black is used for decolourisation of sugar.
34. In graphite, carbon atom is s/
hybridised having 3 covalent
bonds with 3 other carbon atoms in the same plane. The 4th
electron of C does not participate in bonding, remains free and is
responsible for electrical conductivity of graphite.
35. Antidote for CO poisoning is carbogen. Carbogen is a mixture of
90% oxygen and 5-10% carbon dioxide.
36. The element carbon belong to IV A group as it oxide, CO 2 when
dissolved in water forms carbonic acid.
C + O2 - CO2
CO 2 + Hp -➔ H 2CO3
Carbonic acid
37. Producer gas is a mixture of CO + N 2 • Its calorific valu e is low
due to high percentage of nitrogen.
38. Water glass is sodium silicate Na 2SiO3 .
2 SnCl 2 + 2HgCl 2 -
39. In the heavier elements of group TITA, IVA, and VA, the ns
electrons have extra stability and hence, do not take part in bond
formation. The reluctance of s-electron pair to take part in bond
formation is known as the inert pair effect. The inert pair effect
increases as the atomic number increases in the group.
Lead (Pb) is the element of group 14(IVA) hence, it shows inert
pair effect, hence for lead compounds + 2 oxidation state is more
predominant.
40. In SiFt and SiCtJ-, SiFt is known due to the small size of
F atoms. The small six F atoms can be easily accommodated
around Si atom to fonn SiFt while in SiCIJ-, six large Cl atoms
cannot be accommodated around Si atom.
41. Tin exists in three so lid forms, grey tin, white tin and rhombic tin
and all these three forms are interconvertible as :
18°C 16 1°C
grey ~ white ~ rhombic.
White tin is the most stable fonn. The conversion ofwhite tin into
grey tin takes place very slowly at 18°C (transition temperanire).
However, if the temperatme is low as - 50°C and a small amount
of grey tin is also present, the conversion becomes very rapid.
This conversion is known as tin disease or tin pest.
42. MCl 2, oxidation state of M =+
2
MCl 4, oxidation state of M = + 4
Higher the oxidation state, smaller the size.
Greater the polarizing power, greater the covalent characteristics.
Hence, MCl 4 is more covalent and MCl 2 is more ionic.
43. The simplest glass is soda glass which is also called soft glass.
Glass is super-cooled liquid mixnire. The composition of soft
glass is Na 2O -CaO · 6SiO 2•
44. Pure amorphous silicon is prepared by heating finely div ided
silica with magnesium powder.
SiO 2 + 2Mg- Si + 2Mg0
MgO can be removed by washing the residue w ith di lute HCI and
left SiO 2 is removed by treating with HF. This is because HF
reacts with SiO2 to form SiF4 .
SiO2 + 4HF- SiF4 + 2H2O
Hence, in the preparation of amorphous silicon, HF is used to
remove left over silico, SiO 2.
45. Water gas is a mixnire of carbon monox ide and hydrogen. It is
obtained by passing steam over red-hot coke. It is a good
fuel gas.
C + H 20 - CO + H2
'-v--'
Water gas
46. The purest form of coal is anthracite, because it has highest
percentage of carbon.
47. Pb reacts with dilute HNO 3 and produces NO.
3Pb + 8HNO 3 - 3Pb(NO3 h + 2N O + 4H 2O
Doi.
48. Crystalline form of silica is called quartz.
49. C-60 is called Buckminsterfullerene. It was discovered in 1990
as a constituent of soot. Its s hape is like a soccer ball.
50. Silica (SiO2 ) is used for making optical instrnments.
51. Buckminster fullerene is C---60 (allotrope of carbon).
52. Stannous chloride (SnCl2 ) is a good reducing agent. It reduces
HgCl2 into Hg (grey precipitate), in two steps.
SnCl4 + Hg2Cl 2 J,
White
SnCl 2 + Hg2 Cl2 - SnC1 4 + 2Hg J,
Grey
53. Carbon dioxide gas remains present in aerated water and
soft-drinks.
54. The chemical formula of sindhur is Pbp4 • It is also called red
lead or trilead tetraoxide. Red lead is used as a red pigment in
making anti mst and also as an oxidising agent in glass and match
industries.
55. Double chain silicates Double chain silicates can be formed
when two simple chains are joined together th rough the third
oxygen atom of SiO 4 tetrahedra. These strncnires are called
amphiboles, and they are well known. The most numerous and
best known amphiboles are the asbestos minerals. These are
based on the strnctural unit of (Si 4O 11) ~ . The structure of
amphiboles is
. 0 )611-
Strnctme of amphiboles (s14 11 ,.
56. The stmcture of silicates has been found with the help of X-ray
di ffraction technique. All silicates have tetrahedral Sio:- ion as a
basic bu ilding unit i.e. all silicates are composed of many units .
 p -block Elements I 249
Tetrahedral shape of(SiO4 )4- ion is due to s/
hy bridisation of Si 59. Agate is SiO 2•
atom. Sheet silicates are formed w hen three oxygen atoms 60. Si is used in making transistor. It is a semiconductor.
(bridging O-atoms) of each (SiO4 )4- unit are shared.
61. R3SiCl on hydrolysis can only form a dimer.
Hence, the general formula of sheet silicates is (Si2O 5 ).2n- H20
R3SiCI - R3SiOH
R3SiOH + R3SiOH - R3Si- O- SiR3
-H20

62. The tendency of catenation depends upon the strength of element-

element bond which is described in terms of element-element
bond energy.

Element C- C Si- Si Ge-Ge Sn-Sn

Bond Energy 354 222 167 155

(KJ/mol)

1
Thus, the correct decreasing order of catenation property of group
(Si205);' sheet
14 elements is as follows
57. In Silicon diovide, each Si atom is surrounded by four O-atoms C >> Si > Ge "' Sn > Pb
and single O-atom is shared between two Si-atoms. The stmcture 63. CF4 has more ionic character than CCl 4 , SiF4 and SiC1 4 .
can be shown as:
Hence, it ha.s more lattice energy and thermal stability.
I I 64. Silica reacts with metal carbonate forming silicate with the
0 0
I I evolution of CO2 .
Si Si Na2CO 3 + SiO 2 ~ Na2SiO3 + CO2 i
./
o./ 0I '--o./ 0I 'o......._ Sodiwn silicate

I I 65. Silica on heating with carbon at high temperanrre gives

carbomndmn (silicon carbide)
58. Tin is oxidised to metastannic acid when it is treated with nitric
acid. SiO2 + 3C ~ SiC + 2CO
Carborundum
Carbomndum is very hard substance.
12
Organic Chemistry :
Soine Basic Principles and Techniques

QUICK REVIEW
• Hydrides of carbon (hydrocarbon) or their derivatives are • Functional group are atoms or group of satoms
known as organic compounds. responsible for their chemical behaviour e.g. alcohol
• On the basis of number of sigma (cr) bond, they differ in ( -OH) .
shapes as • Homologous series of compounds differ from its
cr-bond Hybridisation
r
Shape
I previous and successive members by -CH2 , e.g. alkane
(CH4 , C2 H6 )
4 sl tetrahedral
?
HJPAC Nomenclature
3 sp- trigonal planar
• According to IUPAC nomenclature, the name of an
2 sp linear organic compound consists of three parts- prefix, word
root and suffix.
Structural Representations of Organic Compounds
• The word root is the basic unit of the name and tells us
There are several ways to represent the organic compounds: number of carbon atoms in principal chain.
• Dash structure In these structure all bond pairs are • Suffix tells us functional groups present in the molecule.
replaced by (- ) dash. They may be primary suffix (refers to the linkage between
• Condensed structure In these structure except double and C-atoms) or secondary suffix (refers to the functional
triple bonds all bonds are omitted. groups present in the molecule), secondary suffix is added
• Bond line structure The C-Cbonds in the molecules are to the name after primary suffix.
shown by zig-zag line. • Common prefix.es are alkyl groups and groups or atoms
which are not regarded as principal functional groups.
Classification of Organic Compounds
• Order of preference for the choice of principal functional
Organic compounds are classified as
groups:
Compounds are classified as
carbox.ylic acid > sulphonic acid > anhydride > esters >
acid halide > acid amide > nitrile > aldehyde > ketone >
Acyclic or Cyclic or closed chain alcohol > amine.
open chain
e.g. CH4, CH3CHO Isomerism
Homocyclic Heterocyclic Isomerism is the phenomenon when compounds have same

t Alicyclic e.g.
cyclopropane
e.g. furane

Aromatic e.g. benzene

molecular formula but differ in structures, atoms or spatial
arrangement.
 Organic Chemistry Some Basic Principles and Techniques
Isomerism
Structural Stereo
isomerism isomerism
• Structural isomerism is the isomerism which arises when
compounds have similar molecular formula but differ in
way of bonding. Their types are:
(i) Chain isomerism They have different carbon
skeleton, position differ in position of bond or
functional group etc, e.g. C5 H 12 •
(ii) Position isomerism it arises due to difference in the
position of substituent atom or functional group on the
carbon skeleton, e.g. C4 H 8 .
(iii) Functional Compounds having the same molecular
formula but different functional groups, e.g. C3 H6 0.
(iv) Metamerism These have different alkyl groups with
same functional group, e.g. C4 HJO.
• Stereoisomerism This phenomenon arises when
compounds having similar molecular and structural formula
differ in their spatial arrangement. Their types are optical
and geometrical.
• The different relative spatial arrangements which arise
because of rotation around the single bond are known as
rotational isomers or conformations.
• Ethane mainly exists in the staggered form as it is more
stable than eclipsed form.
• The order ofstability ofdifferent conformations of n-butane
is as follows:
chair conformation > twist boat conformation > boat
conformation > half-chair conformation.
• Geometrical or cis-tra11s isomerism is not possible if one
or both the doubly carbon atoms carry two similar
substituents.
So, terminal alkenes doesn 't show geometrical isomerism.
• Ring structures also exhibit geometrical isomerism due to
fixed position of group in the ring. All disubstituted cyclic
compounds show geometrical isomerism.
• The necessary condition for a molecule to be optically
active is that molecule should be chiral.
• When the molecule is unsymmetrical, total nun1ber of
stereoisomers = 2n (n is the number of chiral carbon atoms).
• When molecule is symmetrical and has even number of
chiral carbon atoms, total number of stereoisomers
= 2(n - I) + i(nl 2 - I).
• When molecule is symmetrical and has odd number of
chiral carbon atoms, total number ofstereoisomers= i<n - t) .
I 251
Reaction Mechanism and Intermediates
• Reaction Mechanism is the sequential information of each
step involved in a reaction.
• Cleavage in a covalent bond may be of two types,
homolytic or heterolytic. In homolytic cleavage, free
radical species are produced. These species are
paran1agnetic. In heterolytic cleavage ionic species such
as carbocation, carbanion are produced.
• Free radicals, electrophiles and nucleophiles are attacking
species. Free radicals have odd electron.
• Electrophiles (electron loving species) are positively
charged or neutral but electron deficient species.
Nucleophiles (nucleus loving species) are negatively
charged or neutral but electron rich species.
Inductive Effect
• Inductive effect is a permanent displacement of shared
pair of electrons along chain of carbon atoms due to the
presence of polar covalent bond at one end of the chain.
• Order of decreasing- I-effect for different electron with
drawing groups-
+
R 3 N->-N0 2 >-CN>-COOH>-F
> - Cl> - Br> -I> -OCH3 > -OH> -C6 H 5
• Order of decreasing + I effect for different electron
releasing groups-
-a- > -Coo- > (CH 3 ) 3 C-> (CH 3 ) 2 CH
- > CH 3 CH2CH2- > CH 3 CH 2 - > CH3
Electromeric Effect
Electromeric effect is a temporary displacement of
n-electrons in a multiple bond towards one of the bonded
atom. The effect is + E if transference of n-electrons occurs
towards atom where attacking species attaches and the effect
is - E if transference of n-electrons occurs away from the
atom where the attacking group attaches.
Mesomeric Effect
• The system having multiple bonds in conjugation or lone
pair in conjugation with n-bonds exhibits resonance or
mesomeric effect.
• When electron displacement is towards the group, it is
- M or - R-effect. - N02 > C=O,- C - N, - COOH
groups are called + Mor+ R effect groups. When electron
displacement is away from the group, the effect is called
+Mor +R effect. -NH2, -NHR, -NR 2 ,--!?H,-2R
252 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Resonance Effect For example,

• It is polarity developed due to the interaction of two rr bond (i) Free radical substitution reaction
or rr bonds with lone pair of electrons present on the /!,.or hv
CH4 + Cl 2 ~ CH3 Cl + HCl
adjacent atoms.
(ii) Nucleophilic substitution reaction
• It is a permanent effect.
• When the electrons moves away or towards the atom or C2 H 5 I + KOH(aq) ~ C2 H 5 OH + KI
group attached to the conjugated system, + R or - R effect (iii) Electrophilic substitution reaction
is produced. Cl
• Resonance hybrid structure has lower heat of combustion,
lower heat of hydrogenation and higher heat of formation
as compared to the most stable contributing structure.
© + Cl, ""'' @+HCI
• Adclition, reactions are given by organic molecules having
Hyperconj ugation multiple bonds.
Hyperconjugation is also known as Baker Nathan effect or no (i) Free radical adclition reaction,
bond resonance. More the number of hyperconjugative
structures, more is the stability, but the stability provided by CH 3 CH = CH2 + HBr l\,roxides l CH3 CH 2 CH 2 Br
hyperconjugation will not be as much as provided by
(ii) Electrophilic addition reaction,
resonance. Br
Properties of Reaction Intermediates I
CH CH = CH + HBr Absenceof CH 3 -CH-CH3
3 2 peroxides
• Stability order of carbocations is as follows :
+ + +
(C6H 5 h C> (C6H 5 h CH> (CH 3 ) 3 C (iii) Nucleophilic adclition reaction,
Weakly
+ + +
> C 6H 5 CH2 > (CH 3 ) 2 CH> CH2 =CH-CH2 C = 0 + HCN basic

+ + +
> R-C= CH 2 > CH 3 CH2 > R-CH = CH • Elimination reactions involve the removal of atoms or groups
+ + from organic compound to give unsaturated molecule.
> C6Hs > CH3 > CH - C (i) ~ -elimination,
• Stability order of carbanions is as follows : CH 3 CH2 OH Cone. H 2so4 CH2 = CH2 + H 2 O
ethanol ethene
(C6H 5 h C> (C6H 5 h CH> C 6H 5 -CH2
(ii) a-elimination involves the loss of two atoms or groups
>ally!> CH 3 > 1°> 2°> 3°R occurs from the same atom of the substrate molecule.
• Stability order of free radicals is as follows :
. . . Purification
(C6H 5 h C > (C6H 5 h CH> C 6H 5 -CH2

> H2 C =
. . .
CH-CH > R{3°> 2°> 1° )> CH
The process of removing impurities is called purification.
• Crystallisation It is used to purifying solid organic
. 2 3
compounds and based on the difference in solubilities of
>CH 2 = CH 2 compound and impurities in a solvent.
• Carbocations and free radicals have sp 2 hybridised carbon • Distillation It is used to separate a volatile liquid from a
atom and planar in shape. Carbanions have sp hybriclised3 non-volatile impurity or two liquid having large clifference
in their boiling point e.g. chloroform and aniline.
carbon atom and pyramidal in shape.
(i) Fractional Distillation It is used to separate the
• Carbenes are the species having divalent carbon bearing no
liquids, boiling points of which are nearly equal i.e.,
charge and surrounded by sextet of electrons. Carbenes
within the limit of 10 to 15 K.
may be singlet (sp 2 hybridised or triplet sp hybriclised). In
(ii) Steam Distillation This technique is used for
general triplet carbene is more stable than singlet carbene.
purifying steam volatile compounds that are
Types of Organic Reaction immiscible with water.
• Substitution reactions involve replacement of an atom or • Chromatography It is based on the difference in the sates
group from the organic molecule with another similar at which the components of a mixture are adsorbed on a
part. suitable adsorbent.
 Organic Chemistry Some Basic Principles and Techniques I 253
Suitable adsorbent Sodium extract + sodium nitroprusside ➔ Purple colour
Adsorption
• Test for X (Cl, Br, I) : Sodium extract + X 2 + AgNO 3
Partition
~ white ppt (Cl). Dull yellow ppt (Br). Yellow ppt (I).
I paper

+
Column +
Thin layer
• Test for P-Fused sample with Na 2O 2
+ H2 0 + cone. HNO 3 + b. ➔ Yellow ppt.
Qualitative and Quantitative Analysis (Cooling, ammonium molybdate)
Used to detect element present in a sample. • Quantitative analysis is used to detect percentage of
elements present in sample.
• Test for C and H-Organic compound burnt in air ~
CO2 and H 2 O fom1ed turns anhy. CuSO 4 blue, CO2 turns • Kjeldahl's method cannot be used for the compounds
lime water milky. having nitro groups, azo groups, nitroso group, azoxy
compounds and nitrogen in the ring because nitrogen in
• Test for N-sodium extract + FeSO4 + cone. H2 SO4 ➔
these compounds is not quantitatively converted into
Prussian blue colour.
ammonium sulphate.
• Test for S-Sodium extract + acetic acid + lead acetate ➔
• In Kjeldahl 's method for estimation of nitrogen, K 2 SO4 is
Black ppt
added to raise the boiling point of sulphuric acid.

Topic 1
Classification and Nomenclature of Organic Compounds
2014 4. The number of sigma and pi-bonds in 1-butene-3-yne are
1. Name of following compound according to IUPAC [lndraprastha CETJ
nomenclature is [UPSEEJ (a) 6 sigma and 4 pi (b) 7 sigma and 3 pi
(c) 5 sigma and 5 pi (d) None of these

<rNO, 5. C11H24 can contain maximum methyl group upto [RPETJ

(a) 0 (b) I (c) 6 (d) 11
6. Which of the following mentioned is a type of hydrocarbon?
OCH3 (a) Saturated hydrocarbon [J&K CETJ

(a) 4-methoxy-2-ni trobenzaldehyde (b) Unsaturated hydrocarbon

(c) Aromatic hydrocarbon
(b) 4-formyl-3-nitroanisole
(c) 4-methoxy-6-nitrobenzaldehyde (d) All of the above
(d) 2-formyl-5-methylnitrobenzene 7. Which one of the following acid does not have acarboxylic
2. The IUPAC name of the following compounds is [AMU] group? [BCECEJ
(a) Methanoic acid (b) Ethanoic acid
CH 2 -CH-CH2
(c) Propanoic acid (d) Picric acid
I I I 8. What is the IUPAC name of isopropylamine? [DCEJ
CH CN CN
(a) 1, 2, 3-tricyanopropane (a) Propan-2-amine (b) Ethanamine
(b) propane-1 , 2, 3-trinitrile (c) 2-aminotoluene (d) Propan-1-amine
(c) 3-cyanopentane-1, 5-dinitrile
(d) 1, 3, 5-pentanetrinitrile
2013
3. TheIUPAC nan1e ofthe compound 9. IUPACnameofCH3CH= C-CH3 is [KCETJ
I
CH2 =CH-CH(CH3)z is [Indraprastha CETJ
(a) 1,1-dimethy-1-2-propene
(b) 2-vinyl propane
F2
CH3
(c) 3-methy-1-butene
(a) 2-ethyl butene (b) 2-ethyl but-2-ene
(d) 2-vinyl propene
(c) 3-methyl pent-2-ene (d) None of these
254 I Chapterwise & Topicwise Engineering Entrances Solved Papers
10. IUPAC name ofCH2 = CH-CH(CH2CH 3 ) f = CH2 2010
16. The IUPAC name ofCH3-CH-CH= C- CHO is
Br
is [UPSEE]
I I
OH CH3
(a) 4-bromo-3-ethyl-l, 4-pentadiene (a) 4-hydroxy-l-methylpentanal [Manipal]
(b) 2-bromo-3-ethy1-1, 4-pentadiene (b) 4-hydroxy-2-methylpent-2-en-l-al
(c) 2-bromo-3-ethyl-l, 5-pentadiene (c) 2-hydroxy-4-methylpent-3-en-5-al
(d) None of the above (d) 2-hydroxy-3-methylpent-2-en-5-al
11. IUPAC name of the following compound is [OJEEJ 17. Correct structural formula of compound
CH 3 5-nitro- 3-methoxy-3-methylhexanoyl chlo1ide is
I NO2 OCH3 0 CMPPET]
CH3-CH 2 - CH -CH2 - CH CH2 -CH 2 -CH 3
I I I
(a) CH3 -CH-CH2 - C - CH 2 -C-CI
II
I
f~
CH3 CH3 NO2 Cl
CH 3
CH3
(a) 4-isopropyl-6-methyloctane I I I
(b) 3-methyl-5-(1-methyl ethyl)octane (b) CH3-CH- CH-C-CH2 -CHO
(c) 3-methy 1-5-isopropy!octane I
(d) 6-methyl-4-(1-methylethyl) octane OCH3

2012 fH3

12. The IUPAC name of d ;,

(a) bicyclo (2, 1, 0) p entane
[Manipal]
(c) CH3 -CH2 -CH-CH2 -CH
I
Cl
I
OCH3

(b) 1, 2-cyclopropyl-cyclobutane (d) CH3 -CH2 - r H - f- rH-CH3

(c) I, 2-methylene cyclobutane
(d) cyclopentane-(4, 3)-annulene Cl O OCH3

13. The IUPAC name of CH3CHOHCH2CH(CH3 )CHO is

(a) 2-hydroxy-4-methyl-pentanal
(b) 4-hydroxy-2-methyl-pentanal
(c) 2-hydroxy-2-methyl-pentanal
[AMU]
18. ThelUPACoameof Y ;,
CHO

Br
[KCET]

(d) 2-methyl-pent-4-ol-l-al (a) 2-methyl-3-bromohexanal

(b) 3-bromo-2-methylbutanal
2011 (c) 2-bromo-3-bromobutanal
(d) 3-bromo-2-methylpentanal
[KCET] 19. Which of the following is phenyl ethanoate? [Guj CETJ
14. TheIUPACnameof ~ O H is
(a) but-3-enoic acid
(b) but-1-enoic acid (a) @-cooCH3 (c) @ - c o CH3
(c) pent-4-enoic acid
(d) prop-2-enoic acid
15. Which one of the following is s-butyl phenyl vinyl
(b) ©- COOCOOH (d) ©- COOC2H 5

methane? [WB JEE] 20. The IUPAC name of acryldehyde is [RPETJ

Ph Me (a) prop-2-en-l-al (b) propenyl aldehyde
(c) but-2-en-l-al (d) propenal
(b) "(
21. The IUPAC name of the compound,
~Me C 2H 5 -C-CH2 OH is [JCECEJ
II
CH2
(a) 2-ethylprop-2-en-l -ol
(d)~Me (b) 2-hydroxymethylbutan-1-o I
(c) 2-methylenebutan-l-o 1
Ph Me (d) 2-ethyl-3-hydroxyprop-l-en
 Organic Chemistry Some Basic Principles and Techniques I 255
2009
22. The IUPAC name of the following compound, is 29. What will be the compound if two valencies of carbonyl
group are satisfied by two alkyl groups?
(a) Aldehyde [lndraprastha CET]
(b) K etone
(c) Acid
~rn ( d) Acidic anhydride
Br [IITJEE]
30. What is the formula of tertiary butyl alcohol? [Guj CETJ
(a) 4-bromo-3-cyanophenol
(b) 2-bromo-5-hydroxybenzonitrile (a) CH 3 -CH(CH3 )-CH2 -OH
( c) 2-cyano-4-hydroxybromobenzene (b) CH 3 -(CH2 ) 2 OH
( d) 6-bromo-3-hydroxybenzonitrile (c) CH 3 -CH(OH)-CH2 -CH3
23. The IUPAC name of neopentane is [AIEEE] (d) (CH 3 h ·C-OH
(a) 2-methylbutane (b) 2,2-dimethylpropane 31. Write the IUPAC name of [DCEJ
(c) 2-methylpropane (d) 2,2-dimethylbutane
CH 3 - 0 - f H - CH 2 - CH 3
24. IUPAC name of(CH 3h CCI is [Manipall
(a) n-butylchloride CH3
(b) 3-chlorobutane (a) 3-methoxybutane
(c) 2-chloro- 2-methyl propane (b) 2-methoxybutane
(d) t-butyl chloride ( c) 3-methyl-3-methoxypropane
(d) butoxy methane
25. The correct IUPAC name of the following acid is
32. Give the correct IUPAC name for [DCEJ

--:>c =cQOH CH 3
I
CH 3 ·CH2 OCH·CH 2 ·CH2 ·CH2 CI
(a) Z-3-ethyl-4-methylhex-3-en-l-oic acid [Kerala CEE]
(b) Z-3-ethyl-4-methylhexanoic acid (a) 2-ethoxy-5-chloropentane
(c) Z-3,4-diethylpent-3-en-1-oic acid (b) l-chloro-4-ethoxy-4-methylbutane
(d) E-3-ethyl-4-methylhex-4-en-l-oic acid ( c) 1-chloro-4-ethoxypentane
( e) E-3-ethyl-4-methylhex-3-en-1-oic acid (d) Ethyl-1-chloropentylether

26. Pick out the correct statement from the following and 2008
choose the correct answer from the codes given below.
33. The correct decreasing order of priority for the functional
I. Hexa-1, 5-diene is a conjugated diene.
groups of organic compounds in the IUPAC system of
IT. Prop-I, 2-diene is conjugated diene.
nomenclature is [AIEEEJ
III. Hexa-1, 3-diene is a conjugated diene.
IV. Buta-1, 3-diene is an isolated diene. (a) - COOH, - SO3 H, - CONH2 ,- CHO
V. Prop-I, 2-diene is a cummulative diene. [Ke rala CEE] (b) - SO3 H,- COOH, - CONH 2 ,- CHO
(a) I, II (b) H, III (c) IV, V ( c) - CHO,- COOH,- SO3 H, - CONH 2
(d) II, V (e) III, V (d) - CONH 2 ,- CHO, -SO3 H,- COOH
27. The correct name fo~w;ng hydmrarl>on fa 34. TheIUPACnameofC2 H 5 - 0- CH<CH3 is
CH 3
[BITSAT, AMU, EAMCETJ
(a) tricyclo (4. 1.0) heptane [UPSEE] (a) ethoxy propane
(b) bicyclo (5.2.1) heptane (b) l, I-dimethyl ether
( c) 2-ethoxy-iso-propane
(c) bicyclo (4. 1.0) heptane
( d) 2-ethoxy propane
( d) bicyclo ( 4. 1.0) hexane
28. Which of the following represents neo-pentyl alcohol?
(a) CH 3 CH(CH 3 )CH 2 CH 2 OH [AMU]
[MIITCETJ
(b) (CH 3h C-CH2 OH
(a) 4-propoxy pentane (b) pentyl-propyl ether
(c) CH 3 (CH 2 ) 3 OH
(c) 2-propoxy pentane (d) 2-pentoxy propane
(d) CH 3 CH2 CH(OH)C 2 H 5
256 I Chapterwise & Topicwise Engineering Entrances Solved Papers

36. The IUPAC name for tertiary butyl iodide is [KCET] 2007
(a) 4-iodo butane 44. The IUPAC name of ~ is [AIEEE]
(b) 2-iodo butane
(c) 1-iodo-3-methyl propane
(a) l, l -diethyl-2, 2-dimethylpentane
(d) 2-iodo-2-methyl propane
(b) 4, 4-dimethyl-5, 5-diethylpentane
37 . The chemical name of anisole is [Ke rala CEE] (c) 5, 5-diethyl-4, 4-dimethylpentane
(a) ethanoic acid (b) methoxy benzene (d) 3-ethyl-4, 4-dimethylheptane
(c) propanone (d) acetone 45. The IUPAC name of the compound,
(e) propanol
CH 2 - CH - COOH is [BITSAT]
38. The IUPAC name of CH3 - CH= CH- C =
CH is I I
(a) pent-3-en-l-yne [WBJEE] OH NH2
(b) pent-3-en-4-yne (a) 2-amino-3-hydroxypropanoic acid
(c) pent-2-en-4-yne (b) l-hydroxy-2-aminopropan-3-oic acid
(d) pent-2-en-3-yne (c) 1-amino-2-hydroxypropanoic acid
39. In cyclopropane, cyclobutane and cyclohexane, the (d) 3-hydroxy-2-aminopropanoic acid
common group is [UPSEE] 46. The IUP AC name of the following compound is
I I [Manipal]
(a) - T- (b) CH2
I
I
(d) - CH
I
40. The IUPAC name for
Cl (a) bicyclo [2, 2, O] octane (b) bicyclo [O, 2, 2] hexane
I (c) bicyclo [2, l, 1] hexane (d) bicyclo [2, 2, O] hexane
CH 3 - C- CH 2- CH=CH- CH 3 is
I
H [UPSEE]
(a) 5-chloro-hex-2-ene [MHT CET]
(b) 2-chloro-hex-5-ene (a) 2-ethoxy pentane (b) 4-ethoxy pentane
(c) l -chloro- l -methylpent-3-ene (c) pentylethyl ether (d) 2-pentoxy ethane
(d) 5-chloro-5-methylpent-2-ene
48. The IUPAC name ofCH3 COCH(CH3 ) 2 is [MP PET]
41. Give the IUPAC name of the following compound. (a) isopropylmethyl ketone
[OJEEJ (b) 2-methyl-3-butanone
(c) 4-methylisopropyl ketone
(d) 3-methyl-2-butanone
49. Crown ethers are nan1ed as X-crown-Y. In the following
(a) I, l, 3-trimethylcyclohex-2-ene crown ether, X and Y respectively, are [Kerala CEEJ
(b) l , 3, 3-trimethylcyclohex-1-ene
(c) I, I, 5-trimethylcyclohex-5-ene
(d) 2, 6, 6-trimethylcyclohex-1-ene
42. IUPAC name ofCH3 - 7 H-CH 2 -CHO is
Cl [J&KCET]
(a) 3-chlorobutanol (a)6andl2 (b)l8and6 (c)24and6
(b) 3-chlorobutanaldehyde (d) 6 and 24 (e) 6 and 18
(c) 3-chlorobutanal
(d) 2-chlorobutanol SO. The correct IUPAC name o f ~ is
43. t-butyl alcohol is [BCECE] ~ [WB JEE]

(a) 2-methylpropan-2ol (a) 1-cyclopropyl cyclobutane

(b) 2-methylpropan-l ol (b) l, 1-dicyclobutane
(c) 3-methylbutan-l-o] (c) l-cyclobutane-1-cyclopropane
(d) 3-methylbutan-2-ol (d) None of the above

51 . What is the co1Tect IUPAC name of
<rN~?
OCH3
(a) 4-methoxy-2-ni trobenzaldehyde
(b) 4-fonnyl-3-nitro anisole
(c) 4-methoxy-6-nitrobenzaldehyde
(d) 2-fonnyl-5-methoxy nitrobenzene
52. The IUPAC aame of ~ is
0
(a) l-cyclohexa-2, 4-dienylethanone
(b) 3-cyclohexa-2, 4-dienylethanone
(c) l -cyclohexa-3, 5-dienylethanone
(d) 3-cyclohexa-3, 5-dienylethanone
53. The IUPAC name of the compound
(CH 3 )iCH - CH= CH- CHOH- CH3 is [EAMCETJ
(a) 5-methylhex-3-en-2-ol
(b) 2-methylhex-3-en-5-ol
(c) 2-hydroxy-5-methyl-3-hexene
(d) 5-hydroxy-2-methyl-3-hexene
54. TheIUPACnameofC6 H 5 COClis
(a) benzoyl chloride
(b) benzene chloro ketone
(c) benzene carbonyl chloride
(d) chloro phenyl ketone
2006
55. The IUP AC name of the compound shown below is
&B,
(a) 2-bromo-6-chlorocyclohex-1-ene
(b) 6-bromo-2-chlorocyclohexene
(c) 3-bromo- 1-chlorocyclohexene
(d) l-bromo-3-chlorocyclohexene
56. IUPAC name of the following compound is
H3 C C CH3
(a) 3, 5-dimethylcyclohexene
(b) 3, 5-dimethyl- 1-cyclohexene
(c) 1, 5-dimethyl-5-cyclohexene
(d) 1, 3-dimethyl-5-cyclohexene
Organic Chemistry Some Basic Principles and Techniques I 257
[UPSEE J 57. The epoxide ring consists of which of the following?
[VITEEEJ
(a) Three membered r ing with two carbon and one
oxygen
(b) Four membered ring with three carbon and one
oxygen
(c) Five membered ring with four carbon and one
oxygen
(d) Six membered ring with five carbon and one oxygen
58. IUPAC name of the following compounds is [VITEEEJ
~
H3C- CH2 - C- H2C- CH2 - C-OCH3
~
[OJEE J (a) ethyl-4-oxoheptanoate
(b) methyl-4-oxoheptanoate
(c) ethyl-4-oxohexanoate
(d) methyl 4-oxohexanoate
59. The IUPAC name of the comp~ ~ is
(a) 3, 3-dimethyl-1-hydroxy cyclohexane [Manipal]
(b) 1, l -dimethyl-3-hydroxy cyclohexane
(c) 3, 3-dimethy-1-cyclohexanol
(d) 1, 1-dimethyl-3-cyclohexanol
60. IUPAC name of the compound
CH3 CH3 CH3
\/ I
[J&K CETJ CH CH2
I I
CH 3CH2CH 2 CH - CH- C-CH 2CH3 is
I I
CH3 IH2
CH3
(a) 5-methyl-4-isopropyl-6, 6'-diethyloctane[MHT CETJ
(b) 3, 3-dimethyl-3-ethyl-5-isopropyloctane
(c) 3, 3-diethyl-4-methyl-5-(1, I-dimethyl) octane
(d) 3, 3-diethyl-4-methyl-5-(1'-methyl ethyl) octane
CAIEEEJ 61. IUPAC name ofCH3CH2C(Br) = CH- Cl is
(a) 2-bromo-1-chloro butene- I CWB J EEJ
(b) 1-chloro-2-bromo butene-I
(c) 3-chloro-2-bromo butene-2
(d) None of the above
[BITSAT]
62. The IUPAC name ofCH 3- C- CH- CH3 is
II I
0 CH3
(a) 2-methyl-3-butanone [Guj CETJ
(b) 3-methyl-butan-2-one
(c) 3-methyl butanone
(d) None of the above
258 I Chapterwise & Topicwise Engineering Entrances Solved Papers

63. The IUPAC name of the compound CH3 CONHBr is 69. The systematic (IUPAC) name of the compound with the
(a) 1-bromoacetamide [Jamia Millia Islamia ] following structural formula will be [AMUJ
(b) ethanoylbromide

2005
(c) N-bromoethanamide
(d) None of the above

64. Bicyclo (1, I, 0) butane is [BITSAT]

&
(a) l-ethyl-2-methyl cyclohexene
(b) 2-methyl-1-ethyl cyclohexene
(a) [ ] > (b) [IJ (c) 3-ethyl-2-methyl cyclohexene
(d) 4-ethyl-3-methyl cyclohexene
(c) <I> (d) □ 70. The IUPAC name of(CH3 ) 3 C- CH= CH 2 is
(a) 1, I , l -trimethyl-2-propene [Guj CETJ
65. Which of the following is a primary halide? [ManipalJ (b) 3, 3, 3-trimethyl-2-propene
(a) Isopropyl iodide (c) 2, 2-dimethyl-3-butene
(b) Secondary butyl iodide (d) 3, 3-dimethyl-1 -butene
(c) Tertiary butyl bromide 71. Glycerol is an alcohol which can be classified as
(d) Neo hexyl chloride (a) trihydric (b) monohydric [J&K CETJ
(c) dihydric (d) hexahydric
66. IUPAC name of H3 C- r = CH- rH-CH 3 is
72. The compound which contains all the four 1°, 2° ,3° and4°
Cl CH 3 carbon atoms is [J&K CETJ
[KCET] (a) 2, 3-dimethylpentane
(a) 2-chloro-4-methyl-2-pentene (b) 3-chloro-2, 3- dimethylpentane
(b) 4-chloro-2-methyl-3-pentene (c) 2, 3, 4-trimethylpentane
(c) 4-methyl-2-chloro-2-pentene (d) 3, 3-dimethylpentane
(d) 2-chloro-4, 4-dimethyl-2-butene 73. Which of the following compounds has incorrect IUPAC
67. The IUPAC name of the following compound is nomenclature? [Jamia Millia Islamia]
HOOC-CH2 -CH- CH 2 -CH2 -COOH
I
COOH [Kerala CEEJ
(a) 2(carboxymethyl)-pentane-l, 5-dioic acid
(b) 3-carboxyhexane- l, 6-dioic acid
(c) butane-I, 2, 4-tricarboxylic acid 3- methyl butanal
0
(d) 4-carboxyhexane- l, 6-dioic acid II
(e) 1, 2-dicarboxy pentanoic acid (c) CH3 fH CCH 2 CH3 (d) CH3 fHfHCH 3
68. The IUPAC name of CH3 - CH2 - CHO is [UPSEEJ
CH3 H C OH
3
(a) propanal-1 (b) 2-methylbutanal 2-methyl-3- pentanone 2-methyl -3-butanol
(c) butanal-1 (d) pentanal-1
 Topic 2
Fission of Bonds and Electron Displacement Effects
2012
1. Which one of the following is not true regarding
electromeric effect? [KCET]
(a) It is temporary effect
(b) It operates on multiple bonds
(c) It requires on attacking reagent
(d) It results in the appearance of partial charges on the
carbon atom
2. Which of the following is possessed by a nucleophile?
(a) A lone pair of electron [OJEEJ
(b) Positive charge
(c) Negative charge (a) 1 (b) 2 (c) 3 (d) 4
(d) None of the above
7. The correct order of increasing basicity of the given
2011 conjugate bases (R =CH3 ) is [AIEEE]
- - - -
3. Among the following compounds, the most acidic is (a) ~COO< H_s:= C< ~ < ~H2
(a) p-nitrophenol [IIT JEE] (b) R < H_C= C< RCOO< NH 2
(b) p-hydroxybenzoic acid (c)RCO<?<NH2 <_HC_ C<~
(c) o-hydroxybenzoic acid (d) RCOO< HC=C< NH 2 < R
(d) p-toluic acid 8. Inductive effect involves [Manipal]
4. The total number of contributing structures showing (a) delocalisation ofCJ-electrons
hyperconjugation (involving C-H bonds) for the (b) displacement ofCJ-electrons
following carbocation is [IIT JEE] (c) delocalisation of 1t-electrons
H,COCH,CH, (d) displacement of1t-electrons
9. Chloroacetic acid is a stronger acid than acetic acid. This
can be explained using [KCETJ
(a) - M-effect (b) - I-effect
(a) three (b) five (c) eight (d) six (c) + M effect (d) + I-effect
5. Formic acid is a stronger acid than acetic acid. This can be 10. Which of the following has most acidic hydrogen?
explained using [KCET] (a) 3-hexanone [Punjab CETJ
(a) + M-effect (b) - I-effect (b) 2, 4-hexanedione
(c) + I-effect (d) - M-effect (c) 2, 4-hexanedione
(d) 2, 3-hexanedione
2010 2009
6. Amongst the following, the total number of compounds
11. The correct acidity order of the following is [IITJEE]
soluble in aqueous NaOH is [IIT JEE]

H,C6CH' OH OH COOH COOH

6¢6¢ Cl
I II III
(a) III > IV > II > I (b) IV > III > I > II
(c) III > II > I > IV (d) II > III > IV > I
260 I Chapterwise & Topicwise Engineering Entrances Solved Papers

12. Electromeric effect is [UP SEEJ

(a) permanent effect (b) temporary effect
( c) resonance effect (d) inductive effect
13. Given,
OMe

B•~'
A•~ c-~
is influenced by the hyper conjugation effect of group R. If
OH OH OH R sequentially is
The decreasing order of the acidic character is [DCEJ I. CH3 - II. CH3 - CH2 -
(a)A>B>C (b)B>A>C CH3
(c)B> C> A (d) C> B> A I
N.H 3C- C-
2008 I
CH3
14. Hyperconjugation involves overlap which of the following
orbitals ? [IIT JEE] The increasing order of speed of the above reaction is
[Guj CETJ
(a) cr - cr (b)cr - p
(a) IV< IIl< II < I (b) I <II <III< IV
(c) p - p (d) 1t - 1t
(c) I <IV< IIl <II (d) III < II < I < IV
15. The correct stability order for the following species as
20. Dichloroacetic acid is a stronger acid than acetic acid. This
[IITJEEJ
is due to the occurrence of [J&K CETJ
(a) mesometic effect (b) hyperconjugation
( c) inductive effect ( d) steric effect
I II III IV 21. CH3 CH 2 Cl undergoes homolytic fission, produces
(a) II > IV > I >
(b) I > II > III >
III
IV
.
(a) CH CH and Cl
$
(b) CH3 CH 2 and Cl
[BCECEJ

3 2
(c) II > I > IV > III $
(d) I > III > II > IV (c) CH 3 CH2 and Cl
16. The electrophile E e attacks which benzene ring to 22. The basicity ofaniline is less than that ofcyclohexylamine.
generate the intem1ediate cr-complex. Which of the This is due to [Jamia Millia IslamiaJ
following cr-complexes is of lowest energy? [AIEEE]
(a) +R effect of- NH 2 group
N02 (b) - I effect of - NH2 group
(c) - R effect of- NH 2 group

(a) H~E (b) @)<; (d) hyperconjugation effect

23. Orbital interaction between the cr-bonds of a substituent
group and a neighbouring 1t-orbital is known as [DCEJ
(a) hyperconjugation
(b) inductive effect
(c) steric effect
(d) electric quadrapole interactions
17. Mesometic effect involves delocalisation of [KCET] 2006
(a) pi-electrons 24. Among the following, the least stable resonance structure is
(b) sigma-electrons
~
<tl o ~ [IIT JEE]
8 o
(c) protons
( d) None of these
18. Which of the following species does not exert a resonance
(a) e f (b) <tl I
0e 0e
effect? [KCET] 8
+
(a) C 6 H 5NH 2 (b) C 6 H 5 NH 3 ~o (f)~o
(c) C6 H 5 0H (d) C 6 H 5 Cl (c) 7 (d) 7
oe oe
 Organic Chemistry Some Basic Principles and Techniques I 261
25. +I-effect is shown by [KCET] 31. The correct order for homolytic bond dissociation energies
(a)-CH3 (b) - Br (d) - N02
(c) - Cl (Win kcal/mol) for CH 4 (A),C2 H 6 (B)and CH3 Br(C),
under identical experimental conditions, is [J&K CETJ
26. Which one of the following compounds is most acidic?
(a)C>B>A (b)B>C>A
(a) CJ-cH2-CH:r-<)H (b) ©( OH
N02
[UPSEEJ ( c) C > A > B (d) A > B > C
32. Chlorobenzene is o, p -directing in electrophilic
substitution reaction. The directing influence is explained
~ OH ~ OH by [J&KCETJ
(c)~ (d)~ (a) +M of Ph (b) +I of Cl
CH3 (c) +M of Cl (d) - 1 of Ph
27. The highest electrical conductivity of the following 33. C- H bond energy is about 101 kcal/mo) for methane,
aqueous solutions is of [UPSEEJ ethane and other alkanes but is only 77 kcal/mol for C- H
(a) 0.1 M difluoroacetic acid (b) 0.1 M fluoroacetic acid bond ofCH3 in toluene. This is because
[Jamia Millia Islamia]
( c) 0 .1 M chloroacetic acid (d) 0.1 M acetic acid
(a) of inductive effect due to - CH 3 in toluene
$ HHr (b) of the presence of benzene ring in toluene
28. R 3 N - CH =CH 2 ~ product.
(c) of the resonance among the structures of benzyl
Predominant product is
EB
radical in toluene
(a)R3 N-CH-CH 3 (d) aromaticity of toluene
I 2005
Br
(b) R 3 N- CH 2 - CH 2 - Br 34. Which of the following resonating structures of
$ e l-methoxy-1, 3-butadiene is least stable? [IITJEE]
(c) CH2 =CH- NR 3 Br e $

( d) No reaction (a) CH - CH=CH- CH=O- CH 3

2
e $
29. The reaction intermediate produced by homolytic cleavage (b) CH 2 =CH 2 - CH- CH=O-CH3
of a bond is called [J&K CETJ e $

(a) carbene (b) carbocation (c) CH - C H- CH=CH- O- CH 3

2
( c) carbanion (d) free radical e $
(d) CH 2 =CH- CH- CH- O - CH3
2006 35. Amongst the following, the compound that can most
30. Which kind of fission is favoured by sunlight? [WB JEE] readily get sulphonated is CKCETJ
(a) Heterolytic fission (b) Homolytic fission (a) benzene (b) toluene
(c) Both (a) and (b) (d) None of these ( c) nitrobenzene (d) chlorobenzene

Topic 3
Reaction Intermediates
2014
1. Among the following, the strongest nucleophilic is 3. Which is the least stable carbocation ? [AMUJ
(a) C2H5SH (b) CH3COO- [VITEEEJ
(c) CH3NH2 (d) NCCH 2 + +
ITT. (CH3)3C IV. (CH 3)J CCH2
2. Order of reactivity for the following compounds, is (a) I (b) II (c) III (d) IV
l. CH30---@-cH2 TI. @ - - cH2 2013
4. A solution of (- d) 1-chloro-1-phenylelnane in toluene a
+
III. H3C---@-CH2 IV. CH3CH2 [UPSEE] racemises slowly in the presence of a small amounts of
SbC15 due to the formation of [JEE Mains]
(a) IV < II < III < I (b) II < IV < III < I (a) carbanion (b) carbene
( c) IV < II < I < III (d) II < IV < I < III ( c) carbocation (d) free radical
262 I Chapterwise & Topicwise Engineering Entrances Solved Papers

5. The order of the stability of the following carbocations 12. Most stable carbonium ion is [JCECE]
+ + +
I. CH2 = CH- CH2, TT. CH3- CH2- CH2 , (b) (CH 3 ) 3C
+ +
CHz (d) C 6 H 5 CH 2

m 6
(a) III > II > I (b) I > III > II
[JEE Mains]
2009
13. In the following carbocation, H/CH 3 that is most likely to
migrate to the positively charged carbon is [IIT JEE]
(c)I > II > III (d) III > I > II
H H
2012 I 12+ 5 41
H3 C- C - 3 C- C-CH3
t Bu0-
6. PhCHCIBr ~ carbene. I I I
OH H CH 3
In the reaction, which of the following is most probable?
(a) CH 3 at C-4 (b) Hat C-4
(a) : CHBr (b) : CHCl [Manipal]
(c) CH 3 at C-2 (d)HatC-2
(c) : CPhBr (d) : CPhCl
14. Arrange the carbanions, in order of their decreasing
7. Among the following carbocations stability.
+ +
Ph 2 CCH 2 Me(I), PhCH 2 CH2 CHPh(II), (CH 3 h C, CCl 3 ,(CH3 )z CH,C6 H 5 CH 2 , [AIEEEJ
+ +
Ph 2 CHCHMe(III) and Ph 2 C(Me)CH 2 (IV), the order of (a) C 6 H 5 CH 2 > CCI 3 > (CH 3 hC> (CH 3 h CH
stability is [WB JEE] - - -
(b) (CH3 h CH> CCl 3 > C6 H 5 CH 2 > (CH3 )3 C
(a) IV > II > I > III (b) I > II > III > IV
(c)II > I > IV > III (d)I > IV > III > II (c) CCl 3 > C 6 H 5 CH 2 > (CH 3 h CH> (CH 3 hC
- - - -
8. The stability of Me 2 C= CH2 is more than that of (d) (CH3 hC> (CH 3 )zCH>CH2 >CC13
MeCH2 CH=CH2 due to the [WB JEE] 15. Geometry of methyl free radical is [UPSEE]
(a) inductive effect of Me groups (a) pyramidal (b) planar (c) tetrahedral (d) linear
(b) resonance effect of Me groups
(c) hyperconjugative effect of the Me group 16. Relative stabilities of the following carbocations will be in
(d) resonance as well as inductive effect of Me group the order
e e EB
2011 CH 3 CH 3 CH 2 CH2 OCH3
A B C
9. Consider thiol anion (RS 9 ) and alkoxy anion (RO9 ) . (a)C>B>A (b)C<B<A
Which of the following statements is correct? [AIEEE] (c)B>C> A (d)C> A>B
(a) RS9 is less basic and less nucleophilic than R09
(b) RS6 is less basic but more nucleophilic than R09
2008
(c) RS9 is less basic and more nucleophilic than R06 17. Which one of the following carbanions is the least stable?
(d) RS6 is more basic but less nucleophilic than R09 (a) CH 3 CH2 (b) HC = C- [Kerala CEE]
10. Which one of the nitrogen atoms in (c) (C6 H 5 h c- (d) CH3
0 (e) (CH 3 ) 3 C-
II
H 2 N-NH-C-NH2 is the most nucleophilic? 2007
I II III 18. The compound which gives the most stable carboniwn ion
(a) Only III (b) Only I [KCETJ on dehydration is [BITSAT]
(c) Only II (d) All three N-atoms
(a) CH 3 CH(CH 3 )CH 2 OH
2010 (b) (CH 3 h COH
11. Which of the following is not true for carbanions? (c) CH 2 = CHCH 2 CH 2 OH
(a) The carbon carrying the charge has eight valence (d) CH3 CHOHCH2 - CH3
electrons [Manipal] 19. Due to the presence of an unpaired electron, free
(b) They are formed by heterolytic fission radicals are [UPSEE]
(c) They are paramagnetic (a) cations (b) anions
(d) The carbon carrying the charge is sp 3-hybridised (c) chemically inactive (d) chemically reactive
 Organic Chemistry Some Basic Principles and Techniques I 263
2006
20. The increasing order of stability of the following free The cotTect sequence of the stability of these is
radicals is [AIEEE] (a) II < I < III < IV
. . . (b) II < III < I < IV
CMHT CET]
(a) (CH 3 h CH < (CH 3 h C < (C6 H 5 h CH
. (c) III < l < II < IV
(d) IV < III < I < II
<(C 6 H 5 h C
. . . 2005
(b) (C6H 5 h C < (C6H 5 h CH < (CH 3 h C
. 22. Which is the most stable carbocation? [J&K CET]
< (CH3 )i CH
. .
(c) (C6H 5 )z CH < (C6H 5 h C < (CH 3 ) 3 C
. (a) iso-propy1 cation
(b) Triphenylmethyl cation
(c) Ethyl cation
. .< (CH3 h CH. (d) n-propyl cation
(d) (CH3 )2 CH < (CH3 h C < (C6H5 h C 23. Bromination ofa1kanes involves [J&K CETJ

<(C H h CH
. (a) carbanions (b) carbocations
6 5 (c) carbenes (d) free radicals
21. Consider the following carbocations, 24. Reaction of phenol with chloroform/sodium hydroxide to
+ + give o-hydroxy benzaldehyde involves the formation of
T. ½ HsCH2 TI. ½HsCH2CH2
[J&KCET]
(a) dichloro carbene (b) trichloro carbene
(c) chlorine atoms (d) chlorine molecules

Topic 4
Isomerism
2014
1. The correct combination of names for isomeric alcohols CUPSEEJ
with molecular fo1mula C 4 H 10 0 is/are [JEE Advanced]
(a) t-butanol and 2-methyl propan -2-ol
(b) t-butanol and 1, 1 dimethylethan- 1-ol
(c) n-butanol and butan- 1-ol
(d) iso-butylalcohol and 2-methylpropan-1-ol (a) geometrical isomerism
2. The total number(s) of stable conformers with non-zero (b) optical isomerism
dipole moment for the following compound is/are (c) geometrical and optical isomerism
[JEE Adavanced] (d) structural isomerism
Cl 6. Geometrical isomerism is reflected by which of the
Br-+--CH3 compounds? [Indraprashtha CET]
Br+-Cl (a) 3-phenyl- l-butene (b) 2-phenyl- l -butene
CH3 (c) 1, 1-diphenyl-l-propene(d) l-phenyl-2-butene
(a) 3 (b) 2 (c) 4 (d) 5 2013
3. Which of the following isomerism is shown by 7. The number of possible structural isomers of butene are
ethyl acetoacetate? [VITEEEJ (a) 3 (b) 2 (c) 4 [Ke rala CEE]
(a) Geometrical isomerism (d)S (e)l
(b) Keto-enol tautomerism 8. Disymmetric object is one which is [Kerala CEE]
(c) Enantiomerism
(d) Diastereoisomerism (a) superirnposable on its mirror image
(b) non-superimposable on its mirror image
4. How many enols (including stereo isomers) exist for (c) optically inactive
3-hexanone? [Manipal] (d) achiral
(a) Two (b) Three (c) Four (d) Six
264 I Chapterwise & Topicwise Engineering Entrances Solved Papers
9. The compound without a chiral carbon atom is [UPSEEJ l 5. The most contributing tautomeric enol form of
CH 3 CH 3 MeCOCH2 CO 2 Et is [WBJEE]
I I (a) CH 2 = (OH)CH 2 C02Et
(a) Br CH 2 CHCH 2 Br (b) C 2 H 5 CH2 CHCH2 Br (b) MeC(OH) = CHC0 2 Et
(c) CH3CH 2 CHCH 2 Br (d) HOOC CH (Br) COOH (c) MeCOCH = C(OH)O Et
I I (d) CH 2 = C(OH)CH = C(OH)OEt
CH3 CH 3
16. Total number of isomers for the molecular formula
(e) OHC-CH(OH)-CH2 0H C 4 H 10 0 is [OJEE]
(a) 3 (b) 4
2012 (c) 6 (d)7
10. Which of the given statement(s) aboutN, 0 , P and Q with
17. Which of the followng shows optical isomerism? [OJEEJ
respect to M is/are correct? [HT JEE]
(a) Butan-1-ol
Cl (b) Butan-2-ol
H~H (c) Butene
HO~HO (d) But-2-enol
HOYH Cl
18. Which of the following is a chiral molecule? [AMU]
CH3 CH3
M 0 ,#CH3 r - /CH3
(a) [ I (b) L_j
~ C H3 ~CH3
H~OH H~H

HOYH HOYH
Cl Cl
p Q
(a) Mand N are non-mirror image stereoisomerism 19. Ibuprofen contains [EAMCETJ
(b) Mand O are identical
(a) only S-enantiomers
( c) M and P are enantiomers
(b) only R-enantiomers
( d) Mand Q are identical
(c) racemic mixture of both Rand S enantiomers
11. How many chiral compounds are possible on (d) both Rand S -enantiomers are active pain colour
monochlorination of2-methyl butane? [AIEEEJ
20. Products of the reaction are
008 ~2 ~4 006 H H H3C Br
12. The structure of cis-bis (propenyl) ethene is [Manipal] )c = c( ~ H ) c = c~H
H 3C CH3 Br "-CH3
(a)~ (b)~
(a) meso-compounds [Guj CETJ
(b) racemic mixtures
(c) _ ) = C (d)~ ( c) mixtures of racemic and meso-compounds
(d) None of the above
13. Which compound shows geometrical isomerism among 2011
the following? [MP PET]
21. Amongst the given options, the compound (s) in which all
CH 3
the atoms are in one p lane in all the possible confom1ations
I (if any), is (are) CIIT JEE]
(a)CH 3-C-H (b)HO-C-H
II I (a) H"- - C/H
CH3-C-H COOH H2c/c- ~CH2
(c) CH3CH 2 -CH2CH 3
- / H
14. The well known compounds (+)-lactic acid and (- ) -lactic (b) H-C= C-C~
CH2
acid, have the same molecular fom1ula, C 3H6 0 3. The
(c) H2C=C=O
correct relationship between them is [WB JEE]
(a) constitution isomerism (b) geometrical isomerism ( d) H2C = C = CH2
( c) identicalness (d) optical isomerism
 Organic Chemistry some Basic Principles and Techniques I 265
22. The maximum number of isomers (including 32. Which of the following is the correct order of priority of
stereoisomers) that are possible on monochlorination ofthe groups in D -glyceraldehyde? [Guj CETJ
following coumpound, is [HT JEE] (a) OH (1), CHO (2), CH 2OH (3) and H (4)
CH3 (b) OH (1 ), CH 2 OH (2), CHO (3) and H ( 4)
I
___,,,.,c...__,___
(c) CH 2 OH (1), CHO (2), OH (3) and H (4)
H3CH2C I CH2CH3 (d) CHO (1), OH (2), CH 2 OH (3) and H (4)

H 33. The structures (CH 3 h CBr and CH3 (CH 2 hBr represent
(a) 2 (b) 4 (c) 6 (d) 8 (a) chain isomerism [RPETJ
(b) position isomerism
23. Identify the compound that exhibits tautomerism.[AIEEE] ( c) chain as well as position isomerism
(a) 2-butene (b) lactic acid ( d) functional isomerism
(c) 2-pentanone (d) Phenol
34. Which of the following compounds will show
24. The maximum number of possible optical isomers in metamerism? [JCECEJ
1-bromo-2-methyl cyclobutane is [KCETJ (a) CH3 ---CO--C2H 5 (b)C2 H 5-S-C2 H 5
(a) 4 (b) 2 (c) 8 (d) 16 (c) CH 3 -O-CH3 (d) CH3-0-C2H5
25. Which one of the following is the most energetic
conformation of cyclohexane? [KCET] 2009
(a) Boat (b) Twisted boat 35. The total number of cyclic structural as well as
( c) Chair (d) Half chair stereoisomers possible for a compound with the molecular
formula C 5H 10 is [HT JEE]
26. Which one of the following will show optical
isomerism? [WB JEE] w2 ~4 W6 W7
H H 36. The alkene that exhibits geometrical isomerism is
I I (a) propene [AIEEE]
(a) HO-r-CO 2H (b) H 3C-r-CO2 H (b) 2-methyl propene
(c) 2-butene
H OH ( d) 2-methyl-2-butene
CH3 CH3 37. The number of stereoisomers possible for a compound of
I I the molecular fommla
(c) H 3C-f-CO2 H (d) H 3C-f-CO2H CH3---CH= CH---CH(OH)-Me is [AIEEEJ
H Cl (a)3 (b)2
(c) 4 (d) 6
27. Which of the following compounds exhibit rotamers? 38. Select R-isomers from the following
(a) 2-butene (b) Maleic acid [Guj CET]
IH3
H-tOH D
+ OH
(c) Butane (d) Fumeric acid

2010
28. The total number of cyclic isomers possible for a
CJI H
hydrocarbon with the molecular formula C4 H 6 is CHO CH3
(a) 1 (b) 3 [IIT JEE] I II

HC-f~,
(c) 5 (d) 7
29. Out of the following, the aikene that exhibits optical
isomerism is
(a) 3-methyl-2-pentene
[AIEEE]
(b) 4-methyl- 1-pentene
H-fOH CH2CH3
3

H
( c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
30. Angle strain in cyclopropane is [Manipal] IV V [Ke rala CEE]

(a)24°44' (b)9°44' (c)44' (d) - 5° 16' (a) I and III (b) II, IV and V
(c) I, II and III ( d) II and m
31. Which among the following statements is correct with (e) I, III and V
respect to the optical isomers? [Manipal]
39. The number of isomeric alkanes having the molecular
(a) Enantiomers are non-superimposable mirror images fommla C5 H 12 is [UPSEEJ
(b) Diastereomers are superimposable min-or images
( c) Enantiomers are superimposable mirror image (a) three (b) five
(d) Meso-fonns have no plane of symmetry ( c) nine ( d) thirty two
266 I Chapterwise & Topicwise Engineering Entrances Solved Papers
40. The following compound differ in 50. Maleic acid and fumaric acid are [VITEEEJ
H "- /Cl H"' /Cl (a) positional isomers (b) geometrical isomers
C=C, /C=C, ( c) enantiomers (d) functional isomers
H/ 'a a 'H [UPSEEJ 51. The total number of acylic iosmers including the
(a) configuration (b) conformation stereoisomers (geometrical and optical), with the
( c) structure (d) chirality molecular formula C 4 H 7 Cl is [ManipalJ
41. Racemic compound has [UPSEEJ (a) 12 (b) 11 (c) 10 (d) 9
(a) equimolar mixture ofenantiomers 52. Which of the following compounds is not chiral ?
(b) 1 : I mixture of enantiomer and diastereomer (a) l -chloro-2-methyl pentane [MHT CETJ
( c) I : I mixture of diastereomers (b) 2-chloropentane
( d) I : 2 mixture of enantiomers ( c) 1-chloropentane
42. Which of the following does not contain chiral carbon (d) 3-chloro-2-methyl pentane
atom? [lndraprastha CET, CGPETJ 53. The number of isome1ic ethers with molecular formula
(a) Lactic acid {b) 2-chlorobutanoic acid C 4 HI OO is/are [MHT CET]
( c) Tartaric acid (d) Succinic acid (a) one (b) two (c) three (d) fow·
43. A molecule having three different chiral carbon atoms, 54. Which one of the following compound will show optical
how many stereoisomers it will have? [Guj CETJ iosmerism ? [MP PET]
ws ~3 ~9 006 (a) (CH 3 ) 2 - CH- CH2 - CH3
44. What is the structural formula of fumaric acid? [Guj CETJ (b) CH 3 - CHOH- CH 3
(c) CH 3 - CHC1- CH 2 - CH 3
H 3 C-C-COOH H 3 C-C-COOH (d) CH 3 - CC1 2 - CH 2 - CH3
(a) II {b) II 55. How many optically active stereomers are possible for
HOOC-C-CH3 H 3 C-C-COOH
butan-2, 3-diol ? CKCETJ
H-C-COOH H-C-COOH (a) 1 (b) 2 (c) 3 (d) 4
(c) II (d) II 56. Methoxy methane and ethanol are CKCETJ
H-C-COOH HOOC-C-H (a) position isomers (b) chain isomers
45. Example of geometrical isomerism is [CGPETJ ( c) functional isomers (d) optical isomers
(a) 2-butanol (b) 2-butene (c) butanal (d) 2-butyne 57. Acyclic stereoisomer having the molecular formula
C 4 H 7 Cl are classified and tabulated. Find out the correct
46. The number of isomeric pentyl alcohols possible is [DCEJ
set of numbers. [Kerala CEEJ
(a) two (b) four (c) six (d) eight
Geometrical Optical
2008 (a) 6 2
47. The absolute configuration of (b) 4 2
HO2C CO2H (c) 6 0
(d) 4 0
HO~oH (e) 5 2
H [AIEEEJ
(a)S,S (b)R,R (c)R,S (d) S, R 58. Which one of the following compounds is capable of
existing in a meso form ? [Kerala CEEJ
48. Which of the following compound (s) has Z-configuration?
(a) 3, 3-dibromopentane (b) 4-bromo-2-pentanol
CI" _ / Br II. CI" _ /F (c) 3-bromo-2-pentanol (d) 2, 3-dibromopentane
I. H/C-C"F H/C-C"Br (e) 2, 4-dibromopentane
Br, /CH 3 59. Which of the following will exhibit cis-trans isomerism?
m. c,)c = c"H (a)CH 2 Br - CH 2Br (b)CBr3 - CH 3 [WBJEEJ
[BITSAT, AMU, EAMCETJ
(c) CHBr = CHBr (d) CBr2 = CH 2
(a) Only I (b) Only II (c) Only III (d) I and III
60. How many primary amines are possible with the formula
49. According to Cahn-Ingold-Prelog sequence rules, the
C 4 H 11 N? [WBJEEJ
correct order of priority for the g iven groups is [BITSATJ
(a)-COOH >-CH 2OH > - OH> -CHO Wl ~2 ~3 004
(b)-COOH > -CHO > -CH 2 OH > --OH 61. The number of possible alkynes with molecular formula
(c) - OH > -CH 2OH >-CHO > -COOH C 5 H 8 is CUPSEEJ
(d)--OH > -COOH >-CHO>-CH 2 OH (a)3 (b)4 (c)5 (d)6
 Organic Chemistry some Basic Principles and Techniques I 267
62. Which of the following does not exhibit tautomerism ? 71. Identify, which of the below does not possess any element

(a) o=Q=o (b) o==Oo [OJEEJ

of symmetry ? [VITEEEJ

Vo
(a)(+)(- ) tartaric acid
(b) Carbon tetrachloride
(c) (d) ~o (c) Methane
(d) Meso-tartaric acid
0 0 72. Among the following four structures I to IV
63. Which one of the following monoenes does not exhibit CH3 O CH3
geometric isomerism ? [J&K CETJ I II I
C 2 H5 - CH - C 3 H 7 CH 3 - C-CH - C2H 5
(a) C 4 H 8 (b) C 3 H 6 (c) C 5 H 10 (d) C 8 H16 (I) (Tl)
64. Least stable conformer of cyclohexane is [J&KCET]
H
(a) chair (b) boat
(c) twist boat (d) planar hexagon
I
H - Ce
65. Optical isomerism is shown by [BCECEJ I
H
(a) propanol-2 (b) butanol-2 (c) ethanol (d) methanol (Ill)
66. The absolute configuration of the following [DCEJ it is true that [MP PET]
CH3
(a) all fow- are chiral compounds
H----¥- Cl
Cl- f - -H are
(b) I and II are chiral compounds
(c) only ill is a chiral compound
(d) IT and IV are chiral compounds
C2Hs
(a) 2S, 3R (b) 2S, 3S (c) 2R, 3S (d) 2R, 3R 73. How many chiral carbon atoms are present in
2, 3, 4-trichloropentane? CKCETJ
2007 (a)4 (b) I
67. The number of stereoisomers obtained by bromination of (c) 2 {d) 3
trans-2-butene is [IIT JEE] 74. Which one ofthe following shows functional isomerism?
(a) 1 (b) 2 (c) 3 (d) 4 (a) C2H4 (b) C3H6 [KCETJ
68. Which of the following molecules is expected to rotate the (c) C2H 5 OH (d) CH 2Cl2
plane of plane polarised light? [AIEEEJ 75. Geometrical isomerism is shown by CKCETJ
CHO (a)-C- C- (b)C=C
(a) HO+H (b) ~ (c)-C - C- (d) None of these
H
CH2OH 76. The nun1ber of isomers for the compound with the
molecular formula C 2 Br ClFI is [Kerala CEE]
H2NHNH2
(c) H ..., ,,., H (a)3 (b)4 (c)5 (d) 6
Ph Ph (e) 7
77. Geometrical isomerism is possible in [WBJEE]
69. Which of the following conformations of cyclohexane is
(a) acetone oxime
chiral? [AIEEEJ
(b) isobutene
(a) Twist boat(b) Rigid (c) Chair (d) Boat (c) acetophenone oxime
70. Tautomerism is exhibited by [BITSAT] (d) benzophenone oxime
78. Ethers are isomeric with [WBJEE]
(a) 0 - CH=CH - OH
(a) aldehydes
(b) o==Q=o (b) ketones
(c) both aldehydes and ketones
(d) alcohols
(c) 0-f=O 79. Which of the following will have a meso-isomer also?
(a) 2-chlorobutane [UPSEE, Jamia Millia Is lamia]

(d) o-c:-<=f;H (b) 2, 3-dichlorobutane

(c) 2, 3-dichloropentane
(d) 2-hydroxypropanoic acid
6H CH3
268 I Chapterwise & Topicwise Engineering Entrances Solved Papers

80. Amongst the following compounds, the optically active 2006

alkane having lowest molecular mass is 88. Increasing order of stability among the three main
[UPSEE, Jamia Millia Islamia] conformations, (i.e. Eclipse, Anti, Gauche) of
(a) CH3 - CH 2 - CH 2 - CH 3 2-fluoroethanol is [AIEEEJ
CH3 (a) Eclipse, Gauche, Anti (b) Gauche, Eclipse, Anti
I (c) Eclipse, Anti, Gauche (d) Anti, Gauche, Eclipse
(b) CH3 - CH 2 - CH- CH 3
H 89. The compound, whose stereo-chemical fommla is written
below, exhibits x geometrical isomers and y optical
I isomers
(c)CH3- C- <J
I
C2Hs
(d) CH3- CH 2 - C =CH
81. In this reaction, The values ofx and y are [BITSAT]
CH3CHO+ HCN~ CH3CH(OH)CN (a)4and4 (b)2and2 (c)2and4 (d)4and2
H·OH CH3CH(OH)COOH 90. How many asymmetric carbon atoms are present in
an asymmetric centre is generated. The acid obtained T. 1,2-dimethylcyclohexane
would be [UPSEEJ IT. 3-methylcyclopentane and
TIT. 3-methylcyclohexene ? [BITSAT]
(a) 50% D + 50% L-isomer (b) 20% D + 80% L-isomer
(c) D-isomer (d) L-isomer (a) Two, one, one (b) One, one, one
(c) Two, none, two (d) Two, none, one
82. Isomers of prop ionic acid are [UPSEE]
91. Geometrical isomerism is possible in case of [ManipalJ
(a) HCOOC 2 H 5 and CH3 COOCH3
(a) pentene-2 (b) propane (c) pentane (d) ethene
(b) HCOOC2 H 5 and C 3 H 7 COOH
(c) CH3 COOCH3 and C 3 H 7 OH 92. How many isomers are possible for the alkane C 4 H10 ?
(d) C 3 H7 OHand CH3 COCH3 (a) 3 (b) 5 [Manipal]
(c) 2 (d) 4
83. Metamers of ethyl propionate are [UPSEEJ
93. The number of isomers of the compound with molecular
(a) C 4 H 9COOHand HCOOC4 H 9
fommla C 2H 2 Br2 is [Manipal]
(b) C4 H9COOHand CH 3 COOC3 H 7
(a)4 (b)3 (c)5 (d)2
(c) CH3COOCH3 and CH3COOC3 H 7
94. C 6 H 5 C = N and C 6 H 5N = C exhibit which type of
(d) CH 3 COOC3 H 7 and C 3 H 7 COOCH3
isomerism? [Manipal]
84. Which of the following compounds is optically active ?
(a)(CH 3 )iCHCH2OH (b) CH3 CH 2OH [AMUJ
(a) Position (b) Functional
(c) Metamerism (d) Dextro-isomerism
(c) CC1 2F2 (d) CH3 CHOHC2 H 5
95. The number of meso-fom1s in the following compound is
85. n-pentane, iso-pentane and neo-pentane are examples for
isomers of the type [J&K CETJ HOOC- CH(CH 3 )· CH(OH)· CH(Cl)
· CH(OH)CH(CH3 )· COOH CMHT CETJ
(a) geometrical (b) optical
(a) 3 (b) 4 (c) 8 (d) 16
(c) chain (d) positional
96. Which of the following compounds is optically active ?
86. Different structures generated due to rotation about, C- C
[MPPET]
axis, of an organic molecule, are examples of [J&K CETJ (a) 1-butanol (b) Isopropyl alcohol
(a) geometrical isomerism (c) Acetaldehyde (d) 2-butanol
(b) conformational isomerism 97. Propanal and propanone are (MP PET]
(c) optical isomerism
(d) structural isomerism (a) functional isomers (b) enantiomers
(c) chain isomers (d) structural isomers
87. For which of the following parameters the structural
isomers C 2 H 5 OH and CH3 OCH3 would be expected to
98. How many structural isomers are possible for C 4 H 9Cl?
have the same values? (Assume ideal behaviour) (a) 2 (b) 4 (c) 8 (d) 10 [MP PET]
(a) Heat of vaporisation [Jamia Millia Islamia] 99. The number of optical isomers of CH 3 CH(OH)
(b) Vapour pressure at the same temperature CH(OH)CHO is [Kerala CEEJ
(c) Boiling points (a) zero (b) 2 (c) 3 (d) 4
(d) Gaseous densities at the same temperature and pressure (e) 6
 Organic Chemistry some Basic Principles and Techniques I 269
100. How many optically active stereoisomers are possible for 11 0. Number ofisomers possible for C 4 H 8 0 is [Manipal]
butane-2, 3-diol ? [Kerala CEE]
(a)3 (b)4 (c)5 (d)6
wo
(e) 4
~1 ~2 003 111. The name of the compound [Ke rala CEE]

101. Pick out the alkane which differs from the other members
of the group. [AMU]
~
is
(a) 2,2-dimethyl propane (b) Pentane
(a) (2Z, 4Z)-2, 4-hexadiene (b) (2Z, 4E)-2, 4-hexadiene
(c) 2-methyl butane (d) 2,2-dimethyl butane
(c) (2E, 4Z)-2, 4-hexadiene (d) (4E, 4Z)-2, 4-hexadiene
102. n-pentane and 2-methylbutane is a pair of [J&KCET] (e) (2E, 4E)-2, 4-hexadiene
(a) enantiomers 112. Which of the following Fischer's projection fommla is
(b) stereoisomers identical to D-glyceraldehyde? [Ke rala CEE]
( c) diastereomers
( d) constitutional isomers CH20H CH20H
C H3'-._C/H (a) OH- tCHO (b) H-tOH
103. H3C"-c = c/ "-cooH
H3C/ "-H H CHO
Compound can exhibit [J&KCET] CHO CHO
(a) geometrical isomerism
(b) tautomerism (o) HO- t CH,OH (d) H-tCH,OH
( c) op tical isomerism
( d) geometrical and optical isomerism H OH
104. The isomers which are interconverted through rotation H
around a single bond are [J&K CET]
(e) H~- tCH,OH
(a) conformers (b) diastereomers
( c) enantiomers (d) position isomers
CHO
105. 2-pentanone and 3-methyl-2-butanone is a pair of
113. Eno! content is highest in [OJEE]
isomers. [J&K CET]
(a) acetone (b) acetophenone
(a) functional (b) chain (c) positional (d) stereo
(c) acetic acid (d) acetyl acetone
106. Which of the following is a dynamic isomerism?
114. Which of the following is a pair offunctionaJ isomers?
(a) Metamerism [Jamia Millia Islamia]
(a) CH3COCH 3 , CH 3CHO [EAMCETJ
(b) Geometrical isomerism (b)C 2H 5 C02H,CH 3C0 2CH3
( c) Tautomerism (c) C2H 5 C0 2H, CH3C0 2C2Hs
( d) Coordinate isomerism (d) CH 3C0 2H, CH3CHO
107. The reason for the loss of optical activity of lactic acid
115. What kind of isomerism is possible for
when -OH group is changed by H is that l-chloro-2-nitroethene? [J&KCET]
[Jamia Millia Islamia]
(a) chiral centre of the molecule is destroyed (a) Functional group isomerism
(b) molecules acquires asymmetry (b) Position isomerism
(c) EIZ isomerism
( c) due to the change in configuration
( d) structural changes occur ( d) Optical isomerism
116. Which of the following will be chiral ? [J&K CETJ
2005 (a) CH3CHCl 2 (b) CH 3 C HBrCl
108. Which type of isomerism is shown by (c) CD 2Cl 2 (d) CH 2C1Br
2, 3-dichlorobutane ? [AIEEE] 117. Which of the following shows geometrical isomerism ?
(a) Structural (b) Geometric [BCECE]
(c) Optical (d) Diastereomer (a) C2 H 5 Br (b) (CH 2) (COOH)z
109. Nitroethane can exhibit which one of the fol1owing kinds (c) (CH)z (COOH)i (d) C2H6
of isomerism [Manipal] 118. Geometrical isomerism is not shown by
(a) Metamerism (a) 1, 1-dichloro-1-pentene [Jamia Millia Islamia]
(b) Optical activity (b) 1, 2-dichloro-1-pentene
(c) Tautomerism ( c) 1, 3-dichloro-2-pentene
(d) Position isomerism ( d) 1, 4-dichloro-2-pentene
270 I Chapterwise & Topicwise Engineering Entrances Solved Papers

119. Racemic mixture is fonned by mixing two 120. Maximun1 enol content is in [Jamia Millia Islamia]
(a) isomeric compounds [Jamia Millia Islamia] 0 0 0
(b) chiral compounds
( c) meso compounds
(a)
)l (b)
)l)l
( d) enantiomers with chiral carbon 0 0 0
(c) (d)
) lH )l)lH

Topic 5
Methods of Purification of Organic Compounds
2012 2007
1. Identify the binary mixture(s) that can be separated into 6. Match the following columns.
individual compounds, by differential extraction as shown
Column I Column II
in the given scheme. [HT JEE]
A. Glycerol 1. Sublimation
NaOH (aq) !Compound 1 I B. o-nitrophenol 2. Beilstein' s test
+
Binary mixture containing C. Anthracene 3. Victor-Meyer's method
ICompound 2 I
Compound 1 and D. Halogens 4. Steam distillation
Compound 2 NaHCO3 (aq) !Compound 1 I E. Molecular weight 5. Vacuum distillation
ICompound 2 I 6. Eudiometry
(a) C 6 H 5 OHand C 6 H 5 , COOH Codes
(b) C 6 H 5 COOHand C 6 H 5 CH2 OH A B C D E [KeralaCEE]
(c) C 6 H 5 CH 2 OHand C 6 H 5 OH (a) 5 4 I 2 3
(d) C 6 H 5 CH 2 OHand C 6 H 5 CH2 COOH (b) 4 5 I 6 2
(c) 6 4 I 3 2
2009 (d) 5 4 6 2 3
2. Naphthalene can be easily purified by [UPSEEJ (e) 4 6 2 3 5
(a) sublimation (b) crystallisation 7. Fractional distillation is a process by which the separation
( c) distillation (d) vaporisation of different fractions from mixture of solution is carried by
making use which of the following property of the
2008 fractions ? [J&K CETJ
3. Which of the following process is suitable for the (a) Freezing point (b) Boiling point
purification of aniline? [Keral a CEE] (c) Melting point (d) Solubility
(a) Simple distillation 8. Which of the substances is purified by sublimation ?
(b) Fractional distillation (a) Benzoic acid (b) Camphor [DCEJ
( c) Fractional crystallisation (c) Naphthalene (d) All of these
(d) Steam distillation
( e) Azeotropic distillation 2006
4. For the purification, isolation and separation of organic 9. A mixture of camphor and benzoic acid can be separated
compounds, the latest technique followed is [Guj CETJ by [Manipal]
(a) chromatography (a) sublimation (b) extraction with a solvent
(b) steam distillation ( c) chemical method ( d) fractional crystallisation
(c) fractional crystallisation
1O. Which of the following reagents will be fruitful for
( d) sublimation
separating a mixture of nitrobenzene and aniline?
5. The best method to separate the mixture of ortho and para (a)Aq. NaHCO 3 (b)H 2 O [MHT CETJ
nitrophenol ( 1:1) is [DCEJ (c) Aq. HCl (d) Aq. NaOH
(a) vaporisation (b) colour spectrun1 11. Which method is used to separate sugars ? [Guj CETJ
( c) distillation (d) crystallisation
(a) Fractional crystallisation (b) Sublimation
(c) chromatography (d) Benedict's reagent
 Topic 6
Qualitative and Quantitative Analysis of Organic Compounds
1. The sodium extract of an organic compound on acidification 9. In Kjeldahl's method, ammonia from 5g of food
with acetic acid and addition of lead acetate solution gives a neutralises 30 cm3 of 0.1 N acid. The percentage of
black precipitate. The organic compound contains nitrogen in the food is [KCETJ
(a) nitrogen (b) halogen [VITEEEJ
(a) 0.84 (b) 8.4 (c) 16.8 (d) 1.68
(c) sulphur (d) phosphorous
10. 0.765 g of an acid gives 0.535 g of CO 2 and 0.138 g of
2. For the reaction represented by the equation. H 2 0. Then, the ratio of the percentage of carbon and
CX 4 + 202 ~ CO2 + 2X 2 0. 9.0 g ofCX 4 completely hydrogen is [JCECEJ
reacts with 1.74 g of oxygen. The approximate molar mass
of X will be [Manipal]
(a) l 9:2 (b)l8 :ll (c)20 : 17 (d) l :7
(a) 20 (b) 40 (c) 60 (d) 80 2009
3. In estimation of nitrogen, by Kjeldahl's method, CuSO 4 11. An organic compound on heating with CuO produces
acts as an [UPSEEJ CO 2 but no water. The organic compound may be
(a) oxidising agent (b) reducing agent (a) carbon tetrachloride [ManipalJ
(c) catalysing agent (d) hydrolysing agent (b) chloroform
(c) methane
4. On complete combustion, 0.246 g of an organic compound
(d) ethyl iodide
gives 0.198 g of CO2 and 0.1014 g ofH 2 0. The ratio of
carbon and hydrogen atoms in the compound is [AMUJ 12. Lassaigne's test for the detection of nitrogen fails in
(a) 1 : 3 (b) 1 : 2 (c) 2: 5 (d) 2: 7 (a) H 2 N-CO-NHNH 2 • HCl [Kerala CEEJ
(b) NH 2 -NH2 ·HCl
2013 (c) NH 2 -CO-NH2
(d) C 6 H 5 -NH-NH2 ·HCl
5. On combustion, a gaseous hydrocarbon gives 0.72 g of
(e) C 6 H 5 CONH 2
water and 3.08 g of CO 2 . The empirical formula of the
hydrocarbon is [JEE Mains] 13. 0.25 g of an organic compound on Kjeldahl's analysis
gave enough ammonia to just neutralise 10 cm3 of
(a) C 2 H 4 (b) C 3 H4 (c) C 6 H 5 (d) C7 H 8
0.5 M H 2 SO4 . The percentage of nitrogen in the
2012 compound is [Kerala CEEJ
6. An oxygen contauung organic compound was found to (a) 28 (b) 56 (c) 14 (d) 112
contain 52% carbon and 13% hydrogen. Its vapour density is (e) 42
23. The compound reacts with sodiwn metal to liberate 14. Which one of the following compounds gives white
hydrogen. A functional isomer of this compound is CKCETJ precipitate with AgNO 3 ? [OJEEJ
(a) ethanal (b) methoxy methane

~
(c) methoxy ethane (d) ethanol

2011 (a) (b) ~,Cl

7. 1.2 g of an organic compound on Kjeldahl station liberates
ammonia which consumes 30cm' of 1 N HCI. The percentage Br
of nitrogen in the organic compound is [KCETJ
(a) 30 (b) 35 (c) 46.67 (d) 20.8

2010 (d) None of these

8. 29.5 mg of an organic compound containing nitrogen was
digested according to Kjeldah l's method and the evolved 2008
an1Illonia was absorbed in 20 mL of 0.1 M HCI solution.
15. When SCN- is added to an aqueous solution containing
The excess of the acid required 15 mL of 0.1 M NaOH
Fe(NO 3 ) 3 , the complex ion produced is [VITEEEJ
solution for complete neutralisation. The percentage of
nitrogen in the compound is [AIEEEJ (a) [Fe(OH 2 )z (SCN)] 2 + (b) [Fe(OH 2 )
5
(SCN)] 2+
2
(a) 59.0 (b) 47.4 (c) 23.7 (d) 29.5 (c) [Fe(OH 2 ) 8 (SCN)] + (d) [Fe(OH 2 )(SCN)]6 +
272 I Chapterwise & Topicwise Engineering Entrances Solved Papers
16. Which of the following complex formation indicates 23. The compound formed in the positive test for nitrogen with
presence ofsulphur in the organic compound when sodiwn the Lassaigne's solution of an organic compound is
nitroprusside is added to sodium extract ofthe compound? (a) Fe 4 [Fe(CN)6 h [Jamia Millia Islamia]
[OJEEJ (b) Na 3 [Fe(CN) 6 ]
(a) Fe 4 [Fe(CN)6 h (b) Na 2 [Fe(NO)(CN)5 ] (c) Fe(CN)3
(c) Fe 4 (CNS) 3 (d) Na 4 [Fe(CN)5 NOS] (d) Na 4 [Fe(CN) 5 NOS]
17. During the fusion of an organic compound with sodium 24. The ammonia evolved from the treatment of 0.30 g of an
metal, nitrogen of the compound is converted into organic compound for the estimation of nitrogen was
(a) NaNO 2 [Jamia Millia Islamia] passed in 100 mL of0.1 M sulphuric acid. The excess of
(b) NaNH 2 acid required 20 mL of0.5 M sodium hydroxide solution
(c) NaCN for complete neutralisation. The organic compound is
(d) NaNC (a) acetamide [Jamia Millia Islamia]
2007 (b) benzamide
(c) urea
18. Acidified sodium fusion extract on addition with ferric ( d) thiourea
chloride solution gives blood red colouration which
confirm the presence of [KCET] 2006
(a) Sand Cl (b) N and S 25. An organic compound which produces a bluish green
(c) N (d) S coloured flame on heating in presence of copper is
19. Presence ofhalogen in organic compounds can be detected (a) chlorobenzene (b) benzaldehyde [KCETJ
by using [KCETJ (c) aniline (d) benzoic acid
(a) Leibig's test (b) Duma's test 26. 5.6 g of an organic compound on burning with excess of
(c) Kjeldahl's test (d) Beilstein's test oxygen gave 17.6 gofCO 2 and 7.2 gofH 2 0. The organic
20. An organic compound having molecular mass 60 is found compound is [Ke rala CEEJ
to contain 20% C, 6.67% H and 46.67% N while rest is (a) C 6 H 6 (b) C 4 H 8
oxygen. On heating, it gives NH 3 along with a solid (c) C3 H 8 (d) CH 3 COOH
residue. The solid residue gives violet colour with alkaline (e) CH 3 CHO
copper sulphate solution. The compound is [UPSEEJ 27. Quantitative measurement of nitrogen in an organic
(a) CH 3 CH 2 CONH 2 (b) (NH 2 )i CO compound is done by the method [WB JEE]
(c) CH 3 CONH 2 (d) CH 3 NCO (a) Berthelot method (b) Beilstein's method
21. Na 2 S + Na 2 [Fe(CN)s NO]~ purple colour. (c) Lassaigne's test (d) Kjeldahl's method
It is due to [OJEEJ 2005
(a) Na 4 [Fe(CNh NOS] (b) Na 3 [Fe(CN)5 NOS] 28. How much ofsulphur is present in an organic compound, if
(c) Na 4 [Fe(CN)5 NO] (d) Na 4 [Fe(CN)5 NOS] 0.53 g of the compound gave 1.158 g of BaSO 4 on
22. Liebig's test is used to estimate [DCE] analysis? [Ke rala CEE]
(a) H (b) C (a) 10% (b) 15% (c)20%
(c) Both C and H (d) N (d) 25% (e) 30%
 Topic 7
Types of Organic Reactions
2013 2011
1. KI in acetone undergoes SN 2 reaction with each P,Q, R 7. The total number of possible alkenes by
and S. [JEE Mains] dehydrobromination of 3-bromo-3-cyclopentylhexane

aCCI using alcoholic KOH is [IITJEE]

(a)l (b)3 (c) 5 (d) 7
H3G-CI >-Cl ~Cl 8. Which one of the following is an intermediate in the
reaction of benzene with CH3Cl in the presence of
P Q R S anhydrous AlCI 3? [KCETJ
The rates of reaction vary as (a)Cl+ (b)CH3
(a)P > Q > R >S (b)S > P > R > Q +
(c)P > R > Q > S (d)R > P > S> Q
2. Which one of the following compounds does not follow (d)o
Markownikoffs rule? [JEE Mains]
9. The ease of dehydrohalogenation of alkyl halides with
(a) CH3-CH= CH2
alcoholic KOH is [WB JEEJ
(b) CH 3 CH=CHCH3
(a) 3° < 2° < l 0
(c) CH3-CH-CH= CH2 (b)30> 20 > 10
I (c)3°<2°> 1°
CH3 (d)3°>2°<1°
(d) CH 3-CH2 -CH=CH2
3. In SN 1 reaction, the racemisation takes place. It is due to 10. The ease of nitration of the following three hydrocarbons
(a) inversion configuration [Manipal] follows the order [WB JEE]
(b) retention of configuration
( c) conversion of configuration
(d) Both (a) and (b)

2012
4. Which of the following statements is not true for SN l
reaction ? [KCET]
(a) 3° alkyl halides generally react through SN I reaction (a) II = III ,,, I
(b) The rate of the reaction does not depend upon the (b) II > I > III
molar concentration of the nucleophile (c) III > II > I
(c) 1° alkyl halides generally react through SN I reaction (d) I =Ul>II
(d) It is favoured by polar solvents
11. Reaction of methyl bromide with aqueous sodium
5. Under identical conditions, the SN 1 reaction will occur hydroxide involves CKCETJ
most efficiently with [WB JEE]
(a) racemisation
(a) tert-butyl chloride (b) SN I mechanism
(b) 1-chlorobutane ( c) retention of configuration
( c) 2-methyl- 1-chloropropane ( d) SN 2 mechanism
(d) 2- chlorobutane
12. Which one of the following has the most nucleophilic
6. Which one of the following will most readily dehydrated in nitrogen? CKCETJ
acidic solution? [AMU]

(a)~
OH
(b)~
0 OH (a) 0 N
(b)
0
N
I
~
H
(c) (d) ~ aNHCOCH3 aNH2
OH (c) (d) I
OH
274 I Chapterwise & Topicwise Engineering Entrances Solved Papers
13. Consider the following compounds, LAH
20. I. CH3CH 2 Br ~ C 2H 6 and
OCH3 NO2
LAH

6 0 II
6III [Punjab CETJ
II. (CH 3 h CBr ~

The reason for this is

alkene,

(a) (I) SN 2, (II) E I mechanism

(b) (I) SN 1, (II) E 2 mechanism
[OJEEJ

Arrange the above compounds in the con-ect order ( c) (I) SN 1, (II) E 1 mechanism
according to their reactivity towards electrophile. ( d) (I) SN 2 , (JI) E 2 mechanism
(a) II > III > I 0
(b) III < I < II
(c) I > II > III 21. In the compound @-!-o-@
(d) l=dl > III
Ring I Ring II
2009 electrophilic substitution occurs at [OJEE]
14. In electrophilic aromatic substitution reaction, the nitro (a) ortho/para-position at ring I
group is meta-directing because it [Manipal] (b) meta-position at ring I
(c) ortholpara-position at ring II
(a) decreases electron density at ortho and
( d) meta-position at ring II
para-positions
(b) decreases electron density at meta-position 22. Arrange the following compounds in order of their
(c) increases electron density at meta-position decreasing reactivity towards an electrophile, E fIJ . [AMUJ
( d) increases electron density at ortho and para-positions I. Chlorobenzene
15. The electrophile involved in the sulphonation of benzene is II. 2, 4-dinitrochlorobenzene
III. p-nitrochlorobenzene
(a)so; (b) sot CManipaIJ
(a) Ill> II> I (b) II> Ill> I
(c) H 3 0+ {d) S03
(c) I> Ill> II (d) I> II> III
16. Which of the following would react most readily with 23. C 2H 5 Cl+ aq. NaOH ~ C 2H 5 OH + NaCl
nucleophiles? [UPSEEJ this reaction is [lndraprastha CET]
Cl (a) electrophilic substitution ofl order

(a)~ (b) ~
~ O CH 3
(b) electrophilic substitution of II order
( c) nucleophilic substitution ofl order
( d) nucleophilic substitution of II order
Cl 24. The least active electrophile is [DCE]
/O- CH3
Cl

(c) $NO2
(a) H3C = C~
0

17. In which of the following ways, does the hydride ion tend 2008
to function ? [UPSEEJ 25. Following reaction,
(a) An electrophile (b) A nucleophile (CH3 h CBr+H 2O-----? (CH 3 h COH+ HBr
( c) A free radical (d) An acid
is an example of [MHTCET]
18. The reaction of sodium ethoxide with iodoethane to form (a) elimination reaction
diethyl ether is termed as [UPSEEJ (b) free radical substitution
(a) electrophilic substitution (c) nucleophilic substitution
(b) nucleophilic substitution ( d) electrophilic substitution
(c) electrophilic addition 26. Formation of cyanohydrin from a ketone is an example of
( d) radical substitution
(a) electrophilic addition [WB JEE]
19. Dehydration of alcohol usually goes by [UPSEEJ (b) nucleophilic addition
(a) E 1 mechanism {b) E 2 mechanism ( c) electrophilie substitution
( c) E 1cb mechanism (d) SN 2 mechanism ( d) nucleophilic s ubstitution
 Organic Chemistry some Basic Principles and Techniques I 275
2006
27. In a compound ~ E ' electrophilic substitution

has occurred. The substituent-E are methyl,

- CH2 CI, - CCl 3 and - CHCl 2 . The correct
increasing order of these substituents towards electrophilic
35· u OH
+ CHCl3 + NaOH ~ C( CHO
The electrophile involved in the above reaction is
O- N!

$
substitution is [OJEEJ (a) dichloromethyl cation (CHCl 2 ) [AIEEE]
(a) - CH3 < - CH 2 Cl < - CHCl 2 < - CC1 3 (b) dichlorocarbene (:CCl 2 )
(b) - CH3 < - CHC1 2 < - CH 2 Cl < - CCl 3
(c) - CC1 3 < - CH 2 Cl < - CHC1 2 < - CH3 (c) trichloromethyl anion (CC1 3 )
$
(d) - CCl 3 < - CHCl 2 < - CH 2 Cl < - CH3 (d) fonnyl cation (CHO)
28. Protic solvent is [UPSEE] 36. Which of the following is arranged according to the nature
(a) diethyl ether (b) n-hexane indicated ? [OJEEJ
(c) acetone (d) ethanol +
(a) Electrophile - NO 2 , Br+,
29. Which of the following will be easily nitrated? [UPSEEJ
CH3
Nucleophile -CH 3OH, N°i

(•)©
+
(b) Electrophile - NO 2 , CH 3 OH,
Nucleophile - Br+, N 3
(c) Electrophile - CH3OH,N3 .
Nucleophile - No; , Br+
( d) Electrophile - Br+ , N 3 ,
+
Nucleophile -CH 3OH, NO 2
30. Dehydration of alcohol is an example of which type of 37. Which of the following solvents are aprotic?
reaction ? [J&K CETJ I. NH 3 II. SO 2
(a) Substitution III. CH 3CN IV. CH 3CO 2H [J&K CETJ
(b) Elimination (a) I, II, III (b) I, III, IV
(c) Addition (c) II, III (d) I, III
( d) Rearrangement
38. RX + i- ~ R - I+ x- is an example of ....... reaction.
31. Conversion of chlorobenzene to phenol involves (a) nucleophilic addition [J&K CETJ
(a) electrophilic substitution [J&K CETJ (b) nucleophilic substitution
(b) nucleophilic substitution (c) electrophilic addition
( c) free radical substitution ( d) elimination
(d) electrophilic addition
2005
2007 39. The decreasing order of nucleophilicity among the
32. Which of the following is least reactive towards following nucleophiles is
nucleophilic substitution reaction? [Manipal] I. CH 3c - o- II. CH3O-
(a) (CH 3 h C - Cl II 0
(b) CH 2 = CHCl 0

-0-II
11
(c) CH 3 CH 2 Cl III. CW IV H 3C S-O-
(d) CH 2 = CHCH 2 CI .
0
33. The Kolbe's electrolysis proceeds via [WBJEE] (a) Ill, II, I, IV (b) II, III, I, IV [AIEEE]
(a) nucleophilic substitution mechanism (c) IV, III, II, I ( d) I, n, III, IV
(b) electrophilic addition mechanism 40. The reaction,
(c) free radical mechanism 0 0
( d) electrophilic substitution reaction II II
34. During nitration of benzene, the attacking electrophile is R- C- X+Nu- ~ R - C- Nu+x-
(a) NO3 (b) NO2 [DCE, OJEEJ is fastest when Xis [AIEEE]
(c) No; (d) HN03 (a) OCOR (b) OC2 H5 (c) NH 2 (d) Cl
276 I Chapterwise & Topicwise Engineering Entrances Solved Papers
41. Grignard reagent adds to [KCET] 46. Which of the following cannot undergo nucleophilic
(a) C = 0 {b) - C = N substitution under ordinary conditions ? [J&K CETJ
(c) C = S (d) All of these (a) Chlorobenzene
42. Vinyl chloride undergoes [UPSEE] (b) Tert-butylchloride
(c) Isopropyl chloride
(a) Only addition reactions (d) None of the above
(b) Only elimination reactions
(c) Both (a) and (b) 47. Which of the following is an electrophile? [J&KCETJ
(d) substitution reactions (a) H 2 O (b)SO 3
43. In the nucleophilic substitution reactions (SN 2 or SN I), the (c) NH 3 (d) ROR
reactivity of alkyl halides follows the sequence [AMUJ 48. Alkyl halide can be conve11ed into alkene by [BCECE]
(a) R - I > R - Br > R - Cl > R - F (a) nucleophilic substitution reaction
(b) R - CI > R - F > R - Br > R - I (b) elimination reaction
(c) R - F > R - Cl > R - Br > R - I (c) Both (a) and (b)
(d) R - I > R - F > R - Cl > R - Br (d) rearrangement
44. The following compound will undergo electrophilic 49. Nitration of benzene is [BCECE]
substitution more readily than benzene [Guj CET] (a) electrophilic substitution
(a) nitrobenzene (b) benzoic acid (b) electrophilic addition
(c) benzaldehyde (d) phenol (c) nucleophilic substitution
(d) nucleophilic addition
45. The function of AlCl 3 in Friedel-Craft's reaction is
50. Which of the following is most reactive towards
(a) to absorb HCI [Guj CET]
nucleophilic substitution reaction ? [DCEJ
(b) to absorb water
(c) to produce nucleophile (a) CH 2 = CH- Cl (b) C6 H 5 Cl
(d) to produce electrophile (c) C 6 H 5 CH 2 Cl (d) ClCH 2 - CH = CH 2

Answers
TOPICl Classification and Nomenclature of Organic Compounds
1. (a) 2. (a) 3. (c) 4. (b) 5. (c) 6. (d) 7. (d) 8. (a) 9. (c) 10. (b)
11. (b) 12. (a) 13. (b) 14. (a) 15. (c) 16. (b) 17. (a) 18. (d) 19. (d) 20. (a)
21. (a) 22. (b) 23. (b) 24. (c) 25. (e) 26. (e) 27. (c) 28. (b) 29. (b) 30. (d)
31. (b) 32. (a) 33. (a) 34. (d) 35. (c) 36. (d) 37. (b) 38. (a) 39. (b) 40. (a)
41. (b) 42. (c) 43. (a) 44. (d) 45. (a) 46. (d) 47. (a) 48. (d) 49. (b) 50. (a)
51. (a) 52. (a) 53. (a) 54. (a) 55. (c) 56. (a) 57. (a) 58. (d) 59. (c) 60. (d)
61. (a) 62. (b) 63. (c) 64. (c) 65. (d) 66. (a) 67. (b) 68. (a) 69. (d) 70. (d)
71. (a) 72. (b) 73. (d)
TOPIC2 Fission of Bonds and Electron Displacement Effects
1. (d) 2. (a) 3. (c) 4. (b) 5. (b) 6. (d) 7. (d) 8. (b) 9. (b) 10. (b)
11. (a) 12. (b) 13. (c) 14. (b) 15. (d) 16. ( d) 17. (a) 18. (b) 19. (a) 20. (c)
21. (a) 22. (a) 23. (a) 24. (a) 25. (a) 26. (b) 27. (a) 28. (b) 29. (d) 30. (b)
31. (d) 32. (c) 33. (c) 34. (c) 35. (b)
TOPIC3 Reaction Intermediates
1. (a) 2. (a) 3. (d) 4. (c) 5. (d) 6. (d) 7. (b) 8. (c) 9. (b) 10. (b)
11. (c) 12. (c) 13. (d) 14. (c) 15. (b) 16. (a) 17. (e) 18. (b) 19. (d) 20. (a)
21. (a) 22. (b) 23. (d) 24. (a)
 Organic Chemistry some Basic Principles and Techniques I 277

TOPIC4 Isomerism
1. (a, c, d) 2. (a) 3. (b) 4. (c) 5. (b) 6. (d) 7. (a) 8. (b) 9. (a) 10. (a, c)
11. (c) 12. (b) 13. (a) 14. (d) 15. (b) 16. ( d) 17. (b) 18. (b) 19. (c) 20. (b)
21 . (b,c) 22. (c) 23. (c) 24. (a) 25. (d) 26. (b) 27. (a) 28. (c) 29. (c) 30. (a)
31 . (a) 32. (a) 33. (c) 34. (b) 35. (c) 36. (c) 37. (c) 38. (c) 39. (a) 40. (c)
41 . (a) 42. (d) 43. (a) 44. (d) 45. (b) 46. (d) 47. (b) 48. (d) 49. (d) 50. (b)
51 . (a) 52. (c) 53. (c) 54. (c) 55. (b) 56. (c) 57. (a) 58. (e) 59. (c) 60. (d)
61 . (a) 62. (a) 63. (b) 64. (d) 65. (b) 66. (b) 67. (b) 68. (a) 69. (a) 70. (a)
71 . (a) 72. (b) 73. (c) 74. (c) 75. (b) 76. (d) 77. (c) 78. (d) 79. (b) 80. (c)
81 . (a) 82. (a) 83. (d) 84. (d) 85. (c) 86. (b) 87. (d) 88. (c) 89. (b) 90. (d)
91 . (a) 92. (c) 93. (d) 94. (b) 95. (b) 96. (d) 97. (a) 98. (b) 99. (d) 100. (c)
101. (d) 102. (d) 103. (c) 104. (a) 105. (b) 106. (c) 107. (a) 108. (c) 109. (c) 110. (d)
111. (a) 112. (b) 113. (d) 114. (b) 115. (c) 116. (b) 117. (c) 118. (a) 119. (b) 120. (b)
TOPIC5 Methods of Purification of Organic Compounds
1. (b, d) 2. (a) 3. (d) 4. (a) 5. (c) 6. (a) 7. (b) 8. (d) 9. (b) 10. (c)
11. (c)
TOPIC6 Qualitative and Quantitative Analysis of Organic Compounds
1. (c) 2. (d) 3. (c) 4. (c) 5. (d) 6. (b) 7. (b) 8. (c) 9. (b) 10. (a)
11. (a) 12. (b) 13. (b) 14. (b) 15. (b) 16. (d) 17. (c) 18. (b) 19. (d) 20. (b)
21. ( d) 22. (c) 23. (a) 24. (c) 25. (a) 26. (b) 27. (d) 28. (e)
TOPIC7 Types of Organic Reactions
1. (b) 2. (b) 3. (d) 4. (c) 5. (a) 6. (b) 7. (b) 8. (c) 9. (b) 10. (b)
11. ( d) 12. (a) 13. (c) 14. (c) 15. ( d) 16. (c) 17. (b) 18. (b) 19. (a) 20. (d)
21. (c) 22. (c) 23. (d) 24. (c) 25. (c) 26. (b) 27. (d) 28. (d) 29. (a) 30. (b)
31. (b) 32. (b) 33. (c) 34. (c) 35. (b) 36. (a) 37. (a) 38. (b) 39. (b) 40. (d)
41. (d) 42. (c) 43. (a) 44. (d) 45. (d) 46. (a) 47. (b) 48. (b) 49. (a) 50. (c)
 Explanations
Topic 1 Classification and Nomenclature of Organic Compounds

1.
¢:NO, I
CH3 -
CH3 CH3 CH3
21 3
T _ T _ T _ CH3
I 4 I 5

CH3 CH3 CH3 Methylgroup-6

OCH3
6. Hydrocarbons are the compounds of carbon and hydrogen only.
Since, more priority group attached is - CHO (aldehyde), Saturated hydrocarbon (e.g. alkanes), unsaturated hydrocarbons
nitro (- NO2 ) and alkoxy (- OCH3 ) group have lower order. (e.g. alkenes, alkynes) and aromatic hydrocarbons (e.g. benzene
Hence, the correct name of the compound according to IUPAC is and its derivatives) are the types of hydrocarbons.
4-methoxy-2-nitrobenzaldehyde.
4 3 2
7. Picric acid is nitro compound instead of carboxylic compound. It
2. CH2 - CH- CH2 is a yellow coloured highly explosive compound.
I I I OH
5
CN CN CN 1

y
3•cyanopentane- I, 6-dinitrile 02NhN02
Note However, according to latest TUPAC recommendation, if
three same functional groups are present then a ll the three are
not included in the main chain and the compound name is as NO,
3 2 I 2, 4, 6-trinitrophenoi (picric acid)
CH2 - CH- CH2
8. The structure of iso-propylamine can be represented as
I I I ICH3
CN CN CN
I, 2, 3-tricyanopropane 3 2 I
3. Structural formula of the given compound is CH3 - CH -NH2
l 2 3 4
H 2C =CH- ?H - CH3 :. IUPAC name is propan-2- amine.

CH 3 I 2 3
9. CH3- CH = T- CH3
This compound has one double bond and one substituent
(- CH3). In accordance with the preference mle, preference is 4CH2
given to double bond over alkyl group. I
Therefore, naming is done from doubly bonded carbon of left sCH3
side and hence, the IUPAC name of the given compound is So, the name is 3-methylpent-2-ene.
3-methyl - I-butene. 5 4 3 2 1

4. Thinking process 10. CH2 =CH- ?H- ? = CH2

(i) Draw the structure of l-butene-3-yne and count the number
CH3CH 2 Br
of single and multiple bonds.
(ii) A double bond contains one sigma and one pi-bond while a The IUPAC name of this molecule is
triple bond contains one sigma and two pi bonds. 2-bromo-3-ethyl- 1, 4-pentadiene
H,.to 10 CH3
"c c.!Q_c == c.!Q...H
W'jo In IIG lo
2,i
I 2 3' 4 5 6 7 8
11. C H 3- CH2 - CH- CH 2- TH- CH 2 - CH2 - CH3
H
CH
Total number of sigma and pi-bonds
= (5 + I+ I) cr + (0 +I+ 2) 1t i.e. 7cr, 31t H 3C
/ \CH
3
Thus, the number of cr and 1t-bonds in l-butene-3-yne are 7 sigma Straight chain which contains large number of side chains taken
and 3 pi. as parent chain and colmting starts from that side where the side
5. In long chain, alkyl groups, - CH3 becomes part of the whole chain is nearest. Hence, the IUPAC name of the given, compound
alkyl group. is 3-methyl-5-( I -methyl) octane.
I
Thus, in C 11H 24 or CH3(CH2 ) 9 CH3, minimlm1 number of methyl
group is 2 But maximum number of methyl groups, in the 12. According to IUPAC nomenclature, the IUP AC name of ~ is
following structure are 6. bicyclo (2, I, 0) pentane. LJ
 Organic Chemistry Some Basic Principles and Techniques I 279
H
5 1 3 2 I
4
13. CH 3- C- CH2 - CH - CHO

OH
I
CH 3
I
IUPAC name is 4-hydroxy-2-methyl pentanal
22.
:~CN Br
0 0 Cyano group has the highest priority therefore, parent name must
~ 4 3 II be benzonitrile. Br occurs at 2-position, and hydroxyl at
14. 4 ~ 2 I OH or CH2= CH~2/c~ 5-position, by alphabetically order. Hence, the IUPAC name is
But-3-enoic acid CH OH 2-bromo-5-hydroxy benzonitrile.
2
23. The structure of neopentane is
Ph CH 3

15. Me
6

+ Me
1/"' ~
1

Phenyl

~ Vinyl
CH3f

1CH
I

CH 3
Thus, the TUPAC name is 2, 2-dimethyl propane
- CH 3

3
2 I
CH3- CH2 - TH- CH- ~ 24. CH3- ? - CI
CH3 3CH3
2-chloro-2-methylpropane

Here, s-butyl is secondary butyl.

5 4 3 2 I
16. CH 3- ? H-CH=r- CHO
E-3- eihyl-4-methylhex-3-en-1-<>ic acid
OH CH3 The configuration of this compound is E because bulkier groups
4-hydroxy-2-methylpent•2· en• I-al are present at opposite of the double bond.
17. The structural formula of the compound 26. In conjugated diene, alternate single and double bonds are
5-nitro-3- methoxy-3-methyl hexanoyl chloride is as present, while in cummulative diene, double bonds are present at
N02 CH3 0 adjacent positions.
I 2 3 4 5 6
6 sl 4 31 2 II
1
I. H 2 C=CHCH 2 CH2 CH=CH2
CH3 - CH- CH2 - T- CH2 - C- CI Hexa · I, 5-diene

OCH3 It is an isolated diene.

I 2 3
18. The TUPAC name of the given compound is TT. H 2 C=C=CH 2 ⇒ Tt is a cumulative diene.
Prop-I, 2--diene

lr,
I
I 2 3 4 5 6
ITT. H 2 C=CH- CH=CHCH 2 CH 3
Hexa -1 , 3-diene
It is a conjugated diene.
Br I 2 3 4
IV. H 2 C=CH- CH=CH2
3-bromo-2-methylpentanal Buta - 1, 3-diene

19. Esters are named by prefixing the name of the alkyl or aryl group It is a conjugated diene.
(of OR' part) before the name of the parent acid and changing the V. Prop-I, 2-diene is a cumulative diene.
suffix ic acid to ate. Hence, the structure of phenyl ethanoate is Hence, statement ITT and V are correct.

0-coa+ciH5
20. The stmcture ofacryldehyde is CH2=CH- CHO.
Hence, the TUPAC name is prop-2-en-l-al.
27.
O>
Bicyclo (4, 1, OJ heptane

2 I
This compound contains 7 carbon atoms, so the corresponding
21. C2H 5 - C- CHpH alkane is heptane. Two bridges contain 4 and I carbon atom
311 respectively and one bridge does not contain any carbon atom.
CH2 So, the name of the compound is bicyclo (4, I, 0) heptane.
2-ethylprop-2-en -1-ol
280 I Chapterwise & Topicwise Engineering Entrances Solved Papers

CH 3 I
I 3 12 I
28. CH 3- T- CHzOH or (CH3hC- CHzOH is neo-pentyl 36. H3C- T - CH3

CH 3 CH3
1-butyl iodide
alcohol.
Carbonyl group Carbonyl group Its IUPAC name is 2-iodo-2-methyl propane.
25. R "- ~
(a) H/C=O
R
"~
(b) R/C = O 37. The structure of anisole can be represented as
Aldehyde Ketone
(2 valencies ofC satisfied (2 valencies of C satisfied ~;
by one Rand H) by 2 R-groups)

0
II Anisole

(c)
R"-
- /c =0
R- C"- It is an ether and the name of ether is given as alkoxy alkane, so,
(d) R- C/0 its name is methoxy benzene.
H<J Acid
C-attached to one II 38. The IUP AC name of given compound is
Rand one OH group 0
Acidic anhydride 5 4 3 2 I
(where, R - alkyl group)
(here, valencies of C are satisfied CH3- CH=CH- C = C- H
by one O and R-group)
pent -3-en • 1• yne
CH3
I 39. The structures of cyclopropane, cyclobutane and cyclohexane are
30. CH 3- ?- CH 3 or (CH 3)3C- OH is the fonnula of tertiary as

OH
butyl a lcohol as in it, - OH group is attached to tertiary carbon. H 2C- CH2
31. While naming ethers, larger alkyl group fonns the parent chair
I I
H 2C-CH2
and lower alkyl group fonns a part of alkoxy group. Cyclobutane
2 3 4
CH 3-0- C H-CH2 -CH3
itH3 Hence, the common group in cyclopropane, cyclobutane and
2- rrethoxybutane cyclohexane is - CH2 group.
32. According to IUPAC system, ether are named as alkoxy alkanes. I
40. First the longest continuous chain of carbon atoms is selected.
The large alkyl group forms the parent chain while lower alkyl
Now, numbered the chain from the side containing senior
group is taken with ethereal oxygen and forms a part of alkoxy
fi.mctional group ( i.e. the group placed above in the seniority
group.
table).
1
CH Cl
I 3
6 Is 4 3 2 1
CH 3 - CH2 - 0 - CH- CH 2 - CH2 - CH 2CI CH3- ? - CH2 - CH =CH- CH 3
2 3 4 5
2-ethoxy•S•chloropentane
H
33. The correct decreasing order of priority for the functional groups 5-chloro-hex -2-ene
of organic compounds in the IUPAC system is
- COOR > S03H > - COOR > COCI 41.
4~2

> - CONH 2 > - CN > - CH =0 s~

6
1,3,3-trimethylcyclohex- l-ene

2-ethoxypropane
The above compound is an ether and its name is written as alkoxy 3-chlorobutanal

alkane. Oxy is attached with the lower alkyl group. Hence, the The order of priority is - CHO > - Cl.
IUPAC name of above compound is 2-ethoxy propane. 43. 2-methylpropan-2-ol is tert-butyl alcohol.
H CH3
I 2 I 3 4 S I
35. H3 C- C- CH2 - CH2 - CH3 H3C- T -CH3
I
O- CH 2 - CH2 - CH3 OH
2- propoxy pentane
 Organic Chemistry Some Basic Principles and Techniques I 281
6 2
COCl
44.

©
7~1
52. Benzoyl chloride
3-ethyl-4, 4-dimethylheptane

3 2 I
45. TH2- ?H- COOH Cl
OH NH2
2-aminc~J-hydroxy propanoic acid 55. 6~~
5U B r
I 4

... 'Cl] Unsaturation (double bond) is given priority over halogen, then
lowest set of locants.

n
2 So, the correct IUPAC name is 3-bromo-1- chlorocyclohexene.
This compound contains 6 C-atoms, thus, corresponding alkane is I
hexane. Three bridges contain 2, 2 and atoms, respectively. Hence,
correct TUPAC name is bicycle [2, 2, OJ hexane. 56.
I 2 3 4 5 H 3C CH3
47. CH 3 - ?H- CH2 - CH 2 - CH3 4

Its TUPAC name is 3, 5-dimethylcyclohexene.

OC2H 5
2-ethoxy pentane CH 2.__________
0
57. The structural formula of epoxide is I _,.....--0.
CH 2
II
48. Here, keto (- C- ) functional group is given priority. Hence, the Thus, it consists of three membered ring with two carbon and
0 one oxygen.
II
IUPAC name is CH3 - C- <;:H-CH3
I 2 I3 4
CH3
3-methylbut.m -2-one
or 3-methyl · 2-but.mone

49. X-crown-Y, 18-crown-6 F irst nu mber X is the total number of C

and O-atoms in the ring and second number Y is the number of 59. ~
6r\4
oxygen atom in ring. HO 2

Carbon with - OH group is given C 1 thus it is

50. 3, 3-dimethyl-1-cyclohexanol.
3'~ 60. Select longest possible carbon atom chain, number it and name
4' 3 compom1d according to IUPAC rules.
1-cyclopropyl cyclobutane
H 32C CH3
In the above strucn1re, the smaller ring will be considered as a
substin1ent while larger cycle will be considered as main chain. \/
¢:
1
CHO CH CH2 CH 3
1 s 1 6 sl 4 31 2 1
6 2 N02 CH3 -CH 2 -CH 2 -CH- CH-C-CH2 -CH 3
51.
s :::::-... I 3 I I
4
CH 3 CH2CH3
3, 3-diethyl -4-methyl •5•( I' -methyl ethyl) •octane
OCH 3
4-methoxy-2-nitmbenzaldehyde Br
I

4½6
5
61. CH3 CH 2 C= CH- Cl
4 3 2 1
52. 2-bromo-1-chloro butene• I
3 :::::-.._ I
I 2 3 4
2
62. CH 3 - ~ - ? H- CH 3
0
I -cyclohexa-2,4-dienylethanone 8 CH3
6 5 4 3 2 I 3-rrethyl-butan -2-ore
53. CH3 - ?H- CH=CH- ?H- CH3
CH 3 OH
5-methylhex·3•en •2-ol
282 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Fission of Bonds and Electron

~ Topic 2
Displacement Effects
63. CH 3 - C- NHBr
N •bromoethanamide
1. In electromeric effect, there is complete transfer of Jt- electrons

64. <1> from one atom to other to produce temporary polarity on atom
joined by multiple bonds
" / Electrophile added > " + - /
Its IUPAC name is bicyclo [I , I, OJ butane. / C = C" Electrophile remoYed / C - C"
65. Neo hexyl chloride is a primary halide as in it, Cl-atom is attached
Therefore, there is no required partial charge on substrate (i.e.
to a primary carbon.
C-atom ).
CH 3
I 2. Nucleophi les are the species/substances containing atoms which
CH 3- ? - CH2- CH 2CI have atleast an unshared (lone) pair of electrons e.g. alcohols

CH 3 .. ..
(R- 0 - H), ether (R- O- R), ammonia ((N H 3), amines
I 2 3 4 5
66. H 3C - r= CH- ? H- CH 3 (R- NH2), water (H- R - H) and cyanides (R - C- N) etc.

Cl CH3 3. A monosubstituted benzoic acid is stronger than a monosubstituted

2-chloro-4-methyl -2-pentene phenol as former being a carboxylic acid. Among the given
I 2 3 4 5 6 substituted benzoic acids, or/ho-hydroxy acid is strongest acid
67. HOOC- CH2- CH- CH2- CH2- COOH although - OH causes electron donation by resonance effect
tooH which tends to decreases acid strength. It is due to a very high
stabilisation of conjugate base by intramolecular H-bond which
IUPAC name of the above compound is outweigh the electron donating resonance effect of - OH
3-carboxyhexane- I , 6-dioic acid. 0
eco-
CC
68. IUPAC name ofCH3CH2CHO is propan-1-al. COOH
~W I !
OH /4'- H

sh 0/

69.
6u
4-ethyl-3-methyl cyclohexene
The overall order of acid-strength of given four acids is
o,tho-hydroxybenzoic acid (pKa = 2.98) > Toluic acid pKa =
4.37) > p-hydroxybenzoic acid (pKa = 4.58) > p-nitrophenol
(pKa = 7.! Si
4. There are total 6cx - H to sp2 carbon and they all can participate in
CH3
hyperconjugation.
4 31 2 I
70. H 3C - C- CH =CH 2
I
CH 3

IUPAC name is 3, 3-dimethy l-1-butene.

Three strucures Two structures
71. Glycerol is a trihydric alcohol. It is CHpH- CHOH- CH2OH.
It contains three hydroxyl group. It is present in nature in oils and 5. Electron withdrawin group has - /-effect while electron donating
fats as its carboxylic esters. group has + /-effect. In CH 3COOH, the alkyl group (- CH3) due
to its greater +/-effect increases the electron density on oxygen
72. 3-chloro-2, 3-dimethyl pentane contains all the four 1°, 2°, 3° and
atom of the O- H bond. Due to this, the release of W ion in
4° carbon atoms.
acetic acid will be more difficult as compared to formic acid.
1° 1°

co
CH3 CH 3 COOH OH COOR
I I 2° 1°
CH3- C - C- CH 2- CH3
I" f" 13• and
CH3 Cl /4-
3-chloro-2-3-dimethyl pentane

73. CH3- T H- TH- CH3

CH3 OH are soluble in aqueous NaOH. Benzylic alcohol is less acidic than
3-methylbutan -2-ol water so not soluble in aqueous. NaOH.
 Organic Chemistry Some Basic Principles and Techniques I 283
o- 13. According to Lewis, electron acceptor compounds are called acids.
1 Therefore, compounds having tendency to accept electrons will be
R- C=O : In carboxylate ion, the more acidic. The correct order of acidic character is as follows:
negative charge is present on oxygen, a most electronegative OM~

9
element here, thus it is resonance stabilised.
HC=C- : Carbon is sp-hybridised so its electronegativity is
increased higher relative to nitrogen.

N H 2 : N itrogen is more electronegative than sp3-hybridised

::::,.__

OH
(A)
<

9 OH
(C)
C-atom. From the above discussion, it is clear that the order of the
stabi lity of conjugated bases is as
14. Hyperconjugation arises due to the partial overlap ofa sp3 orbital
RCOO- > HC= C > N H 2 > R- (a C-H <J bond) with the empty p-orbital of an adjacent
and higher is the stability of conjugated bases, lower will be basic positively charged carbon atom.
character. Hence, the order of basic character is as
Rcoo- < HC= c- <NH2 <R-
8. Inductive effect involves only displacement (and not
delocalisation) of o-electrons.
9. - Cl is an electron w ithdrawing,(i.e. - I showing) group. It
w ithdraws electrons when attached to the carboxylic acid and
decreases the electron density on the oxygen atom. This will
facilitate the re lease ofH + by making O- H bond more polar and
thus - Cl increases the acidity of acetic acid when attached at, 15. I > III > IT > IV
a position because of -/-effect. J
1O. Active methylene group

,----'--+ II kJ~ + M-effect, hyperconjugation (6 Hs) and

+ I effect (2 Me-groups)
H3C- CH2- C + CH2 C- CH3
II L ______ ,
+ M-effect, hyperconjugation (3 Hs) and
0 2, 4-hexanedione0 + I effect (I-Me group)

When methylene group (- CH2 ) is attached with two electron

w ithdrawing groups (like - CHO, C=O,
- COOH, - CN, - X, etc), its acidity will increase due to
~ Hyperconjugation (5 Hs) and + /-effect
- /-effect of the electron withdrawing groups. (2° carbocation)

11. A carboxylic acid is stronger acid than phenol, hence both III and

~~
IV are stronger acids than both I and II. Also IV has a methyl
group that gives electrons donating inductive effect and decreases Hyperconjugation (2 Hs) and + /-effect
the acid strength. Therefore, III is stronger acid than IV. Between (1°carbocation)
I and II, the dominant electron withdrawing inductive effect of
chlorine increases acid strength of phenol slightly, hence II is 16. Electron withdraw ing group stabilises the arenium ion
stronger of phenol slightly, hence II is stronger acid than I. o-complex at meta position.
Thus, the overall order is : 17. Mesomeric effect involves complete transfer of 1t or lone pair of
(a) III > IV > II > I electrons to the adjacent atom or covalent bond. Hence, it
12. Electromeric effect occurs only in the presence of attacking involves de localisation of pi (1t) electrons.
reagent. It operates in the mo lecules having multiple bond. Since, +
it exists only on the demand of attacking reagent, it is a temporary 18. Among the given species, G;H 5 N H 3 does not exert a resonance
effect. e.g. effect.
_ C ~ Attacking reagent

)c-°~ ~ )c- ~- (IT)

1 Stmcture IT is not possible because in it, nitrogen contains
H IOvalence electrons.
284 I Chapterwise & Topicwise Engineering Entrances Solved Papers

19. The rate ofreaction is influenced by the hyperconjugation effect Phenoxide ion is stabilised due to following resonating structures.
of group R. It depends on the electron donating power of alkyl
group (R). The electron releasing power of R-group depends on :o) :o :o

0-G-V-
the number of hydrogen present on o: carbon. The increasing
order of speed with R-group in the reaction is
CH3 H 3C
H 3C-{- < ) cH-< CH3-CH 2- < CH 3- e
n rn
CH3 H3C
i.e. rv < rrr < n < I
20. Dichloroacetic acid due to the presence of two electron
with drawing chloro groups (- l showing group) is more acidic
than acetic acid(+ l showing - CH3 group).
21. In homolysis, the covalent bond is broken in such a way that each JV
resulting species known as free radical.
27. Fluoro group causes negative inductive effect increasing
CH CH - Cl Homolytic CH CH + ·c1
3 2 fission 3 2 ionisation, thus 0.1 M difluoroacetic acid has highest electrical
conductivity.
22. - NH2 has + R-effect, it donates electrons to the benzene ring. As a
result, the lone pair of e lectron on the N-atom gets delocalised over
the benzene ring and thus it is less readily available for protonation. F-+-z-+-i -+-0-+-H
Hence, aniline is a weaker base than cyclohexylamine.
ffi EB t
5-6-◊
e HBr
28. R3N-+-CH =CH2 -
e
Due to R3N-(e-withdrawing tendency) carbocation will

S~O
appear farther to that (terminal).
Hence, product is R3N-CH2-CH2Br.
29. In homolytic cleavage, covalent bond is c leaved in such a way
that each atom takes its shared electrons with itself and free
radicals are formed.
Resonance in aniline
Homolytic fission •
23. Orbital interaction between the cr-bonds of a substituent group A • • B -------> A + s•
Free radicals
and a neighbouring n-orbital is known as hyperconjugation.
30. Homolytic fission is favoured by sunlight. In it, each bonded
H H+ ~
atom takes away its shared electrons and thus free radicals are
H- t - CH=CH 2 H H- C =CH-CH 2
I I produced.
H H
(I) (II) Cl-Cl~ Cl° + c 1·

H e H e 31. The order ofhomolytic bond dissociation energies ofCH4 , C2H6

H H-tH+=CH - CH2 H H+t=CH- CH2

I
and CH3Br is as
CH 4 > C2H6 > CH3Br
H
(IV) t,H (kcal/mot) 105 100 70
(UI)

24. Two positive charges present at the adjacent place, elevates the 32. Chlorobenzene is o, p directing in electrophilic substitution
energy, thus lowers the stability most. reaction. The directing influence is explained by+ M of Cl-atom.
25. + I-effect is shown by -CH 3while - l effect is shown by - Br,
-Cl and -N0 2.
26. Phenols are much more acidic than alcohol due to the stabilisation
ofphenoxide ion resonance.

6H-6
phenol phenoxide ion
+if
+ M--effect of chlorine atom
 Organic Chemistry Some Basic Principles and Techniques I 285
33. ·: C-H bond in toluene has partial double bond character due to S. The order of stability of carbocation
resonance.
:. C-H bond in toluene has less energy as compared to others.
34. The octet of all atoms is complete in structures a and b. The molecule in
which all the atoms have completed octet is more stable than atom
which have incomplete octet. Larger the number of resonating
structures, larger will be the stability, thus structures a and bare stable.
6 CHl > CH, - CH-CH,> CH, - CH, - CH,

Benzyl
(more resonance
s tablised)
Allyl
(resonance
stabilised)
Propyl
(stablised by
+ /-effect of
CH2CH3 group)
lT1 II
In strucnire (d), the electron deficient of positive charged carbon is
duly compensated by one pair electrons of adjacent oxygen atoms 6. PhCI CHBr ' eu0- PhC-CIBr ~ Ph CCI
while such neighbour group support is not available in structure (c). - tBuOH
Hence, structure (c) is least stable in comparison to strucnrre (d). 7. Larger the number of phenyl groups or methyl groups Iinked
35. In toluene, (-CH3) group is present which has + /-effect and to a carbocation greater w ill be the stability ofa carbocation.
increases electron density at ortho and para position. While in
Thus, the correct order of stability will be
sulphonation,-SO 3 acts as an electrophile. Therefore, it (-SO3H)
Ph H
attacks on ortho and para position readily.
I I
Ph - C - CH2CH3 > PhCH2CH2- C- Ph
Topic 3 Reaction Intermediates + +
(I) (II)
1. Nucleophiles are those substances w hich can donate a pair of electrons.
Me
They can be neutral or negatively charged. The nucleophilic power
depends on the tendency of species to donate the electrons. Due to the
H I
> Ph 2CH- C+ > P h - ? -~H2
presence of + !-effect, it increases. Hence, higher the + !-effect,
higher the nucleophilic power.
I
CH Ph
3 (IV)
Further, C 2H 5SH is more nucleophilic than CH 3Coo- , CH 3NH 2 (Ill)
because S being less electronegative than O and N has a more tendency
to donate their lone pair of electrons. 8.
M' .,,,.--H
/C=C"--. has 6-hyperconjugate forms while
2. Due to the presence of phenyl group, carbocations (I), (2) and (3) are Me H
more stable than (4). Moreover presence of phenyl group, increases MeCF.:&.__ / H
stability of carbocation through delocalisation of electrons. Hence, / C=C"--. has 2-hyperconjugate forms.
carbocations (I) and (3) are more stable than carbocation (2). Presence H H
of- OMe group i.e. + M- group is more active than - Me group i.e.+ l
Therefore, MeiC=CH2 is more stable than
group. Hence, carbocation (2) is more stable than carbocation ( I).
MeCH2 CH=CH2
Hence, the correct order is 4 < 2 < 3 < I
3. Stability of carbocation depends upon the number ofhyperconjugative
9. Nucleophilic strength increases down a column of the
Periodic Table (in solvents that can have hydrogen bonds,
structure. More the number of hyperconjugative structures (i.e. more
such as water, alcohols, thio alcohols).
the number of hydrogen atoms attached directly to a-carbon atom)
more is the stability of carbocation. Nucleophilic strength <
Thus, the order of stability of given carbocation is
CH 3 Basic stregnth >
I 6
Thus, RS is more nucleophilic but less basic than RO.-
CH 3- C+ >
I (6a· H hyperconjugative stnx:ture)
IO. When the nucleophilic site is the same, nucleophil icity
CH3 parallels basicity. It means more basic the nucleophile,
m stronger is the nucleophile.
(9 - o -H,9
hyperoonj ugative structure)
H 2N(I) is the most nucleophilic.
CH3
+ I + 0 o-
CH 3 C~ 2 CH2 > CH3- ? - CH2 11 I +
(2- o -H 2-hyperconjugative CH H 2 N-NH-C-NH 2 f---4 H 2N-NH-C =NH2
structure) 3 I TI III
TV
Noo- H. So, no
hyperconjugative structure
+ o-
Thus, (CH3 ) 3 C CH2 (IV) is least stable carbocation among the given.
SbCI s +
+ I
f---4 H 2 N - NH = C- NH2
4. CI- CH-CH 3 ------? Ph- CH- CH3 + SbCl6
I Toluene Carbocation
(planar)
0
Ph(d) II
Ph- ?H- CH3 + SbCls Further more the NH2 group away from the - C- group is
not involved in resonance. H ence, its lone pair is readi ly
Cl available.
(d and /) mixture
286 I Chapterwise & Topicwise Engineering Entrances Solved Papers

11. Carbanions contain even number of valence electrons and thus, O- CH3 is also an electron donating group, thus it w ill increase
show diamagnetic behaviour. the stability of carbocation, hence the correct order of stability
CH 3 isC > B > A.

12.
+
C2H 5 and CH3-T 1(1)
are stabilised by hyperconjugation.
17. An organic ion with a pair of available electrons and a negative
charge on the central carbon atom is called a carbanion. E lectron
attracting group (-CN, C=O) increases stability and
CH 3 electron releasing group (-CH 3) decreases the stability of
EB carbanion. In (CH3) 3C-, three - CH3 groups (electron releasing
In ¼ H sCH2 benzyl group is resonance stabilised. Tn the triphenyl
methyl carbonitun ion, the 1t-electrons of all the three benzene group) are present, so it is least stable.
rings are delocalised w ith the vacant p -orbital of central carbon + H+ +
atom. So, it is resonance stabilised. Therefore, it is the most stable 18. (CH3hC- OH _ H (CH 3) 3C
2O
of the given carbonium ions. Also, more the number ofresonating Tertiary alcohol 3 ° carbocation
structures more will be the stability. Hence, the most stable is (more stable)
carbonimn ion is (C6 H 5 ) 3 C + . + H+
CH 2=CH- CH2- CHpH -
13. Hydride shift from C-2 w ill give the most stable resonance, - H20
stabilised carbocation as +
CH 2 =CH-CH 2-CH 2
O
I carbocation
I (D+ '4
S
H3C - C - C - C - CH3 -➔
(less stable)
Increasing order of stability of carbocation.
3
I I I IO carbocation < 2° carbocation < 3° carbocation
OH H CH3
19. Free radicals have unpaired electrons, but are neutral chemical
H H species and are highly reactive.
I + I
H 3C - C- C- C- CH3 ~ CH 3 + CH3 -➔ CH 3-CH 3
(. I I I 20. Free radicals stability
.OH H CH3
H H
I I
H 3C - C- C- C- CH3
Highly stable by delocalisation of electrons by 3 Ph groups.
I+ I I
:o H CH 3
'--H
(A resonance stabilised carbocation) 9-hyperconjugative hvdrogens and + /.effect

,S
14. Cl 21. Resonance and inductive effect decide stability of carbocations.
I
6CH, 6CH, CH,6CH,
EB EB EB EB
CI - C- >
i - M-effect and - !-effect of
Cl - Ph group
It involves ~d1t backbonding
CH 3
(I) (II) (Ill)
CH 3 I (resonance (no resonance) ( resonance and (resonance and
I > CH 3 - C- only) less+ /-effect
by one Me group)
more+ /-effect
by 2 Me groups)
> CH 3 - CW
+ !-effect is exerted by
I
two - CH3 groups
CH3 : . Correct order of stability is II < I < III < IV.
destablising the carbanion + /-effect is exerted by three -CH3
groups, thus destablises the carbanion 22. Ary! carbonilUn ions are more stable than alkyl carbonium ions. The
order of stability of carbocation is. Triphenyl methyl > diphenyl
15. Number of hybrid orbitals =Number ofcr-bonds + Number of fps methyl > benzyl > ally I > 3° > 2° > I O > methyl carbocation
23. Bromination of alkanes in the presence of sunlight involves the
cr-bonds = 3 formation of free radical. e.g.
fps= 0 CH4 7Br2 CH3Br
Mechanism
: . Number of hybrid orbitals= 3 + 0 = 3
2
Hence, hybridisation is sp and geometry is planar. Initiation Br- Br ~ Br" + Br·
Propagation CH4 + Br" -➔ CHj + HBr
16. The dispersal of the positive charge stabilises d1e carbocation. More
CHj + Br- Br -➔ CH3Br + Br"
the number of alkyl groups greater the dispersal of positive charge
Termination Br" + Br" -➔ Br2
and therefore, more the stability of carbocation, thus C 2 > CH; . f½
 Organic Chemistry Some Basic Principles and Techniques I 287
24. Phenol reacts with chloroform and NaOH to give o- hydroxy
benzaldehyde or salicylaldehyde. In this reaction,
dichlorocarbene (: CCl 2) electrophile is generated. This reaction
is called Reimer-Tiemann reaction.
OW+ CHC1 3 - HOH + : CCl3
Un>table

: CC13 -➔ Cl- + : CC1 2

Dichlorocarbene

Topic 4 Isomerism
1. The combination of name for possible isomeric alcohols with 5. Compounds which do not show geometrical isomerism has one
molecular formu la C4H 10O is/are carbon attached with double bond has same groups attached
(- CH3). The given compound shows optical isomerism because
Formula Names it contains asymmetric carbon.
n-butyl
alcohol/n-butanol/butan -1 - ol

CH3- ? H- CH2- OH isobutyl alcohol/2-methyl

propan -1- ol
CH3
Mirror image
CH3- CH2- ? H- OH Secondary butyl alcohol
butan -2 -ol 6. Geometrical isomerism is reflected by those molecules which
CH 3 contains(= ) bond. For geometrical isomerism, it is essential that
the group attached to the (=)bond are different. Geometrical is
Tertiary butyl alcohol/ tert
isomers exists in two form, - Z (Zusamann) type cis form and
butanol/
2- Methyl propan - 2-ol - E (Eutegamann) type trans form.

00 OOH, /H~
C=C 3 4
(b)H / 1 2'cH - CH3(a)
2. The conformations of the given compund are as follows I
C6Hs

w
Cl CH3 3-phenyl-1-butene
B~Cl
Br- + - -CH3 = Cl- + - -Br Same group (H) is present on the C - I atom
B,
Br- t - -Cl Br- t - -Cl
CH3 CH3
H3C CH3

Stable conformers (with µ* 0)

Br Same group H present on C .. 1atom
Br~Cl I 2 3
B,~ C l B,~CI
(c) ¼ Hs- r = r - CH3CH 1, 1-diphenyl-l- propene

CH3 V Br Bryc1 Cl- Y CH3 ¼ H sH

CH3 CH3 CH3 Same (¼Hs) group present on C - I atom
H
(Me - Me) gauche (Br - Me) gauche (Cl -Me) gauche I
These three have non-zero dipole moment due to (d) C6H5- CH2 - C = CH- CH3
I - phenyl - 2 - butene
non-cancellation of all dipole moment created by C- Cl and
C- Brbond.
___,_
3. CH3- rr- CH2- rr- OC2H5 ..---
0 0
(Keto)
 288 I Chapterwise & Topicwise Engineering Entrances Solved Papers

7. The number of possible strucn1ral isomers of butene are

CH3 - CH2- CH=CH 2
Butene- I H~OH~ 'H , ~OH
CH3 - CH=CH- CH3 ~u
Butene-2 HO~H
HO
Cl
2-methylpropene-1
p
Cl
So, the nwnber of isomers are three.
8. D isymmetric object never superimposed on its mirror
image.
:=f=g:
CH3
9. A carbon atom which is bonded to four different atoms or p
group of atoms in molecule is known as chiral carbon M and P are superimposable mirror images, hence enantiomers.
atom.
a CH3 H

Thus,
I
d-T- b chiral carbon atom
HO H

-~ HO

carbon atom.
C

CH3
I
So, Br CH 2 CHCH2 Br is a compound without a chiral

1 O. Converting all of them into fischer projection.

HO

* Cl
Q
H HO H

Cl
HO- + -H
H+ -OH
Cl CH3

-----> ~g=f=:
CH3
M and Q are non-identical, they are distereomers.
Q

11. CH 3- CH2 - CH- CH 3

I
M M CH3
2-methyl butane

AH
H'-r(>H C H3
HO~H
H+ -OH
Cl
I
+ CH3- CH2 - ? - CH 3
Cl
Cl N N CH3
(Tl) m
Since, M and N have - OH on same side and opposite side
respectively. They cannot be mirror image, they are + TH2- CH2- ?H- CH3
diastereomers. Cl (N) CH3
Cl I and III have chirality (*). Thus, in all four (including enantiomers)
✓ OH
Y8~
OH H Cl optical isomers are obtained.
0 - Ho _ Ho- + -H 12. The two propenyl group attached to l , 2 position of carbon in
Cl HO+ -H cis form.
CH3 CH3 CH3 CH =CH
CH 3- CH=Cff '---CH=CH- CH 3
13. Geometrical isomers have same structural formula but differ in spatial
Mand O are identical.
arrangement of group around the double bond.
Note F ischer projection represents eclipse form of sawhorse H 3C- C- H CH 3- C- H
projection. By comparison purpose, similar type of II II
eclipse conformers must be drawn is both vertically up H 3C- C- H H- C- CH 3
or both vertically down. (cis-form) (1rons-fom1)
 Organic Chemistry Some Basic Principles and Techniques I 289
COOR HOOC 20. Cis-alkene on halogenation produces racemic mixture.
I I 21. The compounds with sp2-hybridisation lie in the same
14. H- C- OH HO- C- H
I I plane. In both (b) and (c), all the atoms are present in one
CH 3 H 3C single plane.
(+) latic acid H lactic acid sp2
Both are optical isomers because they rotate the plane of polarised light /2-:.-:--sp2 H"-. JI'
H - C==C - C~ H C=C=C
in opposite direction. I+-- Straight --->-1 ~ C/ C/~ straight --+I
0 H O O- H 0 I
II I II I II H
15. CH3- C- ? - C- OC2H 5 f--------7 CH3 - C = ? - C- OC2
In (a) I, 3-butadiene, conformational change is possible
H H between C2- C3 bond in which atoms will be present in
(Keto form) Eno! form more than on s ingle plane.
More stable due to intramolecular H-bonding. In (d) allene, the terminals H- C- H planes are
16. Isomers ofC4H 10 are as follows: perpendicular to one another.

(i) CH3CH 2 CH 2 CHpH (ii) CH3- ? H- CH2CH3 22. ~ - ~Cl+

Butanol - 1

~ ++ +/'y'
OH (I)
Butanol -2

CH 3 CH 3
I I
(iii) CH3- CH - CH 2 - OH (iv) CH3 - ? - OH
2,. methyl propaool • I l____c1
CH 3 (II) (III) (IV)
2-methyl propan .2,.ol
I has one chiral carbon= two isomers, i.e. two enantiomers.
(v) CH3CH 2 - O- CH2CH3 II has two chiral carbons and no symmetry= four isomers.
Diethyl ether
III and IV have no chiral carbon, no stereoisomers.
(vii) CHp- CH 2CH2CH 3 0
Methyl propyl ether II
23. CH 3 CH 2 - CH2 - C- CH3 ___,_
17. For optical isomerism, there must be a chiral C- atom
keto form
H H H H OH
I I I I I
H- T- T_ T _ T- H Butan -2-ol CH3CH2 CH 2 - C=CH2
(enol form)

18.
,---!/CH3
l___J
H OH H H
24.
B,t {CH'
'"¾-CH3 trans- l-bromo-2-methyl cis-1-bromo-2-methyl
cyclobutane (2 optical isome rs) cyclobutane (2 optical isomers)
Here, C I and C 2 are asymmetrical, due to which it is a chiral molecule.
19. Ibuprofen is a racemic mixture of both Rand S enantiomers. Total optical isomers are 4.
Since, reactant is cis-alkene, therefore product will be racemic. of the 25. The stability order of conformation of cyclohexane is
reactant is trans, then the product will be meso compound. chair > twist boat > boat > half chair.
Hence, half chair is less stable due to torsional and angle
strain.
26. Only compounds containing central carbon-atoms exhibits
optical isomerism. The carbon which is attached to four
different-substituents is said to be chiral in nature. Among
the given compounds, only compound (b) exhibits optical
isomerism because the central carbon is attached to four
different substituents, hence it is chiral, therefore optically
active.
27. 2-butene exhibit rotamers. Rotamers are the isomers
S (+) Ibuprofen formed by restricted rotation.
290 I Chapterwise & Topicwise Engineering Entrances Solved Papers

28. Cl¼ can have five cyclic isomers

[>=, [>-, [>-, o,[SJ CH3CH2CH2 - SCH3,

Methyl proply thioether
CH3- S-C- CH 3
I
CH3
Methyl iso-propyl rhioether
H 35. The total number of cyclic isomers are six as shown below
I
29. CH 3- CH 2 - f - CH=CH2
CH 3
3-methyl -1-pentene
(It has one chiral centre.)

30. Angle strain, a = _.!. ( I 09°28' - e]

2
In case of cyclopropane,
e = 60°
a = _.!. (I 09°28' - 60°) = 24 °44'
2
36. Geometrical isomers are shown by those alkenes in which each
31. Enantiomers are non-superimposable mirror images, e.g. lactic doubly bonded carbon atom is attached to two different groups/
acid substin1ents.

H 3C H

H3C>=<H
propene 2-methyl propene cis-2-butene
(no geometrical isomer (no iwmer)
due to same substiluent)
Diastereomers are non-superimposable and are not the mirror
images of each other. Moreover, meso form has plane of
symmetry. H,C>=<CH,
32. The structure of D - glyceraldehyde is as
H3C H
CHO 2-methyl-2-butene
(no. iwmer)
H + - OH
CH20H S 4 3 .2 I
37. The given compound is C H 3- CH = C H- CH- CH3
The priority of groups is decided by the following rules: I
OH
(i) Atom hav ing higher atomic number gets higher priority.
Number of stereoisomers = nu mber of optical isomers + number of
(ii) If the priority cannot be decided by rule l , then the next
geometrical isomers.
atoms are considered for priority assignment.
In this compound, number of optical isomers= i = 2,
(iii) Where there is a = bond or == bond both atoms are 1
H number of geometrical isomers = 2 = 2 ,
number of stereo isomers = 2 + 2 = 4
I
considered to be dup licated or triplicated (- C=O has 38.
higher priority than - CH20H).
Hence, the correct order of priority of groups in
D-glyceraldehyde is as :
OH ( l ), CHO (2), CHpH (3) and H (4)
CH3
I
33. H 3C- C- Br and CH3CH 2CH2CH2Br are chain as well as
I
CH3
position isome rs .
34. Compounds having biva lent functiona l group (like ~O,
-----
- 0 - , - S- etc) with atleast 4 carbon atoms (in case of
ether and thioether) or atleast 5 carbon atoms (in case of
R-form S-form ; R- form
ketones) exhibit metamerism.
 Organic Chemistry Some Basic Principles and Techniques I 291
44. The structural formula of fumaric acid is
r!H3© CDT ~
CD
~,T &,,
H-C- COOH
rrr. Cl --=ro- H -
II
(trans-butane- I, 4-dioic acid)
HOOC- C- H
g H2CH3 45. 2-butene contains a double bond and the groups attached with
@ ;R- fom1
double bonded carbon atoms are different, it exhibits
geometrical isomerism and the geometrical isomers are as

©
TV. H ° I O H -
~~3 CD H3C"-
H /
/CH3 H3C"-
C=C,
' CI H
/H
/C=C,
'CH3
cis-form trans-form

CH2CH3 46. 11-pentanol, 2-pentanol, 3-pentanol, 2-methylbutanol,

CD 2-methylbutan-2-ol, 3-methylbutanol, 2, 2-dimethylpropanol
@ and 3-methyl butan-2-ol (8 isomers)
COOH 2

ffi
H: rH ~H
V. H 3C NH2 ;S-fonn
2
Q)~ HOOC
H o,
©
39. The isomeric alkanes having the molecular formula C 5H 12 are as
COOH

(i) ~
1J•pentane
(ii) N iso-pentane
(iii)
neo-,pentanc
48. When the groups with higher priority (i.e. with high atomic
number) are present on same side of double bond, then the
(2-methyl butane) (2, 2-dimcthyl propane) configuration is Z but when present on opposite side of double
bond, the configuration is E.
. Cl "....,. . / Br
(1) /C=~
H F
(Z)
Since, in the above structures, position of Cl is different, these are
position isomers, which is a type of structural isomerism.
(Priority : Cl > H and Br > F)
41. An equimolar mixture of the enantiomers (dextro or laevo forms) is Cl F
called racemic mixture.
It is represented as di-form or± form and is optically inactive due to
(ii) )c=c(
H Br
external compensation. Separation of racemic mixture into d-and (E)
/-forms is called resolution.
(Priority : Cl > H and Br > F)
42. The carbon atom for w hich four valencies are satisfied by four
different groups, is termed as chiral carbon atom. The structures of Br"....,. /CH3
the given compounds are as (iii) ,.,..-C=c(
H H Cl/ "-H
I. I. (Z)
(a) CH3 - C- OH (b) CH3CH2 - C- COOH (Priority Br > Cl and CH 3 > H)
I I Hence, compounds (i) and (iii) have (Z)configuration.
COOH Cl
Lactic acid 2-chlorobutanoic acid 49. According to Cahn-Ingold-Prelog sequence rules, the priority of
groups is decided by the atomic number of their atoms.
COOH
When the atom (which is directly attached to the asymmetric
I carbon atom) of a group has higher atomic number, then the
H - *C - OH CH2COOH
group gets higher priority. Groups with atoms of comparable
(c) I* (d) I atomic number having double or triple bond, have high priority
H- C- OH CH2COOH
than those have single bond.
I Succinic acid
COOH Hence, the order of priority of groups is

.
Tartaric acid

(where, C = c hiral carbon atom)

-OH > -COOH >-CHO> -CHzOH
50. The structures of maleic and fomaric acids are given below
Hence, succinic acid does not contain any chiral carbon atom. H-C-COOH H-C-COOH
43. The number ofstereoisomers = 2" II II
H-C-COOH HOOC-C-H
(here, n = chiral carbon atom) T hus, number of stereoisomers (maleic acid) (fumaric acid)
= 23 = 8 molecular forrnula (4 H 40 4) molecular formula (CiH4 0 4)
292 I Chapterwise & Topicwise Engineering Entrances Solved Papers
The structures of fumaric and maleic acid suggest that they are 53. Isomers ofC4H 100 are as follows:
geometrical isomers because they have same molecular formula
but different spatial arrangement of atoms around a double bond. (i) H 3C-CH2 -CH2-CH2-OH
butanol - 1
51. Twelve in all (ii) H 3C-CH- CH2- CH3
(a) Six geometrical isomers
6H
. CH3CH2~ / Cl butanol-2
(1) /C=C~ CH3
H H (iii) CH3- 6H-CH2-OH
2-methyl propanol-1
.. CH3CH2~ /H
(11) /C=C~ CH3
H Cl (iv) H 3C-6-0H
H3C"-. /CH3 I
CH3
(iii) )c=C~ 2-methyl propan-2-ol
H Cl
(v) H3C- CH2- O-CH2-CH 3
Diethyl ether

/CH3
(vi) H3C-O-CH"'-.
CH3
Methyl isopropyl ether

(vii) o"'
/CH3

CH3- CH2- CH3

Methyl propyl ether

Hence, three isomeric ethers are possible.

54. Compound CH 3-CHCI-CH2-CH3 shows optical isomerism
due to the presence of chiral carbon atom.
H chiral carbon atom
I
CH3- c·- cH2-CH3
I
Cl
H
55.
(viii) CH3_.!6-CH=CH2

:=f=::
I
Cl
(c) Four structural isomers
Cl
CH3
(ix) CH3CH2-6=CH2 Butane-2-3-diol

CH 3 where, C = asymmetric C-atom

I It is a symmetrical molecule, so the number of optically active
(x) CH3-C=CHCI
stereomers = 2" - 1
CH2CI
(n = number of asymmetric C-atom) = 22 - 1
=21 = 2
(xi) CH3-6=CH2
56. In methoxymehtane (CH3OCH 3) and ethanol (CH3CH2OH)
(xii) CICH2-CH2-CH=CH2
,functional groups are different but both have similar molecular
52. To be optically active, compound or structure should posses a formulae.
chiral or asymmetric carbon atom. Thus, 1-chloropentane is not
chiral. Thus, these are functional isomers.
 Organic Chemistry Some Basic Principles and Techniques I 293
If same groups or atoms attached with double bond bearing
carbon, then alkene does not show geometrical isomerism.
H "- / Br H"- /Br
C C
II II
cis form C, C
H/ 'Br Br/ "-H
.. CH3CH2~ / H
(11) /C=C~ 60. The possible primary amine with the fonnula C4H 11N are
H Cl (i) CH 3CH 2CH 2CH 2NH 2
trans form
CH3
2 geometrical isomers
I
(ii) CH 3-CH-CH 2-NH 2
CH 3
I
(iii) CH 3-C-CH3
I
NHz
(iv) CH3-CH 2- CH-NH 2
I
CH3
trans form
2geometrical isomers
61. C 5H 8 has three possible alkynes. These are
CH 3CH 2-CH2C=CH, CH3CH2C=C-CH3
Pent -1-yne Pent-2-yne

CH 3
CH 3- 6H-C=CH
3-methyl but-1-yne
62. The compounds which contain active methylene group at the
cis form adjacent position of carboxyl group show tautomerism.

o=O=o
2geometrical isomers

CH,~CH-!~CH,] 2oprical isomern

Number of optical isomers = 2n = 2 1 = 2
Hence, total number of geometrical isomers= 6
Total number of optical isomers = 2
58. Those compounds which contain two or more asymmetric carbon
atoms but are optically inactive due to the presence of plane of
symmetry, are called meso compounds. Meso compounds are
optically inactive due to internal compensation.Out of the given
compounds, only 2,4-dibromopentane has a plane of symmetry,
so it is a meso compound.
CH3
I the fact that its bonds are not at 109.5°. It also has torsional strain.
~ y- Br
H-C-H
I
H---C- Br
I has a carbon atom attached to four different atoms or groups.
CH3
2, 4-dibromopentane (mew co"1)0und)
59. Due to restricted rotation about double bond, the alkene s hows
geometrical isomerism because the relative position of atoms or
groups attached to the carbon atoms of the double bond get
fixed.
This compound does not contain active methylene group, hence
does not exhibit tautomerism. Moreover, this compound is highly
stable due to extensive cross conjugation.
63. The main conditions for exhibiting geometrical isomerism are :
(i) Presence of double bond.
(ii) Presence ofdifferent groups on same double bonded carbon.
(iii) Presence of atleast one similar group on adjacent double
bonded carbon atoms.
3 2 I
:. C3J-4(CH 3-CH=CH 2 ) does not exhibit geometric
isomerism due to the presence of same group on double bonded
carbon atom (C1).
64. Planar hexagon confonner has considerable angle strain due to
Due to the presence of these strains, planar hexagon conformer of
cyclohexane is least stable.
65. Optical isomerism is shown by an asymmetric carbon atom which
So, butanol-2 is optically active.
H
H 3C-CH 2-6-CH 3
I
OH
butanol-2
294 I Chapterwise & Topicwise Engineering Entrances Solved Papers

66. In 3
69.\)<J
;,=f=~' CiHs
Chair form is unsymmetrical due to the absence of any element of
symmetry. Two chiral centres, but plane of symmetry within
molecule ⇒ optically inactive
70. Tautomerism It is functional isomerism in w hich the isomers are
readily interchangeable and maintain a dynamic equilibrium with
Priority of groups for Ci carbon is Cl > C 3 > CH3 > H. each other.
3 OH

0 - C H = 6H ~ o - CH CHO 2

I ~
2
4 >----+------< 1---->-
2- ---1 3 Enol form Keto form

71. (+)and (-) tartaric acids do not possess any element ofsymmetry.
72. C hiral compounds w hich have one chiral centre. All four atoms
2 4 or groups attached to carbon are different. Thus, Tand TT are chiral
S-configuration i.e. S
compotmds.

Priority of groups for C-3 carbon is 73. The structure of 2, 3, 4-trichloro pentane is
Cl > C -2 carbon > CH 3 > H H H H H H

2
) @ '~ H-t-t~t-e-t-H
I I I I I
H Cl Cl Cl H

03
>----+-----< 4 ~ 1---->-
3- ---1 3
Hence, two chiral carbon atoms are present in
2, 3, 4-trichloropentane.

0 74. Ethyl alcohol shows functional isomerism w ith dimethyl ether.

CiH5 OH CH3- O- CH 3
3 Alcohol Ether
75. Geometrical isomerism is shown by C=C only when identical
S-configuration i.e. 3S
groups are not present on the double bonded carbon atoms.
CH 3 76. Molecular formula C 2BrClFT six isomers are possible.

Br2 , CCI 4
I
H- C- Br
anti-addition I
trans-2-butene H- C- Br
I
CH 3
meso form
Number of stereoisomers for meso compound= 2n- 1 = 22- 1 = 2
(Z) (Z)
(here, n = number of chiral C-atoms)
68. The molecule, which is optically active, has chiral centre, is 77. Acetophenone oxime can show geometrical isomerism.
expected to rotate the plane of polarised light.
H 5 C6 "- /CH 3 H 5C 6"- /CH 3

HO+H CH2OH
HO/
N
C
II
\J
syn.- fonn
a
C
N
II

anti- form
"-oH

One chiral centre ⇒ optically active 78. Ethers show functional isomerism with alcohols.
79. (a) CH3-CH-CH2CH3
I
Cl
One asymmetric carbon atom, forms d and /-optical isomers.
 Organic Chemistry Some Basic Principles and Techniques I 295
(b) Two asymmetric carbon atoms, forms d, land meso forms. 86. The different arrangement of atoms in space that results from the
carbon-carbon single bond free rotation by 360° are called
CH 3
conformations or conformational isomers and this phenomenon is
H- C- *ICl called conformational isomerism.
Plane of ______ -+---___ _ 87. In CH3CHpH, there is intermolecular H-bonding, while it is
s y m ~ H - *C - CI absent in isomeric ether CH30CH 3
I Larger heat is required to vaporise CH 3CH20H as compared to
CH 3 CH 30CH3, thus (a) is incorrect.
Meso due to internal compensation CH 3CH 20 H is less volatile than CH30CH3, thus vapour pressures
are different, thus (b) is incorrect.
Boiling point ofCH3CHiOH> CH 30CH3, dms (c) is incorrect.

Dens1ty - -, due to 1"dea1be hav1our

. =-Mass . .
at a given temperature
Two asymmetric carbon atoms but do not have symmetry. Hence, Volume
meso form is not formed. and pressme, volume and molar mass are same. Hence, they have
.
(d) CH3-CH- COOH
same vapour density.

I 88. HO-CH2-CH2-F
OH
H
One asymmetric carbon atom, meso form is not formed.
80. CH 3- ,CH- -<] contains asymmetric carbon, thus optically H
I
CH 2 CH3
active. H
81. Lactic acid obtained in the given reaction is an optically active
compound due to the presence of chiral C-atom. It exists as d and I
forms whose ratio is I : I. Gauche conformation is comparatively more stable due to
3 hydrogen linkage in between F and H (at 0-atom), hence order is
CH ""
/C=O + HCN ---t Eclipse, Anti (staggered), Gauche.
H 89. The given compound form two geometrical isomers and two
optical isomers.
fH3 I
CH 3
H-C-OH + HO- C -H

82. Isomers of propionic acid are as

I
CN
50% L- isomer
I
CN
50% D- isorner
90.uLCH3

I , 2-dimethyl
Q CH3
None

cyclohexane 3-methyl
0 0 cyclohexene
II II contain two, and one asymmetric carbon atoms, respectively .
CH3-C-OCH3 H- C -OC2Hs
Methyl ethanoate Ethyl formate 91. Pentene-2 exhibit cis and trans-isomerism.
83. Metamers of ethyl propionate are as 92. Two isomers
CH3COOC3H 7 , C 3H 7 COOCH 3 CH 3-CH-CH 3
84. CH3CHOHC2H 5 is optically active because it has chiral c• -atom
I
CH3
H /so-butane

CH 3-<'.:~C2H 5 CH 3-CH2-CH 2- CH3

6;; Chiral carbon atom
11-butane

93. The structure of isomers form C2H 2Br2 are

85. The compounds which differ in the nature of carbon chain are
called chain isomers, e.g. H"-. / H
CH 2= CBr2; / C = C"-.
CH3-CH2-CH2-CH2-CH3 , Br Br
11-pentane cis-isomer TT

'rH3 CH3
CH 3-C:H-CH 2 - CH 3 H3C-6-CH 3
iso-pentane I
CH3
11eo-pentane
296 I Chapterwise & Topicwise Engineering Entrances Solved Papers

95. Number of meso structures in compound having odd number of 102. n -pentane and 2-methyl butane are constitutional isomers or

chiral carbon atoms and symmetrical molecule= i~ -¾) chain isomers or skeletal isomers.
103. A compound could be optically active only when it contains,
Given, n= 5 atleast one asymmetric carbon atom or a chiral centre.
:. Number of meso forms= 2512 - 112
= 22 = 4 CH3"-•/H
H3C C
96. 2-butanol is optically active as it contain a chiral carbon atom. "-c = c/ "-cooH
H3C/ "-H
CH2
I 104. The isomerism which arises due to rotation about a C- C is
CH 3- CH 2 --C-OH
called conformational isomerism and the isomers are called

97. Propanal and propanone are functional isomers

* conformational isomers or rotational isomers or conformers.
105. 2-pentanone and 3-methyl-2- butanone are chain isomers because
they differ in carbon skeleton.
Hp ,
/ C=O, CH 3CH 2CHO CH3CH 2CH2COCH3
H3C 2-pentanone
98. There are four structural isomers are possible for C4H 9 CI
3-rnethyl -2-butanone

(b) CH3-CH 2-TH-CH3 106. Tautomerism is a dynamic isomerism because two forms (keto
Cl and enol) of substance cannot be separated, thus, they are in
dynamic equilibrilm1 with each other.
Cl 107. When -OH group of lactic acid is replaced by H, then chiral
(c) CH3-CH-CH,CI (d) CH3- 6 -CH3 carbon is lost.
I - I
CH3 CH3
~

CH3
Lactic acid
H- ~~OH
99. 'r :. Its optical activity is lost.
H-T~OH . .
108. CH3-CH-CH-CH 3
CHO
I I
2
Cl Cl
Possible number of optical isomers = 2n = 2 = 4
There are two chiral C-atoms (*).
100. The structure of butane-2, 3-diol is as Thus, optical isomerism is possible.
H H 109. Nitroalkanes exhibit tautomerism. In it, a-H-atom is labile and
CH3-6~--6~CH3 form nitrolic acid.
OH
I
OH OH
I
H3C- CH 2- N '
7 ~ H3C- CH= <
·: Optical isomers in compounds have similar asymmetric 0 0
carbon atom, which are even in mm1ber = 2n- 1
110. There are six isomers possible for the compounds having
Here, n = 2 molecular formula C4H 8 O, which are as follows:
: . Total number of optically active stereoisomers 0
= 22- 1 = 2 II
CH3CH2C-CH3, CH3CH2CH2CHO,
101 . 2, 2-dimethyl butane is 6-carbon hydrocarbon (¼H 14). (i) (ii)

CH3
CH 3-6-CH 2-CH3
I
CH3 H3C "- /CH2OH
H/c = c"-H
Rest all are the chain isomers of pentane (C5H1:z) . (cis)
(iv)
CH3 CH3
H3C "- / CH2 OH
H 3C-<'.:-CH3 H 3C-6H- CH2-CH3 CH 3CH2CH2CH 2CH3 H / C= C"-H
I 2-inethyl butane n-pentane
(Irons)
CH3 (iso•pentane)
(v)
2, 2-dimethyl propane
(neo-pentane) and CH2=CH-CH 2CH 2OH
(vi)
 Organic Chemistry Some Basic Principles and Techniques I 297
0 0 OH ............ O
111. The name of the c o m p o u n d ~ is
II II I II
CH 3-C-CH2-C-CH3 ~ CH 3- C=CH- C-CH3
CHO acetyl acetone (Enolform 76%)
112. Ht-OH (Ketoform 24%)

CH 20H In acetyl acetone, the enol form is stabilised by H-bonding, hence

it has more enol content than other.
D-glyceraldehyde has the above formula. So, the Fischer's
projection formula which is identical to it, is Topic 5 Methods of Purification of
CHPH Organic Compounds
Hr-OH 1. For separation by differential extraction, one of the component
CHO must form salt with the given base so that the salt will be extracted
in aqueous layer leaving other component in organic layer.
113. The amount of enolic form is highest in acetyl acetone due to the
(a) Both phenol and benzoic acid form salt with NaOH, hence
stabi lisation of enolic form by hydrogen bonding
this mixn,re cannot be separated.
0 0 0 - H ... O (b) Benzoic acid forms salt with NaOH while benzyl alcohol
11 11 I II does not, hence the mixnrre can be separated using NaOH.
CH3- C- CH2- C-CH3 - CH3-C=CH- C- CH3
keto fu1111 (24%) j: Also benzoic acid forms salt with NaHC03 but benzyl
alcohol does not, hence NaHC0 3 but benzyl alcohol does
Q .. ,H - 0 not, hence NaHC0 3 can be used for separation.
II I (c) Neither benzyl alcohol nor phenol form salt with NaHC03 ,
CH3- C- CH=C-CH 3
enolic fo1111 (76%) mixture cannot be separated using NaHC03.
(d) C6H 5 CH2COOHforms salt with NaOH, ¼H 5CHpHdoes
114. Carboxylic acid and esters show functional group isomerism.
not, hence mixn1re can be separated using NaOH.
When two compounds have same molecular formula but different
C6H 5CH2COOH forms salt with NaHC03 · ¼H 5CHpH
functional groups, then functional isomerism arises.
does not, hence mixture can be separated using NaHC0 3•
e.g. C2 H 5COOH and CH3COOCH3
2. Substances which sublimes on heating are usually purified by
115. The strncture of 1-chloro-2-nitroethene is as
sublimation. Hence, naphthalene is purified by sublimation.
N02"- /Cl
H/c = c,H 3. Those organic compounds, which are volatile in steam are
purified by steam distillation. Since, aniline is a steam volatile
In this compound, E-Z isomerism is possible because it is highly compotmd, hence it is purified by steam distillation.
substituted alkene. T he E-Z system of nomenclature is developed 4. Chromatography is a modern technique used for the separation of
by Cahn, Inglod and Prelog. mixtures into its components, purification of compounds and also
116. A carbon atom which is attached by four different groups is called to test the purity of compounds.
an asymmetric carbon atom or chiral centre. 5. In mixture of o -nitrophenol and p -nitrophenol, o-nitrophenol is
H steam volatile due to intra molecular hydrogen bonding whereas
CH 3-6~CI p -nitrophenol is less volatile due to intermolecular hydrogen
I bonding.
Br
OH, / lntramolecular
117. The compounds must fulfill two conditions to show geometrical ~-,, H-bondmg

isomerism.
(i) The compound should have at least one C=C. l8J ~=-0 ~
(ii) The two groups attached to same carbon atom must be
different. o-nitrophenol O %0- H -
1 0 = N lQl
Out of given choices, only (c) fulfill both conditions and shows 02N Q Intermolecular
H-bonding
Q OH
geometrical isomerism. p-nitrophenol
H-C-COOH
II 6. Sublimation conversion of solid directly into gaseous phase. The
H-C-COOH liquid state does not exist.
(c)
2-butene- l , 4-dioic acid e.g. Naphthalene, anthracene.
118. I, 1-dichloro-1-pentene does not exhibit geometrical isomerism. Beilstein test is a simple chemical test used for the detection
119. Racemic mixture is formed by mixing two chiral compounds. halogens.
120. Keto and enol forms are interconvertable. The enol content will Victor-Meyer's method Standard laboratory method for
be maximum when enol form is stabilised by hydrogen bonding. determining the molecular weight of a volatile liquid.
298 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Steam disti llation vaporisation of the volatile constituents of a
liquid. It is special type of distillation for a temperature sensitive
materials like aromatic natural compounds. e.g.
ortho- nitrophenol, cinnamaldehyde.
Vacuum distillation at reduced pressure. It is generally used in
case of high boiling liquids which decompose below their normal
boiling points, cannot be purified by disti llation at atmospheric
pressure e.g. glycerol. Eudiometry it is the process of determining
the constin1ents of a gaseous mixnire by eudiometer. It is used for
ascertaining the purity of air or amount of 0 2 in it.
7. Disti llation is used to purify liquids and based on difference in
their boiling points. When the boiling points of liquids are very
closed to each other, then fractional distillation is used.
8. Compound which sublime on heating can be purified by sublimation
method. Benzoic acid, camphor and naphthalene sublime on
heating, hence they are purified by sublimation method.
9. Aqueous solution of NaHCO3 can be used to separate benzoic
acid from its mixture with camphor. Benzoic acid form water
soluble sodium benzoate with NaHCO 3. While camphor do not
react with NaHCO3 followed by differential extraction ofsolvent.
1O. The reagent selected should be such that only one of components
to be separated, reacts with it.
Aniline + aq. HCI ➔ salt, which is water soluble.
Nitrobenzene + aq. HCI ➔ no reaction
:. aq. HCI is used to separate aniline and nitrobenzene.
11. Chromatography method is used to separate sugars.

Topic 6 Qualitative and Quantitative Analysis of Organic Compounds

1. The sulphur containing organic compounds when fused sodium 73 7
Moles of O= .4 = 4.59
metal give sodium sulphide Na2 S which react w ith lead acetate 16
solution and forms black ppt of PbS, which confirms the presence
Atoms of O = 4.59 x NA
of sulphur in the compound.
Simplest ratio : C : H: 0 = 1.83 : 4.57: 4.59
Fusion
2Na + S - - Na 2S = 1 : 2.5 : 2.5 = 2: 5 : 5
Thus, the ratio of atom of carbon and hydrogen in the compotmd
Na2S + (CH3 COO)2 Pb - - PbS + 2CH3COONa is 2: 5.
Black
pp! 5. 18 g H 2O contains 2g H.
2. CX4 + 202 -- CO 2 + 2X2 O 2
lmol 2mol 0.72 g H 2O contains x o.n
= 0.08 gof H
:2x32 18
:64
44 g CO 2 contains 12 g C.
·: 1.74 g 0 2 reacts wid1 9.0 g CX4 •
9 64
64 g 0 2 will react with x = 331 g CX4
3.08 g CO 2 contains Ex
44
3.08 = 0.84 g C
1.74
: . Molecular mass of CX4 = 331
C: H = 0.84 : 0.08
33 1= 12 +4X 12 1
33 1 12
X = - =79.8,.,,80 = 0.07: 0.08 = 7 : 8
4 Empirical formula= C7 H 8
3. Kjeldahl 's method is used in estimation ofnitrogen atoms present
in an o rganic compound. Organic compound is heated with Cone. 6.
H 2 SO4 in presence of K2SO 4 (which raises boiling point of Atomic Relative number Simple
Element % weight
H 2 SO4 ) and CuSO4 (catalyst), the nitrogen present in the of atoms ratio
compound is converted into ammonium sulphate, (NH4 ) 2 SO4. C 52 12 4.33 2
4 _ %ofC= Ex WeightofCO2 xl00 H 13 I 13 6
44 Weight of organic compound
0 35 16 2.18 I
=Ex 0 .1 98 x 100 = 21.95%
44 0.246 :. Empirical formula of compound= C 2H6O
% of H = 2 x __W_ e_igh
_ t o_f_H~2~O_ x_ l_0 0
__ :. Empirical formula weight = 2 x 12 + 6 x 1 + 16 = 46
18 Weight of organic compound :. Molecular weight= 2x Vapour density = 2 x 23 = 46
= 2 X 0 .1014 X 100 = 4 _57 46
n= - = l
18 0.246 46
% ofO = 100- 2 1.95 -4.57 = 73.47 :. Molecular formula of compound = Ci~O
2 95 :. compound liberates H2 with Na.
Moles of C = 1. = 1.83
12 :. It is alcohol.
Atoms of C = 1.83 xNA :. Compound is C2HsOH ethanol.
4 57 A functional isomer of ethanol is CH 3 OCH 3 (methoxy methane)
Moles of H = - = 4.5
1 7. Percentage of N in an organic
Atoms of H = 4.57 x NA
 Organic Chemistry Some Basic Principles and Techniques I 299
1.4-x-
compound = - N-x- 1.4-
V =- x Ix
--30 = 35 17. When organic compound is fused with sodium meta l, nitrogen
w 1.2 of the compound is converted into sodium cyanide as
8. Weight of organic compound= 29.5 mg Na + C + N - NaCN
NH 3 + HCl - NH4Cl 18. Acidified sodium fusion extract on addition of ferric chloride
HCl + NaOH - NaCl + HzO solution gives blood red colouration, which confirms the
(remaining) 15 x 0.1 M presence ofN and S.
= 1.5 nTI10I Na+ C+ N+ S ➔ NaSCN
Sodium Sulphocyanide
Total millimole ofHCl used= 2
Millimole used by NH 3 = 2- 1.5= 0.5 3NaCNS + aq · FeCl 3 - Fe(CNS)3 + 3NaCI
Red
Weight ofNH 3 = 0.5 x 17 mg= 8.5 mg (ferric thiocyanide)

Weight of nitrogen= ~ x 8.5 mg= 7 mg 19. Presence of halogen in organic compound can be detected by
17 Beilstein 's test.
9. From Kjeldahl's method,
. 1.4 X N XV 20. Percentage Simple
P ercentage of nitrogen = - - - - - Element Perce nt.age
W atomic weight ratio
).4 X 0. 1 X 30 C 20.0 20.0 = 1.66 1.66 = l
8.4%
5 12 1.66
0 535 H 6.67 6.67 = 6.67 6.67 = 4
10. %ofC=E x · x 100 = 19.07
44
0.765 1 1.66
0 138 N 46.67 46.67 = 3.33 3.33 = 2
%ofH =2 x · x 100= 2.004
18 0.765 14 1.66
Ratio of% ofC: H = 19: 2 (approx.) 0 26.66 26.66 = 1.66 1.66 = 1
11. Since, the compound on heating with CuO produced CO2, it 16 1.66
contains carbon. Again, it does not produce water, hence it does Empirical formula = CH4N 2O
not contain hydrogen. So, the organic compound is carbon Empirical formula weight
tetrachloride (CCl 4).
= 12 + (4 XI)+ (2x 14)+ 16= 60
12. Lassaigne's test is given by those nitrogenous compounds in which
= mol. formula weight 60 =
carbon is also present alongwith nitrogen. Tn NH 2 · NH2 · HCI, 11 1
carbon is absent, so it do not gives Lassaigne's test. emp. formula weight 60
13. From Kjeldahl's method, :. Molecular formula= CH 4N 2O
. l.4xNxV Given compound gives biuret test i.e. violet colour with
Per cent o f nitrogen = - - - - -
W alk. CuSO4 solution. T hus, given compound is urea
= 1.4x 0.5x 2x 10 = % (NH2hCO.
56
0.25 21. Na 2S + Na 2[Fe(CN) 5 NO] - Na4 [Fe(CN) 5NOS]
sodium nitroprusside sodium thio nitro
14. A chloride linked with alkyl group is replaced with NO 3 on solution prusside (purple colour)
reaction with AgNO 3 and give white precipitate of AgCI.

$
CH2Cl CH2NO3 22. Liebig's method is used to estimate carbon and hydrogen.

C in an organic compound H J94

CO2 + H 2O
+ AgNO3 - + AgCll
white
precipitate
%C= x E
Weight of CO 2 x 100
44 Weight of compound
Br Br
% H =2 X Weight of H2O X 100
15. On adding SCN- to an aqueous solution ofFe(NO 3h, a blood red 18 Weight of compound
colour, due to the formation of [Fe(H20)s(SCN)r+ complex, is 23. Tf nitrogen is present in organic compound then sodium extract
obtained. This test is used for the detection of Fe3+ ion. contains NaCN.
SCW + Fe(NO3 )3 + 5H2O - [Fe(OH2)s(SCN)f+ + 3NO3 Na + C + N Fuse NaCN
Blood red colour

16. The formation of sodium thionitropmsside (blue) shows the FeSO4 + 6NaCN - Na 4 [Fe(CN;\s] + Na 2 SO 4
(A)
presence of sulphur.
Na 2S + Nai[Fe(NO)(CN)5 J - Nai Fe(CN)5NOS] A changes to Pmssian blue FeiFe(CN\;h on reaction with
Sodium Sodium nitroprusside Sodiwn thionitroprusside FeC13.
extract purple 4FeC1 3 + 3Na4 [Fe(CN\;] -➔ FeiFe(~h + 12NaCI
300 I Chapterwise & Topicwise Engineering Entrances Solved Papers

24. Let unreacted 0. 1 M (= 0.2 N) H 2SO4 = V' mL . Also, 1°.2°,3°

SN2 ______ Alkyl Halides
:. 20 mL of0.5 M NaOH = V' mL of0.2 N H 2 SO 4
20 X 0.5 = V' X 0 .2
1° alkyl halide but (C- CI) bond
V' = 50mL
energy is decreased by electron
Used H 2SO4 = 100- 50 = 50 mL s. w ithdrawing (¼ H 5CO) group, a case
. 1.4NV of(-/-effect). Thus, maximum rate in
% o f nitrogen = - - -
w Si; 2 reaction
where,
V = volume of H 2SO4 used
Q. >-c1 2° alkyl halide, rate is minimum
1° alkyl halide
4
% of nitrogen l. x 0.2 x 50 = 46.67%
0.30 R. ~Cl 1° ally lic halide but allylic 1°
carbocation is resonance stabilised in
% of nitrogen in Si; 1 reaction
14
(a) CH3 CONH 2 = x IOO = 23.73%
59 Thus, reactivity order is S > P > R > Q .
(b) ¼ HsCONH2 = 14 x 100 = 11.48% 2. Markownikoff's m le does not apply on symmetrical alkenes.
122
28 CH 3CH= CH· CH 3 (butene - 2) is a symmetrical alkene.
(c) NH2CONH2 = x JOO= 46.67%
60 3. In Si; I reaction, the racemisation takes place due to inversion
28 and retention of configuration.
(d) NH2CSNH2 = x IOO = 36.84%
76 4. In Si; I reaction, rate of reaction depends upon the concentration
Therefore, the organic compound is urea. of the substrate only.
25. Halogen containing compounds (C6H 5CI) It does not depend upon the concentration of the nucleophile. In
When placed in a flame, the presence of halogen is revealed by a this type of reaction, covalent nucleophile reacts/ attacks on
green to blue flame. substrate.
2° and 3° alkyl halides react through this mechanism.
26. Organic compound ..lQ4 CO2 + Hp
17.6g 7.2g S. Si; 1reaction is most effective in 3° carbon
12 17.6 (CH 3) 3- C- CI CH3CH 2 CH2 CH 2 CI
%ofC= - x - x 100 = 85.7% ten-butyl chloride (3") 1-chlorobutane ( I °)
44 5.6
72 CI- CH 2- CH(CH3)CH 3 CH 3CH 2CH(Cl)CH3
% ofH = 2 X · X 100 = 14.28% 2- methyl - 1- chloropropane (I
0
2-chlorobutane (2")
)
18 5.6
Relative number
6. Due to the presence of tautomeric effect, a - His acidic w ith
Element Percentage Simplest ratio respect to - OH group. So, it will be dehydrated readily in
of atoms
acidic solution.
C 85.7 85.7/12=7. 14 7.1 417.14 = I 7. The substrate has duee different types ofC- H , therefore first,
H 14.28 14.28/ 1 = 14.28 14.2817.14 = 2 three structural isomers of alkenes are expected as

Hence, empirical formula of compound = CH 2

: . Molecular formula of compound = C4H 8
27. Kjeldahl and Duma's methods are used for the quantitative
estimation of nitrogen in an organic compound. In the Kjeldahl
method, the nitrogen element of organic compound is changed to
the ammonia. 2 types of C-H

28. % ofS = ~ x wt. of BaS04

x 100
233 wt. of organic compound
58
=~ X l.1 X 100=30%
233 0 .53
TT III
Topic 7 Types of Organic Reactions
The last two alkenes II and III are also a capable of showing
1. Acetone is an aprotic solvent and can dissolve both the nucleophile geometrical isomerism, hence two geometrical isomers for each
and the substrate and dms Si; 2 reaction is favoured of them will be counted giving a total of five isomers.
 Organic Chemistry Some Basic Principles and Techniques I 301
8. CH; acts as an intermediate in the given reaction (Friedel-Craft's 17. Hydride ion is formed when hydrogen atom accept a electron, so
alkylation). It is an example of electrophilic aromatic substitution. it has a tendency to donate electron. Since, hydride ion (H-) has a
In this reaction, CH; is electrophile. tendency to donate electron, it functions as nucleophile.
18. When sodium ethoxide reacts w ith iodoethane, diethyl ether is
9. Such dehydrohalogenation follow £ 2 mechanism. The driving
obtained (Williamson's synthesis) The mechanism of this
force of such reactions is the stability ofalkene produced. Since, reaction is as follows
tertiary alkyl halide can give more substituted alkene, it reacts
C2HpNa ~ C2Hp- + Na+
fastest followed by secondary and primary, i.e. 3°> 2° > 1°.
6- 6-
10. - CH 3 is ring activating group, while - N02 is ring C2H50- + ½ H5 - I Slow [C2H5- 0 - C2H5- I]
nucJ.,,phile transition state
deactivating. The order is II>I>ITT.
Fast C2H sOC2Hs + r
Since, the reaction involves substitution of a group by a
11. nucleophile, it is an example ofnucleophilic substitution reaction.
19. Alcohols undergo dehydration usually by EI mechanism. This
is because elimination is preferred in case of tertiary alcohols,
Backside attack Transition state
e.g.
Since, the reaction rate depends upon the concentration of both
reactant and nucleophile, it is a~ 2 reaction. It involves inversion H3 C°" r--,, + H3 C°"
of configuration. H 3C
7
c- OH + W ➔ (CH 3h - C ...!_ OH -H > H3C 7C+
20
H3C I H3C
12. Nucleophiles are the species which have excess of electrons. H
Among the given species, the lone pair of nitrogen of pyrrole is
H- H
involved in de localisation of the ring, thus, are not available for ~ CH 3- CH 3 + HBr
donation. In aniline, the lone pair is involved in conjugation with SN2
the 1t-electrons of the ring while in pyridine, these are relatively CH 3

free for donation. Thus, nitrogen of pyridine

nucleophilic.
O N
is most CH3 -
1
I
-Br

CH3
(phenyl and - COCH3 both are electron withdrawing groups,
thus decreases the nucleophilicity of nitrogen).
0
11 ··-@
13. Activating groups like - OCH3, - OH etc. activates the benzene
ring towards electrophilic substin1tion w hile deactivating groups 21.
/r;\_
~ C- R 0
like - N02, -COOH etc, deactivates the benzene ring towards
Ring I RingD
electrophilic substitution. Thus, order of reaction towards
electrophile (of the given compounds) is as I > II > III Electrophilic substitution reaction takes place in compounds in
which 1t-electrons are highly delocalised. The electrophile
14. When nitro group is present in the benzene nucleus, it w ithdraws
attacks the region of high electron density, therefore electrophilic
electrons from oandp-positions. Thus, the electron density at the
substinltion occurs at ortholpara position at ring II.
o and p-positions decreases and m-positions become positions of
comparatively higher electron density. Therefore, electrophilic 22. Chlorobenzene has only one deactivating group, i.e. - CI. In 2,
4-dinitrochlorobenzene three deactivating group, i. e. two - N0 2
attack occurs at m-positions.
and one - CI are present and p-nitrochlorobenzene two
15. The electrophile involved in the sulphonation of benzene is S03. deactivation groups, i.e. one N0 2 and one Cl are present. So, the
2H2S04 ------t S03 + Hp+ + Hso:; order of reactivity is I > III > II.
16. Nucleophile always attacks on electron deficient site. 23. The given reaction can be represented as
Presence of electron withdrawing groups such as N02,CHO etc; NaOH ------t Na+ + OH-
decreases the electron density on benzene nucleus, hence such
H H H H
groups activate the ring towards nucleophi lic attack. While
presence of electron releasing groups such as R or OR increases 0-
OH -
"/
C- Cl HO - -C + c1-
"/
the electron density, thus deactivates the nucleus towards
nucleophilic attack.
I I
CH3 CH3
N02 group activates the ring more than Cl towards nucleophilic trasition state

,u,,k, hffire ~ ="' =<lily w;d, oocleophHe. Since in this reaction, a nucleophile replaces the other group, it is
a example ofnucleophilic substitution reaction. The mechanism
shows that the rate depends on the concentration of both alkyl
halide and nucleophile. So, it is an example of~2 (nucleophilic
substinition of II order) reaction.
N02
302 I Chapterwise & Topicwise Engineering Entrances Solved Papers

X In this process one group is replaced by other, hence it is a substitution

r
24. In the given electrophiles lci<- c
01
X J I
[CH 3C =0] group is
process and both the leaving and attacking groups are nucleophilic,
therefore it is an example of nucleophilic substitution reaction.
32. Chlorine of vinyl chloride (CH2=CHCI) is non-reactive (less
the same. So, only X affects their activity, i.e. we have to discuss
reactive) towards nucleophilic substitution reaction because it shows
activity due to
the following resonating structure due to + M-effect of-Cl atom.
(a) - OCH3 (b) - CI o- o+
CH 2=CH- CI: f-----4 CH 2- CH =Cl
,< - N
(",/_ Me •• II
Me (d) - S-CH3
In stmcture TI, Cl-atom have positive charge and partial double
Since, amines are less actives, therefore, electrophile (c) wi ll be bond character with C of vinyl group, so it is more tightly
least active. attracted towards the nucleus and it does not get replaced by
25. (CH3) 3CBr + H 20 - (CH3)3C- OH + HBr nucleophile in SN_ reaction.
Br is subsituted by - OH- (nucleophile) 33. The Kolbe's electrolysis proceeds via free radical mechanism.
~ I (unimolecular nuclerophilic substitution reaction) For example, when sodium propionate is electrolysed, ,1-butane,
ethane, ethylene are obtained. The propionate ion discharges at
26. Ketone undergoes nucleophilic addition reaction because
the anode to form free radicals.
nucleophilic end of reagent attack first followed by electrophilic
end of reagent. C2 H 5COO- - C2 H 5Coo• + e-
o- OH
C2H5COo• - CiH 5• + CO2
I Slow H+ 2CiH; - C4H io
R- i - R + CW ~ R- C- R ~ R- t - R C2 H; + C2H; - C2H 4 + CiH 6
I Fast I
CN CN 34. During nitration of benzene the attacking electrophile is No;.
ketone
cyanohydrin It is fonned as follows by reaction between HN03 and H 2S04 .
$
27. Chlorine atoms are strongly e lectro negative (show negative I. HN03 + H 2S0 4 ~ H- O- N0 2 + HS0 4
inductive effect i.e. - /-effect). They deactivate the ring towards I
electrophilic reaction. The increasing order of substituent-E H
towards electrophilic substin1tion is $
____,_
TI. H- O- N02 .,------ H 20 + NO;
---CCl 3 < - CHCl 2 < - CH 2CI < - CH 3 I Nit:ronium
28. H20, ROH, R- COOH etc; are protic solvents because they are H ion
polar in nature and contain a hydrogen directly bonded to oxygen e
9
while other are aprotic sovents as they do not have a hydrogen 35. CHC1 3 + OH - CCl 3 + H20
bonded directly to the oxygen. They are especially favourable for e
~ I reactions. Whi le aprotic solvents cannot have hydrogen bond
CCl3 - :cc12 + c,-
to the nucleophile because they do not have hydrogen bonded to 36. Electrophiles are the species having a tendency to accept a pair
nitrogen or oxygen. They are favourable for ~ 2 reactions. of electron, e.g. NO;, Br+ etc. Nucleophiles are the species
29. Nitration of aromatic compounds takes place by an having a tendency to donate a pair of electron. e.g. CH30H, N 3
electrophile. The electrophile will be more attracted towards
electron rich positions in benzene ring. Hence, electron donating 37. A solvent molecu le lacking a polar X - H bond is called aprotic
groups w ill be easily nitrated. Toluene will be most easily solvent. NH 3, S02 and CH 3CN are aprotic solvent while
nitrated among these compounds due to presence of electron CH 3COOH is protic solvent.
donating group (i.e., CH 3). Nitrobenzene w ill be most slowly
nitrated due to the presence of electron withdrawing group (i.e. , 38. RX + r➔ R - I+ x-

N02 ). CH3N02 wi ll be formed by free radical substitution of This reaction is an example of nucleophilic substitution.
CH 4
39. If acid is weak, its conjugate base (nucleophile) is strong and
30. Dehydration of alcohol involves the loss of two atoms or groups vice-versa.
from the adjacent carbon atoms, hence it is an example of 0 0
~elimination reaction. II II
p CL + H+ p CL + (A) CH 3- c - o- is conjugate base of CH 3COH (I)
CH 3CHpH ~ CH3CH20H2 - H20
Ethanol (B) CH 30 - is a conjugate base of CH 30 H (TI)
p CL + p CL
(C) CN- is a conjugate base ofHCN (TII)
CH 3CH 2 ~ CH2 =CH 2

Cl OH
-H
Ethene
(D) H 3C -0- S03 is a conjugate base

31.
© ©
Chlorobenzene
NaOH

Phenol
of H 3C - O - S 03 H(TV)

Acidic nan1re ofTV > I > III > TI and nucleophilicity

of II > TII > I > IV.
 Organic Chemistry Some Basic Principles and Techniques I 303
0 0
II II
40. R-C-X + N£ -----t R-C-N£ + x-
Best leaving group (poorest nucleophile) is ct 0 , thus fastest
reaction is with Cl.
41. Grignard reagent reacts with C=O, -CaaaaN, C=S as follows
R
I /OH
C=O + RMgX -----t C-OH + Mg '-.. X

R
I OH 46. C-CI bond in aryl chloride is stable due to delocalisation of
- C == N + RMgX -----t -C = O + Mg< X
electron by resonance. Also, C-CI bond possess a double bond
character like vinyl chloride, hence ~ reactions are not possible
R
I OH in chlorobenzene under ordinary conditions.
C = S + RMgX -----t C-SH + Mg/
'-.. X

42. Vinyl chloride (CH2=CHCI) undergoes addition and

elimination reactions. Substitutions reaction is shown by
compounds having single bonds only.
43. The correct order of reactivity is
c't: ©1[,trong
O
RI > RBr > RCI > RF

-= a- \'- ' o
It is due to the fact, that weaker the base, better it will be the
leaving group. Hence, 1 is the best leaving group. -- I

44. During electrophilic substitution electrophile attacks the double 0

bond of benzene ring. The aromatic compounds having electron
donating groups undergo electrophilic substitution more easily 47. The species which are electron deficient and accept a pair of
due to favouable effect of electron donating group. electron are called electrophile. Hence, SO3 is a electrophile as it
contains an electron deficient centre. While H2O, NH 3 and

©
COOR

©
R-0-R are nucleophiles.
48. R-CH2-CH2 X + KOH(alc.)-----t
(a) (b) R-CH=CH2 + KX + H 2O
Nitrobenzene Benzoic acid Alkyl halide undergo [3-elimination to form alkene.
49. During nitration benzene ring is attacked by No; and hydrogen
OH
of benzene ring is replaced by NO2 group.

Benzaldehyde
(d)
©
Phenol
(i) NO2, COOR and CHO groups are electron withdrawing
:. Nitration of benzene is electrophilic substitution because NO!
is an electrophile.
50. During nucleophilic substitution weaker nucleophile is replaced
by stronger nucleophile. The compound having C-CI bond
which can be most easily broken will be most reactive towards
groups. So, they decrease the reactivity of organic
nucleophilic substin1tion reaction.
compounds.
In vinyl chloride CH 2=CH-CI and chlorobenzene C6H 5CI the
(ii) - OH group is electron donating group, so it increases the
C-CI bond has partial double bond character due to resonance.
electron density in benzene ring and increases the rate of
reaction. :. They do not give nucleophilic substitution reaction easily.
- Ell

.·.©
OH CH2=CH- ~}: ~ CH 2-CH=CI

benzyl chloride, give nucleophilic substinition easily because the

ood«goes substimtioo most easily. carbocation formed is stabilised due to resonance.
45. The ftmction of AICl 3, in Friedel-Craft reaction, is to produce - Cl- Ell
CH 2 =CH-CH 2CI ~ CH 2 =CH-CH 2
electrophile, which later add to benzene nucleus Allyl chloride Allyl
+ Ell
CH3-CH2-CH2CI + AICl 3 -----t CH 3-CH 2-CH 2 + AICl 4 - CH2-CH=CH 2
Carbocation
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Hydrocarbons
QUICK REVIEW
• Hydrocarbons are the organic compounds of carbon and vzf\1 RCOONa _E_
lectrolysis
_;;__ R-R (at anode)
(
hydrogen only. They can be saturated (contains only single
bond between carbon) or unsaturated (atieast one double or (Kolbe's electrolysis)
triple bond). (vii) Corey House Synthesis Alkyl halide reacts with
dialkyl copper reagent to give alkane.
• Saturated compound are alkanes, also called paraffins with
general formula CnHzn + 2 . Carbon shows tetrahedral Preparation of Methane
geometry with sp 3 hybridisation and 109°28' bond angle.
Al 4 C 3 + 12H2 O ~ 4A1(OH) 3 + 3CH4
• Unsaturated hydrocarbons can be with double bond
(alkenes or olefins) with general formula C,.H2,. or Preparation Method of Alkenes
(alkynes) with triple bond with general formula C,, H2 ,. _ 2 . (i) RC-= CR' ~ Cis-alkene
H2
• Alkenes are sp 2 hybridised with trigonal planar shape at
I 20° and alkynes are sp hyb1idised with linear shape at I 80°. (ii) Alkyne ~ Trans alkene
Liq. NH 3
• Nomenclature Alkane - Root word + ane
AJkene - Root word + ene (iii) RX ~ Alkene (Dehydroha1ogenation)
CH 3 CH 2 X KOH CH 2 = CHz
Alkyne - Root word + yne
(dehalogenation with vicinal derivative).
• Alkanes exhibit only chain isomerism (if have more than
4 carbon atoms). Alkenes exhibit chain, geometrical (iv) CH3 CH 2 OH H 2so4 CH 2 = CH2
170'C- Hj)
isomerism, whereas alkynes exhibit chain and position
isomerism. In cis form of geomettical isomerism, same (Dehydration)
groups lie on same side and in trans on opposite side. (v) In Wittig reaction aldehyde or ketone react with
methylene triphenylphosphine
Preparation Methods of Alkanes (C6 H5 ) 3 P = CH 2 to give alkene
(1) CH 2 = CH 2 + H2 ~ CH3 - CH 3 (addition) e.g. CH3 CHO + (C6 H 5 h P = CH 2
~ CH 3 CH=CH 2 + (C6 H 5 h P =0
Zn. H+
(ii) R- Cl R- H + HCI 3
CH /""' C = O+ (C H h P = CH ~
(iii) R- Cl __N_a _ R- R 6 5 2
Dry ether
CH3
(Wurtz reaction, not for alkane with odd number of
C-atoms) CH3 "'-
/ C =CH2+ (¼Hs)3 P=O
(iv) RMgK + H 2 O ~ R-H + MgKOH
CH3
(v) RCOONa NaOH R-H (Decarboxy lation)
eao
 Hydrocarbons I 305
Preparation Method of Alkynes
(vii) CH 2= CH2
(i) CaC 2 + 2H 2 0 ~ Ca(OHh + C 2H 2 Ethylene
H,O
~ CH 3 · CH20H
Warm Ethanol

6Ag (viii) Unsymmetrical alkenes follow Markownikoffs rule

~ in addition reaction. The negative part of reagent gets
CH3 -C= C-CH3 + 6AgCl attached to double bonded carbon atom which has
But -2-yne least number of H-atoms with peroxide
anti-Markownikoff's rule-vice versa happens.
• Thermal decomposition of alkanes in absence of air is
called cracking or pyrolysis. CH2 CH2C l CH 2 CI
• Alkanes form different conformers due to difference in
(ix) 2 II + S 2 Cl 2 ~I I +S
CH 2 Sulphur CH 2 CH 2
arrangement caused by rotation of C-C bond. monochloride "'- /

Conformers of Alkanes
s
Mustard gas
• Staggered-Most stable groups for apart ~' W.<fichloro diethyl
sulphide
• Eclipsed-Least stable, groups very close. (x) Dienes with alternate double and single bonds are
• Skew or gauche-Intermediate conformation. known as conjugated dienes.
(xi) Diel's Alder reaction Conjugate diene
Properties of Alkanes
(i) Boiling point and melting point increases with molar
mass bp decreases with branching. ( +111~0
(ii) CH4 ~: CH 3 Cl + HCl (halogenation)

... ( 3n +
(m) C,.H 2 n +2 + - -
1) 02 Combustion
2 Properties of Alkynes
nC02 + (n + I) H 20 (i) Their melting point and boiling point increases with
(iv) CH 4 + 0 2 ~ CH3 OH increase in molecular mass. They are lighter than
M0203 water.
Anhy (ii) These are acidic due to presence ofH-atom at tem1ind
(v) n-alkane ~ Branched alkane
AICl3 = bonded C-atoms.

(vi) n-alkane crp 3 Aromatic hydrocarbon (iii) -C= C - ~ -CBr2 -CBr2 -

Al203

-CH=C-
(vii) Higher alkane ~ Aromatic hydrocarbon
973 K 1
OH
Properties of Alkenes Tautorn:risation
(i) Their boiling point and melting point increases with - CH - C-
2 II
increase in molar mass. Boiling point of cis form is 0
higher bu t melting point is higher for trans form.
(v) Alkyne Trans-alkene
(ii) CH 2 =CH2 + HBr ~ CH 3 CH 2Br
Addition reaction follows Markownikoffs rule. _ _P_d l_ B_as_o _4 -➔ c·is-a lkene (addition)
(Lindla(s catalyst)
reaction
(iii) Alkene + H 2 0 ~ Alcohol
( vi) Ozonolysis
CH 2 0H 0
I
CH 2 0H
Ethylene glycol
RC= CR' + 0 - 0
'o/ ~ R- CIC-R'
I I ~ -H202

Zn / H:z()
0 0
(v) RCH= CHR + 0 3 ~ 2RCHO RCOOH + R'COOH
High temperature Na/ Liq. NH3
(vi) Polymerisation n-alkene - - - - - - + Polyene (viii) RC= CH RC=CNa+
fl
pressure (alkylide fom1ation)
Na/Liq. NH3 does not reduce terminal alkyne.
306 I Chapterwise & Topicwise Engineering Entrances Solved Papers

CH2OH Aq lKMn0 4

(ix) HC=CH + 2HCHO ~ I COOH

C = C-CH2OH

(x)
CH
Ill
CH
+HOC!~
CHOH

CHCI
II ~
HOCI

-H:P
CHO
I
CHCl 2
©
~ Anhy.AICI
CHJCI C H CH3
Anhy. AICl3

(toluene) (Friedel Craft's reaction)

(xi) Polymerisation
l8) 3 6 5
CHJCOCI
n-acetylene - Polyacetylene C6 H 5 COCH3 (acetophenone)
Anhy. AICl3
873K
Acetylene - - -- Benzene 3H2
Red hot tube
~ C6H12
CH3YYCH3
CH CH = CH
3 Propene
Cone. H2S04
y CH3
UV 500 K

Mesitylene
Reactivity Towards Electrophilic Substitution
(i) -NH2 , -NHR, -NHCOCH3 , -OH,
Tests for Unsaturation - CH3 - o,p-directing
(i) All unsaturated hydrocarbons have ability to form (ii) Halogens are o/p clirecting but deactivating groups.
sulphonated compounds are soluble in cone. H 2 SO4
(iii)
while saturated compounds don't.
(ii) Copper and silver alkylides obtained by passing -NO2 , -CN, -CHO, -CO, -COOH, -SO 3 H
alkynes ofin ammonical solution ofcuprous chloride are meta-directing and deactivating groups.
and silver nitrate respectively showing presence of
~Cl
acetylenic hydrogen atom.
2C H Cl + CCI CHO~ CCI C H ~
(iii) Decolourisation of bromine water shows unsaturation. 6 5 3 H2S04 3 ~ Cl
(iv) Decolourisation ofKMnO4 is test ofunsaturation.
• For aromatic compound Huckel's rule-cyclic, planar
00) A nthracene DDT

have conjugate system and (4n + 2)1t-electrons.

• Octane number defines efficiency of fuel. Higher octane
• Benzene (C6 H6 ) All carbon sp 3 hybridised showing
number is favourable, and can be enhanced by percentage
resonance. of branched chain alkene and aromatic hydrocarbons.
Preparation of Benzene Antiknocking compound reduce knocking, e.g. tetraethyl
ISOO"C lead.
(i) CH=CH ---➔ Benzene
Red hot tube • Synthetic petrol is prepared by Fischer-Tropsch process.
nCO + (2n +I)H2 ~ Cn H2n+2 + n H20.
Petrol of octane number 80 it contains 80% iso-octane and
20% n-heptane.
(ii)
• LPG is butane. Cetane is hexadecane. Kerosene is
Properties of Benzene C10 -C16 carbon atom. Green oil is obtained at 270-360°C
(i) They burn with sooty flame by distillation of coal tar. Oil gas is mixture of
CH4 + CO + CO2 + H 2
 Topic 1
Preparation of Aliphatic Hydrocarbons
2014
1. The synthesis of 3-octyne is achieved by adding a 10. n-propyl bromide on treating with alcoholic KOH
bromoalkane into a mixture of sodium amide and an produces CKCET]
alkyne. (a) propane (b) propene (c) propyne (d) propanol
The bromoalkane and alkyne respectively are
11. (CH 3 h CMgCI on reaction with D 2 0 produces
[JEE Advanced]
(a) (CH 3 ) 3 COD (b) (CD 3 h CH CKerala CEEJ
(a) BrCH 2 CH 2 CH 2 CH 2 CH 3 and CH3 CH 2 C- CH
(c)(CH 3 ) 3 CD (d) (CD 3 h CD
(b) BrCH2 CH 2 CH 3 and CH3 CH 2 CH2 C=CH
(e)(CD 3 ) 3 COD
(c) BrCH2 CH 2 CH 2 CH 2 CH 3 and CH3 C=CH
12. 2-chloro-3-methylbutane is treated with sodium in ethereal
(d) BrCH2 CH 2 CH 2 CH 3 and CH 3 CH 2 C = CH
solution, then it will give [Indrapras tha CET, CGP ET]
2. Wurtz reaction involves the reduction of alkyl halide with
(a) 2,4-din1ethylhexane
(a) Zn/HCl (b) HI [Manipall (b) 3,5-dimethylhexane
(c) Zn/Cu couple (d) Na in ether (c) 2,3,4,5-tetramethylhexane
3. Decarboxylation of sodium propionate leads to the (d) 2,6-dimethyloctane
formation of [KCET] 13. The major product formed when a 3, 3-dimethyl butan-2-ol
(a) methane (b) ethene is heated with concentrated sulphuric acid, is [Guj CET]
(c) propanone (d) ethane (a) 2, 3-dimethyl-2-butene
4. The products formed in reaction is (are) (b) 2, 3-dimethyl-1-butene
Dry ether (c) 3, 3-dimethyl-1-butene
C 2 H 5 Br + 2Na + CH 3 Br -----+ [AMU] (d) cis and trans isomers of 2, 3-dimethyl- l-butene
(a) ethane 14. An alkyl halide by formation of its Grignard reagent and
(b) propane heating with water yields propane. What is the original
(c) butane alkyl halide ? CBCECEJ
(d) ethane, propane and butane
(a) Methyl iodide (b) Ethyl iodide
5. What is Zin the following reaction? (c) Ethyl bromide (d) Propyl bromide
_Na_O_H_/C_a_O➔ Z 15. Meso-dibromobutane on debromination gives [DCE]
CH3 -CH2 --CO;Na+ [EAMCET]
(a) propane (b) n-butane (a) trans-2-butene (b) cis-2-butene
(c) ethane (d) ethyne (c) I -butene (d) 1-butyne

2009 2008
6. A Wittig reaction with an aldehyde gives [VITEEE] 16. Wet ether is not used as a solvent in Wurtz reaction,
because the water present in it [DCE]
(a) ketone compound (b) a long chain fatty acid
(c) olefin compound (d) epoxide (a) hydrolysis RX to ROH (b) reduces RX to RH
(c) destroy the Na metal (d) reacts with R-R
7. A mixture of 1-chlorobutane and 2-chlorobutane when
treated with alcoholic KOH gives [Manipal] 17. Methyl bromide is converted into ethane by heating it in
ether medium with [Jamia Millia Islamia]
(a) I -butene
(b) 2-butene (a) Al (b) Zn (c) Na (d) Cu
(c) iso-buty lene
(d) mixture of I-butene + 2-butene
2007
18. The reagent(s) for the following conversion, is/are
8. Thermal decomposition of alkanes in the absence of air is
called [MP PET] Br~ ~ H =H
(a) cracking (b) oxidation Br
(c) combustion (d) hydrogenation (a) alcoholic KOH [IITJEE]
400 600 (b) alcoholic KOH followed by NaNH 2
9. CH 3 CH 2 CH3 - X + Y, X and Y are
"C l CKCETJ (c) aqueous KOH followed by NaNH 2
(a) hydrogen and methane (b) hydrogen and ethylene (d) Zn / CH 3 OH
(c) ethylene and methane (d) None of these
308 I Chapterwise & Topicwise Engineering Entrances Solved Papers

19. By which one of the following compounds both CH4 and 29. When sodium propionate is heated with soda lime, the
CH 3 -CH3 can be prepared in one step? [Manipal] product formed is [Guj CETJ
(a) CH 3 I (b) CH3 0H (a) methane (b) ethane
(c) CH 3 CH 2 I (d) C 2 H 5 0H (c) ethene (d) ethyne
20. For synthesis ofl -butene, CH3 Mgl should be treated with 30. The reaction conditions used for converting
1, 2-dibromopropane to propylene are [J&K CET]
[MHTCET]
(a) propene (b) 2-chloropropene (a) KOH, alcohol/~ (b) KOH, water/~
( c) Zn, alcohol/~ ( d) Na, alcohol/~
(c) ally! chloride (d) ethyl chloride
31. By Wurtz reaction, a mixture of methyl iodide and ethyl
21. Butene-I may be converted to butane by reaction with
iodide gives [BCECE]
(a) Zn-HC l (b) Sn-HCl [MP PET]
(c) Zn-Hg (d) Pd/H2 (a) butane
(b) ethane
22. Pure methane can be produced by [WBJEE]
(c) propane
(a) Wurtz reaction ( d) a mixture of the above three
(b) Kolbe's electrolytic method
(c) soda lime decarboxylation 2005
( d) reduction with H2 32. What would be the product formed when l-bromo-
23. Alkyl halides react with dialkyl copper reagents to give 3-chlorocyclobutane reacts with two equivalents of metallic
(a) alkenyl halides (b) alkanes [UPSEE] sodium in ether ? [IIT JEE]
(c) alkyl copper halides (d) alkenes ,---------< Cl
24. Product fo1med on electro!ysis ofpotassium salt offumaric (a) 17 (b) L_J
and maleic acid is [OJEE]
Br~
(a) ethane (b) ethene
( c) ethyne (d) methane (c) Q (d) 0
25. Al 4 C 3 on hydrolysis yields [OJEE]
33. Which one of the following methods is neither meant for
(a) nitrogen gas (b) methane gas
the synthesis nor for separation of amines ? [AIEEE]
(c) hydrogen gas (d) carbon dioxide
(a) Curtius reaction (b) Wurtz reaction
26. Aqueous solution of an organic compound, A on
(c) Hofmann m ethod (d) Hinsberg method
electrolysis liberates acetylene and CO2 at anode. A is
(a) potassium acetate [EAMCETJ
34. Iso-propyl bromide on Wurtz reaction gives [BITSATJ
(b) potassium succinate (a) hexane
(c) potassium citrate (b) propane
(d) potassium maleate (c) 2, 3-dimethyl butane
( d) neo-hexane
27. CaC2 + H2 0 ~ X 35. The carbide which reacts with water to form ethyne is
HCOOH + HCOOH, X is CDCEJ (a) CaC2 (b) SiC (c) Mg 2 C 3 [Kerala CEEJ
(a) C 2 H 4 (b) C 2 H 2 (d) Al 4 C 3 (e) Be 2 C
(c) C 2 H 6 (d) Ca(OHh 36. The chemicals and the reaction conditions required for the
preparation of ethane are [EAMCETJ
2006 (a) C2 H 5 I, Zn -Cu, C2 H 5 0H
28. Which of the following reagents when heated with ethyl (b) CH 3 Cl, Na, H 2 0
chloride, forms ethylene ? [EAMCET]
( c) KOOC-CH = CH-COOK electrolysis
(a) Aqueous KOH (b) Zn/HCl (d) CH 3 C0 2 Na, NaOH, CaO, ~
( c) Alcoholic KOH (d) HI
 Topic 2
Properties of Aliphatic Hydrocarbons
2014 2013
1. Isomers of hexane, based on their branching can be 8. The nwnber of optically active products obtained from the
divided into three distinct classes as shown in the figure. complete ozonolysis of the given compound [JEE Mains]
The correct order of their boiling point is
[JEE Advanced] CH3 CH3 H
f f I
I[+ a n d ~J u [ ~ a n d ~]
CH3CH= CH-C-CH = CH - C - CH = C-CH

H
II
CHCH3
H
(a) 0 (b) 1 (c) 2 (d) 4
m [~ ]
A the compound A is
(a) I > II > III (b) III > II > I [OJEE]
(c) II > III > I (d) III > I > II
2. The major organic compound formed by the reaction of If
(a) CH 3 -CH2 -C-CH 3
1, 1, 1- trichloroethane with silver p owder is
(b)CH 3 -CH2 -CH2 CHO
(a) acetylene (b) ethene [JEE Mains]
(c) CH 3 -CH2 -CH2 -COOH
(c) 2-butyne (d) 2-butene (d) None of the above
3. What are the shapes of ethyne and methane? [EAMCETJ
(a) Square planar and linear
2012
(b) Tetrahedral and trigonal planar 10. Which branched chain isomer of the hydrocarbon with
( c) Linear and tetrahedral molecular mass 72u gives only one isomer of mono
(d) Trigonal planar and linear substituted alkyl halide? [AIEEEJ
4. Which one of the compound does not dissolve in (a) Te1tiarybutyl chloride (b) Neo-pentane
concentrated H 2 SO 4 ? [IPUCET] (c) ]so-hexane (d) Neo-hexane
(a) Hexane 11. 2-hexyne gives trans-2-hexene on treatment with
(b) Benzene (a) Pt/H 2 (b) Li/NH 3 [AIEEEJ
(c) Ethylene (c) Pd/BaSO 4 (d) LiAlH 4
(d) Aniline
12. Propyne on ozonolysis gives [OJEEJ
5. What is one of the products of the addition of HBr to
(a) CH 3 COOH + HCOOH (b) CH3 COOH + HCHO
2-butene? [IPUCET]
( c) CH 3 CHO + HCHO ( d) CH3 CHO + HCOOH
(a) 1-bromobutane
13. Which of the following is a conjugated diene? [AMU]
(b) 2-bromobutane
( c) 1,2-dibromobutane (a) CH 3 CH=C=CHCH3
(d) 2, 3-dibromobutane (b) CH 2 = CHCH2 CH= CH 2
6. Which of the following is correct order according to (c) CH2 = CHCH 2 CH 2 CH= CH2
boiling point? [RPETJ (d) CH 2 = C-CH= CH2
(a) n-pentane < n-hexane < 2, 3-dimethyl butane I
CH3
(b) n-pentane < 2, 3-dirnethyl butane< n-hexane
(c) 2, 3-din1ethyl b utane< n-hexane < n-pentane
(d) n-hexane < 2, 3-dirnethyl butane< n-pentane
2011
14. Ozonolysis of an organic compound gives formaldehyde as
7. Ethylene can be converted into alcohol by treatment with
one of the products. This confirms the presence of
(a) aq KOH [J&K CET]
(a) two ethylenic double bonds [AIEEEJ
(b) dil. H2 SO 4 (b) a vinyl group
(c) moist silver oxide (c) an iso-propyl group
(d) Zn/HCI (d) an acetylenic triple bond
310 I Chapterwise & Topicwise Engineering Entrances Solved Papers
15. Ozonolysis of an organic compound A produces acetone 22. The compound with highest boiling point [JCECE]
and propionaldehyde in equimolar mixture. Identify A (a) n-hexane (b) n-pentane
from the following compounds. [AIEEE] (c) 2, 2-dimethylpropane (d) 2-methylbutane
(a) 2 -methyl-1-pentene (b) 1-pentene 23. In the series,
(c) 2-pentene (d) 2 -methyl-2-pentene
16. Identify Band Din the following sequence ofreactions.
The compound Z is [Punjab CET]
(a) CH3CH2CH = CH2 (b) CH3COCH3
(c) CH3 CHO (d) CH3CH2CH 2CHO

2009
24. When acetylene is passed through dil. H 2SO 4 in presence
ofHgSO 4 , the compound fo1med is [UPSEE]
(a) ether (b) acetaldehyde
(a) Methanol and bromoethane [KCET] (c) acetic acid (d) ketone
(b) Ethyl hydrogen sulphate and alcoholic KOH 25. Mustard gas is a CUPSEE]
(c) Ethyl hydrogen sulphate and aqueous KOH
(d) Ethanol and alcoholic KOH (a) oil gas (b) poisonous gas
(c) fuel gas (d) life gas
2010 26. In the following reaction,
17. One mole of a symmetrical alkene on ozonolysis gives two RCH2CH= CH 2 + IC! ~ A
moles ofan aldehyde having a molecular mass of 44 u. The Markownikoff's product A is [AMU]
alkene is [AIEEE]
(a) RCH 2 f H-CH 2I (b) RCH 2 f H-CH 2CI
(a) propene (b) I-butene
(c) 2-butene (d) ethene Cl I
18. Which compound does not give prec1p1tate with (c) RCH 2-C=CH 2 (d) RCH=CH-CH 2 I
anlflloniacal silver nitrate solution? [MP PET] I
(a)C2H 5 -C = CH
I
(b) CH3-C-C-CH3 27. The1mal decomposition of [AMU]
CH3
I 0- EB e gives
CH2NMe3OH
(c)CH 3 -CH-C=CH
(d) Ph-CH2 -C=CH
19. According to Markownikoffs rule, what will be the major
(a) C)=cH2 (b) 0=9 NMe2
product of reaction,
HBr (c) C)=cH20H (d) o - CH3
CH 2= CH-CH3 ~ ? [MPPET]
Br
28. An organic alkadiene on reductive ozonolysis produces
I
(a) CH3-CH-CH3 I. acetaldehyde
TI. acetone
(b) Br-CH2-CH2 -CH3
ITT. 2-methylpropane -1,3-dial
(c) CH2= CH-CH2Br
The formula of alkadiene will be
(d) CH 2=C=CH2
[lndraprastha CET, CGPMT]
20. Propyne on passing through red hot copper tube forms
(a) CH3C= CH CHCH = CHCH3
(a) benzene
(c) mesitylene
(b) toluene
(d) None of these
[RPET] I I
CH3 CH3
21. Which of the following is the predominant product in the (b) CH3fHCH = fCH = CHCH 3
reaction of HOBr with propene? [JCECE]
CH 3 CH3
(a) 2-bromo-1-propanol
(b) 3-bromo-1-propanol (c) CH3 C = CHCHC = CHCH3
(d) CH3Cll2CHCH=!=CHC = CH2
(c) 2-bromo-2-propanol
CH~ CH3 I
(d) l-bromo-2-propanol CH3 CH3
 Hydrocarbons I 311
2008
29. In the following sequence of reactions, the alkene affords 36. Which one of the following compounds will react with
the compound B methyl magnesium bromide? [MHT CETJ
(a) CH3 CH2CH 2CH 2 CH3
CH3CH=CHCH3 ~ A H;O B
(b)CH 3CH = CH -CH = CH 2
The compound B is [AIEEE] (c) CH3 -C = C-CH2CH3
(a) CH3CH 2CHO (b) CH3COCH3 (d) CH 3 CH 2 CH2C = CH
(c) CH3CH 2COCH3 (d) CH3CHO 37. Ammoniacal cuprous chloride will give red precipitate with
30. The hydrocarbon which can react with sodium in liquid which one of the following ? [MP PET]
ammonia is [AIEEEJ (a) CH3 -C - C-CH3
(a) CH3CH 2CH 2 C= CCH 2 CH 2CH3 (b) CH3 -CH = CH 2
(b) CH3 CH2C=CH (c) CH3 -C=CH
(c) CH3CH = CHCH3 (d) CH3 -CH = CH-CH3
(d) CH3CH2C = CCH 2 CH3
38. The reaction of CH 3 -C= C - o - ~ O-H with
31. The treatment of CH 3 MgX with CH3C=C- H
I I -
produces [AIEEE] H3 C H
(a) CH3-CH = CH 2
(b) CH3 C - C-CH3 HBr gives predominantly. [Kerala CEE]
H H H Br
I I I I
(c)CH3- C = C-CH3 (a) CH3 - C - C - o - ~0 -H
(d) CH4
I I -
H 3C H
32. What are X and Y respectively in the following reaction?
Br H
[BITSAT, AMU, EAMCETJ
y X
I I
Z-product f--C-- 2-butyne ~ E- product (b)CH 3 -C---C-o-~ O-H
I I -
(a) Na/NH 3 (liq.) and Pd/BaSO 4 + H2 H3 C H
(b) Ni/140°C and Pd/BaSO4 + H2 Br H
(c) Ni/140°C and Na/NH 3 (liq.) I I
(d) Pd/BaSO4 + H2 and Na/NH 3(1iq.) (c) CH3 - C - C -o ~- O-H
I I -
H CH3
33. CH3 CH3 + HNO3 ~ ? [VITEEE]

(a) CH3CH2NO2
H3i f
(b) CH3CH2 NO2 + CH 3 NO 2
(d) CH3 -,-,-0-Br
(c) 2CH3 NO 2
(d) CH 2 = CH 2 Br
H
H
Br
34. An alkene on vigorous oxidation with KMnO4 gives only
acetic acid. The alkene is [ManipaIJ
I I
(e) CH3 - C - C - o ~-Br
(a) CH3CH 2 CH = CH 2 I I -
(b) CH3CH = CHCH3 H3 C H
(c) (CH3 hC=CH 2 39. The dihalogen derivative X of a hydrocarbon with three
(d) CH3 CH = CH2 carbon atoms reacts with alcoholic KOH and produces
35. Oxidation of 1-butene with hot KMnO4 solution produces another hydrocarbon which forms a red precipitate with
ammoniacal Cu 2 Cl 2 . X gives an aldehyde on reaction with
(a) CH3CH 2COOH + HCOOH [ManipaIJ
aqueous KOH. The compound Xis [Keral a CEEJ
(b) CH3CH2 COOH +CO 2
(a) 1, 3-dichloropropane (b) 1, 2-dichloropropane
(c) CH3COOH + CO 2
(c) 2, 2-dichloropropane (d) 1, 1-dichloropropane
(d) (CH3 hC=O + CO2 (e) 1, 3-dichloropropene
312 I Chapterwise & Topicwise Engineering Entrances Solved Papers
40. Which one of the following gives, on ozonolysis, both 48. When C 2H2 , CH 4 and C 2H 4 passes through a test tube
aldehydes and ketones ? [WB JEE] which have ammoniacal Cu 2Cl 2, find out which gas
(a) Me 2 C==CHMe comes out unaffected from test tube ? [BCECE]
(b) Me 2 C=CMe2 (a) C2 H2 and CH4 (b) C 2 H2 and C2 H4
(c) MeCH 2- C(Me) = CMe 2 (c) C2 H4 and CH4 (d) C 2 H2
(d) MeCH(Me)- CH = CHMe
49. In the following reaction,
41. The major product Pin the following reaction is
C2H2 HgSo:,2i2S04 X ;;:::::::=! CH3CHO.
CH3- CH=CH2 ~ p [WBJEE]
peroxide
What is X? [BCECE]
(a) CH3CH 2 CH 2 I (a) CH3 CH2 0H (b) CH3- 0 - CH 3
(c) CH3CH2 CHO (d) CH 2 = CHOH
50. Acetylene and HCHO react in presence of copper acetylide
catalyst to form [DCEJ
(a) l-butyne-1, 4-diol
42. A compoundX on ozonolysis followed by reduction gives (b) 2-butyne-l, 2-diol
(c) 2-butyne- l , 4-diol
an aldehyde C 2H 4 0 and 2-butanone. Compound Xis
[UPSEE]
(d) None of these
(a) 3-methyl pentene-2 (b) 3-methyl pentene-3 51. In the reactions,
(c) 3-methyl hexene-3 (d) 3-ethyl pentene-3 B Lindlar catalyst/ H 2
A

o~
43. Select the reagent for the following reaction, [OJEEJ
A and B are geometrical isomers. Then, [DCE]

OHC-(CH2) 4 -CHO (a) A is cis and Bis trans

(b) A is trans and B is cis
(a) Se02 (c) A and Bare cis
(b)03 ,Zn / H2 0 (d) A and B are trans
(c) 0 3 , H20 2-CH3COOH
(d) PCC 2007
44. An alkyne combines with a conjugated diene to give an 52. Cyclohexene on ozonolysis followed by reaction with zinc
unconjugated cycloalkadiene. The most likely title of this dust and water gives compound E. Compound Eon further
reaction is [OJEEJ treatment with aqueous KOH yields compound F.
Compound F is [IIT JEE]
(a) Schotten-Baumann reaction
(b) Hofrnann-bromamide reaction
(c) Pinacol-Pinacolone rearrangement (a) 0 - - CHO (b) 0 - C H O
(d) Deils-Alder reaction
45. A hydrocarbon of molecular formula C 6 H 10 reacts with
sodamide and the same on ozonolysis followed by (c) 0 - c o oH (d)CCOOH
hydrogen peroxide oxidation gives two molecules of COOH
carboxylic acids, one being optically active. Then, the
hydrocarbon may be [Guj CETJ 53. Which of the following reactions will yield,
(a) 1-hexyne 2, 2-dibromopropane ? [AIEEE]
(b) 3-hexyne (a) CH3 -C = CH+ 2HBr~
(c) 3-methyl-1-pentyne (b)CH3CH = CHBr + HBr ~
(d) 3, 3-dimethyl-1-butyne
(c) CH=CH + 2HBr~
46. 1-butyne on hydration gives [J&K CETJ (d) CH3- CH = CH 2 + HBr ~
(a) butyne-1, 2-diol (b) butane- 1-ol (i) X
54. CH 3- C = C -CH 3 - - - - - - +
(c) butane-2-ol {d) butane-2-one (ii) Zn/ Hi)

47. Which of the following alkenes gives an acetaldehyde on CH3-C-C-CH3 . In the above reaction X is
ozonolysis ? [J&K CETJ II II [BITSAT]
(a) Ethene (b) Propene
0 0
(c) I -butene (d) 2-butene (a) HN03 (b) 02
(c) 0 3 (d) KMn04
 Hydrocarbons I 313
55. Reaction ofHBr with propene in the presence of peroxide 62. Which one of the following has the minimum boiling
gives [Manipall point? [Jamia Millia Islamia]
(a) iso-propyl bromide (b) 3-bromo propane (a) n-butane (b) 1-butyne
(c) ally! bromide (d) n-propyl bromide (c) I-butene (d) !so-butene
56. Under which one of the following conditions, does the
2006
reaction, CH = CH + CH 3 OH ~ 63. CH 3 - CH = CH 2 + NOCI ~ P
CH 3 O-CH = CH 2 take place? [Ke rala CEEJ
Identify the adduct [IIT JEE]
(a) NH4 OH / 80° C
(b) Cone. H 2 SO4 / 160° C (a) CH 3- C H - C H 2 - CH 2
(c) Anhydrous ZnC1 2 / 150° C I I I
Cl NO Cl
(d) Dilute HCl/fHF, 80°C
(e) CH3 OK / 160- 200° C
57. Which of the following will yield trans product from (d) CH 2- CH 2- CH2
butyne? [OJEEJ I I
NO Cl
(a) LiAlH4 (b) Na/Liq.NH 3
(c) NaBH4 (d) Ni catalyst 64. HBr reacts with CH 2= CH- OCH 3 under anhydrous
58. Propene on reaction with hypochlorous acid to give conditions at room temperature to give [AIEEEJ
[OJEEJ (a) CH 3 C HOand CH 3 Br

(a) ICI
OH
(b) ~ O H
Cl (b) BrCH 2 CHOand CH3 OH
(c) BrCH 2 - CH 2 - OCH3
(d) H 3 C - CHBr - OCH3
65. What is the product formed when acetylene reacts with
~
OH
(c) Cl (d) ~ hypochlorous acid ? [MHT CETJ
(a) CH 3 COCI (b) ClCH2 CHO
(c) Cl 2 CHCHO (d) ClCH 2 COOH
59. Propyne on passing through red hot iron tube gives

(•) A (b) % [OJEEJ

66. The Markownikoff's rule is the best applicable to the
reaction between
(a) C2H 4 + HCI
(c) C 3 H 6 + HBr
[Ke rala CEE]
(b) C 3 H 6 + Br2
(d) C 3 H 8 + Cl 2

(o) ©X ( d) None of these

(e) C2 H 4 + 12
67. An alkene on reductive ozonolysis gives 2-molecules of
CH 2 (CHO) 2 . The alkene is [Ke rala CEEJ
(a) 2, 4-hexadiene
CHO CH 2CHO (b) 1, 3-cyclohexadiene
60. Ozonolysis products of an olefin are I and I (c) 1, 4-cyclohexadiene
CHO CH 2CHO ( d) I-methyl- I , 3-cyclopentadiene
(e) 1, 2-dirnethyl cyclopropene
Olefin is [AMU]

(a) 0 68. The test for unsaturation

(a) Iodine water

is confinned by the
decolourisation of which of the following ?
(b) CuSO 4 solution
[WB JEE]

(c) 0 ( c) B romine water ( d) All of the above

69. When a mixture of methane and oxygen is passed through
61. Identify Bin the following reaction, heated molybdenum oxide, the main product formed is
(a) methanoic acid (b) ethanal [AMUJ
CH2=CH2 + HCl Anhy.AICl 3) A + 2 [H] (c) methanol (d) methanal
Zn-Cu B + HCI 70. Ethylene reacts with 1% alkaline KMnO4 to fom1
~H 50H [EAMCET] [Guj CET]
(b) C 2 H 6 (a) oxalic acid (b) ethylene glycol
(d) C 2 H 5 OH (c) ethyl alcohol (d) HCHO
314 I Chapterwise & Topicwise Engineering Entrances Solved Papers
71. In the following reaction, A and B, respectively are Compound formed A is [BITSAT]
HBr
A~ C 2 H 5 Br
B
~ A [J&KCET]

(a) C 2 H4 , ale. KOH / t:,,.

