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Physical Chemistry JEE
Physical Chemistry JEE
1-66
1.1 Chemistry and its Scope (1), 1.2 Brief History of Chemistry (2), 1.3 Matter and Energy (2), 1.4 Elements and
Compounds (4),1.5 Mixtures (6), 1.6 Alloys (7),1.7 Physical and Chemical Changes (8),1.8 Laws of Chemical
Combination (9), 1.9 Dalton's Atomic Theory (11), 1.1 0 Atoms, Molecules and Formulae (12), 1.11 Atomic and
Molecular Mass (13), 1.12 Avogadro's Hypothesis (16), 1.13 Mole Concept (17), 1.14 Equivalent Masses or
Chemical Equivalents (20),1.15 Methods for the Determination of Atomic Mass (21), 1.16 Types of Formulae
(23), 1.17 Percentage Composition of a Compound (23), 1.18 Determination of Empirical and Molecular
Formulae (25), 1.19 Chemical Equation (27), 1.20 Measurement in Chemistry: Fundamental and Derived Units
(28), Miscellaneous Numerical Examples (32), Summary and Important Points to Remember (39), Questions (42),
. Answers (43), Practice Problems (43), Objective Questions (48), Assertion-Reason Type Questions (55), Answers
to Objective and Assertion-Reason Type Questions (56), Brain Storming Problems for lIT Aspirants (57), Answers
(61), Integer Answer Type Questions (62), Answers (62), Linked Comprehension Type Questions (63), Answers
(65), SelfAssessment (65),Answers (66).
67-149
2.1 Introduction (67),2.2 Cathode Rays-Discovery of Electron (67),2.3 Positive Rays-Discovery of Proton
(69),2.4 Rutherford Experiment-Discovery of Nucleus (69), 2.5 Moseley Experiment-Atomic Number (70),
2.6 Discovery of Neutron (71),2.7 Rutherford Model (71), 2.8 Electromagnetic Radiations (72), 2.9 Emission
Spectra-Hydrogen Spectrum (73),2.10 Quantum Theory ofRadiation (75), 2.11 Bohr's Atomic Model (78), 2.12
Sommerfeld's Extension of Bohr Theory (82), 2.13 Particle and Wave Nature of Electron (87),2.14 Heisenberg
Uncertainty Principle (88), 2.15 Wave Mechanical Model ofAtom (90),2.16 Quantum Numbers (92), 2.17 Pauli's
Exclusion Principle (96), 2.18 Aufbau Principle (97), 2.19 Hund's Rule of Maximum Multiplicity (Orbital
Diagrams) (98), Electronic Configuration of Elements (99); 2.20 Photoelectric Effect (101),2.21 Some other
Fundamental Particles (102), 2.22 Isotopes (102), 2.23 Theories of Nuclear Stability (103), 2.24 The Whole
Number Rule and Packing Fraction (104), 2.25 The Magic Numbers (104), Miscellaneous Numerical Examples
(106), Summary and Important Points to Remember (109), Questions (114), Answers (116), Practice Problems
(116), Objective Questions (123), Assertion-Reason Type Questions (136), Answers to Objective and Assertion-
Reason Type Questions (137), Brain Storming Problems for lIT Aspirants (138), Answers (142), Integer Answer
Type Questions (143), Answers (143), Linked Comprehension Type Questions (144), Answers (147), Self
Assessment (148),Answers (149).
150-211
3.1 Radioactivity (150),3.2 Characteristics of Radioactive Radiations (150), 3.3 History of the Discovery of
Radioactivity (151),3.4 Analysis of Radioactive Radiations (151), 3.5 Cause of Radioactivity (152), 3.6 Theory of
Radioactive Disintegration (153), 3.7 Group Displacement Law (155), 3.8 Radioactive Disintegration Series
(157), 3.9 Rate of Disintegration and Half Life Period (158), 3.10 Average Life (162), 3.l1 Radioactive
Equilibrium (162), 3.12 Units of Radioactivity (163), 3.13 Artificial Transmutation (165), 3.14 Artificial
Radioactivity (167), 3.15 Nuclear Fission (167), 3.16 Nuclear Fusion (170), 3.17 Synthetic Elements Including
Transactinides (171), 3.18 Applications of Radioactivity (172), Miscellaneous Numerical Examples (175),
(viii)
Summary and Important Points to Remember (179), Questions (183), Answers (184), Practice Problems (185),
Objective Questions (189), Assertion~Reason Type Questions (198), Answers to Objective and Assertion-Reason
Type Questions (199), Brain Storming Problems for lIT Aspirants (200), Answers (204), Integer Answer Type
Questions (205), Answers (205), Linked Comprehension Type Questions (206), Answers (209), SelfAssessment
(210),Answers(211).
212-315
4.1 Introduction (212), Section 1: Gaseous State-4.2 The Gaseous State (212), 4.3 Gas Laws (213), 4.4 Ideal
Gas Equation (215), 4.5 Dalton's Law of Partial Pressures (220), 4.6 Diffusion of Gases and Graham's Law of
Diffusion (221),4.7 Kinetic Theory of Gases (226), 4.8 Maxwell-Boltzmann Distribution of Molecular Speeds
(228),4.9 van der Waals' Equation (232), 4.10 Critical Phenomenon and Liquefaction of Gases (233), 4.10.1
Experimental Methods for Liquefaction of Gases (234), Section 2 : Liquid State- 4.11 The Liquid State (242),
Section 3: Solid State-4.12 The Solid State (247), 4.13 Forms of Solids (248), 4.14 Isotropy and Anisotropy
(248),4.15 Differences between Crystalline and Amorphous Solids (248), 4.16 Types of Symmetry in Crystals
(249), 4.17 Space Lattice and Unit Cell (249), 4.18 Crystal Systems (250), 4.19 Designation of Planes in
Crystals-Miller Indices (251), 4.20 Crystallography and X-Ray Diffraction (252), 4.21 Analysis of Cubic
Systems (254),4.22 Packing ofIdentical Solid Spheres (258), 4.23 Types of Crystals (261), 4.24 Imperfection in
Solids (265), 4.25 Magnetic Properties (270), Miscellaneous Numerical Examples (273), Summary and Important
Points to Remember (276), Questions (282), Answers (283), Practice Problems (283), Objective Questions (288),
Assertion-Reason Type Questions (300), Answers to Objective and Assertion-Reason Type Questions (302), Brain
Storming Problems for lIT Aspirants (303), Answers (308), Integer Answer Type Questions (309), Answers (309),
Linked Comprehension Type Questions (31 0), Answers (313), SelfAssessment (314), Answers (315).
316-390
5.1 Introduction (316), 5.2 Solvent and Solute (316), 5.3 Types of Solutions (316), 5.4 Methods of Expressing the
Concentration of a Solution (316), 5.5 Solutions of Gases in Liquids (Solubility of Gases) (322), 5.6 Solutions of
Liquids in Liquids (325), 5.7 Theory of Fractional Distillation (329), 5.8 Solutions of Solids in Liquids (330), 5.9
Colligative Properties of Dilute Solutions (332), 5.10 Lowering in the Vapour Pressure (332), 5.11 Elevation of
Boiling Point (Ebullioscopy) (336), 5.12 Depression of Freezing Point (Cryoscopy) (338), 5.13 Osmosis and
Osmotic Pressure (342), 5.14 van't Hoff Theory of Dilute Solutions (344), 5.15 Determination of Molecular
Masses (345), 5.16 Reverse Osmosis (347), 5.17 Abnormal Colligative Properties (347), Miscellaneous
Numerical Examples (352), Summary and Important Points to Remember (356), Questions (360), Answers (360),
Practice Problems (361), Objective Questions (365), Assertion-Reason Type Questions (378), Answers to
Objective and Assertion-Reason Type Questions (379), Brain Storming Problems for lIT Aspirants (380),
Answers (385), Linked Comprehension Type Questions (386), Answers (388), Self Assessment (389), Answers
(390).
391-419
6.1 Introduction (391), 6.2 Particle Size and Colloidal State (391), 6.3 Types of Colloidal Solutions (392), 6.4
Preparation of Colloidal Solutions (393),6.5 Purification of Colloidal Solutions (394),6.6 Properties of Colloidal
Solution (395),6.7 Emulsions (399),6.8 Classification of Colloids Based on the Type ofPartidt:s of Dispersed
Phase (399), 6.9 Gels (40 I), 6.10 Applications of Colloids (402), Summary and Important Points to Remember
(403), Questions (405), Answers (406), Objective Questions (406), Assertion-Reason Type Questions (413)
Answers to Objective and Assertion-Reason Type Questions (414), Brain Storming Problems for lIT Aspirants
(415), Answers (416), Linked Comprehension Type Questions (416), Answers (417), Self Assessment (418),
Answers (419).
(ix)
les AND
420-517
7.1 Introduction (420),7.2 Terms Used in Thermodynamics (420), 7.3 Internal Energy (424), 7.4 First Law of
Thermodynamics (425),7.5 Enthalpy (426), 7.6 Heat Capacity (426),7.7 Expansion of an Ideal Gas (427), 7.8
Graphical Representation of various Thermodynamic Processes and the Calculation of Work done by Graphical
Methods (429), 7.9 louie-Thomson Effect (430), 7.1 0 Thermochemistry (434),7.11 Heat of Reaction or Enthalpy
of Reaction (434), 7.12 Enthalpy of Formation or Heat of Formation (436), 7.13 Enthalpy of Combustion or Heat
ofCombustion (437), 7.14 Enthalpy of Solution or Heat of Solution (439), 7.15 Enthalpy ofNeutralisation or Heat
ofNeutralisation (439),7.16 Enthalpies ofPhysical Changes (Phase Changes) (441),7.17 Hess's Law (The Law of
Constant Heat Summation) (441), 7.18 Influence of Temperature on the Heat of Reaction or Kirchhoff's
Equation (444), 7.19 Bond Energy or Bond Enthalpies (444), 7.20 Determination of Lattice Energy (Born-Haber
Cycle) (450), 7.21 Experimental Determination of the Heat of Reaction (451), 7.22 Limitations of First Law of
Thermodynamics (452), 7.23 Spontaneous and Non-spontaneous Processes (453), 7.24 Entropy (456), 7.25
Entropy Change During Phase Transitions (458), 7.26 Second Law of Thermodynamics (460), 7.27 Gibbs Free
Energy, (G), Change in Free Energy and Spontaneity (461), 7.28 Standard Free Energy Change (466), 7.29
Relationship between Standard Free Energy Change (aG") and Equilibrium Constant (466), 7.30 Physical
Significance of Gibbs Free Energy Change (Free Energy and Useful Work) (469), 7.31 Absolute Entropies and
Third Law of Thermodynamics (469), 7.32 Conversion of Heat into Work-The Carnot Cycle (471),
Miscellaneous Numerical Examples (473), Summary and Important Points to Remember (477), Questions (481),
Answers (482), Practice Problems (482), Objective Questions (489), Assertion-Reason Type Questions (501),
Answers to Objective and Assertion-Reason Type Questions (503), Brain Storming Problems for lIT Aspirants
(504), Answers (509), Integer Answer Type Questions (510), Answers (510), Linked Comprehension Type
Questions (5II),Answers(515), SelfAssessment(515),Answers(517).
518-591
8.1 Introduction (518),8.2 Rate of Reaction (Average and Instantaneous Rate) (519), 8.3 Law of Mass Action
(Guldberg and Waage, 1864) (523), 8.4 Rate Constant (523),8.5 Collision Theory of Reaction Rate (Arrhenius
Theory of Reaction Rate) (524), 8.6 Molecularity of Reaction (529),8.7 Order of Reaction (530),8.8 Pseudo-
Order Reaction (531),8.9 Reaction Mechanism (535), 8.10 Reactions of Various Orders (536),8.11 Methods for
Determination of Order of a Reaction (540), Miscellaneous Numerical Examples (548), Summary and Important
Points to Remember (554), Questions (557), Answers (558), Practice Problems (558), Objective Questions (565),
Assertion-Reason Type Questions (579), Answers to Objective and Assertion-Reason Type Questions (580), Brain
Storming Problems for lIT Aspirants (581), Answers (586), Integer Answer Type Questions (586), Answers (586),
Linked Comprehension Type Questions (587), Answers (588), SelfAssessment (589), Answers (591).
592-655
9.1 Introduction (592), 9.2 State of Chemical Equilibrium (593), 9.3 The Law of Chemical Equilibrium
(Application of Law of Mass Action) (594). 9.4 Reaction Quotient or Mass Action Ratio (597), 9.5 Activation
Energies for Forward and Backward Reactions (599), 9.6 Standard Free Energy Change of a Reaction and its
Equilibrium Constant (600),9.7 Equilibrium Constant Expressions for Some Reactions (601), 9.8 Le Chatelier's
Principle (608), 9.9 Application of Le Chatelier's Principle to Physical Equilibria (610), 9.10 Calculation of
Degree of Dissociation from Density Measurements (611), Miscellaneous Numerical Examples (612), Summary
and Important Points to Remember (621), Questions (624), Answers (625), Practice Problems (625), Objective
Questions (629), Assertion-Reason Type Questions (643), Answers to Objective and Assertion-Reason Type
Questions (644), Brain Storming Problems for lIT Aspirants (645) , Answers (649), Integer Answer Type Questions
(650), Answers (650), Linked Comprehension Type Questions (651), Answers (653), Self Assessment (654),
Answers (655).
(x)
IONICEQUILI.BR1U M 656-731
10.1 Introduction (656), 10.2 Ostwald's Dilution Law (656), 10.3 Common Ion Effect (658), 10.4 Solubility
Product (660), 10.5 Acids and Bases (668), 10.6 Relative Strength of Acids and Bases (671), 10.7 Acid-Base
Neutralisation-Salts (673),10.8 Ionic Product of Water (674),10.9 Hydrogen Ion Concentration-pH Scale
(675),10.10 pH of Weak Acids and Bases (676)g 10.11 Buffer Solutions (679),10.12 Salt Hydrolysis (686), 10.13
Theory of Indicators (693), Miscellaneous Numerical Examples (695), Summary and Important Points to
Remember (700), Questions (705), Answers (706), Practice Problems (706), Objective Questions (711),
Assertion-Reason Type Questions (726), Answers to Objective an~Assertion-Reason Type Questions (727), Brain
Stormingl?roblems for lIT Aspirants (728), Answers (732), Integer Answer Type Questions (732), Answers (732),
Linked Comprehension Type Questions (733),Answers (735), SelfAssessment (736), Answers (737).
Elf;CT,ROC'H,EMISTRV
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774-865
Section 1: Electrolytes and Electrolysis- 12.1 Introduction (774), 12.2 Preferential Discharge Theory (775),
12.3 Faraday's Laws of Electrolysis (776), 12.4 Applications of Electrolysis (778), Section 2: Conductance and
Conductors-12.5 Arrhenius Theory of Electrolytic Dissociation (784), 12.6 Factors Pertaining to Degree of
Ionisation (786), 12.7 Electrolytic Conductance (786), 12.8 Kohlrausch's Law (789), 12.9 Theory of Weak
Electrolytes (789), Section 3 : Electrochemical Cell-12.l0 Electrochemical Cell (792), 12.11 Daniell Cell
(792), 12.12 Salt Bridge and Its Significance (793), 12.13 Representation of an Electrochemical Cell (Galvanic
Cell) (794), 12.14 Electrode Potential (794), 12.15 Standard Electrode Potential (795), 12.16 Reference Electrode
(Standard Hydrogen Electrode, SHE or NHE) (795), 12.17 Measurement of Electrode Potential (795), 12.18 EMF
of a Galvanic Cell (797), 12.19 Reversible and Irreversible Cells (797), 12.20 Some other Reference Electrodes
(797), 12.21 Prediction for Occurrence of a Redox Reaction (798), 12.22 Electrode and Cell Potentials-Nemst
Equation (798), 12.23 Electrochemical Series (803), 12.24 Primary Voltaic Cell (The Dry Cell) (808), 12.25
Secondary Voltaic Cell (Lead Storage Battery) (809), 12.26 Fuel Cell (809), 12.27 Concentration Cells (809),
12.28 Commercial Production of Chemicals (811), Miscellaneous Numerical Examples (816), Summary and
Important Points to Remember (824), Questions (829), Answers (830), Practice Problems (831), Objective
Questions (839), Assertion-Reaso)}. Type Questions (852), Answers to Objective and Assertion-Reason Type
Questions (853), Brain Storming Problems for lIT Aspirants (854), Answers (858), Integer Answer Type Questions
(859), Answers (859), Linked Comprehension Type Questions (860), Answers (863), Self Assessment (863),
Answers (865).
866-899
Adsorption : 13.1 Introduction (866), 13.2 Distinction between Adsorption and Absorption (866), 13.3
Mechanism of Adsorption (867), 13.4 Types of Adsorption (Adsorption of Gases) (867), 13.5 Adsorption
Isotherms (868), 13.6 Adsorption from Solution Phase (870), 13.7 Adsorption Isobars and Isostere (870),
(xi)
13.8 Applications of Adsorption (871), Catalysis : 13.9 Introduction (872), 13.10 Homogeneous and
Heterogeneous Catalysis (872), 13.11 Types of Catalysis (873), 13.12 Characteristics of Catalysis (874), 13.13
Theories of Catalysis (876), 13.14 Acid-Base Catalysis (878),13.15 Enzyme Catalysis (879),13.16 Catalysts in
Industry (882), 13.17 Zeolites (883), 13.18Automobile Catalytic Converter (883), Summary and Important Points
to Rqmember (884), Questions (886), Answers (886), Practice Problems (887), Objective Questions (888),
Assehion-Reason Type Questions (893 ),Answers to Objective and Assertion-Reason Type Questions (894), Brain
Storming Problems for lIT Aspirants (895), Answers (897), Linked Comprehension Type Questions (897),
Answers (897), SelfAssessment (898), Answers (899).
~()LUMETRICANALYSIS 900-945
14.1 Important Termed used in Volumetric Analysis (900), 14.2 Concentration Representation of Solution (900),
14.3 Classification of Reactions Involved in Volumetric Analysis (901),14.4 Calculation of Equivalent Mass of
Different Substances (902),14.5 Acid-Base Titrations (907),14.6 Titration of Mixture of NaOH, Na2C03 and
NaHC0 3 by Strong Acid Like HCl (908),14.7 Redox Titrations (916),14.8 Iodometric and Iodimetric Titrations
(916), Questions (926), Answers (931), Objective Questions (932), Assertion-Reason Type Questions (937),
Answers to Objective and Assertion-Reason Type Questions (937), Brain Storming Problems for lIT Aspirants
(938), Answers (941), Linked Comprehension Type Questions (942), Answers (944), Self Assessment (944),
Answers (945).
1..1' CHEMISTRY AND ITS SCOPE (2) Inorganic chemistry: It deals with the study of all
known elements and their compounds except organic
Chemistry is a branch of physical science which deals with the compounds. It is concerned with the materials obtained from
study ofmatter, its physical and chemicalproperties, its chemical minerals, air, sea and soil.
composition, the physical and chemical changes which it (3) Physical chemistry: It is concerned with the physical
undergoes and the energy changes that accompany these properties and constitution of matter, the laws of chemical
processes. combination and theories go.verning reactions. The effect of
All objects in this universe are composed of matter. Most of temperature, pressure, light, concentration, etc., on reactions
these objects are visible (solids and liquids) but some are come under the scope of physical chemistry.
invisible. Chemistry is termed as a material science because it is (4) Analytical chemistry: It deals with various methods of
concerned with all material substances such as air, water, rocks, analysis of chemical substances both qualitative and quantitative.
minerals, plants, animals including man, the earth on which we It includes chemical and physical methods of analysis.
all live, and other planets. According to one of the famous A number of specialised branches have been introduced as to
scientists of twentieth century, Linus Pauling, Chemistry is the
cope with the extraordinary expansion in the subject of
science of substances, their properties, their structure and their
chemistry. Some of the specialised branches are:
transformations.
(i) Biochemistry: It comprises the studies of the substances
Chemistry is a very interesting subject which touches almost
related to living organisms and life processes.
every aspect of our lives, our culture and our environment. It has
(ii) Medicinal chemistry: It deals with the application of
changed our civilization to a great extent. The present day
chemical substances for the prevention and cure of various
chemistry .has provided man with more comforts for a healthier
diseases in living 'beings.
and happier life. A large number ormaterials which we use these
days were unknown at the turn of the century. A few decades (iii) Soil and agriculture chemistry: It deals with the:
back, our clothes and footwears were exclusively of natural analysis and treatment of soils so as to increase its fertility for the'
origin such as vegetable fibres, wool, hair, skin of animals, etc., better yields of crops. It is concerned with the chemicals used as
but, now the synthetic fibres produced in chemical factories have fertilizers, insecticides, germicides, herbicides, etc.
largely replaced them. Modem chemistry has given man new (iv) Geochemistry: It includes the study of natural
plastics, fuels, metal alloys, fertilizers, building materials, drugs, substances like ores and minerals, coal, petroleum, etc.
energy sources, etc. (v) Industrial chemistry: It deals -with the study of
During the last few decades, the expansion of chemistry has chemical processes for the production of useful chemicals on a
been tremendous. The field has become wide and complex. For large scale at relatively low costs.
convenience and better understanding of the subject, it has been (vi) Nuclear chemistry: It is the most recent branch. It
divided into various branches. The four main branches of includes the study of nuclear reactions, the' production of
chemistry are: radioactive isotopes and their applications in various fields.
(1) Organic chemistry; (2) Inorganic chemistry; (vii) Structural chemistry: It deals with various
(3) Physical chemistry; (4) Analytical chemistry. techniques used for elucidation of the structure of chemical
(1) Organic chemistry: It is concerned with the study of substances. It is concerned with the properties of substances in
compounds of carbon except carbonates, bicarbonates, cyanides, terms of their structure.
isocyanides, carbides and oxides of carbon. It is actually the (viii) Polymer chemistry: It includes the study of chemical
study of hydrocarbons and their derivatives. substances of very high molecular masses of the order of 100,000
or greater, called polymers-natural or artificial. This branch is
2 G.R.B. PHYSICAL CHEMISTRy.fDR COMPETITIONS
gaining popularity as the use of plastics, rubber, synthetic fibres, Pri~~tley and Carl Scheele. Priestley was a very conservative
silicones, etc., is on the increase thes~ days. scientist. Even after his discovery of oxygen, he still believed in
(ix) Limnochemistry: It deals with the study of chemistry phlogiston theory.
involved in the river water or water reservoirs. (v) Modern period: Lavoisier (1743-1793), a French
(x) Phytochemistry: It includes the study of chemistry of plants. chemist, is regarded as the father of modern chemistry. He
Thus, it can be said iliat theteisno othel'bfaQ,c1(ofscience presented the exact explanation of combustion by proposing that
~4ichis so wide in its<scope as cheniistty;" . " . oXY8¢I1 is necessary for combustion. This concept was largely
responsible for the overthrow of the phlogiston theory. Among
t~2 aRIEFHISTORY OF CHEMISTRY his other contributions, he showed that water is composed of
hydrogen and oxygen, proposed the theory of indestructibility of
It is difficult to specify the date when science of chemistry came fl\atter, presented a clear defmition of an element and proposed a
into existence; however, its 'groWtli must have gone side by side system of chemical nomenclature.
with the growth of civilization. Broadly, the history of chemistry Another major step towards modem chemistry was taken in
can be studied under five periodS of its development. the first decade of the nineteenth century when the English
(i) Ancient period up to 350 A.D.: In ancient times, many chemist, John Dalton, postulate~ that all elements are made up
chemical operations such as souring of milk, conversion of sweet of atoms. He pictured atoms as tiny, indestructible units that
juices into wines, the conversion of wines into vinegar, etc., were could combine to form compound atoms or molecules. Dalton
known: Around3000,RC'" techniques of making glass, pottery, proposed that each element has its own kind of atom,s and the
pigments, dyes, perfuines and extraction of metals especially atoms of different elements differ in essentially nothing but their
gold* and silver were known in China, India, Egypt and Greece. masses. He determined the relative fl\asses of atoms of many
The beginning of chemistry as a science could probably be set elements. Thus, a new era had begun. The other important
about 400 B.c., when the theory was proposed that everything is chemists of this period are:
cOlllPosed of four elements: earth, air, fire and water. The first (a) Richter-Law of Reciprocal Proportions (1794)
.. bQOkof chemistry was written in Egypt around 300 A.D. The
(b) Proust-Law of Definite Proportions (1799)
terril chemistry meant the Egyptian art.
(c) Gay-Lussac-Law of Combining Volumes of Gases
(ii) The aicli"emicai period (350-1500): During this (1808)
period, scientists called alchemists tried to discover two things:
(d) Avogadro-Avogadro Hypothesis (1811)
an elixir of life which could make m:an eternally young and a
(e) Berzelius-Introduced the Modem Symbols for
philospher's stone which could transmute base metals like zinc,
Elements (1813)
copper, iron, etc., into gold. The alchemists failed in their efforts
because no philospher's stone and elixir of life actually existed (f) Faraday-Laws of Electrolysis (1833)
but we are indebted to them for designing new types ofapparatus (g) Thomas Graham""':"'Law of Gaseous Diffusion (1861)
and for discovering new chemical operations such as distillation, (h) Mendeleev-Periodic Law and Periodic Table (1869)
sublimation, e~traction of gold by amalgamation process and (i) Arrhenius-TheoryofIonization (1887)
preparation of caustic alkalies from ashes of plants., (j) Henry Becquerel-Discovery of Radioactivity (1896)
(iii) tlatro chemistry period (i500~1650): . During this (k) Madam Curie-Discovered Radium and Polonium
era, chemists paid their attention towards medico-chemical (1898)
problems. They believed tllat the primary object Of c4emistry was The twentieth century is' regarded as an active era of
to prepare medicines and not to make gold from base metals. chemistry. During this period, chemistry has fl\ade many
DUring this period, the study of gases was begun and quantitative contributions to human knowledge and civilization. Now, we live
experiments were undertaken for the first time. Robert Boyle in a world of synthetic fl\aterials. Chemistry of today is actually
(1627-1691) found that when it metal is heated in air, the mass· helping in solving major problems of our present day civilization
increases. He also established the relationship between volume such as population explosion, food and diseases, depletion of
and pressure of a gas. In 1661, Boyle wrote. the book 'The sources of energy, depletion of natural sources and environmental
Skeptical Chyrnist' in which he criticised' the hasic ideas of pollution ..
alchemy.
(iv) The phlogiston period (1650-1774): The phlogiston 1::~, MATTER AND ENERGY
theory was proposed by Ernst Stahl (1660-1734). Phlogiston
Besides life, matter a~denergy are regarded the two fundamental
was described as a substance in a combustible fl\aterial which is
entities with which whole of the universe is composed of. Matter
given off when the material bun:J.s. This theory persisted for about,
is anything that has mass and occupies space. All bodies in the
100 years arid was a centre of much controversy. During the end
universe conform to this definition. Mass is the quantity of matter
of the eighteenth century, much work was done with gases,
in a particular sample of matter. Mass ofa body is constant and
especially by Joseph Black, Henry Cavendish, Josepth
does not change regardless of where it is measured. The mass of a
-",. ~ . '
*Gold was probably the ftrst metal to be used because it occurred as a free metal in the earth. :
t Iatro is a Greek word m~aning a physician.
BASIC PRINCIPLES 3
body would be the same on the moon as it is on the earth. Our structure and are very near to one another. This form of matter is
senses of sight and touch usually tell us that an object occupies associated with minimum amount of energy.
space except in the case of colourless, odourless and tasteless in liquid state, substances have no definite shape but possess a
gases where some other evidence is required to satisfy the fixed volume. There is slight effect of pressure and temperature
definition of matter. on their volumes. They have the ~perty of flowing. The
The term weight should not be used in place of mass as it has a particles are nearer to one another than in a gas and this form of
different meaning. The term weight refers to the force with which matter is associated with energy more than solids.
an object is attracted towards earth. An object resting on earth In a gaseous state, substances have no definite shape and
experiences a force called its weight, W, that is equal to its mass volume. Gases fill completely any vessel in which they are
m, mUltiplied by the acceleration due to gravity g, thatis, confined and thus occupy the whole space available to them.
W=mg There is a large effect of pressur-eand temperature on their
The weight of an object thus depends on the value of' g' which volumes. The particles are far apart from one another and move
varies from place to place. However, the mass of an object is with very high speeds in all possible directions. This form of
determined by comparing the weights of two objects, one of matter is associated with maximum amount of energy.
known mass, the other of unknown mass in the same location on Sublimation
earth as both experience the same gravitational acceleration.
Solidification
Matter is indestructible, i, e., it can -neither be -created, nor
destroyed, but it can change its form; thus, the total quantity of Solid Liquid , Gas
matter of the universe is constant. ' .~~
Energy is defined as the capacity of doing work. Freezing Condensation
Anything which has the capacity to push the matter from one place
to another possesses energy. There are various forms of energy + energy + energy
such as heat, light, etc. Energy is neither created, nor destroyed, but Solid '~ Liquid ~ Gas
-energy . ,- energy
can only be transformed from one form of energy to another.
AbsorPtion 'of energy
The world became aware of the fact that matter can be
converted into energy with the discovery of nuclear reactions, Release of energy
especially nuclear fission and nuclear fusion. The relationship Depending on temperature and pressure, a substance can exist
between mass and energy was given by Einstein. The. famous in anyone of the three forms of matter.
relation is: ... ' (ii) Chemical classification: Matter exists in nature in the
2
E =mc form of chemical substances. A pure substa~ce is defined as a
where, E = energy, m = mass and c = velocity of light. variety of matter, all samples of which have same composition
and properties. Pure substances are divided into elements and
On account of this equation, the 'above two 'laws are
compounds. Most of the materials found in nature are in the. form
amalgamated into a single statement:
of mixtures consisting of tWo or more substances. There are two
"The total amount of matter and energy available in the types of mixtures-Homogeneous and Heterogeneous. Both
universe is fIXed." types of mixtures can be separated into their components (pure
Example 1. Calcula(e the amount of energy released in substances) by mechaniCal and physical methods. Th~
ergs, calories and in joules when 0.001 kg ofmass disappears. classification can be summarized in the following way:
[Given, Velocity of light = 3 X 108 ms-1 ]
Matter
Solution: According to Einstein equation, E lne
2
I '
m=0.00Ikg=lxlO- kg;c=3xI0 ms-
E
3 8
9xlO13 J
lJ = 10 erg = 0.24 cal
9xlO 13 xl0 7 erg=9x10 13 x 0.24 cal
1 1 . r Physical Pure,
1
Solids Liquids Gases Mixtures
= 9 x 1020 erg me.~ods substances
2.16 x 1013 cal
I
ClaSSification of Matter I
Homogeneous
1'
Heterogeneous
(i) Physical classification:, Matter can exist in anyone of
three forms, (a) solid, (b) liquid and (c) gas: Chemical
In the solid state, substances are rigid. They have a definite Compounds Elements
methods
shape and fixed volume. There is negligible effect of changes in
pressure and temperature on their volumes. The individual
particles that make up a solid occupy definite positions in the Inorganic Organic
4 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Properties of Matter: Properties are the characteristic (iii) or from names of the elements in other languages such as
qualities with the help of which different kinds of matter can be Latin, German, etc.
commonly recognised. In chemistry, substances are distinguished Na-Sodium (Latin name Natrium)
by two types of properties, viz (i) Chemical properties and (ii) Cu-Copper (Latin name Cuprum)
Physical properties.
Fe---Iron (Latin name Ferrum)
The chemical properties of substances are those in which they
undergo change in composition either alone or by interactions with Ag-Silver (Latin name Argentum)
other substances, i. e., to form new substances having different Pb-Lead (Latin name Plumbum)
compositions from the substances which undergo change. Au-Gold (Latin name Aurum)
The properties of substances which are observed in absence of K-Potassium (Latin name Kalium)
any change in composition under specific physical s~ate are
Hg-Mercury (Latin name Hydragyrum)
termed physical properties. Colour, density, melting point,
boiling point, hardness, refractive index, thermal conductivity, W-Tungsten (German name Wolfram)
electrical conductivity, malleability, ductility, etc., are some Out of 117 elements known, 88 have been isolated from
examples of the physical properties. The properties of matter can natural sources and the remaining have been prepared by
be further classified into two: (i) Intensive properties and (ii) artificial means. The man made elements are:
Extensive properties. The intensive properties are those which
S.No. Name Symbol S.No. Name Symbol
do not depend upon the quantity of matter, e.g. , colour, density,
melting point, boiling point, refractive index, etc. These 1. Neptunium Np 16. Hassium or Hs or
properties are same irrespective of the quantity of the substance. Unniloctium Uno
Chemical properties are also intensive properties. The extensive 2. 17. Meitnerium or
Plutonium Pu Mtor
properties of matter depend on the quantity of matter. Volume, Unnilennium Une
mass, weight, energy, etc., are the extensive properties.
3. Americium Am 18. Ununnilium Uun
:1;4 ELEMENTS AND COMPOUNDS 4. Curium Cm 19. Unununium Uuu
Elements are pure substances that cannot be decomposed into 5. Berkelium Bk 20. Ununbium Uub
simpler substances by chemical changes. The smallest particles 6. 21.
Californium Cf Ununtrium Uut
of an element possess the same properties as the bigger particles.
An element can also be defined as a pure substance which 7. Einsteinium Es 22. Ununquadium Uuq
consists of only one type of atoms. Due to discovery of isotopes, 8. Fermium Fm 23. Ununpentium Uup
this definition does not seem to be correct. The modem definition
9. Mendelevium Md 24. Ununhexium Uuh
of an element is that it is a simple individual which has a definite
atomic number (see atomic structure) and has a defmite position in 10. Nobelium No 25. Ununoctium Uuo
the periodic table. It carmot be decomposed in a chemical change. 11. Lawrencium Lr 26. Technetium Tc
In chemistry, the elements are the chemical alphabet and
compounds are the words, i. e. , combinations of elements. 12. Kurchatovium Ku 27 Promethium Pm
There are presently 117 different elements known. Every 13. Hahnium Ha 1 28.• Astatine At
element has been given a definite name and for convenience a 14. Seaborgium or Sg or \29. Francium Fr
nick name which in· chemical language is called a symbol. Unnilhexium Unh
Symbol is a small abbreviation to represent a full and lengthy
name of the element. Symbols have been derived: 15. Nielsbohrium or Bhor
Uns
(i) either by taking the first letter of the name of the element Unnilseptium I
which is capitalized: The elements from S. No. 1 to 25 are called transuranic
O-Oxygen N-Nitrogen F- Fluorine elements. The credit for the discovery of most of the transuranic
C-Carbon H-Hydrogen U- Uranium elements goes to the scientist G.T. Seaborg. The first artificially
P-Phosphorus S-Sulphur 1- Iodine produced element was technetium. It was synthesised in 1937 by
scientists at the University of California at Berkley.
(ii) or by taking the first letter and one more letter from the Most of the earth's crust is made up of a small number of
name of the element. The first letter is always capitalized. elements. Only ten of the naturally occurring elements make up
Ca-Calcium Ni-Nickel AI-Aluminium 99% mass of the earth's crust, oceans and atmosphere. The
Mg-Magnesium Co-Cobalt Bi-Bismuth following table shows the abundance of highly abundant
CI-Chlorine Br-Bromine Sa-Barium elements in nature:
Note: Among the naturally occurring elements, lH is lightest and 2~~ U is the heaviest atom.
l
BASIC PRINCIPLES I' 5
Abundance of Elements (Earth's Crust, Oceans and generally (i) brittle, (ii) non-lustrous, (iii) having low melting
Atmosphere) and boiling points, (iv) non-conductors of heat, (v) capable of
Oxygen 49.5% Chlorine 0.19% forming acidic oxides or neutral oxides, (vi) not capable of
evolving hydrogen from acids, and (vii) capable of forming
Silicon 25.7% Phosphorus 0.12%
volatile hydrides.
Aluminium 7.5% Manganese 0.09% There are some elements which do not fit completely into
Iron 4.7% Carbon 0.08% either the metal or non-metal class. Elements which have some
Calcium 3.4% N'$. Sulpur 0.06% '$. properties of both metals and non-metals are called semi:metals
t'-
Sodium 2.6% 0\ 0\ Barium 0.04% d or metalloids. The semi-metals are silicon, germanium, arsenic,
antimony and tellurium. .
Potassium 2.4% Chromium 0.033%
The above classification of elements is a rough one as certain
Magnesium 1.9% Nitrogen 0.030%
metals. like lithium, sodium, potassium possess low density;
Hydrogen 0.87% Fluorine 0.027% certain non-metals like hydrogen and graphite (a form of carbon)
Titanium 0.58% Zirconium 0.023% are good conductors of electricity. Metals rarely combine with
one another while non-metals combine with one another to form
If the entire universe is considered, then 90% of matter is
compounds. Metals and non-metals commonly combine with .
hydrogen. Helium is the second most abundant element
each other to form compounds.
amounting to 9% and the remaining elements make up only 1%
of the universe with oxygen, neon, carbon and nitrogen next in
Compounds
order of decreasing abundance.
The commercial use of an element depends not only upon its Compounds are also pure substances that are composed of
abundance but also upon its accessibility. Some of the common two or more different elements in a fixed proportion by mass.
elements such as copper, zinc, tin and lead are not abundant but Compounds containing more than four elements are rare. The
are found in nature in rich deposits from which these can be properties of a compound are altogether different from the
easily extracted. On the other hand, the elements such as titanium properties of the elements from which it has been constituted.
and zirconium which are found in abundance in nature are not The compound water has a definite composition, i. e., 11.2%
widely used because their ores are not rich and their extraction is hydrogen and 88.8% oxygen, Thus, the two are present in the
difficult and expensive. ratio of 1 : 8 by mass. The properties of water are totally different
from the properties of hydrogen and oxygen both. Hydrogen and
Metals, Non-metals and Metalloids oxygen are in gaseous state while water is in liquid state under
ordinary atmospheric conditions. Oxygen supports combustion
All the elements may be classified into two groups, metals while hydrogen is combustible but water is normally used for
and non-metals. The division is based on both physical and extinguishing fire. Component elements in compounds can be
chemical properties. separated only by chemical means and not by physical methods.
Metals are regarded as those elements which possess the Compounds are classified into two types:
following properties:
(i) Organic compounds: The' compounds obtained from
(i) They are generally solids at ordinary conditions. Mercury living sources are termed organic compounds. The term organic
is an exception which is in liquid state. is now applied to hydrocarbons (compounds of carbon and
(ii) They are lustrous in nature. hydrogen) and their derivatives.
(iii) They possess high density. (ii) Inorganic compounds: .! The compounds obtained from
(iv) They are good conductors of electricity and heat. non-living sources such as roc~ and minerals are termed
(v) They are malleable and ductile. inorganic compounds. The compounds of all elements except
(vi) They possess generally high melting and boiling points. hydrocarbons and their derivatives are included in this category.
(vii) They react with mineral acids liberating hydrogen. The number of organic compounds is very large in comparison to
(viii) They form basic oxides. inorganic compounds.
(ix) They form non-volatile hydrides if combine with Some Specific Properties of Substances: Some specific
hydrogen. properties of substances are given below:
(i) Deliquescence: The property of certain compounds of
(x) They have molecules usually mono-atomic in the vapour
taking up the moisture present in atmosphere and becoming wet
state. when exposed, is knpwn as deliquescence. These compounds are'
Sodium, calcium, aluminium, copper, silver, zinc, iron, nickel, known as deliquescent. Sodium hydroxlde, potassium hydroxide,
gold, mercury, etc., are the examples of metals. anhydrous calcium chloride, anhydro;us magnesium chloride,
The non-metals do not show the above properties. Six of the anhydrous ferric chloride, etc., are the hamples of deliquescent
non-metals, carbon, boron, phosphorus, sulphur, selenium and compounds. Sodium chloride is noti deliquescent but when
iodine, are solids. Bromine is the only liquid non-metal at room common salt is placed in atmosphere it becomes wet due to
temperature and normal pressure. The remaining non-metals; presence of an impurity of magnesium chloride.
nitrogen, oxygen, fluorine, chlorine, hydrogen, helium, argon, (ii) Hygroscopicity: Certain compounds combine with the
neon, krypton, xenon and radon are gases. Non-metals are moisture of atmosphere and are converted into hydroxides or
6 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
hydrates. Such substances are called hygroscopic. Anhydrous microscppic .~evel. Tlle, c~mponeIits cm,m,ot, ~e s~en"by pak~ ~~
copper sulphate, quick lime (CaO), anhydrous sodium carbonate, a
or with the' heIp of microscope. The mixture is, uniform,
etc., are of hygroscopic nature. throughout having a single phase*. The homogeneous ri:riXttire is
(iii). Emorescence: The property of some crystalline isotropic in nature, i. e" every portion of it has the same
substances of losing their water of crystallisation on exposure composition and properties. '
, and becoming powdery on the surface is called efflorescence. Alloys such as brass, steel, 22-carat gold; solutions such as
Such salts are known as efflorescent. The examples are: common salt dissolved in water, sugar dissolved in water, iodine
Ferrous sulphate (F eSO4' 7H2 0), sodium carbonate dissolved in carbon tetrachloride, benzene in toluene, methyl
(Na2C03·lOH20), sodium sulphate (Na2 S04,lOH20) , potash alcohol in water; gasoline (a mixture of hydrocarbons), air, etc.,
alum [K 2S04 'Al2 (S04)3 ·24H 2 0] , etc: are some of the examples of homogeneous mixtures.
(iv) Malleability: This property is shown by metals. When A heterogeneous mixture is not uniform. It can have two or
the solid is beaten and does not break but is converted into a thin more phases. The components can be seen by naked eye or with
sheet, it is said to possess the property of malleability. Copper, the help of a microscope. It has anisotropic properties, i.e.,
gold, silver, aluminium, lead, etc"can be easily hammered into properties are not uniform throughout the mixture. Soil, a
sheets. Gold is the most malleable metal. mixture of sulphur and sand, a mixture of iron filings and sand,
(v) Ductility: The property of a metal to be drawn into smoke, etc., are the examples of heterogeneous mixtures.
wires is termed ductility, Copper, silver, gold, aluminium, iron, The components of a mixture differ in many of their physical
et<;:., are ductile in nature. Platinum is the most ductile metal. and chemical properties. The advantage of this difference is taken
(vi) Elasticity: When the stress is small" the ;solid:, in the separation of a mixture. The method of separation
completely regains its original shape, size or volume after the employed should not bring about the destruction of anyone of the
deforming force is removed. The solid is then said to be elastic. components. Some preliminary techniques based on physical
Steel, glass, ivory, etc., are elastic bodies. properties are described here in brief.
(vii) Plasticity: When stress is increased on a metal, a limit , (i) Filtration: This method is useful when one of the
is reached beyond which, if the stress is removed, the solid does components is an insoluble solid in a solvent. The insoluble solid
not come back to its original shape Or size. It acquires a permanent is obtained by filtration of the suspension through filter-paper.
deformation. Such materials can be given any shape without any For example, common salt containing sand is separated by
difficulty. filtration. The mixture is mixed with water. It is shaken so as to
(viii) Brittleness: The solid materials which, break into dissolve common salt. The sand remains insoluble. The
small pieces on hammering are called brittle. The solids of suspension is put to filtration. ,The sand cplleqts ,on the,
non-metals are generally brittle in nature. filter-paper. It is taken in a baSin and 'dried hy heating. The filtrate .
(ix) Hardness: A material is said to be harder than the other is taken in evaporating dish and heated till whole of the water is
if it can scratch it. The hardness is measured on Mho's scale. For evaporated. Solid common salt is thus obtained in the dish.
this purpose, ten minerals have been selected which have been Sugar containing charcoal, potassium nitrate containing saw
assigned hardness from 1 to 10. dust or mixtures having insoluble components can be separated
Hardness Mineral by filtration.
Hardness Mineral
(b) Sublimation: It is a process in which a solid'substance is
Talc 6 Orthoclase directly converted into its vapours by ~lication of heat and vapour is
2 Gypsum 7 Quartz reconverted into solid by subsequent cooling. The method is used
Calcite Topaz when one of the components undergoes sublimation and other
3 8
components are not decomposed by heating. For example, naphtha-
4 Fluorite 9 Corundum lene can be separated from common salt by sublimation. Similarly, a
5 Apatite 10 Diamond mixture of ammomwn chloride and potassiwn chloride can be
separated by sublimation as ammoniwn chloride sublimes on heating.
On Mho's scale, hardness of diamond is maximum and that of
(iii) Distillation: It is a process of converting a liquid into
talc is ri1inimum. If a material can scratch topaz but cannot
its vapour by heating and then condensing the vapours again into
scratch corundum it possesses hardness equal to 8.
the same liquid by cooling. Thus, distillati()n involves
vaporisation and condensation both.
1'.5 MIXTURES
Distillation =Vaporisation + Condensation
A mixture is a material containing two or more substances either This method is employed to separate liquids which have
/ elements or compounds or both in any proportion. Substances different boiling points or a liquid from non-volatile solid or
which form a mixture are milled components. Components are solids either in solution or suspension. The mixture of copper
present in the,mixtQre without loss of their identity. There are two sulphate and water or mixture of water (b.p. 100°C) and methyl
types of mixtures-:-homogeneous, and heterogeneous. In a alcohol (b.p. 4SOC) can be separated by this method.
homogeneous mixture, the components are mixed uniformly to
* Phase is defiried. as part ora system which hasunifonn properties and composition. A solution or mixture of sugar and water is a one phase system.
Every drop of the solution has same properties and sartte cdmpOsition.
BASIC PRINCIPLES . I
(Iv) Magnetic separati(ln: If one of the components of a Mixture
.--_ _ _ _...II_A_m....,agnet is moved in the mixture
mixture has magnetic properties, it can be separated by using Ii
magnet. Iron is separated from a mixture of iron filings and
Iron filings attracted Residue
sulphur by moving a magnet through the mixture. by magnet . 1Heated
(v) Solvent extraction: This method is based on the
preferential solubility of one of the components ofthe rnixture in
a particular solvent (usually a low-boiling organic solvent) which Vapours Residue
1
forms a distinctly separate layer with the other liquid if present in (Common salt + sand)
the mixture. For example, iodine present in water can be .
1Cooled
Shaken with
recovered with the help· of ether or carbon disulphide. For this Naphthalene water and filtered
method, a separating funilel is utilized. The aqueous solution of
iodine is taken in separating funnel to which ether is added. The
I
Filtrate Residue
funnel is shaken. Two layers are formed. The upper layer which
is dark brown consists of ether and iodine and the colourless Ewpo""",,
lower layer consists of only water. The lower layer is taken out.
to dryness .IDriOO ,.
The coloured layer is then poured out and ether is removed Common salt Sand
cautiously by distillation when iodine is left behind.
Two immiscible liquids such as water and oil can also· be (c) (i) Ammonium chloride sublimes on heating,
separated by the use of a separating funnel. (ii) Potassium chloride is soluble in water,
(iii) Powder~d glass is insoluble in water.
Example 2. How will you separate the following mixtures?
(a) Sulphur, potassium nitrate and charcoal, 1.6· ALLOYS
(b) Sand, common salt, iron filings and naphthalene, When two or more elements are melted together and resulting
liquid is allowed to solidify, the product so obtained'is called an '
(c) Powdered glass, ammonium chloride and potassium alloy ifit possesses metallic properties. An liiloymay consist of a
chloride. mixture of a metal with another metal, a metal with a non-metal·
Solution: or a metal with both metal and non-metal.
(a) (i) Sulphur is soluble in carbon disulphide, Alloys are prepared because they have properties more
(ii) Potassium nitrate is soluble in water, suitable,for certain applications than do the simple metals. Alloys
(iii) Charcoal is insoluble in carbon disulphide as are used because they are harder and stronger, have desirable
casting properties, special physical properties such as magnetic "
well as in water.
properties and resistance to corrosion in certain environments.
Mixture Meltingipoint of an alloy is normally lower than the melting point .
Stirred with CSz and filtered of eith¢r of the pure components. Thcnt}al and' .. 'electrical. - .
r------------L------~ ~ conduct~vities are n~n:nally reduced in alloys'. ... .. .... . c- -.' ...
I
Filtrate (soln. of sulphur is CS0 Residue
An fllloy contammg one component mercury IS called .
amalgam. Most of the metals form amalgams. Iron, platininn,
tungsten, etc., are few metals which do not form amalgams.
1Evaporated Alloys are mainly classified into two distinct types, namely
ferrous 'and non-ferrous. Ferrous alloys always contain iron,
Sulphur carbon and one or two of the other elem~nts such as manganese,
Filtrate Residue nickel, chromium, copper, vanadium, molybdenum, tungsten,
etc. When the percentage of carbon in the alloy is below 0.1, the
1Dried·
I Evaporated to
dryness
3. Gennan Cu 56%, Zn 24%, Utensils, resistance coils (i) Combination: Two or more substances react to form one
silver Ni20% product. When a compound is obtained by the direct reaction
4. Gun metal Cu87%, Machine parts, guns between elements, it is termed direct union or synthesis.
Sn 10%,Zn3%
2HCI C+O z
S. Rolled gold Cu 95%,Al5% Artificial j ewellery
6. Magnalium AI94%,Mg6% Balance beams, light 2Mg + O 2 = 2MgO
instruments
7. Electron Mg95%, Zn 5% Construction of aircraft (ii) Decomposition: When a compound is broken down
into two or more simple constituents, the change is called
8. Duralumin Al 95%, Cu 4%, Making aeroplanes
decomposition. Often heat is utilised for the decomposition. Such
Mn 0.5%, Mg 0.5%
decomposition is termed thermal decomposition.
9. Type metal Pb 82%, Sb 15%, Making printing types
Sn3% 2HgO = 2Hg + O 2 ; 2KCI03 = 2KCI + 30 2
10. Solder Pb 50-70%, Soldering CaC0 3 = CaO+ CO2; 2NaHC0 3 = Na 2C0 3 + H 20+ CO2
Sn 30-50% (iii) Substitution: When one element enters .into a
11. Britannia Sn 93%, Tableware compound by the replacement of the other element, the change is
Sb5%,Cu2% termed substitution.
12. Wood's metal Bi 50%, Pb 25%, Electric fuses and other
CuS04 + Zn Cu + ZnS0 4 ; C 2H 6 + Cl 2 = C 2H s CI + HCI
Sn 12.5%, Cd 12.5% safety devices
13. Nichrome Ni 60%, Cr 15%, Electrical resistances 2KI + Cl 2 = 2KCI + 12 Zn + 2HCI = ZnCl 2 + H2
Fe 25% (iv) Addition: Something is added to a chemical substance
14. Constantan Ni 40%, Cu 60% Electrical resistances without elimination.
15. Monel metal Ni 70%, Cu 30% Chemical plants KI+I2 = KI3
16. lnvar Ni 35%, Steel 65% Surveying instruments,
C2H 4 + HBr = C2HsBr
pendulums, chronometers
OH
17. Stainless Fe 89.4%, Cr 10%, Utensils, ornamental
steel Mn 0.35%, C 0.25% pieces. CH3CHO+ HCN = CH3CH<
CN
1.7 PHYSICAL AND CHEMICAL CHANGES (v) Internal rearrangement: When nothing is added or
nothing is eliminated from a chemical substance but due to
Matter undergoes two types of changes; physical and chemical. A
rearrangement of the various atoms present in a molecule, a new
physical change is one in which a substance changes its physical
compound comes into existence. When ammonium cyanate is
state but keeps its chemical identity. In physical change, a new
heated, a new substance urea is formed.
substance does not come into existence. Mass remains the same.
Physical properties are altered. This is a temporary change. For NH 4 CNO= NH2CONH 2
example, water shows all of its chemical properties whether it is
The chemical change is termed isomerisation, when one
in the form of ice or water or steam. Ice melts to form water and
isomer is converted into another.
water can be converted again into ice by placing it in a freezer.
CH 3
When 10 g of ice melts, 10 g of water is obtained. Melting,
- evaporation, condensation, frc()zing, sublimation, distillation,
CH 2 -CH 2-CH3 AlU3iHCI) CH -bH-CH
passing of electric current through metallic conductor, making of 3 3
n-Butane 300"C 2-Methyl propane
magnet from an iron piece, are some examples of physical
changes. (vi) Polymerization: Two or more molecules of a
In a chemical change, a new substance or substances come substance combine to form a giant molecule,
into existence. The starting materials called reactants, are used up 3C2 H 2 - C6 H 6
and new substances called products, are formed. The Acetylene Benzene
composition of the new substances is different from that of the nHCHO (HCHO)n
starting materials. It is a permanent change as it is not easy to Fonnaldehyde Para fonnaldehyde
obtain the starting materials again from the products.
(vii) Double decomposition: An exchange of partners
Energy is always released or absorbed when chemical or occurs between two compounds.
physical changes occur. Energy is required to melt ice and energy I I
is required to boil water. Conversely, the condensation of steam AB+CD= AD+CB
to form liquid water always liberates energy, as does the freezing L.....J
. of liquid water to form ice. Chemical changes either release I I
energy (exothermic) or adsorb energy (endothermic). BaCI 2 + Na 2 S04
L-.....J
= BaS04 + 2NaCI
Chemical changes are of various types. The important ones
are: I I
KOH + HCl = KCl + H 20
L--J
BASIC PRINCIPLES 9
The reaction is also termed neutralisation, i. e., a reaction For example, carbon dioxide can be obtained by using anyone
between an acid and a base to form a salt and water molecule. of the following methods: '
I I
(a) by heating calcium carbonate,
FeCl 3 + 3HOH Fe(OHh + 3HCl
L..::....----l (b) by heating sodium bicarbonate,
Water
(c) by burning carbon in oxygen,
Reaction of above type is termed hydrolysis. (d) by reacting calcium carbonate with hydrochloric acid.
Whatever sample of carbon dioxide is taken, it is observed
1.8 LAWS OF CHEMICAL COMBINATION that carbon and oxygen are always combined in the ratio of
12 : 32 or 3 : 8.
In order to understand the composition of various compounds, it The converse of this law that when same elements combine in
is necessary to have a theory which accounts for both qualitative the same proportion, the same compound will be formed, is not
and quantitative observations during chemical changes. always true. For example, carbon, hydrogen and oxygen when
Observations of chemical reactions were most significant in the combine in the ratio of 12 : 3 : 8 may form either ethyl alcohol
development of a satisfactory theory of the nature of matter. (C2 H 5 0H) or dimethyl ether (CH 3 0CH 3 ) under different
These observations of chemical reactions are summarised in experimental conditions.
certain statements known as laws of chemical combination.
(iii) Law of multiple proportions: This law was put
(i) Law of conservation of mass: The law was fIrst stated forward by Dalton in 1808. According to this law, if two
by Lavoisier in 1774. It is also known as the law of elements combine to form more than one compound, then the
indestructibility of matter. According to this law, in all chemical different masses of one element which combine with a fIXed
changes, the total mass Qf a system remains constant or in a mass of the other element, bear a simple ratio to one another.
chemical change, mass is neither created nor destroyed. This ..Hydrogen and oxygen combine to form two compounds H 2 0
law ~as tested by Landolt. All chemical reactions follow this (water) and H 2 0 2 (hydrogen peroxide).
law. Thus, this law is the basis of all quantitative work in
In water, Hydrogen 2 parts Oxygen 16 parts
chemistry.
In hydrogen peroxide, Hydrogen 2 parts Oxygen 32 parts
Example: 1.70 g ofsilver nitrate dissolved in 100 g ofwater
is taken. 0.585 gofsodium chloride dissolved in 100g ofwater is The masses of oxygen which combine with same mass of
hydrogen in these two compounds bear a simple ratio 1 : 2.
added to it and chemical reaction occurs. 1.435 g of silver
chloride and 0.85 g of sodium nitrate are formed. Nitrogen forms fIve stable oxides.
Np Nitrogen 28 parts Oxygen 16 parts
Solution: Total masses before chemical change
Nitrogen 28 parts Oxygen 32 parts
Mass of AgN0 3 + Mass ofNaCI + Mass of water
Nitrogen 28 parts Oxygen 48 parts
=1.70g + 0.585g + 200.0g Nitrogen 28 parts Oxygen 64 parts
202.285 g N20 s Nitrogen 28 parts Oxygen 80 parts
Total masses after the chemical reaction, The masses of oxygen which combine with same mass of
nitrogen in the five compounds bear a ratio 16 : 32 : 48 : 64 : 80
= Mass of AgCl + Mass of NaN0 3 + Mass of water
or I : 2 : 3 : 4 : 5.
1.435 g + 0.85 g_+ 200.0 g (iv) Law of reciprocal proportions: This law was given
= 202.285g· by Richter in 1794. The law states that when definite mass of all
element A combines with two other elements Band C to form
Thus, in this chemical change,
two compounds and if Band C also combine to form a
Total masses of reactants = 'total masses of products compound, their combining masses are in same proportion or
bear a simple ratio to the masses of Band C which combine
This relationship holds good when reactants are completely
with a constant mass of A.
converted into products.
~(~)-----~-----
In case, the reacting materials are not completely consumed,
the relationship will be
Total masses of reactants = Total masses of products
r~ fR
+ Masses of unreacted reactants
(ii) Law of definite or constant proportions: This law
was presented by Proust in 1799 and may be stated as follows:
A chemical compound always contains the same element
combined together in fixed proportion by mass, i.e., a NaCI
chemical compound has a fIXed composition and it does not
For example, hydrogen combines with sodium and chlorine to
depend on the method of its preparation or the source from
form compounds NaH and HCI respectively.
which it has been obtained.
10 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
In NaH, Sodium 23 parts Hydrogen one part . Example 4. In an experiment, 2.4 g of iron oxide on
In HCI, Chlorine 35.5 parts Hydrogen one part reduction with hydrogen yield 1.68 g of iron. In another
Sodium and chlorine also combine to fonn NaCI in which 23
experiment, 2.9 gO/iron oxide give 2.03 g of iron on reduction
with hydrogen. Show that the above data illustrate the law of
parts of sodium and 35.5 parts of chlorine are present. These are
constant proportions.
the same parts which combine with one part of hydrogen in NaH
and HCl respectively. Solution:
In the first experiment
/
(~)
~. ~o
. The~ssoflrorioxide = 2.4 g
The mass ofJron after reduction 1.68g
S(B)~~O(c)
The mass of oxygen = Mass of iron oxide - Mass of iron
(2.4 - 1.68) O.72g
Ratio of oxygen and iron = 0.72: 1.68 1: 2.33
. 802 .
• In the second experiment
Hydrogen combines with sulphur and oxygen, to fonn The mass of iron oxide = 2.9 g
compounds H 2 S and H 20 respectively. The mass of iron afteueduction 2.03 g
In H2 S, Hydrogen 2 parts SUlphur 32 parts The triass of oxygen (2.9.;.. 2.03) ~ 0.87 g
In H 20, . Hydfogen 2 parts Oxygen 16 parts
Ratio of oxygen and iron = 0.87: 2.03 =1: 2.33
Thus, according to this law, sulphur should combine with Thus, the data illustrate the law of constant proportions, as in
oxygen in the ratio of 32 : 16 or a simple multiple of it. Actually, both the experiments the ratio of oxygen and iron is the same.
both combine to fonn S02 in the ratio of 32 : 32 or 1 : 1.
The law of reciprocal proportions is a special case of a more EXample S. Carbon combines with hydrogen to form three
general law, the law of equivalent masses, which can be stated compounds A, B and C. The percentages ofhydrogen in A, Band
as under: Care 25, 14.3 and 7.7 respectively. Which law of chemical
"In all chemical reactions, substances always react in the . combination is illustrated?
ratio oftheir equivalent masses." Solution:
(v) Law of gaseous volumes: This law was enunciated by
Gay-Lussac in 1808. According to this law, gases react with Compound % of Hydrogen % of Carbon
each other in the simple ratio of their volumes and if the product
is also in gaseous state, the volume of the product also bears a A 25.0 (100 - 25.0) = 75.0
simple ratio with the volumes of gaseous reactants when all B 14.3 (100 -14.3) = 85.7
volumes are measured under similar conditions of temperature
and pressure. . C 7.7 (100 - 7.7) = 92.3
landmark in the history of chemistry. The main points of Dalton's Some elements exist in more complex molecular forms. The
atomic theory are: molecule of phosphorus consists of four phosphorus atoms and
(i) Elements consist of minute, indivisible, indestructible the molecule of sulphur consists of eight sulphur atoms. Such
particles called atoms. molecules having more than two atoms are said to be polyatomic.
(ii) Atoms of an element are identical to each other. They A representation of the molecule of an element involves use of a
have the same mass and size. subscript to the right of the elemental symbol. The diatomic
(iii) Atoms of different elements differ in properties and have molecule of chlorine is represented as C1 2 , whereas molecules of
different masses and sizes. phosphorus and sulphur are represented as P4 and S8'
(iv) Compounds are formed when atoms of different elements respectively.
combine with each other in simple numerical ratios such The molecule is the smallest possible unit of a compound
as one-to-one, one-to-two, two-to-three and so on. which shows the properties of the compound. The molecules of
(v) Atoms cannot be created, destroyed or transformed into all compounds contain two or more different types of atoms.
atoms of other elements. These differ from the molecules of elements which contain only
(vi) The relative numbers and kind of atoms are always the one type of atoms.
same in a given compound. Thus, it becomes clear that atoms are the components of
The theory convincingly explained the various laws molecules and the molecules are components of elements or
of chemical combination, but the theory has undergone a compounds.
complete shake up with the modem concept of structure of atom. The formula is a group of symbols of elements which
However, the Daltonian atom still retains its significance as the represents one molecule of a substance. The formula of a
unit participating in chemical reactions. The following are the substance represents its chemical composition. Water consists of
modified views regarding Dalton's atomic theory: molecules containing two hydrogen atoms and one oxygen atom
(i) The atom is no longer supposed to be indivisible. The which are represented as H 2 0. The subscript to the right of the
atom is not a simple particle but a complex one. symbol for hydrogen indicates the number of hydrogen atoms
(ii) Atoms of the element may not necessarily possess the contained in a molecule. No subscript follows the symbol for
same mass but possess the same atomic number and oxygen which means, by convention, that only one atom of
show similar chemical properties (Discovery of oxygen is contained in the molecule.
isotopes). The subscripts representing the number of atoms contained in
(iii) Atoms of the different elements may possess the same a molecule of a compound are in no way related to the number of
mass but they always have different atomic numbers and atoms present in the molecule of a free element. Although both
differ in chemical properties (Discovery of isobars). hydrogen and oxygen are composed of diatomic molecules, a
(iv) Atoms of one element can be transmuted into atoms of water molecule contains only one atom of oxygen and two atoms
other element. (Discovery of artificial transmutation). of hydrogen. The two hydrogen atoms present in H2 0 are not
molecular hydrogen but rather two hydrogen atoms that have
(v) In certain organic compounds, like proteins, starch,
chemically combined with an oxygen atom.
cellulose, etc., the ratio in which atoms of different
elements combine cannot be regarded as simple. There For a chemical formula to be correct, it must contain two
are a number of compounds which do not follow the law pieces of information: (i) it must indicate the elements in the
of constant proRortions. Such compounds are called make up of the compound, and (ii) it must indicate the combining
non-stoichiometric compounds. ratio of atoms of these elements in the particular compound. The
first information is provided by including in the formula correct
chemical symbols for all the elements in the compound. The
1.~Oi ATOMS, MOLECULES AND FORMULAE second piece of information is provided by subscripts, i.e.,
An atom is the smallest particle of an element. The atom of numbers written to the right slightly below the chemical symbols
hydrogen is the smallest and the lightest. Atoms take part in of the elements.
chemical combination and remain as indivisible. All atoms do not Nitric acid is a combination of hydrogen, nitrogen and oxygen
occur free in nature. Avogadro introduced the idea of another giving a base formula RNO. These elements combine in the ratio
kind of particles called the molecules. A molecule is the smallest I : 1 : 3. Therefore, the correct formula for nitric acid is RN0 3 •
particle of an element or compound that can have a stable Some compounds are composed of ions rather than of
and independent existence. A molecule of an element consists molecules. Ions differ from atoms and molecules by being
of one or more atoms of the same element. Certain elements are electrically charged particles of matter. The charges may
capable of existence as single atoms and their atoms can be be positive or negative I and generally vary in magnitude.
regarded as molecules. A molecule of an element that consists of The positively charged idns are called cations and negatively
one atom only is called monoatomic molecule as in the case of charged ions are called: anions. Simple cations· and anions
inert gases. Oxygen is not stable in atomic form but is stable in come into existence by IQss and acceptance of an electron or
molecular form. A molecule of oxygen is diatomic in nature, i. e., electrons by neutral atoms respectively. Ions that consist of
its molecule consists of two oxygen atoms. Hydrogen, nitrogen, several atoms held together by chemical bonds similar to those
fluorine, chlorine, bromine, iodine are also diatomic like oxygen. involved in the molecules are called polyatomic ions or complex
BASIC PRINCIPLES 13
ions. These complex ions differ from molecules in the sense that Common Name Chemical Name Chemical Formula
they bear a charge. Some of the common complex ions are:
Indian nitre Potassium nitrate KN0 3
N03" Nitrate PO~- Phosphate NH 4+ Ammonium
Limestone Calcium carbonate CaC0 3
so~- Sulphate CIO; Perchlorate PH4+ Phosphonium Lunar caustic Silver nitrate AgN03
Blue vitriol Copper sulphate CuS0 4,5HP Pyrene Carbon tetrachloride CCl 4
Baking soda Sodium bicarbonate NaHC0 3 Picric acid 2,4,6-Trinitrophenol C6H 2(OH)(N°2)3
Caustic potash Potassium hydroxide KOH Sid ammoniac Ammonium chloride NH4CI
Sugar oflead Lead acetate (CH 3COO)2Pb
Carbolic acid Phenol CJIsOH
Chile saltpetre Sonium nitrate NaN0 3 Sand Silicon dioxide Si02
Carborundum Silicon carbide SiC Table salt (Common Sodium chloride NaCI·
salt)
Corrosive sublimate Mercuric chloride HgCl2
TEL Tetra-ethyl lead Pb(C 2H s)4
Calomel Mercurous chloride Hg2Cl 2
Tear gas Chloropicrin CCl 3N02
Dry ice Carbon dioxide (solid) CO 2
Washing soda Sodium carbonate Na2C03,IOH20
Formalin Fonnaldehyde HCHO
(40% solution) Water glass Sodium silicate Na2Si03
Grain alcohol (Spirit) Ethyl alcohol . C2H sOH White vitriol Zinc sulphate ZnS°4 ,7H 2O
of mass is taken as a standard. For this purpose, mass of one atom Thus,
of hydrogen was assumed as unity and was accepted as standard. 23
Tbe atomic mass of an element can be defined as tbe number lamu' 1.9924 x 10- = 1.66 X 10- 24 g or 1.66 x 10- 27 kg
wbich indicates how many times tbe mass of one atom of the 12 .
element is heavier in comparison to the mass of one atom: of
hydrogen.
A =Atomic mass of an element
Mass of one atom of the element
A == Atomic mass of an element =----------------------
lamu
Mass of one atom of the element
The atomic masses of some elements on the basis of carbon-l 2
Mass of one atom of hydrogen are given below:
In 1858, oxygen atom was adopted as a standard on account of Hydrogen 1.008 amu Iron 55.847 amu
the following reasons: Oxygen 16.00 amu Sodiuml 22.989 amu
(i) It is much easier to obtain compounds of elements with
Chlorine 35.453 amu Zinc 65.38 amu
oxygen than with hydrogen as oxygen is more reactive than
hydrogen. Magnesium 24.305 amu Silver 107.868 amu
(ii) The atomic masses of most of the elements. become Copper 63.546 amu
approximately whole numbers but with hydrogen as standard the
atomic masses of most of the elements are fractional. The actual mass of an atom of an element
The mass of one atom of natural oxygen was taken to be 16.0. The atomic mass of an element in amu x 1.66 x 10-24 g
Thus, atomic mass of an ~lement So, the actual mass of hydrogen atom
1.008 x 1.66 x 10-24 == 1.6736 X 10-24 g
element
Similarly, the actual mass of oxygen atom
16 th part of the mass of one atom of oxygen
16 x 1.66 x 10-24 = 2.656 X 10-23 g
Mass of one atom of the element x 16 It is clear from the above list of atomic masses that atomic
Mass of one atom of oxygen masses of a number of elements are not nearly whole numbers.
Actually, the above values are average relative masses. Most of
By accepting oxygen as a standard, the atomic mass of the elements occur in nature as a mixture of isotopes.
hydr6gen comes as 1.008, sodium 22.991 and sulphur 32.. 066. (Isotopes-the atoms. of the same element having different
In 1961, the International Union of Chemists selected a new atomic masses). With very few exceptions, however, elements
unit for expressing the atomic masses. They accepted the stable have constant mixtures of isotopes. Chlorine is found in nature as
isotope of carbon (12 C) with mass number of 12 as the standard. a mixture containing two isotopes CI-35 (34.969 amu) and CI-37
(36.966amu).These are found in the ratio of75.53% (CI-35) and
Atomic mass of an element can be defined as the number
24.47% (CI-37). Therefore, the average relative mass of chlorine
which indicates bow many times the mass of one atom of the
is calculated as:
element is heavier in comparison to 112 th part of the mass of
(34.969 x 0.7553)+ (3'6.966 x 0.2447)= 35.46 amu
one atom of carbon-ll (12 C).
Based on the average mass, the atomic mass of chlorine is
A == Atomic mass of an element 35.46 or 35.5 amu but it is never possible to have-an atom having
a relative mass 35.5 amu. It can have relative mass of about 35.0
Mass of one atom of the element or 37.0 amu depending on the particular isotope. Thus, average
~ th part of the mass of one atom of carbon -12 relative mass of any naturally occurring sample of chlorine is
35.46 or 35.5 amu as it is a mixture of two isotopes present in
= Mass of one atom of the element x 12 definite proportion. The same reasoning applies to all other
Mass of 'One atom of carbon -12 elements.
[The quantity' A' was formerly known as atomic weight. The average atomic masses of various elements are
However, this term is no longer used as the word 'weight' means det~ed by multiplying the atomic mass of each is.otope by its
gravitational force.] fractional abundance and adding the values thus obtained. The
Atomic mass unit: The quantity .
~
12
mass of an atom of fractional abundance is determined by· dividing percentage
abundance by hundred.
carbon-12 (12 C) is known as the atotinc~aSS unit and is
~ " m·X a+nxb
abbreviated as amu. The actual mass of one atom of carbon-l 2 is Average ISOtOPIC mass = - - - - - -
. m+n
1.9924 x 10-23 g or 1.99.24 x 10-26 kg.
here, a, b are atomic masses of isotopes in the ratio m : n.
*The term Dalton is used for one atomic mass unit, 1 Dalton = 1 amu.
11. BASIC PRINCIPLES 15
..
Average IsotOPIC mass =-x X a+ X
b the mass of a molecule of a substance relative to the mass of an
100 100 atom of hydrogen as 1.008 or of oxygen taken as '16.00 or the
mass of one atom of carbon taken as 12. Molecular mass is a
here, x, y are percentage abundance of the two isotopes
number which indicates how many times one molecule of a
(y= 100-x).
substance is heavier in comparison to l~th of the mass of
Example 11. Boron has two isotopes boron-1O and boron-II
whose percentage abundances are 19.6% and 80.4% respectively. oxygen atom or l~ th of the mass of one atom of carbon-12.
What is the average atomic mass of boron?
M = Molecular mass
Solution: Mass of one molecule of the substance .
Contribution of boron-1O 10.0 X 0.196 = 1.96amu
12 th mass of one atom of carbon -12
Contribution of boron-II =ll.Ox 0.804 = 8.844amu
The mass of a molecule is equal to sum of the masses of the
Adding both =1.96+ 8.844 10.804amu atoms present in a molecule. One molecule of water consists of2
Thus, the average atomic mass of boron is 10.804 amu. atoms of hYQrogen and one atom of oxygen. Thus, molecular
. mass of water (2 x 1.008) + 16.06 18.016amu. One molecule
Example 12. Carbon occurs in nature as a mixture of of H 2 S04 (sulphuric acid) consists of2 atoms of hydrogen, one
carbon-12 and carbon-13. The average atomic mass ofcarbon is atom of sulphur and four atoms of oxygen. Thus, the molecular
12.011. What is the percentage abundance of carbon-12 in mass of sulphUric acid is
nature?
Solution: Let x be the percentage abundance of carbon-12;
=(2x 1.008)+ 32.00+ (4 x 16.00)
then (100 - x) will be the percentage abundance of carbon-I 3 . = 98.0160r 98.016amu
So, Mass of oxygen = 2.5 x 32 80.0g (ii) Molecule: The smallest particle of a substance (element or
compound) which has free or independent existence and possesses
Example 14. Calculate the gram atoms in 2.3 g ofsodium. all characteristic properties of the substance. A molecule of an
element is composed of like atoms while a molecule of a compound
Solution: No. of gram atoms 2.3 == 0.1 contains fixed number of atoms of two or more different elements. A
23
[Atomic mass of sodium 23 g] molecule may be broken down into its constituent atoms but the
atom is indivisible during a chemical change.
Example 15. Calculate the mass of 1.5 gram molecule of Avogadro after making the above differentiation, presented a
sulphuric acid. hypothesis known as Avogadro hypothesis which can be stated
Solution: Molecular mass of as follows:
H 2 S04 =2x 1+ 32+ 4 x 16= 98.0amu "Under similar conditions of temperature and pressure,
Gram-molecular mass of H 2 S04 =98.0g equal volumes of aD gases contain equal number of molecules."
Mass of 1.5 gram molecule of H 2 S04 =98.0x 1.5=147.0g Avogadro hypothesis explains successfully the formation of
hydrogen chloride.
Example 16. Calculate the actual mass ofone molecule of Hydrogen + Chlorine = Hydrogen chloride
carbon dioxide (C0 2 ),
I vol I vol 2 vol
Solution: Molecular mass of CO 2 = 44 amu nmolecules nmolecules 2n molecules
larrru 1.66xlO- 24 g I molecule I molecule 2 molecules
24 I 1
So, The actual mass of CO 2 == 44 x 1.66 x 10- '2 molecule '2 molecule I molecule
23 I atom I atom I molecule
7.304 X 10- g
(Both hydrogen and chlorine are diatomic in nature.)
Thus, the hypothesis explains that the molecules of reacting
1i.~_~~ AVOGADRO'S HYPOTHESIS gases break up into constituent atoms during chemical change
According to Dalton's atomic theory, elements react with each which then combine to form new molecules of the product or
other in the simple ratio of their atoms. Gay-Lussac proposed that products.
gases combine in simple ratio of their volumes. In an attempt to
correlate Dalton's atomic theory with Gay-Lussac law of gaseous Applications of Avogadro's hypothesis
volumes, Berzelius stated that under similar conditions of 0) Atomicity*: Atomicity means number of atoms present
temperature and pressure, equal volume of all gases contain in one molecule of an elementary gas. Hydrogen, oxygen,
the same number of atoms. This hypothesis was subsequently nitrogen, chlorine, etc., are diatomic in nature. Noble gases are
found to be incorrect as it failed to interpret the experimental monoatomic while ozone is triatomic in nature. Avogadro's·
results and contradicted the very basic assumption of Dalton's hypothesis helps in determining the atomicity of elements.
atomic theory, i. e., an atom is indivisible. For example, the (ii) Relationship between molecular mass and vapour
formation of hydrogen chloride from hydrogen and chlorine density: The vapour density of any gas is the ratio of the
could not be explained on the basis of Berzelius hypothesis. densities of the· gas and hydrogen under similar conditions of
Hydrogen + Chlorine = Hydrogen chloride
temperature and pressure.
I vol I vol 2 vol Density of gas
n atoms natoms 2n compound atoms Vapour Density (V.D.)
Density of hydrogen
I atom I atom 2 compound atoms
Jiatom Ji atom I compound atom Mass of a certain volume of the gas
Mass of same volume of hydrogen at
i. e., for the formation of I compound atom of hydrogen the same temp. and pressure
chloride, ~ atom of hydrogen and ~ atom of chlorine are needed.
In other words, each atom of hydrogen and chlorine has been If n molecules are present in the given volume of a gas and
divided which is against Dalton's atomic. theory. Thus, the hydrogen under similar conditions of temperature and pressure,
hypothesis ofBerzelius was discarded. Mass of n molecules of gas
The Italian scientist, Amedeo Avogadro, in 1811, solved the V.D.=---------------------
Mass of n molecules of hydrogen
above problem by proposing two types of particles from which
whole of the matter is composed.of. Mass of I molecule of gas
(i) Atom: The smallest particle of an element that can take
part in chemical change but generally cannot exist freely as such. Mass of I molecule of hydrogen
*Atomicity can be ascertained with the values of ratio of two specific heats of gases ( ~; )
1 g of hydrogen occupies volume at NTP = 1 mL 1 mole of electrons means 6.02 x 1023 electrons.
. 0:00009
The type of entity must be specified when the mole
Ig mole of hydrogen (2.0 16 g) occupies volume at NTP designation is used. A mole of oxygen atoms contains 6.02 x 10 23
i 2.016 = 22400 mL = 22.4 litre oxygen atoms. and a mole of oxygen molecules contains
0.00009 6.02 x 1023 oxygen molecules. Therefore, a mole of oxygen
According to Avogadro's hypothesis, equal volumes of molecules is equal to two moles of oxygen' atoms,
different gases contain same number of molecules under similar i. e. , 2 x 6.02 x 1023 oxygen atoms.
conditions of temperature and pressure. Thus, 22.4 litre or 22400 How much does one mole weigh? That depends on the nature
mL of any gas at NTP will contain one gram mole or its molecular of particles (units). The mass of one mole atoms of any element
mass in grams. is exactly equal to the atomic mass in grams (gram-atomic
Loschmidt number: Number of molecules in 1 em3 or 1 mL mass or gram atom) of that element.
of a gas at S.T.P. is known as Loschmidt number. For example, the atomic mass of aluminium is 27 amu. One
. 6.023x10 23 amu is equal to 1.6{i x 10-24 g. One mole of aluminium contains
LOSChmidt number = --.---
22400 6.02 x 1023 alJlIl1inium atoms.
= 2. 68x 1018 molecules mL-1 Mass of one atom aluminiUm = 27 x 1.66 x 10-24 g
(iv) Molecular formula: Avogadro's hypothesis helps in Mass of one mole aluminium =27 x 1.66 x 10-24 X 6.02 x 1023
[mding the molecular formulae of gases. Under similar =27g
conditions of temperature and pressure, 2 volumes of ozone after This is the atomic mass of aluminium in grams or it is one
decomposition give 3 volumes of oxygen. gram atomic mass or one gram atom of aluminium.
Deco~tion Similarly, the mass of 6.02 x 10 23 moleC"!Iles (1 mole) of a
Ozone ) Oxygen
2 vol 3 vol substance is equal to its molecular mass in grams c.r
gram-molecular mass Or gram molecule. For example,
2 molecules 3 molecules molecular mass of water is 18 amu. Thus, mass of one mole of
I molecu1e 3/2 molecules water will be 18 x 1.66 x 10-24 X 6.02 x 1023 , i. e., 18 g. This is
the molecular mass of water in grams or one gram-molecular
1 molecule 3 atoms
mass or one gram molecule.
Thus, the fonnula of ozone is ° 3, Mole concept is also applicable to ionic compounds which do
not contain molecules. In such cases, the fonnula of an ionic
1~t3 MOLE CONCEPT. compound represents the ratio between constituent ions. The
mass of 6.02 x 1023 fonnula units represents one mole of an ionic
For the counting of articles, the unit dozen or unit gross is compound.
commonly used irrespective of their nature. For example, one
dozen pencils means 12 pencils or one dozen apples means 12
... O°C or 273 K temperature and one atmosphere or 760 rom ofHg or 76 cm ofHg pressure are known as the standard conditions of temperature and
pressure (STP) or normal conditions oftemperature and pressure (NTP).
18 I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
One mole ofBaC1 2 = 6.02 x 1023 BaCl 2 units Number of water mOlecules in one mole of water
23
= 208.2g BaCl 2 6.02 x 10
Molecular mass (fomrula mass) of BaCl 2
Number of molecules of water in 0.05 moles
:::: 6.02 x 1023 Ba 2+ ions + 2 x 6.02
X 10
23 CI- ions 0.05 x 6.02 x 1023
= 137.2+ 71.0 = 208.2g 3.01Ox 1022
One mole of a substance will have mass equal to formula As one molecule of water contains one oxygen atom,
mass of that substance expressed in grams. So, number of oxygen atoms in 3.010 x 1022 molecule of
It has been established by Avogadro's hypothesis that one water 3.010x 1022
gram-molecular mass of any gaseous substance occupies a
volume of 22.4 litres at NTP. One gram-molecular mass is Example 19. Calculate the mass of a single atom of
nothing but one mole of substance. Thus, one mole, sulphur and a single molecule ofcarbon dioxide.
i. e. , 6.02 x 1023 molecules of any gaseous substance occupies Solution:
22.4 litres as volume at NTP.
The following formulae satisfy the above discussion. Gram-atomic mass of sulphur = 32g
1 mole of a substance:::: 6.02 x 1023 particles ofthe substance Gram-atomic mass
Mass of one sulphur atom
Number of moles of a sub~tance 6.02 x 1023
Mass of substance in gram 32
::::---- 5.33 X 10-23 g
Mass of one mole of the substance in gram 23
6.02 x 10
No. of particles
Further, Number of moles = 23 Formula of carbon dioxide = CO 2
6.02 x 10
Molecular mass of CO 2 12+2xI6=44
Thus, Gram-molecular mass of CO 2 44 g
No. of particles = Mass of substance in gram Gram-molecular mass
6.02 x 10 23 Mass of one mole of the substance in gram Mass of one molecule of CO 2
6.02x
Mass of one atom of an element
Gram atom of an element = 4 4 = 7.308 x 10-23 g
6.02 x 1023
6.02 x 1023
Mass of one molecule of a substance Example 20. What is the mass of3.01 xl 022 molecules of
Gram-molecular mass of the substance ammonia?
=
6.02 x Solution: Gram-~olecular mass of ammonia 17 g
Number of molecules
:::: Vohune of gas in litres at NTP x 6.02 x 1023 Number of molecules in 17g (one mole)ofNH3 = 6.02 x 1023
22.4 Let the mass of 3.01x 1022 moieculesofNH3 be =xg
3.01 x 1022 x
,£ : :: ::: _SOME SOLVED eXAMPLES\ :::: : : ; So,
6.02x 1023 17
Example 17. A piece ofcopper weighs 0.635 g. How many 22
or x 17x 3.01x 10 =0.85g
atoms ofcopper does it contain? IeEE (Bihar) 19921
6.02x 1023
SolutiOn: Gram-atomic mass of copper:::: 63.5 g
Example21. From 200 mg of CO2 , 1021 molecules are
Number of moles in 0.635 g of copper 0.635 == 0.01
63.5 removed. How many moles ofCO2 are left?
23
Number of copper atoms in one mole = 6.02 x 10 Solution:
Number of copper atoms in 0.01 moles O.Olx 6.02 x 1023 Gram-molecular mass ofe02 :::: 44 g
6.02 x 1021
Example 18. How many molecules o/water-and oxygen Mass of 10 21 molecules of CO2 . 44 x 1021 = 0.073 g
6.02 x 1023
atoms are present in 0.9 g ofwater?
Mass of CO 2 left = (0.2 - 0.073) = 0.127 g
Solution: Gram-molecular mass of water :::: 18 g
Number of moles in 0.9g·of water = 0.9 = 0.05 Number of moles of CO 2 left 0.127 = 2.88 x 10- 3
18 44
BASIC PRINCIPLES I 19
23
::Example 22. How many molecules and atoms of oxygen 6.02 x 10
are present.in 5,6 lUres of oxygen (0 2 )at NTP?
x 60x 60x 24 x 365
Solution: We know that, 22.4 litres of oxygen at NTP
contain 6.021< 1023 molecules of oxygen, = 19,089x 109 years = 1.9089x 1010 years
6. 25 g of MC1 4 contains 0.5 mol chlorine then its molecular active metals. A known mass of the active metal· is reacted with
mass is: (DPMT 2007) dilute mineral acid. Hydrogen gas thus evolved is measured
(a) 100g mol- 1 ,b) 200g mol- l under experimental conditions. The volume of hydrogen is then
reduced to NTP conditions. The mass of liberated hydrogen is
(c) 150g mol- l (d) 400g mol- l
determined using density of hydrogen (0.00009 at NTP).
[Ans. (b)]
[Hint: I mol of MCI 4 contaiils 4 mol of chlorine Equivalent IllIlSS Mass of element x 1.008
.,' 0.5 mol chlorine is present in 25 g of MCl 4 Mass of hydrogen
;;4 mol chlorine will be present in~ x 4, i.e.,200 g ofMCI 4.] Mass of element x 1.008
0.5
Volume in mL ot' hydrogen displaced atNTPx 0.00009
Equivalent mass of a substance (element or compound) is defmed (ii) Oxide formation method: A known mass of the
as the number of parts by mass of the substance which element is changed into oxide directly or indirectly. The mass of
combine or displace directly or indirectly 1.008 parts by mass oxide is noted.
of hydrogen or 8 parts by mass of oxygen or 35.5 parts by Mass of oxygen (Mass of oxide Mass of element)
mass of chlorine or 108 parts by mass of silver.
The equivalent mass is a pure number. When the equivalent Thus, the equivalent mass of the element
:-
mass of a substance is expressed in grams, it is called gram Mass of element x8
equivalent mass. For example, equivalent mass of sodium is 23, (Mass of oxide Mass of element)
hence, its gram equivalent mass is 23 g. • /
Mass of element x 8
The equivalent mass of a substance may ha~e different values
under different conditions. The -equivalent mass of an element Mass of oxygen
may vary with change of valency. For example, copper fornts two (iii) Chloride formation method: A known mass of the
oxides CUO and Cu 2 0. In CUO, 63.5 parts of copper combine element is changed into chloride directly or indirectly. The mass
with 16 parts of oxygen. Thus, equivalent mass of copper in this of the chloride is determined.
oxide is 6~5 31.75. In Cu 20' 2 x 63.5 parts ofcopper combine Mass of chlorine (Mass of chloride Mass of element)
with 16 parts of oxygen; thus, the equivalent mass of copper in Thus, the equivalent mass of the element
this oxide is:
Mass of element x 35.5
2 x 63.5 = 63.5
(Mass of chloride Mass of element)
2
Relation between atomic mass, equivalent mass and Mass of element x 35.5
valency: Suppose an element X combines with hydrogen to
. fom a compound, XH n , where n is the valency of the element X.
(iv) Metal to metal displacement method: A more active
n parts by mass of hydrogen combine with atomic mass of metal can displace less active metal from its salt's solution. For
elementX. example, when zinc is added to copper sulphate, copper is
1 part by m\lSS of hydrogen combines with precipitated. A known mass of active metal is added to the salt's
Atomic mass of element solution of less active metal. The precipitated metal after drying
n is accurately weighed. The masses of the displacing metal and the
.. Atomic mass of element. h . displaced metal bear the same ratio as their equivalent masses. If
B y ab ove defiImtlOn, IS t e eqUlva- El and E2 are the equivalent masses of two. elements and
n ml and m2 their respective masses, then,
lent mass of the element.
Atomic mass ml =~
Thus, Equivalent mass m2 E2
n
Knowing the equivalent mass of one metal, the equivalent
or Atomic mass Equivalent mass x Valency
mass of th.e other metal can be calculated.
Note: 'Detailed discussion'on equivalent masses of compounds (acids,
bases, salts, oxidising agents, reducing agents, etc.,) will be (v) Double decomposition method: This method is based
taken in chapter on volumetric analysis. on the following points:
The following methods are, used for the determination of (a) The mass of the compound reacted and the mass of
equivalent mass of elements. product formed are in the ratio of their equivalent masses.
(i) Hydrogen displacement method: This method is used (b) The equivalent mass of the compound (electrovalent) is
for those elements which can evolve hydrogen from acids, i.e., the sum of equivalent masses of its radicals.
BASIC PRINCIPLES 21
(c) The equivalent mass of a radical is equalto the fonnula (a) 4 (b) 2 (c) 3 (d) 1.5
mass of the radical divided by its charge. [ADS. (d)]
a 2E(~)] ·
ApproXlmate . mass 0 fth e metaI = -----.",....---
atOlTIlC
.
6.4
. Specifjc heat
9. The percentage of an element Mis 53 in its oxide of mlllecular 6.4 114.3
fonnula M 203' Its atomic mass is about: 0.056
[PET (Kerala) 2oo8J
(a) 45 (b) 9 (c) 18 (d) 38 Valency = Approximate atomic mass _ 114.3 3.1 '" 3
(e) 21 Equivalent mass 36.21
[Ans. (e)]
., . Mass of element Hence, exact atomic mass = 36.21 x 3 = 108.63
[HIDt: Eqwvalent mass of element = '. x 8
. Mass of oxygen Example 27. On dissolving 2.0 go/metal in sulphuric
53 " acid, 4.5lg o/the metal sulphate wasformed. The specific heat of
=-x8:::9
47 the metal is 0.051 cal g-I. What is the valency of the metal and
Atomic mass = Equivalent mass x Valency exact atomic mass?
=9x3 =27 amu.] Solution: Equivalent mass of SO~- radical
10. The equivaLent weight of a metal is double than that of
oxygen. How many times is the weight of its' oxide greater Ionic mass = 96 = 48
than the weight of metal? Valency 2
22 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Relative
Atomic Simplest
fUUSTRATfONSOF,OB]ECTlviQUESY}'ONS Element Percentage
mass
number of
ratio
atoms
Molecular equations are thoSe in which reactants and products Measures. This revised set of units is known as the
are represented in the form of molecules. International System of Units (abbreviated SI). Now the SI
BaCl 2 + Na 2 S0 4 BaS04 J, + 2NaCl units have been accepted by the scientists all over the world in all
2NaOH + H 2 S0 4 Na 2 S04 J, + 2H 2 0 branches of science, engineering and technology. '
Ionic equations are those in which reactants and products are The SI system have seven basic units. The various
written in ionic form. The molecular equation fundamental quantities that are expressed by these units along
BaCl 2 + Na2S04 BaS04 J, + 2NaCI with their symbols are tabulated below:
can be written in ionic form as:
Basic pbysical quantity Unit Symbol
Ba 2+ + 2CI- +2Na + + SO~- BaS04 J, + 2Na + + 2Cl-
Ba 2+ + SO~- = BaS04 J, Length Metre m
Note: Calculations based on chemical equations have been dealt in the Mass Kilogram kg
chapter 'Stoichiometry' in 'Inorganic Chemistry'.
Time Second s
1~20;' MEASUREMENT IN CHEMISTRY: Temperature Kelvin K
FUNDAMENTAL AN.D DERIVED UNITS Electric current Ampere amp orA
Chemistry is an experimental science. An experiment always Luminous intensity Candela cd
involves observation-of a· phenomenon under certain set of
conditions. The quantitative scientific observation generally Amount of substance Mole mol
requires the measurement of one or more physical quantities such
Sometimes, submultiples and multiples are used to reduce or
as mass, length, density, volume, pressure, temperature, etc.
enlarge the size of the different units. The names and symbols of
A physical quantity is expressed in terms of a number and a
sub-multiples and multiples are listed in the table given below.
unit. Without mentioning the unit, the number has no meaning. For
The name for the base unit for mass, the kilogram, already
example, the distance between two points is "four" has no meaning
contains a preftx. The names of other units of mass are obtained
unless a specific unit (inch, centimetre, metre, etc.,) is associated
by substituting other prefixes for prefix kilo. The names of no
with the number. The units of physical quantities depend on three
other base units contain prefixes.
basic units, i.e., units of mass, length and time. Since, these are
independent units and cannot be derived from any other units, they The use of SI system is slowly growing, however, older
are called fundamental units. It was soon realised that the three systems are still in use. Furthermore, the existence of older units
fundamental units cannot describe all the physical quantities such in scientific literature demands that one must be familiar with
as temperature, intensity of luminosity, electric current and the both old and new systems.'
amount of the .substance. Thus, seven units of measurement, Submultiples Multiples
namely mass, length, time, temperature, electric current, luminous
intensity and amount of substance are taken as basic units. All Prefix Symbol Sub-multiple Prefix Symbol Multiple
other units can be derived from them and are, therefore, called deci d 10- 1 deca da 10
derived units. The units of area, volume, force, work, density,
centi c 10-2 hecto h 102
velocity, energy, etc., are all derived units.
milli m 10-3 kilo k 103
SI Units of Measurement micro 10-6 mega M HI'
Jl
Various systems of units were in use prior to I91'l0. The 10-9
nano n giga G 109
common ones are the following:
pico P 10- 12 tera T 1012
(i) The English or FPS system: The system uses the foot,
the pound and the second for length, mass and time femto f 10- 15 peta P 1015
(ii) MKS system: Here M stands for metre (a unit of zepto z 10-21 zeta Z 102 1
length), K for kilogram (a unit of mass) and S for second (a unit yocto 10-24 yotta Y 1024
of time). This is a decimal system. .
(iii) CGS system: Here the unit oflength is centimetre, the Greek Alphabets
unit of mass is gram and the unit of time is second. It is also a
Alpha A IX Nu N v
decimal system.
MKS system often known as metric system was very popular Beta B ~ Xi .:. ~
throughout the world, but the drawback with this system was that Gamma r y Omicron 0 '0
a number of different metric units for the same quantity were Delta 11 5 Pi n 11:
used in different parts of the world. In 1964, the National Bureau
of Standards adopted a slightly modified version of the metric
system, which had been officially recommended in 1960 by an
Epsilon
Zeta,
Eta
E
Z
H
,E Rho
Sigma
T\lu
P
L
p
cr
international body, General Conference of Weigbts and l'J 't 't
BASIC PRINCIPLES 29
Theta e e UpsiloJ:l. r \) frequently by chemists. Certain other units which are not a part of
Iota I t Phi <I> .<\1 SI units are still retained for a limited period of time. The term
Kappa Chi atmosphere (atm), the unit of pressure, falls into this category.
K 1( X X
Few of the old units along with conversion factors are given
Lambda A A Psi lJ' lJf below:
Mu M j.t Omega Q ro Length: The interatomic distances are reported in units of
Numerical Prefix. angstrom (A), nanometre (nm) or picometre (pm).
lA= 10-8 cm= 10- 10 m
Prefix VaHue Prefix Value
Inm=10-7 cm=10-9 m=WA
Herni (II2) Deca 10
Mono Undeca 11 Ipm=W- IO cm 10- 12 m 10-2 A
Sesqui 1":
2
Dodeca 12 Inm 103 pm
DiorBi 2 Trideca 13 Mass: The basic unit of mass is generally taken as gram (g).
Tri 3 Tetradeca 14 The gram is 10-3 kg.
Tetra 4 Pentadeca 15 I kilogram (kg) = 103 g
, Penta 5 Hexadeca 16
Hexa 6 Heptadeca 17 1 milligram (mg)= 10-3 g
Hepta 7 Oetadeca 18 1 microgram (Ilg) =10-6 g
Oeta 8 Nonadeca 19 While dealing with atoms arid molecules, the term atomic
Nona 9 Eicosa 20 mass unit (amu) is used. One amu is taken exactly as ..!.. of the
. 12
SI Units for Some Common Derived Quantities mass ~f an atom of the carbon isotope, C : I2
Pressure: There are three non-S1 units for pressure which Values of Some Useful Constants
are commonly used.
F\lndamental
(a) Atmosphere (atm) is defined as the pressure exerted by a Value In old units Value in SI units
constant
column of mercury of 760 mm or 76 cm height at O°C.
(b) Torr is defined as the pressure exerted by a I mm column 'Avogadro's
of mercury at O°C. number(N)
(c) Millimetre of mercury (mm Hg). Atomic mass . 1.6605 X 10-24 g 1.6605 X 10-27 g
These three units are related as: unit (amu)
Bohr radius (~) 0.52918A = 0.52918· 5.2918 X 10-11 m
latm=760torr 760mmHg 76cmHg 1.013 x 105 Pa
x 10-8 cm
Energy: Calorie has been used in the past as a unit of energy
Boltzmann 1.3807 X 10-23 JK- 1
measurement. The calorie was defmed as the. amount of heat constant (k)
required to raise the temperature of one gram of water from
14.5"C to 15.5°C. One calorie is defined as exactly equal to 4.184 Charge on e1ectron(-) 4.8029 x 10-10 esu (-) l.6021 X 10-19 coul
(e)
joules.
Ical 4.184 J or 11 = 0.2390 cal Charge to mass 1.7588 x 108 coul g-1
ratio el m of
1kcal = 1000 cal ==4.184 kJ electron
Conversion factors
I angstrom (A) = 10-8 cm=1O- IO m==IO-1 nm=10 2 pm
1 inch 2.54 cm.
39.37 inch = I metre
or
1
0.0821lit atm deg- mol-
1.987
1
I
8.314 x 107 erg deg-1mor' 8.314 J K- mol-
.
1
..
1calorie (cal)=4.1840x 10 7 erg =4.184 J Velocity of light 2.9979 x 1010 cm seC l 2.9979 X 108 m sec-I.
(c) in vacuum or 186281 miles sec-I
2.613 x 1019 eV
Faraday (F) 9.6487 x 104 C I equiv.
lcoulomb (coul) =2.9979 x 109 esu or 96500 C/equiv.
, 1curie (Ci) = 3.7 X 1010 disintegrations sec -I 0.8988xl0 1O N m 2C-2
lelectron volt (eV) 1.6021 x 1O-12 erg = L6021 x 10- 19 J or9x 109 N m 2e 2
(a) 33.3 ~(has only one decimal place) posses~ed by the least precise term used in the calculation.
3.11 Examples are:
0.313 (a) 142.06
Sum 36.723 f-, (answer should be reported x 0.23 ~(two significant figures)
to one decimal place) 32.6738 ~ (answer should nave two
So, accurate atomic mass Eq. mass x Valency Example 27. Weighing 31 04 carats (1 carat::: 200 mg), the
Cullinan diamond was the largest natural diamond ever found.
= 100 x 2= 200g How many carbon atoms were present in the stone?
.. Mol. mass 199.88_
A tOI11lClty ==--- 1 Solution: Mass of the stone
At. mass 200
= 3104 x 200= 620800mg::::: 620.8g
Hence, mercury molecules are monoatomic. Number of atoms of carbon
Example 23. How many grams of CaO are required to
Mass in gram x 6.023 x IOZ3
neutralise 852g ofP401O? (lIT 2005)
Gram-atomic mass
Solution: The reaction will be:
6CaO+ P4010 ~2Ca3(P04h 620.8 x 6.023 x 10 23 =3.12 X 1015
12
852 g P40 lO == 3 mol P40 lO Example 28. A cylinder of compressed gas contains
1 mole of P4010 neutralises 6 moles ofCaO. nitrogen and oxygen in the ratio 3: I by mole. If the cylinder is
known to contain 2.5 x 104 g ofoxygen, what is the total mass of
.. 3 moles OfP401O will neutralise 18 moles of.CaO.
the gas mixture?
Mass of CaO= 18;- 56=1008g
Solution: Number of moles of oxygen in the cylinder
. ' Example 24. If 1 grain is equal to 64.8 mg, how many\
Mass in 2.5 x 10 4
moles of aspirin (mol. wt: == 169) are present" in ,'tt 5 grain aspirin \
tablet? . \ Molecular mass in gram 32
Solution: Mass of aspirin in the tablet == 64.8 x 5 324 mg = 781.25
== 0.324g NumberofmoiesofN 2 3x781.25 2343.75
Number of moles = Mass = 0.324 Mass of nitrogen in the cylinder 2343.75 x 28
Molar mass 169
65625g
1.92 x 10-3
= 6.5625 x 104 g
Example 25. If the volume occupied in a crystal by a
Total mass of the gas in the cylinder
molecule of NaCI is 47 x 10-24 mL, calculate the volume of the
crystal weighing Ig. = 2.5 xl 04 + 6.5625 X 104 9.0625 X 104 g
Solution: Number of molecules of NaCI Example 29. Atmospheric air has 78% N z ;21% 02;
Mass x 6.023 x 1023 0.9 % Ar and 0.1 % CO 2 by volume. What is the molecular mass
Molar mass
_1_' x 6.023 x 1023 = 1.03x·1022
ofair in the atmosphere?
Solution:
.
Molecular mass of mixture
58.5
,L %ofeach M 1
- - - - x 0 ar mass
Volume of crystal = L03 x 1022 x 47 X 10-24 = 0.484 mL 100
,Example 26. A plant virus is found to consist of uniform 78 21 0.9 0.1
= x 28+-x 32+-x40+-,x44=28.964
cylindrical particles of 150 A in diameter and 5000 A long. The 100 100 100 100
specific volume ofthe virus is 0.75cm 3 /g. Ifthe virus is considered
Example 30. The famous toothpaste Forhans contains 0.76
to be a single particle, find its molecular mass. (lIT 1999)
g of sodium per gram of sodium monofluoroorthophosphate
Solntion: Volume of cylindrical virus = nrzl
Solution:
Molar mass ofNa3P04F 3 x 23 + 31+ 16 x 4 + 19= 183
183 g Na3P04Fcontains 19 g fluorine
22. x gram of CaC03 was completely burnt in air. The mass of the
.. 0.76g Na3P04Fcontains 19 x 0.76g fluorine solid residue formed is 28 g. What is the value of' x' in gram?
183
(EAMCET 20(5)
:::: 0.0789 g= 78.9 mg fluorine (a) 44 (b) 200 (c) 150 (d) 50
Number of fluorine atoms [Ans. (d)]
_M_ass_in--=-_ _ x 6.023 xl 0 23 [Hint: CaC0 3(s) CaO(s) + CO 2 (g)
lOOg 56g
Gram-atomic mass
56 g residue 100 g CaC0 3
= 0.0789 x 6.023 x 1023
19 :. 28 g residue 50g CaC03]
= 2.5 x 1021 atoms 23. The mass of carbon anode consumed (giving only carbon
dioxide) in the production of270 kg of Al metal from bauxite
t~;txample31. An alloy of iron (54.7%), nickel (45%) and by Hall process is:
manganese (0.3%) has a density of 8.17 g/cm 3 . How many (a) 270 kg (b) 540 kg (c) 90 kg (d) 180 kg
iron atoms are there in a block of alloy measuring [Ans. (c)]
10cmx 20cmx 15 cm? [Hint: 3C + 2Al Z0 3 --,--74Al + 3C02
3x 12g 4X27=108g
Solution:
Volume of the block of alloy = lOx 20x 15cm3 .: 108 g Al is produced by consuming == 36 g carbon
:. 270 x 103 g AI will be produced by consuming
:::: 3000cm 3
,Mass of the block 3000 x 8.l7g ::::2451Og 36 x 270 x 103 g carbon
108
Mass of i,ron in the block
54.7 x 24510; 13406.97 g 90 x 103 g':" 90 kg carbon]
100
24. The equivalent mass of an element is 4. Its chloride has
Number of iron atoms in the block __M_a_ss__ x 6.023x 10 23
Atomic mass vapour density 59.25. Then the valency ofthe element is:
004 003 ~2 WI
13406.97 x 6.023 x 1023 [Ans. (b)]
56
[Hint: Molecular mass of MCI n == 59.25 x 2 = 118.5
:::: 1.442 X 1026
a + 35.5 x n= 118.5 ... (i) .
iiS'Example 32. An analysis of pyrex glass showed 12.9%
B 20 3 , 2.2% A12 0 3 , 3.8% Na20, 0.4% K 20 and remaining is Equivalent mass x n + 35.5 x n =118.5
Si0 2. What is the ratio ofsilicon to boron atoms in the glass ? 4n + 35.5n == 118.5 ... (ii)
'(BCECE 20(7)
n= 3]
Solution:
25. Sulphur trioxideis prepared by the fol1owing two reactions:
Percentage compositio~ ofB z 0 3 12.9%
S8(s) + 802 (g) ~ 8S02~g)
Percentage composition of
SiOz 100 - [12.9 + 2.2 + 3.8 + 0.4] 2S02(g) + 02(g ) ~ 2S03 (g)
How many grams of S03 are produced from 1 mole S8?
80.7%
(a) 1280 (b) 640
,. Mass . 12.9
NumberofmoiesofB 20 3 == =-=0.184 (c) 960 (d) 320
, Molar mass 70 [ADs. (b)]
Number of moles of boron atoms 2 x 0.184 [Hint: From the given reaction, it is clear that, I mole Sg will
give 8 moles of S03'
Number of moles ofSi0 2 Mass = 80.7 = 1.345 :. Mass of S03 formed will be = 80 x 8 = 640 g.]
Molar mass 60 26. Calculate the number of millilitresa.t STP of H2 S gas needed
Number of moles of silicon atoms 1.345 to precipitate cupric sulphide completely from 100 mL of a
Number of atoms of silicon NA x 1.345 :::: 7.3 solution containing 0.75 g ofCuCI 2 in 1 L.
(a) 21.4 (b) 14.2
Number of atoms of boron NA x 0.184 1
(c) 41.2 (d) 124
Where, NA = Avogadro's number [Ans. (d)]
BASIC PRINCIPLES 39
[Hint: CuCl 2 + H2S ~ CuS + 2HCI the values of x and yare:
(a) 40,40
Number of moles of H2S = Number of moles of CuCl 2
(c) 30,30
=~=~.00557 [Ans. (a)]
134.5
[Hint: In RHS, there are 40 hydrogen atoms, hence only
Volume of H 2S =0.00557 x 22400 =124.8 mL J option (a) will be suitable.]
27. In the reaction,
As 2 SS +xHN0 3 ~5H2S04 + yN0 2 +2H 3 As0 4
+ 12H2 0
21. Dalton's atomic theory: Every element is composed of 31. Gram molar volume: The volume occupied by one
small indivisible, indestructible particles called atoms. gram-molecular mass of any gas at NTP (O°C or 273 K and
Atoms of the same element are identical but differ in one atm or 76 em ofHg as pressure). Its value is 22.4 litre.
properties, mass and size. of atoms of other elements. Atoms 32. Vapour density:
of differe1Jt elements combine in. simple ratio to form Density of a gas
compounds. The relative number. and kind of atoms are V.D.
Density of hydrogen
always the same in a given compound. Atoms cannot be
Mass of a certain volume of a gas
created or destroyed.
Mass of same volume of hydrogen
22. Atom: The smallest particle of an element that takes part
in a chemical reaction. under same temperature and pressure
23 •. Molecule: The smallest· particle of· art element or 2Y.D.= Molecular mass
compound that can have a stable existence. 33. Mole: Amole(mol) isdefmed~sthenutnber of atoms in
24. For:mula: Gronp of symbols of elements which represents P,9 g of carbon-12 .. The number Qfatoms..is 6,07X10 23 •
one molecule of a substance. It represents also the chemical This number is called Avogadro's number.
composition. Mass of substan~e in gram
1
N 0.0f moes=--------------------~-------
25. Atomic
.
mass: Atomic mass of an1 element is the·ratio. of·
. Mass of one mole of the substance in gram
mass of one atom of an element.to 12th part of the mass of No. of particles
carbon.,,12. . i'
6.02 X 1023
Atomic mass of an element Volume of gas in Htres at NTP
= Mass of one atom of the element X 12 = 22.4
Mass of one atom of carbon-12 Mass of one atom of an element
26. Atomic mass unit (amu): ~th mass of carbon-12. It is Gram atom o'f an element
= 6.02 x
equal to 1.66 x 10-24 g.
Atomic mass of an el<~ment Mass of one molecule of a substance
Gram-molecular mass of a substance
Mass of one atom of the element
lamu 6.02 x 1023
34. Equivalent mass: The number of parts by mass of the
The actual mass of an atom of element Atomic mass in
substance which combine Or displace directly or indirectly
amu x 1.66 x 10-24 g. 1.008 parts by mass of hydrogen or 8 parts by mass of
The atomic masses of elements are actually average relative oxygen or 35.5 parts by mass of chlorine or 108 parts by
masses because elements occur as mixture of isotopes. mass of silver.
27. Gram-atomic mass or Gram atom: Atomic mass The equivalent mass of an element may vary with change of
expressed in grams. It is the absolute· mass· in grams of valency.
6.02 x 1023 atoms of any element. Eq. mass of an element
Mass of element in Mass of eleme;nt x 1.008
N 0.0f gram atoms = .
. Atomic mass of the element in grams Mass of hydrogen
Mass of element x 11200
28. Molecular mass: It indicates how many times one =-------------------------------
Volume in mL of hydrogen displaced at NTP
molecule of a substance is heavier in comparison to ~th of
. mass of one atom of carbon-12. Mass of a molecule is equal
= Mass of element x 8
Mass of oxygen
to sum of masses of the atoms present in a molecule.
29. Gram-molecular mass· or Gram molecule: Molecular Mass of element x 35.5
mass expressed in gram. It is the absolute mass in gram of Mass of chlorine
6.02 x 1023 molecules of any substance. . . m· E
35. Metal to metal displacement: _1 =_1
No. of gram molecules ~ E2
Mass of a substance in 36. Double decomposition: AB + CD ~ AD + CB
ppl.
. Molecular mass of the substance in gram
Mass of AB massofB
30. Avogadro's hypothesis: Under similar conditions of Mass of AD
temperature and pressure, equal volumes of all gases contain
same number of molecules. . Atomic mass of an element
:: Eq. mass of 1he element x Valency
I
BASIC PRINCIPLES 41
Questions
1. Match the following, choosing one item from Column-X and 2. Matrix Matching Problems:
the appropriate related item from Column-Y. (According to the new pattern of lIT Screening)
[A] [A] Match the Column-X and Column-Y:
Column-X Column-Y Column-X Column-Y
( a) Efflorescence (i) Homogeneous mixture (a) Vapour density (i) Unitless
(b) Malleability (ii) Heterogeneous mixture (b) Mole (ii) I mol electrons
(c) Alloy (ii9 Mole (c) 12 g carbon (iii) Collection of 6.023 x 1023
(d) "1 amu (iv) (l/12)th mass of atoms
carbon-l 2 1
(d) 96500 C . (iv) Molecular mass x -
2
(e) Sulphurandsand (v) Tendency to lose water of
crystallisation [B] Match the Column-X and Column-Y:
(f) Amount of substance (vi) Property ofmetalbeiilg .... -Column-X .Column-Y
hammered into thin sheets
(a) 1.6 g CH4 (i) 0.1 mol
[B]
(b) 1.7 gNH) (ii) 6.023 x 1023 electrons
Column-X Column-Y
(c) HCHO (iii) 40% carbon
. (a) Equal volumes of all (i) Dalton's atomic theory (d) C6H 120 6 (iv) Vapour density =15
gases contain equal
[C] Match the Column-X and Column-Y:
number of molecules at
NTP. Column-X Column-Y
(b) The atom is indestruc- (ii) Law of conservation of (a) 1 amu (i) Heaviest particle of atom
tible. mass (b) Proton (ii) 1.66 x 10-27 kg
(c) All pure samples of the (iii) Avogadro's law
same compound contain (c) Neutron (iii) 931.5 MeV
the same elements (d) a-particle (iv) Positively charged
combined in the same
[D] Match the Column-X with Column-Yfor the reaction:
proportion by mass.
A +B2 ~AB2
(4) Total mass before and (iv) Dulong and Petit's law
after the chemical Column-X Column-Y
reaction is same.
(a) 300 atoms of A + 200 (P) B2 is limiting reagent
(e) Atomic mass (v) Gay-Lussac's law molecules of B2
6.4
(b) 100 atoms of A + 100 (q) A is limiting reagent
Specific heat molecules of B2
(f) Gases react in simple (vi) Law of constant (c) 5 mol of A +2.5 mol (r) None of the reactant is in
ratio of their volumes. proportions ofB2 excess
[C] . (d) 2.5 mol of A + 5 mol (s) 200 molecules of A B2 will
ofB2 be formed
Column-X Column-Y
(a) Most abundant element (i) Platinum
(b) Most abundant metal (ii) Diamond
(c) Liquid at room temp. (iii) Aluminium
"
(d) Hardest substance (iv) Plutonium
(e) Most ductile metal (v) Mercury
(f) Transuranic element (vi) Oxygen
· BASIC PRINCIPLES 43
1. [A] (a-v); (b-vi); (c-i); (d-iv); (e-il); (f-iii) 2. [A] (a-i, iv); (b-iii); (c-iii); (d-ii)
[B] (a-iii); (b-i); (c-vi); (d-ii); (e-iv); (f-v) [B] (a-i, ii); (b-i, ii); (c-iii, iv); (d-iii)
[C] (a-vi); (b-iii); (c-v); (d-ii); (e-i); (f-iv). [C] (a-ii, iii); (b-ii, iv); (c-i); (d-iv)
[D] (a-p, s); (b-r); (c-p); (d-q).
1. The density of mercury is 13.6 glmL. Calculate the diameter [Ans. 9.41 x 1023 CH 4 molecules, 9.41 x IOz3 carbon atoms and
of an atom of mercury assuming that each atom of mercury is 37.64 X 1023 hydrogen atoms.]
occupying a cube of edge-length equal to the diameter of
mercury atom. [Hint: No. of moles of methane = 25.0
(Atomic mass of mercury 200) 16.0
[Ans. 2.9 x 10-8 cm] One molecule of methane contains one carbon atom and four
2. A metal M of atomic mass 54.94 has a density of 7.42 g/cc. hydrogen atoms.]
Calculate the apparent volume occupied by one atom of the 12. How much sugar (C1 zH 22 0 11 ) will be required if each person
metal.
[Ans. 1.23 x 10-23 cc] on the earth is given 100 molecules of sugar? The popUlation
o(the earth is 3 x 1010.
3. Find the charge of I g ion ofN 3- in coulomb.
[Ans. 2.894 x 105 coulomb] [Ans. 170.43 X 10- 11 g]
13. A mixture of hydrogen and oxygen contains 20% by mass of
4. Calculate the volume at NTP occupied by 6.25 g of nitrogen.
hydrogen. What is the total number of molecules present per
[Ans. 5.0 litre] gram of the mixture?
5. 10 mL of hydrogen contains 2 x 103 molecules of hydrogen at [Ans. 7.528 x 1022]
certain pressure and temperature. Calculate the }lumber of [Hint: In I gram of the mixture, 0.2 g of hydrogen and 0.8 g of
molecules of oxygen whose volume is 200 mL at the same
temperature and pressure. oxygen are present. Moles of Hz = 0.2 = 0.1, moles of oxygen
2
4
[Ans. 4 x 10 molecules]
= 0.8 = 0.025. Calculate the number of molecules of hydrogen
6. The masses of equal volumes of a gas and hydrogen are 25.6 g 32 .
and 0.8 g respectively under same conditions of temperature and oxygen and then add.]
and pressure. Find the molecular mass of the gas. 14•. How many electrons ate present in 18 mL of water?
(MLNR 1995)
[Hint: Y.D. of the gas 25.6 32.0
0.8 [Hint: 18 mL water = 18 g water:::: I mole water 6.02 x 1023
Molecular mass 2 V.D. 2 x 32.0= 64.0] molecules, each molecule consists 10 electrons (8 electrons per
oxygen atom, 2 electrons for two hydrogen atoms). Total
7. One litre of a gas at NTP weighs 1.97 g. Find the molecular electrons = 10 x 6.02 X 1023 = 6.02 X 1024]
mass of gas.
15. Sulphur molecule is known to be composed ofS atoms of the
[Ans. 44.128]
element. In a sample of 192 g of pure sulphur, calculate (i)
8. How many moles of water are present in one litre of water? number of g-atoms of sulphur; (il) number of atoms of
[Ans. 55.5 moles] sulphur; (iii) number of moles of sulphur; (iv) number of
9. Calculate the mass of 6.02 x 1021 molecules of nitrogen. molecules of sulphur.
[Ans. 0.28 gJ [Ans. g-atoms = 6; No. of atoms 6 x 6.02 x 1023 ; No. of
10. 1.5276 g ofCdCl 2 was found to contain 0.9367 g of cadmium. moles = 0.75; No. of molecules =4.52 x 1023]
Calculate the atomic mas~ of cadmium.
[Ans. 112.54] [Hint: The atomic mass of sulphur is 32.]
Mass of Cd x 35.5 16. The vapour density of a mixture containing N02 and N 20 4 is
[Hint: Equivalent mass of cadmium
Mass of CI 38.3 at 27°C. Calculate the moles of NO z in 100 g of the
mixture. (MLNR 1993)
= 0.9367 x 35.5= 56.27
0.5909 [Hint: Mol. mass of mixture 2 x 38.3 76.6
Atomic mass Equivalent mass x Valency]
11. Calculate how. many methane molecules and how many No. of moles in 100 g of mixture = 100
76.6
hydrogen and carbon atoms are there in 25.0 g of methane?
(MLNR 1990; Dhanbad 1992) Let a g ofN02 is present in mixture.
44 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Moles ofN0 2 + Moles ofN 20 4 Moles of mixture 23. Use the data given inthe following table to calculate the molar
a 100 a 100 mass of naturally occurring argon: . , ..
-+_._-=-- or a= 20.10 g
46 92 76.6 Isotope Isotopic molar mass Abundance
MoiesofN02 in mixture 20.10:= 0.437] 36Ar 35.96755 g mol- I 0.337%
46
38 Ar 37.96272 g mor l
0.063%
17. Calculate the number of oxygen atoms in 88 CO 2 , What g
would be the mass of CO having the same number of oxygen 4°Ar 39.9624 gmor l 99.6%
atoms? (BITS 1990)
[Ans. 39.947]
[Hint: 88 g CO 2 = 2 moles of CO 2 , One molecule consists of 2
24. Density of oxygen atNTP is 1.429 g/litre.' Calculate the
oxygen atoms. standard molar volume of the gas.
No. of oxygen atoms = 2 x 2 x 6.02 x 1023 = 24.08 x 1023 [Ans. 22.39 litre mol-I]
25. How many iron atoms are present in a stainless steel ball
CO molecule has one oxygen atom.
bearing having a radius of 0.254 cm? The stainless steel
Mass of CO containing 24.08 x 1023 oxygen atoms contains 85.6% Fe by weight and has density of7.75 glcm 3 .
__2_8---,;:;:- x 24.08 x 1023 112 g) [Ans. 4.91 x 1021 ]
26.. The nucleus of an atom. X is supposed to be a sphere with a
18. Density of water at room temperature is 1.0 g cm-3. How many radius of 5 x 10- 13 cm. Find the density of the matter in the
molecules are there in one drop of water if its volume is 0.1 atomic nucleus if the atomic weight of X is 19.
cm3? [Ans. 6.02 x 1013 glmL]
[Ans. 3.34 x 1021 molecules] 27. Calculate the number of atoms of each element present in
[Hint: Mass of one drop:= Vol. x d 0.1 xl = 0.1 g 122.5 g ofKC10 3 .
[Ans. Number of atoms of'K' = 1 x 6.023 X 1023
No. of moles = 0.1; No. of molecules 6.02 x 1023 x 0.1 ]
Number of atoms of 'Cl' = 1 x 6.023 X 1023
=0
18 . ·18
19. Naturally occurring bqron consists of two isotopes, whose Number of atoms of '0' 3 x 6.023 x 1023 ]
atomic masses are 10.01 and 11.01. The atomic mass of
28. In an experiment, 1.0 g CaC03 on heating evolved 224 mL of
natural boron is 10.81. Calculate the percentage of each
isotope in natural boron. (MLNR 1994) CO2 at NTP. What mass of Cao (calcium oxide) is formed?
[Ans. % of isotope with atomic mass 10.01 20; % of isotope [Ans. Mass ofCaO = 0.56 g]
with atomic mass 11.01 = 80] [Hint: Mass of 224 mL of CO 2 =44 x 224 0.44 g)
[Hint: Let x be the percentage of the isotope with atomic mass 22400
10.01. 29. What mass of potassium chlorate (KCI03 ) on heating gives
1.491 g of potassium chloride (KCl) and 0.6721itres of oxygen
IO.Olxx+l1.01(l00-x)~1O.81 or x=20]
atNTP?
100 100
[Ans, Mass ofKCI0 3 = 2.451 g]
20. Chlorine has isotopes 3sCI and 37 Cl. There are three 35CI
[Hint: Mass of 22.4 litre of oxygen at NTP = 32 g)
isotopes for every 37 CI isotope in a sample of chlorine.
30. A compound AB completely decomposes into A and B on
Calculate the atomic mass of chlorine.
heating. 50 g of AB, on strong heating, gave 40 g of A. How
[Ans. A = 3 x 35 + 37 x 1 == 35.5 ] much quantity of AB should· be decomposed by heating to
4 obtain 2.5 g of B? How much quantity of A will be produced
21. Natural hydrogen gas is a mixtUre of IH and 2H in the ratio of in the process?
5000 : 1. Calculate the atomic mass of the hydrogen: [Ans. 12.5 g AB is to be decomposed, 10.0 g of A will be
[Ans. 1.000199] produced.]
22. Chromium has tne following isotopic composition: [Hint: AB...-? A + B)
50g 4()g 109
. FractioDai
Mass number Isotopic mass 31. If 12.6 g of NaHC0 3 is added to 20.0 g ofHCI solution, the
abundance
residue solution is found to weigh 24.0 g. What is the mass and
50 49.9461 x volume of CO2 released at NTP in the reaction?
52 51.9405 0.8379 [Ans. 8.6 g CO 2 released. Volume at NTP = 22.4 x 8.6 = 4.378
53 52.9407 0.0950 44
litre]
54 I 53.9389 0.0236 32. (i) 5.06 g of pure cupric oxide (CUO), on complete reduction
Calculate the value of x. by heating in a current of hydrogen, gave 4.04 g of
[Ans. 0.0435] metallic copper.
BASIC PRINCIPLES 45
(ii) 1.3 g of pure metallic copper was completely dissolved 39. Phosphorus and chlorine form two compounds. The first
in nitric acid and the resultant solution was carefully contains 22.54% by mass of phosphorus and the second
dried and ignited. .1.63 g CuO was produced in the j4.88% of phosphorus. Show that these data are consistent'
process. Show that these results illustrate th~ law of with law of multiple proportions.
constant proportions. (Hint: The ratio of the masses of chlorine which combines with
(Ans. In both cases, the ratio of copper and oxygen is 1 : 0.25. a fixed mass of phosphorus in two compounds is 3 : 5 which is a
Hence, the law of constant proportions is illustrated.] simple whole number ratio. Thus, the data illustrate law of
33. Metal M and chlorine combine in different proportions to multiple proportions.]
form two compounds A and B. The mass ratio M : CI is 40. A and B are two hydrocarbons. A and B are heated separately
0.895: I in A and 1.791 : 1 in B. What law of chenrical in excess of oxygen when 0.028 g of A gave 44.8 mL CO2 and
combination is illustrated?' 0.044 g of B gave 67.2 mL CO2 at NTP. Show that the results
[Ans. Masses of metal which combine with 1 part of chlorine are in' agreement witlt law of multiple proportions.
are in the ratio of 1 : 2, which is a simple ratio. Hence, law of [Hint: Determine the masses of CO2 at NTP and then masses of
multiple proportions is illustrated.] .
carbon.
34. 2.8 g of calcium oxide (CaO) prepared by heating limestone . 44
were found to contain 0.8 g of oxygen. When one gram of (A) Mass of CO 2 = 22400 x 41.8 == 0.088 g,
oxygen was treated with calcium, 3.5 g of calcium oxide was
'Mass of carbon == 0.024 g, mass of hydrogen 0.004 g.
obtained. Show that the results illustrate the law of definite
44
proportions. (B) Mass of CO 2 == - .-x 67.2 == O.l32g,
22400
35. By means of the given analytical results show that law of
Mass of carbon = 0.036 g, mass of hydrogen == 0.008 g.
multiple proportions is true:
Thus, the masses of carbon combining with same mass of
Mercurous chloride Mercuric chloride hydrogen are in the ratio of 4 : 3 which is a simple ratio. Hence,
Mercury = '84:92 % Mercury = 73.80% law of multiple proportions is followed.]
41. Aluminium oxide contains 52.9% aluminium' and carbon
Chlorine 15.08% Chlorine = 2620% dioxide contains 27.27% carbon. Assuming the validity of the
[Ans. The masses of mercury which combine with I part of law of reciprocal proportions, calculate the percentage of
chlorine are in the 'ratio of 2 : I, which is a simple ratio. Hence, aluminium in aluminium carbide.
law of multiple proportions is illustrated.] [Hint: From the data, it is observed that the ratio of masses of
36. 1 g of a metal, having no variable valency, produces 1.67 g of aluminium and carbon in aluminium carbide should be 3 : 1 or its
its oxide when heated in air. Its carbonate contains 28.57% of simple mu1tiple. Hence, percentage of aluminium iIi aluminium
the metaL How much oxide will be obtained by heating 1 g of carbide = 2.4 x 100. = 75.0]
the carbonate?
[Ans. 0.477 g] 42. Two volumes of ammonia, on dissociation gave one volume of
nitrogen and three volumes of hydrogen. How much hydrogen
Mass of metal Mass of metal in 1g of carbonate
[Hint: will be obtained from dissociation of 40 mL ofNH) ?
Mass of oxygen x
[Ans. 60 mLl
i.e., x == 0.1914 g of oxygen 43, The following results were obtained by heating different
oxides oflead in a current of hydrogen:
Mass of oxide = 0.2857 + 0.1914 = 0.4771 g] . (a) 1.393 g oflitharge gave 1.29~ g oflead.
37. 0.36 g of Mg cbmbines with chlorine to produce 1.425 g of (b) 2.173 g of lead peroxide gave 1.882 g oflead.
magnesium chloride. 9.50 g of anothefsample of anhydrous (c) 1.721 g of red lead gave 1.552 g oflead.
magnesium chloride gave, on electrolysis 2.24 litre of chlorine Show that these results ar.e in accordance with the law of
at NTP. Show that these data agree with the law of constant multiple proportions .
.proportions. .(Ans. Masses of lead that combine with same mas~Mf oxygen
(Hint: Mass of 2.24 litre of chlorine at NIP == ~ x 2.24 are in the ratio of 4 : 2 : 3 which is a simple ratio. So, 'the results
22.4 are in accordance with the law of multiple proportions.}
== 7.1 g. In both cases, the ratio of masses ofMg and CI is 1 : 3. 44.. Calculate the number of g-moles of CaO that could be
Hence, law of constant proportions is followed.] obtained from 42.54 g of CaC03 and convert. the number of
g-moles to grams.
38. Carbon dioxide contains 27.27% carbon, carbon disulphide
contains 15.97% carbon and sulphur dioxide contains 50% .42.54
[No. of g-moles =: == 0.4254,
sulphur. Show that these figures illustrate the law of reciprocal . 100
proportions. Mass of CaO 0.4254 x 56 == 23.8 !II
[Hint: The masses of oxygen and sulphur which combine with 45. I g of a metal M which has specific heat of 0.06 combines
1 part of carbon are in the ratio of 2.667 : 5.25, i.e., 1 : 2. In with oxygen to form 1.08 g of oxide. What i~ the atomic mass
sulphur dioxide, the masses of sulphur and oxygen are in the ratio ofM? . '
of 1 :. 1 which is a simple multiple of first. Hence, law of
reciprocal proportions is illustrated.]
46 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
. . . 6.4 51. If the equivalent mass of a metal (M) is x and the formula of its
[Hint: A pproxunate atOIll1C mass = = 106.6
0.06
oxide is M m On' then show that the atomic mass of Mis 2xn
m
Equivalent mass of M = I x8 100
[Hint: m atoms of M combine with n atoms of oxygen.
0.08
106.6 1 atom of M combines with!!.. atoms of oxygen.
Valency = - - "" 1 m
100
· 2n
Exact atomic mass = I 00 x I =100 ] Hence, Vaency
I =-
m
,-'
A compound .contains 28% of nitrogen and 72% metal by
mass. 3 atoms of the metal combine with 2 atoms of the Atomic mass = Equivalent mass x Valency
nitrogen. Find the atomic mass of the metal. 2n 2nx]
xx
[Hint: Valency of metal = 2 and valency of nitrogen 3 m m
52. Two oxides of metals A and B are isomorphoUS. The metal A
. I f0 ' . mass of metal 72
EqUlva ent mass nItrogen =-14 ; whose atomic mass is 5,2, forms a chloride whose vapour
. 3 14/3 28 density is 79. The oxide of the metal B contains 47.1%
Equivalent mass of metal = 12 '. oxygen. Calculate the atomic mass of B.
[Hint: Let the valency of A be x. The formula of chloride
Atomic mass of metal == 12 x 2 =24]
= ACl"
47. The chloride of a solid metallic element contains 57.89% by
2 V.D. A + x x 35.5 or x",3
mass of the element. The specific heat of the element is 0.0324
cal deg -1 g -I. Calculate the exact atomic mass of the element. As the two oxides are isomorphous, the valency of B is also 3.
-: Ient mass 0 f B =--
EqUiva 52.9 x 8 = 8.99 atomic mass of
[Hint: Equivalent mass of the element = 57:89 x 355:::: 48.8 -, 47.1'
, . 42.11
B = ~.99 x 3 26.97]
Approximate atomic mass 200 53. A mixture of 1.65 x 1021 molecules of X and 185x ler l
0.0324
molecules ofY weighs 0.6.88 g. If molecular mass ofY is 187,
200 what is the molecular mass of X ?
Val ency =-""4 21 21
.. 48.8 [Hint: A x 1.65 X 10 + 187 x 1.85 x 10 =0.688 A 4135]
23
Exact atomic mass = 48.8 x 4 195.2] 6.02 x 6.02 x 10 '
54. The equivalent mass of a metal is 29.73 and the vapour density
48. Two oxides ofametal contain 63.2% and 69.62% of the metal.
of its chloride is BOA. Find out the atomic mass of the metal.
The specific. heat of the metal is 0.117. What are the formulae
of the two oxides? [Ans. Atomic mass 118.92]
[Ans. M0 2 andM20 3]
2 x V.D. 2 x (BOA)
49. White vitriol (hydrated zinc sulphate) is isomorphous with [Hint: Valency
Eq. mass + 35.5 = (29.73 + 35.5) "" 4]
MgS04 ·7H2 0. White vitriol contains 22.95% zinc and 43.9%
of water of crystallisation. Find the atomic mass of zinc. 55. Calculate the percentage of aluminium, sulphate radical and
water in potash alum.
[Hint: The formula of white vitriol should be znS0 4· 7HP as it
[Ans. Al = 5.6<)010; SO!- 40.51%; Water = 45.57%]
is isomorphous to MgS0 4 ·7H20, i.e., 7 water molecules are
56. Carbohydrates are represented by the general formula
associated with one zinc atom. 7HP = 7 x.18 126. Mass of Zn
with which 126 parts of water by mass ate associated Cm (H2 0)". On heating, in absence of air, they decompose into
22.95 x I 26 = 65. 87. Atomic mass of. zinc.] steam (HP) and carbon. 3.1 g of a carbohydrate,\on complete
= decomposition by heating in absence of air, leave a residue of
.j. 43.~0 .,
1.24 g of carbon. If the molecular mass of the carbohydrate be
50. li\.. solid element. burns in oxygen without a~y change in
J 80, find its molecular formula.
volwne (of gas) under similar conditions 01 temperature and
pressure. If the vapour density of pure gaseous product is 32, [Hint: Determine % of carbon in carbohydrate. It is 40%. Water
what is the equivalent mass of the element? is 60%. Empirical formula == CHzO. Molecular formula
[Hint: One vol. of oxide contains 1 vol. of 02' = 6 x CHP CJI1206']
57. A gaseous hydrocarbon contains 85.7% carbon and 14.3%
One mole of oxide contains one mole of 02' hydrogen. 1 litre of the hydrocarbon weighs 1.26 g at NTP.
Mol. mass of oxide = A + 32 = 2 V.D. 64 Determine the molecular formula of th~ hydrocarbon.
[Ans. C2H4]
So, A = 32 58. Equal masses of oxygen, hydiogen and methane are taken in a
contairier under identical conditions. Find the ratio of their
32 parts of element combine with'32 parts of oxygen.
volumes.
Equivalent mass of element = 32 x 8 8]
[Ans. 1: 16: 2]
So,
32
BASIC PRINCIPLES 47
59. How many moles are there in 1 m 3 of any gas at NTP? [Hint: Formula of divalent hydrated metal sulphate will he
[Ans. 44.6 moles] MS0 4 ·xH20
60. A hydrated chloride of metal contains 18.26% metal and
Molecular mass of salt = 65.4 + 96 + 18x
32.42% chloride ion by mass. The specific heat of metal is
0.16. What is hydrated chloride? = (161.4 + 18x) .
[Ans. CaCI 2 ·6H20] 18x
% of water = x 100 = 43.85
61. 1.878 gof MBrx when heated in a stream of HCl gas was 161.4 + 18x
completely converted to chloride MCl x which weighed 1.0 g. On solving, x=7
The specific heat of metal is 0.14 cal g-l. Calculate .the
.'. Molecular formula of hydrated salt = MS0 4 •7H 20 ]
molecular masses of metal bromide and metal chloride.
70. A person with fever has a temperature of 102.SOF. What is the
[Ans. Mol. mass of metal bromide = 285.54;
temperature in degree celsius?
Mol. mass of metal chloride = 1522]
[Hint: Use C= 5(F- 32)]
62. An au~omobile antifreeze consists of 38.7% C; 9.7% H and . 9
remaining oxygen by weight. When 0.93 g of it are vaporised
71. An ornamental ring contains 275 carats of diamond. How
at 200°C and 1 atm pressure, 582 mL of vapour are formed.
many grams diamond does it have?
Find the molecular formula of the antifreeze.
[Hint: 1 carat = 200 mg
[Ans. C;Ift;02]
:. Mass of diamond = 275 x 200 x 10-3 g]
63. A mineral contained MgO = 31.88 %; Si02 = 63.37% and
H20 = 4.75%. Show that the simplest formula for the mineral
72. 1 volume of a gaseous compound consisting C, H, °
on
complete combustion in presence of 2.5 volume of O2 gives 2
is H2Mg3Si4012.
°
(H = 1; Mg= 24; Si = 28; = 16)
vol. of steam and 2 vol. of CO 2. What is the formula of the
compound if all measurements are made at NTP?
64. How m~ny moles of NH3 are there in 250 cm 3 of a 30%
[Ans. C2H40]
solution, the specific gravity of which is 0.90?
73. 60 mL of a mixture of nitrous oxide and nitric oxide was
[Ans. 3.97 moles]
exploded with excess of hydrogen. If 38 mL of N2 was
65. Haemoglobin contains 0.25% iron by mass. The molecular formed, calculate the volume of each gas in the mixture.
mass of haemoglobin is 89600. Calculate the number of iron
[Ans. NO = 44 mL and N20 = 16 mL]
atoms per molecule of haemoglobin.
[Atomic mass of Fe = 56] 74. For a precious stone, 'carat' is used for specifying its mass. If 1
[Ans. 4 atoms] carat = 3.168 grains (a unit of mass) and 1 gram = 15.4 grains,
find the total mass in kilogram of the ring that contains 0.5
66. A sample of potato-starch was ground to give a starch like
carat diamond and 7 gram gold.
molecule. The product analysed 0.086% phosphorus. If each
molecule is assumed to contain one atom of phosphorus, what [Ans. 7.1 x 10-3 kg]
is the average molecular mass of the material? 75. The density of a gaseous element is 5 times that of oxygen
[Ans. 36000 amu] under -similar conditions. If the molecule of the element is
triatomic, what will be its atomic mass?
67. Insulin contains 3.4% sulphur. Calculate minimum molecular
mass of the insulin. [Ans. 53.33]
[Ans. 941.176 amu] 76. Calculate the number of electrons, protons and neutrons in 1
mole of 18 0 2- ions.
[Hint: For minimum molecular mass, one molecule of insulin
must have atleast orie sulphur atom:] [Ans. Electrons = 10 x 6.023 X 1023
68. Calculate the number of carbon, hydrogen and oxygen atoms Protons = 8 x 6.023 X 1023
in 18 g of glucose. .
Neutrons = 8 x 6.023 x 1023 ]
[Ans. 3.61 x 1023 carbon atoms, 7:22 x 1023 hydrogen atoms,
3.61 x 1023 oxygen atoms] 77. 600 mL of a mixture of 02 and D3 weighs 1 gm at NTP.
69. Hydrated sulphate of a divalent metal of atomic weight 65.4 Calculate the volume of ozone in the mixture.
loses 43.85% of its weight on dehydration. Find the number of [Ans. 200 mL]
molecules of water of crystallisation in the formula of
hydrated salt. [JEE (West Bengal) 2005]
I .'
..;p:OBJECTIVE QUESTIONS
S~t·1: Questions with single correct answer
15. One sample of air is found to have 0.03% carbon dioxide and
1. The father of modetn chemistry is: another sample 0.02%. This illustrates that:
(a) Priestley (b) Lavoisier (a) aids a compound
(c) Dalton (d) Mendeleev (b) air is an element
2. A pure substance can only be: (cr'air does not follow the law of constant proportions
(a) a compound (d) air is a mixture
(b) an element 16. Which one of the following is not a mixture?
(c) an element or a compound (a) Distilled water
(d) a heterogeneous mixture (b) Sugar dissolved in water
3. A pure substance which contains only one type of atoms is (c) Liquefied Petroleum Gas (LPG)
called: . (d) Gasoline
(a) an element (b) a compound 17. Which of the following is a charactelistic property of both
( c) a solid (d) a liquid mixtures and compounds?
4. Which one of the phrases would be incorrect to use? . (a) Their properties are same as those of their components
(a) A mole of an element (b) A mole ofacompound (b) Energy is released when they are formed
(c) Their masses me equal to the sum of the masses of theil'
(c) An atom of an element (d) An atom of a compound
components .
5. A symbol not only represents the name of the element but also
(d) They contain the components in fixed proportions
its:
. 18. Name the scientist who stated that matter can be converted
(a) atomic mass (b) atomic number
into energy:
(c) atomicity (d) atomic volume
(a) Boyle (b) Lavoisier (c) Avogadro (d) Einstein
6. The credit for the discovery of transuranic elements goes to:
19. Which one of the following is not an intensive property?
(a) Hahn (b) Rutherford
(a) Weight (b) Pensity
(c) Seaborg (d) Curie
(c) Refractive index (d) Melting point
7. The most abundant metal in'earth's crust is:
20. The metalloid among the following group of elements is:
(a) iron (b) magnesium
(CPMT 1993)
(c) calcium (d) aluminium
(a) P (b) As (c) Al (d) Po
8. The most abundant element in earth's crust is:
21. Which of the following ailoys does contain Cu andZn?
(a) hydrogen (b) oxygen (e) nitrogen (9) silicon
(lIT 1993)
9. Which one of the elements is not found in nature? (a) Bronze (b) Bras~
(a) Radium (b) Technetium . (c) Type metal (d) Rolled gold
(e) Polonium (d) Helium 22. Which metal is present in german silver?
Ill. Which one of the following is not a compound? (a) Copper (b) Iron (c) Silver (d) . Zinc
(a) Marble' (b) Ozone 23. Which of the following processes results in the formation of a
(c) Carborundum (d) Quicklime neW compound? .
11. Which one of the following is not an element? (a) Dissolving common salt in water
(a) Diamond (b) Ozone (c) Silica (d) Graphite (b) Heating water
12. The direct change from solid to gaseous state is referred to as: (c) Heating platinum rod
(a) dissociation (b) decomposition (d) Heating iron rod
(c) sublimation (d) deliquescence 24. Which one of the following is not a chemical change?
13. Sulphur burns in oxygen to form sulphur dioxide. The (a) Sublimation (b) Combustion
properties of sulphur dioxide are: (c) Electrolysis (d) Rusting
(a) totally different from sulphur and oxygen 25. The law of mUltiple proportions is illustrated by the pair of
(b) similar to'sulphur compounds:
, (c) similar to oxygen (a) sodium chloride and sodium bromide
(d) more similar to sulphur than oxygen (b) water and heavy water
14. Which one of the following statements is incorrect? (c) sulphur dioxide and sulphur trioxide
(a) All elements are homogeneous (d) magnesium hydroxide and magnesium oxide
,(b) Compounds always contain two or more different elements 26. In compound A, 1.0 g nitrogen combines with 0.57 g oxygen,
(c) A mixture is not always heterogeneous In compound B, 2.0 g nitrogen unite with 2.24 g oxygen and in
(d) Air is a heterogeneous mixture compound C, 3.0 g nitrogen combine with 5.11 g oxygen.
These results obey the law of:
I
BASIC PRINCIPLES 49
(a) multiple proportions (b) constant proportions 36. Hydn;,gen combines with .chlorine to iornl HCl. It also
(c) reciprucai proportions (d) none of these combines with sodium to form NaH. If sodium and chlorine
27., Which one is the best example oflaw of conservation of mass? also combine with each other, they will do so in the ratio of
(a) 6 g of carbon is heated in vacuum, there is no change in ·their masses as:
mass (a) 23: 35.5 (b) 35.5 : 23
(b) 6 g of carbon combines with 16 g of oxygen to form 22 g (c) 1 : 1 (d) 23: 1
of CO2 37. Zinc sulphate contains 22.65% Zn and 43.9% H20. If the law
(c) 6 g water is completely converted into steam Of constant proportions is true, then the maSs of zinc required
(d) A sample. of air is heated at constant pressure when its to give 40g crystal!) will be: . .
volume increases'but there is no change in mass (a) 90.6 g (b) 9.06 g (c) 0.906 g (d) 906 g
28. A chemical equation: is balanced according to the law of: 38. 3 g of a hydrocarbon on combustion in excess of oxygen .
(a) multiple proportions (b) constant proportions produces 8.8 g ofCO2 and 5.4 g ofH,20. The data illustrates
(c) reciprocal proportions (d). conservation of mass the law of:
29. S02 gas was prepared by (i) burning sulphur in oxygen, (a) conservation of mass (b)· mUltiple proportions
(ii)· reacting sodium sulphite with dilute H2S04 and (iii) (c) constant proportions. (d) reCiprocal proportions
heating copper with conc. H2 S04 , It was found that in each
case sulphur and oxygen combined in the ratio of 1 : 1. The [Hint: Mass of carbon in 8.8 g CO2 '= ~ x 8.8 2Ag;
44
data illustrates the law of:
(a) conservation of mass (b) multiple proportions Mass of hydrogen in 5.4 g Hp = 2 x 5.4 0.6 g.
(c) constant proportions (d) reciprgcal proportions 18
30. A sample of CaC03 has Ca = 40%, C d 12% and 0= 48%. If Total mass of(e + 1I) = 2.4+ 0.6= 3.0 g]
is
the law of constant proportions true, then the mass of Ca in 39. In the reaction, N2 + 3H2 ~ 2NH3, the .ratio of volllmes of
nitrogen, hydrogenimd ammonia is 1 : 3 : 2. These. figures
5 g of Cac03 from another source will be:
(a) 2.0 g (b) 0.2 g ( c ) 0.02 g (d) 20.0 g illustrate the law of:
31. Potassium combines with two isotopes of chlprine (a) constant proportions (b) Gay-Lussac
. eSCI and 37CI) respectively to form two samples of KCI. (c) multiple proportions (d) reciprocal proportions
40. Two volumes of anllllonia, on dissociation gave Qne volume of
Their formation follows the law of:
nitrogen and three volumes of hydrogen. How much hydrogen
(a) constant proportions (b) multiple proportions
will be obtained from the dissociation of 10 litre ofNH3?
(c) reciprocal proportions (d)" none of these
(a) 30 litre (b) 10 litre (c) 15 litre (d) 2Q litre
32. Different proportions of oxygen in the various oxides of
41. If6litre ofH2 and 5.6 litre ofCl 2 are mixed and exploded in
nitrogen, prove the law of:
an eudiometer, the volume of HCI formed is:
(a) reciprocal proportions (b) multiple proportions
(a) 6.0 litre (b) 5.6 litre (c) 11.2litre (d) 11.6litre
(c) constant proportions (d) conserv~tion of mass
42. The law of constant proportions was enunciated by:
33. One part of an element A combines with two p<!l'ts of B
(a) Dalton (b) Berthelot (c) Avogadro (a) Proust
(another element). Six parts of eleI'llelit C combine wjth four
43. An important postulate ofDalton:s atomic theory is:
parts of element B. If A and C combine together, the ratio of
(a) an atom contains electrons, protons and neutrons
their masses will be governed by~
(a) law of definite proportions (b) atom can neither be created nor destroyed nor divisible
(c) all the atoms. of an elemeht are not -identical
(b) law of multiple proportions
(d) all the elements are available in nature in the form of
(c) law of reciprocal proportions
atoms
(d) law of conservation of mass
44. The atomic masses of the elements are usually fractional because: .,:'.
34. H2S contains 5.88% hydrogen, H20 ~ontains 11.11 % hydrogen
(a) elements consist of impurities
. while S02 contains 50% sulphur. These figures jllustrate the
(b) these are mixtures of allotropes"
law of:
(e) these are mixtures ofisobars
(a) conservation of mass (b) constant proportions
(d) these are mixtureS of isotopes
(c) multiple proportions (d) reciprocal proportions
35. Number.of atoms in"4.25 g ofNH3 is: (AFMC 2010)
of
·45. The chemical formula a particular compound represents:
3 (a) the size of its molecule
(a) 6.023xl023 . (b) 4x6.023xl02
(b) the sQ.ape of its molecule
(c) l. 7 X 1024 (d) 4.5 x 6.023 x 1023 (c) the total number of atoms in a molecule
. w (d) the number of different types of atomS in a molecule
[Hint: Number of molecules ofNH 3 =- x 6.023 X 1023
. M . 46. Which one of the following properties of an element is not
= 4.25 x 6.023 x 1023 variable?
17 (a) Valency (b) Atomic mass
Number of atom = 4 x 4.25 x6.023xto2, (c) Equivalent mass (d) All of these
17
= 6.023 x 102']
50 GR B. PHYSICAL CH~MISrIW FOR COMPI::TITIONS
41. 1 amu is equal to: 57. 74.5 g of a metallic chloride contains 35.5 g of chlorine. The
(a) 1.00758 g (b) 0.000549 g equivalent mass of the metal is:
(c) l66xlO-24 g (d) 6.02 X 10-23 g (a) 19.5 (b) 35.5 (c) 39.0 . (d) 78.0
48. Which one of the following relationships is correct? 58. The product of atomic mass and specific heat of any element is
a constant, approximately 6.4. This is known as:
(a) At. mass = 6.4 x Sp. heat.
(a) Dalton's law (b) Avogadro's law
(b) At. mass x Sp. heat = 6.4
(c) Gay-Lussac law (d) Dulong Petit's law
(e) At. mass x 6.4 = Sp. heat
(d) At. mass x Sp. heat x 6.4 = 1
59. The molecular mass of chloride, MCl, is 74.5. The equivalent
mass of the metal M will be:
49. A I g of an element gives A2 g of its oxide. The equivalent mass
(a) 39.0 (b) 74.5
of the element is:
(c) 110.0 (d) 35.5
(a) A2 - Al X 8
[Hint: Mol. mass = At. mass + 35.5 = Eq. mass x valency +35.5,
Al
Valency of M from the formula Mel is 1]
(c) Al X 8 60. 1 g of hydrogen is found to combine with 80 g of bromine. 1 g
A2 - Al
. ".
50. Al g of an element gives A2 g of its chloride; the equivalent
of calcium combines with 4 g of bromine. The equivalent mass
of calcium is:
mass of the element is: (a) 10 (b) 20 (c) 40 (d) 80
(a) _A---,I~ x 35.5 (b) A2 x 35.5 61. 2.8 g of iron displaces 3.2 g of copper from a solution of
A2 - Al A2 - Al copper sulphate. If the equivalent mass of iron is 28, the
equivalent mass of copper will be:
(c) A2 - Al x 35.5 (d) A2 - Al x 35.5
(a) 16 (b) 32 (c) 48 (d) 64
Al A2
62. The specific heat of a metal of atomic mass 32 is likely to be:
51. Which one of the relationship is wrong? (a) 0.25 (b) 0.24 (c) 0.20 (d) 0.15' .
(a) 2 Y.D. = Mol. mass
63. The equivalent mass of an element is 4. Its chloride has a
(b) At. mass = Eq. mass x Valency
vapour density 59.25. The valency of the element will be:
6.4
(c) At. mass = - - - (a) 4 (b) 3 (c) 2 (d) 1
Sp. heat 64. The equivalent mass of iron in the reaction,
H I ' Mol. mass
(d) va ency = - - - - 3Fe + 4H20 = Fe 30 4 + 4H2 would be:
Eq. mass (a) 21 (b) 56 (c) 42 (d) 10
52. In ml g of a metal A displaces rnzg of another metal B from its 65. The specific heat ofa bivalent metal is 0.16. The approximate
salt solution and if their equivalent masses are EI and E2 equivalent mass of the metal will be:
respectively, then the equivalent mass of A can be expressed (a) 40 (b) 20 (c) 80 (d) 10
as: 66. A sample of pure calcium weighing 1.35g was quantitatively
converted to 1.88 g of pure calcium oxide. Atomic mass of
(a) EI = rnz x E2
ml calcium would be:
(a) 20 (b) 40 (c) 16 (d) 35S
(c) EI = ml ;2 rnz (d) EI = ~: x E2 67. A metal oxide is reduced by heating it in a stream of hydrogen.
It is found that after complete reduction, 3.15 g of the oxide
53. When the specific heat of a metallic element is 0.214 cal g -I , have yielded 1.05 g of the metal. We may conclude that:
the atomic mass will be closest to which one ofthe following? (MLNR 1991)
(a) 1 (b) 12 (c) 30 (d) 66' (a) atomic mass of the metal is 4
S<l. Approximate atomic mass of an element is 26.89. If its (b) atomic mass of the metal is 8
equivalent mass is 8.9, the exact atomic mass ofthe element is: (c) equivalent mass of the metal is 4
(a) 26.89 (b) 8.9 (c) 17.8 (d) 26.7 (d) equivalent mass of the metal is 8
55. When an element forms an oxide in which oxygen is 20% of 68. Compounds with identical crystal structure and analogous
the oxide by mass, the equivalent mass ofthe element will be: chemical formula are called:
(a) 32 (b) AO (c) 60 (d) 128 (a) isomers (b) isotones
56. 0.32 g of a metal gave on treatment with an acid 112 mL of (c) allotropes (d) isomorphous
,/ hydrogen at NIP. Calculate equivalent mass of the metal: 69. Which pair of the following substances is said to be
,. I[AMtJ'(Eilgg.. ) lOlO] isomorphous?
(~) 58 (b 32 (c) 11.2 (d) 24 (a) White vitriol and blue vitriol
[Hint.: Mass of metal that displaces 11200 mL hydrogen at STP (b) Epsom salt and Glauber's salt
wHl b-o it~ equivalent mass. (c) Blue vitriol and Glauber's salt
:. Equi"~Jent mass of metal = 0.32 x 11200 = 32] (d) White vitriol and epsom salt
112
BASIC PRINCIPLES 51
c mass of chlorine is 35.5. It has two isotopes of atomic (c) 18.1 >.< 1023 molecules of CO2
~5 and 37. The percentage o~}~!#lyier~sotope is: (d) 3 g-atoms of CO2
, (b) 15 (c) 20'" (d) 25 85. Which among the following is the heaviest?
c mass of boron is 10.81. It has two isotopes with 80% IPMT (Kerala) 20061
)% abundance respectively. The atomic mass of the (a) One mole of oxygen
~ having 80% abundance is 11.01. The atomic mass of (b) One molecule of sulphur trioxide
ler isotope is: ( c) 100 amu of uranium
.81 (b) 11.01 (c) 10m (d) 21.82 (d) 10 moles of hydrogen
)f chlorine combines with a metal giving III g of its (e) 44 g of carbon dioxide
Ie. The chloride is isomorphous with MgCl2 . 6H2 0. The 86. The largest number of molecules is in:
; mass of the metal is: • (a) 28 gofCO (b) 46 gofC2H sOl:;l
(b) 30 (e) 40 (d) 69 (c) 36 g ofHzO (d) 54 g ofN2 0 s .
lpour density of a volatile chloride of a metal is 59.5 and 87. Which of the following has the smallest number of molecules?
Lllvalent mass ofthe metal is 24. The atomic mass of the (a) 22.4 x 103 mL of CO2 gas
1t will be:
(b) 22 g of CO2 gas
(b) 48 (c) 24 (d) 12
(c) 11.2 litre of CO2 gas
xide of an element possesses the molecular formula,
(d) 0.1 mole of CO 2 gas
. If the equivalent mass of the metal is 9, the atomic
)f the metal will be: 88. Thetmmber of grams of H2 S04 present in 0.25 mole of H2 S04
(b) 18 (c) 9 (d) 4.5 is:
lolecular mass of a compound having formula MO and (a) 0.245 (b) 2.45 (c) 24.5 (d) 49.0
tlent mass 20 is: 89. Number of molecules in I litre of oxygen at NTP is:
, (b) 40 (c) 28 (d) 20 3 3
(al 6.02 x ItY (b) 6.02x 102
~sity of air is 0.001293 g mL- 1• Its vapour density is: 32 22.4
·3 (b) 14.3 (c) 1.43 (d) 0.143
Divide with the density of hydrogen, i.e., 0.00009 g (c) 32 x 22.4 (d) 32
22.4
90. 4-.6 x I (iI~'atoms of an element weigh 13.8 g. The atomic mass
,f a substance when vaporised occupy a volume of 5.6
ofthe. element is:
. NTP. The molecular mass of the substance will be:
(a) 190 (b) 180 (c) 34.4 (d) 10.4
(b) 2M (c) 3M (d) 4M
apour densities of two gases'are in the ratio of I : 3.
molecular masses are in the ratio.oJ:
.3 (p) I : 2 (c) 2: 3 < (d) 3: 1
ganic compound on analysis was found to contain (c) 3 x 6.02 X 1023 (d) 4 x 6.02 X 1023
Vo of sulphur. The molecular mass of the 'eompound, if its 92. The total number of protons in 109 of calcium carbonate is:
llie contains. two sulphur atoms, is: (CPMT1992)
10 (b) 2000 (a) 3.01 i5x 1024 (b) l5057 x loZ4
1000 (d) 200000 "
tomic mass of an element is p. If valency is 3, the (cl. 2:0478 x. 1024 (4) 4.0956 x loZ4
r density of the volatile chloride will be: '" - 93. 19.7 kg of gold was recovered from a smuggler. The atoms of
,.75 (b) 6.675 (c) 667.5 - (d) 81 gold recovered are: (Au = 197) .
msity of a gas 'A' is three times that of a gas 'B'. If the . (a) 100 (b) 6.02 x 1023
lliar mass of A is M, the molecular mass of B is:
(c) 6.02 X loZ4 (d) 6.02 x loZ5
(b) M/3 - (c).fjM (d) M
94 .. The molecular mass of CO2 is 44 amu and Avogadro's number -
.fj is 6.02 x I oZ3. Therefore, the mass of one molecule of cn, is:
r density of a volatile substance is 4 in comparison to (a) '7.31 x 10-23 (b) 3.65 x 10-23 .-
le (Cl4 1~ Its molecular mass will be:
(b) 2 »(c) 64 (d) 128 (c) lOI X 10-23 (d) 2.01 x 10-23
e the wrong statement: 95. Equal volumes of different gases at any definite temperature
nole means 6.02 x 1023 particles and pressure have:
olar mass is mass of one molecule (a) equal weights (b) equal masses
olar mass is mass of one mole of a substance (c) equal densities (d) equal nlunb(=r of !1]ok.,;
olar mass is molecular mass expressed in grams 96. A gaseous mixture contains oxygen and nitrc)fycil in the ,.,,!iu vf
lIe of CO2 contains: (MLNR 1990; CBSE 1993) I : 4 by mass. Therefore, the ratio of their l:!!miYcr
Vl "'-" 1 n23 ..............-"" ,....c r-" molecules is:
G.R. B. PHYSICAL CHEMISTRY FOR COMPETITIONS,
m will react with ethyl alcohol to give: 110. A compound of aluminium and chlorine is composed of9.0 g
,of hydrogen (b) one mole of oxygen Al for every 35.5 g of chlorine. The empirical formula of the
'ofNaOH, (d) 1/2 mole of hydrogen compound is:
an atom of carbon is: (a) AICI (b) AICl 3 (c) AICl 2 (d) AICl 4
(b) 1.99 x 10-23 g 111. The haemoglobin from red corpuscles of most marnmels
contain approxImately 0.33% of iron by mass. The molecular
(d) 1.99 x 1023 g
mass of haemoglobin is 67200. The number of iron atoms in
of moles of Hz in 0.224 litre of hydrogen gas at each molecule of haemoglobin is:
'(MLNR 1994) (a) 4 (b) 3 (c) 2 (d) 1
(b) 0.1 (c) 0.01 (d) 0.001 112. The percentage ofP20 s in diarnmonium hydrogen phosphate,
:Jf 1 g helium at NTPin litres is: [(NH4 )2 HP04 ] is: (CPMT 1992)
(b) 0.56 (c) 2.8 (d) 0.28 (a) 23.48 (b) 46.96
24
s to contain 1.0 x 10 particles, the mass of ope (c) 53.78 (d) 71.00
;en is: 113. The percentage of nitrogen in urea (NH2CONH2), is: '
(b) 5.32 g (a) 38.4 (b) 46.6 (c) 59.1 (d) 61.3
(d) 16:0 g 114. The chloride of a metal has the formula MCI 3 . The formula of
)f 1 litre capacity each are separately filled with
°
[e, 02 and 3 , At the same temperature and '
ratio of the number of atoms of th.ese gases
its phosphate is:
(a) M 2P04 ' (b) MP04 (c) M 3P0 4 (d) M(P04 )2
115. 10 g of hydrofluoric acid gas occupies 5.6 litre of volume at
ferent flasks would be:
NTP. If, the empirical formula of the gas is HF, then its
1 (b)2:1:2:3 molecular formula will be: (At., mass ofF = 19)
3 (d) 3 : 2: 2 : 1
(a) HF (b) H3F3
mperatirre and pressure, two flasks of equal
filled with H2 and'SOz separately. Particles which (c) H2F2 (d) H4F4
10
lUmber, in the two flaskes are: [Hint: Molecular mass - x 22.4 =40]
(b) electrons 5.6
:s (d) neutrons 116. Calcium pyrophosphate is represented by the formul.a
a mixture of 6.02x 1023 oxygen atoms and Ca ZP20 7 . The molecular formula of ferric pyrophosphate is:
ydrogen molecules at NTP is: (a) Fe 2P2 0 7 (b) FePZ0 7
(b) 33.6 litre (c) Fe(P20 7 )3 (d) Fe4(PZ07)3
(d) 22.4 litre 117. The percentage of available chlorine in a sample of bleaching
of molecules' present in a drop of water, if its ' powder, CaOClz ·2H2O, is:
)5mL, are: (a) 30 (b) 50 '(c) 43.5 (d) 59.9
,21
(b) 1.66 x102 2
n 8. SI unit of energy is:
~3 (d) 1.66x 1024 (a) kg m 2 S-2 (b) kg m- I S2
was 'found tocolltain nitrogen and oxygen in the (c) kg m 2 S-I (d) kg m 2 8 2
n 28 g and oxygen 80 g, The formula ()f the
119. One ~cro gram is equal to:
(a) 10:3 g , (b) 103 g (c) 106 g (d) 10-6 g
(b) N 2 0 3
(d) N;04 " 120. Significant figures in 0.00051 are:
t formula of a compound cOQ.tain"ing sb% of W5 ~3 002 ~4
At. mass = 10) and 50% of the element.y. (At. 121. ' The number of significant figures in 6.02 xloZ 3 is:
;: {(IIlI" 1994J
(a) 23 (b) 3 (c) 4 (d) 26
(b) X 2Y
(d) X 2Y 3 " , 122. Express 0:006006 into scientific notation in three significant
digits:
til X (At. mass 75) and Y (A!. mass = 16),
ivea compound having 75.8% of X. The f~rmula
(a) 6.01x io-
3 (b) 6.006 x 10-3
lund i s : ( M L N R 1991) (~) 6.00 x 10":3 (d) 6.0 x 10-3
(by X 2 Y 123. The proper value of significant figures in 38:0+ 0.003;5
(d) X 2Y 3
+ 0.00003 is:
a certaincornpound was found to contain iodine
(a) 38 (b) 38.0035
in the ratio of 254': 80. The formula of the
: (At. mass ofl = 127,0 = 16) (c) 38.00353' (d) 38.0
(b) 12 0 124. Which of the following is the correct unit for measuring
nuclear radii?
(d) 120s
(a) Micron " (b) Millimetre
BASIC PRINCIPLES 53
~r to prepare 1 litre normal solution of KMn0 4, how 137. The density of a liquid is 1:2 glmL. There are 35 drops in 2
~ams of KMn04 are required if the solution is to be mL. The number of molecules in one drop (m.lar mass of
I acid medium for oxidation? (PET (MP) 2002) liquid = 70) is:
8g (b) 31.6 g (c) 62 g (d) 790 g (a) (1.21 NA
.
(b)(~J·
35
2 NA
'
!U1 oxide of a metal is converted to chloride completely . 35)
rields 5 g chloride. The equivalent weight of metal is: L2 .
(c)--z NA (d) 1.2NA
(KCET2002) (35)
.25 (b) 3.325 (c) 12 (d) 20 13lt A sample of PCI 3 contains iA mole;' the substance. How
:rofatoms 558.5 g Fe (At. wt. ofFe= 55.85 g morl) is: many atoms are there in the sample? IeEE (KeraJa) 20.04/
(AlEEE 20.0.2.) (a) 4 (b) 5/ 4'
ice that in 60 g carbon (b) 6.023 x lcY 3 (c) 8.431 X 1023 (d) ,572 x IcY
lfthat of8 g He (d) 558.5 x 6.023 x 1023 (e) 2A09 x lcY4
efix 1018 is: [MEE (Kerala) 2062J . .
139. The eqUivalent weigh
. N OH J;Yi"O ~
. NaH PO + H is:
2 4 2
°
I of ,nosphoric acid H 3P0 4 in the
~a (b) exa (c) kilo (d) nano reaction, a + 4 lBHU (Pre.~ 20051
:ga (b) 49 (c) 25 (d) 9&
mce in density is the basis of: LMEE (Kerala) 20.02) (all? Only one hydrogen ofH 3P04 is replaced, i.e,its basicity
ra filtration (b) molecular sieving ='1
. 1· MoleCular mass
wity separation (d) molecular attraction EqUlva ent mass = 98 = 98]
)mic absorption Ie Ids Basicity I
' 1 , j
:ctlVe of the source, pure sample of water ai:;'en. This is 140. 5.6 g of an organic compound on burning with excess of
-0 mass of oxygen and 11.11 % mass of)\''Kerala) 20.0.21 oxygen gave 17.6 g of CO2 and 7.2 g H20. The organic
led by the law of:
",.anJtrcompos1't'IOn compound is: [PET (Kcrala) 200.61
[lservation of mass .W)constant volume (a) C6H6 (b) C4Hs (c) C3HS (d) CH3 COOH
lItiple proportion (e) CH3CHO
141. The decomposition of a certain mass of CaC03 gave 11.2 dm3
y-Lussac~~l~electron weigh one kilogram? . of CO 2 gas at STP. The mass of KOH required to completely
lanv r [IIT(S.creening) 20.021 neutralise the gas i s : · (KCET 2006)
3 x 1023 (b) 1 x 1031 (a) 56 g (b) 28 g (c) 42 g (d) 20 g
9.108 3 1
[Hint: 11.2 dm of CO 2 at STP - mole CO 2
:3 X 1054 I 2
(d) X 108
9.108 9.1 08 x 6.023 KOH + CO 2 ~ KHC0 3
he numbers: 161 cm; 0.161 cm; 0.0161 cm. The
of significant figure for three numbers is:
~ mole CO2 will be neutrali)'ed by ~ mole KOH, i.e, 28 g KOR]
[AFMC CPune) 200.2l 142. How many moles of magnesium phosphate, Mg 3 (P04 )2' will
,5 (b) 3,3,3 (c) 3,3,4 (d) 3,4,4 contain 0.25 mole of oxygen atoms? (AIEE.E 2006:)
me of the following laws directly explains the law of (a) 0.02 (b) 3.125 x 10-2
Ition of mass? (AFMC 20(2)
(c) 1.25 X 10-2 (d) 2.5 x 10-2
d's rule (b) Dalton's law
[Hint:
gadro's law (d) Berzelius hypothesis .: 8 mole oxygen atoms are present in 1 mole Mg3 (P04 )2
las maximum number of atoms?
[Ill' (S.creening) 20031 :.0.25 mole oxygen atoms will be present in.!. x 0.25 mole
· 8 ·
. C(12) (b) 56 g Fe(56) Mjffi (PO 4}z' i. e., 3.125 x 10-2 mole Mg3 (PO 4hJ
. AI(27) (d) 108 g Ag(l08) 143. An element, X has the following isotopic composition,
lch of sulphur is present in an organic compound, if 200 X: 90%
:>mpound gave 1.158 g ofBaS04 on analysis?
199 X :8%
[PET (Kerala) 20.651
(b) 15% (c) 20% (d) 25% 202X :2%
the weighted average atomic mass of the naturally- occurring
_of H2 and 20 mL of O2 react to form water, what is element 'X' is closest to : ICDSE (Mt'd.) 2007)
e end oftl:!e reaction? (AFMC 2005) (a) 201 amu (b) 202 amu (c) 199 amu (d) 200amu
G.R:B. PHYSICAL CHEMISTRY FOR COMPETITIONS
age atomic mass of 149. Common salt obtained from sea-water contains 95% NaCI by
8 x 199 ] + [ ~ x 202 ]
mass. The approximate number of molecules present in 109
x 200 ] + [ salt is: (DPMT 2009)
100 100
) amu "" 200 amu] (a) 1021 (b)1022
statement for 14 g CO is : (VMMC2007) ~I~ OOI~
is 2.24 L at NTP [Hint: Mass ofNaCI in 10 g salt:;:: 10 x ~ ::= 9.5 g
1 . 100
pOis to mole of CO
2 Number of molecules ofNael 9.5 x 6.023 x 1023
pondto same mole of CO and N2 58.5
22 23
3
'1" ....nds 3.01 x 102 molecules of CO = 9.78 x 10 "" 10 ]
r of hydi . 150. 109 hydrogen and 64 g oxygen were filled in a steel vessel
) h' h hll;en atoms present III 25.6 g of sucrose
w IC a\ molar mass of 342.3 g, is: and exploded. Amount of water produced in this reaction will
be: [CBSE (PMT) 20091
(VITEEE 2008)
. (a) 3 mol (b) 4 mol
(b\9.91x 1023
(c) 1 mol (d) 2 mol
(d) 44 ,- ..,,23
. 10 64
nber ot mOil;;" vr ~'-""Y"'<;e [Hmt : I1H = - :;:: 5 110 2 - = 2
Mass 4_.
2 2 32
:;:: -----,c.'-
Molar mass 342.3 2H2 + 02 ~ 2HzO
0.075 Case I : If H2 is completely consumed then:
101es of hydrogen atom = 0.075 x 22 nH 0 5 mol
2
toms of hydrogen 0.075 x 22 x 6.023 x 1023 ~''le II: If0 2 is completely consumed then
= 9:?x 1023 ] . htl~ 2
~-:-x2 4 mol
Ipied by one molecule ~f• • (-density = 1 glcm 3) Since, O 2 gives It.~
[CBSE-PMT (Pre.) 2008] hence, it is limiting an!9unt of product on complete consumption
3 cm
3 (b) 5.5 x 10- 23 cm3 equal to 4.] . "'er of moles of water formed will be
3 cm
3
(d) 6.023 x 10- 23 cm 3 151. An organic compound made ot '-.
nitrogen. What will be its molecularYmmd N contains 20%
18 one nitrogen atom in it? ijh£ontains only
iSS of one molecule = . 23 g
. 6.023 x 10 (a) 70 (b) 140 -"Il) 2009]
= 2.98 X 10- 23 g (c) 100 (d) 65
23
M 2.98x 10- [Hint: % N '" Mass of nitrogen x 100
>fie molecule = - - '- = cm 3
Density Molecular mass
"" 3 x 10- 23 cm 3 ] 20 =.!.± x 100
~cn contains as many atoms as in: (KCET 2008)
m=70]
lydrogen (b) 5 g of hydrogen
152. Given that the abundances of isotopes 54 Fe, 56Fe and 57Fe are
Iydrogen (d) I g of hydrogen
5%,90% and 5% respectively, the atomic mass of Fe is:
s consists oruniform cylindrical particles of 1:50A , (IlT 2009)
and 5000A long. The specific volume of virus is
lfthe virus is considered to bea single particle, its (a) 55.85 u (b) 55.95 u
lass is: (c) 55.75 u (d) 56.05 u
)7 g mol-1 (b) 7.90 x 107 g mor I [Hint:AtomicrnassofFe= 5 x54+ 90 x56+ 5 x57
)7 g mol-I (d) 9.70 x 107 g mol-I 100 100 100
55.95 amu]
lme of single virus = n?h 153. The number of atoms in 0.1 mol triatomic gas is:
= 3.14 x (75 x 1O- 8 i x (5000 x 10- 8 ) (N A = 6.02x 1023 mol-I) ICBSE (PMT) 2010]
8.836 x 10- 17
cm 3 (a) 6.026x 1022 (b) 1.806x 1023
. I .' Volmne 8.836 X 10- 17 cm 3 (c) 3.6x 1023 (d) 1.8x 1022
mg e ViruS =
, Specific volmne 0.75 Ig [Hint: No. of atoms = O.lx 3 x6.02x 1023
16
1.178xlO- g :;:: 1. 806 X 1023 ]
ss of virus 1.178 x 10- 16 x 6.023 X 10 23
questions given below may have more 4. Select the numbers with same significant figures:
than one correct answers (a) 6.02 x 1023 (b) 0.25
(c) 6.60 x 10- 34 (d) 1.50
'the following relationships are wrong?
3 S, Which are isomorphic to each other?
l"" 0.1 har (b) 1 litre = 1 r.m (a) CuS04·5HP· (b) ZnS04·7HzO
0.239 cal (d) 1 eV;-:1.11 x 10--4 J (c) FeS04·7H20 (d) FeS04·8H20
If the following numbers have same significant 6. 11.2 L of a gas at STP weighs 14 g. The gas could be:
(a) N2 (b) CO
) (b) 0.60 ~c) 6.0 (d) 60 (c) NO z (d) NzO
fthe following }).ive the same mass? 7, 8 g O2 has same number of molecules as that in:
oole of 02 gas (a) 14 g CO (b) 7 g CO
nole of SC?2 gas (c) 11 g CO2 (d) 22 g COz
3 x 1022 molecules of S02 gas
4 x 1023 molecules of0 2 gas
e' QUESTIONS :: :
: 1
t
\
3. (a) . 4. (d) 5. (a) 6. (e) 7. (d) 8. (b)
1. (e) 12. (e) 13. (a) \4. (d) 15. (d) 16. (a) \
9. (a) 20. (b) 21. (b) 22. l\l) 23. (d) 24. (a) 1
7. (b) 18. (d) 29. (c) 30. (a) J
31. (d) 32. (b)
5. (a) 36. (a) 37. (b) 38. (a) 39. (b) 40. (e)
3. (b) 44. (d) 45. (d) 46. (ti) 47. (e) 48. (b) \
t
1. (d) 52. (b) . 53. (c) 54. (d) 55. (a) 56. (b) i
9. (a) 60. (b) 61. (b) 62. (e) 63. (b) 64. (a)
7. (e) 68. (d) 69. (d) 70. (d) 71. (e) 72. (e)
5. (a) 76. (b) 77. (d) 78. (a) 79. (d) 80. (a)
3. (b) 84, (a) 85. <e) 86. (e) 87. (d) 88. (e)
1. (d) 92. (a) 93. (d) 94. (a) 95. (d) 96. (e)
9, (e) 100. (a) 101. (a) l'6't,(b) 103. (c) 104. (d)
7. (b) 108. (d) 109. (d) 110. (b) 111..(a) 112. (e)
5. (e) 116. (d) 117. (e) 118. (a) ,"1.Q, (d) l~o.(e)
3. (d) 124. (d) 125. (b) 126. (a) 127. (a) 12K.:(b)
."
L (d) 132. (b) 133. (e) 134. (a) 135. (e) ,"ll.· (d)
). (d) 140. (b) 141. (b) 142. (b) 143.• (d) ·'144. (a)
7. (b) 148. (a) 149. (e) 150. (b) 151 •. (a) 152. (b)
.: 0.5 g Se is present in 100 g enzyme. 10. Ifl021 molecules are removed from 100 mg CO 2 , then number
'II be present In
. -100' x 78.4
. of moles of CO 2 left are:
~ Se WI g enzyme
0.5 (a) 6. lOx. 10-4 (b) 2.8x 10-3 .
= 15680amu (c) 2.28x 10-3 (d) 1.36 x 10-2
= ~.568x 10 amu]
4
[Hint: Number of molecules in 100 mg CO 2
mber of moles of a gas in I m 3 of volume at NTP is: Mass x 6.023 x 1023
(b) 0.446 (c) 1.464 (d) 44.6 Molar mass
1m 3 1000 L
= 0.1 x 6.023 x10 23
1000 44
nber ofnnles =--= 44.6]
22,4 = 1.368 X 1021
:d number of electrons present in 18 mL water (density Molecules remaining = 1.368 x 1021 1021 0.368 X 1021
) is:
21
:3x 1023 (b) 6.023 x 1024 ..
N urnb er 0 f mo Ies remammg
0.368xl0
= ---~
3x 1.025 (d) 6.023 x 1021 6.023 x
'.
\
\
on one gram ion of Al 3+ ion is: LHint: In the isotope I~C: Number of protons 6
1
: e coulomb (b) - x NA x e coulomb Number of neutrons 8
3
New atomic mass will be 2 x 6 + ~ x 8 16
ecoulomb (d) 3 x NA x e coulomb 2
. 16-14 .
3
: gram ion of A1 + means one mole ion of AI 3+. % Increase In mass = x 100 = 14.28% ]
14· .
mole A1 + 3
3 x e x ~ coulomb.]
17. The mass and charge of I mole electrons will be:
lass ofNzO as well as CO2 is 44 g mol-I. At 25°C (a) I kg; 96500 C (b) 0.55 mg; 96500 C
:essure, 1 L N 2 0 contains n molecules of gas. The (c) 1.55 mg; 96500 C (d) 5.5 mg; 96500 C
~02 molecules in 2 L under same conditions will
18. The simplest formula of the compound containing 50% X
(atomic mass 10 amu) and 50% Y (atomic mass 20 amu) is: .
(b) 2n (a)XYz (b)X 2Y (C)X 2Y3 (d)XY-
[Hint: Element <>4 ""mmle ratio Simplest ratio
. is dissolved in 1 L water. The number of ions of
in 1 mL of this solution will be: 50 5
X 50 =5 -=2
19 22 20 10 2.5
1 (b) l2 x 10 (c) l2 X 1020 (4) o.v2 X 10
nber of mol.,,, of !'laCI 50 = 2.5 2.5
Y 50
Mass = 5.85 = 0.1 20 2.5
Molar mass 58.5
Formula = X 2Y]
lUS (Na + + cr )in 1 L 19. Rest mass of 1 mole neutrons (mn ::: 1.675 X 10-27 kg) is:
(a) 1.8 X 10-3 kg (b) l.008 x 10-4 kg
= 2 x 0.1 x 6.023 x 1023
(c) 1.08 X 10-3 kg (d) 1.008 x 10-3 kg
= 12.046 X 1022
[Hint: .Mass of 1 mole neutrons
12.046 X 1022 1.675 x 10-27 X 6.023 X 1023
)TIS in 1 mL L2x 1020]
1000 = 1.008 X 3
10- kg]
de has the formula X 20 3 '} t can be reduced by 20. Loschmidt number is the number of:
give free metal and water. 0.1596 g of metal oxide (a) molecules present in I mL of a gas at STP
g of hydrogen for complete reduction. The atomic (b) molecules present in 1 gram mole of a gas at STP
al in amu is:
(c) atoms present in 1 mL of a gas at STP
(b) 155.8 (c) 5.58 (d) 55.8
(d) atoms present in I gram mole of a gas at STP
P3 + 3H z ----7 2X + 3HzO 21. Which of the following statements is incorrect?
ml 31001
48) g 6g . 108 -23
(a) One gram mole of sIlver equals - - x 10 g
i2 is required by 0.1596 g oxide 6.023
ill be required by 159.6 g oxide (b) One mole of CH4 and 17 g of NH3 at NTP occupy same
volume
2a + 48 = 159-./5
(c) One mole Ag weighs more than t~at o~~o moles o~Ca
a = 55.8
(d) One gram mole of CO 2 is 6.023 x loZ times heaVier than
tomic mass of metal M. ] one molecule of CO2 .
(PH3 ) decomposes to produce vapours of One atom of an element 'X' weighs 6.664 x 10-23 gm. The
and H2 gas. What will be the change in volume number of gram atoms in 40 kg of it is:
LL of phosphine is decomposed? (a) 10 (b) 100 (c) 10000 (d) 1000
(b) 500 mL The density of a liquid is 1.2 g/mL. There are 35 drops in 2
(d) 500 mL mL. The number of molecules in I drop is (molecular weight
PH 3(g) ----7 Pig) + 6H2(g) ofliquid 70):
4 mL
10 mL
----7
----7
1 mL
100
4
6 mL
~ x 100
4
(a) ~.~ NA (b) C5Y
l
NA
[Hint: Na2S04·nH20"
nolecules in one drop = L22 x NA ]
(35) Molar mass (l42+lSn)
ne of a liquid will contain 4 mole? Molar mass of Mass of water == 12.6 x (142 + ISn)
oand its density is 1.4 glmL: ' 26.S
(b) 1.6 L (c) 0.8 L (d) 4.8 x l(J23 L 126'
18n'" - ' x (142+ 18n)
t x L liquid contain 4 mole of it. 26.8
n 7]
Mass
.ber of moles 29. Consider the following data:
Molar mass
Element Atomic weight
4 = x x 1000 x 1.4 A 12.01
. 2S0
B 35.5
x = 4 x 2S0 '" O.S L]
1.4 x 1000 A and B combine to form a new substance X. If 4 moles of B
combine with 1 mole of A to give I mole of X, then the weight
ratio of Fe 2+ to Fe 3+ in a mixture of FeS04 and
of I mole of X is:
having equal number of sulphate ions in both
(a) 154 g (b) 74 g (c) 47.S g (d) 160 g
I ferric sulphates is:
30. How many moles ofNa + ions are in 20 mi of 0.4 MNa3P04?
(b) 3: 2
(a) 0.008 . (b) 0.024 (c) 0.05 (d) 0.20
(d) none of these
, MV 0.4 x 20
S04 ~ Fe2+ + SO~- [Hint: No. of moles ofNa 3P0 4 =
1000 1000
04)3 ~ 2Fe3+ + 3S0~- = 0.008
Number of moles ofNa+ '" 3 x Number of moles ofNa 3P04
mole SO~- ions are furnished by both FeS0 4 and
3 x 0.008 = 0.024]
31. The element whose one atom has mass ofl 0.86 x 10-26 kg is:
moles of Fez+ "'x
(a) boron (b) calcium (c) silver (d) zinc
moles ofFe3+ =2 x 32. An electric discharge is passed through a mixture containing
3 50 cc of 02 and 50 cc of Hz. The volume of the gases formed
2 (i) at room temperature, (ii) at 110°C will be:
: Fe3+ ::x:-x
3 (a) (i) 25 cc (ii) 50 cc (b) (i) 50 cc (ii) 75 cc
= 3: 2]
(c) (i) 25 cc (ii) 75 c c ( d ) (i) 75 cc (ii) 75 cc
[Hint: 2H 2 (g) + 02(g) ~ 2Hp
f electrons present in 3.6 rng of N~ are:
(b) 1.2 x Hro (c) 1.2 x 1022 (d)2x 10- 50 cc Hz will combine with 25 cc 02 to form 50 cc Hp
3
Q21
:. 02 left '" 25 cc
umber of electrons in one ion ofNH! 10
At room temperature, HP will be in liquid state but at llO°.C, it
'ions in 3.6 mg NH! will be gaseous. Thus, volume of gases at 25°C and 110°C will be
3 25 cc and 75 cc respectively.]
3.6x 10- x 6.023 X 1023 ", 1.2x 1020 33. The mass of carbon p(esent in 0.5 mole ofK 4[Fe(CN)6] is:
IS
(a) 1.8 g (b) 18 g (c) 3.6 g (d) 36 g
ber lh,lectrons in 3.6 mg NH~ = 1.2 x 1020 x J/J [Hint: 1 mole of~[Fe(CN~ ]contains 6 mole carbon, i.e., 72 g
=1.2xl02 11 carbon,]
:tion 4A + 2B + 3c -----7 A 4 B 2C 3 , what will be the 34. Caffeine has a molecular weight of 194. If it contains 28.9%
. moles of product formed, starting from one mole of by mass of nitrogen, number of atoms of nitrogen in one
Ie of Band 0,72 mole ofC? : molecule of caffeine is:
(b) 0.3 (c) (d) 2.32 0.14 004 ~6 ~2 W3
A + 2B +3C
001 0,6 mol 0,72 !lJl1
:.......-? A4 B2C 3 [Hint: Mass of nitrogen in 194 amu caffeine 2S.9 x 194
.100
~ent case, reactant 'C' wili be the limiting reactant = 56amu
will give least amount of product on being completely :. One molecule of caffeine will contain 4 atoms of nitrogen.]
35. Chlorine can be prepared by reacting HCI with Mn02' The
~ives I mol product, reaction is represented by the equation,
>,
'C' will give 0.24 mol of product.] Mn02(s) + 4HCI(aq.) ~ CI 2 (g)+ MnCI 2 (aq,) + 2H 20(l)
of Na 2 S04'nH2 0 contains 12.6 gm of water. The Assuming that the reaction goes to completion, what mass of
, is: conc. HCI solution (36% HCI by mass) is needed to produce 2.5 g
- - _....... _ -
60 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
36. What is the mass per cent of oxygen in Al2(S04k18H20? x = Atomic mass of metal
The molar mass ofthis substance is 666.43 g/mol : .: 0.006 g Hz reduces 0.1596 g M 20 3
(a) 9.60 (b) 28.8 (c) 43.2 (d) 72
:. 6 g Hz will reduce 0.1596 x 6 gMz03 = 159.6Mz0 3
37. 0.25 g of an element 'M' reacts with excess fluorine to produce 0.006
0.547 g ofthe hexafluoride MF6 • What is the element? 2x + 48 = 159.6
(a) Cr (b) Mo (c) S e d ) Te 2x = 111.6
38. How many electrons are present in 2 x 10-3 moles of 1~02-? x=55.8].
(a) 1.2 x 102 1 (b)9.6x 1021 (c)1.2x 1022 (d) 1.9 x 1022 46. In a compound ofm~lecular formula AmBn:
39. Fluorine reacts with uranium to form UF6 . (a) number of equivalents of A, B 'and AmBn are same
U(s) + 3F2 (g} UF6 (g) (b) number ofmru..es of A, Band AmBn are same
How many fluorine molecul~s are required to produce 2 mg of (c) m x moles 01 A n x moles of B = (m + n) X moles of
UF6 from an excess of uranium? The molar mass ofUF6 is 352 AmBn
(d) n x moles of A = m x moles of B = (m + n) x moles of
g mol-I.
AmBn
(a) 3.4 x 101 8 (b) I X 1019 (c) 2 X 1019 , (d) 3.4 x 102 1 47. 4.4 g of CO 2 and 2.24 litre of H2 at STP are mixed in a
40. What is the formula of a substance with mass percentages of container. The total number of molecules present in the
°
35.79% for S, 62.92% for and 1.13% for H? container will be:
(a) H ZS03 (b) H 2 S04 (c) HiSz07 (d) H 2 S2 0 g (a) 6.02"2 x 1023 (b) 12044 x 1023
41. In 1811, Avogadro calculated the formula of camphor by (c) 6.023 X 1026 . (d) 6.023 x 10M
means of elemental chemical analysis and by measuring the
density of its vapour. Avogadro found the density to be 3.84 48. A partiillly dried clay mineral contains 8% water. The original
gIL when he made the. measurement at 210°C at 1 atrn sample contained 12% water and 45% silica. The % of silica in
pressure. Which of the following is the correct formula of the partially dried sample is nearly:
camphor? (a) ~O% (b) 49%
(a) CIO H140 (b) CIO HI6 0 (c) ClO H I6 0 2 (d) C IO H18 0 (c) 55% (d) 47%
(e) None ofthese [Hint: Initial stage: Clay Silica Water
[Hint: Pm = dRT 43% 45% 12%
Final stage: (92 - x) x 8%
m = dRT = 3.84 x 0.0821 x 483 = 152.27
P 1 Ratio of silica and clay will remain constant, before and after
drying.
:. C IOH IIJ will be the correct formula.]
45 x
42. A quantity of aluminium has a mass of 54 g. What is the mass
of same number of magnesium atoms? 43 92-x
(a) 12.1 g (b)24.3 g (c) 48.6 g (d) 97.2 g x == 47%]
43. When 1 L of CO2 is heated with graphite, the vQlume of the 49. Which ofthe following is isomorphous with MgS04 ·7H20?
gases collected is 1.5 L. Calculate the number of moles of CO (a) Green vitriol (b) Blue vitriol
produced at STP: . (c) Red vitriol (d) Vitriol of mass
1 28 1 (d) 14 50, In the reaction;
(a) 11.2 (b) 22.4 (c) 22.4 22.4 I '-7 2NO
CO + 2 O 2 -------7 COz; N2 + Ory
[Hint: cO2 (g)+ C(s) -------7 2CO(g)
I-x 2x 10 ~ of mixture containing ('~<oon monoxide and nitro~en
Total volume = 1 - x + 2X = 1 + x 1.5 requn-ed 7 mL oxygen to form CO~ and NO, on combustIOn.
x = 0.5 L The volume 9fN2 in the mixture will be:
.. Volume of CO = 2 x 0.5 = 1 L (a) 7/2 mL t'0) 1712 mL (c) 4 mL (d) 7 mL
1
Nwnber of moles of CO = - - ] [Hillt: CO(g) +.~ O,(g) ---t CO 2(g)
22.4 x ·2-
xl2
44. Which of the following has greatest number of atoms?
(a) 1 g of butane (C4 H IO ) (b) 1 gofhitrogen (Nz) y y
(c) 1 g of silver (Ag) (d) Ig of water (H2 0) x + y= 10 ... (i)
°
45. A metal oxide has the formuia M 2 3' It can be reduced by Hz
to give free metal and water. 0.1596 g of M 2 0 3 required 6 mg
X
-+ y=7 ... (ii)
2
OfI:I2 for complete reduction. The atomic mass of the metal is:
Solving eqs. (i) and (ii),
(a) 27.9 (b) 79.8 x=-6 . and y=4]
(c) 55.8. (d) 159.8 51. 1.44 g of titanium (Ti) reacted with excess of0 2 and produced
[Hint: M 20 3 + 3H z -------7 2M + 3HzO x. gm of a nonstoichiometric compound Ti 1.440 ! . The value 0 f
. ,
,; (2x + 48) g 6g x is:
I
BASIC PRINCIPLES 61
(b) 1.77 Following questions may bave more tban one correct options:
(d) None of these
1. 1l.2 L of a gas at STP weighs 14 g. The gas could be:
Ile reaction:
(a) NzO (b) N02 (c) N2 (d) CO
Ti +02 ~ Til.4401
2. In which of the following pairs do 1 g of each have an equal
101es of titanium = Number of moles ofTil.440] number of molecules? .
1.44 x
(a) N 20 and CO (b) N2 and C30 Z
48 48 x 1.44 + 16
(c) N2 and CO (d) N 20 imd CO2
x=1.77g] 3. 8 g of oxygen has the same number of molecules as in:
le of75% alcohol by mass (d = 0.8 g/cm 3 ) must be (a) 11 g CO2 (b) 22 g CO2 (c)7 g CO (d) 14 g CO
pare 150 cc of 30% alcohol by mass (d 0.9 4. Which of the following has three significant figures?
(a) 6.02 x 1023 (b) 0.25
(b) 56.25 mL
(c) 6.60 x 10-34 (d) 1.50
(d) 3356mL
V mL of alcohol was used .. 5. 1 mole of I~ N 3- ions contains:
~ x V x 0.8 ~ x 150 x 0.9 (a) 7 x 6.023 X 1023 electrons (b) 7 x 6.023 x 1023 protons
100 100 (c) 7 x 6.023 X 1023 neutrons (d) 14 x 6.023 x 1023 protons
V= 67.5 mL]
6. 1 g atom of nitrogen represents:
(a) 14 g nitrogen
(b) 11.2 litre ofN 2 at NTP
(e) 22.4 litre ofN2 at NTP
(d) 6.023 x 1023 molecules ofN 2
.'.
'fIeIZ4
'ect option
2. (b) 3. (a) 4. (d) 5. (b) 6. (e) 7. (a) 8. (a).
10. (a) 11. (d) 12. (b) 13 .. (c) 14.. (d) 15. (e) 16. (b)
18. (b) 19. (d) 20. (a) 21. (a) . 22. (d) 23. (c) 24. (c)
26. (a) 27. (c) 28. (d) ~9. (a) 30. (b) 31. (d) 32. (e)
34. (a) 35. (b) 36. (d) 31. (b) 38. (e)· 39. (b) 40. (e)
42. (c) 43. (c) 44. (a) 45. (c) ';;46. (a) 47. (1;» 48. (d)
50. (c). 51. (b) 52. (c)
'e than one correct options
2. (e, d) 3. (a,c) 4. (a, c, d) 5. (b,'c) 6. (a)
-.
r4f#eIZ4
t
lrofluoric acid gas occupies 5.6 litres of volume at Molecular formula of metal chloride = MCt,
e empirical fonnula of the gas is HF, then its Molecular inass = [n x 9.02 + n x 35.5J:: 132
fonnula in the gaseous state will be: .. 11::3
(b) H2F2 (c) H3F3 (d) H4F4 :. Atomic mass of metal:: 3 x 9.02 = 27.06 J
, species having different percentage composition of 2. The vapour density of a mixture containing N02 and N2 0 4 is
38.3 at 27°C. The moles ofN0 2 in 100 moles of mixture are:
)OH and C 6H I2 0 6 (b) CH 3 COOH and CzHsOH (a) 33.48 (b) 53.52 (c) 38.3 (d) 76.6
CH 3 and HCOOH (d) CzHsOH and CH 30CH 3 3. At STP, 5.6 litre of a gas weighs 60 g. The vapour density of
°
.od ofNa, C and contains 0.0887 mo(Na, 0.132
2.65 x 1022 atoms of carbon. The empirical fonnula
gas is:
(a) 60 (b) 120 (c) 30 . (d) 240
lpound is: 4. Which of the following two substances have same vapour
(b) Na 3C 50 2 density? .
°
(d) Na O.0887 C 2.65 x 10 22 0.132 (a) Glucose (b) Fructose (c) Sucrose' (d) Starch
5. Let NH4HS(s) is heated in a closed vessel to decompose.
4
loids are extracted from the extracts of the plants
na. Marijuana owes its activity to tetrahydro The vapour density of the mixture will be:
rich contains 70% as many as carbon atoms as (a) equal to that ofNH4 HS
~ and 15 times as many hydrogen atoms as oxygen (b) lesser than thatofNH4 HS
m of tetrahydro cannabinol is 0.00318. (c) greater than that ofNH4 HS
lowing questions: ' (d) cannot be predicted
If mass of the compound is:
mu (b) 314 amu (c) 143 amu (d) 341 amu • Passage 6
:If fonnula of the compound is:
Precision refers to the closeness of a set of values obtained fol'
3002 (b) C21HI403 identical measurement of a quantity. Precision depends on the
460 (d) none of these limitations of measuring devices and the skills with which it is used.
of oxygen atoms in 1 mol of the' tetrahydro However, accuracy refers to the closeness ofa single measurement to
lol is: its true value.
(b)NA The digits ina properly recorded measurement are known as
3
~ = 6.023 X 102 significant figures. These are meaningful digits in a measured or
ge composition of carbon in the compound is: calculated quantity. The greater the number of significant figures in
;% (b) 70.85% (c) 80.25% (d) 59.64% a reported risult. smaller is the uncertainty and greater is the
precision. The zeros at the beginning are not counted. The zeros to
15 the right of a decimal point are counted. In the numbers that do not
contain a decimal point. "trailing" zeros may 01', may not be
~ity 'of a compound is defined as the ratio of mass of a . significant. The purpose ofzeros at the end of a number is to COfJvey
, of gas to the mass of the same volume ofhydrogen the correct range ofuncertainty. .,
tical conditions oftemperature and pressure. . Answer the following questbms:
Mass ofcertain volu~~o[lfas (22.4 L) at STP 1. If repeated measurements give values close to one another, the
Mass ofsame volume ofH 2 gas (22.4 L) at STP number is:
Mw (a) surely precise . (b) surely accurate
=-
2 (c) surely precise and accurate (d) all of these are correct
~lecular: mass of gas =Vapour density x 2 2. The number of significant figures in a measUred number
, is a unitless quantitj; it is unaffected by variation of contains how man;, uncertain {lUmber of digits?
!d pressure. . (a) Zero (b) 1
llowingquestions: . (c) 2 (d) Cannot be predicted
density· ofa metal chloride ;is 66. Its oxide contains 3. In the number,2.4560, there are .5 signifkruitdigits. Which one
tal. The atomic mass of the metal is: ' is the least significant !iigit?
(b) 54 ,; (c) 27.06 (d) 2.086 (a) 2 (b) 4 (c) 0 (d) 6
, Number of equivalents = ~umber of equivalents. 4. if we add 296.2 and 2.256, we get the answer as 298.456 g.
of metal of oxygen The number of significa~t figures in the result are:
53 47 006 ~5 W4 003
-:::::-
E 8 5. In which of the following numbers, all the zeros are not
significant?
E = 9.02
BASIC PRINCIPLES 65
[/I~
Passage 1. 1. (c) 2. (c) 3. (d) 4. (d) 5. (a) 6. (c) 7. (a)
Passage 2. 1. (c) 2. (a, c) 3. (b) 4. (b) 5. (b)
Passage 3. 1. (d) 2. (a, b) 3. (d) 4. (c) 5. (b) 6. (b, c) 7. (a)
Passage 4. 1. (b) 2. (a) . 3. (a) 4. (c)
Pl)ssage 5. 1. (c) 2. (c) 3. (b) 4. (a, b) 5. (b)
Passage 6. 1. (a) .2. (b) 3. (c) 4. (c) 5. (d)
¢ SELF ASS·ESSMENT r~
ASSIGNMENT NO.1
(a) Statement-! is true; statement-2 is true; statement-2 is a 20. 'Match the Column-I with Colunm-I1: '
corre,t explanation for statement-I. Column-I' Column-II
(b) Statement-I is true; statement-2 is true; statement-2 is not (a) N2 (P) 40% carbon by mass
, a correct explanation for statement-I. (bY CO (q) Empirical formula CH20
(c) Statement-lis true; statement-2 is false. (c) C6H1Z Oq (r) Vapour density = 14
(d) Statement-l is false; staternent-2 is true. (d) CH3 COOH (s) 14NA (NA 6.023 X 1023 )
16. State"ment-I: Avogadro's number is a dimensionless quantity. electrons in a mole
Bet:ause 21. Match the Column-I with Colunm-II:
Statement-2: It is a number of atoms or molet:ules in one Column-I Column-II,
gram mole. (a)IL (P)10- 5 N
17. Statement-I: An element has variable equivalent mass.,
Because (b) I J ' (q)0.2389 cal
Statement-2: The valency of element is varia~le. (c) 9.9 x 106 ,erg (r) 10- 3 m3
18. Statement-I: Vapourdensity ofCH4 is halfo(:0i. ' (d) J Dyne ;. (s) 6.25 X l(j8 eV
" 0" " - \
SECTION-IV' "
Matrix-Matching Type Questions
This section contains 3 questions. Each question contains
statement given in two columns which have to be matched.
, Statements (a, b, c and d) in Column~I have to bematchedwith
statements (p, q; r and s) in Colunm-II. The answers to these
questions have to be appropriately bubbled as i1iustrated in the
following example&:, . '
If the correct matches are (a-p,s)(b-q,r); (c-p,q) and (d-s);
then the correctly bubbled 4 x 4 matrix should be as follows:
p q r s
a
G @ (0 e
b
®e0 0
c
G e (0 0
d
® @ (0
"
. I. (a) 2. (c) "
:J..(b) 4. (a) 5. (a) 6. (c) 7. (c) 8. (d)
.' 9. (a) 10. (c) n. (a, d) 12. (a"b, c) 13. (a, b, c) 14; (a, c) 15. (b, c, d) 16. (a)
17. (b) 18. (c) 19. (a) 20., (a-r, s) (b-r, s) (c-p, q) (d-p. q) 21. (a-r) (b-q, s) (c-q) (d-~)
22. (a-p) (b~p, r,s) (c-r){d-q, s)
ATOMIC·STRUCTURE
These particles carrying negative charge were called negatrQns -,J.6622x 10-19 coulomb. Since,
by Thomson. ch~}~~: known, it was, thus, de . rge.
Thename 'negatron' was changed to 'electron' by Stoney. ~Illl of the electron: Th be
(vi) Cathode rays produce X-rays. When these rays fallon a calculated from the value of eI m
material having high atomic mass, new type of penetrating rays
of very small wavelength are emitted which, are calle4 X-rays. e
m -
(vii) These rays affect the photographlc plate. ' elm
(viii) These rays can penetrate through thin foils of solid
= 9.1096 x 10-
28 gor9.1096x
materials and cause ionisation in gases through which they pass.
(ix) The nature of the cathode rays is independent of: This is termed as the rest mass of the electron, i. e. , mass of the
(a) the nature of the cathode and electron when moving with low speed. The mass of a moving
'.. 'c:''J£ (brtheg~s·lh th~Odlscharge tube. electron may be calculated by applying the following formula:,
In 1897, J. J. Thomson determined the elm value
. I' rest mass of electron
M f
(charge/mass) of the electron by studying the deflections of "". 0 movmg e eclron = - ~1- (~)'
cathode rays in electric and magnetic fields. The value of e / m has
been found to be -1.7588 x 108 coulomb/g.
[The path of an electron in an electric field is parabolic, given
as: where v is the velocity of the electron and c is the velocity of light.
eE 2 When v becomes equal to c, mass of the moving electron becomes
y=--x infinity and when the 'velocity of the electron becomes greater
2
2mv than c, mass of the electron becomes imaginary.
where, y = deflection in the path of electron in y-direction
Mass of the el~trgn relative to that of hydrogen atom~
e = charge on electron
E intensity of applied electric field Mass of hydrogen atom = 1.008 amu
m = mass of electron
v velocity of electron
=1.008 x 1.66 x 10-24 g (since 1 amu =1.66 x 10-24 g)
x =distance between two parallel electric plates = 1.673 X 10-24 g
within which electron is moving. 24
The path of an electron in a magnetic field is circular with Mass of hydrogen atom 1.673 x 10-
radius 'r given as: Mass of the electron 9.1 096 x 10-28
mv
r= 1837
eB
, 1
where, m= mass of electron Thus, Mass of an electron =-- x mass of hydrogen atom
v = velocity of electron 1837
e = charge on electron 1.008
B.= intensity qf applied magnetic field 1837
The radius of the path is prQPortional to momentum.] = 0.000549 amu
By performing a series of experiments, Thomson proved that An electron can, thus, be defined as a subatomic particle
whatever be the gas taken in the discharge tube and whatever which carries charge -1.60 x 10-19 coulomb, i.e., one unit
be the material of the electrodes, the value of e / m,ts always
negative charge and has mass 9.1 x 10-28 g, i. e. , _l_th mass of
the same. Electrons are thus common universal constituents of , 1837
all atoms. the hydrogen atom (0.000549 amu).
J.J. Thomson gave following relation to calculate [Millikan's oil drop method is used to determine the charge on
c~arge/mass ratio: an electron by measuring the' terminal velocity of a charged
e E spherical oil drop which is made stationary between two
m= rB2 electrodes on which a very high potential is applied.
where the terms have USual significance given before 61c 11r
. = 1.7588x lOll Ckg- 1
Charge on an electron' q' = E
(VI + v2 )
Electrons are also produced by the action of ultraviolet light or , where, 11 = cQefficient of viscosity of the gas medium
X-rays on a metal and i)'0111 heated filaments. J)-particles emitted 'VI' v 2 termlnal velocities
by radioactive materials are also electrons. E = field strength
The first precise measurement of the charge on an electron V
was made by Robert ,A. Millikan in 1909 by oil drop r =radius of the oil drop = 11 911 J
V2(/ cr)g
experiment. The charge on, the electron was found to be
(f density of oil; cr = density of gas; g gravitational force)]
A roM1CSTRUC!LfFl~ 69
2~3 POSITIVE RAYS-DISCOVERY OF present on the electron. Hence, for a smaller value of e / m, it is
PROTON definite that positive particles possess high mass.
Ox) e / m value is dependent on the nature of the gas taken in
With the discovery of electrons, scientists started looking for
the discharge tube, i. e. ,positive particles are different in different
positively charged particles .which were naturally expected gases.
because matter is electrically neutral under ordinary conditions.
Accurate. measurements of the charge and the mass of the
The first experiment that led to the discovery of the positive
particles obtained in the discharge tube containing hydrogen, the
particle was conducted by Goldstein in 1886. He used a
lightest of all gases, were made by lJ. Thomson in 1906. These
perforated cathode in the modified cathode ray tube (Fig. 2.2). It 4
particles were found to have the e / m value as + 9.579 x 10
was observed that when a high potential difference was applied
between the t':lectrodes, not only cathode rays were produced but coulomb/g. This was the maximum value of elm observed for
also a new type of rays were produced simultaneously from any positive particle. It· was thus assumed that the positive
anode moving towards cathode and passed through the holes or particle given by hydrogen represents a fundamental particle of
canals of the cathode. These rays were termed canal rays since positive charge. This particle was named proton by Rutherford
these passed through the canals of the cathode.. These were also in 1911. Its charge was found to be equal in magnitude but
named anode rays as these originated from anode. When the opposite in sign to that of electron.
properties of these rays were studied by Thomson, he observed Thus, proton carries a charge + 1.602 x 10-19 coulomb,
that these rays consisted of positively charged particles and e.,
i. one unit positive charge.
named them as positive rays. The mass of the proton, thus, can be calculated.
19
e 1.602x 10-
Mass of the proton = =- ---- 4
elm 9.579x 10
Positive
rays = 1.672 X 10-24 g
+
or = 1.672 x 10-:27 kg
~r~L~~~\ ';:~;~E:
(i) Since, most of the a:"particles went straight through the
metal foil undeflected, it means that there must be very large
empty space within the atom or the atom is extraordinarily
hollow.
/l\j/":~~:
(ii) A few of the a-particles were deflected from their original
paths through moderate angles; it was concluded that whole of
RadioaCtive"
substance;'
(Polonium)
~</
I_._~
.
'\ " the positive charge is concentrated and the space occupied by this
positive charge is very small in the atom. When a-particles come
closer to this point, they suffer a force of repulsion and deviate
Lead plate from their paths.
Deflected The positively charged heavy mass which occupies only a
a-particles small volume in an atom is called nucleus. It is supposed to be
Fig. 2.3 present at the centre of the atom.
(iii) A very few of the
Largely deflected Slightly deflected
a7particles a-particles a-particles suffered strong ~
deflections or even returned on ~ t
their path 'indicating that the 9- "0
nucleus is rigid an.d a-particles /') I!?
recoil due to direct collision with 'O:Ill
the heavy positivelycbarged mass. .z ~
oal
The graph between angle of
scattering and the number of - Scattering angle
a-particles scattering in the
Fig. 2.4 (b)
corresponding direction is as
shown in Fig. 2.4 (b).
Information of Rutherford's scattering equation can be
memorised by the following relations:
Slightly deflected (a) Kinetic energy of a-particles:
a-particles N=KI/[(1I2)mv2]2
Fig. 2.4(8) (b) Scattering angle '8':
Consider an a-particle of mass' m' moving directly towards a N =K 2 /[sin 4 (8/2)]
nucleus with velocity 'v' at any given time. As this a-particle (c) Nuclear charge:
approaches the nucleus, its velocity and hence kinetic energy
N =K 3 (Ze)2
continues to decrease. At a certain distance ro from the nucleus,
the a-particle will stop and then start retracing its depicted path. Here, N = Number of a-particles striking the screen and
This distance is called the distance of closest approach. At this K 1 , K 2 and K 3 are the constants.
distance, the kinetic energy of the a-particle is transformed into
electrostatic potential energy. If Z be the .atomic number of the
;,~~fit MOSELEY EXPERIMENT-ATOMIC
· nucleus, then
./'-
1 2 1 x2e NUMBER
'-mv
2 Roentgen, in 1895, discovered that when high energy electrons in
a discharge tube collide with the anode, penetrating radiations are
produced which he named X-rays (Fig. 2.5).
ATOMIC. STRUCTURE .1 71
Cathode rays van den Broek (1913) pointed outthat the atomic number of
an element is equal to the to~l positive charge contained in the
nucleus of its atom. Rutherford was also having the same opinion
that the atomic number of an element repli.esents the number of
+ protons in the nucleus of its atom. Thus, .
Cathode· Anode Atomic number of the element
= Serial number of the element in periodic table
Detracted
X-rays ~,"--~"" = Charge on the nucleus of the atom of the element
, , '
= Number of protons present in the nucleus of the
'!I." ~\ ",
",,~\ / / L X-rays beam atom of the element
"" - = NU)11ber of extranuclear electrons present in tha
,
" ' atom of the element
2::6
Defracted unit
2.6 DISCOVERY OF NEUTRON
Fig. 2.5 The discovery of neutron was actually made about 20 years after
X-rays are electromagnetic radiations of very small the structure of atom was elucidated. by Rutherford. Atomic
wavelengths (0.1-20 A). X-rays are diffracted by diffraction masses of different atoms could not be explained if it was
gratings like ordinary light rays and X-ray spectra are, thus, accepted that atoms consisted only of protons and electrons .
. produced. Each such spectrum is a characteristic property of the Thus, Rutherford (1920) suggested that in an atom, there must be
element used as anode. present at least a third type of fundamental particles which should
Moseley (1912-1913), investigated the X-ray spectril of 38 be electrically neutral and possess mass nearly equal to that of
different elements, starting from aluminium and ending in proton. He proposed the name for such fundamental particle as
gold. He measured the frequency of principal lines of a particular neutron. In 1932, Cbadwlek bombarded beryllium with a
series (thea-lines in the Kseries) of the spe.ctra. It was observed stream Of a-particles. He observed that penetrating radiations
that the frequency of a particular spectral line gradually increased were produced which were not affected by electric and magnetic
with the increase of atomic mass of the element. But, it was soon fields. These radiations consisted of neutral particles, which were
realised that the frequency of the particular spectral line was called neutrons. The nuclear reaction can be shown as:
more precisely related with the serial number of the element in
the periodic table which he termed as atomic number (Z). He ~Be + iHe ~ I~C + ~n
presented the following relationship: B~ryllium a-particle .Carbon Neutron
~.
Thus, diameter (size) of an atom is 100,000 times the diameter (iii) In the solar syst~!!l, there is only one planet which
of the nucleus.* . revolves in any particular orbit, but in the nuclear atomic model
The radius of a nucleus is proportional to the cube root of the more than one electron may rotate in any particular orbit.
number of nucleons within it.
R RoAI13 em Drawbacks of Rutherford Model
(i) According to classical electromagnetic theory, when a
where, Ro = 1.33 X 10- cm; A = mass number; R ::::: Radius of
13
charged particle moves under the influence of attractive force, it
the nucleus. ' .
loses energy continuously in the form of electromagnetic
Rutherford and Marsden calculated the density of the
radiations. Thus, when the electron (a charged particle) moves in
hydrogen nucleus containing only one proton. an attractive field (created by protons present in the nucleus), it
d = Mass [A x 1.66 X 10-24 g] must emit radiations. As a result of this, the electron should lose
. VoJume energy at every tum and move closer and closer to the nucleus
.( following a spiral path (Fig. 2.7). The ultimate result will be that
it will fall into the nucleus, thereby making the atom unstable.
A x 1.66 X 10-24 Bohr made calculations and pointed out that an atom would
=--~~~------------~
4 .' 8
collapse in 10- seconds. Since, the Nucleus
x 3.14 x (1.33 x 10- 13 )3 X A
3 . atom is quite stable, it means the
=1.685 X 1014 gf cm 3 electrons do not fall into the nucleus,
thereby this model does not explain
(iii) There is an empty space around the nucleus called
the stability ofthe atom.
extranuclear part. In this part, electrons are present. The number
(ii) If the electrons lose energy
of electrons in an atom is always equal to number of protons
continuously, the observed spectrum
present in the nucleus. As the nucleus part of the atom is
should be continuous but the actual
responsible for the mass of the atom, ~he extranuclear part is
observed spectrum consists of well
responsible for its volume. The volume of an atom is about 1015
defined lines of definite frequencies.
times the volume of the nucleus. Electron
8 24 Hence, the loss of energy by the
Volume of the atom = (10- )3 = 10- = 1015 electrons is not continuous in an atom. Fig. 2.7
Volume of the nucleus (l0-13)3 10-39
(iv) Electrons revolve round the nucleus in closed orbits with 2.8 ELECTROMAGNETIC RADIATIONS
high speed. The centrifugal force acting on the revolving These are energy radiations which do not need any medium for
electrons is being counterbalanced by the force of attraction propagation, e.g., visible, ultraviolet, infrared, X-rays, y-rays,
between the electrons and the nucleus. etc. An electromagnetic radiation is generated by osci1lations of a
This model was similar to the solar system, the nucleus repre- charged body in a magnetic field or a magnet in an electrical
sentingthe sun and revolving electrons as planets. The electrons field. The frequency of a. wave is the frequency of oscillation of
are,.therefore, generally referred to as planetary electrons. the oscillating charged particle. These radiations or waves have
electrical and magnetic ·fields associated with them and travel at
Dissimilarities between Nuclear Atomic Model and
right angle to these fields. The following are thus the important
Solar System
characteristics of electromagnetic radiations:
(i) The sun and the planets are very big bodies and uncharged • All electromagnetic radiations travel with the velocity of
while the nucleus and electrons are very sinall objects and charged. light.
(ii) The revolution of the planets in the solar system is • These consist of electric and magnetic fields that oscillate
governed by gravitational forces, while the revolution of in directions perpendicular to each other and perpendicular
electrons around the nucleus is governed by electrostatic forces. to the direction in which the wave is trave1ling.
[
S.No. Name Wavelength (A) . Frequency (Hz) Source
14 1 5 9
l. Radio wave 3xlO -3x10 I x 10 .,.;Ix 10 Alternating current of high frequency
2. Micro wave ,3x101 -6xld' 1 x 109 - 5 X 1011 Klystron tube
3. Infrared (IR) 6x 10 6 -7600 5 x 10" - 3.95 X 1016 Incandescent objects
16 14
4. , Visible 7600-3800 3.95 x 10 -7.9 X 10 Electric bulbs, sun rays
5. I
Ultraviolet (UV) 3800-150 7.9 x 10 14
2 X 10 16
Sun rays, arc lamps with mercuryvapours
6. X-Rays 150-0.1 2x lOll> - 3 X 1019 Cathode rays striking metal plate
7. !y-RaYS O.H).OI 1
19
3 x 10 -3 X 10 20
Secondary effect of radioactive. decay
8. ~osmic rays· ! O.ot-Zero ~ ~ 102°-Infinity .-.
Outer space
"'The diameter of various atoms lies in the range of 0.74 to 4.70 A(1 A :; 10-8 cm),
ATOMIC STRUCTURE 73
"
A wave is always characterized by the following six (vi) Time period: Time taken by the wave for one complete
characteristics: cycle or vibration is called time period. It is denoted by T.
(i) Wavelength: The distance between two nearest crests or I
T==-
nearest troughs is called the wavelength. It is denoted by A
Unit: Second per cycle.
v
(lambda) and is measured in terms of centimetre (em), angstrom
(A), micrometre ().un) or nanometre (nm).
·2~9 EMISSION SPECTRA-HYDROGEN
SPECTRUM
Spectrum is the impression produced on a screen when radiations
of particular wavelengths are analysed through a prism or
• Energy
diffraction grating. It is broadly of two types:
(i) Emission spectra (ii) Absorption spectra.
Difference between Emission and Absorption Spectrum
lA =10-8 em =10-10 m Emission spectrum Absorption spectrum
1 f.,lm= 10-4 em = 1O-ti m 1. It gives bright lines (coloured) It gives dark lines on the brigllt
Inm 10-7 cm= 10-9 m on the dark background. background.
=
1 em 108 A ==10 4 f.,lm==107nm 2. Radiations from emitting It is observed when the white
light is passed through the
source are analysed by the
(ii) Frequency: It is defined as the number of waves which substance and the transmitted
spectroscope.
pass through a point in one second. It is denoted by the symbol radiations are analysed by the
v (nu) and is measured in terms of cycles (or waves) per second spectroscope.
(cps) or hertz (Hz). 3. It may be continuous (if source These are always disconti-
=
AV distance travelled in one second emits white light) and may be nuous.
== velocity == c discontinuous (if the source
c emits coloured light).
or V==-
A Emission spectra: It is obtained from the substances which
(iii) Velocity: It is defined as the distance covered in one second emit light on excitation, i. e. ,either by heating the substances on a
by the wave. It is denoted by the letter 'c'. All electromagnetic flame or by passing electric discharge through gases at low
waves travel with the same velocity, i. e. , 3 x 10 10 cm/sec. pressure or by passing electric current discharge through a thin
filament of a high melting point metal. Emission spectra are of
AV== 3x 1010
two types:
Thus, a wave of higher frequency has a· shorter wavelength (a) Continuous spectra and (b) Discontinuous spectra.
while a wave of lower frequency has a longer wavelength. (a) Continuous spectra: When white light is allowed to pass
(iv) Wave number: This is the reciprocal of wavelength, through a prism, it gets resolved into several colours (Fig. 2.8).
i. e. ,the number of wavelengths per centimetre. It is denoted by The spectrum is a rainbow of colours, i. e., violet merges into blue,
the symbol v (nu bar). blue into green, and so on. This is a continuous spectrum.
_ 1
V==- Ultraviolet
A
l I . Violet 4000 A
It is expressed in cm- or m- .
Indigo
(v) Amplitude: It is defined as the height of the crest or
Blue
tlepth of the trough of a wave. It is denoted by the letter 'a'. It
determines the intensity ofthe radiation. Green
The arrangement of various, types of electromagnetic radiations Yellow
~~~~~~~=======~" Orange
in the order of their increasing or decreasing wavelengths or
frequencies is known as electromagnetic spectrum. ' Red 6500 A
, Frequency
V 3x107 (cycle/sec) )3x10 21 Infrared
).. (cm) = 103 f-(_W_av_el_en_gt_h_ 10-11
'"
,.~
Continuous
"'~ '" !-<
Low energy
~5 ~ High energy Fig. 2.8 Continuous spectrum of white light
ll.l
..l
<,... 0 0
Low frequency i:\:", ~, ;;: High frequency (b) Discontinuous spectra: When gases or vapours of a
~
ll.l
Long wavelength 9~
'">- '">-
~ ~ ~ :i
...l
!!l Short wavelength chemical substance are heated in an electric arc or in a Bunsen
~~ Sl
~ ~ ;;:
'" ..l
;:::l
:><: 'I- a
flame, light is emitted. If ray of this light is passed through a
prism, a line spectrum is produced. This spectrum Consists of a
limited number of lines, each of which corresponds to a different
74 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
wavelength of Ffgbt. The line spectrum of each element is unique. Red Blue-Green Indigo Violet
Hydrogen spectrum is an example of line emission spectrum or
atomic emission spectrum.
When an electric discharge is passed through hydrogen gas at
low pressure, a bluish light is emitted. When a ray of this light is 6563 4861.4340 4102
passed through a prism, a discontinuous line spectrum of several
. isolated sharp lines is obtained. The wavelengths of various lines Fig. 2.9 (a) Balmer series In the hydrogen spectrum
[~
show that these Jines lie in visible, ultraviolet and infrared
regions. All these lines observed in the hydrogen spectrum can be Lyman series: v 1 = RZ
A
2
12
- ..!..]
n:
claSsified into six series.
Speetral series . Discovered by Appearing in n2 =2, 3,4,5, ...
Lyman series Lyman' Ultraviolet region Obtained in emission as well as in absorption spectrum ratio
Balmer series . Balmer Visible region ofm lh to nth wavelength of Lyman series.
~: =(:::)' ·{::::i:=:}
Paschen. series Paschen Infraled region
Brackett'series Brackett Infrared region
Pfund series Pfund Infrared region
=IlZ 2 [..!.. - ~l
Humphrey series Humphrey Far infrared region
Ritz presented a mathematical formula to find the Balmer ser.ies: v =!
A 22 ni.
wavelengths of various hydrogen lines.
=3,4,5,6, .. ;
V=l=~=R[~-~)
A c nl n2'
. n2
Obtained only in emission spectrum.
Absorption Spectrum: Suppose the radiations from a conti- number of wavelengths in the emergent light than in incident
nuous source like a hot body (sun light) containing the quanta of light is called absorption spectrum.
all wavelengths passes through a sample of hydrogen gas, then Let the radiations of wavelengths AI' A2' A3, A4 ,AS are
the wavelengths missing in the emergent light give dark lines.on passed through the sample of hydrogen gas such that AI and A4
the bright background. This type of spectrum that contains lesser are absorbed then the absorption spectrum may be represented as:
ATOMIC STRUCtURE 75
::: :::aW5oME SOLVED ExAMPLES\ a:::"::' " ExampleS. What is the ratio between the energies of two
radiations one with a wavelength of 6000 A and other with
" Example 1. How many protons, electrons and neutrons' 2000 A?
are present in 0.18 g ?~ P? ' ,
Solution: No. of protons in one atom ofP Solution: A) = 6000 A and A2 = 2000A
= No. of electrons in one atom ofP 15 c C
No. of neutrons in one atom of P= (A - Z)= (30-15)= 15 E1 h·-andEz =h·-
Al AZ
30 0.18 '
O.l8g ISP= ::: 0.006 mol E) h· c Az 2000 1
30 Ratio, -=-x-::::; =--=
E z Al h· C Al 6000 3
No. of atoms in 0.006 mol = 0.006 x 6.02 x IOz3
or E z = 3EI
No. of protons in 0:006 mol i~p = 15 x 0.006 x 6.02 x 1023
5.418>< 102z Example 6. Calculate the wavelength, wave number and
frequency of photon having an energy equal to three electron
So, No. of electrons = 5A18 xlOz2 volt. (h =6.62 x 10-27 erg- sec.)
and No. of neutrons 5.418 x lOz2
76 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
::::NhC[ 1
Aabsorbed
- .
Aevolved
J = 2X 101~
6.63 X 10- =1 X 1015 s-I]
_
19
6.63 x
23
:::: 6.023 X 10 X 6.626 X 10-34 X 4. The number of photons of light having wavelength 100 nm
which can provide 1 J energy is nearly:
3 X 108 [ 1 _ 1
440 X 10-9 670 X (a) 107 photons (b) 5 xJOIS photons
:::: 0.1197[2.272 x 106 -1.492x 106 ] (c) 5 x 1017 photons (d) 5 x 107 photons
:::: 0.0933 X 106 J I mol:::: 93.3 kJ I mol [Ans. (c)]
[Hint: E= nhe
Example 17. Photochromic sunglasses, which darken
A
when exposed to light, contain a small amount of colourless
AgCI (s) embedded in the glass. When irradiated with Ught, EA
metallic silver atoms are produced and the glass darkens. he
78 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
5. The atomic transition gives rise to the radiation of frequency (vi) The emission or absorption of energy in the form of
(104 MHz). The change in energy per mole of atoms taking radiation can only occur when an electron jumps from one
place would be: . stationary orbit to another.
(a) 3.99 x 10-6 J (b) 3.99 J f),E:::: E bigh - E low :::: hv
24 30
(c) 6.62 X 10- J (d) 6.62 x 10- J Energy is absorbed when the electron jumps from inner to outer
[Ans. (b)] orbit and is eniitted when it rhoves 'from outer to an inner orbit.
[Hint: E =Nhv .
= 6.023 x loB x 6.626 X 10-34 x 104 X 1(f
= 3.99J]
.2l!~;l~ BOHR'S ATOMIC MODE;L Electrons excited
by absorbing
To overcome the objections of Rutherford's model and to explain
energy
the hydrogen spectrum, Bohr proposed a quantum mechanical (Energy absorbed)
model of the atom. This model w~s based on the quantum theory
of radiation and the classical laws of physics. The important
postulates on which Bohr's model is based are. the following:
(i) The atom has a nucleus where all the protons and neutrons ::::::::;'::::::::::::::::l Energy radia1ed
are present. The size of the nucleus is very small. It is present at when electrons
the centre of the atom. fall back
(ii) Negatively charged electrons are revolving around the n=3 (Energy emitted)
(M) n=4
nucleus in the same way as the planets are revolving around the
(N) n=5
sun. The path of the electron is circular. The force of attraction (0) n=6
between the nucleus and the electron is equal to centrifugal force (P)
. of the moving electron.
Fig. 2.10
Force of attraction towards nudeus centl'ifugal force
(iii) Out of infinite number of possible circular orbits around When the electron moves from inner to outer orbit by
the nucleus, the electron can revolve only on those orbits whose absorbing defini~e amount of energy, the new state of the electron
is said to be excited state (Fig. 2.10).
angular momentur.n * is an integral multiple of !!...., i. e. ,
Using the above postulates, Bohr calculated the radii of.
2n
various stationary orbits, the energy associated with each orbit
mvr:::: n!!.... where m:::: mass of the electron, v:::: velocity of and explained the spectrum of hydrogen atom.
2n .
electron, r = radius of the orbit and n =1; 2, 3, ... number of the Radii of various orbits: Consider an electron of mass' m'
orbit. The angular momentum can have values such as, and charge 't! revolving around the nucleus of charge Ze
(Z =atomic number). Let 'v' be the tangential velocity of the
h , 2h , 3h ; etc., but it cannot have a fractional value. Thus, the revolving electron and ' r' the radius of the orbit (Fig. 2.11). The
21t 2n 21t ,
electrostatic force of attraction between the nucleus and electron
angular momentum is quantized. The specified or circular orbits
(quantized) are called atationary orbits. kZex e kZe 2
(applying Coulomb's law)
(iv) By the time, the electron remains in anyone of the
stationary orbits, it does not lose energy. Such a state is called
v
grou.nd or normal state.
In the ground state, potential energy of electron will be Centrifugal
minimum, hence it will be the most stable state. force
(v) Each stationary orbit is associated with a definite amount
of energy. The greater is the distance of the orbit from the
nucleus, more shall be the energy associated with.it These orbits
are also called energy levels and are numb~red as 1, 2, 3,4, .... or
K, L, M, N, ... from nucleus outwards.
i.e., E, <.E2 < E3 < E4 ...
Fig. 2.11
(E2 - E, » (Ei - E 2 » (E4 - E3 ) ....
n2h2
For hydrogen atom, Z = I; so r = 2 2 ·' . energy m
Kmetlc . n th she11 = 13.6>< Z 2 ev
:'\7
4Tt mke
Now putting the values of h, It, m, e and k,
"1 energy m
. n th sheII -27.2 2x Z
2 V
r= .•
n 2 X (6.625 X10-34 i Potentla
n
e
4 x (3.l4i x (9.1x 10-31 ) x (1.6x 10- 19 )2 x (9x 109 ) Substituting the values of n :::: 1, 2, 3,4, ... , etc., the energy of
electron in various energy shells in hydrogen atom can be
= 0.529x n 2 x 10-10 m:::: 0.S29 x n 2 A calculated.
8 2
= 0.529 X 10- X n cm Energy sbeII E (Joule per atom) E (eV per atom) E (kcal/moI) .
where h:::: 6.625 X 10-34 J-sec, Tt = 3.14 I' ,..21.79 X 10- 19 .!..13.6 - 313.6
m= 9.1x 10-31 kg, e= 1.6 x 10-19 coulomb 2 -5.44 x 10-19 -3.4 -78.4
3 -2.42 X 10-
19 -1.51 -34.84
k 9xl09 Nm2/C 2
4 -1.36 X lQ-19 0.85 -19.6
Thus, radius of 1st orbit
0.529x 10-8 x 12 = 0.529 x 10-8 cm= 0.529 x 1O-10 m
Radius of 2nd orbit
=0.529x 10-8 x 22= 2.11 X 10-8 cm= 2.l1x 10-10 m o o o
Radius of 3rd orbit (for hydrogen atom)
0.529x 10-8 x 32 4.76x 10-8 cm= 4.76x 10- 10 m
2 .
and so on. and E" =£1 X Z (for hydrogen like species)
r" :::: 11 x n 2 fo~ hydrogen atom
2 where, £1 :::: energy of hydrogen fIrst orbit.
and ... r" =0.529 x -n A (for hydrogen like species)
Z
80 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Since, n can have only integral values, it follows that total Interpretation of hydrogen spectrum: The only electron
energy of the electron is quantised. The negative sign indicates in the hydrogen atom resides under ordinary conditions on the
that the electron is under attraction towards nucleus, i. e., it is first orbit. When energy is supplied, the electron moves to higher
bound to the nucleus. The electron has minimum energy in the energy shells depending on the amount of energy absorbed.
first orbit and its energy increases as n increases, i. e. , it becomes When this electron returns to any of the lower energy shells, it
less negative. The electron can have a maximum energy value of emits energy. Lyman series is formed when the electron returns to
zero when n = 00. The zero energy means that the electron is no the lowest energy state while Balmer series is formed when the
longer bound to the nucleus, i. e. , it is not under attraction towards electron returns to second energy shell. Similarly, Paschen,
nucleus. Brackett and Pfund series are formed when electron returns to the
For hydrogen h'ke species such as He . 2+ , etc."
+ ,L· third, fourth and fifth energy shells from higher energy shells
En =Z2 xEn for hydrogen atom. respectively (Fig. 2.l2).
Velocity of an electron: We know that,
Centrifugal force on electron
== force of attraction between nucleus and electron
mv Ze
2 2
(in CGS units) ... (i)
r
The angular momentum of an electron is given as:
mvr= 2n
nhf .. ·(i0
From eqs. (i) and (ii), we have Balmer 1.0--1---1 Brackett
v(;~)= Ze 2
series series
v= ~ [2n;2)
v = ~ x 2.l88 X 108 cmf sec ... (iii)
n
2.188 x 108 Lymanserles
v cm! sec (For hydrogen, Z = 1)
n Fig. 2.12
VI = 2.188x 108 cmlsec Maximum number of lines produced when an electron jumps
1 . .. n(n --, 1)
v2 = x 2.l88x 108 cm!sec from n th level to ground level IS equal t o ' . For example,
2 2
in the case of n = 4; number of lines -produced is 6. (4 -t 3,4 -t 2,
I x 2.188x 108 cm!sec 4 -t 1,3 -t 2, 3 -t 1,2 -t n When an electron returns from n2 .to
3 nl state, the number oflines in the spectrum will be equal to.
Here, VI ,V2 and V3 are the velocities of electron in first, (nz - nl )(nz nl + 1) ,
second and third Bohr orbits in hydrogen. . 2
From equation (iii), If the electron comes back from energy level having energy E 2
VI _ 2 V3 1 to energy level having energy E[, then the difference may be
and - == - and so on.
V2 1 . VI 3 expressed in terms of energy of photon as:
Orbital frequency: Number of revolutions 'pet"'second by E2 - E[ =!lE == hv
an electron in a shell is called orbital frequency; it may be or the frequency of the emitted radiation is given by
calculated as, !lE
v -
Number of revolutions per second by an electron in a shell h
Vel~city 2)V l( Since, !lE can have only definite values depending on the
Circur:.ference = = 2nr h 7 definite energies ofE2 and E 1 , v will have only fixed values in an
atom,
= Z2 x 6.66 x rol5 or v
c !lE
n3 A h
where, E. = Energy offrrst shell. he
Time period of revolution of electron in nth orbit (Tn) : or A
!lE
3 .
Since, hand e are constants, !lE corresponds to definite
~ x 1.5 x 1O-[? sec energy; thus, each transition from one energy level to another will
Z2
produce a light of definite wavelength. This is actually observed
as a line in the spectrum of hydrogen atom.
ATOMIC STRUCTURE 81
I 2 R ;
Pasch"en, 1"Imll =? B raek ett '1Imlt
" = R
21t 2me 4
, 3- 42
where, R= Rydbergconstant= 109743 cm- I
ch 3
This value of R is in agreement' with ,experimentally
Pfund limit R,
52
H~mphrey limit = 6'~
determined value 109677,76 cm- 1 • Rydberg equation for (iii) Intensities of spectral 'lines: The intensities of spectral
hydrogen may be given as, lines in a particular series decrease with increase in the value of
, l
v 1 = R [ -\- -
A nl
-\-J
n2
n2' i. e., higher state.
e.g.,
, Lyman series (2 ---; 1) > (3 ---; 1) > (4 ---; 1) > (5 ---; 1)
("2 ~nl)
ModificatIon of Rydber,gEquation
Balmer series (3 4 2) > (4 ---; 2» (5 ~ 2) > (6---;2) .' .
According to the Rydberg ~quation:
v = 21t J.1Z 2e
.
2
1: 3
4
[_1 __1]
2
, Electronic charge
Cl nl n22 , , The energy required to remove an electron from the groul\d
. , state to form cation, i.~. , to take the electrop to infinity, is called
Reduced mass '11' can be calculated as, ionization energy.
1 1 1
-=-+- IE E"" - Eground
11 m M
where, mass of electron
m IE:::: 0- El (H)= 13.6eV atom-I
and mass of nucleus
M :::: 2.17 X 10- 18 Jatom- I
mM
.. J.1 Z2
m+M IE=- x 13.6eV
(i) First line of a series: It is called 'line of longest , n2
wavelength' or 'line of shortest energy'. Z2
I1 _I_,X
For first line, •
10'
'"
n 12 Z2
2
82 I G. R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(IE)H X Z 2 radial velocity and the other perpendicular to the radius vector
(IEh = 2 called transverse or angular velocity. These two velocities give
.. n
rise to radial momentum and angular or azimuthal momentum.
If an electron is already present in the excited state, then the
Sommerfeld proposed that both the. momenta must be integral
energy required to remove that electron is called· separation
energy. multiples of!!...... [Fig. 2.13 (b)].
21t
E separation E ~ - E excited
h
The following points support Bohr theory: Radial momentum n -
r 21t
(i) The frequencies of the spectral lines calculated from . h
Bohr equation are in close agreement with the Azimuthal momentum =n<l>-
frequencies' observed experimentally in hydrogen 21t
spectrum. nr and n<l> are related to the main orbit 'n' as:
(ii) The value of Rydberg constant for hydrogen calculated n nr + n<l>'
from Bohr equation tallies with that determined n nr + n<l> Length of major axis
or
experimentally. . n<l> n<l> Length of minor axis
(iii) The emission and absorption spectra of hydrogen like (i) 'n<l>'. cannot be zero becau~e un,der this condition, the
species such as He + , Li 2+ and Be 3 + can be explained ellipse shall take the shape of a straIght hne.
with the help of Bohr theory. (ii) 'n<l>' cannot be more than' n'because minor axis is always
Limitations of Bohr Theory smaller than major axis.
" • 't
(iii) 'n<l>' can be equa~ to ' n'.. Under this ~onq.ition, the major
(i) It does not explain the spectra ofmulti-electron atoms.
axis becomes equal to mmor aXIS and the elhpse 41kes the shape
(Ii) When a high resolving power spectroscope is used, it is of a circle. Thus, n<l> can have all integral values up to ' n' but not
observed that a spectral line in the hydrogen spectrum is zero. When the values are less than' n',orbits are elliptical and
not a simple line but a collection of several lines which when. it becomes equal to 'n', the orbit is circular in nature.
are very close to one another. This is known as fine
For n == I, n4J can have only one value, i. e., 1. Therefore, the
spectrum. Bohr theory does not explain the fine spectra
first orbit is circular in nature.
of even the -hydrogen atom.
(tii) It does not explain t~e splitting of spectral lines into a
For n =2, n. can have tWo values 1 and 2, i. e., ~e ~econd
orbit has tWo sub-orbits, one is elliptical and the other IS CIrcular
group of finer lines under the influence of magnetic field in nature.
(Zeeman effect) and electric field (Stark effect).
For n == 3, n4J can have three va~ue.s I, 2 and 3, i..e., t~ird or~it
(iv) Bohr theory is not in agreement with Heisenberg'S has three sub-orbits, two are elhphcal and one IS CIrcular m
uncertainty principle. ' nature.
For n = 4, n4J can have four values I, 2, 3 and 4, i. e., fou~h
III SOMMERFELD'S EXTENSION OF orbit has four sub-orbits, three are elliptical and fourth one IS
BOHR THEORY circular in nature (Fig. 2.14).
To accouht for the fine spectrum of hydrogen atom, Sommerfeld,
in 1915, proposed that the moving electron might descri~e
elliptical orbits in addition to circular orbits and the pucleus IS
situated at one of the foci. During motion on a circle, only the
angle of revolution changes while the distance from the nucleus
remains the same but in elliptical motion both the angles of
revolution and the distance of the electron from the nucleus
change. The distance from the nucleus is termed as~adius v,ector
and the angle of revol\ltion is known as :azimutluda~gle. The
tangential velocity of the electron at a particular instant can be
resolved into two components: one along the radius vector called
V Radial velocity Fig. 2.14
. V (Tangential velocity)
Sommerfeld thus introduced the concept of subenergy shells.
In a main energy shell, the energies of subshells differ slightly
from one another. Hence, the jumping of an electron from one
r-..1----I---..!---1 Major axis
energy shell to another energy shell will involve slightly different
amount of energy as it will depend on subshell also. This explains
to some extent the fine spectrum,Qf hydrogen atom. However,
Minor axis Sommerfeld extension fails to explain the spectra of
(a) (b)
multielectron atoms.
Fig. 2.13
ATOMIC STRUCTURE 'I 83
2i.7xlO- 12
: :: ::::_SOME SOLVED ExAMPLES\ =:::: : .
---'--.,,---'-'- erg = 5.425 x 10-12 erg,
22
~~ii"E~ample 18. Calculate the wavelength arid energy of
radiation emitted for the electronic transition from infinite to and. E"", = 0
stationary state of hydrogen atom, '(Given, R 1.09678 M == Change in energy E"",...., 5.425 X 10- 12 erg ,
xl0 7 m-l,h=6.6256xlO~34J-sandc 2.9979xl0 8 m:s.,-I) Thus, energy required to remove an electron from 2nd orbit
, = 5.425 X 10- 12 erg
Solution: l
A
R[~
nf ·~l
ni According to quantum equation,
c
r~nn~:2, 1
M=h·
A
R or A ~
M
or A I 1 9.11x 10-8 m (h = 6.625 x 10-27 erg - sec; c 3 x 1010 cml sec)
R 1.09678 x 107
and M = 5.425 X 10- 12 erg
We know that,
A (6.625 X 10-27 ) X (3 X 1010 )
E := hv h. c == 6.6256 x 10-34 X 2.9979 x So,
A 9.11 X 10-8 5.425 X 10- 12
=3.7xl0-5 cm
2.17 X 10- 18 J
Thus, the longest wavelength of light that can cause this
Example 19. Calculate the velocity (cm /sec) of an transit40n is 3.7 x 10-5 cm. '
electron placed in the third orbit of the hydrogen atom. Also
calculate the number of revolutions per second that this electron Example 21. Calculate the shortest and longest
makes around the nucleus. wavelengths in hydrogen spectrum ofLyman series,
Solution: Radius of 3rd orbit Or
32 x 0.529 x 10-8 4.761x 10-8 cm Calculate the wavelengths of the first line and the series limit
We know that, for the Lyman series for hydrogen. (R H == 109678 cm- I )
nh nh Solution: For Lyman series, n l I
mvr or v = - -
2n 2nmr For shortest wavelength in Lyman series (i. e. ,series limit), the
3 x 6.624 x 10-27 energy difference in two states showing transition should be
2 x 3.14 x (9.108 x 10-28 )x (4.761 X 10-8 ) maximum, i. e. , n2 00.,
f?L:~_,~~ample 23. Light of wavelength 128181 is emitted when Calculate the longest wavelength of light that will be needed
the electron ofa hydrogen atom drops from 5th to 3rd orbit. Find to remove an electron from the 3rd orbit of the He + ion.
the wavelength ofthe photon emitted when the electron falls from (liT 1990)
3rd to 2nd orbit. Solution: The electronic energy of He + ion in the nth Bohr
St)lution~ We know that, . orbit
== -122.4 eV
Ionisation energy of Li 2+ == -(-122.4) = 122.4 eV
ATOMIC STRUCTURE I· 85
Example 28. The wavelength of a certain line in Balmer 3R
series'is observed to be 4341 A. To what value of 'n' does this 4
correspond? (R H =109678cm- l ) For hydrogen atom,
;;)<:> Example 33. Calculate the wavelength of radiations [Hint: . 1iHe+ ) = Z 211 (H)
emitted, produced in a line in Lyman series, when an electron 22 x E = 4E]
falls from fourth stationary state in hydrogen atom. 8. The number of spectral lines that are possible when electrons
(R H L! X 107 1
111- ) (liT 1995) in 7th shell in different hydrogen atoms return to the 2nd
shell is:
Solution: 1 - R [-I __1_'j\
A- n; ni (a) 12
" [Ans. (b)]
(b) 15 (c) 14 (d) lQ
Llx 10 7 (~, _ _
11 (fl:! - nl )(llz n t + 1)
, '4 ) e 2 [Hint: Number of spectral lines
2
969;6 x IO-10metre (7 - 2)(7 2 + 1) = 15] <
A= 969.6A 2
Example 34. What is the degeneracy of the level of the 9. The ratio of radii of first orbits ofH, He + and Li 2 + is:
(a)I:2:3 (b)6:3:2 (c)I:4:9 (d)9:4:1
. hydrogen atom that has the energy (- RH
, . 9
J, ? [Ans. (b)]
n2
Solution: E =_ RH =_ RH [Hint: r=~ x 0.529 A
n, 'n2 ,9 Z
n 3 rH : rHe + : rLi2+
00=
8x (2;r '
x 22 x 9.1 X 10~28 x (4.Sx 10-10 )4
'r-'- - -
11. What is the energy in eV required to excite the electron from
n =' lto n = 2 state in hydrogen atom? (n = principal quantum
number) teET (J&K) 20061
(2)3 x (6.626x 10-27 )3 (a) 13.6 (b) 3.4 (c) 17 (d) 10.2 '
[Ans. (d)]
[Hint: b.E = E2 EI
[Hint: PE = - 2KE value of mass (m) increases, i. e. • in the case of heavier particles,
the wavelength is too small to be measured. de Broglie equation .
:. PE will change from - 2x to _ 2x is applicable in the case of smaller particles like electron and has
4
no significance for larger particles.
Change in potential energy (- ~ ) - (-2x)
(A) de Broglie wavelength associated with charged
particles
=_::+2x=3x]
2 2 (i) For electron:
to a new theory known as wave mechanical theory of matter. (iii) For a-particles:
According to this theory, the electrons, protons and even atoms,' A=0.10I A
when in motion, possess wave properties.
de Broglie derived an expression for calculating the
rv
wavelength ofthe wave associated with the electron. where, V =accelerating potential oftQe~~particles.
Accoram15to Planck's equation,
'-. '., · · · e (B) de Broglie wavelength associated with
E=hv h·,- ... (i) uncharged particles
:A
The energy of a photon on the basis of Einstein's mass- energy (i) For neutrons:
relationship is h 6.62 X 10-34
A=-- =-======
E = me2 .,. (ii) .J2Em ~2 x 1.67x 10-27 x E
where, e is the velocity of the electron.
Equllting both the equations, we get . = 0.286 A
e
h-=me
2' JE (eV) .
A ...
(ii) For gas molecules:
A =!!-. = h h
me p A=---
mxvnns
Momentum of the moving electron is inversely proportional to
h
its wavelength.
Let kinetic energy of the particle of mass 'm' is E. .J3mkT
I 2 where, k = Boltzmann constant
E=-mv
2 Bohr theory versus de Broglie equation: One· of the
2Em=m 2v
2 postulates of Bohr theory is that angular momentum of an electron
42Em = mv = p(momentum) is an integral multiple of~. This postulate can be derived with the
2n >
So, 21tr= n/.. In the case of bigger particles (having considerable mass), the
/.. 21tr value of uncertainty product is negligible. If the position is
or ... (i)
n known quite accurately, i. e. , Ilx is very small, Av becomes large
from de Broglie equation, and vice-versa. Thus, uncertainty principle is important only' in '
/..= h, the case of smaller moving particles like electrons.
... (ii) • for other canonical conjugates of motion, tIie equation for
mv.'
IT 21tr Heisenberg uncertainty principle may ~e given as:
Thus, -'=---=-- momentum = mass x velocity
mv n
. velocity .
h ==massx xbme
mvr = n . - (v =;: velocity of electron time
, 21t
and r=;: radii of the orbit) == force' x time
momentum x distance == force x distance x time
i. e., . '\.ngu1ar momentum = n . - h . .. ( III
... )
==energy J< time
21t
Ap Ilx == AE At
This proves tlut the de Broglie and Bohr concepts are in .' ·h·
perfect agreement with each other.· ' . AE At Co - (for energy and time)
41t
Similarly, A Ij) AS Co.!!:.... (for angular motion)
iil~ll;. ",HEISENBERG UNCj:RTAINTY 4~
PRINCIPLE . On the basis of this principle, therefore, Bohr picture of an
electron in an atom, which gives a fixed position in a fixed orbit
Bohr theory considers an electron asa material particle. Its
and definite velocity to an electron, is no longer tenable. The best
position and momentum can be determined with accuracy. But,
we can think of in terms of probability of locating an electron
when an electron is considered in the form of wave as suggested
with a probable velocity in a given region of space at a given
by de Broglie. it is not possible to asc~rtain simultaneously the
time. The space or it. three dimensional region round the nucleus
exact position and velocity of the electron more precisely at a
where there is maximum probability of finding an electron of a
given instant since the wave is extending throughout a region of
specific energy is called an atolUic orbital.'
space. To locate the electren, radiation with extremely short
wavelength is required. Radiation that has short wavelength is
very energetic in nature. When it strikes the electron, the Impact
: : ::::a_SOME SOLVED EXAMPLES\a::::::
causes a change in the velocity of the electron. Thus, the attempt Example 36. Calculate the wavelength associated with an
to locate the electron' changes ultimately the momentum of the electron moving with a velocity of10 10 cm per sec.
, electron. Photons, with longer wavelengths are less energetic and 28
Solution,: Mass of the electron = 9.10 x 10- g
cause less effect on the momentum of the electron. Because of
Velocity of electron == 1010 cm per sec
larger wavelength, such photons are not able to locate the
position of an electron precisely. h == 6.62 X 10-27 erg- sec
In 1927, Werner Heisenberg presented a principle known as According to de Btoglie equation,
Heisenberg uncertainty principle which states: "It is ,. h 6.62 X 10-27
/ . . = - = - - 28
----
impossible to measure simultaneously the exact position and . mv 9.l0x 10- x 1010 .
exact momentum of a body as smaU as an electron."
== 7.72x 10- 10 cm
The uncertainty of measurement of position, Ax and the
uncertainty of momentum, IIp or llmv are related by Heisenberg's 0.0772 A
relationship as: Example 37. Calculate. the uncertainty in.the position ofa
1lx·1:!.p Co hi 41t partieie when the uncertainty in momentum is:
or Ilx . llmv Co h I 41t (a) Ix 10-:-3 gcmsec- 1 (b) zero.
where, IT is Planck's constant. Solution: (a) Given, ..
28
for an electron of mass m(9.l0x 10- g), the product of AP= lxlO-3 gcmsec- 1
uncertainty is quite large~ h 6.62 x 1.0-27 erg- sec
6.626 x 10-27 1t == 3.142
Ilx ·llv Co - - ' - - - - -
.41tm According to uncertainty principle,
. h
6.626x 1O-2~ A,;r: .I:!.p Co -
Co - - - - - - - - - 41t
4x 3.14x9JOx . '27
So, Ilx Co .!!:.... • _1_ Co 6.62 x 10- x _I_
'" 0.57 erg- sec per gram approximately
. 41t Ap ··4 x 3.142 10-3 .
Ilx' Av = uncertainty product
=
When Ilx = 0, Av 00 and vice-versa. ' == 0.527 x 10-24 em
(b) When the viuue of Ap 0, the value of Ilxwill be infinity.
I
. ATOMIC STRUCTURE 89
'>', J1x.a~ple 38. .Calculate the momentum ofa p(1rtide which, Example 43. The kinetic energy of an electron is
has a de Brogiie wavelength of2.5 x 10- 10 m. 4.55 x 10-25 J. Calculate the wavelength, (h = 6.6 x 10-34 J-sec,
(h = 6.6 x lQ~34 kgm 2 s -I ) mass of electron = 9.1 x 10-31 kg).
When, the kinetic energy of electron becomes 4 times, the ~.~ WAVE MECHANICAL MODEL OF ATOM
de Broglie wavelength will become half]
The mass of photon having wavelength 1 nm is: The atomic model which is based on the particle and wave nature
14.
of the electron is known as wave mechanical model of the
(a) 2.21 x 10-35 kg (b) 2.21 x 10-33 g
atom. This was developed by Erwin Schrodinger in 1926. This
(c) 2.21 X 10-33 kg (d) 2.21 x 10-26 kg model describes the electron as a three-dimensional wave in the
[ADS. (c)] electronic. field of positively charged nucleus. SchrOdinger
derived an equation which describes wave motion of an electron.
[Hint: A= h
me The differential equation is:
h 6.626 x 10-34 d2W d 2 W d 2W 8n 2m
m - = ---,:-----;:- +--+ +--(E V)W=O.
Ae 1 x 10-9 X 3 X 108 dy2 h2 ;
= 2.21 X 10-33 kg] where, x, y and z are cartesian coordinates of the electron;'
15. The de Broglie wavelength of 1 mg grain of sand blown by.a m = mass of the electron; E = total energy of the electron;
20 ms- I wind is: . V = potential energy of the electron; h = Planck's constant and
(a) 3.3 x 10-29 m (b) 3.3 x 10-21 m W(psi) = wave function of the. electron.
Significance of W: The wave function may be regarded as
(~) 3.3 x 10-49 m (d) 3.3 x 10--42 m
the amplitude function expressed in tenns of coordinates
[Ans. (a)]
34
x, yandz. The wave function may have positive or negative
[Hint: A =.!!..- = 6.626 x 10- = 3.313 x 10-29 m] values depending upon the values of coordinates.
mv 1 X 10-6 X 20 The main aim ofSchrOdinger equation is to give a solution for
16. In an atom, an electron is moving with a speed of 600 m sec-I the probability approach. When the equation is solved, it is
with an accuracy of 0.005%. Certainty with which the observed that for some regions of space the value of Wis positive
position of the electron can be located is: and for other regions the value of W is negative. But the
(h = 6. 6x 10-34 kgm2 s-I ,mas~ofelectron= 9.1 x 10-31 kg) probability must be always positive and cannot be negative. It is,
(AIEEE 2009) thUs, proper to use W2 in favour ofW.
(a) 1. 52x 10-4 m (b) 5.1x 10-3 m Significance of W1. : W2 is a probability factor. It describes
(c) 1.92x 10-3 m (d) 3.84 x 10-3 m the probability of finding an electron within a small space. The
[Ans. (c)] space in which' there is maximum probability of finding an
electron is termed as orbital.
[Hint: ACcuracy in velocity =0.005% .
The solution of the wave equation is beyond the scope of this
Av = 600 x 0.005= 0.03 book. The important point ofthe solution of this equation is that it
100 provides a set of numbers, called quantum numbers, which
According to Heisenberg's uncertainty principle, describe energies ofthe electrons in atoms, information about the
h shapes and orientations of the most probable distribution of
AxmAv;::'- electrons around the nucleus. .
411:
Wave function \If can be plotted against distance Or' from
6.6 X 10-34
Ax = -------:;::;--~- nucleus as,
4x3.14x9.1x x 0.03
1.92xI0-3 m] '"
<.:
17. Velocity of de Broglie wave is given by:
'If
e2 h 2
(a) -
V
(b) ~
me
(c) me
h
(d) VA t
[Ans. (b)]
.h h Node
[Hint: A
mv p
h
p=- 'If
A
mv=
hv t
e
v hv ]
me
1~
(iv) For 2p-orbital, n 2, 1=1, it will have no radial node
but it has only one angular node.
(v ) For 3p-orbital, n 3, 1= l, it will have one radial and one
angular node.
For s-orbitals: ----+ r ----+
For p-orbitals:
°
(n - l) radial nodes + angular' node (n - 1) total nodes.
r
Number of radial nodes = (n -/- 1).
At node, the value of'R 'changes from positive to negative.
(n '2)radial nodes + I angular node = (n I) total nodes.
Plot of Radial Probability Density 'R 2,:
For d-orbitals:
(n - 3) radial nodes + 2 angular nodes (n - I) total nodes. 28 2p
d 2 like all d-orbitals has two angular nodes; The difference is
z .
t\ 1s . .,.
thanhe angular nodes are cones in a d 2 orbital, not planes.
z R2~
Operator form Schrodinger Wave Equation
H'P=E'P (Operatorfonn) r ----+ r ----+ r ----+
~ [ - -h- V ' 2 +v~]
2
The plots of probability, i.e., R2 or '1'2 are more meaningful
whereH= Hamiltonian operator
.
2
81.t m than the plots of functions themselves. It can be seen that for both
Is and2s orbitats, the probability has a maximum value at r= 0,
=1'+ V i.e., in the nucleus. In case of 2s orbital, one more maximum in
Here, t = Kinetic energy operator the probability plot is observed.
V Potential· energy operator
Plot of Radial Probability Function (41tr2R2):
Complete wave function can be given as
In order to visualize the electron cloud within a spherical shell
'I' (r,9,(j)= R(r) e(9)«I>«(j) is placed at radii 'r' and 'r + dY from the nucleus. Thus radial
'---v-' ~
Radial' part Angular part ,probability function describes the total probability qffinding the
Dependence of the wave function on quantum number can be electron in a spherical shell of thickness 'dr' located at the
given as, ' distance r from the nucleus.
'Pn1m (r, 9, (j) Rnl (r) elm (9)«1> m«(j) R.P.F.= (Volume of spherical shell) x Probability density
The function R depend only on 1'; therefore they describe the , . = (41tr 2 dr) x R2
distribution of the electron as a function of r from the nucleus.
These functions depend upon two quantum numbers, n and I. The 18 2s 2p
two functions e and <l> taken together . give the angular
distribution of the electron. N
The radial part ofthe wave function for some orbitals may be
given as, 1
n
312 In the plot of radial probability against 'r', number peaks, i.e.,
o 2 ~
Is
( ) e-Zrlao
region of maximum probability n - I.
92 G.R'.B. PHYSiCAL CHEMISTRY FOR COMPETITIONS
x 2_ 8x + 12 = 0
(x 6)(x - 2) =0
when x-2=0
x=2
r--+ 2r = 2, i.~.,r =~ (Middle value)
llo
X, Y and Z are respectively
(a)R,R 2 and4n?R2 (b) R2, Rand 41t?R2, when x-6=O
2 2 x ='6'
(c)4n?R ,R andR (d) R2, 4n?R2 and R
2r =6
[Ans. (b)]
llo
[Hint: Y will be definitely 'R' because value of R ,cannot be
r = 31lo (Maximum)]
negative, thus X will be R2 and Z will be 41t?R. Z represents
radial probability function; its value will be zero at origin]
2~16 QUANTUM NUMBERS
20. The wave function CI') of 2s is given by :
\f2s 2lrt(:J f
1 BM=~=9.2732x 10-14 J
41tmc
Maximum electrons present in a subshell = 2(21 + I)
1s 2s-orbital
*No energy' shell in atoms of known elements possesses mor" than 32 electrons.
94 I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
z z
Fig. 2.16
When 1= 1, 'm' has three values -1,0, +1. It implies that 'p' dxy dyz d;x .dx2 d;
Orbital i
subshell of any energy shell has three space orientations, i. e. , m ±2 ±1 ±1 ±2 0
three orbitals. Each p-orbital has du-mb-bell shape. Each one is
disposed symmetrically along one of the three axes as shown in Nodal planes:
Fig. 2.16. p-orbitals have directional character. Orbital Nodal planes
Orbital P z Px Py d X)' xz,yz
m
Nodal plane xy
° ±l
yz
±1
zx
d·yz
dzx
XY,zx
xy,yz
When 1= 2,' m' has five values -2, ...:.1, 0, + 1, + 2. It implies d x2 :.. y2 x-y O,x+ y=O
that d-subshell of any energy shell has five orientations, i. e., five dz2 No nodal plane, it has
orbitals. All the five orbitals are not identical in shape. Four. of a ring around the lobe
the d-orbitals dX)'· ,dyz, d zx ,dx 2 - y 2 contain four lobes while
There are seven I-orbitals designated as I 2 2' I y(x 2 y2)'
fifth orbital d z2 consists of only two lobes. The lobes of d X)' • x(x - y)
orbital lie between x and y-axes. Similar is the case for I z(x 2 - y 2) ' Ixyz ,Iz 3, f yz 2 and 1._2'
x< Their shapes are complicated
d yz and d zx' Four lobes of d x2 _ 2 orbital are lying along x and y-
axes while the two lobes of d 2 ~rbital are lying along z-axis and ones.
z
contain a ring of negative charge surrouliQing the nucleus in Positive values of ml describes the orbital angular momentum
xy-plane (fig. 2.16). component in the direction of applied magnetic field while the
negative values of mlare for the components in opposite
direction to the applied magnetic field.
ATOMIC STRUCTURE 95
Degenerate Orbitals
Orbitals which are located at the same energy level on the energy
level diagram are called degenerate orbitals. Thus, electrons have
equal probability to occupy any of the degenerate orbitals.
Px' Py and pz--,------t 3-fold degenerate
d-orbitals --,------t 5-fold degenerate
f-orbitals --,------t 7-fold degenerate
Degeneracy of p-orbitals remains unaffected in presence of
external uniform magnetic field but degeneracy of d and
-3 f-orbitals is affected by external magnetic field.
Fig. 21.6 (a) Space quantization in magnetic field Spin Quantum Number
It is denoted by's' and it was given by Goldschmidt.
Characteristics of Orbitals
Spin quantum number represents the direction of electron spin
(i) All orbitals of the same shell in the absence of magnetic around its own axis_
field possess same energy, i. e. , they are degenerate. (i) For clockwis~ spin,s = + Ji (i arrow representation).
(ii) All orbitals of the same subshell differ in the direction of (ii) For anticlockwise spin, s = - Ji (J- arrow representation).
their space orientation. Spin electron produces angular momentum equal to I-l s given by
, h
(iii) Total number of orbitals in amain energy shell is equal to I-l s = ~s( s + 1) - , where, s = + Ji
n 2 (but not more than 16 in any of the main shells of the known 2n
elements). Total spin of an atom = n x Ji. (n = number of unpaired
n = 1 No. oJ orbitals = (1)2 = 1(ls) electrons)
n = 2 No. of orbitals = (2)2 = 4 (2<>, 2px, 2py, 2pz ) Spin magnetic moment (!-.I. s ) is given by
n = 3 No. of orbitals = (3)2 == 9 (3s, 3Px' 3p y' 3p z , 3d XY' I-ls =~s(s+ 1)~
2nmc
3d yz , 3d zx , 3dx2 _ y2 , 3d z2 )
Each orbital can accommodate two electrons with opposite
n=4 No. of orbitals = (4)2 =16 spin or spin paired; paired electrons cancel the magnetic moment
and develop mutual magnetic attraction as shown in the
The division of main shells into subshells and that of subshell
following Fig. 2.17.
into orbitals has been shown below:
N S
Note: Magnetic quantwn nwnber also represents quantized value of
.. . . MagnetiC field .....,.. .
z-component of angular momeritwn of the electron in an orbital
through the expression
/-
....,,~.- ....,
--, /
... ",--_ .....
--
,/./.................
.
.... "-- .... , .... ,,--~,
............... -- -- , \ /
.
Lz=mC:) /
['
I
. /":'
[
..... :\ I "'. . ','
II
\
I \
/
['
I
/"
[
, ~ I .,.. " "
II
I \
I I \. I I I \ 1
If El is the angle between z-axis and angular momentum vector, 1 1 1 1+1/2 -1121 1 1 1
\ 1 I I \ 1 I [
Lz=L cos El I I
II
,~ // " II,
[
'[
[ I I
II
" ...,"
[
'[
[
jI,
m (~) = ~l(l + I) ~ ." .... _- / , --" jI ~ .... -- / , --" ,t
cos El ..... _-,,., '---~ ' ..... _-,,., '---;/
2n 21t
or m =~l(l + I) cos El
Main shell Subs hells Orbitals S N
1st·shell ___ _
(K-shell) 'n = 1
Fig. 2.17
15 (/= 0) 15(m=0)
2nd-shell -------< "",,- 25 (/ = 0) 25(m=0) Electrons having same spin are called spin parallel and those
(L-shell) n=2 ...............
'---
2p(/=1)
..,,""~O)
-- ------
............ ,2py(m=±1)
having opposite spin are called spin paired.
Spin paired ~ II]]
2Px(m=± 1)
---------------
35(m= 0)
Spin parallel ~ [fJ]
3rd-shell Spin multipliCity: .
(M-shell)
Spin multiplicity = [2:U + 1]
where; s = spin quantum number
e.g., carbon ls2 2<>2 2p2
No. of No. of (iii) Number ofsubshells in a main energy shell is equal to the
Prindplll Aziinutfud Magn~1!' SpiD value ofn. .
eleetrons eleetrons
Q.No. Q. 1\19. Q. No. Q.No.
ona ODa . No. of subenergy
on'· .'1' 'mf '!I' Valueofn Desiguted as
.ubsbeR maiD .beR .beIII
O(s) 0 +Yz,-Yz 2 2 I I Is
2 2 2s,2p
2 O(s) 0 +Yz,-Yz 2 3 3 3s; 3p, 3d
1(P) -I 8· 4 4 4s, 4p, 4d, 4[
+)-;'-)1, \
0 +Yz,-Yz 6 (iv) Number of orbitals in a,main energy shell is equal to n 2 .
+1 +Yz,-Yz n No. of orbitalt
== I s
3 O(s) . 0 +Yz,-Yz 2
-I
2 (2i =4 s, Px; Py' p=
+)1,,-)1, )
+~"-Yz ..
3
1(P) 0 6
(v) . One orbital cannot have more than two electrons. If two
+1 '+Yz,-Yz electrons are present, their spins should be in opposite
-2 +Yz,-Yz 18 directions. .
-I +Yz,-Yz IUlI$IMfONS ·01 iOBJlCTN£QUUOOJt5
2(d) 0 .+ Yz, - Yz lO
23. The orbital angular momentum of an electron in a d-orbital is:
+1 +Yz,-Yz (DeE 2007)
+2 +Yz,-Yz (a).J6~ (b).fi h (c) h . (d) 2h
2n 2n 2n 2n
[Ans. (a)]
ATOMIC STRUCTURE 97
Number of subshells in a .shell = n Is,2s,2p,3s,3p,48,3d, 4p,5s,4d, 5p,6s,4f,5d ,6p, 78, 5f,6d, 7p.
Number of orbitals in a subshell = (21 + 1) The sequence in which various subshells are filled up can also
n = 3, 1 = 2, m = orepresents 3d] be determined with the help of(n + I )value for a given subshell.
The subsheU with lowest (n + I ) value is filled up tirs~.WheD
26. Which of the following is not possible?
[BCECE (Medical) 2007) two or more subshells have same (n + I) value, the.subshell
(a) n = 2, I = I, m = 0 (b) n ::; 2, I::; 0, m::; -I with lowest value of 'n' is fdled up first.
(c) n = 3, I ::; 0, m = 0 (d) n 3, l:::i: I, m:::-I
[Aos. (b)] SubsheU If 1 (If + I)
[Hint: When I = 0, 'm' will also be equal to zero.] Is I 0 1
2s 2 0 2
27. What is the maximum number of electrons in an atom that can
have the quantum numbers n ::; 4, me + 1?
[PMT (Kerala) 2007)
2p
3s
2
3
.I
0
3
3
} Lowest value of n
(a) 4
[ADs. (e)l
(b) 15 (c) 3 (d) 1 (e) 6 3p
48
3
4
'~J'
," .
I
0
4
4
} Lowest value of n
[Hint: n = 4; I 0; me =0 3d 3 2 5
1= 1; me = 1,0, + 1 '"',
1=2; m" = - 2, -1, 0, + I, + 2
4p
58
4
5
1
0
5
5 J Lowest value of n
./ 3; me ::; - 3, - 2, -1, 0, + I, + 2, + 3
There are three orbitals having me = + I, thus maximum numbe~
of electrons in them will be 6.]
98 G.R.B. PHYSIC,AL G~.E;MIl:?TRYFOR COMPETITIONS
Subshell n· ::ud; p x , Py and p z • All the three have sarnt: energy. The electron can
be accomniodated on anyone of thP. 2p-orbitals.fu the case of
~a1u~"of n
4d 4 2
carbon, sixth electron is also accommodated on 2p subshell and
5p 5 : ) . Lowest
its electronic configuration is represented as 1s 2 2s 2 2p2 but three
6s 6 0 ·6
orbital diagrams can be expected ..
~.
4f 4 3
, iJ,ii' .
~
5d
6p
5
6
2
7 1.' Lowest value of n . (I) [He] -
.
- - - ' Electrons are present on two
2s .L 2p .J different orbitals with parallel spins.
7s 7 0 7
, 5f 5 3 8 (ii) [He]i J, 1. -±-- Electrons are.present on two
2s .L 2p.J d'Ifferent
. orb'Ita. Is WI'th opposite
' spms.
.
6d. 6 2 8 ) Low", "lu, of n ,
7 8 (iii) [He] i t i J, _ _ Both the electrons are present on
. The energy of electron in a hydrogen atom and other single L2p.J . one orb'ItaI Wit. h' OPP9SI~
. spms.
. .
electron species like He + , Li 2+ and Be 3+ is determined solely by Experiments show that (i) orbital diagram is correct while (ii)'
the principal quantum number. The energy of orbitals in and (iii) are not correct. This has given birth to a new rule known
hydrogen and hydrogen like species increases as follows: as Hund's rule of maximum multiplicity. It states that electrons
1s< 2s= 2p < 3s= 3p = 3d < 4s= 4p= 4d = 4/ < ... are distributed among the orbitals of a subshell in such..a way·
The complete electronic' configuration of all the known as to give the maximum nuniber of unpaired electrons witll
elements have been given in the table on next page. It is observed parallel spins. Thus, the orbitals available in a subsheH are flrst
that few of the elements possess slightly different electronic filled singly before they begin to pair. This means that pairing of
configurations than expected on the basis of Autbau Prlnelple. electrons occurs with the introduction of .second electron in
These elements have been marked with asterisk (*) sign. s-orbitals, the fourth electron in p-orbitals, sixth electron in
:?2~1:.·; HUND'S RULE OF MAXIMUM d-orbitals and eighth electron in / -orbitals. The orbital diagrams of
nitrogen, oxygen, fluorine and neon are as given below:
. MULTIPLICITY (Orbital Diagrams)
Nitrogen (7) [He] 1t 1 i i
There is one more method of representing the electronic. config-
,. uration which is usually called as orbital diagra.~. In this method,
the' electron is shown by an arrow: upward direction i (clockwise . Oxygen (8) [He] i J, iti"i
spin) and downward direction t (anti-clockwise spin). ~L2p.J
To indicate the distribution of electrons among the orbitals of Fluorine (9) [He] itiJ,iJ,i
an atom, arrows are placed over bars that symbolise orbitals. 2s
C 6 2 2 2
N 7 2 2 3 i
i
0 8 2 .2 4
F 9 2 2 5
i i
Ne 10 2 2 6 (2 p completed)
!
Na U 2 2 6 I
Mg i 12 2
i
2 .6 2
i
. (38 completed)
Al 13 2 2 6 2 1
Si 14 2
P 15 2
2
2
6
6
2
2
2
3
I ,-
i I I
S 16 2 2 6 2 4
CI 17 2 2 6 2 5
AT i i
18 l 2 6 2 6 (3 P completed)
K 19 2 2 6 2 6 1
Ca 20· 2 2 i 6 2 6 2 (48 completed)
Sc 21 2 2 6 2 6 1 2
Ti 22 2 2 6 2 6 2 2
V 23 2 2 6 2 6 3 2
*Cr 24 2 2 6 2 6 5 1
Mn 25 2 2 6 2 6 5 2
Fe 26 2 2 6 2 6 6 2
Co 27 2 2 6 2 6 7 2
Ni 28 2 2 6 2 6 8 2
*Cu 29 2 2 6 2 6 10 1
Zn £10 2 2 6 2 6 10 2 :(3d completed)
Ga 31 2 2 6 2 6 10 2 1
Ge 32 2 2 6 2 6 10 2 2
.As 33 2 2 6 2 6 10 2 3
Se 34 2 2 6 2 6 10 2 4
Br 35 2 2 6 2 6 10 2 5
Kr 36 I 2 2. 6 2 6 10, 2 6 ! (4p completed)
Rb 37
i
2 2 6 2 6 10 2 6 I t
Sr 38 2 2 6 2' 6 10 2 6 2 (5scompleted)
y 39 2 2 6 2 6 10 2 6 1 2
Zr 40 2 2 6 .2 .6 10 2 6 2 2
*Nb 41 2 2 .6 2 6 10 2 (; 4 I
·*Mo 42 2 '2 6 2 6 10 :2 6 5 ' 1
Tc 43 2 2 6 2 6 10 . 2 6 5 2
*Ru 44 2 2 6 2 6 10 2 6 7 1
*Rh 45 2 2 6 '2 6 10 2 6 8 1
i !
·Pd i 46 2 2 .6 2 6 10 2 6 10
*Ag 47 2 2 6 2 .6 10 2 6 10 1
Cd 48 2 i
i 2 6 2 6 10 2 6 10 2 (4d completed)
In 49 2 2 6 2 6 10 2 6 10 2 1
Sn 50 2 2 6 2 6 10 2 6 10 2 2
Sb 51 2 .2 6 2 6 10 2 6 10 2 3
Te 52 .2 2 6 2 6 10 2 6 I 10 2 4
I 53 2 :.t. 2 2
I 6 6 10 2 6 10 2 5
I ,
,I I I
Xe 2 Cf
!
54 I ""'""~~
2 6 2 6
- 10 I
- 2 6 10 2 6 (5p completed)
100 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
m_.tl·~N~ I I K
L M 46 4.P- 4d ,,4/ 56 5p 5d Sf I 6.¥ 6p16d16f 16
Cs 8 18 2 6 6
ffi-f1
I
Ba 8 18 2 6 6 2 (68 completed)
'"La 57 8 18 2 6 6 I 2
'"ee 58 2 8 18 2 6 6 I 2
Pr 59 2 8 18 2 6 10 3 2 6 2
Nd 60 2 8 18 2 6 10 4 2 6 2
'"Pm 61 2 8 18 2 6 10 5 2 6, ' 2
8m 62 2 8 18 2 6 10 6 2 6 2
Eu 63 2 8 18 2 6 10 7 2 6 2
'"Gd 64 2 ,8 18 2 6 10 7 2 6 I 2
Tb 65 2 8 18 2 6 10 9 2, 6 2
Dy 66 2 8 18 2 6 10 10 2 6 2
Ho ,67 2 11 18 2 6 , 10 '11 2 6 2
Er 68 2 8 18 2 6 10 12 2 6 2
Tm 69 2 8 18 2 6 10 ' 13 2 6 :2
Vb 70 2" 8 18 2 6, t6;' 14 2 6 2
Lu 71 2 8 18 2 ,.,6 10 14 2 6 I 2 (4/ completed)
Hf 72 2 8 18 32 6 2 . 2
Ta 73 2 8 18 32 6 3 2
W 74 2 8 /
'i8 32 6 4 2
Re 75 2 $ 18 32 2 6 5 2
Os 76 2 " 8 18 32 2 6 6 2
Ir 77 2 8 18 32 2 6 7 2
'"Pt 78 2.. 8 18 32 2 6 9 1
'"Au 79 2 8 18 32 2 6 , 10, J
Hg 80 2 8 18 32 2 6 10 2 (5d completed)
Tl 81 2 8 18 32 2 6 10 2 1"
Pb 82 2, 8 18 32 2 6 10 2 2
Bi 83 2 8 18 32 2 6 10 2 3
Po 84 2 8 18 32 2 6 10 2 4
At 85 2 8 18 32 2 6 10 2 5
Rn 86 2 8 18 32 2 6 10 2 6(6p completed)
Fr
Ra
'"Ac
·Th
·Pa
PH+
90
91
2
2
8
8
8
8
8
18
18
18
18
18
32
32
32
32
32
2
2
;
2
6
6
6
6
6
10
10
10
10
10
0
2
2
;
2
6
I
2
I
1
2 (7scompleted)
2
2
2
'"U 92 2 ~ 18 32 2 6 10 3 2 6 I 2
·Np 93 2 8 18 32 2 6 10 4 2 6 1 2
Pu 94 2 8 18 32 2 6 10 6 2 6 2
Am 95 2 8 18 32 2 6 10 7 2 6 2
·Cm 96 2 8 18 32 2 6 10 7 2 6 I 2
*Bk 97 2 8 18 32 2 6 10 8 2 6 I 2
Cf 98 2 8 18 32 2 6 10 10 2 6 2
Es 99 2 8 18 32 2, 6 10 11' 2 '6 2
Fm 100 2 8 18 32 2 6 10 12 2 6 2
Md 101 2 8 18 32 2 6 10 B ,2 6 2
No 102 2 8 18 32 2 6 10 14 2 6 2
*Lr 103 2 8 18 32 2 6 10 14 2 6 I 2 (5/ completed)
KuorRf 104 2 8 18 32 2 6 10 14 2 6 2 2
HaorDb. 105' 2 8 18 32 2 6 10 14 2 6 3 2
Sg 106 2 8 18 32 2 6 10 14 2 6 4 2 I!!
Dh 107 2 ,8 18 i,~·g
32 2 6 10 14 2 6 5 2 ,ggi
Hs 108 2 8 18 32 2 6 10 14 2 6 6 2 !Jtj
Mt 109 2 8 18 32 2 6 10 14 2 6 7 2 "8
*UunorDs 110 2 8 18 32 2 6 10 14 2 6 9 I
*Uuuor Rg III 2 8 18 32 2 6 10 14 2 6 10 1
Uub 112 2 8 18 32 2 6 10 14 2 6 10 2 (6d completed)
I
.\
All those atoms which consist 'of at least one of the orbitals
singly occupied behave as paramagnetic materials because these
•
:::=
::[II- I]
hi
o
.. A
are weakly attracted to a magnetic field, while aU those atoms in
which all the orbitals are .doubly occupied behave as . where, Vo and Ao are threshold frequency and threshold'
diamagnetic materials because they have no attraction for wavelength respectively.
magnetic field. However, these are slightly repelled by magnetic Stopping potential: The minimum potential at which the
field due to induction. plate photoelectric. current becomes zero is called stopping
Magnetic moment may be calculated as, potential.
IfVo is the stopping potential, then
11=~n(n+2)BM eVo = h(v- v o )
eh
I BM (Bohr Magneton) -- Laws of Photoelectric Effect
.•. 4nmc·
where, n =no. of unpaired electron (i) Rate of emission of photoelectrons from a metal surface
is directly proportional to the intensity of incident light.