(b) C2 H 5 Cl,aq. KOH f t:,.
(a)
0-1:CH-CH,
(c) CH 3 0 H, aq. KOH I t:,,.
(d) C2 H 2 , PBr3 (b) Q - c H=CHCH 2 Br
72. The major product in the reaction of 2-butyne with Li/liq.
NH3 is

H 3C"" /CH 3
[J&K CET]
(c)
o- CHCH-
I
Br
2 CH2
I
Br
(a) / =~
H H (d) Q=CH,CH-CH,
HC""
3
/H
(b) / =~ Br
H CH3 78. The conversion of propene to propanol is .... type of
(c) CH 3 CH 2 CH 2 CH 3 reaction. [MHT CET]
(d) H 2 C = CH-CH 2 -CH3 (a) hydrogenation (b) hydrat ion
73. In the reaction sequence, (c) hydrolysis ( d) dehydrogenation
79. A gas decolourised by KMnO4 solution but gives no
CH 3CH -CH
- 2
(il03
(ii) H f)/Zn l Pro d ucts w1·11b e
precipitate with ammoniacal cuprous chloride is [KCET]
(a) CH3COCH3 [Jamia Millia Islamia] (a) ethane (b) methane
(b) CH3COCH 2 OH (c) ethene (d) acetylene
(c) CH3COOH + HCOOH 80. An alkene having molecular formula C9 H 18 on ozonolysis
(d) CH3CHO + HCHO
gives 2, 2-dimethyl propanal and 2-butanone. The alkene is
2005 (a) 2, 2, 2-trimethyl-3-hexene [Kerala CEE]
74. 2-methylbutane on reacting with bromine in the presence (b) 2, 2, 6-trirnethyl-3-hexane
of sunlight gives mainly [AIEEE] (c) 2, 3, 4-trimethyl-2-hexene
(d) 2, 2, 4-trirnethyl-3-hexene
(a) l-bromo-3-methylbutane
(e) 2, 2-dimethyl-l, 3-heptene
(b) 2-bromo-3-methylbutane
(c) 2-bromo-2-methylbutane 81. Observe the following reactions and predict the nature of A
( d) l-bromo-2-methylbutane and B [WB JEE]

75. Reaction of one molecule of HBr with one molecule of

I, 3-butadiene at 40°C gives predominantly [AIEEE]
B ::r mcrl
ht HBr >A
(a) l -bromo-2-butene under kinetically controlled r-1
conditions ~
(b) 3-bromobutene under thermodynamically controlled
conditions
(a) A and B both are ~
(c) l-bromo-2-butene
controlled conditions
under thermodynamically V Br

(d) 3-bromobutene under kinetically controlled (b) A and B both are

conditions Br

76• ~

(a) meso diol

~
os04 A , A.IS

(b) racemic diol

CBITSAT]
(c)A is ~ andBis~
Br V
(c) Both (a) and (b) (d) None of the above
~ ~
77. Following compound is treated with NBS (d) A is Br,,}0 Br and B is V Br

O - cH 2 CH=CH 2 + NBS~ A
 Hydrocarbons I 315
82. Which of these does not follow anti-Markownikoffs 87. Acetylene does not react with [Jamia Millia Islamial
rule? [OJEE] (a) Na (b) ammoniacal AgNO 3
(a) 2-butene (b) I-butene (c) 2-pentene (d) 2-hexene (c) HCl (d) NaOH
83. Which reacts with ammoniacal AgNO3 ? [OJEE] 88. Identify Z in the series,
(a) Propyne (b) 2-butyne HBr aq. KOH NaCO
CH2 = CH 2 ~ X ---➔ Y ----4 Z CDCEJ
(c) I, 3-butadiene (d) Pentene 1 excess
2
84. In the sequence of reactions,
C2H4 ~ X AgCN y ~z 89. Propyne and propene can be distinguished by [DCEJ
H2/ Ni '
(a) cone. H 2SO4 (b) Br2 in CC1 4
compound Z is [AMU] (c) alk. KMnO4 (d) AgNO 3 in NH 3
(a) N-rnethyl ethanamine (b) N-propylamine Lindlar's
(c) N, N-clirnethylarnine (d) ethyl cyanide 90. [A] catalyst
85. A gas formed by the action of alcoholic KOH on ethyl
[A] and [B] are respectively [DCE]
iodide, decolourises alkaline KMnO 4 . The gas is
(a) C 2 H6 (b) CH4 [Guj CETJ
(a) cis, trans-2-butene (b) both trans-2-butene
(c) trans, cis-2-butene (d) both cis-2-butene
(c) C 2 H2 (d) C 2H 4
91. When 2-butyne is treated with Pd-BaSO 4 , the product
86. Which is most aciclic of the following ? [J&K CETJ
formed will be [DCEJ
(a) Methane (b) Acetylene
(c) I -butene (d) Neo-pentane (a) cis-2-butene (b) trans-2-butene
(c) 1-butene (d) 2-hydroxy butane

Topic 3
Aromaticity, Structure of Benzene and Aromatic H ydrocarbons
2014
1. Hydrogen bonding plays a central role in the following 3. For which of the following molecule significantµ 7- 0?
phenomena [JEE Advanc ed]

~ ~ ~ ~
(a) ice floats in water
(b) higher Lewis basicity of primary amines than
tertiary amines in aqueous solutions
(c) formic acid is more acidic than acetic acid

i
(d) dimerisation of acetic acid in benzene Cl CN OH SH
2. The reactivity of compound Z with clifferent halogens I TI III IV
under appropriate conclitions is given below. (a) Only r [JEE Mains]
OH Monohalo substituted (b) I and II
derivative when X2 = 12 (c) Only III

Q C(CH3h
Xi Dintalo substituted derivative
when X2 = Br2
Trihalo substituted derivative
(d) III and IV

4. Ph-C=C-CH 3 [VITEEE]
whenX2 = Cl2 ~o
(a) Ph -C"-
The observed pattern of electrophilic substitution can be /CH2
explained by [JEE Mains] H3C
(a) the steric effect on the halogen /OH
(b) the steric effect of the tert-butyl group (c) Ph-C~
/CH
(c) the electronic effect of the phenolic group H3C
(d) the electronic effect of the tert-butyl group
316 I Chapterwise & Topicwise Engineering Entrances Solved Papers
5. Which reagent would you use to carry out the reaction 12. To get DDT chlorobenzene has to react will following
Ethyl benzene ➔ 2 and 4-chloro I-ethyl benzene? compound in the presence of concentrated sulphuric acid
(a) Cl 2 light and heat (b) Cl 2 , FeC1 3 [ManipalJ (a) trichloro ethane [KCET]
(c) SOC1 2 (d) C 2 H 5 Cl, AlC1 3 (b) dichloro acetone
( c) dichloro acetaldehyde
6. Which pair is usually required for a nucleophilic aromatic (d) trichloro acetaldehyde
substitution reaction? [MP CETJ
13. Three fused benzene rings are found in [KCETl
(a) An-NO 2 substitution and a strong electrophile.
(b) A ring bearing a strong activating group and a strong (a) naphthalene (b) anthracene
acid ( c) phenanthroline ( d) triphenyl methane
(c) An aryl halide with an NO 2 and astrongnucleophile. (e) None of the above
( d) An unsubstituted benzene ring and a strong 14. In the oxidation ofC6 H 5 -CH2 -CH3 by KMnO4 the
electrophilic product formed is [OJEEJ
7. The correct statement is [KCET] (a) C 6 H 5 -CH2 -CHO (b) C 6 H 5 -CH2 -COOH
(a) cyclohexadiene and cyclohexene cannot be isolated (c) C 6 H 5 -COOH (d) C 6 H 5 -CH2 -OH
with ease during controlled hydrogenation of
15. The electrophile in the nitration of benzene is [AMUl
benzene
(b) One mole each of benzene and hydrogen when (a) No; (b) NO 2 (c) NO+ (d) NO2
reacted give ..!. mole of cyclohexane and ~ mole 2012
3 3
unreacted hydrogen 16. Which of the following molecules, in pure form is (are)
(c) Hydrogenation of benzene to cyclohexane is an unstable at room temperature ? [IITJEEl
endothermic process

6 (d)6
( d) It is easier to hydrogenate benzene when compared to 0 0
cyclohexene
8. Which of the following is not aromatic [UPSEE] (a) 0 (b) □ (c)
(a) 1, 3-cyclobutadiene
(b) pyridine 17. The non-aromatic compound among the following is
(c) furan [AIEEEJ
( d) thiophene

9. n-C7H16
V2O5, S00'C
l 020atm .
(a) 0 (b) 00
What is B in the above reaction? [AMU] (c) 0s (d) 0 0
(a) Benzyl chloride
(b) Benzal chloride
18. Lindane can be obtained by the reaction of benzene with
(c) Hexachlorobenzene
( d) Benzene hexachloride (a) CH 3 Cl/ anhydrous A1Cl 3 [BITSAT]
(b) C 2 H 5 1 / anhydrous A1Cl 3
10. Which one of the following gives a sooty flame on (c) CH 3 COCI/ anhydrous A1Cl 3
combustion [EAMCETJ (d) Cl 2 in sun light
(a) C 2 H 4
19. Which of the following molecules/species are aromatic
(c) C2 H6 [Manipal]
2013
11. Among P , Q, Rand S, the aromatic compound (s) is/are (a)Q (b)6 (c)l\ (d)+W
[JEE Advanced]

A P
,o 20. Identify C in the following [KCETJ
Cl
AICl3 ~Q @+ CH 3 -fH-CH3
Anhyd. AICI 3
- HCI

0 Cl
~ (NH.th C03 R ~ ~S
0 0 100--IIS°C ,iv A~B
130'(:
Phenol + C

(a)P (b) Q (a) ethanol (b) propanone

(c)R (d) S ( c) cumene hydroperoxide ( d) water
 Hyd rocarbons I 317
21. Ethyl benzene cannot be prepared by [KCET]
(a) Wurtz reaction (b)
0
(b) Wurtz-Fittig reaction
( c) Friedel-Craft's reaction II
C'--~
0
CC
( d) Clemmensen reduction
0
22. By passing excess Cl 2 (g) in boiling toluene, which one of
N02
the following compounds is exclusively fonned [WB JEE]
Me Me

(a)
Cl*Q
~
Cl (b) ~Cl
(c)
Cl~
Cl Cl
~
CliCI CC13 ~N02

(c) (d) © CC
C'--~
0
N02

Cl
23. Friedel-Craft's reaction using MeCl and anhydrous AIC1 3
will take p lace most efficiently with [UPSEE] (d)
(a) benzene (b) nitrobenzene
(c) acetophenone (d) toluene

2010
24. The compounds P , Q and S

i0TCOOHrroCH
,,JV I~ 3 25. o-toluic acid on reaction with Br2 + Fe gives [Manipal]
HO H 3C Q.& O
P II 0
i0TC"O,,JV

H 3C,,JV S
where, separately subjected to nitration using
HN03 I H 2 S0 4 mixture. The major product formed in
each case respectively, is [IIT JEE]
COOH
(a)
HO
26. Which one of these is not true for benzene? CKCET]
N02 0
II 0 (a) It fonns only one type of monosubstituted product

NocH O'c'--
3 0~
(b) There are three carbon-carbon single bonds and three
carbon-carbon double bonds
( c) The heat of hydrogenation of benzene is less than the
H3 C ~ N02 theoretical value
N02 ( d) The bond angle between the carbon-carbon bonds is
120°
318 I Chapterwise & Topicwise Engineering Entrances Solved Papers
27. Benzene on treatment with a mixture of cone. HNO 3 and 36. Toluene on treatment with Cr0 3 and (CH 3 CO)iO
cone. H 2 SO4 at 100°C gives [JCECE] followed by hydrolysis with dil. HCl gives [UPSEEJ
(a) nitrobenzene (b) m-dinitrobenzene (a) benzaldehyde (b) benzoic acid
( c) p-dinitrobenzene (d) o-dinitrobenzene (c) phenol (d) phenylacetaldehyde
28. In the reaction, 37. Which of the following compounds is aromatic? [BCECE]
C H CH
6 5

(a) C 6 H 5 OH
3

the product C is

(c) C 6 H 5 COONa
Oxidation A NaOH B

(b) C 6 H 6
Soda lime

(d) C 6H 5 ONa
C

[Punjab CET]
(•) 0 (b) 6 C6H s
~I
2009
29. The carbon-carbon bond length in benzene is
(a) in between C2 H 6 and C2 H 4
[Manipal] (d) A
HC=CC6 H 5
(b) same as in C 2 H 4
( c) in between C2 H 6 and C2 H2 38. Which one of the following compounds is prepared in
(d) in between C 2 H 4 and C 2 H 2 the laboratory from benzene by a s ubstitution reaction?
30. The strongest ortho/para directing group is (a) Glyoxal [DCEJ
[lndraprasth a CET, CGPET] (b) Cyclohexane
( c) Acetophenone
(a)-NH2 (b)-CH 3
( d) Hexabromocyclohexane
(c)-Cl (d)-C2 H 5
31. Which of the following species is aromatic? [AMU] 2007
e $ 39. Presence of a nitro group in a benzene ring [AIEEE]

(a) 0 (b) 0 (a)

(b)
( c)
activates the ring towards electrophilic substitution
renders the ring basic
deactivates the ring towards nucleophilic substitution

0 0
( d) deactivates the ring towards electrophilic substitution
(c) (d) 40. The compound formed as a result of oxidation of ethyl
EB e benzene by KMnO 4 is [AIEEEJ
(a) benzophenone (b) acetophenone
2008 (c) benzoic acid (d) benzyl alcohol
32. The carbon-carbon bond distance in benzene is [Manipal] A B
41. C?HS 3C12, heat Fe/Br2 Zn / HCI) C
( a) longer than a C-C single bond
Here, the compound C is [BITSATJ
(b) longer than a C = C double bond
(c) shorter than a C = C double bond (a) 3-bromo -2, 4, 5, 6-trichlorotoluene
( d) shorter than a C = C triple bond (b) o-bromotoluene
( c) p-bromotoluene
33. An aromatic compoundX with molecular formula C 8 H 10
(d) m-bromotoluene
produces on nitration one mononitro derivative and three
dinitro derivatives.CompoundX would be 42. Using anhydrous A1Cl 3 as catalyst, which one of the
(a) ethyl benzene (b) m-xylene [Manipall following reactions produce ethylbenzene (PhEt) ?
(c) o -xylene (d) p-xylene (a) H 3 C - CH 2 OH + C6 H 6 [Manipall
34. The overlapping of orbitals in benzene is of the type (b) CH 3- CH = CH 2 + C 6H 6
(a)sp -sp (b)p -p [KCET] (c) H 2 C = CH 2 + C 6 H6
(c) sp 2 -sp 2 (d) sp 3 - sp 3 (d) H 3 C - CH 3 + C6 H6
43. Benzene reacts with chlorine in s unlight to give a final
35. Distillation of acetone with concentrated sulphuric acid product [KCET]
gives [WB JEE]
(a) CC14 (b) C 6H 6Cl 6
(a) diacetone alcohol (b) mesityl oxide (c) C 6Cl 6 (d) C6 H 5 CI
(c) mesitylene (d) propene-2-ol
 Hydrocarbons I 319
44. Pick out the wrong statement. [Ke rala CEE] 51. What is obtained when chlorine is passed in boiling toluene
(a) Toluene shows resonance and product is hydrolysed ? [Manipall

(b) 0+

is non-aromatic
(a) o-cresol
(c) 2, 4-clihydroxytoluene
52. Aromatisation
(b) p-cresol
(d) benzyl alcohol
of n-heptane by passing over
2 (Al 2 0 3 + Cr2 0 3 )catalystat773Kgives
(c) The hybrid state of carbon in carbonyl group is sp
(a) benzene (b) toluene [Manipal, DCE]
(d) The hyperconjugative effect is known as no bond
resonance (c) mixture of both (d) heptylene
(e) Dipole moment of vinyl chloride is less than that of 2 12
methyl chloride
53. C6H5CH3 Cr0 C z [Manipal]

Kf::r-1)1 In the given sequence, Z is

45. 4-nitrotoluene - - - ~ product. The product in the (a) benzaldehyde (b) toluic acid
H2S04
(c) phenyl acetic acid (d) benzoic acid
reaction is [OJEE]
(a) benzoic acid (b) 4-nitrobenzene 54. Benzene can be obtained by heating either benzoic acid
(c) 4-nitrobenzoic acid (d) 2-nitrobenzoic acid with X or phenol with Y. X and Y are respectively [AMUJ
(a) zinc dust and soda lime
46. Friedel-Craft acylation can be given by X is [AMU]
(b) soda lime and zinc dust
O+x A1c13
~IT- R
Vo
(c) zinc dust and sodium hydroxide
(d) soda lime and copper
55. Which of the following reacts with benzene in presence
(a)R - C - CI (b)R - C- R of anhydrous aluminium chloride and forms
II II acetophenone ? [EAMCETJ
0 0
(c)R - C - H (d)R- 0 - R (a) CH3CI (b) CH3 COOH
II (c) CH3CHO (d) CH3COC1
0
47. Identify the substitute group, that acts as ortho-para 56. A cyclic hydrocarbon molecule has all the carbon and
director, during electrophilic substitution in aromatic hydrogen in a single plane. All the carbon-carbon bonds
compounds. [J&K CET] are of same length, less than 1.54 A, but more than 1.34 A.
The C--C bond angle will be [BCECEJ
(a) - NH 2
(c) - S03 H (a) 109°28' (b) 100° (c) 180° (d) 120°
48. According to Huckel's rule an aromatic compound must 57. The conclitions for aromaticity is [Jamia Millia Islamial
possess [J&K CET] (a) molecule must have clouds ofdelocalised n-electrons
(a) (4n + 1) n-electrons (b) ( 4n + 2) n-electrons (b) molecule must contain (4n + 2) n-electrons
(c) 4n n- electrons (d) ( 4n + 3) n-electrons (c) Both (a) and (b)
(d) None of the above
2006
2005
49. Phenyl magnesium bromide reacts with methanol to give
58. Match the following Column I and Column II.
(a) a mixture of anisol and Mg(OH)Br [AIEEE]
(b) a mixture of benzene and Mg(OMe)Br Column I Column II
(c) a mixture of toluene and Mg(OH)Br A. Benzene I. Phosgene
(d) a mixture of phenol and Mg(Me)Br B. Ethylene 2. Silver mirror
50. Two organic compounds A and B both containing only c. Acetaldehyde 3. Mustard gas
carbon and hydrogen, on quantitative analysis gave the
D. Chlorofonn 4. (411 + 2) n-electrons
same percentage composition by weight
5. Carbylamine
C=G!)x 100%, H=C~)x 100%
Codes [UPSEE]
A decolourises bromine water but B does not. A and B A B D
C
respectively are [MHT CET]
(a) 4 3 2 1
(a) C 2 H 2 and C 6H 6 (b) C 6H 6 and C2 H 2 (b) 3 2 I 4
(c) C 2 H4 and C 2 H 6 (d) C 2 H 2 and C2 H 6 (c) 2 4 5 3
(d) 5 I 4 3
320 I Chapterwise & Topicwise Engineering Entrances Solved Papers

59. When chlorine is passed through warm benzene in 61. The presence of the chlorine atom on benzene ring makes
presence of the sunlight, the product obtained iS:Guj CET] the second substituent enter at a position CJ &K CETJ
(a) benzotrichloride (b) chlorobenzene (a) ortho
(b) meta
(c) gammexane (d) DDT
(c) para
60. Aromatic compound among other things should have a (d) ortholpara
1t-electron cloud containing (4n + 2) 1t-electrons where, 62. Which of the following have delocalised electron? [DCEJ
n cannot be [J&K CET]
(a) Benzene (b) Cyclohexane
(a) 1/ 2 (b) 3 {c) 2 (d) 1 (c) CH4 (d) C 2 H 6

Topic 4
Cycloalkanes and Cycloalkenes
2013 2010
1. Match the chemical conversion in Column I with the 5. A dibromo derivative of an alkane reacts with sodium
appropriate reagents in Column II and select the correct metal to fonn an cyclic hydrocarbon. The derivative is
answer using the codes given below the columns. (a) 1, 1-dibromopropane [KCETJ
[JEE Advanced] (b) 2, 2-dibromopropane
(c) 1, 2-dibromoethane
Column I Column II
(d) 1, 4-dibromobutane
I . (i) Hg (OAC)2,
p -)-c1~>= (ii)NaBH4 6. Cycloalkanes are isomeric with [Guj CETJ

Q r ONa ~ r OEt 2. NaOEt

(a) alkanes
(c) alkynes
(b) alkenes
(d) arenes

3. Et-Br 2008
R 7. Which of the following has the maxinmm heat of
hydrogenation ? [Manipal]
4. (i) BH3; H20 2,

s (ii)NaOH (a)
0 (b)
0
Codes
P Q
(a) 2 3
R
1
S
4
P
(b) 3
Q
2
R
1
S
4
(c)
0 (d)

8. The angle strain in cyclobutane is

0 CKCETJ
(c) 2 3 4 1 (d) 3 2 4 1 1 1 1 1
(a) 24°44 (b) 29°16 (c) 19°22 (d) 9°44
2. Cycloalkane has the general formula
9. Which cycloalkane has the lowest heat of combustion per
(a) CnH2n+2 (b) Cn H 2n - 2 (c) CnH2n CH2 group ? [Jamia Millia Islamia]
(e) C2nH2n (a) Cyclopropane (b) Cyclobutane
3. Which of the following cycloalkane gives open chain (c) Cyclopentane (d) Cyclohexane
compound, when reacts with bromine? [OJEEJ
(a) cyclopropane (b) cyclopentane 2007
(c) cyclohexane (d) cyclooctane 10. Angle strain in cyclopropane is CKCETJ
1 1 1
(a) 24°44 (b) 9°44 (c) 44 (d) - 5°161
2012
4. Action of bromine on cyclopentene gives [BITSAT] 2006
(a) cyclopentyl bromide 11. Which will react with NaBH4 ? [OJEE]
(b) 1, 2-dibromo cyclopentane
(a) Benzoic acid (b) Benzamide
(c) cyclopentyl dibromide
(c) Cyclohexanone (d) Acetic acid
(d) No reaction
 Hyd rocarbons I 321
2005
12. Suitable reagents A and B for the following reactions are
[BITSAT]
,.--------(Br
On reductive ozonolysis yields [UPSEE]
□ +A~ U__J (a) 6-oxoheptanal (b) 6-oxoheptanoic acid
(c) 6-hydroxyheptanaI (d) 3-hydroxypentanal
,----/Br
14. Cyclohexene on reaction with OsO4 followed by reaction
D +B~ L_j with NaHSO 3 gives [OJEE]
(a) Br, Br2 (b) Br2 , NBS (a) cis-diol (b) trans-diol
(c) NBS, NBS (d) NBS, Br2 (c) epoxy (d) alcohol

Topic 5
Petroleum Cracking, Knocking and
Coaltar Distillation
2010
1. What will be the octane number of best fuel? [MP PET] 8. Cetane is a compound which has very good ignition
(a) 80 (b) 81 (c) 74 (d) 65 property. Chemically it is [WB JEE]

2. Petrol for aviation purpose must contain [RPET] (a) CH 3 (CH 2 ) 14 CH 3 (b) (CH 3 h C(CH2 ) 11 CH 3
(c) C17 H 34 (d) None of the above
(a) straight chain hydrocarbons
(b) aromatic hydrocarbons 9. LPG mainly contains [UPSEE]
(c) olefinic hydrocarbons (a) ethyne (b) butane (c) methane (d) ethane
(d) highly branched chain paraffins 10. Petroleum is obtained from water gas, name of the reaction
2009 involved is [DCEJ
(a) Fischer-Tropsch (b) Bengoic
3. TEL is a compound used as [UPSEE]
(c) Dow's (d) Kjeldahl's
(a) antibiotic (b) antiseptic
(c) anti.knocking (d) antioxidant 11. Which of the following is correct number of carbon atom
present as the constituent of kerosene oil ?
2008 [Jamia Millia Islamia]
4. Petrochemicals can be used to prepare [Manipal] (a) C10- C16 (b) C4- C6
(a) synthetic fibres (b) pesticides (c) C8- CI6 (d) C12 - C1s
(c) plastics (d) All of these
12. Which of the following increases the octane number ?
5. Gasoline with an octane number of 80 is equivalent in (a) Branching of chain [Jamia Millia Islamia]
knocking characteristics to a mixture of heptane and
(b) Absence of double and triple bond
iso-octane of the following composition [Guj CET]
(c) Non-cyclic alkanes
(a) 20% heptane+ 80% iso-octane (d) None of the above
(b) 90% heptane + I 0% iso-octane
(c) 80% heptane + 20% iso-octane 2005
(d) I 0% heptane + 90% iso-octane 13. Tetraethyl lead is a [BITSAT]
6. Synthetic petrol is prepared by [DCE] (a) solvent (b) petroleum additive
(a) Wurtz reaction (b) by distillation (c) oxidising agent (d) fire extinguisher
(c) F ischer-Tropsch process (d) None of the above
14. In laboratory burners, we use [Manipal]
2006 (a) producer gas (b) oil gas
(c) gobar gas (d) coal gas
7. Which of the following fraction of coaltar distillation is
obtained at 270°-360°C? [MHT CET] 15. Which of the following is present in natw-al gas?
(a) Light oil (b) Middle oil (a) n-butane (b) Ethane [BCE CEJ
(c) Green oil (d) Heavy oil (c) Methane (d) Propane
 Answers
lOe!C..1 Preparation of Aliphatic Hydrocabons
1. (d) 2. (d) 3. (d) 4. (d) 5. (c) 6. (c) 7. (d) 8. (a) 9. (c) 10. (d)
11. (c) 12. (c) 13. (a) 14. (d) 15. (b) 16. (c) 17. (c) 18. (b) 19. (a) 20. (c)
21 . (d) 22. (c) 23. (b) 24. (c) 25. (b) 26. (d) 27. (b) 28. (c) 29. (b) 30. (c)
31 . (d) 32. (d) 33. (b) 34. (c) 35. (a) 36. (a)
TOPIC2 Properties of Aliphatic Hydrocarbons
1. (b) 2. (c) 3. (c) 4. (a) 5. (b) 6. (b) 7. (b) 8. (a) 9. (a) 10. (b)
11. (b) 12. (a) 13. (d) 14. (b) 15. (d) 16. (d) 17. (c) 18. (b) 19. (a) 20. (c)
21 . (d) 22. (a) 23. (b) 24. (b) 25. (b) 26. (a) 27. (a) 28. (a) 29. (d) 30. (b)
31 . (d) 32. (a) 33. (b) 34. (b) 35. (b) 36. (d) 37. (c) 38. (a) 39. (d) 40. (a)
41 . (b) 42. (a) 43. (b) 44. (d) 45. (c) 46. (d) 47. (d) 48. (c) 49. (d) 50. (c)
51 . (b) 52. (a) 53. (a) 54. (c) 55. (d) 56. (e) 57. (b) 58. (a) 59. (a) 60. (c)
61 . (b) 62. (d) 63. (a) 64. (d) 65. (c) 66. (c) 67. (c) 68. (c) 69. (d) 70. (b)
71 . (a) 72. (b) 73. (d) 74. (c) 75. (c) 76. (a) 77. (b) 78. (b) 79. (c) 80. (d)
81 . (c) 82. (a) 83. (a) 84. (a) 85. (d) 86. (b) 87. (d) 88. (c) 89. (d) 90. (a)
91 . (a)
Topic 3 Aromaticity, Structure of Benzene and Aromatic Hydrocarbons
1. (a, b , d) 2. (a, b, c) 3. (d) 4. (a) 5. (b) 6. (c) 7. (a) 8. (a) 9. (b) 10. (d)
11. (a, b , c, d) 12. (d) 13. (b) 14. (c) 15. (a) 16. (b) 17. (a) 18. (d) 19. (c) 20. (b)
21. (a) 22. (d) 23. (d) 24. (c) 25. (C) 26. (b) 27. (b) 28. (b) 29. (a) 30. (a)
31. (b) 32. (b) 33. (d) 34. (c) 35. (c) 36. (a) 37. (d) 38. (c) 39. (d) 40. (c)
41. ( d) 42. (c) 43. (b) 44. (b) 45. (c) 46. (a) 47. (a) 48. (b) 49. (b) 50. (a)
51. (d) 52. (b) 53. (a) 54. (b) 55. (d) 56. (d) 57. (c) 58. (a) 59. (c) 60. (a)
61. (d) 62. (a)
T0PIC4 Cycloalkanes and Cycloalkenes
1. (a) 2. (c) 3. (a) 4. (b) 5. (d) 6. (b) 7. (c) 8. (d) 9. (d) 10. (a)
11. (c) 12. (d) 13. (a) 14. (a)
TOPIC5 Petroleum; (raking, Knocking and Coaltar Distillation
1. (b) 2. (c) 3. (c) 4. (b) 5. (a) 6. (c) 7. (c) 8. (a) 9. (b) 10. (a)
11. (a) 12. (a) 13. (b) 14. (b) 15. (c)
 Explanations
Topic 1 Preparation of Aliphatic Hydrocarbons
1. 3-octyne is obtained by the reaction of I -bromobutane and 8. Thermal decomposition of alkanes in absence of air is called
but-1-yne in presence of sodamide. cracking or pyrolysis.
CH 3CH 2C=CH + NaNH2 - CH3CH2- C=C:Na+ e.g. CH4 IOOO"C> C + 2H 2

CH3CH 2 C=CNa+ + BrCH 2 CH2 CH 2CH3 9. CH 3CH 2CH3 40o- 600°C CH 2 = Q-1 2 + CH4
X y
- CH3CH 2 C=C - CH2CH2 CH2CH 3
3. octyne Hence, X and Y are ethylene and methane, respectively.
2. Wurtz reaction involves the reduction of alkyl halide with Na in 10. Alcoholic KOH is a dehydrohalogenating reagent, so when
n-propyl bromide is treated with alcoholic KOH, propene is
ether RX + 2Na + XR' ~ R- R + 2Na- X obtained.
ether
CH 3CH 2CH2Br + Ale. KOH - CH3CH = CH2 + HBr
Wurtz reaction is a convenient method for the preparation of n-propyl bromide Propene
symmetrical alkanes (R- R), i.e. a lkane containing even number
of carbon atoms. 11. (CH3)3C- MgCI+ D-on - (CH3)3C·D + MgCl(OD)
Grignard reagent
3. Decarboxylation of sodium propionate leads to the formation of [Grignard reagent when reacts with a protic solvent, gives alkane.]
ethane
12. When an alkyl halide reacts with sodium in presence of dry ether,
Ca0.360 K an alkane with the double number of carbon atoms than the parent
CH 3- CH 3 + Na 2C03
Ethane halide, is obtained and this reaction is known as Wurtz reaction.
4 3 2
4. When two different alkyl halides are heated with sodium metal in C H 3- CH- ~H- CI
the presence of dry ether. A mixture of different alkanes (having I II
double or more the number of carbon atoms are present in the CH3 CH3
parent halide) is obtained. The reaction is called Wurtz reaction.
2- chloro-3 methyl butane
C2H 5Br + 2Na + CH3Br Dry ether CH 3-CH3 3 2
Ethane Na
+ CH 3- ? H - ?H- Cl Dry ether
+ C2H 5- C2H 5 + C2H 5- CH 3 -2NaCI
Butane Propane CH3 CH 3
6 5 4 3 2 I
5. CH CH2- CO~a+ + NaOH- - - ea_o_ _ C H3- ?H - ?H- ?H- ?H - CH3
3 Decarl>oxylation
CH3- CH3 + Na 2C03 CH 3 CH 3 CH 3 CH 3
Ethane 2, 3, 4, 5 -tetrarrelhyl hexane
The process of removal of a molecules CO 2 from an organic
compound is called decarboxylation. rH3 CH3 CH3
I I
6. This is also a mean of preparing alkene where, the position of the 13. CH 3 - CH - C- CH3 H 3C - C = C - CH3
I I 2, 3-dimethyl -2,.butene
double bond is definite. In Wittig reaction, aldehyde (- CHO) (m.1jor product)
OH CH 3
and ketone ( C =0) react with methylene triphenyl phosphine
3, 3-dimethyl butane-2-ol
[(¼HshP =CH 2 ] to give alkene.
CH 3CHO + (C6H 5hP =CH2 - 14. In the formation of an alkane from Grignard reagent, alkyl group
CH 3 - CH=CH 2 + (¼;H 5hP=O always comes from Grignard reagent. Hence, the number ofcarbon
Propene Triphenyl pho,phine atoms in the Grignard reagent and alkane formed Grignard reagent
oxide
will be identical. So, the original alkyl halide is propyl bromide.
H3C""
Dry
/C=O + (C6H 5)3P=CH2 - CH 3CH 2CH 2- Br + Mg --➔ CH 3CH2CH2- MgBr
Propyl bromide ether Propylmagnesium halide
H3C
H20
H3C"" ~ CH3CH 2CH3 + Mg(OH)Br
/ C = CH2 + (C6H5)3 P = 0 Propane
H3C 15. Symmetrical optical isomers are called mesomers.
7. On treatment w ith alcoholic KOH, 1-chlorobutane gives I -butene HC
Debromination 3 '--C=C_.,,.,CH3
while 2-chlorobutane gives 2-butene (major) + I-butene (minor).
H/ '--H
Therefore, a mixture of !-butene + 2-butene is formed.
cis-2-butene
meso-dibromobutane
324 I Chapterwise & Topicwise Engineering Entrances Solved Papers
16. In Wurtz reaction alkyl halide reacts with sodium in presence of 24. On electrolysis of potassium salt of fumaric and maleic acid,
dry ether to give alkanes e.g. ethyne gas is obtained.
Dry ether - +
C2H 5C l + 2Na + CIC2H 5 ---➔ C4H 10 + 2NaCl CHCOOK
Butane
CH
In Wurtz reaction, wet ether is not used because wet ether destroy II - +
Ill
CHCOOK CH
the sodium metal. Ethyne
potassiwn
17. Wurtz reaction Alkyl halide reacts with sodium in presence of rnaleate

dry ether to form a lkane is known as Wurtz reaction.

25. Al 4C3 on hydrolysis gives me thane gas.
Ether
CH3Br + 2Na + BrCH3 - - 4 Al 4C3 + 12H2O - 4Al(OH)3 + 3CH4
CH3- CH 3 + 2NaBr -+
CHCOOK CH
Electrolysis
Br Br'-- _ / H Ill
18. H H) f Br
H _Ale.
_KOH__, '-.
./-"-,_
H ./ "'-H
26. II -+
CHCOOK
Potassium maleate
CH
Acetylene
(at anode)
+ 2CO 2 + 2KOH + H2
Cathode

NaNH ) H ---=---H 27. When calcium carbide reacts with water, ethyne is formed.
CaC2 + 2H2O ---➔ C2H 2
V inyl ic bromide is more stable stronger base (- NH2) is required Calcium -Ca(OH) 2 Ethyne
carbide
for elimination.
HCOOH + HCOOH
Zn+HCI Fonnic Formic
19. CHi + 2H CH4 + HI acid acid
Zn - Cu / ~ H sOH
Methane
Dry ether 28. Only alcoholic KOH gives dehydrohalogenation reaction. Ethyl
CH 3 - CH3 + 2NaI chloride reacts w ith alcoholic KOH as
Ethane
H H
20. CH2 =CH - CHzCI+ CH 3MgI - I I
Allyl chloride

CH 2=CH- CH2 - CH 3+ Mg'-.

/I H[l I•rc;lH ~ rn,,..;:', +H,o+Kc1
I-butene '-. C l
HO GJ
29. When sodium propionate is heated with soda lime, ethane is
Butene-I formed.
CH3 - CH2 - CH2 - CH3 CH 3CH 2COONa + NaOH eao > C2H6 + Na 2CO 3
Butane Ethane
Other reagents are successful w ith polar double bonds.
30. 1, 2-dihalogen ( vicinal) derivatives of the alkanes on reaction
22. Methane cannot be produced by Wurtz reaction, Kolbe's with zinc dust and methanol produces alkenes by loss of two
electrolytic method and reduction w ith H 2 because, it has one halogen atoms (dehalogenation).
carbon atom. Alcohol/!!.
Pure methane can be produced by the decarboxylation of sodiwn CH 3 - C H - C H 2 + Zn CH 3CH = CH2
acetate.
I I Propylene
Br Br
- + eao I, 2-dibrormpropane
CH3COONa + NaOH - CH 4 + Na 2CO 3
Soda limo Methane
31. Methyl iodide and ethyl iodide, on treatment with sodium in
23. It is a Corey- house synthesis ofalkanes. ethereal solution, give a mixture of propane, ethane and butane,
as follows
R- X + 2Li ~ R- Li + LiX
ether Alkyl
lithium
CH3I + 2Na + I - CH2CH3 ~ CH 3CH2CH3 + 2NaI
Propane
2R- Li + Cul --4 [R2Cur Li+ + Lil
Lithium CHi + 2Na + I - CH3 - CH 3 -CH3 + 2Nal
dialkyl copper Ethane

rR\ _
DI
r
J Li+ + R- X --4 R- R' + RCu + LiX
C 2H 5I + 2Na + I - C2H 5 - C 2H 5C2H 5 + 2NaI
Butane
lR / Alkane
32. The reaction is Wurtz's type reaction
Corey-house synthesis is used to prepare both symmetrical and
unsymmetrical.

Br
,,0 + Cl

2 N,---"""--, 0 +N,Cl +Nafa

 Hydrocarbons I 325
33. Wurtz reaction is used to prepare alkanes from alkyl halides Hence, all unsaturated compounds having ability to form
Dry ether sulphonated compound are soluble in cone. H 2S04 so while
2R - X + 2Na R- R + 2NaX
sanrrated compound does not dissolve in cone. H 2S0 4 solution.
Dry ether 5. When HBr is added to 2-butene it forms 2-bromobutane.
34. 2CH3 - CHBr + 2Na CH3 - T H- ?H - CH3
I CH3CH =CHCH3 + HBr -
CH3 CH3 CH3 2-butene
l,opropyl bromide 2, 3-dimethyl butane

35. CaC2 + 2H20 - C2H 2 + Ca(OH)2 2-bromobutane

Ethyne
1
Calcium carbide is obtained by following reaction 6. Boiling point ex atomic mass ex .
branching
2275K
CaC03 CaO+ C02 :. The correct order of boiling point at n-pentane (at. moss =72)
Limestone
< 2, 3 dimed1yl butane< n -hexane .
Cao+ 3C _ 2_2_
1 s_K_ (at. mass - 86) (at. mass - 86)

36. Alkyl halides can be reduced to hydrocarbons by means of

Zn - Cu couple in presence of alcohol.
Z.n-Cu
C2J\ + HT
CiHsOH
Ethane
8. Ozonolysis of the given triene occurs as follows :
Topic 2 Properties of Aliphatic CH3 CH3
Hydrocarbons
1. Branching in an alkane, decreases the surface area and its boiling
point also decreases.
CH3CH = CH-C-
'
-
H
CH= CH- C -
'
-
H
CH = CHCH = CH
I

CH3
CHO f
TTI II ~~> 2CH3CHO + tHO + 2HOC - 1- CHO

On moving left to right (III to I) ii

• branching increases Since, none ofilie above dial is chiral, no optically active product
• surface area decreases is obtained.
• boiling point decreases 9. CH3- CH2- C == C- H + Hp
Butyne-1
Hence, correct choice is (b).
2. The reaction is
6Ag
2CH3- C- Cl3 - CH3- C= C- CH3 + 6AgCI CH3-CH2- r=CH2
6 But -2-yne

3. Ethyne C2H 2 OH
Unstable
Number of cr bonds at C-atom = 2 0
Number of lone pair of electron at C-atom = 0
Total 2 + 0 = 2 Tauto1nerisation
CH3- CH 2- C- CH3
II
Hybridisation = sp A
Ethyl methyl ketone or
C2H 2 is linear
2-butanone
Methane (CH4 )
1O. Molar mass = 72 = CnH2n + 2
Number of cr bonds at C-atom = 4
Number of lone pair of electrons at C-atom = 0 = 12n + (2n + 2)
Total 4 + 0 = 4, ⇒ n=S
Hybridisation = sp3 Thus, hydrocarbon is C 5H 12•

0
: . CH 4 is tetrahedral. Since, it forms only single C5H 11 CI isomer, hence, it is
neo-pentane.
CH3
(d) I Cl2
H3C- C- CH3 -
Among the given four only (a) is a saturated hydrocarbon so it I
will not dissolve in cone. H 2 S04 because unsaturated organic CH3
compound causes formation of sulphonated salt in conc.H 2S04 .
326 I Chapterwise & Topicwise Engineering Entrances Solved Papers

11. CH3CH2CH2- C = C- CH3

(b)Li / NH3 17. C.H21,0 = 44
2- hexyne C.H2n = 44 - 16 = 28
n.=2
So, CH3- CH= C H- CH3 is symmertrical alkene.

~ 2--, n-hexane
2-hexyne _(_•J_PVH 18. Only terminal alkynes give precipitate with ammoniacal silver
I nitrate solution. Among the given, CH3- C == C- CH3 is not a
(cJ >cis-2-hexene
Pd/BaS04 terminal alkyne. Thus, it does not give precipitate with
~_ _(_d)_- no reaction ammoniacal AgN0 3.
19. According to Markownikoff's rule, the negative part of the
0 reagent gets attached to that double bonded carbon atom which
has least number ofH-atoms. Thus,
12. CH3C=CH + o - o- CH3 - CIH
Propyne \0/ I I CH2= CH-CH3 ~ CH3- r - CH3
0 0 Br
Cone· H2S04
-~~ CH3COOH + HCOOH 20. 3CH3- C=CH
2 Polymerisation
Propyne
13. Conjugate dienes have alternate single and double bonds bonds.
H3CY CH3
CH3 1/' I
e.g. CH2 =
I
C- CH = CH2
~

CH3
14. Alkenes give carbonyl compounds on ozonolysis. Mesitylene
03 / Zn / H20 6- 6+
Alkene ------+ HCHO + Other carbonyl compound
A 21. CH3CH =CH2 + HOBr - CH3CH - CH2Br
Propene I
OH
1-brom::>- 2--propanol
The addition takes place according to Markownikoff's rule.
To determine alkene, place carbonyl compounds with their 1
22. Boiling point oc Molecular mass oc
0-atom face to face. Replace 0-atom by a double bond Branching
R I'-.... Replace R 1'-.... (": surface area decreases)
R /C= O O=CH2------'---➔ R ,...C =CH2
2 (B) (R) 0-atom by(= ) bond 2,... f :. ,i-hexane has the highest boiling point among the given.
Vinyl group - + CH3I
()-.atoms face to face 23. HC =CH NaNHi
HC == CNa (- Na!)
(Due to ac,d,c HJ
I
Acetyene X
O 3 / H 2 0 / Zn H3C '-...._
15. Alkene /C= 0 + CH3CH2CHO
H3C HC == C·CH3
y
To identify alkene (from ozonolysis products), place these
products with 0-atoms face to face. Replace 0-atoms by =
(double) bond. 24 Dil. H2S04 + HgS0 4
H3C'-...._ • HC = CH HC =CH2
(HOH)
/ c o + _QCHCH2CH3~
unsaturated
site I
H3C b.
atotm face to face
HO..)
I
H3C '----._ 2 3 4 s -- - - - - > H ¾•C ¾•CH3
Tautomerisation

/ C = CHCH2CH3 II
H3C 0
Acetaldehyde
2-methyl -2-pentene
25. Mustard gas is~. W-dichloro diethylsulphide which is prepared by
the action of sulphur monochloride on ethylene.
CH2 CH2 CH2Cl CH2Cl
II + SiCl2 + II - I I +S
CH2 Sulphur CH2 CH2 CH2
monochloride \ /

Mu,tard gas
s
J3,W-dichlorodiethyl sulphide

Since, it is highly poisonous, it is used in chemical warfare.

 Hydrocarbons I 327
26. Markownikoff's addition The negative part of the 33. Ethane gives a mixture of nitroethane and nitromethane.
unsymmetrical reagents adds to a less hydrogenated (more CH3 - CH3 + HN03 ~~2~ l CH3 - CH2 - N02
substituted) carbon atom of the double bond. In ICI, Cl is more B:hane Nitroelhane
(major)
electronegative. So, it will take negative charge, i.e. f'CI - .
+ CH3N02
So, the product is Nitromethane
+ - (minor)
RCH2CH = CH2 + I Cl ~ R - CH2- CH- CH2I
I During nitration, chain fission of alkanes also takes place, so
Cl CH 3N02 is also obtained along with CH3CH2N02.
27. The formation of the alkene in an elimination reaction is called 34 . Since, the alkene of oxidation gives only acetic acid, therefore,
Hofmann elimination (thermal decomposition). Elimination of the alkene must be symmetrical containing two carbon-atoms on
hydrogen occurs from the f>-carbon. So, either side of the double bond, i.e. 2-butene.

o-CH2N~e30H- ~ 0 = CH2 +NMe3 + H20 CH3CH = CHCH 3 KMn04 l 2CH3COOH

35. Oxidation of I-butene first gives a mixture of prop ionic acid and
28. Since, the alkadiene on reductive ozonolysis gives acetaldehyde formic acid. Formic acid, however, gets further oxidised to CO 2
(CH3CHO\ acetone (CH3COCH 3) and and Hp. Therefore, option (b) is correct.
2-methylpropane-l , 3-dial [OHCCH(CH3)CHO], the structure of KMn04
alkadiene will be obtained as CH 3CH 2CH = CH2 + 4(0)- CH3CH2 COOH + HCOOH
H H H I-butene

I ,---------, I I ,---------, ~ C 0 2 + H20

CH3C =i= 0 + 0 =l= C - CH - C =i= 0 + 0 =l= C(CH3h
Acetaldehy~;-------J I L-------~Jcetone 36. CH3 -CH2 -CH2 -C=CH + CH3MgBr
Methyl rmgnesium
CH3 bromide
7 6 5 4 3 2 I
-➔ CH 3 CH= CH- CH - CH= C - CH3 Br
I I CH4 + Mg<
CH3 CH3
2, 4-dimethylhepta-2,5-diene (alkadiene)
C CCH 2CH2CH3 =
Due to the presence of acidic hydrogen (hydrogen attached to
0
triply bonded carbon atom), terminal alkyne (d) will react with
03 /\ methyl magnesium bromide.
29. CH3CH= CHCH 3 ~ CH3 -CH C(H- CH3 )
6~ 37. Ammoniacal cuprous c hloride will give red precipitate with
1-alkynes (terminal alkynes).

1~~i!'.J~
2CH 3 -CH=O
ozonolysis

B
CH3 -C== CH+ 2 [Cu(NH3h]CI ~
CH 3 - C == C - Cu + 2NH4 CI + 2NH3
Red ppl

30. CH 3CH2C=CH Na/liq. NHJ CH3 CH2C=CNa+ 38. The addition of HBr to an alkene is an example of electrophilic
A addition reactions. It takes place by following mechanism.
Considering the options given, it appears correct. Na/liq. NH 3 is
known for metal dissolved reduction. Actually it is truth that H3C - r=r-0-0H~
Na/ liq. NH3 reduces internal triple bond and terminal double

-o-
bond and do not reduce the terminal alkyne due to such alkylide CH3 H
formation.
31. Terminal alkyne has acidic hydrogen which is enough to H3C - ,(±)- CH2 ~ /; OH
protonate the Grignard reagent. H3C
CH3MgX + CH3C = CH ~ CH4 + CH3C== CMgX Less stable carbonium ion

H3C~ / H
32. H3C-C== c - c H3 Na, liq .NH3 / c = c"" + H3C - TH - (
CHt ) ~
-0/; - OH
H CH3 H3C
ami -addition product More stable due to resonance
£-product

syn-addition product
Z-product
328 I Chapterwise & Topicwise Engineering Entrances Solved Papers

5 4
39. X is a three carbon compound with two halogen atom, so its
molecular formula is C3H6Cl 2. Only terminal alkynes give red CH 3 CH2 ~ 3 2/ H
ppt. with ammoniacal Cu 2C12, so the hydrocarbon produced by C=C
the reaction ofX with alcoholic KOH, must be a terminal alkyne CH /
3
"'-cH
I 3
i.e. CH3C == C H. 3- methyl -2 pentene
C H Cl Ale· KOH CHJC == CH Ammoniacal Cu 2CI 2 (i) 0 3
3 6 2
CH 3C = CCu1
Redppl.
43.
0 (ii) Zn-H20

C
Zn -H20 is the reagent for reductive work up
CHO
CHO
of ozonide.
Compound (X) gives an aldehyde when reacts with aqueous
KOH. This suggests that both the halogens are present on same H 20 2 -CH 3COOH would give HOOC - ( CH2 ) 4 - COOR.
terminal carbon atom. Thus, the formula of compound X is 44. An alkyne combine with a conjugated diene to give an
unconjugated cycloalkadiene. This reaction is known as
/Cl

t
Diels-Alder reaction.
CH3 - CH2 - CH "'-
( t. 1-dichloropropane)

and the reactions are as follows

Cl
+ ri11 -► o
Cl Butadiene Acetylene Cyclohexadiene
/ Ale-KOH
CH3CH 2CH"'- - - -..... CH3
Cl I
45. CH3- CH2- CH - C == CH
X
3 -mothyl - 1-pcntyne
Ammoniacal CH3 0 -- 0
_ eu
_ 2c_,_
2- CH3C == CDil
CH3- CH2 -
tH- I
C\ / C H ~
I [OJ
Redppl.
Qzomde
Cl
/ at/. KOH CH 0
CH3CH2CH "'- I 3
Cl CH3- CH2 - CH - COOR+ HCOOH
X Optically active carboxylic acid
I, 1-dichloropropane
OH 46. CH3CH 2C == CH + H 20
2
CH3CH2C< -H o CH3CH2CHO 1-butyne
Unstable OH Propanal OH OH
I HO I
0 CH3CH2C=CH2 ~ CH 3CH2 - C - CH 3
M~ /Me I
40. / C=C"'- ~ Me>( )<Me OH
Unstable
Me H Me 0--0 H -HiO CH3CH2 - C - CH3
Oz.onide
II
0 0 0
II II Butane• 2-one
Me - C - Me + Me - C - H 47. Ozonolysis involves the breaking of double bond and insertion of
Ketone Aldehyde
0 atoms in place of double bond. Therefore, the structure of
41. The product of given reaction will be according to alkene is as
Markownikoffs rule, this is because peroxide effect is applicable -02
H 3C- C= O + O=C- CH3 ~
only in case ofHBr and not effective in case of HI. I I 0 3I H 20
CH 3- CH= CH2 __Hl_➔ CH3 - <;:H - CH3 H H
Peroxide I Acctaldchyde

I (P) H 3C- CH = CH- CH3

2-butene

48. Copper and silver alkylides are obtained by passing alkynes in the
42. X _(_iJ_o_3_ _..... ammoniacal solution of cuprous chloride and silver nitrate
(ii) Zn/ AcOH respectively. These reactions are used for detecting the presence
ofacetylenic hydrogen atom.
The aldehyde should be CH3CHO because the molecular formula
is C2 H 4O.
CH 3CH2~ /H Copper acetylide
Acetylene Amn:miacaJ (red ppt.)
/ C = 0 + 0 = C "'- cuprous chlorid

CH3 CH3
2 - butanone Ethanal
So, alkanes and alkenes remain unaffected.
 Hydrocarbons I 329
55. Reaction ofHBrwith propene in the presence of peroxide gives
49. HC=CH
n-propyl bromide. This addition reaction is an example of
Tautoroorisation
anti-Markownikoff addition reaction.
i.e. it is completed in form of free radical addition.
CH 3CHO
Peroxide
50. CH =CH + 2HCHO - HOH2C - C=C- CHpH CH3- CH2- CH2Br
Acetylene 2-butyne-1, 4-diol n-propyl bromide

R"' /R CH 30 - CH= CH2

51. / C = C"' Methyl ,inyl ether
H H 57. Butyne reacts with Na/liq. NH3 to give trans-product.
cis-alkene
(B) H 3C~ /H
CH3- C==C-CH3 Na/liq.NH3 /C=C"'
T
I+ Hi Lindlar
catalyst H CH 3
trans-pnxluct
R H
Nain ) "'C= C / -
R- C=C - R 58. CH3CH =CH2 + HO Cl+ - CH 3-CH-CH2
A lkyne liq.NH3 / "' Propcne Hypochlorous I I
H R
lrans-alkene acid OH Cl
(A) Propene chloroh)'drin

C
59. Propyne on passing through red hot iron tube gives mesitylene.
52.
0 CHO

s&
CHO
Compound£
CHO
CH3 - C == CH - -7-75_K_ _
Red hot Fe tube

A
l>c~ ~vOH
AcH=O Propyne
H 3C CH3
Mesitylene

I
H
Jntramolecular
aldol condensation
60.
0 03llf20
- - ---+½
CHO

CHO
+ ½
CH2 CHO

CH 2CHO
Dehydration

CompoundF
So, the olefin is O.
53. CH 3- C==CH + HBr - CH3 - ?=CH2
61. CH 2=CH2 + HCl Anhy.AICl 3 CH3CH2Cl + 2[H]

lz:.eu
Br

CiHsOH
C2H6
B
H3C~
B- + 62. /so-butene / C =CH2 has minimum force of attraction
CH 3 - ?- CH3 ~ CH3 - ?- CH3
H3C
Br Br (due to steric hindrance). Thus, minimum boiling point.
2, 2-dibromopropane More stable +
carbocation
63. CH3-CH = CH2+ NOCl- - CH3-CH- CH 2
CH 3-CH = CHBr~ CH 3 -Gl2-CHBr2 I I
Cl NO
CH =CH ~ CH 3CHBr2 This reaction is an example of electrophilic addition reaction
and in it addition takes place according to Markownikoffs
CH3- CH=CH 2 HBr CH3- CHBr - CH3 rule.

64. CH2=CH- O- CH3 HBr CH 3 - ?H - 0- CH3

Br
Ozonide First protonation occurs, two possible intermediates are

CH3 - C- C- CH 3
I II
0 0
330 I Chapterwise & Topicwise Engineering Entrances Solved Papers

CH2 -+- CH -+- OCH3 72. Reaction of a non-terminal alkyne with a solution of an alkali
+ I metal (usually Na or Li or K) in liquid ammonia give a
H (I)
trans-alkene.
(- / -effect destabilises carbocation)
+
and CH 3 - CH - ~ CH 3
(II) H 3C"' /H
( + M effect stabilises carbocation) C=C '-....
II, is more favourable. Hence, Br- attacks, and product is H/ CH
3
CH3 -CH-O-CH 3 73. The reaction is ozonolysis. During the reaction C= Cbreaks to
t give carbonyl compounds.
03
CH CHOH CH3CH = CH2 ~ CH3CHO + HCHO
2 2 Acetaldehyde Formaldehyde
65. Ill + HOCI
Hypochlorous acid
- II
CH CHCI
Acetylene 74. 3° (C-H) bond has minimum bond energy hence, easily cleaved
f CH(OH)27 - H20 CHO giving 2- bromo -2-methylbutane
~ I H H
lhic12 J
Unstable
CHCl 2
Dichloro H 3C - { - { - CH3 ~ CH3 - CH 2 - { - CH 3
Br

acetaldchyde
H CH 3 CH 3
66. According to Markownikoff's rule, the addition of an
unsymmetrical reagent (HX) to an unsymmetric alkene takes place 75. CH 2 =CHCH= CH 2 + HBr-
in such a way that the negative part of die reagent will be attached
CH3CH CH= CH, + CH 3CH =CHCH,Br
to the carbon atom which containing lesser number of H-atom. I - -
Hence, it is best applicable to the reaction between C3H6 and HBr. Br
CH 3CH= CH 2 + HBr - CH 3 - 9H - CH 3 I, 2-addition product I, 4-addition product

Br Addition is through the formation of allylic carbocation.

$ $
CH2 =CHCHCH3 ~ CH 3CH= C HCH2
67. An alkene on reductive ozonolysis gives 2 molecules of (2 ° allylic) (1 ° allylic)
CH 2 (CHO)2. Hence, the alkene is I, 4-cyclohexadiene. ( more stable) (less stable)
,6g_~g~-
0 + 203 CH,CI,

I, 4-cyclohexadien
,-xo-~o,,.-:--
Under mild conditions (temperature "' - 80° C), kinetic product is the
I, 2-addition product and under vigorous conditions (temperature
"' 40° C~ thermodynamic product is the I , 4-addition product.
[zn1H20 Thus, 1-bromo-2-butene is the major product under given
1-Zno (reductive cleavage) condition.
CHO CHO
I I A is meso-diol.
CH2 + CH 2
I I OH
CHO CHO A

68. By adding bromine water to a solution, if the colour of bromine 77. o - C H2CH= CH 2 + NBS~
water decolourise then the compound is unsaturated. This is a
confirmatory test for unsaturation.
0 - C H = CHCH 2Br
69. When med1ane is oxidised in presence of molybdenum oxide
(MoO), it gives medlanal (formaldehyde).
78. Conversion of propene to propanol is hydration
CH4 + 2(0] (MoO) HCHO + H 2O
Formaldehyde OH
H2 S04 I
70. Ethylene reacts with 1% alkaline KMnO 4 gives ethylene glycol. CH 3 - CH= CH2 + H2O _ ____, CH3 -CH-CH 3
Propene Propanol-2
CH2 CH 2OH
II + H2O + 0 !% alkaline I 79. Decolourisation ofKMnO4 (unsaturation test)
KMn04

~
CH 2 CH2OH
Ethylene glycol
Ethene Acetylene
71. H 2C =
A
CH2
HBr
~
Ale. KOH
CH 3CH2Br - - ~ H 2C = CH2
~ A
lCuCl2, NH40H lCu2Cl2, NH40H
Hence, A = C2H 4, B = Ale. KOH / l"1 Noppt. Red ppt.
 Hydrocarbons I 331
CH3H CH3 89. Propyne reacts with AgNO3 in NH3 to give white ppt. of silver
I 1,-------------------, /
80. CH3 -T- C l____ Q_:f:_Q ____ J C"'
acetylide and propene does not react with it (only terminal
alkynes react with AgNO3 in NH 3)
CH3 CH2CH3 CH3-C==CH + AgNO3 + NH3 - CH3 -C== c - Al
Propyne Silver acctylide
CH3 (white ppl)
1 12 3 4 5 6
CH3 - CH= CH2 + AgNO 3 + NH3 - No reaction
CH3-C-CH = C-CH2CH 3
I I 90. Alkynes give different products with different reducing agents.
CH3 CH 3 e.g. with Lindlar's catalyst (Pd / BaSO4 ) or Ni, cis-alkene is
2, 2, 4-trimethyl-3-hexene formed but with Na in liquid NH3 (Birch reduction), trans- alkene
To determine alkene, place these products with O-atoms face to is formed.
face and replace O-atoms by = bond. Lindlar's
catalyst

cis-2.-butene
81. ~ ~ ~ H B r
V kr hv V -----+
B
A
82. Markownikoff's as well as anti-Markownikoff 's mies are valid
for only asymmetric alkenes. 2-butene is a symmetric alkene.
83. Terminal alkynes react with ammoniacal AgNO 3 to give silver
salt as they have acidic hydrogen 91. Hydrogenation in presence of Pd and BaSO4 as syn- addition and
CH3 - C ==CH + AgNO3 + NH4OH ---4
- +
with Na and liquid NH3 at 200 K is anti- addition
CH3 - C == C· Ag + NH4NO3 + H 2O (trans compounds are formed).
84. The reaction is as follows: Pd/ BaSO4

CH 2=CH2 HBr CH3 -CH2Br

X
1CN H 3C-C==C-CH3
2-butyne

cis-2-butene
H2 / Ni
CH 3CH2NHCH3
z reduction CH3CH2NC Topic 3 Aromaticity, Structure of
N -methyl elhanamine Y
Benzene and Aromatic
85. Ethylene is formed by dehydrohalogenation of alkyl halide in Hydrocarbons
presence of alcoholic KOH. Ethylene decolourise alkaline
KMnO4 due to get oxidised by it. 1. (a) Ice floats in water due to low density of ice as compare to
water which is due to open cage like structure (formed by
CH3-CH2I Ale.KOH CH2= CH2
Ethylene
intermolecular H-bonding).
(b) Basic strength of R- NH2 > R3N. It is also explained by
86. In C2H 2, each C-atom is sp-hybridised which contains 50% hydrogen bonding.
s-character. The greater the s-character of an orbital, the bonding H
electron pair will be more inclined towards the nucleus as a result
carbon would acquire a negative charge and hydrogen a positive
I
/ H ---O- H
charge. Hence, it is acidic in nature. R- N R- N - R
H -C== C : H
"-H I
sp sp
I
I R
6
And removal of hydrogen as proton takes place. /"-.
H H
87. Acetylene does not react with NaOH. The pK0 value of (i) Two H-bonds are possible with (ii) No H-bonding is possible with
acetylene is 25. It is very weakly acidic and hence, NaOH is not water present in aqueous solution water present in aqueous solution
(stabilise by solution) (stabi lisation) by solution is very less.
sufficiently alkaline to react with it. On the other hand Na, 0 0
NaH, NaNH2 are more basic than their respective hydoxide and
the weakly acidic acetylene reacts with them.
II II
(c) C C
/"-. /"-.
88. H 2C =CH2 ~ CH3 - CH 2 Br H OH CH3 O - H
X
More acidic due to the presence of Less acidic than HCOOH
Na2C03 hydrogen and due to the absence due to presence of electron
aq.KOH 12 excess of electron donating group donating group
CHI3
z
l odoform
332 I Chapterwise & Topicwise Engineering Entrances Solved Papers

(d) Dimerisation of acetic acid in benzene is due to OH 0

intennolecular hydrogen bonding. I II
f"O - H ---H "'- Ph- C- CH2- CH 3~ Ph- C- CH2- CH 3
H3C - C"'- ,f"C - CH 3
I - H20

O - H --- H OH

2. Steric effect of halogens are as follows Cl 2 < Br2 < 12 • Electronic 5. Ethyl is o Ip directing group. Direct chlorination of ethyl benzene
effect of phenolic group directs the approaching electrophile with Cl2 / FeC1 3 would give mixture of 2 and 4-chloroethyl
towards ortho and para positions. benzene.
Tertiary butyl group has large size so, it causes steric effect C2Hs CzHs

I+
around aromatic nucleus. On the basis of above factors, the
products of the given reactions are as follows :

x,.,,
©¼c0rCI Cl
2, 4-chloro-1-ethylbenzene
~ C(CH3)3
6. An aryl halide with - NO2 substitution are highly activated for
aromatic nucleophilic substitution reaction.
x,-," B, ~ 7. On controlled hydrogenation of benzene with group/metal (like
~ C(CH3)3 Na, Li) and methanol (or ethanol) in liquid NH3, it reduces into

Q1 0
cyclohexadiene and cyclohexene which cannot be isolated.

x,-c,, C l ~ C (CH,J, 0
Benzene
Na. Liq.NH3
CH30H
Cyclohexadiene
+
Cyclohexene

This is because the presence of reducing agent, hexadiene is

Cl
further reduced to hexene, hence statement (a) is correct.
Hence, orientation in electrophilic substitution reaction is Statement (b) is incorrect due to data insufficiency.
decided by
Statement (d) is incorrect because benzene is a stable aromatic
(a) the steric effect of the halogen. compound while cyclohexene can be easily hydrogenated due to
(b) the steric effect of the tert-butyl group. reactive double bond.
(c) the electronic effect of the phenolic group. So, correct choice is (a).
So, (a), (b) and (c) are correct choices.
8. According to Huckel's rule, compound with (4n + 2)1t
3. Drawing the stmcture of organic compounds indicating net
delocalised electron w here n = 0, I, 2 •••and is planar, is aromatic.
dipole moment which includes lone pair and bond angle also
OH

fo the qu;,01~ ,ml ~;oqu;,01~

SH
000
N
Pyridine
~.
Thiophene
Q
Furan
6rr,e- 6rr,e- 6rr,e-
Because 1,3-cyclobutadiene is cyclic and contain 4n 1t -electrons.
OH SH
Hence, is anti-aromatic.
- OH groups and - SH groups donot cancel their dipole Hence, I, 3-cyclobutadiene is not aromatic.
moment as they exist in different conformation
[IIJ
"':o- H "':s•/ H I, 3-cyclobutadiene

¢ ¢
:o
Jc"••"--H
Hg2+ / H+
:s
H/••--,. Toluene
A
Benzyl
chloride
Benzal
chloride

4. Ph- C== C- CH 3 + H 2O ------, 1O. Aromatic compound, e.g. C6H6 give sooty flame on combustion.
OH Benzene bums with sooty flame because it is an unsaturated
I Hg 2 + / H+ compound. In unsaturated compound, carbon extent is more than
P h- C = CH- CH 3 - -----+ hydrogen. So, it gives, sooty flame on burning.
 Hydrocarbons I 333
11 . A species is said to have aromatic character if
~H~
NO2 + HSO4 ~ V
~ N 02
(i) ring is planar.
(ii) the complete delocalisation of1t-electrons.
Step III V + H2SO4
Nitrobenzene
(iii) Huckel's rule, i.e. (4n + 2)1t rnle is followed.
where, n is the number ofrings (4n + 2) 1t-electron delocalised 16. According to Huckel's rule, the compounds which have
(4n) (n = 0, 1, 2, 3 ••·) delocalised 1t-electron in a close-loop are
CI

A
anti-aromatic and characteristically unstable. Compound B satisfy

+ AICl3-----t L
(Aromatic)
+ AlCI;
the criteria of anti-aromaticity

0 + N a H ~ 6 + H2
(Aromatic)
Compound C is anti-aromatic in its resonance form.

Ao
~0
(NH4)2COJ
ll.,I00- 115°C

Compound A has 41t electrons which are also delocalised but do

not constitute close loop, hence, non-aromatic. Compound D is
Aromatic (R)
aromatic, characteristically stable

ao•c 6
0
0 0o

Aromatic (S)

12. DDT is Dichloro Diphenyl Trichloroethane. It can be prepared by

6~6 Tropyllium ion
(aromatic)
treating chloro benzene with chloral.
17. A compound is said to have aromatic character if ring system is
planar (with p-orbital) and there is complete delocalisation of
2cy,c1+ CCl,CHO :;;;;;, > cc1,CH(o-c,
Chlorobenzene Tnchloro
aoetaldehyde
or chloral
0-'
_
Cl
1t-electrons (lone pair may be taken for delocalisation as relay
electrons). This is true in conjugated cyclic system.

13. Structure of anthracene is

~
DDT
Q +--- This pair is used in delocalisation

~ Huckel's rule is followed by when electrons used in

delocalisation = (411 + 2)
There are three fused benzene rings in it.
(including lone-pair)
CH2 - CH3 COOH
where, 11 = 0, I, 2, 3 ...

,. @'•~ @ Benzoic acid

104
2 3

(I , 3-cyclopentadiene)
5
15. In the nitration of benzene, HNO3 of the nitrating mixture, acts as
Ring is planar.
a base as it accepts proton from cone. H 2SO4 and gives protonated
Ring is not conjugated.
nitric acid, which then changes into nitronium ion. Electrophile
Delocalisation of1t-electrons is not possible after C4.
attacking die benzene ring is No; ion.
(4n + 2) 1t-electrons = 4
Mechanism of nitration of benzene Hence, it is not aromatic.
Step I 18. Lindane is (hexachlorocyclohexane). It can be prepared by
H2SO4 ~ fr + HSO4 treating benzene with CI 2 in sunlight.
•• H"'- + + H ClH

U
fr + H - R - N02~H/2 - N02 ~ Hi-i;~:u~i~2
- hv Cl H
0 + 3Clz---=.:..:...... Cl H

StepII O ("-..
+ N02~
EB
C ( N o2
H
Cl
H Cl
Cl

y-benzene hexachloride
orLindane
334 I Chapterwise & Topicwise Engineering Entrances Solved Papers

19. "
L:;;i.
__ 2ne- ⇒ 4n+2 ⇒ n = 0
A

25.
Hence, aromatic.
~ COOH
ortlro-toluic acid

Br
·: Tn the product, - Br is para to - CH 3 and meta to - COOH.

26. The structure of benzene is

Cumene Phenol Propanone (C)

hydroperoxide
Bond order= ____ nru
_ n~b _er_o~f_b~o~n_d~s_ _-
number of resonating stmctures
±3 = 1.33
21. Ethyl benzene cannot be prepared by Wurtz reaction. This
method is suitable for the preparation of symmetrical alkanes. Since, the bond order is in between single and double bond, thus,
it contains delocalised 1t -bond. Hence, it is not possible to obtain
number of single and double bonds in bends in benzene.
27. At 60° (low temperature), mononitration occurs and nitrobenzene
is obtained but at I00°C, nitrobenzene farther undergoes
electrophilic substinition and gives m-dinitrobenzene (as - NO 2
is a meta-directing group).

HN◊)
23. Friedel-Craft's reaction is an electrophi lic substitution reaction 2

and presence of the electron releasing substituent like Me, makes

the benzene nucleus more reactive towards such reactions. Thus,
toluene is most reactive among the given 0 0,nc.

100°c
+ 0,nc. H2S04 C l0N

m-dinitrobenzene
NO?
-

Anhy. AICl3 )
X3,, ~3
[g]'CH3
0
28. C6H5CH3 Oxidation ¼ H 5COOH
A
NaOH

Sodaliire
o-xylene +
C6H 5COONa
(NaOH + CaO)
- - -- - t ¼~ + CO2
i
CH3 B C
p-xylene
29. The carbon-carbon bond length in benzene (1.39 A) in between
24. ~ C O OH ~ -y---:::: COOH thatofC- C (1.54 A)and C = C (1 .34A), i.e. in between that of
HO ~ HO /4' Czl-1<, and C2H 4•
- OH controls the 30. All those groups which contain at least one pair of non-bonding
orientation~ that is NO
ortho-para directing 2 electrons on the atom adjacent to the benzene ring, are ortho and
para directing.
Among the given options, all are ortho and para directing but
their capacity of ortho-para direction follows the order
- OCH 3controls the
orientation
(o/p-dirccting)
..
- NH2 > - CH3 > - C 2H 5 > - Cl

Hence, - N H 2 is the strongest ortho-para directing group.

31. A compound is said to be aromatic if it meets of the following

(i'o,()7 criteria.
(1) The rings of the compound should be planar.
(ii) The cyclic system must contain (4 n + 2) it-electrons. Only
fungBis:activatcd
o
~o
~ o~
(;NOz option (b) contains 61t-electrons, so it is aromatic.
32. According to X-ray analysis, all carbon- carbon bond distance
II 1 ( 1.397 A) are equal in benzene. The bond order of carbon-carbon
and - O- C- Phis _,:;::. bond is 1.5 in benzene.
(o/p-directing) Hence, carbon-carbon bond distance ( 1.397 A) is less than C- C
single bond ( 1.54 A) and more than C = C double bond
(1.33 A).
 Hydrocarbons I 335
33. In µ-xylene, the four nuclear H-atoms are equivalent and hence, 39. - NO2 group withdraw electron from the ring shows - M- effect
only one mononitro derivative is formed. But it gives three dinitro makes ring electron deficient, thus deactivates ring for electrophilic
derivatives (2, 3, 2, 6 and 2, 5) as shown below substitution.
40. Any aliphatic carbon w ith hydrogen attached to it, in combination
H3C -@- CH3 HN03
HzS04) H3C ~ CH3 HNOJ
H2S04) with benzene ring, will be oxidised to benzoic acid by
p-xylene KMn04 / H+
(M.F. CgH10) NO2

~NJ3/NO,
2, 6-dinitro

34. In benzene, all the six carbon atoms are

2. 6-dinitro
CH 3
2, 5-<linitro

sp2- hybridised. Out of

41. ,&
lQJ __ J_Cl_z._he_a_t,1_1_s_K_
- 3HCI

Toluene
these three sµ2-hybrid orbitals of each C-atom, two orbitals
2
overlap with sp -hybrid orbitals of adjacent C-atoms to fonn six
C- C single bonds. The remaining sp2-orbital of each C-atom
overlaps withs-orbital of each H-atom to form six C- H single
sigma bonds. Each C-atom is now left with one unhybridised
µ-orbital perpendicular to the plane of the ring.
35. D istillation of acetone with cone. H 2S04 gives mesitylene.
,& ··~'~0
L g ( B r+ - - ---3H

C
_C_I -

m-bromotoluene

42. By the reaction of benzene with ethylene in presence of

0 anhydrous AICl 3, ethylbenzene is produced.
II Cone. H:iS04
3CH3- C- CH3 - - -- c-CH3
Acetone

0 + CH
2
= CH
2
Anhy. AICl3
9s0 c

43. Benzene reacts with chlorine in presence of sunlight to give

gammexane or benzene hexachloride.
Toluene
CHO

_.:.@ 44. 0 +

is aromatic
Benzaldchyde

H~/C½Hs It contains 3 double bonds (6 1t-electrons).

According to Huckel's mle (4fl + 2) 1t = 61t-electrons
37. E&C where, fl= I
I COOR

~
C6Hs
is aromatic because the compound is cyclic and number of
1t-electrons is 2, which is in accordance with the Huckel's mle,
(4fl + 2) 1t. When, fl= 0, according to this m le, number of
1t-electrons is 4 x O+ 2 = 2.
38. In the given compounds, only acetophenone is prepared by
substitution. Other compounds are prepared by addition reactions.
45.

N02
4-nitrotoluene
+ [OJ
K2Cr201 +
H2S04
$ N02
4-nitrobenzoic acid

46. Friedel-Craft's acylation In this reaction, benzene reacts with

Acetophenone is prepared when benzene reacts with acetyl
acetyl chloride or acetic anhydride in presence of anhydrous
chloride in presence of anhydrous AICl 3 as

-&
AlCl 3.

CICOCH3 AM,. ,&CH' + HCI

lQJ AICl3 lQJ

0
Acetophenone
II
The X is R -C - Cl
336 I Chapterwise & Topicwise Engineering Entrances Solved Papers

47. A group that causes attack to occur chiefly at positions ortho and Benzene can also be obtained by heating phenol with zinc
para to it, is called an ortho-para director, e.g. NH2 , OH, Cl, etc. dust.
48. According to Huckel's m le, the molecules which contain
(4n + 2) 1t-electrons are aromatic.
49. PhMgBr can be protonated by any of the protic solvent, e.g. CH3OH.
Br
6 +2n--L,O+z,o
Phenol Benzene
PhMgBr + CH3 OH ~ Ph- H + Ml
55. Friedel-Craft's acylation It involves the treatment of
Benzene bCH
3 benzene with acetyl chloride or acetic anhydride in presence
of anhydrous aluminium chloride.
50. Given, C=.!.3. x 100%, H= _!_ X 100% COCH3
13 13 0
C = 92.3% ,H = 7.69%
C = 92.3 = 7 _69 = 7.69 = 1
12 7.69
@+ CH3- ~- Cl A ICl3
© +HCI
Acetophenone
H = 7.69 = 7_69 = 7.69 = I
I 7.69 56. Cyclic hydrocarbon, with carbon-carbon bond length between
: . Empirical formula of hydrocarbon is C 1H 1 = CH 1.34 A and 1.54 A, is benzene in which due to resonance,
·: A has empirical fonnula CH and decolourises bromine C-C bond length is 1.39 A, i.e. between 1.34 A-1.54 A.
water. Benzene is a hexagonal molecule with bond angle equal to
: . It is alkyne which is C2H 2 . 120°.
·: B has empirical formula CH and does not decolourise 57. The following are the necessary conditions for compound to
bromine water. be aromatic
: . It is benzene, C6H6 . (I) Molecule must be planar and cyclic.
51. When chlorine is passed in boiling toluene, substitution in side-chain (ii) Conjugated double bond must be present.
takes place and benzyl chloride is obtained which on hydrolysis give (iii) It must have (4n + 2) n-electrons.
benzyl alcohol.

C~ OCI " 0°:HCI

58. Correct matching is
Benzene - (4n + 2) 1t-electrons
Ethylene - Mustard gas
0" Acetaldehyde - Silver mirror
Chloroform - Phosgene
Boiling Benzyl alcohol Benzene has 61t-electrons, i.e. it follows Huckel's rule
(4n + 2)1t -
52.
electrons. Ethylene reacts with SiCl2 to give mustard gas (war
gas).
59. An insecticide, gammexane, is formed. It is also called
Benzene Hexachloride (BHC), though it is wrong. The correct
chemical-name is syn-hexachloro cyclohexane.

0,I __
H~H
CI H
n- heptane
3C_12_➔ Cl Cl
-....-.... sunlight H H
53. Toluene is oxidised to benzaldehyde in presence of chromyl Benzene Cl Cl
chloride. This reaction is called Etard's reaction.

r, J~o
Cl
60. According to Ruckel 's rule, an aromatic compound should have
00A (4n + 2) 1t-electrons where, n is an integer, i.e. 0, I, 2, 3, 4 ...
0
Toluene
[OJ 0
Benzaldehyde
and possesses unusual stability due to the delocalisation of
1t-electrons.
61. The presence of the chlorine atom on benzene ring makes the
54. Benzene can be obtained by heating benzoic acid with soda lime. second substituent enter at ortho or para-position because the
COOH COONa chlorine atom is ortho-para directing.
62. Aromatic compounds have delocalised n-electrons.

o •N•OH~o "'"~°"•O•N.,co,
Benzoic acid Benzene
Out of given choices cyclohexane, CH4 , Cil\ and benzene,
only benzene is aromatic compound. Benzene has six
delocalised 1t-electrons.
 Hydrocarbons I 337
Topic 4 Cycloalkanes and Cycloalkenes
1. Column I Column II Explanation
p )c1~>=0 NaOEt(2) OEt (strong nucleophile) causes dehydrohalogenation of3° alkyl halide.

Q ~ON!~~OEt EtBr(3) 3° butoxide lmdergoes Sis reaction with 1° alkyl halide

/ /
(i) Hg(OAch Mercuration-demercuration add H 2O by markownikoff's rule
R or~oOH without rearrangement.
(ii) NaBH4 (I)

s or-ccH (i) BH3

(ii) H 2O 2 / Off
Hydroboroxidation adds H 2O by anti-Markownikoff 's rule.

2. Cycloalkane has the formula C.Hz,,.

3. Cyclopropane is the most unstable cyclic compound. So, with 10. Angle strain in cyclopropane is 24 °44'
bromine it gives an open chain compound 1, 3-dibromo propane r
e -_L 0 360° 1_r 0 360° 1
CH2- CH2 - CH2
180
- - n tl
180 - - 3 J
/CH2 I I = 180° - 120° = 60°
CH2"'- I + Br2 -----t Br Br
CH2 I, 3-dibromopropane
Angle strain ex = .!. [109°28' - e]
2

4. o+B,,-y-B,
Cyclopropane
= .!. [109°28' - 60° ]= 24 °44'
2

Br
5. ro-dihalides when reacts with sodium metal, gives cyclic
hydrocarbons. This is an example of intramolecular Wurtz reaction.
CH 2 - CH 2CH 2- CH 2 Na
+ (HJ

Cyclohexanone
0
Cyclohexane

l
Br
I
Br
-----t Cyclobutane
-2NaBr

6. Cycloalkanes are isomeric w id1 alkenes because they have same

general formula c.H 21, (i.e. same molecular formula) but
possessing different strnctures. T hey show ring chain isomerism.
7. As the conjugation increases, heat of hydrogenation decreases.
Thus, alkene (c) with two isolated double bonds has the highest
heat of hydrogenation.
8. When carbon is bonded to four other atoms, the angle between 6-oxoheptanal
any pair of bonds = 109° 28' (tetrahedral angle) but the ring of
cyclobutane is square w ith four angles of 90°. 14. OsO4 is a valuable oxidising agent.
So, deviation of the bond angle (angle strain) in cyclobutane It oxidises alkenes to give cis-diols.

0+
o,o, ~,-. a)t<o
= (I 09°28' - 90° ) / 2 fy 0
= 19°28'/2= 9°44'
9. In cyclopropane, the angle strain is maximum. Hence, it is highly
strained molecule and consequently most unstable. The angle
strain in cyclobutane is less than cyclopropane.
Hence, cyclobutane is more stable. This stability increases upto
6 membered rings then decreases from 7 to 11 membered rings
and from d1e 12 membered rings onwards attains the stability of
6 membered ring.
Heat of combustion is a method of measuring chemical stability. .
c!x::=
d'10 1 OH
CIS-
Hence, cyclohexane has the lowest heat of combustion.
338 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Topic 5 Petroleum, Cracking, Knocking and Coaltar Distillation
1. Higher the octane number, better is the foel. Thus, among the
given, 81 is the octane number of best foel.
2. Aviation gasoline has a rating of I 00. Octane number of a foe! can
be improved by enhancing percentage of branched chain alkenes
and aromatic hydrocarbons in the gasoline.
3. Antiknocking compounds are the chemicals which reduce
knocking for improving the quality of gasoline, e.g. TEL
(Tetraethyl Lead).
4. Petrochemicals can be used to prepare synthetic fibres, pesticides
and plastics etc.
5. A petrol is said to have an octane number 80 if it behaves as a
mixture of 80% iso-octane and 20% 11-heptane in a standard test
engine.
6. Synthetic petrol is prepared by Fischer-Tropsch process.
Red hot coke+ Steam - C + Hp - CO + H 2
Water gas
~ + H2 6!~~~~~ Mixn1re ofliquid hydrocarbons
Water gas Cr and Zn
7. Green oil (anthracene oil)is obtained at 270-360°C by distillation
of coaltar. It mainly has anthracene and phenanthrene.
8. Cetane is chemically hexadecane, i.e. CH 3 (CH2 ) 14CH 3 .
9. LPG mainly contains bu tane.
10. Fischer-Tropsch process Jn this method, carbon monoxide
needed is made by passing steam over red hot coke. The water gas
thus, obtained is mixed with hydrogen and passed at a pressure of
5- 10 atm into a chamber containing a cobalt catalyst at 200°C.
nCO + (2n+ 1) H2 - C,,H2n+ 2 + nH 2O
The product is a mixn1re consisting mainly ofliquid hydrocarbons.
11. Kerosene oil has C 10- C 16 carbon atoms.
12. Branching increases the octane number offoel.
13. Tetraethyl lead (C2H 5 ) 4P b is used as an antiknock compound in
gasoline.
14. In laboratory burners, oil gas is generally used.
Oil gas is mixture of CH4 + CO + CO2 + H 2.
15. Nanrral gas is a mixture of gaseous hydrocarbons. Methane
(about 85%) is its main constituent.
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Environmental Chemistry
QUICK REVIEW
Environmental Pollution
Environmental chemistry deals with chemical phenomenon
occurring around us. The adverse effect of undesirable
changes is called environmental pollution.
Pollutants
The substances that cause pollution are pollutants.
Types of Pollutants
(i) Depending upon their physical state, pollutants may
be:
(a) gaseous : oxides ofS, N and C.
(b) particulate : mist, fumes, smoke, smog, dust.
(i1) Depending upon their degradability by microorganisms,
pollutants may be:
(a) Biodegradable that are degraded by
microorganisms, e.g. wastes, sludge, etc.
(b) Non-biodegradable that degrades slowly and
persist in the environment for many decades,
e.g. DDT, plastic, etc.
(iii) Depending upon their formation and existence in
nature, they are of two types:
(a) Primary pollutants are the simple molecules
which persist in the environment in the form they
are formed, e.g. CO, NO2 , SO2 ,etc.
(b) Secondary pollutants are the products fonned
by reactions of primary pollutants. These are more
harmful than primary pollutants, e.g. PAN
(peroxyacetyl nitrate fonned by the photochemical
reaction of hydrocarbons with ozone), NO, NO2 .
Atmosphere
The covering of various gases (air) which surrounds the earth
is called atmosphere. The composition of pure dry air is
N 2 (78.10% ), 0 2 (20.95%), Ar(0.93%), CO 2 (0.032% ), Ne
(18 ppm), CH 4 (1.3 ppm), N 2 0 (0.25 ppm), CO (0.10 ppm),
0 3 (0.02 ppm), S02 (0.001 ppm), N02 (0.001 ppm).
Layers of Atmosphere
(i) Troposphere It is the lowest layer, contain air
(N 2 , 0 2 , CO 2 , etc) and water vapours.
(ii) Stratosphere It contains ozone layer which protects us
from UV-radiation and infrared radiations. Ozone layer
is naturally formed by UV-radiation and oxygen.
(iii) Mesosphere It is the region above stratosphere and
extends from 50-85 km.
(iv) Thermosphere It above the mesosphere is
them1osphere which extends up to 640 km.
Atmospheric Pollution
It is due to alteration in the composition of air due to addition
of foreign materials, (i.e. pollutants).
Tropospheric Pollution
It caused by gaseous air pollutants like NOx, CO 2 , SO_.,
hydrocarbon etc. and particulate pollutants like dust, mist,
fumes, smoke, etc.
Consequences of Gaseous Air Pollutants
(i) Green house effect It is heating up of earth and its
objects due to trapping of IR radiations (thermal
radiations) by CO 2 , CH4 , NO, 0 3 , CFC, water vapour
etc., present in the atmosphere. These gases are termed
as green house gases.
340 I Chapterwise & Topicwise Engineering Entrances Solved Papers

(ii) Global warming It is increase in the temperature of earth Water Pollution

due to increased concentration of green house gases. It may
cause melting of ice caps and glaciers, floods oflow lying areas,
several infectious disease like malaria, sleeping sickness, etc.
(iii) Acid rain When the pH of rain water drops below 5 .6 due to
the presence of acids like H 2 SO4 , HNO 3 , it is called acid rain.
Oxides of N and S are released into the atmosphere from
the1mal p ower plants, industries and automobiles and rue the
main sources of acid rain.
2SO 2 + 0 2 + H 2 O~2H2 SO4
4NO 2 + 0 2 +2H 2 O ~4HNO 3
Smog
It is a se1ious air pollutant in many cities throughout the world.
Actually, the word "smog" is obtained by combining two words, viz. ,
smoke and fog. Smoke + fog ➔ smog
Depending upon the nature ofconstituents fom1ing smog, the smogs
are mainly of two types:
Types of Smog
It is contamination of water due to foreign substances.
• Sources point sources are identifiable sources,
e.g. municipal discharge pipe. Non point sources are
non-identifiable, e.g. run-off from field lawns, acid
rain, etc.
• Causes of water pollution are pathogens, organic
wastes, chemicals (like Hg , NO3 etc), acids, oils,
pesticides, ferti lisers, etc.
• Dissolved Oxygen (DO) below 6ppm, inhibits
growth of fishes.
• Biological oxygen demand is the amount of
oxygen requ ired by microbes to decompose organic
matter per litre of water. For clean water
BOD< 5 ppm.
• Eutrophication is the over population of plant in
water bodies due to the presence of large amount of
nutrients like NO3, PO~- which kills aquatic life.

Classical (Industrial) Photochemical Soil Pollution

Occurs in warm, dry It means alteration in quality, texture and mineral
and sunny climate (day time)
Occurs in cold, content of soil due to foreign substances.
humid climate Formed due to action
(after sunrise) of sunlight on unsaturated Sources of Soil
Generally SO2, hydrocarbons, NO2, produced
by automobiles and industries • Pesticides used to control growth of pests.
H 2O and smoke
Oxidising behaviour, • Herbicides to kill weeds, e.g. NaC1O 3 , Na 2 ASO 3 .
reducing behaviour
peroxyacetyl nitrate • Insecticide to kill insects e.g. DDT, BHC, etc.
[PAN) is the main component.
• Industrial solid waste originated from industries,
Can be suppressed which may b e biodegradable or non-biodegradable,
by radical trapes.
e.g. fly ash, slag, mud, drug, etc.
Note Bhopal gas tragedy (on December 1984) in which about3000
people were killed and about 5000 are still suffering from Control of Pollution
respiratory, lung and eye diseases, was due to leakage of (i) Waste management
methyl isocyanate (MIC) vapours. • Recycling of non-biodegradable materials.
• Degradation by microorganism.
Stratospheric Pollution (Ozone Layer Depletion) • By incinerators or dumping.
• Ozone layer acts as a protective shield in the biospheric ecosystem (ii) Green chemistry
against their exposure to harmful ultraviolet (UV) radiations. In it, the chemicals of daily need are
• The main cause of ozone depletion is the wide spread use of obtained by such reactions that neither use
ch lorofluorocarbons (CFCs.) toxic chemicals nor emit them.
• CFC decompose to produce Cl" radicals and chlorine nitrate, • H 2 0 2 is used for bleaching.
which reacts with ozone to produce oxygen. • Ethanol is obtained from ether by one step
Ozone depletion is also taking place due to NO,., SO 2 ,CH4 , oxidation.
photochemical smog and green house effect.
 Topic 1
Atmospheric Pollution
2013 2008
1. The gas leaked from a storage tank of the Union Carbide 8. Identify the incorrect statements in the following.[AIEEEJ
plant in Bhopal gas tragedy was [JEE Mains] (a) Chlorofluorocarbons are responsible for ozone layer
(a) methyl isocyanate depletion
(b) methylamine (b) Green house effect is responsible for global warming
(c) ammonia (c) Ozone layer does not permit infrared radiation from
(d) phosgene the sun to reach the earth
(d) Acid rain the is mostly because of oxides of nitrogen
2. Use of chlorofluorocarbons is not encouraged because and sulphur
[KCET]
9. Among the following compounds, which one is not
(a) they are harmful to the eyes of people that use it
responsible for the depletion of ozone layer? [BITSATJ
(b) they damage the refrigerators and air conditioners
(a) CH4 (b) CFC1 3 (c) NO (d) Cl 2
(c) they eat away the ozone in the atmosphere
(d) they destroy the oxygen layer 10. In which part of the atmosphere, ozone layer is present?
(a) Stratosphere (b) Troposphere [DCEJ
2012 (c) Mesosphere (d) Thermosphere
3. What is DDT among the following? [AIEEE]
(a) Green house gas
2007
(b) A fertiliser 11. The smog is essentially caused by the presence of
(c) Biodegradable pollutant (a) 0 2 and 0 3 [AIEEE, UPSEE, Jamia Millia Islamia]
(d) Non-biodegradable pollutant (b) 0 2 and N 2
(c) oxides of sulphur and nitrogen
2011 (d) 0 3 and N 2
4. Identify the incorrect statement from the following. 12. Which of the following is secondary pollutant? [ManipalJ
(a) Oxides of nitrogen in the atmosphere can cause the
depletion of ozone layer [AIEEE] (a) CO 2 (b) N 2 0 (c) PAN (d) S02
(b) Ozone absorbs the intense ultraviolet radiations of 13. The photochemical smog can be suppressed by [KCETJ
the sun (a) nitrogen oxides (b) hydrocarbons
(c) Depletion of ozone layer is because of its chemical (c) radical traps (d) formaldehyde
reactions with chlorofluoroalkanes (e) peroxyacetyl nitrate
(d) Ozone absorbs infrared radiations
14. Which of the following is responsible for the depletion of
5. The ozone layer fom1s naturally by [WBJEE] the ozone layer in the upper strata of the atmosphere?
(a) the interaction of CFC with oxygen (a) Polyhalogens (b) Ferrocenes CUPSEE]
(b) the interaction of UV radiation with oxygen (c) Fullerenes (d) Freons
(c) the interactjon of IR radiation with oxygen
(d) the interaction of oxygen and water vapour 2006
15. Pick out the correct statement. [Kerala CEEJ
2010
(a) CO which is major pollutant resulting from the
6. Which compound is mainly responsible for the depletion combustion of fuels in automobiles plays a major role
of ozone layer? [MP PET] in photochemical smog
(a) CO2 (b) CH4 (b) Classical smog has an oxidising character while the
(c) CH 3 0 H (d) CF2 Cl 2 photochemical smog is reducing in character
7. Green house effect is caused by [JCECE] (c) Photochemical smog occurs in day time whereas the
classical smog occurs in early morning homs
(a) N0 2 (d) During formation of smog the level of ozone in the
(b) co atmosphere goes down
(c)NO (e) Classical smog is good for health but not photochemical
(d) CO 2 smog
342 I Chapterwise & Topicwise Engineering Entrances Solved Papers
16. In Antarctica ozone depletion is due to the formation of 18. CFC1 2 is responsible for the decomposition of ozone to
following compound. [KCET] oxygen. Which of the following reacts with ozone to form
(a) Acrolein (b) Peroxyacetyl nitrate oxygen? CEAMCETJ
(c) S02 and S03 ( d) Chlorine nitrate (a)Cl 2 (b)Cl-
(e) Formaldehyde (c) p - (d) Cl
17. The gas that is not considered as a 'green house gas' is 19. Which of the following is not an air pollutant? [EAMCETJ
(a) CO2 (b) CH4 [AMUJ (a) N 2 (b) N 2 0
(c) 0 2 (d) 0 3 (c) NO (d) CO

Topic 2
Water Pollution
2012 2007
1. Which of the following is a measurement of water 2. When rain is accompanied by a thunderstorm, the collected
pollution? [Manipall rain water will have a pH value [MP PET]
(a) PSC (a) slightly lower than that of rain water without
(b)PCB thunderstorm
(c) BOD (b) slightly higher than that when the thunderstorm is not
(d) COD there
(c) uninfluenced by occurrence of thunderstorm
(d) which depends on the amount of dust in air

Answers
TOPICl Atmospheric Pollution
1. (a) 2. (c) 3. (d) 4. (d) 5. (b) 6. (d} 7. (d) 8. (c) 9. (a) 10. (a)
11. (c) 12. (c) 13. (c) 14. (d) 15. (c) 16. ( d) 17. (c) 18. (d) 19. (a)
TOPIC2 Water Pollution
1. (c) 2. (a)
 Explanations
Topic 1 Atmospheric Pollution
1. Methyl isocyanate CH 3 - N = C = 0 (MIC) gas leaked from The reaction once start, continuous for a long time. Thus, a single
the storage tank of the Union Carbide plant in Bhopal gas tragedy. chlorine free radical is able to convert about one lakh ozone
This gas was released from a pesticide manufacturing carbide molecules into oxygen and hence, may lead to massive ozone
plant union. depletion. Thus, chlorofluorocarbons (CF2Cl2)are responsible for
2. Chlorofluorocarbons (freons) being non-reactive, non- the depletion of ozone layer.
inflammable, non-toxic organic molecules are widely used in air 7. The heating up of earth and its objects due to the trapping of
conditioners, refrigerators. Due to very long life time radiations by CO2 and other green house gases like NO, 0 3 , CFCs
(CF2Cl 2 - 12 : 139 yr) and (CFCl3 - 11 :77 yr). These compounds in the atmosphere is called green house effect. Hence, green
ultimately reach the stratosphere where they get broken down by house effect is caused by CO2 •
powerful UV radiations and release chlorine free radicals which acts 8. Ozone layer permits the infrared radiations to pass through but
upon ozone molecule and convert them into molecular oxygen. doesn't permit the higher range of ultraviolet radiation to pass
CFiCl2(g) ~
0
Cl (g) + CF2Cl(g) through.
0
Cl (g) + 0 3( g ) ~ CI0 °(g)+ 0 2(g) 9. In stratosphere the following reactions take place, which are
responsible for the depletion of ozone layer.
Hence, chlorofluorocarbons eat away the ozone in the
N0 + 0 3 - N02 + 0 2
atmosphere. hv • •
CF2 CI2 - C F2 CI + Cl
3. DDT is a non-biodegradable pollutant. hv • •
CFCl 3 - CFCl 2 +CI
4. (a) NO + 0 3 - N02 + 0 2
0 3 + hv - 02+0 Cl+ 03 - CI O+ 02
N0 2 + o - N0 + 0 2 CIO + 0 - Cl + 0 2
Net reaction 203 + h v - 302 Hence, methane (CH 4 ) is not responsible for ozone layer depletion.
Thus, ozone layer is depleted by oxides of nitrogen. 10. Ozone layer is found in the stratosphere region of atmosphere. It
(b) Ozone layer is a protective layer and absorbs harmful UV rays prevents hannful UV radiation from coming to earth.
coming from the Sun. 11. NO, N0 2 , S0 2 and S03 are mainly responsible for smog.
CFCI
2 2 ~ c 1· + CFCI
2 12. Pollutants which are formed by reaction of primary pollutants
CFCl 3 ~ CFCl2 + Cl (persist in the environment in the form they are passed into it) are
0

called as secondary pollutants. Peroxyacetyl nitrates (PAN) are

(c) c1· + 0 3 - c 10 · + 02 secondary pollutants that are formed through reaction between
0 3 + hv - 0 + 02 nitrogen oxides (primary pollutants) and hydrocarbons in the
presence of sunlight while remain ones are primary.
c10· + o - ci + 02
13. Photochemical smog can be suppressed by radical traps. When the
Net reaction 203 + hv - 30 2 compounds are sprayed to the atmosphere, they generate free
Thus, ozone layer is also depleted by reaction with freons. radicals which readily combine with free radical precursors of
(d) is an incorrect statement as ozone absorbs only UV rays. photochemical smog. Among the given, only diethyl hydroxylamine
has been found to possess smog inhibiting characteristics.
5. When UV rays interact with dioxygen molecule (02 ), it gets split
14. Freons or chlorofluorocarbons are responsible for depletion of
up into free oxygen atoms (0) w hich combine with molecules of
the ozone layer in d1e upper strata of d1e atmosphere. They are
oxygen to give ozone.
used as propellants, aerosol spray caps, refrigerants, fire fighting
02 (g) ~ 0 (g) + 0 (g) reagents etc. They are stable and chemically inert compounds.
UV They absorb UV radiation and break down liberating free atomic
O(g) + 02 (g) ~ 0 1 (g) chlorine which causes decomposition of ozone through free
6. Chlorofluorocarbons provide Cl° free radical, w hich reacts with radical reaction.This results in the depletion of the ozone layer.
ozone and converts it into 0 2 as Freons are mainly freon- I (CFCl 3 ) and freon-12 (CF2Cl 2 ). They
form free radical of chlorine in the presence of UV radiation.
CF2CI2 - c 1· + cF2c1 Such free radical decomposes 0 3 as follows
c 1· +01 - c10· +02 c 1· + 0 1 - c10· + 0 2
c10· + o - c 1· + 0 2 c 10 · + 0 1 - c 1· + 202
Chlorine free radical
344 I Chapterwise & Topicwise Engineering Entrances Solved Papers
15. During the formation of photochemical smog, the level of ozone in
the atmosphere goes down.
hv
NO + 0 3 - N02 + 0 2
In the atmosphere the organic compounds rapidly react with
0 3 , N02 to form other noxious photochemical products known as
peroxyacyl nitrates (PANs) and acrolein. smog occurs in warm,
dry and sunny climate, generally during the day time while
classical smog occurs in cool humid climate, generally in the early
morning hou rs of w inter months.
16. In Antarctica during summer season, there exists nitrogen dioxide
and methane that acts as a sink for chlorine free radicals and
prevent much ozone depletion.
CIO. (g)+ N02 (g) - CION02 (g)
Chlorine nitrate
M<thyl free radical
While in w inters, there exist special type of clouds called Polar
Stratospheric Clouds (PSCs) over Antarctica. These clouds are of
two types:
(i) Type I : clouds consists of nitric acid trihydrate.
(ii) Type II : clou ds contain some ice.
These clouds convert CION02 into HOC! and Cl 2 as:
CION02 (g)+ H 20(g) ----HOC! (g)+ HN0 3 (g)
CION0 2 (g)+ HCI (g) ---- Cl 2 (g)+ HN0 3 (g)
During spring season, sunlight causes photolysis of HOC! and Cl 2.
HOC! ( g ) ~ OH° (g)+ c1• (g)
c1; ( g ) ~ 2c1 · (g)
The chlorine free radicals start the chain reaction for ozone
depletion.
17. Oxygen gas does not absorb IR radiation of high wavelengths
reflected back by earth, hence it does not cause 'green house
effect'.
18. CFC's (chlorofluorocarbons) causes depletion of ozone in the
stratosphere. This occurs because ultraviolet light also causes
CFC's to decompose, producing atomic chlorine. The chlorine
radicals react with ozone molecu les, resulting in a net removal
of 0 3 molecules from the stratosphere.
19. N itrogen gas is present in air upto 78% by volume. It does not
cause pollution.
Topic 2 Water Pollution
1. (a) PSC (Polar Stratospheric Clouds) are special type of clouds
formed over Antarctica in winter that play important role in
ozone layer depletion.
(b) PCB (Poly Chlori nated B iphenyls) are toxic chemicals with
high stability and resistance to oxidation. These are used for
fluids in transformers and capacitors.
(c) BOD (Biochemical Oxygen Demand) is a measure of
dissolved oxygen that would be needed by the microorganism
to oxidise organic and inorganic compounds present in
polluted water.
(d) COD (Chemical Oxygen Demand) is the amount of oxygen
(in ppm) that would be required to oxidise the contaminants.
2. During thunderstorm, there is formation of NO which oxidises
to N0 2 and ultimately on hydrolysis gives HN0 3 (acid rain).
N2 + 0 2 - 2NO ~ 2N02 ~ 2N03 +.!.2 0 2
I ffO
2N03 + - 0 2
2 - Nz05 ~ 2HNO (pH< 7).
3
The Solid State
QUICK REVIEW
In solid state constituent molecules, atoms or ions are closely (ii) Covalent solids (covalent bonds), e.g. graphite, diamond,
packed, have no translatory motion although they vibrate about quartz, etc.
fixed position that they occupy in a crystal lattice. (iii) Metallic solids (metallic bonds), e.g. Na, Cu, Fe, etc.
Types of Solids (iv) Molecular solids (van der Waals' forces or hydrogen
Solids are of two types amorphous and crystalline solids. In bond, can be polar or non-polar), e.g. solid CO2 , I2 , etc.
amorphous solids constituents do not possess orderly • A crystal possesses three types of symmetry : p lane of
arrangement over the long range and do not have sharp symmetry, axis of symmetry and centre of symmetry. In a
melting points. White in crystalline solids, constituents are cubical crystal, there are 9 plane of symmetry, 13 axis of
arranged in an orderly manner over long distance and have symmetry and 1 centre of symmetry.
sharp melting points. Crystalline solids are anisotropic while
amorphous solids are isotropic. Like liquids amorphous Unit Cell
solids have a tendency of flow, e.q. glass rubber, plastic etc. A regular array of points (showing atoms or ions) in three
Glass is a supercooled liquid. dimensions is commonly called as space lattice or crystal
lattice and three dimensional group of lattice points which
Classification of Crystalline Solids when repeated in space generates the crystal called unit
Depending upon the nature of interparticle forces, the cell.
solids are:
• Each u nit cell is characterised by distance, a, b and c
(1) Ionic solids (ionic forces, non-directional, high melting along three edges and angles a,~ and y between these
point and boiling point, act as electrolyte, exhibit edges.
isomorphism), e.g. NaCl, KCl, KN0 3 , etc.
There are seven crystal systems and fourteen Bravais lattice (unit cells) corresponding to these seven crystal systems.
Seven primitive unit cells
Primitives Maximum elements
System Interfacial or axial angles Examples
or axial distances of symmetry
Cubic a=b=c a =P =y = 90° 9 planes, 13 axis, 1 centre NaCl, KCl, ZnS, Ag
Tetragonal a=b:;cc a=P=r=90° 5 planes, 5 axis SnO 2 , NiSO4 , ZnO2 , Sn
Orthorhombic a :;c b :;c c a =P = y = 900 3 planes, 3 axis Rhombic S, BaSO 4 ,KNO 3 ,PbCO3
Monoclinic a :;c b :;c c (1. = 'Y = 90°' p :;c 90° 1 plane, I axis Monoclinic S, CaSO4 · 2H2O
Triclinic a:;cb:;cc (1. :;c p :;c 'Y :;c 90° No plane, no axis CuSO 4 · 5Hp, H 3BO3
Hexagonal a=b:;cc (1. = p = 90°, 'Y = 120° 7 planes, 7 axis ZnO, SiO2 (silica), HgS
Rhombohedral a =b= c (1. = 'Y = 90°' p :;c 90° 7 planes, 7 axis Calcite, NaNO3
or trigonal

• For a cubic system, there are only three types of unit cells, simple cubic unit cell, body centred cubic unit cell and face centred
cubic unit cell.
346 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Number of atom in a unit cell

Type of lattice Particles position Contribution to one unit cell Number of atoms
Simple or primitive atom at corners each 8 atoms contribute 1/8 8 x I I 8 = I atom per unit cell
cubic unit cell
Body centred cubic atoms at corner+ I at each 8 atoms contribute 1/8 + one full atom 8 x I I 8 + I= 2 atoms per unit cell
unit cell (bee) body centre
Face centred cubic atoms at corner+ face each 8 atoms contribute l /8 + I / 2 atom on face 8 x I / 8 + 6 x I I 2 = 4 atoms perunit cell
unit cell (fee)

• Coordination number for any crystal system in the number of spheres which are touching a particular sphere.
• The coordination number ofa tetrahedral void and octahedral void is four and six, respectively. Coorclination number in hep and
ccp arrangement is 12 while in bee arrangement it is 8.
• Relation between raclius (r) of a void and the radius (R) of the spheres in the close packing.
For a tetrahedral void: r = 0.225R,
For an octahedral void : r = 0.414 R.
• Relation between number of voids and spheres in close packing. In close packing of n spheres.
Number of octahedral voids = n,
Number of tetrahedral voids = 2n
• Relation between nearest neighbow·s clistance (d), atomic raclius (r) and edge length (a) of cubic unit cell.

Parameter Simple cubic Body centred cubic Face centred c ubic

d d=a ✓3a a
d= - = 0.866a d=✓2 = 0.707 a
r j I !l 2 I
\I/\" r a
r= -
2
r=✓3 !!_ = 0.433 a
4 2
(X
r = ✓2 = 0.3535 a
\'

Coorctination munber 6 8 4
Packing fraction 52.4% 68% 74%

• For ionic solids, the ratio of the radius of cation to that of anion is called radius ratio.

Radius ratio Coordination number Struc tural arrangement Example

Above 0.732 8 Cubic CsCI, CsBr, NH4Br
0.732 - 0.414 6 Octahedral NaCl, NaBr, CaS
0.414 - 0.225 4 Tetrahedral HgS, ZnS, BaS
0.225 - 0.155 3 Triangular Boron oxide

Bragg's Equation Defects in Crystalline Solids

(X-ray diffraction) n'A = 2d sin 0, where n is the order of • Electronic imperfections result from the loss of electrons
reflection, 'A is the wavelength of X-ray light used, d is the from their atoms and ions in covalent compounds and ionic
distance between two planes. crystals respectively. This results in formation of hole.
Density of Solids • Atomic imperfections results from clisplacement or loss of
atoms or ions in their perioclic arrangements in crystals.
. d ('mgcm- 3 ) = - - -
Dens1ty, Z-
X M
--- These are known as point defects.
a3 X NA X 10- 3o
• Schottky defect is caused when equal number of cations and
(where, Z is the number ofatoms per unit cell, Mis atomic mass anions are missing from their lattice sites. Due to this defect
of the elements and a is the edge length in pm). density ofthe crystal decreases, e.g. in NaCl, KCl, CsCl, etc.
 The Solid State I 347
• Frenkel defect is caused when cations are missing from their lattice sites and occupy interstitial sites. Density of the crystal remains
same but dielectric constant value increases.
• F-centres are the sites from where anions are missing and the vacant sites are occupied by electrons. F-centres contribute to
colour of the crystal.
• In doping, small amount of foreign impurity is added in the host crystal to increase its electrical conductivity.
• Dop ing of group 14 elements with group 15 elements produces excess of electrons (n-type semiconductors) and doping of
group 14-elements with group 13 elements produces holes (p-type semiconductors) in the crystal.
• Si and Ge are commonly used for making transistors.

Topic 1
General Properties and Classification of Solids
2013 2007
1. Which of the following exists as covalent crystals in the 5. Glass isa [MPPET]
solid state? [JEE Mains] (a) micro-crystalline solid
(a) Iodine (b) Silicon (c) Sulphur (d) Phosphorus (b) supercooled liquid
(c) gel
2. Which of the following is not co1Tect for ionic crystals ? (d) polymeric mixture
[OJEE]
(a) They possess high melting point and boiling point 2006
(b) All are electrolyte 6. Iodine is a [Jamia Millia Islamia]
(c) Exhibit the property of isomorphism (a) electrovalent solid
(d) Exhibit directional properties of the bond
(b) atomic solid
2011 (c) molecular solid
3. Which one of the following is a covalent crystal? [KCETJ (d) covalent solid
(a) Rock salt (b) rce (c) Quartz (d) Dry ice 2005
2010 7. The ability of a given substance to assume two or more
crystalline structure is called [Manipal]
4. Graphite is a [RPET]
(a) amorphism (b) isomorphism
(a) molecular solid (b) covalent solid (c) polymorphism (d) isomerism
(c) ionic solid (d) metallic solid

Topic 2
Crystal Lattices and Unit Cells, Number
of Atoms in a Unit Cell
2011
1. The number of hexagonal faces that are present in a 3. The unit cell with dimensions a = ~ = y = 90° , a = b cf. c is
truncated octahedron is [HT JEE]
(a) cubic (b) triclinic [Punjab CET]
w2 ~4 ~6 008 (c) hexagonal (d) tetragonal
2010 2008
2. The number of atoms contained in a fee unit cell of a 4. Number of atoms per unit cell of bee is [OJEE]
monoatomic substance is CRPETJ
(a) 1 (b)2
(a) 1 (b) 2 (c) 4 (d) 6 (c) 8 (d) 4
348 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2007 2005
5. For a crystal system a = b = c and ex. = ~ = 'Y -:t 90° [DCEJ 6. Number of atoms in the unit cell of Na (bee type crystal)
(a) tetragonal and Mg (fee type crystal) are respectively
(b) hexagonal (a) 4, 4 (b) 4, 2 [Jamia Millia Islamia]
(c) rhombohedral (c) 2, 4 (d) 1, 1
(d) monoclinic

Topic 3
Closed-Packed Structure, Packing Efficiency
2014
1. A body centric cubic lattice is made up of two different 6. Barium titanate has the perovskite structure, i.e. a cubic
types of atoms A and B. Atom A occupies the body centre lattice with Ba 2 + ions at the comers of the unit cell, oxide
and B occupying the comer positions. One of the comers is ions at the face centres and titanium ions at the body centre.
left unoccupied per unit cell. Empirical formula of such a The molecular fonnula of barium titanate is [BITSATJ
solid is [Manipall (a) BaTiO3 (b) BaTiO4 (c) BaTiO2 (d) BaTiO
(a) AB (b) A2 B 3 (c) A 5B 7 (d) A 8B 1 7. In a face-centred cubic arrangement ofA andB atoms at the
2013 face centred, one of A atom is missing from one corner in
unit cell. The simplest formula of the compound is
2. Experimentally it was found that a metal oxide has formula (a) A 24 B 7 (b) A 7 B 24 [ManipalJ
2 3
M 0 _98 0. Metal M, present as M + and M + in its oxide.
(c) A 1 B 4 (d) AB2
3
Fraction of the metal which exists as M + would be
8. What will be the percentage of free space in bee lattice ?
(a)7.01% (b)4.08% [JEE Mains]
(a) 32 (b) 68 [OJEE]
(c) 6.05% (d) 5.08%
(c) 72 (d) no free space
3. A compound with cubic structure is made of elements A 9. A solid has a structure in which, atoms of W, 0 and Na are
and B. A atoms are at the comers of the cube and B atoms located respectively at the comers, centre ofedge and at the
are at the face centres. The simplest fonnula of compound centre of the cubic lattice. The compound is [AMUJ
is [KCET]
(a) NaWO 2 (b) NaWO 3
(a) A 5 B (c) Na 2 WO 3 (d) NaWO 4
(c) AB
4. Coordination number of Zn in ZnS (zinc blende) is 2011
(a) 6 (b) 4 [OJEEJ 10. The packing efficiency of the two dimensional square unit
(c) 8 (d) 12 cell shown below is [HT JEE]

2012
5. A compound M PX q has cubic close packing (ccp)
arrangement of X. Its unit cell structure is shown below.
The empirical fom1ula of the compound, is [HT JEE]
+-- I --+

(a) 39.27% (b) 68.02 (c) 74.05% (d) 78.54%

11. Percentage of free space in cubic close packed structure
and in body centred packed structure are respectively
! 0
0 -----------1·--·--------o X 0
(a) 30% and 26% (b) 26% and 32% [AIEEE]
M a (c) 32% and 48% (d) 48% and 26%
0 i
12. In a face centred cubic lattice, atom A occupies the corner
0 positions and atom B occupies the face centre positions. If
one atom of B is missing from one of the face centred
points, the formula of the compound is [AIEEEJ
(a) A 2 B (b) AB2 (c) A 2 B 2 (d) A 2 B 5
 The Solid State I 349
2010 2008
13. In NaCl unit cell, all the ions lying along the axis as shown in 20. In a compound, atoms of element Y fom1 ccp lattice and
the figure are removed. those ofelement X occupy 213rd of tetrahedral voids. The
Then the number of Na+ and Cl - ions remaining in the unit formula of the compound will be [AIEEEJ
cell are [MP PET] (a) X 4 Y3 (b) X 2 Y 3 (c) X 2 Y (d) X 3 Y4
Cl Na 21. How many number of atoms are there in a cube based unit
Na ,<.....1- - - - ~ cell having one atom on each comer and two atoms on
I Cl each body diagonal of cube [ManipalJ
I

/
1
Na
~--------
Cl_ .___ _ _ __yNa
Cl- ws ~6 W4 ~9
22. A compound is formed by elements A and B. This
crystallises in the cubic structure where the A atoms are at
the comers of the cube and B atoms are at the body
centres. The sinlplest formula of the compound i{KCETJ
2009
(a) AB (b) A 6B (c) A 8B 4 (d) AB6
14. A compound of 'A' and 'B' crystallises in a cubic lattice
in which 'A · atoms occupy the lattice points at the comers 23. A solid compound contains X, Y and Z atoms in a cubic
of the cube. The 'B · atoms occupy the centre ofeach face lattice with X atom occupying the comers. Y atoms in the
(a) 2 (b) 4 (c) 6 (d) 8 [KCETJ body centred positions and Z atoms at the centres offaces
of the unit cell. What is the empirical formula of the
15. The lattice points of a crystal of hydrogen iodide are
compound? [Ke ral a CEE]
occupied by [UPSEEJ
(a) XY2 Z 3 (b) XYZ3 (c) X 2 Y2 Z 3
(a) HI molecules
(d) X 8 1Z6 (e) XYZ
(b) H atoms and I atoms
( c) H + cations and r
anions 24. What is the structure of NaCl? [OJEEJ
(d) H2 molecules and 12 molecules (a) bee (b) fee
16. In NaCl crystal each c1- ion is surrounded by [UPSEEJ ( c) Interpenetrating fee ( d) None of these
(a) 4 Na+ ions (b) 6 Na+ ions 2007
(c) I Na+ ion (d) 2 Na+ ions 25. The 8 : 8 type of packing is present in [VITEEE]
17. Which set of characteristics of ZnS crystal is correct? (a) MgF2 (b) CsCI
2
(a) Coordination number (4 : 4), ccp, Zn + ion in the (c) KC! (d) NaCl
alternate tetrahedral voids [AMU] 26. In a cubic structure ofdiamond which is made from X and
(b) Coordination number (6 : 6), hep, Zn 2 + ion in all Y, where X atoms are at the comers of the cube and Y at
tetrahedral voids the face centres of the cube. The molecular formula of the
(c) Coordination number (6 : 4), hep, Zn 2+ ion in all compound is [AMU, ManipalJ
octahedral voids (a) X 2 Y (b) X 3 Y (c) XY2 (d) XY3
( d) Coordination number ( 4 : 4), ccp, Zn 2+ ion in all
tetrahedral voids 2006
18. Arrangement of sulphide ions in zinc blende is [Guj CETJ 27. What is the coordination number of body centred cube?
(a) sc (b) hep (c) bee (d) fee (a) 8 (b) 6 CWB JEE]
19. Which is not the correct statement for ionic solids in which (c)4 (d) 12
positive and negative ions are held by strong electrostatic 28. Which of the following statements is not correct?
attractive forces? [DCEJ [J &K CET]
(a) The radius r+ / r - increases as coordination number (a) The unit of surface tension is dynes cm- 1
increases (b) The unit of viscosity coefficient ofa liquid is 'poise'
(b) As the difference in size of ions increases, (c) CsCl crystallises in body centred cubic type of
coordination number increases lattice
( c) When coordination number is eight, the r + / r - ratio s
( d) The coordination number of 2- in ZnS is 6
lies between 0.225 to 0.414 29. In CsCI type structure the coordination number of Cs+
(d) In ionic solid of the type AX (ZnS, Wurtzite), the and Cl- are [Jamia Millia Islamia]
s
coordination number of Zn 2 + and 2 - respectively are (a)6,6 (b)6,8 (c)8,8 (d)8,6
4and4
350 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2005
30. In which of the following crystals alternate tetrahedral 32. The coordination number of Na+ in NaCl is [OJEE]
voids are occupied? [IIT JEE] (a) 6 (b) 8
(a) NaCl (b) ZnS (c) CaF2 (d) Na 2 0 (c) 4 (d)l
31. In an antifluorite structure, cations occupy [BITSAT] 33. What is the number of tetrahedral voids per atom in a
(a) octahedral voids (b) centre of cube crystal? [AMU]
(c) tetrahedral voids (d) corners of cube (a) l (b)2
(c) 6 (d) 8

Topic 4
Calculation Involving Unit Cell Dimensions
2014
1. CsCl crystallises in body centred cubic lattice. If 'a' is its
edge length, then which of the following expression is
correct? [JEE Mains]
(b) res+ + re,- = 3a / 2
(d) res+ + 'er = .fia
2. A metal has bee structure and the edge length of its unit cell (a) 104 pm (b) 125 pm
3
is 3.04 A. The volume of the w1it cell in cm will be (c) 183 pm (d) 57 pm
[VITEEE] 7. An organic compound crystallises in an orthorhombical
21
(a)l.6xl0 cm 3 (b) 2.81 x 10- cm323 cell in the ratio of2: 1. The din1ensions of cell are 12.05,
15.05 and 2.69 A and density is l.419g/cm3 , find molar
(c) 6.02x 10- 23 cm3 (d) 6.6 x 10- 24 cm3
density of the compound [UPSEEJ
3. K.Br crystallises in NaCl type of crystal lattice and its
(a) 207 g/mol (b) 209 g/mol
density is 2.75 g/cm 3 . Number ofunit cell of KBr are (c) 308 g/mol (d) 317 g/mol
(a) 3.6x 1018 (b) 3.6x 1016 [Manipall
(c) 2.34x 1023 (d) 6.02x 1024 2012
4. Volume occupied by single CsCl ion pair in a crystal is 8. Lithium forms body-centred cubic structure. The length of
23 3
7.014 x 10- cm . The smallest Cs-Cs internuclear the side of its unit cell is 351 pm. Atomic radius of the
lithium will be [AIEEE]
distance is equal to length of the side of the cube
corresponding to volume of one CsCI ion pair. The (a) 75 pm (b) 300 pm
(c) 240 pm (d) 152 pm
smallest Cs to Cs internuclear distance is nearly
(a) 4.4 A (b) 4.3 A [KCET] 2011
(c) 4 A (d) 4.5 A 9. Silver (atomic weight = l 08 g mol- 1 )has a density of 10.5
2013 g cm - 3 . The number of silver atoms on a surface of area
10- 12 m 2 can be expressed in scientific notation as
5. If ionic radius of Cs+ and c1- are 1.69A and 1.81 A
y x 1ox . The value of x is [IIT JEE]
respectively, the edge length ofunit cell is [Manipal]
(a) 4.04 A (b) 3.50 A 003 ~5 ~7 ~9
(c) 7.00 A (d) None of these 10. Copper crystallises in fee lattice with a unit cell edge of36 l
6. The ammgement of X - ions around A+ ion in solid AX is pm. The radius of copper atom is [AIEEEJ

given in the figure (not drawn to scale). If the radius of x - (a) 181 pm (b) 108pm
is 250 pm, the radius of A+ is [KCETJ
(c) 128 pm (d) 157 pm
 The Solid State I 351
11. The first order reflection (n = l)from a crystal of the X-ray 21. A metal crystallises in a bee lattice. Its unit cell edge length
from a copper anode tube (A = I. 54 A) occurs at an angle is about 300 pm and its molar mass about 50 g mol- 1•
of 45°. What is the distance between the set of plane What would be the density of the metal (in g cm- 3 )?
causing the diffraction? [Guj CETJ
(a)3.I (b)6.2 [GujCETJ
(a)0.1089nm (b)0.1089m (c) 9.3 (d) 12.4
(c) 0.905 A (d) 1.089 x 10- 9 m
22. For AX ionic crystal to exist in bee structure, the ratio of
2010 radii (rcation ) should be [J&K CETJ
12. The edge length of a face centred cubic cell of an ionic ran,on
substance is 508 pm. If the radius of the cation is 110 pm, (a) between 0.41 and 0.73 (b) greater than 0 .73
the radius of the anion is [AIEEEJ (c) less than 0.41 (d) equal to 1.0
(a)288pm (b)398pm {c)618pm (d)l44pm 23. Total volume of atoms present in a face centred cubic unit
cell of a metal is (r = atomic radius) [BCECEJ
13. The maximum proportion of available volume that can be
filled by hard spheres in diamond is [Manipall (a) 20 7tr3 (b) 24 1tr3
(a) 0.52 (b) 0.34 (c) 0.32 (d) 0.68 3 3
12 3 16 3
14. If the radius of K+ and F- are 133 pm and 136 pm (c) - 7tr (d) - 1tr
3 3
respectively, the distance between K + and F- in KF is
24. The radius of Na+ and Cl- ions are 95 pm and 181 pm
(a) 269 pm (b) 134.5 pm [JCECE]
respectively. The edge length of NaCl unit cell is
(c) 136 pm (d) 3 pm [Jamia Millia Islamia]
2009 (a) 276 pm (b) 138 pm
(c) 552 pm (d) 415 pm
15. Copper crystallises in fee with a unit cell length of361 pm.
What is the radius of copper atom? [AIEEEJ 25. Sodium metal crystallises at room temperature in a body
(a) 108 pm (b) 127 pm (c) 157 pm (d) 181 pm centred cubic lattice with a cell edge a = 4.29 A. The
radius of sodium atom is [DCEJ
16. A solid metal has ccp or fee structure. The relation of side
(a) 1.40 (b) 2.65 (c) 1.85 (d) 2.15
ofcube (a) and radius of atom (r) will be
[lndraprastha CET, CGPET] 2007
(a) a = 2r (b) a = 2✓2 r(c) a = ~ r (d) a = @r 26. The cubic unit cell of Al (molar mass 27 gmol- 1 ) has an
../3 V2 edge length of 405 pm. Its density is 2.7 gcm- 3 . The cubic
unit cell is [Kerala CEEJ
2008
(a) face centred (b) body centred
17. For a crystal, the angle of diffraction (2 0) is 90° and the (c) primitive (d) edge centred
second order line has ad value of2.28A. The wavelength
(e) simple
(in A) of X-rays used for Bragg's diffraction is
[BITSAT, AMU, EAMCETJ
27. How many unit cells are present in a cube shaped ideal
crystal ofNaCl of mass 1.00 g?
(a) 1.612 (b) 2.00 (c) 2.28 (d) 4.00
(Atomic masses Na = 23, Cl = 35.5) [UPSEE, MP PET]
18. An ionic compound is expected to have tetrahedral 21
structure if r+ I r_ lies in the range of [KCETJ (a) 2.57 x 10 (b) 5.14 x 102 1
(c) l.28x 1021 (d) 1.71 x 1021
(a) 0.414 to 0.732 (b) 0.225 to 0.414
(c) 0.155 to 0.225 (d) 0.732 to l
2006
19. KC! crystallises in the same type of lattice as does NaCl. 28. A metallic element has a cubic lattice. Each edge of the unit
Given that 'i-.ia+ l rcr = 0 .55 and rK+ /rc1_ = 0.74. cell is 2 A. The density of the metal is 2.5 g cm- 3 . The unit
Calculate the ratio of the side of the unit cell for KCI to that cells in 200 g of metal are [MHT CETJ
ofNaCI. [Ke rala CEE] (a) IX 1024 (b) IX 1020
25
(a) 1.123 (b) 0.0891 (c) 1.414 (c) I X 1022 ( d) I X 10
(d) 0.414 (e) 1.732
20. The radius ratio in CsCl is 0.93. The expected lattice 29. The radius ratio(::) of an ionic solid (A+ s -) is 0.69.
structure is [UPSEEJ
What is the coordination number of?B- [J&K CETJ
(a) tetrahedral (b) square planar
(c) octahedral (d) body centred cubic (a) 6 (b) 8 (c) 2 (d) 102005
352 I Chapterwise & Topicwise Engineering Entrances Solved Papers

30. A metal has bee structure and the edge length of its unit cell 31. In 01thorhombic, the value of a, b and c are respectively
is 3.04A. The volume of the unit cell incm 3 will be 4.2 A , 8.6 A and 8.3 A. Given the molecular mass of the
21
(a) 1.6x I0- cm 3 23
(b) 2.8lx I0- cm 3
[OJEEJ solute is 155 g mo1- 1 and that of density is 3.3 glee, the
number of formula units per unit cell is [OJEEJ
(c) 6.02x I0- 23 cm3 (d) 6.6x I0- 24 cm3
w2 ~3 ~4 ~6

Topic 5
Imperfections in Solids and Their Electrical and
Magnetic Properties
2013 2008
1. Which one of the following defects in the crystals lowers 7. Schottky defects occurs mainly in electrovalent
its density ? [KCETJ compounds where [VITEEEJ
(a) F-centres defect (b) Interstitial defect (a) positive ions and negative ions are of different
(c) Frenkel defect (d) Schottky defect size
(b) positive ions and negative ions are of same size
2010 (c) positive ions are small and negative ions are big
2. If we mix a pentavalent in1purity in a crystal lattice of (d) positive ions are big and negative ions are small
germanium, what type of semiconductor formation will 8. An ion leaves its regular site occupy a position in the space
occur? [Manipal]
between the lattice sites is called [VITEEEJ
(a) p -type (b) n-type
(a) Frenkel defect
(c) Both (a) and (b) {d) None of these (b) Schottky defect
3. Which is the wrong statement regarding a crystal (c) Impurity defect
containing Schottky defect? [MP PET] (d) Vacancy defect
(a) Electrical neutrality of the crystal is maintained
(b) Entropy of the crystal increases
2007
(c) The density of the overall crystal remains the same 9. Which of the following statements is correct? [EAMCETJ
(d) The density of the overall crystal reduces (a) Silicon doped with boron is a n-type
4. Which ofthe following has the highest value ofenergy gap? semiconductor
(b) Silicon doped with arsenic is a p -type
(a) Aluminium (b) Silver [Guj CETJ
semiconductor
(c) Ge1manium (d) Diamond
(c) Metals are good conductors of electricity
5. Which kind of defect is shown by the given crystal? (d) Electrical conductivity of semiconductors decreases
K+ c1- K + c1- K + c1- [Guj CET] with increasing temperature
Cl- D Cl- K + D K + 10. Schottky defect generally appears in [Manipal]
K+ Cl- D Cl- K + CC (a) NaCl (b) KC! (c) CsCI (d) All of these
Cl- K+ Cl- K+ D K+ 11. The flame colours of metal ions are due to [RPET]

(a) Schottky defect (a) Frenkel defect

(b) Frenkel defect (b) Schottky defect
(c) Schottky and Frenkel defects (c) Metal deficiency defect
(d) Substitution disorder (d) Metal excess defect
6. In a solid lattice, the cation has left a lattice site and is 2006
located at an interstitial position, the lattice defect is 12. The elements commonly used for making transistors are
(a) Frenkel defect [Punjab CETJ (a) C and Si
(b) Schottky defect (b) Ga and In CUPSEEJ
(c) F-centre defect (c) P and As
(d) Valency defect (d) Si and Ge
 Answers
TOPIC 1 General Properties and Classification of Solids
1. (b) 2. (d) 3. (c) 4. (b) 5. (b) 6. (c) 7. (c)
TOPIC2 Crystal Lattices and Unit Cells, Number of Atoms in a Unit Cell
1. (d) 2. (c) 3. (d) 4. (b) 5. (c) 6. (c)
TOPIC3 Closed-Packed Structure, Packing Efficiency
1. (d) 2. (b) 3. (b) 4. (b) 5. (b) 6. (a) 7. (b) 8. (a) 9. (b) 10. (d)
11. (b) 12. (d) 13. (a) 14. (c) 15. (a) 16. (b) 17. (a) 18. (d) 19. (c) 20. (a)
21 . (d) 22. (a) 23. (b) 24. (b) 25. (b) 26. (d) 27. (a) 28. (d) 29. (c) 30. (b)
31 . (c) 32. (a) 33. (b)
Tilf!U_ Calculation Involving Unit Cell Dimensions
1. (c) 2. (b) 3. (a) 4. (c) 5. (a) 6. (a) 7. (b) 8. (d) 9. (c) 10. (c)
11. (c) 12. (d) 13. (b) 14. (a) 15. (b) 16. (b) 17. (a) 18. (b) 19. (a) 20. (a)
21 . (b) 22. (b) 23. (d) 24. (c) 25. (c) 26. (a) 27. (a) 28. (d) 29. (a) 30. (b)
31 . (c)
TOPICS Imperfections in Solids and Their Electrical and Magnetic Properties
1. (d) 2. (b) 3. (c) 4. (d) 5. (a) 6. (a) 7. (b) 8. (a) 9. (c) 10. (d)
11. (d) 12. (d)

Explanations
Topic 1 General Properties and Classification of Solids
1. In silicon, constituent particles are bonded together by covalent bonds, therefore, it exists as covalent crystals in the solid state.
2. Ionic crystals do not have directional bonds as the oppositely charged ions are attracted by electrostatic forces and arranged in a definite ratio.
3. Quartz (SiO 2 ) is a covalent crystal.
4. Graphite is a covalent solid as their C-atoms are bonded by covalent bonds.
5. Glass is a supercooled liquid, which forms a non-crystalline solid. The common lime-soda glass used for bottles and jars is a supercooled
mixture of sodium and calcium silicates.
6. Iodine is molecular solid because weak van der Waals' forces is found between its molecules.
7. The phenomenon by which a certain crystalline compound exists in two or more different crystalline forms, is called polymorphism, e.g.
CaCO 3 occurs in two polymorphic forms, i.e. calcite (rhombohedral) and aragonite (orthorhombic).

Topic 2 Crystal Lattices and Unit Cells, Number of Atoms in a Unit Cell
1. The truncated octahedron is the 14-faced archimedean solid, with 14 total faces: 6 squares and 8 regular hexagons.
The truncated octahedron is formed by removi ng the six right square pyramids one from each point of a regular octahedron as:

Truncated octahedron Truncated octahedron unfolded

in two dimensions
354 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2. In fee ➔ contribution of each atom present at the comer = 1/ 8 6. Number ofBa 2 + ions at comer of u nit cell = .!. x 8 = I
Contribution of each atom at the face centre = I / 2
8
2
Hence, total number of atoms in fee Number of 0 - ions at face centres = 6 x .!. = 3
2
= (8X ¾)+ ( 6 X ½) = I + 3 = 4 Nmnber ofTi4+ ions at body centre= I
Molecular formula BaTiO3
3. The unit cell with dimensions a= b ;cc, a = p = y = 90 is 7. In a cube, there are 8 atoms. Since, one atom A is missing from the
tetragonal. comer. The number of A atoms at the comer= 7
4. For bee unit cell, number of atoms at comers (per unit cell) Number of effective A atoms = 7 comers x I / 8 per corner atom
share = 7 / 8 atom / unit cell
I
= - X8 = 1 Number of effective B atoms
8
= 6 faces x I / 2 per face atom share
Number of atoms at body centre = I
Total number of atoms = 1 + 1 = 2 = 3 atoms / unit cell
Thus, formula of the compound is A7 B3 .
Crystal system Axial distances Axial angles 8
5.
On simplifying, fornmla of the compound is A1 B24.
Tetragonal a=b;cc a =P =r = 90° . fr . total volmne of spheres
8. P· ac kmg action= - - - - - - - -
Hexagonal a=b;cc a * P = 90°,y = 120° volume of unit cell
Rhombohedral a=b=c a =P =y:;c90°
For bee,
Monoclinic a;cb;cc a= r = 90,P * 90°
Number of atoms = 2
6. Number of atoms in unit cell of Na are 2 (bee). Nmnber of atoms
in unit cell of Mg (fee) are 4 . :. Total volume of spheres in bee= 2x±n?
3
8 3
- m·
Topic 3 Closed-Packed Structure, Thus, packing fraction = ½
x I 00 = 68%
P acking Efficiency 64r
1. There is one atom A per unit cell 3✓3
:. Fraction of free space in bee = 100 - 68 = 32%
Number of B per unit cell = .!. x 7 = 2 I
8 8 9. Number ofW atoms present at each corner= 8 x - = 1
Empirical formu la= A 1B718 or A8 B1 8
2. From the valency ofM 2 + and M 3 + it is clear thatthree M 2 + ions Number of O atoms present at the centre of edges = 12 x - = 3
I
3 3
w ill be replaced by two M + causing a loss of one M + ion. 4
Total loss of charge from one molecule ofMO = 1 - 0.98 = 0.02. Number of Na atom present at the centre of cube = I
Total M 3 + ion present in one molecule of Formula of cube= WO 3Na or NaWO3 .
MO = 2 x 0.02 = 0.04 . . 2x nr2 2nr2
Given that M 2 + and M 3 + = 0.98
1O. a = (2✓2r), packmg fraction = ~ = - -2
(2-v 2,-)2 Sr
Thus % of M3 + = 0.04 x I 00 = 4 .08% 3 14
' 0.98 =~= - =0.7854
4 4
3. Number of A atoms per unit cell is 8 x .!. = I = 78.54%
8
I 11. Packing fraction of ccp = ~ = 0.74 ⇒ 74%
Number of B atoms per unit cell is 6 x = 3 3v2
2 % free space in ccp = 26%
The fonnula of the compound= AB3
Packing fraction of bee= 1t✓3 = 0.68 ⇒ 68%
4. In ZnS, each sulphide ion is tetrahedrally surrounded by four zinc 8
ions and zinc ion is surrounded by four sulphide ions. Thus, zinc % free space in bee = 32%
sulphide possesses 4 : 4 coordination.
12. Number of effective A atoms
5. Contribution of atom from the edge centre is 1/4. = 8 comers x I/ 8 per corner atom share
Therefore
= 1 atom / unit cell
number of atoms M = 1/ 4 x 4 (from edge centre)
Number of atoms on faces of a cube = 6 atoms
+ I (from body centre)= 2
If one is missing from one face, nmnber of atoms left = 5
1 1
Number of X = - x 8 (from comers)+ - x 6 (from face centre) :. Number of effective B atoms = 5 faces x I / 2 per face atom
8 2
=4 share=~ per unit cell
2
Empirical formu la= M2 X 4 = MX2 The formula of the compound is AB512.

On simplifying we get, the fromula A 2 B5 ,
13. Since, in a unit cell of NaCl crystal, the ions are arranged in
the following manner.
O=Na+
c 1-1-------0
When all the ions lying along the shown axis are removed
the remaining unit cell contains 4 Na+ and 4 c 1- ions.
14. In the crystalline state of AICl 3 , the c 1- ions from space lattice
with Al 3+ ions occupying octahedral voids Hence, the
coordination number of Al in the crystalline state of A1Cl 3 is
6.
15. Since, HI is a covalent molecule and crystallises in face
centred cubic (fee) stmcture, m molecules are present at the
lattice points of the crystal.
16. In NaCl crystal, c1- ions adopt cubic close packed
arrangement and Na+ ions occupy all the octahedral
sites.Therefore, Na and Cl have I : I stoichiometry. In other
words, each Na+ ion is surrounded by six Cl- ions which are
directed towards the corners of a regular octahedron.
Similarly, each Cl- ion is surrounded by six Na+ ions.
17. ZnS has zinc blende type stmcture (i.e. ccp stmcture). The
s2- ions are present at the comers of the cube and at the
centre of each face. Zinc ions occupy half of the tetrahedral
sites.
Each zinc ion is surrounded by four sulphide ions which are
directed towards the comer ofregular tetrahedron. Similarly,
s2- ion is surrounded by four Zn 2+ ions.
18. Arrangement of sulphide ions (S2-) in zinc blende (ZnS) is
fee w hile Zn 2+ ions occupy alternate tetrahedral voids.
+
19. When coordination number is eight, the radius ratio ~ lies
between 0.732 to 1.000. r 31. In antifluorite structure (Na 2 Otype), the anions are oxide ions. The
20. Suppose atoms of element Yin ccp = I 00
Number of tetrahedral voids = 2 x I 00
2 400
Number of atoms of e lement X = - x 200 = -
3 3
400 X 400
Thus, formula would be X 400'J J'; 00 . = - -
3 Y 300
On simplifying, formula would be X 4 f:i.
The Solid State I 355
21. T here are four body diagona ls. Atoms on the body diagonals are not
shared by any other unit cell. Contribution by atoms on comers
= 8 x .!. = land
8
Contribution by atoms on body diagonal = 2 x 4 = 8
Hence, total number of atoms = 9
22. Since, A atoms are present at the corners of the cube,
Number of A atoms per un it cell = 8 x .!. = I
8
Number of B atoms per unit cell = I
( ·: Present at the body centre of the cube)
Hence, the formula of the compound= AB.
23. Since, atom X is present at comer and one corner is shared by eight
unit cells.
. I
Number of X atoms per umt cell = - x 8 = I
8
Atom Y is present at body centred position and used by only one unit
cell. So, number of Y atoms per unit cell = I
Atom Z is present at the centre of each face, so shared by two unit
cells, thus, number of Z atoms per unit cell = ½x 6 = 3
Hence, the formula of compound = XYZ3
24. NaCl has fee arrangement of ions. The coordination number of Cl- as
well as Na+ ion is six. Therefore, it is termed 6 : 6 coordination crystal.
25. The 8 : 8 type of packing is present in caesium chloride (CsCI). In this
stmcture, each Cs+ ion is surrounded by 8 c1- ions and each c1- ion is
also surrounded by 8 cs+ ions.
I
26. Number of atoms at comer = 8 x - = I
8
I
Number of atoms at face centres = 6 x - = 3
2
:. The formula of the compound is Xf:i.
27. The unit cell of body centred cube has one atom at each of the eight
comers and one atom at the centre of the body. Thus, the atom at
centre remains in contact with 8 corner atoms.
Hence, the coordination number of bee is 8.
28. Zinc blende (ZnS) has ccp arrangement ofS2- and Zn 2+ in alternative
tetrahedral sites. The coordination number of Zn 2+ = 4 and s2- = 4 in
ZnS.
29. In CsCl stmcture, 8 Cs+ ions surrounded by 8 c 1- ions, hence, the
coordination number wi II be 8 , 8.
30. In ZnS structure, sulphide ions occupy all (fee) lattice points w hile
Zn 2+ ions are present in alternate tetrahedral sites.
T herefore, there is one Zn 2+ ion for every s2- ion.
oxide ions form a face centred cubic array and the metal ion (cation)
fi ll all the tetrahedral voids, e.g. - Na 2O.
32. In sodium chloride, each Na+ ion is surrounded by six c1- ions and
Cl- ion is surrounded by six Na+ ions.
T hus, both the ions have coordination number six.
33. In the close packing of'n' atoms, the number of tetrahedral voids are'
2n'. Hence, their number per atom is 2.
Topic 4 Calculation Involving Unit Cell Dimensions
1. In CsCI, Cl- lie at corners of simple cube and Cs+ at the body 6. Given arrangement represents octahedral void and for this
centre. Hence, along the body diagonal Cs+ and Cl- touch each 1:,. (cation) =0.4 l 4 ⇒ 'iA+J =0.4 l 4
other. r_ (anion) ~X-J
So, re, + re, = 2r
Calculation of r ~A•J = 0.414 'en= 0.414 x 250 pm
InMDF, = 103.5 pm"' 104 pm
. ( p ) = ~ZxM
7. Dens1ty 3- -
a xNA
According to question, the length, breadth and height of
orthorhombic cell are different.
ah= 12.05 A= 12.05 x 10- 8 cm
a1 = 15.05 A= 15.05 x 10- 8 cm
..,,.._-+--...-_+-.,--, C \
~ = 2.69 A = 2.69 x 10- 8 cm
(._·· E a -.._ D _:,:-··_.-' Each cell has 2 molecules Z = 2 and N O = 6.023 x 1023
Hence, molar density
Body centred cubic unit cell M = p Xan X ~ X a1 X NA
FD = b = ✓a + a = ..fia z
2 2
1.419 X I 2.05 X I o- 8 X 15.05 X 10- 8
In MFD, c2 = a 2+ b2 = a 2+ (..fia)2 = a 2 + 2a2 X 2.69 X 10- 8 X 6.023 X 10
23
c2 = 3a2 2
1
As, MFD is an equi lateral triangle. = 2084.6 x Io- = 209 g/mol
✓3a=4r ⇒ r= ✓3a 8. In body centred cubic structure, edge length = a = 35 1 pm
4
Radius =r=?
Hence, re{ + 'c1 = 2r = 2 X ✓3 a = ✓3 a Then, r= ✓3a = ✓3 x 35 1 = 152 pm
4 2
4 4
2. Volume of unit cell (V) = a3
9. Volume of one mole of silver atoms
= (3.04 x 10- 8 cm)3
108
= 2.81 x 10- 23 cm 3 =-cm3/mot
10.5
3. As NaCl has fee unit cell, KBr crystallise in fee lattice. . 108 I
Volumeofones1lveratom=- - X cm 3
Thus, in a unit cell of KBr, there are four formula units of KBr 10.5 6.022x 1023
therefore, 4 3 I~ 1 23
So - rcr = - - x - - ---=- 1.708 x 10-
.
Density (p) =
4X119
= 2.75 , 3 10. 5 6.022x 1023
6.023 X 10 23 X a 3 r 3 = 0.407 x 10- 23 cm 3 = 0.407 x 10- 29 m 3
a 3 = 2.873 x 10- 22 cm 3 = 2.873 x 10- 19 mm 3 2
Area of each silver atom, rcr = re (0.407x 10- 29 m 3)2' 3
1019 So, number of silver atoms in given area
Number of unit cells per mm3 = - - = 3.6 x 1018
2.873 10-12
23
4. Volume, V = 7.014 x 10- cm 3 (0.407x 10- 29 m3}21 3 px 2

As smallest Cs to Cs internuclear distance is equal to length of the =1.6xl07 =yX IO'

side of the cube, i.e. a, therefore, So, x =7
23
a3 = 7.014 x 10- cm 3 1O. Copper crystallises in fee lattice.
23 If, r = radius, a = edge length
or a= 1/7.014 x 10- cm3 = 4.125 x 10- 8 cm 3 =4.12 A., 4A
a 361
Then, r = r;;;: = ..fi pm= 127.633 pm"' 128 pm
5. 2(r+ + r-) = ✓3a 2-v2 2 2
2 (1.69 + 1.81)= ✓3a 11. /IA= 2d sine
2 X 3.5 = ✓Ja 1 x 1.54 = 2d sin 45°
1 X 1.54 = 2d X 0.850
7= ✓ 3a 54
7 2d = 1. = 0.905 A
a= ✓3 =4.04 A 0.850
 The Solid State I 357
12. For fee arrangement 2(r+ + ,.- ) = edge length 22. For body centred cubic (bee) strucn1re, the ratio of radius (r+ Ir_)

2(110 + ,.- ) =508 So, ,.- = 144 pm lies in between 0.732 - 1.00.
:. The radius ratio for bee is greater than 0.73.
13. In diamond, the maximum proportion of available volume that
n.J3 23. Volume of an atom= ±nr3
can be fi lled by hard spheres= - - = 0.34 3
16 In fee, number of atoms per unit cell = 4
14. Distance between K+ and F- in KF : .Volume of total atoms
= rK+ + rF _ = 133 + 136 = 269pm 4 3 16 3
= 4 x - nr = - 1tr
. r;:: ✓2.a ✓2 X 361 3 3
15. Infecunitcell -v2a=4r ⇒ r= - = --- 127pm
4 4 24. NaCl has fee strucrure.
4r In fee lattice ,.+ + ,.- = !!_
16. In case of ccp or fee structure 4r = ✓2a ⇒ a = ✓2 2

a= 2✓2r where, a= edge length ,.+ = 95 pm, ,.- = 181 pm

17. Given, angle of diffraction (20) = 90° Edge length = 2,.+ + 2,.-
e =45° = (2 X 95 + 2 X 181) pm
Distance between two planes, d = 2.28 A = 190 + 362 = 552 pm
n = 2 (·: second order diffraction) 25. For a body centred cubic lattice radius,
Bragg's equation is nl = 2d sin 0 .J3 a= 0.433 a
(r) = -
2 x 1c = 2 x 2.28 x sin 45°, "- = 1.612 4
18. Radius ratio (r+lr_) S tructure Therefore, radius of Na+= 0.433 x 4.29 = 1.8575
< 0.155 Linear 26. Density, (p) = ~xM
0. 155-0.225 Planar triangular a xN0
0.225-0.414 Tetrahedral = Z X 27
27
0.414- 0.732 Octahedral . (405 X 10- I0)3 X 6.023 X 1023
0.732- 1 bee z= 2.7 X (405)3 X l0- 30 X 6.023 X 10 =
23
4
27
For face centred cubic unit cell, number of atoms are 4.
27. Mass of one unit-cell (m) = volume x density

r r 3 3 MZ
+ + =a xd=a x - -3
~ = 0.55, ~ + 1 = 0.55 + I N0 a
,. r
c,- c,- MZ 58.5 x4
r +r NO m = 6.02 X 1023 g
Na• Cl - =1.55 ...(i)
rCl- :. Number of unit cells in
I 6.02 X 1023
I g= - = - - - - 2.57 X 1021
m 58.5x4
mass of metal
28. Number of unit cells= - - - - - - -
...(ii) mass of one unit cell
,.c,- Given, edge length of unit cell= 2A= 2 x 10- 8 cm
Eq. (ii) divide by Eq. (i) Mass of metal = 200 g
r +r 174 Density of metal = 2.5 g cm- 3
K+ Cl- = - · - .., J.1 226
'Na. + ,.c,- 1.55 Volume of unit cell = (edge length) 3 = (2 x 10-8 )3
20. The radius ratio of CsCI is 0.93. Hence, its structure is body = 8 x 10- 24 cm3
centred cubic. Mass of one unit cell = volume x density
21. Given, = 8 X 10- 24 X 2.5 = 20 X 10- 24
Molar mass, M = 50 g/mol, NA= 6.02 x I 023 : .Number. of unit cells in 200 g metal
Z = 2 (for bee crystal) mass of metal
Edge length, a= 300 pm= 3 x 10- 8 cm mass of one unit cell

d= z X M3 ~: 50 8 3 6. 15 .., 6.2 200 , = IOX 1024 = 1.0 X 1025

NA X a 6.022 X 10 X (3 X 10- ) 20 X 10-24
358 I Chapterwise & Topicwise Engineering Entrances Solved Papers

29. Relation between radius ratio and coordination number 4. Diamond has the highest value of energy gap as it is a insulator.
5. In the given crystal equal number of cations and anions are missing
Coordination number
(two K+ and two Cl- ) from their normal lattice sites and the crystal
0. 155 - 0.225 3 maintains electrical neutrality. Hence, this is Schottky defect.
0.225 - 0.414 4 6. When an ion (generally cation due to its small size) is missing
0.414-0.732 6 from its normal position and occupy an interstitial site between
the lattice points, the lattice defect obtained is know n as Frenkel
0.732 - I 8 defect.
30. Edge length, a= 3.04 A= 3.04 x 10- 8 cm 7. When equal number of cations or anions are missing from their
3 lattice sites (to maintain electrical neutrality), then the defect is
Volume ofbcc (cubic) cell= a called Schottky defect. The defect is observed in highly ionic
= (3.04 x 10- 8 )3 = 2.81 x 10-23 cm3 compotmds which have cations and anions of similar size, e.g.
z =V N d NaCl, KCI, etc.
31. X X
m 8. Frenkel defects arises when an ion is missing from its normal
4. 2x 8.6x 8.3 X 10- 21 X 6.023 X 1023 X 3.3 position and occupies an interstitial site between the lattice points.
3.84"" 4
155 9. Metals are good conductors of electricity due to the presence of
free electrons. Electrical conductivity of semiconductors
Topic 5 Imperfections in Solids and increases with increase in temperature.
Their Electrical and 10. Schottky defect arises when equal number of cations and an ions
are missing from their sites. This defect is generally found in
Magnetic Properties ionic compounds like NaCl, KCI, CsCI, etc. Where, there is a
1. In an ionic crystal of A+ B- type, if equal number of cations and small difference in the size of cations and anions.
ions are missing from their lattice sites, the defect is called 11. Flame colours are due to metal excess defect. In such defects,
Schottky defect. Because of the missing of ions from the lattice, due to the missing of negative ion from its lattice s ite a hole is
this defect decrease in density. left in a crystal which is occupied by an electron. The electrons
2. On adding a pentavalent impurity with germanium, we get n-type thus, trapped in the anion vacancies are called F-centres.
of semiconductors because pentavalent atoms have I electron These electrons can absorb energy and go into excited states
excess to Ge, after forming 4 covalent bonds with Ge. This excess from ground state. Thus, the absorption of certain wavelength of
free electron is responsible for electrical conductivity. light takes place and crystal becomes coloured according to
complementary colour.
3. In Schottky defect due to missing of ions, the overall density of
the crystal decreases. Moreover, defect leads to randomness, thus 12. Si and Ge are used for making transistors.
entropy also increases.
Solutions
QUICK REVIEW
• Solution A solution is a homogeneous mixture of two or (iii) Mass by volume percentage= WB(g) x 100
more substances (one phase system). The component which MB X V(L)

is present in the greater quantity is called solvent while the (where, MB is the molecular mass ofsolute).
other component is called the solute. . percentage by massx densityx 10
• Mo1anty = - - - - - - - - - - - -
• Solubility The maximum amount of a solute that can be molar mass of solute
dissolved in a given amount of solvent at a given
Note
temperature is termed as solubility at that temperature.
Molarity varies with temperature due to accompanied
• Unsaturated solution A solution in which more solute can change in volume of the solution.
be dissolved without raising temperature is called an
(iv) Molality = WB(g)
unsaturated solution. MB X WA(kg)
• Saturated solution A solution in which no solute can be (where, WA is the mass ofsolvent).
dissolved further at a given temperature is called a saturated (v) Normality
solution.
• Super saturated solution When the solution contains more gram equivalent mass of solute x V (L)
solute than would be necessary to saturate it, then it is Note
termed as supersaturated solution. . molarity x molar mass
• N orma11ty = - - - - - - - -
Henry's Law equivalent mass
It states that, at constant temperature, the solubility of a gas in
a liquid is directly proportional to the partial pressure of the • Normality of acid = molarity x basicity
gas present above the surface of liquid or solution. P <>< x or • Normality of base = molarity x acidity
P = K H X· Where, P is the partial pressure of a gas in • Normality and molarity equations
solution, x is its mole fraction and KH is Henry's law N 1 V1 = N 1 V2
constant. Higher the value of K H at a given pressure, the M 1 V1 = M 2 V2
lower is the solubility of the gas in the liquid. • Normality equation for total no1mality of two non
Concentration of solution reacting solutions.
The various expression for the concentration of solutions NV=N 1V1 + N 1 V2
can be summarised as (where, NV are total normality and total volume of two
. mass of solute (g)
(i) Strength of solution = - - - - - - - solutions.)
volume ofsolution (L) wB
wB (vi) ppm= x Id'
(ii) Mass percentage= x 100 WA+ WB
WA+ WB
nA
(where, WB and WA are the mass of solute and solvent (vii) Mole fraction o f A, XA = - - -
11A + nB
respectively)
360 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Mole fraction of B, Xa = ~ In such solutions, solvent-solvent and solute-solute

nA + na interactions are almost of same type as solvent-solute
interactions.
XA + xB =1
(viii) Mass fraction of A =
wA • Non-ideal Solution
WA+ Wa is one which don't obey Raoult' s law for all concentrations
Mass fraction of B = - ~Wa~- and temperature.
WA+ Wa llH mixing "# 0 and ti V mixing "# 0
(ix) Molality, mole fraction and mass fraction do not change These non-ideal solutions show two types of deviations
with temperature as they involve weights. from the ideal behaviour.
(x) Relationship between molality (m) of a solution and mole (i) Non-ideal solutions showing positive deviations (new
fraction of solute (xa) xa =mMA , interactions are weaker than those in the pure component)
l + m·MA D.Vmixing > 0 and Affmxms
, . > 0.
(where, MA is the molar mass of solvent.) e.g., acetone + CSi
(xi) Relationship between molarity (M), molality (m) and (it) Non-ideal solutions showing negative deviations (new
interactions are stronger than those in the pure component)
density (d) of a solution xa = M · MA ;
M(MA - Ma)+d D.Vmixing < 0 and Affmixing < 0.
(where MA and Ma are molar masses of solvent and solute e.g. acetone + chloroform
respectively)
Vapour Pressure
• The vapour pressure of a solvent is defined as the pressure
l Pao 1 Pao

exerted by the vapours ofsolvent when they are in dynamic VP VP

equilibrium with its liquid at a temperature. It depends
,,
upon the nature of the liquid, temperature and purity of the
liquid. Addition of a miscible solute to a pure solvent 01- XA 0 1
11- XB 0
results in lowering in its vapour pressure.
• The vapour pressure of liquid in solution is known as its • Azeotropic mixtures It is the mixture of two liquids
partial vapour pressure and it is less than the vapour which boil at a constant temperature and distills over
pressure of pure liquid. without any change in composition. These may be of two
types minimum boiling azeotropes and maximum boiling
Raoult's Law azeotropes.
(i) If only solvent (A) is volatile At a given temperature, the • Colligative properties Colligative properties depend
partial pressure of a solvent in a solution containing only on number of solute particle present in the solution
non-volati le solute is directly proportional to its mole and their concentration.
fraction. (i) Relative Lowering of Vapour Pressure
Mathematically, Ps = P;XA
Mole fraction of A in vapour phase,
- --1!.L_
p" -/s
P
= X,,M, =
W
A
[':''
P - Ps
o
l
XA- p
PA+ Pa
Relative lowering of check= mole fraction of solute Where, X8 = mole fraction of solute
(ii) If both components are volatile At a given temperature, p 0 = vapour pressure of pure solvent
the partial vapour pressure of any component of the Ps = vapour pressure of solution
solution is equal to the product of the vapour pressure of
• Relative lowering of vapour pressure in measured by
the pure component and its mole fraction in the solution
Ostwald and Walker method. In this method, the
PA = P;XA and Pa = P;Xa
0 0 apparatus used, contains two bulbs; bulb A contains
PtotaJ = PA + Pa = PAXA + PaXa solution and bulb in contains pure solvent. Loss in weight
(where, PA and Pa are vapour pressures of pure components of solution bulb, w1 oc vapour pressure of solution. Loss in
and XA and Xa are mole fractions of components A and B). weight of solution bulb, w 2 oc vapour pressure of solvent
Ideal and Non-ideal Solution vapour pressure of solution. Therefore, relative lowering
Ideal solution is one which obeys Raoult's law for all range of of vapour pressure,
concentrations and temperatures.
11H mixing = 0 and ti Vmixing = 0
 Solutions I 361
(ii) Elevation in Boiling Point (t-J'b) van 't-Hoff factor,
i = observed value of colligative properties
t:.Tb = Kbm
Where, mis molality of solution calculated value of colligative properties
M = Kb x WB x 1000 . calculated molar mass
! =--------
8
t:.Tb X WA observed molar mass
( where, Kb is molal elevation constant.) (i) For dissociation, i> 1while for association, i < 1
(iii) Depression in Freezing Point (ii) Degree of dissociation,
i- 1
t:.T1 = K 1 m (X, = - -
K f X W8 X 1000 n- 1
MB = - - - - - - -
t:.Tf X WA
(iii) Degree of association,
(where, K I is molal depression constant.) ex. = (1 - i)- n-
n- l
(iv) The molal elevation constant (Kb) and molar
depression constant (K 1 ) are given as • For solution undergoing dissociation or association.
0
2 .) P - Ps .
RT 2 RT ( = IXB
K =__ b _ andK = f l
po
b 1000LV f lO00Lf
(ii) t:.Tb = iK bm
where Lv is the latent heat of vaporisation and L I is
(iii) t:.T1 = iK 1 m
the latent heat of fusion. 1 1
1t = iCRT (whereR = 0.0821 L atmK- mol- )
(v) Osmotic pressure, 1t = CRT
• Greater the value of i, greater the value of t:.Tb and boiling
- !!_RT M - WBRT
7t - V , B - -----;v point of solution.
(i) Greater the value of i, greater the value of t:.T but
• Variation of vapour pressure with temperature (Clausius 1
smaller the value of freezing point.
Clapeyron's equation) (ii) Greater the value of i, larger the value of osmotic
l P2 _ t:.H vap [T2 - T.,] pressure.
ogPt - 2.303R T1 -T2 (iii) Greater the value of i, larger the value of Ii p and smaller
(where, p 1 and p 2 are the vapour pressure ofa liquid at the value of vapour pressure of solution.
T1 and T2 (in kelvin) temperatures) • Nernst Distribution Law,
• Isotonic solutions exert same osmotic pressure as they It states that, at constant temperature when different quantities
have same molar concentrations. Hypertonic solution of a solute are allowed to distribute between two layers of
have higher osmotic pressure than that of solution immiscible solvents in contact with each other then at
separating it by a semipermeable membrane. While, equilibrium the ratio of the concentrations of the solute in two
hypotonic solution have lower osmotic pressure than layers is constant for similar species which may be present.
that of the solution separating it by a semipermeable • In polar region, roads are sprinkled with CaC1 2 to minimise
membrane. the wear and tear of the roads.
van't-Hoff Factor and Degree of Dissociation and • Blood cells don't shrink in blood because blood is isotonic.
Association.
 Topic 1
Types of Solutions and Methods of
Expressing Concentration
2014
1. An aqueous solution of phosphoric acid, H 3 PO 4 being 10. Two solutions ofHCl, A and B have concentrations of0.5
titrated has molarity equal to 0.25 M. Which of the N and 0.1 M respectively. The volume of solutions A and B
following could be nom,ality of this solution? [Manipal] required to make 2L of0.2 N HCl are [AMU]
(a) 0 .25 N (b) 0 .50 N (a) 0.5 L of A + l.5 Lof B
(c) 0.75 N (d) All of these (b) 1.5 L of A+ 0.5 LofB
2. 25 cm3 of oxalic acid completely neutralise 0.064 g of (c)I.0 L ofA+I.0 L ofB
sodium hydroxide. Molarity of the oxalic acid solution is (d) 0.75 Lof A+ 1.25 Lof B
(a) 0 .064 (b) 0 .045 [KCET] 11. The density of a 3M sodium thiosulphate (Na 2 S 2 O 3 )
(c) 0.◊15 (d) 0 .032 solution is 1.25 g/mL. Calculate the per cent by weight of
3. Find the molarity of the solution containing 5.3 g of sodium thiosulphate. [AMUJ
Na 2 CO 3 in 500 mL solution (a) 12.65% (b) 37.92% (c) 0.87% (d) 63.21%
(a) 1.0 M (b) 0.1 M [UPSEE]
(c) 0.25 M (d) 0 .2 M
2011
12. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water
4. 25 mL of3.0 M HCl are mixed with 75 mL of 4.0 M HCI.
gave a solution of density 1.15 g/mL. The molarity of the
If the volumes are additive, the molarity of the final
solution is [HT JEE]
mixture will be [AMU]
(a) 1.78 M (b) 2.00 M (c) 2.05 M (d) 2.22 M
(a) 4 .0 M (b) 3.75 M
(c) 4.25 M (d) 3.50 M 13. A 5.2 molal aqueous solution of methyl alcohol, CH 3 OH ,
is supplied. What is the mole fraction of methyl alcohol in
5. Molality of 2.5 g of ethanoic acid (CH3 COOH) in 75 g of
the solution ? [AIEEEJ
benzene is [J&K CET]
(a) 1.100 (b) 0.190 (c) 0.086 (d) 0.050
(a) 0 .565 mol/kg (b) 0.656 mol/kg
(c) 0.556 mol/kg (d) 0 .665 mol/kg 14. The molality of a urea solution in which 0.0100 g of urea,
[(NH 2 h CO] is added to 0.3000 dm of water at STP is
2

2013
(a) 0.555 m (b) 5.55 x 10-4 m [AIEEE]
6. The molarity of a solution obtained by mixing 750 mL of
0.5 (M) HCI with 250 mL of2(M) HCl will be (c) 33.3 m (d) 3.33 x 10- 2 m
(a) 0 .875 M (b) 1.00 M [JEE Mains] 15. The sum of mole fractions of A, B and C in an aqueous
(c) 1.75 M (d) 0.0975 M solution containing 0.2 moles of each A, B and C is
(a) 0.6 (b) 0.2 (c) 1.0 (d) 1.2 [KCET]
2012
16. A mixtw·e of ethane and ethene occupies 41 L at 1 atm and
7. 29.2% (w/ W) HCl stock solution has density of
1.25 g mL- 1• The molecular weight ofHCl is 36.5 rno1- 1• 500 K. The mixture reacts completely with .!_Q mole ofO 2
3
The volume (mL) of stock solution required to prepare a
to produce CO 2 and H 2 0. The mole fraction ofethane and
200 mL solution 0.4 M HCl is [HT JEE]
ethene in the mixtw·e are
(a) 5.0 mL (b) 6.0 mL
(c) 8.0 mL (d) 15.0 mL R = 0.082L atm K - 1 rnol- 1) respectively [Ke ral a CEEJ

8. Which ofthe following will represent the normality of 10% (a) 0.50, 0 .50 (b) 0 .75, 0.25
(c) 0.67, 0 .33 (d) 0 .25, 0 .75
( w/V) acetic acid? [Manipal]
(e) 0.33, 0 .67
(a) 1.66N (b) 16.6N
(c) 3.32 N (d) 33.2 N 17. How many grams of sulphuric acid is to be dissolved to
prepare 200 m L aqueous solution having concentration of
9. The volume of 0.1 M oxalic acid that can be completely
[H 3 o +] ions 1 Mat 25°C temperature.
oxidised by 20 mL of0.◊25 M KMnO4 solution is
[H = 1, 0 = 16, S = 32 g -mol - 1 ] [Guj CET]
(a) 25 mL (b) 12.5 mL [KCET]
(c) 37.5 mL (d) 125 mL (a)4.9g (b)l9.6g (c)9.8g (d) 0.98 g
 Solutions I 363
2010
18. Out of following which one is not an example of a 29. How many grams ofNaOH will be required to prepare
solution? [MP PET]
500 g solution containing 10% w NaOH solution ?
(a) Air (b) Brass w [Guj CET]
( c) Amalgam (d) Benzene in water (a) 100 g (b) 50 g (c) 0 .5 g (d) 5.0 g
19. In which ratio of volume 0.4 M HCI and 0.9 M HCl are to
be mixed such that the concentration of the resultant 2008
solution becomes 0.7 M? [MP PET] 30. 10cm3 of0.l Nmonobasicacidrequires l 5cm3 ofsodium
(b) 2 : 3 hydroxide solution whose normality is [KCETJ
(a) 4 : 9
(c) 3 : 2 (d) 1 : 1 (a)l.5N (b)0.15N
3 (c) 0.066 N (d) 0.66 N
20. 50 cm of 0.2 N HCI is titrated against 0.1 N NaOH
solution. The titration is discontinued after adding 50 cm 3 31. 2 N HCI solution will have same molar concentration as a
ofNaOH. The remaining titration is completed by adding (a) 4 .0 N H 2 SO 4 (b) 0 .5 N H 2 SO 4 [WB JEE]
0.5 N KOH. The volume of KOH required for completing (c) 1 NH2 SO 4 (d) 2 NH2 SO4
the titration is [KCET] 32. What is the molality of pure water ? [OJEEJ
(a) 12 cm 3 (b) 10 cm3 (a) 1 (b) 18
(c)25cm 3 (d) 10.5cm3 (c) 55.5 (d) None of these
21. Calculate the nomrnlity of 250 m.L aqueous solution of 33. Which one of the following concentration units is
H 2 SO4 having pH= 0.00. [Guj CETJ independent of temperature ? [J&K CETJ
(a) 0.25 N (b) 0.50 N (c) 1 N (d) 2 N (a) Nom1ality (b) Molarity
22. What is the molarity of0.2 N Na 2 CO 3 solution ? [JCECE] (c) Molality (d) ppm
(a) 0.1 M (b) 0 M (c) 0.4 M (d) 0.2 M 34. The volume of water to be added to 100cm3 of
0. 5 N H 2 SO 4 to get decinom1al concentration is CBCECEJ
2009 (a) 400cm3 (b) 450cm3
23. The Henry's law constant for the solubility ofN2 gas in (c) 500cm3 (d) 100cm3
water at 298 K is 1.0 x 105 atrn. The mole fraction ofN 2 in
air is 0 .8. The number ofmols ofN2 from air dissolved in 2007
10 moles of water of 298 Kand 5 atm pressure is 1
35. The density (in g mL- ) of a 3.60 M sulphuric acid solution
(a) 4 x 10-4 (b) 4. 0 x 10- 5
that is 29% H 2 SO 4 (molar mass = 98 g mol- 1) by mass
[IITJEE]
will be [AIEEEJ
(c) 5.0x 10- 4 (d) 4 .0x 10-<;
(a) 1.64 (b) 1.88
24. Two bottles A and B contains 1M and 1m aqueous solution (c) 1.22 (d) 1.45
of sulphuric acid respectively [Manipall 36. 25 mL of a solution of barium hydroxide on titration with
(a) A is more concentrated than B 0. 1 molar solution of hydrochloric acid gave a titre value of
(b) B is more concentrated than A 35 m.L. The molarity of barium hydroxide solution was
(c) concentration of A is equal to concentration of B
(a)0.07 (b)0.14 [MPPET]
( d) it is not possible to compare the concentrations
(c) 0.28 (d) 0 .35
25. Which of the following concentration factors is affected by
37. Molarity ofa given orthophosphoric acid solution is 3M.
change in temperature ? [MHT CET]
It's n01m ality is CKCETJ
(a) Molarity (b) Molality
(a) 9 N (b) 0.3 N (c) 3 N (d) IN
(c) Mole fraction (d) Weight fraction
38. The volume of 10 N and 4 N HCI required to make 1L of
26. Molarity is expressed as [MPPET]
7 N HCI are [KCETJ
(a) Limo! (b) mol/L (c) mol/1000 g (d) g/L
(a) 0.50 L of 10 N HCI and 0.50 L of 4 N HCI
27. What is the total number of moles of H2 SO 4 needed to (b) 0.60 L of 10 N HCI and 0.40 L of 4 N HCI
prepare 5.0 L ofa 2.0 M solution ofH 2 SO4? [UPSEEJ (c) 0.80 L of 10 N HCI and 0.20 L of 4 N HCI
(a) 2.5 (b) 5.0 (c) 10 (d) 20 (d) 0.75 L of 10 N HCI and 0.25 L of 4 N HCI
28. 2.5 L of NaCl solution contain 5 moles of the solute. What 39. Volume of0.6 M NaOH required to neutralise 30cm 3 of
is the molarity ? [UPSEEJ 0.4 M HCI is [AMUJ
3 3 3
(a) 5 M (b) 2 M (c) 2.5 M (d) 12.5 M (a) 20cm (b) 40cm (c) 45cm (d) 30cm3
364 I Chapterwise & Topicwise Engineering Entrances Solved Papers
40. 138 gofethyl alcohol is mixed with 72 gofwater. The ratio 51. 35.4 mL of HCI is required for the neutralisation of a
of mole fraction of alcohol to water is [EAMCET] solution containing 0.275 g of sodium hydroxide. The
(a) 3 : 4 (b) 1: 2 (c) 1: 4 (d) 1: 1 normality ofhydrochlo1ic acid is [WB JEE]

41. One part of solute in one million parts of solvent is (a)0.97N (b)0.142N (c)0.194N (d)0.244N
expressed as [J&KCET] 52. Volume of water needed to mix with 10 mL solution of 1 N
(a) ppm (b) mg/100 cc HCI to get 0. 1N HCI is [UPSEEJ
(c) g/L (d) g/100 cc (a) 900 mL (b) 9 mL (c) 90 mL (d) 100 mL
42. The molarity of the solution obtained by dissolving 2.5g of 53. Equal moles of water and urea are taken in a flask. What is
NaCl in 100 mL of water is [J&K CET] mass percentage of urea in the solution? [UPSEEJ
(a) 0.00428 moles (b) 428 moles (a) 23.077% (b) 230.77%
(c) 0.428 moles (d) 0.0428 moles (c) 2.3077% (d) 0.23077%
43. Which one is correct? [DCEJ 54. An aqueous solution of glucose is 20% in strength. The
(a) Molality changes with temperature volume in which 1 g-mole of it is dissolved will be
(b) Molality does not change with temperature. (a) 9 L (b) 1.8 L [UPSEEJ
(c) Molarity does not change with temperature. (c)8 L (d)0.9L
(d) Normality does not change with temperature. 55. A solution contains 1. 2046 x 1024 hydrochloric acid
44. 40% by weight solution will contain how much mass of the molecules in 1 dm3 of the solution. The strength of the
solute in IL solution, density of the solution is 1.2 g/mL? solution is [AMUJ
(a) 480 g (b) 48 g [DCE] (a) 6 N (b) 2 N (c) 4 N (d) 8 N
(c) 38 g (d) 380 g 56. What is molarity of K+ in aqueous solution that contains
45. To neutralise completely 20 mL of0.1 M aqueous solution 17.4 ppm ofK 2 SO4 (174 gmol- 1)? [Guj CET]
of phosphorous acid (H3 PO 3 1 the volume of 0.1 M (a)2x l0- M 2
(b)2xl0- M 3
aqueous KOH solution required is [Jamia Millia Islamia] (c) 4 x 10- 4 M (d) 2x 10- 4 M
(a) 10 mL (b) 20 mL (c) 40 mL (d) 60 mL 57. Assuming that sea water is a 3.50 weight per cent aqueous
solution of NaCl. What is the molality of sea water ?
2006
(a) 0.062 m (b) 0 .0062 m [Guj CET]
46. Density of a 2 .05 M solution ofacetic acid in water is 1.02 (c) 0.62 m (d) 6.2 m
g/mL. The molality of the solution is [AIEEEJ
58. 5 L of a solution contains 25 mg of CaCO3 . What is its
(a) 1.14 mol kg - 1 (b) 3.28 mol kg - 1 concentration in ppm? (mol. wt. of CaCO3 is 100)
(c) 2.28 mol kg - 1 (d) 0.44 mol kg - 1
(a)25 (b) l [J&KCET]
47. At STP, a container has l mole of Ar, 2 moles of CO 2 , (c) 5 (d) 2500
3 moles of 0 2 and 4 moles of N 2 . Without changing the
total pressure if one mole of 0 2 is removed, the partial 2005
pressure of 0 2 is [MIIT CET] 59. Two solutions ofa substance (non-electrolyte) are mixed in
(a) changed by about 16% (b) halved the following manner. 480 mL of 1.5 M (first solution)
( c) changed by 26% (d) unchanged + 520mL of 1.2 M second solution.
48. How many grams of dibasic acid (mol. wt. 200) should be What is the molarity of the final mixture ? [AIEEEJ
present in 100 mL of the aqueous solution to give 0.1 N? (a) 2.70 M (b) 1.344 M (c) 1.50 M (d) 1.20 M
(a) 10 g (b) 20 g [MHT CET] 60. Molarity of0.2 N H 2 SO 4 is [KCET]
(c) 2 g (d) 1 g (a) 0.2 (b) 0.4 (c) 0 .6 (d)0.l
49. A 5 molar solution ofH 2 SO4 is diluted from 1 L to 10 L. 61. How many moles of Al 2 (SO 4 h would be in 50 g of the
What is the normality of the solution? [MP PET] substance ? [UPSEEJ
(a)0.25N (b) l N (c)2N (d)7N (a) 0.083 mol (b) 0.952 mol
50. Which of the following concentration terms is/are (c) 0.481 mo! (d) 0.140 mol
independent of temperature? [Ke rala CEEJ 62. A solution is prepared by dissolving 24.5 g of sodium
(a) Molarity hydroxide in distilled water to give IL solution. The
(b) Molarity and mole fraction molarity ofNaOH in the solution is
1
(c) Mole fraction and molality (Given, that molar mass ofNaOH = 40.0g mol- )CAMUJ
(d) Molality and normality (a) 0.2450 M (b) 0 .6125 M
(e) Only molality (c) 0.9800 M (d) 1.6326 M
 Solutions I 365
63. The volume of water to be added to N / 2 HCl to prepare 64. Molar solution means 1 mole of solute present in
3 (a) 1000 g of solvent (b) 1 L of solvent [BCECEJ
500cm ofN/ IOsolution is [RPET]
(a) 450cm3 (b) 100cm3 {c) 45cm3 (d) 400cm 3 ( c) l L of solution ( d) 1000 g of solution

Topic 2
Vapour Pressure of Solutions and
Raoult's Law
2014 7. The vapour pressure of a pure liquid A is 40 mm Hg at
1. Vapour pressure in mm Hg of0.I mole of urea in 180 g of 310 K. The vapour pressure of this liquid in a solution with
water at 25° C is (the vapow· pressw·e of water at 2 5° C is 24 liquid B is 32 mm Hg. What is the mole fraction ofA in the
mm Hg) [EAMCET] solution if it obeys the Raoult's law? [Punjab CETJ

(a) 2.376 (b) 20.76 (c) 23.76 (d) 24.76 (a) 0.5 (b) 0.6 (c) 0.7 (d) 0.8

2013 2009
2. Benzene and naphthalene form an ideal solution at room 8. Two liquids X and Y form an ideal solution at 300 K,
temperature. For this process, the true statement(s) is are vapour pressure of the solution containing 1 mol of X and
(a) !).G is positive [JEE Advanced] 3, mo! of Y is 550 mm Hg. At the san1e temperature, if I
(b) !).S system is positive mo! of Y is further added to this solution, vapour pressure
( C) !).S surroundings = 0
of the solution increases by 10 mmHg. Vapour pressure (in
(d) Af1 = 0 mmHg) ofX and Yin their pure states will be, respectively
3. Identify the mixture that shows positive deviation from (a) 200 and 300 (b) 300 and 400 [AIEEEJ
Raoult's law. [Kerala CEE] ( c) 400 and 600 ( d) 500 and 600
(a) CHC1 3 + (CH 3 ) 2 CO (b) (CH 3 )iCO + C 6 H 5 NH 9. A binary liquid solution is prepared by mixing n-heptane
(c)CHC1 3 + C6 H 6 (d)(CH 3 )iCO + CS 2 and ethanol. Which one of the following statements is
(e) C 6 H 5 N + CH 3 COOH correct regarding the behaviour of the solution ? [AIEEEJ
(a) The solution formed is an ideal solution
2012 (b) The solution is non-ideal, showing positive deviation
4. Which of the following will show a negative deviation from Raoult's law
from Raoult's law? [WB JEE] (c) The solution is non-ideal, showing negative deviation
( a) Acetone-benzene (b) Acetone-ethanol from Raoult's law
( c) Benzene-methanol (d) Acetone-chloroform (d) n-heptane shows positive deviation while ethanol
show negative deviation from Raoult's law
2011 10. Vapour pressure of pure 'A' is 70 mm of Hg at 25°C. It
5. A solution of two liquids boils at a temperature more than fom1s an ideal solution with 'B' in which mole fraction ofA
the boiling point of either them. Hence, the binary solution is 0.8. If the vapour pressure of the solution is 84 mm of Hg
shows [KCET] at 25°C, the vapour pressure of pure 'B' at 25°C is
(a) negative deviation from Raoult's law (a) 28 mm (b) 56 mm [Manipal]
(b) positive deviation from Raoult's law (c) 70 mm (d) 140 mm
(c) no deviation from Raoult's law
11. The vapour pressure of two liquids X and Y are 80 and 60
(d) positive or negative deviation from Raoult's law
Torr respectively. The total vapour pressure of the ideal
depending upon the composition
solution obtained by mixing 3 moles of X and 2 moles of Y
2010 would be [Kerala CEE]
6. On mixing, heptane and octane form an ideal solution. At (a) 68 torr (b) 140 torr (c) 48 torr (d) 72 torr
373 K, the vapour pressw·es of the two liquid components (e) 54 torr
(heptane and octane) are I 05 kPa and 45 kPa respectively. 12. One component of a solution follows Raoult's law over the
Vapour pressw·e of the solution obtained by mixing 25 g of entire range 0$ x 1 $ LThe second component must follow
heptane and 35 g of octane will be (molar mass of heptane Raoult's law in the range when x 2 is [AMUJ
= 100 g mol - 1 and ofoctane = 114 g mol- 1) . [AIEEEJ
(a) close to zero (b) close to 1
(a) 72.0 kPa (b) 36. l kPa (c) 96.2 kPa (d)144.5 kPa (c)0$x2 $0.5 (d)0$x2 $1
366 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2008 2006
13. At 80°C, the vapour pressure of pure liquid' A ' is 520 mm 19. On a humid day in summer, the mole fraction of gaseous
Hg and that of pure liquid 'B' is 1000 mm Hg. If a mixture H 2 0 (water vapour) in the air at 25°C can be as high as
solution of 'A' and 'B' boils at 80°C and 1 atm pressure, 0.0287. Assuming a total pressure of 0.977 atm. What is
the amount of' A' in the mixture is (1 atm = 760 mm Hg) the partial pressure of dry air? [Kerala CEEJ
(a) 52 mole per cent [AIEEEJ (a) 94.9 atm (b) 0 .949 atm
(b) 34 mole per cent (c) 949 atm (d) 0.648 atm
( c) 48 mole per cent (e) l.248 atm
( d) 50 mole per cent 20. At 25°C, the total pressure ofan ideal solution obtained by
14. Two liquids X and Y form an ideal solution. The mixture mixing 3 moles of'A' and 2 moles of'B', is 184 torr. What
has a vapour pressure of 400 mm at 300 K when mixed in is the vapour pressure (in torr) of pure 'B' at the same
the molar ratio ofl : 1and a vapour pressure of350 mm when temperature ? (Vapour pressure of pure 'A' at 25°C is
mixed in the molar ratio of l : 2 at the same temperature. The 200 torr) [J&K CET]
vapour pressures of the two pure liquids X and Y (a) 180 (b) 160
respectively are [Ke rala CEE] ~16 ~ 100
(a) 250 mm, 550 mm {b) 350 mm, 450 mm 21. Which one of the following is not correct for an ideal
(c) 350 mm, 700 mm (d) 500 mm, 500 mm solution ? [Jamia Millia Islamia]
(e) 550 mm, 250 mm (a) It must obey Raoult's law
15. Vapour pressure of pure A = JOO torr, moles = 2; vapour (b)Aff = 0
pressure of pure B = 80 torr, moles = 3. Total vapour (c) t.V = O
pressure of the mixture is [OJEEJ (d) Aff = t.V ;c: 0
(a) 440 torr (b) 460 torr (c) 180 torr (d) 88 torr
2005
2007 22. Benzene and toluene form nearly ideal solutions. At 20°C,
16. Equal masses of methane and oxygen are mixed in an the vapour pressure ofbenzene is 75 torr and that oftoluene
empty container at 25°C. The fraction of the total pressure is 22 torr. The partial vapour pressure of benzene at 20°C
exerted by oxygen is [AIEEE] for a solution containing 78 g of benzene and 46 g of
2 1 273 l 1 toluene in torr is [AIEEEJ
00 -
3
~ - X-
3 298
~ -
3
~ -
2
(a) 53.5 (b) 37.5 (c) 25 (d) 50

17. A mixture of ethyl alcohol and propyl alcohol has a vapour 23. A and B are ideal gases. The molecular weights of A and B
pressure of 290 mm at 300 K The vapour pressure of are in the ratio of 1: 4. The pressure of a gas mixture
propyl alcohol is 200 mm. If the mole fraction of ethyl containing equal weights of A and B is p atm. What is the
partial pressure (in atm) of Bin the mixture? [EAMCETJ
alcohol is 0.6, its vapour pressure (in mm) at the same
temperature will be [AIEEEJ (a)E (b) P
(a) 350 (b) 300 (c) 700 (d) 360 5 2
3
18. Formation of a solution from two components can be (c) _E_ (d) P
2 .5 4
considered as
I pure solvent ➔ separated solvent molecules, Af/1 24. In a mixture of A and B, components show negative
II pure solute ➔ separated solute mo lecules, t,.H2 deviation when [Jamia Millia Islamia]
III separated solvent and solute molecules ➔ solution, Aff3 (a) A - B interaction is stronger than A - A and B - B
Solution so fonned will be ideal if [UPSEEJ interaction
(a) Affsoln = Aff1 - Aff2 - Aff3 (b) A - B interaction is weaker than A - A and B - B
(b) Affsoln = Aff3 - Aff1 - Aff2 interaction
(c) Affsoln = Aff1 + Aff2 + Af!3 (C) t. Vmix > 0, Af mix > 0
( d) Affsoln = Aff1 + Aff2 - Aff3 (d) t.Vmix = 0, t.S mix> 0
 Solutions I 367

Topic 3
Colligative Properties
2014 2013
1. Consider separate solution of 0.500 M C2 H 5 OH(aqi 10. Which one of the following solutions exhibits the
0.100 MMg 3 (PO4 )i(aq), 0.250 M KBr (aq)and0.125 maximum elevation in boilin g point? [Manipall
M Na 3 PO4 (aq)i at 25° C. Which statement is true about (a) 0.1 m NaCl (b) 0 .1 m FeC1 3
these solution assuming all salts to be strong electrolytes. (c)0.lm CaC1 2 (d)0.lmBaC1 2
(a) They all have same osmotic pressure [JEE Main] 11. The temperature at which the vapour pressure of a liquid
(b) 0.100 M Mg 3 (PO4 h (aq) has the highest osmotic becomes equal to external (atmospheric) pressure is its
pressure (a) melting point [Ke rala CEEJ
(c) 0.125 M Na 3 PO4 (aq) has the highest osmotic
(b) sublimation point
pressure (c) inversion point
(d) 0.500 M C 2 H 5 OH(aq) has the highest osmotic
(d) critical temperature
pressure ( e) boiling point
2. If the elevation in boiling point of a solution of 10 g of 12. An aqueous solution freezes at- 0.186° Cthen elevation in
solute (mol. wt = 100) in 100 g of water is t-,.Tb, the
boiling point is (Kb = 0.5 12, KI = 1.86) [OJEEJ
ebullioscopic constant of water is [VITJ
(a)0.05 12° C (b)I00.0512°C
(a)IO (b)IO0Tb (c)L-,.Tb (d) t-,.Tb (c) - 0.0512° C (d) None of these
10
3. If the osmotic pressure of a 0.010 M aqueous solution of 2012
sucrose at 27° Cis 0.25 atm, then the osmotic pressure of a 13. K 1 for water is 1.86 K kg mol- 1 • If your automobile
0.010 M aqueous solution of NaCl at 27° C is [ManipalJ radiator holds 1.0 kg of water, how many grams ofethylene
(a) 0 .062 atm (b) 0.12 atm (c) 0.25 atm (d) 0.50 atm glycol (C 2 H 6 O 2 )must you add to get the freezing point of
the solution lowered to - 2.8° C? [AIEEEJ
4. A solution of 1.25 g of P in 50 g of water lower freezing
point by 0.3° C Molar mass of P is 94, (a)72g (b)93g (c)39g (d)27g
K f (water)= 1.86 K kg mo1- 1 • The degree of association 14. For a dilute solution containing 2.5 g of a non-volatile
of P in water is [KCETJ non-electrolyte solute in 100 g of water, the elevation in
(a) 80% (b) 60% (c) 65% (d) 75% boiling point at 1 atrn pressure is 2° C Assuming
concentration of solute is much lower than the
5. Glucose is mixed in 1 litre water, the ratio of t-,.T1 IK 1 concentration of solvent, the vapour pressw·e (mm of Hg)
changed to 10- 3 . The mass of glucose (C6 H 12 O 6 ) is 1
of the solution is (take Kb = 0.76 K kg rnol- ) [AIEEEJ
(a) 180 gram (b) 18 gram [UPSEEJ
(a) 724 (b) 740 (c) 736 (d) 7 18
(c) 1.8 gram (d) 0.18 gram
15. 1.2% NaCl solution is isotonic with 7.2% glucose solution.
6. The molar mass of a solute X in g mo1- 1, if its 1% solution
What will be the van't Hoff factor 'i' for NaCl? [BITSATJ
is isotonic with a 5% solution of cane sugar (molar mass
= 342grnol- 1 ) is [EAMCET] (a) 0.5 (b) 1 (c) 2 (d) 6
(a) 68.4 (b) 34.2 (c) 136.2 (d) 17 1.2 16. The relative lowering of vapour pressure of an aqueous
solution containing a non-volatile solute is 0.0125. The
7. Find the boiling point of a solution of 5.00 g ofnapthalene
molality of the solution is [Manipal]
(C10 H 8 ) in 100 g of benzene. Kb of benzene if 2 .53° el m
the nom1al boiling point of benzene = 800 C [IPU CETJ (a) 0.70 (b) 0.30
(c) 0.125 (d) 0.07
(a) 81°C (b) 85°C (c) 0.9°C (d) 79°C
17. The elevation in boiling point would be highest for
8. Which among the following is a non-colligative property
(a) 0.08 M BaC12 (b) 0.1 5 M KCl [Manipall
(a) elevation in boiling point [J&K CETJ
(c) 0.10 M glucose (d) 0.06 M Ca(NO 3 )z
(b) osmotic pressure 1
(c) refractive index 18. The mass of a non-volatile solute of molar mass 40 g mol-
(d) lowering of vapour pressure that should dissolved in 114 g ofoctane to lower its vapour
pressure by 20%, is [KCETJ
9. 45 g of ethylene glycol (C2 H 6 O 2 ) is mixed with 600 g of
water, what is depression in freezing point? [J&K CETJ (a) 11.4 g (b) 9.8 g
(c) 12.8 g (d) 10 g
(a) 7.9 K (b) 2.5 K (c) 6 .6 K (d) 2 .2 K
368 I Chapterwise & Topicwise Engineering Entrances Solved Papers

19. 58.5 g of NaCl and 180 g of glucose were separately 27. A solution containing 1.8 g of a compound (empirical
dissolved in 1000 mL of water. Identify the correct fommla CH2 0) in 40 g of water is observed to freeze at -
statement regarding the elevation of boiling point (b.p.) of 0.465°C. The molecular formula of the compound is
the resulting solutions. [WB JEE] (K of water= 1.86 kg Kmol - 1) [KeralaCEEJ
I
(a) NaCl solution will show higher elevation of boiling (a) C2 H 4 0 2 (b) C3 H 6 0 3
(b) Glucose solution will show higher elevation of (c) C4 H 8 0 4 (d) C5 H 10 0 5
boiling point (e) C6 H 12 0 6
( c) Both the solutions will show equal elevation of
28. Choose the correct statement.
boiling point.
( d) The boiling point elevation will be shown by neither When concentration of a salt solution is increased
of the solutions. [Guj CETJ
20. The relative lowering of vapour pressure of a dilute (a) Boiling point increases while vapour pressure
solution is equal to mole fraction of solute present in the decreases.
solution. Which of the following law is state this? [OJEEJ (b) Boiling point decreases while vapour pressure
increases.
(a) Henry law
(c) Freezing point decreases while vapour pressure
(b) Avogadro's law increases.
(c) Raoult's law
(d) Freezing point increases while vapour pressure
(d) Law of definite proportion
decreases.
21. The highest osmotic pressure corresponds to the following
solution [AMU] 2010
(a) M II Ourea (b) M II Oglucose 29. The relative lowering of vapour pressure of a dilute
(c)M/lOHCl (d) M /IO BaC1 2 aqueous solution containing non-volatile solute is 0.0125.
22. The correct order of increasing boiling points of the The molality of the solution is about [Manipall
following aqueous solutions [AMU] (a) 0.70 (b) 0.50 (c) 0.90 (d) 0.80
0.0001 M NaCl(I), 0.0001 M Urea(II), 0.001 M 30. At25°C, the highest osmotic pressure is exhibited by 0.1 M
MgC1 2 (III), O.Ql M NaCl (IV) is solution of [ManipaIJ
(a) I < II < III < IV (b) IV < III < II < I (a) urea (b) glucose (c) KC! (d) CaC1 2
( c) II < I < III < IV (d) III < II < IV < I 31. The empirical formula of a non-electrolyte is CH2 0.
A solution containing 6 g of the compound exerts the same
2011 osmotic pressure as that of 0.05 M glucose solution at the
23. The freezing point (in °C) of solution containing 0.1 g of same temperature. The molecular formula of the
K 3 [Fe(CN)6 ](mo!. wt. 329) in 100 g of water (K = 1. 86 compound is CKCETJ
1
K kg mol - 1) is [IIT JEE]
(a) C2 H 4 0 2 (b) C 3 H 6 0 3 (c) C 5 H 10 0 5 (d) C4 H 8 0 4
(a)-2.3x10- 2 (b)-5.7xl0- 2
32. Colligative properties of a solution depends upon
(c) - 5. 7 X 10- 3 (d) - 1.2 X 10- 2
(a) natw-e of both solvent and solute [Punjab CETJ
24. Ethylene glycol is used as an antifreeze in a cold climate. (b) nature of solute only
Mass of ethylene glycol which should be added to 4 kg of ( c) number of solvent particles
water to prevent it from freezing at - 6° C will be (K I for ( d) the number of solute particles
1
water= 1.86 K kg mol - and molar mass ofethylene glycol 33. At a constant temperature, which of the following aqueous
= 62 g mo1- 1) [AIEEE] solutions will have the maxirmun vapour pressure ?
1
(a) 804.32 g (b) 204.30 g (c) 400.00 g (d) 304.60 g (Mo!. wt. NaCl= 58.5, H 2 S04 = 98.0 g · mol- )
25. The empirical formula of a non-electrolyte is CH 2 0. A (a) 1 molal NaCl (aq) [Guj CETJ
solution containing 3 g of the compound exerts the same (b) 1 molar NaCl (aq)
osmotic pressure as that of 0.05 M glucose solution. The (c) 1 molal H2 S04 (aq)
molecular formula of the compound is [KCETJ (d) 1 molar H 2 S04 (aq)
(a) CH2 0 (b) C 2 H4 0 2 (c) C4 H 8 0 4 (d) C 3 H 6 0 3 34. Which of the following would exert maximum osmotic
26. At 25°C a 5% aqueous solution of glucose (molecular pressure ? [RPETJ
weight = 180 g mo1- 1) is isotonic with 2% aqueous (a) Decinormal aluminium sulphate
solution containing an unknown solute. What is the (b) Decinormal barium chloride
molecular weight of the unknown solute. [Kerala CEEJ ( c) Decinormal sodium chloride
( d) A solution obtained by mixing equal voltunes of (b)
(a) 60 (b) 80 (e) 98 (c) 72
and (c) and filtering
(d) 63
 Solutions I 369
35. What is the freezing point of a solution containing 2008
8.1 g HBr in 100 g water assuming the acid to be 90% 43. The vapour pressure of water at 20°C is 17.5 mm Hg. If
ionised? (K for wt = 1.86 K mo1- 1) [JCECE]
18 g of glucose (C6 H 12 0 6 ) is added to 178.2 g of water
I
(a) 0 .85°C (b) - 3.53°C (c) 0°C (d) - 0.35°C at 20°C, the vapour pressure of the resulting solution
will be
2009
(a) 17.675 mmHg (b) 15.750 mmHg [AIEEE]
36. A 6% solution of urea is isotonic with [Manipal] (c) 16.500 mmHg (d) 17.325 mmHg
(a) 1 M solution of glucose 44. When 25 g of a non-volatile solute is dissolved in 100 g of
(b) 0.05 M solution of glucose water, the vapour pressure is lowered by 2. 25 x 1o- 1 mm.
( c) 6% solution of glucose If the vapour pressure of water at 20°C is 17. 5 mm, what is
( d) 25% solution of glucose the molecular weight of the solute ?
37. In countries nearer to polar region, the roads are sprinkled [BITSAT, AMU, EAMCET]
with CaCI 2 . This is [Manipal]
(a) 206 (b) 302 (c) 350 (d) 276
( a) to minimise the wear and tear of the roads
45. Solutions A, B, C and Dare respectively 0.1 M glucose,
(b) to minimise the snow fall
(c) to minimise pollution 0.05 M NaCl, 0.05 M BaCl 2 and 0.1 M A1Cl 3 . Which one
( d) to minimise the accumulation of dust on the road of the following pairs is isotonic ? [MHT CET]

38. A 1% solution of KC! (I), NaCl (II), BaC1 2 (III) and urea (a)AandB (b)BandC
(IV) have their osmotic pressure at the same temperature in ( c) A and D ( d) A and C
the ascending order (molar masses of NaCl, KC!, BaCl 2 46. The vapour pressure of benzene at a certain temperature is
and urea are respectively 58.5, 74.5, 208.4 and 60 g. 640 mm of Hg. A non-volatile and non-electrolyte solid
mo1 - 1 ) . Assume 100% ionisation of the electrolytes at this weighing 2.175 g is added to 39.08 g of benzene. If the
temperature [Kerala CEE] vapour pressure of the solution is 600 mm of Hg, what is
(a) I < III < II < IV the molecular weight of solid substance ? [MHT CET]
(b) III < I< II< IV (a) 49.50 (b) 59.60 (c) 69.60 (d) 79.82
( c) I < II < III < IV 47. Which of the following solutions will have highest boiling
(d) I < III < IV < II point ? [MHT CET]
(e) III < IV < I < II
(a) 0.1 M FeC1 3
39. The difference between the boiling point and freezing point (b) 0.1 M BaCl 2
of an aqueous solution containing sucrose (mo!. wt.= 342 g (c) 0.1 M NaCl
mo1 - 1 ) in 100 g of water is 105.0°C. If K I and Kb of (d) 0.1 M urea (NH 2 CONH2 )
water are 1.86 and 0.5 1 K kg mol - 1 respectively, the
48. Which is not a colligative property in the following?
weight of sucrose in the solution is about [Ke rala CEE]
(a) pH of a buffer solution [MP PET]
(a) 34.2 g (b) 342 g (c) 7.2 g
(b) Boiling point elevation
(d) 72 g (e) 68.4 g
( c) Freezing point depression
40. Which of the following is not a colligative property ? (d) Vapour pressure lowering
(a) Optical activity [UPSEE] 49. Which of the following can be m easured by the
(b) Osmotic pressure Ostwald-Walker dynamic method? [KCET]
( c) D epression of freezing point
(a) Relative lowering of vapour pressure
( d) Elevation of boiling point
(b) Lowering of vapour pressure
41. If 0.1 M solutions of each electrolyte are taken and if all (c) Vapour pressure of the solvent
electrolytes are completely dissociated, then whose boiling ( d) All of the above
point will be highest ? [Indraprastha CET]
50. The freezing point of water is depressed by 0.37°C in a
(a) Glucose (b) KCl 0.01 mo! NaCl solution. The freezing point of0.02 molal
(c) BaC12 (d) K 4 [Fe(CN)6 ] solution of urea is depressed by [WB JEE]
42. The increase in boiling point of a solution containing 0.6 g (a) 0.37°C (b) 0.74°C
urea in 200 g water is 0.50°C. Find the molal elevation (c)0.1 85°C (d)0°C
constant. [Guj CET]
51. On adding 1 g arsenic to 80 g benzene, the freezing point of
(a) I0Kkgmol - 1 benzene is lowered by 0. l 9°C. The formula of arsenic is
1
(b) lOKgmol -
(c) 10 K kg mol (K f = 5.08 K kg mol-1 ) [UPSEE]
( d) 1.0 K kg mol - 1 (a) As (b) As 2 (c) As 3 (d) As4
370 I Chapterwise & Topicwise Engineering Entrances Solved Papers

52. The osmotic pressure (at 27°C) of an aqueous solution 62. The mass of glucose that should be dissolved in 50 g of
(200 mL) containing 6 g of a protein is 2 x 10- 3 atm. If water in order to produce the same lowering of vapour
R = 0 . 080 L atm mo! - 1K - 1 , the molecular weight of pressure as is produced by dissolving l g of urea in the
protein is [UPSEEJ same quantity of water is [Jamia Millia Islamia]
5 5
(a)7. 2 x 10 (b) 3. 6 x 10 (a) I g (b) 3 g (c) 6 g (d) 18 g
(c) l.8x 105 (d) I.Ox 105
53. Osmotic pressure of a solution at a given temperature
2007
(a) increases with concentration [UPSEEJ
63. A 5.25% solution of a substance is isotonic with a
(b) decreases with concentration 1.5% solution of urea (molar mass = 60 g mo! - 1) in the
(c) remains same same solvent. If the densities of both the solutions are
(d) initially increases and then decreases assumed to be equal to 1.0 g cm- 3 , molar mass of the
substance will be [AIEEEJ
54. The vapour pressure of pure liquid A is 0.80 atm. When a
non-volatile B is added to A its vapour pressure drops to (a) 90.0 g mo1- 1 (b) 115.0 g mo1- 1
1 1
0.60 atm. The mole fraction of B in the solution is (c) 105.0 g mol- (d) 210.0 g mol-
(a)0.125 (b) 0.25 [UPSEE] 64. A solution of sucrose (molar mass = 342g/mol) is prepared
(c) 0.5 (d)0.75 by dissolving 68.4 g of it per litre of solution, what is its
osmotic pressure
55. Highest boiling point is found in [OJEEJ
(R = 0.082L atm K - 1 mol- 1) at 273 K ? [BITSAT]
(a) 0.1 M NaCl (b) 0. 1 M BaC12
(a) 3.92 atm (b) 4.48 atm
(c)0.lMsucrose (d)0. lMKCI
(c) 5.92 atm (d) 29.4 atm
56. Isotonic solutions have equal [OJEE]
65. In a 0.2 molal aqueous solution of a weak acid HX, the
( a) vapour pressure (b) osmotic pressure degree of ionisation is 0.3. Taking K I for water as 1.85,
( c) boiling point (d) freezing point the freezing point of the solution will be nearest to
57. Consider the following aqueous solutions and assume (a)-0.481°C (b)-0.360°C [MPPET]
100% ionisation in electrolytes
(c)-0. 260°C (d)+0.480°C
l. 0.1 m urea TT. 0.04 m Ali(S04 ) 3
Ill. 0.05 m CaC1 2 TV. 0.005 m NaCl 66. Which one is a colligative prope1ty? [OJEEJ
The correct statement regarding the above solution is (a) Boiling point (b) Vapour pressure
(a) freezing point will be lowest for solution I [Guj CETl (c) Osmotic pressure (d) Freezing point
(b) freezing point will be highest for solution IV 67. The osmotic pressure is expressed in the units of [OJEEJ
(c) boiling point will be highest for solution IV (a) MeV (b) cal
(d) vapour pressure will be highest for solution II (c) emfs (d) atm
58. A solution containing 4 g of polyvinyl chloride polymer in 68. At temperature 327°C and concentration C osmotic
one litre ofdioxane was found to have an osmotic pressure pressure of a solution is p , the same solutions at
of 4 .1 x 1o- atm at 27°C. The approximate molecular
4
concentration C/2 and a temperature 427°C shows osmotic
weight of the polymer is [J&K CET] pressure 2 atm, value of p will be [DCEJ
(a) 1.5 X 103 (b) 2.4 X 105 (a) 12 (b) 24 (c)~ (d) ~
4 12
(c) 1.0 x 10 (d) 2x 10 7 7 5 6
59. Maximum lowering of vapour pressure is observed in the 69. Which one of the following statements is false?
case of [J&K CET] [Jamia Millia lslamia]
(a) 0.1 M glucose (b) 0. 1 M BaCl2 (a) R aoult's law states that the vapour pressure of a
(c) 0.1 M MgSO4 (d) 0.1 NaCl component over a solution is proportional to its mole
60. Blood cells do not shrink in blood because blood is fraction
(a) hypotonic (b) isotonic [BCECEJ (b) The osmotic pressure (1t) of a solution is given by the
(c) equimolar (d) hypertonic equation 1t = MRT, where, M is the molarity of the
solution
61. What is the amount of urea dissolved per litre if its aqueous (c) The correct order of osmotic pressure for 0.01 M
solution is isotonic with 10% cane sugar solution ? (mo!. aqueous solution of each compound is
wt. of urea = 60) [DCEJ BaC1 2 > KC! > CH 3 COOH > sucrose
(a) 200 g/L ( d) Two sucrose solutions of same molality prepared in
(b) 19.2 g/L different solvents will have the same freezing point
(c)l7. 54g/L depression
(d) 16.7 g/L
 Solutions I 371
2006 2005
70. 18 g of glucose (C6 H I 2 O 6 ) is added to 178.2 g of water. 81. Equimolar solution in the same solvent have [AIEEEJ
The vapour pressure of water for this aqueous solution at (a) different boiling and different freezing points
100°C is [AIEEEJ (b) same boiling and same freezing points
(a) 759.00 Torr (b) 7.60 Torr (c) same freezing point but different boiling point
(c) 76.00 Torr (d) 752.40 Torr (d) same boiling point but different freezing point
71. The freezing point of 1% solution of lead nitrate in water 82. The molar freezing point constant for water is l .86°C/mol.
will be [Manipall If342 g ofcane sugar (C12 H22 O I I ) is dissolved in 1000 g
of water, the solution will freeze at [Manipall
(a) 2°C (b) l°C (c) 0°C (d) below 0°C
(a) -1. 86° C (b) l.86°C (c) - 3.92° C (d) 2 .42° C
72. The amount of urea to be dissolved in 500 cc of water
(K1 = I. 86° C) to produce a depression of O. l 86°C in the 83. The movement of solvent molecules through a
freezing point is [Manipall semipem1eable membrane is called [Manipall

(a)9g (b)6g (c)3g (d)0.3g (a) electrolysis (b) electrophoresis

( c) osmosis ( d) cataphoresis
73. The freezing point of a 0.05 molal solution of a
non-electrolyte in water is [MHTCETJ
84. The osmotic pressure of0.2 molar solution ofw·ea at 27°C
(R = 0 . 082L atrn mol- t K - 1) is [MP PET]
(a) - 0. 093° C (b) 1.86° C
(c) 0. 93° C (d) 0 . 093° C (a) 4 .92 atm (b) 1 atrn (c) 0.2 atm (d) 27 atrn

74. At certain temperature a 5.12% solution of cane sugar is 85. Dry air is passed through a solution containing 10 g of a
isotonic with a 0.9% solution of an unknown solute. The solute in 90 g of water and then through pure water. The
molar mass of solute is [Ke rala CEEJ loss in weight ofsolution is 2.5 g and that ofpure solvent is
0.05 g. Calculate the molecular weight of the solute.
(a) 60 (b) 46.17 (c) 120
(d) 90 (e) 92.34 (a) 50 (b) 180 (c) 102 [Kerala CEE]
(d) 25 (e) 51
75. By dissolving 5 g substance in 50 g of water, the decrease
in freezing point is l .2°C. The gram molal depression is 86. Calculate the molal depression constant of a solvent which
l .85°C. The molecular weight of substance is [WB JEE] has freezing point 16.6°C and latent heat of fusion 180.75
Jg - I · [OJEE]
(a) 105.4 (b) 118.2 (c) 137.2 (d) 154.2
76. The vapour pressure will be lowest for [WBJEE] (a) 2.68 (b) 3.86 (c) 4.68 (d) 2.86
(a) 0. 1 M sugar solution 87. In an osmotic pressure measurement experiment, a 5%
(b) 0 .1 M KC! solution solution ofcompound' X' is found to be isotonic with a
(c) 0. 1 M Cu(NO 3 h solution 2% acetic acid solution. The gram molecular mass
(d) 0 .1 M AgNO 3 solution of X' is [AMUJ

77. Osmotic pressure of 0.4% urea solution is 1.64 atrn and (a) 24 (b) 60
that of3.42% cane sugar is 2.46 atm. When the above two (c) 150 (d) 300
solutions are mixed, the osmotic pressure of the resulting 88. The vapour pressure of water at 23°C is 19.8 mm. 0.1 mole
solution is [UPSEEJ of glucose is dissolved in 178.2 g of water. What is the
(a) 0.82 atrn (b) 2.46 atm (c) 1.64 atm (d) 4 .10 atm vapour pressure (in mm) of the resultant solution ?
78. Relative lowering of vapour pressw·e of a dilute solution is (a) 19.0 (b) 19.602 [EAMCET]
0.2. What is the mole fraction of the non-volatile solute? (c) 19.402 (d) 19.202
(a) 0.8 (b) 0.5 [J&K CETJ 89. Which of the following is incorrect? [J&K CETJ
(c) 0.3 (d) 0.2 (a) Relative lowering of vapour pressure is independent
79. Depression in freezing point is 6 K for NaCl solution if k1 of the nature of the solute and the solvent.
(b) The relative lowering of vapour pressure is a
for water is 1.86 K/kg/mol, amount of NaCl dissolved in colligative property.
1 kg water is [DCEJ (c) Vapour pressure of a solution is lower than the
(a) 3.42 (b) 1.62 (c) 3.24 (d) 1.71 vapour pressure of the sol vent.
80. If a solution containing 0.072 g atom ofsulphur in 100 g of (d) The relative lowering of vapour pressure is directly
proportional to the original pressure.
a solvent (k1 = 7.0) gave a freezing point depression of
0.84°C, the molecular formula ofsulphur in the solution is 90. X is dissolved in water. Maximum boiling point is
[Jamia Millia Islamia] obse1ved when X is ... (0.1 M each) [DCE]
(a) S 6 (b) S 7 (c) S 8 (d) S 9 (a) CaSO4 (b) BaCl 2 (c) NaCl (d) urea
372 I Chapterwise & Topicwise Engineering Entrances Solved Papers
91 . Which bas minimum osmotic pressure ? [DCE] 92. Solution A contains 7 g/L of MgCl 2 and solution B
(a) 200 mL of2 M NaCl solution contains 7 g/L of NaCl. At room temperature, the osmotic
(b) 200 mL of 1 M glucose solution pressure of [DCEJ
(c) 200 mL of2 M urea solution (a) solution A is greater than B
(d) All have same osmotic pressure (b) both have same osmotic pressure
(c) solution B is greater than A
( d) cannot be determine

Topic 4
Abnormal Molar Masses
2014 2009
1. MX 2 dissociates into M 2+ and X - ions in an aqueous 6. van 't Hoff factor of aq. K 2 SO4 at infinite dilution bas
solution with a degree of dissociation (ex.) of 0.5. The ratio value equal to [AMUJ
of observed depression of freezing point of the aqueous (a) 1 (b)2
solution to the value of the depression of freezing point in (c) 3 (d) between 2 and 3
the absence of ionic dissociation. [IIT Advance]
7. If the various terms in the below given expressions have
(a) 1 (b) 2 (c) 3 (d) 4 usual meanings, the van 't Hoff factor (i) cannot be
2. If in a solvent, n simple molecules of solute combine to calculated by which one of the expressions ? [DCEJ
form an associated molecule, ex. is the degree of association, (a) 1tV = ✓inRT
the van 't Hoff factor is equal to [Manipal]
(b) ~Tl = ik1 . m
1 (c) ~Tb= ikb.m
(a) - - (b)l-cx. + ncx,
1- no.
ex,
(c)l - cx. +-
ex,
(d) - - I+ ex,
( d) P~tven\- P solution
P solvent
=i (-n-)
N+n
n n
3. A 2.0 molal sugar solution bas approximately the same
2008
freezing point as a 1.0 molal solution of [IPU CETJ 8. van 't Hoff factor more than unity indicates that the solute
in solution has [Manipall
(a) CaC1 2 (b) CH3 COOH
(c) C 2 H 5 OH (d) NaCl (a) dissociated (b) associated
(c) Both (a) and (b) (d) cannot say anything
2011 9. Abnormal colligative properties are observed only when
4. The degree ofdissociation (cx.)ofa weak electrolyte, AxBY the dissolved non-volatile solute in a given dilute solution
is related to van't Hoff factor (i) by the expression (a) is a non-electrolyte [J&K CETJ
i -1 i- 1 (b) offers an intense colour
(a) ex, = - - - {b) ex. = - - - [AIEEEJ
(x + y - l) x + y+ l ( c) associates or dissociates
(d) offers no colour
x+y -l (d) ex. = X + y + I
()
CCX, = - - ' - - -
10. van't Hoff factor ofCa(NO3 ) 2 is [BCECE]
i -1 i- 1
(a)one (b)two
2010 (c) three (d) four
5. If sodium sulphate is considered to be completely 11. Osmotic pressure observed when benzoic acid is dissolved
dissociated into cations and anions in aqueous solution, the in benzene is less than that expected from theoretical
change in freezing point of water ( ~ T1 ), when 0.01 mole considerations. This is because [Jamia Millia Islamial
of sodium sulphate is dissolved in 1 kg of water, is (a) benzoic acid is an organic solute
1
(K J = l.86Kkgmol- ) [AIEEE] (b) benzoic acid bas higher molar mass than benzene
(a) 0.0372 K (b) 0.0558 K ( c) benzoic acid gets associated in benzene
(c) 0.0744 L (d) 0.01 86 K ( d) benzoic acid gets dissociated in benzene
 Solutions I 373
2007
12. When 20 g ofnaphthoic acid (C11 H 8 0 2 )is dissolved in 50 15. The elevation in boiling point of a solution of 13.44 g of
g of benzene ( K = 1.72 K kg mol- 1 ), a freezing point CuC1 2 in 1 kg of water using the following infom1ation
depression of2 'lis observed. The van't Hoff factor (I) is will be (molecular weight of CuCl 2 = 134. 4 and
(a) 0 .5 (b) 1 [IITJEEJ kb = 0.52Km- 1 ) [IITJEE]
(c) 2 (d) 3 (a) 0.16 (b) 0.05
13. Phenol dimerises in benzene having van't Hoff factor 0.54. (c) 0.1 (d) 0.2
What is the degree of association ? [OJEEJ 16. Ifa is the degree ofdissociation ofNa 2 S04 , the van 't Hoff
(a) 1.92 (b) 0.98 (c) 1.08 (d) 0.92 factor ( i) used for calculating the molecular mass is
[AIEEE]
2006 (a) 1- 2a (b) l+2a
14. Observe the following abbreviations 1tobs = observed (c) l- a (d) 1+ a
colligative property, n eat = theoretical colligative property 17. The van't Hoff factor ofBaCl 2 at 0.01 M concentration is
assuming normal behaviour of solute. van 't Hoff factor ( i) 1.98. The percentage of dissociation of BaC1 2 at this
is given by [J&K CETJ concentration is [Kerala CEEJ
(a) i = 1tobs X 1tca1 (b) i = 1tobs + 1tcat (a) 49 (b) 69
(c) i = 1tobs - 1tcat (d)i = 1tobs (c) 89 (d) 98
1tcal (e) 100

Topic 5
Distribution Law
2011 2006
3 2. Distribution law was given by
1. One gram of silver gets distributed between 10 cm of [WBJEE]
molten zinc and 100 cm 3 of molten lead at 800°C. The (a) Henry
percentage of silver still left in the lead layer in (b) van't Hoff
approximately. Distributed coefficient = 300 [KCETJ (c) Nemst's
002 ~5 ~3 001 (d) Ostwald
 Answers
TOPIC 1 Types of Solutions and Methods of Expressing Concentration
1. (d) 2. (d) 3. (b) 4. (b) 5. (c) 6. (a) 7. (c) 8. (a) 9. (b) 10. (a)
11. (b) 12. (c) 13. ( C) 14. (b) 15. (c) 16. (c) 17. (c) 18. (d) 19. (b) 20. (b)
21 . (b) 22. (a) 23. (a) 24. (a) 25. (a) 26. (b) 27. (c) 28. (b) 29. (b) 30. (c)
31 . (a) 32. (c) 33. (c) 34. (a) 35. (c) 36. (a) 37. (a) 38. (a) 39. (a) 40. (a)
41 . (a) 42. (c) 43. (b) 44. (a) 45. (c) 46. (c) 47. (c) 48. (d) 49. (b) 50. (c)
51 . (c) 52. (c) 53. (a) 54. (d) 55. (b) 56. (d) 57. (c) 58. (c) 59. (b) 60. (d)
61 . (d) 62. (d) 63. (d) 64. (c)
.ID.e!C1_ Vapour Pressure of Solutions and Raoult's Law
1. (c) 2. (b,c,d) 3. (d) 4. (d) 5. (a) 6. (a) 7. (d) 8. (c) 9. (b) 10. ( d)
11. (d) 12. (d) 13. ( d) 14. (e) 15. (d) 16. (c) 17. (a) 18. (c) 19. (b) 20. (b)
21. (d) 22. (d) 23. (a) 24. (a)
Ioe!U Colligative Properties
1. (a) 2. (c) 3. (d) 4. (a) 5. (d) 6. (a) 7. (a) 8. (c) 9. (d) 10. (b)
11. (e) 12. (a) 13. (b) 14. (a) 15. (c) 16. (a) 17. (b) 18. (d) 19. (a) 20. (c)
21 . ( d) 22. (c) 23. (a) 24. (a) 25. (b) 26. (c) 27. (e) 28. (a) 29. (a) 30. (d)
31 . ( d) 32. (d) 33. (a) 34. (a) 35. (b) 36. (a) 37. (a) 38. (e) 39. (d) 40. (a)
41 . ( d) 42. (a) 43. (d) 44. (c) 45. (a) 46. (c) 47. (a) 48. (a) 49. (d) 50. (a)
51 . ( d) 52. (b) 53. (a) 54. (b) 55. (b) 56. (b) 57. (b) 58. (b) 59. (b) 60. (b)
61 . ( c) 62. (b) 63. (d) 64. (b) 65. (a) 66. (c) 67. (d) 68. (b) 69. (d) 70. (d)
71 . ( d) 72. (c) 73. (a) 74. (a) 75. (d) 76. (c) 77. (d) 78. (d) 79. (b) 80. (a)
81. (b) 82. (a) 83. (c) 84. (a) 85. (c) 86. (b) 87. (c) 88. (b) 89. (d) 90. (b)
91 . (b) 92. (c)
TOPIC4 Abnormal Molar Masses
1. (b) 2. (c) 3. (d) 4. (a) 5. (b) 6. (c) 7. (a) 8. (a) 9. (c) 10. (c)
11. (c) 12. (a) 13. ( d) 14. (d) 15. (a) 16. (b) 17. (a)
TOPICS Distribution Law
1. (c) 2. (c)
 Explanations
Topic 1 Types of Solutions and Methods of Expressing Concentration
1. As phosphoric acid is a tribasic acid, its ,,.factor can be I, 2 and 3. 200
= lO00 X 0.4 X 36.5 = 0.08 X 36.5 g
Hence, its normality can be M, 2M or 3M. Where, Mis molarity
of solution. ·: 0.365 g ofHCI is present in 1.0 mL stock solution.
Therefore, N = 0.25, 0.50 or 0.75.
2. Moles of oxalic acid= moles ofNaOH
:.0.08 x 36.5 g HCI wi ll be present in °·080.365
36 5
x · = 8.0 mL

VxN=~ 8. Normality (N) = ~

M E -V
~ X N = 0.064 10 g 10
1000 40 l00 L= l.66 N
60 X 100 ml 60x - -
N = 0.064 x I 000 = 0 _064 1000
25x 40 __ molecular weight x M
9• N [ON changes from + 7 to+ 2]
Normality of oxalic acid = Basicity x Molarity equivalent weight
. _ Normality _ 0.064 _
In acidic medium, equivalent weight ofKMNO4 = ~ = 31.6
⇒ M oanty-
I - - - ' - - - - - 0 .032
Bas.icily 2
5
3. Molar mass ofNa 2CO3 = 106 g/ mol 158
Thus, NKMnO 4 = - X 0.025 = 0.125
5.3 31 .6
Number of moles = - = 0.05 mo!
106 90
Equivalent weight of oxalic acid = = 45
number of moles ofNa 2CO 3 2
Molarity
volwne of solution (L) 90
Noxalicacid = X 0.1 = 0.2
5 45
Molarity= 0.0 x 1000
500 N 1V1 =N2V2
Molarity = 0.1 M 0.2 XV= 0.125 x20
V = 0.125 x20 = 12 _ mL
5
4. On mixing two solutions of same substances, molarity of the final 0.2
mixture 10. NA= 0.5, VA= V L (let)
M = M 1V 1 + M 2V2 For HCI, valence factor = 1
V 1 + V2 N s =Ms = 0. 1, Vs = (2 - V) L
25 X 3 + 75 X 4 From normality equation
25 + 75 NV =NAVA+ NsVs
375 0.2 x2 = 0.5 X V + 0.1 X (2 - V)
= = 3.75 M 0.4 = 0.5 V + 0.2 - 0. 1 V
100
0.2
. ( ) massofsolute(ing)xlO00 2.5x l 000 0.4 V = 0.2 V = - = 0.5
. o1a11ty m =- - - - - - - - - =- - - -
SM 0.4
molecular weight of solute 60 x 75
x mass of solvent (in g) VA = 0.5 Land, Vs = (2 - 0.5) = 1.5 L
= 0.555 rnol/kg oe 0.556 mol/kg 11. Molecular weight ofNa 2SiO3 = 2 x 23 x 2 x 32 + 3 x 16 = 158
_ M V + M 2V2 From, molarity
6. M1- 1 1
v,
+ V2 percentage by weight of solute x density of solution x l 0
= 750 X 0.5 + 250 x2 = 875 = _ M mo las mass of solute
0 875
750 + 250 1000 = percentage by weight ofNa 2SiO 3 x 1.25 x 10
3
7. Mass of HCI in 1.0 mL stock solution 158
29 2 . 3 xl58
= 1.25 X · = 0.365 g :. Percentage by weight of Na 2SiO 3 = - - -
100 1.25 X 10
Mass of HCI required for 200 mL solution of0.4 M HCI = 37.92%
376 I Chapterwise & Topicwise Engineering Entrances Solved Papers
moles of solute I
12. Molarity 17. Molarity, M = x OOO ; where !Vi is mass ofH2SO4 in g,
Wz
volume of solution (L) M 2 x Vol. (mL)
120 M 2 is the molar mass ofH2SO4
moles of urea =- =2
60 I X 98 X 200
W2 = 1000 )9.6 g
Weight of solution = weight of solvent + weight of solute
= 1000 + 120 = 1120 g H2SO4 + 2Hz0 ~ 2Hp+ + sot
112 But according to equation, I mole of H 2SO4 gives 2 mole of
Volume 0g x I = 0.974 L
1.15g/mL I000mL/L [Hp+ ]ions. So, the amountofH 2SO4 to prepare 200 mL solution
having the 1 M concentration of Hp+ ions is
. =-
M o Ianty -= 2 . 05 M
2.000
0.974 19.6/2 = 9.8 g.
moles of solute 5.2 rnol CHpH 18. Solution is a homogeneous mixture of two or more substances.
13. Molality
kg of solvent I kg(= I 000 g) H 2O Since, benzene is insoluble in water, thus does not mixed with
1000 it.
n 1 (CHJ◊H) = 5.2, 112(Hi0)=~ = 55.56 Hence, benzene in water is not an example of solution.
n 1 + ni = 5.20 + 55.56 = 60.76 mol 19. Let the volume of0.4 M HC I is V1 and that of0.9 M HCI is V2•
n1 5.2 We know that,
X CH30H =- - - =- - = 0.086
n1 + n2 60.76 NV = N 1V1 + N 2V2 [·:IMHCI= INHCI]
(Mixture) (for 0.4 M HCI) (for 0.9 M HCI)
moles of solute
14. Molality 0.7 (V1 + V2) = 0.4 V1 + 0.9 V2
kg of water
0.7 Vi + 0.7 V2 = 0.4 Vi + 0.9 V2
0.0 10
Moles of urea =- - mol 0.7 Vi - 0.4 V1 = 0.9 V2 - 0.7 V2
60
0.3 V1 = 0.2 V2
Mass of water at STP (d lg/cm 3 = lkg/dm 3) = 0.3 dm 3 = 0.3 kg
~= 0.2 =~
:. Molality = ~ = 5.55x 10--4 molal V2 0.3 3
60x 0.3
20. When 0.1 N NaOH is used,
15. The sum of mole fractions of all components of a solution is
always one. N 1V1 = N2V2
(For HCI) (For NaOH)
16. pV = nRT ⇒ I X 41 = n X 0.0821 X 500 ⇒ n = 0.998 mol
0.2N X V1 = 50 X 0.1 N
The number of moles of ethane =x _50x0.I_ 3
So, number of moles of ethene = (0.998 - x) V1 - - 25 cm
0.2
Reaction of ethane and ethene with 0 2
When 0.5 N KOH is used, N 1V1 (For remaining HCI)
(i) 2Cif4 + 702 ➔ 4CO2 + 6H2O = N 3 V3 (For KOH)
(ii) C2H 4 + 30 2 ➔ 2CO2 + 2H 2O
0.2N x 25 = 0.5 Nx V3,
According to (i) reactions _0.2x25_
V3- - - - - 10 cm 3
2 mole ethane reacts with = 7 mole 0 2 0.5
7x 21. pH= - log[H+ ] ⇒ log[H+ ]= - pH=0.00
x mole ethane reacts with =- mole 0 2
2
[H+ ] = antilog (0.00)[H+ ]= 1.0 M
According to (ii) reaction
IM H 2SO 4 = 2NH2SO4
I mole ethene reacts with= 3 mole 0 2
250 2
(0.998 -x) mo le ethene reacts = 3 (0.998 -x) mole of 0 2 :. Normality of250 mL solution = x = 0.50 N
7x 10 1000
- + [3 (0.998 - x)] = - mole of 0 2
2 3 . . equivalent weight
22.. M o Ian ty = norma11ty x ~ - - - ~ ~
10 molecular weight
3.5x+2.994-3x= - moleofO2
3 Given, normality ofNa 2CO3 solution= 0.2 N
0.5x = 3.333- 2.994 = 0.3393 Equivalent weight = M
0.3393 Molecular weight =2 M (": Na 2CO 3 is dipositive.)
x = - - = 0.678 mole of ethane
0.5
Molarity = 0.2 x _!!___ = 0. 1 M
moles of ethene = 0.998 - 0.678 = 0.32 2M
0 678 23. According to Henry's law, p = KHX
mole fraction of ethane = · = 0.67
0.998 where, x = mole fraction
0 32
mole fraction of ethene = · = 0. 32"' 0.33
0.998
 Solutions I 377
= 0.8x 5 32. Molality is defined as the numberofmoles per 1000 g of solvent.
. 1000
P N2 = 4 atm :. Molahty of water = - - = 55.5 m
4 18
n = !Ox - -
Ni lx10 5 33. Molality depends only upon weights, not on volumes whereas
other given concentration terms depend upon the volwne of
= 4 x 10-4 moles
solution. Volume ofa solution increases with rise in temperamre
where, but temperanrre does not affect the weights, therefore molality is
independent of temperanire.
''Ni number of moles of nitrogen dissolved
34. N Iv1 = N 2v2
ntt 2o number of moles of slovent
0.5x 100= 0.1 x V2 ⇒ V2 = 500 cm 3
PN 2 partial pressure of gas dissolved
: .Water to be added to 100 cm 3 solu tion
KH Henry's law constant for gas dissolved.
= 500-100 = 400 cm 3
XN2 mole fraction of nitrogen, N 2 in air
. 10 x density x percentage weight of solute
1 ty= - - - ~ - ~ - - ~ - ~ - - - -
35. M oan
24. IM H 2SO4 means I mole H 2 SO4 in 1000 cc of solution whereas molecular weight of the solute
Im means I mole H 2 SO 4 in 1000 g of water(= 1000cc of water). 3 60 98
Total volume of I m solution will be> 1000cc due to extra 1 mole Density = · x = 1.216 "' 122
10 X 29
H 2 SO4 . Hence, number of moles per l000 cc will be less.
Thus, 1 m is less concentrated than 1 M. 36. Let molarity of Ba(OH)z = M 1
25. Molarity gets affected as it is the number of moles per unit Normality= 2 M 1
volume (volume increases with increase oftemperan1re). Molarity of HCl = 0.1 M = 0.1 N
26. Molarity of a solution is the number of moles of the solute per N1V1 =N2V2
litre of solution. Unit of molarity is mol/L. 2 M1
X 25 = 0.1 X 35 M1 = 0.07 M
27. Number of moles= molarity x volume (in L) 37. Orthophosphoric acid (H 3PO4 ) is a tribasic acid.
Number of moles ofH2 SO 4 = 2.0 M x 5.0 L = 10 moles Normality = molarity x basicity
. number of moles of solute Normality= 3 M x 3 = 9 N
28. M o 1anty
volume of solution (in L) 38. Let V litre of ION HCI be mixed w ith (1- V) litre of 4 N HCl to
give (V + 1- V) = I L of7 N HCI.
Molarity = -2_ = 2 M
2.5 v
N I 1+ N 2 2 =N v v
29. Given, in 100 g of solution Na OH present= 10 g IO V + 4 (1 - V) = 7 x 1
:.Tn 500 g of solution NaOH present I0V+4-4V=7
10 X 500 6V=7- 4
50
100 g 3
V = - = 0.50 L
6
So, 50 g ofNaOH will be required to prepare 500 g 10%~NaOH
w Volume of 10 N HCl = 0.50 L
solution. Volume of 4 N HCI = 1- 0.50= 0.50 L
30. Volume ofmonobasic acid= 10 cm 3 39. According to molarity equation
Normality of mono basic acid= 0.1 N Molarity ofNaOH == molarity ofHCI
Volume ofNaOH solution= 15 cm 3 M 1V1 =M2V2
Normality ofNaOH solu tion = ? 0.6 X V1 = 0.4 X 30
_ 0.4 X 30 _ 3
N 1V1 N2V2 V1 - - 20 cm
(for monobasic acid) (for NaOH) 0.6
!Ox 0. 1 N= 15x N 2 138
40. Number of moles of ethyl alcohol = - =3
IN 46
N 2 = - = 0.066N 72
15 Number of moles of water = - = 4
18
31. Relationship between normality and molar concentration is
3 3
Normality= n x molarity (M)
X ~H50H = 3 + 4 =7
where, n = the number of moles ofH+ per mole of the compound
that a solute is capable of releasing (acid) on reacting with base.
4 4
Xtt 20= +4 =
7
In case ofHCl, n = 1 3
Hence, 2 N HCl solution "' 2 M H 2 SO 4 solution. X~HsOH=].!}_=i
In case ofH2SO4 n = 2 XH20 4/7 4
Hence, 4.0 N H 2SO4 solution "' 2 M H2SO4 solution.
378 I Chapterwise & Topicwise Engineering Entrances Solved Papers
41. The concentration is expressed in parts per million (ppm) when 2
one part of solute is dissolved in one million parts of solvent. =(~- )xtOO
10 1+ 2 + 2 + 4
42. Molarity (M)
_ _ _ _ _ _ _w_e_ig~h_t _o_f _so_ l_u_te_ _ _ _ _ _ x
1000
= L~ -i) X 100= 790 "' 8
mo lecular weight of solute x volume of the solution
8
percentage change = - x 100 = 26%
= 2.5 x I000 = 0.428 moles 30
58.5x 100 . number of g- equivalents of solute
43. In molarity and normality, the volume of the solution is
48. N orma I1ty = - - - - - - - - - - - -
volume of solution (in litre)
considered while in molality the mass of the solvent is considered.
Molarity and normality change with temperature because of Given, basicity = 2, mol. wt.= 200,
expansion or contraction of the liquid wid1 temperature. V = 100 mL = 100/1000 L
However, molality does not change with temperature because Normality = 0. 1
mass of the solvent does not change with temperature. Eq. wt.= molecular weight= 200 = l00
percentage by weight of solute x density of basicity 2
. solution x 10 (in litre)
mass/eq. weight
44. M o Ianty = - - - - - - - - - - - - - - ~ - ~ N= - - - - - - - - -
M volume of solution in litre

or 0. l = mass/ JOO
where, M = molecular weight of the solute
100/ 1000
Molari = 40 x 1.2 x 10 ...(i)
ty M X 1000 or 0. l = mass/JOO
0.1
. weight of the solute / M
M o Ian ty = - - - - - - - - - - ... (ii) or mass= 0.1 x 0.1 x 100= 1.0 g
volume of solution (in litre)
49. Molarity ofH2SO 4 = 5 M
From Eqs. (i) and (ii),
Normality of H 2SO4 = 2 x 5 = 10 N
weight of solute 40 X 1.2 X 10
MxlO00 MxlO00 N 1V1 =N2V2
10xl =N 2 xl0
Weight of solute= 480 g
or N 2 =l N
45. H 3PO 3 is a dibasic acid (containing two ionisable protons SO. Mole fraction and molality does not involve volume therefore,
attached to O directly). they are independent of temperature.
H3PO 3 a=="' 2H+ + HP0~- 51. We know that,
0.1 M H 3PO 3 = 0.2 N H 3PO3 40 g ofNaOH = I g eq. ofNaOH
and 0.1 M KOH= 0.1 N KOH 1
0.275 g ofNaOH = - x 0.275 eq.
N1V1 = N2V2 40
(KOH) (H3PO3) I
= - x 0.275 x 1000= 6.88 meq
0 . I V1 = 0.2 x 20 V1 = 40 mL 40
N1V1 = N2V2
46. Molality (m) = M x 100 (HCI) (NaOH)
I000d -MM 1
M =Molarity N I x 35.4= 6.88 (·: meq = NV)
M 1 = Molecular mass d = density N 1 =0.194
2 05
- - - --· - - - - - X 1000
(I 000 X 1.02) - (2.05 X 60) IO X 1 = 0.1 X V2
1 V: _ 10
= 2.28 mol kg-
2 - o.i
. moles of A
47. Mole fraction of A = - - - - V2 = I00mL
total moles
Hence, water needed to mix = 100 - IO= 90 mL
Given, moles of Ar= I, moles of CO2 = 2 ,
53. If moles ofH2O = moles of urea = x
moles ofO 2 = 3, moles ofN2 = 4,
:. Massof H 2O= 18xg
moles of 0 2 removed = 1
mass of urea= 60xg
Mole fraction ofO2 at initial stage
Total mass of the solution = l 8x + 60x
X 100 = ~ X 100 = 30
3
=78xg
1+2 + 3 + 4 10 18x
:. Mass percentage of urea= - - x 100 = 23.077%
Mole fraction of 0 2 at fina l stage 78x
 Solutions I 379
54. ·: 20 g glucose is dissolved in I 00 mL solution 63. Let x mL ofHCI are taken, then
. d"1ssoIved.m = -lOO mL so IutJon
· N 1V1 = N 2V2
:. I g g Iucose 1s I I
20 - xV=- x 500 x = 100 mL
1 180 2 10
180 g (g-mole) glucose is dissolved in = OO x = 900 mL
20 Hence, water needed to add = 500 - 100
=0.9L = 400mL
23
55. 6.023 x 10 molecules ofHCI 1 mole HCI= . moles of solute
64. M o Ianty= - - - - - - -
V of solution in litre
Hence, 1.2046 x I 024 molecules of
:. Molar solution means I mole of solute is present in I L of
HCI =1.2046 x 102423x 1 =2moles HCI solution.
6.023 X 10
Thus, two moles (=two gram-equivalents) ofHCI are dissolved in Topic 2 Vapour Pressure of
one dm 3 (one litre) solution. Therefore, the solution will be 2N. Solutions and Raoult's Law
56. K 2SO4 is 17.4ppmi.e., Hf g("" mL)hasK2SO 4 = 17.4 gK2SO4 1. From Raoult ' s law for very dilute solution
3
17
103 mL has K 2SO4 = .4 ; lO = 0.0 174 g/ L po - Ps =~ X M ⇒ 24 - Ps = 0.1 X _!!_
1 ~ mW N lW
= 0.0 174 mol/L 24 - Ps = 0.24
174 P, = 24 - 0.24 = 23.76 mm Hg
[KzSO4 ]= Ix 10- 4M 2. When an ideal solution is formed process is spontaneous thus
KzSO4 r==' 2K+ + so!- ~G < 0, ~S > 0
[K+ l = 2 X 10- 4 M Ml =0
M surrounding =0
57. 3.50 wt°/o of aqueous solution of NaCl means I 00 g of sea water
3. (CH3)zCO + CSz shows positive deviation from Raoult's law.
contains 3.50 g NaCl.
Water in sea water= 100 - 3.5 = 96.5 g = 0.0965 kg 0 H

Molality =
15
0.62 m
II I
4. CH 3 - C- CH3 , acetone and chloroform, CCl 3 w ill show a
58.5 X 0.0965 Acetone
weight of solute x 10 6 negative deviation due to their association after mixing .
58. ppm=
weight of solution 5. A solution of two liquids whose boiling point is more either of
two pure components is formed by non-ideal solution showing
- X 10-3 X 106
25 - - - - = 5 X 106 X 10-{i = 5 ppm negative deviation.
5000
. M 1V1 + M 2V2 6. Pr= Xtt. AI + Xo. p~ (where, Xtt = mole fraction of heptane
59. Total molarity= - - --~
V1 + V2 XO = mole fraction ofoctane)
1.5 X 480 + 1.2 X 520 25
1.344 M
480 + 520 100 0.45 and : . Xo = 0.55
XH = - 2~5,--'---"-"-3~5-
60. Normality of acid = molarity x basicity - +-
100 114
2
Molarity= N 0. = 0. 1M Pr = 0.45 x I 05 + 0.55 x 45 = 72 kPa
basicity 2
7. According to Raou lt's law,
mass
61. Moles PA= P;XA
molecular weight
Given, mass of Ali{SO 4 ) 3 = 50 g or XA = p1 32mm Hg 0.8
PA 40mm Hg
molecular mass of Al 2 (SO 4 ) 3 = 342
50
: . Moles of Al 2 (SO 4 ) 3 = - = 0.14 mo!
342
62. Given, w = 24.5 g, V = 1 L = 1000 mL M = ?
Mo!. wt. ofNaOH = 23 + 16 + 1 = 40 ...(i)
wX 1000 24.5 X 1000 When, 1 mo! of Y is further added to the solution
W e knowt.hat,. M = - - - = - - - -
mxV 40x 1000 1 4 0 0
560 = p + - + p X -
: . Molarity of solution = 0.6125 M X 5 y 5
380 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Thus, .. . (ii) 15. P total = P;XA + P;XB

On subtraction, (ii - i) where p = vapour pressure
p:=2800-2200 ⇒ p:=600 X = mole fraction
Total moles of A and B = 5
Putting the value of p; in Eq. (i)
p_: + 3 X 600 = 2200
Mole fraction of compound A = 3.
5
p>2200-1800 = 400 Mole fraction of compound B = l
5
9. n-heptane and ethanol forms non-ideal solution. In pure ethanol,
2 3
molecules are hydrogen bonded. On adding n-heptane, its then, P total = I 00 X - + 80 X - = 88 Torr
molecules get in between the host molecules and break chains of the 5 5
hydrogen bonds between them. Due to weakening of interactions, 16. Suppose the equal mass of methane and oxygen =w = Ig
the solution shows positive deviation from Raoult's law. . w/32
Mole fraction of oxygen = - - - - -
10. P = P~XA + P;XB w/32 + w/16
XA = 0.8 :. xn= l-0.8
⇒ 84 = 70 X 0.8 + p; X 0.2 ⇒ 84 = 56 + p; X 0.2 _n_ = .!.
0 28 3/32 3
p 8 = - =140mm
0 .2 Let the total pressure = p

11. Mole fraction of X, 11,: = - - = ~

3 Pressure exerted by oxygen (partial pressure)
3+2 5 I
= Xo2 XPmta.1 =pX)
2 2
Mole fraction of Y, n y = - -
3+ 2 5 17. According to Raoult 's law
0 0
3 2 p = P AXA + P BXB
Pr = Pxnx + p.n.Y =80 X- + 60 X - = 48 + 24 = 72 Torr 290 = 200 x 0.4 + p 0 8 x 0.6
. r 5 5
p 0 8 = 350mm
12. Ideal solution obeys Raoult's law at every range of concentration.
So, the second component must follow. Raoult's law in the range. 18. For ideal solution, W solution =W 1+ W 2 + t,,.H 3
When x2 is O~ x 2 ~ L
19. PH20 =x H20 Ptotal = 0.0287 X 0.977 = 0.028 atrn
13. Pr = P;XA + P;XB
Pmta.1 = Pdry air + PH20
Mixture solu tion boils at I atm = 760 mm = total pressure. Pdry air = Ptotal - PH 20
760 = 520 XA + 1000 (I - XA) = 0.977 - 0.028 = 0.949 atm
XA = 0.5, mot % of A = 50%
14. In 1st case, 20. p = p°-4 (___!!_,i___) + p 8
fl,4 + 118
0
(__!!.i._)
+fl,4 118
When two liquids X and Y are mixed in the molar ratio I : I .
3 2
Moles of X = l ⇒ Moles ofY = I 0
184 = 200 ( - - ) + p 8 ( - - )
3+ 2 3+2
Mole fraction of X (Xx)= .!_
2 3 2
J 84 = 200 XS + P 8 X S
0

Mole fraction ofY (X,y) = .!.

2 184 = 120 + p 08 3_
We know that p = p;x,x + i;xr (p = total pressure ofmixn1re) 5
2
I o I o
⇒
o o
400 X 2 = Px + py .. .(i)
64 = POB -
400 =
2 Px + 2 PY 64 X 5
5
0
For case Ilnd, p 8 = - - = 160Torr
2
When liquids are mixed in the molar ratio of I: 2
21. The ideal solution must
Moles of X = I ⇒ Moles ofY = 2
(i) Obey Raoult's law at all temperanires and pressures
Mole fraction of X (Xx) = .!_ (ii) W = 0
3 (iii) t,,.V = 0
2
Mole fraction of Y(xy) =
3,P = PxXx + PYXr
0 0

:. Statement (d), tiH = t,,.V * 0 is wrong.

I o 2 o o o
22. Mixture contains 78 g benzene= I mole benzene and 46 g toluene
350 = - Px + - py ⇒ 350 X 3 = Px + 2py ... (ii) = 0. 5 mole toluene
3 3
Total mole of benzene and toluene = 1.5 mol
From Eqs (i) and (ii), we get
p;
= 550mm ⇒ p; = 250mm Mole fraction of benzene in mixture = _.!._ = .3.
1.5 3
 Solutions I 381
VP of benzene p; = 75 Torr i - 1 0.6064 - I
CX= - 1- = I
- 0.3936
- -1 - - 1 - 0.5
:. Partial vapour pressure of benzene = p;xb
11 2
2
= 75 x - = 50 Torr = 0.7872 = 78.72"' 80%
3
100 K1 W2
23. Molecular weight. ratio of A and B = I : 4 5. Depression in freezing point, l'lT1 = - - ~ -
w1 M2
:. Mole ratio of A and B, if equal weight of A and B are taken
Given, w 1 = 1 Lt= I 000 g, M2 (solute)= I 80g/ mol
= 4: I l'lT
Partial pressure of B = _!_x P = !:__ __f_ = I 0-3 , 1'l'2 =?
5 5 Kl
24. In a mixture of A and B components show negative duration 10-3 X 1000 X 180
w - ------ 0.18 gram
when A - B interaction is stronger than A - A and B - B 2 - JOO
interaction.
6. For isotonic solutions, 7t 1 = 1t 2
Topic 3 Colligative Properties n 1RT = ,ii_RT
Vi V2
1. This problem deals w ith concept of colligative properties
(osmotic pressure) and van't Hoff factor, Calculate the effective Thus, ~=~
molarity of each solution. V1m1 Vzniz
i.e. effective molarity = van't Hoff factor x molarity
W1 =1 W2 =5
0.5 M C2H 5OH(aq) i = l effective molarity= 0.5 M Vi 'Vz
0.25 M K.Br(aq) i = 2 effective mo larity= 0.5 M "'1 =?
0.1 M MgiPO4 h(aq) i = 5 effective molarity= 0.5 M I 5
m2 =342 - = -
0.125 Na 3 (PO4 )(aq)i = 4 effective molarity= 0.5M m1 342
Hence, all colligative properties are same. 342
m1 = - = 68.4 = X
Thus, they all have same osmotic pressure. 5
Note Assuming Mg3 (PO4 ) 2 is completely soluble. 7. Elevation in boiling point (increase in boiling point of solution
due to addition of solute) can be measured by following given
l OOOx Kb X w
2. We know that, l'lTb = - - -~ - equation.
WxM l'lTb = 1000 x mass of solute x Kb
Where, w = weight of solute molecular mass of solvent x
W = weight of solvent mass of solvent
Kb = ebullioscopic constant of water = 1000 X 5 X 2.53 = _ "' I
0 99
l'lTb = elevation in boiling point 128x100
M = molar mass of solute l'lTb = boiling point of solution - boiling point of solute
l'lT = lOOOxKbx lO ⇒ l'lT. =K I = Boiling point of solution - 80
b lOOx l OO b b
Boiling point of solution= 80 + I= 81°C
3. Osmotic pressure = iCRT. For both the solution, all other 8. The properties of a dilute solution which depends only upon the
conditions are similar except' i' which is 1.0 for sucrose while 2.0 number of particles present in a solution and their concentration
for NaCl are called colligative properties. There are following four types of
colligative properties.
Therefore, osmotic pressure of NaCl = 2 x 0.25 = 0.50 atm
(a) relative lowering of vapour pressure.
4. Step I Calculation ofvan't Hoff factor of P
(b) elevation in boiling point of the solvent
l'lT1 = i X Kl x m (c) depression in freezing point
. K W1 1000 (d) osmotic pressure
=1X 1 x - X - -
W2 J\f1
9. Depression of freezing point is given as
0.3 = i X 1.86 X J. 25 X lOOO l'lT = KI x w x 1000
50 X 94 1 mxW
i= 0.3 X 50 X 94 = _6064
0 Forwater K1 = 1.86g / mol
1.86 X 1.25 X 1000
w = 45 g W = 600 g
Step IT Calculation of degree of association of P degree of Ill (C2~O2) = 2 X 12 + 6 X 1 + 2 X 16 = 62
association.
l'lT = 1.86 X 45 X 100 = 2 _2 K
Since, undergoing association then number of particles after I 62 X 600
association (n) are taken as 2.
382 I Chapterwise & Topicwise Engineering Entrances Solved Papers

10. 6Toc i Xm ⇒ p = 760 - 36 = 724 mm of Hg

W here, T = boiling point of solution 15. ForNaCI, 1t 1V1 =ixn1RT
i = van't Hoff factor 100 1.2
m = molality solution 1t 1 X - - = - - X 0.0821 X TX i .. .(i)
1000 58.5
If m is keeping constant,
For glucose, 1t 2V = niRT
:. Then 6 Tb oc i i.e greater the number of particles after
dissociation ofsolute, higher is their boiling point. n2 x IOO = E x 0.082 1 x T ...(ii)
1000 180
(a) 6 T oc 2 [NaCl gives 2 ions]
·: NaCl and glucose solutions and isotonic.
(b) 6 T oc 4 [FeCI 3 gives 4 ions]
(c) 6 T oc 3 [CaCI2 gives 3 ions]
1t I= 1t2
58 5
(d) 6 T oc 2 [B. CI 2 gives 3 ions] ⇒ i = _22 X · = 1.95 "' 2
180 1.2
Since, i is highest for FeCI 3, thus, 6T is highest for 0.1 m FeCl 3
thus, it will exhibit highest boiling point 16. According to Raou lt's law.
Relative lowering of vapour pressure = mole fraction of solute
11. At the boiling point,
(Xs) = 0.0125
vapour pressure of a liquid = atmospheric pressure. m·MA
Xs= - - ---
12. Given, T1 (freezing point of aqueous solution= -O.I 86°C ) 1000+ m·MA
6T1=T/ - T1 =0- (-0.186°C) 0.0 125 = m xl
8
Since, 6T1 = K1 x molality 1000 + m x18
6 T1 12.5 + 0.25m = 18m
⇒ molality = - -
Kf 17.775m = 12.5m
It is known that, 6 Tb = Kb xm = ~ = 0.70
6T 17.775
6Tb =0.512x ----1.
,.,, _ I 000 · Kb · w .
Kf 17... . ,.•,.,b - - - - - - " - - X /.
0 186 m·W
=0.512 X · = 0.0512°C w
1.86 6Tb oc i· - - - ( : Kb= constant)
w
13. Coolant glycol (C2H6O 2 ) is a non-electrolyte. m· - -
1000
IOOOK w1 or 6Tb oc i·M
6T1 = 2.8°, 6T1 = f
m1w2
(·: Molality = w and asslm1ing, Molality M = molarity)
_ = 1000 X 1.86 X w1 w
⇒ 28 m· - -
62 x l000 1000
W1 = 93.33 g Now, for the given solutions,
(a) For 0.08 M BaCl2, i · m = 3 x 0.08 = 0.24
14. The elevation in boiling point is
(b) For0.1 5 MKCI, i·M = 2 x 0. 15 = 0.30
6Tb =Kb. 111 lrm = molality = w, 1
n2 X 1000J (c) For 0. 10 M glucose, i · M =Ix 0.1 0 = 0. 10
(d) For0.06 M Ca(NO 3 ) 2, i·M = 3 x 0.06 = 0.1 8
[ni = mm1ber of moles ofsolute, w1 =weight ofsolvent in gram] Hence, 6Tb is maximum for 0.15 M KCI solution.
⇒ 2=0.76x~x l 000 ⇒ 171=2 18. p 0 = 100, p = I00 - 20 = 80, m = 40
100 19
M(C8 H 18 )= 114, w= ?, W = 114
Also, from Raou lt's law of lowering of vapour pressure
p 0 -p w M
- 6p ni
- - =x2= _ _ _ .,, _
t7i [ ·: 111 >>172]
--= - X-
p m W
Po 111 + 112 n,
100- 80 w 114 20 w
5 18 --- = - X- or
⇒ -6p=760x-x- 80 40 114 80 40
19 100
=36mmofHg or w = 20 X 40 = I0 g
80
 Solutions I 383
19. Elevation in boiling point, /',.Tb =ix Kb x m

Molal ity of NaCl solution = _!!__ x 1000

w /',.Tl= 0°-(-6°C) = 6°C
58.5
:. 6= 1000x l. 86Xw1 ⇒ w =800g..,804.32g
= 58.5 X 1000 = 1000 62X 4000 I
WH20 WH20
25. (1t) glucose= (1t) unknown compound
Molality of ½H 1p 6 solution
0.05 =2.
~ x l OOO M
= 180 1000
3
M= - - =60
WH20 WH20 0.05
Both the solutions have same molality but the values of i for NaCl 60
n.= - =2 (e.f.m. for CHp = 30)
and glucose are 2 and I respectively. 30
/',.Tb (NaCl) = 2 X /',.Tb (~H1206) So, molecular formula= C2H 40 2
Hence, NaCl w ill show higher elevation of boiling. 26. Solutions having same osmotic pressure are called isotonic
20. According to Raoult's Law, the relative lowering in vapour solutions.
pressure of a dilute solution is equal to the mole fraction of the 1t glucose =1t unknown solute
solute present in the solution i.e,
0 C 1 RT =C 2 RT
P -P = Xn where, Xn = mole fraction of solute
p ' ⇒
V V m l lllz
21. Osmotic pressure, 1t = iCRT 5 2 l80x2
- = - orm2 =- - -=72
ifC,R and Tare constant, thus, 1t ex: i 180 m2 5
For urea and glucose, i = I K1 x 11,z x l000
27. M, = --'------
For HCl and BaC12 , i > 1 - /',.Tl X W1
Due to high ionisation ofBaC1 2 then HCl,
or M _ l.86x l.8x 1000
2 180
isae12 > iHCI - 0.465x 40
: . Order of osmotic pressure will be 180 180
n= - - - - - - - 6
BaC12 > HCl > Urea = glucose emp. fonnula mass 30
22. T ex: i X molality Molecular formula of the compound is C6H 120 6 .
Ifmotality assumed to be equal to molarity, then 28. On increasing the concentration of a salt solution, the boiling
Tex: i xM point of salt solution increases w hile vapour pressure of the
solution decreases.
Larger the value of i and M, higher w ill be the boiling point
29. According to Raoult's law,
I. 0.0001 M NaCl, i = 2, M = 0.0001
Relative lowering of vapour pressure is equal to mole fraction of
T = 2 x 0.000 I = 0.0002 solute,
II. 0.0001 M urea, i=l, w
T = 1 X 0.0001 = 0.0001 p- Ps = n. w m
P n.+N=-;;;wW
III. 0.001 M MgC1 2, i = 3 - +-
m M
T = 0.001 X 3 = 0.003
w
- <<< -
w
TV. 0.01 M NaCl, i = 2 m M
T = 2X0.01 = 0.02 p 0 - p3 w/m w M
--- = - - = - X-
Thus, the order of their boiling points is p0 W m W
IV>ITI>I>II M
23. van't Hoff's factor (i) = 4 {3K+ + [Fe(CN),] 3- } 0.0125= wxl 8
1 mxW
Molali = ~X lOOO = - - w 0.0125
ty 329 100 329 ⇒
1 mW 18
- /',.T1 = iK1 .m = 4 x 1.86 x - - = 2.3 x 10-2 weight of solute (w) xl000
329
molar mass of solute (m)xWeight ofH 20 (W)
/',.Tl= To1-T1
2 Now molality
T1 = -2.3x 10- °C
25
⇒ m = O.Ot X l000 = 0.69"" 0.7
(As freezing point of water is 0°C.) 18
384 I Chapterwise & Topicwise Engineering Entrances Solved Papers
30. Osmotic pressure is a colligative property, i.e. depends only upon 36. Isotonic solutions have same molar concentration
the number of particles or ions in solution. More the number of 6
ions in solution, more will be the osmotic pressure of solution
(i) 0.1 M urea and 0.1 M glucose will have same number of
Molarity of urea =
1
= lM ii
molecules in solution as they do not ionise. 1000
(ii) KCI ➔ K + + Cl- (2 ions) Hence, 1 M solution of glucose is isotonic with 6% urea solution.
(iii) CaC1 2 ➔ Ca 2+ + 2CI- (3 ions) 37. In cotmtries nearer to polar region, the roads are sprinkled with
: . CaC1 2 produces maximum number of ions. CaC12 because CaC12 decreases the freezing point of ice and
therefore, minimise the wear and tear of the roads.
:.It will have highest osmotic pressure.
38. I% solution means I g solute is present in 100 mL of water.
31. Solutions having same osmotic pressure, at a given temperah1re,
. ixwx RT
have same concentration. Osmotic pressure, 1t = - - - -
Concentration of compound = concentration of glucose M xV
6 I. JtKCI = 2 X I X 1000 X RT 0.268 RT
- - =0.05
Mxl 74.5 X 100
6 1t _ 2 x Ix l 000xRT = 0_342 RT
⇒ M= - =1 20g II.
0.05 NaCl - 58.5 X I 00
Empirical fonnu la mass (CH2O) = 12 + 2 + 16=30
molecular mass III 1t
=3x l xl000xRT =0.l 44 RT
n . BaCI 2 208.4 X ] 00
empirical formula mass
IV. 1t =l x l xl00OxRT =0.l 67 RT
= 120 = 4 urea 60x 100
30
Hence, molecular fonnula =(CH 2 O)4 = C4H 8 0 4 Since, temperature is same in all cases, the ascending order of
osmotic pressure is
32. The properties of solution which depend only on the number of
solute particles but not on the nature of the solute taken are called III < IV < I < II
colligative properties. 39. Given, Tb - T1 = 105.0°C
33. One molar (I M) aqueous solution is more concentrated than one ⇒ (100- !:!,.Tb)- (0-1:!,.TJ) = 105°C
molal aqueous solution of the same solute. In solution, H 2SO4 !:!,.Tb+ !:!,.TJ = 5
provides three ions, w hile NaCl provides two ions. Hence, vapour !:!,.Tb + !:!,.T1 = (kb + k1 ) x m (m = molality)
pressure of solution of NaCl is higher (as it gives less ions).
Therefore, I molal NaCl will have the maximum vapour pressure. ⇒ 5 = (1.86 + 0.51)X w X lOOO
342xl00
34. Al 2 (SO4 ) 3 produces maximum number of ions so, it will have
highest osmotic pressure. :. On solving, w = 72g
40. Colligative properties depends only upon the number of solute
35. !:!,.TJ = i x Kf xm
particles.
Since, optical activity depends upon the nature of substance
Ions at equilibrium I - CL CL CL (through which plane polarised light is passed), it is not a
Total ions = 1 - IX+ IX+ IX= I + IX colligative property.
i = I + IX 41. Elevation in boiling point is a colligative property, i.e. depends
1 upon the number of particles. Hence, the electrolyte which give
Given, K1 = 1.86 K rnol-
largest number of particles in the solution, has the highest boiling
mass ofHBr = 8.1 g, mass ofH 2O = 100 g point.
(IX)= degree of ionisation = 90% Since, K 4[Fe(CN~ ]gives largest number ofparticles, i.e. 5, hence
mass ofsolute / rnol. wt. ofsolute it has the highest boiling point.
m (molality)
mass ofsolvent in kg number of moles of solute
42. Molality, m = - - - - - - - - -
8.1 / 81 weight of solution in kg
100/ 1000 l000 x W1 = I000x 0.6 _
0 05
i= 1 +IX= 1+ 90/100= 1.9 m1W2 60 X 200
!:!,.TJ =i x k1 x m [ :.Molecular weight ofNH 2CONH2 = 60]
8 118 1 Given, !:!,.Tb = 0.50
= l.9x l.86x · =3.534°C
100 /1000 !:!,.Tb= Kb x m
!:!,.T1 = (depression in freezing point)= freezing point of water - or 0.50 = Kb x 0.05
freezing point of solution 3 .534 = 0 - freezing point of solution. Kb= 10 K kg rnol- 1
: . Freezing point of solution= - 3.534° C
 Solutions I 385
18 47. Elevation in boiling point is a colligative property, i.e. depends
43. Moles of glucose= - = 0.1 mol
180 only on number of particles or ions. 0. 1 M FeCl 3 gives maximum
178.2 number of ions, thus has highest boiling point.
Moles ofH20 = - - = 9.9
18 48. Certain properties of dilute solution containing non-volatile
nglucose 0.1 0.1 solute do not depend upon the nature of the solute dissolved but
Xglucose =- ~ ~ - - depend only upon the number of particles of the solute present,
n. glucose + n water 0.1+ 9.9 JO
are called colligative properties. Some colligative properties are
According to Raoult's law boiling point elevation, freezing point depression, lowering of
p 0 -p,_ 17.5-p,_0.I vapour pressure. Since, pH depends only upon the molar
----;;;- - Xsolute ⇒ _ - concentration of if ion not on their number, thus, it is not a
17 5 10
colligative property.
So, Ps = 17.325 mm Hg
49. By Ostwald-Walker dynamic method, the relative lowering of
44. Given,
vapour pressure, lowering of vapour pressure and vapour
Weight of non-volatile solute, w = 25 g pressure of the solvent, all can be measured. In this method, the
Weight of solvent, apparatus used, contains two bulbs : bulb A contains solution and
W = 100g bulb B contains solvent. The loss of weight in bulb B gives the
Lowering of vapour pressure, lowering of vapour pressure and total loss of weight in both the
p 0 - Ps = 0.225 mm tubes gives the vapour pressure of the solvent and
Vapour pressure of pure solvent, Relative lowering of vapour pressure
p 0 = 17.5 mm = lowering of vapour pressure
Molecular weight of solvent (HP), M = 18 g vapour pressure of solvent
Molecular weight of solute, m = ? 50. 11~= i K1 m
According to Raoult's law where, 11T1 = depression in freezing point
p - P, = wx M
0
i = van 't Hoff factor
p0 mxW m =molality
0.225 25 X 18 and K1 = freezing point depression constant
17.5 m X 100 For 0.Dl molal NaCl solution
m = 25 X 18 X 17. 5 = 350 g 0.37 = 2 X Kl X 0.01
22.5 K _ 0.37
...(i)
45. Isotonic solutions have same molar concentration of solute i - 2 X 0.01
particles in solution. For 0.02 molal urea solution
: . Effective molar concentration = i x M 11T1 =IX K1 X 0.02
Effective molar concentration for 11T
K - 1 ...(ii)
A = 0.1 x 1 = 0.IM B = 0.05x2= 0.IM i - 0.02
C = 0.05x3 = 0.15M D = 0.lx4 = 0.4M As K1 is a constant value, thus, From Eqs. (i) and (ii) we have
Since, A and B have same molar concentration, 0.37 = 11TI
Thus, A and Bare isotonic with one another. 2 X 0.0 1 0.02
46. Given, vapour pressure of benzene, p 0 = 640 mm Hg l1T = 0.37 X 0.02
⇒
1 2x0.01
Vapour pressure of solution, p = 600 mm Hg
Weight of solute, w = 2. 175 g 11T1 = 0.37° C
Weight of benzene, W = 39.08 g 1000K1 w
51. 11T1 =- - ~
Molecular weight of benzene, M = 78 g mW
Molecular weight of solute, m = ? l1T1 = 0.19° C; K1 = 5.08 kg mol-1, w= I g; W = 80 g
According to Raoult's law, 1000 K w
m= - -~1 -
p -p = wxM
0
11T1W
p0 mxW
= 1000 X 5.08 XI= 334_21
640 - 600 2.175 X 78 0.19 X 80
⇒
640 m X 39.08
Atomic weight of As= 74.92
40 2.175 X 78 334.21
- Hence, number of atoms = - - "" 4
640 m X 39.08 74.92
16x2.175x78 Hence, the formula of arsenic is As4 .
m= ⇒ m = 69.457 "" 69.60
39.08
386 I Chapterwise & Topicwise Engineering Entrances Solved Papers

w wRT 60. Blood cells do not shrink in blood because blood is isotonic.
52. 1tV= - RT, m= - -
m 1tV When a cell is placed in a solution hav ing an isotonic pressure
Here, w = 6 g, 1t = 2 x Io- 3 atm, T = 300 K, (equal to its own) the cell main tains its normal volume. As
isotonic solution has the same osmotic pressure as the cells
R = 0.080 L-atm mol- 1K-1, V = 200 mL = 0.2 L contained in it, there is no concentration gradient.
= 6x 0.080 x 300 = _ x 105
111
2 X 10- 3 X 0.2
36
61. 1tV = -w RT
/Tl

53. According to the Boyle-van't Hoff law, at constant temperature for isotonic solutions, osmotic pressure (1t) is same.
the osmotic pressure of a solution is directly proportional to its ~ = W2
concentration and inversely proportional to its dilution. T hus
m 1V1 m2V2
1t oc C (where, C = concentration).
Hence, the osmotic pressure of a solution at a given temperature V1 = IL
increases with concentration. V2 = I 00 mL = 0.1 L
54. According to the Raoult's law, the re lative lowering of v apour ~= 10
pressure which is produced by dissolving a non-volatile solute in 60 X I 342 X 0.1
a solvent is equal to mole fraction of the solute. ⇒ WI= 17.54 g/L
po- Ps -x 62. According to Raoult's law,
po - B
0
P - Ps = w1M2
where, 0
p = vapour pressure of solvent po W2M 1
p, = vapour pressure of solution 0

To produce same lowering of vapour pressure, P - Ps wi ll be

Xs = mole fraction of B po
0
Given, p = 0.80 atm Ps = 0.60 atrn same for both cases.
= 0.80 - 0.60 = 0.20 = 0.25 W(glucosc) X 18 = W(urea) X 18
XB 0.80 0.80 So,
50 X 180 50 X 60
55. Colligative properties depend upon number of particles in
W(g1ucose) = weight of glucose
solution and concentration of solution. Larger the number of
particles in solution, higher is the colligative properties. W(urea) = weight of urea= 1g 0
Hence, highest boiling point is found in 0.1 M BaC1 2 • W(gtucose) X 18 = ~
W(glucose) =3
BaCli(aq) - Ba 2 + + 2Cl- 50 X 180 50 X 60

56. Isotonic solutions have same osmotic pressure at same temperanrre. 63. If, solutions are isotonic, then their molar concentrations are also
equal.
57. According to colligative property, freezing point w ill be highest
C 1RT =C2RT
for IV solution due to lower concentration of NaCl.
C1 =C2
58. Given, weight of PVC, w = 4 g
If density of both the solutions are assumed to be equal to 1. 0 g
Volume of solution, V = IL cm- 3• 5.25% solution of a substance means I 00g solution
Osmotic pressure, 1t = 4.1 x I 0-4 contains 5.25g solute and thus, I 000g solution contains 52.5g
solute. Similarly I 000g solution contains 15g of urea.
Temperature, T = 27°C = 27 + 273 = 300 K ⇒ 1t V = nRT
· =~
52 5
Hence
or 7t V = ~RT (M = molecular weight) ' M 60'
M
M = molecular mass of the substance
4. 1 X 10-4 X I= _i_ X 0.0821 X 300 M = 52.5 x 60 = 210 g mol-1
M
15
M = 4 X 0.0821 X 300
64. Osmotic pressure (1t) = CRT
4 X 10-4 X I
5 Here, C = concentration of solution
M = 2.4 X 10
C= !!._
59. Lowering of vapour pressure is a colligative property, i.e., V
depends only upon the number of particles of solute and not on w weight in gram of substance
the nan1re of solute. n= - = -~--~------
m molecular weight of substance
0.1 M Glucose - Remains undissociated
V= IL
0.1 M BaCl2 - Ba 2 + + 2CI - ⇒ 3 ions
2 ⇒
C = 68.4
0.1 MMgSO4 - Mg + + SO~ -⇒ 2 ions 342
0.1 MNaCI - Na++ Cl- ⇒ 2ions 7t =
68
.4 X 0.082 X 273
As 0.1 M BaCl 2 gives maximum number of particles, hence it 342
exl1ibits maximum lowering of vapour pressure. = 4.48 atm
 Solutions I 387
65. Given, m = 0.2 73. For non-electrolyte t-.T1 = K f x m
K f = 1.85 ⇒ a = 0.3 Given, m = 0.05,
i =I+ a= 1.3 tJ.1j- = 1.86 X 0.05 = 0.093°C
ti.T1 = molality X K f X i Freezing point of solution
= 0.2x l.85x 1.3= 0.481° t>.Tf = Tfo-Tf
ti.T1 =T/-T1 ⇒ 0.481°=0-T1 0.093= 0-T1 ⇒ T1 = -0.093°C
T1 = -0.481° 74. As isotonic solutions have similar osmotic pressure, thus, they
: . Freezing point = - 0.48 1°C have similar molar concentrations.
66. Osmotic pressure is a colligative property because it depends C1 =C2
upon the number of solute particles but not on the nature of the
solute. ⇒
!1:1 = 112 ⇒ ~= ~
v1 V2 M1V1 M2V2
67. Osmotic pressure (1t) = CRT ⇒ 1t = mol x 11101-1 LK-1 atmx K A 5.12% solution of cane sugar suggest that 51.2g of cane sugar
L
present in 1000 g or IL of water. Similarly, 0.9% solution of
Thus, Unit of osmotic pressure is atm. unknown solute contains 9g of solute in 1000 g or IL of water.
n = atm 51.2 9 9x 342 _
Thus, - - = - - ⇒ M 2 = - - - =60gmol 1
342xl M 2 xl 512
68. 1tV = nRT, 1t = !!...RT ⇒ 1t =CRT
V l000K x w
1t CRT 75. We know that, m = f
=_ l_ l
__!_ ⇒ 1t 1 = p, 1t2 = 2 atm, t>.TxW
1t2 CiRT2 Here, t>.T = l.2°C, K f = 1.85°
C w= 5 g, W = 50 g
C1 =C,C2=
2 = I000 x l.85x 5 = 154 _2 g mol-1
111
Tl = 600K, T2 = 700K l.2x 50
p 2 x C x R x 600 24
------ ⇒ p= - 76. Vapour pressure of a solvent is lowered by the presence of solute
2 C x Rx 700 7 in it. Lowering in vapour pressure is a colligative property, i.e. it
69. (a) PA =XAP~, true depends on the number of particles present in the solution.
Cu(NO3 )i give the maximum number of ions (i.e. 3) so, it causes
(b)1t = iMRT = MRTtrue (ifvan 't Hofffactor i = I) the greatest lowering in vapour pressure of water.
(c) i =[I+ (y- I) x ]y =number of ions x =degree of ionisation 77. Osmotic pressure of two solutions will be added.
i = 3forBaCl 2 x = 1 (strong electrolyte) Hence, osmotic pressure of resulting solution
i = 2forKClx = 1 (strong electrolyte) = 1.64 + 2.46=4.l0atm.
i =(I + x) for CH 3COOH x < <I (weak) 78. According to Raoult's law, the relative loweri ng in vapour
i = 1for sucrose (non-electrolyte) pressure of an ideal solution containing the non-volatile solute is
i (for BaC1 2) > KC I > CH 3COOH > sucrose equal to the mole fraction of the solute.
T hus, ( c) is also true. ·: Relative lowering of vapour pressure= 0.2
(d) t-.T1 = K1 m, K1 is dependent on solvent :. Mole fraction of the solute = 0.2
T hus, freezing points [ T(solvent) - ti.T1 )are different. n
79. ti.T1 =ix K1 x W(kg)
T hus, (d) is false.
⇒
0

6 = 2 X 1.86 X !!_ ⇒
Ps = !!__ 760- Ps = 18/ 180 6
70. P - 0.1
11 = - -- = 1.62
Ps N Ps 178.2/18 9.9 1 2 X 1.86
I 80. Given, mass of solvent (w) = 100 g
760 - Ps = - Ps ⇒ Ps = 752.4 Torr
99
Depression in freezing point (t-.T1 ) = 0.84° C
71. Aqueous solution of any substance (non-volatile) freezes below K1 =7.0
0°C because the vapour pressure of the solution becomes lower
mass of solute (w) = _
than that of pure solvent. 0 072
molecular mass of solute (M)
mxt-.T x W
72. We know that, w(massofsolute)= - -~ 1 - - t>.T = 1000 x K1 ( ~)
lO00x K1
f 11xw M
m = molecular weight of urea (60)
where, 11 = nu mber of atoms of s
ti.T1 = 0.186°C
_ = 1000 X 7.0 X 0.072 ⇒ n =
K1 = 1.86°, W = 500g 0 84 6
nxl00
60x 0. 186x 500
3g
I000x 1.86 S is in S 6 form in solution.
388 I Chapterwise & Topicwise Engineering Entrances Solved Papers

81. Boiling point and freezing point depend on Kb (molal elevation 88. Given, p 0 = 19 .8 mm
constant) and K1 (molal depression constant) of the solvent. 178.2
= 0.1, n8 = - - = 9 .9
n,1
Thus, equimolar solution (of the non-electrolyte) will have same 18
boiling point and also same freezing point. According to Raoult's law
11 ~ = K1 X molality p 0 -p, n,.
19.8-p 0.1
11Tb = Kb x molality - - - =- - - ⇒--- s =- - -
p0 nA+n8 19.8 9.9 + 0.I
Note In this question nature of solute has not been mentioned.
or 198- 10p= l 9.8x0.1 ⇒ 10p=l98-1.98
Hence, we have assumed that solute is non-electrolyte.
10 p = 196.02 ⇒ p = 19.602
82. Molality of cane sugar solution ~=Im 89. According to Raoult's law, the relative lowering of vapour
342 X I
pressure of a dilute solution is equal to the mole fraction of the
We know that, 11T1 = K1 •m= 1.86 x I = 1.86° solute present in the solution, i.e.
11T1 =TJ°-T1 po - P, = _ n_. -
T1 = T/ -11T1 ⇒ 0° c-(l. 86° ) p0 n+N
T1 = - l.86°C 90. Elevation in boiling point is colligative property and depends
Hence, freezing point of solution is -L86° C upon number of ions or molecules or particles.
83. The phenomenon in which, when two solutions of different CaSO4 ~ Ca 2+ + S◊~ - :.2 ions
concentration (one may be solvent) are kept separated by BaCl 2 ~ Ba + + 2Cl- 2
:.3 ions
semipermeable membrane, the solvent molecules start flowing
from dilute solution to concentrate solution. T his is called NaCl ~ Na+ + c 1- :.2 ions
osmosis. Osmosis is a slow process and keeps on happening until Urea ~ no dissociation:. I molecule
the concentration of both solutions become equal.
·: BaCl 2 furnishes maximum ions.
84. 1t =CRT
:. BaCl2 will have maximum boiling point.
Here, C =0.2M
Hence, maximum boiling point is observed when X is dissolved
R = 0.082 atm mo1- 1 K- 1 in BaCl2 •
T = 27 + 273 = 300 K 91. Osmotic pressure°" number of particles
1t = 0.2x 0.082 x 300 :. Solution with least number of particles will have minimum
= 4.92atrn. osmotic pressure.
85. According to Raoult's law (i) NaCl ~ Na+ + Cl- (2 ions)
0
p - Ps = _1_ 1 _ = 0.05 :. Concentration of particles in
p0 n+ N 2.5+ 0.05 NaCl = 2 x 2M = 4M
0.05 I (ii) Glucose does not dissociate
Molecular= - - = -
2.55 51 :. Concentration of particles = Ix 1 M = 1 M
(iii) Urea does not dissociate
Weight of solute=~ X M X _ P_ :. Concentration of particles 1 x 2 M = 2 M
w p-p,
:. Glucose solution will have minimum osmotic pressure.
M = !O x 18 x 51= 102g 92. Osmotic pressure is a colligative property. More the number of
90
particles (or ions) in solution, more will be osmotic pressure.
86. Given, R = 8.3 14 J K- 1 mol-1
NaCl solution
T1 = 273 + 16.6= 289.6K
Given, mass of NaCl = 7 g, V = I L
L1 = 180.75 Jg-1 K1 =?
Concentration = _ _mass
____
R·T} 8.314x (289.6)2 molecular mass
K1 - - - ~ -
-IOOOxL1 IO00x 180.75 7
=- = 0. 119M
⇒ K 1 =3.86kgmo1- 1 58.5
NaCl dissociates as follows
87. 2010
1 .
acetic ac1'd soIution
. =-2 x- - M acetic
1000 . ac1'd NaCl ~ Na++ Cl- (2 ions)
60 X 100
= 0.33 M acetic acid :. Concentration of ions in solution = 2 x 0. 11 9 M = 0.238 M
As the solution of compound X is isotonic to acetic acid solution, MgCl 2 solution
the molarity of solution of X will also be equal to 0.33 M. This is Given, mass ofMgCl 2 = 7 g, V = 1 L
5% solution. Hence, . mass 7
. 5x l000 Concentration= - - - - - = - = 0.0747
Molecular weight of X = - - - - = 150 molecular mass 95
0.33xl00
 Solutions I 389
MgC1 2 dissociates as follows 4. AxBy ~ xA y+ + y Bx-
MgCl 2 ~ Mg2+ + 2CI- (3 ions) (1 -Cl) X(l yCl

: .Concentration of ions in solution= 3 x 0.074 M = 0.222 M After dissociation x

(iii) ·: Number of particles in solution B(NaCl)are more than in i = fl (AxBy) + 11 (Ay+) + II cex-)
solution A.
: . Osmotic pressure of solution B(NaCI) will be more than =I-a+ xa +ya = I + a (x + y- I)
solution A. i- 1
a= - - - -
~T+ y- I)
Topic 4 Abnormal Molar Masses 5. Na 2SO4 ~ 2Na+ + SO~-(van'tHofffactorforNa 2SO 4 =3)
1. MX2 ~ M 2+ + 2x- L'1T =ixK xm
1 1
Van 't Hoff factor for any salt can be calculated using equation
= 3 X l.86X 0.0 1
r
r:m 0.01 1
= - - = 0.0lj
i = I + 0.(11 - I) 1
where, 11 = number of constituent ions
i(MX2 ) = l + o.(3-1) = I +2a = 0.0558 K

(L'iTJ )observed = i = I + 2 a
6. K2S0 4 ~ 2K+ + so~-
(L'iTJ ) ,heoretical It gives 3 ions, hence, the van 't Hoff factor= 3
Given, oc=0.5 7. (a) van't Hoff equation is
i = I + 2 x 0.5 or i =2 nV = inRT
(b) For depression in freezing point,
2. nA ~ An
(I -Cl) (l/ n L'1T1 =ixK1 xm
(c) For elevation in boiling point,
i = l-a + ~
n L'iTb = i X Kb X m

3. Sugar solution is non-polar while all the given option are polar. (d) For lowering of vapour pressure,
F inding the van't factor (i) for all solution.
Relation between molality and freezing point is:
P:tvent
O
-

Psotvent
Psotution i (-I+-I )
N 11
depression in freezing point (L'i T1 ) oc molality.
For sugar solution, (L'i T1 )suga, oe msulll'r
8. van't Hoff factor greater than I means observed value is greater
than calculated value which is so when the solute dissociates.
For ionic solution L'1T1 = K f x ix m
Since, both the solution have same freezing point therefore 9. As the colligative properties depend only upon the number of
particles of solute, so if the non-volatile solute dissociates or
(L'iTJ \u'§Jr = (L'iTJ )ionic associates in the solution, the value of colligative properties
msugar = im deviates, i.e. abnormal colligative properties are obtained.
⇒
i = msugar 10. Ca(NO 3 ) 2 ~ Ca 2+ + 2NO3
m
It fornishes 3 ions per fonnula unit. So, its van'tHofffactor is 3.
Given, msugar =2, m = I
11. Benzoic acid in benzene exists as a dimer. So, number of
⇒ i = 3_ =2 molecules decreases and hence, osmotic pressure decreases.
I
12. Actual molecular weight of naphthoic acid (C11H 8 O 2 ) = 172
Now, check the va lue of i for all given compound
2 Molecular mass (calculated)
CaCl 2 ~ Ca + + 2CI- (completely ionised)
I I
2
i =3 I 000 X Kf X w = I 000 X 1.72 X 20 =
344
W X L'11! 50 X 2
CH3 COOH ~ CH3COO- + H+ (a =degree of dissociation)
van , t H o ff f:actor(1') = -actual molecular weight
~ - = -172 = 0 . 5
1-(l (l (l
--- ----
i= l - a +a+a 1+2a-a= l +a= l +a calculated molecular weight 344
I I I
13. We have, i = I - ~
NaCl ~ Na+ + C l- (completely ionised i =2) 2
I I I
where, x = degree of association
_ • .+ 1+2a-a
C2H 50 + t1 i = ---- = I + a
o o I Here, i = 0.54 ⇒ 0.54 = I - ~
2
Since NaCl completely ionised in solution hence van't Hoff
factor ofNaCl is 2 which is equal to calculated van 't Hoff factor. or 0.54 - I = - ~
2
Hence, 1.0 molal solution ofNaCl has the same freezing point 2.0
molal sugar solution. or - 0.46 = - ~ ⇒ x = 0.92
2
390 I Chapterwise & Topicwise Engineering Entrances Solved Papers
14. van't Hoff factor (i) is given by 17. BaCl2 ---->
.,----- Ba2+
. observed value of colligative property Initial 0.01 M
!= - - - - - - - - ~ - - - - -
normal value of colligative property At equilibrium (0.01 - x) M xM 2.tM
The no1mal value of colligative property is the theoretically . (0.0 1- x) + X + 2x
1= ~ - - ~ - - -
calculated value assuming no association or dissociation. 0.01
i = 1tobs 0.0 1+ 2x
1.98
1tcal 0.01
15. CuCI2 is an electrolyte which ionise in solution as follows ⇒ X = 0.0049
X
CuCl 2 ~ Cu z+ + 2c1- Percentage ofa = - - x 100
1 mo1e O 0 0.0 1
Att = 0 = 0.0049 X I 00 = %
49
After ionisation (I - a) mole a mole 20. mole 0.0 1
Thus, number of particles after ionisation
=l-a + a+2cx=l+2cx Topic 5 Distribution Law
:. van t o 1actor (")
, H ff" number of particles after ionisation
1 = ----~-------- 1. K = concentration of X in solvent A
O
number of particles before ionisation concentration of X in solvent B
1 Concentration of Ag in 10 cm 3 Zn =x
or (i) = + 2cx (On 100% ionisation a= I)
I Concentration of Ag in I 00 cm 3 Pb= I - x
=1+2xi= 3 10
I Concentration of Ag in IO cm 3 Pb = I - x
The elevation in boiling point (when colligative property is 10
abnormal) = XX 10
300
!iTb =i X Kb X Ill (1-x)
m = molality of solution Molality ofCuCl2 solution
or = ~ = 30 = 97%
weight of CuC1 2 in gram 1-x
= molecular weight of CuC1 2 X = 0.967
weight of water (solvent) in kg Concentration of Ag in zinc= I - 0.967 = 0.033
13.44 = 3.3%o= 3%
=D±A.=0.1 m 2. Nemst's distribution law at constant temperature, when different
I quantities of a solute are a llowed to distribute between two
Thus, !iTb = 3 x 0.52x 0.1 = 0.156"" 0.16° C immiscible solvents in contact with each other then at equilibrium
the ratio of the concentration of the solute in two layers is
16. Na2SO4 ~ 2Na + + SO~-
constant for sim ilar species which may be present.
van't Hoff factor i =[I + (y- I) a] where yis the number ofions
Distribution coefficient,
from one mole solute, (in this case, y = 3), a the degree of
K _ concentration of X in solvent A (C 1)
dissociation. 0
- concentration of X in solvent B (C )
i=(l + 2cx) 2
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17
Electrochemistry
QUICK REVIEW
Electrochemistry is the study of production of electricity from
energy released during spontaneous chemical reactions and
the use of electrical energy to can-y out non-spontoneous
chemical transformations.
Electrochemical Cell
An electrochemical cell is a device in which chemical energy
of the redox reaction is converted into electrical energy. The
most common is galvanic cell or a voltaic cell. The
electrochemical cell stops working after sometime because
electrode potential of both the electrodes becomes equal.
Galvanic Cell
• In a galvanic cell, the electrons flow from anode to cathode
through the external circuit. e.g. Daniel cell
• The cell reaction occuring on Daniell cell is
Zn(s) + CuSO4 (aq) ~ Cu(s) + ZnSO 4 (aq)
If a cell uses the redox reaction
Emf of a Cell
• Emf of the cell is the difference of reduction potential of
cathode and anode.
E;,,11 =E;athode - £:,ode
• A standard hydrogen electrode has zero electrode potential
because this electrode potential is assumed to be zero.
• The arrangement of various standard half cells in order of
their decreasing values of standard reduction potentials is
called electrochemical series.
(i) Lower the value of reduction potential greater is its
reducing power.
(ii) Metals having lesser value of standard potential can
displace the other from its aqueous salt solution.
Nernst Equation
• Emf of a cell involving following reaction
aA + bB-uX + yY

_!_ H2 (g) + AgCl(s) ~ H+ (aq) + Cl- (aq) + Ag(s) Nemst equation,

2
E =£ 0
- 0.059 JV log [XY [Y]Y at 298 K
• It is represented as 1
eel cell n [A]° [B]b
Pt / H 2 (g ), HCl (solution) I IAgCl(s)IAg.
where, [ X] [Y] [A] and [B] are molar concentration of
Standard Electrode Potential
X, Y, A and B, respectively and n is the number of
• The electrode potential under the condition of unit electrons involved in the cell reaction.
concentration of all the species in the half cell is called
• For a cell reaction in equilibrium at 298 K
standard electrode potential.
• The half cell in which oxidation takes place is called anode E;,,11 = 0.0591 V log K c
n
and the other half cell in which reduction takes place is
called cathode. • Gibbs energy change t,,.G0 = - nFE0 ,
• In a galvanic cell salt bridge does not participate where, F = I faraday = 96500 C/mol (change on one mole
chemically in the cell reaction. electron).
392 I Chapterwise & Topicwise Engineering Entrances Solved Papers

(i) t-,.G 0 = - 2.303 RT log Kc, Faraday's law of electrolysis

where Kc = equlibrium constant. The quantitative aspect of electrolysis was studied
..) E
( ll cello _ 0.0591 V 1 K extensively by Michal Faraday and his laws of electrolysis
- - - - og C
n are known as Faraday's laws of electrolysis .
Conductance of Electrolytic Solutions (i) W = Zit; where Z is electrochemical equivalent and it
is quantity of electricity.
• The electrical resistance, R = ol I a where, a = area of w,1 E 1
2 (ii) - = -
cross-section of electrodes in cm , I = distance between
W2 E2
electrodes in cm and o= resistivity in ohm cm, unit of cell
constant =cm- 1 • Battery and Fuel Cells
• Specific conductance k (kappa)= l / o • A battery consists of two or more voltaic cells connected in
series. Mainly two types of cells are used in battery.
Conductance C = 1/ R
(i) Primary cells such as dry cell (Lechlanche cell),
I
K =C - = C. Cell constant, mercury cell cannot be used again (not
a rechargeable). Dry cell has a potential of 1.5 V.
where, I = 1cm and a = 1cm2 , K = C units of conductance (ii) Secondary cells such as lead storage battery,
are n - 1 or siemens, S. Units of specific conductance (K) Ni-Cd storage cell can be used again
are n - 1cm-1orScm- 1 • (rechargeable).
During charging, the electrode materials are
• EquivalentconductanceAeq = ~ = K x lOOO converted back to their original forms and the cell
Ceq Normality ' once again starts generating electricity.
where, C eq is the concentration of solution in g eq cm- 3 • Fuel cells are voltaic cells in which reactants are
continuously supplied to the electrodes.
units of equivalent conductance is n - I cm- I (g eq r I or
The common example of fuel cell is hydrogen-oxygen fuel
s cm2 (geq r' . cell. These cells convert energy from combustion of fuel
K K X 1000 . directly into electrical energy.
• Molar conductance, Am =- = . , where, Cm 1s
Cm molanty
Corrosion
the molar concentration of solution in rnolcm- 3 • Unit of It is basically an electrochemical phenomenon. It is the
molar conductivity are n- 1cm 2 rno1- 1 or Scm2 rno1- 1 . process of slow oxidation of metals into undesirable
compounds by action of moisture and other gases present in
For strong electrolytes the plot of molar conductance is ✓
C
atmosphere. The miniature cell reaction is
is linear.
2Fe(s) + 0 2 (g) + 4 H+ (aq) ~ 2Fe 2+ + 2H 2 O(/)
Kohlrausch 's law
• According to Kohlrausch's law, molar conductance at 4 Fe 2+ (aq)+ 0 2 (g)+ 4 H2 O(l)~ 2Fe 2 O 3 (s) + 8H+
infinite dilution; A ~ectrolyte = A ;;.1;00 + A :,ion . /\ :tion and Hydrated ferric oxide (Fe 2 O 3 ·x H 2 O)is rust.
A :0;011 are limiting ionic conductivities expressed in
Scm2 rno1 - 1 . Corrosion of metals can be prevented by barrier protection,
electroplating, galvanization and by connecting object
Molar conductance at given metal to a more electropositive metal (cathodic protection)
concentration (A~n) etc.
• Degree of dissociation a =- - - - - - - - ~ -
Molar conductance at • Several blocks of magnesium are fixed to bottom of ship to
infinite dilution (A;;;) prevent action of water and salt.
Note Equivalent and molar conductance of a solution • The process of zinc plating on iron sheet is galvanisation.
increases with dilution whereas specific conductance • Stainless steel does not rust because chromium forms an
of the solution decreases. Solid NaCl does not conduct oxide layer and protects iron from rusting.
electricity. Pure water does not conduct electricity
because it is almost unionised.
 Topi c 1
Conductance of Electrolytic Solutions
2014 2011
1. The equivalent conductivity of a solution containing 5. AgNO 3 (aq) was added to an aqueous KC! solution
1 1
2.54g of CuSO4 per L is 91.0co- cm2 eq- . Its gradually and the conductivity of the solution was
conductivity would be [VITEEEJ measured. The plot of conductance (A) versus the volume
(a) 2.9x 10- n - cm-
3 1 1 of AgNO3 is [IIT JEE]

(b) l.8x 10- 2 n - 1cm- 1

(c) 2.4 x 10- 4 n - 1cm- 1
(d) 3.6 x 10- 3 Q - 1cm- 1
Aw AbLJ
Volume
I
Volume
II
2. At 298K the molar conductivities at infinite dilution (A:n)
of NH 4 Cl, KOH and KCI are 152.8, 272.6 and 149.8
S cm 2 mo1- 1 respectively. The A:, of NH 4 OH is
Scm2 mo1- I
and % dissociation of0.01 M NH 4 OH with
Am = 25 .15 cm2 mo!- 1 at the same temperature are
AbJ Volume
llI
Volume
IV
(a) 275.6, 091 {b) 275.6, 9.1 [EAMCETl
(a) (I) (b) (II) (c) (III) (d) (IV)
(c) 266.6, 9.6 (d) 30, 84
6. Resistance of0.2 M solution of an electrolyte is 50 Q. The
2013 specific conductance of the solution is 1.3 sm· ' . If
3. An aqueous solution of X is added slowly to an aqueous resistance of the 0.4 M solution of the same electrolyte is
solution of Y as shown in Column I. The variation in 260 Q, its molar conductivity is [AIEEEl
conductivity of these reactions is given in Column II. Match (a) 6250Sm 2 mo1- 1
Column I with Column II and select the correct answer us ing (b) 6.25x 10- 4 Sm2 mo1- 1
the codes given below the lists. [JEE Advanced]
(c)625 x10- 4 Sm2 mo1- 1
Column I Column II (d) 62.5 Sm2 mo1- 1
A. (C2H 5 ) 3 N + CH 3COOH I. Conductivity decreases
x r and then increases. 2010
B. KI (0.1 M)+ AgN0 3 (0.01 M) 2. Conductivity decreases 7. The resistance of IN solution ofacetic acid is 250Q, when
x and then does not change measured in a cell having a cell constant of 1.15 cm- 1 • The
much
equivalent conduction (in ohm_ , cm2 equiv _,) of IN
C. CH COOH + KOH 3. Conductivity increases
3 y and then does not change acetic acid is [Guj CETl
X
much (a) 2.3 (b) 4.6
D. NaOH + HI 4. Conductivity does not (c) 9.2 (d) 18.4
X y change much and then
increases. 2009
8. The one which decreases with dilution is [ManipaIJ
Codes
A B C D A B C D (a) molar conductance
(a) 3 4 2 1 (b) 4 3 2 1 (b) conductance
(c) 2 3 4 1 (d) 1 4 3 2 (c) specific conductance
(d) equivalent conductance
2012 9. By diluting a weak electrolyte, specific conductivity (Kc)
4. The ionic conductance of Ba 2+ and Cl- are respectively and equivalent conductivity (Ac ) change as
127 and 76 n - cm2 as infinite dilution. The equivalent (a) Both increase [lndraprasth a CET, CGPET]
conductance (in n-1 cm 2 ) of BaC1 2 at infinite dilution (b) Kc increases, "-c decreases
will be [BITSAT] (c) Kc decreases, "-c increases
(a) 330 (b) 203 (c) 139.5 (d) 51 (d) Both decrease
394 I Chapterwise & Topicwise Engineering Entrances Solved Papers
10. Given the limiting molar conductivity as 18. If the molar conductance values ofCa 2+ and Cl - at infinite
"~, (HCI) = 425. 9 n - 1 cm2 mo1-
I dilution are respectivelyl 18.88 x 10-4 m 2 mho mo1- 1 and
1 2
77. 33 x 10-4 m 2 rnho mol- then that ofCaC12 is(in m
"~, (NaCl) = 126.4 n - 1 cm2 mol- 1 mho mol- 1) [VITEEE]
1 2 1
"~, (CH3 COONa) = 91 n - cm mol- (a) I 18.88 X 10- 4 (b) 154.66 X 10- 4
The molar conductivity, at infinite dilution, of acetic acid (c) 273. 54 X 10- 4 (d) 196. 21 X 10- 4
(in n- I cm 2 mol - 1) will be [DCE] 19. For strong electrolytes the plot of molar conductance
(a) 481.5 (b) 390.5 vs ✓C is [VITEEE]
(c) 299.5 (d) 516.9
(a) parabolic (b) linear
2008 (c) sinusoidal (d) circular
11. The molar conductivities ofKCl, NaCl and KNO 3 are 152, 20. The units of equivalent conductance, are [J&K CET]
1
128 and 111 S cm2 mol- 1 respectively. What is the molar (a) Qcm 2 equiv - (b) Qcm 2 equiv
conductivity ofNaNO3 ? [VITEEE] (c) n - 1cm 2 equiv - I (d) Q cm2 equiv
2 I 2 I
(a) 101 Scm mol- (b) 87 Scm mol- 21. Pure water does not conduct electricity because it is
(c) - 101 Scm2 mo1- 1 (d) - 391 Scm2 mo1- 1 (a) basic [J&K CET]
12. Which one of the following solutions will have highest (b) almost not ionised
conductivity? [Manip al] (c) decomposed easily
(d) acidic
(a) 0.1 M CH3 COOH (b) 0.1 M NaCl
(c) 0.1 M KNO3 (d) 0.1 M HCl 22. The specific conductance (K) of an electrolyte of 0.1 N
concentration is related to equivalent conductance (A) by
13. Which of the following electrolytic solutions has the least
the following fonnula [J &K CET]
specific conductance? [KCET]
(a) A=K (b)A=lOK
(a) 0.02 N (b) 0.2 N (c) A= 100K (d) A = 10000K
(c) 2 N (d) 0.002 N
23. The limiting molar conductivities A O for NaCl, KBr and
3
14. The resistance of N solution is found to be 2. 5 x 10 n . KCl are 126, 152 and l 50 S cm2 mol- 1 respectively. The
10
A O for NaBr is [Jamia Millia Islamia]
The equivalent conductance ofthe solution is (cell constant
1
= 1.25 cm- ) [Guj CET] (a) 128 Scm2 mo1- 1 (b) 176 Scm2 mo1- 1
(c) 278 S cm 2 mo1- 1 (d) 302 S cm 2 mo1- 1
(a) 2.5 n - I cm 2 equiv - I {b) 5.on- 1 cm 2 equiv - I
(c) 2.5 n - I cm- 2 equiv - 1 {d) 5.on- 1 cm- 2 equiv - 1 24. Molar conductance of electrolytic solution A,,, is [DCE]

15. The value of A:'c. for NH4 Cl, NaOH and NaCl are (a)°"/ (b)oc(l/ A)
(c) oc (1/C) (d) °" (✓
C)
respectively, 149.74, 248.1 and 126.4 n - 1cm2 equiv - 1 •
The value of A;q ofNH 4 OH is [BCECE]
2006
(a) 371.44 25. The molar conductivities A ~aOAc and A ~Cl at infinite
(b) 271.44 dilution in water at 25°C are 91.0 and 426.2 S cm 2 /mol
(c) 71.44 respectively. To calculate A~OAc> the additional value
(d) Cannot be predicted from given data
required is [AIEEE]
16. Which of the following does not conduct electricity?
(a) A oH20 (b) A~c1
(a) Fused NaCl [Jamia Millia Islamia]
(b) Solid NaCl
(c) Brine solution 26. Resistance ofa conductivity cell filled with a solution ofan
(d) Copper electrolyte of concentration 0.1 M is 100 Q. The
2007 conductivity of this solution is 1.29 Sm- 1 • Resistance of
the same cell when filled with 0.2 M of the same solution is
17. The specific conductivity of0.l N KCI solution is 0.0129 520 Q . The molar conductivity of 0.02 M solution of the
n - 1cm- 1 • The resistance of the solution in the cell is 100 electrolyte will be [AIEEE]
Q . The cell constant of the cell will be [BITSAT] (a) 124 x 10-4 S m mol- (b) 1240 x 10- S m 2 mo1-1
2 1 4

(a) 1.10 (b) 1.29 (c) 0.56 (d) 2.80 (c)l.24x10-4 Sm2 mo1- 1 (d)12.4x10-4Sm 2 mor 1

27. Which one of the following has the highest molar
conductivity ? [Ke rala CEE]
(a) Diaminedichloroplatinum (II)
(b) Tetraaminedichlorocobalt (III) chloride
(c) Potassium hexacyanoferrate (II)
(d) Hexaaquocbrornium (III) bromide
(e) Pentacarbonyl iron (0)
28. Ionisation depends upon
(a) pressure (b) volume
(c) dilution (d) None of these
29. What is the effect ofdilution on the equivalent conductance
of strong electrolyte ?
(a) Decreases on dilution (b) Remains unchanged
(c) Increases on dilution (d) None of these
Electrochemistry I 395
2005
30. The highest electrical conductivity of the following
aqueous solutions is of [AIEEEJ
(a) 0.1 M difluoroacetic acid
(b) 0.IM fluoroacetic acid
(c) 0.1 M chloroacetic acid
(d) 0.1 M acetic acid
[WBJEE]
31. Given, II a = 0. 5 cm- 1 , R = 50 ohm, N = 1.0. The
equivalent conductance of the electrolytic cell is [OJEEJ
(a) I0 !:r 1 cm 2 g equiv - 1
(b) 20.rr1 en/ g equiv - 1
[WB JEE]
(c) 300 !r 1 cm 2 g equiv - 1
(d) 100.Q- 1 cm2 g equiv - 1

Topic 2
Electrolytic Cells and Electrolysis
2014 5. Silver is monovalent and has an atomic mass of 108.
1. Suppose that gold is being plated on to another metal in an Copper is divalent and has an atomic mass of 63.6. The
electrolytic cell. The half reaction producing the Au(s) is san1e electric current is passed, for the same length of time
through a silver coulometer and a copper coulometer. If
AuC1 4 ~ Au(s)+4CI- - 3e-
27 .0 g of silver is deposited, then the coorresponding
Ifa0.30 A current run for 15 min, what mass of Au(s)will amount of copper deposited is [Ke rala CEEJ
be plated, assuming all the electrons are used in the (a) 63.60 g (b) 31.80 g
reduction of AuC1 4? The Faraday constant is 96485 c/mol (c) 15.90 g (d) 7.95 g
and molar mass of Au is 197. [Manip all (e) 4.00 g
(a) 0.184 g Au (b) 0.551 g Au 2012
(c) 1.84 g Au (d) 0.613 g Au
6. The approx.inmte time duration in hours to electroplate 30g
2. Impure copper containing Fe, Au, Ag as impurities is ofcalcium from molten calcium chloride using a cwrent of
elect:rolytically refined. A current of 140 A for 482.5s and 5 A is (At. mass of Ca = 40) [KCETJ
decreased the mass of the anode by 22.26 g and increased
(a) 80 (b) 10
the mass of cathode by 22.01 1 g percentage of iron in
(c) 16 (d) 8
irnpw·e copper is (given molar mass Fe = 55.5 g / mo~
molar mass of Cu = 63 .54 g/mol) [KCETJ 7. Read the following statement and predict the
corresponding law? 'At infinite dilution when dissociation
(a) 0.95 (b) 0.85
(c) 0.97 (d) 0 .9 is complete, each ion makes a definite contribution towards
total equivalent conductance of the electrolyte itrespective
2013 of the nature of the ion. [OJEEJ

3. The quantity of electricity required to libreate I I 2 cm 3 of (a) Ostwald's-dilution law (b) Kohlrausch's law
hydrogen at STP from acidified water is [KCET] (c) Nernst equation (d) Ohm's law
(a) 965 Coulombs (b) I Faraday 2011
(c) 0.1 Faraday (d) 96500 Coulombs
8. 9.65 C of electric current is passed through fused
4. When 9.65 C of elecricity is passed through a solution of anhydrous MgCI 2 . The magnesium metal thus obtained is
1
silver nitrate (atomic mass of Ag = l 08 g mo!- ) , the completely converted into a Grignard reagent. The number
an1ount of silver deposited is [KCETJ of moles of Grignard reagent obtained is [KCETJ
(a)16.2mg (b)21.2mg (a)5x10- 4 (b)lxl0- 4
(c) 10.8 mg (d) 6.4 mg
(c) 5 X 10- 5 ( d) I X 10-
5
396 I Chapterwise & Topicwise Engineering Entrances Solved Papers

9. What will be pH of aqueous solution of electrolyte in 19. Use of electrolysis is not done in [Guj CET]
electrolytic cell during electrolysis of CuSO4 ( aq) between (a) production of Na (b) production of water
graphite electrodes? [Guj CET] (c) pmification of metals (d) production of KOH
(a) pH = 14.0 (b) pH > 7.0
(c) pH < 7.0 (d) pH= 7.0 2008
10. Two different electrolytic cells filled with molten 20. Electrolysis of dilute aqueous NaCl solution was canied out
Cu(NO3 )i and molten Al(NO 3 h respectively are by passing 10 mA current. The time required to liberate 0.01
connected in series. When electricity is passed 2.7 g Al is mole ofH 2 gas at the cathode is (IF = 96500 C rno1- 1 )
4 4
deposited on electrode. Calculate the weight of Cu (a)9.65x10 s (b)l9.3xl0 s [IITJEE]
deposited on cathode. 4
(c) 28.95 x 10 s
4
(d) 38.6x 10 s
1
(Cu= 63.5, Al= 27.0 g mol - ) [Guj CETJ
21. When same quantity of electricity is passed through
(a) 190.5 g (b) 9.525 g
aqueous AgNO 3 and H2 SO4 solutions connected in series,
(c) 63.5 g (d) 31.75 g
5.04 x 10- 2 g ofH2 is liberated. What is the mass of silver
2010 (in grams) deposited? (Eq. wts. ofhydrogen = 1. 008, silver
11. A silver cup is plated with silver by passing 965 C of = 108) [BITSAT, AMU, EAMCET]
electricity. The amount of Ag deposited is [Manipal] (a) 54 (b) 0.54 (c) 5.4 (d) 10.8
(a) 107.89 g (b) 9.89 g (c) 1.0002 g (d) 1.08 g 22. When electric current is passed through acidified water for
12. During the electrolysis of molten NaCl solution, 230 g of 1930 s, 1120 mL of H2 gas is collected (at STP) at the
sodium metal is deposited on the cathode, then how many cathode. What is the current passed in amperes?
moles of chlorine will be obtained at anode? [MP PET] [BITSAT, AMU, EAMCET]
(a) 10.0 (b) 5.0 (c) 35.5 (d) 17.0 (a) 0.05 (b) 0.50 (c) 5.0 (d) 50
13. Give the products available on the cathode and the anode 23. The an1ount of electricity required to produce one mole of
respectively during the electrolysis of an aqueous solution copper from copper sulphate solution will be [VITEEEJ
ofMgSO 4 between inert electrodes. [Guj CET] (a) l F (b) 2.33 F (c) 2 F (d) 1.33 F
(a) H 2 (g)and O 2 (g ) (b) O 2 (g )and H 2 (g) 24. The amount ofsubstance deposited by the passage of lA of
(c) 0 2 (g) and Mg(s) (d) 0 2 (g )and SO2 (g) ctment for l s is equal to [OJEEJ
14. A solution of CuSO4 is electrolysed for 10 min with a (a) equivalent mass
current of 1.5 A. What is the mass of copper deposited at (b) molecular mass
the cathode? [Punjab CET] (c) electrochemical equivalent
(a) 2.096 g (b) 0.296 g (d) specific equivalent
(c) 3.029 g (d) 2.906 g 25. When a quantity of electricity is passed through CuSO 4
solution, 0.16 g of copper gets deposited. If the same
2009 quantity of electricity is passed through acidulated water,
15. 1n the electrolysis ofacidulated water, it is desired to obtain then the volume ofH 2 liberated at STP will be
1.12 cc of hydrogen per second under STP condition. The
(given, atomic weight of Cu = 64) [Jamia Millia Islamia]
current to be passed is [Manip al]
(a) 4.0cm3 (b) 56cm3
(a) 1.93 A (b) 9.65 A
(c) 19.3 A (d) 0.965 A (c) 604cm3 (d) 8.0cm 3
16. If'F' is Faraday and 'N' is Avogadro number, then charge
of electron can be expressed as
2007
[Indrap rastha CET, CGPET] 26. How long (in hours) must a current of 5.0 A be maintained
to electroplate 60 g of calcium from molten CaCl 2 ?
(b) F N
(a)F X N (c) - (a) 27 h (b) 8.3 h [VITEEEJ
N F
(c) 11 h (d) 16 h
17. By passing 9.65 A current for 16 min 40 s, the volume of
0 2 liberated at STP will be [lndraprasth a CET, CGPET] 27. The amount ofsilver deposited on passing 2 F of electricity
through aqueous solution of AgNO3 is [MHT CETJ
(a) 280 mL (b) 560 mL
(c) 1120 mL (d) 2240 mL (a)54g (b)l08g (c)216g (d)324g
18. Which substance is obtained in the solution on electrolysis 28. When during electrolysis of a solution of AgNO 3 , 9650C
of aqueous CuSO4 solution using graphite electrodes? of charge pass through the electroplating bath, the mass of
(a) H 2 O (b) H 2 SO4 [Guj CETJ silver deposited on the cathode will be [MP P ET]
(c) Na 2 SO4 (d) Cu(OH)i (a) 1.08 g (b) 10.8 g (c) 2 1.6 g (d) 108 g
 Electrochemistry I 397
29. Aluminium oxide may be electrolysed at I 000°C to furnish 36. A lamp draws a current of 1.0 A. Find the charge in
aluminium metal (atomic mass = 27 u; IF= 96500C). The coulomb used by the lamp in 60 s. [Guj CET]
cathode reaction is (a) 0.6 C (b) 60 C (c) 600 C (d) 0.006 C
Al3+ + 3e- ~ AI 0
37. The charge required to liberate one gram equivalent of an
To prepare 5.12 kg of aluminium metal by this method element is [BCECEl
would require [UPSEE]
(a) 96500 F (b)l F
1
(a) 5.49 x 10 C of electricity (c) l C ( d) None of these
(b) 5. 49 x 104 C of electricity 38. The laws of electrolysis were proposed by [DCEJ
7
(c) l.83x 10 Cofelectricity
(a) Kohlrausch (b) Faraday
( d) 5 .49 x 107 C of electricity (c) Haber (d) Bergius
30. A current of 12 A is passed through an electrolytic
2005
cell containing aqueous NiSO 4 solution. Both Ni and H2
gas are formed at the cathode. The c1ment efficiency is 39. In the electrolysis of water, 1 F of electrical energy would
60%. What is the mass of nickel deposited on the cathode evolve [Manipall
per hour? [WB JEE] (a) l mole ofoxygen (b) 1 g atom ofoxygen
(a)7.883g (b)3.94 1g (c)5. 91g (d)2 .645g ( c) 8 g of oxygen ( d) 22.4 L of oxygen
40. Same amount of electric current is passed through
2006 solutions of AgNO 3 and HCI. If 1.08 g ofsilver is obtained
31. The cathodic reaction of a dty cell is represented by in the first case, the amount of hydrogen liberated at STP in
2MnO 2 (s)+Zn 2+ +2e- ~ZnMn 2 O 4 (s) the second case is [MP PET]
If, there are 8 g ofMnO2 in the cathodic compartment then (a) 224 cm3 (b) 1.008 g (c) l 12cm3 (d) 22400cm3
the time for which the dty cell will continue to give a
41. When electric current is passed through an ionic hydride in
Cllffent of2 mA is [BITSAT]
molten state [Ke ral a CEEl
(a) 25.675 day (b) 51.35 day
(a) hydrogen is liberated at anode
(c) 12.8 day (d) 6.423 day
(b) hydrogen is liberated at cathode
32. In acidic medium MnO4 is converted to Mn 2+ . The ( c) no change takes place
quantity of electricity in Faraday required to reduce (d) hydride ion migrates towards cathode
2
0.5 mole ofMnO 4 to Mn + would be [UPSEE] (e) hydride ion remains in solution
42. On passing 0.5 F of electricity through molten sodium
(a) 2.5 (b) 5 (c) I (d) 0.5
chloride, sodiun1 deposited at cathode will be [AMUJ
33. During electrolysis of water the volume of 0 2 liberated is
(a) 29.25 g (b) I 1.50 g (c) 58.50 g (d) 0.00 g
2.24 dm 3 . The volume of hydrogen liberated, under same
43. What is the quantity of electricity (in Coulombs) required
conditions will be [UPSEE]
to deposit all the silver from 250 mL of I MAgNO 3
(a) 2.24 dm 3 (b) 1.12 dm3 (c) 4.48 dm3 (d) 0.56 dm3 solution ? [EAMCETl
34. What is the time (in sec) required for depositing all the (a) 2412.5 (b) 24125 (c) 4825.0 (d) 48250
silver present in 125 mL of 1 M AgNO 3 solution by
44. Which of the following is not COITect ? [EAMCETl
passing a current of 241.25 A ? (IF = 96500 C)
(a) Aqueous solution of NaCl is an electrolyte
(a) 10 (b) 50 [EAMCET]
(b) The units ofelectrochemical equivalent are g-coulomb
(c) 1000 (d) 100
(c) In the Nernst equation, n represents the number of
35. Assertion (A) A current of96.5 A is passed into aqueous electrons transfe1Ted in the electrode reaction
AgNO 3 solution for I 00 s. The weight of silver deposited (d) Standard reduction potential of hydrogen electrode is
is 10.8 g (Atomic weight of Ag = I 08) zero volt.
Reason (R) The mass of a substance deposited during the 45. Calculate the volume ofH 2 gas at NTP obtained by passing
electrolysis ofan electrolyte is inversely proportional to the
4 A through acidified H 2 0 for 30 min is [DCEJ
quantity of electricity passing through the electrolyte.
[EAMCET] (a) 0.0836 L (b) 0 .0432 L
(c) 0.1 672 L (d) 0 .836 L
(a) Both A and R are cotTect and R is the correct
explanation of A 46. The charge required for reduction of lmole ofCr2 o~- ions
3
(b) Both A and R are correct but R is not the correct to Cr + is [DCE]
explanation of A (a) 96500 C (b) 2 x 96500 C
( c) A is cotTect but R is incorrect (c) 3 x 96500 C (d) 6 x 96500 C
( d) A is incotTect but Reason is cotTect
 Topi c 3
Electrochemical Cells, Galvanic Cells, Nernst Equation
2014
1. In a galvanic cell, the salt bridge [JEE Advanced] Based on the data given above strongest oxidising agent
(a) does not participate chemically in the cell reaction will be [JEE Mains]
(b) stops the diffusion of ions from one electrode to (a)Cl (b)Cr 3 +
another (c) Mn 2 + (d) MnO 4
(c) is necessary for the occurrence of the cell reaction
(d) ensure moving of the two electrolyte solution 8. The standard reduction potential data at 25° C is given
below
2. Given below are the half-cell reactions
£ 0 (Fe 3 + /Fe 2 +) = 0.77 V
Mn 2 + + 2e- ~ Mn; £ 0 = - l.18eV 2
£ 0 (Fe + / Fe) = - 0.44 V
2(Mn 3 + + e- ~Mn 2 + )£0 = +1.5leV 2
£ 0 (Cu + / Cu) = + 0.34 V
The£ 0 for 3Mn 2 + ~Mn+ 2Mn 3 + will be
£ 0 (Cu + / Cu) = + 0.52 V
(a) - 2.69 V, the reaction will not occur [JEE Mains]
£ 0 (0 2 (g) + 4H+ + 4e- ~ 2H2O)
(b) - 2.69 V, the reaction will occur
(c) - 0.33 V, the reaction will not occur
= 1.23 V
(d) - 0.33 V, the reaction will occur E (O 2 (g)+ 2H 2O + 4e- ~ 4OH- ) = + 0.40V
0

3. What is the cell potential (standard emf, £ 0 ) for the £ (Cr 3+ / Cr)=-0.74 V;
0

reaction below? £ 0 (Cr 2+ / Cr)=- 0.91 V

0
[£ 0 = 0.44 Vand £ = + 0.4V]
(Fe2+ I (aq) Fe) (02 (g)/ H ~/OW) Match £ 0 of the redox pair in List I with the values given in
2Fe (s) + 0 2 (g) + 2H2O (/) ~ 2Fe2 + (aq) List II and select the corret answer using the codes given
below the lists. [JEE Advance d]
+ 40H- (aq) [Manipal]
(a) E:11 = - 0.48 V (b) £: 11 = - 0.04 V
Column I Column II

(c) E:11 = + 0.84 V (d) £: 11 = + 1.28 V

P. E 0 (Fe3 + / Fe) I. - 0.36 V

4. ForCr2 o;- + 14H+ + 6e- ~ 2Cr3+ + 7H 2 O ;

Q. E (4Hp ~ 4H+ + 4OW)
0
2. - 0.4 V

£ 0 = 1.33 V At [Cr2o;-] = 4.5 millimole, [Cr 3+] = 15 R. E 0 (Cu 2 + + Cu ---t 2Cu+) 3. - 0.04 V
millimole Eis 1.067 V. The pH of the solution is nearly is s. E 0 (Cr 3 +, Cr 2 +) 4. - 0.83 V
equal to [KCET]
w2 ~3 ~5 004 Codes
5. Zinc is used to reduce iron because [UPSEEJ P Q R S
(a) 4 I 2 3
(a) E red of Zn <E red of Fe (b) Eoxi of Zn < £oxide of Fe
(b) 2 3 4 I
(c) Eoxi of Zn= £oxide of Fe (d) Zinc is cheaper than iron
(c) I 2 3 4
6. Given the reduction potential of Na+ , Mg 2 + , Al 3 +and (d) 3 4 I 2
+ 0 . 0

Ag asENa+/Na =-2.71V;EMg 2 +/Mg =-2.37V; 9. Zn(s) IZn 2 + (aq)IICu 2 + (aq)Cu(s)is [KCET]

(Anode) (Cathode)
E:13+ / Al =- 1.66 V (a) Weston cell (b) Daniell cell
0

E Ag +/ Ag = 0.08 V The least stable oxide is (c) Calomel cell (d) Faraday cell
1O. Aluminium displaces hydrogen from acids but copper does
not. A galvanic cell prepared by combining Cu/ Cu 2 + and
2013 Al/ Al 3 + has an emf of 2.0 V at 298 K. If the potential of
7. Given £~3+ ,er = - 0.74 V copper electrode is +0.34 V, that of aluminimum electrode
0 is [KCET]
E
MnO;j"/ Mn 2 +
= 15 1V·E = l.33V;
. ' Cr~~ - /Cr3+ (a) - 2.3 V (b) + 2.34 V
0

£ Cl/Cl- =1 . 36V·' (c) - 1.66 V (d) + 1.66 V

 Electrochemistry I 399
11. The standard emf. ofa cell Zn/Zn 2 + 11Fe 2 +/Fe, if 18. Which one of the following has a potential more than
2
electrode potentials for (Zn / Zn + ) and (Fe + / Fe) are 2 zero? CKCET]

0.763 V and - 0.44 Vrespectively is [OJEEJ

1
(a) Pt,- H 2 (latm)I HCI (2M)
(a) + 0.323 V (b) - 1.203 V 2
1
(c) + 1.203 V (d) - 0 .323 V (b) Pt,- H 2 (latm)I HCI (0.lM)
2
12. The standard emf for the cell reaction 1
(c) Pt,- H 2 (latm)I HCI (0.5M)
2Cu + (aq) ~ Cu(s) + Cu 2 + (aq) 2
1
is + 0 .36 V at 298 K. The equilibrium constant of the (d) Pt,- H 2 (latm)I HCI (IM)
reaction is [OJEEJ 2
(a) 5 x 106 (b) 1.4 X 1012 19. Given that; Zn 2+ / Zn = - 0.762 V,
(c) 7 .4 X 10
12
(d) 1.2 x 106 Mg 2 +/ Mg = - 2.37V Then,Zn + MgC1 2 ~ ?
(a) ZnCl 2 + Mg (b) ZnCl 2 + MgCl 2 [OJEE]
2012 (c) Zn + Mg (d) No reaction
13. The electrochemical cell shown below is a concentration 20. 1 M solution each of Cu(NO 3 ) 2 , AgNO3 , Hg 2 (NO 3 h
2
cell. M / M + (saturated solution of a sparingly soluble salt, and Mg(NO3 h is electrolysed using Pt-electrodes. The
MX 2 ) l 1M 2+ (0.00001 mol ctm·3 / M) . The emfof the cell values of standard electrode potentials in volts are
depends on the difference in concentration of M 2+ ions at 2
Ag + I Ag= + 0.80 V, Cu +/Cu= + 0.34 V,
the two electrodes. The emfof the cell at298 is 0.059 V.
1
The value of /1.G (kJ mo!- ) for the given cell is (take Hg ;+ / Hg = + 0.79VMg 2 + / Mg = - 2.37V
1
lF = 96500C mo!- ) [HT JEE] The sequence ofdeposition ofmetals on the cathode will be
(a) - 5.7 (b) 5.7 (c) 11.4 (d) - 11.4 (a) Mg, Ag, Cu (b) Mg, Cu, Ag [AMU]
(c) Ag, Hg, Cu (d) Cu, Hg, Ag
14. The standard reduction potential for Zn + / Zn, Ni 2 + /Ni
2

2
and Fe + /Fe are - 0.76, - 0.23 and - 0.44 Vrespectively. 2011
2 2
The reaction X + Y + ➔ X + + Y will be spontaneous 21. Consider the following cell reaction
when [AIEEEJ 2Fe(s) + 0 2 (g)+ 4H+ (aq) ~
(a) X = Ni, Y = Fe (b) X = Ni, Y = Zn 2Fe 2 + (aq) + 2H 2 O(l), £ 0 = 1.67 V
(c)X = Fe,Y = Zn (d)X =Zn,Y = Ni
At [Fe 2+] = 10- 3 M, p02 = 0. 1atrn and pH = 3, the cell
15. In which of the following case, increase in concentration of
ion cause increase in E cell ? [Manipal] potential at 25°C is [HT JEE]
(a) Pt(H2 )I H + (aq) (a) 1.47 V (b) 1.77 V (c) 1.87 V (d) 1.57 V
(b) Ptl Quinhydrone IH+ (aq) 22. The reduction potential of hydrogen half-cell will negative
if [AIEEE]
(c) AglAg + (aq)
(d) Ag, AgCIICl-(aq) (a) p(H2 ) = 1atrn and [H+] = 2.0 M
(b) p(H2 ) = latm and [H+ ] = I.OM
16. Out of Cu, Ag Fe and Zn, the metal which can displace all
others from their salt solution is [Manipal] (c) p(H2 ) = 2atm and [H+ ] = 1.0 M
(a) Zn (b) Cu {c) Ag (d) Fe (d) p(H 2 ) = 2atrn and [H+ ] = 2 .0 M
17. The equilibrium constant of the reaction 23. £ 1 , E 2 and £ 3 are the emfs of the following three galvanic
A(s)+2B+ (aq) ~ A + (aq) + 2B(s);2 cells respectively
I. Zn(s) I Zn 2 + (0.1 M)I ICui+ (IM) ICu(s)
£ 0 cell = 0 .0295 Vis 2 2
II. Zn(s) IZn +(1M)II Cu + ( l M) ICu(s)
[ 2 .3~ RT = 0.059] 2 2
III. Zn(s) IZn +(1M)II Cu + (0.l M)ICu(s)
[KCET]
(a)2x10
2
(b) 3 x 10
2 Which one of the following is true? [KCET]

(c) 2x 105 (d) 10 (a) £ 2 > E 1 > £ 3 (b) £ 1 > E 2 > E 3

(c)E3 >E1 >£2 (d)E 3 >E2 >E1
400 I Chapterwise & Topicwise Engineering Entrances Solved Papers
24. The standard emf of a galvanic cell involving 2 moles Which of the following reaction is feasible? [MP PET]
ofelectrons in its redox reaction is 0.59 V. The equilibrium (a) II (b) I
constant for the red ox reaction ofthe cell is [KCET] (c) III (d) All of these
(a) 1020 (b) 105 (c) 10 (d) 1010 32. At 25°C temperature, the cell potential of a given
25. The standard redox potentials for the reactions electrochemical cell is 1.92 V. Find the value ofx.
Mn 2+ + 2e- ~ Mn and Mn 3+ + e- ~ M 2 + are [Guj CET]
2 2
- 1.18 V and 1.51 V respectively. What is the redox Mg(s) I Mg + (aq)x M 11Fe + (aq) 0 .01 MI Fe (s)
potential for the reaction Mn 3+ + 3e- ~ Mn?
E 0 Mg I Mg 2+ (aq) = 2.37V;E°Fe / F;+ (aq) = 0.45V
(a) 0.33 V (b) 1.69 V (c) - 0.28 V [Kerala CEE]
(d) - 0.85 V (e) 0.85 V (a)x = O. OlM (b)x<0 .01
M
26. The standard reduction potential £ 0 for half reactions are
(c) x > O.oI M (d) x cannot be predicted
Zn= Zn 2+ + Ze, £ 0 = + 0 .76 V 33. The emfofthe cell Ni1Ni 2 + ( 1.0 M) 11Au 3 + (1.0 M)I Au
Fe = Fe 2 + + Ze,E 0 = + 0 .41 V 2
is [£0 (Ni +/Ni) = - 0.25 Vand
The emf of the cell reaction
£ ( Au +/ Au ) = + 1.5 ~
0 3
[JCECEJ
2 2
Fe + + Zn= Zn + + Fe is [WB JEE] (a) 2.00 V (b) 1.25 V
(a) - 0.35 V (b) + 0.35 V (c) + 1.17 V (d) - 1.17 V (c) - 1.25 V (d) 1.75 V
27. Which of the following reactions is correct for a given 34. If the standard electrode potential ofCu 2+ / Cu electrode is
electrochemical cell at 25°C? 0.34 V, what is the electrode potential at O.oI M
2
Pt 1Br2 (g) I Br- (g ) IICl- (aq) I Cl 2 (g) I Pt [Guj CET] concentration of Cu +? (T = 298 K) [Punjab CETJ
(a) 2Br (aq)+ C l 2 (g) ~ 2Cl- (aq) + Br2 (g) (a)0. 399V (b)0.281 V
(c)0.222V (d)0.176V
(b) Br2 (g)+ 2Cl- (aq) ~ 2Br- (aq) + Cl 2 (g)
(c) Br2 (g)+ Cl 2 (g) ~ 2Br- (aq) + 2Cl- (aq) 2009
(d) 2Br- (aq) + 2Cl- (aq) ~ Br2 (g) + Cl 2 (g) 0

35. EFe J+ / Fe
0

= - 0.336 V, EFe2+ / Fe = - 0.439 V. The value of

2010 standard electrode potential for the charge,
Fe 3+(aq)+e- ~ Fe 2+(aq)willbe [AIEEE]
28. The standard emf of a cell involving one electron change is
(a) - 0 .072 V (b) 0 .385 V
found to be 0.591 Vat 25°C. The equilibrium constant of
1 (c) 0.770 V (d) - 0.270 V
the reaction is (F = 96500 C mol - ) [Manipal]
1 5 10 30
36. Daniel cell, anode and cathode are, respectively
(a) I.Ox 10 (b) I.Ox 10 (c) I.Ox 10 (d) I.Ox 10 [Indrapras tha CET, CG PET]
29. £ 0 values ofMg 2 + / Mg is - 2.37 V of Zn 2+ / Zn is - 0.76 2
(a) Zn I Zn + and Cu + I Cu2

V and Fe 2+ / Fe is - 0.44 V. (b) Cu I Cu 2 + and Zn 2+ I Zn

2 2
Which of the statements is correct? [Manipal] (c) Fe1Fe +and Cu +1Cu
2 2
(a) Zn will reduce Fe 2+ (b) Zn will reduce Mg 2 + (d) Cu I Cu + and Fe + I Fe
(c) Mg oxidises Fe (d) Zn oxidises Fe 37. The potential of the following cell is 0.34V at 25°C.
30. What will be the electrode potential of that hydrogen Calculate the standard reduction potential of the copper
electrode is filled with HCl solution of pH value 1.0? half-cell. [Guj CETJ
2
(a) - 59.15V (b) + 59.15 [MPPET] Pt I H 2 ( 1 atm) I H+ (1 M) II Cu + (1 M) I Cu
(c) + 59.1 5mV (d) - 59.15mV (a) - 3.4V (b) + 3.4V
31 . I. Cu+ 2HC1 ~ CuCl 2 + H2 (g) (c) - 0 .34 V (d) + 0 .34 V
0

(£ 2+ =+ 0.34 V) 38. The potential of the cell for the reaction,

Cu /Cu
M(s) + 2H+ (1M) ~ H 2 (g)(l atm) +M 2+(0. 1MJ
II. Zn+ 2HC1 ~ ZnCl 2 + H 2 (g) 2
0 is 1.500 V. The standard reductio n potential for M + I
(£ 2+ =- 0 .76 V)
Zn / Zn M (s) couple is CAMUJ
1
III. Ag+ 2HC1 ~ AgCl+ - H 2 (g) (a) 0.1470 V
2 (b) 1.470V
(c) 14.70V
(d) None of the above
 Electrochemistry I 401
39. In which of the following pairs, the constants/ quantities 47. Electrode potential of hydrogen electrode is ..... volt.
are not mathematically related to each other? [DCEJ (a) 0 (b) + l Co.JEE]
(a) Gibbs free energy and standard cell potential (c) - l (d) None of these
(b) Equilibrium constant and standard cell potential
(c) Rate constant and activation energy 48. The relationship between Gibbs' free energy change (!J.G)
( d) Rate constant and standard cell potential and emf(E)ofa reversible electrochemical cell is given by
40. Small quantities ofsolutions ofcompounds TX, TY and TZ (a)!!.G = nFE (b)flG = nFI E [J&K CETJ
are put into separate test tubes containing X, Y and Z (c) !J.G = - nFE (d) !J.G = E l nF
49. Zn + ~ Zn(s); E
2
solutions. TX does not react with any of these. TY reacts 0
= - 0.76 V
with both X and Z. 1Zreacts with X. The decreasing order Cu 2+ ~ Cu(s); £ 0 = - 0.34 V
of ease of oxidation of the anions X - , y - , z- is [DCEJ
Which of the following is spontaneous? [BCECE]
(a)Y - ,r,x- (b) z- , x - ,y -
(a) Zn 2+ + C u ~ Zn + Cu 2 +
(c)Y- ,x-, z- (d) x - ,z- ,Y-
(b) Cu 2 + + Zn ~ Cu + Zn 2+
2008 ( c) Zn 2+ + Cu 2+ ~ Zn + Cu
0
41. Given, £ c,l+ ic,+l = 0.72 V, E° Fe2+ / Fe+2 = 0.42 V (d) None of the above
The potential for the cell 50. The cell reaction of the galvanic cell
2 2
Cr/ Cr 3+ (0.1 M) IFe 2+(0.0l M) IFe is [AIEEEJ Cu(s)ICu + (aq)II Hg + (aq)IHg(/) is [DCEJ
(a) 0.26 V (b) 0.399 V (a) Hg + Cu 2 + ~ Hg 2 + + Cu
(c)- 0.339V (d)- 0.26V
(b) Hg + Cu 2+ ~ Cu + + Hg +
42. Dipping iron article into a strongly alkaline solution of
(c) Cu + Hg ~ CuHg
sodium phosphate [VITEEEJ
( d) Cu + Hg 2+ ~ Cu 2 + + Hg
(a) does not affect the article
(b) forms Fe 2 O 3 ·xH2 Oon the sw·face 51. Which one of the following condition will increase the
( c) forms iron phosphate film voltage of the cell represented by the equation?
( d) forms fetTic hydroxide 2
Cu(s)+ 2Ag + (aq)~ Cu + (aq) + 2Ag(s)
43. Cu + ( aq) is unstable in solution and undergoes
[Jamia Millia Islamia]
simultaneous oxidation and reduction, according to the
(a) Increase in the dimension of Cu electrode
reaction 2Cu + (aq) ~ Cu 2 + (aq) + Cu(s)
(b) Increase in the din1ension of Ag electrode
choose correct £ 0 for the above reaction, if 2
( c) Increase in the concentration of Cu + ions
£ eu 2+ !Cu = 0. 34 Vand£ eu 2+ /Cu+ = 0. 15 V [MHTCETJ
0 0

( d) Increase in the concentration of Ag + ions

(a)-0.38V (b)+0.49V (c)+0.38V (d)-0.19V
44. The standard reduction potentials at 298 K for the 2007
following half-cell reactions are given 52. The cell, Zn IZn 2+ (l M)I ICu 2+ (1 M)ICu
2
Zn +(aq) + 2e- ~ Zn(s);-0. 762V
(£0 cell = 1.10 V), was allowed to be completely
Cr 3+ (aq)+ 3e- ~ Cr(s);- 0 . 74 V 2
dischaued at 298 K. The relative concentration of Zn + to
2H+(aq)+2e- ~ H 2 (g ); +0.00V
Cu 2+ [Zn 2+ ]) is [AIEEEJ
Fe 3+ (aq)+ e- ~ Fe 2+ (aq); + 0. 77V
[Cu 2+ ]
Which one of the following is the strongest reducing
(a) antilog (24.08) (b) antilog (37.3)
agent? [MHT CETJ (c) l 037 3 4
(d) 9.65x 10
(a)Zn(s) (b)Cr(s) (c)H2 (s) (d)Fe 2+(aq)
53. Given standard electrode potentials
45. The cell reaction is spontaneous, when [MHTCETJ Fe 2+ + 2e- ~ Fe £ 0 = - 0.440 V
(a) £ 0,ed is negative (b) £ 0,ed is positive Fe 3+ + 3e- ~ Fe £ 0 =- 0.036 V
0
(c) !J.G is negative (d) !J.G0 is positive the standard electrode potential (£ 0 ) for
46. Hydrogen gas is not liberated when the following metal is Fe 3+ + e- ~ Fe 2+ is [BITSAT]
added to dil. HCI [KCETJ
(a)+ 0.772 V (b) - 0.772 V
(a) Ag (b) Zn (c) Mg (d) Sn (c)+0.417V (d) - 0.414 V
402 I Chapterwise & Topicwise Engineering Entrances Solved Papers
54. The standard emf of a galvanic cell involving cell reaction (a) increases cell emf
with n = 2 is found to be 0.295 V at 25C0 • The equilibrium (b) increases the current flow
constant ofthe reaction would be ( c) decreases the cell emf
(Given, F = 96500Cmol- 1, R = 8. 3 14 JK- 1 mo!- 1 ) ( d) alter the pH of the solution
11 12 62. For the redox reaction,
(a) 2.0 X 10 (b) 4.0 X 10 [Manipal]
2 10 Zn(s) + Cu 2 + (0.1 M)-➔ Zn z+ (1 M) + Cu(s)
(c) l.Ox 10 (d) I.Ox 10
taking place in a cell, E 0 ce1l is 1.10 V. E 0 ce1l for the cell
55. The standard E ~ values of A , B and C are
+ 0.68 V, - 2.54 V, - 0.50 V respectively. The order of willbe ( 2.303 ~ = 0.0591) [UPSEE, MPPET]
their reducing power is [MIIT CETJ
(a) 2.14 V (b) 1.80 V (c) 1.07 V (d) 0.82 V
(a)A>B>C (b)A>C>B
(c)C> B> A (d)B>C> A 63. Sn + + 2e- -➔
4
Sn 2 +, £ = 0. 13 V
0

56. EMF of hydrogen electrode in te1m of pH is (at 1 atrn Br2 + 2e- -➔ 2Br- ,E0 = 1 . 08V
pressure) [MHT CETJ Calculate K eq for the cell reaction for the cell formed by
RT RT l two electrodes. [AMU]
(a)EH = - xpH (b)EH 2 = - ·-
2 F F pH (a) 104 1 (b) 1032 (c) 10- 32 (d) 10-42
2.303RT
(c)EH 2 = F ·pH (d)EH 2 = 0.059lpH 64. Calculate the emf of the cell
Cu(s) ICu z+ (aq) I IAg + (aq ) IAg(s)
57. Which one of the following nitrates will leave behind a 0
metal on strong heating? [MP PET] Given, E';;., 2+ !Cu = + 0.34 V, E Ag+ /Ag = 0 .80V
(a) Ferric nitrate (b) Copper nitrate (a)+ 0.46 V (b) + 1.14 V [EAMCETJ
(c) Manganese nitrate (d) Silver nitrate (c)+0.57V (d)-0.46V
65. The standard electrode potential of hydrogen electrode at 1
58. An alloy of Pb-Ag weighing 1.08 g was dissolved in
dilute HN03 and the volume made to 100 mL. A silver M concentration and hydrogen gas at 1 atrn pressure is
electrode was dipped in the solution and the emf of the (a) l V (b) 6 V [J&K CETJ
cell set-up Pt(s ), H 2 (g) IH+ (l M) l IAg + (aq) !Ag(s) (c) 8 V (d) 0 V
was 0.62 V. If E~11 = 0 . 80V, what is the percentage of Ag 66. 2Fe 3+ + 31- ~ 2Fe 2 + + 13
in the alloy? (At 25°C, RTIF = 0. 06) [Ke rala CEEJ The standard reduction potentials in acidic conditions are
(a) 25 (b) 2.50 (c) 10 0 .77 and 0.54V respectively for Fe 3+/ Fe 2 + and 13/ r-
(d) 1 (e) 50 couples. The equilibrium constant for the reaction is
59. The standard oxidation potentials of Zn, Cu, Ag and Ni [Jamia Millia Islamia]
electrodes are + 0 .76, - 0 . 34 , - 0. 80 and + 0 . 25 V (a) 6.26 X l 0- 7
(b) 5.33 X 10-
4
respectively. Which of the following reaction will provide 7
(c)6.26x l 0 (d)5.33xl04
maximun1 voltage? [Ke rala CEE]
2
(a) Cu + 2 Ag+ ( aq) ➔ Cu + (aq) + 2 Ag 67. Consider the following E 0 values
(b) Zn + 2 Ag+ (aq) ➔ Zn 2 + ( aq) + 2 Ag 0
E°Fe3+ I Fe2+ = + 0 .77 V, E s n-?+/Sn = - 0 .14 V
(c)H 2 + Ni + (aq) ➔ 2H+(aq)+Ni
2
Under standard conditions the potential for the reaction
( d) Zn + Cu 2+ (aq) ➔ Zn 2 + ( aq) + Cu Sn(s) + 2Fe 3+ (aq) ➔ 2Fe 2 + (aq) + Sn 2 + (aq) is
(e) Zn + 2H+ (aq) ➔ Zn 2 + (aq)+ H2 [Jamia Millia lslamia]
60. The cell reaction of a cell is (a) 1.68 V (b) 1.40 V (c) 0.91 V (d) 0.63 V
2
Mg(s)+Cu +(aq)-➔ Cu(s)+Mg +(aq). If the 2
2006
standard reduction potentials of Mg and Cu are - 2 . 37 and
68. Given the data at 25°C,
+ 0 . 34 V respectively. The emf of the cell is [WB JEE]
Ag + I- ➔ AgI + e- ;E 0
=0. 152V
(a) 2.03 V (b) - 2 .03 V
(c) + 2.71 V (d) - 2 .71 V Ag ➔ Ag+ + e- ;E = - 0 . 800 V
0

61. In the electrochemical reaction, What is the value of log K sp for AgI?

2Fe 3+ + Zn -➔ Zn 2 + + 2Fe 2 + ( 2.303 ~ = 0 .059 V) [AIEEE]

2
increasing the concentration ofFe + [WB JEE]
(a) - 8. 12 (b)+8.612 (c) - 37.83 (d) -1 6.13
 Electrochemistry I 403
69. If the H+ concentration is decreased from 1 M to 10- 4 Mat 77. The standard reduction potentials of Zn 2 + IZn, Cu 2+ ICu
2
25°C for the couple MnO4/ Mn +, then the oxidising and Ag + I Ag are respectively - 0. 76, 0. 34 and 0. 8 V. The
power of the MnO 4/ Mn 2+ couple decreases by following cells were constructed
(a)-0.18V (b)0.18V [BITSATJ
I. Zn I Zn 2+ I1cu2+ I Cu
2
(c) 0.38 V (d) - 0.38 V TI. Zn I Zn + II Ag+ I Ag
2
70. The reduction electrode potential, E of 0.1 M solution of ITT. Cu I Cu + II Ag+ I Ag
M+ ions (ERP = - 2.36 V) is [MHT CET] What is the correct order of E~en of these cell ?
(a) - 4.82 V (b) - 2.41 V (a) II> III> I (b) II> I> III [EAMCETJ
(c) + 2.41 V (d) None of these (c) I> II> III (d) III> I > II
71. Reduction potentials of A, B, C and Dare 0.8 V, 0.79 V, 78. Which will reduce zinc oxide to zinc? [BCECEJ
0.34 Vand - 2.37Vrespectively. Whichelementdisplaces (a)Mg (b) Pb
all the other three elements? [MP PET] (c) Cu (d) Fe
WB ~A ~D ooc 79. The metal that does not displace hydrogen from an acid is
72. Which of the following statements are correct concerning WD ~N [B~ ~
redox prope1ties? (c) Zn (d) Hg
I. A metal M for which £ 0 for the half reaction 80. Which of the following ions can be replaced by H+ ions
Mn+ + ne- = M, is very negative will be a good when H 2 gas is bubbled through the solutions containing
reducing agent. these ions? [Jamia Millia Islamia]
II. The oxidising power of the halogens decreases from (a) Li+ (b) Ba 2+
chlorine to iodine. (c) Cu 2+ (d) Be 2+
III. The reducing power of hydrogen halides increases
81. H 2 cannot be displaced by [Jamia Millia Islamia]
from hydrogen chloride to hydrogen iodide.
(a) Li+ (b) Sr 2+ (c) N 3+ (d) Ag+
(a) I, II and III (b) I and II [Kerala CEEJ
(c) Only I (d) II and III 82. The emfofthe cell, (EZn 2+ /Zn = - 0.76 V)
(e) Only III
Zn I Zn 2 + (lM)IICu 2+ (lM)Cu
73. Given the standard reduction potentials
Zn 2+/Zn=- 0.74 V, Cl 2 / Cl- = 1.36 V (Eeu 2+ /Cu = + 0.34 V)will be [J amia Millia Islamia]
2
H+/..!_H2 = 0V and Fe +/Fe + =0.77V3 (a)+ l.I0V (b) - 1.l0V
2 (c) + 0.42 V (d) - 0.42 V
The order of increasing strength as reducing agent is
[Ke rala CEE]
2005
83. The rusting of iron takes place as follows
(a) c1 - , Zn, H 2 , Fe 2+ (b) H2 , Zn, Fe 2 + , c1-
(c) Cl - , Fe 2+ , Zn, H2 (d) H2 , Fe 2 + , Cl- ,Zn 2H+ + 2e- + ..!.02 ~ H2 O(/);E0 = + 1.23V
2
(e) C l- , Fe 2+, H 2 , Zn
Fe 2+ + 2e- ~ Fe (s);E 0 = - 0.44 V
74. Calculate the equilibrium constant for the reaction, at 25°C
Dlculate llG0 for the net process. CIIT JEE]
Cu(s) + 2Ag+ (aq) ~ Cu 2+ (aq) + 2Ag(s) 1 1
(a) - 322kJ mol- (b) - 161kJ mol-
1
at25°C, E 0cell = 0.47V, R = 8.314 JK- F = 96500Cis (c) - 152kJmo1- 1 (d) - 76 kJmo1- 1
(a)l.8x1015 (b)8.5x10I 5 [Kerala 84. The standard reduction potential of the reaction,
CEEJ H2O + e - ~ ..!_H2 + OH at298 Kis [BITSATJ
10 15
(c) l.8x 10 (d) 85x 10 2
75. The metal used to recover copper from a solution of (a) E o = RT In K ..,
CuSO4 is [WB JEE] F
(a) Fe (b) He (c) Na (d) Ag (b) Eo =- RT In [PH )112 [Off ]
F 2
76. When Cu reacts with AgNO 3 solution, the reaction takes 1/2
(c) Eo =_ RT In [PH 2 ]
place is [WB JEE]
F [H+ ]
(a) oxidation of Cu (b) reduction of Cu
(c) oxidation of Ag (d) reduction ofNO3 ( d) £ 0 =- RT In K
F w
404 I Chapterwise & Topicwise Engineering Entrances Solved Papers

85. The oxidation potential values of A, B, C and D are 91. For cell reaction, Zn + Cu 2 + ~ Zn 2+ + Cu
- 0.03, + 0. 108 V, - 0.07 Vand + 0.1V respectively. The cell representation is [BCECE]
non-spontaneous cell reaction takes place between (a) ZnlZn 2+ IICu 2+ ICu
(a) A and B (b) Band D [MHT CET] (b) Cu ICu 2+ IIZn 2+ IZn
(c)DandA (d)BandC
(c) Cu IZn 2 + IIZn ICu 2 +
86. The h ydrogen electrode is dipped in a solution of pH 3
(d) Cu 2 + IZn IIZn 2 + ICu
at 25°C. The potential would be (the value of 2.303
RT! Fis 0.059 V) [KCET] 92. For the following cell with hydrogen electrodes at two
(a) 0.177 V (b) 0.087 V different pressures p 1 and p 2
(c) 0.059 V (d) - 0.177V Pt(H2 ) I H+ (aq) I Pt (H2 ) emf is given by
87. The standard electrode potential is measured by [KCET] Pt IM P2 [Jamia Millia Islamia]
(a) electrometer (b) voltmeter RT Pt
(c) pyrometer (d) galvanometer (a) - log e -
F P2
88. The standard electrode potentials of Ag +/ Ag is
(c) RT loge.!!..'!:_
+ 0. 80V and Cu +/ Cu is + 0. 34 V. These electrodes are F Pt
connected through a salt bridge and if [Kerala CEE] 93. For a cell given below,
(a) copper electrode acts as a cathode, then E 0cell is 2
Ag I Ag+ 11 Cu + I Cu
+ 0.46V.
(b) silver electrode acts as anode, then E 0ce11 is - 0.34 V Ag + + e- ~ Ag,E0 = x
(c) copper electrode acts as anode, then £ 0cell is+ 0.46V Cu 2+ + 2e- ~ Cu, E 0 = yE0cen is
(d) silver electrode acts as a cathode, thenE~en is - 0.34 V [Jamia Millia lslamia]
(e) silver electrode acts as anode and £ 0cell is + 1.14 V
(a)x+ 2y (b)2x+y
89. Which of the following expression is correct? [OJEE] (c) y - x (d) y - 2x
(a) "'1.G0 = - nFE 0cen 94. A standard hydrogen electrode has zero electrode potential
(b) "'1.Go = + nFEocell because [DCEJ
(c) "'1.G0 = - 2.303RT nFE 0cell (a) hydrogen is easier to oxidise
(d) "'1.G0 = - nF log K c (b) this electrode potential is assumed to be zero
90. The standard reduction potential of Zn and Ag in water at (c) hydrogen atom has only one electron
298 K are, Zn 2+ + 2e- ~ Zn; £ 0 = - 0.76 V and (d) hydrogen is the lightest element
Ag + + e- ~Ag; E 0 = +0.80V. Which of the 2014
following reactions take place? [RPET] 95. For hydrogen-oxygen fuel cell at 1 atm and 298 K
(a) Zn 2+ (aq) + 2Ag(s) ~ 2Ag + (aq) + Zn(s) 1
H2 (g) + - 0 2 (g) ~ H 2 0(l), "'1.G = - 240 kJ
(b) Zn(s) + 2Ag + (aq) ~ Zn 2+ (aq ) + 2Ag(s) 2
2
(c) Zn + (aq) + Ag + (aq) ~ Zn(s) + Ag(s) E 0 for the cell is approximately (Given, F = 96500 C)
2
(d) Zn(s) + Ag(s) ~ Zn + (aq) + Ag + (aq)
(a) 2.48 V (b) 1.25 V CKCETJ
(c) 2.5 V (d) 1.24 V
 Topic 4
Batteries
2012
1. During charging of lead storage battery, the reaction (a) generate heat
occurring at the anode is [AMU] (b) create potential difference between the two electrodes
(a) Pb 2 + + 2e- ~ Pb (c) produce high purity water
(d) remove adsorbed oxygen from electrode surfaces
(b) Pb ~ Pb 2 + + 2e-
(c) PbS04 + 2H2 0 ~ 2Pb02 + 4H+ + SO~ - + 2e- 2006
(d) Pb2+ +so!- ~ PbS04 7. In a galvanic cell, the electrons flow from [AMUJ
(a) anode to cathode through the solution
2010 (b) cathode to anode through the solution
(c) anode to cathode through the extemal circuit
2. Which of the following reactions cannot be a base for
(d) cathode to anode through the extemal circuit
electrochemical cell? [AMU]
8. What is the cell reaction occurring in Daniel cell (Galvanic
(a) H 2 + 0 2 ~ H 2 0
cell)? [J&K CETJ
(b) AgN03 + Z n ~ Zn(N0 3] 2 + Ag
(c) AgN0 3 + NaCl~ AgCl + NaN0 2 (a) Cu(s) + ZnS04 (aq) ➔ CuS04 (aq) + Zn(s)
(d) KMn04 + FeS04 + H 2 S04 ~ (b) Zn(s) + CuS04 (aq) ➔ Cu(s) + ZnS0 4 (aq)
K 2 S04 + Fe 2 (S0 4 h + MnS04 + H 2 0 (c) Ni(s ) + ZnS04 (aq) ➔ NiS04 (aq) + Zn(s)
(d) 2Na(s)+ CdS0 4 (aq) ➔ Na 2 S04 (aq)+ Cd(s)
2008 9. Which of the following statements (or equation) is
3. The electrochemical cell stops working after sometime correct ? [J&K CETJ
because [VITEEEJ
(a) The units ofcell emf are Y.cm- 1

(a) electrode potential ofboth the electrodes becomes zero

(b)~G =- nF
(b) electrode potential of both the electrodes becomes Ecen
equal
(c) ln galvanic cell, chemical energy is transformed into
(c) one of the electrodes is eaten away
electrical energy
(d) the cell reaction gets reversed
(d) Oxidation state of Mn in potassium permanganate is
4. What flows in the intemal circuit of a galvanic cell? +6
(a) Ions (b) Electrons [UPSEEJ
2005
(c) Electricity (d) Atoms
10. A galvanic cell is constructed using the redox reaction,
5. Galvanic cell is a device in which [J&KCETJ
(a) chemical energy is converted into electrical energy _!_ H 2 (g) + AgCl(s) ~ H+ (aq) + c 1- (aq )+ Ag(s)
(b) electrical energy is con verted into chemical energy 2 (RPETJ
(c) chemical energy is seen in the form of heat it is represented as
(d) thermal energy from an outside source is used to (a) Pt I H2 (g) I HCl solution I AgN0 3 solution I Ag
dtive the cell reaction
(b) Ag IAgCl(s) IKCl solution 11 HCl solution,
2007 H2 (g) I Pt
6. In a hydrogen-oxygen fuel cell, combustion of hydrogen (c) Pt I H2 (g) I KCl solution 11 AgCl(s) I Ag
occurs to [UPSEEJ (d) Pt I H2 (g ), HCl solution 11AgCl(s) I Ag
 Topic 5
Corrosion
2009
1. The best way to prevent rusting of iron is [UPSEEJ (a) chromium and nickel combine with iron
(a) making it cathode (b) putting in saline water (b) chromium forms an oxide layer and protects iron
(c) Both (a) and (b) (d) None of these from rusting
(c) nickel present in it, does not rust
2007 (d) iron forms a hard chemical compound with chromium
2. Several blocks of magnesium are fixed to the bottom of a
present in it
ship to [MP PET] 2005
(a) keep away the sharks 5. Corrosion of iron is essentially an electrochemical
(b) make the ship lighter
phenomenon where the cell reactions are CKCETJ
(c) prevent action of water and salt
(d) prevent puncturing by under-sea rocks (a) Fe is oxidised to Fe 2+ and dissolved oxygen in water
is reduced to OH-
2006 (b) Fe is oxidised to Fe 3+ and H2 0 is reduced to o~-
3. The process of zinc-plating on iron sheet is known as (c) Fe is oxidised to Fe 2+ and H 2 Ois reduced to 0 2
(a) annealing (b) roasting [UPSEEJ 2
(d) Fe is oxidised to Fe + and H 2 O is reduced to 0 2
(c) galvanisation (d) smelting
4. Stainless steel does not mst because [AMU]

Answers
TOPICl Conductance of Electrolytic Solutions
1. (a) 2. (b) 3. (a) 4. (c) 5. (d) 6. (b) 7. (b) 8. (c) 9. (c) 10. (b)
11. (b) 12. (d) 13. (d) 14. (b) 15. (b) 16. (b) 17. (b) 18. (c) 19. (b) 20. (c)
21 . (b) 22. (d) 23. (a) 24. (c) 25. (d) 26. (d) 27. (c) 28. (c) 29. (c) 30. (a)
31 . (a)
TOPIC2 Electrolytic Cells and Electrolysis
1. (a) 2. (d) 3. (a) 4. (c) 5. (d) 6. (d) 7. (b) 8. (c) 9. (c) 10. (b)
11. ( d) 12. (b) 13. (a) 14. (b) 15. (b) 16. (b) 17. (c) 18. (a) 19. (b) 20. (b)
21 . (c) 22. (c) 23. (c) 24. (c) 25. (b) 26. (d) 27. (c) 28. (b) 29. (d) 30. (a)
31 . (b) 32. (a) 33. (c) 34. (b) 35. (c) 36. (b) 37. (b) 38. (b) 39. (c) 40. (c)
41 . (a) 42. (b) 43. (b) 44. (b) 45. (d) 46. (d)
TOPIC3 Electrochemical Cells, Galvanic Cells, Nernst Equation
1. (a) 2. (a) 3. (c) 4. (a) 5. (a) 6. (a) 7. (d) 8. (d) 9. (b) 10. (c)
11. (a) 12. (d) 13. (d) 14. (d) 15. (d) 16. (a) 17. (d) 18. (a) 19. (d) 20. (c)
21 . ( d) 22. (c) 23. (d) 24. (a) 25. (d) 26. (b) 27. (a) 28. (c) 29. (a) 30. (d)
31 . (a) 32. (a) 33. (d) 34. (b) 35. (c) 36. (a) 37. (d) 38. (b) 39. (d) 40. (a)
41 . (a) 42. (a) 43. (c) 44. (a) 45. (c) 46. (a) 47. (a) 48. (c) 49. (b) 50. (d)
51 . ( d) 52. (b) 53. (a) 54. (d) 55. (d) 56. (d) 57. (d) 58. (e) 59. (b) 60. (c)
61 . (c) 62. (c) 63. (b) 64. (a) 65. (d) 66. (c) 67. (c) 68. (d) 69. (c) 70. (b)
71. (c) 72. (a) 73. (e) 74. (b) 75. (a) 76. (a) 77. (b) 78. (a) 79. (d) 80. (c)
81. ( d) 82. (a) 83. (a) 84. (a) 85. (a) 86. (d) 87. (b) 88. (c) 89. (a) 90. (b)
91. (a) 92. (b) 93. (c) 94. (b) 95. (d)
TOPIC4 Batteries
1. (c) 2. (d) 3. (b) 4. (a) 5. (a) 6. (b) 7. (c) 8. (b) 9. (c) 10. (d)
TI1f!C..5. Corrosion
1. (a) 2. (c) 3. (c) 4. (b) 5. (a)
 Explanations
Topic 1 Conductance of Electrolytic Solutions
1. Equivalent conductivity is related to conductivity as:
A = kx !OOO ⇒ k = Aeq xC
eq ceq 1000 eq

c.q = concentration of solution in equivalent per litre

2 54
= (91 n- •cm 2eq- 1
) ( · eq cm- 3)= 2.9x 10- 3 n- 1cm- 1
15912x 1000
2. A O mNH4OH = 11.''m(NH4Cl + KOH)- A';,,(KCI)
= 152.8 + 272.6 - 149.8= 275.6 S cm 2 mot- •

Degree of dissociation (a)= A::' = ~ = 0.091

Am 275.6
:.Percentage degree of dissociation = 9.1 %

3. S.No. In burette acid In flask base Curve

I. Strong Strong Conductance first decreases due to formation of H 20

and then increases due to addition of strong electrolyte.

Volume of acid added

II. Strong Weak Conductance increases slightly as NH! (salt) is hydrolysed

forming HCI. After neutral point, it increases rapidly due to
addition of strong electrolyte

Weak acid added

III. Weak Strong Conductivity decreases due to neutralisation of conducting to strong base
strong base and then remains constant due to addition
of weak acid.

IV. Weak Weak Conductivity increases due to formation of ions and then
remains constant due to addition of weak base.
KX added + AgNO3

V. KX Insoluble salt AgX is formed, hence conductance remains

constnat. It increases due to addition of KX.

Volume of acid added

Thus, A ➔ 3, B ➔ 4, C ➔ 2, D ➔ I
2
4. A";,, for BaCl 2 = A";,, Ba + + 211.";,, C l-
:. A';q for BaCl2 = _!_ N;,Ba 2+ + N;,c1- = _!_ X 127 + 76 = 139.5n- 1 cm 2
2 2
408 I Chapterwise & Topicwise Engineering Entrances Solved Papers
5. As AgNO 3 is added to solution, KCI will be displaced according 12. NaCl, KNO3, HCI are strong electrolytes but the size of W is
to following reaction smallest. Smaller the size of the ions, greater is die conductance
AgNO 3(aq)+ KCI (aq) ~ AgCl(s) + KN03 (aq) and hence greater is die conductivity (K = C x cell constant).
For every mole ofKCI disp laced from solution, one mole ofKNO 3 13. Specific conductance is defined as the conductance of one
comes in solution resulting in almost constant conductivity. As d1e centimeter cube (cc) of the solution of an electrolyte. Upon
end point is reached, added AgNO 3 remain in solution increasing dilution, the concentration of ions per cc decreases, so the
ionic concentration, hence conductivity increases. Hence, the specific conductance falls. Thus, specific conductance ""
correct option is (d). concentration of electrolytes, hence specific conductance is
least for the solution for 0.002 N concentration.
6. Specific conductance= conductance x cell constant
1.3 Sm - 1 = __!_ S x cell constant 14. Resistance of N solution= 2.5 x 103 n
50 10
1
Cell constant= 1.3 x 50 m-1 = 65 m-1 1C =- - - x cell constant
resistance
= (65/100) cm-• 1
2.5 X 103 X 1.25
. . 1000 x conductance x cell constant
M oar
I conductw 1ty = - - - - - - - - - - - -
molarity 3
1.25 X lQ- = 5 X 10-4 Q-I cm-I
1000 1 65 2.5
= -- x - x-
0.4 260 100 Equivalent conductance
= 6.25 Scm2 mol- 1 1C X 1000 5 X 10-4 X 1000
= 6.25 X 10- 4 Sm 2 mol- 1 M 1/10
= 5 n-• cm2 equiv- •
. Ient conducuv1ty 1C x I000
. . (A eq) = -
7. Equ1va -C- -
15. A';q (NH4OH) = A';q (NHp) + A';q (NaOH)- A:q (NaCl)
Conductivity (K)= cell conStant = (149.74 + 248.1 - 126.4) = 271.44 Q-1cm 2eq - l
resistance
16. Solid NaCl does not conduct electricity due to absence of free
=- - S cm- I
1.15
ions.
250
1.15 X 1000 17. Specific conductivity (K) = _!_ x cell constant
250 XI R
Cell constant= 1C x R = 0.0129 x 100 = 1.29
Aeq = 4.6 n- 1cm2 equiv- • 18. From Kohlrausch's law
8. The nwnber of ions per cc decreases with dilution and dierefore, A";,,= V+A: + V_A':
specific conductance decreases with dilution.
For CaCl 2, A";,, (CaCl 2) = A~2+ + 2A~-
9. When the solution of a weak electrolyte is diluted, the volume of
the solution increases, hence equivalent conductivity 0-c) = 118.88 X 10-4 + 2 X 77.33 X 10-4
increases. However, during this process, the number of current = 118.88 x I 0-4 + 154.66 x I o-4
carrying particles per cm 3 decreases, hence specific conductivity
(K,)decreases.
= 273.54 x 10-4 m 2 mho mo1- 1
10. Swn of molar conductivity of reactants = sum of molar 19. For strong electrolytes the plot of molar conductance (A"') vs ✓
C
conductivity of products is linear.
Therefore, for the reaction
CH 3COOH + NaOH ~ CH3COONa + HCI
A?,,CH3COOH = /\~ CH3COONa + A~ HCI - A~ NaCl
= 91 + 425.9- 126.4
= 390.5 n-l cm2 mo(- I
11. NaCl + KNO3 -➔ NaNO3 + KCI --le
variation of molar conductance
Smn of molar conductivity of reactant Sum of molar
(Am) with ✓
C for strong e lectrolyte.
conductivity of products
A0 NaNO 3 = A?,, NaCl + A~ KNO3 - A~ KC! • t d 1000 x conductance x cell constant
20. Eqmva1en con uctance =- - - - - - - - - - - -
KCI - NaCl = A~ KCI - /\~ NaCl = 24 normality
Molar conductivities of KNO 3 = 11I So, units are, n- 1 cm 2 equiv- 1 or S cm 2 equiv- 1•
Molar conductivities ofNaNO3 = I 11- 24 = 87S cm2mo1- 1 21. Pure water is almost unionised so, it does not conduct electricity.
 Electrochemistry I 409
22. Equivalent conductance (A)= specific conductance (ic) x <P 1
31. Given,!..= 0.5 cm-
where, <P =volume in cm 3 containing 1 g equivalent of electrolyte a
R=50 Q N =1.0
0.1 g equivalent is dissolve in = 1000 cm 3
.ti d 1 / 0.5
S pec1 1c con uctance (1<) = - = - - = -
I g equivalent is dissolve in= lOOO cm 3 = I 0000cm 3 p R·a 50
0.1
A= 1000 = 0.5 X 1000
1C X
So, A = 10000 K
N 50 .l
23. By Kohlrausch's law
0 0
= 10 n-1 cm 2 g eq-1
I\ NaBr = I\NaCl + /\ KBr - /\ KC!
= 126 + 152- 150= 128 S cm 2 mo1- 1 Topic 2 Electrolytic Cells and
24. Molar conductivity or molar conductance Electrolysis
1000 1. Mass of Au deposited = Number of Faraday passed x eq. mass
(Am)= K XV, A 111 = 1C x - -
Cm 0.30 X 15 X 60 X 197 = O. J 84
1
where, C., = molar concentration (mo! L- ) 96485 3 g
I 2. Amount of impurity= Decreased mass of anode - Increased mass
:. Molar conductance (Am) oc -
C of cathode
25. According to Kohlrausch's law = 22.26 - 22.011 = 0.249 g
0 Amount of pure Cu deposited, W = Zit
II +
= - E- x it=
63 54
· x 140 x 482.5
[NaOAc = CH 3 C- O~a ]
96500 2 X 96500
CH3COO- + A.H.
AOCH3COOH = AO . ..(i)
= 22.239 g
But increased mass of cathode= 22.011 g
HCI = A.H. + A~ ,-
AO ... (ii)
Amount of impurity (Fe)= 22.239- 22.011 = 0.228 g
A~3COONa = A•CH3COO- + A~a + . • . (iii) Now, from Faraday's second law of electrolysis
Wt. ofFe deposited eq. wt ofFe
Thus, on adding (ii) and (iii), if A~a• and A~,- are subtracted we
0
Wt of Cu deposited eq. wt of Cu
can obtained the value of A HOAc· Wt. of Fe deposited 27.55
0

Thus, additional value required is A NaCJ. 0.228 31.77

26. R = I 00 n, K = _!_
R a a
(!_)
!_ (cell constant) = 1.29 x I 00 m - 1 wt., of Fe= 27.55 x 0.228 = 0. 199
31.77
Given, R = 520 Q; C = 0.2 M 0.199
0/ .
10
.
rron 111 .
impure copper = - - x 100
µ (molar conductivity)=?µ= ,c x V 22.26
(iccan be calculated as K = ¾(±)now cell constant is known) = 0.89"" 0.9

1 3. We know that, 96500 coulombs= 11200 cm 3 ofH2

Hence,µ = - - x 129 x lOOO x 10~ m 3
520 0.2 3 96500 X 112
: .112cm ofH 2 = - - - - =965Coulombs
= 12.4 X I0--4 s m 2 rno1- 1 11200
27. The molar conductivity of potassium hexacyanoferrate (TT) i.e. 4. Electricity passed = 9.65 coulombs
K 4 [Fe(CN);]is highest because it gives maximum number of ions The amount of silver deposited=?
on ionisation. We know that, a 96500 coulombs electricity deposited
KiFe(CNk; ] -----) 4K+ + [Fe(CN); ]4- Ag= I 08 g rnol- 1
9 65
28. Ionisation depends upon concentration, temperature, nature of :. 9.65 coulombs w ill deposit, Ag= · x 108
solute and on nature ofsolvent. Ionisation increases on increasing 96500
dilution. = 108 X 10--4g = 10.8 mg

29. The equivalent conductance of strong electrolyte is increased by 5. According to the second law of Faraday's electrolysis.
dilution, because its value is equal to the multiple of Kv and the ~=mz .. .(i)
vo lume of solution. By making dilution the volume of solution E1Ez
increases which also increase the value ofequivalent conductivity. w here, m 1 and m2 = masses of elements,
30. F luoro group causes negative inductive effect increasing £ 1 and £ 2 = equivalent masses of elements
ionization, thus 0. I M difluoroacetic acid has highest electrical E = atomic mass EA = 108 = 108
conductivity. valency < g) I
H 0
E(Cu) = 63.6 = 3 1.8
F-f- 6-+-~-+-0-+-H 2
!
F
410 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Putting the value in Eq. (i), 14. Current (i)= 1.5 A
27.0 =_!!!1._ Time (t) = 10 min= 10 x 60 = 600s
108 31.8 Quantity of electricity passed Q =ix t = (1.5 A) x (600 s)
31.8 X 27.0 = _ =900C
⇒
mz = 108 7 95 g 2
Copper is deposited as Cu + + 2e- - Cu(s)
6. Ca 2+ + 2e- - Ca (at cathode) 2 moles of electrons or 2 x 96500 C of current deposit copper
= 63.56g
I mole CaCl 2 = 2F 63 56
From Q = it ⇒ n · 2F = it 900 C of current will deposit copper = · x 900
2 X 96500
n · 2F 30 2 X 96500
t= - - = - X - - - - = 0.296 g
j 40 5
11.2
28960 15. Number of moles ofH 2 = - -
= 28950 s = 22400
60x 60
Number of equivalence of hydrogen
h = 8.04 h "" 8 h = 1.12 X 2 = l0-4
7. The statement is termed as Kohlrausch 's law. 22400
8. 96500 C current produces 12 g Mg Number ofFaradays required= Io- 4
12 X 9.65 :. Current to be passed in one second
9.65 C current produces= - - -
96500 = 96500 X 10- 4 = 9.65 A
= 1.2 X 10- 3 g Mg
16. If F is Faraday and N is Avogadro number,
1.2-X- -
- - = 5 x 10-s mo I M g
10-3 F
24 charge of electron = -
N
R- X + Mg - RMgX Grignard reagent
5x 10-s 5x 10-s 17. 2 x 96500 Celectricity is used to liberate= 22400mL 0 2 at STP
mol mol
:. 9.65 x I 000 C electricity will liberate
Hence, number of moles of RMgX produced = 5 x Io- 5. 22400 X 9.65 X 1000
9. pH< 7; aqueous solution of CuSO4 is acidic in nature. 2 X 96500
Furthennore some drops of H 2SO4 is also added during
=1120mL
electrolysis.
18. At anode,
lO. wt. of Al deposited = eq. wt. of Al
2H20(/) - 0 2 (g) + 4 W (aq) + 4e-
wt. of Cu deposited eq. wt. of Cu 2
2.7 27/ 3 At cathode, 2eu + (aq) + 4e- - 2Cu(s)
Net electrolysis reaction is
wt. of Cu 63.5/ 2
2Cu 2+(aq) + 2Hp(t) - 2Cu(s) + 4 W(aq) + O 2 (g)
wt. of Cu= 9.525 g
So, H 2O is obtained.
11. Ag++ e- - Ag 19. Use of electrolysis is not done in the production of water.
·: 96500 Care required to deposit Ag= I 08 g
20. 2H 2O + 2e- - H 2 + 2OW
: . 965 C are required to deposit Ag
108 For 0.01 mole H2, 0.02 mole of electrons are consumed charge
= - - X 965= 1.08 g required = 0. 02 x 96500 C = i x t
96500
. . 0.02 X 96500 4
12. NaCl - Na+ + Cl- T1mereqmred= = 19.3xl0 s
10 X 10-3
molten
At cathode, Na+ + e- - Na 21. Given, weight of hydrogen liberated= 5.04 x 10-2 g
At anode, 2CI- - 2e- - Cl2 Eq. wt. of hydrogen= 1.008
When one mole of NaCl is electrolysed, I mole Na and.! mole Eq. wt. of silver= 108
2 Weight of silver deposited, w = ?
Cl, is obtained.
2
Th~s, when 230 g ( }
3
° = IO mol) Na is formed,
According to Faraday's second law of electrolysis,
Weight of silver deposited eq.wt.ofsilver
. . moles of Na 10 Weight of hydrogen liberated eq. wt. of hydrogen
the moles of Cl 2 obtained wi ll be= - - - - = - = 5.0 mol w 108
2 2
5.04 X 10- 2 1.008
13. During the electrolysis of an aqueous solution ofMgSO4 between
2
inert electrodes, the products available on the cathode and the w= 108 X 5.04 X 10- = .4
5
anode are H 2 (g) and O2 (g), respectively. 1.008 g
 Electrochemistry I 411
22. Electrolysis of water takes place as follows 27. According to Faraday's law,
H 20 ~ Ir +OW ExQ
m = ZXQ = - -
cat.hod anode
Oxidation
96500
At anode, OH- - OH + e- 108
m= X 2 X 96500 = 216g
4OH - 2H2O + 0 2 96500
+ Reduction
At cathode 2H + 2e- - H2 28. Ag++ e- ~ Ag
Given, time, t = 1930 s 9650 C = 0.1 F = 0.1 equivalent Ag
Number of moles of hydrogen collected = 0.1 mol Ag= 10.8 g Ag
1120 X 10-3
- - - -moles = 0.05 moles 29. Al 3+ + 3e- ~ Al
22.4
·: 1 mole of hydrogen is deposited by= 2 moles of electrons We have, w = ZQ
: . 0.05 moles of hydrogen will be deposited by= 2 x 0.05 where, w = amount of metal
= 0.10 mole of electrons w= 5.12 kg
Charge, Q = nF = 0.1 x 96500 = 5.12xl03 g
Charge, Q = it Z = electrochemical equivalent
0.1 X 96500= i X 1930 ⇒ i = O.l X
96500 Z = equivalent weight
= 5.0 A
1930
96500
23. CuSO4 ~ Cu z+ + So i- atomic mass
At cathode Cu 2+ (aq) + 2[ ~ Cu(s) electrons x 96500
At anode 2H 2O(/) ~ O 2 (g)+ 4W(aq)+ 4e- 27 27
Z= 5.12x103 = xQ
Thus, for the production of one mole of copper from copper 3 X 96500 3 X 96500
sulphate 2F of electricity is required. 3
Q = 5.12 x 10 x 3 x 96500 C= 5.49 x 107 C
24. According to Faraday Ist law, w = Zit 27
where, w = amount of substance 30. Ni-+ 2e- ➔ Ni (at cathode)
Z = Faraday constant or electrochemical equivalent
. 1 . h fN. mol. wt.
i = current in ampere Eqmva ent we1g to 1 = - - - - -
t = time in second gain of electron
If i = l, t = 1, w = Z 58 7
= · = 29.35
_ Wt. of Cu deposited = eq. wt. of Cu 2
25
Wt. of H 2 produced eq. wt. of H i = 12 A t = I h = 60 x 60 s Z = eq. wt.
' ' 96500
0.16 64 / 2 32
---=--= -
wt. of H 2 W e1.g h tofdepos1t
. N.1= -
Zit-x efficiency
--~
100
0.16 -3
29.35 X 12 X 60 X 60 X 60
Wt. ofH 2 = - = 5 x 10 g
32 7.883 g
96500 X 100
Volume of H, liberated at STP,
-22400 31. 2MnO 2(s) + Zn 2+ + 2e- ~ ZnMn 2Ois)
= - - X 5 X I 0-3 cm3 = 56 cm3 2 x 87 g MnO 2 required 2 x 96500 F charge
2
26. w = 60 g and i = 5 A 8 MnO2 = 2 X 96500 X 8 8873.56 F
g 2 X 87
. . Atomic weight Q = it ⇒ 8873.56 = 2 X 10-
3
X t
Eqmvalent weight of Ca = - - - - -
Valency 3
t=
8873 ·56 X IO = 443678 1.5 s
= 40 = 20 2
2
-4436781.5
- - - - -_ 5135
. d ays
According to first law ofFaraday electrolysis, 24 X 60X 60
. Equivalent weight .
w= Ztt = - - - - - - X1Xt 32. In MnO4 the oxidation number of Mn is + 7.
96500 +7 +2
Mn + 5e- ~ Mn
60 = ~ X 5 X t
96500 In the reaction, 5 electrons are involved hence 5 Faraday will be
96500 X 60 needed for the reduction of I mole ofMnO4.
⇒ t= - - - - s Therefore, for 0.5 mole ofMnO4,
20x 5
96500 X 60 h number ofFaradays required= 2. 5 F
20x5x60x60 33. During electrolysis, volumes of 0 2 and H 2 liberated are in the

= 16.08 h = 16 h ratio of 1: 2. Hence, volume ofH2 liberated will be 4.48 dm 3 .

412 I Chapterwise & Topicwise Engineering Entrances Solved Papers
34. Given 125 ml of I M AgNO3 solution. It means that 41. The ionic hydrides conduct electricity in molten state and liberate
1000 mL of AgNO3 solution contains = I08 g Ag H 2 at anode.
. . 108 X 125
125 mL o f AgNo3 soIution contains = - - - - g Ag CaH 2 + 2H2O - Ca(OH)2 + 2H2 i
1000 42. We know that, I Faraday charge liberates one gram-equivalent of
=13.5gAg a metal, hence 0.5 F charge will liberate
·: 108 g of Ag is deposited by 96500 C
96500
= 0.5 X 23
:. 13.5 g of Ag is deposited by= x 13.5 = 12062.5 C = 11.50 g of sodium (E = 23)
108
Q = it 250
43. 250 ml of I M AgNO 3 contain =
1000
t = Q = 12062.5 = 50
i 241.25 = 0.25 mole AgNO3

35. i = 96.5 A, I= 100 s

·: Electricity required to liberate I g equivalent of metal
= 96500 C
w= 10.8 and Q = it
Q = 96.5 X 100 = 9650C: :. Electricity required to liberate 0.25 g equivalent of metal
·: 96500 C deposited wt. of Ag= I 08 g 96500 x 0.25 C
24125
. 108 X 9650
9650 C deposited wt. of Ag = - - - -
96500 44. The unit of electrochemical equivalent ( Z) is g/C.
So, Assertion is correct but Reason is incorrect. Reason is w=Z·i·t
incorrect because mass of substance deposited is directly
proportional to the quantity of electricity. Z =;'- g/C
l · t
36. Q = it I
45. H2◊- H2 + - 0 2
=lx60=60C 2
37. The charge required to liberate one gram equivalent of an element 2H++2e-- H2
is always equal to I Faraday (i.e. = 96500 C). :. l mole of H 2 is liberated form 2 moles of electrons. 2 moles
38. Laws of electrolysis were proposed by Michael Faraday in electrons = 2F = 2 x 96500C charge
1833. Given, i = 4A, t = 30 min
(i) Faraday's first law 'The mass of any substance deposited 2 x 96500C charge liberates
or liberated at any e lectrode is directly proportional to the = 22400 ml H 2 at NTP
quantity of electricity passed. ' i.e. w oc: Q. 4 x 30 x 60 C charge liberates
22400
Where, w = mass of ions liberated in gram x 4 x30x 60 ml H 2
Q = quantity of electricity passed in coulombs. 2x96500
(ii) Faraday 's second law 'When the same quantity of = 835.6 ml,= 0.836 L ofH 2
electricity is passed through different electrolytes, the
masses of different ions liberated at the electrodes are 46. Cr2◊~- + 6e- - 2Cr 3+
directly proportional to their chemical equivalents.'
. W1 E1 Z1it Ei Reduction of I mol of Cr2◊~- to Cr 3+ required 6 moles of
1.e. - = - or - =- . electrons.
w2 £2 Z2it Ez
Hence, charge required = 6 x 96500 C
39. Hydrolysis of water can be represented by the following
equations Topic 3 Electrochemical Cells,
2Hz0 ~ 0 2 + 4H+ + 4e- Galvanic Cells, Nernst
·: 4 Faraday of charge liberate 0 2 = 32 g Equation
2 1. Functions of salt bridge:
:. I Faraday of charge liberate 0 2 = : g = 8 g
(1) It connects the two half cells and completes the cell circuit.
40. According to Faraday's second law of electrolysis, (ii) It keeps the solutions of two half cells and complete the cell
we have circuit but does not participate chemically in the cell
reaction.
~=5_ (iii) It maintains the diffusion of ions from one electrode to
W2 E2
another electrode.
1.08 108 (iv) A cell reaction may also occu r in absence of salt bridge.
X Sometimes, both the electrodes dip in the same electrolyte
: . Weight of hydrogen (x) = 0.01g solution and in such cases we do not require a salt bridge.
Hence, the volume of hydrogen at So option (c) is incorrect.
STP = 22400x 0.01 _ 1 12cm3 (v) This prevent mixing of two electrolyte solution hence,
2 option (d) is incorrect choice
Hence, correct choice is (a).
 Electrochemistry I 413
2. Standard electrode potential of a cell is given by : P. £ 0 (Fe3+ / Fe)
E: 011 = E:xi + E:d 3
Net reaction Fe + - Fe is obtained from
If E;.,11 is + ve, reaction is spontaneous otherwise it is Fe3+ + e- ➔ Fe2+ n 1 = 1 £; = 0.77 V
non-spontaneous. Fe + + 2e- ➔ Fe n2 = 2
2
E; = - 0.44 V
Mn 2+ + 2e- ~ Mn,E = - 1.18V
0

·:Fe3+ + 3e- ➔ Fe; n3 = 3 E; =?

2Mn 2+ ~ Mn3++2e-,E"=-151V
_ n,E; + t1iE;
E3-
3Mn 2+~ Mn+ 2Mn 3+ ,E =£:xi+ £;
0

00 f'3
= -1.51 + (-118)= -2.69V 0.77 + 2(-0.44)
Negative E;.,11 of the reaction indicates reaction is 3
non-spontaneous. = - 0.11 "" 0.04 V
3. E:11 = E:ihode - £:node
3
Thus, P-(3)
= 0.40 - (- 0.44)= 0.84 V
Net reaction 4H2O ----' 4H+ + 4OH-
4. Cr2 O~- + 14H+ + 6e- - 2Cr 3+ + 7H2 O
is obtained from 2H2O ➔ 0 2 + 4H+ + 4e-n 1 = 4E; = - 1.23 V
3
E = Eo _ 0.059 lo [Cr + f[Hp]7 2H2O + 0 2 + 4e- ➔ 4Olr n2 = 4 E; = + 0.40 V
n g [Cr20~-] [H+ J14

1.067 = 1.33 - 0.059 lo (15 X 10-3)2 X 17

6 g (4.5 x 10-3 )(W) 14 E3- ~ ~~~ -,+2
£;
o _ n 1 + t½E; _ Eo Eo
ll3
0.059 lo rl 225 x I 0--{; lJ = 0.263 = - 1.23 + 0.40 = - 0.83 V
6 g (4.5 X 10-3) (H+) 14 Thus, Q-(4), (R) euz++ C u ~ 2 cu+
I t
lo rl50 X 10-3lj = 26.74
g [W ]'4 I_ Oxidation t
Reduction
log (50 x 10-3) - log (W )' = 26.74
4
2
For this, £ 0 ofCu + - eu+ is also requ ired.
- 1.3010 - 14 log (H+) = 26.74
Cu 2+ + 2e- -➔ Cu n1 = 2 0.34 V
- 14 log [W ] = 26.74 + 1.3010
Cu - Cu+ + e-t½ = 1-0.52 V
pH=
2
8;~41
[pH= - log (W )] 2
Cu + + le- - Cu+ n3 = 1 £; ?
=2 E; = n,E: + ,~; = 2 x 0.34 + I x (- 0.52) = 0. ! 6 V
5. A metal w ith lower SRP (Standard Reduction Potential) can have n3 I
the ability to displace metal with higher SRP from their solutions.
0
Thus, Cu ➔ Cu+ + e- n1 = 1, - 0.52 V
As £ 0 2+ is lower than that of £ 2 + , therefore zinc is used
Zn / Zn Fe / Fe
Cu 2+ +e- ➔ Cu+ n2 =1 0.16V
to reduce iron.
E
0
2n 2 •t2n = - 0.76 V Cu 2+ +Cu ➔ 2Cu+
0
£ 0 =-0.52+ 0.16=-0.36V
EF 2+ F = - 0.44 V.
e I e
Thus, (R)--(1) (S) Cr 3+ - Cr 2+
6. As the value of reduction potential of metal ion increases, the is obtained from
tendency of metal oxide to get reduce into metal increases. Cr 3+ + 3e- ➔ Cr 3 - 0.74 V
Since, reduction potential of only Ag is positive among the given, Cr ➔ Cr 2+ + 2e- 2 + 0.9 1 V
thus Ag2O readily gets reduced to Ag metal. In other words, it can
be said that Ag2O is the least stable oxide among the given. Cr3+ + e- ➔ Cr 2+ ?
7. Higher the SRP, better the oxidising agent Among the given
0
E; = - 0.74 X 3 + 2 X 0.91 = _ 0.4 V
E _
2 • is highest, hence MnO4is the strongest oxidising agent. 1
Mn04 / Mn
Thus, P-(3), Q-(4), R-(1), S-(2)
8. When different number of electrons are involved in a redox 9. Daniell cell is represented as,
reaction
Zn(s)I Zn+ (aq)II eu 2+ (aq) I Cu(s)
~c:1=~a;+ ~a; (anode) (cathode)

- n3 FE; =- n 1FE; - n2 FE; 10. ·: ERHE = Cu/Cu + and 2

ErnE = AI / Al 3+

E n,E: + nzE;
o _
3 -
We know that, £cell = ERHE - ELHE
n3 2= + 0.34 -x
x = + 0.34 - 2 = - 1.66 V
414 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2 2
11. Cell Zn1Zn +11Fe +1fe (d) X = Zn, Y = N i
2 2
Electrode potential for Zn/Zn 2+ = 0.763 V Zn+ Ni + - Zn + + Ni
2
Electrode potential for Fe + /Fe= - 0.44 V E:11 =£;n / Zn2+ + £~j2+ /Ni
EMF of cell = E;,idation + £;eduction = 0.76 - 0.23 = 0.53 V, spontaneous reaction
(Fe) (Zn)
I + _ , +
= - 0.44 + 0.763 = 0.323 V 15. (a) 2 H 2(g) - H (aq) + e £cell = £cell - 0.0591 log [H ]
2
12. Cell reaction 20.1+ (aq) - Cu(s) + Cu + (aq)
(b)
According to Nernst equation,
E = Eo _ 2.303 RT lo ~1

o
nF
0.059 I
glM"+
r
M 1
E = E - - n- ogLM"+ j
r
J 0 ., ,. . oµ+,w+2e-
OH O

or HO
0.059 I r Product 1 E O
Ece11 = E:11 - 0.0591 log [W ]
=E o -- - og L
n
j; = at eqm.1.brmm
Reactants
.
1
(c) Ag(s) - Ag+ (aq)Ecell = E:11 - 0.059 1 log [Ag+]

0 -_ Eo - - - Iog K
0.059 (d) Ag+ (s) + Ci-(aq) - AgCl(s) + e-
11 eq
, 1
lo K = flEo £cell = £cell - 0.0591 log - -
g eq 0.059
[CI- ]
0 36 = E;.11 + 0.0591 log[Cl-]
lo K = I x · = 6.09
g eq 0.059 Thus, £cell increases w ith increase in [Cl-].
6
Keq = 1.2x10 16. The metal placed above in electrochemical series can displace the
metals placed below from their salt solutions. The order of given
13_ t:,G = _ nEF = _ 2 X 0.059 X 96500 kJ = _ l 1.4 kJ metals in series is Zn, Fe, Cu, Ag. Thus, Zn metal can displace a ll
1000 other three metals from their salt solution.
14. A cell reaction is spontaneous, if t:,G 0 < 0
17. A(s) + 2B+ (aq) ~ A + (aq) + 2B(s)
2

Since, t,.G 0 =-nFE:11 Here, fl = number of e- transfer= 2

Thus, E:11 >0 E;e11 = 0.0295 V, Kc = ?
E;.11 = E;, + £; 00 0 0.059
£cell = - - log Kc
Reduction fl
0 059
X + y2+ -----+ x2+ + y 0.0295 = · log Kc
2
log Kc = I ⇒ Kc = 10
Oxidation
1
18. For P t, - H2 (I atm) I H CI (x).
(a) X - N i, Y = Fe 2
Ni + Fe2+ - Ni 2+ + Fe According to Nernst equation electrode potential is given by
_ 0.059 1 I
E:;1N;2+ = + 0.23 V Ecell - - 2- ogx

£;0 2+/Fe = - 0.44 V 1

(a) For Pt, H 2 (I atm) I H CI (2 M)
Thus, E:11 = E~i I N i 2+ + E;e2 • 1Fe
2
E _ 0.0591
cell - - - 1og 2
= - 0.21 V,E;e11 < 0, reaction is non-spontaneous. 2
2 2
(b) X = N i, Y = Zn, N i + Zn + - Ni + + Zn 59
= 0.0 l X 0.3010 = 0.0089
E~i /Ni2+ = 0.23 V 2
I
E: 2• =-0.76V (b) From Pt, - H 2 (1 atrn) I HCI (0.1) M
1 20 2
E:ll = - 0.53 vE;ell < 0 , reactions is £cell = 0.0591 log (0.1)
non-spontaneous. 2
59
(c) X = Fe, Y = Zn = 0.0 l X (- 1) = - 0.0295
Fe + Zn 2+ - Fe2+ + Zn 2
1
(c) For Pt, - H 2 (I atm) I HCI (0.5 M)
£:ll = £;e/ Fe2+ + E;,,2+ / Zn 2
= 0.44 - 0.76 = - 0.32 V Ecell -_ 0.059 1 Iog (0 •5)
E:ll < 0, non-spontaneous is reaction 2
59
= 0.0 l X (- 0.3010)= - 0.0089
2
 Electrochemistry I 415
I 0
0.0591
(d) From Pt, - H 2 (1 atm) I HCI ( I M) 24. £cell = - 2- logKc
2
E cell
_ 0.0591 I
- 2 0g
I_ O
-
⇒ 0.59 = 0.0591 log Kc
2
Hence, (a) has potential more than zero. ⇒
0.59 x 2 = lo K
0.059 g C
19. Metals having higher reduction potential can't displace metal
with lower reduction potential from their salts. Therefore, logKc= 20
Zn(-0.762 V) can' t displace Mg (-2.37) from MgCl 2 salt. Kc= antilog 20 = 1020
20. According to electrochemical series, metals having more Eo nEo
standard electrode potential will deposit rapidly. Therefore, 25. Mn2+ + 2e- -----t Mn - 1.18 V - 2.36 V
sequence of deposition of metals on the cathode will be Mn 3+ + e- -----t Mn 2+ 1.51 V 1.51 V
Ag > Hg > Cu
(+ 0.80 V) (+ 7.09 V) (+ o.34 V) Mn3+ + 3e- -----t Mn - 0.28 V - 0.85V
0 0
21. The halfreactions are 26. £cell = Eanode(op) - Ecathode(op)
Fe(s) -----t Fe2+ (aq) + 2e- x 2
= 0.76- 0.41 = + 0.35 V
0 2 (g) + 4W + 4e- -----t 2H 20
27. 2Br- (aq)+ Cl 2 -----t 2Ci-(aq) + Br2
2Fe(s) + 0 2 (g) + 4H+ -----t 2Fe2+(aq) + 2H 2 0(/)
Bromine is released by chlorine as more reactive halogen
E = Eo - 0.059 lo (1 0-3)2 = 1.57 V displaces less reactive halogen from their salt solutions.
4 g c10- 3 )4 co.1)
28 Eo = 2.303 RT I K
22. Reduction hydrogen half-cell is · cell n.F og eq
H+ I (xM) I Pt(H2 ); Pressure Ptt 2
0
0.0591
Ecell = - - logK0 q (At 298 K)
+ n.
Half-cell reaction is
2 W (aq) + 2e- -----t H 2 (g) 0.591 = 0.0 59 l logKeq
I
Reaction quotient = Q = Ptt 2 I [H+ f ,n = 2 log Keq = 10
-E 0
Ered - red - 0.0591 K eq = l x l0 10
n.
29. Higher the negative value of £ 0 , more is the reducing power. The
Iog Q = O- - - Iog Q
0.0591
order of E 0 values (negative value) is
2
-2.37 >-0.76>-0.44
PH2 [H+] Q E,ed (Mg) (Zn) ( Fe)
I atrn 2.0M 0.25 + ve :. Mg can reduce both Zn + and Fe +. Zn can reduce Fe2+ but not
2 2

I atrn I.OM 1.0 0 Mg2+. Fe cannot reduce Mg and Zn but can oxidise them.
2 atrn I.OM 2.0 - ve
30· Ecell = Eocell - 0.05915
fl
I Q
og
2 atrn 2.0M 0.50 + ve
0
0
For standard hydrogen electrode, Ecell = 0.00 V
E,00 = 0.00 Vfor standard hydrogen electrode
If Q > 1, then Ered = - ve E _ 0.05915 I Q
cell - - fl og
Thus, correct answer is ( c).
23. For the given cell, Given, pH= 1.0
2
E - Eo - 0.059 1 lo [Zn + l [H+J -- l x 10_,Ecell -_ - -
0.059 15 1 _I_
-fl- og [H+ ]
cell - cell 2 g [Cu2+ ]
. 0 0.0591 I o 0.059 1 [·: The reaction occurring is 2H+ + 2e- -----t H 2]
(t) E , = £cell - - - log - = £cell
2 0.1 2 _ - 0.059 15 1og [H+]
..) E _ E 0
0.059 1 I I
-+ --
(u 2 - cell - - 2- og I I
= 0.05915 log (10- 1 )= - 0.05915 V= - 59.15 mV
0
0.0591 °
= £cell - - 2- x O= Ecell 31. Fora reaction to be feasible, the value ofE 0 cell must be positive.
.. .) E E0 0.0591 1 0.1 £ 0 0.0591 I. Cu+ 2HCI -----t CuCl2 + H 2(g)
(m 3 = cell - - - og I = cell + - 2- 0 0 0
2
£cell = Eir, tt 2 - Eeu2>m,
: . £3 > E2 >E,
= 0.00 - (+ 0.34) = - 0.34 V
416 I Chapterwise & Topicwise Engineering Entrances Solved Papers
II. Zn + 2HCI - ZnC12 + Hi(g) 37. Given, £~ell = 0.34 V
0 0 0

£cell =Elf'/H2 -Ezn,./Zn £• = £• ?+ - £•

cell (Cu 1euJ (H 2 1tt')
= 0.00- (- 0.76) = + 0.76 V 0.34 = E
0

,. - 0.00
1 (Cu /Cu)
III. Ag+ HCl - AgCl + Hz(g)
2 E;Cu,. / Cu) = + 0.34
Eo =Eo -Eo
cell tt+1tt 2 Ag,./ Ag 38. Given, product= 0.1 Mand reactant= I M
= 0.00 - (0.80) = - 0.80 V o _ Eo 0.0591 [products]
E - - - 1og
Hence, only reaction (II) is feasible. cell - cell 2 [reactants]

32. £:ell = Ee - EA= - 0.45 - (- 2.37) = 1.92 V

0
1.50 = £cell - 0.02955 log
ro.1
L-1 7j
Mg(s)IMg2+ (aq) x M II Fe2+ (aq) 0.01 M IFe (s)
E:ll = 1.470V
The cell reaction is
2 2
Mg+ Fe + - Mg + + Fe Eo
cell
= Eo
H+1H
- Eo,_ .?+
M11w 2
E = Eo - 0.059 lo [Mg2+ ]
cell cell n g [Fe2+] E:1Ai1-+ = - 1.470
59
1.92 = 1.92 - 0.0 log ~
2 0.01
So, E: 2 +1A1 =1.470V

0- -0.059 lo ~ 39. (a) /iG 0 =- nFE:ell

⇒
- 2 g 0.01
(b) Eo = 2.303 RT logK
x=0.0lM cell nF c

33. For the cell, Ni1Ni 2+ II Au 3+ IAu (c) k = Ae-E.I RT

0 0
Given, £ ,. =-0.25Vand£ :i+ =+ 1.5V 1
Ni /Ni Au /Au 40. Oxidizing tendency ""
Electrode potential
Here, N i is at anode and Au is at cathode.
TX - No reaction
£cell = £c - EA= 1.5 - (- 0.25)
= 1.5 + 0.25= 1.75 V
TY - x,z
0
0.059 n+
rz - X
34. Ecell =£cell + - n- log [M ] ⇒ Order of electrode potential is
TY <TZ <TX
59
Ecell -- 0 .34 + 0.02 1og 10-2 ⇒ Order of oxidation of the anion is

y- > z- > x-
59
= 0.34 + 0.0 X -2= + 0.281 V 2
2 41. Cr I Cr 3+ (0. 1 M) II Fe + (0.01 M) I Fe
3
35. Given, Fe + + 3e- - Fe; Ei° = - 0.336V ...(i) Oxidation half-cell; Cr - Cr 3+ + 3e- x 2
2 Reduction half-cell; Fe + + 2e- - 2
Fe x 3
Fe + + 2e- - Fe; £ 2° = - 0.439 V ... (ii)
We need to calculate Net cell reaction;
2 3
Fe3+ + e- - Fe2+,E3 ° =? ... (iii) 2Cr + 3Fe + - 2Cr + + 3Fe (n= 6)
We can obtain the Eq. (iii) by subtracting Eq. (ii) from Eq. (i) but
£ 0 3 , we can not obtain that way because elec~ode potential is = 0.72 - 0.42
intensive property. That's why we determine £ 3 = 0.30 V
!iG3 = !iG 1 - !iG2 E _ E• _ 0.0591 l [Cr + f
3

(!iG is an extensise property) cell - cell II

og [Fez+ ]3
liG3 = 3 x 0.36 F - 2 x 0.439 F 2
= _ _ 0.0591 lo (0.1)
!iG3 = 0.108 F - 0.878 F 0 30
6 g (0.01)3
- 1 X F X £ 3°= -0.770 F ⇒ E; = 0.770F
= 0.30 - 0.0591 lo 10-2
36. In Daniel cell, oxidation occurs at anode and reduction occurs at 6 g 10-6
cathode. Thus, the element, which has higher negative value of
reduction potential, is used as anode and that with lower negative = 0.30 - 0.0591 log 104
value of reduction potential is used as cathode. 6
·: Reduction potential of Zn is more negative d1an Cu. £cell = 0.2606 V

: . Zn1Zn 2+ is anode and Cu 2+ ICu is cathode.

 Electrochemistry I 417
42. In electrochemical series, iron is placed below sodium, so it 50. Galvanic cell is
2
cannot displace sodium from its salt solution. Hence, no reaction Cu(s) I eu + (aq) 11 Hg2+ (aq) I Hg(/)
takes place.
In the above cell, oxidation of copper and reduction of mercury
Fe + Na 3P04 ----t No reaction
takes place. Its cell reaction is written as
Fe + Na 3P04 ----t No reaction 2
0
Cu(s)+ Hg2+ (aq) ----t Cu +(aq) + Hg(/)
43. From given data (From t,,.G = - n.£°F)
51. Since, reduction occurs at Ag electrode, hence increase in the
(i) Cu(s) ----t Cu 2+ (aq) + 2e-
concentration of Ag+ or decrease in concentration of Cu 2+ will
""-G; =-2x(-0.34)xF increase the voltage.
2
(ii) Cu + (aq) + e- ----t eu+ (aq) t10; = - I x (0.15) F 52. Cell is completely discharged, it means equilibrium gets
On addition, Cu(s) ----t cu+ (aq) + e- • established, £cell = 0
0
Zn I Zn 2+ (1 M) II Cu 2+ ( I M) I Cu
t,,.G;=- I x £ x F
Cell reaction, Zn + Cu 2+ ~ Zn 2+ + Cu
""-G; = ""-G; + ""-G;
=(- 2 x-0.34 x F)+ (-1 x 0.15xF) K = [Zn2+ ]
0 eq [Cu2+ ]
= + 0.68 F - 0.15 F = 0.53 For E = - 0.53 V
0.0591
Cu 2+ (aq) + Cu(s), £ =?
0
0 0
Reaction, 2Cu+ (aq) We know, Eccl! = Ecell - - - log Keq
->.
0 n
So, Cu+(aq)+ e- Cu(s), E = + 0.53 V
E:11 = 0.059 1 logKeq or 1.1 0= 0.02591 logKeq
Cu 2+ (aq) + e-; E = - 0.15 V
0
----->,
Ctt(aq) ~ fl

2 [Zn 2+ ]
0
->. . 2.20 .
2cu+(aq) Cu + (aq) + Cu(s),£ = + 0.38 V
Keq = - -2- = anttlog - - = anttlog 37.3
[Cu +] 0.0591
44. The metals having higher negative value of standard reduction
53. t,,.G = - nFE° Fe2+ + 2e- ----t Fe
0
potential are placed above hydrogen in electrochemical series.
The metals place above hydrogen has a great tendency to donate 0

t,,.G = - 2 X F X (- 0.440 V) = 0.880 F ...(i)

electrons or oxidising power.
The metals having great oxidising power are strongest reducing Fe3+ + 3e- ----t Fe
agent. Zn has higher negative value of standard reduction 0
t,,.G = - 3 X F X (- 0.036)
potential. Therefore, it is the strongest reducing agent.
= 0.108 F ...(ii)
45. t,,.G = Ml -T6.S
On subtracting Eqs. (i) from (ii),
For a spontaneous cell reaction, t,,.H should be negative and t,,.S
Fe3+ + e- ----t Fe2+
should be positive. Hence, t,,.G should be negative.
0

46. The metals, present below hydrogen in the electrochemical t,,.G = 0.108 F - 0.880 F = - 0.772 F
series, cannot liberate hydrogen from the dilute acids.
Among the given metal only Ag is present below hydrogen in
Eo = - l1Go = - - 0.772 F = + 0.772 V
nF lxF
electrochemical series, so it does not evolve hydrogen with dil
HCI. 54. By Nemst equation,
Ag + dil. HCl ----t No reaction • 2.303 RT
£cell = Ecen - - - - - log10 K
47. Standard electrode potential of hydrogen electrode is zero. nF
0 At equilibritun Ece11 = 0
48. The Gibb's free energy change t,,.G and emf (£ of a reversible )

Given that,
electrochemical cell are related by the following expression.
R = 8.314 JK-1 mo1- 1
t,,.G =- nFE;011 =- nFE
T = 25 + 273 K = 298 K
49. Electrode potential of cell must be positive for spontaneous
reaction. F = 96500 C and n = 2
Zn 2+ ----t Zn;
0

£ = - 0.76 V Eo _ 2.303 X 8.314 X 298 lo K

cell - 2 x 96500 g io
Cu 2+ ----t Cu;
0

E = - 0.34 V
0.0591 K
Redox reaction is =- - 1og10
2
Zn ----t Zn 2+ + 2e- (oxidation)
Given that, E:11 = 0.295 V
Cu 2+ + 2e- ----t Cu (reduction) 0 0591
0.295 = · log10 K
Zn + Cu 2+ ----t Zn 2+ + Cu 2
lo K = 0.295 x 2 = IO
glO 0.059)
= - 0.34 - (- 0.76) = + 0.42 V log 10 K = antilog I 0
Ecen is positive, so above reaction is feasible. 10
K = 1 X 10
418 I Chapterwise & Topicwise Engineering Entrances Solved Papers
55. Reducing character is based upon higher negative value of 2
60. Mg - Mg + + 2e- (at anode)
reduction electrode potential.
Thus, order of reducing character is Cu2+ + 2e- - Cu (at cathode)
B>C>A E:i, = (athode - £ :node

56. 2H+ + 2e- - H2 = + 0.34 -(- 2.37) = + 2.71 V

According to Nemst equation, 3
61. 2 Fe + + Zn - Zn 2+ + 2 Fe2+
E=Eo + 0.059I 10 g _ l _ 2 Fe3+ + 2e- - 2 Fe2+
n [W f According to Nemst's equation,
59
E = 0- 0.0 l log [W = 0.0591 pH f [Fe2+ ]2
o RT
2 £cell = Ecell
In ~ - -
nF [Fe J
tJ.
57. AgNO 3 ~ Ag2O -
tJ.
2Ag +
I Ece11 is depend on concentration of Fe2+ .
2 02 2
Therefore, on increasing the concentration of[Fe + ] hence, Ecell
58. Pt(s), H 2(g) IH + (IM) II Ag+ (aq) I Ag(s) decreases.
EMF of cell= 0.62 V, E:_11 = 0.80 V 0 0 0.0591
62. Ecell = Ecell - -- log Q
H2 - 2H+ + 2e- (at anode) n
2
Cu z+ + Zn - Zn + + Cu
2Ag+ + 2e- - 2Ag (at cathode) QIM IM

H 2 + 2 Ag+ - 2 Ag+ 2H+ (overall reaction) Q = [Zn2+ l = __!__ = 10

[Cu 2+] 0.1
2.303RT I
o [W f 59
Ecell =E - 2F og [Ag+ r[H2 l Ecell = I.IO- 0.0 l log IO
2
E = Eo _ 2.303RT lo _ I_ = I. 10 - 0.0295 = 1.0705 V
cell 2F g [Ag+ f 63. Cell reaction will be
Br2 + Sn 2+ - 2Br- + Sn 4+ , E = 0.95 V
0

0.62 = 0.80 + 2 x 2.303 x 0.06 log [Ag+]

2 0.059 0

£cell = - 2 - log Keq

- 0.18 = 0.1 382 log [Ag+ ] ⇒ [Ag+]= 0.05 m
59
0.95 = 0.0 log Keq
: .Mole of Ag+ in 100 mL = 0.05 x JOO 2
1000
0.95 x 2 = lo K ⇒ K ., I0 32
Wt. of Ag+ in 100 mL = 0.05 x _!__QQ__ x 108 0.059 g eq eq
1000
% of Ag in 1.08 g alloy 64. £:,II =E:..i (cathode) - £:,i (anode)
-Eo -Eo
= 0.05 X 100 X 108 X JOO = 50% - Ag+/Ag Cu2++/Cu
1000 X 1.08
= 0.80-(+ 0.34) = + 0.46 V
59. Given Standard oxidation potentials of Zn, Cu, Ag and Ni 65. Standard electrode potential of hydrogen electrode at I M
electrode are + 0. 76, - 0. 34, - 0. 80 and+ 0.25 V, respectively. concentration and 1 atm pressure is zero volts .
Zn 2+ + 2e- -
2
Zn, Ecell = - 0.76 V
66. For the change, 2Fe3+ + 3r ~ 2Fe2+ + 3 r
Cu + + 2e- - Cu, Ecell = + 0.34 V E;,,_11 = 0.77 - 0.54 = 0.23 V
Ag+ + e- - Ag, E cell = + 0.80 V o _ 0.059 I K
2 E - - 2- 0g C
N i + + 2e- - N i, Ecell = - 0.25 V
(a) Cu + 2Ag+ (aq) - Cu2+ (aq) + 2 Ag 0.23 = 0.0591 log Kc
2
E;,,,11 = E:thode - E:node
⇒
7
Kc= 6.26x 10
= 0.80 - 0.34 = 0.46 V
Ecell
(b) Zn + 2 Ag+ (aq) - Zn 2+ (aq) + 2 Ag 67. Sn(aq) + 2Fe3+ (aq) - 2Fe2+ (aq) + Sn 2+ (aq)
= 0.80- (- 0.76) = 1.56 V
Ecell As, E;. =E:,; + E;ect
11
(maximum voltage)
(c) H 2 + Ni 2+ (aq) - 2W (aq) + N i
= E;n ,sn 2+ + E ;e.31Fe2+
0

Given, £ 2+ = - 0.14 V
Ecell = - 0.25 V Sn /Sn
2 2 0
(d) Zn + Cu + (aq) - Zn + (aq) + Cu £Sn / Sn 2+ =+ 0. 14 V
= - 0.34 - ( 0.76) = - 1.00 V
Ecell 0

(e) Zn + 2H+ (aq) - Zn 2+ (aq) + H 2

E 3+
Fe / Fe
2+ = 0.77 V
Ece11 = 0- (-0.76 V) = 0.76 V E:.11 = 0.14 + 0.77 = 0.91 V
 Electrochemistry I 419
68. AgJ(s) + e- ~ Ag(s) + 1; £ =-0. 152
0

77. Given,
2 0
Ag(s) - Ag+ + e- £ 0 =-0.8 Zn + - Zn, E = - 0.76 V
AgJ(s) - Ag+ + r-
£ 0 = - 0.952 2
Cu + - Cu, E
0
= 0.34 V
0 0.059 Ag+ - Ag, E =0.8V
0
£cell = - - log K sp
n
Cell reaction o fJ is,
59 2 2
- 0.952 = 0.0 log Ksp Zn+ Cu + - Zn + + Cu
I
952 E;ell = £oxidation + £,eduction
lo K = -0. =- 16.135
g sp 0.059 = + 0. 76 + 0.34 = + I.I0V
69. The oxidising power ofMnO4/Mn 2+ couple decreases by 0.38V. Cell reaction of JI is,
2
59 Zn+ Ag+ - Zn + + Ag
70. E = E~ + 0.0 I log [M +]
n E: 11 = 0. 76 + 0.8 = + 1.56V
Given, ~ = - 2.36 V, [M+] = 0.1 M Cell reaction of III is,
2
n = !(for M+ -➔ M) Cu + Ag+ - Cu + + Ag

E = E~ + 0.0591 log [M+ ] E:011 = - 0. 34 + 0. 8 = + 0.46

59
n
So, the correct order of E: 11 of these cell is
= - 2.36 + 0.0 J log 0.1 II > I > TTL
I
78. Magnesium is more electropositive than zinc, hence it can reduce
= - 2.36 + 0.0591 X (- I)
Zn 2+ (magnesium is placed above zinc in electrochemical series).
= - 2.36 - 0.0591
Mg + Zn O - MgO + Zn
= - 2.4 19 V
79. Mercury cannot displace hydrogen from acid. The reason can be
71. Among given elements, D has the minimum reduction potential explained on the basis of electrochemical series. The metal,
(- 2.37 V), hence it can displace all other from their salts. which is placed above hydrogen in this series, can displace
72· J. Reducing character °" 1 hydrogen from an acid. Mercury is placed below hydrogen in
Reduction potentials ECS, hence it cannot displace hydrogen from an acid.
II. Oxidising power of halogen decreases from F2 to 12 because 80. The ions which lies below H+ in electrochemical series, displace
their reduction potentials decreases from fluorine to iodine. H+ from solution.
IIJ. The reducing power of hydrogen halides increases from Since, eu 2+ lies below H+ in electrochemical series.
hydrogen chloride to hydrogen iodide, since the stability of the So, Cuz+ ions displace H+ when H 2 gas is bubbled in solution
H-X bond decreases in the same order. Hence, all statements containing these ions.
are correct. 81. The elements wh ich are below H2 in electrochemical series,
73. The substances which have lower reduction potentials are cannot displace Hz.
stronger reducing agents. Hence, the order ofstrength of reducing ·: Out of Li+, Srz+, AJ 3+ and Ag+, Ag+
agent is increases in the fo llowing order
Cl- < Fe2+ < H 2 < Zn is below Hz in electrochemical series, so Ag+ cannot displace Hz.

strength of reducing agent increases 82. Given that, Zn / Zn 2+ 11 Cu 2+ / Cu

0 0.059 So, Zn is at anode and Cu is at cathode.
74. £cell = - - log Kc
2 Given, Znz+ / Zn= - 0.76 V
2
lo K = E:.11 X 2 Cu +/ Cu = + 0.34 V
g C 0.059
£cell = £cathode - £anode
lo K = 0.47 x 2 = 0.34 - (-0.76)
g C 0.059 = 0.34 + 0.76= 1.10 V
15
⇒ Kc= 8 .5 X 10 83. Reactions
2
75. From a solution of CuSO 4, Cu can be recovered by Fe metal. (i) Fe(s) - Fe + + 2e-, £ 0 = + 0.44 V
Because Fe is more reactive than Cu, it replace Cu easily. and d G~ = - nE°F = - 2 X 0.44 X F
76. Cu is placed above Ag in electrochemical series, hence it can I
(ii) 2H+ + 2e- + - 0 2 - H 2O(l); E0 = + 1.23 V
replace Ag from its salts solution. Therefore, the reaction occur as 2
follows and dG; = - 2 x (+ I. 23) x F
0 . . +I
Cu + AgNO 3 Oxidat,on CuNO3 + Ag
420 I Chapterwise & Topicwise Engineering Entrances Solved Papers
. + I ~ 92. LHS half cell H 2 (g) - 2H+ (IM)+ 2e-
Net reaction, Fe(s) + 2H + - 0 2 - Fe + H 2 O(l)
2 P1
6G; = 6 G: + c; RHS half cell 2H+ ( I M) + 2e- - H 2 (g)
= - 2 X (+ 0.44) X F + (- 2 X 1.23 X F) P2

= -0.88 F-2.46 F = -3.34 F

Pl P2
= - 3.34 x96500 I = - 322.31 kJ =- 322 kJ
E:.,11 = 0. 00 V, K = Pz , n = 2
I Pt
84. At anode; - H2 + Olr - H 2O + e-
2 , RT
At cathode; if + e- ~ ¾H2 £cell = £cell - -
nF
log,

Redox change; if + OH- ~ H 2O RT Pz

K =0- - log. -
2F Pt
K= [HzO]
[H+][Ofr] RT Pt
E 11 =- log -
ce 2F e P2
Eo = RT In K
F w
93. AtLHS(oxidation)2x (Ag - Ag++ e- ),E;,; =-x
85. (i) The electrode with higher oxidation potential acts as anode At RHS (reduction)
and electrode with lower oxidation potential acts as cathode. Cu 2+ + 2e- - Cu, E:..i = + y
(ii) Cell reaction is spontaneous when £cell is positive. In case of A 2
2Ag + Cu + ~ Cu + 2Ag+ , £;ell = (y-x)
and B; oxidation potential of A = - 0. 03 oxidation potential of
B = + 0.108. Because oxidation potential of B is more than A, Note £ 0 values remain constant when half-cell equation is
so oxidation of A is not possible. The cell having A as anode multiplied/ divided.
and B as cathode is not possible. Therefore, non-spontaneous 94. Standard hydrogen electrode (SHE) is reference electrode. It is
cell reaction takes place between A and B. used to determine the electrode potential of any half cell. The
86. pH = 3, [W ] = I 0- 3 electrode potential of any standard hydrogen electrode is
arbitrarily taken as zero.
E = E:d + 0.059 log [if ]
95. From 6 G 0 = - nFE0 ,
E = 0 + 0.059 log (10- 3 )
E=+ 0.059(-3)=-0.177V where n = number of moles of electrons transferred = 2
87. Standard electrode potential is measured by voltmeter. F = 96500 C
6 G 0 = - 240 kJ = - 240 x 1000 J
88. E:11 = E:ihode - £:node
Eo = - 240000 = 1_24 V
E~g+/ Ag - Ecu+/ Cu = 0.80- 0.34
- 2 X 96500
= + 0.46
89. The correct relation of E;.11 with free energy of cell reaction and Topic 4 Batteries
equilibrium constant are as follows 1. During charging oflead storage battery, following reactions take
0

6G = - nFE:it place.
and 0
6 G = - 2.303 RT log Keq At cathode, PbSOis)+ 2e- - P b(s)+ so~-(aq)
90. As the reduction potential of Zn is less than that of Ag, hence Zn At anode
will act as anode when a cell is made using them. PbSOis) + 2H 2O - PbO2 (s) + SO~- (aq)+4H+ + 2e-
Hence, the correct cell reaction will be
Total cell reaction is
Zn(s) - Zn 2+(aq) + 2e- (oxidation)
2PbSOis) + 2Hz0 - Pb(s) + PbO2 (s)
2Ag+ (aq) + 2e- - 2Ag(s) + 2SO 4(aq) + 4W (aq)
Zn(s) + 2Ag+ (aq) - Zn 2+(aq) + 2Ag(s)
2. Electrochemical cell are based upon the reaction between various
91. Cell representation is done as follows electrolytes. The reaction given in option (d) does not involve
Anode I Anodic electrolyte II cathodic electrolyte I cathode electrolytes, so it cannot be a base for electrochemical cell.
(i) Oxidation is loss of electron and it takes place at anode. 3. The electrochemical cell stops working after sometime because
Reduction is gain of electron and it takes place at cathode. electrode potential of both the electrodes become equal.
:.For cell reaction, Zn + Cu 2+ -➔ Zn 2+ + Cu
4. In the internal circuit of a galvanic cell ions flow while in the
Zn is anode and Cu is cathode. external circuit, there is a flow of electrons from zinc rod to
:. Cell representation is Zn I Zn 2+ II Cu 2+ I Cu copper rod.
 Electrochemistry I 421
5. Galvanic cell is a electrochemical cell that converts the chemical Topic 5 Corrosion
energy of a spontaneous reaction into electrical energy.
1. During rusting, oxidation of iron takes place, i.e. it acts as anode.
6. Any cell (like fuel cell), works when potential difference is Hence, coating/connecting iron with metal of lower reduction
developed.
potential (in comparison to iron) is the best way to prevent its
7. In a galvanic cell, oxidation (i.e. removal of e-) occurs at anode. rusting. In this process, the metal with low reduction potential
These electrons flow through external circuit from anode to undergoes oxidation (i.e. acts as anode) while iron acts as
cathode. T herefore, the direction of current in external circuit is cathode. (Cathodic protection)
from cathode (- ve) to anode(+ ve).
Use of saline water accelerates the process of rnsting thereby
8. In galvanic cell (Daniel cell) the electrical energy is produced increasing the electric conduction of electrolyte solution formed
from chemical reactions. on the metal surface.
At anode, 2. Blocks of magnesium metal provide cathodic protection and
Zn - Zn 2+ + 2e- (oxidation) protect oxidation of steel.
Atcathode, Cu 2+ + 2e- - Cu (reduction) 3. The process of zinc-plating on iron-sheet is known as
2 galvanisation.
Cell reaction, Zn + Cu + - Zn z+ + Cu
4. Chromium is more electropositive metal than iron. In stainless
or Zn(s) + CuSOiaq) - Cu(s)+ ZnSOiaq) steel, chromium forms an oxide layer and thus it protects steel
9. In galvanic cell the electrical energy is produced from chemical from corrosion.
reactions. i.e. chemical energy is transformed into electrical 5. Fe - Fe2+ + 2e- (anode reaction)
energy.
0 2 + 2Hp + 4e- - 40H- (cathode reaction)
1 O. The cell reaction is,
The overall reaction is
_!_ Hz{g)+ AgCl(s) - H+ (aq)+ Cl- (aq) + Ag(s)
2 2Fe + 0 2 + 2H 20 - 2Fe (OH)i
Obvious ly, here hydrogen is being oxidised and AgCI is getting Fe(OH)i may be dehydrated to iron oxide FeO or further oxidised
reduced. Hence, the correct cell representation will be to Fe(OH)3 and then dehydrated to iron rust, Fei0 3.
Pt I H 2 (g), HCl (solution) II AgCl(s) I Ag
Chemical Kinetics
QUICK REVIEW
It is the study of chemical reactions with respect to reaction The slowest step becomes the rate determining step.
rates, effect of various variables, rearrangement of atoms and • Pseudo unirnolecular reactions are the reactions having
formation of intermediates. molecularity~ 2 but order of reaction is one, e.g. hydrolysis
of ester, inversion of cane sugar.
Order of a Reaction CH3COOC2H5 + H 2O ~ CH3COOH + C2HsOH
• It is decided by mechanism of reaction as well as Excess
concentration of reactants. Order of reaction = I
For the reactions, aA + bB~ cC + dD Molecularity = 2
(i) Rate = _ _!_ d[A] = _ _!_ d[B] = _!_ d[C] = _!_ d[D] • Integrated rate equations for
a & b & c & d & (i) Zero order reaction, k = [A]o - [ A] (ll..) f112 = -
a
(ii) Rate = k[At [BY (k = rate constant); this t 2k
mathematical expression is known as rate law • Rate of zero order reaction depends upon initial
equation. Rate law is determined by experiments. concentration of reactant. The plot of concentration of
(x + y)may be equal to (a+ b )or may not be equal to reactant versus time is linear with negative slope and
(a+b). non-zero intercept.
(iii) Order of reaction- (x + y) (i) First order reaction,
1 1 _ 2.303 [A lo_ 2.303 a _ 0.693
• Units ofrate ofreaction = mol L- s - k. - - - 1og- - - - - 1og- - ⇒ t,12 - - -
t [A] t a-x k
• Unit of rate constant (k) for For first order, half-life is independent of initial
nth order reaction = (mol L- 1 ) 1- "s - 1 concentration plot oflog 10 C versus t gives a straight
:. Zero order reaction = mol L- 1s - t line. Radioactive reactions are of first order.
1 (ii) Second order reaction,
First order reaction =s-
1
Second order reaction= mo1- 1Ls - 1
Third order reaction = mo1- 2 L2s- 1 k=H[~]- ]ol=Ha(:-xJ [A
• Molecularity of a reaction is the total number of
molecules or atoms taking part in a reaction. Molecularity
! 112 = ~ ; ( ! 112 oe ~)
can never be zero, negative or fraction whereas order may (iii) Third order reaction,

k-H[A\ [A;~]- ;t[:~~::;i l

be a natural number, fractional, zero or even negative.
• In case of complex reactions taking place in two or more 2 - 2
steps, the molecularity is derived for each elementary step
of mechanism separately and never added.
l112 = ~ ; ( ! 112
2k·a
oe~)
a
 Chemical Kinetics I 423
• Amount of substance left after n half-lives of a first order where, A is frequency factor, E 0 is energy of activation, R is
reaction = [A]o 12n gas constant and Tis absolute temperature.
E
Time taken in comp letion of75% of the reaction (t) logk = logA - a
2.303RT
= to.1s = 2x 1o.so
A plot of logk with _!_ gives a straight line with
• Factors influencing rate of reaction Concentration of T
slope= - __ Ea_
reactants, temperature, catalyst, surface area of reactants.
2.303R
• The rate of reaction depends upon the physical state of (ii) If k 2 and k i are rate constants at temperature T2 and Ti.
reactants and activation energy of reactants. Usually, rate
Then, log k2 = ~ T2 - Ti] r
of reaction increases with increase in surface area of
reactant particles, and the reactions having low activation k , 2.303R T,T2 l
energy are fast whereas, reactions having high activation Rate of reaction depends upon temperature.
energy are slow. . rate constant at 308 K
T emperature coe ffi1c1ent = - - - - - - -
rate constant at 298 K
• Rate of reaction increases in the presence of a catalyst. It
increases the rate of reaction by providing alternative path The value of temperature coefficient for most of the
of lower activation energy to the reactants. reactions lies between 2 to 3.

Arrhenius Equation Collision Theory

It is a mathematical expression to give a quantitative
relationship between rate constant and temperature.
k = A . e - Ea ! RT
According to collision theory, rate of reaction depends upon
collision frequency and effective collisions. For effective
collisions, molecules should have proper orientation and
sufficient energy (energy equal to or greater than the
threshold energy).

Topic 1
Rate of a Chemical Reaction
2014 2012
1. For the elementary reaction M ~ N, the rate of 5. Which one of the following is wrong about molecularity of
disappearance of M increases by factor of 8 upon doubling a reaction? [WB JEE]
the concentration of M. The order of the reaction w ith (a) It may be whole number or fractional
respect to M is [JEE Advanced] (b) It is calculated from reaction mechanism
(a) 4 (b) 3 (c) 2 (d) 1 ( c) It is the number of molecules of the reactants taking
part in a single step chemical reaction
2. Which factor has no influence on the rate ofreaction?
( d) It is always equal to the order of elementary reaction
(a) Molecularity [J&K CETJ
(b) Temperature 6. For the reaction given below,
( c) Concentration ofreactant 5Br- (aq) + Br03(aq) + 6H+~ 3Br2 (/) + 3H2 0(l)
( d) Nature of reactant The rate of formation of Br2 is related to rate of
2013 consumption of Br- by the following relation [AMUJ

3. Order ofreaction is decided by [KCETJ (a) d[Br2 ] = - ~ d[Br- ]

(a) molecularity dt 3 dt
(b) pressure
( c) temperature (b) d[Br2 ] = _ d[Br- ]
( d) mechanism of reaction as well as relative concentration dt dt
of reactants
(c) d[Br2 ] =2 d [Br- ]
4. Which is correct about zero order reaction? [OJEEJ dt 3 dt
(a) Rate ofreaction depends on decay constant
(b) Rate of reaction is independent of concentration (d) d[Br2 ] =-2 d [Br- ]
( c) Unit of rate constant is concentration - t dt 5 dt
(d) Unit ofrate constant is concentration - t time- 1
424 I Chapterwise & Topicwise Engineering Entrances Solved Papers

7. The initial rate, - d[A] at t = 0 was found to be 2008

dt 12. For a reaction l/ 2A ~ 2B, rate of disappearance of
2.6 x 10- 2 mo! L- 1 s - t for the reaction A + 2B ~ 'A' is related to the rate of appearance of B by the
.. . I d [B ] . expression [AIEEEJ
Products. The m1t1a rate, - - -, att "' 0 1s [AMU]
dt
(a) _ d[A] = ..1:_ d [B ] (b) _ d [A] = ..1:_ d[B]
(a) O.lOmol L- 1 s - 1
& 2 & & 4 &
(b) 2.6x 10- 2 mo! L- 1 s - 1
(c) _ d[A] = d[B] (d) _ d[A] = 4 d[B]
(c)5.2xl0- 2 mo!C 1 s - 1
dt dt dt dt
(d) 6.5 x 10- 3 mo! L- 1 s - 1
13. For the reaction, H 2 + 12 ~ 2HI, the differential rate
2010 law is [MHT CETJ
8. In the synthesis of ammonia by Haber process, if 60 moles (a)_ d[H 2 ] = _ d[I 2 ] = ..1:_ d[HI]
of ammonia is obtained in one hour, then the rate of dt dt 2 dt
disappearance of nitrogen is [MP PET] (b) _ d[H2] = _ d[I2 ] = d[HI]
2
(a) 30 mol/min (b) 6 mol/min dt dt dt
(c) 0.5 mol/min (d) 60 mol/min (c) _ d[H 2 ] = _ d[I2] = d [HI]
9. The differential rate law for the reaction, dt dt dt
4NH3 (g) + 502 ( g ) ~ 4NO(g) + 6H2 O(g) (d) _ d[H 2 ] = _ d[I 2 ] = d[Hl]
[Punjab CET] dt dt dt
(a) _ d[NH 3 ] = _ d[O2 ] = _ d[NO] = _ d [H 2O] 14. In the reaction 3A ~ 2B, rate of reaction + d(B) is
dt dt dt dt dt
(b) d[NH 3 ] = d[O 2 ] = _ ..!_ d[NO] = _ _! d[H2O] equal to [WB JEE]

dt dt 4 dt 6 dt (a) _ _! d[A]
(c)..!_ d[NH3] =_! d[O2] =_! d[NO] =_! d[H2O] 3 dt
4 dt 5 dt 4 dt 6 dt (b) _ ~ d[A]
(d) - 1 d[NH3 ] __ 1 d [O 2 ] _ 1 d[NO] _ 1 d[H 2 O] 3 dt
2d[A]
4 dt 5 dt 4 dt 6 dt (C) + - -
dt
2009 (d) _ 2 d[A ]
10. For the reaction, Cl 2 + 2i- ~ 12 + 2 Cl-, the initial 2 dt
concentration of r- was 0.20 mo! L- 1 and the 15. If the volume of the vessel in which the reaction
1 2 NO+ 0 2 ~ 2NO 2 is occurring is diminished to 1/3
concentration after 20 min was 0.18 mo! L- . Then, the
1
rd of its initial volume. The rate of the reaction will be
rate of formation of 12 in mo! L- would be [OJEEJ increased by [WB JEE]
4 4
(a) 1 X 10- {b) 5 X 10- (a) 3 times (b) 9 times
(c) 1 X 10- 3 {d) 5 X 10- 3 ( c) 27 times (d) 36 times

11. 2N2O 5 ~4NO2 + 0 2 2007

For the above reaction which of the following is not correct 16. For the reaction, N 2 + 3H2~ 2NH 3
about rates of reaction ? [Indraprastha CETJ The rate of change of concentration for hydrogen is
0 .3 x 10-4 Ms- 1 • The rate of change of concentration of
(a) - d[N 2 0 5 ] = 2 d [O 2 ]
dt dt ammonia is [BIT SAT]
4
(b) - 2d[N 2 O 5 ] = d[NO2] (a) - 0.2 X 10-4 (b) 0.2 x 10-
dt dt (c) 0.1 X 10-4 (d) 0.3 X 10- 4
(c) 4d[NO2 ] = d[O 2 ] 17. Rate ofreaction depends upon [OJEE]
dt dt (a) temperature (b) catalyst
(d) - 2d[N2Os] = d[NO2] = 4d[O2] ( c) concentration ( d) All of these
dt dt dt
 Chemical Kinetics I 425
2006
18. The reaction, 2SO2 (g) + 0 2 (g) ~ 2SO3 (g) is (a) 1.3 x 10- 5 Ms- I (b) 0.5 x 10- 4 Ms - 1
can-ied out in a 1dm3 vessel and 2 dm3 vessel separately. (c) 7.6x 10-4 Ms - 1
(d)2x10- 3 Ms- 1
The ratio of the reaction velocities will be [AMU] (e)2.5 x 10- 5 Ms - 1
(a)l : 8 (b) l :4 (c)4:1 (d)8:1 20. Observe the following reaction, 2A + B ~ C . The rate
3 1 1
2005 offom1ationofCis2.2x 10- mol L- min - . What is the
19. For the reaction, 2N 2 O 5 (g) ~ 4NO2 (g) + 0 2 (g) valueof- d[A](inmol L- 1 min - 1 )? [EAMCET]
dt
If the concentration ofNO2 increases by 5.2x 10- 3 Min (a) 2.2 X 10- 3 (b) 1.1 X 10- 3
100 s then the rate of the reaction is [Kerala CEE] (c) 4.4 X 10- 3
(d) 5.5 X 10- 3

Topic 2
Factors Influencing Rate of a Reaction and
Integrated Rate Equations
2014
1. For the non-stoichiometric reaction 2A + B ~ C + D, 4. In a first order reaction, the concentration of the reactant
the following kinetic data were obtained in three separate decrease from 0.6 M to 0.3 Min 15 min. The time taken for
experiments, all at 298 K the concentration to change from 0.1 M to 0.025 M in
minutes is [EAMCET]
Initial Initial Initial rate of
concentration concentration formation of C (a) 1.2 (b) 12 (c) 30 (d) 3
(A) (B) (mol L-1 s-1) 5. For a certain reaction the rate law is rate = k [C] 312 . If the
1 1
0.1 M 0.IM 1.2 X l0-3 rate of the reaction is 0.020 mol C s - when [C] = 1.0 M,
0.1 M 0.2M 1.2 X 10-3 what is the rate when [C] = 0.60 M? [Indraprastha CET]

0.2M 0.IM 2.4 X 10-3 (a) 0.0093 rnol L- 1 s - 1

(b) 0.012 mo! L- 1 s - 1
The rate law for the formation of C is [JEE Mains]
(c) 0.033 mol L- 1 s - 1
(a) dC = k[A] [B] (d) 0.040 mo! L- 1 s - 1
dt
(b) dC = k[A]2 [B] 6. Fora first order reaction ofk = 6.2 x 10- 5 s - 1 , t 314 will be
dt (a) 4.65 X 10- 5 s (b) 2 .24 X 10- 4 s [RPET]
(c) dC = k [A ][B ] 2 (c) 2.24 x 10- s 5
(d) 8.27x 10- s 5
dt
(d) dC = k[A] 2013
dt
7. In the reaction, P + Q ~ R + S the time taken for
2. The half-life of two samples are 0.1 and 0.8 s. Their
75% reaction of Pis twice the time taken for 50% reaction
respective concentration are 400 and 50 respectively. The
ofP. The concentration ofQ. Q varies with reaction time as
order of the reaction is [VITEEE]
shown in the figure. The overall order of the reaction is
(a) 0 (b) 2 (c) 1 (d) 4 [JEE Advance d]

3. A(g) ~ P(g) + Q(g) + R(g '), follows first order [0 ]0

kinetics with a half-life of 69.3 s at 500°C. Starting from
the gas 'A' enclosed in a container at 500° C and at a
[Q]
pressure of 0.4 atm, the total pressure of the system after
230 s will be [KCET]
(a) 1.15 atm (b) 1.32 atm Time
(c) 1.22 atm (d) 1.12 atm (a) 2 (b) 3 (c) 0 (d)l
426 I Chapterwise & Topicwise Engineering Entrances Solved Papers
8. The conversion of A to B follows second order kinetics, 17. For a first order reaction the ratio of times to complete
doubling the concentration of A will increase the rate of 99.9% and half of the reaction is [MP PETJ
formation of B by a factor of [KCET] (a)8 (b)9
(a)4 (b)2 ](c) 10 (d) 12
(c) 1/4 (d) 1/2 18. A first order reaction is 60% complete in 20 min. How long
9. 75% of a first order reaction is completed in 30 min. What will the reaction take to be 84% complete? CKCETJ
is the time required for 93.75% completion of the reaction (a) 68 min (b) 40 min
(in minutes)? [KCET] (c) 76 min (d) 54 min
(a) 45 (b) 120 (c) 90 (d) 60 19. For the second order reaction, A + B ~ Products.
10. The unit of second order reaction rate constant is [OJEEl When a moles of A react with b moles of B, the rate
(a) L- 1 mol s - 1 (b) L2 mol - 2 s - 1 equation is given by
(c)Lmo1- 1 s - 1 (d)s - 1 k2t = -l- ln b(a - x)
235 (a - b) a(b - x)
11. Decay of 92 U is ...... order reaction. [OJEEl
(a) zero (b) first When a>> b, the rate expression becomes that of [AMUJ
(c) second (d) third (a) first order (b) zero order
12. The half-life of two samples are 0.1 and 0.4 seconds. Their ( c) unchanged, second order (d) third order
respective concentration are 200 and 50, respectively.
What is the order ofreaction? [OJEEl 2011
(a) 0 (b) 2 (c) 1 (d) 4 20. The following data were obtained during the first order
decomposition of 2A(g) ➔ B(g)+C(s) at a constant
13. The half-life of a reaction is halved as the initial
volwne and at a particular temperature.
concentration of the reactant is doubled. The order of the
reaction is [OJEEl Time Total pressure in Pascal
(a) 0.5 (b) l (c) 2 (d) 0
At the end of IO min 300
2012 After completion 200
14. An organic compound undergoes first order
decomposition. The time taken for its decomposition to l /8 The rate constant in min - I is [KCETJ
and 1/10 of its initial concentration are t 118 and t 1110 , (a) 0.0693 (b) 69.3
respectively. What is the value of [t,,s] x 10? (c) 6.93 (d) 6.93 x 10- 4
U1110 J
21. The time required for l 00% completion of a zero order
(JogtO 2 = 0.3) [JEE Advanced] reaction is CKCETJ
(a)2 (b)3 (c) 5 (d) 9
(a) ak
15. For a first order reaction, (A) ~
products, the
concentration of A changes from 0.1 M to 0.025 M in 40 a
(c) -
min. The rate of reaction when the concentration of A is k
0.01 Mis [AIEEEJ 22. Consider the following statements in respect of zero order
5
(a) l.73 x 10- M/ min reaction.
(b) 3.47 X 10-4 M/min T. The rate of the reaction is independent of reactant
5 concentration.
(c) 3.47x10- M/ rnin
TT. The rate of the reaction is independent of temperature.
( d) l. 73 x 10-4 M l n1in ITT. The rate constant of the reaction is independent of
temperature.
16. 2N2O 5 ~ 4NO2 + 0 2, IV. The rate constant of the reaction is independent of reactant
If rate and rate constant for above reaction are 2.40 x 10- 5 concentration.
mol L- 1 s - 1 and 3 x 10- 5 s - 1 respectively, then calculate Choose the correct statement/s. [Kerala CEEJ
the concentration ofN 2O 5. [BITSAT] (a) Only I (b) I and II
(a) 1.4 {b) 1.2 (c) III and IV (d) I and Ill
(c) 0.04 (d) 0.8 (e) I and IV
 Chemical Kinetics I 427
23. The rate of the reaction A ➔ products, at the initial 29. For a first order reaction, the concentration changes from
2 0.8 to 0.4 in 15 min. The time taken for the concentration to
concentration of 3.24 x 10- M is nine times its rate at
change from 0.1 M to 0.025 M is [Manipal]
another initial concentration ofl .2 x lo- 3 M. The order of
(a) 30 min (b) 15 min
the reaction is [Kerala CEE]
(c) 7.5 min (d) 60 min
l 3
(a) - (b) 2 (c) - 30. In a reaction A + B ➔ C, the rate expression is
2 4 2
I R = k [A] [ B] 2 . If the concentration of both the reactants is
(d)~ (e) -
3 3 doubled at constant volume then the rate of the reaction
will be [MP PET]
24. For a first order reaction, the initial concentration of a
reactant is 0.05 M After45 min itis decreased by 0 .015 M (a) eight times (b) double
Calculate halfreaction time (t 112 ) [Guj CET] ( c) quadmple ( d) triple
H+
(a) 88.84 min (b) 25.90min 31. CH 3 COOC2 H 5 + H 2 O - - CH3 COOH + C2 H 5 OH
(c) 78.72min (d) 77.20min is an example of ...... order. [MP PET]
25. Give relation between halfreaction time (t 112 ) and initial (a) zero (b) second
concentration ofreactant for (n - I) order reaction. (c) third (d) pseudo first order
11
(a) t 112 oc [R] 0 (b) t 112 oc [R]~- [Guj CET] 32. For a reaction between gaseous compounds,
1 2 2A+B ➔ C + D
(c) t 112 oc [Rn + (d) t 112 oc [R ]t
the reaction rate = k [A][B ]. If the volume of the container
2010 is made 1/ 4 of the initial, then what will be the rate of
reaction as compared to the initial rate? [Guj CETJ
26. The concentration of R in the reaction R ➔ P was
(a) 16 times (b) 4 times
measured as a function of time and the following data is
obtained (c) .!. times (d) _!_ tim es
8 16
[R](molar) 1.0 0.75 0.40 0.10
33. For a zero order reaction [RPET]
t (min) 0.0 0 .05 0.12 0.18
(a) t 112 oc Ro
The order of the reaction is [JEE Advanc ed]
(b) l 112 oc I/ Ro
(a) zero (b) first
(c) t 112 oc R~
(c) second (d) third
27. The time for half-life period of a certain reaction (d) t 112 oc 1/ R~
A ➔ products is I h . When the initial concentration of the 34. In the first order reaction, 75% of the reactant gets
1
reactant 'A', is 2.0 mol L- , how much time does it take for disappeared in 1.386 h. The rate constant of the reaction is
its concentration to come from 0.50 to 0.25 mol L- 1, if it is (a)3.0x10- 3 s - 1 (b)2.8x10- 4 s-1 [RPETJ
a zero order reaction ? [AIEEEJ (c) 17.2x 10- 3 s- 1 (d) l.8x 10- 3 s- 1
(a) 4 h (b) 0.5 h
35. The order of a reaction with rate equal to k C~ 2 C 8112
(c) 0.25 h (d) I h
is [JCECEJ
28. Consider the reaction,
(a)l (b) - 1/ 2 (c) - 3/ 2 (d)2
Cl 2 (aq) + H2 S(aq) ➔ S(s) + 2H+ (aq) + 2Cl- (aq) 1
36. A first order reaction has a rate constant I. I 5 x 1o- 3 s - •
The rate equation for this reaction is, rate= k [Cl 2 ][H 2 SJ How long will 5g of this reactant take to reduce to 3g?
Which of these mechanisms is/are consistent with this rate (a) 444 s (b) 402 s [Punjab CET]
equation? (c) 442 s (d) None of these
T. Cl 2 + H 2S - W + c1- + Cl+ + HS- (slow)
Cl+ + HS- - H+ + c1- + S(fast) 2009
TT. H 2S ~ H+ + HS- (fast equilibrium) 37. The half-life period of a first order chemical reaction is
6.93 min. The time required for the completion of 99% of
Cl 2 + HS- - 2CI- + H+ + S(slow) [AIEEE]
the chemical reaction will be (log 2 = 0.30 I) [AIEEEJ
(a) Only II (b) Both I and II
(a) 230.3 min (b) 23.03 min
(c) Neither I nor II (d) Only I
(c) 46.06 min (d) 460.6 min
428 I Chapterwise & Topicwise Engineering Entrances Solved Papers
38. A reaction was observed for 15 days and the percentage of 42. What is the formula to find the value oft 112 for a zero order
the reactant remaining after the days indicated was reaction ? [Guj CETJ
recorded in the following table. k 2k
Time (days) % Reactant remaining (a) [Rlo (b) [R]o
0 100 (d) 0.693
(c) [Rlo
2 50 2k k
4 39
43. For fourth order reaction, what is the unit of k? [Guj CET]
6 25
(a)(mol / L)- 3 s- 1 (b)(mol/Lt 3 s- '
8 21
10 18
(c) (mol/L)- 3 s (d) (mol/Lr 3
12 15 44. For a reaction between A and B, the initial rate ofreaction is
14 12.5 measured for various initial concentrations of A andB. The
15 10 data provided are
Which one of the following best describes the order and the [A] [BJ Initial reaction rate
half-life of the reaction ? [Kerala CEE]
0.20M 0.30M 5 X 10- 5
Reaction order Half-life (days)
0.20M 0.I0M 5 X 10- 5
(a) First 2
0.40 M 0.05M I X 10- 4
(b) First 6
(c) Second 2 The overall order of the reaction is [DCE]
(d) Zero 6 (a) one (b) two
(e) Third 2 (c) two and half (d) three
39. For the reaction, 2A + B ➔ C + D, the orderofreaction is 45. Given the hypothetical reaction mechanism
(a) one with respect to [B] [AMUJ A ~ B ~ C ~ D ~ E a ndtherateas
(b) two with respect to [A]
Species formed Rate of its formation
(c) three
(d) Cannot be predicted B 0.002 mol/h, per mole of A
40. The plot between concentration versus time for a zero order C 0.030 mol/h, per mole of B
reaction is represented by [AMU]
D 0.011 mol/h, per mole of C
E 0.420 mol/h, per mole of D

The rate determining step is [DCEJ

(a) step I (b) step II (c) step III (d) step IV
2008
46. Under the same reaction conditions, initial concentration of
1. 386 mo I drn- 3 ofa substance becomes half in 40 s and 20
s through first order and zero order kinetics respectively.
Ratio(~) of the rate constants for first order (k1 ) and zero
ko
41. A+ B ➔ Product If concentration of A is doubled, rate order (k 0 ) of the reaction is [JEE advanced]
increases 4 times. If concentrations of A and B both are (a) 0.5rnol- 1 drn- 3 (b) l.0moldrn- 3
doubled, rate increases 8 times. The differential rate
(c) 1.5 mol drn- 3 (d) 2.0 rnol- 1 dm 3
equation of the reaction will be [Indraprastha CET]
47. Ifaplot oflog 10 C versus t gives a straight line for a given
(a)dC = kCAXCa (b)dC = kC~xcJ
dt dt reaction, then the reaction is [VITEEEJ
(c) dC = kC~ xC8 (d) dC = kC~ xct (a) zero order (b) first order
dt dt (c) second order (d) third order
 Chemical Kinetics I 429
48. The half-life period of a first order reaction is I min 40 s. 56. For the reaction, 2A + B ~ A 2 B, the rate law given is
Calculate its rate constant. [VITEEEJ
(a) k[2A][B] (b) k[A] 3 [B] Co.JEE]
(a) 6.93 x I 0- 3 min - t (b) 6.93 x 10- 3 s - 1 3
(c) k[A ][B] (d) k[A]2 [B]
(c) 6.93 X 10- 3 s (d) 6.93 X 103 s
57. The half-life period of a first order reaction is 69.3 s. What
49. A hypothetical reaction, A 2 + B 2 ~ 2AB follows the is the rate constant ? [OJEEJ
mechanism as given below, (a) 0.0 1 s- 1 (b) 0 .1 s- 1
A2 ~A + A (fast) (c) l s - 1 (d) 1os- 1
A+B 2 ~ AB+ B (slow)
58. A reaction involving A, Band C as reactants is found to
A+B~AB (fast) obey the rate law, rate = k[AY[B]Y[C]z . When the
The order of the overall reaction is [Manipal] concentrations of A,B and Care doubled separately, the
I rate is also found to increase two, zero and four times
(a) 2 (b) 1 (c) 1- (d) 0 respectively. The overall order of the reaction is
2
(a) 1 (b) 2 [J&KCETJ
50. Consider the following statements, The rate law for the
(c) 3 (d) 4
acid catalysed hydrolysis of an ester being given as Rate
= k [H+ ][ester] = k' [acid]. If the acid concentration is 59. The following data are for the decomposition of
ammonium nitrite in aqueous solution.
doubled at constant ester concentration
I. The second order rate constant, k is doubled. Vol. ofN 2 in cc Time (min)
II. The pseudo first order rate constant, k is doubled. 6.25 10
III. The rate of the reaction is doubled.
9.00 15
Which of the above statements are correct ? [Manipall
11.40 20
(a) I and II (b) II and III
13.65 25
(c) I and III (d) I, II and III
33.05 Infinity
51. For a reaction, A+ 2B ~ C, rate is given by
The order of reaction is [BCECE]
+ d [C ] = k[A] [B ] , hence, the order of the reaction is
dt (a) zero (b) one
(a) 3 (b) 2 [MHT CETJ (c) two (d) three
( c) l (d) 0 60. For a reaction, the rate constant is 2 .34s- 1 • The half-life
52. After how many seconds will the concentration of the period for the reaction is [Jamia Millia Islamia]
reactant in a first order reaction be halved if the rate
(a) 0.30 s
constant is 1.1 55 x 10- 3 s - 1? [MIITCET] (b) 0.60 s
(a) 600 (b) 100 (c) 60 (d) 10 (c) 3.3 s
(d) data is insufficient
53. For a first order reaction, the half-life period is [MIIT CETJ
(a) dependent on the square of the initial concentration 61. The concentration of a reactant X decreases from 0.1 M to
(b) dependent on first power of initial concentration 0.005 M in 40 min. If the reaction follows first order
( c) dependent on the square root of initial concentration kinetics, the rate of the reaction when the concentration of
( d) independent on initial concentration Xis 0.01 M will be [Jamia Millia Islamia]

54. For a zero order reaction, the plot of concentration of (a) 1.73 x 10- 4 M min - I
reactant versus time is (intercept refers to concentration (b) 3.47 X 10-4 M min - I
axis) [Kerala CEE] (c) 3.47 x 10- 5 M min - t
(a) linear with positive slope and zero intercept (d)7.5 x 10-4 M min - I
(b) linear with negative slope and zero intercept
(c) linear with negative slope and non-zero intercept 2007
(d) linear with positive slope and non-zero intercept
(e) a curve asymptotic to concentration axis 62. Consider a reaction; aG + bH ➔ products
When concentration of both the reactants G and H is
55. A reaction proceeds by first order, 75% of this reaction was
doubled, the rate increases by eight times. However, when
completed in 32 min. The time required for 50%
concentration ofG is doubled keeping the concentration of
completion is [UPSEEJ
H fixed, the rate is doubled. The overall order of the
(a)8min (b)l6min reaction is, [JEE Advance d]
(c) 20 min (d) 24 min
(a) 0 (b) I (c) 2 (d)3
430 I Chapterwise & Topicwise Engineering Entrances Solved Papers
63. Consider the reaction, 2A + B ➔ products
70. ~ versus time is a straight line. Order of reaction is
When concentration of B alone was doubled, the half-life [A]
did not change. When the concentration of A alone was (a) first (b) second [OJEE]
doubled, the rate increased by two times. The unit of rate (c) zero (d) third
constant for this reaction is [AIEEE]
1 1 71. Which one of the following statements is incorrect about the
(a)Lmol- s - (b)nounit molecularity of a reaction? [OJEE]
(c) mol L- 1 s- 1 (d) s- 1
(a) Molecularity of a reaction is the number of molecules
64. The rate of first order reaction is 1.5 x 10- 2 of the reactants present in the balanced equation
(b) Molecularity of a reaction is the number of molecules in
mol L- 1 min _, at 0.5 M concentration of the reactant.
the slowest step
The half-life of the reaction is [Manipal] (c) Molecularity is always a whole number
(a) 0.383 min (b) 23.1 min (d) There is no difference between order and molecularity
(c) 8.73 min (d) 7.53 min of a reaction
65. Which one of the following is a second order reaction ? 72. The reaction, 2N2 O 5 ~ 2N2 O 4 + 0 2 is [OJEE]

(a) H 2 + Br2 ~ 2HBr CKCET] (a) bimolecular and second order

(b) NH 4 NO3 ~ N 2 + 3H2 O (b) unimolecular and first order
(c) bimolecular and first order
(c) H2 + Cl 2 Sunlight 2HCI (d) bimolecular and zero order
(d) CH 3 COOCH3 + NaOH~ 73. Rate of a reaction can be expressed by the following rate
2
expression, Rate = k[ A ] [ B], if concentration of A is
increased by 3 times and concentration of B is increased by 2
CH 3 COONa + CH3 OH
times, how many times rate of reaction increases? [AMU]
66. At 500 K, the half-life period of a gaseous reaction at (a) 9 times (b) 27 times (c) 18 times (d) 8 times
an initial pressure of 80 kPa is 350 s. When the
pressure is 40 kPa, the half-life period is 175 s. The 74. Inversion of cane-sugar in dilute acid is a [J&K CET]
order of the reaction is [Kerala CEE] (a) bimolecular reaction
(a) zero (b) one (c) two (b) pseudo-unimolecular reaction
( d) three (e) half (c) unimolecular reaction
(d) trin1olecular reaction
67. The rate law for a reaction between the substances A and
75. For the first order reaction half-life is 14 s, the time required
Bis given by rate = k [ At [B]"'. On doubling the
for the initial concentration to reduce to l /8 of its value is
concentration of A and halving the concentration of B, [J&K CET]
the ratio of the new rate to the earlier rate of the reaction
will be as CUPSEE]
(a) (14 ) 3 s (b) 28 s (c) 42 s (d) (14 ) 2 s
l 76. Which one is not correct ? [DCE]
(a) 2m+n (b)(m+n)
(a) Rate of zero order reaction depends upon initial
(c)(n-m) (d) i(11 - m) concentration of reactant
(b) Rate of zero order reaction does not depend upon initial
68. For the reaction system, concentration of reactant
2NO(g) + O 2 ( g ) ~ 2NO 2 (g) (c) t 112 of first order reaction is independent of initial
volume is suddenly reduced to half its value by concentration of reactant
increasing the pressure on it. If the reaction is of first (d) t 112 of zero order reaction is dependent of initial
order with respect to 0 2 and second order with respect to concentration of reactant
NO; the rate of reaction will CUPSEE] 77. Which expression is wrong for first order reaction?
(a) diminish to one-fourth of its initial value
(b) diminish to one-eighth of its initial value
(a) k = 2. 303 log (Ao)
(c) increase to eight times of its initial value t Al [DCE]
(d) increase to four times of its initial value
69. The t 112 of the first order reaction is [OJEE]
1
(b) k = - - log
2. 303
(Ao.)
At
(a) dependent of initial concentration
(b) directly proportional to initial concentration (c)-k = -t - log - (At )
2. 303 A0
(c) indirectly proportional to initial concentration
(d) independent of initial concentration (d) Rate = k[A]
 Chemical Kinetics I 431
78. The rate equation for the reaction 2A + B ➔ C is found to 85. For the following homogeneous reaction, the unit of rate
be rate = k [A ] [ B] The correct statement in relation to this constant is A + B ~ C [Manipal]
reaction is that the [Jamia Millia Islamia]
(a) mol- 1 L s - 1 (b)s- 1
(a) unit of k must be s - 1
(c) s (d)s- 1 molL- 1
(b) t 112 is a constant
(c) rate of fo1mation ofC is twice the rate ofdisappearance 86. For a reaction A + B ~ C + D, if the concentration of A
of A is doubled without altering the concentration ofB, the rate
(d) value of k is independent of the initial concentrations gets doubled. If the concentration ofB is increased by nine
of A andB times without altering the concentration of A, the rate gets
tripled. The order of the reaction is [KCETJ
2006
(a) 2 (b) I (c) 3/2 (d) 4/3
79. A reaction was found to be second order with respect to the
87. The following homogeneous gaseous reactions were
concentration of carbon monoxide. If the concentration of
carbon monoxide is doubled, with everything else kept the experimentally found to be second order overall.
same, the rate of reaction will [AIEEEJ I. 2NO - N2 + 0 2
(a) remain unchanged TI. 302 - 203
(b) triple ITT. N 2 0 3 - NO + N02
(c) increases by a factor of four IV. H 2 + I2 - 2HI
(d) double
Which of these are most likely to be elementary reactions
80. The following mechanism has been proposed for the that occur in one step ? [Kerala CEEJ
reaction of NO with Br2 to fonn NOBr (a) Only III (b) I and III
NO(g) + Br2 (g) :.====! N0Br2 (g) (c) I and IV (d) III and IV
N0Br2 (g) + NO (g) ~ 2N0Br(g) (e) I, II and III
If the second step is the rate determining step, the order of 88. Find the two-third life (t 213 ) of a first order reaction in
14
the reaction with respect to NO (g) is [AIEEEJ which k = 5.48 x 10- per second [Kerala CEEJ
(a)I (b)0 13 13
(a) 201 X 10 S (b) 2.01 X 10 S
(c) 3 (d) 2 20 10
(c) 201 X 10 S (d) 0 .201 X 10 S
81. For which order half-life period is independent of initial (e) None of these
concentration ? [BITSATJ
89. The reaction 2A + B + C ~ D + E is found to be first
(a) Zero (b) First
(c) Second (d) Third order in A, second in B and zero order in C. What is the
effect on the rate of increasing concentration of A , B and C
82. Which of the following is not the example of pseudo two times ? [Ke rala CEE]
unimolecular reactions? [BITSATJ
(a) 72 times (b) 8 times
H+
(a) CH3 COOC2H 5 + H 20 ~ CH 3 COOH + C 2 H5 0H (c) 24 times (d) 36 times
(e) None of these
H+
(b) C12H22011 + H20 ~ C6H120 6 + C6H1206 90. In a chemical reaction, two reactants take part. The rate of
Glucose Fructose reaction is directly proportional to the concentration of one
(c) CH3 COC1 + H 20 ~ CH3 COOH + HCl of them and inversely proportional to the concentration of
OH- the other. The order of reaction is [WB JEE]
(d) CH 3 COOC 2H 5 + H 20 ~ CH 3 COOH + C 2H 5 0H
(a) 0 (b) I (c) 2 (d) 4
83. For a first order reaction with rate constant 'k' and initial
concentration 'a', the half-life period is given by IBITSATJ 91. Which one of the following is wrongly matched ? [AMUJ
(a) Saponification of CH3 COOC2 H5 - second order
(a) ln 2 (b) _!_
reaction
k ka
3 (b) Hydrolysis ofCH 3 COOCH 3 - pseudo unimolecular
(c) - - (d) None of these reaction
2k-a2 (c) Decomposition of H 2 0 2 - first order reaction
84. The rate constant for a first order reaction whose half-life, (d) Combination of H2 and Br2to give HBr - first order
is 480 s is [ManipaIJ reaction
(a) 2.88x 10- 3 s - 1 (b) 2.72x 10- 3 s - 1 92. The unit of rate constant of second order reaction
(c)l.44x10- 3 s - 1 (d)l.44s- 1 (a)t - 1 (b)conc - 1 t - 1 [GujCETJ
(c) cone t - 1 (d) conc- 2 t - 1
432 I Chapterwise & Topicwise Engineering Entrances Solved Papers
93. If 'a' and 't 112 ' are initial concentration of reactant and 101. In the first order reaction, the concentration of the reactants
half-life of a zero order reaction respectively, which of the is reduced to 25% in one hour. The half-life period of the
following is correct ? [J&K CET] reaction is [Manipal]
l (a) 2 h (b) 4 h
(a) t 112 « - (b) t 112 « a (c) 1/2 h (d) 1/4 h
a
(c)t 112 « -
1
(d)t 112 «a 2
102. For a reaction, X (g) ~ Y (g) + Z(g )
a2 the half-life period is 10 min. In what period of time would
94. The rate constant of a reaction is found to be the concentration of X be reduced to 10% of original
3 x 10- 3 mo! L- 1 min - I. The order of the reaction is concentration ? [Manipal]
(a)zero (b) l [J&K CETJ (a) 20 min (b) 33 min
(c) 2 (d) 1.5 (c) 15 min (d) 25 min
95. The decomposition ofN2 O 5 occurs as 103. The rate law for the chemical reaction
2N 2 O 5 ~ 4NO2 + 0 2 , and follows Ist order kinetics, 2NO2 Cl ~ 2NO 2 + Cl 2 is
hence [BCECEJ rate = k [NO 2 ][C l] . The rate determining step is
(a) the reaction is unimolecular (a) 2NO2 CI ~ 2NO2 + 2CI [MP PET]
(b) the reaction is bimolecular
(b) NO2 + Cl 2 ~ NO 2 Cl + Cl
(c) f112 °" ao
(c) NO 2 Cl + C l ~ NO2 + Cl 2
( d) None of the above
(d) NO2 CI ~ NO 2 + Cl
96. Rate of a reaction can be expressed by following rate
expression Rate = k[ A ]2 [ B ], if concentration of A is 104. For the reaction A + B ➔ C, it is found that doubling the
concentration of A increases the rate by four times and
reduced by half by what times concentration of B is to be
doubling the concentration of B doubles the reaction rate.
increased to have same rate of reaction ? CDCEJ
What is the overall order of the reaction ? CKCETJ
(a) 4 times (b) 2 times
(a) 4 (b) 3/2 (c) 3 (d) l
(c) 1/4 times (d) 8 times
97. The rate constant ofa first order reaction is 6.9 x 10- 3 s- 1. 105. A first order reaction is 10% complete in 20 min. The time
taken for 19% completion is [Ke rala CEEJ
How much time will it take to reduce the initial
concentration to its 1/ 8th value ? [Jamia Millia Islamia] (a) 30 min (b) 40 min (c) 50 min
(d) 38 min (e) 45 min
(a)l00s (b)200s
(c) 300 s (d) 400 s 106. In a first order reaction, reactant concentration C varies
with time t as [UPSEEJ
2005 (a) 1/ C increases linearly with t
98. Which one of the following statement for order of reaction (b) log C decreases linearly with t
is not c01rect ? [JEE Advanced] ( c) C decreases with l / t
(a) Order can be determined experimentally (d) log C decreases with 1/ t
(b) Order of reaction is equal to sum of the power of 107. In the reaction, 2N2 0 5 ~ 4NO 2 + 0 2 , initial pressure
concentration terms in d ifferential rate law is 500 atm and rate constant k is 3.38 x 10- 5 s - 1. After 10
( c) It is not affected with stoichiometric coefficient of the min the final pressure ofN2 O 5 is [OJEEJ
reactants (a) 490 atm (b) 250 atm
( d) Order cannot be fractional (c) 480 atm (d) 420 atm
99. A reaction involving two different reactants can never be 108. If the rate of reaction A ➔ B doubles on increasing the
(a) bimolecular reaction [AIEEEJ concentration of A by 4 times, the order of the reaction is
(b) second order reaction (a)2 (b) l [J&KCET]
(c) first order reaction (c) 1/ 2 (d) 4
( d) uni molecular reaction
109. Mathematical expression for t 114 i.e. when (1/4/h
100. t 114 can be taken as the time taken for the concentration ofa
reaction is over following first order kinetics can be given
reactant to drop to 3 / 4 of its initial value. If the rate
by [Jamia Millia Islamia]
constant for a first order reaction is k, the t 114 can be written
2.303 2 .303
as [AIEEE] (a) t 112 = - - log 4 (b) t 114 = - - log 2
k k
(a) 0 .75/ k (b) 0.69/ k
2.303 4 2 .303 3
(c) 0 .29/ k (d) 0.10/ k (c) t 114 = - - log - (d) t 114 = - - log -
k 3 k 4
 Chemical Kinetics I 433
110. Consider the following two reactions, k 1 and k 2 are expressed in terms of molarity (mo! L- 1 )and
1
A ~ Product - d[A ] = k 1 [AJ 0 time (s - ) as [Jamia Millia Islamia]
dt (a)s - 1 ,Ms - 1 L- 1 (b)Ms - 1 ,Ms- 1
d[B ] 1
(c)s - 1 ,M- 1 s-1 (d)Ms - 1 ,s - 1
B ~ Product - - - = k 2 [B]
dt

Topic 3
Temperature Dependence of the Rate of a Reaction
and Collision Theory of Chemical Reactions
2014
1. Raw milk sours in about 4 hat 27°C, but in about 48 h in a 6. A chemical reaction was carried out at 300 K and 280 K.
refrigerator at I 7°C. What is the activation energy for The rate constants were found to be k 1 and k 2 respectively.
souring of milk? [Manipall Then [KCETJ
(a) 78.0 kl rnol - 1 (b) 46.21 kl mol- 1 (a) k 2 "'0.25 k 1 (b) k 2 "'0.5 k 1
(c)k2 ,,,4k1 (d)k2 ,,,2k1
(c)23.5 klrnol - 1 (d)80.8 kl mol- 1
7. The rate of a reaction is doubled for every 10° rise in
2. A plot of I / T versus k for a reaction gives the slope
temperature. The increase in reaction rate as a result of
- 1x l 0 4 K. The energy of activation for the reaction is
temperature rise from 10° to 100° is [Ke rala CEEJ
1 1
(Given, R = 8.314K- mol- ) [KCET] (a) 112 (b) 512 (c) 400
1 1 (d) 614 (e) 100
(a) 83.141mol- (b) l.202klmol-
(c)l2.021 mol- 1 (d)83.14kl mo1- 1 2012
3. The rate constant (k1 ) of one of the reaction is found to be 8. N 2 (g) + 2H 2 (g) ~ 2NH 3 (g) + 22 kcal
double that of the rate constant (k2 ) of another reaction.
The activation energy for the forward reaction is 50
The relationship between the corresponding activation
kcal. What is the activation energy for the backward
energies of the two reactions Eal and Ea 2 will be [AMUJ
reaction? [Manipall
(a) Ea l < Ea2 (b) Eal > Ea2 (a) 72 kcal (b) 28 kcal
(c) £ 0 1 = Ea 2 (d)
(c)-72 kcal (d)-28kcal
Eal = 2Ea2
9. A given sample of milk turns sour at room temperature
4. For a reaction taking place in three steps, the rate constan ts
(27°C) in 5 h. In a refrigerator at - 3° C., it can be stored 10
are k 1 , k 2 and k 3 and overall rate constant is k = kl k 3 . If times longer. The energy of activation for the souring of
k2 milk is [KCET]
the energies of activation £ 1 , £ 2 and £ 3 are 60, 30 and
(a) 2.303 x 5 R kl mol- 1
l 0 kJ mol- 1, respectively, then the overall energy of
(b) 2.303 x 3 R kl rnol - 1
activation is [AMU] 1
1 1 (c) 2.303 x 2 .7 R kJ mol-
(a)30 kJ mol- (b)40kJmol- 1
(d) 2.303 x 10 R kl mol-
(c)60 kJ mol- 1 (d) l 00kJrnol- 1
2011
2013
10. The rate ofa chemical reaction doubles for every l 0 ° C rise
5. The rate ofreaction doubles when its temperature changes
of temperature. If the temperature is raised by 50° C., the
from 300 K to 310 K. Activation energy of such a reaction
rate of the reaction increases by about [AIEEEJ
will be(R = 8.314 JTC 1 mol- 1 andlog2 = 0.301)
1 (a) IO times
(a) 53.6 kl rnol - [JEE Mains]
(b) 24 times
(b) 48.6 kl mol- 1 (c) 32 times
(c) 58.5 kl rnol- 1 (d) 64 times
(d) 60.5 kl mol- 1
434 I Chapterwise & Topicwise Engineering Entrances Solved Papers

11. A reactant ( A ) forms two products 2009

A ~ B, Activation energy Ea I 17. For a first order reaction A ➔ P, the temperature (T)
A ~ C , Activation energy Ea 2 dependent rate constant ( k) was found to follow the
equation log k = - (2000)/ T + 6.0
IfEa2 = 2 Ea 1 , then k 1 and k 2 are related as [AIEEEJ
The pre-exponential factor A and the actjvation energy Ea,
(a)k1 = 2k2eEa2 \ RT (b)k1 = k2e Ea 1IRT respectively, are [JEE Advance d]
(a) I.Ox 106 s- 1 and 9.2kJmol- 1
(b) 6.os-1 and l6.6kJmo1-1
12. The activation energy of a reaction at a given temperature (c) I.Ox 106 s-1 and l 6.6kJmo1-1
is found to be 2.303 RT J mol- 1• The ratio of rate constant (d) 1.0 x 106 s- 1 and 38.3 kJ mo1- 1
to the Arrhenius factor is [KCETJ 18. The activation energies of two reactions are E 1 and
(a) 0 .01 (b) 0.1 (c) 0.02 (d) 0.001 E 2 (E1 > £ 2 ). If the temperature of the system is increased
from Ti to T2 , the rate constant of the reactions changes
2010
from k 1 to k; in the first reaction and k 2 to k; in the second
13. The activation energy of exothermic reaction A ➔ B
1 1
reaction. Preruct which of the following expression is
80 kJ mol- • The heat of reaction is 200 kJ mo1- • The correct ? [Ke rala CEE]
activation energy for the reaction B ➔ A (in
1

be
kJ mol- )
[Manipal]
will
(a) k; = k~
k1 k2
(a) 80 (b) 120 (c) 40 (d) 280
14. In the given graph the activation energy, Ea for the reverse
(c) k; < k;
k1 k2
reaction will be [MP PET]

200kJ
(e)~=~=O
k l k2
E I
19. Which of the following statement is in accordance with
Products
l
f
I collision theory ? COJEEJ
E8 . = 150 kJ
I
AH = +100 kJ
I
I. Rate is directly proportional to collision frequency
... + ............ t ··-····-······ TT. Rate depends upon orientation of atoms
Reactants ITT. Temperature determines the rate
Reaction coordinate- (a) Only III
(a)l50kJ (b)50kJ (c) 200 kJ (d) 100 kJ (b) Only I and II
(c) Only II and III
15. By increase in temperature by 10 K, the rate of reaction
( d) All of these
becomes double. How many times the rate of reaction
will be if the temperatur e is increased from 303K to 20. If k 1 = rate constant at temperature T1 and k 2 = rate
353 K? [Guj CETJ constant at temperature T2 for a first order reaction, then
(a) 4 (b) 8 (c) 16 (d) 32 which of the following relations is correct?
(Ea : activation energy) [DCEJ
16. Plots showing the variation of the rate constant ( k) with
temperature (T) are given below. The p lot that follows (a) log 5-_ = 2.303 E (T -T.,)
0 2
Arrhenius equation is CDCEJ k2 R I; T2

(a)lLL 0)1L_T--+ T--+

(b) log~ = ~
k1
(T2 - T;
2.303R T; T2
)

( c) log k 2 = ___!}__g__ ( J; Tz )

!L_ (d)rb_
k1 2.303R T2 + T1

(c) ( d) log 5-_ = ~ ( T, T2 )

k 2 2.303R T2 - T1

T~ T-

2008
21. For a reversible reaction, A ~ B,
which one of the following statements is wrong from the
given energy profile diagram ?[BITSAT, AMU, EAMCET]
Chemical Kinetics I 435
2007
28. The energies of activation for fo1ward and reverse
1
reactions for A 2 + B 2 ~ 2AB are 180 kJ mol- and
200 kJ mo1- 1 respectively. The presence of a catalyst
lowers the activation energy ofboth (fo1ward and reverse)

l 1\-
reactions by 100 kJ mo1- 1 . The enthalpy change of the
reaction ( A 2 + B 2 ➔ 2AB) in the presence ofcatalyst will
be (in kJ mol- 1) [AIEEEJ
A
W300 ~ lW
Reaction coordinate
(c) 280 (d) 20
(a) Activation energy of forward reaction is greater than 29. According to Arrhenius equation, the rate constant (k) is
backward reaction related to temperature (T) as [VITEEEJ
(b) The forward reaction is endothermic
(c) The threshold energy is less than that of activation (a) In k2 = Ea [_!_ __!_]
energy k1 R T1 T1
(d) The energy of activation of forward reaction is equal
to the sum of heat of reaction and the energy of
activation of backward reaction
(b) In :: =- ~ [: , - ;J
22. If Xis the total number of collisions which a gas molecule (c)ln k2 = Ea[_!_ +_!_]
register with others per unit time under particular k1 R T1 T2
conditions, then the collision frequency of the gas
containing N molecules per unit volume is [Manipal] (d) In k2 = - Ea [_!_ + _!_]
k1 R T; T2
(a) X I N (b) NX (c) 2 NX (d) NX 12
23. For the two gaseous reactions, following data are given 30. In the respect of the equation k = Ae- Ea I RT in chemical
A ~ = 1010 e- 20,0001r
B; k1 kinetics, which one of the following statements is correct ?
(a) K is equilibrium constant [MP PET]
C ~ D; k 2 = 1012 e - 24,606I T (b) A is adsorption factor
(c) Ea is energy of activation
the temperature at which k1 becomes equal to k 2 is
(d) R is Rydberg constant
(a)400K (b)l000 K (c)800K [KeralaCEE]
31. The temperature dependence of rate constant (k) of a
(d) 1500 K (e) 500 K
chemical reaction is written in tem1s ofArrhenius equation,
24. A chemical reaction proceeds following fo1mula
k = Ae- El RT . Activation energy (E*) of the reaction can
k = PZe- Ea I RT . Which of the following process will
increase the rate of reaction ? [OJEE]
be calculated by plotting CUPSEE]
l
(a) Lowering of Ea (a) log k vs -
(b) Lowering of P T
(c) Lowering of Z I
(b) log k vs - -
(d) Independent of all the above factors log T
25. The rate of reaction increases with temperature due to (c) k vs T
(a) decrease in activation energy [OJEE] 1
(d)k vs - -
(b) increase in activation energy log T
(c) increase in collision frequency
32. With increase in temperature, rate of reaction
(d) increase in concentration
(a) increases [OJEE]
26. Activation energy ofa reaction [J&K CET]
(b) decreases
(a) is independent of temperature (c) remains same
(b) increases with temperature (d) may increase or decrease
(c) gets doubled for every 10 degree rise in temperature
(d) decreases with temperature 33. Which increases on increase of temperature ? [DCEJ

27. Chemical reactions with very high Ea values are generally (a) Energy of activation (Ea)
(b) Collision frequency (Z)
(a) very fast [Jamia Millia Islamia]
(c) Rate constant (k)
(b) very slow (d) Both (b) and (c)
(c) moderately fast
(d) spontaneous
436 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2006 2005
34. Rate ofa reaction can be expressed by Arrhenius equation 38. Consider an endothermic reaction X ~ Y with the
as k = A e - El RT l n this equat:Ion,
. E represents [AIEEEJ activation energies Eb and E I for the backward and forward
reactions respectively. In general [AIEEEJ
(a) the energy above which all the colliding molecules
will react (a) there is no definite relation between Eb and E
1
(b) the energy below which colliding molecules will not (b)Eb = E1
react (c)Eb>E1
(c) the total energy of the reacting molecuJes at a (d)Eb<Ef
temperature, T 3 9. Unit of frequency factor (A) is [BITSATJ
(d) the fraction of molecules with energy greater than (a) mol/L
the activation energy of the reaction (b) mol/L x s
35. The minimum energy required for the reacting molecules (c) depends upon order of reaction
to undergo reaction is [UPSEE, Jamia Millia Islamial (d) it does not have any unit
(a) potential energy 40. Temperature dependent equation can be written as COJEEJ
(b) kinetic energy (a) In k = In A - eEa l RT (b) Ink = In A+ eEa l RT
(c) thermal energy
(d) activation energy (c) Ink = In A - eRTI Ea (d) None of these
36. The rate constant of a first order reaction at 27°C is 41. Temperature coefficient of a reaction is 2. When
10- 3 min - I . The temperature coefficient of this reaction temperature is increased from 30°C to 100°C, rate of the
is 2. What is the rate constant (in min - i ) at l 7°C for this reaction increases by [Guj CETJ
reaction ? CEAMCETJ (a) 128 times (b) 100 times (c) 500 times(d) 250 times
(a) 10- 3 (b) 5 x 10-4 42. The reason for almost doubling the rate of reaction on
(c)2xl0- 3 (d) 10- 2 increasing the temperature of the reaction system by 10°C is
37. Arrhenius equation is [BCECE] (a) the value of threshold energy increases [J&K CETJ

(a) tili = M + l'!.ng RT (b) collision frequency increases

(b) l'!.G = tili-T-1'!.S (c) the fraction of the molecule having energy equal to
(c) k = Ae- Ea / RT threshold energy increases
(d) activation energy decreases
(d) None of these
 Answers
TOPIC 1 Rate of a Chemical Reaction
1. (b) 2. (a) 3. (d) 4. (b) 5. (a) 6. (d) 7. (c) 8. (c) 9. (d) 10. (b)
11. (d) 12. (b) 13. (a) 14. (b) 15. (c) 16. (b) 17. (d) 18. (d) 19. (a) 20. (c)
TOPIC2 Factors Influencing Rate of a Reaction and Integrated Rate Equations
1. (d) 2. (b) 3. (d) 4. (c) 5. (a) 6. (b) 7. {d) 8. (a) 9. (d) 10. (c)
11. (b) 12. (b) 13. (c) 14. (d) 15. (b) 16. ( d) 17. (c) 18. (b) 19. (a) 20. (a)
21. (c) 22. (e) 23. (d) 24. (a) 25. (b) 26. (a) 27. (c) 28. {d) 29. (a) 30. (a)
31. ( d) 32. (a) 33. (a) 34. (b) 35. (a) 36. (a) 37. (c) 38. (c) 39. (d) 40. (d)
41. (c) 42. (c) 43. (a) 44. (a) 45. (a) 46. (a) 47. (b) 48. (b) 49. (c) 50. (b)
51. (b) 52. (a) 53. (d) 54. (c) 55. (b) 56. (d) 57. (a) 58. (c) 59. (b) 60. (a)
61. ( d) 62. (d) 63. (a) 64. (b) 65. (d) 66. (a) 67. (d) 68. (c) 69. (d) 70. (d)
71. (d) 72. (c) 73. (c) 74. (b) 75. (c) 76. (a) 77. (b) 78. (c) 79. (c) 80. (d)
81. (b) 82. {d) 83. (a) 84. (c) 85. (a) 86. (c) 87. (c) 88. (b) 89. (b) 90. (a)
91. ( d) 92. (b) 93. (b) 94. (a) 95. (c) 96. (a) 97. (c) 98. {d) 99. (d) 100. (c)
101. (c) 102. (b) 103. (d) 104. (c) 105. (b) 106. (b) 107. (a) 108. (c) 109. (c) 110. (d)
ill!U Temperature Dependence of the Rate of a Reaction and Collision Theory of Chemical Reactions
1. (a) 2. (d) 3. (a) 4. (b) 5. (a) 6. (a) 7. (b) 8. (a) 9. (c) 10. (c)
11. (b) 12. (b) 13. ( d) 14. (b) 15. (d) 16. (a) 17. (d) 18. (b) 19. ( d) 20. (b)
21 . (c) 22. (d) 23. (b) 24. (a) 25. (c) 26. (d) 27. (b) 28. {d) 29. (a) 30. (c)
31 . (a) 32. (a) 33. {d) 34. (b) 35. (d) 36. (b) 37. (c) 38. {d) 39. (c) 40. (d)
41 . (a) 42. (b)

Explanations
Topic 1 Rate of a Chemical Reaction
1. For elementary reaction, M ➔ N 4. For zero order reaction, rate of reaction is independent of
Rate law can be written as rate ox [Mt concentration of reactants. dx = k [A]
dt
Rate= k[Mt ...(i)
5. Molecularity of a reaction can never be fractional. It is always a
When we double the concentration of[M]rate becomes 8 times,
whole number.
hence new rate law can be written as
6. SBr- + Br03 + 6H+ -➔ 3Br2 + 3H20
8 x Rate = k [2M )" Rate = k [M)"
8 x Rate k[2M)" I d[Br2 ] =_ I d[Br-] = _ d[Br03]
I I n 3
3 dt 5 dt dt
-=- ⇒ 2 =8=2 :. n=3
8 [2f d[Br2 ] = _ ~ d[Br- ]
dt 5 dt
2. The factors which affect the rate of reaction are as follows:
(i) Temperature (ii) Concentration of reactants 7. A + 2B -➔ Products
(iii) Nature of reactants (iv) Presence of catalyst From rate law -d[ A] =- I d[B]
(v) Surface area of reactants (v) Presence of light dt 2 dt
Hence, molecularity has no influence on the rate of reaction. d[B]=2· d(A]=2x2.6x l 0-2
3. Order of reaction is decided by the mechanism of the reaction as dt dt
well as relative concentration of reactants. = 5.2 x 10-2 mol L-1 s-1
438 I Chapterwise & Topicwise Engineering Entrances Solved Papers
8. In Haber's process, ammonia is synthesised as 15. As we know that, rate of reaction is directly proportional to the
Pe, Mo, 300° C concentration of reactant and inversely proportional to the
N 2 + 3H2 ------ 2NH3 volume of vessel.
High pressure
• • fl
1.e. concentration oc -
. f . 60 . V
Rate of synthesis o ammoni a = - = I mol / nun
60 For a given reaction, 2NO(g) + O 2(g) ~ 2NO 2(g)
:. Rate of disappearance of nitrogen, i.e. Rate of reaction = k[NO f[ 0 2 ]
-d[N2 ]= _!_ d[NH3 ] _!_ Xl = 0.5mol/min
If volume of vessel is reduced by ~d of its initial value, then
dt 2 dt 2 3
9. The differential rate law for the reaction, concentration of compound is increased by 3 times. Hence, the
4NH3(g) + 50 2 (g) - 4NO(g) + 6H2O(g) rate of reaction wi ll be increased by 27 times.
Rate = - _!_ d[NH3 ] = - _!_ d (02] 16. N 2 + 3H 2 ~ 2NH3; d[H 2 ] = - 0.3 x 10- 4 Ms- 1
4 dt 5 dt dt
I d[NO] I d [H2O] Rate= _ _!_ d[Hzl = + _!_ d[NH3]
= + - - - =+ - - - -
4 dt 6 dt 3 dt 2 dt
10. Cl 2 + 2Y- ~ 12 + 2Cl- = d[NH3] =-3. d[ Hi]= _3. x (-0.3 X 10-4 )= 0.2x 10-4
dt 3 dt 3
. d(I2 ] I d [r] 17. Rate of reaction depends upon nature of reactants, concentration
Rate of formation of, 12 = - - = - - --
dt 2 dt of the reactants, temperature and presence of catalyst.
I 0.20 - 0.18 I 0.02 I0-4 I L- 1 · - 1 18. 2SO 2(g) + O 2(g) ~ 2SO3(g)
=- X - - - - = -X - - = 5 x mo nun
2 20 2 20
For this reaction, rate (r1) = k[ SO 2] T[ 0 2] 1 .. .(i)
11. 2N2O 5 ~ 4NO2 + 0 2 On doubling d1e volume of vessel, concentration would be half.

es~ r([
I d (product or reactant] Hence,
Rate=± - - - - -
stoichiometric dt 0
2 1
coefficient Rate (12) = k l ;11) =~ = 8 : I
:. Rate = -=-! d [NzOs] = + _!_ d [N02] = d [02] 3
2 dt 4 dt dt 19. Rate of reaction = _!_ d (NOi) = 5· 2 x I o-
_d[N2O 5 ] = d[O 2 ] 4 dt 4 x 100
or 2
dt dt = 1.3 x 10-5 Ms- 1
_ 2d[N2O 5 ] = d(NO2 ] or d[NO 2 ] = 4d [O 2 ] 20. 2A + B - C
or
dt dt dt dt
Rate of reaction,
12. _!_ A - 2B 2 dt dt dt
2
- d [A] = 2 d[C] = 2 x 2.2 x 10- 3
Remember for, a A - b B, dt dt
I d [A ] I d[B] .
- - - - = - - - = Rate ofreacnon = 4.4 X I 0- 3 mol L- 1 mi n -I
a dt b dt
For the given reaction, Topic 2 Factors Influencing Rate of a
- 2d[ A ] = _!_ d[ B ] = Rate of reaction Reaction and Integrated
dt 2 dt
Rate Equations
Rate of disappearance of A,
__ d[A] _ I d[B] _ I d [B] dC , 1Y
1. We have, r= - =k [A][Bi
dt 2 x 2 dt 4 dt dt
here, x = order of reaction w. r. t. A
13. H2 + 12 - 2HI y= order ofreaction w .r.t. B
Rate of reaction, = - d[H 2 ] = - d[I2 ] = _!_ d[HT] 1.2 X 10-3 = k (0. I )"'CO. I )1
dt dt 2 dt 1.2 X 10-3 = k (0. l '/(0.2)1
- 2d[H2] = - 2d[I2 ] = d[HI]
or 2.4 x 10- 3 = k(0.2'/ (O. l )Y
dt dt dt
R = k[A ]1[B] 0
14. For the reaction, 3A - 2B
As shown above rate of reaction remains constant as the
Rate =- _!_ d[A]=+ _!_ d[B] concentration of reactant (B) changes from 0.1 M to 0.2 Mand
3 dt 2 dt becomes double when concentration of A changes from 0.1 to 0.2
d[B] 2d[A] (double).
+ - - =- - - -
dt 3 dt
 Chemical Kinetics I 439

2. We know that, (1112) 1 =

r Jr-•
la2
rate= k [Cf 2 = 0.020 s- (0.60 mol L-
1
f
1 12

(1112)2 a1 = 0.0093 mol L-1 s- 1

where, n = order of the reaction Hence, the rate of a reaction is 0.0093 mol L- 1s- 1,
Given, (t112 ) = 0.ls, a 1 = 400 w hen [C] = 0.60 M.
(t112h = 0.8 S, Gi = 50 6. Let[A 0 ]=a
. .
On substituting the values, -
0. 1
=
50 T - r J
l-
1
[A ] = a - 3a = !!:_ ⇒ !314 = 2.303 log [Ao]
0.8 400 4 4 k [A]

On taking log both sides, log .Q:..!. = (n - I) log -22_ = 2.303 log a X 4 = 2.303 5 X 2 X 0.3010
0.8 400 k a 6.2x 10-
1 I = 2.24 X 10-4 s.
log - = (11 - I) log -
8 8
7. Time of75% reaction is twice the time taken for 50% reaction ifit
n-l= l ⇒ n=2
is first order reaction w.r.t. P. from graph, [ Q ]decreases linearly
3. A(g) - P(g) + Q(g) + R(g) with time, thus it is zeroth order reaction w .r.t. Q.
At t = 0 0.4 atm 0 0 0 dx =k [Pt[Qt
At time= t (0.4 - x) x x x dt
p -04 Orderw.r.t. P=a=l
P, = (0.4-x)+ x + x + x= 0.4 + 2-c or x = - '- -·-
2 Order w .r.t. Q =b=O
. _ _ p1 - 0.4 _ 2 X 0.4 - p1 + 0.4 _ 1.2 - p, Thus, overall order of the reaction = I + 0 = I
··PA-Po-x-po- - -- - - - --
2 2 2 8. Conversion of A - B follows second order kinetic

From, k -_ - - Iog (Po)

2.303 - Therefore, r= k [A] 2
t PA The concentration is doubled, r = k[2A] 2 = k4 [ A ] 2
0.693 = 2.303 log ( 0.4 X 2) Therefore, the new rate becomes four times.
t 112 230 1.2 - p, . 1
9• !314 IS 2 to
⇒
0.693 = 2.303 log ( ~ )
69.3 230 1.2 - p, tu 2 = I x 30= 15min
2
l o g ( ~ ) = 0.693 X 230 0 _9987 93.75% of reaction can be completed in
1.2 - p, 69.3 X 2.303 4 x t 112 = 4 x 15 = 60 min
~ = antilog (0.9987)~"" 10 l O. According to second order reaction,
1.2 - P, 1.2 - P, 2A - Product
12- I Op,= 0.8 or p, = 1.12 atm Rate of reaction, d[A] oc ( A ]2 or dA = k[A f
4. Since, concentration of the reactant decreases from 0.6 M to 0.3 dt dt
M (i.e. halved) in 15 min, therefore halftime for this reaction be w here, k = Reaction rate constant
15min. then tmit of second order reaction rate constant
i.e. tu 2 = 15 min k = d[A] x - 1- = l or L mol- 1 s- 1
1 4
3/ =2Xtu 2 =2x15=30 min. dt [Af s ·molL-1
5. Given, rate k[CJ31 2 11. All kinds of radioactive decay reactions are of first order
reactions. Thus, decay of 92 U 235 is first order reaction.
where, k = rate constant
[C ] = concentration r l"- I
1 1
12. We know, !l = lGzJ where, t 1 and t2 are the half-life periods
When [C] = 1.0 M , rate of the reaction is 0.020 mol. L- s- , then f2 al
the value of rate constant can be given by when the initial concentrations are a1 and Gz.
rate= k[C
2
f According to question, t 1 = 0.1 s, q 1 = 200
1 1 !2 = 0.4 S, q2 = 50
k=~ ⇒ k = 0.020 mol L- s- [·: l M = mol L -1 ]
01 50 rl-Jr -l)
. [C] 312 [l.0]31 2 mol L- 1 On substituting the values - · =
0.4 200
⇒ k = 0.020 s-1
On taking log on both sides,
The unit k suggest that it is first order reaction. 0. 1 50
Thus, va lue for the rate of reaction can be found out by log - = (n- l)x log -
0.4 200
substituting value of k and C in
0.60 = (n- l)x 0.60
440 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2 303
(n - I)= 0.60 = I = · X 0.3010 ...(ii)
0.60 k
n-1 = 1 3
On comparing Eq. (i) and (ii)!!.= - - "' 10
n=1+1=2 ti 0.3010
13. Relation between half-life time and concentration . k 2.303 I a
I I 18. F or a fitrst ord er reaction, · = - - og - -
l112 °" - - then t,12 °" - 2 - I
t a-x
an - I a
Case I k = 2.303 lo 100
It is for second order reaction thus, order of reaction n = 2 20 g 100- 60
I
1112 °" -
a -_ 20
2.303 I 100 _ 2.303 (I JO
og 40 - 20 og -
I 4)
og
[A l o 2 303
14. For a first order process, kt= In - - = · (1 - 0.6020) = 0.045
[Al 20
where, [ A l O = Initial concentration Case JI k = 2.303 log I 00
[Al = concentration of reactant remaining at time 't' . t 100- 84
[ A lo
⇒ kt 118 = In - - -= In 8 ...(i) t = 2.303 lo I 00 = 2.303 (2 lo IO - lo 16)
[A l0 /8 0.045 g 16 0.045 g g
[Alo 2 303
and kt1110 =In - - -= In 10 ... (ii) = · (2 - 1.2040) = 40.73 min "'40min
[A l o/JO 0.045
t In 8 19. A+ B - Products
Therefore, - 118 = - - = log 8 = 3 log2 = 3 x 0.3 = 0.9
t 1110 lnl0 When a>> b, i.e. reactant 'A' is present in large excess, rate of
reaction does not depend upon its concentration. Hence, it w ill be
!.J.i.L X 10 = 0.9 X 10 = 9.0 of first order.
l1110
20. 2A - B + C
15. By first order kinetics, rate constant

k= ·
2 303
t
log
a-x
(-a-);
a = 0.1 M
2p
2p-x
0
X
0
x After 10 min
0 p p After completion
(a -x) = 0.025 Mt= 40 min
Given, p + p = 200
2 303
k = · lo O. l = 0.0347 min-7 After 10 min, 2p- x + x + x = 300 (given)
40 g 0.025 M
2p+ X = 300
Rate = ( !) x k[A i = 0.0347 x 0.01 = 3.47x 10- M / min-
4 1 X = 300 - 200 = ]QQ
2 303 200 1
k = · log = 0.0693 min-
16. The reaction is of first order and for a first order reaction 10 100
rate, 21. For zero order reactions, [Al = -kl+ [Alo
R =k [Nz0 5 l where, [Alo = initial concentration= a
2.4 x 10- 5 = 3 x 10- 5 x [N20 5 l
[Al= remaining concentration = a - a = 0
2
[NO l= .4 x 10-s = 0.8 mol L-1 On putting values of [Al O and [ A l, we get t = !!_
2 5 3 X 10- s k
. 2.303 a 22. For a zero order reaction rate and rate constant are independent of
17. For a first order reactton, t = - - log - - reactant concentration.
k a-x
(i) For 99.9% completion, t1 = ·
2 303
k
log
1
OO
100-99.9
23• 9 = 3.24 X 10-3
(1.2 X 10-
2)" 9 = (3 3)2/3

-_ -
2.303
- Iog -100 -_ -
2.303
- x Iog l000 Order of reaction = 3.3
k 0.1 k
= 2.303 X 3 .. .(i) 24. For first order reaction,
k
k = 2.303 lo [ A0 l ⇒ k = 2.303 lo 0.05
(ii) For 50% completion, t g [Al 45 g 0.035
2.303 I 100
lz= - k - og 100- 50 k = 2.303 log I .42 ⇒ k = 2.303 x 0.1523 = 0 _0078
45 45
= 2.303 log 100 = 2.303 log 2
k 50 k t 112 =0.693
- - = 88 mm
.
0.0078
 Chemical Kinetics I 441
25. Relation between t I12 and initial concentration of reactant for . 2.303 I [ A ] o
36. F or a fi1rst ord er reaction, t = - - og - -
(n - I) order reaction. k [A]
t" 2 oe [R]~- • [ A] 0 = 5g, [A] = 3g and k = 1.15 x 10- 3 s- 1
26. k, = ~[R] = 0.25 = 5 t= 2.303 lo 2
~t 0.05 1.15 X 10- 3 g 3
k = ~[ R] = 0.60 = 5 2 303
n ~I 0.12 · [lo 5 - lo 3)
1.15 X J0- 3 g g
So, reaction must be of zero order. 2 303
· X 0.2218 = 444 S
[Alo 1.15x 10-3
27. For a zero order reaction k 0 = - -
21112
Since, [A ) 0 = 2 M ,1" 2 = I h
37. Half-life= 6. 93 min ⇒ k =
0 693
· = 0.1
6.93
25
So, k 0 = I and k 0 = fu: or t = 0.50 - 0· = 0.25 h We know, k 1 for 99% per cent completion
t I
ki = 2.303 log(lOO)
28. Slowest step is the rate determining step. Thus, in case I, rate law t 1
is given as rate= k [ Cl 2 ) [H2S].
O. l = 2.303 log 100
While for the reaction given in case II, rate law is given as t I
rate= k [H2 S][C12 ][tt+ i- 1.
0.1 = 2.303 log 102
Hence, only mechanism I is consistent with the given rate law. t
29. Tso= 15 min ⇒
t = 2.303 X 2 = 46.06 min.
k = 2.303 log2 = 2.303 log2 a= 0. I M 0.1
(a-x) = 0.D25 M
T50 15 ' ' 2 days
38. 100 50
2 303
For first order reaction, k = ·
t
log
a-x
(-a-) 50
4 days

8 days
25

2.303 log2 2 x 2.303 log2 25 12.5

15 t Hence, the order of reaction is second.
2.303 log 2 2 X 2.303 log 2 For second order reaction,
15 k - 1 r X 1_ I 50 1_ 1r
t = 30min -2la(a-x)J-2l10o x soJ- 200
I I 200
30. Given, R = k [A ][B] 2
t 112 =~ ⇒ =1/200· 100 100 = 2 days
When [ A) = [2 A ]and B = [2 B]
R'=k [2A][2 Bf=k[2A]4[B]
2 39. Order of reaction is an experimentally determined quantity and
thus, cannot be predicted from the given equation.
= 8 k [A] [Bf ⇒ R' = 8R 40.
Thus, the rate will become eight times.
H+ 1~~-,,,~
31. CH 3 COOC2H 5 + H 2O ~ CH3COOH + C 2H 5OH
Since, in this reaction, water is in excess, it is an example of
Conc.ofR ~
pseudo first order reaction (as rate depends only on the
concentration of CH3COOC2H 5) . Time~
(Variation in the concentration V, time plot for a zero order
32. When volume is reduced to one fourth, concentrations become
reaction.)
four times. Hence, the rate of reaction becomes 16 times as
compared to the initial rate. 41. Let the order with respect to A and B is x and y respectively.
33. For zero order reaction, 1112 oc [ R ] 0• Hence,
Rater = [A J'[B]' ... (i)
34. For first order reaction,
t = 2.303 lo [A ] 0 ⇒ k = 2.303 lo 100 On doubling the concentration of A, rate increases 4 times,
k g [A] l.386x60x60 g 25 4r = [2A f[B]' ... (ii)
k = 2.303 x 0.6021 = 2.8 x 10- 4s- 1
I. 386 X 60 X 60
From Eqs. (i) and (ii), ¾ = (¾r :. x =2

3/ 2 - 1/2 :.Order with respect to A is 2.