Exceptions to Aufbau Principle (ii) The maximum kinetic energy of photoelectrons is
In some cases, it is seen that actual electronic arrangement is directly proportional to the frequency of incident
slightly different from arrangement given by aufbau principle. A radiation; moreover, it is independent of the intensity of
simple reason behind fhis is that half-filled and fuU:'filled light used.
subshells have got extra stability. (iii) There is no time lag between incidence of {ight and
Cr24 -----+ ls2,2!i2l,3i3l3d 4 ,4s2 (wrong) emission of photoelectrons.
2 2 s 1 (iv) For emission ofphotoeJectrons, the frequency ofincident
-----+. lsL,2s 2l,3s 3l3d ,4s (right)
light must be equal to or greater than the threshold
Cu 29 -----+ . ls2, 2s 22l, 3s 23l3d. 9,4s2 (wrong) frequency.
-----+ ls2, 2s22p6, 3s23l3dlO, 4S1 (right)
1t
-
0
0
-4.8029
0
0.1514
0.1454
} Powell (1947)
2.22 ISOTOPES
Isotopes are the atoms of the same element having differen l on atomic mass. Isotopes were first identified in radioactive
atomic masses (see determination of isotopic mass). The term elements by Soddy. In 1919, Thomson established the existence
'isotope' was introduced by Soddy. This is a Greek word of isotopes in a non-radioactive element, neon. Until now, more
=
meaning same position (lsos same, topes = position), since all than 1000 isotopes .have been identified (natural as well as
the isotopes of an e1ement occupy the same position in the artifichd). Out of these about 320 occur in nature, approximately
periodic table. Isotopes of an element possess identical chemical 280 of these are stable and the remaining 40 are radioactive.
properties but differ slightly in physical properties which depend
I
ATOMIC STRUCTURE 103
Conclusions ',' same two particles (i. e., protons) are at least forty times greater
i . .. "
than the repulsive forces; Thus, two major forces exist in the
(i) Number of n~trons present in the nuclei of various
nucleus. These rrre electrostatic and nuclear. The nuclear forces
isotopes of an ~lement is alw~ys different. The number of '
are stronger and the range of these forces is extremely small. The
neutrons is detennined by applying the formula N =A - Z
forces which operate between nucleons are referred to as
where A is mas~ number and Z is atomic number.
exchange forces. In order to account for the stability of the
Hydrogen has tHree isotopes, ~ H, fH and H. i nucleus, a theory known as meson theory was put forward by
A (MIll ~umber) Z No. of neutrons Yukawa, in 1935. Yukawa pointed out that neutrons .and protons
o are held together by very rapid exchange of nuclear particles
called pi mesons. These mesons may be electrically neutral,
2
positive ornegative (designated as nO , n + and n - ) and possess a
'tH 3 2 mass 275 times the mass of an electron. Nuclear forces arise from
Oxygen has tliree isotopes, 16 0 , 170and 18 O. a constant exchange of mesons between nucleons with very high
velocity (practically the velocity of light).
A Z No. of neutrons Let a neutron be converted into a proton by the emission of a
1:0 16 8 8 negative meson. The emitted meson .is accepted by another
proton and converted into a neutron.
llo 17 8 9
--
"J8 . _'"_TT __ "
."
n A ~ p~ +n-
gO 18- 8 '10'
n- + p; ~nB
(ii) In a neutral atom, the number of protons and the number
Similarly, a proton after emitting a positive meson is
of electrons are aht'ays the same, i. e., the electronic converted into a neutron and vice-versa,
configuration of all the isotopes of an element is the
p~ ~nA +n+
same. Thus, all the isotopes of an element show the same
chemical properties. However, the rates of reactions may n+ +nB ~p;
be different for different isotopes of an element.
or simply
(iii) All the isotopes of an element occupy the same position
in the periodic table. n ~ n- + p
(iv) The isotopes of an element differ slightly in physical There may be two more types of exchange, i. e., between
properties. The compounds formed by these isotopes will neutron-neutron and proton-proton, involving neutral pi mesons.
also have different physical properties. p n. 11.0 nO
"'-no '\no orsimply p"--; p and n~n
Determination of Isotopic Mass p It" nit" .n nO
37
Chlorine has two isotopes 17 Cl 3S and 17 Cl ; these are found
in nature in 3 : 1 ratio or 75%: 25% respectively. Isotopic mass'
Mass Defect-Binding Energy
may be calculated as: ". . , . It is observed that the atomic mass of all nuclei (except
Isotopic mass of chlorine hydrogen) is different from the sum of the masses of protons and
neutrons. For example, the helium nucleus consists of2 protons
3s 7
%of
- -- . 0 f Cl35 + %of ct3
Cl - x mass X mass 0 f Cl 37
and 2 neutrons. The combined mass of 2 protons and 2 neutrons
100 100 should be
75 25 = 2 x 1.00758 + 2 x 1.00893
=- x 35 + x 37 =35.5 4.03302 amu
100 100
OR The actual observed mass of helium nuclei is 4.0028 amu. A
Isotopic mass of chlorine . difference of 0.0302 amu is observed between these two values,
This difference is termed as mass defed.
Ratio of Cl 35 x mass of Cl 3s + Ratio of Cl 37 x mass of Cl 37
Mass defect = Total mass of nucleons Observed atomic mass
Sum of ratio
This decrease in mass (i. e., mass defect) is converted into
= 3 x 35 + 1 x 37 = 35.5
energy according to Einstein equation E mc 2 • The energy
4
released when a nucleus is formed from protons and neutrons. is
2.23 THEORIES OF NUCLEAR STABILITY called the binding energy. This is the forfe which holds all the',
Since, a nucleus contains positively charged protons, there must nucleons together in the nucleus. Binding eI1ergy can be d~fined in
exist a strong repulsive force between them. It has been other ways also, i. e. , the energy required tohreak the nucleus· into
calculated that there exists an electrostatic repulsion of constituent protons and neutrons. Binding energy is measured in
approximately six tons between two protons situated at a nuclear ' MeV (Million Electron-Volts), i. e. , 1 aml.l 931 MeV.
distance but at the same time the forces which bind the nucleus Binding energy =Mass defect x 931 MeV
are very high. It has been found that. nuclear forces attracting the
,
104 ' G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Bjnding energy can also be calculated in erg. This is ':t«i THE WHOLE NUMBER RULE AND
Mass defect (amu) x J .66 X 10- 24 x (3 X 1010 )2 erg PACKING FRACTION
6
(l MeV = 1.60 x 10 erg) Aston believed that mass number values (sum of protons and,
The binding energy increases with the increase in atomic neutrons) of isotopes should be whole numbers on the scale of
number of the element. This indicates that heavier nuclei should oxygen ( 16 0 = 16) but actually it was observed that these were
, be' more stable than lighter nuclei. But, it is not so because not integers. The difference in the atomic mass of an isotope and
heavier nuclei above atomic number 82 are unstable. It is thus mass number was expressed by Aston (1927) as packing
clear that total binding energy of a nucleus does not explain the"" " fraction bythe following expression:
stability of the IUlcleus.
The total binding energy of a nucleus when divided -by the P k' fra' Isotopic atomic mass'- Mass number 104
, ac 109 ctlOn = " x
number of nucleons gives the average or mean binding energy Mass number
per nucleon. The binding energy per, nucleon is actually the
measure of the stability of the nucleus. The greater the binding ' the pack~109 fra'
energy per nucleon, more stable is_the nucleus. Thus, ctlOn 0 f IH = l.OO78~ I x 104 78 and
I
Binding energy per nucleon
Total binding energy
the pacmgk ~ fra'ctlon
. '0,f 3sCI
,=
34.980 35.0 x 104 =-5.7. The
Total nwnber of nucleons 35.0
packing fraction of oxygen is zero.
When binding energy per nucleon of a number of nuclei is
It is clear that the value of packing fractlon varies from one---~~
plotted agairlst the corresponding 'maSs number, a graph is
atom to other. This is sometinie positive or zero but more often
, obtained (Fig. 2.19) whose characteristics are as follows:
negative.
Region of A negative packing fraction means that atomic mass is less
greatest stability than nearest whole number and this suggests that some mass has
f:
':> 8
I---r----,--
been converted into energy when the particular isotope has been
constituted. This energy is r~sponsible for nuclear stability. All
those having negative values of packing fraction are stable
Q) nuclei.
67 Apositive packing fraction generally indicates instability of
ju 6 1-1'---+- the nucleus. However, this statement is not correct for lighter
nuclei.
E5 In general, lower the value of packing fraction, the gr~ter is
~ 4H---+- the stability of the nucleus. The lowest values of packing
>.
fractions are observed for transition elements or iron family
~3
c:: indicating thereby maximum stability of their nuclei.
~ 21i---+-
c::
'g ,~~ ,THE MAGIC NUMBERS
iii
It has been observed that atoms with an even number of nucleons
o 20 40 60 80 100 120 140 160180200220 240 in their nuclei are more plentiful than those with odd number.
, Mass number, A - This indicates that a nucleus made up of even number of nucleons
Fig. 2.19 is more stable than a nuclei which consists of odd number of
(i) Binding energy per nucleon increases from l.l to 8.0 nucleons. It has also been observed that a stable nuclei results
MeV from mass number 2to 20. when either the number of neutrons or that of protons is equal to
(ii) Binding energy per nucleon increases from 8 to 8.6 MeV one of the numbers 2, 8, 20, 50, 82, 126. These numbers are
from mass number 20 to 40. ' called magic numbers. It is thought that the magic numbers form
closed nuclear shells in the same way as the atomic numbers of
(iii) Binding energy per nucleon remains 8.6 -8.7 MeV from
mass number 40 to 90. Iron (56) has the maximum value inert gases form stable electronic configuration. In general,
of8.7 MeV per nucleon. elements that have nuclei with magic number of !:fotons as well
(iv) The value of binding energy per nucleon decreases from a.-, magic number of neutrons such as jHe, I~O, 20 Ca, 2~~Pbare
8.6 to 7.5 MeV from masS number 90 to 240. highly stable and found in abundance in nature.
(v) Points for helium, carbon; oxygen lie quite high in the A survey of stable nuclei found in nature shows the following
graph showing that these nuclei are highly stable. trend:
The binding energy per nucleon can be increased in two ways: Protons Even Even Odd Odd
(i) Either by breaking heavy nucleus to those of NeutronS Even Odd Even Odd
intermediate mass numbers (process of fission) or No. of stable nuclei 157 52 50 5
(ii) By fusing lighter nuclei to form heavier nuclei (process Only five stable odd-odd nuclides are known; these nuclides
of fusion). 2H' 6 · 10 14N' d 180 '
are I ',3 LI, sB, 7 an 73 Ta.
•
ATOMIC STRUCTURE 105
.
: : :::n_SOME SOLVED EXAMPLES\ I:::: : : Example 50. Write down the values of quantum numbers
of all the electrons present in the outermost orbit of argon
Example 46. The minimum energy required to overcome (At. No. 18).
the attractive forces between an electron and the suifaceof Ag Solution: The electronic configuration of argon is
metal is 5.52 x 10- 19 J. What will be the maximum kinetic energy 1s 2 , 2s 22p 6 , 3s 2 3p2x 3p2y 3p2z
of electrons ejected out from Ag which is being exposed to UV Values of quantum numbers are:
light ofA = 360A'? n / m s
Solution: Energy ofthe'photon absorbed 3i 3 0 0 +~.-~
h . c 6.625 X 10-27 X 3 X 1010 3p; 3 ±l +~.-~
=- =--------:::---
8
A 360 x 10- 3p.~ 3 ±1 +~,-~
= 5.52 X IO- It erg 3p; 3 0 +~,-~
= 5.52 x 10- 18 J Example 51. (a) An electron is in 5f-orbital. What
E(photon) work function + KE possible values ofquantum numbers n, I, m and s can it have?
KE=5.52xlO- 18 -'7.52xIO- 19 , (b) What designation is given to an orbital having
(i) n = 2, I =I and (ii) n = 3, 1= O? .
=47.68 X 10- 19
J
Solution: (a) For an electron in 5f-orbital, quantum numbers
"''''E,lample 41~ Let a light ()f wavelength' Aand intensity ']' are: .----,-~--~-
when, A is halved, average energy will increase but it will not 3s-e1ectron has the highest energy. Its quantum numbers are:
become double. 1 1
n=3, 1=0, m=O" s=+ ' 2 or--2
(b) Rate of emission of electron per second 'x' will become
double when intensity ] is doubled. Average energy of ejected Example 53. An element has 8 electrons in 4d-subshell.
electron, i. e., 'y' will be unaffected by increase in the intensity of Show the distribution of 8 electrons in the d-orbitals of the
light. . ' element with~n small rectangles.
'" Example 48. How many orbits, orbitals and electrons are Solution: 4d-subshell has five d-orbitals. These are first
there in an atom having atomic mass 24 and atomic number 12? occupied singly and then pairing occurs. The distribution can be
Solution: shown in the following manner:
Atomic number = No. of protons = No. of electrons = 12 4d
Electronic configuration 2, 8, 2 [iJ,!iJ,!H! i ! i J
No. of orbits = (K. Land M ) Example 54. How many elements would be in the third
No. of orbitals on which electrons are present period ofthe periodic table if the spin quantum number ms could
=(one 1s + one 2s + three 2p + OI~e 3s) I
have the value - - ,0 and + - ?
I
Example 49. A' neutral atom has 2K electrons, 8L 2 2
electrons and 6 M electrons. Predict from this: Solution:
(a) its atomic number, (b) total number of s-electrons. (c) total n=3,/=O,m=0
number ofp:electrons, (d) total number ofd-electrons.
Solution: (a) Total number of electrons ' . ms = -1/ 0 +1/
~
/2,,72
These examples will give the sharp edge to the aspirants for Solution:
lIT and various other entrance examinations. Coulombic force of attraction =Centrifugal force
Exa.mple 1. The SchrOdinger wave equation for hydrogen 1 Zexe mv 2
atom is
4nEo T=~
_ 1 (1 [2
'112s - - - - - -
)3/2 ro ] -rlao
-- e . where, v:= velocity of electron
4~n ao ao
ao = distance between electron and nucleus
where ao is Bohr radius. If the radial node in 2s be at· ro ' then
find r in terms ofao. (liT 2004) 1 Ze 2 _ 2
-----mv
Solution: Given, 4nEo ao .
_ 1 (1 [2
'112s - - - - - -
)3/2 ro ] e -rlao
-- KE
1 2 1 Ze 2
-mv = - - - ; r -
2 . ' ~nEQ·.Lao
4~n ao ao
PE=-2xKE .
'II~s = Qat node 1 I, Ze 2
-2x~x-=
4ntb· 2ao
Example 3. Hydrogen atoms are excited from ground
state. Its spectrum contains wqvelength 486 nm. Find, what
ro = 2a o transition does the line corresponds to. Also find from this
information what other wavelengths will be present in the
Example 2. Consider the hydrogen atom to be a proton
spectrum?
embedded in a cavity of radius ao (1!ohr radiUS) whose charge is
neutralized by the addition ofan electron to the cavity in vacuum Solution: Wavelength 486 nm, i. e., 4860, A indicates that
infinitely slowly. Estimate the average total energy ofan electron the spectrum is in visible region, i. e. , Balmer series.
in its ground state in a hydrogen atom as the work done in the
above neutralization process. Also, if the magnitude of average 1. = Rz.2 [_1 ....:_11
KE is half the magnitude of average potential energy, find the A nr ni
average potential energy. (lIT 1996)
ATOMIC STRUCTURE 107
•
_ _1_ _ g ::::: 109677.76 x 12 [~- ~l . [1 1J
=109678 - - -
32 4 2
4860x 10- 2 n2
. .~ = V~
Given, Ax ::::: [""h : : : 0.726 X 1O-I7 integers on rriultiplyingby 2.
:.Charge of the negatron will be
~:::::m~V 19
3.2 x 10- =.1.6 X 10- 19 C
. ~ 17 2
or AV= P ::::: 0.726 x 10- =7.98 x 1012 ms- I '. . .
m 9.1 x "Example 8. When a certain metal was irradiated .with
light offrequency 12x 1016 Hz, the photoelectrons emitted had
Example 5. How much· energy will be released when a
sodium ion and a chloride ion, originally at infinite distance are twice the kinetic energy as did photoelectrons emitted when the "
brought together to a distan.ce of2. 761 (the shortest distance of same metal was irradiated with light offrequency 2.0x 1016 Hz.
approach in a sodium chloride c rys tal)? Assume that ions act as Calculate v 0 for the metal.
point charges, .each with a magnitude of 1.6 x 10- 19 C. Solution: Applying photoelectric equation,
Permittivity constant of the medium is 9x 109 Nm 2C -2.
KE hv-hvo
Solution: Energy released
" KE
9 19 or (v-vo)==
== _ K = _ 9 X 10 x (16 X 10- )2 = -8.35 X 10- 19 J h
r . 2.76 x 10- 10 Given,
. Example 6. The angular momentum of an electron in a
... (i)
Bohr orbit ofH-atom is 4.2178 X 10-34 kg m 2/sec. Calculate the
spectral line emitted when an electron fails from this level to the
next lower level. and ... (ii)
. "h
Solution: We know, mvr= n Dividing equation (i) by equation (ii),
21t
34 v 2 -vo == = 2KEI =2
4.2178x 10-34 = n x 6.626 x 10-
2x 114 VI - Vo KEI KEI
=8.0 X 1015 Hz
108 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
A==
.
h
28
[m=9.108x 10- g
. h 6.626 X 10-27 erg ~sec
1 Solution: Uncertainty in velocity
A
uv= 600 x 0.005 3
::::.x 10-2
. .
ms -I
100 .
~2mx KE leV= 1.602 x 10- 12 erg According to Heisenberg's
.. ---- •. - - -- uncertainty
-
principle
--c- -- - .,---------
c- 7 -
6.626 x 10:"27 h
AtAv~-
4rcm
~2 x 9.108 x 10-28 x 2.5 x 1.602 x 10- 12
At ~ h
== 7.7 x 10-8 cm 4nmAv
c.· Example 10.· Consider the following two electronic
transition possibilities in a hydrogen atom as pictured below: 6.63 x 10- 34
~----------------------
·4x3.l4x9.1x
=tt
n=3
. n=2 == 1.9 x to- 3 m
1. Atom is the smallest indivisible particle of matter 8. Isotones: These are atoms of different elements having
(proposed by John Dalton in 1808). same number of neutrons in the nucleus, e.g.,
2. All atoms except hydrogen atom are composed of three
ItC: l~, 19O
fundamental particles, namely, electron, proton and neutron.
Hydrogen atom has one electron and one proton but n~ neutron.
9. Electromagnetic radiations are energy waves containing
(a) Electron: The nature and existence of electron was both electric and magnetic vector perpendicular to each other.
established by experiments on conduction of electricity through
(i) These are transverse waves.
gases, i.e., discovery of cathode rays. In 1897, J.J. Thomson
(ii) They do not need any medium for their propagation. They·
determined e/ m value (-1.7588 x 108 coulomb/g) and proved travel with the velocity of light. '
that whatever gas be taken in the discharge tube and whatever be
the material ofthe electrodes, the value of e/ mis always the same. (iii) v:::: C ,V =frequency, c =veiocity oflight,
A '
Electrons are, thus, common universal constituents of all atoms. A = wavelength
Electron is a' subatomic pru.:ticle which carries charge
V ='= .~1. T
I wave'Ilwiwer, .:.;,;I = tIme
. per1
' 'od.
-1.60 x 10-19 coulomb, i.e., one unit negative charge and has A," v
maSs 9.1xlO-28 g (or 9.1 x 10-31 kg), i.e., _l_th mass of (iv) According to Planck's quantum theory, the energy is
1837 emitted or absorbed in the fOlTIl of energy packets called quanta.
hydrogen atom (0.000549 amu). The name electron was given by Quantum of visible light is called photon.
Stoney. ' Energy of one quantum == hv
(b) Proton: The nature and existence of proton was
established by the discovery of positive rays (Goldstein 1886). ==h5..
A
Proton is a subatomic particle which carries +1.6x 10- 19
coulomb or one unit positive charge and has mass 1.672 x 10-24 g h = Planck's constant
27
(or 1.672 x 10- kg), i. e., 1.0072 amu. The el m was determined 6.626 x 10-34 J sec
by Thomson in 1906 and the value is +9.579 x 104 coulomb/g. It
"': 10. Hydrogen spectrum: Hydrogen spectrum is a line
was named as proton by Rutherford. spectrum. The lines lie in visible, ultraviolet and infrared regions~
(c) Neutron: It is a subatomic particle which carries no All the lines can be classified into five series. Ritz presented a
charge. Its mass is 1.675 x 10-24 g (1.675 X 10-27 kg) or 1.0086 mathematical formula to find the wavelengths of various lines,
amu. It is slightly heavier than proton. It was discovered by
Chadwick in 1932 by bombarding beryllium with a.-particles. -.!.=V=R[~-~l
A. n n l 2
4.
Density of nucleUs = 108 tonnes/cc
Atomic number (Z) =Number of protons in the nucleus
Brackett series
Pfund series
} (IRregion) 4
5
5,6,7,8, ...
6,7,8,9, ...
S. Mass number (A) =Number of protons + Number of Balmer series consists offour prominent lines Ha., IIp, Ry and
neutrons H3 having wavelength 6563 A, 4861 A, 4340 A and 4102 A
6. Isotopes: These are atoms of same element having respectively. . .
same atomic number but different mass numbers, e. g., Balmer equation is,
<l H, ;H, fH): mCI, r;Cl) -.!.=R[~ __
l2 ]
A 22 n
7. Isobars: These are atoms of different elements having
same mass number but different atomic numbers, e.g., where, H == 3,4,5,6, ...
The Rydberg formula is used to calculate the wavelength of
:~Ar, teK, ~Ca any line of the spectrum
I
110 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
E=--
Z2 2n 2 mK.2'e4
2 (xii) Ionization energy =E~ - En'
n h2
RE = - l3.6 eV (Rydbetg energy) I, and 12 are ionization energies of two elements 1 and 2.
2
(v) En :::;:E\ln 2 ;En =E1 X~forhydrOgen-likespecies.
n . (xiv) AE'{Energy of transition) := RE
. , . ..
[-i-.n, -~)n2
(vi) Velocity of electrons in a particular shell or orbit can be
calculated as: . . }{f::::-13.6 eV
ATOMIC STRUCTURE 111
with velocity v is given by the relationship A = ...!!:.- ; where, h is 1= 0, 1,2,3, ... ,(n -1)
mv 1= 0 (s-subshell); 1= 1(p-subshell); I = 2 (d-subshell);
Planck's constant. 1=3 (f-subshell). .
The wave nature was cQnfl11lled by Davisson and Germer's Orbital angular momentum of electron
experiment.
Davisson and Germer gave some modified equations for = ~/(l + l)..!!...- = ~/(l + 1)/i
calculation of de Broglie wavelength: 2n
A= h ; where, E = kinetic energy of the particle. when I = 0, electrons revolve in a circular orbit and when I 0, *
·hEm the electrons revolve round the nucleus in an elliptical path.
(iii) Magnetic quantum number: It is denoted by 'm'. It
A= h ; where, q = charge ofthe particle accelerated by describes the orientations of the subshells. It can have values
~2qVm from -I to +1 including zero, i. e., total (21 + 1) values. Each valQe
corresponds to an orbital. s-subshell has one orbital, p-subshell
the potential of V volt.
has three orbitals (p x , P y and p z), d-subshell has five orbitals
15. Heisenberg uncertainty principle: It is imp~ssible to
. (d xy " d}'2' d zx , d> _ y2 and d z2) and f-subshell has seven
measure simultaneously,both the position and moment"umof any
microscopic particle with accuracy. Mathematically, orbitals. One orbital can .accommodate either one or two
h electrons but not more than two. s-orbital is spherically
llx I:l.p::: 4n; where, llx = uncertainty 10 position and
symmetrical and non-directionaL p-orbitals have dumb-bell
I:l.p = uncertainty in momentum. It introduces the concept of shape and are directional in nature. Four d-orbitals have double
probability of locating the electron in space around the nucleus. dumb-bell shape but· d z2 has a baby soother shape. The total
16. de Broglie concept as well as uncertainty principle have numl?er of orbitals present in a main energy level is 'n 2 '.
no significance in everyday life because they are significant for (iv) Spin quantum number (s): It describes the spin orthe
only microscopic systems. electron. It has values + II2 and '-'1/2. (+) signifies clockwise
17. When radiations of a certain minimum frequency (vo ), spinning and (-) signifies anticlockwise spinning.
called threshold frequency, strike the surface of a metal, electrons
called photoelectrons are ejected from the surface. The ininimum
Spin angular.momentum = ~s(s +. l)..!!...-
2n
energy required to eject the electrons from the metal surface is
called threshold energy or work function.
( where, s = ~J
Absorbed energy = Threshold energy + Kinetic energy of
photoelectrons Total spin of an atom or an ion = n x.!.; where, 'n' is the
E=Eo +KE 2
number of unpaired electrons.
1 2
hv=hvo +-mv Spin !Jlultiplicity of an atom = (2rs + 1)
2
I
112 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Singlet state (Nonnal) Singlet excited 22. Autbau principle: Aufbau is a Gennan word meaning
i.! ± building up. The electrons are filled in various orbitals in an order
of their increasing energies. An orbital of lowest energy is filled
Spin multiplicity 1 first. The sequence of orbitals in the order of their increasing
;: : n:s+ 1 Spin multiplicity 1 energy is:
]S, 2s, 2p,3s, 3p,4s, 3d, 4p,5s,4d, 5p,6Y, 4.f, 5d, 6p,7s, 5f,6d, ...
=2xO+l=1 The energy of the orbitals is governed by (n +/) rule.
Triplet excited state (i) Subshell with lower of (n + I) has lower energy, hence
1 filled fIrSt, e.g., .
i 3p(n + 1 = 4) will be filled before 3d(n + I 5).
Spin multiplicity (ii) When (n + I) values are same, then the subshell with
lower value of 'n' is filled fIrst, e. g. ,
2XG+~)+1=3 3p(n+I=4) will be filled before 4s(n+1 4.)
because 3p has lower value of n..
19. (i) Number of subshells in a shell =n 23. Hund's rule: No electron pairing takes place in the
orbitals in a subenergy shell until each orbital is occupied by one
(ii) Number of maximum orbitals in ashell =n 2
.. ~le.ctro.n~ ~it1!~p..!U:~!Ie.Lspi!1' Ex:a(;.t1YJ!1l1f:fill~ar~~~llYiJi.lle.~
(iii) Number ofmaxiInum orbitals in a subshell =21 + 1 orbitals make the atoms more stable, i. e., p ,p ,d , d ,.f
(iv) Maximum number of electrons in a shell ;:::: 2n 2
(v) MaximUm number of electrons in a subshell
and /4 configurations are most stable.
All those atoms which consist of at least one orbital singly
=
2(21+ 1)
occupied behave as paramagnetic while all those atoms in
(vi) Z-component of the angular momentum depends
which all the orbitals are doubly occupied are diamagnetic in
upon magnetic quantum number and is given as:
nature.
, h) . Magneticmoment;::::~n(n+2)BM .
Lz =ml21t n = number of unpaired electrons
(vii) Number ofradiaVspherical nodes in any orbital 24. Half-filled and fully-filled suhshells have extra stability
due to greater exchange' energy and spherical symmetry
=(n~/:"'l)
around the nucleus.
]s orbital has no node; 2s orbital has one spherical
25. It is only dz2 orbitals which do not have four lobes like
node; 2porbitalhas no spherical node; 3porbital has
other d-orbitals.
one spherical node.
26. The d-orbital whose lobes lie along the axes is d 2 2 •
(viii) Schrodinger wave equation does not give spin x -)'
quantum number. . 27. Wave mechanical model of atom: It was
(ix) A plane passing through the nucleus at which the SchrOdinger who developed a new model known as wave
probability of finding the electron is zero, is called mechanical model of atom by incorporating the conclusions of de
nodal plane. Broglie and Heisenberg uncertainty principles. He derived an
The number of nodal plane in an orbital 1 = ... equation, known as Schrodinger equation.
.\'-Orbitals have no nodal plane; p-orbitals have one d 2", d 2", d 2", 8x2m
nodal pJane, d-orbitals have two nodal planes and so - -2+ - - + - - + (E-V)", 0
on. dx dy2 dz2 .
20. Pauli's exclusion principle: No two electrons in an The solution of the equation provides data which enables us to
atom can have the same set of all the four quantum numbers, i. e., calculate the probability of finding an electron of specific energy.
an orbital canuot have more than 2 electrons because three It is pOssible to determine the regions of space around the nucleus
quantum numbers (principal, azimuthal and magnetic) at the where there is maximum probability of locating an electron of
most may be same but the fourth must be different, i. e., spins specific energy. This region of space is tenned orbital.
must be in opposite directions. It is possible to calculate the
'" is the amplitude of the wave at a point with coordinates
maximum number of electrons which can be acconunodated on a
x, yand z. 'E' is total energy called eigen value and V denotes the
main energy sheD or slibenergy shell on the basis of this potential energy of the electron;
principle.
",2 gives the probability offmding the electron at (x, yand z).
21. Electronic configuration: The arrangement of
electrons in various shells, subshells and orbitals in an atgm is Operator form of the equation can be given as:
tenned electronic configuration. It is wrltten in tenns of nl x HW = E",
where n indicates the order of shell, 1indicates the subshell and x
the number of electrons present in the subshell.
ATOMIC STRUCTURE 113.
if ;: [- 4
8n m
1
A? :.- V called Hamiltonian operator·
.
30. Plot of radial probability density 'R 1 ,:
=T+V
T= Kinetic energy operator t \. 1ISS. ." . . .
2s 2p
(a) Radius of eleGtron orbit (P) Principal quantum (a) Orbital angular momentum (P) Principal quantum
number of the electron in a hydrogen- number
(b) Energy of electron (q)-Azimutbalquantum. like at.Qmi,G orl:>ita,l
number (b) A hydrogen-like one electron (q) Azimuthal quarttum
(c) Energy of subshell (r) Magnetic quantum wave function obeying Pauli number
number principle
(d) , Orientation of the atomic (s) Spin quantum number (c) Shape, size and ori,entation (r) Magnetic quantum
of hydrogen-like atomic , number
orbitals
orbitals
[K] M.atch the List-I with List-II: (d) Probability density of (s) Electron spin quantum
List-I List-ll electron at the nucleus in number
hydrogen-like atom
(a) ElectrolJ. cannot exist in (P) de Broglie wave
[0] Match the List-lWith List-II: . ,(lIT 2006)
the nucleus :~!:-.
(a) VnlKn ?' (p) 0 [P] Match the Column-! with Column-II:
(b) lfradius of nth orbit oc Enx; x = ? (q) Column-I Column-ll
(c) Angular momentum in lowest orbital (r) - 2 (a) Orbital angular (P) ~s (s + l)h/2n
momentum of an electron
(d) 1 ocZY ; y=? (s) 1
r" (b) Angular momentwn of (q) ~n (n + 2) BM
electron
(c) Spin angular mQ,mentum (r) nh/2n
of electron
(d) Magnetic 'moment of atom (s) h/2n
116 G.R.B. PHYSICAL CHEMI,STRY FOR COMPETITIONS·
[Q] Match the Coh,unn-l with Column-II: [R] Match the Column-I with Column-II:
Column-l (;vlumD~lI .- Column-I Column-II
(a) Scintillation (P) , Wave nature (a) Radial function R (P) Principal quantum
(b) Photoelectric effect (q) P~\ltiCle nature' number 'n'
(c) Diffraction (r) Particle nature dominates (b) Angular function e (q) Azimuthal quantum
over wave nature number 'I'
(d) Prin~iple of electron " (s) Wave nature dominates (c) Angular function CP (r) Magnetic quanfum
microscope over particle nature number'm'
(d) Quantized angular (s) Spin quantum number's'
momentum
1. [A] (i-e); (ii-d); (iii-f); (iv-b); (v-a); (vi-'c) [I] (a-,r, s) (b-p, s) (c~, r) (d-p, q)
[B] (i-d); (ii-a); (iii-b); (iv-'---f); (v-c); (vi-e) [J] (a-p) (b-p) (c--p, r) (d-r)
[C] (i-f); (ii-d); (iii-:-:a); (iv-e); (v-,b);(vi-c) [Kl{a-rHb--p)(c~;s) (d-r)-
2. [A] (a-q, r, s) (I~r) (c-p) (d-dpes not match) [L] (a-r) (~)(c-p) (d-s)
[B] (a-q, s) (b-p, s) (c-r, s) (d-fP, s) [M] (a-r, p) (b-r) (c-q) (d-s)
[C] (a-r, s) (b-p) (c-q) (d-q)~ [N] (a-p) (b-s) (c-p, q, r) (d-p, q)
[D] (a~, r) (b-p, q) (c-s) (d-p, q) [0] (a-r, s) (b-p, q) (c-p) (d-q)
[E] (a-q, r) (~, r, s) (c~p) (d-p) [P] (a-s) (b-r) (c-p) (d-q)
[F] (a-p, r) (~, s) (c~, s) (d-p, r) [Q] (a-q) (b-r) (c-p) (d-p, s)
[G] (a~, r)~) (c-s) (d~, r)
[R] (a-p, q) (~, r) (c-r) (d~, s)
[H] (a-r, s) (~, s) (c~, p) (d-p, r)
RACTICEPROBLE • '
1. An atom of an element contains 13 electrons. Its nucleus has 14 4. Calculate the number of neutrons in 18 mL of water. (Density
neutrons. Find out its atomic number and approximate atomic of water = 1)
mass. An isotope has atomic mass 2 units higher. What will be [Ans. 48.16 x 1023 ]
the number of protons, neutron~ and electrons in the isotope?
[Hint: One molecule of water contains = 8 neutrons J
[Ans. At. No. =13, atomic mass =27; the isotope will have
same number of protons and electrons 13 but neutrons will be 5. Find (i) the total number of neutrons and (ii) the total mass of
14 + 2 = 16] neutrons in 7 mg of 14C (assuming that mass of neutron
2. From the following find out groups of isotopes, isobars and mass of hydrogen atom). '
isotones: [Ans.(i) 24.08 x 1020 and (ii) 4 mg]
16 0 391(, 14C 239U 14N 40C 238U 77G'
8 '19 6 ' 92 , 7 , 20 a, 92 '-32 e, 6. Calculate the wavelength of a photon in Angstroms having an
17As 18 0 76G 78S energy of 1 electron volt.
33 ' 8 '32 e, 34 e
[Ans. Isotopes--same at. no. but different at. masses. [Hint: 1 eV = i.602 x 10- 19 joule;
16 0 18 0' 239 238 ' 77Ge 76 Ge h 6.62 x 10-34 J-s, c='3 X 108 ms- I
8 ' 8 '92 U ',92 U , 32 '32
h· c . 7 3
Isobars-same atomic masses but different at. numbers A= - :::: 12.42 x 10- m = 12.42 x 10 A]
E
14C 14N_ 77Ge 771>c
6 ',7 '32 '33'~ 7. ' A photon of light with wavelength 6000 A has an energy E.
Calculate the wavelength of photon of a light which
Isotones-same number of neutrons,
corresponds to an energy equal to 2E.
I~O, l~C; :gK, jgca;T:As, nSe] [Ans. 3000 A]
3. An element has atomic' number 30. Its cation has 2 units 8. Calculate the energy in kilocalorie per mol of the photons of
positive charge. How many protons and electrons are present an electromagnetic radiation of wavel~ngth 5700 A.
in the cation? [Ans. 56.3 kca1 per mol]
[Ans. Protons = 30, Electrons =28]
ATOMIC STRUCTURE I 117
28. The wavelength of the first member of the Balmer series of 33. The velocity of an electron in certain Bohr orbit of H-atom
hydrogen is 6563 x IO-IO m. Calculate the wavelength of its bears the ratio I : 275 to the velocity of light. (a) What is the'
second member. quantum number 'n' of the orbit? (b) Calculate the wave
number of the radiation when the electron jumps from (n + I)
[Hint: :1 [;2 -),
== RH and :2 RH [;2 12 J
4 state to ground state.
[Ans. v 9.75 x 104 em-I]
5 16 20
==-x v I 3 X 1010 8
1..1 36 3 27 [Hint: (a) - = orv == == 1.09 X 10 em
c 275 275
nh nh
1..2 == 20 x 6563 X 10- 10,:" 4861 X 10.- 10 m] . v == - - == ------_=_~
27 21tmr 21tm X 0.529 x I
29. According to Bohr theory, the electronic energy of hydrogen h
or 11= -------:~-
atom in the nth Bohr orbit is given by, 21tm X 0.529 x XV
2176 x 10- 19 6.625 X 10-27
Ell == J
2 X 3.14 x 9.1 x
Calculate theiongest wavelength of light that will be needed
=2
to remove an electron from the 2nd orbit of Li 2 + ion. .
(b) Thus, II + 1 = 2 + 1 3. The electron jumps from 3rd orbit to
[Ans. 4.059 x 10-8 m] 1st orbit.]
30. Calculate the frequency, energy.. and .wavelengili<of the
radiation corresponding to spectral. line of lowest frequency in
34. Find out the wavelength of the next line in the series having
Lyman series in the spectra of hydrogen atom. Also c'alculate lines of spectrum of H-atom of wavelengths 6565 A, 4863 A,
4342 A and 4103 A.
. the energy of the corresponding line in the spectra of Li 2+.
(lIT 1991) [Ans. 3972 A]
7
[Ans. I.. == 121'; X 10- m;v = 2.47 x lOIS cycle , [Hint: All these lines are in visible region and thus, belong to
Balmer series, Next line is, therefore, from 7th orbit.]
E 16.36 X 10- 19 j, ELi 2+ ~ EH 9 x i6.36 X 10- 19 J
147.27 X 10-19 J]
35. Which jump is responsible for the wave number of emitted
radiations equal to Q.7490 x 106 m- I in Lyman series of
31. Calculate the ratio of the veIocity oflight and the velocity of
electron in the 2nd orbit. of a hydrogen atom. (Given hydrogen spectrum? (R 1.09678 x 107 m- 1 )
h = 6.624 X 10-27 erg-sec;m . 9.108 x 10- 28 g; [ADs. 3]
r 2.11 X 10-8 cm) 36. Calculate the ionisation energy of the hydrogen atom. How
[Ans. 273.2] . much energy will be required to ionise 1 mole of hydrogen
32. What hydrogen-like ion has the wavelength difference atoms? Given, that the Rydberg constant is 10974 X 107 m- I .
betWeen the first lines of Baf~er and Lyman series equal to [Ans. IE per hydrogen atom = 2.182 x 10-1.8 J
59.3 nm (RH = 109678 em-I)? IE per mole = 1314 kJ mol-I]
[Hint: Wavelength df 1st line in Balmer series, 37. Calculate the ionisation energy of (a) one Li 2 + ion and (b) one
r =Z 2RH
I..B
[l.. _l..J
22 32
2. R Z2
36 H
mqJe ofLi2+ ion. (Given, R == 10974 X 10-7 m- I )
[Ans. (a) 19.638 x 10- 18 J (b) 1.118 X 104 kJ mol-I]
t.. _ 36 38. A series of lines in the spectrum of atomic hydrogen lies at
or
B - 5R Z 656.46 nm, 4i6.27 nm, 439.17 nm and 410.29 nm. What is the
. H
wavelength of the next line in this series? What is the
Wavelength of 1st line in Lyman series is, ionisation energy of the atom when it is in the lower state of
J....
I..L Z2R
B [~
12 l..l
22.
transition?
[Ans. I..nexl 397.15 nm; IE = 3.40 e':l
4 39. A certain line of the Lyman series of hydrogen and a certain
or AL == ----;:-2
. 3xRH Z line of the Balmer series of He + ion have nearly the same
wavelength. To what transition do they belong? Small
Differencel..B - I..L = 59.3 X 10-7 == ~ - ~ differences between their Rydberg constant may be neglected.
5RHZ 3RH Z
[Ans. Hydrogen Helium
1
RHZ2
[36
5" '3
4J 2~1
3 __ 1
4 __ 2
6 __ 2
88 4 __ 1 8 __ 2]
z 2 == 7 . 9.0
59.3 x 10- x 109678 x 15 40.. What element has a hydrogen-like spectrum whose lines have
.. , or Z='3 wavelengths four times shorter than those of atomic hydrogen?
[ADS. He+]
Hydrogenclike species is Li 2+.]
ATOMIC STRUCTURE 119
41. What lines of atomic hydrogen absorption spectrum fall 53. CalCulate the momentum of the particle which has de Broglie
within the wavelength ranges from 945 to 130 nm? . wavelength I A (10- 10 m)and h = 6;6 x 10-34 J- se<;.
[Ans. 97.3; 102.6; 121.6 nm] [Ans. 6.6 x 10-24 kgm sec-I]
42. The binding energy of an electron in the ground state of an
54. The uncertainty of a particle in momentum is 3.3 x 10-2
atom is eq:ualto 24.6 eV Find the energy required to remove
both the electrons from the atom. . ,kg ms-I. Calculate the uncertainty in its positiQ'Q.
[Ans. 79 eV] (h = 6.6 x 10-34 J- sec)
43. What is the ratio of the speeds of an electron in the first and [Ans. 3.1 x 10- 14 m]
second orbits of a hydrogen atom?
55. Calculate the product of uncertainties of displacement and
[Ans. 2; 1] .
velocity ofa moving electron having a mass 9,1 x 10-28 g.
44. Find out the number of waves made by a Bohr electron in one
complete revolution in its third orbit. (lIT 1994) [Ans. 5.77 x 10-5 m2 S-I]
[Ans. 3] [Hint: ~ ·Ilv ~ ~]
45. The wave number of first line in Balmer series of hydrogen is 4~ .
15200 cm -I. What is the wave number of first line in Balmer 56. (a) A transition metal cation x 3 + has magnetic morrient .,[35
series ofBe 3+? BM. What is the atomic number of x 3+?
[Ans. 2.43 x 105 cm- I ] (b) Select the coloured ion and the ion having maximum
46. Calculate the speed of an electron in thegroJln(istate of
hydrogen atom. What ·fraction of the speed of light is this
1111 1111 11 1 D
value? How long does it take for the electron to complete one magnetic moment (i) Fe +, (ii) Cu +, (iU) Sc 3+ and
2
[Ans. 4.69 A]
[Hint: (a) 26, 26Fe~ 3d 6 4s 2
48. The radius of the fourth orbit of hydrogen is 0.85 nm. Fe3i; ~ 3d 5 4sO
Calculate the velocity of an electron in this orbit
(me 9.1 x 10-31 kg).
Il =In(n + 2) =..J5X7 = 55
Both these ions will be coloured and magnetic moment of Fe2 +
[Ans. 5.44 x 105 m sec-I]
will be greater.]
49. A beam of electrons accelerated with 4.64 V was passed 57. A photon of wavelength 4000 A strikes a metal surface, the
through a tube having mercury vapours. As a result of work function of the metal being 2.13 eV Calculate (i) energy
absorption, electronic changes occurred with mercury atoms 9f the photon in eV; (ii) kinetic energy of. the emitted
and light was emitted. If the full energy of single electron was photoelectron and (iii) velocity of the photoelectron.
converted into light, what was the wave number of emitted
[Ans.E = 3.10 eV; KE= 0.97 eV; Velocity = 5.85 x 105 Ins-I]
light?
[Hint: I eV = 1602 X 10-19 J]
[Ans. : 3.75 x 104 em- I I
so. An electron jumps from an outer orbit to an inner orbit with
58. Calculate the ratio between the wavelengths of an electron and
the energy difference of 3.0 eV. What will be the wavelength a proton, if the proton is moving at half the velocity of the
of the line and in what region does the emission take. place? electron (mass of the proton = 167 x 10-27 kg; mass of the
[Ans. A 4140A; visible region] electron = 9.11 x 10-28 g).
[Hint: leV 1.6 X 10- 12 erg] [Ans. 9.2455 x 10-2 m]
h
51 •. The first ionisation energy of a certain atom took place with an [Hint: Applyde. Broglie equation, A
absorption of radiation of frequency 1.5 x 1018 cycle per
second. Calculate its ionisation energy in calorie per gram atom. Wavelength of electron
[Ans. 1.43 x 108 cal l
[Hint: 1 calorie 4.18 x 107 erg Wavelength of proton
Apply E = h x v x Avogadro's number]
52. Find the wavelength associated' with an electron which has 59. A moving electron has 2.8 x 10-25 J of kinetic energy.
mass 9.1 x 10-28 g and 'is moving with a velocity of lOS cm Calculate its wavelength.
sec-I. (Given h 6.625 x 10- 27
erg-sec) (Mass of electron = 9.1 x 10-3,1 kg)
77. Find out the wavelength of a track star running a 100 metre I mv 2 :::K Zex e
dash in 10.1 sec, if its weight is 75 kg. 2 ro
[Ans. 8.92 x 10-37 m] For Rutherford experiment,
78. At what velocity ratio are the wavelengths of an electron and a
proton equal? . .! mv 2 5.5 MeV::: 5.5 x )(1' x 1.6 x 10-19 J::: 8.8 X 10-13 J
2
24
(me == 9.1 x 10-28 g and mp = 1.6725 X 10- g) 9
8.8 X 10- 13 = 9x10 x2x79x
[Ans. Ve = 1.8 X 103] 10
vp 15
10 == 4.136 X 10- m
79. Through what potential difference must an electron pass to
have a wavelength of500 A? 10 = 4.IHm]
[Ans. 6.03 x 10-:4 eV ] 84. Photoelectrons are liberated by ultraviolet light of wavelength
h 3000 A from a metallic surface for which the photoelectric
[Hint: Use A== ~] threshold is 4000 A. Calculate de Broglie wavelength of
,,2eV m
electrons emitted with maximum kinetic energy.
80. Calculate the velocity of an ~-particle which begins to reverse
[Ans. A == 12 X 10-9 m]
its direction at a distance on X 10- 14 m from a scattering gold
nucleus (Z == 79). [Hint:
[Ans. 2.346 x 107 m! sec] KE = Quantum energy - Threshold energy. ..
81. Two hydrog~n atoms collide head.on and end up with zero 6.626 X 10-34 X3 X 10& 6.626 X 10-34 x 3 X 108
kinetic energy. E~ch then emits a ph:oton with a wavelength 3000x 4000 x
121.6 nm. Which transition leads to this wavelength? How
fast were the hydrogei1 atoms travelling before the collision? == 6.626 X 10- 19 4.9695 X 10-19
(Given, RH == 1.097 X 107 m- I and"'H == 1.67 X 10-27 kg) == 16565 X 10-19 joule
IAns. nl I; 112 = 2; 4.43 X 10 4
m sec-I]
[Hint: Wavelength is in UV region; thus nl will be 1.
.! mv 2 1.6565 x 10- 19
2
7
-----;;,::: 1.097 X 10 x 12 X'(112
12L6 x
- :~)
"1.
m4v 2 = 2 x 16565 X 10-19 x 9.1 X 10-31
mv = 5.49 x 10-25
112 2 34
I 2 he A ::: ...!:. = 6.626 X 10- = 1.2 X 10-9 m]
.- mv :::- mv 5.49 x
2 A
34 8 8S. Show that de Broglie wavelength of electrons accelerated V
-I x.
167 X 10-27 XV
2
:::
6.626 X 10- x 3 X 10
------;c-~-
volt is very nearly given by:
2 1216 x
v 4.43 X 104 m sec-I] AOn A) Iv50)112
(
82. Show that the wavelength of electrons moving at a velocity
very small compared to that of light and with a kinetic energy
of V electron volt can be written as,
[Hint: A= b
v'l,eVm
~
.A=~X
12.268 10-8 cm 2 ]1/2
",A= _h_ x 1020 A
.JV [ 2eVm
Use the relation, A =
[Hint: h
.J2Em =[ (6.626 x 10- )2 x 10
34
JI/2
20
[150J1I2]
Here, h = Planck's constant 2 x 16 X 10- 19 x V x 9.1 X 10-31 V
m ::: 9.1 X 10-28 g (mass of e- )
86. A 1 MeV proton is sent against a gold leaf (Z = 79). Calculate
E Kinetic energy of electron
== V 12
, eV== V x 1.6 X 10- erg]
the distance of closest approach for head-on collision.
[Ans. 1.137 x 10- 13 m]
83. What is the distance of closest approach to the nucleus of an
a-particie whiCh undergoes scattering by 1800 in z,} .
Geiger-Marsden experiment? [Hint: d == . 2 ' Do hke Q.No. 83]
. 41tco(M mv )
[Ans. 10 = 4.13 fm]
87. What is the energy, momentum and wavelength of the photon
[Hint: For closest approach, emitted by a hydrogen atom when an electron makes a
transition from n == 2 to n I? Given that ionization potential
is 13.6 eV.
•
122 .1 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
--!?OBlECTlVEQUESTIONS
Set-1: Questions with single correct answer (a) electrons (b) protons (c) neutrons (d) nucleus
13. Rutherford's scattering experiment is related to the size ofthe:
1. The ratio of elm for a cathode ray: (a) nucleus (b) atom (c) electron (d) neutron
(a) varies with a gas in a discharge tube 14. When alpha particles are sent through a thin metal foil, most of
(b) is fixed them go straight through the foil because:
(c) varies with different electrodes (a) alpha particles are much heavier than electrons
(d) is maximum ifhydrogen is taken (b) alpha particles are positively charged
2. Which of the following statements is wrong about cathode . (c) most part of the atom is empty space
rays? (d) alpha particles move with very high velocity
(a) They trav~1 in straight lines towards cathode 15. The radius of an atomic nucleus is of th~ order of:
(b) They produce heating effect [PMT (MP) 1991]
(c) They carry negative charge (a) 10- 10 cm (b) 10- 13 cm
(d) They produce X-rays when strike with material having
(c) 10-15 em (d) 10-8 cm
high atomic masses
3. Cathode rays are: 16. Atomic size is of the order of:
(a) electromagnetic waves (b) stream of a-particles (a) 10-8 cm(b) lO-IO cm (c) 10- 13 cm(dj l(r'6 cm
(c) stream of electrons (d) radiations 17. Atoms may be regarded ·as comprising of protons, neutrons
4. Cathode rays have: and electrons. If the mass attributed by electrons was doubled
(a) mass only (b) charge only and that attributed by neutrons was halved, the atomic mass of
(c) no mass and no charge (d) mass and charge both 12C would be:
S. Which is the correct statement about.proton? (a) approximately the same (b) doubled
(a) It is a nucleus of deuterium (c) reduced approx. 25% (d) approx. halved
(b) It is an ionised hydrogen molecule is. Positive ions are fonned from neutral atoms by the loss of:
(c) It is an ionised hydrogen atom (a) neutrons (b) protons
(d) It is an a-particle (c) nuclear charge (d) electrons
6. Neutron was discovered by: 19. The nitrogen atom has 7 protons and 7 electrons. The nitride
(a) 1.1. Thomson (b) Chadwick ion will have:
(c) Rutherford (d) Priestley (a) 10 protons and 7 electrons
7. The discovery of neutron came very late because: (b) 7 protons and 10 electrons
(a) it is present in nucleus (c) 4 protons and 7 electrons
(b) it is a fundamental particle (d) 4 protons and 10. electrons
(c)· it does npt move 20. A light whose frequency is equal to 6 x 1014 Hz is incident on a
(d) it docs not carry any charge metal whose work function is 2eV (h = 6.63 x 10- 34 Js,
leV'" 1.6 x. 1O- 19 J). The maximum energy of electrons
S. The fundamental particles present in equal numbers in neutral
emitted will be: (VlTEEE 2008)
atoms (atomic number 71) are:
(a) 2.49 eV (b) 4.49 eV (c) 0.49 eV (d) 5.49 eV
(a) protons and electrons (b) neutrons and electrons
[Hint: Absorbed energy = Threshold energy
(c) protons and neutrons (d) protons and positrons
+ Kinetic energy of photoelectrons
9. The nucleus of the atom consists of:
Absorbed energy hv .
(a) protons and neutrons
(b) , protons and electrons
= 6.626 x·lO- 34 x 6 X 10 14
(c) neutrons and electrons = 3.9756 x 10- 19 J
(d) protons, neutrons and electrons 19
3.9756 X 10- =2.49 eV
10. The absolute value of charge on the electron was determined by: 1.6 x 10- 19
(a) l1. Thomson (b) RA. Millikan
2.49 2 eV + Kinetic energy of photoelectron
(c) Rutherford (d) Chadwick Kinetic energy of photoelectron = 0.49 eV]
11. Atomic number of an element represents: (CBSE 1990) • 21. The size ofthe nucleus is measured in:
(a) number of neutrons in the nucleus (a) amu (b) angstrom
(b) atomic mass of an element (c) em (d) fermi
(c) valency of an element
22. The highest value of el m of anode rays has been observed
. (d) number of protons in the nucleus when the discharge tube is filled with:
12. Rutherford's experiment on .scattering of a-particles showed (a) nitrogen (b) oxygen (c) hydrogen (d) helium
for the first time that the atom has: [CMC (Vell~re) 1991]
124 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
23. The particle with 13 protons and 10 electrons is: . (c) Dempster's mass.spectrograph .
(a) Al atom (b) A1 3 + ion (d) all of the above
(c) nitrogen isotope (d) none ofthese 36. Mass spectrograph helps in the detection of isotopes because
24. Which of the following atoms contains the least number of they:
neutrons? (a) have different atomic masses
(a) 2~iu (b) Z:U (b) have same number of electrons
(c) have same atomic number
(c) 2~jNp
(d) have same atomic masses
25. The number of neutrons in dip~sitive zinc ion (Zn 2+ , with 37. Which of the following statements is incorrect?
mass number 70) is: (a) The charge on an electron and proton are equal and
(a) 34 (b) 36 . (c) 38 (d) 40 opposite
26. Which of the properties of the elements is a whole number? (b) Neutrons have no charge
(a) Atomic mass (b) Atomic number (c) Electrons and protons have the same mass
(c) Atomic radius (d) Atomic volume (d) The mass of a proton and a neutron are nearly the same
27. Increasing order (lowest first) for the values of e / m 38. The charge on positron is. equal to the charge on:
(charge/mass) for electron (e 1 proton (p), neutron (n) and (a) proton (b) electron
a-particle (a lis: (c) a-particle (d) neutron
(a) e, p, n,a (b) n, p, e,a 39. Discovery ofthe nucleus of an atom was due to the experiment
(c) n,p,a,e (d) n,u,p,e carried out by: .
28. The mass of neutron is ofthe order of: (a) Bohr (b) Rutherford
(a) 10-27 kg (b) 10-26 kg (c) Moseley (d) Thomson
(c) 10-25 kg (d) 10-24 kg 40. Isobars are the atoms of: (CBSE 1991)
29. The. atomS of various isotopes of a particular element differ (a) same elements having same atomic number
from each other in the number of: (b) same elements having same atomic mass
(a) electrons in the outer shell only (c) different elements having same atomic mass
.(b) protons in the nucleus (d) none ofthe above
(c) electrons in the inner shell only 41. Which of the following pairs represents isobars?
(d) neutrons in the nucleus (a) ~Reand iRe fi
(b) Mg and ~iMg
30. Isotopes of the same element have: (c) t~K and ~gCa (d) tgK and ?gK
(a) same number of neutrons 42. Na + ion is isoelectronic with: (CPMT 1990)
(b) same number of protons (a) U+ (b) Mg2+ (c) Ca 2+ (d) Ba 2+
(c) same atomic mass
43. The triad .of nuclei that is isotonic is:
(d) different chemical properties
31. Which of the following conditions is incorrect for a well (a) I:C, IjN, I~F (b) l~C, IjN, IgF
behaved wave function (\if)? [EAMCE;T (Engg.) 2010]
(a) \if must be finite (b) \if must be single valued
. (c) \if must be infinite (d) \if must be continuous 44. Sodium atoms and sodium ions:
32. Atomic mass of an element is not a whole number because: (a) are chemically similar
(a) it contains el~trons, protons and neutrons (b) both react vigorously with water
(b) . it contains isotopes (e) have same number of electrons
(c) it contains allotropes (d) have same number of protons .
(d) aU of the above fi g
45. In Cl and Cl, which of the following is false?
33. Nucleons are: (a) Both have 17 protons
(a) protons and neutrons (b) Both have 17 electrons
(b) neutrons and electrons (e) Both have 18 neutrons
(c) protons and electrons (d) Both show same chemical properties
(d) protons, neutrons and electrons 46. Which of the following is isoelectronie with neon?
34. Isotopes of an element have: . (a) 0 2 - (b) F + (c) Mg (d) Na
(a) different chemical and physical properties 47. Neutrino has:
(b) similar chemical and physical properties (a) charge + I, mass 1 (b) charge 0, mass 0
(c) similar chemical but different physical properties (c) charge - L mass 1 (d) charge 0, mass 1
(d) .similar physical and different chemical properties 48. Positronium is the name given to an atom-like combination
35. Isotopes are identified by: . formed between: (JIPMER 1991)
(a) a positron and a proton
(a) positive ray analysis
(b) a positron and a neutron
(b) Astons' mass spectrograph
I
ATOMIC STRUCTURE 125
(c) a positron and an a-particle 61. A 600 W mercury lamp emits monochromatic radiation of
(d) a positron and an electron wavelength 331.3 nm. How many photons are emitted from
49. An isotone of ~~Ge is: the lamp per second? [PET (Kerala) 2010]
(a) ~iGe. (b) j~As (c) I!Se (d) j!Se (h == 6.626 x 10-34 Is, velocity oflight 3x 108 ms-I)
50. Which of the following does not characterise X-I1lYs? (a) Ix 1019 (b) Ix 102°
1
(lIT 1992) (c)lxl02 (d) Ix 1023
(a) The radiations can ionise gases 2
(e) Ix 102
(b) It causes ZnS to fluorescence
[Hint: Power Energy
(c) Deflected by electric and magnetic fields Time
(d) Have wavelengths shorter than ultraviolet rays
600= nhc
51. X-rays are produced when a stream of electrons in an X-ray Axlsec
tube: 34 8
600 == n X 6.626 10- x 3 X 10
(a) hits the glass wall ofthe tube
33L3x
(b) strikes the metal target 21
n==lx10 ]
(c) passes through a strong magnetic field v
62. Out of X-rays, visible, ultraviolet, radiowaves, the largest
(d) none of the above
frequency is of:
52. Radius of a nucleus is proportional to:
(a) X-rays (b) visible
(a) A (b) A I/3 (c) A2 (d)A 2/3 (c) ultraviolet' (d) radiowaves
53. The nature of positive rays produced in a vacuum discharge 63. The wave nnmber 'which,corresponds to electromagnetic
tube depends upon: radiations of 600 nm is equal to:
(a) the nature of the gas filled (a) 1.6 x 104 cm- I (b) O.l6x 104 cm- 1
(b) nature ofthe material of cathode
(c) nature of the material of anode (c) 16 x 104 cm- I (d) 160 x 104 cm- i
(d) the potential applied across the electrodes 64. Line spectrum is characteristic of:
. 54. Electromagnetic radiation with maximum wavelength is: (a) molecules (b) atoms
(MLNR 1991) (c) radicals (d) none of these
(a) ultraviolet (b) radiowaves 65. Which one of the following is not the characteristic of
(c) X-rays (d) infrared Planck's quantum theory of radiation? (AIIMS 1991)
55. The ratio of energy of radiations of wavelengths 2000 A and (a) The energy is not absorbed or emitted in whole number
4000 A is: . (eDSE 1994) multiple of quantum' .
(a) 2 (b) 4 (c) 1/2 . (d) 1/ 4 (b) Radiation is associated with energy
56. The ratio of the diameter of the atom and the diameter of the (c) Radiation energy is not emitted or absorbed continuously
nucleus is: . but in the form of small packets called quanta
(a) 10 5
(b) ItY (cPO (d) 10- 1 (d) This magnitude of energy associated with a quantum is
proportional to the frequency
57. The ratio of the volume of the atom and the volume of the
nucleus is: 66. Which of the following among the visible colours has the
minimum wavelength? .
(a) 1010 (b) 1012 (c) 1015 (d) 102°
(a) Red (b) Blue
58. Which of the following statements is incorrect?
(a) The frequency of radiation is inversely proportional to its (c) Green (d) Violet
67. The spectrum of helium is expected to be similar to that of:
wavelength
(b) Energy of radiation increases with increase in frequency (a) H (b) Na (c)He+ , (d) Li+
(c) Energy of radiation decreases with increase in wavelength 68. According to classical theory. if an electron' is moving in a:
(d) The frequency of radiation is directly proportional to its.• circular orbit around the nucleus:
wavelength . (a) it will continue to do so for sometime
59. Visible light consists of rays with wavelengths in the (b) its orbit will continuously shrink
approximate range of: (c) its orbit will continuously enlarge
(a) 4000A to 7500 A (d) it will continue to do so for all the time
(b) 4 x 10-3 cm to 7.5 x 10-4 cm 69. Bohr advanced tlJe idea of:
(a) stationary electrons (b) stationary nucleus
(c) 4000 nm to 7500 nm
(c) stationary orbits (d) elliptical orbits
(d) 4 x 10-5 m to 7.5 x 10-6 m
70. On Bohr stationary orbits:
60. Which of the following statements concerning light js false? (a) electrons do not move
(a) It is a part of the electromagnetic spectrum (b) electrons move emitting radiations
(b) It travels with same velocity, i.e., 3 x 1(Yo cm/ s (c) energy ofthe electron remains constant
(c) It cannot be deflected by a magnet
(d) angular momentum ofthe electron is..!!...
(d) It consi,ts A photons of same energy . 2n
126 G.R.B. PHYSICAL CHEMISTRY FOR CoMPETITIONS
93. The ionisation energy of the electron in the ls-orbital of the (a) 15,200cm- I (b) 60,800cm- 1
hydrogen atom is 13.6 eY. The energy of the electron after
(c) 76,000 cm- 1 (d) 1,36,800cm-:- 1
promotion to 2s-orbital is: IISC (Bihar) 1993)
(a) -3.4eV (b) -13.6eV 103. "The position and the velocity of a small particle like electron
(c) -27.2eV (d) O.OeV cannot be simultaneously determined." This statement is:
94 .. Which electronic level would allow the hydrogen atom to (a) Heisenberg uncertainty principle
absorb a photon but not to emit it? (b) Pauli's exclusion principle
(a) Is (b) 2s (c) 3s (d) 4s (c) aufbau's principle
95. The spectral lines corresponding to the radiation emitted by an (d) de Broglie's wave nature ofthe electron
electron jumping from 6th, 5th' and 4th orbits to second orbit 104. de Broglie equation describes therelationship of wavelength
belong to: associated with the motion of an electron and its:
(a) Lyman series (b) Balmer series (a) mass (b) energy (c) momentum (d) charge
(c) Paschen series (d) Pfund series 105. If the magnetic quantum number of a given atom is
96. The spectral lines corresponding to the radiation emitted by an represented by then what will be its principal quantum
electron jumping from higher orbits to first-Orbit belong to: number? [BHU (Pre.) 2005)
(a) Paschen series (b) Balmerseries (a) 2 (b) 3 (c) 4 (d) 5
(c) Lyman series (d) None of these J06. Which of the following relates to photons both as wave motion
and as a stream of particles? (IlT 1992)
97. In a hydrogen atom, the transition takes plac.efrOll1n 3 to
n = 2. If Rydberg constant is 1.097 x 107 m-I, the wavelength (a) Interference (b) Diffraction
of the emitted radiation is: (c) E == hv (d) E = me2
(a) 6564A (b) 6064 A 107. If uncertainty in the positiOil of an electron is zero, the
(c) 6664A (d) 5664 A uncertainty in its momentum would be:
[Hint: Apply.!. = R
A
[~
x j} Ca) zero,
(c) > h/(4n)
(b) < hI(4'n)
(d) infinite
108. Which one of the following explains light both as a stream of
98. The speed ofthe electron in the 1st orbit of the hydrogen atom
particles and as wave motion?
in the ground state is (e is the velocity oflight):
(a) Diffraction (b) A = h/ p
e e e e
(a) 1.37 (b) l370 (c) 13.7 (d) 137 (c) Interference (d) Photoelectric effect
109. A body of mass x kg is moving with velocity oflOO msec- I . Its
[Hint: Velocity of electron in the 1st orbit, v = h/(2nmr)
de Broglie wavelength is 6. 62 X 10-35 m. Hence x is:
, = 2.189 X 108 em/sec., velocity of light, c = 3 X 10 10 ern/sec. (h == 6.62x 10-34 J sec) [CET (Karnataka) 2009)
Ratio c/v l37] (a) 0.25 kg (b) 0.15 kg
99. , Find the value of wave number v in terms of Rydberg's (c) 0.2 kg (d) 0.1 kg
constant, when transition of electron takes place between two 110. A 200 g cricket ball is thrown with a'speed of 3.0 x 103 cm
levels ofHe+ ion whose sum is 4 and difference is 2. sec-I. What will be its de Broglie's wavelength?
(a) 8R (b) 32R (II =6.6 X 10-27 g cm2 sec-I ) [CET (Gujftrat) 2008)
9 9 (a) 1.1 x 10-32 cm (b) 2.2 x 10- 32 cm
(c) 3R (d) None of these (c) 0.55 x 10-32 cm (d) Il.Ox 10-32 cm
4
Ill. The electronic configuration of a dipositive ion M 2+ is 2, 8, 14
[Hint: nl +~ 4; n2 -nj 2 and its atomic mass is 56. The number of neutrons in 'the
V RZ2[~_~J nucleus would be:
nl ni ( (a) 30 (b) 32 (c) 34 (d) 42
112. An element with atomic number 20 will be placed in which
=R X 22 [~- ~J
2
32R] period of the periodic table?
1 3 9
(a) 5th (b) 4th (c) 3rd (d) 2nd
100. With the increasing principal quantum number, the energy
113. The frequency of radiation emitted when the ekc~on falls
difference between adjacent energy levels in hydrogen atom:
from n 4 to n 1 in a hydrogen atom will be (Given
(a) increases (b) decreases
ionisation energy of H=2.18x 10- 18 Jatom- 1 and
(c) is the same (d) none of these h = 6.626 X 10-34 Js): [Manipa, (Me d.) 2007)
101. An electron in an atom: rCEET (Bihar) 1992] (a) 1.54 x 1015 S-I (b) 1.03 x 1015 8- 1
(a) moves randomly around the nucleus
(b) has fixed space around the nucleus
(c) 3.08 X 101 5 Cd) 2 x 1015 s-i
(c) is stationary in various energy levels 114. In a multi-electron atom, which of the following, orbitals
(d) moves around its nucleus in definite energy levels described by the three quantum numbers will have the same
102. The wave number of first line of Balmer series of hydrogen is energy in the absence of magnetic and electric fields?
15200 cm- I • The wave number ofthe first Balmer line ofLi 2+ (AIEEE2005)
ion is: [liT !}~f:r:'i'''~';,,~~ 1992] (i) 17 = I, I=: 0, m 0 (ii) n == 2, I 0, m = 0
I
128 I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(iii) n =: 2, I I, m =: I (iv) n =: 3, I=: 2, m =: I 127. Any p-orbital can accommodate up to: (MLNR 1990)
(v) n =: 3, I ::= 2, m =: 0 (a) 4 electrons
(a) (i) and (ii) (b) (ii) and (iii) (b) 2 electrons with parallel spins
(c) (iii) and (iv) (d) (iv) and (v) (c) 6 electrons
115. Which of the ions is not having the configuration ofNe? (d) 2 electrons with opposite spins
(a) Cl- (b) F - (c) Na + (d) Mg2+ 128. How'many electrons can fit into the orbitals that comprise the
116. Which ofthe following has the maximum number of unpaired 3rd quantum shell n =: 3?
d-electrons? (KeET 2008) (a) 2 (b) 8 . (c) 18 (d) 32
(a) Ni 3+ (b)Cu+ (c)Zn2+ (d) Fe2 + 129. The total number of orbitals in a principal shell is:
117." Which of the following expressions gives the de Broglie (a) n (b) n2 (c) 2n 2 (d) 3n 2
relationship? IJEE (WB) 2008) 130. Two electrons in K-shell will differ in:
h h (a) principal quantum number
(a) p =: - (b) A
mv mv (b) spin quantum number
(c) A =: h
h (c) azimuthal quantum number .
(d) Am=
mp p (d) magnetic quantum number .
118. The principal quantum number of an atom is related to the: 131. Which one of the following orbitals has the shape of a
(MLNR 1990) baby-boother ?
(a) size of the orbital (a) dxy (b) d x 2 - y 2 (c) d z 2 (d) Py
(b) orbitafangular momentum
132. Which one of the following represents an impossible
(c) spin angular momentum
arrangement? (AIEEE 2009)
(d) orien.tation ofthe orbital in space n I m s n I m s
119. The magnetic quantum is a number related to:
(a) 3 2 - 2 112 (b) 4 0 o 1/2
(a) size (b) shape
(c) 3 2 . -3 112 (d) 5 3 o 112
(c) orientation (d) spin
120. The principal quantuIn number represents: (CPMT 1991)
(a) shape of an orbital
(b) nU!l).ber of e~ectrons in an orbit
(c) distance of electron from nucleus
(d) numbei: of orbitals in an orbit
121. The quantum number not obtained from the Schrodinger's
wave equation is: (lIT 1990)
(a) n (b) 1 (c) m (d) s
122. In a given atom, no two electrons can have the same values for
all the four quantum nU!l).bers. This is called: (CPMT 1990)
(a) Hund's rule (b) Pauli's exclusion principle
(c) Uncertainty principle (d) aufbau principle
123. The atomic orbital is:
(a) the circular path of the electron
(b) elliptical shaped orbit .
(c) three-dimensional field around nucleus
(c) 21 + I (d) 41 + 2
. (d) the region in which there is maximum probability· of
finding an electron [Hint: Number of electrons with same spin
·124. If the ionization energy for hydrogen atom is 13.6 eV, then the 1 x Total no. of electrons
ionization energy for He+ ion should be: 2
1 .
I PMT (Haryana) 2004] =: - x 2 (21 + 1) =: (21 + 1)]
(a) 13.6 eV (b) 6.8 eV 2
(c) 54.4 eV (d) 72.2 eV 136.. Which of the following represents the correct set of four
125. Principal,. azimuthal and magnetic quantum numbers are quantum numbers of a 4d-e1ectron? (MLNR 1992)
respectively related to: (a) 4,3,2, + 112 (b) 4,2, 1,0
(a) si?e,shape and orientation (c) 4,3, - 2, + 112 (d) 4,2, i, 1/2
.(b) shape, size and orientation 137. Values of magnetic orbital quantum number for an electron of
(c) size, orientation and shape M-shell can be: (PET (Raj.) 2008]
(d) none of the above (a) 0, 1,2 (b)-2,-1,0,+1,+2
126. Energy of e1ectron·in the H-atom is determined by : (c) 0, 1,2,3 (d) 1,0,+1
(a) only n (b) bothn and I 138. Correct set of four quantum numbers for the outermost
(c) n, I and m (d) all the four quantum numbers . electron of rubidium (Z = 37) is:
ATOMIC STRUCTURE 129
(a) 5,0,0,1/2 (b) 5, 1,0, 112 149• The energy ofaa~lectron of 2p y' orbital is:
.(c) 5,1, 1.112 (d) 6,0,0,112 (a) greater than 2px orbital
139. Which one of the following subshells is spherical in shape? (b) less than 2pz orbital
(a) 4s (b) 4p (c) 4d (d) 4f (c) equalto 2sorbitil
140. In hydrogen atom, the electron is at a distance of 4.768 A from (d) same as that of2px and 2pz orbitals
the nucleus. The angular momentum of the electron is : 150• The two electrons occupying the same orbital are
. [EAMCET (Med.) 2010] distinguished by: .
(a)· 3h . (b) ~ (a) principal quantum.number
211: 211: (b) azimuthal quantum number
h (d) 3h (c) magnetic quantum number
(c) -
11: 11: (d) spin quantum number
n2 151. The maximum number of electrons in a subshell is given by
[Hint: r = - x 0.529 A
z the expression: (AIEEE 2009)
n2 (a) 41 + 2 (b) 4/- 2
4.768 = x 0.529
1 (c) ()./ + I (d) 2n2
n=3 152. The electronic configuration of an atom/ion can be defined by
nh __ 3h] which of the following1
:. Angular m()mentum (mvr)
211: 211: (a) A1.dbau PriI1ciple
141. Total number of m values for n 4 is: (b) Pauli's exclusion principle
(a) 8 (b) 16 (c) 12 (d) 20 (c) Hund's rule of maximum mUltiplicity
142. What is the total number of orbitals in the shell to which the (d) All of the above
g-subshell first arise?
153. An electron has a spin quantum number + 112 and a magnetic
(a) 9 (b) 16 (c) 25 . (d)36 quantum number 1. It cannot be present in:
[Hint: For g-subshell, / = 4 (a) d-orbital (b).forbital (c) s-orbital (d) p-orbital
:. It will arise in 5th shell. 154. The value of azimuthal quantum number for electrons present
Total number of orbitals in 5th shell == n2 = 25] in 4 p-orbitals is:
143. In Bohr's model, if the atomic radius of the first orbit 1j, then (a) 1
radius offourth orbit will be : [BHU (Screening) 2010] (b) 2
161. [Ar] 3dlO 4sl electronic configuration belongs to: . 169. The radial probability distribuuon curve obtained for an
[PET (MP) 20081 orbital wave function ('If) has 3 reaks and 2 radial nodes. The
(a) Ti (b) Tl (c) Cu (d) V valence electron of which one of the following metals does
162. How many unpaired electrons are ther~ in Ni2+ ? (Z 28) this wave function ('If ) correspond to ?
(a) Zero (b) 8 (c) 2 (d) 4 [EAMCET (Med.) 20101
163. The electronic configuration of chromium (Z 24) is: (a) Co (b) Li (c) K (d) Na
[PMT (MP) 1993; BHU (Pre.) 20051 [Hint: Na ll ls2, 2s22l, 3s 1
'----v----'
(a) [Ne] 3i3 p 6 3d 44i (b) [Ne] 3s2 3p 6 3d 54s1 Valence electron
Number of radial node =: n-l-I (n == 3)
(c) [Ne] 3i3p 6 3d l 4i (d) [Ne] 3i 3p64i4p4
3-0-1 = 2]
164. The number of d-electrons in Fe 2+ (At. No. 26) is not equal to 170. ~pton (At. No. 36) has the electronic configuration [A]
that of the: (MLNR 1993) 4s 3d 104 p 6. The 37th electron will go into which one of the
(a) p-electrons in Ne (At. No. 10) . following sub-levels?
(b) s-electrons in Mg (At. No. 12) (a) 4/ (b) 4d
(c) d-electrons in Fe atom (c) 3p (d) 5s
(d) p -electrons in Cl- ion (At. No. 17) 171. An ion which has 18 electrons in the outermost shell is:
165. If the electronic structure of oxygen atom is written as (CBSE 1990)
f--2p---+ (a) K + Q » Cu.+ (c) Cs+ (d) Th 4 +
172: Which ofthe following has non-spherical shell of electronJa
ls2, 2s2 !i.j, 1i.j, 1 . 1; it would violate: fISC (Bihar) 1993]
(lIT 1993)
(a) Hund's rule (a) He (b) B (c) Be (d) Li
173. Which one of the following sets of quantum numbers is not
(b) Pauli's exclusion principle
possible for an electron in the ground state of an atom with
(c) both Hund's and Pauli'sprincipJes
atomic number 19? [PET (Kerala) 2006;
(d) none of the above
CET (Karnataka) 2009]
166. The orbital diagram in which 'aufbau principle' is violated,is:
(a) n = 2, I 0, m == 0 (b) n = 2, I = 1, m 0
2s f - - 2 p---+
(c) n = 3, I =: I, m -1 (d) n 3,1=2,m=±2
(a) [ill I i.j,1 i I (e) n 4,1=0,m=0
174. Helium nucleus is composed of two protons and two neutrons.
(b) If the atomic mass is 4.00388, how much energy is released
when the nucleus is constituted?
(c) :1 i.j, i (Mass of proton == 1.00757, Mass of neutron == 1.00893)
(a) 283 MeV (b) 28.3 MeV
(d) :1 i.j, :1 (c) 2830 MeV (d) 2.83 MeV
175. Binding energy per nucleon of three nuclei A, B and Care
167. The manganese (Z = 25)has the outer configuration: 5.5, 8.5 and 7.5 respectively. Which one of the following
4s ( 3p ) nuclei is most stable?
(a) [illi i.j, II i il i l i II i !I (a) A (b) C
(c) B (d) Cannot be predicted
(b) [ill 176. The mass of jLi is 0.042 less than the mass of 3 protons and
4 neutrons. The binding energy per nucleon in j Li is:
(c) (ill :1 i .j, il j.j, :1 i .(BHU1992)
(a) 5:6 MeV (b) 56 MeV (c) 0.56 MeV (d) 560 MeV
(d) 0 II j.j, II i.j, II i i i 177. Meson was discovered by:
(a) Powell (b) Seaborg
168. Which of the following elements is represented by the (c) Anderson (d) Yukawa
electronic configuration? 178.. In most stable elements, the number of protons and neutrons
f--2p-c-? are:
(a) odd-odd (b) even-even
(c) odd-even (d) even-odd
179. Nuclear particles responsible for holding all nucleons together
are:
(a) electrons (b) neutrons
(c) positrons (d) mesons
(a) Nitrogen (b) Fluorine 180~ The introduction of a neutron into the nuclear composition of
(c) Oxygen (d) Neon an atom would lead to a change in: (MLNR 1995)
ATOMIC STRUCTURE 1.131
(a) its atomic inass (a) 3 (b) 4 (c) 2 (d) 1
(b) its atomic number 191. A certain negative ion has in its nucleus 18 neutrons,and
(c) the chemical nature of the atom 18 electrons in its extranuclear structure. What is the mass
(d) number of the electron also number of the most abundant isotope of X ?
181. Which of the following has highest orbital angular (a) 36 (b) 35.46 (c) 32 (d) 39
momentum? 193. Which of the following statements is not correct?
(a) 4s (b) 4p (c) 4d (d) 4f
(a) The shape of an atomic orbital depends on the azimuthal
181. Which of the following has maximum number of unpaired
quantum number .
electrons? (PMT (Raj.) 2004; BHU (Pre.) 2005)
(b) The orientation of an atomic orbital depends on the
(a) (b) Fe 2+ (c) C0 2+ (d) C0 3+ magnetic quantum number
183. An electron isnot deflected on passing through a certain (c) The en~rgy of an electron in an atomic orbital of
region,because: multielectron atom depends on the principal : quantum
(a) there is no magnetic field in that region number
(b) there is a magnetic field but velocity of the electron is (d) The number of degenerate atomic orbitals of one type
parallel to the direction of magnetic field depends on the values of azimuthal and magnetic qUa)1tum
(c) the electron is a chargeless particle numbers
(d) none ofthe aboye 194. Gases begin to conduct electricity at low pressure because:
184. In MiHik1m's oil drop experiment, we make~use of:
(CSSE 1994)
(a) Ohm's law (b) Ampere's law (a) at low pressures gases tum to plasma
(c) Stoke's law (d) Faraday's law .(b) colliding electrons can acquire higher kinetic energy due to
185. A strong argument for the particle nature of cathode rays is: increased mean free path leading to ionisation of atoms
(a) they can propagate in vacuum (c) atoms break up into electrons and protons
(b) they produce fluorescence (d) the electrons in atoms can move freely at low pressure
(c) they cast shadows
195. An electron of mass m and charge e, is accelerated from rest
(d) they are deflected by electric and magnetic fields through a potential difference V in vacuum. Its final speed will
186. .As the speed of the electrons increases, the measured value of be: (eBSE W94)
charge to mass ratio (in the relativistic units):
(a) increases (a) ~ (b) 2eVIm
(b) remains unchanged (c) J(eVI2m) (d) J(2eVlm)
(c) decreases .
(d) first increases and then decreases 196. The difference in angular momentum associated with .the
187. Which of the following are true for cathode rays? electron in the two successive orbits of hydrogen atom is:
(a) It travels along a straight line (a) hln (b) hl2n (c) hl2 (d) (n -1)hI2lt
(b) It emits X -rays when strikes a metal 197. Photoelectric effect can be explained by assuming that light:
(c) It is an electromagnetic wave (a) is a form of transverse waves
(d) It is not deflected by magnetic field (b) is a form of longitudinal waves
ISS. Three isotopes of an element have masl' numbers, M, (M + 1)
(c) can be polarised
and (M + 2). If the mean mass number is (M + 0.5) then
which of the following ratios may be accepted for (d) consists of quanta .
M, (M + 1), (M + 2)in that order? 198. The photoelectric effect supports quantum nature of Jight
(a) I : 1 : I (b) 4: 1 : 1
because:
(a) there is a minimum frequency of light below which no
(c) 3 : 2 : 1 (d) 2 : 1 : 1
photoelectrons are emitted .
189. The radii of two of the first four Bohr orbits of the hydrogen
(b) the maximum kinetic energy of p\1otoelectrons depends
atom are in the ratio I : 4. The energy difference between them
only on the frequency oflight and not on its intensity
maybe: . .. .
(a) either 12.09 eV or 3.4 eV (6) .either 2.55 eV or 10.2 eV (c) even whet! metal surface is faintly illuminated the
photoelectrons leave the surface immediately
(c) either 13.6 eV or 3.4 eV (d) either 3.4 eV or 0.85 eV
(d) electric charge of photoelectrons is quanti sed
190. Photoelectric emission is .observed from a surface. for
frequencies VI and v 2 ofthe incidentradiafion (VI> V2 ).Ifthe 199. The mass ofa proton at rest is: .(CB.SE 1991)
maximum kinetic energies of the photoelectrons in the two (a) zero (b) 1.67 x 10-:-35 kg
cases are in the ratio 1 : k then the threshold frequency V 0 is (c) one amu (d) 9 x 10-31 kg
given by:
200. Momentum of a photon of wavelength A is: (eBSE 1993)
(a) v 2 - VI (b) k VI ~V2 (c) _k--=.._..!.. (d) v 2 - VI 2
k-l k-l k k (a) hlA (b) zero (c) hAle (d) hAle
191. The number of waves made by a l30hr electron in an orbit of 201. When X-rays pass through air they:
maximum magnetic quantum number +2 is: . ( a) produce light track in the air
(b) ionise the gas
.....
132 G.R.B. PHYSlpAL C~EMISTRY .FOR COMPETITIONS
(c) Rutherford (d) Sommerfeld (d) helium nuclei, which impinged on a metal foil and got
210. The uncertainty in momentum of an electron is 1 x 10-5 kg scattered
ms -1. The uncertainty in its position will be: 219. How many moles of electrons weiflt one kilogram?
(h = 6.62 x 10-34 kg.m2 .s) (CBSE 1999; BHU 2010) (Mass of electron = 9.108 x 10- J kg, Avogadro's number
(a) 1.05 x 10-28 m (b) 1.05 x 10-26 m = 6.023 x 1023 ) (lIT 2002)
(c) 5.27x 10-30 m (d) 5.25 x 10-28 m (a) 6.023 x 1023 (b) _1_ X lerl
9.108
211. The Bohr orbit radius for the hydrogen atom (n = 1) is
approximately 0.530 A. The radius for the first excited state (c) 6.023 x 10S"4 (d) I x 108
9.108 9.108 x 6.023
(n = 2) orbits is: (CBSE 1998) 7
(a) 0.13 A (b) 1.06 A (c) 4.77 A (d) 2.12 A 220. If the electronic configuration of nitrogen had ls , it would
have energy lower than that of the normal ground state
212. The number of nodal planes in px.orbital is: (lIT 2000)
configuration ls22i2p 3 because the electrons would be
(a) one . (b) two (c) three (d) zero
closer to the nucleus. Yet ls7 is not observed because it
213. The angular momentum (L) of an electron in a Bohr orbit is violates: (liT 2002)
given as: (lIT 1997)
I
I 133
(a) Heisenberg uncertainty principle 230. In ground state, the radius of hydrogen atom is 0.53 A. The
(b) Hund's rule radius ofLi 2 + ion (Z =3) in the same state is: .
(c) Pauli's exclusion principle (PET (Raj.) 2007]
(d) Bohr postulates of stationary orbits (a) 0.17 A (b) 1.06 A (c) 0.53 A (d) 0.265 A .
221. The orbital angular momentum of an electron in 2s-orbital is: 231. How many d-electrons in Cu + (At. No. = 29) can have the spin
(lIT 1996; AIEEE 2003; PMT (MP) 2004) quantum number (- ~ f! (SCRA 2007)
I h (a) 3 (b) 7 (c) 5 (d) 9
(a)+-- (b) zero 232. Which of the following electronic configurations, an atom has
22'1t
the lowest ionisation enthalpy? [CBSE (Med.) 2007)
h
(c)- (d)Ji !!.... (a) li2s 2 2p 3 (b) li2s'22p6 3s1
2'1t 2'1t
(c) ti2s 2 2p 6 (d) li2s 2 2p s
222. Calculate the wavelength (in nanometre) associated with a
proton moving at I x I (fl m sec -I. 233. The measurement of the electron position is associated with an
uncertainty in momentum, which is equal to 1 x 10- 18 g cm s - I.
(mass of proton = 1. 67x 10-27 kg, h::::; 6.63 x 10-34 J sec)
The uncertainty in electron velocity is: (mass ofan electron is
(AIEEE 2009)
9 x 10- 28 g) ICBSE-PMT (Pre.) 2008]
(a) 0.032 nm (b) 0.40 nm
(a) Ix lOS ems- I (b) Ix lotI cms- I
(c) 2.5 nm (d) 14 nm
(c)lxI09 cms-' . (d)lxI0 6 cms- 1
-[1IiDt ~A=~,/~ 16~'~~~"~~:nj3~ 234. The ionization enthalpy of hydrogen atom is L312 x 1 0 ! J - - -
mol-I. The energy required to excite the electron in the atom
::::; 0.397x 10-9 m 0.4 nm] from n = 1 to n = 2 is : (AIEEE 2008)
223. The value of Planck's constant is 6.63 x 10-34 J-s. The (a) 9.84 x lOS J mol- I (b) 8.51 x lOS J mor l
velocity of light is 3 x I rf mI sec. Which value is closest to the (c) 6.56 x lOS J mol-I (d) 7.56 x lOS J mol- I
wavelength in nanometer of a quantum of light with frequency [Hint: El ::::; - I.312 X 106 J mol-'
of8x lotS sec-I? . (CBSE(PMT) 2003] 6
E _EI _ 1.312xlO J 1- 1 ...
18 2- 2 - - 4 mo
(a) 5 x 10- (b) 4 x 10' 2
(c) 3 X 107 (d) 2 x 10-25 t.E= (E2 - EI)::: 1.312 X 10 (l-~) 6
(a) nl I, n2 = 2, 3, 4 .. .
3. Which is correct for any kind of species?
(b) n 1 == 2, n2 =3,4,5 .. . (a) (E2 - EI ) > (E3 - E 2 ) > (E4 - E 3 )
(b) (E2 -E,)«E3 E 2 )«E4 E 3 )
(c) nl == 3,n2 4, S, 6 .. .
(d) nl == 4, n2 5,6,7... (c) (E2 -E,)=(E3 E 2 )=(E4 E 3 )
138. Ionization energy of He+is 19.6 x 10- 18 J atom-I. The energy (d) (E2 - El ) = 1/4(E3 - E2 ) 1/9(E4 - )
oftne first stationary state (n == I) of-Li 2+ is: (AIEEE 2010) 4. No. of visible lines when an electron returns from 5th orbit to
:.../ (a) -22x 10-15 J atom- l (b) 8:82 x 10-17 J atom-I ground state in H spectrum is:
(a) 5 (b) 4 (c) 3 (d) 10
(c) 4.4lxlO-16 J at9m-' (d) -4.41 x 10- 17 J atom-'
S. Quantum numbers I 2 and m 0 represent which orbital?
Z2
[Hint: =-1 (a) dxy (b) dxz _ y2 (c) d z2 (d) d zx
lLi&!- zi 6. If n and I are principal and azimuthal quantum numbers
respectively, then the expression fo,{ calculating the total-
lLi&!- . numbers of electrons in allY energy level is:
I 11 I n-1
9 2(21 + I)
f ,&!-= - x19.6x 10- 18 (a) L 2(21 + 1) (b) L
LI 4 1 0 1= 1
I=n+' I=n-I
= 44.1 X 10- 18
(c) L 2(21 + 1) (d) L 2(2/ + 1)
=4.41 X 10-'7 J atom- 1
1=0 1=0
E ,&!- = -4.41 x 10- 17 J atom-I] 7. Order of no. ofrevolutionlsec YI' Y2, Y3 and Y4 forI, II, III and
@LI
13. When a light of frequency vI is incident ona metal surface the 20. CQnsider the followip.g sets, of quantum numbers:
photoelectrons emitted have twice the kinetic energy as did the ',; "n ' '. ','/;T; :. '. , . • m s
photoelectron emitted when the same metal has irradiated with (A) 3 0 0 + Yz
light of frequency V2' What will be the value of threshold (B) 2 2 + Yz
frequency?
(C) 4 3":'2 - Yz
(a) Vo = VI v2 (b) Vo VI 2V2
(d) Vo = VI + v 2
(D) I 0 -1 - Yz
(c) Vo = 2v, - v 2
14.. Heisenberg's uncertainty principle is not valid for:
(E) 3 2 3 +Yz
Which of the following sets of quantum numbers is not
(a) moving electrons (b) motor car possible? [eBSE (Med.) 2007]
(c) stationary particles (d) all of these (a) (A), (B), (C) and (D) (b)(B), (D) and (E)
15. Consider these electronic configurations for neutral atoms; (c) (A) and (C) (d) (B), (C) and (D)
(i) li2s2 2p 6 3s1 (1i) li2s2 2p 6 4sl 21. For three different metals A, B, C photo-emission is observed
Which of the following statements is/are false? one by one. The graph of maximum kinetic energy versus
(a) Energy is required to change (i) to (il) frequency of incident radiation are sketched as :
(b) (i) represents 'Na' atom (BHU (Screening) 2010)
~~ KL~-."-.
(c) (i) and (ii) represent different elements
(d) More energy is required to remove one electron from (i) than
(ii).
16. For the energy levels in an atom which one of the following
statements is/are correct?
(a) There are seven principal electron energy levels v- v-
(b) The second principal energy level can have 4 subenergy (a) (b)
levels and contain a maximum of 8 electrons
(c) The M energy level can have a maximum of 32 electrons
(d) The 4s subenergy level is at a lower energy than the 3d
subenergy level
17. Which of the following statements are correct for an electron
that has n = 4 and m :::: -:- 2 ?
(a) The electron may be in ad-orbital v- v-
. (c) (d)
(b) The electron is in the fourth principal electronic shell
(c) The electron may be in a p-orbital 22. For which of the following species, the expression for the
(d) The electron must have the spin quantum number = + 1/2
18. The angular momentum of electron can have the value(s): energy of electron in the nth [En:::: 13.6 Z2 J
atom-I has
(a) h (b) h
the validity? [SHU (Mains) 2010)
2n n
(a) Tritium (b) Li 2 +
(c) 2h (d)~~
n 22n (c) Deuterium (d) He 2+
19. Which ofthe following statements is/are wrong?
(a) If the value of 1= 0, the electron disttibution is spherical
(b) The shape of the orbital is given by magnetic quantum no.
(c) Angular moment of Is, 2s, 3s electrons are equal
(d) In an atom, all electrons travel with the same velocity
136 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Set-1 S.t-2
The questions given below consist of an 'Assertioa' (A) and
the 'ReasGII' (R). Use the following keys for the appropriate The questions given below consist of two statements as 'Assertion'
answer: (A) and 'Reasoa" (R); while answering these choose anyone of
them:
(a) If both (A) and (R) are correct and (R) is the correct reason for
(a) If (A) and (R) are both correct and (R) is the correct reason for
(A).
(A).
(b) If both (A) and (R) are correct but (R) is not the correct
(b) If (A) and (R) are both correct but (R) is not the correct reason
explanation for (A).
for (A).
(c) If (A) is correct but (R) is incorrect.
(c) If (A) is true but (R) is false.
{d} If(A) is incorrect but (R) is correct.
(d) Ifboth (A) and (R) are false.
I. (A) F-atom has less electron affinity than cr atom. 11. (A) A special line will be seen for 2px - 2py transition.
(R) Additional electrons are repelled more effectively by 3 p (R) Energy is released in the form of wave of light when the
electrons in CI atom than by 2p electrons in F-atom. electron dropsfrom2px to -2py orbital. (AHMS 1996}--
2. (A) Nuclide rgAI is less stable than ~Ca. U. (A) Ionization potential of Be (At. No. = 4) is less than B (At.
No. =5).
(R) Nuclide having odd number of protons and neutrons are
generally unstable. . (lIT 1998) (R) The first electron released from Be is of p-orbital but that
from B is of s-orbital. (AIlMS 1997)
3. (A) The first IE of Be is greater than that of B.
13. (A) In Rutherford's gold foil experiment, very few a-particles
(R) 2p-Olbital is lower in energy than 2s.
are deflected back.
4. (A) The electronic configuration of nitrogen atom is
(R) Nucleus present inside the atom is heavy.
represented as:
If rt Iii
14. (A) Limiting line in the Balmer series has a wavelength of
DO
and not as:'
[J[] 364.4mm.
(R) Limiting line is obtained for a jump of electron from
n = 00.
[U 15. (A) Each electron in an atom has two spin quantum numbers.
(R) Spin quantum numbers are obtained by solving
(R) The electronic configuration of the ground state of an Schrodinger wave equation.
atom is the one which has the greatest mUltiplicity. 16. (A) There are two spherical nodes in 3s-orbital.
5. (A) The atomic radii of the elements of oxygen family are (R) There is no planar node in 3s-orbital.
smaller than the atomic radii of corresponding elements of 17. (A) In an atom, the velocity of electron in the higher orbits
the nitrogen family. keeps on decreasing.
(R) The members of oxygen family are all more (It) Velocity of electrons is inversely proportional to radius of
electronegative and thus have lower value of nuclear the orbit.
charge than those of the nitrogen family. II. (A) If the potential difference applied to an electron is made 4
6. (A) For n = 3, I may be 0, I and 2 and may be 0, ±l and 0, ±l times, the de Broglie wavelength associated is halved.
and±2. (R) On. making potential difference 4 times, velocity is
(R) For each value of n, there are 0 to (n - 1) possible values doubled and hence d is halved.
of I; for each value of I, there are 0 to ±l values of m. 19. (A) Angular momentum of Is, 2s, 3s, etc., all have spherical
7. (A) An orbital cannot have more than two electrons. shape.
(R) The Iwo electrons in an orbital create opposite magnetic (R) Is, 2s, 3s,etc., all have spherical shape.
field. 10. (A) The radial probability of Is electron first increases, till it is
I. (A) The configuration ofB-atom cannot be 1s2 2s2 . maximum at 53 A and then decreases to zero.
(R) Hund's rule demands that the configuration should disph~! (R) Bohr radius for the first orbit is 53 A.
maximum multiplicity. 11. (A) On increasing the intensity of incident radiation, the
9. (A) The ionization energy ofN is more than that ofO. number of photoelectrons ejected and their KE increases.
(R) Electronic configuration of N is more stable due to half- (R) Greater the intensity means greater the energy which in
filled 2p-orbitals. tum means greater the frequency of the radiation.
18. (A) p-orbital is dumb-bell shaped. ll. (A) A spectral line will be seen for a 2px 2py transition.
(R) Electron present in p.:orbital can have anyone of the three (R) Energy is released in the form of wave of light when the
values of magnetic quantum number, i.e., 0, +1 or-I. electron drops from 2px to 2py orbital. (VMMC 2007)
I
• Set-1
1. (b) 2. (a) 3. (c) 4. (d) 5. (c) 6. (b) 7. (d) 8. (a)
9. (a) 10. (b) 11. (d) 12. (d) 13. (a) 14. (c) 15. (b) 16. (a)
17. (c) 18. (d) 19. (b) 20. (c) 21. (d) 22. (c) 23. (b) 24. (a)
25. (d) 26. (b) 27. (d) 28. (a) 29. (d) 30. (b) 31. (c) 32. (b)
·33. (a) 34. (c) 35. (d) 36. (a) 37. (c) 38. (a) 39. (b) 40. (c)
41. (c) 42. (b) 43. (d) 44. (d) 45. (c) 46. (a) 47. (b) 48. (d)
49. (d) SO. (c) 51. (b)· 52. (b) 53. (a) 54. (b) 55. (a) 56. (a)
57. (c) 58. (d) 59. (a) 60. (d) 61. (c) 62. (a) 63. (a) 64. (b)
65. (a) 66. (d) 67. (d) 68. (b) 69. (c) 70. (c) 71. (a) 72. (d)
73. (d) 74. (b) 75. (c) 76. (d) 77. (b) . 78. (d) 79. (a) 80. (d)
81. (b) 82. (b) 83. (c) 84. (a) 85. (b) 86. (a) 87. (b) 88. (c)
89. (b) ...94)~J4!L. !1.. _(at .. !2.Jd), 93. (a) 94. (a) 95. (b) 96. (c)
97. (a) 98. (d) 99. (b) 100. (b) 101. (d) 102. (d) 103. (a) 104. (c)
105. (c) 106. (c) 107. (d) 108. (b) 109. (d) 110. (a) 111. (a) ~ 112. (b)
113. (c) 114. (d) 115. (a) 116. (d) 117. (b) 118. (a) 119. (c) 120. (c)
121. (d) 122. (b) 123. (d) 124. (c) 125. (a) 126. (a) 127. (e) 128. (e)
129. (b) 130. (b) 131. (c) 132. (c) 133. (c) 134. (b) 135. (c) 136. (d)
137. (b) 138. (a) 139. (a) 140. (a) 141. (b) 142. (c) 143. (c) 144. (a)
145. (b) 146. (c) 147. (d) 148. (c) 149. (d) 150. (d) 151. (a) 152. (d)
153. (c) 154. (a) 155. (c) 156. (a) 157. (a) 158. (c) 159. (c) 160. (d)
161. (c) 162. (c) 163. (b) 164. (b) 165. (a) 166. (b) 167. (b) 168. (b)
169. (d) 170. (d) 171. (b) 172. (b) 173. (d) 174. (b) 175. (c) 176. (a)
177. (d) 178. (b) 179. (d) 180. (a) 181. (d) 182. (a) 183. (a, b) 184. (c)
185. (a) 186. (a) 187. (b) 188. (b) 189. (b) 190. (b) 191. (a) 192. (c)
193. (c) 194. (b) 195. (a) 196. (a) 197. (d) 198. (a) 199. (c) 200. (a)
201. (a) 202. (c) 203. (c) 204. (a) 2OS. (a) 206. (b) 207. (c) 208. (c)
209. (d) 210. (c) 211. (d) 212. (a) 213. (a) 214. (e) 215. (a) . 216. (b)
217. (d) 218. (d) 219. (d) 220. (c) 221. (b) 222. (b) 223. (b) 224. (d)
225. (c) 226. (a) 227. (c) 228. (d) 229. (c) 230. (a) 231. (c) 232. (b)
233. (c) 234. (a) 235. (a) 236. (a) 237. (c) 238. (d) 239. (b) 240. (c)
• Set-2
1. (a) 2. (b) 3. (a) 4. (c) 5. (c) 6. (d) 7. (a) 8. (a)
9. (a) 10. (a) 11. (a) 12. (a) 13. (e) 14. (b, c) 15. (c, d) 16. (a, d)
17. (b, c) 18. (a, b, c) 19. (c) 20. (b) 21. (d) 22. (a, b, c)
r"~~;~7"'.i;l:lmii~ __it·]O$'i~GJu;t·]:j·4$~ftI~~~~~
IOBJECTIVE QUESTIONS] for ( lIT ASPIRANTS' .~ .I
The following questions contain a single correct option:
4. Maximum value (n + I + m) for unpaired electrons in second
1. The configuration of Cr atom is 3d 54s1 hut not 3d 44s 2 due to excited state of chlorine l7Ci is:
reason RI and the configuration of Cu atom is 3d 10 4S1 hut not (a) 28 (b) 25
3d 94s 2 due to reason R 2 , RI and R2 are: (c) 20 (d) none of these
(a) R 1: The exchange energy of 3d 54s1 is greater than that of [Hint: Configuration in second excited state may be given as:
3d 44s 2 •
R 2 : The exchange energy of 3d 10 4s1 is greater than that
of3d 94s 2 •
(h) R1: 3d 54s1 and 3d 44s 2 have same exchange energy but
3d 54s1 is spherically symmetrical.
n 3 3 3 3
2 3]
2 . Total n + 1+ m = 25]
R 2 : 3d 104s1 is also spherically symmetricaL m -I o +1 +2 +1
( c) R 1 : 3d 5 4s 1 has greater exchange energy than 3d 4 4i.
5. Which of the following is correctly matched?
R 2: 3d 104s1 has spherical symmetry.
(a) Momentum ofH-atom when electrons
(d) R 1 : 3d 54s1 has greater energy than 3d 4 4i.
R 2: 3d 104s1 has greater energy than 3d 94i·. return from n := 2 to n I 3Rh
4
[Hint: 3d 54s I is correct because it has greater exchange (b) Momentum of photon Independent of wavelength
possibilities of unpaired electrons. of light
1-2, 1-3, 1-4, 1-5
11 I 111 11 11 I :~~~~~lf~es:
(10)
2-3,2-4,2-5
3-4,3-5
(c) elm ratio of anode rays Independent of gas in the
discharge tube
2 3 4 5 (d) Radius of nucleus (Mass no.)1/2
4-5
[Hint: 1 = R [~ ~J := 3R
3d I04s 1 is correct because 3d to-orbitals are spherically A 12 22 4
symmetrical. ] h
A=-
2. Which of the following graphs is incorrect? p
p h = h x 3R 3Rh]
A 4 4
t
v
6. In hydrogen spectrum, the third line from the red end
corresponds to which one of the following inter-orbit jumps of
I the electrons from Bohr orbit of hydrogen?
(a) 4 ~ I (b) 2 ~ 5 (c) 3 ~ 2 (d) 5 ~ 2
7. In which of the following pairs is the probability of finding the
electron in xy-plane zero for both orbitals?
(a) (b)
(a) 3d yz , 4dx 2 - y 2 (b) 2Pz, d z 2
(c) 4dzx',3pz (d) None of these
tv tv 8. In which of the following orbital diagrams are both Pauli's
exclusion principle and Hund's rule violated?
I I (a)@] I I II J, I I (b)
r----,---.-:----.
@] I t It J, II
z ----+ n--+
(c) (d) (C)@] IH Itt I J, I (d) @] IHI II I
3. Which among the following is correct of 5B in normal state?
9. The distance between 3rd and 2nd Bohr orbits of hydrogen
2s 2p atom is:
(a) 0.529 x 10-8 cm (b) 2.645 x 10-8 cm
(a) [ill I I I Against Hund's rule
(c) 2.1l6xI0-8 cm (d) 1.058xlO-8 cm
2
[Hint: 1j r2 = (3 - 22) x 0.529 X 10-8 cm]
. (b)[i] L......!--'--'--'---' Against aufbau principle
as well as Hund's rule 10. Which diagram represents the best appearance of the line
(c) [ill '---'--'---'-----" Violation ofPau!i's exclusion spectrum of atomic hydrogen in the visible region?
principle and not Hund's rule (PET (Kerala) 2007)
(d) [ill I'----!...--"---,
L-I
Against aufbau principle
I
ATOMIC STRUCTURE 139
Increasing wavelength 17. A photosensitive material would emit electrons if excited by
photons beyond a threshold. To overcome the threshold, one
(a) would increase: (VITEEE 2007)
(a) the voltage applied to the light source
(b) the intensity of light
(b)
(c) the wavelength of light
(d) the frequency oflight .
(c) 18. Which of the following electronic configurations have the
highest exchange energy?
3d 4s
(d)
1 I I (a) I iii i I IITJ
(b) ITJ
(e)
11111 II II III (c) i
11. The 'm' value for an electron in an atom is equal to the number
of m values for 1= I. The electron may be present in: (d) IT]
~a) 3dx2 _ y2 . (b) 5~(X2_y2) 19. Which of the following graphs correspond to one node?
(c) 4/3
x Iz
(d) noneofthese
[Hint: Total values of m (21 + I) = 3 for 1 = 1 t
'If
m 3 is for f-subshellorbitals.]
12. If m = magnetic quantum number, I = azimuthal quantum
number, then:
(a) m=I+2 (b) m 2P + 1 -lao -lao
m-I (a) (b)
(c) 1= - (d) 1= 2m+ 1
2
[Hint: Magnetic quantum number 'm' lies between (-I, 0, + I);
thus total possible values of 'm' wiH be (21 + I). t t
m -I 'If 'If
m 21+1, i.e.,. 1= 2 ]
-lao
13. What are the values of the orbital angular momentum of an
electron in the orbitals Is, 38, 3d and 2p?
(0) (d)
(a) 0,0, .J61i, J2 Ii· (b) I, I, J4 Ii, J2 n
(c) 0, 1,.J6 Ii, J3 Ii (d) 0,0,50 1i,.J61i 20. Angular distribution functions of all orbitals have:
(a) I nodal surfaces (b) (l-l)nodal surfaces
[Hint: Orbital angular momentum = ~l(l + 1) h = ~1(1 + 1)il] (c) (n + I) nodal surfaces (d) (n 1- I)nodal surfaces
21£
21. If uncertainty in position and momentum are equal then
14. After np-orbitals are filled, the next orbital filled will be:
uncertainty in velocity is: [CBSE.PMT (Pre.) 2008]
(a) (n + l)s (b) (n + 2)p (c) (n + l)d (d) (n + 2)s
IS. The ratio of (E2 - Ej ) to (E4 E3 ) for the hydrogen atom is (a) fI
V;:
(b) fh
V"2n
(c) _1
2m
fI
V;:·
(d).!
m
fI
V;:
approximately equal to:
(a) ·10 (b) 15 (c) 17 (d) 12 h
[Hint: tJ,x·Ap;;:-
[Hint: 41£
(-~)-(-n 1 1
"9 - 16 _ 7 4
----x
7 1
Ap~ H.: when tJ,x = IIp
108 '" 15 ]
(-±) 3 144 3 mAv;;: rT
-(-I) 4 f41t
16. Which ofthe following electronic configurations hal1 zero spin Av;;:_I_
2m
fE]
V;:
multiplicity?
22. The number of waves made by a Bohr electron in an orbit of
(a) It Ii maximum magnetic quantum number 3 is:
(a) 3 (b) 4 (c) 2 (d) 1
(c) I i I J, [Hint: m == 3, I = 3, n = 4
[Hint: Spin multiplicity =(2u + 1)] For, n = 4, number of waves will be 4.]
140 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
E2(H) = - 13.6 eV (a) 1..= 1.23 (b) 1..= 1.23m (c) 1.23 nm
(d) 1..= 1.23
1 .r;;, Jh .JV V
E 3 (He+ ) -
- 13.6 x 4 eV 40. An excited electron ofH-atoms emits of photon of wavelength
-- -9-
A and returns in the ground state, the principal quantum
number of excited state is given by :
For negative value of E2 , E3 will also be negative.] (a) ~AR (AR - I) (b) ~ (A~~ I) .
35. What is the ratio of the Rydberg constant for helium to·
hydrogen atom? (c) I (d) ~(AR - I)
(a) 1/2 (b) lI4 (c) lI8 (d) 1/l6 ~AR (AR -I) AR
[Hint:
-2n 2mZ 2e4
R = --,,-----
ch 3 [Hint: ±=R[~~ - ~] =RU- ~J
RHe = 2 X 22 = 8
RH Ixe ~=~ A.RA.R-I ]
RH =.!.] 41. A dye a!>sorbs a photon of wavelength A and re-emits the same
RHe 8 energy into two photons of wavelength AI and 1..2 respectively.
36. If the kinetic energy ofa particle is doubled, de Broglie The wavelength A is related to AI and A2 as : _____ _
wavelength becomes: (a) 1..= 1..11..2 (b) 1..= AI + 1..2
(a) 2 times (b) 4 times (c) .J2 times (d) _1_ times (AI + A2 i 1..11..2
.J2 (c) 1..= 1..11..2 (d) A~ A~
[Hint: 1..= _h_ , where, E = Kinetic energy of the particle AI + A2 AI + 1..2
.J2Em 42. The radii of maximum probability for 3s, 3p and 3d-electrons
h h
AI = - - ; 1..2 = ---;::::==- are in the order :
.J2Em J2x2Em (a) (rmax) 3$ > (rmax) 3p > (rmax )3d
Al =..fi i.e. A =~] (b) (rmax) 3$ = (rmax) 3p =(rmax )3d
1..2 ' , 2 ..fi
(c) (rmax) 3d > (rmax) 3p > (rmax )3$
37. Imagine an atom made up of a proton and a hypothetical
particle of double the mass of the electron but having the same (d)(rmax) 3d> (rmax) 3$ > (rmax )3p
charge as the electron. Apply the Bohr:s atomic model and Following questions may have more than one correct options:
consider all possible transitions of this hypothetical particle to 1. Select the correct relations on the basis of Bohr theory:
the fIrst excited level. The largest wavelength photon that will
be emitted has wavelength A (given in terms of the Rydberg (a) velocity of electron oc.!. (b) frequency of revolution oc ~
n n
constant R for the hydrogen atom) equal to: 1
9 . 36 18 (c) radius of orbit oc n 2Z 4
(d) force on electron
(a) 5R (b) 5R (c) 5R (d) i n
oc
R
[Hint: Energy is related to mass: 2. To which of the following species, the Bohr theory is not
applicable?
En oem
The longest wavelength Amax photon will correspond to the (a) He (b) Li 2+ (c) He 2+ (d) H-atom
transition of particle from n = 3 to n = 2 3. The magnitude of spin angular momentum of an electron is
given by: .
A~x =2R(;2~ ;2) (a)S = ~s(s + 1) in (b) S =:s 2:
A
max
=!!]
5R J3 h "1 h
(c) S =-x- (d) S =±-x-
38. What is ratio of time periods (11. I T2 ) in second orbit of 2 2n . 2 2n
hydrogen atom to third orbit ofHe+ ion? [Hint: Spin angular momentum == Js(s + I) ~
(a) -.! (b) 32 (c) 27 (d) 27 2n
27
n3
27 32 8
S=~.!.22(.!. + I) ~
2n
=.J3
22n
x~ ]
[Hint: T 00-
Z2 4. Select the correct confIgurations among the following:
T n
.-1.=_1_
3 x Z2 23 X_
_2 = _ 22 =_]
32 (a) Cr (Z= 24):[Ar] 3d 5,4sl
T2 zf ni
x 12 X 33
27 (b) Cu (Z = 29): [Ar] 3d 10, 4s1
39. The de Broglie wavelength of an electron accelerated by an (c) Pd (Z= 46):[Kr] 4d 1O,5so
electric fIeld of V volt is given by :
(d) Pt (Z = 78): [Xe] 4d 10 4i
I
5. Which among the following statements is/are correct? 11. The maximum kinetic energy of photoelectrons is directly
(a) lJI2 represents the atomic orbitals proportional to ... of the incident radiation. The missing word
can be:
(b) The number of peaks in radial distribution is (n - I)
(a) intensity (b) wavelength
(c) Radial probability density Pnl (r) 41t? R;/(r}
(c) wave number (d) frequency
(d) A node is a point in space where the wave function (lJI ) has 12. Rutherford's experiment established that:
zero amplitude
(a) inside the atom there is a heavy positive centre
6. Select the correct statement(s} among the following: (b) nucleus contains protons and neutrons
(i) Total number of orbitals in a shell with principal quantum
(c) most of the space in an atom is empty
number 'n' is n 2
(d) size of nucleus is very small
(ii) Total number of subs hells in the n th energy level is n
13. Which of the following orbital(s) lie in the xy-plane?
(iii) The maximum number of electrons in a subshell is given
by the expression (41 + 2)
(a) d x2 _ y2 (b) dX), (c) dxz (d) Fa
(iv) m = 1+ 2, where 1 and m are azimuthal and magnetic 14. In which ofthe following sets of orbitals, electrons have equal
. quantum numbers .orbital angular momentum?
(a) (i), (iii) and (iv) are correct (a)13and2s (b) 2sand2p (c) 2p and 3p(d) 3pand3d
(b) (0, (ii) and (iii) are correct 15. Which ofthe following orbitals have no spherical nodes?
(c) (ii), (iii) and (iv) are correct (a) 13 (b) 2s (c) 2p (d) 3p
(d) (i), (iiyand (iv) are correct Hi~ For a'snellofpriiiCipalquaniiirri Ilurnber'n~~4, tnere are:~
7. Which among the following are correct about angular (a) 16 orbitals (b) 4 subshells
momentum of electron? (c) 32 electrons (maximum) (d) 4 electrons with 1= 3
17. The isotopes contain the same number of:
(a) 2 n (b) 1.5!: (c) 2.5ft (d) 0.5!:
1t 1t (a) neutrons (b) protons
8. Which of the following is/are incorrect for Humphrey lines of (c) protons + neutrons (d) electrons
hydrogen spectrum? 18. Which of the following species has less number of protons
(a) n2 7 -7 n! = 2 (b) n 2 10 -7 n! = 6 than the number of neutrons?
(c) n2 5 -7 n! = 1 (d) n2 11-7 n! = 3 (a) !~C (b) 19F (c) nNa (d) fiMg
9. In the Bohr's model ofthe atom: 19. The angular part of the wave function depends on the quantum
(a) the radius of nth orbit is proportional to n 2 numbers are:
(b) the total energy ofthe electron in the n th orbit is inversely (a) n (b) I . (c) m (d) s #
proportional to 'n' 20. Which of the following species are expected to have spectrum
(c) the angular momentum of the electron is integral multiple ,similar" to hydrogen? '
of h/21t (a)He+ (b) He 2+ (c)'U 2 + (d)U+
(d) the magnitude of potential energy of an electron in an orbit 21. Which of the following statements is/are correct regarding a
is greater than kinetic energy hydrogen atom?
10. Which among the following series is obtained in both (a) Kinetic energy ofthe electron is maximum in the first orbit
absorption and emission spectrums?
(b) Potential energy of the electron is maximum in the first orbit
(a) Lyman series (b) Balmer series
(c) Radius of the second orbit is four times the radius of the
(c) Paschen series (d) Brackett series first orbit
(d) Various energy. levels are equally spaced
[;/I~ ..-:- - - - - - - - - - - - - - - - - - - - - 1
• Single ,correct option
1. (e) 2. (d) 3. (c) 4. (b) :5~ (a) 6. (d) 7. (d) 8. (d)
9. (b) 10. (c) 11. (b) 12. (e) 13. (a) 14. (a) 15. (b) 16. (c)
17. (d) 18. (b) 19. (b) 20. (a) 21. (c) 22. (b) 23. (a) 24. (b)
25. (a) 26. (b) 27.. (b) 28. (a) 29. (b) 30. (c) 31. (b) 32. (b)
33. (b) 34.. (e) 35. (e) 36. (d) 37. (e) 38. (b) 39. (e) 40. (b)
41. (e) 42. (a)
[~. ~'
.... ~
....
I
1. (1) 2. (5) .3. (3) 4.. (4) 5. (1) 6. (3) 7. (6) 8. (5)
9~ (6) l(t (5)
I
144 I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
[Hint: _1-
AHe+
=RHZ2 [J.. -J..J
22 3 2
1. Radius of first Bohr orbit of muonic hydrogen atom is:
(a) 0.259 A (b) 0.529 A
207 207
= 109678 x 4 [:6J (c) 0.529 x 207 A (d) 0.259 x 207 A
2. Energy of first Bohr orbit of muonic hydrogen atom is:
AHe+ =1641.1 A]
(a) - 13.6 eV (b) -13.6 x 207eV
2. How many lines in the spectrum will be observed when 207
electrons return from 7th shell to 2nd shell?
(c) + 13.6 eV (d) +13.6 x 207 eV
(a) 13 (b) 14 (c) 15 (d) 16 207
[Hint: Number of lines in the spectrum 3. Ionization energy of muonic hydrogen atom is:
= (1~ - nl )(~ - n) + I) (a) +13.6 eV (b) +13.6 x 207eV
2 207
_ (7-2)(7-2+ 1) IS
(c) - 13.6 ~V (d) -13.6 x 207eV
2 207
7- 4. Angular momentum of 'muon' in muonic hydrogen atom may
ll1~~~
be given as:
6-
S- 15 lines in the spectrum.] (a) h (b) ~
(c) h (d) h
'IE 2n 4'IE 61t
4-
5. Distance between first and third Bohr orbits of muonic
3- hydrogen atom will be:
2- 2
(a) 0.529 x 2A (b) 0.529 x 7A
3. The wavelength of first line of Balmer spectrum of hydrogen 207 . 207
will be: (c) 0.529 x 8A (d) 0.529 A
(a) 4340 A (b) 4101 A (c) 6569 A (d) 4861 A 207 207
[Hint: .!.A = RH [J.. -~J
n2
22 • Passage 3
for fIrst line n = 3,
I [ I I]
-=109678 - - -2
A. 22 3
Nuclei that have 2,8,20,28,50,82 and 126 neutrons or protons
are more abundant and more stable than other nuclei ofsimilar mass.
It is suggested that in the nuclear structure ofthe numbers 2, 8, 20,28,
A= 6569A] 50, 82 and 126, which have become known as magic, nu11ll}(!rs, the
4. In which region of electromagnetic spectrum does the Balmer nuclei possessing magic numbers are spherical and have zero
series lie? quadruple moment and hence they are highly stable. Nuclear shells
(a) UV (b) Visible are filled when there are 2, 8, 20, 28, 50, 82 and 126 neutrons or .
protons in a nucleus. In even-even nuclei all the neutrons and protons
(c) Infrared (d) Far infrared
are paired and cancel out spin and orbital angular momenta.
ATOMIC STRUCTURE 145
Answer the followhig questions regarding the stability of The only way to explain the results, Rutherford found,. was to picture
nucleus: an atom as being composed of a tiny nucleus in which its positive
1. Which of the following element(s) is/are stable though having charge and nearly all its mass are concentrated. Scattering of
odd number of neutrons and protons? a-particles is proportional to target thickness and is inversely
(a) ~Li (b) I~B (c) iRe (d) IjN . proportional to the fourth power of sin %' where, (-) is :'cattering
2. Stable nuclei having number of neutrons less than number of
angle. Distance ofclosest approach may be calculated as:
protons are:
2
(a) iH (b) ~He Z;Z2e
1:. =-.--
mill 4nEoK
3. Doubly magic nucleus is ...
(a) 2~iPb (b) 2~Pb (c) 2~~Pb (d) 2~;Bi where, K kinetic energy ofa-particles.
Answer the follOwing questions:
4. Which among the following has unstable nucleus?
1. Rutherford's a'particle scattering experiment led to the
(a) IjN (b) l~N (c) I~N (d) 1~0 . con~lusion that: '
5. Which of the following has zero spin and angular momentum? (a) mass and energy are related
(a) ~~Ca (b) iH (c) I~C (d) {jCI (b) mass ,and positive charge of an atom are concentrated in
the nucleus .
(c) neutrons are present in the nucleus
• Passage4
(d) atoms are electrically rieutrill·
The substances which contain species wi{h unpaired electrons in 2. From the a-particle scattering experiment, Rutherford
their orbitals behave as paramagnetic substances. Such. substances concluded that:
are weakly attracted by the magnetic field. The paramagnetism is (a) a-particles can approach within a distance of the order of
expressed in terms of magnetic moment. The magnetic moment is 10'-14 m of the nucleus
related to the number of unpaired electrons according to the
(b) the radius of the nucleus is less than 10- 14 ~
following relation:
(c) scattering follows Coulomb's law
Magnetic moment,!l ~n(n + 2) EM (d) the positively charged parts of the atom move with
extremely high velocities
where, n number of unpaired electrons. 3. Rutherford's scattering formula fails for very small scattering
BM stands for Bohr magneton, a unit of magnetic moment. angles because:
(a) the gold foil is very thin
IBM = eh = 9.27 x 10-24 Am2 orJT- 1
4nmc (b) the kinetic energy of a-particles is very high
(c) the full nuclear charge of the target atom is partially
Answer the following questions: screened by its electron
1. Which of the. following ions has the highest magnetic (d) there is strong repulsive force between thea-particles and
moment? nucleus of the target
(a) Fe 2+ '(b) Mn 2+ (c) Cr 3+ (d) V 3+ 4. Alpha particles that come closer to the nuclei:
2. Which of the following ions has magnetic moment equal to (a) are deflected more (b) are deflected less
that ofTi 3+: . .
(c) make more collision (d) are 'slowed down more
(a) Cu 2+ (b) Ni2+ (c) C0 2+ Cd) Fe 2+ 5. Which of the following quantities will be zero for alpha
3. An ion of a d-block element has magnetic moment 5.92 BM particles at the point of closest approach to the gold atom, in
Select the ion among the following: Rutherford's scattering of alpha particles?
(a) Zn 2+ (b) Sc 3+ (c) Mn 2+ (d) Cr 3+ " (a) Acceleration (b) Kinetic energy
4. In which ofthese options do both constituents of the pair have (c) Potential energy (d) Electrical energy
the same magnetic moment?
r
(a) Zn 2+ and Cu + (b) C0 2+ and Ni 2+ • Passage 6.
(c) Mn4+ andCo + 1 (d) Mg2+ and Sc+
The splitting ofspectral lines by a magnetic field is called the
5. Which of the following ions are diamagnetic? Zeeman effect 'after the Dutch physicist Pieter Zeeman. The Zeeman
(a) H~2+ (b) Sc 3+ (c) Mg2+ . (d) 0 2- effect is a vivid confirmation of space quantization. Magnetic
quantum number 'm' was introduced during the study of Zeeman
• Passage5 effect. 'm' can have the (21 + 1) values (-1,0, + I). Magnetic
quantum number represents the orientation of atomic orbitals in
At the suggestion of Ernest Rutherford, Hans Geiger and Ernest three-dimensional space. The normal Zeeman effect consists of the
Marsden bombarded a thin gold foil by a-particles from a polonium splitting ofa spectra/line offrequency Vo into three components, i.e.,
source. It was expected that a-particles would go right through the
e . e
roil with hardly any deflection. Although, most of the alpha particles --B; v 2 Vo +--B
indeed were not deviated by much, a few were scattered through very 4nm 4nm
large angles, Some were even scattered in the backward direction. Here, B is magnetic field.
1.46 .1 G.RB. PHYSICAL CHEMISTRY FOR COMPETITIONS
Answer the following questions: .' 3. Which of the following quantum numbers is not derived from
1. Which of the following statements is incorrect with reference SchrOdinger wave equation?
to the Zeeman effect? ., (a) Principal. (b) Azimuthal
(a) In a magnetic field, the energy of a particular atomic state (c) Magnetic (d) Spin
. depends on the values of'm' and 'n' . 4. In any subshell, the maximum number of electrons having
. (b) Zeeman effect is us~d to calculate the elm ratio for an same value of spin quantum number is:
electron
(c) Individual Spectral lines split into separate lines. The (a)~l(l+l) (b) 1+2 (c) 21 + I (d) 41 + 2
distance between them is independent ofthe magnitude of 5. The orbital angular momentum for a 2p-electron is:
.the magnetic field .
(d) Tile Zeeman effect involves splitting of a spectral line of
(a) J3 Ii (b) 16 Ii (c) zero (d) J2'!!'-'
2n
frequency Vo into tbree components
2. A d-subshelt· in an atom in the presence and absence of • Passage 8
magnetic field is: .
Dual nature ofmatter was proposed by de Broglie in 1923, it was
lea) five~fold degenerate, non-degenerate
experimentally verified by Davisson and Germer by diffraction
(b) seven-fuld degenerate, non-degenerate
experiment. Wave character of matter has significance only for
(c) five-fold degenerate, five.:fold degenerate microscopic particles. de Broglie wavelength or wavelength of
·'(d) non-degenerate, five-fold degenerate matter wave can be calculated using the following relation:
3~ Which among the·. following. is/are . correct about the
orientation of atomic- orbitals in space? A= h
(a) s-orbitals has single orientation mv
(b) d-subs4ell orbitals have three orientations along
where, 'm' and v' are the mtl$S and velocity of the particle.
x, yand z directions .
de Broglie hypoth~sis suggested that electron. waves were being
(c) f-subshell have seven orientations in their orbitals
diffracted by the target, much as X-rays are. diffracted by planes of
(d) None of the above·
atoms in the crystals.
t Zeeman effect explains splitting of spectral'lines in: Answer the following questions:
(a) magnetic field .(b) electric field
1. Planck's constant has same dimension as that of:
(c) both (a)' and (b) (d) none of these
(a) vvork (b) energy
i. Inpresence of magnetic field, d-suborbit is:
(c) power (d) angular momentum
(a) five-fold degenerate {b) three-fold degenerate
2. Wave nature of electrons is shown by:
(c) seven-fold degenerate (d) non-degenerate
(a) photoelectric effect (b) Compton effect
(c) diffraction experiment Cd) Stark effect
Passage 7 3. de 'Broglie equation is obtained by combination of which of
Spin angular . momentum of an electron has no analogue in the following theories?
classical mechanics. However, it turns out that the treatment ofspin (a) Planck's quantum theory
angular momentum is closely analogous to the treatment of orbital (b) Einstein's theory of mass-energy equivalence
angular momentum. (c) Theory of interference
Spin angular momentum ~ s(s + 1) Ii (d) Theory of diffraction'
4. Which among the following is not used to calculate the de
Orbital anE,ular momentum = ~'l(l + I) It
Broglie wavelength?
Total spin of an atom or ion is a multiple ofl.. .Spin mUltiplicity is
. . . 2
(a) A';'~ (b) A h
"v mV
a factor to confirm the electronic configuration of an atom of' ion. h . h
(c) A"" r;:;::;- (d) A"" - _ .
. Spin multiplicity =(n:s + 1) v2Em ~2qVm
-. . . $
5. The wavelength .of matter waves associated with a body of
Answer the following qurstiolls: mass 1000g moving with a velocity of 100 mlsec is:'
1. Total spinofMn 2+ (Z 25)ion will be: . (a) 6.62 x 1O-39 .cm (b) 6.62 x 10-36 ern .
. (c) 6..626 X 10- 36 m (d) 3.31 x 10-32 m
(aY ~ (b) 1 (c) 5
2 ·2 2 6. An electron microscope is used to probe the atomic
2. which of the following electrq'~ic configurations have fo~r arrangements to a resolution of 5 A. What should be the electric
spin multiplicity? potential to which the electrons need to .be accelerated ?
(VITEEE 2008)
(a) 2.5 V (b) 6 V
(c) 2.5 kV (d) 5 kV
I
• Passage 9 . . • Passage10
Orbital is the region in an atom where th~ probability ()Jfinding:
the electron is maximum. It represents three-dimensional motion oj The hydrogen-like species Li2+ is in a spherically symmetric state. .
an electron around the nucleus. Orbitals do ,not specify a definite S I with one radial node. Upon absorbing light the ion undergoes·
path according to the uncertainty principle. An orbital is described transition to a state S 2' The state S 2 has one radial node an? its
withthe,help o/waveJunction 'If. Whfmever an electron is described energy is equal to the ground state energy oj the hydrogen atom.
by a wave jUnction., we say that an electron occupies that erbital. (liT 2010)
Since, many wave Junctions are possible Jor an electron, there are Answer the following question;:
many atomic orbitals in an atom. Orbitals have different shapes; 1. The state S I is :
except s-orbitals. all other orbitals have directional character. OOb ~~ ~~ ~~.
Number oj spherical nodes in an orbital is equal to (n 1- 1). [Hint: 2.s: iss~etrical having one radial node.]
Orqital angular momentum oj an electro'n is ~ I (l + I) 'Ii. 2. Energy of the. state S I in uilits of the hydrogen atom ground
Answer the following questions: state energy is: . '
1. Which of the following orbitals is not cylindrically (a) 0.75 (b) 1.50 (c) 2.25 Cd) 4.50 .
. 9 ~
symmetrical about z-axis? E .2+(2s) --x 13.6
(apd z2 (b)4pz (c) 6s (d) 3dyz ~~~ u =2~]
EH -13.6 "
2. The nodes present in 5p-orbital are:
(8,) one planar, five spherical (b) one planar, four spherical 3. The orbital angular momentUm quantum mimber of the state
(c) one planar, three spherical(d) four spherical S2 is:
3. When an atom is pla~ed in a magnetic field, the possible (a) 0 (b) I (c) 2 (d),3
number of orientations for ~n· orbital .of azimuthal quantum [Hint: Orbital angular momentuniquantum number .of 3p
number 3 is: subsheU, i.e., I == 1
(a) three (b) one (c) five (d) seven
4. Orbital angular momentum of J-electrons is:
(a).fi'li' (b)/31i (c)JJi'li (d)21i
5. Which of the following orbitals haslhave two nodal planes?
(a)dxy (b)d yz (c)dx2 _ y2 (d)Allofthese
[/I~
Passage 1. 1, (b) 2, (c) 3. (c) 4. (b) 5. (c)
Passage 2. 1. (b) 2. (b) 3. (b) 4. (b) 5. (c)
Passage 3. 1. (a, d) 2. (a, b) 3. (c) . 4. (c) 5. (a)
Passage 4. i. (b) .2. (a) "3. (c) 4. (a, c) S. (b, c, d)
Passage 5. 1. (b) 2. (a, b, c) 3: (c,.d) 4. (a) 5. (b)
Passage 6. 1. (b) 2. (d) 3. (a,c) 4. (a) S. (d)
Passage 7. 1. (c) 2. (a) 3. (d) 4. (c) 5. (d)
Passage 8. 1. (d) 2. (c) .3. (a, b)
• 4. (~) S. (c) 6. (b)
Passage 9. 1. (d) 2. (c) 3. (d) 4. (c) S. (d)
Passage 10. 1. (b) 2. (c) 3. (b)
148 I G.R.B. PHYSICAl- CHEMISTRY FOR COMPETITIONS
aft®0 A=_h_
J2qVm
produced when the radiation particles collide with matter. elements. At present over forty such materials are known' to exist
Radium produces 134.7 cals of heat per gram per hour. in nature.
(iv) Physiological effect: Radioactive radiations have
serious physiological effects, which may be cumulative over a
period of time. Even a short exposure to intense source of
radiations is sufficient to cause painful inflammation. Gamma
rays are most effective. In general, abnormal cells are more
affected than the healthy cells. On account of this property Electroscope
radiations are used to destroy cancerous tumours. box
(v) Ionisation of gases: This is the most important effect
observed .in the case of radioactive radiations. Radiations
produce ionisation in the gases through which they are passed.
This effect is used for quantitative measurement of p+++++
radioactivity. The radiations cause a number of molecules of the Air
~ 1> r---:--+--
~
Ionisation
gas to lose electrons"'and pass into positive ions. The electrons chamber
immediately become attached to the neutral molecules, thus 1>
making them negative ions. The total ions of one sign are equal Radioactive
material'
to the total ions of the other type. The rate of production of
these ions is proportional to the intensity of radiation. The
extent, to which a definite .quantity of a gas is rendered a
conductor by a radioactive substance, is a measure of. the
radioactive power of a radioactive substance. The apparatus used
for this purpose is called electroscope (Fig. 3.1).
Fig. 3.1 Electroscope for measurement of radioactivity
Geiger-Muller counter is based on this effect. The ionisation
chamber consists of 90% argon and 10% ethyl alcohol vapour at 3.4 ANALYSIS OF RADIOACTIVE
10 mm pressure. Due to ionisation, a flow of current occurs, RADIATIONS
which is measured after amplification.
In 1904, Rutherford and his co-workers observed that when
radioactive radiations were subjected to a magnetic field or a
3.3 HISTORY OF THE DISCOVERY OF
strong electric field, these were split into three types, as shown in
RADIOACTIVITY Fig. 3.2. The rays which are attracted towards the negative plate
In 1895, Henri Becquerelwasstudying the effect of sunlight on are positively charged and are called alpha (a.) rays. The rays
various phosphorescent minerals, among them a uranium ore. which are deflected towards the positive plate are negatively
During a period of several cloudy days, he left the uranium charged and are called beta (P) rays. The third type of rays which
sample in a drawer along with some photographic paper wrapped are not deflected on any side but move straight are known as
in black paper. Much to his surprise, he discovered that the gamma (y) rays. The important properties of these .radiations are
photographic paper had been fogged by exposure to some tabulated on next page:
invisible radiation .1fom uranium. He called this mysterious
property of the ore 'radioactivity'. Radioactivity means 'Y·rays y-rays
ray-emitting activity. He further observed that the radioactive +
mineral emitted these mysterious radiations day after day and + a.-rays
month after month and the emission seemed to be endless. The +
emission was completely unaffected by physical and chemical +
conditions. A year later, in 1896, Marie Curie found that besides + !3-rays
uranium and its compounds, thorium was another element which +
possessed tbe property of radioactiviry. In 1898, Marie Curie. +
and her husband P. Curie observed that the. uranium ore +
'pitchblende', contained more activity than was expected from
the uranium which it contained. It must be obviously due to the . _____ Radioactive --__
presence of some other radioactive elements which were far more -- substances, ---
radioactive than uranium. Finally, they isolated two new
radioactive elements polonium andradium.
Almost in the same period, G. C. Schmidt reported that
thorium compounds possessed radioactivity. In 1901, A~
Fig. 3.2 . (a) Deflection of radioactive rays in electric field
Debieme and F.S. Giesel discovered another new radioactive
and (b) Emission of radioactive rays and their
element actinium in uranium minerals. Further systematic deflection in a magnetic field.
researches led to the. discovery of many more radioactive
··152. I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
"
1. Nature These consist of These consist of y-rays are simi- 5. Photographic a-particles affect !3-rays effect on y"rays have little
small. positively negatively char- lar to X-rays. effect . the photographic a photographic effect on photo-
charged particles ged particles These are neu- plate. plate is greater graphic plate.
which are merely which have the tral in nature .. than a-particles.
nuclei of helium s.ame elm value They have very Like cathode
atoms, each con- as the cathode small wave- rays, !3-rays pro-
sisting of 2 pro- rays. ~rays are lengths of the duce X-rays.
tons . and • 2 merely elect- order of 10- 10 to
6. Effect on a-particles p..particles have y-rays have very
neutrons. These rons. The ~rays 1O- l3 m..
are represented as are represented zinc sulphide produce. little effect on little effect on
screen luminosity on ZnS ZnS screen due ZnS screen.
iHe aL?flor _?e. screen due to high to low kinetic
2. Velocity The a-rays are The ~rays are They travel with kjnetic' energy. energy.
ejected with high much faster than the velocity of Note:
velocities ranging a-rays.' They light
0) The quantum energy ofy-rays emitted by a radioactive substance
from 14 x 109 to have generally can have unique and discrete values. '.
17 x I 09 crn!sec. different veloci- (ii) The energy of f;X.-particles emitted by a radioactive substance
. . ties sometimes
The v. eloclty of bin th (a-emitter) has unique value.
·· d approac. g e
a-rays d~pen s velocity of light (iii) The energy of p..particles emitted by a radioactive substance,
upon the .kmd of $-emitter) can have any value between zero and end point
nucleus from energy.
which they are.
. emitted. 3.5 CAUSE OF RADIOACTIVITY
3. Penetrating' a-particles have p..rays are more Due to high ve- Except in the case of ordinary hydrogen, all other nuclei contain
power small penetrating penetrating locity and both neutrons and protons. A look at the stable nuclei shows that
power i'lue to than a-particles. non-material the ratio nl p (neutrons/protons) in them i$ either equal to I or
relatively larger This is due to character, y-rays more than 1. The ratio is "" lin all the light-stable nuclei up to
size. They are. small size- and are 10 10 times'
stopped by a high'" velocity. more.' penetrat-
calcium (ig
Ca) and thereafter the ratio is greater than 1 and
piece of alu- These are stop- ing than a-rays.
increases up to 1.6 for heavy stable nuclei as shown in the
minium. foil of ped by a.1 cm following table: .