35. Given,r=kCA 's If concentration of A and B both are doubled,
. = 3 + ( - ') = -3 - - I = 1 8r = [2An2B]' ... (iii)
:.Order ofreact1on
2 2 2 From Eqs. (i) and (iii), we get
442 I Chapterwise & Topicwise Engineering Entrances Solved Papers

I I I 47. A graph between the log concentration

- =-·- [·: x=2]
8 (2f (2)1 (log C)ofreactant and time tfor the first order
reaction gives a straight line, whose slope is
k
_!_ = _I_ . __!__ ⇒ _!_ = _I_ ⇒ 2Y = 2 equal to- - -.
8 (2)2 2Y 8 4 X 2Y 2.303
kt
y= I log10 CA = - - - + log 10(C,.)0
2.303
Hence, differential rate equation is, Hence, the order of the above reaction is one.
r oc [ A n Bl
, I
or -
dC
dt
2
= kCA X CB 48. t112 = 100 s

(where, CA and C8 = concentrations of A and BJ k = 0.693 = 0.693, k = 6 _93 x I ◊-3 s-1

f112 100
R
42. T112 = Tso, x = -
2 49. From slow step, rate = k [ B2] [A]
R R
Tso = - So, Tso ex: R :. Tso ex: - From 1st equation Keq = [ A J2
ko ko [A2l
Therefore, the formula of t 112 for a zero order reaction is [Rlo_ or [A] = .JKeq[A2 ] = K~ 2 A4' 2
2k
2 112 112
43. Units of k = conc 1- nc 1 Hence, rate = k[B2 ] K~ [A2 ] = k'[A2 ] ( B2 ]
(mol / L) 1- 4 s- 1 I
Hence, order= 1-
(mol / Lf 3s- 1 2
SO. Pseudo first order rate constan t is doubled as well as rate of
Therefore, the unit of k is (mo!/ Lf 3s- 1for fourth order reaction.
reaction is doubled. It may be noted that in presence of acid,
44. If the order ofreaction w.r.t. A is n and the order ofreaction w.r.t. hydrolysis of ethyl acetate is a pseudo tmimolecular reaction but
Bis m, rate law becomes the actual value of k depends upon the concentration ofH+ ions,
Rate= k [A]" [Br otherwise rate constant of a reaction is constant at constant
Froml 5xl0-s=[0.20f[0.30]m ... (i) temperature.

From II 5 x l◊-s = [0.20f (0.10]"' ... (ii) 51. Rate(+dc)=k[A][B]

dt
From III Ix 1◊- = [0.40f [0.05]"'
4
... (iii)
Thus, the order ofreaction w.r.t. A = I
or !O x 10-s = (0.40]" [0.05]m The order of reaction w.r.t. B = I
5 X 1◊-S _ ro.20]n [0.307"' Total order of reaction = I + I = 2
From Eqs. (i) and (ii) 5 x 10-s 0.20 0. 10 -l J 52. Rate constant k = 1. 155 x I ◊-3 s- 1

I = (3t ⇒ (3)0 = (3t ⇒ m = 0 k = 2.303 log - a- ·: a= a, (a-x) =!:

t ~-zj 2
From Eqs. (ii) and (iii),
t 112 -
2.303 Iog a - - - - ~ Iog 2
2.303
5x10-s = (o.20)"(0.10)"' - - k- a / 2- 1.155xJ0- 3
!O x 10-s 0.40 0.05 2 303
· X 0.3010
_!_ = (.!.)nX (~)o 1.1 55 X l◊-3
3
2 2 0.05 0.693 X I 0 s
600
1.155
⇒

or t = 0.693 = 0.693 = 600 s

112
Overall order of the reaction = n. + m = I + 0 = I. k l.155 x!0-3
45. The slowest step is the rate determining step. Formation of B I
53. l112= - -
(i.e. step I) is the slowest step, therefore step T is the rate (a)" - 1
determining step.
w here, n. = order of reaction
46. F irst order kinetics, ki = 0.693 = 0.693 s-1 a = initial concentration
1112 40
For first order reaction, n. = 1
Zero order kinetics, ko = ~ = 1.386 1 I
21112 2 X 20 1112= 1-=-T a= o=0
a a
Hence, !J_ = 0·693 = 0.5 mol- 1dm-3 Thus, for a first order reaction, t 112 is independent of initial
ko 1.386 concentration.
 Chemical Kinetics I 443
54. For a zero order reaction, the plot of concentration of reactant
61. k = 2.303 log A0
versus time is a straight line (linear) w ith a negative slope and t A
non-zero intercept. 2 303 2 303
= · lo ----2:..!_ = · lo 20 = 0.075
40 g 0.005 40 g
I '""""'" [Al, Rate of reaction when concentration of Xis 0.01 M w ill be
t - k 1
0.075 x 0.0 1 = 7.5 x 10-4 M min- •
[A)
62. aG + bH - Products
t --+ Suppose order of reaction = n
When concentration of both G and H is doubled then rate
.
55 . F or fiirst order react.ton, k. = -
2.303 I a
- og 10 - - increases by eight times.
t (a-x) Rate= k (reactants)" ⇒(8) = k (2)"
where, a = initial concentration
(2)
3
= k (2)" ⇒ n = 3
x = change in concentration during time 't'.
If75% of the reaction was completed in 32 min, then When concentration ofG is doubled keeping the concentration of
k _ 2.303 lo I 00 _ 2.303 lo 4 H fixed, the rate is doubled.
- 32 glO (100 - 75) - 32 glO Rate= [G ]1 then, rate= [G J 1[H ] 2
1
k = 0.0433 min- 63. 2A + B - Products
Hence, time required for the completion of 50% reaction. [BJ is doubled, half-life didn't change
2.303 I 100 2.303 I . Half-life is independent of change in concentration ofreactant i.e.
t = 0.0433 og10 (100 - 50) = 0.0433 ogio 2 = 16 mm first order. F irst order w.r.t. to B when [A] is dou bled, rate
increased by two times.
56. For the reaction, 2A + B - A2B ⇒ First order w.r.t. A
According to rate laws, Hence, net order ofreaction = I + I = 2
Rate oc concentration of reactants Unit for the rate constant= conc.< 1 - n) t-1
2
Rate=k[AJ [B]
r
= (mol L-1 1· s- 1 = Lmo1- 1 s-1
where, k = rate constant
64. For the first order reaction
57. For first order reaction,
Half-life period (t1n) =
0 693
·
k
Rate ( !) = k [A] w here, [ A] ➔ concentration of reactant
0 693 1 k = rate constant
where, k = rate constant k = · s- = 0.01 s- 1
69.3 Given that, dx = 1.5 x 10-2 mol L-1 min - I
dt
58. ·: On doubling the concentration of A, the rate of reaction k =? and [A ] = 0.5M
becomes two times.
1.5 X 10-2 = k X 0.5
: . The order of reaction w .r.t. A is I .
·: On doubling the concentration of B, the rate of reaction k = 1.5 X 10-2 = 3 X 10-2 min- I
does not change. 0.5
: . The order of reaction with respect to Bis 0. For first order reaction,
·: On doubling the concentration of C, the rate of reaction .ti . d ( ) 0.693 0.693 .
H a If-1epeno
I t I12 = - - = - -_-2 = 23 . I mm
becomes four times. k 3 x 10
: . The order of reaction w ith respect to C is 2. 65. The reaction is said to be of second order if its reaction rate is
: . The overall order ofreaction = I + 0 + 2 = 3. determined by the variation of two concentration terms of
59. For first order reaction, reactants.
k = 2.303 log _ a_ CH 3COOCH 3 + NaOH - CH3COONa + CH30
t a-x is an example of second order reaction.
k = 2.303 lo 33.05 = 2 x 10- 3 min-1 66. p 1 = 80 kPa, (f 112 ) 1 = 350 s
10 g 33.05 - 6.25 P2 = 40 kPa, (t112h = 175 s
Constant values of k calculated for different times, shows first 80 = 350 =2
order reaction. 40 175
60. Given that, k = 2.34 s- 1 f!J_ = (t1d1 = a,
Unit of 'k' suggest that the reaction is of first order, hence for Tst Pi (t112h a2
Time --+
order reaction, ⇒ t I12 oc a (zero order reaction)
_ 0.693 _ 0.693 _ 0 30 67. Rate becomes xY times if concentration is made x times of a
1112------- • S
k 2 .34 reactant giving /h order reaction.
444 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Rate= k [A]"[B] m 78. 2A + B - C
Concentration of A is doubled hence x = 2, y = n and rate Rate= k [A][ BJ It represents second order reaction,
becomes= 2" times. Concentration of B is halved, hence x = 11 2 Thus, unit of k is M- 1 s-1.

(2I)"'
:. Hence, option (a) is false.
and y = m and rate becomes = times T50 is dependent of concentration but not constant.

Net rate becomes = (2)" ( 1r times = (2)"- Ill times.

:. Hence option (b) is false.
_ _!__
2
d [A]= d [Cl, thus option (c) is correct.
dt dt
2 79. r <>< [CO] 2 and r' <>< [2CO] 2 and r' oe 4 [CO] 2
68. ( ~;) = k[NO] [O2 ]
r' 4 [CO] 2
Hence, - = r' = 4 r
nNo "o2 dx
-
k 2 r [CO] 2
=k ( - ) 2(
- ) ⇒( ) = - 3 (,'No) (no)
2
V V dt V
80. Rate= k [NOBr2 ][NO]

(!)• k((~t,) •8(!)

... (i)
But NOBr2 is in equilibrium

Keq = [NOBri ] ⇒ [NOBr 2 ] = Keq[NO][Br2 ] ...(ii)

[NO][Br2 ]
69. The ha lf-life period of a first order reaction is independent of the Putting the [NOBr2 ] in (i)
. .. l . f h 0.693
1mt1a concentration o t e reactant. tt12 = - - Rate= k · Keq [NO] [Br2 ] [NO]
k
Hence, rate= k · Keq [NOf[Br2 ]
1
70. If- -2 versus time is a straight line then the order of reaction is
[Al Rate = k' [NOf[Br2 ]
third. where, k' = k · Keq
71. Order may or may not be equal to molecularity. The order, of reaction with respect to NO(g) is 2.
72. 2Np 5 ~ 2N2O 4 + 0 2 is bimolecular but of first order. 81. For first order reaction, half-life period is independent of initial
concentration.
73. Given, R 1 = k[A f[B]
82. Pseudo first order reactions are those reactions w hich are not
According to question, R2 = k[ 3 A f [ 2B] truely first order but show first order kinetics under specifie
=kX9[Af2 [B] conditions. For example, acidic hydrolysis of an ester and
hydrolysis of cane sugar.
= 18 x k [ A f[ B] = 18 R1
. In 2 0.693
83. F or fi1rst ord er reaction, t 112 = - or t 11 2 = - -
74. C12H22O11 + H2O Dil-acid) C6Hl2O6 + C6Hlp6 k k
Excess Glucose Fructose 0.693
When one of the reactant is present in large excess, the second 84. We know that, t 112 = - -
k
order reaction confirms to the first order and is known as pseudo
or k = 0.693 = 0.693 = l .44 x 10-3 s-1
unimolecular reaction.
t 112 480

75. N =N 0 x(¾)" 85. For the homogenous gaseous reaction,

A+ B ~ C, the rate law is
I N 0 =N0 x (')" n=3
8 2 dx=k[A][B] ork= dx molL-t
dt dt x [Al[ BJ time x mol L- 1 x mo! L-1
T= 11 X t 112 = 3 X 14 = 42 s
76. The rate of zero order reaction is independent of the concentration or unit ofrate constant 'k' is mo1-1 L time-• or mo1-1 L s- 1.
of the reactants or the concentration of the reactant do not change
86. A + B -➔ C + D
with time. Thus, the rate of reaction remains constant.
dx dx Rate (r) = k[A ]° [BJ b ...(i)
- =k (a-x) O ⇒ - =k or Rate=k
dt dt 2r = k[2A ] [BJ b
0
...(ii)
77. The rate for first order reaction is expressed as 3r=k[Aj°[9B]b ... (iii)
A- Products Rate = - d[ Al, Rate = k[ A ] Dividing Eq. (ii) by Eq. (i)
dt
2 = 2° or a= I
and the rate constant (k) is given as
Dividing Eq. (iii) by Eq. (i)
k = 2.303 log [A0 ]
t [ A, l 3 = 9b 3 = 32b or 2b = I or
or b = 112
. I 3
-k= - t - log [A,] So, order of reaction = I + - = -
or 2 2
2.303 [ A0 ]
 Chemical Kinetics I 445
87. 2NO --4 N 2 + 0 2 97. Given, N O = initial concentration = I
Rate= k [NOf N = concentration after time I = 1/ 8

⇒ N = No Gr or½= IGr
Hence, order of reaction is 2. H 2 + 12 --4 2HI 3
Rate = k [H2 ][ 12 ) k=6.9xl0- s-•
Hence, order of reaction is (I + 1) = 2 Therefore, these reactions
0.693 0 693
are most likely to be elementary reactions that occur in one step. 11=31112 = - - · = I 00s
k 6.9 X 10-3
88. Let, initial concentration = a
T = n X 1112 = 3 X 100= 300 s
. I . 2
F ma concentrat10n = a - - a = -
a
:. After 300 sit w ill be reduced to 1/ 8oforiginal concentration.
3 3
2.303 a 98. Options (a), (b) and (c) are correct for order of reaction but
1213 = - - log - - option (d) is not correct because order of a reaction can be in
k a/ 3 fraction or zero or complete positive and negative number.
2 303 13
· lo 3= 2.0 1 X 10 S 99. There are two different reactants (say A and B).
5.48 X l0-l 4 g
A + B --4 Product
89. The rate law for the reaction is as Thus, it is a bimolecular reaction.
dx 2 o 2
r = - = k(A) (B) (C) = k (A) (B) If dx =k[A][B]
di di
On increasing the concentration of A, B and C two times. It is second order reaction.
/ = dx = k (2A) (2 B)2(2C)0 = 8k (A) (B)2 dx)
di
If, ( di = k [ A ] or = k [ B]
Thus, the rate increases eight times. It is first order reaction. Molecularity is independent of rate, but is
90. The order of reaction is zero. Suppose the following reaction takes the sum of the reacting substances thus it cannot be unimolecular
place. reaction.
A + B --4 Product 100. A --4 Product
1
Rate= k [A ][Bf Initially a 0
Order=!+ (-1)=0 After time t (a -x) X

a
91. Combination of H 2 and Br2 to give HBr is a zero order reaction as
the rate of reaction is not affected by the concentration of reactants .
After t 11 4
(a-¾) 4
hv For the first order kinetics,
H 2 + Br2 --4 2HBr
92. For nth order reaction the tmit of k is expressed as k = 2. 303 log(- a - .)
1 I a-x
conc.< - ,q C 1• Hence, for second order reaction, the unit of rate
4
constant is as conc.<1 - 2J C 1 or conc.- 1 C 1. 2.303 a 2 ·303 log - 0.29
k = - - log - ⇒ 1114 = 3 =- -
93. For zero order reaction, integrated rate equation is t114 3a k k
kl=[A] 0 - [ A] 4
a 101. For first order reaction,
If [ A) 0 = a,[A]= - , t= 1112
2 k = 2.303 log _ _a_= 2.303 log-2-
k 1112 = a -
a
2 k ⇒ l112 = 2, ⇒ f112 = 2 k
a a
~2 G-~ ~2 ~-rj

'112 °" a :. 2.303 log 2 = 2.303 log__!!_

94. For zero order reaction, t112 I a/4
1
mol-L- I L-1 s - I ⇒ 2.303 X 0.3010 = 2 _ X log
Rate= k [A f = k = - - =mo 303 4
s t,12

95. For an nth order reaction, t 112 °" ~ t _ 0.30 10 _ 0.3010 _ I h

a
112
- log 4 - 0.6020 - 2
:. For first order reaction, 1112 °" ~ °" a
0
. 102. X (g) --4 Y (g) + Z (g)
a
The reaction is a first order reaction.
96. Given, R1 =k[Af [B J
Hence, k = 0.693 = 2.303 log - a-

1r
Let concentration of Bis changed by x times. t112 t (a-x)
0.693 = 2.303 _ a_
Then, R2 = k ( [xB)= k x ¾ [Af [ BJ 10
10 I ga/10
X ,2 2.303 X IO I 0 .
= or t = - - - - x og 1 = 33 mm
4 xk[A J [BJ as R2 =Ri,thusx=4.
0.693
446 I Chapterwise & Topicwise Engineering Entrances Solved Papers

103. Rate= k [NO2 [CI] Topic 3 Temperature Dependence of

Hence, rate determining step is NO2CI - NO 2 + CI the Rate of a Reaction and
104. A+ B - C Collision Theory of
On doubling the concentration of A, rate of reaction increases by Chemical Reactions
4 times.
:. Rate oc:[Af (w.r.t. A) t. Iog -k2 = Iog -11 = -Ea ( -
T2 -Ti
-)
However, on doubling the concentration of B rate of reaction k 1 t2 R T1 · T2
increases two times.
:.Rateoc: [B)(w.r.t. B)
lo
48
= _!;__ ( JO ) ⇒E = 78.0 kJ mol-1
g 4 8.314 300 X 290 a
Thus, overall order of reaction = 2 + 1 = 3.
2. If a plot is drawn between 1/T and Ink then according to
105. I 0% of the reaction is completed in 20 min. Next 20% of the Arrhenius equation,
reaction will be completed in next 20 min. E
Ink = lnA- - a
Hence, I 0% + 9% = 19% of the reaction will be completed in RT
20 + 20 = 40 min. Here, slope= - Ea ⇒ - 1 x 104 = _!;__
106. For first order, R 8.314
-K Ea =8.314 X 104 1=83.14 kJmol- 1
log [CJ = - - + log [C ] so that the plot of log[C)
2303 3. From Arrhenius equation,
-K
versus twill be linear with slope= - - and intercept= log [C 1· K = Ae-E.IRT, on taking log, we get
2303
E
logk = logA - a
2.303 RT
f l~ lope =2.3i3 For reaction I, log k 1 = log A -
Ea1
.. .(i)
loge ~ 2.303RT
Ea2
t- For reaction II, logk2 = logA - ...(ii)
2.303 RT
Thus, the plot of log [C] decreases linearly with t for first order
reaction. Eq. (i) -Eq. (ii), we get,
107. From the unit ofrate constant (i.e. s-1~ it is clear that the reaction Iogk 1 - Iogk2 = logA -
Ea1 f
-llogA
Ea2 l
is of fi rst order. 2.303 RT 2.303 RT j
2Np5 - 4NO2 + 0 2 lo ~ =- Eal + Ea2
Hence, for first order reaction, k· = -
. 2.303
- Iog -Po g k2 2.303 RT 2.303 RT
t P, I
2 303 5 5 log2 = - - -(-E01 + E02 )
5 2.303 RT
: . 3.38 x 10- = · log 00 or log 00 = 0.00880
!Ox 60 p, P,
or Ea2 = E01 + 2.303 RT log2
500 . 500
- = anti log 0.00880 = 1.02 Pr = - = 490 atm Thus, Ea2 > Ea1•
Pr 1.02
4. Given k = kik3
108. For the reaction A ➔ B. On increasing concentration of reactant , k2
by 4, rate becomes double. From Arrhenius equ ation, k = Ae-Eal RT
Hence order of reaction is 1/2. Ae- Ei / Rr . Ae- E3/ RT
2.303 a Ae- Ea/ RT = -----,=--,-,=--
Ae- E2 / RT
109. t = - - lo g - -
k (a-x)
Ea = E 1 + E3 - E2 = 60 + 10 - 30
If t=t114;x=al4 = 70 - 30 = 40 kJ mol-
1

2.303 I a 2.303 I 4
1114 = - k - og (a - I /4a) = - k - og3
S. From Arrhenius equation, log k 2 = ~ (_!_ - _!_)
k 1 2.303R T2 T1
110. A - Product
Given, k 2 = 2, T2 = 3 IOK ⇒ T1 = 300 K
_d[ A]=k [Af k1
dt I
On putting values,
Units of k 1 = M s- 1

B-
d[B]
Product or - - - = k2 [ B] ⇒
lo 2 - -Ea
g - 2.303 X 8.314 310
(-1--_I_)300
dt
Units of k 2 = l s-
1 ⇒ Ea = 53598.6 J/mol
= 53.6 kJ/ mol
 Chemical Kinetics I 447
6. By the increase in temperature the activation energy decreases. 14. In the given grap h, Ea = E,, + l'l H
So, the rate of reaction increases. here temperature difference is
20 K . At IO K, the rate constant is doubled. Therefore, here is four where, E: = activation energy of reverse reaction
times. Hence, ki = 0.25. 150 = E,, + 100
E;, = 50 kJ
7. 10 ~ 20 ~ 30 ~ 40 ~ 50 --1.4
15. By increasing IO K temperature the rate of reaction becomes
double. When temperature is increased from 303 K to 353 K, the
60 ~ 70 ~ 80 256
> 90 ~ 100 O

rate increases in steps of IO and has been made 5 times. Hence,

So, increase in reaction rate is 512. the rate of reaction should increase 25 times i.e. 32 times.
8. Ni(g) + 3H 2 (g) ~ 2NH 3 (g) + 22kcal 16. k = Ae- EalRT,
·: Activation energy for the forward reaction = 50 kcal As temperature increases k increases exponentially.
:. Activation energy for the backward reaction 17. Comparing the slope and intercept of the given equation with the
= 50 + 22 = 72 kcal following Arrhenius equation,
E
9. Energy of activation is given by log k = - a + log A
2.303RT
r
log k 2 = ____!!__g_ T2 - T 11
k 1 2.303R T1T2 l J Hence, log A = 6 i.e. A = I<f s- 1
Comparing slope gives Ea = 38.3 kJ/mol
Here, kz = ~ T1 = 27°C = 300 K, 18. For first order reaction,
k1 10'
_ 2.303RT T2 l k1
Ti =-3°C=270K E , - - - - 1- og - ... (i)
(T1 - Ti) k1
lo r
~ _ ___!iE__ 270 - 3001
l
g 10 - 2.303 R 270 x 300 J
... (ii)
- I =- ~ 30
2.303R 270 X 300
Given, E 1 > E2
Ea = + 2.303 X 2700 X R J mol- 1 2.303RT1T2 l k 1 2.303RT1T2 I k2
⇒ - - - ~ og- > - - - ~ og -
= + 2.303 x 2.7 x R kJ mo1- 1 (T1 - T2) k1 (T1 - T2 ) k2

10. For every 10°C rise of temperature, rate is doubled. Thus, k; k;

- >-
temperature coefficient of the reaction = 2 k, ki
When temperature is increased by 50°, rate becomes 19. According to collision theory,
= 250/ 10 = 25 times= 32 times (i) The reaction rate depends on collision frequency and
effective collisions. For a molecule to have effective
11. A ~ B, A ~ C, By Arrhenius equation, collision it should fulfill two conditions; proper orientation
R1=i e-Ea1IRTandk2=le- Ea2IRT and sufficient energy.
(ii) The collision rate i.e. the number of collisions taking place
(A' is Arrhenius constant) (Since, Eai = 2Ea 1) in unit time per un it volume is also termed as collision
k2 = A' e-2Ea1IRT frequency (Z) and is given by
2 i
A'e- EallRT E IRT Z = 1tn. (j uav
t =e al ✓2
A e- iEalRT
(iii) Greater the temperature, greater w ill be the collision rate.
k, = k2 ~al I RT 20. For a first order reaction, Arrhenius equation is given as
12. Arrhenius equation is, k =A. e-Ea!RT
Rate constant, k = Ae- Ea I RT w here, Ea = energy of activation
k = Ae- 2.303 RT! RT ⇒ !!:._ = e- 2303 k2 e- Ea l R1j
A -k
·1
= e- Ea/RT2
On solving, we get!!:.__ = Io- 1 = eEal RT2 - Ea I R1j
A
13. Ea (A ➔ B) = 80 kJ mol-
1
=e; (__!_ _ __!_)= e; (Ti -T, )
Heat of reaction (A ➔ B) = 200 kJ mol-
1 T2 T1 T 1 T2
For (B ➔ A) backward reaction, Taking log on both the sides, we get
Ea (B ➔ A)= Ea (A ➔ B) + heat of reaction
= 80 + 200 = 280 kJ 1nol-
1 k
log ---1. = log eEa
R (T -T) = __E (T-T1)
_ 2 _ _t a_ _2
__
k1 T1 T2 2303R T1 T2
448 I Chapterwise & Topicwise Engineering Entrances Solved Papers

28. A2 + 8 2 ~ 2A B
/ Threshold energy(Er)
Ea (forward)= 180 kJ mol-1

21. )'! T\ f :~°'of,,_ Ea (backward)= 200 kJ mo1-1

In the presence of catalyst

j :. : : : :~J:: : i:;~. ~;,.,

~ A
of ~, ,eact;oo
Ea (forward)= 180 - 100 = 80 kJ mol- 1
Ea (backward)= 200 - I 00 = I 00 kJ mol- 1
Reaction coordinate ---+ l'l H = Ea (forward) - Ea (backward)
= 80 - 100= - 20 kJ mo1-1
where,
Ea = activation energy of forward reaction 29. Arrhenius equation is written ask= Ae-E.I RT
E; = activation energy of backward reaction Taking logarithm, above equation may be written as
E I
The above energy profile diagram shows that Ea > E; In k = In A - ___!!_ x -
The potential energy of the product is greater than that of the
R T
reactant, so the reaction is endothermic. In k 1 = In A - Ea x __!__ ...(i)
Ea =E; + M R Tl
E I
E1 = Ea OT E 1 > E~ In k2 = In A _ ___!!_ x - ...(ii)
R T2
22. Number of collisions of one molecule/unit time = X
Subtracting the Eq. (i) from Eq. (ii)
Ea r I
Number of collisions of N molecules/unit time= NX.
I 7
As in one collision, two molecules are involved, collision
frequency= NX / 2.
In K2 - Ink, =RlT, - TzJ
23. Given, k1 = I 0 10e- 20,000JT k2 Ea r I I7
k2 = 1ot2e-24jj()('JT k1 = k2 ln~=RlT1 -T2J
JOI0e- 20,000/T = JO12e-24ti06/T 30. k=A e-E.i nr
- 20,000 24ti()6 4ti()6 k = rate constant
e- T- + - T- =!Ozer= 102 A = pre-exponential factor, frequency factor
On taking log both sides, Ea = activation energy
4606 = lo 102 R = gas constant
2.3O3T g T = temperature
4606 31. Arrhenius equation, k = Ae-EI RT
2 lo 10 X T =
g 2.303
4606 In k = In A - __!!_
T= ----
2.3O3 X 2
RT
E
or logk = log A- - - - -
= 4606 = IOOOK 2.303 RT
4.606 Hence, Eis calculated w id1 the help of slope ofd1e graph plotted
24. According to formula k = PZe- E.,
RT, if Ea is less then K
between log k v, -.
I
becomes greater. T
25. When heat energy is supplied, kinetic energy of reactant 32. With increase in temperature reaction rate increases due to
molecules increases. This w ill increase the number of collisions increase in number of molecules having threshold energy.
and ultimately rate of reaction will be enhanced. 33. The collision frequency (Z) and rate constant (k) increase on
26. According to Arrhenius equation, the relationship between the increase of temperature.
activation energy and temperature is With the increase in temperature, the average kinetic energy of
k = Ae-Ea! RT the molecules increases and this leads to an increase in number of
-Ea collisions per unit time (Z). The rate constant (k) of a reaction is
⇒ log k = + log A also increases w ith increase of temperature.
2.303RT
34. k = Ae-EI RT
: . Activation energy decreases with rise in temperature, thereby
increasing the rate of the reaction. E is activation energy, it is that energy, which molecule must
27. Reactions having low Ea are fast reactions and reactions having have to give the product.
high Ea are slow reactions. If the Ea is high, then the munber of 35. The minimum energy required by reacting molecules to undergo
effective collisions w ill be small and the reaction w ill be slow. reaction is called activation energy.
 Chemical Kinetics I 449
. k + 10 Thus, Er> Eb
36. Temperature coefficient,= - ' - -
k, 39. Unit of A depends on unit of k.
10 3 40. Arrhenius equation gives relation of rate constant with
=2= - (k,+10= 10-3 Given) temperature.
kI
k =A. e- Eal RT
10-3
k= - IO X 10-4 = 5 X I0-4
' 2 2 On taking logarithm, we get In k = In A - ,!;_ In e
37. Arrhenius equation gives relation between rate constant and
RT
E
temperanire of a reaction. It can be written in many forms, as or In k= In A- - 0
k = Ae- Ea / RT RT
. rate of reaction at 35°C
where, k = rate constant 41. Temperanrre coefficient = - - - - - - - - - = 2
rate of reaction at 25°C
E0 = activation energy
T = absolute temperature Thus, increase in rate is two times, w hen temperanrre is increased
I 0°C. Hence, by the increase of 70°C (I 00 - 30 = 70°C), the
A = frequency factor
increase in rate will be
38. X ➔ Yis an endothermic reaction l:!Jl = + ve =(2)7 (·: 70° = 7 X 10°)
Eb = energy of activation of backward reaction
= 128times
Er= energy of activation of forward reaction
42. On increasing the temperature the kinetic energy of the reacting
l:!Jl = heat of reaction molecules increases and hence, nmnber of collisions increases.
Thus, Er= Eb + l:!Jl So, the rate of reaction will also be increased.
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 Surface Chemistry
QUICK REVIEW
• Surface chemistry deals with phenomenon that occur at the Adsorption Isotherm
surfaces or interfaces. Many important phenomenon such as • In Langmuir's model of adsorption of a gas on a solid
corrosion, electrode processes, heterogeneous catalysis, surface, the mass of gas striking a given area of surface
dissolution and crystallisation occur at interfaces. is proportional to the pressure of the gas. A plot of
extent of adsorption (xi m) versus pressure (p) at
Adsorption constant temperature is called as adsorption isotherm.
• It is the existence of a substance at an interface in a different • Langmuir's Adsorption Isotherm It is represented
concentration than in the adjoining bulk phase. It occurs due
to the presence of unbalanced forces at the surface. It is a by following the relation: ~ = _____!!f!__
m l+bp
spontaneous process (.tlG = Aff - TtlS) for the adsorption,
tlG, Mi and tlS must have negative sign. (where, a and bare two Langmuir's parameters)
• Adsorption is a phenomenon in which a substance is At very high pressure, ~ = ap; (l + bp "' bp)
unifonnly distributed throughout the substance. It occurs at m bp
uniform rates. X
(i) When adsorption and absorption occur side by side it is known At very low pressure, - = ap; (1 + bp"' 1)
m
as sorption.
.
(ii) The extent of adsorption of a gas on a solid depends on nanire Langmurr's adsorption
. . h
1sot em1 -x = -ac-
of the gas, pressure of the gas and the temperanrre of the gas. m l+bc
(iii) Activated charcoal is used to remove colouring matter from where, c is the equilibrium concentration, i.e. when
pure substances. It works by adsorption. adsorption is complete.
• In physisorption, particles of the adsorbate are held to the • Freundlich adsorption isotherm (when adsorbate
surface of adsorbent by weak van der Waals' forces. It is forms a monomolecular layer on the surface of the
non-specific, reversible and multimolecular in nature. Aff is adsorbent).
20-40 kJ mol- 1• It occurs at low temperature.
• In chemisorption, particles of the adsorbate are held to the
surface of the adsorbent by chemical forces. It is specific, where,
reversible and unimolecular in nature. Aff is m = mass of adsorbent, x = mass of the gas adsorbed
40- 400 kJ mo1- 1 • p = pressure, k = constant, n = integer
High temperature is favourable. n is always greater than 1, indicates that amount of the
• Methylene blue, from its aqueous solution is adsorbed on gas adsorbed does not increase as rapidly as the pressure.
activated charcoal at 25° C. For this process, the adsorption is At low pressure, ~ « p 1
accompanied by a decrease in enthalpy. m
At high pressure, ..::.. « p 0
m
 Surface Chemistry I 451
At moderate pressure, ~ oc p' 1" • In auto-catalysis one of the product acts as catalyst, e.g. the
m oxidation of oxalic acid by acidified KMn04 .
Freundlich adsorption isotherm·, ~ = k"C " where
. ' n > I • The catalytic reaction that depends upon the pure
m
substances of the catalyst and the size of reactant and
A graph of log xi mis p lotted against log p. The slope of
product molecule is called shape selective catalysis,
line and its y-axis intercept correspond to ..!. and log k e.g. zeolites are good shape selective catalyst.
n
respectively. • Enzymes are specific biological catalyst that possess well
y defined active sites. The action ofenzymes in living system
is to enhance the rate of biochemical reactions, e.g.
hydrolysis of urea.

/
/
~ a slope = J_
n
• Catalytic promoters when mixed with catalyst in small
quantities increase their efficiency while presence of
catalytic poisons destroy the activity of catalyst.
log k=lntercept
0 ~--------+X Colloidal System Solution
logp ---+ • Colloidal solution is of heterogeneous in nature, consists of
two phases dispersed phase and dispersion medium. In
• Plots of extent of adsorption (xi m) versus temperature at
lyophilic colloids, the particles of dispersed phase have a
constant pressure are called as adsorption isobars
great affinity for dispersion medium while in lyophobic
Catalyst colloids, there is no affinity between particles of dispersed
phase and dispersion medium.
• Catalyst is a substance which speeds up (positive catalyst)
and speeds down (negative catalyst) a chemical reaction • Sols of gold atoms and sulphur molecules are
multimolecular colloids. In these colloids, particles are held
without itself being used up. This phenomenon is known as
together by van der Waals' forces. Colloidal solutions of
catalysis.
starch, cellulose and proteins are macromolecular colloids.
Catalyst is specific in nature. It cannot initiate the reaction
or change the position of equilibrium. A positive catalyst Micelles are the cluster or aggregated particles fom1ed by
lowers the activation energy by providing a new pathway. association of colloid in solution (associated colloid).
In reversible reaction, the catalyst decreases the activation • The formation of micelles takes p lace above a particular
energy of both forward and backward reaction. temperature known as Kraft temperatw·e (Tk ) and above a
particular concentration known as critical micelle
• Homogeneous catalysis Reactants and catalyst are in
concentration (CMC).
same phase.
Potassium stearate is obtained by saponification of an oil or
e.g . acid hydrolysis of methyl acetate, hydrolysis of
fat. It is an example of micelle or associated colloid.
sucrose in presence of dilute hydrochloric acid.
HCI (/) • The process of conve1ting a freshly prepared precipitate
(i) CH 3 C00CH 3 (aq)+H 2 0 ( l ) ~ into colloidal fonn by the addition of suitable electrolyte is
CH 3 C00H(aq)+ CH 3 0H(aq) called peptisation and the electrolyte used for this purpose
H2S04(/) is called peptising agent.
(ii) C12 H 22 0 1I (aq) + H 2 0 ( / ) ~ In peptisation, ions of the electrolyte are adsorbed by the
Sucrose
C 6 H 12 0 6 (aq)+C6 H I2 0 (aq) particles of precipitates.
6
Glucose Fructose • Dialysis is the process of separating the particles ofcolloid
• Heterogeneous catalysis Reactants and catalyst are in from those of crystalloid by means of diffusion through a
different phase. suitable membrane. When dialysis is carried out by
V20, applying electric field, it is called electrodialysis.
e.g. (i) 2S02 (g) + 0 2 (g) ~ 2S03 (g)
Urea present in a collo idal solution cannot be removed by
electrodialysis whereas, NaCl, K 2 S04 , CaC1 2 , MgC1 2
can be removed.
... Pt(s)
(m) 2H 2 0 2 (/) ~ 2H 2 0(/) + 0 2 (g) • Movement ofcolloidal particles at random in zig-zag motion
(iv) Haber's process using Fe as catalyst is known as Brownian movement. This movement is due to
Fe(s) the bombardment of dispersion medium particles over
N 2 (g) + 3H2 (g) ~ 2NH3 (g) dispersed phase pa1ticles. It helps in providing stability to
colloidal sol by not allowing them to settle down.
452 I Chapterwise & Topicwise Engineering Entrances Solved Papers
• When light passes through a colloidal sol, its path becomes
visible because of scattering of light by particles. It is
called Tyndall effect and the illuminated path of the beam
is called Tyndall cone.
• E lectrophoresis is the migration of colloidal particles
towards the oppositely charged electrodes under the
influence of applied electric field. The coagulation of the
lyophobic sols can be carried out by electrophoresis.
• The minimum concentration of an electrolyte in
millimoles per litre of the electrolyte solution which is
required to cause the coagulation or flocculation of
colloidal sol is called flocculation value.
I dispersed phase and the dispersion medium are liquids.
Flocculation value oc - - - - - - -
Coagulating power
The coagulating behaviour of electrolyte is governed by
Hardy-Schulze rule. It states that,
(i) the ions having opposite charge to sol particles cause
coagulation.
(ii) coagulating power of an electrolyte is directly
proportional to the fourth power of the valency of the
ions causing the coagulation.
(iii) coagulation power of different cations in decreasing
order as follows:
Al 3+ > Mg 2+ >Na+ (to coagulate negative sols)
Topic 1
Adsorption
2014
1. In Langmuir's model of adsorption of a gas on a solid
surface [VITEEEJ
(a) the rate of dissociation of adsorbed molecules
from the surface does not depend on the surface
covered
(b) the adsorption at a single site on the surface may
involve multiple molecules at the same time
(c) the mass of gas striking a given area of surface is
proportional to the pressure of the gas
(d) the mass of gas striking a given area of surface is
independent of the pressure of the gas
2. In physical adsorption, the adsorbent and adsorbate are
held together by the [Manipal]
(a) ionic forces
(b) covalent forces
(c) van der Waals' forces
(d) H-bonding
3. For Freundlich isotherm, a graph of a log xi m is plotted
against log p . The slope of the line and its y-axis intercept,
respectively corresponds to [KCETJ
(iv) coagulation power of different anions in decreasing
order as follow.
[Fe(CN) 6 ]4- > Pot> so~- > c1 -
(to coagulate positive sols)
• Gold number is the term used to measure the protective
powers of hydrophilic colloids. It is defined as number of
milligrams of the dry protective colloid required to just
prevent the coagulation of 10 mL ofred gold sol when I mL
of I 0% solution of sodium chloride is added to it. Lower is
the value of gold number, greater is the protective power.
Gold sol is a multimolecular colloid.
• Emulsions are the colloidal solution in which both the
Emulsions are classified as oil in water (O/W) emulsions
(e.g . milk, vanishing cream, etc.) and water in oil (O/W)
emulsions (e.g. butter, cold cream, cod liver oil, etc.).
• Cow milk is a natural emulsion stabilised by casein.
• In case of cuts, bleeding is stopped by applying alum,
which acts as a coagulating agent.
• Liquid dispersed in solid medium- gel
• Liquid dispersed in gas- mist/fog (aerosol)
• Liquid dispersed in liquid-emulsion
I I
(a) - , k (b) log - , k
n n
I I
(c) - , log k (d) log - , log k
n n
4. Assertion (A) van der Waals' forces are responsible for
chemisorption. Reason (R) High temperature is favourable
for chemisorption.
The correct answer is [EAMCETJ
(a) A is incorrect but R is correct
(b) Both A and R are correct and R is the correct
explanation of A
(c) Both A and R are correct and R is not the correct
explanation of A
( d) A is correct but R is incorrect
5. What is the value ofl/ n in Freundlich adsorption isotherm?
(a) Between 2 and 4 in all cases [J&K CETJ
(b) Between 0 and 1 in all cases
( c) 1 in case of chemisorption
(d) 1 in case of physical adsorption
 Surface Chemistry I 453
2013
6. Methylene blue, from its aqueous solution, is adsorbed on 10. During the adsorption of a gas on the surface of a solid,
activated charcoal at 25° C . For this process the correct which of the following is true? [KCET]
statement is [JEE Advanced] (a) !!G> 0, till< 0, t:..S < 0
(a) the adso1ption requires activation at 25° C (b) !!G< 0, till< 0, t:..S < 0
(b) the adsorption is accompanied by a decrease in (c) !:'J.G < 0, till< 0, t:..S > 0
enthalpy (d) !:'J.G< 0, till> 0, t:..S < 0
(c) the adsorption increases with increase of temperature
(d) the adso1ption is irreversible 2011
11. During the adsorption of krypton on activated charcoal at
2012 low temperature [KCET]
7. The given graph/data I, Il, Ill and IV represent general (a) !:'J.H> 0and !!S < 0 (b) !:'J.H < 0and !!S < 0
trends observed for different physisorption and (c) !:'J.H> 0and t:..S > 0 (d) !:'J.H < 0and !!S > 0
chemisorption processes under mild conditions of
temperature and pressure. Which ofthe following choice(s) 2010
about I, II, Ill and IV is (are) correct? [HT JEE] 12. Which of the following is a wrong statement for
p constant p constant physisorption? [Guj CETl

i~~
(a) It is a reversible reaction
(b) Reaction requires an energy of activation
I. § _§ (c) The value of adsorption enthalpy is low
~ al (d) It generally occurs at a low temperature
.,:

T T 2009
200 K 13. Which of the following statements is incorrect regarding
250 K physisorption? [AIEEEl
(a) It occurs because of van der Waals' forces
III.
(b) More easily liquefiable gases are adsorbed readily
(c) Under high pressure it results into multin1olecular
layer on adsorbent surface
p
Af-lads = 150 kJ mo, 1 (d) Enthalpy of adsorption (t':'J.Hadsorption) is slow and
positive
(a) I is physisorption and Il is chemisorption
(b) I is physisorption and III is chemisorption 14. Rate of physical adso1ption increases with [Manipall
(c) IV is chemisorption and Il is chemisorption (a) decrease in surface area
(d) IV is chemisorption and Ill is chemisorption (b) decrease in temperature
8. Choose the correct reason(s) for the stability of the (c) decrease in p ressure
lyohobic colloidal particles. [HT JEE] (d) increase in temperature
(a) Preferential adsorption of ions from the solution 15. From the following which is not a surface phenomenon?
(b) Preferential adsorption of solvent on their smface (a) Corrosion [Kerala CEEl
from the solution (b) Crystallisation
(c) Attraction between different particles having (c) Heterogeneous catalysis
opposite charges on their surface (d) Water and its vapour in a dossed vessel
(d) Potential difference between the fixed layer and the (e) None of the above
diffused layer of opposite charges around the
16. FreUJ1dlich equation for adsorption of gases (in amount of
colloidal particles
x g) on a solid (in amount of mg) at constant temperature
9. According to Freundlich adsorption which of the following can be expressed as [DCEl
is correct? [AIEEE] X }
(a) log -= logp+ -logk
(a) !... <><- po m n
m X 1
(b) log - = log k + - log p
(b) !... O<. p' m n
m X
(c) - <><-pn
(c) !... <><- p"n m
m X }
(d) All of the above are correct for different range of (d) - = log p +- log k
m n
pressure
454 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2008
17. Which one of the following graphs represents Freundlich 22. Which of the following is not correct ? [DCE]
adsorption isothenn ? [BITSAT, AMU, EAMCET] (a) Enthalpy of physical adsorption is less compared to

(b) ,,,lb_ enthalpy of chemical adsorption

(b) Milk is an example of emulsion
( c) Physical adsorption increases with the increase in
temperature
( d) Smoke is an aerosol
log P ----+
2007

(c)loglt:: 23. Which one of the following characteristics is not correct for
physical adsorption ?
(a) Adsorption on solids is reversible
[UPSEE, MP PET]

log P ----+ (b) Adsorption increases with increase in temperature

( c) Adsorption is spontaneous
18. Freundlich adso1ption isothenn is [MHT CET] (d) Both enthalpy and entropy ofadsorption are negative
(a)~ = kp 11" (b) x = mkp
11
" 24. If (xi m) is the mass of adsorbate adsorbed per unit mass of
m adsorbent. p is the pressure ofthe adsorbate gas and a and b
11
( c) x I m = kp - ( d) All of these are constants, which ofthe following represents "Langmuir
19. Plot oflog xi magainst log pis a straight line inclined at an adso1ption isotherm" ? [Kerala CEE]
angle of 45°. When the pressure is 0.5 atm and Freundlich
(a) log(;)= log (i) + ± log p
parameter, k is 10, the amount ofsolute adsorbed per gram
of adsorbent will be (Jog 5 = 0 . 6990) [Kerala CEE] X b I
(b) - = - + -
(a) 1 g (b) 2 g (c) 3 g m a ap
(d)5g (e)2.5g
20. Which among the following statements are correct with (c) ~ = l+bp
m ap
respect to adsorption of gases on a solid?
I. The extent of adsorption is equal to kp11 according to (d) - 1 - = :!..+ p
Freundlich isotherm. (x i m) b a
II. The extent of adsorption is equal to kp 11 " according to
(e) - 1- =!: + _!_
Freundlich isotherm. (x i m) a ap
III. The extent of adsorption is equal to (I + bp) / apaccording
to Langmir isotherm. 25. Activated charcoal is used to remove colouring matter
IV. The extent of adsorption is equal to ap I (I + bp) according from pure substances. It works by [KCETJ
to Langmir isotherm. (a) oxidation (b) reduction
V. Freundlich adsorption isotherm fails at low pressure, where ( c) bleaching (d) adsorption
k, a and b are constants and p is pressure.
2005
(a) I and III (b) I and IV [Guj CET]
26. The extent of adsorption of a gas on a solid depends on
(c) II and III (d) II and IV [KCET]
21. Identify the correct statement for the adsorption of a real (a) nature of the gas (b) pressure of the gas
gas on charcoal at 1 atm and l5°C. [J&K CET] ( c) temperature of the gas (d) All of these
(a) Gases which are small in molecular size are adsorbed 27. Which of the following is not a characteristic of
more chemiso1ption ? [Guj CETJ
(b) Decrease in pressure increases the extent ofadsorption
( c) Gases which are easily liquefiable are adsorbed more (a) Aff is the order of 400 kJ
in quantity (b) Adsorption is irreversible
(d) Gas which has a behaviour similar to an inert gas is (c) Adsorption may be multimolecular layer
adsorbed more ( d) Adsorption is specific
 Topic 2
Catalyst and Catalysis
2014 2008
1. In the case of autocatalysis [KCET] 8. Hydrolysis ofurea is an example of [UPSEE]
(a) product catalysis (a) homogeneous catalysis
(b) solvent catalysis (b) heterogeneous catalysis
(c) reactant catalysis (c) biochemical catalysis
(d) heat produced in the reaction catalysis (d) zeo Iite ca ta1ysis
9. An example for autocatalysis is [Jamia Millia Islamia]
2013
(a) oxidation of NO to N0 2
2. Which one of the following is an example of homogeneous
(b) oxidation of S02 to S03
catalysis? [Kerala CEE]
(c) decomposition of KC10 3 to KC! and 0 2
(a) Haber's process of synthesis of ammonia (d) catalytic conversion of water gas to methanol
(b) Catalytic conversion of sulphur dioxide to sulphur (e) oxidation ofoxaiic acid by acidified KMn04
trioxide in the contact process
(c) Catalytic hydrogenation of oils 2007
(d) Catalytic conversion of water gas to methanol 10. The action of enzymes in living system is to [Manipal]
(e) Acid hydrolysis of methyl acetate
(a) supply energy to tissues
2012 (b) create immunity
(c) circulate oxygen
3. Which of the following reaction requires catalyst? (d) enhance the rate of biochemical reactions
(a) S + 0 2 ~ S02 [Manipal] 11. A biological catalyst is [Manipal]
(b) C + 0 2 ~ CO2 (a) the N 2 molecule (b) an enzyme
(c) 2S02 + 0 2 ~ 2S03 (c) an amino acid (d) a carbohydrate
(d) All of the above V20s
12. 2S0 2 (g) + 0 2 (g) ~ 2S0 3 is an exan1ple for [KCETJ
2010 (a) neutralisation reaction
4. Catalyst in a reaction [MPPET] (b) homogeneous catalysis
(a) lowers the activation energy (c) heterogeneous catalysis
(b) increases the rate of reaction (d) ineversible reaction
(c) Both (a) and (b) 13. The efficiency ofenzyme catalysis is due to its capacity to
(d) initiates the reaction [Kerala CEE]
5. Which one of the following is an example for homogeneous (a) form a strong enzyme-substrate complex
catalysis? [KCET] (b) change the shape of the substrate
(a) Manufacture of sulphuric acid by Contact process (c) lower the activation energy of the reaction
(b) Manufacture of ammonia by Haber's process (d) form a colloidal solution in water
(c) Hydrolysis of sucrose in presence of dilute (e) decrease the bond energies in substrate molecules
hydrochloric acid 14. In homogeneous catalysis CWB JEE]
(d) Hydrogenation ofoil
(a) the reactants, catalyst and products are in the same
6. A catalyst is a substance which [WBJEE] phase
(a) increases the equilibrium constant of the reaction (b) the catalyst and reactants are in the same phase
(b) increases equilibrium concentration of products (c) the catalyst and products are in the same phase
(c) does not alter the reaction mechanism (d) the reactants and products are in the same phase
(d) changes the activation energy of the reaction 15. The decomposition ofhydrogen peroxide can be slowed by
7. The velocity of oxidation of oxalic acid by acidified the addition of acetamide. The latter acts as a [WB JEE]
KMn04 increases as the reaction progress. It is an example (a) detainer
of [UPSEE] (b) stopper
(a) promoters (b) catalytic poisons (c) promoter
(c) autocatalysis (d) inhibitors (d) inhibitor
456 I Chapterwise & Topicwise Engineering Entrances Solved Papers
16. In a chemical reaction, catalyst [OJEEJ 2006
(a) decreases the energy of activation 21. Active charcoal is a good catalyst because
(b) increases the energy of activation (a) made up of carbon atoms [Jamia Millia IslamiaJ
(c) does not change energy of activation (b) is very reactive
(d) None of the above (c) has more adsorption power
17. Assertion (A) Catalyst increases the rate of a (d) has inert nature toward reagent
reaction.
Reason (R) In presence of a catalyst, the 2005
activation energy of the reaction increases. 22. Which of the following reactions is an example of
The correct answer is [EAMCETJ heterogeneous catalysis? [AMUJ
(a) Both A and R are correct and R is the correct
(a) 0 3 + 0 ~ 202 (gas phase)
explanation of A
(b) Both A and R are correct but R is not the correct (b) 2C0(g) + 0 2 (g) ~ 2C02 (g)
explanation of A
(c) A is correct but R is incorrect 0
(d) Assertion is not correct, but Reason is correct II
(c) CH3- C- 0C2H 5 (/) + H 20(/)
18. Which of the following reaction is an exan1ple for 0
homogeneous catalysis ? [J&K CETJ H,S04 II
~ CH3- C- 0H(/) + C 2H 5 0H(l)
2
(a)2H 20 2 (/) Mn0 (s) 2H20(l)+02(g)
(d) C0(g) + 2H2 (g) eu,zno-cr:103 CH30H(/)
(b) 2S02 (g) + 02 (g) V 2 0s(s) 2S03 (g)

(c) 2C0(g) + 0 2 (g) NO(g) 2C02 (g) 23. Which of the following is an example for heterogeneous
catalysis reaction ? [EAMCETJ
(d) H 2 (g) + C 2H 4 ( g ) ~ C 2H 6 (g)
(a) 2S02 (g)+ 0 2 ( g ) ~ 2S03 (g)
19. A catalyst [Jamia Millia Islamia] (b) Hydrolysis of aqueous sucrose solution in the presence
(a) lowers the activation energy of aqueous mineral acid
(b) changes the rate constant (c) 2H 20 2 ( l ) ~ 2H 2 0(/)+ 02(g)
(c) changes the product
(d) Hydrolysis of liquid in the presence of aqueous mineral
(d) itself destroys in the reaction
acid
20. Identify the correct statement regarding enzymes.
24. In a reversible reaction, the catalyst [Guj CETJ
[Jamia Millia l slamia]
(a) increases the activation energy of the backward reaction
(a) Enzymes are specific biological catalysts that can (b) increases the activation energy of the forward reaction
normally function at very high temperatures (c) decreases the activation energy of both forward and
(T-J000K) backward reaction
(b) Enzymes are no1mally heterogeneous catalysts (d) decreases the activation energy of forward reaction
that are very specific in their action 25. Formation of ammonia from H2 and N 2 by Haber's process
(c) Enzymes are specific biological catalysts that
using Fe is an example of [J&K CETJ
cannot be poisoned
(d) Enzymes are specific biological catalysts that (a) heterogeneous catalysis (b) homogeneous catalysis
possess well defined active sites (c) enzyme catalysis (d) non-catalytic process
 Topic 3
Colloids and Emulsions
2014 2012
1. Peptisation involves [VITEEEJ 9. Which of the following will be the most effective in the
(a) precipitation of colloidal particles coagulation ofFe(OH)3 sol? [BITSATJ
(b) disintegration of colloidal aggregates (a) Mg 3 (P04 h (b) BaC12
(c) evaporation of dispersion medium (c) NaCl (d) KCN
(d) Impact of molecules of the dispersion medium on the 10. Four different colloids have the following gold number,
colloidal particles which one has most effective action? [ManipalJ
2. Potassium stearate is obtained by the saponification of an
(a) 5 (b) 10 (c) 15 (d) 13
oil or fat. It has formula CH 3 -(CH2 ) 16 -COOK. The
11. The colloidal solution is purified by the following process
molecule has a lyophobic terminal CH 3 and a lyophilic
tem1inal-COOK. Potassium stearate is an example of (a) disintegration (b) peptisation [MP PETJ
(a) lyophilic colloid [Manipal] (c) filtration (d) dialysis
(b) lyophobic colloid 12. All colloidal dispersions have [KCETJ
(c) macromolecular colloid
(a) low osmotic pressure
(d) micelle or associated colloid (b) no osmotic pressure
3. Gold sol is not [MIITCET] (c) high osmotic pressure
(a) a macromolecular colloid (d) very high osmotic pressure
(b) a lyophobic colloid 13. Milk is a kind of [OJEE, MPPETJ
(c) a multimolecular colloid (a) sol (b) gel
(d) negatively charged colloid
(c) emulsion (d) mixture
4. Cow milk, an example of natural emulsion is stabilised by 14. Negatively charged colloidal solution of clay in water will
(a) fat (b) water [RPETJ need for precipitation the minimum amount of [AMUJ
(c) casein (d) Mg 2 + ions (a) aluminium sulphate (b) potassium sulphate
(c) sodium hydroxide (d) hydrochloric acid
2013
5. The coagulating power of electrolytes having ions 2011
3 2 l 5. Which one ofthe following does not involve coagulation ?
Na+ , Al + and Ba + for arsenic sulphide sol increases in
the order [JEE Mains] (a) Formation of delta regions [KCETJ
(a) Al 3+ < Ba 2 + < Na+ (b) Na+ < Ba 2+ < Al 3+ (b) Peptization
(c) T reatment of drinking water by potash alum
(c) Ba 2 + < Na 2+ < Al 3+ (d) Al 3+ < Na+ < Ba 2 + (d) Clotting of blood by the use of ferric chloride
6. Lyophilic sols are more stable than lyophobic sols because 16. Associated colloid among the following is [Kerala CEE]
(a) the colloidal particles have negative charge [ManipalJ (a) enzymes (b) proteins
(b) the colloidal particles have positive charge (c) cellulose (d) starch
(c) the colloidal particles are solvent (e) sodium stearate
(d) None of the above 17. Which of the following has maximum coagulation power
7. In the case of small cuts, bleeding is stopped by applying with ferric hydroxide sol ? [Guj CETJ
potash alum. Here alum acts as [KCETJ (a) Cryolite (b) K 2 C 2 0 4
(a) fungicide (b) disinfectant (c) K 3 [Fe(CN)] 6 (d) K 4 [Fe(CN) 6 ]
(c) germicide (d) coagulating agent
8. When a beam oflight is passed through a collodial solution 2010
it [Ke rala CEE] 18. Which of the following electrolytes is least effective in
(a) is reflected (b) is scattered coagulating ferric hydroxide solution? [ManipalJ
(c) transmitted (d) absorbed (a) KBr (b) K 2 SO4
(e) refracted (c) K 2 Cr0 4 (d) K 4 [Fe(CN) 6 ]
458 I Chapterwise & Topicwise Engineering Entrances Solved Papers
19. Which is the wrong pair? [MP PET] 2008
T. Starch solution : sol 29. Among the following, the surfactant that will form micelles
II. Aq. NaCl : true solution in aqueous solution at the lowest molar concentration at
Ill. milk : emulsion ambient conditions, is [HT JEE]
TV. Aq. BaS04 : true solution (a) CH 3 (CH 2 ) 15 N+ (CH 3 h Br-
(a) Only I (b) Only III
(b) CH 3 (CH 2 ) 11 OSO3Na +
(c) Only IV (d) Only II
(c) CH 3 (CH 2 ) 6 COO- Na+
20. Mention the type of reaction to obtain Au (sol).
Reaction, 2AuC1 3 + 3HCHO + 3H2 O ~ 2Au(sol) (d) CH 3 (CH 2 )ll N+ (CH 3 h Br-
+ 3HCOOH + 6HCI
30. Gold numbers of protective colloids A, B, C and D are
(a) Hydrolysis (b) Oxidation [Guj CETJ
0.50, 0.01, 0.10 and 0.005, respectively. The correct order
(c) Reduction (d) Double decomposition
of their protective powers is [AIEEEJ
21. The size of colloidal pa1ticles is in between [JCECEJ
7 9 cm 9- 11
(a)D<A<C< B (b)C<B<D<A
(a) 10- - 10- (b) 10- 10- cm (c) A<C< B <D (d)B< D< A< C
(c) 10-5 _ 10- 7 cm (d) 10- 2 - 10- 3 cm
31. The continuous phase contains the dispersed phase
2009 throughout, example is [VITEEE]

22. Among the electrolytes Na 2 SO4 , CaC1 2 , Al 2 (SO4 hand (a) water in milk (b) fat in milk
(c) water droplets in mist (d) oil in water
~H4 Cl, the most effective coagulating agent for Sb 2 S 3 sol
lS [IITJEE] 32. Bleeding due to a cut can be stopped by applying ferric
chloride solution in the laboratory.
(a) Na 2 SO4 (b) CaCl 2 This is due to [Manipall
(c) Al 2 (SO 4 ) 3 (d) NH4 Cl
(a) coagulation ofnegatively charged blood pa1ticles by
23. The ion that is more effective for the coagulation of As 2 S 3
Fe 3+ ions
sol is [Kerala CEEJ
(b) coagulation of positive( y charged blood particles by
2
(a) Ba + c1- ions
(d) so~- (c) reaction taking place between ferric ions and the
haemoglobin forming a complex
24. Which one ofthe following impurities present in colloidal (d) common element, iron, in both F eCl 3 and haemoglobin
solution cannot be remove by electrodialysis?
33. Peptisation denotes [MHT CETJ
(a) Sodium chloride [Kerala CEEJ
(b) Potassium sulphate (a) digestion of food
(c) Urea (b) hydrolysis of proteins
(d) Calcium chloride (c) breaking and dispersion into colloidal state
(e) Magnesium chloride (d) precipitation of solid from colloidal dispersion
25. Which is more powerful to coagulate the negative 34. Blue colour of water in sea is due to [MHT CETJ
colloid? [UPSEE] (a) refraction of blue light by impurities
(b) Na 3 PO4 (b) refraction of blue sky by water
(a) ZnSO4
(c) AIC13 (d) K 4 [Fe(CN) 6 ] (c) scattering of light by water
(d) None of the above
26. Select wrong statement. [AMUJ
35. The basic principle ofCottrell's precipitator is [KCETJ
(a) If a very small amount of AICI 3 is added to gold sol,
coagulation occurs, but if a large quantity of AICI 3 is (a) Le-Chatelier's principle
added, there is no coagulation. (b) peptisation
(b) Organic ions are more strongly adsorbed on charged (c) neutralisation of charge on colloidal particles
surfaces in comparison to inorganic ions. (d) scattering of light
(c) Both emulsifier and peptising agents stabilised 36. The colour of sky is due to [KCETJ
colloids but their actions are different. (a) transmission of light
(d) Colloidal solutions are thermodynamically stable. (b) wavelength of scattered light
27. From the following which is not an emulsifier?[Guj CETJ (c) absorption of light by atmospheric gases
(a) Agar (b) Milk (c) Gum (d) Soap (d) All of the above
28. If liquid is dispersed in solid medium, this is called [DCEJ
37. Alloy is an example of [UPSEEJ
(a) sol (b) emulsion (a) gel (b) solidified emulsion
(c) liquid aerosol (d) gel (c) solid solution (d) sol
 Surface Chemistry I 459
38. Which of the following is not a property of colloidal 51. Which of the following is not correct ? [EAMCET]
solution? [UPSEEJ (a) Milk is a naturally occurring emulsion
(a) Heterogeneity (b) Particle size > 100 nm (b) Gold sol is a lyophilic sol
(c) Tyndall effect (d) Brownian movement (c) Physical adsorption decreases with rise in temperature
(d) Chemical adsorption is unilayere
39. The number of moles of lead nitrate needed to coagulate
52. The colloidal system ofa solid dispersed in liquid medium,
2 moles of colloidal [ Agl] i- is [Ke rala CEE]
is called [J&K CET]
(a) 2 (b) l (c) 1/ 2 (d) 2/3
(a) aerosol (b) sol (c) gel (d) foam
(e) 5/2
40. The phenomenon observed when a beam of light is passed 2006
through a colloidal solution is [J&K CET] 53. Size ofcolloidal particles is in the range [UPSEE]
(a) cataphoresis (b) dielectrophoresis (a)0.05mµ - 0.lmµ (b)25 µ- 30µ
(c) coagulation (d) Tyndall effect (c) 0.1 µ - 1mµ (d) 10µ - 20µ
41. In colloid particles, range of diameter is [BCECEJ 54. The disperse phase, dispersion medium and nature of
(a) 1 to 100 nm (b) 1 to 1000 cm colloidal solution (lyophilic or lyophobic) of 'gold sol'
(c) 1 to 1000 mm (d) 1 to 100 km respectively are [EAMCETJ
42. Which has least gold number ? [BCECEJ (a) solid, solid, lyophobic
(a) Gelatin (b) Starch (c) Albumin (d) Blood (b) liquid, liquid, lyophobic
(c) solid, liquid, lyophobic
43. Which one of the following is a lyophilic colloidal (d) solid, liquid, lyophilic
solution ? [DCEJ
55. Which of the following is not a method of preparation of
(a) Smoke (b) Gold sol colloidal solution ? [J&K CETJ
(c) Starch aqueous solution (d) Cloud
(a) Electrical dispersion (b) Peptization
44. Which of the following electrolyte will have maximum (c) Coagulation (d) Mechanical dispersion
flocculation value for Fe(OHh sol? [Jamia Millia Islamia]
56. The gold numbers of some colloidal solutions are given
(a) NaCl (b) Na 2 S below.
(c) (NH 4 hPO 4 (d) K 2 SO 4
Colloidal solution Gold number
2007 A 0.01
45. Sulphw· colloid is prepared by [MPPET] B 2.5
(a) mechanical dispersion (b) oxidation C 20
(c) electrical dispersion (d) reduction The protective nature of these colloidal solutions follow
46. Colour of colloids depend on which of the factors? the order [J&K CETJ
(a) Size (b) Mass [MP PET] (a)C>B>A (b)A>B>C
(c) Charge (d) Nature (c)A = B = C (d)B>A>C
47. When a sulphur sol is evaporated sulphur is obtained. On 57. Gold number is associated with [Guj CETJ
mixing with water sulphur sol is not formed. The sol is (a) electrophoresis (b) protective colloids
(a) lyophilic (b) reversible [KCET] (c) Tyndall effect (d) isotonic solutions
(c) hydrophobic (d) hydrophilic 58. Tyndall effect would be observed in [Guj CETJ
48. On adding l mL of solution of l 0% NaCl to 10mL of gold (a) solvent (b) solution
sol in the presence of0.25 g of starch, the coagulation is just (c) colloidal solution (d) precipitate
prevented. The gold number of starch is [Kerala CEE] 59. When dilute aqueous solution of AgNO3 (excess) is added
(a) 0.25 (b) 0.025 (c) 2.5 to KI solution, positively charged sol of Ag! is fom1ed due
(d) 25 (e) 250 to adsorption of [BCECEJ
49. The formation of colloid from suspension is [WB JEE] (a) NO3 (b) 0 2 (c) Ag + (d) K+
(a) peptisation (b) condensation 60. Tyndall effect shown by colloids is due to
(c) sedimentation (d) fragmentation [Jamia Millia Islamia]
50. Which ofthe following has maximum value offlocculating (a) scattering of light by the particles
power ? [WB JEE] (b) movement of particles
(a) Pb 2 + (b) Pb 4+ (c) Sr 2+ (d) Na+ (c) reflection of light by the particles
(d) coagulation of particles
460 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2005
61. Lyophilic sols are [IITJEE] 65. Lyophilic sols are more stable than lyophobic sols because
(a) irreversible sols the particles [Kerala CEE]
(b) they are prepared from inorganic compounds (a) are positively charged (b) are negatively charged
(c) coagulated by adding electrolytes (c) are solvated (d) repel each other
(d) self-stabilising (e) are heavy
62. The volume of a colloidal particle, Ve as compared to the 66. An example of dispersion of a liquid in a gas is [UPSEEJ
volume of a solute particle in a true solution Vs, could be (a) milk (b) vegetable oil
(c) foam (d) mist
(a) Ve "'103 [AIEEE]
Vs 67. Fog is a colloidal solution of [J&K CETJ
(b)Ve s:10- 3 (a) solid in gas (b) liquid in gas
Vs (c) gas in liqttid (d) gas in solid
(c) Ve "'1023 68. The concentration of electrolyte required to coagulate a
Vs given amount of As 2 S 3 sol is minimum in the case of
(a) magnesium nitrate [Guj CET, KCETJ
(d) Ve "' l
(b) potassium nitrate
Vs
(c) potassium sulphate
63. The disperse phase in colloidal iron (HI) hydroxide and (d) aluminium nitrate
colloidal gold is positively and negatively charged,
69. Pick out the statement which is not relevant in the
respectively. Which of the following statements is not
discussion of colloids. [Guj CETJ
correct ? [AIEEEJ
(a) Sodium aluminium silicate is used in the softening of
(a) Coagulation in both sols can be brought about by
hard water
electrophoresis
(b) Potash alum is used in shaving rounds and as a styptic
(b) Mixing the sols has no effect
in medicine
(c) Sodium sulphate solution causes coagulation in both
(c) Artificial rain is caused by throwing electrified sand
sols
on the clouds from an aeroplane
(d) Magnesium chloride solution coagulates the gold sol
(d) Deltas are formed at a place where the river pours its
more readily than the iron (III) hydroxide sol
water into the sea
64. An emulsifier is a substance which [KCETJ
70. An emulsion is a colloidal dispersion of [BCECEJ
(a) stabilises the emulsion (a) a liquid in a gas (b) a liqttid in a liquid
(b) homogenises the emulsion (c) a solid in a liquid (d) a gas in a solid
(c) coagulates the emulsion
(d) accelerates the dispersion of liquid in liquid

Answers
TOPIC 1 Adsorption
1. (c) 2. (c) 3. (c) 4. (a) 5. (b) 6. (b) 7. (a, c) 8. (a) 9. (d) 10. (b)
11. (b) 12. (b) 13. ( d) 14. (b) 15. (e) 16. (b) 17. (c) 18. (a) 19. ( d) 20. (d)
21. (c) 22. (c) 23. (b) 24. (e) 25. (d) 26. (d) 27. (c)
T0PIC2 Catalyst and Catalysis
1. (a) 2. (e) 3. (c) 4. (c) 5. (c) 6. (d) 7. (c) 8. (c) 9. (e) 10. (d)
11. (b) 12. (c) 13. (c) 14. (b) 15. (d) 16. (a) 17. (c) 18. (c) 19. (a) 20. (d)
21 . (c) 22. (d) 23. (c) 24. (c) 25. (a)
TOPIC3 Colloids and Emulsions
1. (b) 2. (d) 3. (a) 4. (c) 5. (b) 6. (c) 7. (d) 8. (b) 9. (a) 10. (a)
11. (d) 12. (a) 13. (c) 14. (a) 15. (b) 16. (e) 17. (d) 18. (a) 19. (c) 20. (c)
21 . (c) 22. (c) 23. (e) 24. (c) 25. (c) 26. (a) 27. (b) 28. (d) 29. (a) 30. (c)
31 . (c) 32. (a) 33. (c) 34. (c) 35. (c) 36. (b) 37. (c) 38. (b) 39. (b) 40. (d)
41 . (a) 42. (a) 43. (c) 44. (a) 45. (b) 46. (a) 47. (c) 48. (e) 49. (a) 50. (b)
51 . (b) 52. (b) 53. (c) 54. (c) 55. (c) 56. (b) 57. (b) 58. (c) 59. (c) 60. (a)
61 . (d) 62. (a) 63. (b) 64. (a) 65. (c) 66. (d) 67. (b) 68. (d) 69. (a) 70. (b)
 Explanations
Topic 1 Adsorption
1. In Langmuir's adsorption isotherm, the mass of gas striking a 7. Graph I represents physisorption as in physisorption,
given area ofsurface is proportional to the pressure of the gas adsorbents are bonded to adsorbate through weak van der Waals'
X k'p force. Increasing temperature increases kinetic energy of
as
m l + kP adsorbed particles increasing the rate of desorption, hence
amount of adsorption decreases.
2. In physical adsorption, the adsorbent and adsorbate are held
Graph III also represents physical adsorption as extent of
together by weak van der Waals' forces.
adsorption increasing with pressure.
3. According to Freundlich adsorption isotherm..:..= k/1" Graph II represents chemisorption as it is simple activation
m
energy diagram of a chemical reaction.
Taking log both side log..:.. = _!_ log p + log k Graph IV represents chemisorption as it represents the potential
m m energy diagram for the formation of a typical covalent bond.
8. Lyophobic sol, gets stabilised by preferential adsorption of ions
on their surface developing a potential difference between the
fixed layer and the diffilsed layer.
9. By Freundich adsorption isotherm
-X = k..p 1/n (in between low and high pressure)
m
X l
>< I E: Intercept = log k wheren = 1,- oc p (in low pressure range)
m
.8' y-axis
-logp when n is large,..'.:.. = k (independent of pressure)
m
(Graph between log!._ against log p)
m Thus, ..'.:.. oc p 0 (in high pressure range when saturation point is
m
4. van der Waals' forces are not responsible for chemisorption. reached).
These forces are involved in physisorption. For chemisorption,
high temperanire is favourab le. It increases with increase of
temperanire.
_/L (-k P)0C

0
5. Freundlich adsorption isotherm is given by X ~~ocp )

X 11 X l m
_:_ =kp n or log - = logk+ - logp
m m n

Graph between log..'.:.. and log pis a straight line w ith slope ..!. and
m n Pressure ( p)
intercept log k. Thus value of..!. lie between 0 and I in all cases.
n 10. During the adsorption of a gas on the surface of a solid, there is
decrease in surface energy, i. e. it is an exothermic process.
Therefore, !:lH < 0. Again when a gas is adsorbed, the freedom of
movement of its molecules becomes restricted. This leads to
slope =J... decrease in the entropy of the gas after adsorption. Therefore,
XIE: n t,,S < 0. From equation t'lG = t'lH - Tt'lS, t'lG can be negative if
0)
.Q
process is spontaneous. Since, adsorption process is a
spontaneous process, therefore, t'lG < 0.
} logk 11. Adsorption is an exothermic process, thus t'lH is negative
logp- (i.e.l:lH < 0). Moreover, adsorption results in more ordered
arrangements of molecules, thus entropy decreases (i.e. t,,S < 0).
6. Physical adsorption takes place with decrease in enthalpy, t'lG = !:lH - Tt,,S. Hence, low temperan1re favours d1e reaction.
thus exothermic change.
It is physical adsorption and does not require activation. 12. When the particles of the adsorbate are held to d1e surface of the
adsorbent by the physical forces, the adsorption is called physical
Thus, (a) is incorrect. Being physical adsorption !:lH < 0 thus,
(b) is correct. adsorption or physisorption. It is a reversible process and usually
Exothermic reaction is favoured at low temperature thus, (c) is occurs at low temperature. The value of adsorption enthalpy is
incorrect. low in this process. Tt forms multimolecular layers. No activation
Physical adsorption is always reversible, thus, (d) is incorrect. energy is required in this process.
462 I Chapterwise & Topicwise Engineering Entrances Solved Papers
13. Adsorption is an exothermic process, i.e. energy is released 23. As temperature increases desorption increases.
against van der Waals' force of attraction (physisorption). Adsorbent+ adsorbate~ Adsorbed state + M
Hence, /'Jf is always negative.
Adsorption is exothermic process (forward direction), desorption
14. Physical adsorption decreases with increasing temperature or rate is endothermic process (backward direction).
of physical adsorption increases with decreasing temperature. According to Le-Chatelier's principle increase in temperature
15. The phenomenon that takes place at the surface, are termed as favours endothermic process.
surface phenomenon. Among the given processes, all processes
24. Ifx I m is the mass of adsorbate per unit mass ofadsorbent, pis the
take place at the surface, so option (e) is correct.
pressure of the adsorbate gas and a and b are constants, then
16. According to Freundlich equation,
Langmuir's adsorption isotherm is given as
..:_ oc p lln or ..:_ = kplln ..:._ ___!!E._ I I+ bp
m m or - - - - -
m I + bp xI m ap
or log..:.. = logkp11" I I b
m -- = - + -
x/m ap a
X I
or log- = logk + - logp
m fl 25. Activated charcoal is used for decolourising and deodorising
17. When we plot a graph between log(x / m)and logp, a straight line
sugar solution during the process of manufacture of sugar due to
its adsorbing property.
with positive slope will be obtained. This graph represents the
26. Adsorption of a gas on a solid depends on
Freundlich adsorption isotherm.
(a) Nature of the gas and solid
/ 4-(~•P) (b) Pressure
X ,.,,,(~- p•) (c) Temperature (decreases with increase in temperature)
m
27. In case of chemisorption, adsorption is only monolayer. All other
options are correct about chemisorption.
Pressure (p)
Graph of Freundlich adsorption isotherm
Topic 2 Catalyst and Catalysis
18. Freundlich adsorption isotherm is
1. In the case of au tocatalysis the product catalysis the reaction.
xl m=kp 11n
2. Homogenous catalysis is that catalysis when the reactants,
Here p, k and n are constant. products and the catalysts are in the same physical state, i.e. in the
Note Freundlich isotherm is not applicable at high pressure. same phase. In the alternate (e) i.e. in the acid hydrolysis of
. 1sot1erm
. 1 . 1.s -X = k-p 1/n methyl acetate, the reactants methyl acetate, products H 2O and
19. Freundlich adsorplton equat10n catalyst (dil. HCI or dil. H 2SO 4 acids) are in the same (liquid)
m
phase. So, acid hydrolysis of methyl acetate is one of the example
On taking log both sides
ofhomogenous catalysis out of all other alternatives.
X I
log - = log k + - log p 3. Reaction (a) and (b) are exothermic and spontaneous so do not
m fl
X I need catalyst. On the other hand, conversion of SO2 into SO3
log - = log 10 + - log 0.5 need catalyst. Catalyst used for this reaction may be Pt nor V2O 5
m n (contact process) or NO (lead chamber process).
I V20s
(·: Slope= - = tan 8 = tan 45° = I) 2SO2 + 0 2 ---t 2SO 3
ll

log..:_ = I + ~ log (5 x 10-1) 4. A catalyst increases the rate of the reaction by decreasing its
m. I activation energy.

log..:_= I + 0.6990 - I = 0.6990 ⇒ ..:_ = 5.00= 5g 5. In homogeneous catalysis, reactants and catalyst are in the same
m m phase.
20. Extent of adsorption= kp 11n (Freundlich adsorption isotherm) Pt (s}
(a) SO2 (g) + O 2 (g) . . - SO 3 (g) (Contact process)
The amount of gas adsorbed does not increase as rapidly as the
ap It is an example of heterogeneous catalysis.
pressure. The extent of adsorption = (I + bp)
(Haber's process)
(Langmuir's adsorption isotherm) where k , a, bare constants and
pis pressure. It is an example of heterogeneous catalysis.
HCI (aq)
21. Gases which have high critical temperature, have strong van der ~
(c) C 12 H 22 0 11 (aq) + HzO(aq) C6H 12O6 + C6 H 12 0 6
Waals' forces of attraction and hence, are adsorbed to a greater
extent. It is an example of homogeneous catalysis.
22. Physical adsorption decreases with increase in temperature, (d) Oil(/) + Hz(g) (Hardening) fat
Pt(s)
whereas chemisorption first increases and then decreases with
increase in temperature. Thus, it is also an example of heterogeneous catalysis.

6. A catalyst changes the activation energy of the reaction. As a
result, the reaction follows an alternate path and the rate of
reaction will change.
7. When one of the products ofa reaction acts as a catalyst for that
reaction, the phenomenon is known as autocatalysis.
When KMnO4 solution is added to oxalic acid, the
disappearance of pink colour is slow at start but as soon as some
Mn 2+ ion are formed the disappearance ofcolour becomes fast.
2MnO4 + sept + 16W -----t 2Mn 2+ + I0CO2 + 8H2O
Catalyst
or 2KMnO4 + 5H2C2O4 + 3H2SO4 -----t
2MnSO4 + K2SO4 + 8H2O + I0CO2
Catalyst
Mn 2+ ion (or MnSO4 ) acts as catalyst in this reaction.
8. Enzymes are biological catalysts produced by living cells which
catalyze the biochemical reactions in living organisms.
Hydrolysis of urea by urease (enzyme) is an example of
biochemical catalysis.
0
II Urease
H 2N-C-NH2 + H p ~ 2NH3 + CO2
Urea
9. Autocatalysis is a process in which one of the product behaves as
a catalyst.
e.g. 2KMnO4 + 5H2C2O4 + 3H2SO4 -----t
K 2SO4 + 2MnSO4 + 8H 2O + I0CO 2
Acts as catalyst
The pink colour ofKMnO4 disappears slowly on reaction with
oxalic acid, but the rate of disappearance of colour fastens after
sometime due to the formation of MnSO4 which acts as
autocatalyst for the reaction.
10. The action of enzyme in living system is to enhance the rate of
biochemical reactions.
11. A biological catalyst is an enzyme.
V20s
12. 2SO 2(g) + 0 2 ~ 2SO 3 (g)
Solid
Topic 3
In this reaction reactants as well as the catalyst are present in
more than one phase hence it is an example of heterogeneous
catalysis.
13. The efficiency of enzyme catalysis is due to its capacity to lower
the activation energy of the reaction. Enzymes are biocatalysts
which increases the rate of reaction without being consumed in the
reaction. In case of equilibrium reactions, catalyst help in attaining
the equilibrium quickly without disturbing the equilibrium.
14. Homogeneous catalysis When the reactants and catalyst are in
the same phase, the catalysis is known as homogeneous
catalysis.
Mn0 2(,)
e.g. 2 KClO 3 (s) --➔ 2KCl(s) + 3O2(g)
15. The decomposition of H 2O 2 can be slowed by the addition of
acetamide. Acetamide act as an inhibitor.
Catalytic poisons or inhibitor are those substances which
decrease or inhibit the activity of catalyst.
16. In a chemical reaction the catalyst decreases the activation
energy of reaction and hence, increases the rate of reaction.
Surface Chemistry I 463
17. A catalyst increases the rate ofreaction because in the presence of
catalyst the activation energy of the reaction decreases.
18. When the reactants and catalyst are in the same phase, the catalysis
is known as homogeneous.
NO(g)
In this reaction both reactant and catalyst are in the gaseous phase.
19. A catalyst lowers the activation energy and increases the rate of
reaction. It is not consumed during reaction.
20. Normal optimum temperature of enzymes is between 25°C to
40°C hence (a) is false. Similarly, (b) and (c) are also false.
Enzymes have well defined active sites and their actions are
specific in nature.
21. Active charcoal has greater surface area. So, it has more
adsorption power.
22. CO(g) + 2 H2(g) Cu,Z,,O-Cri0 3 <•\ CH3 OH(l)
In this reaction, reactants and catalyst are in different physical
states, hence it is an example of heterogeneous catalysis.
In this reaction, reactant and catalyst are in different phase, hence
it is an example of heterogeneous catalysis.
24. A catalyst increases the rate of reaction by decreasing its
activation energy. In a reversible reaction, catalyst decreases
activation energies of both, forward and backward reactions,
equally, thereby increasing rate of both reactions equally. Thus,
equilibrium is approached quickly.
25. In heterogeneous catalysis, the reactant and the catalyst are in
different phases.
In the Haber's process the reactants are in gaseous phase while
catalyst (Fe) in solid phase. Hence, it is an example of
heterogeneous catalysis.
Colloids and Emulsions
1. Peptisation is a process in which freshly prepared precipitate
disintegrate into colloidal solution.
2. Potassium stearate is an example of micelle.
3. Gold sol contains particles ofvarious sizes having several atoms of
gold. Thus, it is a multimolecular colloid instead of
macromolecular colloid.
4. Cow milk is stabilised by casein.
5. According to Hardly Schulze rule, greater the charge on
oppositely charged ion, greater is its coagulating power. Since
arsenic sulphide is a negatively charged sol, thus, the order of
coagulating power is Na+ < Ba 2+ < Al 3+.
6. Lyophilic sols are more stable than lyophobic sols because the
colloidal particles are solvated the reaction.
7. B leeding is stopped by applying potash alum. Here potash alum
acts as a coagulating agent.
8. When a beam of light is passed through a colloidal solutions, it is
scattered.
464 I Chapterwise & Topicwise Engineering Entrances Solved Papers
9. According to Hardy-Schulze rule, coagulation power ions is
directly proportional to charge on ion.
·: Fe(OH)3 is positively charged colloid
: .It will be coagulated by anion.
(a) Mg3(PO4)i ~ 3Mg2+ + 2Po!-
(b) BaC12 ~ Ba2+ + 2Cl-
(c) NaCl
(d) KCN
·: PO[ has highest charge among the given anions.
: . MgiPO4)i is the most effective in coagulation ofFe(OH)3sol.
10. Protective power of lyophillic colloid is measured in terms of
gold number. Lower the value of gold number, better is the
protective power of a protective colloid. Thus, the order will be
(a)5 > (b) 10 > (d) 13 > (c) 15
11. Colloidal solutions are purified by dialysis and electrolysis
methods .
12. Colloidal particles are bigger aggregates. Thus, the number of
particles in the colloidal solution is comparatively small as
compared to true solution. Hence, the values of colligative
properties (e.g. osmotic pressure) are of smal I order as compared
to values shown by trne solutions at same concentrations.
13. An emulsion is a liquid-liquid has colloidal system. Tf a mixture
of two immiscible or partially miscible liquids is shaken, a
dispersion ofone liquid in the other is obtained which is termed as
emulsion, e.g. milk, vanishing cream, butter, cream etc.
14. (a) Ali(SO4)3 - 2Al3+ + 3SO~-
(b) KiSO4 - 2K+ + so~-
(c) NaOH - Na+ + OH-
(d) HCI - H+ + Cl-
Since, aluminium sulphate has maximum positive charge, thus its
congulating power is maximum. Therefore, for precipitation its
minimum amount will be required.
15. Coagulation is the phenomenon of conversion of colloidal sol
into precipitate while in peptization, a fresh precipitate is
converted into sol by adding electrolyte. Hence, it is clear that
peptization does not involve coagulation.
16. Sodium stearate is an example of associated colloids. Colloidal
solution of enzymes, proteins, cellulose and starch are the
examples of macromolecular colloids.
17. Ferric hydroxide sol is positively charged sol. Tt is coagulated by
negative ions. Larger the charge on anion, larger is its coagulating
power or smaller is its floccu lation value. Tn KiFe((N\], the
anion (Fe((N\]4-- has highest charge, therefore KiFe((N\] is
most effective in coagulating Fe(OH)3 sol.
18. Fe(OH)3 is a positively charged sol, thus coagulated by negative
ion (anion). Smaller the charge on anion, smaller is its
coagulating power or higher is its flocculation value.
(a) KBr - K+ + Br-
(b) K2SO4- 2K+ + sot
( C) K2CrO4 - 2K+ + Cro~-
(d) K4 [Fe((N\] - 4K+ + [Fe((N\:f-
·: Br- has smaller charge.
:.KBr is least effective in coagulating Fe(OH)3 sol.
19. BaSO4 is insoluble in water and thus, it does not form true
solution with water.
20. The gold sol is obtained by the reduction of AuCl 3.
2AuCl 3 + 3HCHO + 3Hp - 2Au + 3HCOOH + 6HCI
21. The size of colloidal particles is in the range of I 00 nm to I nm or
10-5 cm to I 0- 7 cm.
22. Sb2S3 is an anionic sol, therefore cation of highest valency (Al 3+
in the present case) would be most effective coagulating agent.
23. Since, As2~ is a negatively charged sol, the ion bearing the
highest positive charge, is more effective for its coagulation, Al 3+
has the highest positive charge, i.e. + 3, so it is more effective for
the coagulation of As2S 3 sol.
24. Electrolysis is the technique by whic h electrolytic impurities can
be removed. Hence, urea, being non-electrolyte cannot be
removed by this method.
25. Negative colloid is coagulated by positive ion or vice-versa.
Greater the valency of coagulating ion, greater will be
coagulating power.
(a) ZnSO4 - Zn 2+ + so!-
(b) Na 3PO4 - 3Na+ + PO!-
(c) AICl 3 - 3
Al + + 3Cl-
(d) K 4 [Fe(CN)s] - 4K+ + (Fe(CN)s]4--
Since, in AICl 3, the valency of positive ion (coagulating ion) is
highest, it is the most powerfbl coagulating agent among the
given to coagulate the negative colloid.
26. The phenomenon of the precipitation of a colloidal solution by the
addition of the excess of an electrolyte is called coagulation. When
oppositely charged sols are mixed in almost equal proportions,
their charges are neutralised. So, statement (a) is wrong.
27. The substances that stabilised emulsions are called emulsifiers.
Agar, gum and soap all were emulsifier while milk is an
emulsion, not an emulsifier.
28. When a liquid (dispersed phase) is dispersed in solid (dispersion
medium), the colloidal solution is termed as gel.
29. Sodium dodecyl sulphate (SDS) CMC (mm)> - 10
Hexadecyl trimethyl ammonium bromide (CTAB)
Note At a certain concentration surfactant molecules start to
aggregate and form micelle, the concentration is called
critical micellisation concentration (CMC).

30. H igher the gold number, lesser will be the protective power of
colloid.
31. The continuous phase contain the dispersed phase throughout.
Example is water droplet in mist.
32. B leeding due to cut can be stopped by applying FeC1 3 or alum
solution. This is due to coagulation of negatively charged
colloidal blood particles (albuminoid substance) by positively
charged Fe3+ ions.
These substances are used as styptic (which check the flow of
blood).
33. The dispersal of a precipitated material into colloidal solution by
the action of an electrolyte in solution is called peptisation and the
electrolyte is called a peptising agent.
34. The colour of a colloidal solution depends on the wavelength of
the light scattered by the dispersed particles, which in turn
depends on the size and the nature of particle. The colour of water
in sea is blue due to the scattering of light by water.
35. In Cottrell 's precipitator, the charged particles are attracted
towards the walls of precipitator, here they lose their charge and
coagulate.
Hence, the basic principle of Cottrell's precipitator is the
neutralisation of charge on colloidal particles.
36. The blue colour of sky is due to Tyndall effect, i.e., the colloidal
particles adsorb light, become self luminous and then scatter light
of different wavelengths in all possible directions.
37. Alloy is a mixture of two or more elements which has metallic
properties. Brass is an alloy of Cu and Zn. Alloy is an example of
solid sol. Some kinds of steel are alloys of Fe and C and can be
considered as solid solutions in which carbon atoms are located in
some of the space between iron atoms.
38. Suspension Colloidal solution True solution
Particle size> I00 nm 1 nm - I00 nm < I run
Colloidal solution is a heterogeneous solution which contains
particles of intermediate size. The particles of a colloidal solution
have diameters between 1 to 100 nm. Colloidal solution shows
the optical property (i.e. Tyndall effect and Brownian
movement).
2 54. Colloidal solu tion of gold is obtained when dispersed phase is
39. In lead nitrate, lead is present as Pb + ion. While there is only one
2 solid and dispersion medium is liquid.
negative ion per mole of colloid. Hence, one mole Pb + can
coagulate two moles of[AgI]r.
40. On passing a beam of light through a colloidal solution, the
colloidal particles adsorb light energy and then emit it in all the
possible directions. T his phenomenon is called scattering of light
or Tyndall effect.
No te Tyndall effect is not observed in true solutions.
41. In colloid particles, the range of diameters i.e. particle size is of
the order of I to 100 nm.
42. The gold number of the given compounds is
Gelatin - 0.005 to 0.1
Starch - 15 to 25
Albmnin - 0.1 to 0.2
B lood or haemoglobin - 0.03 to 0.07
So, gelatin has the least gold number.
Surface Chemistry I 465
43. Starch is an example of lyophilic (water loving) colloidal
solution. Lyophilic colloids are those colloids which form
colloidal solution in contact wid1 water.
1
44. Flocculation value oe - - - - - - -
Coagulating power
Fe(OH)3 is a positively charged sol.
To coagulate Fe(OH)3, negative charge e lectrolyte is used and
greater the value of negative charge, coagulating power w ill be
strong. Among the given electrolytes, NaCl has lowest
coagulating power.
So, its flocculation value will be maximum.
45. Sulphur sol is prepared by the oxidation of H 2S by bromine.
Br2 + H 2S ----t 2HBr + ~
46. Colour of colloidal solution depends upon particle size. As d1e
particles size increases, the colour of gold sol changes from red to
blue and finally to golden.
47. Hydrophobic sol are irreversible in nature. T hey have no affini ty
between the dispersed phase and the dispersion medium (H 20).
Further once precipitated, they do not form the colloidal sol by
simple addition of water.
48. Gold number is d1e number of milligrams of a hydroph ilic colloid
that will just prevent the coagulation of IO mL of a gold sol on
addition of I mL of I 0% NaCl solution.
:. Gold number= 0. 25 x 1000 = 250
49. The formation of colloid from suspension is called peptisation.
The process of converting a precipitate (suspension) into
colloidal particles by adding suitable electrolyte is known as
peptisation.
50. The phenomenon of change of colloidal state to suspension state
is called flocculation of colloidal solution. According to
Hardy-Schulze rnle, d1e flocculating power of electrolyte
increases with valency of ion of electrolyte.
51. Gold is a lyophobic sol.
52. When the dispersed phase is solid and dispersion medium is
liquid, then the colloidal system is called sol.
53. The size of colloidal particle is 0.1 µ - Imµ or I 00 nm - I nm.
Substances like metals caru1ot be brought into the colloidal state
simply by bringing them in contact with water and therefore,
special methods are devised for the purpose.
Hence, d1ey are known as hydrophobic or lyophobic colloids.
55. Colloidal solution is prepared by electrical dispersion, peptization
and mechanical dispersion. It is not prepared by coagulation
because coagulation is the phenomenon of the precipitation of
colloidal solution by the addition of the electrolyte.
56. Smaller the value of gold number, greater will be the protecting
power of the protective colloid.
Hence, protective nature of A, Band C is as
Colloidal solution A > B > C
Gold number 0.01 2.5 20
57. Gold number is associated with protective colloids.
466 I Chapterwise & Topicwise Engineering Entrances Solved Papers
58. Tyndall effect would be observed in colloidal solution. 65. Lyophilic sols are more stable than lyophobic sols due to the
AgN03 + KI ~ AgI + KN0 3 fact that lyophilic colloids are extensively solvated.
Excess 66. Colloid Dispersed phase Dispersion medium
(From Positively Milk Liquid Liquid
AgN03) charged sol
Foam Gas Liquid
59. When aqueous solution of AgN03 is added to KI solution, Mist Liquid Gas
positively charged sol of AgI is obtained due to the adsorption of Vegetable oil Liquid Liquid
Ag+ ions on AgI molecules.
60. Tyndall effect is shown by colloidal solution due to scattering of :. Mist is colloid which has liquid dispersed in gas.
light by their particles. 67. Fog is an example of aerosols i.e. it is a colloidal solution of
61. Lyophilic sols are self-stabilising because these sols are reversible liquid in gas, where liquid is dispersed phase and gas is
and are highly hydrated in the solution. dispersion medium.
62. Size of colloidal particles= 1 to 100 nm (say 10 nm). 68. As2~ sol is a negative sol due to preferential adsorption ofS2-
4 1 4 ions (As 2~JS2-. Hence, a cation is needed to coagulate it.
Ve= nr = n(IO)3 According to Hardy-Schulze rnle, aluminium nitrate will be
3 3 the most efficient to coagulate it, as it gives the most valent
Size of true solution particles "' I nm aluminium ion (Al 3+ ), hence it is required in minimum amount.
4 3
(i.e. coagulation value is least for Al(N0 3h.
Vs= 3 n (I)
69. The action of sodium aluminium silicate (zeolite) on hard
Thus, Ve= 103 water is not an example of colloidal action. It is actually the
Vs simple chemical substitution of calcium salts with zeolite so
that calcium zeolite precipitates out, and hardness of water
63. Mixing the sols together can cause coagulation since the charges are
removes.
neutralised.
70. Emulsions are colloidal system in which dispersion medium
64. The substance which is added to stabilise the emulsion is known as and dispersed phase both are liquids. So, emulsion is dispersion
emulsifier or emulsifying agent. of liquid in liquid.
Emulsions are of two types:
(i) Water in oil
(ii) Oil in water
Nuclear Chemistry
QUICK REVIEW
Nucleus
• The nucleus consists of two basic elementary particles
protons and neutrons. About 20 different particles such as
positron, mesons and neutrino, etc., are produced during
nuclear reactions.
• Mass defect, binding energy and neutron(n ) /proton(p)
ratio, these are the three factors which are responsible for
Disintegration of Nucleus
stability of nucleus.
Mass Defect
A mass loss takes place in the formation ofnucleus is mass
defect. Greater is the mass defect, more is the stability of
nucleus.
Mass defect, tim = I: mass of reactants - 1: mass of
products
Binding Energy
Binding energy is the amount of energy lost in the
formation of nuclide from its nucleons.
E = mc2
. . binding energy
Average bmdmg energy = - - -~ - ~ -
number of nucleons
931.65 MeV energy is produced when lu (1.66 x 10- 27 kg)
is lost in the form of energy. More the binding energy per
nucleon, more stable is the nucleus.
Nuclear Reactions
Neutron-Proton Ratio
• The nuclei whose n/p ratio is one are quite stable. For the
nuclei having atomic number more than 20, the n ip ratio
increases upto 1.56. Such nuclei are stable. The nuclei
whose n Ip ratio lies above or below stability belt are
unstable and emit a and P -particles to attain stability.
• Magic numbers are 2, 8, 20, 28, 50 or 82 protons in nucleus
or 2, 8, 20, 28, 50, 82 or I 26 neutrons in nucleus. These
number impart stability to nucleus.
• Nuclides have a definite number of protons and neutrons
and consequently definite atomic number and mass number.
• During radioactivity, a, p and y-particles are emitted.
a-particles are emitted by clisintegration of nuclei while
P-particles are formed by breaking of neutron. y-particles
are emitted during a- or P- decay.
• The relative penetrating power of a, p, y and neutron is
n > 'Y > p> a . Electrical field can deflect a and P-particles.
Gamma rays have no mass and no charge. Order of velocity
r>P>a.
• Group displacement law The emission of a-particle
from nuclide displaces the daughter nuclide two places left
to the parent nuclide whereas emission of P-particle
displaces the daughter nuclide one place right to the parent
nuclide.
• Emission of an a -particle followed by the emission of two
p -particles result in the formation of an isotope.
Emission of p -particle always results in the formation of
an isobar.
• Nuclear reactions involve the redistribution of protons and
neutrons present in the reactant. It means, total number of
protons and neutrons present in the reactants and products
remain same (sum of mass number and atomic number on
two sides of the reaction must be equal).
468 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Thus, nuclear reactions involve in conversion ofone nuclei Nuclear Reactor
to another. These reactions also involve loss in mass as a
In a nuclear reactor, fission is carried out in a controlled
result of this large amount of energy is released. Mass,
manner to produce energy which is used for peaceful
energy and momentum is conserved in nuclear reactions.
purposes. Main components of a reactor are as follows:
In nuclear fusion reactions, nuclei fuse into one another to
form a bigger nuclei while in nuclear fission reactions, (i) Fuel rods- enriched U 235 , Pu 239 , U 233 , etc.
nucleus breaks into two or more smaller nuclei.
(ii) Control rods- boron-steel or cadmiwn (to absorb
• The thorium series (4n 1 uranium series (4n + 2) and excess neutrons).
actinium series ( 4n + 3 )are natural radioactive series while
neptunium series (4n + I) is a series of man-made (iii) Moderator- heavy water or graphite (slows down the
materials. The (4n + 3)series is called actinium series but it fast moving neutrons).
sta11s from U - 235. (iv) Coolant- heavy water, molten metal such as Na.
• Disintegration constant The disintegration constant is (v) Breeder reactor is used pa1tly for carrying the fission of
given by (A) = - dN_ U235 and partly to produce plutonium (Pu 239 ).
N
Hence, a breeder reactor produces more fissionable
The unit of A is time- ' . nuclei that it consumes.
~I\, = - - og -No (wh ere N O 1s
2.3031 ... 1amount wh'l
. the m1t1a 1e N Radio Carbon Dating
t N
is the amount left after time t) Carbon dating is the technique to find out the age of
archaeological objects such as wood, plant and animal fossils.
Half-Life Period By knowing the equilibrium concentration ofC-14 in a living
0 693 matter as well as in a dead matter at a particular time, the age
• The half-life period given by, t 112 = ·
A of material can be determined. It was discovered by W.F
• Half-life period of a particular radioactive substance is Libby.
independent of initial amount of the radioactive substance. Uses of Radioisotopes
• Amount left after n half-lives= N
2n
° Radioisotopes are also used to solve many problems in
medicine, agriculture and industry.
(i) ~~ I to diagnose and treat thyroid gland.
1
. . I f 112
• Average life penod, 't = - = - - = 1.44 t 112
A 0.693
• Activity of radioactive element = AN
f
(ii) ~ P in treatment of leukemia.

• The SI unit of radioactivity is Becquerel (Bq ). It is equal to (iii) ~ Co in cancer.

one disintegration per second.
(iv) ft Na in detection of amount of blood in the body.
I Curie (Ci) = 3.7 x 1010dps = 3.7 x 1010 Bq
I Rutherford (Rd) = I 0 6 dps = I 06 Bq
(v) n for treating blood cancer.
P

• Quantitative estimation of element present in trace

• In induced radioactivity, a new radioactive isotope of a quantities is made by neutron activation analysis.
known element is prepared from a non-radioactive element.
• Age of minerals and rocks is determined by geological
Transmutation of Elements dating. By knowing the ratio of Pb 206 to U238 and A, we
Transformation of an element into another by bombarding it can find age of mineral.
14
with high energy particle is known as artificial transmutation C and 0 18 radioactive isotopes are used as tracers in
of elements. tagging technique to study the mechanism of reactions.
• Packing fraction
Actual isotopic mass - mass number 4
Critical Mass = -- - - - - - - - - --xl0
Mass number
Critical mass is the minimum amount of fissionable material
which is required to support a self sustaining chain reaction Packing fraction has zero value for C-12 because its actual
under a given set of conditions. isotopic mass= 12.
 Topic 1
Nucleus : Constitution and Stability
2012
1. Which of the following has magic number of neutrons? 7. The nucleus of an atom can be assumed to be spherical.
27 (b) 26 Fe56 . The radius of the nucleus of mass number A is given by
( a) 13 Al [Marupal]
(c) 83 Bi209 (d) 92 U238 1.25 x 10- 13 x A 11 3 cm. Radius of atom is one A. If the
mass number is 64, then the fraction of the atomic volume
2. The cause of instability of nucleus is [MPPET] that is occupied by the nucleus is [Manipall
(a) high proton, electron ratio 3
(a) 1.0 X 10-
(b) high proton, neutron ratio (b) 5.0x 10- 5
( c) low proton,electron ratio (c) 2.S x 10- 2
(d) low proton, neutron ratio (d) 1.25 X 10- 13
2011 2006
3. Which of the following ratio will give stability to daughter 8. In terms of energy 1 u is equal to [Manipal]
element, when radioactive parent element has less number (a) 100 J (b) 931.1 kcal
of protons compared to number of neutrons? [Guj CET] 7
(c) 931.1 MeV (d) 10 erg
(a)N+l (b)N-1 (c)N- 1 (d)N + l 9. The value of amu is which of the following? [WB JEE]
Z+l Z+ l Z-1 Z-1
(a) 1.57 X 10- 24 kg
2009 (b) 1.66 x 10- 24 kg
(c) 1.99 X 10- 23 kg
4. Energy released, when one atom of uranium undergoes ( d) 1.66 x 10- 27 kg
nuclear fission according to the following reaction
is (atomic mass of U= 235.060, Ba = 143.881 and 10. Calculate the mass loss in the following
Kr= 89.947) about [Ke rala CEE] 2H
1 + 13H ~ 24H e + on
1

235 I 144 90 I
92 U + on ~ 56Ba + 36Kr + 2on (Given the masses: 2 H = 2.014, 3 H= 3 . 016;
(a) 235 MeV (b) 208 MeV He = 4 .004, n = I. 008 u ) [Kerala CEE]
(c) 931.5 MeV (d) 5. 33x 1023 MeV (a)0 . 018u (b)0.18u
(e) 20. 8 MeV (c)0.0018u (d) l. 8u
(e) 18 u
2008
11. The energy released in an atom bomb explosion is mainly
5. If the mass defect of 5B 11 is 0.081 u, its average binding due to [BCECEJ
energy (in MeV) is [BITSAT, AMU]
(a) release of neutrons
(a)8.60 (b)6.85 (b) release of electrons
(c) 5.60 (d) 5.86 ( c) greater mass of products than initial material
6. The mass of helium atom of mass number 4 is 4 .0026 u , ( d) lesser mass of products than initial material
while that of the neutron and proton are 1.0087 and 1.0078 12. Nuclides CBCECEJ
respectively on the same scale. Hence, the nuclear binding (a) have specific atomic numbers
energy per nucleon in the helium atom is nearly (b) have same number of protons
(a) 5 MeV (b) 7 MeV [Manipal] (c) have specific atomic number and mass numbers
(c) 10 MeV (d) 14 MeV ( d) are isotopes
 Topic 2
Radioactivity and Effect of Emission (Group Displacement Law)
2013
1. In the nuclear transmutation! Be + X ➔ !Be + Y, (X, Y) 9. Decrease in atomic number is not observed during
is (are) [JEE Advanced] (a) a-emission (b) P-emission CUPSEEJ
(a)(-y, n) (b)(p,D) (c)(n,D) (d) (y, p) ( c) positron emission ( d) electron capture
10. The relative penetrating p ower of a, p,'Y and neutron (n)
2012 follows the order [DCEJ
2. The periodic table consists of 18 groups. An isotope of (a)a>P>y>n (b)n>y> P >a
copper, on bombardment with protons, undergoes a (c) p> a> n > y (d) None of these
nuclear reaction yielding element X as shown below. To
which group, element X belongs in the periodic table? 2008
11.
23 Na is more stable isotope of Na. Find out the process by
[IITJEE]
(a) I (b)VII (c)VIII (d) III which ~1 Na can undergo radioactive decay [Manipal]
24 (a) p- emission (b) a-emission
3. 1 1 Na is radioactive and it decays to [WB JEE]
20 ( c) P + emission ( d) K-electron capture
( a) 9 F and a-particles
(b) 13 Al 24 and position 12. The number ofa and P-particles emitted in nuclear reaction
( c) 11 Na 23 and neutron 90
Th 228 ~ 83 Bi 212 are respectively, [Manipal]
( d) 12 Mg 24 and P-particles (a)4, 1 (b)3,7
4. 7 N 14 can be converted into 8 0 17 and proton by (c)8, 1 (d)4,7
combination with which one of the following? [OJEE] 13. Which of the following has the maximum penetrating
(a) a -particle (b) Neutron power ? [MHT CET]
( c) Proton (d) Deuterium (a) a -particle (b) Proton
(c) y- radiation (d) Positron
2010
14. In successive emission ofa and ~ particles, the number of
5. How many alpha and beta particles will be released in the
a and B-particles should be emitted for the conversion of
nuclear reaction given below 23
92 u k to 82 Pb 206 are [MHT CET]
Th 232 --➔ Pb 20s?
90 82 · [MP PET]
(a) 7a, sp (b) 6a, 4P (c) 4a, 3P (d) 8a, 6P
(a) 6a and 4P (b) 6aand 6P 15. Which one of the following statements is not correct?
(c) 4aand 6P (d) 4a and 4P
(a) ~4 C is a non-radioactive isotope of carbon [MP PET]
6. Find the neutron-proton ratio in the daughter element when
2
one a-particle is emitted by ~~ U. [Guj CET]
(b) ~ Co is an unstable radioisotope of cobalt
( c) BF3 is a Lewis acid
(a) 146/92 (b) 144/92
(c) 146/90 (d) 144/90
( d) CN- is a very strong ligand
7. By natural radioactivity U 238 undergoes by following
16. ~~ X - 3a - P ~ Y . The element Y is
8
[OJEEJ
change,
n u23s ~ u.,. ~ u y · (a) ~1
6
Pb (b) ~F Pb
Determine the atomic and mass number of U Y.
( a) 92 and 234 [Punjab CET] 17. Which among the following are correct with respect to the
(b) 90 and 236 unit of radioactivity ?
(c) 90 and 234 I. The ST uni t of radioactivity is curie (Ci)
(d) 91 and 234 TT. I Ci= 3.7 x 10 10 disintegrations s- 1
TIT. I Bq =3.7 x I0 1°Ci
2009
TV. The STunit of radioactivity is Becquerel (Bq)
8. The total number ofa and ~ particles emitted in the nuclear 10
reaction V. I Ci= 3.7 x I0 Bq [Guj CET]
92 U23s ~ s2Pb214 is [IITJEE] (a) I and III (b) IV and V
(a) 2 (b)4 (c)6 (d) 8 (c) I and II (d) II and IV
 Nuclear Chemistry I 471
18. The number of beta particles emitted in the radioactive 27. When any radioactive element emits !>-particle some
. from 238 U to 206 Pb 1s
decay senes · [J&K CET] product is obtained. They both are [MP PET]
92 82
(a) 10 (b) 8 (c) 6 (d) 2 (a) isotopes (b) isobars
( c) isomers ( d) isotones
19. Highest ionising power is exhibited by [BCECE]
28. Electrical field is used to deflect CMP PET]
(a) cx.-rays (b) P -rays
(c) r-rays (d) X-rays (a) ex. and P-particles (b) ex. and r-particles
(c) ex., pand y-particles (d) P and r-particle
20. The number of ex. and P-particles emitted in the nuclear
29. During the transformation of 6X ~ dye the number
reaction O

Th 228 ~ Bi212 are of!>-particles emitted is [Kerala CEEJ

90 83 [BCECE]
(a)(b - d)/ 4
(a) 4cx. and IP (b) 3cx. and 7P (b) ( c - a)+ I/ 2 ( b - d)
(c) 8cx. and IP (d) 4cx. and 7P (c)(a - c) - 1/2(b - d)
(d) (b - d)+ 2(c - a)
2007 (e) (b-d) + l/ 2(c- a)
21. A positron is emitted from n
Na. The ratio of the atomic
30. An artificial radioactive isotope gave ~4 N after two
mass and atomic number of the resulting nuclide is
successive P-particle emissions. The number of neutrons in
( a) 22/10 {b) 22/ 11 [IIT JEE]
the parent nucleus must be [AMUJ
(c) 23/10 (d) 23/12
(a) 9 (b) 14
22. The radio nuclide ~l Th
4
undergoes two successive (c) 5 (d) 7
!>-decays followed by onecx.-decay. The atomic number and 31. What is the correct order of velocity of alpha (ex.) , beta (P)
the mass number respectively of the resulting radio nuclide
and gan,ma (r)rays? CJ&K CETJ
are [MPPET]
(a) 92 and 234 (b) 94 and 230 (a)cx.>P>y (b)cx.>y>P
(c) 90 and 230 (d) 92 and 230 ( c) y > CX. > p (d) 'Y > p> CX.
23. A radioactive substance 88 X 228 (HA) emits 3cx. and 3P 2005
particles to form' Y'. To which group oflong form of the 32. The spontaneous disintegration of ~~ 8 Uby the loss ofeight
periodic table does' Y' belong? [EAMCET]
a-particles and six !>-particles terminates at [AMUJ
(a) IVA (b)VA {c)VIA (d)VTIA
24. Uranium with a mass number 237 and atomic number 92,
(a) ~1°Ra (b) ll 0
Po

changes to a nucleus with atomic number 90 and mass (c) ~l8

Th (d) ~~ Pb
6

number 233 on emission of [J&K CET] 33. Loss of a beta particle is equivalent to [J&KCET]
( a) P-particle (b) r-particle (a) increase of one neutron only
( c) a-particle (d) positron (b) decrease of one neutron only
(c) Both (a) and (b)
2006 (d) None of the above
25. In the transfom1ation of WU to ~~4 U, if one emission is an 34. P-pa1ticle is emitted in a radioactive reaction when
a -particle, what should be the other emission (s)? (a) a proton changes to neutron [Jamia Millia Islamia]
( a) Two p- [AIEEE] (b) a neutron changes to proton
(b) Two p- and one P + ( c) a neutron changes to electron
(c) One p- and one 'Y ( d) an electron changes to neutron
( d) One p+ and one p- 35. Penetrating power of waves are [DCEJ
26. Gamma rays have [Manipal] (a)y>cx.>P
(a) no mass and no charge (b)r<cx.>P
(b) Only mass (c) y> X-ray
(c) Only charge
(a)y>cx.<P
( d) Both mass and charge
 Topic 3
Radioactive Disintegration Series and
Rate of Radioactive Decay
2014 2009
1. A certain radioactive isotope ; X (half-life = IO days) 8. Lead is the final product formed by a series of changes in
decays to given : ~ ; X. If 1.0 g of X is kept in a sealed which the rate determining state is the radioactive decay of
vessel find the volume of He accumulated at STP in uranium-238 with a half-life of 4 .5 x 109 yr. What would
20 days. (Molar mass of ; X = 253 u) [JEE Advanced] be the age ofa rock sample originally lead free in which the
(a) 22.40 mL (b) 33.40 mL molar proportion of uranium to lead is now 1 : 3?
(c) 55.40 mL (d) 66.40 mL [Kerala CEE]
2. The half-life of 14 Cis 5570 yr. How many years will it take (a) 1.5 x 109 yr (b) 2 .25 X 109 yr
for 90% of a sample to decompose? [BITSAT] (c) 4. 5 x 108 yr (d) 9.0x 109 yr
(a) 5.570 yr (b) 171700 yr (e)l3xI09 yr
(c) 18600 yr (d) 50100 yr 9. For a radioactive decay the value of K = 2. 7x 10- 3 s - 1
2013 and initial concentration is 160 mol/L. After 100 s the
concentration of radioactive element is [OJEE]
3. A radioactive isotope has a-life of 10 yr. What percentage
of the original amount of it remain after 20 yr? [KCET] (a) 72 mol/L (b) 122 mol/L (c) 50 mol/L (d) 80 mol/L
(a)O (b) 12.5 l O. When a radioactive substance is kept in vacuum, the rate of
(c) 8 (d) 25 its disintegration per second [AMU]

4. A sample of radioactive substance with half-life of 3 days (a) increase considerably

was found to contain only 3g of it, when received exactly (b) is not affected
12 days after sealing. The amount of the radioactive ( c) suffers a slight decrease
substance when it was sealed, was [Kerala CEE] (d) increases only if the products are gaseous
(a)6g (b)12g 11. Half-life pe1iod of a radioactive element is 100 yr. How
(c)24g (d)36g long will it take for its 93.75% decay?
(e) 48 g [lndraprastha CET, CG PET]
(a) 400 yr (b) 300 yr (c) 200 yr (d) 193 yr
2010
12. 4n + I series is known by which name? [Guj CET]
5. The half-life period of uranium is 4 .5 billion years. After
9 .0 billion years, the number of moles of helium liberated (a) Actinium (b) Neptunium
from the following nuclear reaction will be [MP PET] (c) Thorium (d) Uranium

92
u23s ➔
90
Th 234 + He4
2
2008
(a) 0.75 mo! 13. If the disintegration constant of isotope is
(b) 1.0 mo! 1.237 x 10-4 yr- I, then half-life period will be [MP PET]
(c) I 1.2 mo!
(a) 280 yr (b) 560 yr (c) 5600 yr (d) 2800 yr
(d) 22.4 mo!
14. Two radioactive elements X and Y have half-lives of6 min
6. 2 part of a radioactive compound undergoes decay in 2 h. and 15 min respectively. An experiment starts with 8 times
4 as many atoms of X as Y . How long it takes for the number
Calculate its half-life time. [Guj CET]
of atoms of X left equals the number of atoms of Y left ?
(a) 60 min (b) 45 min (a) 6 min (b) 12 min (c) 48 min [Kerala CEE]
(c) 30 min (d) 15 min (d) 30 min (e) 24 min
7. If 8.0 g of a radioactive isotope has a half-life of 10 h. The 15. A freshly cut tree and a wooden artifact have 30.4 and 15.2
half-life of2.0 g of the same substance is [Punjab CET] countsg - 1 rnin - 1 ofC-14ofhalf-lifeof5700yr. Theage
(a)2.5h (b)5h of the artifact in years would be [Guj CETJ
(c)I0h (d)40h
(a) 2850 (b) 5700 (c) 570 (d) 6930
 Nuclear Chemistry I 473
16. The half-life period of a radioactive isotope is 4.8 min. 2006
Starting with 1 mg of the isotope, how much of it would 26. A san1ple of rock from moon contains equal number of
remain after l O min ? [J&K CETJ 9
atoms of uranium and lead t 112 for U = 4 . 5 x 10 yr. The
(a) 0 .5 mg (b) 0.726 mg age of the rock would be [Manipal]
(c) 0. 126 mg (d) 0.236 mg
(a) 2 .25 x 109 yr (b) 13.5 x 10 9 yr
17. Which of the following is not co1rect? CBCECE]
(c) 9.0x 10 9 yr (d) 4 .5 x 109 yr
0.693 1
(a) t I12 = - - (b) N = N 0 e - k
k 27. The half-life period of a radioactive material is 15 min.
1 l What per cent of radioactivity of that material will remain
(c) - - - = In kt 112 (d) None of these after 45 nlin ? [Manipal]
N N0
(a) 17.5% (b) 15% (c) 12.5% (d) 10%
18. If 50% of a radioactive substance dissociates in 15 min, 2 19
28. 84 Rn is a member of actinium series. The other
then the time taken by substance to dissociate 99% will be
member of this series is CWB JEE]
(a) 50 min (b) 100 min [DCE]
(a) 84 Ac22s (b) 90 Th 232
(c) 99 min (d) 150 min
(c) ts p 35 (d) 92 U23s
2007 14
29. What is the half-life of 6 C , if its disintegration constant is
19. A radioactive element gets spilled over the floor ofa room. 1
Its half-life period is 30 days. If the initial activity is ten 2 .31 X 10-4 yr- ? [UPSEE]
times the pemlissible value, after how many days will it be 4 3
(a) 0.3 x 10 yr (b) 0.3 x 10 yr
safe to enter the room ? CAIEEE]
(c) 0.3 x 108 yr (d) 0.3 x 102 yr
(a) 1000 days (b) 300 days
(c) IOdays (d) 100 days 30. The activity ofa radioactive substance falls to 87.5% of the
initial value in 5 yr. What is the half-life of the element?
20. The half-life of a radioactive isotope is 3 h . If the initial
mass of the isotope were 256 g, the mass of it remaining (a) 52 yr (b) 104 yr [UPSEEl
undecayed after 18 h would be [MP PE T]
(c) 26 yr (d) 13 yr
(a) 4.0 g (b) 8.0 g 31. A radioactive isotope decays at such a rate that after
(c) l 2.0g (d)16.0 g 192 min only 1/16 of the original an1ount remains left. Its
half-life is CAMUl
21. The radioactive isotope ofcesium - 137 of weight 8 g was
(a)32min (b)48min (c) l 2min (d)24min
collected on 1st February, 2006 and kept in a sealed tube.
On 1st July 2006 it was found that only 0.25 g of it 32. If half-life period is 100 yr, average life is nearly
remained. The half-life period of the isotope is (a) 100 yr (b) 70 yr [Guj CETl
(a) 37.5 days (b) 30 days [Ke rala CEE] (c) 144 yr (d) 90 yr
(c) 25 days (d) 50 days 33. The activity of a radioactive nuclide is 2 x IO 7
(e) 60 days disintegrations per minute (dpm). After 23.03 min, its
22. The half-life pe1iod of radioactive element is 140 days. activity is reduced to 2 x I 0 6 dpm. What is the average life
After 560 days, 1 g of element will reduce to [WB JEE] (in nlin) of th is nuclide ? [J&K CETl

(a)¾g (b) ¾ g (c)ig (d) ~g (a) 100 (b) 10 (c) I (d) 0.1
1
23. Half-life ofa radioactive element is 16 h. What time it will 2005
take for 75% disintegration? [AMU] 34. If the half-life of an isotope Xis IOyr, its decay constant is
(a) 32 days (b) 32 h (a) 6.932 yr- 1 (b) 0 .6932 yr- 1 [Manipal]
(c) 48h (d)l6h (c) 0.06932 yr- 1 (d) 0.006932 yr- 1
226 35. A radioactive isotope has a half-life of 10 days. If today
24. Thehalf-lifeofRa is 1620yr, the decay constant (k)is
125 mg is left over, what was its original weight 40 days
(a) 0.000452 (b) 0.0004278 [J&K CET]
earlier ? CKCETJ
(c) 0.04278 (d) 0.004278
(a) 2 g (b) 600 mg (c) I g (d) l.5 g
25. A radioactive isotope has a half-life of 27 days. Startmg 14
with 4 g of the isotope, what will be mass remaining after 36. T112 of C isotope is 5770 yr. Time after which 72% of
75 days? [DCE] isotope left is COJEEl
(a) 100 g (b) 50 g (c) 0.58 g (d) 1.58 g (a) 2740 yr (b) 274 yr (c) 2780 yr (d) 278 yr
474 I Chapterwise & Topicwise Engineering Entrances Solved Papers
37. A radioactive substance takes 20 min to decay 25%. How 39. A wooden box excavated from Indus valley had an activity
13
much time will be taken to decay 75%? [OJEEJ of 1.18 x 10 disintegration per minute per g of carbon.
(a) 96.4 min What is the approximate age of this civilisation ? CRPETJ
(b) 68 min (a) 4000 yr (b) 5700 yr
(c) 964 min (c) 8100 yr (d) 6000 yr
(d) 680 min
40. Half-life of a substance A following first order kinetics is 5
38. The half-lives of two radioactive nuclides A and B are days. Starting with 100 g of A, amount left after 15 days is
1 and 2 min respectively. Equal weights of A and B are
(a) 25 g [Jamia Millia Islamia]
taken separately and allowed to disintegrate for 4 min.
(b) 50 g
What will be the ratio of weights of A and B disintegrated ?
(c) 12.5 g
(a) 1 : 1 {b) 5 : 4 [EAMCETJ (d) 6.25 g
(c) 1 : 2 (d) 1 : 3

Topic 4
Artificial Transmutations and Nuclear Reactions
2011
1. Bombardment of aluminium by a-particle leads to its 6. The reaction, fj Al + i He ~ ff Si+ : H is of the type
artificial disintegration in two ways, (i) and (ii) as shown.
(a) nuclear fusion [MP PET]
Products X, Y and Z respectively are,
(b) nuclear fission
(ii) (c) chemical reaction
27AI- - - -_.30p +y

';oj r ( d) transmutation
7. Isotope of uranium used in atomic bomb is
(a) ~~
7
u (b) ~~
8
u (c) ~
9
u (d) ~~
[MP PET]
5
u
30 Si+X 30Si+Z
14 14
[IITJEE] 8. The product P of the nuclear reaction,
(a) proton, neutron, positron 235 U
92 + 0t n ~ p+ 36 Kr
92 + 3 0t n is , [WB JEE]
(b) neutron, positron, proton
(c) proton, positron, neutron (a) ~!1 Sr (b) ~!' La (c) ~!' Ba (d) ~!1 Cs
( d) positron, proton, neutron
2. A radioactive atom iM emits two a -particles and one 2007
~particle successively. the number of neutrons in the 9. Which of the following nuclear reactions will generate an
nucleus of the product will be [WB JEE] isotope ? [AIEEEJ
(a)X- 4- Y (b)X- Y- 5 (a) Neutron particle emission
(c)X- Y- 3 (d)X- Y- 6 (b) Positron emission
( c) a -particle emission
3. j Li + A ➔ i He + B. A andB are respectively [Guj CET] ( d) P-particle emission
(a)(D, a) (b) (a, n) 10. A nuclear reaction of ~~5 U with a neutron produces ~ Kr
(c)(n,o.) (d)(p,o.)
and two neutrons. Other element produced in this reaction
2010 is [VITEEE]

4. The number of neutrons emitted when

2
~ U undergoes (a) ~r Te (b) ~~ Cs
4
(c) ~f Ba (d) ~f Ba
controlled nuclear fission to 1~ Xe and ~ Sr is
1
[HT JEE] 11. What is the fuel of atomic pile ? [MHT CETJ

(a) I (b) 2 (c) 3 (d) 4 (a) Thorium (b) Sodium

(c) Uranium (d) Petroleum
2008 12. The radioactive isotope ~~ Co which is used in the
5. Identify the nuclear reaction that differs from the rest. treatment of cancer can be made by (n, p )reaction. For this
(a) Positron emission (b) K -capture [Ke rala CEE] reaction the target nucleus is [UPSEEJ
(c) P-decay
(e) y-decay
(d) a -decay
w:~ ~~~ ~:M w~~
 Nuclear Chemistry I 475
13. 7 N 14 when attacked by double charged helium ion, it emits 22. Hydrogen bomb is based on the principle of [AIEEEJ
a proton and [OJEEJ (a) artificial radioactivity
(a) g016 (b) 7 Nts {c) g017 (d) 9 Fl8 (b) nuclear fusion
(c) natural radioactivity
14. The only, most stable nucleus fom1ed by bombarding, (d) nuclear fission
either 13 Al 27 by neutrons or 11Na 23 by deuterons, is 23. A photon of hard gamma radiation knocks a proton out of
(a)15P30 (b) 14Si30 [J&KCETJ t1Mg nucleus to form [AIEEEJ
(c) 12Mg24 (d) 56Bat37 (a) the isobar of nNa
15. Consider the following nuclear reactions
238M ~ yXN + 2 4H XN AL + 2A+
(b) the nuclide Na :t
92 2 e; y ~B I-'· (c) the isobar of parent nucleus
Number of neutrons in the product ~ Lare ( d) the isotope of parent nucleus
(a) 142 [Jamia Millia Islamia] 24. In which of the following nuclear reaction neutrons is
(b) 144 emitted ? CKCETJ
(c) 140
(d) 146
(a) tJ Al + 1He ~ ?f P
(b) ~ C+ :H~ ?N
2

2006
(c) ff P ~ ffsi
16. Cadmium rods are used for which purpose [WB JEE]
(a) emit electrons (b) absorb neutrons
1
(d) ~: Am + iHe~ ~j5 Bk
( c) emit neutrons (d) absorb electrons 25. Which of the following cannot be accelerated? CKCETJ
17. The radiant energy from the sun is due to [UPSEEJ (a) a-particle
(a) combustion (b) nuclear fusion (b) ~-particle
( c) nuclear fission (d) chemical reaction (c) Protons
18. Which of the following is not correct? [EAMCETJ (d) Neutrons
(a) Nuclei of atoms participate in nuclear reactions 26. Match Column I and Column II and select the con-ect
(b) 20 Ca 40 and 18 Ar 40 are isotones answer using the code given below the lists.
(c) I u of mass defect is approximately equal to Column I Column IT
93 1.5 MeV (Nuclear reactor (Substance used)
( d) Uranium (U238 ) series is known as(4n + 2) series components)
19. Water used as moderator in nuclear reactor is called A. Moderator I. Uranium
(a) heavy water (b) hard water [Guj CETJ B. Control rods 2. Graphite
( c) nuclear water (d) critical water
C. Fuel rods 3. Boron
20. What is X in the following nuclear reaction ?
D. Coolant 4. Lead
I I Na
23
+ on I ~ II N a 24 + X [J&KCET]
5. Sodium
(a) 1 H 1 (b) 2 He
4

(c) 1 H
2
{d) "{-ray (gamma ray) Codes [Kerala CEE]
A B C D
2005 (a) 2 1 3 5
(b) 2 3 I 5
21. 174N + 42 H e ~ X + 1I H, X 1s
.
[DCEJ (c) 5 2 1 3
(a)~8 o (b)~7 o (d) 3 4 I 2
(c) i4 N (d) ~5 N (e) 4 3 2 1
 Topic 5
Applications of Radioactivity
2008
1. Which one of the following radioactive isotope is used in 3. Which of the following is used in the treatment of blood
the treatment of cancer ? [MP PET] cancer ? [WB JEE]
(a) P32 (b)It3 t (c)Co60 (d)Na 24 (a) 113 1
(b) p 32
2007
(c) Rn
2. The age of a specimen t is related to the daughter/parent (d) 1121
ratio of number of atoms (D IP ) by the equation
(A = decay constant) [Ke rala CEE] 4. Radiocarbon dating was discovered by [DCEJ
(a) GN Lewis
(a)t = ~ln{~} (b)t = f1n{1+;} (b) J Williard Gibbs
(c) WF Libby
(c) t = ~ In{ 2 + ; } (d) t = i In { 1+ ~} (d) W Nemst

(e) t = ~ 1n{2 + ~}

Answers
.Ille!C1 Nucleus : Constitution and Stability
1. (c) 2. (d) 3. (b) 4. (b) 5. (b) 6. (b) 7. (d) 8. (c) 9. (d) 10. (a)
11 . (d) 12. (c)
TOPIC2 Radioactivity and Effect of Emission (Group Displacement Law)
1. (a, b) 2. (c) 3. (d) 4. (a) 5. (a) 6. (d) 7. (d) 8. (d) 9. (b) 10. (b)
11. (a) 12. (a) 13. (c) 14. (d) 15. (a) 16. ( d) 17. (b,d) 18. (c) 19. (a) 20. (a)
21 . (c) 22. (c) 23. (d ) 24. (c) 25. (a) 26. (a) 27. (b) 28. (a) 29. (b) 30. (a)
31 . (d) 32. (d ) 33. (b) 34. (b) 35. (c)
TOPIC 3 Radioactive Disintegration Series and Rate of Radioactive Decay
1. (d) 2. (c) 3. (d) 4. (e) 5. (a) 6. (a) 7. (c) 8. (d) 9. (b) 10. (b)
11 . (a) 12. (b) 13. (c) 14. (d) 15. (b) 16. ( d) 17. (c) 18. (c) 19. ( d) 20. (a)
21 . (b) 22. (d ) 23. (b) 24. (b) 25. (c) 26. (d) 27. (c) 28. (d) 29. (a) 30. (c)
31 . (b) 32. (c) 33. (b) 34. (c) 35. (a) 36. (a) 37. (a) 38. (b) 39. (c) 40. (c)
TOPIC4 Artificial Transmutations and Nuclear Reactions
1. (a) 2. (b) 3. (d) 4. (c) 5. (e) 6. (d) 7. (d) 8. (c) 9. (a) 10. (d)
11 . (c) 12. (c) 13. (c) 14. (c) 15. (b) 16. (b) 17. (b) 18. (b) 19. (a) 20. (d)
21 . (b) 22. (b) 23. (b) 24. (a) 25. (d ) 26. (b)
TOPIC5 Applications of Radioactivity
1. (c) 2. (d ) 3. (b) 4. (c)
 Explanations
Topic 1 Nucleus: Constitution and Stability
1. Magic numbers are 2, 8, 20, 28, 50 or 82 protons in nucleus or 2, 8, 8. I u = 1.67 x I 0-24 g
20, 28, 50, 82 or 126 neutrons in nucleus. These number impart
Energy equivalent to this mass can be calculated by using the
stability to nucleus.
27 relation,
(a) 13 AI , number of neutrons = 27- 13 = 14
E = mc2
56
(b) 26Fe , munber of neutrons = 56 - 26 = 30
209
Here m = 1.67 X 10- 24 g
(c) 83 Bi , number of neutrons = 209 - 83 = 126
238
c= 3 x 10 10cm s- 1
(d) 92U , number of neutrons =238-92=146
E = l.67 X 10-24 X (3 X 10 10/ergs
2. For a stable nucleus !!_ = I and for a unstable nucleus, !!_ ~ 1.5.
p p 1.503 ~ 10-J J = 1.503 X 10-IOJ
Therefore, low p I n ratio will cause instability of nucleus. 10
19
3. Lighter nuclides (up to Z = 20) have n I p ratio = I, while heavier Now, 1.6 x 10- J = I eV
nuclides have n I p ratio greater than one to over come I 18
1J = 19 eV = 6.25 X 10 eV
proton-proton repulsion. For stable daughter nuclei, the ratio is 1.6 X 10-
N-1
1.503 X 10-IOJ
Z+I
4. Mass defect, f'o..m = :E mass of reactants -:E mass of products = 6.25 X 10 18
X 1.503 X 10-10eV

f'o..m = 235.060 - (143.881 + 89.947+ 1.009) = 9.393 X 108 eV

= 0.223 I u = 939.3 MeV"' 931.1 MeV
Binding energy or the energy released 9. The amu represents atomic mass unit. It is used in place of
= 0.223 x 931 MeV = 207.6 MeV= 208 MeV unified mass unit.
11
5. Given, f'o..m for 5 B = 0.081 u I u = I avogram = laston = I dalton
I
Number of nucleons= 11 1 u = - x mass ofC-12 atom
12
Binding energy= 931 x 6.m MeV= 931 x 0.081 = 75. 4 11MeV
. . binding energy
Average bmdmg energy= - - - - - - - = __!__ X 1.9924 X 10-ZJ g= J.66 X 10-24 g
number of nucleons 12
75 41 1 = 1.66 X 10- 27 kg
= . = 6.85 MeV
II
10. Total mass of
6. He atom has 2p + 2n.
fH + fH -------t iHe+ /,n.
Hence, f'o..m = (2 x I .0078 + 2 x I .0087) - 4.0026 = 0.0304 u
In the above reaction,
: . Energy released= 0.0304 x 931 .5 MeV = 28.3 MeV
28·3 Total mass ofLHS = 2.0 14 + 3.016 = 5.030
. d'mg energy per nucIeon = -
B 111 - = 7 M eV (approximate
. Iy)
4 Total mass ofRHS = 5.0 12
7. Radius of nucleus= 1.25 x 10- 13
x A cm 113 Mass loss while forming products
13
= 1.25 x 10- x 64 113 cm = :E mass of reactants - :E mass of products
=5.030-5.012 =0.0 18u
= 1.25 x 10- 13 x 4 cm = 5 x 10-13 cm
11. The source of large energy, produced during atom bomb
Radius of atom = IA = 10- 8 cm explosion, is the mass defect occurring during the fission
Volume of nucleus/volume of atom reaction, which is converted into energy equivalent to mass
(4/ 3)7t (5 X 10-13 )3 I 25 X 10-39 defect.
(4t3)n c10-s)3 10-24 12. Nuclides have a definite number of protons and neutrons and
consequently definite atomic number and mass number. Such
= 125 X 10- IS= 1.25 X 10- 13 as oxygen nuclei contain 8 protons and 8 neutrons (8 0 16 ) .
Topic 2 Radioactivity and Effect of Emission (Group Displacement Law)
1. ~Be+ ~X - :Be+ 1Y 11. nip ratio of TiNa = 13/11 i.e. greater than unity. To achieve

~n -
Atomic number same stability, it would tend to become unity. This can happen if
4+a=4+c n decreases orp increases. To do so, a neutron changes into proton
and an electron (13--particle) which is emitted.
9+b=8+d
:p+ ~1e$-1)
If X = ~'Y, then a = 0, b = 0, Y = lf1 , then c = 0, d = I
If X = :p, then a = 1, b = I, Y = D, then c = f i d =2
12. 90Th22s - 33Bi212+x(1ex)+ (l113)
228=212 + 4x or 4x= l 6 orx=4
!Be + ~'Y - !Be+ ~1
90 = 83 + 2x - y = 83 + 8 - y or y = I
~Be+ :P - :Be+ fD 13. y-radiations are neutral, so not deflected by electric and magnetic
2. Balancing the given nuclear reaction in terms of atomic number field. Thus, have maximlU11 penetrating power.
(charge) and mass number given 238 206 4
14. 92U - 82Pb + 111iHe + n _/
29Cu6J + iH1 - 6on1 + 2He4+1H 1 + 26xsi
On comparing both sides
The number 26 correspond to transition metal 'Fe' which belongs
th 238 = 206 + 4m ⇒ m = 8
to 8 group of modem periodic table.
92 = 82 + 2m - n ⇒ 2m - n = IO ⇒ n= 6
3. i ,Na24 - i2Mg24 + -1130 ex-particles emitted, m = 8
(Stable)
13-particles emitted, n = 6
4. 7N14 + 2He4 - 3011 + ,H1 4
15. ~ C is a radioactive isotope of carbon. It is useful in the age
5. 90Th 232 - s2Pb20s+x2He4 + Y-1eo determination of fossil.
(I-particle ~ -particle
ng - Jo '16 -ll ?lfu..
On comparing, 16. 88 X - 82 Pb - 83 · tli(Y).
X = 232- 208 17. The SI unit of radioactivity is Becquerel (Bq).
232 = 208 + 4x - 0 ⇒ 6
4 I Ci= 3.7 x 10 10 disintegration s- 1
⇒
90 = 82 + 2x - y 90 = 82 + 2 X 6 - y I Ci= 3.7 x 1010Bq
90-94=-y ⇒ y=4
1 Bq = I disintegration s-1
Thus, 6ex and 4!3--particles are emitted during this reaction.
2 2 18. Number of l3-particles = 2 x number of ex-particles - change in
6. ~~U - ~ Th + iHe
Daugther atomic munber
element
. 238 - 206
Number of ex-particles= - - - - = 8
·: Number of protons in daughter e lement= 90 4
·: Number ofneutrons in daughter element = 234 - 90 = 144 Number of[3-particles = 2 x 8 - (92- 82) = 16- 10 = 6
n 144 19. Highest ionising power is exhibited by a-rays. This is 100 times
- = -
p 90 greater than !3-rays and I 0,000 times greater than y-rays. This is
238 due to high kinetic energy of ex-particles.
7. Since, one ex-particle is emitted from 92 U , hence Ux w ill have
20. Let the number of a-particles emitted by nuclear reaction are
mass number= 238 - 4 = 234.
x and 13 -particles emitted by nuclear reaction are y.
Atomic mm1ber = 92 - 2 = 90 90 Th228 - 33Bi212 + x (2He4) + Y C,eo)
From Ux one !3--particle has been emitted to produce UY' which
228 = 212 + 4x ⇒ 4x = 228 - 212
w ill have
16
mass number =234 x= - =4
4
atomic number= 90 + 1 = 91 90= 83 + 2x- y
8.
2
t~u - 2
~iPb + 6iHe + 2 _?e@) 90 = 83 + 2 X 4 - y
Hence, total mm1ber of particles emitted in the given nuclear 90- 83- 8 = - y
reaction is 8. y=I
9. {A - x+fA + -le° 21. ftNa - f~Na + -~e
ll-particle
-P - ll
4
-n
During !3--emission atomic number is increased by one unit while 22. ~Th - - ~i X - ~oy
atomic mass remains the same.
23. ~~ X -
8
~~ Y + 3a + 313
6

10. Penetrating power is the highest for neutral particles.

II A group vn A group
Penetrating power follows following order
n > 'Y > 13 > ex. 24. 92U231 ~ 90X233
 Nuclear Chemistry I 479
25. 92U238 - 92U234 + 2He4 + 2 -1eo Topic 3 Radioactive Disintegration
26. Gamma rays are electromagnetic radiations with the velocity Series and Rate of
same as that of light. Radioactive Decay
27. Atomic mass is not affected by l3-emission hence the product 1. Mass of X decay = 0.75 g
obtained after P -emission is a lways an isobar of the parent
0 75
species. Moles of X decayed= · = moles of He formed
253
75 224
V(mL)of He at STP = 0. x 00 = 66.40 mL
A and B are isobars. 253
28. a-particles are positively charged whereas p -particles are 14
2. Half-life of C(,112l = 5570 yr
negatively charged particles. Hence, these can be deflected by
electric field. However, y-particles being neutral cannot be Lets, consider that the initial concentration of sample is I 00 and
deflected by electric field. concentration remaining after I years is IO as 90% is decomposed.
So,
29. During the transformation of b X 0 - d~- [R 0 ] = 100 ⇒ [R]= 10
Time = 1yr
The number of p -particles emitted is (c - a)+ _!_ (b - d).
2 k = 0.69 = 0.69 ⇒ k = 2.303 log [R0 ]
Because by the emission of one P-particle atomic number is 1112 5570 1 [R ]
increased by one unit but mass number is unchanged.
0.69 = 2.303 lo 100 (lo l0 = l)
30. Atomic number increases by one after the emission of one 5570 I g 10 g
P-particle. Hence, the parent nucleus (which on two successive 0.69 2.303
14 14
P-emission gave 7 N ) must be 5 X . 5570 t
Hence, number of neutrons in parent nucleus= 14 - 5 = 9. 2.303 X 5570
1 = - - - - 18590.8 = 18600 yr
31. The order of velocity ofcx, pand y-rays is 0.69
Y > P > a co
3. We know that C,. = -
(3 x 108 m/s)(2.36 x 108 m/s) (2 x 107 m/s) to 2"
(2.83 x 108 m i s.) C,. = concentration after n half-lives
n = number of half-lives
32 238U -8n 2060 s -o~ 206pb
• 92 76 82 c• = initial concentration
Thus, after emission of 8cx-and 6P-particles ~ 8 U will terminate I 1
C,. = 2 = - = 0.25 or 25%.
2 4

n-
at ~g6Pb.
4. 1112 = 3 days, N = 3g, T = 12days
33. Loss of a P-particle is equivalent to decrease of one neutron only.
where, fl= number of half-life, T = total time, 1112 = half-life
p+ e- + v
I= n. X 1112 ⇒ 12 = fl X 3 ⇒ fl= 4
Hence, by the emission ofa l3-particle atomic number is increased
On putting the value of n in the following equation,
by one unit.
34. In P-particle emission, neutron changes to proton. N=N0 (½)" ⇒ 3=Nox(½r
~fl -➔ :H + ~ e 1

35. Wavelength
3 = N OX l61 ⇒ N O = 3 X 16 = 48 g

ex: - - - cx: - - - - - - 5. Given, 1112 ofU = 4.5 billion year, I= 9.0 billion year
energy penetrating power
We know that, t = 1112 x n ⇒ 9.0 = 4.5 x n.
: . Shorter the wavelength, higher will be the energy and
penetrating power. n=2 ⇒ N =N0 x(½)" = l x (½r =¾
Wavelength ofy-rays = 0.1 - 1.0 A
Wavelength of X-rays = 1.0 - 10 A :. The amount ofU disintegrated = I - __!_=I = 0.75
4 4
Penetrating power of a-particles is less due to high mass. 92U23s - 90Th234 + 2He4
P-particles have higher penetrating power due to less mass. I mol I mol
0.75 mol 0.75 mol
: . Order of penetrating power is
y > X-rays > a :. 0.75 mo l of 2He4 are obtained.
480 I Chapterwise & Topicwise Engineering Entrances Solved Papers

15. t 112 ofC-14=5700yr

6_ A= 2.303 log - a - = 2.303 10g_ a_ = 2.303 10g 4
t a-x 2 a- -3 a 2
⇒ t-
14
,I\, = 0.693 _-2.303 C of
- 1og~,4~ - cut tree
4 -----
5700 A C of wooden artifact
= 2.303 log 2 = 0.69 h- 1
2.303 X 5700 lo 30.4 = S?Ol. 6 "" 5700
_ 0.693 _ 0.693 _ 1h- 0 . 0.693 g 15.2 yr
1112-- A- - 0.693 - - 6 mm
16. Given, half-life period, t 112 = 4.8 min
7. Half-life is independent of initial concentration. Thus, it remains
same. initial amount, N O = I mg
8. All radioactive processes follow first order kinetics. Initially total time, t = 1O min
sample is free from lead. If its proportion is x, the amount of k = 0.693 = 0.693
sample at time T is 4x. f112 4.8
0.693 2. 303 I 4x
og- k = 2.303 log N 0
4.5 x 109 yr T x ⇒
t N
T = 2 X 4.5 X 109 yr= 9.0 X 109 yr 0.693 = 2 . 303 log_!_
or
_ 2.303 N 4.8 10 N
9. K - - - 1og10 - 0
t N 1
⇒ log N = 0.62689
_3 _2.303 160 I 160
2 .7 x 10 - 1og 10 N or og10 N =01172
.
100 N = 0.236 mg
160 17. According to the law of radioactive decay, 'the quantity of a
or = antilog 0. 1172 = 1 .309
N radioactive element which disappears in unit time (rate of
disintegration) is directly proportional to the amount present' .
N = ~ =122.23
1. 309 -dN, =AN
1O. Rate of disintegration is not affected by environmental conditions. dt
0.693 0.693 -I where, A = radioactive constant
11. Decay constant, k =- - =- - yr
l112 100 N, =Nae-'J.J
2.303 a
Also, decay constant, k =- - log - - ⇒ In_!!__ = - kt
t a-x No
k = 2.303 lo 100 In No= kt
t g 100 - 93.35 N
0 693 2 303
· = · 1ogl6 (': log 16 = 4 x log 2) - I - - I = I n kt 11 2 1.s not correct.
100 t N N0
t = 2.303 X 100 X 4 X 0.3010 Half-life period is defined as the time required by a given amount
400
0.693 yr of the element to decay to one-ha!f of its initial value.
12. 4n + 1 series is also known as neptunium series. It is the only 0.693
f112= - /\, -
artificial series.
13. H a If- l1·r,e peno
. d = - - - -0.693 ----- 18. Radioactive disintegration is a first order reaction, hence
disintegration constant (k) k = 2.303 log- a-
0.693 = 5600 t a-x
1.237 X l 0---4 yr yr k = 2.303 10 100
14. Let the initial amount of Y = 1
15 g lOO- 50

So, the initial amount of X = 8 also, k = 2.303 log 100

t 100- 99
X decomposes as
t 2 3 4 I s I 2.303 g 100 = 2.303 g 100
8-4- 2- 1- - - - 10 10
2 4 15 50 t 1
1 1
Number of half-lives of X = 5 - log2 = - log JOO
15 t
1 1
Y decomposes as I ~ - ~ - 0.30 10 2
2 4
15 t
Number of half-lives of Y = 2
2 X 15 .
So, total time T = n x 1112 = 5 x 6 = 30 min t= - - =99mm
0.3010
or T = n X t 112 = 2 X 15 = 30 min
 Nuclear Chemistry I 481
238 206
19. Activity oc N 26. One atom of 92U produces one atom of 82Pb on decay.
238 206
Therefore, the number of atom ofU and Pb in a rock sample
; = Gr or ~=Gr or 10=2n is equal only when half of the number ofU238 originally present
0 1
decay to give same number of Pb206. Thus, the time elapsed will
Taking on both side
I be equal to the half-life period ofU238 .
Iogl0 = n.log2 ⇒ n. = - - = 3.32
0.301 27. T = 45 min, 1112 = 15 min
time= n. x half-life T= nXl112

= 3.32 x 30 = 99.6"' 100 days 45

n.= - =3 ⇒ n.=3
15
20. C =co(½r
N =N0 xGr
y= total time=~=
6 ( C 0 = 256 g)
f112 3 Let N0 =I
6 I I I
N = Ix- N =- ⇒ N = - x I 00 = 12.5%
1) 256
C(undecayed) = 256 ( 2 = 64 = 4 g 8' 8 8
28. The series 4n + 3 is known as actinium series. It shows that if
21. Cs-137=8gon IstFeb2006 mass number is divided by 4 then the remainder must be 3.
0.25 g left on 1st July 2006 Hence, the another member of this series is 92 U 235 .
235
8 g reduces to 0.25 g in 5 x 30 days = 58 + Remainder 3
4
T = n. x t 112 ⇒ 150 days= 5 x t 112
150 0.693 0.693
29. f112= - -
t 112 = - days= 30 days k 2.3 1X 10-4
5
22. T=n.Xl112 30. ·: A = 2.303 log No
t N
560
where, 1112 = half-life period, n. = ..!_ = =4 Here, I= 5yr, N 0 = 100,N = 87.5
f112 140
:>-. = 2.303 Io 100 = 0.0267 - 1
5 g87.5 yr
0.693 0.693
1112 = - - = - - = 25.95yr= 26 yr
:>-. 0.0267
31. Given, I = 192 min
N 1
⇒
⇒
2 - = - 1112=?

:0 = (1r 1:0 = Gr
N0 16

(!)-
l

⇒
We know that, -N = - tvi
Gr= Gr n=
2 N0 2
total time
n.= - - -
half-life
Total time= n x half-life = 2 x 16= 32 h
0.693 or
24. Decay constant (k) = - -
1112
4 = 192
1620 = 0.693 ⇒ 0 693
k = · = 0.0004278 111 2
k 1620
⇒ t 112 = -192 = 48 mm
.
25 _ k = 0.693 4
1112
32. 1av = I .44l\l 2
t -- 2.303 logN o ⇒ 1112 = 27days 1112 = 100 yr
k N
lav = 1 .44x 100=144yr
k = 0.693 = 0.0257 day-1 ⇒ t = 2. 303 lo No
27 0.0257 g N k - 2.303 N 0 _ 2.303 2xl07 _ 2.303 IO
33.
- - t - ogN- 23.03 og2xld'- 23.03 1og
1 1
N O = 4 g, N = ?, t = 75 days
2.303
75 = - - log-
4
⇒ N =0.58g
k = 0.1 min - I ⇒
0 693 0 693
t 112 = ·
= · = 6.93 min
0.0257 N k 0.1
Average life (T) = 1.44 x 1112 = 1.44 x 6.93 = 10 mi n
482 I Chapterwise & Topicwise Engineering Entrances Solved Papers

34 _ /\, = 0.693 = 0.693 = 0 _0693 yr-I Topic 4 Artificial Transmutations

t112 10 and Nuclear Reactions
35. N = N 0( -1)" n = -40 = 4 1. (i) ~1AI + 1He(cx) - f~Si + .ix
2 ' IO X is proton : H.
4 4
125 _ N l N _ 125 x 2 _
1000 - 0( ) 2 ' 0- 1000 - g
2 (ii) ~1Al + iHe(cx) - {~+ ~

36. For a first order reaction (like radioactive decay),

Y is neutron Jn. {~P - {~Si + ?z
k = 0.6932 = 2.303 log N 0 Z is positron +~e
t 112 t N, 2 MX -o. Nx-4 -o. oX-8 - ~ ...X-8
• Y~ y-2 ~ Y- 4 -----"--7 l" Y- 3
0.6932 = 2.303 log 100 Number of neutrons= Mass number. - Atomic number.
5770 t 72 =X-8-Y+3=X-Y-5
2.303 X 5770 X 0.143
t = ------- 2742 "' 2740yr 3. 1Li + :H - ;He + i He
0.6932 (p) (0.)
37. For radioactive decay (first order reaction) 4. 92U235-4 54Xel42+ 3gSr9() + 3onl
_ 2.303 N _ 2.303 N
k - - - 1og- 0 - - - 1og- 0 5. Positron emission, K-capture, 13-decay and a-decay, all of
t1 N,I 12 N,2
these processes cause change in either atomic number or in
_._2.303 lo I 00 = 2.303 lo I 00 mass number or in both but y-decay do not cause any change
20 g 75 t2 g 25 either in mass number or in atomic number, so it is different
_ log4 from the rest.
f2 - 20 x --
4
6. The conversion of one element into another by artificial means,
log-
3 i.e. by means of bombarding w ith some fundamental particles
0.6020 96 . like as alpha particle, is known as artificial transmu tation, e.g.
t2 = 20 x - - - = .4 mm
0.1249 f;Al + iHe - {~Si+ :H
o.-particle
38. For A, t 112 = 1 min
7. Wu is used in atomic bomb.
: . Part of A remained after 4 min (i.e . 4 half-life) will be= _!_ 8. The complete nuclear reaction is
16
:. Part of A disintegrated in the same period = ~ ~
5
U+
1
o'1 - i: Ba + j~Kr + 3
1
~1
16 9. ix - 1-1x + on1
For B , t 112 = 2 min
Isotopes are species having same number of proton, bu t different
: . Part of B remained after 4 min (i.e. 2 half-life) = __!__ number of neutron.
4

: . Part of B disintegrated in the same time= 24 10. i~5U + /in - j~ + 1~4Ba + 2 /in
In the nuclear reaction atomic number and mass are conserved.

~n-
Hence, ratio of disintegrated weights of A and B
11. U ranium and plutonium is using now a days as a fuel in atomic
=~:2= 15:12=5 : 4 pile.
16 4
12. ~Ni + ~Co+ :H
39. dN =A · N (n) (p)
dt
1 1 (n and p means that neutron attacks and proton liberates).
1. 18 X 1013 = - X - X 6.023 X 1023
T 12 13. iN+
4
iHe - :H + fo
23
6.023 X 10 .
or T = ---...,.,,.--13 mm 14. 13Al27 + o''I - 12Mg24 + 1H3
1.18 X 10 X 12
i1Na23+ iH 2 - 12Mg24+ oflt
6.23 X 1023
T = - - - - - - - - - - - - yr
I. I 8 X 1013 X 12 X 60 X 24 X 365 15. ~ M -
8
{N + 2 iRe
= 8100yr X =230 ⇒ Y= 88
40. C=co(¾Y
~~ON - iL + 2 ?e(l3+)
A=230=n + p
Y = total time = 3 = 100 (J.)3= I2.5 g B = 86= p
half-life 2
n= 144
 Nuclear Chemistry I 483
16. Cadmium rods are used to absorb neutrons in nuclear reactors, 26. Moderator Graphite
because cadmium is neutron absorber. Control rods Boron
17. The radiant energy from the sun is due to nuclear fusion. Fuel rods Uranimn
18. Isotone are the species having same number of neutrons. In Coolant Sodimn
40 40
20 Ca , number of neutrons is 20 and in 18 Ar , number of
neutrons= 22. So, 20 Ca
40
and 40
18 Ar are not isotones. Topic 5 Applications of Radioactivity
19. Heavy water (020) is used as moderator in nuclear reactor. 1. The y-radiation emitted by Co -60 are used in the treatment of
cancer, as they can bum cancerous cells.
20. 11 Na
23
+ on' - 11Na
24
+ y-ray
14 4 17 1
2. Age of specimen (t) is related to the daughter/parent ratio of
21. 7 N + 2He - 80 + 1H number of atoms (D IP) by equation.
(X)
D=P(l-i')
Atomic number and atomic weight of reactant and products
should be the same. where, A. = decay constant
22. 4 [H - iHe + 2 ?e + energy D
p
= I - i ' ⇒ I + Dp = i '
It is the principal reaction of hydrogen bomb.
23. TiMg + 'Y - [H + ffNa t=±111(1 + ~)
Thus, nuclide of nNa is formed. 3. f;P is used in the treatment of blood cancer.
24. gAJ + iHe - ~~ + /,,1 4. The carbon-dating technique is used to find out the age of
25. Neutrons are neutral so they can not be accelerated. archaeological objects. This technique was studied by Willard
Li bby and got the Nobel prize for the same.
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21
p- Block Elements
QUICK REVIEW
Elements belonging to the group 13 to 18 of the perioclic table
are called p -block elements. Their valence shell electronic
2
configuration is ns2 np1- 6 except He (ls ).
Group 15 Elements
Nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb)
and bismuth (Bi) belong to VA group or 15th group of the
periodic table. Elements of nitrogen family are called
pnicogens and their compounds are called pnictides as these
elements fom1s pungent smelling compounds.
• Electronic configuration of these elements is ns 2 np 3 .
These elements are extra stable due to completely filled
s-subshell and half-filled p-subshell. These elements exhibit
+ 3 and + 5 oxidation states.
• Dinitrogen preparation Dinitrogen is prepared by the
liquefaction and fractional distillation of air.
(i) In the laboratory dinitrogen is prepared by treating an
aqueous solution of ammonium chloride with
sodium nitrite.
NH 4 Cl(aq) + NaN0 2 (aq) ~ N 2 (g) + 2H2 0 (/)
+ NaCl (aq)
(ii) Very pure nitrogen can be obtained by the thermal
decomposition of sodium or barium azide.
Ba(N3 ) 2 ~ Ba + 3N2
2NaN3 ~ 2Na + 3N2
Oxides of Nitrogen
All oxides of nitrogen (except NO and N 2 0) and phosphorus
are acidic in nature. Unlike other oxides of nitrogen, nitrous
oxide (N2 0) is not poisonous.
NO and N0 2 are paramagnetic due to the presence of
unpaired electrons in their molecules. N02 is called mixed
anhydride because it gives a mixture of HN0 2 and HN0 3
upon dissolution in water.
(i) Nitrous oxide (N2 0) is also known as laughing gas.
It is prepared by heating ammonium nitrate.
Heat
NH4 N0 3 ~ N2 0+ 2H2 0
(ii) Dinitrogen pentaoxide (N2 0 5 ) is obtained by
dehydrating HN0 3 with P2 0 5 .
4HN03 + P4 0 10 ~ 4HP03 + 2N2 0 5
• Oxoacids of nitrogen N itrous acid and nitric acid are
two main oxoacids of nitrogen. Nitrous acid (HN0 2 ) is
unstable and occurs only in aqueous solution. It acts as
oxidising and reducing agent and possess complex fonning
ability.
Reactivity Towards Hydrogen
Elements of 15th group form hydrides such as
NH 3 , PH 3 , AsH 3 SbH3 and BiH 3
(i) PH3 < AsH 3 < NH 3 < SbH3 < BiH3 boiling points
in increasing order.
(ii) NH 3 > PH3 > AsH 3 > SbH3 > BiH3 bond angles in
decreasing order.
(iii) NH 3 > PH3 > AsH 3 > SBH 3 > BiH3 bond strength
in decreasing order.
(iv) NH 3 > PH3 > AsH 3 > 5bH3 > BiH3 thermal
stability in decreasing order.
(v) NH 3 < PH3 <AsH 3 < SbH3 < BiH3
reducing character in increasing order.
 p-Block Elements I 485
Oxoacids of Phosphorus • Sulphuric acid Preparation by contact process
Hypophosphorous acid (H 3 P0 2 ) is monobasic and reducing 1/ 8 S 8 + 0 2 ~ S02
agent. VO
2 5
2 S02 (g) + 0 2 (g) 2S03 (g)
(i) Orthophosphorus acid (H 3 P03 ) is dibasic and 2 bar 720 V
reducing agent. S03 (g)+ H 2S04 ~ H 2S2 0 7 (Oleum)
(ii) Orthophosphoric acid (H 3 P04 )is weak tribasic acid. H2S20 7 + H 20 ~ 2H2 S04 (96. 98%)
(iii) Metaphosphoric acid (HP03 ) is monobasic and It is dibasic and strong oxidising agent.
exists as trimer.
(iv) Pyrophosphoric acid (H4 P20 7 ) is tetrabasic acid. Group 17 Elements
(v) Hypophosphoric acid (H4 P20 6 ) is tetrabasic acid.
• F, Cl, Br, I and At are the members ofgroup-17 (halogen
(vi) Pyrophosphorus acid (H4 P20 5 )is dibasic acid.
family). General valence shell configuration of these
· ns 2 np 5 .
e1ements 1s
Group 16 Elements
• Oxygen (0), sulphur (S), selenium (Se), tellw·ium (Te) and • Solubility of 12 is more in KI than in pure water. 12 when
polonium (Po) are the elements of VI A group. The first dissolved in potassium iodide solution (aq) results in
four elements are collectively known as chalcogens formation of polyhalide 13 ion which increases the solubility
• Electronic configuration of these elements is ns 2 np 4 . of 12 in water.
• Oxidation states Oxygen shows an oxidation state of - 2 l 2 (s)+ KI(aq) ~ KI 3 (aq) ~K+ (aq) +I3(aq)
in most of its compounds and - 1 state in peroxides . It
Due to absence of d-orbitals, fluorine does not form
shows only +2 state in OF2. Other elements of this group
polyhalides.
also show +2, +4 and +6 oxidation states. On moving down
the group, the stability of +6 oxidation state decreases due • Reactivity with Hydrogen Hydrides of halogens are
to inert pair effect. covalent in the gaseous state and behave as acids in the
• Reactivity with hydrogen Elements of 16th group form aqueous solution.
hydrides such as H 2 0, H 2S, H 2 Se, H 2Te and H 2 Po. (i) HI > HBr > HCl > HF acidic strength
(i) H 2 0> H 2S> H 2Se > H 2 Te melting and boiling (i1) HI > HBr > HCl > HF reducing character
point in decreasing order. (iii) HF > HI > HBr > HCl boiling points
(ii) H 2 0> H 2S> H 2Se> H 2 Te bond angle, dipole 3ox- ~ 2x- + xo;
moment and thermal stability in decreasing order.
• Oxoacids of halogens All the oxyacids of halogens are
(iii) H 2 Te> H 2 Se> H 2S > H 20 acidic, covalent and monobasic.
reducing character in decreasing order. (i) Them1al stability in decreasing order
• Reactivity with oxygen E02 and E0 3 HCIO 4 > HCIO 3 > HCIO 2 > HCIO
(i) Dioxides e.g. S02 , Se02 , Te0 2 . HI0 3 > HBr0 3 > HC10 3
(ii) Trioxides e.g. S03 , Se03 , Te03 . HClO> HBrO> HIO
• Diox ides can be prepared directly by burning. (ii) Acidic strength of oxoacids in decreasing order
• The acidic nature of dioxides and trioxides decreases in the HCIO> HBrO> HIO
order HCI04 > HC10 3 > HCI02 > HCIO
S02 > Se02 > Te02 and S03 > Se03 > Te0 3 (iii) Oxidising power in increasing order
• The acidic nature of a particular element increases with HC10 4 < HC10 3 < HC10 2 < HCIO
increase in oxidation number of the central element for • Halogen reacts with NH 3 and form different products.
example, SO< S02 < S03 8NH3 + 3Cl 2 ~ N 2 + 6NH4 Cl
• Reactivity with halogens EX 2 , EX 4 and EX 1 All the (Excess)

elements of group 16 form hexafluoride. Their stability NH 3 + 3Cl 2 ~ NC1 3 + 3HC1

decrease in the following order SF6 > SeF6 > TeF6 but (Excess)

ease of hydrolysis increases in the reverse order. SF4 is a Bromine also reacts with ammonia in the same way but the
gas, SeF4 is liquid and TeF4 is solid at room temperature. reaction of iodine with ammonia is different.
The tetrafluorides of group 16 can act both as a Lewis acid 2NH 3 + 312 ~ NI 3 · NH 3 + 3HI
and as a Lewis base. Explosive
486 I Chapterwise & Topicwise Engineering Entrances Solved Papers
• Pseudo halogens CN- , SCN- , OCN- possess properties similar to halide ions and contain atleast one N atom. The
con-esponding dimeric molecules such as (CN)i, (OCN)i (SCN) 2 are called pseudohalogens.

Group 18 Elements
• Consists of He, Ne, Ar, Kr, Xe and Rn having ns2np 6 (except He whose electronic configuration is ls2 ) .
All these elements are called noble gases, inert gases, the rare gases of atmosphere or aerogenes.
• Xenon because of its lowest ionisation energy can form compounds with oxygen and fluorine. No true compounds of helium,
neon and argon is as yet reported.
Compounds of Xe and F
Xe+ F2 673 K) XeF Xe+ 2F 873 K) XeF Xe + 3F S?3K ) XeF6
2 2 4 2
I bar ' I bar ' 60-70 bar

A mixture of20% He + 80%, 0 2 is used by deep sea divers. He is used for filling balloons and air ships due to its non-inflammable
nature and as a heat transfer agent in gas cooled atomic reactors. Ne is used in discharge lamps and signs (advertising). Ar is used
for filling incandescent metal filament electric bul bs. Radon is used in the treatment of cancer.
Fischer Ringe method is used is separate nobles gas mixture from air using 90% Ca C 2 and I 0% Ca Cl 2 .

Topic 1
Group 15 Elements
2014
1. The product formed in the reaction of SOC1 2 with white 7. The statements that is not con-ect is [KCETJ
phosphorus is [JEE Advanced] (a) hypophosphorous acid reduces silver nitrate to silver
(a) PC1 3 (b) SO2 Cl 2 (c) SCl 2 (d) POC1 3 (b) t r
in solid state PCI 5 exists as [PC1 4 [PCI 6
(c) pure phosphine is non-inflammable
2. Which of the following properties is not shown by NO?
(d) phosphorus acid on heating disproportionates to give
(a) It is diamagnetic in gaseous state [JEE Mains] metaphosphoric acid and phosphine
(b) It is a neutral oxide
(c) It combines with oxygen to form nitrogen dioxide
8. The bond angle in NF3 (I 02.3° ) is smaller than NH 3
(d) Its bond order is 2.5 (107.2°). This is because of CWB JEE]
3. Which has the smallest size ? [VITEEE] (a) large size ofF compared ofH
2 (b) large size ofN compared ofF
(a)Na+ (b)Mg + (c)A1 3 + (d) p 5+
(c) opposite polarity ofN in the two molecules
4. Solid N 2 O 5 is [Manipal] (d) small size ofH compared to N
(a) ionic (b) covalent 9. Which one of the following is least covalent in nature?
(c) coordinate covalent (d) metallic (a) NF3 (b) BiF3 [AMUJ
5. Which of the following phosphorus is the most reactive? (c) PF3 (d) SbF3
(a) Red phosphorus (b) White phosphorus l 0. Which of the following oxides, at the same concentration
(c) Scarlet phosphorus (d) Violet phosphorus when dissolved in water, results in the most acidic
6. The nitrite ion in represented by solutions ? [IPUCETJ
I. [0-N=OJ6 II. [N=0-0)6
Which of the structures represents possible resonance
11. Which is the anhydride of nitric acid ? [IPUCET]
fon-ns of this ion ? [Manipall
(a) Only I (b) Only II (a) NO (b) NO 2
(c) N 2 0 3 (d) N 2 0 5
(c) Both I and II (d) Neither I and I
 p-Block Elements I 487
2013
12. Concentrated mtr1c acid, upon long standing, turns 20. Among the following, the number of compounds that can
yellow-brown due to the fonnation of [JEE Advanc ed] react with PC! 5 to give POCl 3 is 0 2 , CO 2 , S02 , H 20 ,
(a) NO (b) N0 2 H 2S04 , P4 0 10 . [IITJEE]
(c) N 20 (d) N204 (a) l (b)2
(c) 3 (d) 4
2012 21. Which one of the following oxides of nitrogen dimerises
13. The reaction of white phosphorus with aqueous NaOH into a colourless solid/liquid on cooling ? [Ke rala CEEJ
gives phosphine along with another phosphorus containing
(a) N 20 (b) NO (c) N 20 3
compound. The reaction type, the oxidation states of
(d) N02 (e) N 20 5
phosphorus in phosphine and the other product are
respectively [HT JEE] 22. The least stable hydride of 15th group elements is
(a) redox reaction, - 3 and - 5 (a) NH 3 (b) PH 3 (c) AsH3 [Kerala CEE]
(b) redox reaction, 3 and + 5 (d) SbH 3 (e) BiH 3
( c) disproportionation reaction, - 3 and + 5
23. An element belongs to group 15 and third period of the
( d) disp roportionation reaction, - 3 and + 3
periodic table. Its electronic configw-ation will be
14. The molecule BF3 and NF3 both are covalent compounds, (a) ls22.s-2 2p3 (b) ls22.s-22p4 [WBJEE]
but BF3 is non-polar and NF3 is polar. 2 2 2 2 6 2
The reason is that [BITSAT] (c) ls 2.s- 2p 6 3s23p 3 (d) ls 2.s- 2p 3s23p
(a) boron is a metal and nitrogen is a gas in uncombined 24. N0 2 is not obtained on heating [WBJEE]
state
(b) BF3 bonds have no dipole moment whereas NF3 bond (a) AgN03 (b) KN0 3
have dipole moment (c) Cu(N03 )i (d) Pb(N0 3 )i
( c) atomic size of boron is smaller than that of nitrogen
(d) BF3 is symmetrical molecule whereas NF3 is 2010
unsymmetrical 2 5. Ammonia is dried over [Manipal]
15. Which of the following is tetrabasic acid? [Manipal] (a) slaked lime (b) calcium chloride
(a) Orthophosphorus acid ( c) phosphorus pentoxide ( d) quicklime
(b) Orthophosphric acid 26. The structural formula of hypophosphorous acid is
( c) Metaphosphoric acid CEAMCET]
( d) Pyrophosphoric acid
0 0- H
16. The stable bivalency ofpb and trivalency of Bi is
II I
(a) due to d contraction in Pb and Bi [WB JEE] (a) p (b) p
(b) due to relativistic contraction of the fu.orbitals of Pb w·,.,-- 1'----o H 1'----H
and Bi, leading to inert pair effect H OH
( c) due to screening effect
0
( d) due to attainment of noble liquid configuration 0
17. Which of the following is most acidic hydride ofnitrogen?
II II
(c) p (d) p
(a) N 3H (b) NH3 [OJEEJ H / 1 '----oH
HO/ 1 '----oH
OH
(c) N 2H 4 (d) Both N 3H and NH 3 OH
18. Soid PCl 5 exists as [AMU]
27. Phosphorns pentoxide is widely used as [Guj CET]
(a) PCl! (b) PC1 5 (a) bleaching agent (b) dehydrating agent
(c) PCl! and PC1 6 (d) PC1 6 (c) oxidising agent (d) reducing agent
28. Given areH 3P0 2 , H 3P0 3 , H3 P0 4 and H 4P2 0 7 .
2011 Which of the above oxoacids results into two series of
19. ExtrapureN2 canbeobtainedbyheating [IITJEE] salts ? [Guj CET]
(a) NH 3 with CuO (b) NH4N0 3 (a) H 3 P0 2
(c) (NH 4 ) 2 Cr20 7 (d) Ba(N3)i (c) H3 P0 4
488 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2009
29. The reaction ofP4 with X leads selectively to P4 0 6 . The Xis 40. Match the Column I (Molecules) with Colunm II (Boiling
(a) dry 0 2 [IIT JEE] points) and select the correct answer.
(b) a mixture of0 2 and N 2
Column I Column JI
(c) moist 0 2
( d) 0 2 in the presence of aqueous NaOH A. NH 3 I. 290K
30. In which of the following, NH 3 is not used? [ManipaIJ B. PH3 2. 211 K
(a) Tollen's reagent c. AsH3 3. 186K
(b) Nessler's reagent D. SbH3 4. 264 K
(c) Group reagent for the analysis of IV group basic
E. BiH3 5. 240K
radicals
( d) Group reagent for the analysis of m group basic
Codes [OJEEJ
radicals
A B C D E
31. The reaction of P4 with aqueous NaOH gives [OJEEJ
(a) 3 2 5 4 1
(a) P(OHh (b) 5 3 2 4 1
(c) P(OH)s (c) 1 4 5 2 3
(d) 1 2 3 4 5
32. IfN0 2 (N 2 0 4 ) is dissolved in NaOH, we get solution of
41. H 3 P0 3 has .......... non-ionisable P- Hbonds. [OJEEJ
(a) NaN0 2 [lndraprastha CET, CGPETJ
(a)3 (b) l
(b) NaN03 (c) 2 (d) None of these
(c) mixture ofNaN02 and NaN03
(d) NaN04 42. Which of the following(s) when heated give nitrogen gas?

33. Which element is used in the preparation of pesticides ? (a) (NH4 )z Cr2 0 7 (b) Ba(N3 ) 2 [OJEEJ
(c) NH 4 N03 (d) Both (a) and (b)
(a) Arsenic (b) Bismuth [Guj CETJ
(c) Antimony (d) Nitrogen 43. Which of the following is the correct order of increasing
enthalpy of vaporisation ? [Guj CETJ
2008 (a) NH 3 < PH 3 < AsH 3 (b) AsH3 < PH 3 < NH 3
34. The correct order ofreducing abilities of hydrides of (c) PH 3 < AsH 3 < NH3 (d) NH 3 < AsH 3 < PH 3
V group elements is [BITSAT, EAMCET, AMU]
44. The catalyst used in the manufacture of anunonia is
(a) NH3 < PH3 < AsH 3 < SbH 3 < BiH3
(a)V205 (b)Pt [J&K CETJ
(b) NH3 > PH 3 > AsH 3 > SbH3 > BiH3
(c) NH3 < PH3 > AsH 3 > SbH 3 > BiH3 (c) Fe (d) Ni(C0)4
(d) SbH3 > BiH3 > AsH 3 > NH 3 > PH 3 45. Which is tribasic acid ? [BCECE]
35. Reaction of PCl 3 and PhMgBr would give [VITEEEJ (a) H 3 P0 2
(a) bromobenzene (b) chlorobenzene (c) H 4 P2 0 7
(c) triphenylphosphine (d) dichlorobenzene 46. Liquor ammonia bottles are opened only after cooling.
36. The most stable hydride is [Manipal] This is because [Jamia Millia IslamiaJ
(a) NH3 (a) it is a mild explosive
(c) AsH 3 (b) it generates high vapour pressure
(c) Both (a) and (b)
37. Which of the element of nitrogen family produce
(d) it is a lachrymatory
maximum number of oxyacids ? [MP PET]
47. The atomicity of phosphorus is X and the PPP bond angle
(a) N (b) P (c) As (d) Sb
in the molecule is Y. What are X and Y? [DCEJ
38. Which of the following pairs is obtained on heating
(a)X=4,Y= 90° (b)X=4,Y=60°
anunonium dichromate ? [WB JEE]
(c) X = 3, Y = 120° (d) X = 2, Y = 180°
(a) N 2 and H 2 0 (b) N 2 0and H 2 0
(c) N0 2 and H 2 0 (d) NO and N0 2 2007
39. The correct order of acidic nature of oxides is in the order 48. Correct order of decreasing thermal stability is as
(a)NO < N 2 0 < N 2 0 3 < N02 <N2 0 5 [OJEE] (a) NH 3 > PH 3 > AsH 3 > SbH3 [BITSATJ
(b)N2 0 <NO < N 20 3 < N02 <N2 0 5 (b) PH 3 > NH 3 > AsH 3 > SbH3
(c)N2 0 5 <N0 2 < N 20 3 < NO < N 20 (c) AsH 3 > PH 3 > NH 3 > SbH3
(d)N20 5 < N 2 0 3 <N0 2 < NO < N 20 (d) SbH3 > AsH 3 > PH 3 > NH 3
 p -Block Elements I 489
49. Which one of the following pentafluorides cannot be 60. Zinc and cold dil. HNO 3 reacts to produce [BCECE]
formed? [BITSAT]
(a) PF5 (b) AsF5 (c) SbF5 (d) BiF5
50. Sodium pyrophosphate is represented by which of the 61. The sides of safety matches contains [BCECE]
following fonnula ? [Manipal, WB JEE]
(a) red phosphorus + sand powder
(a) Na 2 P2 O 4 (b) Na 4P2 O 5
(b) P4S3
(c) Na 4 P2 O 7 (d) Na 2 P2 O 5
(c) Ca 3 (PO) 4 + glass pieces
51. What are the products obtained when ammonia is reacted (d) KClO3 , KNO 3, sulphur+ antimony
with excess chlorine ? [WB JEE]
(a) N 2 and NC1 3 (b) N 2 and HCl 2007
(c) N 2 and NH4Cl (d) NC1 3 and HCl 62. Which one is con-ect statement ? [DCE]
52. Reaction ofHNO3 with I, S, P and C gives respectively (a) Basicity ofH 3 PO4 and H 3 PO 3 is 3 and 3 respectively
(a) HI0 3 , H 2 SO 4 , H 3 PO4 and CO 2 [WBJEE] (b) Acidity ofH 3 PO4 and H 3 PO 3 is 3 and3 respectively
(b) HI03 , H 2 SO 4 , H 3 PO 3 and CO2 (c) Acidity ofH 3 PO4 and H 3 PO 3 is 3 and2 respectively
(c) HI0 2 , H 2 SO 4 , H 3PO4 and CO (d) BasicityofH3 PO 4 and H 3 PO 3 is 3 and 2 respectively
(d) 12 0 5 , SO2 , P2 Oand CO2
53. Red P can be obtained by white P by [WBJEE] 2006
(a) heating it with a catalyst in an inert atmosphere 63. Which of the following statement is true? [AIEEE]
(b) distilling it in an inert atmosphere (a) H 3PO3 is a stronger acid than H 2 SO 3
(c) dissolving it in CS 2 and crystallising (b) In aqueous medium HF is a stronger acid than HCl
(d) melting it and pouring the liquid into water (c) HC1O4 is a weaker acid than HC1O 3
54. ThebasicityofH3 PO4 is [WBJEE]
(d) HNO3 is a stronger acid than HNO 2
002 ~3 ~4 oos 64. The decreasing values of bond angles from NH 3 (107° )to
55. Liquor ammonia is [WB JEE] SbH3 (91° )down the group-15 of the periodic table is due
to [AIEEE]
(a) ammonium hydroxide
(b) liquefied ammonia gas (a) increasing bp-bp repulsion
(c) concentrated solution of NH 3 in water (b) increasing p-orbital character in sp 3
(d) a solution of NH 3 in alcohol (c) decreasing lp-bp repulsion
56. The con-ect order of boiling points of the hydrides of (d) decreasing electronegativity
nitrogen family is [OJEEJ 65. The treatment of Cu with dilute HNO 3 gives [Manipal]
(a) NH 3 > PH3 > AsH 3 > SbH3 (a) N 2 0 (b) NO
(b) PH3 < AsH3 < NH3 < SbH3 (c) NH! (d) NO 2
(c) NH 3 < PH3 < SbH3 < AsH 3
(d) NH 3 < PH 3 < AsH3 < SbH3 66. Which of the following oxyacids of phosphorus is a
reducing agent and monobasic ? [Manip al]
57. NaNH2 + N 2 O ~ X + NaOH+ NH 3 .
(a) H 3PO 2 (b) H 3PO3
What is the X ? [OJEE]
(c) H 3 PO 4 (d) H 4 P2 O 6
(a) N3Ni (b) Na 3N
67. Pnicogens are the elements of group CMHT CET]
(c) NaN3 (d) None of these
(a) 15 (b) 13
58. P4 + 3NaOH + 3H2 0 ~ A + 3NaH2 PO2 , here A is
(c) 8 (d) zero
(a) NH 3 (b) PH3 lAMUJ 68. Which of the following fom1s vortex ring? [MHT CET]
(c) H 3PO4 (d) H 3PO 3 (a) P2 0 5 (b) PH 3
59. The following are some statements related to VA group (c) NH 3 (d) P4 O10
hydrides. 69. As the number of - OH groups increases in
I. Reducing property increases from NH 3 to BiH3.
hypophosphorus acid, phosphorus acid and phosphoric
II. Tendency to donate lone pair decreases from NH3 to BiH3 .
acid, the acidic strength [MHT CET]
III. Thermal stability of hydrides decreases from NH 3 to BiH3 .
IV. Bond angle of hy drides decreases form NH3 to BiH3 . (a) increases
(b) decreases
The con-ect statements are [EAMCET]
(c) remains nearly same
(a) I, II, III and IV (b) I, III and IV (d) remains appropriately same
(c) I, II and IV (d) I and IV
490 I Chapterwise & Topicwise Engineering Entrances Solved Papers
70. Pb reacts with dilute HNO 3 gives [MPPET] 2005
(a) NO (b) NH4 NO 3 81. Which is most thermodynamically stable allotropic form of
(c) N 2 O 5 (d) NO 2 phosphorus ? [IIT JEE]
71. Which gas is evolved by the treatment of magnesium with (a) Red (b) White
very dilute solution ofHNO 3 ? [WB JEE] (c) Black (d) Yellow
(a) N 2 (b) NO 2 82. Which blue-liquid is obtained on reacting equimolar
(c) H 2 (d) H 2 0 amounts of two gases at - 30° C? [IITJEE]
72. PCl 3 and cold water reacts to produce which of the (a) N 2 O (b) N2 O3
following ? [WB JEE] (c) N 2 0 4 (d) N 2 0 5
(a) H 3PO 3 (b) H 3PO2 83. The number of hydrogen atom(s) attached to phosphorus
(c) H 4 P2 O 7 (d) H 3 PO4 atom in hypophosphorus acid is [AIEEEJ
73. Which phosphorus reacts with KOH solution to produce (a) three (b) one
phosphine gas ? CWB JEE] (c) two (d) zero
(a) White phosphorus 84. Dinitrogen pentoxide (N 2 O 5 ), a colourless solid, is
(b) Red phosphorus prepared by [BITSATJ
(c) Both (a) and (b)
(d) None of the above (a) heating NH4 NO 2 with an excess of oxygen
74. Which ofthe following oxide does not form acidic aqueous (b) dehydrating HNO3 with Cao
solution ? [WB JEE] (c) dehydrating HNO 3 with P4 O10
(b) NO 2 (d) heating a mixture ofHNO2 and Ca(NO3)z
(d)NO 85. Incorrect statement for pyrophosphoric acid H 4 P20 5 is
75. The metal which does not fom1 ammonium nitrate by (a) it contains P in+ 5 oxidation state CBITSATJ
reaction with dilute nitric acid is [AMU] (b) it is dibasic acid
(a) Al (b) Fe (c) Pb (d) Mg (c) it is strongly reducing in nature
76. In the electrothermal process, the compound displaced by (d) it contains one P -O-P bond
silica from calcium phosphate is [AMU]
86. In which of these processes platinum is used as a catalyst?
(a) calcium phosphide
(b) phosphine (a) Oxidation of ammonia to form HNO 3 [Manipall
(c) phosphorus (b) Hardening of oils
(d) phosphorus pentoxide (c) Production of synthetic rubber
(d) Synthesis of methanol
77. Hydrolysis of NCI 3 gives NH3 and X. Which of the
87. Iron is dropped in dil. HNO 3, it gives [Manipal]
following is X ? [EAMCET]
(a) HCIO4 (b) HC1O3 (a) ferric nitrate
(b) ferric nitrate and NO2
(c) HOCI (d) HCIO2
(c) ferrous nitrate and ammonium nitrate
78. Calcium cyanamide on treatment with steam produces (d) ferrous nitrate and nitric oxide
(a) NH 3 + CaO [Guj CETJ 88. When p lants and animals decay, the organic nitrogen is
(b) NH 3 + CaHCO3 converted into inorganic nitrogen. The inorganic nitrogen
(c) NH 3 + CaCO3 is in the fom1 of CKCETJ
(d) NH 3 + Ca(OH)z
(a) ammonia (b) elements ofnitrogen
79. What is the product fonned when phosphorus trioxide is (c) nitrates (d) nitrides
dissolved in water ? [J&K CET]
89. Which of the following is not correct? [EAMCET]
(a)HPO 3 (b)H 3 PO4 (c)H 3 PO 3 (d)HPO 2
(a) Ammonia is used as refrigerant
80. Hypophosphorus acid, H 3PO2 is [BCECEJ (b) A mixture ofCa(CNh and C is known as nitrolirn
(a) a monobasic acid (c) A mixture of Ca{H 2 PO4 )z and CaSO4 -2H2O is
(b) a tribasic acid
known as superphosphate of lime
(c) a dibasic acid
(d) Hydrolysis ofNCl 3 g ives NH 3 and HOCl
(d) not acidic at all
 p-Block Elements I 491
90. The structure of 01thophosphoric acid is [Guj CET] 92. In Ostwald process of manufacturing of HN0 3 , catalyst
0 H used is [BCECEJ
i I (a) Mo (b) Fe (c) Mn (d) Pt
(a) H-O-P-0-H (b) O~P-0-H
93. When heated NH 3 is passed over CuO, gas evolved is
bI 6I (a)N2 (b)N20 [BCECEJ
(c) HN0 3 (d) N0 2
H H
94. Which of the following is kept in water ?
r
[BCECE]

(c)O~P-0-H (d)H-OP= O
? (a) White phosphorus
(c) Potassium
(b) Sodium
(d) Calcium
I 95. White phosphorus is [DCEJ
H (a) a monoatomic gas
91. Which of the following is a tribasic acid ? [J&K CET] (b) P4 , a tetrahedral solid
(a) H 3 P04 (b) HP03 (c) P8 , a crown
(c) H 4 P2 0 7 (d) H 4 P2 0 6 (d) a linear diatomic molecule

Topi c 2
Group 16 Elements
2014
1. Consider the following statements. 6. Among the following observations, the correct one that
T. NCl 5 does not exist while PCl 5 does. differentiates between SOi - and SO~ - is [WB JEE]
IT. Both 0~ and NO are paramagnetic. (a) both form precipitate with BaCl 2 , so;- dissolves in
UT. The three C-0 bonds are not equal in carbonate ion.
HCl but SO~ - does not
TV. Lead prefers to form tetravalent compound.
Which of the above statements are incorrect ?
(b) so; - forms precipitate with BaC12 , so;- does not
(a) I and m (b) I, III and IV [BITSAT] (c) so;- forms precipitate with BaC1 2 , so;- does not
(c) II an III (d) III and IV
( d) both form precipitate with BaCl 2 , so~- dissolves in
2. When the substances CC1 4 , CH 4 and CF4 are arranged in
order of increasing boiling point, what is the correct HCl but so; - does not
order ? [Manip all
(a) CC1 4 , CF4 , CH4 2013
(b) CH4 , CF4 , CCl4 7. The correct statements (s) about 0 3 is (are)
(c) CF4 , CC1 4 , CH 4 [JEE Advan ced]
(d) CF4 , CH4 , CC1 4 (a) O-Obond lengths are equal
3. (SiH 3 ) 3 N is [Manipal] (b) thermal decomposition of03 is endothermic
(c) 0 3 is diamagnetic in nature
(a) planar (b) pyramidal
( d) 0 3 has a bent structure
( c) octahedral (d) tetrahedral
4. A crystalline solid X reacts with di!. HCl to liberate a gas
8. The atomicity of sulphur in rhombic sulphur is [KCETJ
Y. Y decolourises acidified KMn0 4 • When a gas Z is (a)l (b)2 (c)4
slowly passed into an aqueous solution of Y, colloidal (d)6 (e)8
sulphur is obtained X and Z could be respectively 9. When H2 S gas is passed through nitric acid, the product is
(a) Na 2S, S03 (b)Na 2 S04 , H 2S [KCET] (a) rhombic S [Kerala CETJ
(c)Na 2S03 ,H2 S (d)Na 2 S04 ,S02 (b) prismatic S (colloidal)
5. Conversion of oxygen into ozone is non-spontaneous at ( c) amorphous S
( d) monoclinic S
(a) all temperature (b) high temperature [KCET] (e) plastic S
(c) room temperature (d) low temperature
492 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2012
10. The ore that is concentrated by the froth floatation process 20. A gas, that relights glowing splinter, is
is [KCET] [Indraprastha CET, CG PET]
(a) cryolite (b) cuprite (b) 0 2
(c) calamine (d) chalcopyrites (d) NO 2
21. Which element is not considered as 'chalcogens'?
2011
(a) Selenium (b) Oxygen [Guj CET]
11. Which of the following statements regarding sulphur is
(c) Sulphur (d) Polonium
incorrect ? [AIEEE]

(a) SO2 molecule is paramagnetic 2008

(b) The vapour at 200°C consists mostly of S 8 rings 22. Which of the following salt would give SO2 with hot and
(C) At 600°C the gas main]y consists of S2 molecules
(d) The oxidation state of sulphur is never less than+ 4 in di!. H 2SO 4 and also decolourises Br2 water? [Manipal]
its compounds (a) Na 2 SO3 (b) NaHSO4
(c) Na 2 SO4 (d) Na 2 S
12. Which one of the following is not true at room temperature
and pressure? [WB JEE] 23. Excess ofPCl 5 reacts with cone. H 2 SO4 giving [KCET]
(a) P4 0 10 is a white solid (a) chlorosulphonic acid (b) thionyl chloride
(b) SO2 is a colourless gas (c) sulphuryl chloride (d) sulphurous acid
(c) SO3 is a colourless gas 24. The element evolving two different gases on reaction with
(d) NO 2 is brown gas cone. sulphuric acid is [Ke rala CEE]

2010 (a) P (b)C

(c) Hg (d) S
13. Sulphuric acid has great affinity for water because (e) Sn
(a) it hydrolyses the acid [Manipal]
25. Select the incon-ect statement among the following.
(b) it decomposes the acid
[WBJEE]
(c) acid forms hydrates with water
(d) acid decomposes water (a) 0 3 is used as germicide for purification of air
(b) In 0 3 , 0 - O bond length is identical with that of
molecular oxygen.
14. Oxalic acid when heated with cone. H 2 SO 4 , gives
(c) 0 3 molecule is angular in shape.
(a) H 2O 2 and CO2 (b) CO and CO 2 [Manipal] (d) 0 3 is an oxidising agent.
(c) H 2O 2 and CO (d) CO2 and H 2 S
26. In the laboratory H 2 S gas is prepared by using black lumps
15. Which compound does not has S-S bond ? [MP PET] and di!. H 2 SO 4 . The black lumps are [J&K CET]
(a) Na 2 S2 O 4 (b) Na 2 S4 O 6 (a) FeSO 4 (b) MnO2
(c) Na 2 S2 O 3 (d) Na 2 S2 O 7 (c) FeS (d) FeSO3
16. Oleum is chemically [Punjab CET] 27. Ozone is used for purifying water because [BCECE]
(a) H 2 SO3 (b) H 2 SO5 (a) it dissociates and release oxygen
(c) H 2 S2 0 7 (d) H 2 S2 0 8 (b) do not leave any foul smell like chlorine
17. The substance which does not liberate oxygen on treatment (c) kills bacteria, cyst, fungi and acts as a biocide
with ozone is [RPET] (d) All of the above
(a) PbS (b) HCl (c) SO 2 (d) Hg 28. H 2 Sis not a/an [BCECE]

2009 (a) reducing agent (b) acidic

(c) oxidising agent (d) None of these
18. The fw1ction of Fe(OHh in the contact process is
(a) to remove arsenic impurity [Manipal] 2007
(b) to detect colloidal impurity 29. When cone. H2 SO 4 is heated with P2 O 5 , the acid is
(c) to remove moisture
converted into [KCETJ
(d) to remove dust particles
(a) sulphur trioxide
19. Concentrated sulphuric acid can be reduced by
(b) sulphur d ioxide
(a) NaCl (b) NaF [Kerala CEE]
(c) sulphur
(c) NaOH (d) NaNO 3 (d) a mixture of sulphur dioxide and sulphur trioxide
(e) NaBr
 p-Block Elements I 493
30. Which among the following statements are correct ? 41. Which of the following is not correct? [EAMCETJ
I. Carbon monoxide is neutral whereas SO3 is acidic. S ilent electric
II. Potassium oxide is basic whereas nitrous oxide is (a) 30, - - - 203 ; 11H = - 284.5 kJ
- discharge
acidic.
III. Aluminium and zinc oxides are amphoteric. (b) Ozone undergoes addition reaction with unsaturated
IV. Sulphur trioxide is aciclic whereas phosphorus carbon compounds
pentaoxide is basic. (c) Sodium thiosulphate reacts with I 2 to form sodium
V . Carbon dioxide is neutral whereas sulphur d ioxide is tetratbionate and sodium iodide
amphoteric. [Kerala CEE] (d) Ozone oxidises lead sulphide to lead sulphate
(a) II and Ill (b) I and IV 42. At T (K.), 100 L of dry oxygen is present in a sealed
(c) I and III (d) II and IV container. It is subjected to silent electric discharge, till the
(e) III and V volumes of oxygen and ozone become equal. What is the
volume (in litres) of ozone formed at T (K)? [EAMCETJ
31. Sulphur does not exist as S 2 molecule because [WB JEE]
(a) 50 (b) 60
(a) it is less electronegative
(c) 30 (d) 40
(b) it is not able to constitute pre- pre bonds
(c) it has ability to exhibit catenation 43. Copper turnings on heating with cone. H 2SO 4 produce
( d) of tendency to show variable oxidation states (a) H2S (b) 02 [Guj CETJ
32. Polyanion formation is maximum in [WB JEE] (c) SO3 (d) SO 2
(a) nitrogen (b) sulphur 44. The molecular formula of dithionic acid is [J&K CETJ
(c) oxygen (d) boron (a) H2S 2O 4 (b) H 2S 2O 6
33. Olewn is [WBJEE] (c) H 2S 2O 5 (d) H 2S 2 O 7
(a) castor oil (b) oil of vitriol 45. In presence ofmoisture, SO2 can [BCECEJ
(c) fuming H 2 SO 4 (d) None of these (a) act as oxidant (b) act as reductant
34. Which of the following is not a peroxy acid? [EAMCETJ (c) gain electron (d) not act as reductant
(a) Perphosphoric acid (b) Pernitric acid
(c) Perdisulphuric acid (d) Perchloric acid
2005
35. The catalyst used in the manufacture ofH 2SO 4 by contact 46. Which of the following is not oxiclised by 0 3 ? [IITJEEJ
process is [J&K CET] (a) KI (b) FeSO4
(c) KMnO4 (d) K 2 MnO4
(a) V2 O 3 (b) V2O 5 (c) FeO (d) Cu
47. SO2 + H 2S ~ Product.The final product is [OJEEJ
2006 (a)H 2 O + S
36. SO2 doesnotactas CBITSAT] (c) H 2 SO3
(a) bleaching agent 48. Which one ofthe following pairs ofreactants does not form
(b) oxidising agent oxygen when they react with each other ? CEAMCETJ
( c) reducing agent
(a) F2 , NaOH solution (hot, cone.)
(d) dehydrating agent
(b) F2 , H 2 0
37. If an allotropic form changes slowly to a stable fom1. It is (c) Cl 2 , NaOHsolution (cold, clilute)
called [MIIT CET] (d) CaOCl 2 , H 2SO4 (dilute, small amount)
(a) enantiotropy (b) dynamic allotropy 49. In the manufacture of s ulphuric acid by contact process,
(c) monotropy (d) None of these Tyndall box is used to [Guj CET, KCETJ
38. The most abundant element in the earth crust is [MP PET] (a) filter dust particles
(a) 0 (b) Si (c) H (d) C (b) remove impurities
39. Industrial name ofH 2S 2 0 7 is [WB JEE] ( c) conve11 SO 2 to SO3
( d) test the presence of dust particles
(a) pyrosulphuric acid (b) Marshall 's acid
(c) oleum (d) A ll of these 50. Which requires catalyst ? [J&KCET]

40. Bleaching action of SO2 is due to its [WB JEE] (a) S + 0 2 ~ SO 2

(b) 2SO2 + 0 2 ~ 2SO 3
(a) oxiclising property (b) acidic property ( c) C + 0 2 ~ CO2
( c) basic property (d) reducing property ( d) All of the above
 Topic 3
Group 17 Elements
2014
1. Among the following oxoacids, the correct decreasing 9. R, S andT,respectively, are [JEE Adv anced]
order of acid strength is [JEE Mains] (a) SO2Cl 2 ,PCl 5 and H 3PO 4
(a) HOCl> HC1O2 > HCIO 3 > HC1O3 (b) SO2Cl 2 , PC1 3 and H 3PO 3
(b) HCIO4 > HOCI > HCIO 2 > HC1O 3 (c) SOC12 , PCl 3 and H 3PO 2
(c) HC1O4 > HC1O 3 > HCIO 2 > HOCl (d) SOC1 2 , PC1 5 and H 3 PO 4
(d) HC1O 2 > HCIO 4 > HCIO3 > HOCI 10. Bleaching powder loses its power on keeping for a long
2. Iodine is formed when potassium iodide reacts with a time because [KCETJ
solution of [VIT] (a) it changes into calcium hypochlorate
(a) ZnSO4 (b) it changes into calcium chloride and calcium
(b) CuSO 4 hydroxide
(c) (NH 4 )z SO 4 (c) it absorbs moisture
(d) Na 2 SO4 ( d) it changes into calcium chloride and calcium chlorate
3. The high oxidising power of fluorine in due to its 2012
(a) high electron affinity [Manipal]
11. Which of the following halides reacts (s) with
(b) high heat of dissociation and low heat of hydration
AgNO 3 (aq) to give a precipitate that dissolves in
( c) low heat of dissociation and high heat of hydration
Na 2 S2 0 3 (aq)? [IITJEE]
(d) high heat of dissociation and heat of hydration
t,. (a) HCI (b)HF
4. MnO2 + HCI ~ A (g) (c) HBr (d) Hl
573 K 12. 25 mL ofhousehold bleach solution was mixed with 30 mL
A (g) + F2 (excess) ~ B (g)
of0.50 M KI and 10 mL of 4 N acetic acid. In the titration
B (l) + U (s) ~ C (g)+D (g) of the liberated iodine, 48 mL of 0.25 N Na 2S 2 0 3 was
The gases A, B, C and D are respectively [KCET] used to reach the end point. The molarity of the household
(a) Cl 2 , ClF, UF6 , ClF3 bleach solution, is [IIT JEE]
(b) Cl 2 , CIF3 , UF6 , CIF (a) 0.48 M (b) 0.96 M
(c) 0 2 , OF2 , U 2O3, O2F2 (c) 0.24 M (d) 0.024 M
(d) 0 2 , O 2F2 , U2O3, OF2 13. Bleaching powder contains a salt of an oxoacid as one of its
5. The hydrides of the first elements in groups 15- 17, namely components. The anhydride of that oxoacid, is [IIT JEE]
NH3 , H 20 and HF respectively shows abnormally high (a)Cl 2O (b)Cl 2 O 7
values for melting and boiling points. This is due to (c) ClO 2 (d) Cl 2 O 6
(a) small size ofN, 0 and F [WB JEE]
14. Which of the following is not a pseudohalide? [OJEEJ
(b) the ability to form extensive intermolecular H-bonding
(c) the ability to form extensive intramolecular H-bonding (a)Rcoo- (b) N 3
(d) effective van der Waals' interaction (c) CNO- (d) CN-
6. The interhalogen having dimeric structure is [AMU] 15. The relative basic character of the following is [AMUJ
(a) C IF3 (b) BrF3 (c) IF3 (d) IC13 (a) Clo- < ClO2 < CIO3 < ClO 4
7. Among the following molecule which has the zero dipole (b) CIO;j < CIO3 < c1O; < Clo-
moment ? [J&K CET] (c) CIO3 < CIO;j < ClO2 < ClO-
(a) BF3 (b) H 2 O (c) NF3 (d) ClO2 (d) ClO2 <Clo- < CIO3 < CIO4
2013 2011
8. P and Q respectively, are the sodium salts of
16. Which of the following is used to prepare Cl 2 gas at room
(a) hypochlorous and chloric acids [JEE Advanced]
temperature from concentrated HCl? [WB JEE]
(b) hypochlorous and chlorous acids
( c) chloric and perchloric acids (a) MnO 2 (b) H 2 S
(d) chloric and hypochlorous acids (c) KMnO4 (d) Cr2 O 3
 p-Block Elements I 495
2010
17. In halogen's group which element has highest electron 27. The correct order of heat of formation of halogen acids is
affinity? [MP PET] (a) HI > HBr > HCl > HF [UPSEEJ
(a) F (b) Cl (b) HF > HCl > HBr > HI
(c) Br (d) I (c) HCl > HF > HBr > HI
18. Which one is the anhydride ofHClO 4 ? [Punjab CET] ( d) HCl > HBr > HF > HI
(a) Cl02 (b) Cl 2 0 7 28. When chlorine reacts with di!. NaOH under cold
(c) Cl 2 0 (d) Cl 2 0 6 conditions, the oxidation state of chlorine changes from
zero to [J&K CETJ
19. Which of the following compounds gives chlorine dioxide
when it reacts with S02 in the presence of acid ? (a) - 1and + 5 (b) +land+ 4
(a) Sodium chloride [Guj CETJ (c) +Sand + 3 (d) -1 and+ 1
(b) Sodium chlorate 29. Which of the following dissolves in water but does not give
(c) Sodium perchlorate any oxyacid solution? [DCEJ
(d) Sodium chlorite (a) S02 (b) OF2
20. In the manufacture of bromine from sea water, the mother (c) SC14 (d) S03
liquor containing bromide is treated with [JCECEJ
(a) carbon dioxide (b) chlorine
2007
(c) iodine (d) sulphur dioxide 30. Identify the incorrect statement among the following.
(a) Ozone reacts with S02 to give S03 [AIEEEJ
2009 (b) Silicon reacts w ith NaOH(aq) in the presence ofair to
21. CIO- disproportionate into [OJEE] give Na 2 Si03 and H 2 0
(a) C l- and 0 (b) c1- and Cl0 3 (c) Cl 2 reacts with excess ofNH 3 to give N 2 and HCl
(c) C l and 0 (d) Cl- and o- ( d) Br2 reacts with hot and strong NaOH solution to give
NaBr, NaBr04 and H 2 0
22. The following species will not exhibit disproportionation
reaction [AMU] 31. Among K, Ca, Fe and Zn, the element which can fom1
(a) CIO- (b) Cl02 more than one binary compound with chlorine is
(a) Fe (b) Zn [Manipal]
(c) C l0 3 (d) Cl0 4
(c) K (d) Ca
23. Correct order of electron affinities of halogens is
32. Which one of the following reacts with glass? [MHT CETJ
(a) F > Cl > Br > I [lndraprastha CET, CG PET]
(a) H 2 S04 (b) HF
(b) I > Br > Cl > F
(c) HN0 3 (d) K 2 Cr2 0 7
(c)Cl > F > I > Br
( d) Cl > F > Br > I 33. Which one of the following can be purified by
sublimation ? [MHT CET]
24. In which case, the order of acidic strength is not correct?
(a) HI> HBr> HCl [DCEJ
(b) HI04 > HBr0 4 > HC104
(c) HC104 > HC10 3 > HC102 34. Iodine readily dissolves in potassium iodide solution
(d) HF> H 2 0> NH 3 giving CWB JEE]

2008 (a) r (b) KI-

(c) KI2 (d) KI3
25. Which one of the following reactions does not occur ?
[BITSAT, AMU, EAMCET] 35. Which of the following is anhydride of perchloric acid ?
[UPSEE, WB JEE]
(a) F2 + 2Cl- ~ 2F- + Cl 2
(a) Cl 2 0 7 (b) Cl 2 0 5
(b)Cl 2 + 2F- ~ 2Cl- + F2
(c) Cl 2 0 3 (d) HClO
(c) Br2 + 2r ~ 2Br- + 12
36. Which among the following factors is the most important
(d) Cl 2 + 2Br- ~ 2Cl- + Br2
in making fluorine the strongest oxidising agent?
26. Which of the following pairs has bleaching property? (a) Electron affinity [UPSEE, Jamia Millia Islamia]
( a) 0 3 and N02 (b) 0 3 and H 2 S [MP PET] (b) Ionisation enthalp y
(c) S02 and Cl 2 (d) Cl 2 and N0 2 (c) H ydration enthalpy
(d) Bond dissociation energy
496 I Chapterwise & Topicwise Engineering Entrances Solved Papers

37. Most acidic oxide among the following is [AMU] 49. When I 2 is passed through KCI, KF and KBr solutions
(a) Cl 2 O 5 {b) Cl 2 O (a) Cl 2 and Br2 are evolved [WB JEE]
(c) Cl 2 O 3 (d) Cl 2 O 7 (b) Cl 2 is evolved
38. Least stable oxide ofchlorine is CBCECEJ (c) Cl 2 , Br2 and F2 are evolved
(a) Cl 2 O (b) ClO2 (d) None of the above
(c) Cl 2 O 7 (d) ClO3 50. Fluorine exhibits an oxidation state of only - 1 because
39. Which reaction is not valid? [DCEJ (a) it can readily accept an electron [UP SEE]
(a) HCl + F2 ~ HF + Cl 2 (b) it is very strongly electronegative
(b) HF + Cl 2 ~ F2 + HCI (c) it is a non-metal
(c) Zn+ HCl ~ ZnCl 2 + H2 (d) it belongs to halogen family
(d) Al + HCI ~ AICl 3 + H2
51. The deficiency of iodine in diet causes CUP SEE, Guj CETJ
2006 (a) rickets (b) night blindness
( c) beri-beri ( d) goitre
40. What products are expected from the disproportionation
reaction of hypochlorous acid ? [AIEEEJ 52. Among the halogens, the one which is oxidised by nitric
acid is [AMUJ
(a) HC1O3 and Cl 2 O (b) HC1O2 and HC1O4
(a) fluorine (b) iodine
(c) HCl and Cl 2 O (d) HCl and HC1O 3
( c) chlorine (d) bromine
41. Which of the following is called Berthelot's salt?
53. Observe the following statements.
(a) {NaPO3 ) 6 {b) NaOCl [BITSATJ
T. Bleaching powder is used in the preparation of chloroform.
(c) KC1O 3 (d) KHF2
TI. Bleaching powder decomposes in the presence ofCoCl 2 to
42. Solubility of iodine in water may be increased by adding liberate 0 2•
(a) chloroform [Manipall ITT. Aqueous KHF2 is used in the preparation of fluorine.
(b) potassium iodide The correct combination is [EAMCETJ
( c) carbon disulphide
(a) I, II and III (b) Only II
( d) sodium thiosulphate
(c) I and III (d) I and II
43. Apatite is an ore of [MIIT CETJ
54. The bond dissociation energy of Cl 2 , Br2 and 12 follow the
(a) fluorine (b) chlorine (c) bromine (d) iodine
order [J&K CET]
44. Which one of the following has lowest bond dissociation (a) Cl 2 > 12 > Br2 (b) 12 > Br2 > Cl 2
energy ? [MP PET] (c) 12 = Cl 2 = Br2 (d) Cl 2 > Br2 > 12
(a) CI-CI (b) F-F
(c) Br- Br (d) I- I 55. When chlorine is passed through concentrated solution of
KOH, the compound fom1ed is [BCECE]
45. When F2 reacts with hot and concentrated NaOH then
(a) KC1O 4 (b) KC1O 3
following will be obtained [MP PET] (c) KCIO 2 (d) KClO
(a)O 2 (b)H 2
56. Which one will liberate Br2 from KBr ? [BCECE]
(c)Na 2 O (d)Na
46. Which of the following chloride is water insoluble ? (c) HI (d) Cl 2
(a) HCI (b) AgCI [WB JEE] 2005
(c) Both (a) and (b) (d) None of these 57. The correct order of the thermal stability of hydrogen
47. I 2 dissolves in Kl solution due to the formation of halides (H-X)is [AIEEE]
(a) KC 2 and 1- (b) K +, rand 12 [WB JEE] (a) HI > HCI < HF > HBr
(c) 13 (d) None of the above (b) HCI < HF > HBr < HI
(c) HF > H Cl > HBr > HI
48. Fluorine is the best oxidising agent because it has ( d) HI > HBr > HCl > HF
(a) highest electron affinity [WB JEE] 58. KF combines with HF to form KHF2 . The compound
(b) highest £:d contains the species [BITSATJ
(c) highest E~xid (a) K +, F- and H+ (b) K +, F - and HF
( d) lowest electron affinity ( c) K + and [HF2 r (d)[KHFt and F 2
 p-Block Elements I 497
59. Which of the following compounds is not an 62. Which of the following is most volatile ? [J&K CET]
"interpseudohalogen"? [BITSAT] (a) HF (b) HCI
(a) Cl 2N 3 (b) BrCN (c) ClCN (d) ICN (c) HBr (d) HI
60. The correct order of acidity of halogenic acids is [OJEEJ 63. The correct order of pseudohalide, polyhalide and
(a) HF < HCl < HBr < HJ (b) HI < HBr < HCl < HF interhalogen are [DCEJ
(c) HI < HCl < HBr < HF (d) HF < HBr < HI < HCl (a) BrI2 , OCN- , IF5
61. Aqua-regia is [OJEE] (b) IF5 , BrI2 , OCN-
(a) I: 3 cone. HNO 3 and cone. HCl ( c) OCN- , IF5 , Brl2
(b) I: 2 cone. HNO 3 and cone. HCl (d) OCN- , Brl2, IF5
(c) 3: lconc. HNO 3 and cone. HCI
(d) 2: I cone. HNO 3 and cone. HCl

Topic 4
Group 18 Elements
2014
1. Under ambient conditions, the total number of gases 5. The structure ofXeOF4 is [EAMCET]
released as products in the final step of the reaction scheme (a) trigonal bipyramidal (b) square planar
shown below is [JEE Advanced] ( c) square pyramidal ( d) pyramidal
Complete 6. The molecular ion XF2 bas three pairs of non-bonding
hydrolysis
P + Other product
1 HO-/H20
electrons around the central atom. The bond angle
F-X - F will be closest to
(a) 180°
[Inderaprastha CET]
(b) 120°
Q
(c) 109° (d) 90°

! Slow disproportionation
in HO- ./ H20

Products
7. Which of the following sets have correctly matched each
molecule or ion and its geometry ?

Trigonal
[IPUCETJ

(a) 0 (b) I Tetrahedral T-shaped Square planar

pyramidal
(c) 2 (d) 3
(a) CH4 BCl 3 N03 s01-
2. Which one of the following is used for the separation of
noble gas mixture from air ? [BITSATJ (b) so~- NF3 ICl3 XeF4
( a) Charcoal (c) CH4 N03 Gal 3 SnC14
(b) 90% CaC2 + 10% CaCl 2
(c) Soda lime + potash solution (d) CC1 4 PF3 IC13 SF4
(d) 90% CaCO 3 + 10% urea
8. Which of the following pairs contains isoelectronic
3. Which of the following pair have identical shape ? species ? [IPUCET]
(a) CH4 , SF4 (b) BC1 3 , ClF3 [BITSATJ (a) Be and Li+ (b) p + ands-
(c) XeF2 , ZnCl 2 (d) SO2 , CO2 (c) N2 - and Ne (d)O 2- and Na+
4. The structure of XeF6 is experimentally determined to be 9. Which of the following sets has the atoms and/or ions in the
distorted octahedron. Its structure according to VSEPR correct order of increasing size ? [IPUCETJ
theory is [WB JEE] (a) Ne< F- < O 2-
( a) octahedron (b) Br- < Cl- < F-
(b) trigonal bipyramid (c) Na+ <Mg 2+ <Al 3 +
( c) pentagonal bipyramid
(d) tetragonal bipyramid (d) P < S< Cl
498 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2013 2009
10. The unbalanced chemical reactions given in Column I 16. Which one of the following reaction of xenon compounds
show missing reagent or condition (?) which are provided is not feasible? [AIEEE]
in Column II. Match Column I with Column II and select (a) Xe03 + 6HF ~ XeF6 + 3H2 0
the correct answer using the codes given below the (b) 3XeF4 + 6H2 0 ~ 2Xe + Xe03 + 12HF + 1.5 0 2
columns. [JEE Advanc ed] (c) 2XeF2 + 2H 2 0 ~ 2Xe + 4HF + 0 2
Column I Column TI (d) XeF6 + RbF ~ Rb[XeF7 ]

I. NO 17. Argon is used [Manipal]

A. Pb02 + H 2S04 ~ PbS04 + 0 2 + (a) in filling airships
Other product
(b) to obtain low temperature
2. 12 ( c) in high temperature welding
B. Na 2Si03 + Hp~ NaHS0 4 +
( d) in radiotherapy for treatment of cancer
Other product

c. N 2H 4 ~ N 2 + Other product
3. Warm 2008
4. Cl 2 18. The inert gases producing maximum number of
D. XeF2 ~ Xe+ Other product compounds are [MPPET]
(a) He and Ne (b) Ar and Ne
Codes
A B D A B D (c) Kr and Ne (d) Ar and Xe
C C
(a) 4 2 3 1 (b) 3 1 1 4 19. Which is the most easily liquefiable rare gas? [KCET]
(c) 1 4 2 3 (d) 3 4 2 1 (a) Xe (b) Kr
(c) Ar (d) Ne
2011
20. Helium is used in balloons in p lace of hydrogen because
11. In Ramsay and Rayleigh's isolation of noble gases from it is [KCET]
air, the nitrogen of the air is finally converted into [KCET]
(a) incombustible
(a) NaN02 only (b) NO and N02 (b) lighter than hydrogen
(c) NaN03 only (d) NaN0 2 and NaN03 ( c) radioactive
12. Platinum, palladium and iridium are called noble metals (d) more abundant than hydrogen
because [WB JEE] 21. Which of the following noble gases is most reactive?
(a) Alfred Nobel discovered them (a) He (b) Ne [BCECE]
(b) they are found in native state
(c) Ar (d) Xe
(c) they are shining lustrous and pleasing to look at
( d) they are inert towards many common reagents o; r
22. The formation of [PtF6 is the basis for the formation
of xenon fluorides. This is because
2010 [Jam.ia Millia Islamia]
13. Helium-oxygen mixture is used by deep sea divers in (a) 0 2 and Xe have comparable sizes
preference to nitrogen-oxygen mixture because [Manipal] (b) Both 0 2 and Xe are gases
(a) helium is much less soluble in blood than nitrogen (c) 0 2 and Xe have comparable ionisation energies
(b) nitrogen is much less soluble in blood than helium (d) Both (a) and (c)
(c) due to high pressure deep under the sea nitrogen and 23. Xenon hexafluoride reacts with silica to form a xenon
oxygen react to give poisonous nitric oxide compound X. The oxidation state of xenon in Xis [DCE]
(d) nitrogen is highly soluble in water
(a)+2 (b)+4
14. Molecules of a noble gas do not posses vibrational energy (c) + 6 (d) 0
because a noble gas [KCET]
24. The noble gas used in atomic reactor, is [DCE]
(a) is monoatomic
(a) krypton (b) oxygen
(b) is chemically inert
( c) neon ( d) helium
(c) has completely filled shells
( d) is diamagnetic 2007
15. Which of the following is the life saving mixture for an 25. When radioactive minerals like clevite, monazite and
asthma patient? [Punjab CET] pitchblende are heated to 1273 K in vacuo the noble gas
(a) Mixture of helium and oxygen obtained is [BITSAT]
(b) Mixture of neon and oxygen (a) Rn (b) Kr
(c) Mixture of xenon and nitrogen (c) He (d) Ne
(d) Mixture of argon and oxygen
 p-Block Elements I 499
26. The noble gas mixture is cooled in a coconut bulb at 173 K. 32. Noble gases are adsorbed by [Manipal]
The gases that are not adsorbed are [KCET] (a) anhydrous calcium chloride
(a) Ne and Xe (b) He and Xe (b) ferric hydroxide
(c) Ar and Kr (d) He and Ne (c) cone. H 2 SO4
27. Which one of the following noble gases is used in miner's (d) activated coconut charcoal
cap lamps ? [EAMCET] 33. In clathrates of xenon with water, the nature of bonding
(a) Helium (b) Neon (c) Argon (d) Krypton between xenon and water molecule is [MHT CETJ

28. Which one of the following represents noble gas (a) dipole induced dipole interaction
configuration ? [BCECE]
(b) coordinate
( c) hydrogen bonding
(a) Js 2 ,2s 2 2p 6 ,3s 2 3p 6 3dIO ,4s2 4p 6 4dIO, ( d) covalent
5s2' 5p6 5d6' fu,2 34. For advertisement, the coloured discharged tubes contain
(b) ls2 , 2s 2 2p 6 , 3s2 3p 6 3dIO, 4s 2 4 p 6 4d 10 , (a) He (b) Ne [UPS EE]
ss2sp65d1 ,6s-2 (c) Ar (d) Kr
6 6 10 4s 2 4 6 4d 10
(c) ls2 ,"'-> 2 2
'">• 2 p , 3s 3 p 3d. , p , 35. End-product of the hydrolysis ofXeF6 is [UPSEE]
5s 2 5p 6
10 (a) XeF4 O (b) XeF2 O 2
(d) ls ,2s 2p 6 ,3s 3p 6 3d ,4s 4p 6 4/1 ,
2 2 2 2 4
(c) XeO3 (d) XeO3
ss2 5p 6 5d
1

36. What is the co1Tect order of occurrence(% by weight) in air

29. The gas not adsorbed by coconut charcoal is [BCECE] of Ne, Ar and Kr? [EAMCETJ
(a) He (b) Ne (c) Ar (d) Kr (a)Ne > Ar > Kr (b)Ar > Ne > Kr
30. Which one of the following statements regarding helium is (c)Ar > Kr > Ne (d)Ne > Kr > Ar
incorrect ? [Jamia Millia Islamia]
(a) It is used to fill gas balloons instead of hydrogen
2005
because it is lighter and non-inflammable 37. In Fischer-Ringe's method of separation of noble gas
(b) It is used as a cryogenic agent for carrying out mixture from air, .......... is used. [EAMCETJ
experin1ents at low temperatures (a) 90% CaC2 + 10% CaC1 2
(c) It is used to produce and sustain powerful (b) coconut charcoal
superconducting magnets
(c) soda lime+ potash solution
( d) It is used in gas-cooled nuclear reactors
(d) 90% CaCO3 + 10% urea
2006 38. Which inert gas have highest boiling point ? [BCECEJ
31. The noble gas which is not found in atmosphere [BITSAT] (a) Xe (b) Ar
(a) Ne (b) Ar (c) Rn (d) Kr (c) Kr (d) He

Answers
TOPIC 1 Group 15 Elements
1. (a) 2. (a) 3. (d) 4. (a) 5. (b) 6. (a) 7. (c) 8. (c) 9. (b) 10. (c)
11. (d) 12. (b) 13. (c) 14. (d) 15. (d) 16. (b) 17. (a) 18. (c) 19. ( d) 20. (d)
21 . (d) 22. (e) 23. (c) 24. (b) 25. (d) 26. (a) 27. (b) 28. (b) 29. (b) 30. (b)
31 . (d) 32. (c) 33. (a) 34. (a) 35. (c) 36. (a) 37. (b) 38. (a) 39. (b) 40. (b)
41 . (b) 42. (d) 43. (c) 44. (c) 45. (b) 46. (c) 47. (b) 48. (a) 49. (d) 50. (c)
51 . (d) 52. (a) 53. (a) 54. (b) 55. (c) 56. (b) 57. (c) 58. (b) 59. (a) 60. (c)
61 . (a) 62. (d) 63. (d) 64. (d) 65. (b) 66. (a) 67. (a) 68. (b) 69. (c) 70. (a)
71 . ( c) 72. (a) 73. (a) 74. (d) 75. (c) 76. (d) 77. (c) 78. (c) 79. (c) 80. (a)
81 . ( c) 82. (b) 83. (c) 84. (c) 85. (a) 86. (a) 87. (c) 88. (a) 89. (b) 90. (a)
91 . (a) 92. (d) 93. (a) 94. (a) 95. (b)
 Answers
Topic2 Group 16 Elements
1. (d) 2. (b) 3. (a) 4. (c) 5. (b) 6. (a) 7. (a,c,d) 8. (e) 9. (b) 10. (d)
11. (d) 12. (c) 13. (c) 14. (b) 15. (d) 16. (c) 17. (c) 18. (a) 19. (e) 20. (b)
21. (d) 22. (a) 23. (c) 24. (b) 25. (b) 26. (c) 27. (c) 28. (c) 29. (a) 30. (c)
31 . (b) 32. (b) 33. (c) 34. (d) 35. (b) 36. (d) 37. (c) 38. (a) 39. (c) 40. (d)
41. (a) 42. (d) 43. (d) 44. (b) 45. (b) 46. (c) 47. (a) 48. (c) 49. (d) 50. (b)
Topic 3 Group 17 Elements
1. (c) 2. (b) 3. (c) 4. (b) 5. (a,b) 6. (d) 7. (a) 8. (d) 9. (a) 10. (d)
11. (a,c,d) 12. (c) 13. (a) 14. (a) 15. (b) 16. (c) 17. (b) 18. (b) 19. (b) 20. (b)
21. (b) 22. (d) 23. (d) 24. (b) 25. (b) 26. (c) 27. (b) 28. (d) 29. (b) 30. (d)
31 . (a) 32. (b) 33. (d) 34. (d) 35. (a) 36. (c) 37. (d) 38. (a) 39. (b) 40. (d)
41. (c) 42. (b) 43. (a) 44. (d) 45. (a) 46. (b) 47. (c) 48. (b) 49. (d) 50. (b)
51. (d) 52. (b) 53. (d) 54. (d) 55. (b) 56. (d) 57. (c) 58. (c) 59. (a) 60. (a)
61. (a) 62. (d) 63. (d)
Topic4 Group 18 Elements
1. (c) 2. (b) 3. (c) 4. (c) 5. (c) 6. (a) 7. (b) 8. (d) 9. (a) 10. (d)
11. (d) 12. (d) 13. (a) 14. (a) 15. (a) 16. (a) 17. (c) 18. (d) 19. (a) 20. (a)
21 . (d) 22. (d) 23. (c) 24. (d) 25. (c) 26. (d) 27. (d) 28. (c) 29. (a) 30. (c)
31 . (c) 32. (d) 33. (a) 34. (b) 35. (c) 36. (b) 37. (a) 38. (a)

Explanations
Topic 1 Group 15 Elements
1. This problem is based on chemical properties of phosphorus. 5. White phosphorus is highly reactive, bursting into flames when
White phosphorus on reaction with thiony l chloride (SOCl2 ) exposed to air, and is thus stored under water. The P- P -P
produces phosphoms trichloride. angle is much smaller (60°) than the normal tetrahedral angle
Pis) + 8SOCl 2 (/) - 4PCl 3 (/) + 4SO 2 (g) + 2SzCl 2 (g) (I 09°-28). Therefore, P4 molecule are highly strained. Due to this
angle strain white phosphorus is very reactive.
But if amount of thionyl chloride (SOCl 2) is in excess then it
produces phosphorus pentachloride 6. In structure TT, position ofN is changed which is not allowed in
resonance. It is symmetric anion with equal N- O bond length
P4 + I0SOCl 2 (/) - 4PCl 5 + 10SO2
7. Pure phosphine gas is not inflammable at nonnal temperature but
Hence, (a) is the correct choice.
on heating upto 150°C, it catches fire and produces phosphorus
2. NO is paramagnetic in gaseous state because in gaseous state, it pentoxide.
has one unpaired electron.
Total number of electron present= 7 + 8 = 15 e-
2PH3 + 402 - Pp 5 + 3H2O
8. In NF3, N is less electronegative as compared to F but in NH3, it is
Hence, there must be presence of an unpaired electron in gaseous more electronegative than H. And in case ofsame central atom, as
state while in liquid state, it dimerises due to unpaired electron. the electronegativity of other atoms increases, bond angle
3. As the nuclear charge per electron is maximum in P 5 +. Atomic decreases. Thus, bond angle in NF3 is smaller than that in NH3
size decreases with increasing effective nuclear charge. ps+ has because of the opposite polarity ofN in these molecules.
more effective nuclear charge than other. Therefore, its size is
smallest.
4. Solid N 2O 5 is ionic. X-ray diffraction shows that solid Np 5
exists as NO1NO3 (nitronium nitrate). It is covalent in vapour
phase.
 p -Block Elements I 501
+I
9. In case of same anionic (non-metallic) species, the covalent
character of molecule depends upon the size of central atom and [PiO) - NaH 2 P0 2 ]as well as reduced
- 3
decreases with increase in the size of central atom. [P4 (0) - PH3 ]. Therefore, this is an example of
Here, the order of size of central atom is disproportionation reaction. Oxidation number of phosphoms in
N < P < Sb<Bi PH3 is - 3 and in NaH2P0 2 is + I. However, + I oxidation
Hence, BiF3 is least covalent in nature. number is not given in any option, one might think that
10. Metallic oxides are basic in nature while non-metallic oxides are NaH2P0 2 has gone to ftrrther decomposition on heating.
t,. +5
acidic in nature.
2NaH2P02 - Na 2HP04 + PH3
Lithium does not form peroxide. Further, oxides of lithium are
basic in nanrre. 14. BF3 is symmetrical planar, although it has polar bonds but
When CO 2, N 20 5 and B 20 3 are added to water at the same resultant dipole moment is zero. In NF3 lone pair cause distortion,
hence polari ty arises.
concentration, the following reactions occur
1S. H 4Pp7 pyrophosphoric acid is tetra basic acid because it has
CO 2 + H 20 _,_ H 2 C0 3
4 ionisable H-atoms attached to O - atoms.
Np 5 + Hp ~2HN03
Hence, it gives 4 H+ ions in aqueous solution.
Bp3 + 3H p - 2H3B03 or 2B(OH)3
0 0
(Boric acid or orthoboric acid) II II
H 3B03 is a very weak acid infact it is a non-protonic acid. It HO- P- 0 - P- OH
does not give protons in water while it OH- ion of water to I I
r
form [B(OH)4 and H+ ion as follows OH OH

B(OH)3 + H 20 - [B(OH)4 f + H+ 16. s2Pb = ... 6s26/

These released W make the solution acidic. 83 Bi =... 6s26p3
H 2C03 when added to water gives Due to inertness of 6s2 electrons in Pb and Bi, they show
bivalency and trivalency respectively, instead of tetra and
H 2C03 + H2 ~ Hp+ + HC03
pentavalency. This is called inert pair effect.
It is also a weaker acid in comparison to HN03.
17. Hydrazoic acid, N3H is the most acidic in nature. It dissolves Mg,
So, N 2 0 5 makes the solution most acidic.
Zn, Al etc., to form azides.
11. Dinitrogen pentoxide on hydrolysis gives nitric acid
+ e
N 2 0 5 + Hp - 2HN03 N=N=N - N=N==N
Its structure is similar to organic anhydrides which undergoes I
hydrolysis to give organic acids. Therefore, it is also called H
anhydride of HN03. 18. X-ray studies have been shown that solid PCl 5 is a salt containing
0 0 0 0 t
tetrahedral cation, [PC1 4 and octahedral anion, [ PCl6 r
II :I
<ih'tr~o R
/C"-_).C"-
O ·.
Organic anhydride
R
Dinitrogen pentaoxide
+ +
H 20 H 20

1 0
1 0
Tetrachlorophosphonium ion Hexachlorophosphate ion
0 0 In vapour phase, PCl 5 have a trigonal bipyramidal shape.
I + I II + II
/N"- /N"- /c"- /c"- Heat
19. Ba(N3)z ~ Ba(s) + 3N2(g)
0 OH HO 0 R OH HO 0
Organic acid
Nitric acid Azide salt ofbaritrrn can be obtained in purest form as well as the
decomposition product contain solid Ba as by-product alongwith
12. N02 is a brown coloured gas and imparts this colour to gaseous nitrogen, hence no additional step of separation is
concentrated HN0 3 due to long standing. required. Other reactions are
Heal
4HN0 3 - 2H20 + 4N02 + 0 2 NH 4N0 3 ~ Np+ 2Hp
13. The reaction of white phosphoms with aqueous alkali is Heat
P4 + 3NaOH + 3Hp - PH3 + NaH2P0 2 2NH3 + 3Cu0 ~ 3Cu + 3H20 + N2
Heat
In the above reaction phosphoms is simultaneously oxidised {NH4)2Cr201 ~ Cr2 0 3 + 4H20 + N 2
502 I Chapterwise & Topicwise Engineering Entrances Solved Papers
20. PCl 5 produces POCl 3 with the following reagents. 25. Quicklime, CaO is used to dry ammonia, as w ith other given
PCl5 + SO 2 - POCI 3 + SOCl 2 dehydrating agents ammonia reacts as.
4NH 3 + CaCl 2 - CaCl2 · 4NH3
PCl 5 + Hp - POCl 3 + 2HCI
4NH3 + 2P2O 5 - 4NH 4PO 3
PCl 5 + H 2SO 4 - SO 2Cl 2 + 2POCI 3 + 2HCI
Ca(OH)z is never used as dehydrating agent.
6PCI 5 + Pp 10 - I0POCl 3
26. The formula ofhypophosphorus acid is H 3PO 2.

21. NO2 is brown reactive gas with pungent odour, paramagnetic but
w p
dimerise to solid N 2O 4•
w·---- 1'--..oH
o~/o o~/o H
N N
27. Phosphorus pentoxide acts as a powerful dehydrating agent. It
+ I
. N
dehydrates HNO 3 to N 2O 5, H 2SO 4 to SO3, HC1O4 to Cl 2O 7 etc.
4HNO 3 + PP 10 2N2O 5 + 4HPO3
N cf'~o -
/ ~ 2H 2SO4 + P4 O 10 - 2SO 3 + 4HPO 3
0 0 N2O4
Dimensation ofN(½ 4HClO 4 + P4 O 10 - 2Cl 2O 7 + 4HPO3
28. Phosphorus acid (H 3PO3) is a diprotic acid. It forms two series of
22. Thermal stabi lity of hydrides of nitrogen family decreases
gradually from NH 3 to BiH3. salts such as NaH 2PO 3 and Na 2HPO3 but none ofd1e type NaPO 3
with NaOH. Its structure is as
Because as we move down the group the size of the central atom
increases and hence its tendency to form covalent bond with 0
comparatively small H-atom decreases. In other words, the M -H II
bond strength decreases and hence the therma l stability goes on p
ff'..,.., I'--..OH
decreasing as we move from NH3 to BiH3.
NH3 > PH 3 > AsH3 > SbH 3 > BiH3 OH
23. General valence shell electronic configuration of 15th group 29. White phosphorus on reaction with limited supply of oxygen
elements is n.s 2np3 where, n =period number. Thus, for n = 3, the gives lower oxide P4O 6 . Therefore, air (02 + N 2 ) is a good source
electronic configuration of the element is ls2, 2s2, 2p6, 3s 2 , 3p3. for controlled supply of oxygen and the best choice for controlled
oxidation of white phosphorus into lower oxide P4O6.
t:,. I
24. KNO3 - KNO 2 + - O 2
2

30. Potassium tetraiodomercurate (II), i.e. Ki(Hgl4 ] dissolves in

KOH solution to give Nessler's reagent. Nessler's reagent is used
to test NH; ions.
PCl 3 + 3PhMgBr - P(Ph)3 + 3Mg
Triphenyl
phosphine
< Cl

°'B
r
31. P4 + 3NaOH + 3Hz0 - 3NaH2PO 2 + PH3
36. Thermal stability of the hydrides decreases gradually from NH3
32. N itrogen d ioxide (NO 2)exists as a dimerNp4 .
to BiH3. This is due to the reason that atomic size of the element
W11en it is disso lved in sodium hydroxide or any other alkali, a
increases down the group and M- H bond strength decreases.
mixture of nitrate and nitrite is obtained.
where, Mis the element of 15th group.
2NO2 + 2NaOH - NaNO2 + NaNO3 + H p
Sodium Sodium 37. Phosphorus, element of nitrogen family (15th group), produces
nitrite nitrate
maximum number of oxyacids.
33. Pesticides are the compounds that destroy insects (pests). In e.g. H 3PO2, HPO2, H3PO3, H 4P2O5, HPO3, H3PO 4 , H 4 P2O7.
ancient time, arsenic compounds were used as pesticides.
38. Ammonium dichromate on heating gives nitrogen, chromic oxide
34. The reducing character of the hydrides of group 15 elements and water.
depends upon the stability of hydrides. W id1 progressive decrease I!.
in stability, the reducing character of hydrides increases as we (NH4 )zCr2O 7 - N 2 + Cr2O 3 + 4Hp
move down the group. 39. The acidic character of oxides increases w ith increase in d1e
Thus, ammonia, being stable has least reducing ability. The order oxidation munber of element.
of reducing abilities ofV group hydrides is +I +2 +3 +4 +5
NH3 < PH 3 < AsH 3 < SbH3 < BiH3 N 2 0, NO N 2 O3, NO2 N 2 0 5 - --
~ ~ - -~ - - -~ Increases
35. W11en phosphorus trichlo ride reacts with phenyl magnesitun Neutral Acidic character
bromide (Grignard's reagent), all the three chlorine atoms ofPCl 3 Hence, d1e correct order of acidic nature of oxides is
are replaced by pheny l group of phenyl magnesium bromide and N 2 O <NO <Nz03 < NO2 <N2 O 5.
triphenyl phosphine is obtained.
 p -Block Elements I 503
40. Except ammonia (NH3), the boiling point generally increases 48. The thennal stability of the hydrides ofnitrogen family or group I 5
down the group due to increase in magnitude of van der Waals' elements decreases on moving downwards in the group. Therefore,
forces. Ammonia shows intermolecular hydrogen bonding, NH 3 is d1e most stable and BiH3 is the least stable. The stability of
hence its boiling point is higher than AsH3, but lower than the hydrides of group 15 elements decreases in the order
SbH3. NH 3 > PH3 > AsH3 > SbH3 > BiH3
49. The+ 5 oxidation state of Bi is unstable due to inert pair effect.
NH 3 PH 3 AsH3 SbH3 BiH 3
Thus, BiF5 cannot be formed. As we move down the group, there
238.5 K 185.5 K 210.6 K 254.6 K 290K is reluctance of ns electrons to participate in bond formation and
this phenomenon is called inert pair effect.
41. Structure ofH3PO 3 is 50. Sodium pyrophosphate is represented by Na4 P2 O 7 . It is sodium
0 salt of pyrophosphoric acid (H4P2O 7 ) , which may be considered
II
p
to be made up by two molecules of ortho phosphoric acid
H'.,,. I. . . . .OH (H 3PO4 ), eliminating one molecule of Hp.
OH 0 0 0
4NnOH )
Hence, it has one non-ionisable P- H bond.
II -H20 II II -4H20
P- OH~ P - 0 - P [H-atoms of OH
t,
/"-.. /"-.. /"-.. are replaced by Na]
42. (NH4 ) 2Crp 7 ----t N 2 + Crp3 + 4H2 O HO OH HO OH HO OH
(H4P207) 0 0
Ba(N3 h ~ 3N2 + Ba Pyrophosphoric
acid
II II
P - O - P
NH4NO 3 ~ N 2O + 2H2 O /"-.. /"
Na+o- o -Na+ o -Na+ o -Na+
43. Order of increasing enthalpy of vaporisation is Sodium pyrophosphate
PH3 < AsH 3 < NH3 (Na4P207)

The enthalpy ofNH3 is higher due to the H-bonding.

44. When nitrogen and hydrogen in the ratio of I : 3 are mixed at high 51. Ammonia on reaction with excess of chlorine gives nitrogen
trichloride.
temperature (750 K) at 200- 250atm pressure and in the presence
of Fe and Mo, ammonia is obtained. This process is called NH 3 + 3CI2 ----t NCl 3 + 3HCI
Haber's process. Excess
Fe,Mo
52. 12 + I 0HNO 3 ~ 2HIO3 + I 0NO 2 + 4H2 O
750K, t,
200-250atm S + 6HNO3 -➔ H 2 SO 4 + 6NO 2 + 2H2O
In this process finely divided iron (Fe) acts as catalyst and t,
P4 + 20HNO3 ----t 4H3PO4 + 20NO2 + 4H2 O
molybdenum (Mo) acts as catalyst promoter. t,
45. H 3PO4 is tribasic acid. C + 4HNO 3 ----t CO2 + 4NO 2 + 2H2O

0 53. Red Pis obtained from white P by heating it with a catalyst in an

II
p
inert atmosphere.

H0/ 1'-...0H Pis) 573 K Pis)

White CO2 or Coal gas Red phosphorue
OH phosphorus
As it contains three replaceable hydrogens.
54. The structure of H 3PO4 is.
46. Liquor ammonia bottles are opened only after cooling because it
It can lose three H+ ions so, its basicity is three.
has high vapour pressure and it is mild explosive.
47. White phosphorns has the molecular formula P4 both in solid and
vapour state at moderate temperature. The four atoms present in
the molecule are arranged at the comers of tetrahedron, so the
PPP bond angle is 60°. At higher temperature (above 700°C), it
dissociates to give diatomic molecules as P4 ~ 2P2
Structure of P4 55. Liquor ammonia is concentrated solution of ammonia in water,
while liquid ammonia is liquefied ammonia gas.
56. The boiling point of NH3 is higher due to the presence of
hydrogen bonding. The order of boiling point of hydrides of
nitrogen family is as
Hydride . PH 3 < AsH 3 < NH 3 < SbH3
BP 185 218 239.6 256.
504 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Hence, X = NaN 3
- 190°C
NaN3 + NaOH + NH3
(X)
65. The treatment of Cu with dilute HNO3 gives NO (nitric oxide).

2HNO3 -
[Cu + 0 -
H2O + 2NO + 3(0)
CuO)x3
58. This is the laboratory method of preparing phosphine gas. 3Cu + 2HNO 3 - 3CuO + H 2 O + 2NO
P4 + 3NaOH + 3Hz0 - PH3 + 3NaH 2PO2 66. Hypophosphorus acid (H3PO 2 ) is a monobasic acid which act as
Phosphine
reducing agent. In this molecule, two P--H bonds are responsible
(A)
for its reducing character and one O- H bond is responsible for
59. The reducing property of the hydrides ofl S group increases from its monobasic acid character.
NH3 to BiH 3
NH3 < PH 3 < AsH 3 < SbH3 < BiH 3
The tendency to donate lone pair or basic strength decreases from
NH3 to BiH 3
NH3 > PH3 > AsH 3 > SbH 3 > BiH3
Thermal stability of VA group hydrides decreases from NH3 to
BiH 3 67. Members of group 1S or VA of periodic table are called
NH3 > PH3 > AsH3 > SbH3 > BiH 3 pnictogens. They include N, P, As, Sb and Bi.
Bond angle of 15 group hydrides decreases from NH3 to BiH3 68. Phosphine forms vortex rings of P2O 5 when it comes in contact of
NH3 > PH 3 > AsH 3 > SbH3 > B iH 3 air. These rings are in the form ofw hite smoke.
:. They are used in making smoke screens in warfare.
60. Zn + 10HNO 3 - 4Zn(NO 3 ) 2 + NH4NO 3 + 3H 2O
(Cold, dil) Ammonium 0 0 0
nitrate II II II
:. Zn reacts with cold dil. HNO3 to produce NH 4NO 3 . 69. / p ~H / p ~H /p\"OH
With dil. HNO 3 it produces - NP (nitrous oxide) HO H HO OH HO HO
With cone. HNO3 it produces - NO 2 (nitrogen dioxide) H 3PO2 H 3PO3 H 3PO 4
61. The head of match stick contains KCIO3 , KNO3 , sulphur and
antimony. The sides of match box contains red phosphorus and Although the number of - OH groups is increasing in H 3PO2
sand powder. ( I OH group), H 3PO 3 (2 OH group) and H 3PO4 (3 OH group), yet
acidity does not increase much. This is due to the fact that the
62. Orthophosphoric acid (H3PO4 ) is a tribasic acid because it has
number ofunprotonated oxygen, responsible for enhancement of
three replaceable hydrogen atoms. acidity due to inductive effect, remains the same, as a result
Hence, the basicity ofH3PO4 is 3. Its structure is as dissociation constant also remains nearly same.
0 70. Pb reacts with dilute HNO3 to produce NO.
II
p
3Pb + 8HNO 3 - 3Pb(NO3)z + 2NO + 4H 2 O
HO..,...-\'OH Dil.
OH
H3P04 (tribasic acid) 71. Magnesium and dilute HNO 3 reacts to produce H 2 gas.

While phosphorus acid (H3PO 3 ) is a dibasic acid because it has Mg + 2HNO 3 Mg(NO 3 ) 2 + H2 t
Dilute Hydrogen
two replaceable hydrogen atoms. nitric acid
Hence, the basicity of H 3PO 3 is 2. Its strncture is as
72. PCl 3 and cold water reacts to produce orthophosphorus acid
0
(phosphorns acid) H 3PO 3 .
p
II
PCl 3 + 3HOH - H 3PO 3 + 3HCI
H..,...-\'OH
OH 73. White phosphorns on heating with aqueous solution of KOH
H3P03 (dibasic acid) produce phosphine (PH 3) gas.
P4 + 3KOH + 3H2O - 3KH2PO2 + PH3
+ ,f/0 White Potassium Phosphine
63. H-+- O -++- N "- _ H-+- O-+- N=O.
0 phosphorus hypophosphite
Polarity along O - H in HNO3 is more in comparison to 74. All other oxides of nitrogen except N 2O 5 and N 2O 3 are acidic in
- 0-H in HNO 2. nature. NO is neutral in nature. N 2 O 5 from HNO 3 and N 2 O 3 forms
Hence, HNO 3 is stronger acid than HNO2 . HNO2 in aqueous solution.
64. NH3 > PH3 > AsH 3 > SbH 3. Nz0 5 + HzO- 2HNO 3
Nitric acid
As the electronegativity of central atom decreases, bonded
electron polarises towards central atom more, so, repulsion N 2 O3 + H 2O- 2HNO 2
Nitrous
increases and bond angle increases. acid
 p -Block Elements I 505
75. Al, Fe, Mg all reduce dilute HNO3 into NH 4NO 3 while Pb gives 86. Platinum acts as catalyst in the oxidation of ammonia to form
NO with dilute nitric acid. nitric oxide. This reaction is used in the Ostwald's method of
nitric acid preparation.
3Pb + 8HNO3 - 3Pb(NO3)i + 2NO + 4H2O
Dilute
4NH3 + 502 75
:"c 4NO + 6H2O
76. In electrothermal process, silica is heated with calcium phosphate
when phosphorus pentoxide is obtained. It is then reduced by 2NO + 0 2 - 2NO2
coke in electric ftrrnace to get white phosphorus. 4NO2 + 0 2 + 2H2O - 4HNO3
2Ca3(PO 4 ) 2 + 6SiO2 ~ 6CaSiO3 + P4 O 10 87. Iron is oxidised to ferrous nitrate and nitric acid is changed to
ammonium nitrate.
Pp 10 + IOC ~ P4 + IOCO 4Fe + 10HNO3 - 4Fe(NO 3)2 + NH4NO 3 + 3H 2O
Oil.
77. Hydrolysis ofNCI 3 gives NH 3 or NH4OH and HOC! as
88. The inorganic nitrogen exists in the form of ammonia, w hich may
NCl 3 + 4H2O - NH4OH + 3HOCI
be lost as gas in the atmosphere, may be acted upon by nitrifying
78. Calcium cyanamide on treatment with steam produces NH 3 and bacteria, or may be taken up directly by plants.
CaCO 3. 89. A mixnire of calcimn cyanamide CaCN2 and coke (C) is called
CaCN 2+ 3H2 O - 2NH 3 + CaCO3 nitrolim. It is used as a fertilizer and can be prepared by passing
79. When phosphorus trioxide is dissolved in water, phosphorus acid nitrogen on CaC2.
(H3PO 3) is formed. 1100°C
P4O6 + 6H2O - 4H3PO3 CaC2 + N 2 - CaCN2 + C
N itrolim
80. Hypophosphorus acid is a monobasic acid as it forms one type of
90. Orthophosphoric acid (H3PO4 ) is a tribasic acid. H ence, its
salts, e.g. sodium hydrogen phosphite (NaH 2PO 2 ).
strucnire can be represented as Of- P(OHh
NaOH + H 3PO2 - NaH 2PO2 + H 2O
Hypophosphorus acid has two hydrogen atoms attached to 0
phosphorus and one hydrogen atom attached to oxygen atom
i
H- o - p - O- H
0
II I
0
(which is ionisable), i.e. H - P-OH
I I
H
H
(Ip + crbp = I + 3 = 4)
81. B lack phosphorus is highest thermodynamic stable form in red,
Hence, hybridisation of P in H 3PO4 is sp3 and thus, it is
black, white and yellow allotropic forms of phosphorus because
its ignition temperan1re is highest. tetrahedral in shape.
Hence, it is inert and has a layered strucnire. 91. H 3PO 4 (orthophosphoric acid) is a tribasic acid because it has
82. Equimolar amounts ofNO(g) and NO2 (g) at - 30° C give N 2O 3(/) three replaceable hydrogen atoms.
which is a blue liquid. Hence, the basicity of H 3PO 4 is 3. It strncture is as
0
NO(g) + NO2(g) - JO"C Np3(/)
Blue
II
P - OH
83. Hypophosphorus acid (H3PO2 ) is a monobasic acid and has only HO/ "-oH
one ionisable H, two H-atoms are directly attached to (H3P04) (tribasic acid)
phosphorus. Thus, the correct statement is (c).
H 92. Ostwald process of manufacturing ofHNO3,
I 4NH3 + 502 ~ 4NO + 6H2O + Heat
H- P - O- H
II 2NO + 0 2 -
50"C
2NO 2(g)
0
84. 4HNO3 + P4O 10 - 2N2Os + 4HPO3 3NO2 + H2O - 2HNO3 + NO
:. Pt is catalyst in Ostwald process.
85. In pyrophosphoric acid, P is in + 3 oxidation state.
93. 3CuO + 2NH3 - 3Cu + N 2 + 3Hp
0 0 :. N 2 gas is evolved when CuO reacts with NH 3 .
II II 94. ·:White phosphorns is most reactive and most important allotrope
/p~O--Jp'\_ of phosphorus. It is insoluble in water.
H OH 6H H :. It is kept in water to prevent it from catching fire.
(Dibasic acid)
506 I Chapterwise & Topicwise Engineering Entrances Solved Papers

95. Phosphorus exists in several allotropic forms. Out of them red and 5. Ozone is not stable at high temperature so it decomposes into
white are most common or red phosphorus is most stable form of oxygen at high temperature 203 - 302. T hus, the reverse of
phosphorus. White phosphorus or yellow phosphoms is the most this reaction is non-spontaneous at high temperanire.
reactive and poisonous allotrope ofphosphorus. It is solid at room
temperanire. It catches fire in air, hence kept in water. It has
6. SO~- and Soi- when treated with BaC1 2, give white ppt. of
tetrahedral stmcture. BaS0 3 and BaS04 respectively.
BaCl 2 + so;- - BaS03 + 2CI-
Bariwn
sulphide

BaC1 2 + SO~- - BaS04 + 2CI-

Barium
sulphate

Out of these two, SOi- is soluble in HCI but SO~ - does not.
White phosphorus (tetrahedral solid) 7. Due to resonance, bond-lengths between two atoms are equal.
Species is said to be diamagnetic, ifall electrons are paired.
Process is endothermic if it takes place with absorption of heat
Topic 2 Group 16 Elements ••EB
1. I. In nitrogen, d-orbita ls are absent hence, it does not fonn
..-f'o"- e
NCl 5. Thus, NCl 5 does not exist but PCl 5 does. Q-----:g:
TT. o; and NO are isoelectronic and contains one unpaired Bent molecule

electron each, thus, both are paramagnetic. All electrons paired thus, diamagnetic
III. In carbonate ion co~-
all three C- 0 bonds are identical 20 3 - 302 ; Af/ 0 = - 142 kJ mol-
1

due to resonance Exothermic

-•o
:o X -•• Thus, (b) is incorrect (a, c, d) are correct.
··'-'----c= O.· - ·~~~c= V~o- - :o ••-
.. ·
- •• /
:a...... •
:. ·· ..·o // ··o·•
··'c-
• p 8. Rhombic sulphur means S8 .
So, the atomicity of 'S' in rhombic sulphur is 8.
4
IV. Pb2+ is more stable than Pb + due to inert pair effect, The strucnire of su lphur molecule (Sg)
hence, prefers to form divalent compounds.
<>,~
Thus, the incorrect statements are ITT and TV. V'
2. All are non-polar, molar mass follows the boiling points.
s--......_s~s,,...-s
107° /
The molar mass of these substance follow the order
CH4 < CF4 < CC1 4 •
\ s,,...-s--......_s
The boiling point increases w ith increasing molar mass. Puckered S-tnetnbered ring of S 8

3. In (SiH3 ) 3 N, lone pai r of the nitrogen is transferred to the empty 9. When H 2S gas is passed through nitric acid, colloidal sulphur is
d-orbitals ofsilicon (prt - drt overlap) thereby causing planarity formed as
of unit. H 2S + 2HN03 - 2H 20 + 2N02 + S
SiH3 SiH3 SiH3 10. Chalcopyrites (CuFeSz), a sulphide ore, is concentrated by froth
I It I floatation process.
N - N - N Froth Flotation is a process for selectively separating hydrophobic
H3Si / ~ SiH3 H3Si / "'- SiH3 H3Si "7'"'- SiH3 materials from hydrophilic.

Resonating stmcnire of (SiH 3 ) 3 N. 11. Oxidation states of sulphu r are

4. Na2S03 (X) reacts with dil. HCI to liberate S0 2 gas (Y). This S0 2 - 2 in H 2S
gas decolourises acidified KMn04 . On passing H 2S gas (Z) into
aqueous solution of S02 (i.e. H 2S03 ~ colloidal sulphur is 0 in Ss
obtained. Complete reactions are as follows +2 in 5zo~-
Na 2S03 + 2HCI - 2NaCI + Hp + S0 2 +4 in S0 2
X y
+6 in S03
2KMn04 + 2Hz0 + 5S02 -
Purple y KiS04 + 2MnS04 + 2H2S0 4
Thus, incorrect. (valency can be less than 4.)
Colourless
H2S03 12. S03 is colourless, crystalline transparent solid at room
Aqueous
temperature.
solution of
y
13. H 2S0 4 forms hydrate with water. That's why it has great affini ty
H 2S03 + 2H 2S - 2S + 3H 20
towards water.
z Colloidal
sulphur
 p-Block Elements I 507
14. ?OOH + Cone. H 2S04 --4 CO+ CO 2 + H p 23. PC1 5 reacts with cone. H 2S0 4 to give sulphuryl chloride by
replacing its hydroxyl groups with chlorine atoms.
COOH
Oxalic acid
S02 (0Hh + 2PC1 5 --4 S02Cl 2 + 2POC1 3 + 2HC1
Concentrated H 2S04 is a strong dehydrating agent. or Sulphuryl

15. The stmctures of the given compounds are as

82
SO4 chloride
Sulphuric acid

0 0 0 24. Only carbon reacts with cone. H 2S0 4 to give two different gases.
0
I I I I
.,.,S- ONa C + 2H2S0 4 --4 CO 2 + 2S02 + 2Hp
NaO/S- S'--ONa NaO- s - s- s...-- I (Cone.)
I
0
o While other elements react with cone. H 2S04 with the evolution
(N32S406)
of only one type of gas.
25. In 0 3 , 0 - 0 bond length is not identical with that of the
0 0
I I molecular oxygen. It is found to be intermediate of 0 - 0 and

<lf'--o/f=O 0=0 bond lengths.

This is due to resonance.
6Na ONa
(Na2S207)
Thus, Na2Si07 does not contain S - S bond.
16. Oleum is chemically H 2Si07 (pyrosulphuric acid).
In ozone, bond angle of 0 - 0 - 0 is 116.8° and bond length
(0- 0) is 1.278 J....
26. In laboratory, H 2S is prepared by treating ferrous sulphide (black
lumps) with dil. H 2S04.
FeS + H 2S04 - - 4 FeS04 + H 2S
17. 3S02 + 0 3 --4 2S0 3 27. Ozone is used for purifying water because ozone ki lls the
2Hg+ 0 3 --4 HgzO+ 02 bacteria, cysts, ftmgi, mold, parasites, viruses, contaminates etc.
It is one of the effective way of eliminating microorganism in the
2HC1 + 0 3 --4 Cl 2 + 0 2 + Hp
water.
PbS+ 403 --4 PbS04 + 40 2
Ozone is most effective oxidant (secondary to Fz). It inactivates
Hence, S02 doesn' t librate oxygen with ozone. and oxidises organic matter, contaminates, pesticides, viruses and
18. The function of Fe(OH)3 in the contact process is to remove bacteria faster than chlorine. Ozone do not form TMH which
arsenic impurity. Fe(OH)J is a positive sol, hence it removes have unpleasant odour and also carcinogenic. Ozone is very good
arsenic impurity which is a negative sol. The contact process is biocide. Ozone also absorbs UV radiation.
the current method of producing sulphuric acid
28. (a) H 2S acts as a reducing agent, because it can reduce PbO into
19. Concentrated sulphuric acid, being a strong acid, oxidises
bromides and iodides but not chlorides and fluorides since, the PbS.
later are more electronegative. Hence, it can be reduced only by PbO + H 2S --4 PbS + H 20
NaBr among the given options. (b) It is acidic in nature. In chalcogens, the acidic nature of
+6 - I +6 - I hydride increases from H 20 to H 2Te.
H 2 S04 + Na Br ~ NaH S0 4 + HBr
(c) It is not an oxidising agent.
0 +4
~ 2H 20+ Br2 + S0 2 29. When cone. H 2S0 4 is heated with Pp 5, the acid is converted into
Reduction sulphur trioxide.
20. Since, fuels bum faster in the presence of oxygen, when a
2H2S04 + 2P20 5 --4 2S03 + 4HP03
glowing splinter comes in contact with oxygen, it relights. This is Sulphur trioxide
also a test for oxygen.
21. In group 16 and period VT the oxygen, sulphur, selenium are 30. I Carbon monoxide is neutral and S03 is acidic.
chalcogens (ore forming) while polonium being radioactive III Aluminium and zinc oxides are amphoteric, so aluminium
forms a less number of compounds and is not considered as and zinc oxides react with both as acid and base.
chalcogens. Alp 3 + 6HC1 --4 2AJC1 3 + 3Hp (with acid)
22. Na2S03 reacts with hot and dil. H 2S04 to give S0 2 gas which Alz0 3 + 2NaOH + 3Hp --4 2NaAl(OH)iwith base)
decolourise bromine water. ZnO + H+ --4 Zn 2+ + Hp (in acid)
Na2S03 + H 2S04 - - 4 Na 2S04 + S02 + H 20
Br2 + H 20 --4 2HBr + [OJ ZnO + 20W + H 20 --4 [Zn(OH)4 f- (in base)
S0 2 + [OJ --4 S03 Hence, (I) and (ITT) are correct.
Decolourisation of bromine water.
508 I Chapterwise & Topicwise Engineering Entrances Solved Papers

31. Sulphur does not form prt -pTt bond due to its larger size, hence 43. Copper turnings on heating with cone. H 2SO4 produce SO 2.
does not exist as Si molecules. The S = Sbond is weaker because Cu + 2H 2SO4 - CuSO4 + 2H 2O + SO2
sulphur has smaller size. It is difficult for two atoms to come at
44. H 2S:iO 4 - Dithionous acid
small enough distance. Hence, the µ-orbitals overlap is small and
the rt bond is weak. H 2S:iO6 - Dithionic acid
H 2SiO 5 - Disulphurous acid
32. Polyanion formation is maximum in sulphur. This is due to the
fact that sulphur shows maximum catenation in the group. H 2S:iO7 - Disulphuric acid
33. Oleum is obtained by dissolving sulphur trioxide in H 2SO4 . 45. In presence of moisture, SO2 acts as a reducing agent as it gives
nascent hydrogen. It reduces hydrogen peroxide into water.
SO3 + H 2SO4 (cone.) - H 2SiO 7
Oleum SO 2 + 2H 2O - H 2SO 4 + 2H
Oleum is also called fuming sulphuric acid because it fumes in HP2 + 2H - 2Hp
moist air due to sulphur tri oxide.
46. (a) 2KI + H2O + 0 3 .. 2KOH + 02 + 12
34. Perchloric acid is not a peroxy acid while perphosphoric acid, Ox1d1sed
pernitric acid and perdisulphuric acid are the examples of peroxy
(b) 2FeSO4 + H2SO 4 + 03 - Fei(SO4 )3 + H 2O + 0 2
acid.
Oxidised
35. V2O 5 (vanadium pentaoxide) is used as a catalyst in the
(c) KMnO4 + 0 3 - No reaction
manufacture of H 2SO 4 by contact process since, it is not easily
poisoned. Because in KMnO4, oxidation state of Mn is+ 7. Hence, it is
the highest oxidation state of Mn, so KMnO4 is not oxidised
36. SO 2 acts as a reducing agent, oxidising agent and as a bleaching
by ozone.
agent. It does not act as dehydrating agent.
(d) 2K2MnO4 + H2SO4 + 0 3 -➔
37. (i) Enantiotropy When two forms of a solid substance exist Oxidised
together in equilibrium w ith each other at a particular
temperature under normal pressure 47. In the reaction of SO2 and H 2S, SO2 acts as oxidising agent and
e.g. SR ~ SM H 2S acts a.s reducing agent.
(ii) Dynamic allotropy If different allotropic forms exist in SO2 + 2H2S - 2H2O + 3S J,,
equilibrium over a range of temperature.
(iii) Monotropy Ifan a llotropic form changes s lowly to a stable 48. Cl 2 + 2NaOH - NaCl + NaCIO + H 2O
Cold,di l.
form. e.g. 0 3 - 02
Chlorine reacts w ith cold and dilute NaOH to give sodium
:. Monotropy is correct answer.
hypochlorite.
38. The most abundant element in the Earth cmst is oxygen.
49. Dust is a colloid which shows Tyndall effect.
39. H 2S2O 7 (pyrosulphuric acid) is industrially known as oleum. Hence, Tyndall box is used to test the presence of dust in gaseous
40. SO 2 acts as bleaching agent due to its reducing property. mixture, as dust decrea.ses the effectiveness of catalyst.
50. Platinised asbestos or vanadium pentaoxide (Vp 5 ) is used as
SO 2 + 2Hp - H 2SO 4 + 2H
Coloured matter + [HJ - Colourless matter. catalyst in the preparation of sulphur trioxide from SO2 and
oxygen.
41. The formation of ozone from oxygen is an endothermic reaction
not exothermic reaction. 2SO + 0 Pt, asbestos 2SO + H t
2 2 orvp5 3 ea
Electric
D ischarge
Topic 3 Group 17 Elements
So, statement
Silent 1. Decreasing order of strength of oxoacids
302 ~ 203; t::,.H = - 284.5 kJ
Discharge HC1O4 > HClO3 > HCIO 2 > HOCI
is not correct statement. Reason Consider the stmctures of conjugate bases of each
oxyacids of chlorine.
42. 30 2 E lectric 203
Discharge 0:
II
Cl Cl ~c1:
•.•~ II " o:
··-
.o ·o •. 0 = ..~11 " ··-
.o:
2 . ·.. ~ .. .. :o:-
:o II
..
x+ - x =I00L
3 Negative charge is more delocalised on ClO 4 due to resonance,
5
- x = 100 or x = 60 L 0 2 hence CIO 4 is more stable (and less basic).
3 Hence, we can say as the number of oxygen atoms(s) around
2
Volume ofO3 = - X 60= 40 L Cl-atom increases as oxidation number of Cl-atom increases and
3 thus, the ability of lose the H + increases.
 p -Block Elements I 509
2. CuSO4 + 2K.l - Cul 2 + K 2SO4 11. Solubi lities of silver halides in water decreases from fluoride
(AgF) to iodide (AgD. Silver fluoride is readily soluble in water,
2Cul2 - 2Cul + 12
Cuprous iodide hence when AgNO 3 solution is added to HF solution (HF being
weak acid, its solution maintain very low concentration ofF-), no
3. The high oxidising power of fluorine is due to its low heat of precipitate of AgF is formed.
dissociation and high heat of hydration. Due to its smallest size,
HCl, HBr and HI being all strong acids, form precipitates of
the~e is considerable repulsion in the non-bonding electrons
AgCI, AgBr and Agl when AgNO 3 solution is added to their
which weakens the F- F bond. Thus, bond dissociation energy
aqueous solution.
ofF2 is low.
H CI (aq) + AgNO 3 (aq) - AgCI (s) + HNO3 (aq)
4. MnO2 + 4HCI - Cl 2 + MnC12 + 2H2O
Curdy white
(A)
HBr (aq) + AgNO3 (aq) - AgBr (s) + HNO3 (aq)
Cl 2 + F2 - ClF3
Pale yellow
(in excess) (B)
HI (aq) + AgNO3 (aq) - Agl (s) + HNO3 (aq)
3CIF3 + U - UF6 + 3ClF Yellow
(C) (D)
The solubilities decreases from AgCI to Agl, AgCI dissolves in
5. Hydrides of N, 0 and F because of the small size and high aqueous ammonia, AgBr dissolves only slightly in concentr ated
electronegativity of elements, have ability to form extensive ammonia while Agl does not dissolve in ammonia solution.
intramolecular (i.e. between two molecules) hydrogen bonding. Na 2SiO 3 solution dissolve all three, AgCI, AgBr, Agl by forming
Thus, a large amount of energy is required to break these bonds
i.e. the melting and boiling points of hydrides of these element;
complex [Ag(SiO3 h J3-
as S20;- is a stronger complexing agent
are abnormally high. than ammonia.

6. Among the given interhalogen compounds, only ICl 3 exist as 12. The involved redox reactions are
2H+ + oc1- + 2r - c1- + 12 + H 2O ...(i)
12Cl6 , i.e. exists in dimeric form.
D imeric structure of 12 Cl6 is 12 + 25io;- - 2r + spt ...(ii)

Also the n-factor of S20~ - is one as

Cl"-._ /Cl"-._ /CI ]
1 1
[ c1/ "'-c1/ "'-c1 2SiO~ - - S4OJ- + 2e-
(one electron is produced per unit of SiOi-)
7. BF3 has symmetrical structure in which the three B- F bonds are
oriented at an angle of 120° to one another. Also the three bonds Molarity ofNa 2S2O 3 = 0.25 N x 1 = 0.25 M
lie in one plane and the dipole moments of these bonds cancel one mmol ofNa 2SiO 3 used up= 0.25 x 48 = 12
another giving net dipole moment equal to zero. Now, from stoichiometry ofreaction
F (ii) 12 mmol ofSiOi-
} ,20° would have reduced 6 mmol of I,.
F/tj..(F From stoichiometry of reaction -
(i) mmol ofOCI- reduced= mmol in 12 produced= 6
8., 9. Plan ⇒ Molarity of household bleach solution
2NaOH + Cl 2 Cold NaCl + NaOCI + H,O
p - =~=0.24 M
25
6NaOH + 3Cl2 ~ 5NaCl + NaCIO 3 + 3H 3O Shortcut Method

HOCI NaOH NaCIO Milliequivalent ofNa 2S2O 3 = milliequivalent of OCI-

Hypochlorous p = milliequivalent of OCI-
acid
= 0.25 X 48 = 12
HCIO NaOH NaCJO
Chloric acid
3
Q
3 Also,,1-factorofOCl- =2[CI+ - Cl- ,gain of2e-]

Cl 2 + SO2 - SO 2Cl2 mmol of oc1- = !3. = 6 mmol. Remaining part is solved in

2
R
the same manner.
I0SO2 Cl 2 + P4 - 4PCl 5 + 10SO2
s 13. Bleaching powder is Ca(OCl)CI. Therefore, the oxoacid whose
salt is present in bleaching powder is HOCI.
PCls + 4H2O - H 2PO 4 + 5HCI
Anhydride ofHOCI is Clp as
T
2HOCI - Cl 2O + H 2O
10. B leaching powder loses its power on keeping for a long time
because it changes into calciu m chloride and calcium chlorate. Note The oxidation number of element in anhydride and oxoacid
The fonnation of compound are given below remains the same.
6CaOCl 2 - 5CaCl 2 + 6Ca(C1O 3 ) 2
510 I Chapterwise & Topicwise Engineering Entrances Solved Papers
14. Pseudohalides are the combinations of more than one 26. The pair of SO2 and C1 2 has bleaching property.
electronegative atoms which have one unit negative charge. In the presence of moisture, SO 2 acts as a bleaching agent.
e.g. CN◊- , CN- etc.
RC◊◊- is not a pseudohalide
SO 2 + 2H2O - H 2SO4 + 2[H]
The nascent hydrogen bleaches the colour of the substance, thus
15. Generally with decrease in number of oxygen atoms, basic
SO 2 bleaches by reduction while CI 2 bleaches by oxidation.
character increases. Therefore, the order of basic character is as
follows H 2O + C1 2 - HCI + HCIO
CIO 4 < CIO3 < ClO 2 < Cl◊- HCIO - HCI + [O]
16. 2MnO4+ 16W + IOCI- - 2Mn
2
+ + 5CI2 + 8H 2 O [O] + Coloured substances - Colourless substances
27. The order of bond dissociation energy of hydrogen halide (or
17. The energy liberated when an electron is added to an isolated
halogen acid) is as
gaseous atom is called electron affinity. Thus, as the size Hydrogen halide HF> HCI > HBr > HI
increases, lesser energy is liberated and hence, electron affinity Bond dissociation
decreases. But the electron affinity of Cl is higher than the
energy kJ mol- 1 566 43 1 366 299
electron affinity ofF although F has smaller size. This is because,
Bond dissociation energy oc heat of formation
the incoming electron, in case of F experience a greater force of
As bond dissociation energy decreases, the heat of formation of
repulsion from the outer electrons of F. Thus, to overcome the
halogen acids also decreases.
repulsion, some released energy is utilised. Hence, lesser energy
is released. Thus, the electron affinity is highest for Cl. Hence, the order of heat of formation of halogen acids is
18. 2HCIO4 - Clp7 + H 2O HF > HCI > HBr > m
Hence, Cl 20 7 is the anhydride of HCIO4 • 28. When chlorine reacts with di lute and cold NaOH, sodium
chloride and sodium hypochlorite are formed.
19. Commercially, chlorine dioxide is prepared by passing SO2 gas
2NaOH (cold) + C1 2 - NaCl + NaCIO + H 2 O
into a mixture of sodium chlorate and H 2 SO4 having NaCl in Sodium
traces. hypochlorite
T race Let, oxidation state of Cl in NaCl is x.
2NaCIO 3 + SO2 + H 2 SO4 ~ 2CIO 2 + 2NaHSO4
Solium chlorate NaCl Chlorine NaCl + I + x = 0, x = - I
dioxide Let, oxidation state of Cl in NaCIO is x .
20. C1 2 being a stronger oxidising agent, oxidises bromide present in NaCIO + I+ x - 2= 0
the mother liquor to Br2. x -1 =Ox=+ 1
2Br- + CI 2 - Br2 + 2CI- :.Oxidation states of chlorine changes rrom O to - I and + I .
From mother Bromide
liquor 29. OF2 dissolves in water but does not give any oxyacid solution.
While SO2 , SCl4 , and SO3 give oxyacid solution in water.
21. The hypochlorites disproportionate on heating as follows
SO 2 + H 2◊ - H 2SO 3
3CI◊- - 2CI- + CIO 3 Sulphurous acid
22. In disproportionation reaction, compounds are simultaneously SCI4 + 3H2◊- H 2 SO3 + 4HCI
fonn ed that contain a given element in a more oxidised and more Sulphurous acid
reduced state than the initial one. In CIO4, oxidation number of Cl
is +7 and it cannot increase it forther, so CIO 4 will not get SO 3 + H2◊ - H 2SO 4
Sulphuric acid
oxictised and so, will not undergo disproportionation reaction.
23. Usually, electron affinity decreases on moving down a group but 30. Br2 reacts with hot and strong NaOH to give NaBr, NaBrO 3 and
fluorine due to its smaller size has a low value of electron affinity H 20.
in comparison to chlorine beacause the incoming electron 31. A binary compound is that compound which is formed by two
experience greater repulsion. Thus, the order of electron affinity different elements. Metals or elements which shows variable
is as Cl > F > Br > I. oxidation states can form more than one binary compound. In the
24. The acidic strength of oxyacids decreases downwards in a group. given compounds, Fe shows + 2 and + 3 oxidation states. So, it
The correct order of acidic strength of oxyacids of halogens is can form two binary compounds with chlorine as FeC12 and
FeCI 3•
HCIO4 > HBrO4 > ffiO 4
32. Silica (SiO 2) is present in the glass. This silica reacts with
25. With progressive increase in atomic number, the reduction
potential of halogens decreases, thus oxidising power also hydrofluoric acid.
decreases. Hence, a halogen with lower atomic number will SiO 2 + 4HF - SiF4 + 2H 2O
oxictise the halide ion of higher atomic number and therefore, will SiF4 + 2HF - H 2 SiF6
liberate them from their salt solution. Fluorosilicic acid
Hence, the reaction C1 2 + 2F- - 2Cl- + F2 Note HF is used for the etching of glass.
is not possible.
 p-Block Elements I 511
33. In the sublimation, the solid substance converts into vapours 45. F2 on reaction with hot and cone. alkali (NaOH) gives sodium
directly. Iodine is found in solid state w hile F2 and Cl 2 are found fluoride and oxygen.
in gaseous state and Br2 is found in liquid state. So, iodine can be 2F2 + 4NaOH - 4NaF + 0 2 + 2H z0
purified by sublimation.
46. AgCI is water insoluble chloride. It is a white crystalline solid is
34. Iodine readily dissolves in potassium iodide solution giving well known for its low solubility in water.
KI3.
47. I2 forms complex ion Ii in KI solution due to w hich it dissolves in
KI + I2 - Kiiaq)
it.
KI3 (aq) ~ K+ (aq) + 13(aq)
48. Fluorine has highest (ed (equal to + 2.9 V) due to which it can
Note I2 is more soluble in an aqueous solution of KI than in pure easily accept an electron and hence, it is the best oxidising
water, it is due to the formation of polyhalide (Ti ion). agent.

35. Chlorine heptoxide (Clz07 ) is the anhydride of perchloric acid. 49. Upper halogen can replace lower halogen from their compounds
solution because a more electronegative halogen displaces less
" electronegative halogen from its halide.
2HC1O4 - Cl 2O 7 + Hp
SO. Fluorine exhibits an oxidation state of only - I because it is very
36. F2 has the most negative 6.G 0 value which is dependent on strongly electronegative element (maximum electronegativity in
hydration enthalpy. the periodic table).
Hydration entha lpy of F - (515 KJ mol"1). Flourine has greater 51. The deficiency of iodine in diet causes goitre.
electron-electron repulsion among the lone pair in the same sized 52. Nitric acid oxidises iodine into iodic acid (HTO 3) .
F2 molecule where they are much closer to each other.
Hence, enthalpy of dissociation of F2 is lower than Cl2 which I 0HNO 3 + I2 - 3ffiO3 + I0NO2 + 4H2O
Jodie acid
makes it better oxidising agent.
37. In case ofCl2O 7 , Cl has+ 7 oxidation state (maximum oxidation 53. Reaction of ethyl alcohol with bleaching powder to form
state) and also have hig hest oxygen content. So, it is most acidic. chloroform takes place as
CH3CHzOH + Cl 2 - CH 3 ·CHO + 2HCI
38. The stability of oxides increases with increase in oxidation state
of halogen. CH 3CHO + 3Cl2 - CCl3 · CHO + 3HCI
2CCl 3 ·CHO + Ca(OH)2 - 2CHCl 3 + (HCOO)iCa
Oxide Oxidation state of halogen Decomposition of bleaching powder is catalysed by cobalt
Cl 2O + I chloride.
2
ClO 2 +4 2CaOCl 2 CoCl 2CaCl2 + 0 2
CIO 3 +6 54. The bond dissociation energy of C l2 , Br2 and I2 is as
Cl2O 7 +7 Molecule Cl 2 > Br2 > I2
Dissociation 242.6 192.8 151 .1
:.Cl2O is least stable oxide of chlorine. enthalpy (kJ mol- 1)
39. A more electronegative halogen displaces less electronegative
55. When chlorine is passed into hot concentrated solution of KOH,
halogen from its halide. Fluorine is more electronegative than
potassium chlorate is formed.
chlorine hence, it can displace Cl from HCI while chlorine cannot
displace fluorine from HF. Therefore, the following reaction is 6KOH + 3Cl2 - 5KCI + KClO 3 + 3H 2O
Potassiwn
not valid. chlorate
HF + Cl 2 - F2 + HCI 56. Chlorine can replace bromine from KBr solution, as it is placed
40. 3HOCI - 2HCI + HCIO 3 above bromine in VITA group in periodic table.
41. Potassium chlorate (KCIO 3 ) is known as Berthelot's salt. It is the Cl 2 + 2KBr - 2KCI + Br2
salt of chloric acid, HCIO3. 57. In a group, 6.G1 °(HX) changes from negative to positive
42. The solubility ofl2 in water increases by the addition of KI due to downwards.
formation ofpolyhalide ion, i.e. I3. HF(g) 6.G = - 273.20 kJ mol- 1
KI + I2 - KI3 (aq) ~ K + (aq) + I 3(aq)
HI(g) 6.G = + 1.72 kJ mol- 1
Thus, HF is thermally stable and HI not.
43. Apatite is CaF2 · 3CaiPO4 ) 2 . It is an ore offluorine with calcium.
Thus, HF > HCI > HBr > m.
44. The increasing o rder of bond dissociation of group 17 element, 58. KF + HF - KHF2 ~ K+ + [HF2 r
I - I < Br - Br < F - F < C l - CL
59. Pseudohalide ions combine together to form interpseudohalogen
As we move down the group, the size of the atom increase. As a
compounds. Cl 2N 3 is not an interpseudohalogen.
result, bond length of X 2 molecule would also increases on
moving down the group. Thus, the energy required to break 60. The correct order of acidic strength of halogen acids is
longer bond is less than the energy required to break shorter HF < HCI < HBr < HI
bonds. T hat is why I- I has the lowest bond dissociation energy. This is due to the reason that as the size of halogen increases,
512 I Chapterwise & Topicwise Engineering Entrances Solved Papers
H-X bond becomes weaker and thus, HX easily donate proton. CO2 gas is absorbed by KOH solution. Thus, a mixnire of inert
Hence, HT is the strongest acid and HF is tJ1e weakest acid. gases are obtained.
61. Aqua-regia is the mixture of 3 part cone. HCI and I part cone. 3. Molecules/compounds and their shape can be arranged as
HNO 3. It is a very strong acid whic h can dissolve noble metals.
Compound Shape
62. The bond strength ofH-X decreases from HF to HI because the
dissociation energy ofH- X bond decreases from HF to HI. XeF2 Linear
Hydrogen halide H- F H- Cl H-Br H- T ZnCl 2 Li near
D issociation energy 566 431 366 299 BCI 3 Triangular planar
(kJ mo1- 1) HI is most volatile. CIF3 T-shaped
63. Pseudohalide They are combination of more than one CH4 Tetrahedral
electronegative atoms which have one unit negative charge, SF4 See-saw
e.g. OCW,CW. SO 2 Bent
Polyhalide ions The complex ions which are formed by reaction CO 2 Linear
of halogens among themselves are called polyhalide ions,
e.g. T3, BrT2. 4. In XeF6 , Xe, the central atom contains, 8 valence electrons. Out
Interhalogens They are the compounds which are formed of which 6 are utilised with fluorine in bonding (i.e. it contains six
halogens react among themselves. One ofd1e halogens behave as bond pairs of electrons) while one pair remains as lone pair.
cation and other acts as anion.
e.g. IF5 , ICl 5 , BrF3.

Topic 4 Group 18 Elements

1. XeF6 o n complete hydrolysis produces XeO3 . XeO 3 on reaction
F~
with OH- produces HXeO 4which on further treatment with OH-
undergo slow disproportionation reaction and produces XeOt F
alongwith Xe(g), Hp(!) and O 2 (g) as a by-product. Thus, the total pairs = 6 + I = 7
Oxidation half-cell in basic aqueous solution. Hence, its shape is pentagonal bipyramid according to VSEPR
theory.
HXeO4 + SOW ~ Xeo:- + 3H2O + 2e-
5. XeOF4 has square pyramidal structure.
Reduction half-cell in basic aqueous solution
HXeO 4 + 3H 2O + 6e- ~ Xe + 7OH-
Balanced overall disproportionation reaction is
4HXeO 4 + 8OW ~ 3Xeo:- + Xe + 6H2O
2 products
Complete sequence of reaction can be shown as
XeF6 + 3H 2O ~ XeO 3 + 3H 2F2 6. This problem is based on concept of valence shell electron pair
(P) repulsion (VSEPR) theory.
l OH -
According to VSEPR theory extent ofrepulsion among bond pair
(bp) and lone pairs (lp) can be represented as
HXeo;;- bp -bp < bp -lp < Ip -Ip

l
(Q)
OH - /Hz()
(disproportionation) Molecular ion XF2 has d1ree pairs of non-bonding electron hence
compound must be of ABl'l type. Which have two possible
strucn1res either trigonal bipyramidal or square pyramidal.
xeo:- (s) + Xe(g) + Hp(!) + 0 2 (g)
e e
2. The method used to separate noble gas mixture from air is called
F
Fischer-Ringe's method. When air free from moisture and CO 2
is passed over a heated mixn1re (800°C) of 90%,
CaC2 + 10% CaCl 2 in an iron sealed n1be, the following
reactions take place.
800°C
CaC2 + N 2 ~ CaCN2 + C
2C + 0 ~ 2CO I II
C+ 02 ~ CO 2 Among various possible structures of XF2 above w ritten two
2CaC2 + 3CO2 ~ 2CaCO3 + SC strucn1res have minimum energy and minimum repulsion hence
most stable structure have 180° bond angle for F-X -F.
CuO+ CO ~ Cu + CO 2
 p -Block Elements I 513
7. Using VSEPR theory correct set of compound according to their And according to rule (ii) anions are larger than their parent
corresponding structure is atoms. So, on the basic of both th e rules the correct increasing
(b ) Structures are as shown below size of atoms and/or ions is Ne < F- < 0 2 -.
Note In case of Br-, c1-, r, the correct order will be

Q FQF F- <Cl-< Br-. In caseofNa+, Mg2 + andAJ 3 +, the correct

order will be Al 3 + <Mg2 + < Na+.

rs
0 Xe In case of P, S, Cl, d1e correct order will be Cl < S < P.
I ()II Warm(3)

01
- CI
. /s"'-··
0 :9: I .p:e
N
F/ \"'-F
10. A 2PbO2 + 2H 2SO4 ~ 2PbSO4 + 0 2 + 2Hp
Cl 4
0 F B Na 2SP3 + 4H2O Cli< J 2NaHSO4 + 6HCI
Tetrahedral Trigonal pyramidal T-shaped Square p lanar
C N2H4 ~ N 2 + 4ffi
8. The term 'isoelectronic' means 'equal charge'. Thus, the
NO ( 1)
isoelectronic species are e lements or ions that have the same or D XeF2 ~ Xe + 2NOF
equal number of electrons. Now, let's check all the given options Thus, A - (2), o-
(3), B - (4), c - (1)
and find which of them fulfi lls this criteria.
11. Rayleigh-Ramsay Separation Method
(a) Be and Li+
2 Electric spark
Electron configuration of Be = [He] 2s N 2 + O2 ----'-➔ 2NO
Number of electron = 4 2NO + 0 2 - 2NO 2
Electronic configuration of Li+ = ls
2 2NaOH + 2NO2 - NaNO2 + NaNO3 + H 2O
Number of electron = 2 12. P latinum, palladium and iridium are not attacked by strong acids.
(b) p+ and S- So, these are called noble metals.
Electronic configuration of p + = [Ne] 3s2 3 p 2 13. In blood, He is much less soluble than nitrogen, hence He - 0 2
m!xture is used by deep sea divers in preference to N 2 - 0 2
Number of electron = 14 mixture.
Electronic configuration of S- = [Ne] 3s 2 3p1
14. Since, noble gases are monoatomic, these do not possess
Number of electron = 17 vibrational energy as monoatomic molecules do not vibrate.
(c) N 2 - and Ne
15. Mixture of helium and oxygen is the life saving mixture for asthma
Electronic configuration ofN2 - = ls 22.s22p5 or [He] 2p5 patient because helium is less soluble in blood than nitrogen.
Number of electron = 9 16. XeF6 has much tendency to hydrolyse. The reverse reaction is
Electronic configuration of Ne more spontaneous.
= ls22s22p6 or [He] 2p6 XeF6 + 3H2O - XeO 3 + 6HF
Number of electron = 10 17. Argon is used in high temperature welding and other operations
(d) 0 2 - and Na+ which require a non-oxidising atmosphere and the absence of
2 2
Electronic configuration of 0 - = [He] 2s 2p6 nitrogen.
Number of electron = IO 18. The inert gases producing maximum number of compounds are
Electronic configuration of Na+ =[Ne] 1s22s22p6 Ar (argon) and Xe (xenon) due to their low ionisation energy.
Number of electron = 1O 19. Xe is most easily liquefiable rare gas because interatomic
interactions increases with increasing atomic number.
Thus, it is clear that both 0 2and Na+ contains 10 electoms.
Hence, these are isoelectronic species. 20. Helium (He) is a non-flammable (incombustible) gas and its
lifting power is 93% as compared to flammable hydrogen gas,
9. Before solving this, we should know certain facts regarding size due to these reasons it is used in filling balloons and other lighter
of elements and ions. air-crafts.
(i) In a periodic table on going from left to right in a period, the
atomic radius of the elements decreases w hile on going 21. Lower is the ionisation potential of an element, more would be its
down a group of the periodic table, the atomic radius of reducing power and also reactivity.
elements increases. As we move down the group, the reactivity of noble gases
(ii) Cations are smaller than their parent atoms while anions are increase due to d1e decrease in ionisation energy.
larger than their parent atoms. Hence, xenon is most reactive.
2
In case of Ne, F - and 0 -, they belongs to same period. So, 22. The first ionisation energy of xenon is quite close to that of
according to rule (i) the atomic size should follow the order oxygen and d1e molecular diameter of xenon and oxygen are
0 > F > Ne. But here O and F are present in the form of their almost identical. Based on the above facts it is suggested that
anions, i.e. 0 2 - and F- . since, oxygen combines with PtF6 , so xenon should also form
similar compound w ith PtF6.
514 I Chapterwise & Topicwise Engineering Entrances Solved Papers
23. Xenon hexafluoride reacts with silica to form XeOF4 as
2XeF6 + SiO2 - XeOF4 + SiF4
The oxidation state of xenon in XeOF4 is calculated as
x-2- 1
XeOF4
x+(-2)+4x(- 1)=0
x-2-4=0
x=+6
24. In atomic reactors, helium gas is used. It is a lso used in filling
lighter air-crafts such as ai r-ships, weather balloons etc.
25. These radioactive minerals have entrapped He atoms, produced
from a-particle, which they give on heating in vacuo.
26. When the mixture of noble gas is cooled in a coconut bulb at
173 K then Ar, Kr and Xe are adsorbed on charcoal while H e and
Ne are not adsorbed.
27. Krypton is used in miner's cap lamps.
28. Option (c) has noble gas configuration as it has 8 electrons in
valence shell.
29. He gas is not adsorbed by coconut charcoal.
30. Helium is not used to produce and sustain powerful
superconducting magnets. All others are the uses of helium.
31. Noble gases are present in atmosphere in minute quantities except
Rn, which is radioactive and is formed by decay of Ra.
32. Noble gases are adsorbed by coconut charcoal. T he adsorption of
different noble gases occur at different temperatures, hence,
charcoal is used to separate these gases.
Helium is not adsorbed by charcoal (as it is very difficultly to
liquefiable the gas).
33. Clathrate formation involves dipole induced dipole attraction
(-: water is polar molecule and Xe is non-polar).
34. For advertisement the coloured discharged tubes contains Ne.
35. The end product of the hydrolysis of XeF6 is XeO 3.
H20 H20 H20
XeF6 ~ XeOF4 ~ Xe02F2 ~ XeO3
36. The correct order of occurrence in air is
Ar >Ne>Kr
37. Fischer R inge method is used to separate noble gas mixture from
air. Air free of CO2 is passed over a heat mixture of90% CaC2
and IO % Ca Cl 2. A mixture of inert gases are obtained.
38. The boiling point of inert gases increases w ith increase in
molecular weight due to increase in van der Waals' forces.
·: Xe has largest size, among inert gases.
:. Xe has highest boiling point.
22
The d-andf-Block Elements
QUICK REVIEW
d-Block Elements
The elements whose differentiating electron enters in
(n - l)d-sublevel are called d-block elements. The d-block
elements in which the atoms or ions have incomplete
d-orbitals are called transition elements. The general outer
electronic configuration of d-block element is
(n - l)dl - 10 nsOor I or2 _
• Zn, Cd and Hg have completely filled (n - l)d orbitals so
they do not show much resemblance with other transition
elements.
• d-block elements are present as 3d, 4d, 5d and 6d series
in the periodic table.
• The transition elements exhibit typical characteristic
properties. This is due to their small atomic sizes, large
nuclear charges and the presence of unpaired d-electron.
General Characteristics
In general atomic radius and ionic (ions and same charge)
in a given series show progressive decrease in radius with
increasing atomic number.
However, the variation within a series is quite small.
Atomic and Ionic Radius
The atomic and ionic radius of the elements of 4d-series
are higher than 3d-series as the number of shells increases
on moving down the group.
Ionisation Energy
Elements of 5d transition series have higher ionisation
energies than elements of 3d and 4d transition series due
to greater effective nuclear charge and poor shielding
effect of 4 / -electrons.
Oxidation States
Minimwn oxidation state shown by any transition element is
equal to ns electrons and the highest oxidation state is equal to
the sum ofnsand (n - l)d electron.+ 2oxidation state becomes
more stable while + 3 oxidation state becomes less stable as we
move from left to right in the periodic table. Highest oxidation
state (+ 8)is shown by Ru and Os (4d and 5d series elements).
Standard Electrode Potential
Standard reduction potential (SRP) of M 2+ / M values
increases from left to right as IP values increases (except Zn).
• Cu cannot displace H 2 from acids because it has highest SRP
value which is+ 0.34 V.
• Mn, Ni and Zn have more negative standard reduction
potential values than expected because Mn and Zn have
10
d 5 and d stable electronic configuration.
Colour
Transition elements form coloured complex compound.
Transition metal ions have unpaired d-electrons, due to this
intra d-d transition takes place. The ions such as
Sc 3+ , Ti 4+, Cu+, Hg 2+, Cd 2+ and Zn 2+ having completely
empty or fully filled 3d-orbitals do not show any d-d transition
and hence appear colourless.
Magnetic Properties
Most of transition elements show paramagnetism. It arises due
to the presence of unpaired electrons in atoms, ions or
molecules. Magnetic property depends upon the number of
unpaired electrons in d-orbitals. Mn have maximum
paramagnetic character. µ = ,Jn( n + 2), where, n is the number
of unpaired electrons.
516 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Catalytic Properties Potassium permanganate Preparation
Transition elements on account of their variable valency have • It is prepared from the pyrolusite [MnO2 ] ore. The ore is
the ability to form intermediate compounds very readily, thus treated with KOH (or) K 2 CO3 in presence of atmospheric
acting as good catalysts. oxygen or any other oxidising agent to give K 2 MnO4 . It is
purple coloured crystalline compound and is fairly soluble
Complex Formation in water. KMnO4 act as an oxidising agent in alkaline,
Transition metals show complexing property due to their very neutral and acidic solution.
small size, high positive charge density and presence of vacant Potassium Dichromate (K 2Cr20
orbitals of suitable energy to accept the pair of electrons. 7)
It is prepared from chromite ore [FeO· Cr2 0 3 ] . Chromite ore
Nature of Oxides is treated withNa 2 CO3 to convert into Na 2 Cr2 O7 • Itis mixed
with KC! gives K 2 Cr2 O 7 . Itis orange red coloured crystalline
While moving along a period from Sc to Zn basic nature
solid. On strong heating it decomposes and gives oxygen. It
decreases and acidic nature increases. Behaviow· differs when
acts as a powerful oxidising agent in acidic medium (di!.
oxidation states are different.
H2 SO 4 ).
Oxide MnO Mn3O4 Mn2 O3 MnO2
oxidation + 2 + 8/3 +3 +4
/-Block Elements
state of Mn Amphoteric MnO
3 Mn2 0 7 These are called inner transition elements. General electronic
+6 +7 configuration off block elements is
Weakly
acidic
Strongly
acidic (n - 2) J'-14(n - l)do- 1ons2 .
Oxidation VO V2Os • Lanthanum and actinium doesn't belong to /-block
state ofV + 2 +5 elements as they do not have any electron in 4/ and 5/
Basic Amphoteric subshell respectively. However, their properties resemble
with elements of 4/ and 5/ series.
(i) Iron Fe2 + is green while Fe 3+ is yellow. • As we move from La to Lu, there is slow decrease in size.
• Fe 3+ is stronger oxidising agent than Fe 2 +. This is known as lanthanide contraction. With increase in
atomic nwnber, effective nuclear charge increases due to
• Mohr's salt [FeSO 4 ·(NH4 )iSO 4 ·6H2 O] is light imperfect shielding of / -electrons (due to diffused shape of
green double salt and it is resistant to atmospheric /-orbitals), this results in contraction in size of
oxidation. 4/-subshell.
• FeSO4 · 7H2 0 is green vitriol.
(ii) Copper CuSO 4 • 5H2 0 is green vitriol. Atomic Radius
Atomic radius of second row transition elements are almost
• Basic copper acetate, Cu(CH3 COO)i · Cu(OH)i
similar to those of third row of transition elements. Zr-Hf
(verdigris) is used as a green pigment in paints.
and Nb-Ta pairs have same atomic radius due to effect of
• Cu Cl 2 and CuBr2 are covalent while Cu F2 is ionic. lanthanide contraction.
(iii) Silver and Gold
• AgNO 3 silver nitrate is called lunar caustic. Its Oxidation State
aqueous solution is called indelible ink. Most stable oxidation state of lanthanide is + 3. Along with
(iv) Mercury Hg z+ salts are more stable than Hgt salts. + 3 oxidation state, certain metals show+ 2and + 4 oxidation
state (to attain J 0 , f 1 or / 4 configuration).
• Mercury fom1s alloys with all metals except iron and
Actinides usually exhibit + 2oxidation state. These also show
platinum.
+ 4, + 5 and + 6 oxidation state. The ions with 5J 0 , 5 f 1, and
• HgCl 2 is corrosive sublimate, it is poisonous and
best antidote for it is white of an egg. 5/1 4 are colourless.

• Hg 2 Cl 2 is calomel. With NH 4 OH it forms a black Some Alloys of Cu

mixture ofHg + Hg(NH 2 )Cl.
(v) Compounds of Zinc
• Rinmann's green is a green pigment. It is ZnO· CoO.
• Zinc sulphide + barium sulphate is lithopone, a white
paint.
• Zinc oxide (ZnO) is called philosopher's wool.
• ZnSO4 · 2H 2 O is white vitriol.
• Brass 70-80% Cu + 30-20% Zn
• Bronze 80-90% Cu + 20-1 0% Sn
• Bell metal 72-80% Cu + 28-20% Zn
• Gun metal 85% Cu + 5% Sn + l 0% Zn
• Mone! metal 70% Cu + 30% N i
• Constantan 60% Cu + 40% Ni
• German silver 50-60% Cu + 30% Zn+ 20% Ni
 Topic 1
Transition Elements and their Compounds
2014
Directions (Q. Nos. 1-2) Read the 7. Which one of these is not known? [KCET]
An aqueous solution of metal ion M 1 reacts separately (a) CuC1 2 (d) CuBr2
with reagents Q and R in excess to give tetrahedral and 8. The electronic configuration of Cu is [WBJEE]
square planar complexes, respectively. An aqueous 2 6 9 2
solution of another metal ion M 2 always forms (a)[Ne] 3s ,3p , 3d , 4s
tetrahedral complexes with these reagents. Aqueous (b) [Ne] 3s2 , 3p 6 , 3d 10 ,4s 1
solution of M 2 on reaction with reagent S gives white (c)[Ne] 3s2 ,3p 6 , 3d 3 ,4s 2 , 4p 6
precipitate which dissolves in excess of S. The reactions
are summarised in the scheme give below (d) [Ne]3s 2 ,3p s ,3ds
. ,4s2 ,4p 4
[JEE Advanced] 9. Metal ion responsible for the Minamata disease is
Scheme
(a)Co 2+ (b)Hg 2+ [WBJEEJ
Tetrahedral ex~ss M 1 exc~ss Square planar (c) Cu 2+ (d) Zn 2+
Q R 10. Cupric compounds are more stable than their cuprous
Tetrahedral ~ M 2~ Tetrahedral
counterparts in solid state. This is because [WB JEE]
/ ' ..,,,;,m0n, '=""' (a) the endothermic character of the 2nd IP ofCu is not so
high
(b) size of Cu 2+ is less than Cu +
White precipitate ~
excess
Precipitate 2
(c) Cu + has stable electronic configurations compared
Dissolves
to cu +
1. M 1 , Q and R, respectively are (d) the lattice energy released for cupric compounds is
(a) Zn i + , KCNandHCl (b) Ni 2 + ,HCI andKCN must higher than Cu +
(c) Cd 2 + , KCN and HCl (d) Co 2 +, HCI and KCN 11. Which is not true for describing the catalytic activity of
2. Reagent S is transition metals? [AMUJ
(a) K 4 [Fe(CN) 6 ] (b) Na 2 HPO 4 (a) Their ability to adopt multiple oxidation states
(c) K 2 CrO 4 (d) KOH (b) Their ability to fom1 bonds between reactant
molecule and atoms of the surface of catalysts
3. Mercury is a liquid metal because [BITSATJ (c) Increasing the concentration of reactants at the
(a) it has a completely filled d-orbital that causes d-d catalyst surface
overlapping (d) Strengthening the bonds in the reacting molecules
(b) it has completely filled d-orbital that prevents d-d 12. Which one of the following transition element has the
overlapping lowest value of enthalpy of atomisation? [AMUJ
(c) it has a completely filleds-orbital
(d) it has a small atomic size (a) Cr (b) Cu (c) Zn (d) M
4. Which of the following has the maximum number of 13. Which one of the following ions has same number of
unpaired d-electrons? [VITEEE] unpaired electrons as those present in V 3+ ion? [EAMCETJ
2
(a) Fe + (a) Fe 3 + (b)Ni 2+ (c)Mn 2 + (d)Cr 3+
(c) Zn 14. What is the ground state electron configuration of the
5. Which of the following does not represent the correct order Mn 2+ ion? [IPUCET]
1 5 3
of the property indicated? [VITEEEJ (a)[Ar]4s ,3d (b)[Ar]4s2,3d
3 3 3
(a) Sc3+ > Cr + > Fe + > Mn + -ionic radius (c) [Ar]3d 5
(d) [Ar]3d 4
(b) Sc < Ti < Cr < Mn- density
15. The colour of transition metal compound is due to
(c) Mn 2+ > Ni 2+ > Co 2+ < Fe 2+ -ionic radius
(d) FeO < CaO < MnO < CuO - basic natw·e (a) complete ns subshell [J&K CETJ
(b) small size metal ions
6. The element which forms ions in dimeric state is
(c) incomplete (n - l)d-subshell
(a) mercury (b) nickel [Manipall (d) absorption of light in UV region
(c) iron (d) cadmium
518 I Chapterwise & Topicwise Engineering Entrances Solved Papers
16. Paramagnetism is exhibited due to which one of the 24. For the given aqueous reaction which of the statement(s) is
following reason? [J&K CET] (are) true? [IIT JEE]
(a) Presence of unpaired electrons Dilute H2S04
(b) Presence ofcompletely filled electronic subshell KI + K 3 [Fe(CN)6 ]
Excess
(c) By non-transition element
(d) By elements with noble gas configuration Brownish-yellow solution
17. Silver, gold, platinum, iron, copper and titaniwn are part of ! ZnS04
the [J&K CET] (White precipitate + Brownish-yellow filtrate)
(a) minerals (b) transition metals ! Na 2 S2 0 3
(c) salts (d) All of these Colourless solution
18. Why d-block element fonn complexes? [J&KCET] (a) The first reaction is redox reaction
(b) White precipitate is Zn 3 [Fe(CN)6 h
(a) Due to large size and high nuclear charge
(c) Addition of filtrate to starch solution gives blue
(b) Due to small size and low nuclear charge
colour
(c) Due to small size and high nuclear charge (d) White precipitate is soluble in NaOH solution
(d) None of the above
25. Irons exhibits + 2 and + 3 oxidation states. Which of the
2013 following statements about iron is incorrect? CAIEEEJ
19. Which of the following arrangements does not represent (a) Ferrous oxide is more basic in nature than the ferric
the correct order of the property stated against it? oxide
[JEE Mains] (b) Ferrous compounds are relatively more ionic than the
(a) V2+ < Cr 2+ < Mn 2+ < Fe 2+ corresponding ferric compounds
(paramagnetic behaviour) (c) Ferrous compounds are less volatile than the
(b) Ni 2+ < Co 2+ < Fe 2+ < Mn 2+ (ionic size) corresponding ferric compounds
(d) Ferrotts compounds are more easily hydrolysed than
(c) Co 3+ < Fe 3 + < Cr3 + < Sc3+ (stability in aqueous
the corresponding ferric compounds
solution)
(d) Sc < Ti< Cr< Mn (number ofoxidation states) 26. Green vitriol is [BITSAT]

20. Four successive members of the first row transition (a) ferrous sulphate (b) tin oxide
elements are listed below with atomic nwnbers. Which one ( c) zinc oxide (d) ferrous carbonate
of them is expected to have the highest £~ 3+ 1 M 2+ value? 27. Which of the following in Rinmann's green? [Manipall
(a) Cr (Z = 24) [JEE Mains] (a) ZnO (b) ZnS+ BaSO4
(b) Mn (Z = 25) (c) ZnSO 4 -7H 2 O (d) ZnO-CoO
(c) Fe (Z = 26) 28. A metal gets coated with a green basic carbonate when
(d) Co (Z = 27) exposed at atmosphere. Metal is [MP PET]
21. The catalytic activity of the transition metals and their (a) copper (b) zinc (c) iron (d) silver
compounds is described to [Kerala CEEJ 29. The colour of Cut containing salt is CMPPET]
(a) their chemical reactivity
(b) their magnetic behaviour (a) white (b) blue (c) orange (d) yellow
( c) their unfilled d-orbitals 30. Silver iodide is used for producing artificial rain because
(d) their ability to adopt multiple oxidation states and Agl [KCET]
their complexing ability (a) is easy to synthesise
(e) None of the above (b) has crystal structure similar to ice
22. What is the general electronic configuration for 2nd row (c) is insoluble in water
transition series? [OJEEJ (d) is easy to spray at high altitude
(a) [Ne] 3d 1- JO, 4s 2 (b)[Ar]3d 1- 1 2
JO, 4s -
2011
(c) [Kr]4d 1 - IO, 5s 1 - 2 (d) [Xe]5d 1 - IO, 5s 1 - 2
31. In chromite ore, the oxidation number of iron and
2012 chromium are respectively CKCETJ

23. The colour of light absorbed by an aqueous solution of (a) + 3, + 2 (b) + 3, + 6 (c) + 2,+ 6 (d) + 2, + 3
2
CuSO4 is [HT JEE] 32. The spin only magnetic moment of Fe + ion (in BM) is
(a) orange-red (b) blue-green approximately CKCETJ
( c) yellow (d) violet (a) 4 (b)7 (c) 5 (d) 6
 The d-and f-Block Elements I 519
33. The bonds present in the structure of dichromate ion are 41. The spin only magnetic moment ofMn 4+ ion is nearly
(a) four equivalent Cr-Obonds only [Kerala CEEJ (a) 3 BM (b) 6 BM [KCET]
(b) six equivalent Cr-Obonds and one 0--0bond (c) 4 BM (d) 5 BM
( c) six equivalent Cr- 0 bonds and one Cr-Cr bond
[Punjab CETJ
( d) eight equivalent Cr-0 bonds
(e) six equivalent Cr-0 bonds and one Cr-0-Cr (a) green salt (b) Glauber's salt
bond (c) Mohr's salt (d) alum
34. Anhydrous ferric chloride is prepared by [WB JEE] 43. Amongst the following, the lowest degree of
(a) dissolving Fe(OHh in concentrated HCl paramagnetism per mole of the compow1d at 298 K will be
(b) dissolving Fe(OHh in dilute HCl shown by [Punjab CETJ
(c) passing dry HCI over heated iron scrap (a)MnS04 · 4H 2 0 (b)NiS04 · 6H2 0
( d) passing dry Cl 2 gas over heated iron scrap (c) FeS04 · 6H 2 0 (d) CuS0 4 -SH 2 0
35. When dil. H 2 S04 is added to aqueous solution of 44. Which of the following is correct? [Punjab CETJ
potassium chromate, yellow colour of solution turns to (a) Duralumin : A1 + Cu + Mg + Ag
orange colour. It indicates [Guj CETJ (b) German silver : Cu + Zn + C
(a) chromate ions are reduced (c) Gun metal : Cu + Zn + Sn
(b) chromate ions are oxidised ( d) Solder : Pb + Al
(c) monocentric complex is converted into dicentric 45. Which of the following is called white vitriol ?
complex [Punjab CET]
(d) oxygen gets removed from chromate ions
(a) ZnC1 2 (b) MgS04 · 7H 2 0
36. Copper exhibits only + 2 oxidation state in its stable (c) A1 2 (S04 h (d) ZnS04 -7H 2 0
compounds. Why ? [Guj CETJ
46. Which of the following is not co1Tect about transition
( a) Copper is transition metal in + 2 state metals ? [Punjab CET]
(b) + 2 state compounds of copper are formed by
(a) Their compounds are generally coloured
exothermic reactions
(b) They can form ionic or covalent compounds
( c) Electron configuration of in + 2 state is [Ar ]3d 9, 4s0
(c) Their melting and boiling points are high
(d) Copper gives colow·ed compounds in + 2 state
(d) They do not exhibit variable valency
37. German silver alloy contains [Guj CETJ /!,.
(a) zinc, silver and copper 47. K 2 Cr2 0 7 ~ K 2 Cr0 4 +0 2 + X
(b) nickel, silver and copper In the above reaction, X is [Punjab CET]
(c) germanium, silver and copper (a) Cr03
( d) zinc, nickel and copper (c) Cr2 0 3
2010 48. Choose the correct reaction to prepare rnercurous chloride
( calomel) [Guj CETJ
38. The co1rect order of £~ 2+ 1 M values with negative sign for
/!,.
the four successive elements Cr, Mn, Fe and Co is [A.IEEE] (a) HgC1 2 + H g ~ (b) Hg + Cl 2 ~

(a)Mn > Cr > Fe > Co (b)Cr > Fe > Mn > Co (c) HgC1 2 + SnC12 ~ (d) Both (a) and (c)
(c)Fe > Mn > Cr > Co (d)Cr > Mn > Fe > Co 49. Carbon content of [RPET]
39. Of the following outer electronic configurations of atoms, (a) steel is in between those ofcast iron and wrought iron
the highest oxidation state is achieved by which one of (b) cast iron is in between those of steel and wrought iron
them ? [Manipall ( c) wrought iron is in between those ofsteel and cast iom
( d) steel is higher than that of pig iron
(a)(n -l)d 2 ,ns2 (b)(n -l)d 5 ,ns1
50. Which one of the following transition metal ions is
(c)(n - l)d 3 , ns 2 (d)(n - l)d 5 ,ns2
diamagnetic ? CRPETJ
40. KMn04 in basic medium is used as [MPPET] (a) Co + 2
(b) Ni + 2

(a) strong oxidising agent (c) Cu 2+ (d) Zn 2+

(b) strong reducing agent 51. A transition elementX has the configuration[Ar] d 4 in its
( c) strong hydrogenating agent + 3 oxidation state. Its atomic number is [JCECEJ
( d) poor reducing agent
(a) 25 (b) 26 (c) 22 (d) 19
520 I Chapterwise & Topicwise Engineering Entrances Solved Papers
52. Which of the following statements concerning transition 61. What is the oxidation state of iron in Mohr's salt? [OJEEJ
elements is false ? [JCECEJ (a)+3 (b)0
(a) They are all metals (c)+2 (d)+l
(b) They easily form complex coorclination compounds 62. The gas obtained by reaction of K 4 Fe(CN)6 with cone.
( c) Compounds containing their ions are mostly coloured
( d) They show multiple oxidation states al ways cliffering H2SO4 is [OJEEJ
by units of two (a) H 2S (b)CO
(c) NO 2 (d) CO 2
2009
63. Magnetic moment of manganese in (NH 4 ) 2 MnBr2 is
53. The oxidation number of Mn in the product of alkaline
(a) 3.87 BM (b) 5.91 BM [OJEEJ
oxidative fusion ofMnO 2 is [HT JEE]
(c) 4 .89 BM (d) 2.82 BM
w2 ~3 ~4 006 64. MnO4 reacts with bromide ion in alkaline medium to
54. In context with the transition elements, which of the g ive [OJEEJ
following statement is incorrect ? [AIEEEJ
(a) MnBr4 (b) MnOBr2
(a) In addition to the normal oxidation state, the zero
(c) MnO 2 , Br0"3 (d) MnO, BrO
oxidation state is also shown by these elements in
complexes 65. Atomic radius of Ti, Zr and Hf vary [lndraprastha CET]
(b) In the highest oxidation state, the transition metal (a)Ti > Zr > Hf (b) Ti < Zr < Hf
shows basic character and form cationic complexes ( c) Ti < Hf < Zr ( d) Ti < Zr = HF
( c) In the highest oxidation state of the first five
transition elements (Sc to Mn), all the 4s and 4d 66. The following two reactions HNO 3 with Zn are given as
electrons are used for boncling ( equations are not balanced)
( d) Once the d 5 configuration is exceeded, the tendency I. Zn + cone. HN0 3 ~ Zn (N0 3 ) 2 + X + H20 (A)
to involve all the 3d electrons in bonding decreases TI. Zn + di!. HN03 ~ Zn (N0 3)i + Y + Hp (B)

55. The magnetic moment of a transition metal ion is /Is BM. In reactions I and II, the compounds X and Y respectively,
are [DCEJ
Therefore, the number ofunpaired electrons present in it, is
( a) 3 (b) 4 [Manipall (a) NO 2 and NO (b) NO 2 and NO2
( c) 1 (d) 2 (c) NO and NO 2 (d) NO 2 and NH4 NO3

56. 'Hydride gap' is referred to which region of the periodic 2008

table ? [Kerala CEE] 67. Among the following, the coloured compound is
(a) Groups 3, 4 and 5 {b) Groups 5, 6 and 7 (a) CuCl (b) K 3 [Cu(CN)4 ][IITJEEJ
(c) Groups 4, 5 and 6 (d) Groups 7, 8 and 9
(e) Groups 6, 7 and 8 (c) CuF2 (d)[Cu(CH 3 CN) 4 ]BF4

57. A compound in which a metal ionMx+ (Z = 25)has a spin

68. Which of the following is not a characteristic of transition
elements ? [VITEEEJ
only magnetic moment of ✓'24 BM. The number of
(a) Variable oxidation states
unpaired electrons in the compound and the oxidation state
(b) Formation of coloured compounds
of the metal ion are respectively [Ke ral a CEE]
( c) Formation of interstitial compounds
( a) 4 and 2 (b) 5 and 3 (c) 3 and 2 (d) Natural radioactivity
(d)4and3 (e)3andl
69. The magnetic moment of a salt containing Zn2+ ion is
58. Stainless steel has iron and [UPSEE]
(a) 0 (b) 1.87 [VITEEE]
(a) Cr (b) Cu (c) Co (d) Zn
(c) 5.92 (d) 2
59. Formation of coloured ions by transition metals signifies
70. Hair dyes contain [VITEEE]
(a) absorption of light from UV range [UPSEEJ
(a) coppernitrate (b) gold chloride
(b) emission of light
( c) silver nitrate (d) copper sulphate
( c) presence of unpaired electrons in sand p-orbitals
(d) complimentary colours to the absorbed light 71. Which of the oxide of manganese is amphoteric?
(a) MnO2 (b) Mn 20 3 [Manipal]
60. Transition metal ions show colour because [UPSEEJ
(c) Mn 2O 7 (d) MnO
(a) they absorb light
(b) they emit light 72. Which of the following ions is colourless in solution ?
( c) they are paramagnetic (a) V 3+ (b) Cr 3+ [MHT CETJ
(d) they exhibit d -d transition (c) Co +2 3
(d) Sc +
 The d-and f-Block Elements I 521
73. Mercury is a liquid metal because [KCET] 82. When oxyhaemoglobin changes to deoxyhaemoglobin,
(a) it has a completely filled s-orbital Fe 2+ ion changes from [DCE]
(b) it has a small atomic size (a) diamagnetic to paramagnetic
(c) it has a completely filled d-orbital that prevents d-d (b) paramagnetic to diamagnetic
overlapping of orbitals ( c) diamagnetic to ferromagnetic
(d) it has a completely filled d-orbital that causes d-d
( d) paramagnetic to ferromagnetic
overlapping
74. Which one of the following reactions will occur on heatmg 2007
AgN0 3 above its melting point? [Ke rala CEE] 83. Which of the following transition metal ions will have
(a) 2AgN03 ~ 2Ag + 2N02 + 0 2 definite value of magnetic moment ? [BITSAT]
(b) 2AgN03 ~ 2Ag + N 2 + 302
3
(a) Sc + 3
(b) Ti + (c) Cu J+ (d) Zn 2+
(c) 2AgN03 ~ 2AgN0 2 + 02 84. Which of the following compound is expected to be
(d) 2AgN03 ~ 2Ag + 2NO + 20 2 coloured ? [BITSAT]
(e) 2AgN03 ~ Ag 20 + N 203 + 02 (a)Ag 2 S04 (b)CuF2 (c)MgF2 (d)CuCl
75. Pick out the correct statements from the following. 85. Which of the following compounds volatilises on heating?
I. Cobalt (III) is more stable in octahedral complexes. (a) MgC1 2 (b) HgC12 [VITEEE]
II. Zinc forms coloured ions or complexes. (c) CaC12 (d) FeC1 3
III. Most of the d-block elements and their compounds are
ferromagnetic. 86. Among the following the compound that is both
IV. Osmium shows (VIII) oxidation state. paran1agnetic and coloured is [VITEEE]
V. Cobalt (II) is more stable in octahedral complexes. (a) K 2Cr2 0 7 (b) (NH 4 ) 2 [TiCl 6 ]
(a) I and II (b) I and III [Kerala CEE] (c)VOS04 (d) K 3 [Cu(CN)4 ]
(c) II and IV (d) I and IV 87. Corrosive sublimate (HgC1 2 ) can be used to distinguish
(e) II and V between [MHT CET]
76. Which of the following is not a member of 3d-transition (a) formic acid and acetic acid
series ? [WB JEE] (b) acetaldehyde and butanone
(a) Fe (b) Co ( c) formaldehyde and propanone
(c) A u (d) Cu ( d) All of the above
77 . KMn0 4 (acidic/alkaline) is not decolourised by [UPSEE] 88. Which of the following group of transition metals is called
coinage metals ? [MP P ET]
(a) Mohr salt (b) oxalic acid
(c) benzene (d) propene (a) Cu, Ag, Au (b) R u, Rh, Pd
(c) Fe, Co, Ni (d) Os, Ir, Pt
78. The highest oxidation state exhibited by transition metals is
89. The atomic numbers of vanadium (V), chromium (Cr),
(a) +7 (b) + 8 [J&KCET]
manganese (Mn) and iron (Fe) are respectively 23, 24, 25
(c) + 6 (d) + 5
and 26. Which one of these may be expected to have the
79. Which one of the following statements is not true with highest second ionisation enthalpy ? [MP PET]
regard to transition elements ? [J&K CET]
(a) V (b) Cr (c) Mn (d) Fe
(a) They readily fom1 complex compounds
90. Formation ofcoloured solution is possible when metal ion
(b) They show variable oxidation states
in the compound contains [KCET]
( c) All their ions are colourless
(a) paired electrons (b) lone pair of electrons
(d) Their ions contain partially filled d-electrons
( c) unpaired electrons ( d) None of these
80. The highest magnetic moment is shown by the transition
metal ion with the configuration [Jamia Mi.Ilia Islamia]
91. Which of the following ions has a magnetic moment of
2 5.93 BM ?
(a) 3d (b) 3d 5 (Atomic number V = 23, Cr= 24, Mn= 25, Fe = 26)
(c) 3d 7 (d) 3d 9
(a) Mn 2 + (b) Fe 2+ (c) Cr 2 + [Kerala CEE]
81. A transition metal ion exists in its highest oxidation state. It (d) y 3+ (e) Cr 3+
is expected to behave as [Jamia Mi.Ilia Islamia]
92. When hydrogen peroxide is added to acidified potassium
(a) a chelating agent
dichromate, a blue colour is produced due to formation of
(b) a central metal in a coordination compound
( c) an oxidising agent (a) Cr03 (b) Cr2 0 3 (c) Cr0 5 [Ke rala CEE]
( d) a reducing agent (d) CrO~- (e) Cr20 ~-
522 I Chapterwise & Topicwise Engineering Entrances Solved Papers

93. Excess of KI reacts with CuSO4 solution and then 107. Bronze is a mixture of [UPSEE, Manipal]
Na 2 S 2 O 3 solution is added to it. Which of the statements (a) Pb + Sn (b)Cu + Sn (c)Cu + Zn (d) Pb + Zn
is incorrect for this reaction ? [UPSEE, WB JEE]
108. In photography we use [Manipal]
(a) Cu 2 12 fonned (b) Cul2 is formed
(a) Agl (b) NH 3 (c) AgCl (d) AgBr
( c) Na 2 S 2 0 3 is oxidised (d) Evolved 12 is reduced
109. Match the following Columns.
94. Which of the following is philosopher's wool? [WB JEE]
Column I Column II
(a) ZnO (b) HgO (c) Ag 2 O (d) CuO
Metal ions Magnetic moment (BM)
95. Ferrous sulphate (FeSO 4 · 7H 2 O) is known as [WB JEE]
A. Cr 3+ l. ✓35
(a) vermillion (b) G lauber's salt
B. Fe2+ 2. -✓30
( c) green vitriol (d) Mohr's salt
96. The magnetic moment of Cu 2 + ion is
c. Ni2+ 3. ✓
24
[OJEEJ
D. Mn 2+ 4. ✓IS
(a) 2.73 (b) zero (c) 1.93 (d) 1.73
97. Cl 2 + HgO ~ ? [OJEE]
5. ./8
(a) Cl 2 0 + HgCl (b) Cl 2 0 + HgC1 2 Codes [Kerala CEE]
(c) C lO + HgCl (d) ClO + HgC12 A B C D A B C D
98. The magnetic moment of a transition metal ion is 3 .87 BM. (a) 1 3 5 4 (b) 2 3 5 1
The number of unpaired electrons present in it is [AMU] (c) 4 3 5 1 (d) 4 5 3 1
2 3
w2 ~3 ~4 oos (e) 5 1
110. Philosopher's wool on heating with BaO at 1100°c
99. Which of the following pair of transition metal ions, have
produce CUPSEE]
the same calculated values of magnetic moment?
(a) Ba + Zn C12 (b) BaCdO 2
(a) Ti 2 + and V 2+ [EAMCET]
(b) Fe 2 + and Cu 2+
(c)BaZnO 2 (d) BaO 2 + Zn
(c) Cr 2+ and Fe 2+ 111. What is the correct order of spin only magnetic moment
(d) Co 2+ and Ti 2+ (in BM) of Mn 2+, Cr 2+ and V 2+ ? CEAMCETJ

100. Mone! metal is an alloy of [J&KCET] (a) Mn 2+ > V 2 + > Cr 2+ (b) V 2 + > Cr 2+ > Mn 2+
(a) Cu, Ni, Fe, Mn (b) Cu, Sn, Zn (c) Mn 2+ > Cr 2 + > V 2+ (d) Cr 2 + > V 2+ > Mn 2+
(c) Cu, Sn, P (d) Cu, Zn 112. Brass is an alloy of Cu with [Guj CETJ
101. Which metal gives hydrogen gas on heating with hot (a) Al (b) Sn (c) Ag (d) Zn
concentrated alkali ? [BCECE] 113. A white precipitate is formed on adding KI to CuSO 4
(a)Ag (b)Ni (c)Zn (d)Cu solution. It is of [Guj CETJ
102. Which of the following is used as purgative? [BCECE] (a) Cu 2 I 2 (b) C ul 2 (c) Cu 2 S (d) Cu 2 SO 4
(a) H gS (b) Hg 2 Cl 2 (c) HgC1 2 (d) ZnSO4 114. The 3d-block element that exhibits maximum number of
103. Gun metal is [BCECE] oxidation states is [J&K CET]
(a) Cu + Zn (b)Cu + Sn + Zn (a) Sc (b) Ti (c) Mn (d) Zn
(c)Cu + Sn (d) Zn + Sn 115. Among the following ions (hydrated), the colourless metal
104. KI and Cu SO 4 solutions on mixing produce [BCECE] ion is [J&K CET]
(a)Cu+ 2
(b)Cu + 2
(c)Fe + (d)Mn 2+
(a) Cu 2l 2 + K 2SO 4 (b) Cu 2l 2 + 12 + K2SO4
(c) C ul2 + K 2 SO4 (d) Cul2 + I2 + K 2 SO4 116. Which of the following is used as indelibleink?
105. Which do not decolourise KMnO4 aqueous solution? (a) Aqueous CuSO 4 solution [J&K CET]
(b) Aqueous AgNO 3 solution
(a) C 20~- (b) HSOj' [DCE]
(c) Aqueous NaCl solution
(c) cot (d) sot (d) Aqueous NaOH solution
2006 117. Ford-block elements the first ionisation potential is of the
order [Jamia Millia Islamia]
106. The 'spin-only' magnetic moment [in units of Bohr
(a) Zn > Fe > Cu > Cr
magneton, (µ 13 )] ofNi 2+ in aqueous solution would be
(b) Sc = Ti < V = Cr
(Atomic number of N i = 28) [AIEEE] (c)Zn < Cu < Ni < Co
(a) 2.84 (b) 4 .90 (c) 0 (d) 1.73 (d) V > Cr > Mn > Fe
 The d-and f-Block Elements I 523
118. Which of the following is amphoteric? 127. Number of electrons in 3d-orbital of v2+, Cr2+, Mn 2+
[Jamia Millia Islamia] 2
and Fe + are 3, 4, 5, and 6 respectively. Which of the
(b) CuO (d) NiO following ions will have largest value of magnetic moment
( µ )? [AMU, Jamia Millia Islamia]
2005 (a) V2 + (b) Cr 2+
119. Which pair of compounds is expected to show similar (c) Mn 2+ (d) Fe2+
colour in aqueous medium ? [IIT JEE]
128. Railway wagon axles are made by heating iron rods
(a) FeC1 3 and CuC1 2 {b) VOC1 2 and CuC1 2 embedded in charcoal powder. This process is known as
(c) VOC1 2 and FeC1 2 (d) FeC1 2 and MnC1 2 [Guj CET]
120. Which of the following is deliquescent? [BITSATJ (a) tempering (b) case hardening
(a) ZnC1 2 (b) Hg 2 Cl 2 ( c) sherardising ( d) annealing
(c) HgC1 2 (d) CdC1 2 129. The form of iron having the highest carbon content is
121. Which of the following pairs of elements cannot form an (a) cast iron (b) wrought iron[J&K CETJ
alloy ? [KCETJ ( c) stainless steel ( d) mild steel
(a) Zn, Cu {b) Fe, Hg 130. Cr0 3 dissolves in aqueous NaOH to give [J&KCET]
(c) Fe, C (d) Hg, Na
(a) Crot (b) Cr(OH)3
122. Which of the following types of metals form the most
efficient catalysts ? [KCETJ (c) Cr2 0~- (d) Cr(OH)z
(a) Alkali metals (b) Alkaline earth metals 131. Brass, bronze and German silver have one common metal.
( c) Transition metals (d) A ll of these This is [J&K CETJ
123. Effective magnetic moment ofSc 3+ ion is [Kerala CEE] (a) Zn (b) Fe (c) Al (d) Cu
(a) I .73 {b) 0 132. Which of the following is the green coloured powder
(c) 5.92 (d) 2.83 produced when ammonium dichromate is used in fire
(e) 3.87 works ? [J&K CET]
124. Potassium permanganate acts as an oxidant in alkaline and (b) Cr03
acidic medium. The final products formed from KMnO4 in (d) Cr0(0 2 )
the two conditions are respectively [Kerala CEEJ 133. When calomel reacts with NH4 OH solution, the compound
(a) Mn0 2 - and Mn 3 + (b) Mn 3+ and Mn 2+ formed is CBCECEJ
(c) Mn 2+ and Mn 3+ (d) Mn0 2 and Mn 2+ (a)NH 2 - Hg-Cl (b)Hg 2 Cl 2 NH 3
(e) Mn 2 +, Mn02 (c) Hg(NH 3 h Cl 2 (d) HgC1 2 NH 3

125. Mohr salt is made up of which combination of salt ? 134. Copper sulphate solution reacts with KCN and gives

(a) Ammonium sulphate and potash [UPSEEJ (a) K 3 [Cu(CN) 4 ] (b)CuCN CBCECEJ
(b) Ammonium sulphate and fe1Tous sulphate (c) Cu(CN)z (d) K 2 [Cu(CN) 4 ]
(c) Ammonium sulphate and copper sulphate 135. Least paramagnetic property is shown by [DCEJ
(d) Ammonium sulphate and magnesium sulphate (a) Fe (b) Mn (c) N i (d) Cu
126. KMn04 in basic medium is reduced to [OJEE] 136. Zn does not show variable valency because of [DCEJ
(a) K 2 Mn04 (b) Mn0 2 (a) complete d-subshell (b) inert pair effect
(c) Mn(OH) 2 (d) Mn 2+ ( c) 4s2-subshell ( d) None of these
 Topic 2
Inner-Transition Elements
2014
1. An /-shell containing 6 unpaired electrons can exchange Which of the above is/are true? [Ke rala CEE]
(a) 6 electrons (b) 9 electrons [VITEEEJ (a) I and III (b) II and III
(c) 12 electrons (d) 15 electrons (c) Only II (d) I and II
(e) Only I
2. Due to lanthanide contraction [Manipal]
(a) Fe, Co, Ni have equal size 2009
(b) Zr and Hf have equal size 10. Knowing that the chemistry of lanthanoids (Ln) is
(c) all /-block ions have equal size dominated by its+ 3 oxidation state, which of the following
(d) all isoelectric ions have equal size statements is incorrect ? [AIEEEJ
3. The correct statement is [KCET] (a) Because of the large size of the Ln (III) ions its
(a) the earlier members of lanthanoid series resemble compounds is predominantly ionic in character
calcium in their chemical properties (b) The ionic sizes of Ln (III) decrease in general with
(b) the extent of actinoid contraction is almost the same increasing atomic number
as lanthanoid contraction (c) Ln (III) compounds are generally colourless
(c) in general, lanthanoid and actinoids do not sh ow (d) Ln (III) hydroxide are mainly basic in character
variable oxidation states
11. Which lanthanide compound is used as a pigment?
(d) Ce 4+ in aqueous solution is not known
(a) CeO 2 (b) Ce(OHh [Guj CETJ
4. The lanthanoid which exhibits + 4 oxidation [AMUJ
(c) Lu(OHh (d) Tb(OHh
(a) Pm (b)Sm (c)Ce (d)Gd
5. What elements are present in / -block series? [J &K CET]
2008
(a) Lanthanoids 12. Larger number of oxidation states are exhibited by the
actinides than those by the lanthanides, the main reason
(b) Actinoids
being [AIEEEJ
(c) Lanthanoids and actinoids
(d) Lipids (a) 4 /-orbitals more diffused than the 5/-orbitals
(b) lesser energy difference between 5/ and 6d than
6. What are lanthanides and actinides? [J&K CET]
between 4 f and 5d-orbitals
(a) Inner-transition element (b) Noble gas
(c) more energy difference between 5 f and 6d than
(c) Normal element (d) Transition element between 4 f and 5d-orbitals
2011 (d) more reactive nature of the actinoides than the
lanthanides
7. The outer electronic configuration of Gd (atomic number
64) is [AIEEE] 13. The point of dissimilarity between lanthanides and
5
actinides is [MHT CET]
(a) 4/3, 5d , 6s 2
(b) 4/ 8
, 5d 0
, 6s 2

2
(a) three outennost shells are partially filled
(c) 4/4, 5d4, 6s (d) 4/7, 5d 1 , 6s2 (b) they show oxidation state of + 3 (common)
8. In context of the lanthanoids, which of the following (c) they are called inner-transition elements
statements is not correct ? [AIEEEJ (d) their are radioactive in nature
(a) There is a gradual decrease in the radius of the 14. Most common oxidation states of Ce (cerium) are
members with increasing atomic number in the series (a) +3, +4 (b) +2, +3 [MHT CET]
(b) All the members exhibit + 3 oxidation state (c) +2, +4 (d) +3, +5
(c) Because of similar prope1ties the separation of
lanthanoids is not easy 15. The correct order of ionic radius ofY 3+, La 3+, Eu 3+ and
(d) Availability of 4 / -electrons results in the formation of Lu 3+ is [Guj CETJ
compounds in + 4 state for all members of the series 3 3 3
(a) y + < La + < Eu + < Lu + 3

9. Consider the following statements. (b) Lu 3 + < Eu 3+ < La 3 + < y 3 +

I. La(OH)3 is the least basic among hydroxides oflanthanides. (c) La 3+ < E u 3+ < Lu 3+ < y 3 +
II. Zr4 + and Hf 4 + possess almost the same ionic radius.
(d) Y 3+ < Lu 3+ < Eu 3+ < La 3+
III. Ce4+ can act as an oxidising agent.

16. The most stable oxidation state of lanthanides is
(a) + 2 (b) + 4 [J&K CET]
(c) 0 (d) + 3
17. Which of the following has got incompletely filled
/-subshell ? [DCE]
(a) Gadolinium (b) Lutetium
(c) Lawrencium (d) Tantalum
18. Lanthanide contraction is due to increase in [DCEJ
(a) shielding by 4/-electrons (b) atomic number
(c) effective nuclear charge
(d) size of 4 /-orb itals
2007
19. Identify the incorrect statement among the following.
(a) d-block elements show irregular and erratic chemical
properties among themselves [AIEEEJ
(b) La and Lu have partially filled d-orbitals and no other
partially filled orbital
(c) The chemistry of various lanthanoids is very sin1ilar
(d) 4/ and Sf-orbitals are equally shielded
2006
20. The actinoides exhibit more number of oxidation states in
general than the lanthanoides. This is because [AIEEEJ
(a) the 5/-orbitals are more buried than the 4 /-orbitals
(b) there is a similarity between 4 f and 5/-orbitals in
their angular part of the wave function
(c) the actinoids are more reactive than the lanthanoids
(d) the 5/-orbitals extend further from the nucleus than
the 4 /-orbitals
21. Lanthanides are [ManipaIJ
(a) 14 elements in the sixth period (atomic number= 90 2005
to 103) that are filling 4 / -sublevel
(b) 14 elements in the seventh period (atomic number
= 90 to 103) that are filling 5/-sublevel
(c) 14 elements in the sixth period (atomic number
= 58 to 7 1) that are filling 4/-sublevel
(d) 14 elements in the seventh period (atomic number
= 58 to 7 1) that are filling 4/-sublevel
The d-and f-Block Elements I 525
22. The lanthanide contraction is responsible for the fact that
(a) Zr and Zn have the same oxidation state [UPSEEJ
(b) Zr and Hf have about the same radius
(c) Zr and Nb have similar oxidation state
(d) Zr and Y have about the same radi us
23. Cerium (Z = 58) is an important member of the lanthanides.
Which of the following statements about cerium is
incorrect ? [Jamia Millia Islamia]
(a) The common oxidation states of cerium are + 3 and
+4
(b) The + 3 oxidation state of cerium is more stable than
the + 4 oxidation state
(c) The + 4 oxidation state of cerium is not known in
solutions
(d) Cerium (IV) acts as an oxidising agent
24. Which one of the following exist in the oxidation state
other than + 3 ? [DCEJ
(a) B (b) Al
(c) Ce (d) Ga
25. Lanthanide contraction is caused due to [AIEEEJ
(a) the appreciable shielding on outer electrons by
4 /-electrons from the nuclear charge
(b) the appreciable shielding on outer electrons by
5d-electrons from the nuclear charge
(c) the same effective nuclear charge from Ce to Lu
(d) the imperfect shielding on outer electrons by
4 /-electrons from the nuclear charge
26. Which belongs to the actinides series ? [J&K CETJ
(a) Ce
(b) Cf
(c) Ca
(d) Cs
 Answers
TOPICl Transition Elements and their Compounds
1. (b) 2. (d) 3. (b) 4. (a) 5. (a,c) 6. (a) 7. (b) 8. (b) 9. (b) 10. (d)
11. (d) 12. (c) 13. (b) 14. (c) 15. (c) 16. (a) 17. (b) 18. (c) 19. (a) 20. (d)
21 . (d) 22. (c) 23. (b) 24. (a,c,d) 25. (d) 26. (a) 27. (d) 28. (a) 29. (a) 30. (b)
31 . (d) 32. (c) 33. (e) 34. (d) 35. (c) 36. (b) 37. (d) 38. (a) 39. (d) 40. (a)
41 . (c) 42. (c) 43. (d) 44. (c) 45. (d) 46. (d) 47. (c) 48. (d) 49. (a) 50. (d)
51 . (a) 52. (d) 53. (d) 54. (b) 55. (a) 56. (d) 57. (d) 58. (a) 59. (d) 60. (d)
61 . (c) 62. (b) 63. (b) 64. (c) 65. (d) 66. (d) 67. (c) 68. (d) 69. (a) 70. (c)
71 . (a) 72. (d) 73. (c) 74. (c) 75. (d) 76. (c) 77. (c) 78. (b) 79. (c) 80. (b)
81 . (c) 82. (a) 83. (b) 84. (b) 85. (b) 86. (c) 87. (a) 88. (a) 89. (b) 90. (c)
91 . (a) 92. (c) 93. (b) 94. (a) 95. (c) 96. (d) 97. (b) 98. (b) 99. (c) 100. (a)
101. (c) 102. (b) 103. (b) 104. (b) 105. (c) 106. (a) 107. (b) 108. (d) 109. (c) 110. (c)
111. (c) 112. (d) 113. (a) 114. (c) 115. (a) 116. (b) 117. (a) 118. (c) 119. (b) 120. (a)
121. (b) 122. (c) 123. (b) 124. (d) 125. (b) 126. (b) 127. (c) 128. (d) 129. (a) 130. (a)
131. (d) 132. (c) 133. (a) 134. (a) 135. (d) 136. (a)
TOPIC2 Inner-Transition Elements
1. (d) 2. (b) 3. (a) 4. (c) 5. (c) 6. (a) 7. (d) 8. (d) 9. (b) 10. (c)
11. (a) 12. (b) 13. (d) 14. (a) 15. (d) 16. (d) 17. (a) 18. (c) 19. (d) 20. (d)
21. (c) 22. (b) 23. (c) 24. (c) 25. (d) 26. (b)

Explanations
Topic 1 Transition Elements and their Compounds
Solutions (Q. Nos. 1-2) Plan This problem can be solved by using [ZnCl4 ]2- HCl(Q) zn2+ KCN(R) [Zn(CN)4 ]2-
concept of chemical reactions of transition metal ions colour and Tetrahedrat excess (M2) excess Tetrahedral
structure of transition metal compounds.
Here, among given four option Ni2+ and Zn 2+ has ability to form
tetrahedral as well as square planar complex depending upon
~~v
types of reagent used. Zn(OH)i ~?.,':s l [Zn(OH)4 ]
2
-
White ppt. Soluble
N i 2+ on reaction w ith KCN forms square planar complex
Zn 2+ on treatment w ith excess of KOH produces [Zn(OH)4 ] 2-.
[N i(CN)4 ] 2- due to strong field strength of CN.
Hence, (I .) M is Ni 2+, Q is H Cl and R is KCN. (2.) Sis KOH.
Ni 2+ + 4KCN ~ [Ni(CN) 4 ] 2- + 4K+ 1

3. The electronic configuration of mercury is [Xe]4/IO, Sd , 6s2.

Square planar 10

1. While on reaction with HCI, Ni 2+ forms stable tetrahedral Its d-subshell is completely filled, thus, it prevents the
overlapping of d-orbitals (d-d overlapping).
complex [Ni(Cl)4 ] 2-. Zn 2+, on the other hand, on reaction w ith
KCN as well as HCl produces tetrahedral complex because of its Hence, it is liquid metal at room temperature.
d 10 electronic configuration. 4. Fe2+ = [Ar] 3d~ 4s0 ⇒ 4 unpaired e lectrons
4HC1
~ [ZnCl4 ]
2
- + 4H+ Cu + = [Ar] 3d 4s ⇒ 0 unpaired electron
1
~
0

Zn = [Ar] 3d , 4s 2⇒ 0 unpaired e lectron

10
Zn 2+ (Zn(CN) 4 ] 2- + 4K+
Ni 3+ = [Ar] 4d7, 4s0⇒ 3 u npaired electrons
[Zn(OH) 4 ] 2-+ 4K+
Excess Whire ppt Hence, Fe2+ possesses maximum number of unpaired electrons.

2. Complete reaction sequence can be shown as: 5. The ionic radius of d-block elements differ in the different
oxidation states and for any given oxidation state, radius
[NiCl ]2- HCl(Q) Ni2+ KCN(R) [Ni(CN)4 ]2- gradually decreases w ith increase in the nuclear charge.
4 excess (~ excess
Square planar
 The d-and f-Block Elements I 527

Element Sc Ti Cr V Cr Mn Fe Co Ni Cu Zn
2
Ionic radius (pm) M + - 90 88 84 80 76 80 76 72 72 72
M3+ 81 76 74 69 66 64 66 63 - - -

Hence, the correct order would be Among these, only Zn has completely filled configuration and
Sc3+ > Cr 3+ > Mn 3+ > Fe3+, contains all paired electrons. Thus, metallic bonding is weakest in
Mn 2+ > Fe2+ > Co2+ > Ni 2+. case of Zn and hence, it has the lowest value of enthalpy of
atomisation.
6. The mercury (I) or mercurous ion, Hgz2+ is unique and exists as a
dimer. The evidence for its dimeric structure, comes from the fact 13. 23 V = (Ar) 3d3, 4s 2
that it is diamagnetic whereas the ion, Hg+ would be v3+ = (Ar) 3d2, 4 s 0 ⇒ 2 unpaired electrons
paramagnetic owing to the presence of one unpaired electron.
The ion Hg/+ is formed by the loss of one s-electron from each 26 Fe = (Ar) 3d6,4s2
mercury atom and two atoms then share the other electron in a Fe3+ = (Ar) 0
3d 5 , 4 s ⇒ S unpaired electrons
covalent bond Hg+ - Hg+.
7. Cupric iodide is not stable. It changes into cuprous iodide. 28 Ni = [Ar) 3d8,4s 2
2CuI2 ~ Cu 2I2 + I2 Ni 2+ = [Ar] 3d8 , 4s0 ⇒ 2 unpaired electrons
8. Atomic mm1ber of Cu is 29. 25Mn = [Ar] 3d , 4s2
5
Thus, it electronic configuration can be written as
Cu 29 = 1s2, 2s2, 2p6, 3s2, 3p6, 3d 10 , 4s 1 Mn 2+ = [Ar) 3d 5 ⇒ S unpaired electrons

(Since, fully filled orbitals are more stable, so one electron from
4s-orbital transfers into 3d-orbital.)
The electronic configuration of neon is
Ne10 = ls2, 2s , 2µ6
2 Thus, Ni 2+ has same number of unpaired electrons as that ofV3+
Thus, using inert gas configuration ofNe, the configuration of Cu
can also be represented as
Cu 29 = [Ne]3s 2 , 3p6, 3d 10, 4s 1
9. Eating animal flesh poisoned with mercury (Hg2+) causes
deformity, which is known as minamata. It is characterised by
diarrhoea, hemolysis, impairment of various senses, meningitis
and death.
10. Electronic configurations of cuprous (Ctt) and cupric (Cu 2+)
ions are as follows.
Cu+= (Ar) 3d 1~ 4s 0
Cu 2+ = [Ar] 3d9 ,4s0
Thus, electronic configuration of Cu+ is more stable but it is less
stable because in Cu 2+ due to small size of Cu 2+, the nuclear
charge is sufficient to hold 27 electrons but in Cu+ such as
condition is not true. Further, the IInd IP of Cu is not very high as
compared to its Ist IP. Consequently a large amount of lattice
energy is released for cupric compotmds as compared to Cu+
compounds.
11. Catalytic activity of transition metals depends upon their ability
to shown variable (multiple) oxidation states and to form bonds
with the reactant molecules, however not on the strength of the
bonds formed further, increase in the concentration ofreactants at
the surface of the catalyst reduces the activity of catalyst.
12. Electronic configuration of the given elements are as follows.
24 Cr = (Ar) 3d5, 4s 1
29 Cu = (Ar) 3d 10, 4s 1
10 2 (iii) Vacant orbitals with suitable energy to accept lone pair of
30 Zn =[Ar]3d ,4s
25 Mn = (Ar) 3d5, 4s2
24 Cr = [Ar] 3d5, 4s 1
Cr 3+ = (Ar) 3d 3, 4s0 ⇒ 3 unpaired electrons
ion.
14. Mn 2+ is formed when 2e- are lost by M n atom. The atomic
number of Mn atom is 25. lts electronic configuration is
Mn(2S) = 1s2, 2s2, 2µ6, 3s2, 3µ6, 3d 5, 4s 2
But ls~ 2s2, 2µ6, 3s2, 3µ6 is the electronic configuration of Ar
[a noble gas]. Thus, the above electronic configuration ofMn can
be written as
Mn(2S) = (Ar) 3d5, 4s 2
[Here, [Ar]= noble gas electronic configuration of argon]
In the formation of Mn 2+ , 2e- are lost from 4s-orbital of Mn
atom, thus leaving behind only (Ar)3d 5. Hence, the grotmd state
electronic configuration ofMn 2+ ion would be [Ar] 3d5.
15. Most of the compounds of transition metals are coloured in solid
state or solution. This is due to their incomplete
(n -l)d-subshell. Their colour arises from the excitation of
electron from d-orbitals of lower energy to d-orbitals of higher
energy (i.e. d-d transition).
16. Paramagnetism is exhibited in species due to presence of one or
more tmpaired electrons which are attracted by the magnetic
field.
17. Ag(group 11 ), Au (group 11), Fe (group 8), Cu (group 11) and
Ti (group 4) belongs to d-block elements, so these are transition
metals.
18. d-block elements form complexes due to following factors.
(i) Very small size
(ii) High positive nuclear charge
electrons.
528 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2 25. (a) FeO > Fej)3 (basic) true.

19. (a) V + = 3 unpaired e lectrons
2
Cr + = 4 unpaired electrons (b) FeC12 > FeC1 3 (ionic), larger the charge, greater the
polarising power and thus greater the covalent nature. Thus,
Mn 2+ = 5 unpaired electrons
true.
Fe2+ = 4 un paired electrons (c) Fe2+ salts are more ionic thus less volatile than Fe3+ salts.
Hence, the order of paramagnetic behaviour should be Thus, true.
v2+ < Cr 2+ = Fe2+ < Mn 2+ (d) Greater the covalent nature, more easily they are hydrolysed.
Thus, FeCl 3 is more hydrolysed than FeCl 2.
(b) Ionic size decreases from left to right in the same period.
Thus, statement (d) is incorrect.
(c) (As per data from NCERT)
Co 3+ I Co2+ = 1.97; Fe3+ I Fe2+ = 0. 77; 26. Hydrated ferrous sulphate, FeSO4 · ?H p is known as green
Cr 3+ I Cu 2+ = - 0.4 1 vitriol.
3
Sc + is highly stable (it does not show +2).
27. Formula Name
(d) The oxidation states increases as we go from group 3 to group
7 in the same period. (a) ZnO Philosopher's wool
20. SRP value normally increases from left to right in the period of (b) ZnS + BaSO4 Lithopone
d-block elements. Some SRP values are exceptionally high due to (c) ZnSO4 · 7H2O White vitriol
stability of product ion, e.g.
(d) ZnO-CoO Rinmann's green
Eoc,3+1c,i+ = - 0.41 V
28. When copper is exposed to atmosphere, a green coating of basic
E\e3+/ Fe2+ = + 0.77 V
copper carbonate gets deposited over its surface. This is called
E oMn 3+/Mn 2+ = + 1.57 V corrosion of copper.
E oo,l+icoi+ = + 1.87 V
29. The Cu/+ ions contain cu+ ion. Cu+= [Ar]3d 10 .
Thus, E~3 + 1Mi+ is highest for Co.
The electronic configuration of eu+ ion is [Ar]3d 10 .
21. Transition e lements on account of their vari able (multiple)
valency have the ability to form intermediate compounds readily, Since, there is no unpaired electron, thus the salts containing this
thus acting as good catalysts. Hence, the catalytic activity of the ion is colourless. These salts are white in colour.
transition metals and their compounds is described to their ability 30. Silver iodide has similar crystal structure to ice. So, it is used for
to adopt multiple oxidation states and their ability to form producing artificial rain. The procedure is called 'cloud seeding'.
complexes.
31. Actual composition of chromite ore (FeCr2 O4 ) is FeO · Cr2O 3 . In
22. Transition element have three series 3d, 4d and Sd. 3d series has
FeO, the oxidation state ofFe is + 2 while in Crp3, the oxidation
element 2 1 (Sc) to 30 (Zn) atomic number. 4d series has element
state of Cr is +3.
39 (Y) to 48 (Cd) atomic number. Thus, [Kr]4d 1 -io, 5s 1 - 2 is the
2
general configuration of the Tlnd row series. 32. 26 Fe = [Ar]3d 5 ,4s2, Fe + = [Ar] 3d6
23. The aqueous solution of CuSO4 consist of the complex Number of unpaired electrons, n = 4
[Cu(H2O)4 ] 2+ ion which absorb radiation in orange-red region
µ =..jn (n + 2) =.J4(4 + 2) = 4.89 "' SBM
and impart deep blue colouration to solution.
Oxidation 2
33. Dichromate ion, Cr2O 7 - consists of two tetrahedral sharing one
+3 (-1) +2 comer w id1 Cr--0--Cr bond angle of 126°.
24. K3[Fe(CN)6l + KI ~ K4[Fe (CN)6] + Kl3
I (Excess) t (Brownish yellow
Reduction solution consisting
ofl 3ions)

KI3 is actually fonned between 12 and 1- ions thus, oxidation state

of one I is - I and for other two I-atoms it is taken as zero. Hence,
when KI changes to 13, it is considerd as oxidation reaction. Thus,
Thus, dichromate ion contains all six equivalent Cr--0 bonds
in the above reaction both oxidation and reduction takes place
with bond length of 163 pm and one Cr--0--Cr bond with bond
and hence, it is a redox reaction.
angle of 126°.
13 + 2Na 2SiO 3 ~ Na 2S4O6 + 2Nal + 12
Brownish Clear solution (Turns starch 34. Anhydrous Ferric chloride, FeCl3 is prepared by passing dry Cl 2
yellow into b lue)
filtrate gas over heated iron scrap.2Fe + 3Cl 2 ~ 2FeCl 3.
2KiFe(CNk;] + 3ZnSO4 ~ K 2Zn[Fe(CNk;] + 3K 2SO4 35. On acidifying, the yellow colour of K 2CrO 4 changes to
Whiteppt
The above formed white ppt is soluble in NaOH solution as orange-red due to the reformation ofK2Cr2O 7 .
2K2 CrO 4 + H 2SOc-~ K 2Crp 7 + K 2SO4 + H 2O
K 2Zn[Fe(CN};] ~ [Zn(OH)4 ]2- + [Fe(CN\; ] 4 + (Ye llow) Orange red

The above reaction suggests that the change in colour of solution
is due to the interconversion of monocentric complex into
dicentric complex.
Note This interconversion is due to the fact that in K 2Cr2O 7
solution, orange-red Cr2O7 2- ions are in equilibrium with
yellow Cro/- ions.
Crp/- + H 2O ~ Cro/- + 2H+
Orange red Yellow
On the addition of an acid, the above reaction proceeds in
the backward direction producing orange solution
containing Cr2O 7 2- ions.
36. The stability of Cu 2+ (aq) rather than Cu+ (aq) is due to much
The d-and f-Block Elements I 529
Since, paramagnetic character oc unpaired electrons.
Thus, Cu.SO4 · 5Hp has the lowest degree of paramagnetism
among the given at 298K as Cu 2+ion has least number of
unpaired electrons.
44. Gun metal has a composition of Cu = 88%, Sn = I 0%, Zn = 2%
45. Zinc sulphate hepta hydrate (ZnSO4 · 7H2O) is called white
vitriol. When it is heated with barium sulphide, it forms a white
pigment lithopone.
46. Transition metals can form ionic or covalent compounds and their
melting and boiling points are high. Their compounds are
generally coloured and they usually exhibit variable valency.

more negative LlhydH 0 ofCu 2+ (aq)than eu+, which compensates 47. Potassitun dichromate, on heating gives oxygen and chromic
oxide (Cr2O 3 ).
for 2nd ionisation enthalpy of Cu.
I!.
37. German silver alloy contains zinc, copper and nickel. 4K2Cr2O 7 ~ 4K2Cr04 + 302 + 2Cr2O 3
(X)
38. Usually across the first transition series, the negative values for
standard electrode potential decrease except for Mn due to stable 48. Mercurous chloride (calomel) is prepared by heating HgCl2 and
d 5 configuration. Hg in iron vessel.
I!.
So, correct order Mn > Cr > Fe> Co. HgCl 2 + Hg ~ Hg2Cl 2
39. Maximum oxidation state exhibited by d-block elements
It can also be prepared by the reduction of mercury (II) chloride
(OS)= number of ns-electrons + number of (n - I) d-electrons.
by tin (II) chloride in a limited quantity.
(a) OS= 2 + 2 = 4 (b) OS = 5 +I= 6 I!.
2HgCl 2 + SnCl 2 ~ Hg2Cl 2 + SnCl 4
(c) OS= 3 + 2 = 5 (d) OS = 5 + 2 = 7
2
: . (n -1) d 5 , ns configuration w ill ach ieve the highest oxidation 49. Steel is the most important commercial variety of iron having
state. percentage of carbon 0.25 -2 (between cast iron and wrought iron).
40. In basic medium, the following reaction takes place 50. Outer electronic configuration of
3d1
2KMnO4 + 2KOH ~ 2K2MnO4 + Hp + [OJ
Due to the presence of nascent oxygen [OJ, KMnO4 (in basic Co2+= I1~ I1~11 11 11 I(3 unpaired electrons paramagnetic)
medium) behaves like an strong oxidising agent.
3d8
41. The electronic configuration of Mn is

25 Mn = [Ar] 3d5, 4s2

Ni2+= 11~11~11~11 11 1(2 unpaired paramagnetic)
electrons thus

3d9
Mn 4 + = [Ar] 3d3 ( I unpaired electron thus
Thus, three u npaired electrons are present.
Cu2+= 11~ 11~11~11~11 I paramagnetic)
: .Spin only magnetic moment, µ = ,Jn (n + 2) 3c/10
n=3 Zn2+= 11~ 11~11~11~11~I (no unpaired electrons,
thus paramagnetic)
µ = ,j3 (3 + 2) = ✓IS= 3.87"' 4 BM
Thus, zinc ions have all paired electrons hence, it is diamagnetic.
42. FeSO4 ·(NH4 ) 2 SO 4 · 6H2 O is called Mohr's salt. 4
51. Given, X = [Ar] d
2
43. In MnSO4 · 4H2O, Mn is present as Mn +
·: The complete configuration of the ion,
5 0
3d 4s
X3+ = ls2 , 2s2 , 2/, 3s2 3/, 3d4
2
Mn + = 11I 1111111 I D (unpaired electrons= 5)
In CuSO 4 · 5H2O, Cu is present as Cu 2+
X = ts2, 2s2 , 2p6, 3s2, 3/, 3d5 4s2
: .The atomic number of the element is 25 and the element is Mn.
3d9 4s0
2
Cu + = I1~ I1~ I1~ I1~11 I D 2 (unpaired electron= I)
52. Transition element exhibit variable oxidation states because their
d-electrons also take part in bonding alongwith s-electrons.
In FeSO4 · 6Hp, Feis present as Fe + However, the difference between two oxidation states is not
3d 6
0
4s always two.
2
Fe + = I1~11 111111 I D (unpaired electrons= 4) Fusion
53. 2MnO2 + 4KOH + 02 ~ 2K2MnO4 + 2H2 0
In NiSO4 · 6Hp, Ni is present as Ni 2 +
Oxidation number of Mn in KiMnO 4 is
3d8 4s0
,2+ 2x(l) + x + 4(-2)=0
NI = 11~11~l t l1111 □ (u npaired electrons= 2)
x= + 6
530 I Chapterwise & Topicwise Engineering Entrances Solved Papers

54. As oxidation state increases, electronegativity increases thus 64. 2MnO4 + Br- + H 2 O - 2MnO 2 + Br03 + 2O~
acidic character increases not basic.
Hence, MnO 4 produces MnO 2 and BrO3 on reaction with
55. µ = ,Jn (n + 2) bromide ion in alkaline medium.
⇒ ..Jl5 =.Jn(n+ 2) 65. Ti, Zr and Hf belong to IV B group of periodic table and in a
group atomic radius increases on moving down. However, the
n=3 transition metals of 4d-series have nearly the same radius as that
56. Elements having electronegativity in the range of 1.35 -1.82 do of metals of 5d-series due to lanthanide contraction. Hence, the
not form stable hydride. T hus, leads to hydride gap. These are order of atomic radius is
present in the middle of the periodic table, i.e. belong to groups 7, Ti< Zr "' Hf
8 and 9. Due to nearly equal atomic radii, Zr and Hf are called chemical
57. Spin only magnetic moment, twins.
µ = .Jn (n+ 2) = ✓'24 66. Zn + 4HNO 3 - Zn(NO3)z + 2NO 2 + 2Hp
Cone. (X)
n2 + 2n- 24 = 0
4Zn + I 0HNO 3 - 4Zn (NO 3)z + NH 4N O 3 + 3Hp
(n+ 6)(11 -4)= 0 Dilute (Y)
2 9
n=4 [·: n = - 6notpossible] 67. In CuF2 , Cu + ion exist, having d configuration. Thus, it
Here, n is the number of unpaired electrons. contains one unpaired electron in their d-orbitals which causes
(d-transition) and hence, imparts colour to the compound. In the
The electronic configuration of the metal ion Mx + is
crystalline form, CuF2 is blue coloured.
Z (25) = 1s2, 2s2 , 2p6, 3s2, 3p6, 4s2, 3d5
While in rest of the compound, Cu exists as Cu+ ion with
Since, four unpaired electrons are present, the oxidation state d 10 electronic configuration having no unpaired electron w hich
must be +3. can cause d-d transition.
z3+ (25) = 1s2, 2s 2 , 2p6, 3s2 , 3/, 3d4 68. Natural radioactivity is not a characteristic of transition elements.
58. Stainless steel is an alloy of iron with chromium and nickel. Its General properties of transition elements are:
composition is 82% Fe and 18% Cr + Ni. It resists corrosion and (i) Formation of coloured salts
used for making automobile parts and utensils. (it) Formation of complex salts
59. Transition metals due to the presence of partially filled d-orbitals, (iii) Magnetic properties
are coloured. (iv) Formation of interstitial compounds
The unpaired electron present in partially fi lied d-orbital is (v) Formation of alloys etc.
excited to the higher energy d-orbital by absorbing energy from
visible light and thus exhibits the complementary colour to the 69. Magnetic moment ofZn 2+ is calculated as:
absorbed light. Due to which, the transition metal ions appear µeffective = ,Jn (n + 2) BM
coloured.
where, n = number oflmpaired electrons
60. Only those transition metal ions which contain unpaired electrons 2
30 Zn = ls , 2s22p6, 3s23p63d
10
,
2
4s
in their d-orbitals are coloured. Since, colour appears when the 2 2 10 10
unpaired d-electron absorb energy and gets excited to the higher Zn + = ls2, 2s 2p6, 3s23p63d , 3d
energy d-orbital. Hence, the reason of appearance of colour is
d-d transition.
11~ 11~11~11~11~I
n.=0
61. Mohr's salt is (NH4 ) 2 SO4 · FeSO4 · 6Hp. So, magnetic moment of Zn 2+ = zero.
Here, Fe is present as FeSO4. TI1erefore, its oxidation state can be
70. Silver nitrate is used in making hair dyes because, it reduces to
calculated with in only FeSO4.
metallic silver and finely divided silver is black in colour.
X + (-2) = 0
71. The oxides are generally amphoteric if the metal is in the
x=+2 intermediate oxidation state. The oxides of Mn have the
62. The reaction can be represented as: following behaviour:
I!.
K4 [Fe((:N\] + 6H2 SO4 + 6H2O - 2K2 SO4 Oxide MnO Mn 3O4 Mn2O3 MnO2 MnO3 Mn2O 7
O.S of +2 +8/3 +3 +4 +6 +7
+ FeSO 4 + 3(NH4 )iSO 4 + 6CO i Weakly Strongly
Mn
acidic acidic
Hence, the gas released in the above reaction is CO. Amphoteric

n ~~=~.~'~'~'~'~'~ Hence, the oxides of Mn, i.e. Mn 30 4 , MnO2 , Mn 2 O 3 are in their

intennediate oxidation state thus, these are amphoteric in
character.
: . Number of unpaired electrons in Mn are equal to 5.
72. V (23) = [Ar) 3d3 , 4s2
: . Magnetic moment of Mn is calculated as :
(two unpaired electrons)
Mn=-J,1 (n+ 2)= ✓5 (5 + 2)=-J35 = 5-91 BM
 The d-and f-Block Elements I 531
Cr(24) = (Ar) 3d5 ,4s 1 79. Most of the transition metal ions due to presence of unpaired
3 3 d-electrons are coloured.
Cr + = (Ar] 3d , 4s° (three unpaired electrons)
80. Magnetic moment = ,Jn (n + 2) BM
Co (27) = (Ar) 3d7, 4s2 where, n is the number of unpaired electrons. Maximum the value
Co2 + = [Ar]3d7, 4s0 (three unpaired electrons) of unpaired electron, greater the value of magnetic moment.

Sc(21) = (Ar) 3d ,4s 21 (2 unpaired electrons)

Sc3+ = (Ar] 3d0 , 4 s0 (no unpaired electron)

3d 5 = 11 1 1 1 1 11 I1 I (5 unpaired electrons)
3
Thus, in Sc + no unpaired d-electron is present.
Hence, no d-d transition is possible and thus, it is colourless ion. 3d 7 = 11 1 1 1 1 1 1 1 1 I (3 unpaired electrons )
73. The electronic configuration of mercury (Hg) (80) is,
(Xe] 4 / 0 , 5d 10 , 6s2. Tts d-subshell is completely filled, thus it 3d9 = 11~ 11~ 11~ [ 1~ [ 1 I (I unpaired electron)
prevents the overlapping of d-orbitals (d-d overlapping).
So, 3d5 has highest value of magnetic moment.
Hence, it is liquid metal at room temperature.
81. A transition metal ion existing in the highest oxidation state is
74. Silver nitrate decomposes to silver nitri te on heating above its expected to behave as an oxidising agent by undergoing
melting point (212°C). reduction and converting into lower oxidation state.
2120
Note 2AgNO 3 > c 2AgNO 2 + 0 2
82. When oxyhaemoglobin changes to deoxyhaemoglobin,
On heating above 450°C (red hot), silver nitrate decomposes Fe2+ ion changes from diamagnetic to paramagnetic.
to metallic silver, oxide of nitrogen and oxygen.
> 4500C 83. Value of magnetic moment depends upon number of unpaired
2AgNO 3 - -~ 2Ag + 2NO2 + 0 2 electrons. All except Ti 3+ ( 3d 1) have either fully filled
75. V and T. Co 3+ have higher charge density than Co2+, so Co3+ is d-subshell (i.e. Zn 2+, Cu+) or empty d-subshell (i.e. Sc3+). As
more stable in octahedral complexes.
such only Ti 3+ has a net value of magnetic moment.
TT. Zn exhibits only + 2 oxidation state. So,
Magnetic moment of
Zn 2+ = (Ar] 3d 10, 4s0
Ti 3+ = ,Jn (n + 2)BM = .Ji<t+T)BM = ✓3 = l.73BM
Since, it does not contain any unpaired electron, its 10
compounds are colourless. 84. Ag2SO4 contains Ag+ (4d ) and is colourless. CuF2 contains
2 9
Cu + (3d ) and is coloured due to the presence of one unpaired
ITT. d-block elements are generally paramagnetic and sometimes
diamagnetic, but not ferromagnetic. electron in d-orbital of Cu 2+. MgF contains Mg2+ and is
2
IV. Osmium and ruthenium are VITI group elements, so can colourless while CuCI contains Cu+ (3d 10)and is also colourless.
exhibit the highest oxidation state + 8 in their oxides, e.g.
Hence, CuF2 is expected to be coloured.
OsO 4•
Hence, statement T and TV are correct. 85. HgCl 2 compound is easily volatile. They are insoluble in water

76. Au is a member ofSd-series. Fe, Co and Cu all are the members of and soluble in acids.
3d-series. 86. The oxidation state of vanadium in VOSO 4 is + 4.
77. Organic compounds containing double(=) or triple(==) bond in V(Z = 23] = [Ar] 3d3 ,4s2
the side chain decolourise acidic/alkaline KMnO 4. Benzene does
not decolourise the acidic/alkaline KMnO4 , due to the V 4 + [Z = 23] = (Ar) 3d 1 ,4s0
delocalisation of1t-electrons. It has one unpaired electron hence, it is paramagnetic in nature.
While propene decolourises the alkaline KMnO4 due to the
presence of(=) double bond. Ferrous ammonium sulphate and Further, it can exhibit d-d-transition due to this unpaired electron.
oxalic acid decolourise the KMnO 4 in acidic medium. Thus, VOSO4 is paramagnetic as well as coloured compound.
2KMnO4 + I0FeSO4 + 8H 2SO 4 ----4 87. Corrosive sublimate gives black ppt. of calomel with formic acid
but it does not react with acetic acid.
K 2SO4 + 2MnSO4 + 5Fei(SO4) 3 + 8H2O
2HCOOH + 2HgCl2 ----4 Hg2Cl2 + CO2 + H 2O
2KMnO4 + SC2Hi04 + 3H2SO4 -
CH 3COOH + HgCl2 - No reaction
KiSO4 + 2MnSO4 + I0CO2 + 8H2 O
88. Cu, Ag, Au group of elements are called coinage metals as these
78. Maximum oxidation state of transition metals = number of are used in minting coins.
electrons in (11 - I) d -orbital + number of electrons in ns orbital.
The electronic configuration of 89. Cr=(ArJ l11 1[ 1[ 1 [ 1 1 IJJ
1 6 2 3ds 4s'
Os= [Xe] 4 / 4, 5d , 6s
: .Maximum oxidation state= 6 + 2 = 8
Cr+= [Ar] 11 1 1 [ 1 [ 1 [ 1 ID (highly stable electronic
: .The highest oxidation state exhibited by transition metal is + 8 3as 4so configuration)

e.g. OsO 4. (By first IP)

532 I Chapterwise & Topicwise Engineering Entrances Solved Papers

This is stable electronic configuration, due to the presence of 99. Cr2 + (Z = 24) [Ar] 3d4 4s0 (4 unpaired electrons)
exactly half-filled orbitals. Hence, formation of Cr 2+ by second 2
Fe + (Z = 26)[Ar] 3d 6 ,4s0 ; (4 unpaired electrons)
IP requires maximum enthalpy.
Ti 2+[z = 22][Ar ]3d2 ,4s0 (2 unpaired electrons)
90. Formation of coloured solution is possible when metal ion in the
compound contains unpaired electrons. e.g. v2+[ Z = 23] [ Ar ]3d3 ,4s 0
(3 unpaired electrons)
Cu+ = 3d 10 , 4s0 (colourless) 2
Cu +[z = 29][Ar]3d4,4s0 (I unpaired electron)
2 9 0
Cu + = 3d ,4s (blue) 2 7
and Co +[z = 27][Ar ]3d ,4s0 (7 unpaired electrons)
91. Magnetic moment = .J11 (n + 2) BM 2 2
As, Cr + and Fe + have same number of unpaired electrons,
where, n = number of unpaired e lectrons hence they have the same value of magnetic moment.
5.93 = .Jfl (n + 2) 100. Mone) metal or constantan is an alloy of Cu(30%), Ni(67%),
Fe(3%), Mn.
On solving, we get
101. Zn + 2NaOH ----t Na 2ZnO 2 + H 2
n=5
:. Zn liberates hydrogen w ith hot cone. alkali.
Thus, Mn 2+ ion (3d 5 ) has 5 unpaired electrons and magnetic
102. HgS is used in ayurvedic medicine as makardhwaja.
moment is 5.93 BM.
HgCl 2 is poisonous and its antidote is egg white.
92. Acidified potassium dichromate is oxidised to unstable blue
ZnSO4 is used in eye lotion.
coloured chromium peroxide, which is soluble in ether and
produces blue coloured solution. Hg2Cl 2 is used as purgative in medicine and in making standard
calomel electrode.
K2Cr2O1 + H2SO4 + 4H2O2 ----t
103. Gun metal is an alloy of Cu (88%) + Sn (10%) + Zn (2%).
2CrO 5 + K 2SO4 + 5Hz0
Blue colour 104. CuSO4 + 2KI ----t Cul2 + KzSO4
Note CrO 5 rapidly decomposes in aqueous solution into Cr 3+ 2Cttl2 ----t
and oxygen. Cuprous iodide
whiteppt.
93. If, excess ofKJ is added to an acidified solution ofCuSO4, I 2 is
105. Potassium permanganate is a powerful oxidising agent in neutral,
produced by the oxidation of I - which reduces Cu 2+ to Cul (or
alkaline or acidic solution because it liberates nascent oxygen.
Ct1zl2)- The aqueous solution ofKMnO4 can be decolourised by cp~-,
2CuSO4 + 4KI~ 2CuI ! [or Cu 212 ]+ 12 + 2K2SO 4 HSO3and SOi-, while COi- cannot decolourise aqueous KMnO 4
White ppt.
solution.
12 produced can be determined by titrating with hy po solution
2
(Na 2S2O 3 ) in which 12 is reduced into 1 and Na 2Sz03 is oxidised 106. Ni + = [Ar]3d8 I 1~ I 1~ I 1~ 11 I 1 I
into Na2Sp6 . Number of unpaired electrons= 2
12 + 2Na2SzO3 -----) 2Nal + Na 2S4O6 Hence, n _+_2_) = ✓
magnetic moment = .J_n_(_ 8 = 2.84
Hence, CuI2 is not formed in the given reactions.
107. Bronze is a mixture ofCt1 (75-90%) and Sn (10-25%).
94. ZnO is known as philosopher 's wool because it is very light,
108. AgBr, silver bromide is used in photography.
white, soft wooly powder.
95. Ferrous sulphate (FeSO 4 · 7H 2O) is known as green vitriol.
109. Magnetic moment,µ = .J11 (n + 2)
Cr 3+ (Z = 24) = 3d ,4s0 , µ = .J3 (3 + 2) = ✓15
3
96. The electronic configuration of Cu 2+ is
Fe + (Z = 26) = 3d 6 ,4s0,µ = .J4 (4 + 2) = ✓'24
2
Cu 2+ = [Ar] 3d9
Hence, it has one unpaired electron.
N i + (Z = 28): 3d8 ,4s0, µ = .J2 (2 + 2) = ✓8
2
Magnetic moment(µ) = .Jn (n + 2) = .,/TTI+2) = 1.73
Mn2+ (Z = 25): 3d5 ,4s0, µ = .J5 (5 + 2) = -/35
97. The complete reaction can be represented as:
11 O. Philosopher's wool on heating with BaO at 1100°C produce
2Cl 2 + HgO ----t Cl 2O + HgCl 2
Mercuric Mercuric BaZnO2•
oxide chloride
1100°C
BaO + ZnO Ba ZnO 2
98. 3.87 = .J fl (fl + 2), where, fl is the number of u npaired electron
111. Spin only magnetic moments depend upon the number of
(3.87)2 = fl (n + 2) unpaired electrons, more the number ofunpaired electron, greater
15=fl2 + 2n will be the spin only magnetic moment.
2
fl + 2fl - 15 = 0 25 Mn = ls2 , 2s2,2p6, 3s2,3p6,3d5 , 4 s 2
On solving we get, fl = 3
 The d-and f-Block Elements I 533
Mn 2+ = ls 2 , 2s 2, 2p6, 3s2, 3p6, 3d 5 , 4s0 So, 23 V=
2 3
ls , 2s2,2p6, 3s2, 3/, 3d , 4s2

11111 1111 11 y 4+ = is2 , 2s2,2p6, 3s2, 3p6,3d 1,4s0

Number of unpaired electrons= 5

24 Cr = ls2 , 2s2, 2p6, 3s2, 3p6,3d5 , 4s 1 Number of unpaired electron = I
2 0 2 10 1
Cr= is2, 2s ,2p6, 3s2, 3/, 3d4, 4s and 29 Cu = is2, 2s ,2/, 3s2, 3/, 3d , 4s

1111 1111 I Cu 2+ = ls2, 2s 2,2p6, 3s~ 3p6,3d9

Number of unpaired electrons= 4 11~11~ll l1~ 111

2 2 2 3 2
23 V = ls , 2s , 2p6, 3s , 3p6, 3d , 4s Number of unpaired electron = I
2
V + = ls2, 2s2, 2p6, 3s2, 3/, 3d , 4s
3 0 Hence, VOC1 2 and CuCl 2 show similar colour.
120. ZnCl2 is deliquescent.
121. Alloy is a homogeneous mixture of two or more metals. Mercury
Number of unpaired electrons= 3 forms amalgams (alloy) with gold, silver and tin. But it does not
So, the correct order of spin only magnetic moment is react with iron or platinum.
Mn 2+ > Cr2+ > v2+ 122. Many of the d-block (transition) elements and their compounds
act as catalyst. Catalytic property is probably due to the
112. Brass is an alloy of copper (60-80%) with zinc (20-40%).
utilisation of (n - 1) d-orbitals for the formation of interstitial
113. A white precipitate of cuprous iodide is formed on adding KI to compounds.
CuSO4 solution.
123. Magnetic moment depends upon number of unpaired electrons.
2CuSO 4 + 4KI ~ Cuzl2 + 2~SO4 + I2 In Sc3+, there is no unpaired electron. So, its effective magnetic
White ppt
moment is zero.
114. Mn exhibits the maximum number of oxidation states. 124. In alkaline medium
Mn (Z = 25) [Ar] 3d5 , 4s 2 In alka line solution, MnO4 ion (Mn= +7) is first reduced to
It can show +2, +3, +4, + 5, +6 and +7 oxidation states. Mno!- ion (Mn= +6) and then to insoluble MnO 2 (Mn= +4).
115. Transitional metal ions having electronic configuration (n - I) do
2 KMnO4 +2KOH~ 2K2MnO4 + H 2O + 0
or (n - I) d 10 are colourless while those have (n - I) d 1- 9 are (Mn = + 7) Green
Purple (Mn = + 6)
coloured.
Cu+ = [Ar] 3d 10 : (colourless) 2K 2MnO4 +2H2O ~ 2MnO2 + 4KOH + 30
Green Colourle~
2 9 (Mn - +6) (Mn ..+4)
Cu + = [Ar]3d : (coloured)
In acidic medium
Fe2+ = [Ar] 3d 6 : (coloured)
2
In acidic medium (dil. H 2SO4), MnO4 ion is reduced to Mn +
Mn 2+ = [Ar] 3d 5 : (coloured)
ion.
116. Aqueous silver nitrate solution is used as indelibleink. This
2KMnO 4 + 3H 2SO4 ~ K 2 SO4 + 2MnSO4 + 3Hz0+ 50
indelibleink is also called electron ink which stains the skin on (Mn=+7) (Mn =+2)
exposure to u ltraviolet light, leaving a mark that is impossible to
Thus, due to the release of nascent oxygen by KMnO4 in both the
wash off and is only removed as external cells are removed.
mediums, it acts as a strong oxidant. Hence, the products from
117. The ionisation energies increase w ith increasing atomic number. KMnO 4 in the two conditions are respectively MnO 2 and Mn 2+.
The trend is irregular among d-block elements due to stable
electronic arrangement. 125. Mohr's salt is FeSO4 · (NH4 )iSO 4 · 6H2O

Sc Ti V Cr Mn Fe Co N i Cu Zn
:.Tt is double salt having FeSO 4 and (NH4 )zSO4 •
Element
126. In basic medium potassimn permanganate is reduced to first
IE (kJ/mol- 1) 631 656 650 652 7 17 762 758 736 745 905
manganate and then to manganese dioxide (colourless).
:. Zn > Fe > Cu> Cr is correct order. 2KMnO4 + 2KOH ~ 2K2MnO4 + HzO + 0
118. Among the given oxides, only VzO 5 is amphoteric. While CuO, 2K2MnO4 + 2H 2O ~ 2MnO 2 + 4KOH + 20
V2O 3 and NiO are basic in nature. 2KMnO4 + HzO ~ 2MnO2 + 2KOH + 3[0]
119. Colour of transition metal ion salt is due to d-d transition of 127. Magnetic moment(µ) = .Jn (n + 2) BM where,' n' is the number
unpaired electrons of d-orbital. Metal ion salt having similar of unpaired electrons. As magnetic moment depends upon the
number of unpaired electrons ind-orbitals shows similar colour in number of unpaired electrons, thus, greater the number of
4 unpaired electrons, larger is their magnetic moment.
aqueous medium. In VOC1 2 , vanadium is present as V + and in
2
CuCl2 , copper is present as Cu +.
534 I Chapterwise & Topicwise Engineering Entrances Solved Papers
23 y2+ = [Ar] 3d3 (n = 3) 136. The elements hav ing incomplete d-orbital can show variable
4 oxidation state (because the electrons move within the two levels
2
24 Cr + = [Ar] 3d (n = 4) of d-orbitals itself)
2
25 Mn + = [Ar] 3d5 (n = S) ·: Zn has completely filled d-orbital, thus, it does not show
2
variable oxidation state. It always show + 2 oxidation state.
26Fe + = [Ar] 3d6 (n = 4)
Hence, magnetic moment will be maximum for Mn 2+(equal to Topic 2 Inner-Transition Element
5.92 BM) as it contains maximum number of unpaired
1. In order to attain maximum stability of half-filled orbitals,
electrons.
electrons shift from one orbital to another within the same
128. Annealing is the process of cooling a hot molten metal slowly. subshell. The energy released during the shifting of electrons is
Railway wagon axles are made by heating iron rods embedded in called exchange energy.
charcoal powder (annealing) so that these might not break due to The six unpaired electrons present in f-subshell can undergo IS
sudden change in temperature. exchanges which can be shown as:
129. Cast iron has the highest percentage of carbon. It contains
2 to 4.5% of carbon alongwith impurities such as sulphur, silicon,
phosphorus etc. It is the least pure form of iron.
130. CrO3 dissolves in aqueous NaOH to give sodium chromate, an
I illIUlliO I
5 exchanges for electron I 3 exchanges for electrons 3
oxo salt of Cr. ~ ~
CrO 3 + 2NaOH ~ Na 2CrO 4 [or Cro!- l + H 2O
Sodium chromate 4 exchanges for electrons 2 2 exchanges for electrons 4
131. Brass is an alloy of Cu and Zn.
Bronze is an alloy of Cu and Sn.
German silver is an alloy of Cu, Zn and Ni. I exchanges for electrons 5

Hence, Cu is the common metal in brass, bronze and German Thus, total number of exchanges = S + 4 + 3 + 2 + 1 = IS
silver.
2. As a resulting of lanthanide contraction (contraction in atomic
132. Ammonium dichromate on heating gives green coloured powder radius of 4f-series of elements because of imperfect shielding of
ofCr2O 3 . forbitals), the normal increase in size from Sc ➔ Y ➔ La
6 disappears after lanthanide and the pairs of elements like Zr-Hf,
2(NH4 ) 2 Crp 7 ~ 2(NH4 )iCrO4 + Crp 3 + 302
Chromic Nb-Ta have nearly same size.
oxide
3. The earlier members of lanthanoid series resemble calcium in
H20 their chemical properties, e.g. hydroxides of both of them are
133. HgCl2 + 2NH 4 OH - - - - t Hg + NH2HgCI + NH 4 Cl
Mercuric
ionic and basic.
amino chloride 4. The electronic configuration of the given elements are as follows.
: . HgC1 2 on reaction with NH4 OH forms mercuric amino chloride. 5
61 Pm = (Xe) 4 / , Sd0 , 6s2
134. Addition of KCN to CuSO4 solution first causes reduction and
then precipitates CuCN (cuprous cyanide). This reacts with 62 Sm = (Xe] 4 .f, Sd0 , 6s2
excess CN- forming to a soluble four coordination complex,
58 Ce = [Xe] 4 J2, Sd , 6s2
0
[Cu(CN)S- or K [Cu(CN)4 ]
Which is tetrahedral in shape. =(Xe) 4J7,Sd 1, 6s2
64 Gd
2CuSO4 + 4KCN - 2CuCN + (CN)2 + 2V2SO4 From the electronic configurations, it is clear that only Ce can
CuCN + 3KCN - K 3[Cu (CN)4 ] exhibit an oxidation state of +4 alongwith + 3 because in that state
135. The element having unpaired electron is paramagnetic. More the it achieves stable configuration ofnobel gas xenon.
munber of unpaired electrons, more will be paramagnetic 5. /-block series is divided into two series viz 4/ -series and
character. Sf-series. The members of 4/ series are called lanthanides or
Mn (25) = ls2, 2.s-2, 2/, 3s2, 3/,4s2, 3d5 whereas that of S/ -series are called actinides.
6. Lanthanides and actinides constin1te transition series within
: . 5 unpaired electrons transition series and their last electron occupies the
Fe (26) = Is2 , 2s2 , 2p6, 3s2 , 3p6, 4s2, 3d6 antipenultimate shell, so they are named as inner-transition
elements also.
: . 4 unpaired electrons
7. The electronic configuration of Gd (64) is :
Ni (28) = ls 2 , 2s2, 2p6, 3s2, 3p6, 4s2 , 3d8
[Xels4
: . 2 unpaired electrons
Cu (29) = Is2, 2s2, 2/, 3.s-2, 3/, 4s 1, 3d 10
11 111 1 11 111 1 11 1
6s2
1 unpaired electron
Mn has maximum and Cu has least paramagnetic property.
I I w

All the e lectrons of 4f-orbital are unpaired, hence stable.
Thus, Gd (64) has electronic configuration as
[Xe]s4 4 f 7 , 5d 1, 6s2
8 2
Instead of [Xe]s4 4f , 6s
8. (a) There is a gradual decrease in the radius of the lanthanoids
with increasing atomic number-a case of lanthanide
contraction. Thus true.
(b) Ionisation potential for the formation of Lu3+ is
comparatively low, hence +3 oxidation state is favourable.
Thus true.
(c) Due to lanthanide contraction - Zr and Hf, Nb and Ta, Mo
and W have the same size and thus similar properties and thus
separation is not easy. Thus trne.
(d) Formation of + 4 state requires very high energy, thus
incorrect.
9. The basic character of hydroxides decreases from La(OH)3 to
Lu(OHh Due to smaller size of Lu, the Lu- OH bond attains
more covalent character. Thus, the statement I is incorrect.
II. Due to lanthanide contraction, ionic radius of zr4+ and Hf4+
are nearly same. Thus, statement II is trne.
III. The maximum oxidation state of Ce is +4, it can be easily
converted (or reduce) into lower oxidation state. Thus, Ce4+ can
act as an oxidising agent.
10. The most common oxidation state of lanthanoid is + 3.
Lanthanoids in + 3 oxidation state usually have unpaired electron
in / - subshell and impart characteristic colour in solid as well as
in solution state due to f - f transition (except lanthanum and
lutetium).
11. Ceria or cerium oxide, CeO2, a lanthanide compound is used as a
pigment and as a polishing agent for glass.
1 14
12. Lanthanoids (Xe) 4 f - , Sd0- 1, 6s2
1 14
Actinides [Rn) 5 f - ,6d0- 1,7s 2
Lanthanoides and actinides use core d and !-orbitals to show
higher oxidation state. As actinoides have comparatively low
energy difference between f and d-orbitals, they show more
oxidation states.
13. Lanthanides and actinides both are not radioactive. Except
promethium, all lanthanides are non-radioactive. While all
actinides are radioactive.
14. Cerium Ce58 = (Xe)4/, 5d 1, 6s2
Its most stable oxidation state is + 3 but + 4 is also existing.
15. Ionic radius of lanthanide (La 3+) decreases with increase in
atomic number.
y 3+ < Lu 3+ < Eu 3+ < La 3+
The d-and f-Block Elements I 535
Because Eu and Lu are the members of lanthanide series (so they
show lanthanide contraction) and La is the representative
element. y 3+ ion has lower ionic radii as comparison to La 3+
because it lies immediately above in periodic table.
16. The general electronic configuration for lanthanides is
(Xe) (n - 2)f 1 - t
4
(n -1) d 1ns2.
·: After the loss of both of the 6s-electrons and also the solitary
d-electrons, the lanthanoides gain stable configurations.
:.(+ 3) oxidation state is most common among lanthanides.
17. Gadolinium (Z = 64) [Xe] 4 J 7 ,5d 1, 6s 2
Lutetium (Z= 71) (Xe) 4 j14,Sd 1, 6s 2
1
Lawrencium (Z= 103) [Rn] sj14,6d , 7s2
14
Tantalrnn (Z = 73) [Xe) 4 / 3
, 5d , 6s 2
Hence, gadolinium has got incompletely filled f-subshell.
18. Lanthanide contraction is due to the imperfect shielding of
f-electrons due to the diffused shape off-orbitals. Therefore, as
the atomic number increases effective nuclear charge increases
and this results in contraction of size of the 4 f-subshell.
19. 4 f and 5 !-belongs to different shell, experience different
amount ofshielding.
20. The actinoids (5 /-elements) exl1ibits more number of oxidation
states in general than the lanthanoid because 5/-orbitals extend
forther away from the nucleus than the 4 !-orbitals.
21. Lan than ides are the 14 elements of III B group and sixth period
(atomic number = 58 to 71) that are filling 4 f-subshell of
antipenultimate shell from 1 to 14. Actually, they are placed
below the periodic table in horizontal row as lanthanide series.
22. Lanthanide contraction, cancels almost exactly the normal size
increase on descending a group of transition elements, thus Nb
and Ta, Zr and Hf have same covalent and ionic radius
23. +3 and +4 states are shown by Ce in aqueous solution. Thus,
statement (c) is incorrect.
24. Boron (B), aluminium (Al) and gallium, (Ga) are present in III A
group. They show +3 oxidation state. While cerium (Ce) is a
lanthanoid. It is present in lanthanide series. It shows + 3 and + 4
oxidation states.
25. Lanthanoid contraction is due to ineffective shielding produced
by larger /-subshell.
26. The fourteen elements which follow actinium from thorium
(Z = 90) to lawrencium (Z = 103) are called actinoids. They
involve the filling of 5f-subshell. Californium (Cf) has the
atomic number 98 and its configuration is as
0
Cf (Z = 98) = [Rn] 5 f' , 6d 0 , 7s2
Hence, it is a member of actinide series.
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Coordination Compounds
QUICK REVIEW
• Coordination Compounds are those in which a central
metal atom or ion is attached with a fixed number of groups
or molecules (ligands) through coordinate bonds.
• Double Salts when dissolved in water clissociate almost
completely into ions in the same way in which the
individual components of the double salts do. It means in
aqueous solution, they give the test of all their constituent
ions.
• In complex compounds, the central metal atom or ion can
act as Lewis acid and ligands act as Lewis base. In complex
compounds central metal may exists in zero, positive or
even in low negative oxidation state.
• Chelating ligand is a neutral molecule, free raclical or ion
with two or more lone pairs ofelectrons on different atoms.
Formation of chelate rings always increases the stability of
a complex.
• 1t-acid ligand are capable of accepting an appreciable
amount of 1t-electron density from the metal atom into
empty 1t or 1t * orbital of their own.
Werner's theory of coorclination compounds
• According to Werner's theory of coordination compounds,
primary valencies correspond to the oxidation number of
metal atom or ion while secondary valencies correspond to
the coorclination number of metal atom or metal ion.
Primary valencies are ionisable while secondary valencies
are non ionisable.
IUPAC Nomenclature of Complex
Compounds
• The positive part of a coorclination compound is named
first and is followed by the name of negative part.
• The ligands are named first followed by the central metal.
The prefixes cli-, tri etc. are also used to inclicate number of
each kind of Iigand present.
• The oxidation state of central metal is indicated in roman
numbers in parantheses.
• If a complex species has negative charge, the name of the
central metal ends in -ate.
Isomerism
• Ionisation isomerism arises when complex compounds with
same molecular formula give clifferent ions in solution.
• Linkage isomerism arises when a complex contains a
monodentate ligand with more than one donor atoms.
• Coordination isomerism arises when there is exchange of
ligands between complex cation and complex anion.
• Hydrate isomerism arises when different number of water
molecules present in the coordination sphere.
• Geometrical isomerism arises when two identical ligands
occupy adjacent positions to each other (cis-isomer) or
placed opposite to each other (trans-isomer)
• Square planar complexes of the type MA 2 X 2 , MABX 2 ,
MA 2 XY and MABXY and octahedral complexes of the type
MA 4 X 2 , MA 3 X 3 show geometrical isomerism....:.._The
complex of the type M(AA hX2 (where, AA is
symmetrical bidentate ligand) also shows geometrical
isomerism.
• Tetrahedral complexes do not show geometrical isomerism
because the relative positions of unidentate ligands
attached with central metal atom are the same with respect
to each other.

• Geometrical isomerism is very common in complexes with
coordination number 4 and 6.
• In [Ma 3 b3 ] type octahedral coordination entity when three
same ligands are occupying adjacent position in the
polyhedra is known as facial (fac) isomer whereas when
three same ligands are occupying position around the
meridian of the octahedral, it is known as meridional (mer)
isomer.
• Compounds of type MA 2 X 2 Y2 , MA 2 X 2 Y2, MA 2 XY2L,
MABXY2L, M ( AA ) 3 , M ( AA ) 2 X 2 shows optical
isomerism.
• MA 2 X 2 Y 2 shows both geometrical and optical isomerism.
Valence Bond Theory (VET)
• According to valence bond theory (VBT), the metal atom
or ion under the influence of ligands can use (n - l)d,
ns, np, nd orbitals for hybridisation to yield square planar,
tetrahedral or octahedral geometry. These hybridised
orbitals then overlap with ligand orbitals which can donate
an electron pair for bonding.
• A complex compound may be inner orbital complex or
outer orbital complex depending upon whether d-orbitals
of th e inner shell or outer shell are involved in
hybridisation. Inner orbital complex is generally high
spin complex while outer orbital complex is generally
high spin complex.
• Under the influence of a strong ligand, the electrons can be
forced to pair up against the Hund's rule of maxinrnm
multiplicity.
Magnetic Properties of (Coordination compounds)
• [NiCl4 ] 2 - is paramagnetic while [Ni(CN)4 ]2- is
diamagnetic. It is due to the fact that c1- is a weak field
ligand, it cannot pair up 3d-electrons against Hund's rule
and Ni 2 + is sp 3 hybridised (tetrahedral shape) with two
unpaired electrons. While CN- is a strong field ligand,
causes pairing so, Ni2 + becomes dsp 2 hybridised (square
planar shape) with no unpaired electrons (diamagnetic).
• Structure of [Cu(NH3 ) 4 J2 + is an exceptional case. In this
complex one electron from 3d-subshell is promoted to
4 p -subshell. The repairing eight 3d-electrons pair up in
four 3d-orbitals followd by dsp 2 hybridisation. The
resulting complex is square planar with one unpaired
electron in 4 p-orbital. It is therefore, paramagnetic.
• Pt (11) and Au (111) always form square planar complexes
whether ligands are strong or weak.
• All octahedral complexes of Ni 2 + Cu + , Zn 2 + and Co 2 +
are outer orbital complexes.
Coordination Compounds I 537
Crystal Field Theory (CFT)
• The crystal field theory is based on the effect of different
crystal fields provided by the ligands on the degeneracy of
d-orbitals of central metal atom or ion. The conversion of
degenerate d-orbitals into different sets of orbitals having
different energies is known as crystal field splitting.
• The difference of energy between the two sets of
degenerate orbitals as a result of crystal field splitting is
known as Crystal Field Stabilisation Energy (CFSE),
denoted by 11 0 .
• Order of increasing field strength of ligands is as follows
1 <Br-< S ~ <Cl-< S 2- < F- <OH-< C2 0~- < H2 O
< NCS 2 - < EDTA 4 - < NH 3 <en "' so; - < bipy < Phen
NO 2< CH3< C6 H5< CN- < CO
• The given complex compound is paramagnetic if one or
more unpaired electrons are present in the d-subshell. If the
complex doesn't contain any unpaired electron, it is
diamagnetic.
• Magnetic moment, µ = .Jn(n + 2) BM
• When light of certain frequency falls on the complex, it
absorbs light from visible range for transition of electron
from lower to higher level. Colour of the compound is the
complementary colour of the absorbed light. This is known
as d-d transition.
• Some complexes likes Cro; - , Cr2 o; - , Mno; etc, have
d 0 configuration of metal ion but have intense colour. In
these cases, the colour is due to charge transfer and not due
to d-d transition.
Metal Carbonyls
• In organometallic compounds, carbon must be bonded to
metal direct!y. Zeise' s salt, ferrocene and dibenzene
chromium are some of the examples of n-complex
organometallic compounds. Trimethyl aluminium is an
example of a-bonded complex. Metal carbonyls such as
[Fe(CO)s ], [Ni(CO)4 ] have characteristics of both O' and 7t
complexes.
• Carbonyls containing metal and CO only are known as
homoleptic carbonyls. d-block metals form most stable
carbonyls.
Stability Constant
• The stability of coordination compounds is measured in
terms of stepwise stability (or formation) constant K or
overall stability constant (13). For a given reaction;
M + 4L ~ ML4
[ML4 ]
~4 = [M][L]4
538 I Chapterwise & Topicwise Engineering Entrances Solved Papers

The instability constant or the dissociation constant of coordination compounds is defined as the reciprocal of the fom1ation
constant.
• Ligands such as CO, NO+ and CN- which are capable of accepting an appreciable amount of electron density from the metal
atom into empty 7t or1t • orbital of their own are called 1t-acceptor or 1t-acid ligands. On the other hand, in case of ligands such as
oxo ions in which the ligands have filled 1t-orbitals and act as 1t donors, transfer of electron density take place from ligand to the
metal atom.

Topic 1
General Terms
2014
1. The octahedral complex of a metal ion M 3 + with four 2012
monodentate ligands Li ,Lz , L3 and L 4 absorb 8. The atomic number of cobalt is 27. The EAN of cobalt in
wavelengths in the region of red, green, yellow and blue, Na 3 [Co(N0 2 ) 4 Cl 2 ] is [KCETJ
respectively. The increasing order ofligand strength of the
four ligands is [JEE Mains] (a) 24 (b) 36
(c) 34 (d) 35
W~<½<Lz<li ~Li<~<½<~ 9. Which of the following is a negatively charged bidentate
(c) ½ < 0. < L4 < li (d) li < ½ < L4 < ½ ligand ? [KCETJ
2. The equation which is balanced and represents the correct
(a) Cyano (b) Ethylenediamine
product (s) is [JEE Mains]
(c) Acetato (d) Dimethylglyoxime
(a) Li 20+ 2KC1 ~ 2LiCl + K 20
2 10. Oxidation state of Fe in [Fe(H2 0)5 NO+ ]S04 is [OJEEJ
(b) [C0Cl(NH3 )st+ SH+ ~ Co ++ SNH! + c1-
(c) [Mg(H2 0)6 ] 2 + + (EDTA)4 - (a) 0 (b) I (c) 2 (d) 3
ExcessNaOH [Mg (EDTA)]2+ + 6H 0
2 2010
(d) CuS0 4 + 4KCN ~ K 2 [Cu(CN)4 ] + K 2S04 11. The correct structure of ethylenediaminetetraacetic acid
3. In which one of the pairs of ion given, there is an ion that (EDTA) is [ITT JEE]
forms a coordination compound with both aqueous sodium
hydroxide and ammonia and an other ion that forms a
HOOCCH~ /H COOH2
(a) N- CH= CH- N
coordination compound only with aqueous sodium
hydroxide ? [KCET] HOOCCH{ "t:H2 COOH
2 2
(a) Pb +, Cu + 2
(b) Zn +, Al +3 HOOC "'- / COOH
(b) N- CH 2 - CH 2 - N
(c)Cu 2+,zn 2+ (d)AI 3 +,Cu 2+
HOOC / "----cooH
4. The oxidation state and covalency of Al in
2 HOOCCH2"'- /CH2 COOH
[AlCI(H 2 0)5 ) +, respectively are [EAMCET]
(c) /N- CH 2 - CH2 - N""-
(a)+6,6 (b) + 3,6 (c)+2,6 (d)+3,3
HOOCCH2 CH2 COOH
5. What is the oxidation nun1ber of Pt in K[PtNH3Cl 5 ]?
(a) 0 (b) + I [lndraprastha]
(c) + 2 (d) + 4
6. EDTA can fom1 complex with how many number ofdonor
atoms ? [J&K CETJ
(a) One (b) Two (c) Six (d) Three

2013 12. A group of atoms can function as a ligand only when

7. EDTA 4 - is ethylenediarninetetraacetate ions. The total (a) it is a small molecule [Manipall
number of N-Co-0 bond angles in [Co(EDTA)r (b) it has an unshared electron pair
complex ion is [JEE Advanced] (c) it is a negatively charged ion
(a)8 (b)9 (c) 2 (d) 10 (d) it is a positively charged ion
 Coordination Compounds I 539
13. Which complex compound obeys 18-electron rule ? 2007
2
(a) [V(CO) 5 ] {b) [Fe(NH 3 ) 6 ] + [MP PET] 22. The effective atomic number of Cr (atomic number = 24)
(c) [Ni(CO)6 ] (d) [Mn(I-12 O)6 ] 2+ in [Cr(NH 3 ) 6 ]Cl 3 is [BITSATJ
(a) 35 (b) 27 (c) 33 (d) 36
2009 23. Which of the following is hexadentate ligand ?
14. The oxidation state of Fe in the brown ring complex (a) Ethylene diamine CVITEEEJ
[Fe(H 2 O) 5 NO]SO4 is [Manipal] (b) Ethylene diamine tetra acetic acid
(a) + 3 (b) 0 (c) + 2 (d) + 1 (c) 1, 10-phenanthroline
(d) Acety1acetonato
15. The name of the ring structure complex compound formed
between metal ion and polydentate ligand is [Guj CETJ 24. In the coordination compound, K 4 [Ni(CN)4 ], the
(a) simple complex oxidation state of nickel is [MPPET]
(b) chelate complex (a)- 1 (b)O (c) + l (d) + 2
(c) polynuclear complex 25. The number of unidentate ligands in the complex ion is
(d) None of the above called [KCETJ
2008 (a) oxidation number (b) primary valency
(c) coordination number (d) EAN
16. Which of the following system is most stable for a chelate?
26. The oxidation state of iron in K 4 [Fe(CN)6 ] is CKCETJ
(a) Two fused cyclic system [MP PET]
(b) Three fused cyclic system (a) 1 (b) 4 (c) 3 (d) 2
(c) Four fused cyclic system 27. Which complex cannot ionise in solution? CKCETJ
(d) Five fused cyclic system
(a) [CoCl 3 (NH 3 h]
17. The oxidation state and effective atomic number (EAN) of (b) K 4 [Fe(CN) 6 ]
2
cobalt [CoF6 ] - respectively, are [MP PET] (c) K 2 [Pt(F6 )]
(a) 3 and 36 (b) 4 and 35 (d) [Pt(NH 3 ) 6 ] Cl 4
(c) 4 and 37 (d) 2 and 35 28. The oxidation number of platinum in [Pt(NH 3 ) 5 Cl]Cl 3 is
18. A complex compound in which the oxidation number of a [OJEEJ
metal is zero, is [KCET] (a) 2 (b) 3 (c) 4 (d) 6
(a) K 4 [Fe(CN) 6 ] (b) K 3 [Fe(CN)6 ] 29. What is the EAN of nickel in Ni(CO) 4 ? [AMUJ
(c) [Ni(CO) 4 ] (d) [Pt(NH 3 ) 4 ]Cl 2
(a) 38 (b) 30 (c) 36 (d) 32
19. A ligand can also be regarded as [KCET]
30. The tetrahedral complexes have coordination nun1ber
(a) Lewis acid (b) Bronsted base
[J&K CET]
(c) Lewis base (d) Bronsted acid
20. The primary and secondary valencies of chromium in the W3 ~6 ~4 ws
complex ion, dichlorodioxalatochromium (III), 31. The coordination number of a central metal atom in a
respectively are [Ke rala CEE] complex is determined by [Jamia Millia Islamial
(a)3,4 (b)4,3 (c)3,6 (a) the number of ligands around a metal ion bonded by
(d)6, 3 (e)4,4 CJ-bonds
(b) the number of ligands around a metal ion bonded by
21. Two isomers X and Y with the formula Cr(H2 O) 5 C1Br2 1t-bonds
were taken for experiment on depression in freezing point. (c) the number of ligands around a metal ion bonded by
It was found that one mole of X gave depression CJ- and 1t-bonds both
corresponding to 2 moles of particles and one mole of Y (d) the number of only anionic ligands bonded to the
gave depression due to 3 moles of particles. The structural metal ion
formula of X and Y respectively, are [Ke rala CEE]
(a) [Cr(H 2 O) 5 Cl]Br2 ; [Cr(H2 O)4 Br2 ]Cl· H 2 0
2006
(b) [Cr(H 2 O)s Cl]Br2 ; [Cr(H2 Oh C1Br2 · 2H 2 OJ 32. How many EDTA (ethylenediaminetetraacetic acid)
molecules are required to make an octahedral complex
(c) [Cr(H2 O) 5 Br]BrCl; [Cr(H 2 O) 4 C1Br]Br- H 2 O
with a Ca 2+ ion ? [AIEEEJ
(d) [Cr(H 2 O)s Cl]Br2 ; [Cr(H 2 0)4 ClBr]Br· H 2 0
(a) six (b) three
(e) [Cr(H 2 0) 4 Br2 ]ClH2 O; [Cr(H 2 0)5 Cl]Br2
(c) one (d) two
540 I Chapterwise & Topicwise Engineering Entrances Solved Papers
33. [Pt(NH 3 ) 6 ]Cl 4 complex gives [MPPET] 40. The coordination number and oxidation number ofX in the
(a) 4 ions (b) 3 ions following compound [X(SO4 )(NH 3 ) 5 ]Cl will be
(c) 2 ions (d) 5 ions (a) 10 and 3 (b) 2 and 6 [Manipal]
( c) 6 and 3 ( d) 6 and 4
34. The coordination number ofCu in [Cu(H 2 O) 4 ] 2+ complex
41. Which compound is zero valent metal complex? [KCETJ
is [MP PET]
(a) [Cu(NH3 ) 4 ]SO4 (b) [Pt(NH3 h Cl 2 ]
( a) 2 (b) l (c) 3 ( d) 4
(c) [Ni(CO)4 ] (d) K 3 [Fe(CN) 6 ]
35. The metal ion in complex A has EAN identical to the
42. The compound having the lowest oxidation state of iron is
atomic number of krypton. A is
(atomic number of Cr = 24, Fe= 26, Pd = 46) [J&KCET] (a) K 4Fe(CN)6 (b) K 2FeO4 [UPSEE]
(a) [Pd(NH 3 ) 6 ]Cl 4 (b) [Cr(NH 3 ) 5 Cl]SO4 (c) Fe 2O 3 (d) Fe(CO)s
(c) Na 4 [Fe(CN)6 ] (d) K 3 [Fe(CN)6 ] 43. A complex compound of Co 3+ with molecular formula
36. The complex that doesn't give a precipitate with AgNO 3 CoClx · yNH 3 gives a total of 3 ions when dissolved in
solution [J&K CET] water. How many Cl- ions satisfy both primary and
secondary valencies in this complex? [EAMCETJ
(a)[Co(NH 3 h Cl 3 ] (b)[Co(NH 3 ) 6 ]Cl 3
(c) [Ag(NH 3 )z ]Cl (d) [Cr(NH 3 ) 4 CI 2 ]Cl (a) 3 (b) l (c) 4 (d) zero
37. The number of moles of ions given on complete ionisation 44. Pick out the complex compound in which the central metal
ofone mole of[Co(NH3 ) 6 ]Cl 3 is/are [J&K CET] atom obeys EAN m le strictly. [Guj CETJ

(a)4 (b)3 (c)2 (d)l (a) K 4 [Fe(CN) 6 ] (b) K 3 [Fe(CN) 6 ]

38. The coordination number in a/an .......... complex may (c)[Cr(H 2 O) 6 ]Cl 3 (d)[Cu(NH 3 ) 4 ] SO4
increase to 8. [J&K CET] 45. Ethylene diarnine is an example of [J&K CETJ
(a) cobalt (b) osmium (c) nickel (d) iron (a) monodentate ligand (b) bidentate ligand
( c) tridentate ligand ( d) polydentate ligand
2005
46. The oxidation number of cobalt in K[Co(CO)4 ] is
39. The oxidation state of Cr in [Cr(NH3 ) 4 Cl 2 t is
(a) 0 (b) + l [AIEEE] (a)+ l (b) + 3 [J&K CET]
(c) + 2 (d) + 3 (c) - 1 (d) - 3

Topic 2
Nomenclature and Isomerism
2014 Codes
1. Match each coordination compound in Column I with an P Q R S p Q R s
appropriate pair of characteristics from Column IT and (a) 4 2 3 l (b) 3 l 4 2
select the correct answer using the code given below the (c) 2 I 3 4 (d) I 3 4 2
columns. (en = H 2NCH 2CH 2N H 2 ; atomic numbers : 2. Which of the following will not fom1 optical isomers ?
Ti = 22; Cr= 24; Co= 27; Pt = 78) [JEE Advanced] 3
(a)[Co(enh ] + [BITSATJ
Column I Column II (b) [Co(NH 3 h (NO 2 h]
(c) [Pt(en) 2 C l 2 ] 2 +
P. [Cr(NH3) 4 Cl 2 ] Cl I. Paramagnetic and
exhibits ionisation (d) [CrC12 (ox)i ] 3 -
isomerism
3. The IUPAC nan1e of the complex ion formed when gold
Q. [Ti(H 2O)sCl](NO 3) 2 2. Diamagnetic and exhibits dissolves in aqua-regia is [Karnataka CETJ
cis-trans isomerism (a) tetrachloridoaurate (III) (b) tetrachloridoaurate (I)
R. [Pt( en)(NH:i)Cl ]NO3 3. Paramagnetic and ( c) tetrachloridoaurate (II) ( d) dichloridoaurate (III)
exhibits cis-trans 4. In which year, IUPAC draft recommends that anionic
isomerism
ligands will end with iodo so that chloro would become
S. [ Co(NH3) 4 (NO 3)i ]NO3 4. Diamagnetic and exhibits chiorido? [J&K CET]
ionisation isomerism
(a) 1994 (b) 1984 (c) 2000 (d) 2004
 Coordination Compounds I 541
5. According to IUPAC system, what is the correct name of 2011
the compound [Cr(NH 3 h (H 2 O)3 Cl 3 l [J&K CET] 14. The volume (in mL) of 0.1 M AgNO 3 required for
(a) Ttriamminetriaquachromium (III) chloride complete precipitation of chloride ions present in 30 mL of
(b) Triamminetriaquachromiumchloride (III) O.Ql M solution of[Cr(H2 O) 5 Cl] Cl 2 , as silver chloride
(c) Tetraammoniumtriaquachromium (III) chloride is close to [ITT JEE]
(d) None of the above
(a)3 (b)4 (c)5 (d)6
2013 15. Which one of the following complex ions has geometrical
6. The pair(s) of coordination complexes/ions exhibiting the isomers ? [AIEEEJ
same kind of isomerism is (are) [JEE Advanced] (a) [Co(enh ] 3+ (b) [Ni(NH 3 ) 5 Brt
(a) [Cr(NH 3 )s Cl] Cl 2 and [Cr(NH 3 ) 4 Cl 2 ]Cl (c)[Co (NH 3 ) 2 (enh ] 3+ (d)[Cr(NH3 ) 4 ( en)] 3+
t
(b) [Co(NH 3 ) 4 Cl 2 and [Pt(NH 3 h (H 2 O)Clt
16. The lUPAC name of the complex [Co(NH 3 ) 4 Cl 2 ]Cl is
(c) [CoBr2 Cl 2 ]2 - and [PtBr2 Cl 2 ]2-
(a) dichlorotetraamminecobalt (III) chloride [KCETJ
(d) [Pt(NH 3 h (NO3 )] Cl and [Pt(NH 3 ) 3 Cl] Br
(b) tetraamminedichlorocobalt (III) chloride
7. Which of the following complex species is not expected to (c) tetraamminedichlorocobalt (II) chloride
exhibit optical isomerism ? [JEE Mains] (d) tetraamminedichlorocobalt (IV) chloride
3
(a) [Co(enh ] + t
(b) [Co(en) 2 C l 2 17. Excess of silver nitrate solution is added to 100 mL of
(c) [Co(NH3 ) 3 Cl 3 ] (d) [Co(en)(NH3 )Cl2 t 0.01 M pentaaquachlorochromium (III) chloride solution.
The mass of silver chloride obtained in grams is
8. One mole of the complex compound Co(NH3 ) 5 Cl 3 gives (atomic mass of silver is 108). CKCETJ
3 moles of ions on dissolution in water. One mole of the
(a) 287 x 10- 3 (b) 143.5 x 10- 3
same complex reacts with two moles of AgNO 3 solution to
yield two moles of AgCl. The structure of the complex is (c) l43.5x10- 2 (d)287x10- 2
(a)[Co(NH 3 ) 4 Cl]Cl 2 • NH 3 [Manipall 18. Ammonia gas does not evolve from the complex
(b) [Co(NH 3 ) 4 Cl 2 ]Cl· NH 3 FeCI 3 · 4NH 3 but is gives white precipitate with aqueous
(c) [Co(NH3 ) 3 Cl 3 } 2NH 3 solution of AgNO3 . Coordination number of central metal
(d) [Co(NH 3 ) 5 Cl]Cl 2 ion in above complex is six. Give lUPAC name of the
9. lUPAC name ofK 3 Fe(CN)6 is [KCET] complex. [Guj CETJ

(a) potassium ferricyanide (a) ammoniumtrichlorotriammineferrum (III)

(b) hexacyano ferrate (III) (b) tetraammineroferrum (III) chloride
(c) potassium hexacyano ferrate (III) (c) dichlorotetraammineferrate (II) chloride
(d) potassium hexacyano ferrate (II) (d) dichlorotetraammineferrum (III) chloride
10. The pair of [PtCl 2 (NH 3 ) 4 ] Br2 and [PtBr2 (NH3 ) 4 ]Cl 2 2010
constitutes a pair of CKCEEJ 19. The ionisation isomerof[Cr(H 2O) 4 Cl(NO 2 )] a is
(a) coordination isomers (b) linkage isomers (a) [Cr(H 2 O)4 (02N)] Cl 2 [ITT JEE]
(c) ionisation isomers (d) optical isomers
(b) [Cr(H2 O) 4 Cl 2 ](NO2)
11. The existence of two different coloured complexes of (c) [Cr(H 2O)4 Cl(ONO)] Cl
t
[Co(NH 3 ) 4 Cl 2 is due to [OJEEJ (d) [Cr(H 2O) 4 C l 2 (NO 2 )]· H 2O
(a) ionisation isomerism (b) coordination isomerism 20. Total number of geometrical isomers for the complex
(c) linkage isomerism (d) geometrical isomerism [RhCl(CO)(PPh 3 )(NH2 )] is [IlTJEE]
(a) 1 (b) 2 (c) 3 (d) 4
2012
21. A solution containing 2.675 g of CoC1 3 · 6NH3 (molar
12. Which among the following will be named as 1
mass = 267.5 g mol - ) is passed through a cation
dibromidobis (ethylenediamine) chromium (III) bromide ?
exchanger. The chloride ions obtained in solution were
(a) [Cr(en)3 ] Br3 (b) [Cr(enh Br2 ]Br [AIEEEJ treated with excess of AgNO 3 to give 4.78 g of AgCl
(c)[Cr(en)Br4 r (d)[Cr(en)Br2 ]Br (molar mass = 143.5 g mo1 - 1) . The formula of the
13. Which of the following is correct lUPAC name for complex is (Atomic mass of Ag= 108 u) [AIEEEJ
K 2 [Cr(CN)2 0 2 (Oh NH 3 ]? CBITSATJ (a) [Co(NH 3 ) 6 ]Cl 3
(a) Potassium amrninecyanoperoxodioxochromatic (III) (b) [CoC12 (NHh ] 4 Cl
(b) Potassium amminecyanoperoxodioxochromium (II) (c)[CoC13 (NH 3 h ]
(c) Potassium amrninecyanoperoxodioxochromium (VI)
(d) [CoCl(NH 3 )s ]Cl2
(d) Potassium amminedicyanodioxoperoxochromate (VI)
542 I Chapterwise & Topicwise Engineering Entrances Solved Papers
22. Which one of the following has an optical isomer ? 31. For the given complex [CoCl 2 ( en)(NH 3 )z t ,the number
(en= ethylenediamine) [AIEEE] of geomettical isomers, the number of optical isomers and
3 total number of isomers ofall type possible respectively are
(a) [Zn(en)(NH 3 ) 2 ]2+ (b) [Co(enh ] +
(a) 2, 2 and 4 (b) 2, 1 and 3 [DCE]
(c) [Co(H O) ( en)] 3+
2 4 (d) [Zn(en)z ]2+
( c) 2, 0 and 2 ( d) 0, 2 and 2
4
23. Both Co 3 + and Pt + have a coordination number of six.
32. For square planar complex of platinum (II),
Which of the following pairs of complexes will show
[Pt(NH 3 )(Br)(Cl)Py ] z+, how many isomeric forms are
approximately the same electrical conductance for their
0.001 M aqueous solutions? [Manipal] possible ? [DCE]

(a) CoC1 2 -4NH 3 and PtC1 4 -4NH 3 (a) Two (b) Three (c) Four (d) Six

(b) CoC1 3 · 3NH3 and PtC1 4 · 5NH3 2008

(c) CoC13 · 6NH 3 and PtC1 4 -5NH3
(d) CoC1 3 · 6NH 3 and PtC1 4 · 3NH3
24. The IUPAC name ofK 2 [Ni(CN) 4 ] is
(a) potassium tetracyanonickelate (II)
(b) potassium tetracyanatonickelate {III)
(c) potassium tetracyanatonickel (II)
(d) potassium tetracyanonickel (III)
25. Which of the following can part:J.c1pate in linkage
isomerism? [Punjab CET]
(a) NH 3
(c) H 2 N CH2 CH 2 NH2
26. Which of the following 0.1 M complex compound
solutions will have the minimum electrical conductivity?
(a) Hexammineplatinum (IV) chloride [Guj CET]
(b) Chloropentaammineplatinum (IV) chloride
(c) Dichlorotetrammineplatinum (IV) chloride
( d) Trichlorotriarnmineplatinum (IV) chloride
2009
27. The number of water molecule(s) directly bonded to the
metal centre in CuSO4 · 5H2 0 is [IIT JEE]
(a) 1 (b) 2 (c) 3 (d) 4
28. Which of the following has on optical isomer ? [AIEEE]
(a) [Co(NH 3 h cit
(b) [Co(en)(NH3 ) 2 ] 2+
(c) [Co(H O) (en)] 3+
2 4
( d) [Co(en)z (NH 3 )z ] 3+
29. Which of the following pairs represents linkage isomers ?
[AIEEE]
(a)[Cu(NH 3 ) 4 ][PtC1 4 ] and [Pt(NH 3 )4 ][CuCl 4 ]
(b) [Pd(PPh 3 )z (NCS)z ] and [Pd(PPh 3 )z (SCN)z ]
(c) [Co(NH 3 )s ]NO3 SO 4 and [Co(NH 3 )s SO4 ]NO3
(d) [PtC1 2 (NH 3 ) 4 ]Br2 and [PtBr2 (NH3 ) 4 ]Cl 2
33. The IUPAC nameof[Ni(NH3 ) 4 ][NiCl 4 ] is [IITJEEJ
(a) tetrachloronickel (II) - tetraamminenickel (II)
[KCET] (b) tetraamminenickel (II) - tetrachloronickel (II)
(c) tetraamminenickel (II) - tetrachloronickelate (II)
( d) tetrachloronickel (II) - tetraammine nickelate (0)
34. [Co(NH3 ) 5 SO4 ]Br and [Co(NH3 ) 5 Br]SO4 are a pair of
.......... isomers. [BITSAT, AMU, EAMCET]
(a) ionisation (b) ligand
( c) coordination ( d) hydrate
35. The IUPAC name of the given compound
[Co(NH3 )5 Cl]Cl2 is [VITEEEl
(a) pentaarninocobaltchloridechlorate
(b) cobaltpentaamminechlorochloride
( c) pentarnmine chloro cobalt (III) chloride
( d) penta amino cobalt (III) chlorate
36. For the square planar complex [Mabcd]
(where, M = central metal and a, b, c and d are
monodentate ligands), the number of possible geometrical
isomers are [Manipall
(a) 1 (b) 2 (c) 3 (d) 4
37. The IUPAC name of[Co(NH3 ) 6 ] [Cr(C2O 4 h] is
[MPPET]
(a) hexaaminecobalt (III) tris (oxalato) chromium
(b) hexaaminecobalt (III) tris ( oxalato) chromate (III)
( c) hexaaminecobalt tris ( oxalato)chromium (III)
( d) hexaaminecobalt (III) chromium (III) oxalate
38. TheIUPACnameofK 4 [Ni(CN) 4 ]is [MPPET]
(a) tetrapotassium tetracyanonickelate (II)
(b) potassium tetracyanonickel (II)
(c) potassium tetracyanonickelate (0)
( d) potassium tetracyanonickelate (II)
39. Which of the following can exhibit geometrical isomerism?
(a)[MnBr4 ]2- (b)[Pt(NH3 ) 3 Clt [OJEEJ
(c) [PtC1 2 · P(C2 H 5 ) 3lz (d) [Fe(H2 O)s NO] +
2

30. The IUPAC name of[Co(NH 3 ) 5 ONO] 2+ ion is

40. Fae-mer isomerism is associated with which one of the
(a) pentaamminenitritocobalt (IV) ion [Manipal] following complexes? [M =central metal] [Guj CETJ
(b) pentaamminenitrocobalt (II) ion
( c) pentaamminenitritocobalt (III) ion (a)[M(AA ) 2 ] (b)[MA 3 B 3 ]
(d) pentaamminenitrocobalt (V) ion (c)[M(AA ) 3 ] (d)[MABCD]
 Coordination C ompounds I 543
41. The number of ions fonned when hexaminecopper (II) 50. Benzoylacetonato beryllium exhibit isomerism of the
sulphate is dissolved in water is [J&K CET] type [J&K CET]
(a) 1 (b) 2 (c) 4 (d) 6 (a) structural
(b) geometrical
2007 (c) optical
42. TheIUPAC nameof[Ni(PPh 3 )z Cl 2 ] 2+ is [VITEEEJ ( d) conformational
a
(a) bisdichloro(triphenylphosphine)nickel (II)
(b) dichlorobis(triphenylphosphine)nickel (II)
a(l)b
( c) dichlorotriphenylphosphinenickel(II) 51. Octahedral complex a~J~b is [DCEJ
( d) triphenylphosphinenickel (II) dichloride b
(a) cis (b) trans (c) mer (d)fac
43. Which of the following coordination compounds would
exhibit optical isomerism ? [Manipall
52. Type of isomerism shown by [Cr(NH 3 ) 5 NO 2 ]Cl 2 is

(a) Pentaamminenitrocobalt (ill) iodide (a) optical (b) ionisation [DCEJ

(b) Diamminedinitroplatinum (II) ( c) geometrical ( d) linkage
( c) Trans-dicyanobis ( ethy lenediamine)
(d) Trans-(ethylenediamine) cobalt (III) bromide 2006
44. IUPAC nameofNa 3 [Co(NO2 ) 6 ] is [KCET] 53. The IUPAC name for the complex
(a) sodium hexanitrito cobaltate (II) [Co(NO2)(NH 3 ) 5 ]Cl 2 is [AIEEEJ
(b) sodium hexanitro cobaltate (III) (a) nitrito-N-pentamn1inecobalt (III) chloride
(c) sodium hexanitrito cobaltate (III) (b) nitrito-N-pentamminecobalt (II) chloride
( d) sodium cobaltinitrite (II) (c) pentaamminenitrito-N-cobalt (II) chloride
45. Which one of the following octahedral complexes will not (d) pentaamminenitrito-N-cobalt (III) chloride
show geometrical isomerism? (A and Bare monodentate
54. The IUPAC name of K 2 [PtCl 6 ] is [UPSEEJ
ligands) [UPSEE]
(a) hexachloroplatinate potassium
(a) [MA 4 B 2 ] {b) [MA 5 B]
(b) potassium hexachloroplatinate (IV)
(c)[.MA 2 B 4 ] (d)[MA 3 B 3 ]
( c) potassium hexachloroplatinate
46. According to IUPAC nomenclature sodium nitroprusside ( d) potassium hexachloroplatinum (IV)
is named as [UPSEEJ
55. What istheIUPAC nameofNa 2 [Fe(CN) 5 NO]? [OJEEJ
(a) sodiumpentacyanonitrosylfe1Tate (JI)
(a) Pentacyanonitroso sodium ferrate
(b) sodiumpentacyanonitrosylferrate (III) (b) Pentacyanonitroso sodium ferrate {II)
( c) sodiumnitroferricyanide
( c) Sodium pentacyanonitroso ferrate (II)
( d) sodiumnitrofe1Tocyanide ( d) Sodium pentacyanonitroso ferrate
47. The IUPAC name of compound K 3 [Fe(CN)5 NO] is
(a) pentacyano nitrosyl potassium ferrate (II) [OJEEJ 2005
(b) potassium cyano pentanitrosyl ferrate (II) 56. Which kind of isomerism is exhibited by octahedral
(c) potassium pentacyanonitrosyl ferrate (III) Co(NH 3 ) 4 Br2 Cl? [IITJEEJ
( d) potassium pentacyanonitrosyI ferrate (II) (a) Geometrical and ionisation
48. Give name of the complex, name should specify the (b) Geometrical and optical
position of ligands. [AMU] ( c) Optical and ionisation
PH --------- CO (d) Geometrical only
:3""' / :
, Ir ' 57. Which of the following compounds shows optical
CIL/_______
"" : PH3
isomerism? [AIEEE]

(a) bistransphosphinecarbonylchloroiridium [II]

(a) [Co(CN) 6 J3- (b)[Cr(C2 O 4 )J ] 3-
(b) carbonylchlorobistransphosphineiridium [III] (c) [ZnC14 ]2- (d) [Cu(NH 3 ) 4 ] 2+
( c) carbonylchlorobistransphosphineiridium [I]
58. Which is not true of the coordination compound
( d) chlorocarbonylbistransphosphineiridium [I]
[Co(en)i Cl 2 ]Cl ? [Ke rala CEEJ
49. Which one amongst the following, exhibit geometrical (a) Exhibits geometrical isomerism
isomerism ? [J&K CET] (b) Exhibits optical isomerism
(a) [Co 111 (NH 3 ) 5 Br]SO4 {b) Co 111 [EDTA] 1- ( c) Exhibits ionisation isomerism
(c) [Cr 111 (SCN) 6 ] 3- (d) [Pt rr (NH 3 ) 2 Cl 2 ] (d) Is an octahedral complex
(e) Is a cationic complex
544 I Chapterwise & Topicwise Engineering Entrances Solved Papers

59. The coordination compounds, (a) linkage isomerism

3 (b) geometrical isomerism
[Co(NH3 ) 6 ]3+ [Cr(CN) 6 ] -
(c) optical isomerism
and [Cr(NH 3 ) 6 ] 3 +[Co(CN) 6 ] 3- are the examples of (d) None of the above
(a) linkage isomerism [AMU] 61. TheillPACnameofthecompound[CuCl 2 (CH 3 NH 2 h] is
(b) coordination isomerism
(a) dichloro bis (dimethylamine) copper (II) [DCE]]
(c) ionisation isomerism
(b) dichloro bis (methylamine) copper (II)
(d) geometrical isomerism
(c) dimethylaminecopper (II) chloride
60. [Fe(NO 2 h Cl 3 ] and [Fe(O-NOh Cl 3 ]shows [DCEJ (d) b is(dimethylamine) copper (II) chloride

Topic 3
Bonding in Coordination Compounds
2014
1. The question when worked out will result in one integer 6. Match the following columns. [EAMCETJ
from Oto 9 (both inclusive).
Column I Column TT
A list of species having the fommla XZ4 is given below
A. sp3 I. [Co(NH3 \]3+
XeF4 , SF4 ,SiF4 , BF4, BrF4, [Cu(NH 3 ) 4 ] 2 +
B. dsp2 2. [Ni(CO)4 ]
[FeC1 4 ] 2 - , [CoC14 ] 2 - and[PtCl 4 ] 2 -
c. sp3d2 3. [Pt(NHJ2 Cl2 ]
Defining shape on the basis of the location of X and Z D. ds/ 4. [CoF6 f-
atoms, the total number of species having a square planar
5. [Fe(CO)s]
shape is
(a) 3 (b) 2 Codes
(c) 4 (d)) 6 A B C D A B C D
2. Among [Fe(H2 0)6 ] 3 +, [Fe(CN)6 ] 3 - , (a) 5 2 4 3 (b) 2 3 4 5
(c) 2 3 1 5 (d) 3 2 4 1
species, the hybridisation state of the Fe atom are,
respectively [VITEEE] 7. The anti-cancer drug cis-platin has the formula
Pt(NH 3 h Cl 2 . There is another isomer, trans-platin, that
( a) d 2 sp 3 , d 2 sp 3 , sp 3d2
.
is not medically active. What is the shape of cis-platin ?
(b) sp3 d2 'd2sp3 ,d2 sp3 [Indraprastha]
2 2
(c) sp 3d ,d sp 3 ,sp 3d
2
(a) Tetrahedral (b) Octahedral
(d) None of the above (c) Square p lanar (d) Trigonal b ipyramidal
3. Which of the following is coITect statement? 8. The colour in the coordination compounds can be readily
(a) [Co(NH 3 ) 6 J2 + is paramagnetic [Karnataka CET] explained in terms of [J&K CETJ
2
(b) [MnBr4 ] - is tetrahedral (a) spectrochemistry (b) chelate effect
r
(c) [CoBr2 (en)i exhibits linkage isomerism (c) crystal field theory (d) None of these
2
(d) [Ni(NH3 ) 6 ] + is an inner orbital complex 2013
4. The spin only magnetic moment value (in BM unit) of 9. Consider the following complex ions, P,Q and R.
Cr(CO) 6 is [AMU]
P = [FeF6 ] 3 - ,Q= [V(H 2 O) 6 ] 2 +and
(a) zero (b) 2.84 2
R=[Fe(H 2 O) 6 ] +.
(c) 4.90 {d) 5.92
5. The ratio of magnetic moment (spin only value) between The cotTect order of the complex ions, according to their
spin-only magnetic moment values
[FeF6 ] 3 - and[Fe(CN) 6 ] 3 - is approximately [AMU]
(in BM) is [JEE Advanced]
(a)4 {b)2 (a)R<Q<P (b)Q<R<P
(c) 5 (d) 3
(c)R<P<Q (d)Q< P<R
 Coordination Compounds I 545
2012
10. NiC1 2 [P(C2 H 5 h (C 2 H 5 )h exhibit temperature dependen 19. The complex ion which has the highest magnetic moment
t magnetic behaviour (paramagnetic/diamagnetic). The among the following is [Ke rala CEE]
coordination geometries of Ni 2 + in the paramagnetic and (a) [CoF6 ]3- (b) [Co(NH3) 6 ] 3 +
diamagnetic states are respectively [IIT JEE] (c) [Ni(NH3 ) 4 ] 2+ (d) [Ni(CN) 4 ] 2 -
(a) tetrahedral and tetrahedral (e)[Fe(CN)6 ]4 -
(b) square planar and square planar
(c) tetrahedral and square planar 20. The correct statement with respect to the complexes
2
(d) square planar and tetrahedral Ni(CO)4 and [Ni(CN) 4 ] - is [Kerala CEEJ
11. What is the magnetic moment of[FeF6 ]3 - ? [Manipal] (a) nickel is in the same oxidation state in both
(b) both have tetrahedral geometry
(a) 2 BM (b) 5.9 BM (c) 7 BM (d) 35 BM (c) both have square planar geometry
12. In [NiCl 4 ]2- , the type of hybridisation for Ni is [AMUJ (d) have square planar and tetrahedral geometry
3 2 3 respectively
(a) sp d (b) dsp (e) have tetrahedral and square planar geometry
(c) sp 3
(d) dsp 2 respectively
13. Maximum value of paramagnetism is shown by [AMU] 2010
(a)[Fe(CN)6 ]3- (b)[Cr(CN)6 ] 3- 21. The complex showing a spin-only magnetic moment of
(c)[Co(CN)6 ]3- (d)[Sc(CN\] 3- 2.82 BM is [IIT JEE]
(a) Ni(CO) 4 (b) [NiCl 4 ]2-
2011 2
(c) Ni(PPh 3 ) 4 (d) [Ni(CN)4 ] -
14. Geometrical shapes of the complexes formed by the reaction
2 22. Which one of the following complex is an outer orbital
of Ni + with Cl- , CN- and H 2 0, respectively, are
complex? [Manipal]
(a) octahedral, tetrahedral and square planar CIIT JEE]
(b) tetrahedral, square planar and octahedral (Atomic numberofMn = 25, Fe = 24, Co = 27, Ni = 28)
(c) square planar, tetrahedral and octahedral (a) [Fe(CN)6 ]4- (b) [Mn(CN)6 ]4-
(d) octahedral, square planar and octahedral 3
(c) [Co(NH3 ) 6 ] + (d) [Ni(NH 3 ) 6 ] 2+
15. Among the following complexes (K-P), K 3[Fe(CN) 6 ](K),
23. Which one of the following is wrongly matched fKCET]
[Co(NH3) 6 ]Cl 3 (L), Na 3 [Co(oxh ](M)
(a) [Cu(NH3 ) 4 ] 2 + - Square planar
[Ni(H 2 O)6 ]Cl 2 (N), K 2 [Pt(CN) 4 ](O)and
[Zn(H 2 O)6 ](NO 3 ) 2 (P) the diamagnetic complexes are (b)[Ni(CO) 4 ] - Neutral ligand
(c)[Fe(CN6 )]3 - - sp 3 d 1
(a)K,L,M,N (b)K,M,O,P CIITJEEJ
(c)L,M,O,P (d)L,M, N,O (d) [Co(enh ] 3+ - Follows EAN rule
16. Which of the following facts about the complex 24. Show the coordination number of the metal ion, its
[Cr(NH 3 ) 6 ]Cl 3 is wrong? [AIEEEJ oxidation number, the number of electrons in d-orbitals
2 and the number of unpaired electrons in d-orbitals
(a) The complex involves d sp 3 hybridisation and is
octahedral in shape respectively in complex [Co(H2 O)4 SO3]CI. [Guj CET]
(b) The complex is paramagnetic (a) 6, 3, 6, 4 (b) 6, 3, 6, 0 (c) 5, 3, 6, 4 (d) 5, 3, 6, 0
(c) The complex is an outer orbital complex 3
25. [Sc(H 2 O)6 ] + ion is [JCECE]
(d) The complex gives white precipitate with silver nitrate
solution (a) colourless and diamagnetic
(b) coloured and octahedral
17. The magnetic moment (spin only) of[NiC14 ] 2- is (c) colourless and paramagnetic
(a) 1.82 BM (b) 5.46 BM [AIEEEJ (d) coloured and paramagnetic
(c) 2.82 BM (d) 1.41 BM
2009
18. Among the ligands NH 3, en, CN- and CO, the correct order
26. In spectrochemical series chlorine is above than water,
of their increasing field strength, is [AIEEEJ
i.e., Cl> H 2 0, this is due to [IIT JEE]
(a)CO < NH 3 < en < CN- (a) good 1t-acceptor prope1t ies of Cl
(b) NH 3 < en < CN"" < CO (b) strong cr-donor and good 1t-acceptor properties ofCl
(c) good 1t-donor properties of Cl
(c)CN- <NH 3 < CO < en
(d) larger size of Cl than H2 0
(d)en < CN- < NH 3 < CO
546 I Chapterwise & Topicwise Engineering Entrances Solved Papers
27. Match the following columns. 34. Which of the following shell, fom1 only an outer octahedral
complex ? [UPSEEJ
Column I Column II
(a)d 4 (b)d 8
A. [Ni(CN)4 ]2- 1. (c) d 6
(d) None of these
B. Chlorophyll 3
2. sp ; paramagnetic 35. Hybridisation, shape and magnetic moment of
K 3 [Co(CO3 h ] is [OJEEJ
C. Ziegler-Natta catalyst 3. Non-planar
(a) d 2 sp 3 , octahedral, 4.9 BM
D. [NiCl 4]2- 4. Mg2+
(b) sp 3 d 2 , octahedral, 4.9 BM
E. Deoxyhaemoglobin 5. Planar
(c) dsp 2 , square planar, 4.9 BM
6. ds/; diamagnetic
(d) sp 3 , tetrahedral, 4.9 BM
Codes [Kerala CEE]
36. [Ni(CN) 4 ] 2- , [MnBr4 ] 2- and [CoF6 ] 3- , geometry,
A B
C D E hybridisation and magnetic moment ofthe ions respectively,
(a) 6 4I 2 3 are [OJEEJ
(b) 2 4I 6 3
(a) tetrahedral, square planar, octahedral :
(c) 2 4I 6 5
(d) 6 4I 2 5 sp 3 , dsp 2 , sp 3 d 2 : 5.9, 0, 4.9
(e) 2 4
3 6 5 (b) tetrahedral, square planar, octahedral:
28. Which of the following species will be diamagnetic ? dsp 2 , sp 3 , sp 3 d 2 : 0, 5.9, 4.9
4 3
(a) [Fe(CN) 6 ] - (b)[FeF6 ] - [AMUJ
(c) square planar, tetrahedral, octahedral:
3
(c) [Co(C2 O 4 h ]- (d) [CoF6 ] 3- 2 3 2 3
dsp ,sp , d sp : 5.9, 4.9, 0
29. Which complex compound possesses sp 3d 2 hybtidisation? (d) square planar, tetrahedral, octahedral:
(a) [Fe(NH ) ] 3+
3 6 (b) [Fe(CN) ]4- [Guj CETJ 6 dsp 2 , sp 3 , sp 3 d 2 : 0, 5.9, 4.9
(c) [Fe(CN)6 ] 3- (d) [Fe(Cl)6 ] 3- 37. The reaction, [Fe(CNS) 6 ] 3- ~ [FeF6 ] 3- talces place
30. When EDTA solution is added to Mg 2+ ion solution, then with [OJEEJ
which of the following statements is not true? [DCEJ (a) decrease in magnetic moment
2 (b) increase in magnetic moment
(a) Four coordinate sites of Mg + are occupied by
EDT A and remaining two sites are occupied by water (c) decrease in coordination number
molecules (d) increase in coordination number
(b) All six coordinate sites of Mg 2+ are occupied 38. The number of unpaired electrons in the square planar
2
(c) pH of the solution is decreased. [Pt(CN) 4 ] - ion is [J&K CETJ
(d) Colourless [Mg-EDTA] 2 - chelate is formed 002 ~I ~0 ~3
2008 39. Which has maximum paramagnetic character? [DCEJ
2
31. In which of the following octahedral complexes of Co (a) [Fe(CN)6 ]4- (b) [Cu(H 2 O) 4 ] +
(atomic number 27) will be magnitude of L'l 0 be the (c) [Cu(NH3 ) 4 ]
2
+ (d) [Mn(H 2 O) 6 J2+
hlghest? [AIEEEJ
40. In which of the following complex ion, the central metal
3
(a)[Co(CN) 6 ] - 3
(b)[Co(C2 O 4 ) 3 ] - ion is in a state of sp 3 d 2 hybridisation?
3
(c) [Co(H 2 O)6 ] + (d) [Co(NH3) 6 ] 3+ [Jamia Millia Islamia]
32. The number of unpaired electrons calculated in (a) [CoF6 )] 3- (b) [Co(NH3 )6 ]3+
3
[Co(NH3 ) 6 ]3+ and [Co(F6 )] - are [VITEEEJ (c) [Fe(CN) 6 ] 3- (d) [Cr(NH3 ) 6 ] 3 +
(a)4and4 (b)0and2
(c)2and4 (d)0and4 2007
41. Which one of the following has a square planar geometry?
33. An octahedral complex is fom1ed when hybrid orbitals of
the following type are involved [KCETJ (Atomic Number of Fe= 26, Co = 27, Ni= 28, Pt = 78)
2 2
(a) sp3
(b) dsp 2 (a) [CoCl 4 ] - (b) [FeCl 4 ] - [AIEEEJ

(c)d 2 sp 3 (d) sp 2 d 2 (c)[NiC1 4 ]2- (d)[PtCI 4 ]2-

 Coordination Compounds I 547
42. Which of the following complex has zero magnetic 50. The magnetic moment of[Co(NH 3 ) 6 ]Cl 3 is [OJEE]
moment (spin only)? [VITEEEJ
(a) 1.73 (b) 2.83
(a) [Ni(NH 3 ) 6 ]Cl 2 (b) Na 3 [FeF6 ] (c) 6.6 (d) zero
(c) [Cr(H 2 O) 6 ]SO 4 (d) K 4 [Fe(CN)6 ]
2 2 51. Hybridisation, shape and magnetic moment of[N i(CN)4 ] 2-
43. Among [Ni(CO)4 ]2- , [Ni(CN) 4 ] - and [NiC14 ] -
ion [OJEEJ
species, the hybridisation states of the Ni atom are, 2
(a) dsp , square planar, zero
respectively (Atomic number of Ni = 28) [ManipalJ
2 2 2 (b) dsp2, square planar, 1.73
(a) sp 3 , dsp , dsp (b) sp 3 , dsp , sp
3
2
3 3 2 2 3 (c) sp 3 d , octahedral, zero
(c) sp , sp , dsp (d) dsp , sp , sp 2 3
(d) d sp , octahedral, 1.73
44. CN- is strong field ligand. This is due to the fact that
(a) it carries negative charge [Manipal]
52. Excited state configuration of Mn 2+ is [AMUJ
(b) it is a pseudohalide (a) fig (b) lige:
(c) lige: (d) tige~
(c) it can accept electrons from metal species
(d) it forms high spin complexes with metal species
45. Considering H 2 0 as weak field ligand, the number of 53. Potassium ferrocyanide is an example of [J&K CETJ
unpaired electrons in [Mn(H 2 0)6 ] + will be 2 (a) tetrahedral (b) octahedral
(c) square planar (d) linear
(Atomic number of Mn = 25) [Manipal]
54. The number of unpaired electrons in Ni(CO) 4 is[BCECEJ
(a) three (b) five (c) two (d) four
(a) 0 (b) I (c) 3 (d) 4
46. In an octahedral structure, the pair ofd-orbitals involved in
d 2sp 3 hybridisation is [ManipalJ 55. Which one of the following shows maximun1 value of
paramagnetic behaviour? [BCECEJ
(a) d .<2 - 2, d z2
y (a)[Sc(CN)6 ] 3- (b)[Co(CN)6 ] 3-
(c)d2,dxz 2
z (c) [Ni(CN)4 ] - (d) [Cr(CN) 6 ]3 -
47. The geometry ofNi(CO) 4 and Ni(PPh 3 h Cl 2 are 56. Which one of the following has square planar structure?
2
(a) both square planar [Manipal] (a)[Ni(CN)4 ] - (b) [Ni(CO)4 ] [BCECEJ
(b) tetrahedral and square planar respectively (c) [NiC1 4 ]2- (d) All of these
(c) both tetrahedral
(d) square planar and tetrahedral respectively 57. The type of hybridisation in tetrahedral complexes of metal
48. Ammonia forms the complex ion [Cu(NH3 ) 4 ]2+ with atom is [DCEJ
2 2
copper ions in the alkaline solutions but not in acidic (a) dsp (b) d sp
2
solutions. What is the reason for it ? [MP PET] (c) sp 3 (d) sp
(a) In acidic solutions hydration protects copper ions 58. The con-ect order of magnetic moments (spin only values
(b) In acidic solutions protons coordinate with ammonia in BM) among the following is
molecules forming NH! ions and NH 3 molecules are
(atomic number of Mn= 25, Fe = 26, Co = 27)
not available [Jamia Millia Islamia]
(c) In alkaline solutions insoluble Cu(OH) 2 is
precipitated which is soluble in excess of any alkali
2
(a)[MnC14 ] - > [CoC1 4 ]2- > [Fe(CN)6 J4-
(d) Copper hydroxide is an amphoteric substance (b) [MnC14]2- > [Fe(CN)6 ] 4- > [CoC1 4 ] 2-
49. Which of the following statements is not correct? (c)[Fe(CN)6 ]4- > [MnC1 4 ] 2- > [CoC1 4 ]2-
[Ke rala CEE] (d)[Fe(CN)6]4- > [CoC1 ] 2 - > [MnC1 ] 2-
4 4
(a) The complexes [NiC1 4 ] 2- and [Ni(CN) 4 ] 2- differ in
the state of hybridisation ofnickel 2006
(b) The complexes [NiC1 4 ] 2- and [Ni(CN) 4 ] 2- differ in 59. Nickel (Z = 28)combines with a uninegative monodentate
the magnetic properties ligand x - to form a paramagnetic complex [NiX 4 ] 2 - .
2 2
The number of unpaired electron(s) in the nickel and
(c) The complexes [NiC1 4 ] - and [Ni(CN) 4 ] - differ in
geometry geometry of this complex ion are respectively [AIEEEJ
(d) The complexes [NiC1 4 ] 2- and [Ni(CN) 4 ] 2- differ in (a) one, tetrahedral
primary valencies of nickel (b) two, tetrahedral
(e) Nickel ion has the same secondary valency in the (c) one, square p lanar
2 2 (d) two, square planar
complexes [NiC14 ] - and [N i(CN) 4 ] -
548 I Chapterwise & Topicwise Engineering Entrances Solved Papers
60. The crystal field splitting energy for octahedral (11 0 ) and 2005
tetrahedral (11 1 ) complexes is related to [BITSATJ 65. Which one of the following cyano complexes would exhibit
4 the lowest value of paramagnetic behaviour?
( a) 11 1 =- 110 (b)
9 (Atomic number of Cr= 24, Mn= 25, Fe= 26, Co = 27)
I (a)[Co(CN) 6 ] 3- (b)[Fe(CN) 6 ] 3 - [AIEEE]
11
I
= -2 110
( c )[Mn(CN) 6 ] 3- 3
( d)[Cr(CN) 6 ] -
4
(d) 110 =- 11 1 66. The value of the 'spin only' magnetic moment for one of the
9
following configurations is 2.84 BM. The correct one is
61. The ion which exhibits green colour [BITSAT]
(a) d 5 (in strong ligand field) [AIEEE]
(a) Cu 2+ (b) Mn 2+
(b) d 3 (in weak as well as strong ligand fields)
(c)Co 2 + (d)Ni 2+ (c) d 4 (in weak ligand field)
62. Which of the following is diamagnetic in nature ? (d) d 4 (in strong ligand field)
(a)[Fe(CN) 6 ] 3 - (b)[NiC1 4 ] 2- [MHT CETJ 67. I. K 4 [Fe(CN)6 ] II. K 3 [Cr(CN)6 ]
(c) [Ni(CO)4 ] (d) [MnC1 4 ] 2- III. K 3 [Co(CN) 6 ] IV. K 2 [Ni(CN) 4 ]
63. Which of the following complexes are not correctly Select the complexes which are diamagnetic.[Kerala CEE]
matched with hybridisation of their central metal ion ? (a) I, II and III (b) II, III and IV
T. [Ni(CO)4 Jsp3 Tl. [Ni(CN)4 ] 2- sp3 (c) I, III and IV (d) I, II and IV
lll. [CoF6 ]3- d 2sp3 TV. [Fe(CN\] 3- sp3d 2 (e) II and IV
Select the correct answer using the codes given below 68. How many unpaired electrons are present in the central metal
(a) I and II (b) I and III [Kerala CEE] ion of[CoC1 4 ] 2 - ? [OJEE]

(c) II and IV (d) I, III and IV W3 ~4 W5 w2

(e) II, III and IV 69. What is the magnetic moment ofK 3 [FeF6 ]? [OJEE]
64. Which of the following statements is not correct? (a) 5.91 BM (b) 4.89 BM (c) 3.87 BM (d) 6.92 BM
[EAMCET]
70. The most stable ion is [Jamia Millia Islamia]
(a) In oxyhaemoglobin Fe 2+ is paramagnetic
(a) [Fe(OH)5 ] 3
- (b) [FeC16 ] 3-
(b) During respiration the size ofFe 2+ increases when
it changes from diamagnetic to paramagnetic state (c) [Fe(CN) 6 ] 3
- (d) [Fe(H 2 O) 6 ] 3 +
(c) Four haeme groups are present in haemoglobin
( d) Haeme is the prosthetic group and it is non-protein
part

Topic 4
Bonding in Metal Carbonyls
2014 2010
1. The bond order between Ni-Cbond in Ni(CO) 4 is 4. In which compound synergic effect is present? [MP PET]
2
(a) one (b) two [AMUJ (a) [Ni(CO)4 ] (b) [NiCl 4 ] -
( c) less than two (d) more than two (c)[CuCl4 ] 2- (d)[Mn(H 2 O) 6 ] 2+
2. Which one of the following oxidation state is not possible 5. Ziegler-Natta catalyst is [JCECE]
in metal carbonyls [AMUJ
(a)(Ph 3 P) 3 RhCI (b) K[PtC13 (C2 H 4)]
(a) + I (b)O (c) [Al 2 (C2 H 5 ) 6 + TiC1 4 ] (d) [Fe(C2 H 5 h]
(c) - I (d) + 2
3. Which is the metal present in the coordination compound 2009
chlorophyll ? [J&Kl 6. Which of the following is an organometallic compound?
(a) Ca (b) Mg (a) Lithium methoxide (b) Lithium acetate [UPSEE]
(c) K (d) Na (c) Lithium dimethylamine (d) Methyl lithium
 Coordination Compounds I 549
2008
7. Which one is an organometallic compound in the 13. Which of the following doesn't have a metal-carbon bond?
following? [MPPET] (a) Al(OC 2 H 5 h [Manipal]
(a) C2 H 5 ONa (b) C 2 H 5 - S- S- C 2 H 5 (b) C2 H 5 MgBr
(c) Al 2 (CH 3 ) 6 (d) Al(C 6 H 5 S)3 (c) K[Pt(C 2 H 4 )Cl 3 ]
8. Which of the following is an organometallic compound ? (d) Ni(CO) 4
(a) Ti(C 2 H 5 ) 4 (b) Ti(OC2 H 5 ) 4 [MP PET] 14. Coordination compounds have great importance in
(c) Ti(OCOCH 3 ) 4 (d) Ti(OC6 H 5 ) 4 biological systems. In this context which of the following
9. In metal carbonyl (organometallic) complexes, the M - C statements is incorrect ? [Jamia Millia Islamia]
bond is [J&K CET] (a) Chlorophyll is green pigment in plants and contain
(a) ionic calcium
(b) covalent with ionic character (b) Haemoglobin is the red pigment of blood and
(c) covalent contains iron
(d) coordinate covalent (c) Cyanocobalamin is vitamin B12 and contains cobalt
(d) Carboxypeptidase-A is an enzyme and contains zinc
2007
2006
10. Among the following metal carbonyls, C-Obond order is
lowest in [HT JEE] 15. In Fe(CO)5 , the Fe-Cbond possesses [AIEEEJ

(a) [Mn(CO) 6 t (b) [Fe(CO)s] (a) 1t-character only

(c) ionic character
(b) both cr and 1t-characters
(d) a -character only
(c) [Cr(CO) 6 ] (d) [V(CO) 6 r 16. Estimation of calcium and magnesium is done by
11. In the Grignard reaction, which metal forms an (a) EDTA (b) oxalate [UPSEEJ
organometallic bond ? [VITEEE] (c) phosphate (d) None of these
(a) Sodium (b) Titanium
(c) Magnesium (d) Palladium
2005
17. Wruch of the following is not an organometallic
12. Which of the following is considered to be an anti-cancer
compound?
species ? [Manipall
(a) C2 H 5 ONa (b) CH3Mgl [J&K CETJ
(c) Tetraethyl tin (d) KC4 H 9
(a) Cl ~ !H
CH2]
2
18. Ziegler-Natta catalyst is an organometallic compound
containing [J&K CETJ
[
Cl ~ Cl (a) iron (b) titanium
(c) rhodium (d) zirconium
(b) [ Cl ~ Cl] 19. Then-bonded organometallic compound which has ethene
as one of its component is [J&K CETJ
Cl ~ Cl
(a) Zeise's salt (b) ferrocene
(c) dibenzene chromium (d) tetraethyl tin
20. CH 3MgI is an organometallic compound due to
(a) Mg-I bond [Jamia Millia Islamia]
(b) C-Ibond
(c) C-Mg bond
(d) C-Hbond
 Topic 5
Stability of Coordination Compounds
2009
1. What is the overall formation equilibrium constant for the ion [ML4 ] 2- ion, given that ~ 4 for this complex is 2.5 x 1013 ?
14
(a) 2.5 X 1013 (b) 5 x 10- 13
(c) 2.5 x 10- [Ke rala CEE]
13 14
(d) 4.0 x 10- (e) 4.0 x 10-

Answers
TOPIC 1 General Terms
1. (b) 2. (b) 3. (b) 4. (b) 5. (d) 6. (c) 7. (a) 8. (b) 9. (d) 10. (b)
11. (c) 12. (b) 13. (b) 14. (d) 15. (b) 16. (d) 17. (b) 18. (c) 19. (c) 20. (c)
21 . (e) 22. (c) 23. (b) 24. (b) 25. (c) 26. (d) 27. (a) 28. (c) 29. (c) 30. (c)
31 . (a) 32. (c) 33. (d) 34. (d) 35. (c) 36. (a) 37. (a) 38. (b) 39. (d) 40. (c)
41 . (c) 42. (d) 43. (b) 44. (a) 45. (b) 46. (c)
TOPIC2 Nomenclature and Isomerism
1. (b) 2. (b) 3. (a) 4. (d) 5. (a) 6. (d) 7. (c) 8. (d) 9. (c) 10. (c)
11. (d) 12. (b) 13. ( d) 14. (d) 15. (c) 16. (b) 17. (a) 18. (b) 19. (b) 20. (c)
21 . (a) 22. (b) 23. (c) 24. (a) 25. (d) 26. (d) 27. (d) 28. (d) 29. (b) 30. (c)
31 . (b) 32. (b) 33. (c) 34. (a) 35. (c) 36. (c) 37. (b) 38. (c) 39. (c) 40. (b)
41 . (b) 42. (b) 43. (d) 44. (b) 45. (b) 46. (b) 47. (d) 48. (c) 49. (d) 50. (c)
51 . (d) 52. (d) 53. (d) 54. (b) 55. (c) 56. (a) 57. (b) 58. (c) 59. (b) 60. (a)
61 . (b)
T0PIC3 Bonding in Coordination Compounds
1. (c) 2. (c) 3. (a,b) 4. (a) 5. (d) 6. (b) 7. (c) 8. (c) 9. (b) 10. (c)
11. (b) 12. (c) 13. (b) 14. (b) 15. (c) 16. ( C) 17. (c) 18. (b) 19. (a) 20. (e)
21 . (b) 22. (d) 23. (c) 24. (c) 25. (a) 26. (b) 27. (a) 28. (a) 29. (d) 30. (a)
31 . (a) 32. (d) 33. (c) 34. (b) 35. (b) 36. (d) 37. (b) 38. (c) 39. (d) 40. (a)
41 . (d) 42. (d) 43. (b) 44. (b) 45. (b) 46. (a) 47. (c) 48. (b) 49. (d) 50. (d)
51 . (a) 52. (b) 53. (b) 54. (a) 55. (d) 56. (a) 57. (c) 58. (a) 59. (b) 60. (a)
61 . (d) 62. (c) 63. (e) 64. (a) 65. (a) 66. (d) 67. (c) 68. (a) 69. (a) 70. (c)

TOPIC4 Bonding in Metal Carbonyls

1. (d) 2. (d) 3. (b) 4. (a) 5. (c) 6. (d) 7. (c) 8. (a) 9. (d) 10. (b)
11. (c) 12. (c) 13. (a) 14. (a) 15. (b) 16. (a) 17. (a) 18. (b) 19. (a) 20. (c)
TOPIC5 Stability of Coordination Compounds
1. (a)
 Explanations
Topic 1 General Terms
1. Ligand field strength °" Energy oflight absorbed 6. EDTA is a hexadentate ligand, so it can form complexes with 6
1 donor atoms.
O<: - - - - - - - - - - -

Wavelength of light absorbed

Wavelength of absorbed light decreases
-00CCH2
\ N-
.. .