6.1 rom thick- thick sheet of Neutron-proton ratio in some stable nuclei
npss. aluminium.
. . l1C 14N 16 20 40 64
':::Zr l~Sn l::Nd ,~Hg
Isotope 6' 7 sO loNe 20 Ca 30Zn
. Cardboard Aluminium Lead
n 6 1 8 10 20 . 34 50 70 90 122
a---f-- p 6 7 8 10 20 30 40 50 60 80
. I 1.13 1.25 1.40 1.50 1.53
nip
i
(J)
c
100
I, . 35 8
16.
19
16
= 1.2
l3-emission
358--t
16 . 17 35Cl+ °e
-I
e
s
Cl>
~O
I~p ~(~ <1) Positron emission
9 - - t .8 0 + +1°e
z 9 p. 17 p 17
15 60
Co Lies below stability belt, it has a heavy .
..c
E n 58 nucleus and it decays by K-electron
ISfAg =- 1.23 capture.
-2. 40 p 47
12iAg+ _?e--t I~Pd + hv
20
It is a neutron rich species. It undergoes
n 146
2~~U -=: =1~9 decay by a-emission.
p 92
o 20 40 60 80 100 iJrh + iHe
21~ U - - t . 239
.
Number of Protons ----'--"'"
.
nucleus of the new element, called daughter element, possesses Isoters No. of atoms'" same, CO 2 , N2 0
atomic mass' or atomic mass number less by four units and No. of electrons same,
nllclearcharg~ of.atomic number less by 2 units because physical properties same.
(£·particle has mass of 4 units and nuclear charge of two units. Isodiapheres I ~otopicexcessmass(N-P) 92 U235 , 90Th231
The daughter element' after a-emission is called 'an .- same.
isodiaphere of parent ~Ienient.
-IX .
214Pb
82 ~
214Bi
83 + °e
-I
(Lead) (Bismuth)
Parent element ~ Daugh~er element
234 T h 234
Atomic mass W W- 4 90 ~ 91 Pa + -I°e
Atomic number Z Z- 2 (Thorium) (Protoactinium)
Examples
(i) Polonium eJ1 Po) belongs to group 16 (VIA) of the
periodic table. On losing an alpha particle, it is transformed into
lead (2~g Pb) which belongs to group 14 (IVA), i. e., two places to ::::::I_SOME SOLVED EXAMPLES\.I:::: : :
the left ofthe parent element, polonium.
Example 1. Calculate the number of neutrons in the
2i1Po ---7 2~gPb
remaining atom after emission of an alpha particle from 2t~ U
16 14
(VIA) (IV A) atom.
Solution: On account of emission of an alpha particle, the
(ii) Bismuth eJi
Bi) belongs to group 15 (VA) of the periodic
atomic mass is decreased by 4 units and atomic number by 2
table. It emits all alpha particle resulting in the formation of units.
thallium which belongs to group 13 (IlIA), i. e. , two places to the So, . Atomic mass of daughter element 234
left of the parent element, bismuth.
Atomic number ,of daughter element 90
213B'! 209TI
81
83
Number of neutrons atomic mass ~ atomic number
15 13
(VA) (III A) = 234 90?= 144
(iii) Carbon e:C) belongs to group 14 (IV A) and emits a Example 2. Radioactive diSintegration of 2i~Ra takes
i3-particle forming nitrogen ejN) which belongs to group 15 place in the following manner into RaC,
-a -a -a -~
(V A), i, e" one place to the right of the parent element. Ra ---7 Rn ---7 RaA ---7 RaB ---7 RaC
I:C ---7 liN + _~e Determine mass number and atomic number of Rae.
'(IV A) (V A)
Solution: Parent element is 2~~Ra.
(iv) Phosphorus (?~ P) belongs to group 15 (VA) and emits a .Atomic mass = 226
i3-particle forming sulphur (?i
S) which belongs to group 16 Atomic number
._/
= 88
(VIA), i. e., one place right to the parent element. RaC is formed after the emission of 3 alpha particles: Mass of
f~ P ---7 iJ S + _~ e 3 alpha particles = 3 x 4 := 12'
(V A) (VIA) So, Atomic mass ofRaC (226 - 12) = 214
156 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(c)
.
d+(~1
2
c (d) 2c - d +a b
j
3.8 RADIOACTIVE DISINTEGRATION SERIES
[Arts. (c)]
Elements beyond bismuth are all radioactive in nature. Most of
[Hint: No. of a-particles =:: ( a 4 b) them have several radioactive isotopes. These radioactive
elements . disintegrate to give new elements which again
Zj - 2a+ ~ Z2 . disintegrate to form other elements and so on. The process
~= -Z[ + 2a continues till a non-radioactive end product is reached.
(a - b)
=d c+ 2 - - - "The whole chain of such elements starting from the parent
4 element (radioactive) to the end element (non-radioactive) is
(a - b) called a radioactive series or a family".
=d+----c]
2 All the naturally occurring radioactive elements above atomic
2. A radioactive nuclide emits y-rays due to: number 82 belong to one of the three radioactive series. These are
(a) K -electron capture known as: .
(b) nuclear transition from higher to lower energy state (i) Thorium series . (ii) Uranium series
(c) presence of greater number of neutrons than protons (iii) Actinium series
(d) presence of greater number of protons thari neutrons Uranium and thorium series have been named on the basis of
[Ans. (b)] long lived isotopes of 238 U and 232 Th. The parent element of
[Hint: After a, J3-emission, nucleus goes to excited state; actinium series is 235 U but originally it was thought to be an
when it returns to normal state, emission of y-radiations takes isotope of actinium, 227 Ac. The three series are also referred to 4n
. place.] (thorium), 4n + 2 (uranium) and 4n + 3 (actinium) series as when
3. In which of the following transformations, the ~-particles are the mass numbers of various members belonging to these series
emitted? when divioed by four, either there is no remainder (as in thorium
(a) Proton to neutron (b) Neutron to proton \series) or the remainder is 2 (as in uranium series) or 3 (as in
" actinium series). The end product in all the three series is an
(c) Proton to proton (d) Neutron to n~utron
,.isotope of lead which is stable and non-radioactive in nature. The
[Ans. (b)] •
[Hint: ~n ---7 :H
+ _~e + antineutrino] following table shows the main characteristics of three
fadioactiveseries: .
4. In the radioactive decay:
AX
Z
AY
- - 7 Z+I
A- 4
- - 7 Z-l
A - 4 *
z - - 7 z-i Z - Atomic.'-,'"
masses
Halflife.
the sequence of emission is: First. Last when No.ofa.- No. of (3-
of first
(a) a,~,y (b) ~,a,y (c) y,a,~ (d) ~,y,a Series mem- mem- divided partieles particles
member
[Ans. (b)] her her by 4, the emitted emitted
in years
remain-
[Hint: 1x -
_~e ---7 z+ ~y; z+ lAy - iRe ---71=iz; ~
der
A 4z _y ---7 A-4Z * ]
Z-l Z-l
Thorium 2~~Th 1.4 x 10 10 2~~Pb 0 6 4
(4n)
5. Which of the following elements is an isodiaphere of 2~i U?
'ta) 2~3Bi (b) 2~2Pb (c) 23.kTh (d) 2t\Pa Uranium 2~~U 4.51 x 10 9 2~~Pb 2 8 6
(4n + 2)
[ADS. (c)]
[Hint: Is.odiapheres are formed by a-emission. Actinium 2~~U 7.07 x 108 z~~Pb 3 7 4
niz
U - iHe ---7 239~Th (Isodiaphere)] (4n + 3)
~212B·7
(c) 3 and 4 respectively (d) 3 and 8 respectively -~ -0: -0: -[3
[Ans. (b)] 208
Pb /
[Hint: ---7 1x t.-;r 82 "'-
-~
/
~[3
83 1 "'-
-[3~ -0:
in mass number ! 2 212 Po 212
82 Pb
Number of a-particles = 84 .
44
Z 2 x Number of a-particles + Number of~-particles Z - 3
158 'I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(ii) Uranium s.eries [(4n +2) series}: series in nature whose isotopic masses carry a numerical
-a -I} -I} a -a -a relationship of 4n + 1 The most reasonable explanation for the
2t~U - t 2t<iTh -t 2tiPa -t 2tiu -t 2igTh -t 2~;Ra - t 2~lRn absence of this series in nature was that no member of this series
was sufficiently long lived to have survived over the years since
210Tl' " 214 Pb I the series might have been formed. Except the last member, all
'~~Pb(" "('~po~
other members of this series have been obtained by artificial
means. The name of this series is given on the long lived isotope
' ) 'klBi ( ' 82 , of neptunium (Hal( life' 2~~ Np 2.25 X 10 6 years). This family
-0 /-13 ' -~ ~' . differs from the other three naturally occurring series in the
, 2~! P02~~ At
.',
following respects:
13
207 Tl
81. '
-13 227
90
Th -IX
-13 2~ TI -IX
. 2~; Pb/ 22k\Bi ~ 'k\Pb ." '~Po In this series, seven alpha and four beta particles are emitted.
-"
~21l PO , -13 84
3.9 RATE OF DISINTEGRATION AND HALF
LIFE PERIOD
Only 18radioactive isotopes with atomic number 82 or less, The radioactive decay of the different radioactive substances
are found in nature. 14 C is the exception because it < is , differ widely. The rate of disintegration of a given substance
, continuously synthesized in our atmosphere. All these natural depends upon the nature of disintegrating substance and its
radioactive elements have half-life longer than I 09yrs (age of total amount. The law of radioactive disintegration may be
earth). Another 45 ,radioactive isotopes having atomic number defined' as "the quantity of ra(}ioactive substance which
greater than 82 are also found innatuni and fall in above three disappears in unit time is directly proportional to the
natural decay series. amount* of radioactive substance present or yet not decayed."
The quantity of the radioactive substance which disintegrates or
Similarities between Radioactive Series disappears in unit time is called rate of disintegration.
(i) In' all the series, there is an element of zero group with Tbe rate of disintegration decreases with time as the
atomic number 86. This element comes in the gaseous state and is amount of radioactive substance decreases with time. One of
called emanation. Different names are given to three isotopes. the most important characteristics of the radioactive
These are radon in uranium series, thoron in thorium series and disintegration is that a certain definite fraction of a radioactive
actinon in actinium series. sample undergoes disintegration in a definite period of time. This
(ii) In all,the series, the last product is an isotope of lead time period does not depend upon the initial amount of the
(atomic number 82), 206Pb in uranium series, 207 Pb in actinium radioactive substance.
series while 208 Pb in thorium series. Due to this reason, lead is For example, whatever be the amount (initial) of 131 I taken, it
found in nature as a mixture of these three isotopes. becomes half within 8 days. This has been shown in Fig. 3.4 (a).
(iii) In all the series, there are certain elements which Initial amount of 131 I The amount of 131 I after 8 days
disintegrate in a branching process by emitting either ex or 20 grams 10 grams
B-particles. The species thus formed are then disintegrated in 10 grams 5 grams
such a way as to give a common product. 5 grams 2.5 grams, etc.
Rutherford mtroduced a constant known as half life period. It
Neptunium series [(4n +1) series]: For many years
is defined "as the time during which half the amount of a
scientists speculated upon the failure to find a disintegration given sample of the radioactive substance disintegrates".
Amount of a radioactive substance can be taken in terms of number of atoms or moles or grams, milligrams, etc.
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 159
4t112
cr
I· o= - No
-N
16 2/
IS
.16
[ 1 ] No .
No=I--
16
o
'---v--'
8 16 24 32 40. 48
nt1l2
. (Ir
- No [I nr]No
tl12 Days-- .\2
Amount of radioactive substance left after n half life periods
Fig. 3.4 (a)
. N=Gr No
i
'Qi
No and . total time T
where, n is a whole number.
:::
nx t 112
~:::.SOME SOLVED EXAMPLES\ ::::.:: :
U
:"
c:
"C
0) .
Example 10. The half life period of radium is 1.580 years.
. >- How do you interpret this statement?
«I
0
~ Solution: Whatever quantity of radium is taken, it shall
c:
:" become half after the expiry of 1580 years. The following table
'0 explains the statement:
....
0)
..0 Quantity of radium Quantity of radium
E at present after 1580 years
::l
Z
100 atoms' 50 atoms
tll2 2tl12 3tl12 4tl12 50 gram 25 gram
Time ----+ 5 mole 2.5 mole
Fig. 3.4 (b) Example 11. The radioactive isotope 137 Cs has a half life
period of30 years'fjStarting with I mg of J37 Cs, how much would
Every radioactive element is characterised by a definite constant remain after 120years?
value of half life period, Half life period of an element is also a Solution: At this time, we have 1.0 mg of 137 Cs; after 30
measure of its radioactivity, since shorter the half life period, .the years, we shall have Qne half of the original, or 0.50 mg; after 60
greater is the number of disintegrations and hence greater its .years, we shall have 0.25 mg; after 90 years, we shall have 0.125
radioactivity. Half life periods vary from billions of years fQr mg and, finally, after 120 years, we shall have 0.0625 mg.
some radioisotopes to a fraction of a second. After30 years 0.50 mg
Halflife period is represented as t 112' 60 years 0.25 mg
Let the initial amount of a radioactive substance be No. 90 years 0.125 mg
After onehalflife period (t1l21 it becomes = No 12 120 years 0.0625 mg
After two half life periods (2t 112)' it becomes =N 0/4 Alternative solution: Total time I 20 years
We know that, . total time = n x t 112
After three half life periods (3t 112)' it becomes = N 0/8 So, 120' nx30
and Arter n half life periods (nt 1l2 )', it shall become = Gr No Thus, the quantity of the isotope left after· .
n4
(1)4 No =(1\4
Thus, for the total disintegration of a radioactive four halflife periods =l'2 '2). xl
substance an infinite time will be required. 1
-= 0.0625mg
16
160 G.R.B. PHYSICAL OtiEMISTRY FOR COMPETITIONS
. " Example 12.' A radioactive element has half life period of Example 15. A radioisotope has tll2 5 years. After a
30 days. How much ~fit ~ill be left after 90 days? given amount decays for 15 years, what fraction o/the original
Solution: Total time = 90 days isotope remains?
Solution: Half life (t 112 ) == 5 years
Half life (t I12 ) 30 days
Time for decay (T )::= 15 years
We know that, total time =n x tll2 ,
We know that, T = n x tl12
So, 90= n x 30 So, 15 = n x 5
n==3 or n=3
Thus, quantity left after three half life periods, . Let the original amouI¢ be = No
, Let the amount left after three half life periods be N
1 3
::= (z) No [N 0 original amount] fraction N / No
,I I
== xNo==-No
8 8,
We know that, N= lz1)11 '
r
No
Example 13. The half life period of 2~~PO is 140 days, In N _(1)11 _((\3
Solution: Original quantity of the isotope (N 0) I g Thus, after 15 years lth of the original amount remains.
, Final quantity of the isotope NO. 25 g 8
Exampl.e 16.' if in 3160 years, a radioactive substance
We know !hat, becomes onejourth of the original amount, find its half life
period.
N 1
1 == - (1)11 xl Solution: ---
So, No 4
4 ..2
1
or
I"
So,
4 UY'
2)
m
Time taken T == n X tl12
n=2
== 2 x 140
280 days
or
or
lz'Ifn=2
(~r
Example14. The half life period oj. 234 U is 2.5 X 105 We know that, total time' T' =n xt 112
years. In how much time is the quantity of an isotope redJlced to So, 3160' 2xt Jl2
25% of the original amount? 3160
or = 1580 years
tll2 =
Solution: Initial amount of this isotope No == 100 2
Final amount of the isotope N == 25 The halflife period of the radioactive substance is 1580 years.
or n==2
0.693
--
2.303 1
- - oglO -
(No)
2x x N
Time taken T nxt ll2 1
2 loglo 2 = log
(NNO)\
= 2x 2.5x 105 5
= 5x 10 years
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 161
Relationship between !talC life period and radioactive" A x No. of atoms of element undergoing decay
disintegration constant. .
= 0.69-3 .x mass. x Avogadro's number
When t:;::: t 1/2 , N t1l2 atormc mass
2
Putting the values in eq. (vi) Parallel Path Decay
2.303 No 2.303 2
1
I\, 1oglo ~- = - ' - 1ogIO Let a radioactive element 'A' decays to 'B' and 'c' in two
tl/2 . No/2 tll2 parallel paths: '
The value oflog 10 2 is 0.3010,
·
S0,
1 0.693
1\,=-- or
t1l2
t1l2 =
. 0.693
A
A<B C
Thus, half life period of a given radioactive substance does not Decay constant of
depend on the initial amount of a radioactive substance but depends 'A' Decay constant of' B' + Decay constant of' C'
only on the disintegration constant of the radioactive element. AA AB + AC ' ." (i)
Here, AB = [fractional yield of B] x A A
3.10 AVERAGE,LIFE' AC :;::: [fractional yield of C ] x A A '
It is the sum of the periods of ~xistence of aU the atoms Maximum Yield of Daughter Element
divided by the total number' of atoms of the radioactive
Let a radioactive element' A' decays to daughter element' B' .
SUbstance.
' AI'" TotaI'~'
Ihe tIme 0 f aIIthe atoms A )B .
verage he = , ,
Total nun1ber of atoms AA and AB are decay constants of 'A' and 'B'. Maximum
fo=
t dN I activity time of daughter element can be calculated as:
==---
No A t
max
= 2.303
(AB AA)
10 [AS] i
glO AA
Thus, average iife of a radioactive element is the inverse of its
disintegration'or decay constant.
I t 1 '2 3.11 RADIOAC11VE EQUILIBRIUM
Average life = -'- = 1.44t1l2
A 0.693 Let us consider thafa radioactive element A disintegrates to give
The average life of a radioactive substance is 1.44 times of its B which is also radioactive and disintegrates into C.
half life period. . A ----t B ----t C
The element B is said to be in radioactive equilibrium with A if
Alternatively:
or .
At = loge l; J
iN
equilibrium, then we have
Rate of formation of B = Rate of decay of A = AIN 1
and Rate of decay of B :;::: AzN 2
e AI =NO
-
At radioactive equilibrium,
N AINI =A 2 N 2
N -At A2 11 Al Average life of A
, or --:::!e or =- - -
No N2 'AI 11 A2 Average life ofB ZB
i 1 N
.Let t ; then = e- 1 Thus, the number of atoms of A and B are in: the ratio of
A No e their average life peri9~s.
N I Nl A2 _0.6931 (t1l2 h
-- 0.3679
.I No 2.718 N2 ~ - 0.693'/ (t1l2)1
2.303 log 10 N o
We know tha.t, A As one helium atom is obtained by disintegration of one atom
t N. of radioisotope, the total number of atoms of the radioactive
~""= 2.303 I"oglo, 1'7'6 =.
0113'
mmute -I
isotope which have disintegrated in one hour
5 = 3.01 x 10
20 or 0.0003 x 1024
. d = 0.693 =0.693
HaIf JI'f'epeno - - = 6 . 1 mmutes
. The number of atoms of the radioactive isotope left after one
A 0.113 'hour,
Example 21. You have O.lg atom of a radioactive isotope N = (6.023 X 1024 - 0.000301 X 1024 )
1 X (half life 5 days)~ How many atoms will decay during the
11th day? 6.0227 X 10 24
Solution: Amount of radioactive substance = 0.1 g atom 1 2.303 No
, Using, "" - - 1og-
So,· ' No 0.1 x Avogadro's number t N
0.1 x 6.02 xl 0 23 , 24
1 2.303 1 6.023 x 10
= 6.02 x 10 22
atoms "" - - og - - - - - - 0 : - : -
t 6.0227 X 10 24
6.02 x 1022
Number of atoms after 5 days = ' = 3.01 X 10
22
= 2.303 x 2.1632x 10-5 =4.982xlO-5 hr- I
2
t 112 = 0.693/ (4.982 x 10-5 x 24 x 365) 1.58 years'
, , ,3nIxIO n , 'n'
Number of atoms after 10 days = = 1.505 x 10 Example 23. Calculate the average life of a radioactive
2
substance whose halflife period is 1650 years.
, Let the number of atoms left after 11 days beN.
We know that, Solution: Average life = 1. 44 x t 112
2.303 No = 1.44 x 1650= 2376 years
t A 1oglO N
Example 24. 90 Sr shows ~activity and its half life period
0.693
Given, t 11, A , No = 6.02 x 1022 is 28 years. What is the activity of a sample containing 1 g of
5 90 Sr?
22
11 ,2.303 x5 10 6.02 x 10 Solution: Activity = No. of atoms disintegrating per second
So,
0.693 glo N
22
:::: A x total number of atoms
or log 10 6.02 x 10 11 x 0.693 = 0.6620 0.693
N 2.303 x 5 A=-------
28 x 365 x 24 x 60 x 60
n 23
6.02 x 10 = Antilog 0.6620 = 4.592 6 0?3 X 10
N
Total number of atoms in 1 g of 90Sr
,
=-' -----
90
So, N 6.02 X 10 22 1.3109 X 1022 . . 0.693 6.023 x 10 23
Actlvlty = x ----
4.592 28x 365x 24x 60x 60 90
Atoms decayed during 11 th day = 5.25 X 1012 disintegrations per second
, [1.5050 x 1022 - 1.3109 x 1022 ]
5.25x 1012
0.1941 x 1022 141.89 curie
21
3.7 x 1010
1.941 x 10
. Example 25. A chemist prepares 1.00 g ofpure IJ C. This
Example 22. 109 atoms of an a-active radioisotope are
disintegrating in a sealed container. In one hour, the helium gas , isotope has halflife of21 minutes, decaying by the equation:
c;Uected atSfP is 11.2 cm 3 . Calculate the half life of the radio UC~lIB+Oe
6 5 1
1 I
isotope. (a) What is the rate ofdisintegrationper second (dps) at start?
Solution: Amount of radioactive isotope = 109 atoms, '
c'b) What a~e the activity and specific activity of IJ C at start?
23
or No tOx 6.023 X 10 atoms
(c) How much of this isotope ( 1~ C) is left after 24 hours of its
6.oi3 x 10 24
atoms
prep~ration ?
3
22400 'cm of helium contains == 6.023 x lOr atoms
6 02~ x 10 23
Solution: (a) Applying, - a; = ANO '
11.2 cm 3 of helium will contain = _._-1....._ _ x 11.2 atoms
22400 0.693 1x 6.02 X 10 23
x------
= 3.01 x 1020 atoms 21 x 60 11
= 3x 1019 dps
I
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 165
,
. 3 X 1019 10 .. = -
ActiVity 0.693
- x -W- x. 6023 X 1023
(b) Activity = . 10 (1 curie = 3.7x 10 dps)
tll2 ·At. wt.
3.7 x 10
= 8.108x lOs curie 3.7x 10 10 = 0.693 x _1_. x 6.023 x 1023
{112 226
Sp. activity = 3 x 1019 X 10 3 = 3 X 10 22 dis/ kg s It will give the half life in seconds.]
=8.108xW II curie 17. Assuming that 226 Ra (til 2 == 1.6 X 103 yrs) is in secular
equilibrium with 238 U (t1l2 == 4.5 X 109 yrs) in a certain
.
(c) Applymg,N=No ( -1 •
n J
. t
. [ n= - = 24 x 60 = 68.S7 1 mineral, how many grams of radium will be present in for
. 2 . tll2 21 J every gram of 238 U in this mineral?
. N = 1x GJ 6S.57 = 2.29 X 10-21 ~ (a) 3.Tx 10-7
(c) 3.4 X 10- 7
(b) 3.4 x 107
(d) 3.7 x 107
rUUSTRATfdNf Of OBlECflVE-QU£STiONS [Ans. (c)]
NI 22~a _ tll2 226Ra
13. The time of decay for the nuclear reaction is given by [Hint:
N 2 238U - t 112 238 U
t = 5t1l2 . The relation between mean life 1: and time of decay
w/2261.6xHi3
't' is given by: ~ = 3.4 x 10-7 g]
. 1 1/ 238 4.5 x 109 '
(a) 21: In 2 (b) 51: In 2 (c) 21:4 In 2 (d) 4 In 2
1: 18. A certain radioactive isotope decay has a-emission,
AIX~ A I -4 y
[Ans. (b)] ZI .. ZI-2
[Hint: t = 5t ll2
half life of X is 10' days. If 1 mol of X is taken initially in a
In 2
t=5x- sealed container, then what volume of helium will be
A collected at STP after 20 days?
t=51:ln2r (a) 22.4 L (b) 11.2 L (c) 16.8 L (d) 33.6 L
14. The activity of a sample of radioactive element 100 A is 6.02 [Ans. (c)]
curie. Its decay constant is 3.7 x 104 S-I. The initial mass of [Hint: After 20 days 0.75 mol helium. will be formed.
the sample will be: :. Volume of helium at STP = 0.75 x 22.4 .
(a) 10- 14 g (b) 10-6 g (c) 10- 15 g . (d) 10-3 g ==16.8L]
[Ans. (c)]
[Hint: Activity = A x_w_ x 6.023 X 1023 3.13 ARTIFICIAL TRANSMUTATION
At. wt.
Transmutation is defined as the conversion of one element
6.02 x 3.7 x 1010 = 3.7 X 104 x ~ x 6.023 X 1023 into another or one type of atom into another. When this
100
15 conversion is achieved by artificial means, it is termed ··as
W=IO- g]
artificial transmutation. .
15. A fr<;:shly prepared radio medicine has half life 2 hours. Its The conversion of elements into one. another has been -the
activity is 64 times the permissible safe value. The minimum dream of the human race for many centuries. In the middle ages,
time after which it would be possible to treat the patients with it was popular under the name of ' Alchemy'. Alchemists were
the medicine is:
unsuccessful in this attempt as they were having .very little
(a) 3hrs (b) 9 hrs (c) 24 hrs (d) 12 hrs knowledge about the structure of atom. With the background of
[Ans. (d)] the clear picture of the structure of the atom, modem scientists
Hint: N=No(~r have realised that to convert one element into another, the
nucleus should be attacked and altered.
The first indication that a stable nucleus could be disrupted
was given by Rutherford in 1.919: He observed that when
nitrogen was bombarded with high speed a.-particles from 214 Po,
protons were emitted. Thus, nitrogen was changed into an isotope
n = 6 half lives of oxygen .
.. time=2x6=12hrs]
16. . .One gram of 226 Ra has an activity of nearly 1 Ci. The half life
Later on, Rutherford .and Chadwick showed that many other
of 226 Ra is: -
elements from boron to potassium with the excepticlr of carbon
(a) 1582 yrs (b) 12.5 hrs and oxygen - could be transmuted by bombardment with
(c) 140 days (d) 4.5 x 109 yrs a-particles. However with heavier elements, there was only
fAns. (a)] scattering of a-particles as these suffered a force of repulsion. It
fRint: Use the following relation for calculation of activity: was, thus, concluded that to bring transmutation in heavier
166 'I G.R.B. PHYSICALCHEMISTRY FOR COMPETITIONS
elements, the projectiles must have higher, energies than , 3. Often accompanied by release or Accompanied by release or ab- .
a-particles obtained from natural sources. It was suggested by .absorption of tremendous sorption of, relatively small
.Gatnow in 1928 that a proton <l H) would be a much more amount of energy. amount of energy.
effective projectile than an a-particle, but it was not available as a 4.' Rate of reaction is independent Rate of reaction is influenced by
high speed particle. , of external factors such' as tem- external factors.
The charged particles, like alpha particles, protons, deuterorts perature, pressure and catalyst.
can be made much more effective projectiles if they have high
Example 26. Calculate the energy in the reaction
velocity. Out of all the instruments which have been devised for
accelerating projectiles, the one. which has attracted the widest 2 : H + 2 ~n ~ iHe
interest is the cyclotron ofE.O. Lawrence. The projectile can be
, . accelerated to the speed of25,000 miles per second. Given, H 1.00813 amu, n 1.00897 amu and
The discovery of neutron by Chadwick, in 1932, added He 4.00388amu
another projectile for transmutation. The neutron being Solution: Loss of mass in the given nuclear reaction
electrically, neutral can penetrate easily into the atomic nucleus. ::: 2(1.00813+ 1.00897)- 4.00388
Although neutrons; are the most effective and versatile of
projectiles, yet they suffer the objection that they inust be = 0.03032 amu
produced, by transmutation at the time (If use. High speed E'lergy released::: 0.03032x 931 = 28.3 MeV
neutrons are obtained when berylliiim-9 is bombarded with
, a-particles, Types of Nuclear Reactions
~ Be + iHe ---? I~C + ~n (a) Projectile capture reactions: The bombarding particle
is absorbed with or without the emission ofy-radiations.
and slow neutrons are obtained by bombarding lithium-7 with 2~U + ~n ---? 2~iu + y
protons. tI Al + ~n ---? r~Al + y
~Li+'lH ---? lBe+ ~n (b) Particle-particle reactions: Majority of nuclear
In general, for the transmutation of lighter elements, charged reactions come under this category. In addition to the product
particles like alpha particles, protons, deuterons are used while nucleu&;.an elementary particle is also emitted.
for heavier elements, neutrons are used. 23N
II a + IIH,---? 12 23M'g + on
I
terrible explosion due to release of enonnous amount of energy. percentage of 235 U in the sample is increased. The chain reaction
The chain reaction is shown in Fig. 3.7. , can be carried out under two conditions: (a) uncontrolled' (atom,
bomb) and (b) controlled (nuclear reactors).
Nuclear fuels: Nuclear fuels are of two types:
(i) Fissile materials: These, on bombardment with slow
neutrons, directly produce a chain reaction leading to release of
energy. Three fissile materials are in use at present. These are
f-----n 235 U, 239 Pu and 233 U. 235 U is obtained from natural sources
while 239 Pu and 233 U are obtained by artificial transmutation.
(ii) Fertile materials: A fertile material is one which by
itself is non-fissile in nature, can be converted into a fissile
material by reaction with neutrons. 238 U and 232 Th are fertile
materials. 238 U is converted into 239 Pu by the following nuclear
reaction:
238 U + In - - t 239U*~ 239Np*~ 239Pu
92 0 92 (23 min) 93 (2.3 days) 94
Before
The chain reaction is seif-propagating if theva.lue of explosion
multiplication factor is more than I.
Multiplication factor, ~
No. of neutrons produced in one step
K;::-------------
No. of neutrons produced in preceding step
At the time
The value of K is 2.5 for 235 U and 0.5 for 238 U. This shows of explosion
that if all other factors ate ignored, natural uranium which is a,
mixture of three isotopes CZ38 U = 99.29%, 235 U =0.7%,
234 U = 0.0006%) is not suitable for a chain reaction. The (a)
following two factors hinder the self-propagation of a chain Subcritical
reaction: 235U
Subcritical
(i) Leakage of neutrons from the system.
(ii) Presence of non-fissionable material.
"lithe system IS such that loss of neutrons is more than theIr ·-1- l
' 235 U'
TNT explosive
(0)
the system can be reduced by suitable choice of size and shape of Fig. 3.8 (a), (b) a'nd (c) various designs used in the assembly
the fissionable material. The second source of loss of neutrons is of atom bomb. (The atom bomb is made in two or more
due to absorption of neutrons by non-fissionable material. It may pieces of the fissile material each smaller than the critical
be reduced by careful purification of natural uranium, i. e.,natural size. The moment these pieces are forced together, the
uranium is submitted to the process of enrichment by which the bomb explodes with terrific violence).
•
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 169
2. To produce a strong beam of neutrons: These neutrons called thermonuclear reactions. Fusion reactions are highly
are used lor making various isotopes which do not occur in .exothermic'in nature because loss of mass occurs when heavier
nature. For example; i~p and ~~Co are produced from the nuclei is formed from the two lighter nuclei. To initiate a fusion
following nuclear reactiops: reaction is difficult, but once it is started, its continuity is
maintained due to huge release of energy. Some examples of the
52 Te + In
130
0 --1 131 + °e
531 -I fusion reactions are given below: .
31 P , 32p tH+ tH--1 iHe+24.9MeV
15 + on --1 15
32S+ 'n 32p+ IH
iH+ ?H--1 iHe + 2 hn + 11.0 MeV
16 0 --1 15 I l H+ fH--1 iHe + 20.0 MeV
59Co+'n
27 0 --1 ~Co tH+ iH--> iHe+ hn + 17.8 MeV
The non-radioactive isotope is taken iil aluminium capsule jLi + ~H--1 2 iHe + 17.7 MeV
which is placed inside the aluminium balL The ball is rolled into Hydrogen bomb is based on fusion reactions. Energy released
the reactor'where it is bombarded by neutrons slowed down by is so enormous that it is about 1000 times that of anatomic bomb.
paraffin wax. The bombardment is continued for required period, In hydrogen bomb, a mixture of deuterium oxide (D 20) and
which varies from element to dement. tritium oxide (T2 0) is enclosed in a space surrounding an
(c) Power plant (to generate electricity): The heat produced . ordinary atomic bomb. The temperature produced by the .
is utilised in generating steam which runs the steam turbines. The explosion of theatomiCoomb iriitiafestherusionreactlon--
electric generator is connected to the turbirie. The electric power
is obtainedfrorri the generatpr. The atomic reactor when used for
f t
between Hand H releasing huge amount of energy. The first
hydrogen bomb was exploded in 1952. So far, it has not been
.production ofelectricity is termed power plant. possible to bring about fusion under controlled conditions.
The first nuclear reactor was assembled by Fermi and his It is believed that the high temperature of stars including the
co-workers at the University of Chicago in the United States of sun is due to fusion reactions. Bethe and Weizsaeker, in 1939,
America, in 1942. In India, the first nuclear reactor was put into proposed that a carbon-nitrogen cycle. is responsible for the
operation at Trombay (Mumbai), in 1956. production of solar energy in which hydrogen is converted into
helium. The cycle is:
I~C+ lH-->I~N+y
13 N --1 13 C + +10 e
7 6
I~C+ lH-->ljN+y
I~N+ ~H-->I~O+y
I50--> 15 N + De
8 7 +1
Condenser 15 N +
7
IH --1 126 C+ 4He+y
I. 2
1 4 0 .
or 4 IH--> 2He+2+le+24.7MeV
I~ C acts as a kind of nuclear catalyst.
E. Saltpeter, in 1953, proposed· a proton-proton chain
reaCtion:
IH IH
1 + 1 -->1
2H + +Ie+y
0
92 U+ I2H~ 238Np+i
Nuclear Fusion '
0 n,
Nuclear Fission 238 93
(i) This process oCcurs' in This process occurs' in lighter
Elements 93 and 94 were produced using neutrons (obtained
heavy nuclei. nuclei.
during fission) instead of accelerated positive nuclei. Neutron
Oi) The heavy nucleus splits The lighter nuclei fuse together to capture by 238U followed by f)-emission gives isotopes with mass
into lighter nuclei of form a heavy nucleus. number 239.
comparable masses,
(iii) The binding energy per The binding energy per nucleon ~~U+ ~n~ 2~U~ 23~Np~ 23~pu
nucleon increases. increases.
2~Pu kana-emitter with half life of2.4 x 104 years.
(iv) This reaction occurs at This occurs at a very high'
, ordinary temperature, temperature. Americium is formed in a similar way.
(v) The energy liberated in one The energy liberated in one fusion is /- 239 P (n, y) 240 P (n, y) 241 Pu -II 241 Am
94 U ~ 94 U ~ 94' ~ 95
fission is about 200 MeV. about 24 MeV.
(vi) This can be controlled. This cannot be controlled. As Z increases, the efficiency of nuclear reactions with
neutron bombardment falls sharply. Instead, nuclides in the
(vii) Products of fission are Products of fusion are usually Z = 95 to 99 range are bombarded with beams of helium nuclei
usually unstable stable and non-radioactive in
accelerated in the cyclotron to form nuclides with atomt_~'_c,~__ ~~
radioactive in nature. nature.
numbers 96 to 10 1.
(viii) Percentage efficiency is Percentage efficiency is high.
4He~ 10 n
less. % efficiency 94 Pu +
239 2
242Cm+
96
% efficiency =~x 100=0.38
= 200 x 100= 0.09 5x 931 2~~Am + iHe ~ 2~~Bk + 2~n
236x 931 [rH + ~ -t iHe + ~n
+ 17.8 MeV} 2~~ Cm + iHe ~ 2~Cf + ~n
(ix) The links of fission The links of fusion reactions are,
reactions are neutrons. protons.
2~Cf+ iHe~ fgciFm+2~n
249 Cf 18 263 . I .
+ 80 ----;I06Unh+40n
98
21. A nuclear.reaction of 2t~ U with a neutron produces ~~Kr and
208
82
Pb + 58F
26 e
265 I
----; 108 Uno + on two neutrons. Other element produced in this reaction is:
(a) l~iTe (b) l~CS .(c) l~~Ba . (d) l~Ba
The elements up to 100 (fermium) undergo radioactive decay (VITEEE 2007)
mainly by emitting a.-particles or ~-particles. The elements [Ans. (d)]
become increasingly unstable as the atomjc number increases and
nobelium has a half life of only t:hTee seconds. With these heavy 235 U
36Kr + 56Ba + 2 ~n]
.
[Hint: + Ion ---+ 90
92
144
elements, spontaneous nuclear fission becomes the most 22. The product P of the nuclear. reaction
important method of decay. 252Cf could become a valuable 235U I P + 36Kr
92 1·
92 + on ~ + 3(on)lS;
neutron source.
The IUPAC names for the elements Z> 100 have been (a) I~JSr (b) I~JLa (c) l~~Ba (d) I~JCS
given below: [JEE (WB) 2008J
Unu Uns [Ans. (c)]
10 1 Unnilunium 107 Unnilseptium
[Hint: Let symbol of element is 1£P.
102 Unnilbium Unb 108 Unniloctium Uno
92=Z+ 36
103 Unniltrium Unt 109 Unnilennium Une
Z=56
104 Unnilquadium Unq 110 Ununnilium Uun 235 + 1 M + 92 + 3
105 Unnilpentium Unp III Unuriunium . Uuu'--
M= 141
106 Unnilhexium Unh 112 Ununbium Uub Thus, the element P will be IfJ Sa]
Elements with an even number of protons in the nucleus are
usually more stable than their neighbours with odd atomic 3.18· APPLICATIONS OF RADIOACTIVITY
numbers, i. e., they are less likely to decay. Also nuclei with both
(8) Use ofy-rays: y-rays are used for dhiinfecting food grains
an even number of protons and an evyn number of neutrons are
and for preserving foodstuffs. Onions, potatoes, fruits and fish,
more likely to be stable. A nucleus is more stable than average if
etc., when irradiated with y-rays, can be preserved for long,
the numbers of neutrons or protons are 2, 8, 20, 28, 50, 82 or 126.
periods. High yielding disease resistant varieties of wheat, rice,
These are called 'magic numbers'and can be explained by the
groundnut, jute, etc., can be developed by the application of
~hell ~tructure of the nucleus. This theory also requires the
nuclear radiations. The y-radiations are used in the treatment of
mclUSIOn of numbers 114, 164 and 184 in the series of magic
cancer. The y-radiations emitted by cobalt-60 can burn cancerous
numbers. The stability is particularly high if number of Rrotons
cells. y-radiations are used to sterilize medical instruments like
and the number of neutrons are magic numbers. Thus, 2 8~ Pb is
syringes, blood transfusion sets, etc. These radiations make the
very stable with 82 protons and (208 82) 126 neutrons. This
rubber and plastics objects heat resistant.
suggests that nuc1idesas Uuq (Z = 114, A = 278), Uuq (Z = 114,
(b) The age of the earth: The age of the earth has been
A ~ 298) ~d Ubh (Z = 126, A 310) might be stable enough to
eXist. ConSiderable efforts are being made to produce elements esti.mat.ed by uranium dating technique. The uranium ore (rock)
which IS found in nature is associated with non-radioactive lead
114 and 126 but the present techniques have so far only
succeeded in producing unstable isotopes. The elements up to which is believed to be the end product of radioactive
disintegration of uranium. A sample of uranium rock is analysed
Z 112 have been reported so far.
. for 238 U and·)06 Pb contents. From this analysis, let the quantities
~'OF OBJECTIVE QUESTIONS in mole-be N = 238U mole, No 238U mole + 206 Pb mole.
19. The radioactive isotope ~~Co which is used in the treatment of . Applying disintegration equ~tion,
cancer can be made by (n, p) reaction. For this reaction, the if' 2)03 log 10 -;
target l1J.lcleus is:
(a) ~Ni~ (b) i~Co
238U + 206 Pb
(c) ~Ni (d) ~~Co 2.303 log 10 ---::----
IManipal (Med.) 2007j . U
[Ans. (c)] 206Pb]
== 2.303 log 10 1 + - -
[Hint: ~Ni + ~n ---+ ~~Co + :H] [ 238U
0.693
9
2.303 x 4.51 x 10 x 0.00397
"
So, .t= 2.303 x 5760 1og -
0.693 " 0.6
(lJ
0.0412 x 109 0.05945 X 109 years = 2.303 x 5760 x 0.2201
0.693 0.693
Hence, age of the mineral is 5.945 x 107 years. 4213 years
(c) Radio carbon dating: By using the halflife period of (d) Potassium-Argon method: The decay of radioactive
14C, it is possible to determine the age of various objects. In potassium isotope to argon is widely used for dating rocks. The
living material the ratio of 14 C to 12 C remains relatively constant. geologists" are able to date entire rock samples in this way,
When a tissue in an animal or plant dies, 14 C decreases because because potassium-40 is abundant in micas, feldspars and
the intake and utilization of 14C do not occur. Therefore, in the hornblendes. Leakage of Argon is however problem if the rock
dead tissue the ratio of 14C to 12C would decrease, depending on has been exposed to temperature above 125" c."
the age of the tissue. The age of the dead tissue is determined in (e) Rubidium-Strontium method: This method of dating
the following way. A sample of dead tissue is burnt to carbon is used to date ancient igneous and metamorphic terrestrial rocks
dioxide and the carbon dioxide is analysed for the ratio of 14C to as well as lunar samples. It is based on disintegration by beta
12c. From this data, the age of the dead tissue can be determined. decay of 87 Rb to 87 Sr. This method is frequently used to check
Thus: potassium-argon dates, because the strontium daughter element is
~
fI.
2.303 IoglO l/-N o J " not diffused by mild heating like argon.
t N IUJ.IS'reATIDNS OF OBJECTIVE OUIESTltONS
0.693
- - Ioglo - \)
2.303 0 (N 23. A wooden artifact sample gave activity of 32 I)-particles per
tll2 of C 14 t N second while the freshly cut wood gave activity of 64
No =Ratio ofC 14 I C 12 in green plant or atmosphere I)-particles per second in G. M. counter. Calculate the age of
the wooden artifact (t1/2 of 14C 5760 yrs) :
N Ratio of C 14 I C 12 in wood (a) 11520 yrs (b) 5760 yrs
or (c) 2880 yrs (d) 1440 yrs
[Ans. (b)]
No Activity ~f green plant per unit mass
N == Activity of wood per unit mass
[Hint: 0.693 == 2.303 l~glO (No)
tl/2 . \N
Although, the met\1od is suitable to a variety of organic
materials, accuracy depends on the half life to be used, variations 0.693 == 2.303
5760
10glo. (64)
32
in levels of atmospheric carbon-14 and contamination. (The half
life raaio cathi)n was redefined from 5570 ± 30years to 5730 ± 40 tage 5760 yrs 1 . "
years by IUPA.C). The rapid disintegration of carbon-14 24. The analysis of a rock shows thatthe relative number of 206 Pb
generally limits the dating period to approximately 50,000 years. and 238 U atoms is Pb/U == 0.25. If tl/2 of 238 U is 4.5 X}09
Example 28. The m;,Junt of "I: C isotope in a piece of yrs, then the age of the rock will be: .
wood is found to be one-fifth of that present in a 'fresh piece !Jf (a) 2.303 (4.5 x 109 ) log (~)
" 14 0.693 4
wood. Calculate the age ofwood. (Halflife of" C 5577 years)
I
174 .1 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
mounted. A patient table (or couch) is positioned perpendicular thickness of materials, to test the wear and tear inside a car engine
and axial to the gantry so that it is able to travel along that axis. and the effectiveness of various lubricants. Radioactive carbon
Topographic images are produced by using an X-ray source has been used as a tracer in studying mechanisms involved in
and a detector moving in a coupled way relative to the patient. In many reactions "of industrial importance such as alkylation,
CT a thin fan beam of radiation rotates in a circular or spiral polymerisation, catalytic synthesis, etc.
motion "around the patient. Thousands of projected X-ray signals (iv) Analytical studies: Several analytical procedures can
are reconstructed by computer algorithms to produce digital CT be used employing radioisotopes as tracers.
. images, displayed by a high-resolution monitor. In this way the 1. Adsorption and occlusion studies: A small amount of
whole body can· be imaged from head to toe. radioactive isotope is mixed with" an inactive substance and the
activity is studied before and after adsorption. Fall in activity
Radiation Dosage in the Radiotherapy of Cancer
gives the amount of substance adsorbed.
Radiations and the particles emitted by radioactive nuclei are 2. Solubility of sparingly soluble salts: The solubility of
harmful for living organisms. These radiations cause genetic lead sulphate in water may be estimated by mixing a known"
disorders by affecting DNA. amount of radioactive lead with ordinary lead. This is dissolved"
Effect of biological radiations can be measured in terms of the in nitric acid and precipitated as lead sulphate by adding
unit called RAD. sulphuric acid. Insoluble lead sulphate is filtered and the activity
RAD = Radiation absorbed dose of the water.is measured. From this, the amount of PbS0 4 still
I RAD = The radiation which deposits I x 10-2 J of present in water can be estimated.
energy per kilogram of tissue. 3. Ion-exchange technique: Ion exchange process __oL
In order to measure biological destruction by radiation, an separation is readily followed by measuring" activity of
successive fractions eluted from the column.
other unit REM was introduced.
4. Reaction mechanism: By labelling oxygen of the water,
REM = RAD x RBE
mechanism of ester hydrolysis has been studied.
RBE = Relative biological effectiveness
RBE for a-particle = 10 unit ·#0 * ~O
RBE for ~ and y radiation = 1 unit
R-C( +HOH ~ R-~ * +R'OH
OR' OH
RBE for neutron = 5 unit
(ii) In agriculture: The use of radioactive phosphorus 32 p " 5. Study of efficiency of analytical separations: The
in fertilizers has revealed how phosphorus is absorbed by plants. efficiency of analytical procedures may be measured by adding a
This s"tudy has led to an improvement in the preparation of known amount of radioisotope to the sample before analysis
fertilizers. 14C is used to study the kinetics of photosynthesis. begins. After the completion, the activity is again determin~d.
The comparison of activity tells about the efficiency of
(iii) In industry: Radioisotopes are used in industry to
separation.
detect the leakage in underground oil pipelines, gas pipelines and
water pipes. Radioactive isotopes are used to measure the
N=l(~r 4
ordinary CO 2 for a biological tracer experiment. "Ii
order that
10 3 cm 3 of the diluted gas at NTP should have 104 dis/min, how
many !-lCi of radiocarbon-14 are needed to prepare 60 L of the"
." 1
N UllU:,;:,r 0"fd"
ecayed mo 1es = 1- -1 = -3 diluted gas?
4 4
Number ofrnoks of helium formed Solution: 10 cm 3 of the diluted gas at NTP
, a. a. A = 7.098 x 10 years
(a) A (b) N 0 + (d) -+No
i (c) No a. , Example 8., Calculate the mass of C 14 (half life 5720
Solution: Maximum number of nuclei w.ill be present when years) atoms which:give 3.7 x 10 7 disintegrations per second.
Rate of decay::: Rate of formation Solution: Let the mass of 14C atoms be mg.
AN a.
a. , Number of atoms in mg of 14C = m x 6.02 x 1023
"or, N=- 14
A
A = 0.693 == 0.693 = 3.84 X 10- 12 sec-I
Example 5. The half life of 212 Pb is 10.6 hour. It under-
half life 5720 x 365 x 24 x 60 x 60
goes decay to its daughter (unstable) element 212 Bi of half life
dN '
60.5 minute: Calculate the time at which the daughter element We know that, - =A·N
will have maximum activity. dt
i. e. , Rate of disintegration A x no. of atoms
Solution: Apb 0.693 = 1.0896 x 10-3 min-1
10.6 x 60 3.7x 10 7 = 0.693 x m x 6.02 x 1023
5720x 365.::<44x'~Q.}( 60~.~4'"
12
0.693
60.5
11.45 x 10-3 min-I = 3.84 X 1O- X'l1fi (j:02 ~;r023>
i
'.
14
2.303 So, m= 2.24 x 10-4 g
t = - 1o g
ABi
-
max ABi - Apb Apb Example 9. Prove that time required for 99.9% decay of a
radioactive species is almost ten times its half life period.
2.303 1 11.45 x 10-3
, X og----~
2.303 No
(11.45 X 10-3 - 1.0896 X 10-3 ) 1.0896 X 10-3 Solution: ' We know that, t = --log -
A N
227.1 min No 100, N'; (100 - 99t9) =0.1
Example 6. A radioactive isotope is being produced at a · reqUIre
: ' delor 999
constant rate x. Halflife of the radioactive substance is y'. After So, T1me . 0/0/ decay, ,2.303 100
t =- - 1og-
sometime, the number of radioactive nuclei becomes constant,
A 0.1
the value of this constant is ..... . ::: 2.303 x 3
Solution': At the stage of radioactive equilibrium, A'
Rate of formation of nuclide = Rate of decay of nuclide ' . d _ 0.693
Half lifepeno --A-
x=AN
x xy
= Time required for 99.9% decay 2.303 x 3 A
(In 2)/ y In 2 So, ---x--
Ha1flife period A 0.693
• Example 7. 2~~ U by successive radioactive decay
changes to 2~~ Pb. A sample of uranium ore was analysed and
Example 10. Half life of a radioactive substance A is two
found to contain 1.0 g of 238 U a~d 0.1 g of 206 Pb. Assuming that
times the halflife ofanother radioactive substance B. Initially the
, all 206 Pb has ac~mulated due to decay of 238 U, find the age of
number of nuclei of A and Bare N A and' NB respectively. After
the ore (half life of 238 U 4.5 x 10 9 yrs). ' three half lives of 'A', number of nuclei of both become equal.
N
~ Solution: Number of moles of 238 U = I The ratio of~ will be:
238 NB
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 177
1 .1
(a) - (c) - No. of atoms which have disintegrated = 0.75 x 2.68 x 10 18
2 3 = 2.01 X 10
18
Solution: We know that, the amount remaining after n half
lives can be calculated as: Example 14. A certain radioisotope ~ X (Half life =10
iY. Ifl g atom of i X is kept in sealed vessel,
Gr days) de~ays to;
r
N=No
how much helium will accumulate in 20days?
radioactive nucleus for one mean life. Solution: Mass defect (26.9815+ 2.0141)
Solution: Probability for survival =..!!....- = e -.1.1 (24.9858 + 4.0026)
. No O.OOnamu
= 1Gf =i Solution:
'gh f d" .
Wel t 0 ra lOactlve potasslUm =
75000 x 0.012 . 0.35
x-
Decayed moles = 1-114 = 3/4 . 100 100
Moles of 'He' fonned 3 x 3/4 = 9/4 = 0.0315 g
9 .. 0.693 X Weight ber
Volume of , He' at STP 22.4 x A cttVlty = x A'
yogad '
ro s num
4 t1/2 Atomic weight
= 50.4litre Activity ;;:; . 0.693 x 0.0315 x 6.023 x 1023
Example 18. A sample ofpitchblende is found to contain 1.3 x x 365x 24x 60 40
50% uranium and 2.425% of lead. Of this .lead only 93% was' = 4.81 X 105 dpm
Pb 206 isotope. If the disintegration constant is 1.52 x 10- 10 yr- I ,
Example 21. The sun radiates energy at the rate of
how old could be the pitchblende deposits?
4 X 1026 Jsec- l . If the energy of fusion process is 27 MeV,
. 50
Solution: Moles ofU 238 = = 2.1 X 10-
3
calculate the amount of hydrogen that would be consumed per
100x 238 day for the given process.
Moles of Pb 206 ..", 2.425 x 93 = 0.109 x 10-3 4 IH ~ iHe+2 ~e.
100 100 x 206
- - -
- " ~'.
", "'.
180 GH.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
9. Some radioactive elements undergo a and ~-decay in parallel IH ----t ~n + +~ e + neutrino + energy
path. Positron emission and K -electron capture are similar
C.
223Fr+4He , 'because both processes lower the number of proton by one
87 2
KJ unit.
227 Ac
89 .
18.
K,
- 227
90
Th + _I0 e
N umber of a-particles' x' = --''---:::'' ... (i)
4
Overall decay constant K = K 1 + K 2
Number of~-particles can be calculated using the following
K
Fractional yield of Fr = _,_I relation: '
K
Z, - 2x + Y Z2 ... (ii)
Fractional yield of Th 19. There are three natural and one artificial decay series:
K Uranium series (4n + 2)
10. At equilibrium, 238 U ) 2~~Pb
92 . (ga, 6jl)
A----tB~C ... Thorium series (~n)
AA
Amountof'A'
----'---=-=
232
90
Th
(6a, 4/1)
) 208
.82
Pb
Amount of' B' As tl12A Actinium series (4n + 3)
235 U 207
11. If an element undergo~s simultaneous a and ~-decay, then 92 82 Pb
't a'tl)
Artificial series is also called neptunium series:
,A =Aa + AI); 't =- - - (4n+ I)
't a + 'tf\ 237 Np _ _ _~ 2~Bi
93 (7a,
12. a-particles and y-rays have line spectra, but ~-particles have
a continuous spectrum. 20. If both parent and daughter elements belong to actinide
series (89-103) then they will belong to same group, i. e. ,
13. Geiger-Muller counter is used for detecting a, and
third group.
~-particles, cloud chamber is used for detecting radioactive
238 U 4He ----t 234 Th
radiations and for determining their paths, range and 92 2 90
3rdgroup 3rdgroup
energy. In scintillation counter, the particles of radiations a<f\<y
are detected by the flashes of light produced in the 21. ----7) Increasing penetrating power
scintillator. a>f\>y
14. In every nuclear reaction representing transformation of one ----7) Decreasing ionising power
a>f\>y
nucleus to other, the conservation' of charge number, ----7) Decreasing luminosity on ZnS screen
nucleons, energy c.nd linear momentum is followed. '
22. Emission of one 'a' and two 'W particles form an isotope of
15. a-emission takes place when nl p ratio is lower than required
the parent element :
for nuclear stability.
f'A- iHe-2 °e]----t M ;A
, 4 :H----t iHe + 2[+~ e] + energy
a-particle emission shifts the daughter element two positions 23. There are only 81 stable elements having one or more
left in the periodic table. non-radioactive isotopes. ,
24. No stable isotope exists for the elements above 2~~ Bi. Thus,
zMA 42He ----t zM_ 24B •
bismuth is the heaviest stable element.
(Here, A and Bare isodlapheres to each other.) 25. Two elements earlier than bismuth (Tc and Pm) are
16. ~-emission takes place when nIp ratio is higher than the radioactive.
required value for nuclear stability.
26. Isotop~ Use
~ n ~ : H + _~ e + antineutrino + energy 60 Co Cancerous tumour detection and treatment.
, Emission of I1-particles increases the atomic number by one
Detection and treatment of thyroid
hence, the daughter element occupies one position right to disorders.
the parent element. .
59 Fe Anaemia.
f'A L~e)----tz+~B
;/ 32 P Leucaemia and agriculture research.
Here, A andi B are isobars; thus ~-emission is isobaric
24Na 'Location of blood clots and circulatory
transformation. disorders.
17. In artificial radioactive elements, positrons are evolved 74 As Detection of presence of tumours.
'when nIp ratio is lower than the required value for nuclear
90 Y Treatment of joint effusion and arthritis.
stability.
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 181
18 0Used in the study of mechanism of The nucleus bombarded is called target; the particles used
photosynthesis. for bombarding are called projectiles and the particles
Radioactive Brain scan. emitted are called subsidiary particles.
technetium 32. Particle accelerator: Various particle accelerators are
Note: Radioactive isotopes of carbon, chlorine and nitrogen used to give projectiles like protons, deuterons, a-particles
ate also used in the study ofvarious reactions. and other cationic projectiles having sufficiently high kinetic
27. Radiocarbon dating: This method is used to detennine energy to overcome the electrostatic repulsions of the target
age of wood. nuclei. Commonly used particle accelerators are linear
accelerators, cyclotron and synchrotron. Synchrotron is used
1
F\,
2.303 IoglO
--
(N-oI.1 as proton accelerator.
t N .I
33. Reactions of nuclear transfonnation are represented as:
-0.693
---
14
_ 2.303 IoglO - 0 ) (N ~ Be + iHe ----? l~C + ~n or ~Be (an) I~C
tl/ 2 C tage· N
~rNa + :H----? ~~Mg·+ ~n or nNa(pn) ~~Mg
No = 14a 12C in freshly cut wood or in the atmosphere
~i Al + ~n ----? riNa + iHe or ~iAI (na) ?iNa
or activity of freshly cut wood.
34. Artificial radioactivity was first studied by Irene Curie. In
N 14 C ;12 C in the given sample of wood or activity
this process, a stable nucleus is converted to radioactive
of given sample of wood. isotope on bombardment ors1.litableparl~Cle:· R8:dioactive-
28. Uranium dating or t'ock dating: It is used to calculate the isotope produced undergoes artificial decay.
age of a sample of rock and mineral, i. e. , before how many . 27 Al + 4He ----? 30 P + I n
13 2 15 0
years it was separated from the fire ball of earth. . Stab Ie Unstab Ie
30 p 30S'1 +
2.303 I (N 0 \J
F \ , - - - oglO I -
1 _ 15 ----? 14 0
+1 e
(
t1l2 = 2 .55 mm
.)
t \. N .. 35. Nuclear fission is the process in which a heavy nucleus
0.693 2.303 I
- - oglo -
(N 0) breaks up into two smaller nuclei on bombardment with
neutrons. Energy is released in the process of fission along
tl/2 238 U t age N
with freshly prepared neutrons.
=(2~8 + 2;6)
2~U+ ~n~~~u~ :~:::::::~:
No
N W
238
where, W amount of uranium in the sample 144C 90 21on
w = amount of 206Pb in the sample . 55 S + 37 Rb +
29. The force which binds the nucleons together in the nucleus is Mass defect of the reaction is converted to huge amount of
called nuclear force. These forces are short range forces energy.
operating over very small distances (l fermi, 10- 15 rri). Am (Mass defect) = L Masses of reactants L Masses
Nuclear forces are 1021 times stronger than electrostatic of products
forces. Energy released = Amc 2 .
30. Hideki Yukawa of Japan discovered mesons in 1935. If mass defect is I amu then 931.5 MeV energy is released.
Protons and neutrons are held together by their fast mutual 36. Critical mass: It is the minimum mass of fissionable
exchange. material required that will lead to a self~sust<l.ining chain
IH+ _I01l:----?ln
1 0 fission reaction. For 2t~ U, the critical mass is between 1 to
1 0 IH 100 kg.
on + +111: ----? 1
37. The material which directly undergoes fission is tenned as
:H+ g1l:----?:H
1 0 . 1
fissile material such as 235 U, 239 pU and 233 U. The material
on+ 0!J,----? on which can be converted to fissile material is tenned fertile
31. Artificial nuclear transmutation: Conversion of one material such as 2t~ U and 2~t Th.
element to other by bombardment of a stable element with
high speed subatomic particles. The first artificial 38. Breeder reactors not only involve the fission of 2~~ Ubut also·
transmutation was achieved by Rutherford in 1915 when he converts fertile material into fissile material, e. g., 238 U is
bombarded Ij N with a-particles emitted by 2~~ Po. converted to 239 Pu:
IjN+ iHe----? I~O+:H _~e _~
2~~ U + ~n ----? 2~ U ----? 2~ Np ----? 2~ Pu
27A1
13 +1
on 2 7M
----? IH
12 g + 1
182 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS'
39. Nuclear fission is a chain reaction. If it is uncontrolled, 44. Energy ofa star (sun) is due to nuclear fusion; this energy is
explosion occurs as in the atom bomb. Two or more pieces of called stellar energy. .
. fissile material (235 l) or 239 Pu ) having subcritical mass are 45. Hydrogen bomb is much more powerful than atom bomb and
brought. together rapidly by . means of conventional there is no restriction of critical mass in this bomb.
explosion. The subcritical masses combine to be 46. Neutron activation analysis is a teclmique of fmding .the
supercritical and then chain fission starts,. releasing large trace amount of an ;~lement present with the other. The trace
amount of energy. element is activated by bombarding with neutrons. It is a
40. The controlled chain fission reaction takes place.in nuclear . non-destructive method, e. g. , traces of silver present in lead
. reactors., In the~ reactors the energy is used for peaceful paintings can be detected by neutron activation analysis.
purposes. The heat energy produced in the nuclear reactors 47. Spallation reactions: It is similar to fission but differ in
. can be used to generate electricity. A ~ctor consists of: the fact that they are brought about by high energy.
(i) enriched fuel 2~ U (2-3%). - bombarding particles or photons. A number of smaller
(ii) heavy water (D 2 0) or graphite moderator. It slows particles are released along with the product, e.g.,
down the speed of fast moving neutrons.
(iii) control rods made of boron and cadmium. These 2~~ U + ~He ----+6 }H+ 13 ~n + ~iRa
rods absorb some neutrons and thereby control the
rate of nuclear fission. 48•. The isotope ~ H has nIp = 0 and i H has nIp = 2 which is
(iv) liquid alloy of sodium and potassium is used as a maximum.
coolant. .49. Only l~ C haS zero packing fraction. Packing fraction is
41. Nuclear fusion is the process in which two nuclei of light maximum for hydrogen and minimum for iron.
atoms fuse to fonn heavy nuclei with the liberation large .
-amount of energy. - - - .. Isotopic mass':'" Mass number
Packing fraction = x 10 4
rH+ rH----+ ~He + 23x 108 kJ/mol - . Mass number
rH+ iH----+ ~He+ ~n + 17.2x 108 kJ/mol Elements with negative packing fraction are stable because
42. Fusion reactions are thennonuclear reactions which require sOme of their mass is converted to binding energy.
very high temperature (106 K or more). . 50.I! C is produced in upper atmosphere due to bombardment of
43. Hydrogen bomb involves nuclear fusion. cosmic ray neutrons on atmospheric nitrogen.
RADtOAqJWITY AND NUCLEAR TRANSFORMATION 183
Questions
1.. Match the List-I and List-II and pick the correct answer from (c) Charge number is (r) Nuclear fusion
the codes given below: [PMT (Kerala) 20061 conserved
List-I List-II (d) Mass of products formed (s) Nuclear fissiori
(AtomiclMolecular (Corresponding pairs) is less than the mass of
.~ . species) reactants
(A). fSotopes I. 2~~ Ra and 2~~Ac [E] Match the Column-I with Column-II: .
II
(BtlSobars
".,:'.-~~/
2. t~Ar and igK . Column-I Column-II
.~(y:) lsotones 3. ;Hand tH (a) a-rays (P) Radiations, undeviated
in electric field .
(D) Isoster-s. 4. ~~Uand z~Th
(b) Il-rays (q) Produced when
(E) lsodiapheres 5. COz and NzO electrons strike metal
. (a) A-2, B-1, C-4, D-5, E-3 surface
(b) A-2, B-5, C-l, 0--4,E-3 (c) y-rays (r) Highest deflection in
(c) A-3,~lX--':2, D-5, E-4 electromagnetic field~~.~
(d) A-5, B-4, C-l, D-2, E-3 (d) X-rays (s) Nucleus of helium
(e) A-5, B-3, C-l, D-2, E-4 [F] Match the Column-I with Column-II:
2. Matrix Matching Problems (For lIT aspirants): Column-I Column-ll
[A] Match the Column-I with
.,. Column-II: ,. (a) a-emission (P) Mass number changes
Column-I Column-II (b) Il-emission (q) Atomic number and mass
(a) StabUity of nucleus (P) Depends on mass number are affected
number (c) y-emission (r) Atomic number decreases
(b) Density of nucleus (q) Packing fraction (d) \3+ -emission (s) Atomic number increases
(c) Spin angular momentum (r) Binding energy per
of proton nucleon 3. Write th~ complete nuclear"reactions:
(d) Dimensionless quantity (s) Independent of mass (a) ~Be+ iHe ~ I~C + ............. .
number (b) fH ~ ~He + ............ ..
[B] Match the Column-I with Column-II: (c) IjN + iHe~ I~O+ ............. .
Column-I Column-II (d) 2~iu + ~n ~ ~~Sr + Xe + 3 bn
(a) 21 3rd life (p) 63.2% decay (e) 7L' I
3 I+on~ 2 42H
e+·............ .. "
(b) Average life (q) 75% decay
.(f) 2~~ U + .............. ~ 2~iu ~ 2~jNp + ............ ..
(c) 11 A (r) 2 x tl/2
(g) [jN + ~n ~ fH + ............ ..
(d) Ten times of halflife (8) 99.9% decay
(h) ~ Li + .............. ~ ~Be + y - radiations
[Cl Match the nuclear transformations of Column-I with the
particles emitted of Column-II: (i) rH+ .............. ~ iHe+ ~n
Column-I Column-II (j) 27Al
13 + onI ~ 24N II a + ............ ..
(a) 209 . 4H 21 [A
83B1 + 2 e ~ 85 t + ... (P) :H (k) rjAI + iHe~ + .............. IH
235 U
(I)" 92 + on ~ .............. + 137T
1 .
(b) :Be+ iHe~ I~C+ ... (q) iHe 52 e + 97Z
40 r (fIT 2005) .
(c) ~Mg(~n ... ) tiNa (r) I2H (m) ~~Se~ .............. +2}e (HT 2005)
4. Write the particles"emitted from each nuclide in the following
(d) f~Na (fH ...) r6Ne (s) ~n
reactions:
(1)] Match the Column-i with Column-II: (a) 231Th ~ 23l pa 282JAc
90 (i) 91
Column-I Column-II
(b) 217 At ~ 113Bi ~ 209 T1
(a) Binding energy per (P) \3-decay 85 (i) 83 (ii) 81
nucleon increases (c) 239 U ~ 239Np 2~gpu
92 (i) 93.
(b) Mass number is conserved (q) a-decay
(d) 30p~ 30Si
15 (i) 14
184 G.RB. PHYSICAL CHEMISTRY FOR COMPETITIONS
5. Find the atomic number and mass number of the last member 9. To which group of the periodic table does the last member of
in the following series: the following series belong?
-ct -ct -ct -f:\ -f:\
(a)
226Ra
188 Rn RaA RaE RaC (a) 2~ U 23~Np ~ 2~Pu
ct -'f:\ - fl - ct.•
III Group
(b) fA B----+C~D~E -fl -f:\
(b) 140 Cs ~ 140 Ba ~ 140 La
6. Complete the following: 55 56 57
- ct -f:\
I Group
(a) 238 X ~ Y ~ 91Z ct ct
214 13. -fl (e) 2~1Ra 2~~Rn ~ 2~PO
(b) A~B~84C
II Group
7. Write the equations forthe following transformations:
10. Name the process represented below:
(a) :gK (p, d) (b) 'iN(n, p) (e) ~rNa (a, p)
(a) 23i2 U + ~n 1~~Ba + ~Kr + 3 ~n + 200 MeV
(d) ~Be (a, n).
8. . To which radioactive families do the following nuclides
(b) fH + tH iHe + ~n + 17.6 MeV
belong? (c) ~~Cu + iHe + 400 MeV ~ rJCl + 14 iH + 16 ~n
222Rn, 228Ra, 207Pb, 209Bi, 233Pa. (d) I~B + iHe ~ 137N + ~n
~136c++re.
[A~
1. (c) A-3, B-1, C-2, D-5, E-4 4. (a) (i) J3 (ii) a (b) (i) a (ii) a (c) (i) J3 (ii) J3 (d) (i) +~ e
2. [A] (a-p, q, r);(b s);(c s):(d ql 5. (a) Atomic mass 214, Atomic number 83
[Bl (a - q, r); (b p); (c p); (d - :;) (b) Atomic mass M - 8, Atomic number == Z 2
[C] (a s);(b s);(c-p);(d-q) -ct -13
6. (a) 238 X· ~ 234 y ~ 234 Z
[D] (a-p, q, r, s);(b-p, q, r, s);(c-p,q, r, s);(d-p, q, r, s) 92 90 91
[E](a-s);(b-r);(c p);(d p,q) -f:\
[F] (a - p, r)(b - s)(e - q)(d q)
(b)2~i A 2~jB 2i1c
3. (a) ~Be +iHe ~ I~C + ~n; 7. (a) igK + iH~ ?gK+ ~H (b) IjN + ~n ~ l:C + iH
(b) ?H~ ~He+ _~e;
(e) [iNa + iHe ~ f~Mg + iH(d) ~Be + iHe --,) I~C + ~n
(c) )4N+4He~
7 2
17 0+ IR
8 l'
(d) 22iu + ~n ~ ~~Sr + 1~!Xe + 3 ~n; 8. 222Rn belongs to (4n + 2) family, i.e" uranium family.
228 Rabelongs to (4n) family, i.e., thorium family.
( e) 7L' I
3 l+on~ 2 4H o.
2 e+_le, 207 Pb belongs to (4n + 3) family, i.e., actinium family.
(f) 2g~U + ~n ~ 2~U ~ 2gjNp + je; 209 Bi belongs to (4n + 1) family, i. e., neptunium series.
233 Pa belongs to (4n + 1) family, i.e., neptunium series.
(g) liN + ~n ~ I~C + ~H;
9. (a) 2~Pubelongs to actinide series, hence it is present in III
(h) jLi + :H ~Be + y-radiations;
group.
(i) [H+ iH~ iHe + ~n;
(b) 14~8Ce belongs to lanthanide series, hence it is present in III
(j) fIAI + ~n ~ tiNa + iHe; group.
(k) gAl + iHe ~ f~Si + ~H; (c) 21~Po belongs to VI group.
(I) 2~U + ~n ~ 2 ~n + 1~~Te + ~6Zr; ;; 10. (a) Nuclear fission (b) nuclear fusion (c) spallation reaction
(m) ~~Se ~ ~~Kr + 2 _?e (d) artificial radioactivity.
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 185
• RACTICE PROBLEMS.'
1. Half life of 24Na is 14.8 hours. In what period of time will a Rate =
0.693
x--x
W N
sample of this element lose 90% of its ~t:tivity? tl/2 At. wt.
[ADs. 49.17 hour] 3
6.4 x 107 = 0.693 x 28.207 x 10- X 6.023 X 1023
2. A ~-particle emitter has. a half life of 60.6 min. At any instant tll2 238
of time, a sample of this element registers 2408 counts per
tll2 = 7.729 X lOll sec 2.45 X 104 years
second. Calculate the counting rate after 1.5 hours.
[ADs. 860 counts per sec] (ii) Use, 0.693 = 2.303 loglO (N I 0
n. Hydrolysis.of ester was studied by isotopic .Iabelling method. is 32 days. Calculate the time after which the laboratory will
Write down the structures of products 4 and B in the given be safe for use; .
Teaytion: (lIT 2000) [Ans. 192 days] .
o [Iifnt:, No =64N .
, II 18
0.693' 2.303 I No
CH3-C-O-:c-H+ HOH~ A +B oglO -N'
tl/2 t
o 0.693 ,;,,2.303 log 10 [ 64N ]
II 18
32. ,t N
[ADs. (A) CH3- C- OH; (B)CzH s - 0 - H]
12. Arrange the following species in decreasing order of chemical . ,', t = 192 days] c' ,
reactivity and radioactivity: 17. Radium lIas, a half life 1600 years and its daughter elemi;lnl ,
lH, tH, fH radon has a half life 3.82 days. In an enclosure,tbe volume of.'
'radon was found constant for a week. Explain and calculat~
[Ans.Reactivity : H > fH > tH . the ratio of the number of radium and radon nucIe.i..Will the
.. 3H 2H IH]
, Radi oactiVltyi",?j >1 . ratio be constant after 400 years?
13. The half life of 212Pb is 10.6 hours and that of its daughter [Ans. 1528):< 105 ]
element 212 Biis60.5 minutes. Afterhow.. much time will th~ ·}"t~ooi~t; ";~~;;~+~"N'i(Ra)-;,;t1l2(Rn)
daughter element have maximum activity? N 2(Rn) tdRa)
[Ans. 3.78 hours]
NI 1600 x 365
[Hint: A = '{).693 . Ad 0:693 = 0.01145 min- I Nz 3.82
P 10.6 x60 ' 60.5 '
= 1.528 x lOs]
= 0.QQI089 min- 1
18. Calculate the raciius and den~ity of 2:;;2 u.
2.303 I Ad
(A - A ) oglo T:
tmax
.d P P
[ADs. R = 6.8 X 10- 13 cm; d = 2.979 X 10 14 g I ecl
[Hint: R =Ro A 113 = 1.1 X 1O- IS (235)113 =6.788 X 1O- IS m
- 2.303 10 [0.01145 ]
- 0.01145- 0.001089, glO 0.001089 = 6.788 x 10-13 cm
24
222.275810 0.01145 d = WIV = 235 x 1.66 x 10- g I cc
. glo 0.001089
! x 1t x (6.788 x 10- l3
i
= 227.1 min 3
= 3.785 hours] = 2.979 X 10 14 glee]
14. Radioactive element is spread over a room, its half life is 30 19. 2~U decays with emission of a and (3-particles to form
days. Its activity is 50 times the permissible value. After how ultimately 2~iPb. How many a and (3-particles are emitted per
many days will it be safe?
[Ans. 169.30 days] atom of Pb produced?
44. The half life period of l~~Ce is 13.11 days. It is a ~-particle 47. The disintegration rate of a certain radioactive sample at any
instant is 4750 dpm. Five minutes later, the rate becomes 2700
emitter and the average energy of the ~-particle emitted is
dpm. Calculate half life of sample.
0.442 MeV. What is the total energy emitted per second in
watts by to mg of l~JCe? [Ans. tliZ = 6.13 minute]
[Ans. 1.84 watt] 48. One of the hazards of nuclear explosion is the generation of
90Sr and its subsequent incorporation in bones. This nuclide
[Hint: Rate of disintegrations per sec A x No. of atoms has a half life of 28.1 years. Suppose one microgram was
23
0.693 x 6.023 x 10 x om absorbed by a new-born child, how much 90Sr will remain in
13.11 x 24 x 60 x 60 141 his bones after 20 years? (ffr'1995)
[Ails. 0.61 J.l.g]
Total [')-particles emitted = 2.61 x 1013
2.303 1 initial
Total energy emitted = 2.61 x 1013 x 0.442 1.1536 x 1013 MeV [Hint: - - og
A remaining
Energy in erg = (1.1536 x 1013)(1.6 x 10-6 ) o . 2.303 -I 20 ... I I . .
II. = 28.1 Y t = y, ImtJa = J.l.g, remammg =x J.l.g
13
. 1.1536 X 10 x 1.6 X 10-6 1 84 ]
Energy m watt = 7 . watt
10 20 = 2.303 x 28.1 log 1
0.693 x
45. A sample of ~gSr has an activity of 0.5 mq; What is its x 0.61j.Lg] .
specific activity? (t112 of ~gSr = 19.9 years) . 49. It has been estimated that the carbon-14 in the atmosphere is
12 1 responsible for producing 60 atoms of nitrogen-14 and 60
[Ans. 7.4 x 10 dis. 8- ]
electrons every hour for each gram of carbon. We can quote
[Hint: Rate of disintegrations A x No. of atoms this disintegration rate as 60 counts hour- 1 g-l. A sample of
So, No. of atoms sea shell found near a sea shore was found to have a count of 4
7 counts hour- I g-I. Estimate the age of the shell.
0.5 x 3.7X 10 x 19.9 x 365 x 24 x 60 x 60 14 .
(tIl2 for C = 5730 years).
0.693
[Ans. 21000 years (approximately)]
1.675 x 10 16
50. Upon irradiating. californium with neutrons, a scientist
16
Mass =90 x 1.675 X z310 = 2.50 X 10-6 discovered a new nuclide having mass number of 250 and half
6.023 X lO g life of 0.5 hours. Three hours after the irradiation, the
7 observed radioactivity due to the nuclide was 10 dis/min. How
Speel'fiIC actiVIty
.. = 0.5 x 3.7 x 610 .=.
74 X 1012 dIS
.
g -I many atoms of the nuclide were prepared initially?
2.5 x 10-
[Ans. 2.8 x 104]
46. Calculate the Q-value of the reaction;
~Li + ~n ---7 iHe + ~H
Given, ~Li 6.015126 amu, iHe = 4.002604 amu
fH 3.016049 amu, bn = L008665amu
[Ans. +4.7835 MeV]
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 189
=~ OBJECTIVE QUESTioNS
Set-1 : Questions with single correct answer 12. The velocity of a-rays is approximately:
1. Natural radioactivity was discovered by: (a) equal to that of the velocity oflight
(a) Rutherford (b) Becquerel (b) ~th of the velocity of light
(c) Curie (d) Schmidt 10
2. Radioactivity is due to: (c) 10 times more than the velocity of light
(a) stable electronic configuration (d) uncomparable to the velocity oflight
(b) unstable electronic configuration 13. a-rays have ionisation power because they possess:
(c) stable nucleus (a) lesser kinetic energy
(d) unstable nucleus (b) higher kinetic energy
3. Radioactivity is essentially: (c) lesser penetration power
(a) a chemical activity (b) a physical property (d) higher penetration power
(c) a nuclear property . (d) a property of non-metals 14. The radiations from a naturally occurring radioactive
substance as seen after deflection by a magnetic field in one
4. Radioactivity is. generally found in:
direction are:
(a) light nuclei (b) stable nuclei
(a) definitely a-rays (b) definitely ~-rays
(c) heavy nuclei (d) nuclei ofintermeilim\;'rinx;y.r·
- '\e}-both a and ~-rays (d) eithera or ~-rays
5. The activity of radioisotope changes with:
15. Which of the following statements about radioactivity is
(a) temperature (b) pressure
wrong?
(c) chemical environment (d) none of these
(a) It involves outer electrons activity
6. The rays are given offby a radioactive element from:
(b) It is not affected by temperature or pressure
(a) nucleus (b) valence electrons
(c) It is an exothermic process
(c) all the orbits (d) outer orbit
(d) The radioactivity· of an element is not affected by any
7. The alpha particles are: other element compounded by it
(a) high energy electrons 16. The radioactivity of uranium minerals is usually more in
(b) positively charged hydrogen ions comparison to pure uranium, This is due to presence of, .. in
(c) high energy X-ray radiations the mineral.
(d) double positively charged helium nuclei (a) actinium (b) thorium
8. The emission of beta particles is from: (CSSE 1999) (c) radium (d) plutonium
(a) the valence shell of an atom 17. Radioactive disintegration differs from a chemical change in
(b) the inner shell of an atom being: (MLNR 1991)
(c) the nucleus due to the . nuclear conversion (a) an exothermic change
proton --'i' neutron + electron , (b) a spontaneous process
(d) the nucleus due to the nuclear conversion (c) a nuclear process
neutron --'i' proton + electron (d) an unimolecular first order reaction
9. Identify the nuclear reaction that differs from the rest: 18. The ionising power of a, ~ and y-rays is in the decreasing
(a) Positron emission (b) K-capture order:
(c) ~-decay (d) a-decay (a) a > ~ > y (b) ~ >a > y
(e) y-decay [PET{Kcrala) 20081 (c) y > a > ~ (d) ~ > y >a
[Hint: Only y-emission does not change the nip 19. Which of the following radiations have least effect on both the
.(NeutronlProton, ratio) of the parent element.] photographic plate and zinc sulphide screen?
10. Gamma rays are: (MLNR 1990) (a) a-rays (b) ~-rays
(a) high energy electrons (c) y-rays (d) All have equal effect
(b) low energy electrons 20. y-rays are emitted from a nucleus due to:
(c) high energy electromagnetic waves (a) high nip ratio
(d) high energy positrons (b) excess energy possessed by nucleus after emission of a or
1t . Radium:;; a radioactive substance. It dissolves in dilute H2 SO4 ~-particles
and form!> _ ,;,,'rnpound radium sulphate. The compound is: (c) fission reaction
(a) no longer radiuactive (d) fusion reaction
(b) half as radioactive .:.s [he radium content 2 i. If a radioactive substance is placed in vacuum at IOcr C, its
(c) as radioactive as the radium content rate of disintegration in comparison to one atmospheric
(d) twice as radioactive as the radium content pressure:
190 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
[Hint: 1 millicurie = 3.7 x 107 disintegrations per sec (a) I g of the sample (b) 0.5 g ofthe sample
1.5 millicurie = 5.55 x 107 disintegrations per sec (c) ~.25 g of the sample' (d) 0.01 g of the sample
57. 14C has a half life of 5760 years. 100 mg of the sample
5.55 x 107 containing 14C is reduced to 25 mg in: [PET (Raj.) 2006J
- - - = A = 1.37 xlO- ll ]
No (a) l1S20 years (b) 2880 years
48. One curie of activity is equivalent to: (c) 1440 years (d) 17280 years
(a) 3.7 x 10'7 disintegrations per sec 58. If 3 I 4 quantity of radioactive substance disintegrates in 2
hours, its half life period will be: (BHU 2006)
(b) 3.7 x 1010 disintegrations per sec (a) IS minutes (b) 30 minutes
(c) 3.7 x 10' 4 disintegrations per sec (c) 60 minutes (d) 90 minutes
(d) 3.7 x 103 disintegrations per sec 59. Initial mass ofa radioactive element is 40 g. How many grams
49. A sample ofi2K contains invariably ~Ar. This is becausei2K
of it would be left after 24 years if its half life period is of 8
years?
has tendency to undergo: . [JEE (Orissa) 2006J
(a) a-decay (b) positronium decay (a) 2 (b) S . (c) 10 (d) 20
(c) ~-decay (d) y-decay 60 .. Half life of radium is 1580 years. It remains 1116 after the
years ....... : (VMMC 2007)
50. The value of disintegration constant of a radioactive isotope:
(a) 1S80yrs (b) 3160yrs (c) 4740yrs (d) 6320yrs
(a) decreases with increasing temperature .
61. If hal~life period of radium is 1600 years, its average life
(b) decreases with increasing pressure period will be: .. .. .. ... . ............ . .... -
(c) increases with increasing concentration
(a) 2304 years (b) 4608 years
(d) is independent of temperature, pressure and concentration
(c) 230.4 years (d) 23040 years
51. If the amount of a radioactive substance is increased three
62. A radioactive isotope having a half life of 3 days was received
. times, the number of atoms disintegrating per unit time would:
after 12 days. It was found that there were 3 g of the isotope in
(a) be double
the container. The initial mass ofthe isotope when packed was:
(b) not be change
(a) 48g (b) 36g (c) 24g (d) 12g
(c) be triple
63. Radioactivity of a radioactive element remains I I 10 of the
(d) be .!.rd of the original number of atoms original radioactivity after 2.303 seconds. The half life period
3 is:
52. The half life of a radioactive element depends upon: (a) 2.303 (b) 0.2303 (c) 0.693 (d) 0.0693
(a) the amount of the element ~ 2.303 I ' a
[Hint: 1\.=-- oglO--
(b) the temperature t (a-x)
(c) the pressure
2.303 1 0.693
(d) none of these or A = --loglO - - = 1, T =- - = 0.693]
2.303· 1110 A
53. The decay constant of a radioactive sample is A. The half life
and mean life of the sample are respectively: (MLNR 1990) 64. A freshly prepared radioactive source of half life period 2
(a) 1/A, In 2/A (b) In 2/A, 11 A hours emits radiations. of intensity which is 64 times the
(c) A In 2, II A (d) AI Pn2' 1/A permissible safe level. The minimum time after which it would
54. Average life of a radioactive substance is: be possible to work with this source is:
(a) 0.44 times ofhalflife (b) 2.44 times ofhalflife (a) 6 hours (b) 12 hours
(c) 1.44 times ofhalflife (d) 0.693 times ofhalflife (c) 24 hours (d) 48 hours
55. Radium has atomic mass 226 and half life of 1600 years. The 65. A radio isotope has a half life of 10 days. If today there is 125
number of disintegrations per second per gram are: g of it left, what was its mass 40 days earlier? .
. . . (EAMCET 1991)
(BHU 1990)
(a) 600 g (b) 1000 g (c) 1250 g . (d) 2000 g
(a) 4.8 x 10'0 (b) 3.7 x 108
66. The half life period of four isotopes is given below:
(c) ,9.2 x106 (d) 3.7 x 10'0 (i) 7.6 years (ii) 4000 years
[Hint:
. No. of disintegrations per sec =A (iii) 6000 yeal'S (iv) 3.2 x lOs years
Total no. of atoms in one gram ofRa Which of the above isotopes is m~st stable?
0.693 (a) (iv) (b) (iii) (c) '(ii) (d) (i)
1600 x 365 x 24 x 60 x 60 67. The first indication that a stable nucleus can be broken down
or Ne ')f disintegrations per sec was afforded by:
0.693 x 6.023 x 1023 (a) Rutherford (b) Madam Curie
= 1600 x 365 x 24 x 60 x 60 x 226 ] (c) Soddy (d) Schmidt
68. The .first stable isotope which was transmuted by artificial
56. A radioactive sample has a half life 1500 years. A sealed tube
means was:
containing I g of the sample will contain after 3000 years:
(MLNR 1994) (a) l~O (b) IjN (c) l~C (d)' ~Be
192 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
69. The instability of a nucleus is due to: (AIIMS 1999) 79. A positron is emitted from ~fNa. The ratio of the atomic mass
(a) high, proton: electron ratio and atomic number of the resulting nuclide is: (lIT 2007)
(b) high, proton: neutron ratio (a) 22110 (b) 22/11 (c) 23110 (d) 23/12
(c) low, proton: electron ratio [Hint: : H ~ ~n + +~ e
(d) low, proton: neutron ratio Positron
70. When ;;Al is bombarded with a-particles, a radioactive On positron emission, proton is converted to neutron, therefore,
isotope of phosphorus i~Pwith the emission of ... is formed. atomic number decreases by one unit but atomic mass remains
[CET (Gujarat) 20061 constant.
(a) neutrons (b) protons n . 23]
: rat1o·=~
(c) positrons (d) electrons p 10
71. Nuclear reaction accompanied with emission of neutron(s) is: 80. Hydrogen bomb is based on the principle of: (AIEEE 2005)
[PMT (MP) 1991) (a) nuclear fission (b) natural radioactivity
(a) i;Al + iHe ~ ~~P + ~n (c) nuclear fusion (d) artificial radioactivity
81. In nuclear reactors, the speed of neutrons is slowed down by:
(b) I~e + iH ~ I~N
(a) heavy water (b) ordinary water
(c) ;~P~ ?SSi + re (c) zinc rods (d) molten caustic soda
82. Which of the following is not a fissile material?
(d) 2~~Am + iHe ~ 2:iBk + ?e
(a) 235U (b}.238 U
72. Which of the following transformations is not correct?
(c) 233U (d) 239Pu
( a) 75A 4H 78B
33 s + 2 e ~ 35 r + Ion
83. Which one of the following statements is wrong?
(b) ~Li + iH ~ ~Be+ ~n (a) An atom bomb is based on nuclear fission
(c) iiSc + ~n ~ i~ea + ~n (b) In atomic reactor, the chain reaction is carried out under
control
(d) 2~Bi + ;H ~ 2~~PO + ~n (c) Fission reactions are the sources of sun's energy
73. The reaction, 2~iu + ~'1z ~ 1~~Ba + ~~Kr + 3 ~n represents: (d) Hydrogen bomb is always associated with atomic bomb
(a) artificial radioactivity 84. The fuel in atomic pile is:
(b) nuclear fission (a) carbon (b) sodium
(c) nuclear fusion (c) petroleum (d) uranium
(d) none of these 85. Large energy released in atomic bomb explosion is mainly due
74. I~e in upper atmosphere is generated by the nuclear reaction: to:
WET (MP) 19931 (a) conversion of heavier to lighter atoms
(a) IjN + iH~ lie + +~e+ iH (b) products having lesser mass than initial substance
(c) release of neutrons
(b) IjN ~ lie + +~e (d) release of electrons
(c) IjN+~n~l~e+lH 80. One gram of mass is equal to:
(d) IjN+ lH ~ I~e + iHe . (a) 5 x 1010 erg (b) 9 x 1020 erg
75. In the transformation of 2~~ U to 2~i U, if one emission is an (c) 7 x 105 erg (d) 11 x I{p erg
a-particle, what should be the other emission(s)?
87. If the energy released by burning 1 g of carbon is 3 x lOll erg,
.' (AIEEE 2(06)
then the amount of energy released by converting I g of
(a) two B- (b) two B- and one B+ carbon completely to nuclear energy would be equivalent to
(c) oneB- andoney energy produced by burning ...... g of carbon.
[Hint: 2~ U ~ 2~iu + iHe + 2_~ e] (a) 106 (b) 108
(c) 9 X 1020 (d) 3 x 1010
76. The reaction, ; H + fH ~ ~He + ~n is called:
. (CPMT 1')90) 88. Liquid sodium is used in nuclear reactors. Its function is:
(a) fusion (b) fission (a) to collect the reaction products
(c) endothermic reaction (d) spontaneous reaction (b) to act as heat exchanger
77. When the nucleus of uranium is bombarded with neutrons, it (c) to absorb the neutrons in order to control the chain'
breaks up into two nuclei of nearly equal mass. This process is reaction
called: (d) to act as moderator to slow down the neutrons
(a) nuclear fission (b) nuclear fusion 89. A sample of rock from moon contains equal number of atoms
(c) phYSIcal change (d) artificial radioactivity of uranium and lead (t1/2 for U = 4.5 X 109 years). The age of
the rock would be: IlJGET Manipal (Medical) 20061
78. Which one of the following is an artificial fuel for nuclear 9
reactors? . (a) 9.0 x 10 years (b) 4.5 x 109 years
(a) 238 U (b) 239Pu (c) 235U (d) 232 T h (c) 13.5 x 109 years (d) 2.25 x 109 years
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 193
112. Enrichment of uranium is made by: , 124. Thiosulphate ion (S20~-) on acidification changes to S02
(a) distillation (b) diffusion along with precipitation of sulphur,
(c) evaporation (d) bleaching 35S32S0~- + 2H+ ~ H 20 + S02 + S
113. Let us consider emission of a-particle from uranium nucleus:
which is the correct statement?
92 U235 - 2He
4
~ 90 Th
231
(a) S35 is in sulphur (b) S35 is in S02
e 92 e o e= 90
(c) S35 is in both (d) 8 35 is in none
p= 92 P 2 p=90
125. A radioactive element decays as,
n = 143 n 2 n '"" 141
a decay {-2illP decay
Shortage of two electrons in t"!"iorium is <,iue to: X y ~---,-----) Z
(a) conversion of electron to positron 11/2 ; 2 days
(b) combination with positron to evolve energy which oithe following statements about this decay process is
(c) annihilation incolTect?
(d) absorption in'the nucleus (a) After two hours, less than 10% of the initial X is left
114. Artificial radioactive elements are present in: (b) Maximum amount of Y present at any time before 30 min
(a) s-block (b) p-block (c) d-block (d) j~block is less than 50% of the initial amount of X
115. Half life of 6C 14 , if its A. is 2.13 x 10-4 yrs, is: ' ','l':9) (c) Atomic number of X and Z are same
(a) 3.5 xl04 years (b) 3 x 103 years (d) The mass number of Y is greater than X .
126. Among the following nuclides, the highest tendency to aecay
(c) 2 x 102 years (d) -4 x 103 years
by 03+) emission is: '
116. The 60 Co isotope decays with a half life of 5.3 years. How , (a) 59CU (b) 63 Cu (c) 67 Cu (d) 68 CU
long would it take for 7 i 8 of a sample of 500 mg of 6OCo to
disintegrate? 127; Identify [A] and [B] in the following:
(a) 21.2 years (b) 15.9 years 2i~Ac ~[A] '~RnPEE (WB) '.tOW)
(c) 10.6 years (d) 5.3 years (a) Po, Rn Th, Po (c)Ra, Th (d) Th, Ra
117. Isotope of uranium used in atomic bomb is' [Hint: 2~~Ac 22JoTh 2;~Ral
!PET {MP} 20081 128. f)-particle is emitted in radioactivity by: (AIEEE
('a) 237 U
92 ' (d) 2~U (a) conversion of proton to neutron
118. Which among the following is wrong about isodiapheres? (b) from outennost orbit
(a) They have the same ditference of neutrons and protons or , (c) conversion of neutron to proton
same isotopic number
(d) l3-particle is not emitted
(b) Nuclide and its decay product after a-emission are
129. The nuclear reaction,
isodiapheres
(c) zA M -----7 z _ 2BM - <I + 2He 4 ~~Cu + iHe-~ gCI + 14 :H + 16lP
'A' and' B' are isodiapheres is referred to as: WET (MP) 20lf2i
(d) All are correct (a) spallation reaction (b) fusion reaction
119. At radioactive equilibrium,the ratio of two atoms A and B are (c? fission reaction (d) chain reaction
3.1 x 109 : I, Ifhalflife of 'A' is 2 x 1010 yrs, what is halflife of 130. 226Ra disintegrates at such a rate that after 3160 yrs only one
'B'? fourth of its original amount remains. Half life of 226Ra will
(a) 6.45 yrs (b) 4.65 yrs (c) 5.46 yrs (d) 5.64 yrs be: , WET (MP)
120. The decay constant for an a-decay ofTh 232 is 1. 58 x 10- 10 S,-1 . (a) 790 years (b) 3160years
How many a-decays occur from 1 g sample in 365 days?
(c) 1580 years (d) 6230 years
(a) 2.89x 1019 (b) 1.298 x 1019
131. 2~U nucleus absorbs a neutron and disintegrates into 13~Xe,
(c) 8.219x 1019 (d) None of these
j:Sr and 'x'. What will be the product x?
121. :What percentage of decay takes plac~ in the average tife of a ICBSE {P:\'!T)
substance?
(a) 3-neutrons (b) 2-neutrons
(a) 63.21% (b) 36.79% (c) 90% . (d) 99%
(c) a-particles (d) f)-particles
122. SI unit of radioactive decay is:
(a) curie
,.
(b) rutherford a
132. A radioisotope, tritium H) has half life of 12,3 years. If the
initial amount of tritium is 32 mg; how many milligrams of it
(c) becquerel i (d) all of these
would remain after 49.2 years? (P1VH')
123. The number of neutrons acc'ompanying the formation of 1~~ Xc , (a) 1 mg (b) 2 mg
and j~Sr from the absorPtion of a slow neutron by 2~ilI (c) 4 mg (d) 8 mg
followed by nucl...:ar fission is: I~)99', 133. The radio nuclide 2~6 Th undergoes two successive j3-decays
(a) 0 (b) 2 (c) 1 (d) ). followed by one a-decay. The atomic number and mass
number of the resulting radio nuclide are: (ARn~E 1~J!J3~
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 195
(a) 92, 234 (b) 94, 230 (c) 90, 230 (d) 92, 230 (a) I g ofRa (b) I g ofRaS04
134. The half life of a radioactive isotope is three hours. If the (e) 1 g ofRaBr2 (d) I g of Ra(HP04 )
initial mass of isotope were 256 g, the mass of it remaining ,145. An artificial transmutation was carried out on liN by an 0.-
lUldecayed after 18 hours would be: (AIEEE 2003) particle which resulted in an unstable nuclide and a proton.
(a)4g (b)8g (c)12g (d)16g What is the ratio of the atomic mass to the atomic number of
135. Consider the following nuclear reactions: the unstable nuclide? (SCR~ 2009)
31. The nuclide X undergoes a-decay and another nuclide Y,J3-- (iii) 2iz U + ~n ---? 1~~Ba + j~Kr + 3 ~n
decay. Which of the following statements are correct?
I. The 13- -particles emitted by Y may have widely different (iv)' ~~As + fH---? ~~Mn + 9:H + 12 hn
speeds. (v) ~H + fH ---? ~He + ~n
2. The a-particles emitted by X may have widely different Answers:
speeds. A: Projectile capture
3. Thea-particles emitted by X will have almost same
B: Spallation
speed.
C: Fusion
4. The J3-particles emitted by Y will have the same speed.
D: Projectile capture and particle emission
(a) I and 3 are correct (b) 2 and 3 are correct
E: Fission
(c) :3 and 4 are correct (d) I and 4 are correct
Select the. correct answers according to the given codes:
32. Fill in the blank space with a suitable answer selected from the
Codes: .(i) (ii) (iii) (iv) (v)
list below. Write only the letter (A, B, C, ... ,etc) of the correct
answer in the blanks. (~ A DEB C
Answer {b) DCA E B
(c) ABC D E
(i) 12 C+ IH---? 13 N
61 7
(d) E D C B A
(ii) gAl + :H ---? riMg + iHe
19. (A) Nuclear isomers have same atomic number and same mass another inverse square force which is very powerful,i.e.,
number but with different radioactive properties. .. nuclear force.
(R) U(A) and U(Z) are nuclear isomers. 24. (A) K -shell electron capture is detected by analysing the
20. (A) The emission of a-particles results in the formation of wavelength of X-ray emitted.
isodiapheres of parent element. (R) The wavelength of the X-ray is characteristic of the
(R) Isodiapheres have same isotopic number. daughter element and not the parent element.
. Cl (l. -(3
25. (A) Half life ofa radioactive isotope is the time required to
21. (A) 2t~U (IlIB)~ A ~ B ~ C decrease its mass number by half.
(R) Element B will be of IIA group.
(R) Half life ,of radioactive isotopes is independent of initial
22. (A)f3-particles are deflected more than a-particles in a given
amount of the isotope.
'electric field. .
26. (A) In a nuclear fission process, the total mass of fragments is
(R) Charge on a-particles is larger than on J3-particles.
always greater than the mass of the original nucleus. .
23. (A) The nucleus of gold is stable even though there is a very
. strong coulombic repulsion among the protons. (R) Difference in the mass due to the fission of a heavy
(R) The inverse square coulomb force is exactly balanced by nucleus is converted into energy according to mass-energy
conversion.
• Set-2
1. (b) 2. (b) 3. (a, b,c) 4. (b) 5. (c) 6. (c) 7. (a) S. (a)
9. (c) 10. (b) 11. (b) 12. (c) 13. (b) 14. (d) 15. (b, c, d) 16. (c, d)
17. (b, d) 18. (a, d) 19. Ca, d) 20. (a, b, c) 21. (b) 22. (d) 23. (c) .24. (d)
25. (c) 26. (d) 27. (d) 28. (b) 29. (a) 30. (b) 31. (a) 32. (a)
[~~Z~'~~~t.e~t~i
1. (d) 2. (d) 3. (b) 4. (a) 5. (b) 6. (c) 7. (b) 8. (a)
9. (c) 10. (c) 11. (c) 12. (d) 13. (a) 14. (a) 15. (d) 16. (a)
17. (b) 18. (a) 19. (a) 20. (c) 21. (b) 22. (a) 23. (c) 24. (b)
25. (d) 26. (e)
200 I' , GRS.' PHYSICAL CI-:IEMISTRyFOR COMPETITIONS
=! x ~ x No xE X 1.6 X 10- 19
x Hf Jsec~1 , On dividing the above equations, we get
T 200 ' ,
R2 =1(ll - /2)
'" 8WN oE X10-16 watt per second] RI
T '
2. In nuclear fission, 0.01% mass is converte9 into energy. The
energy released by the fission of 100 kg mass will be:
In (~~) =A(/I' - 12)
(a) 9 x 1(j5 J(b) 9xlOII kJ (c) 9 X 1017 J (d) 9 x lO13kJ
-1 = (I) 12l
---"-'---=--
, '001 A. In (R2 IR I )
lHint: l\m = 100 K-'-, =om kg
100 ' T = (II - 12) ]
E =l\md- =0.01 x (3 x 108 i J , In (R2 IR1)
=? X 10 14 J =9 X lOll kJ] 7. Isodiapheres are the atoms of two elements having same
3. The activitY ofa radioactive substance is Rl at time tl and 112 at values of:
,time t2 (> II ). Its decay constant is A.. Then: (a) p/ n (b)(p - n) (c)(n - p) (d) n x p
(a) Rill =R2/2 , (b)R 2 =Rl i·(12- 11) LHint: Isodiapheres are funned by a-decay
, , MA _ 4He~ M-4
Z-2 B
'
Z 2
(c) R2 =Rl ;(11 - 12) (d) RI R2 = constant
t2 - II (n - p)in 'fA =(M - Z) - Z =(M - 2Z)
M 4 '
'-R 1) e- At2 (n-p)in" Z:2B={(M-4)-(Z-2)} (Z-2)
lHint: ---1 =-'~-- R2 = R/,,(II - (2) ]
RI ~ e-~tl '
= {M - Z -2} - Z + 2
4. The age of a specimen 'I' is related to the daughter/parent rati!) =(M -2Z)
by the equation: :. (n - p) ofisodiapheres are same.]
(a)t=~ln(~) "
(b) 1= -.!. In
'A.
(1 + DP) 8. In a sample of radioactive material, what fraction of the initial
number of active nuclei will remain undisintegrated after half
of a half life of the sample?
,A
=-1 In ( 2 + -P (d) I D)' , (a).! (b) _1_ (c) , (d) Ii-I
4 21i Ii
5., A radioactive substance is being produced at a constant rate of lHint: 0.693 =2.303 log (N 0)
200 nuclei/seC. The decay constant ofthe substance is 1 treC -I. , 1112 'I N
After what time will the number of radioactive nuclei become
2.303 x log 2 _ 2.303 I (No),
100? Initially, there are no nuclei present. . - - - ,- oglo -
11/2 (tI/2/2) N'
(a) 1 sec (b) 2 sec , (crln (2) sec (d) In ~2).sec,
10gIO (2112) =log10 ( :0 )
".int: N =No eAl
100 =200e-)( I
(:J= ~]
RADIOACTIVITY AND NUCLEAR TRANSFORMATION 201
(~r = 1!0
[Hint:
1..2 =0.693 =4.304 x 10- 3 sec-I
161
N =64]
2.303 1
tmax =;---:;- og ~ 16. A sample of radioactive material has mass 'm', decay constant
1\.1 - 1\.2 1\.2 A and molecular mass 'M.lf N A is Avogadro's number, the
2.303 I 3.786 x 10- 3 initial activity of the sample is: .
3.786 x 10- - 4.304 x 10- og 4.304 x 10- 3 (a) Am (b) A m (c) AmN A. (d) ~MeA
. M. M
== _ . 2 ..303 [_ 0.05569]
5.183 x 10- 4 17. A .-adioactive nucleus can decay by two different processes.
247.5 sec] The mean value period for the first process is Z\ .and that for
11. Fusion reaction takes place at high temperature because: the second process is Z2' The effective mean value period for
the two processes is:
(a) atoms are ionised at high temperature
(b) molecules break up at high temperature (a)Zi +Zz (b)Z\ +Zz (C)~Z\Z2 (d) ZI 2
Z
t=Toln(698) ]
595 :0 =(~r .
~=Gr
. 595
15. 80% of the radioactive nuclei present in a sample are found to
remain ul.1decayed after one day. The percentage ofundecayed n=6
nuclei left after two days will be: t=2x6 12 hours]
(a) 64 (b) 20 (c) 46 (d) 80
202 G,R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
[Hint:
X ----7 Y
tl12 := 6.93 X 109 yrs]
=A What is the age of the rock?
nt dt
(a) 2.079 X 1010 years (b) 1.33 x 109 years
~(lA) -A (constant) 1 (c) 1.94 x 1010 years (d) IOld years
dt
a-emission ~ -emission ~ -emission [Hint: No =1+ 7 = 8 (Initial moles ofX )
34. 2~j Bi )A ------7) B )C
N I . (Remaining moles of X)
p-emission u-.emission
We know;
---4)D )E
'E' is.an element of stable nucleus. What is the element 'E'? 0.693 := 2.303 10gr N Q.)
tllz t \N
(a)2~iTI (b) 2i;Pb (c) 2~3Hg (d) 25J: Au
0.693 == 2.303 log ~
35. A radioactive element decays. to one third of its initial amount 6.93 x t 1
in time' t'. What fraction of the element would be left after 0.5
t time? t 2.079 X 10 10 years]
(a'73
I 1
(c)-
3
(d)j1 38. If the relation between time of decay (t) and half life period
(t1l2) is (t 4 t il2 ); the relation between t and mean life (1)
1S:
[Hint:
..
A=--Iog
2.303· ·lfNO\
-I
. t N /
(a) In 2 (b) Tf4 In 2 (c) 4T In 2 (d) 2T In 2
T2
-N = 1.mtIme
. "
t Following questions may have more than one correct options:
No 3
1. Which of the following nuclei are doubly magic?
2.303
A=--loglO 3 ... (i) (a) iHe (b) I~O (c) 2~~Pb (d) 2~~ U
t
After 0.5 t time: 2. Which of the following make up an isotonic triad?
A = 2.303 10 .l( No) ... (ii) (a) 146c, 1680, 157N (b) ~~Ge, ~~As, nGa
.. O.St g N
40 40 40 (d) 233 U 232 Th, 239 p.
(c) i8 Ar, 19 K, 20 Ca 92 , 90 94 U
Equating (i) and (ii) we get
N 1 3. In the decay proceSs:
N =J3] -u -~ -f:l
o A~B~C~D .iViiJ
36. Two radioactive isotopes A and B of atomic mass X and Yare (a) A and Bare isodiapheres (b) A and D are isotopes·
mixed in equal amount by mass. After 20 days, their mass ratio (c) B, C and D are isobars (d) A and Care isotones .
is found to be 1 : 4. Half life of 'A' is 1 day. What will be the 4. A nuclide X undergoes a-decay and another nuclide Y
halflife of B ? undergoes ~-decay. Which of the following· statements are
(a) 1.11 day (b) 0.6237 day correct? .
X y (a) The tl-particles emitted by Y may have widely different
(c)O.ll-day (d) 1.11- day
Y X •speeds
[Hint: Let 1 g of both A and B are taken initially. WA and WB (b)The a-particles emitted by X may have widely different
are the amounts left after 20 days. speeds .
A = 2.303 10 _I (c) The a-particles emitted by X 'will have almost the same
A 20 gW speed
A
, 2.303 I 1 (d) The tl-particles emitted by Y will have the same speed
AE = - - og
20 WB 5. Which among the following nuclides is/are likely to be stable?
A - A = 2.303 10 WE (a) f~P (b) tiMg
(c) Il~In (d) Iljg Cd
A B 20 gW
A 6. Which among the following is/are fissile?
2.303 log 4 = 0.0693 (a) 2395ZU (b) 2~~U (c) 2~pu (d) 2~~pu
20
0.693 7. Select the correct statements among the following:
0.0693 (a) The decay of mass during miclear fusion and nuclear
fission are 0.1 % and 0.23 I % respectively
= 0.693 ~ 0.0693
0.6237 (b) Lesser is the half life, more dangerous is the radioactive
I
element
0.693
tl/2B = 1.11 day] (c) K-electron capture emitsy-rays
0.6237
37. A sample of rock from the moon was found to contain the (d) Nuclear forces are about 1021 times stronger than
elements X and Y in 1:7 ratio by mole. Element X is coulombic forces
radioactive, it decays to Y with half life of 6.93 x 109 years
204 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
8. A radioactive element has atomic number' Z' and mass nU.mber 11 .. The correct starting material and end product of different
'A'. Select the correct statements among th~ following: disintegration series are:
(a) Both 'A' and '2' decrease ina-decay (a) 232Th,208Pb . (b) 235U,206Pb
(b) Both 'A' and 'Z' remain unchanged in y-decay (c) 238U,207Pb (d) 237 Np ,209 B i
(c) 'A' remains unchanged and'Z' decreases by one; the
12. Select the wrong statement(s):
processis called ~+ (positron) decay or K -electron capture
(a) Nuclear isomers contain the same number of protons and
(d) Both 'A' and 'Z' increase in the nuclear isomerism neutrons
9. When nucleus of an electrically. neutral atom undergoes a (b) The decay constant is independent of the amount of the
radioactive decay process, it will remain neutral after the substance taken
. decay if the process is:
(c) 1 curie 3.7 x l(YO dis
(a) an a-decay (b) a ~-decay
(c) a y-decay (d) a K -capture process (d) Actinium series starts with 238U
, 10. Which of the folloWing. is/are characteristics of nuclear 13. Which of the following are synthetic elements? .
forces? (a) Tc (b) Pu (c)Np tal U
(a)These forces operate within small distances of2 x 10-13 em 14. Which of the folloWing nuclides belong to actinhim (U23S)
series? " . . ' .
(b) These forces drop to zero rapidly at a distance greater than (a) 213 pO .(b) 21Spo (c) 222Rn (d) 207Pb
104 x loZ fermi
15. In a nuclear reactor, heayy water is used to:
(c) They follow inverse square 1aw (a) transfer the heat from the reactor
(d) They are stronger than electrostatic forces of attraction (b) provide high speed neutrons for the fission reaction
. (c) reduce the speed of fast moving neutrons
(d) increase the speed of neutrons
'~""
[ ..... ~, '.
[.~~"---------------------II
1~ (8) 2. (5) 3. (1) 4.(7) 5.. (4) 6. (1) 7. (3)
..
206 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
decayed to 2~~Pb, The decay process is: (c) 230 Th (d) 226 Ra __ 222Rn
skeleton, wood: etc. Using carbon dating, materials have been dated 3. Select the incorrect information about 232 Th :
to about 50,000 years with accuracy. (a) It belongs to third group of actinide series
Answer the following questions: (b) 232Th is fissile material
1. 14C exists in atmosphere due to: . (c) It is a fertile material
(a) conversion of 12C to 14C (d) It belongs to 4n series
(b) combustion of fossil fuel
(c) bombardment of atmospheric nitrogen by cosmic ray • Passage 5
neutrons
(d) none ofthe above Geiger-Nuttal proposed that the activity oj a nucleus is inversely
2. A wooden piece is 11520 yrs old. What is the fraction of 14C proportional to its half or average life. Thus, shorter the half life oj
activity left in the piece? an element, greater is its radio(J:ctivity, i.e., greater the number oj
(a)0.12 (b) 0.25 (c) 0.50 (d) 0.75 atoms d.isintegrating per second. Half life and average life are
related with each other.
[Hint: 0.693= 2.303 log OJ\ .(N
tll2 . tage N 0:693 _ 1: X 0 693 or
A - .
0.693 = 2.303 10 (N o'I
5760 11520 g~N / Answer the following questions:
1. The halflife periods of four isotopes are given:
~ =0.25] 1= 6.7 years; II = 8000 years; HI = 5760 years; IV =2,35~x-
No
105 years.
3. In the process of photosynthesis, O2 gas is released from:
Which of these is most stable?
(a) CO2 . (b) H 2 0
(c) both H 2 0 and CO 2 (d) mechanism is not confirmed
WI MIT ~rn ~N
2. Mark the incorrect relation:
4. A piece of wood from an archeological' source shows a 14 C
(a) No = NeAl (b) 't' = 1.44to.5
activity which is 60% of the activity found in fresh wood .. ~.
today. The age of archeological sample will be:
(a) 4246 yrs (b) 4624 yrs ( c) 4628 yrs (d) 6248 yrs (c) N = No ( nn
-) (d) tll2 A In 2
. \2
5. A sample of ancient wooden boat is found to undergo
3. Half life of a radioactive element is 10 years. What percentage
9 dpm g - 1 of 14 C. What is the approximate age of the boat? .
of it will decay in 100 years? .
The rate of disintegration of wood recently cut down is
(a) 0.1% (b) 100% (c) 99.9% (d) 10%
15 dpmg- 1 Of I4 C.
(a) 4246.5 yrs (b) 5384 yrs (c) 4628 yrs (d) 2684 yrs
• Passage 6
• Passage 4 It has been estimated that the total energy radiated by the sun is
3.8 x 1026 J per second. The source oj energy oj stars is a
The mineral monazite is a rich source oj thorium, available in
thermonuclear reaction called nuclear Jusion. Fusion reactions are
large quantity in Kerala. A typical monazite sample contains 9%
not controlled. It is presumed that the. energy oj stars is due to two
Th0 2 and 0.35% U 30 g • 20sPb and 206Pb are the stable end products processes called proton-proton cycle and carbon-nitrogen cycle.
in the radioactive decay series oJ232 Th and 238 U r.espectively. All the Fusion cannot rake place at ordinary temperature. Thus. hydrogen
lead in monazite is oj radiogenic origin. . bomb uses a small fission bomb, which on explosion causes the
The isotopic ratio oj 208 Pb Th was Jound to be 0.104. The temperature to rise very high, about 107 K. We have yet to see how a
. half lives oj Til and U are 1.41 x 1010 years and 4.47 x 109 years hydrogen bomb can be used Jor peaceJul life-sustaining purpose .
., Energy released in the process aJJusion is due to mass deject. It is
respectively.
. also called Q-value.
Answer·. the following questions:
1. The time elapsed since the formation of monazite sample will Q t:,.mc2 , t:.m = mass deject
be:. Answer the fono"!;:~.questions:
(a) 1.34 x 109. years (b) 2.01 x 109 years 1. The bindine; energy per micleon of tH and iHe are l.l MeV
(c) 1.41 x 1010 years (d) 4.47 x 109 years and 7 MeV respectively. If two deuteron nuclei react to form a .
'
[H mt: - - = 2.303 1og -No)
0.693. l' single helium nucleus, then the energy released is:
Ca) 13.9 MeV (b) 26.9 MeV (c) 23.6 MeV (d) '19.2 MeV
tl12 Th tage . N
2. Mass equivalent to the energy 931 MeV is:
'0.693 == 2.303 log (1.104) (a) 6.02 x 10-27 kg (b) 1662 x 10-27 kg
tage
(c) 16.66 x 10-27 kg (d) 16.02 x 10-27 kg
tage 2.01 X 109 years]
3. Fusion reaction takes place at about:
2. . Estimated isotopic ratio of 206 Pb /238 U in the monazite
.(a)3xI02 K (b)3x 103 K
sample will be:
(a) 0.166 (b) 0.266 (c) 0:366 (d) 0.466
• (c) 3 X 104 K (d) 3 x 106 K
208 . G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
4. A star has 1040 deuterons. It produces ~nergy via the process: • Passage 8
r H + rH~ iH+ lH
Radioactive decay follows first order kinetics. The disintegration
rH+ iH~ ~He+ ~n of radioactive elements does not depend on the temperature. Unlike
If the average power radiated by the star is lO16 W, then the chemical first order reactions, . the nuclear reactions are also
deuteron supply of the star is exhausted in a time of the order independent of catalyst. Mean life and half life of nuclear decay
1 0.693'
of: process are 't = A and t!l2 = A . There are. a number of
(a) 106 sec (b) 108 sec (c) l(yzsec (d) lO16 sec
radioactive elements in nature; their abundance is directly
S. In a nuclear reaction,
proportional to half life. Amount remaining after· n half lives of
rH+ rH~ ~He+ ~n radioactive elemeniscan be calculated using the re{ation:
if the masses ofrHand ~He are 2.014741 amu and 3.016977
amu'respeCtively, then the Q-value of the reaction is nearly:
(a) 0.00352 M~V (b) 3.27 MeV
(c) 0.82 MeV (d) 2.45 MeV Answer tbe f{dlowing questions:
1. Which is/are true aboutthe decay constant?
• Passage7 (a) Unit 00.. is time- I .
(b) A is independent of temperature
. Moderator is a material whichis used to slow down the neutrons (c) A depends on initial amount of element taken
produced during l1UclearfISsion. The neutrons from the source are of
(d) Adepends on the nature of radioactive element
high speed and energy. Heavy water or graphite moderators slow
2. Amount of radioactive element (activity) decreases with
down the speed of the neutrons. The energy offast moving neutrons
passage of time as: .
decreases from 2MeV to 0.02535 eV;- it corresponds to the velocity of
(a) linearly (b) exponentially
220 m sec -1. At this velocity, the neutrons are in thermal equilibrium
with the moderator. Such neutrons are called 'thermal neutrons '. (c) parabolically (d) all of these
Thermal neutrons cause forther fission reaction. The essential 3. Half life of 6OCO is 5.3 yrs, the time taken for 99.9% decay
characteristics of moderators are: will be:
(i) its molar mass must be low, (a) 0.53 yrs . (b) 53 yrs
(ii) it should not absorb neutrons, (c) 530 yrs (d) 5300 yrs
(iii) it should undergo elastic collisions with neutrons. 4. Rate of radioactive decay is:
Answer tbe following questions: . (a) independent of time
1. The moderator in a reactor: (b) independent of temperature
(a) absorbs neutrons (c) dependent on catalyst
(b) accelerates neutrons (d) dependent on the amount of element not yet decayed
(c) slows down neutrons S. Select the correct relations:' .
(d) absorbs thermal energy produced in the reactors 0.693 1
(a) tl/2 '= - - (b) 1: = ~
2.. A good moderator should: . A A
[ri~
~1. 1. (b) 2. (c) 3. (a) 4. (a) 5. (b)
~2. 1. (b) 2. (a) 3. (a) 4. (a) 5. (b) 6. (d)
~3. 1. (c) 2. (b) 3. (b) 4. (a) 5. (a)
Pauage4. 1. (b) 2. (c) ·3. (b)
Patage5. . 1. (d) 2. (d) 3. (c)
P~6. 1. (c) 2. (b) 3. (d) 4. (c) 5. (b)
Pas. . 1., 1. (c, d) 2. (d) 3. (d) 4. (b) 5. (a, c)
Pauagt8.. 1. (a, d) 2. (b) 3. (b) 4. (b, d) 5. (a, b, c, d) " ."<
SECTION-I 9. The decay of mass during nuclear fission and fusion are:
(a) 0.1% and 0.231% (b) 0.231% and 0.1%
Straight Objective Type Questions (c) 0.4% and 0.2% (d) 0.3% and 0.3%
This section contains 10 multiple choice questions. Each [Hint: Greater mass is converted to energy in nuclear fusion as
question has 4 choices (a), (b), (c) and (d), out of which only compared to "that of fission.].
ope is.correct. . 10. On large 'scale, tritium is produced by which of the following
X
1. I~ quantity of a radioactive substance decays in 2 hrs, its nuclear reactions? (SCRA 2009)
half life would be: (a) ~Li ~11 -? iHe + ~T
(a) 1 hour (b) 45 minutes
(b) ~ D + ~D -? ~T + : H
(c) 30 minutes (d) 15 minutes
2. Radio carbon dating is done by estimating in a specimen: (c) liN + 611 -? I~C liT
Ie 0) 010
(d) Statement-l is false; statement-2 is true.
a
16. Statement-I: ~-particles are emitted by nucleus.
Because
Statement-2: Following transformation takes place in ~-emission. b 10 e Oi0
, 1on~, IH
ee0 0
0
1 +_I e
17. Statement-I: Nuclide i&Ca is less stable than igca. c
Because
'Statement-2: Nuclides having even number of nucleons are
stable.
d
® 0) 0 01
18. Statement-I: Energy is released in the nuclear fusion of 21. Match the Column-I with Column-II:
hydrogen nuclei to form helium nuclei.
Column-I Column-II
Because
Statement-2: Binding energy per nucleon of helium is greater (a) ;D + 1T --7 iHe + ~n + Energy (p) {3-emission
than hydrogen. (b) ~Be+ iHe~ I~C+ ~n (q) Artificial transmutation '
19. Statement-I: 1~!Ba + e- ~ I~~CS + X-ray 24M
It is an example of K -electron capture.
( c ) 12, g + 4H
2 e~
27S'
14 1 +
1
on (r) Discovery of neutrons
, Because ( d)ln~lH+
o 1-1
0e (s) Hyqrogen bomb
Statement-2: Atomic number of daughter nuclide decreases 22. Match the Column-I with Column-II:
by one unit in K -electron capture.
'Column-I Column-II
[Hint: Nucleus may capture electron from K -shell and the
vacancy is filled by electrons from higher shells; X-ray is released (a)n p++ ... .. (p) Positron emission
in this process.] (b)p+ ~n+ ... .. (q) {3-emission
20. Statement-I: The plot of atomic number (v-axis) versus
(c) X-ray emission (r) K -electron capture'
number of neutrons (x-axis) for stable nuclei shows a
curvature towards x~axis from the line of 45° slope as atomic (d) 4 [\ H] ~ ..... + 2 ~+ + Energy ,(s) q-ernission
number is increased.
Because SEC1"ION..V
Statement-2: Proton-proton electrostatic repulsions begin to Linked Comprehension Type Questions
, overcome attractive forces involving protons and neutrons in Nucleus of an atom resembles with a drop ofliquid. Density of
heavier nuclides. (lIT 2008) nucleus is very high, i.e., 108 tonne I cc or 130 trillion tonnes
[Hint: m -3. This density is about a trillion times greater than that of
t
Number of
water. Density of nuclei of all elements are same, it is
independent of atomic number or atomic mass. However, the
protons radius of nucleus depends on the mass number. Surface
tension of nucleus is also very high, i.e., about 1.24 x 1018
I
-
Number of neutrons
In heavier nuclei, attractive forces between proton-neutron
,overcome proton-proton electrostatic repulsion.]
times, the surface tension of water.
Answer the following questions:
23. The radius of l~ C nucleus is:
(a) 5 x 10- 15 m ' (b) 1.4 x 10- 15 in
SEC1-ION-IV (c) 3.5 X 10- 15 m (d) 6 x 10- 15 m
Matrix-Matching Type Questions
[Hint: r IQ x A Ji3 where A =Mass number
This section contains 2 questions. Each question contains
statements given in two columns which have to be matched. ro = 1.4 x 10- 15 m]
Statements (a, b, c and d) in Column-I have to be matched with 24. Ratio of volume of atom and nucleus is:
statements (p, q. r and s) in Column-II. The answers to these (a) 108 : 1 (b) 1015 : 1 (c) 1013 : I (d)Hj2:1
questions have to be appropriately bubbled as illustrated in the
25. Radius of nucleus is directly proportional to:
following examples:
(a) A2 (b) A l13 (C)[A]3 (d) A
lfthe correct matches are (a-p, s), (b-q, r), (c-p, q) and (d-s),
then correct bubbled 4 x 4 matrix should be as follows:
[,4~ ,
I
1. (c) 2. (c) 3. (b) 4. (b) 5. (b) 6., (a) , 7. (c) 8. (a)
9. (a) 10. (b) 11. (a, b) 12. (a, b) 13. (a; b, c, d) 14. (a, b, c) 15. (a, c, d) 16. (a)
17. (d) 18. (a) 19. (b) 20. (c) 21. (a -s)(b -q, r)(c cq) (d - p)
22. (a -q)(b -p)(c-r)(d -s) 23. (c) 24. (b) 25. (c)
•
4
STATES OF MATTER
4.,.1- INTRODUCTION.
Matter is capable of existing in three physical states: solid, liquid
and gas. Matter is anything which has mass and occupies space.
Any substance can exist in either of three states depending on
temperature and pressure. Liquid and solid states are condensed
• •••
••••
••
••
•
•• •
Cool or
....~r_es_s_ur_;
increase
Heat or
bJ ~
Heat
~
••••
decrease
states as they have much higher densities. Both liquids and gases pressure
are termed as fluids as they have flowing ability. ••• Liquid Solid
The three states of a substance are interconvertible by Gas
variation of temperature and pressure. A liquid state is
intermediate between the gaseous state (complete molecular Fig. 4.1 Schematic representation of states of matter
randomness) and the solid state (orderly arrangement of Some common characteristics of three forms of matter are
molecules). summarised below:
~T'
The relationship between the volume and the pressure of a gas
was studied by Robert Boyle in 1662. He found that increasing t
p
the pressure at constant temperature on a sample of a gas causes
the volume of the gas to decrease proportionately, i. e., if the
pressure is doubled, the volume becomes half and so on. Boyle's 1N ---'-+-
law states that at constant temperature, the volume of a
Fig. 4.2(0)
sample of a gas varies inversely with the pressure.
., ~"
,~ .
jg
log P d. 1.0
Q)
E
::l
(5
log V - - >
Fig.4.2(G)
(ii) Charles'law: It relates the volume and temperature of a
: -200 -100 0 100 200 300 "C
given mass of a gas at constant pressure. o 73 173 273 373 473 573 K
I;xperiments have shown that when 273 mL sample of a gas at Temperature -
O°C is heated to 1°C, its volume increases by 1 mL, i. e., it
become~ 274 mL. At 10°C, the volume increases to 283 mL if the Fig. 4.3
pressure remains constant in both cases. Similarly, when 273 mL This is Charles' law. It can be stated as follows:
sample of gas at O°C is cooled to -1°C, its volume decreases to
The volume of a given amr,unt of a gas at constant
272 mL while at ":'lOoC.the volume decreases to 263 mL if the
pressure varies directly as its absolute temperature.
pressure remains constant.
Thus, all gases expand or contract by the same fraction of their V oc T (if pressure is kept constant)
volumes at O°C per degree change of temperature, i. e. , for each Charles' law can be verified experimentally by plotting the
degree change of temperature, the volume of a sample of a gas values of volumes of a given amount of a gas under respective
changes by the fraction I of its volume at O°e. absolute temperatures at constant pressure. The straight line
. 273 confirms the above statement. ..
Let the volume of a given amount of a gas be Va at O°e. The (iii) Pressure~temperature law: It relates the pressure and
temperature is increased by to C and the new volume becomes VI . a
absolute temperature of a given mass of gas at constant volunie.
Thus, v..t
.
== Va + Va x t == Va (I +
273
_I_J
273
Volume remaining constant, the pressure ofa given mass
of a gas increases or decreases by 1 of its pressure vt ooe
273
or V. == V. (273 +
t a 273
tJ . ... (i) per degree change of temperature:
Po XI
A new temperature scale was introduced known as Kelvin PI =Po + - -
273
scale or ahsolute scale named after the British physicist and
mathematician Lord Kelvin. The lower limit of the scale is or PI =Po (1+_273 t
_)
STATES OF MATTER 215
R =P x V Pressure x Volume
or P = P. (273 + t1 or
I 0 273) T Temp.erature
Force Force
or !l= Po P ressure = = ----,-
T To Area (Length) 2
2.303 log 10
.
(
t.no
~J : : -{M hf
R
g 1 Example 2. A sample of a gas occupies 600 mL at 27°C
and 1 atm. What will be the volume at 127°C if the pressure is
kept constant?
These relations are valid under isothermal conditions for
Solution: VI = 600 mL TI == 27 + 273 = 300 K
density, pressure and number of moles.
If temperature is not constant then the relations of barometric T2 :;:: 127 + 273 = 400 K
dx
RT
M
(~= density == d J
2x
So,
200 Given, d==8.0kgm-3 ; R=8.314JK- 1 mol-I;
2x 1000x400
or T = - 40 + 273 == 233 K
200 x 0.5
and M == 36.5 g mol-I 36.5 x 10-3 kg mol- I
== 8000mL
Substituting the values in the above equation,
Example 5. A sample of a gas occupies a volume of 512
. P 8.0x 8.314 x 233 424.58x 103 Pa
mL at20°C and 74 cm ofHg as pressure. What volume would this
36.5x 10-3
gas occupy at STP?
Solution: Example 8. A certain quantity of a gas occupies 100 mL
Initial conditions Final conditions (SIP) when collected over water at 15°C and 750 mm pressure. It
~ =74 em P2 =76cm occupies 91.9 mL in dry state at NTP Find the aqueous vapour
pressure at l5°e.
1\ e
=20 C=(20+273) 293K, T2 oec= 273K Solution: Let the aqueous vapourpressure be p rnm.
VI 512mL V2 =?
Initial conditions NIP conditions
We know that, PI (dry gas) (750- p)mm P 2 ==760rnm
TI
VI = loomL V2 = 91.9 mL
74 x 512
TI == 15 + 273 == 288 K T2 273 K
293 Applying gas equation,
So,
v. _ 74 x 512x 273 xloo
-C.--_.....:::-C _ _
760x91.9
2 - 293 x 76
288 273
464.5mL 750 p== 760 x 91.9x 288
or
Example 6. 3.7 g of a gas at 25°C occupied the same 100x 273
volume as 0.184 g of hydrogen at 17°C and at the same pressure.
736.8mm
What is the molecular mass of the gas?
Solution: For hydrogen, p = 750- 736.8
w O.l84g; T==17+273=290K; M==2 13.2mm
Example 9. A balloon of diameter 20 m weighs 100 kg.
We know that, PV w RT Calculate its payload if it is filled with helium· at 1.0 atm and
M
27°e. Density of air is 1.2 kg m -3.
0.184 x R x 290 ... (i) (R = 0.082 dm 3 . atm K -I mol -I ) (lIT 1994)
2
For unknown gas, Solution:
w =3.7 g; T 25 + 273 298 K; M=? Volume of balloon == 4 TCr 3 =4 x 22 x (10)3 4190.47m 3
3 3 7
PV = 3.7 x R x 298 ... (ii)
M Mass of the air displaced 4190.47 x 1.2 == 5028.56 kg
Equating both the equations, PV
No. of moles of helium in the balloon
3.7 x R x 298 0.184 x R x 290 RT
M 2 1x 4190.47 X 10 3
== 170344
or M 3.7x 298 x 2 = 41.33 0.082 x 300
0.184 x 290
Mass of helium == 4 x 170.344 x 10 3 g =681.376 kg
Example 7. What is the pressure ofHCl gas at -40°C if its
density is 8.0 kg m-3 ? (R 8.314 J K -I mol-I) Mass of filled balloon == 681.376 + 100 == 781.376 kg
Solution: Equation for ideal gas,
Payload =Mass of air displaced - Mass of filled balloon
PV=~RT
M = 5028.56~ 781.376 4247.184 kg
218 I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Example 10. The density of a gas is 0.259 gel at 400 K Example 13. The density of oxygen is 1.43 g atSTP
and 190 ton: Find its molar mass. Determine the dens tty of oxygen at 17°C and 800 ton:
Solution: 760 torr = 1 atm Solution: Applymg . the "100"ffiula d = -MP
RT
190
So, 190 torr =- atm MP1
760 At STP,
RT,
d [PI = 760 torr; 11 = 273 K; d l 1.43g
We know that, P=-RT
M
At given conditions, d, = MPz
d - RT2
or M=-RT
P [P2 = 800 torr; Tz 290 K;d z ?]
190 dz P? xTI-
Given, d = 0.259 gL- 1 ; P= atm; So, --
760 d1 T2 PI
R = 0.0821 L- atm K- I mol-I; T 400K T
or x~xdl
PI Tz
0.259 x 0.0821 x 400 x 760
M =--------- 34.02 g mol-I _- 800·x273
190 - x 1. 43'
760 290
Example 11. The density of phosphorus vapour at 310°C
=1.417gL- 1
and 775 torr is 2.64 g dm- 3 . What is the molecular formuia of
phosphorus? Example 14. A car tyre has a volume of 10 litre when
d d inflated. The tyre is inflated to a pressure of3 aIm at 17°C with
Solution: We know that, P RT or M=-RT . ail: Due to driving the. temperature of the lyre increases to 47°C.
M P
(a) What would be the pressure at this temperature? (b) How
775 many litres of air measured at 47°C and pressure C?fl atm should
Given, d = 2.64 g dm-3 ; P atm'
760 ' be let out to restore the l:yre to 3 atm at 47°C?
R = 0.0821 dm 3 atm K- 1 mol-I Solution: (a) At constant volume,
. amoecue=--
I I 123.939974 or 3.31 atm
NO.ofPatomsm . '"
31
(b) Pressure to be decreased in tyre
Hence, molecular formula of phosphorus P4
3.31 3.0 0.31 atm
Example 12. What percentage of a sample of nitrogen Let the volume of the gas to be taken out at 1 atmospheric
must be allowed to escape ifits temperature, pressure and volume pressure be V. As the temperature remains constant, i. e., 47°C,
arechangedjrom no°e, 3.0atm and1.65L to 1 IO°C,0.7atm and Boyle's law can be applied to determine V.
1.0L respectively?
lxV O.3lxlO
Solution:' Applying the formula, m (mass of the gas)
PV x M ,under both th'
or v = 3.1 litre
-~- e con d"thons,
RT Example 15. Oxygen is present in a one litre flask at a
. 3.0 x 1.65 x 28 pressure of 7.6x 10- 10 mm of Hg. Calculate the number of
Mass of gas before escapmg= 3.42 g oxygen molecules in theflask at O°e.
0.0821 x 493
PV
. 0.7 x 1.0 x 28 . Solution: n= ... (i)
Mass of gas after escapmg = 0.62 g RT
0.0821 x383
10
Percentage of nitrogen allowed to escape 7.6x 10- 10- 12
P= = atm
760
._ Q62) x 100 81.87
3.42 V = lL, T = 273 K, R 0.0821 L atm K- 1 mol-I
STATES OF MATIER' 219
Pm 3 x 34 V 1/100
[Hint: d - 4.14 g L- I ]
• RT 0.0821 x 300 VB 11200
V
5. Coefficient of volume expansion of a gas is: VB =2']
I 2
(a) 273 (b) 273 9. A bubble of volume VI is at the bottom of a pond at 15°C and
1.5 atrn pressure. When it comes at the surface, it observes a
(c) 2~3 (d) 2~3
[Ans. (a)]
pressure of I atrn at25°C and has volume V2;give (V2) :
. ~
[Hint: According to Charles' law, (DCE 2006)
VI = Vo (1 + _t_)
273
(a) 15.5
[Ans. (d)]
(b) 0.155 (c) 155.0 . (d) 1.55
VI = Vo (1 + at)
[Hint: PI VI = P2V2
TI T2
a = _1_ Coefficient of volume expansion
273 VI PzTl
Here, Vo = Volume at O°C and VI =Volume at t DC] 1.5 x 288
---.1.5]
6. A gas has a vapour density 11.2. The volume occupied by I Ix 298
gram of the gas at STP will be:
(a) 1l.2 L (b) 22.4 L (c) I L (d) 10 L 4.5 DALTON'S LAW OF PARTIAL
[Ans. (c)] PRESSURES
Mass When different gases that do not react chemically with each other
[Hint: Number of moles = - - - -
Molar mass are enclosed in the same container, they intermix rapidly and
exert a definite pressure. Again, each of the gas in the mixture
Mass
exerts its own individual pressure if it is present only in the same
2 x Vapour density container at the same temperature. John Dalton, in 1801,
established the relation between the pressure of the mixture of
2 x 11.2 22.4 gases and individual pressures of the constituent gases. This
relationship is known as Dalton's law of partial pressures. If
Volume of gas = n x 22.4 L states that,
1 At a given temperature, the total pressure exerted by two or
= x 22.4 L = 1 L]
22.4 more non-reacting gases occupying a definite volume is equal to
the sum of'the partial pressures of the component gases.
7. When a gas is heated from 25°C to 50°C at constant pressure
• Mathematically,
of 1 bar, its volume:
(a) increases from Vto 2V P= PA +"PB + Pc + ...
(b) increases from Vto 1.5V when P is the total pressure and p A , P B , Pc, . .. are the partial
(c) increases from V to 1.084V pressures of the component gases J1, B, C, ... respectively. The
(d) increases from Vto 1.8V
pressure that a component gas of the gaseous mixture
[Ans. (c)] would exert if it were only present in the volum~ under
consideration at a given temperature, is the partial pressure of
[Hint: VI = V2 the component.
Tl T2
~=~ Derivation of Dalton's Law
298 323 Let n l and n2 be the no. of moles of two non-reacting gases
323 'A' and 'B' filled in a vessel of volume' V' at t~mperature T.
V2 = V X = 1.084 V ]
298 Total pressure in the vessel 'F'may be calculated as,
8. The molecular weights of two ideal gases A and Bare
PV=(n l +n2)RT ... (i)
respectively 100 and 200. One gram of A occupies V litre of
volume at STP. What is the volume (in litre) occupied by one Individual or partial pressure may be calculated as,
gram of Bat STP? (EAMCET 2006) P AV nlRT ... (ii)
V
(a) - (b) V (c) V 2 (d) 2V PBV = il2RT ... (iii)
2
[Ans. (a)] Adding eqs. (ii) and (iii), we get
[Hint: Under identical cenditions of temperature and pressure: (PA +PB)V=(nl +n2)RT ... (iv)
VA Comparing equations (i) and (iv), we get
VB nB P == PA + PB (Dalton'S expression)
STATES OF MATTER 221
Dividing eq. (ii) by (i), we get This ability of a gas to mix spontaneously and to form a
. homogeneous mixture is known as diffusion. It is due to this
-.....!.....-=X A
P nl + nl
phenomenon that we can readily detect the fragrance of a flower
or a perfume or bad smell of hydrogen sulphide, sulphur dioxide,
PA x A x P chlorine, etc., when these are evolved or used in any work in
where, x A = mole fraction of 'A'. laboratory or in industry.
Similarly, dividing eq. (iii) by (i), we get
Effusion
PB xP
=XB
It is a process in which a gas is allowed to escape under
i.e., Partial pressure of a component
pressure througb a fine orifice or a small aperture made in
Mole fraction x Total pressure
the wall of a closed container. The difference between diffusion
Relationship between Total Pressure and Individual and effusion is that in the former case, the gas spontaneously
Pressure (before Mixing) of the Constituent Gases at streams through a porous partition while in the case of effusion,
Constant Temperature the gas is forced out through a small hole by applying some
At constant temperature, let V; volume of a gas A at a pressure external pressure. However, both the processes are essentially the
PI be mixed with V1 volume of gas B at a pressure Pl' Both these same.
gases do not react chemically. . Instantaneous rate of effusion is directly proportional to the
instantaneous gas pressure and inversely proportional to the
Totalyolume = Vj + V2 square root of molar mass. '
Let the total pressure be P and partial pressures of A and B be dP KP
P A and P B respectively. Applying Boyle's law,
dt JM
P A (VI + V2 ) PI V; ... (i)
and PB (VI + V2 ) P2 Vl ... (ii) _r P2 dP =~ rt dt
Adding eqs. (i) and (ii),
JP1 P JM Jo
PA + PB In(;~ J J!M
or P PIV; + P2 V2 InP 1
Vl +V2
In the laboratory, it is often convenient to collect a gas over
water. When a gas is collected over water, the observed pressure Hence, partial pressure decreases exponentially with time as
of the gas is equal to the sum of the pressure of dry gas and the
pressure of water vapour. . ,
Therefore, the pressure of dry gas
= pressure of moist gas pressure of water vapour 1
=pressure of moist gas aqueous tension p
,
density of gas II rz=lM I
r2
density of hydrogen
density of gasI
density of hydrogen
:::
or
:: =J¥ ~~: =
Theoretical separation factor for single step f'
nl I nz
.2..= t =~= {d; = 1M2
rz Yz V2 Vd; VM I
n'~ z
log _2::: log rn'ln'J
_I_ _
t
M[ nil nz
(iii) Effect of pressure on rate of diffusion: When pressure
is not constant then rate of effusion may be taken proportional to
pressure.
n (M J
- Iog - z -1
- og - -n:i1
) (n{ I
2 Mj , nil n 2
1
roc-- rocP
.JM 210g ( nil n 2
l
J'
~
[Hint: - ---
o,
second to diffuse through the same hole. Calculate the molecular
formula of the compound. (1I(lll~'19V9)
/02 -, IV! gas
I
226 I G.R.B.' PHYSICAL CHEMISTRY FOR COMPETITIONS
~
2 32
4= -.- or 16
Mg~s' lV/gas
or
[Hint:
13. The time taken for effusion of64 mL of.oxygen will be same
as the time taken for' the effusion of which of the following
ga5es under identical conditions?
(a) 64 mL of Hz (bj 100 ofN2 " Derivation of Kinetic Gas Equation
\c)64rl1L of COl '" (d) 45.24 mL ofSO/' On the basis oftne postul(ltes of kinetic theory of gases, it is
[4l.ns .. ' (d)] possible to derive the mathematical expression, commonly
,'!."
1';.
known as kinetic gas equation, i. e. ,
[aint: 102 =
12
'gas PV= - mnc
3
64 ~ . 64
V =~ 32 or V = 45.2~mLl where, P = pressure of the gas, V == volume of the gas, In mass
of a molecule, n number of molecules presbnt in the given
14. Which of the following pairs of gases will have identical rate amount of a gas andc root mean square speed.
of effusion under similar c;onditions? l11eroot me~m square speed (rms speed) may be define}! as the
(a) Diprotium and dideuterium square root qf the mean of squares ohhe individualspeed of all
(b) Carbon dioxide and ethane' the molecules.
(c) Dideuter;um and helium 2 '. 2. ·2, . 2.
CI + C2 +C 3 + .. , + CII
(d) Ethene and ethane . qns spe:ed=
[Ans.«c)] n
[Hint: Dideuteritttn and hC'liumhave same molar'mass,hence
ti1ey\ViH diffuse with.idcnticai rate :under identical conditions,]
15. Two gas bulbs A and B are connected by a tube having a
• 'fcm
stopc6~k. BjJlb A.'hasa volume of 100 mL and contains
hydrogen. After. opening the' gas from 11 to the evacuated
bulbB, the pressure falls down to 40%. Tile voh.l'me(mL) of
B must be: ' [PET (Khala) 2006]
(a) 75 (b) 150 (c) 125 ,(d)2QO .
Before
(e) 250 'collision Ux ·
[Ans. (b)]
A
. [Hi~t: P1V j (A) + P2Vi B) = PR (VI + "-,-+-'----E;-;--'-;-:-+,./
: After -Ux
; 190 x InQ.:+ 0 x Vz = 40(100 + V2 ) I collision'
.)----------
V2 = 250 - 100 = 150 mL 1 ./
:;/- .
J /:
/
4~7KINETIC 'tHEORY OF GASES
,1'" /
/
/
./
STATESOFMATIER 227
~
Consider a certainmass of a gas enclosed in a; cubical vessel of P == 1 mnc-
side'l' cm. Letthe total number of gas mole<;:ules be 'n' ami mass 3 V
of each molecule be 'm'. Let c be the root mean square speed. 1 . ?
Speed can be resolvedinto three components,i. e.;Ux'~y andU z or PV=~ mnc·-
3 .
parallel to the edges of the con.tainer (i.e, ,parallel to thJ:ec. axes x,
yand z ). . . This equation is taIled: kinetic\~as equation; .
C
2
=U2x +U 2 +U 2 For one gram mole of the gas,
'"Y z
n N (Avogadro's number)
· Consider the movement of a single molecule between opposite
.~ 6.02 Xi0 23
faces A and Bparallel to x~axis. When the molecule strikes with
one wall of the container, it bounces back with the same speed m x N =M molecular mass of the gas.
and subsequently strikes the opposite waH. The above kinetic equation can pe written as: .
The momentum of the molecule before collision with · ...··prr 1 c ..
. . r' =- M2
face A =mUx ' 3·
The momentum of the molecule after collision =. mUx .2 3PV
or c =
The change in momentum in one collision =mUx ~ (~ill (;x ) M
The ratio R / N is constant and is known as Boltzmann (i) The root mean square speed: The speed in kinetic gas'
constant. Its numerical vallie isl.~8 x lO-16 erg K'I molecule -I.
equation, PV = 2mnc 2
, is the hypothetical speed possessed by
3
4.8MAXWELL-BOLTZMA,NN DISTRIBU"nON all the gas molecules when the total kinetic energy is equally
OF MOLECULAR SP£EDS distributed amongst them. The total kinetic energy of the n
molecules of the gas is sum of the kinetic energies of the
The gas molecules are moving in all possible directions. They individual molecules.
collide with one another and also with the walls of the container. Total kinetic energy
As a result of collisions, the speed and, direction of the gas
121212 12
molecules are ever changing, i.e., all the molecules in a given = - mCI + - mC 2 + - mC3 + ... + - mc ... (i)
2 2 2 2 11
sample of gas do not have the same speed.
The distribution of gas molecules among different possible Let c be the veloCity possessed by each of the n molecules;
then,
speeds was studied by MaxweU and Boltzmann using the theory
1 7
of probability. The results are mathematically expressed as, total kinetic energy 11 X - mc- ... (ii)
e
--
1I1u
2RT
2
2
u du Equating both the equations,
121? 1212
11 X - mc.
2.
12
- mCI + mc, + mC3 + ... +;- mc"
m J312 _111112
2 2 2 - 2 2
= 4nN [ - - e 2RT u 2 du
2nkT' or
n
. Here, N = Total number of molecules, M = molar mass of gas
. This expression gives the number of molecules (dNu) having or c
speed between u and (tl + du) at temperature (T).
A plot of fraction of molecules in the speed range (u + du ~ Thus, rms speed is defined as the square root of the mean of
1
- ' - - '. \
(dNU .
agamst speedu 'IS: the squares of the speed of all the molecules present in the given
N du) . sample of the gas. The value of c is determined by using the
following expressions:.
" (2Rf (iii) DistIibutign of molecular speed also depends upon the
It is equal to fAT' molecular mass of the gas. At similar temperature a heaviei' gas
molecule has a naITOW distribution of speed than those of lighter
This is related to rms speed by the following relationship: gas molecules.
Most probable speed = {.JI) rms = 0.816 rms
(iv) The fraction of molecules having speeds greater than
minimum goes on increasing with increase in speed. It reaches to
a maximum value and then begins to decrease.
or rms 1.224 most probable speed (v) As long as temperature of the gas is constant, the fraction
The three kinds of molecular speeds are related to each other having a particular speed remains the same inspite of the fact that
as: the molecules change their speeds due to collisions. '
Mostpr6bable speed: Average speed: rms speed The increase in the temperature of the gas increases the
molecular speed. As a result, the most probable speed increases
I2RT. V8RT . l3RT with the increase of temperature and the distribution curve shifts
VM·1tM·. M towards right. The general shape of the curve remains the same
[8' but the maxima of the curve becomes somewhat flat at a higher
= J2: V-;:-13 temperature, i.e., there is a wider distribution of molecular speeds
= 1 : 1.128: 1.224 and the fraction of the molecules having high speeds increases.
However, the fraction of molecules possessing mostprobab~__
rms speed at any temperature to C may be related to its value at
speeds decreases with increase in temperature. ' '
STP as:
/(273+t) ,
. ... (i)
Co ~ 273 '
... (ii)
1 dNu
1 T == (27 + 273) ==300 K
16 2
Ndt
R 8.321 K-1 mol-I
and
Substituting the values in above equation = 48356 em! sec
= 483,56 m! see
c= 3 x 8314:>< 288 473.79 ms-1
0.032 Average speed = ~8RT
--
Example 40. Calculate the root mean square' speed of nM
hydrogen molecule at STP ,
7.57 x 10 3 N 2 . )3RT
Calculate tIle roqt mean square speed and
fn- . [Hi~t: VI '" M
temperature of the gas molecules. If the rati() of most probable
speed to the rootn!ean squarespeed is 0.82, ca!culate)he 'most T2 2T, M 2 = M 12
probable speed of these mole'cules at this temperature. '
(liT t 993) '°2 =
'f h 2.0x 19. The translational kinetic energy of an ideal gas depends only
Solution: Amount 0 t e gas = ' " nlole on its: . , '
6.023 x lO~"
(a) pressure (b) force
Given, V I litre =1O~Jm3; P == 7.57 X10 3 Nm-2 , (c) temperatul'e (d) molar mas.s
R 8.314JK- 1 mol"']. [Ans. (c)]
, ..... . .·PV 3 . '
Applying PV = nRT or T = [Hint: KE 2 RT :. Kinetic energy depends on temperature,]
I1R
20. At what temperature is the rms speed of H2 moleci1les the
10-3 x 7.57x ]0 3
T= ?l = 274.2K same as that of oxygen molecules at 1327°C?
2.0x 10- x 8.314 (a)I73K (b) lOOK (c)400K(d)523K
[Ans. (b)] "
6.023 x I
~DS OF OBJECTIVE QUESTIONS 21. If the temperature of I mole bfa gas is increascd'by 50°C,
ealcuHite the change in kinetic energy of the sy.stem: ".
16. At what temperature is the root mean square speed of N2 gas (DCE 2006 )
(a). 62.32 J (b) 6.235 J (c) 623.5J (d) 6235.0 J
equal to that of propane gas at STP?
[Ans. (c)]
(a) 173.7°C (b) 173.7 K (c) 273 K (d) ~40°C
["'ns. (b)] [Hint: .E= l'RT
2 . .(Kinetic .energyofl
. '. mole
[Hint: v rms (N 2 ) == v rm S<C 3H g )
6.£=3 R(T + 50) ~ RT
2 .. · 2
pRT == ~3R 273 3 . 3 ....
28. 44 -R~50 -x8.3J4x50
2 2
T=173;7K] = 623.55 J]
17. At what temperature is the kinetic energy of a gas molecule 22. At same temperature, calculate the llltio ofiwerage velocity or
half of its value at 327°C? S02 toCH4 : . . (DeE 2006)
(a) 13.soC (b) 150°C (c) 27°C (d) -123°C (a) 2:3 (b) 3:4 (c)l:i (~,;6
IAns. (c)] [Ans. (c)]
b==[~nr3 JX4N
where'r == radius of gas molecule
N == Avogadro's number
(b) Pressure correction: A molecule in the interior of the
gas is attracted by other molecules on all sides. These forces,
4.9 . VAN DER WAALS' EaUATION
thus, are not effective,· as equal and opposite forces cancel each
The gas which conforms to all of the postulates of kinetic theory other. However, a gas molecule which is just going to strike the
or which obeys Boyle's law and Charles' law l~gii\ly for all values waH of the vessel experiences an inward pull due to unbalanced
of temperature and pressure or which strictly follows the general attractive forces. Therefore, it strikes the wall with less
gas equation (PV nRT) is called ideal or perfect gas. Actually momentum and the observed pressure will be less than t~e ideal
no gas is ideal or perfect in nature. Under ordinary conditions, pressure.
only those gases nearly behave as ideal or perfect which have Pideal Pobs + pI
very low boiling points such as nitrogen, hy?rogen, etc. where P' is the pressure correction.
At low pressure and moderately high temperature, the-real
gases approach ideal behaviour (see fig.). Pressure Correction Depends upon Two Factors'
(i) The attractive force exerted on a single molecule about to
Real] atT strike the wall is proportional to the number of molecules per unit
----- Ideal 3
,OM
volume in the bulk of the gas.
\\=.. :Id:e:alll gas
!
Real] at T2
---- Ideal
(ii) The number of molecules striking the wall which is also
t
p
PV l
Real Jat T1
proportional to the number of molecules per unit volume of the
gas. .
~--- Ideal
Both these factors are proportional to .the density of the gas.
L..-.._ _ _ _ _ (T3> T2 >T 1 )
~
, If ~)(3b)
= PYc = 2 7 b = 0.375
RT t
R(~)
, 27Rb, /
Gas .P",(abn)
2.3
,VQlum.e.~
12.8, ' 65 33.2
Fig. 4.10 (b) Isotherms of carbon dioxide according to Ne' 26.9 41.7 44.4
van der'Waals~ equation, c
(c) C()oling by Adiabatic Expansion Involving The extent to which a real gas departs from ideal behaviour is .
Mechanical Work expressed in terms of compressibility factor.
When a gas· is allowed to expand adiabatically against a . Z = Molar volume of real PV",
pressure, it does some external work at the cost of its kinetic Molar volume of ideal gas (VIII) RT
energy, due to which its temperdtur~ falls. This principle is used
in Claude's process for liquefaction of air. The; apparatus is When Z > I, V", > 22.4 L at STP and when Z < 1, Vin < 22.4 L
shown in Fig. 4.11 (c). at STP.
Pure, ·and dry air is compressed to about 200 atmospheric . (i) Z 1for ideal gas. Deviation from the unity indicates extent
pressure and then passed through the tube T. Compressed air of imperfection or non-ideality.
divides itself into two parts at 'A' and a 'portion enters through 'C' (ii) Real. gases have Z"" 1 at low pressure and high
fitted with an airtight piston. There, it expands, pushing .the temperature. In this case, the real gas behaves like ideal gas.
piston outward and performs some external work. . (iii) Z> 1 shows that it is difficult to compress the gas as
compared to ideal gas. It is possible at high pressure. In this case,
'T' repulsive forces dominate.
D (iv) Z < I shows that the gas is easily compressible as
Compressure compared.to ideal gas. It is possible at intermediate pressure. In
this case, attractive forces are dominant.
t . Plots of Compressibility Factor against Pressure
Z>1
t Ideal gas
Z
Fig. 4.11 (c) Claude's apparatus for liquefaction of air (I) At very low pressure, PV RT, i.e., Z "" 1
(ii) At low pressure, PV <RT, Z< 1
The temperature of the gas thus falls. Cooled air then enters Z<1 (iii) At high pressure, PV > RT, i.e.; Z > 1
the chamber at B and cools the incoming air. Thetemperature of
P--
air is also reduceq on expansion due to Joule-Thomson effect.
The process continues until the air liqt\efies. Fig.4.12(a) Variation of compressibility factor against
. ~
,~-""
(iii) In case of easily liquefiable gas like cal> Z dips largely Ratio of Molar Heat Capacity
below ideal line in low pressure region, see Fig. 4.12 (a). It is denoted as y.and it represents atomicity of the gas.
Specific Heat of Gases 5
. C R
Amount of heat required to raise the temperature. ofl g of a For mono atomic ga,'I, (y) = ~ = 1.66
substance through laC is called its specific heat. It can be . Cv 3
measured at constant pressure and at constant volume. 2 R.
Molar specific heat, i. e. ,heat required to raise 1 gram mole of
a substance through laC is called heat capacity.
2R
For diatomic gas, (y) =.L 1.40
Heat Capacity at Constant Volume ~R
It is denoted by C v. It may the heat supplied to one mole of a 2
substance to increase the temperature through I °c at constant Cp
volume. .
F ..
or tnatoLllC gas, (y) = -
. Cv
= 4R
3R
= 1.33
•
We know from kinetic theory that,
1 2 1 2 3 Na'\lNne YAt"f¥ty
PV -mnc or -mnc =-RT
3 2 2 He 5 3.01 1.99, 1.661
Thus, kinetic energy E
3 RT N2 6.95 4.96 . 1.99 1.4 2
2
When temperature is raised through 1°C then the increase in O2 6.82 4.83 1.99 1.4 2
kinetic energy may be given as: CO 2 8.75 6.71 2.04 1.30 3
3 3 3
Increase in kinetic energy -R(T+l) -RT=-R H2S 8.62 6.53 2.09 . 1.32 3
2 2 2
Now, C v . ~ R since at constant volume, heat supplied to raise Example 46. Specific heat of a monoatomic· gas at
2 constant volume is 315 J K -I and at a constant pressure is
the temperature is used up to increase the kinetic energy only.
525 J kg -I K -I. Calculate the molar mass of the gas.
3
Cv = - R (for mOIioatomic gases only, since monoatomic
2 Solution: Cp M x 525 and Cv Mx315
gases undergo translational motion only] where, M is the molecular mass.
3 R + x [for di and polyatomic molecules; vibrational C p -C v R (R=8.314JK,1 marl)
2
Mx525 Mx315=8.314
and rotational motions also contribute to
the total kinetic energy] M (525 315) = 8.314
where factor' x' varies from gas to gas and its value is zero for M = 8.314 = 0.0396 kg mol- I 39.6 g mol-I
monoatomic gases. 2lO
Example 47. Calculate the pressure exerted by 16 g oj'
Heat Capacity at Constant Pressure methane in a 250 mL container at 300 K using van der Waals'
It is denoted by C p; it may be defined as heat supplied to 1 equation. What pressure will be predicted by ideal gas equation?
mole of a substance in order to increase the temperature through a= 2.253 atm L2 mol -2, b 0.0428 L mol -I ,
1°C at constant pressure.
R = 0.082ILatmK- 1 mol-I
Heat supplied at constant pressure will be used in:
16
(i) Increasing kinetic energy, which is equal to ~2 R . + x. For Solution: GIven, 16 g CH4 = 1mole
16
monoat~mic
. gas increase in kinetic energy is equal to 3 R when
2
Applying van d7 wa:l~: elquation,
P (~)r p+ ~
\
The ideal gas equation predicts that, [AnS'. (b)]
p nRT" 1 x 0.082 Ix 300 = 98.52 a~m
.[Hint: nb) == nRT
V 0.250
Example 48. Calculate the' temperature of the gas if it
obeys van der Waals' equation from the following data. Aflask of For n I, (p +a. \(.v .:.P...) = iRT
2 . '., 4V2) , '2 2·
..
.
2.5 litre contaihs 10 mole of a gasundJ;- 50'atrrl. Given
a = 5.46atm Zitre 2 mol ::2 and b=o.03Ilitremol- l .
Solution: Given that, 26. van derWaals' constants of two gases .Kandt are as given:
P = 50 atm; V 2.5litre, n =: 10; a = 5.46 atm litre mol-
2 2
; a (litre-atm mol-2 ) b (litre mol ~l)
Gas X '5.6 . , OJ/65
,:~;~J)iQJlli~rervql-l;
i
R :=O.08211itre- atJ;nK- mQEt",
ctasY ·5.1. 0,012
Applying van der Waals' equation, . What is correct about the two gases?-
(b) Te(X) = Te(Y)
[
p+ant
V
J(V -nb)= .nRT (a) Te(X) > TeeY)
(c) Ve(X» Vc(Y) (d) Vc(Y) > Vc(X)
[Ans.(q)1
an2 (Hint: Gas X. Gas l'
[p+ (V-nb)
Vc = 3b 3 x 0,065 = 0.195 3 x 0.012 0.036]
or T= ---.~~. _ _c ' - - _
27. Select the correct statements about van der Waals' constant
nR
'b',
(2.5-10x 0.031)
r\ So.;.5,46XIOO)'
. (2.5i .
I'. Itisexc1uded volume
.~ "if:".;";.':;
IlLIlSTM1rONS
,'r.j
.
:,.
. 366.4 K
10 X 0.0821
'~il':.··
OF 'OBJECTIVE QUESnQNS ,
~_.,·.:~<'.:n
2. Its unitis mol litre- 1
3. It depends on intermolecular force
4. Its value ddpends on molecular size'
(a) 2,3 {b).I, ~,4. . (c).2, 3, 4 (d) 3, 4
[Ans. (b)]
23 •. At high.temperature and low pressure, the van der Waals' ; 28" .. Gases X, Y,
equation is reduced tp:
(a)(p+ a V· RT (b}PV=RT
(c)P(V b) RT
The gas with the highest critical temperature is: .
• [Ans.. (b)] . " . [PEt(K~rala) 2006[
[Hint:,At high temperatur·eand lowpressure,V. in (a); P (bJ Q '(c) Y (d),Z
comparison'to'liarid( ;2) is negligible in comparison to P. (e) X
[Ans. (e)]
Hence, the equation reduces to PV ~. RT .]
[Hint! . Cntic~1 temperattu-e, Tc
24. The constant'a'in'vander Waals'eqilatiOl1 is maximum in: 27Rb
(a) He (b) H2 :. treater is the value of (al b~ more is the criti~~i temperature
of gas:
(c) 0 2 , ( d ) N H ' l
[Ans. (d)]. . For gas X, Te will be maximum.
[Hint: Intermolecular force ofNH3 is maximum, hence its van T = 8a
del' Waals' constant (a) will also be maximum.] c . 27Rb . ; , .....
25. The van der Waals' equation for 0.5 mol gas is: ~ for X = c= 240; for all: oth~rgases, (!!.)
is lesser.]
b 0.025 " ' . ' b, '.
(
(a) I P+
a I/V . 2RT
=- 29. At high pressure, van der Waals' equ3,tion becomes:
\ \ 2 2
(DPMT 2006)
.. a
(2Vb)= RT (a) PV =C.RT (b)PV=,R], +v
(c) PV ==:RT-!!:.. Cd) pi! =RT + Pb
(C)(p+ a (2V-4b)=RT V
[Ans.' (d)]
STATES OF MATIER. 239
~ nb)
2
[Hint: (p + a n (V nRT
Solution:
P(V ~b)=RT .
. PV =RT +Pb]
_}60m (76 + 38) cm
2£ + 5 46 + 5 + 44.5 cm
L= 45.25cm
When the tube is held at 60° with the vertical, the mercUry Also P2 12a = Pill a
column will slip down.
12 = Pill.
Py + 5eos 60° = P x
P2
5 '.
Py = 2.5cmHg ... (i) 76x 10 (c)
2 ---8--' =9.3 em
From end X, Po x 45.25=Px x 44.5 76+-'-
P _ 45.25 P .fi
.... (ii)
x - 44.5 0 Example 54. The stop cock connecting two bulbs of
volume 5 litre and 10 litre containing an ideal gas at 9 atm and 6
From end Y, Po x 45.25 = Py x 46
atm respectively, is opened. What is the final pressure in the two
. P 45.25 P ... (iii) bulbs if the temperature remains the same?
y
46 0
Solution: PI VI + PZV2 PR (VI + V2 )
Substituting the, values of Px and Py in equation (i) we get
9x 5+ 6x lO=PR (15)
Po = 75.4
PR = 7atm
Example 53. A lOcm column ofair is trapped by a column
of Hg, 8cm long, in a capillary tube horizontally fixed as shown where, PR resultant pressure after mixing.
below, at latm pressure. Calculate the length of air column when Example 55. At what temperature is the average velocity
the tube islzxed at the same temperature (a) vertically with open ofO2 molecule equal to the root mean square velocity at 27°C?
,end up (b) vertically with open end down (c) at 45° with the -:;B~Jl\D1jJit95)
horizontal with open end up.
Solution: .
~8RT =
1---10cm--->4 nM M
8RT 3R x 300
nM M
T = 353.57 K
(a)
t = 80.57° C
. Example 5~. The composition of the equilibrium mixture
for the equilibrium Cl 2 ~ 2 CI at 1400 K may be determined
(b) by the rate of diffosion of mixture through a pin hole. It is found
that at 1400 K, the mixture diffuses 1.16 times as fast as krypton
l
diffuses under the same conditions. Find ihe degree' of
dissociation ofC1Q. equilibrium. '(II(jIt1)<)~5)
or Pill a = P2 12 a Solution: Equilibrium of dissociation of Cl 2 may ~e :.
where, a area of cross section of tube represented as:
11 '/2 = length of air column 02(g) ~ 20(g)
P2 =76+8=84cm 1=0 a 0
teq a(l 0:) 2a 0:'
12 = Pill = 76x 10
P2 84 Total moles = a(l- a ) + 2aa = a(l + a )
MCI2
= 9.04 em M mix = =--
a(l + a) (1 + a )
Pilla P2 12 a
(b) P2 = 76 8 68cm
76x 10
68
11.17 cm
R" ~:~:
1.16= - - -
(c) When the tube is held at 45° with open end up, the weight
. of Hg is borne partially by the gas and partially by the Hg.
Vertical height of Hg is a measure of additional pressure on gas, a; a = 0.1374
i.e.,
Example 57. A gaseous mixture of helium and oxygen is 0.5= 100 x V
found to have a density of 0.518 g dm- 3 at 25°C and 720 torr. 0.0821 x 273
What is the per cent by mass of helium in this mixture? V 0.1l2litre
Solution: We know that, Pm::: dRT According to van der Waals' equation~
RT r He 2rCH4
242 G;RB. PHYS!CALCHEMISTRyFoRGOMPETIT!ONS
Substanee
. ~. . . ·····.···~·········.r,'W(: .
Water 4.6 17.5 55.0 355.5 760.3
Ethyl alcohol. 12.2 43.9 135.3 812.6 1693.3
Diethvl ether I 185.3 442.2 921.1 2993.6 4859.4
It is observed that non-polar or less polar liquids such as
diethyl ether and ethyl alcohol possess fairly high vapour
pressures on account of weak intermolecular forces (cohesive
forces) whereas polar molecules such as water which have
Fig. 4.13 (a) Evaporation in a closed vessel stronger intermolecular forces possess relatively lower vapour
pressures.
trapped. The return of the molecules from the vapour state'to the
The simplest method for measuring vapour pressure is the
liquid state is known as condensation. As evaporation proceeds,
barometric method. It consists of two barometer tubes as shown
the number of molecules in the vapour state increases and, in
in Fig. 4.14. A small quantity of the liquid is introduced into one
turn, the rate of condensation increases.
of the tubes. It changes into vapour and rises into vacuum above
The rate of condensation soon becomes equal to the rate of the
evaporation, i. e., the vapour in the closed container is in
equilibrium with the liquid. Vapour
Evaporalion~
~
Liquid ~ Vapour
Condensation
Rate of condensation
Time-
Fig. 4.14 The barometric method for measurement of
Fig: 4.13 (b) vapour pressure
At equilibrium, the concentration of molecules in the vapour the mercury. Some more of the liquid is introduced and the
phase remains unchanged. The pressure exerted by the vapour in process is continued till a small amount of the liquid is visible on
equilibrium with liquid, at a given temperature, is called the 'the surface of mercury. The difference in the levels of mercury in
vapour pressure. Mathematically, it is given by the gas equation: the two tubes is noted and this measures the vapour pressure of
the liquid at atmospheric temperature. The measurement can also
p=!!... RT CRT be made at any desired temperature by surrounding the tubes with
V
a jacket maintained at that temperature.
where, C is the concentration of vapour, in moVlitre. The vapour pressure of a given liquid at two different
In closed vessel, temperatures can be compared with the help of
Rate of evaporation ex: e - EI RT (Boltzmann factor) Clausius-Clapeyron equation.
Thus, rate of evaporation remains constant at constant
temperature.
Since, the rate of evaporation increases and rate of
condensation decreases with increasing temperature, vapour
2.:R [~ - ;J
where, M/ is the latent heat of vaporisation and R is the molar gas
pressure of liquids always increases as temperature increases. At
constant.
any given temperature, the vapour pressures of different liquids
are different because their cohesive forces are different. Easily The actual form of Clausius-Clapeyron equation is:
vaporised liquids are called volatile liquids and they have -M/
_ _v_sP:....+A
10glO P
relatively high vapour pressures. Vapour pressure values (in mm 2.303RT
.,
Note: Vapour and gas: A gas can be liquefied only below critical temperature, by applying pressure. There is no characteristic critical temperature for
vapours.
I
:
, '
!
I
Sfope of the line I
I
-LiH\lap e I
I
I
:--
2.303R i -0.50
I
I
~ ,
I
I
I
:; I
I
I
! I
I
I
I
I
I
I
1fT ~ ,
I
I
B (i) (Ii)
force of adhesion between the molecules of water and the Let YI and d t be the surface tension and density Of water and
molecules of glass of the capillary tube is greater than the force of 12 and d 2 be surface tension and density of the liquid whose
• cohesion between water molecules. Due to this, surface of water surface tension' is to be determi~_d.-Usjng a .stalagmometer the
in a glass capillary tube curves upwards in convex shape and then number of drops fonned by the same volume of water and liquid
the force of surface tensi9" of water pulls the water up into the is detennined.
tube. The water rises into a capillary tube to such a height that the 11. :ntdz
weight of resulting water column is just balanced by the force of 12 n Zd 1
surface tension. Using the above relation, the surface tension Of the liquid, 1 2,can
The rise of oil in a lamp wick: and flow of water from the roots be calculated.
of a tree to upper parts are also the examples of capillary action .
. N~te; Attlrecriu\':al temperatuie. surfa\':etensl0n oniqUid~ #(wbere the meniscus between the liquid and the v~ di~-s).
SurfaCe tension is scalar quantity. ;. y. - - '. . .~ _ •
I
G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Sutface tension afthe liquid can also be measured by ~apillary one having lower velocity will experience a rel1miing effect due
rise method. ' to the internal friction between the two layers. This internal
friction or resistance is called viscosity.
-rcos9 Imagine a liquid to be made up of a large number of thin
cylindrical coaxial layers.
It has been found that force of friction '.f' between two
cylindrical layers each having area ' A' sq. cm separated by a
distance •x' cm and having a velocity difference v cm Isec i~ .
given by:
rhpg .!
Fig. 4.1.9
(p :;: density of liquid) Here,." is., a constant known as coefficient of viscosity. If x:;::; I
Y = 2cos e
cm, A = Icm 2 and v = lcm1sec., then /='11.
If angle of contact between glass and liquid is zero, i. e.,
cose 1, then ' ' Thus, coefficient of viscosity can be defined as the force per
unit area needed to maintain unit difference of velocity
rhpg
1=-2- between two consecutive parallel layers of the liquid which
are one centimetre apart.
Effect of temperature on surface tensi~ : Surface tension Coefficient of viscosity is expressed in dyne cm -'2, sec. It is
decreases with rise in. temperature because the intermolecular more commonly expressed as poise, centipoise (10-2 poise) and
force also decre8l)es with rise in temperature. The decrease in millipoise (I 0-3 poise), after the name of Poiseuille who derived
surface tension with rise in temperature continues till ctitical the formula and gave the method for its determination. 1 poise is
temperature at which the surface tension of liquid becomes zero, equal to a force oft dyne per unit area whlch maintains a velocity
i.e., menisCus between liquid and vapour disappears. difference of 1 cm per second between two parallel consecutive
According to EOtvos equation, layers of the liquid 1 em apart.
M)2/3 The reciprocal of the coefficient ofviscosity is called Fluidity
Y= (P . =K(tc-1) (4)) .
III :;: Fluidity =!
:.As t increases, y decreases linearly, when t :;: t c ' y ::: 0, here '11
t c is the critical temperature. Liquids with low viscosity are terme4 mobile and others with
(xii) Viscosity high viscosity are called viscous.
Viscosity depends on the following factors:
All liquids have a characteristic property of flow. Some
(a) Intermolecular forces: The liquids with high
liquids like water, alcohol, ether, etc., flow, quickly· while
intermolecular attractive forces offer greater resistance to the
glycerine, castor oil, molasses, etc., flow very slowly. The
flow of molecules and thus possess high viscosity:
property of tbe liquids wbicb determines tbeir resistance to
(b) Molecular mass: The flow of molecules is inversely
flow, is called viscosity.
proportional to its mass. Liquids' having high molecular mass
When a liquid flows through a pipe, all parts of it do not move possefs greater viscosity. . .
. .
at the same rate. The thin layer in immediate contact with the wall ~
of the pipe is almost stationary. The velocity of flow of each generally increases as' the branching in. the chain increases.
successive layer of liquid increases progressively as we proceed Symmetrica:l molecules have low viscosity,
inward towards the centre. At the centre, the flow becomes
fastest. Each layer ofliquid moving with greater velocity over the
I
"
(d) Tempertlture: Intermo lecular forces decrease with rise .,... (e) Pressure: the increase of pressure increases the
in temperature. Thus, viscosity decreases with the increase of intermolecular forces. Thus, the viscosity of a given liquid
temperature. This property is used to select the lubricant for !l increases with increase of pressure.
machine and engine. The variation of viscosity with temperature' (f) Density : Viscosity of a liquid increases with increase in
can be expressed by the fOllowing relationship: density whil6 that of gas decreases.
11:::: Ae-EaIRT ... (i) Measurement 4)f viscosity: Viscosity' is generally
determined by Ostwald's method. It involves the comparison of
where, A Pre-exponential factor (constant) time of flow of equal volumes of two liquids through the same
E(/ =Activation energy capillary using an apparatus called viscometer.
Taking logaritlm1 of equation (i) we get: 2= dXI
1 n", dw x (II'
log 10 n == log 10 A x- .. ·Oi)
2.303R T
where, 11 w , n == coefficients of viscosity of water and liquid
respectively; d:::: density of liquid; d w =density of water;
t == time of flow of liquid; t w :z:: time of flow of water.
log 10
n2 Ea
~ = 2.303R 1} - T2
[I I] Point of similarities:
(i) Both viscous force and solid friction come into action
where ever there is relative motion.
where n 2 is the coefficient of viscosity at temperature T2 and (it) Both these forces oppose the motion.
111 is the coefficient of viscosity at temperature TI . (iii) Both are due to molecular attraction.
, (v) Melting point: The temperature at which the solid and Crystalline solids are anisotropic. Magnitude of some of the
the liquid forms of a substance exist at equilibrium or both the physical properties of crystalline solids such as refractive index,
forms have same vapour pressure, is called the melting point. On coefficient of thermal expansion, electrical and thermal
supplying heat energy, the particles acquire sufficient energy and conductivities, etc., is different in different directions, within the
move away from their fixed positions in space. This results in the crystal. For example, in the crystal of silver iodide (AgI), the
formation ofliquid state. The solids have definite melting points coefficient of thermal expansion is positive in one direction and
, depending on the strength of binding energy. However, in some negative in the other direction.
solids (a~orphous solids)'" the melting point is not sharp. B D
* Melting point of a solid depends on the structure of the solid. It is used for the identification Of solids whether it is crystalline or amorphous.
. STATES OF MATTER· 249
Crystaillne 'sollds Amorphous sollds axes of symmetry are called diad, triad, tetrad and hexad,
respectively, if the original appearance is repeated twice (after an
6. Crystals are bound by plane Amorphous solids do not have .. angle of 180°), thrice (after an angle of 120°), four times (after an
faces. Tqe angle between any well defined planes. angle of 90°) and six times (after an angle of 60°) in one rotation.
two faces is called intertilcial an- When an amorphous solid is bro-
These axes of symmetry are also called two-fold, three-fold.
gle. For a given crystalline solid, ken, the surfaces of the broken
it is a definite angle and remains pieces are generally not flat and
four-fold and six-fold. respectively.
always constant no matter how intersect at random angles. In general, if the same appearance of a crystal is repeated on
the faces develop. . through an ang1e 0 f -
rotatmg 3600
- .. around an"Imagmary aXIS,. t he
When a crystalline solid is ham- n .
mered, it breaks up into smaller axis is called an n -fold axis.
crystals of the same geometr>cal In all, there are 13 axes of symmetry possessed by a cubical
shape. .
crystal like NaCI as shown in Fig. 4.22 (c), (d) and (e).
7.. An important property of crys- Amorphous solids do not have (iv) Elements of symmetry: The total number of planes.
tals is their symmetry. There are: any symmetry. axes and centre of symnletry possessed by a crystal are tenned as
(i) plane of symmetry, (ii) axis of elements of symmetry. A cubic crystal possesses a total of 23
symmetry and (iii) centre of elements of symmetry.
symmetry.
• Planes of symmetry =(3 + 6) =9 [Fig. 4.2.2 (aland (b)]
4~16' TYPES OF SYMMETRY IN CRYSTALS Axes of symmetry (3 + 4 + 6) =13
(i) Centre of symmetry: It is such an imaginary point within [Fig. 4.22 (c), (d) and (e)]
the crystal that any;line drawn through it intersects the surface of
the crystal at equal distances in both directions. A crystal always
Centre of symmetry =1 [Fig. 4.22 (f)]
possesses only one centre of symmetry [Fig. 4.22 (f)]. Total number of symmetry elements 23
Oi) Plane of symmetry: It is an imaginary plane which
passes through the centre of a crystal and divides it into two equal 4.17. SPACE LATTICE AND UNIT CELL
portions such that one part is exactly the mirror image of the
All crystals are"polyhedra consisting of regularly repeating arrays
other.
of atoms, molecules or ions which are the structural units. A
A cubical crystal like NaCI possesses, in all, nine planes of crystal is a homogeneous portion of a solid substance made of
symmetry; three rectangular planes of symmetry and six diagonal
regular pattern of structural units bonded by plane surfaces
planes of symmetry. One plane of symmetry of each of the above
making definite angles with each other. The geometrical form
is shown in Fig. 4.22 (a) and (b).
consisting only of a regular array of points in space is called a
tV lattice or space lattice or it can be defined as an array of points
showing how molecules, atoms or ions are arranged in different
Axis of four-fold
sites, in three-dimensional space. Fig. 4.23 shows a space lattice. A
space lattice' can be subdivided into a number of small cells
known as unit cells. It can be defined as the smallest repeating
unit in space lattice which, when repeated over and over again,
results in a crystal of the given substance or it is the smallest
of symmetry of symmetry symmetry (three) block or geometrical figure from which entire crystal can be built
(a) (b) (c) up by its translational repetition in three-dimensions. A unit cell
:,
tV
of a crystal possesses all the structural properties of the given
crystal For example, if a crystal is a cube, the unit cell must also
have its atoms, molecules or ions arranged so as to give a cube.
$ I,I,
8, .
,
JI----Jl~-.._-~/
,
I
Lattice
points
I
,
,
,"
I
W-y
~ ,U
, \b ~ .
, -SX b
All crystals do not have simple lattices. Some are more
~-y / I>§-y bV / Yen /
complex. Bravais pointed out that there can be 14 different ways Simple Body-centred Simple End-centred
in which similar points can be arranged in a three-dimensional (c) Tetragonal and monoclinic space lattices
space. Thus, the total number of space lattices belonging to all the
seven crystal systems are 14.
The crystals belonging to cubic system have three kinds of
Bravais lattices. These are:
c
(i) Simple cubic lattice: There are points only at the corners
of each unit.
(U) Face-centred cubic lattice: There are points at the comers Triclinic Hexagonal Rhombohedral
as well as at the centre of each of the six faces of the cube. (d) Triclinic, hexagonal and rhombohedral space lattices
•
STATES OF MATTER
3
(iii) Body-centred cubic lattice:There are points at the a xd
comers as well as in the body-centre of each cube. ',Number of mol per unit cell = M
The number of Bravais space lattices in a given system is =
where, M molar mass
listed in the following table and shQwn in Fig. 4.24. Number of moleCUles per unit cell= Number of mole
No. of . '
x Avogadro' s number
Crystal .. . 3
, space'.: Lattice type a 3 xd a· xdxN
system ". Z= xN=----
lattices ;
M M
1. Cubic 3 Simple, face-centred and body-centred. Calculation of number of constituertt units in
2. Orthorhombic 4 Rectangular and body-centred rectan- hexagonal unit cell
gular prism; rhombic and body-centred (i) Constituent units at each comer oCunt~Cell iSCOftllT10n"
rhombic prism. among six unit cells hence contribute 1/6th to each unit cell.
3. Tetragonal 2' Simple and body-centred tetragonal (ii) Constituent unit at edge is common to three unit cells
prism. hence contribute 1I3rd to each unit celL
4. Monoclinic 2 Monoclinic parallelopiped, monoclinic (iii) Constituent units present at the body centre is considered
face-centred parallelopiped. in single unit cell.
(iv) Constituent unit at face centre 'is common between two
5. Triclinic Triclinic parallelopiped. unit cells hence contribute 112 to each unit cell.
6. Hexagonal Hexagonal prism.
7. Rhombohedral Rhombohedron.
In various unit cells, there are three kinds of lattice points:
points located at the comers, points·in the face-centres and points
that lie entirely within the unit cell. In a crystal, atoms located at
the comer and face-centre ofa unit cell are shared by other cells
and only a portion of such an atom actually lies within a given
unit cell. .
(i) A point that lies at the comer of a unit cell is shared among
eight unit cells and, therefore, only one-eighth of each such point
lies withln the given unit cell.
Fig. 4.25 Hexagonal unit cell
(ii) A point along an edge is shared by four unit cells and only
one-fourth of it lies within anyone cell.
(iii) A face-centred point is shared by two unit Gells and qnly In thehexagonaJ unit cell (Fig 4.25), t2 comers, 2 face centres
one half of it is present in a given unit ceiL and 3 constiruent Mits wlthin the unit cells me Dccupied~ hence
(iv) A body-cel.itred point lies entirely within the unit cell and' effective number of con$tituent units.present in the unit cell may
contributes one complete oint to the cell. be calculated as
~--~---------------------- 1 occupied + 1 occupied Central
Contrlbutioa to one unit eeU' z 6 x comers 2 x",lacecIutres + constltuen.' f UlUts
.
118 1 1
Edge 1/4
=-x 12+-x2+3
6 2
Face-centre 112 6
Body-centre
Total number of constituent units per unit cell 4.19 DESIGNATION OF PLANES IN
=-1 x occuple. d comers + 1 x occuple. dedge-centres CRYSTALS-MILLER INDICES
8 4
Planes in crystals are described by a set· of integers (h, k and I)
+ 1 x occupied face-centres + occupied body-centre. . known as Miller indices. Miller indices of a plane are the
2
reciprocals of the fractional intercepts of that plalle on the various
Determination ofNumber of Constituent units per unit cell:
crystallographic axes. For calculating Miller indices, a reference
Let edge length of cube = a cm plane, known as parametral plane, is selected having intercepts
Density of substance = d g cm-3 a, band c along x, yand z-axes, respectively (Fig. 4.26). Then,
Volume of unit cell =a 3 cm 3 the intercepts of the unknown plane are given with respect to
Mass of unit cell volume x density = (a 3 X d) g a, band c of the parametral plane.
252 G.R.B. PHYSICAL CHEMISTRY FOR COMP.ETITIONS '
=1:J2: ~
= I : 1.414: 0.577
y y y
Fig. 4.29 X-ray reflection from crystals Example 64. The first order reflection ofa beam ofX-rays
0.!jwavelength l.54Afrom the (lOO)face ofa crystal of the simple
254 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
cubic type occurs at an angie ofl1.29°. Calculate the length of AC 2 = AB2 +BC 2 = a 2 +a 2 = 2a 2
the unit cell. or AC J2a
Solu$n: Applying Bragg's equation, Now, in .!l ADC,
2dsin8::::nA AD 2 .= AC 2 +CD 2
Given,8 11.29°, n:::: 1, A = 1.54 A = 1.54 X 10-8 cm = (F2a)2 +a 2 ::: 3a 2
d = 1.54 X 10-
8 8
1.54 X 10- = 3.93 X 10-8 cm
or AD 13a
2 x sin 11.29° 2xO.1957 d 13 a
a 2
d bkl = =a 13
Jh 2 +k 2 +.1 2 d=2r=-a
2
a = 3.93 x 10- cm
8
=length of the unit cell or Atomic radius, r=
13 a
4
Example 65. When an electron in an excited state of Mo
atom falls from L to K-shell, an X-ray is emitted. These X-rays are (c) Face-centred cubic unit cell
diffracted at angle of7.75° by planes with a separation of2.64 A. The distance between the two
What is the difJerence in energy between K-shell and L-shell in nearest neighbours is represented
Mo, assumfngajirst order difJraction (sin 7.75° 0.1349)? by length AB or BC, i. e., half of the
Solution: According to Bragg's equation: face diagonal, .4 C.
AC
nA 2d sin 8 d=AB=BC=-
2 Fig. 4.32
Ix A = 2x 2.64 sin 7.75° = 2x 2.64 X 0.1349 Face-centred cubic un!t
In MCD, AC 2 CD 2 + AD2
A =0.712A cell
2
a 2 +a = 2a 2
Energy difference between K and L-shell of Mo AC=J2a
hc
34 8
6.626xI0- x3xI0 =2.791xlO- 15 J AC J2 I
or d:::-= a=-a
A O,712x 2 2 J2
4.21
.
ANALYSIS OF CUBIC SYSTEMS
d
1
2r=-a
"
J2
The following characteristics are reflected by cubic systems . rad'lUS, r =
or A tomlC I a
when analysed mathematically:
(i) Atomic Radius (ii) No •.of Atoms Per Unit Cell
It is defined as half the distance between nearest neighbouring
Different types of cubic unit cells are given in following figure:
atoms in a crystal. It is expressed in terms of length of the edge .,
® ~ a
'a' of the unit cell of the crystaL
(a) Simple cubic unit CQ:U : In a
simple cubic unit cell, atoms at the
comers touch each other along the edge.
Distance between the nearest
B._---"'a--..
®
I
I
I
I
I
I
II II II
8
I ' I , I
neighbours,
d=AB:::: a=2r
i.... :!.·
• . *
.....:1:
. .
, , ~,' .
(where r = radius of the atom) . Fig. 4.30 v
rt]~
r a =G.5a
2
. (b) Body-centred cubic unit
cell : The distance between the
two nearest neighbours is repres-
ented by length AE or ED, i.e.,
1/8 atom 1 atom 1/2 atom
half of the body diagonal, AD.
Simple cubic Body centred cubic Face centred cubic
d AE=ED AD (a) (b) (c)
2 Fig. 4.31
In .!lABC, Fig. 4.33 (a) Simple or primitive cubic .lattice;
~Body·centred cubic unit cell
(b) Body-centred cubic latti~~ (c) FacErcentred cubic lattice
STATES OF MATTER I
=- - =-rr = .
3
(a) Simple cubic structure~ Since, each comer atom is r ' = -v
· f actIOn rra /6 052
Pac k mg
shared by eight surrounding cubes, therefore, it contributes for ~ V a3 6
8 i. e., 52% of the unit cell is occupied by atoms and 48% is empty.
of an atom.
(b) Face-centred cubic str~ture: Since, four atoms are
Thus, for simple cube = 8 x.~ = 1atom per unit cell present in a unit cell, their volume is
8
(b) Face-centred cubic structure: Since, the structure v =4 x (~rr,.3)
possesses 8 comer atoms and six at the centre of each face, the
contribution will be Putting the value of r = a~,
2,,2
= 8x~ + 6 x ~ (Face atom is shared by two cubes)
136rr(2~r ::n
8 2
a3
= 1+ 3 = 4 atoms per unit cell v= =
(c) Bociy-centred cubic structure: Since, the structure
Volume of unit cell, V = a 3
possesses 8 comer atoms and one body-centre, the contribution
3
will be = 8 x ~ + 1= 2 atoms per unit cell. Packing fraction =3-v2a
rr~ =. . r r;:;- =0.74
8 3
j""I/2
(iii) Coordination Number i. e., 74% of unit cell is occupied by atoms and 26% is empty.
It is define<t'as the number of nearest neighbours that an atom (c) Body-centred cubic structure: Since, two atoms are
has in a unit cell. It d'epe)1dsiUpon structure. present in aunit cell, their volume is
(a) Simple cubic strp,tture: Coordination number = 6
(b) Face-centred cubic structure: Coordination number =12 v = 2 x (~rrr3 )
(c) Body-centrei"cubic structure: Coordination number = 8
(iv) D~!Islty of Lattice Matter . the value ofr=-
Puttmg -/3 a, 'v' = 2x -4 rr x [-/3)3
- a
Knowing the unit cell dimensions, the theoretical density of a 4 3 4
crystal can be calculated as: -/3rr a 3
. ate
Density f h umt. ce 11 = - -
Mass
-- of -unit-cell
-- 8
Volume of the unit cell Volume of unit cell, V = a 3
=8xX 1.
AIl: atom at the face of the cube contributes ~ to the unit cell. many aton:s does 208 g of the element contain?
Hence, number of atoms of B in the unit cell: 6 x ~ = 3. Solution: Volume of the unit cell =(288 x 10-10 )3
Thus, th~ formula is AB 3 •
Example 67. At room temperature, sodium crystallises' in
=23.9 X 10-24 cm 3
body-centred cubic lattice with a:= 4.24 A. Calculate the
the()retical density of sodium (At. mass of Na = 23.0). Volume of 208 g of the element: _20_8 =28.88 cm 3
7.2
Solution: A body-centred cubic unit cell contains 8 atoms at
the 8 comers and 1 in the centre. Number of unit cells in 28.88 cm3 :::: _ _2_8_.88---:C"":'
Hence" 23.9x
Total number of atoms in a unit cell = 8 x ~+1 2 = 12.08 X 1023 unit cells
8
Each bcc structure contains 2 atoms.
STATES OF MATTER
" 257
23
So, Total atoms in 12.08 x 10 unit cells Example 74. Tke density ofcrystalline sodium chloride is
23 2.165 g cm -3. What is the edge length of the wiit cell.
= 2 x 12.08 X 10
= 24.16x 10 23 What would be the dimensions of cube containing one mole of
NaCl? .
Example 71. Lithium forms body-centred cubic crystals.
Solution: We know that,
Calculate the atomic radius of lithium if the length of the side ofa
unit cell of lithium is 351pm. N/MJ
Solution: In body-centred cubic crystals, p= lNA
r
13 a where; p = density = 2.165 gcm-3
4 M molar mass = 58.5 '
. 13 '
=,- x 351pm 151.98pm NA Avogadro's number = 6.023 x 1023 .
4
N = number of formula unit per unit cell
.Example 72. Ammonium chloride crystallises in a
= 4 (for fcc)
body-centred cubic lattice with a unit distance of 387 pm.
Calculate (a) the distance between oppositely charged ions in the 3 N (M
' .' 4 [ 58.5 ]
lattice and (b ) the radius of the NH4+ ion if the radius ofCI-ion a = NA pl = 2.165 6:023 X,10 23 .
is 181pm.
1. 794 X 10-22
Solution: (a) In a body-centred cubic lattice, oppositely
charged ions touch each other along the cross-diagonal of the a :: 5.64 X 10-8 cm
cube. . I Molar mass 58.8
So, 2rc +2ra = 13a M oarvoume=
1
Density
::.--
2.165
or rc + ra = 13 a 1 3
2 Edge length (a) [58.8 J / = 3 cm
13 x 387 = ~35.15 pm
2.165-
2 . Example 75. The density of potassium bromide crystal is
2.75 g cm -3 and the length ofan edge ofa unit cell is 654 pm. The
(b) Given that, ra 181 pm
unit cell ofKBr is one ofthree types ofcubic unit cells. How many.
. rc = 335.15- 181.0= 154.15pm formula units of KBr are there iii a unit cell? Does the urdt cell
have a NaCl or CsCI structure? .
Example 73. The unit cell cube length for LiCI (NaCl
structure) is 5.14A. Assuming anion-anion contact, calculate the Solution: . We know that,
ionic radius for chloride ion. .. N [M 1
Solution: In a face-centred cubic lattice, anions touch each p= NA J
other along the face diagonal of the cube. . 3·'
N=pxa x NA
4rCl - =-F2a M
.J2 a x 6.023 X 1023 .
3.89=4
4
Number of mass points per unit cell = 4
= .J2 x 5.14 1.82A·
4 It is NaCI type crystal, i.e., fcc structure.
Alternative: Distance between U+ and.Cl- ion Example 76. A unit cell of sodium chloride has four
formula units: The edge length of unit cell is 0.564 nm. What is
5.14 = 2.57 A CI- the denSity of sodium chloride? (liT May 1997)
~~CI
2
ZM Ax 58.5
Thus, distance between two chloride ions Solution: p =- - = - - - ' - - - - - - - - -
a 3 N (5.64 X 10-8 )3 x 6.023 X 10 23
=J (2.57i + (2.57)2
=2.16gcm-3
3.63A . 2.57 A
Example 77. Chromium metal crystallises with a
Hence, body-centred cubic lattice. The length of the unit cell edge is
radius of Cl- 3.63 = 1.82A found to be 287 pm. Calculate the atomic radius. What would be
2 the density of chromium in g/cm 3 ? (ItT July 1997)
258 I G.RB. PHYSICAL CHEMISTRY FOR COMPETITIONS
1
'Solutiou: In body-centred cubic unit cell, In bec unit cell, Z=2
aJ3 4r ..
, N'
Number of unit cells = ~ = 0.5 N A]
" 2
where, a = edge length,' r =radius of atom '
33. Sodium metal exists in bec unit cell. The distance between
r=c aJ3 = J3 x '4.29 ::::: 1.8574 A nearest sodium ;atoms is 0.368 nm. The edge length of the,
4 4 unit cell is: '
(a) 0.368nm (b)0.184nm
Example 78. When heated above 916°C, iron changes its
crystal structure from body-centred cubic to cubic closed packed (c) 0.575 nm (d) 0.424nm
lAns. (d)]"
structure. ASsuming that the metallic radius of the atom does not ,
change, ealcJlate the ratio of density of the bcc crystal to that of [Hint: In bee unit cell, aJ3 == 4r
the cep crystal. 4r 2
Solution: In body-centred packing, the efficiency of ,a=-,-=-x2r
Pllcking is 67.92%. In the cubic closed packing, the packing
..[3 J3
2
efficiency is 74.02%. == J3 x 0.368= 0.425 nm]
Let d l be the density when packing efficiency is 74.02% and
d 2 is the density when packing efficiency is 74.02%. ' 34. Ifth~ distance between Na+ and CI ions in NaCI crystal is
265 pm, then edge length of the unit cell will be? '
di = 67.92~~~.918 (a) 265 pm (b) 530 pm (c)795pm (d) 132.5 pm ,
dl 74.02 [Ans. (b)l'
[Hint: In NaCl:
IIlUmA1fONS OF OB)ECl"IVE QI:IESIIONS Edge length = 2 x distance between Na+ and CI -, ions,
= 2 x 265 = 530 pm] ,
30. AD. element 'A' has face-centred cubi.:: structure w~th edge 35. The interionic, distance for caesium chloride crystal will be:
, length equal to 361 pm. The apparent radius of atom 'A' is: , ' IPl\IT (MP) 2007] ,
(a) 127.6 pm ' (b) 180.5 pm ' ' 2a
(c) 160.5 pm' (d) 64 pm (a) a (b)~ (c) a/3 (d) /3
, 2 2
[Ans. (a)] ,
TAns. (c)]
[Hint: For face-centred 1.!llit cell,
a.Ji = 4r 4.22 PACKING ,OF IDENTICAL SOLID
361 x 1.414 ,SPHERES
----==r
4 The constituent particles in the formation of crystals are either
r 127.6 pm] atoms, iens' or molecules. These particles' may' be of various
31. , The packing fraction of the element that crystallises in simple shapes and thus, the mode of packing ,of these particles' will
cubic arrangement i s : ' , change ac«ording 'to their shapes. The simplest way will be to
consider these particles as spheres of equal size. The packing of
W~ OO~ ~~ 00% , spheres is done in such away as to use the available space in the
roost economical mal1Qer.
[Ami. (b)]
[Hint: In simple unit cell a == 2r
Z=I
, Occupied volume
Packing fraction == ---.::..----
Total volume
± 'ltr
3 ±'ltr
3
=_3_=_3_'_=~)
i
I
a3 (2r)3 6
32. Arrangement (i) , Arrangement. (ii)
How' many unit c.ells are present in 39 g of potassium that
crystallises in body-centred cubic structure? Fig. 4.35 -Two common ways ofpacki~g spheres
(a)N A ,(b)]I[ A
, " 4 "
(c) 0.5 N A (d) 0.75 N A • of equal size
There are two common ways .in which spheres of equal size
,[Ans. (c)]
can be packed. This has been shown in Fig~ 4.3~. The
" ~ass arrangement (i) is more economical in comparison to
[Hint: Number of atoms == x NA
i\tomicmass arrangement (ii) as 60.4% volume is occupied in arrangement (i)
'and 52.4% volume in arrangement (ii), Arrangement (i)
= 39 xNA'=N A ,
39 • , represents a close packing of spheres.
I
STATES OF MAnER
In arrangement (i), the spheres are packed in such a manner , spheres and IS a9breviated as hcp or ABABAB,. .. This is shown
that their centres are at the comers of an equilateral triaag!e. Each in Fig. 4.38. Iii' the second way, spheres are placed on the
sphere is surrounded by six other similar spheres as shown in Fig. unoccupied hollows of the first l~yer, marked by 'crosses'. It is
4.36. This arrangement can be extended iQJmeedimensions by observed that spheres of the third layer do not come over th9seof
adjusting spheres on the top- of hollows or' voids of the first layer. This arrangement of close packing is referred to as
two-dimensional layer which is called the first layer or 'A' layer. , ABC: However, it is noted that spheres in the fourth l~er will
in
There are two types of hollows the first layer which have been correspond with those in the first layer. When such an
marked by dots (.) and cross (x). All the hollows are equivalent. arrangement is continued indefmitely, the system is found to
The spheres of the second layer may be put either on hollows possess cubic symmetry 'and called cubic close packing Of
marked by dots or by crosses. Half of the hollows remain spheres and is abbreviated as ccp or ABCABC . .. This is shown
unoccupied in the second layer (Fig. 4.37). The second layer is in Fig. 4.39. The system ABCABC ... shows that there is a sphere
marked as 'B' layer. The spheres have been placed on the hollows at the centre of each face of the unit cube an~ thus, this system is
marked by dots. ' also referred to as face-centred cubic or fcc. - ,
Three-fold
Three spheres C
at the corners Six,spheres
of afjl equilateral surrounding B
,triangle a spherl:'
A
C
B
A
, Fig. 4.36 qlose picking of spheres
(a) (b) (c)
~
hcp or ccp, each sphere is surrounded by
twelve other spheres shown in Fig., ,4.40.
There is a third arrangement of packing of I
I
I
spheres which is known as body-centred, I
I
Rg. 4.37 Building of second layer (8" sho,wn shaded) cubic arrangement (bee). This arrangement '
covering hollows marked by dots ( • ); The , is obtained when the spheres in tp.e first
hollows ~arked by a cross (x) unoccupied layer are slightly opened up, i. e. ,none of the
I
To build up:the third lIiyer of spheres, there are two alternative spheres touches each other. In the second I,
I
ways. In the' first way the spheres are placed on the hollows of layer, the spheres are placed at the top of
second layer. it is observed that each sphere of th4'd layer lies
exactly above the spheres of first layer. When this arrangement is
continued indefinitely, the system obtained. is found to possess
hollows in the first layer. In the third layer,
spheres are placed exactly above the first
layer. Each sphere in this system of packing
€®'
Fig. 4.40
is in contact with eight spheres, four in the
hexagonal symmetry and is called hexagonal close packing of Coordination
lower layer and four in the upper layer. This
arrangement has been shown in Fig. 4.41. number in hcp.\,
GJoid axis and ccp structure -•.
_ Most of the metals belonging to s-block'
and d-block elements possess anyone of the following clo~
packing arrangements: 7
~."
f ~-, - ..- - -- ~ 4
/
0000 /
3 /
,,
,
K
\
\
::'>. .-t- /7'-.
I
I
/
O-Packing sites
• - Octahedral voids
(A) (B) ,
\
\
I
1/
/
~/
Fig. 4.41 (A) Body-centred cubic packing of spheres
(B) Body-centred cubic arrangement '" ....... 0' .......
"-
.......
.I/ff.
In a multilayered closest-packed structure, there is a
tetrahedral void above and below each atom, hence there are
twice as many tetrahedral voids as those of closest-packed
constituent units.
Tetrahedral and octahedral 'voids can be located as
- - - - - Second closest packed layer
Fig. 4.43 Octahedral voids --~--Tetrahedral voids
-----Octahedral voids'
Location of Octahedral and Tetrahedral Voids in Cubic -----Tetrahedral voids
Close Packing - - - - - First closest packed layer
Octahedral void.s: In the Fig. 4.44 a unit cell of ccp or fcc
lattice is drawn .. Corners .and face-centres are the packing sites. In . fWJ51RATfONS OF OBJfCnVf QUESTIONS
the face-centred cubic unit cell; octahedral voids are located at
. the body~centre and all the' edge certres of cube. 36. In a compound, atoms of element Yformccp lattice and those
Number of constituent units at packing sites == 8x 1 +6x 1 == 4 of element x.o,ccupy 2/3rd tetrahedral voids. The formula of
8 2 . the compound will be: (AlEEI': 2110X)
. Number of octahedral voids (one at body-centre a~d twelve at . (a)X 3Y4 (b)X 4Y3' (c)X 2Y3 (d)X 2Y
[Ans. (b)]
edge-centres) == 1+..!. x 12: 4 I .
. " 4 [Hint: Let number of atoms of Yused in packing = n
I
STATES OF MATTER 261
Number of tetrahedral voids =2n . ions have coordination number six. In CsCI, each Cs + ion is
2 4 surrounded by eight Cl- ions and vice-versa. Thus, both the ions
Number of atoms of X = x 2n := - n
3 3 have coordination Dl:lmber eight. In the case of CaF2 , the
coordination number of Ca 2+ - is eight while that of F - ion, is
Y:X:=lI:!lI =3:4
3 four.
Fonnula of compound == X 4Y3] The coordination numbers commonly encountered in ionic
37. A solid compound contains X, Yand Z atoms in a cubic lattice crystals are 8 (body-centred cubic arrangement), 6 (octahedral,
with X atoms occupying the comers, Y atoms in the body arrangement) and 4 (tetrahedral arrangement). '
centred positions and Z atoms at the centre of the faces of the It is impossible for both anions and cations to have closed
unit cell. What is the empirical fonnula of the compound? packed structures but if one of the ions is much bigger than the
(a) XY2Z3 (b) XJZ3 (c) X 2Y2Z3 (d) X 8YZ6 other, it is common for the bigger ions alone to approach a closed
(e)XYZ packed structure and smaller ions to fit into holes in this stru~re.
[Ans. (b)] Iri ionic crystals, the coordination numbers as well as the
1 geometrical shapes of the crystals depend mainly on the relative
[Hint: Number of atoms of X in a unit cell x 8"" I sizes of the ions. The ratio of the radii of the positive and negative
8
ions is called radius ratio. .
Number of atoms of Y in a unit cell = I '
Radius of positive ion (cation). r +
Number of atoms of Z in a unit cell = .!. x 6 == 3 Radius ratio = =_c_
2 Radius of negative ion r _
a
Empirical fonnula of the compound == X'YZ3] ,
Common coordination numbers are 3, 4; 6 and 8.
38. In a crystalline solid, atoms of X fonn fcc packing and the
atoms of Yoccupy all octahedral voids. Ifall the atoms along The following table shows the radius ratio values, permitted
one body diagonal 'are removed then the simplest fonnula of coordination numbers and the shapes of ionic crystals:
the crystalline solid will be :
(a) XY (b) X 4Y3 (c) X sY4 (d) X 4YS Radius ratio . Permitted Arrangement of
coordination .anions round the Example
(r/ I r;;)
[Ans. (c)] number cations
[Hint: Number of atoms of Xin fcc packing (at comers and face 0.155- 0.225, 3 Plane Triangular B2 0 J
8 x .!. +6 x .!. = 4
centFes of cubic unit cell)
, 8 2 0.225- 0.414 4 Tetrahedral ZnS
Number of atoms of Yat octahedral voids = 4 0.414- 0.732 ·6 Octahedral NaCI
Along one body diagonal there are two X atoms and one Yatom. 0.732-1.000 8 Cubic (body-centred) CsCI
Number of effective atoms of X after removal
Types of Structure of Ionic S'olit:
I 15
4 2x-=- Crystal structure of ionic solids are described into following
8 4
, . types: .
Number of effective atoms of Y after removal = 4
, 1
Crystal structure I
X:Y=~:3 (Type)
Example
4
= 5:4 1. Rock salt NaCI, LiCl, KBr, Rbi, AgCI, AgBr, FeU, LiiV
.. Simplest fonnula = Xs14 ] 2. Cesium chloride CsCI, CaS, CsCN
3. Fluorite CaF2, U0 2, BaCi2 , HgF2
4.23 TYPES OF CRYSTALS 4. Antifluo'rite K20, K2S, Li 20, Na20, Na2S
Crystals are classified into four main types depending upon the 5. Nickel Arsenite NiAS, NiS, FeS, CoS
nature of forces that hold the constituent particles together in the
crystal lattice. . 6. Rutile Ti0 2 , Mn02 , sn02
1. Ionic crystals: The forces operating in ionic crystals are 7. Perovskite CaTiO:;, BaTiOJ • SrTiOJ
, /
, electrostatic. The lattice points in such cryslals are occupied by, 8. Zinc blende . ZnS, CuCI, <;::dS, HgS .
positively and negatively charged ions. Each ion is surrounded by (sphalerite)
the largest possible number of oppositely charged, ions .. This
number of oppositely charged ions' surrounding each ion' is 9. Wurtzite ZnS, ZnO, BeO, M~S, AgI
termed its co()rdination number. The coordination numbers of Packing of ions in ionic crystal (Formation of NaC!
positive or negative ions Diay be same or different: For example, crystal): The formation ofNaCI crystal can be explained in the
in .sodiu~ chloride, each Na + ion is surrounded by six Cl- ions· following manner. The two ions fonn one ion-pair of opposite
and each CI- ion is surrounded 'by six Na + ions. Thus, both the charges by the electrostatic f"rce of attmction. Each of the ions
~62 J G,RB. PHYSICAL. CHEMISTRY FOR COMPETITIONS
has a strong residual field around it and will naturally attract Here,4r_ =..fia and (2r_ +'2r+) a
!qlother ion-pair much. in the same way as two magnets attract Pacldng fraction (<Il) :
each other, i. e., a cluster is formed. Two clusters combine
1
3
together to give it unit cell. Finally, large number of un# cells .<I>=4x-n
4 - J
+r! ) =1t- [(r+ +1.
unite togetHer to form ttv"ee-dimemsional cubic crystal. . 3 a3 3J2 r_
The unit cell of sodium chloride has fom sodium ions and four
chlotide ions.
(ii) Wurtzite structure: It has hexagonal close-packed Fe 3+ ions to maintain electrical neutrality. :'~i]P": .'
. ' . ~~r'::J'~J ". .
(hcp) structure. S2- ions adopt hcp arrangement and Zn 2+ ions [Normal Spinel Structure.: Spinel is the coililrioli ruiIile ·of.
occupy half of the tetrahedral sites. . .. . the mineral, MgAl204' ne. crystal structlii'e of this mitieral is
.The above structures are termed 4 : 4 arrangement· 'possessed also called spinel structure. In this .type of structUre, both
by ZnO, AgI, SiC, etc. tetrahedral and octahedrill voids' are sinl'ultaneously occupied.
CaF2 crystal: The Ca 2+ ions are arranged in cCp General formula of the compound having spinel structure .is .
arrangement, i. e. , Ca 2+ ions are present at all comers and at the
°
AB 2 4 where' A' stands for a divalent cation apd' B' stands for a' : .
trivalent cation; It has a cubic .close packed arrangement of oxid~ ,
centre of each face of the cube. The fluoride ions occupy all the ions. Half of the octahedral voids are occupied b}'trjvalent.·
tetrahedral sites. This is 8 : 4 arrangement, i. e. , each ca
2+ ion is cations and one-eighth of the tetrahedral voids are occtipiedby
surrounded by 8 F - ions and ea~h F - ion by four Ca 2+ ions. divalent cations. ..... .
Ferrites are ·the spinel type compo~ds" having the general
formula AFei04where A stands for divalent catioh such as
./ + ../ ../ Zn?+. F~rrites are used for~ing powerfiil, permanent" and
• . •
."", /' ..,/
nOIi-rustingmagnets. Ferrites are used in telephones and memory
, ,
• ... • \ I
unitS of computef\'J . .
- i/
.. •
..,/ ./ 2. Structure oi1ce30 4 : Magnetite, Fe 30 4, is considered as a
./ ,
,, ,,,
./ -/; ,, . mixed oxid,e. .It contains mix~e of FeOand Fe 20 3. It has aD.
• , ' I,,
,~ • hiverse sp,inei sttucture. Oxide ions (0 2-) from face-centred
~
, /" -V'''/
~ ,,/
/" c~bic arr~geme~t. Dipositive ions (Fe2+) are present in
:,i octahedr~l v~i&' and tripositive ions (Fe 3+) ~eequally
Fig. 4.51 Fluorite structure-Structure of;calcium fluoride distributed among tetrahedral and octahedrai voids.. .
Number of 0 2- iolls in the'unit cell . = 4
Structure of Sodium Oxide.(~a20),.......Antifluorite Thus, Number oftetrahedral voi~ = 8
. Structure fl; . . . and Number of octlhedralJ\Toids = 4
Sodium oxide ·has antifluorite structure. The structure is . N~ber-ofFe2+ ions present in octahedral void = 1 .
similar to the structure of calcium fluoride with the :differenc.e . Number ofFe 3"t ions pr~sent ill tetrahedral void = 1
that the anions occupy .the positions of cations and vice-versa.
. N~beT of Fe 3+ ions present in octahedral void = 1
(i) .It has cubIc close packing arrangement of 0 2- ions, i.e., .
Thus, half~f1he octahedral voids ~e OCCUpied by Fe 2+ and
.these ions are present at the comers and !it the centres of all the
Fe 3+ ions and o'ne-eighth of the tetrahedTal voids are occupied by
six faces of the unIt. Sodium ions on the other hand, are present at· .
fe"3~ ions: . ,', . .
the sites ofall the tetrahedral voids ..
\ '-"
."
-!F., .
... ~
264. I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
3. Structure of Fei)3 : If all the Fe 2+ ions are replaced by different elements. These atoms are held together by covalent
Fe + ions, then ~ every three Fe 2+ ions can be replaced by two
3 bonds. Covalent crystals are of two types:
Fe 3+ ions. to maintain electrical neutrality, the ratio between Fe (i) The covalent bonds extend in three~dimensions fonning a
°
and will now be 2 : 3, i.e., we get Fe203' giant interlocking structure. Examples are diamond, silicon
carbide (SiC), aluminium nitride, etc.
Properties of Ionic Crystals
In diamond, each carbon atom is Sp3 ~hybridized and thus,
(i) Physical state: Ionic crystals are crystalline solids' at
covalently bonded to four other carbon atoms present at the four
room temperature. They are never liquids or gases under ordinary
comers . of a regular tetrahedron. This leads to a rigid
. temperature and pressure as the ions do not have freedom of
three~dimensional network. The entire crystal is regarded as one
. movement.
large carbon molecule and is called 'a macromolecule. The
Since, high energy is required to separate canons and anions structure of diamond explains the properties such as high density,
from one another from their alloted positions on accoun( of very non~conducting nature, extreme hardness and high melting and
strong. electrostatic forces of attraction, the ionic crystals: are boiling point of the diamond.
quite hard, have low volatility and have high melting and
boiling points.
(ii) .Electrical conductivity: Ionic crystals are insulators,
f. e. , do not conduct electricity in solid state. The reason is that
ions are held firmly in fixed positions in the crystal lattice and
cannot move when electric field is applied. However, when
melte~ they become good conductors of electricity, i. e. , ions
are free to move in liquid medium.
(iii) Solubility: Ionic crystals are soluble in polar solvents
or. solvents having high values of dielectric constant. They are
insoluble in non~polar solvents. When they in non~polar
medium colloidal solutions are formed, e.g., kerosine oil.
The dissolution of an ionic crystal in· a polar depends on • Carbon atom
the relative magnitudes oflattice and . ' Fig. 4.52 Structure of diamond
MX (s) + Energy ----7 M + (g)
(Ionic crystal) (Lattic~ energy)' . (ii) The covalent bonds extend in two~dimensions forming a
. giant layer. These layers are then held together by van der Waals'
M+ (g)+ x (Solvent) ~ [M (Solvent)x t +BEriergy
(Solvated ion) , (Heat of hydration)
forces. Examples are· graphite, boron nitride (BN), cadmium
X - (g) + y (Solvent) ----7 [X (Solvent) y
, (Solvated ion)
r+ Energy
,.;,~(Heat of hydration)
iodide, etc.
, In graphite, each carbon is sp2 ~hybridized and is thus bonded
~ ,,'
The ionic compound will be soluble if tota~'~ydration energy to three carbon atoms in the same plane. The C-C distance is
is higher thart lattice energy. \j
1.42 A which is intermediate between single bond distance (1.54
. ' Ionic crystals are good cJ}nductors in moit~lJ state or when A) and double bond distance (l.33 A). The unit cell consists of a
dissolved in water.' • 'f:';> ' hexagon of six carbon atoms. The unit cells are interlocked
(iv) Brittleness: Ionic solids are highly 'brittle in nature. giving a layer or sheet structure. The distance' between two
When external force is applied, these are easily broken into adjacent layers is 3.35 A. The structure explains the properties of
pieces. Ionic solids are composed of parallel layers which contain graphite such as being. soft, good conductor of electricity, flaky
cations and anions. When ~xtemal force is' applied, one layer and slippery.
slides a' bit over the other aQd like ions come in tront of each
other. Due to repulsion between two layers the ionic solid breaks
down.
Ionic crystals have high ,density due to close packing.
(v) Isomorphism: IonIC crystals possess same crystalline
structure, i. e. , show isomorphism if the ions (cations and, anions)
have same. electronic configuration. NaF and MgO are
isomorphous compounds.
Na+ F- and Mg2+ '
2,8 2,8 2,8
2 .. Covalent crystals: In covalent crystals, the lattice points Fig. 4.53 Structure of. graphite
are occupied' by neutral atoms either of same element' or of
"
STATES OF MAnER J. 265
In general, the packing of atoms in covalent crystals is loose in Ionic Covalent' Metallic Molecular"
Property
comparison to ionic and metallic crystals. Thus, covalent crystals , crystals crystals crystals crystals
have open structure. •
1. Constituent Positive'and [Neutral Ipositive ion IMolecules
3. Metallic crystals: The metallic crystals have positive particles negative atoms in polar
metal ions as lattice points surrounded by a sea of mobile occupying, ions sea of or non-polar
electrons. Each electron beiongs to a number of positive ions and lattice electrons
each positive ion belongs to a number of electrons. The force that points
binds a metal ion to a number of electrons within its sphere of i. Binding Electrostatic Shared Electrostatic !Weak polar
influence is known as metallic bond. Metallic crystals mostly force attraction pairs of attractions forces or van
electron's between 'der Waals'
belong to cubic face-centred (fcc), cubic body-centred (bcc) and
'IPOSitive ions forces
hexagonal close-packed (hcp) systems. Metallic crystals exhibit and electrons
the following properties: 3. Hardness Hard and Very hard Hard or soft Very soft
(i) Good conductors: On account of the presence of brittle
mobile electrons, metals are good conductors of electricity. The 4. Melting and High Very high High or low Low
electrical conductivity decreases with increase of temperature. boiling
This is due to the fact that positive ions also begin to oscillate point~
with the increase of temperature. The oscillation of positive ions 5. Electrical Bad Bad Good Bad
hinders the movement of mobile electrons. Metals are also good conductivity conductors; conductors conductors conductors'
conductors of heat. Good with few
conductors exceptions
(ii) Lustre: When freshly cut or scratched, most of the in fused
metals have a shining surface. When light falls on freshly cut state or in
surface, the electrons get excited. The excited electrons give off solution
energy in the form of light when they return to their original 6. Examples Ice, solid
r""I'.
NaCI, !Diamond, Cu, Na, Fe
position and hence the metal looks bright. The metallic properties IKN03, CO 2
are explained on the basis that the metallic bond is CaF2 igmphite,
carborun-
non-directional and non-rigid. The result is that M 11+ ions can be Idum
easily moved from one lattice site to' another. The nearest
neighbours can be thus changed easily and new metal bonds can ,.4.24 IMPERFECTION IN SOLIDS
be formed readily. This explains why metals are malleable and
An ideal crystal is one which has the same unit cell containing
ductile.
the same lattice points across the whole crystal. Any departure
(iii) Physical characteristics: Most of the metals are quite from perfectly ordered arrangement ofconstituent particles in the
hard and tough. They are malleable and ductile. They have high crystals is called imperfection or defect;
tensile strength. Except alkali metals, they have high melting and Perfect of ideal crystals can exist only at absolute zero or zero
boiling points. They also possess elasticity. Kelvin. At absolute zero the crystalline substances have zero
entropy; i.e., have no randomness. Above absolute zero-, entropy
4. Molecular crystals: In molecular crystals, the lattice points
or randoumess increases, i.e., some deviations from perfectly
are occupied by molecules which' do not carry any charge. The
ordered arrangem~nt takes places.
forces responsible for binding these molecules are dipole-dipole
attractions and van der Waals' forces. Dipole-dipole forces are The, imperfection may be intrinsic or extrinsic. Crystalline
present in solids when polar molecules occupy the lattice points as defects can profoundly after the properties of a solid material.
in the case of water. van der Waals' forces are more general and Imperfections or defects not only aher the'properti.es but also give
occur in all kinds of molecular crystals. The binding energy in rise to new characteristics. Extrinsic defects due to presence of
molecular crystals is" therefore, weak. Molecular crystals show the certain impurities give rise to interesting changes in the
following general properties: properties. For example, gem stones are crystals containing
impurities that 'give them beautiful colours. The presence ofFe 3+
(i) They are generally soft and easily compressible.
ions makes sapphire blue and Cr 3+ .ions presence makes ruby red.
(ii) They have low melting or boiling points. (Gems are actually crystals of Al 2 0 3 which is colourless).
(iii) They are bad conductors of electricity as the electrons are There are mainly two types of imperfections.
localised in the bonds. 1. Electronic imperfections
(iv) They have low density. 2. Atomic imperfections.
The following table provides a comparative summary of the
properties of various types of crystals:
266 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
I,. Equal number of cationic and 'Some ions are displaced from,
anionic vacancies 3re present in norinallattice sites to the intersti- Anion vacancies in alk;ali metai halides are .produced by
thisdefect. . , t i a l sites. ..<' ' , 'heating the metal' halides, in the atmosphere of alkali metal
268 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
vapours. Metal atoms get adsorbed on the surface of the metal . of the host ions, vacancies are created. For example, if molten
halides. Halide ions move towards the surface and combine with NaCl containing a little SrCI 2 or CaCI 2 as impurity is allowed to
inetal ions formed by the adsorbed atoms on account of their cool, some lattice sites will be occupied either by Ca 2+ ions or
ionisation. The electrons released in the process diffuse into the Sr 2+ IOns
. . Iace 0 f N a + Ions.
mp . For every C a 2+ Ion
. or Sr 2+ lon,
.
crystal and. occupy anion vacancies. The electrons trapped in two Na + ions are removed in the crystal lattice in order to
anion vacancies are referred to as F-centres. 'F' stands 'for maintain electrical neutrality. Thus, one of these lattice sites is
FarbeR, a 'German word, meaning colour. Greater is the number occupied by Ca 2+ or Sr 2+ ion and the other site remains vacant.
F-centres, more is the intensity of colour. For example, non-stoi- Cationic vacancies developed due to introduction of impurity
chiometric sodium chloride with excess sodium is yellow, non- cause higher electrical conductivity of ionic solids. Addition' of
stoichiometric; potassium chloride with excess of potassium is about 0.1 % SrCI 2 to NaCI increases the electrical conductivity
violet and non-stoichiometric; lithium chloride with excess of by 10000 times. Solid solution of CdCI 2 and AgCl is another
lithium is pink. example of this type of impurity defect.
(b) Excess cations occupying interstitial positions: Metal
excess defect may also be developed by the presence of extra Electric Properties of Solids
cation in the interstitial site. Electrical neutrality is achieved by On the basis of electrical conductivity, solids are divided into
an electron presence in another interstitial site. This defect is three categories:
similar to Frenkel defect. For example, when ZnO is heated, it (i) Metals (ii) Insulators (iii) Semiconductors
loses oxygen and turns yellow. Metals have conductivity 10 8 ohm-I cm -I and insulators
ZnO~Zn2+ +(1/2)02 +2e have10- 12 ohm-I cm- I .
(a) Metals possess high tensile stress. On heating, some covalent bonds are broken to give free
(b) Metals are usually hard and solid. eleetrons. These free electrons make it semiconductor.
(c) Some metals like alkali and alkaline earth· metals show Width of forbidden zone in semiconductors is very low; thus
photoelectric effect, i. e. , ejection of electron from metal surface on heating, electrons are easily tossed to conduction band from
when exposed to light of appropriate energy. valence band and conduct electric current.
(d) Metals have low ionization energy. (ii) Extrinsic semiconductors or Impurity
(e) Strength of metallic bond depends on the following semiconductors: These are formed by dopping impurity of
factors: lower or higher group.
Strength increases with: n-type Semiconductor
(i) increase in number of valence electrons, Dopping of higher group impurity forms· n-type
(ii) increase in charge on the nucleus, semiconductor, e.g., when 'As' is dopped to 'Ge', an extra
(iii) decrease in size ofpo~itive metal iO!l' valence electron of arsenic makes the mixture n-type
Valence band: Group of electrons containing valence semiconductor. Current carriers are negatively charged, hence
electrons. called n-type.
Conduction band: The free electrons for conduction
constitute conduction band. Extra valence
electron forming
Band structure of metals may be given as shown in Fig. 4.59. n-type semiconductor
Conduction band
Valence band
n-type Semiconductors
Conduction band
Valence band
, ./ , ./
, /Ge, /Ge, ./
Ge /Ge G-"e~_,c.-- p-hole
~ 'Ge ' Ga04---"Ge (electron
Ge/ 'Ge..... 'Ge/ deficient
/ 'Ge/ 'Ga./ 'Ge..... band)
Conduction band
-+-- Forbidden zone· / ' G e..... " . / "
Valence band p-type Semiconductors
Fig. 4.60
~."'~~~~~ Conduction band
(i) Intrinsic semiconductors:
These are insulators at room Acceptor le.vel
temperature and become semiconductors when temperature is Valence band
raised.
Fig. 4.62 p-type Semiconductor
G.A.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
. ",r.r
Insulators: Such substances do not conduct el~ctric current; (ii) Diamagnetic Solids
"'z='
their conductivity is very low. Width of forbidden zone between The solids, which are weakly repelled by external magnetic
valence and conduction band i&very big; hence electrons are not field, are called diamagnetie solids and the property thus
tossed from valence ' . . , e~hibited is called diamagnetism.
band to conduction Conduction band ." "In diamagnetic solids, all electrons have paired spins, i.e., only
ban.d. On heat{ng,,>~~\ .• ,.I'\' Forbidden zone ,fully filled orbitals are present. Examples are: NaCI, Ti0 2,
they decompose but .. Valence blimd Zr0 2, KCI etc. Some diamagnetic solids like Ti0 2 show para
do not' give free.···,;·· .... . ' < .... . .
magnetism due to presence of slight non-stoichiometry:
conducting " . . Fig. 4.6~ .'
electrons. . (Iii) Ferr0n:tagnetic'Sollds
Examples: Classiflcation of transition metal oxides The solids which are strongly attracted by external magnetic
field and do not lose their magnetism when the external field is
Metallic semiconductors InsulatorS removed, are called ferromagnetic solids. The property thus,
vo , FeO, V2 0 S MnO exhibited is termed ferromagnetism.
TiO ,Ferromagnetic substances can be permanently magnetised.
. Fe203,Mn203
C0 3 0 4 , Mn 30 4 Only three elements, iron (Fe), cobalt (Co) and nickel (Ni) show
ferromagnetism at room temperature. Some other examples are:
.CuO EuO, Cr02, etc. Cr02 is the oxide used to make magnetic tapes
CU20 for use in cassette recorders.
TiO and NbO become superconductors at low temperature, Ferromagnetism arises due' to spontaneous alignment of
about 2 K. magnetic moments due to unpaired electrons in' the same
direction as shown below (Fig. 4.65).
4;25 MAGNETIC PROPERTIES
t Parallel spin
I 11III 111 '1111 1t I
(I) ParamagnetiC Solids
(spin in the .
The presence of one or more unpaired electrons In an atom; . same direction)
molecule or ion gives rise to paramagnetism. Such materials are
weakly attracted in the field.· When they are placed in it magnetic Fig. 4.65 Ferromagnetism
field they become parallel to the field. Domain significance of
unpaired electrons are given below: Mechanism of magnetisation of ferroml!gnetic substances:
Unpaired electron in one atom interacts strongly with unpaired
electron of neighbourhood atom, thus they align themselves
'9i' .1> ~ rt spontaneously in a common direction in a small volume of solid
called domains. Magnetic moments of all atoms in a domain are /
..,~
parallel to each other hence the do'main possesses a net magnetic
-e.. J25 jO dipole moment. In absence of external magnetic field, the
,
direction of magnetic moments in different, domains' .are
'&.. ,f?! -6+ )0 randomly oriented in different direction. When external magnetic
field is applied then the domains in which-the magnetic moments
'(In absenoe of magnetic field) (In presence of magnetic field) are parallel to external field, expandat the expense of remaining
domains and ultimately all the magnetic moments align
Fig. 4.64
themselves in the direction of external magn~tic field.
,Resultant magnetic. field for n-unpaired' electrons may be
calculated as:
-- - --'--
External magnetic field .
f.!M = In(n+ 2)
The magnetic field produced by unpaired electrons is due to---
--
(a) their spin and (b }their orbital motion.
. Magnetic moment is measured in Bohr Magnetqn (BM)
, ~ , ~.
BM=-~: . .' ,
.. 4n.)iicF ' . Fig. 4.66 Magnetisation of ferromagnetic substance
f.!s = 1.73 8M (one unpaired electron)
f.!s ~.'2.83 BM (two unpaired electrons) (iv) Antiferromagnetic Solids
.. f.!s. = 3.87 8M (three unpaired electrons)
f.!s = 4.90BM (four unpaired electrons)
The solids which are expected to show paramagnetism or
ferromagnetism on the basis of unpaired electrons, but act~ally
"~.
1. Diamagnetic Repelled weakly in magnetic field. Such 'solids' have Benzene,·NaCi, ..... Insulators ,'/'
only paired electrons. ' .1l1l1l1l1l Ti0 2.,V20 S' etc.,
3. Ferromagnetic Also, have unpaired electrons, Strongly attracted 'in ii,iiii i F~,Ni, Co, cr02 Cr02 is us~ in au-
magnetic field. Such solids can be permanently magnet- dio, video tapes,
ised, On heating to a temperature called Curie Point,
these solids change to paramagnetic solid.
, '
4. Antiferromagnetic In these !lolids, unpaired electrons align themselves in Cr2C3' CoO, COP4' Used in the instru-
such away that resultant magnetic moment is zero. F~O:i' MnO, Mn02 ments of magnetic
susceptibility .
measurement
5. Ferrimagnetic Unpaired electrons align themselves in such a way ~hat i J. J. i J. J. i J. J. . F~04' ferrites
there is a net magnetic mom\:lnt. , OR·
iiJ.J.J.itJ.J.J.ii .
and so on
I
.272 I' G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
1. Piezoelectricity When a crystal of dielectrics is subjected to Development of charge in i Quartz and Used in mechanical
mechanical stress, then small magnitude cur- some part ofcrystal. IRochelle salt electric transducer,
rent is produced. It ,is called direct e.g., in record player,
Piezoelectric effect. transmission of direct
'signals, sounding of
. sea depths. '
2. Anti piezoelectricity In some solids, electric field develops me- Crystal suffers elastic defor~
chanical effect. mation in an electric field
3. Ferroelectricity "1 Plez,oelectriccrystals having permanent di- iii iii Ba TiO}, KH 2P0 4 Electromagnetic
. poles are said to possess ferroelectricity. Rochelle salt appliances.
, 'r, '
4. Anti ferroelectricity I' Pieioelectric crystals with zero dipole ~e PbZr0 3
said to possess anti ferroelectricity. Lead zirconate
" I
5. Pyroelectricity . Some polar crystals produce electric impulse Crystals of tartaric Used in fire alarms,
on heating. acid , and thermostat
, Superconductors
Copper and most other metals are good conductors of thereafter even higher values of Tc for other copper containing
electricity. But even the best conductors present some resistance oxides: 90 K for YBa 2 Cu 3 0 7, 125K for TI2Ca2Ba2Cu301O
to the flow of electricity and a part of electrical energy is and 133 Kfor HgCa2Ba2Cu308+x.[YBa2Cu307 is also called
converted into heat energy. Thus, generators, turbines, motors of 1-2-3 compound, i.e., I yttrium, 2 bariums and 3 coppers].
all kinds" transmission lines and other electrical equipment Room temperature 'Te' superconductors are yet to be
always operate at less than I 00% efficiency. .discovered. The great advantage of these materials that offer no
A superconductor is a material that loses all electrical electrical resistance is the elimination of heating effects as
resistance below a characteristic temperature called the superc 'electricity passes through. The energy saving and efficiencies
conducting transition temperature, ~.e., a superconductor that would be realised are substantial. Superconducting coils of
presents no resistance to the flow of electricity. wire could store electricity (in principle) forever, since no energy
Electrons move freely through a superconductor without any is lost. Thus, the energy can be tapped as needed. One of the most
resistance or friction. dramatic properties of a superconductor is its ability to levitate a
This phenomenon was discovered, in 1911, by the Dutch magnet. When a superconductor is cooled below its Tc and a
scientist Heike Kamerlingh Onnes, who found that mercury magnet is lowered towards it, the superconductor and magnet
abruptly loses its electrical resistance when it is, co'oled with repel each other and the magnet hovers above the superconductor
liquid helium to 4.2 K. Below' its critical t~mpeniture (Tc), a ' as though suspended in midair. The potential application of this
superconductor becomes a perfect conductor and an electric effect will be in the high speed, magnetically levitated trains. '
current, once started, flows indefinitely without loss of energy. Some applications of superconductors already exist. For
Most metals "become superconductors at very low temperatures example, powerful superconducting magnets are essential
"(generally around 2-5 K), but this temperature is far too cold for components in the magnetic resonance imaging (MRI)
any commercial applications. instruments used in medical diagnosis. Superconductors are also
Since, 1911, scientists have been searching for materials that used to make the magnets that bend the path of the charged
s\fperconduct or at, higher temperatures and more than 6000 particles in high energy particle accelerators. All the present
superconductors are now known. Niobium alloys are particularly applications, however, use' conventional :;mperconductors
good superconductors and in 1973, a niobium alloy, Nb 3Ge, was (Tc :5 20 K). Of course, the search goes on for materials with
found to show superconductivity at 23.2K. The situation changed higher values of Tc' For applications such as long distance
dramatically in 1986 when MiiDer and Bednorz reported a Tc of electric power transmission, the goal is a material that super-
conducts at room temperature. '
35K for the non-stoichiometric barium lanthanum copper oxide,
Bi:h La 2 - xCu0 4 , where x has a value of about 0.1. Soon
m··~
(a) calculate the length of the edge ofa unit cell. Example 10. A solid AB has the NaCI structure. Jfradius
(b) What is the distance between Cs + and CI - ions? of the cation A+ id20pm; calculate the maximum value of the
(c) Whatis the radius ofCs+ ion if the radius ofCrion is radilff of the anionB"". .:" ,
180pm?
Solution' We know that,
.
Solution: Since, NaCl has octahedral structure,
+
Thelin:riting ratio r~ = 0.414
(a) Z rB
M
Z 1, lCs+ + lCI- ::: ICsCl or
- =--=--=290pm
rB
rl 120
0.414 0.414
M 168.5
3 23 Example 11. You are given marbles of diameter 10 mm.
1= a x3.99x 6.023 x 10
They are to be placed such that their centres are lying in a square
168.5 bond by four lines each' of length 40 mm. What will be the
a = 4.123 X 10-8 <;m= 412 pm arrangement of marbles in a plane, so that, maximum number of
marbles elln be placed inside' the area. Sketch the diagram aMf
. (b) Distance between Cs + and Cl- ions derive expression for the number of marbles per unit area.
(lIT 2003)
aJ3 412 x.J3 = 356.8 pm
Solution:" In order to accomodate maximum number of
2
sph~:res, there should be hcp (hexagonal closed packing).
(c) res+ + '(r = 356.8
Area of square having spherical marbles 16cmz
res+ + 180= 356.8
Maximum number of spheres = 14 (full) + 8 (half)
res+ 176.8pm
Number of spheres = 18
E:x;ampie 8. If NaCl is doped with 10-3 mol per cent of
SrCl2 ' what is the concentration ofcation vacancy ? Per unit area (per cm 2) 18 1.125
16
Solution:
"
Na+ ' Cl- Nil+ cr Length PQ of square = 4 cm
I Cl- Na+
Number of cationic vacancies per mol
10- x 6~023 x 10
3 23
Cl- Na+
100
, ,',' Example 9. A metal crystallises into two cubic phas<;s,
c
face-centred cubic (fcc) and body-centred cubic (bce) whose
unit lengths are 3.5 and 3.0 A respectively. Calculate the ratio of
densities offcc and bcc. (IfF 1999) CD = 10 sin 60°:: 10.J3 sJ3
2
x At. mass
'Solution; Density offcc Example 12. Calc~late the density of diamond from .the
Av.no.xV1 '
fact that it has face-centred cubic structure with two atoms per
. . b Zz x At. mass, lattice point and a unit cell ofedge length 3.569 A.
and d ensIty 10 cc = -=-----
, ,'Av.no.xVz SoiuticJ1: Z::;: 8,M = 12
, 1'3 xp xN
Z::::--'---
M
For fcc Zl 4; VI = a 3 = (3.5 x 10-8 )3 '. ZM 8xl2
Densltyp = --'=,-:-.----'---:::--:----'---:;:::-
For bec . Z2 = 2; V2 = 0 3
= (3.0 X' W: 8 )3 1 N (3.569x 10- )3 x 6.023 X 1023
3 8
d fix
8
4 x (3.0 X 10- )3 = 1.259 :: 3.506g cm-3
d bee 2x (3.5 X 10-8 )3 , ,
i
I
STATES OF MA'fTER I· 275
Example 13. .An' element crystallises into a structure X 0.53 x 6.023 x 1023 .,
=~------~----------'-r---
which may he described by a cubic unit cell having one atom at 6.94
each corner of the cube and two atoms on one of its diagonals. If
=2
. the volume of this unit cell is 24 x 10-24 cm 3 and density of
'Example 17. Cu metalcry;tallises in face centred cubic
element is 7.2 g / cm 3 . Calculate the number of atoms present in.
lattice with cell edge. a 361.6 pm. What is the density of Cu
200 g of the element.
crystql? (Atomic mass ofcopper 63.5 amu, NA = 6.023 X 1023 )
Solution: Number of atoms in a unit cell (Z) 1 + 2= 3
reBSE-PM; (Mains) 20081
. l3 xp xN
Z~ t Solution: We know
M , 3 .
3 Z=a xdxNA
1 xp xN
M M
Z
d:::: ZM
24 x 10-24 x 7.2 x 6.023 x 10 23 ... (i)
34.69 a, 3NA
·3
__Mass
_ _ x 6.023 x 1023 Z:::: 4 for fcc unit cell; M :::: 63:5 g mor I
Number of atoms
Molar mass
tv.=361.6 x 10:- 10 cm; Nfl =6.023 x 1023
= 200 x 6.023 X 1023 ::: 3.47 x 1024
34.69 Putting these values in (i), we get
;'~:~~~Ejllmple 14. Analysis shows that nickei o~de has formula d= 4 x 63:5". = 8.94 g Co;-3 "
Nio,9S01' ,Whatfraction of nickel exist as Ni 2+ artil Ni 3+ ions? (36L6x 10- 10 )3 x 6.023 X 10 23 ' '
, .
Solution: Let number of Ni 3+ ions = x ';:::' 'Elample 18. An LPG cylinder' weighs 14.8' kg when
empty. When full, it weighs 29 kg and shows a pressure of 2.5
NumberofNi 2+ ions = (0.98 x) atm. In the course of use at 27°C, the weight of the full cylinder
reduced to 23.2 kg. Find out the volume of n.;,butane in cubic .'
Since, molecule is neutral, its total charge is zero.
metres used up at 27~C and1 atm. .
(+3 x x) + (0.98 - x)x2- 2:::: 0 (MoleculaFmass ofn butane == 58] ,ICBSE-pl\fr (!\1ains) 20081
Solution : Mass ofn-butane used = 29"': 23.2 == 5.8 kg
x =0.04, i.e., Ne+ = 0.04; Ni 2+ =0.94
Num·b er 'or moles of butane
' used 5800
- - ;:100
Example 15. . Calcium crystallises in face-centred cubi; . 5.8 '-.
unit cell with a = 0.556nm. Calculate denSIty if ' V = nRT ,lOOx 0.0821 300
(i) it contained OJ % Frenkel defect. P 1
(it) it contained 0.1 % Schottky defect. . " ~. ' == 2463 litre
Solution: (i) Frenkel defect does not alters the d~ity of
solid. '=2.463 m 3
4Ox4 Example 19. r and r _ represents radius of Na + and
+ "
Na ct. .'
cr ions respectively. If 'n' is the number ofNaClunits per unit
cell then give the equation you will use to obtain molar volume.
:::: 1.5455 g / cm 3 , [CBSE-PMT (Mains) 2009J
(ii) Schottky defect lowers the density of solid Solution: "Edge length of unit cell 'a':::: 2(r + + r - )
Na CI
known as kinetic gas equation, bas been derived. mor: ~d 'units of b are litre Of" dm or m • This equation is
2 3 3
=0.9213 x nus
218 GRB. PHYSICAL CHEMISTRY FOR COMPETITIONS
',7. ' Compressibility factor: The extent of d~viation ofa a - -'1_ (for,all gases)
real gas from 'ideal bebaVi~ur is expresse~in terms of v ~ 273
compress~bility factor, Z.
At constant pressure, increase involum~ of a gas, per degree
PV', .". rise of temperature percc of gas at O"C is called coefficient of
Z -'-; Z is unitless quantity.
" nRT 'l
j,:;. volume expansion., Similarly,.the pressure, coefficient' a p is
defined as, ' .
(i) Forideal gas Z =I ..
(ii) For real gas Z:;t 1. a p == PI -:- Po =-,1-' (l:'1.or aII'
gases)
When Z < 1, there is negative deviation from i4ealo'ehaviour . P0 x t 273 , . {7-
and the gas is' more compressible than itteaLgaS. (ii) CO, Nz., C 2 H4 and B2H.6 hllVe same moIir ma~s (28) and
, .When Z> 1, there' is positive' deviation ~~ideal behaviour shoW sarr,e rate of diffusion under id(lIltical cOfiditions. , . .
imd the gas is less compressible than ideal gast!· .' (iii), Atmolysis is the process 10 separate two gases on ·~he
, 8.· Critical ph~n9menon:, (i) Critical temperature is that basis, of difference in their deIl$ities and rate of diffusion...
temperature' abovi which,tbegas caDnQtbe liquefied with the _, (i~) Average molecular mass of air is 29. If a gas has
help o(pressure (ii) 'Critical pressure is the minimum pressure molecular mass less than air, it is lighter than air and if it has
required to liquefy the gas at critical temperature (iii) Critical moleCular mass greater than air, it is heavier than air, e.g., Cl 2
. ,volume is the volume ,occupied by one, mole of the gas at its (71), CO 2 (44) and S02 (64) are heavier than air, while H2 (2),
critical temperatu~ and critical pressure. , ije (4), NH3 (17) and H 20 (18) are lighter than air.
. , '. a, Sa . ' 11. Transport pheno~ena of gases:
, Vc =3b: PI;=;:; 27b2 T: = 27bR """.~ (i) Collision diameter (0')= Distance of closest approach
" Boyle's temperature: It is the temperature abovCII which ~he '. when two molecules are under collision. .
gas behaves like.. an ,ideal gas. In ~ of van der.Waals·
. .:'. .
':'~.:
, constants, ,:,1 ":r~·: ~·:l"·.':~
. . .' a
. Boyle's temperature(TB ) == -
.' . '. '. ' . Rb
I I,
. . .,' TB > T c , • t4-- 0' ----JIt1 '/
lattice or an .lU'rny of ~int~ wowing how molecules.. atoms Of Bra~ presented a re!atiooship Mtwoen the wavelen!lth of the
ions are lUTt\ngediu dltl'er~ut: sites, in tbfee..dimensiOMI space is . Xwrays and the distince between the planes,
called ~. lattice,
~""2dsina
.T1w mWlt>it fOpoati~ unit in a SpaQe lattic~· whiQh wlwn
oopoated over and over again f(I&ults in a crystal of tlw given Where, 11 is an inwger such as. l.~, 3... ,' A the wavdength, €I is is
su\:la~ce iii termed· ~t geU. A unit cell poss~ all the the distance between ~ting pJaues. of particles<md e the angle
stt\lctural propertieso~ t~given ct'Y~t The edges of the unit of deflection Of glancing aJlgle.
cell are desijMted as "a. band c, tl.OO the angl~ between thfee 18. eh;\r_ct.th:s;Qfcqbic·systernll:.
ll\U\ginary axes as a., tl mld YNS~tively. . (i), Number of. atorns~ per unit. cell: (a) Shnplc c.ubjc
16~ Cry$(lll sys~,rn$: . ~ven types of hasic or primitive • stTuc~ne atom PQr unit cell, (b) Fact}-centred cubic
unit cells have been fec~ised among crystals. ~ aN: atmcture-4 atoms per unit cell and (c) Body·oontred cubic
L Cubw . a:,;;; be :. c (t"" a,;
y 9(f NaCl. KCl. ZnS
structUre:-2 atoms per un\t cell.
2. onllofhomhic 4::#:b~c Q,.::;,~ 'f "" 9()? .KNO:!. BaSQ4 (it) DtI)sity oflaJticematter "" If XM3.
Noxa
3. 'r~.wg®al . (l ",,/1 '" cd:;;;. fl '" y '" 9tf NH~Qr, SnO:f
4. MOOOQlinic. a 'Ii b :;II. C l':( "" 'I:;; 9W • MooQQlimc sulphur, where; n is the number of atoms in wlit cell, M is the atomic mass
I.\.~ go:' caSO,* • 2H~O . Of molecular mass.. Nois Avogadro's number '\}ld a edge length
Qfthe cullic unit celt '. .
ail; b~r. Q.~*Y;; ~ CuSO<t·SH2O, .
• .~ a3aO~ .. (ill) . At011\icradi.u$~ .
Q ",1J, ~ C Q:;;; f:\ =i; ~; lnO. Agl. SiC • .(a) Simpk cubic ool~RadiusQfatom a
. ,,;;;;IN . 2
1. Rhom~ «""H,;c «:;;;f:\:;;;y.9tJ' NaN~.CaC03 (b) Fa\»Q(lnttOO cubic ceU'-""R~dius ofatom == ~
AU Q~ 00 not have simple la.ttiQt)S. Theft) can he 14 212
diffeNllt ways in wh~ similtw ptlints can be ammgedin a th.fee
Qi~ s~, T~~tals ~longi"g toa oubk syst~n haw (c) .&d)H~entfed cubic .U-Radiusoi;tom::
. .J3
4 a
thNe kinds of l""~: . . '"
(i) Sb.nple cubi~ Ja~c~i' Thew aN points only I.\t tb~ . I? Close.. packing, of constitueAts; It refers to the-
QQ.QWfS. Qf ~tlCh unit: . . arrangement in which constituen~upy maximum available
(ii) ,Fa~e~en~f't;~' ~~a,.i~ lattice:.. Th~w aN po~nts at the spape. The two common types of cl~ packing are:
,(a) AB AB ." arnmgement This· gives hexagonal close
oo.n\(IfS ai!w(\ll as at the centre of ~aQh Qfthe ~x faces of the cube,
packing. - .
(~1:l\WJy~c~p..ed.cp~i,-;Jant~~L 'Thew aN points at ~
eQrnt)fS. as w~U ~ in Ui~ centw .of each cv"be, (be) ABC ABC '" arnmgement. This gives CUbical close-
~king, •
., . Ty~ \\f~tti~ pOO.l! C~tiQn to ~ wU( ~ll
In ~ packing of constituents. some interstitial si~s aoo
c~ ~ left T~ ~tes aN te~ vtilds. ~ interstitial s.i~ between
E~ . K
fQur sphews is tetrah~ and betwee-n six spheres is ootah~.
. Fac~.wmrt< ~ T~ ~e QCQupied by hard spheres in hop; cep (fcc) is 14%;
800y~tr\i ') in bQc it is 68o/~ in simple cubic it is 52% and in diamon<l it is.
34O/~ thus. only fcc and hcpaN cl~ packed stl'\lC~s'"
•. "~\\~ Qf alj~i metals ~~Q~ ~ of·Cs..... ~wn . (i)· hQp is ~1 in lW. M~ Ca. Cr, Mo. V anct.2n.
tw~ QX~. _ $\\lph~ of ~l~ wtb··:tMWs
(-i) QQP is p~nt in Fe. Cu. Ag. A\L, ~. At and N\,
~~~ W Mdhalm· Q(.~lver ~~~ Ail ba'le ~ (m) bQQ ~nt in alkali metals, .is
SAlt (NiCl ~) st~~,
0'<') All ~ g~ ha"e C\lp structure except belium which
.• CsC•• Csllr. Cst, TiCl. T~ TU haw esC. ~ ~t\tN. has. hQP stf\\Qture. . .
• CUCl. C\\Bt. CuI, A3l. ~ ~w ~nQ. hl_ stf\\9tuw . If <»' a.phews. aN PNSJmt tn packtng. th~ the numbers of
(~AS~), •
te~l and ootahedral voids aoo 2n and n n:~tiv~ly. '
• StCl~, Stf'~. ·&Cl~, ~~, CdF l ' agF ~ ht\~~ tluoril~ 2(); TJt.~,:.coOJ:'d!n.atioJl! n.~~~r:. TOO n~aws.t neighbours.
(C~:a)~-' . . w_th whi~h a gi"en sphere is in cootact i&~led coordination
• N(\~Q, K~O,~~s,. K~Shave anmluoo~(Li~O~) ~,It ~nds "pQn struc~.
s~tuw.
(a) ~ «uhWSlruQ~: ~iMtioo numb« :: 6
17.', ~~ag(~ Ja~:, W~ x..~s ar~ In!.1\d~. on a ~~w (h) ~tNd ~ stNc~; c~natkm n\lIDbel' "" 12
~c, th~~ ~~t\t~iuto ~ Q~~atl(\ ~~ ~~l~ .:tn·
(c) ~~entredcu~ struc~; coordiMtioo numbfit "" 8
di~ut~ Ftom.~h oft~ p,l~ x~ aNQ~&Qt~,
STATES OF MATIER .1 281
For iook solids, th~ {aUo of the: radi~ C)f cation \0 that Qf throughout the whole of the crystal. At absorutelet'O, the crystals
anion is caUe\! radiuS" mHo, The: ta.dius ta.uo for a givcm are: ide:al put with rise in tempemtufe. 'there is a chance of
coordination n~mber is fixed, distortion, .T~ def~t may ~. at a point along a line or over a
For radius ratio (0,155- (U~) wordination nl.lmller = 3 surface. .
(i) SchQttky defect: This def~t is cau.sed if some of the
For radius ratio (6,225- 0,414) wordination num~r= 4., •
lattice points ~ woccupied, The Points which ~ unoccupied
For radius ratio (0,414- 0,132) coordination number = 6 ~ called vacancies or holes. The number of missing positive and
For radius ratio ({},732-1.0) cootdination numoor = 8
.
21. lIfypes of crystals: ~ing upon the: Ra~ of
. . . negative ions is the same and, thus. the crystal is neutral. Such
defect is conunon in ionic compounds with high coordination
forces that hold the constituent pa.rticl~s. together. in the: crystal number where the ctations and anions are: of similar size, e.g"
.lattice, crystals ~ classlfie\!\nto four types: • . Nap, KCl. KDr, etc. ' •
.. (i) Ionic crystals: The fQrc.es are electrostatic,~ la~ (fi) Frenkel~: This defectt is cau.sed when some of the
points. are occupied by pos"iv~l~d. ne:gati'l~ly charged looS, ~ ions Qf ~ latti~' ~upy interstitial sites leaving lattice sites
These crystals <U~ quite hard, haw low volatility and have: hig.h vacant ~his defoot appears generaJly in ionic crystals in which
melting and boiling points.. These are ins\da\OfS. hl.lt bewme- good anion is much latger in sae than th.. cation, e,g.. Agar, ZnS.
contructors in molten state, Th~se a~ solubl~ in polat solvtnts .. In ~hottk.y defoot, density decteases while in Frenkel defect it
and highly brittle in natu~, NaCl. KCl. '&C1 2 , etc" belong to this remains the same, In both the defects. electrical conductivity is
class. • observed to SQOl.e: extent The ovetall ~hero.ical cOmposition of
. Oi) Coyalent crystals:', The wnstlwenl ~rtkl~. are the the substance dOes. not change, Howe., there ~ other defects
atoms of same or different elements. whi~ ~ hdd by strong . in which there is change in ovet'all chemical combination, Such
covalent bonds, These SQlids ~. ye:ry hard and have: very high defects ~ ~ aq.s~tfk defects. In such crystals,
melting points., Diamond and catOOnmdum ~lQ~ to this. class.. there i~~ of oitbel' pooitive pmicles or negative particles,
(iii). Metallic crystals: . Th~ m~alli~ cfyst~s. have positiv, Howev•• the ~s~ is. neutn\l in natwo,'
metal ions. as. )attic~ points sult'Qunded by a sea of mobile Positive particle excess defects: (i). A. negative ion may 6e
electroni. Each electron belongs to a number ofpos.itive ions and missing ooro. the lattie» site which is ~Up\~ by an extra
each positive ion belongs \0 a number Qf e:l~trons, The f~e that ~lecttron. (ii) An ~itta'l)()sitive particle i& pment in the interstitial
binds. a metal ion to a number of ~lectrons is known as m~taUlc position, T~ maintain neutrality, an extra el~tron also occupies a
bond, Met~lliQ Qryst~ls' mOstly' belong. to fQC. bec I;Uld he-p pla.~ in the intetstitial sJ)aCf. Such crystals are u.sually col~
systems, These are good conductQl'S, possess lustre: and aw hard, . and semiconduQtors..
tough. malleahle and ductile in na~, Positive particle deficiency defect! One of the positiv~
(iv) , Molecular crystals: The constitu~nt witsofm()l~ular ~les may ~ missing. from its lattice site, The extra negative
crystals are molecul~s, Th~ forces holdin~ the molecu.les ~ charg~' may be balan~ if a nearby positive particle aQqwres
weak. van der Waals' fQrces, MQloo\lh.\r s~ds. ~ soft and ~~tra :pQsitive ch~, ~h ~stals are alSQ semtcxmductors.,
vaporise easily. These: ~ bad conductors. Qf elootriQity and J3x.ample-s. Me: FeO, FeR NlO, etc,
.p%sess.low den~ty,Examples aN ice. solid. CO~. etQ, C~in ®f~ts in crystals arls.e du.e to Pfe~~ of chemical
/. 22. Ddects. in crystals: A~ ideal crystal is the on~ which impurities. Ih~1l' are bQ.wn as impuritydll'~ts, .
has the same wit cell1loo.ntaining the same lattice points
282 G.R.B .. PHYSIC,4L CHE~JIISTRV FOF! :;::O~iiPET!TIOj\~S
-10 Ma~'l"TIx
Mat,-;h Type QU!':3tlolD§: [D] Match the Column-I with Column-II:
[A]Match the crystalline solids in Colun'm-I with the Column-I Column-II
coordination number of their ions in Column-II:
(a) Boyle's temperature (P) a/Rb
Column-I Column-II
(a) CsCl (P) Coordination number of cation = 8 (b) ~ (Inversion temperature) (q) 8a/27Rb
(b) CaF2 (q) Coordination number of anion = 4 2
(c) ZnS (r) Coordination number of cation = 4 (c) Critical temperature (r) The gas cannot be
(d) Na 2 0 (s) Coordination number of anion = 8 liquefied above this
temperature, on
[B] The diagrams below depict the different processes for a applying pressure
given amount of an ideal gas_ Match the Column-I and
Column-II: (d) Critical pressure (s) a/27b 2
l~ l.~
[E] Match the Colunln~I with Column-II:
.column-I Column-II
(a) Real gas at high. (P) PV=RT+Pb
v- 11N -,-+- pressure
(i) (ii)
(b) Force of attraction (q) PV= nRT
,among gas molecules
is negligible
(c) At high temperature (r) 2=1
and low pressure
T- T-
(iii) (iv)
(d) Real gas at N.T.P. (s) (p+ ;22}V - nb)= nRT
i -7 initial state,
f -7 final state [F] Match the Column-I with Column-II:
Column-I Column-II
Column-I Column-II
(a) Fig. (i) : System proceeding (P) Temperature will'
from initial state to final state remain constant 3
(a) Internal energy of gas (P) 2RT
(b) Fig. (ii) : System from initial (q) Pressure will
state to final state 'decrease (b) Translational kinetic
(q) ~RT
(c) Fig. (iii) : System proceeding (r) Volume will be energy of ~as molecules 2
from initial state to fmal state' constant (c) The temperature at which (r) ....:J.73°C
(d) Fig. (iv) : System proceeding (s) Temperature may , ~here ill no molecular
from initial state to final state mcrease or motion
decrease or may
(d) The lowest possible (s) 3.716 kJ at 298K
first increase and
temperattire at which gas
then decrease
molecules have no heat
[C] Match Column-I with Column-II for ideal gases:
[G] Match the Cp'IUmJ,,-I with Col\lmn·II:
Column-I Column-II
, Column-I (A)lumn-II
( a) If temperature of given (P) Average speed of gas
gas is increased will increase (a) NaCl (PJ Schottkydefimt
(b) If the pressure of a given (q) Root mean square (b) ZnS (q) Frenkel defect
, gas is increased at speed of gas molecules,
(c) AgBr'L (r) 'Develops yellow colour on heating
'constant temperature will increase
due to F-centre
(c) If the den~\ty of a given (r) Most probable speed of
(d) KCl (s) Develops blue/violet colour.on
'gas is lowered at ' gas molecules will
heating due to F-centre
constant temperature increase
"
~
[1] Match the crystal system in Column-I with Bravais lattice
in Column-II: (c) Most probable velocity (r)
-
1. A gas occupies a volume of 250 cm 3 at 745 torr and 25°c'
What atlditional pressure is required to reduce the gas volume
to 200 cm 3 at the same temperature?
PROBLEMS-
[AilS. 17.13]
[Hint: 11 == Pressure at the surface:; 1atm
== 76.0 x 13.6 x 981 dyne/cm2
[AiDS. 186.25 torr]. Pz == Pressure at a. depth of 50 m
2. A vessel of 120 cm3 contairis ~. certain mass of a gas at 20°C .= 76.0 x 13ix 981 + (50 x 100) x 1 x 981 dyne/cm 2
and 750 torr pressure. The gas was transferred to a vessel of == 981 [76.0 x 13.6 + 5000]
volnme 1'80 cm 3 • Calculate the pressure of the gas at the same = 981 x (6033.6) dyne/cm 2
temperature. .
[Ans. 500 torr] . Now apply Boyle's law; PI VI :; PzVz
3. A gaseous system has a volnme of 580 cm3 at a certain or == 76.0 x 13.6 x 981 = 0.1713
VI P2 ' 981 x 6033.6
pressure. If its pressure is increased by O.96Jiiltm, its volume
becomes. 100 cm3 . Determine the pressure of the system. % = 0.1713 x 100 = i7.13]
[Ans. 0.2 atm] 5. A sample of gas at room temperature is placed in an evacuated.
[Hint: p.;< 580 == (P + 0.96)100] bulb of v61ume 0.51 dm 3 and is found to exert a pressure of
4. A gas filled freely collapsible balloon is pushed from the 0.24 atm~ The bulb is connected to another evacuated bulb
surface level of a lake to a depth of 50 m. Approximately what whose volume is 0.63 dm3 • What is the new pressure'of the
per cent of its original v.,lnme will the balloon finally have, gas at room temperature?
assuming that the gas behaves ideally and temperature is same ~<\ns. 0.1074 atm]
/
at the surface and at 50 m depth?
284 G.R.B.' PHYSICAL CHEMIS1RY FOR COMPETITIONS
6. It is desired to increase the volume of 800 cm3 of a gas by 20% 15. Calculate the volume occupied by 5 g of acetylene gas at 50°C
keeping the pressure constant. To whattemperature should the and 740 rom of pressure. (liT 1991)
gas be heated, if the initial temperature is 22°C? IAns. 5.23 litre]
[Ans. 81Q.c] 16. Calculate the volume occupied by 7 g of nitrogen gas at 27°C
7. A chamber of constant volume contains hydrogen gas. When and 750 rom Hg pressure. (MLNR 1992)
the chamber is immersed in a bath of melting ice (O°C) the (Aos. 6.24 IiUe]
pressure ofthe gas is 800 tOtT. What pressure will be indicated 17. A spherical balloon of 2 I em diameter is to be filled up with
when the chamber is brought to 100CC? hydrogen at NTP from a cylinder containing the gas at 20 atm
[Ans. 1093 t o r r ] " and 27°C. The cylinder can hold 2.82 litre of water at NTP.
8. Calculate the volume occupied by 4.045 x I 0~3 molecules of Calculate the number of balloons that can be filled up....
(MLNR 1991)
oxygen at 27°C and having a pressure of700 tOtT.
[Ans. 17.97 dm).] [Aos. 10]
[Hiot: Volume of one balloon
' Nfl " 4,045 x IOn 0 672' P 700 atm ,
;: ~ nr3 ;: ~ x 22. x (21)).;: 4851 cm3
. lOt: o. 0 roo es n ::
[H '3:::';;; -
6.023 x 1O~ '760 ~.
3·372·
Now Use the gas equation, PY ::: uRT ]
;: 4.851 litre
9. Calculate the moles of hydrogen present in a 500 cm 3 sample
Let n balloons be filled; thus,. total volume of hydrogen used in
of hydrogen gas at a pressure of 760 rom ofHg and 27°C. filling balloons '.~
[Ans. 2.03 x 10-2 mol]
;: 4.85 I x n litre
(Hint: 500 cm3 :: 0.5 L, 760 rom ofHg = I atm. Now apply the.
Total volume of hydrogen in the cylinder at NTP,
. py)
gas equation, u '= RT Y =: 20 x 2.82 x 273,:::: 51.324 litre
300 x I
10. Calculate the volume occupied by' 4 mole of an ideal gas at
Actual volume ofH" 'to be transferred to balloons
2.S x Iff Nm- 2 pressure and 300 K temperature.
;: 51.324 - 2,82 (2.82 litre retained in the cylinder)
[Ans. 39.9 dro3] :::48.504 litre
[Hint: Y "" nRT , Given, n:: 4; R:::: 8314 NmK- 1 mol-I; . . 48 504
l' No. of balloons fined' n' '" - ' - == 10] .
, . 4.851
T = 300;1'= 2.5 x lOS Nm-2) i\
18•. An open vessel at 27°C is heated until three--fifth of the air in it
11. What is the volume occupied by 11 g of carbon dioxide at has been expelled. Assuming that the volume of the vessel
27"(; and 78.0 rom ofHS pressure? remains coostant. fmd the' temperature to which the vessel has
[Ans. tiliUe) been heated? (MLNR 1990).
(Hint: 780 rom of Hg = 780 atm; w '= 11 g; M "" 44 g mol-i. lAos. 477"C)
760 [Hint: Both volume and pressure are constant as the v:essel is
w RT open,
NowapplyY:: M .-;;-]
.'.e., nlBTI :;: n/tT2
12. A certain quantity ()f a gas occupies 200 mL when collected or "l""li
OVef watetat 15"C and 745 rom pressure. It occupies 182.6 mL "2 TI
in dry state at NTP. Firui the vapour pressure of water at 1soc.
IAns. Bmm] If Il, ;:. 1, I~;:
_. 1 -
3 2
-5
13. The density of a gas i~ found to be U)7 ~ L-I at 30°C and 2 T~
atmospheric pressure, What is its density at NTP?
-52 ::; -=-
300
or T? ;: 750 K 477' C ]
-
lAos. 1J49;L-I) 19. A gaseous mixture of He and 02 is found to have a density of
Dl~' D.. 0.518 g L-1 at 25"C and 720 torr, What is the per cent by mass
[Hiot: Apply F.I :: -:- R~"" P,. = -'" RT?
M - M -
ofheliwn in this mixture?
~;~ 1 [Ans. 19.88]
Dl', Dili (Hint: first detennioo the average molecular mass and then
14. At ~ top of a mountain." the ~m.eter reads O°C and the nUmbel- Qf ndes. ofheliwn and ox.ygen.
~ef ~ 700 mm Hg., At the bottom of the- mountain MoleS t)fhel~ = 0.665~ Moles. of oxygen = 0.335
the ~~ ~ lODe and \~ pressure 160 mm Hg. u_~ 4 x (t665
Com~ the ~ty of ~ ail' at the top with that at the 1,..,..".". per cent 0
f>..-*ti
no:1 wn => x 100
4 x 0.665 + 32 x 0335
oon~
[Ans. t.~ : I} ::: 19.831
[Hint: Density is in\'~tscl.}' ~ to "'~. 20. A sample ofoatural gas is 85,20/.. methane and 14.&0/0. ethane
by ~ What is the density of this mixture at IgoC and 748
dtQp- "" VI> '" T~I: ;: 303 x 100 '" un ] mmHg?'
~\O)ft\ VI 1; ~ 213 x 166 1 [ADS. 0.74gL- 1]
STATES OF MAnER 285
[Hint: Molecular mass of mixture, 29. At room temperature, ammorua gas at. one atmospheric
M =85.2 x 16 + 14.8 x 30 13.632 + 4.44 "" 18.07 pressure and hydrogen chloride at P atmospheric pressure are
100 100 allowed to effuse through identical pinholes from opposite
PM dRT ends of a glass tube of one metre length and uniform cross
d = PM =748 x 18.07 _ 0.74 L-I ] reaction. NH4 CI is first formed at a distance of 60 cm from the
RT 760 0.0821 x 291 g. end through which HCl gas is sent in. What is the value'of P?
[Ans. 2.198 atm]
21. 125 mL ofa gas A of pressure 500 mm is mixed with 200 mL r;;;- .
of another gas B at a pressure of 300 mm in a vessel of 150 mL [Hint:' rHel == I~ X PHC1 ]
capacity. What will be the total pressure of the resulting rNH3 VMHCI PNHl
mixture if the temperature is kept constant? 3<1. 'The rate of effusion of an unknown gas (X) through ~ pinhole
LAns. 816.67 mm] ...
is found to be 0.279 times the mte of effusion of hydrogen gas
22. Two vessels' whose volumes are in the ratio 2: 1 contain through the same pinhole, if both are at STP. What is the
nitrogen and oxygen at 800 mm and 680 mm pressures molecular mass ofthe unknown gas? [CEE (Bihar) 1991]
respectively, when they are connected together what will be
[Ans. 25.69]
the pressure of the resulting mixture? •
31. In a 2 m long narrow tube, HCl is allowed to diffuse in the tube.
[Ans. 760 mm]
from one end and NH3 from the other end. If diffusion is
23. A 10 litre flask at 298 K contains a gaseous mixture of CO· and started at the same time, predict at what poitit the white fumes
CO2 at a total pressure of2 atm. If 0,20 mole of CO is present, ofNH4 CI will form? .
find its partial pressure and also that of CO 2 ,
[Ans. NH4CI will form at 1.1886 m from the NH3 end of the
[Ans, Partial pressure of CO::: 0.49 atm; partial pressure of tube]
=
CO 2 1.51 aim] 32. The composition of air is approximately 80% N2 and 20%0 2
24. Calculate the total pressure in a mixture of 4 g of oxygen and
3 g of hydrogen confined in a total volume of one litre at o°c. by mass. Calculate density of air at 293' K and 76 cm Hg
38. At what .temperature will the rms speed of hydrogen be the 48. A chamber contains mono atomic 'He' at STP, determine its
same as that of oxygen at 25°C? number density.
[Ans. 18.62 K or - 2~4.38° C] [Ans. 2.68 x 1025 m-3]
39 .. Calculate the 'average rms and most probable speed of S02
[Hint: Number density = .!...
molecules at 27°C. kT
[Ans. 3.15 x 104 cm/sec, 3.419 x 104 cm/sec, (where, k= Boltzmann constant)
2.792 x 104 cm/sec] PV =nRT
40. The. average speed at temperature 11 and most probable speed . R
=(nxN )-T
4
at T2 . of CO 2 gas is 9 x 10 cm/ sec. I;;alculate the values of . N
11 and T2 • =(n x N )kT
[ADs. 1682.5 K, 2143.4 K] P nxN ..
- = - - = number denSity
4L How many times would the average molecular speed of kT V . .
nitrogen increase as its temperature is raised from -73°C and .Number density = 1.01 X !05 = Z.<i8 X 1025 m-3 ]
127°C? 1.38 x 10 2 x 273
[Ans. 1.414 times] 49. Two perfect gases at absolute temperature 11 and T2 are mixed.
42. A 4 : 1 molar mixture of He and CH4 is contained in a vessel at . There is 1\0 loss of energy. Find the temperature of the mixture
20 bar pressure. Due to hole in tlie vessel the gas mixture leaks if masses of molecules are ~ and "Iz and the number of moles
out. What is the composition of the mixture effusing out . _0f'i:he gases are nl and n2 respectively.
~ (in 1994)
.
initially? __ nlTI + nzT2 ]
[Ans.8:1] [Ans. T
nl + nz
[Hint: Partial pressure ratio of He and CH4 is 16 : 4. .
[Hint: Let final temperature is T
For diffusion rHe _ ~MCH4 X PHe 333
- niRTI + - nzRT2 = - (n i + nz)RT
rCH 4 M He PCH 4 2 22.
nHe = {16 x 16 =8 T = niTI + nzT2 ]
ncH 4 V4 4 ni + nz
i. e. , mole ratio of diffusion for He and CH 4 is 8 : 1.] 50. van der Waals' constant' b' for oxygen is 32 cm3 /mo!. Assume
43. Pure 02 diffuses through an aperture in 224 second, whereas b is four times the· actual volume of a mole of "billiard-ball"
mixture of O 2 and another gas containing 80% 02 diffuses O 2 molecules and compute the diameter of an 02 molecule.
from the same in 234 second. What is the molecular mass of 51. The speed often particles in metre/sec are 0, 1,2,3,3,3,4,4,
gas?' 5 and 6. Find (a) average speed (b) the root mean square speed
[Ans. 46.6] (c) most probable speed. .
44. 56 g of nitrogen are confined to a 6 litre flask at 37°C . [Ans. cav = 3.1 m sec-I, Sm, = 12.5 m sec-I, '1np = 3 m sec-I]
. Calculate its 'pressure using van der Waals' equation for
52. Using van der Waals' equation, calculate the constant' a' when
nitrogen. a = 4.17 atm litre 2 mol- 2 and b = 0.037 litre mol-I.
~o moles of a gas confined in a four litre flask exerts a
[Ans. 8.1l75atm] pressure of 11 atm at a temperature of 300 K. The valUe of' b'
45. One mole of carbon dioxide was found to occupy a volume of is 0.05 litre mol-I. (II~ 1998)
1.32 litre at 48°C under a pressure of 16.4 atm. Calculate the [Ans. 6.46 atm litre 2 mor2]
pressure that would have been expected froni: .
53. (a) Calculate the pressure exerted by 5 moles of CO 2 in one
(i) the ideal gas equation,
(ii) van der Waals' equation. litre vessel at 47°C using van der Waals' equation. Also, reRort
(a = 3.59 atm litre 2 mor I; b = 4.27 X 10-3 litre mol-I the pressure of the gas if it behaves ideally in nature. Given
. that a = 3.592 atm litre 2 mol-2, b = 0.0427 litre mol-I.
and R = 0.0821litre-atm K- I mol-I)
(lIT 2002)
. [Ans-: (i) 19.96 atm (ii) 18;64 atm] (b) If volume occupied by CO 2 molecule is negligible, then
46. GfllCJflate'the compressibility factor for S02, if 1 mole of it calculate tqe pr~ssure exerted by one mol of CO2 ga,sat 273 K.
occupies 0.35 litre at 300 K and 50 atm pressure. Comment on . (Ill' 2000)
the result. .lAns. (a) 77.218 atm, 131.36 atm and (b) 0.9922 aim]
[Hint: Z= PV = 50 x 0.35 = 0.711 54. A compound alloy of gold and copper crystallises in a cubic
nRT 1 x 0.0821 x 300 lattice. in which gold atoms occupy corners of cubic unit cell
Since, Z < 1; the gas S02 will be more compressible than ideal and copper atoms occupy the centre of faces of cube. What is
gas.] formula of alloy compound?
4~i The average velocity of gas molecules is 400 m/ sec. Calculate [Ans. AuCu 3]
its rms velocity at the same temperature. (lIT 2003) 55. A compound formed by elements A and B crystallises in the
[Alls. 434 m/sec] cubic structure where A atoms are at the corn~rs of the cube
STATES OF MIlIHER 287
and Batoms at the centre of the cube. What is the formula of e,,', , A metallic element crystallises into a lattice containing a.
the compound? sequence of layers of AB AB AB ... Any packing of spheres
AB] leaves out voids in the lattice. What percentage by volume of
56 A fcc element (atomic mass == (0) has a cell edge of 400 pm. this lattice is empty space? (lIT 1996)
What is its density? [Ans. 26%]
[i\ reS·. 6.13 g Cm'-3] 6-5.. A lead(II) sulphide crystal has an NaCI structure. What is its
density? The edge length of the unit cell is' 500 pm.
Apply density = Z X M ,Z= 4 and V", (4 10-8 )3
NoxV
X
=
No 6.023 x J02 3 ; atomic mass: Pb 207.2, S = 32.
cm 3 (1 pm = 10-12 m:::; 10-10 em)] 12.708 gem-3]
The unit eell of metalli:c gold is face-centred cubic.
The face-centred unit cell of nickel has an edge length of
(a) How many atoms occupy the gold unit cell?
352.39 pm. The density of nickel is 8.9 g cm- 3 . Calculate the
(b) What is the mass of a gold unit cell?
value of Avogadro's number. The atomic mass of nickel is 58.7
(a) 4 atoms (b) 1.308 xl021 g]
and 1 pm is equal to 1O- 1O cm.
C. 7. Polonium crystallises in a simple cubic unit celL It has atomic
6.029 X 1023 ]
mass 269 and density 91.5 kg m - 3 • What is the edge length of
:;~, The unit cell of aluminium is a cube with an edge length of its unit cell?
405 pm. The density of aluminjum is 2.70 g em-3 . What type [AsS', .15 ..59 x 10-8 em]
of unit cell of aluminium is? The unit cell of nickel is a face-centred cube. The length of its
[i,.as. The unit cell is face-centred] side is 0.352 nm. Calculate the atomic radius ofnickeL
Apply the formula, density = Z x M and find the value O.I24nm]
NoxV . 69. Determine the simplest formula of an ionic compound in
ofZ.] . which cations arl; present at the comers and the anions occur at
59" A substance forms face-centred cubic crystals. Its density is the centre of each face.
1.984 g cm-3 and the edge length of the unit cell is 630 pm. AB3; A and B are cation and anion respectively.]
Calculate the molar mass of the substance. Sodium metal crystallises in a body-centred cubic lattice'with
[A[['~' 74.70 g mOrl] cell edge, a = 4.29 A. What is the radius of sodium atom?
5Q', Molybdenum forms body-centred cubic crystals whose (lIT .1994)
density is 10.3 g em-3. Calculate the edge length of the unit 1.8576 A]
celL The molar mass ofMo is 95.94 g mol-I. [HiEt: 4r .J3a]
[.~[,s. 313.9 pm] : J' • If three elements P, Q and R crystallise in a cubic type lattice
An element crystallises in a structure having a fcc unit cell of with P atoms at the corners, Q atoms at the cube centre and R
an edge 200 pm. Calculate its density if 200 g of this element atoms at the edges, then write the formula of the compound.
contains 24 x t 02 3 atoms. PQR3]
4.166 g cm- 3] The first order reflection of the beam of X-ray from a given
200
[Hbt: Molar mass: x 6.023 x 1023 = 5fr.19 g mor l .crystal occurs at S'15'. At what angle will be the third order
24 x reflection?
=a3 (200 x 10- 10)3
For fcc, Z = 4, V 15° 56 ']
Apply density = ~ ]
The figures given below show the location 'of atoms in three
'. NoxV crystallographic planes in a fcc lattice. Draw the unit cell for
61.. The element chromium exists in bcc lattice. with unit cell edge the corresponding structure and identify these planes in your
2.88 x 10- 10 m. The density of chromium is 7.2 x I(Y kg m-3 . diagram. (liT 2000)
~m~
How many atoms does 52 x 10-3 kg of ChrOinium contain?