CH 2 - CH 2 - N
.. /
CH2COO

L -..OOCCH2I "CH2COO-
Absorbed light Red Yellow Green Blue

As the energy of wavelengths absorbed increases, greater extent Since, EDTA 4 - bonds to a metal ion through six donor atoms,
of crystal-field splitting, hence higher field strength of the ligand. (2 nitrogen and 4 oxygen atom) it forms highly stable complxes.
Increasing order 7. EDTA is a multidentate ligand as it can donate six pairs of
Energy : Li < L 3 < L 2 < L 4 electrons, two pair from the two nitrogen atoms and four pair
(Red) (Yellow) (Green) (Blue) from the four terminal oxygens of the - coo- groups.
Ligand field strength : L 1 < L 3 < L 2 < L 4 - 00CCH2v• .• /CH,coo-
N -CH2CH2- N -
2. (a) Li 2O + KCl - 2LiCI + K 2O OOCCH/ "CH2Coo-
This is wrong equation, since a stronger base KiO cannot be The structure of a chelate of divalent Co2 + with EDTA is shown
generated by a weaker base Li 20. as
2
t
(b) [CoCl(NH 3) 5 + SW - Co + (aq) + SNH! + Cl-
This is correct. All ammine complexes can be destroyed by /co~
adding W9 . Hence, on adding acid to [CoCl(NH3)5 1 it gets
converted to Co2 + (aq) NH! and Cl-.

(c) [Mg(H2O:l6] 2+ + EDTA4- :;H-

c.."(Ces5

This is wrong, since the formula of complex must be

[Mg(EDTA)f- .
2
[Mg(EDTA)] + + 6H2O
d co-cyH,
0~ --~-
I

{f)1-~H,
J - J CH2

(d) The 4th reaction is incorrect. It can be correctly represented as

2CuSO4 + 10 KCN - 2K3[Cu(CN)4 ] octCH2 CH2
+ 2KiSO4 + (CN)i i
3. Zn 2 + , Al3 +
(i) Zn(OH)2 + 2NaOH - Na 2[Zn(OH)4 ]
Sodium tetrahydroxozincate (II)
o"/
co
Each N has four N- Co- O bonds and thus tota l eight
ZnCl2 + 4NH 3 - [Zn(NH 3)4 Cl 2 ] N- Co--O bonds.
Anhydrous Dichlorotetraarmnine
zinc (II) 8. EAN of Co in NaJlCo(NOz)4 Cl 2 ]
(ii) Al(OH)3 + NaOH - Na[Al(OH)4 r = Atomic number of Co ± oxidation state of Co + 2 x number of
electron taken from NO2 and Cl
At 3+ + 3NH 3 - Al(NH3)3
= 27 - 3 + 2 X (4 + 2) = 36
4. [ AICl(H2O)5 ] 2+ 9. Bidentate ligands have two donor (e- donor) atoms. So, they can
Let oxidation state of Al is x . linked with central metal ion in two ways. e.g., ethylene diamine
x + (- I) + S (0) = + 2 ⇒ x = + 3 (en) dimethylglyoxime (dmg) etc.
Covalency of Cl = I, covalency of Hp= S CH2- NH2"" H 3C-C - C- CH 3
:. Total covalency = I + S = 6 I I I
5. Oxidation number of central metal ion can be calculated by using CH2-NH2 / -o -N N- o -
the concept that oxidation state of whole compound is always (en) "-../
(dtng)
zero (0) or equal to charge present on it as a whole.
dmg is negatively charged.
Here, K[PtNHp 5 ] ~ K+ + [Pt(NH 3)Ct5 r 10. [Fe(H2O)5NO+ ] SO4
Let, oxidation state of Pt is x
x+ J x0 + Sx-1=-I Let oxidation state of Fe= x
x-5 =-I ⇒ x = S-1 =4 x+Sx0 + l-2 = 0
Hence, (d) is the correct choice. x-1=0,x=+ I
552 I Chapterwise & Topicwise Engineering Entrances Solved Papers

11. EDTA structure is 21. One mole of X gave depression corresponding to 2 moles of
HOOCH2~ /H2COOH particles, i.e. on ionisation X gives 2 moles of ions, thus it
/N- CH2- CH2- N "> contains only l ion outside the coordination sphere and its
structural formula is [Cr(H2O)4 Br2 ]Cl· H 2O while Y gives
HOOCH2C CH2COOH 3 moles of ions, thus it contains two ions outside the coordination
12. A species or group of atoms can act as ligand only when it carries sphere and its structural formula is [Cr(HP)5Cl]Br2.
an unshared pair, i.e. lone pair of electrons. 22. Effective atomic number = electrons in Cr 3+ + electrons from
13. The complex which contains I 8 valence electrons, follows 6NH 3 ligands.
18-electron rnle. = 2] + 6 X 2 = 33
(a) In [V(CO)5 ], The number of valence electrons 23. Ethylene diaminetetraacetate ion is a hexadentate ligand because
= S + (2 x S) = IS e- it has six donor centres.
(b) In [Fe(NH 3\ J2+, The number of valence electrons - OOC-CH2 CH2Coo -
"> "" •• /
= 6+ (6x 2)= 6+ 12= 18 e- / N- CH 2- CH2- N ">
OOC· CH2 CH2Coo-
(c) In [Ni(CO\], The number of valence electrons Ethylene diaminetetraacetate ion
= 10 + (2 X 6) = 22e-
24. KiNi(CN)4 ] ~ 4K+ + (Ni(CN)4 ]4-
(d) In [Mn(H2O\ f+, The number of valence electrons
x + (4 x- l) = -4 ⇒ x-4 =-4 ⇒ x=0
= 5 + (6 X 2) = 17 e- 25. The munber of unidentate ligand in the complex ion is called
Thus, only [Fe(NH~ ] 2+, follows 18-electron rnle. coordination number.
14. Let the oxidation state of Fe in [Fe(H2O)5 NO]SO4 is x. 26. Let the oxidation state of iron in K 4 [Fe(CN};] is x.

[Fe(H2O)5 N0 )2+ 4 (+ 1) + x + 6 (- 1) = 0
4+x-6=0
⇒ x+0+l=2
x=+2
x=+I
27. [CoC1 3 (NH3h] cannot ionise in solution because three chloride
Here, NO exists as nitrosyl ion (NO+). ions satisfy primary and secondary valencies. It will not be
15. The compound in which ligands form ring with the metal are precipitated by the addition of AgNO3.
called chelate complex.
29. Let the ON of Pt in [Pt(NH3) 5 Cl]Cl 3 is x.
16. Greater is the number of chelate rings, greater is stability of the
x + 5 X (0) - 1 - 3 = 0
chelate. Hence, five fused cyclic system is most stable for a
chelate. x-4=0
x=+4
17. Effective atomic number (EAN) = Atomic number of metal
29. Effective atomic number (EAN)
-Oxidation number+ Coordination number x2
= Atomic number - 0 . S + 2 x C. N
For [CoF6 f-, the oxidation state of cobalt is 4. = 28 - 0 + 2 X 4 = 28 + 8 = 36
EAN = (27 - 4) + 6 x 2 = 23 + 12 = 35 30. The coordination number (C N) of a metal atom in a complex is
18. CO is a neutral ligand, so the oxidation state of metal in metal the total number of bonds formed by metal with ligands.
carbonyls is always zero. In case of tetrahedral complexes the munber of bonds formed
(Ni(CO)4 ] between metal and ligand is four. So, coordination number is also
X + (0 X 4) = 0 four.
x=0 31. Coordination number is the maximtun covalency shown by a
19. A ligand is a species that is capable ofdonating an electron pair(s) metal or metal ion. It is the maximum number of ligands attached
to the central metal ion. The substances which are capable of to metal by sigma bonds or coordinate bonds.
donating an electron pair are called Lewis base, so a ligand is also 32. EDTA (Ethy lenediaminetetraacetic acid)
a Lewis base. -ooccH\ / c H 2coo-
20. The formula of dichlorodioxalatochromium (HD is / J'!-CH2-CH2-J'!"
[Cr(Cli)(ox}i ] 3- -OOCCH2 CH2Coo-
Primary valency of a metal (Cr) in the complex
It is hexadentate (6 electron pairs) that's why for octahedral
= oxidation number of that metal = + 3 complex only one EDTA is required.
Secondary valency of chromitun in complex
33. [Pt(NH~]C14 complex gives five ions in the solution.
= coordination number = + 6
[Pt(NH~]C14 ~ [Pt(NH 3\ ]
4
+ + 4 Cl-
(·: Coordination number is the number of ligands attached to the
central metal ion and oxalate ion is a bidentate ligand, i.e. can 34. The total number of monodentate ligands attached to the central
coordinate at two positions.) metal is known as coordination number. Hence, in [Cu(HP)4 ] 2+
coordination munber of Cu atom is 4.
 Coordination Chemistry I 553
35. EAN = Z - (ON)+ 2 (CN) 42. (!) The sum of oxidation states of al I atoms in a compound is zero.
where, ON = oxidation number (ii) Oxidation state of metal in carbonyl is zero.
CN = coordination number (a) K 4 [Fe(~]
Let, oxidation state of Fe in K4[Fe(~] = x
Z = atomic number
[Fe(~]4-: + 4 + X + (-1 X 6) = 0
x= + 2
EAN=26-(2)+ 2(6)=26-2 + 12=36
(b) K 2FeO4
36. [Co(NH3)3Cl 3 ] does not give a precipitate with AgNO 3 solution
Let, oxidation state of Fe in K 2FeO 4 = x
because all the chloride ions are non-ionisable.
+ lx2+x + (-2x4)=0
[Co(NH3)3Cl 3 ] ~ Does not ionise x=+6
37. [Co(NHl\ ]Cl3 gives four mole of ions on complete ionisation. (c) FeiO3
[Co(NH3~]Cl 3 ~ [Co(NH~f+ + 3Cl- Let, oxidation state of Fe in Fep3 = x
38. Os(Z = 76) : [Xe] 4 f 4
1 , 5d6, 6s 2 2-r + (- 2 X 3) = 0
or 2-r = 6
Hence, the coordination number in an osmium complex may
increase to 8. x=~=+3
2
39. [Cr(NH3)4 Cl 2 t (d) Fe(CO)s
Let oxidation state of Cr = x
Oxidation state of Fe in Fe(CO)5 = 0
NH3 =0
:. Oxidation state ofFe is least in Fe(CO)5.
Cl =-1
Net charge = + I 43. As cobalt is present as Co3+ and coordination munber of cobalt is
6, the molecular formula of compound should be CoCl 3 · yNH3.
[Cr(NH3)4 Cl2 t Now, as it gives a total of three ions when dissolved in water, its
x + 4 x O + 2(-1) = + I structural formula must be [CoCl(NH3) 5 ]Cl 2
x=+3 [CoCl(NHJ5 ]Cl 2 ~ [CoCl(NH3)5 ]2+ + 2CI-
40. Coordination number is the number of ligands cr-bonded to Thus, only one c1- ion is satisfying both primary and secondary
meta l-atom. Hence, coordination number of X in valency of Co3+ in this compound.
[ X (SO4 )(NH3) 5 ]Cl is 6. Let oxidation state of X in the complex
44. For KiFe( ~ ], the EAN ofFe2+ ions= (26 - 2 + 12) = 36.
be 'y', then
y+ (- 2) + 5 (0) + (- I)= 0 Hence, it follows EAN rnle, as its EAN is equal to number of
y-2- 1 =0 electrons of Kr (inert gas), i.e. 36.

41. [Cu(NHJ4 ]SO4

y=+3
? H2-NH2
..
45. Ethylenediamine is a bidentate ligand.

Oxidation numbers of Cu CH2---t{f-{2

⇒ x+ 4 x0-2=0
x-2=0 46. Let the oxidation number of cobalt is x in K[Co(CO)4 ].
x= + 2 l + x + 0=0
Oxidation Number of Cu=+ 2 x=-1
Oxidation Number of Pt in [Pt(NH 3hC1 2 ]
x+2x0 + 2x- 1=0
Topic 2 Nomenclature and
x-2=0 Isomerism
x=+2 1. Molecular orbital electronic configuration (MOEC) for various
Oxidation Number ofNi in [Ni(CO)4 ] coordination compounds can be drawn using VBT as MOEC for
[Cr(NH3)4 Cl2 ]Cl is
x+4x0=0
x=0 3d 4s 4p
Oxidation Number of Fe in K 3[Fe(CNk;] 11 11 11 Ixx Ixx I EJ lxx lxx lxx l
NH3 Cl Cl
3 x (+ I) + x + 6 x - I = 0
3 + x-6=0 Number ofunpaired electrons (n) = 3
x= + 3 Magnetic properties = paramagnetic
: . [Ni(CO)4 ] is zero va lent compound. Geometrical isomers of[Cr(NHJ4 C1 2 i+ are
554 I Chapterwise & Topicwise Engineering Entrances Solved Papers
4. According to recommendations of IUPAC of 2004, there should
add ido in the end while naming anionic ligands such as, c1- , Br-
and r ions.
5. [Cr(NH:i)3 (H2O) 3]Cl 3
IUPAC name is triamminetriaquachromium (III) c hloride.
MOEC of[Ti(H2O)5 Cl](NO3)i] is 6. Depending on the strncture of the complex, different types of
isomerism are shown.
111 lxx lxx l I~ lxx lxx lxx ll~~~
Hi0H2O H 2O H 2O H 2O Cl Complex Isomerism
n=1
Magnetic properties = Paramagnetic A. [ Cr(NH 3) 5 Cl)Cl 2 Neither ofstrnctural
Ionisation isomers of [Ti(H2O)5 Cl](NO3 )z are [Cr(NH:i)4Cl 2 ]Cl nor stereoisomerism
[Ti(H2O)5 Cl ](NO3h and [Ti(Hp)5 (NO:i)]Cl(NO3)
MOEC of[Pt[en](NH:i)Cl]NO 3 is B. [Co(NH:i)4 Cl2 t Cl

I1l I1l I1l I1l Ixx I E] Ixx Ixx I I ._I -'-"--'-L-'

H,®NH,
en en NH3Cl
n=O
H3N NH3
Magnetic property =Diamagnetic Cl
Ionisation isomers are [Pt(en)(NH3)Cl] NO3 and
Tra11sWrtCI
[Pt(en)(NH 3)(NO 3)] Cl
t
MOEC of[Co(NH 3)4 (NO 3h ]NO3 is

I1l I1l I1l Ixx Ixx I E] Ixx Ixx Ixx I

[Pt(H2O)(NH:i)2Cl
H,°[SJ_NH'
Pt
NH3NH3 NH3 NH3NO3NO 3
II= 0
Cl Cis NH3
Magnetic property = Diamagnetic
Geometrical isomers are
NO3 NO3
H,°[2JNH,
Pt
H3N "- I / NO3 NO3"-- I /NH3
Co and Co H3N Trans Cl
H3N / I "-NO3 N03/ I "-- NH3
NO3 NO3
Trans Cis
C. [ CoBr2Cl 2 ]2- sp3 tetrahedral
Thus, magnetic property and isomerism in given coordination [PtBr212 ]2 - dsp2-square planar
compounds can be summarised as:
P. [Cr(NH3)4 Cl 2 ]Cl ➔ Paramagnetic and exhibits cis-trans D. [Pt(NH3)3(NO3)]Cl [Pt(NH:i)3NO 3]Cl) . .
Ionisation
isomerism (3) [Pt(NH:i)3Cl]NO3
Q. [Ti(H 2O)sCl](NO3)2 ➔ Paramagnetic and exhibits ionisation
isomerism (I) [Pt(NH3)3Cl] Br [Pt(NH:i)3Cl]Br) . .
Ionisation
R. [Pt(en)(NH3)Cl ]NO 3 ➔ Diamagnetic and exhibits ionisation [Pt(NH 3) 3Br]Cl
isomerism (4)
S. [Co(NH:i)4 (NO:i)2 ]NO3 ➔ Diamagnetic and exhibits cis-trans 7. Optical isomerism is exhi bited by only those complexes which
isomerism (2) lacks elements of symmetry.
P ➔ 3,Q ➔ 1 ,R ➔ 4,S ➔ 2 [Co(NH:i)3C l3] shows facial as well as meridional isomerism.
Hence, (b) is the correct choice. But both the forms contain plane of symmetry. Thus, this
complex does not exhibit optical isomerism.
2. Optical isomerism is shown by only those complexes which lack
symmetry. Complex [Co(NH3)3(NO2 h] shows facial and 8. [Co(NH:i) 5C l] Cl2 gives 3 moles of ions as.
meridional isomerism. Both isomers of this complex contain [Co(NH:i) 5 C l]Cl2 ~[Co(NH3) 5 Cl]2 + + 2CI-
plane of symmetry. So, it will not fonn optical isomers.
It also gives two moles of AgCI
3. Aqua-regia is a solution containing cone. HCI and cone. HNO3 in
[Co(NH:i)5 CI]2+ + 2AgNO 3 ~
the ratio 3 : I . It dissolves noble metals like Au, P t etc. [Co(NH:i) 5Cl] (NO3h + 2AgCI
HNO 3 + 3HC1 ~ 2H 2O + 2Cl + NOCI
9. K 3Fe(~ potassium ferricyanide, is potassium hexacyano
Au + 3Cl ~ AuCl 3
ferrate (III).
AuCl 3 + HCI ~ AuC1 4
Tetrachloridoaurate (IITJ
 Coordination Chemistry I 555
10. [PtC1 2(NHJ 4 ] Br2and [PtBri(NHJ4 ]Cl2 shows ionisation 20. [M (abed)] complex is square planar so will have three geometrical
isomerism because in ionisation isomerism the difference isomers.
arises from the position of groups within or outside the
coordination sphere. Therefore, these isomers give different
ions in the solution.
11. The complex is of the type MA4 B2 with coordination 2.675
21. Mole ofCoC1 3 · 6NH 3 = - - = 0.01
number 6. It shows geometrical isomerism. ci.s form is 267.5
violet coloured and trans from is green. AgNO3(aq)+ Cl-(aq) -➔ AgCl j, (white)
12. Two Br, two (en) and one Cr are parts of the complex. 4 78
Charge on the complex is Moles of AgCl = · = 0.03
143.5
2 (Br) = - 2] 0.0 1 mole CoC1 3 · 6NH 3 gives = 0.03 mol of AgCl
2 (en)= 0 =+ I :. I mole CoCl3 • 6NH3 ionises to give= 3 mol of c1-
l(Cr)=+3
Hence, the formula ofcompound is [ Co(NH1\:; ]Cl 3.
Thus, complex ion is [Cr(en)iBr2 t 22. Complex [Co(en)3j3+ has no plane of symmetry and centre of
Since, anion is bromide, thus complex is [Cr(enhBr2 ] Br. symmetry that's why it is optically active.
13. The IUPAC name ofKi[Cr(CN)iOi(O)2NH 3]is potassium
amminedicyanodioxoperoxochromate (VI).
14. mmol of complex = 30 x 0.01 = 0.3 Also, I mole of
complex [Cr(H2O)5 Cl]Cl2 gives only two moles of chloride
ion when dissolved in solution
[Cr(H2O)sCl]Cl2 - [Cr(H20)sClf+ + 2Cl- Mirror
⇒ mmol of Cl- ion produced from its 0.3 mmol = 0.6
23. Co3+ and Pt4+ have 6 coordination number.
Hence, 0.6 mmol of Ag+ would be required for precipitation. CoC1 3 · 6NH3 and PtC1 4 · SNH3
⇒ 0.60mmolofAg+ =0.IMxV(inmL) ⇒ V =6mL lnsollllion
[Co(NH3\;]Cl3 [Co(NHJ\sf+ + 3Cl-
15. Complex Isomerism shown
[PtCl(NHJs ]Cl3 lnsolu1ion > [PtCl(NHJsf+ + 3Cl-
(a) [Co(en)f + Optical only Number of ionic species are same in the solution of both complexes,
(b) [Ni(NHJ5 Brt No geometrical isomer therefore their equimolar solutions will show same conductance.
24. The IUPAC name ofKz[Ni(CN)4 ] is potassium
(c) [Co(NHJ2 ( en)2 ] 3+ Cis and trans
tetracyanonickelate (II).
(d) [Cr(NH3Men)] 3+ No geometrical isomer 25. Linkage isomerism is exhibited by ambidentate ligands (ligands having
two coordination sites). e.g. NO 2 .
16. [Co(NH3)4 Cl 2 ]Cl, Its IUPAC name is tetraammine If the bonding is through N, the ligand is named as nitro and if it is
dichloro cobalt (III) chloride. through 0, it is named as nitrito
NO2 - nitro- N
17. Number of moles of pentaaquachlorochromium (III)
chloride in the solu tion. ONO- - nitrito- O
0.01 X 100 = 0.00 J
fl= 26. The formula of given complex are as follows:
1000
(a) Hexammineplatinum (IV) chloride [Pt{NHJ\s ]Cl4
I mole of[Cr(H2O)5 Cl]Cl 2 gives 2 moles of chloride ions.
(b) Chloropentammine platinum (IV) chloride [Pt(NH 3) 5Cl]Cl 3
Moles of chloride ions = 0.001 x 2 = 0.002
(c) Dichlorotetrammineplatinum (IV) chloride [Pt(NHJ4 Cl2 ]Cl2
Mass of AgCl produced= 0.002 x 143.5 = 287.0 x 10- 3 g
(d) Trichlorotriammineplatinum (IV) chloride [Pt(NH3) 3Cl 3]Cl
18. [Fe(NH3kC1 2 ]CI In aqueous solution the complex ionise as
Tetraammine dichloroferrum (III) ch loride [Pt(NHjhC1 3]Cl ~ [Pt(NHJ Cl 3 + c 1- t
19. The ionisation isomer of[Cr(Hi0)4 Cl(NOi)]CI is Trichlorotriammineplatinum (IV) chloride 2 chloride ions, i.e. it gives
[Cr(H2O)4 C1 2 ]NO2 because of exchanging of ligand and produces the minimum number of ions in the solution. Hence, it has the
counter ions. minimum electrical conductivity.
27. [Cu(H2O) 4]SO4 · H 2O coordination number of Cu is 4.
556 I Chapterwise & Topicwise Engineering Entrances Solved Papers

28. Cis-form of[Co(en)2 (NH 3)2 ]3+ is optically active. 38. The TUPAC name of KiNi(CN)4 ] is potassium
tetracyanonickelate (0).
39. [PtC12 · P(C2H 5)3 h can exhibit geometrical isomerism, the
geometrical isomers are
(C2Hs)/"" / Cl"" /Cl
Pt Pt
c,/ ""c,/ ""P(C2H5)3
Trans -isomer
29. Linkage isomerism is casued due to presence of ambidentate
ligands. [Pd(PPh 3)z(NCS)2 ] and [Pd(PPh 3h(SCN)2 ] are linkage
isomers due to SCN, which is a ambidentate ligand.
30. [Co(NH3)5ONOf+
Pentaamminenitritocobalt (TII) ion.
31. (a) Geometrical isomers have same structural formula but differ
40. Fae-mer isomerism is associated with [MA 3
A A
B 3 ] type complexes.

in spatial arrangement of groups.

(b) Different arrangement of atoms or groups in three B~-t7:A B~+:7:A
: M : : M :
dimensional space results in two optical isomers which are
images of each other. sVf:'2~A B~1-~B
B A
Cis-isomer (-Fae isomer) '.lran.s-isomer (Mer-isomer)

41. The formula of hexaamminecopper II sulphate is [Cu(NHJk; ]SO4.

It dissolves in water as
[Cu(NH3\ JSO4 ~ [Cu(NH1l6f+ + so~-
Tran.s (wrtNH,) Trans (wrtCI) Cis
2 ions
(optically inactive) (optically inactive) (optically inactive)
Therefore, number of geometrical isomers, optical isomers and 42. The TUPAC name of (Ni(PPh:i)2Cl 2f+ is dichlorobis
total number of isomers are 2, I and 3 respectively. (triphenylphosphine) nickel (JI).
32. [Mabcd] type complexes exist in three isomeric forms. 43. Tris-(ethylenediamine) cobalt (JII) bromide ([Co(en)3 ]Br3)
NH3 ~ Py NH3~ B r exhibits optical isomerism.

Br ~ C l C l ~ Py
3+

en
NH3 ~ Py

Cl ~ Br Mirror
d-form I-form
33. TUPAC name is tetraamrninenickel (II)-tetrachloronickelate (TI).
34. [Co(NH3)5SO4 ]Br ~ [Co(NH3)s SOS+ Br- 44. The TUPAC name of Na 3[Co(NO2k;] is sodium
[Co(NH3)5Br]SO4 ~ [Co(NH3 ) 5Brf+ + SO~- hexanitrocobaltate (ITT).

The molecular formula of both of the above compounds is same
but on ionisation they give different ions in solution, so they are
called ionisation isomers.
35. The TUPAC name of the compound [Co(NH3) 5Cl]Cl 2 is
pentaamrnine chloro cobalt (ITT) chloride.
36. For [Mabcd] square planar complex, the number of possible
geometrical isomers is three w hich is obtained by fixing the
position of one of the ligands say awhile the other ligands b, c and
dare placed trans to it.
37. [Co(NH3k;][Cr(Cz04 hl its TUPAC name is hexaamrninecobalt
(ITT) tris (oxalate) chromate (III).
45. [ MA 5B] due to absence of symmetry of B ligand cannot exist in
the form of cis, trans isomer.
46. IUPAC name of sodium nitropmsside Na 2[Fe(CN)5NO]is sodium
pentacyanonitrosyl ferrate (III) because in it NO is neutral ligand
and the oxidation number of Fe is JII, which is calculated as
2 x ON of Na + ON of Fe + 5 x ON of CN
+ 1 x ON of NO = 0
2x(+ !) + ON of Fe + 5x(-l) + lx0=0
ON of Fe = 5-2 = + 3
47. K 3[Fe(CN)5NO]
Potassitun pentacyanonitrosyl ferrate (JI).
 Coordination Chemistry I 557
48. The name of complex is 55. Na 2[Fe(CN)5NO]
carbonylchlorobistransphosphineiridium (I). Sodium pentacyanonitroso ferrate (ID.
49. [Ptn (NH3 hC1 2 ]shows geometrical isomerism. 56. Octahedral Co(NHJ)4 Br2CI shows ionisation and geometrical
isomerism. In ionisation isomerism ligands show different

Cl
C •<1NH' Cis NH3
H N2
~-P-

3
; , 1__?
_c~,
J NH3

Trans
coordination sphere and the anions present outside the
coordination sphere. These are exchanged w ith each other as
follows
[Co(NH3) 4 Br2 ]Cl -----'- [Co(NH3 ) 4Br2 + Ci- t
(orange yellow) (pale yellow) r
[Co(NH~4 BrCl]Br -----'-

50. Benzoylacetonato beryllimn exhibit optical isomerism as follows 11

In geometrical isomerism, coordination number of central atom

Me"- /Me
C=O O=C (cobalt) is six and shape is octahedral, so it shows following
HC / "-se / "CH geometrical isomers.
~c=o/ "-o- c-7"' Br Br
Ph / '-...Ph
H3
i
N -·-'j"'-··N H H N --t--Br
i
1, 1 1 t 1 , , , , \, , , , , , 1, , , , , , , , , , , , , , , , , n Mirror image 3 . .. i /
i '•,. i / i 3
1
I
I /
co
,,· I ••,
I '•, I
1
I
I '-. , ,, I
!I / Co·,..,_ !I
I ,·
1
I '· I
H 3N ---T-- NH 3 H N --r--NH
3 i 3
Br NH 3
Trans-isomer Cis-isomer
bis (benzoylacetonato) beryllium (TT) complex 57. Mirror image is not superimposable hence, optical isomerism is
51. When the three ligands (with same donor atoms) are on the same possible.
triangular face of the octahedron, the isomer is calledfacial orfac
isomer.
The octahedral complex is facial orJae isomer.

a~ b

a~ b
b 58. The coordination compound [Co(en)2 C1 2 ]Cl doesn't show
In this complex, the three ligands are on the same triangular face ionisation isomerism.
of the octahedron. 59. When ligands are exchanged between metal atoms, coordination
52. [Cr(NH3) 5 NO2 ]Cl2 compound shows linkage isomerism because isomerism results. Hence, [Co(NH3\][Cr(C~ ] and
[Cr(NH3\; ][Co(CN)6 ] represents coordination isomerism.
it has NO2 group which is ambidentate ligand. It can be linked via
N atom (- NO2 ) or via O atom (--ONO) to form two different 60. Linkage isomerism is shown by those complexes w hi£h have an
isomers. ambidentate ligand such as NO 2, CN- and SCN etc. In
53. [Co(NO2 )(NH3 ) 5 ]Cl2 [Fe(NO 2))CIJJ, N is donor atom w hile in [Fe(ONO)3 C1 3 ] , 0 is
donor atom.
Pentaammine nitrito-N-cobalt (III) chloride.
54. K2 [PtC16 ] 61. The IUPAC name of the compound [CuCl 2 (CH3NHihl is
dichloro bis (methy lamine) copper (ID.
Potassium hexachloroplatinate (IV).
 2
Topic 3 Bonding in Coordination 3. (a) [Co(NH~ ] + in this ion, Co is present as Co2 + · NH3, being
Compounds strong field ligand, pair up d1e unpaired electrons.
Electronic configuration of
1. Plan T his problem includes concept of hybridisation using VBT,
VSEPR theory etc. Co2 + = 3d7 , 4s0 , 4p0
XeF4 , BrF4, [Cu(NH 3) 4 ] 2 +, [PtC1 4 ) 2 - are square planar as 3d 4s 4p
shown below.
I1l I1l I 11111I □ I I
Electronic configuration of Co 2
+ in = [Co(NH~ J2 +
3d 4s 4p

I1l I1l I1l I 1I I □ I I I I '--I _L___L____L__J___J

3d 4s 4p

I1l I1l I1l I1l I1l I [1] I1l I1l I1l I IL. .,-1~I----'----------------'--------
i
One unpaired
electron

Due to the presence of one unpaired electron, [ Co(NH3\; ]2+ is

paramagnetic.
(b) [MnBr4 f- In this ion, Mn is present as Mn 2 +. Br, being weak
field ligand, leave unpaired electrons of the metal ion as such.
Electronic configuration of
Mn2+ =3d5 ,4s0 ,4µ°
3d 4s 4p

11111111111 □ I I
Electronic configuration ofMn 2 + in (MnBr4 f- =

sp3 hybridisation

Due to sp3 hybridisation, shape of[MnBr4 f- is tetrahedral.

Hence, correct integer is (4). (c) Linkage isomerism occurs when two or more atoms in a
monodentate ligand may functions as a donor. Therefore,
2. Fe= 3d6, 4s2
[CoBr2 (enhr does not exhibit linkage isomerism.
3d 4s 4p 4d

I1l I 1111111I OD I I I I I (d) [Ni(NH3\; ] 2+ In this ion, Ni is present as Ni2 +

(Fe(H20)6]3+ =3d6 Electronic configuration ofNi2 + = [Ar] 3d8 4s0

3d 4s
I1l I1l I1l I 111I □
sp3d2 hybridisation
NH 3 is a strong field ligand, it can pair up electrons only if they
are more than 4 and less than 8.
Electronic configuration ofNi in

I 1l I 1l I 1I I I 0 I I I I
X X X X X
[Ni(NH 3 \ ] 2 + =
3d 4s 4p 4d
d 2sp 3 hybridisation
I1l I1l I1l I 111I 0 I xI x I x11
'----x~Ix-'-1---- ___L__J___J

sp3d2 hybridisation

Since, (n - I) d, i.e. 3d orbital does not take part in hybridisation,

sp 3d 2 hybridisation it is not an inner orbital complex. It is an outer orbital complex.
 Coordination Chemistry I 559
0 4p
4. In Cr(CO~ Cr is present as Cr 3d 4s
0
Cr or Cr = [Ar] 3d , 4s
5 1
I1lI1lI1lI 111I [ID I I
CO being strong field ligand pairup the unpaired electrons of Cr. [Ni(CO)4 ]=
3d 4s 4p

I 1l I1l I1l I I1lI1lI1lI1lI1lI 0 spI hybridisation

I I I
□
X X X
Cr= [Ar) 3

In this condition, number of unpaired electrons, fl= 0 ITT. [Pt(NH 3)2 Cl 2 ]

Magnetic moment, µ = ✓fl (fl + 2) Here, Pt is present in its ground state. NH3 being a strong ligand,
= ✓0(0+ 2)=0BM pair up the unpaired electron of Pt.
9 1
78 Pt= [Xe) 5d , 6s
5. In [FeF6 ]'- and [Fe(CN~ ]'- both, Fe is present as Fe3+.
Pt2 + =[Xe] 5d8 , 6s0
FeJ+ = [Ar ) 3d5, 4s0 , 4p0 , 4d 0
5d 6s 6p
11111111111 □ I1lI1lI1lI 111I □ I I
F- being a weak field ligand, is not capable to pair up these [Pt(NH3)4 Cl2 ] =
unpaired electrons but CN- does this.
Hence, is case of I1lI1lI1lI1l I I 0 I I IX X X

[FeF6]'- = [Ar]
dsp2 hybridisation
3d 4s 4p 4d
I 111111111IE [lxxlxxlxxllxxlxxl I IV. [CoF6 ]'-
F- F- F- F- F- F- Here, Co is present as Co3+ ion, F being weak field ligansd is
Number of unpaired electrons = 5 unable to pair up its unpaired electrons.
Magnetic moment, µ 1 = ✓5 (5 + 2) = ./35 Co3+ =[Ar] 3d,4s0
In case of 3d 4s 4p 4d
[Fe (~]3- =[Ar], 3d 5,4s 0 l1l l 1 1 1 1 1 1 1 1 □ ~1~I~l~I~ I ~I~

CW CW CN- CW CW CW
I 1lI 1111111I [J I xI xI xI I~x ~Ix~I ~~
Number of unpaired electron= I
sp3d 2 hybridisation
Magnetic moment, µ 2 = ✓l (I + 2) = ✓3
V. [Fe(CO)5 ]
. µ, ./35
Ratio ofµ 1 and µ 2, - = r::: = 3.41 "' 3 Here, Fe is present in its ground state. CO being a strong field
µ2 v3
ligand, pair up the unpaired electron
6. I. [Co(NH 3\]' + 26Fe = [Ar] 3d , 4s2
6

Here, Co is present as Co3+ ion. NH3 being strong field ligand

3d 4s 4p
pair up the unpaired electrons of Co.
27 Co=[Ar)3d 4s
7 2
⇒ Co3+ =[Ar)3d6 4s 0
I1lI1111111I [ID I I
3d 4s 4p [Fe(CO) 5 ] =

I1lI 1111111I □ I I I1lI1lI1lI1l I I 0 I I I I

X X X X

[Co(NH~f + = dsp3 hybridisation

I1l 1l 1l I I I 0 I I I I
I I X X X X X 7. Cis-platin is a life saving drug with the molecular formula of
Pt(NH:i)2 Cl 2 . It is also called cis-diamminedichloridoplatinum
d2sp3 hybridisation (TI). From its molecular formula, its shape seems to be tetrahedral
as its coordination number is 4 but tetrahedral complexes do not
II. [Ni(CO)4 ] show geometrical isomerism (because the relative) positions of
Here, Ni is present in its ground state. CO being a strong field the ligands attached to the central metal atom are same with
ligand, pair up the unpaired electrons of Ni respect to each other). Since, it shows geometrical isomerism
2
28 Ni = [Ar] 3d 4s
8 (cis and trans platin) are optically active. Since, it is optically
active, therefore it must be square planar.
560 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Hence, its molecular shape is square planar, with the bond angles
around the centre molecule, Pt equals to 90° w hile between the
nitrogen and hydrogen atoms it is approximate ly 109°.5. Thus,
dsp 2
Pt(NH 3)iC12 is a square planar complex.
The above electronic arrangement gives dsµ2 hybridisation and
c~·'\'. 7 NH3 c~'\-. 7 NH3 therefore, square planar geometry to the complex.
. Pt ' : Pt :
11. Number of unpaired electrons in Fe = 5
Cl / . -\_:°NH3 H
3
/ . - \_:'Cl Magnetic moment, µ = .Jn(n + 2) = .J5(5 + 2)
Cis-isomer 'lrans-isomer
= ../35 =5.9BM
8. The coloured nature of solutions of coordination compounds is 12. For[NiCl4 f-
explained on the basic of crystal field theory. According to this
theory, in such compounds, the energy difference between two H = -l (number of valence electrons m
. central atom + number of
sets of d-orbitals is usually small. So, excitation of an electron 2
from lower energy to higher energy is very easy and can be monovalent atoms surrounding central, atom + charge on ion
achieved even by the absorption of low energy radiations of with sign)
1
v isible region. As a result of the absorption of such selected = 2 (6 + 4 - 2) = 4
wavelengths of visible light, the complexes appeared coloured.
9. Spin only magnetic moment = .JN (N + 2) BM. when N is the :. Hybridisation for Ni in [NiC1 4 ]2- is sp3.
munber of unpaired electrons. In the presence of weak ligand (as 13. Paramagnetism depends upon the munber of unpaired electrons.
H2O, c 1-, F-) there is no pairing of electrons, and electrons Since, CN- is a strong field ligand, it causes pairing of electrons.
donated by ligands are filled in outer vacant orbitals. In the
presence of strong ligand (as CN-, CO, NH3, en ) electrons are (a) In [Fe(CN~ ]3 - , Fe3 + = Ar [3d 5 ]
paired and electrons from ligands are filled in available inner
orbitals. = [Ar] [ 1l [1l [ 1 [
Atomic Unpaired Magnetic One tmpaired electron.
Complex ON EC
no.of electrons moment
(b) In [Cr(CN~] 3 -, Cr 3 + = Ar [3d3 ]
P : [FeFd - 26 +3 [Ar]3d 5 5 ..J35BM
weak ligand = [Ar] [ 1[1[1[
Q: 23 +2 [Ar] 3d3 3 ✓ISBM
[V (H2O~f+ Three unpaired electrons.
weak ligand (c) In [Co(CN~] 3 - , Co3 + = Ar [3d 6 ]
R: 26 +2 [Ar] 3d6 4 ✓24BM
[Fe(HP)6 f+ = [Ar] [ 1l [1l [1l [
weak ligand No unpaired electron.
Thus, order of spin-only magnetic moment is Q < R < P. (d) In[Sc(CN~ ] 3 -Sc3 + =Ar(3d)o
10. In the given complex, N iC1 2 {P(C2H 5 ) 2 (C2H 5 )h, nickel is in + 2
= [Ar] ~[~~~~
oxidation state and the ground state electronic configuration of
N i2 + ion in free gaseous state is No unpaired electron.
3d8 4s 0 4p0 Hence, [Cr(CN\]3 -will show maxiimun paramagnetism.
Ni2+= I1l I1l I1l I1 I1 I □ I I 2
14. Ni + + 4CN' - [Ni(CN)d-

For the given four-coordinated complex to be paramagnetic, it Here, Ni 2+ has d 8 -configuration w ith CN- as strong ligand.
must possess unpaired electrons in the valence shell. To satisfy 3d8 4s 4p
this condition, four lone pairs from the four ligands occupies the
four sp3 hybrid orbitals as I1l I1l IRIRI•\__dsp
~ EJ CT •I
2~

d 8 -configuration in strong ligand field gives dsp2 hybridisation,

spJ hence square planar geometry.
Ni 2+ + 4CI- - [NiC14 ] 2-
Therefore, geometry of paramagnetic complex must be
Here Ni 2+ has d 8-configuration with c 1- as weak ligand.
tetrahedral. On the other hand, for complex to be diamagnetic,
there should not be any unpaired electrons in the valence shell. 3d8
This condition can be fullfilled by pairing electrons of3d orbitals
against Hund's rule as I 1l I 1l I 1l I 1I 1I EJ I• • I• • I• • I
\__ sp2 _ _ _...,,
 Coordination Chemistry I 561
d 8 -configuration in weak ligand field gives s/ hybridisation, hence
tetrahedral geometry.
Ni2+with H 2O forms [Ni(H 2O\s f+ complex and H 2O is a weak ligand. I 1l I 1l I 1l I 111 I
3d sp3

I1l I1l I1l I 1 11 I 4d b

4s 4p
R 1-:-:~1 ..~I .. I I·· I·· I 4s0 4p

~ sp3d2 _ _ ___,
3d
Therefore, [Ni(H2O\ f+has octahedral geometry.
15. For a diamagnetic complex, there should not be any unpaired electron in
I1l I1l I1l I 1 11 I
the valence shell of central metal. 0 IxIxIx I
In K 3[Fe(CN\s], Fe (III) has d 5-configuration (odd electrons), hence it is 4st t4p
paramagnetic. In [Co(NH3 \ ]Cl3, Co (III) has d 6-configuration in a strong sp3
ligand field, 3
Four sp hybrid orbitals
hence all the electrons are paired and the complex is diamagnetic. sp3-hybrid orbitals, tetrahedral
In Na 3[Co(ox)J ), Co (III) has d 6-configuration and oxalate being a
Cl- is a weak ligand and thus unpaired e lectrons are not
chelating ligand, very strong ligand and all the six electrons remains paired. Lone pairs from 4 Cl- are accommodated in four
paired in lower t2g level, diamagnetic.
In [Ni(HP\ )C1 2 Ni (II) has 3d8 -configuration and H 2O is a weak ligand
s/ hybrid orbitals.
hence N = tmpaired electron = 2, paramagnetic
3d Magnetic moment (spin only)
= .jN (N + 2) BM= ✓8 = 2.828 BM
I1l I1l I1l I 1 11 I
4s 18. Based on spectrochemical series, ligands arranged in
R r:-1·•·1··1 increasing order of crystal field strength are as
~ sp3<J2 - -~ Paramagnetic NH3 < en < CN- < CO
19. In [CoFi'- complex ion Co3+ is s/d 2 hybridised. F- is
In KlPt(CN)4 ], Pt (TI) has d 8 -configuration and rn-
is a strong ligand, weak ligand and cannot pair up the d-electrons so,
hence all the eight electrons are spin-paired. Therefore, complex is complex is high spin. Due to four unpaired electrons it is
diamagnetic. highly paramagnetic.
In [Zn(H2O\](NO3 )i, Zn(II) has 3d 10 configuration with all the ten 20. In [Ni(CO)4 ), Ni is in zero oxidation state. It has
electrons spin paired, hence diamagnetic. tetrahedral geometry but is diamagnetic. In [Ni(CN)4 f-,
Ni is in + 2 oxidation state. It is dsp2 hybridised and have
....,.3 ~ [Cr(NH~6 ] + + 3CI-
3
16. [Cr(NH3\ ] Cl AgCI-L
Coordinate Ionisable
White precipitate square planar shape. The compound is diamagnetic.
sphere
21. Ni : 3d8 ,4s2 Ni 2+ : 3d8
Cr(24) =[Ar) 3d5 4s1
Since, Cl is a weak field ligand, it doesn't cause pairing of
Cr 3+ =[Ar ]3d3 , 4s0 electron.
Indicates lone-pair ofNH3 donated to Cr
(a) d 2sp3 hybridisation, octahedral, thus, correct. I 1l I 1l I 1l I 1 11 I □
3d3 4s 4p
(b) There are three upaired electrons, hence paramagnetic, thus correct.
(c) d 2sp3-inner orbital complex, thus incorrect. Number of unpaired electrons, n = 2
µ = .jn(n + 2) = .j2(2 + 2)BM = ✓8 BM
(d) Due to ionisable c1- ions, white precipitate with AgNO3, thus
correct. =2.82BM

Therefore, (c) is wrong. 22. The complex in which nd orbitals are used in
hybridisation, are called outer orbital complex.
17. [NiC1 4 F; oxidation munber ofNi,
(a) [Fe(CN\)4- =
x-4=-2
3d 4s 4p
x=+2
Ni<28l =[Ar ]3d 8
,
2
4s
[Ar) I1~I1~ I1~ IxIxI 0 IxIxIxI
d 2sp 3 (inner-orbital)
562 I Chapterwise & Topicwise Engineering Entrances Solved Papers

(b)[Mn(CN\ ]4- =
3d 4s 4p oxidation state of Sc is + 3.
[A r] I 1l I 1l I 1l I xlI 4x 1 ixl xj x1xI
I
4 t t2 4 4 4 3 Sc (ground state)
3d
11I I I I II ] I I I
4s 4p

d2sp3 (inner-orbital)
Sc3+ ~I__,_I__,_~__,__,I D .__I__,___.___,
3d 4s 4p ·: Sc3+ has no unpaired electron.
(Ar) I1~ I1~I1~IxIxI 0 IxIxIxI :. [Sc(H2O\ J3+ is diamagnetic and colourless.
d 2sp3(inner-orbital)
26. When ligands are arranged in ascending order of crystal field
(d) [Ni(NH 3\f+ = splitting energy, !Y,., they produce a spectrochemical series.
In comparison to H 2O, Cl is strong cr-donor and good n-acceptor,
3d 4s 4p 4d
therefore it is a strong ligand than H 20.
[Ar] I1~I1~I1~ I 111 I0 IxIx IxI~Ix~Ix~I~~ Hence, in the spectrochemical series CI is above than water.
sd 3d 2 (outer-orbital)
27. (a) (Ni(CN)4 r- 2
23. (a) In [Cu(NHj)4 f+, Cu is present as Cu 2+ N i (28) = [Ar] 3d8 4s
2
Cu + = (Ar ]3d9 4s0 Ni2+ = (Ar] 3d8 , 4s
3d8
3d 4s 4p 11~ 11~ 11~ 11 11 I
(Ar) I1~I1~I1~ I1~ IxI 0 IxIx11I
Since, CN- is a strong field ligand, it causes pairing of electrons.
dsp 2 hybridisation 3d 3s 3p
⇒ square planar geometry :. [NiCN4]2- = (Ar] l1 ~11~11~11~l xl ~ll xlxl
(NH 3 being a strong field ligand shifts one electron from CN- CN-CN-CN-
3d-orbital to 4p-orbital.) dsp'l hybridisaLion
(No unpaired electron
(b) In [Ni(CO)4 ], CO is a neutral ligand. = diamagnetic)
(c) In [Fe(CN\f- , Fe is present as Fe3+ . (b) Chlorophyll contains Mg2+ ion.
Fe3+ = (Ar] 3d 5 4s 0
(c) Ziegler-Natta catalyst is Ti4+ + (C2 Hs)3 AI.
[Fe(CN);]3- = (Ar]
(d) [NiCld-
(Ar) I1~ I1~ 11IxIxI 0 IxIxIxI In this case, c1- is a weak field ligand, so doesn't cause pairing.
Hence,
3d 4s 4p
Thus, its hybridisation is d2sp3 not sp3d2, i.e., it is an inner orbital [NiCI4)2- = [Ar] I1~ I1~ I1~ 1111I ~ 11 xIxIxI
~ d Cl Cl Cl Cl
complex. U npatre
electrons sp3 hybridisation
(d) [Co(en)3 y+ contains tota l 36 electrons, i.e. follows EAN mle.
(e) Deoxy haemoglobin is non-planar
24. Coordination number is the number of ligands in the coordination
28. (Fe(CN);]4- ~ Fe + ~
2
1s3,2s2,2p6, 3s2, 3/, 3cl'
sphere. Hence, the coordination number of cobalt ion in
[Co(H2 O)4SO3 ]Cl is 5. (strong field)
Let the oxidation number of Co is x. 4d
X + 4(0) + (- 2) + (-1) = 0

x+0-2-1=0 ⇒ x=3
l1~11~11~l~l xl ~l!.xlxlxj
3d d'-sp3 4p
Number of electrons in d-orbital are six.
3,f CN- is strong field ligand, it causes pairing w hi le C2 o!- and F-
Co3+ = I1~ I1I111111 are weak field ligands and don ' t causes pairing.
4
Numbre of unpaired electrons ind-orbital are 4 because H 2O is a Hence, [Fe(CN)t; ] - due to the absence of unpaired electrons is
weak ligand and therefore, pairing of d-electron is not possible. diamagnetic.
 Coordination Chemistry I 563
4
29. Cl, being a weak field ligand, does not cause pairing of 34. d Fonns outer complex in high spin and fonns inner complex in low
d-electrons of the metal atom and thus, fonns outer orbital spin. It cannot form octahedral complex.
complex as. d 6 In low spin it fonns inner octahedral complex and in high spin
In [Fe(Cl\ ] 3-, Fe is present as Fe3+ fonns outer octahedral complex.
Fe3+ = [Ar]3d5 4s0 4 µ° d 8 Fonns only outer spin octahedral complex.

35. In K 3[Co(C03h], cobalt shows the + 3 oxidation state i.e. (d") ion.
111111111 11 □ ~I~ Hence, Co(+ 3) has four unpaired electrons so, it is paramagnetic.
3-
[Fe(Cl\] = The magnetic moment of Co(+ 3)
3d 4s 4p 4d in K 3[Co(CO:i)3 ] = .Jn(n + 2) BM= ,J4(4 + 2) BM= 4.9 BM
[Ar] 11 11 11 11 11 I 0 I xIxIxI ~Ix~Ix~I~~ where, n = number of unpaired electrons
sp 3 c/2hybridisation co~- is a weak field bidentate ligand, so 3CO~- ligands occupy six

30. [H2EDTAf- + Mg2+ ~ [MgEDTAf+ + 2W

orbitals, thus it shows s/d 2 hybridisation and octahedral in shape.
(a) In this complex, four donor sites are occupied by oxygen 36. For [Ni(CN)4 ]2-, oxidation state of Ni is+ 2.
and two donor sites are occupied by nitrogen. CN- = strong field ligand
(b) This complex is six coordinated. Ni 2+ (ground state)=
( c) Complex [MgEDTA] 2- is colourless. 3d8 4s0
(d) Increase in [H+ ], decreases pH of the solution. 11~11~11~1 11111 J
31. CFSE (crystal field splitting energy) for octahedral complex,~ 0 In [Ni(CN)4 ] 2-
depends on the strength of negative ligand. Spectrochemically it 4s

00
3d 4p
has been found that the strength of splitting is as follows
CO> rn- > N02 > en > NH3 > PY > Ni +=
2
I1~ I1~I1~I1~lxxlI~
CN CN CN CN
Ncs- > H20 > 0 2- > ox2- > oH- > r >
dsp2
CI- > SCN- > S2- > Br- > 1
dsp2 hybridisation, i.e. square planar geometry, zero unpaired
Therefore, magnitude of ~0 will be highest in case of electron, i.e. zero magnetic moment.
[Co(~] 3- .
For[MnBr4 f-,oxidation state of Mn is+ 2. Br- =weak field ligand
32. In both [Co(NH~] 3+ and [CoF6 ] 3\ Co is present as Co3+. Mn 2+ (in ground state)
Thus, the electronic configuration of Co is 3d 4s
7
27 Co= [Ar] 3d , 4s
2
1 1 1 1 1 1 1 1 111 □ ~1~~
27 Co +
3
= [Ar] 3c/', 4s 0 In [MnBr4 ] 2-,

In case of [Co(NH~]3+, NH3 is a strong field ligand, so 2

Mn += l11111111 1l[ § I Jxxlxxlxxl[
pairing of electrons in 3d-orbital takes place. Bf Bf Bf Bf
3
27 Co + =[Ar]3d ,4s
6 0 sp3
3d6 s/ hybridisation, i.e. tetrahedral geometry, five unpaired electrons, i.e.
magnetic moment = 5.9
~
(no unpaired electron)
Co3+ in ground state =[Ar ],3d7 ,4s2
3d 4s 4p
In [CoF6 j3+, Fis a weak field ligand, thus doesn't cause pairing.
Hence,
11~ 1111 1111 I[ 11 I I
3 0 For [CoF6 ]3-, oxidation state of Co is +3.
27 Co + = [Ar] 3c/', 4s
F- =weak field ligand in [CoF6 ] 3-
3d 6 l1~11l1 l1l1I 4s 4p
4 unpaired electrons Co3+= I1~ 11 11 1111I §:I lxxlxxlxxl
33. Hybridisation Geometry of complex
sp3 Tetrahedral xxxx
dsp2 Square planar F"' F"'

d\p3 ,?,;.
Octahedral
2
s/d hybridisation, i.e. octahedral geometry four unpaired
sp2d2 Not possible
electrons, i.e. magnetic moment is 4.91 BM.
564 I Chapterwise & Topicwise Engineering Entrances Solved Papers
37. F- is a weak field ligand and [FeF6 ] 3- is an outer-orbital complex (c) [Fe(~]3- ion
[FeF6 ] 3- complex= 3d 4s 4p

3d 4s 4p I1~ I1~ I1~ I XI I 0 I I XI XI

X X

111 1111111IIEJ lxxlxxlxxll d 2sµ3- hybridisation

4d 4d

EE],______.__I~
II I I I I
sp3d2
(d) [Cr(NHJ\f+ ion
[FeF6 ]3- shows sp3d 2 hybridisation and Fe3+ has five unpaired
3d 4s 4p
electrons. Tn [Fe(CNS\f-, CNS- is a strong field ligand and is
inner orbital complex.
111111lxlxl GJl xl xlxl
2
d s/-hybridisation
[Fe(CNS),,]3- 4d
3d 4s 4p
I I
I1~ I1~ 11lxxlxxl I~ lxxlxxlxxll
NH3 and CN- are strong Iigands. So, they form their inner orbital
sp3d 2 -hybridisation
complex.
[Fe(CNS~f- shows d 2s/ hybridisation and has one unpaired
41. Cl- is a weak ligand but Cl- cause the pairing of electron with
electron.
large P t2+ and consequently give dsp2 hybridisation and square
Hence, the reaction
3
planar geometry.
[Fe(CNS),, ] - - [Fe~ ]:,..
42. Ferrocyanide ion [Fe(~]4-- is diamagnetic in nature hence
Takes place with increase in magnetic moment. K4EFe(CN),, ] complex has zero magnetic moment.
38. The electronic configuration Pt= [Xe]4 /4, Sd9 , 6s 1
3d 4s 4p
Pt2+ = [Xe] 4 / 14 , Sd 8 , 6s0
Fe atom I1~ 11 11 I 111 I [ill I I I
[Pt(CN)4 f- = [Xe]4/14
5d 6s 6p
Fe(II) 11~1111 1111 I D ~I~~
11~11~11~11~1xI 01 xI xi
dsµ2 hybridisation
[Fe(CN)6]4-- l1 ~11~11~lxxlxxl E] jxxlxxlxxl
~ square planar t t
or CN- CJ<
t t t t
CJ< CJ< CN-
2
No unpaired electron is present in [Pt(CN)4 ] - ion. d2,µ3 hybridisation
2
39. Paramagnetic character ox number of unpaired electrons. 25 Mn + 43. I. In Ni(C0)4, nickel is sp3-hybridised because in it oxidation
ion has maximum unpai red (five unpaired electrons) electrons.
state of Ni is zero. So, configuration of
So, [Mn(H 2 0),, ]2+ is most paramagnetic. 8 2
28 N i = Js2, 2s2,2p6, 3s2,3/,3d , 4s
40. Electronic configuration ofCo3+ ion 3d3 4s2 4p
3d 4,0 4p
11~11~11~111 111:111 I I
<a) 11~ 11 1111 11I □ I I I 3d10 4s 4P
3d
N i(C0)4 I1~ I1~ I1
~I1~I1~ I ~I I XI XI XI
~
3
sp -hybridisation
4s 4P 4d
II. In [N i(CN)4 ] 2 -, nicke l is present as Ni 2+, so its configuration
0 lxl xlxl lxlxl I
= 1s2, 2s22p6, 3s23/3d8
3d 4s 4p
F- is a weak ligand. It cannot pair up electrons w ith d-subshell
and forms outer orbital octahedral complex.
11~11~11~11111□ '--I~
3d 4s 4P

[Ni(CN4)] -11~11~11~11~1 XI 01 XIXI

(b) [Co(NH~f+ ion 2
3d 4s 4p
~11~~11~~11~1~
x1---,
xI ~ I IxIxIxI dsµ2-hybridisation

2
CN- is strong field ligand, hence it makes Ni 2+ electrons to be
d s/-hybridisation
4d paired up.
I I III. In [NiCl 4 y- species, nickel is present as Ni2+, so its
con figuration
= ls2, 2s2,2p6, 3s2,3p6,3d8
 Coordination Chemistry I 565
3d 4s 4p 3d 4s 4p

11~ 11~11~ 11 11 I □ I I I N i-atom I1~ I1~ I1~ 1 1 11 I [ill ~I~~

3d 4s 4p

[Ni(Cl4)] - 11~ I1~ I1~ 11 11 I 0 I I I I

----- Ni (ID I1~ I1~ I1~ 1 1 11 I □ ~I~~
2
X X X

----- EJ lxxlxxl
si-hybridisation 2
[Ni(CN4)] - I 1~ I 1~ I 1~ I 1~ lxxl
2
Cl- is weak field ligand, hence N i + electrons are not paired. t1si hybridisation
44. CN- is strong field ligand because it is an example of
It has no unpaired electron hence, its magnetic moment is zero.
pseudohalide. Pseudohalide ions are stronger coordinating
ligands and they have the ability to form cr bond and 1t-bond. 52. Configuration ofMn 2+ is [Ar] 3d 5
45. In [Mn(H2O)6] 2~ Mn is present as Mn 2+ or Mn (II), so its According to CFSE (crystal field stabilisation energy), in excited
2
electronic configuration state ofMn + ion, three electrons go in t'¾I level (dXJ" dy, and dzx)
= ts2, 2s2 2/, 3s23/3d5 and two electrons go in e8 level (d, and d
r X
2
- y2
).

3d 4s 4p 53. KiFe(CN\ ] ~ 4K+ + [Fe(CN\ ]4--

11 11 11 11 11 1[]1 I I The oxidation number of Fe in [Fe(CN\ ]4- is+ 2.
4d 2
Fe + = ts2, 2s22p6, 3s2 3p63d6, 4s0 4 p
I I I 3d6 4s 4p
In [Mn(Hp\] 2+, the coordination number of Mn is six, but
in presence of weak field ligand, there will be no pairing of
I1~I1~ I1~ I I I ~I I I I I
X X X X X
CNCN CN CNCNCN
electrons in 3d. So, it will form high spin complex due to presence
Since, CN- is a strong field ligand, pairing occurs and the
of five unpaired electrons.
hybridisation of[Fe(CN\ ]4-- is d
2
s/
and structure is octahedral.
In [Mn(H2O\ f+
54. Oxidation state ofNi in Ni(CO)4 is zero.
3d 4s 4p 4d
11 11 11 11 11 I ~ II I I I I I I I
X X X X X
3d 4s 4p

Unpaired electrons
Ni= I1~ I1~ I1~ 11 11 I ill11 I I
sp3i:l2-hybridisation
3d 4s 4p
46. In the formation of d s/
2
hybrid orbitals, two (11 - l)d orbitals of Ni= l1~11~ 11~ 11~ 11~ 1 1=1 I I I
e8 set, i.e. (n -1) d,2 and (n - 1) dx2 _ 2 orbitals, one ns and three s/-hybridisation
2
np(npx, npy and np,)orbitals combimitogether and form six d sp3
CO is a strong ligand. It causes pairing of electrons.
hybrid orbitals.
Hence, there is no tmpaired electrons in Ni(CO)4 •
47. N i(CO)4 and Ni (PPhJ)2 Cl 2 are tetrahedral in geometrical shape,
55. [Sc(CN\F
because coordination number of Ni is four in both cases.
2 1
Sc= 21 = ts2, 2s 2/, 3s23p6, 4s2, 3d
48. The ione pair of electron present with nitrogen w ill not be
available to be donated, as W will form NH/ in acidic medium. 3d 4s 4d

49. The primary valencies of N i, in the complexes [Ni(Cl4 )Y- and

3
Sc + = I I I ID I I
No unpaired electron
[Ni(CN)4 ]2- is same, i.e. (+ TI). Primary valencies are those
valencies w hich a metal exhibits in the formation of its simple
salt, these are non-directional. It is also referred as oxidation state 3d 4s 4p
of central metal atom. I
N i (G.S.) 1~ 11~ 11~ 11 11 1 [ill I I I
SO. In [Co(NH:i\J3+ the oxidation state of Co is+ 3. 3d 4s 4p
[Co(NH3)6J3+ Ni2+ 1~ I I1~ 1~ 11 1 1 I □ I I I
I
3d 4s 4p
I1~ I 1~ I 1~ lxxlxxl EJ lxxlxxlxxl
t?si hybridisation dsp2 hybridisation
square planar shape
[Co(NH3\]3+ does not contain unpaired electron hence, its
magnetic moment is zero. It has no unpaired electron hence, diamagnetic.
51. [Ni(CN)4 ] 2- ion has ds/ hybridisation, zero magnetic moment [Co(CN\F
and square planar structure.
566 I Chapterwise & Topicwise Engineering Entrances Solved Papers

3d 4s 4p 2 2 8
59. 28 Ni = (Ar]3s 3/4s 3d
Co Ground
state
11~ 11~ 11 11 11 I ill] I I I 2
Ni + 2
= (Ar] 3s 3/ 3d 8
3d 4s 4p
Co3+ 11~ 1 1 11 11 I I I□ I I I I I I I□ I I I I
11~ 1~ 1~ 1 1
'----------,---
3+ 3d 4s 4p
si
~~eto~~g 11~ 11~ 11~ 1 I I□ I I Nickel has two unpaired electrons and geometry is tetrahedral
due to sp3 hybridisation.
It has no lmpai red electron, so diamagnetic
60. 111 is roughly 4/9 times to 110 .
[Cr(CN\f-
61. The compounds of nickel are green coloured due to d - d
3d 4s 4p
transition in presence of ligand in Ni 2+ cations.
Cr Ground
state
11 11 1 ~ 11 11 1
3
q;J
p~I~ 1~1
4 62. Diamagnetic substances have all paired electron.
(a) Fe((:N\] 3-Oxidation state of Fe=+ 3
11 11 11 1 I I DJ l~l~I~
Cr3+
3d 4s 4p 3d 4s 4p
cr3+
(duetoCNl 11 ~ 11 I I I I □ l'---'l'---'I'---'
3
Fe + 11 11 11 11 11 ID I I I
4
It has one unpaired electron so, paramagnetic.
56. N i(CN)!-
d~=~~ri~ 11~ 11~ 11 1 I I □I I I
d2sp3 hybridisation
3d 4s 4p
Ni Ground
state
I I
11~ 11~ 1~ 1 11 I illJ I I I It has one unpaired electron and is paramagnetic.
3d 4s 4p (b) [NiC14 ]2- Oxidation state of Ni = + 2
Ni2+ 11~ 11~ 11~ 11 11 I□ I I I 3d 4s 4p
2
Ni +11~11~ 11~ 111 1 1 [11 I I
'-,-----v------
sp3-bybridisation
dsp2 hybridisation
square planar shape Jt has two unpaired electrons and is paramagnetic.
(c) Ni(CO)4 Oxidation state ofNi = 0
[NiC1 4 ]2-
3d 4s 4p
N i is in + 2 oxidation state.
3d 4s 4p
I I I I I
Ni (G.S.) 1~ 11~ 11~ 11 11 □
3d 4s 4p
Ni +
2
I I I I
11~ 1~ 11~ 1 1 □ I I I I~~~~~=-==--'
I I I I I .D
Pa~ring ot 1~ 1~ 1~ 1~
e due to :==:'I .:::::::::;
I I
sp3 hybridisation
tetrahedral shape CO group dsp2.bybridisation

It has no unpaired electron and is diamagnetic.

N i(CO)4
Oxidation state of N i is zero. (d) [MnC1 4 ] 2-Oxidation state ofMn = + 2

3d 4s 4p 3d 4s 4p
N i(O)
I
11~ 11~ 11~ 1 1 1 1 [ill I I I Mn2+ 1 I I1 I1 I1 I1 I D I I I ~

3d 4s 4p sp 3 hybridisation
Ni (pairing
of e lectrons 11~ 11~ 11~ 11~ 11~ 1
due to CO)
□
~=I=':::r' :. It is paramagnetic as it has five unpaired electrons.
sp3 hybridisation 63.
Complex Hybridisation
tetral:iedral shape

57.
[Ni(CO) 4 ] sp3
Hybridisation Shape
dsp2 Square planar [Ni(CN) 4 ] 2- dsp 2
sp3 Tetrahedral [CoF6 ] 3- sp3d 2
sp2 Trigonal planar [Fe(CN)6 ] 3- d2sp3
Hence, in tetrahedral complexes metal atom is s/ hybridised. 64. Haemoglobin is porphyrin complex of ferrous iron being
58. Number of unpaired electrons in (Fe(CN\] 4---is zero. coordinated to four nitrogen atoms and additionally coordinated
Thus, magnetic moment= .)fl (fl + 2) = 0 BM to a water molecule. The water molecule appears to be
replaceable reversible by a molecule of oxygen to give
(n =unpaired electrons) fl in (MnCl 4 ]2- = S, ✓'35 BM 2
oxyhaemoglobin. Fe + is diamagnetic due to strong field ligands.
flin [CoCl 4 ]2- = 3, ✓IS BM
 Coordination Chemistry I 567
Hence, number of unpaired electrons is five as F is weak ligand.
Unpaired Magnetic
65. Complexes Hybridisation
electrons moment Magnetic moment = .Jn (n + 2)
[Co(CN\)3- d
2
s/ 0 0 = .js (5 + 2) = 5.91 BM

[Fe(CN\Y- d s/
2
✓3BM 70. CN- and OH- are strong nucleophiles.
1
[Mn(~y- d 2sp3 2 ✓8BM However, [Fe(OH)5 f- is not formed, thus, Fe[CN)i;jl- is most
stable ion.
[Cr(CN\Y- d 2sp3
3 ✓15BM

Thus, least paramagnetism is in (a).

Topic 4 Bonding in Metal Corbonyls
66. (a) d 5 in strong field 1. CO forms synergistic 1t-back bonds with transition metals. It
includes three components to give a partial triple bond. A <J bond
n = unpaired electron = I
p eg is formed by the overlapping of non-bonding sp hybridised
electron pair ofC with the bonding orbital of d , sand p-orbitals of
metal. Filled d-orbitals of the metal also overlaps with a pair of1t
- - ~ 1 It2g anti-bonding orbitals of carbon of CO. To form such a bond, the
oxidation state of metal atom must be lower than two.
Magnetic moment = .Jn(n + 2) BM 2. For the formation of 1t back bond (which is generally exist)
= ✓3 BM= 1.73 BM between metal and the carbony l carbon, the oxidation state of the
metal must be lower than + 2. Thus, + 2 oxidation state is not
(b) d 3 in strong/weak field
p eg possible in metal carbonyls.
3. Chlorophy ll is a green pigment present in plant and contains
magnesium metal.
- - ~ 1 112g 4. The M - C 1t-bond in metal carbonyl which is fonned by the
n=3 donation of an electron pair from a filled d-orbital of metal into
Magnetic moment = ✓15 = 3.87 BM the vacant anti-bonding 1t-orbital of CO, strengthens the
M - C <J- bond. This is called synergic effect and is usually
(c) ct in weak field
p eg observed in metal carbony ls. Thus, [N i(CO)4 ] exhibits synergic
effect.
S. Al 2 (CiHs)i; + TiCl 4 is Ziegler-Natta catalyst.
~ t2g
6. Organometallic compounds are those in w hich metal is linked
n=4 directly with carbon. CH 3Li, methyl lithium due to the presence
of metal-carbon bond, is an organometallic compound.
Magnetic moment= .fiA = 4.90 BM
4 7. An organometallic compound is considered as a su bstance
(d) d in strong field
contains a carbon-metal bond, e.g. AliCH31.
8. Ti(C2H s)4 is an organometallic compound because there is direct
bonding of metal ion w ith carbon.
9. Metal carbonyl are regarded as the coordination compounds
n =2 formed by the donation of lone pair of electrons of CO into the
Magnetic moment= ✓8 = 2.83 BM suitable empty orbital of zero valent transition metals such as N i,
Fe etc.
67. Structures KiFe(CN\ ], K 3 [Co(~], K2 [N i(CN)4 ) are Therefore, the M--C bond is coordinate covalent.
diamagnetic. l 0. (a) Mn+ = 3d5 , 4s 1• Tn presence of CO effective configuration
68. In [CoC1 4 f- ion, central metal atom, i.e., cobalt is in + 2 = 3d6, 4s0.
oxidation state. Three lone pair of back bonding with vacant orbital ofC in CO.
7 2
Hence, 27 Co = [Ar) 3d , 4s (b) Fe0 = 3d6, 4s2. In presence of CO effective configuration
2
27 Co + = [Ar)3d7 = 3d8 .
11~ 11~ 11 11 11 I Four lone pair for back bonding with CO.

Hence, number ofunpaired electrons is three as CI is weak ligand. (c) Cr0 = 3d5 , 4s 1• Effective configuration = 3d6. Three lone
pair for back bonding with CO.
69. In the complex K 3[FeF6 ], Fe is present in +3 oxidation state.
(d) v - = 3d4 , 4s2. Effective configuration= 3d~ Three lone pair
26Fe=[Ar]3d6,4s
2
⇒ Fe3+ =[Ar] 3d5
for back bonding w ith CO.
11111111111 Maximum back bonding in Fe(CO)5 , therefore CO bond order is
lowest here.
568 I Chapterwise & Topicwise Engineering Entrances Solved Papers

11 . In the Grignard reaction magnesium metal forms an 18. Ziegler-Natta catalyst is an organometallic compound containing
organometallic bond. titanium. It is TiCl4 and (C2H 5) 3 AI. It is used in the preparation of
Dry ether polyethylene.
RX + Mg - ---. R- Mg- X
Grignard reagent 330-350 K , 1-2 aim
TiCI 4 + (CzH5h AI
12. (c) is Isomer of[Pt (NH3)zCl2 ] which is used as an anti-cancer
drug for treating several types of malignant tumours. + c H 2- CH2+n
Polyethylene
H 3N~ p Cl
19. Zeise's salt, K(PtCl 3 (C2HJ ] is a n-bonded organometallic
~ (cis -platin)
H 3N Cl compotmd. Its structure is as :
H'\,_ / H
13. Al(OC2Hs)3 doesn't have metal-carbon bond (i.e. it is not an
example of organometallic compound) c~
H H
I I
C~ ~ ----;;?'f
I
1

Pt ,' H
;-H
0 - 7- 7- H
H H H H
Cl ~ ---·::-~~•'c:t
I I / 20. CH 3MgI (Grignard reagent) is an organometallic compound due
H- 7 - 7 -0 - AI~ to C- Mg bond.
H H H H
I I Topic 5 Stability of Coordinations
0 - C- C- H
I I Compounds
H H
1. p4 for [ML4 f- can be written as
14. Chlorophyll contains Mg, hence (a) is incorrect statement.
15. Metal carbonyl organometallic compounds possess both cr and
p = [ML4]2- = 2.5 x 1013
4 [M2+ ][C ] 4
n-characters.
16. Estimation of calcium and magnesium is done by EDTA.
The overall formation equilibrium constant can be written as
2
[ ML ] -
17. Organometallic compounds have carbon-metal bond, hence K= 4
[M2+ ][L-1]4
CH 3Mgl, tetraethyl tin and KC4 H9 are organometallic
compounds while C2H 50Na is not an organometallic compound K=P4 = 2.5x l 013
due to absence of carbon-metal bond.
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Haloalkanes and Haloarenes
QUICK REVIEW
Alkyl Halides
• Alcohols on treatment with halogen acids gives alkyl
halides.The reactivity order of alcohols being 3° > 2° > 1°
while that of halogen acids being HI> HBr> HCL
• Pure alkyl chlorides are prepared by the action ofSOCl 2 on
alcohols in the presence of pyridine.
ROH R-Cl + soit + HCli
Escape
• Iodination of alkanes is reversible process, hence
formation of iodoalkanes is possible in the presence of
oxidising agent like HI03 which oxidises the HI produced.
• Alkyl fluorides are generally prepared by halide exchange
reaction (Finkelstein reaction and Swarts reaction), e.g.
Acetone
R-Cl + Nal RI + NaCl
2CH3 CH2 Cl + Hg 2F2 ~ 2CH3 CH 2 F+Hg2 Cl 2
• Addition of halogen acids to unsymmetrical alkenes takes
place according to Markownikoff's rule. However, in the
the presence of peroxide such as (C6 H5 COO)i, addition of
HBr takes place against Markownikoff 's rule.
Nucleophilic Substitution Reaction
It in alkyl halides proceed either by SNl or by SN 2 type
mechanism.
• In SN 1 type reaction, rate of reaction is dependent on the
concentration of alkyl halide. In SNI reaction, partial
racemisation occurs with inverted product predominant in
yield.
• Reactivity of halides towards SN 1 reactions is as follows :
Benzyl/allyl > 3° > 2° > 1°.
• SN 2 type reaction proceed in one step and rate of the
reaction depends on the concentration of alkyl halide as
well as nucleophile. In SN2 reaction, only inverted product
is formed.
• Reactivity of halides towards SN2 reactions is as follows:
J O > 2° > 3° > Neo-pentyl halides
Reaction with KCN and AgCN
• Alkyl halides when react with metal cyanide such as KCN
give alkyl cyanides as main product because KCN is
predominantly ionic and both C and N atoms are in a
position to donate lone pair but the attack takes place
mainly through C-atom because C--C bond is more stable
than C--N bond. On the other hand, alkyl halides when
react with AgCN give isocyanides as main product because
AgCN is mainly covalent in nature and only N-atom is free
to donate lone pair.
• Dehydrohalogenation It is governed by Saytzeff's
rule. It states that dehydrohalogenation occurs in such a
way that the major product is more highly substituted
alkene. It means major product is the one where number of
H-atoms across the double bond is minimum, e.g.
Ale. KOH
- KBr, -Hf)
CH 3 -CH= CH-CH3
~
C (80%)
CH3 -CH2 -CH=CH2
(20%)
Ease of dehydrohalogenation among halides 3° > 2° > 1°.
570 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Reaction with Metals
• Alkyl chlorides, bromides and iodides when react with Mg
in the presence of dry ether give alkyl magnesium chlorides,
bromides and iodides respectively. These compounds are
known as Grignard reagents. These are highly reactive and
react with any source of proton to give hydrocarbons.
Allylic Substitution
• Allylic substitution, e.g. allylic bromination can be carried
out by treating alkene with N-bromosuccinirnide (NBS)
and allylic chlorination can be carried out by treating
alkene with sulphuryl chloride at 475 Kin the presence of
light and traces of organic peroxide.
Polyhalogen Compounds
Carbon compound having more than one halogen atom are
usually refered to as polyhalogen compounds.
C hloroform
• It is prepared either from CH 3 COCH3 or CH3CH 2 OH or
CH3CHO. These compounds on heating with a paste of
bleaching powder and water gives chloroform.
CHC1 3 + (HCOO)iCa
• Chlorofom1 on oxidation gives phosgene gas.

CH 2= CH-CH2 -Br ~ CH 2 = CH-CH3

/av
2CHCl 3 + 0 2 ~ 20= C<CI +2HC1
Chloroform Cl
Phosgene or
carbonyl chloride

• Phosgene is harmful poisonous gas. Therefore, to check

the oxidation of chloroform, it is stored in dark coloured
Aryl Halides
bottles filled up to brim.
• These can be prepared from benzene diazonium chloride
through Sandmeyer reaction or Gattermann reaction. In DDT
Sandmeyer reaction, Cl ofCuCl is attached to benzene ring. • Chlorobenzene on reaction with chloral in the presence of
• Direct halogenation of benzene is carried out in the 80% H 2 SO4 gives DDT.
presence of halogen carrier. The function of halogen C6H5Cl + CCl3CHO 80% H2S04
carrier is to generate the electrophile for the attack.
Cl 2 + FeC1 3 ~ Cl++ FeCI;j c1,c~--@c1
• Side chain chlorination of ethyl benzene gives
1-chloro- l-phenyl ethane is the major product and
l-chloro-2-phenyl ethane is the minor product because
benzylic free radical (formed in first case) is more stable Cl
DDT (insecticide)
than 1° free radical (formed in second case).
• Ary! halides and vinyl halides (CH 2 = CH-X)are less • IUPAC name of DDT is 2, 2-bis (4-chlorophenyl)-1,1,
reactive than alkyl halides and are not easily hydrolysed . I -trichloroethane. It is non-biodegradable. It slowly
changes to another compound 2, 2-bis-(4-chlorophenyl)- 1,
• Presence of electron withdrawing groups like
1-dichloroethene by the loss of one molecule ofHCl which
- NO2 , -CN, - COOH etc., in o and p -positions of
hinders with the egg shell fom1ation of birds and eggs
halogen atom, makes the halogen active and easily
break before hatching.
replaceable by other nucleophile while presence of electron
releasing group like -NH2 , - R etc., deactivate nuclear
halogen towards nucleophilic substitution.
 Topic 1
Methods of Preparation of Alkyl Halides
2012
1. Which one of the following is not fom1ed when a mixture (c) 2, 2-dimethye I butane and 2-methy I pentane
of methyl bromide and bromobenzene is heated with (d) 2, 3-dimethy I butane and 2-methy 1 pentane
sodium metal in the presence of dry ether? [KCET] (e) 2-methyl pentane and 2, 2-dimethylbutane
(a) Diphenyl {b) Propane 5. Number of monochloro derivatives obtained when
(c) Toluene (d) Ethane neo-pentane is chlorinated, is [J &K CET]
(a)one (b)two
2009 (c) three (d) four
2. The best method for the conversion of an alcohol into an
6. The catalyst used in the preparation ofan alkyl chloride by
alkyl chloride is by treating the alcohol with [Manipal]
the action of dry HCI on an alcohol is
(a) PCl 3
(a) anhy. AlC1 3 [Jamia Millia Islamia]
(b) PC1 5
(b) FeCl 3
( c) SOC! 2 in the presence of pyridine
(c) anhy. ZnC1 2
( d) dry HCl in the presence of anhydrous ZnCI 2
(d) Cu
3. The final product, in the below reaction, is [OJEE]
NH2 2007
Ao
LS:2,J BrifOW X NaNOi/HCI
X ~Z
HBF3
7. The molecular formula ofdiphenyl methane

Q - c H2 - 0 i s C13H 12 _

F
How many structural isomers are possible when one of the
Br*Br hydrogen is replaced by a chlorine atom? [Manipall
(a) ~ (a)6 (b)4
(c)8 (d)7
Br
2005
Br Cl

©t:'
8. Of the five isomeric hexanes, the isomer which can give
(c) r:§(F (d)
two monochlorinated compounds is
(a) 2-methy I pentane
[AIEEEJ

(b) 2, 2-dimethy I butane

(c) 2, 3-dimethyl butane
( d) n-hexane
2008
9. Tertiary butyl alcohol gives tertiary butyl chloride on
4. Of the isomeric hexanes, the isomers that give the minimum treatment with [OJEEJ
and maxin1wn number of monochloro derivatives are
(a) cone. HCl/anhy. ZnC1 2
respectively [Ke rala CEE]
(b)KCN
(a) 3-methyl pentane and 2, 3-dimethyl butane (c) NaOCI
(b) 2, 3-dimethy 1 butane and n-hexane (d) Cl 2
 Topic 2
Properties of Alkyl Halides
2014
1. In SN 2 reactions, the correct order of reactivity for the 5. An incorrect statement with respect to SN! and SN2
following compounds CH 3 Cl, CH 3 CH2 Cl, (CH 3 )z CHCI mechanisms of alkyl halide is [KCET]
and (CH 3 h CCI is [JEE Main]
(a) a strong nucleophile in an aprotic solvent increases
(a) CH3 CI > (CH3 h CHCI > CH2 CH 2 CI > (CH 3h CCI the rate or favours SN2 reaction
(b) CH 3 Cl > CH3 CH2 Cl > (CH 3 h CHCI > (CH 3 h CCI (b) competing reaction for a SN2 reaction is
(c) CH3 CH 2 Cl > CH3 Cl > (CH 3 ) 2 CHCI >(CH3 ) 3 CCI rearrangement
(d) (CH 3 ) 2 CHCI > CH 3 CH 2 Cl > CH 3 Cl > (CH 3 h CCI (c) SN! reactions can be catalysed by some Lewis acids
2. What will be the product of the reaction, (d) a weak nucleophile and aprotic solvent increases the
rate or favours SNI reaction
CH 3
6. Which of the following haloalkanes would undergo
I
H 3 C - ~ Br + Na-0-CH 3 ~ ? reaction faster? [AMU]

I
CH 3 Q-cH2c1Q-c1
[BITSAT]

(a) CH3 -C= CH 2 I. II.

I ~I ~Cl
CH3
CH 3 III. IV.
I (a) Only I (b) Only II
(b) CH 3 -O-r-CH3 (c) Only III (d) Only IV
7. Which one of the following is more readily hydrolysed by
CH3
SN 1mechanism? [EAMCET]
(c) CH3 - CH 2 - CH 2 -CH3
(a) (C6 H 5 )i C(CH3 )i (b) C 6 H 5 CH 2 Br
(d) CH 3 - r - CH 3 (c) C 6 H 5 CH(CH3 ) Br (d) (C6 H 5 ) 2 CHBr
CH 3 8. Anti-Markownikoff's addition ofHBr is observed in
(a) propane [J&K CET]
3. Arrange the following compounds in the increasing order
(b) but-2-ene
of their boiling points. [BITSAT]
(c) pent-2-ene
CHr,...._ (d) All of the above
I. CH<" CH- CH2Br
II. CH3CH2 - CH2 - CH2 - Br 2013
CH3 9. Which of the following alkyl halides is used as a
I methylating agent? [KCET]
III. CH3- T - CH3
(a) C2 H 5 Br (b) C 6 H 5 Cl (c) CH3 CI (d) C 2 H 5 Cl
CH3 10. The order ofreactivities of methyl halides in the formation
(a) II < I < III (b) I < II < III of Grignard reagent is [KCET]
(c) III < I < II (d) III < II < I (a) CH 3 l > CH 3 Br > CH 3 CI
4. Which reagents would you use to carry out the reaction (b) CH 3 Cl > CH 3 Br > CH 3 I
(c) CH 3 Br > CH 3 CI > CH 3 I
Ethyl benzene~ 2 and 4-chloro- l -ethyl benzene?
(d) CH 3 Br > CH 3 l > CH 3 Cl
(a) Cl 2, light and heat [Manipal]
11. Ethyl iodide when heated with sodium in dry ether gives
(b) Cl 2 , FeC13
pure [OJEE]
(c) SOCl 2
(d) C2 H 5 CI, AIC1 3 (a) C4 H 10 (b) C 2 H 6 (c) C 3 H 8 (d) C 2 H 5 OH
 Haloalkanes and Haloarenes I 573
2012
12. 2-bromopentane with ale. KOH yields a mixture of three 20. Which one of the following forms propane nitrile as the
alkenes. Which of the following alkene is predominant? major product? [KCET]
(a) 1-pentene (b) Cis-2-pentene [BITSAT] (a) Ethyl bromide+ alcoholic KCN
(c) Trans-2-pentene (d) Cis-1-pentene (b) Propyl bromide + alcoholic KCN
(c) Propyl bromide + alcoholic AgCN
13. Alkyl halide is converted into alcohol. This is an example
(d) Ethyl bromide+ alcoholic AgCN
of ...... reaction. [OJEE]
21. Grignard reagent is not prepared in aqueous medium but
(a) addition (b) displacement
(d) complex prepared in either mediun1, because [RPET]
(c) substitution
(a) the reagent is highly reactive in ether
2011 (b) the reagent does not react with water
14. The product of reaction between alcoholic silver nitrite (c) the reagent becomes inactive in water
with ethyl bromide is [Manipal] (d) the reagent reacts with water
(a) ethene (b) ethane 2009
(c) ethyl nitrile {d) nitro ethane
22. An alkyl halide (RX) reacts with Na to fom1
15. Which halide does not get hydrolysed by sodium
4, 5-diethyloctane. Compound RX is [Kerala CEE]
hydroxide? [MP PET]
(a) CH 3 (CH 2 h Br
(a) Vinyl chloride (b) Methyl chloride
(b) CH 3 (CH2 )iCH(Br)CH 2 CH3
(c) Ethyl chloride (d) Iso-propyl chloride
(c) CH 3 (CH 2 hCH(Br)CH 3
16. Alkyl iodide reacts with NaCN to give alkyl cyanide and
(d) CH 3 (CH2 ) 5 Br
small amount of alkyl isocyanide. Fom1ation of these two
(e) CH 3 Br
products is due to the [MP PET]
23. Which of the following compounds has the highest boiling
(a) ionic character ofNaCN
point? [OJEE]
(b) nucleophilic character ofCN-
(c) ambidentate character of CN- (a) CH 3 CH2 CH 2 CI
(d) electrophilic character of CN- (b) CH 3 CH 2 CH2 CH 2 Cl
(c) CH 3 CH(CH3 )CH 2 Cl
17. Following is the substitution reaction in which -CN
(d) (CH3 h CCI
replaces - CL

R -Cl + KCN ~ R -CN + KC!

2008
Alcoholic 24. The organic chloro compound, which shows complete
To obtain propane nitrile, R-Cl should be [KCETJ stereochemical inversion during an SN2 reaction is [AIEEE]
(a) chloroethane (b) 1-chloropropane (a) (C2 H 5 ) 2 CHCI (b) (CH 3 hCCI
(c) chloromethane (d) 2-chloropropane (c) (CH 3 ) 2 CHC1 (d) CH 3 C I
18. Which of the following is not true for the hydrolysis of 25. t-butyl chloride preferably undergo hydrolysis by [BITSAT]
t-butyl bromide with aqueous NaOH? [KCET] (a) SNI mechanism
(a) Reaction occurs through the SNI mechanism (b) SN2 mechanism
(b) The intermediate formed is a carbocation (c) Any of(a) and (b)
(c) Rate of the reaction doubles when the concentration (d) None of the above
of alkali is doubled 26. I , 2-dibromoethane reacts with alcoholic KOH to yield a
(d) Rate of the reaction doubles when the concentration productX. The hybridisation state of the carbons present in
oft-butyl bromide is doubled X respectively, are [VITEEE]
2010 (a) sp, sp (b) sp 3 , sp 3
2
19. 9.65 C of electric current is passed through fused (c)sp 3 , sp (d)sp 3 , sp 2
anhydrous magnesium chloride. The magnesium metal
thus, obtained is completely converted into a Grignard 27. In the reaction, 2A + dry silver oxide~ ether+ 2Ag X
reagent. The number of moles of the Grignard reagent A is a /an [MHT CET]
obtained is [KCET]
(a) primary alcohol (b) acid
(a)5 x l0- 4 (b) l xl0- 4
(c)5xl0- 5 (d)Ixl0- 5
(c) alkyl halide (d) alcohol
574 I Chapterwise & Topicwise Engineering Entrances Solved Papers
28. Alkyl halides are less soluble in water because [OJEEJ Codes [EAMCETJ
(a) they ionise in water A B C D A B C D
(b) they do not form H-bonds with water (a) 5 3 4 1 (b) 1 2 3 4
(c) they are highly viscous (c) 3 4 1 2 (d) 4 1 4 2
(d) they have very strong C-X bond 35. In a group of isomeric alkyl halides, the order of boiling
29. Predict the product, [OJEEJ points is [J&K CETJ
OH (a) primary < secondary < tertiary
(b) prima1y > secondary < tertiary
A
u (i)PBr3
(ii) ale.KOH
(c) primary < secondary > tertiary
(d) prima1y > secondary > tertiary
36. The conversion of ethyl chloride into diethyl ether takes
place by [BCECEJ

(a) 0 ; : OH
(b)V
(a) Williamson's synthesis (b) Perkin's reaction
(c) Wurtz reaction (d) Grignard reaction
Br 2006

(c) 6 37. CH3 Br + Nu- ~ CH 3 -Nu + Br- . The decreasing

order of the rate of the above reaction with nucleophiles

(Nu-) A to D is
2007 [Nu - = (A) Pho-, (B) AcO- , ( C) HO- ],(D) CH3 o - )
2H2/ Ni (a)D>C>A>B (b) D > C > B > A [AIEEEJ
30. X + KCN ~ CH 3 CN ~ CH3 CH 2 NH 2
(c)A>B>C>D (d) B> D>C> A
What is X ? [BITSATJ
38. Reaction of trans-2-phenyl-l-bromo cyclopentane on
(a) CH3 CH 2 Cl (b) CH3 CI reaction with alcoholic KOH produces [AIEEE]
(c) CH3 CH 2 CH 2 Cl (d) (CH 3 )i CHCl (a) 4-phenyl cyclopentene
31. 1-chlorobutane on reaction with alcoholic potash gives (b) 2-phenyl cyclopentene
(a) but-1-ene (b) butane-1-ol [MHT CET] (c) I-phenyl cyclopentene
(c) but-2-ene (d) butane-2-ol (d) 3-phenyl cyclopentene
32. An alkyl halide reacts with alcoholic ammonia in a sealed 39. The structure of the major product formed in the following
tube, the product formed will be [KCETJ reaction is [AIEEEJ

Y
(a) a primary amine Cl NaCN
(b) a secondary amine ,,::- ~
(c) a tertiary amine
(d) All of the above I
33. Maximum number of molecules of CH 3 I that can react
with a molecule ofCH 3 NH 2 are [KCETJ
~Cl
003 ~4 ~2 00 1 (b) N C ~

YCN
34. Match the following columns. I

Column I Column JI
(d)
(Reactants) (Products)

I
B. C2H 5 Cl , aqueous ethanolic AgCN 2. C2H 4
40. RX+ A ~ RNC,A is [VITEEE]
C. C2H 5 Cl, aqueous ethanolic AgN0 2 3. CH3CH20H
(a) AgCN
D. C2H 5Cl, ethanolic KOH (b) KCN
(c) NaCN
(d) HCN
 Haloalkanes and Haloarenes I 575
Reduction
41. CH3Br + KCN (ale. ) ~ X ----➔ Y.
Na +CiH50H
What is Y in the series ? [MP PET]
(a) CH3 CN (b) C 2H 5CN
(c) C 2 H 5 NH2 (d) CH3 NH2
42. Which of the following statements regarding the SN l
reaction shown by alkyl halide is not correct?
[Kerala CEE]
(a) The added nucleophile plays no kinetic role in SN l H CH3 OH
reaction
(b) The SNl reaction involves the inversion of (a) mixtureof(K)and (L) (b) mixtureof(K)and(M)
configuration of the optically active substrate (c) Only (M) (d) Only (K)
( c) The SN I reaction on the chiral starting material ends 47. Tertiary alkyl halides are practically inert to substitution by
up with racemisation of the product SN 2 mechanism because of [AIEEE]
( d) The more stable the carbocation intermediate the (a) steric hindrance
faster the SN l reaction (b) inductive effect
(e) Polar protic solvent increases the rate of SN l reaction. (c) instability
43. In the following sequence of reactions, [UPSEE] ( d) insolubility
Reduction Y Y. 48. Elimination of bromine from 2-bromobutane results in the
C2H5Br AgCN l X , IS
fom1ation of [AIEEE]
(a) n-propylamine (b) iso-propylamine (a) predominantly 2-butyne
(c) ethylamine (d) ethyl methyl amine (b) predominantly I-butene
44. On treating a mixture of two alkyl halides with sodium (c) predominantly 2-butene
metal in dry ether, 2-methyl propane was obtained. The ( d) equimolar mixture of 1 and 2-butene
alkyl halides are [AMUJ 49. 1-chlorobutane on reaction with alcoholic potash gives
(a) 2-chloropropane and chloromethane (a) I-butene (b) 1-butanol [BITSAT]
(b) 2-chloropropane and chloroethane (c) 2-butene (d) 2-butanol
( c) chloromethane and chloroethane
50. Which of the following haloalkanes is most reactive?
(d) chloromethane and 1-chloropropane
(a) 1-chloropropane (b) 1-bromopropane [KCETJ
45. CH3Br + OH ~ CH 3 OH + Br- reaction proceeds
(c) 2-chloropropane (d) 2-bromopropane
by SN 2 mechanism. Its rate is dependent on the
concentration Qf [J&K CET] 51. Ethyl chloride on heating with AgCN forms a compound
X. The functional isomer of X is CKCET]
(a) CH3 Br, OH (b) Only CH 3 Br
(a) C2H 5NC (b) C 2H 5NH2
(c) Only OH (d) CH3Br, CH3OH
(c) C2 H 5CN (d) None of these
2005 52. When 32.25 g of ethyl chloride is subjected to
46. The following compound on hydrolysis in aqueous acetone dehydrohalogenation reaction the yield of the alkene
will give [HT JEE] formed is 50%. The mass of the product fom1ed is (atomic
mass of chlorine is 35.5) [Kerala CEE]
CH 3CH 3CH3
(a) 14 g (b) 28 g (c) 64.5 g
(d) 56 g (e)7 g
53. Which of the following applies in the reaction,
CH CHBrCH2 CH3 Ale. KOH
3
I. CH3CH= CHCH3 (major product)
TI. CH2 = CHCH2CH 3 (minor product) [OJEE]
(a) Markownikoff's rule (b) Saytzeff's rule
(c) Kharasch effect (d) Hofrnann's rule
576 I Chapterwise & Topicwise Engineering Entrances Solved Papers
54. Identify X and Y in the following sequence : (a) A = C 2H 2 , B = C2 H 6
X y (b) A = C2 H 5 Cl,B = C2 H 4
C 2H 5 Br ~ product ~ C 3 H 7 NH2 [OJEEJ
(c) A = C 2 H 4 , B = C2 H 5 Cl
(a) X = KCN,Y = LiAIH 4 (d) A = C 2 H 5 Cl,B = C2 H 5 Cl
(b) X = KCN,Y = H 3 O + 57. The order of reactivities of methyl halides in the fom1ation
(c) X = CH3 Cl,Y = AlC1 3 /HCI of Grignard reagent is [Guj CETJ
(d) X = CH3 NH2 ,Y = HN02 (a) CH 3 I > CH 3 Br > CH 3 CI
55. Compound 'A' reacts with alcoholic KOH to yield (b) CH3 Cl > CH3 Br > CH3 1
compound 'B ', which on ozonolysis followed by reaction (c) CH 3 Br > CH 3 CI > CH3 I
with Zn /H 2O gives methanal and propanal. Compound (d) CH 3 Br >CH 3 I >CH 3 CI
'A' is [AMU]
58. Which of the following that cannot undergo dehydrohaloge-
(a) 1-propanol (b) 1-butanol nation is [J & K CETJ
( c) 1-chlorobutane (d) 1-chloropentane (a) iso-propyl bromide
56. Identify A and B in the following reactions (b) ethanol
(c) ethyl bromide
A Aq. :•OH C2H5 OH AgOH B [EAMCET]
(d) None of the above

Topic 3
Preparation and Properties of Aryl Halides
2014 2013
1. The final product obtained in the reaction, is [VITEEEJ 4. Compound (A), C 8 H 9 Br gives a white precipitate when

a Br Mg/ether
A
Heavy water
is
warmed with alcoholic AgNO 3 • Oxidation of(A )gives an
acid (B), C 8 H 6 O 4 . (B) easily forms anyhydride on
heating. Identify the compound (A) . [JEE Main]

(a) o/CH,B, (b) ©(::,B,

(a) @ (b)[g(D

(c) ©YOH (d) [§(OD (o)

CH3

$,B,
2. What will be the end product (B) in the following
sequence ofreactions? [AMU]
CH3

5. An equimolar mixture of toluene and chlorobenzene is

y
~ B , (() KM..O,'()S
(ii)H20!l-f
A Cao + 4NaOH ) B
Heat
treated with a mixture of cone. H 2SO4 and cone. HNO 3 .
Indicate the correct statement from the following.

Br
(a) 1, 2-dibromobenzene
(a) p -nitrotoluene is formed in excess
(b) equimolar amounts of p-nitrotoluene and
p -nitrochlorobenzene are formed
[WB JEE]

(c) p-nitrochlorobenzene is formed in excess

(b) 1, 2-dibromobenzaldehyde
(c) 1, 3-dibromobenzene
(d) 1, 4-dibromobenzene
3. Benzyl chloride (C 6 H 5CH 2 Cl) can be prepared from
toluene by chlorination with
(a) Cl 2
(c) SOCl 2
( d) m -nitrochlorobenzene is formed in excess
6. Four compounds, toluene (I), o -dichlorobenzene (II),
m -dichlorobenzene (III) and p - dichlorobenzene (IV) are
arranged in order of increasing dipole moment. The
[Guj CETJ co1rect order is [AMUJ
(b) SO2 Cl 2 (a) IV < I < III < II (b) I < TI < III < IV
(d) NaOCI (c) II < IV < III < I (d) IV < III < II < I
 Haloalkanes and Haloarenes I 577
2010
11. Which one of the following chlorohydrocarbons readily
7. In the chemical reactions, the compounds 'A' and 'B'
undergoes solvolysis ? [J&K CETJ
respectively are [AIEEE]
NH2 (b) @-c1
@ _ NaNQi
HCl, 278K
_____, A -HBF4
-B

(a) nitrobenzene and tluorobenzene

(b) phenol and benzene 2007
(c) benzene diazonium chloride and tluorobenzene
(d) nitrobenzene and chlorobenzene 12. The reaction of toluene with Cl 2 in presence of FeC1 3 gives
predominantly [AIEEEJ
2009 (a) benzoyl chloride (b) benzyl chloride
8. In the preparation of chlorobenzene from aniline, the (c) o and p-chlorotoluene (d) m-chlorotoluene
most suitable reagent is [AMU]
13. Decomposition of benzene diazonium chloride by using
(a) chlorine in the presence of ultraviolet light Cu 2 Cl 2 / HCI to form chlorobenzene is [KCETJ
(b) chlorine in the presence of AICl 3
(a) Raschig reaction (b) Sandmeyer's reaction
(c) nitrous acid followed by heating with Cu 2 Cl 2
(c) Kolbe's reaction (d) Cannizzaro's reaction
(d) HCI and Cu 2 Cl 2
14. The compound formed on heating chlorobenzene with chloral
2008 in the presence of concentrated sulphuric acid is
9. The major product of the following reaction is [UPSEE, Jamia Millia lslamia]
[IITJEE]
(a) gammexane (b) DDT
(c) freon (d) hexachloroethane
Me~r
F e e AgN03
~ PhSNa 15. X ~ yellow or white ppt
I /2 Dimethyl fonnamide HN03
Which of the following cannot be X? [AMU]
NO2
(a) V B r (b) (CH 3)iCHCl

Me~b MeGh
~ F ~ F
(a) (b)
I /2 I /2

I
NO2 NO2 2006
16. Fluorobenzene (C 6 H 5 F) can be synthesised in the laboratory
(a) by heating phenol with HF and KF [AIEEEJ
Me Me~b
~ ~SPh ~ SPh (b) from aniline by diazotisation followed by heating the
(c) I ,,::; (d) I ,,::; diazonium salt with HBF4
(c) by direct tluorination of benzene with F2 gas
(d) by reacting bromobenzene with NaF solution
NO2 NO2
17. Which of the following statements about benzyl chloride is
10. Among the following which one has weakest incorrect? [AMUJ
carbon-halogen bond? [Manipal] (a) It is less reactive than alkyl halides
(a) Benzyl bromide (b) It can be oxidised to benzaldehyde by boiling with copper
(b) Bromobenzene nitrate solution
(c) Vinyl bromide (c) It is a lachrymatory liquid and answers Beilstein's test
(d) Benzyl chloride (d) It gives a white precipitate with alcoholic silver nitrate
578 I Chapterwise & Topicwise Engineering Entrances Solved Papers
18. Chlorobenzene gives aniline with [Jamia Millia IslamiaJ 22. p-nitrobromobenzene can be converted to p-nitroaniline
(a) NH3 /Cu 2 0 by using NaNH 2 • The reaction proceeds through the
(b) NH3 /H2S04 intermediate named [OJEEJ
(c) NaNH 2 (a) carbocation (b) carbanion
(d) None of these (c) benzyne (d) dianion

2005
19. Chlorination of toluene in the presence of light and heat Br/ Fe
followed by treatment with aqueous NaOH gives A. Compound A is OJEE
(a) o-cresol [K.eral a CEEJ
(b) p-cresol
CC13
(c) mixture of o-cresol and JrCresol
(d) benzoic acid
~Q Br
(e) 1, 3, 5-trihydroxy toluene (b) lgJ
20. Which of the following statements is incorrect regarding
benzyl chloride? [MHT CET]
CCl3 CC13
(a) It gives white precipitate with alcoholic AgN0 3
(b) It is an aromatic compound with substitution in the
side chain
(c) It undergoes nucleophilic substitution reaction
(d) It is less reactive than vinyl chloride
(,) A (~ $
Br Br
Br
21. For the preparation of Jrnitroiodobenzene from
24. Reaction of alkyl halides with aromatic compounds in
Jrnitroaniline, the best method is [WB JEE]
presence of anhy. Al Cl 3 is known as [Guj CETJ
(a) NaN0 2 / HCl followed by KI
(a) Friedel-Craft reaction
(b) NaN02 / HCl followed by CuCN (b) Hofmann degradation
(c) LiAlH4 followed by 12 (c) Kolbe's synthesis
(d) NaBH4 followed by 12 (d) Beckmann reanangement

Topic 4
Polyhalogen Compounds
2012 2010
1. When chloroform is treated with chlorine in the presence 4. Which of the following does not answer iodoform test?
of sunlight, it yields [ManipalJ (a) n-butyl alcohol [ManipaIJ
(a) urotropin (b) pyrene (b) Acetophenone
(c) chloropicrin (d) chloritone (c) Acetaldehyde
(d) Ethylmethyl ketone
2011 5. On warming with silver powder, chloroform is converted
2. Which of the following compounds is not formed in into [RPETJ
iodoform reaction of acetone? [WB JEE] (a) acetylene
(a) CH3 COCH 2 1 (b) hexachloroethane
(b) ICH 2 COCH 2 I (c) 1, 1, 2, 2-tetrachloroethane
(c) CH3 COCHl 2 (d) ethylene
(d) CH3 COCl 3
6. When tetrahydrafuran is treated with excess HI, the
3. Which of the compounds when brominated turns to meso product formed is [Ke rala CEEJ
2, 3-dibromobutane? [Guj CET]
(a) 1, 4-diiodobutane
(a) Cis-2-butene (b) 1, 4-butanediol
(b) Iso-butane (c) 2-iodotetrahydrofuran
(c) Butane (d) 4-iodo-1-butanol
(d) Trans-2-b utene (e) 2, 5-diiodotetrahydrofuran
 Haloalkanes and Haloarenes I 579
2009
7. Which of the following will not respond to iodoform test? 16. Chloropicrin is obtained by the reaction of [Manipal]
(a) Ethyl alcohol [Indraprastha CETJ (a) steam on carbon tetrachloride
(b) Propanol-2 (b) nitric acid on chlorobenzene
(c) Propanol-1 (c) chlorine on picric acid
(d) Ethanal (d) nitric acid on chloroform
17. Which of the following will not form a yellow precipitate
2008 on heating with an alkaline solution of iodine? [Manipall
8. Ethyl ortho formate is fom1ed by heating ...... with sodium
(a) CH 3 CH(OH)CH 3 (b) CH 3 CH 2 CH(OH)CH3
ethoxide. [BITSAT]
(c) CH 3 OH (d) CH 3 CH2 OH
(a) CHCl 3 (b) C 2 H 5 OH
(c)HCOOH (d) CH3 CHO
18. lodoform test is not given by [Manipal]
(a) HCHO (b) CH 3 CHO
9. What happens ifCC1 4 is treated with AgNO 3 ? (c) CH 3 COCH3 (d) C2 H 5 OH
(a) A white ppt of AgCl will form [Manipall 19. 2, 2-dichloro propane on hydrolysis yields [MHT CETJ
(b) NO2 will be evolved
(a) acetone (b) 2, 2-propane diol
(c) CCl 4 will dissolve in AgNO3
(c) isopropyl alcohol (d) acetaldehyde
(d) Nothing will happen
20. Which of the following does not answer iodoform test?
10. Iodoform is obtained when ethanol is heated with [Kerala CEE]
(a) KI and aqueous KOH [Manipal] (a) n-butyl alcohol (b) Sec-butyl alcohol
(b) 12 and aqueous KOH (c) Acetophenone (d) Acetaldehyde
(c) 12 /aqueous KI (e) Ethyl methyl ketone
(d) HI and HI0 3
21. lodoform can be obtained on warming NaOH and iodine
11. lodoform test is not given by [MHT CETJ with [WB JEE]
(a) 2-pentanone (b) ethanol (a) CH 3 -CH2-CH(OH)CH3
(c) ethanal (d) 3-pentanone
12. Which one of the following pairs is the strongest pesticide? ~
(b) (CH3 )iCH-C-C2H 5
(a) chloroform and benzene hexachloride [MP PET]
(b) DDT and 666 (c) CH 3 -rr-OCH 3
(c) 666 and ether
0
(d) lsocyanides and alcohol
(d) (CH 3 h CCH2 OH
13. Chloroform gives a trichloro derivative of an alcohol on
reaction with [Guj CETJ
22. CHCl 3 reacts with cone. HNO 3 to give [OJEEJ
(a) concentrated nitric acid (a) CC1 3 NO2 (b) CH3 NO 2
(b) aqueous alkali (c) CH 3 CN (d) CH3 CH 2 NO2
(c) acetone and alkali 23. Hexachloroethane is also called [OJEE]
(d) a primary amine and an alkali
(a) artificial sweetner (b) artificial can1phor
14. Which one of the following does not give iodoform? (c) artificial polymer (d) None of these
[J&KCET]
24. CaOCl 2 + H 2O ~ Ca(OH) 2 + X
0
II X+CH 3 CHO ~ Y
(a) @- C-CH3 Y + Ca(OH)i ~
(a) CH 3 CH(OH)i
CHCl 3 . What is 'Y'? [EAMCETJ
(b) CH 2C l 2
(c) CC1 3 CHO (d) CC1 3 COCH3

2006
25. Among the following the one that gives positive iodoform
2007 test upon reaction with 12 and NaOH is [AIEEEJ
15. Which of the following ketones will not respond to (a) CH 3 CH2 CH(OH)CH 2 CH 3
iodoform test ? [BITSAT]
(b) C 6 H 5 CH2 CH 2OH
(a) Methyl isopropyl ketone
(c) H 3 C-CH-CH2 OH
(b) Ethyl isopropyl ketone
(c) Dimethyl ketone
I
CH 3
(d) 2-hexanone (d) PhCHOHCH 3
580 I Chapterwise & Topicwise Engineering Entrances Solved Papers

26. What is the product A in the following? 2005

Cl _____,,........ Cl + Mg ~ A [BITSAT] 31. Which of the following gives iodoform test? [VITEEE]

(a) 6 (a) CH 3 -CH2 (OH)

(c) (CH 2 OH) 2
(b) C 2 H 5 CHO
(d) None of these
(b) Cl-Mg_____,,........ Mg-Cl
32. The reaction in which phenol differs from alcoho l is
(c) Both (a) and (b)
(d) None of the above (a) it undergoes esterification with carboxylic acid
(b) it reacts with ammonia [KCET]
27. Chloroform, when kept open, is oxidised to [WB JEE]
(c) it fom1s yellow crystals of iodoform
(a) CO2 (b) COC1 2 (d) it liberates H2 with Na metal
(c) CO2 , Cl 2 (d) None of these
33. Which one of the following compounds when heated with
28. Ethyl alcohol is used as a preservative for chloroform KOH and a primary amine gives carbylan1ine test?
because it [UPSEE]
(a) CHC1 3 (b) CH3 Cl COJEEJ
(a) prevents aerial oxidation of chloroform
(c) CH 3 OH (d) CH 3 CN
(b) prevents decomposition of chloroform CCl3
(c) decomposes phosgene to CO and Cl 2
(d) removes phosgene by converting it to ethyl carbonate 34. In the reaction sequence, X ~ Y
-------, Ao
FeCl 3 H2S04
29. Which of the following is added to chloroform to slow
CC13
down its aerial oxidation in the presence of light?
(a) Carbonyl chloride [EAMCET]
I
c1-@-cH-@-c1
(b) Ethyl alcohol
(c) Sodium hydroxide
(d) Nitric acid compound 'X' is [AMU]
(a) chlorobenzene (b) benzene
30. Which of the following will not give positive iodoform (c) toluene (d) biphenyl methane
test? [Jamia Millia l slamia]
35. Methyl ketone is identified by CBCECE]
(a) CH 3 CH 2 CHOHCH3 (b) CH3 CH 2 CH 2 COCH3
(a) lodoform test (b) Fehling's solution
(c) CH3 CH 2 COCH2 CH3 (d) CH3 COC6 H 5
(c) Tollen's reagent (d) Schiffs reagent

Answers
TOPIC 1 Methods of Preparation of Alkyl Halides
1. (b) 2. (c) 3. (a) 4. (d) 5. (a) 6. (c) 7. (b) 8. (c) 9. (a)
TOPIC2 Properties of Alkyl Halides
1. (b) 2. (a) 3. (c) 4. (b) 5. (b) 6. (c) 7. (a) 8. (a) 9. (c) 10. (a)
11. (a) 12. (c) 13. (c) 14. (d) 15. (a) 16. (c) 17. (a) 18. (c) 19. (c) 20. (a)
21 . (d) 22. (b) 23. (b) 24. (d) 25. (a) 26. (a) 27. (c) 28. (b) 29. (a) 30. (b)
31 . (a) 32. (d) 33. (a) 34. (c) 35. (d) 36. (a) 37. (a) 38. (d) 39. (d) 40. (a)
41 . (c) 42. (b) 43. (d) 44. (a) 45. (a) 46. (a) 47. (a) 48. (c) 49. (a) 50. (d)
51 . (c) 52. (e) 53. (b) 54. (a) 55. (c) 56. (d) 57. (a) 58. (b)
TOPIC3 Preparation and Properties of Aryl halides
1. (b) 2. (c) 3. (a) 4. (d) 5. (a) 6. (a) 7. (c) 8. (c) 9. (a) 10. (a)
11. (d) 12. (c) 13. (b) 14. (b) 15. (a) 16. (b) 17. (a) 18. (a) 19. (c) 20. (d)
21 . (a) 22. (c) 23. (a) 24. (a)
TOPIC4 Polyhalogen Compounds
1. (b) 2. (b) 3. (d) 4. (a) 5. (a) 6. (a) 7. (c) 8. (a) 9. (d) 10. (b)
11. (d) 12. (b) 13. (c) 14. (b) 15. (b) 16. (d) 17. (c) 18. (a) 19. (a) 20. (a)
21 . (a) 22. (a) 23. (b) 24. (c) 25. (d) 26. (a) 27. (b) 28. (d) 29. (b) 30. (c)
31. (a) 32. (c) 33. (a) 34. (b) 35. (a)
 Explanations
Topic 1 Methods of Preparation of Alkyl Halides
1. This is an example ofWurtz-Fittig reaction. For structure (i),
Ether

~
CH 3 - Br + 2Na + Br- CH 3 ~ + CH3 - CH 3 + 2NaBr
Methyl Methyl Ethane
bromide bromide (a) ~ Cl (b)
Br CH 3

~ lSJ i ~
Cl

A (c) ~ (d)
Cl

lSJ + 2Na + Br- CH 3

Methyl
+ 2NaBr

~
Bromobenzene bromide Toluene
(in excess) (e)
Cl
~ B r Br ~ ~
~ + 2Na l8,J ~ l8,J l8,J (5 monochloro derivatives (maximum) are possible]
Diphcnyl 5. The number of monochloro derivatives of a compound depends
Propane cannot be prepared from this reaction. upon the type of hydrogen present in the compound.

2. The best method for the conversion of an alcohol into an a lkyl The structure of neo-pentane is
chloride is by treating the alcohol with SOCl 2 in the presence of CH 3
pyridine. I
H 3C- C-CH 3
ROH + SOCl2 ~ RCI + HCI + SO2 I
The other products being gases escape leaving behind pure CH 3
alkyl halide.
·: It contains only one type of hydrogens.
:. It will give only one monochloro derivative.
CH3
H 3 C- 6-CH 2Cl
I
CH 3

6. -OH group is converted into -Cl group by SOC12 or anhydrous

ZnClzfconc. HCl or HCI etc.
7. The molecular formula of diphenyl methane shows four isomers
in form of monochloro derivatives.

4. The possible isomers of hexane are

Br Br Q-cH-0 2
H
(Diphenyl methane)C 13 12

~
Monochloro Derivatives
(i)
2-methyl pentane
(ii)
~
3-methyl pentane

(iii)
~
2,3-<limcthyl butane
(iv)
~
2,2--dimethyl butane

Out of these structures (iii) and (i) have respectively minimmn

and maximum number of monochloro derivatives.
For structure (iii), (iii)

(a) /
1"'ryl/ (b) ~Cl (iv)

[Only 2 monochloro derivatives (minimum) are possible]

582 I Chapterwise & Topicwise Engineering Entrances Solved Papers

5. This problem includes concept ofSi. l and Si. 2reaction and factor
8. (A) 2-methyl pentane ~ five types of monochlorinated
compounds affecting Si. l and Si. 2 reaction. During Si. 2 reaction of alkyl
halide, inversion of configuration takes place instead of
(B) 3-methyl pentane ~ four types of monochlorinated rearrangement.
compounds While ~ I reaction occurs through the formation of carbocation
intermediate which is favoured by the presence of Lewis acid and
(C) 2, 2-dimethyl butane ~ three types of monochlorinated aprotic solvent. Rearrangement of product is also possible in this
compounds case.
(D) 2, 3-dimethyl butane ~ two types of monochlorinated CH3X + KOH (aq) - -- CHp H + KX
compounds 6. Reactivity of haloalkanes in Si.las well as~ 2 reaction depends
upon the strength ofC- X bond. The strength ofC- CI bond is
(E) n-hexane ~ three types of monochlorinated compounds much greater as compared to C- I bond or the bond length of
9. Tertiary alcohols readily react with Lucas reagent (anhy.ZnCI:! C- I bond is much greater as compared to C- CI bond.
cone. HCI) to give white turbidity due to the fonnation of halide. Thus, C- I bond breaks readily and hence/",/'-.. I is the most
reactive haloalkane among the given halide towards Sr, 2 as well
CH 3 CH3
I ZnCl2/ HCI I as ~ I reactions.
CH3 - C- OH - - ---> CH3- C- CI 7. The order ofreactivity of halides towards Sr, 1reaction is benzyl >
I I
CH3 CH 3 ally! > 3°> 2°> 1°> Me.
Therefore, the order of hydrolysis by Sr, I mechanism is
CH3 H
Topic 2 Properties of Alkyl Halides
I I
1. Steric hindrance (crowding) is the basis ofSr,2 reaction, by using C6Hs- y - ¼ Hs > C6Hs- y- ¼Hs
which we can arrange the reactant in correct order of their
CH3 Br
reactivity towards Sr,2 reaction. (a) (d)
1
Rate of Sr,2 oc - - - - - - - - H H
Steric crowding of 'C' CH I I
3
I > C6H 5 - C- CH3 > ¼ H 5 -C-Br
CH 3CI > CH 3CH2CI > CH 3 - <;::H- CI > CH1 - <;::- Cl I I
(Less I' I I Br H
aowded) CH CH (c) (b)
3 3
3' 8. According to anti-Markownikoff's effect, in the presence of
(More
aowded) peroxide, addition of HBr to unsymmetrical double bond is
opposite to that ofMarkownikoff 's rule. According to this effect,
As steric hinderance (crowding) increases, rate of Si. 2 reaction
Br- ions adds with carbon having more number ofH-atoms.
decreases.
ROOR
Note The order of reactivity towards Sr, 2 reaction for alkyl
halides is 9. CH 3CI is used as a methylating agent. The methylating agent, is
primary halides > secondary halides > tertiary halides . one which is used for the introduction of methyl group.
( I ') (2') (3')
10. Among alkyl halides, iodides are least stable hence these form
2. When tertiary alkyl halide is treated with sodium alkoxide then Grignard reagent easily. Hence, the correct order of reactivity in
elimination reaction competes over substitution reaction because formation of Grignard reagent is
alkoxides are not only nucleophiles but strong base as wet I. CH3I > CH3Br > CH3CI
Therefore, alkenes are formed instead of ethers.
11. It is Wurtz reaction
III < I < II.
Dry ether
C2H 5 I + 2Na + IC2H 5
So, C4H 10 is formed.

3. Boiling point decreases with increase in branching. Compound ?

12. CH 3CH 2CH 2 HCH3
(III) has two branches, compound (I) has one branch and
Br
compound (II) is a normal alkyl halide with no branch.
+ CH 3CH 2CH =CHCH3
So, the boiling point is minimum for compound (III) and
By Saytzeff's rule, substituted alkenes are more stable.
maximum for compound (II).
Hence, out of cis and trans forms, trans product is more stable.
4. Ethyl is of p directing group. Direct chlorination of ethyl benzene
13. RCI + KOH ~ ROH + KCI
with Cl2 / FeCl 3 would give mixture of2 and4-chloroethyl benzene.
Thus, above reaction is an example of substitution reaction. In
this reaction, -OH group substitutes -Cl.
 Haloalkanes and Haloarenes I 583
14. C2H 5Br + AgNO2 (alc.) ~ C2H 5NO2 + AgBr 21. Grignard reagents are highly reactive and react with any source of
Nitro ethane proton to give hydrocarbons. It is therefore necessary to avoid
even traces of moisture from a Grignard reagent.
15. In vinyl chloride, the C-CI bond acquires some double bond
22. Since, the alkyl halide RX gives 4, S-diethyloctane, when reacts
character due to resonance.
with Na, it must be CHiCH2)zCH(Br)CH2CH 3.

C ~ C H ~: f------t C H 2 -
Vinyl chloride
CH = ti: 2CH3CH2 CH 2 <;::H- Br
J
Na
Dry ether

CH 2CH 3
Thus, it is very difficult to break C- CI bond. Hence, viny l
chloride does not get hydrolysed by NaOH. CH2CH3 C H2CH3
16. CN- (cyanide) is an ambidentate ligand, i.e. it can donate
I I
CH 3(CH2) 2 C H - CH--(CH2) 2- CH 3
electrons to the alkyl iodide either by using carbon or by using
nitrogen. The reaction is known as Wurtz reaction.
23. Straight chain alkyl halides have greater boiling point than their
~
R - I + NaC ==N
+
➔ R - C=N + KI + R - N =C
-
isomers. Therefore, CH 3CH 2 CH2CH2 CI has highest boiling point.
24. Nucleophilic substitution bimolecular (~2) prefers less
~ (Major) (Minor)
sterically hindered site to attack. Lesser the steric hindrance
better the ~2 reaction. So, ease of reaction is 1° > 2° > 3°.
In principle, the reaction can occur either through carbon or ~2 involves inversion of configuration stereochemically
nitrogen. But in practice, the reaction mainly occurs through (Walden inversion).
carbon as carbon behave like a strong nucleophile.
17. C2H 5CI + KCN -➔ C2H 5CN + KCI
O,loroetllane Alcoholic Propanenitrilc

18. The reaction between tert-butyl bromide and hydroxide ion

yields tert-butyl alcohol and follows the first order kinetics. The
rate of reaction depends upon the concentration of only one
reactant, which is tertiary butyl bromide. 25. Tertiary halide preferentially undergo ~I substitution as they

Stepll
(CH 3)JCBr ~5
Tert-butyl bromide ow
H3C
A CH3

+ + Bre
CH3
can give stable carbocation.

H 3C- tt-CI
CH 3

H3
~~ > (H3C)3C+
Carbocation
~ (H3C)3COH
I-butyl alcohol

Tert-butyl carboeation 1-butyl chloride

A
CH3
26. Alky l halides give elimination reaction with alcoholic KOH and
Step 11 y ield an alkene or alkyne (from dihalides) e.g.
+mr fast
(CH3)3COH sp sp
Tert-butyl alcohol Ale. KOH
Br- CH 2 - CH 2 - Br CH=CH
CH3 CH 3 I, 2-dibromo ethane t. Acetylene

19. MgCl 2 -➔ Mg2+ + 2Cl- Hence, product has both sp -hybridised carbon.
[Mg2+ + 2e- -➔ Mg (atcad1ode)] 27. An alkyl halide on heating with dry silver oxide gives ether.
2F I mol
2R- X + Ag2O ~ R- 0 - R + 2AgX
·: 2F(2 x 96500 C) deposits Mg= I mol Alkyl halide Dry Ether

1 9 65
: . 9.65 C charge will deposit Mg= x · Sx 10- 5 mol 28. Alkyl halides are less soluble in water. They are polar but fail to
2 X 96S00 form H-bonds with water.
Dry ether
RBr + Mg RMgBr
Grignard reagent
In order to prepare Grignard reagent, one mole of Mg is used per 29.
mole of reagent obtained. Thus, by S x Io- 5 mo! mg,
5 x Io- 5 mole of Grignard reagent are obtained.
30. RCI + KCN -➔ RCN + KCI
Alkyl Alkyl
20. When ethyl bromide reacts with alcoholic KCN, propane nitrile is chloride cyanide
obtained as main product
CH 3CI + KCN -➔ CH3CN CH 3CH2NH2
C2H 5 Br + ale. KCN ~ C2H 5CN + KBr Methyl Methyl Ethyl amine
Ethyl bromide propane nitrile chloride cyanide (Primary amine)
584 I Chapterwise & Topicwise Engineering Entrances Solved Papers

Chloride is an I O aliphatic carbon w hich is substituted easier in

comparison to iodide which is arylic and more stable due to
CH 3- CH2 - CH = CH 2 + HCI delocalisation hence, difficult to substitute.
Butene- I 40. RX + AgCN ~ RNC + AgX
Alkyl isocyanide
32. When an alkyl halide reacts with a lcoholic ammonia in a sealed tube When alkyl halide reacts with silver cyanide, isocyanides are
then a mixture of primary, secondary and tertiary amine is formed. obtained.. It is due to nucleophilic substitution in the presence of
RX+ NH 3 ~ RNH2 + HX Ag+.
pri-amine
Nal(zH50H) CH CH NH
Reduction 3 2 2
RNH2 + X R ~ R2NH + HX (Y)
sec-amine
42. Statement (b) is not correct regarding the ~ I reaction for alkyl
R2NH + XR ~ R3N + HX
halide because in ~ I reaction no inversion takes place.
I.er-amine
The removal of X and the attachment of OH-will take place from
33. CH3NH2 ~
- Hl (CH3) 2NH- ~
HI the same side.
+ R- X ~ R+ + x- R++ow ~ ROH
CH3 l
(CH3)3N --➔ (CH3)4 N r
Hence, three molecules of CH 3I is used. 43. C2H 5B r Ag CN➔ C2H5NC
- _ R
_ ecl
_ u_c_tio_n_ C2H5NH. CH3
(X) ())
Ethyl isocyanide Ethyl methyl amine
34. Reactants Products
44. This is Wurtz reaction. 2-chloropropane and chloromethane
C 2 H 5 CI, moist Ag2 0 CH3CH20H reacts in the presence of dry ether to form 2-methyl propane.
C2 H 5 Cl, aqueous ethanolic AgCN CH3CH2NC Ether
CH 3CI + 2Na + CI- CH- CH 3 -➔
C 2 H 5Cl, aqueous ethanolic AgN0 2 CH3CH 20NO I
CH3
C 2 H 5 Cl, ethanolic KOH C2H4

35. Alkyl halides with branched and more spherical shapes have
lower boiling point as a result of their smaller surface area. 45. CH3Br + OH- ~ CH30H + Br-
So, order of boiling points is primary> secondary > tertiary. This reaction proceeds by ~ 2 mechanism.
36. Willian1son's synthesis Rate oe [substrate][nucleophile].
C2H 50Na+ CIC 2H 5 ~ C2Hs0C2H 5 + NaCl Rate oe [CH3Br] [OW].
Diethyl ether
46. The product (K) is formed through simple substitution while
37. Nucleophilicity order is, maj or product (L) is formed through H- shift via ~ I reaction

_
CH3 -+- O>H -+-- 0 >
_ @'o- (i >CH3- c- o-
and methoxy group stabilises the carbocation intermediate of
product (L).
+ /-effect JJ
Negative
N egalive charge
comparatively
charge stable stable

38. Anti-elimination, means - H and the - Br both departing group

must be present at dihedral angle of 180° (anti).

OH q H H

Br
p

H
h
Ale. KOH)

Anti el~ination

H
3-phenylcyclopentene
H OH CH3
(K) minor product
+
CH3 CH3CH3

(Ye , NaCN ) (YCN

39.
y DMF y H H CH3
(L) major product
I I
 Haloalkanes and Haloarenes I 585
47. In ~2 reaction, nucleophile and alkyl halide react in one step. 55. 1-chlorobutane gives bu tene- I on reaction with ale. KOH
R R R (dehydrohalogenation) which on ozonolysis yields methanal
and propanal. The reaction is as follows
I
R-C-Br + Nu- ~
""- /
Nu ...... C ..... Br ale. KOH
I I CH3CH2CH 2CH 2CI A
CH 3CH2CH=CH 2
R R 1-chlorobutane I-butene

Thus, tertiary carbon is under steric hindrance thus reaction does not
take place until (C- Br) bond breaks
103
CH 3CH2CHO + HCHO
R R Propanal Meilianal
R- 6- Br ~ R- 6@ + Br-
I I
R R
which is then ~ I reaction. 56. Ethyl chloride can be converted into ethanol either by its
al kaline hydrolysis or by its reaction with moist AgOH.
48. CH 3CH2<,::HCH3 ~ CH3CH 2CHCH 3~
I @ - tt+ C2H5CI Aq. ~OH C2H 5OH AgOH C2H5Cl
Br (A) (B)
CH 3CH2CH=CH 2 + CH 3CH=CHCH3 57. Among alkyl halides, iodides are least stable, hence these
Less substituted More substituted form Grignard reagent easily. Hence, the correct order of
II I reactivity in formation of Grignard reagent is
Stability ofI > TI hence, I is predominant.
CH3I > CH3Br > CH3CI.
49. Alkyl halides in the presence of strong alcoholic alkali give
58. Ethanol cannot undergo dehydrohalogenation as it does not
elimination reaction.
contain any halogen.
H~
CH3- CH2- 6HV1H2 ~ Topic 3 Preparation and
Properties of Aryl Halides
CH3CH2CH =CH2 + H 2O + ci-
50. Order of reactivity of alkyl halide iodide > bromide > chloride >
fluoride and tertiary > secondary> primary.
51. C2H 5CI + AgCN ~ CiH5NC + AgCI
(X)
Heavy water

c6 (B)
Ftmctional isomer of X is C2H 5CN. 2. KMnO4 (alkaline) converts the alkyl chain attached directly to
Dehydrohalogenation benzene nucleus into - COOK group.
52. C2H 5C I - - - - - - - - - - . C2H 4
Hydrolysis converts - COOK into - COOR group, i.e. we
(24 + 5 + 35.5) (24 + 4)
get a carboxylic acid.
64.5 g ofC2H 5C I forms= 28 g C2H 4 The carboxylic acid group when fused with hot sodalime
32.25 g of C 2H 5CI will form=~ x 32 .25 = 14 g C2H 4 (NaOH + CaO~ it gets converted into - H with the removal
64.5 of CO 2 gas, (decarboxylation step).
yield of alkene = 50% of 14 g = ~ x 14 = 7 g

N"','.:;::~,r &B,
100
53. Alkyl halides on heating with alcoholic KOH give c.o•:•o•
dehydrohalogenation reaction to yield alkene. If in reaction, more
than one alkenes are formed, then according to Saytzeff, the most
highly substituted alkene is the major product.
y Br
y Br
-CC½
(Decarboxylation)

CH 3- ? H- i H-CH3 - HP [CH3
Br
?H=
Br
1~~~::J 2, 4 -dibromo
benzoic acid
'A'

5 y i11
6 Br
CH 3- CH=CH-CH3 + Br- 4~ 2
Major product 3
Br
54. Ethyl bromide on treating with KCN, gives ethyl cyanide, which on I, 3 -dibromobenzene
reduction gives propyl amine.
3. Toluene may undergo two different types of chlorination viz
nuclear and side-chain.
LiAIH4 CH3 CH2CH2NH2 Nuclear chlorination is achieved in cold, dark and in the
Propytarnine
presence of halogen carrier.
586 I Chapterwise & Topicwise Engineering Entrances Solved Papers

~+CI,~•&Cl-9
CI CI Cl

o-chlorotoluene
CI
p-chlorotoluene
6 (J~
o-nitrochloro
benzene
N02
+
¢
p-nitrochloro
Side-chain chlorination is favoured by high temperanrre, light benzene
(very low yield)
and in the absence of halogen carrier. Thus, when chlorine is
passed through boiling toluene solution in the presence of 6. The order of dipole moment will be TV < J < JJJ < JI.
sunlight, substitution takes place in side chain.
Cl

Toluene
@:. c&c~
Benzyl chloride Benzyl chloride
c&'
Benzotrichloride JI
$ CI
Nuclear chlorination occurs through ionic mechanism while IV
side-chain substitution occurs through free-radical mechanism.
NaNQi
4. Compound A gives a precipitate w ith alcoholic AgN03 ,so it must o - N = NC1
7. HCI, 278K
contains Br in side chain. On oxidation, it gives C8 ~04 , which
shows the presence of two alkyl chains attached directly with the
benzene nucleus. Since, compound B gives anhydride on heating
the two alkyl substituent must occupy adjacent (I , 2) positions.
Thus, A must be
Schiemann's reaction

+
NH, N=NC1 Cl

~
~
CH2Br
Alcoholic
AgN03
8.
©·~· © 6 (Diazotisation)
Cu2Cl2
Sandmeyer's
reaction
+N2

l
CH3
9. PhS- is a strong nucleophi le and dimethyl formamide (DMF) is a
highly polar aprotic solvent. Condition indicates that
Oxidat;~OH @¢O nucleophilic substitution (Sr, 2) takes place at 2° benzylic place,
stereochemically, it involves inversion of configuration.
~ ~o o
~COOH
0
Phthalic anhydride

5. As toluene and chlorobenzene, both can react with mixnire of

cone. H 2S04 and cone. HN0 3 , but - CH 3 being more reactive,
toluene w ill yield p -nitrotoluene in excess. 10. C- X bond in benzyl bromide is much weaker than in vinyl

6 ~~~:.~NO,+ 9 N02
bromide and bromobenzene since the benzyl cation left after the
removal of the bromide ion is stabilised by resonance. Further,
C- Br is weaker than C- Cl bond. Therefore, C6 H 5CH 2Br has
the weakest C- X bond.
11. Solvolysis ofhaloalkanes follows first order kinetics. During this
process an intermediate carbocation is formed. Therefore, the
halohydrocarbon which gives more stable carbocation undergoes
p-nilrotoluene
(excess) solvolysis readily.
 Haloalkanes and Haloarenes I 587
CH 3
12.
V
1i0 I
uene
Cl2, FeCl3

(CI')
Chlorination
electrophilic
substitution
p-chlorotoluene

aq I
NaOHl
o-chlorotoluene

13. This reaction is known as Sandmeyer's reaction.

~ ,- c.,csmo
~ + N,
Benzene Chlorobenzene
Diaz.onium chloride

20. Benzyl chloride is very reactive. It readily gives white precipitate

14. CC1 3 CH0 + 2 @ - c 1 with alcoholic AgN0 3 at room temperature. It also rearu ly
Chloral Cl undergoes nucleophilic substitution. Its structure is as fo llows
Chloro benzene

Cl¢:

H p + c 1- cI -
I
c
I
-0-
~ /; Cl
Vinyl chloride (CH 2 =CH - Cl), on the other hand, is less
Cl H reactive than benzyl chloride due to resonance.
DDT
r
l CH 2 =CH- ~J .
··. __ CH - 0
CH =CIJ
E9 l
2

©
15. X ---➔
AgN03
yellow or white ppt. Br
21. p-nitroiodobenzene can be prepared from p-nitroaniline as follows

~ ~~~'
Th, ,::: n,,ctioa Is aot givca by
N,~rno
because in bromobenzene, halogen is directly attached with the
benzene ring. NH2 N;c1- I
NH2 p-nitroiodobenzene

16•
V NaNOz, HCI
Diazotisation

17. Benzyl chloride is more reactive than a lkyl halides. Benzyl

22. Ary! halides in the presence of strong base like NaNH2, gives
nucleophilic
intermediate.
substin11ion reaction through benzyne

carbocation is stabilised by resonance hence, benzyl chloride

easily gives nucleophilic substitution reaction.
NaNH2
Cl NH2
- HBr

18. ~Q
l8J + NH 3 + Cu20 zoo"c
ww pressure
~Q
l8J + 2CuCl
Br
Chl orobenzene Aniline
588 I Chapterwise & Topicwise Engineering Entrances Solved Papers

6. Tetrahydrofuran when treated with excess HI, give

1, 4-diiodobutane.
23.

As- CC1 3 group is meta-directing. 0 Q

+ 2HI -----t ICH2CH2~H2CHiJ + H2O
I, 4-duodobutane

24. Friedel-Craft reaction In this reaction a lkyl halides react with

aromatic compounds in the presence of AIC13 or FeC13 to form 7. Iodoform test is given by only those compounds which contain
alkyl substituted aromatic compounds. either CH 3C=O or CH 3CH- OH group.
I I
@
Benzene
(a) CH
31
H
H- OH (b) CH
31
H- OH

CH 3
Ethyl alcohol Propanol -2

Topic 4 Polyhalogen Compounds (c) CH3CH 2CHPH

Propanol - 1
+ HCl
Carbon tetrachloride Ethanal
or pyrene
Hence, propanol-1 due to absence of above given groups, does
0 0 not give positive iodoform test.
II 01- II 8. CHC13 + 3C2H 5ONa -----t CH(OC2H 5 ) 3 + 3NaCl
2. CH 3- C- CH 3 - CH3- C- CH2I + Olr Ethyl ortho
formate
0 0
II II 9. CC1 4 is a covalent compound, therefore, it does not ionise to give
0 1-
CH 3- C- CH 2I - CH 3- C- CHI2 + Olr c 1- ions hence, it does not give white ppt. of AgCl when treated
with AgNO 3 solution. There is no reaction to evolve NO2 · CC1 4
i?
CH3- C- CHI2~
o,- i
CH 3- C- CI3 + Olr
will form a separate layer as it is immiscible with water.
10. For iodoform reaction, we need an oxidising agent which is
provided by only 12 /KOH, i.e. IO- ion.
0 0
II OH- / Hypoiodide ion first oxidises CH 3CH 2OH ~ CH3CHO
CH 3- C- CT3 - CH 3- C "-- + CHI3 and then brings about iodination of CH 3CHO to I3C· CHO.
o- Alkaline hydrolysis of CT3CHO then gives CHI3. The other three
reagents do not contain any oxidising species and hence, fail to
give iodoform test.

7ran.s-but-2-ene
: r=: CH 3
11. Iodoform test is given by compounds which have (CH3- CO- )
group or CH 3- CH-
OH
I
group.

Hence, 2-pentanone, CH3CHO and C2H 5OH give this test. But
Meso-2,3-<libromo
butane 3-pentanone does not give iodoform test. Actually, iodoform test
can be used to distinguish methy l ketones rrom ketones.
4. lodoform test is given by the compounds containing either 12. DDT and 666 (¼H6C l6 or benzene hexachloride) is the pair of

CH 3CO -
I
g roup or CH 3CHOH group.
strongest pesticides.
/CH3 NaOH HO"--._ / CH3
The stmctures of the given compounds are as 13. CHC13 + O=C"-._
- C
CH3 Cl 3C / "--cH3
(a) CH3CH2CH2CH2OH
Chloretone
(b) CH3CO¼Hs ( !, I, 1-trichloro
2 -methyl -2-propanol)
(c) CH3CHO
14. Methyl alcohol (CHpH) does not give iodoform test.
(d) CH3COC2H 5
:. n-butyl alcohol does not give iodoform test because it does not 15. All the except ethyl isopropyl ketone gives iodoform test in this
question.
possess the CH3CO- or CH3 CHOR group.
I
5. 2CHC13 + 6Ag ~ CH =CH + 6AgCl
 Haloalkanes and Haloarenes I 589
16. Chloroform on reaction with nitric acid give chloropicrin (nitro 23. Hexachloroethane is also called artificial camphor. Its stmcture is
chloroform) according to following reaction, as
CHCl 3 + HN0 3 ~ C(N02 )Cl 3 + H 20 Cl Cl
Nitrochloroform CI- 6-t-CI
(chloropicrin)
I I
17. An organic compound forms yellow precipitate of iodoform with Cl Cl
12 in the presence of alkali, if it has CH3CO- group directly or it
has 24. Ca0Cl 2 + Hp - Ca(OH)z + Cl 2
(X)
I CH 3CHO + Cl 2 -➔ CCl3CHO
CH 3- CHOH group.
(X) (Y)
18. Iodoform test is given by those compounds which have 2CCl3CHO + Ca(OH)2 - 2CHC13 + (HCOO)iCa
- CH3CO group or on oxidation yields this group. HCHO does (Y)
not give this test. 25. For positive iodoform test, alcohol molecule must have
Cl OH CH 3- CH- group.
I Hydrolysis
I
19. CH 3- C- CH3 CH3- 6 - CH3
I I OH
Cl OH Ph- CH- CH3 CHI3 + Ph- Coo-
2, 2-dichloro propane Unstable
I
OH
- H20 CH3- IT- CH3
Mgorl.n
0 26. CH 2 - CH2 - CH2 - - -- v + MgCl 2
or2Na
Acetone I I
Cl Cl
20. n-butyl alcohol (CH3CH 2CH 2CH 2 0 H) does not give iodoform
test because it does not possess the CH3CO- or CH3CHOH a and <0-dihalogen derivative of an alkane on treatment with
group. Mg or Zn or Na gives cycloalkane.

21. The compound containing 27. Chloroform is oxidised to a poisonous gas, phosgene (COC12 ) by
atmospheric oxidation.
w ?H 2CHCl 3 + 0
light
2 -----> 2COCl 2 + 2HCI
CH 3- C- and - CH- CH3 Carboxyl chloride
(Phosgene)
groups on heating w ith sodium hypoiodite (NaOI) or 12 with
aqueous NaOH or aqueous Na 2C03 gives yellow ppt. of 28. Ethyl alcohol converts phosgene to ethyl carbonate.
iodoform and the reaction is known as iodoform. COC12 + 2C2H 50H ➔ (C2H 50)z CO + 2HC1
H3C- CH2- CH- CH 3 + or - Phosgene Diethyl carbonate
I 29. Ethyl alcohol is used as a negative catalyst for the aerial oxidation
OH
of chloroform in presence of light. So, ethyl alcohol is added to
0 chloroform.
CH 3- CH 2 - C-
II CH 3 + y- + H p
30. Iodoform test is positive for compounds which have
0
0 II
II CH 3- C group or 2° alcohol group.
CH3- CH2 - C- CH3 + OY- - H
(a) CH 3- CH2 - 6 - CH 3
I
OH
0 Has 2° alcoholic group
II 0
CH 3CH 2 - C- CI3 + HONa II
~C- 0Na
(b) CH3- CH 2 - CH 2 - C- CH 3

CH 3- CH2 -
l + CHI Has CH3 CO- group

3 0
lodoform
II
22. Chloroform reacts w ith cone. HN03 to give chloropicrin which is (d) CH 3- C- C6 H 5
Has CH3 CO- group
used as tear gas.
:. Compounds in choice (a), (b) and (d) give positive
CHCl 3 + HN0 3 ~ CCl 3N02 + Hp iodoform test.
Chloropicrin
590 I Chapterwise & Topicwise Engineering Entrances Solved Papers

34. This is the preparation method of DDT (dichloro diphenyl

trichloroethane).
Cl
·: T his compound doesn't have CH3CO-
group.
:. It does not give positive iodoform test.
31. The iodoform test is given by compounds which have
or 2° alcoholic

0
Benzene(X)

Cl
.~•6 Chlorobenzene ( Y)

CH3 - C-
i or CH3 - CH-
OH
I
group. 2 ¢ + CCI 3CHO 4
HiS0 )
- H20
Chloral
In the given compounds only CH3CH2OH gives positive
iodoform test as it has CH - CH- group. H CCl3
I
OH
32. Iodoform test is given by those compounds which has
c1-0-~!-0-c1 I

CH 3 - (:- C/H or CH 3- CH- units. 35. (a) Iodoform test is done to detect the presence of CH 3CO
group in organic compounds.
~ 6H (b) Fehling's solution identifies aldehydes.
Hence, this test is not given by phenol (C(;H5 - OH). (c) Tollen's reagent identifies aldehydes.
33. Carbylamine test is a characteristic test of aliphatic and aromatic (d) Schiffs reagent identifies aldehydes.
primary amines. In this test, amine is heated with chloroform and 0
alcoholic potash when a bad smelling isocyanide (carbylamine) is II
Methyl ketone is CH3- C-R
formed.
RNH 2 + CHCl 3 + 3KOH (ale.) ~
RN ---, C + 3KCI + 3H2O
~
·: It has CH 3- C group. It is tested by using iodoform test.
Alkyl isocyanide
(Bed smelling) The compound having CH3CO group give yellow ppt. on
reaction with I2 and aqueous alkali.
Alcohols, Phenols and
Ethers
QUICK REVIEW
• Aldehydes, ketones and carboxylic acids can be reduced to • On dehydrogenation, primary alcohols give aldehydes,
alcohols. The reduction of carbonyl compounds and esters secondary alcohols give ketones.
to alcohols by using alcoholic sodium is known as Tertiary alcohols are not dehydrogenated. They are
Bouveault-Blanc reduction. dehydrated to alkenes.
• Lithium aluminium hydride (LiAlH4 ) reduces a variety of • Primary (1 °) alcohols can be oxidised to aldehydes stage by
organic compounds to corresponding alcohols without Collin's reagent (Cr03 •2C5 H 5 N) or pyridinium
attacking the double bond. e.g. chlorochromate (PCC) in anhydrous medium.
CH3 -CH=CH--CHO + 2[H] (_i) ~A~H4 dry ether • In the oxidation of alcohol by acidified K 2 Cr2 0 7 , its
Crotonaldehyde (u) 2 colour changes from orange to green due to the fom1ation
CH3-CH = CH--CH2 OH ofCr2 (S04 )J.
Crotonyl alcohol • Tertiary (3°) alcohols are resistant to oxidation due to lack
Sodium borohydride (NaBH 4 ) reduces aldehydes, ketones ofa-hydrogen.
and acid chlorides without attacking other reducible • Pinacol-Pinacolone rearrangement involves dehydration
groups, e.g. of diols through the formation of carbocation intermediate
CH3 -CH= CH--CHO + 2[H] which rearranges to more stable compound.
NaBH4 OH OH CH3
----➔ CH 3 --CH=CH-CH 2 0 H
H 20 or alcohol I I H+ I
CH 3 -C-C-CH3 ~ CH 3 -C-C-CH3
• By the use of Grignard reagent I I -HiO II I
(i) HCHO gives primary alcohols CH3 CH3 o CH3
(ii) RCHO gives secondary alcohols Pinacol Pinacolone
(iii) RCOR' gives tertiary alcohols • Commercially phenol is prepared from cumene.
Methanol cannot be prepared from Grignard's reagent and
aldehyde or ketone. It can be prepared from CH3 MgBr by C6 H 5 CH(CH3 ) 2
treatment with 0 2 . Cumene

• Hydroboration oxidation reaction, the addition of water to

an alkene is syn, anti-Markownikoff while in
oxymercuration-demercuration reaction, the addition of • Phenols are more acidic than alcohols but less acidic than
water to an alkene is anti-Markownikoff. acetic acid.
592 I Chapterwise & Topicwise Engineering Entrances Solved Papers

• Presence of electron withdrawing groups increases the • Benzenediazonium salts react with phenol in weakly
acidity of phenols while presence of electron releasing alkaline medium giving coloured substance called azo
group decreases the acidity of phenols, e.g. p-nitrophenol dyes. This reaction is called coupling reaction.
> o -nitrophenol > m -nitrophenol and m -cresol > p -cresol
> o -cresol. 0-N= NCJ-+~ OH Alkal~:~tium

• Greater the number of electron withdrawing groups at Benzenediazonium Phenol

o- and p- positions with respect to -OH group, more is the
acidic character, e.g. 2, 4, 6-trinitrophenol > 2,
4-dinitrophenol > 4-nitrophenol > 2-nitrophenol.
• Picric acid > p-nitrophenol > o-nitrophenol >
m -nitrophenol > p-chlorophenol > phenol > cresols.
• In the Reimer-Tiemann reaction, the electrophile used is
:CCl 2 (dichloromethylene).
• In Kolbe's reaction, sodium phenoxide when heated with
CO2 followed by acidification gives salicylic acid as the
main product. Salicylic acid is the starting material for the
manufacture of2-acetoxybenzoic acid (aspirin).
chloride
0-N=N-0-0H Orange dye
• Absolute alcohol (I 00% ethanol) is prepared from rectified
spirit (95.6%) alcohol.
Power alcohol consist of a mixture of absolute alcohol and
petrol roughly in the ratio 20 : 80 in the presence of a
solvent such as benzene, ether or tetralin.
Methylated or denatured spirit Drinking alcohol is
denatured (rendered unfit for drinking) by the addition of
poisonous substance like methyl alcohol, acetone or
pyridine.
• p-nitrophenol has the maximum dipole moment among the
isomeric o -, m - and p-nitrophenols. This is due to the
highest and longest charge separation. (-OH group has+ R
effect while -NO2 group has - R effect).
• Both simple and mixed ethers can be prepared by
Williamson's synthesis.
• The reaction involves the nucleophilic attack of alkoxide
ion on alkyl halide according to SN 2mechanism.
• In order to prepare ether such as ethyl tertiary butyl ether,
we must use ethyl halide (1°) and sodium tertiary
butoxide. If tertiary alkyl halide and sodium ethoxide is
used, then alkene is fo1med.

6 ONa OH CH3
I
+ CO2 '°"K &COON, C 2 H 5 -ONa + CI-1 3 -C-Br
I
CH3
Sodium Sodium
phenoxide salicylate CH3
I
OH ~ CI-1 3 - C+ C 2 H5 OH+ NaBr
COOH
dil.HCI

& ~
0
Salicylic acid
II
CH2
• Ary! alkyl ethers are prepared by reacting sodium
phenoxide on alkyl halide, e.g.
C2 H5 Br + C 6 H 5 ONa ~ C6 H 5 OC2 H5 + NaBr
CH3CO"'-o
Ethyl bromide Sodium phenoxide Ethyl phenyl ether

l
OCOCH3
CH3CO/ • Ary! alkyl ethers cannot be prepared by using sodium
alkoxide with aryl halide because cleavage of C-X bond
is difficult due to partial double bond character.
~COOH • In reaction of ethers with halogen acids, the order of
l) + CH3COOH reactivity of halogen acid is HI > HBr > HCI.
Aspirin • In case of unsymmetrical alkyl ethers, the smaller alkyl
group forms the halide due to steric factors.
 Alcohols, Phenols and Ethers I 593
The reaction follows SN 2 mechanism.
CH 3 -O-CH(CH3 h + HI~ CH3 I + (CH3 h CHOH
• In case of alkyl aryl ethers, alkyl group always forms the alkyl halide and the other product is phenol.
e.g. CH 3 -0-C6 H 5 +HI~ CH 3 l + C6 H 5 OH
• Methyl tert-butyl ether when reacts with cone. HI, gives methyl alcohol and tertiary butyl iodide. This reaction follows
SN I mechanism. Methyl tert-butyl ether when reacts with anhydrous gaseous HI, then gives methyl iodide and tert- butyl
alcohol. The reaction follows SN 2 mechanism.
• Ethers having ex-hydrogens on exposure to ozonised oxygen or oxygen in presence of sunlight fo1m peroxides.
OOH
0 2 ,1iv I
e.g. (CH 3 h CH-O-CH(CH3 h ~ (CH3 ) 2 CH-O-C- CH3
I
CH3
Peroxides are highly poisonous and decompose violently even at low concentration. Hence, ethers should not be distilled or
evaporated to dryness.

Topic 1
Preparation of Alcohols
2014 2010
1. Ethanol is CH3 CH 2 OH. Which species is fom1ed when ethanol 6. Argo!, a brown cmst, formed during the fermentation
acts as a Bronsted base? CIPUCETJ of grape juice contains CRPETJ

(a) CH 3 CH2 O- (b) CH 3 C+H 2 (a) CO2

(c) CH3 CH 2 O+H 2 (d) H 3 O+ (b) fused oil
(c) potassium hydrogen tartarate
2. Ethylene can be converted into alcohol by treatment of (d) lye
(a) Aq. KOH (b) H 2 SO4 as catalyst [IPUCETJ
(c) Moist silver oxide (d) Zn/HCI 2009
7. Ketone upon treatment with Grignard reagent gives
2013
(a) primary alcohol [UPSEEJ
3. The alcohol obtained by the hydrolysis of oils and fats is
(b) secondary alcohol
(a) glycol (b) glycerol [KCETJ (c) tertiary alcohol
(c) propanol (d) p enta nol (d) aldehyde
2012 ~ NaBH4
?
4. In the conversion of ethanol into methanol which of the s. ~ ' r , COOH 6 [OJEEJ
0
following reagents will be used? [Manipall
(a) K 2 Cr2 O 7 / H 2 SO4
(c) Cl 2 + aq. KOH
(b) NaOH + CaO
(d) All of these (a) XooH 0
2011 H
5. Among the alkenes which one produces tertiary butyl alcohol
on acid hydration?
(a) CH3 CH 2 CH= CH 2 (b) CH3 CH= CH- CH3
[WB JEE] (c) X'oH 0
H
(d)co

(c) (CH 3 hC=CH 2 (d) CH3 - CH=CH2

594 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2008 2006
9. Hydroboration oxidation of4-methyl octene-1 would give 14. Which of the following combinations can be used to
(a) 4-methyl octanol [VITEEEJ synthesise ethanol? [AMU, KCET]
(b) 2-methyl decane (a) CH 3 Mgiand CH 3 COCH3
(c) 4-methyl heptanol (b) CH 3 Mgland C 2 H 5 OH
(d) 4-methyl-2-octanone (c) CH 3 Mgi and CH 3 COOC 2 H 5
10. For the sequence of reactions, (d) CH 3 Mgland HCHO
C2H5Mgl H20/ H+ 15. The enzymes which are used to convert starch into ethyl
A - - - B - - - tert-pentyl alcohol. alcohol are [UPSEE]
The compound A in the sequence is [MHT CET] (a) maltase, diastase
(a) 2-butanone (b) acetaldehyde (b) diastase, maltase, zymase
(c) acetone (d) propanal (c) invertase, zymase
11. Identify the product/s in the following reaction. ( d) invertase, diastase, maltase
BH3 H202/ 0H -
16. In fermentation by zymase, alcohol and CO2 are obtained
3CH3CH = CH 2 ~ X - - - - from [BCECE]
products+ H 3 BO3 [Kerala CEE] (a) inve1t sugar (b) glucose
(a) CH3CH 2 CH 2 OH ( c) fructose (d) A.II of these
(b) CH 3 CHOHCH3
(c) CH3CH 2 CHO 2005
(d) CH 3 CH2 OH+ CH3 OH 17. Grignard reagent reacts with HCHO to produce [BITSAT]
(e) CH3CHO + CH3OH
(a) secondary alcohol
12. Which among the following compounds will give a (b) anhydride
secondary alcohol on reacting with Grignard's reagent (c) acid
followed by acid hydrolysis ? (d) primary alcohol
I. HCHO TI. C2H5CHO
IV. C2H5COOH 18. C 6 H 5 -CH=CHCHO~ C 6 H 5 CH= CHCH 2 OH
Select the correct answer using the codes given below. In the above sequence X can be [Manipal]
(a) Only II (b) Only III [Guj CETJ (a) H 2 /Ni
(c) I and IV (d) II and IV (b) NaBH 4
(c) K 2 Cr2 O 7 /H+
2007
(d) B oth (a) and (b)
13. Acid catalysed hydration of alkenes except ethene leads to
the formation of [UPSEEJ
19. Ethyl alcohol can be prepared from Grignard reagent by
the reaction of [UPSEEJ
(a) mixture of secondary and tertiary alcohols
(b) mixture of primary and secondary alcohols (a) HCHO
(c) secondary or tertiary alcohol (b) R 2 CO
( d) primary alcohol (c) RCN
(d) RCOCl
 Topic 2
Properties of Alcohols
2014
1. The correct combination of names for isomeric alcohols 5. The final product (IV) in the sequence of reactions
with molecular fo1mula C 4 H10 0 is/are [JEE Advanced] PBr:i Mg
CH 3 CHOH ~ I ~ [VITEEE]
(a) tert-butanol and 2-methyl propan-2-ol I Ether
(b) tert-butanol and 1, 1-dimethy 1ethan-1-ol
CH 3
(c) n-butanol and butan-1-ol
( d) iso-butyl alcohol and 2-methyl propan-1-ol
Directions (Q. Nos. 2-3) Schemes 1 and 2 describe sequential
transformation of alkynes M and N . Consider only the major (a) CH 3 -CHOCH2 CH 2 OH
products formed in each step for both schemes. I
(i) NaN H2 (excess) CH 3
(ii) CH3CH21 (I equivalent) (b) CH3 -CHCH 2 CH 2 Br
/ H - - ~ ~ - - - - + X (Scheme l )
(iii) CH31 ( I equivalent) I
HO (M) (iv) H2, Lindlar's catalyst CH3
(c) CH 3 -CH- CH 2 CH 2 OH
(i) NaN H2 (2 equivalent)
I
(ii) /'-/OH CH 3

/
r= H - - - -o+,- - - - - - . . .y (Scheme 2)
.
Br I

(iii) H3 (mild)
(d) CH 3 - rHOCH 2 CH 3

(N) (iv) H2, Pd/C CH 3

(v) Cr03 6. 0.44 g of a monohydric alcohol when added to
methylmagnesiurn iodide in ether liberates at STP,
2. The product X is 112cm3 of methane. With PCC the same alcohol forms a

K
H 3CO carbonyl compound that answers silver mirror test. The
monohydric alcohol is [KCET]
(a)
(a) H 3 C-CH-CH2 -CH 3
H H I
OH
(b) (CH3 h C-CH 2 OH

( c) H 3 C-CH-CH2 -CH 2 - CH 3
I
OH
(d) (CH3 h CH-CH 2 OH
3. The correct statement with respect to product Y is
7. The correct statement regarding the following compounds
[JEE Advanced]
(a) it gives a positi:i,e Tollen's test and is a functional is [KCET]
OH OH OH
isomer of X

~ ~
(b) it g ives a positive Tollen's test and is a geometrical
isomer of X
(c) it gives a positive iodoform test and is a functional
/'y
.
OH OH OH
isomer ofX
I II III
(d) it gives a positive iodoform test and is a geometrical
isomer ofX (a) all three compounds are chiral
4. The most suitable reagent for the conversion of (b) Only I and II are chiral
( c) I and III are diastereomers
R-CH2 - O H ~ R-CHOis [JEE Mains] (d) Only I and III are chiral
(a) K.MnO4
8. Hydrogen bonding is maximum in [IPUCET]
(b) K 2 Cr2 O 7
(c) Cr03 (a) diethyl ether (b) triethyl amine
(d) PCC (pyridiniurn chlorochromate) (c) ethanol (d) None of these
596 I Chapterwise & Topicwise Engineering Entrances Solved Papers

9. The relative case of dehydration of alcohols follows 2010

following order [J&K CET] 17. From amongst the following alcohols the one that would
(a) tertiary > secondary > primary react fastest with cone. HCl and anhydrous ZnC1 2 is
(b) primary > secondary > tertiary (a) 2~butanol [AIEEEJ
(c) secondary > tertiary > primary (b) 2-methyl propan-2-ol
(d) tertiary > primary > secondary (c) 2-methylpropanol
(d) 1 butanol
2013
18. The main product of the following reaction is
10. An unknown alcohol is treated with the "Lucas reagent" to
detem1ine wheter the alcohol is primary, seconda1y or C 6 H 5 CH 2CH(OH)CH(CH3 )z Cone. HzS04 ? [AIEEEJ
tertiary. Which alcohol reacts fastest and by what
mechanism? [JEE Mains]
(a) Secondary alcohol by SNl
(b) Tertiary alcohol by SN 2
(c) Secondary alcohol by SN 2
(d) Tertiary alcohol by SNl
11. Which of the following alcohol is unable to tum orange
colour of chromic acid to green? [Manipall
(a) 1° alcohol
(b) 2° alcohol
(c) 3° alcohol
(d) Allyl alcohol
12. Power alcohol is a mixture of [KCET] H5 C6CH2CH2 '-..
(a) 80% petrol + 20% ethanol + small quantity of benzene (d) /C= CH2
(b) 80% ethanol + 20% benzene + small quantity ofpetrol H3C
(c) 50% petrol + 50%ethanol + small quantity ofbenzene
19. Which compound will have highest boiling point?
(d) 80% petrol + 20% benzene + small quantity ofethanol
(a) CH4 (b) CH3 OH [MP PET]
13. When ethylene glycol is heated with acidified potassium
(c) C2H 5 OH (d) HCHO
permanganate, the main organic compound obtained is
20. An oxygen containing organic compound upon oxidation
(a) oxalic acid [Kerala CEEJ
fom1s a carboxylic acid as the only organic product with its
(b) glyoxal
molecular mass higher by 14 units. The organic compound
(c) formic acid
(d) acetaldehyde is [KCET]
(e) 2-hydroxy ethanol (a) an aldehyde
(b) a primary alcohol
14. Upon treatment with I 2 and aqueous NaOH, which of the
(c) a secondary alcohol
following compounds will fotm iodoform? [WB JEE] (d) a ketone
(a) CH3CH 2CH 2CH2CHO 21. The density of glycerol is higher than propanol due to
(b) CH 3 CH 2COCH 2CH3
(a) van der Waals' attraction [Guj CETJ
(c) CH3CH 2CH 2CH2CH 2OH
(d) CH 3 CH 2CH 2CH (OH)CH 3 (b) hydrogen bonding
(c) ionic bonding
2011 (d) more number of covalent bonds
15. Consider the following reaction, 2009
C 2H 5 OH + H 2SO 4 ~ Product 22. The reaction involved in the oil of winter green test is
Among the following, which one cannot be formed as a t,,.

product under any conditions? [AIEEEJ salicylic acid - - - - product. The product is treated
Cone. H 2SO4
(a) Ethyl hydrogen sulphate (b) Ethylene with Na 2CO 3 solution. The missing reagent in the above
(c) Acetylene (d) Diethyl ether reaction is [Manipall
16. The compound which gives turbidity immediately with (a) phenol
Lucas reagent at room temperature is [KCET] (b) NaOH
(a) butan-1-ol (b) butan-2-ol (c) ethanol
(c) 2-methyl propan-2-ol (d) 2-methyl propan-1 -ol (d) methanol
 Alcohols, Phenols and Ethers I 597
23. Lucas test is associated with [Manip al] 32. Catalytic dehydrogenation of a primary alcohol gives a
(a) aldehydes {b) phenols (a) secondary alcohol (b) aldehyde [KCETJ
(c) carboxylic acids (d) alcohols ( c) ketone ( d) ester
24. The function of ZnCl 2 in Lucas test for alcohols is IDCEJ 33. The compound on dehydrogenation gives a ketone. The
(a) to act as acid catalyst and react with HCl to form original compound is [KCETJ
H 2 ZnC1 4 (a) primary alcohol (b) secondary alcohol
(b) to act as base catalyst and react with NaOH to form (c) tertiary alcohol (d) carboxylic acid
Na 2 Zn(OH) 4
34. RCH2CH 2OH can be converted to RCH 2CH2COOH by
(c) to act as amphoteric catalyst
( d) to act as neutral catalyst the following sequence of steps CWB JEE]
(a) PBr3 , KCN, H 3 O+ (b) PBr3 , KCN, H 2 / P+
2008 (c) KCN, H 3 O+ (d) HCN, PBr3 , H 3 O+
25. Ethylene glycol reacts with excess of PC15 to give
35. In Lucas test an alcohol reacts immediately and gives
( a) l, 1-dichloroethane [BITSATJ insoluble chloride. The alcohol is [UPSEEJ
(b) 1, 2-clichloroethane
( c) I, I, I-trichloroethane (a) CH 3 OH (b) CH 3 CH2 OH
(d) 2, 2-clichloroethane (c) (CH 3 )z CHOH (d) (CH3 h COH
36. Which one of the following will most reaclily be
26. The correct order of reactivity of hydrogen halides w ith
dehydrated in aciclic conclitions ? [BCECE]
ethyl alcohol is [BITSAT]
(a) HF > HCl > HBr > HI 0 OH OH
(b) HCl > HBr > HF > HI
(a))U (b)~
( c) HBr > HCl > H I > HF
(d) HI > HBr > HCl > HF
27. When ethyl alcohol is heated with cone. H 2 SO4 , the
product obtained is
(a) CH 3 COOC 2H 5
(c) C 2 H 6
(b) C2H2
(d) C 2 H 4
[VITEEEJ (c)~
0

OH
(d)½
2007
28. Ethylene glycol gives oxalic acid on oxidation with 37. In the following sequence of reactions,
(a) acidified K 2Cr2 O 7 [VITEEEJ
CH 3 CH 2 O H ~ A ~ B HCHO) C~D
(b) acidified KMnO4 ether
(c) alkaline KMnO4 the compound 'D' is [AIEEEJ
(d) periodic acid (a) butanal (b) n-butyl alcohol
29. The correct order of boiling point for primary (l 0), (c) n-propyl alcohol (d) propanal
secondary (2°) and tertiary (3°) alcohols is [MHT CET] 38. The -OH group of an alcohol or the -COOH group of a
(a) I O > 2° > 3° carboxylic acid can be replaced by-Cl using [Manipall
(b)30>20>]0
(a) phosphorus pentachloride
(c)2°>l 0 >3°
(b) hypochlorous acid
(d)2o>3o>lo
( c) chlorine
30. The alcohol that produces turbidity immecliately with ( d) hydrochloric acid
ZnCl 2 / cone. HCl at room temperature [MHTCET]
39. During dehydration of alcohols to alkenes by heating with
(a) I -hydroxy butane concentrated H 2 SO4 the initiation step is [MP PET]
(b) 2-hydroxy butane
(a) protonation of alcohol molecule
(c) 2-hydroxy-2-methyl propane
(b) formation of carbocation
(d) l-hydroxy-2-methyl propane
( c) elimination of water
31. Primary, secondary and tertiary alcohols are clistinguished ( d) formation of an ester
from one another by [MP PET]
40. Denatured alcohol is CKCET]
(a) Ninhydrin test
(a) ethanol + methanol
(b) Tollen's reagent (b) rectified spirit+ methanol + naphtha
( c) Lucas test (c) undistilled ethanol
(d) Wittig reaction ( d) rectified spirit
598 I Chapterwise & Topicwise Engineering Entrances Solved Papers
41. Glycerol on heating with oxalic acid at l l 0°C gives 47. An organic compound' X' on treatment with pyridinium
(a) ethanol (b) methanoic acid [WB JEE] chlorochromate in dichloromethane gives compound 'Y'.
(c) ether (d) acetone Compound 'Y', reacts with 12 and alkali to form
triiodomethane. The compound ' X' is [EAMCETJ
42. The dehydration ofbutan-1-ol gives [WBJEE]
(a) C2 H 5 OH (b) CH 3 CHO
( a) ] -butene as the main product
(c) CH 3 COCH3 (d) CH 3 COOH
(b) 2-butene as the main product
(c) equal amounts of ]-butene and 2-butene 48. Which one of the following alcohol is used as an antifreeze
(d) 2-methyl propene reagent for making explosives ? [J&K CETJ
43. Methanol cannot be dried with anhydrous CaCl 2 because (a) Glycerol (b) G lycol (c) Ethanol (d) Phenol
(a) CaC1 2 dissolves in it [WB JEE] 49. Which one can differentiate between C2 H 5 OH and
(b) it is not good dehydrating agent CH 3 OH? [BCECE]
(c) it forms a solid CaC1 2 ·4 CH 3 OH (a) H 2 0 {b) Na 2 C03 + 12
(d) it reacts with CH 3 OH (c) NH 3 (d) HCl
44. Among the following compounds which can be dehydrated 50. An unknown compound' D' first oxidised to aldehyde and
very easily ? [UPSEE, Jamia Millia Islamia] then acetic acid by a dilute solution of K 2 Cr2 O 7 and
(a) CH 3 CH 2 CH 2 CH2 CH 2 OH H 2 SO4 . The compound 'D' is [BCECEJ
OH (a) CH 3 OH (b) C2 H 5 OH
I (c) CH 3 CH2 COOH (d) CH 3 CH 2 CHO
(b) CH 3 CH2 CH 2 CHCH 3
51. A fruity smell is obtained by the reaction of ethanol with
CH 3 (a) CH 3 COCH3 (b) PC1 5 [BCECEJ
I (c) CH 3 COOH (d) CH 3 CHO
(c) CH 3 CH 2 CCH2 CH3
6H 2006
52. Pinacol is [BITSATJ
(d) CH 3 CH2 CHCH 2 CH2 OH
(a) 3-methylbutan-2-ol
I (b) 2, 3-dimethyl-2, 3- butaned:iol
CH 3
45. Cyclohexanol on reaction with PBr3 in presence of (c) 2, 3-dimethyl-2-propanone
pyridine gives [OJEE]
(d) None of the above

(a) bromocyclohexene 53. 2-propanol + NaBr Reflux ) X. What is X ? [MP PET]

(b) bromocyclohexane (a) 2-bromopropane (b) Propane
(c) 1-bromocyclohexanol ( c) Propene ( d) Propanone
( d) None of these 54. Which of the following will not react with NaOH?
OH

(a) 0 2N*N<Jj>) C,H; OH CWBJEEJ

NO2

(d) CH(CNh
55. The correct order of ease of dehydration of following is

Q-oH Q-oH Q-oH

l II III
(a) I > II > III (b) III > II > I [WB JEE]
(c) I > ill > TI (d) III > I > II
56. Alcoholic beverages contain CUPSEEJ
(a) iso-propyl alcohol (b) n-propyl alcohol
(c) ethyl alcohol (d) methyl alcohol
 Alcohols, Phenols and Ethers I 599

57. In the reaction, A

Oxidation
acetone----+ acetic
2005
63. The best method to prepare cyclohexene from
acid,A is [UPSEEJ cyclohexanol is by using [IIT JEE]
(a) 1-propanol (b) 2-butanol (a) cone. HCl + ZnC12
(c) 2-propanol (d) ethanol (b) cone. H 3 PO 4
. Oxidation NH3
(c) HBr
58. In the reaction, CH3 OH- - - - + A ~ B; A and B (d) cone. HCl
are [UPSEE] 64. Glycerol is oxidised by bismuth nitrate to produce
(a) HCHO, HCOONH4 (b) HCOOH, HCOONH 4 (a) oxalic acid [BITSATJ
(c) HCOOH, HCONH2 (d) HCHO, HCONH2 (b) meso oxalic acid
(c) glyceric acid
59. When compound X is oxidised by acidified potassium
(d) glyoxylic acid
dichromate, compound Y is formed. Compound Y on
reduction with LiAIH 4 gives X. X and Y respectively are 65. Which of the following is dihydric alcohol? [Manipall
(a) C 2 H 5 OH, CH3 COOH CEAMCETJ (a) Glycerol
(b) CH3 COCH3 , CH3 COOH (b) Ethylene glycol
(c) C 2 H 5 OH, CH3 COCH3 (c) Catechol
(d) CH3 CHO, CH3 COCH3 (d) Resorcinol

2 Cl 3Cl2 66. An organic compound A containing C, H and O has a

60. CH3 CH 2 OH step-I CH 3 CHO~ Cl 3 CCHO pleasant odour with boiling point of 78°C. On boiling A
with concentrated H2 SO4 , a colourless gas is produced
In above reactions the role of Cl2 in step 1 and step 2
respectively is [EAMCETJ which decolourises bromine water and alkaline KMnO 4 •
The organic liquid A is [KCETJ
(a) oxidation, chlorination (b) reduction, chlorination
(c) oxidation, addition (d) reduction, substitution (a) C2 H 5 Cl
(b) C 2 H 5 COOCH3
61. Lucas reagent is [Guj CETJ
(c) C2 H 5 OH
(a) cone. HCl and anhydrous ZnC1 2 (d) C 2 H 6
(b) cone. HNO 3 and hydrous ZnC1 2
(c) cone. HCl and hydrous ZnC1 2 67. In the reaction, C 2 H 5 OH 3
:;;~) X
(d) cone. HNO 3 and anhydrous ZnC1 2 (vapour)

62. In the following reaction, X and Y respectively are The molecular fo1mula of X is [EAMCET]
(a) C4 H 6 0 (b) C4 H 10 0
C 2 H 5 OH KMn04 /H+ X y CH CO C H (c) C2 H 4 0 (d) C2 H 6
H2S04 l ll. 3 2 2 5

(a) CH 3 OH, C 2 H 5 OH [J& KCET] 68. Which of the following compounds is most acidic?
(b) CH 3 CHO, CH 3 OH (a) CH4 (b) C2 H 6 CBCECEJ
(c) CH 3 CO 2 H, C 2 H 5 OH (c) CH= CH (d) C2 H 5 OH
(d) C2 H 4 , CH 3 CO2 H

Topic 3
Preparation, Properties and Uses of Phenols
2014
1. The reactivity of compound Z with different halogens The observed pattern of electrophilic substitution can be
under appropriate conditions is given below explained by [JEE Advance d]

OH ~ monohalo substituted derivative

(a) the steric effect on the halogen
whenX2 = I2 (b) the steric effect of the tert-butyl group

Q (Z)
X2

C(CH3)J
dihalo substituted derivative
whenX2 = Br2
trihalo substituted derivative
when X2 = Cl2
(c) the electronic effect of the phenolic group
(d) the electronic effect of the tert-buty1 group
600 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2. For the identification of P-naphthol using dye test, it is 7. What reaction does hydroquinone undergo most readily?
necessary to use [JEE Advanced] (a) SN 2substitution (b) Hydrolysis [Manipal]
(a) dichloromethane solution of P-naphthol ( c) Oxidation ( d) Reduction
(b) acidic solution of P-naphthol

©
OH
(c) neutral solution of P-naphthol
(d) alkaline solution ofl3-naphthol
8, C,H,COC- X Ni<rarioo > [KC,m
3. Sodiwn phenoxide when heated with CO 2 under pressure
at 125° C yields a product which on acetylation produces
C. [JEE Mains] Y (major product). Y is

(a) @ - c o o ~ N 02
r8r--oNa + CO ~ B ~ C
l8) 2 Salm Ae:iO

(b) HO ~ COO ~ N02

The major product C would be
OCOCH3 OH

$-COCH,
(c) 0 2N ~ c o o - @
(a) @-cOOH (b)
(d) 0 2 N ~ C O O ~N02

COCH3 9. lodoform reaction is answered by all, except [KCET]

OCOCH3 (a) CH 3 -rH-CH 2 -COOH

OH
(d) ©LcooH (b) CH 3 CHO
(c) CH 3 -CH2 -0H
4. Which of the following compounds will give positive (d) CH 3 -CH2 -CH2 0H
iodoform test with 12 and NaOH? [BITSAT] 10. When phenol is treated with D 2 SO4 / D 2 0 , some of the
(a) C 6 H 5 COC6 H 5 (b) CH 3 CH 2 CHO hydrogens get exchanged. The final product in this
(c) C 6 H 5 COCH2 CH 3 (d) C 6 H 5 -CH-CH3 exchange reaction is [WB JEE]
I OD OD
OH
5. Identify the correct product formed during the following
reaction
CH3
[BITSAT] (a)
H
~I D (b) D*~I H
D* H H H
D D
< > r + cH3
OHOH
OD OD

(c) 0(
CH3

C- CH3
(c) D*~H (d) H*~H
H
I
D D
I
D
II H H
0
CH3 11. X~ Benzoquinone, Identify X and y in the given
(d) IV reaction. [EAMCET]
'{~CH3 y y
0 X X
OH OH
6. What represents the best method producing salicylic acid?

(a) Benzoic acid, strong base, high temperature

(b) Toluene, strong base, water, high temperature
[VITEEE]
(•)6 Zn (b)
0 Na2Cr20 7
IH2S04

(c)o
( c) Phenol, base, carbon dioxide then acid OH OH
( d) Bromobenzene, carbonic acid, high temperature
Na2Cr20 7
IH2S04
(d)
0 Zn
 Alcohols, Phenols and Ethers I 601
2013
12. The major product(s) of the following reaction is (are) 16. An organic acid without a carboxylic acid group is

A
9 Ao,000'8"
o., ...,......,
(a) picric acid
( c) vinegar
(b) oxalic acid
( d) ascorbic acid
[KCETJ

17. The order ofmelting point ofortho, para, meta nitrophenol

is [OJEE]
(a)o>m>p (b)p>m>o (c)m>p>o (d)p>o>m
SO3H
2012

Br*; B, Bc~B, ~ &B,

18. The reaction of phenol with excess ofbromine water gives
(a) 11rbromophenol [MP PET]

SO3H
Br Y Br
Br)y\Br Br)y\Br
Br SO3H
(b) o-and p-bromophenol
( c) 2, 4-clibromophenol
(d) 2, 4, 6-tribromophenol
(P) (Q) (R) (S) 19. Which one of the following properties is exhibited by
phenol? [WB JEE]
(a)P (b) Q [JEE Advanced]
(c)R (d) S (a) It is soluble in aq. NaOH and evolves CO2 with
aq. NaHCO 3
13. In the following reaction, the product(s) formed is (are) (b) It is soluble is aq. NaOH and does not evolve CO,
with aq. NaHCO3 -
(c) It is not soluble in aq. NaOH but evolves CO2 with

¢ OH

CH3
Chlorofonn
NaOH
+ CHC13 - - - - - >

2011
aq. NaHCO 3
(d) It is insoluble in aq. NaOH and does not evolve CO 2
with aq. NaHCO3

20. Phenol is heated with a solution of mixture of KBr and

KBrO 3 .The major product obtained in the above reaction is
[AIEEE]
(a) 2-bromophenol (b) 3-bromophenol
(c) 4-bromophenol (d) 2, 4, 6-tribromophenol
21. Which of the following reagents may be used to clistinguish
between phenol and benzoic acid? [AIEEEl
(a) Aqueous NaOH (b) Tollen's reagent
(a) P (major) [JEE Advanced] (c) Molisch reagent (d) Neutral FeCI 3
(b) Q (minor) 22. The correct order of acid strength of the following
(c) R (minor) compounds is
(d) S (major) I. Phenol TT. p-cresol
14. Reimer-T iemann reaction involves [Manipal] ITT. m-nitrophenol IV. p-nitrophenol [AIEEE]

(a) carbon ium ion intem1ediate (a) III > II > I > IV (b) IV > III > I > II
(b) carbene intermediate (c) II > IV > I > III ( d) I > II > IV > III
( c) carbanion intermediate 23. The conversion of rn-nitrophenol to resorcinol involves
( d) free radical intennediate respectively CKCETJ

/CH3 (a) hydrolysis, cliazotisation and reduction

(b) diazotisation, reduction and hydrolysis
(c) hydrolysis, reduction and cliazotisation

15. ~"CHI;::: A+B

Identify A and B
(a) Phenol, acetone
(c) Benzoic acid, acetone
(d) reduction, cliazotisation and hydrolysis
24. Phenol can be converted too-hydroxy benzaldehyde by
(a) K olbe's reaction [Kerala CEEJ
[Manipal] (b) R eimer-Tiemann reaction
(b) Phenol, acetaldehyde (c) Wurtz reaction
(d) Benzaldehyde, ethanol ( d) Cannizaro reaction
(e) Sandmeyer's reaction
602 I Chapterwise & Topicwise Engineering Entrances Solved Papers

25. Two aromatic compounds having formula C 7 H 8 0 which 33. In the reaction for dinitration
are easily identifiable by FeC1 3 solution test (violet
colouration) are [WB JEE]
(a) o-cresol and benzyl alcohol Cone. X
(b) m-cresol and p-cresol HN03 .
(c) o-cresol and p-cresol ~CH,
(d) methyl phenyl ether and benzyl alcohol The major dinitrated productXis [WBJEE]
26. The correct order of decreasing acidity of nitrophenols will
be [WBJEE]
(a) m-nitrophenol > p-nitrophenol > o-nitrophenol
(b) o-nitrophenol > m-nitrophenol > p -nitrophenol
(c) p -nitrophenol > m-nitrophenol > o-nitrophenol
(d) p-nitrophenol > o-nitrophenol > m-nitrophenol
Reaction Reaction
27. Chlorobenzene - - ---i Phenol - - ----t
X y
Salicylaldehyde
(c)
X and Y reactions are respectively ... .. .
(a) Fries rearrangement and Kolbe-Schmidt [Guj CET]
(b) Cumene and Reimer-Tiemann
(c) Dow and Reimer-Tiemann 34. Phenol on treatement with diethyl sulphate in presence of
(d) Dow and Friedel-Craft NaOH gives [UPSEEJ

2010 (a) phenetole (b) anisole

(c) diphenyl ether (d) diethyl ehter
28. Acidity of phenol is due to [Manipal]
35. Salicyl aldehyde is obtained when phenol is heated with
(a) hydrogen bonding CHCl 3 and aqueous NaOH. This reaction is known by
(b) phenolic group
which name? [Guj CETJ
(c) benzene ring
(d) resonance stabilisation of its anion (a) Carbyl amine reaction
(b) Hofmann's reaction
29. When phenol is treated with excess of bromine water, it (c) Reimer-Tiemann reaction
gives [Manipal] (d) Kolbe-Schmidt reaction
(a) m-bromophenol 36. Correct acidic order of the following compounds is
(b) o-and p-bromophenol [lndraprastha CET]
(c) 2, 4-dibromophenol

© ~ ~
OH
(d) 2,4,6-tribromophenol
Alkali
Fusion
C

In the above sequence, C is [Manipal] CH3 NO2

(a) o-bromophenol I II ITT
(b) p-bromophenol (a) I > II > III (b) III > I > II
(c) m-bromophenol (c) II > III > I ( d) I > III > II
(d) 2, 4, 6-tribromophenol
2008
31. Phenol ~ fom1s a tribromo derivative "X" is [KCET] 37. Phenol, when it first reacts with concentrated sulphuric
(a) bromine in benzene acid and then with concentrated nitric acid, gives
(b) bromine in water (a) 2, 4, 6-trinitrobenzene (b) o -nitrophenol [AIEEEJ
(c) potassium bromide solution (c) p -nitrophenol (d) nitrobenzene
(d) bromine in carbon tetrachloride at 0°C
38. When o- or p -phenol sulphonic acid is treated with
2009 bromine water, the product fom1ed is [Manipall

32. The major product obtained on interaction of phenol with (a) 2, 4-dibromophenol
sodium hydroxide and carbon dioxide is [AIEEEJ (b) 2, 4, 6-tribromophenol
(c) 3-bromophenol boric acid
(a) benzoic acid (b) salicylaldehyde (d) 3, 5-dibromophenol
(c) salicylic acid (d) phthalic acid
 Alcohols, Phenols and Ethers I 603
39. The final product of the following reaction is/are 44. Picric acid is a stronger acid than acetic acid and benzoic
acid. It contains [J &K CET]
OH

@ CHCl3
KOH
X 50% KOH [MHTCET]
(a)-S0 3 Hgroup
(b) two -COOH groups
(c) phenolic group
(d) three-COOH groups
OH OH 45. The following reaction is known as [BCECEJ

@re\§)
(a)
0 r O ~ HCI + HCN ::~~ > cc----::::OH
OH OH V ~ CHO

(b)
©fCH 0H @[COOK
2
+
(a) Perkin reaction
(b) Gattermann reaction
(c) Kolbe reaction
(d) Gattermann-a.ldehyde reaction
~ CH2 0H ~COOK
(c) + 0 46. Which of the following compound would not evolve CO 2
when treated with NaHC0 3 solution?
(a) Salicylic acid [Jamia Millia Islamia]
(b) Phenol
(c) Benzoic acid
(d) 4-nitrobenzoic acid
47. By heating phenol with chloroform in alkali, it is converted
40. Phenol on heating with CC14 and aqueous KOH gives into [Jamia Millia Islamia]
salicylic acid. This reaction is [MP PET] (a) salicylic acid (b) salicylaidehyde
(a) Friedel-Craft reaction (c) anisole (d) phenyl benzoate
(b) Diels-Alder reaction 48. C 2H 5 0Hand C 6 H 5 0Hcan be distinguished by [DCEJ
(c) Reimer-Tiemann reaction
(a) Br2 + H20 (b) FeC1 3
(d) Wittig reaction (c) I2 + NaOH (d) Both (b) and (c)
41. Among the following, which is least acidic? [KCETJ
(a) phenol (b) o-cresol 2007
(c) p -nitrophenol (d) p -chlorophenol 49. Phenol is more acidic than alcohol because
42. An organic compound 'X' with molecular fommla, [BCECE, MHT CET]
C 7 H 8 0 is insoluble in aqueous NaHC03 but dissolves in (a) phenol is more soluble in polar solvents
NaOH. When treated with bromine water' X'rapidly gives (b) alcohol does not lose hydrogen atom
'Y' C 7 H 5 0Br3 . [Ke rala CEE] (c) phenoxide ion is stabilised by resonance
(d) phenoxide ion doesn't exhibit resonance
The compounds' X' and' Y' respectively, are
50. On reacting with neutral ferric chloride, phenol gives
(a) benzyl alcohol and 2, 4, 6-tribromo-3-methoxy
benzene (a) red colour (b) blue colour [J&K CETJ
(b) benzyl alcohol and 2, 4, 6-tribromo-3-methyl phenol (c) violet colour (d) green colow·
(c) o-cresol and 3, 4, 5-tribromo-2-methyl phenol 51. Carbolic acid is [BCECE]
(d) methoxybenzene and 2, 4, 6-tribromo-3-methoxy
(a) HCOOH (b) CH3 COOH
benzene
(c) C6 H 5 COOH (d) C 6 H 5 0H
(e) m-cresol and 2, 4, 6-tribromo-3-methyl phenol
43. Benzoylation of phenol in alkaline medium is known as 2006
(a) Friede l-Crafts reaction [WB JEE] 52. When benzene sulphonic acid and p -nitrophenol are
(b) Wurtz-Fittig reaction treated with NaHC0 3 , the gases released respectively are
(c) Schotten-Baurnann reaction (a) S02 , N02 (b) S02 , NO [IIT JEE]
(d) Sabatier Senderens reduction (c) S02 , CO2 (d) CO 2
604 I Chapterwise & Topicwise Engineering Entrances Solved Papers
53. The structure of the compound that gives a tribromo 61. To distinguish between salicylic acid and phenol one can
derivative on treatment with bromine water is [AIEEEJ use [Jamia Millia Islamia]
(a) NaHCO 3 solution (b) 5% NaOH solution

(a) J'.'.'
~ OH
2005
(c) neutral FeCl 3 (d) bromine water

62. When phenyl magnesium bromide reacts with t-butanol,

&OH
the product would be [IIT JEE]
(a) benzene
(o) (b) phenol
(c) !-butyl benzene
(d) t-butyl phenyl ether
63. Strength of acidity is in order [BITSAT]
54. Phenol on reaction with CHC13 and NaOH give

~ ~
benzaldehyde. lntermediate of this reaction is [DCEJ
(a) carbocation
( c) radical
(b) carbanion
(d) carbene
55. What amount of bromine will be required to convert 2 g of
phenol into 2, 4, 6-tribromo phenol? [MHT CETJ
c$J
CH3
fN02
N0 2 N02
(a) 4.00 (b) 6.00 (c) 10.22 (d) 20.44 (I) (II) (III) (IV)
56. Phenol can be distinguished from ethanol by the following
reagents except [Ke ral a CEE] (a) II > I > III > IV
(b) Ill > IV > I > II
(a) sodium (b) NaOH/12
(c) I > IV > m > II
(c) neutral FeC1 3 (d) Br2 / H 2 O
(d) IV > III > I > II
(e) phthalic anhydride/cone. H 2 SO 4 and NaOH
64. Which of the following compow1ds is weakest acid?
57. Picric acid is [UPSEE]
CUPSEE]
(a) 2, 4, 6-tribromophenol (b) sym-trinitrophenol
(c) trinitrophenol (d) 2, 4, 6-trinitrotoluene 0 2N
58. Curnene process is the most important commercial method
(a) b -o - H (b) 0 2N - o - O- H
for the manufacture of phenol. Curnene is [AMU]
(a) I-methyl ethyl benzene (b) ethyl benzene N02
(c) vinyl benzene (d) propyl benzene
59. Phenol gives characteristic colouration with [Guj CETJ (o) 0 2N---q--O- H(d) O,N---Q-0- H
(a) iodine solution
(b) bromine water N02 N02
(c) aqueous FeCl 3 solution
(d) arnmonium hydroxide 65. Phenol _N_aN_o_ 2 '- H- 4..... B ~ C
2_so_ NaOH D name of
60. Which is obtained on treating phenol, with dilute HNO 3 ? the reaction is [Guj CETJ
(a) Liebermann's reaction

(a) J'.'.
~ N 02
(b) ~NO,
V
(b) Phthalein fusion test
( c) Reimer-Tiemann reaction
(d) Schotten-Baumann reaction
66. Which is not correct ? [J&KCET]
OH (a) Phenol is more acidic than acetic acid
(b) Ethanol is less acidic than phenol
(c) 0 2N * N
I 0
2
(d) None of these ( c) Ethanol has higher boiling point than ethane
~
(d) Ethane is a non-linear molecule
N02
 Topic 4
Ethers
2014
1. The acidic hydrolysis of ether (X) shown below is fastest 6. One mole of an organic compound A with the formula
when [JEE Advanced] C3 H 8 Oreacts completely with two moles of HI to form X
and Y. When Y is boiled with aqueous alkali it fom1s Z. Z
answers the iodoform test. The compound A is CKCET]
(a) propan-2-ol (b) propan-1 -ol
OR~ OH+ROH (c) ethoxyethane (d) methoxyethane
7. A simple method to remove peroxides from ethers is to
treat them with an aqueous solution of [JCECE]
(a) KI (b) KCNS
(a) one phenyl group is replaced by a methyl group (c) Na 2 S 2 O 3 (d) Br 2
(b) one phenyl group is replaced by a para-methoxyphenyl 8. Acetic anhydride reacts with diethyl ether in the presence
group of anhydrous AlCI 3 to give [JCECE]
(c) two phenyl groups are replaced by two para-
(a) CH3 CH2 COOH {b) CH3 CH2 COOCH 2 CH 3
methoxyphenyl groups
(d) no structural change is made to X (c) CH3 COOCH3 (d) CH3 COOC2 H 5
2. Which of the following compounds will not react with 2009
Mg metal in the presence of ether to give a Grignard
9. An organic compound C3 H6 0 neither gives precipitate
reagent? [Manipal]
with semicarbazide nor reacts with sodiwn. It could be
(a) CH2 =CHBr (b) CH3 CH 2 I
(c) CH2 OHCH 2 Br {d) CH3 OCH 2 CH3 I (a) CH3 CH2 CHO {b) CH3 COCH3 [UPSEE]
3. When CH 2 =CH-O-CH 2 -CH3 reacts with one
(c) CH2 = CHCH2 OH (d) CH2 =CHOCH3
10. Which one of the following compounds will not react with
mole of HI, one of the products formed is [KCET]
CH3 MgBr? [UPSEE]
(a) ethane {b) ethanol (c) iodoethene (d) ethanal
(a) Ethyl acetate {b) Acetone
HI (c) Dimethyl ether (d) Ethanol
4. C6 H 5 -0-CH2 CH3 ~ Y +Z
/j.
11. What is the hybridisation of carbon and oxygen in
Identify Y and Zin the above reaction [EAMCET]
electronic structure of ether? [Guj CET]
y z (a) sp 3 and sp 2 (b) sp 3 and sp 3
2 2
(a) C6H5OH H3CCH3 (c)spandsp (d)sp andsp
(b) C2H5I C6H 5CHO 2008
(c) ¼Hsl CH3CCH2OH 12. If the boiling point of ethanol (molecular weight= 46) is
(d) ¼ HsOH H3CCH2T 78°C, what is the boiling point ofdiethyl ether? (molecular
weight = 74) [BITSAT]
2010 (a) 100°C (b) 78°C
5. In the reaction, (c) 86°C (d) 34°C
13. Anisole is the product obtained from phenol by the reaction
Q - o c H3 ~ the products are, [AIEEE]
known as [VITEEEJ
(a) coupling {b) etherification
(a) Br-O-OCH3 and H2 (c) oxidation (d) esterification

14. Tert-butyl methyl ether on heating with anhydrous HI in

{b) 0 -Br and CH3Br
ether gives [Manipall
(a) CH3 OH+ (CH 3 ) 3 Cl
(c) O-BrandCH3OH {b) CH3 I + (CH 3 ) 3 COH
(c) CH3 I + (CH 3 ) 3 Cl
(d) 0 - o H and CH3Br (d) None of the above
606 I Chapterwise & Topicwise Engineering Entrances Solved Papers

15. Anisole can be prepared by the action of methyl iodide on 22. An ether is more volatile than an alcohol having the same
sodium phenate. The reaction is called [KCET] molecular formula. This is due to [MP PET]
(a) Wurtz's reaction (b) Williamson's reaction (a) dipolar character of ethers
(c) Fittig's reaction (d) Etard 's reaction (b) alcohols having resonance structures
16. The products obtained when benzyl phenyl ether is heated (c) intermolecular hydrogen bonding in ethers
with HI in the mole ratio 1 : l are [Ke rala CEEJ (d) intermolecular hydrogen bonding in alcohols
I. phenol II. benzyl alcohol 23. In Williamson's synthesis [WB JEE]
III. benzyl iodide IV. iodobenzene (a) an alkyl halide is treated with sodium alkoxide
(a) I and m (b) III and IV (b) an alkyl halide is treated with sodium
(c) I and IV (d) II and IV ( c) an alcohol is heated with cone. H2 SO4 at 130°C
(e) II and III (d) None of the above
17. Which of the following does not react with sodium metal ? 2006
(a)(CH 3 )iO (b) CH3 CH 2 OH [UPSEEJ
24. Williamson 's synthesis is used for the preparation of
(c) CH 3 COOH (d) C 6 H 5 OH
(a) acid (b) ester [MP PET]
OH
18. ij + CH2 I2 + NaOH ~ ( c) ether ( d) alcohol
25. The cleavage of an aryl-alkyl ether with cold HI gives
~OH
(a) alkyl iodide and water CUPSEEJ
The product is [OJEEJ
(b) aryl iodide and water
0 (c) alkyl iodide, aryl iodide and water
(a)©() (d) phenol and alkyl iodide
0 26. Which of the following compounds when heated w ith CO
at l 50°C and 500 atrn pressure in the presence of BF3
~ O C H3 forms ethyl propionate ? [EAMCETJ
(c)~ (a) C2 H 5 OH (b) CH 3 OCH 3
OH
(c) C2 H 5OC2 H 5 (d) CH 3 OC2 H 5
19. The products obtained when anisole is heated in a sealed 27. Ethyl chloride reacts with sodium ethoxide to form a
tube with HI are [J&K CET] compound A . Which of the following reactions also yields A?
OH I (a) C2H 5Cl, KOH (ale.), L'1 CEAMCETJ
(b) 2C2 H 5 OH,conc. H 2 SO 4 , 140° C
(a)@+ CH31 (b)@+ CH30H
(c) C2H 5Cl, Mg (dry ether)
(d) C 2 H 2 , di!· H 2SO 4 , HgSO 4

OH I 28. Formation of diethyl ether from ethanol is based on a

(a) dehydration reaction [EAMCETJ

(c) @@ + (d) CH3OH + CH3I (b) dehydrogenation reaction

( c) hydrogenation reaction
(d) homolytic fission reaction
20. The reaction,
2005
C 2 H 5 ONa + C 2 H5 I ~ C 2 H 5OC2 H 5 + NaI
29. The product obtained by heating diethyl ether with HI is
is known as [Jamia Millia Islamia ]
(a) C2H5 I (b) C 2 H 5OH [BITSATJ
(a) Kolbe's synthesis
(b) Wurtz's synthesis (c) C2H 5OH+ C 2 H 5I (d) C2H 5-C2 H 5
(c) Williamson's synthesis 30. M ethyl phenyl ether can be obtained by reacting
(d) Grignard's synthesis (a) phenolate ions and methyl iodide [J&K CETJ
(b) methoxide ions and bromobenzene
2007 (c) methanol and phenol
21. In Williamson's synthesis ethoxy ethane is prepared by (d) bromobenzene and methyl bromide
(a) passing ethanol over heated alumina [Manipal] 31. In which of the following reactions the product is an ether?
(b) heating sodium ethoxide with ethyl bromide (a) C6 H 6 + CH 3 COCl/anhydrous AJC1 3 [EAMCETJ
(c) treating ethyl alcohol with excess of H 2 SO 4 at
(b) C 2 H 5 Cl + aq. KOH
430-440 K (c) C6 H 6 + C 6 H 5 COC1/anhydrous AJC1 3
( d) heating ethanol with dry Ag 2 0 (d) C 2 H 5 Cl + C 2 H 5 ONa
 Alcohols, Phenols and Ethers I 607

Answers
TOPIC 1 Preparation of Alcohols
1. (c) 2. (b) 3. (b) 4. (d) 5. (c) 6. (c) 7. (c) 8. (a) 9. (a) 10. (c)
11. (a) 12. (a) 13. (c) 14. (d) 15. (b) 16. (b) 17. (d) 18. (b) 19. (a)
TOPIC2 Properties of Alcohols
1. (a,b,c,d) 2. (a) 3. (c) 4. (d) 5. (c) 6. (b) 7. (d) 8. (c) 9. (a) 10. (d)
11. (c) 12. (a) 13. (c) 14. (d) 15. (c) 16. (c) 17. (b) 18. (a) 19. (c) 20. (b)
21. (b) 22. (d) 23. (d) 24. (a) 25. (b) 26. (d) 27. (d) 28. (c) 29. (a) 30. (c)
31. (c) 32. (b) 33. (b) 34. (a) 35. (c) 36. (a) 37. (c) 38. (a) 39. (a) 40. (a)
41. (b) 42. (b) 43. (c) 44. (c) 45. (b) 46. (c) 47. (a) 48. (a) 49. (b) 50. (b)
51. ( C) 52. (b) 53. (a) 54. (b) 55. (b) 56. (c) 57. (c) 58. (b) 59. (a) 60. (a)
61 . (a) 62. (c) 63. (b) 64. (b) 65. (b) 66. (c) 67. (c) 68. (d)
TOPIC3 Preparation, Properties and Uses of Phenols
1. (a,b,c) 2. (d) 3. (a) 4. (d) 5. (d) 6. (c) 7. (c) 8. (a) 9. (d) 10. (a)
11. (b) 12. (b) 13. (b,d) 14. (b) 15. (a) 16. (a) 17. (b) 18. (d) 19. (b) 20. (d)
21 . (d) 22. (b) 23. (d) 24. (b) 25. (a) 26. (d) 27. (c) 28. (d) 29. (d) 30. (d)
31 . (b) 32. (c) 33. (a) 34. (a) 35. (c) 36. (b) 37. (b) 38. (b) 39. (b) 40. (c)
41 . (b) 42. (e) 43. (c) 44. (c) 45. (d) 46. (b) 47. (b) 48. (d) 49. (c) 50. (c)
51 . (d) 52. (d) 53. (a) 54. (d) 55. (c) 56. (a) 57. (b) 58. (a) 59. (c) 60. (c)
61 . (a) 62. (a) 63. (b) 64. (a) 65. (a) 66. (a)
TOPIC4 Ethers
1. (c) 2. (c) 3. (d) 4. (d) 5. (d) 6. (d) 7. (a) 8. (d) 9. (d) 10. (c)
11. (b) 12. (d) 13. (b) 14. (b) 15. (b) 16. (a) 17. (a) 18. (a) 19. (a) 20. (c)
21 . (b) 22. (d) 23. (a) 24. (c) 25. (d) 26. (c) 27. (b) 28. (a) 29. (c) 30. (a)
31 . (d)
 Explanations
Topic 1 Preparation of Alcohols
1. In accordance to Bronsted-Lowry concept, an acid is a substance 7. Ketones give an addition product having more number of carbon
(molecule or ion) which possesses a tendency to donate a proton atoms with Grignard reagent, which on hydrolysis gives an
whereas base is a substance (molecule or ion) which possesses a alcohol (3°).
tendency to accept a proton by donating their lone pair of electron
to a proton. Hence, R, ~~ R,
B + H+ -----'- BH+ ' C = O + R'MgX - ' C- OMgX
[Bronsted base possesses [Bronsted acid possesses R/ '-.._) R/ I
a tendency to accept a proton] a tendency to donate a proton] R'
Addition product
••
In case of CH 3CH 2 O H, 0-atom possesses two lone pair of H20 R"'-c/R'
electrons, therefore, it\an easily accepts a proton by donating
+
_-M
_ gX(
_ O_H )_, R / "'-oH
their lone pair to a proton thereby forming a CH3CH2 0 H2. Tertiary alcohol

CH3CH2QH+
.n+ H ~ CH3CH20H2
+ Formaldehyde gives primary alcohol with Grignard reagent while
any other aldehyde except fomaldehyde give secondary alcohol.
[Bronsted base] Bronsted acid
[tendency to accept [tendency to 8. NaBH 4 reduces aldehyde to primary ( I0 ) alcohol.
a proton] release a proton]

Hence, when ethano l acts as a Bronsted base, it forms

+
~
~ ' - , - , COOH
0
~
NaBH4 CCJ OH
COOH
CH 3CH 2 OH2. The name of this species is protonated alcohol.
2. CH2=CH2 Dil·H2S04 CH3- CH2 HS04 9. Terminal alkenes react rapidly with diborane to form primary
E thylene trialkyl boranes which on oxidation gives primary alcohols.
::~ ) CH 3CH20 H CH3
Ethanol I
3CH3(CH2)3- CHCH2CH=CH2 BH1 orB2H6
3. Glycerol is obtained by the hydrolysis (either by alkali or by 4-methyl octene
steam) offats and oils.
CHpOCC17H 35
I
T HOOCC17H 35 + 3NaOH - -
[CH3(CH2lJJ::~H2CH2- CH+
CHpOCC17H35 CH 3
Fat
I
+ 3C17H 35COONa HPi /NaOH CH3(CH2)3- CHCH2CH2CH20H
Soap 4-methyl octanol
[OJ CH3CHO [OJ
(In general hydroboration oxidation involve the addition of water
Kp-p7 / H2S04 K2Crp7 !H,S04
according to anti-Markownikoff's rnle).
NaOH +CaO Cl2 aq. KOH OMgI
fl
CH4 - - CH3CI -
- KCl
CH30H I
10. H3C- C=O H3C- CH2- C- CH3
CH3 I I
CH3 CH3
H+ I 'A' 'B'
5. (CH3)iC=CH 2 - - CH 3-C-CH3 Acetone OH
+
CH3 I
- C- CH 3
-H+ I I
- - CH3-C-CH3 CH3
I ten-pentyl alcohol
OH
I-butyl alcohol
11. 3CH3CH =CH2 + BH1 (CH3CH2-CH2➔3 B H202/0 W
6. During fermentation of grape juice, a brown crust is formed at d1e 3CH3CH2CH20H + H3B03
top which is called argol. This contains potassium hydrogen
tartrate and is used for the preparation of tartaric acid and Rochelle
salt.
 Alcohols, Phenols and Ethers I 609
H DiaStase
I 15. 2(C6H10O5)11 +nH2O- - - nC12H22O11
12. C2H5CHO + RMgX - C2H5- C- OMgX Starch Maltose
Grignard I Maltase
reagent R C12H22O11 + H2O- -- 2C6H12O6
R Maltose Glucose
+ OH I
~ C2H5 CHOR+ Mg< C6H12O6 Zymase 2C2H5OH + 2CO2
Ethyl alcohal
sec. alcohol X
16. Zymase enzyme act on glucose and give ethyl alcohol and carbon
dioxide.
C6H12O6 Zymase 2C2H5OH + 2CO2 i
H20/H + Ethyl alcohol
CH3- CH =CH2 ~ CH3CHCH3
I 17. Aldehydes and ketones on reaction with RMgX followed by
OH subsequent hydrolysis in acidic medium gives alcohol. e.g.;
2° alcohol
HCHO (i)RMgX RCH2OH + Mg(OH)X
EB ( ii) Hp/H+ 1° alcohol
2° alcohol th rough 2° carbocation (CH3CHCH3)
OH
H20/H+ CH CHO (i) RMgX CH3 - CHOR + Mg(
CH3- C=CH2 ~ (CH3)JCOH 3
(ii)Hp/H +
I 3° alcohol 2° alcohol I "- X
CH3 R

EB _,,oH
3° alcohol through 3° carbocation [(CH3)JC] + Mg./
"--., X
CH3
CH3- tH- CH=CH2 HiO/H + 18. NaBH4 and LiAIH4 attacks only carbonyl group and reduce it
CH3 CH3 into alcohol group.
I Rearrangement I They do not attack on double bold~•.
CH3 CH- CH- CH3- ~ ~--- CH3- C- CH2CH3
EB
2° carbocation
EB
l C6H5- CH=CHCHO
Cinnarnic aldehyde
~
C6H5- CH=CH · CH2OH
Cinnamicalcohol
CH3 CH3
I I 19. RMgX + HCHO- 1° alcohol
CH3- CH - CH- CH3 CH3- C- CH2CH3 Grignard
reagent
I I
OH OH (RMgX) + RCHO- 2° alcohol
2° alcohol 3° alcoho l
(RMgX) + RCOR'- 3° alcohol
Thus, best alternate is (c). 0
14. When HCHO reacts with CH3Mgl, ethanol is fonned. II
CH3MgBr + H- C-H
H Grignard reagent Formaldehyde
I H
HCHO + CH3Mgl - H- C- OMgl
I I H20/H +
- CH3- C- H - ---+CH3CH2OH
CH3 I Ethyl alcohol
OMgBr
H20/H + CH3CH2OH + Mg< I
"-OH
Topic 2 Properties of Alcohols
1. Plan This problem is based on strncture and nomenclature of
organic compound. Draw the stmcture of each compound and
H30• ~
write IUPAC name of the given compotmd. Match the molecular mild I
formula of given compound with molecular formula of OH
compound given in choices. The combination of names of
possible isomeric alcohols with molecular formula C4H10O is/are
Thus, X and Y are fi.mctional isomers of each other and Y
Formula Names gives iodoform test due to the presence ofCH3CO group as
n-butyl Indicated. Hence, correct choice is ( c).
alcohol/n-butanol/butan-1-ol PCC
4. R- CH2OH - R- CH=O
CH3- CH - CH2- OH !so-butyl alcohol/2-methyl
I propan-1-ol Pyridinium chlorochromate is the mild oxidising agent with
CH3 causes conversion of alcohol to aldehyde stage. While others
causes conversion of alcohol to acid.
CH3- CH2- CH - OH

CH 3 CH3
I
Secondary butyl
alcohol/butan-2-ol 5. CH 3 - CH -
I
O H ~ CH3 - CH -
I
Br Mthg
e ~
1
I Tertiary butyl alcohol/ tert CH3 CH3
CH3- T- OH butanol/2- methyl propan-2-ol CH3 - TH - MgBr
CH 3 CH3

Hence, all choices (a), (b), (c) and (d) are correct. 1 c~/CH2
2. Plan This problem can be solved by using the concept of
nucleophilic substitution reaction, oxidation reaction and CH 3 - CH - CH2CH2OH H20 CH 3 - CH - CH2CH2OMgBr
reduction reaction including strength of nucleophile and
regioselectivity. Reaction of scheme I can be completed as
I I
CH3 CH3
=H
HO~
NaNH2
6
(I)
0~
e (II) = 3-methyl butanol

6. This problem includes conceptual mixing of mole concept,

Among two naked nucleophilic group I and IT, IT is more Tollen's test, reaction of carbony l compound and fi.mction of
nucleophilic and then will react selectively as follows Grignard reagent. Follow the steps given below to solve this
questions. Calculate the molecular mass of a alcohol using the
~H2J concept of mole concept. Now use the concept of Tollen 's test to
e ~e
0 (M) identify the correct substrate as among aldehyde and ketone only
aldehyde undergo To lien's test.
Aldehyde can be prepared by the reaction of primary alcohol with

H
l
H2 Lindlar's catalyst
(produces cis alkene)

H
PCC.
ROH + CH3MgI -
AtSTP 0.44 g
/
CH4 + Mg " '
112cm 3 OR
I

"'-----/ ? 22400 cm3

~ 0.44 X 22400
H 3CO :. Molecular mass of alcohol =- - - - - = 88
112
Hence, using the concept of regioselectivity we come on Since, alcohol oxidised with PCC [pyridinium chlorochromate
the conclusion that fina l product is correctly represented or Corey's reagent C 5H 5NH+Cr03Cl- )to form a carbonyl
by strncture (a).
compotmd (aldehyde), w hich gives positive silver mirror test
3. Plan T his problem can be solved by using the concept of hence carbonyl compound must be an aldehyde therefore it
iodoform test and fi.mctional isomerism. must be a primary alcohol.
Iodoform test The compound containing - COCH3 or PCC
- CH(OH) group will undergo iodoform test. (CH3hC-CH2OH - (CH3hC-CHO
m= 88
PCC

NaNH2
6
C
Br=:{o~ (CH3)2CH- CH2OH
m=74
-➔ (CH3)2CH- CHO

/ H I equivalent NaNHi(l eq)

N In the given options, (b) and (c) are primary alcohols having
molecular masses 88 and 74 respectively.
Hence, only (b) will be the correct choice.
 Alcohols, Phenols and Ethers I 611
7. 14. All alcohols containing the group CH 3CHOH-linked to carbon
or hydrogen atom i.e. methyl carbinols can be distinguished from
2-R, 3-R configuration, so it is a chiral other alcohols by the iodoform test.
compound. [OJ
CH 3CH 2CH2CH(OH)CH3 - CH3CH2CH2COCH3
Keto methyl group
0
2-R, 3-S configuration, i.e. it has plane of II
symmetry or in other words, rotation of CH 3CH 2CH2 C- CH3 + 312 + 4NaOH -
Keto methyl group
half part is cancelled by the other
half, so it is not a chiral compound. 0
II
CH 3CH 2CH2 C- ONa + CID3 + 3H2O + 3NaI
lodofonn
yellow (ppt)
2-S, 3-S configuration, so it is also a
chiral compound.

C2 H 5HSO4
Ethyl hydrogen sulphate
8. Ethanol contains hydroxyl group, - OH w hich can easily form
H-bonds with its other molecules that can be shown as
/ H
O -H-----O
CH3-CH{ I
(H-bonds)
I
CH,- CH3
C2H5OC2H5
Diethyl ether
CH2=CH2
Ethylene

Thus, due to H-bonding these molecules remain associated with
one another. Hence, it form maximum number of H-bonds.
However, this bonding is absent in CH3CH2OCH2CH3 among
these molecules although it contains O-atom but no H-atom is
linked to O while in triethyl amine, no H-atom is linked to N-atom
in H-bonding.
But N is more electropositive than 0. Hence H-bond is weak
9. The ease of dehydration of alcohols is Tertiary > Secondary >
Primary.
10. The reaction of alcohol with Lucas reagent is mostly as
(a), (b), (d) may be formed but (c) is never formed. Hence, correct
choice is (c).
16. In case of 3° alcohols (tertiary alcohols) turbidity appears
immediately at room temperature.
17. The reaction of alcohol with cone. HCI and anhydrous ZnCl2
following SN I pathway, so greater the stability of carbocation
formed, faster is the reaction. 2-methyl propan-2-ol gives
3° carbocation. Hence, it reacts rapidly with cone. HCI and
anhydrous ZnCl2 (Lucas reagent).
~I

reaction and the rate of reaction is directly proportional to the

stability of carbocation formed in the reaction. Since, 3° R- OH
forms 3° carbocation (most stable) hence it will react fastest.

R3COH Conc.HCI R3CCI + H2O

Tertiary Anhy. ZnCI 2
alcohol
-
Turbidity appears immediately
11. 3° alcohol offers resistance to oxidation. Hence, Cr 3 + ions are
not formed, and the solution does not tum green.
12. Edianol in the presence of small quantity of benzene, mixed with
petrol (i.e . 80% petrol + 20% ethanol + small quantity of
benzene) is called power alcohol. It is used for veh icle fuel.
13. When ethylene glycol is heated with acidified KMnO4 , the
following reaction occurs
IH20H KMn04/l·f" HCOOH 19. The boiling point of alcohols is higher than the boiling points of
+ corresponding alkanes and aldehydes due to H-bonding. As the
CH2OH HCOOH molecular mass increases, boiling point increases.
Ethylene glycol 2 moles of formic acid
Thus, C2H 5OH has the higher boiling point among the given.
i.e. formic acid is formed.
612 I Chapterwise & Topicwise Engineering Entrances Solved Papers
20. Because the difference in mass between - CH2OH group and 30. Mixture of anhydrous ZnCI 2 and cone. HCI is known as Lucas
- COOH group is 14, thus the compound which undergoes reagent. Lucas test is used for the distinction between primary,
oxidation is a primary alcohol. (- CH 2OH is the fi.mctional secondary and tertiary alcohols.
group of primary alcohols). The tertiary alcohol reacts immediately with Lucas reagent
RCH2OH - RCOOH producing n1rbidity.
(R + 31) (R + 45) The secondary alcohol gives nrrbidity within 5-10 min and
Primary alcohol Acid primary alcohol does not give turbidity at all at room temperan1re.
21. The density of glycerol is higher than propanol due to extensive In the given alternates, 2-hydroxy- 2-methyl propane is
intermolecular hydrogen bonding. Glycerol contains three - OH 3 ° alcohol, so it is more reactive.
groups while propanol contains only one - OH group. 31. Primary, secondary and tertiary alcohols are distinguished by
22. Methanol reacts with salicylic acid in the presence of a few drops Lucas test. A mixnrre of anhydrous ZnCI 2 + cone. HCI is called
ofconc. H 2SO4 to g ive methyl salicylate having the smell ofoil Lucas reagent. 2-hydroxy-2 methyl propane is 3° alcohol and
of winter green. gives turbidity immediately with Lucas reagent.
OH OH 32. Primary alcohols get dehydrogenated with reduced copper at
COOH
+ CH 3OH --=---➔
A @'COOCH, 573 K, to give corresponding aldehydes.
573
Methanol Cone. H2S04 R- CH 2OH Cu, K R- CHO + H 2
Methyl salicylate Primary alcohol Aldehyde
Salicylic acid
23. Lucas test is used to distinguish primary, secondary and tertiary 33. Secondary alcohols on dehydrogenation with Cu at 573 K give
alcohols. ketones.
573
24. 2HCI + ZnCl2 - H2ZnCl4 )cH- OH Cu, K ) c =0 + H 2
ROH+ H2ZnCl2 - RCI + ZnCl2 + H2O + HCI Secondary alcohols Ketone
3 PBr KCN
ROH+ HCI ZnCl 2 RC I + H 2O 34. RCH2CH2OH ----=--+ RCH2CH2Br------i,

25. Ethylene glycol reacts with excess of PCl5 to give ethy lene HO+
RCH2CH2COOH~RCH2- CH2- CN
chloride.
CH2CI 35. A mixture of cone. HCI + anhy. ZnCI 2 is called Lucas reagent. In
CH2OH
I + 2PCI5 - I + 2POC13 + 2HCI Lucas test tertiary alcohols immediately give turbidity while
CH2OH CH2Cl secondary alcohols give nrrbidity after 5 min. Primary a lcohols
Ethylene glycol 1, 2-dichloro give no reaction with Lucas reagent at room temperature.
ethane
CH3OH/ CH3CH OH Cone HCI + anhy-ZnCl 2 No reaction
26. Among hydrogen halides, as the size of halide ion increases, its 2
Primary alcohol
reactivity towards ethyl alcohol also increases. Thus, the order of
reactivity of hydrogen halides is and hence, no white cloudiness on turbidity at room temperanrre.
ID > HBr > HCI > HF (CH )2CHOH Cone HCI +anhy-ZnC1 2
27. When ethyl alcohol is heated with cone. H 2SO4 at I 60°-l 70°C, 3
Secondary alcohol
the product obtained is ethylene (C2H 4 ).
W hite cloudiness or turbidity appears w ithi n about 5 min.
CH3- CH2OH + H2S◊4- CH3CH2HSO4 + H2O
Ethyl hydrogen sitlphate (CH )JCOH Conc HCI + anhy-ZnClt
16 700
3
CH3- CH2HSO4 0-~ S CH2=CH2 + H 2SO4 Tertiary alcohol
Ethylene White cloudiness or nrrbidity appears immediately.
but at lower temperature ether is formed. 0 OH
28. In the presence ofHNO 3 or alkaline KMnO 4 36. Dehydration of ~ gives stable conjugated alkene.
CH2OH [OJ CHO [OJ COOR [OJ COOR COOR
I ~1 ~1 ~ 1 - 1 0 OH
CH2OH
Ethylene
glycol
CH2OH
Glycolic
aldehyde
CH2OH
Glycolic
acid
CHO
Glyoxalic
acid
COOR
O~alic
ac,d
~
29. Alcohols with same molecular weight are expected to have 37. CH3CH20H ~CH3CH2- I Mg, ether
almost same boiling point however two more factors other than (A)
molecular weight are important, they are namely H-bonding and OH
surface area of molecule. I
Both these factors are least in 3° alcohols and maximum in CH3CH2CH2 + Mg(OH)I
I O alcohols. Hence, 3° alcohols have least boiling point while (D)
n-propyl alcohol
I O alcohols have maximum boiling point.
 Alcohols, Phenols and Ethers I 613
OMgI 43. Methanol cannot be dried w ith anhydrous CaCI 2 because it forms
HO I a solid CaCl2 · 4CH 3OH (addition compound).
~CH3- CH2 - CH2
44. Dehydration of alcohol is in order I O < 2° < 3°
(C)
Thus, (c), a 3° alcohol is dehydrated very easily.
The compound 'D' is n-propyl a lcohol.
45. Cyclohexanol on reaction w ith PBr3 in the presence of pyridine
38. The - OH group of alcohol or the - COOH group of a
gives bromocyclohexane.
carboxylic acid is replaced by - Cl using phosphorns penta-
chloride (i.e. PCl5) Br
ROH+ PCl5 - RCI + POCl3 + HCI
Alcohol Alkyl halide
36+H,PO,
RCOOH + PCI5 - RCOCI + POCI3 + HCI
Acid Acyl halide Bromocyclohexane

39. Protonation of - OH is (initiation) step. Conversion of poor

+
leaving group (- OH ) into good leaving group (- OH2).
H H H H H

H- C-
I C-I 0..- H + H+ Fast ~
.
H-
I C-I 0\1
C-
+
0- H
I I .. I I ..
H H H H
Ethanol Protonated
alcohol
H H
~H- !lJ+
-H20
~ H"'-c=c/H
I I H/ "'-H
+w
PCC
H H Ethene 47. C2H 5OH + [O] . CH Cl l CH3CHO
(X) Ill 2 2 (Y)
Protonated
alcohol CH3CHO + 4NaOH + 312- CHT3 + HCOONa
40. Ethyl alcoho l is made unfit for drinking purpose by adding some (Y) (Yellow ppt)
poisonous substance as methanol, naphtha, pyridine, mbber, etc. triodomethane
It is called denatured alcohol. + 3H 2O + 3Nal
48. Glycerol is generally used as an antifreeze reagent for making
41. Glycerol react w ith oxalic acid at 110°C temperature, it gives
explosives.
methanoic acid (formic acid).
49. CH 3OH and C2H 5OH can be differentiated by using Na2CO3 and
CH2 ~ H CH2OOC- COOH I2 · CiH5OH gives yellow precipitate of CHI3 whereas CH 3OH
I 110°c I does not react with it.
CHOR + H OOC- COOH- CHOH
I Oxalic acid - H20 I C2H5OH + 4I2 + Na2CO3- CHT3
CH2OH CH2OH lodoform (Yellow ppt)
Glycerol
+ 5Nal + HCOONa + 3CO2 + H2O
CH 2OH . 2 Cr2Oi CH 3COOH
K
50. D 0 XJdation Aldehyde
+H2-C02 I H2SO4 Acetic acid
- -~ CHOH + HCOOH
I
Formic acid I O alcohol on oxidation gives aldehyde having same number of
CH2OH carbon and aldehyde on oxidation gives acid having same number
of carbon atoms. It means, D will be alcohol having two carbon
42. The dehydration of 1-butanol gives 2-butene as the main product atoms that is C2H 5OH (ethyl alcohol) and the alcohol on
because 2-carbocation is stabler than I 0 • oxidation will give CH 3CHO (acetaldehyde).

C2H5OH [OJ) CH3CHO~CH3COOH

(D) Ethanal Ethanoic acid
CH 3CH2- CH2- CH! Ethyl alcohol
1° carbocation
Alcohol + Acid ~ Ester
1
H~hift
51.
ROH RCOOH RCOOR
(fruity smelling) alcohol

+ (C2H5OH) when react with acid they produce ester and esters
CH3- CH =CH- CH 3 f-- CH3CH2- CH- CH3 have fmity smell.
2-butene - H+ 2° carbocation C2H5OH + CH3COOH - C2H5COOCH3 + H2O
Ethyl alcohol Acetic acid Fruity smell of ester
614 I Chapterwise & Topicwise Engineering Entrances Solved Papers
52. 2, 3-dimethyl butane-2, 3-diol is known as pinacol.
62. C2H 5OH + [O] KMn0 4 /H+ > CH 3COOH
CH 3 CH 3
I I Ethanol (X)
CH3- C - C- CH3 Ethanoic acid
I I
OH OH ½HsOH (Y) CH3COOC2H5
H~04 / l'i. Ethyl ethanoate
(Esterification)
53. CH3- CH- CH3 + NaBr Re~llX CH3- CH- CH3 + H2O
I I Hence, X = CH3COOH, Y = C2H5OH
OH Br
2-propanol 2-bromopropane 63. The best method to prepare cyclohexene from cyclohexanol is by
(X) cone. H 3PO4 because in the given options dehydrating agent is
cone. H 3PO4.
X is 2-bromopropane.
54. C2H 5OH (ethanol) is a very weak acid, hence it does not react
w ith NaOH. However, it reacts with metallic sodium because in
aqueous NaOH , there are mobile Na+ and Ofr. So alcohol
should not be able to react with Na +to form water and salt too, as
it can be considered as an acid.
Cyclohexanol
55. The correct order of stability of carbocation is as follows

So, the correct order of case of dehydration is TIT > TT > I.

56. Alcoholic beverages contain (3-40)% of ethyl alcohol.
Cyclohexene

CH2OH CH2OH COOR

I [OJ I [OJ I
58. CH3OH Oxidation HCOOH~ HCOONH4
(A) (B)
64. THOR ---4 co
1
---4
?o
CH2OH CHiOH COOR
59. When ethyl alcohol is oxidised by acidified potassium Glycerol Dihydroxy Meso oxalic
acetone acid
dichromate, CH 3COOH (Y) is obtained as
3C2H 5OH + 2K2Cr2O 7 + 8H 2SOc---t 65. Glycols are dihydric alcohols (having two hydroxy l groups).
X Ethylene glycol is the first member of this series.
3CH3COOH + 2Cr2(SO4h + 2K2SO4 + I IH2O CH2OH
y
I
Carboxylic acid undergoes reduction with LiAIH4 to give CH2OH
primary alcohol as Ethylene glycol
0
II 66. The organic liquid A is C2H5OH
CH3- C- OH (i) Ethyl alcohol is a colourless liquid with a characteristic
(Y) pleasant smell, having boiling point 78.1 °C.
So, X is CH3CH 2OH and Y is CH3COOH.
(ii) C2H50HConc. H~04 CH2=CH2
Cl 2
60. CH3CH2OH s tep
~ CH 3CHO (w hich decolourises Br2 water and alk. KMnO4)
I
67. Alcohols are oxidised by hot copper to give aldehydes.
The above reaction is an example of oxidation. Due to oxidation
- CH2OH group is oxidised to - CHO group. C2H5OH 3 ;;d Acetaldehyde
CH3CHO or C2H4O
3Cl2
CH3CHO Step 2
C13 · C · CHO
Hence, X = CH 3CHO
In the second step chlorination takes place. In chlorination 68. Proton donors are acids. Among the given choices C2H 5OH can
hydrogen atom changes by chlorine.
give proton (H+) most easily.
61. Cone. HCI + anhydrous ZnCl2 is called as Lucas reagent. It is
:. C2H 5OH is most acidic among C2H 6 , CH4,
used to distinguish primary, secondary and tertiary alcohol.
CH ==CH and C2H 5OH
 Alcohols, Phenols and Ethers I 615
Topic 3 Preparation, Properties and Uses of Phenols
1. Plan This problem includes concept of effect of steric and 3. It is a Kolbe SchmiReaction
electronic effect on reactivity of organic compounds. Steric effect ONa COONa

~ + co ~ ©f
of halogens are as follows Cl 2 < Br2 < I2 . Electronic effect of
phenolic group directs the approaching electrophile towards
ortho and para positions. Tertiary bu tyl group has large size so it ~ 2
Salm
cuases steric effect around aromatic nucleus.
Sodium Sodium
On the basis of above factors the products of the given reactions phenoxide salicylate

are as fo llows 0

©foc-rn,
COOH II

Aspirin (pain killer)

2- acetoxy benzoic acid
(C)

The second step of the reaction is an example of acetylation

reaction.
Hence, C =Aspirin
0
II
4. Aldehydes and ketones possess (- C- CH3) group will give
positive iodoform test.
Apart from methylated carbonyl compounds, alcohols with

Hence, orientation in electrophilic substitution reaction is decided

[CHa-i:-l gro"p also g;ve positive lodoform test.

by
(a) the steric effect of the halogen. J2 and
C6H 5- <;:H- CH 3 ~ CHl3 + C6HsCOONa
(b) the steric effect of the tert-butyl group. I NaOH Jodoform
(c) the electronic effect of the phenolic group. OH
So, (a), (b) and (c) are correct choices. 5. Pinacol-Pinacolone Rearrangement The diol is converted
2. Plan This problem can be solved by using the concept of into a-hydroxy ketone when reacted in the presence of acid is
synthesis of dye using electrophilic aromatic substitution believe to proceeds through rearrangement of carbocation as
reaction. In basic (alkaline) solution naphthol exists as shown.
naphthoxide ion which is strong o, p-directing group.
OH Oe

©©f ~ ©©J
Ill
--000,cf
Thus, formation of dye can be shown as
N=N - Ph

~ O H _ [ P _h_-_~_==
_NJ_ c _ 1 - - ~ o OH
~ Alkaline solution LglgJ Basic of carbocationic rearrangement is due to relief from angle
strain.
Thus, (d) is the correct choice.
616 I Chapterwise & Topicwise Engineering Entrances Solved Papers
i.e. any compound containing CH3CO- group of any
OH o-Na• compound which on oxidation give such group or their

O+N,on~Q+n,o
halogen derivatives in which halogen is substin1ted from
6.
CH3 group give this reaction.
(iii) CH 3COCH2COOC2H 5 does not give haloform reaction
Sodium active methylene group.
phenoxide

l+CO, In spite of the presence ofCH3CO group in it. The reason is

the presence of active methylene - CH2 - group which
OH OH prevents the conversion of CH 3CO- to CX3CO-
COOH &COONa (a necessity for the reaction).
~ I ~ (iv) The outline of the mechanism is seen as
,✓,;.
&
2-hydroxy Sodium Step I Halogen first oxidises (only in case of alcohols to
benzoic acid (Salicylic acid) salicylate
carbonyl compounds) and then halogenated the compound to get
It is a Kolbe Schmidt reaction. CX3 Tl- group. (If CH3- CIH- is taken it is first converted
7. Hydroquinone get oxidised very easily 0 X
OH 0 to CH 3- ?H - by alkali and oxidised followed by

$ ¢ OH
Hydroquinone
[OJ

0
p-benzoquinone
OH

halogenation) i.e. CH 3- TH-

X
Alkali
~

X2
8. Phenol on reaction with benzoyl chloride produces phenyl --¼ CH3- IT- ~ CX3 IT-
Oxidation
benzoate by means of nucleophilic substitution reaction. Which
on further treatment with nitration using HNO3 IH2SO4 produces O 0
the desired product. The complete sequence of the above reaction Step IT This CX3- IT- is then hydrolysed by alkali as
can be shown as
0
@ - 0 H + c 1o c - @ NaOH )
HOH

©- C(io-@ - HN
_ OyH
-"---'z'-
S0-'-
4 --+
CX3 -:-\; -
: I
0
~ CHX3 + HO- (,:;-
Halofonn
0
II

Step Ill The - IT- OH is further reacts with alkali to give

0
9. Iodoform reaction is a type of haloform reaction which can be salt and water as
defined in a general way as
- IT- OH + NaOH ~ - IT- O- Na + + H2O
0
II t,. 0 0
CH 3 - C- R + 4NaOH + 3X2 ~
(Alkali) Hence, among given form choices only (d) will not give iodoform
0 test.
II 10. In acidic medium, phenol exists in the following resonating
R- c- o- + CHX3 + 3NaX + 3H2O strncn1res.
(Halofonn)

3-et-~-~6
Important facts related to haloform reaction are as:
(i) KOH may also be used as alkali.
(ii) The compounds which can give this test must contain either
one of these
CH3- IT- ; CH3- ,H- ; CH3- r - ; CX3- IT-
Since, olp positions are electron rich sites, so electrophile will
o OH Cl 0 attack on these site, i.e. hydrogen of these sites get exchanged by
D (deuterium).
CHX 2- IT- ; CH2X _ IT_
Hence, the final product of the reaction is
0 0
 Alcohols, Phenols and Ethers I 617

e (_o
~ y• -
D*ODD
I: which is formed as CCl2 n ; C I, +~
H H - N

D CH3 CH3

OH CHCl2 ¢rOHCHO
Olr ::,-' I
:::--..