6.04 x 1023 ] '.}
-PYOBlECI!!e gUEmoNs ·
Set-1: Questions with single correct answer S6
[H int: liN '" -
I ~ 28 "" 2;
1. At constant temperawre, the product of pressure and volUlne·
ofa given amount ofa gas is Constant. This is: II-rl =xN~ X~()tal
(a) Gay-Lussaclaw (b) Charles' law l
= xIO=4atm~
(c) Boyle's law (d) Pressure law l+
2. A curve dra~ at constant temperature is called an isothenn. Po, :: lO-4 = 6atm]
This shows the relationship between: a
12. 273 n'll. of gas at stP was tlkel\ In ~7"C Ul\(l\SOO mm ~\lrt,
(a) P and.! (b) PVand V the final volume ()fthe gas \\IOllld be: . (CPMT 1992)
V tal 273 mt (b) 300 mt •
. i (c) 380 mt (d) S8~ mt •
(c) V and P (d)P and V
13. The density ot'the aas is equal to:. (CBSE 1991)
3. Charles' law is relJresented mathematically as:· (8) tIP (b) }JPIRT (e) Pj~T (d) MW
[P = PressUl'e, V::: Volul\te, r::: temperat\ll"e; R = Gas
(a)~ ". KV()1 . (b) l't "" KVo constant; It = nllmber()fmole, AI = mol~ularmass]
t
14. The density ()fa gas is 1.96,4 g dm-s at 273 K and 16 em Ha.
(c) ~.""Vo(I+2;3} (d) ~ =:Vo(l+ 2~3) the gas is: . .(KeET 2006)
(a) CH.. (b) C 21\ .(c) COl (d) Xc
4. Correct gas equation is: [UGET (Manipal Medical) 2006) 15. Compressed oxygen is sold at a pressure ()f 100 atMosphere In
(a) IV! ",,1; (b) ViT2 "" Vl 71 cylinder of 49 litre, the number ()f 1\\()les of o~b:\ the
8
P:<V2 T2 PI Pl cylinder is: ..
(a) 400 (b) 100 (e) 'lOG (d) :tOO
(c) ~1[ = P'J,T;2 (d) ViV, = p, P.
1[T2 I '). [Hint: One mole occupies a volume approi~mately l4.S Utre
Vi Vi
under ordinary ~tmospheric conditions,] . .•
5. In general gas equation, PV = nRT, V is the volume of:
16. If the pressure and absolute temperilwre of 2 litre of carbon
(a) n moles ofa gas (b) any amount ora gas
dioxide are doubled, the volume of carbon ,dioxide would
(c) one mole ofk gaS (d) one gram ofa gas become: • (eBSE 1991)
6~ In the equation of state of an ideal gas PI' = nRT, the value of (8) 7litre (b) S litre (c),4.lItre (d) 2 litre
universal gas constant would depend only on: (CPMT 1991) 17. One gram mole of a gas at NtP occupies 22.4 litr.e as "ol~me,
(a) the nature of the gas (b) the units of measurement This fact was derived from:'
(c) the pressure of the gas (d) the temperature of the gas (8) Dalton's theory (b) AvogadtQ's hyllt)thesis
7. The value of gas constant per degree per mol is approximately: (c) BerteHus hyllt)thesis (d) law of gaseous volumes *
WI~ 002~ ~3~ 004~ 18. 4.4 g ofCOz contains how many ntre of CO2 at STP?
8. Which one ofthe following is not the value of R? (AFMC 2004)
(a). 1.99 cal K- 1 mol-I (b) 0.0821Iitre:atln K- 1 mol- l (a) 2.4 litre (b) 2.24 litre (c) 44 litre (d) 22,4 litre
(c) 9.8 keal K- 1 mot' (d) 8.3 J K- 1 mol-I 19. Five gram each of the following gases at 8'7"C and 7S0 mm
9. One litre of a gas collected at NTP will occupy at 2 pressure are taken. Which of them will have the least volume1
. atmospheric .pressure and 27"C: • • , . ' , ( M L N R 1991)'
300' r ~ (b) 2 x 300 I'tre (a) HF (b) HC! (c) HBr (til Ht
(a) 2 x 273 ltre . , "2n 1 20. If molecular mass of02 and S02 are 32 and 64 respectively. tf
one litre of 02 at 15°C and 7S0 mm pressure contains N
273 r (d) 2 x 273 litre
(c ) -
2x -
300 ltre • 300 molecules\ the number-of molecules in two litre of S02 under
the same conditions of temperature and pressure will be:
10. 10 g of a gas at atmospheric pressure is cooled from 273°C to (MLNR 1991)
O°C keeping the volume constant; its pressure would become: (a) 2N (b) N (c} NIl (d) 4N
(a) -I atm I
(b) -.- atm (c) 2 atm (d) 273 .atm• n. Rate of diffusion ora sas is:
2' 273 (a) directly proportional to its density
11. 56 g of nitrogen and 96 g of oxygen are mi)(ed isothermally (b) directly proportional to Its molecular mass
and a total pressure of 10 atm, The partial,ressures of oxygen (c) directly propol'tional to the square of its molecular IbliS!!
and nitrogen (in atm) are respectively: IPET (KeraJa) 20101 (d) inversely proportional to the square root of its molecular millis
(a) 4, 6 (b) 5,5 (c) 2,8 (d) 8,2 22. The rate ofdiffusimt of hydrogen Is ·about: (CPMT 1991)
(e) 6,4 '(a) 0nG-halfthat of helium (b) 1.4 times that othellum
(c) twice that of heHum (d) four times that ofhellum
SrATESOF MATTER 289-
23. The rate of diffusion of methane at a given temperature is
(a) 1. (b) ~
twice that of gas X. The molecular mass of gas X is: 2 9
(lIT 1990; MLNR 1995) (c) I (d) 16
(a) 64.0 (b) 32.0 (c) 4.0 (d) 8.0 9 17
24. Some moles of 0z diffuse through a small opening in 18 35. A gaseous mixture of2 moles of A, 3 moles of B, 5 moles ofC
second. Same number of moles of an unknown gas diffuse and 10 moles of D is contained in a vessel. Assuming that
through the same opening in 45 second. Molecular mass of the gases are ideal and the partial pressure of C is 1.5 atm, the total
unknown gas is: pressure is:
(a) 3 atm (b) 6 attn (c) 9 atm (d) 15 atm
(a) 32 x (45)2 (b) 32 x (18)2
(45)z [Hint: 5 moles of C produce pressure 1.5 atm; therefore partial
(l8i
pressures of D =3 atm, B'; 1.5 x 3 =0.9 atm and
(c) (32i x 45 (d) (32)2 x ~ 5
18 45
A = 1.5 x 2 0.6 atm]
25. A bottle of dry ammonia and a bottle of dry hydrogen chloride 5
connected through a,long tube are opened simultaneously at 36. 50 mL of a gas A diffuse through a membrane in the same time
both the ends. The white ring first formed will be: as for the dif'fUSion of.40 mL of gas B under identical
(a) at the centre of the tube conditions of pressure and temperature. If the molecular mass
(b) near the ammonia bottle of A is 64; that of B would be: (CBSE 1992)
(c) near the HCI bottle (a) 100 (0) 250 (c) 200 (d) 80
(d) throughout the length of the tube 37. 3.2 g of oxygen (At. mass = 16) and 0.2 g of hydrogen (At.
. 26. 0.5 mole of each Hz, SOz and CH4 are kept in a container. A mass I) are placed in a 1.12 litre flask at O°C. The total
hole was made in the container. After 3 hours, the order of pressure of the gas mixture will be: (CBSE 1992)
partial pressures in the container will be : (a) I atm (b) 2 atm (c) 3 atm (d) 4 atm
ICET (Karnataka) 20091 38. Select the correct statement:
(a) Pso z > PCH 4 > PHz (b) PHz > Pso z > PCH4 In the gas equation;PV = nRT (CBSE 1992)
(c) PHz > PCH 4 > Pso 2 (d) Pso z > PH z > PCH 4 (a) n is the number of molecules of a gas
(b) n moles of the gas have volume V
27. The mass of 6.02 x 1023 molecules of CO is:
(c) V denotes volume of one mole
(a) 28 g (b) 14 g (c) 7.0 g (d) 56 g (d) P is the pressure ofthe gas when only one mole of gas is
28. 10 g of hydrofluoric acid occupy 5.6 litre·ofvolume at NTP. present '
The empirical formula ofthe gas is HF. The molecular formula 39. The density of a gas at 27°C and I atm is d. Pressure
of the gas will be (At. mass of fluorine 19): remaining constant, at which of the following temperatures
(a) H4F4 (b) HF will its density become 0.75d? (CBSE 1992)
(c) H3F3 (d) H2Fz (a) 20°C (b) 30°C (c) 400 K (d) 300 K
29. A.frre extinguisher contains 4.4 kg of CO2 , The volume of 40. If 4 g of oxygen diffuse through a very narrow hole, how much
CO2 delivered by this fire extinguisher at room temperature is: hydrogen would have diffused under identical conditions?
(a) 24.5 litre
(c) 10 x 24.5 litre
(b) lOOx 24.5 litre
(d) 1000 x 24.5 litre (a) 16 g (b) I g (c) i g (d) 64 g
30. The number of moles of Hz in 0.224 litre of hydrogen gas at
wl2
STP is: (MLNR ] 994) , [Hint:
(a) 1 (b) 0.1 (c) 0.01 (d) 0.001 4/32
31. A gas has a vapour density 11.2. The volume occupied by 1 g 41. A closed vessel contains equal number of hydrogen and
ofthe gas at NTP is: nitrogen molecules. The total pressure is 740 mm ofHg. IfNz
(a)IL (b)11.2L (c) 22.4L (d)4L moiecules are removed, the pressure would become/remain:
32. "The total pressure exerted by a number of non-reacting gases (a) double of740 mm ofHg
is equal to the sum of partial pressures of the gases under the (b) one-ninth of 740 mm ofHg
same conditions" is known as: (c) unchanged
(a) Boyle's law (b) Dalton's law (d) one-half of740 mm ofHg
(c) Avogadro's law (d) Charles' law 42. the pressure P exerted by a mixture of three gases having
33. Equal masses of methane and oxygen are mixed in an empty partial pres.sures Fi ,Pz and P3 is given b;..y·_,_ __
container at 25°C. The fraction of the total pressure exerted by
oxygen is: (a) P = p[ +P2 P3 (b) P = ~Fi + P2 + P3
(a)-
1 2
(c) - 1.
(d) x 273 (c) P Fi-PZ +P3 (d) P Fi +P2 +P3
3 3 3 298 43. Two sealed containers of same capacity at j:Qe same
34. Equal masses of methane and hydrogen are mixed in an empty temperature are filled with 44 g of hydrogen gas in one and 44
container at 25°C. The fraction of the total pressure exerted by g of CO2 in the other. If the pressure of CO2 is I atrn, what is
hydrogen is: the pressure in the hydrogen container?
(a) 1 atm (b) Zero atm (c) 22 atm (d) 44 atm
-
290 G.R.B. PHYSICAL CHEMISTRVFoR COMPETITIONS
44 .. Absolute zero is the temperature where all gases are expected (c) low temperature
to have: (d) high temperature
(a) different volumes (b) same volume 56. In a closed vessel, a gas is heated from 300 K to 600 K; the
(c) zero volume (d) none of~ese kinetic energy becomes/remains:
45. If a gas is heated at constant pressure, its density: (a) double (b) half . (c) same (d) four times
(a) will decrease (b) will increase 57. A mixture contains 56 g of nitrogen, 44 g of CO2 and 16 g of
(c) may increase or decrease (d) will·remain unchanged methane. The total pressure of the mixture is 720 mm Hg. The
46. Density of neon wilLbe highest at: partial pressure of methane is: (EAMCET 1991)
(a) SIP (b) O"C, 2 atm (a) 180 mm (b) 360 mm (c) 540 mm (d) 720 mm
(c) 273"C, 1 aJrn (d) 273°C, 2 atm 58.' The root mean square speed, of an ideal gas at 27°C is 0.3
, 47. Equal masses of ethane and hydrogen are mixed in an empty rnIsec. Its rms velocity at 927°C ,is: ,(EAMCET 1991)
container at 25"C. The fraction of the total pressure exerted by (a) 3.0 rnIsec (b) 2.4 rnIsec (c) 0.9 rnIsec (d) 0.6 rnIsec
hydrogen is: (lIT 199;J) 59. The rms speed at NTP of the species can be calculated from
(a) ] : 2 (b) I: 1 (c) 1 : 16 (d) 15: 16 the.expression: (EAMCET 1990)
48. Ac,cording to kinetic theory of gases:
(a) there are intemiolecular attractions
(a) f? (b) ~3: (c) ~3: (d) all of these
(b) molecules have considerable volume 60. At constant volume, for a fixed number of mole of a gas, the
(c) there is no intermolecular attraction pressure of the gas increases with rise oftemperature due to:
(d) speed of molecules decreases for each collision (a) increase in average molecular speed
49. Postulate of kinetic theory is: (b) increased rate of collisions amongst molecules
(a) atom is indivisible '(cl' increase in molecular attraction
(b) gases combine in simple ratio (d) decrease in mean free path
( c) there is no influence of gravity on the molec'llies of the gas 61. N.on-ideal gases approach ideal behaviour:
(d) none of the above '" (lIT 1999; KCET 2004)
50. Which of the following statements is not consistent with the (a) high temperature and high pressure
postulates of kinetic theory of gases? (b) high temperature and low pressure
(a) .Gases consist of large number of tiny particles (c) low temperature and high pressure
(b) .Particles are in const~t motion (d) low temperature and low pressure
(c) All the particles have same speed 62. The nltio of root mean square speed and average speed ofa gas
(d) Pressure is due to hits recorded by particles against the molecule, at a particular temperature, is:
walls of containing vessel (a) I: 1.086 (b) 1.086: I
51. A helium atom is two times heavier than a hydrogen molecule. (c) 2: 1.086 (d) 1.086: 2
At 298 K, the average kinetic energy of a helium atom is: 63. Most probable speed, average speed and rms speed are related
(a) two times that of a hydrogen molecule as:
(b) four times that of a hydrogen molecule (a) 1 : 1.224: 1.128 (b) 1.128: 1 : 1.224
(c) half that of a hydrogen molecule (c) 1 : 1.128 : 1.224 (d) 1.224: 1.128 : 1
(d) same as that of a hydrogen molecule 64. In a closed flask of 5 litre, 1.0 g of H2 is heated from
52 .. The kinetic theory of gases predicts that total kinetic energy of 300-600 K. Which statement is not correct? (CBSE 1991)
a gas depends 9n: (a) The rate of collision increases
(a) pressure of the gas (b) The energy of gaseous molecules increases
(b) temperature of the gas (c) The number of mole of the gas increases
(c) volume of the gas (d) Pressure of the gas increases
(d) pressure, temperature and volume of the gas 65. The root mean square speed is expressed as:
]112
~T
112 [
53. If a gas is allowed to expand at constant temperature then:
(a). [ %RT ] (b)
(a) number of molecules of the gas decreases
(b) the kinetic energy ~fthe gas molecules decreases
(c) the kinetic energy of the gas molecules increases (c) [3:] (d) [3:f2
(d) the kin~tic energy of the gas molecules remains the same
66. The rms speed ofhydrogenmoJecules at room temperature is
54. Gases deviate from ideal behaviour because molecules: 2400 m S-I. At room temperature the rms speed of oxygen
(a) are colourless (b) are spherical molecules would be:
(c) attract each other (d) have high speeds (a) 400 ms- l (b) 300 ms- l
55. Deviations from ideal behaviour will be more if the gas is
(c) 600 ms- I
(d) 1600 ms- I
subjected to:, .
(a) low temperature and high pressure
(b) high temperature and low pressure /
•
STATES OFMATIEFl
(b) r\ P + an22)
V
(V - b) = nRT
.
(c) a is small and b is large
(d) constants a and b are large
81. When the universal gas c~mstant (R) is divided by Avogadro's
(e) (P+;z](V+b)=nRT number (N), their ratiojs called:
(a) Planck's constant (b) Rydberg's constant
2 (c) Boltzmann's constant (d) van der Waals' constant
(d) P = nRT n a
(V - nb) - V2 82. The compr~s~ibility factor of a gas is defined as Z = PV. The
72. In van der Waals' equation of state for a non-ideal gas the term • RT
that accounts for intermolecular force is: . compressibility factor of an ideal gas is: [PMT (MP) 2004]
are:
rP + anV J
\
2
2
(V - nb)= nRT
84. A mixture of three gases X (density 1.0), Y (density 0.2) andZ
(density OA) is enclosed in a vessel at constant temperature.
When the equilibrium is established, the gas/gases:
(a) atom litre 2 mor z (b) atom litre mol-2
(a) X will be at the top of the vessel
(e) atom litre mol- 1 (d) atom litre 2 mort (b) Y will be at the top of the vessel
74. If 1000 mLof gas A at 600 torr and 500 mL of gas Bat 800 torr (c) Z will be at the top of the vessel I
are placed in a 2 litre flask, the final pressure will be: (d) will mix hOmogeneously throughout the vessel
(a) 2000 torr (b) 1000 torr 85. 16 g of oxygen and 3 g of hydrogen are mixed and kept at 760
(c) 500 torr (d) 400 torr mm pressure at O°e. The total volume occupied by the mixture
75. Two samples of gases A and B are at the same temperature. will be nearly: [CMC (Vellore) 1991]
The molecules of A are travelling four times faster than the (a) 22Alitre (b) 33.6litre (c) 44800 mL (d) 4480 mL
molecules of B. The ratio of m A / mB of their masses will be': 86. Which of the following expressions does not represent Boyle's
(a) 16 (b) 4 (c) 114 (d) 1116 law?
2
[Hint. mA C 2 ] (a) PV constant (b) VOC 1
2 P
ms C1
76. The root mean square speed of a certain gas at 27°C is (c) V1T2 = V21] (d) FWi = P2V2
3 x lO4 em s-!. The temperature at which the velocity will be 87. When an ideal gas undergoes unrestricted expansion, no
6x 104 cms-! is: . cooling occurs because the molecules:
(a) ~4°C (b) 108°C (c) 1200 K (d). 600 K (a) exert no attractive forces on each other'
77 .. The temperature at which real gases obey the ideal gas laws (b) do work equal to loss o( kinetic energy
over a wide range of pressure is called: mPMT 2009) (c) collide without loss of energy
(a) critical temperature (b) Boyle temperature (d) are above the inversion temperature
(c) inversion temperature (d) reduced temperature 88. Which of the following mixture of gases at room temperature
does not follow Dalton's law of partial pressures?
292 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(a) NOz and 0z (b) NH3 and HCI (a) N molecules of 02 (b) 2N molecules of02
(c) CO and COz (d) SOz and 02 N N
(c) - molecules of 02 (d) - molecules of 02
89. The speed possessed by most of the gaseous molecules is: 2 4
(a) most probable speed (b) average speed 100. A balloon filled with N20 is pricked with a sharper po~t and
(c) root mean square speed (d) none of these plunged into a tank of CO2 under the same pressure and
90. In which of the foHowing pairs the gaseous species diffuse temperature. The balloon will:
through a porous plug along with the same rate of diffusion? (a) be enlarged (b) shrink
(EAMCET 1(90) (c) collapse completely (d) remain unchanged in size
(a) NO, CO (b) NO, COz 101. The three states of matter are solid, liquid and gas. Which of
(c) NH3 • PH 3 (d) NO, Czl\; the following statements is true about them?
91. Which of the following statements is correct? (a) Gases and liquids have viscosity as a common property
(a) 3PV = mnc z is the expression for real gases (b) The molecules in all the three states possess random
(b) At normal temperature and pressure most gases behave translational motion
nearly as ideal gases (c) Gases cannot be converted into solids without passing
(c) The molecules of real gases have both volume and mutual through the liquid phase
attraction (d) Solids and liquids have pressure as a common property
(d) Pressure depends on number of molecules and volume 102. Strong intermolecular forces exist in;
92. For one gram molecule of an ideal gas: (a) gases (b) liquids
PV 3 . PV (c) amorphous solids (d) crystalline solids
(a) =-cal. (b) -=2cal 103. Association of molecules in water is due to: .
T 2 T
PV PV (a) covalent bonding (b) hydrogen bonding
(c) -:::: 8.31cal (d) -:::: 0.0821cal (c) ionic bonding (d) van der Waals' forces'
T T
104. Which of the following statements is wrong?
93. When helium is allowed to expand into vacuum, heating effect
is observed. This is due to the fact that: . (a) Evaporation is a spontaneous process
(a) helium is an inert gas (b) Evaporation is a surface phenomenon
(b) heHum is a noble gas (c) Vapour pressure decreases with increase of temperature
(c) helium is an ideal gas (d) The vapour pressure of a solution is always less than the
(d) the inversion temperature of helium is very low vapour pressure of a pure solvent
105. Normal boiling point of a liquid is that temperature at which
94. At STP,. the order of mean square velocity of molecules of
H2, N2, O2 and HBr is: (CBSE 1991) vapour pressure oJ 1'be liquid is equal to:
, ,,-.
I
STATES OF MATTER 293
111. The rise of a liquid in a capillary tube is due to: 120. A match box exhibits: (PET (MP) 19931
(a) viscosity (b) osmosis (a) cubic geometry (b) monoclinic geometry
(c) diffusion (d) surface tension (c) orthorhombic geometry (d) tetragonal geometry
112. With increase in temperature, the fluidity of liquids: 121. In the crystal of CsCI, the nearest neighbours of each Cs ion
(a) increa~s (b) decreases are: (PET (MP) 19931
(c) remains constant (d) may increase or decrease (a) six chloride ions (b) eight Cs Ions
113. If 111 and 112 are the coefficients of viscosity of two liquids, (c) six Cs ions .. (d) eight chloride ions
d l and d z their densities and tl and t z the flow times in 122. ,How many chloride ions are tberearound sodium ion in
Ostwald viscometer, then: sodium chloride crystal?
(a):!lL dl t 2 (b) .!!L=d2t z 003 008 W4 006
11z dzt l . 112 d 1tl 123. The number of atoms contained in one face-centred cubic unit
cell of monoatomic substance is:
(c) :!lL = dltl (d) :!lL = 1Pl\lT (Vellorc) 2006; PET (MP) 20071
'1z d zt 2 '12 d 1t2
(a) 1 (b) 2 (c) 4 (d) 3
114. Which of the following expressions regarding the unit of 124. The number of close neighbours in a body-centred cubic
coefficient of viscosity is not true? lattice of identical spheres is:
(a) dynecm-2 sec (b) dynecm2 sec-I
(a) 4 (b) 12 (c) 6 (d) 8
2
(c) Nm- sec =
(d) 1 poise 10- 1 Nm- 2 sec 125. The coordination number of each sphere in (hcc) arrangement
115. The boiling points of water, ethyl alcohol and diethyl ether are is:
100°C, 78.SoC and 34.6°C respectively. The intermolecular ' (a) 8 (b) 12 (c) 6 (d) 4
forces will be in the order of: 126. Bragg's law is given by the equation: (BHU 1990)
, (a) water> ethyl alcohol> diethyl ether (a) nA=28sin8 (b) nA=2dsin8
(b) ethyl alcohol> water> diethyl ether
(c) diethyl ether> et!,lyl alcohol> water (c) 2nA = d sin 8 (d) n 8 = ~ sin 8
2 2
(d) diethyl ether> water> ethyl alcohol 127. In Bragg's equation for diffraction of X-rays, 'n'represents:
116. The unit cell in a body centered cubic lattice is given in the (a) the number of mole (b) quantum number
figure. Each sphere has a radius, r and the cube has a side, a. (c) the order of reflection (d) Avogadro's number
What fraction of the total cube volume is empty.(T1FR 2010) 128. The coordination number for an atom in a primitive cubic unit
cell is:
(a) 6 (b) 8 (c) 10 (d) 12
129. The number of atoms per unit cell in a simple cubic,
face-centred cubic and body-centred cubic are . .
respectively:
(a) 1,4,2 (b) 4, 1,2
(c) 2,4, 1 (d) 4,8,2
130. In a solid lattice, the cation has left a lattice site and is located
at interstitial position, the lattice defect is: (VITEEE 2007)
(a) interstitial defect (b) vacarlcy defect
8 ? 4 ? (c) Frenkel defect (d) Schottky defect
(a) i--ft- (b) -3·ft-a3 131. Schottky defects occur mainly in ionic compounds where :
3 a3
(VITEEE 2008)
4 ?
(c) ~ (d) 2-3'ft a3 (a) positive and negative ions are of different size ,
(b) positive and negative ions are of same size
117. Which one is not the property of crystalline solid? (c) positive ions are small and negative ions are big
(a) . Isotropic (d) positive ions are big and negative ions are small
(b) Sharp melting point 132. What type of crystal defect is indicated in the diagram below?
(c) A definite and regular geometry Na+ Cl- Na+ cr Na+ Cl-
(d) High intermolecular forces Cl- Cl- Na+ Na+
118. The number of crystal systems known is: Na+ Cl- cr Na+ CI-
007 008 W6 004 Cl- Na+ Cl- Na+ Na+ (AIEEE 2004)
119. Tetragonal crystal system has the following unit cell
(a) Frenkel defect (b) Schottky defect
dimensions: (PMT (MP) 1993\
(c) Interstitial defect (d) Frenkel and Schottky defects
(a) a = b = c and a = ~ y = 90° = 133. In a closed packed array of N spheres, the number of
(b) a=b*canda=~=y=90°
tetrahedral holes is:
(c) a * b * cand a = ~ y 90° = = (a) NI2 (b) N
(d) a = b * c and a = ~ 900 , Y = 120°
(c) 4N (d) 2N
I
294 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
134. In a closed packed array of N spheres, the octahedral holes are: (a) They are anisotropic
(a) NI2 (b) 2N (c) 4N (d) N (b) They are rigid and incompressible
135. AB crystallizes in a body centred cubic lattice with edge (c) They melt over a wide range of temperature
length ~ a' equal to 387 pm. The distance between two (d) There is no orderly arrangement of particles
oppositely charged ions in the lattice is: [CBSE (PMT) 20101 145. Which defect causes decrease in the density of a crystal?
(a) 335 pm (b) 250 pm (a) Frenkel (b) Schottky
(c) 200 pm (d) 300 pm (c) Interstitial (d) F -centre
[Hint: Distance between two oppositely charged ions r;
146. For tetrahedral coordination number, the radius ratio l(;+ I is:
(r+ + r-) = aJ3 = 387xJ3 (KCET 2008)
2 2 (a) 0.732- 1.0 (b) 0.225:'" 0.414
335.14 pm] (c) 0.414 - 0.732 (d) 0.155 0.225
136. Germanium or silicon becomes semiconductor due to: 147. What is the total number of ions present in one unit cell of
. (a) Schottky defect (b) chemical impurity . sodium chloride lattice? (EAMCET 2006)
(c) Frenkel defect (d) none of these (a) 2 (b) 6 (c) 12 (d) 8
137. A particular solid is very hard and has a high melting point. In 148. The formula for determination of density of cubic unit cell is:
solid state it is a non conductor and its melt is a conductor of a3 N 0 - 3 (b) Z x No -3
()
a --gcm ---gcm
electricity. Classify the solid: [CMC Vellore (Med.) 2008) ZxM M xa 3
(a) 415xlO-23 joule (b) 2490 X 10-22 joule (a) 234.2 ml s (b) 342.2 ml s
(c) 1245 x 10-23 joule (d) 830 x 10-22 joule . (c) 432.2 ml s (d) 243.2 ml s
165. At a temperature T K, the pressure of 4 g argon in a bulb is P.
157. If increase in temperature and volume of an ideal gas is two
The bulb is put in a bath having a temperature higher by SO K
time~, then initial pressure of P changes to:
than the first one. 0.8 g of argon gas had to be removed to
[JEE (Orissa) 2006) maintain original pressure. The temperature T is equal to:
(a) 4P (b) 2P (c) P (d) 3P (lIT 1999)
158. The average kinetic energy of one molecule ofan ideal gas at (a) 510 K . (b) 200 K
27°C and I atm pressure is: (EAMCET 2009)
(c) 100 K (d) 73 K
(a) 900 cal K- I mol-I 166. ,At 2SoC and 730 mm pressure, 380 mL of dry oxygen was
(b) 6.21x 10-21 J rl molecule-I collected. lethe temperature is constant, what volume will the
(c) 336.7 J K- I molecule-I oxygen occupy at 760 mm pressure? (CBSE 1999)
(d) 3741.3 J K- I mol-I (a) 265 mL (b) 365 mL (c) 569 mL (d) 621mL
167. Which of the following solids shows electrical conduction?
[Hint: KE ~~T (CBSE 1999)
2N
(a) Graphite (b) Potassium chloride
=~x 8.314 x 300
2 6.023 x 1023 (c) Diamond (d) Sodium chloride
= 6.21x 10-21 J K- 1 molecule-I] 168. Schottky defect in solids is due to:
(PMT (Vcllorc) 2006; VITEEE 20061
159. The respective speeds of five molecules are 2, I.S, 1.6, 1.6 and
(a) a pair of cation and anion vacancies
1.2 km/sec. The most probable speed in km/sec will be: .
(b) occupation of interstitial site by a pair of cation and anion
(a) 2 (b) 1.58 (c) 1.6 (d) 1.31
(c) occupation of interstitial site by a cation
160. if one mole of a monoatomic gas ( y = ~) is mixed with one (d) occupation of interstitial site by an anion'
169. Copper crystallises in face-centred cubic lattice with a unit cell
mole of diatomic gas ( y ~). the value ~f y for the mixture is: . length of 361 pm. What is the radius of copper atom in pm?
[CBSE (PMT) 2009; AIEEE 2009)
(a) 1.40 (b) 1.50 (c) 1.53 (d) 3.07 (a) 108 (b) 128 (c) 157 (d) 181
161. The root mean square speed of hydrogen molecule of [Hint: a..fi = 4r
an ideal hydrogen gas kept in a gas chamber at (PC 361x..fi =4r
is 3180 metre/second. The pressure on the hydrogen gas-
r= 128 pm] ~
is: (density of hydrogen gas is 8.99 x 10-'2 kg 1m3 ,
J 70. The second OTder Bragg diffraction Qf X~rays with X = I A
1 atmosphere =-1.01 x lOS N 1m2) from a set of parallel planes in a metal oc<;!lfS at an angle of '
(a) 1.0 atmosphere (b) I.S atmosphere 60°. The distance between the scattering planes in the crystal
(c) 2.0 atmosphere (d) 3.0 atmosphere is: (CBSE 1998)
162. CH4 diffuses two times faster than a gas X. The number _of (a) 0.575 A (b) l.OOA
molecules present in 32 g of gas X is: (N is Avogadro number) (c) 2.00 A (d) 1.15 A
171. According to Graham's law at a given temperature, the ratio of
IEAMCET (Engg.) 2010)
the rates of diffusion rA I 'B of gases A and B is given ,?y: '
(a) N (b) N (c)N (d) N (JIT~998)
-a!
2 4 16 1/2 I12
(a) PA • ,MA (b)' MA . PA
[Hint: rCH 4
PB ( MB )
MB (PB J
'gas mCH4
2= rm; (C)PA:M B )
112
(d) MA .(PPB J
1/2
,
V16 PB ( MA MB A \
~=64 172. The root mean square~elocity of an ideal gas at constant
Number of molecules =__w_ _ x N pressure varies with density as: [IJT(Scrcening) 20(0)
molar mass
32 N
(a) 2 d (b) d (c) ..Jd (d) 1I..Jd
= 64 xN 2"] 173. Match the following:
_List~I List-II
163. At what temperature would the rillS speed of a gas molecule
(A) Inversion temperature (i)·a/ Rb
have twice its value at 100°C?
(B) Boyle's temperature (ii) 8a /27Rb
(a) 4192 K (b) 1492 K
(c) 9142 K (d) 24(}1 K (C) Critical temperature (iii) 2a / Rb
164. Find the rms speed of an argon molecule at 27°C (Molecular (a) A-(i), B-{ii), C-(iii) (b) A--(iii), B-{ii), C--{i)
weight of argon = 40 gm I mol): (c) A-(iii), B-{i), C-(ii) (d) A-(i), 8--(iii), C-(ii)
2961 G. A.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
174. For three different gases values of van der Waals' constant 'a' and (d) Cannot· be predicted unless the volumes of the gases are
'b' are given. What is the correct order of liquefaction of gases? given
Gases a b 183. Which of the following exhibits the weakest intermolecular
X2 1.3 0.090 forces? (AIIMS 2000)
Yz 4.1 0.023 (a) NH) (b) HCI (c) He (d) H20
22 2.2 0.075 184. The compressibility of a gas is less than unity at STP.
Therefore: [lIT 2000; PMT (MP) 2004]
(a) XZ>Yl>Z:! (b) YZ >22 >X 2
(a) Vm > 22.4 litre (b) Vm < 22.41itre
. (c) Z:! > Y2 > X z (d) Xl> 22 > Y2
(c) Vm == 22.4 litre (d) Vm 44.8 litre
175. Match the following:
List-I List-II 185. The rms velocity of hydrogen is J7 times the rms velocity of
(A) Pc (i) 3b nitrogen. 1fT is the temperature of the gas: (liT 2000)
(B) II;, (ii) 8al27bR (a) T(H z ) T(N2 ) (b) T(H2 ) > T(N z )
(C) Tc (iii) a I 27b 2 (c) T(Hz)<T(Nz ) (d) T(H z )=J7T(Nz )
(a) A-{i), B-{ii), C-{iii) (b) A-{iii), B-{ii), C-{i) 186. The kinetic energy of any gas molecule at O°C is:
(a) zero (b) 3408 J
(c) A-{ii), B-{iii), C-{i) (d) A-{iii), B-{i), C-{ii)
176. By what factor does the average velocity of a gaseous (c) 2 cal (d) 5.66 x 10-21 I
molecule increases when the absolute temperature is doubled? 187. Densities of two gases are in the ratio 1 : 2 and their
(DUMET 2010) temperatures are in the ratio 2 : 1; then the ratio of their
(a) 1.4 (b) 2 (c) 2.8 (d) 4.0 respective pressures is: (BHU 2000)
177. The van der Waals' constant' a' for different gases have been (a) I : I (b) 1 : 2 (c) 2: I (d) 4: 1
given as : 188. Gas equation PV == nRT is obeyed by: (BHU 2000)
Gas a(atm L2 mol-2) (a) only isothermal process (b) only adiabatic process
02 1.36 (c) both (a) and (b) (d) none of these
N2 1.39 189. An ideal gas will have maximum density when: (CPMT 2000)
CH4 2.25 (a) P=0.5atm,T=600K (b) P=2atm,T 150K
NH3 4.17 (c) P = I atm, T = 300K (d) P = LOatm, T == 500K
The gas that can be most easily liquefied is : 190. The following graph illustrates: (JIPMER 2000)
[JEE (Orissa) ZOIO[
(a) 02 (b) N2 (d) NH3
178. Match the following:
List-I List-II
(A) Urms /[jav (i) 1.22
(B) Uav IU nip (ii) 1.13
(C) UrmslUmp (iii) 1.08
(a) A-{iii), B-{ii), C-{i) (b) A-{i), B-{ii), C-{iii) Temp. (O"C) -
(c) A-{iii), B-{i), C-{ii) (d) A-{ii), B-{iii), C-{i)
179. louie-Thomson coefficient is zero at: (a) Dalton's law (b) Charles'law
(a) critical temperature (b) inversion temperature (c) Boyle's law (d) Gay-Lussae's law
(c) absolute temperature (d) Boyle's temperature
191. 4.4 g of a gas at STP occupies a volume of2.24 L. The gas can
180. At a constant pressure, what should be the percentage increase
be: [CET (Haryaua) 2000)
in temperature for a 10% increase in volume?
(a) 02 (b) CO (c) NO z (d) CO2
(a) 10010 (b) 11% (c) 8.9%' (d) 12.5%
181. 5 g of unknown gas has pressure P at a temperature T K in a 192. At O°C and one atm pressure a gas occupies 100 cc. If the
vessel. On increasing the temperature by 50'C, I g of the gas pressure is increased to one and a half time and temperature is
was given out to maintain the pressure P. The original increased by one-third of absolute temperature, then final
temperature was: volume of the gas will be: (DCE 2000)
(a) 73 K (b) 100 K (a) 80 cc (b) 88.9 cc (e) 66.7 cc (d) 100 cc
(c) 200 K (d) none ofthese 193. Pressure of a mixture of 4 g of02 and 2 g ofH2 confined in a
182. Which of the following expressions correctly represents the bulb of 1 litre at O°C is: (AIIMS 2000)
relationship between the average molar kinetic energy, KE of (a) 25.215atm (b) 31.205atm
CO and N z molecules at the same temperature? (e) 45.215 atm (d) 15.210 atm
[CBSE (PMT) 2000) 194. Density ratio of O2 and H2 is 16: L The ratio of their rms
(a) KEco == KEN 2 velocities will be: (AHNIS 2000)
(b) KEco > KEN z (a) 4: I (b) I : 16 (c) 1 : 4 (d) 16: 1
- --
(c) KEco < KENz
STATES OF MATTER 297
195. The rate of diffusion of a gas having molecular weight just 203. A crystal lattice with alternate +ve and -ve ions has radius
double of nitrogen gas is 56 mL S-I, The rate of diffusion of ratio 0.524, its coordination number is:
nitrogen will be: (CPMT 2000) IPMT (Manipal) 2002]
(a) 79.19 mL S-1 (b) 112.0 m'L s-l (a) 4 (b) 3 (c) 6 (d) 12
(c) 56 mL S-1 (d) 90.0 mL S-1 204. The major binding force of diamond, silicon and quartz is:
196. The density of air is 0.00130 glmL. The vapour density of air [MEE (Kcrala) 2002]
will be: (DCE 2000) (a) electrostatic force (b) electrical attraction
(a) 0.00065 (b) 0.65 (c) 14.4816 (d) 14.56 (c) covalent bond force (d) non-covalent bond force
197. If 300 mL of a gas at 27°C is cooled to 7°C at constant (e) van der Waals' force
pressure, its final volume will be: (AIIMS 2000) 205. A compound is formed by elements A and B. This crystallizes
(a) 135 mL (b) 540 mL (c) 350 mL (d) 280 mL in the cubic structure when atoms A are at the corners of the
198. For an ideal gas, number of moles per litre in terms of its cube and atoms B are at the centre of the body. The simplest
pressure P, gas constant R and temperature Tis: formula of the compound is: (DPMT 2009)
(AIEEE 2002) (a) AB (b) AB2 (c) A2B (d) AB4
(a) PTfR (b) PRT (c) PfRT (d) RTfP 206 .. The coordination number of a metal crystallizing in a
199. The van der Waals' equation reduces itself to the ideal. gas hexagonal close packed (hcp) structure is: [PET (MP) 20041
equation at: [MEE (Kerala) 2001; CBSE (PMT) 20021 (a) 6 (b) 12 (c) 8 (d) 4
(a) high pressure and low temperature 207. The crystal system of a compound with unit cell dimensions
(b) low pressure and low temperature a = 0.387, b = 0.387, c = 0.504 nm and a = ~ = 900 and
(c) low pressure and high temperature
y = 1200 is: (AIIMS 2004)
(d) high pressure alone (a) cubic (b) hexagonal
200. Which of the following volume (V), temperature (T) plots (c) orthorhombic (d) rhombohedral
represents the behaviour of an ideal gas at one atmospheric 208. The maximum number of molecules is present in;
pressure? (lIT (Screening) 2002; PET (Kerala) 2007] [CBSE (PMn 2004]
(a) 15 L ofH2 gas at STP (b) 5 L ofN2 gas at STP
(c) 0.5 g ofH2 gas (d) 10 g of O2 gas
(22.4 L
at 273 K)
~36373 at
8L
K)
(22.4 L
at 27~ K)
~28373 at
6L
K)
209: The root mean square velocity of one mole of a monoatomic
gas having molar mass M is Urms ' The relation between
average kinetic energy (E) of the gas andUrms is:
t . [lIT (S) 2004)
Vfl) I • Vel)
T(K)- T(K)-
(a) (b) (b)Urms ~:!
(22.4 L (22.4 L
(d)U
rms
= ~ 3M
E
at 273 K) at 273 K) 210. Which of the following is not a property of liquid state?
t t (14.2 L
VeL) .........._ - _ Vel) "--_a_t3_7_3_K) IBHU (Pre) 20051
(a) Intermolecular force of attraction in a liquid is quite large
T(K)- T(K)-
(b) All liquids accompanied by cooling on evaporation
(c) (d) (c) Lower the boiling point ·of a liquid, greater is its vapour
pressure at room temperature
(22.4L (d) A liquid boils at higher temperature at the top of a
at 273K) mountain than at the sea level
Vel) 211. A certain sample of a gas has a volume of 0.2 litre measured at
1 atm pressure and O°C. At the same pressure but 273°C, its
volume will be: [BHU (Pre) 2005]
T(K)- (a) 0.4 L (b) 0.8 L (c) 27.8 L (d) 55,6 L
(e) 212. When electrons are trapped into the crystal in an'ion vacancy,
the defect is known as: [BHU (Pre) 20051
201. The following is a method to determine the surface tension of (a) Schottky defect (b) Frenkel defect
liquids: feET (J&K) 2007]
(c) stoichiometric defect (d) F-centres
Ca) single capillary method (b) refractometric method 213. In'the equation of state of an ideal gas PV = nRT, the valueof
(c) polarimetric method Cd) boiling point method the universal gas constant R would depend only on the:
202. The crystalline structure ofNaCI is: rCET (J&K) 20071 (KCET 2005)
(a) hexagonal close packing (b) face-centred cubic (a) nature of the gas (b) pressure of the gas
(c) square planar (d) body-centred cubic (c) units ofthe measurement (d) none of these
298 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
214. If Z is the number of atoms in the unit cell that represents the (a) remain unchanged (b) be doubled
closest packing sequence ABC ABC ... , the number of (c) increase fourfold (d) be halved
tetrahedral voids in the unit cell is equal to: (AIIMS 2005) (e) be reduced to one-fourth
(a) Z (b) 2Z (c) ~ (d) Z [Hint: Use ~Vl = ~Vz ]
2 4 T, Tz
215. Equation of Boyle's law is: (I)PMT 2005) 223. To what temperature must a neon gas sample be heated to
(a) dP = _ dV (b) dP =+ dV double the pressure, if the initial volume of a gas at 7SOe is
P V .p V decreased by 15%? (PET.(Kerala) 20051
(c) d 2p = dV (d) d 2P = + d 2V (a) 319°e (b) 592°e (c) l28°e (d) 60 0 e
P dT P dt (e) 90 e
0
(a) ~r (b) ~r (c) 2r (d) ~r 224. The surface tension of which of the following liquids is
maximum? ICBSE (Pre) 2005)
217. ~fvrms is 30R I12 at 27°e, then calculate the molar mass of the (a) e 2 Hs0H (b) CH 30H (c) H 2 0 (d) C6H6
gas in kilogram: (DPMT 2005) [Hint: (c) Due to hydrogen bonding, H 20 has the highest
(a) I (b) 2 (c) 4 (d) 0.001 intermolecular force, hence its surface tension is also
maximum.]
[Hint: v rrns =~3~T 225. An element(with atomic mass = 250 g) crystallises in a simple
cube. If the density of unit cell is 7.2 g cm -3 ,what is the radius
30Rl12 = ~3 x RmX 300 ofthe·element? [JEE (Orissa) 2006)
(a) 1.93 x 10-6 em (b) 1.93 x 10-8 em
m =O.OOlkg]
(c) 1.93 x 10-8 A (d) 1.93 x 10-8 m
218. The pressure exerted bx,.1 mole of methane in a 0.25 litre
container at 300 K using van der Waals' equation (given [Hint: Z=13xpXNA
=
, a 2.253 atm L2 mol-z, b = 0.0428 L mol-I) is: M
. (JEE (Orissa) 2005) 1= x 7.2 x 6.023 x 1023
[3
(a) 82.82 atm (b) 152.51 atm 250
(c) 190.52 atm (d) 70.52 atm I =3.86 X 10-8 em·
219. An ionic compound has a unit cell consisting of' A' ions at the 1= 2r (for simple cubic unit cell)
corners of a cube and 'B' ions on the centres of the faces ofthe
I 3.86 X 10-8
cube. The empirical formula for this compound would be: r =- = 1.93 X 10-8 em]
IAIEEE 2005; CET (Karnataka) 20091 2 2
226. Dominance of strong repulsive forces among the molecules of
(a) AB (b) AzB
the gas (Z = compressibility factor): (AIIMS 2006)
(c) AB3 (d) A3B
(a) depends on Z and indicated by Z '" 1
220. Which one of the following statements is not true about the
effect of an increase in temperature on the distribution of (b) depends on Z and indicated by Z > I
molecular speeds in a gas? (c) depends on Z and indicated by Z < I
(a) The most probable speed increases (d). is independent of Z
(b) The fraction of the molecules with most probable speed [Hint: When Z> I, the gas is less compressible than ideal
increases gas and the repulsive forces dominate.]
(c) -The distribution becomes broader 227. Total volume of atoms present in a face-centred cubic unit cell
(d) The area under the distribution curve remains the same as of a metal is (r is atomic radius): (AIEEE 2006)
under the lower temperature 20 3 24 12 16
(a) - 1tr (b) - 1t? ('_ (c) - 1t? . (d) - 1t?
221. A gas can be liquefied: (AFMC 2005) 3· 0 3 3 3
(a) above its critical temperature 228. If we know the ionic radius ratio in a crystal of ionic solid,
(b) at its critical temperature what can be known of the following? (CET (Gujarat) 20061
(c) below its critical temperature (a) Magnetic property
(d) at any temperature (b) Nature of chemical bond
222. If the absolute temperature of a gas is doubled and the pressure (c) Type of defect
is reduced to one-half, the volume ofthe gas will: (d) Geometrical shape of crystal
(PET (Kerala) 2005]
STATES OF MATTER
r! --;J
(2/
C. Force Qf attraction is
negligible
(iii) PV = RT + (2/ V (c) (dTJ
dV
=K
p
(d)
,T T p
=0
D. Volume of molecules is
. negligible
(2 '\
j
(iv) ( P + V 2 (V - b) = RT 9. In the following statements :
(A) ideal gases are liquefied only at very low temperatures
(a) A (iv), B (ii), C (i), D (iii) (B) ideal gases can not be liquefied
(b) A (i), B (ii), C (iii), D (iv) (C) ideal gas behaviour is observed by real gases at low
(c) A (iv), B (iii), C (ii), D (i) pressures
(D) ideal gases do not exist
(d) A (iv), B (ii), C (iii), D (i)
The correct statements are: (ISAT 2010)
3. van der Waals' constants for three different gases are given:
(a)A,B,CandD (b) A, BandC
Gases (2 b (c) B, C and D (d) C and D
X 3.0 0.025 10. Which of the following relationships is/are not true?
I2RT
Y 10.0 0.030 (a) Most probable velocity ~ M
Z 6.0 0.035
Which is correct? (b)PV = ~kT
(a) Maximum critical temperature-Y
(c) Compressibility factor Z == PV
(b) Most ideal behaviour--X nRT
(c) Maximum molecular volume-Z
(d) Average kinetic energy of gas =..!. kT
(d) All are correct 2
4. What is the ratio of mean speed of an 0 3 molecule to the rrns 11. According to kinetic theory of gasi?s: (UT 1991)
speed of an 02 molecule at the same T ? (a) the pressure exerted by a gas is proportional to mean
(a) (3n 17)1I2 (b)(16J 9n )112 square velocity ofthe molecules
(c) (3nf2 (d) (4n/9)112 (b) the pressure exerted by the gas is proportional to the root
mean square velocity of the molecules
(c) oxygen has a higher ci:itical temperature and a higher [Hint: PV =nRT
inversion temperature than hydrogen
PV:::: W RT
(d) the critical temperature and inversion temperature of m
oxygen is very low W
U. 2 mole 'He' is mixed with 2 gm of Hz. The molar heat capacity Ro V:::: RT ... (i)
232
at constant pressure for the mixture is: w
PN V =-RT ... (ii)
(a) 17R (b) IlR (c)4R (d) 3R 2 28
6 6 2
P~ = 28
[Hint: C f\ for 'He' = 5 R; C P2 for H2 == 7 R PN2 32
· 2 2
nHe = 2; nH2 = 1
P~ =0.875PN2 ]
5 7 17. KCI crystallises in the same type oflattice as does NaCI.Given
nlC PI + nzC P2 2x-R+ Ix R
Cp 2 2 thatrNa + /'cr == 0.55 and rK+ /r,:T 0.74. Calculate the ratio
nl + nz 3
of the side of the unit cell for KCl to that ofNaCI
17R .
6
= ] [PET (Kcrala) 200S1
(a) 1.123 (b) 0.891 (c) 1.414 (d) 0.414
12. The van der.Waals' constant' a' for the gases 0z, N z, NH3 and
(e) 1.732
CH4 are1.36, 1.39,4.17 and 2.253 respectively, the gas which
can be most easily liquefied is: . [Hint: 0.74
. (a) 0z (b) N2 (c) NH3 (d) C~
[Hint: The van der Waals' constant' a' is directly proportional
to the intermolecular force; hence, the gas with greater value +I 1.55 ... {l)
of' a' can be most easily liquefied.] .
13. At what temperature will the molar kinetic energy of 0.3 mole r +
.1L + 1= 1.74 ... (2)
of 'He' be the same as that of 0.4 mole of argon at 400 K?
(a) 700 K (b) 500 K (cl 800 K (d) 400 K
'Cr
Dividing (2) by (I)
[Hint: KE 2 nRT 1.74
2 - =--"'---""-- x --"'-'---
n =1, for molar kinetic energy 1.55
(2 2
x Ix Rx T) Helium
(2 2
x 1x Rx 400) Argon
r
K
+ +r _
CI:::: 1.122]
rNa+ + 'el-
T=400K]
lS. 8: 8 coordination of CsCI is found to change into 6: 6 coor-
14. Let ~ and P be the saturated partial pressure and partial
dination:
pressure of water respectively. Then the relative humidity is
(a) on increasing the pressure
given by:
P (b) on increasing the temperature
. (a) Ps + P x 100 (b) - x 100 (c) on decreasing the pressure
Pa P,
(d) on decreasing the temperature
P
(c) ~ x 100 (d) (P + Pa ) xlOO 19. An alloy of Cu, Ag and Au is found to have copper constituting
P ccp lattice. If silver atoms occupy the edge-centres and gold is
15. Molar volume of a mono atomic gas at Po and To is 0.5 times its present at body-centre, the alloy has the formula:
molar volume at 10Po and at the same temperature. Ignoring (a) Cu 4 Ag 2Au (b) Cu 4Ag 4Au
the value of the van der Waals' constant 'a', the radius of the
(c) Cu 4Ag 3Au (d) CuAgAu
gas molecules is given by:
113 [Hint: In ccp an:angement, eu atoms occupy the corners and
(a) 0. 8RTo (b) Q. 6RTo face-centres.
[ )
Po Pr/f1t :. Number of Cu atoms = 8 x .! + 6 xl:::: 4
8 2
(c) l
(
3RTo
20Po N1t)
\113
I (d)
(
3RTo
20Po1t )
1/3
Number of silver atoms =Number .of edge - centres x!..4
=12x-41 = 3
where, N = Avogadro's number
16. A vessel is filled with a mixture of oxygen and nitrogen. At Number of gold atoms:::: I (at body -centre)
what ratio of partial pressures will the mass of gases be :. Formula of alloy =CU4Ag3Au]
identical? 20. The anions (A) form hexagonal closest packing and atoms
(M) occupy only two-third of octahedral voids in it; then the
(a) P(02) o.785P(N2 ) (b) P(02)= 8.75P(N2 )
general formula of the compound is:
(c) P(02) =114P(Nz ) (d) P(02) 0.875P(N2 )
(a) MA (b) A2 (c) M zA 3 (d) M3A2
I
STATES OF MATTER
21. In a face-centred cubic of A and B-atoms in which A atoms are 29. WhiCh of the following compounds represents an inverse 2: 3
at the comers of the unit cell and B-atoms at the face-centres, spinel structure')
one of the A-atoms is missing from one corner in unit cell. The (a) Felli [Fell Fe lll ]04 (b) Pb0 2
simplest formula of the compound is: (c) Al 2 0 3 Cd) Mn 3 0 4
(a) A7B3 (b) AB3 (c) A7B24 (d) A gB 2l 30. A solid solution of CdBr 2 in AgBr contains:
1 7 (a) Schottky defects
[Hint: Number of A atoms = - x 7 -
8 8 (b) Frenkel defects
1
Number of B atoms = 6 x - = 3 (c) Colour centres
2 (d) Frenkel as well as Schottky defects
A:B=7: 37 : 24 31. Which of the following cOlTectly represents the relation'
8 between capillary rise' h' and capillary radius 'r' ?
Molecular formula = A7B 24 ]
II~ 11\ .
22. Select the incorrect statement(s):
(a) Schottky defect is not shown by CsCI
(b) Frenkel defect is shown by ZnS
(c) hcp and ccp structures have different coordination hi
hi " -
numbers I ' f __
I
(d) at high pressure, the coordination number increases r_
23. Select the incorrect statement: (a) (b)
(a) In CsCI unit cell, r
Cs
+ + rCl - == J3
2
I
I
(b) In NaCI unit cell, rNa+ + rq_ 2
(c) In CsCI unit cell, 68% space is void
(d) In NaCl unit cell, 26% space is void
24. The ionic radii ofRb + and I - are 1.46 and 2.16 A respectively. r-- r -+
The most probable type of structure exhibited by it is: (e) (d)
(a) CsCI (b) NaCI (c) ZriS (d) CaF 2
25. Perovskite is a mineral with the formula CaTi0 3 • Which ofthe
[Hint: Capillary rise decreases with increase in the radius of
positive ions in the crystal is more likely to be packed in. the
tube.]
octahedral holes?
32. There is a depression in the surface of the liquid in a capillary
(a) Ti 4+ (b) Ti 2+ (c) Ca 2+ (d) O~
when:
26. Which of the following is incorrect ?[RHU (Sereening) 20(8) (a) the cohesive force is smaller than the adhesive force
(a) A real gas behaves like ideal gas over a wide range of (b) the cohesive force is greater than the adhesive force
pressure (- 100 atm) at Boyle point (c) the cohesive and adhesive forces are equal
(b) A real gas behaves like an ideal gas over a wide range of (d) none ofthe above is true
pressure (~ 100 atm) at critical temperature of the gas.
[Hint: Depression in the surface takes place When
a
Along one body diagonal there will be two X atoms, one Y A and balloon Bare 800 mL and 1800
atom and·two Z atoms are found and are removed . mL respectively. When the balloon
.' ' . I 15 system is heated; which one will
Number of atoms of X will be ::::: 4 - x 2 burst first?
, 8 4
Number;oi~t~ms of Y will be = 4 I ::::: 3 (a) Inner balloon (A)
(b) Outer balloon (B)
Number of'at6ms ofZ will be 8- 2=6
(c) Both balloons simultaneously
(d) Cannot be predicted
STATES OF MATTER 307
ptt=
(a) NH41 (b) MgO (c) MnO (d) ZnS
9. Which of the following compounds represent a normal 2: 3
t
P
!t
spinel structure?
(a) rv~gll AI~II04 (b) COil (Colllh04
(c) Zn(TiZn) 0 4 (d) Ni(CO)4
10. Which type of crystals contain· only one Bravis lattice?
v- p- (a) Hexagonal (b) Triclinic
(a) (b) (c) Rhombohedral (d) Monoclinic
11. At which temperature, is a fenimagnetic solid con....erted to a
ferromagnetic solid?
308 G.R.S. PHYSICAL CHEMISTRY FOR COMPETITIONS
~l/~v, I//p,
~,
(d) None of these
15. Which of the following diagrams correctly describes the (b)
behaviour of a fixed mass of an ideal gas? (T is measured in K) (aJ
[PMT (Kerala) 2007; eMS Vellore (Med.) 2008;
CET (Punjab) 20(8) -273°C 1°C
Temp(K) --II>
ConstantT Constant V (V1 > V2 > v:;) (P1 < P z < P3)
~
t t Isotherms isotherms
~ ~T'
p P
I
t ~T2
v- T-- (c) 11.,;
(a) (b)
Constant T Constant T Volume --+ - - P----'
i
PV
t
PV
(T1 < Tz < T 3 ) (T1 < Tz < T3)
p- V-
(c) (d)
. -
C~.~.(~I.}-~-----------I
Single correct option
1. td) 2. (a) 3. (e) 1. (c) 5. (a) 6. (d) 7. (b) 8. (d)
9. (a) 10. (c) 11. (a) 12. (c) 13. (d) 14. (b) 15. (c) 16. (d)
17. (a) 18. (b) 19. (c) 20. (c) 21. (c) 22. (a, c) 23. (c) 24. (b)
25. (a) 26. (c) 27. (b) 28. (b) 29. (a) 30. (d) 31. (b) 32. (b)
33. (c) 34. (e) 35. (b) 36. (a) 37. (a) 38. (b) 39. (d) 40. '(b)
41. (a) 42"/ (c) 43. (d) 44. (c) 45. (b) 46. (c)
7. 'The curve has which of the following characteristics? (a) zero refractive index (b) zero surface tension
(j)It has symmetrical distribution of molecules against (c) zero viscosity (d) zero critical temperature
molecular velocity, 7. Gas A can be liquefied at room temperature by applying
(ii)The area under the curve gives the total number of pressure but gas B cannot. This reflects:
molecules, (a) critical temperature of B is less than that of A
(iii)The maxima of the curve shifts towards right as the - (b) critical temperature of B is greater than that of A
tempe~ture is raised. ;< ~ (c) A and B have critical temperature greater than room
(iv) The area under the curve is independent of temperature, temperature
Select the correct statements from the codes given below: (d) critical temperatures of both are equal
(a) (i), (ii) (b) (i), (ii) and (iii) 8. The values of critical volumes of four gases A, B, C and Dare
(c) (ii), (iii) and (iv) (d) all are correct 0.025 L, 0.312 L, 0.245 Land 0.432 L respectively. The gas
with larger diameter will be:
(a) A (b)D
• Passage 3 (c) B (d) C
The essential conditions for liquefaction ofgases were discovered 4
[Hint: .Vc 3b 3x4Nx-nr'l]
by Andrews in 1869 as a result of his study of 3
pressure-volume-temperature relationship for CO2 , It was found that
above a certain temperature, it was impossible to liquefy a gas
• Passage4
whatever the pressure was applied. The temperature below which the Kinetic theory of gases is a generalization offered by Maxwell,
. gas can be liquefied by the application of pressure alone is called Boltzmann, Clausius, etc., to explain the behaviour of ideal gases.
critical temperature (Tc ). The pressure required to liquefy a gas at This theory assumes that ideal gas molecules neither attract nor
this temperature is called the critical pressure (Pc)' The volume repel each other. Average kinetic energy of gas molecules is directly
occupied by one m91e of the substance at the critical temperature proportional to the absolute temperature. A gas equation called
and pressure is called critical volume. Critical constants are related kinetic gas equation was derived on the basis of kinetic theory,
with van der Waals' constant as follows: PV I mnu 2
a 8a "3
Vc :::: 3b, Pc :::: - - 2 ' Tc
27b 27Rb Answer the following questiol"
Answer the following questiol'., 1. Gas Density
1. The relationship between Pc, Vc and Tc is: A 0,82 g L- 1
(a) PcVc RT (b) PcVc :::: 3RTc B 0.26gL- 1
3 3 O,51gL- 1
5
(c) PcVc = RTc (d) PcVc :::: 8 RTc C
Pick up the correct statement/statements:
2. Which of the following parameters is three times the van der 1. gas A will tend to lie at the bottom.
Waals' constant 'b'? 2. the number of atoms of various gases A, Band Care
(a) Critical volume (b) Critical temperature same.
(c) Vapour density (d) Critical pressure 3. the gases will diffuse to form homogeneous mixture,
3. The critical temperature of: 4. average kinetic energy of each gas is same,
(a) a substance means the temperature above which the (a) 2,3 (b) 1,4' (c) I (d) 3,4
substance is in vapour form "'. 2. Select the incorrect statement(s) about the real gases:
(b) a gas is the temperature below which it can be liquefied by I. The molecules attract each other.
application of pressure
2. They show deviation from Boyle's and Charles' law.
(c) water is lOO°C , 3. Volume of gas molecules are negligible.
(d) none of the above
4. The molecules have negligible mass,
4. The pressure required to liquefy a"1ns ~ -at the critical
(a) 2,3 (b) 1,4 (c) I (d) 3,4
temperature ts called:
3. The average kinetic energy per molecule of an ideal gas is
(a) reduced pressure (b) critical pressure
equal to:
(c) vapour pressure (d) atmospheric pressure
(a) 0,5 kJ (b) O.5RT
5. Gases A BCD (c) 1.5kT (d) 1.5R:F
Pc (atm) 2.2 14 35 45 4. Which of the following do not pertain to the postulates of
r;, (~) 5.1 33 127 140 kinetic theory of gases?
Which of the above gases cannot be liquefied at 100 K and 50 - (a) The gas molecules are perfectly elastic
atm? (b) Speed of gas molecules are ever changinJ
(a) D only (b) A only (c) Pressure exerted by the gas is due to the collision of
(c) A'andB (d) C andD molecules with the walls of the container
6. At critical point, the meniscus between liquid and vapour (d). Kinetic energy of a gas is given by the sum of 273 and
disappears due to: temperature in Celsius scale
314 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
SECTION-I 9. If the graph is plotted for 1 mol gas in such a way that PV is
plotted against P then intercept of the graph for real gas will be:
Straight Objective Type Questions
(a) RT + Pb + a (b) RT
This section contains 14 multiple choice questions. Each
(c) RT - Pb + a (d) RT + Pb + ab + a
question has 4 choices (a), (b), (c) and (d), out of which only
one is correct. 10. The ratio of Boyle's temperature and critical temperature for a
x gas is:
1. Boyle's temperature offour gases are given below:
, 1
(d) ~
8 (b) 27
Gases ABC D (a)- (c) -
g- TB . 120 K 25 K 500 K 410K 27 8 '2 1
'G which gas can be liquified most easily? 11. With which of the following elements silicon should be doped
,i so as to give p-type semiconductor? ICBSE (PMT) 20081
WA ~B ~C ~D
Ie 2. A gas is enclosed in Ii vessel of volume Vat temperature 1\ and (a) Selenium (b) Boron (c) Germanium (d) Arsenic
h pressure P; the vessel is connected to another vessel of volume 12. Total volume of atoms present-in a face centred cubic unit cell
'r of a metal is (r is atomic radius): p{PMER 20081
V / 2 by a tube and a stop cock. The second vessel is initially
'it
evacuated. If the stop cock is opened, the temperature of (a)16 n ? (b)20n? (c) 24 n ? (d)gnr3 .
second vessel becomes T2 • The first vessel is maintained at a 3 3 3 3
temperature 1\. What is the final pressure ~ in the apparatus? 13. How many effective Na + .and cr ions are present respectively
Ct
(a) 2PT2 (b)2PT2 (c) PT2 (d) 2PT2 in the rocksalt (NaCl). If ions along the axis joining opposite
2T2 +1\ T2+21\ 2T2 +1\ 1\+T2 faces are removed ?
.-'
3. The ratio of rate of diffusion of gases A and B is 1: 4. If the . (a)4,~ (b)~,~ (C)~,4 (d) 3,3
ratio of their masses present in the mixture is 2 : 3, what is the
ratio of their mole fraction? 14. Kinetic energy and pressure of a gas of unit mole are related as :
1 2 3', E
(a)-
1
(b)-
1
(c)- (d)~ (a)P=2E (b)P=-E (c)P=-E (d)P=-
8 12 16 24 3 2 2
4. D~nsity of a gas at STP is 2g / L while the expected density is
1.8 g / L assuming its ideal behavi~ur. Then: SEC1"ION-1i
(a) gas behaves ideally
(b) forces of attraction are dominant among gas molecules Multiple Answers Type Objective Questions
(c) forces of repulsion are dominant among gas molecules 15. Which of the following measure the deviation from ideal
, (d) none of the above behaviour of gas?
5. In a crystalline solid, anions B are arranged in ccp lattice and
(a) Collision diameter (b) Collision frequency
cations A occupy 50% of the octahedral voids and 50% of the (c) Compressibility factor (d) van der Waals' constant 'a'
tetrahedral voids. What is the formula of the solid? 16. In face-centred cubic unit cell:
(a) AB (b) A3B2 (c) A2B2 (d) A2B3 (a) face di~gonal·ofthe cube is a.fi or 4r
6. In a compound XY2 0 4 , oxide ions are arranged in ccp and (a = edge length, r = radius of constituent units)
cations X are present in octahedral voids. Cations Y, are (b) effective number of atoms in the unit cell is 4
equally distributed among octahedral and tetrahedral voids. ' (c) 8 tetrahedral voids per unit cell
The fraction of the octahedral voids occupied is: , (d) rank of the unit cell is 3
1 1 1 1 17. Which of the following mixtures of gases at room temperature
(a) "4 (b) "2 (c)(j (d)"S
follow Dalton's law of partial pressures?
7. An ideal gas: (a) NO and 02 (b) CO and CO2
(a) can be liquefied if its temperature is more than critical (c) NH3 and HCl (d) S02 and O 2
temperature 18. A real gas can be liquefied:
4r
(b) can be liquefied if its pressure is more than critical pressure (a) under adiabatic expansion
(c) cannot be liquefied at any pressure and temperature (b) above critical temperature
;ell (d) can be liquefied if its temperature is more than Boyle's (c) when cooled below critical temperature under applied pressure
temperature (d) at temperature lower than critical temperature and
8. A mineral is made of calcium, titanium and oxygen Ca 2+ ions pressure higher than critical pressure
located at comers, Ti 4 + ions at the body-centre and 0 2- ions at 19. Which of the following statements is (are) correct?
face-centres of the unit cell. The molecular formula of the (a) In body-centred cubic unit cell, the coordination number is
mineral is ....... 12
(a) CaTi 30 4 (b) CaTi03 (c) CaTi0 2 (d) CaTi 20 3 (b) The coordination number of each type of ion in CsCl is 8
STATE;S OF MAnER' 315
(c) A unit cell of an ionic crystal shares some of its ions with Statements (a, b, c and d) in Colurrm-I have to be matched with
neighbouring unit cell statements (p, q, rand s) in Colurrm-II. The answers to these
(d) If rNa+= 95 pm; rCl - = 181 pm; then edge length of unit questions have to be appropriately bubbled as illustrated in the
cell ofNaCI is 552 flm following examples:
If the correct matches are (a-p,s); (b-q,r); (c-p,q) and,(d-s);
SECTION-III then correct bubbled 4 x 4 matrix should be as follows:
Assertion-Reason Type Questions p q r s
This section contain'S 6 questions. Each question contains
Statement-l (Assertion) and Statement-2 (Reason).' Each
a®®0 ®
question has following 4 choices (a), (b), (c) and (d), out of
which only one is correct.
b ® ® 0 CD
c ® @ CD
(a) Statement-l is true; statement-2 is true; statement-2 is a
correct explanation for statement- L
0
(b) Statement-l is true; statement-2 is true; statement-2 is not d ® ® 0 0
a correct explanation for statement-I.
(c) Statement-l is true; statement-2 is false. 26. Match the Colurrm-I with Column-II:
(d) Statement-l is false; statement-2 is true. Column-I Column-II
20. Statement-I: The pressure inside the LPG cylinder remains (a) 'High temperature (P) Z oF I
constant even when it is in use at room temperature. ' a
(b) Extremely low pressure (q) Pb <-
Because V
Statement-2: Vapour pressure of any liquid is independent of (c) Very high pressure (r) Z::: 1
its amount; it, depends only on temperature. a
21. Statement-I: If a gas has compressibility factor (Z) greater (d) Low pressure (s) Pb >
V
than unity, then repulsive forces are dominant.
27. Match the Colunm-I with Colunm-II:
Because
Statement-2: Value of Z decreases with increase in pressure. Column-I Column-II
22. Statement-I: The value of Boyle's temperature for a real gas (a) Constituent units occupy only comers (P) 67.98%
. (Tn
IS a J. (b) Constituent units occupy comers as
. ' well as face-centres
(q) 26.17%
Rb Because
Statement-2: At Boyle's temperature, Tn, real gases behave (c) "'Constit:uent units occupy comers and (r) 74.01%
ideally over a long range of pressure. body~centre
23. Statement-l: CaC03 shows polymorphism.
(d)' Constituent units occupy comers and (s) 52.33%
Because
edge-centres
Statement-2: CaC03 exists in two forms called aragonite and
calcite. ' 28. Match the Colunm-I with Colunm-II: (UT 2007)
24. Statement-l: Lead zirconate is piezoelectric solid. Column-I
'"
Column-II
Because
Statement-2: Lead zirconate crystals have no dipole moment. (a) Simple cubic ana (P) Have these cell
25. Statement-l: Band gap in germanium is small.
face-centred cubic parameters. abc
Because, anda ~=y
Statement-2: The energy spread of each germanium atomic (b) Cubic and rhombohedral (q) Are two crystal systems
energy level is infinitesimally small. (liT 2007),; (crql;i.bf$'1wd tetragonal (r) Have only two
~ ,. -, ".':": ,:;,'
crystallography angles
SECTION-IV of 90°
Matrix-Matching Type Questions {dj~:Hexagonal and (s) Belong to same crystal
This section contains 3 questions. Each question contains monoclinic system
statement given in two colurrms which'have to be matched.
.
[J4~', -------!~/~.- - - - - - - - - I ..
I
1. (c) 2. (a) 3. (b) 4. (b) 5. ,(b) 6. (b) 7. (c) 8. (b)
9. (b) , 10. (b) 11. (b) 12. (a) 13. (d) 14. (b) 15. (c, d) 16. '(a, b, c)
17. (a, b, d) 18. (a, c, d) 19. (b, c, d) 20. (c) 21. (c) 22. (b) 23. (a) 24. (c;)
25. (c) 26. (a-p) (b-p) (c-p, s) (d-p, q) 27. (a-8) (b-r) (c-p) (d-q) 28. (a-p, s) (b-p, q) (c-q) (d-q, r)
5
SOLUTIONS
(General and Colligatlve Properties)
Mass percentage of solute Mass of solute x 100 (vi) Mole fraction: This method is used when the solution
Mass of solution is constituted by mixing two or more components. It is defined as
the ratio of number of moles of one component to the total
Mass of solute
= x 100 number of moles of the solution (i.e., all the components). Taking
Mass of solute + Mass of solvent three components A, Band C.
Mass of solute
=Volume of solution x Density of solution
xlOO Components A B C
Mass (in gram) WI w2
. Mass of solute . . Molecular mass m] m2
The ratio -_.... IS termed as mass fraction.
Mass of solution
No. of g moles
Thus, ml m2
Mass percentage of solute = Mass fraction x 100 Total number of g moles
ml m2 m3
10% solution of sugar means that 10 gram of sugar is present
in 100 gram of the solution, i.e., 10 gram of sugar has been Thus, Mole fraction of A =
dissolved in 90 gram of water. wJ
-+
(ii) Per cent by volume: It is defined as the volume of ml m2 m3
solute in mL present in 100 mL solution.
Volume of solute Mole fraction of B fB
Per cent of solute by volume = x 100
Volume of solution mJ m2
(iii) Per cent mass byvolume: It is defined as the mass of
solute present in 100 mLof solution. Mole fraction of C =
WI
Per cent of solute mass by volume -+
m1 m2 m3
Mass of solute
----xIOO The sum of mole fractions of a solution is equal to 1, i. e~
Volume of solution
fA + IB + .fc '~~'."
(iv) Strength or concentr~tion (Gram per litre): It is In a binary solution,
defined as the amount of the solute in gram present in one litre of
the solution. Mole fraction of solute + Mole fraction of solvent = I
Concentration of solution Let n moles of solute (B) andN moles of solvent (A) be present
Mass of solute in gram in Ii solution.
=
Volume of the solution in litres Mole fraction of solute _11_ ~XB
N+n
Mass of solute in gram
~ x 1000
Volume of the solution in mL Mole fraction of solvent ~= X A
N+n
Concentration in gram per litre is also tenned as strength of
the solution. Let W g of the solute be present in V litre of solution; Thus, X A +XB =I
then Mole fraction is independent of temperature of the solution.
(vii) Molality: It is defined as the number of moles of the
Strength or concentration of the solution ; gL- I solute present in 1 kg of the solvent. It is denoted by m
lNote: V is not the volume of the solvent. V is actually the final Number of moles of solute
volume after dissolving a definite quantity of solute in the Molality (m) = --~--------
Number of kilo-grams of the solvent
solvent.]
(v) Paris per million (ppm): When the solute is present in Let WB gram of the solute of molecular m~s mB be present in.
trace quantities, it is convenient to express the concentration in WA gram of the ~01vent, then
parts per million (ppm).lt is defmed as the quantity of the solute
in gram present in 106 gram of the solution. Molality (m) = x 1000
mB xW A
Mass of solute 10
opm= x 6 Relation between mole fraction and molality:
• Mass of solution
n N
Atmospheric p0!lution in cities is also expressed in ppm by X B =--andX A =
. N+n N+n
volume. It refers to the voluT.e of the pollutant in 106 units of
volume. 10 ppm of S02 in air means 10 mL of S02 is present in Moles of solute
- - - - - - =: --"'---'-=-
Mass of solute in 1 litre : :;: ~ x (1000 x d ) g Dividing both numerator and denominator by (n A + nB ),
100
1000x d
:::;:: (xx d x lO)g M x------------
nB
Number of moles of solute in I litre --'-'-- x mA + x mB
nA+nB nA+nB
Massof solute in gram x x d x 10
xlOOOxd
Gram molecular mass of solute mB M
xAm A +xBmB
,where mB molecular mass of s,olute
(ix) Normality: It is defined as the number of gram
M:::;:: xxdx 10 equivalents of solute present per litre of solution. It is denoted by
mB 'N'.
Molarity of dilution: Number of gram equivalents of solute
Normality (N)
Before dilution After dilution Number of litres of the solution
MtVt M 2V2 or Normality x Number. of lit res of the solution
Number of gram equivalents ofthe solute
SOLUTIONS
Example 8. The density ofa 2.03 M sQlution ofacetic acid V&' No. of moles of S20~- ions::: No. of moles of Na2S203
(molecular mass 60) in water is 1.017 glmL. Calculate the .
molality of the solution. =3
Solution: Strength of the solution MolalityofS20~- ions: 3 x1OO0=3.86m
Molarity x mol. mass 776
== 2.03 x 60 121.8 gl L Example 10. A solution is prepared by dissolVing 5.64 g of
Density ofsolution = 1.017 gl mL glucose in 60 g of water. Calculate the following:
Mass of 1 litre of solution = 1000 mL x 1.017 gl mL (i) mass per cent ofeach ofglucose and water;
"" 1017 g (ii) molality of the solution,
895.2 (iii) mole fraction of each ofglucose and water.
Mass·of water ::=1017 -121.8 = 895.2 g = kg
1000 Solution: (i) Total mass of solution
Molality = 2.03 x 1000 ::: 2.267 m ::: 5.64 + 60.= 65.64 g
895.2
Mass per cent of glucose = 5.64 x 100 = 8.59%
, Example 9. The density of a 3 M sodium thiosulphate 65.64
solution (Na2S 203 ) is 1.25 glmL. Calculate (i) the percentage by
Mass per cent of water::: (100 - Mass per cent of glucose'
mass of sodium thiosulphate, (ii) the mole fraction of
sodium thiosulphate and (iii) molalities ofNa + and SzO;- ions. :;: (100 8.59)=91.41%
Solution: (i) Mass of 1000 mL ofNa zS 2 0 3 solution (ii) No. of mores of glucose = 5.64
180
1.25 x 1000= 1250 g . 60
Mass of water in kg = - -
Mass ofNa z Sz 0 3 in 1000 mL of3 Msolution . 1000
3 x Mol. mass of NazSz03 Mo11 '
a lty 5.64 x -
=-- 1000
- : 05'
. 22 m
180 60
= 3x 158= 474 g
Mass percentage ofNazS203 in solution (iii) No. of moles of glucose = 5.64 :;;;; 0.0313
180
474 x 100 37~92 . 60
No. of moles of water:;;;; - :;;;; 3.333
1250 18
Alternatively, M :::: x x d x 10 Molefraction of glucose; 0.0313 =.0.0093
mA 3.333 + 0.Q313
3 xX 1.25 x 10 Mole fraction of water = 3.333 :::: 0.9907
158 3.333 + 0.0313
x= 37.92 Example 11. What would be the molality of a solution
made by mixing equal volumes of 30.0% by mass of H 2 S04
(ii) No. of moles of Na 2S2 0 3 :;: 474 =3 (density 1.218g cm- 3 ) and 70% by mass of H 2 S0 4 (density
158
1.61Og cm-3 )?
Mass of water =(1250 - 474)::: 776 g
Solution: Let 100 mL of one solution be mixed with 100 mL
776
No. of moles of water =- : 43.1 of the other solution.
18 Mass of 100 mL of 30% H 2 S04 100 x 1.218 :::: 121.8 g
Mole fraction of Na2S203 = .3 . =_3_=0.065 Mass of H 2 S04 in 12L8 g of 30% H2 S0 4
43.1 +3 46.1
30
:::: - X 121.8 g 36.54 g
(iii) No. of moles of Na+ ions 100
2 x No. of moles of Na2S203
. . " Mass of water = (1.21.8 - 36.54) :::: 85.26 g
=2x3 6
MassofloomLof70%H2 S04 100x1.6l 161.0g
· fN + . No. of moles of Na + ions !\1ass of H2S04 in 161.0 g of 70% H 2 S04
Mo1a1lty 0 a Ions - . - - - - - - -
Mass of water: in kg 70
=- x 161.0 g = 112.7 g
6 100
=-xlOOO
776 Mass of water.::: (161.0 -112.7)
..
=48.30 g
= 7.73-m Total H 2 S04 in solution = 36.54 + 112.7: 149.24 g
322 , A.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Ws 0.0438g/mL
5.5' SOLUTIONS- OF GASES IN LIQUIDS
"Example 14. How many Na+ ions are present in 50mL of , (Solubility of Gases)
a 0. 5 M solution ofNaCl?
, MV All gases are soluble in water as well as in other liquids to a
Solution: Number of moles ofNaCI = - - greater or lesser extent. Solutions of gases in water play an
1000
important role in our daily life. The common examples are
0.5 x 50 = 0.025 carbo rated beverages, i.e., soft drinks, household cleaners
1000 containing aqueous solutions of ammonia, formalin-an aqueous
NaCI---? Na + + Cl- solution of , formaldehyde, etc. The natural waters contain
Number of moles of Na + = Number of moles of NaCI dissolved; 02 which is vital for the existence of aquatic life in sea,
! 0.025 ' . rivers and lakes.
The solubility of a gas in a liqui4 is expressed in terms of
'Number of ions of Na + 0.025 x 6.023 X 10 23
absorption coefficient. It is defined as the volume of the gas in
1.505 X 10 z2 mL that can be dissolved by 1 mL of a liquid solvent at the
SOLUTIONS 323
temperature of the experiment at one atmospheric pressure. The (y == rnx) passing through origin. Fig. 5.2 shows the variation of
volume of the gas is measured at STP. Thus, if v is the volume of solubility of some gases against equilibrium pressure. The
the gas dissolved, reduced to STP, V is the volume of the solvent straight line graphs show the validity of Henry's law.
and P is pressure of the gas in atmospheres, then the absorption
coefficient, a, Is given by . Slope of the line
'tan 0': K
v
i tan 01 = K(for N2)
VP
The following factors affect the solubilities of gases in liquids: .
(i) Nature ofthe gas and solvent: Generally, the gases which
can be easily liquefied are more soluble in common solvents. For·
yN'
.' ,,~.. ~\ 61 ~
tan 02 : K(for 02)
The gases which react with the solvent posses higher solubility.
Pressure of gas ~
For example, HCI and NH3 are highly soluble in water. overtiquid .
Oxygen, nitrogen and carbon dioxide are much more soluble
Fig. 5.2 Variation of solubility of a gas with pressure
in ethyl alcohol than in' water. at the same temperature and
pressure. If solubility of the gas is known at one particular pressure.,
(ii) Temperature: The solubility of most of the gases'in then it can be calculated at other pressures using the followin!t
liquids decreases with increase of temperature as the dissolution relation,
is an exothermic process. When water is heated in a beaker, ~==PI ... (ii)
bubbles of air are formed on the sides of the glass before the m2 P2
water boils. As the temperature rises, the dissolved air molecules
begin to ."boil out" of the solution long before the water itself . where 'mI' is the solubility of the gas at pressure 'PI' and 'm2' is
boils. the solubility of the gas at pressure 'P2 '.· .
When a mixture of two or more non-reacting gases is brought
t in contact with a solvent, each constituent gas dissolves in
~0.003 proportion to its own partial pressure. Henry's law can be applied
is to each individual gas independent of the presence of other gas. If
gO.002
we use the mole fraction oftne gas in the solution as a measure of
a its solubility, then the law can be stated as, "molefraction of the
il 0.001
:l
'0
gas in a solution· is proportional to the partial pressure' of the
rJ)
'. 20 40 60 80 100120 . gas."
Temperature CC) ~ xocp
.Fig. 5.1 Temperature dependence of O2 gas where, x ==·mole fraction of the gas in solution
solubility in water and p == partial pressure of the gas.
The reduced solubility of molecular oxygen in hot water has a
or x=K' p
direCt bearing on thermal pollution~ i.e., the heating of the
environinent--:usually waterways-to temperatures that are 1
or p= K,x==KHx ( KH == },) .. :(iii)·
harmful to its living inhibitants.
(iii) Pressure : The most important factor which influences . K H is called Henry's law constant. Different gases havt::
the solubility of a gas in a liquid is the pressure. The .effect of diff~rent' values of KHat a defmite temperature for a given
pressure on the solubility of the gas in the liquid is given by solvent.
Henry's law, which states that the solubility of a gas in a liquid is
directly proportional to the pressure of the gas over the solution TableS.l Values ofHenry~s Law Constant (K H ) for Some
. at a definite temperature. The solubility is taken as the mass of Common Gases in Water
the gas dissolved per unit volume of the liquid ..Thus, if m is the
Gas Temperature (K) XJI
mass of the gas dissolved per unit volume of the solvent and P is
the pressure of the gas in equilibrium with the solution, then He 293 144.97
mocp Hz 293 69.16
f
: i s =KP 3.1 x lOt x 4 = 0.12 mol litre-I p Mass of NaCI = 58.5 x 0.125 = 7.32 g]
:. 6. Density of a 2.05 M solution of acetic acid in water is 1.02
ExampIe;l8./ The pdrtial pressure of ethane.: q~?r a ':"; glmL. The molality of the solution is: (AJEEE 20(6)
saturated soltiiiofo containing 6.56 x 10-2 g of ethane t~~ [. b~r. If (a) 1.14 mol kg- I (b) 3.28 mol kg- l
the solution conlains 5 x 10-2 g 'of ethane, th{!n wha{sh~tt bifhe (e) 2.28 mol kg:-l (d) 0.44 mol kg-I
partial pressuJ pf the gas? . • ....,,_ ... [ADs. (e)]
Solution: ~ = PI . [Hint: m= ¥xlOOO 2.05x 1000
S2 P2 1000d MmB 1000x 1.02- 2.05 x 60
=.2.28 mol kg-I]
I
SOLUTIONS
'" 325
7. The hardness of water sample containing 0.002 mol of (0.5 0.1) x = 0.4- 0.2
magnesium sulphate dissolved in a litre of water is expressed OAx = 0.2
as: ; -i-'F'f -:<":',,-;~,-,) 2-0n:; x = 0.5L
(a) 20 ppm (b) 200 ppm (c) 2000 ppm (d) 120 ppm :. 0,5 L of A and 1.5 L of B should be mixed.]
(e) 240 ppm
,[Ans. (b)] ~~6 SOLUTIONS OF LIQUIDS IN LIQUIDS
6
[Hint: 10 g water contains (0.002 x 1000) mol MgS04 When one liquid dissolves in another, the molecules of the
1 mol MgS04 1 mol CaC0 3 solvent are caused to move apart so as to accommodate the solute
2 mol MgS04 ;E 2 mol CaC0 3, i.e.,2 x 100 g CaC03 molecules. Similarly,the solute molecules must also be separated
so that they can take their places in the mixture. In both these
. . Hardness of water = 200 ppm]
processes, energy is required. Finally, as the solute and solvent
8. The density (in g mL-1) of a 3.6 M sulphuric acid solution, molecules are brought together, energy is released because ofthe
i.e., 29% H2 S04 (molar mass == 98g mor l ) by mass will be: attractive forces between them. When solute and solvent,
('>"IEEE 20()7) molecules are strongly attracted to each other, more energy is
(a) 1.45 (b) 1.64 (c) 1.88 (d) 1.22 released in the final step. Three cases may arise under these
[Ans. (d)] circumstances. The overall dissolution process results either in
evolution of heat or absorption of heat, or energy released in the
[Hint: M = x x d x 10 final step is the same as the energy absorbed in the first two, i. e. ,
ms
net change is zero.
3.6 x 98 '" 1.22 mL-l] Examples:
29 x 10 ' g 1. Benzene and carbon NO evolution or absorption
9. I litre solution containing 490 g of sulphuric acid is diluted to tetrachloride: of heat.
10 litre with water. What is the normality of the resulting 2. Acetone and water: Evolution of heat.
solution? (~';crt \~I;U7) 3. Ethyl alcohol and water: Absorption of heat.
(a) 0.5 N (b) 1.0 N (c) 5.0 N (d) 10.0 N A liquid mayor may nof be soluble in another liquid.
[Ans. (b)] Depending upon the relative solubility of a liquid in another, the
[Hint: N : : ; - 'xL1000
__
490 x 1000 10 following three cases are possible:
Es xV 49 x 1000 Liquid-Liquid Systems .'
N/V I =N Z V2
__________~I --------------1
IOxl N 2 xlO 1. Liquids that are 2. Liquids that 3. Liquids that
N z = 1] completely - are partially are practically
10. 250 mL ofa Na 1 C0 3 solution contains 2.65 g ofNa 1C03 . 10 miscible. miscible. immiscible,
mLofthis solution is added toxmL of water to obtain 0.001 M Examples: Examples: Examp!Js:
Na 2 C03 solution. The value of x is .... Benzene and Ether and wa- Benzene
toluene; ter; Phenol and water;
(Molecular mass ofNa 1 C03 = 106 amu) [SHe (Mains) 20081
Ethyl alcohol and water; Carbon tetra-
(a) 1000 (b) 990 (c) 9990 (d) 90
and water; Nicotine and chloride and
[Ans. (b)] Carbon tetra- water. water; Ben"
[Hint: Molarity of solution. chloride and zene and
M
Ws x 1000 = 2.65 x 1000 0.1 benzene. alcohol.
ms X V 106 x 250
M/V1 =M2 V2 Miscible liquids form three types of solutions, which can be
0.1 x 10 =0.001 (10 + x) ideal or non-ideal solutions.
x= 990mL] • > Ideal' solution:. An ideal solution is' one in which the '
H.The yolumes ohwo-HCI s{)lutions A (O:5N ) and B (0.1 N) to molecules attract one another with equal force irrespective of
their nature. Thus, a solution composed of two components
be mixed for preparing 2 L of 0.2 HfiC! are : , _, ____ _
A andB will bean ideal one if- the forces between
EAMCET (IVIed) 2(}o8!
A and A, Band B should be the same. An ideal solution
(a) 0.5 L of A + 1.5 L of B
(b) 1.5 L of A + 0.5 L of B
possesses the follOWIng characteristics:
(c) 1 L ofA + I L of B (i) Volume change of mixing should be zero.
(d) 0.75 L of A + 1.25 L ofB AVmix 0; Vsolvent + Vsolute = Vsol ...1ion
[ADs: (a)] (ii) Heat change on mixing should be zero.
[Hint: Let x L of A and (2 x) L of B are mixed. MI mix = o(Heat is neither absorbednor evolved.)
M1V/ + M 2V2 =MR(V/ + V2 ) (iii) There should be no chemical reaction between solvent
0.5 x x + 0.1 (2 - x) 0.2 x 2 and solute.
326 (7, R. B. PHYSICAL CHEMISTRY FOR COMPETITIONS '
Solvent+ Solute ~ Solution (vi) Ideal solutions must obey Raou!t's law at all
1Non-i~l
H2 0 + NH3 ~NH40H concentratious.
H 20 + CO 2 ~H2C03 The following are some of the binary mixtures which show the
H 2 0 + CaO ~Ca(OHh properties of ideal solutions:
(a) Benzene and toluene,
(iv) Solute molecules should not dissociate in the ideal (b) Carbon tetrachloride and silicon tetrachloride,
solution. (c) n-Hexane and n-heptane,
(d) Ethylene dibromide and ethylene dichloride.
NaCI Aqueous medi"n; Na + + CI- ) Raoult's Law
Non-ideal
Aqueous mediwn
H 2S04 )' 2H + + SO~- According to this law, the partial pressure of any volatile
constituent of a solution at a constant temperature is equal to
the vapour pr~ssure of pure constituent multiplied by the
(v) Solute moleculeS should not associate in ideal solution.
mole fraction of that constituent in the solution.
2
'0'
" eOOH Dissolved
benzeneIn
. . •
(ASS0711on)
err.
~
0-.+0
O---HO
,y
+0 0-
"'-
I """OH---OVC( ) 'I Non-Ideal
b
.
~.
Let a mixture (solution) be prepared by mixing n A mole ofo
liquid A and nB mole of liquid B. Let P A and PB be the partial
pressures of two constituents A and B in solution and P ~ and P ~
the vapour pressures in pure state respectively....
Non-ideal solutions
Ideal solutions
Positive deviation from Raoult's law Negative deviation from Raoult's law
I. Obey Raoult's, law at every range of Do not obey Raoult's.law. Do not obey Raoult's law.
concentration.
=
2. IlH mix 0; neither heat is evolved nor IlH mix > O. Endothermic dissolution; heat IlH mix < O. Exothermic dissolution; heat
absorbed during dissolution. - is absorbed. is evolved.
3. AVmix 0; total volume of solution is AVmix > O. Volume is increased after AVmix < O. Volume is decreased during
equal to sum of volumes of the dissolution. dissolution.
co~ponents.
6. Escaping tendency of 'A' and 'B' should 'A' and 'B' escape easily showing higher Escaping tendency of both components
be same in pure liquids and in the.solu- vapour pressure than the expected value. 'A' and 'B' is lowered showing lower
tion. vapour pressure than expected ideally.
~ ~
:::l
tJ)
<Jl
pg :::l
<Jl
<Jl
~ ~
0. 0-
....
:::l
....
:::l
....
:::l
0
0.
0
0.
o
0.
~ ~ ~
Fig. 5.3
Relation between Dalton's Law and Raoult's Law: pressure of the solution and the mole fraction of methanol in the
The composition of the vapour in equilibrium with the vapour.
solution can be calculated applying Dalton's law of partial Solution: Mol. mass of ethyl alcohol == C zHs OH = 46
pressures. Let the mole fractions of vapours A and B be 60
f A arid f B respectively. Let P A and P B be the partial pressures No. of moles of ethyl alcohol = - 1.304
46
of vapours A and B respectively and total pressure P.
Mol. mass of methyl alcohol = CH 3 0H = 32
PA=fAP ... (i) . 40
PB == fB P ... (ii) No. of moles of methyl alcohol = = 1.25
32
PA X A p~ ... (iii)
~ X A' , mole fraction of ethyl alcohol ::: 1.304 = 0.5107
PB =X B pg .. , (iv) .. . 1.304 + 1.25
Equating eqs. (i) and (iii),
fA P=X A p~ ,X B', mole fraction of methyl alcohol 1.25
or
X A p~ PA 1.304+ 1.25
fA = 0.4893
P P
Similarly, equating eqs. (ii) and (iv), Partial pressure of ethyl alcohol X A .p~ ::: 0.5107x 44.5
. . 0
- X B PB =PB 22.73 mmHg
f B- -
P P Partial pressure of methyl alcohol = X B .p~ 0.4893 x 88.7 .
Thus, in case of ideal solution the vapour phase is richer with = 43.40 mmHg
more volatile component, i.e., the one having relatively greater Total vapour pressure of solution = 22.73 + 43.40
vapour pressure. = 66.13mmHg
Example 19. The vapour pressures of ethanol and, Mole fraction of methyl alcohol in the vapour
methanol are 44.5 mm and 88.7 mm Hg respectively. An ideal Partial pressure of CH3 0H 43.40 :=c 0.6:":63
.solution is formed at the same temperature by mixing 60 g of
Total vapour pressUre' 66.13
ethanol with 40 g of methanol. Calculate the total vapour
328 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Example 20. Two liquids A and B form an ideal solution. 25 = 0.25' n - 35 0.3
At 300K, the vapour pressure of a solution containing 1mole ofA 100 ' B - 114
change in composition. snch a mixture which boils at constant It is never possible to separate a mixture completely into the
temperature and distils over completely at the same pure components A and B. It mainly gives a constant boiling
temperature without any change in composition, is called mixture (azeotropes) which can never be separated by
constant boiling mixture or azeotropic inixture. distillation. .
Consider the distillation of a mixture of composition x. , There are several liquid pairs which form maximum boiling
The vapour given off has the composition xl' The composition of point azeotrope. Some examples are tabulated below:
residual liquid will shift towards A. In the mean
% Composition Boiling point
time thecompositioRofthe distillate shifts towards C. Ultimately Mixture
of azeotrope (pressure .. 1 atm)
by repeated fractional distillation, the mixture of composition C ---.-~-----.~-----~---.~-'---
will be obtained as distillate and pure liquid A will be left as 1. Nitric acid-Water 68% Nitric acid 125.SoC
residue. It will never be possible to have pure B. 2. Acetic acid-Pyridine 65% Pyridine 139.0°C
When a mixture of composition y is distilled, th~pour given 3 .. Chlorofonn-Acetone 80% Chlorofonn 65.0°C
off has the coml?,osition Yl'j. e., the composition~ residual
liquid will Shifttowards R Ultimately the mixture of composition 4. Hydrogen chloride- 79.8% Water 108.6°e
Water
C will be obtained as distillate and pure liquid B will be left as
residue. It will nev~r be possible to have pure A.
There are several liquid pairs which form minnnum boiling 5.8 SOLUTIONS OF SOLIDS IN LIQUIDS
point azeotropes. Some examples are given in the table:
Solutions of this type are most common. In solutions of solids in
Table 5.3 Some Azeotropic,Mixtures liquids, the liquid is invariably referred to as a solvent and the
solid dissolved in it as the solute. If a solute is added in small'
% Composition of Boiling point
Mixture amounts at a time to a given amount of a solvent at a constant
azeotrope (pressure = 1 atm)
--..-- temperature, with vigorous stirring or the solvent after each
1. Water-Ethanol 95.97 Ethanol 78,15°C addition, a stage is reached when the added solute no more
2. Pyridine-Water 57.00 Pyridine 92.60°C disappears, i. e. ,goes into solution but remains undissolved. The
solution is then said to be saturated. A solution which remains in
3. . Ethanol-Benzene 32.40 Ethanol 67.80°C
contact with undissoived solute is termed as saturated. It can
4. Acetic acid-Toluene 28,00 Acetic acid 105.40°C also be defined as one which is in eqUilibrium with the excess
Solutions of type-UI (Negative deyiations from Raoult's of solid at a particular temperature.
law): The boillng temperature-composition curves for the The amount of solute dissolved in 100 g of a solvent to form a
liquid and vapour phases have been shown in Fig. 5.6. The curves saturated solution at a given temperature is termed the solubility
meet at point C. At this point, both liquid and vapour phases have of the solute in the given solvent at that temperature. Each
same composition, The constant-boiling mixture has maximum substance has a characteristic solubility in a given solvent at a
boiling point. de.finite temperature.
When a solid is added to the solvent, the particles from the
solid diffuse into it. The solute. and solvent molecules move
c
t constantly in the solution phase. Some of the particles of the
solute retJ,lm to the solid state due to collisions. Thus, two
e
'0
A
opposite processes operate simultaneously.
c.. k,.. :
Cl
.5 ! 9(qcy, (a) Dissolution: Particles of solute leaving the solid and
'5 ,, ,,
I ,
dissolving in the solvent.
co (b) Recrystallisation: Solute particles returning to the solid
'Y 'Y1
A 100% form. .
80% -
Composition 8 100%
AO% When these two processes move with same speed, an
equilibrium stag~ is reached,
Fig. 5.6 Boiling temperature-composition
. curves in binary solution of type-III Solute (solid) ~ Solute (dissolved)
Consider the distillation of a mixture of composition x. The Thus, a dynamic equilibrium exists in a saturated solution.
vapour coming off is richer in A as indicated by composition When a saturated solution prepared at a higher temperature is
Xl . The composition of the residual liquid shifts towards C. As the
cooled, it gives a solution which contains usually more of solute
distillation proceeds, the composition Of the distillate moves than required for the saturated solution at that temperature. Such
towards A and that of residue towards C. a solution is referred to as a supersaturated solution. It is
Similarly, a mixture of composition lying between Band C, usually unstable and changes to saturated solution when excess
say y, on distillation will give vapour richer in B as indicated by of solute comes out in solid state. '
composition Yl' The composition of residual liquid shifts The: following factors influence the solubility of a solute in a
towards C and di'stillate towards A on repeated distillation, liquid:
SOLUTIONS
f-~
1. Nature of solute: The solutes (solids) can be classified as II Vi
ionic and non-ionic solids. The ionic solids consist of positively 170
~V ~rr;
and negatively charged ions. It is the force of attraction between 160 r-
/ ./ V I i
the ions, L e., lattice energy which opposes the tendency of a 150
I /~ 1.0,
solute to dissolve. This force of attraction is different in different ~ 140
j/ ..:.-
f?1- t
V
~ 130
I ~l
ionic solids depending on the charges present on the ions and if I
C)
120 i d
distance between ions (ionic radii). The ionic solutes having high 0
~'"A / ' V
lattice energy like BaSO 4 are less soluble while those having less
0
Q;
110
100
~,. V L 'f:,.'O{ ____.....-
lattice energy have more solubility. The ions are solvated by the ,c. I. /1 / ....- ~
90
solvent molecules and in this process energy (known as hydration ~ ~f?/ J.:--
80
70 ~w~
energy) is released. When the hydration energy is high, the ionic :0
:::J --/ ,
~
~
~/1'
(5
s'olid is more soluble. CIl
60 V ' ...... ~a2so~ All
Many non-ionic substances dissolve in polar solvents due to
50
1<..,9.C =?
hydrogen bonding. Generally, if the solute and solvent have
__ ';c,rA. ~ .- ~ NaCI
/"
similar characteristics, i. e. , both are polar or both non-polar, the 40
30 1~~~2~O4- ,---
~ftf
solubility is high and if both are dissimilar, the solubility is found
low. 20 ,--,'"
Na~'e,oy
10
2. Nature of solvent: Ionic solids dissolve to a larger extent Ft-1
in a solvent having a high dielectric constant as compared to 10 20 30 40 50 60 70 80 ,90 100
solvents oflow dielectric constants. Dielectric constant of water Temperature in degree celsius
is 80 while that of methyl alcohol is 33.5. An ionic solid,
therefore, dissolves more readily in water than in methyl alcohol. Fig.5.7 Solubility curves of some compounds
Benzene has a very low dielectric constant of 2.3 and, hence, 1. Mass of empty dish w g
ionic solids do not dissolve in benzene. 2. Mass of dish + solution = WI g
For non-ionic solids, the guiding principle is 'like dissolves 3. So, Mass of solution (wI - W) g
like', Le., if the solvent is polar, it will dissolve the polar solutes 4. Mass of dish + residue ~ W2 g
and if it is non-polar, it will dissolve the non-polar solutes in it. So, Mass of residue = (w2 w) g x g
3. Temperature: The solubility of a solute in a given and Mass of solvent (Mass of solution
solvent varies appreciably with temperature. A few curves drawn - Mass of residue )
between solubility in water and temperature are given in Fig. 5.7. = (WI - W) - (W2 - W)
It is observed that the solubility of NaCI increases' very = (WI W2)= yg
slightly with an increase in temperature whereas those of
KN0 3 ' NaN0 3 , AgN03 and KI, etc., increase greatly. A Thus, the solubility of salt = x x 100 g per 100 g ~f solvent.
y
sharp break in a solubility curve indicates the formation of
a compound whose ~olubility is different from that of the Example 23: 50 g of a saturated aqueous solution of
substance from which it has been formed as in the case of potassium chloride at 30°C is evaporated to dryness. when 13.2 g'
N a 2 SO4 ·lOH2 O. It losses its water of crystallisation at ofdry KCf was obtained. Calculate the solubility ofKCf in water
32.3°C and is converted into anhydrous form. There are few at 30°C.
substances like calcium acetate, cerium sulphate, calcium Solution: ' Mass of water in solution (50-13.2) 36.8g
chromate, etc., which show a decrease in solubility with rise in
temperature. Solubility of KCl = Mass ofKCl x 100 13.2 x 100= 35.87
. Mass of water 36.8 g
Generally, solubility depends on heat of solution. If a
substance dissolves with absorption of heat, the, solubility Example 24. How much copper sulphate will be required.
increases with rise of temperature. On the other hand, if a to saturate 100 g of a dilute aqueous solution ofCuSO4 at 25° C
substance dissolves with evolution of heat, the solubility if 109 of the dilute solution leave on evaporation and dlying 1.2
decreases with rise of temperature. g of anhydrous CuSO4? The solubility ofCuSO4 in water at 25° C
Determination of solubilil); The solubility of salts is is 25.
generally determined by gravimetric method. First of all a Solution: 100 gof dilute solution of CUS04 contain
saturated solution is prepared. Some part of this saturated = 1.2 x 10= 12.0g CUS04
solution is weighed out in a porcelain dish. The solution is Mass of water present in dilute solution
evaporated slowly to dryness ona sand bath. The dish is cooled = (100-12) 88g
and weighed again. The observations are recorded as follows: To saturate 100 g of water, CuS0 4 required 25 g
332 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
So, to saturate 88 g of water, CuSO 4 required ~x88 termed lowering in vapour pressure and the ratio [ Po ~P S ] is
100
=22g
termed relative lowering in vapour pressure.
Thus, the mass of CuSO 4 to be added to 100 g of dilute
solution to saturate it (2212)=IOg Raoult, in 1886, established a relationship between relative
lowering in vapour pressure and composition of the solution after
5.9 COLLIGATIVEPROPERTIES OF a series of experiments in various solvents. The relationship is
DILUTE SOLUTIONS known as Raoult's law. It states that the relative lowering in
A dilute solution is one in which the amount of the solute is vapour pressure oCa dilute solution is equal to mole fraction
very small in comparison to the amount of the solvent. The of the solute present in the solution.
dilute solutions show more or less ideal behaviour as the heat and If n moles of solute be dissolved in N moles of the solvent, the
volume changes, accompanying the mixing of solute and solvent, mole fraction of the solute will be _n_ .
are negligible for all practical purposes. Dilute solutions obey n+N
Raoult's law, . Po - Ps n
Dilute solutions containing non-volatile solute exhibit some Accordmg to Raoult's law, = -'--
special properties which depend only upon the number of solute Po n+N
particles present in the solution irrespective of their nature. These This is the mathematical expression for Raoult's law.
properties are termed as colJigative properties. The colligative [Modified form of Raoult's law: The above relationship
properties are: can be written as,
(i) Lowering in the vapour pressure, n+N N
(ii) Elevation inthe boiling point, -=-=--=--=1+-
Po - P s n n
(iii) Depression in the freezing point and
(iv) Osmotic pressure. Po _ 1 =N or --""-"-_ == N .
or
Colligative ·properties are the properties of dilute solutions, Po Ps n Po - p, II
that is why these are termed as colligative properties of dilute
solutions. These properties are related to one another. Thus, if po-ps=n WAX~
or
one is measured, the other can be calculated. The importance of Ps N rnA wB
these properties lies in the fact that they provide methods for the
This equation gives accurate results and is easy to apply.]
determination of molecular masses of dissolved solutes. The
results are excellent if the following three conditions are Derivation of Raoult's Law for a Dilute Solution
satisfied: When a non-volatile solute is dissolved in a volatile solvent, a
(i) The solution should be very dilute. fraction of the surface of solvent is blocked by solute molecules
(ii) The solute should be non-volatile. where no evaporation occurs. Thus, under similar conditions, the
(iii) The solute does not dissociate or associate in sQlution. , vapour pressure is decreased. The vapour pressure of the
solution, thus, depends, upon the number of molecules of the
5~10 LOWERING IN .THE VAPOUR solvent present on the surface of the solution. The number of
PRESSURE such molecules is proportional to mole fraction of the solvent.
So, the vapour pr~ssure of solution,
When a non-volatile solute is added ,to a solvent, the vapoUr
pressure is lowered due to the following reasons: 'Ps'oc~
(i) Percentage surface area occupied by the solvent decreases. n+N
Thus, the rate of evaporation and vapour pressure decreases. The " N
solute molecules occupy the surface, and so the per cent surface or Ps k · - -
,area occupied by the solvent decreases. -n.¥N·
(ii) According to Graham's law-G}.evaporation, (k is proportionalityfaetor)
. 1 For pure solvent, n=0
Rate 0 f evaporatIOn oc ~
"density N
When a non-volatile solute is dissolved in a liquid, its density
and hence, Po =k == k '" (ii)
O+N
increases. Thus, both rate of evaporation and vapour pressure are Putting the value of kin eq. (i)
lowered. N
If Po is the vapour pressure of pure solvent and Psis the Ps =Po--
n+N
vapour pressure' of the solution, the 'difference (Po - P s ) is
Note: Isopiestic solutions: Two solutions having same vapour pressure at same temperature are known as isopiestic solutions.
SOLUTIONS 333
Solution: According to Raoult's law, Example 28. What mass of non-volatile' solute· (urea)
Po - p~ n needs to be dissolved in 100 g of water in order to decrease the
Po n+N vapour pressure of water by 25%. What will be the molality of
n solution? . (liT 1993)
or I1p=--· Po Solution: Using Raoult's law in the foHowing form,
n+N
50 '500 . Po - Ps wM
Given: n - = 0.146; N = = 27.78 and Po = 23.8
342 18 Ps Wm
Substituting the values in the above equation,
0.146 If Po = 100mm, then Ps 75mm
I1p = x 23.8 0.124 mm Hg
0.146+ 27.78 100 75 wX 18
Example 26. The vapour pressure of pure benzene at a ' 75 100x 60
certain temperature is 640mm Hg. A non-volatile solid weighing.
2.l75g is added to 39.0gofbenzene. The vapour pressure of the w=ll1.1
solution is 600 inm Hg. What is the molecular mass of the solid , w x 1000 111.1 x 1000
substance? (liT 1990; M~NR 1992) M01alty
. I =--- 18.52 m
mxW 60x 100
. Solution: According to Raou1t's law,
Po Ps =_n_ Example 29. A current of dry air was bubbled through a
Po n+N . bulb containing 26.66 g of an organic compound in 200 g of
water, then through a bulb at the same temperature, containing
Let m be the molecular mass of the solid substance.
water and finally through a tube containing anhydrous calcium
n=2.175· N 39 0.5 chloride. The loss of mass in bulb containing water was 0.087 g
m' 78
and gain in mass of the calcium chloride tube was 2.036 g.
(molecular mass of benzene 78) Calculate the molecular mass of the organic substance.
Po = 640 rom; Ps = 600 mm
Substituting the values in above equation,
Po Ps Loss in mass bulb
Solution:
2.175 Po Gain in mass of CaCl 2 tube
640 600 2.175 0.087
640 2.175+ O.5m 2.036
m
m 2.175 x 16-2.175 65.25 Let the molecular mass of the organic substance be m
According to Rao'ult's law,
0.5
Example 27. A solution containing 30 g of a non-volatile Po Ps
"'--"-~=---
wlm
solute in exactly 90g of water has a vapour pressure of21.85mm 'Po w W
-+
of Hg at 25°C. Further, 18 g of water is then added to the m M
solution; the new vapour pressure becomes 22.15 mm of Hg at 26.66
25°C. Calculate (a) molecular mass of the solute and (b) vapour 0.087 m =____
26.66 _
pressure of water at 25°C. (~llNR [<)90)
2.036 _26_.6_6 + _20_0 26.66+ 200 m
Solution:. Let the vapour pres~ure of water at 25°C be Po
m 18 18
and molecular mass of the solute be m
Usirig Raoult's law in the following form, m= 53.75
Po - Ps wM Example 30. The vapour pressure of a dilute aqueous
Ps Wm solution ofglucose is 750mm Hg at 373K. Calculate (i) molality,
(ii) mole fractio.n of the solute.
For solution (I), (Po - 21.85) 30x 18
21.85 90x m
... (i) solution: Po = Vapour pressure of water 373 K = 760 at
mmHg
' (II) (Po -22.15) 30Xl.8
. IutlOn
For so , = --- ." (ii) Using Raoult's law in the following fonn,
22.15 108 x m
Dividing eq. (i) by eq. (ii), Po Ps wM
(Po 21.85) 22.15 108 6 Ps Wm
--'-"--"----- x - - - - -
21.85 ( Po - 22.15) 90 5 760- 750
or ~x18
Po = 23.87 mm of Hg 750 Wm
Substituting the value of Po in eq. (i) w 10
or
m= 67.9 Wxm
SOLUTIONS 335-
[Ans. (d)] vapour pressure of water at 25°C is 17.5 rnm, what is the
molecular mass of the solute? [EAMCET (Engg) 2008j
[Hint: nA = = 100 = 5.55 (a) 206 (b) 302 (c)318 (d) 276
rnA 18
[ADS. (c)]
n 34.2 0.1 [Hint:
B .342 100/18
(17.5 0.225)= 17.5 x----~
x = 5.55 = 5.55 0.982 100/18+ -
A
5.55 + 0.1 5.65
p= poxA 17.275 (100 +~) 100
23.75 x 0.982 23.33 rum] 17.5 18 mB 18
21. Lowering of vapour pressure due to a solute in I molal
aqueous solution at 1000e is: 0.987 ( 5.55 + !:) 5.55
(a) 13.44 mm Hg (b) 14.12 mm Hg 25
(c) 31.2 mm Hg (d) 35.2mmHg 5.55 + - = 5.628
mB
[Ans. (a)]
mB '" 318mm]
x 1000
[Hint: m XB = mole fraction of solute
(l-xB)m A
rnA molar mass of solvent
5~11 ELEVATION OF BOILING POINT
1= x 1000 (Ebullioscopy)
(I xB)xl8 The boiling point of a liquid is the temperature at which its
XB 0.0176 vapour pressure is equal to the atmospheric pressure. The
vapour pressure of a liquid is lowered when a non-volatile solute
xA = 1- 0.0176= 0.9824 is added to it. Hence, the temperature of the solution when its
P = poxA vapour pressure will be equal to atmospheric pressure will be
= 760 x 0.9824 = 746.62 higher than the temperature of the pure solvent. In other words,
the boiling point of the solvent is elevated by the addition of
tlp = Po P = 760 746.62
non-volatile solute. The difference in the boiling point of the
'" 13.4 ] solution and the boiling point of the pure solvent is termed
22. The mass of a non-volatile solute (molecular mass = 40) elevation of boiling point.
which should be dissolved in 114 g octane to reduce its vapour Elevation of boiling point,
pressure to 80% will be: (t1T) Boiling point of the solution - Boiling point of pure
(a)20g (b)30g (c) 109 (d)40g solvent
[ADS. (e)] This can be better understood by plotting a graph of vapour
[Hint: If Po 100, then P 80
. pressure against temperature for a pure solvent and two solutions
of different concentrations. The curves orthe solutions always lie
P= Po XA below the curve of th,e pure solvent. The line poe represents the
80 = 100 xXA atmospheric pressure. To', TI and T2 represent the boiling points
xA =0.80 of pure soJvent, solution I and solution II respectively. The
114/114 vapour pressure of pure solvent, solution I and solution II at'
1141114 + wB /40 temperature To are Po, p] and P2 respectively.
'0,8=---
1 + Ws /40
1 + Ws = 1 t
40 0.8
wB 10 g]
. 23. 3g urea is dissolved in 45g of water. The relative lowering of
vapour pressure is : IComed (Karnataka) 20081
(a) 0.05 (b) 0.04 (c) 0.02 (d) 0.01
[Ans. (c)]
3 To T1 T2
(HiDt: ns = 0.05; 45 = 2.5
60 18 Temperature :......-
Assuming that the solutions are very dilute, these curves may K
Then, I1T=-==K b
, be approximately taken as straight lines near the boiling point. lOOO
Thus, AA CE and AABD are similar.
. AC AE K b is called molal elevation constant. II 'J:; defined as the
Therefore, --- elevation in boiling point produced when 1 mole of the solute
AB AD
T2 -To == is dissolved in 1000 g of the solvent.
or
T\ -To Po PI Thus, K 1000K b
I1T2 11P2
or Putting this value in eq. (i),
1111 I1Pj
or I1T ex: I1P I1T == 1000K b WA
... (iii)
From Raoult's law for dilute solution, mA WB.
Po - Ps _ WB xm A or I1T == Molality x K b
Po .,mB XWA
straight lines and CB is also nearly a straight line. The ABEC and
K
ABDF are similar. AT
100
EC BE
So,
DF BD =K'
WB
If - == I and W A = 1000 g
mB
K
AT
1000
Kf
Kf is called molal depression constant.
T Z T1 To
It is defined as the depression of freezing point produced
Temperature -
when 1 mole of solute is dissolved in 1000 g of the solvent.
Fig. 5.11 Thus, K == 1000Kr
. From Raoult's law for dilute solurions, Putting this value in eq. (i),
Po - Ps wB. mA
Po mB w A AT == 1000Kf -=-- ... (iii)
mB wA
* This relation may alsQ'be written as:
' W O O Kr x W
AT
ImxW
where W and Ware the masses of solute and sol ver:t respectively and m =molecular mass of solute.
SOLUTIONS
or AT = molality x K J (iv) Solute does not form a solid solution with solvent in frozen state,
i.e., only solvent separates in solid state on freezing the solution.
KJ is characteristic of a particular solvent and can be (v) Equimolal quantities of different substances dissolved in the
calculated from the thermodynamical relationship . same quantity of solvent bring out the same depression in
0.002 2 freezing point of the solvent under identical conditions.
SOLUTIONS
(b) 0.512 (c) 0.512 (d) 0.0512 Difference between Osmosis and Diffusion
(a) 0.186
1.86 The two processes, diffusion and osmosis, can be
[Ans. (d)) distinguished in terms of the following aspects:
[Hint: llT = K j x m (i) In diffusion, solute as well as solvent molecules flow in
0.186 = 1.86 x m opposite directions while in osmosis the flow of solvent
m 0.1
molecules occurs in one direction only.
(ii) For osmosis, a semipermeable membrane* is required
llT = Kb x m =0.512 x 0.1 = 0.0512) while for diffusion it is not required.
30. The amount of urea to be dissolved in 500 cc of water
( K r 1.86) to produce a depression :::'" :JJ 86°C in the Semipermeable membrane
freezing point is: (UGET (ManipaJ) 2006) "A membrane which allows the solvent molecules to pass
(a)9g (b)6g (c)3g (d)O.3g through it but prevents the passage ofsolute molecules through it
[Ans. (c)] is called a semipermeable membrane." . . .
[Hint: '-'AT =-- K j x wB X 1000 Examples of semipermeable membranes are too many.
mB x WA Parchment paper, membranes covering the animal and plant cells
x 1000 and many gelatinous inorganic substances such as calcium
0.186 1.86 x
60x 500 phosphate and copper ferrocyanide, etc., act as semipermeable
WB = 3 g] membranes. Animal and plant membranes are not all completely
semipermeable. The best semipermeable membrane used is
31. What should be the freezing point of aqueous solution
. prepared by deposition of copper ferrocyanide, CU2[Fe(CN)6]'
containing 17 g ofC 2 H sOH in 1000 g of water (Kj for water
in the pores of a porous pot.
J.86deg kg mol-.1)?
Working of semipermeable membrane : Sev~ral theories
(a) 0.69°C (b) 0.34°C have been put forward to explain thewv,~...~ng Vi semIllt:rmeable
(c) O.O°C (d) 0.34°C membrane. These are :
[Ans. (a)]
(a) The sieve theory: The theory was suggested by Traube.
[Hint: llT =Kr x x 1000 = 1.86 x 17 x 1000 = 0.69 According to this theory, a semipermeable membrane contains a
mB x WA 46 x 1000 large number of small pores which eet like a sieve. The pores
Freezing point of solution =0 - 0.69; 0.69° C] allow the smaller molecules of solvent to pass through it but does
.not allow the larger molecules of solute to do so. However, this
5.13 OSMOSIS AND OSMOTIC PRESSURE theory fails in those cases of semipermeability where the solute
molecules' are smaller than the solvent molecules.
Osmosis: When a semipermeable membrane is placed between (b) The solution theory : According to this theory, a
a solution and a solvent, it is observed that solvent molecules membrane is permeable to those substances which dissolve in it
enter the60lution arid the volume of solution increases. It is also and is impermeable to those which are insoluble in it. Thus, a
observed that if two solutions of unequal concentrations are layer of phenol acts as a semipermeable membrane when placed
separated by a semipermeable membrane, the solvent molecules
between a solution of Ca(N03 h. Phenol allows water to pass
from a solution of lower concentration move towards a solution through it because water is soluble in phenol. It is impermeable to
of higher concentration. This phenomenon was first observed by
Ca(N03 h because Ca(N03 h is insoluble in phenol.
Abbe Nollet (1748) and termed as Osmosis (Greek, osmos to
(c) Vapour pressure theory : According to this theory, a
push). Osmosis is defined as the spontaneous flow of solvent
solvent can pass through a semipermeable membrane because the
molecules through semipermeable membrane from a pure
vapour pressure of the pure solvent is higher than the vapour
solvent to a solution or from a dilute to a concentrated
pressure ofthe solution. This theory is widely accepted because it
solution.
explains the phenomenon of osmosis.
The phenomenon of osmosis can be demonstrated by the
Osmotic pressure: A porous pot is taken and a
following experiment:
semipermeable membrane of copper ferrocyanide is deposited in
Two eggs of same size are taken and their outer hardshell is its walls. It is fitted with a long glass tube with the help of a
removed by dissolving in dilute hydrochloric acid. One of the rubber stopper. It is filled with concentrated aqueous sugar
eggs is placed in distilled water and the other in saturated salt solution and placed in distilled water. Osmosis occurs and the
solution. level· of the solution in glass tube rises over a period of time.
After sufficient time, it is noticed that the egg placed in water After a few days, the level becomes stationary. At this
swells up and that placed in salt solution shrinks. In the first case, eqUilibrium state the hydrostatic pressure of the liquid column
water enters the concentrated egg fluid while in the second case, exactly balances the tendency which enables the water molecules
water comes out of the egg as salt solution is more concentrated to pass through semipermeable membrane.
than the egg fluid. ,
* Membranes which allow the passage of only solvent molecules through them are called semipermeable membranes. Egg membrane, goat's bladder
and cell membranes can serve as semiperineable membranes but these are not perfect for laboratory measurements. Artificial membranes of gelatinous
inorganic substances such as copper ferrocyanide are used these days as semipermeable membranes.
I
SOLUT.IONS I 343
Maximum level solution in order to stop the flow of the solvent into the
- .
solution through semipermeable membrane is equal to
: I
. Hydrostatic
pressure
Initial level
0smotic pressure.
hypertonic because solvent concentration is greater in hypotonic 5.14 VAN'T HOFF THEORY OF DILUTE
solution. This phenomenon is known as plasmolysis. The change SOLUTIONS
in cell can be observed under a microscope. When the plant cell is.
van't Hoff realised that an analogy exists between gases and
placed in the solution of same osmotic pressure as that of the cell
solutions provided osmotic pressure of solutions is used in place
fluid, no change in the structure of the cell is observed. Such
of ordinary gas pressure. He showed that for dilute solutions of
solutions having same osmotic pressures are termed isotonic. By non-electrolytes the following laws hold good:
putting, therefore, cells of the same kind into solutions of
1. Boyle-van't Hoff law: The osmotic pressure (P or 1t)
different concentrations, it can be ascertained whether the
solution is hypertonic or hypotonic or isotonic. of a solution is directly proportional to its concentration (C )
when the temperature is kept constant. The concentration of the
or poc_1
V
or PV constant or 1t V constant
(A) (8)
van't Hoff presumed that the osmotic pressure is due to the
Fig.5.15 Plasmolys,is' bombardment of solute molecules against the semipermeable
membrane as the gas pressure is due to hits recorded by gas
, Some biological explanation on the basis of osmosis are given molecules against the walls of its container.
below: . '
2. Pressure~Temperature law (Gay-Lussac-van't Hoff
(i) In animals, circulation of water to all parts of body takes
law): Concentration remaining same, the osmotic pressure of a
place due to osmosis. . .
dilute solution is directly proportional to its absolute temperature
(ii) Plant roots absorb water from soil due to osmosis. Concen- (T), i.e., .
tration of cell sap illside the root hair cells is higher than that of
water present in the soil. Water enters the root cells due to
endosmosis. P 1t
or - = constant or - := constant
(iii) Water absorbed by plant roots is circulated in the entire T T
. plant body and reaches to the top of a tall tree due to osmosis. Combining the two laws, i. e., when concentration and
(iv) Osmosis helps in plant growth and germination of s~eds. temperature both are changing, the osmotic pressure will be
(v) Red blood cells burst when placed in water; it is due to given by:
endosmosis. pocCT
(vi) Vari?us functions of plants are controlled by osmosis,
e.g., stretchmg of leaves and flowers, opening and closing of or p:= kCT
flowers.
(vii) Use of salt and sugar in pickles and jams acts as or
1
P=k·_·T
V
( ~ince, C == ~)
preser~atives. It prevents growth of bacteria and fungi by
osmOSIS. or PV STornV ST
(viii) Dead bodie3 swell under water due to endosmosis.
S is called molar solution constant.
(ix) When dried fruits and vegetables are placed in water, they
Here, V is the volume of solution containing one gram mole of
slowly swell and return to the original form. It is again due to
the solute. The value of S comes out to 0.082 litre atm K- 1 mol- 1
endosmosis of water into the fruits and vegetables.
'. Intravenous drip of saline water: Saline drip to the patients which is in agreement with the value of R, the molar gas constant.
IS also based on the principle of osmosis. In case, the solution contains n gram moles in V litre, the general
equation would become:
(i) A 0.91% solution of NaCI in water is isotonic to human
blood. Hence, in this solution red blood cells neither swell nor PV nST or1tV=nST
shrink. 3. Third law: Equimolecular solutions of different solutes
(ii) Aqueous solution of NaCI with concentration less than exert equal osmotic pressure under identical conditions of
0.91 % is hypotonic to blood. On placing red blood cells in this temperature. Such solutions which have the same osmotic
solution, endosmosis results into bursting ofRBCs. pressure are termed isotonic or iso-osmotic. When two isotonic
(iii) Aqueous solution ofNaCI with concentration more than solutions are separated by a semipermeable membrane, no flow
of solvent molecules is observed on either side.
0.91 % is hypertonic to blood. On placing red blood cells in it
exosmosis or plasmolysis results into shrinking of cells.
SOLUTIONS
n = WB and V V' Here, i l and i z are van't Hofffactor'for the two solutes.
mB
Thus, the equation PV = nST becomes: ······1
•••••• SoME SOLVED EXAMPLE51••••
•••···•.
PV ' = wB ·ST , Example 49. 200 em 3 ofan aqueous solution contains 1.26
me
g of a polymer. The osmotic pressure of such solution at 300 K is
wB xS xT found to be 2.57 x 19-3 bar., Calculate the molar mass of the
or me -
- --"PV-' - - polymer. .
Knowing the value of P experimentally, the value of mA ' i. e. , 1tV WB RT
Solution:
molecular mass of the solute can be determined. ma
Consider two solutions I and II having ni and n2 moles of the
,WB RT
solute in VI and V2 · litres of solution respectively. Let PI and P2 me=-x-
be their osmotic pressures at the same temperature (T). V 1t
= 0.083 litre atm per degree per mol m2 =0.877 x 342 = 59.987
5
Example 54.What is the volume ofsolution containing Ig
mole of sugar that will give rise to an osmotic pressure of OF OBJECTIVE quESTIONS
1atmosphere at O°C?
.Solution.: Applying the equation PV == n· ST, 32. . Find out the osmotic pressure of 0.25 M aqueous solution of
urea at 27°C (R 0.082 litre atm K- 1 mol-I, R =.1.987 cal
V=n xSxT
P K-1mor I). ICET (Gujarat) 10081
(a) 6.15 atm (b) 0.615 atm (c) 0.0615 atm (d) 61.5 atm
Given,n = 1,P == latm, S = 0.0821 and T == 273K [Ans. (a)]
SOLUTIONS 34L
[Hint: Tt = CRT
37. The temperature at which 10% aqu~~us solution (~) of
= 0.25 x 0.0821 x 300
= 6.157 atm] glucose will exhibit the osmotic pressure of 16.4 atm, is :
3 l
33. Two solutions of glucose have osmotic pressures 1.5 and 2.5 (R 0.082dm atm K-1mol- ) IPMT (Kerala) 2008)
atm. I litre of first solution is mixed with 2 litre of second (a) 360°C (b) 180 K (c) 90 K (d) 300 K
solution. The osmotic pressure of the resultant solution will (e) 360 K
be: [Ans. (e)]
(a) 1.62 attn (b) 6.12 attn (c) 1.26 atm (d) 2.16 atm [Hint: TtV :=:nRT
[Ans. (d)]
TtV=W RT
[Hint: Tt IVl + Tt ZV2 Tt R (VI + V2) m
. Table 5.6 Illustrations of van't HOff Factor "i' for Different Solutes
No. of particles In van't Hoff
.Example Abnormal
S. Solute type Ionisation or associadon the solution from factor'i' molecular mass
No. t mole solute
1. Non-electrolyte Urea, sucrose, glucose .- J 1 mnormal
2. ~inary electrolyte
ABtype
NaCl, KCl
CH3CO(JR, etc.
AB
I - a-
A+ + B-
a- a
2 1+ a 1+ a
mnormal
AB3 ~ A 3+ + 3B-.
I
4. puatemary . AlCI 3, K 3[Fe(CN h] . 4 1 + 30. . ~ormal
~lectrolyte AB3 or PeC1 3, K 3P0 4 . . I-a a 3a 1+30.
iA3B type A3B ~ 3A+ + B 3- . 4 1 + 30. mnormaJ
I -a- 3a a 1+ 30.
= (£¥7 )obs.
(AP}nonnal
1+(~ l)a
Thus, van't Hoff factor' i ' = _-,-n~-,--_ < 1if n is 2 or more
1
(ATb )Obs.= (AT! )obs.
1- i
(ATb )normal (AT! )nonnal a=---
I lin
Actual no. of in solution
=-------''--------
No. of particles taken As, Colligative property oc I
moL mass
(i) Suppose one molecule of an electrolyte gives' n' ions on
Observed colligative property . Normal mol. mass
dissociation and' a' is its degree of ionisation. Obviously, So, ==
Number of ions produced na Normal colligative property Observed mol. mass
and Number of unionised molecules = I a Normal mol.
Thus, i=------.:...-
Total number of particles in solution 1- a + na Observed mol. mass
= 1+ (n -l)a In case of dissociation,
Thus,
. . l+(n l)a f
-Normal
- - -moL
- -mass
- = I·+ ( n-. 1) a> I
van't Hoff factor' i' = --'---'-- > Ii n is 2 or more Observed mol. mass
I
Observed mol. mass will always be less than normal mol. mass.
i-I
and a=-- In case of association,
n 1 . _ Normal mol. mass -_ I + ( --
1-
1 a< 1 I.)
(ii) Suppose 'n' molecules associate to form one giant Observed mol. mass n
molecule and' a' is the degree of association; then. Observed mol. mass will always be higher than normal mol. mass.
nA (A)"
(I-a) alll Relathm between osmotic pressure and vapour pressure
Total number of particles in solution 1- a + a / n Let an aqueous dilute solution filled in a capillary tube is
closed at one end by a semipermeable membrane. The tube is
=1+(~-IJa placed in pure solvent (water). Entire apparatus is closed by a
beUjar. At osmotic equilibrium, the belljar is saturated with water
. ;
SOLUTIONS 349
vapour. At equilibrium osmotic pressure (1t) becomes equal to Partial pressure of immiscible liquids
hydrostatic pressure. Let 'A' and 'B' be the two volatile and immiscible liquids; p A
1t=hxd ... (i) and p B be the partial pressures of 'A' and' B' respectively.
where 'h' is height in the column, 1t is osmotic pressure. . _PA .=_nA
Then,
Let, Po = Vapour pressure of pure solvent PB nB
p Vapour pressure of solution where, M A and M B are molar' concentrations of 'A' and 'B'
respectively.
_ WA ImA
PB WBlm E
......r----- Saturated space where, W A and WB are weights of' A' and' B', m A and mB are
with water vapour molecular weights of' A' and' B' respectively.
Example 58. Phenol associates in benzene to a certain
L~---+-- Solution e;tent for a dimer. A solution containing 20 x 10-3 kg ofphenol in
1.0 kg of benzene has its freezing point decreased by 0.69 K.
Pure solvent
Calculate the fraction of the phenol that has dimerised (Kf of
benzene is 5.12°K kg mol-I). .
. Semipermeable
membrane Solution: Observed mol. mass
1000xK f Xw
=---~--
WxllT
Fig. 5.16 3
x 5.12x 20x 10- := 148.4
Pressure at level 4 = Po; Pressure at level 0. = p. Pressure at Ix 0.69
4 will be greater than pressure at 0.. Then
Normal mol. mass of phenol (C 6 HsOH) =94
Po - P = hD ... (ii)
Normal mol. mass 94
where'D' is density of solvent vapour at pressure Po. So,
Observed moL mass 148.4
Dividing eq. (i) by eq. (ii), we have,
1t hd d
Po - p hD D
94 . a;
at a ftxed temperature diD is constant. 1--
.. 1t = constant ( Po - p) ... (iii) 148.4 2
Let 6.T be the depression in freezing point. 6.Pobs. = No. of particles after dissociation
6.T = Kf x molality 6.Ptheo. No. of particles when there is no dissociation
2
= 1.86 x =0.151K I+(n-l)a. xU7
0.0821 x 300 --'--;---'--- = 2.4
I
Freezing point =(27.3 0.151) =272.749 K or - 0.151° C
So, 6.Pobs. = 2.4 X 6.Ptheo. = 2.4 x 5.84
Example. 2. Calculate the amount ofNaCI which must be =·14.02mm
added to 100 g water so that freezing point is depressed by 2 K
For water, Kf 1.86K kg mol-I. Po Ps:: 6.Pobs. = 14.02
Solution: NaCI is a strong ele\,:trolyte. It is completely Ps Po 14.02= 760-14.02:: 745.98mrn
dissociated in solution. Example 4. Calculate the osmotic pressure of solution
Degree of dissociation, a. obtained by mixing 100 mL of 3.4 % solution of urea (molecular
mass = 60) and 100 mL ofl.6% solution ofcane sugar (molecular
NaCI + CI- • mass 342) at 20°C.
(n = 2)
--=2
2 Total volume of solution =(100 + 100) = .200 mL
6. Ttheo . = Q.2litre.····
'. .
or 6. Ttheo . = 1 PV = (Total numbitr ofmoles} x. S x T
Let w g of NaCI be dissolved in 100 g of water. 00614 ..... ,'" ....•.
1000 x xw P = -'-~ x 0.0821 x 293:: 7.385 atm
So, 6. Ttheo . =.---""---
0.2
Wxm
Example S. Calculat~ the normal boilingpoint ofa sample
or w 6.r;heo
. xWxm I x 100 x 58.5 \t .. ofsea water found to contain 3.5%ofNaCI and O. 13% ofMgCl2 by
1000x K f 1000x 1.86 mass. The normal boiling point of water is 100°C and K b (water)
0.51 K kg mol -I. Assume that both the salts are completely
=3.145g' ionised.
Example 3. The degree of dissociation ofCa(N03 h in a Solution: Mass ofNaCI = 3.5 g
dilute solution containing 14 g of the salt per 200 g of water at
100°C is 70%. If the vapour pressure of water is 760 mm, No. of moles of. NaCl = ~
calculate the vapour pressure ofsolution. (lIT 1991) 58.5
SotUTIONs"
-
Number of ions furnished by one molecule ofNaCI is 2; 100
Volume of solution:::: litre '
So, actual number of moles of particles furnished by 1.04 x 1000
sodium chloride:::: 2 x 3.5
58.5 n; = 2 x 3.5 x1.04x 1000x 0.0821 x 293 = 29.93 atm
58.5 100 -
Similarly, actual number of moles of particles furnished by
'Example 8. Molality of a solution in aqueous medium is
.
magnesIum chl'd
on e:::: 3 X -
0.13
-' 0.8 . Calculate its mole fraction and the percentage by mass of
95 solute if molar mass of solute is 60.
Solution: We know that,
Total number of moles of particles;::; (2 x 3.5 +3 x 0.13,)
58.5 95 ~ 'm x 1000
... (i)
(l-xB)xm A
== 0.1238
wl),ere, xB :::: mole fraction of solute'
Mass of water = (100- 3.5- 0.13)= 96.37 g ~~~Z kg mA = molar mass of solvent
0.8= xB x 1000
Molality :::: 0.1238 x 1000 = 1.2846 (l-xB)x 18
96.37 x B == 0.014
tlTb :::: Molality x Kb Let WB =x g, W A =100 g
=1.2846 x 0.51= 0.655 K w X 1000
mB= '
Hence, boiling point ofsea water:::: 373.655 K or lOQ.655"C. mB XWA
"Example 6. ' A solution of a non-volatile solute in water 0.8= xX 1000
has a boiling point of375.3K. Calculate the vapour pressure of 60x 100
water above this solution at 338 K. Given, Po (water) :::: 0.2467
x=4.8%
atm at 338K and K bfor water = 0.52.
Example 9. Calculate the boiling point of a solution
Solution: tlTb:::: (375.3 - 373.15):::: 2.15 K
containing 0.61 g of benzoic acid in 50 g of CS 2 (I) assuming
We know that, 84% dimerisation of the acid. The boiling point and K b ofCS 2
tlTb =: Molality X Kb are 46.2 0 C and 2.3 K kg mor l r.espectiveiy. (lIT 1997),
Solution: tlT :::: i x K b x Molality
2.15:::: Molality x 0.52
. K
==lX b xwx1000
---
Molality:::: 2.15 :::: 4.135 , mXW
0.52
i-i
i. e;, 4.135 moles of the solute present in 1000 g of water (55.5 a=---
1 lin
moles).
0.84::::~
Mole fraction of water :::: 55.5 :::: _5_5_.5_ 1 112
4.135+ 55.5 59.635 i= 0.58 '
Vapour pressure of water above solution tlT:::: 0.58 x 2.3 x 0.61 x 1000:::: 0.1334
:::: Mole fraction x Po 122x 50
T
To::= 0.1334
:::: ~ X 0.2467 =: 0.23 atm T :::: T~ + 0.1334::: 46.2 + 0.1334:::: 46.3334
59.635
Example 10. A very small amount of a non-volatile solute
,:'Example 7. Sea water is 3.5% by mass of a salt and has a
(that does not dissociate) is dissolved in 56.8cm 3 of benzene
density 1.04 g cm -3 at 293 K. Assuming the salt to be sodium
(density 0.889 g cm- 3 ).At room temperature, vapour pressure of
chloride. calculate the osmotiC pressure of sea water. Assume
complete ionisation of the salt. ' this solution is 98.8 mm Hg while that of benzene is 100 mm Hg.
Find the molality of the solution. If the freezing temperature of
Solution: Mass ofNaCI :::: 3.5 g this solution is 0.73 degree lower than. that ofbenzene, what is the
value of molal freezing point depression constant of benzene?
No. of moles:::: 3.5 , (DT199~
58.5 tlp ,
Solution: -=X A
Actual number 6f moles of particles of solute in solution
Po .
2x 3.5 100- 98.8
--- XA
58.5 100
3541 ~.R.B. PHYSICALCH6MISTRYFOR COMPETITIONS
X A =0.012 w= 56.66g
Molality = X A X 1000 = 0.OI2x ~OOO= 0.1557
(1- X A )mB' 0.988 x 78 V=~
d
AT = KI x Molality 50= 56.66
0.73 = KI x 0.1557 d
KI =4.688 < d =1.13 gl cm~
~if,:rtlilDp~ 11. The solution ofa non-volatile solute in water ~4::tx.lDple 14. A 1.2% solution of NaCI is isotonic with
freezes at - 0.30 0 C. The vapour pressure ofpure water at 298 K 7.2% solution ofglucose. Calculate the van ~ HoJJfactor ofNaCl.
is 23.51 mm Hg and KI for water is 1.86 degree/molal. (MLNR 1997)
Calculate the vapour pressure ofthis solution at 298 K . Solution: NaCl glucose
(liT 1998) = 7t(glucose)
Solution: AT = KI x Molality =C 2RT
0.3 = 1.86 x Molality
iCt = C2
Molality = 0.161 {12I:S.5J = 7.2~I80
' XA x 1000
. 'M0 lal tty = --"'---- i = 7.2x 58.5 = 1.95
(I-XA )xmB
1.2 x 180
. 0.161= X A x 1000 [l'J~ii3IDple IS. 1.4 g of acetone dissolved ,in 100 g of
(I-XA)I8 benzene gave a solution which freezes at 277.12 K. Pure benzene
X A =0:00289 freezes at 278.4 K. 2.8 g ofsolid (A) dissolved in 100 g ofbenzene
gave a solution which froze at 277.76 K. Calculate the molecular
tJ.p =XA mass of(A). (lIT 2000)
Po. Solution:. We .know that,
23.51- Ps = 0.00289 AT= K x wx 1000
23.51 f mxW
Ps =23.442mm when:, AT = Depression in freezing point
~Yf:.EiaiDpie 11. x g of a non-electrolytic compound (molar
mass = 200) is dissolved in 1.0 litre of0.05 M NaCI solution. The Kf = Molal depression constant of benzene
osmotic pressure of this solution is found to be 4.92 aim at. 27 0 C. w == Mass of solute
Calculate the value of' x' . Assume complete' dissociation ofNaCI
m = Molecular mass of solute'
and ideal behaviour of this solution. (liT 1998)
Solution: W = Mass of solvent
(i) For NaCI: 7t = iCRT = 2 x 0.05 x 0.0821 x 300 Case I: (278.4 _ 277.12)= K x 1.4 x 1000
=2.463 attn I 58x 100
(ii) For unknown compound: . 14
1.28= KI x 58 ... {I)
7t=CRT =-=- x 0.0821 x 300= 0.1 23 lx attn
200 Case n: (278.4- 277.76)= K x 2.8x 1000
f
Total osmotic pressure 7t = 7tJ + 7t2 m(A) x 100
....
i~~"* p.le 13. The freezing point of a solution containing· Dividing eq. (l) by eq. (2), we get
50 cm 3 of ethylene glycol in 50 g of water is found to be -34° C.
m(A) =232
Assuming ideal behaviour, calculate the density of ethylene glycol
. (KI for water = 1.86K kg mol- t ). (lIT 1999)
ii.'~"iulDpIe16. To 500 cm 3 of water, 3.0x 10-3 kg ofacetic
"
acid is added. /f23% ofacetic acid is dissociated, what will be the
Solution: AT= K x wX 1000 depression in freezing point? Kf and denSity ofwater are 1.86 K
I mxW kg-I morl andO.997gcm-3 respectively. (lIT 2000)
Solution! Mass of solute = 3.0 x 10-3 kg =3.0 g
34 = 1.86 x wX 1000 .
. 62x 50 Molecular mass of solute = 60
SOLUTIONS 1355.
Mass of solvent = 500 x 0.997 = 498.5 g Solution: Molal elevation constant may be calculated as~
We know that, K _ RTo 2 (where, To =boiling point of pure solvent
b(()OO - 1000 Lv Lv = latent heat of vaporization
' . . ((l ) ::: -i-I
Degree 0 fd lssoclatlon .- . pergram
n-I RTo2 .. AHv
= Lv = - - )
0.23= i-I l000 AHv mB
2-1 mB (here; AHv =molar latent heat of .
vaporization .
or i = 1.23
mB = molar mass of solute)
AT =i x K f x molality
·
Smce, AC' AHv
L.W v = - -
1. SoiufioHi It is a homogeneous mixture .of two of more 4. Solutions of liquids In liquids! Miscib.1e liquids form
components· whose concentration can be varied within certain three types of solutions which may be ideal or non-ideal solutions.
limits. A solution containing only two components is termed a Ideal solution is that in which the attractive forces among the
. binary solution:. One component is called the solute while other solute and solvent molecules are of the same order as that of
as solvent. The component having the same physical state as the solute intramolecular and solvent intramolecular forces. The W
solution is called the solvent. In solutions, in which the two mix~g and I:!V mixing in such solutions is zero. Ideal solutions
components have the same physical state, the component present obey Raoult's law.
in larger proportion is termed the solvent and the other The solutions in which solute-solvent interactions are
componen:t is called solute. different from solute-solute and solvent-solvent interactions are
2. $()tubiUtyi A solution is said to· be saturated when it called non~ideal solutions. The non-ideal solutions do not obey
contains as much solute as it can dissolve at a particular Raoult's law for all concentrations.
temperature in presence of the undissolved solute. A super- W mix *" 0 and I:! V*"O in these solutions. There are two types
saturated solution contains more. quantity and an unsaturated of deviations from the ideal behaviour. .
solution contains less quantity of the solute than a saturated (i) If I:! Vmix > 0 and W mix > 0, then non-ideal solutions
solution. . . . show positive deviations, Such solutions form a constant boiling
The amount of the solute in grams which can dissolve at a mixture of defmite cOInposition (azeotropic mixture) having
particular temperature in 100 grams of the solvent when the . boiling point less than either of both the liquids. In these
solution is saturated is termed solubility of the solute. solutions . solvent-solvent and solute-solute interactions are
3. SolubUlty of a 11l8tH It liquid: Gases which can be stronger than solvent-solute interactions. Examples are:
.easily liquified are more soluble in common solvents. The gases H20+CH3 0H;H 2 0+ C2~OH; C6H6 + CH3 0H;
which form ions in water are highly soluble in water. The C 6H6 + CCI 4 ; (CH 3 hCO+ C 6H6; (CH 3 h CO+ C2~OH.
solu~ility of a gas generally decreases with rise in temperature (ii) If I:!Vmix < 0 and W mix < 0, then non-ideal solutions
and mcreases with increase in pressure. show negative deviations, In these solutions, solvent-solvent and
Mass of gas dissolved per unit volume of a solvent is directly solute-solute interactions are weaker than solvent-solute
proportional to the pressure of the gaS at a given temperature. interactions. Such solutions also form azeotropic mixture having
This is Henry's law. boiling point higher than either of the two solvents. Examples
m KP (at constant temperature)
where, m is the mass of gas dissolved per unit volume of solvent,
P is pressure of the gas in equilibrium with the solution and K is
proportionality constant.
357
}, Mass percentage %(WIW) Mass of solute Number of parts by mass of solute per hun- No effect
x 100
Mass of solution dred parts of the solution.
1.,. Gram per litre gIL Mass of solute in grams Amount of the solute in grams present in Changes' with change
Volume of solution in litres - one litre of solution. of temperature.
$, Parts per million ppm Mass of solute Number of parts by mass of solute per 1(f No effect
X 106
Mass of solution parts of solution.
4, Molarity M Number of moles of solute Number of moles of solute per litre of solu- Changes with challge
Number of litres of solution tion . of temperature. '
$. Formality F Number of formula mass Number of formula mass in grams present Changes with change
Number of litres of solution per litre of solution. of temperature.
-
(" ~"W§ mw~ The partial pressure of any volatile
constituent of a solution at a constant temperature is equal to the
pressure. (po ~ Ps J is called relative lowering in vapour
vapour pressure of pure constituent multiplied by mole fraction
pressure.
of that constituent in the solution.
The relativ~ lowering in vapour pressure of a solution
P A == mole fraction of A x p~ ~ X A X p~ containing non-volatile solute is equal to the mole fraction of the
In the case of binary solution of two volatile liquids, the total solute present in the solution. this is Raoult's law.
vapour pressure of such solution can be given as: Mathematically,
Total vapour pressure of solution == p~ x X A + p~ X X B Po - Ps X n
. Po == solute == n+N
== P A + PB
Mole fraction of component A in vapour phase, Let w g of the solute (mol. mass == m) be dissolved in W g of
i. e., YA ==~== p~ XA solvent (molecular mass == M).
P p~ X A + p~ XB Po-Ps .wlm
Po wlm+WIM
p~ XB
similarly, YB == --~--=-- If the solution is very dilute wi m in denominator can. be
p~ X A + p~ XB neglected.
7. etl~y~ "~~~} The properties of dilute Po - P s _ wi m_ wM !'l.p
solutions containing non-volatile solutes, which depend upon the Po - WI M - mW or Po m A wB
number of solute particles in solution are called colligative
properties. These properties do not depend upon the natUre of ' .. Eley!l;Cicm M Wi~~: The boiling point of a
solutes and solvents. The four colligative properties are: solution containing non-volatile solute is always higher than the
(i) Relative lowering in vapour pressure boiling point of a pure solvent. The increase in boiling point is
(ii). Elevation in the boiling point termed elevation and represented' as !'l.Tb'
(iii) Depression in the freezing point I1Tb oc Molality of the solution
(iv) Osmotic pressure.
or !'l.Tb == m x K b . (K b is a molal elevation constant)
All these properties are dependent on the concentration of
solutes in solution. lOOOxK b Xw IOOOxK b xW A
or !'l.Tb == or . !'l.Tb == -----"---.....:-::-
!S.• ~o/~ JMy~iJ.l t'qHf "~fg:: When' a Wxm wBxmA
non-volatile solute is dissolved' in a solvent, its vapour
pressure decreases. ( Po - P s )is known as lowering in vapour where, W == mass of solute; m ==. molecular mass of solute;
W == mass of solvent
358 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
i.e., P=~.RT
mxV
Molecular masses of electrolytes observed by the methods
Best method for the determination of osmotic pressure is based on colligative properties are always leSs than nonnal
Berkeley and Hartley's method. molecular masses.
The tenn hypertonic and hypotonic are applied to compare the
osmotic pressures of two solutions. The solution having lower
SOLUTIONS
= dRT
R gas constant in attn mL I deg I mol, i. e. , 82.1 . 7t =I1Tb X - --
lOOOK
14. Variation of vapour pressure with temperature b
(Clausius-ClapeyrOli equation): (ii) Osmotic pressure 7t and freezing point depression I1T, :
log 10 (PPr
2
) =~ [..!.. - ..!.]
2.303R 7j T2 7t =I1T, x - dRT
--
lOOOK ,
where, ~ =vapour pressure at7j (iii) Elevation in boiling point and relative lowering of
P2 =vapour pressure at T2 vapour pressure:
fjJ[ = latent heat of vaporization per mole
15. Variation of vapour pressure of a liquid with external
I1Tb =tOOOK b X -l1P ; mA =molar mass ofsolvent
mA Po
pressure:
(iv) Depression in freezing point and relative lowering of
IOglO(P2)=
PI 2.303RT
(P2-~) vapour pressure:
/
• .360 G,R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Questions
1. Match the following:. [D] Match the solutions in Column-I with their osmotic
Set-I properties in Column-II:"
Set-II
Column-I Column-II
(A) 10 vol HzOz 1. Perhydrol
. (a) SI: 0.1 M glucose, (P) S 1 and S 2 are isotonic
(B) 20 vol H Z02 2.5.358N Sz: O. lM urea ;
(e) 30 vol H Z02 , 3.1.785N (b) SI: 0.1 M NaCI, (q) No migration of solvent
Sz-0:lMNazS04 ~ross the membrane
(D)100 vol HzOz 4.3.03 %
(c)SI:O.lMNaCI, (r) 8.1 is hyp.ertonic to Sz
The correct match is : . Sz:O.1MKCl
(a)A-4,B- 3,C-2,D-I (d) SI:O.l M CuS04 , (s) SI is hyPotonic to S2
(b)A-l,B-2,C-3,D-4 Sz: O.IM sucrose
(c}A - I, B-3, C - 2, D- 4 [Note; Assume that the electrolytes are Completely ionised.]
(d) A- 4, B-2, C-:- 3, D -I (CPMT (UP) lOO8] [E] Match the solutions in Column-I with their colligative
2. _Matrix Matchillg Problems (For lIT asp.irants): properties in Column-II:
[A] Match the solutes in Column-I with the van't Hoff factors Column-I Column-II
in Column-II: '
(P) Solution with highest
Column-I Column-II
boiling point
(a) K 4 [Fe(CN)6] (P}I+IX
(b) 0.1 M NaCI (q) Solution with van't Hoff
(b) Al Z ( S04)3 (q) Greater than 1
factor greater than 1
0.
II (c) 0.1 M glucose (r) Solution with lowest
(cl NHZ-C-NH2 .(r) (1 + 4a- ) osmotic pressure
(d) CaClz (s) I (d) 0.1 M CaClz (s) Solution with lowest
IX =Degree of ionhation. freezing point
[B] Match the s,olutionsin Column-I with their nature in .[Note: Assume that the electrolytes ate completely ionised.]
Column-II: . [FJ Match ..the concentration terms of List-I with their
Column-I Column-iI informations in List-II: .
(a) Benzene + toluene (p) Non-ideal solution List-I List-II
(b) .Ethanol + water (q) Ideiil solution (a) Molarity (P) Number of gram formula mass
(c) Benzene + chloroform (r) !llf mix > 0 of solute dissolved per litre of
solution
(d) Carbon tetrachloride ( s) !llf mixing = 0
+ chloroform (b) Molality (q) Number of moles of solute
[C] Match the s0lutions in Column-I with their nature in dissolved per kg of solvent
. Column-II: (c) F<lrmality (r) Depends on temperature
Column-I Column-II (d) Strength of solution ( s) Numberof moles of solute
(a) n-hexane + n heptane (P) Can be perfectly dissolved per litre of solution
separated by distillation
(b) Acetone + chloroform (q) Maximum boiling •
azeotrope
(c) Acetone + aniline (r) Cannot be perfectly
separated by distillation
(d) Ethanol + water (s) Nearly ideal
1. (a) A-4, B-3, C-2, D-1. [D] (a-p, q); (b--s); (c-p, q); (d-r)
1. [AJ (a-q, r); (b-q, r); (o-s); (d-p, q) [E] (a-p, q, s); (b-q); (c-r); (d-q)
[B] (a-q, s); (b--p, r); (c-p); (d-s) [F] (a-r, s); (b-q); (o-p, r); (d-r)
[C] (a-p, s); (b-q, r); (c-q, r); (d-r)
1. 15 g of methyl alcohol is present in 100 mL of solution. If the [JJjpj; After mIXlng number of moles of sugar present
density of solution is 0.96 g mL- l , calculate the mass
= 2 x 3 + 3 x 2.5 =13.5; Final molarity = 13.5 = 1.35 M ]
percentage of methyl alcohol in solution. . 10 .
[Aus. 15.625%] '4, If20.0 mLof 1.0 M calcium chloride and 60 mL of 0.2 M CaC1 2
2, A solution is prepared by dis~lving IS g of cane sugar in 60 g are mixed, what will be the molarity of the fmal solution?
water. Compute the mass per cent of each component of solution.
[J\.Ds. 0.40 M]
[4»s, Mass percentage of sugar 20%, Mass percentage of water
80%]
IS. Calculate the molarity of each of the ions in a solution when
3.0 litre of 4.0 MNaCI and 4.0 litre of2.0 MCoCI 2 are mixed
$. The density of the solutionofa salt X is 1.15 gmL- I .20 mLof . and diluted to 10 litre.
the solution when completely evaporated gave a residue of
[.I\.I),s. Molarity Na + = 1.2 M; Molarity C02+ = 0.8 M; Molarity
4.6 g of the salt. Calculate the mass percentage of the solute in
solution. CI- =2.8 M]
[ADS. 20%] [lfint: NaCI = Na+ + CI-
I rool. I roole 1 rool.
4. (a) 5.85 g ofNaCI is dissolved in 200 mL of water. What will 3x4roole 12roole 1211101.
be the molarity of this solution?
Co0 2 = Co 2 + + 2Cr .
L4JJs.. 0.5 M] I roole. I mole 2 roole
2 x 4 rook 8 roole 16 roole
(b) Calculate the molarity of the solution obtained by
dissolving 20.6 g NaBr in 500 mL of water. . Total CI- ions 28 mole]
[.us. 0.4 M] U;, What volume of 96% H2 S04 solution (density 1.83 g/mL) is
6.. The density of a solution containing 40% by mass of HCI is required to prepare 4 litre of 3.0 M H2 S04 solution?
1.2 g/mL. Calculate the molarity ofthe solution. [Ans. 670 rnL]
[_s.. 13.15M] '[llbl,,: First detennine the molanty of 96% H2S0 4 and then
6. Concentrated sulphuric acid has density of 1.9 g/mL and 99% dilute to get the desired solution.]
H2 S04 by mass. Calculate the molarity of the acid. 17.. Calculate the molarity of each ion in solution after 2.0 litre of
[.4...s. 19.19 M] 3.0 M AgN03 is mixed with 3.0 litre of 1.0 MBaC12 •
7. A mixture of alcohol and water contains 54% water by mass. LAos. Molarity ofBa 2+ 0.6M; Molarity of NO; = 1.2 M)
Calculate the mole fraction of alcohol in this solution.
L_. 0.25]
[mn.t: BaCI2 + 2AgN03 = 2AgCI J.. + Ba(N03)2
;8~ What amount of oxalic acid is' required to prepare 250 mL
Initial 3 mole 6 mole 6 mole Ag+ will react
Ba2+ Ag+
0.1 N solution (Given: molecular mass of oxalic acid = 126)? with 6 mole cr to fonn
[MIs. 1.575 g] 6moieCr 6 mole AgCl(s)
~. 7.45 g of potassium chloride is dissolved in 100 g of water. NO;,
What will be the molality of the solution? After 3 mole 6 mole
[Ms.' 1m] reaction Ba2+ NO;
t~. A solution is prepared by mixing 50 g sugar in 100 g of water
at 25 c C. Calculate the following: Total volume 3.0 + 2.0 =' 5 litre. ]
(i) Mass per cent of water. 18. The density of a 10.0% by mass of KCI solution in water is
(ii) Mole fraction of sugar. 1.06 g/mL. Calculate molarity, molality and mole fraction of
(iii) Molality of the solution. KCI in this solution.
[Aas. (i) 66.6 (ii) 0.0256 (iii) 1.46 m] [~s.. Molarity 1.42 M; Molality = 1.489 m; mole fraction of
U. A solution contains 25% water, 50%ethanoic acid and 25% KCI=0.026)
ethanol by mass. Compute the mole fraction of each 19,. Calculate the molality and mole fraction of the solute in an
component: aqueous solution containing 6 g of urea per 500 g of water
L.. Mole fraction of water = 0.5022; (MoL mass of mea =:: 60).
Mole fraction of ethanoic acid = 0.3013; [AIls. Molality =0.2 M; Mole fraction =0.00359]
Mole fraction of ethanol. 0.1965] 2.0.. Calculate the molality of I litre solution of 93% H2 804
12. Find the amount of 98% pure Na 2 C03· required to prepare (mass/volume). The density of the solution is 1.84 g/rnL.
5 litres of2 N solution. , <ML.NR 1993)
[Ans. 540.8 g impure Na2C03] [ .....s.. 10.428 mJ ,
13. Calculate the final molarity when 2.0 litre of 3.0 M sugar 21. Molarity of H2 S04 is 0.8 and its density is 1.06 g/cm 3. What.
solution and 3.0 litre of 2.5 M sugar solution are mixed and will be its concentration in tenns of molality and mole
then diluted to 10 litres with water. fraction. ICBS.E (Mains) 20OS}
[Aus. m = 0.814; xH2S04 :: 0.014 )
362 G.R.B. PHYSICAL CHEMISTRY FOR COMPE:TITIONS
, .
22. A 6.90 M solution of KOH in water contains 30% by mass of 33. Calculate the mass of a non-volatile solute of molecular mass
KOH. Calculate the density of the solution. 40, which should be dissolvCd in 114g of octane to reduce the
[Ans. 1.288 g mL-1 ] vapour pressure to 80%.
[Ans. 10 g]
23. How many kilograms of wet NaOH containing 10010 water are
34. to g ofa certain non-volatile Solute was dissolved in 100 g of
required to prepare 60 litre of a 0.5 M solution? .
water at 20° C. The vapour pressure was lowered from 17.3555
[Ans. 1.33 kg] to 17.235 mm. Calculate the molecular mass of the solute.
24. In an experiment, 18.0 g of mannitol was dissolved in 100 g of [Ans. 257.45]
water, The vapour pressure of solution at 20° C was 17.226 mm 35. 0.534 g of solute is dissolved in 15 g of water then freezing
of mercury. Calculate the molecular mass of mannitol. The point temperature changes from O°C to -1.57°C. Molal
vapour pressure of water at 20°Cis 17.535 mm afmercury. depression constant of water, K f = 1. 85 K kg morl . Find out:
[Ans. Molecular mass of mannitol =181.02]
(i) Molal concentration
25. The vapour pressure of water at 200Cis 17.53 mm. Calculate
(ii) Molecular mass of solute (AIPMT (Mains) 20091
the vapour pressure of a solution at 200 C containing 6 g of (Alis. 0) 0.848 (ii) 41.98 amu]
urea in 100 g of water (molecular mass of urea = 60). 36. Addition of 0.643 g of a compound to 50 mL of benzene
[Ans. Vapour pressure of solution = 17.22 nun] (density 0.879 g/mL) lowers. the freezing point from 5.51° C to
=
26. The vapour pressure of ether (molecular mass 74) is 442 mm 5.03° C. If K f for benzene is 5.12,' calculate the molecular
Hg at 293 K. If 3 g of a compound A are dissolved in 50 g of mass of the compound. (lIT 1992)
ether at this temperature, the vapour pressure falls to 426 mm [ADS. 156]
Hg. Calculate the molecular mass of A aSsuming that the 37. A solution made by dissolving 0.32 g of a new compound in
.' solution of A is very dilute. 25 g of water has freezing point 0.201°C. Calculate the
[Ans. m = 123] molecular mass of the new compound.
[Ans. 118.4]
27. 18.2 g of urea is dissolved in 100 g of water at 50° C. The 38. The boiling point of a solution of 0.1050 g of a substance in
lowering of vapour pr~ssure produced is 5 mm.Hg. Calculate' 15.84 g of ether was found to beO.1°C higher than that of pure
the molecular mass of urea. The vapour pressure of water at ether. What is the molecular mass of the substance (Molecular
500 C is 92 mm Hg. elevation constant of ether per 100 g is 21.6)? (MLNR 1991)
[ADs. 57.05] [Ans. 143.18]
39. Calculate the' freezing point and the .boiling point at
[Hint: Use Po - P. = _n_ ,as the solution is not very dilute]
Po n+N I atmosphere of' a solution containing 30 g cane sugar
(molecular mass 342) and ISO g water.
28. Calculate the vapour pressure of a solution at IOWC Given: Kb = 0.513 and Kf = 1.86.
containing 3 g of cane sugar in 33 g of water. (Ans. . Boiling point 100.3; Freezing point - 1.09°C]
[Ans. 756.36 nun ofRg] 40. When 36.0 g of a solute having the empirical formula CH20 is
[Hint: Apply Po - P. = wM as the solution is very dilute. dissolved in 1.20 kg of water, the solution freezes at - 0.93" C.
Po Wm What is the molecular formula of the compound?
Po =760mm ofHg atlOO°Cand m:= 342] I [Ans. C2R 40 2 ]
29. An aqueous solution containing 28% by mass or'a liquid A 41. In winter, the normal temperature in Kullu valley was found to
=
(molecular mass 140) has a vapourpressure ofl60 mm at be, - II ° C. Is a 28% (by mass) aqueous solution of ethylene
3T C. Find the vapour pressure of pure liquid A' (the vapour glycol suitable for a car radiator?
pressure of water at 37°Cis 150 tnm). Kf for water = 1.86 K kg mor I.
[Ans. PA = 358.3 nun] [Ans. Yes. The given solution freezes at - 11.66° C]
[Hint: Apply Ptotal := mole fraction of liquid A x PA + mole 42. Latent heat of fusion of water is 80 calJg and its normal
fraction of water x PW' Mass of water = 100 - 28 = 72 g] freezing point is O°C.Calculate molal depression constant for
30. At 25° C, the vapour pressure of pure benzene is' 100 torr, =
water. (R 1.987cal)
while that of pure ethyl,alcohol is 44 torr. Assuming ideal [Ans. 1.86 K kg mol-I]
behaviour, calculate the vapour pressure at 25° C of a solution 43. A solution containing 7.5 g of urea (molecular mass = 60) in
which contains 109 of each substance. I kg ·of water freezes at the same temperature as another
[ADS. 64.775 torr] solution containing 15 g of solute' A' in the same amount of
3] • Estimate the lowering of the vapour pressure due to solute in a water. Calculate molar mass of' A'.
] .0 molal aqueous solution at 100° C [ADs. 120]
[ADs. 14nunofRgorl4torr] 44. Calculate the osmotic pressure of a decinormal solution of
32. Find the molality of a solution containing a non-volatile solute NaCI which is ionised to 80% at 27° C.
if the vapour pressure is 2% below the vapour pressure of pure [Ans. 4.43 atm]
water. (Dhanbad 1990)
45. What is the volume of a solution containing 2 g mole of sugar
[Ans. 1.133 m]
that will give rise to an osmotic pressure of I atmosphere at
S1lP? .
[ADs. 44.81itre]
SOLUTIONS
46. If the osmotic pressure of 5 g per litre solution of a compound 55. What should be the osmotic pressure of a solution of urea in
at 27° Cis· 0.025 atm, calculate the molecular mass of the water at 300C which has boiling point 0.052 K higher than
compound. pure water? Assume molarity and molality to be the same. K b
[Ans. 4926] for water is 0.52 K kg moi-I .
47. The osmotic pressure of blood is 7.65 atmosphere at 37°C. [Ans. 2.487 atm]
How much glucose should be used per litre for an intravenous 56. 4.0 g of a substance A dissolved in 100 g H 20 depressed the
injection that is to have same osmotic pressure as blood? freezing point of water by 0.1° C while 4.0 g of another
[Ans. 54.18 g of glucose per litre] substance B depressed the freezing point by 0.2° C. Which
48. 10 g of cane· sugar (molecular mass = 342) in I x 10-3 m 3 of one has higher molecular mass and what is the relation?
solutioh produces an osmotic pressure of 6.68 x 104 Nm-:-2 at [Ans. M A =2MH ]
57. A solution containing 28 g of phosphorus in 315 g of CS2
273 K. Calculate the value of S in SI units.
(boiling point 46.30 C) boils at 47.980 C. The molal elevation·
[Hint: S == PV constant for CS 2 is 2.34 K kg mol-I. Calculate the molecular
nxT
mass of phosphorus and deduce its formula in CS 2 •
Given: V == 1 X 10-3 m 3; P == 6.68 x 104 Nm-2;
[Ans. 123.8, P4]
10
n==- T=273 58. A solution of two volatile liquids A and B obeys Raoult's law.
342'
3
At a ce.rtain· temperature it is. found that when the pressure
S = 6.68 x lit x 1 x 10- x 342 = 8.3684 J K- 1 mol-I] abQve the mixture in equilibrium is 402.5 mm of lig, the mole
10 x 213 fraction of A in the vapour is 0.35 and in the liquid it is 0.65.
49. A 250 mL water solution containing 48 g of sucrose What are the vapour pressures of two liquids at this
=
(molecularrnass 342) at 300 K is separated from pure water temperature?
by means of a semipermeable membrane. What pressure must [Hint: Let PAand PH be the partial pressures of vapours and p~
be applied on solution as to prevent osmosis? and p~ be the vapour pressures of two liquids respectively.
[Ans. 13.8 atm]
50. What would be the osmotic pressure of 0.05 M solution of
PA =0.65 PAoand· PH =0.35PH0
sucrose at 5° C? Find out the concentration of a solution of PA + PH =402.5 (given)
glucose which would be isotonic with this solution of sucrose. In vapour phase,
(Molecular mass of sucrose = 342, Molecular mass of ~ =0.35 or PA = 0.35 x 402.5 = 140.875 rom
glucose = 180) PA + PH
[Ans. 1.14 atm;.Concentration of glucose soln. = 9.0 gIL] So, p~ =216.72 rom and pZ = 747.5 rom]
51. Calculate the osmotic pressure of 0.5% solution of glucose
59. Calculate the amount oeice thatwill separate out on cooling a
(molecular mass 180) at 18° C . The value of solution constant
solution containing 50 g of ethylene glycol in 200 g water to
is 0.0821·litre-atm K- I mol-I.
9.3°C(Kf for water = 1.86K kg mol-I). . (liT 1995)
[Ans. 0.6628 atm]
52. At 10° C , the osmotic pressure of urea solution is 500 mm. The [Hint: AT =Kf Xm
solution is diluted and the temperature is raised to 2SO C, when =
9.3 1.86·x m
the osmotic pressure is found to be 105.3 mm. Determine or m=5
extent of dilution. Thus, solution of5.0 molality will have freezing point of - 9.3 0 C.
[Hint: Original solution ... (i) Let W g water be needed to prepare 5.0 molal solution containing
50
- mole of ethylene glycol.
After dil:ution ... (ii} 62 . .
So, 50 x 1000 =5.0
or 62xW
hl.. 1.2 kg ethylene glycol [ ~H20H 1was added in a car radiator 10glO [
P2
fJ J
1=~ (.! J..J]
2.303R Ii T 2.
CH20H
99, Calculate the increase in vapour pressure of water per
containing 9 litre water. The freezing of water was just atmosphere rise in external pressure at 10 0 C. The vapour
prevented when car was runnirig in the Himalayan valley at pressure of water at 10° C and I atm is equal to 9.2 mm.
temperature 4°C. Sudden fuunderstorm in the valley
[Am, 0.1%]
lowered the temperature to 6°C. Calculate the amount of ice
separated.
[A~s. 3 kg ice]
[Hint; Use loglO(~J = 2.303RT (Pz fJ)
x 1000 VI ~ molar volume of liquid]
t:.T K f x A --? Solute; B --? Solvent
x we
mA An aqueous solution of H2 S04 has density 1.84 g/mL.
6 == 1.86 x 1200 x 1000 Solution contains 98% H2S04 by mass. Calculate:
62xwe , (i) molarity of solution
We == 6000 g (ii). overall molarity of solution
[Weight of ice =Total weight of H2 0
wt. of H2 0 at - 60 C (iii). molar volume
9000 6000 3000g == 3 kg] .(iv) specific volume
2 g mixture of glucose and sucrose is dissolved in 1 litre water (v) relative decrease in vapour presStlre with respect to
at 298 K to develop osmotic 'pressure of 0.207 atm. Calculate .water, assuming H2S04 as non-ele«trolyte this high at
percentage composition of glucose and sucrose by mole as concentration.
well as by mass. [~t) (i) . M == x x d x 10
[~. me
Percentage by mole: glucose 65.194, sucrose 34.806; == 98 x 1.84 x 10 = 18.4
Percentage by mass:, glucose 50, sucrose = 50.] 98
6,3. If benzoic acid (mol. mass 122) is associated into double (ii) Weight of solution (1 litre) =1000 x 1.84 1840 g
molecules when dissolved, in benzene and the osmotic We (weight of H2S04 ) = ~ x 1840 1803.2 g
pressure of a solution of 5 g of benzoic acid in 100 mL 100
benzene ijl 5.73 atm at 10°C, what is the percentage association wA (weight of water) 1840 1803.2 36.8 g
of benzoic acid? Total number of moles = WA + we = 36.8 + 1803.2
[A»s,. 80%] mA 18
me 98
[mat;: n = iCRT = i n RT == 2.044 + 18.4 == 20.444
V Overall molarity = 20.444
5.73 =i x 5/122 x 0.0821 x 283 (iii) Molar volume = Volume = 1000
0.1 . Total moles 20.444
i = 0.6017
=48.914 mL/mol
1 0.6017 '" 0.8
1 (iv) Specific volume _1_ = _1_ mL/g 0.543 mL/g
density 1.84
% association 80% ] ,
(v) Molality (m) = We x 1000 98 x 1000 500
~. 0.1 formal solution ofNaCI is found to be isotonic with 1.10% mB x wA 98 x 2
solution of urea. Calculate the apparent degree of ionization of
x 1000
NaCl. m==
(l-xB)m A
[AIls. 0.83]
[Hi.nt·: n NaC1 = n urea 500 = --",_x_I_OO_O_
1 {1- xe)xI8
=nx RT
V Xe == 0.9
[Hiiif~ (i) Letxlitreof0.341 MHCland 1 litre of 0.143 MHCI Use, Po. P 'ltm
be mixed to obtain 0.243 M HCL Po dRT
MIVj + M ZV2 ==MR(V1 + V2 ) 1- P 25.224 x 18
0.341xx+0.143xl 0.243 (i+x) 1 (1 x x 0.0821 x 373
(0.341- 0.243)x 0.243 - 0.143
P =0.958 atm]
0.098x == 0.1
71, Calculate the osmotic pressure at 25 ° C of a solution
x == 1.0204 litre
containing 1 g of glucose and I g of sucrose in I litre of
Total volume 1 + x == 2.0204 litre solution. . .
Since, vOlume is greater than 2 litre, hence water is to be added.
If it were not known that the solute was a mixture of glucose
(ii) Let x litre of 0.143 M HCI and I litre of 0.341 M HCI are
and sucrose, what would be the molecular weight of solute
mixed to obtain 0.243 MHCl.
corresponding to the calculated osmotic pressUre?
M1V1 + M 2V2 == MR(V1 + V2 ) [,1\118; 0.207 atm,236.384]
0.143 Xx+ 0.341 xl == 0.243(1 + x)
[Hlriti Use; 'ltV = (nl + nz)RT to calculate osmotic pressure
O.lx == 0.098 I I \ .
x == 0.98 litre 'It X 1 = + -j
180 342
x 0.0821 x 298
Total volume == 1 + x == 1.98 litre
Since, volume is less than two litres, no water is to be added.] == 0.207 atm
69. What is the vapour pressure of a solution of glucose which has Use; 'ltV == ~ RT to calcuJate molar mass of solute.
an osmotic pressure of 3 atmosphere at 20° C? The vapour
/ m
pressure of water at 20°C is 17.39 rnm. Consider the density 2
0.207 xl -:- x 0.0821 x 298
of solution equal to that of solvent. m
[Ans. 17.35 mm] m = 236.384]
[Hiiiti Use: l!.p == 'ltm ] 7i. 100 mL aqueous solution of glucose with osmotic pressure
Po' dRT 1.2 atm at 25°C is mixed with.300 mL aqueous solution of
urea at 2.4 atm at 25° C. Calculate the osmotic pressure of
70. The osmotic pressure. of an aqueous solution of a
mixture.
non-electrolyte is 18.8 atm at 15° C. What will be the vapour
pressure of this solution at 100° C (Density of water at [Anj, 1.68 atmj
100°C"" 19/cc)? [itiiiti Use: 'ltIVI + 'ltzVz ='ltR(VI + V2 )
[Ans. 0.958 atm]
[Hliitl Use, ~ == 'lt2 to calculate osmotic pressure at 100°C.
TI T2
1.2 x 100 + 2.4 X 300 :.':: 1.68 atmj'
18.8 =~
500 .
278 373
'lt2 25.224 atm
7. The solubility of a gas in liquid increases with: 18. 'Among the following, that does not form an ideal solution is:
(a) increase in temperature (a) C6~ and C 6HsCH3 (b) C 2HsQ and C 2 Hs0H
(b) reduction of gas pressure . (c) C 6HsCI and .C6HsBr (d) C 2 HsBr and C 2HsI
(c) decrease in temperature and increase of gas pressure 19. Which of the following solution pairs can be separated by
(d) amount of liquid taken fractional distillation?
8. Saturated solution ofNaCI on heating becomes: (a) Water-HN03 (b) Water-HCI
(a) supersaturated (b) unsaturated (c) Benzene-toluene (d) C 2Hs0H-water
(c) relnains saturated (d) none oftbese 20. When two liquids A and B are mixed, their boiling points
9. A supersaturated solution is a metastable solution whose bec9me greater than both of them. The mixture is:
concentration: (a) ideal solution
(a) is equal to the solubility of the substance in solvent (b) non-ideal solution with negative deviation from Raoult's law
(b) is less than the solubility (c) non-ideal solution with positive deviation from Raoult's law
(c) exceeds the solubility (d) normal solution .
(d) continuously changes 21. The azeotropic mixture of water (b. pt. 1000 C) and HCI
10. When a crystal of a solute is introduced into a supersaturated (b. pt. 85° C) boils at 108.5 0 C. When this mixture is distilled,
solution of the solute: . it is possible to obtain:
(a) the solute dissolves (a) pure Hel
(b) the solution becomes unsaturated (b) pure water
(c) the solution remains supersaturated (c) pure water as well as HCI
(d) . the excess of solute crystallises out . (d) neither HCI nor H20 in their pure states
11. An electrolyte dissolves in water if: 22. Pressure cooker reduces cooking time because:(CPMT 1990)
(a) lattice energy is less than hydration energy (a) the heat is more evenly distributed inside the cooker
(b) . lattice energy is greater than hydration energy (b) a large flame is used
. (c) lattice energy is equal to hydration energy (c) boiling point of water is elevated
(d) dissolution is endothermic (d) whole matter is converted into stearn
12. The solubility of a substance is defined as the amount of solute 23. A molal solution is one that contains one mole of a solute in:
in grams; (a) 1000 g of the solvent (b) one litre of the solution
(a) present in 100 g of the solvent
(c) one litre of the solvent (d) 22.4 litre of the solution
(b) present in 100 g of the solution
24. In which mode of expression, the concentration of the solution
(c) present in 100 mL of the solution remains independent of temperature?
(d) present in I litre ofthe solution.
(a) Normality (b) Molality (c) Molarity (d) Formality
13. Which of the following will form an ideal solution?
25. 8 g NaOH is dissolved in one litre of solution. Its molarity is:
(a) C 2 Hs0Hand water (b) HN03 and water
(a) 0.8 M (b) 0.4 M (c) 0.2 M (d) 0.1 M
'(c) CH0 3 and CH3COCH3 (d) C6~ and C 6HsCH3
14. Which of the following shows positive' deviation from 26. If 18 g of glucose is present in 1000 g of solv~nt, the solution
Raoult's law? . is said to be: '." ' . ..
(a) C6~ and C 6HsCH3 (b) C6~ and C0 4 t
·'i/?:]ilfImoliB.' 1(6to, Im9.,I~:(crq;~~Iilf :M>Q.I molal~·:-~:::·.
27.' Th~ molarity ofpuie w~ter is: .... [CMC (VeUore) 1991]
(c)CH0 3 and C 2Hs0H (d) CHQ3 and CH3COCH3 .
15. Which of the following shows negative deviation from (a) 100M (b) 55.6M (c) 50M (d) IBM
Raoult's law? 28. For preparing' 0; I' M solution of H2 S04 in one litre,we need
(a) CH0 3 and acetone (b) C6~ and C 2Hs0H H2S04 :
(c) C 6HsCH3 and C6~ (d) C6~ and CCl 4 (a) 9.8g (b) 4.9 g (c) 49.0 g (d) 0.98 g
16. An azeotropic mixture of two liquids boils at a lower 29. Mole fractiOJi ofC 3 Hs(OHh in a solution of36 g of water and
temperature than either of them when: 46 g of glycerine is: (CPMT 1991)
(a) it is saturated (a) 0.46 (b) 0.36 (c) 0.20 (d) 0.40
(b) it does not deviate from Raoult's law 30, H20 2 solution used for hair bleaching is sold as a solution of
(c) it shows negative deviation from Raoult's law
approximately 5.0 g H2 0 2 per 100 mL of the solution. The
(d) it shows positive deviation from Raoult's law
molecular mass ofH2 0 2 is 34. The molarity of this solution is
1j. A maxima or minima obtained in the temperature composition approximately:
curve of a mixture of two liquids indicates: (a) 0.15 M (b) 1.5 M (c) 3.0 M (d) 3.4 M
(a) an azeotropic mixture
31. The number of moles ofsolute per kg of a solvent is called its:
(b )an eutectic formation .
(a) molarity (b) normality
(c) that the liquids are immiscible with one another
(c) mole fraction (d) molality
(d) that the liquids are partially miscible at the maximum or
32. 1000 g aqueOU$ solution of caC03 contains 109 of calcium
minimum
carbonate. Concentration of the solution is:
. SOLUTIONS 367
st. If the various tenns in the following expressions have usual (a) 0.66M (b) 0.32M (c) 0.066M (d) 0.033M
meanings, the van't Hoff factor 'i' cannot be calculated by 6J. 'If 3 g of glucose (molecular mass 180) is dissolved in 60 g of
which of the following expression? water at 15°C, then the osmotic pressure of this solution will
(a) nV 4i nRT be:
(b) I!.Tf = ixK f Xm (a) .0.34 attn (b) 0.65 attn (c) 6.57 attn (d) 5.57 attn
(c) I!.Tb=ixKbxm 64. The relationship between the values of osmotic pressure of
(d) P~lvent -Psolution
P~lvent
=
N +n
i[_n_J 0.1 M solutions of KN03 (PI) and CH3COOH (P2 ) is:
(a) ~ = P2 (b) P2 > PI
53, Semipenneable membrane is that which pennitsthe passage (c)~= (d)PI ,>:P2
1~+P2 PI +P2
of: . . (CPMT 1:990)
. (a) solute molecules only (is. An electrolyte' A gives 3 ions and B is a non-electrolyte. If .
0.1 M solution of B produces an osmotic pressure P, then
(b) solvent molecules only
0.05 M solution of A will produce an osmotic pressure,
(c) solvent and solute molecules both
assuming that the electrolyte is completely ionised: .
(d) neither solute nor solvent molecules
(a) UP' (b) P (c) o.5P (d) 0.75P
$4, Which inorganic precipitate acts as semipenneable
66. l' molat solution of a non-volatile and non-electrolyte
membrane?
compound will produce an osmotic pressure ....... at O°C.
(a) Calcium sulphate (b) Barium oxalate
(a) 1 attn (b) 44.8 attn (c) 10.0 atm (d) 22.4 atm
(c) Nickel phosphate (d) Copper ferrocyanide
61. If 0.1 M solution of glucose andO.1 Mureasolution are placed
55. During osmosis, flow of water through a sem!penn~b!e on two sides of a semipenneable membrane to equal heights,
membrane is: [CBSE(Medi'Cal) 2006] then it will be correct to say that: .' (CaSE 1992)
(a) from solution having higher concentration only (a) there will be no net movement across the membrane
(b) from both sides of semipenneable membrane with equal (b) glucose will flow towards urea solution
flow rates
(c) urea will flow towards glucose solution
.(c) from both sides of seri:ripenneable membrane with unequal
(d) water will flow from urea solution towards glucose solution
flow rates
68. Which solution will exert highest osmotic pressure?
(d) fr.om solution having lower concentration only
(a) I M glucose solution (b) 1 Murea solution
56, At constant temperature, the osmotic pressure of a solution is:
I (c) I M alum solution (d) 1 MNaCI solution
(a) directly proportional to the conc~ntration
69. Which is the correct relation between osmotic pressure of
(b) inversely proportional to the concentration
0.1 MNliCi solution and 0.1 MNa2S04 solution?
(c) directly proportional to the square of concentration
(a) The ,osmotic pressure of Na2S04 is less than NaCl
(d) directly proportional to the square root of concentration solution
51. Osmotic pressure observed when benzoic acid is dissQlved in (b) The osmotic pressure of Na2S04 is more than NaCI
benzene is less than that expected from theoretical solution
conside~tions. This is becau~e: . ,[MGlMS '(\\lardba) 2""8] (c) Both have same osmotic pressure
(a) benzoic acid is organic solute
(d) None ofthe above
(b) benzoic acid has higher molar mass than benzene
70. A 0.6% urea solution would be isotonic with:
(c) benzoic acid gets associated in benzene [CEt(I(arnataka) >2009]
(d) benzoic acid gets dissociated in benzene
(a) 0.1 M glucose solution (b) 0.1 MKCI solution
58. Blood'cells do not shrink in blood because blood is: (c) 0.6% glucose solution (d) 0.6% NaCl solution
fPMt '(MM) ,2007]
71. Which one of the following solutions will have highest
(a) hypertonic (b) isotonic
osmotic pressure? (Assume .that all the salts are equally
(c) equimolar (d) hypotonic dissociated. )
59. Isotonic solutions have the same: (a) 0.1 M Al 2(S04h
(a) density (b) molar concentration (b) OJ MBaCl 2
. (c) nonnality (d) strength
(c) 0.1 MNa2S.o4
60. The osmotic pressure of solution increases if: (CPMT 1991) (d) The solution obtained by mixing equal volumes of (b)
(a) temperature is decreased and (c)
(b) concentration is decreased 72. The following solutions have equal concentratioBS. Which one
.(c) number of solute particles is increased will show minimum osmotic pressure?
(d) volume is increased (a) BaCl2 (b) AgN03
61. The, osmotic. pressure of a 5% solution of cane sugar (c) Na2S04 (d) (~hP04
(molecular mass 342) at 15°C is: 73. A solution of a substance containing 1.05 g per 100 mL was
(a) 3.46 attn (b) 3.64 attn (cl 4.0 atm (d) 2.45 atm found to be isotonic with 3% glucose solution. The molecular
61. A solution has an osmotic pressure of 0.821 atm at 300 K. Its , mass of the substance is:
concentration would b e : ( I I T 1990) (a) 31.5 (b) 6.3 (c) 630 (d) 63
SOLUTIONS 369
74. The osmotic pressure of equimolar solutions of BaCI 2 , NaCI (c) boiling point of the solution becomes higher than that of
and glucose will be in the order:· solvent .
(a) glucose> NaCI > BaCl 2 (b) BaCl 2 > NaCI > glucose (d) all are correct .
(c) NaCl> BaCl 2 > glucose (d) NaCl > glucose> BaCl 2 86. The molal elevation constant is the ratio of the elevation in
boiling point to:
75. At 25°C, the highest osmotic pressure is exhibited by 0.1 M
solution of: (CBSE 1994) (a) molarity (b) molality
(c) mole fraction of solute (d) mole fraction of solvent
(a) CaCl2 (b) KCI (c) glucose (d) urea
87. In cold countries, ethylene glycol is added to water in the
76. The plant cell will shrink when placed in:
radiators of cars during winters. It results in:
(a) water (b) a hypotonic solution
(a) reducing viscosity (b) reducing specific heat
(c) a hypertonic solution . (d) an isotonic solution
(c) reducing freezing point (d) reducing boiling point
77. The osmotic pressure of it solution at 273 K is 2.5 atm. Its
88. The best colligative property used for the determination of
osmotic pressure at 546 K under similar conditions will be:
molecular masses of polymers IS:
(a) 0.5 atm (b) 1.0 atm (c) 2.5 atm (d) 5.0 atm (a) relative lowering in vapour pressure
78. Which one of the following pairs of solutions will be expected (b) osmotic pressure
to be isotonic under the same temperature? (c) elevation in boiling point
. [CET (Gujarat) 2006; AMU (Medical) 20091
(d) depression in freezing point
(a) 0.1 MureaandO.l MNaCI
89. Ebullioscopy is concerned with:
(b) 0.1 Murea and 0.2 MMgCl2
(a) osmotic pressure of a solution·
(c) 0.1 MNaCI and 0.1 MNa2S04
(b) elevation of boiling point of a solution
(d) O.l MCa(N03h and 0.1 MNa 2 S04 (c) depression in freezing point of a solution
79. An aqueous· solution of methanol in water has vapour
(d) relative lowering in vapour pressure of a solution
pressure:
90. Cryoscopy is concerned with:
(a) less than that of water (b) equal to that of water
(a) osmotic pressure ofa solution
(c) more than that of water (d) equal to that of methanol
(b) elevation of boiling point of a solul'~on
80. An aqueous solution is 1 molal in KI. Which change will cause
(c) depression in freezing point of a solution
the vapour pressure ofthe solution to increase? .
[CBSE (PMT) 20101 (d) relative lowering in vapour pressure of a solution
(a) Addition ofNaCl (b) Addition of Na2S04 91. Molecular mass of a non-volatile solute can be determined by:
(a) Cryoscopic method (b) Victor-Meyer's method
(c) Addition of 1 m~lal KI (d) Addition of water
(c) Graham's method (d) Duma's method
81. Osmotic pressure of a solution containing 0.1 mole of solute
92. Beckmann's thermometer measures:
per litre at 273 K is (in atm):
(a) boiling point of the solution
(a) O.l x 273 (b) O.l x 0.0821 x 273 (b) freezing point of the solution
0.0821 1
1 (d) O.l x 0.0821 (c) any temperature
(c) - x 0.0821 x 273 1 273 (d) elevation in boiling point or depression in freezing point
0.1
82. A solution of urea contains 8.6 g per litre. It is isotonic with a 93. The freezing point of 1% of lead nitrate solution in water will
5% solution of a non-volatile solute. The molecular mass of be: [UGET (ManipaJ) 2006)
the solute will be: (a) 2°C (b) 1°C (c) O°C (d) below O°C
(a) 349 (b) 34.9 (c) 3490 (d) 861 94. A solution of 1.25 g of non-electrolyte in 20 g of water freezes
83; The hard shell of an egg was dissvlved in HCL The egg was at 271.94 K. If K f is 1.86 Kkg mol- 1 then molecular mass of
then placed in a concentrated solution of NaC!. What will the solute will be:
happen? (a) 207.8 (b) 179.79 (c) 209.6 (d) 109.5
(a) The egg will shrink 95. The ratio of the value of colligative property for KCI solution
(b) The egg will swell to that of sugar solution at thc same concentration is nearly:
(c) The egg will become harder (a) 1 (b) 2 (c) 0.5 (d) 2.5
(d) There will be. hardly any visible change 96. The freezing point order of the solution of glucose is:
84. Blood has been found isotonic with: (a) 10%>3%>2%> 1% (b) 1%>2%>3%> 10%
(a) saturated solution ofNaCI (c) 1%>3%>10%>2% (d) 10%> 1%>3%>2%
(b) saturated solution ofKCI 97. Which one of the following solutions has the highest b.p.?
(c) saturated solution of 1 : I mixture ofN",CI and KCI [UGET (Manipal) 2006]
(d) normal sodium chloride solution (a) 0.1 M NaCl (b) 0.1 M urea
85. When a solute is dissolved in a solvent: (c) 0.1 M BaCI2 (d) 0.1 M glucose
(a) vapour pressure of the solvent is decreased 98. The freezing point of 1 molal NaCl solution assuming NaCl to
(b) freezing point of the solution becomes less than that of be 100% dissociated in water is:
solvent
370 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(a) 1. 86°C (b) 3.72°C (a) KCl (b) BaCI2 (c) K 2S04 (d) C 6HI2 0 6
(c) + 1.86°C (d) + 3.72°C 114. A solution containing 3.3 g of as:.:bstance,in 125 g of benzene
9"9. Which of the following 0.1 M aqueous solutions will have the (b.pt. 80°C) boils at 80.66°C. If K b for benzene is 3.28 K kg
lowest freezing point? . (MLNR 1990) mor l the molecular mass ofthe substance will be:
(a) K 2S04 (b) NaCI (c) Urea (d) Glucose (CP:MT 1992)
100. The freezing point of a 0.05 molal solution of a (a) 130.29 (b) 129.20 (c) 132.20 (d) 131.20
non-electrolyte in water is: (MLNR 1990) 115. The elevation in boiling point of a solution of 109 of a binary
(a) - 1.86°C (b) 0.93°C (c) 0.093°C (d) O.93°C elbctrolyte (molecular mass 100) in 100 g of water is ATb . The
101. The :freezing point of equimolal aqueous solution will be value of K b for water is:
highestfor: (lIT 1990) (a) A~b . (b) 10 (c) lOATb (d) ~~
(a) qH;;NH3Cl (b) Ca(N03)2
(c) La(N03 )3 (d) C 6HI2 0 6 (glucose) 116. The molal freezing point constant for water is 1.86 K kg mor I.
101. Elevation in boiling point was 0.52°C when (j g of a compound Therefore, the freezing point of 0.1 MNaCI solution in water is
X waS dissolved in 100 g Qf water. Molecular mass of the expected to be: (MLNR 1994)
compound X is: (K b for water is 0.52 per 1000 g of water.) (a) - 1.86°C (b) - 0.186°C(c) - 0.372°C (d) + 0.372°C
(a) 120 (b) 60 (c) 600 (d) .180 117. Equal volumes of M 120 urea solution and M 120 glucose
103. The molal freezing point constant for water is ·1.86. If 342 g of solution are . mixed. The mixture will have osmotic pressure:
cane sugar is dissolved in 1000 g of water, the solution will (a) equal to either of the solution
freeze at: . (b) less than either of the solution
(a) 1.86°C (b) - 1.86°C (c) 3.92°C (d) 3.92°C (c) higher than either of the solution
104. The molal elevation consta~t of water is 0.51 .. The boiling (d) zero
point of 0.1 molal aqueousNa.cI solutionis nearly:(IIT 1991) 118. Assuming the salts to be unionised in solution, which ofthe
(a) 100.05°C (b) 100.l°C (c) 100.2°e (d) 101.0°C following has highest osmotic pressure?
l~S. The molal elevation of an unknown solution is equal to the (a) I%CsCl (b) l%RbCl (c)l%KCl (d) l%NaCf
· molal elevation of 0.1 M solution of urea. The concentration of 119. Pure benzene freezes at 5.3°C. A solution of 0.223 g of phenyl
unknown solution is: acetic acid (C6Hs CH2 COOH)in 4.4 g of benzene (K f 5.12
(a) 1M (b)om M . (c) 0.1 M (d) none of these K kg morl) freezes at 4.47°C ..From the observation one can
l06. Benzoic acid dissolved in benZene will show a molecular mass conclude that: (AFMC 2010)
of: . , (a) phenyl acetic acid exists as such in benzene
(a) 122 (b) 61 (c) 244 (d) 366 (b) phenyl acetic acid undergoes partial ionization in benzene
107. If the observed andnonnal osmotic pressures of a KCI (c) phenyl acetic acid undergoes complete ionization in
solution are.5.85 and3.20atm, the degree of dissociation of benzene
KCI is: (d) phenyl acetic acid dimerizes in benzene
(a) I (b) 0.082 (c) 0.82· (d) '0.28 no. The movement of solvent molecules from higher
lOS. The van't Hoff factor ofa 0.005 M aqueous solution ofKCI is concentration to lower concentration through sernipenneable
1.95. The degree of ionisa~on of KCI is: membrane under pressure is tenned:
(a) 0.95 (b) 0,97 . (c) 0,94 (d) 0.96 (a) ;smosis (b) reverse osmosis
tb'~. If the observed and nonnal osmotic· pressures of 1% NaCI (c)' dialysis (d) diffusion
solution are 5.7 and 3.0 atm, the degree of dissociation of t21. During depression of freezing point experiment, an
· NaCI is: equilibrium is established between the molecules of:
(a) 0.9 (b) 1.0 (c) 0.57 (d) 0.3 (EAMCET 2009)
llO. Which one of the following salts would have the same value of (a) liquid solvent and solid solvent
the van't Hoff factor as that of K3Fe(CN)6? (CSSE 1994) (b) liquid solute and solid solvent
(a) AI 2(S04h (b) NaCI (c) liquid solute and solid solute
· (c) Na2S04 (d) Al(N03 )3 (d) liquid solvent and solid solute
HI·. Equimolal solutions of A and B show depression in freezing In. The molecular weight of benzoic acid in benzene as
point in the ratio of2 : I. A remains in nonnal state in solution. determined by depression in freezing point method
B will be in ... state in solution. corresponds to: (liT 1996)
"
(a) nonnal (b) associated (a) ionisation of benzoic acid
(c) hydrolysed (d) dissociated (b) dimerization of benzoic acid
1.'':2. The values of observed and calculated molecular· mass of (c) trimerization of benzoic acid
Ca(N03 )2 are 65.4 and 164 respectively. The degree of (d) solvation of benzoic acid
ionisation of the salt will be: 12"3. If 0.15 g of a solute, dissolved in 15 g of solvent, increases the
(a) 0.25 (b) 0.50 (c) 0.60 (d) 0.75 boiling point by U216°C over that of the pure solvent, the
Jftl~. Which of the following compounds corresponds to van't Hoff molecular mass of the substance is (Molal elevation constant
factor to be equal to 2 in dilute solution? . . for the solvent is 2.16): (CBSE 1999)
SOLUTIONS 371
In the solution, A - B interactions are: 149. The molal b.pt. constant forwatefls LI.513°Ckg mol-'. When
(a) similar to A - A and B - B interactions 0.1 mole of sugar is dissolved in 200 g of water, the solution
(b) greater than A - A and B - B interactions boils under a pressure of 1 atm at: (AlIMS 1991)
(c) smaller than A - A and B - B interactions (a) 100.513°C (b) 100.0513°C
(d) unpredictable (c) 100.256°C (d) 1Ol.025°C
140. The best and accurate method for determining 'osmotic 150. The correct expression relating molality (m), molarity (M),
pressure is: (AFMC 1995) density (d ) and molar mass (M 2) of a solute is:
(a) negative pressure method
(b) Berkeley and Hartely method (a)m- M (b)m- M
d +MM2 ' d -MM2
(c) Morse and Frazer method
, (d) Preffer's method (c) m = d + MM 2 (d) m = d - MM 2
141. If all the following four compounds were sold at the same
M M
price, which would be cheapest for preparing an antifreeze 151. The expression relating mole fraction of solute (x2 ) and
solution for a car radiator? (AMU 1997) molarity (M ) of the solution is:
(a) CH30H (b) C 2 H50H MM MM
(a) x 2 = , (b) X 2 = '
(c) C 2H4 (OH}z (d) C 3 H5(OHh M(M, -M 2 )+p . M(M, -M2)-P
142. What is the osmotic pressure of the solution obtained by _M(M,-M2)+P (d) _M(M,-M2 )-p
()
cx 2 - x2 - ,
mixing 300 cm3 of 2% (mass-volume) solution of urea with MM, MM,
300 cm3 of3.42% solution of sucrose of20°C? (where P is the density of solution and M, and M2 are the
(R = 0.082 L atm K-' mol-I) (SCRA 2009) molar masses of solvent and solute, respectively.)
(a) 5 atm (b) 5.2 atm (c) 2.6 atm (d) 4.5 atm 152. The boiling point of a solution of 0.11 g of a substance in 15 g
of ether was found to be O.I°C higher than that of pure ether.
[Hint: nV = [( : : tea + (:: tcroJRT The molecular weight of the substance will be (Kb = 2.16):
[PET (MP) 2002]
n x 600 = [~+ 3 3.42J 0.082 x 293
x (a) 148 (b) 158 (c) 168 (d) 178
1000 60 342 153. 2.5 litre of 1 MNaOH solution are mixed with another 3 litre
n x 0.6 = (0.1 + 0.03) x 0.082 x 293 of 0.5 M NaOHsolution. Then the molarity of the resulting
n = 5.2atm] solution is: [CBSE (PMT) 2002]
143. A solution of 1 molal concentration of a solute will have (a) 0~80M (b) l.OM (c) 0.73M (d) 0.50M
lllaximum boiling point elevation when the solvent is: 154. In a mixture, 'A' and 'B' components show the negative
[PMT (MP) 2000) deviations as: (AlEP2002)
(a) ethyl alcohol (b) acetone (a) ~Vmix > 0
(c) benzene . (d) chloroform (b) ~Vmix < 0
144. :Isotonic solutions have: (DPMT 2000) (c) A - B interaction is weaker than A - A and B - B
(a) same boiling point (b) same vapour pressure interactions
(c) same melting point (d) same osmotic pressure (d) none of the above reasons is correct
145. The depressions in freezing point for 1 M urea, 1 M glucose 155. A soluti,?n contains non-volatile solute of molecular mass M 2.
and 1 MNaCI are in the ratio: [CET (Haryana) 2000) Which of the following can be used to calculate the molecular
(a) 1 : 2 : 3 (b) 3 : 2 : 2 mass of solute in terms of osmotic pressure?
(c) 1: 1 : 2 (d) none of these [CBSE (PMT) 2002]
146.' An aqueous solution of 6.3 g oxalic acid dihydrate is made up
to 250 rnL. The volume of 0.1 NNaOH required to completely
(a) M2 = rnz VRT
1t
(b) M2 = (i JR:
,neutralize 10 rnL of this solution is: (lIT 2001)
(a) 40 rnL (b) 20 mL (c) 10 rnL (d) 4 rnL (c) M=(i JnRT
2
,(d) M2 = (rnzJ
- -1t
V RT
147. The vapour pressure of a solvent A is 0.80 atm. When a
non-volatile substance B is added to this solvent, its vapour (rnz = mass of solute; V = volume of solution; n = osmotic
pressure drops to 0.6 atm. The mole fraction of B in the pressure)
solution is: iPMT (MP) 2000) 156. 0.6 g of an organic compound when dissolved in 21.7 g water
(a) 0;25 (b) 0.50 (c) 0.75 (d) 0.90 freezes at 272.187 K. The molar mass of the organic
148. An aqueous solution of sucrosy, C12 H 22 011 , containing compound is close to:
(K f of water is 1.86 deglmolality; freezing point is 273 K)
34.2 gIL has an osmotic pressure of 2.38 atmospheres at 17° C.
For an aqueous solution of glucose, C 6 H12 0 6 , to be isotonic (SCRA2009)
with this solution, it would have: (AMU 1997) (a) 61 g mol-' (b) 63 g mol-'
(a) 34.2gJL (b) 17.1g/L (c) 65 g mol-' (d) 67 g mol-'
(c) 18.0 gIL J,d) 36~0 gIL of glucose
SOLUTIONS
157. Osmotic pressure of urea solution at 10°C is 500 mrri. Osmotic (d) The relative lowering of vapour pressure is directly
. pressure ofthe solution becomes 105.3 mm, when it is diluted proportional to the original pressure
and temperature raised to 25°C. The extent dilution is: 165. Calculate the molal depression constant of a solvent which has
[PMT (MP) 2004) freezing point 16.6°C and latent heat of fusion 180.75 J g -I.
(a) 8 times (b) 5 times (c) 4 times (d) 7 times [JEE(Ori!\1Sa)2005)
158. The average osmotic pressure of human blood is 7.8 bar at Ca) 2.68" (b) 3.86 (c) 4.68 (d) 2.86
37°C. What is the concentration of an aqueous NaCl solution 166. If for a sucrose solution, elevation in boiling point is O.loC
that could be used in blood stream? (AIIMS 2004) then what will be the boiling point of NaCI solution for same
(a) 0.15 mollL (b) 0.30 mollL molal concentration? (B~U (Pre.) 2005)
(c) 0.45 mollL (d) 0.60 mollL· (a) O.loC (b) 0.2°C (c) 0.08°C (d) O.OloC
159. Camphor is often used in molecular mass determination 167. Which has minimum osmotic pressure? . (DeE 2005)
because: ICBSE-PMT (Pre.) 2004) (a) 200 mL of2 MNaCI solution
(a) it is readily available (b) 200 mL of 1 M glucose solution
(b) it has very high cryoscopic constant (c) 200 mL of2 Murea solution
(c) it is volatile (d) All have same
(d) it is a solvent for organic substances 168. Solution A contains 7 gIL of MgCl 2 and solution B contains
160. A 0.004 M solution of Na2S04 is isotonic with a 0.010 M 7 gIL of NaCl. At room temperature, the osmotic pressure of:
solution of glucose at same temperature. The apparent degree (DeE 2005)
of dissociation ofNa2S04 is: [lIT (S) 2004) (a) solution A is greater than B
(a) 25% (b) 50% (c) 75% (d) 85% (b) both nave same osmotic pressure
161. Which ofthe following liquid pairs shows a positive deviation (c) solution B is greater than A
from Raoult's law? IAIEEE 2004; AMU (Med) 2007) (d) can't determine
(a) Water-hydrochloric acid (b) Benzene-methanol 169. The van't Hoff factor for BaCl2 at 0.01 M concentration is
(c) Water-nitric acid (d) Acetone-chloroform 1.98. The percentage dissociation of BaCl 2 at this
162. Which one of the following statements is false? concentration is: [rET (Kerala) 2005)
(AIEEE 2004) (a) 49 (b) 69 (c) 89 (d) 98
(~) Raoult's law states that vapour pressure of a component (e) 100
over a solution is proportional to mole fraction 170. Equimolar solutions in the same solvent have: (AlfEE 2005)
(b) The osmotic pressure (1t) of a solution is given by the (a) same boiling point but different freezing points
relation 1t = MRT where M is molarity of the solution (b) same freezing point but different boiling points
(c) The correct order of osmotic pressure for 0.01 M aqueous (c) same freezing and boiling points
solution of each component is: (d) different freezing and boiling points
BaCl2 > KCl > CH3COOH > Sucrose 171. A solution of urea (mol. mass 56 g mol-I) boils at 100.18°C at
(d) Two sucrose solutions of same molality prepared in the atmospheric pressure. If Kf and Kb for water are 1.86 and
different solvents will have the same freezing point 0.512 K kg mol- I respectively, the above solution will freeze
depression at: [CBS¥-fMT (Pre.) 2005]
163. A solution of sucrose (molar mass = 342 g mol-I) has been (a) 0.654°C (b) - 0.654°C -
prepared by dissolving 68.5 g of sucrose in 1000 g of water. (c) 6.54°C (d) - 6.54°C
The freezing point of the solution obtained will be: 172. If 0.5 g ofa solute (molar mass 100 g mol-I) in 25 g of solvent
(K f for water = 186 K kg mol-I) [CBSE (PMT) 2010) elevates the boiling point by 1 K, the molar boiling point
(a) -0.372°C (b) -D.520°C constant of the solvent is: IfMT (K~rala) 2006]
(a) 2 (b) 8 (c) 5 (d) 0.5
(c) +0.372°C (d) -D.570°C
(e) 10
(Hint: I1T =K f X wB X 1000 173. Osmotic pressure observed when benzoic acid is dissolved in
mBxwA
benzene, is less than that expected from theoretical
= 1.86 x 68.5 x 1000 considerations. Thisis because: [KCET 2006)
342 x 1000 (a) benzoic acid is an organic solute
=0.372 (b) benzoic acid has higher molar mass than benzene
Freezing point of solution = 0 - 0.372°C (c) benzoic acid gets associated in benzene
= -D.372°C] (d) benzoic acid gets dissociated in benzene
164. Which of the following is incorrect? [CET (J&K) 2005) 174. A 5% solution by mass of cane sugar in water has freezing
( a) Relative lowering of vapour pressure is independent of the point of271 K and freezing point of pure water is 273.15 K.
nature of the solute and the solvent The freezing point of a 5% solution (by mass) of glucose in
(b) The vapour pressure is a colligative property water is: (AIIMS 2006)
(c) Vapour pressure of a solution is lower than that of the (a) 271 K (b) 273.15 K (c) 269.07 K (d) 277.23 K
solvent
/
374 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
6. In which of the following cases does osmosis take place if the 11. Which is a dimensionless quantity?
solutions are separated by a semipermeable membrane? (a) Mole fraction (b) Molality
(a) 0.1 MNaCI and 0.2 M glucose (c) % by wt. ofsolvent (d) % by wt. of so lution
(b) 0.1 M sucrose and 0.1 M fructose 12. Which ofthe following concentration terms is/are independent
(c) 0.05MK4[Fe(CN)6]andO.1MCa~lz of temperature? ' [PET (Kerala) 2006;
(d) 10-3 MCaCl z and 1.5 x 1O-3 MNaCI CET (Gujarat) 2006; DCE 2007]
(a) Molarity
7. Match the following:
(b) Molarity and mole fraction
Solute (equimolar) 11: (OP) ratio
(c) Mole fraction and molality
(i) Urea, glucose, fructose (A) 1: 0.8: I (d) Molality and normality
(ii) NaCI, MgClz, K 2S04 (B) I : 2: 3 (e) 'Only molality ,
(iii) AliS04h, Na3P04,K4Fe(CN6) (C) 1 : 1 : 1 13. In the depression of freezing point experiment, it is found that:
(lIT 1999)
(iv) Glucose, NaCI, CaCh (D) 2: 3: 3 (a) the vapour pressure of the solution is less than that of pure
(i) (ii) (iii) (iv) solvent,
(a) A B C D' (b) the vapour pressure of solution is more than that of pure
solvent
(b) B D C A (c) only solute molecules solidifY at the freezing point
(d) only solvent molecules solidifY at the freezing point
(c) D B A C 14. Which of the following is/are correct for a solution of a
particular concentration?
(d) C ,D A B (a) Molarity is always less than molality
(b) Formality is equivalent to molarity
(c) Mole fraction is equivalent to mass fraction
8. Match the following graph:
(d) Normality of H 2 S04 solution is double than its molarity
A 15. Effect of adding a non-volatile solute to a solvent is:
(a) to lower the vapour pressure
(b) to increase its freezing point
•
(c) to increase its boiling point
I (d) to decrease its osmotic pressure
16. Whichofthe following formls an ideal solution?
BP
(a) Ethyl bromide + ethyl iodide
(b) Ethyl alcohol + water
(c) Chloroform + benzene
Mole fraction (d) Benzene + toluene
17. Osmotic pressure of a solution is:
A (i)( +) deviation (a) directly proportional to the molar concentration of the
B (ii) Ideal solution
C (iii) (-) deviation (b) inversely proportional to the molecular weight of the
solute
(a) (A) (i), (B) (ii), (C) (iii)
(c) inversely proportional to the temperature
(b) (A) (iii), (B) (ii), (C) (i)
(d) directly proportional to the volume of the solution
(c) (AHii), (B) (iii), (C) (i)
18.' Which ofthe following is/are true?
(d) none of these
(a) For the same solution, elevation in boiling
9. Vapour pressure of methyl alcohol and ethyl alcohol solutions
point = depression in freezing point
is represented by P = 1l5xA + 140 where x A is the mole
pO (b) van't Hoff factor for a dilute solution of BaCl2 is 3
fraction of methyl alcohol. The value of lim -.!L is: (c) Elevation in boiling point is due to increase in vapour
XA .... O xB pressure
(a) 255 (b) 115 (d) Depression in freezing point is due to decrease in vapour
(c) 140 (d) 135 pressure
10. To 10 mL of I M BaC12 solution 5 mL of 0.5 M K 2 S04 1: 19. In the following question, more than one of the answers given
added, BaS04 is precipitated out. What will happen? may be correct. Select correct answer and mark it according to
(a) F.pt. is increased (b) B.pt. is increased the code: [BHU (Mains) 2008]
(c) F.pt. is lowered (d) B.pt. is lowered A solution containing components A and B exhibits positive
deviation from Raoult's law only when
to.
SOLUTIONS 3r7-··
['~~~:·'-·'·:?li~6£ii!?r~~:-,"· c~~m~~~,' I
• Set-1
1.(a) 2.(c) 3. (b) (d)4. (b)
5. 6. (d) 7. (c) 8. (b)
9. (c) 10. (d) 11. (a) 12. (a) 13. (d) 14. (c) 15. (a) 16. (d)
n (a) 18. (b) 19. (c) 20. (b) 21. (d) 22. (c) 23. (a) 24. (b)
25. (c) 26. (d) 27: (b) 28. (a) 29. (c) 30. (b) 31. (d) 32. (d)
33. (b) 34. '(a) 35. (d) 36. (c) 37. (b) 38. (c) 39. (b) 40. (d)
41. (a) 42. (a) 43. (b) 44. (c) 45. (d) 46. (b) 47. (b) 48. (d)
49. (c) 50. (c) 51. (b) 52. (a) 53. (b) 54. (d) 55. (d) 56. (a)
57. (c) 58. (b) 59. (b) 60. (c) 61. (a) 62. (d) 63. (c) 64. (d)
65. (a) 66. (d) 67. (a) 68. (c) 69. (b) 70. (c) 71. (a) 72. (b)
73. (d) 74. (b) 75. (a) 76. (c) 77.(d) ,78. (d) 79. (a) 80. (d)
81. (b) 82. (a) 83. (a) 84. (d) 85.(d) 86. (b) 87. (c) 88. (b)
89. (b) 90. (c) 91. (il) 92. (d) 93. (d) 94. (d) 95. (b) 96. (b)
"
97. (c) 98. (b) 99. (a) 100. (c) 101. (d) 102. (b) 103. (b) 104. (b)
105. (c) 106. (c) 107. (c) 108. (a) 109.- (a) 110~ (d) 111. (b) i12. (d)
113. (a) 114. (d) 115. (a) 116. (c) 117. (a) 118. (d) 119. (d) 120. (b)
121. (a) 122. (b) 123. (d) 124~ (c) 125. (cr' 126. (b) 127~ (a) 128. (b)
'. 129. (d)
(d)
130. (b)
138. (c)
131. (a)
(c)
132. (b)
140. (b)
133. (a)
(a)
134. (b)
142. (b)
135. (b)
143. (c)
136. (a)
(d)
'., 137.
145. (c) 146. (a)
139.
147. (a) 148. (c)
141.
149~ (c) 150. (b) 151. (a)
144.
152. (b)
153. (c) 154. (b) 155~ (b) 156. (b) 157. (b) 158. (b) 159. (b) 160. (c)
161. (b) 162. (d) 163. (a) 164. (d) 165. (b) 166. (b) 167. (b) 168. (a)
169. (a) 170. ,(d) 171. (b) 172. (c) 173. (c) 174. (c) 175. (d) 176. (b)
177. (d) 178. (a) 179. (c),
. 180. (c) 181. (a) 182. (a) 183. (a) 184. (b)
185. (c) 186. (d) 187. (b) 188. (a) 189. (a) 190. (b) 191. (c)
:. . ~~)<~~~ :~-i:~';;'~~-~:;::/;;~-~;,:'"' :' _, ~:t, '. -t.'_.··''i1J;;;;:~:f$\::... "... " "i,:.~\t.<~~:·:~: ..~::~~~.'~.r: ·~.-~1::
[" -:;-,SSt:aDO".!f'Q$9N'6f:YPE QUESllGN$;· "
.-,- ."", " :--..'"" .,!:_tt-·.F,.: ..-~ "-;: "",":';'~~~, .. ~·!."1:'::..M-\"!.'i~\1.1:'-~~.'_ . :" ." ":,\,: . .i-.'
1. (d) (a)
2. (c)
3. ,4.(c) (a)
5. 6. (a) 7. (c) 8. (d)
',9. (a) 10. (c) 11. (c) 12. (a) 13. (a) 14. (b) 15. (a) 16. (c)
17. (c) 18. (a)
380 G. R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
1p~
Assume the temperature is constant at 25°C.
Vapour Vapour pressure data (2S°C):
pressure.
Benzene 75 mmHg
Toluene 22 mm Hg
(a) The vapour will contail\ higher percentage of benzene
0.2 0.4 0.6 0.8 1 (b) The vapour will contai~ higher percentage of toluene
(a)PQ + RS (b)PQ+QR +RS ( c) The vapour will contain equal amount. of benzene and
toluene .
(c)SR +SQ (d)PQ+QR
(d) Not enough information is given to make a prediction
14. Y g ofa non-volatile organic substance of molecular mass M is
[Hint: A: Benzene B : Toluene '
dissolved in 250 g benzene. Molal elevation constant of
benzene is K b • Elevation in its boiling point is given by: P= PA + PB
o 0
(a) M (b) 4K by (c) Kby (d) Kby P = PA X A + PB XB
Kby M 4M M I I
=75 x + 22x-
2 2
[Hint: IlT = Kb x x 1000
. mB XWA
= 37.5 + II = 48.5
y x 1000 4Kb y Mole fraction of benzene in vapour, YA PA = 37.5 0~78'
=Kb X M x250 =-;;;t] P 48
Similarly, mole fraction oftoluene in vapour, YB 0.22
15. Which of the fonowing represents correctly the changes in
:. The vapour will contain higher percentage of benzene.]
thermodynamic properties during the formation of I mole of
an ideal binary solution?
382 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
19. When 1.2 g of sulphur is melted With 15g of naphthalene, the (a) th~re is positive deviafion from Raoult's law
solution freezes at 77 .ZOC. What is the molar mass of tbis form (b) there is negative deviation from Raoult's law
ofsulphur? (c)there is no deviation from Raoult's law
Data fOf naphthalene: (d)molecular masses of A and B are also required for
Melting point (m.pt.) 80°C calculating the deviation
Freezing point depression constant K f 6.80 K m- I I 2
[Hint: xA =3' ,xe = 3
(a) ISO g mol-I (b) 190 g mol-I
P = P~ xA + P~ xe
(c) 260 g mol- 1 (d) 450 g mol-1
= 150X.!+ 240 x 2 = 50+ 160=21Omm
[Hint:tJ.T = K x we x 1000 3 3
. f me xWA
Pexp < PcaJculated
K x 1000 :. There is negative deviation from Raoult's law.]
me -fx
tJ.T wA 27. A compound MX 2 has observed and normal molar masses
= 6.S x 1.2 x 1000 '" 190] 65.6 and 164 respectively. Calculate the apparent degree of
2.8 15 ionization of MX 2: .
20. Which concentrations can be calculated if the mole fractiot} . (a) 75% (b) 85% (e) 65% (d) 25%
and density of an aqueous solution of HCI are known? NormalllX)iar mass
[Hint:
I. Molality 2. Molarity 3. Percentage by mass Observed llX)lar mass
(a) 1 only (b) 3 only = 164 =2.5
(c) 1 and 2 only (d) 1,2 and 3 . 65.6
21. The vapour pressure of a liquid in a closed container depends i 1
IX= , n =3 (number of ions)
on: . n-l
(I) temperature of liquid (2) quantity of liquid
= 2.5 -1 = 1.5 = 0.75
(3) surface area of the liquid 3 -1 2
. (a) I only (b) 2 only :. Percentage ionization of MX2 will be 75%.]
. (c) I and 3 only (d) 1,2 and 3 28. Compound PdCI4 · 6H20 is a hydrated complex; I molal
·22. A solution is prepared by dissolving a 2.5 g sample of an aqueous solution of it has freezing point 269.28 K. Assuming
unknown compound in 34 g of benzene (C6~) boils at 1.3 SoC ·100010 ionization of complex, calculate the molecular formula
higher than pure benzene. Which expression gives the molar of the complex (Kf for water =1.86 K kg mol-I):
mass of the unknown compound?
Compound :Kb (a) [Pd(H20)6]CI4 (b) [Pd(HzO)4Clz]CI2· 2HzO
1 (c) [Pd(H20hC13]CI·3H20 (d) [Pd(H20hCI4l4H20
C6~ 2.53°Cm-
[Hint: tJ.T = i xKf x m
(a) 2.53 x 2.50 34
(b) 1.38 x - x 2.50 (273 - 269.28) =: i x 1.86 x I
1.38 2.53
3.72 i x 1.86
2.53 1
(c) 2.5 X 103 X - X- (d) 2.50 x 103 x 1.38 x 2.53 i= 2
. 34 1.38 34 i I
IX=--
23. If liquids A and B form an ideal solution: n-l
(a) the free energy of mixing is zero 2-1
(b) the free energy as well as entropy of mixing are zero 1=--orn=2
n-l
(c) enthalpy of mixing is zero
Thus, the complex should give two ions in the solution, i.e., the
(d) the entropy of mixing is. zero
complex will be (Pd(HzOh03]CI·3H20] .
24. Solute A is· a ternary electrolyte and solute B is a 29. Inulin is dissolved in suitable solvent and the osmotic pressure
non-electrolyte. If O.IM solution of B produces an osmotic ',(n) of solutions of various concentrations (glcm 3 ) , C is
pressure of2P at temperature 3T K thenO.05M solution of A
measured at 27~C. The slope of plot ofn against C is found to
at T K will produce an osmoticpressirre of: ,
be4.1 x 10-3. The molecular mass of inulin is: .
(a) P (b) UP (c) 2P (d) lOP
25. Which of the following plots represents the behaviour of an (a) 6x 106 (b) 3 X 106 (c) 6x 103 (d)3 x l<t
ideal binary liquid solution? [Hint: 1tV nRT
=:
,
SOLUTIONS
XB X 1000
Slope ofthe line will be RT , m m=l
m (1- xB)mA
xB = mole fraction of solute
i.e. , RT =4.lx W- 3 x 1000 mA == molar mass of solvent
1 = --'''-----
m (1 xB)XI8
m = RT ~._0_82_1_X_I_00_0-.o-x_3_0_0
= ..
-4.-1-x--;; 4.1 x 10-3 XB == 0.0176, xA 0.9824
P= POXjf
= 6x nf] P = 760 x 0.9824
30. pH of a 0.1 M monobasic acid is measured to be 2. Its osmotic = 746.624
pressure at agiven temperature T K is: !J..p = Po - P 760 ...: 746.624
(a) O.lRT (b) O.1IRT • l.IRT
(c) (d) O.OIRT . '" 13.4 mm Hg]
[Hint: . HA H+ + A- 34. The temperature at which the molarity of pure water is equal
t=O C o 0 to its molality is:
C-Ca ea Ca (a) 273 K (b) 298K
[H+ Ca.; [H+j=;: lO-pH (c) 277 K (d) none of these
35. Isopiestic solutions have:
Ca 10-2
(a) same vapour pressure (b) same osmotic pressure
O.1a =10-2 (c) same freezing point (d) same hoiling point
a==O.1 36. Molarity and molality of a solution of caustic soda are
i-I i respectively 11.12 M and 94.12 m. The density t>fthe solution
a==--; 0.1=
n-I 2 is:
i = 1.1 (a) 0.556 g mL- 1 (b) 5.56 g mL -I
(c) 55.6 g mL- 1
1t "'" iCRT (d) none of these
= 1.1 x 0.1 x RT = 0.1 IRT ]
31. The amount of ice that will separate on cooling a solution [Hint: d =M l r
,m
+ molar mass of SOlute)
1000
containing 50 g of ethylene glycol in 200 g water at -9.3°C,
K
f
1.86Kkg mol-I: ., d= 11.12(-._1_+~)
94.12 1000
(a)38.7lg (b)38.71mg (c)42g (d) 42 mg
= 0.556 g mL-1 ]
WB x 1000
[Hint:!J..T K f x --"'--- 37. Which of the following solutions has osmotic pressure nearer
mB x wA
to that of equimolar solution of K4[Fe(CN)6] ?
9.3 = 1.86 x 50 x 1000 (a) Na2S04 (b) BaCl 2
62xwA
(c) Al 2 (S04h . (d) C12H22011
W A = 161.29 g (amount of water present at ~ 9.3°C) 38. Equal amounts of a solute are dissolved in equal amounts of
:. Amount of ice separated == 200 -161.29 two solvents A and B. The lowering of vapour pressure for the
== 38.71 g] solution A is twice the lowering of vapour pressure for the
32. 2 moles each of liquids A and B are dissolved to form an ideal solution B. If M A and M B are the molecular weights of
solution. What will be the mole fraction· of B in .the vapour solvents A and B respectively, then:
phase? (a)MA MB (b)MA==MBI2
.',
p~ = 120 torr; p~ = 80 torr. (C)MA 4MB (d)MA 2MB
(a) 1/4 (b) 112 (c) 3/5 . (d) 2/5 Following questions may hayemore than one correct options:
[Hint: P = PA +PH ]. Consider the following solutions:
I. I M sucrose II. I M KCl
P == p~ xA
+ P~ xB
2 . 2 III. 1 Mbenzoic acid in benzene.IV.l M(NH3hP04
=120x-+ 80x Which of the following is/are true?
4 4 (a)All solutions are isotonic
:d: 60 +40 = 100 torr
(b) III is hypotonic ofI, II and IV
YB == mole fraction of B in the vapour phase .
(c) I, II and ~II are hypertonic ofIV
40 2
(d) IV is hypertonic of I, II and III
Ptota! 100 == 5 ]
2. Osmotic pressure of the solution depends on:
.33. Lowering of vapour pressure in 1 molal aqueous solution at (a) nature of solute
100°C is: .
(b) nature of solvent
(a) 13.44 mmHg (b) 14.12 mm Hg (c) temperature
. (c)31.2mmHg (d) 35.2 mmHg
(d) molar concentration of solute
[Hint: Molality and mole fraction are related as follows:
384 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
3. The following is a graph plotted between the vapour pressures 2. The osmotic pressure of solution of Y will be lower than
of two volatile liquids against their respective mole fractions. that of X
3. The freezing point of the solution of X will be fower than
pg . that ofY .
4. The relative lowering of vapour pressure of both the
solutions will be the same
Vapour
pressure
1PA
0 Vapour
pressure Select the correct answer from the codes given below:
1 (a) 1,2,3 (b) 2, 3,4 (c) 1,2,4 (d) 1,3,4
7. For a given value of degree of dissociation, which of the
following have correct van't Hoff factor?
(a) NaCI i 2+a
(b) Ca(N03h 1+ 2a
(c) K 4 [Fe(CN)6] i = 1+ 4a
Which of the following statements are correct?
(d)(NH3 hP04 i = 3+ a
(a) WhenxA = I and xB == 0, then p = p~
8. 1 mole benzene (P~'lZene = 42 rom) and 2 mole toluene
(b) WhenxB == I and xA 0, then p = p~ (P~luene 36 rom) will have:
(c) WhenxA = I and xB == 0, then p < p~ (a) total vapour pressure 38 rom
(d) WhenxB ==1 and xA==o,thenp>p~ (b) mole fraction of vapours of benzene above liquid mixture
4. Which of the following combinations are correct for a binary is 7119 .
solution, in which the solute as well as solvent are liquid? (c) positive deviation from Raoult's law
(a) C 61\ and C 6 H5CH3 ; MSol > 0; 8Vso1 0 (d) negative deviation from Raoult's law
[Hint: P p~ X A + p~ x B A ~ Benzene, B ~ Toluene
(b) CH3 -
°II
C CH3 and CHCI 3 ; MSol < 0; 8VSo1 < 0 = 42 x 1. + 36 x 2
3 3
(c) H 2 0 and HCI; MSol > 0; 8VSo1 < 0 114
(d) H 2 0 and C 2 H sOH; 8Hso1 > 0~8~SOI > 0 =-=38mm
3
5. A solution containing 0.1 g of a non-volatile organic substance Mole fraction of benzene in vapour == Pbenzene = 42/3
P (molecular mass tOO) in 100 gof benzene raises the boiling PIOta! 38
point of benzene by 0.2° C, while a solution containing 0.1 g of = 7/19]
another non-volatile substance Q in the same amount of 9. The decrease in freezing point of an aqueous solution of a
benzene raises the boiling point of benzene by 0.4° C. What is substance is 1.395 J( and that in the freezing point of a
the ratio of molecular masses of P and Q ? (SCRA 2007) benzene solution of the same substance is 1.28 K. The
(a) 1:2 (b) 2:1 (c) 1:4 (d) 4:1 substance:
Kb x ( WB X 1000 ) (a) dissociates in aqueous solution as well as in the benzene
(8T )p rn B x WA p solution
[Hint:
(8T )g K ( x 1000 I (b) forms complexes in the solution
(c) associates in the benzene solution
b X rnB x WA )g
(d) . dissociates in the aqueous solution and not in the benzene
1000 J solution
0.2 _ ( 100 x 100 p 10. The vapour pressure of water at T (K) is 20 rom Hg. The
0.4 - ( 0.1 x 1000 J. following solutions are prepared at T (K):
100 x rnB Q I. 6 g of urea (mol. wt. = 60) is dissolved in 178.2 g of water.
II. 0.01 mole of glucose is dissolved in 179.82 g of water.
1. = (rnB)Q III. 5.3 g ofNa2C03 (mol. wt. = 106) is dissolved in 179.1 g of
2
100 water.
=50
rnB Identify the correct order in which the vapour pressures of
• • (rnB)p : (rnB)Q = 100: 50 solutions increase: IEAMCET (Medical) 2006)
2: 1] (a) III, I, II (b) II, III, I (c) I, II, III (d) I, III, II
6. Consider 0.1 M solution of two solutes X and Y. The solute X [Hint:
behaves as uni-univalent electrolyte while the solute Y 6/60 6
dimerises in solution. Which of the following statements are I. XB = +-
nA + nB 178.2118 60
correct regarding these solutions?
=0.01
1.. The boiling point of solution of X will be bigher than.. that
~Y . tlp =xB 0.01
Po
SOLUTIONS 385
, O.Of II: 'Consider ·lowermg. '9{ "vapour pressure (Ap), elevation in
II Xg = = -;-;::;;::-=--
. nA + no 179.82 + 0.01 boiling point (!!.Tb ) and depression in freezing point (!!.Tf ) of
18 a solvent for the same molar concentration of each of the
= 0.001 following three solutes:
t:.p = 0.001 1. BaCl2 2. NaCl 3: MgCl2
Po Which of the following is/are the correct sequence?
. (SeRA 2009)
III. Xo '" ~ = 17 9. 1 06
5 311
0.005
nA + no __ . + 5.3 (a) !!.p:3<2<1 (b) !!.Tb:1>2>3
18 106 (c) !!.Tf : 3 <2 < I (d) None of these
Ap . [Hint: van't Hoff factOr of both BaC12 and MgClz are same, i,e.,
- = Uo
Po 3, hence none of the given sequence are correct.]
= 3 x 0.005
=O.oI5
.. Vapour pressures of solutions will increase in the following
sequence:
(lII) < (I) < (II).]
[?4~';
• Single correct option
1. (b) 2. (d) 3. (a) 4. (a) 5. (b) 6. (b) 7. (c) 8. (b)
9. (d) 10. (c) 11. (d) . 12. (a) 13. (c) 14. (b) 15. (c) 16. (a)
17. (e) 18. (b) 19. (b) 20. (d) 21. (a) 22. (c) 23. (c) 24. (a)
25. (c) 26. (b) 27. (a) 28. (c) 29. (a) 30. (b) 31. (a) 32. (d)
33. (a) 34. (c) 35. (a) 36. (a) 37. (c) 38. (b)
i 1
• Passage 1 [Hint: ex, , n = 5 since, K 4[Fe(CN)6] gives 5
n-l
ions in the solution
-iA 1.24 M aqueous solution ofK1 has density ofl.15 g/cm 3.
0.6= i-I
Answer the following questions about this solution: 5-1
i =: 3.4]
1. Percentage composition of solute in the solution is:
(a) 17.89 (b) 27.89 (c) 37.89 (d) 47.89
5. A solution of benzoic acid dissolved in benzene such that it
undergoes molecular association and its molar mass
2. Molality of this solution will be:
approaches 244. Benzoic acid molecules will exist as:
(a) 2.61 (b) 1.31 (c) 4.12 (d) 3.12
(a) dimer (b) monomer
3. What is the freezing point of the solution if 'the KI is
(c) tetramer (d) trimer
completely dissociated in the solution?
6. -The molar mass of the solute sodium hydroxide obtained from
(a) - 4.87°C (b) 3.22°C
the measurement of the osmotic pressure of its aqueous
(c) - 1.22°C (d) None of these
solution at 27°C is 25 g mOrl. Therefore, its dissociation
4. Experimental freezing point of the .solution is 4.46°C. What percentage in this solution is: [eET (J&K) 2009J
% ofKI is dissociated?
(a) 75 (b) 60
(a) 82% (b) 90% (c) 83% (d) None
(c) 80 (d) 70
5. Normality of this solution is: NOIDml molar mass
WQ~ 001~ M2~ 003n [Hint: i= ... (i)
AbnomJal molar mass
i 1
• Passage 2 a ~
n-l
The colligative properties of electrolytes require a slightly i =: 1+ ex, for binary electrolyte
different approach than the one used for the colligative properties of 40
non-electrolytes. The electrolytes dissociate into ions in a solution. It'
1+ a = 25; ex, 0.6
is the number of solute particles that determines the colligative % ionisation 60 ]
properties of a solution. The electrolyte solutions, therefore, show
abnormal colligative properties. To account for this effect we define • Passage3
a quantity called the van i Hoff factor, given by:
M.any chemical and biological processes depend on osmosis
Actual number of particles in solution after dissociation
which is, the selective passage ofsolvent molecules through a porous
Number of formula units initially dissolved in solution membrane from a dilute solution to a mo~e concentrated one. The
osmotic pressure 1t" depends on molar concentration of the solution
1 ( Jor non - electrolytes);
(1t CRT). If two solutions are of equal solute concentration and,
i > 1 ( for electrolytes, undergoing dissociation) hence, have the same osmotic pressu.re, they are said to be isotonic.
i < I ( for solutes, undergoing association). If two solutions are of unequal osmotic preSS/ires, the more
concentrated solution is said to be hypertonic and the more diluted
. Answer the following questions:
solution is described as hypotonic.
1. Benzoic acid undergoes dimerisation in benzene solution. The Osmosis is the major mechanism for transporting water upward
van't Hoff mctor 'i' is related to the degree of association 'a' in the plants. Transpiration in the leaves supports the transport
ofthe acid as: mechanism of water. The osmotic pressure of seawater is about 30
(a) i 1 a (b) i= 1 + a atm; . this is the pressure that must be applied to the seawater
. a (separated from pure water using a semipermeable membrane) to get
(c) i =: 1-- (d) i = 1 + a drinking water.
2 2
Answer tbe foUowing questions:
2. A substance trimerises when dissolved in a solvent A. The
van't Hoff factor' i' for the solution is: 1. A plant cell shripks when it is kept in:
(a) 1 (b) 113 . (a) hypotonic solution (b) hypertonic solution
(c)3 (d) unpredictable (c) isotonic solution (d) pure water
3. For a solution of a non-electrolyte in water, the van't Hoff 2. 4.5% solution of glucose would be isotonic with respect to
factor is: ' ....... solution of urea.
(a) always equal to 0 (b)::;; 1 (a) 4.5% (b) l3.5%
(c) always equal to 2 (d) > 1 but < 2 (c) 1.5% (d) 9%
3. Glucose solution to be injected into the bloodstream must have
4. 0.1 M K 4 [Fe(CN)6] is 60% ionized. What will be its van't same ..... as that of the bloodstream.
Hoff factor? (a) molarity (b) vapour pressure
(a) 104. (b) 2.4 (c) 3.4 (d) 4.4 (c) osmotic pressure (d) viscosity
SOLUTIONS 387
4. .Isotonic solutions have same:
.
CH20H
(a) density (b) molarity I
(c) molality (d) mole fraction (c) CHOH. (d) C 6HI2 0 6
(e) normality I
CH20H
5. Osmotic ryse of a solution depends on:
2. 124 g each of the two reagents glycol and glycerol are added
(a) density (b) temperature
in 5 kg water ot the radiators in the two cars. Which of the
(c) nature of solvent (d) none of these following statements is wrong?
(a) Both will act as antifreeze
• Passage4
(b) Glycol will be better
(c) Glycerol is better because its molar mass is greater than
glycol
(d) Glycol is more volatile than glycerol
3. 620 g glycol is added to 4 kg water in·the radiator of a car.
What amount of ice will separate out at - 6°C? K J = 1.86 K
kg mol-I:
A 8 (a) 800 g (b) 900 g (c) 600 g (d) 1000 g
4. If cost of glycerol, glycol and methanol are same, then the
sequence of economy to use these compounds as antifreeze
Compartments 'A' and 'B' have the following combinations of will be:
solutions: (a) glycerol> glycol> methanol
A B (b) methanol > glycol> glycerol .
1. 0,1 MKCI 0.2MKCI . (c) methanol = glycol = glycerol
2. 0.1% (m/V ) NaCI 10% (mIV) NaCI (d) methanol > glycol < glycerol
3. 18 giL glucose 34.2 giL sucrose 5. Which among the following is the most volatile and the best
4, 20% (mlV ) glucose 10% (mIV) glucq~e antifreeze?
Answer the following questions: (a) CH 30H (b) C 2H sOH (c) Glycol (d) Glycerol .
1. Indicate the solutions which is/are isotonic:
. (a) 1 only (b) 3 only (c) 4 only (d) 2 only • Passage 6
2. The solutions in which the compartment 'B' is hypertonic: The solutions which boil at constant temperature like a pure
(a) 1,2 . (b) 2,3 (c) 3, 4 (d) 1,4 liquid and possess same composition in liquid as well as vapour state
3. Indicate the solution(s) in which the compartment' A' will are called azeotropes. The components of azeotropescannot be
show the increase in volume: separated by fractional distillation. Only non-ideal solutions form
(a) 1 (b) 2 (c) 3 . (d) 4 azeotropes. Solutions with negative deviation form maximum boiling
4. Indicate the solution(s)in which the compartment' B' will azeotrope and the solutionswithpositive deviation form miriimum
show the increase in volume: boiling azeotrope. Boiling poin't ofan azeotrope is never equal t~~e
(a) 1,2,4 (b) 1,2 (c) 2, 3 (d)3,4 boiling points of any ofthe components ofthe azeotrope.
5. The solution in which there will be no change in the level of Answer the following questions: .
the solution in the compartments' A' and 'B' is: 1. The azeotropic solutions of two miscible liquids:
(a) 1 (b) 2 (c) 3 (d) 4 (a) can be separated by simple distillation
(b) may show positive or negative deviation from Raoulfs
'l~w .
• PassageS (c) are supersaturated
(d) behave like single pure component and boil at a fixed
The boiling point elevation and the freezing point depression of
temperature
solutions have a number of practical applications, Ethylene glycol
(CHPH ,CHPH) is used in automobile radiators as an antifreeze 2. Solutions which distill without any change in composition or
because it lowers the freezing point of the coolpnt. The' same temperature are called:
substance also helps to prevent the radiator coolant from boiling (a) saturated (b) supersaturated
away by elevating the boiling point. Ethylene glycol has low vapour (c) ideal (d) azeotrope
pressure, We can also use glycerol as antifreeze, For boiling point 3. The azeotropie mixture of water and HCI boils at 108Se.
.elevation to occur, the solute must be non-volatile, but no such This solution is:
restriction applies .to. freezing point depression, For example. (a) ideal
methanol (CH PH), a fairly volatile liquid that boils only at 65°C is (b) non-ideal with positive deviation
sometimes used as antifreeze in automobile radiators. (e) non-ideal with negative deviation
Answer the foUowing questions: (d) cannot be predicted
1. Which of the following is a better reagent for depression in
freezing point but not for elevation in boiling point?
388 G.RB. PHYSICAL CHEMISTRY FOR COMPI;TITIONS
4. 100 mL liquid A and 50 mL liquid B are mixed to form 138 mL Answer the following questiOlis:
solution: IUs: 1. The freezing point ofthe solution Mis:
(a) ideal solution (b) high boiling azeotrope (a) 268.7 K (b) 268.5 K (c) 234.2 K (d) 150.9 K
(c) low boiling azeotrope '(d) none of these 2. The vapour pressure of the solution Mis:
5. Which, among the following combinations is maximum (a) 39.3 mmHg (b) 36.0mmHg
boiling azeotrope? (c) 29,5 mm Hg (d) 28.8 mm Hg
(a) H2 0 + CH30H (b) CCl 4 + CHCI3 3. Water is 1idde<l{to,~<S9Iution Msuch that the mole fraction of
(c) (CH3hCO + C 2H50H (d) H2 0 + HN03 water in the solutIon b~omes' 0.9: The boiling point of this
solution is: .
• Passage 7 (a) 380.4 K (b) 316.2 K (~)375.5 K (d) 354.7 K
The properties such as boiling point, freezing point and vapour (lIT 2008)
pressure of a pure solvent change when solute molecules are added . [Hint:
to get homogeneous solution. These are called colligative properties. XB X 1000 0.1 x 1000
1. Molality m
Applications of colligative properties, are very useful in daY-lo-day (l-xB) mA 0.9 x 46
life. One of its examples is the use of ethylene' glj/Col and water = 2.415
mixture as anti-jreezing liquid in the radiator ofautomobiles.
t:.T=Kf Xm
A solution M is prepared by mixing ethanol and water.
= 2 x 2.415 = 4.83
The mole fraction of ethanol in the mixture is 0:9:'
Freezing point of solution 155.7 - 4.83 150.9 K
Given : Freezing point depression constant of' wilter
=
(Kf for water) 1.86K kgmor 1 •
, 2. P == pOXA'
= 40x 0.9 = 36mmHg
Freezing point depression constant of ethanol (Kf for ethanol) 3. When water becomes solvent, the molality of solution
1
= 2.0Kkgmor " will be:
Boiling point elevation' constant of water (K b for water) m = x 100 = 0.1 x 1000 = 6:172
= 0.52K kg mor I XA x mA 0.9 x 18
Boiling point elevation constant of ethanol (K b for ethanol) t:.T=Kb x m=0.52 x6.172 = 3.209
1.2K kgmor l Boiling point of solution 373 + 3.209
Standard freezing point of water = 273 K =376.2K]
Standardfreezing point ofethanol: 155.7 K
Standard boiling point of water = 373 K
Standard boiling point ofethanol 351.5 K ,
Vapour pressure ofpure water 32.8- mm Hg
Vapour pressure ofpure ethanol = 40 mm Hg
Molecular weight of water = 18 g mor I
Molecular weight of ethanol' = 46 g mor 1
In answering the following questions, consider the solutions to be
ideal dilute solutions and solutes, to be non-volatile and
non-dissociative.
[~~
Passage 1. 1. (a) 2. (b) 3. (a) 4. (c) , 5. (b)
Passage 2. 1. (c) 2. (b) 3. (b) 4. (c) 5. (a) 6. (b)
Passage 3. 1. (b) 2. (c) 3. (c) 4. (b) 5. (a, b)
Passage 4. 1. (b)') 2. (a) 3. (d) 4. (b) 5. (c)
Passage 5. 1. (a) 2. (c) 3. (b) 4. (b) 5. (a)
Passage 6. 1. (b, d) 2. (d) 3. (c) 4. (b) 5. (d)
. Passage 7. 1. (d) 2. (b) 3. (b)
SOLUTIONS 389--
¢ SELF ASSESSMENT ¢
ASSIGNMENT NO.5
(b) Statement-l is true; statement-2 is true; statement-2 is not Statements (a, b, c and d) in Column-I have to be matched with
a correct explanation for statement.:t. statements (p, q, rand s) in Column-II. The answers to these
(e) Statement-l is true; statement-2 is false. questions have to be appropriately bubbled as illustrated in the
(d) Statement-l is false; statement-2 is true. following examples:
18. Statement-I: Solubility of ionic compounds in water depends If the correct matches are (a-p,s), (b-q,r), (c-p,q) and (d-s),
on both the lattice energy and the hydration energy. then correct bubbled 4 x 4 matrix should be as follows:
Because p q r s
Statement-2: Ionic compounds dissolve in water when their
hydration energy exceeds the lattice energy. a
e®0 01
----
19. Statement-I: Isotonic solutions have same molar
concentration.
Because
b
0 0
®
Statement-2: Solutions which have same osmotic pressure at
same temperature are known as isotonic solutions.
c
e· 0 0
[Hint: It is not necessary that solutions at same molar
concentration have same osmotic pressure, eg.,
d
®®0 0
1t(O.1M NaCl) > 1t(0.1 M glucose) because NaCI is ionised] 23. Match the Column-I with Column II:
20. Statement-I: The vapourpressure of 0.1 M Hg 2Ci 2 is equal Column-I Column-II
to 0.1 M AlCI 3 solution. (a) CCl4 + CHCl 3 (P) Raoult's law
". Because (b) C 6 H6 + H20 (q) Nearly ideal solution
. Statement-2: 0.1 M AlCI 3 and 0.1 M Hg 2Cl 2 give different (c) PA oc x A (r) Negative deviation from RaouIt's law
numbers of ions in a solution. (d) PA < P~XA (s) Positive deviation from Raoult's law
21. Statement-I: Elevation in boiling point will be high if the 24. Match the Column-I with Column II:
molal elevation constant of solvent is high. Column-I Column-II
Because
(Species completely ionised) (van't Hoff factor)
Statement-2: Elevation in boiling point is a colligative
(a) Hg 2Cl 2 (P)5
property.
(b) K 3[Fe(CN)6] (q) 4
11. Statement-I: Ethylene glycol is used as antifreeze for the
radiator of a car. '. (c) Ca3(P04h (r) 1
Because (d) glucose (s)3
. Statement-2: Ethylene glycol dissolves in water with the help 25. Match the Column-I with Column II:
of hydrogen bond and it lowers the fre,ezing point. Column-I Column-II
(a) Mole fraction (P) mol kg- J
SECTION-IV (b) Molality (q) Depends on temperature
Matrix-.Matdiing 'iype Questions (c) Molarity (r) Unitless
. This section contains 3 questions. Each question contains (d) Normality (s) Indepen~ent of temperature
statements given in two columns which have to be matched.
true solutions, the size of the particles of solute is very small and, phase or the continuous phase. This phase forms the larger part
thus,' these cannot be detected by any optical mean$ and freely of the icolloidalsolution. Depending' upon the physical· state of
, diffuse through membranes while ~ suspensions the' size of the disperSed and dispersion phases, the types of colloidal ~~l~tions
particles is large enough arid, thu~, clln be seen even by naked eye given in table 6.2 are possible. . ;:,~;' .•
and do not pass through filter paper. A colloidal sol;ution of gas in gas is not possible as'gaks are
True solutions are homogeneous systems while suspensions completely mispi~le and always form.tru.e.solutions. . .
Lyophobic and Lyophilic COlloid~.·;:,;;\·
are heterogeneous. These ate two extreme systems and. the
colloidal state is an iritermediate between the two. If we start with
... , '.
particles of large size (suspension) and go on subdividing them Colloidal solutions in which the disperSed~phaSelias very little
till we reach the size of particles found in solution,there is affinity for the dispersion phase are termed as lyophobic (solvent
continuous change in the characteristics. During transition, the hating) colloids. These are also termed suspensoids. Colloidal
, mixture passes through an intermediate state which shares the solutions of metals which have negligible affinity for solvents are
characteristics of both. This has been shown in Fig. 6.1. examples of this type. Generally, lyophobic sols are less stable.
On evaporation of solvent, the residue cannot be easily
100mll- 1mll ...·.. transformed back into colloidal state by ordinary means.
Lyophobic colloids are, therefore, also called irreversible
colloids.
Suspension . Colloidal solution True solution
Table 6.2 .--_.
000000 000000000 0000000010
000000 oc>Oc>ooooo 000000000
. Dispersed
Dispersion. '
1dlA 10.11. pbase
S.No. pbase Name . EX3qlpleS ..
(Colloidal
(Solvent)
. Fig. 6.1 , partides)
A system is said to be in colloidal state if particles of one or 1. Gas Liquid Foam Froths of air
more components have tbe size range*. loA to 10 3 A. 2. . Gas Solid Solid foam Pumice stone,
However, it is not possible to draw it sharp line of demarcation , dri~ sea foam
between colloidal. state and suspension.. The properties of one 3; Liquid Gas Liquid Cloud,'mist
. gradually appear into those of the other. Roughly speaking, the aerosol.
colloidal state is a heterogeneous dispersion of solute particles 4. Liquid. Liquid Emulsion· Milk; cream
of size ranging between loAful0 3 A into a solvent. . . 5. Liquid Solid Gel Jellies,curd,cheese
Some properties of the three systemS (suspension colloids and 6. Solid Gas Aerosol Smoke,haze
true solutions) are summarized ititable 6:1. 7. Solid Liquid. Sol Goldsol, sulphursol
8. Solid Solid Solid-sol Ruby glass,minerals, .
TYPES OF COlLOrOAL SOLU"FlONS . gems
The colloidal solutions consist of two-phases, one of which is Colloidal solutions in which the dispersed. phase has··
dispersed in the other, .This is called dispersed. phase, the considerable affinity for the dispe(Sion phase, i.e., colloidal
internal phase or the discontinuons phase. The phase in which solution, can be prepared by bringing them together, are called
the dispersion is done is termed dispersion phase, the external lyophilic (solvent loving) colloids. These are also known as
, Table 6:.3· Comparison of Lyophobic 'and Lyophilic Sols
. '.
S.No. Property Lyophobic sols (SuspenSoid) LYoPIillic Sols (Emnlsold)
1. Preparation Carinot be easily prepared. Special methods Can easily be prepared by shaking or warming
.are required for l'reparation. the substance with solvent.
2. Stability Are less stable. Atemore··stable.
3. Reversibility Are irreversible. Are reversible.
4. Viscosity· Viscosity is nearly the same a~ that of solvent. Viscosity, is much higher than that of solvent.
5. Surface tension Surface tension is almost the same as that of Surface tension is usually low.
the solvent.
6. Hydration or solvation These are less solvated as the particles h;l.Ve less These are highly solvated as the particles have
affinity for solvent. great affinity for solvent.
7. Charge The particles carry a characteristic charge either The particles have little or no charge at all.
positive or negative.
8. Visibility '·Particles can be seen under microscope. Particles cannot be seen under microscope.
9. Coagulation Easily coagulated by addition of electrolytes. Cannot be easily coagulated.
emulsoids. Gelatin, proteins, starch; etc., are the examples of this Suspension
type. Colloidal solutions of this type are mQre stable and .are also
known as reversible colloids since.the residue left on evaporation
can be readily transformed back into colloidal state· simply by
adding solvent. When the dispersioIl medium is water, the above
colloidal solutions rure termed as hydrophobic and hydrophilic. i
(For comparison, seehable 6.3) , '
. The. colloidalsolptio~s are al~o named ~ccording. tOi t~e "
disperslOn phase or :m~dlum used.\ The colloIdal solutions tn'
alcohol and benzene. are known as alco~ols and benzosols .
r~sp.ec~VelY. ~e COllOidalsolution~:Vhe.re mater i~ used as the
·dispersion medlUIn are called hydro~rls or\aquasols~ . Fig. 6.2
, :' 1 I; \ ." .1 .
Note: Colloidal solutions of solids in liqui~ ar~ abbrevi~ted as sols. colloidal graphite and gum arabic in lampblack colloidal solution
(Indian ink).
i I· !
·6.4 PREPARATION OF COLLOIDA~ 2. Electro-dispersion (Bredig'sarc method): This method is
SOLUTIONS :I \ suitable for the preparation of colloidal solutions of metals like
. gold, silver, platinum, etc. An arc is struck between the metal
1. Preparation of lyophilic sols: \rhe c?lloidal solutions of electrodes under the surface of water containing some stabilizing
lyophilic colloids like starch, glue, gelatin, !:etc., can be readily
prepared by dissolving these substances in wfiter either in cold or
on warming. Solutions of colloidal electrolyt~s such as soaps and ~----Metal rod
dye stuffs can also be prepared similarly.
2. Preparation of lyophobic sols: To get a substance in
colloidal form either the substance in bulk is broken down into 'm~gIBm~~tlce
t~ bath
Electric arc
fme particles of colloidal dimension (1. A to 103 A) or increasing
the size of molecular particles as to form larger aggregates. In
some cases, a third substance is" usually added to mcrease the ~~~~~~~~1~~~~~Lwater + KOH
stability of the sol. These substances are called stabilizers. Th~s,
there are two ways by which the lyophobic sols can be prepared: Fig. 6.3
(i) Dispersion methods: By splittmg coarse aggregates of agen~s such as a trace of KOH. Thewater is cooled by immersing
a substance into colloidal size. ' . the container in·a.n ice bath. The intense heat of the arc vaporises
'(ii) Condensation methods: By aggregating very smail . some of the metal which condenses under cold water.
particles (atoms, ions or moI~ules) into colloid;d size. Note: I. This method is not suitable when the dispersion medium
is all organic liquid as considerable charring occurs.
Table 6.4 . 2. !his method cOinprises.both dispersion and condensation.
S. No. . Dispersion methods·.1 Condensation ,methods 3. Ultrasonic dispersion: The s~und waves of high
1. Mechanical dispersion Exchange of solvents frequency are usually called ultrasonic waves. These waves can
2. Electro-dispersion Change of physical state be produced when quartz crystal discs are connected with a high
Chemical methods: frequency generator. The application of ultrasonic waves for the
,3. Ultrasonic dispersion
preparation of colloidal solutions was frrst introduced by Wood
4. Peptization (i) Double decomposition
and Loomis, in 1927. Various substances like oils, mercury,
(ii) Oxidation·
sulphur, sulphides and oxides of metals can be dispersed into
(iii) Reduction
(iv) Hydrolysis
colloidal state very easily with the help of ultrasonic waves.
4. Pepmation: The dispersion of a freshly precipitated
material into colloidal solution by the action of an electrolyte in
Dispersion Methods
solution is termed peptization. The electrolyte used is called a
1. MechaniCal dispersion: Solid material is fIrst :finely peptizing agent. .
ground by usual methods. It is then mixed with dispersion medium
. A few examples of sols obtained by peptization are:
which gives a .coarse suspension.· The suspension is now
(i) Freshly prepared ferric hydroxide on treatment with a
. introduced into the colloid mill. The simplest form of colloid mill
consists of two metal discs held at a small distance apart from one small amount of ferric chloride solution at once forms a dark
red~ish brown solution. Ferric chloride acts as a peptizing agent.
another and capable of revolving at a very high speed (about 7000
revolutions per minute) in opposite directions. The particles are (ii) Freshly prepared stannic oxide on.treatment with a small
ground down to colloidal size and are then dispersed in the liquid. amoUnt, of dilute hydrochloric acid forms a stable colloidal
A .stabilizer is often added to stabilize the colloidal solution. solution ofstanmc oxide.
Colloidal graphite (a lubricant) and printing ink are made by this (iii) Freshly precipitated silver chloride can be converted into a
method. Tannin is used as a stabilizer in the preparation of coiloidal solution by adding a small amount of hydrochloric acid~
394 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(iv) Cadmium sulphide can be peptized with the help of Organic reducing agents such as formaldehyde, phenyl
. hydrogen sulphide. hydrazine, tannic acid, etc., can also be used .
The process of peptization thus involves the adsorption of AgN0 3 + tannic acid Silver sol
suitable ions (supplied by the electrolyte added-particularly a
AuCl 3 + tannic acid ----t Gold sol
common ion) and electrically chargt¥l particles then split from
the precipitate as colloidal particles. . (d) HydrolYSiS: Colloidal solutions of some salts can be
prepared by hydrolysis. A colloidal solution of ferric hydroxide is
Condensation Methods obtained by boiling a dilute solution oHerric chloride.
1. By exchange of solvents: If a solution of sulphur or FeCl 3 + 3HzO----t Fe(OH) 3 +3HCI
phosphorus prepared in alcohol is poured into water, a colloidal Red sol
. solution of sulphur or phosphorus is obtained due to low The colloidal solution of silicic acid is also obtained by
solubility in water. Thus, there are a number of substances whose hydrolysis of dilute solution of sodium silicate with 4N
colloidal solutions can be prepared by taking a solution of the hydrochloric acid which is added drop by drop with constant
substance in one solvent and pouring it into another solvent in stirring.
which the substance is relatively less soluble.
2. By change of physical state: Colloidal solutions of 6.5 PURIFICATION OF COLLOIDAL
certain elements such as mercury and sulphur are obtained by . SOLU1"IONS
passing their vapour through cold water containing a stabilizer Colloidal solutions prepared by above methods generally contain
(an ammonium salt or a citrate). excessive amount of electrolytes and some other soluble
3. Chemical methods: The chemical methods involve impurities. The presence of traces of electrolyte is essential for
chemical reactions in a medium in which the dispersed phase is the stability of the colloidal solution but larger quantities
sparingly soluble. A condition of supersaturation is produced but coagulate it. It is, therefore, necessary to reduce the concentration
the actual precipitation is avoided. Some familiar reactions used of these soluble impurities to a requisite minimum. The process
are: used for reducing these impnrities to a requisite minimnm is
(a) Double decomposition: (i) Arsenious sulphide sol: A known as purificatiou of colloidal solution. The purification of
1% solution of arsenious oxide is prepared in hot water. The colloidal solution is carried out by the following methods:
solution is cooled, filtered and is then gradually added to water (i) Dialysis*: It is a process of removing a dissolved
saturated with hydrogen sulphide, whilst a stream of Hz S is being substance from a colloidai solution by means of diffusion
pass~d through the solution. This is continued till an intense through suitable membrane. Since, particles in true solution (ions
yellow-coloured solution is obtained. Excess of Hz S is removed or smaller molecules) CaJ;1 pass through animal membranes
by bubbling hydrogen through the solution. (bladder) or parchment paper or cellophane sheet but colloidal
AS 2 S 3 +3H zO particles do not, the above can be used for dialysis. The appaiatus
Yellow sol used for this purpose is called dialyser. A bag of suitable
(ii) Antimony sulphide sol: A 0.5% solution of potassium membrane containing the colloidal solution is suspended in a
antimonyl tartarate is added drop by drop to water saturated with vessel through which fresh water is continuously flown
HzS, whilst H 2 S is being passed through the solution. Orange (Fig. 6.4). The molecules and ions diffuse througQ the membrane
coloured solution of antimony sulphide is obtained. into the outer water and pure colloidal solution is left behind.
CH(OH)COOK' CH(OH)COOK
2 I +3H zS----t2 I Dialysing membrane
CH(OH)COO(SbO) CH(OH)COOH
+ Sb + 2H 2 0 Water + Crystalloid
2S3
Orange sol
CrystallOid
(b) Oxidation: A colloidal solution of sulphur is obtained
Sol particle
by passing H 2S into a solution of sulphur dioxide.
2H zS + S02 ----t 2H z0 + 3S
Sol Fig. 6.4
Sulphur sol can also be obtained when Hz S is bubbled through (ii) Electro-dialysis: Ordinarily, the process of dialysis is
an oxidising agent (bromine water or nitric acid). quite slow. It can be made faster by applying an electric field if
(c) Reduction: Colloidal solutions of metals like gold, the dissolved substance in the impure colloidal solution is only
silver, platinum, lead, etc., can be obtained when their salts electrolyte. The process is then named electro-dialysis. The
solutions are acted upon by reducing agents. colloidal solution is placed between two electrodes. while pure
water is taken in a compartment on each side. Electrodes are
2AuCl 3 + 3SnCl 2 ----t 3SnCl 4 + 2Au . fitted in the compartment as shown in Fig. 6.5. The ions present
Sol
'*B1ood i~ a colloidal solution. In case of kidney failure, blood cannot be purified. Under such condition, the blood is separated from dissolved toxic
impurities. by dialysis and re-introduced in the blood stream. "
I
in the colloidal solution migrate out to the oppositely charged higher viscosity and lower surface tension in comparison to the
electrodes. dispersion medium.
S. Colligative properties: Colloidal particles are bigger
aggregates. Thus, the number of particles in the colloidal solution
Dialysing membrane is comparatively small as compared to true solution and hence,
the values of colligative properties (osmotic pressure, lowering in .
vapour pressure, depression in freezing point and elevation in
boiling point) are of small order as compared to values shown by
true solutions at same concentrations.
6. Tyndall effect: If a heterogeneous solution placed in
dark is observed in the direction oflight, it appears clear and if it
is observed from a direction at right angles to the direction of
Fig. 6.5 light beam, it appears perfectly dark. Colloidal solutions show a
(iii) Ultrafiltration: Ultrafiltration is the process of mild to strong opalescence, when viewed at right angles to the
separating the colloidal particles from the solvent and soluble path of light, i. e. , the path of the beam is illuminated by a bluish
solutes present in the colloidal solution by especially prepared light. This effect was first observed by Faraday and later studied
filters, which are permeable to all substances except the colloidal in detail by Tyndall and is termed as Tyndall effect. The bright
particles. cone of the light is called Tyndall cone (Fig. 6.6). The Tyndall
CoJloidal particles can pass through ordinary filter paper effect is due to the fa~t that colloidal particles absorb light energy
because the pores are too large. However, the pores of filter paper and then scatter in all directions in space. This scattering oflight
can be reduced in size by impregnating with colloidion solution illuminates the path of beam in the colloidal dispersion.
and subsequently hardened by soaking in formaldehyde. The
usual colloidion is a 4% solution of nitro-cellulose in a mixture of Eye 14 Eye 14
alcohol and ether. An ultra-filter paper may be prepared by
soaking the filter paper in a colloidion solution and hardened by
formaldehyde and finally dryil'lg it. Thus, by using ultra-filter
paper, the colloidal particles are separated from rest of the
materials. Ultrafiltration is a slow process. To speed up the
Light {
source
::::->:-:-»>
ecce:,', ... ..
,
. .. . .
process, pressu~e or suction is used.
The colloidal particles left on the ultra-filter paper are then ~
,>:-:,:-:-:
stirred with fresh dispersion medium (solvent) to get a pure
True solution Colloidal solution
colloidal solution.
Fig. 6.6
;'11\ PROPER1"IES OF COLLOIDAL SOLUTION Tyndall effect can be observed during the projection of picture
in the cinema hall due to scattering of light by dust and smoke
1. Heterogeneous character: Colloidal solutions are
heterogeneous in character as they consist of two phases: particles present there. Tyndall effect is observed only when the
(a) dispersed phase and (b) dispersion medium. following two conditions are satisfied:
(i) The diameter ofthe dispersed particles is not much smaller
2. Visibility: It is not possible to see colloidal particles with
than the wavelength of the light used; and
naked eye or with the help of microscope. It is a well known fact
that no particle is visible if its diameter is less than half the (ii) The refractive indices of the dispersed phase and the
wavelength of the light used. The shortest wavelength of the' dispersion medium must differ greatly in' magnitude. This
visible light is about 4000 A or 400 n1J..t. Hence, no particle of
diameter less than 200 n1J..t can be seen. The size of colloidal
particles is less than 200 n1J..t .
14- Eye
Recently, three new techniques have been developed to
determine the size and shape ofthe colloidal particles. These are:
(i) Scanning electron microscope (SEM).
(ii) Transmission electron microscope (TEM). Light , Tyndali cone
source
(iii) Scanning transmission electron microscope (STEM).
3. Filtrability: Colloidal particles pass through an ordinary
filter paper. However, the particles do not pass through
parchment and other fine membranes.
4. Surface tension and viscosity: The surface tension and Colloidal solution
viscosity of lyophobic sols are not very different from those of
the dispersion medium. On the other hand, lyophilic sols show Fig. 6.7
.
396 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
. condition is satisfied by lyophobic sols. The. lyophilic sols show positive or negative. A list of some common sols with the type of
little or no Tyndall effect as there is very small difference in the charge on their particles is given in table 6.5.
refractive indices of the dispersed phase and the dispersion
. TabJe 6.5
medium.
Some examples of Tyndall effects are: S.No. Positively charged Negatively charged
(i) Blue colourotsky and seawater
L Metallic· hydroxides, e.g., Metals, e.g., copper, silver,
(ii) Visibility of tails of comets Cr(OH)" AI(OHh and gold-sols.
(iii) Twinkling of stars. Fe(OHhsols.
Tyndall effect is used to distinguish between a. colloidal and· 2. Basic dyestuffs, e.g., methyl- Metallic sulphides. e.g.,AS 2 S3,
true solution. Zsigmondy, in 1903,.used Tyndall effect to setup ene blue sol. Sb 2Sj, CdS sols..
an apparatus known as ultramicroscope. An intense beam of
3. Proteins in acidic·medium. Acid dyestuffs, Ie.g., . eosin,
light is focussed on the colloidal solution contairied in a glass congo red-sols. \
vesseL The focus of the light is then observed with a microscope
at right angles to the beam. Individual colloidal particles appear
. 4. Oxides, e.g., Ti02 sol. Sols of starch, gpm; gelatin,
clay, charcoal, etcJ
as bright stars against a dark background. Ultramicroscope does
not render visible the actual colloidal particles but only the light The charge on the sol particles is due to otie or more of the
scattered by them. Thus, ultramicroscope does not provide any follOwing reasons: .
information about the size and shape 'of colloidal particles. (i) Due to the presence of acidic or basic groups: A protein
7. Colour: . The colour: of colloidal solution depends on the molecule has a carboxylic group and a basic· NH2 group. The
wavelength of light scattered by the dispersed· particles .. The particles of proteins in sols can either have positive charge or
<
wavelength of light further depends on· the size and nature oithe negative
. charge depending
. upon the pH of the medium.
.
particles. The colour of colloidal solution also changes with the . .... + . .
way the observer receives the light. For example, milk and water · . .././NH2 . . . .. NH3. . _ (aCl'd'lC
mixture appears .blue .when viewed.by the reflected light and CH2'-.:. + HCl:---1' CH2 " +CI d')
. . "COOH . . . . 'COOH. . me mm
looks red by the transmitted light: Finest gold sol is red in colour.. GlyCine
As size of the particles increases, it beco~espurple,Jhen blue
and fmally golden yellow. .. . . · .·/N'B2 ... ' ... ' NH2 , . '. .
8. Brownian movement: When colloidal solutions are. CH 2", + NaOR:--~ CH2 ( .. ..•. +Na++H20
viewed under a powerful ultramicroscope, the colloidal particles . COOH . .. "COO~;
Glycine Negillively charged:
app~ar to be in a state of continuous motion in zig-zagdirectiotis
. .
all over the field of view. This motion was fjrst observed by the (alkaline. medium)
IsoeleCtric point of a conoid: 'Incase ofdolloidalsolution ..
Summary of Electrokinetic Phenomena [Fe(CN) 6 J4- > PO~- > SO~- > CI-
Motion Causing Potential:
The minimum concentration of an electrolyte in millimole
Sedimentation Potential Streaming Potential per litre required to canse precipitation of a sol in 2 hours is
caUed flocculation valne. The smaller the flocculating value, the
Medium rests but dispersed Medium moves but dispersed higher will be the coagulating power of an ion.
particles move. particles rest.
Flocculation value of an ion depends on its charge:
Potential Causing Motion: Flocculation value ex _1_ where Z = charge of ion '
(Z)6
Electrophoresis Electro-osmosls
Flocculation value of M±, M 2± , M 3±" M 4± ions lies in
Medium rests but dispersed Medium moves but dispersed
following ratio.
particles move. particles rest.
1 I 1 1
11. Coagulation or precipitation: The stability of the (ll : (2)6 : (3)6 : (4)6
lyophobic sols is due to the presence of charge on colloidal 1 : 0.0156 : 0.00137 : 0.00024
particles. If, some how, the charge is removed,the particles will 100 : 156 : 0.137 : 0.024
come nearer to each other and thus, aggregate or flocculate and
Coagulation of lyophilic sols: There·are two factors which
settle down under the force of gravity.
are responsible for the stability of lyophilic sols. These factors
The flocculation and settling down of the colloidal particles is
are the charge and solvation of the colloidal particles. When these
called coagulation or precipitation of the sot: '
two factors are removed, a lyophilic sol can be coagulated. This
The coagulation of the lyophobic sols can be carried out by is done (i) by adding electrolyte and (ii) by adding suitable
following methods: solvent. When solvents such as alcohol and acetone are added to
(i) By electrophoresis: . In electrophoresis, the colloidal hydr~philic sols, the dehydration of dispersed phase occurs.
particles move towards oppositely charged electrode. When these Under this condition, a small 'quantity of electrolyte can bring
come in contact with the electrode for long, these are discharged about coagulation.
and precipitated. ' 12. Protection of colloids: Lyophilic sols are more stable
(ii) By mixing two oppositely charged sols: When than lyophobic sols. This is due to the fact that lyophilic colloids
oppositely charged sols are mixed in almost equal proportions, are extensively solvated, i. e. ,colloidal particles are covered by a
their charges are neutralised. Both sols may be partially or sheath of the liquid in which they are dispersed.
completely precipitated as the mixing of ferric hydroxide (+ve Lyophilic colloids have a unique property of protecting
sol) and arsenious sulphide (-ve sol) bring them in precipitated lyophobic colloids. When a lyophilic sol is added to the lyop-
form. This type of coagulation is called mutual coagulation or hobic sol, the lyophilic particles form a layer around lyophobic
meteral coagulation. particles and thus, protect the latter· from electrolytes. Lyophilic
(iii) By boiling: When a sol is boiled, the adsorbed layer is colloids used for this purpose are called protective colloids.
disturbed due to increased collisions with the molecules of The lyophilic colloids differ.in their protective power. The
dispersion medium. This reduces the charge on the particles and protective power is measured in terms of Gold Number. This
ultimately they settle down to form a precipitate. number was. introduced by Zsigmondy and is defined as the
(iv) By persistent dialysis: On prolonged dialysis, the number of milligrams of a lyophilic colloid that will just
traces of the electrolyte present in the sol are removed almost prevent the precipitation of 10 mL of a gold solon the
completely and the colloids become unstable. addition of 1 mL of 10% sodium chloride solution.
(v) By addition of electrolytes: When excess of an The gold numbers of some of the common protective colloids
electrolyte is added, the colloidal particles are precipitated. The are listed below:
reason is that colloidal particles take up ions carrying charge
opposite to that present on themselves. This causes neutralisation Table 6.6
leading to their coagulation. The ion responsible for
S.No~ Proteetlve Colloid Gold Number
neutralisation of charge on the particles is called the flocculating
ion. A negative ion causes the precipitation of positively charged 1. Gelatin 0.005-0.01
sol and vice-versa. 2. Haemoglobin :~"··(·0.03
It has been observed that, generaUy, the greater the valency
3. Gum arabic 0.15
. of the flocculating ion added, the greater is its power to cause
precipitation. This is known as Hardy-Schulze rule. In the 4. Egg albumin 0.08-0.10
coagulation of a negative sol, the flocculatmg power ofNa + , 5.. Potato starch 25
Ba2+ andAl 3+ ions is in the order of: 6. Sodium oleate 0.4
A1 3+ > Ba 2+ > Na +
7. Gum tragacanth, 2
Siinilarly, in the coagulation of a positive sol, the flocculation
8. Starch 25-50
power of CI- , SO;- ,PO~- and [Fe(CN) 6 J4- is in the order of:
THE COLLOIDAL STATE 399
Higher is the gold number, lower will be the protective power. heavy metal salts of fatty acids, long chain alcohols, lampblack,
Thus, gelatin and starch have the maximum and minimum etc.
protective powers. The use of protective colloids is widespread. Emulsions c'an be diluted with any amount of the dispersion
Gelatin is added in the preparation of ice cream as protective medium. On the other hand, the dispersed liquid, when mixed,
agent to the colloidal particles of ice. Argyrol, used as eye drops, forms at once a separate layer. The droplets in emulsions are
is a silver sol protected by organic material: . often negatively charged and can be precipitated by electrolytes.
Some facts: They also show Brownian movement and Tyndall effect.
(i) Blood is a colloidal solution, it is not coagulated by the Emulsions can be broken into constituent liquids by heating,
electrolytes (NaCI, Ca 3 (P0 4 h etc.) present in blood itself freezing, centrifuging, etc.
because proteins present in blood act as protective colloid. Detection of emulsion: Following tests can be used to
(ii) Milk of human mother is better protected than cow's and detect the type of emulsion:
buffaloes milk.
(i) Dye test: An oil soluble dye is shaken up with the
(iii) The proteins which are not coagulated at their iso-electric emulsion and a drop is seen under microscope. If coloured drops
pH are ~etter protective colloid. are seen, the emulsion is water in oil type otherwise of oil in
(iv) Ageing : It is spontaneous destabilisation of colloidal water type.
solution. In this process, dispersed is separated from dispersion
(ii) Viscosity test: Water in oil type emulsion has greater
medium by itself, i.e., no artificial method is used.
viscosity than oil in water type emulsion.
Congo Rubin Number (iii) Electrical conductivity test: Electrical conductivity of
oil in water type emulsion is much greater than water in oil type
Ostwald proposed that it is the amount of protective colloid in emulsion. If electrolyte like NaCI is added to qil in water type
mg which prevents the colour change in 100 mL of 0.0 I % Congo emulsion, its conductivity greatly increases.
rubin dye solution to which 0.16 g equivalent of KCI are added
(iv) Spreading test: Water in oil type emulsion easily
when observed after 10-15 min.
spread on the surface of an oil but not on the surface of water.
13. CoIJigative properties: The value of colligative
properties are of very small order because they have very small (v) Dilution test: Oil in water type emulsion can easily be .
van't Hoff factor. diluted with water. On the other hand water in oil type emulsion
cannQt be diluted with water. For example, milk-which is oil in
nAs 2 S 3 - - 7 (As 2 S 3 )n .
water type emulsion can be diluted with water, but butter or milk
n:::: 1000
" 1 I cream which are water in oil type emulsion cannot be diluted with
van't Hoff factor i - - water.
1000
(vi) Coalescence: It is the phenomenll of disappearance of the
Colligative properties are directly proportional to the van't
boundary between two particles (generally droplets or bubbles)'
Hoff factor.
in contact. Coalescence leads to the reduction of the total surface
area. The flocculation of an emulsion, viz., the formation of·
6.7 EMULSIONS aggregates, may be followed by coalescence. In extensive
condition, the coalescence leads to the formation of a macrophase
These arc liquid-liquid colloidal systems, i. e. , the dispersion of and emulsion is said to break. Coalescence of solid particles is
finely divided droplets in another liquid. If a mixture of two called sintering.
immiscible or partially miscible liquids is shaken, a coarse
dispersion of one liquid in the other is obtained which is called
~.6~81 CLASSIFICATION OF COLLOIDS
emulsion. Generally, one of the two liquids is water. There are
two types of emulsions:
BASED ON THE TYPE Of PARTICLES
(i) Oil dispersed in water (OIW type), OF DISPERSED PHASE
(ii) Water dispersed in oil (W10 type). Depending upon the type of particles of dispersed phase, colloids
In the first system, water acts as dispersion medium. Examples are classified as:
of this type of emulsions are milk and vanishing cream. In milk, (i) Multimolecular, (ii) Macromolecular" (iii) Associated
liquid fat is dispersed in water. colloids.
In the second system, oil acts as dispersion medium. Conimon (i) Multimolecular colloids: On dissolution, a large number
examples of this type are butter and cream. of atoms or smaller molecules of a substance aggregate together
Emulsions of oil and water are unstable and sometimes they to form species having size in colloidal dimension (diameter less
separate into two layers on standing. For the stabilization of an than 1 nm). The species thus formed are called multimolecular
emulsion, a third component called emulsifying agent is usually colloids. For example: Gold sol, sulphur soL In these colloids, the
added. The emulsifying agents form an interfaciallilm between particles are held together by van der Waals' forces.
suspended particles and the medium. The principal agents for (ii) Macromolecular colloids: Macromolecular substances
OIW emulsions are proteins, gums, natural and synthetic soaps, dissolve in suitable solvent to form solutions inwhich the size of
etc. For W10 emulsions, the principal emulsifying agents are macromolecules lie in colloidal dimension. These are called
I
400 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
I
. macromolecular colloids and they are quite stable. For example: Micellisation with cationic te~'als are also known, e.g., in
Starch, cellulose, proteins and enzymes, etc. cetyltrimethyl ammonium chloride.;\1t may be diagramatically
(iii) Associated. colloids: Substances whose molecules represented as : .!
C12H,,~03 Na'
Surfactants are those substances which are preferentially
adsorbed at the interfaces like air-water, oil-water and
solid-water interfaces. Thus, it is the surfactant which is
responsible for micellisation and emulsification. Surfactants are
divided into three categories:
(i) Cationic surfactants: Such substances on ionisation
give a cation having hydrophobic and hydrophilic group, e.g.,
cetyl pyridinium chloride,
Fig. 6.10
C16H33-CN +CC
The negative ions aggregate~~to form a micelle of colloidal
size. The negative ion has a long hydrocarbon chain and a polar Cetyltrimethyl ammonium chloride, C I6 H 33 (CH 3 hN+Cr
group (-COO-) at one end. In micelle formation, the long
Octadecyl ammonium chloride, C 1s H 37 NH;CI-
. hydrocarbon chain (tail) which is insoluble in water is directed
towards the centre while the soluble polar head is on the surface Ionisation of these compounds may be represented as,
Water
in contact with water (Fig. 6.10). The charge on the micelle is C1s H37 NHiCI- ~ C1s H 37 NHi
responsible for the stability of this system. The cleansing action (Hydrophobic end) (Hydrophilic end)
of soap is due to these micelles. The grease stain is absorbed into (ii) Anionic surfactants: Such substances give anion
. the interior of the micelle and gets detached from the fabric. The which act as surfactant, e.g.,
dust particles sticking to the stain are also removed. This action is
S,!dium Pahnitate C1sH31 COONa
similar to emulsification of grease.