CH 3 CH 3
(S)(major)
D* O D D (S) Major as stable due to intramolecular H-bonding.
Repeat at
the other o and
p-pos1tion
I _,,:;:,
D

(X)
Phenol
¢ 0
14. In the Reimer-Tiemann reaction carbene intermediate is formed.
CHCl3 + OH- ~ H2O + CCl3 ~

Cl-+ : CCl2
p-,benzoquinone
Dichloro carbene
12. - OH group is activating group and is o- and p-directing. Also
- SO3H is a better leaving group and is knocked out by Br- .

A
y
OH
Br2 water
O -~-~-,
OH

9 . ,_.,
B r ~ Br
~cc,,~l&~c,, j ~~ &CHc1,
I LcH
oLcHo
~ lo J~ o ~o
L cH(OH)i
SO3H SO3H
Phenol Ortho-attack
Sulphonic acid
Unstable Salicylaldehyde
(2-hydroxy benzaldehyde)

15.
CH3
/CH3 I

para-attack 2, 4, 6-tribromophenol
13. Phenolic compounds in alkaline solution react with chloroform
~,CH,~~-~~JH
,~ O
~.::
Cumene Cumene
(CHCl 3 ) at a temperature lower than that of CHCl 2 to form (lsopropyl hydroperoxide
ortho-isomer as the maj or product (due to greater stability benzene)
OH
resulting from intramolecular hydrogen bonding).

@
0
9
II
- c1- + CH3 - C- CH 3
HO~ - CCl3 H2O + CCl3 ~ : CCl2 Acetone
'--..__..)' Dichloro Phenol
carbene
(A) (B)
618 I Chapterwise & Topicwise Engineering Entrances Solved Papers
16. An organic acid w ithout carboxylic group is picric acid. It is 2, 4, On the other hand presence of electron withdrawing group in the
6-trinitrophenol. It has phenolic group. ring stabilise phenoxide ion and increases the acidic nature of
OH phenols. Further, meta-isomer is less acidic then para because it
is stabilised by inductive effect only whereas para-isomer is
N20* N02 stabilised by both inductive and resonating effect. Thus, correct
1/' I order is TV > III > I > TT.
::::-....
OH
NO2
Picric acid
2, 4, 6-trinitrophenol 23.
Reduction
[HJ
A
~
Diazotisation
NaN02 - HCl(O")
17. Due to intra molecular hydrogen bonding in ortho-isomer, it has NH2
least melting point Due to effective intermolecular hydrogen

&
bonding and close packed strucn1re is para isomer, it has highest
melting point among the isomers. So the order is
Para > meta > ortho
(l 14° C) (97°C) (45°C) OH
Resorcinol
18. Phenol reacts with excess of bromine water to yield precipitate of
2, 4, 6-tribromophenol. OH

(J(CHO
@ Phenol
+ 3B,, ~
Br~Br
~ + 3HBr
24.

Phenol
(i) CHCl3;NaOH
(ii) H20/HC I

Salicylaldebyde
(Reimer-Tiemann's reaction)
Br 25. o-cresol contains phenolic group, thus it gives violet colouration
(2,4, 6-tribromophenol)
Whiteppt with FeCl 3 whereas benzyl alcohol doesn' t contains phenolic
group, hence no colouration with FeC1 3.
19. Phenol is a weak acid. It reacts with NaOH to produce salt.
Hence, identifiable.
C 6H 5OH + NaOH ~ C 6H 5ONa + H 2O
Sodium phenoxide
Phenols are weaker acids than carboxylic acids or even weaker
than carbonic acid.
It is because of this reason phenols do not decompose carbonates
26. >
and bicarbonates evolving CO2 gas.
20. Br2 is formed by a redox reaction :
SBr- + BrO3 + 6W ~ 3Br2 + 3H2O Due to - l and - R influence, NO 2 in
ortho-position should have raised the acidity to
--OH group is the activating group and there is SE at o-and
the maximum extent. But it is due to
µ-positions g1v111g yellowish white precipitate of
intramolecular H-bonding, ortho-nitrophenol is
2, 4 , 6-tribromophenol.
less acidic than para-nitrophenol.

0 +3B,2
27. Chlorobenzene Dow's process

Reimer- Tiemann
reaction
Phenol

Salicylaldehyde

28. After the loss of W ion, phenol forms phenoxide ion. The
phenoxide ion is resonance stabilised, thus makes the phenol
21. Reagent Phenol Benzoic acid Conclusion more acidic.

ld -~-~
Aqueous Salt Salt formation No specific colour change
NaOH formation
Neutral Violet Buff-coloured Thus, FeCl3 can be used
FeCl 3 colour precipitate to make distinction.

~-6J
22. Phenols are acidic in nature due to resonance stabilisation of
phenoxide ion. Presence of electrons releasing groups such as
- CH3 destabilises ion and decreases the acidic namre of
phenols.
(Resonating stn1cture of phenoxide ion)
 Alcohols, Phenols and Ethers I 619
OH OH 34. Diethyl sulphate in the presence of NaOH acts as alkylating

© "''o/"'
agent, it causes alkylation of phenol to give ethyl phenyl ether
3Br2 +H2O
+ 3 HBr which is also called phenetole.
29.
C6H sOH + NaOH - C6HsO- Na + + H2O
Phenol
Br C6H sO- Na+ + (C2H5)2SO4 -
2,4,6-tribromophenol Diethyl sulphate

© ©
SO3H OH Phenetole

©
35. In Reimer-Tiemann reaction salicylaldehyde is obtained when
30. H2SO4 (()N,QH ~ ~ phenol is heated w ith CHCl3 and aq. NaOH.
30K (ii) H+IH2O
OH OH
Benzene (A) (B)
Benzene
sulphonic acid
OH
Phenol
A + CHCl, + N,OH(R.e,mer-r ,emann
lS:;J
@(CHO

reaction) Salicylaldehyde

~
Br2

"''o/"' 0
Br
2,4,6-tribromophenol
36. Presence of electron withdrawing group such as NO2, CHO etc, on
benzene nucleus, makes phenol more acidic by stabilising
phenoxide ion while presence of electron releasing groups such as
-CH3,-C2H 5 destabilises the phenoxide ion, thus makes the
(C) phenol less acidic. Hence, the order ofacidity of given compound is
OH OH OH
OH OH

31.
©Phenol
3BrifH2O
LI

"''o/"' Q + 3HBr $>©>$

NO2 CH 3
Br III II
2,4,6-tribromophenol

OH

A ~
OH

~
OH OH OH

((N
O,
OH

32.
Uc U NaOH)
02
COONa ~
U
Salicylic acid
COOR 37.
6 Cone. H2SO4
sulphonation
¢SO3H
Cone. HNO3
I

First sulphonation is the means to block para position and to

reduce the reactivity of phenolic ring against strong oxidising
33. agent HNO 3. (The use of cone. HNO 3 over phenol cause the
oxidation of ring mainly).
The strong acidic medium in second step cause desulphonation
(ipso mechanism) also.
38. Like nitration, bromination of o-or p-phenolsulphonic acid occurs
with simultaneous replacement of SO3H group by Br atom to
ultimately give 2, 4, 6-tribromophenol.
OH

@rso,H B,~e,

Br
2, 4, 6-tribromophenol
620 I Chapterwise & Topicwise Engineering Entrances Solved Papers

39. Phenol on reaction with chloroform and KOH gives

salicylaldehyde, which with 50% KOH solution undergoes
Cannizzaro's reaction.

50% KOH )
+ CHC1 3 + (aq.) KOH
2, 4, 6-trinitrophenol
(picric acid)

45. In the presence of anhydrous ZnC1 2, phenol form salicylaldehyde.

50% It is Gattermann-aldehyde reaction.
KOH 46. Phenol does not decompose sodium carbonate or sodium
(Cannizzaro's
reaction) bicarbonate, i.e. CO2 is not evolved because phenol is a weaker
acid than carbonic acid.
40. Phenol on heating with CC1 4 and aqueous KOH gives salicylic 47. Reimer-Tiemann Reaction In this reaction phenol reacts with
acid. T his reaction is Reimer-Tiemann reaction. chloroform and alkali to fonn salicylaldehyde.
OH

NaOH © r CHCI,
aq. NaOH,
60°c
Phenol
41. When an electron attracting group ( like - NO2 , - Cl) is attached
to the phenol ring, it stabilises the negative charge on the oxygen of
phenoxide ion. Due to this reason acidic character of phenol
increases.
But when an electron donating group (like - CH3) is attached to
the phenol ring, it destabilises the ring and hence, acidic character
of phenol decreases. Salicylaldehyde

Thus, the correct order of acidic character is p-nitrophenol > 48. C2H 5OH and C6H 5OH can be distinguished by neutral FeC13
p -chlorophenol > phenol > o-cresol.
solution or I2 + NaOH solution. C2H 5OH gives iodoform test
42. Compound 'X' (C7HgO) is insoluble in aqueous NaHCO3 but with I2 + NaOH solution while phenol does not give yellow ppt.
soluble in NaOH, so it is a phenol. Since, the number of carbon of iodofonn.
atoms remains the same after bromination, the compound must be
6.
meta cresol and reactions takes place as follows C2H5OH + 4I2 + 6NaOH ~ CHI3
OH lodoform

J: Br2 BrYyBr
C6HsOH + I2 + NaOH ~ No reaction.
+ HCOONa + 5NaJ + 5H2O

C 6H 5OH reacts with neutral FeC13 solution to give purple colour

~ C H3 ~CH3 while C2H 5OH does not give any colour with neutral FeC13
m-cresol (X) (C7HgO) Br solution.
2, 4, 6,- tribromo
3- methyl phenol 49. Due to resonance the phenoxide ion is more stable whereas
(Y) resonance is not possible in a lkoxide ion.
43. The process of benzoylation of compounds containing active e
hydrogen such as phenol, ani line, alcohol, etc. , with benzoyl
chloride in the presence of aqueous NaOH is called
Schotten-Baumann reaction.

6
OH

+ C0H,COCI
NaOH
6
OCOC6H 5

+ HCI
6-6e-6e6 ~
:::,....
1~
6-
:::,....
I

Phenyl benzoate R- O 9 no resonance is possible,

44. Picric acid is 2, 4, 6-trinitrophenol. It is due to the presence of Since, phenoxide ion is better stabilised by resonance, the phenol
three -/ showing - NO2 grou ps, is more acidic than acetic acid has more tendency to form phenoxide ion by releasing W ion.
and benzoic acid. So, phenols are acidic in nature.
 Alcohols, Phenols and Ethers I 621
50. Phenol reacts with neutral FeCI 3 solution to give violet colour
OH

@ 38,, B,iB,
complex which is soluble in water.
6C6HsOH + FeCl3- [Fe(OC6Hs)d- + ------>
Violet colour complex 55.
+ 3H+ + 3HC1
Br
51. Phenol (C6HsOH) is carbolic acid.
Molecular weight of phenol = 12 x 6 + I x 6 + 16 = 94
52. Benzene sulphonic acid and p-nitro phenol react with NaHCO3
Molecular weight ofBr2 = 3 x 160 = 480
and evolve CO2 gas. 94 g of phenol requires= 480 gofBr2
SO3H SO3Na 480
2 g of phenol requires = x 2 = 10. 22 g

@ + NaHCO,------>@ + H,O + CO,

94
56. Phenol cannot be distinguished from ethanol by sodium because
both evolve hydrogen with sodium.
OH ONa 2C6H 5OH + 2Na- 2C6H 5ONa + H 2 i

rqi + N,Hco,------> rqi + H,O + co,

2C2H 5OH + 2Na- 2C2H 5ONa + H2 i
57. Picric acid is sym-trinitrophenol.

NO2 NO2 OH

Because benzene sulphonic acid and p-nitrophenol are stronger O,N~ NO,
acids, so they are capable to evolve CO2 with NaHCO 3.
HCO3 + H+ - H2O + CO2 i
Acid NO2
2, 4, 6-trinitrophenol
53. m-cresol due to phenoxide ion in H2O solvent, gives
tribromoderivative at all ortho and para positions. 58. Cumene is iso-propyl benzene (I-methyl ethy l benzene). On
CH 3 oxidation it gives phenol.

Br~Br

Y'oHBr

Cumene
B,*OH

~o
hydroperoxide
OH

Br
Dibromo derivative + (CH3)zC= O
Acetone
54. Reimer-Tiemann reaction this involves the treatment of phenol Phenol

&
with chloroform in aqueous sodium hydroxide solution followed
59. Phenol g ives characteristic colou ration (violet) with aqueous
by acid hydrolysis. Salicylaldehyde is formed.
FeC1 3 solution.
O~a+ 60. - OH group is an activating group, hence increase electron

CHCl3 ~CHO H++ H20 0 CHO density on o-and µ- position in benzene ring. Thus, phenol very
easily undergoes nitration (electrophilic substitution and give
NaOH ~ trinitrophenol, i.e. picric acid.
Salicylaldehyde

In the above reaction, chlorofonn first reacts with sodilun OH

hydroxide to produce dichloro carbene which is the intermediate

y
Dil. HN03
0 2N * N 0 2
in this reaction
H
I
Cl- C - Cl
ow •• •• Phenol
---4 Cl- C - Cl - Cl- C + Cl NO2
I I I 2, 4, 6-trinitrophenol
Cl Cl Cl (picric acid)
Dichlorocarbene
622 I Chapterwise & Topicwise Engineering Entrances Solved Papers

61. Salicylic acid+ NaHC03- effervescence of CO 2 Topic 4 Ethers

Phenol+ NaHC0 3- No reaction
1. Plan This problem can be solved by using the concept of
:. NaHC0 3 is used to d istinguish between phenol and salicylic stability of carbocation and SN I reaction. When two phenyl
acid. groups are replaced by two para methoxy group, carbocation
62. Phenyl magnesium bromide reacts w ith t-butanol to produce formed w ill be more stable. As the stability of carbocation formed
benzene because phenyl group (electronegative group) is increases, rate of acidic hy drolysis increases.
associated w ith active hydrogen of alcohol, i.e. -H of - OH OCH3
group of alcohol.
C6H5MgBr + (CH 3)3C- OH -
C6H 6 + (CH3)3CO- MgBr
OCH3 group indicated
63. Proton donors are acids. T he acidity of phenol increases by
presence of electron w ithdraw ing groups (e.g. - N02 group)
@-~ by arrow increases
the stability of carbocation

$
electronically (by + M-effect)
because these groups weaken th e 0 - H bond and stabilise the
phenoxide by resonance.
More the number of electron withdrawing group in compound
more will be acidity. On the other hand electron donating group
(e.g. CH 3)decrease the acidity of phenol because they strengthen OCH 3
More stable carbocation
the 0 - H bond. Therefore, correct order of acidity is
Hence (c) is the correct choice.
2. Compounds containing acidic hydrogen cannot be used in
Grignard's synthesis and the compound CH20HCH 2Br contains
~ N O,> ~ > ~ > ~ acidic hydrogen.
3. Ally! ethyl ether on reaction with HI produces ethanal and ethyl
N02 N02 CH3 iodide by means of necleophilic substitution reaction as shown
below
III > IV > > II
64. Electron withdrawing groups (like- N0 2) increase the acidity of
~c H
cHz- D·O - w,-
CH2 - CHr....:..;_--'---7
phenols by stabilising corresponding phenoxide ion. The effect of CH 3CH =O + CH 3CH2I
- N0 2 group will be minimum at m-position due to lack of Ethanal Ethyl ioidide
increased delocalisation of electrons in it. Hence, m-nitrophenol
is the weakest acid among these. 4. When an alkyl aryl ether is reacted with halogen acid (HX), the
products are always phenol and an alkyl halide.
65. Phenol NaNOi / H~o. B ~ C ~ D
C 6H 5 - 0- CH 2 - CH3 + HI ioo•c l
This is Liebermann's nitroso reaction of phenol. When phenol is
warmed w ith soditun nitrite and I cc. cone. H 2S04, blue colour is C6HsOH + CH3 - CH2 - I
Phenol Ethyl iodide
obtained w hich on adding water, becomes red. This again turns to y z
blue on adding NaOH. Deep blue colour is due to the formation of
sodium salt of indophenol.

6. Molecular formula C3H 80(C,,H2,, + 20) suggests that the

Sodium salt of indophenol organic compound is either alcohol or ether. Since, the compotmd
(deep blue) on reaction w ith m gives two different compounds, It must be an
tmsymmetrical ether, and its formula must be CH30C2H 5
66. Phenol are less acidic than carboxylic acid, because carboxylate ( methoxyethane).
ion is relatively more stable as compared to phenoxide ion.
CH30C2H5 + 2HI - CH3I + C2H50H
Methoxyethane (X) (y)
C2H50H+ 6NaOH+4I2 -
Aqueous
CHI3 + HCOONa + 5H 20 + 5Nal
Carboxylate ion Phenoxide ion lodoforrn
 Alcohols, Phenols and Ethers I 623
7. Ether peroxide oxidises KI into I2 and itself gets reduced to ether. ONa OCH3
Therefore, KI is added to remove peroxides from ethers.
21 -
Ether peroxide + 2e- -
I2 + 2e-
ether + 02
CH 3T +
Methyl iodide © ©
Sodium
phenate
~

Anisole
+ N,I

8. C2H50C2H5 + (CH3CO)iO AICl 3 CH3COOC2H5

16. Benzyl phenyl ether is an unsymmetrical ether so halide ion of HI
Diethyl ether Acetic anhydride Ethyl acetate
is attached to the simple alkyl group and reaction takes place by
9. Alcohols (-OH) react with sodium and carbonyl compounds following mechanism.
()C=O) give precipitate with semicarbazide. (i) Protonation of ether
Since, the compound with molecular formula, C3H60 does not
give precipitate with semicarbazide and does react with sodium, C6H5CH20C6Hs + H I - C6H5CH2- 0 - C6Hs + 1
~
it is neither a carbonyl compound nor an alcohol. Hence, it must Benzyl phenyl ether I
H
be an ether, i.e. CH 2 = CHOCH 3.
10. Grignard reagent (RMgX) reacts with only those compounds (ii) Nucleophilic attack
$
which contains acidic hydrogen or which contains carbonyl group.
I-
1
+ C6H5CH2 o - C6H5-
D imethyl ether (CH 30CH 3) due to the absence of both acidic
hydrogen and carbonyl group does not react with Grignard
Nucleophile J
reagent. C6H5CH 2I + C6HsOH
Benzyl iodide Phenol
11. CH 3 - O- CH 3 sp3 and sp3-hybridisation of carbon and 17. Only acidic compounds such as acetic acid, phenol and alcohol
sp3 ;P~ sp3 react with sodium metal. Ether is not acidic in nature, hence it
does react with sodium metal.
oxygen in electronic strncture of ether.
2CH3CH20H + 2Na- 2CH3CH 20Na + H2
12. Molecular weight of diethyl ether is more than ethanol. Ethanol Sodium ethoxide
Therefore, it should have higher boiling point than ethanol. But it
is not so. 2CH3COOH + 2Na- 2CH3COONa + H 2
Acetic acid Sodium acetate
It is due to intermolecular hydrogen bonding. Ethyl alcohol has
intermolecular hydrogen bonding but diethyl ether has no 2C6HsOH + 2Na- 2C6Hs0Na + H2
hydrogen bonding. Phenol Sodium
phenoxide
The compounds shows intermolecular hydrogen bonding has
higher melting point and boiling point than compounds having no CH3- 0 - CH3 +Na- No reaction
hydrogen bonding. Therefore, the boiling point of diethyl ether 18. Catechol is most acidic out of all dihydric phenols.
will be less than ethanol (78°C).
13. In the presence ofNaOH or KOH, phenol reacts with alkyl halide (8y'OH NaOH
and gives phenolic ether (C 6H 50R).
C6H50H + NaOH _ Hp C6Hs0- Na ~ OH
RX
- NaX C6H5- 0 - R

Vapou rs of C6H 50 H and CH 30H, with red hot Th02 (thoria)

give anisole (phenolic ether). The reaction is Williamson's synthesis type reaction.
Th02 19. When an alkyl aryl ether is heated with HI, halogen goes with
C6H50H + CH30H~ C6H50CH3 + H20
Anisole alkyl group. Therefore, heating anisole (methyl phenyl ether)
with HI phenol and methyl iodide are obtained.
14. Here, ether is the solvent. Being less polar, it favours SN2
reaction and the nucleophile 1- attacks the I O carbon of CH 3. OCH3 OH

~1
~CH3
,eSN2
1 + CH30-C-CH3~CH3T+
I I
H CH3
CH3-C-OH
CH3
I
I
CH3
© ©
Anisole
+ m---->
Phenol
+ CH,!

20. Williamson's synthesis It involves the heating of alkyl halide

15. The reaction of alkyl halide with sodium alkoxide to give ether with sodium or potassium alkoxides. This reaction is used for the
(alkoxy alkane) is known as W illiamson's synthesis. In this preparation of ethers, e.g.
reaction an ether (anisole) is prepared by the action of alkyl halide
C2H50Na + C2H5I - C2H5- 0C2H5 + NaI
(methyl iodide) on sodium alkoxide (sodium phenate), so it is an
example of W illiamson's synthesis.
624 I Chapterwise & Topicwise Engineering Entrances Solved Papers

21. CH CH ONa + C H Br Williamson's 27. Ethyl chloride reacts with sodium ethoxide to form diethyl ether
3 2 2 5 as
synthesis
Sodium ethoxide Brorno ethane
C2H 51Cl + NalOC2H5 - C2H 5 -O-C2H5 + NaCl
CH3CH2OCH2CH3 + NaBr Diethyl ether
Ethoxyethane
Diethyl ether is also obtained by reaction of ethyl alcohol with
22. Alcohol has polar H which makes intermolecular H-bonding cone. H2SO4 at 140°C.
possible. Ether is non-polar hence no H-bonding. Lack of
H-bonding in ether makes it more volatile than alcohol. CH3CH2OH + HOCH2CH3 Cone HzS04 l
140°c
23. Williamson's synthesis is the best method for the laboratory
preparation of both simple and mixed ethers and involves the C2H5-O-C2H5 + H2O
Diethyl ether
action of sodium alkoxide on a suitable alkyl halide.
C2H5- Br + C2H 5ONa- 28. Ethanol on dehydration in presence of cone. H2SO4 at 140°C,
Ethyl bromide gives diethyl ether.
C2H5- O- C2H5 + NaBr Cone. H:z$04
C2H5 -Cl + C6H5- ONa - Diethyl ether
2C2H5OH 1400c C2H5-O-C2H5 + H2O
Diethyl ether
C6H5-O-C2H5 + NaCl 29. C2H5OC2H5 + HI- C2H5OH + C2H5I
Ethyl phenyl ether
30. Methyl phenyl ether is obtained by the reaction ofphenolate ions
24. Williamson's synthesis is used for the preparation of ethers. and methyl iodide.
RCl + NaOR' Williamson's R- 0 - R' + NaCl C6HsO- + CH3I- C6H5OCH3 + r
syntheSIS Ether Methyl phenyl ether

31. Alkyl halides react with sodium alkoxide to give ether. This is
25. C6H 50- R Cold HI C6H5OH + RI called Williamson's synthesis of ether.
Aryl -alkyl ether Phenol Alkyl iodide
/',.
26. Diethyl ether when heated with CO at 150°C and 500 atm
C2H 5Cl + C2H5ONa- C2H5OC2H 5 + NaCl
Ether
pressure in presence of BF3 forms ethyl propionate.
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Aldehydes, Ketones and
Carboxylic Acids
QUICK REVIEW
Preparation of Aldehydes and Ketones
• In Rosenmund's reaction, acid chlorides are reduced with
hydrogen in boiling xylene using Pd or Pt as catalyst
supported over BaSO4 (to prevent further, reduction of
aldehyde catalyst is poisoned by BaSO4 or sulphur or
quinoline). Formaldehyde cannot be obtained by
Rosenmund's reduction because formyl chloride is
unstable at room temperature.
• Stephen reduction of alkyl or aryl halides with
SnC1 2/HCl followed by hydrolysis with boiling water
gives aldehydes.
• Ketones cannot be prepared from acid chloride (RCOCl)
and Grignard reagent because as the ketones produced,
they react fUither with Grignard reagent to produce
tertiary alcohol on subsequent hydrolysis.
• In the reaction of methyl benzene with CrO3 , acetic
anhydride is used to trap benzaldehyde as benzylidene
diacetate to avoid its further oxidation to benzoic acid.
• Methyl benzene is converted to benzaldehyde through
Etard's reaction. If the side chain contains alkyl groups
higher than -CH3 group, then corresponding aldehydes
are formed.
e.g.
(i) Cr02Cl2
(ii) H20
Phenyl ethanal
Carbonyl Group
The C = 0 group is known as the carbonyl group and the
compounds containing C = 0 group are known as carbonyl
compounds.
Properties of Carbonyl Compounds
• Reactivity order among aldehydes and ketones is as follows
HCHO > CH3 CHO > CH3 CH2CHO
> CH3COCH3 > C2HsCOCH3> C2H5COC2H2
Ease of nucleophilic attack on carbonyl carbon depends
upon two factors :
(a)+ I -effect of alkyl group
(b) steric hindrance.
• Aromatic aldehydes and ketones are less reactive than
cotTesponding aliphatic analogues because increase in
electron density on the carbonyl carbon due to + R or
+ M-effect of benzene ring makes the attack ofnucleophile
slow.
• Cyanohydrins on hydrolysis followed by heating produce
ex., P-unsaturated acids. e.g.
H 3 C, H C, /OH
/'C= O+ HCN ~ 3 'C
H H / "-CN
CH2 = CH-COOH
Acrylic acid
626 I Chapterwise & Topicwise Engineering Entrances Solved Papers
• On thermal decomposition, acetaldehyde gives
CH4 + CO and acetone gives ketene (CH 2 = C = 0)
and methane.
• Distinction between aldehydes and ketones can be done
by Tollen's test or Fehling's solution test or Schiff's
reagent test. These test are not given by ketones.
Benzaldehyde reduces Tollen's reagent but it does not
reduce Fehling's or Benedict reagents.
• All aldehydes including benzaldehyde and aliphatic
methyl ketones react with sodium hydrogen sulphite
and form insoluble, crystalline bisulphite addition
products. These products are useful for separation and
purification of aldehydes.
• The reduction of carbonyl compounds to alkanes by
using Zn-Hg/HCI is known as Clemmensen's
reduction while the reduction of carbonyl compounds
to alkanes by using hydrazine and KOH/glycol is
known as Wolff-Kishner reduction.
Clemmensen reduction is not applicable to C= 0
compound containing acid sensitive groups like --OH
or sterically hindered ketones.
• Meerwein Ponndorf Verley reduction (Reduction
with aluminium isopropoxide in excess of isopropyl
alcohol) is a selective reduction which reduces
>C = O to> CHOR
• Aldehydes and ketones having a-Hatom in presence of
dilute alkali undergo aldol condensation to form
P-hydroxy aldehyde and P-hydroxy ketone.
• Aldehydes without a-H atom such as HCHO or
C6 H 5 CHO in presence of 50% NaOH undergo
Cannizaro's reaction (selfoxidation reduction process)
• Ce11ain mono alkylated aldehydes such as 2-methyl
• Complete hydrolysis of nitrites under acidic or alkaline
conditions gives carboxylic acids.
Carboxylic Acids
• Acid or alkaline hydrolysis of esters, anhydrides, amides and
acid chlorides gives carboxylic acids.
• Grignard reagents react with dry ice (CO 2 ) in ethereal pollution
and produce salts of carboxylic acids which on acidification
with mineral acids give corresponding carboxylic acids.
Properties of Carboxylic Acids
• Acidic strength of different carboxylic acids in decreasing
order:
• HCOOH> C6 H 5 COOH> C6 H5 CH 2 COOH>
CH 3COOH > (CH3 ) 2 CHCOOH >
> (CH3 )J C-COOH
➔ CH3CH 2 CC1 2 COOH >
CH3CHCH(Cl)COOH > CH 2 ClCH(Cl)CH2 COOH
I
Cl
➔ CF3COOH > CCI 3 COOH > CBr3 COOH >
NO 2 CH 2 COOH> FCH 2 COOH
ClCH2 COOH > BrCH2 COOH
COOH
~%, $ OH>~:O, >

N02
>
$>Cl
propanal ((CH 3 h CHCHO) has an a-H atom also
undergo Cannizaro's reaction.
• Aldehydes and ketones on reaction with PCI 5 or SOC! 2
give gem. dichlorides. No HCI gas is given out. e.g.
/Cl
C = O + PCl 5 ~ C"- + POCl 3
Cl

$ >CH COOH>$
/Cl COOH COOH
C= O + SOCl 2 ~ C"- + SO2
Cl
3
• Aldehydes react with monohydric alcohols in presence
of dry HCl gas to yield alkoxy alcohol intermediate,
known as herniacetals, which on further reaction with OH NH2
alcohol give a gem-dialkoxy compound known as Presence of a group having - I- effect in alkyl group increases the
acetal. Ketones react with ethylene glycol under same acidic strength of carboxylic acids and vice-versa. Presence of
conditions to yield cyclic products known as ketals. electron attracting group at p-position increases acidic strength
of aromatic acids and vice-versa. Presence of any substituent at
• Alkyl benzene on oxidation with alk. KMnO 4 always
ortho position increases acidic strength of aromatic acids
give benzoic acid irrespective of chain length. e.g. (ortho-effect) .
 Aldehydes, Ketones and Carboxylic Acids I 627
• o -substituted benzoic acids are usually stronger acids than undergo ex,-halogenation with Cl 2 and Br2 in the presence
benzoic acid regardless of the nature of the substituents of red phosphorus (Hell-Volhard Zelinsky reaction).
(ortho-effect). • Lactic acid is a-hydroxy propionic acid
• Carboxylic acids are stronger acids than phenols since (CH 3 - CHCOOH)
carboxylate ion is better stabilised by resonance than I
phenoxide ion. OH
• Methanoic acid and its sodium salt acts as a reducing agent It gives iodofo1m test. Lactic acid on mild oxidation with
due to the presence of -CHO group. It reduces Tollen's FeSO4 / H 2 O 2 gives pyruvic acid ((CH 3 COCOOH).
reagent, Fehling 's reagent, chloride and KMnO4 . • Electron deficiency on acyl carbon and basicity ofleaving
• On heating with sodalime at 630 K, carboxylic acids group is responsible for the following order ofreactivity of
undergo decarboxylation to form alkanes containing one C acid derivatives towards nucleophilic acyl substitution
atom less than the corrresponing carboxylic acid. reaction,
• Electrolysis of an aqueous solution of sodium/potassium R-COCI >(RCO)iO >R-COOR' >RCONH 2 .
salts of fatty acids gives alkanes (Kolbe's electrolytic • + I-effect of CH 3 group makes C-CI bond weaker while
reaction). - I-effect of C 6 H 5 group makes C-CI bond stronger.
• Dry distillation of calcium salts of fatty acids give • Urea is synthesized in laboratory by heating ammonium
aldehydes or ketones. cyanate.
• Decarboxylation of silver salts of fatty acids in presence of LI.
NH4 CNO ---,R_earra_n_ge_rre_n_t➔ NH 2 CONH2
Br2 in refluxing CCl 4 gives alkyl/aryl bromide (1 C-atom
Ammonium Urea
less). This is Hindsdiecker reaction. cyanate

• Carboxylic acids are reduced to primary alcohols with On heating above l 32°C urea gives biuret
LiAlH4 or better with di borane in ether solution and also (NH 2 CONHCONH 2 ).

Topic 1
Preparation of Aldehydes and Ketones
2014
1. The most suitable reagent for the conversion of
3_ X Ozonolysis Y+Z
R- CH 2 - OH~ R - CHO is (Reductive)

(a) KMnO4 [JEE Mains, Kerala CEEJ Y can be obtained by Etard's reaction, Z undergoes
(b) K 2 Cr2O1 disproportionation reaction with concentrated alkali. X
(c) Cr03 could be CKCETJ
(d) PCC (pyridinium chlorochromate)
2. Shown below are four possible synthesis of (a) © r C = CH
propionaldehyde. Which one would not work? [ManipalJ
0 (b) ©rCH = CH 2
H PCC) II
(a) .,/"---....0/ ~ H
CH = CH -CH3
0 0 (c) ~l8J
H II (i) LiAIH4 II / CH3
(b)~O/ (ii)H+ ) ~H (r\yCH = C"-.
(d) l8) CH3
0 0
(c) IICH (i)DIBAL-H II 4. When CH 2 = CH-O-CH2 -CH3 reacts with one
~0/ 3 (ii)ff+ ~H
mole of HI, one of the products formed is [KCETJ
0 0
d) II CH (i) LiAIH4 (0-t-Bu)J II (a) ethane (b) ethanol
( ~Cl/ 3(ii)H+ )~H (c) iodoethene (d) ethanal
628 I Chapterwise & Topicwise Engineering Entrances Solved Papers

5. Acetophenone cannot be prepared easily starting from 2012

(a) C 6 H 5 CH(OH)CH3 (b) C 6 H 5 CH3 [KCETJ 13. Which of the following process is used for the preparation
(c) C 6 H 5 C= CH (d) C 6 H 6 of acetone? [BITSATJ
6. The reaction ofH2 is given below (a) Haber's process
H2 + CO + R-CH = CH 2 ~ (b) Wacker's process
R-CH 2-CH2 -CHO is specifically called as (c) Wolff-Kishner reaction
(d) Gatterman-Koch synthesis
(a) hydrogenation (b) reduction [Kerala CEEJ
(c) hydroformylation (d) dehydration 2011
(e) formylation
14. Which of the following gives an aldehyde on dry
7. The reagents to carry out the following conversion are
distillation? CKCETJ
Me =~Me ~ I( Me (a) Calcium formate + calcium acetate
(b) Calcium acetate + calcium benzoate
0
(c) Calcium acetate
(a) HgS0 4 / dil. H2S04 [WBJEEJ (d) Calcium benzoate
(b) BH3 ; H20 2 /Na0H
(c) Os0 4 ; H10 4 2010
(d) NaNH2 /CH 3 I; HgS04 /di!. H2S04 15. Collin's reagent is used to convert [Manipal]

0 (a) C = 0 ~ CHOH
(b)-CH20 H ~ CHO
8. ~ C H , (c) -CHO~ -COOH
(d) -CHO~ -CH20H
The above ketone will not be formed by [AMU]
16. Which set of products is expected on reductive ozonolysis
(a) reaction of benzene and acetyl chloride in the
of the following diolefin?
presence of A!Cl 3
(b) reaction of acetonitrile with phenyl magnesium CH3
bromide in ether followed by hydrolysis I
(c) treatment ofacetyl chloride with dibenzyl cadmium CH3 CH = C-CH= CH 2 [Punjab CETJ
(d) addition of water to phenyl acetylene in the presence
(a)CH 3 CHO; CH 3 COCH = CH2
of mercuric sulphate and dilute sulphuric acid.
(b)CH 3 CH = C(CH3 )CHO; CH 2 0
9. What will be the product/s ifbenzyl chloride is heated with (c)CH 3 CHO;CH3 COCHO;CH 2 0
a concentrated aqueous KOH solution? [AMU]
(d) CH3 CHO; CH3 COCH3 ; CH20
(a) Benzaldehyde
(b) Benzoic acid 2009
(c) Benzyl alcohol and sodium benzoate 17. Which of the following on heating with aqueous KOH,
(d) An aldol produces acetaldehyde? [AIEEEJ
10. What type of compound is shown below? (a) CH3COCl
0 (b) CH3CH 2CI
II (c) CH2ClCH 2CI
H-C-CH 2 -CH3 [Indraprastha CET]
(d) CH3CHC12
(a) An alcohol (b) An aldehyde 18. The compound which is not formed during the dry
(c) A ketone (d) None of these distillation of a mixture of calcium formate and calcium
11. Carbonyl compounds are constituents of [J&K CETJ acetate is [Manipall
(a) fabrics, drugs (b) fabrics, plastics (a) methanal (b) propanal
(c) flavourings, plastics (d) All of the above (c) propanone (d) ethanal
19. The compound which forms acetaldehyde when heated
2013 with dilute NaOH, is [Manipall
12. When a mixture of calcium acetate and calcium formate is
(a) 1, 1-dicholoroethane
dry distilled, the product formed as [KCETJ (b) 1, 1, I -trichloroethane
(a) ethanal (b) butanone (c) 1-chloroethane
(c) methanal (d) acetophenone (d) 1, 2-dichloroethane
 Aldehydes, Ketones and Carboxylic Acids I 629
2008
CHO 24. Which one of the following can be oxidised to the

20. @ +? AICl3
HCl )
@ coITesponding carbonyl compound?
(a) 2-hydroxypropane
(b) ortho-nitrophenol
[Manipal]

Identify the reactant. [VITEEE] (c) Phenol

(a) H 2 0 (b) HCHO (d) 2-methyl-2-hydroxypropane
(c)CO (d) CH3 CHO 25. Stephen's reduction is used to prepare aldehyde from
21. The product Pin the reaction, [Ke rala CEEJ (a) alcohol (b) alkyl cyanides [WBJEEJ
(c) alkanones (d) acid chlorides
#N 26. 3-pentanol on reaction with aluminium tertiary butoxide in

u~
the presence of acetone gives [OJEEJ
HO' (a) 3-pentanal (b) 2-pentanal
+ CH 3MgBr ~ Q .....:.:i:::... Pis (c) 3-pentanone (d) 2-pentanone
OCH 3
2006
C- H
21 A + H
• 2
Pd/BaS04
O(
I[
0

CN
(a) ~ ~ - C l [DCE]
(b)v
Vo
CHO
0
II
i
C- CH3

(b)
Q OCH3
(c) C
r(YC- NH2 (d)
V
,,:::-

28. Which one of the following product is formed when

0 calcium salt of adipic acid is heated? [BITSATJ

(c) ~OCH
(d)
6:Hi
II
(a)
CH 2-
I
CH2 "-.

CH2 - CH2
/0

CH,CH2 CO "-.
(c) I -
CH 2- CH2"-.
(b) I
CH2 - CH 2
/C = O

CH 2CH 2COOH
/C= O (d) I
3 OCH3
CH 2CH2 CO CH 2CH2COOH
29. When calcium acetate is distilled, it will produce which of
the following compound? [WB JEE]

(a) CH 3 COOH (b) CH3 CHO

(c) CH 3 COCH3 (d) All of these
30. Which reaction is used for the preparation of
22. When a mixture ofcalcium benzoate and calcium acetate is acetophenone? [WB JEE]
dry distilled, the resulting compound is (a) Reimer-Tiemann reaction (b) Wurtz-Fittig reaction
(a) acetophenone [Jamia Millia Islamia] (c) Friedel-Craft's reaction (d) Cannizaro's reaction
(b) benzaldehyde
31. The reagent used in Gatte1mann Koch aldehyde synthesis is
(c) benzophenone
(d) acetaldehyde (a) Pb/BaS04 [WB JEE]
(b) alkaline KMnO4
2007 (c) acidic KMnO4
23. The catalyst used in Rosenmund reaction is [VITEEEJ (d) CO + HCl
(a) Zn/Hg 3 2. Calcium formate on distillation gives CUPSEEJ
(b) Pd/BaS04 (a) HCOOH (b) CH3 COOH
(c) Raney Ni (c) CH 3 CHO (d) HCHO
(d) Na in ethanol
630 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2005
33. The best reagent to convert pent-3-en-2-ol into pent-3-en-2-one is [AIEEE]
(a) pyridinium chlorochromate (b) chromic anhydride in glacial acetic acid
( c) acidic dichromate ( d) acidic p ermanganate
34. By combining the two calcium salts of carboxylic acids we are preparing 2-butanone. Find the correct pair from the following.
(a) Calcium formate + calcium propanoate (b) Calcium acetate+ calcium propanoate [MHT CETJ
(c) Calcium acetate + calcium acetate (d) Calcium formate+ calcium acetate
35. Which of the following, compounds is the reactant in Rosenmund's reduction? [EAMCET]
(a) CH 3 C0 2 H (b) CH 3 CHO
(c) CH 3 CH 2 Cl (d) CH 3 COC1

Topic 2
Properties of Carbonyl Compounds
2014
1. The major product in the following reaction is 4. Which of the following compounds will give positive
[JEE Advanced] iodoform test with I2 and NaOH? [BITSATJ
0 (a) C6 H 5 COC 6 H 5 (b) CH 3 CH 2 CHO
~ {i) CH3MgBr, dry ether, 0°C (c) C6 H 5 COCH 2 CH 3 (d) C 6 H 5 -CH-CH 3
Cl CH3 {ii)Aqueous acid I
OH
5. What will be the order of reactivity of the following
carbony I compounds with Grignard' s reagent? [VITEEEJ
H"- H"-
/C = O /C = O
H H 3C
I II
H 3C"- (CH3) 3 C "-
/C = 0 /C = 0
H3C (CH 3) 3C
III IV
(a) I > II > III > IV (b) IV > III > 11 > I
(c) II > I > IV > III (d) III > II > I > IV
6. How many enols (including stereo isomers) exist for
2. How many chiral centre are possible for the product of 3-hexanone? [Manipall
following reaction? [BITSATJ
(a) Two (b) Three (c) Four (d) Six
0 7. The compound C 6 H 5 CH = N-N = CHC6 H 5
CH3, ll +_ CH {i) Michael
is produced by the reaction of an excess of benzaldehyde
/ ....._H -----y 3 addition ) A
CH3 II {ii) OH- with which compound? [Manipall
0 (a) NH3 (b) NH2 NH2
(a) 1 (b) 0 (c) 3 (d) 2 (c) Hydroxyl amine (d) Phenyl hydrazine
3. Arrange the following compounds in the increasing order 8. Which of the following statements is not true for
of nucleophilic addition reaction [BITSATJ acetaldehyde? [Manipall
I. HCHO II. CH3COCH3 (a) It will undergo an aldol condensation reaction
III. ¼H5 COCH 3 TV. ¼ H5CO¼H 5 (b) It will undergo a Cannizaro reaction
(a) I < II < III < IV (b) IV < III < II < I (c) It will undergo a haloform reaction
( c) IV < II < III < I (d) III < IV < II < I (d) Enolisation is catalysed by acid or base
 Aldehydes, Ketones and Carboxylic Acids I 631

9. -YH + CH3 Mg Br Ether ) A H20IW B

15. The intermediate J in the following Wittig reaction is
[WBJEE]
0
The IUPAC name of B is [KCET]
0- PPh B
3 r
(i) n-BuLi
(ii)CH2 =0)
[J]
~
O=
(a) 3-methylbutan-2-ol
PPh3
(b) 2-methylbutan-3-ol
(c) 2-methylbutan-2-ol
(b) C)<c)
(d) pentan-2-ol
10. The compound of molecular fommJa C 5 H 10 O(A) reacts (\/0,
(c) l._/vPPh3
wiJI ToJlen's reagent to give silver minor but does not
undergo aJdol condensation. The compound A is
16. The order of compounds in their reactivity towards HCN
(a) 3-pentanone [Ke rala CEE]
is [AMU]
(b) 2, 2-dimethylpropanal
(d) 3-methylb utanal (a) acetaldehyde < ketone < methyl tert-butyl ketone
( e) 3-methyl-2-butanone < di-tert-butyl ketone
(b) di-tert-b utyl ketone < methyl tert-butyl ketone
11. Identify the combination of compounds that undergo aldol
< acetone < acetaldehyde
condensation followed by dehydration to produce (c) di-tert-butyl ketone < acetone < methyl tert-butyl
but-2-enal [Ke rala CEE] ketone < acetaldehyde
(a) methanal and ethanal (b) two moles of ethanal (d) Acetone < acetaldehyde < di-tert-butyl ketone
(c) methanal and propanone (d) ethanol and propanone < methyl tert-butyl ketone
(e) two moles of ethanol
17. What kind of isomerism is exhibited by the compounds
12. An organic compounds with the molecular formula CH 3 CH 2 CHO and CH3 COCH 3 ? [J&KCET]
C 8 H 8 O fom1S 2, 4-DNP derivative, reduces Tollen's (a) Geometrical isomerism
reagent and undergoes Cannizaro reaction. On vigorous (b) Functional isomers
oxidation, it gives 1, 2-benzenedicarboxylic acid. The (c) Tautomers
organic compound is [Ke rala CEE] (d) Metan1ers
(a) 2-ethylbenzaldehyde (b) 2-methylbenzaldehyde 18. When acetaldehyde is heated with dilute sodium hydroxide
(c) acetophenone (d) 3-methylbenzaldehyde solution, the product is [J&K CET]
(e) phenylacetaldehyde
(a) ethanol and sodium acetate
13. Among the following structures the one which is not a (b) paraldehyde
resonating stmcture of others is [WB JEE] (c) aldol
0 0 o 08 ( d) brown resin

Me,~Me Me,O~Me 2013

I II 19. Which of the following organic compounds answers both
iodoform test and Fehling's test? CKCETJ

Me,
M III
Me
Me, ~ _
0
0

IV
0
(a) Methanal
( c) Propane
(b) Ethanol
(d) Ethanal
20. An important industrial solvent, also a laboratory reagent,
(a) Only I (b) Only II called 2-butanone, is nothing but CKCETJ
(c) Only III (d) Only IV (a) methyl ethyl ketone (b) dimethyl ketone
14. In the following reaction, the product E is (c) diethyl ketone (d) propyl ketone

fHO (i) NaOH E

[WBJEE]
(e) methyl propyl ketone
21. If formaldehyde and KOH are heated, we get CKCETJ
CHO (ii) H+
(a) methane (b) methyl alcohol
CH2 O H CHO (c) ethyl formate (d) acetylene
(a) hHo (b) I
CO 2 H
22. Oxidation of aldehydes gives [KCEEJ
(a) esters (b) acids
CO2 H (c) ethers ( d) alcohols
{d) ho2H (e) esters and acids
632 I Chapterwise & Topicwise Engineering Entrances Solved Papers

23. Reactivity towards nucleophilic addition reaction of 28. In the given transformation, which of the following is the
T. HCHO TT. CH3 CHO [OJEEJ most appropriate reagent? [AIEEEJ
IIT. CH 3COCH 3 is
(a) II > III > I (b) III > II > I
Jg( CH = CHCOCH3 Reagent

(c)I > II > III (d) I > III > II

HO ~ CH= CHCH2 CH3
24. After completion of the reactions (I and II), the organic
compound(s) in the reaction mixtures is (are) COJEEJ
HO~

Reaction I H3C
A 0
CH3
Br2
(1.0mol)
Aqueous/
EB
(a) NH 2 NH 2 , OH (b) Zn-Hg/ HCI
(1.0 mol) NaOH (c) Na, Liq. NH 3 (d) NaBH4
O Br2 29. HCHO was treated with a reagent X . The product formed
Reaction II H3C A (1.0 mol)
CH3 CH3COOH)
(1.0 mol)
upon hydrolysis in the presence of an acid gave C2 H 5 OH
The reagent X is [KCETJ
(a) alcoholic KOH (b) alcoholic KCN
(c) CH 3 MgI (d) aqueous KOH
30. Upon treatment with A1(OEt) 3 followed by usual reactions
(work up) CH3 CHO will produce [WB JEE]
(a) Only CH 3 COOCH 2 CH 3
(b) a mixture of CH 3 COOH and EtOH
(c) Only CH 3 COOH
(d) Only EtOH
31. An organic compound 'A' burns with a sooty flame. It is
neagtive towards Tollen's reagent test and positive for
ONa Brady's reagent test. The compound 'A' is [OJEEJ
+ CO2~ B~
5 atm
C
Ac20
(a) Acetophenone (b) Acetone
(c) Salicylic acid (d) Bezaldehyde
(a) Reaction I P and Reaction II P 32. Which of the following does not give Cannizzaro's
(b) Reaction I U, acetone and Reaction II Q, acetone reaction? [OJEEJ
(c) Reaction I T, U acetone and Reaction II P (a) CC13 CHO (b) C 6 H 5 CHO
(d) Reaction I R acetone and reaction II S acetone
(c) HCHO (d) CH 3 CHO
25. Among H-CHO,CH3CHOand C 6 H 5 CHO, which will
undergo Cannizzaro's reaction? [OJEEJ 2011
(a) HCHO and CH3 -CHO 33. The major product of the following reaction is [IITJEEJ
(b) CH3-CHOand C 6 H 5 CHO
(c) C 6 H 5 CHOand HCHO
(d) All of the above
0 0
H+(hydrous)

(a) a hemiacetal (b) an acetal

2012 (c) an ether (d) an ester
26. The number of aldol reaction(s) that occurs in the given 34. Trichloroacetaldehyde was subjected to Cannizzaro's
transformation is [HT JEE] reaction by using NaOH. The mixture of the products
OH OH contains sodium trichloroacetate ion and another
CH3CHO + 4HCHO Cone. aq. NaOH ~ + HCOO- compound. The other compound is [AIEEEJ
(a) 2, 2, 2-trichlorethanol
HO OH (b) trichloromethanol
(a) 1 (b) 2 (c) 2, 2, 2-trichloropropanol
(c) 3 (d) 4 (d) chloroform
27. lodoform can be prepared form all except [AIEEEJ 35. Silver min-or test is given by which one of the following
compounds? CAIEEEJ
(a) ethyl methyl ketone
(b) iso-propyl alcohol (a) Acetaldehyde
(c) 3-methyl-2-butanone (b) Acetone
(d) iso-buty1 alcohol (c) Formaldehyde
(d) Benozophenone
 Aldehydes, Ketones and Carboxylic Acids I 633
36. The reagent with which both acetaldehyde and acetone (a) CH 2 = CH- CH-COOR
react is [KCET] I
(a) Fehling's solution (b) 12 / NaOH
OH
(b) CH 2 = CH-CH-OH
(c) Tollen's reagent (d) carbonic acid
I
37. Reaction of formaldehyde and ammonia gives [WB JEE] CN
(a) hexamethylene tetramine (c) CH3 CH2 - CH-COOH
I
(b) bakelite OH
(c) urea (d) CH3 -CH-COOR
(d) triethylene tetramine I
38. Which of the following reactions convert acetone into OH
hydrocarbon having same number of carbon atoms? 45. Benzaldehyde reacts with ammonia to fo1m [JCECE]
(a) Wolff-Kishner reaction [Guj CET] (a) benzaldehyde ammonia (b) urotropine
(b) Hofmann reaction (c) hydrobenzamide (d) ammonium chloride
(c) Grignard reaction 46. The most reactive compound towards fo1mation of
(d) Reduction with LiAIH4 cyanohydrin on treatment with HCN followed by
acidification is [JCECEJ
2010 (a) benzaldehyde (b) p -nitrobenzaldehyde
39. In the scheme given below, the total number of (c) phenylacetaldehyde (d) p-hydroxybenzaldehyde
intramolecular aldol condensation products formed from
'Y' is [IIT JEE] 2009
47. An organic compound Xis oxidised by using acidified
00
(i) 03 y (i) NaOH(aq)
(11) Xn, H20 (11) heat K 2 Cr2 0 7 . The product obtained reacts with phenyl
hydrazine but does not answer silver mirror test. The
(a) I (b) 2 (c) 3 (d) 4 possible structure of X is [Manipal]
40. Which one of the following undergoes reaction with 50% (a) CH3 CH2 0H (b) CH3 -C-CH3
sodium hydroxide solution to give the corresponding II
alcohol and acid? [Manipall 0
(a) Phenol (b) Benzaldehyde (c)(CH 3 ) 2 CHOR (d) CH3 CHO
(c) Butanal (d) Benzoic acid 48. CH 3 COOH X Cu y Dilute Z
300"C ) NaOH
41. The compound obtained when acetaldehyde reacts with
dilute aqueous sodium hydroxide exhibits [KCET] In the above reaction, Z is [Manipal]

(a) geometrical isomerism (a) butanol (b) aldol (c) ketol (d) acetal
(b) optical isomerism 49. A compound 'A' having the molecularformulaC5 H 12 0,on
(c) neither optical nor geometrical isomerism oxidation gives a compound 'B' with molecular formula
(d) both optical and geometrical isomerism C 5 H 10 0. Compound 'B' gave a 2, 4-dinitrophenylhy-
drazine derivative but did not answer haloform test or
42. Benzaldehyde and acetone can be best distinguished using
silver mirror test. The structure of compound 'A' is
(a) Fehling's solution [KCET]
[Ke rala CEE]
(b) sodium hydroxide solution
(a) CH3 -CH2 -cH2 -CH2 -CH2 -0H
(c) 2, 4-DNP
(d) Tollen's reagent (b)CH 3 -CH 2 -CH2 fH-CH 3
43. Identify the reaction which is used to obtain 13- hydroxy OH
ketone. [Guj CET] (c) CH3 -CH2 -CH-CH2 -CH3
(a) Condensation reaction I
(b) Aldo! condensation
OH
(d) CH3 -CH2 - CH -CH 2 -OH
(c) Cross aldol condensation
(d) Cannizzaro reaction I
CH3
44. CH CHO+ HCHO Di!. NaOH ) A
3
Heat

The structure of compound B is [RPET]

634 I Chapterwise & Topicwise Engineering Entrances Solved Papers
5 0. Cross aldol condensation occurs between [UPSEEJ 59. An aromatic compound 'X' with molecular formula
(a) two same aldehydes C 9 H 10 O gives the following chemical tests
(b) two same ketones I. Forms 2, 4-DNP derivative,
(c) two different aldehydes and ketones II. Reduces Tollen's reagent,
(d) None of the above III. Undergoes Cannizzaro reaction and,
51. Main product obtained from the reaction of ammonia and IV. On vigorous oxidation 1, 2-benzenedicarboxylic acid is
formaldehyde is [UPSEEJ obtained. Xis [DCE]
(a) formic acid (b) methylamine CHO
(c) methanol (d) urotropine ~C2Hs
52. Which of the following compounds would be the main
product of an aldol condensation of acetaldehyde and
(a) l8J
acetone? [UPSEEJ
(a) CH3 CH = CH-CHO (b) CH3CH = CHCOCH3
(c) (CH3)zC = CH-CHO (d) (CH 3 )zC = CHCOCH3
53. An organic compound of molecular formula C 3H6 0 did not
give a silver mirror with Tollen' s reagent, but gave an oxime
with hydroxylarnine, it may be [OJEEJ
(a) CH3 -CO-CH3
(b) C2 H 5 CHO
(c) CH2 = CH-CH 2 -OH 2008
(d) CH3- O-CH = CH 2 60. In the following reaction sequence, the correct structures
54. In a reaction RCHO is reduced to RCH 3 using amalgamated ofE, F and Gare [ITT JEE]
zinc and concentrated HCl and wanning the solution. The 0 0
reaction is known as [AMUJ
(a) Meerwein-Ponndorf reaction PhAAOH~ £ Na6H )F + G
(b) Clemmensen's reduction (*implies BC labelled
(c) Wolff-Kishner reduction Carbon)
(d) Schiff's reaction
55. Which of the following reactions can be used to change
benzaldehyde to cinnarnic acid?
(a) Perkin's reaction [lndraprasth a CET, CGPET]
(b) Knoevenagel reaction 0 0
(c) Reformatsky reaction and ketones
(d) Benzoin condensation (b) E= PhACH F= PhAONa G=CHl3
3
56. Which factor/s will increase the reactivity of )C =0
group? [AMU]

I. Presence ofa group with positive inductive effect.

II. Presence of a group with negative inductive effect.
Ill. Presence of large alkyl group.
(a) Only I (b) Only II (c) I and III (d) II and III
57. What is the oxidation number of carbonyl carbon in
acetophenone? [Guj CETJ
(a) + 3 (b)+l
(c) + 2 (d)Zero 61. Acetone on addition to methyl magnesiwn bromide forms
a complex, which on decomposition with acid gives X and
58. Which product is obtained on reduction of methanal in the
Mg(OH)Br. Which one of the following is X?
presence of concentrated NaOH? [Guj CETJ
(a) Formic acid and methyl alcohol (a) CH 3 OH [BITSAT, AMU, EAMCET]
(b)CO+H 2 (b) (CH 3h COH
(c) Methyl alcohol (c) (CH 3 ) 2 CHOH
(d) Formic acid (d) CH3CH 2 OH
 Aldehydes, Ketones and Carboxylic Acids I 635
62. The end product 'C' in the following sequence of chemical
reactions is
CH3COOH CaC03 A ~B NH:i()H C [Manipal]
(a) acetaldehyde oxime (b) fo1maldehyde oxime (c) 9'CH(OH)·COOH
(c) methyl nitrate (d) acetoxime
OH
63. Which reaction, intermediate is formed during the
condensation reaction between acetaldehyde and CH 3
formaldehyde? [MHT CETJ
- +
(a): CH 2 CHO(b) CH2 CHO (c) CH 2OH
+

64. Which of the following organic compounds answers to both

(d): CHCHO (d) y
NCH(OH)·COOH

iodoform test and Fehling's test? [KCETJ OH

(a) Ethanol (b) Methanal (c) Ethanal (d) Propanone 68. Predict the product, CUPSEE]
65. The reactant ( X ) in the reaction,

(a)(f
COOH
(b) (f
CHO
CUPSEEJ

6 (i) MeMgBr
(ii) H30+

~ 0
MeoOH
(c)v
~ CH 3 (a)
QM, (b)

66. Which of the following, is an example ofaJdol condensation? OH 0

(a)2CH3COCH3 Dil. NaOH
CH3C(OH)CH 3CH 2COCH3
[UPSEE]
(c)
&Me (d)
&'Me
(b) 2HCHO Dil.NaOH > CH OH
3
(c) C6 H 5 CHO+ HCHO Di!. NaOH C 6 H 5 CH 2 OH
( d) None of the above
The compound B is [OJEEJ
67. p-cresol reacts with chloroform in alkaline medium to give
the compound A which adds hydrogen cyanide to form the (a) CH3- CH- CH 2 - CHO
compound B. The latter on acidic hydrolysis gives chiral I
carboxylic acid. The structure of the carboxylic acid is OH
[UPSEEJ (b) CH3 - fH- CH2 - COONa
OH
0
II
(a) 9'CH,COOH (c) CH3- CH-CH2 - C- CH3
I
OH OH
CH 3 OH 0
NCH2COOH I II
(b) y (d) CH3 - C- CH 2 - C-CH3
I
CH3
OH
636 I Chapterwise & Topicwise Engineering Entrances Solved Papers

CHO 2007
70. ©( CHO
(i) C-Onc. NaOH
(ii) H20/H+
[OJEE] 75. A compound X undergoes reduction with LiAIH 4 to yield
Y . When vapours of Yare passed over freshly reduced
copper at 300° C, X is formed. What is Y? [DCEJ
COOH (8yCOOH (a) CH 3 COCH3 (b) CH 3 CHO
(arc}r
)~ (b) ~ (c) CH 3 CH2 OH (d) CH 3 OCH3
COOH CH 2OH 76. The product formed in the aldol condensation of
acetaldehyde is [DCEJ
(8yCOOH (8yCH2OH (a) CH 3 CH2 CH(OH)CHO (b) CH 3 CI-I(OH)CH2CHO
(c)~ (d) ~ (c) CH 3 CH(OH)COCH3 (d) CH 3 CH 2 CH 2 CHO
OH CHO 77. Aldo! condensation is given by [VITEEEJ

X
0 0 (a) trimethyl acetaldehyde (b) acetaldehyde
( c) benzaldehyde ( d) formaldehyde
71. ( + NaOH~
78. In which of the below reaction do we find cx.,!>-unsaturated
0 0
carbonyl compounds undergoing a ring closure reaction

(a)
(°H and
NaOXO with conjugated dienes?
(a) Perkin reaction
[VITEEEJ
(b) Diels-Alder reaction
(c) Claisen rearrangement (d) Hofmann reaction
OH NaO 0

(b) C OH

OH
and 2CO2
79. C 6 H 5 CHO~?
(a) (C6 H 5 CHN)z CH- C 6 H 5 (b) C 6 I-I 5 NHCH 3
(c) C6 H 5 CH 2NH 2 (d) C 6H 5 NHC 6H 5
[VITEEEJ

(c)
(CHO and NaiCO3
80. Formalin is the commercial name of
(a) formic acid
(b) fluroform
[MHT CET]

CHO ( c) 40% aqueous solution of methanal

(d)
XOH and
(°Na [J&K CET]
(d) para-formaldehyde
81. Which does not react with Fehling's solution?
(a) CH 3 CHO (b) C 6H 5 CHO [MHTCETJ
OH ONa
(c) C6H12O6 (d) HCOOH

~
82. The product formed when hydroxylamine condenses with
72. is a carbonyl compound is called [KCETJ
l__O~O-R (a) hydrazide (b) oxime
(a) an ester (b) an anhydride ( c) hydrazine ( d) hydrazone
( c) acetal (d) hemiacetal 83. Selfcondensation of acetaldehyde in the presence of dilute
alkalies gives [WB JEE]
73. Aldehyde with NH 2 · NH 2 fom1s [BCECEJ
(a) an acetal (b) an aldol
(a) hydrazones (b) aniline
(c) mesitylene (d) propionaldehyde
(c) nitrobenzene (d) None of the above
84. What product is formed in the reaction [OJEEJ
74. Claisen condensation is not given by [BCECEJ
0
(a) @ - c o o - @ II
C- H
(8yo C2H50Na ?.
l8,)
(b) CH 3CH2COO @ +NHfNH2

( 8 y CONH2

(c)@-coOCH3
(a) l8,J
(8yNH2
( d ) @ - c oo C H2CH2CH3
(c) l8,J (d) None of these
 Aldehydes, Ketones and Carboxylic Acids I 637
85. The product fonned in the reaction [OJEEJ 90. A and B in the following reaction are [DCE AMUJ
0
R - C- R' ~ A~ R"-c / OH
II II KCN R/ "-cH2 NH2
~Q
~
C- CH3
LiAIH4 ?is
0

OH (a) A = RR' c(_ ~:, B - LiAlH4

I
~ C H- CH3 (b) A = RR'c( OH ,B- NH 3
(b) ~ COOH

(c) A = RR' c( OH , B =HpEB

CN
(d) None of these
(d) A = RR' CH 2 CN,B =NaOH

CHO

~
91. Which one of the following is reduced with zinc and
hydrochloric acid to give the corresponding hydrocarbon?
86. + HCHO NaOH > X+Y [OJEEJ (a) Ethyl acetate [Jamia Millia Islamia]
~OMe (b) Acetic acid
OMe (c) Acetamide
(d) Butan-2-one
Identify X and Y.

CH20H H 2006

(a) 0~
~OMe
+ HCOOH (c) + CH3COOH
OMe
92. The increasing order of the rate of HCN addition to
compow1ds A - D is
(A) HCHO
(C) PhCOCH 3
(B) CH 3COCH 3
(D) PhCOPh [AIEEEJ
OMe OMe (a)A<B <C < D (b)D<B<C<A
(c) D < C < B <A (d)C< D < B < A
CH20 H CH20H 93. Compound (A )(molecular formula C 3 H8 0) is treated with

(b)@ + HCOOH (d)@ + CH,CHO

acidified potassium dichromate to form a product B
(molecular formula C 3 H6 0). 'B' forms a shining silver
m.itTor on wanning with ammoniacal silver nitrate. 'B'
when treated with an aqueous solution ofH 2NCONHNH2
87. X Cone.
- - NaOH
---t Furo1c
. ac1'd + Fwy1a1coho1. · HCl and sodium acetate gives a product' C'. Identify the
structure of 'C' . [MHT CETJ
Compound X is [OJEEJ
(a) CH3CH2 CH = NNHCONH 2
r{ OyCH20H (b) (CH3 )iC=NNHCONH 2
(a) lLJ (c) (CH 3 ) 2 C = NCONHNH 2
(d) CH3 CH 2CH=NCONHNH2

(c) rr0 CHO

(d)
r{O¥CH3
lLJj
88. On reaction with hydroxylamine, aldehydes produce
94. Benzaldehyde on refluxing with aqueous alcoholic KCN
produce
(a) cyanobenzene (b) cyanohydrin
[MHT CET]

(c) benzoyl cyanide (d) benzoin

(a) ketoxime (b) hydrazone [J&K CETJ
(c) semicarbazone (d) aldoxime 95. Tollen's reagent is [MPPET]

89. CH3 COCH3 and CH3 CH 2 CH0can be distinguished by (a) [Ag(NH3 )2 ]N03
(b) [Ag(NH3 h ]Br
(a) FeCl 3 (b) Tollen's reagent [DCEJ
(c) Both (a) and (b)
(c) NaHS0 3 (d) 2, 4-DNP
(d) None of these
638 I Chapterwise & Topicwise Engineering Entrances Solved Papers

96. The enol form of acetone after treatment with D 2 0, give 104. Aldehydes can be oxidised by [Jamia Millia Islamia]
[Kerala CEE] (a) Tollen's reagent (b) Fehling's solution
(a) H 3G-C=CH 2 (c) Benedict solution (d) All of these
(b) H 3 C- n - CD 3
I 2005
OD 0
105. How will you convert butan-2-one to propanoic acid?
(c) H 2 C= C- CH2 D (d) H 2 C=C- CHD 2
I I (a) Tollen's reagent [IIT JEE]
OH OH (b) Fehling's solution
(e) D 2 C=C - CD3 (c) Na0H/I 2 / H+
I (d) NaOH/ NaI/ H+
OD

97. Benedict's solution is not reduced by [WB JEE] 106. Me 0 - 0 - CHO + (X) CH~~;N•
(a) formaldehyde (b) acetaldehyde
(c) glucose (d) acetic anhydride Me0-0-CH=CHCOOH
98. 2-pentanone and 3-petanone can be distinguished by
(a) Cannizzaro's reaction (b) Aldo! condensation The compound ( X) is [IITJEE]
(c) Iodoform reaction (d) Clemmensen's (a) CH 3 - COOH (b) BrCH2 - COOH
reduction (c) (CI-I 3 CO)i0 (d) CHO- COOH
99. Which of the product is formed when acetone is reacted 107. Cyanohydrin of which of the following forms
with barium hydroxide solution? lactic acid? [BITSAT,DCE]

w TH3 (a) HCHO

(c) CH 3 CHO
(b) CH 3 COCH 3
(d) CH3 CH 2 CHO
(a)CH 3 - C- CH2 - C- CH 3 [EAMCETJ
I 108. Acetone and acetaldehyde can be distinguished by
OH (a) Molisch test (b) Tollen's test [BITSATJ
0
(c) Schiffs test (d) lodoform test
II
(b) CH3 - C- CH - CH- CH3 109. Which of the following can be used to differentiate between
I I aldehyde and ketone? [MHT CETJ
CH 3 OH
(a) Ammoniacal AgN0 3

(c) CH3 -
~
C- CH- CH- CH3
(b) Ammoniacal AgN0 3 in the presence oftartarate ion
(c) 12 in the presence of base
I I (d) Ammoniacal AgN0 3 in the presence of citrate ion
OH CH3
110. Benzaldehyde reacts with methyl amine to give [MP PET]
OH OH
I I (a) C 6 H 5 NH 2 (b) C 6 H 5 CH2 NI-I 2
(d) CH3 - C- C- CH3 (c) C 6 H 5 CH=NCH3 (d) C 6 H 5 CONH2
I I 111. ) G- CN group is called [MP PET]
CH 3 CH3
I
100. When acetaldehyde is heated with Fehling's solution, a red OH
precipitate is formed. Which of the following is that? (a) hydroxy nitrite (b) hydroxy cyanide
(a) Cup (b) Cu [EAMCETJ (c) cyanohydrin (d) hydroxy isocyanide
(c) CuO (d) CuS04 112. A compound A has a molecular fommla C 2 Cl 3 0H. It
101. Acetone reacts with Grignard reagent to form [Guj CETJ reduces Fehling's solution and on oxidation, gives a
(a) 3° alcohol (b) 2° alcohol monocarboxylic acidB. A can be obtained by the action of
(c) ether (d) No reaction chlorine on ethyl alcohol. A is [KCETJ
102. The end products in the Cannizzaro reaction of (a) chlorofo1m (b) chloral
benzaldehyde are [J&KCET] (c) methyl chloride (d) monochloroacetic acid
(a) PhC0 2 H,PhCH 2 0 H (b) PhC0 2 H, PhCH 2 C0 2 H 113. Benzyl alcohol and sodium benzoate is obtained by the
(c) PhCH 2 0H, PhCOCH 3 {d) PhC0 2 H,PhCOCH 3 action of sodium hydroxide on benzaldehyde. This reaction
is known as [KCETJ
103. Acetals are [BCECE]
(a) Perkin's reaction (b) Cannizzaro's reaction
(a) ketones (b) diethers (c) Sandmeyer's reaction (d) Claisen condensation
(c) aldehyde (d) hydroxy aldehydes
 Aldehydes, Ketones and Carboxylic Acids I 639
114. A compound, containing only carbon, hydrogen and 119. The acetophenone can be converted to etbylbenzene by
oxygen, has a molecular weight of 44. On complete reaction with [AMUJ
oxidation, it is conve1ted into a compound of molecular (a) LiAJH4 (b) H 2 NOH
weight 60. The original compound is CKCETJ (c)Pd / BaS04 -H 2 (d)Zn-Hg / HCI
(a) an aldehyde (b) an acid 120. 3-hydroxybutanal is fom1ed when (X) reacts with (Y) in
(c) an alcohol (d) an ether
dilute ( Z) solution. What are X, Y and Z? CEAMCETJ
115. CH3 - CHO + HCN~ A
X Y Z
Compound A on hydrolysis gives [Ke rala CEEJ
(a) CH3CHO, (CH 3 h CO, NaOH
(a) CH3 - CH 2 - COOH
(b) CH3 CHO, CH 3 CHO, NaCl
(b) CH3- CH 2 - CH2 - NH 2
(c) CH3 - CO - COOH (c) (CH 3 h CO, (CH 3 h CO, HCl
(d) CH3 -CO - CH=NOH (d) CH3 CHO, CH 3 CHO, NaOH
(e) CH3 - CH- COOH 121. The reaction of an organic compound with ammonia
I followed by nitration of the product gives a powerful
OH
explosive, called RDX. The organic compound is
116. Which of the following does not undergo Cannizz.aro's (a) phenol (b) toluene [Guj CETJ
reaction? [Kerala CEEJ (c) glycerine (d) formaldehyde
(a) Benzaldebyde (b) 2-methylpropanal 122. Identify the organic compound which, on beating with
(c) p-methoxybenzaldebyde (d) 2, 2-dimethylpropanal strong solution of NaOH , pa1tly converted into an, acid
(e) Formaldehyde salt and partly into alcohol. [Guj CETJ
117. Which of the following will form two isomers with
(a) Benzyl alcohol (b) Acetaldehyde
semi carbazide ? [OJEEJ
(c) Acetone (d) Benzaldehyde
(a) Benzaldehyde (b) Acetone 123. An important reaction of acetone is auto condensation in
(c) Benzoquinone (d) Benzophenone the presence of concentrated sulphuric acid to give the
118. In the reaction sequence, aromatic compund [Guj CETJ
CH3CH2MgBr H30l!l (a) mesitylene (b) mesityl oxide
A --=---=--~ B ~ C 5 H 12 0 compound A is
(c) trioxan (d) phorone
(a) 1-propano l (b) propanol-3 [AMUJ
124. Which of the following does not give Fehling solution
(c) ethanal (d) 2-propanol test? [BCECEJ
(a) Acetone (b) Propanal (c) Ethanal (d) Butanal

Topic 3
Carboxylic Acids, Preparation and Properties
2014
1. Sodium phenoxide when heated with CO2 under pressure 2. In the reaction
at 125°C yields a product which on acetylation producesC. CH3COOH LiAIH4 A ~ B Ale. KOH
C,
ONa
+ CO2 ~ B~ C the product C is [JEE Mains]
5atJn AczO
(a) acetaldehyde
The major product C would be [JEE Mains] (b) acetylene
(c) ethylene
OCOCH3 (d) acetyl chloride
& cooH J:~7;0H 3. What represents the best method for producing salicylic
(a) LS:2J (b)ly acid? [ManipalJ
(a) Benzoic acid, strong base, high temperature
COCH3 (b) Toluene, strong base, water, high temperature
OH OCOCH 3 (c) Phenol, base carbondioxide then acid
(d) Bromobenzene, carbonic acid, high temperature
&coOCH3
(c) LS:2J (d)~
~COOH
640 I Chapterwise & Topicwise Engineering Entrances Solved Papers
4. Match the following columns. [KCET] 2013
Column I Column II
12. The compound that does not liberate CO 2 on treatment

A. Acetic acid I. Stephen with aqueous sodium bicarbonate solution is

(a) benzoic acid [JEE Advan ced]
B. Sodium phenate 2. Friedel-Crafts
(b) benzenesulphonic acid
C. Methyl cyanide 3. HVZ
( c) salicylic acid
D. Toluene 4. Kolbe's (d) carbolic acid (Phenol)

Codes 13. The total number of carboxylic acid groups in the product
A B C D A B C D P is [JEE Advance d]
(a) 3 I 4 2 (b) 4 2 3 I 0 0
(c) 2 3 I 4 (d) 3 4 I 2
0 (i)H30 + A p
5. The correct increasing order of the acid strength ofbenzoic (ii)03
acid (I), 4-nitrobenzoic acid (II), 3, 4-dinitrobenzoic acid (i ii) H202

(Ilf) and 4methoxybenzoic acid (IV) is [Ke rala CEEJ

( a) I < II < III < IV (b) II < I < IV < III (a)S (b)2 (c)4 (d)3
( c) IV < I < II < ill (d) IV < II < I < III 14. An organic compound A upon reacting with NH3 gives B.
(e) I < IV < II < III On heating, B gives C. C in the presence of KOH reacts
6. Among the following compounds, the one(s) that gives with Br2 to give CH 3 CH 2 NH 2 . A is [JEE Mains]
(give) effervescence with aqueous NaHCO 3 solution is (a) CH 3 COOH
(are) [WB JEE] (b) CH 3 CH 2 CH2 COOH
(CH 3 CO)i OCH 3 COOH PhOHCH3 COCHO (c) CH 3 -rH-COOH
I TI ill IV
(a) I and II (b) I and III (c) Only II (d) 1 and IV CH 3
7. Which of the following acids dissociates to the greatest (d) CH 3 CH 2 COOH
extent in aqueous solution? [Indraprasatha CET] 15. The reaction of CO2 with sodium phenoxide at 400 K
(a) Trichloroacetic acid (b) Acetic acid result in [Manipal]
( c) Chloroacetic acid (d) Dichloroacetic acid
(a) benzoic acid
8. What will be the end product ( B) in the following sequence (b) sodium benzoate
of reactions? [AMU] ( c) salicylaldehyde
(d) sodium salicylate
CH3 Br . 16. Which one of the following reacts with Grignard reagent to
{t) KMn04/0H A Cao + 4Na0H ) B fom1 an addition product which can be hydrolysed to a
(i i) H20/H+ Heat
carboxy lie acid ? [Manipal]

Br (a) 0 2 (b) CO 2
(c) SO 2 (d) None of these
(a) I, 2-dibromobenzene
17. Vinegar is dilute aqueous solution of [Manipall
(b) I, 2-dibromobenzaldehyde
(c) 1, 3-dibromobenzene (a) ethanoic acid (b) benzoic acid
( d) I, 4-dibromobenzene ( c) citric acid ( d) oxalic acid
9. Which acid is present in vinegar? [J&K CET] 2012
(a) Formic acid (b) Acetic acid 18. The compound that undergoes decarboxyliation most
(c) Butyric acid (d) Tartaric acid
readily under mild condition is [IIT JEE]
10. Which one ofthe following acid does not have a carboxylic
COOH
group? [J&K CET]
(a) Methanoic acid
(c) Propanoic acid
(b) Ethanoic acid
(d) Picric acid
(b)Cr°
Dry ether COOH
~COOH
Identify Z from the following.
(a) Ethyl acetate (b) Acetic acid
[EAMCET]
(c) V
(c) Propanoic acid (d) Methyl acetate
 Aldehydes, Ketones and Carboxylic Acids I 641
Directions (Q. Nos. 19-20) In the following reactions 25. Which of the following acid reduces Tollen' reagent?
sequence, the compound J is an intennediate. (a) Formic acid (b) Acetic acid [OJEE]
(CH 3 C0)20 (i)H2,Pd/ C K (c) Lactic acid (d) Oxalic acid
I -CH3COONa
- - - J - (11)SOCl2
..- - - - - +
26. Which one of the following is an example of
(iii) anhyd. AICI 3
Hell-Volhard-Zelinsky reaction? [AMU]
J (C9 H 8 0 2 ) gives effervescence on treatment with
NaHC03 and positive Baeyer's test. [HT JEE] (a) RCOOH
19. The compound!, is
(i) B61 red P

0
0~ H (b) R 2 CHCOOH - - - - + R 2 CCOOH
J:OH

(a) (b) uH (ii) H20+ I

Br

00-?CH
I
3
H6H ,✓,:;.
(c) r'YCOOH ":' >~ n
~COOH ~
(c)
;::,..._
(d) : I 0
PCl 5
20. The compound K is (d) RCOOH ~ RCOCl

(a)(X) (b)~
~O~o
2011

(c)W 0
(d)o=>=O
27. The strongest acid amongst the following compounds is
(a) CH3 COOH (b) HCOOH [AIEEEJ
(c) CH3 CH2 CH(Cl)C0 2 H (d) ClCH 2 CH 2 CH2 COOH

2010
21. With reference to the scheme given, which of the given 28. Consider the acidity of the carboxylic acids
statement (s) about T,U, V and Wis (are) correct?

h
I. PhCOOH II. o-N02¼ H4 COOH
ITT. p-N02C6H4COOH TV. m-N02½H4COOH
Which of the following order is correct? [Manipall
LlA,H,<~•=l
(a) I > II > III > IV (b) II > IV > III > I
H3C T
V
ero /W
3
1
U (CH3CO)JO ) W [IIT JEE]
(c) Il > IV > I > ITI (d) II > III> IV > I
29. Which reaction is suitable for the preparation of
(a) Tis soluble in hot aqueous NaOH cx.-chloroacetic acid? [Manipal]
(b) U is optically active (a) Hell-Volhard-Zelinsky reaction
(c) Molecular formula of Wis C10H 18 0 4 (b) Nefreaction
(d) V gives effervescence on treatment with aqueous (c) Stephen's reaction
NaHC03 (d) Perkin condensation
22. What product is formed when cyclohexanone is oxidised? (i) KCN
(a) HOOC. (CH2 ) 4 · COOH [Manipall
30. CH 3 COOH Y (ii) Hp+ X. Here, Xis
(b) CH3 CH2 COOH (a) glycollic acid [RPET]
(c) CH3 (CH 2 ) 4 COOH (b) a-hydroxy propionic acid
(d) None of the above (c) succinic acid
23. Which of the following reagent is used to distinguish (d) malonic acid
between methanoic acid and ethanoic acid [MP PET] 31. Identify Din the following reaction [Punjab CETJ
(a) Tollen's reagent (b) FeCl 3 solution (i)C02 B
(c) NaOH solution (d) Na 2 C03 solution CH=CH + CH 3MgBr -CH4 J A (ii)HJO

24. Identify the method by which Me 3 CC02 H can be

prepared. [WB JEE] D Tautomerisation
1
HgS04
H2S04
C
(a) Treating 1 mole ofMeCOMe with 2 moles ofMeMgI
(b) Treating 1 mole ofMeC02 Me with 3 moles ofMeMgI (a) HOOC- CH2 - COOH
(c) Treating 1 mole ofMeCHO with 3 moles ofMeMgI (b) OHC- CH 2- COOH
(d) Treating 1 mole of dry ice with 1 mole of Me 3 CMgI (c) OHC- CH2 - CHO
(d) HO- CH= CH- COOH
642 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2009
32. A liquid was mixed with ethanol and a drop of 39. The gas evolved on heating alkali fo1mate with sodaiime
concentrated H2 SO4 was added. A compound with a fruity is [VITEEE]
smell was formed. The liquid was [AIEEEJ (a) CO (b) CO 2
(a) CH3OH (b) HCHO (c) hydrogen (d) water vapour
(c) CH3COCH3 (d) CH3COOC2 H 5 40. Carboxylic acids readily dissolve in aqueous sodium
33. Which of the following is a better reducing agent for the bicarbonate, liberating carbon dioxide. Which one of the
following reduction? following is correct? [Manipall
RCOOH ~ RCH2OH [Keral a CEEJ (a) Free carboxylic acid and its conjugate base are of
comparable stability
(a) SnCL2 /HCl (b) NaBH4 /ether (b) The free carboxylic acid is more stable than its
(c) H 2 / Pd (d) N 2 H 4 / C2H 5 ONa
conjugate base
(e) B 2 H 6 /ether
(c) The conjugate base of the carboxylic acid is more
34. Oxidation of which compound is not possible? COJEEJ stable than the free carboxylic acid
(a) CH3-COOH (b) CH3-CO-CH3 (d) The conjugate acid of the carboxy lic acid is more
(c) CH3-CHO (d) CH3-CH2 -OH stable than the free carboxylic acid
35. Which of the following represents the correct order of the 41. End product of the following reaction is
activity in the given compounds? [OJEEJ CH3CH 2 COOH ~ X Ale-KOH> [MHTCET]
red P
(a)CH 3COOH> BrCH2 COOH> CICH 2 COOH
>FCH 2 COOH (b) CH, CH 2 COOH
(b) FCH2 COOH> CH3COOH> BrCH2 COOH
I -
> CICH 2 COOH OH
(c) BrCH2 COOH> CICH 2 COOH> FCH 2 COOH
(c) CH 2 = CHCOOH (d) CH 2 CH COOH
>CH 3COOH I I
(d) FCH2 COOH> CICH2 COOH> BrCH2 COOH Cl OH
>CH3COOH
42. The reaction, RCOOH + N 3H
36. ' - . . , _ ~ ~ RNH 2 + CO 2 + N 2 is called [MPPET]
LJ . CF3COOH l X. Identify X [OJEE] (a) Lossen reaction (b) Schmidt reaction
(c) Curtius reaction (d) Ullmann reaction
43. Which of the following acids has the smallest dissociation
(a) ~ (b)"Q<J
constant ? [WB JEE]

~COOH
~ ~ lH (a) CH3CHFCOOH
(b) FCH 2 CH 2 COOH
(c) L_J (d) ~ - - - - - - - (c) BrCH 2 CH 2 COOH
(d) CH3CHBrCOOH
37. The correct order ofacidic strengths ofthe carboxylic acids
44. In the following reaction,
is [DCE]
(a) formic acid < benzoic acid < acetic acid RCH COOH ~ X ExcessNH 3 Y
2
(b) formic acid < acetic acid < benzoic acid The major amounts of X and Y are CUPSEEJ
(c) acetic acid < formic acid < benzoic acid
(d) acetic acid < benzoic acid < formic acid (a) RCHBrCONH2 ; RCH(NH 2 )COOH
(b) RCHBrCOOH; RCH(NH 2 )COOH
2008 (c) RCH 2 COBr; RCH 2COONH4
38. Identify A and B in the following reaction (d) RCHBrCOOH; RCH 2 CONH 2
B A 45. The property which distinguishes fonnic acid from acetic
CH3 - CH3 f--CH3COOH ~ CH3CH2 OH
acid is CUPSEEJ
[BITSAT, AMU, EAMCET] (a) Only ammonium salt of formic acid on heating gives
A B amide
(a) HI+ red P LiAIH 4 (b) when heated with alcohol/H2 SO4 only acetic acid
(b) Ni/£\ LiAIH4 forms ester
(c) LiAIH4 HI +red P (c) Only acetic acid forms salts with alkali
(d) Pd- BaSO4 Zn + HCl (d) Only formic acid reduces Fehling's solution
 Aldehydes, Ketones and Carboxylic Acids I 643
52. Lemon gives sour taste because of [MHT CETJ
~ C O OH Ba(OH)2
(a) citric acid (b) tartaric acid
46
· ~ 300°c (c) oxalic acid (d) acetic acid
COOH
53. Reaction of acid with alcohols is also known as
~COOH (a) esterification [MHT CET, J&K CETJ
(a)~ (b) saponification
OH (c) alkalisation
0 (d) None of the above
II 54. Given below are some statements concerning fomlic acid,
C
(c)
~COOH
l8J (d) rc3Y' b whlch of them is tme? [WB JEE]

~~/
(a) It is weaker acid than acetic acid
(b) It is reducing agent
(c) When its calcium salt is heated, it fom1s a ketone
C (d) It is an oxidising agent
0 55. Acetic acid reacts with PCl 5 to form [WB JEE]

4 7.
Jl
LJ .,....COOEt H +
0
~ A ~B
(a) CH 2ClCOOH
(c) CH3 COC1
(b) CHC1 2COOH
(d) CH3 COOC1
56. Which of the following gives oxalic acid? [WBJEE]
The compound B is [OJEEJ (a) Heating of acetic acid
(b) Action of nitric acid on glucose
(c) Acidic hydrolysis of cyanogen
~COOH (d) Strong heating of sodium formate
(a)~ (b) LJ 57. In a set of the given reactions, acetic acid yielded a
product C.
0 CH3 COOH + PCI 5 ~ A

(c) Ci (d)
r("VCOOH
LJ
Alcoholic KCN DiluteHCI
Product C would be
A
~ H6
anh_ AICI 3 B
CzH 5MgBr
ether C

[UPSEEJ
48. In the reaction, R- X A B C2Hs
I
The product B is [Jamia Millia Islamia] (a) CH3 CH(OH)C6H 5 (b) CH3 - C(OH)C6H 5
(a) alkyl chloride (b) aldehyde (c) CH3 CH(OH)C2H 5 (d) CH3 COC6Hs
(c) carboxylic acid (d) ketone
58. CH3COOH LiAIH 4 A + CH3COOH H 3o+ B + H20
2007
In the above reactions, A and B respectively are
49. When CH 2 = CH- COOH is reduced with LiAJH4 , the
(a) CH3 COOC2 H 5 ,C2 H 5 0H [EAMCETJ
compound obtained will be [AIEEE, UPSEE, MP PET] (b) CH3CHO, C 2H 5 0 H
(a) CH3- CH 2- COOH (c) C2H 5 0H,CH3CHO
(b) CH 2 = CH- CH 20H
(d) C 2H 5 0H,CH3COOC2 H5
(c) CH3CH 2 CH 20H
(d) CH3CH2 CHO 2006
50. 2, 4-dichlorophenoxy acetic acid is used as [BITSATJ 59. The correct order of increasing acidic strength of the
(a) fungicide (b) insecticide compounds is [AIEEEJ
(c) herbicide (d) moth repellant I. CH3 COOH II. MeOCH2COOH
51. The weakest acid amongst the following is [VITEEEJ Me"-
III. CF3COOH N . / CHCOOH
Me
(a) ClCH 2COOH
(b) HCOOH (a) IT < IV < I < Ill
(c) FCH2 CH 2 COOH (b) IV < I < III < II
(c) IV < I < II < Ill
(d) CH 2 (I)COOH
(d) I < IV < III < II
644 I Chapterwise & Topicwise Engineering Entrance Solved Papers

60. Complete the following reaction RCOOH P

2
i 5
?
68. Which reagent can convert acetic acid into ethanol?
(a) Na + alcohol (b) LiAlH4 + ether [BCECEJ
(a) acid anhydride (b) ketone [MP PET]
(c) H2 + Pt (d) Sn + HCl
(c) aldehyde (d) ester
69. Among the following, the most acidic is
61. Identify the compound Z in the reaction sequence
[Jamia Millia Islamia]
CH3CH2COOH~X Br2 + KOH Y HN02 Z; (a) CH3COOH (b) ClCH 2 COOH
(a) CH3 0 H [Kerala CEE] (c) Cl 2CHCOOH (d) Cl 2CHCH2COOH
(b) CH3CH2 NH2 2005
(c) CH3 CH 2 0H 70. 4-methylbenzene sulphonic acid reacts with sodium
(d) CH 3 CH2 CH 20 H acetate to give [ITT JEE]
(e) CH3 NH2 COONa

$ $
CH3
62. Propionic acid and KOH reacts to produce which one of
the following ? [WB JEE]
(b)
(a) + CH3COOH +so,
(a) Potassium propionate
(b) Propyl alcohol
(c) Propionaldehyde S03Na CH3
(d) Does not react

$
?COCH3 S03Na
63. Saturated fatty acids are represented by which of the

~
formula? [WB JEE]
(c) +so, (d) + NaOH
(a) Cn Hn02 (b) CnH3n02
(c) CnH2n+I (d) CnH2n02
CH3 CH3
64. The acid which contains the aldehyde group is [UPSEEJ
(a) acetic acid 71. Among the following acids which has the lowest pK0
(b) formic acid value? [AIEEEJ
(c) benzoic acid
(a) CH3 CH2 COOH
(d) prop ionic acid
(b) (CH3 )zCH- COOH
65. The reagent which does not give acid chloride on treating
(c) HCOOH
with a carboxylic acid is [AMU]
(d) CH3 COOH
(a) PC1 5 (b) Cl 2
72. Liquid obtained by distillation of red ant is [MP PET]
(c) SOC1 2 (d) PC1 3
66. The Hell-Volhard-Zelinsky reaction is used for preparing (a) formaline (b) formaldehyde
(a) p-halo acid (b) r-halo acid [Guj CETJ (c) formic acid (d) formyl chloride
(c) cx.-halo acid (d) acid halide 73. Colouration ofBr2 /CC1 4 will be discharged by [OJEEJ
67. When CH3 COOHreacts with CH3 - Mg X , CBCECEJ (a) cinnamic acid (b) benzoic acid
(c) o-phthalic acid (d) acetophenone
(a) CH3 COX is formed
(b) hydrocarbon is formed 74. Acetic acid will be obtained on oxidation of [J&K CETJ
(c) acetone is formed (a) ethanol (b) propanal
(d) alcohol is formed (c) methanal (d) glyoxal
 Topic 4
Derivatives of Carboxylic Acids
2014
1. Different possible them,al decomposition pathways for Decreases as [KCET]
peroxyesters are shown below. Match each pathway from (a) I > III > II (b)l > II > III
Colwnn I and select the correct answer using the code (c) II > I > III (d)III > l > II
given below the lists. [JEE Advanced]
4. C H COOH (il NH 3 p NaOBr Q (i) Cone. H 2SO4 R
~-P................, K + R'O' 6 5 (ii),.. (ii) Heat of 460 K
-CO2T
R is [KCET]
0 Q (a) o-bromo sulphanilic acid
~ fQ -C02t R' + R'O' - R' + X'
+ Carbonyl compoundT (b) sulphanilamide
R ~7 "---R'- (c) sulphanillic acid
f----R-➔ RCO' 2+ R'O' ~ R' + X' (d) p-bromo sulphanilamide
-C½ + Carbonyl
compound t
5. Who has synthesised the organic compound 'w·ea' for the
first time? [J&K CET]
..__--=s=--➔ RCO' ,+ R'O' - R' + R'O'
- -C02t (a) Friedrich Wohler (b) Berzelius
(c) Kolbe (d) Berthelot
Column I Column IT 6. Which compound is responsible for perfumery?
0 (a) Ketones (b) Ethers [J &K CETJ
P. Pathway p I / 0' II (c) Alcohols (d) Esters
. CJI5CH2~ 0 'CH3
! 2012
7. In the given reaction, identify compoundC. [BITSATJ
0
II CO2Et (i) NaOH/t. (A)~ (B) NaOH ) (B)
~ (ii) H 3o+

OH
R. Pathway R 3.

(a) ~
OH 0
(b)~
0
HO O

(c) ~ OH 0
(d)~

Codes 8. Oil of winter green is [KCET]

P Q R S P Q R S (a) a carboxylic acid (b) an alcohol
(a) 1 3 4 2 (b) 2 4 3 I
(c) a ketone (d) an ester
(c) 4 l 2 3 (d) 3 2 1 4
2. Which of the following isome1ism is shown by ethyl 2011
acetoacetate? [VITEEEJ 9. Sodium ethoxide has reacted with ethanoyl chloride. The
(a) Geometrical isomerism compow1d that is produced in the above reaction is
(b) Keto enol tautomerism
(a) diethyl ether (b) 2-butanone [AIEEEJ
(c) Enantiomerism
(c) ethyl chloride (d) ethyl ethanoate
(d) Diastereoisomerism
10. Give IUPAC name of the product, when acetamide is
3. The acidic strength of active methylene group in
heated with anhydrous phosphorus pentoxide. [Guj CETJ
I. CH3COCH2COOC2H 5
(a) Ethyl atnine (b) Propane nitrile
II. CH3COCH2COCH3
(c) Cyano methane (d) Ethane nitrile
III. C2Hs00CCH2COOC2H 5
646 I Chapterwise & Topicwise Engineering Entrances Solved Papers
11. Acetic anhydride is prepared in the laboratory by heating 18. When acetamide is treated with Br2 and caustic soda, the
sodium acetate with CRPET] product formed is [MHT CET]
(a) ethyl chloride (b) acetyl chloride (a) N-brommide (b) bromoacetic acid
(c) cone. H 2S04 (d) zinc dust (c) methanamine (d) ethanamine
19. An ester (A )with molecularfo1mulaC9 H 10 0 2 was treated
2010 with excess of CH3MgBr and the complex so fo1med was
12. In the reaction treated with H 2S04 to give an olefin (B) . Ozonolysis of
(i) NaOH/Br2 (B) gave a ketone with molecular formula C 8 H 8 0 which
H3C
-0-
I/
-
~ C,:7'0 ------➔ T
"'-NH2 ( i i ) - o - ~c<
-
0

Cl
shows positive iodoform test. The structure of (A) is
(a) C6HsCOOC 2H 5 [MHT CET]
(b) C 6H 5 COOC6Hs
[IITJEE]
(c) C6 H 5 COOCH3
(d) p-H3CO - C 6H 4 - COCH3
20. The most suitable reagent A, for the reaction

is/are [AMU]
(a) 0 3 (b) H 2 0 2
(c) Na0H-H 20 2 (d) m -chloroperbenzoic acid

2008
21. Which of the following will produce only one product on
reduction with LiAlH4 ? [WB JEE]
(a) C2H 5 COOCH 2CH3
(b)CH 3 CH 2COOCH 2CH 3
13. Which one of the following will undergo meta-substitution
(c) CH3COOC2Hs
on monochlorination? [RPET]
(d) CH3COOCH2CH2CH3
(a) Ethoxybenzene (b) Chlorobenzene
22. Which one of the following pairs gives effervescence with
(c) Ethyl benzoate (d) Phenol
aqueous NaHC0 3?
14. Identify Zin the sequence,
CH 3 COC1 CH3COCH3
CH3COONH4 ~ X (I) (IT)

(a) CH3 CH 2CONH 2 (b) CH3 CN [JCECE] CH 3 COOCH3 CH3 COOCOCH3

(111) (IV) [WBJEE]
(c) CH3 COOH (d) (CH 3 C0)20
15. Potassium cyanate is heated with ammonium sulphate. The (a) I and II (b) I and IV
product formed is [OJEE] (c) II and Ill (d) I and III
(a) urea (b) ammonia 23. Which of the following diacid readily gives anhydride on
(c) potassium sulphate (d) ammonium cyanide heating ? [J&K CET]
(a) Fumaric (b) Maleic acid
2009 (c) Malic acid (d) Terephthalic acid
16. When acetamide is hydrolysed by boiling with acid, the 24. Hydroxamic acid test is employed to detect [J&K CET]
product obtained is [VITEEE]
(a) ketones (b) aldehydes
(a) acetic acid (b) ethyl amine
(c) esters (d) amides
(c) ethanol (d) acetamide
25. Which of the following would undergo Hofmann reaction
17. Ethyl acetate is obtained when methyl magnesium bromide
to give a primary anline? [Jamia Millia Islamia]
reacts with [Manipal]
(a) RCOCl (b) RCONHCH3
(a) ethyl formate (b) ethyl chlorofo1mate
(c) RCONH 2 (d) RCOOR'
(c) acetyl chloride (d) carbon dioxide
 Aldehydes, Ketones and Carboxylic Acids I 647
2007
26. In the following reaction, 33. CH 3 CH 2 CONH 2 ~ CH 3 CH 2 CH 2 NH 2 , Xis [DCEJ
(a) Pt/H 2 (b) Ni/H2 (c) LiA1H 4 (d) Zn
Cone. HN03 X 34. On mixing ethyl acetate with aqueous sodium chloride, the
composition of the resultant solution is
(a) CH3COOC2 H 5 + NaCl [Jamia Millia IslamiaJ
The structure of the major product X is [IITJEE] (b)CH 3 C00Na + C 2 H 5 0H
(c) CH 3 COCI + C2 H 5 0H+ NaOH
o
(a) Q N~ N
H
--c::::
I
O
2
.&
(d) CH 3 Cl + C2 H 5 C00Na
35. Acetyl bromide reacts with excess ofCH 3 Mgl followed by
treatment with a saturated solution ofNH4 Cl gives
(a) acetone [Jamia Millia Islamia]
(b) acetamide
(c) 2-methyl-2-propanol
(d) acetyl iodide
36. Rate of reaction,
0
R - C< + Nu - ~

z
is fastest when Z is [Jamia Millia lslamia]
(a) Cl (b) NH 2 (c) OC2 H 5 (d) OCOCH3

2006
37. Which one of the following can produce hydrogen when
treated with metallic sodiwn? [WB JEE]
(a) (CH 3 ) 2 NH (b) CH3NH 2
(c) C 6 H 5 NH2 (d) CH 3 CONH2
27. trans-esterification is the process of [VITEEEJ
38. The silver salt of a fatty acid on refluxing with an alkyl
(a) conversion of an aliphatic acid to ester halide gives an [AMUJ
(b) conversion of an aromatic acid to ester
(a) acid (b) ester (c) ether (d) amine
(c) conversion of one ester to another ester
(d) conversion ofan ester into its components namely 39. An organic compound is boiled with alcoholic potash. The
acid and alcohol product is cooled and acidified with HCI. A white solid
28. Urea on slow heating gives [VITEEE] separates out. The starting compound may be [AMUJ

(a) NH 2 CONHN02 (b) NH 2 CONHCONH 2 (a) ethyl benzoate (b) ethyl formate
(c) HCNO (d) NH 2 CONH2 ·HN03 (c) ethyl acetate (d) methyl acetate
40. A nitrogen containing organic compound gave an oily
/J"
29. CH3 - CH- CH- CH3 istheanhydrideof [MHT CETJ
liquid on heating with bromine and potassium hydroxide
solution. On shaking the product with acetic anhychide, an
(a) 1, 2-butane diol (b) 2,2- butane diol antipyretic drug was obtained. The reactions indicate that
(c) 2,3-butane diol (d) 1, I-butane diol the starting compound is [AMUJ
30. The product formed in the reaction n-hexanamide (a) aniline (b) benzamide
+Br2 + KOH , is [OJEE] (c) acetamide (d) nitrobenzene
(a) hexanamine (b) propanamine 41. What is obtained when acetyl chloride is heated with
(c) bu tanamine (d) pentanamine benzene in presence of anhydrous AJCI 3 ? [BCECEJ
(a) Acetyl benzoic acid (b) Anisole
31. (CH 2CO)z 0 + RMgX H 2o)? [OJEEJ
(c) Acetophenone (d) Cholorobenzene
(a) ROOC(CH2 )COOR (b) RCOCH 2 CH 2 COOH 42. The refluxing of (CH 3 )z NCOCH 3 with acid gives
(c) RCOOR (d) RCOOH
(a)(CH 3 ) 2 NH+ CH3 COOH [BCECEJ
32. Amides are fonned by the reaction of acid chloride with (b) (CH 3 h NCOOH+ CH4
(a) NH 2 NH 2 (b) NH 3 [J&KCET] (c) 2CH3 0H + CH 3 CONH2
(c) NH 2 0H (d) C 6 H 5 NHNH 2 (d) 2CH3 NH 2 + CH 3 COOH
648 I Chapterwise & Topicwise Engineering Entrances Solved Papers
46. Urea is preferred to ammonium sulphate as a nitrogenous
fertiliser because [Guj CETJ
(a) it is more soluble in water
(b) it is cheaper than ammonium sulphate
(c) it is quite stable
(d) it does not cause acidity in the soil
47. Which is the most reactive of the following? [J&K CETJ
(a) Ethyl acetate
(b) Acetic anhydride
(c) Acetamide
(d) Acetyl chloride
2005 48. A carboxylic acid is converted into its anhydride using
H+ (a) thionyl chloride [J&K CETJ
44. CH 3 COOCH 3 + excess PhMgBr ~ product ~ X.
(b) sulphur chloride
The product X, is [OJEEJ (c) sulphuric acid
(a) I , 1-diphenylethanol (b) I, 1-diphenylethanol (d) phosphorus pentoxide
(c) methyl phenylethanol (d) methyl phenylketone 49. Acetamide is [DCEJ
45. Ethyl benzoate reacts with PC! 5 to give [GujCET] (a) highly acidic
(a) C 2 H 5 Cl + C 6 H 5 COCI + POC1 3 + HCI (b) highly basic
(b) C2 H 5 CI + C 6 H5 COCI + POC13 (c) neutral
(c) CH 3 COCI + C 6 H 5 COCI + POCI 3 (d) amphoteric
(d) C2 H 5 CI + C 6 H5 COOH + POC13

Answers
TOPIC 1 Preparation of Aldehydes and Ketones
1. (d) 2. (b) 3. (b) 4. (d) 5. (b) 6. (c) 7. (d) 8. (c) 9. (a) 10. (b)
11. (d) 12. (a) 13. (b) 14. (a) 15. (b) 16. (c) 17. (d) 18. (b) 19. (a) 20. (a)
21 . (d) 22. (a) 23. (b) 24. (a) 25. (b) 26. (c) 27. (a) 28. (b) 29. (c) 30. (c)
31 . (d) 32. (d) 33. (b) 34. (b) 35. (d)
T0PIC2 Properties of Carbonyl Compounds
1. (d) 2. (a) 3. (b) 4. (d) 5. (a) 6. (c) 7. (b) 8. (b) 9. (a) 10. (b)
11. (b) 12. (b) 13. (d) 14. (c) 15. (a) 16. (b) 17. (b) 18. ( c) 19. ( d) 20. (a)
21 . (b) 22. (b) 23. (c) 24. (c) 25. (c) 26. (d) 27. (d) 28. (b) 29. (c) 30. (a)
31 . (a) 32. (d) 33. (b) 34. (a) 35. (a,c) 36. (b) 37. (a) 38. (a) 39. (a) 40. (b)
41 . (d) 42. (d) 43. (b) 44. (a) 45. (c) 46. (b) 47. (c) 48. (b) 49. (c) 50. (c)
51 . (d) 52. (b) 53. (a) 54. (b) 55. (a) 56. (b) 57. (c) 58. (a) 59. (a) 60. (c)
61 . (b) 62. (d) 63. (a) 64. (c) 65. (b) 66. (a) 67. (c) 68. (b) 69. (a) 70. (b)
71 . (a) 72. (c) 73. (a) 74. (a) 75. (c) 76. (b) 77. (b) 78. (b) 79. (a) 80. (c)
81 . (b) 82. (b) 83. (b) 84. (b) 85. (b) 86. (a) 87. (c) 88. (d) 89. (b) 90. (a)
91 . (d) 92. (c) 93. (d) 94. (d) 95. (a) 96. (a) 97. (d) 98. (c) 99. (a) 100. (a)
101. (a) 102. (a) 103. (b) 104. (d) 105. (c) 106. (c) 107. (c) 108. (b) 109. (a) 110. (c)
111. (c) 112. (b) 113. (b) 114. (a) 115. (e) 116. (d) 117. (a) 118. (b) 119. (d) 120. (d)
121. (d) 122. (d) 123. (a) 124. (a)
TOPIC 3 Carboxylic Acids, Preparation and Properties
1. (a) 2. (c) 3. (c) 4. (d) 5. (c) 6. (a) 7. (a) 8. (c) 9. (b) 10. (d)
11. (b) 12. (d) 13. (b) 14. (d) 15. (d) 16. (b) 17. (a) 18. (b) 19. (a) 20. (c)
21. (a,c,d) 22. (a) 23. (a) 24. (d) 25. (a) 26. (b) 27. (c) 28. (d) 29. (a) 30. (d)
31. (b) 32. (d) 33. (e) 34. (a) 35. (d) 36. (c) 37. (d) 38. (c) 39. (c) 40. (c)
41 . (c) 42. (b) 43. (c) 44. (b) 45. (d) 46. (c) 47. (a) 48. (c) 49. (b) 50. (c)
51 . (d) 52. (a) 53. (a) 54. (b) 55. (c) 56. (c) 57. (b) 58. (d) 59. (c) 60. (a)
61 . (c) 62. (a) 63. (d) 64. (b) 65. (b) 66. (c) 67. (b) 68. (b) 69. (b) 70. (a)
71 . (c) 72. (c) 73. (a) 74. (a)
TOPIC4 Derivatives of Carboxylic Acids
1. (a) 2. (b) 3. (c) 4. (c) 5. (a) 6. (d) 7. (d) 8. (d) 9. (d) 10. ( d)
11. (b) 12. (c) 13. (c) 14. (c) 15. (a) 16. (a) 17. (b) 18. (c) 19. (a) 20. (d)
21. (c) 22. (d) 23. (b) 24. (c) 25. (c) 26. (b) 27. (c) 28. (b) 29. (c) 30. (d)
31. (b) 32. (b) 33. (c) 34. (a) 35. (c) 36. (a) 37. (d) 38. (b) 39. (a) 40. (b)
41. (c) 42. (a) 43. (b) 44. (a) 45. (b) 46. (d) 47. (d) 48. (d) 49. (d)

Explanation
Topic 1 Preparation of Aldehydes and Ketones
1. R- CH 20H ~ R- CH=O In order to select the other correct choice we will use the concept
Pyridinium chlorochromate (PCC) is the mild oxidising agent of Cannizzaro reaction which is a type of disproportionation
which causes conversion of alcohol to aldehyde stage. While reaction. Cannizzaro reaction is a characteristic reaction of
others cause conversion of alcohol to acid. carbonyl compounds having no a-hydrogen atom. As, Z
undergoes disproportionation (Cannizzaro Reaction), this
Note PCC(C5H 5NH+Cr0 3CI-) is the complex of pyridine, Cr03 , suggests that Z do not have a-H-atom. Thus, Z must be
and HCI in I : I : I ratio. formaldehyde. The chemical reaction occurring in the compound
2. The above synthesis of propionaldehyde would not work because can be sequentially written as
LiAIH4 will reduce aldehyde further to alcohol.
0
II .,,..H (i) LiAIH4 ) ....._ .,,......._
~o...... (ii)H. ....._.,.... "'OH

3. Ozonolysis reaction The substrated containing C=C double In Etard reaction toluene is oxidised to benzaldehyde with a
bond on ozonolysis using 0 3 followed by reductive cleavage of solution of chromyl in CSz or CC14 is as
ozonide using Zn/H20 2 produced two carbonyl compounds. CH3 CHO

~
Carbonyl compound obtained after reduction ozonlysis of(b), (c)
and (d) are as follows

~CH=CH2
l_S) H26:1ZJ
H---..__
~C=O
l9 + 0 = c(H
H
l8J
(X)
CrOzClz/CS2
H30+
© (Y)

Cannizzaro reaction with HCHO can be written as

Benzaldehyde Formaldehyde H, 0$
H; c = 0 Cone. NaOH ) CH20H + HCOONa
H,...._
CH=CH"CH [gJC=O H
3~
H20vZn
Q + O=C/
"cH
4. Ally! ethyl ether on reaction with HI produces ethanal and ethyl
iodide by means of nucleophilic substitution reaction as shown
3
Benzaldehyde Acetaldehyde below
H,I
C\
CH2 = CH L• i
Rr
I
CH2 - wr
CHr-=·'-~
CH3CH = 0 + CH3CH2I
Ethanal Ethyl iodide

Hence, X would be a benzaldehyde. 5. Acetophenone cannot be prepared easily starting from toluene,
In each case, benzaldehyde is produced as one product but on the (;;H5 CH3 because preparation of acetophenone from toluene can
other hand, formaldehyde, acetaldehyde and acetone are only be done by using multi step reaction. From rest of the
produced as other products. compounds, it can be made easily.
650 I Chapterwise & Topicwise Engineering Entrances Solved Papers
OH 0 Thus, acetophenone is not the product of reaction (c).
I II
C6H 5 - CH -
[OJ
CH 3 ~ C6H 5- C- CH 3
/:J
61
0 CHC12 CH "-. HC = 0
O
II
C6H5 == CH Hgz+, H
2504
C6H5 - C- CH3 9. 6'.::::: Concentrated 6'.::::: -:0
~ aqueous ~ ::::...,
KOH
C6H6 + CH3COCl Anhy. A ICl3 C6H5COCH3 Benzyl -2KCI Benzaldehyde
chloride
6. In the given reaction, there is the addition of a hydrogen atom T hus, benzaldehyde is obtained when benzyl chloride is heated
(H) and a forrnyl group (- CHO group), thus, the given reaction
with concentrated aqueous solution of KOH. The obtained
is specifically called hydroformylation or carboforrnylation or
aldehyde because of the absence ofa-hydrogen atom further reacts
oxo process.
with concentrated aqueous KOH solution to give benzyl alcohol
IOO"C,High pressure
and potassium benzoate, i.e. it undergoes cannizaro reaction.
CoH(C0)4
10. Compound shown above is an example of aldehyde because it
contains - CHO group.
R- CH 2- CH2- CHO
I I

7. Me -== + NaNH2 -NH3 Me -== C - Na I

:
O:I

: II :
H OH 1CH3l i H______
I __
- c +- c H2-
I
CH3

Me-
I I
C=C - CH 3 HgS04 Me~C - CH 1
dilH2S04 - 3 Aldehyde group
(Addition of

1 Tautomerisation water) While in case of alcohol, ketone and ester there is a necessity of
presence of following group written in front of their name.
Me - CH2- ~- CH3 orMeilMe Functional group
I- - -I
Alcohol R-~QtJ~
0 0 Ketone
(Here, Me means methyl group) T hus, the correct set ofreagents is
NaNH 2/ CH 3I; HgSO4 / dil. H 2SO 4.
8. The given ketone is acetophenone.

6
0 Ester
II
(i)
O
Benzene
+
cety
chlonde
AICl3
C~3C~Cl (Friedel Crafts )
reaction) -HCI
CH,
(where, R = alkyl group)
11. Carbonyl group(> C=O) is present in fabrics, drugs, plastics,
Acetophenone
ketone flavourings etc.
(ii)CH3C == N + C6H5MgBr - CH 3C = NMgBr OCCH3
H COO"-Ca Dry distillation )
I 12. +
CH3 Hcoo/
C6Hs
J,H20 Calcium acetate Calcium fonnale

0 2CaCO3 + 2CH 3CHO

II Acetaldehyde
or ethanal
CH 3- C - C6H 5
Acetophenone 13. When propylene or propene is treated with a solution of PdCl 2
ketone
containing a catalytic amount of CuCl 2 in presence of oxygen or
~ air, it oxidised to acetone.
Ether
2¼H 5CH 2 COCH 3 + CdCl 2
Benzylrrethyl ketone

HgS04 The above reaction is called Wacker's process

(iv) ¼H5- C=CH ~ C6H 5- C=CH2
Hi$04 I Note Here, PdCl 2 acts an oxidising agent. As, PdCl 2 is an expensive
(Addition of water) OH reagent, the reaction is usually carried out in the presence of
co oxidant such as CuCl 2 which reoxidised as Pd to PdCl2 and it
Tauto merisation
¼ H 5- C- CH3 self reduced to Cu(I) Then reoxidised itself to Cu(II) chloride by
II air.
0
(AcetopheJW:me Pd + 2CuCl 2- PdCl2 + 2CuCI
ketone)
4CuCI + 4 HCI+ 0 2 - 4CuCl 2 + 2H 2O
 Aldehydes, Ketones and Carboxylic Acids I 651
14. Dry distillation of calcium formate with calcium acetate yield
ethanol or acetaldehyde. (HCOO)iCa + (CH3COO)iCa
Dry distillation
2CH3CHO + 2CaC03
15. Collin's reagent is used for selective oxidation of IO alcohols to
aldehydes (or to prevent the oxidation of aldehydes to
carbocyclic acids) -CH 20 H [alcohol] ➔ CHO. It is a I : 2
complex of chromitun trioxide-pyridiniwn
CH3
I 03
16. CH3CH=C- CH=CH2 ~

. 0 CH3 . 0 .
; .,;<J ;x;< 3•methoxy acetophenone
'P'
CH3- 1 Hl( , - fH)( IH2
0/--.:,,.p 0/--·1\o
22.
1Zn/H20
CH3CHO + CH3COCHO + CH20 calcium benzoate calcium acetate.
0
0 0 t, II
~ 2C6H 5 -C-CH 3 + 2CaC03
17. CH3-~- CI (aq.)KOH CH3-~- o-K+ + HCI
23. In Rosenmund's reaction, the acid chlorides are converted to
CH3CHzCI (aq.)KOH CH3CHzOH + KC) corresponding aldehydes by catalytic reaction.
This reaction is carried out of passing hydrogen gas through
CICH2-CH2CI (aq.)KOH HOCH2- CH20H boiling xylene solution of acid chloride in presence of Pd as
catalyst supported over BaS0 4 and partially poisoned by the
CH3CHCl2 aq. KOH CH3- CH(OH)i -➔ CH:,-CH =O addition of sulphur
Intermediate Acetaldehyde
0
18. Propanal is not formed during the dry distillation of a mixture of II rd 4
calcium formate and calcium acetate. CH 3- C- CI + H2 • aaso CH3CHO + HCI
Dry di~illation Acctyl chloride Acetaldehydc
(HCOO)iCa HCHO+ CaC03
24. 2-hydroxypropane or secondary alcohol is oxidised into
propanone (corresponding carbonyl compound because in
2-hydroxypropane, secondary alcoholic group is present and it is
(HCOO)zCa + (CH3COO)zCa ~ 2CH3CHO + 2CaC03 oxidised into ketone).
Cl [OJ
CH3 - r - CH3 ~ CH3 - rr- CH3
19. CH3 - t- H Dil.NaOH
OH 0
ti Unstable
2-hydroxypropane
(s-alcohol)
Propanone
(ketone)
I, I ~dichloroethane

l
CH3CHO + H20
25. Stephen's reduction Aldehyde can be prepared from alkyl
cyanides. e.g.
Acetaldehyde
CH3-C = N + 2[H] SnCl 2 / HCI CH3-CH = NH-HCI
Ether Acetaldiminc hydrochloride

20. @Benzene
+ co
Carbon
AICl3
HCI
Acctaldehyde

monoxide
Benzaldchyde 26. Aluminium tertiary butoxide is used as an oxidising agent for the
oxidation of secondary alcohols into ketones.
The reaction is known as Gatterrnann-Koch formulation.
652 I Chapterwise & Topicwise Engineering Entrances Solved Papers

CH3- CH2- TH- CHz- CH3 Al [ OCMe3 h i acetone For the above conversion, only suitable reagent is chromic
anhydride in glacial acetic acid. Others will also effect (C = C)
OH bond.
3-pentaool
34. Calcium salts of carboxylic acid on heating give carbonyl
Me"
CH 3- CH2 - TI-CH 2- CH3 +Me / CHOR compound.
0 lsopropyl (a) (HCOO)zCa + (CH3CH 2COO)zCa
3-pcntanone alcohol Calcium fomnte Calcium propanoate

27. The given reaction is Rosenmund reaction, - 2CH 3CH2C- C + 2CaCO3

P ropanal 11

i (b) (CH 3COO)2 Ca + (CH 3CH2COO)zCa

0

cb c~~(A)
Pd/BaS04
Calcium acetate

(c) (CH3COO)zCa + (CH3COO)zCa

Calciurn propanoate
0
2CH 3- ~ - CH2- CH 3 + 2CaCO3
2-butanone

Calcium acetate CaJcium acetate

So, compound (A) is benzoyl chloride. 0
28. Calcium adipate on dry distillation gives cyclopentanone.
II
~ 2CH 3- C- CH3 + 2CaCO3
Acetone
CH2 - CH 2 - CO o , A
I Ca ~ / (d) (HCOO)zCa + (CH 3COO)2 Ca
Calcium formate Calcium acetate
CH2 - CH 2 - ._C_
O_O_ __, 0
~ 2CH3 - Ethanal
Calcium adipate
~- H + 2CaCO3
CH 2 -CH,
I - CO + CaCO3
CH2 -CH 2 35. Rosenmund's reduction involves the reduction of acid halide into
Cyclopcntanone aldehyde by means of Pd/BaSO4 •

29. Calcium acetate on distillation produce acetone. CH3COCI

rd
'!~ 04
CH 3CHO + HCI
C H 3 ~Ca
0 0··1
1st1 1·
ation ) CH3COCH3 + CaCO3
CH3 COO Acetone Topic 2 Properties of Carbonyl
Calcium acetate
Compounds
30. Acetophenone can be prepared by Friedel-Craft's reaction. By
treating benzene with acetyl chloride in presence of anhydrous 1. This problem includes concept of nucleophilic addition reaction
aluminium chloride, acetophenone is obtained. of carbonyl compound (ketone here) and intramolecular
nucleophilic substinition reaction.
Anhyd. AICI 3
½ H 5H + CICOCH 3 ½H5COCH 3 + HCI Complete reaction sequence is as shown below
Benzene Aoetyl Acetophenone
chloride 0
31. The Gattermann-Koch aldehyde synthesis is as follows Cl~ CH3MgBr, dry ether, 0°C
CH3 Nucleophilic addition reaction

01 ,...._...._
Benzene
+ CO + HCI---->
AICJ
Anhyd.

3
()::::,....C
HIO

Benzaldehyde
+ HCI aq. acid
intramolecular
nucleophilic
substitution reaction
32. Calcium formate on distillation gives HCHO. / \ /CH
~oXcH: + MgXCI
(HCOO)zCa Dis1illation l HCHO + CaCO3
2° Hence, correct choice is (d).
33. CH 3 - CH- CH = CH- CH 3- - -
1 2. M ichael addition The addition of enone to an a,p-unsanrrated
OH carbonyl compound at the P -carbon is called Michael addition.
Pent -3-en -2 -ol CH3- C- CH = CH- CH 3 This reaction basically involves 1,4- addition of a doubly
II stabilised carbon nucleophile to an a,P-unsanirated carbonyl
0
Pent -3-en - 2-one compound.
 Aldehydes, Ketones and Carboxylic Acids I 653
7. Condensation ofNH2NH2 at both nitrogens w ith C6 H 5CHO gives
the desired product.

@-cHO + NH2-
Benzaldehyde l NH2
@-cHO

@ - c H = N- NH2 _ _ _ ___,

@ - c H = N- N=C + H - @

8. Acetaldehyde contains a-H, so it undergoes aldol condensation

rather than Cannizzaro reaction.
9. Addition ofCH 3MgBr to carbonyl compound produces addition
product by means of nucleophilic addition reaction. It is then
undergoes hydrolysis as shown below

The number of chiral centre in product is one which is ~ H + CH3MgBr

represented by star (*). 0
3. Reactivity of nucleoophilic addition reaction depends upon the
H 3C 0 - MgBr H3C OH
electron deficiency of carbonyl group and steric hindrance. Steric
hindrance decreases the rate of reaction. This steric hinderance is ~
Ether
H 3C -
I I
C - C- H
H3o+
~H
I I H
3C - C- C-
2
minimum in methanal and maximum in benzophenone. Further, 4
I I 13 1
aromatic ketones are less reactive than aliphatic analogues due to H CH 3 H 1CH
3
the presence of+ R - effect of the benzene ring which increases 3-methy lbutan-2-ol
the e lectron density on carbonyl carbon. Hence, the correct order
is IV < III < TT < I 10. Since, the compound reacts with Tollen's reagent so it must
0 contain a - CHO (aldehyde) group. Further, it does not give
II aldol condensation, it means that in it, a-hydrogen atom(s) is
4. Aldehydes and ketones possessing (- C- CH3) group will give (are) absent. The strncnrre of the given compound is as
positive iodoform test. Apart from methylated carbonyl 0 CH3

oompo~ds, ,kohols with [ CH,1:~) group , loo give

o: II o:
CH 3CH2 C- CH 2CH 3 CH3C- CHO
3-pentanone
(No-CHO group but
o.-H atoms present)
I
I
CH3
2, 2-dimethyl propanal
positive iodoform test. (have - CHO !l)"Oup and
o:-H atom is absent)
12and
NaOH CHI3 + ¼H5COONa Tautomerism 1l
lodoform CH3
I o:
CH 3 CH CH2CHO
5. As the number and the size of the alkyl groups increases, on a 3-hydroxy-2-pentene 3-irethyl butanal
carbonyl carbon reactivity decreases. Hence, the reactivity order (No - CHO !l)"oup) (have - CHO !l)"Oup and
o:-Hatoms)
is
CH 3 0
H"-. H"-. CH3"-. (CH3)3C"-.
/C=O> /C=O > /C=O> /C=O I II
H H3C CH3 (CH3)3C CH3CH- C- CH 3
3-methyl -2-butanone
TT III IV (No -CHO!l)"Oup
Ct• H atoms present)

6. Four enols, two pairs of geometrical isomers. Thus, A is 2, 2-dimethylpropanal (as it contains a - CHO group
CH 3- CH 2- C - CH2- CH2- CH3~ but no o:-H atom).
II 3-hexanone 11. On reversing the process of aldol condensation in the following
° CH3- CH2- T =CH- CH2- CH3
manner, we get two moles of ethanal.

l OH
Eno! formll
CH3- CH = C - CH2- CH2- CH3
H20
CH 3CH =CHCHO --➔ CH3 CH- CHH2CHO
But -2-enal Hydration
OH
I
13-hydroxy aldehyde
I or aldol
OH
Reversing
(Eno! form I)
654 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Thus, the combination of compounds to give then given product
is two moles of ethanal.
12. Since, the compound forms 2, 4-DNP derivative, so it must be a
carbonyl compound.
It reduces Tollen's reagent and undergoes Cannizzaro reaction,
so it must contain a - CHO group and no a-H atoms.
Thus, its possible formula may be CH3C6H 4CHO. Since, it gives
1, 2-benzene-dicarboxylic acid when subjected to oxidation, so
- CH3 and - CHO gropus must be present at successive
positions. Thus, the stmcture of the compound must be
The reactions occurring are as follows
CHO CHO COOR
16. As the number/size of alkyl group attached to the carbonyl carbon
increases, their reactivity towards HCN (addition-elimination
reaction) decreases due to steric hindrance.
Hence, the order of reactivity of different compounds towards
HCN is di tert-butyl ketone < methyl tert-butyl ketone< acetone <
acetaldehyde.
or [(CH 3) 3CJiC=O < (CH3)3CCOCH3
< CH3COCH3 < CH3CHO.
17. CH3CH2CHO CH 3COCH3
(Aldehyde) (Ketone)
Since, molecular formula of above given compounds is same, i. e.
C 3~0 and functional groups present in them are different,
therefore both these compounds show functional isomerism and
are called as functional isomers.

Ct"'
2-methylbenzaldehyde
&
CH3
Tollen 's
reagent
(Ag20)
&CH3
I ,,,::;.
+ 2 Ag 18. When acetaldehyde (2 moles) is heated with dilute NaOH
solution, aldol obtained.
CH3- y=O + HCH2 - y=O

H H
Dil. NaOH

19. Iodoform test is given by those carbonyl compounds which

0
II
contains CH3- C- group while Fehling's test is given by
13. Resonating structures involves movement of electrons, but they aldehydes only. Thus, Iodoform test and Fehling's test are
do not involve movement of atom or group of atoms. performed by ethanal.
CH3CHO + 2Cu 2+ + SOH-~ CH 3COO- +3Hz0 + Cup
Ethanal Fehling's solution Cuprous oxide
(Red ppt)
Me......_OUMe ~ Me......_O~Me
I I II
20. The structure of 2-butanone is
0
II
0 o- CH 3- C- CH2 - CH3
Me......_oUMe Hence, it is methyl ethyl ketone.
TH 21. Formaldehyde and KOH on heating produce methyl alcohol.
2HCH=O + KOH ~ CH 30H + HCOOK
Thus, structure JV is not a resonating structure of others.
Formaldehyde Methanol
14. Aldehydes lacking a-H atom, undergo Cannizzaro reaction if
The above reaction is Cannizaro's reaction.
treated with concentrated alkali (NaOH), i.e. one mole of the
aldehyde is reduced to alcohol and other mole is oxidised to salt 22. Complete oxidation of aldehyde from acids as
of acid.
R- CHO ~ R- COOH
Thus, the given aldehyde (glyoxal) undergoes intramolecular
Cannizaro reaction, i.e. its half part is oxidised and half is Note On partial oxidation, aldehydes give alcohols.
reduced. 23. The nucleophilic addition reaction is the characteristic addition of
carbonyl compounds. Reactivity order of carbonyl compounds is
cl HO (i) NaOH (Ceonc) clH20H in the order.
(ii)W H'---. H 3C'-.__ H3C'-.__
CHO C02H /C=O> /C=O> /C=O
H H H 3C
This is due to increase in the intensity of charge on carbon of
carbonyl group due to+ /-effect of alkyl groups. Thus, making
carbonyl group less reactive towards nucleophilic substitution
reaction.
 Aldehydes, Ketones and Carboxylic Acids I 655
24. When acetone reacts with Br2 in basic medium, bromoform is o- CH,OH
formed. I I - H2 0
H- C - C- CHO ~
Reaction I I I
CH3COCH3 + 3Br2 + 4NaOH H CH2OH
I mol 3 mol
~ mol I mol CH2OH O 0
3 I II II
~ CH 3COONa + CHBr3 + 3NaBr + 3H2O Step IV HOCH2- T- - C- H + H- C- H
(U ) (T)

When CH 3COCH3 and Br2 are in equimolar quantity, all the Br2 CH2OH
(limiting reactant) is converted into desired products and 2/3 OH OH
mole ofCH3COCH3 remains tmreacted, being in excess.
When acetone reacts with Br2 in acidic medium, there is
Cannizzaro )
reaction ~ +Hcoo-
monobromination of acetone. HO OH
Reaction JI
In the last step, formaldehyde is oxidised and the ot11er aldehyde
CH3COCH 3 + Br2 - - -- CH3COCH2Br + HBr is reduced giving the desired product.
I root I mol (P) 27. Iodoform is formed from
In reaction I, (!]) and (T) are formed and acetone (reactant) (i) CH3CHpH 0
remains unreacted. (ii) CH3CHO II
In reaction TI (P) is formed. (iii) All corbonyl compounds of the type R- C- CH3
(iv) 2° alcohol R- CHOH
25. Cannizzaro reaction is possible in those aldehydes where
a-hydrogen atoms are absent. I
e.g. HCHO, ¼ H 5CHO CH3
0 0
2HCHO NaOH
!;
HCOONa + CH3OH II II
(a) CH3CH2- C- CH3, R- C- CH3 Yes
(b) CH3THCH3, R- THCH3 Yes
26. The given reaction is an example of repeated aldol condensation OH OH
followed by Cannizaro reaction. 2° alcohol

Step I CH3CHO + OH- ~ CH2- CHO + Hp (c) CH3 - I[- JH - CH3, R- [ - CH3 Yes
0 0 CH3 0
II CH3

OH
I
(d) CH3- T-OH No
H20 I
- CH2 - CH 2- CHO CH3

0 o- 28. (a)
II 1
Step II H- C- H + CH- CHO H-C
I I
CH2OH H
o-
1
H- C- CH- CHO
I I (b)
Zn(Hg)/HCI
H CH2OH HCI attack

___:,.
Step III HOCH2 - CH- CHO + HO-
I Na/NH3
( Y CH =
AJ CHCOCH3
CHpH O (c)
NaO
- II
HOCH2- C- CHO + H- C- H HCI attack 2° alcohol as well as (C=C) bond.
I NaBH4
CHpH (d) - - ~- Low yield
656 I Chapterwise & Topicwise Engineering Entrances Solved Papers

H'-... 36. Methyl ketones (acetone) and acetaldehyde both give

29. W ,,,-C = 0 + CH 3MgI iodoform test.
Grignard reagent (X)
Formaldehyde 0
II
CH 3- C - H I R + 312 + 4NaOH -

Al ( ~H 3) s
0
30. 2CH 3CHO ----➔ CH 3COOCH 2CH 3 II
Acetaldehyde Tischenko reaction Ethyl acetate Cffi3 + H /R-C-ONa + 3NaT+ 3H 2O

COCH3 37. 6HCHO + 4NH 3 - (CH 2 \N4 + 6Hz0

©
Hexamethylene
tetramine

31. CH:~~CH, 38. In Wolff-Kishner reduction, carbonyl compounds are

reduced to alkanes with same number of atoms by using
Acetophenone Salicylic acid Benzaldehyde
NH2 · NH2 and KOH / glycol.
Since, given compound 'A' bums with flame, therefore it must be CH 3 CH 3
aromatic compound. Again when it reacts with Brady's reagent (acidic I - H20 I
2, 4-dinitrophenyl hydrazine solution), it yields orange precipitate. CH3-C=O + H2N· NH2 ~ CH3-C=NNH2
Therefore, it must be aldehyde (d) or ketone (a). But ketone 'A' does
not perform Tollen's reagent test, therefore it must be a ketone. Hence, CH 3
'A' is acetophenone. I
~ C H3 - y - H
32. In Cannizzaro's reaction, aldehydes which have no a-hydrogen,
undergo disproportionation, in the presence of strong base, to form H
Propane
equal amounts of the corresponding alcohol and salt of carboxylic
acid. Acetaldehyde due to the presence of 3a-hydrogen atoms, does
not perform this reaction.
2CCl3CHO + NaOH --➔ CCl3COONa + CCl3CH 2OH
39.
(X) (i)OJ

(a) 5 O 7
2C6H 5CHO + NaOH - C6H 5COONa + C6H 5CH2OH 4~8 (i)NaOH(aq)
(b)
3 ~ 9 (ii)Heat
2HCHO + 2NaOH - HCOONa + CH 3OH 2 O 10
(c)

33. Dihydropyran reacts with alcohols in the presence of anhydrous H+ to For aldol condensation C-5 and C-7 can attack to C-1
form acetals. Thus, option (b) is correct. similarly C-2 and C-10 can attack to C-6 but all give same
product.

l_o}
~ • +-

."";.;)
"I" H
0~
.
Q/.
+,J
H~CH2R
40. A + NaOH - alcohol + acid
Thus, it is Cannizaro reaction. A is thus, aldehyde without H

Q_Q"0
.()/H
CH2R
Q
Dihydropyron

-
H+
0 OCH2R
ata-carbon (like ¼ H 5CHO, HCHO). Hence, benzaldeyhde
tmdergoes Cannizaro reaction.
2C6H 5CHO + NaOH - ¼ H 5CHzOH + C6H 5COONa
Berrzaldehyde Alcohol Acid
(Acetal)
41. When acetaldehyde is treated with aqueous sodium
34. Cannizzaro's reaction is given by aldehydes (RCHO) lacking H at hydroxide solution, it undergoes aldol condensation
a-carbon or lacking a-carbon (as in HCHO). With NaOH, there is (because of the presence ofa-H atom) as
formation of acid salt (RCOO- ) by oxidation and alcohol (RCH 2OH)
CH CHO + HCH CHO Oil. aqueous
by reduction. 3 2 NaOHl
a c1 o a A •
I I II I CH3CH=CHCHO t--CH3 C H(OH)CH2CHO
2CI- C - CHO + NaOH ~ Cl - C - CONa + CI - C- CH,OH (Showsgeometrical isomerism) Aldo!
I "" I I - (Shows optical isomerism)
Cl ) C_I _ Cl 42. With Fehling's solution, benzaldehyde as well as acetone
cx~rbon without H By ox1datton By reduction
2, 2, 2-trichloroethanol do not react while with To lien's reagent, benzaldehyde gives
precipitate but acetone does not react.
35. All aldehydes including reducing sugar (as glucose, fructose) give Hence, Tollen's reagent is used to distinguish them.
Silver-mirror test (with Tollen's reagent).
43. Aldehydes and ketones containing a-hydrogen atom
RCHO + 2(Ag(NH 3) 2 f + 30W ~ tmdergo self condensation in the presence ofa dilute alkali to
form j3-hydroxy aldehyde or j3-hydroxy ketone. This reaction
RCoo- + 2Ag J, + 4NH3 + 2H2O is called aldol condensation.
Silver mirror
 Aldehydes, Ketones and Carboxylic Acids I 657

Ba(OH)2 CH3- CH 2TH- CH2- CH3 - ~;0 >

OH
'Z' alcohol
(Cofl1X)und 'A)
0 OH (CsH12O)
II I
CH3 - C- CH2- C- CH3
I Ketone
(Compound 'B)
CH3 (CsH1oO)
jl-hydroxy ketone
(4-hydroxy-4-methyl pcntan-2-one) 50. Aldo! condensation is given by those aldehydes and ketones

44. H-
?iT + CH3- ?iC- H
Dil. NaOH
:;:::=::::::::::::::::::::::::~ H-
?H
T- CH2- CHO
which have at least onea-H atom. When this reaction takes place
between two different aldehydes and ketones, it is called across
aldol condensation, e.g.
H H 0--.__ OH
6. HCN CH3-
II \ Off" I
C + HCH2CCH3 ~ CH3- C- CH2COCH3
----+ CH2 = CH- CHO---+ CH2 = CH- CH- COOH I
H30+ I o.-Hatom acetone ]
H H
OH Aootaldehyde 4-hydroxypcntan-2-<me

?H
36
H- C= O
+ CH3CHOHCH2CHO + (CH3)i C - CH2COCH3
3-hydroxyl butanol 4-hydroxy-4methyl
45. + 2NH3 -- -3H-20
~ from 2 molecules of pentan-2one
acetaldehydc (From 2 molecules ofacetone)

51. When ammonia (NH3) reacts with formaldehyde (HCHO),

46. Addition of HCN to a carbonyl compound is a nucleophilic
hexamethylenetetramine which is also known as urotropine, is
addition reaction. -N02 group being electron withdrawing
formed. Urotropine is used as a medicine to treat urinary
increases the polarity ( or electron deficiency) of carbonyl carbon
infections.
and thus, makes the C = 0 group ofbenzaldehyde more reactive
towards HCN. 6HCHO + 4NH 3 - (CH2\N4 + 6H20
Formaldehyde Ammonia 1.Jrotropine
47. As the product obtained does not answer silver mirror test, the
product must be a ketone. Ketones are obtained by the oxidation
of secondary alcohols by using acidified K 2Cr20 7 . Thus, Xis Major

secondary alcohol, i.e. (CH 3)i CHOR. + CH 3CH(OH)CH2CHO

+ (CH 3)2C(OH)CH2COCH3
H3C"-C=CHOH + [OJ Acidi fied H3C"-C =O
H3C/ K2Cr20, H3C/ + (CH3)iC(OH)- CH2CHO
I!.
Secondary alcohol Acetone
CH3CH(OH)CH2COCH3 -H ➔ CH3CH =CHCOCH3
(X) 20
Major product Major product (25%)

53. (i) Organic compound gave an oxime with hydroxyl amine,

therefore, it must be an aldehyde or ketone.
(ii) Organic compound did not give silver mirror with Tollen's
Dil. reagent, therefore, it cannot be an aldehyde.
NaOH Therefore, compound is ketone and its molecular formulae
(aldolconde nsation)
with be CH3COCH3.
54. In Clemmensen's reduction, aldehyde (RCHO) and ketones
CH3- CH - CH2CHO (R-CO-R') are reduced into hydrocarbons (R-R' ) by zinc
I amalgam and cone, HCl
OH
(Z)Aldol Zn amalgamated
RCHO + 4[H] Cone. HCI
49. Since, the compound 'B' gave a 2, 4-dinitrophenylhydrazine
derivative but did not answer halogen test or silver mirror test, it 55. Aromatic aldehydes reacts with aliphatic acids anhydrides in the
must contains a C = 0 group, but it is neither a methyl ketone presence of sodium salt of the same acid as base to form
nor an aldehyde. condensation products which upon hydrolysis give
Moreover, compound 'B' is obtained by the oxidation of a, 13-nnsaturated acids. This reaction is called Perkin
compound 'A' having molecular formula C 5H 120, so the condensation. For example, when benzaldehyde is heated with
compound must be a secondary alcohol. acetic anhydride in the presence of sodium acetate, the products
thus formed on hydrolysis gives cinnamic acid.
658 I Chapterwise & Topicwise Engineering Entrances Solved Papers

C6H5 CH= 0 + H2CHCO"'- CH3 COONa, 453 K H 3C"'- /CH3 + Mg/OH

Benzaldehyde /0 -~----➔
CH3CO -H20 H C/ C"'-OH "'-Br
3
Acetic anhydride 'X'or (CH3 l)COH
2-methyl propanol-2

62. CH 3COOH eaco 3 (CH3COO)iCa

'A'
Condensation product

c:l2~·~ i\
0

Y ro ysts
l C6HsCH=CHCOOH + CH3COOH
Cinnamic acid _. -
(CH3)iC =NOH
Acetoxime
( Cl,-~ unsaturated acid) Acetic acid
63. The a-hydrogen atoms of acetaldehyde due to - /- effect of
56. Carbonyl carbon becomes more reactive towards nucleophilic C = O group is slightly acidic in nature. In crossed aldol
addition depending upon the magnitude of the positive charge on condensation between formaldehyde and acetaldehdye in the first
the carbonyl carbon atom. The introduction of negative inductive step OH- ion (from the base added) abstracts one of these acidic
effect showing group (-/-effect) increases the reactivity while a-hydrogens to form carbanion or enolate ion which is stabilised
introduction of alkyl group (+ /-effect) decreases the reactivity. by resonance.
So, large alkyl group decreases the reactivity of > C = 0. 0 0
HO- + H- CH2 - g - H ~
Hp + : CH2 - g - H
64. The compound which contains - COCH 3 group in its structure,
give positive iodoform test and the compound which contains
- CHO group give positive Fehling's test.
Thus, oxidation number of carbonyl carbon in acetophenone In ethanal, CH3CHO both the groups are present, hence it
is+ 2 responds to both iodoform test and Fehling's test.
Cone. NaOH CH3CHO + 3 I2 + 4 NaOH ~ CHI3 J, + 3 NaI
58. HCHO HCOOH + CH3OH lodoform
Methanal Formic acid Methyl a lcohol
+ 3H2O+ HCOONa
Thus, reaction is called Cannizaro's reaction.
CH 3CHO + 2Cu (OH)2 Nao~ CH3COONa + Cup J, + H 2O
59. (a) X forms 2, 4-DNP derivatives, it shows that it is a carbonyl Fehling 's Red ppl.
compound (> C=O). solution

(b) It reduces Tollen's reagent, it shows that it has an aldehyde
group.
(c) It undergoes Cannizaro reaction, that also shows the presence
of an aldehyde having no a-hydrogen.
(d) On vigorous oxidation, it produces I, 2-benzenedicarboxylic
65. Perkin reaction is the condensation reaction in which aromatic
aldehyde is heated with an anhydride of an aliphatic acid in the
presence ofsodium salt of the same acid to form a,~ -unsaturated
acid.
CHO

© ·~~~~f
acid. It shows that groups are present at 1,2-position on
benzene ring.
Thus, the correct structure of the compound Xis
~ (t
CHO
©Y½H,
benzaldehyde
(X)
CH=CH·COOH

CH,COOH+©
cinnamic acid
0 0 0
II II II 66. Aldehyde and ketone having a-hydrogen atom undergo aldol
condensation in presence of dilute base to give !3-hydroxy
60. Ph /c'-.......~H2/~'-.......0H Decarboxycatton
Heat (-COz)) Ph/c'-.......CH3
Acetophenone aldehydes or ketones. Acetone has a-hydrogen atom, hence it
Keto acid
E will give aldol condensation reaction
(lodofonn
reaction) 2CH3COCH3 Dil. NaOH H3C)C- CH2COCH3
lz!NaOH H3C I
OH
~-hydroxy ketone

67. - OH is more activating than - CH3 in o, p directing thus

- CHO goes to ortho wrt., - OH group.
Acetone Complex
 Aldehydes, Ketones and Carboxylic Acids I 659

$
OH 74. In Claisen condensation aromatic aldehydes having no
ex-hydrogen atom react with aldehyde, ketones or esters having
Reimer-~emann )
reaction
ex-hydrogen atom in presence of dilute alkali to form a,
+ CHCl, + OW [3-unsaturated carbonyl compound. e.g.
CH3
CH3
p-cresol C6H5CHO + HJ- coo@ Dil. NaOH
OH H OH
CH3
•~, $ - L - O H ·~· $ - CH(OH)COOH
C6H5CH=~- coo---@+ H2O
o,J>-unsaluraled carbonyl compound
CH 3 CH 3
(8) Claisen condensation is not given by
68. Nucleophiles that are relatively weak bases such as CN-, RNH 2
and x- give conjugate addition, whereas strong bases such as
R- Li, R- Mg- X give direct addition.

~ b t t a c k here
as it does not contain a-hydrogen atom.
75. Aldehydes are reduced by LiAJH4 to alcohols and alcohols are
U ~Attack here
Conjugate addition
U
Direct addition
oxidised by copper to give aldehydes.

0 HOH

6 MeMgBr
(GR)

HgS04
MeoOMgBr MeoOH
) I ~

Oil
I
/OH
+ Mg"Br
~ CH 3CHO
(X)

76. The aldehydes containing a-hydrogen undergo self addition in

presence of a base to form products called 'aldols'. The reaction
69. CH=== CH Dil. H§O)
4
CH3CHO ----,-N.,...aO"'H,,..--➔ is called 'aldol condensation'.
Acetaldehyde [AIdol condensation ]
[A] Example Two molecules of acetaldehyde combine with each
CH3- CH- CH2 - CHO other in presence of di!. NaOH to form 3-hydroxybutanal.
I OH
OH
aldol OH- I
(B) CH3CHO + HCH2CHO- CH 3- CH- CH2 - CHO
3-hydroxybutanal
This reaction is followed by acidic oxidation and aldol (aldol)
condensation, respectively.
77. Aldo! condensation is given by acetaldehyde due to the presence
CHO ©:COONa of a-hydrogen atom.
70. © : Cone. NaOH l CH 3CHO + H · CH 2CHO
CHO CH2OH Dil. NaOH) CH - CH- CH - CHO+ ROH
3 I 2
COOR
OH
~ Aldol
H+
©:
CHpH
78. The addition of ex, [3-unsaturated carbonyl compound, with
This reaction is an example of intramolecular Cannizaro' s
conj ugated diene is called Diel's-Alder reaction.
reaction.
Cf-Ii
7 1. (
0

0
X 0
+ NaOH (aq)
O
+ II
CH-CHO
Acrolein
(Dienophilc)
~
0-cHO
Adduct

It is like the saponification reaction of esters.

72. Acetals are dialkoxy compounds is which alkoxy groups are
attached to the same carbon atom. Thus, the given compound is
an acetal.
73. Aldehydes and ketones with NH 2 · NH2 forms hydrazones.
RCHO + H 2N · NH2- RCH = N · NH2 + H 2O
Hydraz.one
RiCO + H 2N · NH2- R2C = N · NH2 + H 2O Hydrobenzamidc
660 I Chapterwise & Topicwise Engineering Entrances Solved Papers

80. 40% aqueous solution of formaldehyde (methanal) is called as
formalin .
Note Formalin used as disinfectant and preservative for biological
specimens.
81. Aromatic aldehyde i.e. C6 H 5CHO are not able to reduce Fehling's
solution but it gives Cannizaro's reaction with alkali.
89. Ketone and aldehyde can be distinguished by Tollen's reagent,
Fehling's solution and Schiffs reagent. Thus, CH 3COCH3
(ketone) and CH 3CH2CHO (aldehyde) can be distinguised by
Tollen's reagent. CH3CH 2CHO reacts with Tollen's reagent to
give silver mirror while CH 3COCH 3 does not react.
CH 3CH 2CHO + Ag2O ~ CH3CH2COOH + 2Agj,
Silver mirror

"
82. / C=O + H 2NOH ~
Carbonyl
COIT1)0und
Hydroxyl
amine
"
/C=NOH + H 2O
Oxime CH 3 COCH3 + Ag2O ~ No reaction

83. The self condensation of acetaldehyde in presence of dilute 90_R- C- R' ~ R" c/oH LiAm 4 R "-c/oH
KCN R'/ "-CN R' / "-CH 2NH 2
alkalies is called aldol condensation and the product is known as 11
aldol. 0
H 0 91. Carbonyl compounds are reduced to corresponding alkanes with
I II (Zn + cone. HCI).
CH 3 - C=O + HCH2- C-H It is called Clemmensen's reduction.
0
Oil. NaOH
CH3CH2·C- CH3
II Zn (Hg)+ HCI CH3CH2CH2CH3
92. Addition of HCN is nucleophilic addition. Greater the electron
deficiency on carbon atom carbonyl group higher the rate of
reaction.
Hence,

~
Ph - C- Ph <Ph - C- CH 3
~
0 0
II II
< CH 3- C- CH 3 < H-C- H
85. Ketones on reduction with LiAIH4 gives secondary alcohol. 93. As B forms a shining silver mirror warming with ammoniacal
silver nitrate, B must be an aldehyde which can be obtained by the
0 oxidation of alcohols. The complete series of reaction can be
II represented as
( 8 yC- CH
~ :2[H] CH 3CH 2CHO
(B)
Propanal
CHO CHzOH

86. rb
~OMe
+ HCHO NaOH A"
~OMe
+ HCOOH
CH3CH2CH = NCONHNH2

Thus, compound C is CH3CH 2CH = NCONHNH 2

94. Benzaldehyde on reaction with ale. KCN tmdergo condensation
(C)

OMe OMe reaction to give benzoin.

0
It is an example of crossed Cannizaro's reaction. II
2Cc;H 5CHO C6H 5 - CHOH- C - C6H 5
LJ
KCN(alc.J
0 CHO r{OyCOOH Benzoin
87.
(X)
Conc.NaOH)
LJ
Furoic acid
95. Tollen's reagent is ammoniacal solution of AgNO3, i.e.
[2moles] [ Ag(NH3 )i ]NO3,
96. CH 3 - C =CH2 + DzO ~ H 3C- C =CH2
I I
OH OD
Enol form of acetone
Furyl alcohol

Tt is an example of Cannizaro's reaction. 97. Benedict solution is readily reduced by aldehyde. It doesn't
88. - <;:=0 + NH2OH ~ - C= NOH + H 2O oxidise anhydrides.
I Hydroxylamine I 98. 2-pentanone and 3-pentanone can be distinguished by iodoform
H H test. CH3COCH2CH2CH 3 (2•pentanone) gives positive iodoform
A ldehyde Aldoxirre
test while CH3 CH2COCH 2 CH3 (3-pentanone) doesn't give
iodoform test.
 Aldehydes, Ketones and Carboxylic Acids I 661
99. When treated with Ba (OH)i, acetone undergoes aldol 106. This reaction is an example of Perkin's reaction because in it a,
condensation to fonn diacetone alcohol. (>-unsaturated acid is obtained with aromatic aldehydes.
0 H 0 Therefore, (X) is acetic anhydride i.e. (CH3CO2)O.
II .,-----..._ I II
CH3-C
I
CH 3
+ CH2 - C - CH3 MeO
-0- CHO +
CH3CO"o CH3COONa
/
CH3CO
(,\J

OH 0
Meo-Q-cH=CHCOOH + CH3COOH
Ba(OH)2 I II
CH3-?-CH2- C - CH 3
107. Carbonyl compound + HCN-
CH3
Diacetone alohol
. ~
cyano hy cir111 H20/ H+ Hy ciroxy act'd

100. When acetaldehyde is heated with Fehling solution, a red COOH

precipitate of Cu 2O is obtained, I
Lactic acid is H 3C - C- H
CH3CHO + 2Cu (OH)i + NaOH
I
- CH3 · COONa + eupJ, + 3H 2O OH
Red
0
101. Acetone reacts with Grignard reagent to form tertiary alcohol. 11 •
Thus, CH 3 - C- H + HCN ~
H3C'y..
H3C /" = 0 + R-MgX -
H3C '-s
H3C /T- OMgX
Acetaldehyde

R
H3~)c(~; H30 + :3C)c<iioH
HC, /X
~ 3 'C-OH + Mg Cyanohydrin
H 3C / I '-s oH
R Hence, cyanohydrin of acetaldehyde forms lactic acid.
3° alCQhol 108. Acetaldehyde on heating with Tollen's reagent give silver mirror
102. Aldehydes which does not contain a-hydrogen atom undergo self test while acetone is not oxidised by Tollen's reagent (Ketones
oxidation and reduction on treatment with cone. solution ofalkali. oxidise only under drastic condition).
This reaction is called Cannizaro reaction. 109. Aldehydes are oxidised by weak oxidising agents like Tollen's
CHO CHO COOH reagent (which is ammoniacal AgNO 3) but ketones cannot be

©© ©
~OH oxidised by them.
50%Na0H RCHO + 2(Ag(NH 3hf 30W RCOO + 2Ag t
+ + Aldehyde Tollen 's reagent silver mirror

Benzaldehyde (2 molecules) Benzyl Benzoic acid

alCQhol
103. Aldehydes and ketones condense with alcohol to give acetal and Ketone + Tollen's reagent - No reaction.
ketals respectively, e.g. 110. Benzaldehyde reacts with methyl amine to give Schiff's base
/OC2Hs C6H 5- CHO + H 2NCH3- C6H 5CH = N · CH 3 + H 2O
CH3CHO + 2C2H 5OH - CH 3CH '- SchiJT'sb3"'
-H20 OCiHs
Acetal
111. C- CN group is called cyanohydrin.
104. Aldehydes are strong oxidising agents. They oxidise by Tollen's I
reagent (ammoniacal AgNO3 to Ag), Fehling's solution (toCu 2O) OH
and Benedict solution (to Ct1 2O). These reactions are used to
112. Molecular formula of A= C2Cl 3OH
detect the presence of aldehyde group in compound.
As (A) reduces Fehling's solu tion and on oxidation gives a
105. Tollen's reagent, Fehling solution and NaOH /Nal/H+ are not monocarboxylic acid (B). It means (A) must be an aldehyde.
able to change butan-2-one (ketone) into propanoic acid because CCl CHO
these are mild oxidising agents, so NaOH/12 firstly form 3 (A)
iodofonn along with C 2H 5COONa with butan-2-one (ethyl This is further confirmed by the reaction
methyl ketone). In these C 2H 5COONa reacts with acid (H+) to
[ OJ Cl2
give C 2H 5COOH (propanoic acid). C2H5OH + Cl2 Q,cidation CH3CHO Chlorination) CCl3CHO
0 A = Chloral [CCl 3CHO]
II
CH 3- C- CH2- CH 3 + 312 + 4NaOH
Bulan -2-one 113. 2½H5CHO NaOH ½H5CH2OH + ¼H 5COONa
Cannizzaro's
(ethyl methyl ketone) reaction
- CHI3 j, + C2H 5COONa + 3Nal + 3H 2O This reaction is given by aldehydes which doesn't have
lodofonn a-hydrogen atom.
C2H 5COONa + w- C2H 5COOH + Na+
Propaooic acid
662 I Chapterwise & Topicwise Engineering Entrances Solved Papers

114. On complete oxidation the obtained compound shows increment 120. Aldehydes having a-H-atoms undergoes aldol condensation in
in molecular weight of only 16. It means only one oxygen atom is the presence of di!. NaOH and yield ~hydroxy aldehydes.
added here. This condition is fulfilled by only aldehyde which on OH
oxidation gives acid. I
CH 3CHO + CH3CHO NaOH CH3CH · CH 2CHO
RCHO~RCOOH 3-hydroxy butanal

:.Original compound must be 121. Formaldehyde with ammonia gives a medicinal compotmd
hexamethylene tetram ine (urotropine), which on nitration gives
CH 3CHO ~ CH 3COOH
Molecula weight 44 Molecula weight 60 one of the most powerful explosive, named cyclonite or RDX
(Research Development Explosive)
6HCHO + 4NH 3 ---4 (CH 2~N4 + 6H20
Urotropine or
Hexarrethylene tetraTJUne

116. 2, 2-methyl propanal does not undergo Cannizaro's reaction due

to absence of a-H atom.
117. Benzaldehyde forms two isomeric semicarbazone with
semicarbazide.

N02

C6H5 '--.... ,,......- H

I
/ N '-----._
i H 2C
I
CH2
I + 3HCHO + NH3
NH2COHN/ N'0
Syn 0 2N - N~ /N-N02
CHz
ROX (.synatrimethylene trinitramine)
118. Alcohols on reaction with Grignard reagent (RMgX) give
hydrocarbon on hydrolysis, hence the compound' A' cannot be an 122. Benzaldehyde lacks a-hydrogen atom, hence tmdergo Cannizaro
alcohol as the product is a oxygen containing compound. The reaction in which it disproportionate into benzyl alcohol and
compound' A' must be propanal. The reaction will be as follows sodium benzoate.
CH 3CH2CH= O + CH 3CH2MgBr~ 2Ci,HsCHO Cone. NaOH C6HS. CH20H + C6HsCOOK
(A)

CH 2CH 3 CH 2CH3 123. Three moles of acetone condense in presence of cone. H 2S04 to
I H30+ I give mesitylene.
CH3CH 2 CH- OMgB r ~ CH3CH 2 CH-OH
(B) j, pentanol -3(CsH120)

119. Clemmensen reduction can be used to convert acetophenone into 3CH3COCH 3

acetone
ethyl benzene as it reduce C = 0 group into CH 2

~ 124. Fehling's solution is cupric ion complex with tartrate anion.

V
Acetophenone
C
'----CH3 Zn-Hg/conc.HCI

Ethyl benzene
Aldehydes reduce it to red precipitate. The red precipitate is
chemically Cu:P . Fehling's solution test is given by aldehydes
only. Thus, acetone being a ketone do not give this test.
Topic 3 Carboxylic Acids, Preparation and Properties
ONa OH OH Friedel-Craft's reaction In Friedel-Crafts reaction,

~
toulene is heated either with alkyl halide or acyl halide in
&cooNa &cooH
1. l8J + CO2 ~2~;; ) LgJ Oil. HCI) LgJ the presence of a catalyst (anhydrous AICl 3).

Sodium phenoxide Sodium salicylate 2-hydroxy

(B) benz.oic acid LCH3l
[Salicylic acid (B)]

Aci<) or OCOCH3 LgJ +~

CH3CO"-o
CH3CO/ ©fCOOH Toluene
CH 3

Hell-Volhard-Zelinsky reaction In HVZ reaction,

2-acetoxy benzoic carboxylic acids having an a-hydrogen atom like acetic
acid (Aspirin)
(C) acid are halogenated at the a-position on treatment with
halogen (Chlorine or bromine) in the presence of small
OCOCH3 amount of red phosphoms to give a-halocarboxylic
&cooH acids.
Hence, C is l8J CH3 COOH
Acetic
<;::H2- COOH
(ii) H 2 0 1
Acid
2. This problem is based on successive reduction, chlorination and Cl
elimination reaction. To solve such problem, use the function of the given Chloroacetic
acid
reagents.
Kolbe's reaction Kolbe's reaction involves electrophilic
(0 LiAIH4 causes reduction attack of very weak electrophilic (CO2 ) on activated
(ii) PCl 5 causes chlorination ortho (major) of para (minor) position of sodium
(iii) Ale. KOH causes elimination and produces alkene. phenoxide or sodium phenate. Sodium phenoxide is
Hence, the complete series of reaction can be represented as generated by treating phenol with NaOH.

CH3COOH

CH3CH2CI
(B)
LiAIH 4

Ale. KOH l
CH3CH2OH
(A)

CH2=CH2
Ethylene
(q
PCls

;(V • "" ,6:' "'co,, ;.V:,coo~¢

Benzene
h- (u)W
Sodium phenoxide o-hydroxy
0

~
h-

or sodium phenate benzo1c acid or COOH

3. Salicylic acid is produced from sodium phenoxide which is obtained by o-sal,cy ltc acid p-hydroxy
treating phenol with base, NaOH. The sodium phenoxide so formed is benzoic acid
heated with CO 2 at 400K under a pressure 4-7 atmospheres followed by
acidification gives 2-hydroxybenzoic acid or salicylic acid as the main 5. Acidity of carboxylic acid (or benzoic acid) depends
product upon the stability of benzoate ion formed. More the
number of electron withdrawing groups attached to

lN,
CQJ
+ CO2 -40"""0K""--+ ~OO
~7atm
H COONa
LgJ
benzene nucleus, more is the dispersal of negative charge
and hence, more is stability of carboxylate ion which in
tum increases the acidity of the respective, carboxylic (or
benzoic) acid.
Phenol Sodium
phenoxide Presence of electron releasing substituent like - OR
OH
group however decreases the acidity by decreasing the

°''"" ©fCOOH stability of generated benzoate ion. Thus, the correct

increasing order of acidity of given compounds is IV < I<
II < III.
Salicylic acid
6. Only carboxylic acids and their derivatives like
4. Stephen reaction In this reaction, cyanides on partial reduction by anhydride are capable to give effervescence with aqueous
SnCl 2/HCI forms an imine hydrochloride, which on subsequent NaHCO 3 solution,
hydrolysis with boiling water yields an aldehyde. I. (CH 3CO)zO + 2NaHCO3
SnCl2/ HCI H20 - 2CH3COONa + H2O + CO2
CH3CN + 2H - - - CH 3CH=NH ~ CH3CHO
Methyl cyanide Acetaldehyde II. CH3COOH + NaHCO3 - CH 3COONa + Hp
664 I Chapterwise & Topicwise Engineering Entrances Solved Papers
7. The halogen atom has electron withdrawing - /-effect. Because 11. When Grignard's regent is treated with CO2, a magnesium
of this, the chlorine atom withdraws electrons from the 0 - H complex is formed, which on further hydrolysis yields
bond. As a result, the electron density in the 0 - H bond monocarboxylic acid.
decreases. It facilitates the release of H+ ions by making the Dry ether
0 -H bond weaker. Further, the chlorine atom because of its-/ CH 3- Mg- Br + CO 2
effect, stabilises the chloroacetate ion relative to acetate ion by 0
dispersing the negative charge. As a result of these two effects, II H 0+ /Br
chloroacetic acid is a stronger acid than acetic acid. CH 3- C- 0 - MgBr ~ CH3COOH + Mg,

0,c-<) G,~m,~<)
I. TI.
12. NaHC03 ~ Na+ + HC03
HC03is decomposed by acid releasing CO 2.
'OH

HC03 + H+ - H 20 + CO2
In case (I) + /-effect of - CH3 group intensifies the negative If acid is stronger than HC0 3then CO2 is released.
charge on the carboxylate anion and thus makes acetate ion less Phenol is less acidic and thus, does not liberate CO2 with
stable. While (II) strncture shows that - /-effect of the chlorine NaHC03.
atom disperse the negative charge on the carboxylate anion and
makes chloroacetate anion more stable. 13. Reactant is cyclic anhydride and changes to dicarboxylic acid on
hydrolysis.
Further, greater the number of electron-withdrawing substituents,
Also there is decarboxylation on heating if p -ketoacid.
greater would be the dispersal of the negative charge and hence,
Ozonolysis cleaves (C =0) bond and H 20 2 oxidises - CHO to
stronger will be the acid. In chloroacetic acid only one EWG is
- COOR group.
present, while in dichloroacetic acid two EWG are present and in
trichloroacetic acid, three EWG are present.
Therefore, trichloroacetic acid is the strongest acid and will
dissociate to the greatest extent.
8. KMn04 (alkaline) converts the alkyl chain attached directly to
cx>=} 0 0

(OH;O'

benzene nucleus into - COOK group. Hydrolysis converts 0 0

- COOK into - COOR group, i.e. we get a carboxylic acid. Anhydride

The carboxylic acid group when fused with hot sodalime

(NaOH + CaO), it gets converted into - H with the removal of O O l>, Dccarbo- c¢O
CO2 gas, (decarboxylation step).Thus, the complete series of OOHH --'-o
xyl~atio
- 2C02
~n - I ~
reaction can be represented as:

0 0 0

¢rCH3

Br
Br(i)KMn04'0H-

(ii) H20/J-I
¢rCOIOHB,
::::-.._

Br
O.OHN.O"

-CO,
t,.

(Decarboxyj;.tion)

2, 4-d ibromo

:¢r
benzoic acid
'A'

Thus, number of - COOR groups in P =2

0
Br
t, 3-dibromo benzene 14. CH 3 CH2 -
II
C- OH ~
NH3
CH 3 CH2COONHc=-+
t,.

9. 5-8% aqueous solution of acetic acid is called vinegar. (A) 0 (B)

1O. P icric acid is nitre compound instead of carboxylic compound. It II 8 2

CH3 - CH2 - C- NH2 ' ' KOH CH3 - CH2- NH2
is yellow coloured highly explosive compound. Hofmann
(C) bromamide (D)
reaction
OH
ONa OH

y
0 2NYYN02

N02
15. @+ CO, - K-o-lbe~4~~re-~ -cll-·on..... &COONa
Sodium salicylate
2, 4, 6-trinitrophenol
(picric ac,d)
 Aldehydes, Ketones and Carboxylic Acids I 665
0 0 treatment witha anhy. AlC1 3 brings about cyclisation to give
II II cyclic ketone (k), i.e. T-indanone
16. RMgBr + C=O - R- C- OMgBr CH2CH2COOH V CH2CH2COCl
Grignard O SOCl2 I
reagent II OH

rn1
V .&
W,HzO J R - C - OH + Mg/ 3-phenyl propanoic
carboxylic acid "- Br acid Anhy.AICl3
(Cyclisaiton/ ~
17. The dilute aqueous solution (7 to 8%) ofethanoic acid (acetic
acid) is called vinegar. 0
1-indanone
18. It is a !3-keto acid which undergoes decarboxylation in very mild (K)
condition, i.e. on simple heating. This occur through axis
21. (a) T is an ester so get hydrolysed in hot aqueous alkali.
member cyclic transition state as
o\_A ~

D
CH3

~-lo
V 2
)
~oHl
p J Tautomerisation )
cro
Cyclohexanone
H3C T
0 NaOH(aq)
hot

(b) LiAIH4 reduces ester to alcohol as

H O ~ C-
Soluble in aqueous NaOH
ONa

CH3
(i) Ordinary carboxylic acid requires soda-lime catalyst for
decarboxylation. T + LiAlH4 - HO~OH
(ii) Final step of decarboxylation in the above shown (Optically inactive)
mechanism involves tautomerism, therefore, for
decarboxylation of P-keto acid by above mechanism, the 'U' has no chiral carbon so is not optically inactive.
acid must contain an cx-H. (c) U on treatment with excess of acetic anhydride forms a
diester as
COOH

Thus, a◊ re,dHy ood~g°" d~a,bo,ylatioo

under mild conditions.

19. Since, the compounds J with molecular formula, C9 H8 0 2 gives
effervescence with NaHC0 3 and a positive test with Baeyer's (d) U on treatment with Cr03 I H+ undergoes oxidation to
reagent. Thus, J is an unsaturated carboxylic acid. As J is obtained diacid which gives effervescence with NaHC0 3•
by treatment of compound (I) with (CH 3CO)i O in the presence
ofCH 3CrOONa, therefore compounds (I) must be benzaldehyde. COOH
W ("'"''- NaHC03 CO j
which undergoes Perkin reaction with (CH 3COh in the U C O3 2
+ r - ~ COOR
presence of CH 3COONa to form cinnamic acid (J) which is an H3C V
a,p.. unsan1rated acid.
0
II ,, (J
6~
JQ4 HOOC (CH2)4COOH
Adipicacid
(YCH = CHCOOH
Thus, ~"'''°"° a,,ooo,, 23. Due to the presence of - CHO group, methanoic acid (HCOOH)
.,,,,._,,,,, (Perkin condensation)
V
Cinnamic acid
can reduce Tollen's reagent.
J(MFC9HsQv
HCOOH + Ag20 - CO2 + H 20 + 2Ag J.,
Silve mirror
20. Treatment of compound (J) with H 2, Pd/C reduces the double
bond to give corresponding saturated acid, i.e. But no - CHO group is present in ethanoic acid (CH 3COOH), so
3- phenylpropanoic acid. it cannot reduce Tollen's reagent.
24. Me 3 CC0 2Hor 2,2-dimethyl propanoic acid can be prepared as
C (CH3h
I
Cinnamic acid 3-phenyl propanoic
0 = C = 0 + (CH 3h - C - MgI - 0 = C- OMgI
acid (I mole) (lmole)
(J)
OH
This sanrrated 3- phenyl propanoic acid on treatment with SOCl 2 ~ (CH3hC- COOR + Mg /
gives the corresponding acid chloride which upon subsequent "-r
666 I Chapterwise & Topicwise Engineering Entrances Solved Papers

25. Formic acid is unique amongst simple carboxylic acid as it 33. Carboxylic acids when treated with either diborane or LAH, get
contains a hydrogen atom instead of an alkyl group. Thus, formic reduced to primary alcohols. Diborane is a better reagent than
acid may be regarded both as an aldehyde as well as a carboxylic LAH for such conversion, as it does not affect other functional
acid. Like aldehydes, it reduces Toll en's reagent. groups such as ester, nitro, halogens, etc.
Tollen's reagent (AgNO3 + NH4OH + NaOH solution) reacts R - COOH + B 2H6 ~ R - CH2OH
H 30
with - CHO group of which COOR reduced into the reagent 34. Oxidation of CH 3COOH is not possible.
silver mirror.
AgNO3 + NHpH - AgOH + NH 4NO 3 35. The acidity of halogenated acid increases almost proportionately
with the increase in electronegativity of the halogen present.
2Ag0H - Agp + H2O Therefore, the correct order is
HCOOH + Ag2O - CO2 + Hp + 2Ag FCH2COOH > CICH2COOH > BrCH2COOH > CH 3COOH
Silver mirror

26. When aliphatic carboxylic acids react with bromine in the

presence of red phosphoms, they give ex-halogenated acids. This
reaction is known as Hell-Volhard-Zelinsky reaction.
''(__j"
36.
., . ._ 1'-- CF3COOH
NaOH
~ C O OR
l_J
37. Acidic strength is the tendency to give H+ ions. Formic acid do
not contain any alkyl(+/ -effect exerting) group, therefore it is a
stronger acid than benzoic acid or acetic acid --COOR group of
27. Electron withdrawing group(- / effect) stabilizes the anion, and benzoic acid is attached to sp2 carbon of phenyl ring, thus it is
thus increases acidic nature. more acidic than acetic acid in w hich COOR group is attached to
Thus, (c) or (d) > (a), (b) acidic s/hybridised carbon atom. The correct order of acidic strength
Farther the electron withdrawing group from the --COOR of given acids is
group, its effect in increasing acid strength decreases thus (c) with CH 3COOH < C6H 5COOH < HCOOH
Cl at ex-position is stronger than (d) with Cl at y-position.
38. Acetic acid on reduction with lithium aluminium hydride
28. -NO 2 group at any position shows electron withdrawing effect, (LiAIH4 )gives ethyl alcohol while on reduction with HT and red P
thus acid strength is increased. But o-nitro benzoic acid believed gives ethane.
to have ortho effect. As a result, resonance gets prevented.
Hence, its acid strength is maximum, thus, the order of acid CH 3COOH Li~H4 CH3CH2OH
Ethyl alcohol
strength (IT) > (ITT) > (TV) > (I).
(The effect is more pronounced at para-position than meta.) CH COOR Red p + HJ
3 B

29. CH3COOH c121 :ed P CH2CICOOH Hence, reagent A and Bare respectively, LiAIH4 and Hl/red P.
39. Generally soda-lime removes CO2 from an acid but in case of
This reaction is called Hell-Volhard-Zelinsky reaction.
alkali formate it gives alkali carbonate and hydrogen.
CH2- COOR HCOONa + NaOH eao> Na 2CO3 + H 2
I
COOR 40. RCOOH + NaHCO3 ~ RCOONa + H 2O + CO2
Malonic acid
or RCOOH + HCO3 ~ RCOO- + H 2O + CO2
31. CH= CH + CH3MgBr- -C-H- ➔ CH = CMgBr
4 (A) Conjugate base, RCoo- is more stable. That is why equilibrium
shifts in the forward direction.

CH-C-C-OH
i (i) CO2
(ii) H30+
41. CH3CH2COOH--R-
~~\-➔ CH3 CHCOOH
(B)
(HVZ reaction) 6I
HO- CH= CH-COOH_T_a_
ut_
om_e_ri_sa_ti_on~
(C) Alcoholic WH CH2 = CHCOOH
( elunma.hon) Acrylic acid

CHO-CH2-COOH
Cone. H§04
(D) 42. RCOOH + N 3H
Hydrazoic Pri~ry
acid an:une
32. A liquid + C2H 5OH Cone. HiS0 4 Compound
(Fruity smell) It is Schmidt reaction.
Fruity smell is the characteristic property of ester, thus reaction 43. Group or atom attached with - COOR group showing negative
can be considered as follows inductive effect, makes the acid stronger or acid has larger
dissociation constant. - Br shows poor negative inductive effect
and also far away from - COOR, which makes
Acetic acid Ethyl acetate BrCH 2CH2COOH weakest acid and hence, it has smallest
( fruity srrell) dissociation constant
 Aldehydes, Ketones and Carboxylic Acids I 667
44. When an acid is heated with Br2 in presence ofP,a-H atom of the 55. Acetic acid reacts with PCl5 to form acetyl chloride.
acid is replaced by bromine atom. This reaction is called CH 3C00H + PCl 5 ~ CH 3C0CI + P0Cl 3 + HCI
Hell-Volhard Zelinsky reaction. NH2is a better nucleophile than Acetic acid Acetyl chloride

Br- replaces Br from a- bromo acid. 56. Oxalic acid is prepared by the acidic hydrolysis of cyanogen.
RCH C00H
2
Br2 I P _
HVZ reaction
R- CH- COOH y==N H20/ H+ COOR
I
I C=N COOR
Br oxalic acid
(X)

57. CH3C00H + PCl 5 ~ CH 3C0CI

Excess l R- CH - COOH (A)
I C0CH3
NH2

45. Formic acid HC00H a lso contain a - CHO group, so gives some
(Y)
__
c6_H_6
Anhy. AICl3
_➔ LgJ
~o (i) C2H 5MgBr
(11) Ether hydrolysis
reducing properties of aldehydes
I HI 0 I aldehyde group 58. CH3C00H + 4H LiAIH 4 CH3CH20H + HP
(A)
OH
Ho+
CH 3CH 20H + CH 3C00H ~ CH3C00C2H 5 + H 20
Formic acid is a very strong reducing agent. It reduces Tollen's (BJ
reagent, Fehling's solution and mercruric chloride. Acetic acid do
not give these reaction. 0 0
Thus, formic acid distinguishes from acetic acid by Fehling's Me'-s II II
59. Me/CH- C- 0-H < CH 3- C- 0-H
solution as formic acid gives red ppt. of cuprous oxide with
Fehling's solution while acetic acid does not. 0 0
~ C O OR ~COOR II F II
46. ~
8
;:~
2
lQJ + CO2 i < Me- 0 - CH2 - C- 0H < ~➔C-C-0- H

Phthalic acid COOR -/-effect increases acidity. + /-effect decreases acidity.

In the presence ofBa(0H)i when heated phthalic acid undergoes -CF3 exerting more-!- effect than Me0-
decarboxylation. MeiCH- exerting more +!-effect than - CH 3
60. P20 5 is dehydrating agent, hence acid gives anhydrides on
O COOR OO dehydration by Pp 5•
~
61. CH3CH2C00H ~ CH3CH2C0NH2
8 2
--CO2 ' + KOH
(o.,ll-keto acid) (Decarboxylation) Propionic acid A Propionamide
(X)
(A) (B)
CH3CH 2NH 2 HN0 2 CH3CH 20 H
48. R- X Alcoholic) R- CN Dil. HCI R- COOH Ethyl amine Ethyl alcohol
KCN Alkyl cyanide Carboxylic acid (J-) (2)

62. Propionic acid and KOH reacts to produce potassium propionate.

49. CH2 = CH-COOR
CH 3CH 2C00H ~ CH3CH2C00K+ Hp
LiAJH4 reduces - COOR group to - CHPH group without Propionic acid Potassiwn propionate
affecting C=C bond.
63. The monocarboxylic acids are called fatty acids, because some of
50. 2, 4-D or 2, 4-dichlorophenoxy acetic acid is used as a herbicide. the higher members were obtained from fats. The general formula
51. The strength of carboxylic acid depends upon the nature of the is RCOOH or C.H2n02-
electron withdrawing halogen atom. Greater the electron
-'
withdrawing influence of the halogen atom stronger will be the 64. Formic acid H - C = ~contains - COOR as - CHO
acid. T he electron withdrawing effect of the halogen decreases as group. (>.) I
F > Cl > Br> I. OH ,-
Hence, CH 2(I)· C00H is the weakest acid among these. 65. PCl 3, PCl 5 and S0Cl2 are used to replace - OH group of an
52. Citric acid is fotmd in lemon. T herefore, lemon gives sour taste. alcohol or an acid by - Cl group
53. Acids react with alcohols give ester, this process is known as 0 0
esterification. II II
RCOOH + R'OH~ RCOOR' R- C- OH + PCl 5 ~ R- C- CI + P0Cl 3 + HCI
Acid Alcohol
0 0
54. Formic acid also act as a reducing agent as it can reduce Toll en's
reagent, Fehling's solution, mercuric c hloride and KMn04 etc.
II II
R-C-OH + S0Cl 2~ R-C- CI + S02 + HCI
668 I Chapterwise & Topicwise Engineering Entrances Solved Papers
When acid reacts with CI2 in presence of red phosphorus, 71. Out of the given acids, strongest is HCOOH, thus it has
<X-chloro acid is obtained. (Hell-Vohlard-Zelinsky reaction). highest K 0 value. [Since, pK 0 = - logK0 ]
CI 72. By distillation of red ant, formic acid is obtained.
Red p I 73. Benzoic acid, o-phthalic acid and acetophenone inspite of having
CH 3CH 2COOH + Cl 2 ----;r--7 CH 3CHCOOH + HCI
a-chloropropionic acid double bonds, does not give unsaturation test (addition with
Br2 / CCI 4 ) as they are aromatic compounds and are quite stable
66. The He!1-Volhard-Zelinsky reaction is used for preparing a-halo
due to large resonance energy. Cinnamic acid, on the other hand
acid.
has a double bond outside the benzene ring (in the side chain)
CH 3- CH 2- COOH ~ ~~~ l CH 3- ? H-
1
COOH hence it gives unsaturation test.
CH=CHCOOH CHBr- CHBr- COOH
Cl

©
a-chloropropanoic acid

67. Carboxylic acids react with Grignard's reagent to give alkanes.

~o
lgJ CCl4
+ Br --'---+
CH 3COOH + CH3MgX - CH 3COOMgX + CH4 Cinnamic acid Dibromo cinnamic acid
Methane

68. Lithium aluminium hydride is a powerful reducing agent. It 74. Acetic acid is obtained by the oxidation of ethanol with alkaline
reduces acetic acid into ethanol. KMn04.

CH 3COOH L~:4 CH 3CH 0 H 2 C2HsOH + [OJ AlkalineKMn0 4 CH3COOH

Ethanol Acetic acid

69. Proton donors are acids. Electrons withdrawing groups increase
acidity. More the number of electrons w ithdrawing groups more
w ill be acidity. Closer the electrons w ithdrawing group to proton
more will be acidity.
:.Cl 2 CHCOOH, has highest acidity among
CH3COOH , CICH2COOH, Cl 2CHCOOH , Cl 2CHCH2COOH
70. 4-methyl benzene sulphonic acid is stronger than acetic acid thus,
it will re lease acetic acid from sodium acetate.
Topic 4 Derivatives of Carboxylic
Acids
1. This problem can be solved by using the stability of radical obtained
after fragmentation of peroxyester. Allylic radical are more stable
than alkyl radical, so when there is a possiblility of formation of allyI
radical, it will undergo fragmentation through formation of ally!
radical. i.e. fragmentation produces stable radical.

On the basis of stability of radical, fragmentation can be done as

Column I Column II E:-.1>lanation

P.

Q.

o·
R. C6 H 5 - C02 + CH3- d- CH 3 - co2 Ph + CH3- CO- Ph + CH3
I
C6Hs
C6 H 5 - CO2+ CH3 0
s.
L c6H; +co2
P ➔ I, Q ➔ 3, R ➔ 4, S ➔ 2, Thus, (a) is the correct choice. 3. Acid strength in active methylene compounds can be decided by
0 0 two factors
II II (i) Presence of electron withdrawing group
2. CH 3- C- CH2 - C- OC2H 5 ~ (ii) Stability of enolate anion obtained after removal of H+.
(Keto)
Higher the electron withdrawing ability of substituents attached
OH 0 to electron w ithdrawing groups higher wi ll be acidic strength of
I II methylene group.
CH3- C= CH- C- OC2H 5
(Enol)
 Aldehydes, Ketones and Carboxylic Acids I 669
0 0
II II
Electron withdrawing ability of CH 3CO- is greater than CH3CHzO- C- Thus, CH3- C- increases acetic strength of active methylene
0
II
compound to greater extent than CH 3CH 2O- C- .
0 0
II II
Number of CH3 - C- group Number of - C- OCH2CH 3 group

0 0
II II
I. CH 3- C- CH2 - C- O- C2H 5 2 0

0 0
II II
IT. CH3- C- CH 2 - C- CH3
0 0
II II
CH3CHzO- C- CH 2- C- OC2H 5 0 2

On the other hand stability of enolate anion obtained after the 5. German chemist Friedrich Wohler in 1828, synthesised the
removal of W can be explained as keto group stabilises enolate organic compound 'urea' for the first time in laboratory.
anion to more extent than ester. Ketone group stabilises enolate Due to this experiment, vital force theory of organic compounds
anion by resonance through one side only while ester stabilises by was rejected.
both side ofketo group which can be shown as
0 0 o- NH3 + HCNO ~ ~4CNO NH4 CNO ~ N1if?.f
Ammonia Hydrogen mmomum
PMI, 3
Organic compounds
11 II I 1 4 4 .fY~fS 4 4 4 3 cyanate
/C - CH3 e /C - CH3_ ,,f'C - CH3 Inorganic compounds
CH2"- ~ CH"-,_ =CH2"-
C- CH3 C- CH3 C- CH3 6. Esters are sued for making perfumes.
II II II
~ COOH
0 0 0
0 (i) NaOH/t.
7. ~ C O O C 2Hs (ii) H o+ >
CH3- O- t - CH2- t - CH3 less tautomerism will be seen 3 (A)
0 0 t. (decarboxylation)
due to lesser availability of C 1 atom for tautomerism (as at this ---COz
C-atom > C=O bond is in conjugation with the lone pair of NaOH H3C"-,_
electron of neighbouring oxygen attached). ketal condensation /C - CH - C- CH3
Further, in CH3-O-C-CH 2 -C-CH3 as both the C-atoms
H5C2 I I II
OH CH3 0
II II
0 0 8. Methyl salicy late is also known as oil of winter green. It is an
of > C=O bond have similar stations hence, tautomerism organic ester.
decreases further. That's why correct order of acidity can be
~COOCH3
arranged as IT > I > IIT and correct choice is (c).
~CH
Methyl salicylate
(oil of w inter green)

r9 o-
Benzoic
acid
Ammonium
benzoate
Benzamide Aniline
9. CH3 -
'-11
C- Cl~CH3 -
I
C- Cl ~
~Ho-
Et)

~ CH3
~ ~ CH
- ytjl ~ OC2Hs + c1-
3- C-
Aniline Sulphamic
acid
◊C2Hs
S03H
This is by ~ reaction. Cl- is a better leaving group than
Sulphanilic
acid C 2Hs0- and ethyl ethanoate is fonned.
670 I Chapterwise & Topicwise Engineering Entrances Solved Papers

10. CH3CONH2 CH3CN

Acetamide Ethane mitrile

Acctylchloride Sodium. acetate Acetic anhydride

r
12. H3C - o - N H2

~o

l
~Cl OH

CoH5 -C-CH 3
I
CoHs-C=CH2

H,c-0-NH-Lo CH3
I I
CH3
(B)

13.
Ethyl benzoate m--chloro ethyl benzoate

14. CH3COONH4 ~ CH3CONH2 P 2~s

20. Baeyer-Villiger oxidation involves transformation of a ketone
Acetamide (- H 2o)
into ester by reaction with a peracid. The net change is the
insertion of an oxygen atom between the carbonyl carbon and an
adjacent carbon of the ketone. So, it is an example of
CH3CN
Methyl cyanide Acetic acid Baeyer-Villiger oxidation, the most suitable reagent is
(l') (2) m-chloroperbenzoic acid.

lJ~
15. 2KCNO + (NH4 ) 2 SO4 - 2NH4 CNO + K 2SO4
NH4CNO ~ NH2CONH2 /'-... m-chloroperbenzoic
Urea 'CH3 _ _
acid-

16. In the presence of dil. HCI, acetamide is hydrolysed by boiling,

the product obtained is acetic acid (CH3COOH).
21. Only ethyl acetate tmdergoes reduction with LiAJH4 to give only
CH3CONH2 + HzO + HCI - CH 3COOH + NH4 CI
ethyl alcohol, other esters given in option on reduction gives a
17. Ethyl acetate is obtained when metJ1yl magnesium bromide reacts
mixture of alcohols.
with ethyl chloroformate.
O OMgBr 1 r CH3 COOCH2 CH3 + 2H2
LiAIH4
~ 2CH3CH2 OH

CH3MgBr + Cl - ~ - O- C2H5 - [c1- i - 0 - C2H 5 j 22. Due to strong negative inductive effect shown by - Cl and
- OCOCH3 group, acid chloride and acid anhydride are highly
0 CH 3 reactive among acid derivatives. They react independently with
CH3 - ~- 0 - C 2H5 + MgBrCI j, water even in the absence of catalyst to give carboxylic acid.
Ethyl acetate 0 0
18. Amides react with bromine and caustic soda to give their II
CH3-C-Cl NaHC03(aq)
II
corresponding primary amines. Thus, acetamide gives CH 3 - C -ONa + CO2 + HCl
methanamine. This reaction is known as Hofmann's bromamide 0
degradation reaction.
NaHC03(aq)
II
0 2CH3 - C- ONa + CO 2
II 343K
H 3 C- C- NH2 + Br2 + 4KOH- 23. cis-dioic acid readily gives anhydride on heating. Since, maleic
Acetamide acid is a dioic acid it gives maleic anhydride readily.
2KBr + K2CO3 + H 3C- NH2 + 2Hz0
Methanamine H "'-. /COOR
C HC-CO~
II II ,.,..o
C Hc-co,.,..
H/ ""'COOR Maleic anhydride
Maleic acid

24. Hydroxamic acid test is used to detect presence of esters.
In hydroxamic acid test a few crystals or a few drops of the
substance is dissolved in l mL of 95% ethanol + I mL of l M
HCI. Then, a drop of 5% FeC13 is added.
Formation of characteristic colour shows the presence of acyl or
ester group.
0 0
II II
Aldehydes, Ketones and Carboxylic Acids I 671
/°\
Hence, CH3 - CH- CH - CH3 is the anhydride of 2, 3-butane
diol.
30. When amide is heated with a mixture of Br2 in the presence of
NaOH or KOH amine is formed which has one carbon atom less
than original amide. This is called Hofmann's degradation

l
reaction.
R - C- OR + H2NOH- R- C- NHOH
Hexanamide + Br2 + 4KOH- Pentanamine
+ K2C03 + 2KBr + 2H20
-➔
FeCl3 [ II
R- C- NOH Fe 0
II
CH2 - C
31. I O + RMgX -
25. In this reaction, acid amide group reacts with Br2 in presence of
CH2- rr
NaOH or KOH to give primary amine group. The amine is one
carbon less than the parent amide. So, the reaction is known as 0
Succinic anhydride
Hofmann degradation reaction.
t,.
RCONH2 + Br2 + 4KOH - RNH2+ 2KBr + K2C03 + 2H20

26. 0 - - --
(ii) Mg(OH)X

0
II
R- C- CH2-CH2 - COOH
32. RCOCl + NH3- R- CONH2
Acid chloride Amide

Ring I is more active, electrophilic shbstitution takes place over 33. Amides are reduced by lithimn aluminium hydride (LiAJH4 ) or
ring I. - NH- C- Ph is ortho para directing. para product is sodium and ethyl alcohol into primary amines.
II 0
0
predominating. II LiAIH4
CH3CH2 - C- NH 2 + 4[H]-----'4 CH3CH2 CH2NH 2 + H 20
27. trans esterification is the process of conversion of one ester to Propanamide Propyl amine

another ester. 34. Aqueous NaCl is neutral hence there is no reaction between ethyl
0 acetate and aqueous NaCl.
II fr, R' ONa 0 0
R-C-OR' + R" - OH
Ester Reflux II II
0 35. CH3 - C- Br + CH3MgI-CH 3- C- CH3
II 0
R- C- OR"+R'OH II
fr, C2H50Na
CH3COOC4H9 + C2H 50H CH3- C- CH3 + CH3MgI-
Reflux
n-butyl acetate
CH3COOC2H5 + C4H9 0H CH3
Ethyl acetate I
CH - C- OMgI aq. NH4 Cl
28. Urea on slow heating gives biuret. 3 I
CH3
H 2N · CONH · H + H 2N CONH2 ~➔ 2-rrethyl -2-propanol

H2NCONH · CONH2 + NH3 36. c1- is the best leaving group being the weakest nucleophile out of
Biuret Ammorna
0
II
OH OH NH2, Cl-, o- - C2H 5 and o- - C- CH3.
I I
29. CH3 - CH- CH- CH3 37. CH 3CONH2 on treatment with metallic sodium produce
2, 3-butane diol
hydrogen.
/0\ CH3CONH2 + Na- CH3CONH- Na++ -I H2 i
2
CH3-CH-CH-CH3 + H20
672 I Chapterwise & Topicwise Engineering Entrances Solved Papers
38. The silver salt of fatty acid on refluxing with an alkyl halide, give an
ester.
?-Na+
RCOOAg + R' Cl_!➔ RCOOR' + AgCl
~ CH3 - ?- CH3
ester CH 3
39. The reaction occurs as follows
C6H 5 COOC2H 5 + KOH ~ ¼ H 5COOK + C2Hs0H 44. The reaction occurs as follows
Ethyl benzoate
0
½ H 5 COOK + HCl------t C6H 5COOH + KCl II PhMgBr
White solid CH3 - C- OCH 3
40. Benzamide undergoes Hofmann-bromamide reaction with Br2 /KOH :OMgBr
to give aniline. This aniline give paracetamol (antipyretic drug) with I - Mg(Br)OCH 3
CH3- C -OCH3
acetic an hydride. I
CONI-!i NH2 Ph

0
Benz.amide
+ 4KOH + B,, -> 0
Aniline
+K,co, + 2KB,+ 2H,O CH3-C -
OH

Ph
I
I
Ph -
H+
cH3 -C-Ph
OMgBr
I
I
Ph
NH2 NH2 I, 1-dephcnyl ethanol
1 Ph MgBr

"''6..: (CH3CO),O -> ( ) + CH3COOH

45. PCl 5 is a chlorinating agent. Tt adds to ethyl benzoate to give
ethyl chloride and benzoyl chloride.
PCls
C6H 5COOC2H 5 ~ ½ H 5COCI + C2H 5CI + POC13
):CH3
Paracetamol
46. Urea is one of the most important fertilizer as it does not
change pH of soil. Urea, after hydrolysis gives ammonia and
41. When, benzene is heated with acetyl chloride, in presence of CO2 . Ammonia is taken up by plants leaving behind
anhydrous A1Cl3, electrophilic substitution takes place and CO2 · CO 2 is a very weak acidic oxide.
acetophenone is obtained. The reaction is known as Friedel-Craft's Tt doesn't affect pH of soil
acylation.
2
NH2CONH2 H 0 2NH3 + CO2
Urea
47. The order of reactivity of acid derivatives is as
Methy l phenyl ketone
RCOCI > (RC0)2 0 > RCOOR' > RCONH2
(acetophenone) Hence, acetyl chloride is the most reactive among these.
48. Carboxylic acid is converted into its anhydride by using
42. Amides on acidic hydrolysis give acid and an amine.
phosphoms pentaoxide.
Hence, N-dimethylacetamide will give acetic acid and dimethyl
amine on hydrolysis. 2RCOOH P2 0s
Carboxylic acid
Acid anhydride

49. The acid amides are amphoteric in nature. Tn amides, the lone
pair of electrons on N atom remains delocalised (in
resonance) with (C =0) group.
:. Amides are not much basic but infact they are amphoteric
in nature.
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27
Nitrogen Containing
Compounds
QUICK REVIEW
Amines
• Amines are the derivatives of ammonia, obtained by Physical Properties of Amines
replacement of one, two or three hydrogen atoms by alkyl/ Amines are polar and hence form intermolecular H-bonds
aryl groups. and therefore they have higher boiling points. The order of
• Amines are classified as primary (1 °), secondary (2°) and boiling points of amines are I O amine > 2° amine > 3°
tertiary (3°) depending upon the number ofH atoms in NH 3 amine.
molecule which get replaced by alkyl (R) or aryl (Ar) groups. Basic Character of Amines
R
NH ~ R - NH ~ "-NH • Order of basic strength of different amines.
3 +R 2 +R , / (i) (CH 3 lJN< CH3 NH 2 < (CH 3 )zNH
Ammonia Primary R
Secondary (in aqueous solution)
R' (ii) C 2 H 5 NH 2 < (C2 H 5 )J N < (C2 H 5 )zNH
~R-N/
+R "-R" (in aqueous solution)
Tertiary (iii) CH 3 CH 2 CH 2 NH 2 < (CH 3 CH 2 CH 2 hN <
(CH 3 CH 2 CH2 )z NH (in aqueous solution)
Preparation of Amines
• Gabriel's phthalimide synthesis produces primary
aliphatic amines. It is not used for production of secondary
or tertiary amines. Aromatic primary amines can also not
be prepared by this method.
(fr)~<~<$<~< Br Cl
• In Hofmann bromamide reaction prin1ary amide on heating
with aq. KOH and Br2 gives primary amine with one
carbon atom less. This reaction is therefore, regarded as
degradation reaction.
• Carboxylic acid on warming with HN 3 (hydrazoic acid) in
the presence of cone. H 2 SO4 gives primary amine. The
yield of amine is quite high.
674 I Chapterwise & Topicwise Engineering Entrances Solved Papers
(v) Cyanides and lsocyanides
Note ortho substituted anilines are normally weak bases than
aniline whether the substin1ent is electron releasing or
electron withdrawing in narure ( ortho effect). Nitro Compounds
Note Cyclohexylamine is more basic than aniline because
electron pair on nitrogen in cyclohexylamine can be easily
donated.
• As the s-character of the hybrid orbital containing lone pair
of electron increases, the basic character decreases.
RNH2 > RN=CHR > 0 RCN
25% s-character 33.3% s-character 50¾ s-character
• Amines undergo alkylation and acylation. Benzoylation of
amines in presence of NaOH is known as
Schotten-Baumann reaction.
• Nitration of aniline is carried indirectly, i.e. first
acetylating with acetic anhydride to fom1 acetanilide and
then it is nitrated to produce nitro derivatives. Nitro
derivatives are hydrolysed to obtain desired product.
Diazonium Compounds
Hinsberg's Test
• Primary, secondary and tertiary amines can be
distinguished by Hinsberg's test or Hofmann test. In
Hinsberg's test benzene sulphonyl chloride (C 6 H5 SO2 Cl)
is used while in Hofmann test CS 2 and HgC1 2 are used.
• Carbylamine test In carbylamine reaction, only primary
amines on heating with ethanolic KOH form isocyanides or
carbylarnines which have foul smell. This reaction is used
to test I O amines.
• Nitrous acid test On reacting with nitrous acid, primary
amines gives diazonium salts.
(i) Secondary amines reacts with HNO 2 to form a
yellow green only layer ofN-nitrosoamines.
(ii) Tertiary amines readily dissolve in HNO3 forming
crystalline trialkyl ammonium nitrate.
• Azo dye test is used to distinguish aliphatic primary amines
from aromatic primary amines.
• Alkyl halides with KCN (alcoholic) gives alkyl cyanides as
the main product and with AgCN (alcoholic) gives alkyl
isocyanide as the main product. Aryl cyanides can be
prepared from arene diazonium salts by Sandmeyer's
reaction.
• Reduction of cyanides to corresponding amines by
sodium-alcohol is known as Mendius reaction.
• The nitro group in nitrobenzene is a deactivating group and
deactivates both the ortho and para positions in the ring
due to conjugation. As a result of this meta position
becomes comparatively of high electron density and hence
electrophilic substitution occurs at meta position.
• Nitrobenzene does not respond to Friedel-Craft's reaction
because the ring has been highly deactivated and both R +
and RCO+ ions are not in a position to attack the ring.
• Primary, secondary and tertiary nitroalkanes react in
different manner with nitrous acid. This is known as Victor
Meyer's test for distinction between 1°, 2° and 3°
nit.rRalkanes. lk HNO
~lJ P rutroa ane + 2 ~ Nitrolic acid
NaOH or
KOH
Red colour
(ii) 2° nitroalkane + HNO 2 ~ Pseudonitrole
(Blue colour)
(iiz) 3° nitroalkane + HNO 2 ~ No reaction.
• Diazotisation Diazonium salts have the general formula,
+ -
ArN2X, where, x- may be Cl- ,Br- ,HSO4,NO3,
+ +
etc. The N 2 (-N =
N) is called diazo group diazonium
salts are prepared by the conversion of a primary aromatic
amines into their diazonium salts (diazotisation).
• Coupling reaction Coupling reaction between
diazonium salt and activated compound such as amine,
dialkyl aniline or alkyl aniline in a weakly acidic medium
and a phenol in a weakly alkaline medium takes place at
para position to amino or phenolic group. Ifpara position
is occupied, coupling takes place in the ortho position. If
both ortho and para positions are occupied, coupling
either does not occur or a substituent like
-COOH, -SO3 H present in the p-position is replaced by
azo group (-N = N-) .
 Topi c 1
Preparation and Properties of Nitro Compounds
2012 6. The structure of the compound fom1ed, when nitrobenzene
1. Identify C in the following reaction, [BITSAT] is reduced by lithium aluminium hydride (LiA1H 4 ) is

@-y- y-@
6 '""'"
NO2 (a) [BITSAT, EAMCET, AMU]

A N,NO, B N,NH, C. H H

(a) Benzamide
( c) Chlorobenzene
(b) Benzoic acid
(d) Aniline
2. Which of the following compounds reacts slower than
(b)© NHOH

benzene in electrophiJic substitution? [AMU]

CH3 NH2
N-@
(a() (b)6 (c)@-N

NO2 OH

(c)6 (d)6 7. Secondary nitro alkanes can be converted into ketones by

using Y. Identify Y from the following. [VITEEE]
2010
R'-.. R'-..
3. Reduction of nitrobenzene in the presence of Zn / NH4 Cl R / CHNO2+ Y ~ R/C = 0
gives [Manipal]
(a) Aqueous HCl (b) Aqueous NaOH
(a) azobenzene
(c)KMnO 4 (d)CO
(b) hydrazobenzene
(c) N-phenyl hydroxylamine ~ HNO,. A
8• lS,J Br2 B
(d) aniline ~ FeBr3 )

2008 The compound B is [OJEE]

4. Toluene is nitrated and the resulting product is reduced NO2

with tin and hydrochloric acid. The product so obtained is
diazotised and then heated with cuprous bromide. The (a) ~ -
(b)
reaction mixture so formed contains. [AIEEE] ~Br
(a) mixture of o and p-bromotoluenes
(b) mixture of o and p -dibromobenzenes NO2
(c) mixture of o and p-bromoanilines
(d) mixture of o and m-bromotoluenes (d) ~-
5. Nitrobenzene is reduced by Zn and alcoholic potash Br~Br
mixture to get [BIT SAT]
(a) C 6 H 5 -NH2
(b) C 6 H 5 -NH-NH-C6 H 5 9. Nitration ofnitrobenzene at 125°C with mixed acids gives
(c) C 6 H 5 -N-N - C6 H 5 (a) meta-dinitrobenzene [J&K CET]
(d) C 6 H 5 -NH-CO- C6 H 5 (b) ortho-dinitrobenzene
( c) para-dinitrobenzene
(d) 1, 3, 5-trinitrobenzene
676 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2006
(a) SiC
10. C 6 H 5 NO 2 Sn/ HCI ➔ C6 H 5 X, 'X' is identified as CWBJEE ]
(c) KMnO4
(a) NO (b)-NH 2
(c) NHOH (d) None of the above 2005
11. Which of the following reactions can produce aniline as 13. Which of the following is not a nitro derivative?
main product? [EAMCET] (a) C6 H 5 NO2 [Manipall
(a) C 6 H 5 NO2 + Zn / KOH (b) CH3CH 2ONO
(b) C 6 H 5 NO2 + Zn / NH4 Cl 0
(c) C 6 H 5 NO 2 + LiAJH 4
(d) C 6 H 5 NO2 + Zn I HCl
(c) CH 3 TH-N:(
12. In the reaction, CH3 0
NO2 NH2 (d) C 6 H 5 (OH)NO 2
14. Which of the following compounds is soluble in benzene
1YNO~~-
LSJ LS(N02
but almost insoluble in water?
(a) C2H 5 OH (b) CH3CO2H
[EAMCET]

(c) CH3CHO (d) C 6 H 5NO2

Xis [Jamia Millia l slamia ]

Topic 2
Preparation and Properties of Cyanides and lsocyanides
2014
1. How many sigma and pi-bonds are there in the molecule of
dicyanoethene (CN-CH= CH--CN)? [VITEEE] (a) acetic acid, methanol
(a) 3 sigma and 3 pi (b) 5 sigma and 2 pi (b) acetone, methane
(c) 7 sigma and 5 pi (d) 2 sigma and 3 pi (c) ethanoic acid, eth ane
(d) ethanoic acid, methane
2. The IUPAC name of the following compound is [AMU]
5. Which compound is known as alkyl carbylamine?
CH2--c:H--c:H2 (a) R · CN (b) R · NC [Guj CET]
I I I (c) Ar· CN (d) Ar · NC
CN CN CN
(a) 1, 2, 3-tricyanopropane 2006
(b) propane- I , 2, 3-trinitrile 6. Alkyl cyanides undergo Stephen reduction to produce
(c) 3-cyanopentane- I, 5-dinitrile (a) aldehyde [VITEEE]
(d) 1, 3, 5-pentanetrinitrile (b) secondary amine
(c) primary amine
2010 (d) amide
3. Final product of hydrolysed alkyl cyanide is [MP PET] 7. Benzamide can be converted into benzonitrile with
(a) RCOOH (b) RCONH 2 (a) H3O+ (b) OH-/ H2O [J & K CET]
$
(c)R-C= NH (d)R-C= NH (c) KCN (d) P2O 5
I 8. The compound with foul odour among the following is
OH [J & K CET]
2009
4. Identify A and Bin the reaction given below. ~NC ~CN
(a)~ (b)~
Hydrolysis A Decarboxylation
Ethane nitrile B
aq. H2S04 Sodalime
+ 2Hp I!,
~NH2
- CO2
-NH
3 [Guj CET] (c)~
 Nitrogen Containing Compounds 1677

2007
9. Which is not the property of ethanenitrile (CH 3 CN)? ➔
(a) CH 3 CH2 NH2 (b) CH3 CH 2 N=C
[BITSAT]
(c) CH 3 C = N (d) CH3 CH2 ·OH
(a) Undergoes acidic hydrolysis to give carboxylic acid
(b) Undergoes alkaline hydrolysis to give salt of 16. Acetonitriles on hydrolysis produce which of the
carboxylic acid following? [WB JEE]
(c) It tautometises to give methyl isocyanide (a) Amine (b) Acid
(d) It gives carbylamine reaction with chloroform (c) Amides (d) Carbonyl compounds
1O. Ethyl isocyanide on hydrolysis in acidic medium generates
(a) ethylamine salt and methanoic acid [MP PETI 17. In the reaction, R-C= N + 4 (H)~ RCH 2 NH 2
(b) propanoic acid and ammonium salt X can be [Jamia Millia Islamia, UPSEE]
(c) ethanoic acid and ammonium salt (a) LiA1H4 (c) Ni (d) 2KBr
(d) methylamine salt and ethanoic acid
18. Methyl cyanide gives on hydrolysis [Guj CET]
11. Aliphatic nitrites are prepared by the treatment of alkyl
(a) methyl amine (b) acetic acid
halides with [J&K CETI (c) formic acid (d) ethyl amine
(a) sodium cyanide 19. The molecular fo1mula ofbenzonitrile is [J&K CET]
(b) sodium isocyanide
(c) sodium isocyanate (a) C 6 H 5 CN (b) C 6 H 5 NC
(d) cyanamide (c) C 6 H 5 CNO (d) C 6 H 5 NCO
12. Reduction of alkyl nitriles, produces [J&K CETI 2005
(a) secondary amine (b) primary amine 20. The reduction of which of the following compound would
(c) tertiary amine (d) amide yield secondary amine? [Manipal]
13. Which one of the following does not have sp 2 hybridised (a) Alkyl nittile
carbon? [UPSEE, Jamia Millia l slamia ] (b) Carbylamine
(a) Acetone (b) Acetic acid (c) Ptimary amine
(c) Acetonitrile (d) Acetamide (d) Secondary nitro compound
21. Acetonitrile on reduction gives [MIIT CETJ
2006 (a) propanamine (b) methanamine
14. In the reaction, (c) ethanamine (d) None of these
HCI X Boiling H20 Y. 22. Which one does not liberate NH 3 when undergoes
CH 3 CN + 2H ~
hydrolysis? [OJEE]
Thetem1 Y is [BITSAT] (a) Acetani1ide (b) Acetonittile
(a) acetone (b) ethanamine (c) Acetamide (d) Phenyl isocyanide
(c) acetaldehyde (d) dimethyl amine 23. KCN reacts readily to give a cyanide with [J&K CETJ
15. An organic compoundA having molecular formula C 2 H 3 N (a) ethyl alcohol (b) ethyl bromide
on reduction gave another compound B, upon treatment (c) bromobenzene (d) chlorobenzene
with nitrous acid B gave ethyl alcohol.
24. In alkyl cyanide alkyl group attached with [BCECEJ
On wa1ming with chlorofom1 and alcoholic KOH, it
formed an offensive smelling compound C. The compound (a) C ofCN group
C is [MHT CETI (b) N of CN group
(c) Either C or N of CN group
(d) Both C and N of CN group
 Topic 3
Preparation of Properties of Amino Compounds
2014
1. In the reaction shown below, the major product(s) formed
is/are [JEE Advanced]
para-fonn
CH2NH2

(\NH, 0
Acetic
anhydride
CH2CI2 l
p d ( )
ro uct s
The true statement about the product is
(a) it does not exist as Zwitter ion
(b) it does not act as inner salt
[BITSAT]

(c) -SO 3 diminishes the basic character of -NH2

(d) -NH 2 displays a powerful basic character
H 5. NH2
tnCH3 h
~
A"20 A Br2
CH3COOH
B H2~
H
C
0
(a) NH2 + CH3COOH CH3
0 The final product C in the above reaction is [VITEEE]
NH
NHCOCH3

(b)
H
NnCH3 + CH3COOH
(•)o/8,
0 0 CH3

(c)o/B
, COCH3

CH3

@ e 6. Which of the following processes does not yield a primary

NH3CH2COO amine? [Manipal]
N.
(d) H (a) CH3COCH 3 + NH 3 + H2 ~
~CH3 N-
(b) CH 3CH 2CN + H2 140
~

0 0
(c) CH CHO + H NOH Na,~HsOH
3 2
2. Considering the basic strength of amines in aqueous
4
solution, which one has the smallest pK b value? (d)CH 3CHO + N2CH2 NaBH

(a) (CH 3 h NH (b) CH 3NH 2 [JEE Mains] 7. An aromatic compound A (C 7 H 9 N) on reacting with
(c)(CH3hN (d)C6 H 5 NH 2 NaNO 2 / HCl at 0°C forms benzyl alcohol and nitrogen
3. Arrange the following in correct order ofbasicity. gas. T he number of isomers possible for the compound
A is

000
CKCET]
(a) 5 (b) 7
(c) 3 (d) 6
I I 8. An amine C 3H 9 N reacts with benzene sulphonyl chloride
H H
to form a white precipitate which is insoluble in aq. NaOH.
II m [BITSAT] The amine is [WB JEE]
(a) I > II > III (b) IIl > II > I
(c) II > I > III (d) I > III > II
 Nitrogen Containing Compounds I 679
Me\_ /Me Me\_A 18. Aniline + Excess ofBr2 ~ ? Co.JEE]
(a) N (b) N Me (a) Tribromo benzene
I H (b) m -bromo aniline
(c) 3, 4, 5-tribromo aniline
Me Me
(c) Me/\_/NH2 (d)
Me
A NH2 2011
(d) 2, 4, 6-tribromo aniline

9. The correct order of basic strength in aqueous solution is 19. The major product of the following reaction is [IITJEE]
(a)(CH 3 )iNH>CH3 NH 2 >(CH 3 ) 3 N [AMUl ~o
(b) (CH 3 hN>(CH 3 ) 2 NH>CH 3 NH 2 ~c"- (i)KOH
(c)CH 3 NH 2 >(CH 3 h N>(CH 3 h NH ~/NH
(d) (CH 3 h N>CH 3 NH 2 >(CH 3 h NH c~
0
10. Amongst the following, the most basic compound is
(a) benzylamine (b) aniline [AMU]
(c) acetanilide (d) p-nitroaniline
11. What is Zin the following reaction sequence?
(i) NaN02 + HCl/ 273 K
(ii) H 3P02 + H20
(iii) CO, HCI anhy. AICl3/CuCI
C6HsNH2 Z. [EAMCET]
(a) C 6H 5 C0 2 H (b) C 6H 5 0H
(c) C 6H 5 CHO (d) C 6 H 6
12. What is IUPAC name of iso-propylamine? [J&K CET]
(a) Propan-2-amine (b) Ethanamine
(c) 2-aminotoluene (d) Propan-1-amine

2013
13. Aromatic primary amines can be distinguished from
aliphatic primary amines by [Manipall
(a) Tollen's test
(b) action on red litmus paper
(c) azo dye test
(d) action with dil. HCI
14. N-methyl aniline on reaction with nitrous acid gives
(a) N-nitroso-N-methylaniline [Manipal]
(b) p-nitroso-N-methylaniline 20. Amongst the compounds given, the one that would form a
(c) p-nitro-N-methylaniline brilliant coloured dye on treatment with NaN0 2 in dil.
(d) N-nitro-N-methylaniline HCI followed by addition to an alkaline solution of
15. Unpleasant smell of carbylamine is obtained when ~-naphthol is [IIT JEE]
chloroform and alcoholic KOH are heated with [KCET]
(a) any aliphatic amine
(c) any primary amine
(b) any amine
(d) any aromatic amine
(a)v
r0TN(CH3)i
(b) V
r0r'NCH3

16. The main product of the reaction ofCH 3 CONH2 with Br2
in aqueous potassium hydroxide medium is [OJEE]
(a) CH3-CH 2 -NH 2 (b) CH3Br
(c) CH3CONHBr (d) CH3NH2
21. n-butylamine (I), diethylamine (II) and N, N-din1ethylethy-
2012 lamine (ITI) have the same molar mass.
17. When aniline reacts o il of bitter almonds, condensation The increasing order of their boiling point is
takes place and benzyl derivatives are formed. These are [Kerala CEE]
known as [Manipall (a) III < II < I (b) I < II < III
(a) Millon's base (b) Scruff's reagent (c) II < III < I (d) II < I < III
(c) Benedict reagent (d) Scruff's base (e) III < I < II
680 I Chapterwise & Topicwise Engineering Entrances Solved Papers
22. Choose the inco1Tect statement. [Ke rala CEE] 30. Consider the following reaction,
(a) Primary amines show intermolecular hydrogen bonds CH Sn/HCI X--Co=-H..:.p;c
__ l _..,. y + HCl
6 5 No 2---➔
(b) tert-butylamine is a primary amine
(c) Tertiary amines do not show intermolecular hydrogen What is Y? CRPET]
bonds (a) Acetanilide (b) Benzanilide
(d) Iso-propylamine is a secondary amine (c) Azobenzene (d) Hydrazobenzene
(e) Amines have lower boiling points as compared to 31. Which of the following is most basic in nature? [RPET]
those of alcohols of comparable molecular mass
(a) NH3 (b) CH3 NH 2
23. Compare boiling point of isomeric alkyl amines. (c) (CH 3 ) 2 NH (d) C 6 H 5 N(CH 3 )z
(a)l 0 > 2° > 3° (b)l 0 > 2° < 3° [GujCET]
(c)l 0 < 2° < 3° (d)l 0 < 2° > 3°
2009
32. Given the following sequence of reactions,
2010
24. Which one of the following compounds will dissolve in an
alkali solution after it has undergo reaction with Hinsberg's
reagent? [Manipal] The major product C is [BITSAT]
(a) CH3 NH2 (b) (CH 3 h N (a) CH3 CH2NH2 (b) CH3 -CH 2 C-NHBr
(c) (C2 H 5 )iNH (d) C 6 H 5 NHC 6 H 5 II
25. The correct sequence of reactions to convertp-nitrophenol 0
into quinol involves [KCET] (c) CH 3 · CH 2 -COONH4 (d) CH3 · CH 2 C-NBr2
(a) reduction, diazotisation and hydrolysis II
(b) hydrolysis, diazotisation and reduction 0
(c) hydrolysis, reduction and diazotisation 33. Amino group is ortho,para-directing for aromatic
(d) diazotisation, reduction and hydrolysis electrophilic substitution. On nitration of aniline, a good
amount of m-nitroaniline is obtained. This is due to
A
(a) in nitration mixture, ortho, para-activity of NH 2
NH3 B1"2
B~ C ~ D , Dis [KCET] group is completely lost [BITSAT]
11 alkali
(b)-NH 2 becomes -NH;, which is m-clirecting
(a) CH3 Br (b) CH3 CONH 2
(c) -NH 2 becomes -NH+ SO4, which is m-clirecting
(c) CH3 NH2 (d) CHBr3
(d)-NH 2 becomes -NW No; , which ism-directing
27. In the chemical reaction,
CH 3 CH 2 NH 2 + CHCI 3 + 3KOH ~ A + B + 3H2 0 34. Choose the amide which on reduction with LiAJH4 yields a
The compounds A and B are respectively secondary amine [Kerala CEE]
(a) CH3 CH 2 CONH 2 and 3KC1 [Punjab CET] (a) ethanamide (b) N-methylethanamide
(b) C2 H 5 NCand K 2 CO 3 (c) N, N-dimethylethanamide (d) phenylmethanamide
(c) C 2 H 5 NCand 3KC1 (e) butanamide
(d) C2 H 5 CNand 3KC1 35. Name of method use to separate primary, secondary and
28. Why do 2° and 3° amines fail to undergo the carbylamine tertiary amines is CUPSEEJ
test? [Guj CET] (a) Hofmann method (b) Lucas method
(a) They combine with chloroform to give a stable (c) Victor Meyer method (d) Kolbe method
compound 36. Comparing basic strength ofNH3 , CH3 NH 2 and
(b) They react with alcoholic KOH C 6 H 5 NH 2 it may be concluded that [AMUJ
(c) The nitrogen atom of the amine group does not have
the required number of hydrogen atoms (a) basic strength remains unaffected
(d) All the given reasons are conect (b) basic strength of alkyl amines is lowest
(c) basic strength of aryl amines is lowest
29. C 2 H 5 NH 2 HNOi A ~ B ~ C. (d) basic strength ofNH3 is highest
Recognize the compound C from the following [Guj CET] 37. Which of the following is strongest base?
(a) propanenitrile (a) C6H 5NH2 [lndraprastha CET, CGPET]
(b) methylamine (b) p -NO2 -C6 H4 NH2
(c) ethylamine (c) m-NO2 -C6 H 4 NH 2
(d) acetamide (d) C 6 H 5 CH 2 NH 2
 Nitrogen Containing Compounds I 681
38. From the following compounds which does not react with 45. An organic an1ino compound reacts with aqueous nitrous
C 6 H 5 SO2 CI? [Guj CET] acid at low temperature to produce an oily nitrosoamine.
(a) C 2 H 5 · NH 2 (b) CH3 · NH2 The compound is [UPSEEJ
(c) (CH 3 )iNH (d) (C2 H 5 )JN (a) CH 3 NH 2 (b) CH3CH 2 NH 2
(c) CH 3 CH2 NHCH 2 CH3 (d) (CH 3 CH2 ) 3N
2008 46. C 5 H 13 N reacts with HNO 2 to give an optically active
39. Aniline reacts with ... to yield ... as the final product.
alcohol. The compound is [OJEEJ
(a) bromine, 2-bromoaniline [BITSAT]
(b) bromine, 2, 4, 6-tribromoaniline (a) pentan-1-amine
(b) pentan-2-amine
(c) chloroform/ KOH, phenyl cyanide
(c) N, N-dimethylpropan-2-amine
(d) acetyl chloride, benzanilide
(d) N-methylbutan-2-amine
40. Which will not go for diaz.otisation ? [VITEEE]
47. Which of the following amines can be directly oxidised to
(a) C 6 H 5 NH 2 (b) C 6 H 5 CH 2 NH 2 the corresponding nitro compound by potassium
pe1manganate ? [Guj CETJ
H 2 N"' H 2 N""
(c) / C6 H4 (d) / C6 H 4 (b) CH3 -CH-CH 3
H3 C 0 2N I
41. On heating benz.yl amine with chloroform and ethanolic NH2
KOH, product obtained is [MHT CET] (d) (CH 3 h C-NH 2
(a) benz.yl alcohol (b) benzaldehyde 48. In the following reaction sequence predict the compound
(c) benz.onitrile (d) benzyl isocyanide XandY.
42. Gabriel's synthesis is used frequently for the preparation of NH2
which of the following?
( a) Primary amines
[MP PET]
(b) Primary alcohols
h
~
Excess Br2 X (i! NaNO:i{HCI )
(11) H3P02
y
( c) Tertiary amines (d) Tertiary alcohols
43. The reaction of CHC1 3 and alcoholic KOH with CH3
p-toluidine gives [Kerala CEE] The compound X and Y are [Guj CET]

(a) ~ B, and ~ B ,

CH3 CH3

44. The correct order of increasing basic nature of the

(b)
B , ~ B,
~ and y
B,1()1 B'

following bases is [Kerala CEE] CH3 CH3

NH2
I.
(Y
:::::-.._
(c)
Bc~B,
~ and y
Bcl()IB'

Br Br

rYNH2 (d) ~
J;Br
m.T and

N02 CH3
(a) II < V < I < III < IV (b) V < II < I < III < IV 49. Aniline is prepared in presence ofFe/HCI from [BCECEJ
(c) II < V < I < IV < III (d) V < II < I < IV < III (a) benzene (b) nitrobenzene
(e) II < V < IV < III < I ( c) dinitrobenz.ene ( d) None of these
682 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2007 57. Hofmann's bromamide reaction is to convert [KCETJ

50. Which one of the following is the strongest base in aqueous (a) acid to alcohol (b) alcohol to acid
solution ? CAIEEEJ ( c) amide to amine ( d) amine to amide
(a) Trimethylamine (b) Aniline
(c) Dimethylamine (d) Methylamine 58. The strongest base among the following is [Kerala CEEJ

51. Reaction of cyclohexanone with dimethylamine in the (a) C 6 H 5 NH 2 (b) (C6 H 5 ) 2 NH

(c) NH 3 (d) (C2H 5 ) 2 NH
presence of catalytic amount of an acid fom1S a compound
of water during the reaction is continuously removed. The (e) C2H 5 NH2
compound fom1ed is generally known as [UPSEE, AIEEEJ 59. In the following reaction, X Bromination y
(a) an amine (b) an imine
NaN02 Z Boiling tribromo benzene. X is [WB JEE]
(c) an enamine (d) a Schiffs base + HCI CiH;OH
52. Decreasing order of basic nature in aqueous solutions (a) benzoic acid (b) salicylic acid
(a)C6 H 5 NH 2 > NH 3 > CH 3 NH2 > (CH 3 ) 2 NH [DCEJ (c) phenol (d) aniline
(b) NH 3 > C 6 H 5 NH2 > CH 3 NH 2 > (CH3 )z NH 60. The compound will react most readily with NaOH to fonn
(c) (CH 3 )i NH > CH3 NH 2 >NH 3 > C 6 H 5 NH2 methanol is [WB JEE]
(d)CH 3 NH 2 >(CH 3 )zNH > NH 3 > C6 H 5 NH2 (a) (CH 3 ) 4 N+I- (b) CH 3 OCH3
53. Which one of the following is most basic? [DCEJ (c) (CH 3 ) 3 s +r (d) (CH 3)J Cl
(a) FCH2 NH2 (b) FCH 2 CH 2 NH 2 61. Reaction of aniline with benzaldehyde is [WB JEE]
(c) C 6 H 5 NH 2 (d) C 6 H 5 CH 2 NH 2
(a) substitution (b) addition
54. Aniline reacts with cone. HNO3 to give [BITSAT] (c) condensation (d) polymerisation

(a) HN-@-NH
2 2
62. Hinsberg's reagent is
(a) C6 H 5 COC1 (b) CH 3 COC1
[WB JEE]

(c) C6 H 5 CH2 Cl (d) C 6 H 5 SO 2 Cl

63. The bad smelling substance fonned by the action of
alcoholic caustic potash on chloroform and aniline is
(a) nitrobenzene (b) phenyl isocyanide [AMUJ
(c) phenyl cyanide (d) phenyl isocyanate
64. Reduction of aniline with acetyl chloride in presence of
NaOH produce CBCECEJ
(c) O ==O= o (a) aniline hydrochloride (b) acetanilide
(c) p -chloroaniline (d) a red dye
65. CHC1 3 + C 6 H 5 NH 2 + 3NaOH~A+3B+3C
~ N 02
(d) ~ In the above reaction, the product A is [BCECEJ
(a) chlorobenzene (b) phenyl isocyanide
55. Carbylamine reaction is given by aliphatic [VITEEE] (c) phenyl cyanide (d) phenyl chloride
(a) primary amine 66. The molecular fo1mula C 3 H 9 N cannot represent [BCECEJ
(b) secondary amine (a) 1° amine (b) 2° an1ine
( c) tertiary amine (c) 3° amine ( d) quarternary salt
( d) quaternary ammonium salt
67. Which of the following is the strongest base?
56. Iso-propyl amine with excess of acetyl chloride will give [Jamia Millia Islamia]
(a) (CH 3 CO)zN-CH-(CH3 )i
(b) (CH 3 )iCH-~-COCH3
[MHTCETJ
(a) o-NH 2

H
(c) (CH 3 h CHN(COCH3 )z
(d) CH 3 CH 2CH 2 -N-COCH3

k
 Nit rogen Containing Compounds I 683
2006 7 6. Ethylamine on acetylation gives [BCECEJ
68. CH3 NH2 + CHCI 3 + KOH ~ Nitrogen containing (a) N-ethyl acetamide (b) acetamide
compound + KC! + H 2 0. (c) methyl acetamide (d) None of these
Nitrogen containing compound is [HT JEE] 77. High basicity ofMe 2 NHrelative to Me 3 N is attributed to
(a) CH3 - C= N (b) CH3 -NH-CH3 (a) effect of solvent [Jamia Millia Islamial
+ + - (b) inductive effect of Me
(c) CH3 -N= C (d) CH3 N = C (c) shape ofMe 2 NH
(d) shape ofMe 3 N
69. y : M e
2005
N/Me~
- I '-...Et 78. Dye test can be used to distinguish [DCEJ
OH n-Bu (a) ethylamine and acetamide
The alkene formed as a major product in the above (b) ethylamine and aniline
elimination reaction is CAIEEEJ
( c) urea and acetamide
(d) methylarnine and ethylarnine
~ 79. Benzyl amine reacts with nitrous acid to give [DCE]
(a) Me
(a) azobenzene (b) benzene
(c) benzyl alcohol (d) phenol
(YMe ("'yMe 80. Methyl amine reacts with methyl iodide. For completion of
(c)v (d)v reaction, how many moles of methyl iodide are required ?
(a) 1 (b) 2 [MHT CET]
70. The decreasing order of basic characters of the three (c) 3 (d) 4
amines and ammonia is CMHT CETJ 81. Identify the product in the following sequence
(a) NH 3 > CH3 NH2 > C 2 H 5 NH2 > C 6 H 5 NH 2
3 4 5-tribromoaniline (i) Diazotisation> ? [Kerala CEE]
(b) C2 H 5 NH 2 > CH 3 NH 2 > NH 3 > C 6 H 5 NH 2 ' ' . (ii) H3P02 .
(c)C6 H 5 NH 2 > C 2 H 5 NH2 > CH3 NH 2 > NH 3
(d)CH 3 NH 2 > C 2 H 5 NH 2 > C 6 H 5 NH 2> NH 3 (a) 3, 4, 5-tribromobenzene
(b) 1, 2, 3-tribromobenzene
71. The amine which will not liberate nitrogen on reaction with
(c) 2, 4, 6-tribromobenzene
nitrous acid is [Ke rala CEEJ
(d) 3, 4, 5-tribromonitrobenzene
(a) trimethylamine (b) ethylamine (e) 3, 4, 5-tribromophenol
(c) sec-butylamine (d) t-butylamine
82. Among the amines (A) C 6 H 5 NH 2 , (B) CH 3 NH 2 ,
(e) iso-propylamine
(C) (CH 3 h NH , (D) (CH 3 h N, the order ofbasicity is
72. In the reaction,
(a) A < B < D < C [Ke rala CEEJ
RNH2 HN02 A +B +Ci; Cis [UPSEE] (b)C < D < B < A
(a) NH 3 (b) N 2 (c) 0 2 (d) CO 2 (c) A > B > C > D
73. Aniline gives a precipitate with bromine. The colour of (d) B < C < D < A
(e)D < C < B < A
precipitate is [Guj CETJ
83. Nitration of aniline in strongly acidic medium, result in the
(a) red (b) black (c) blue (d) white
fom1ation of m -nitroaniline also. [Ke rala CEEJ
74. Aniline on oxidation with Na 2 Cr20 7 and H 2 S04 gives
This is because
(a) benzoic acid [J&K CETJ
(b) m-amino benzoic acid (a) amino group is meta orienting during electrophilic
(c) Schiff's base substitution reaction.
( d) p-benzoquinone (b) nitro group goes always to the meta position
irrespective of the substituents.
75. n-propylarnine yields a volatile compound X on warming
( c) nitration of aniline is a nucleophilic substin,tion
with ale. alkali and chloroform. X has an offensive odour.
reaction in strongly acidic medium.
The structure of X is CJ&K CETJ
(d) in strongly acidic conditions aniline is present as
(a)CH3CH2CH 2 CN (b)(CH 3 )iCHCN aniliniurn ion.
(c)CH 3 CH 2 CH 2 NC (d)(CH 3 )iCHNC (e) strong acids generate nitrite anion which can attack
only the meta position.
684 I Chapterwise & Topicwise Engineering Entrances Solved Papers
84. Which of the following compounds will form alcohol on 85. A gaseous carbon compound is soluble in dilute HCI. The
treatment with NaNO 2, HCI / H2O at 0°C? [AMU] solution on treating with NaNO 2 gives off nitrogen leaving
(a) (CH3)CHNH2 (b) C6HsNH2 behind a solution which smells of wood spitit. The carbon
compound is [Guj CETJ

(c) CH3----@--NH2 (d) H2N----@--NH2 (a) HCHO (b) CO (c) C 2 H 5 NH 2 (d) CH3NH 2

Topic 4
Preparation and Properties of Diazonium Salts
2014
1. The reagent with which the following reaction is best 5. Aniline when diazotised in cold and then treated with
accomplished is [WB JEE] din1ethyl aniline gives a coloured product. Its structure
Me Me would be [Manipal]

~ ~~
(a) CH3N H - 0 - N = N-0-NHCH3

H (b) CH3-0-N = N-O-NH2

(c) (CH3) z N - 0 - N = N - 0
2011
2. In the chemical reactions, (d) (CH 3) z N - 0 - N = N - 0 - N H2
NH2
6. Benzene diazonium chloride on reaction with phenol in

©.~~:KA °"~ B,
weakly basic medium gives
(a) diphenyl ether
(b) p-hydroxy azobenzene
[WB JEE]

Compounds A and B respectively are [AIEEE] (c) chlorobenzene

(a) fluorobenzene and phenol (d) benzene
(b) benzene diazonium chloride and benzonitrile
NH2

2009
(c) nitrobenzene and chlorobenzene
(d) phenol and bromobenzene
7. © 0) N-IHC'
(ii)CuCN/H30+
A;A is [OJEEJ

3. Which one of the following is not the correct reaction of CN COOH CHO OH
aryl diazoniu.m salts?
(a) C 6H 5 N; c 1- + Ct1 2Cl 2 ~ C 6H 5 Cl
+ - Heat
(b) C 6H 5 N2 Cl + HBF4 ~ C 6H 5 F
[DCEJ
(a)© (b)© (c)© (d)©
(c) C 6H 5 N;c1- + H 3PO2 ~ C 6H5 PO4
2006
(d) C 6H 5 N; c1- + SnC1 2 / HCl ~ C 6H 5 NHNH 2
8. Benzene diazonium chloride on treatment with hypo
2007 phosphorus acid and water in the presence of Cu +catalyst
produce [MHT CETJ
4. When aqueous solution of benzene diazoniwn chloride is
boiled, the product formed is [VITEEEJ (a) benzene
(b) toluene
(a) C 6H 5 CH 2 OH (b) C 6H 6 + N 2 (c) aniline
(c) C 6H 5 COOH (d) C 6H 5 OH
(d) chlorobenzene
 Answers
TOPIC 1 Preparation and Properties of Nitro Compounds
1. (d) 2. (c) 3. (c) 4. (a) 5. (b) 6. (c) 7. (a) 8. (a) 9. (a) 10. (b)
11. (d) 12. (d) 13. (b) 14. (d)
TOPIC2 Preparation and Properties of Cyanides and lsocyanides
1. (c) 2. (a) 3. (a) 4. (d) 5. (b) 6. (a) 7. (d) 8. (a) 9. (d) 10. (a)
11. (a) 12. (b) 13. (c) 14. (c) 15. (b) 16. (d) 17. (a) 18. (b) 19. (a) 20. (b)
21 . (c) 22. (d) 23. (b) 24. (a)
TOPIC3 Preparation of Properties of Amino Compounds
1. (a) 2. (a) 3. (c) 4. (c) 5. (d) 6. (d) 7. (a) 8. (b) 9. (a) 10. (a)
11. (c) 12. (a) 13. (c) 14. (a) 15. (c) 16. ( d) 17. (d) 18. (d) 19. (a) 20. (c)
21 . (a) 22. (d) 23. (a) 24. (a) 25. (a) 26. (c) 27. (c) 28. (b) 29. (c) 30. (b)
31 . (c) 32. (a) 33. (a) 34. (b) 35. (a) 36. (c) 37. (d) 38. (d) 39. (b) 40. (b)
41 . (d) 42. (a) 43. (c) 44. (a) 45. (c) 46. (b) 47. (d) 48. (b) 49. (b) 50. (c)
51 . ( c) 52. (c) 53. (d) 54. (c) 55. (a) 56. (c) 57. (c) 58. (d) 59. (d) 60. (a)
61 . ( c) 62. (d) 63. (b) 64. (b) 65. (b) 66. (d) 67. (d) 68. (d) 69. (b) 70. (b)
71 . (a) 72. (b) 73. (d ) 74. (d) 75. (c) 76. (a) 77. (a) 78. (b) 79. (c) 80. (c)
81 . (b) 82. (a) 83. (d) 84. (a) 85. (d)
TOPIC4 Preparation and Properties of Diazonium Salts
1. (a) 2. (b) 3. (c) 4. (d) 5. (c) 6. (b) 7. (b) 8. (a)

Explanations
Topic 1 Preparation and Properties of Nitro Compounds
1. + - This is because that nitro group is electron w ithdrawing group

6N~H, 6
N2Cl NH2
and reduces the electron density in nitrobenzene ri ng while there
is no such effect operating in benzene. As a result electron density
NaNO:!
in benzene ring is higher than that in nitrobenzene ring and hence
HCl,O"C
the electrophile w ill attack benzene ring faster t11an nitrobenzene.
Nitrobenzene (A) (B) (C)
Aniline Diazonium salt Aniline 3. Reduction of nitrobenzene by Zn and NH4Cl gives N-phenyl
hydroxylamine.
Hence, (C) is aniline.
NHOH

©
2. Due to the presence of electron witJ1drawing group,
nitrobenzene reacts slower than benzene in electrophilic
substinition reactions.
'"'""P + H,O
N itro group is m-directing substituent and it make further
N-phenyl hydroxylamine
electrophilic substitution more difficult. E lectrophilic
substinition of benzene occurs faster than t11at of nitrobenzene.
686 I Chapterwise & Topicwise Engineering Entrances Solved Papers
4. The product formed will be the mixture of oand p-bromotoluenes. 7. Secondary nitroalkanes can be converted into ketones by using
aqueous HCI.

,,Q,,-c-~-"~- 2
~-~-~ -3 ➔ &NO,+ ¢ N0 2
R--....___
R
R--....___
2 ,.,...cHN02 + HCI ~ 2 ,.,...c= 0 + N20 + H20
m R

Sn/HCI Nitrobenzene meta-bromo

(Reduction of NO:?)
(A) nitrobenzene
(B)

A
v +y
~NH2
- N02 is a meta-directing group. As it is also a deactivating
group, so no chance of introduction of second - Br atom.
Hence, (B) is meta-bromo nitrobenzene.
9. Nitrobenzene on nitration gives m-dinitrobenzene as - N0 2
NH2 group is meta-directing.
N02
NaNOi,HCI

~
dia:zohsation
Conc.HNOJ
lS:2-,J Cone. H2S04
~NO,
Nitrobenzene m-dinitrobenzene
(A)

In this reaction the attacking reagent is No;.

Sn / HCI

I CuBr,heat
Sandmeyer's reaction
10. ¼ H sN02
Nitrobenzene [HJ
Nitrobenzene on reduction with Sn and HCI produce aniline.
Hence, X is identified as - NH2 group.
l I. Reduction of nitrobenzene in acidic medium forms aniline as

~ AONH2
lgJ + 6[H] Zn/HCI lS:2-,J
Nitrobenzene Aniline

12. Reduction ofN02 group to NH2 group takes place by Fe / HCI.

5. N itrobenzene is reduced by Zn and alcoholic KOH into

~
hydrazobenzene.

C6H 5 -NH-NH-C6H 5 + Hz0

Hydrazobenzene
@__ NO, "'"' NO,
13. CH 3CH 2 - 0 - N = 0 is a nitrite derivative, hence it is not a
6. N itrobenzene on reduction with lithium aluminium hydride nitro derivative. Nitrite ion (0- N = 0) is an ambident
(LiAIH4 ) gives azobenzene. nucleophile since, it has two sites (oxygen and nitrogen) through
N02 which it can attack an alkyl halide. Whereas attack through
nitrogen gives nitro compounds attack through oxygen gives

2@-=.@-N - N-@ nitrites.

14. Nitrobenzene is insoluble in water but soluble in benzene alcohol
Nitrobenzene Azobenzene etc. Solubility of amines decreases w ith increase in molar mass due
Aromatic nitro compounds on reduction with LiAIH4 give azo to increase in the hydrophobic part which retard the formation of
compounds and not primary amines. Aliphatic nitro compounds H-bonds. Hence, aromatic amines are insoluble in water.
are reduced to primary amines wid1 LiAIH4•
Topic 2 Preparation and Properties of Cyanides and Isoc yanides

1. N 2" c _Q_ c;; 0 c_Q_c O N

lo 10" lo 2n
H H
7 sigma and 5 pi
Benzamide Benzonitrile

Hence, dicyanoethene have 12 bond (7 cr and Sn). Here, Pz0 5 is a dehydrating agent.
l 4 3 2 8. Isocyanides (carbylamines) are foul odour compounds.
· CH2 - CH - CH2
NC
I
5 CN
I II
CN CN
3-cyanopentane-1, 5-dinitrile
@(bo,re~ '""""''"')
Note However, according to latest IUPAC recommendation, if has foul odour
three same functional groups are present, then all the three are
9. Carbylamine reaction is given by aliphatic and aromatic primary
not included in the main chain and the compound is name as. amine. CH3CN does not give carbylamine reaction with
3 2 I chloroform because it is not an amine.
CH2- CH- CH 2
CH 3CNundergoes acidic hydrolysis to give carboxylic acid.
I I I
CN CN CN CH 3CN HiOl i f CH 3CONH2 HiOl if CH COOH+ NH
I, 2, 3- tricyanopropane
3 3
Acetic acid
3. Alkyl cyanides are hydrolysed by both acid and alkalies to CH 3CN undergoes alkaline hydrolysis to give salt of carboxylic
carbocyclic acids w ith the evolution of ammonia. Partial acid.
hydrolysis of al kyl cyanides to acid amides may be achieved with
alkaline H2O2. CH 3CN NaOH ) CH3CONH2 NaOH) CH COONa+ NH 3
HiO HiO Sodfurn acetate
Partial
R- C==N
hydrolysis
R- CONH2 CH3CN tautomerises to give methyl isocyanide.
Alkyl cyanide All..-yl arnide CH 3 - C == N ~ C ,_ N - CH3
Complete
hydrolysis tt+
RCOOH + NH 3 10. C2H5NC + H2O ~ HCOOH + C2HsNH2
Carboxylic acid Formic acid Ethylarninesalt

C2H 5NH 2 + H+ ~ C2H 5~

HOH Decarboxylation
4. CH 3CN CH 3COOH CH4
aq. H;iS04 Soda lime 11. R- X + NaCN DMSO> R- CN + NaX
Ethane Ethanoic acid Methane
nitrile +2H 20 (A) 6
(B) Alkyl halide Aliphatic cyanide
- NH3
-CO 2
12. R- CN + 4[H] >R- CH 2NH2
Hence, (A) and (B) are ethanoic acid and methane respectively. Primary arnine
Alkyl nitrites
5. The name ofisocyanides is carbylamine, and when it is attached
w ith an alkyl grou p, the compound is called alkyl carbylamine,
i.e. RNC. In alkyl cyanide alkyl group is attached to carbon atom
of-CN and nitrogen is present on the end.
+ -
R-C=N: R-N=C: 0
Alkyl cyanide Alkyl isocyanide
II
(alkyl carbylarnine)
(c) CH3 - C == N (d) CH 3 - C- NH 2
6. An alkyl cyanide is dissolved in ether or better in ethyl formate or sp3 sp sp3 sp2
ethyl acetate, and reduced with SnC12 and HCl and then steam 2
Acetonitri le does not contain sp hybridised carbon.
distilled. The who le process is called Stephen reaction. In this
process alkyl cyanide is reduced to aldehyde. 14. SnC1 2 + 2HC1 (g)~ SnC14 + 2[H]
CH3- C= N+ 2[H] + HCl SnCl2+HCI CH 3CN + 2[H]+ HCl~ CH3CH = NH· HCl
Methyl cyanide ether (X)

H20
CH 3-CH = NH· HCl ~ CH 3CHO +NHp :;i~ CH 3CHO+ NH4Cl
Ethyl irnine hydrochloride Acetaldehyde (Y)

There is no analogous method for the preparation of ketones.
7. With P2O 5 benzamide loses a water molecule and gives
benzonitrile.
(X) is acetaldimine hydrochloride and (Y) is acetaldehyde.
When an ethereal solution of an alkyl cyanide is reduced with
stannous chloride and hydrochloric acid the product is steam
distilled an aldehyde is produced the reaction known as Stephen's
reaction.
688 I Chapterwise & Topicwise Engineering Entrances Solved Papers

15. CH 3- C=N
Reduction
CH3CH2NH2 ~ CH3CH20H
HONO Topic 3 Preparation and Properties
Methyl cyanide Ethanatnine Ethanol of Amino Compounds
(A) (B)
1. The product will be
CHCl3,KOH ➔
CH 3CH 2NH2- - - - CH3CH2N=C N
(B) Btl1yl isocyanide
(C)
knCH3

6;
16. Acetonitriles on hydrolysis produce carboxylic acids w ith the
evolution of ammonia. 0
0 NH2 + CH3COOH.
II
CH 3- C=N ~ CH3- C-NH2 0
Acetonitrile Acetamide
Regioselectivity means which group will react selectively in the
0
presence of two or more than two functional groups.
II
CH,--C -
Acetic acid
OH + NH3
is more nucleophilic hence,
faster than CONH2.
NH
Here, among two functional group - NH2 and - CONH2, NH2
2 group will undergo reaction
17. R- C= N + 4[H) LiAIH 4 RCH2NH2
CH2 - NH2 O O
Reduction with Na and alcohol or LiAIH4 is called Mendius
reduction. + CH 3- C - 0 -
II II
C- CH3 ~
CHCI

18. Methyl cyanide gives acetic acid on hydrolysis. C- NH2 0

0 II 11
II 0 CH2 - NH - C- CH3
CH3CN CH3- C - NH2
~
H20I H'° H20I H'°
+ CH3COOH
CH 3COOH + NH 3
~C- NH2
19. Molecular formula ofbenzonitrile is ¼H 5CN.
II

6
0
- CH2- NH2 is more nucleophilic than - IT-NH 2.

Phenyl cyanide or 0
benzonitrile Hence, correct choice is (a).
20. Carbylamine (or isocyanides) give secondary amine on reduction. 2. Order of basic strength of aliphatic amine in aqueous solu tion is
as follows (order of Kb)
R- N ➔ C Ni/H 2 R- NH- CH3
Carbylamine Secondary amine (CH3)iNH > CH3NH2 > (CH3)JN> G;H 5NH2
21. Acetonitrile on reduction gives ethanamine.
Reduction
..
As we know, pKb = - log Kb
So,(CH3)iNHwill have smallest pKb value.
CH3CN LiAIH
4
CH3CH 2NH2
Acetorutnle EthanaJmne
In case of phenyl amine, N is attached to sp2 hybridised carbon,
22. Isocyanide on hydrolysis forms primary amine not ammonia.
hence it has highest pKb and least basic strength.
H+
C6H 5NC + H 20 --=-=-➔ C6H 5NH 2 + HCOOH 3. Hybridisation ofN-atom in below compounds are sp2, sp3 and sp3
23. Ethyl bromide reacts w id1 KCN to give ethyl cyanide. respectively.

24. R- C==N
C2H 5Br + KCN(alc.) ~ C2H 5CN + KBr
Ethyl bromide Ethyl cyanide OCJI
sp
2 N'
sp
3 N

: . Alkyl group is attached to carbon atom of CN group in alkyl H

TI
cyanide.
Greater ilie s-character more will be electronegativity ofN-atorn
and lesser will be its basicity on iliis basis I is less basic than TI.
 Nitrogen Containing Compounds I 689
Conjugation If lone pair of electron of N is involved in
conjugation, it decreases the basicity of compound due to lesser Benzyl amine shows following five isomers.
availability oflone pair for donation to show basic nature.

II III
H H
Lone pair invo lved in formation of aromatic sextet of 61t-electron
(least basic).
So, the correct order ofbasicity is II > I > III.

V
8. Since, the amine gives white precipitate with benzene sulphonyl
chloride which is insoluble in aq. NaOH, so it must be a
secondary amine ( i.e. amine hav ing RNHR group).
Me
Among the given compound, only \/\Me is a secondary
I
H
amine, so it represents stmcmre of given amines.
9. In general, the basic strength of amines increases as the number of
Sulphanilic acid exists as a dipolar ion in w hich has acidic as well electron releasing groups (+ I showing group like - CH3)
as basic groups in the same molecule. Such ions are called Zwitter increases due to more availability of nitrogen to donate its lone
ions or inner salts. pair of electrons. But in aqueous solution, two other factors, i.e.
steric effect and solvation effect, also involves due to which
tendency of tertiary (3°) amines to loose their lone pair of
electrons, i.e. basicity reduces.
Thus, the order of basicity, if the electron releasing group in
methyl, in aqueous solution is
(CH3)iNH > CH3NH2 > (CH3}3N
10. In benzylamine (Cc;H 5CH2NH2 ) the lone pairofN does not involve
in delocalisation and are avialable for donation but, in other given
~Br compounds the lone pair ofN involve in delocalisation and thus,
HOH➔ ly not available for donation as shown below
+
CH 3
[CJ

If the non-substimted product is to be prepared the activation

influence ofthe- NH2 group must be moderated which is usually
done by acetylation ( - NH 2 ------t - NHCOCH3).
8Aniline
------t
6
NH:.
- ~ So on

NH2 CH3
6. CH 3CHO+CH2N 2 ------t CH 3_____6
------t
NaBH4 JCH3- CH- CH3 h'
Acetanilide
I

. A2
+
OH
7. Compound A (C7 H 9 N) is benzyl amine (C6H 5CH 2NH2 ). It reacts
w ith NaNO2 /HCI at 0°C to form benzyl alcohol and N 2 gas. y ------tSo on
CH2NH2 CH 2OH

@-,~o @+N,t
(A)
NO2

Thus, benzylamine is the most basic compound among the given

compounds.
690 I Chapterwise & Topicwise Engineering Entrances Solved Papers

+
N=NCl- Amino group being o-p-directing. Activates the benzene and

11. @ ,©
A niline
NaN()i+HCI
273 K
Benzene diazonium
H3P02+H20

CHO
hence, further substitution in aniline is very-easy and in some
case (e.g. bromination) substitution takes place at all available
positions forming poly substituted products even under normal
conditions.
chlo ride
19. It is the first step of Gabriel's phthalimide synthesis. The

@
Benzene
CO+HCI, Anhy. AIClyCuCl2
Gattennann-Koch reaction
©
Benzaldehyde
hydrogen bonded to nitrogen is sufficiently acidic due to two
a-carbonyls.
0 0

3CH3 o = }- H + Olr~ H,O + q ,

1 2
12. CH3- b H - NH2 o Co
/so•propylamine

IUPAC name= propan-2-amine 1

13. Aromatic primary amine reacts with nitrous acid to give
diazonium salt while primary aliphatic amine gives alcohol with
nitrous acid. ~w-~w
+ -
NH2 N 2Cl
0 o-
@+ + 2HCJ NaNO, --"'--'4 @+ +
Benzene diazoniwn
N,CJ H,O
The conjugate base formed above act as nucleophile in the
subsequent step of reaction. As shown above, the nucleophile
exist in three resonating form, one may think of oxygen being the
c hloride donor atom in the nucleophilic attack. However, nitrogen act as
: . Aromatic primary amines give azo dye test. donor as it is better donor than oxygen.
RNH2 + HN02 - ROH + N2 + H 20 0

c¢-1H,-o-B,
Alcohol
14. N-methyl aniline on reaction with nitrous acid gives N-nitroso-N-
methylaniline.
½H5 - NH - CH 3 + HONO -
N •rnethylani line C H _ N - CH + HzO (c1 0
6 s I 3 0
NO
N-nitroso• N-methylanil ine

15. Primary amines on heating with chloroform and alcoholic KOH

<-""-+Ot;+C
H,-o-B,
produce foul smelling carbylamine (isocyanide).
0
R- NH2 + CH P1
+ 3KIOH - R- NC + 3KC1 + 3H20
l socyamde Bromine is not substituted in the above reaction as 1t 1s m
(foul smell)
resonance with benzene ring giving partial double bond character
16. This is Hofmann's bromamide reaction. In this reaction, product to C -Br bond, hence difficult to break.
compound has one less C atom than reactant. So, it causes
shortening ofC chain.
R- CONH2 - R - NH2
ClCH2 -Qy~
-
Br:
•• ~ clCH2 -0-
-
" Br

CH 3CONH2 + Br2 + 4KOH -➔ CH 3NH2 20. As we know, benzene diazonium salt forms brilliant coloured dye
+ 2KBr + 2Hz0 + K 2C03 with J3-naphthol, the compound under consideration must be
p-toluidine as it is a primary aromatic amine. Primary aromatic
amine, on treatment with NaN02 in dil. HCl forms the
corresponding diazonium chloride salt.
17.
NH2 NaN02
N NI! c 1-
Aniline Benzaldehyde Schi trs base HCI
or anils H 3C H3C ~

18.
l:
LSlJ
2

+ 3Br2 -
Br~Br
~ + 3HBr
~OH

vV jl.naphlhol

Br
2, 4, 6•tribromoaniline (sym•tribromoaniline)
 Nitrogen Containing Compounds I 691
21. Intermolecular H-bonding is more in primary amines than in
29. C2H 5NH 2 HN0 2 C2H 50 H ~ C H CI
2 5
secondary amines as there are two H-atoms available for
Ethylamine - N2 Ethanol Ethyl chloride
H-bonding. Tertiary amines do not have intermolecular H-bonding (A) (8)
due to absence ofH-atoms available for H-bonding. Therefore, the
order of boiling points of the given amines is as follows ~ C2HsNH2
n-butylamine (T) diethylamine (II) N, N-dimethylethyl amino (Ill) Ethylamine
nC4H 9 NH2 > (C2H 5 ) 2NH > C2H 5N(CH 3)z The compound (C) is ethylamine. (C)

b.p. 350.8 K b.p. 329.3 K b.p. 310.5 K Sn/HCI

30. C6H 5NO2
22. /so-propylamine is a primary amine because one hydrogen atom Nitrobeniene Aniline
(X)
of ammonia is replaced by iso-propyl group.
NH2 Ci;H 5CONHCi;H 5 + HCI
I Benzani Iide
(Y)
CH 3- CH- CH 3
! 0 amine 31. The basic character of amines depends upon the capacity of nitrogen
atom to donate an electron pair. More the ability of nitrogen atom to
23. The order of boiling points of the isomeric amines is as follows donate electron pair, more will be the basic character. In presence of
Primary amines > secondary amines > tertiary amines. electron releasing groups (+/ showing group, - CH3) the basic
(!0> 20> 30) character of amines increases due to more availability of electrons
The degree of association however depends upon the extent of on nitrogen atom. Tertiary amines are least basic due to steric
H-bonding. Since, 1° amines have two, 2° amines have one hindrance caused by three bulky alkyl groups.
while 3° amines have no hydrogen linked to nitrogen, therefore, :. The order of basic character is
among isomeric amines, I O amines have the highest while 3° HN(CH3)z > CH 3NH2 > N(CH3) 3 > NH 3
amines have the lowest boiling point. NaCN
-HCI
32. CH 3CH 2T- CH 3CH 2CN
24. CH3NH2 + C6HsSO2Cl ~ Ct,H sSO2NHCH3 (A)
IO amine H insberg's N - methyl be.nzene
reagent sul phonamide Br2/ NaOH CH CH NH
3 2 2
Partial hydrolysis (C)
NaOH
C6H 5SO2N(Na)CH3
(alkali)
Soluble sodium salt 33. On direct nitration of aniline, lone pair of electrons present at
nitrogen atom will accept proton from the nitrating mixture to

~ ~
give anilinium ion which is meta directing.

©
SNHCI ~OOH NaNO:z!HCI Et>

~ ,,,o,•~~
25. ~ (Reduction)) ~ (Diazotisation) ~,~;m

NO2 NH2 N = NCl OH

p-nitrophenol Quinol
A nilinium ion
aq. KOH
CH3CH2OH 34. Secondary amides such as N-methylethanamide on reduction
a
(A) with LiAIH4 give secondary amines.
CH3COOH NH 3 CH3COONH4 CH 3CONHCH 3+ [H) CH3CH2NHCH3 + H 2O
Acetic acid N -methylelhanamide T' amine
(8)
35. In Hofmann method, a mixture of primary, secondary and tertiary
___:\➔ CH 3CONH2 CH3NH2 amines is treated with diethyloxalate, where primary amine forms
Acetamide Methylamine
solid oxamide, secondary amine forms a liquid, oxamic ester
(C) (D)
whereas tertiary amine remains unaffected.
27. CH 3CH2NH2 + CHC13 + 3KOH (COOC2H 5)z + 2HNHR ~ (CONHR)z + 2C2H 5OH
~ CH3CH2NC + 3KC1 + 3H p Diethyl oxalate 1° amine Solid
(A) (8) CONR2
This reaction is known as carbylamine reaction. (COOC2H 5)z + HNR2 - I
2° amine COOC2H 5 + C2H 5OH
28. Secondary and tertiary amines fail to undergo the carbylamine Liquid
test because they react with alcoholic KOH.
(COOC2H 5)z + NR3 - No reaction
R- NH2 + CHC1 3 + 3KOH ~ R- NC+ 3KCI + 3H 2 3° amine
1° amine 36. Presence of methyl group increases the electron density on nitrogen.
The above reaction is known as carbylamine reaction and is So, increases the basicity. Aniline is a weaker base than the primary
generally used to convert primary amine into isocyanide. aliphatic amines and this may be explained by resonance.
The lone pair ofN is involved in resonance, thus not available for
(R)2NH+ CHC13 + 3KOH ~No reaction
2° amine donation. That's why basic strength of aryl amines (aniline) is
lowest.
692 I Chapterwise & Topicwise Engineering Entrances Solved Papers

¢ ¢
37. Aliphatic amines (in which amino group is attached with alkyl NH2 NC

~~
group) are more basic than aromatic amines (in which amino
group is bonded directly w ith benzene nucleus). Hence, + CHCl, + 3(,ic)KOH • + 3KC1+ 3H,O
C6H 5CH2NH2 (benzylamine), being an aliphatic amine, is the
most basic among the given compounds.
38. Tertiary amines, due to lack ofH-atom attached directly w ith N, CH3 CH 3
p-toluidine 4-methyl phenyl
does not react with benzene sulphony l chloride (¼H 5SO2Cl), i.e. isocyanide
Hinsberg's reagent. (C2H 5 ) 3 N is a tertiary amine, so does not
react w ith C6H 5SO2Cl. 44. - OCH3 is strongest electron releasing group (+M effect) which
opposes most the dispersion oflone pair ofelectron of nitrogen into
39. Aniline reacts with Br2 to give 2, 4, 6-tribromoanil ine not the ring. Thus, - OCH3 being at para position imparts highest
bromoaniline as basicity.
NO2 being at meta position stabilises the electron pair of nitrogen

@+3B,,~ B,vB:3HB, only by - / effect. While NO 2 being present at para position due to
- M effect and -/ effect stabilises the lone pair of electron of
nitrogen, most and impart least basicity.

~ NH2 ~NH2 YNH2

Br
2, 4, 6- tribromoaniline ~ <V <:: :c-.. I
O2N
40. Only I O aromatic amine (primary aromatic amine) forms
diazonium salts at low temperature (0°-5°C). A ~eaction in which NO2
- NH 2 group is converted into diazo group (- N N) is called =
diazotisation. Diazotised salts are stable in cold aqueous solution.
0 +
¼ H 5NH2 + HCl 0"-
5 c ¼ Hs NH 3 Cl-
Hence, correct order of increasing basicity TI<V<I<III<IV.
NaNO2 + HCl O"-s•c HNO2 + NaCl
45. Secondary amine on reaction w ith aqueous HNO2 at low
+ oo s c
0 +
temperature produces yellow oily nitrosoamines.
¼Hs NH 3 Cl- + HNO 2 ~ ¼Hs N2 Cl- + 2H 2O
CH 3 CH 2NHCH 2CH 3 is secondary amine.
H 2N'-...._ H 2N'-...._
¼ H 5NH2 , _.,,.,-cy4 ,_.,,.,-¼H4 are aromatic primary 46. HNO2 reacts to give an alcohol means the compound is primary
H 3C 0 2N amine. C5H 13N means C 5H 11NH 2 (primary amine)
amines, so undergo diazotisation but C6H 5 CH 2NH2 (aliphatic Optically active alcohol means C5H 11 segment contains a chiral
amine) will not undergo diazotisation. carbon.
41. It is carbylamine reaction,

CH 2NH2 c r CH2NC
CHCl3 ) I
KOH, ::::,.__
cr CiHsOH
Benzylamine Benzyl
isocyanide Pentan-2-amine

42. Gabriel's synthesis is used for the preparation of 1° amines. this 47. Primary amine having 3° carbon attached to it can be directly
process, oxidised to corresponding nitro compound by K.MnO 4 •

coNH~ ():co
I '--:: NK~ ():co
I '--:: NR
(CH 3 ) 3 C- NH2 ~
[OJ
KMn04
(CH 3 ) 3 C- NO2

CO ✓.:, CO DMF ✓.;, CO

Phthalimide Potassium phthalimide N-alkylphthalimide
Excess Br2 (i) NaN(½/HCI

CC
COOH 0-s· c
H20llr + RNH2
COOH
Phthalic acid Primary amine

43. Aliphatic and aromatic primary amines on warming with CHC1 3

and alcoholic KOH form isocyanide or carbylamine which has
very unpleasant smell. This reaction is known as carbylamine Br~Br
reaction. Since, p- toluidine contains an aromatic primary amine ~ (ii)H3P(½
group, it undergoes similar reaction and give 4-methyl pheny l
1socyanide.
CH3
 Nitrogen Containing Compounds I 693
49. Aniline is prepared by the reduction of nitrobenzene in acidic 58. (C2H 5 )z NH (2° amine) is the strongest base. Basic nature of
medium. amines is due to presence of lone pair of electron on nitrogen
N02 NH2 atom which is available for the bond formation with Lewis acid.

@+ @+
Due to the +l effect 2° amine is better base than 1° amine and
0 NH 3. In case of aromatic amines the lone pair on nitrogen atom is
6H "'" , 2H,O involved in resonance, therefore, not available for bond
Nitrobenzene Aniline formation, so aromatic amines are less basic.
50. In aqueous solution, basicity order
dimethyl amine> methyl amine> trimethylamine > aniline
20 10 30

Hence, dimethylamine is the strongest base.

51.
0 / CH3
O + HN"-
CH3
-
0-N"-
-
/CH3
CH3
Keto Enamine

6-+~B)N<~:: _j
The compound formed is an enamine. Br
52. Basic nature of an amine depends upon availability of lone pair 1, 3, 5-tribromo
benzene
on nitrogen atom. If lone pair is easily available the compound
would be more basic. Due to + I effect of methyl group, 60. The compound (CH 3)4 N+r will react most readily with NaOH
methylamine is more basic than ammonia and dimethylamine is
to form med1anol.
more basic than methylamine. While aniline is a weaker base than
ammonia due to delocalisation of lone pair of nitrogen atom at (CH3)4 Wr + NaOH- (CH3)4 N+OW+NaI
different position.
Hence, the correct decreasing order of basic nature is. (CH3)4N+ow ~(CH3hN + CH30H
Methanol
(CH3)zNH > CH3NH2 > NH3 > C6H 5NH2
61. Reaction of aniline with benzaldehyde is condensation reaction.
53. Benzylamine (¼H 5CH2NH 2 ) is more basic than aniline H
(C6H 5NH2 ) because N-atom of aniline is delocalised over the
J Condensation
benzene ring. However in benzylamine the lone pair of electrons ¼H5 - C =0 + H 2N¼Hs ---➔
on the N-atom is not conjugated with the benzene ring and Benzaldehyde Aniline
therefore it is not delocalised. Hence, the lone pair of electrons on C6H 5CH = NC6H 5+ Hp
the N-atom in benzylamine is more readily available for Benzylidene aniline
protonation than that on the N-atom of aniline. Thus, the
benzylamine is a stronger base than aniline. 62. @ - i- c1 or C6H 5S02CI is called Hinsberg's reagent.
II
54. @-NH2 7o~ o==<:)=o
3
) 0
It is used for the rustinction of 1°, 2°, 3° amine.
Benzoquinone
63. Action of alcoholic caustic potash on chloroform and aniline
55. Carbylamine reaction is given by aliphatic and aromatic primary forms a bad smelling compound phenyl isocyanide.
amine hence, it can be used for the distinguish of primary amine ¼H5NH2+ CHC1 3 + 3KOH(alc.)-
with secondary and tertiary amine. In this reaction, a primary Aniline Chlorofonn
amine reacts with chloroform and alcoholic KOH to give ¼HsNC + 3KCI + 3H20
poisonous substance isocyanide. Phenyl iS()Cyanide
~
RNH2 + CHCl 3 + 3KOH(alc.)- RNC + 3KCI + 3Hp This reaction is called carbylamine reaction and it is actually the
Primary amine Alkyl test of primary amines.
isocyanide

56. (CH3)iCH · NH2 + 2CH3COCI -(CH3)z CH- N(COCH3) 2 64. C6H 5NH2 + Cl- COCH3 NaOH C6 H 5NHCOCH3+ HCI
/so-propyl amine -HCI (Tertiary amine) Aniline Acetyl chloride Acetanilide
(priamine)
65. CHCl3 + ¼H5NH2 + 3NaOH- C6H 5NC
57. Hofmann's bromamide reaction is used to convert amide to Phenyl iS()Cyanide
{A)
amine.
RCONH2+ Br2 + 4KOH- RNH2 + K 2 C03 + 2KBr + 2Hp
Amide Amine
694 I Chapterwise & Topicwise Engineering Entrances Solved Papers

66. C3H 9 N represents following structures 74. Aniline on oxidation with Na 2Cr20 7 and H 2S0 4 gives
H p -benzoquinone.
I

~ ¢
CH 3CH2CH2NH 2; CH3CH 2 - N- CH3; CH 3- N- CH 3
Propanamine N-metl1yl etl1anamine N,N-dimethyl methanamine
O
( I amine) (2° amine) (3° amine)
:.Quaternary salt cannot be represented by C 3H 9N.
Aniline
67. CH 3- (an electron releasing (+!) grou p) increases electron 0
p-benzoquinone
density at N-atom hence, basic nature is increased. (quinone)

(a) ~ NH2 (b) ~ N H--+- ~~3 75. Primary amines react with ale. alkali and choroform to give an
offensive odour compound, i.e. isocyanide. This reaction is called
carbylamine reaction.
(c) ~ NH, CH 3CH 2CH 2NH2+ CHCl3 + 3KOH ~ CH3CH 2CH 2NC
n-propyl amine (Alcohol) Propyl isocyanide
CH3
½ Hs decreases electron density at N-atom thus basic nature is +3KC1+ 3Hz0
decreased. (Lone-pair on N in aniline compounds is delocalised 76. Ethylamine, on acetylation, gives N-ethyl acetamide.
along with 1t-electrons in benzene). Thus, (d) is the strongest base. CH3COCI
C2H 5NH 2 t,. C 2H 5NHCOCH 3
68. CH 3NH2 + CHC13 + 3_f0H _~ CH3NC + 3KCI + 3H20 N-ethyl acetamide
CH 3NC or CH 3- N == C methyl isocyanide or methyl
77. Electrons donors are bases. Greater the stabilisation of cation
carbylamine. This reaction is an example of carbylamine reaction
formed by loss of electron more will be basicity of amine.
and it is used for the distinction of primary-amines from secondary
2° amine is more basic than 3° amine because 2° amine is
and tertiary-amines or identification of primary amino group.
stabilised by hydrogen bonding with solvent molecule.
78. C2H 5NH2 + HN02 ~ C2H 50 H + N 2 + H 20
69. ~i~Me
H H
N,
I CH2-CH3l3 1
Ethylamine
(I O aliphatic amine)
Ethyl alcohol

CH 2-CH2-CH 2-CH3 NH2

133 132
There are four ~-hydrogens in this quartemary ammonium salt.
On heating quartemary ammonium salt it undergoes Hofmann
@+ HNO, ,::~, Ora"g' rolo=d dye

elimination (abstraction of most acidic hydrogen which is ~ 1). Aniline

Hence, major product is CH 2=CH2 (least substituted alkene). :. Dye test is used to distinguish between I O aliphatic and
70. Electron withdrawing groups (e.g. benzyl) decrease the basicity I O aromatic amine.
of amines. Electron donating groups (e.g. alkyl) increase the CH2NH2 CH20H
acidity of amines.
: .The correct order of basicity of amines is
C 2H 5NH2 > CH3NH2 > NH3 > C6H 5NH2
71. Trimethylamine is a tertiaryamine. It dissolve in cold nitrous acid
79. @+
Benzylamine
BONO----'> @
Benzyl alcohol
+ N, + H,O

to form salts which decompose on warming to nitrosoamine and

alcohol. It will not liberate nitrogen. 80. CH3- NH2+ 3CH3I ~ (CH3)4 N+r
Methyl amine Quartemary
(CH3)JN + HN02 ~ [(CH3)JNHf N02 ammoniwn salt
Trimethyl ammonium nitrite Therefore, 3 moles of CH3T (methyl iodide) are required for
reaction with methylamine.
72. RNH 2 HNOz ROH + H20 + N2 t
{A) (B) (C) NH2 N!Cl-
73. Aniline reacts with bromine and give white ppt. of 2, 4,
6-tribromoaniline.
81. ~ - NaNOiJHCI ~ H3P~
3
()
1

@+3B,, -,B,yB:3HB,
Bry Br Bry Br B r ~ Br
Br Br Br
3, 4, 5-tribromoaniline

82. The order ofbasicity among the following amines is

(CH3) 2NH > (CH 3)3N > CH 3NH2 > C6H 5NH 2
2, 4, 6-tribromo or, A < B < D < C is the correct order of basicity.
aniline white ppt
 Nitrogen Containing Compounds I 695
83. On direct nitration of aniline, lone pair of electrons present at 4. When aqueous solution of benzene diazonium chloride is boiled,
nitrogen atom will accept proton from the nitrating mixture to it gives phenol.
give anilinium ion which is meta directing. Ntc1- OH

© • H,O - © • N, + HCI
Benzene Phenol
d iazonium chloride
Anilinium
ion 5. Aniline on diazotisation in cold (at 0° to 5°C) gives benzene
84. Aliphatic primary amines on treatment with NaNO2 / HCl gives diazonium chloride.
alcohols with evolution of nitrogen gas.
0- NH2 + NaNH2 + 2HC1

0- N
0-S°C
Diazotisation

= N-Cl + NaCl + 2H2O

(CH 3) 2CHOH + N 2 + H2O
Benzene diazonium chloride
85. It is methylamine which being basic, dissolves in dilute H CI. It
reacts with NaNO 2 evolving nitrogen gas and leaving behind This benzene diazonium chloride on coupling reaction
methyl alcohol which has smell of wood-spirit. with dimethyl aniline gives a coloured product, i.e.
p-(N, N-dimethyl) amino azobenzene (azodye).
CH 3NH2~ CH 3NH2 · HCI

CH3NH2 + HNO2 NaN0 2 IHCI CHpH

Methyl alcohol
+ N2 i + H 2O 0-N = N·Cl + H-o-N(CH3)i NaOH )

Topic 4 Preparation and Properties 0- N = N - 0 - N(CH3) 2+ HCl

of Diazonium salts
6. Benzene diazonium chloride reacts with phenol in weakly basic
1. H 3PO 2 is the reagentthat converts - N;c1- group into H. During medium gives p -hydroxy azobenzene.
this process N 2 and HCl gases are released and H 3PO 3 is formed.
N 2Cr

~
Benzene diazonium Phenol
chloride
•~ • @ • HCl + N,t
Weakly basic
@ - N = N - @ - OH + HCI
Me Me medium
p-hydroxy azobenzene
+ -

~=" 25' :r. .6

+

Benzene diazonium Benzonitrile

NaN02IHCI
273 K
~!~~~~OH
chloride (B)
(A)
Aniline Benzene Cyanobenzene {A) Benzoic
diazonium chloride acid
Formation ofA is by diazotisation and formation of B from A is by N 2CI
~ reaction.

@
3.
6 1

• .".~. O • H,PO, + N, + HCI

S.

diazonium
chloride
+ H;PO, + H,O c,C,
Benzene Hypophosphorous
acid
@
Benzene
+ N, + HCI + H;PO,
Phosphorus
acid
Biomolecules
QUICK REVIEW
• All living systems are composed of various organic
compounds namely carbohydrates, proteins, fats or lipids
and nucleic acids. These organic compounds are referred
as biomolecules.
• Carbohydrates These include polyhydric aldehydes or
polyhydric ketones and large polymeric compounds which
can be broken down into polyhydric aldehydes or ketones.
• On the basis of hydrolysis, carbohydrates are classified as
monosaccharides, disaccharides, polysaccharides.
Carbohydrates are also classified as reducing or
non-reducing sugars.
• Except ketotriose (dihydroxy acetone), all aldose and
ketoses (monosaccharides) contain asymmetric carbon
atoms and are optically active. Naturally occwTing form of
glucose is dextro form.
It shows mutarotation (change in value of specific
rotation). All reducing sugars which exist in hemiacetal
and herniketals forms undergo mutarotation in aqueous
solution.
• Mutarotation It is the spontaneous change of a specific
rotation of an optically active compound towards an
equilibrium value.
• All monosaccharides, in the free state exist in the pyranose
form. In the combined state, some monosaccharides such as
ribose, 2-deoxyribose, fructose etc., exist in furanose form.
• Glucose, an aldohexose (C H 12 0 6 )can be prepared from
cane sugar (sucrose) and stlrch. In glucose, all six carbon
atoms are linked in straight chain and the carboxyl group is
present as an aldehydic group. It contains primary alcoholic
group.
• D and L indicates the relative configuration of a particular
stereoisomer which represents their relation with a
particular isomer of glyceraldehyde. (+)-glucose is
assigned D-configuration.
• Glucose does not restore pink colour of Schiff's reagent
and also does not give 2, 4-DNP test.
The pentaacetate of glucose does not react with
hydroxylamine which shows that no free -CHO group is
present in glucose.
• In monosaccharides, like glucose, if -OH group attached
to C 1 is towards right, it is called an a-form and if the
-OH groups attached to C1 is towards left it is called
P-form. Such type of pair ofstereoisomers which differ in
configuration only around C1 are called anomers.
Monosaccharides which differ in configuration at a carbon
atom other than the anomeric carbon are called epimers.
• The six membered cyclic structure of glucose is called
pyranose structure (aor P ). It is more correctly
represented by Haworth structure.
• Fructose is a ketohexose, obtained along with glucose by
the hydrolysis of disaccharide, sucrose. It is a
laevorotato1y, i.e. D -(- )-fructose, compound.
• ( + ) - sucrose, ( + ) - lactose, (+)- maltose and
(- ) - cellobiose are disaccharides. Disaccharides may be
either reducing or non-reducing. e.g. sucrose is
non-reducing, while maltose is reducing sugar.
• Lactose is known as milk sugar.
• In polysaccharides, different monosaccharide units are
linked to one other by glycosidic linkages. The
polysaccharide inulin is a polymer of fructose. Starch
consists of two compounds, amylose (20%) and
amylopectin (80%).
Amy lose is a linear polymer while amylopectin is a highly
branched polymer. Both are composed of a -D- glucose
units linked by glycosidic linkages.
• Cellulose is a straight chain polysaccharide composed of
P-D-glucose units which are joined by P-glycosidic
linkages between C- 1 of one glucose unit and C-4 of the
next glucose unit. Another polysaccharide glycogen is the
storage material of animals.
• Glycogen is known as animal starch. Its structure is similar
to amylopectin.

• Proteins These are the class of biologically important
compounds. Upon hydrolysis protein gives only a-amino
acids. An amino acid is a bifunctional organic molecule
that contains -COOH group and - NH 2 group.
• All proteins upon hydrolysis give only a-amino acids.
Protein is the only natural a-amino acids secondary amine.
• - NH 2 group is basic and -COOH group is acidic
therefore, in neutral solution a-amino acid exists in an
internal ionic form called Zwitter ion (dipolar ion). The
intermediate pH at which the amino acid shows no
tendency to migrate towards any of the electrodes and
exists the equilibrium when placed in an electric field is
known as isoelectric point.
• Polypeptides are the polymers of a-amino acids. 1n
polypeptides, amino acids are linked by peptide linkage
(- CONH- ). Insulin is a polypeptide hormone produced in
the pancreas. It contains 51 amino acids arranged in two
chains (21 and 30 amino acid residues) which are
cross-linked at two places by disulphide bonds(- S-S-).
• Proteins are of two types-fibrous (e.g. Keratin in hair, skin,
etc.) and globular (e.g. Insulin and albumins).
• Primary structure of protein refers to the number and
sequence of the amino acids in its polypeptide chains.
Secondary structure of a protein refers to fixed
configuration of a polypeptide skeleton. Secondary
structure of protein is mainly of two types a-helix and
~-pleated sheet structure. Tertiary structure of a protein
refers to its complete three dimensional structure.
• The coagulation of proteins is known as denaturation.
Denaturation causes a change in the secondary and tertiary
structures of proteins while primary structure remains
intact. Denaturation can be done with the help of heat and
UV rays or by adding chemicals such as acids, bases and
organic solvents etc.
• Enzymes These are essential biological catalysts which
catalyze the biochemical reactions. These are globular
proteins and possess specificity. Enzymes reduce the
magnitude ofactivation energy ofany biochemical reaction.
• Molisch's test It is a general test for carbohydrates while
Ninhydrin test is given by all proteins. Millon's test is given
by proteins which yield tyrosine on hydrolysis. Nitroprusside
test is given by proteins which contain - SH group.
Alkaline solution of prote ins gives biuret test due to the
presence of - CONH linkage. Some proteins give
Molisch's test as it is possible that aldehydes are also
released when mixing proteins.
• Vitamins These are complex organic molecules required
in small amounts for the no1mal metabolic processes and
for the life, growth and health of man and anin1als.
Vitamins A, D, E and K are fat soluble vitamins while
vitamin B-complex and vitamin C are water soluble
vitamins.
Biomolecules I 697
• In biological system, two types of nucleic acids are found .
These are deoxyribonucleic acid (DNA) and ribonucleic
acid (RNA). Nucleic acids are polymers consist of
nucleotides. Nucleotide consists of nitrogenous base,
pentose sugar (ribose or deoxyribose sugar) and
phosphates. 1n DNA nitrogenous bases are of four types
adenine, guanine, cytosine and thymine. While in RNA
uracil is present in place of thymine.
• Adenine and guanine are purines while uracil, thymine and
cytosine are pyrimidines.
• A nucleoside contains two basic components of nucleic
acids a pentose sugar and a nitrogenous base. While a
nucleotide contains three basic components of nucleic acid,
a phosphoric acid, nitrogeneous base and a pentose sugar.
Nucleotides are linked together between 5' and 3' carbon
atoms of the pentose sugar by phosphodiester linkages.
• DNA molecule is a double helix structure (Watson and
Crick). The two polynucleotide strands are linked up by
hydrogen bonding between the nitrogenous base molecules
of their nucleotide monomers. Adenine links with thymine
and guanine with cytosine with the help of two and three
hydrogen bonds, respectively.
• Synthesis ofa protein involves two steps, transcription and
translation. In transcription, synthesis of RNA takes place.
While in translation, synthesis of protein occurs in
cytoplasm of a cell with the help of ribosomes.
• The DNA sequence that codes for a specific protein or a
polypeptide is called a gene. Therefore, every protein in a
cell has a corresponding gene. The relation between the
nucleotide triplets and the amino acid is called genetic code.
• DNA fingerprinting is used to determine the paternity ofan
individual, to identify the radical groups to rewrite
biological evolution, in forensic laboratories, identification
of dead bodies, etc.
• Hormones These are the chemical substances, produced
by endocrine glands in the body and are released directly in
blood stream. These are of two types steroid and
non-steroid. Steroid hormones are of two types, sex
ho1mones and adrenal cortex hormones. Insulin, oxytocin,
vasopressin, angiotensin are peptide hormones. Adrenaline
and thyroid hom1ones are the examples of amine hormone.
Deficiency of hormones causes metabolic disturbances
such as diabetes and goitre etc.
• Lipids These are waxy or oily substances having long
chain alkyl parts. Triglycerides and waxes are simple lipids
while glycolipids and lipoproteins are conjugated lipids.
Phosphoglycerides are phospholipids. Lecithin present in
egg is an example of phospholipid.
• Addition of antioxidant to oil minimises rancidity.
• Iodine value is related to oils and fats. Iodine value
measures the drying quality of oil. It is defined as number
of centegram of 12 that can be taken by 1 g of oil.
 Topic 1
Carbohydrates
2014
1. Which of the following pairs give positive Tollen's test? 7. Among the following statements about the molecules X
(a) Glucose, sucrose [VITEEE] and Y, the one(s) which is (are) correct?
(b) Glucose, fructose CHO CHO
(c) Hexanal, acetophenone
(d) Fructose, sucrose
H~i~H H~i~H
2. Which of the following compounds does not undergo H OH HO H
mutarotation? [Manipal] H OH HO H
(a) Glucose (b) Sucrose (c) Ribose (d) Fructose CH2OH CH2OH
3. If two isomers have been classified correctly as anomers, X y
they may be also called [Manipal] (a) X and Y are diastereomers [WBJEE]
(a) conformers (b) enantiomers (b) X and Y are enantiomers
(c) tautomers (d) diastereomers (c) X and Y are both aldohexoses
4. Which two of the following aldohexoses give the same (d) X is D-sugar and Y is L-sugar
osazone derivative? [Manipal] 8. The monosaccharide constituents of lactose are
CHO CHO (a) a -D-glucose and !3-D-fructose [AMU, EAMCETJ
(b) a-D-glucose
H~i~H H~i ~H (c) P-D-glucose
H OH HO H (d) P-D-glucose and P-D-galactose
H OH H OH
CH2OH CH2OH
2013
I 11 9. Synthesis of each molecule of glucose in photosynthesis

:~1= =~i=
involves [JEE Mains]
CHO CHO
(a) 18 molecules of ATP (b) 10 molecules of ATP
(c) 8 molecules of ATP (d) 6 molecules of ATP
H OH HO H 10. Glucose reacts with methyl alcohol to give [ManipalJ
H OH H OH (a) a-methyl glucoside (b) P-methyl glucoside
CH2OH CH2OH (c) Both (a) and (b) (d) None of these
III IV 11. A certain compound gives negative test with ninhydrin and
positive test with Benedict's solution, it is [DCE, KCETJ
(a) I and IV (b) I and III
(a) an amino acid (b) a monosaccharide
(c) II and III (d) III and IV
(c) a lipid (d) a protein
5. The statement that is not correct is [KCET]
12. Which of the following is an aldohexose? [KCETJ
(a) aldose or ketose sugars in alkaline medium do not
isomerise (a) Cellulose (b) Sucrose
(b) carbohydrates are optically active (c) Glucose (d) Raffinose
(c) penta acetate of glucose does not react with 13. Which of the following is an example of ketohexose?
hydroxy!amine (a) Mannose [VITEEE, OJEEJ
(d) lactose has glycosidic linkage between C 4 of glucose (b) Galactose
and C1 of galactose unit (c) Maltose
6. The carbohydrate used as storage molecule in animal is (d) Fructose
(a) sucrose (b) glycogen [Kerala CEE] 14. Glucose and mannose are [OJEEJ
(c) maltose (d) glucose (a) epimers (b) anomers
(e) fructose (c) ketohexoses (d) disaccharides
 Biomolecules I 699
2012
15. Which of the following compounds can be detected by 24. How can you say that glucose is cyclic compound?
Molisch's test? CAIEEEJ (a) Glucose undergoes Tollen's reaction [Guj CETJ
(a) Nitro compounds (b) Sugars (b) Glucose reacts with phenyl hydrazine
(c) Amines (d) Primary alcohols ( c) Glucose fails to react with sodium hydrogen sulphite
( d) Glucose reacts with nitric acid
16. Which of the following tests is performed by
carbohydrates? [Manipal] 2010
(a) Biuret test (b) Nitroprusside test 25. The correct statement about the following disaccharide
(c) Ninhydrin test (d) Molisch's test is [IITJEE]

vr:1
17. Sucrose is not a reducing sugar since [KCET]
0

"'X:H
(a) it conains no free aldehyde or keto group adjacent to a
CHOHgroup
(b) it is built up of a fructose unit
(c) it is optically active
H6H "0CH2CH20 /
~
CH20H

(d) it is chemically stable H OH OH H

(A) (B)
18. Polysaccharides have which of the following linkage?
(a) Glycosidic linkage {b) H-bond [OJEE] (a) Ring (A) is pyranose with a-glycosidic link
( c) Peptide linkage (d) No linkage (b) R ing (A) is furanose with a-glycosidic link
( c) Ring (B) is furanose with a-glycosidic link
2011 ( d) R ing (B) is pyranose with a-glycosidic link
19. The following carbohydrate is [IITJEE]
26. Which of the following hexoses will fom1 the same
H OH osazone when treated with excess phenyl hydrazine?
H--o (a) D-glucose, D-fructose and D-galactose [Manipal]
HO OH (b) D-glucose, D-fructose and D-mannose
HO (c) D-glucose, D-mannose and D-galactose
H (d) D -fructose, D-mannose and D-galactose
(a) a ketohexose (b) an aldohexose 27. Which of the following is the first member of
(c) an a-furanose (d) an a-pyranose monosaccharides? [MP PET]
20. The change in the optical rotation of freshly prepared 0
solution of glucose is known as [AIEEE] II
(a) tautomerism (b) racemisation (a) CH 2OH- C- CH 2 OH
(c) specific rotation (d) mutarotation (b)CH 2 OH- CHOH-CHO
21. a -maltose consists of [KCET] (c) CH 2 OH- CHOH- CHOH-CHO
(a) one a-D-glucopyranose unit and one 0
~D- glucopyranose unit with 1-2 glyosidic linkage II
(d) CH 2 OH-CHOH-C- CH 2 OH
(b) two a -D -glucopyranose units with 1-2 glycosidic
linkage 28. The sweetest carbohydrate is CMPPET]
(c) two ~D-glucopyranose units with 1-4 glycosidic (a) sucrose (b) glucose
linkage ( c) fructose ( d) lactose
(d) two a -D-glucopyranose units with 1-4 glycosidic
linkage 29. The letter 'D ' in D-glucose signifies [KCET]

22. In aqueous solution glucose remains as [WBJEE] (a) configuration at all chiral carbons
(b) dextrorotatory
(a) only in open chain form
(c) that it is a monosaccharide
(b) only in pyranose form
(d) configuration at a particular chiral carbon
(c) only in furanose fom1
( d) in all three forms in equilibrium 30. Which of the following compounds, when heated at 483 K
turns to caran1el? [Guj CET]
23. How glucose is related with fructose? [Guj CET]
(a) Glucose
(a) Functional group isomerism
(b) Sucrose
(b) Rotamers
( c) Fructose
(c) Position isomerism
(d) Lactose
( d) Geometrical isomerism
700 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2009
31. The two functional groups present in a typical AcO
carbohydrate are [AIEEE]
oo +
(a) - OH and - COOH AcO H H
(b) - CHO and - COOH 0 OH H
(c) C=O and - OH
( d) - OH and- CHO H O O OH H H H OH
32. A diabetic person carries a packet of glucose with him H
always, because [KCET] + o OH H H H OH
(a) glucose reduces the blood sugar level slowly
(b) glucose increases the blood sugar level slowly H OH
(c) glucose reduces the blood sugar level

9
( d) glucose increases the blood sugar level almost
Ac:~H A ~ c
Q H: Ac: OO+
instantaneously (c) H H H
33. The monosaccharides having anomeric carbon atom are + O OAc H O OAc H O OAc H H
(a) geometrical isomers [UPSEE]
(b) cx.-and ~-optical isomers H OAc H OAc H OAc
(c) having symmetrical carbon atoms
( d) None of the above
Ac:QH A o c
OH: A ~ cO:o +
34. A carbohydrate is treated with cx.-naphthol and cone. ~ H H H
H 2 SO 4 . What colour will be formed at the junction of two HH OH HO HH
liquids? [OJEE] + 0 H
(a) Blood-red (b) Violet OAc OAc OAc OAc OAc OAc
(c) Brown (d) Orange
38. cx.-D(+)-glucose and ~-D-(+)-glucose are [AIEEEJ
35. If two moles of glucose are oxidised in the body through
(a) conformers (b) epirners
respiration, the number of moles of ATP produced are
(c) anomers ( d) enantiomers
(a) 19 (b) 38 [AMU]
39. A mixture of amylose and amylopect:in is called [BITSATJ
(c) 57 (d) 76
(a) lactose (b) starch
36. Which compounds is obtained, when glucose reacts with
(c) cellulose (d) sucrose
excess C 6 H 5 - NH· NH 2 ? [Guj CET]
40. Hydrolysis of sucrose with dilute aqueous sulphuric acid
(a) Glucosazone
yields [BITSAT, AMU, EAMCETJ
(b) Gluconic acid
(a) 1 : 1 D-(+)-glucose; D-(- )-fructose
(c) Glucose phenyl hydrazone
( d) Saccharic acid (b) l : 2 D-(+)-glucose; D-(- )-fructose
(c) 1 : 1 D-(- )-glucose; D-(+)-fructose
2008 (d) 1 : 2 D-(- )-glucose; D-(+)-fructose
37. Cellulose upon acetylation with excess acetic anhydride/ 41. Milk changes after digestion into [VITEEEJ
H 2 S0 4 (catalytic) gives cellulose triacetate whose (a) cellulose (b) fructose
structure is [IIT JEE] ( c) glucose ( d) lactose
AcO
42. Which of the following does not form an oxin1e?
O
AcO H:}- 1+ (a) Glucose
(b) Glucose pentaacetate
[ManipalJ

AcO H: ; r - o \ / O H H ( c) Arabi nose

( d) Galactose
(a) ~0\/oHH H OAc
43. Glucose molecule reacts with 'X' number of molecules of
phenyl hydrazine to yield osazone. The value of 'X' is
+ o HH H OAc
(a) four (b) one [MHT CETJ
H OAc (c) two (d) three
 Biomolecules I 701
44. Which set of terms correctly identifies the carbohydrate 54. Which one of the following is an example of a
shown? non-reducing sugar? [J&K CET]
(a) Sucrose (b) Lactose
( c) Maltose ( d) Cellobiose
55. Methyl cx.-D-glucoside and methyl- j3-D-glucoside are
HOH,~ H
(a) epimers [BCECE]
(b) anomers
H OH ( c) enantiomers
T. Pentose TT. Hexose ( d) conformational diastereomers
III. Aldose IV. Ketose
56. Iodine test is shown by [BCECE]
V. Pyranose VI. Furanose [Kerala CEE]
(a) glucose (b) starch
(a) I, III and VI (b) I, III and V
(c) glycogen (d) polypeptide
(c) II, III and V (d) II, III and VI
(e) 1, IV and VI 2006
45. Diabetes is detected, using . . . . . . for testing mine of 57. The te1m anomers of glucose refers to [AIEEE]
patients. [OJEE] (a) isomers of glucose that differ in configurations at
(a) Fehling's solution (b) Tollen's reagent carbons one and four (C-1 and C-4)
(c) Benedict's solution (d) Baeyer's reagent (b) a mixture of(D)-glucose and (L)-glucose
46. The anomeric carbon in D(+) glucose is [J&K CETJ ( c) enantiomers of glucose
(d) isomers of glucose that differ in configuration at
(a) C-1 carbon (b) C-2 carbon carbon-one (C-1)
(c) C-5 carbon (d) C-6 carbon
58. Main constituent of plants is [BITSAT]
47. Glucose contains in addition to aldehyde group
(a) cellulose (b) starch (c) fructose (d) lipids
[Jamia Millia Islamia]
59. When glucose reacts with bromine water the main product
(a) one secondary OH and four primary OH groups is [BITSAT]
(b) one primary OH and four secondary OH groups
(a) gluconic acid (b) glyceraldehyde
(c) two primary OH and three secondary OH groups
(c) sorbitol (d) saccharic acid
(d) three primary OH and two secondary OH groups
60. Raffinose is [MP PET]
2007 (a) trisaccharide (b) disaccharide
48. Which of the following indicates open chain structure of ( c) monosaccharide (d) polysaccharide
glucose? [BITSAT] 61. Glucose is a/an CUPSEE]
(a) Pentaacetyl derivative of glucose (a) polyhydroxy ketone (b) alcohol
(b) Cyanohydrin formation with HCN ( c) hydrate of carbon (d) pentahydroxy aldehyde
(c) Reaction with Fehling's solution
62. Lactose gives on hydrolysis [Guj CET]
(d) Reaction with Tollen's reagent
(a) glucose
49. Cellulose is a polymer of [BITSAT] (b) glucose and galactose
(a) glucose (b) fructose (c) ribose (d) sucrose (c) fructose
50. Number of chiral carbon atoms in ~-D-(+)- glucose is ( d) glucose and fructose
(a) five {b) six [Manipal] 63. All monosaccharides ...... Tollen's reagent. [J&K CET]
(c) three (d) four (a) oxidises (b) condense with
51. Sucrose on hydrolysis gives [MHTCET] (c) reduces (d) add to
(a) glucose and maltose (b) glucose and lactose 2005
(c) glucose and fructose (d) only glucose
64. The two fom1s of D-glucopyranose obtained from the
52. Glucose gives silver mirror with arnmoniacal silver nitrate solution ofD-glucose are called [IIT JEE]
because it has [MHT CET]
(a) isomers (b) anomers
(a) aldehyde group (b) ester group ( c) epimers ( d) enantiomers
(c) ketone group {d) alcoholic silver nitrate
65. Which of the following compounds is folll1d ablll1dantly in
53. Complete hydrolysis of cellulose gives [MP PET] nature? [Manipal]
(a) D-fructose (b) D-ribose (a) Fructose (b) Starch (c) Glucose (d) Cellulose
(c) D-glucose (d) L-glucose
702 I Chapterwise & Topicwise Engineering Entrances Solved Papers

66. Water insoluble component of starch is [KCET] 70. Which of the following enzymes hydrolysis starch to
(a) amylopectin {b) amylose glucose? [AMU]

(c) cellulose (d) None of these (a) Amylase (b) Invertase

(c) Lactase (d) Maltase
67. Sucrose molecule is made up of [KCET]
(a) a glucopyranose and a fructopyranose 71. An organic compound answers Molisch's test as well as
(b) a glucopyranose and a fructofuranose Benedict's test. But it does not answer Seliwanoffs test.
Most probably, it is [Guj CETJ
(c) a glucofuranose and a fructopyranose
(d) a glucofuranose and a fructofuranose (a) sucrose (b) protein (c) fructose (d) maltose
68. Ribose is an example of [UPSEE] 72. Energy is stored in our body in the form of [Guj CETJ
(a) ketohexose (b) disaccharide (a) ATP (b) ADP
(c) pentose (d) polysaccharide ( c) fats ( d) carbohydrates
69. The carbohydrate that will yield glucose and fructose on 73. Which is incorrect? [J&K CETJ
homogeneous catalytic hydrolysis in the presence of dilute (a) Glucose is a disaccharide
sulphuric acid is [AMU] (b) Starch is a polysaccharide
(a) cellulose (b) maltose ( c) Glucose and fructose are not anomers
(c) starch (d) sucrose (d) Invert sugar consists of glucose and fructose

Topi c 2
Proteins and Enzymes
2014 2013
1. The number of disulphide linkages present in insulin are 5. A tetrapeptide has - COOH group on alanine. This
[BITSAT, KCET] produces glycine (Gly), valine (Val), phenyl alanine (Phe)
(a) I (b) 2 (c) 3 (d) 4 and alanine (Ala), on complete hydrolysis. For this
2. Which of the following describes the overall three tetrapeptide, the number of possible sequences (primary
dimensional folding of a polypeptide? [Manipal] structures) with - NH 2 group attached to a chiral centre is
[JEE Advance d]
(a) Primary structure
(a) 7 (b) 5 (c) 4 (d) 8
(b) Secondary structure
(c) Tertiary structure 6. A compound with molecular mass I 80 is acylated with
( d) Quaternary structure CH 3 COCI to get a compound with molecular mass 390.
The number of amino groups present per molecule of the
3. 1.78 g of an optically active L-amino acid (A) is treated
former compound is [JEE Mains]
with NaNO 2 / HCI at 0° C, 448 cm 3 of nitrogen was at STP
(a)2 (b)5 (c)4 (d)6
is evolved. A sample of protein has 0.25% of this amino
7. a-helix is found in [Ke rala CEE]
acid by mass. The molar mass of the protein is
(a) DNA (b) RNA (c) lipid
(a) 36500 g mol - 1
( d) carbohydrates (e) protein
(b) 34500 g mol - 1 [KCET]
(c) 35400g rno1- 1 2012
(d) 35600 g mol - 1 8. The substituents R1 and R2 for nine peptides are listed in
the table given below. How many of these peptides are
4. The number of amino acids and number of peptide bonds positively charged at pH = 7.0?
in a linear tetrapeptide (made of different amino acids, are EB
respectively [WBJEEJ H 3 N- CONH- CH- CONH- CH- COONH
(a) 4 and 4 (b) 5 and 5 I I I
(c)5and4 (d)4and3 H EB
- CH- COO
I
H
 Biomolecules I 703
Peptide 17. An electric current is passed through an aqueous solution
I H H of a mixture of alanine (isoelectric point 6.0) glutamic acid
(3.2) and arginine (10.7) buffered at pH 6. What is the fate
II H CH3
of the three acids? [WB JEE]
III CH2COOH H
(a) Glutamic acid migrates to anode at pH 6 . Arginine
N CH2CONH2 (CH2)4NH2 p resent as a cation and migrates to the cathode
V CH2CONH2 CH 2CONH2 Alanine in a dipolar ion remains uniformly
VI (CH2)4NH2 (CH2)4NH2 distributed in solution
VII CH2COOH CH 2CONH2 (b) Glutamic acid migrates to cathode and others remain
uniformly distributed in solution
VIII CH20H (CH2)4NH2 (c) All three remain uniformly distributed in solution
IX (CH 2)4NH2 CH3 ( d) All three move to cathode
[IITJEE] 18. Which of the following is present in animals like cow,
(a) 2 (b) 4 (c) 6 (d) 8 buffaloes etc. to digest compound like paper, cloth etc?
9. Dialysis can be used to separate [KCET] (a) Urease (b) Cellulase [Guj CETJ
(c) Silicones (d) Sucrose
(a) protein and starch (b) glucose and protein
(c) glucose and NaCl (d) glucose and fructose 2010
10. Which of the following is a simplest amino acids? [OJEE] 19. The total number of basic groups in the following form of
(a) Glycine (b) Alanine lysine is
(c) Leucine (d) Valine +
H 3N - CH 2 - CH 2 - CH2 - H2C O
11. Which of the following element is present in haemoglobin?
\CH- C// [IIT JEE]
(a) Na (b) Ca [OJEE, J&K CET]
I \
(c) Fe (d) Au H 2N o-
12. Which one of the following statements is correct? [AMU] 001 ~2 ~3 ~4
(a) All amino acids except lysine are optically active 20. Biuret test is not given by [AIEEE]
(b) All amino acids are optically active
(a) carbohydrates (b) polypeptides
(c) All amino acids except glycine are optically active
(d) All amino acids except glutamic acids are optically (c) urea ( d) proteins
active. 21. Which one of the following is not a protein? [Manipall
13. Hydrolysis of proteins give [AMU] (a) Wool (b) Nail
(a) a-amino acids (c) Hair (d) DNA
(b) P-amino acids 22. The enzyme pepsin hydrolyses [Manipal]
(c) y-amino acids (a) proteins to amino acids
(d) mixture ofall, i.e.a, Py-amino acids (b) fats to fatty acids
(c) glucose to ethyl alcohol
2011 (d) poloysaccharides to monosaccharides
14. A decapeptide (mol. wt. 796) on complete hydrolysis gives
23. In alkaline medium, alanine exits predominantly as
glycine (mol. wt. 75), alanine and phenylalanine. Glycine
contributes 47% to the total weight of the hydrolysed (a) anion (b) Zwitter ion [KCETJ
products. The number of glycine units present in the ( c) cation ( d) covalent form
decapeptide is [Irr JEE]
24. Give the pOH range for the isoelectric point of the
003 ~4 ~5 ~6 amphoteric ion of an amino acid [Guj CETJ
15. In an alkaline medium, glycine predominantly exists as/in (a) 5.5 to 6.3 (b) 2 .5 to 5.0
a/an [KCET] (c) 7.7 to 8.5 (d) 9.0 to 10.7
(a) cation (b) anion
25. Denaturation of proteins leads to the loss of its biological
(c) Zwitter ion (d) covalent form activity by [JCECE]
16. Which one of the following does not correctly match with (a) formation of amino acids
each other? [KCET] (b) loss of primary structure
(a) Silk-polyamide (b) Lipase-enzyme (c) loss of both primary and secondary structures
(c) Butter-fat (d) Oxytocin-enzyme (d) loss of both secondary and tertiary stuctures
704 I Chapterwise & Topicwise Engineering Entrances Solved Papers
2009
26. There are 20 naturally occurring amino acids.The 33. Which amino acid has irnidazole ring? [OJEEJ
maximum number of tripeptides that can be obtained is (a) Alanine (b) Leucine
(a) 8000 {b) 6470 [OJEEJ ( c) Tyrosine ( d) Histidine
(c) 7465 (d) 5360 34. Helical structure of protein is stablilised by [OJEEJ
27. Sanger's method is used to identify [OJEEJ (a) peptide bond (b) hydrogen bond
(a) C-terminal amino acid (b) N -terminal amino acid (c) van der Waals' force (d) dipole association
( c) side chain (d) molecular weight protein 35. Which one of the following statements about amino acids
is not trne? [Guj CETJ
2008
(a) They are constituents of all proteins
28. Which of the following is a heterocyclic amino acid? (b) They are all high m elting solids
(a) Glycine (b) A lanine [DCEJ (c) Most naturally occurring amino acids have
(c) Phenylalanine (d) Tryptophan D-configuration
29. Which of the following set consists only of essential amino ( d) They are characterised by isoelectric point
acids? [VITEEEJ 36. The a-amino acid which does not give purple colour in the
(a) Alanine, tyrosine, cystine ninhydrin test is [J&K CET]
(b) Leucine, lysine, tryptophane (a) proline (b) glycine (c) lysine (d) aspartic acid
(c) Alanine, glutamine, lycine 37. At pH = 4, glycine exists as [Jam.ia Millia Islamial
(d) Leucine, proline, glycine + +
(a) H 3N - CH 2 - COO- (b) H 3 N - CH 2 - COOH
30. The compound, which give a positive ninhydrin test and a
negative Benedict's solution test, is [MHT CETJ (c) H 2 N - CH 2 - COOH (d) H 2 N - CH 2 - COO-
(a) a monosaccharide (b) a disaccharide
( c) a lipid (d) a protein
2007
38. The secondary structure of a protein refers to [AIEEEJ
31. A tripeptide is written as glycine-alanine-glycine. The
correct structure of the tripeptide is [WB JEE] (a) a-helical backbone
0 CH3 (b) hydrophobic interactions
(c) sequence of a -amino acids
(a) NH, l (NH~NH}-___ COOR (d) fixed configmatjon of the polypeptide backbone
39. Which one is the correct representation of peptide bond?
0 CH3 0 0
II II
(a) H- C- N- (b) - C- N - [BITSATJ
CH3 0 CH3
I I I
NH/~( NH ~ NH A
H
(b) COOH OH
I
0 (c)H- C- N - ( d) None of these
0 1 I

(c) NH,l(NH~Nw''--coon 40. In aqueous solution, amino acids mostly exist as [BITSATJ
(a) NH 2 - CHR- COOH (b) NH2 - CHR- COO-
0 CH3 + +
CH3 0 (c) NH 3- CHR- COOH (d) NH 3- CHR- C00-
41. Which one of the following structures represents the
(d) NH2 ~(NH~ NH---------cooH peptide chain ? [UPSEE, Manipall
H 0
0 CH3
I I II
32. A Zwitter ion is [UPSEEJ (a) - N - C- N- C- NH- C- NH- 0
(a) negatively charged ion without metal atom II I I
0 H
(b) a heavy ion with a small charge on it
H H
(c) an ion with positive and negative charge at different
points on it
I I I I I I I I
(b) - N - C- C- C- C- N - C- C- C
(d) a positively charged ion without a metal atom II I I I I I I
0
 Biomolecules I 705
H H H H 53 . Which of the following exists as Zwitter ion ?
I I I I I I I I (a) p-aminophenol [Ke rala CEEJ
(c) - N- C- C- N -C- C- N - C- C- N - C-
1 II I II I I II I (b) Salicylic acid
0 0 0 (c) Sulphanilic acid
(d) (d) Ethanolamine
H O H
(e) p-amino acetophenone
I I I I II I I I I I
- C- N - C- C- C- N - C- C- N- C- C- C- 54. Which of the following compound shows aromatic
1 I I I I I II I I properties? [WBJEEJ
H 0
(a) Valine (b) Leucine
42. The correct statement in respect of protein haemoglobin is (c) Serine (d) Tyrosine
that it [Manipal]
55. Amino acids have peptide linkage which is [WB JEE]
(a) functions as a catalyst for biological reactions
(a) - CO- NH- (b) - C- NH 2
(b) maintains blood sugar level
(c) SO- NH- (d) - CO- N -
(c) act as an oxygen carrier in the blood
(d) forms antibodies and offers resistance to diseases 56. Proteins are CUPSEEJ
43. Protein gives blue colour with [MHT CET] (a) polypeptides with low molecular weights
(b) polypeptides with high molecular weights
(a) benedict reagent (b) iodine solution
(c) polymers of amides
(c) ninhydrin (d) biurete
(d) polymers of secondary amines
44. Zwitter ion is fo1med by [MHTCET]
57. Pick out the one which does not belong to the fan1ily.
(a) aniline (b) acetanilide
(a) Pepsin (b) Cellulose [AMUJ
(c) benzoic acid (d) glycine
(c) Ptyalin (d) Lipase
45. The amino acid which is not optically active is [KCET]
58. An achiral amino acid [Guj CETJ
(a) lactic acid (b) serine
(c) alanine (d) glycine (a) alanine (b) valine (c) leucine (d) glycine
46. Which functional group participates in disulphide bond 59. The product formed in the reaction of glycine with benzoyl
formation in proteins? [UPSEEJ chloride + aq. NaOH is [J&K CETJ

(a) Thiolacetone (b) Thiol (a) PhCOCH 2 NH 2 (b) PhCH 2NH 2

(c) Thioether (d) Thioester (c) PhCONHCH 3 (d) PhCONHCH2C0 2H

47 . Which amino acid has phenyl- OH group? [OJEEJ 2005

(a) Lysine (b) Arginine (c) Proline (d) Tyrosine 60. Which of the following is an amphoteric acid? [KCETJ
48. Which of the following biomolecules acts as specific (a) Glycine (b) Salicylic acid
catalysts in biological reaction ? [EAMCET] (c) Benzoic acid (d) C itric acid
(a) Carbohydrates (b) Lipids 6 1. A nanopeptide contains .... .. peptide linkages. [KCETJ
(c) Vitamins (d) Enzymes (a) 10 (b) 8 (c) 9 (d) 18
49. Polypeptides having molecular weights above 10000 are 6 2. An example of a sulphur containing amino acid is [KCETJ
known as [J&K CET]
(a) lysine (b) serine (c) cysteine (d) tyrosine
(a) amino acids (b) hormones
63. The enzyme that is used to dissolve blood clot is [AMUJ
(c) proteins (d) terminal amino acids
(a) trypsin (b) renin
50. Which one of the following is a conjugated protein? (c) streptokinase (d) tyrosinase
(a) Phosphoprotein (b) Glycoprotein
64. Peptides are formed from [J&K CETJ
(c) Chromoprotein (d) All of these
(a) aliphatic amines (b) carbohydrates
2006 (c) a -amino acids (d) aromatic amines
51. Which destroy antigens? [BITSAT] 65. A substance forms Zwitter ion. It can have functional
(a) Insulin (b) Antibodies groups [Jamia Millia Islamia]
(c) Chromoprotein (d) Phosphoprotein (a) - NH2 , - COOH
52. The main structural feature of protein is [MP PET] (b) - NH2, - S03H
(c) Both (a) and (b)
(a) ester linkage (b) ether linkage
(d) None of the above
(c) peptide linkage (d) All of these
 Topic 3
Nucleic Acids, (DNA, RNA) and Protein Synthesis
2014
1. Which one of the following bases is not present in DNA? 10. Monomer of nucleic acid is [AMU]
(a) Quinoline (b) Adenine [JEE Main] (a) nucleotides (b) nucleoxides
(c) Cytosine (d) Thymine (c) aminoacids (d) carboxylic acid
2. The sugar moiety present RNA molecule is [Kerala CEE] 11. Which base is present in RNA but not in DNA ?
[Jamia Millia Islamia]
(a) P-D-2-deoxyribose (b) P-D-galactose
(a) Uracil (b) Cytosine (c) Guanine (d) Thymine
(c) P-D-fructofuranose (d) P-D-ribose
(e) P-D-glucopyranose 2006
3. In DNA, the consecutive deoxynucleotides are connected 12. The pyrimidine bases present in DNA are [AIEEEJ
via [WBJEE] (a) cytosine and adenine (b) cytosine and guanine
(a) phosphocliester linkage (c) cytosine and thymine (d) cytosine and uracil
(b) phosphomonoester linkage 13. The purine base present in RNA is [BITSATJ
(c) phosphotriester linkage
(a) guanine (b) thymine (c) cytosine (d) uracil
(d) amide linkage
14. Which one of the following is not present in RNA?
2012 (a) Uracil (b) Thymine [Manipal]
4. Which of the following will explain synthesis of RNA? (c) Ribose (d) Phosphate
(a) Translation (b) Coagulation [Manipal] 2005
(c) Transcription (d) Replication 15. In both DNA and RNA, heterocylic base and phosphate
ester linkages are at [AIEEEJ
2011
5. The presence or absence of hydroxy group on which
(a) C~ and c;
respectively of the sugar molecule
carbon atom of sugar differentiates RNA and DNA ? (b) c; and C~ respectively of the sugar molecule
(a) I st (b) 2nd [AIEEE] (c) C~ and C~ respectively of the sugar molecule
(c)3rd (d)4th (d) C~ and c; respectively of the sugar molecule
6. Which one is not a constituent of nucleic acid? [WB JEE]
16. How many hydrogen bonds are present between pair of
(a) Uracil thymine and adenine in DNA ? [BITSAT]
(b) Guanidine (a) I -hydrogen bond (b) 2-hydrogen bonds
(c) Phosphoric acid (c) 3-hydrogen bonds (d) No bonds occur
(d) Ribose sugar 17. Which of the following is not present in a nucleotide?
2007 (a) Cytosine (b) Guanine [KCETJ
(c) Adenine (d) Tyrosine
7. A sequence of how many nucleotides in messenger RNA
18. In biological systems, the RNA molecules direct the
makes a codon for an amino acid ? [UPSEE, Manipal]
synthesis of specific proteins which are characteristics of
(a) Three (b) Four each kinds of organism. This process is known as
(c) One (d) Two (a) transcription (b) mutation [Kerala CEEJ
8. The reason for double helical structure of DNA is (c) replication (d) translation
operation of [MP PET] (e) flocculation
(a) van der Waals' forces 19. If one strand of DNA has the sequence TATGACTG, the
(b) dipole-dipole interaction sequence in the complimentary strand would be [AMUJ
(c) hydrogen bonding (a)ATACAC T C (b)ACGTTGAC
(d) electrostatic attractions (c)ATACTGAC (d)ATACTGCA
9. Which of the following is true? [OJEE] 20. RNA contains [Jamia Millia Islamia]
(a) Nucleoside + phosphoester bond= nucleotide (a) ribose sugar and thymine
(b) DNA's are nucleotide and RNA's are nucleoside (b) ribose sugar and uracil
(c) Nucleotide + phosphoester bond= nucleoside (c) deoxyribose sugar and uracil
(d) None of the above (d) deoxyribose sugar and thymine
 Topic 4
Lipids, Vitamins, Hormones and Pigments
2012 9. Match the following Columns.
1. Which of the following hormone, is responsible for the Column I Column IT
growth of animals? [BITSAT] A. Vitamin A I. Scurvy
(a) Auxin {b) Insulin B. Vitamin B 12 2. Hemorrhagic condition
(c) Adrenaline (d) Somatotropin C. Vitamin C 3. Sterility
2. Metabolic function in hwnan bodies is carried out by D. Vitamin E 4. Xerophthalmia
(a) lipids (b) peptides IMP PET] E. Vitamin K 5. Pernicious anaemia
(c) nucleic acid (d) enzymes
Codes [Kerala CEE]
2011 A B C D E
3. Progesterone is secreted by ... .... [Guj CET] (a) 3 4 5 2 l
(a) thyroid {b) ovaries (b) 3 4 5 I 2
(c) adrenal (d) testes (c) 4 5 I 3 2
(d) 3 5 4 2 2
2010 (e) 4 5 3 I 2
4. Lipids are [Manipal] 10. Which of the following compounds is not of the
(a) nucleic acids occurring in plants lipid series ? [MPPET]
(b) proteins occurring in animals (a) Fat (b) Soap
(c) carbohydrates occurring in plants (c) Oil (d) Lard
(d) fats of natural origin 11. Dalda is prepared from oils by IKCET]
5. Which one of the following statements is true? [KCETJ (a) oxidation (b) reduction
(a) Saponification of oil yields a diol (c) hydrolysis (d) distillation
(b) Drying ofoil involves hydrolysis
2009
(c) Addition of antioxidant to oil minimises rancidity
(d) Refining of oil involves hydrogenation 12. Mammals' fats are hydrolysed to relase fatty acids by
6. Night-blindness may be caused by the deficiency of (a) amylase (b) lactase [AMU]

vitamin [Punjab CET] (c) lipase (d) insulin

(a) A (b) B (c) C (d) D 13. The one which has least iodine value is [Guj CET]

7. Match the following Columns. (a) sunflower oil (b) ginger oil
(c) ghee (d) groundnut oil
Column I Column IT 14. Iodised salt prevents . . . . . . . . . [Guj CET]
A. Vitamin-B 12 I. Sterility (a) TB (b) anaemia
B. Vitamin-B6 2. Haemorrhagic condition (c) goitre (d) beri-beri
C. Vitamin-E 3. Pernicious anaemia 15. Which lipid is not obtained by the hydrolysis of simple
lipid and compound lipid from the following? [Guj CET]
D. Vitamin-K 4. Skin disease
(a) Cholesterols (b) Neutral fats
Codes [Guj CET] (c) Carotenoids (d) Terpenes
A B C D A B C D 2008
(a) I 2 3 4 (b) 2 3 4 I
(c) 3 4 I 2 (d) 3 4 2 I 16. Waxes are esters of [KCETJ

8. The chemical name of vitamin B1 is (a) glycerol

[JCECE]
(b) long chain alcohols
(a) ascorbic acid {b) riboflavin (c) glycerol and fatty acid
(c) pyridoxine (d) thiamine (d) long chain alcohols and long chain fatty acids
708 I Chapterwise & Topicwise Engineering Entrances Solved Papers
17. Which one of the following is a non-steroidal hormone? Codes [Kerala CEE]
(a) Estradiol [Ke rala CEE] A B C D E
(b) Prostaglandin (a) 4 3 1 5 2
( c) Progesterone (b) 5 3 4 I 2
(d) Estrone (c) 3 2 I 5 4
(e) Testosterone (d) 2 4 I 3 5
(e) I 5 4 2 3
18. Insulin regulates the metabolism of [Jamia Mil1ia Islamial
29. Phospholipids are esters of glycerol with [UPSEEJ
(a) minerals (b) amino acids
(a) one carboxylic acid residue and two phosphate groups
( c) glucose (d) vitamins
(b) three phosphate groups
19. A distinctive and characteristic functional group of fats is (c) three carboxylic acid residues
(a) a peptide group [Jamia Mi llia Islamia] (d) two carboxylic acid residues and one phosphate
(b) an ester group groups
( c) an alcoholic group 30. Hardening of fat (lipid) is due to [OJEEJ
( d) a ketonic group (a) hydrogenation (b) dehydrogenation
( c) halogenation ( d) dehydrohalogenation
2007
31. Insulin production and its action in human body are
20. Iodine value related to [BITSAT]
responsible for the level of diabetes. This compound
( a) fats and oils (b) alcohols belongs to which of the following categories ?
(c) esters (d) hydrocarbons [Jamia Millia Islamia]
21. The hormone that helps in the conversion of glucose to (a) a coenzyme (b) a hom1one
glycogen is [Manipall ( c) an enzyme (d) an antibiotic
(a) cortisone (b) bile acids 32. Vitamin B 6 is known as [Manipal]
(c) adrenaline (d) insulin
(a) Pyridoxin (b) Thiamine
22. The enzyme which hydrolysis triglycerides to fatty acids
(c) Tocopherol (d) Riboflavin
and glycerol is called [Manipall
(a) maltase (b) lipase (c) zymase (d) pepsin 2006
23. Fats are ester of [MIITCET] 33. Which one of the following is an ester ? [UPSEEJ
(a) sugar (b) glycerol (a) Coconut o il (b) Kerosene oil
( c) tributyrine (d) polypeptide (c) Soap (d) Glycerine
24. Wax is [MPPETJ 34. Calciferol is [Guj CETJ
(a) alcohol (b) ester (c) ketone (d) acid (a) vitamin (b) antibiotic
25. The process used in the conversion oftriolein to tristearin is (c) hormone ( d) antipyretic
(a) hydrolysis (b) hydration [MP PET] 2005
(c) hydrogenation (d) dehydrogenation
35. An example for a saturated fatty acid, present in nature is
2 6. A metal present in vitamin B 12 is [KCET, B CECEJ
(a) oleic acid (b) linoleic acid [KCETJ
(a) aluminium (b) zinc (c) linolenic acid (d) palmitic acid
(c) iron (d) cobalt
36. Which of the following biomolecules contain
27. Acrolein test is positive for [KCET] non-transition metal ion ? [KCETJ
(a) polysaccharides (b) proteins (a) Vitamin B12 (b) Chlorophyll
(c) oils and fats (d) reducing sugars ( c) Haemoglobin (d) Insulin
28. Match the following Columns. 37. Which of the following compounds is known as the
Columns I Columns JI antisteri.lity factor ? (AMUJ

A. Thymine 1. Pyrimidine base

(a) ex,-tocopherol (b) Retinol
(c) Calciferol (d) Pyridoxine
B. Thiamine 2. Enzyme
C. Insulin 3. Cell-wall component
38. Which of the following hormones is excreted from adrenal
co11ex ? [AMUJ
D. Pepsin 4. Hormone
(a) Cortisone (b) Estrogen
E. Phospholipids 5. Vitamin B 1
( c) Progesterone ( d) Testosterone
 Biomolecules I 709
39. Which of the following is not co1Tect? [EAMCET] 40. The tripeptide hormone present in most living cells is
(a) Chlorophyll is responsible for the synthesis of (a) glutathione (b) glutamine [Guj CET]
carbohydrates in plants (c) oxytocin (d) ptyalin
(b) The compound formed in the addition of oxygen to 41. Ascorbic acid is also known as [J&K CETJ
haemoglobin is called oxyhaemoglobin
(a) vitamin A (b) vitamin B
(c) Acetyl salicylic acid is known as aspirin
(c) vitamin C (d) vitamin D
(d) The metal ion present in vitamin B12 is Mg 2+
42. Fat on hydrolysis gives which alcohol ? [BCECEJ
(a) Glycerol (b) Propanol (c) Butanol (d) Ethanol

Answers
TOPICl Carbohydrates
1. (b) 2. (b) 3. (d) 4. (b) 5. (a) 6. (b) 7. (b,c,d) 8. (d) 9. (a) 10. (c)
11. (b) 12. (c) 13. ( d) 14. (a) 15. (b) 16. (d) 17. (a) 18. (a) 19. (b) 20. (d)
21 . ( d) 22. (d) 23. (a) 24. (c) 25. (a) 26. (b) 27. (b) 28. (c) 29. (d) 30. (b)
31 . (c,d) 32. (d) 33. (b) 34. (b) 35. (d) 36. (a) 37. (a) 38. (c) 39. (b) 40. (a)
41 . (c) 42. (b) 43. (d) 44. (a) 45. (c) 46. (a) 47. (b) 48. (a) 49. (a) 50. (a)
51 . ( c) 52. (a) 53. (c) 54. (a) 55. (b) 56. (b) 57. (d) 58. (a) 59. (a) 60. (a)
61 . ( d) 62. (b) 63. (c) 64. (b) 65. (d) 66. (a) 67. (b) 68. (c) 69. (d) 70. (a)
71 . ( d) 72. (a) 73. (a)
TOPIC2 Proteins and Enzymes
1. (b) 2. (c) 3. (d) 4. (d) 5. (c) 6. (C) 7. (e) 8. (b) 9. (b) 10. (a)
11. (c) 12. (c) 13. (a) 14. (d) 15. (b) 16. (d) 17. (a) 18. (b) 19. (b) 20. (a)
21. ( d) 22. (a) 23. (a) 24. (c) 25. (d) 26. (a) 27. (d) 28. (d) 29. (b) 30. (d)
31. (c) 32. (c) 33. (d) 34. (b) 35. (c) 36. (a) 37. (b) 38. (a) 39. (b) 40. (d)
41. (c) 42. (c) 43. (c) 44. (d) 45. (d) 46. (b) 47. (d) 48. (d) 49. (c) 50. (d)
51. (b) 52. (c) 53. (c) 54. (d) 55. (a) 56. (b) 57. (b) 58. (d) 59. (d) 60. (a)
61. (b) 62. (c) 63. (c) 64. (c) 65. (c)
TOPIC3 Nucleic, Acids, (DNA, RNA) and Protein Synthesis
1. (a) 2. (d) 3. (a) 4. (c) 5. (b) 6. (b) 7. (a) 8. (c) 9. (a) 10. (a)
11. (a) 12. (c) 13. (a) 14. (b) 15. (a) 16. (b) 17. (d) 18. (d) 19. (c) 20. (b)
TOPIC4 Lipids, Vitamins, Hormones and Pigments
1. (d) 2. (d) 3. (b) 4. (d) 5. (c) 6. (a) 7. (c) 8. (d) 9. (c) 10. (b)
11. (b) 12. (c) 13. (c) 14. (c) 15. (b) 16. (d) 17. (b) 18. (c) 19. (b) 20. (a)
21. ( d) 22. (b) 23. (b) 24. (b) 25. (c) 26. (d) 27. (c) 28. (e) 29. (d) 30. (a)
31. (b) 32. (a) 33. (a) 34. (a) 35. (d) 36. (b) 37. (a) 38. (a) 39. (d) 40. (a)
41. (c) 42. (a)
 Explanations
Topic 1 Carbohydrates
1. Aldehydes and a-hydroxy ketones give positive Tollen's test.
Glucose is a polyhydroxy aldehyde and fructose is an a-hydroxy
ketone.
2. Sucrose does not have free hemiacetal group, so does not undergo
mutarotation.
3. Anomers differs in configuration only at C-1 carbons, they are
simultaneously diastereomers.
4. I and III are C-2 epimers. C-2 epimers give same osazone on
treatment with phenylhydrazine.
5. Aldose and ketose sugars in alkaline medium may isomerises.
Aldose and ketose sugar undergo isomerisation in the presence of
alkaline solution of alkaline earth aluminate catalyst.
6. In animals, the excess glucose is stored in the form of glycogen,
which is synthesised and stored mainly in liver and muscles.
Glycogen consists of long polymeric chains of glucose units
connected by an alpha acetal linkage.
7. Both the given molecules contain 6 carbon atoms with an
aldehyde group, so these are called aldohexoses. In X, the - OH
attached to second last carbon is on right hand side while in Y it is
on left hand side, so Xis D-sugar and Yis L-sugar. X and Y are the
mirror images of each other, i.e. these are enantiomers.
8. Lactose on hydrolysis with dilute acid, produces an equimolar
mixntre of !3-D (+) -glucose and !3-D (+ }-galactose, thus, its
monosaccharide constituents are P -D-glucose and P -D-galactose.
HOQCH20H H H r 2::H
I -H2 0
H the disaccharides (except sucrose) are reducing agent.
5 Sucrose does not have free aldehyde or keto group adjacent to
H OH CH20H
'3-D(+ )-galactose 6
'3-D(+)-glucose
(+)-lactose
11. Monosaccharides gives positive test with Benedict's solution
because they are reducing sugars but they give negative test with
ninhydrin because this test is performed by proteins, peptides and
amino acids.
12. In carbohydrate chemistry, the chain of six carbon atoms is aldose
and having a group ofaldehyde is known as aldohexose, as glucose.
13. The term hexose refers to the presence of six carbon atoms and
term keto shows the presence of ketonic group. Thus, the
compound which contains 6 C atoms and one ) C =0 group is
called ketohexose. Among the given only glucose and frnctose
are six carbon containing compounds. Out of them, glucose
contains an aldehyde group w hile frnctose contains a ketonic
group. Hence, the example of ketohexose is frnctose.
14. Carbohydrates which differ in configuration at a carbon other
than tJ1e anomeric carbon differ in configuration around C2 and
hence these are C2 epiners.
15. Molisch's test is for carbohydrates. Add two drops of alcoholic
solution of a-naphthol to the carbohydrate solution under study.
Add cone. H 2S04 slowly by the side of the test tube. A violet ring
is formed at the junction of the two liquids if carbohydrate is
present.
16. Molisch's test is a general test for carbohydrates while ninhydrin
test is given by all proteins. Nitroprnsside test is given by proteins
which contains - SH group. Due to the presence of - CONH
linkage, alkaline solution of proteins give biuret test.
17. Carbohydrates which can reduce Toll en's reagent or Fehling's
solution are called reducing sugars. All the monosaccharides and
) CHOH group, therefore it fails towards Tollen's reagent
and Fehling' s solution.
18. In polysaccharides, different monosaccharide units are linked to
one another by glycosidic linkages. e.g.amylose and amylopectin
are composed ofo-D glucose units linked by glycosidic linkage.
19. Here, the-OH ofhemiacetal group is equatorial therefore, it is a
!3-pyranose of an aldohexose.
20. A spontaneous change in the specific rotation of a solution of an
optically active compound is called mutarotation. Hemiacetal
forms ofo and !3-D-glucose are stable in solid state but in aqueous
solution, there is opening of the cyclic structure which gives
solution of constant specific rotation.

:;o:
9. 6C02 + 12 NADPH + 18 ATP ~ (;H 1z06

:~+c~~ ~
+ 12 NADP + 18 ADP
10. Glucose reacts with CH 30H in the presence of dry HCI gas to
give a and P-methyl glucoside.
H~ffl
OH
HO H ---->.
..--- HO H
H OH H OH H OH
½H 110 5 ·OH + HOCH 3
DryHCI
~ C6H 1.05 · OCH3 + H 20 H 0 H OH H
Glucose 0. and !3-rrethyl CH2OH CH 2OH CH 2OH
glucoside 13-D-glucose O-glucose a - D-glucose
specific rotation + 52.6° [O:]=+ 112 .2 °
[CL] = + 18.7 °
 Biomolecules I 711
112.2" (pure a-anomer) 30. On heating slowly sucrose melts and if allowed to cool, solidities
to pale-yellow glassy mass called barley sugar. At 483 K, it loses
water and forms a brown amorphous mass called caramel.
31. Carbohydrates are optically active polyhydroxy aldehyde or
t 5?:§~ --- --- ------ -- +- mixture of polyhydroxy ketones.
~ (pure a- and~-)
)c=O, OH functional groups of typical ketose.
- CHO, OH functional groups of typical aldose.
18.7° (pure ~-anomer) 32. Sometimes the blood sugar level of diabetic patients decreases
time -+ suddenly. So, diabetic patients generally carry a packet of glucose
which can increase the blood sugar level almost instantaneously.
21. a-maltose is composed oftwoa-D-glucose units in which C-1 of
33. C I carbon of monosaccharides is called anomeric carbon. When
one glucose is linked to C-4 of another glucose unit.
the - OH group attached with C I carbon is towards right, it is
22. ~ -D-glucose ~ D-glucose ~a-D-glucose
called a-form and when the - OH group is towards left, it is
("" 64%) ~ (open chain.,, 0.02%) ~ (.,, 34%) called [3-form. Such pair of optical isomers which differ in the
23. Glucose is aldohexose and fmctose is ketohexose. Hence, these configuration only around anomeric carbon are called anomers.
are functiona l group isomers. H OH HO H Anomeric
"/ " / ...-carb
24. Despite having, the aldehyde group, glucose does not give, C C ~
2, 4-DNP test, Schiff's test and it does not form the hydrogen . / I7O
Anomeric
17 (asymmetric)
carbon
sulphite addition product with NaHSO 3. It shows that glucose is a (asymmetric)
cyclic compound. (l-form ~-form
25. Ring A is pyranose (6 membered ring containing one O-atom)
with a-glycosidic linkage and ring B is furanose with 34. This is Molisch's test of carbohydrates. In this experiment, violet
~ -glycosidic linkage. ring is formed at the junction of two liquids.
35. I mole of glucose is oxidised to give 38 moles of ATP. So,
26. D-glucose, D-fmctose and D-mannose will form the same
osazone when treated with excess of phenyl hydrazine because 2 moles will give 2 x 38 = 76moles of ATP.
they differ only in 1st and 2nd carbon atoms which are
transformed to the same form. CHO CH=N·NH¼;Hs
CHO CH2OH CHO I I
CHOH CHOH
I I I 36. I I
G5H 5NH·NH 2
H- C- OH C=O HO- C- H (CHOH)3 ~H5NH2
(CHOH)3
I I I I I - NH3
HO- C- H HO- C- H HO- C- H CH,OH CH2OH
I I I Glucose Glucosephenyl
hydrazone
H- C- OH H- C- OH H- C- OH
I I I CH=N.NH¼Hs
H- C- OH H- C- OH H- C- OH I
C=N-NHC6H5
I I I I
CH2OH CHpH CH2OH (CHOH)3
D-glucose D-rructose D-mannase
I
They form the following osazone CH2OH
Glucosazone
CH=NNH¼#s
I 37. Cellulose is a straight chain polysaccharide composed of
C=NNH¼Hs D-glucose units which are joined by [3-glycosidic linkages
I between C-1 of one glucose and C-4 of the next glucose. In one
(CHOH)3 unit only three hydroxy groups are free to form acetate, that's
I why called cellulose triacetate.
CHPH 38. a-D(+) glucose and [3-D(+) glucose are anomers
Glucosazone
27. Glyceraldehyde (CH 2OH- CHOH- CHO) is the first member
of monosaccharide. HO~_,~\
~( ~\
HO '" " ~ O H
28. Fmctose is the sweetest carbohydrate in organic compounds. It is HO ~ H61 • HO HO •
about two times sweeter than glucose and four times sweeter than OH
maltose. o:-anomer J3-anomer

29. Letter 'D' before the name of monosaccharide reveals that the 39. A mixture of amylose and amylopectin is called starch.
- OH group at the second carbon atom is towards the right i.e. it Amylose is a water soluble fraction while amylopectin is water
only shows the configuration at a particular chiral carbon. insoluble fraction.
712 I Chapterwise & Topicwise Engineering Entrances Solved Papers
40. On hydrolysis with dilute aqueous sulphuric acid, sucrose gives a 46. The C- 1 carbon of D(+) glucose is called anomeric carbon or
equimolar mixture ofD-(+) glucose and D-(-)-fructose. glycosidic carbon and the pairs of stereoisomers differ in
H2S04 configuration around C- 1 are called anomers.
C ,2H22011 + Hp ---➔ C6Hlp6 + ½ H 1206
Surcose D-{+)glucose D-(-) fructose
47. Strucnrre of glucose
I I CHO } Aldehyde group
Sucrose is dextrorotatory but after hydrolysis gives I
CHOH
dextrorotatory glucose and laevorotatory fructose, laevorotatory I
fructose is more, so the mixn1re is laevorotatory. CHOH Sec alcoholic group
41. Lactose present in milk changes into glucose and galactose after I
CHOH
digestion.
I
42. Glucose pentaacetate does not form an oxime because the CHOH
glycosidic -OH group is not free since, it is involved in ring I
CH20H } Pri. alcoholic group
formation. As a result, it cannot get converted into the open chain
form, required for the formation of oxime. 48. Glucose reacts with acetic anhydride in the presence of
CHO CH=N-NHC6H 5 anhydrous ZnC1 2 to form pentaacetyl glucose which indicates the
I I presence of 5 -OH groups in glucose molecule and the open
CHOH Q;H NHNH CHOH chain stmcnrre of glucose.
43. I s ; I CHO
(CHOHh - Hi) (CHOH)3
I
I I (CHOH)4 + 5(CH3C0)2 0
CH20H CHpH
G lucose Phenyl hydra.zone I
CHpH
Glucose
CHO
ZnCl2 I
11 (CHOCOCH3 ) 4 + 5CH3COOH
I
CH20COCH 3
Pentaacetyl glucose

49. Cellulose is a polymer of glucose. ~D(+)- glucose units are

attached to each other by C 1 to C4 bonds through ~-glycosidic
linkage in strucntre of cellulose.
SO. The number of chiral carbon atoms in ~-D (+) glucose are five.
HO H
'\./
Thus, only three phenyl hydrazine molecules and one molecule of
glucose is required to form osazone.
44. This compound contains five carbons atoms, so it is a pentose. Its H-C~H
r.~ I
first carbon contains- Hand -OH group. This suggests that it is I. o
an aldose (i.e. contains aldehyde group). Since, its structure is
similar to furan (a heterocyclic compound), so it has furanose I. - C ~
HO
structure. H-C-OH

H-1•
HOH,(f--{f
~O':i~ I
CH20H

51. Sucrose gives glucose and fructose on hydrolysis with invertase

enzyme.
H OH
C 12H220 I I + H20 Jnvertase ) C6H 1206 + C6H 1206
Hence, this compound is a pentose, aldose and have furanose Sucrose Glucose Fructose
structure.
52. Glucose gives silver mirror with ammonical silver nitrate because
45. Benedict's solution contains CuS0 4 , Na 2C03 and sodimn citrate. of presence of-CHO group (aldehyde group) in the structure of
This permits formation of a complex, which lowers the glucose.
concentration of Cu(H) ions to such an extent that it does not CHpH(CHOH)4 CHO + Agp
permit the precipitation of insoluble Cu(OH)2• Tollen's
reagent
Benedict's solution is more stable than Fehling's solution and is
not affected by substance like uric acid present in urine. Hence, it ~ CHpH(CHOH)4 COOH + 2Ag t
Q luconic acid Si lver mirror
is preferred to detect the presence of glucose in urine.
 Biomolecules I 713
53. Partial hydrolysis of cellulose gives the disaccharide cellobiose 64. Two forms ofD-glucopyranose area-D-(+)-glucopyranose and
(C 12H 2i0 11) . Cellobiose resembles maltose (which on acid ~-D(+)-glucopyranose. These are anomers (a pair of
catalysed hydrolysis yields two molar equivalents ofD-glucose) stereoisomers whic h differ in configuration only around
in every respect except one the configuration of its glycosidic first-carbon atom are called anomers).
linkage.
54. The sugar which cannot reduce Fehling solution and Tollen's
reagent are called non-reducing sugars e.g. sucrose and all H~E7H
21

«:J :H I '"'
polysaccharides. H-C-OH
55. Methyl a-D-glucoside and methyl [3-D-glucoside are anomers.
A pair of stereoisomers which differ in configuration only
around C 1 are called anomers. In methyl a-D glucoside, the
methoxy - OCH3 group at-C 1 is towards right while in methyl
~-D glucosides the - OCH3 group at C is towards left. 51
H-C
56. Starch+ iodine- blue colour~ blue colour dis.1ppears 61
CH2OH
~ blue colour reappears Ct-D(+)-glucopyranose J}-D(+)-glucopyranose
So, iodine test is given by starch.
65. Cellulose is the most abundant polysaccharide. It is the essential
57. Anomers of glucose are cyclic diastereomers (epimers) differing in constituent of the cell-wall of a ll green-plants.
configuration at C-1 existing in two forms a and~' respectively.
66. Amylopectin consists ofD-glucose units from 300 to 600. So it is
insoluble in H 2O .
HO ~ o \ HO~o\ OH 6 7. Sucrose molecule is made up of a glucopyranose and a
fructopyranose.
HO ~ HO~ 6 8. (i) K e to hexose It is carbohydrate having 6C atoms and a
OH OH OH ketonic group.
Ct-fonn ~fonn
(ii) Disaccharide It is carbohydrate which on hydrolysis gives
58. Main constituent of plants is cellulose. Wood is 50% cellulose 2 molecules of monosaccharides.
while cotton wool is almost pure cellulose. (iii) Polysaccharides These carbohydrates give more than two
molecules of monosaccharides on hydrolysis.
2
59. CH 2OH(CHOH)4 CHO Br / H:P CH OH(CHOH) COOH (iv) P entose It is a 5 carbon atoms monosaccharide e.g. Ribose
Glucose ox1dat1on 2 4
Gluconic acid
(CsH 10Os) ·
60. Raffinose is a trisaccharide. It gives three moles of 69. Sucrose is a disaccharide and it yields one molecule each of
monosaccharides on hydrolysis. glucose and fructose on hydrolysis.
H+
C 18H 32O 16 + 2H 2O - Glucose+ Fructose+ Galactose H+
C12H22O, 1 + H2O ~ C6H1P6
CHO Sucrcose Glucose
I
61. Glucose is a pentahydroxy a ldehyde. (CHOH)4
I 70. Amylase enzyme acts on starch and hydrolyse it to glucose.
CH,OH
Glu'c;ose 71. Maltose gives Molisch's test as well as Benedict's test but it does
62. Lactose gives glucose and galactose on hydrolysis. not give wine red colour, on heating with a few crystals of
H20 resorcinol and cone. HCI (Seliwanoff's test). Sucrose and
Lactose~ Glucose + Galcactose fructose give this test.
H
72. Energy is stored in our body in the form of a adenosine
63. All monosaccharides reduce Tollen's reagent into silver mi1Tor.
triphosphate (ATP) which release energy, by breaking phosphate
CHO COOH
bonds, when we require it.
I I
e. g. (CHOH)4 + Agp - (CHOH)4 + 2Agl 73. Glucose is a monosaccharide. The chemical composition of
I Tollen' s I Silver glucose is c;H 12O6.
CH2OH reagent CH2OH mirror
Glucose Gluconic acid
Topic 2 Proteins and Enzymes
1. Insulin is composed of two peptide chains referred to chain A and Glycine is optically inactive thus it cannot be on the N-terrninal
B. Chain A of 2 I residues and chain B of 30 residues are cross side.
linked by two disulphide bridges. Thus, possible combinations are
2. The tertiary structure of proteins refers to three dimensional Phe-Gly-Val-Ala
folding of polymer chain. Phe-Val-Gly-Ala
3. From van-Slyke method for estimation of amino acids Val-Gly-Phe-Ala
0 Val-Phe-Gly-Ala
+
H 3N -
II
CH- c - o - - - - - - - >
NaN02 / HCI Thus, in all four possible combinations.
I o°C 0 0
R II II
1.78g 6. R- NH2 + CH3 - C- CI -----t R- NH- C- CH 3
(- HCI)

HO- ~ H- COOH + H 2O + N2 Since, each - COCH 3 group displaces one H atom in the
I 448cm3 0
R 2240ocm3
II
. .d 1.78 X 22400 reaction of one mole of CH 3 - C- CI with one - NH2 group,
M o Iar mass of l -ammo act = - - - - - 89
448 the molecular mass increases with 42 unit. Since, the mass
·: Protein has 0.25% of amino acid by mass increases by (390-180) = 210, hence the number of - NH2 group
. 89xl00 _, is2.!.Q=5.
:. Molar mass ofprotem = - - - 35600 g mol
0.25 42
4. Combination of four amino acid units gives a linear tetrapeptide, 7. a-helix is found in proteins.
in which three peptide bonds are present. 8. The amino acid remain in Zwitter ionic form completely at its
0 H CH3 isoelectric point. Amino acids with additional acidic group have
II I I their isoelectric pH less than 7.0 and increasing pH above
H 2N- CH2- C- OH + H-N- CH - COOR isoelectric point makes them anionic. On the other hand, amino
0 0 acids with additional basic group have their isoelectric pH greater
II II than 7.0 and decreasing pH below isoelectric point (by adding
+ H2N- CH2- C- OH + H 2N- CH2- C- OH acid solution) makes them cationic. The given peptide with
following R 1 and R2 are basic, will remain protonated (cationic) at
0 H CH 3 0 H pH= 7.0.
II I I II I
H2N- CH2 ~ - CH- ~ - CH2 Peptide R1 R2
Peptide bond Peptide bond
IV CH 2CONH2 (CH2)4NH2
0 0
II II VI (CH 2)4 NH2 (CH2)4NH2
- c-y - CH 2- C- OH VIII CH 2OH (CH2)4NH2
H IX (CH 2)4NH 2 CH 3
Peptide bond
(Tetrapeptide) 9. Dialysis is used to separate glucose and protein from body.
5. A peptide linkage is hydrolysed to two free amino acids. 10. Amino acids contain both amine (- NH 2) and carboxylic
,'6__ _ ' , (- COOH) groups. These are obtained by the replacement ofH
atom of the alkyl group by - NH 2 group in carboxylic acids.
,: II , H 2NCH2COOH (glycine) is the simplest amino acid.
H2N - CH- C -NH.,-.. CH - COOR
I \, ~,, I 11. Haemoglobin (Hb) is the iron containing oxygen transport
R ' --r-'
Peptide
R' metalloprotein in the red blood cells of all living beings.
12. Glycine is a-amino acetic acid with no chiral carbon, thus
0 optically inactive.
H
H 2N - CH -
11
C- OH - H2N - CH-
•
COOH I
H- C- COOH
I I I'-,_Achiral carbon
R R'
.
C is chiral carbon tetrapeptide and has four amino acids joined by
NH 2
13. Proteins are macromolecular polymers of a-amino acids bonded
three peptide Iinkage. by peptide linkage. They on hydrolysis, yield a-amino acids
- COOH group is on alanine part, thus it is at fixed C-terrninal farther.
position in each combination.
 Biomolecules I 715
14. A decapeptide has nine peptide (amide) linkage as 26. Namrally occurring amino acids are 20.

o/
0
('cl 'o/
0 0 0
V 'o/ 0 Hence, number of possible tripeptides = 203 = 8000
27. 1 Fluoro-2,4-dinitrobenzene is called sanger's reagent and is used
-CONH- for determination of N-perminal amino acid sequence in a
bond polypeptide chain.
Therefore, on hydrolysis, it will absorb nine water molecules. 28. Tryptophan is a heterocyclic amino acid.
Hence, total mass of hydrolysis product H 2N- CH- COOH
=796+ 18x9=958
mass of glycine in hydro lysis product
tH27=JQJ
= 958 X 47 = N
450
100 I
H
munber of glycine molecule in one molecule of decapeptide
29. Essential amino acids (10) are as follows:
= 450 = 6
(i) Arginine (ii) Histidine
75
(iii) Isoleucine (iv) Leucine
0 0 (v) Lysine (vi) Methionine
II II (vii) Phenylalanine (viii) Threonine
15. H- r - C- O-H ~ H-? H- C- O-
(ix) Tryptophane (x) Valine
:NH2 +N8:i 30. Only proteins give positive ninhydrin test. They give blue colour
Glycine Zwitter ion with ninhydrin.
In alkaline medium, an amphoteric Zwitter ion changes to anion.
16. Oxytocin is a hormone
17. At pH= 6, glutamic acid exists as a dianionic species and
migrates to anode while arginine exists as cationic species and
moves to cathode. Alanine does not migrate to any electrode at its
isoelectric point. Glycine Alanine Glycine

18. Cellulase enzyme is present in the stomach of grazing mammals. l-2H20

It digests cellulose.
0
19. Lysine contains two basic groups.
II
20. B iuret test is characteristically given by the compound having
0 N H 2 j( NHYc'---NH~cooH
II
- C-NH - functional group. Hence, carbohydrates do not 0 CH3
respond to Biuret test.
32. Zwitter ion or inner salt has acidic and basic groups in the same
21. Proteins are the polymer of amino acids and contain polypeptide molecule.
bonds. DNA, however, are the polymers of nucleotide and
A Zwitter ion is a dipolar ion w ith positive and negative charge at
contain no polypeptide bond. Hence, DNA is not a protein.
different points on it.
22. Pepsin hydrolysis proteins into amino acids as
e.g. Sulphanilic acid exists as a Zwitter ion.
Proteins ~ Amino acids.

~-~
23. In alkaline medium, alanine exists as anion.
CH -CH-NH Basic medium CH - <;:H- NH
3 I 2 (pH > 7) ) 3 I 2

COOH COO-
Alanine S03
24. The pH at which a particular amino acid does not migrate under Sulphanilic acid Zwitter ion
structure (II)
the influence of an electric field is called isoelectric point of that
amino acid. 33. Histidine is the unique amino acid which contains imidazole ring.
The pH range for the isoelectric point is from 5.5 to 6.3 or the
pOH range for the isoelectric point is from 7.7 to 8.5.
25. Upon heating, the proteins get coagulated. This process is called
denan,ration of proteins. During this process, the secondary and
tertiary structures get destroyed but primary strucnire remains
Histidine lmidazole
intact. ring
716 I Chapterwise & Topicwise Engineering Entrances Solved Papers
34. The helical structure of protein is stabilised by hydrogen bonds 43. When protein is boiled with a dilute solution of ninhydrin
between amide group of the same peptide chain. These bonds are (triketohydrindin), a blue colour is produced.
formed by - NH- group of one unit and oxygen of carbonyl
group of the third unit. This H-bonding is responsible for holding Protein + Ninhydrin solution ~ Blue colour
helix in a position. 44. Zwitter ion is fonned by amino acid. Glycine is amino acid.
35. Most naturally occurring amino acids have L-configuration. Zwitter ion of glycine is
+
36. Ninhydrin test is highly specific for primary amines. Proline NH3-CH2- Coo-
being a secondary amine gives a yellow orange colour with
45. Glycine is optically inactive amino acid due to the absence of
ninhydrin whereas all other a-amino acids give a blue-purple
chiral carbon atoms.
colour with ninhydrin.
CH 2 - COOH
37. At pH = 4, an amphoteric Zwitter ion strncture changes into
I
cation when an acid is added to it. NH2
G lycine

46. Disulphide bond may be reduced to thiol by means of reagents,

i.e. NaBH 4 , which shows the presence ofthiol group in disulphide
bond fonnation.
38. Primary strncture involves sequence of a-amino acids
47. Tyrosine has phenyl --OH group. Its structure is as
polypeptide chain. Secondary structure involves a-helical and
~ -pleated sheet like structures. NH3- CH-COOH
39. Peptides are compounds formed by the condensation of two or
JH2-(Q)-OH
more same or different a-amino acids. The condensation occurs
between amino acids with the elimination of water.
H2N- CH 2COOH + H 2N- CH- COOH -H 0 48. Enzymes are the biological catalysts. They are specific in nature
Glycine I 2 and catalyse the biological reaction.
CH3 49. Proteins are polypeptides with molecular weights more than
Alanine I 0000. These are fonned by the combination of more than I 00
r-◊-----:
molecules of amino acids. A polypeptide is formed by the
: II : combination of less than I 00 amino acid molecules.
H 2N- CH2 ~ C- N-+-CH-COOH
: I :I SO. Conjugated proteins on hydrolysis give a non-protein portion
~ ____f!_J CH3 alongwith ex-amino acid. The non-protein portion is called
prosthetic group.
/
Peptide bond
Protein Prosthetic group
40. In aqueous solutions, amino acids mostly exist as Zwitter ions.
R Phosphoprotein Lipid ( e.g. lecithin)
+ I Glycoprotein Sugar
NH3- CH-coo- Chromoprotein Colouring matter such as red
Zwitter ion
coloured protophyrin
41. The peptide linkage (- NH- CO- ) is formed by the
condensation of amino acids molecules. Since, all of them have non-protein part hence, all of them are
HNH- CH-C- OH + H · NH - CH- C- OH conjugated protein.
I II I II 51. Antibodies present in the blood destroy antigens.
R O R 0
52. The main strucn1ral fean1re of protein is peptide linkage.

~ - HN- CH- C- NH- CH - C- + c - NH+

-H2o I II I II II
R O R 0 0
53. Sulphanilic acid exists as Zwitter ion.
Hence, following structure represents the peptide chain.
H
I I
H
I
- N- C- C- N- C- C- N- C-
1 II
0
H
I
I
O

II
0
42. Haemoglobin acts as oxygen carrier in the blood because four
I I
I
II
C-
¢ ¢
Sulphanilic acid
so;-
zwitterion
2
Fe + ions of each haemoglobin can bind with four molecules of
0 2 and fonn oxyhaemoglobin. It exists as a dipolar ion, which has acidic and basic groups in the
same molecule.
4Hb + 402 ~ Hb4Os
Oxyhaemoglobin
 Biomolecules I 717
54. The aromatic properties can only be represented by tyrosine. Topic 3 Nucleic Acids (DNA, RNA) and
Tyrosine is a-amino P(p-hydroxyphenyl) propionic acid. It has
aromatic nucleus. It is an aromatic amino acid.
Protein Synthesis
NH 2 1. Quinoline is an alkaloid, it is not present in DNA. DNA has four
I nitrogen bases, i.e. adenine, guanine, cytosine and thymine.
H 2 C- CH-COOH
2. The sugar moiety present in the RNA molecule is 13-D-ri bose.

¢
OH
HOH
20
H
5

4
O

H
OH
I

55. Two or more amino acids unite through a bond (-CO-NH-) 3 2

which is known as peptide bond or peptide linkage. OH OH
13-D-ribose
56. Proteins are polypeptides with high molecular weights. (5 carbon compound)
57. Cellulose is a polysaccharide (carbohydrate) while rest three are
enzymes. Enzymes are chemically complex proteins which act as 3. In DNA, the consecutive deoxynucleotides are linked through
catalyst in biological activities. phosphodiester linkage.
58. Glycine is an achiral amino acid w hile all other amino acids are 0
chiral. I
5CD
O HBase-I
H 4 I
I
H H H
H 2N- C- COOH
I 3 2
H 0 OH
Glycine I
HO - P=O
59. Glycine reacts with benzoyl chloride in the presence of aqueous I
NaOH to give benzoylglycine (Hippuric acid). 0
5I
Aq. NaOH
HOOC· CH2NH2 + PhCOCI t,.
Glycine Benzoyl chloride QH Base-TI
4 I
PhCONHCH2COOH + HCI H H
Benzoylglycine
3 2
( Hippuric acid)
60. Glycine (NH2CH 2COOH) is an amphoteric acid as it contains 0 OH
both acidic and basic groups. I
HO - P=O
61. A nanopeptide contains 8 peptide linkages.
62. Structure of cysteine is
I
0
/NH2 4. In transcription, synthesis of RNA takes place while in
HSCH 2CH"" translation, synthesis of protein occurs is cytoplasm ofa cell.
COOH 5
63. Streptokinase converts plasminogen into plasmin and used for H 0 ~ 2 0OH
dissolving blood clots. 4 I
5· H H
64. By the condensation of a-amino acids peptides are formed.
H 2 H
H 2N- CH2 COOH + H 2N- CH2 - COOH
~ H 2N- CH2 - CONH - CH 2COOH HO OH
-H 20 Peptide bond
13-D-ribose used in RNA, at 2nd carbon - OH group is present
65. The compounds having - NH2 and --COOH or - NH2 and 5
- S03H groups exist as Zwitter ion e.g.
H0 ~ 2 0H

¢ ¢
4 I
H H
H H
3 2
HO H

S03 S03 13-D-deoxyribose used in DNA, at 2nd carbon - OH group is

Zwirterion Sulphanilic acid missing.
718 I Chapterwise & Topicwise Engineering Entrances Solved Papers
6. Guanine is the constituent of nucleic acid and not guanidine.
7. A sequence of three nucleotides in messenger RNA makes a
codon for an amino acid because four bases in messenger RNA
adenine, cytosine, guanine and uracil have been shown to act in
the form of triplet.
8. Hydrogen bonding is involved molecular force in the DNA
molecule.
Watson and Crick observed the purine-pyrimidine type of
hydrogen bonding (instead of purine-purine and
pyrimidine-pyrimidine).
9. Nucleoside + phosphoester bond = nucleotide.
1O. Monomer of nucleic acid (DNA or RNA) is nucleotides.
11. Uracil is present in RNA but not in DNA.
12. In DNA, cytosine and thymine are pyrimidine bases.
13. Uracil, thymine and cytosine a re pyrimidine bases while adenine
and guanine are purine bases. RNA contains uracil in place of
thymine.
In the structure of DNA, thymine always joins with adenine by 2
H-bonds and guanine always joins with cytosine by 3 H-bonds.
20. RNA contains ribose sugar and uracil.
Topic 4 Lipids, Vitamins, Hormones
and Pigments
1. Somatotropin is the hormone, secreted by anterior lobe of
pitutary gland. It is also called growth hormone as it stimulates
protein-synthesis, glycogenesis and some other biological
activities. Its deficiency causes midgets or dwarfism.
2. Metabolic function in human bodies is carried out by enzymes.
The three main constituents of food, viz carbohydrates, fats and
proteins are subjected to the action of various enzymes to form
simple constituents capable of being absorbed by small intestine
e.g. pepsin and ptyalin.
3. Progesterone is a hormone, secreted by ovaries.
4. Naturally occurring fats are called lipids.

14. Thymine base is not present in RNA. Uracil is found in place of 5. Saponification of oils yields a trio I (glycerol). Drying (hardening)
thymine. of oil involves hydrogenation. Refining of oil is done by
distillation or other such processes but not by hydrogenation.
15. Synthesis of RNA/DNA from phosphoric acid, ribose and
Antioxidants are added to prevent the oxidation of oil, thus they
cytosine is given below
minimise rancidity.
NH2
6. Deficiency of vitamin- A causes night-blindness.

r2t~--~ :(io
7. V itamin D e ficiency disease
Vitamin B 12 Pernicious anaemia
Vitamin B6 Skin disease
O = l~~----~:OCQ,o~?~~- L , Vitamin E Sterility
4 t ',, __ H::m;o
OH H H __ __,
V itamin K Haemorrhagic condition
H 3 H
2 8. The chemical name of vitamin B 1 is thiamine.
OH 9. Column I Column II
Thus, ester linkages are at Cs' and Ct' of sugar mo lecule. Vitamin A Xerophd1almia

OH
I 5'
,AJ
06l1A
Vitamin B 12
Vitamin C
Vitamin E
VitaminK
Pernicious anaemia
Scurvy
Sterility
Hemorrhagic condition

O=P-I O- C
.Q HN 4'
2
I'
0 10. Sodium or potassium salts of fatty acid are known as soap. Soap
OH H H does not come in lipid series.
H 3
, H 11. Oils (liquid glycerides) react with hydrogen in the presence of
2' metal catalyst (like nickel) to give saturated glycerides
OH OH (semi-solid glycerides) i.e. fats. Thus, vegetable ghee (dalda) is
obtained by the hydrogenation (reduction) of oils.
16. There are two hydrogen bonds present between pair of thymine
Oils + H 2 - Dalda
and adenine w hile three hydrogen bonds are present between
12. Fats and lipids are hy drolysed by lipase.
cytosine and guanine.
17. A nucleotide contains a pentose sugar [deoxyribose (in DNA) or 13. Ghee has least iodine value among the given options because it is
ribose (in RNA)], nitrogenous base [such as adenine or guanine or the least unsaturated.
thymine (in DNA) or cytosine or uracil (in RNA)] and a 14. Iodised salt prevents goitre.
phosphate molecule. 15. Derived fats like sterols (cholesterols), ketone bodies,
18. In the molecular biology transcription is used for RNA synthesis hydrocarbons, terpenes, carotenoids etc. are obtained by the
and translation for protein synthesis. hydrolysis of simple lipids and compound lipids. However,
19. T A T G A C T G neutral fats (fats and oils) are not synthesised by this mehtod.
16. Waxes are the esters of higher fatty acids w ith higher monohydric
A T A C T G A C alcohols such as mericy l and cetyl alcohols.

17. Prostaglandin is not a steroidal hormone. It is a derivative of fatty
acid.
18. Insulin regulates metabolism of carbohydrates (glucose).
19. Fats are also known as triglycerides. These triglycerides are the
triesters of fatty acid with glycerol. So, the characteristics feature
of fat is an ester group.
Biomolecules I 719
29. Phospholipids are esters of glycerol w ith two carboxylic acid
residues and one phosphate group.
Hence, phospholipids may be regarded as derivative of glycerol
in which two hydyroxyl groups are esterified w ith fatty acid,
while third is esterified w ith phosphoric acid.
30. Hardening of fat (lipid) is due to hydrogenation.

20. Iodine value is related to oils and fats. Iodine value measures the Oil (liquid) + H 2 ~ Vanaspati ghee
drying quality of an oil. More the unsaturation, better is the Solid
drying quality of an oil. When an oil is treated with I 2, it adds to 31. Insulin is a hormone build up of two polypeptide chains.
double bond. Iodine value is defined as the number of centigrams 32. Vitatmin ~ is called pyridoxin. It is fotmd in fiuits, green-vegetables,
ofI2 that can be taken by I g of the oil.
milk, etc. Due to its deficiency, anaemia disease is caused.
21. Insulin hormone helps in the conversion of glucose into glycogen
33. Fats and oils are esters of glycerol with higher fatty acids. Hence,
by the liver and skeletal muscles. Insulin is secreted by pancreas
coconut oil is an ester.
that lowers blood glucose level.
CH,OOCR CH,OH 34. Calciferol is the chemical name of v itamin D.
I - Lipase I - 35. Palmitic acid= C 15H 31 COOH
22. CHOOCR + 3H2O hydrolysts> CHOH + RCOOH
I Fatty acid Saturated monocarboxylic acids form a homologous series which
I
CH2OOCR CH,OH has a general formula C,,H2n+ 1 COOH. Out of all the options only
Gly;.,rol palmitic acid follows this.
23. Oils and fats are triglycerides. (esters of higher carboxylic acids 36.
w ith glycerol). e.g. palmitin. Biomolecule Metal ion
CH 2OCOC 15H 3 1 Vitamin B 12 Co (transition metal)
I Chlorophyll Mg (non-transition metal ion)
CHOCOC 15H 3 1
I Haemoglobin Fe (transition metal)
CH2OCOC 15H 3 1
Pahnitin (fat) Insulin S (non-metal)
24. Wax contains ester group. These are the esters of high molecular
37. cx-tocopherol is vitamin E. It acts as an antisterility factor. Its
weight of monohydric alcohol and high molecular mass of deficiency can cause sterility.
monocarboxylic acid.
38. Adrenal glands are important endocrine glands in human-body.
25. Triolein is an unsaturated glyceride while tristearin is a saturated Its cortex part secretes the hormone 'cortisone'.
glyceride. Hence, the conversion of triolein to tristearin can be
39. Vitamin B 12 or cyanocobalamine contains cobalt and not
affected by hydrogenation. Triolein + H2 ~ Tristearin magnesium.
26. V itamin B 12 contains cobalt metal. The chemical name of 40. The tripeptide hormone present in most living cell is glutathione.
vitamin B 12 is cyanocobalamin. It is made up of 3 amino-acids viz glycine, glutamic acid and
27. It is the test for fat.When fat is heated in the presence ofKHSO4 cysteine. It also acts as co-enzyme in various cells.
(dehydrating agent) the glycerol portion of the molecule is 41. Vitamin C is also called ascorbic acid. The deficiency of vitamin
dehydrated and form unsantrated aldehyde CH 2 = CH- CHO C causes scurvy. It is present in amla, tomatoes, orange, cabbage,
(acrolein), a bad smelling compound. lemon, etc.
CH2OH
28.
Column I Column II I
42. Fat + NaOH or KOH - CHOR + Sodium or potassium salt
Thymine Pyrimidine base
I
Thiamine V itamin B 1 CH,OH
Gly;erol
Insulin Hormone
of fatty acid.
Pepsin Enzyme
:. Glycerol is alcohol, formed by hydrolysis of fats.
Phospholipids Cell wall component
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Polymers
QUICK REVIEW
Polymers
• Polymers and macromolecules both are high molecular
mass substances but polymer has essentially a repeating
structural unit while a macromolecule may or may not
have. e.g. polythene is a polymer while chlorophyll is a
macromolecule (single giant molecule).
The small molecules which constitute the repeating units in
a polymer are called monomer units and the process by
which these monomers are converted into polymers is
called polymerisation.
• Natural polymers are found in nature. e.g. proteins,
polysaccharides, etc. These are biodegradable. Synthetic
polymers are man-made and generally non-biodegradable.
e.g. nylon, dacron, etc. Biopolymers are the polymers
which control the various life processes in the bodies of
animals and plants. e.g. proteins.
• Semisynthetic polymers are obtained from natural
polymers. Rayon and some other cellulose derivatives such
as celJulose nitrate, cellulose acetate are semisynthetic
polymers.
Types of Polymers
• On the basis of structure of polymers, these can be
classified into linear polymers, branched chain polymers
and cross-linked polymers. Linear chain polymers have
high magnitude of intermolecular forces of attraction and
therefore, have high tensile strength (nylon, polyester)
while branched chain polymers are irregularly packed and
have low tensile strength. Cross linked polymers are three
dimensional network polymers. These are hard, rigid and
brittle (bakelite, formaldehyde resin).
• Depending upon the intermolecular forces, polymers are
of four types-elastomers, fibres, thermoplastics and
thermosetting polymers. In elastomers (natural rubber) the
polymeric chains are held together by weak inte1molecular
forces. Fibres (nylon-6,6, dacron) have strong
intem1olecular forces, so they have high tensile strength
and less elasticity.
• Thermoplastic polymers can be easily softened on
heating therefore, can be remoulded, recast and reshaped.
e.g. polythene, polystyrene, PVC, etc. Thermosetting
polymers on heating get highly cross-linked to form hard
infusible and insoluble products and cannot be remoulded
or reshaped, e.g. bakelite.
• Addition polymers such as polythene, teflon, etc., are
formed by addition reaction and generally involve one
monomer unit (unsaturated). Condensation polymers such
as nylon-6,6 are formed by condensation process with
elimination of smalJ molecules like H2 0 and involve more
than one monomer unit having two active functional groups.
• Homopolymers are formed from one type of monomers. e.g.
polythene is a homopolymer of monomer ethene.
Copolymers are formed from two or more types of
monomers. These are more important. e.g. saran is a
copolymer of vinyl chloride and vinylidene chloride.
• Chain growth or addition polymerisation involve a
series of reactions each of which consumes a reactive
particle and produces another similar one. The reactive
particle may be free radicals or cations or anions. Polythene,
polypropylene, teflon, PVC, polystyrene and polybutadiene
are some of the chain growth polymers.

• Free radical polymerisation is initiated by organic
peroxide such as benzoyl or t-butyl peroxide. Chain
transfer agents determinate chain reaction and inhibit
further polymerisation. e.g. CC14 , CBr4 , etc. These are
also known as inhibitors.
• Step growth or condensation polymerisation involves a
series of independent steps. Each step involves the
condensation between two bifunctional monomers.
Nylon-6,6, bakelite are the examples of step growth
polymerisation.
Some Important Polymers
• Teflon, also known as polytetrafluoroethylene (PTFE) is
used for coating of non-stick utensils.
It is formed by the polymerisation of tetrafluoro ethene
(CF2 = CF2 ) molecules.
• Polyacrylonitrile or orion is formed by addition
polymerisation of acrylonitrile.
• Polyamides possess amide linkages while polyesters
possess ester linkages.
• Terylene (dacron) is a condensation polymer of ethylene
glycol and terephthalic acid.
• Nylon-6, 6 is prepared by condensation polymerisation of
adipic acid and hexamethylenediamine.
• Ny lon-6 or perlon is obtained from monomer caprolactam.
• Bakelite is a polymer offormaldehyde (HCHO) and phenol
(C6 H 5 0H).
• Natural rubber is a polymer of isoprene,
i.e. 2-methy1-1 , 3-butadiene.
Polymers I 721
• Natural rubber is vulcanised (heating of rubber with
sulphur) to improve its properties. During vulcanisation,
sulphur forms cross-links at reactive sites (double bonds,
allylic-CH2 and alpha to double bond are reactive sites in
rubber molecules).
• Polyurethanes are polymers of urethane. These are
obtained by condensation of toluene diisocyanate with
ethylene glycol.
• Phenol-formaldehyde polymers are obtained by
condensation of phenol with formaldehyde in the presence of
either an acid or a base catalyst. First a linear product called
novolac is obtained (used in paints) which on further heating
with HCHO undergoes cross-linking to form bakelite.
Polydispersity Index
• Polydispersity index, PDI gives an idea about homogeneity
of a polymer.
= weight average molecular mass (Mw)
PDI - - - - - - - - - - - , -
number average molecular mass M,.
• Biodegradable polymers such as polyhydroxy butyrate
(PHB), poly-~-hydroxy butyrate-co-~ -hydroxy valerate
(PHBV), polyglycolic acid (PGA), etc; and their
degraded products don't cause any serious affects on
environment.
• Low density polythene (LDP) is obtained by free-radical
polymerisation of ethylene while high density polythene
(HDP) is obtained by coordination polymerisation of
ethylene.
• Ziegler-Natta catalyst [(C2 H 5 )J Al + TiCI 3 or TiCI 4 ] is
used as a catalyst in the polymerisation of olefins.
 Topic 1
Polymers : Its Classification and Modes of Polymerisation
2014

l
1. Which one is classified as a condensation polymer? 7. Identify the copolymer from the following. [EAMCET]
(a) Dacron (b) Neoprene [JEE Mains]
(c) Teflon (d) Acrylonitrile
2. A copolymer of ethene and vinyl chloride contains
alternate monomers of each type. What is the mass
(a) t H 2 -CH=CH-CH 2 -
1H-CH 2

C6Hs
percentage of v inyl chloride in this copolymer? [BITSAT] n

(a) 38% (b) 69% (b) +CF2 -CF2 +,,

(c) 72%

(a) Nylon-6,6
(d) 82%
3. Which of the following has an ester linkage?
(b) Dacron
[VITEEE] (c) tCH 2 - y= CH-CH 2
Cl
t. n
(c) PVC (d) Bakelite
4. Which one of the following is the structure of
(d) tH,1 J
polyacrylonitrile?

tH,-r1
[Manipal]

Cl r
(a)
c:r 8. The process of fo1mation of polymers from respective
monomers is called
(a) polyacrylonitrile
[J&KCETJ
(b) copolymerisation

tH,-fJ
(c) polymerisation (d) None of these
9. Polycondensation products of dicarboxylic acids and diols
(b)
CN[ are
(a) polyamides (b) neoprene
[J&KJ

(,)tH,-Il
(c) glyptal (d) polyesters
10. PD I for natural polymers is generally close to [Manipall
(a) 0 (b) I (c) I O (d) 100
11. The most suitable property for molecular weight

tH,-r-1
determination of polymers is [MPPET]
(a) osmotic pressure
(b) lowering of vapour pressure
(d)

c::J
5. Terylene is not a [Karnataka CET] 2012
(c) elevation in boiling point
(d) depression in freezing point

(a) copolymer 12. Which one ofthe following is not a condensation polymer?
(b) polyester fibre (a) Nylon-6, 6 (b) Nylon-6 [AMUJ
(c) chain growth polymer (c) Dacron (d) Buna-S
(d) step growth polymer
2011
6. Cellulose, protein and starch are classified as
(a) natural polymers [Indraprastha CET] 13. Which type of polymer is bakelite? [Guj CET]
(b) aldehydes (a) Addition polymer
(c) esters (b) Homopolymer
(d) synthetic polymers (c) Condensation polymer
(d) Biopolymer
 Polymers I 723
14. The polymer containing strong intermolecular forces, i.e. 24. Which of the following alkenes is most reactive towards
hydrogen bonding, is CAIEEEJ cationic polymerisation? [ManipalJ
(a) teflon (b) nylon-6,6 (a) CH 2 = CHCH 3 (b) H 2 C= CHCI
(c) polystyrene (d) natural rubber (c) H 2 C= CHC6 H 5 (d) H 2 C= CHC0 2 CH 3
15. Synthetic rubber is [MP PET] 25. Which of the following is not a polymer? CMP PET]
(a) polyisoprene (b) polychloroprene (a) Teflon (b) Petroleum
(c) polythene (d) polyesters ( c) Cellulose ( d) Natural rubber
16. An example of natural biopolymer is [RPET]
(a) teflon (b) nylon-6,6 (c) rubber (d) D NA
2008
26. Rayon is [MHT CET]
2009 (a) natural silk (b) artificial silk
17. Among cellulose, polyvinyl chlo1ide, nylon and natural ( c) regenerated fibre ( d) synthetic fibre
rubber, in which of the polymer intermolecular force of 27. In case of condensation polymers, [J&K CETJ
attraction is weakest? [HT JEE]
(a) high molecular weight polymers are formed all at
(a) Nylon (b) Polyvinyl chloride once
( c) Cellulose (d) Natural rubber (b) lower molecular weight polymers are formed all at
18. Buna-N synthetic rubber is a copolymer of CAIEEEJ once
Cl (c) molecular weight of polymer rises throughout the
reaction
I (d) have no specific relation to their molecular weights
(a) H 2 C= CH-C = CH 2 and
H 2 C = CH-CH = CH 2 28. Which one of the following is a chain growth polymer?
(b) H 2 C = CH-CH= CH 2 and (a) Starch (b) Nucleic acid [Manipal]
H 5 C 6 -CH= CH 2 (c) Polystyrene (d) Protein
(c) H 2 C = CH-CNand H 2 C= CH-CH= CH 2 29. Nylon-6,6 is not a [MHTCET]
(d) H 2 C = CH-CNand H 2 C-C= CH 2 (a) condensation polymer (b) polyarnide
I (c) Both (a) and (b) (d) None of these
CH 3
30. Nylon threads are made of [MP PET, UPSEE]
19. Which one of the following is a condensation polymer? (a) polyvinyl polymer (b) polyester polymer
(a) R ubber (b) Protein [Manipal] (c) polyamide polymer (d) polyethylene polymer
(c) PVC (d) Polythene
20. Which one of the following is a copolymer? [UPSEE]
2007
31. Which one is chaingrowth polymer? [DCEJ
(a) Saran (b) Orlon
(c) PVC (d) Teflon (a) Teflon (b) Nylon-6
(c) Nylon-6,6 (d) Bakelite
21. Which type of polymer is cellulose diacetate fibre?
(a) Synthetic (b) Natural [Guj CETJ
(c) Semi-synthetic (d) None of these 32. Mark out the most unlike form of polymerisation of
CH 2 = CH-CH=CH 2 CAMUJ
22. Given the polymers, A= nylon-6, 6, B = buna-S,
C = polythene. Anange these in increasing order of their
intermolecular force (lower to higher). [DCE] (a)
(a)A<B<C (b)A<C<B
(c)B<C<A (d)C<A<B (b)
23. If M w is the weight average molecular weight and M,.
is the number average molecular weight of a polymer,
the polydispersity index (PDI) of the polymer is given
by [BITSAT] (c)

(a) M,. (b) MW

MW M,.

(c)Mw xM,, (d) 1 (d)

MwxM 11
724 I Chapterwise & Topicwise Engineering Entrances Solved Papers

33. Nylon-6,6 is an example of [BITSATJ 38. Which of the following is called polyamide?
(a) poly propylene {b) polyester (a) Terylene [Jamia Millia Islamia]
(c) polyamide (d) polystyrene (b) Rayon
(c) Nylon
34. Which of the following is biodegradable polymer?
(a) Polythene (b) Bakelite [EAMCET]
(d) Orlon
(c) PHBV (d) PVC 2005
35. Which of the following is a biodegradable polymer? 39. Synthetic polymer which resembles natural rubber is
(a) Cellulose (b) PVC [Guj CETJ (a) neoprene (b) chloroprene [ManipaIJ
(c) Nylon-6 (d) Polythene (c) glyptal (d) nylon
2006 40. Three dimensional molecules with cross-links are formed
36. Which of the following is a condensation polymer? in the case of a CKCETJ
[Jamia Millia l slamia ] (a) thermoplastic (b) thermosetting polymers
(c) Both (a) and (b) (d) None of these
0
41. The number average molecular mass and mass average
II molecular mass of a polymer are respectively 30,000 and
(a) NH- C- (CH2)s
40,000. The polydispersity index of the polymer is
n (a)< 1 (b) > l (c) 1 [Kerala CEE]
(d) 0 (e)-1
(b) Rubber
(c) Polyvinyl chloride 42. Condensation product of caprolactam is [BCECEJ
(d) Polyeth ylene (a) nylon-6 (b) nylon-6,6
37. Which of the following is cross-linked polymer? (c) nylon-60 (d) nylon-6, 10
(a) Teflon [Jamia Millia Islamia ] 43. Natural rubber is which type of polymer? [DCEJ
(b) Orlon (a) Condensation polymer (b) Addition polymer
(c) Nylon (c) Coordination polymer (d) None of these
(d) Bakelite

Topic 2
Polymers of Commercial Importance
2014 2013
1. The catalyst used for olefin polymerisation is 4. Bakelite is a [Ke rala CEE]
(a) Ziegler-Natta catalyst [BITSATJ (a) urea formaldehyde resin
(b) Raney nickel catalyst (b) phenol formaldehyde resin
(c) Wilkinson catalyst (c) polyethylene
(d) Merrifield resin (d) artificial rubber
2. What is incorrect regarding natural rubber? [ManipaIJ (e) polyvinyl chloride
(a) It is cis-polyisoprene 5. Natural rubber is a polymer of [Ke rala CEE]
(b) It is amorphous in nature (a) styrene
(c) It has syndiotactic stereochemistry (b) styrene and 1, 3-butadiene
(d) Molecules of rubber have coiled conformation (c) tetrafluoroethylene
3. Novolac, the linear polymer used in paints is (d) 2-methyl-l, 3-butadiene
[Ke rala CEEJ (e) 3-methyl-l, 2-butadiene
(a) copolymer of 1, 3-butadiene and styrene
6. The common acid used in the manufacture of rayon and
(b) obtained by the polymerisation of methyl methacrylate
plastic is [Ke rala CEEJ
(c) initial product obtained in the condensation of phenol
and formaldehyde in the presence of acid catalyst (a) methanoic acid (b) ethanoic acid
(d) obtained by the polymerisation of caprolactam (c) propanoic acid (d) butanoic acid
(e) copolymer of melamine and formaldehyde (e) malonic acid
 Polymers I 725
2012
7. The polymer polyurethanes are fom1ed by treatmg 16. Glyptal polymer is obtained from glycol by reacting with
diisocyanate with [BITSAT] (a) malonic acid [JCECE]
(a) butadiene (b) isoprene (b) phthalic acid
(c) glycol (d) acrylonitrile (c) maleic acid
8. Which of the following polymers turns yellowish on (d) terephthalic acid
exposure to sunlight? [MPPET] 2009
(a) Polystyrene (b) Nylon 17. The polymer which is used in non-sticky kitchenwares is
(c) Polyethylene (d) Styrene butacliene resin
(a) PVC (b) teflon [UPSEE]
9. Neoprene is a polymer of [OJEE] (c) rayon (d) isoprene
(a) vinyl chloride (b) propene 18. Which polymer is used in controlled drug capsules?
(c) isoprene (d) chloroprene (a) SBR (b) PTFE [Guj CET]
(c) PHBV (d) PAN
2011
10. Thermosetting polymer, bakelite is formed by the reaction
2008
of phenol with [AIEEE] 19. Terylene is a polymer obtained from [MHTCET]
(a) CH3 CH 2 CHO (b) CH3 CHO (a) ethylene glycol and glycerol
(c) HCHO {d) HCOOH (b) ethylene glycol and glyceraldehyde
11. The monomers used for the preparation of nylon 2-nylon 6 (c) ethylene glycol and terephthalic acid
is/are [Kerala CEE] (d) None of the above
(a) caprolactam 20. The monomers ofbuna-S rubber are [KCET]
(b) alanine and aminocaproic acid (a) vinyl chloride and sulphur
(c) glycine and aminocaproic acid (b) butadiene
(d) hexamethylenediamine and adipic acid (c) styrene and butadiene
(e) glycine and amino valeric acid (d) isoprene and butadiene
12. Natural rubber is not used in makmg footwears for polar 21. F2 C= CF2 is a monomer of [UPSEE]
regions because [Guj CET] (a) teflon (b) nylon (c) glyptal (d) buna-S
(a) natural rubber becomes soft at temperature lower 22. In the reaction sequence,
than 10°C

~
(b) natural rubber becomes brittle at temperature lower
than 10°C
c5H H,SO, X Nylon-6
(c) natural rubber melts at temperature lower than I 0°C
(d) natural rubber becomes stronger at temperature lower
than 10°c Xis [UPSEE]
(a) cyclohexanone
2010 (b) caprolactam
13. Which of the following compounds is used in the (c) HO (CH2) 6 NH2
formation of nylon-6,6? [Punjab CET] (d) hexamethyJene cliisocyanate
(a) Sulphur hexafluoride (b) Aclipic acid 23. Which one of the following is not a correct match?
(c) Sulphurous acid (d) Phthalic acid [Guj CET]
14. Which compound polymerises to neoprene? [Guj CET]
Polymer Monomer/s
(a) CH2 = CHC1
(a) Teflon Tetrafluoroethylene
(b) CH 2 =C·Cl-CH=CH2
(b) Plexi glass Methyl methacrylate
(c) Cl 2 C=C·Cl2 (c) Orlon Glycerol, phthalic anhydride
(d) F2C=CF2 ( d) Buna-S Styrene, 1,3-butadiene
15. Which of the following is a monomer ofteflon? 24. Which of the following is currently used as a tyre cord?
(a) Difluoroethane [Guj CET] (a) Polyethylene [DCE]
(b) Trifluoroethane (b) Polypropylene
(c) Tetrafluoroethane (c) Bakelite
(d) None of the above (d) Nylon-6
726 I Chapterwise & Topicwise Engineering Entrances Solved Papers

2007 28. The plastic household crockery is prepared by using

25. Bakelite is a product of the reaction between [BITSATJ (a) melamine and tetrafluoroethane [DCEJ
(b) malonic acid and hexamethylenediamine
(a) formaldehyde and NaOH
(c) melamine and vinyl acetate
(b) aniline and urea
( d) melamine and formaldehyde
( c) phenol and methanal
(d) phenol and chloroform 2006
26. Match Column I with Column II and select the correct 29. PVC polymer can be prepared by which ofthe monomer?
answer using the codes given below. (a)CH 3 CH = CH 2 [WBJEEJ
Column I Column II (b) C 6 H 5 CH = CH 2
(Polymers) (Monomers) (c) CH 2 =CH 2
A. Buna-N I. Phthalic acid and ethylene glycol (d) CH 2 =CH- Cl
B. Nylon-6, 6 2. Terephthalic acid and ethylene glycol
2005
C. Dacron 3. Hexamethylene ctiamine and adipic
acid 30. Which of the following is fully fluorinated polymer?
D. G lyptal plastic 4. Isobutylene and isoprene (a) PVC (b) Thiokol [AIEEEJ
5. Acrylonitrile and butadiene (c) Teflon (d) Neoprene
31. Dacron is a polymer of [BITSAT]
Codes
(a) ethylene glycol and fo1maldehyde
A B C D
(a) 2 1 4 5 (b) ethylene glycol and phenol
(b) 3 4 1 2 (c) ethylene glycol and phthalic acid
(c) 4 3 2 1 (d) ethylene glycol and terephthalic acid
(d) 5 3 1 2 32. Name of compound/compounds used in preparation of
(e) 5 3 2 1 nylon-66. [MHT CET]
27. Catalyst used in dimerisation of acetylene to prepare (a) e-caprolactam
chloroprene is [WB JEE] (b) hexamethylenediamine and adipic acid
(a) HgS04 + H 2 S04 (c) dimethyl terephthalate
(b) Cu 2 Cl 2 (d) hexamethylene diamine
(c)Cu 2 Cl 2 + NH 4 Cl 33. Teflon polymer is formed by the polymerisation of
( d) Cu 2 Cl 2 + NH4 OH (a) CH 2 = CH-CN (b) F2 C = CF2 [UPSEEJ
(c)Cl 2 C =CH 2 (d)H 2 C=CHC1

Answers
TOPIC 1 Polymers : Its Classification and Modes of Polymerisation
1. (a) 2. (b) 3. (b) 4. (b) 5. (c) 6. (a) 7. (a) 8. (c) 9. (d) 10. (b)
11. (a) 12. (d) 13. (C) 14. (b) 15. (b) 16. (d) 17. (d) 18. (c) 19. (b) 20. (a)
21 . (c) 22. (c) 23. (b) 24. (c) 25. (b) 26. (C) 27. (c) 28. (c) 29. (d) 30. (c)
31. (a) 32. (d) 33. (c) 34. (c) 35. (a) 36. (a) 37. (d) 38. (c) 39. (a) 40. (b)
41 . (b) 42. (a) 43. (b)
.Illf!C1_ Polymers of Commercial Importance
1. (a) 2. (c) 3. (c) 4. (b) 5. (d) 6. (b) 7. (c) 8. (d) 9. (d) 10. (c)
11. (c) 12. (b) 13. (b) 14. (b) 15. (d) 16. (b) 17. (b) 18. (c) 19. (c) 20. (c)
21. (a) 22. (b) 23. (c) 24. (d) 25. (c) 26. (e) 27. (c) 28. (d) 29. (d) 30. (c)
31. (d) 32. (b) 33. (b)
 Explanations
Topic 1 Polymers : Its Classification Modes of Polymerisation
1. Dacron is a condensation polymer of ethylene glycol and 5. Terylene is a copolymer ofterephthalic acid and ethylene glycol.
terephthalic acid. Formation of dacron can be shown as It is a polyester fibre.

nH o - c-@-c-
0
II
Terephthalic acid
II
0
OH + nHO -
1
CH2 - CH2 -
Ethylene
~~-
--{211-I) H20 Polymensat,on
OH nHOoc-@-coOH + nHOCH2 CH2 OH
Terephthalic acid
Ethylene g lycol

--.l
- _-<211-- -1>"-20 o c - @ - coo - CH 2 - c H2 - o 1
1 I
t
Terylene
(dacron)
c-@-c- OCH2 - CH2 - 0t
II
0
II
0 Dacron n
Since, it is a product of condensation polymerisation, in which
there is a repetitive condensation reaction between bifunctional
Here, elimination of water occurs. So, this reaction is known as monomer, the process is called step growth polymerisation and
condensation polymerisation. the polymer is known as step growth polymer.
2. The structure of copolymer of ethene and vinyl chloride is shown 6. Polymers are very high molecular mass compounds which are
below prepared by the combination of large number of repeating
structural units joined together through covalent bonds.
Ethcne Vinyl chloride Polymers may be synthetic or natural. While aldehydes and esters
are the organic compounds which contain functional groups,

~ t CH,~CH,CH,~r~+ - CHO (aldehydic) and RCOO- (ester). Though starch,

cellulose and protein are naturally organic compounds but they
contain large number of repeating structural units.
Hence, these are natural polymers.
Copolymer
7. When two or more different monomer units are allowed to
Molecular weight of ethene (CH2 CH2 ) = 28 polymerise, a copolymer is formed which contains multiple units
Molecular weight of vinyl chloride (CH 2 CHCI) = 62.5 of each polymer used, in the same polymeric chain.
Empirical formu la weight of copolymer Copolymerisation
nCH2 =CH- CH = CH 2 + n CH=CH 2
= 28 + 62.5 = 90.5 I, 3-butadiene J

Mass% of vinyl chloride in the copolymer

C6Hs
= 62.5 X 100 = 69 _06 "" 69% Styrene
90.5
3. When a diacid is condensed with dialcohol,the polymer obtained
contains ester linkage.

nHOCH2CH2OH + nHOoc - @ - c o OH
Ethylene glycol
(dialcohol) Terephthalic acid
(diacid)

-<2n-1)H20 l
1 o - CH2CH2 - ~ - - @ - c o
(Ester linkage)
J
1, Butadiene styrene
(addition polymer)
n

Dacron
8. Polymers are the high molecular mass compounds which are
formed by the combination of a large number of one or more
types of simple molecules or units (called monomers). This
Polymerisation process is known as polymerisation.
4. nCH2 =rH
9. Polycondensation products of dicarboxylic acids and diols are
CN called polyesters having ester linkage -+COO+- .
Acrylonitrile n e.g. terylene or dacron.
Polyacrylonirile
728 I Chapterwise & Topicwise Engineering Entrances Solved Papers
15. Synthetic rubber or neoprene is a polymer of
chloroprene (2-chlorobuta-1,3-diene). Hence, it is
Ethylene glycol Terephthalic acid also called polychloroprene.
·CH -<; CH-CH Polymerisation
II 2-1 - - 2
~
(2n- 1), H20
l o - CH2 CH 2 - oII c o _
- 0 - co t , CI
Chloroprene
0 n
Terylene

L,- r- CH- CH,}

10. POI abbreviates as polydispersity index of polymer.

PDT = MW
l CI
Neoprene or polychloroprene
ll

Mn
16. DNA is a natural biopolymer.
For natural polymers, PDT = I.
17. Nylon has amide linkage capable of forming
and for synthetic polymer, PDT > I
intermolecular H-bonding as
11. Molecular weight of polymers is determined easily with the help of van 't Sites capable of fonning H-bonding
Hoff equation of osmotic pressure.
w
pV=nST= - ST
111

12. Buna-S is an additive copolymer. It is a polymer of 75% butadiene and 25% iI_) _CH,CH,CH,CH,CH,l
styrene. Tt is also known as artificial/synthetic rubber.
C6Hs n
Nylon.6
I p I . •
nCH2=CH- CH=CH 2 + 11CH2 =CH oymens:ation Due to H-bonding, nylon has strong intermolecular
I, 3-butadiene Styrene attraction. Cellulose is a polyhydroxy compound, also
C6Hs capable of forming strong intermolecular H-bonding.
I Polyvinyl chloride is a polar polymer due to carbon

f:
+CH2 CH = CHCH2 CH2 - CH+ 11 chlorine bond and it possess strong dipole-dipole
(butadiene styrene copolymer) attraction. Natural rubber is polyisoprene, a
Buna-S

13. Bakelite is a condensation polymer of formaldehyde (HCHO) and phenol

(C6 H 5 0H) formed by the loss of water molecules. Hence, bakelite is a hydro=OO,, w1~::"::1ttractioa
synthetic condensation polymer.
0
II
14. Nylon-6,6, is a polyamide containing - C- NH group belong to the class of
fibre. These polymers have strong intermolecular forces like hydrogen cis-poly isoprene
Natural rubber
0
II
bonding between - C- NH group of successive chains. 18. Buna-N acnmlly abbreviated from where Bu
represents 1,3-butadiene, Na represents sodium and
I N represents nitrile (acrylonitrile). Thus, Buna-N is
H O H
obtained by the copolymerisation of
I II I 75% I , 3-butadiene and 25% acrylonitrile (vinyl
~c/N~N/C~c/N'--._,/ cyanide) in the presence of sodium metal.
II I 11 nCH2 = CH-CH = CH2 + nCH2 = <;H
0 H O I, 3- butadiene(75%) I
CN
Addition Crylonitrile (25%)
H 0 H copolymerisation
I II I
/"---_c/N~N/C~c/N'--._,/
II I II
0 H 0
Hydrogen bonding in nylon-6,6
Buna- N (NRB)
 Polymers I 729
19. Proteins are the condensation polymers ofo:-amino acids containing Condensation
A-B+A A-B-A
amide linkages (also called peptide linkage).
A-B-A+B ------t A-B-A-B
The product of each step is again a bifunctional molecule

fco-r}
20. Saran is a copolymer of vinyl chloride and vinylidene chloride.
which can react with other monomer and dimer molecules
until a long chain polymer is formed. Thus, the molecular
weight of polymer rises throughout the reaction. Further, in
this process, no initiator is required and it is also called step
growth polymerisation.
nCH2 = CHCI + nCH 2 =CCl 2 -

-bl
28. Chain growth polymerisation requires an initiator (such as

t
organic peroxides) to produce a free radical to which the
monomers are added in a chain fashion. Initiators are added in a
I
H 2 - CH- CH2 I very small quantities and are decomposed by heat, light or
oxidation-reduction reaction to produce reactive species, i.e.
Cl Cl free radical. Polystyrene is an example of chain growth polymer
n
Saran because in it, styrene molecules are associated in the form of
While orion, PVC and teflon are addition homopolymers. monomer.
21. Cellulose diacetate (used in making threads) is a semi-synthetic
polymer as it is obtained from natural polymer (i.e. cellulose) by
chemical modification.
22. Buna-S is a elastomer, thus has weakest intermolecular forces.
Nylon-6,6, is a fibre, thus has strong intermolecular forces like
H-bonding. Polythene is a thermoplastic polymers, thus the
intermolecular force present in polythene is in between elastomer and
fibre. Thus, the order of intermolecular force of these polymers is
buna - S < polythene< nylon - 6,6.
B C A

23. The ratio of weight average molecular weight and the number
average molecular weight is called polydispersity index (PDT). 29. Nylon-6,6 is a polyamide fibre which is manufactured by the
condensation polymerisation of adipic acid and
PDI= Mw
he7m:1ylene diamin~
Mn

t 1
where, M., =weight average molecular weight ll II
C-(CH2 ) 4 - C- NH-(CH2 ) 6 - NH
Mn= number average molecular weight
POI is unity for natural monodispersed polymer but for synth etic 11

polymers, it is always greater than unity.

Nylon - 6, 6
24. In cationic polymerisation, carbocations are formed. Greater the
stability of the carbocation, more reactive is the alkene. Since, the 30. Nylon threads contain amide linkages thus, these are made up
stability of the intermediate carbocation follows the order of polyamide. Some common nylons are
+ + Nylon-6
CH3 - CHC6H 5 > CH3 - CHCH 3 >
0
+ +
CH 3 - CH - Cl > CH3 - CHC02 CH 3 II Heat
n[H2N - (CH2\ - C- OH] . .
Polymensat1on
Therefore, reactivity decreases in the same order. Thus, styrene is
most reactive.
25. Teflon, cellulose and natural rubber are examples of polymer, but
petroleum is dark yellow-brown, lighter than water, oily liquid found
tNH ~CH,),-gJ
Nylon-6,6
in impervious rocks in the earth. It is made up of long chain
hydrocarbons. n[H 2N-(CH2\;- NH2] + n [HOOC- (CH2)rCOOH]
26. Rayon, an artificial textile material composed of regenerated and
purified cellulose of wood pulp or cotton. Thus, it is known as
High pressure 1553 K

regenerated synthetic fibre.

27. The process of condensation polymerisation takes place in the
following man ner.
A+ B Condensation A_B
Monomers Dimer Nylon-6, 6 ""Amide
linkage
730 I Chapterwise & Topicwise Engineering Entrances Solved Papers

31. Chain growth polymers are formed by the chain growth 40. When heavily branched molecules or chains are heated, they result in
polymerisation or chain polymerisation. This polymerisation hard infusible and insoluble three dimensional or extensively
process involves a series of reaction each ofwhich consumes a cross-linked products. These three dimensional or extensively
reactive particle and produces another similar particle cross-linked products are called thermosetting polymers.
resulting a chain reaction. Teflon is a chain growth polymer. It
is the polymer oftetratluoroethy lene. 4 1. PDT = A!:_, = 40,000
Mn 30,000
=weight average molecular mass

ir'_r1
Here, M w
Mn= number average molecular mass
So, the value is more than I .
32. The sttuerure. a,ggeos illlt 42. Caprolactam is w idely used for preparing nylon-6. For this, it is first
hydrolysed with water to form amino acid. On heating, this amino
acid polymer gives nylon-6.
polymerisation takes p lace due to the loss ofvinylic hydrogen
atom, which is not possible.
33. Nylon-6,6 contains an amide linkage--(CONH) therefore, it is
a polyamide polymer.
34. PHBV (poly [>-hydroxy butyrate-co-f>-hydroxy-valerate), a
&
Caprolactam
";° H,N - (CH,),- COOHl
Heat
Polymerisation
polyester, is a copolymer of 3-hydroxy butanoic acid and
0
3-hydroxy pentanoic acid. As it contains functional group in
their polymer chains which can be dissociated into small
fragments by enzymes, therefore, PHBV is a biodegradable
-f HN - (CH2)-
Nylon-6
d
1

-3n
polymer.
43. Nanrral mbber is obtained from the later of the plant named as Hevea
35. Cellulose is a biodegradable polymer.
brasiliensis.
36. (i) Addition polymers are those in which monomer lmits
It is a linear addition homopolymer of isoprene.
combine w ithout loss of small molecules. Rubber, polyvinyl
chloride and polyethylene are addition polymers.
(ii) Condensation polymers are those in which monomer units
condense to form large units alongwith loss of small tCH,-tCH-CHl
tHN-i- l;,
molecules like H 2 O,NH 3 .
Natural rubber

(CH,), ,mide H,kage. fom<d by

Topic 2 Polymers of Commercial
Importance
condensation of -COOR group with - NH2 group. It is 1. Ziegler-Natta catalyst [TiC14 + Al(C2 H 5 ) 3 ] is used as a catalyst in
accompanied by loss ofwater molecules. So, it is a condensation
polymer. the polymerisation of olefins.

37. (i) Teflon, orion and ny lon are straight chain polymers. 2. Natural rubber is cis-polyisoprene or cis-1 , 4-polyisoprene.

i
+
(ii) Bakelite is cross-linked condensation copolymer of phenol
3C~ _ / H H3C ~ / H
and formaldehyde. /c - c~ / CH2~ /CH2~ /c = C,
38. ( 1) Terylene is a polyester as it has ester linkages. H2 CH2 C= C CH2 'CH2
CH/ ~H
(ii) Nylon is a polyamide as it has amide linkages.
(iii) Orlon and rayon are synthetic fibres. cis- l, 4-polyisoprene

39. Neoprene is the most commonly used synthetic rubber. It is a Since, the above structure shows that methyl groups are present on
homopolymer of chloroprene (2-chloro-buta-1,3-diene). It the same side of zig-zag backbone, therefore nanrral rubber has iso
resembles in appearance with natural rubber. tactic stereoche mical arrangement not syndiotactic
Polymerisation [or alternate arrangement].
nCH2 = CH-C=CH2 - - --
1 3. When phenol is condensed w ith formaldehyde in the presence of a
Cl base, initially a mixture of o and p-hydroxy benzyle alcohol is
obtained out of which, o-forms undergo self condensation to give a
CH -CH= C-CH linear polymer called novolac.
2 I 2

Cl

n
Neoprene
 Polymers I 731
7. nO=C=N- R- N=C=O + nHO- R'- OH -

@ OH

Phenol
+ HCHO
Fonnaldehyde
ow>
&OHCH OH
Q
o-hydroxy
2
+
~OH
Q
Diisocyanate
0
II
+ c - NH- R- NH- C- O- R'- O-+,,
0
Glycol

II
benzyl alcohol CH OH
2 Polyurethanes
p-hydroxy benzyl
OH alcohol C6Hs
I
L9J
H ~ C H2OH
-nH20
8. nCH2 =CH + 11CH2 =CH- CH=CH,
Styrene Butadiene

C6Hs
-

I
fc&CH,~CH,t - + CH2 - CH- CH 2 - CH=CH - CH2 -f,,
Styrene butadiene resin

This resin turns yellowish on exposure to sunlight.

Novolac 9. Neoprene is an addition polymer of chloroprene. It gives an
(linear polymer) artificial rubber when heated with ZnO or MgO.
4. Bakelite is a phenol formaldehyde resin formed when phenol is Cl
condensed with formaldehyde in the presence of a base. This results I
in the mixture of o and µ-hydroxy benzyl alcohol which again
condenses to give a highly cross-linked bakelite polymer.
nCH2=CH- C= CH2
Polymerisation
r r' l
- CH, - CH =C- CH,-
;I:
lSJ + HCHO ~
L-cH,OH
lQ_J - +
~OH
0
L -
10. Bakelite is a thermosetting plastic formed by reaction of
-J,,

phenol with HCHO in the presence ofconc. H 2SO4 .

H 20 OH

L - C H20H
nLSJ +n
~OH -,-,-,,/1H2C*OHCH2~
Q -nH,O Q Q
nHCHO + 11 ~
U I!,.
cone. H 2SO4
OH OH
CHiOH CH2 OH
CH2
-H,C--qr-CH,~CH,--
x2
JQl ?H2 ?H2
•H,C CH,t§JCH, OH
Bakelite

It is thus cross-linked polymer, condensation taking place at o

and p-positions.
5. Natural rubber is a hydrocarbon polymer built up from the monomer
isoprene as 11 . Nylon 2-nylon 6 is an alternating polyamide copolymer of
CH3 glycine and amino caproic acid. It is a biodegradable
polymer.
1 2 I 3 4 Polymerisation
nCH 2 = C-CH=CRi nH2NCH2COOH+ 11H 2N(CH2 ) 5 COOH -
lsoprene (or 2-tnethyl-1, 3-butadiene) (I. 4-addition) Glycine Aminocaproic acid

0
II
[HN- CH2CONH(CH2 ) 5 C J
Nylon -2- nylo n -6

12. Natural rubber is a linear polymer ofisoprene

Natural rubber
(2-methyl - I, 3 -butadiene). Tt becomes soft at high
6. Rayon and plastic polymers are manufactured with the help of temperature (335 K) and brittle at low temperature(< 283 K),
ethanoic acid (CH3 COOH). so it is not used in making footwears for polar regions.
732 I Chapterwise & Topicwise Engineering Entrances Solved Papers
13. Hexamethylene diamine and adipic acid is used in the formation of
ny lon-6,6.
nH2 N- (CH 2 ) 6 - NH2 + nHOOC- (CH2 ) 4 - COOH
Hexam.,thylenediamine Adipic acid
,&
lS:2J ::,~CH-CH~CH,l
+
Butadiene

),-~1
Styrene
r o o1
tNH-(CH,J.-NH-L(CH,
Nylon -6,6
14. Neoprene is a synthetic rubber. It is prepared by polymerisation of
chloroprene (2-chlorobuta -1, 3-diene).
21. Teflon is a polymer oftetrafluoroethy lene. It is used for coating
Polymerisation articles and cookwares to make them non-sticky.
nCH2 = TCH = CH2
nF2 C = CF2 . Hear - [F2 C -CF2 t,;-
Cl Tetrafluoroethylene H tgh pressure Teflon
Chloroprene

Nylon-6,6 is a polymer of adipic acid and hexamethylene

diamine.Glyptal is a polymer of ethylene glycol and phthalic acid.
Buna-S is a polymer ofbutadiene and styrene.
15. Teflon is an addition polymer oftetrafluoroethylene. 22. Caprolactam is the monomer of nylon-6.
Heat
nF2 C= CF2 + F2C- CFrl,;
pressure
-f nl
6
Teflon
Tetratluoroethylene
NOH H2S04 t i-{O 540 K
16. Glyptal or is a condensation copolymer of ethylene glycol and \_) --'--'---? HN-(CH2)s-C J,.
phthalic acid. Nylon-6
Cyclohexane Caprolactam
n HO - CH2 - CH2 - OH + nHOOC@COOH oxime X
ethylene
glycol Q Thus, X is caprolactam.

1
Phthalic 23. Orlon is a polymer of acrylonitrile (CH2 = CH - CN).
acid
24. Nylon-6 is used in the manufacture of tyre cord. It is a polymer
of caprolactam. It contains amide linkage.

1r rl
f
OCH2- CH200C@COO 25. OH
----nH2O
0
----t

Glyptal

17. Teflon (polytetrafluoroethylene is a polymer of tetrafluoroet-

n
n
©
Phenol
+ nH CHO
Fonnaldehyde
(methane!)
----nHzO

1[Q[e:~:J9JI
26. Buna-N is a polymer of acrylonitrile (CH 2 = CH(CN)) and
hylene and is used for coating on non-stick utensils. butadiene (CH2 =CH-CH= CH2 ).
Polymerisation Nylon-6,6 is a polymer ofhexamethy lene diamine
(NH2 - (CH 2 ) 6 - NH 2 ] and adipic acid
18. PHBV (poly-!3-hydroxy butyrate-co-!3-hydroxy valerate) is used in [HOOC- (CH 2 ) 4 - COOH].
controlled dmg capsules.
Dacron (terylene) is a polymer ofterephthalic acid
19. Ethylene glycol on reaction with terephthalic acid forms the
polymer terylene (also known as dacron) w hich is used as (HOOC-@- COOH) and ethylene glycol
synthetic fibre.
nHOCH2 · CH2 OH+ nHOOC · C6 H 4 · COOH (HOCH2 - CH 2 OH).
Ethylene glycol Terephthalic acid
Glyptal plastic is a polymer ofphthal ic acid
-11Hp_j, 0 0
II II rc3'rCOOH )
+-OCH 2 -CH 2 - O - C-C6 H 4 -C+,;
(polymer) ( ~ C O OH
Terylene

20. Buna-S rnbber is a lso called SBR, Styrene Butadiene Rubber. It is and ethylene glycol (HOCH2 - CH2 OH).
a copolymer of75% butadiene and 25% styrene.
 Polymers I 733
is fully fluorinated polymer.
27. 2HC:aaaCH ~c~i
4
H 2 C = CH-C = CH
Vinyl acetylene 31. nHO-CH 2 -CH 2 - 0H +
Ethylene glycol
HCI CH2 = CH-C =CH2
I Polymerisation
Cl n [Hooc---@--cooH] ---nH20
Chloroprene

i
Terephthalic acid
Polymerisation 0 0
~
-fCH 2 - CH = C-CHd,,
I
Cl
28. The unbreakable plastic household crockery is made from
t 0 - CH2- CH2- 0 -
Dacron
II ~ CII
C

Ethylene glycol and terephthalic acid on condensation give dacron.

11

polymer of formaldehyde (HCHO) and melamine.

32. Nylon-6,6 is a polymer of adipic acid and hexamethy lene
H 2N'-/N......_,,,--NH2 diamine.
I QI + HCHO Polymerisation Melamine
polymer
nHOOC- (CH2 ) 4 - COOR + H 2N - (CH2 ) 6 NH2
NJN Formaldehyde Adipic acid Hexamethylene diatnine

NH2
Melamine
29. The monomer used for the preparation of PVC (Polyvinyl

1n
chloride) polymer is vinyl chloride, i.e.
CH 2 =CH -Cl.
33. (i) CH2 = CH - CN (acrylonitrile) polymerises to form PAN.
nCH 2 = CHCJ --------, CH 2 - (ii) CH2 = CHCI (viny l chloride) polymerises to form PVC.
Peroxide
Vinyl chloride di n (iii) F2 C = CF2 (tetrafluoroethylene) polymerises to form teflon.

PVC
Chemistry in Everyday Life
QUICK REVIEW
• Drugs These are chemicals which interact with
macromolecular targets and produce a biological response.
When biological response is therapeutic and useful, these
chemicals are called medicines and are used in diagnosis,
prevention and treatment of diseases. Chemotherapy is
the use of chemicals for therapeutic effect.
• Drugs usually interact with biomolecules, such as
carbohydrates, lipids, proteins and nucleic acids. These are
called drug target. Drug should be designed in such a way
that it reaches the target without being metabolised in
between.
• The proteins which perform the role of biological catalysts
in the body are known as enzymes.
• Some drugs can block the binding site of the enzyme and
prevent the binding of the substrate or can inhibit the
catalytic activity of the enzyme. Such drugs are known as
enzyme inhibitors.
• Antipyretic It is a drug which is responsible for lowering
the temperature of feverish body. Aspirin is an important
antipyretic. Chemically it is acetyl salicylic acid. Derivatives
of p-aminophenol are also used as antipyretic. For
example-phenacetin (4-ethoxyacetanilide), paracetamol
(4-acetamidophenol) etc.
• Analgesics These are the drugs which relieve or decrease
pain. These may be narcotics (examples-morphine,
codeine and heroin) or non-narcotics (examples-ibuprofen,
analgin, naproxen, diclofenac sodium etc.) Narcotics cause
addiction while non-narcotics don't cause addiction.
Aspirin and analgin are analgesics as well as antipyretic.
• Antimicrobials These are used to cure infections due to
microorganisms. These may be bactericidal (which kiJI the
microorganisms in the body) or bacteriostatic (which
inhibit the growth of microorganisms).
The common example of antimicrobial drug is
sulphanilamides and their derivatives such as
suJphadiazine, sulphadimidine etc. Sulphonamides in
combination with trimethoprim are preferred in the
treatment of infections of urinary tract.
• Antibiotics These are used as drugs to treat infections
because of their low toxicity for humans and animals.
These are produced by or derived from living cells.
These may be broad spectrum antibiotics or narrow
spectrum antibiotics.
Penicillin G is narrow spectrum antibiotic, it is effective
against single organism or disease while ampicillin,
amoxycillin and chloramphenicol are broad spectrum
antibiotics used against a wide range of bacteria.
• Antiseptics and disinfectants These are the chemicals
which either kill or prevent the growth of microorganisms.
Antiseptics are applied to the living tissues while
disinfectants are used to inanimate objects such as floors,
drainage system etc. Sometimes same substances can act as
an antiseptic as well as disinfectant. For example 0.2%
solution of phenol is an antiseptic while its 1% solution is
disinfectant. Commonly used antiseptic dettol is a mixture
of chloroxylenol and terpineol.
• Antihistamines These diminish or abolish the main
actions ofhistamine released in the body and hence prevent
the allergic reactions. For examples synthetic drugs,
brompheniramine (Dimetapp) and terfenadine (seldane),
act as antihistamines (antiallergic). Cimetidine (Tegamet)
and ranitidine (Zantac) drugs are used to prevent the
interaction of histamine with the receptors present in the
stomach wall (antacid).
• Antacids These are used in the treatment of acidity.
Sodium hydrogen carbonate or a mixture ofaluminium and
magnesium hydroxide are used as antacids.

Metal hydroxides are better antacids because these do not
increase the pH above neutrality.
• Tranquilisers or hypnotics These are used for the
treatment of stress, mild and severe mental diseases.
Derivatives of barbituric acid are used as tranquilisers to
release mental tension and to reduce anxiety.
Sedatives act as depressant and supress the activities of
nervous system.
Antifertility drugs are used to prevent unwanted
pregnancies in women.
Birth control pills essentially contain a mixture of synthetic
estrogen and progesteron derivatives. Both of them are
hormones. Progesteron supresses ovulation.
• Norethindrone It is an example ofsynthetic progesterone
derivative most widely used as antifertility drug. The
estrogen derivative which is used in combination with
progesterone derivative is ethynylestradiol (novestrol).
• Dye It is a synthetic or natural colouring matter which is
used to stain materials especially fabrics.
(i) Azodyes contain one or more azo group
(-N = N-). These are highly coloured.
e.g.- aniline yellow, methyl red, methyl orange and
congo red.
(ii) Triaryl methane dyes have central carbon atom
bonded to three aromatic rings. One of which is in
quinonoid form. e.g.-malachite green.
(iii) Alizarin is an example of anthraquinone dye and
phenolphthalein is an example of phthalein dye.
(iv) Indigo is the oldest known dye. Neel used as blueing
agent in launda1y is not indigo, it is ultra marine.
(v) Mordant dyes are applied to fabrics with the help of
certain additional substances known as mordants.
Alizarin is a typical mordant dye. It gives rose red
colour with Al 3+, blue colour with Ba 2 +, violet
colour with Fe3+.
(vi) Vat dyes are insoluble in water and cannot be applied
directly. In reduced form (colourless) they are
applied to fabrics and then fabric is exposed to air or
some oxidising agent to develop colour. e.g. indigo.
• Chemicals in food Chemicals are added to food for their
preservation and enhancing their appeal.
(i) Anti-oxidants retard the action of oxygen on food.
Butylated hydroxy anisole (BHA) and butylated
hydroxy toluene (BHT) are important anti-oxidants.
(ii) Artifical sweetners act as substitute for sugar. e.g.
aspartame, alitame, sucralose etc.
Chemistry in Everyday Life I 735
(iii) Food preservatives prevent spoilage of food due to
microbial growth. Table salt, sugar, vegetable oil,
sodium benzoate and S02 (source ofS0 2 is potassium
metabisulphite) are common preservatives.
• Pheromones are chemicals capable of acting outside the
body of the recreting individual to impact the behaviour of
the receiving individual. There use among insects has been
particularly well documented.
• Detergents and soaps These are cleansing agents.
• Soaps are sodium or potassium salts of long chain fatty
acids such as stearic acid.
• Saponification It is the process in which soaps are formed
by heating fat with aqueous sodium hydroxide solution.
Bithional is used in medicated soaps to impart antiseptic
properties in soaps.
• Chemically detergents are either sulphates or sulphonates
oflong chain hydrocarbons and these are better than soaps
as they lather easily with hard water. Detergent molecules
associated with branched hydrocarbon chains cause
pollution. These days the amount of branching can be kept
to minimum to prevent pollution.
Detergents are classified as :
(i) Anionic detergents, these are sodium salts of
sulphonated long chain alcohols or hydrocarbons.
(ii) Cationic detergents, these are quaternary ammonium
salts of amines with acetates, chlorides or bromides
as anions. Cetyltrimethyl ammonium bromide is
cationic detergent and is used in hair conditioner.
(iii) Non-ionic detergents, these are esters of high
molecular mass alcohols. Liquid dishwashing
detergents are of non-ionic type.
• Rocket propellents are the combinations of an oxidiser and
fuel.
• Composite propellants consist of a blend or mixture of a
fuel and an oxidiser. e.g. polyurethane or polybutadiene
used as fuel and ammonium perchlorate acts as an oxidiser.
• Double base propellants consist of nitroglycerine or
nitrocellulose.
• Hydrazine, methyl nitrite, nitromethane are some of the
examples of mono liquid propellants.
• Biliquid propellants consist ofa combination of an oxidiser
and a fuel. e.g. kerosene and liquid oxygen.
• Hybrid propellants employ a solid fuel and liquid oxidiser.
e.g. a mixture of acrylic rubber and liquid N 2 0 4 .
 Topic 1
Chemicals in Medicines
2014 2010
1. Which of the following statement is not true about the drug 10. The correct structw-e of the drug paracetamol is
barbital? [BITSAT]
(a) It is used in sleeping pills (a) HO ---@- CONH 2 [Manipall
(b) It is a non-hypnotic drug
(c) It is tranquilliser (b) HO ---@- NHCOCH3
(d) It causes addiction
2. Which set has different class of compounds? [VITEEEJ (c) Cl ---@- CONH2
(a) Tranquillisers-equanil, heroin, valium
(b) Antiseptics-bithional, dettol, boric acid (d) Cl ---@-co CH3
(c) Analgesics-naproxen, morphine, aspirin
(d) Bactericidal-penicillin, aminoglycosides, ofloxacin 11. Chloramine-T is a [MHT CETJ
3. What are the substances which mimic the natural chemical (a) disinfectant (b) antiseptic
messengers? [EAMCET] (c) analgesic (d) antipyretics
(a) Antibiotics (b) Antagonists 12. Aspirin is an acetylation product of CMHT CETJ
(c) Agonists (d) Receptors (a) o-hydroxybenzoic acid (b) o-hydroxybenzene
4. Use of chemicals for therapeutic effect is called (c) m-hydroxybenzoic acid (d) p-dihydroxybenzene
(a) medicines [J&K CETJ 13. Tranquillisers are also known as CMHT CETJ
(b) chemotherapy
(a) psychosomatic durgs
(c) drug-target interaction
(b) psychotherapeutic drugs
(d) phototherapy
(c) psychosystolic drugs
2013 (d) None of the above
5. Aspirin is [Kerala CEEJ 14. Which one among the following is not an analgesic?
(a) acetyl salicylic acid (b) 2-methoxy benzoic acid (a) Ibuprofen [Kerala CEEJ
(c) acety I oxalic acid (d) methyl benzoic acid (b) Naproxen
(e) ethoxy benzoic acid (c) Aspirin
(d) Valium
2012 (e) Diclofenac sodium
6. The carboxyl functional group (-COOH) is present in 15. Which among the following is not an antibiotic ?
(a) picric acid (b) barbituric acid [11T JEE] (a) Penicillin (b) Oxytocin [Kerala CEE]
(c) ascorbic acid (d) aspirin (c) Erythromycin (d) Tetracycline
7. Which of the following antibiotics was first discovered? (e) Ofloxacin
(a) Ampicillin (b) Amoxycillin [OJEEJ 16. Benzalkonium chloride is a [AMU]
(c) Penicillin (d) Chloramphenicol
(a) cationic sw-factant and antiseptic
8. Which of the following is antipyretic and analgesic? (b) anionic surfactant and soluble in most of organic
(a) SuJphaguanidine (b) Paracetamol [AMU] sovlents
(c) Penicillin (d) Phenol (c) cationic sufactant and insoluble in most of organic
solvents
2011 (d) cationic sw-factant and antin1alarial
9. Paracetamol is [WBJEE] 17. Which of the following is used as a ''morning after pill''?
(a) methyl salicylate (a) Norethindrone [Guj CETJ
(b) phenyl salicylate (b) Ethynylestradiol
(c) N-acetylp-amino phenol (c) Mifepristone
(d) acetyl salicylic acid (d) Bithional
 Chemistry in Everyday Life I 737
2009
18. Paracetamol is a/an [KCET] 25. Tincture of iodine is [BCECE]
(a) antipyretic (b) analgesic (a) aqueous solution of 12
(c) Both (a) and (b) (d) antimalarial (b) solution of 12 in aqueous KI
19. Bithional is an example of [AMU] (c) alcoholic solution of 12
(d) aqueous solution of KI
(a) disinfectant (b) antiseptic
(c) antibiotic (d) analgesic 26. Chemically aspirin is known as [BCECE]
20. The functional groups present in 'salol' are [EAMCET] (a) salicylic acid
(a)-NH2 and -OR (b) salicylaldehyde
(b)-OHand -COR (c) 2-acetoxybenzoic acid
(c)-NH2 and -COOH (d) phenyl salicylate
(d)-OHand -COOR 2007
21. Match the following columns.
27. Chloramphenicol is [DCE]
Column I Column II (a) narrow spectrum antibiotic
A. Sodimn perborate I. Disinfectant (b) broad spectrum analgesic
B. Chlorine 2. Antiseptic (c) broad spectrum antibiotic
c. Bithional 3. Milk bleaching agent (d) broad spectrum antibacterial
D. Potassium stearate 4 . Soap
2006
Codes [DCE] 28. Which of the following is bacteriostatic? [Kerala CEEJ
A B C D (a) Penicillin (b) Erythromycin
(a) I 2 3 4
(c) Amino glycodine (d) Ofloxacin
(b) 2 3 4 I
(e) Bithional
(c) 3 I 2 4
(d) 4 I 2 3 29. Phenacetin is used as [WBJEE]
(a) antipyretics (b) antiseptics
H
(c) analgesic (d) antimala1ials
22. The drug N~
I .is used as [DCE] 30. The reagent(s) used in the preparation of aspirin from
( . A CH salicylic acid [J&K CETJ
N I 2 (a)SOC12 ,pyridine (b)(CH3 CO)iO,H+
CH2 - NH 2 (c) CH3 CO2 H,HC1 (d) CH 3 Cl,A1Cl 3
(a) vasodilator (b) analgesics
(c) antacid (d) antiseptic
2005
31. Antiseptic chloroxylenol is [KCET]
23. The drug used to bring down the fever are known as
(a) 4-chloro-3, 5-dimethyl phenol
(a) analgesic (b) antibiotic [DCE]
(b) 3-chloro-4, 5-dimethyl phenol
(c) antipyretic (d) sulpha drugs (c) 4-chloro-2, 5-dimethyl phenol
24. Which of the following gives paracetamol on acetylation? (d) 5-chloro-3, 4-dimethyl phenol

,&
32. 4-chloro-3, 5-dimethyl phenol is called [Guj CETJ

(a) LNH
l8J
z (b)
~NH2
[DCEJ
(a) chloramphenicol
(c) barbital
(b) paracetamol
(d) dettol
33. Compound A given below is [GujCETJ
OCOCH3
©YCOOH
A
(a) antiseptic (b) antibiotic
(c) analgesic (d) pesticide
738 I Chapterwise & Topicwise Engineering Entrances Solved Papers
34. The pH value of gastric juice in human stomach is about 1.8 and in the small intestine it is about 7.8. The pK a value of aspirin is
3.5. Aspirin will be [Jamia Millia Islamia]
(a) completely ionised in the small intestine and in the stomach
(b) unionised in the small intestine and in the stomach
( c) ionised in the small intestine and almost unionised in
the stomach
( d) ionised in the stomach and almost unionised in the small intestine

Topic 2
Chemicals in Food and Pheromones
2014 2011
1. Butylated hydroxy toluene as a food additive acts as 3. Which of the following is pheromone? [Guj CETJ
(a) antioxidant [KCETJ (a) Linalool (b) Disparlure
(b) flavouring agent ( c) BHA ( d) Alifame
( c) colouring agent
(d) emulsifier 2007
2. Food prese1vatives prevent spoilage offood due to microbial 4. The safest and the most common alternative of sugar is
growth. The most commonly used preservatives are (a) glucose [UPSEEJ
(a) table salt, sugar [J&K CETJ (b) aspartame
(b) vegetable oils and sodium benzoate ( c) saccharin
(c) C 6 H 5 COONa ( d) cyclodextrin
( d) All of the above

Topic 3
Chemicals as Dyes and Cosmetics
2014 2011
1. For the identification of ~-naphthol using dye test, it is 3. Match metal ion Colunm I with colour Column II in the
necessary to use [JEE Advanced] presence of alizarin.
(a) dichloromethane solution of~-naphthol Column I Column II
(b) acidic solution of~-naphthol Sr 2+ 1. B lue
A.
(c) neutral solution of~-naphthol
B. Mg2+ 2. P ink
(d) alkaline solution of~-naphthol

2012 c. AIJ+ 3. Violet

D. Ba 2+ 4. Red
2. Alizarin is an example of [BITSAT]
(a) triaryl dye
Codes [Guj CETJ
(b) azo dye
(c) vat dye
A B C D A B C D
(a) I 4 3 2 (b) 2 I 4 3
( d) anthraquinone dye
(c) 3 2 I 4 (d) 2 3 4 I
 Chemistry in Everyday Life I 739
2010 2006
4. Which type of dyes are not used to dye nylon and polyester 8. Which of the following is red dye ? [OJEE]

(•) @-N~Nt
fibres? [Guj CET] OH
(a) Vat dyes (b) Basic dyes
(c) Disperse dyes (d) Insoluble azo dyes

2008
5. An insoluble dye is reduced to a soluble colourless leuco
form by an alkaline reducing agent. The fibre is soaked in
the dye solution and then exposed to air to develop the (b) © - N= N---@ N(CH3)i
colour. The dye is [Guj CET]
(a) mordant dye (b) vat dye (c) © - N= N---@- OH
(c) azo dye (d) clirect dye
(d) © - N= N---@-NH2
2007
6. Alizarin belongs to the class of [BITSAT]
(a) Vat dye (b) Mordant dye
2005
(c) Basic dye (d) Reactive dye 9. Which of the following compounds is an azo dye? [AMUJ
7. Which one is basic dye ? [DCE] (a) Martins yellow (b) Malachite green
(c) Methyl orange (d) Mercurochrome
(a) Orange-I (b) Phenolphthalein
(c) Anthraquinone (d) Aniline yellow

Topic 4
Cleansing Agents
2011
1. Select the detergent that is used to prepare cosmetics. (a) Sodium ethyl sulphate
(a) DDBS [Guj CET] (b) Sodium acetate
(b) Polyethylene glycol (c) Urea
(c) Cetyltrirnethyl ammonium chloride (d) Cetyltrirnethyl ammonium bromide
(d) LAS 5. Pick out the statement which is not true? [Kerala CEEJ
2. Which of the following is known as invert soap? [RPET] (a) Tetrazine is harmful edible colour
(a) Pentaerythritol monostearate (b) Alitame is an artificial sweetner
(b) Sodium stearyl sulphate (c) BHT is an antioxidant
(d) Sodium alkyl sulphate is a cationic detergent
(c) Trin1ethyl stearyl ammonium bromide
(e) The perfo1mance of a rocket propellant is measured
(d) Ethoxylated nonyphenol
in terms of specific impulse
2009 2006
3. Bithional is added to soap as an adclitive to function as a/an 6. Soaps can be classified as [WBJEE]
(a) Softener [Ke rala CEE]
(a) carbohydrates (b) ether
(b) hardener (c) salts of fatty acids (d) None of these
(c) dryer
(d) buffering agent 2005
(e) antiseptic 7. Which of the following represents soap? [DCE]

2007 (a) C17 H 35 COOK

4. Which of the following forms cationic micelles above (b) C17H35COOH
certain concentration ? [Manipal] (c) C15H31COOH
(d) (C17 H35C00) 2 Ca
 Topic 5
Rocket Propellants
2014 2007
1. Which one of the following acids is used as an oxidiser in 5. H 2 O 2 used in rocket has the concentration [BITSAT]
rocket fuel? [AMU]
(a) 50% (b) 70% (c) 30% (d) 90%
(a) HC104 (b) HN02 (c) H 3 P0 4 (d) HN03
6. Which of the following could act as a propellant for
2012 rockets ? [MP PET]
2. Which of the following is not used as propellant? (a) Liquid hydrogen + liquid nitrogen
(a) Hydrazine (b) UDMH [Manipal] (b) Liquid oxygen + liquid argon
(c) Liquid hydrogen + liquid oxygen
(c) MMH (d) Phenyl hydrazine
(d) Liquid nitrogen + liquid oxygen
2009
2006
3. Which of the following is a double base propellant?
7. The hybrid rocket propellant consists of [Kerala CEE]
(a) Methyl nitrate and nitromethane [Kerala CEE]
(a) acrylic rubber and liquid nitrogen tetraoxide
(b) Nitroglycerine and nitrocellulose
(b) polyurethane and ammonium perchlorate
( c) Kerosene and alcohol
(c) nitroglycerine and nitrocellulose
(d) Acrylic rubber and liquid N 2 O 4
(d) liquid hydrogen and liquid oxygen
(e) Nitromethane and H 2 O 2
(e) hydrogen peroxide
2008 8. A hybrid rocket propellant uses [DCEJ
4. Which of the following is used as an oxidizer in rocket (a) a liquid oxidiser and a solid fuel
propellants ? [Kerala CEE] (b) a composite solid propellant
(a) Alcohol (b) Acrylic rubber ( c) a bi1iquid propellant
(c) Hydrazine (d) Polyurethane (d) a solid, liquid and gas as a propellant
(e) Ammonium perchlorate

Answers
TOPIC 1 Chemicals in Medicines
1. (b) 2. (a) 3. (c) 4. (b) 5. (a) 6. (d) 7. (c) 8. (b) 9. (c) 10. (b)
11. (b) 12. (a) 13. (b) 14. (d) 15. (b) 16. (a) 17. (c) 18. (c) 19. (b) 20. (d)
21 . (c) 22. (a) 23. (c) 24. (d) 25. (c) 26. (c) 27. (c) 28. (b) 29. (a) 30. (b)
31 . (a) 32. (d) 33. (c) 34. (c)
TOPIC 2 Chemicals in Food and Pheromones
1. (a) 2. (d) 3. (b) 4. (b)
TOPIC3 Chemical as Dyes and Cosmetics
1. (d) 2. (d) 3. (d) 4. (a) 5. (b) 6. (b) 7. (d) 8. (a) 9. (c)
TOPIC4 Cleansing Agents
1. (c) 2. (c) 3. (e) 4. (d) 5. (d) 6. (c) 7. (a)
ill!C_5_ Rocket Propellants
1. (d) 2. (d) 3. (b) 4. (e) 5. (d) 6. (c) 7. (a) 8. (a)
 Explanations
Topic 1 Chemicals in Medicines
1. Barbital is a sleep-producing drng, i.e. hypnotic tranquilliser. It 11. Antiseptics drugs cause destrnction of microorganisms, which
causes addiction. produce, septic diseases, e.g. dettol, savlon, acriflavin, boric acid,
2. Heroin is not a tranquilliser, it is a narcotic analgesic. Equanil and phenol, iodoform, KMnO 4 and some dyes such as chloramine-T,
valium are tranquillisers. methylene blue.
12. Aspirin is OCOCH3
3. An agonist is a chemical that binds to a receptor and activates the
receptor to produce a biological response. It is a substance which &COOH
mimic the natural chemical messengers.
4. The branch of science which deals with the treatment of diseases
using suitable chemical compounds is called chemotherapy. In which is acetylated product of salicylic acid (o- hydroxybenzoic
this branch, chemicals are used for their therapeutic effect. acid).
OCOCH3 OH OCOCH 3
5.
C( COOH
~COOR
LsJ + CH3COCI ~
~ C O OH
+ HCI LQJ
Acetyl salicylic acid
(aspirin) Salicylic acid Acetyl salicylic acid
(aspirin)
6. Structures of the various compounds are
13. Tranquillisers are the drngs w hich are used to relieve mental
OH
ailments. These are also known as psychotherapeutic drngs as
they act on the central nervous system.

y
0 2N y Y N o2
14. Analgesics are used for relieving pain. Ibuprofen, naproxen,
aspirin and diclofenac sodium all are examples of non-narcotic
analgesics.
N02
Picric acid Barbituric acid Valium is used for relieving tension and mental stress, so it is a
(a) (b) tranquilliser, not analgesic.
OH COOR 15. Antibiotics are the chemical substances produced by
microorganisms (bacteria, fungi, etc.), that can inhibit the growth
HO~O ~ O Y CH3 of other microorganisms, e.g. penicillin, erythromycin,

HO OH
Uo tetracycline, ofloxacin but oxytocin is a peptide hormone which
is secreted by master gland.
Ascorbic acid Aspirin
(c) (d) 16. Benzalkonium chloride, also known as alkyl dimethyl benzyl
ammonium chloride is nitrogeneous cationic surfactant and it is
used as a antiseptic.
7. Penicillin was the first discovered antibiotic. Antibiotics are used
as drngs to treat infections because of their low toxicity for v X C nH2n+1C1-
htmrnns and animals.
8. Antipyretic drugs reduce body temperature in fever and analgesic
dmgs provide relief from pain. Paracetamol and asiprin act as n = 8, 10, 12, 14, 16, 18
both antipyretic as well as analgesic. 17. Mifepristone is a synthetic steroid that checks the effect of

$ ;,
OH progesterone. It is used as a "morning after pill" .
18. Paracetamol is an antipyretic and analgesic. It is used to lower the
temperature of the body in high fever and to relieve pain.
9. N~"'tyl p-,m;oo phoool
19. Bithional is antiseptic which is generally added to medicated
soap to reduce the odour produced by bacterial decomposition of
NHCOCH 3 organic matter on the skin.

10. The correct structure of drng paracetamol (4-acetamidophenol)

is (b).

Ho - @ - NHCOCH3
Paracetamol
742 I Chapterwise & Topicwise Engineering Entrances Solved Papers
20. The functional group present in salol are - OH and - COOR. Chloramphenicol is rapidly absorbed from the gastro-intestinal
Salo! is phenyl salicylate. Its strucnrre is as tract and hence, can be given orally. These can be used for curing
typhoid, acute fever, dysentery, whooping cough, etc.

C§(COOC,H
OH
28. Erythromycin is a bacteriostatic. It inhibits the growth of
5 microorganisms.
29. Phenacetin is used as antipyretics.
Salo!

21. The correct matching is as follows:

~ Hs
Chemical Use
Sodium perborate Milk bleaching agent
Chlorine Disinfectant NHCOCH3
Phenacetin
Bithional Antiseptic
Potassium stearate Soap 30. Aspirin (2-acetoxy benzoic acid) is an analgesic. It is obtained by
acetylating salicylic acid w ith acetic anhydride and cone. H 2SO4•
22. The given structure is of histamine that acts as a
neurotransmitter and vasodilator.
23. Analgesics These drugs relieve pains, e.g. novalgin, aspirin, etc.
Antibiotics These drugs are produced by microorganisms and are
OH
COOR
+ (CH3C_O hO
Cone.
H
2 4
S0
C§(
0
OCOCH3
COOR
+ CH3COOH
Acetic
capable of destroying other microorganisms, e.g. penicillin etc. Salicylic acid anhydride Aspirin

Antipyretics These drugs bring down the body temperature in 31. Structure of chloroxylenol is given below
high fever, e.g. paracetamol, aspirin etc.

Sulpha drugs Generally these drugs have antibacterial action,

e.g. sulphadiazine etc.
24. The structure of an important antipyretic, paracetamol is
H
,CiCH, Cl

$
Chloroxylenol
(4-chloro-3, 5-dimethyl phenol)

32. 4-chloro-3,5-dimethyl p henol is chloroxylenol. It is main

constinient of dettol, which is responsible for its antiseptic and
NHCOCH 3 disinfectant prtoperties.
OH
So, p-amino phenol gives paracetamol on acetylation.
25. Tincnire of iodine is prepared by d issolving iodine and KI in
water and making the solution with rectified spirit. So, it is
alcoholic solution ofI2• H,V$'CH,
U. &~OH ~ COOH Cl
(4-chloro-3,5-dimethyl phenol)

33. Aspirin (2-acetoxy benzoic acid) is an analgesic.

2-acetoxy benzoic
acid (aspirin) or
Acetyl salicylic acid
34. Aspirin is a moderate acid (pK0 = 3.5), hence is almost unionised
Salicylic acid in stomach due to strong acidic meditlfl1 of it (because ofHCI). It is
due to common ion effect. While in small intestine, the medium is
alkaline, hence aspirin will be sufficiently ionised in small
intestine.

~ C
HO Topic 2 Chemicals in Food and
Pheromones
Salicylaldehyde Phenyl salicylate
1. Butylated p-hydroxyanisole (BHA), butylated p -hydroxy toluene
27. Broad spectrum antibiotics are the antibiotics which are effective (BHT), esters of gallic acid are the examples of antioxidants.
against several types of harmfol microorganisms. Tetracycline, These chemicals retard the action of oxygen on the food material
chloromycetin and chloramphenicol are the common examples of and help in its preservation.
broad spectrum antibiotics.
 Chemistry in Everyday Life I 743
2. The chemicals which are used to protect food from microbes 5. Vat dyes are soluble in water and cannot be directly applied.
action, i.e. which arrest the process of fermentation, acidification These are reduced to soluble colourless leuco form by an alkaline
and any other decomposition of food are known as food reducing agent. e.g.
preservatives. Table salt, sugar, vegetable oil, v inegar, sodium
benzoate (C6H 5COONa), sodium metabisulphite (Na 2Si_05), 0
v itamin E etc. are food preservatives. II
3. Disparlure is a pheromone that attracts insects. ~ C 'c= (N
4. The safest and the most common alternative ofsugar is aspartame.
~N/ '---c ~
101 Reduction ,

Topic 3 Chemicals as Dyes and I II

H 0
Cosmetics Indigo (blue, water insoluble)

1. In basic (alkaline) solution naphthol exists as naphthoxide ion OH H

which is a strong o, p-directing group. I I
OH 0 6
C~c - c/N)§J
o
©r§r ~©r§r N/ ~C
Ill I I
-s©@f;e H OH
I ndigo (white leuco base)

6. Alizarin is mordant dye. Alizarin gives a bright red colour with

aluminium and a blue colour with barium.
Thus, formation of dye can be shown as 7. Basic dyes contain salts of amino or substituted amino group
N=N-Ph (- NH2 or - NR2) which in acid solution form water soluble
OH
@&
OH cations. These dyes attack the anionic sites present on the fabrics

©1§1 [PI/N..,.N]Cl-
alkaline solution
and then get attached to them.
Aniline yellow is a basic dye. Its structure is as

2. Alizarin is an anthraquinone dye. It gives a bright red colour with @-N N--@-NH2
aluminiwn and a blue colour with barium. Aniline yellow
(p-amino azobenzene)

*OH 0
OH- '::.Al/ -
0
H20

c(&OH ?I "'
9. Methyl orange is an azo dye. It is an acidic dye.

H03S-O-N=N-O-N(CH3)i
Methyl orange

0
Alizarin-aluminium complex
Topic 4 Cleansing Agents
3. Sr2+ - pink 1. Cetyltrimethyl ammonium chloride is a cationic detergent. It is
Mg2+ - v iolet used to prepare cosmetics because it possesses germicidal
A! 3+ - red properties. It is used in hair conditioner.
2 2. A class of synthetic detergents in which the surface-active part of
Ba + - blue
the molecule is the cation, e.g. trimethyl stearyl ammonium
Alizarin is a mordant dye. It gives different colour to the fabric bromide.
with different metal ions. 3. Bithional is added to soap to impart antiseptic properties. It
4. Vat dyes are not used to dye nylon and polyester fibres but used to reduces odour produced by bacterial decomposition of organic
dye cotton fibres. Basic dyes, disperse dyes and insoluble azo matter on the skin.
dyes, however, are used to dye ny lon and polyesters.
744 I Chapterwise & Topicwise Engineering Entrances Solved Papers
4. Cetyltrimethyl ammonium bromide being a cationic detergent
forms cationic micelle above the certain concentration.
S. Sodium alkyl sulphate is an anionic detergent as it gives anion,
which acts as surfactant.
RCH2 - OS0 3Na~ RCH2 - 0S03 + Na+
Sodium alkyl Anionic part
sulphate
6. Soaps can be classified as salts of fatty acids. Because soaps are
formed by the alkaline hydrolysis (NaOH) of oils or fats which
produce sodium sa lts of fatty acids (soaps) and glycerol.
7. Soaps are the sodium or potassium salt of higher fatty acids, e.g.
C 17H 35COOK(potassium stearate).
These are obtained by alkaline hydrolysis of oils and fats . The
reaction is called saponification.
Topic 5 Rocket Propellants
1. Rocket fuels generally contain two substances one the fuel and
other the oxidiser. Oxidiser is an oxygen rich substance and used
to prov ide oxygen for burning process. Common oxidisers used
for this purpose are nitric acid (HN0 3), hydrogen peroxide
(HP2 \ N 2 0 4 etc.
2. Rocket propellants ants are a combination of an oxidiser and fuel.
Phenyl hydrazine cannot act as propellant.
3. The molecules which contain both the oxidizer and the fuel
elements in the same molecule are called double base propellants,
e.g. nitroglycerine and nitrocellulose.
In this nitrocellulose gels in nitroglycerine and sets to a solid
mass.
4. A propellant is a combination of an oxidiser and a fuel. Among
the given only ammonium perchlorate is used as an oxidiser
(solid oxidiser) while other are generally used as a fuel in rocket
propellant.
S. H 2 0 2 is used as an oxidant for rocket fuel and has 90%
concentration to be used in rockets.
6. Liquid hydrogen and liquid oxygen is a good fuel.
7. Hybrid propellants consist of solid fuel (acrylic rubber) and
liquid oxidiser (liquid nitrogen tetraoxide, N 20 4 ).
8. Hy brid propellants are the propellants which consist ofsolid fuel
and a liquid oxidiser. For example, liquid Np4 (liquid oxidiser)
and acrylic rubber (solid fuel).
Analytical Chemistry
QUICK REVIEW
• Qualitative analysis of any given inorganic mixture is done
in the following steps:preliminary tests, wet tests for acidic
and basic radicals.
• An important preliminary test for metal ions identification
is flame tests. Not all metal ions give flame colour ions.
Some important characteristic flame colours shown by
metals are given in the following table:
Me tal ion Flame colour
• All common metal sulphates are soluble in water except
PbSO 4 , Hg 2 SO 4 and BaSO4 while CaSO 4 and Ag 2 SO4
are sparingly soluble.
• All common metal hydroxides are insoluble in water
except those of group IA metals.
• All common sulphides, s2- are insoluble in water except
those of the group IA and group IIA metals and ammonium
ion.

Lt Crimson red Analysis of Acidic Radicals

Na+ Golden yellow For systematic analysis of acidic radicals, these radicals
can be divided into three groups:
Rb+ Reddish violet
(z) Group 1 or dilute acid group It includes those
Ca 2+ Brick-red radicals, which are decomposed by dilute acids.
Sr2+ Red CO~- , HCO3, s2- , SO~- , NO2 and CH3 Coo-
Ba2+ Apple green belong to this group.
(ii) Group 2 or concentrated acid group Radicals are
eu2+ Blue decomposed by cone. H 2 SO4 (group reagent), x -
(halides), NO3, c 2 o t radicals belong to this group.
Borax Bead Test
(iii) Group 3 or special group Radicals such as so;-,
• Borax bead test is given by those substances which give
coloured bead when heated with borax. Colour of bead sot , PO~- are identified by specific tests.
gives idea of substance. The colour of bead is different in
Analysis of Basic Radicals
oxidising and reducing flames.
• Analysis of basic radicals involves three basic steps:
• Microcosmic salt bead test is similar to borax bead test and (i) Preparation of original solution.
in it microcosmic salt bead is used in place of borax bead
(ii) Separation of basic radicals in different groups.
test. Sodium metaphosphate combines with metallic oxides
(iii) Confirmation of basic radicals by their specific tests.
to form orthophosphates, which are coloured.
• To prepare original solution, following solvents are used
Solubility Rules for Common Compounds strictly in the order given below :
• All common nitrates, NO 3- , acetates, CH 3 coo- are (i) Cold water (ii) Hot water
soluble in water. (iii) Dil. HCI (iv) Cone. HCl
746 I Chapterwise & Topicwise Engineering Entrances Solved Papers

• For analysis ofbasic radicals, original solution is treated with specific reagents (group reagents) to separate cations. All the salts
have been classified into zero to VI group on the basis of salt precipitated.
Tests for basic radicals
Group Basic radicals Group reagent Precipitate as Explanation
D il. HCI Chlorides • Ksp values of chlorides are low, hence
(AgCI, Hg2 Cl 2 ,PbCl 2 ) precipitated. Other have higher Ksp
values not precipitated.
IT Cu 2+ , Cd 2+ , Pb2+ ,Hg2+ H 2S gas in the Sulphides (CuS, As2~,etc). • Ksp values of Ilnd group sulphides are
presence low, hence, precipitated by low [S2- ]
Bi 3+ ,Sb3+ ,Sn 2+ ,As 3+
ofdil. HCI ion. HCI (due to H+ common ion)
decreases the ionisation of weak acid
2
H 2S which gives low [S -] ions. Hence,
group IT sulphides are precipitated
while others with high Ksp values are
not precipitated.
ITT Al3+ , Cr 3+, Fe3+ NHpH in the Hydroxides (Al(OH)3 ,etc.) • Ksp values of IIIrd group hydroxides
presence ofNH4CI are low. NH4CI decreases ionisation of
weak NH4OH due to common ion
effect. Low [OH-] is only sufficient to
precipitate group ITI cations as their
hydroxides.
IV Zn 2+ , Ni2+, Mn 2 +, Co2+ H,S in ammoniacal Sulphides (ZnS, N iS, etc.) • K sp values of sulphides of group IV are
medium high. Ionisation of H 2S increases in
basic medium. Hence, group IV cations
I are precipitated as sulphides due to
I increasing [S2- ].
V Ca2+ , Ba 2+, Sr 2+ (NH4 )iCO 3 + NH4 CI Carbonates • K sp values of carbonates are less than
(CaCO 3 ,BaCO3 ,SrCO3) that of group VI (Mg2+) hence,
precipitated before Mg2+.

VI Mg2+ (Na+ , K+) also NHpH + Na2HPO 4 White precipitate (MgHPO 4 )

2
included (only for Mg +)

Zero D il. NaOH NH3 gas is evolved

 Topic 1
Preliminary Test
2014 2006
1. What colour is imparted into the flame when lithium is 3. Which of the following radicals gives the apple green
burnt? [J&K CET] flame during flame test ? [BCECEJ
(a) Golden yellow {b) Brick red (a) Ba 2+ 2
(b) Sr +
(c) Crimson red (d) Grassy green (c) Ca 2+ (d) Cr 3+
2007 4. Borax bead test of Cr (chromium) is

2. In borax bead test, the coloured ions give characteristic (a) green [Jamia Millia Islamia]
coloured beads due to the formation of [WB JEE] (b) blue
(a) metal borates {b) metal metaborates (c) violet
(c) metal phosphates (d) metal tetraborates (d) brown

Topic 2
Wet Test for Acidic Radicals
2011 2009
1. The yellow precipitate formed during the chromyl chloride 4. The incorrect statement in respect ofchromyl chloride test is
test is chemically [KCET] (a) formation ofred vapours [Manipal]
(a) chromic acid (b) lead chromate (b) formation of lead chromate
(c) lead acetate (d) sodium chromate (c) formation of chromy1chloride
(d) liberation of chlorine
2010 5. To an aqueous solution containing anions a few drops of
2. A white crystalline salt A reacts with dilute HCl to liberate acidified KMn0 4 are added. Which one of the following
a suffocating gas Band also forms a yellow precipitate. The anions, ifpresent will not decolourise the KMnO4 solution?
gas B turns potassium dichromate acidified with dilute
(a) C (b) CO~- (c) S2- [Kerala CEE]
H2 SO4 to a green coloured solution C. A, B and C are
respectively. [KCET] (d) N02 (e) Cl-
(a) Na 2 S03 , S02 , Cr2 (S04h 6. A white-coloured inorganic compound, on heating, gives a
(b) Na 2 S 2 0 3 , S02 , Cr2 (S0 4h gas which turns lime water milky and residue is left which
(c) Na 2 S, S02 , Cr2 (S0 4h is yellow when hot and turns white on cooling. The
compow1d is [CG PET]
(d) Na 2 S04 , S02 , Cr2 (S04h
(a) Pb(N0 3 ) 2 (b) PbC03 (c) BaC03 (d) ZnC03
3. A mixture of salts (Na 2 S03 + K 2 Cr2 0 7 ) in a test tube is
treated with dil. H2 SO4 and resulting gas is passed through 2008
lime water. Which of the following observations is correct 7. A salt on treatment with dil. HCl gives a pungent smelling
about this test? [DCEJ gas and a yellow precipitate. The salt gives green flame test
(a) Solution in test tube becomes green and lime water and a yellow precipitate with potassium chromate. The salt
turns milky is [Manipal]

(b) Solution in test tube is colourless and lime water turns (a) NiS04 (b) BaS2 0 3 (c) PbS 2 0 3 (d) CuS04
milky 8. In the brown ring test, the brown colour of the ring is due to
(c) Solution in test tube becomes green and lime water (a) ferrous nitrate CKCET]
remains clear (b) ferric nitrate
(d) Solution in test tube remains clear and lime water also (c) a mixture ofNO and N0 2
remains clear (d) ferrous nitrososulphate
748 I Chapterwise & Topicwise Engineering Entrances Solved Papers
9. The brown complex obtained in the detection of nitrate 2006
radical is formulated as [Fe(H 2O)5 NO]SO4 . What is the 13. The brown ring test for nitrates depends on [KCET]
oxidation number of Fe in this complex? [WB JEE]
(a) the reduction of nitrate to nitric oxide
(a) + 1 (b) + 2 (b) oxidation of nitric oxide to nitrogen dioxide
(c) + 3 (d) 0 (c) reduction of ferrous sulphate to iron
2007 (d) oxidising action of sulphuric acid
10. AgCl dissolves in a solution of NH 3 but not in water 14. Brown ring in the test of NO3 is fom1ed due to the
because [VITEEE] fom1ation of [WBJEE]

(a) NH3 is a better solvent than H 2O (a) FeSO4 · NO (b) [Fe(SO4 ) 2 · NO]H2O
(b) Ag+ forms a complex ion with NH3 (c) Fe(SO4 ) 3 · NO (d) None of these
(c) NH3 is a stronger base than H 2O
2005
(d) the dipole moment of water is higher than NH3
15. MnO 2 and H 2SO4 added to NaCl, the greenish-yellow gas
11. Brown ring is made for [WB JEE]
liberated is [OJEE]
(a) NO3 (b) Cl- (c) 1- (d) Br-
(a) Cl 2 (b) NH 3 (c) N 2 (d) H 2
12. Silver chloride dissolves in aqueous ammonia due to 16. Which of the following doesn't give a ppt. with silver
formation of [OJEE] nitrate solution? [J&K CET]
(a) [Ag (NH 3h t (b)[Ag (NH3h ] (a) Ethyl bromide (b) Sodium bromide
Ag (NH4 h t
( C) [ (d) [Ag (NH 4 ) 2 ] (c) Calcium chloride (d) Sodium chloride

Topi c 3
Wet Test for Basic Radicals
2014
1. Black precipitates form in many metal ion solutions, then 4 . The coloured solution S contains [JEE Advan ced]
which anion is used as a precipitating agent? [IPUCETJ (a) Fe 2 (SO4 h (b)CuSO 4
(a) c1- (b) s2 - (c) Po!- (d) co~- (c) ZnSO 4 (d) Na 2 Cr04
5. Which one of the following metallic hydroxides does not
2013 dissolve in sodium hydroxide solution? [KCET]
2. Upon treatment with ammoniacal H 2 S, the metal ion (a) Zn(OHh (b) Al(OH) 3
solutions that precipitates as a sulphide is [JEE Advanced] (c) Fe(OHh (d) Pb(OHh
(a) Fe(III) (b) Al(III) (c) Mg(II) (d) Zn(II)
2010
Directions (Q. Nos. 3 - 4) Read the following information 6. In the analysis of basic radicals, NH4 OH and NH4 Cl give
carefully and answer the following question. precipitate with [MP PET]
An aqueous solution of a mixture of two inorganic salts, (a) I-group radicals
when treated with dilute HCl, gave a precipitate (P) and (b) II-group radicals
filtrate (Q). The precipitate P was found to dissolve in hot (c) III-group radicals
water. (d) IV -group radicals
The filtrate (Q) remained unchanged, when treated with
H 2S in dilute mineral acid medium. However, it gave a 2009
precipitate (R) with H2 Sin an ammoniacal medium. The 2 2 2 2
7. Out of Cu +, Ni +, Co + and Mn +, which is dissolved
precipitate R gave a coloured solution (S), when treated when H2 S is passed through it in the presence of dil.
with H 2O 2 in an aqueous NaOH mediwn. HCl? [OJEE]
3 . The precipitate P contains [JEE Advanced] (a) Cu 2+ (b) Ni 2+
2
(a) Pb + (b)Hg~+ (c)Ag+ (d)Hg 2+ (c) Co 2+ (d) Mn i+
 Analytical Chemistry 1749

2008 2006
8. The only cations present in a slightly acidic solution are 17. A solution when diluted with H 2 O and boiled, it gives a
F e 3+ , zn 2+ and Cu 2+ . The reagent that when added m . white precipitate. On addition of excess NH4 Cl/NH4 OH ,
3
excess to this solution would identify and separate Fe + in the volume of precipitate decreases leaving behind a white
one step is [Manipal] gelatinous precipitate. Identify the precipitate which
dissolves in NH4 OH/NH 4 CL [IIT JEE]
(a) 2M HCl (b) 6M NH 3
(c) 6M NaOH {d) H 2S gas (a) Zn(OH )z (b) Al(OHh (c) Mg(OH) 2 (d) Ca(OH )z

9. Fe(OHh can be separated from Al(OH) 3 by the addition 18. CuSO 4 decolourises on addition ofKCN, the product is
of [WBJEE] (a) [Cu(CN) ] 2-
4 [IITJEE]
(a) NaCl solution (b) di!. HCl solution (b) Cu 2 + get reduced to form [Cu(CN) 4 ] 3-
( c) NaOH solution (d) NH4 Cl and NH4 OH (c) Cu(CN)z
(d) CuCN
10. The hydroxide insoluble in NH 4 OH + NH4 Cl is
19. Which of the following sulphides is yellow in colour?
(a) Al(OH) 3 (b) Ca(OHh CUPSEEJ
(a) CuS (b) CdS [WB JEE]
(c) Zn(OH) 2 (d) Mg(OH)i
(c) ZnS (d) Cos
11. The dark blue colour ofthe solution formed when excess of
ammonia is added to a solution of copper (II) sulphate is 20. The principle involved in the classification of basic
due to the presence of the ion [Guj CET] radicals, is [BCECE]

(a) [Cu(OH) 4 (H 2O)i ]2- (b) [Cu(H 2O)6 J2+ (a) common ion effect (b) solubility product
( c) valency of radicals ( d) strength of salt
(c) [Cu (NH4 ) 2 (H 2O) 4 ] 4+ (d) [Cu(NH3 ) 4 (H 2O) 2 ] 2+
21. Copper sulphate solution, when added to an excess of
2007 ammonium hydroxide, forms a complex compound due to
12. A solution of a metal ion when treated with K1 gives a red (a) [Cu (NH3 )z ] 2+ [Jam.ia Millia Islamia]
precipitate which dissolves in excess K1 to give a (b)[Cu (NH 3 ) 4 ]2+
colourless solution. Moreover, the solution of metal ion on (c)[Cu (NH3)6]2+
treatment with a solution of cobalt (II) thiocyanate gives (d) Cu 2+
rise to a deep blue crystalline precipitate. The metal ion is 2
[IITJEE] 22. Fe + ion is distinguished from Fe 3+ ion by
[Jamia Millia Islamia]
(a) Pb 2+ (b) Hg 2+ (c) Cu 2+ (d) CO 2+
(a) BaC12 (b) KCN
13. In Nessler's reagent for the detection of ammonia the (c) NaNO3 (d) NH4 SCN
active species is [BITSATJ
(a) H g 2 Cl 2 (b)Mg 2+ (c)Hg 2 12 (d) H gl~- 2005
23. A metal nitrate reacts with Kl to give a black precipitate
14. When H 2 S gas is passed in a metal sulphate solution in
which on addition of excess of Kl convert into orange
presence ofNH4 OH, a white precipitate is produced. The
colour solution. The cation of metal nitrate is [IIT JEE]
metal is identified as [Manipal]
(a)Hg 2+ (b)Bi 3+ (c) Pb 2 + (d)Cu +
(a) Zn (b) Fe (c) Pb (d) Hg
15. Prussian blue is obtained by mixing together aqueous 24. IfFe 3+ and Cr 3 + both are present in group III ofqualitative
solution of Fe 3+ salt with [J&K CETJ analysis, then distinction can be made by
[Jamia Millia l slamia]
(a) ferricyanide
(b) ferrocyanide (a) addition ofNH4 OHin presence ofNH4 Cl when only
(c) hydrogen cyanide Fe(OHh is precipitated
(b) addition of NH4 OH in presence of NH 4 C l when
( d) sodium cyanide
Cr(OHh and Fe(OHh both are precipitated and on
16. An aqueous solution contains the following ions, Hg~+, adding Br2 water and NaOH, Cr(OH)3dissolves
2 2 2
Hg +, Pb +, Cd +. Which of the following precipitates (c) precipitate of Cr(OH)3 and Fe(OHh as obtained in
is/are obtained by the addition of di!. HCl? [DCEJ (b) are treated w ith cone. HCl when only Fe(OHh
(a) Hg 2 Cl 2 and PbC12 (b) Hg 2Cl 2 dissolves
(c) PbC12 and HgCl 2 (d) PbCl 2 (d) Both (b) and (c) are correct
 Answers
Tilfil1 Preliminary Test
1. (c) 2. (b) 3. (a) 4. (b)
TOPIC2 Wet Test for Acidic Radicals
1. (b) 2. (b) 3. (a) 4. (d) 5. (b) 6. (d) 7. (b) 8. (d) 9. (a) 10. (b)
11. (a) 12. (a) 13. (a) 14. (a) 15. (a) 16. (a)
TOPIC3 Wet Test for Basic Radicals
1. (b) 2. (d) 3. (a) 4. (d) 5. (c) 6. (c) 7. (a) 8. (b) 9. (c) 10. (a)
11. (d) 12. (b) 13. ( d) 14. (a) 15. (b) 16. (a) 17. (a) 18. (d) 19. (b) 20. (b)
21 . (b) 22. (d) 23. (b) 24. (d)

Explanations
Topic 1 Preliminary Test Topic 2 Wet Test for Acidic Radicals
1. Chromyl chloride test When the mixture is heated with solid
1. Colour Cation
K 2 Crp7 , with cone. H 2SO 4 and a soluble chloride like NaCl,
Golden yellow Na+ orange red vapours of chromyl chloride, CrO2Cl2 are produced.
Brick red Ca 2+ K2Crp 7 + 4NaCI + 3H2SO4 (cone.) -
t,,
2CrO2Cl 2 + KiSO4
Crimson red u+ Orange red vapour

Grassy green eu2+, aot, T 13+ + Na2 SO4 + 3H 2 O

When vapours of chromyl chloride are passed into aqueous
2. Borax is widely used in qualitative analysis, since it gives NaOH solution , yellow colour solution ofNa 2CrO4 is obtained
coloured beads with transition metal salts of Cu, Fe, Cr, Mn, Co which on reaction with acetic acid and lead acetate gives yellow
and Ni. ppt. ofPbCrO 4• This test is called chromyl chloride test.
The chemistry of the borax bead test is as follows: Hence, the yellow precipitate formed during chromyl chloride
Na2Bp7 · I0H 20 ~ Na2B 4 O7 + 10 H 2 O test is chemically lead chromates PbCrO4•
74 CrO 2C1 2 + 4NaOH - Na 2 CrO4 +2NaCI + 2H2 O
Na 2B 4O 7 0-c 2NaBO2 + Bp3 Yellow
Sodium metaborate Boric anhydride (CH 3COO)iPb+ Na 2 Cr04 - PbCrO4 J, +2CH 3 COONa
Gl~bead Yellowppt
CuSO4 + Bp3 - CuO · Bp3 + SO3 2. Tums the colour of acidified K2Cr2O 7 green, thus it is SO 2 and
Copper (11) metaborate
(green when hot, blue when cold)
SO 2 is obtained alongwith yellow precipitate when th iosulphate
Thus, coloured beads are formed due to the formation of metal is treated with di lute acids. Thus, A is Na 2SiO3 , Bis SO2 and C is
meta borates. Cr2 (SO4 lJ.
Since, SO2 has a suffocating odour, thus B must be SO 2 gas. As
3. Ba2+ ions give the apple green flame during flame test. SO 2 gas turns acidified K 2Cri07 green, this suggests that
When paste of salt in cone. HCl, is burnt on a spatula, the C (green colour solution) must be Cr3+ ions. SO2 is obtained
following coloured flame appears for different radicals. when thiosulphate salts are treated with dilute acids. Thus, A will
Sr 2+ Crimson red be Na 2S2O 3 , Bwill be SO2 and Cwill be Cri(SO4 ) 3 [or Cr 3+ ion].
Ca2+ Brick red The reactions involved are as follows
Na+ Golden yellow Na2 5iO3 + 2HCI - SO2 t
Sodium thiosulphate Suffocating gas
4. In borax bead test
~) ~)
Cr3+ gives blue bead
eu
2
+ gives blue green bead + 2NaCI + H 2O + SJ, (ppt)
Ni 2+ gives Yellow
brown bead
Mn 2+ gives pink bead K 2 Crp7 + 3SO2 + H 2SO4 - K 2SO4 + Cr2 (SO4 ) 3 + Hp
Green
(C)
 Analytical Chemistry I 751
3. Na2SO3 with dil. H 2SO4 produces SO 2 gas which turns K 2 Crp 7 9. The brown coloured complex obtained in the detection of nitrate
and lime water into green and milky, respectively. radical is formulated as [Fe(H2 O)5 NO] SO 4. This complex
Na2SO3 + H 2 SO4 - Na 2SO4 + H 2O + SO 2 i formally contains Fe (I) and NO+, since Fe (TT) gains one electron
from NO which changes to NO+. Thus, the univalent character of
KiCr2O 7 + H 2SO4 + 3SO2 - KiSO4 + Cri(SO4 ) 3 + H 2O iron in the complex is justified by the presence of a coordinated
Qreen
Ca(OH)z + SO2 - CaSO3 j, + H 2U NO+ group.
Milky 10. AgCI dissolves in the solution ofNH 3 but not in water because Ag+
Since, the obtained gas turns lime water milky, it must be SO2 forms a complex ion, [Ag(NH 3 h ]with aqueous NH3 •
2-
and the anion present in the compound must be SO3 . AgCI + 2NH3 (aq)~ [Ag(NH3 )z]CI
Diammine silver (I) chloride
4. Chromyl chloride test is used for detecting er- ions. Chlorine is (soluble)
not liberated in this test. 11. In ring test, a brown ring of nitrate ions.
4NaCI+ KiCr2O 7 + 3H2SO4 -➔ K 2 SO4 + 2Na 2SO4 FeSO4 (aq)+ NO(g) + 5H2 O(/) ~ [Fe (H2 O)5 NO]SO 4
Dark brown ring
2CrO 2 Cl 2 i + 3H2 O
Chromyi chloride If formed at the junction H 2SO4 and [FeSO4 + nitrate solution]
(reddish brown vapour) 12. Silver chloride dissolves in aqueous ammonia due to d1e formation
CrO2 Cl2 + 4NaOH - 2NaCI + Na 2 CrO4 + 2Hp of diammine silver (I) chloride or [Ag(NH3 )z tion.
Yellow
AgCI + 2NH 3(aq)~ [Ag(NH3 )i]CI
Na2CrO4 + (CH 3COO)zPb - 2CH3COONa+ PbCrO4 Soluble
Lead chromate
yellowppt 13. The brown ring in d1e test ofNO3 is formed due to the formation
5. In cot, C is present in its highest oxidation state, i.e. + 4 offerrous nitrososulphate. This test depends upon the reduction of
state, so its further oxidation is not possible, it only undergoes NO3- (nitrate ions) by Fe2+ ions.
reduction. Acidified KMnO4 is a strong oxidising agent but it NO3+ 3Fe2+ + 4H+ ~ NO+ 3Fe3+ + 2Hp
cannot oxidise COi-·
Fe2+ +NO + 5Hp ~ [Fe(H2O)5 NOf+
Hence, it will not be decolourised by coi-- Brown complex

6. The residue left after the liberation of CO2 is yellow when hot 14. Brown ring in the ring-test ofNO3 is formed due to the formation
and turns white on cooling, so it is ofZnO and the cation present ofFeSO4 · NO at the junction of two liquids.
in the compound is Zn 2+.
15. The addition ofMnO2 and H 2SO4 to NaCl solution evolves a Cl 2
Hence, the white coloured inorganic compound is Zn. gas which is yellowish-green in colour.
2
Thus, Zn + + COi- - ZnCO3
and the reactions are as follows 2NaCI + MnO2 + 3H2SO 4 - 2NaHSO 4 + MnSO4 + 2Hp
A + Cl 2i
ZnCO 3 - ZnO + CO2 i Yellowish
Yellow
16. Ethyl bromide doesn't give a precipitate with AgNO3 solution
CO2 + Ca(OH)z - CaCO 3 + H2O
Litne water O,lciwn carbonate because it doesn't give free Br- ions to react with AgNO 3 solution.
(milky)

7. Since, the salt on treatment with dil. HCI gives a pungent Topic 3 Wet Test for Basic Radicals
smelling gas (SO2 ) and a yellow ppt.(S) it must contain SiOi- 1. Metal ions of group IV cations as Co2+ and Ni2+ are precipitated as
(thiosulphate ion) and further since it gives green flame test, it black coloured sulphides when H 2Sgas is passed into d1eir alkaline
must contain Ba 2+ ion. Therefore, salt is BaSiO3. salt mixture solutions.
Salt solution + NH4OH + NH4 ~ Pass H 2S
8. On adding freshly prepared FeSO 4 solution and then cone. (Gas)
H2 SO4 to water extract of salt mixture carefully by the sides of j,
test-tube, a dark brown ring of ferrous nitroso sulphate, Results in black ppt (green salt) of
FeSO4 · NO is formed at the ginction of two liquids.
NiS
NaNO 3 + H 2SO4 ~ NaHSO4 + HNO3 Black ppt (dark blackish brown
2HNO 3 + 6FeSO4 + 3H2 SO4 ~ salt)of CoS
3Fei(SO4 ) 3 + 2NO i +4Hp 2. Group IV cations like Zn 2 +, Mn2+, Ni2+, Co2+ are precipitated as
sulphides . This is because Ksp(ZnS) is very high and Zn 2+ is
FeSO4 + NO ~[Fe· NO] SO4
Ferrous precipitated as ZnS by high concentration ofs2- formed when H 2Sis
nitrososulphate passed in ammoniacal solution.
(Brown ring)
H 2S ~ 2W + s2- (I)
H+ + OW ~ H 2O j, (TI)
752 I Chapterwise & Topicwise Engineering Entrances Solved Papers
Reaction (I) is favoured in forward side if H+ is removed 9. Fe3+ and Al3+ both belongs to group III of inorganic analysis and
immediately by OW (NH40 H). both are precipitated as their hydroxides on adding group reagent,
2
Zn + + s-
2
~ ZnS J, i.e. NHpH in presence ofNH4CI.
White ppt Fe3+ + 30H- - Fe(OH) 3
Fe3+ and Al 3+ are precipitated as hydroxide while Mg2+ 3
Al + + 30W - Al(OH)3
precipitated as MgHP04• But only ppt. of Al(OH)3 is soluble in NaOH solution. Hence,
3. Mixture of two in organic salts HCI l P (ppt) Fe(OH)3 and Al(OH)3 are separated by using NaOH solution.

.
No reaction suggests
H2S
- ♦
w
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