Sodium Oleate C 17 H35 COONa
Some other examples of micelle systems are as follows:
and salts of sulphonic acid having molecular formula
(i) Sodium lauryl sulphate CH3 -(CHz)ll S04 Na+
C n HZn + 1 S03M where~ M+ = Na +, K+, NH~, etc.
(ii) Sodium oleate C 17 H 3S COO- Na +
Water
(iii) Cetyltrimethyl ammonium bromide; C1s H 31 COONa ~ C1s H31 - COO- + Na+
CH3 (CH 2 )15 N+ (CH3 )3 Br (Hydrophobic (Hydrophilic
end) end)
THE COLLOIDAL STATE 401
"'-I
Cn H Zn + I (OCH zCH 2 )x OH
0(1)
~E
:::lQ)
_c
c·-
(1\(1)
>.0
(I)
'------v----~' '--v---'
(Hydrophobic end) (Hydrophilic end) G)
II:
0.01 0.02
Kraft point: The temperature above which a surfactant Concentration of sodium dodecyl sulphate
forms micelle is called kraft point. (mol dm-3)
,....,......,
as,
-72!!!!=--;;;c--+--- Entrapped liquid
Ml" = ll~ + TllSo
= -2. 303RT z d(log CMe)
dT .
Fig. 6.13 I·
PhYSical Properties of Critical Micelle Concentration Gel may shrink on keeping by loosing some of the liqu~held
Physico-chemical properties of surfactant solution changes
sharply in the region of the C.M.C. Variation of physico-chemical
by them. This is known as syneresis or weepirtg geL Some gels of
liquify on shaking and reset on being allowed to stand.This~
properties of surfactant solution with concentration is reversible Sol-Gel transformation is known as thixotropy/ The
represented in following figure: softening behaviour of a marshy land under trading is du.e; to
thixotropic behaviour of bent0nite clay present in such soils.
402 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Elastic g!,)l can imbibe water when placed in it and undergo· precipitated. The particles thus, settle uown on the floor ofthe
swelling, non-elastic gels are incapable of doing so. This chamber. The precipitator is called cottrell precipitator.
phenomenon is known as imbibition or swelling.
Dust free gases
~. . APPLICATIONS OF COLLOIDS ... II ~.:..
Most of the substances, we come across in our daily life, are Chimney
colloids. The meal we eat, the clothes we wear, the wooden
furniture we use, the houses we live in, the newspapers we read,
are largely composed of colloids.
The applications of colloid chemistry are limitless. These can
be divided mainly into two classes:
.I. Natural applications
2. Technical applications
1, Natural Applications
(i) Blue colour of the sky: Colloidal particles scatter blue
light. Dust particles along with water suspended in air scatter Fig. 6.14.
blue light which reaches our eyes and the sky looks blue to us.
(ti) Purification of drinking water: The water obtained
(ii) Fog, mist and rain: When a large m~s of air,
from natural sources often contains bacteria and suspended
containing dust particles, is cooled below its dewpoint, the
impurities. Alum is added to such water so as to destroy the
moisture from the air condenses on the surfaces of these particles
bacteria as well as to coagulate the suspended impurities and .
forming fine droplets. These droplets being colloidal in nature
make water fit for drinking purposes.
continue to float in the air in the form of mist or fog.
(iii) Medicines: Most of the medicines in use at;,6colloidal
Clouds are aerosols having small droplets of water suspended
in nature. For example, argyrol is a silver sol used as an eye
in air. On account of condensation in the upper atmosphere; the
colloidal droplets of water grow bigger and bigger in size, till lotion. Colloidal antimony is used in curing kala-azar. Colloidal
gold is used for intramuscular injection. Milk of magnesia (an
they come down in the form of rain. Sometimes, the rainfall
emulsion) is used for stomach disorders. Colloidal medicines are
occurs when two oppositively charged clouds meet.
more effective because these are easily assimilated.
It is possible to cause artificial rain by throwing electrified
sand or spraying a sol carrying charge opposite to the one on (Iv) Tanning: Animal hides are colloidal in nature. When a
hide, which has positively charged particles, is soaked in tannin,
clouds from an aeroplane.
which contains negatively charged colloidal particles, mutual .
(iU)Food articles: . Milk, butter, halwa, ice creams, fruit
coagulation takes place, which results in the hardening ofleather.
. juices, etc., are all colloids in. one form or the other.
The process is termed as tanning. Chromium salts have also been
(Iv) Blood; Blood is a colloidal solution of an albuminoid·
used in place of tannin.
substance. The styptic action of alum and ferric chloride solution
(v) Cleansing action of soaps and detergents: Already
is due t? coagulation of blood forming a clot which stops further
described in section 6.8.
bleeding. .
(vi) Photographic plates and films: The photographic
(v) sons~ Fertile~ soils are colloidal in nature· in which
plates or films are prepared by coating an emulsion of the light
humus acts as a protlMive colloid. On account of colloidal
sensitive silver bromide in gelatin over glass plates or celluloid
nature, soils absorb moisture and nourishing materials.
films.
(vi) FfJrDlation ~f delta~ River water is colloidal solution
(vii) Rubber industry: Latex is a colloidal solution of
of clay. Seawater contains a number of electrolytes. When river
rubber particles which are negatively charged. Rubber is
water meets the seawater,. the. electrolytes present in seawater
obtained by coagulation of latex.
coagulate the ~olloidal solution of clay which gets deposited with
the fOrpJ.ation of delta. (viii) Industrial products: Paints, inks, synthetic plastics,
rubber, graphite lubricants, cement, etc., are all colloidal
2. Technical Applications solutions. Asphalt emulsion is used in road construction.
.(i) Electrical precipitation of smoke: Smoke is a colloidal (ix) Disinfectants: The disinfectants such as dettol and
·solution of solid particles such as carbon, arsenic compounds, lysol give emulsion of oil in water type when mixed with water.
dust, etc., in air. The smoke, before it comes out from the . (x) In ~etallurgy: Su.1phideores are concentrated by
chimney, is led through a chamber containing. plates having a froth-flotation process. In this process; pulverised ore is treated
charge opposite to that carried by smoke particles. The particles with emulsion of pine oil.
·on coming in contact with these plates lose their charge and get
.'
THE COLLOIDAL STATE 403
The positive ion is effective in coagulating negative sol and Emulsifying agent: It is added to "H vII and water emulsion
vice-versa. The effectiveness of anion is governed by to increase its stability. It has polar and non-polar groups; the
Hardy-Schulze rule; The rule states that the precipitating power former attaches to water and the latter to oil and so binds them
of an ion depends upon its valency, i. e. ,higher the valency of the together in an emulsion. Soaps and detergents act as emulsifying
ion greater is the precipitating power of the ion. agents.
For negative sol, the power varies as M 3+ > M2+ > M+ and 8. Gel: It is a colloidal system in which liquid is dispersed
for positive sol the power varies as [Fe(CN)6 ]4- > SO~- > Cl-. in solid. Fruit-jellies, cheese, etc., are the examples of gels. Gels
may be elastic or non-elastic according to their mechanical
Flocculating value: It is the minimum concentration in properties.
millimoles per litre of an electrolyte required to cause
9. Applications of colloids: The applications can be
precipitation of a sol in 2 hours. The smaller is the flocculating
divided mainly into two classes:
power greater shall be the precipitating power of an ion.
(x) Protective action: Lyophilic sols are more stable than (i) Natural applications:
lyophobic sols. Thus, lyophilic colloids have the property of (a) Blue colour of the sky
protecting lyophobic sols. When a lyophilic sol is added to (b) fog, mist and rain
lyophobic sol, 'the lyophilic particles form a layer around
(c) Food articles
lyophobic particles and thus protect them from electrolytes. The
(d) Blood
protective power oflyophilic colloid is measured in terms of gold
number. It is defined as the number of milligrams of a lyophilic (e) Soils
colloid that will just prevent the precipitation of 10 mL of a gold (f) Formation of delta
solon the addition of 1 mL of 10% NaCI solution. Lower the gold (ii) Technical applications:
number, higher will be the protective power. Gelatin (Gold
Number 0.005,....().01) and starch (Gold Number 25-50) have the (a) Electrical precipitation of smoke
maximum and mitrimum protective powers. (b) Purification of drinking water
(xi) Coacervation: The loss of the stability ofa lyophilic sol, (c) Medicines
quite ofien,resuits in a separation of the system into two liquid (d) Tanning
phases. The separation of colloidal sol into two liquid phases is (e) Cleansing action of soaps and detergents
called coacervation. (f) Photographic plates and films
7. Emulsion: It is a colloidal solution ofa liquid in (g) Rubber industry
another immiscible liquid. Emulsions are usually of two types: (h) Paints, inks, plastics, lubricants, cement, etc.
(a) Oil in water-Examples: Milk, cream, face cream, etc.
(b) Water in oil-Examples: Bl,ltter, cold cream, etc.
THE COLLOIDAL STATE 405
3. The coagulation of 100 mL of a colloidal solution of gold is 4. For the coagulation of 100 mL of arsenious sulphide solution,
completely prevented by adding 0.25 g of starch to it before 5 mL of I MNaCI is required. What is the coagulating power
adding 10.mL of 10% NaCI solution. Find out the gold number of NaCl?
of starch. [Hint: Total volume after addition of 5 mL of I M NaCI
(Hint=.lOmL of 10% NaCI solution is added to 100 mL of solution 105 mL
solution of gold. Thus, 105 x molarity of NaCI in colloidal solution 5 xl
Thus, I mL of 10% NaCl solution has been added to 10 mL
solution of gold. Molarity of NaCI in colloidal solution = 2..
105
Since, 100 mL gold solution required = 0.25 g starch
= 0.25 x 103 mg starch Concentration in millimole = ~ x 1000
105
3
So, 10 mL gold solution required = 0.25 x 10 X 10 47.6]
100
25 mg starch
Thus, by definition, the gold number of starch is 25.]
1. [A] (i-~ (ii-g); (iii-b); (iv-a); (v-:-h); (vi~); (vii-d); 2. [A] (a-r, s) (b-r, s) (c-p) (d-q)
(viii-e) [B] (a-r, s) (b-r) (c-p) (d-q)
[B] (i-b); (ii---'-f); (iii-a); (iv-b);(v~); (vi-d); (vii-e); [C] (a-q-u) (b-p-w) (c-p-v) (d-r-x)
(viii-g) [D] (a-r, s) (b-s) (c-p) (d-q) .
[C] (i--e-3); (ii-d-l); (iii-a--6); (iv-b-5); [E] (a-q, s) (b-q) (c-'-p) (d-r)
(v~-2); (vi-f- 4). [F] (a-q) (b-p) (c~r) (d-s)
....!£:::OBlECTIVEQUESTIONS
Set-1: Questions with Single correct answer a
7. Which of the following forms colloidal solution in water?
1. Difference between crystalloid and colloid is of: (CP\1T 1990)
(a) particle size (b) chemical composition (a) NaCI (b) Glucose (c) Ba(N03h (d) Starch
(c) ionic character (d) solubility 8.. The number of phases present in colloidal solution is:
2. Substances whose solutions can readily diffuse through (a) 2 (b) 4 (c) 3 (d) 1
animal membranes are called: 9. The colloidal system of a solid dispersed in liquid medium is
(a) colloids (b) crystalloids called: [CET (J&K) 26071
(c) electrolytes (d) non-electrolytes
(a) aerosol (b) sol (c) gel (d) foam
10. When dispersed phase is liquid and dispersion medium is gas,
3. Suspensions are:
the colloidal system is called:
(a) visible to naked eye
(b) invisible through microscop~' (a) smoke (b) emulsion (c) cloud (d) gel
(c) not VIsible by any means 11. Water loving colloids are called as:
(d) invisible under electron microscope (a) hydrophilic (b) hydrophobic
4. The size of the colloidal particles is in between: (CPl\IT 1990) (c) lyophobic (d) irreversible
(a) 10-7 _10-9 em (b) 10-9 -10- 11 cm 12. An emulsion is a colloidal solution consisting of:
(e) 10-5 10-7 em (d) 10-2 _10-3 em (a) two solids (b) two liquids
(c) two gases (d) one solid and one liquid
5. The size of it colloidal particle is: JP1\fT (1\11') 19901
13. The colloidal solution of gelatin is known as:
(a) > 0.1 ~ (b) 1 IIlt to 0.1 ~ (a) solvent loving (b) reversible
(c) <O.lml-l (d) morethan30ooIIlt
(c) hydrophilic (d) all of these
6. Ifliquid,is dispersed in solid medium, then this is called:
14. Sol is a type of colloid in which: (Raj.) IOnSl
• (DCE 20(9)
(a) solid is dispersed in liquid
(a) sol (b) emulsion
(b) liquid is dispersed in solid
(c) liquid aerosol (d) gel
(c) gas is dispersed in liquid
(d) solid is dispersed in solid
THE COLLOIDAL STATE
40. When excess of electrolyte is added to a colloid it: 51. Which of the following is not a property of hydrophilic sols?
(CBSE 1990) (a) High concentration of dispersed phase can be easily
(a) coagulates (b) g~ diluted attained
(c) precipitates (d) does not change (b) Coagulation is reversible
41. The colloidal solutions of gold prepared by different methods (c) Viscosity and surface tension are nearly as that of water
have different colours. This is due to: (MLNR 1993) (d) The charge on the particles depends on the pH value of the
(a) difference in size of colloidal particles medium; it may be positive, negative or even zero
(b) different concentration of gold 52. Gelatin is added in manufacture of ice cream in order to:
(c) presence of different types of foreign particles (a) prevent formation ofa colloid
(d) the variable valency of gold (b) stabilise the colloid and prevent crystallisation
42. The capacity of an ion to coagulate a colloidal solution (c) cause the mixture to solidify easily
depends on: . (d) improve flavour
(a) its shape 53. Which one of the following will act as best protective colloid?
~ (b) the amount of its charge (a) Gelatin (Gold No. 0.005)
(c) the sign of the charge (b) Starch (Gold No. 25)
(d) both, the amount and the sign o( the charge (c) Gum arabic (Gold No. 0.15)
43. Lyophilic sols are more stable than lyophobic sols because:
. (AFMC 1998) (d) Egg albumin (Gold No. 0.08).
54. Gold number is a measure of the:
(a) the colloidal particles have positive charge
(a) protective action by a lyophilic colloid on lyophobic
(b) the colloidal particles have negative charge
colloid
(c) the colloidal particles are solvated
(b) protective action by a lyophobic colloid on lyophilic
(d) there are strong electrostatic repulsions colloid
44. Which of the following will have the highest coagulating (c) number of mg of gold in a standard red gold sol
power for As2S 3 colloid?
(d) none ofthe above .
. (a) PO~- . (b) A1 3 + (c) S~- (d) Na +
55. On addition of one mL solution of 10% NaCI to 10 niL gold
45. A negatively charged suspension of clay in water ·will need for . sol in presence of 0.025 g of starch, the ,coagulation is just
precipitation the minimum amount of: prevented. The gold number of starch is:
(a) aluminium chloride ".. (b) potassium sulphate (a) 25.0 . (b) 2.5 (c) 0.25 (d) 0.025
(c) sodium hydroxide (d) hydrochloric acid· 56. The stability oflyophobic sols is due to:
46. Which of the following electrolytes is least effective in (a) Brownian motion only
causing flocculation offerric hydroxide sol? (MLNR 1991) . (b,1 electric chjlrge'oniy
(a) K3Fe(CN)6 (b) K 2 Cr04 , (eY b~tb BrowniaIl ffiQtf<)n and electric charge
(c) KEr (d) K 2S04 (d) particle size
47. Fe3+ ions coagulate blood. This show blood contains colloidal 57. Which one of the fl8tJQwing colloidal solutions is positive sol.?
particles bearing: . .. (CPMT 1992)
(a) negative charge (a) Blood
(b) positive charge (b) Clay soil
(c) no charge (c) Smoke
(d) either positive or negative charge . (d) Gelatin in strongly acidic solution
48. Gold number is a measure of: (CPMT 1991) 58. All colloidal solutions show:
(a) stability of colloidal system (a) very high osmotic pressure
. (b) coagulating power of a colloid (b) high osmotic pressure
(c) size of colloidal particles (c) low osmotic pressure
(d) efficiency of the protective colloid (d) no osmotic pressure
49: Gold number is a measure of: [PET (MP) 2004) 59. Which of the following is associated colloid?
(a) the amount of gold present in the colloidal solution (a) Soap (b) Detergent
(b) the amount of gold required to break the colloid . (c) Both (d) None of these
(c) the amount of gold required to protect the colloid 60. Which of the following is an emulsifier?
(d) none ofthe above (a) Oil (b) Soap (c) Solvent (d) KCI
so. Which of the following methods is used for destruction ofa 61. An emulsifier is a substance which:
colloidal solution? (a) helps in the dispersion ofIiquid in liquid
(a) Condensation (b) stabilises the emulsion
(b) Dialysis ( c) coagulates the emulsion .
(c) Diffusion through animal membrane (d) purifies the emulsion
(d) Addition of an electrolyte
THE COLLOIDAL STATE
62. The gold numbers of some colloidal solutions are given (a) flocculation value (b) gold number
below: (c) protective value (d) coagulation number
Colloidal solution Gold number 76. Purple of cassius is:
A 0.01 (a) colloidal solution of silver
B 2.5 (b) colloidal solution of gold
C 20 (c) colloidal solution of platinum
The projective powers of these colloidal solutions follow the (d) oxy acids of gold
order: [CET (J&K) 2006; AIEEE 2008] 77. Which type of molecules form micelles?
(a) C> B > A (b) A > B > C (a) Polar molecules (b) Non-polar molecules
(c) A B C (d) B > A > C (c) Surfactant molecules (d) Any of these
63. Dialyser is a name given to: 78. The name aquadag is given to the colloidal solution of:
(a) lyophilic colloids (a) copper in water (b) platinum in water
(b) lyophobic colloids (c) gold in water (d) graphite in water
(c) to a membrane which can separate colloids from the solution 79'1 A li4ui~ is found to scatter a beam of light but leaves no
(d) none of the, above ! .. resi4udvhen passed through the filter paper. The liquid can be
64. Floccull"/-tion value is expressed in terms of: describ,d as: ! I· • (AIIMS 1993)
(a) millimole per litre (b) mol per litre (a) a suspension i : (b) oil'
(c) gram per litre (d) mol per millilitre (c) a colloidal sol. (d) true solution
65. Which of the following has minimum flocculation value? . 80. Point out the false statement: [CET (Punjab) 1991]
[PET (MP) 1990] (a) colloidal sols, are homogeneous
(a) Pb 2 + (b) Pb 4+ (c) Sr 2 + (d) Na+ (b) colloidal sols. carry +ve or -ve charge
66. The charge of As2 S3 sol is due to the absorbed: '(c) colloidal sols. show Tyndall effect
(a) It . (b) OIr (c) 0 2 - (d) S2- (d) the size of colloidal particles ranges between 10--2000 A
67. Which oftl;le following has maximum flocculation value? 81. The potential difference between the fixed charged layer and
(a} [Fe(CN)6t-' (b) CI- the diffused layer having opposite charge is called:
(a) colloidal potential (b) zeta potential
(c) SO~- (d) PO~-
(c) electrostatic potential (d) none of these
68. Above critical micelle c·oncentration, particles get: 82. An example ofmicelle is:
[AMU (Medical) 2006]
(a) As20 3 sol.
(a) associated (b) dissociated (b) ruby glass
(c) both (a) and (b) (d) none of these . (c) Na 2 C03 solution
69. Continuous phase contains dispersed phase throughout.
(d) sodium stearate concentrated solution
Example is: (VJTEEE 2008)
83. Surface tension oflyophilic sols. is: [PMT (MP) 1992]
(a) water in milk (b) fat in milk
(a) Ic.werthan H2 0 (b) more than H2 0
(c) water droplets in mist (d) oil in water.
'(c) equalto H2 0 (d) none of these
70. The movement of dispersion medium in an electric field when
the dispersed particles are prevented from moving is called:
is
84.' Which not shown by sols.? [PMT (MP) 1992]
(a) Adsorption (b) Tyndall effect
(a) cataphoresis. (b) electrophoresis
(c) Flocculation (d) Paramagnetism
(c) electro-osmosis (d) Brownian movement
85. An example of solid-solid system is:
71. To coagulate gelatin sol, which of the following is most
(a) smoke (b) coke
effective?
(c) synthetic gems (d) pumice stone
(a) NaCl (b) Na3P04 (c) AlCI 3 (d) Alcohol
72. The emulsifying agent in milk is: [EAMCET (Med.) 2010J 86. Detergent action of synthetic detergents is due to their:
( a) lactic. acid (b) fat
(a) interfacial area (b) high molecular weight
(c) ionisation (d) emulsifying properties
(c) lactose (d) casein
87. Blood contains:
73. Colloidal solutions of metals like Cu, Ag, Au and Pt are
generally prepared by using: (a) positively charged particles
(a) peptization (b) Bredig's arc method (b) negatively charged particles
(c) exchange of solvent (d) oxidation method (c) neutral particles
74. Silver iodide is used for producing artificial rain because AgI: (d) negatively as well as positively charged colloids
(a) has crystal structure similar to ice 88. Acolloidal solution always has at least: (CPMT 1993)
(b) is easy to spray at high altitudes (a) one-phase (b) more than two-phases
(c) is easy to synthesise (c) a true solution (d) two phases
(d) is soluble in water 89. Silica gel is commonly used as:
7S. The minimum concentration of an electrolyte required to (a) wetting agent (b) drying agent
cause coagulation of a sol. is called: (c) solvent (d) catalyst
410 G.R.B. PHYSiCAL CHEMISTRYFOR~COMPEtrTlONS
90. Which is not a colloidal solution of gas in liquid? (c) concentration of electrolyte added to destroy the micelles
(a) Froth (b) Foams with tiny bubbles (d) concentration of micelles at room temperature
(c) Mist (d) Whipped cream 102. Cod liver oil is: (CPMT 1997)
91. Fog is a colloidal solution of: (a) fat dispersed in water (b) water dispersed in fat
(MLNR 1995; PMT (MP) 1991] (c) water dispersed in oil (d) fat dispersed in fat
(a) liquid particles dispersed in gas 103. Which is not lyophilic colloid? (PMT (MP) 1998}
(b) gaseous particles dispersed in liquid (a) Milk (b) Gum (c) Fog (d) Blood
(c) solid particles dispersed in liquid 104. At the critical micelle concentration, the surfactant molecules:
(d) solid particles dispersed in gas (CBSE 1998)
92. Emulsions of polyvinyl acetate are used in: (a) decompose (b) dissociate
(a) polishes (b) latex paints (c) associate (d) become completely soluble
(c) fireworks (d) rayons lOS. Which of the following ions can cause coagulation of
93. When white light is passed through a colloidal solution proteins? (KCET2000)
containing fine suspended particles of gold, then the scattering - (a) Ag+ (b) Na + (c) Mg2+ (d) Ca z+
light seen in a direction different from that of incident light is:
106. In Brownian movement or motion the paths of the particles
(a) yellow coloured (b) blue coloured are: (KMEE 2000)
(c) green coloured (d) red coloured (a) linear (b) zig-zag
94. When a sulphur sol is evaporated, solid sulphur is left. On (c) uncertain (d) curved
mixing with water no colloidal sol is formed. The sulphur sol
107. Which is used for ending charge on colloidal solutions?
is:
(CBSE 2000)
(a) hydrophilic (b) hydrophobic
(a) Electrons (b) Electrolysis
(c) reversible (d) lyophilic
(c) Positively charged ions (d) Compounds
9S. Tails of comets are visible due to:
108. Cloud or fog is a colloidal system in which the dispersed phase
(a) Tyndall effect (b) reflection
and the dispersion medium are: (KCET 2000)
(c) Brownian movement (d) none of these
(a) gas, liquid (b) liquid, gas
96. Milk is an example of:
(c) liquid, liquid (d) solid, solid
[CPMT 1995; PET (MP) 2004; CET (J&K) 2004]
109. The electrolyte which has the least effect in the coagulation of
(a) fat dispersed in water Fe(OH)3 sol is: [KCET 2008}
(b) water dispersed in fat (a) potassium carbonate (b) sodium sulphate
(c) water dispersed in oil (c) potassium ferrocyanide (d) potassium iodide
(d) fat dispersed in fat 110. Blood may be purified by: [PMT (MP) 20001
97. Smog is an example of: (a) dialysis (b) electro-osmosis
(a) .ice dispersed in air (c) coagulation (d) filtration
(b) water dispersed in air 111. Gold number was given by:
(c) smoke dispersed in air (a) _Ostwald (b) Zsigmondy
(d) smoke and water dispersed in air (c) William and Chang (d) Langmuir
98. Peptization denotes: [ISM (Dhanbad) 19941 112. The diameter of colloidal particle ranges from: (KCET 2004)
(a) digestion offood
(a) 10-9 m to 10-6 m (b) 10-9 m to 10- 12 m
(b) hydrolysis of proteins
(c) breaking of dispersion into colloidal state (c) 103 m to 10-3 m (d) 1O-3 6
m to 10- m
(d) precipitation of a solid from colloidal state 113. The Tyndall effect is not observed in:
99. Whipped cream is an example of: (a) suspensions (b) emulsions
Dispersion Medium Dispersed Phase (c) colloidal solutions (d) true solutions
(a) Liquid Gas 114. Which one is example of Micelle's system?
(b) Liquid Liquid (a) Soap + water (b) Rubber + benzene
(c) Liquid Solid (c) Protein + water (d) None of these
(d) Gas . Liquid 115. Sedimentation potential is the reverse of:
100. Cottrell precipitator acts on which ofthe following principle? (a) electro-osmosis (b) electrophoresis
(a) Hardy-Schulze rule (c) electrokinetic potential (d) Dom potential
(b) Distribution law 116. Smoke has generally blue tinge. It is due to:
(c) Le Chatelier's principle (a) scattering (b) coagulation
(d) Neutralization of charge on the colloidal particles (c) Brownian motion (d) electrophoresis
101. CMC (critical micelle concentration) is: 117. On adding AgN03 solution to KI solution, a negatively
(a) concentration at which micell~s are destroyed charged colloidal sol will be formed in which ofthe following
(b) concentration at which micelle formation starts conditions?
THE COLLOIDAL STATE
,(a) 100 mL ofO.! M AgN0 3 +100 mL ofO.! M KI 130. Potassium stearate is obtained by the saponification of an oil
(b) 100 mLofO.l MAgN03 + 50 mLofO.2 M KI or a fat. It has formula CH3 - (CH2)16 - COo- K+. The
(c) 100 mLofO.2 M AgN03 + 100mLofO.l MKI molecule has a lyophobic end (CH 3- ) and a lypophilic end
(d) 100 mLofO.l M AgN03 + 100 mLofO.l5 M KI COo- K+. Potassium stearate is an example for:
118. Peptization ofSnOz by NaOH gives: [PET (Kerala) 2005]
(a) [SnOz]SnO;- :2Na+ (b) [SnOz ]Sn 4 + :02- (a) lyophobic colloid
(b) lyophilic colloid
(c) [Sn02]Na+ : OIr (d) [Sn02 ]Sn 4 + : OIr
(c) multimolecular colloid
119. Alum helps in purifying water by: (AlEEE 2002)
(d) macromolecular colloid
(a) forming Si complex with clay particles
(e) associated colloid or micelle
(b) sulphate part whlch combines with the dirt and remove it
(c) aluminium which coagulates the mud particles 131. Which one of the following forms micelles in aqueous
solution above certain concentration? [CBSE (PMT) 2005)
(d) making the mud water soluble
(a) Dodecyl trimethyl ammonium chloride
120. Surface tension of lyophilic sols is: [PMT (MP) 20021
(b) Glucose
(a) lower than that of H 20 (b) equal to that of H20 (c) Urea
(e) more than that of H20 (d) none of these (d) Pyridinium chloride
121. Arsenic sulphide is negative sol. The reagent with least 132. Muddy water can be purified through coagulation using:
precipitating power is: [PMT (ManipaJ) 2002J [CET (J&K) 2005]
(a) AICl 3 (b) NaCI (c) CaF2 (d) glucose (a) common salt (b) alums
122. Which one of the following is correctly matched? (c) sand (d) lime
[CEE (Tamil Nadu) 2002) 133. The disperse phase in colloidal iron(III) hydroxide and
(a) Emulsion-curd (b) Foam-mist colloidal gold is positively and negatively charged
(c) Aerosol-smoke (d) Solid sol-cake respectively. Which of the following is not correct?
(AIEEK 2005)
123. When HzS gas is passed through nitric acid, the product is:
[CEE (Kerala) 20021 (a) Magnesium chloride solution coagulates the gold sol more
readily than iron(III) hydroxide sol
(a) rhombic sulphur (b) prismatic sulphur
(b) Sodium sulphate solution causes coagulation in both sols
(c) amorphous sulphur (d) monoclinic sulphur
(c) Mixing of the sols has no effect
(e) plastic sulphur
(d) Coagulation in both sols can be brought about by
124. Tyndall effect is shown by: [CECE (Bihar) Pre 2004]
electrophoresis
(a) precipitate (b) sol
134. An emulsifier is a substance which: (AIEEE 2005)
(c) plasma (d) solution
(a) stabilises the emulsion
125. On addition of one mL of 10% NaCl solution to 10 mL gold
(b) homogenises the emulsion
sol in presence of 0.25 gm of starch, the coagulation is just
prevented, starch has gold number: fPMT (MP) 2004) ( c) coagulates the emulsion
(a) 0.25 (b) 0.025 (c) 2.5 (d) none of these (d) accelerates the dispersion ofliquid in liquid
126. Which of the following forms cationic micelles above certain 135. Gold number is associated with: [BHU (Mains) 2007;
concentration? [CBSE (PMT) 20041 AMU (Engg.) 2010J
(a) Sodium dodecyl sulphate (a) electrophoresis
(b) Sodium acetate (b) purple of cassius
(c) Urea (c) protective colloid
(d) Cetyltrimethyl ammonium bromide (d) amount of pure gold
127. The smog is essentially caused by the presence of: 136. Which one of the following is a false statement?
(AIEEE 2004) iPMT (Kerala) 2007)
(a) 02 and 0 3 (a) Cell fluid is an example of sol
(b) 02 and N2 (b) Butter is an example of gel
(c) oxides of sulphur and nitrogen ( c) Hair cream is an example of emulsion
(d) 0 3 and N z (d) Whipped cream is an example of foam
128. Which one of the following is most effective in causing the (e) Cheese is an example of emulsion
coagulation of an AS zS3 sol? (EAMCET 2009) 137. The presence, of electric charge on colloidal particles is
(a) KCI (b) AIC1 3 indicated by the property, called: ICET (J&K) 2007]
(a) dialysis (b) solubility .
(c) MgS04 (d) K3[Fe(CN)61
129. The fresh precipitate can be transformed in colloidal solution (c) electrophoresis (d) osmosis
by: JCET (J&K) 2004) 138. Which of the following properties are characteristic of
(a) peptization (b) coagulation lyophobic sols? (SCRA 2007)
(c) diffusion (d) none of these 1. Low viscosity, 2. High viscosity, 3. Reversibility and
4. Coagulation by electrolytes at low concentration
412 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
• Set-1
1. (a) 2. (b) 3. (a) 4. (c) 5. (b) 6. (d) 7. (d) 8. (a)
9. (b) 10. (c) 11. (a) 12. (b) 13. (d) 14. (a) 15. (c) 16. (a)
17. (b) 18. (c) 19. (b) 20. (d) 21. (d) 22. (c) 23. (c) 24. (a)
25. (a) 26. (c) 27. (b) 28. (d) 29. (c) 30. (a) 31. (c) ·.32: (ti)
33. (d) 34. (b) 35. (c) 36. (d) 37. (a) 38. (d) 39. (b) 40. (a)
41. (a) 42. (d) 43. (c) 44. (b) 45. (a) 46. (c) 47. (a) 48. (d)
49. (d) 50. (d) 51. (c) 52. (b) 53. (a) 54. (a) 55. (a) 56. (c)
57. (d) 58. (c) 59. (c) 60. (b) 61. (b) 62. (b) 63. (c) 64. (a)
65. (b) 66. (d) 67. (b) 68. (a) 69. (a) 70. (c) 71. (d) .72. (d)
73. (b) 74. (a) 75. (a) 76. (b) 77. (c) 78. (d) 79. (c) 80. (a)
81. (b) 82. (d) 83. (a) 84. (d) 85. (c) 86. (d) 87. (b) 88. (d)
89. (b) 90. (c) 91. (a) 92; (b) 93. (b) 94. (b) 95. (a) 96. (a)
97. (d) 98. (c) 99.· (a) 100. (c) 101. (b) 102. (c) 103. (c) 104. (c)
105. (a) 106. (b) 107. (b) 108. (b) 109. (c) 110. (a) 111. (b) 112. (a)
113. (d) 114. (a) 115. (b) 116. (a) 117. (d) 118. (a) 119. (c) 120. (a)
121. (d) 122. (c) 123. (c) 124 •. (b) 125. (d) 126. (d) 127. (c) 128. (b)
129. (a) 130. (e) 131. (a) 132. (b) -133. (c) 134. (a) 135. (c) 136. (e)
137. (c) 138. (c) 139. (b) 140. (a) 141. (a) 142. (b) 143. (c) 144. (b)
145. (a)
• Set-2
\
• • LI~~~~:~~~fPJtt;HENSIONTYPE Q~ESTlONS·.B;
" ~ '~"':"_","",.;. ;' c', ., .• ,,".' . ': :~;, f' _ '. " , . ,
• Passage 1
2. What type of molecules form micelles?
There are certain substances which behave as normal, strong
electrolytes at low concentration but at higher concentration they (a) Non-polar molecules
behave as colloidal solutions due to the formation of aggregated (b) Polar molecules
particles. Such colloids are called associated colloids and the (c) Surfactant molecules
aggregated particles are called micelles. Soaps and detergents are (d) Salt of weak acid and weak base
the examples of associated colloids. The formation of micelles takes 3. Micelles are formed only: '
place above certain concentration called critical micellization (a) below the CMC and the Kraft temperature
concentration (CMe) and a characteristic temperature. (b) above the CMC and below the Kraft temperature
Answer the following questions: (c) above the CMC and above the Kraft temperature
. 1. Micellesare: (d) below the CMC and above the Kraft temperature
(a) emulsions cum gels 4. Above. CMC, the surfactant molecules undergQ:
(b) associated colloids (a) dissociation (b) aggregation
(c) adsorbed catalysts (c) micelle formation (d) all of these
(d) idealsolutions
THE COLLOIDAL STATE 417
5. Micelles are used in: . .•.~J)assag~3 .
"....
(a) detergents (b) magnetic separation
The process of dialysis finds application in the purification of
(c) petroleum recovery (d) all of these
blood by artificial kidney. In this method, impure blood is introduced
in the artificial kidney apparaltts,. where the wa51e material
• Passage2 (electrolyte) diffuses through the memhrane. The membrane used in
Emulsions are also the. colloidal solutions in which disperse the dialyser is different from the· membrane used in osmosis. '['hese
phase as well as dispersion medium a';'e liquids. It may be oil in membranes allo wthe movement of ions through them.
water or water in oil type. Bancroft proposed that the phase in which Blood is a negatively charged sol. The haemoglobin particles
the emulsifier is more soluble becomes the outer phase of the carry a positive charge. Blood is slightly alkaline ,(pH 7.36-7.42).
emulsion. Emulsifiers can be used to stabilize the emulsion. Soaps, Acidic salts like alum and FeCl3 decrease the pH olthe bloud and the
detergents, proteins and gum. etc., are used as emulsifiers. denaturation of globular proteins present in blood takes place. Due
Answer the following questions: to denaturation, these globular proteins become fibrous which are
1. Addition oflyophilic solution to the emulsion fonns: insoluble and stop bleeding. Blood is lyophobic in natllre.
(a) a protective film around the dispersed phase Answer the following questions:
(b) a protective film around the dispersion medium 1. To stop bieeding, FeCl 3 is applied locally because:
(c) an aerosol (a) FeCl 3 seals the blood vessels
(d) true solution (b) FeCl 3 changes the direction of blood flow
2. Which of the following examples is/are oil in water type (e) FeCl 3 reacts with blood to form a solid substance which
emulsion? seals the blood vessel .
(a) Ink (b) Detergent (d) FeCl 3 causes denaturation of proteins present in blood
(c) Soap (d) Milk 2. Which of the following colloidal solutions does not contain
3. Emulsions canbe destroyed by: negatively charged particles'!
(a) the addition of emulsifier which tends to form another (a) Fe(OHh (b) As2 S3 (c) Blood . (d) Gold sol
emulsion 3. The coagulating power of an electrolyte for blood decreases in
(b) electrophoresis with high potential the order:
(c) freezing (a) Na+, AI 3+, Ba2+ (b) PO~-, SO~-, Cl-
(d) all of the above (c) Ae+, Ba 2+, Na+ (d) a-, SO~-, PO!-
4. Which of the following is homogeneous? 4. Which of the following statements is/are not true?
(a) Milk (b) Paint (a) Blood is positively charged sol
(c) Shampoo (d) None of these (b) Soap solution contains ionic miceiles as the colloidal
5. Milk is an emulsion in which: particles
(a) milk fat is dispersed in water (c) Blood is purified by the process of dialysis
(b) a solid is dispersed in water (d) Ca 2+ and K+ cause coagulation of blood if added in
(c) a gas is dispersed in water excess
(d) lactose is dispersed in water 5. Which of the following isiare lyophobic colloids?
(a) Blood (b) Starch (c) Gelatin (d) Gold
<i? SEtFASSESSMENT¢
ASSIGNMENT NO.6.
SECTION-I SECTION-II
Straight Objective 'fYpe Questions
This section contains 10 multiple choice questions. Each Multiple Answers Type Objective Questions
question has 4 choices (a), (b), (c) and (d), out of which only 11. Which ofthe following are lyophilic in nature?
one is correct. (a) Gum (b) Sulphur (c) Starch (d) Protein
1. Dbpersed phase and dispersion. medium in butter are 12. Surfactant molecules form micelles in aqueous solution,
respectively: [EAMCET (Medical) 2007] which:
(a) solid and liquid (b) liquid and liquid (a) tend to congregate due to their hydrophobic tails
(c) liquid and solid (d) solid and solid (b) are colloidal-sized cluster of molecules
2. Which one of the following acts as the best coagulating agent (c) Provide protection due to their hydrophobic head
for ferric hydroxide sol? IPMT (Kerala) 2007] (d) none of the above
(a) Magnesium chloride (b) Hydrochloric I:)cid 13. Crystalloid and colloid differ with respect to:
(c) Aluminium chloride (d) Potassium oxalate (a) Tyndall effect
(e)· Potassium ferricyanide (b) particle size
3. The colloidal sol found effective in the treatment of eye (c) diffusion through animal or vegetable membrane
disease is: (d) number of particles per unit volume of solution
. (a) colloidal sulphur (b) colloidal antimony 14. Select the correct statements among the following:
(c) colloidal silver (d) colloidal gold (a) Milk is emulsion offat in water
4. When alcohol is added to the saturated solution of calcium (b) An emulsifIer stabilizes the emulsion
acetate in water then we fIrst of all get sol which changes to (c) Emulsifier forms a thin film around the droplets of
gelatinous mass called solid alcohoL Solid alcohol is ........ . dispersed phase
(a) aerosol (b) gel (d) Milk is an emulsion of protein in water
(c) solid foam (d) solid sol 15. Which ofthe following statements are true?
5.' Colloidal solutions of gold prepared by different methods are (a) Flocculation value is inversely proportional to the
of different colours because of: coagulating power .
(a)· variable valency of gold (b) Colloidal silica is a protective colloid
(b) impurities produced by different methods (c) Alum is used for cleaning muddy water
(c) different diameters of colloidal gold particles (d) Gelatin is added in ice cream, ii acts as emulsifier
(d) different concentration of gold particles
6. Emulsions of polyvinyl acetate are used in: SECTION.;.III
(a) polishes (b) latex paints
(c) fire works (d) rayons Assertion-Reason Type Questions
7. The outcome. of internal liquid of gel on shaking is caned: This section contain~~:5 questions. Each question contains
(aj syneresis . (b) imbibition Statement-l (Assertion) and Statement-2 (Reason).· Each
question has following 4 choices (a), (b), (e) and (d), out of
(c) thixotropy (d) precipitation
which ?llly one is correct.
8. Which of the following shows the maximum hydrophobic
(a) ,Statement-l is true; statement-2 is true; statement-2 is a
behaviour?
. correct explanation for' statement-I.
(a) Adenine (b) Glucose
(b) Statement-l is true; statement-2 is true; statement-2 is not
(c) Stearic acid (d) Glycine a correct explanation for statement-I.
9. The solution of natural rubber in benzene is an example of: (c) Statement-l is true; statement-2 is false.
(a) lyophobic colloids (b) macromolecular colloid (d) Statement-l is false; statement-2 is true.
(c) multimolecular colloid (d) associated colloid 16. Statement-I: Micelles are formed by surfactant molecules
10. When NaCI solution is added to Fe(OHh sol then: above the critical micellar concentration (CMC) .
. (a) [Fe(OHh ]Fe3+. is formed Because
(bn~e(~H)~lCl- is foimed. Statement-2: The conductivity of solution having surfactant
molecules decreases sharply at the CMC. (lIT 2007)
(c) Fe(OHh is coagulated
[Hint: Micellisation takes place above certain minimum
(d) [Fe(OHh]Na+ is formed
concentration called critical micellar concentratiori (CMC). Each
micelle contains at least 100 molecules, therefore conductivity of
solution decreases sharply at the CMC.]
THE COLLOIDAL STATE 419·
17. Statement-I: Aqueous gold colloidal solution is red in colour. 19•. Statement-I: Colloidal solutions are electrically neutral..
Because Because
Statement-2: The colour arises due to scattering of light by Statement-2: Dispersed phase and dispersion medium are of
colloidal gold particles. same charge.
18. Statement-I: An emulsion becomes stable if soap is added to ;20. Statemeitt-l: Colloidal sol scatter the beam oflight while true
. it. solutions do not.
Because Because
Statement-2: Soap contains hydrophobic and hydrophilic Statement':'2; The particles in colloidal sol are bigger than
parts. those of true solutions.
,'.,..
[:).f~f~.~:.
'.
--------~-___II
. ;;.~ .. '
INTRODUCTIO~ given set of conditions but does not tell anything about the rate at
which the given process may proceed. It is only concerned with
Thermodynamics is a Greek word. Its literal meaning is motion initial anel final states of the system. For example,
or flow (dynamics) of heat (thermos). However, the term is used thermodynamics predicts that the reaction between oxygen and
in a more general way. Thermodynamics is the branch of hydrogen is possible under ordinary conditions but does not tell
science which deals with all changes in energy or transfers of whether the reaction is fast or slow.
energy that accompany physical and chemical processes. It is
concerned with interconversion of various forms of energy. .7.2 TERMS USED IN THERMODYNAMICS
Chemical thermodynamics is the branch of
Before we study the laws of thermodynamics, it is necessary to
thermodynamics which deals with the study of processes in
define some of the basic terms which are frequently used in its
which chemi,cal energy is involved.
discussion:
, ,Or
(i) System, Surroundings and Boundary: A system is
Chemical thermodynamics is one of the branches, of defined as a specified part of the universe or specified portion
physical ~emistry which deals with transport of heat either of the matter which is under experimental investigation and
as a result of physical change or as a result of chemical the rest of the universe, Le., all other matter which can
change.
interact with the system, is surroundings.
Chemical thermodynamics is concerned with the following
Anything which separates system and surroundings is called
questions:
boundary. The boundary may be real or imaginary; it may
(i) When two or more substances are put together, will they
be rigid or non-rigid; it may be a conductor or a non-conductor of
react?
heat. The terms diathermic wall and adiabatic wall are used for
(ii) If they do react, what energy changes will be associated conductor and non-conductor of heat boundaries respectively.
with the reaction?
For example, a reaction is carried out in a beaker. The contents
(iii) If a reaction occurs, at what concentrations of the of the beaker constitute the system, beaker serves as boundary
reactants and their products will equilibrium be established? and the beaker, the air and anything else in the vicinity constitute
Thermodynamics is not concerned with the total energy of the the surroundings.
.body but only with energy changes taking place during the
(ii) Types of System: There are three types of system:
transformation. The study of thermodynamics is based on three
(a) Isolated system: This type of system has no interaction
generalisations derived from experimental results. These
with its surroundings. The boundary is sealed and insulated.
generalisations are known as first, second and third law of
Neither matter nor energy can be exchanged with surroundings.
thermodynamics based on human experience and there is no
, A substance contained in an ideal thermos flask is an example of
formal proof for them. Scientists are of the view that nothing
an isolated system.
contrary to these laws will ever occur.
(b) Oosed system: This type of system can exchan~e
Limitations of thermodynamics: (i) The laws of
energy in the form of heat, work or radiations but not matter WIth
thermodynamics apply only to the matter in bulk, i.e.,
its surroundings. The boundary between system arid
macroscopic system and not to individual atoms or molecules of
surroundings is sealed but not insulated. For example, liquid in
the macroscopic system. Thermodynamics does not deal with
contact with vapour in a sealed tube forms a closed system. Heat
internal structure of atoms and molecules. (ii) Thermodynamics
can be transferred through the walls of the tube to the
can only predict the feasibility or spontaneity of a process under a
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 421
surroundings but total amount of matter remains the same as Density Number of moles
vapours cannot escape. Temperature Gibbs free energy
(c) Open system: This type of system can exchange matter
Pressure Enthalpy
as well as energy with surroundings. The boundary is riot sealed
and not Prsulated. Sodium reacting with water in an open beaker Mole fraction Entropy
is an &'ample of open system as hydrogen escapes and heat ofthe Molar enthalpy Internal energy
reaction is transferred to the surroundings.
Molar entropy
On the basis of composition, there are two types of systems:
Refractive index
(1) Homogeneous system: A system is said to be
. homogeneous when it is completely uniform throughout. A Specific heat
homogeneous system is made of one-phase only. Examples are: a Viscosity
. pure single solid, liquid or gas, mixture of gases and a true
Surface tension
solution.
(2) Heterogeneous system: A system is said to be Dielectric constant
heterogeneous when it is not uniform throughout, i. e. , it consists When the total mass, temperature, volume, number of moles
two or more phases. Examples are: ice in contact with water, tw<1 and composition have definite values, the system is said to be in a
or more immiscible liquids, insoluble solid in contact with ·a definite state. When there is any change in anyone of these
liquid, a liquid in contact with vapour, etc. properties, it is said that the system has undergone a change of
(iii) Thermodynamic Properties: These are of two types: state. '
(a) Iutensive properties: The properties which do not. (iv) State Functions or State Variables: Fundamental
depend upon the quantity of matter present in the system or size of properties which determine the state of a system are referred to as
the system are called intensive properties. Pressure, temperature, state variables or state functions or thermodynamic
density, specific heat, surface tension, refractive index, viscosity, parameters. The change in the state properties depends only
melting point, boiling point, volume per mole, concentration, etc.,' upon the initial and final states of the system, but is independent
are the examples of intensive properties of the system. of the manner in which the change has been brought about. In
(b) Extensive properties: The properties whose magnitude other words, the state properties do not depend upon a path
depends upon the quantity of matter present in the system are followed.
called extensive properties. Following are the state variables that are commonly used to
Extensive property is an additive propertY of the system. For a describe the state of the thermodynamic system:
heterogenaous system consisting of several phases, the total
1. Pressure (P) 2. Temperature (T)
value of.. extensive property will be equal to the sum of
3. Volume (V) 4. Internal energy (E)
contributions from several phases.
5. Enthalpy (H) 6. Entropy (8)
The following are some salient features of these properties:
7. Free energy (G) 8. Number of moles (n)
(i) In a system having two or more substances, the extensive
property will depend not only on the independent variables but (v) Thermodynamic Processes: When the thermodynamic
also on the number of moles of different componerits present in it. system changes from one state to another, the operation is called a
(ii) If an extensive property is expressed per mole or per gram, process. The various types of the processes are:
it becomes intensive property. For example, mass and volume are (a) Isothermal process: The process is termed isothermal
extensive properties but density (mass per unit volume) and if temperature remains fixed, i. e. , operation is done at constant
specific volume (volume per unit mass) are intensive properties. temperature. This can be achieved by placing the system in a
(iii) The product, sum and ratio of intensive properties are also constant temperature bath, i. e., thermostat. Fer an isothermal
intensive properties. Let X and Ybe two intensive properties, then process dT = 0, i. e. ,heat is exchanged with the surroundings and
X aX ..
(X + Y) ; XY ; ; - are mtensIve propertIes.
. the system is not thermally isolated.
Y ay (b) Adiabatic process: If a process is carried out under
(iv) Let X and Ybe the two extensive properties, then such condition that no exchange of heat takes place between the
(a) (X + Y) will also be an extensive variable. system and surroundings, the process is termed adiabatic. The
system is thermally isolated, i. e., dQ = O. This can be done by
(b) X and -ax WI'11 b' . varia
e mtensIve . bl es.
Y ay keeping the system in an insulated container, i. e. , thermos flask.
In adiabatic process, the temperature of the system varies.
Extensive and intensive properties (c) Isobaric process: The process is known as isobaric in
which the pressure remains constant throughout the change, i. e. ,
IDtensive properties
dP=o.
Molarity Heat capacity (d) isochoric process: The process is termed as isochoric
Molality Mass in which volume remains constant throughout the change, i. e.,
dV=O.
Concentration Volume
i
/
422 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(e) Cyclic process: When a system undergoes a number·of Pext == intensity factor
different processes and finally returns to its initial state, it is A V capacity factor
termed cyclic process. For a cyclic process dE = 0 ani! dH = O. Work (w) is a path-dependent function, it is a manifestation of
(1) Reversible process: A process which occurs energy. Work done on a system increases the energy of the system
infinitesimally slowly, i. e., opposing force is infinitesimally and work done by the system decreases the energy of the system.
smaller than driving force and when infinitesimal increase in the Work done on the system, w + ve
opposing force can reverse the process, it is said to be reversible Work done by the system, w == - ve
process. In fact, a reversible process is considered to proceed Heat may be defined as the quantity of energy which flows
from initial state to final state tbrough an' infinite series of between a system and its surroundings on account oftemperature
infmitesimally small stages and at every stage it is virtually in difference. Heat always flows from high temperature to low
state of equilibrium. A reversible process is an ideal process and temperature.
canp.ot be realised in practice. Heat absorbed or evolved, ~Q = ms At
(g) Irreversible process: When the process .goes from where, m mass of substance, s:::: specific heat .
initial to final state in single step in fmite time and cannot be and At "'" temperature difference.
reversed" it is termed as irreversible process. I.n such a case (i) Heat flowing into the system, ~Qor MI + ve.
equilibrium state exists only at the initial and fmafstages of the
The process in this case is endothermic in which the
process. An irreversible process is spontaneous in nature. It is
temperature ofthe system is raised and that ofthe surroundings is
real and canbe perforined in practice. All natural procefises are
lowered.
irreversible in nature.
(ii) Heat flowingout of the system, AQor MI::::- ve.
ReverSibte process . Irreversible proeess The process in this case is exothermic in which the
temperature of the system is lowered and that ofthe surroundings
.1. It is an ideal process and takes It is. a spontaneous process and is raised.
infinite time. takes finite time.
Units of Heat and Work: The unit of heat is calorie (cal). It
2. The driving force is infinitesi- The driving force is' much is defined as the quantity of heat required to raise the temperature
mally greater than the opposing greater than the opposing force. of one gram of water by loe.
force. Since, heat and work are interrelated, S1 unit of heat is the
3. It is in equilibrium at all stages. Equilibrium exists in the initial joule(J).
and final stages only, I joule ~ 0.2390cal
4. Work obtained is maximum. ,Work obtained is not maximum. l.calorie = 4.184 J
5. It is difficult to realise in It can be performed in practice. 1 kcal =4.184 kJ
prllctice. 1 litre -atrn =1 0 1.3 J
Nature of Work and Heat 1.013 X 10 9 erg
Work is a mode, of energy transfer to or from a system with
= 24.206 cal
reference to the surruundings. If an object is displaced tbrough a
distance d x against a force ofF, then the amount of work done is . :.; ::::a_SoME SOLVED ExAMPLES\:::::::
defined as
Wo··Fxdx i,·Example 1. A gas expands by 0.5 litre against a constant
There are many types of work and all of them could be pressure ofone atmosphere. Calculate the work done in joule and
expressed as the product of two factors: calorie.
(i) an intensity factor, Solution: Work = - Pext X volurnechange
(ii) a capacity factor.
:::: -1 x 0.5 0.5 litre -atrn
Some ofthem are:
( a) Gravitational work = (mg ) X h :::: 0.5 x 101.328J = - 50.664 J
where, m = mass of body, g = acceleration due to gravity, 0.5Iitre-atrn -0.5 x 24.20cal =-12.l0cal
h = height moved. . ' . ,Example 2. One mole of an ideal gas is put through a
(b) Electrical work charge x potential series of changes as shown in the graph in which A, Band C
QXV mark the three stages of the system. At each stage the variables
where, Q = charge, V == potential gradient are shown in the graph ..
(c) Mechanical work = P ext (V2 VI) Pext AV (a) Calculate the pressure at three stages ofthe system.
where, Pext = external pressUre, AV increase or decrease in (b) Name the processes during the following changes:
volume. ' (i) A to B (ij) B to C (iii) C to A and (iv) overall change.
Work. associated with change in volume of a system against
external pressure is called mechanical work.
I
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY ·1423
=-PxdV= 12x 10 5 x 5x 10-3
24.0 (L) ----------,-----[:7lAI B = 6000J
. . I
I Work done in the process B -7 C is zero as volume remains
. I
, . . I
I
constant.
I
. I
Work done in the process C -7 D (The process is contraction,
1,2.0
.
V
-
(Ll --------------.
I
I
c .
. I
i
I
I
hence work is done on the gas)
. =P x dV =2x 105 x5x 10-3
I I
I I
I I
I
I
I
I
= 1000J
I I
I
I
I
I
(ii) Work done in the. process D -7 A is zero as volume
remains constant.
300 K 600 K
T • Net work done in the wl;1ole cycle = - 6000 + 1000 5000 J
Solution: (a) At stage A: i. e. , net work is done by the gas.
;Example 4. Calculate tlie work done when 1.0 mole; of
V 24.0L;T=300K;n l;R 0.08211itre-atmK-1 mol-: 1
water at 373 K vaporizes against an atmospheric pressure ofl.O
Substituting these values in the ideal gas equation, . aimosphere. Assume ideal gas behaviour.
Solution: Thevolume occupied by wateris very small and
PV=nRT,
thus the volume change is equal to the volume occupied by one
P = 1 x 0.0821 x 300 = 1.026atm gram mole of water vapour.
24.0 V nRT l.Ox 0.0821 x 373 31.0 litre
At stage B: Volume remains the same but temperatUre P 1.0
changes from 300 K to 600 K. Thus, according to pressure law, W=-Pext xAV -(1.0)x(31.0)litre-atm
the pressure will be doubled at B with respect to A.
Pressure at B 2 x 1.026= 2.052 atm = - (31.0) x 101.3 J = - 3140.3 J
At stage C: Temperature is 300 K and volume is half that of Example 5. Identify different steps in the following cyclic
stage A. Thus, according to Boyle's law, the pressure at C will be process:
doubled with respect to A.
Pressure at C = 2 x 1.026= 2.052atm
Temperature At A ,B
(b) (i) During the change from A to B, volume remains
and F is 11 and at C,
constant,"'the process is isochoric.
(ii) During the change from B to C the pressure remains
constant, the process is isobaric. .
I
p
DandEisT2
Tl >T2
.
/
424 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
. T 1, 20 atm. T 20 t 201't contribute to 'the absolute value of internal energy for a given .
A~r
substance in a given state is impossible. But one thing is certain
am, 'ffi that the internal energy of a particular system is a definite
quantity at the given moment, irrespective of the manner by
which it has been obtained. Internal energy like temperature,
p
pressure, volume,' etc., is a state function, i.e., total of all
C possible kinds of energy of a system is called its internal
T1, 2 atm, 10 litre
energy*.
v- It is neither possible nor necessary to calculate the absolute
(a) Calculate TI and T2 . value of internal energy of a system. In thermodynamics, one is
(b) Calculate !lE, q and W in calories in each step of cyclic concerned only with energy change which occurs when the
ptocess. system moves from one state to another. Let dE be the difference
Solution: (a) At A : of energy of the initial state (E j ) and the final state (E f ), then
!lE=E f -
PV = nRT
!lE is positive if E f > E i and negative if E f < E j'
20 x 1= 1x 0.0821 X TI A system may transfer energy to or from the surroundings as
Ii 243.6K heat or work or both,
AtB: PV nRT Characteristics of Internal Energy
20x 10= I x 0.0821 X T2 (i) Internal energy of a system is an extensive property.
T2 = 2436.05 K (ii) Internal energy is a state property.
(b) Path AB: Isobaric process (!lE = 0, q = W ) (iii) The change in the internal energy does not depend on the
path by which the final state is reached.
W =P8V = 20x 9= 180litre~atm (iv) There is no change in internal energy in a cyclic process.
180x 101.3 cal
:=
Thermal Equilibrium and Zeroth Law of
4.185
Thermodynamics .
= 4356.9 cal (Work in compression is positive) When a hot body is kept in contact with a cold body, the cold
Path BC: Isochoric process body warms up and the hot body cools down. The internal energy
w=o of the hot body decreases and that of cold body increases. The
. 3 transfer of energy from the hot body to a cold body is a
qv =8U = n C v 8T = ] x - R x (2436 - 243.6) non-mechanical process. The energy that is transferred from one
2
body to the other, without any mechanical' work involved , is
:::: ~ X 2 x 2192.4= 6577.2 cal called heat.
2
Two bodies are said to be in thermal equilibrium if no transfer
It is cooling process: qv == 6577.2 cal of heat takes place when they are placed in contact.
Path CA: It i.~ i"athermal compression dE o The temperature concept can be stated precisely by the fact
that systems in therm(11 equilibri;!m with each other have the
q = W = 2.303 nRT log, V2 same temperature.
VI
Courses of thermodynamics usually deal with the three laws:
. 10 the first, second and third laws, which constitute the subject
q =W 2.303 x 1x 2 x log -- = 1122.02cal
I matter of thennodynamics. However, at present an ever
increasing use is made in thermodynamics of the law of thennal
INTERNAL ENERGY equilibrium formulated by R. Fowler in 1931, i.e., the Zeroth law
of the,'7Tlodynamics. This law was formulated after the first and
Every !';ystem having some quantity of matter is associated with a
definite amount of energy. This energy is known as internal the second laws had been enunciated.
energy. The exact value of this energy is not known as it includes This law states: If two systems are in thermal equilibrium with a
all types of energies of molecules constituting the given mass of third system, they are also in thermal equilibrium with each other. .
matter such as translational, vibrational, rotational, the kinetic Conversely, the law can be stated as follows:
and potential energy of the nuclei and -electrons within r!"e Ifthree or more systems are ill thermal contact with each other
individual molecules and the. manner in which the molecules 1\' by means ofdiathermal walls alld are all in thermal equilibrium
linked together, etc. The internal energy is denoted by E. together, then any two systems taken separately are in thermal
equilibrium with each other.
E E translational + E rotational + E vibrational + E bonding + E electronic + ,.,
Now let us consider three systems A, Band C a') shown in Fig.
,\ccurate measurements of some forms of energy which 7.1. It is an experimental fact that if system A is in thermal
*The word internal is often omitted and the word energy implies internal energy of a system.
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 425-
equilibrium with system C and system B is also in thermal 1he net energy change of a dosed system is equal to heat
equilibrium with system C, then A and B are in thermal ab~orbed plus the work done on the system.
equilibriUl\1 with each other. Or
The net energy change of a dosed system is equal to heat
absorbed minus the work done by the system.
Or
It is impossible to construct a mobile or perpetual machine
that can work without consumption of any fuel energy.
;':Jl:,,,ample 7. If 500 calorie of heat energy are added to a
system and the system does 350 calorie of work on the
surroundings, what is the energy change ofthe system?
Solution: Heat absorbed, q 500cal
Work done by the system, w 350cal
Applying the first law of thermodynamics,
Fig. 7.1 Systems in therma.1 equilibrium
M = q + w 500+ (-350)= 150calorie
[,lit, FIRST LAW OF THERMODYNAMICS Example 8. If 100 calorie of heat are added tothe same
system as in example 1 and a work of 50 calorie is done on the
This law has been stated in vario¥s forms but is merely the law of system, calculate the energy change of the system.
conservation of energy. It was given by Robert Mayer and
Helmholtz. Solution: Heat absorbed, q = 100 cal
(i) Energy cannot be created or destroyed but it can be Work done on the system, w + 50 cal
converted from one form to another. Applying the first law of thermodynamics,
(ii) The total energy of the universe is constant. I:lE = q + w = (100 + 50) = 150calorie
(iii) Whenever a quantity of one kind of energy disappears, an In the above two examples, the final state is same but the paths
exactly equivalent quantity of energy in some other form must adopted are different. Thus, the change in energy of the system
appear. depends on the initial and final states but does not depend on the
(iv) It is impossibie to construct a perpetual motion machine path by which the final state has reached, q and ware, therefore,
which could produce work without consuming energy. not state functions but M is a state function.
(v) The total energy of an isolated system remains constant
though it may change from one form to another. Some useful conclusions drawn from the first law:
When a system is changed from initial state to the final state, it !:lE =
q+w
undergoes a change in the internal energy from E i to E f' Thus, (i) When a system undergoes a change !:l E 0, i. e. , there is .
!:lE can be written as: no increase or decrease in the internal energy of the system. the
M'='Er ~-Ei first law of thermodynamics reduces to
The change in internal energy can be brought about in two o q+w
ways: m q w
(a) Either by allowing the heat to flow into the system (heat absorbed from surroundings work done by the system)
(absorption) or out of the system (evolution). m w=-q
(b) By doing work on the system or the work done by the (heat given to surroundings = work done on the system)
system.
(ii) If no work is done, w = 0 and the first law reduces to
Consider a system whose internal energy is El . If the system is
supplied q amount of heat, the internal energy of the system will M=q
become E1 + q. Now if work w is also done on the system, the i. e. , increase in internal energy of the system is equal to the heat
final internal energy becomes E 2 • Thus, absorbed by the system or decrease in internal energy of the.
system is equal to heat lost by the system.
E2 '='E1 +q+w
(iii) If there is no exchange of heat between the system and
or E1 = q+ w
surroundings, q = 0, the first law reduces to
or M q+w
This is the mathematical statement of the first law of M w
thermodynamics. In this statement, q is the heat absorbed and w is It shows that if wmk is done on the system, its internal energy
the work done on the system. will increase or if work is done by the system, its internal energy
In case q is the heat absorbed and w the work done by the will decrease. This occurs in an adiabatic process.
system, then the relationship becomes (iv) In case of gaseous system, if a gas expands against the
M=q+ (-w)""q-w constant external pressure, P, let the volume change be !:lV. The
The first law of thermodynamics may also be stated as: mechanical work done by the gas is equal to -P x !:lV.
426 G.R.B. PHYSICAl.: CHEMISTRY FOR COMPETmONS
7~7 EXPANSION OF AN IDEAL GAS surroundings and the temperature remains constant throughout
the expansion; •
(i) Isothermal Expan'Sion The work done by the gas in each step of expansion can be
In an isothermal expansion, heat is allowed to flow into or ou}- given as,
of the system so that temperature remains constant throughout the . dw (P~X! -dP)dV=-Pext ·dV=-PdV
process of expansion. Since, for an ideal gas, the internal energy,
dP· dV, the product of two infinitesimal quantities, is neglected.
llE, depends only on temperature, it follows that at constant
The. total amount of work done by the isothermal reversible
temperature, the internal energy of the gas remains constant, i. e. ,
expansion of the ideal· gas from volume VI to volume V2 is,
llE is zero.
therefore,
llE=O
w=_fV2 PdV
According to first law of thermodymimics, VI
llE q+w For an ideal gas, p=nRT
Since, for isothermal process, llE 0, hence V
q=-w So, w -nRT fV2 dV
JVI V
This shows that in isothermal expansion, the work is done by V2 •
the system at the expense of heat absorbed. The magnitude of q or Integrating, W = - nRT log e - =- 2.303nRT log
w depends on the manner in which the process of expansion is VI VI
carried out, i. e. ,whether it is carried reversibly or irreversibly. At constant temperature, acc.ording to Boyle's law,
Calculation of A Hcan be done according to the following PIVI =P2 V2
equation:
or V2 =~
H=oE+PV VI P2
or AH = llE + A(PV)
So, W = - i.303nRT log
or AH = llE + A.(nRT ) P2
Since, for isothermal process, llE and AT are zero Isothermal compression work of an ideal gas may be derived
. respectively, hence, similarly and it has exactly the same value with positive sign.
AH 0 . V .
wcompression 2.303nRT log ..J... = 2.303nRT log
Work done in reversible isothermal expansion V2 PI
Consider an ideal gas enclosed in a cylinder fitted with a
weightless and frictionless piston. The cylinder is not insulated. Work done in irreversible isothermal expansion
The external pressure, Pex! , is equal to pressure of the gas, Pgas' Two types of irreversible isothermal expansions are observed,
Let it be P. i. e., (i) Free expansion and (ii) Intermediate expansion. In free
Pex! P gas P expansion, the external pressure is zero, i. e. , work done is zero
when gas expands in vacuum. In intermediate expansion, the
If the external pressure is decreased by. an infinitesimal'
external pressure is less than gas pressure. So, the work done
amount dP, the gas will expand by an infmitesimal volume, dV.
when volume changes from P1 to V2 is given by
As a result of expansion, the pressure of the gas within the 2
cylinder fans to Pgas - dP, i. e., it becomes again equal to the W = - f V Pext X dV = - Pex! (V2 -
VI
Vi )
external pressure and,· thus, the piston comes to rest Such a
Since, Pext is less than the pressure of the gas, the work done
process is repeate~ for a number of times, i. e. ,in each step the gas
during intermediate expansion is numerically less than the work
expands by a volume dV.
done during reversible isothermal expansion in which Pex! is
Since, the system is in thermal equilibrium with the
almost equal to Pgas'
surroundings, the infinitesimally small cooling produced due to
expansion is balanced by the absorption of heat from the Maximum work: The work done by the system always
depends upon the external pressure. The higher the value of Pext ,
the more work is done by the gas. As Pex! .cannot be more than
Pexl dp Pgas' otherwise compression will occur, thus the largest value of
Pex! can be equal to P gas . Under this condition when expansion
occurs, the maximum work is done by the gas Qn the surroundings.
}dV
(ii) Adiabatic Expansion
In ·adiabatic expansion, no heat is allowed to enter or leave the
Pgas
system, hence, q Q Whenthis value is substituted in first law of
thermodynamics, AE q + w, we get llE = w.
In expallsion, work is done by the system on the surroundings,
Fig. 7.2 hence, w is negative. Accordingly AE is also negative, i.e.,
428 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(~r
internal energy decreases and therefore, the temperature of the
system falls. In case of compression, M is positive, i.e., internal or I ... (x)
energy increases and therefore, the temperature of the system
(~r
rises.
The molar specific heat capacity at constant volume of an or I
P2V2
ideal gas is given by .
C v (~~)v
=
or
or
PI V; Y
PVY
P2V/ ... (xi)
... (xii)
constant
or dE=C v ·dT ... (i)
and for finite change M = C v AT ... (ii) Thus, knowing y, Vi ,V2 and initial temperature, TI , the final
temperature, Tz , can be readily evaluated.
So, w=M=C v AT ... (iii)
ModifYing the eq. (x),
The value of AT depends upon the process whether it is
reversible or irreversible.
CV IT2
T}
dT = - R
T
J V2
VI
dV
V
In free expansion, the external pressure is zero, i. e. , work done
is zero. Accordingly, AE which is equal to w is also zero. If Mis
zero, AT should be zero. Thus, in free expansion (adiabatically),
v V AT =0, M:= 0, w = 0 and AH = O.
C v loge - R log -"l:.. = R log -.l.
TI eVe V In intermediate expansion, the volume changes from VI to V2
1 2
against external pressure, Pc'!.t •
T R V R VI
or log -"l:.. log -"l:.. -log- ... (vii) .W = - P cxt (V2 - VI )
1j Cv VI Cv Vz
i _--+---Isobaric process i
Isothermal process
Adiabatic process
Isochoric process V1 V2
Volume ----to-
Volume ----to- Fig. 7.6 Shaded area gives the work done by the gas when
Fig. 7.3 (a) pressure remains constant
w exp == - Pext (V2 - Vi )
Expansion
Compression. = - ve work
i
p
Volume ----to-
i
p
~ Volume ----to-
i
Fig. 7.3 (c) V, V2
Fig. 7.3 (b) Volume ----to-
2. Let a gas is compressed from Vi or VI by an external Fig.7.7 Shaded area represents the work done by the gas
pressure of Pext ' The work done on the gas can be calculated by when both pressure and volume vary
the shaded a:rea of the graph represented in following Fig. 7.4. 5. Work done by a gas undergoing cyclic process : It is
Work done on the gas, w== - Pext (VI - Vi) detennined with the help of following three graphs.
= + ve work, Since VJ < Vi
(~~~1T1) i PN1T,
i I!!
:::l
Cf)
~P2V2T~~
• • Cf)
NPN2T 2
. I!! ~ •.• .,----<Il--...,.
Cf)
I!! :. : m
:::l
Cf)
a.. : ~
a..
~ Volume ----+- Volume ----to- Volume ----to-
(a) (bj (c)
VI Vi Shaded area Shaded area Shaded area
Volume ----to- gives the work gives the work gives the net work
~~~~ ~oo~~ ~~~~
Fig. 7.4 Single step compression of ideal gas against
external pressure Pext Fig. 7.8 Complete cyClic process of a gas
..
430 G.R.B. 'PHYSICAL CHEMISTRY FOR COMPETITIONS
6. Work done by the gas in a closed path ABCA. 9. Ifthe state of a system changes in such a way that its volume
remains constant, the process is called isochoric. Following three
plots represent isochoric process.
ip2"'~',A
",
:!!
:::l
~ P ....
!1l
,
1 B'
'
C
• P
it---- i
V P
0: .: .:
. .
V1 V2 '
Volume ----II>
Fig. 7.9 The gas in closed cyclic process ABCA V ----II> T ----II>
(a) (bl
Work done = Area of shaded triangle Fig.7.12 Isochores of Ideal Gas
I' ,,
= -' x Length of base x Length of perpendicular
2 10. If the state of system changes in such a way that pressure is
I constant, the process is called isobaric. '
=- X (V2 VI )(P2 - PI )
2
7. Let a system of gas passes from initial state A to B in
following three ways. The work done by the gas will be
calculated by the shaded area, P V P
A,
~B
V ----II> T ----II> T ----..
(a) (b) (el
Fig.7.13 Isobars of Ideal Gas.
i
P o io
, V----II>
P
T----II>
(b)
The experimental set-up is shown in Fig. 7.15. It consists of a temperature. Most of the gases have inversion temperature near
thermally insulated tube fitted with a porous plug and two about room temperature and thus cool at room temperature when
weightless and frictionless pistons X and Y. Two sensitive expansion is done. However, the inversion temperature for H2 is
thermometers are fitted on both the sides of the porous plug to - 80° C. Thus, at room temperature hydrogen warms on
record temperature. expansion. In order to produce further cooling by Joule-Thomson
Porous plug effect in hydrogen, it is necessary that it should be first cooled to
- 80° Cby either cooling devices.
The value of inversion temperature has been calculated by
using van der Waals' equation, .
2a
T=
, Rb
1
1
I
,
I
I
I
I
~"lfi;''Example 12. Calculate the work done when 50 gof iron is "Ex8ltaple 15. 5 moles of an ideal gas expand isothermally
dissolved in HCl at 25° C in (t) a clo.',ed vessel and (iI) an open and reversiblyfinm a pressure oflOatm to 2atm at 300K. What is
beaker when the atmospheric pressure is I atm. the largest mass which can be lifted through a height ofl metre in
Solution: (i) When the reaction is carried in a closed vessel, this expansion?
the change in volume is zero. Hence, the work done by the system Solution: Work done by the system
will be zero. (ii) When iron dissolves in HCI, hydrogen is p,' P
produced. = - nRT log _I := - 2.303nRT log _-L
e p. p. .
Z 2
Fe + 2HCI ~ FeCI 2 + H2
56g 10
50 g
I mole
=: 2.303 x 5.x 8.314 x 300 log -:= 20.075 X 103 J
2. x 50 mole 2
56
Let M be the mass which can be lifted through a height of 1 m.
Vohnue of hydrogen produced at 25° C
\Vork done in lifting the mass
nRT 50 0.0821 x 298
=-- -x----- 21.84 L
P 56 1 =Mgh = M x 9.8x 11
This is equal to volume change when the reaction is carried in So, M x 9.8 = 20.075 x 10 3
open beaker.
Work done by the system = - P!3.V -l.Ox 21.84 M := 2048.469 kg
21.84 litre -atm = 2212.39 J ~~~EX'ample 16. Two moles of an ideal monoatomic gas at
Example 13. 5 mole of oxygen are heated at constant NTP are compressed adiabatically and reversibly to occupy a
volume from 10° C to 20° C. What will be
the change in volume of 4.48 dm 3 • Calculate the amount of work done, AE,
the internal energy ofgas? The molar heat ofoxygen at constant final temperature and pressure of the gas. C v for ideal gas
pressure, (!p 7.03 cal mol-I deg- I and R 8.3IJ mor l 12.45J K -I mol-I.
deg- I •
Solution: For an ideal gas, y = Cp 1.667
8.31 ca1 mo I-I deg -I Cv
Solution: R 8.311 mol -I deg- I
4.18 Initia!,volume, Vi 2 x 22.4 44.8dm 3
I
= 1.99 cal mol-I deg- Initial pressure, PI = 1atm
We know that, -Cv R Initial temperature, 1] = 273 K
or C v =Cp R = 7.03 1.99= 5.04 cal mol- 1 deg- I Final volume, V2 :::: 4.48dm 3
Heat absorbed by 5 mole of oxygen in heating from 10° C to Let th~ final pressure be P2 and temperature be T2 •
20"C Applying PI V; Y PzV/
5 x C v x!3.T = 5x 5.04 x 10= 252cal
Since, the gas is heated at constant volume, no external work or =: lI'V2)Y (4.48)1.667.
is done, . P2 VI 44.8
£~, w=O
So, change in internal energy will be equal to heat absorbed, . or (10)1.667
!lE q+w 252+ 0= 252 cal
Example 14. Calculate the amount of work done by 2 Pz (1 0i'667 (PI I given)
mole ofan ideal gas at 298 K in reversible isothermal expansion
log P2 = 1.667 log 10= 1.667
from 10 litre to 20 litre.
Solution: Amount of work, done in reversible isothermal Pz antilog 1.667:= 46.45 atm
expansion, 46.45 x 4.48 x 273
Final temperature pzV.2·7'1
1,
Example 17. A certain volume of dry air at NTP is te,mperature 290.0 K. Calculate the final temperature of water .
expanded reversibiy to four times its volume (a) isothermally (specific heat of water = 4.184 JK -I g-I).. (lIT 1993)
(b ) adiabatically. Calculate thefinal pressure and temperature in Solution: Work done P x dV = 3.0 x (5.0- 3.0)
each case, assuming ideal behaviour.
= 6.0 litre -atm = 6.0 x 10 1.3 J
(~; for air = 1.4) . =607.8J
Let IlT be the change in temperature.
Solution: Let VI be the initial volume of dry air at NTP.
Heat absorbed = m xs x IlT
(a) Isothermal expansion: During isothermal expansion,
the temperature remains the same throughout. Hence, final = to.Ox 18x 4.184 x IlT
temperature will be 273 K. . Given, P x dV = mX sX IlT
Since, IlT P x dV _ _ _ _60_7_.8_ _
or 0.807
=0.25atm mXs 1O.0x 18,Ox 4.184
Final temperature 290 + 0.807 = 290.807 K
(b) Adiabatic expansion:
:.> . Example 20. 109 ofargon gas is compressed isothermally
1', (V. J
---.!...=-.-l. y-I and reversibly at a temperature of 27° C from 10 litre to 5 Utre.
Calculate q, w, AE and AIl for this process.
T2 VI
R = 2 cal K -I mol -I , log 2 0.30. Atomic weight ofAr= 4U
14-1
273 = 4VI =40.4 (lIT 1997)
Tz (
VI )
'
Solution:
V.
w = - 2.303nRT log -.-l.
. Vi
. 273
T2 = - = 156.79K 10 5
4°·4 2.303 x - x 2 x 300 log - = 103.635cal
40 10
10
S;:>!"lliJtalD.ple23. A swimmer coming out Of a pool is covetted
2.303 x 1 x ~.314 x 400x 0.3010 . 'witli afllm ofwater weigh in. ftbout 80g.1fow much heat must be
= - 2305.3 J (Work is done by the system) supplied to evaporate this water? .
q = - w == 2305.3 J (Heat is absorbed by the system) Soiution: q = mL
'i,'L~i~_a...ple 19.
A gas expands from a volume of3.0dm3 to = 80 x 40.79
3
5.0dm against a constant pressure of3.0atm. The work done 18
during expansion is used to heat 10.0 mole of water of = 181.28kJ
434 G.R.B. PHY,SICAL
. CHEMISTRY FOR
,
COMPETITIONS
'A\I\Q, THERMOCHE;MISTRY
Thermochemistry is !.t branch of physical c~emistry which is
1. 5 moles of an ideal gas at 27°C ex~ands isothermally and concerned with energy changes accomJpanying chemical
reversibly from a volume of 6 L to 60 L. The work done in kJ transformations. It is also termed as chemical energetics. It is
is: based on the frrst law of thermodynamics.
(a) -14.7 (b) -28.72 (c) +28.72 (d) ~56.72 Chemical reactions are accompanied by evolution or
[Ans. (b)] absorption of heat energy. When reactants combine together to
form new products, there is readjustment of energies. During a
[Hint: W == - 2.303nRT log chemical reaction, the chemical bonds between atoms in the
VI
reactant molecules are rearranged in the product molecules, i.e.,
/ =- 2.303 x 5 x 8.314 x 300 log 60
6
chemical bonds in the reactants are broken down and new
chemical bonds are formed in the products. Energy is needed to
= -28.72 kJ] break the bonds of reactants and energy. is released in. the
formation of new bonds of products.
2. . 10 moles of an ideal gas confmed to a volume of 10 L is
released into atmosphere at 300 K whe,re the pressure is I bar. Exothermic Reactions
The work done by the gas is: Heat is evolved in these chemical reactions. It is possible
(R = 0.083 L bar K -I mol-I) when the bond energy of reactants is less than the bond energy of
(a) 249 L bar (b) 259 L bar (c) 239 L bar (d) 220 L bar products.
[Ans. (e)] . . At constant pressure,
[Hint: Initial volume, VI =10 L !JJI (Hp HR ) -ve, i.e., Hp <HR
V (final) == nRT == 10 x 0.083 x 300 :: 249L At constant volume,
2
p 1 AE=(Ep ER ) ve, i.e., Ep <ER
W =P L\V =I x (249 10)
Endothermic Reactions
== 239 L bar] Heat is absorbed in these chemical reactions. It is possible
3. ·1 litre~atm work is approximately equal to: when the bond energy of reactants is greater than the bond energy
(a) 101.3 J (b) 8.314 J (c) 931 J ( d ) 19.2 J of products. .
[Ans. (a)] At consti,lnt pressure,
[Hint: 0.0821litre-atm == 8.314 J (values of gas constant)
!JJI =Hp - HR + ve, i.e., Hp >HR
:.llitre-atm = 10l.3 J]
4. A system absorb~ 20 kJ heat and also does 10 kJ of work. The. At constant volume,
net internal energy of the system: AE =E pER =+ ve,
(a) increases by lO kJ (b) decreases by 10 kJ Sign conventions:
(c) increases by 30 kJ (d) decreases by 30 kJ AQ AE !JJI
[Ans. (a)] (-) (- )/{-)
Exothermic
[Hint: L\U =)q + w =20 -10 = 10 kJ]
Endothermic (+) (+f (+)
5. One mole of a gas is heated at constant pressure to raise its
temperature by 1'lC. The work done in joules is: Exothermic and endothermic chemical equations can be
(a) 4.3 (b)-8.314 . represented as:
(c) ~16.62 (d) unpredictable NaOH(aq.) + HCI(aq.) ~ NaCI(aq.) + H 2 0(l)
[Ans. (b)] Exothermic ..' + 13.7 kcal
[Hint:' w = -nR L\T or w= -P L\V . { NaOH(aq.) + HCI(aq.) ~ NaCI(aq.) + H 0(l);
2
(or enthalpy of reaction) is actually the difference between the . The difference between the two values is equal to the heat
enthalpies of the products and the reactants when the quantities absorbed when 12 g of diamond is converted into 12 g of
of the reactants indicated by the chemical equation have amorphous carbon. This is termed as heat of transition.
completely reacted. Mathematically,
C (diamond) ----'? C (arriorphous); Ml 3.3 kcal
Enthalpy of reaction (or heat of reaction)
(iii) Enthalpies of solution: Enthalpies of reaction differ
Mf mp -IRR
when in one case dry substances react and in another case when
For example, the equation the same substances react in solution. For example, in the
H2 (g) + CI 2(g) = 2HC1(g) + 44.0 kcal orMf = :.....44 kcal reaction between hydrogen sulphide and iodine, .
indicates that when 2 g of hydrogen ( 1 mole) completely reacts H 2 S(g)+ 12(g)----'?2Hl + S; I1l;I
, = -17.2kcal
with 71 g of chlorine (l mole) to form 73 g ofHCI (2 mole), the
H2 S(g ) + 12 (solution) ----'? 2Hl (solution) + S;
amount of heat evolved is 44.0 kcal or the enthalpy decreases by
44.0 kcal or the reactIng system loses 44.0 kcal of heat or the Mf = _. 21.93 kcal
enthalpy change of the reaction, Mf = - 44.0 kcal. (iv) Temperature: Heat of reaction or enthalpy of reaction
Consider the following reaction: also depends on the temperature at which the reaction is cat:rj.ed
out. This is due to variation in the heat capacity of the system
CZH 4 (g)+ 3°2 (g) = 2CO z + 2H zO(I);!ill = -335.Skcal
with temperature. Due to this reason, entlullpies of reaction are
The equation indicates that reaction has been carried between calculated and expressed at a standard temperature of 25° Cor
1 mole of C2H4 and 3 mole of oxygen at constant volume and 298 K. However,if the reaction is not carried out at 25° C, the
25° C. The heat evolved.is 335.S kcal or the internal energy of the . temperature at which the reaction is performed, is indicated.
system decreases by 335.S kcal. (v) Reaction carried out at constant pressure or constant
Consider another reaction: volume: When a chemical reaction occurs at constant volume,
Os) + H 2 0(g)=CO(g)+ H2 (g) - 31.4 kcal the heat change is called the enthalpy of reaction at constant
or Mf 31.4kcal volume. However, most of the reactions are carried out at
constant pressure; the enthalpy change is then termed as the
This reaction indicates that 1 mole of carbon (12 g) reacts with enthalpy of reaction at constant pressure; The difference in the
1 mole of steam (IS g) to form I mole of CO and I mole of values is negligible when solids and liquids are involved in a
hydrogen and 31.4 kcal of heat is absorbed. The enthalpy of the chemical change. But, in reactions which involve gases, the
. system increases by 31.4 kcal or the total enthalpy of the products difference in two valueS is considerable. For this purpose see
. is 31.4 kcal more than the enthalpy of reactants. section 7.5.
/
Factors which Influence.~he Heat of Reaction !ill+6.nRT=Mf
There are a number of factors which affect the magnitude of or qy + 6.nRT = qp
heat of reaction.
(0 Physical state of reactants and products: Heat energy qv == heat change at constant volume, .
is involved for changing the physical state of a chemical q p = heat change at constant pressure.
substance. For example, in the conversion of water into steam, 6.n = total number of moles of products - total number of moles
heat is absorbed and heat is evolved when steam is condensed. of reactants
Considering the following two reactions: Bcill,aDlple 24. The heat of combustion of ethylene at 18° (:
·1· . and at constant volume is -335.S kcal when water is obtained in
H 2 (g)+ -02 (g)=H 2 0(g); Mf = -57.Skcal liquid state. Calculate the heat of combustion at constant
· 2 ·
pressure and at I'so C.
H 2 (g)+.! 0z(g)= H 20(l); Mf = - 6S.32kcal Solution: The chemical equation for the combustion of
2 C 2 H 4 is
It is observed that there is difference in the value of Mf if C2 H 4 (g)+ 30.3(g)= 2C02 (g) + 2H 2 0(1);!ill= - 335.8 kcal
water is obtained in gaseous or liquid state. Mf value in second I mole 3 moles 2 moles
case is higher because heat is evolved when stearri condenses. No. of moles of reactants =(1 + 3) = 4
Hence, physical state always affects the heat of reaction. .
No. of moles of products = 2
(il) AUotropic forms of the element: Heat energy is also
involved when one allotropic form of an element is converted So, 6.n = (2 - 4) = - 2
into another. Thus, the value of MI depends on the allotropic Given,!ill = - 335.Skcal, 6.n 2, R 2x 10-3 kcal
form used in the reaction. For example, the value or'Mf is
and T (1S + 273) = 291 K
different when carbon in the form ofdiamond or in amorphous
form is used. Applying Mf = llE + 6.nRT
C (diamond) + 02 (g) ----'? CO 2(g ); Mf = '- 94.3 kcal =-335.S+ (-2)(2 x 10-.3 )(291)
C (amorphous) + 02 (g) ----'? CO 2 (g); Mf 97.6kcal == -336.964 kcal
436 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
i1ftil"lPple 25. The enthalpy of formation of methane at The knowledge of standard heats _.. <onnation of various
constant pressure and 300 K is -75.83 kJ. What will be the heat of substances can be used to calculate the heats of reactions under
formation at constant volume? (R = 8.3 J K -I mol -1 ) standard conditions, i. e. ,~ .
Solution: The equation for the fonnation of methane is 'AHO for' [swnof thestan?ard] [swnof thesta~d]
. = heats of formation - heats of formation
C(s)+ 2H 2 (i) CH4 (g); AH", -75.83 kJ the reaction
2 moles 1 mole of products of reactants
formation is called standard heat of formation or standard AHo ':" AHf (products) - AHf (reactants)
f
enthalpy of formation. It is denoted by M (volume constant) =[AHf (C02) + 2AHf (H:P) ] [AHf (CH4) + 2AHf (02) ]
f
or!1H (pressure constant). ;:= [-393.5+ 2x(-286.2)] [-74.8+ 2x 0]
It is very difl1cult to determine absolute values of enthalpies of = - 393.5 - 572.4 + 74.8
substances. However, relative enthalpies, of substances can be = -891.1kJ
determined if the enthalpies of free elements at 25° C and I
~,~j:#.nple 27. The standard heats offormation at 298 Kfor
atmospheric pres.sure are taken arbitrarily as zero.
CCI4 (g),H 20(g),C02(g)andHC1(g) are -25.5, -57.8,-94.1
. Consider th~ reaction between carbon and oxygen at 25° Cto
form carbon dioxide under atmospheric pressure. and-22.1 kcal mol-l respectively. Calculate L1H~98 for the
reaction.
C(S)+02(g.)=C02(g); AH=AHf ==-393.5kJ
,
'/
are called endothermic compounds and are less stable than the ;:= [-94.1 + 4 x (- 22.1)] [- 25.5 + 2x (- 57.8)]
reactants.' The compounds which have negative enthalpies of =-94.1-88.4+25.5+ 115.6
formation are known as, exothermic compounds and are more
stable than reactants. = -182.5+ 141.1 = 41.4 kcal
CHEMICAL THERMODYNAMICS AND,THERMOCHEMISTRY 1437
~~;f:~~\E~ample 28. The molar heat offormation ofNH4N03 (s) These substances are, therefore, termed as fuels. An adult
is -367.5kJ and those ofN zO(g )and H 20(1 ) are + 8 1.46 kJ and requires 2500 to 3000 kcal of energy per day. Since, the values of
-285.78 kJ respectively at 25°C and 1 atmospheric pressure. enthalpies of combustion of different food articles are known; it
Calculate the All and IlE for the reaction, becomes easy to calculate our daily requirements and thus select
the articles ~f food so as to secure a balanced diet.
NH4N0 3 (s) ----" N 20(g) + 21120(1 )
The grading of food articles and various fuels can be done on
Solution: AlI° All! (products) - All! (reactants) the basis of the values of enthalpies of combustion.
The energy released by the combustion of foods or fuels is
=[AlIf (N;P) + 2x AlIf (H;P}] - [All! (NH4N03)] usually compared in terms of their combustion energies per gram.
It is known as calorific value. Tbe amount of beat produced in
'" 81.46+ 2x (-285.78) (-367.5) calorie or joule wben one gram of a substance (food or fuel) is
= 81.46- 571.56+ 367.5 completely burnt or oxidised.
-122.56 kJ When methane bums, 890.3 kJ 11101-1 of energy is released.
We know that, All IlE + AnRT CH4 (g) + 202 (g ) ----" CO 2 (g) -+ 2H z0(1),
1 mole(16g)
or IlE All AnRT
AHrn4 ':"- 890.3 kJ
An = I; R = 8.314 X 10-3 kJmol- 1 K- 1 ; T = 298K
IlE =-122.56 - (l )(8.314 X 10-3 )(298) So, the calorific value of methane:::: - 890.3 :::: - 55.6 kJ/ g
16
:::: -122.56 - 2.477 Caiorific values of some important foodstuffs and fuels are
iven below:
=-125.037kJ
FUel " Calorftte, value (kJ/g) " ~FoOd Ciiloflfle value (kJ/iJ:::
"~if:3'~ ENTHALPY OF COMBUSTION OR Wood 17 Milk 3.1
HEAT OF COMBUSTION Charcoal 33 Egg 6.7
Enthalpy of combustii.)U is the amount of heat evolved or Kerosine 48 Rice 16.7
decrease in enthalpy when 1 mole of the substance (compound or Methane 55 Sugar 17.3
element) is completely oxidised. The enthalpy of combustion, LPG 55 Butter 30.4
i. e., All is always negative. For example, H dro en 150 Ghee 37.6
CH4 (g) +,20~ (g) ----" CO 2 (g) + 2H 2 0; Out of the fuels listed, hydrogen has the highest calorific
All = - 890.3 kJ value; H;owever, it is not used as domestic or industrial fuel due to
C2 Hs OH(I) + 30 z (g) ----" 2COz (g) + 3H2 0( I); some technical problems. Of the various constituents of our food,
fats and carbohydrates serve as the main sources of energy. The
All :::: - 1367.4 kJ
calorific value of proteins is quite low.
2Cz H6 (g) + 70 z (g) ----" 4COz (g ) + 6H2 0(l); (U) Entbalpies of formation: Enthalpies of formation of
All = -745.6kcal , various compounds, which are not directly obtained, can be
Since, 2 mole of CzH6 are involved, hence enthalpy of calculated from the data of enthalpies of combustions easily by
combustion of ethane the application of Hess's law.
:::: _ 745.6 _ 372.8 kcal Heat of reaction == 1: Heat of combustion of reactants
2 - 1: Heat of combustion of products
1 ,
C(s)+ 2 °2(g)----"CO(g);AH=-26:0kcal,
/
438 G.R.B .. PHYSICAL CHEMISTRY FOR COMPETITIONS
ii!Jt;,*a...ple 30. In a Gobar gas plant, gobar gas is formed by AH = AHI (products) - ' AHI (reactants)
bacterial fermentation of animal refuse . .It mainly 'contains
methane and its heat of combustion is -809 kJ mol ~l according [AHI(A1ZO) +2AHI (Fe)]-[2AHI (A1) + AHJ(FcZ0 3)j
to follOwing equation: = (-399+ 2 X 0)- [2x 0+ (-199)]
CH4 +202 ~COz +2HzO; AH=-809kJmor l = - 399+ 199= -200kcal
How much gobar gas would have to be produced per day for a At. mass of aluminium = 27, Mol. mass of Fez 0 3 = 160
small village of 50 families, if it is assumed that each family
requires 20,000 kJ of energy per day? The methane content in Volume of reactants 160 + 2x27 =50.77cm3
gobar gas is 80% by mass. S.2 2.7
Solution: Energy consumption of 50 families per day
Fuel value per cm 3 = 200 = 3.92 kcal
50 x 20,000 kJ = Ix 106 kJ SO.77
. 809 kJ of energy is obtain~d by h.urning methane =16 g r~l{E~ample 33. When 2 mole ofC zH 6 are completely burnt,
I x 106 kJ of energy will be obtained by burning methane 3129 kJ of heat is liberated. Calculate the heat offormation' of
C ZH 6 • AHI forCO z and HzOare -39SkJ and -286kJ respec-
16 x 106 = 1.98 x 104 g tively.
809 Solution: The equation for the combustion of C z H6 is:
= 19.8 kg
2C z H 6 +70 z ~4C02 +6Hz O; AH=-3129kJ
Since, methane content in gobar gas is 80% by mass, hence,
the mass of gobar gas needed . AH AHI (products) - AHI (reactants)
100 =[4x AHI (C02) +6x AH(Hp)]-[2x tlHI (CZ H 6)
= - x 19.8= 24.7Skg
80,
+ 7 AHI (02)]
~jample31. The standard molar heats of formation of
ethane, carbon dioxide and liqUid water are -21.1, -94.1 and -3129=[4 X (-39S)+ 6x (-286)] [2x AHf{C2H o) + 7x 0]
. - 68.3 kcal respectively. Calculate the standard molar heat of or 2 x AHf(C2H6) = -167
combustion ofethane. .
Solution: The required chemical equation for combustion So, AH - 167 = - 83.5 kJ
I (C2H 6) 2 .
of ethane is
2C z H6 (g)+ 702 (g) 4COz (g) + 6H zO(I); tlHo =? ~;;E:Jiample 34. The standard heats oJformation ofCH4 (g ),
COz~g) and H 20(g) are -76.2, -398.8 and -241.6 kJ mol ~I
The equation involves 2 moles ofCzH 6 ; heat of combustion
AHo r(!spectively. Calculate the amount ofheat evolved by burning 1m 3
of ethane will be
2 ofmethane measured under normal conditions. (lIT 1990)
Solution: The required equation for the combustion of
AHo = ~(products) - ~(reactants) methane is:
Solution: C 2H4 + 302 ---72C0 2 + 2H 20 equivalent of an acid is neutralised by 1 gram equivalent of a base
a litre 2a litre in dilute solution. Some examples are:
CH 4 + 202 ---7 CO 2 + 2H 20 Strong acid +,Strong base = Salt + Water; Mf = -13."7 kcal
~ .
(3.67 - a) litre (3.67 - a) litre HN0 3 (aq.) t ~ilOH(aq.) = NaN0 3 (aq.) + H 20(/);
Given, 2a + 3.67 - a = 6.11 Mf = -13.7 kcal
HC1(aq.) + NaOH(aq.) = NaCl(aq.) + H 2 0(/); .
a = 2.44 litre
Mf = -13.75 kcal
Volume of ethylene in mixture = 2.44 litre
1 1
- H 2S0 4(aq.) + NaOH(aq.)=- Na2S04(aq.) + H20(/);
Volume of methane in mixture = 1:23 litre 2 2 .
Mf = -13.7kcal
Volume of ethylene in I litre mixture = 2.44 = 0.6649.1itre
3.67 It is observed that heat of neutralisation of a strong acid
against a strong base is always nearly the same, i.e., 13.7 kcal or
Volume of methane in llitre mixture = 1.23 = 0.335i litre 57 kJ, no matter what acid or base is employed. This constant
3.67
value is explained with the help of theory of ionisation. Both acid
24.45 litre of a gas at 25° Ccorrespond to 1 mole. and base are present in aqueous solution in the form of ions and
Thus, heat evolved by burning 0.6649 litre of ethylene when mixed, the following reaction oCcurs:
= - 1423 x 0.6649 = - 38.69 kJ H+ +A- + B+ +OH- B+ +A- +H 0; Mf=-13.7kcal
24.5 2
Strong acid Strong base Salt
and heat evolved by burning 0.3351 litre of methane
Cancelling the ions which are common on both the sides,
=_ 891 x0.3351=-12.21kJ H+ +OH- =H 20; Mf=-13.7kcal
24.45
So, total heat evolved by burning 1 litre of mixture Thus, beat of neutralisation of a strong acid and a strong
base is merely the heat of formation of water from H + and
=-38.69- 12:21
OH- ions. This is the common reaction whenever a strong acid
=-50.90kJ and a strong base are mixed and that is why the heat of
neutralisation is same.
7.1.4 ENTHALPY OF SOLUTION OR HEAT However, when a strong acid and
a weak base or a weak acid
OF SOLUTION and a strong base or a weak acid and a weak base are mixed in
The amount of heat evolved or absorbed when 1 mole solute is equivalent amount, the heat evolved or change in enthalpy is less
dissolved in excess of solvent (about 200 mole) is called heat of than 13.7 kcal. This is shown in the following examples:
solution. HC1(aq.) + NH 4 0H(aq.)= NH 4 Cl(aq.) + H 2 0(l);
Strong Weak
Some examples, of heat of solution are: Mf = -12.3 kcal
H 2S04 (/) + aq. = H2S0 4(aq.); Mf = - 20.2 kcal
HCN(aq.) + NaOH(aq.) = NaCN(aq.) + H 20(l);
KC1(s) + aq. = KC1(aq.); Mf= 4.4 kcal Weak . Strong
Mf = -12.3 kcal
KOH(s) +aq. = KOH(aq.); Mf = -13.3 kcal
Heat of ideal solution is taken zero. CH 3 COOH(aq.) + NH 4 0H(aq.) =CH 3 COONH 4 (aq~) +H 20(l);
Weak Weak .
Generally, dissolution of substances in a solvent is a Mf= -11.9 kcal
disintegration process. This process needs energy. In such cases,
energy is absorbed, i. e., Mf is positive. But in some cases, The reason for the lower value is that part of the heat energy
besides the process of breaking or ionisation, there is hydrate evolved is utilised in the complete ionisation of a weak acid or a
formation. During hydration heat is evolved. The net result is that weak base or both. Hence, the net heat of neutralisation is less
heat is either evolved or absorbed. There are also cases in which than 13.7 kcal. The neutralisation of NH 40H withHCl can be
heat of separation of ions is just equal to the heat of hydration and explained in the following way:
there is very little heat effect as in the case of sodium chloride. NH 4 0H(aq;)=NH; (aq.) + oir (aq.); Mf =Q
The heat of solution of NaCl is very small as the heat of and NH; (aq.) + Cl- (aq.) + H+ (aq.) + OH- (aq.)=NH; (aq.) .
ionisation is nearly equalto the heat of hydration.
+ Cl- (aq.) + H20(l);
'1~~5 ENTHALPY OF NEUTRALISATION OR Mf =-13.7kcal
HEAT OF NEUTRALISATION or NH 4 0H(aq.) + H+ (aq.) + Cl- (aq.) =NH; (~q.)+ Cl- (aq.)
x sp. heat x (T2 -11 ) (iii) 100 mL of 0.2 M HCl will give
Q is the heat evolved by the neutralisation.
0.2 x 100J = 0.02 mole of H + ions
. ( 1000
Therefore, the enthalpy of neutralisation:::: x 1000 x .!
. 100 x
and 100 mL of 0.3 M NaOH will give
where, x =normality of the acid or base.
I:~riaple 36. 150 mL of 0.5 N nitric acid solution at 0.3 x 100) 0.03moleofOH- ions
25.35°C was mixed with 150 mL of 0.5 N sodium hydroxide 1000
solution at the same temperature. The final temperature was
recorded to be 28.77° C. Calculate the heat of neutralisation. of i.e., 0.02 mole ofH + ions react with 0.02 mole ofOH ions to'
nitric acid with sodium hydroxide. fonn 0.02 mole of water molecules.
Solution: Total mass of solution =150 + 150 300 g Heat evolved in the formation of 0.02 mole of water
Q= Total heat produced:: 300 x (28.77 25.35)cal ==0.02x 57.1= 1.142kJ
= 300 x 3;42 1026cal (iv) 400mLofO.2M H2 S04 will give
.
S?-
Heat of neutralisation ::::
150
x I 000 x I
0.5 x 0.2 x 4001 =O.l6moleof H + ions
1000 )
1026 I
== - - x 1000 x - ::: 13.68 kcal
150 0.5 and 600 mL of O. 1M KOH will give
•
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 441---"
x+ y
(~X6001
1 ... (i)
0.06moleofOH ions
1000 .) x x 13.7 + yx 12.7= 13.5
Solving eqs. (i) and (ii), we get
.... (ii)
HCI(aq.) + NaOH{aq. ) ~ NaCI(aq.) + H 20{aq. ) Enthalpy of vaporization of a liquid gives an idea about the
strength of intermolecular forces operating' between the
Solution: (a) Number of moles ofHCI and NaOH added
molecules Of the liquid. .
MV = I x 50 = 0.05 (iii) Enthalpy of sublimation: Sublimation is the process
1000 1000 in which a solid on heating is directly converted into vapour state.
Mass of mixture· = V x d 100x 1= 10~g It is the heat change in converting 1 mole of a solid directly into
Heat evolved, q ms AT = 100 x 4.18 x (27.5 - 210) its vapour at a given temperature below its melting point.
12(s)~ 12 (g); AH = 14.9kcal
= 100 x 4.18 x 6.5J = 2717 J =2.717 kJ
The enthalpy of sublimation of a solid is equal to the sum of
(b) The involved reaction is: enthalpy of fusion and enthalpy of vaporization.
HC1(aq.) + NaOH(aq.)~NaCl(aq.)+ H 2 0
AHsublimation AH fus + AH vap
AH Heat evolved per mol
-2.717 =-54.34kJ l<i11: HESS'S LAW (The Law of Constant
0.05 Heat Summation)
.LExample 40. The enthalpies of neutralisation of a strong This law was presented by Hess in 1840. According to this
acid HA and weaker acid HB by NaOH are -13.7 and -12.7 law, if a chemical reaction can be made to take place in a
kcal/eq. When one equivalent of NaOH is added to a mixture number of ways in one or in several steps, the total enthalpy
containing I eqUivalent ofHA and HB ; the enthalpy change was change (total heat change) is always the same, i. e., the total
-13.5kcal. In what ratio is the base distributed between HA and enthalpy~change is independent of intermediate steps involved
HB? .
in the change. The enthalpy change of a chemical reaction
So.lution: Let x equivalent ofHA and yequivalent ofHB are depends on the initial and final stages only. Let a substance A
taken in the mixture be changed in three steps to D with enthalpy change from A to
442 G.R.B. PHYSICAL. CHEMISTRY FOR COMPETITIONS
B Mfl calorie, from B to C Mf 2 calorie and from C to D Mf3 (ii) For the determination of enthalpies of extremely slow
calorie. Total enthalpy change from A toD will be equal to the reactions.
sum of enthalpies involved in various steps. (iii) For the determination of enthalpies of transformation of
Total enthalpy change one allotropic form into another.
Mf steps Mfl + Mf2 + Mf3 (iv) For the determination of bond energies.
Mfreaction =k Bond energies of reactants
Now if D is directly converted into A, let the enthalpy change
- k Bond energies of products
be Mfdirect. According to Hess's law Mf steps + Mf direct = 0, i. e. ,
(v) For the determination of resonance energy.
Mfsteps must be equal to Mf direct numerically but with opposite
sign. In case it is not so, say Mfsteps (which is negative) is more (vi) For the determination oflattice energy.
than Mfdirect (which is positive), then in one cycle, some energy Thermochemical calculations: For making thermochemical
will be created which is not possible on the basis of first law of calculations, the following points are kept in mind: .
thermodynamics. Thus, Mf steps must be equal to Mf direct (i) Write down the required thermochemical equation. For
numerically. example, if heat of formation of methane is to be
Hess's law can also be verified experimentally with the help of determined, write down the following equation:
following examples: C(s)+ 2H2 (g)= CH4(g); Mf=?
(i) Formation of carbon dioxide from carbon: (ii) Try to obtain the required equation from the given data.
First method: Carbon is directly converted into CO 2 (g). This can be done in two ways:
(a) By adding, subtracting and multiplying the various
C(S) + 02(g) = CO 2 (g); A H =-94.0kcal given thermochemic!l1 equations. Or
Second method: Carbon is first converted into CO(g) and (b) Heat of reaction:::: Total enthalpies of products - Total
then CO(g) into CO 2 (g ), i. e. ,conversion has been carried in two enthalpies of reactants
steps: Note: In case of calculation of heat of fonnation, the enthalpies of free
1 elements can be arbitrarily fixed as zero at 25 0 C and 1
C(s) + - 02 = CO(g); Mf = - 26.0 kcal
2 atmospheric pressure.
I \,.J!:~mple 41. Calculate the standard heat offormation of
CO(g) + - 02 = CO 2 (g ); Mf = - 68.0 kcal carbon disulphide (I). Given that the standard heats of
2 ,
combustion of carbon (s), sulphur (s)and carbon disulphide (I)
'Totalenthalpy change C(s) to CO 2 (g); . Mf:::: -94.0kcal are -393.3,293.7 and -1108.76 kJ mol -\ respectively.
(ii) Formation of ammonium chloride from ammonia and Solution: Required equation is
hydrochloric acid: C(s)+2S(s) CS 2 (1); Mfl =?
First method: Given,
NH3 (g) + HCI(g) = NH4 CI(g); "'Mf 42.2 kcal
NH4 Cl(g ) + aq. = NH4 CI( aq.); Mf "" + 4.0 kcal
C(s)+ °2 (g)---+ CO2(g) (Mf= -393.3 kJ) ...(i)
S(s) + 02(g)---+ S02(g) (Mf:::: - 293.72 kJ) ... (ii)
NH3 (g) + HCl(g) + aq. = NH4 CI(aq.); Mf :::: - 38.1 kcal
CS z(I) + 302 (g) CO 2(g)+ 2S02 (g) ...(iii)
Second method:
(Mf :::: -1108.76 kJ)
NH3 (g) + aq. = NH3 (aq.); Mf 8.4kcal
HCl(g) + aq. = HC1(aq.); =
Mf -17.3 kcal
First method: Multiply the eq. (ii) by 2.
NH3(aq·) + ijCl(aq. )=NH4 CI(aq.); Mf "" -12.3 kcal 2S(s) + 202 (g) 2S0 2 (g) ... (iv) (Mf:::: - 587.44 kJ)
NH3 (g)+ HC1(g) + aq.=NH 4 CI(aq.); Mf 38.0kcal Adding eqs. (i) and (iv) and subtracting eq. (iii),
[c(s) + 2S(s) + 302 (g) CS 2 (I) - 302 (g)
Conclusions
CO2 (g) + 2S02 (g)- CO 2 2S02 ]
(i) The heat of formation of compounds is independent of
C(s) + 2S(s) ---+ CS 2 (I)
the manner of its formation.' .
This is the required equation.
(ii) The heat of reaction is independent of the time consumed
in the process. . Thus, Mf( =-393.3 587.44+1108.76::::128.02kJ
. (iii) The heat of reaction depends on the sum of enth~pies of Standard heat of formation of CS 2 (l ) = 128.02 kJ
products minus sum of the enthalpies of reactants. Second method:
(iv) Thermochemical equations can be added, subtracted or C(s) + 02 (g) ---+ CO2 (g); (Mf:::: - 393.3 kJ) ... (i)
mUltiplied like algebraic equations. S(s) + 02 (g) ---+ S02 (g); (Mf:::: ~ 293.72 kJ) ... (ii)
Applications of Hess's Law CS 2 (I) + 302 (g) ---+ CO 2 (g) + 2S02 (g);
(Mf::; -1108.76 kJ) ... (iii)
(i) For the determination of enthalpies of formation of those
compounds which cannot be prepared directly from the From eqs. (i) and (ii),
elements easily using enthalpies of combustion of Enthalpy of CO 2 == - 393.3 kJ
compounds. Enthalpy of S02 "" - 293.72 kJ
I
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 443
The heats offormation ofCaO(s), CaC 2 (s) and CO(g) are bond. The energy required to. break the bond is termed bond
-151.6, -14.2 and -26.4 kcal respectively. dissociation energy. The more precise definition is:' .
The amount of energy required to break one mole of bond of a
Solution: Ml = L MI'f (products) - LMI'f (reactants)
. particular type between the atoms in the gaseous state, i.e., to
separate the atoms in the gaseous state under I atmospheric
=[Mtf (CaC2) + Mtf (CO) ] - [MfJ (CaO) + 3A H'f (C) ]
pressure and the specified temperature is called bond dissociation
=[-14.2- 26.4]- [-151.6+ 3x 0] energy. For example,
= -40.6+ 151.6= 111.0 kcal H-H(g)~2H(g); MI = + 433 kJmol- 1
For formation of 64 g of CaC2 111.0 kcal of heat is required. CI- Cl(g) ~ 2CI(g); MI = + 242.5 kJ mol- 1
So, heat required for making 2000 g of .
H - Cl(g) ~ H(g) + CI(g ); MI =+ 431kJ mol- 1
CaC2 111.0 x 2000 = 3468.75 kcal
64 I-I(g)~21(g); MI + 15.1kJmol- 1
H-I(g)~H(g)+ I(g); MI ~ + 299 kJ mol-'
"i.ij:lINFLUENCE OF TEMPERATURE ON
.. THE HEAT OF REACTION The bond dissociation energy of a diatomic molecule is also
called bond energy. However, the bond dissociation energy
OR
depends upon the nature of bond and also the molecule in which
KIRCHHOFF'S EQUATION the bond is p;resent. When a molecule of a compound 'contains
Let us consider a reaction occurring at constant pressure. Heat of more than one bond of the same kind, the average value of the
reaction at constant pressure may be given as: dissociation energies of a given bond is taken. This average
MI=Hp -HR bond dissociation energy required to break each bond in a
eompound is called bond energy.'"
Differentiating the above equation with respect to 'T' at
Consider the dissociation of water molecule which consists of
constant pressure, we get:
MlT2 MIT, ACp (T2 - T,) one-third of the energy of dissociation ofNH3 and those ofC-H
AN AN
bond in CH4 is equal to one-fourth of the energy of dissociation
T2 TI =AC p ofCH 4·
Tz - Tl · . 1664
Bond energy C-H=-- =416kJmol- 1
Above equation is Kirchhoff's equation. It is. used to 4
calculate heat of reaction at a temperatufe provided it is known at [CH4(g)~C(g)+ 4H(g); MI = 1664 kJrnol- 1 ]
another temperature.
Change in heat of reaction due, Ito per degree change in Application of Bond Energy
temperature is equivalent to heat capacity difference between 1. Heat of a reaction = L Bond energy of reactants .
reactant and product.' I
L Bond energy of products
Kirchhoff's equation at constant volume may be given as:
Note:· In case of atomic species, bond energy is replaced by heat of
AE -AE
T2 TI =AC v atomization.
. Tz -Tl 2. Determination of resonance energy: When a
compound shows resonance, there is considerable difference
'j;'~i. BOND ENERGY OR BOND ENTHALPIES between the heat of formation as calculated from bond energk~.::...,
and that determined experimentally.
When a bond is formed between atoms, energy is released. Resonance energy. = Experimental or actual heat of formation
Obviously same amount of energy will be required to break the - Calculated heat of formation.
"'Bond energy isalsQcalled, theheatoffortnation of the bond from gaseous atoms constituting the bond with reverse sign.
H(g)+ Cl(g)~H~Cl(g); All =-431kJmoF 1
Bond energy ofH--:-Cl=.;.. (enthalpy offonnation) = - (- 431) =:; + 431 kJ mol-I
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 445
Solution:
,; :::::I_SOME SOLVED EXAMPLES\ I:::::: H
(All the products are free atoms) Bond energy of N ==N, N =N, 0=0 and N =0 bonds is
946,418, 498and607 kJmol-1 respectively. (lIT 1991)
= 2x 415+ 2x 326
= 830+ 652= 1482kJ . Solution: N=N(g)+ ~ (O=O)~ N=N=O(g)
2 '
'3;~: :E:i~niple 48. Calculate the enthalpy of the following'
reaction: 1
Mf !(NfJ) = [Mf(N==N) + '2 Mf(O=4))] - [Mf(N=4)) + Mf(N=N)]
H2C=CH2(g)+H~(g)~CH3 -CH3(g)
1
The bond energies of C-H, C-C, C = C and H-H are 99, = (946+ - x 498) - (607 + 418)
2
83,147 and 104 kcal respectively.
= 946+ 249-607- 418
Solution: The reaction is:
H H H H = 1195 - 1025 = 170 kJ mol-I
7. MI; 298 K of methanol is given by the chemical equation: PC1 3 (l) + Cl z (g) ~ PCls (s); ill = -137 kJ
(AIIMS 2005) The value of Mlf of PC Is is:
I
(a) CH4(g) + - 0z(g) ------7 CH30H(g) (a) 454.5 kJ mol- l (b) - 454.5 kJ
2 . (c) -772 kJ mol- l (d) - 498 kJ mol- l
(b) C (graphite) + ..!. 0z (g ) + 2H2 (g ) -'-------7 CH30H(l) [Ans. (b)]
2 . 1 3 635
[Hmt: - P4(s) + - CI 2(g) ~ PCIs(l); I1Jl = - - kJ
(c) C (diamond) +..!. 02(g) + 2H2(g) ------7 CH30H(I) 4 2 2
2
PCI 3 (1) + CI 2(g) ~ PCIs(s); I1Jl = -137 kJ
(d) CO(g) + 2H2(g) ------7 CH30H(l)
[Ans. (b)]
[Hint: In the process of formation, the compound must be On adding,.!. P4(s) + ~ CI 2(g) ~ PCls(s); I1Jl = -454.5 kJ]
4 2
formed from constituent elements in their standard state.]
8. The standard molar heat of fonnation of ethane, CO 2 and H2 ° 12. The enthalpy of combustion at 25°C of H2, cyclohexane
(I ) are respectively -21.1, -94.1 and --68.3 kcal. The standard (C6H12 ) and cyclohexene(C6HIO) are -241, -3920 and
molar heat of combustion of ethane will be: -3800 kJ/mol respectively. The heat of hydrogenation of
(a) -372 kcal (b) -240 kcal cyclohexene is: [CBSE (Med.) 2006]
(c) 162 kcal (d) 183.5 kcal (a) -121 kJ/mol (b) +121 kJ/mol
[Ans. (a)] (c) -242 kJ/mol (d) +242 kJ/mol
, 7 [Ans. (a)]
[Hint:. C2~(g) + - 02(g) ~ 2C0 2(g) + 3H20(g)
2 [Hint: H2(g)+.!.02(g)~H20(1) (11Jl=-241kJ) ... (i)
2
I1H = 2I1Jlf (CO z) + 3I1H.f(HzO) - I1JlJ (CZ H6) 17
= 2(-94.1) + 3(-68.3) -
(-211) = - 372 kcal] C6HlO + "2 °2(g) ~ 6C0 2(g) + 5H 20(l) ... (ii)
9. When ethyne is passed through a red hot tube, then fonnation (11Jl = - 3800 kJ)
of benzene takes place: C6Hl2 + 90 2(g) ~ 6C0 2(g) + 6H 20(I) ... (iii)
l (11Jl = - 3920 kJ) .
ill; (C2H 2)(g) = 230 kJ mol-
Eq. (i) + eq. (ii) - eq. (iii) gives
l
ill; (QjH 6)(g) = 85 kJ mol- I1Jl = - 241- 3800 - (-3920) =-121 kJ
Calculate the standard heat of trimerisation of ethyne to for C6HlO + H2 ~ CJI12]
benzene. 13. Given that:
3CzH z (g) ~ C 6H6 (g) 2Fe(s) + ~ 0z (g) ~ Fe203 (s) (ill =-193.4 kJ) ... (i)
(a) 205 kJ morl (b) 605kJ mol- l 2
(c) - 605 kJ mol- l (d) -205 kJ mol- l Mg(s)+..!. 0z(g)~MgO(s)(ill=-140.2kJ) ... (ii)
[Ans. (c)] 2
[Hint: I1Jlreaction = 11Jl;(Q, H6) - 311Jl;(CzH z) What is MI of the reaction?
3Mg + Fe Z 0 3 ~ 3MgO+ 2Fe [JEE (Orissa) 2005)
= 85 - 3(230)
(a) ~227.2 kJ (b) -272.3 kJ
= - 605 kJ mol-I] (c) 227.2 kJ (d) 272.3 kJ
10. F2 (g ) + 2HCI(g ) ------7 2HF(g) + Cl 2(g ); [Ans. (a)]
[Hint: Subtracting equation 1st from 2nd multiplied by 3,
MfO = - 352.18 kJ 3
2Fe(s)+ "2 0z(g) ~ Fez0 3(s)
Mf; (HF) = - 268.3 kJ
3
(11Jl ; -193.4 kT) ... (i)
The heat of fonnation ofHCl will be: 3Mg(s) +"2 02(g) ~ 3MgO(s) (11Jl = -420.6kJ) ... (ii)
(a) -22 kJ mol- l (b) 88 kJ mol-I
Subtracting eq. (i) from (ii),
(c) -92.21 kJ mol- l (d) -183.8 kJ mol- l
[Ans. (c)] 3Mg(s) + Fez03 ~ 3MgO + 2Fe; I1Jl = -420.6 - (-193.4)
= -227.2 kJ]
•
448 'G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
22. Calculate the enthalpy of fonnation of I1Hf for C2 HsOH 26. The bond energies of C= C and C-C at 298 K are 590 and
from tabulated data and its heat of combustion as represented 331 kJ mol-1 re~pectively. The enth~lpy of polymerisation
by the following equations: per mole of ethylene is:
H2 (g)+ ~02(g) H 20(g) ... (i) (a)-70kJ (b)-12kI (c)12kI (d)-68kJ
(MIo -2418kJ mol-I) [Ans; (b)]
cO 2 (g) ... (ii) [Hint: The polymerisation of ethene may be represented as
(l1Ho 393.5 kJrnol- l ) nCH2 CHz -f-CH z -- CH z +/1
3H2 0(g)+2C02 (g) ... (iii) one mole ofC C bond is decomposed and two molt;s ufC----C
(MIo = -1234.7 kJ) bonds are formed per mole of ethene.
(a) -2747.1 kJ mol-I (b) -277.7 kJ mol- 1 :. AH = 590 2 x 331 -72 kJ per mol of ethylene.]
(c) 277.7 kJ mol- 1 (d) 2747.1 kJ mol-I 27. For the reaction,
[ADS. (b)] 2H2(g)+02(g) 2H2 0(g); 11H=-571kJ
[HiDt: Required equation: bond energy of (H-H) 435 kJ; of (0==0) = 498 kJ; then
2C(s) + 3H2 (g) + Yz02(g) C2H sOH(l) calculate the average bond energy of (O-H) bond using the
above data. (DeE 2005)
2C(s) + 20 2(g) 2CO z(g); AHO = -2 x 393.5kJ (a) 484 kJ (b) - 484 kJ (c) 271 kJ (d) -271 kJ
3 [Ans. (a)]
3H2(g) +
2
02(g) ---dHz0(g); AHo
.
=- 3 x 241.8 kJ
[Hint: 2(H--H) + 0 =0 2(H-O-H)
3HP(l) + 2C02(g) ---7 C2H sOH(l) + 30 2 (g); I1H ~(BE)reaclants ~(BE)prndl1CtS
AHo ::: + 1234.7 kJ -571 == [2 x 435 + 498] 4 x (BE)o_H
2C(s) + 3H2 (g) + I 02(g) ---7 CzHsOH(I); 28. Use the bond energies in the table to estimate I1H tor this
2 reaction:
AHo = -277.7 kJ mol-I CH2= CH2+ CI 2 ---7 CtCH2 - tHCl 2
23. . Which of the following methods for calculation of heat of a Bond. C-C C=C C-Cl C-H O-Cl
reaction is not correct?
Bond energy 347 612 331 414 243
(a) I1H reaction ~ I1HJ products ~ 11H,. reactants
(kJ/mol)
(b) I1H reaction ~(BE)reacrants ~(BE)producls
(c) I1H reaction ~l1Hcomb. (reactants) ~l1Hcomb. (products) (a) I1H = - 684 kJ (b) I1H =-154 kJ
(d) I1H reaction ~solution (reactants) ~11Hsolution (products) (c) I1H =+ 89 kJ (d)11H +177kI
[ADS. (d)] [Ans. (b)]
24. Heat of combustion of diamond and graphite are -94.5 kcal [Hint:
and -94 kca1!mol respectively. What will be the heat of AHreaction ~(BE)rcactant' - ~(BE)prnducts
transition from diamond to graphite? [(BEk=c + 4(BEk_H + (BE)Cl_C1]
(a) 0.5 kcal (b) +0.5 kcal (c) 1 kcal (d)-1 kcal
- [4(BEk_H + 2(BE b_Cl + (BE)c_c]
[Ans. (b)]
[(BE)c=c + (BEkl_C1] - [2(BEk_cl + (BEk_cl
[Hint: AH AH ""mb. IdialOOnd) - AH comb. (graphite)]
[612+243] [2x331+347]=-154kJ]
25. For the reaction,
~9. Heat of tormation of 2 moles of NH] (g J is -90 kJ; bond
3N zO(g) + 2NH3 (g) ---7 4N2 (g ) + 3H2 0(g);
M-fO = -: 879.6 kJ energies of H-H and N-H bonds are 435. kJ and 390 kJ
mol-I respectively. The value of the bond energy of N == N
If 45.9 kJ rnol- I ;
will be:
I1Hj[ H 20(g)] -:24L8kJrnol- 1 (a) 412.5 kJ (b) - 945 kI (c) 412.5 kJ (d) 945 kJ mol-I
then I1Hj[N20(g)] will be: [Ans. (d)]
H
(a) +246 kJ (b) +82 kJ' I
(c) -82 kJ (d) -246 kJ [Hint: N N + 3(H--H)---72N--H ;
I .
AH == -90 kJ
[Ans; (b)] I
H
AHrcaction = ~(BE)reactants ~(BE)products
-90 [(BE)N=rN + 3(BE)H __ H]- [6(BE)N_H 1
-90 x + 3 x 435 - 6 x 390
+ 2 AH/ [NH 3 1} ] x 945 kJ mol- 1 ]
450 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
30. If values of Mf; of ICI(g ), Cl(g) and I(g) are respectively H2(g)+ ~02(g)~H20(l) =-286kJ) ...(ii)
17.57,121.34, 106.96 J mol-I. The value ofI-C1 (bond CzH2(g)+ 2~02(g)~ 2C02 (g)+ Hz0(l) ... (iii)
energy) in J mol- 1 is: (Mf -131OkJ)
(a) 17.57 (b}210.73 (c) 35.l5 (d) 106.96 The heat offormation of acetylene is: (VITEEE 2007)
[Ans. (b)] (a) 1802 kJ mol- 1 (b) + 1802 kJ mol- 1
[Hint: The process will be: (c) + 237 kJ moI- 1 (d) - 800 kJ mol- 1
I(g) + Cl(g) ~ I-Cl(g); Mfo =17.57 J morl [Ans. (c)]
Mf = Heat of atomisation of I(g) and Cl(g) [Hint: Required equation is:
- Bond energy of I-CI bond 2C(s) + H 2 (g) ~ C~2(g)
17.57 = 12L34 + 106.96 - x It can be obtained by adding eqs. (i) and (ii) and then
x = 210.73 J mol-I] subtracting eq. (iii) from it.
31. Calculate the Mf in joules for: Heat of formation of acetylene
C (graphite) ~ C (diamond) = (-787) + (- 286) - (-1310)
from the following data: +237kJmol- l ]
C (graphite) + 02 (g ) ~ CO2 (g); MfO = - 393.5 kJ
. C(diamond) + 02(g)~ CO2(g); Mfo = - 395.4 kJ .7.~0 DETERMINATION OF LATTICE
[CET (J&K) 2006) ENERGY (Born-Haber Cycle)
(b) - ~8.9 x 10
3
(a) 1900
3 Lattice energy of an ionic compound is defined as the amount of
(c) 190000 (d) +788.9 x 10
energy released when one mole of the compound is formed by the
[Ans. (a)] interaction of constituent gaseous cations and gaseous anions.
[Hint: C (graphite) + 02(g) ~ CO 2 (g) ; MfO = - 393.5 kJ
A+(g)+B-(g)~A+B- + Energy
CO 2 (g) ~ C (diamond) + 02(g); MfO =+ 395.4 kJ I mole (Lattice energy)
~
Given that, the standard states for iodine and chlorine are
12 (s) and Cl 2(g ), the standard enthalpy of formation for ICI
(g) is :
(a) -14.6 kJ mol- 1 (b) -16.8 kJ morl
(AIEEE 2006)
lp EA
(c) +16.8kJmol- 1 (d) +244.8kJ mol- 1 1 Na(s) SUblimation) Na(g)
2 CI12(9) AHsub
[Ans. (c)]
[Hint: The reaction is:
1 1 . Dissociation
12(8) + Cl 2(g) ~ IC1(g) 1.....-----=~=-----CI(g)
2 2 ~D
1 1
tJ.f H I _ C1 =[ 2 tJ.H'2(S) -> 12(g) + 2 tJ.H 1_ 1
Fig. 7.17
+ ~ tJ.H C1 - Cl J-[tJ.H I_ CI ] The formation of sodium chloride can occur either by direct
combination of sodium(s) and chlorine(g ) or in various steps.
1 I 1
=[-x62.76+ x151+-x242.3]-[211.3] Let the heat of formation of sodium chloride by direct
2 2 2
combination be -Q.
= 16.73 kJ mol-I]
The various steps in the formation of NaCl are the following:
33. Given that: In each step, either energy is absorbed or released.
2C(s)+02(g)~2C02(g) (Mf=-787kJ) ... (i)
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 451
-,.
452 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
various fonns of energy, i. e., their interconversion into one A process which has an urge 'or a natural tendency to occur
. another in exactly equivalent amounts. The law has stood the test either oj its own or after proper initiation under the given set oj
of time as no transfonnation has violated the principle of conditions is known as spontaneous process.
conservation of energy. However, the first law of Spontaneous process does not mean that it takes place
thennodynamics has a number of limitations. instantaneously. It simply implies that the process has an urge to
1. The law does not give any information about the take place and is practicaify feasible. The actual speed of the
direction in which flow of energy takes place. For process may vary from very low to extremely fast. The rusting of
example, if two systems A and B which are capable of iron is a slow spontaneous process while the neutralisation
exchanging heat are brought in contact with each other, reaction between an acid and an alkali is a fast spontaneous
the first law of thennodynamics will only tell us that one process. It is a matter of experience also that all natural processes
system loses energy and other system gains the same are spontaneous and are irreversible, i. e. , move in one direction
amount of energy. But the law fails to tell whether the only. The reverse process which can be tenned as non-
heat will flow from system A to B or from system B to A. spontaneous can be made to occur only by supplying external
In order to predict the direction of the flpw of heat, one energy. For example, water can be made to flow upward by the
more parameter, i. e., temperature is required. The heat use of some external agency or energy is always required to lift
actually flows from a system which has higher the ball from the ground. The natural (spontaneous) processes
temperature. The process continues till both the systems follow a non-equilibrium path and as such are irreversible but
attain the same temperature. The law fails to answer why these processes proceed up to establishment of equilibrium. At
heat energy does not flow from cold system to hot system equilibrium state, the process stops to occur any further. Heat
though the energy is conserved in this way also. flows from a hotter body to a colder body till the temperature of
2. The law does not explain why the chemical reactions do both bodies becomes equal; there is no further flow of heat and
not proceed to completion. we say that the system has attained equilibrium. Some of the
3. The law does not explain why natural spontaneous familiar examplesof spontaneous processes are listed below:
processes are irreversible. (a) Spontaneous processes where no initiation is required
4. The law does not contradict the existence of self-acting (i) Dissolution of sugar or salt in water
refrigerator. Sugar + water ~ Aqueous solution of sugar
5. The law does not contradict the existence of 100% Salt + water ~ Aqueous solution of salt
efficient engine. "
(ii) Evaporation of water from water reservoirs such as
6. The difference between spontaneous and ponds, lakes, rivers, sea, open vessels, etc.
non-spontaneous processes is insignificant in view of the
H20(l)~ H 20(g)
first law.
The answers to above limitations are provided by second law of (iii) Flow of heat from a hot body to a cold body.
thennodynamics. However, before we study this law, let us (iv) Mixing of different gases.
understand the terms spontaneous, entropy and free energy. (v) Flow of water down a hill.
(vi) Reaction between Hz (g ) and 12 (g )to fonn HI(g).
1~18:1 SPONTANEOUS AND H 2 (g)+ I2(g)~2HI(g)
NON-SPONTANEOUS PROCESSES
(vii) Reaction between nitric oxide gas and oxygen to fonn
One of the main objectives in studying thennodynamics, as far as nitrogen dioxide.
chemists are concerned, is to be able to predict whether or not a
reaction will occur when reactants are brought together under a 2NO(g) + 02 (g ) ~ 2NO z (g)
special set of conditions (for example, at a certain temperature, (viii) Melting of ice into water.
pressure and concentration). A reaction that occurs under the
H20(S)~H2°(l)
given set of conditions is called a spontaneous reaction. If a
reaction does not occur under specified conditions, it is said to be (ix) A piece of sodium metal reacts violently with water t()
non-spontaneous. fonn sodium hydroxide and hydrogen gas.
The term spontaneity means the feasibility of a process. In 2Na(s)+ 2H20(l)~2NaOH(aq.)+ H 2 (g)
nature, we observe many processes which occur of their own. For
example, water flows down the hill without the help of any (x) When a zinc rod is dipped in an aqueous solution of
external agency, heat flows from a conductor at high temperature copper sulphate, copper is precipitated.
to another at low temperature, electricity flows from high CuS04 (aq.) + Zn(s) ~ Zns0 4 (aq.) + Cu(s)
potential to low potential. There are processes which require
some initiation before they can proceed. But once initiated, they (b) Spontaneous processes where initiation is required
proceed by themselves. The burning of carbon, burning of fuels (i) Reaction between H2 and ° 2 : This reaction is initiated
and petrol, etc., require some initiation. These processes are by passing electric spark through the mixture.
Electric
tenned· as spontaneous on account of their feasibility, i. e. , these 2H2 (g) + 02 (g) ----+ 2H 20(/)
can occur without the help of external work. spark
454 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(ii) N2 (g) + 3H 2 (g) ~ 2NH3 (g); !JJ[= -ve spontaneously in a direction in which randomness qf the system
2NH3(g)~ N 2 (g)+ 3H 2 (g); !JJ[= +ve increases.
Another example of achieving more randonmess is the sugar
N 2 (g)+ 3H2(g)~2NH3(g) dissolving in water. Before· the solid sugar dissolves, the sugar
(c) Reactions having zero!JJ[: A number of reactions are molecules are organized in a crystal. As the molecules' dissolve, .
known in which neither energy is evolved nor absorbed, but these they become distributed randomly and uniformly throughout the
are spontaneous. For example, esterification of acetic acid is a liquid. The opposite process never occurs, i. e. , sugar cubes do riot
spontaneous process. !JJ[ ofthis reaction is zero. form from the solution.
CH 3COOH + C2HsOH~ CH 3 COOC2H s + H 20
Thus, the second factor which is responsible for the
spontaneity of a process is the tendency to acquire maximum
(d) Exothermic reactions fail to achieve completion: randomness.
Every exothennic reaction rarely proceeds to completion even On the basis of second factor we may also explain the
though !JJ[ remains negative throughout. In fact, all spontaneous spontaneity of endothermic processes.
reactions proceed in a direction until an equilibrium is attained. (i) Decomposition ofcalcium carbonate:
Since, some spontaneous reactions are exothermic and others
CaC0 3 (s) ~. CaO(s) + CO 2 (g); !JJ[ = +178.3 kJ mot~l
are endothermic, it is clear that enthalpy alone cannot account for ..
spontaneity. There must be some other factor responsible for This process is spontaneous because the gaseous CO 2 produced
spontaneity or feasibility of a process. is more random than solid calcium carbonate.
2. Tendency to acquire 'maximum randomness: There is (ii) Evaporation ofwater:
another natural tendency that must be taken into account to H20(/)~H20(g); !JJ[=+44kJmol- 1
predict the direction of spontaneity.
Nature tends to move spontaneously from a state oflower The gaseous state of a substance is more random than the liquid·
probability to one of higher probability, i.e., things tend to state. Thus, evaporation of water is spontaneous which proceeds
in the direction ofmore randomness.
change from organized to disorganized. To illustrate what this
statement means, we consider a spontaneous process of Similarly, fusion of ice is also spontaneous because the
intermixing of two inert gases for which !JJ[ is zero. Two process again proceeds in the direction of more random state, i. e. ,
different inert gases, let us say helium (He) and neon (Ne), are liquid state is more random in comparison to solid state.
originally contained in different glass bulbs, separated by a H20(s)~H20(l); !JJ[= +6.06kJ mol-I
stopcock as shown in Fig. 7.20(a). To make the system as closed
(iii) Dissolution ofNH 4Cl in water:
one, the entire system is perfectly insulated.
When the valve is opened, the intermixing of the two inert NH4CI(s) + aq. ~ NH; (aq.) + Cl- (aq.);
1
gases occurs due to diffusion into one another. As the gases are !JJ[ = + IS.lkJ mol-
inert, there is no chemical interaction between them, the heat
When solid NH4 Cl(s) is dissolved in water, its ions become free.
change during intermixing is negligible. The process of
Free ions move randomly in all directions. Thus, the solution is a
intermixing is a spontaneous process. If the proce~s is examined
more random state as compared to solid NH4 Cl. Thus, the
critically, it is observed that when the valve is opened, both the
process of dissolution will be spontaneous because randomness
gases are provided larger volume to occupy, i. e., each gas
increases on dissolution.
achieves its own most probable distribution, independent of the
presence of other gas. The final distribution is clearly much more (iv) Decomposition of merClfric oxide:
\
probable than the initial distribution. There is, however, another 2HgO(s)~2Hg(/)+ 9i(g); !JJ[ = +9Q3kJ mol-I
maximum
randomness: Like energy factor, the randonmess factor has
-He oNe also certain limitations. For example, in the liquefaction of a gas
Fig. 7.20 (a) Fig. 7.20 (b) or in the solidification of a liquid, the randonmess of the particles
Inert gases before mixing Inert gases after mixing decreases but still these processes are spontaneous. Thus, like
useful way oflooking at this process. The system has gone from a energy factor, randomness alone cannot be the sole criterion for
highly ordered state (all the helium molecules on the left, all the the spontaneity of a process. .
neon molecules on the right) to a more disordered or random Overall tendency as driving force for a spontaneous
state. Mixed gases cannot be separated on their own. Thus, process
diffusion is a spontaneous process acquiring more randomness.
From the above discussion, it is apparent that the spontaneous
In general, nature tends to move spontaneously from more
processes occur because of the two tendencies:
ordered to more random states, or a process proceeds
(i) Tendency of a system to achieve a state of minimum
energy.
456 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
_1
initial and final states of the system. It is independent of the
spontaneity.
manner in which the change has been brought about, i. e. , whether
ENTROPY the change has been brought about reversibly or irreversibly.
Several factors influence the amount of entropy that a system
Why do systems tend to move spontaneously to a state of has in a particular state. In general, ,
maximum randomness or disorder? The answer is that a (i) The value of entropy depends on the mass of the system.
, disordered state is more probable than an ordered state because Hence, it is an extensive property.
the disordered state can be achieved in more ways. The following (ii) A liquid has a higher entropy than the solid from which it
example illustrates the point. Suppose that you shake a box is formed. In a solid, the atoms, molecules or ions are
containing 10 identical coins and then count the number of heads fixed in position; in the liquid, these particles are free to
o
(H) and tails (T). It is very unlikely that all the I coins will come move past one another, i. e., liquid structure is more
up heads; i. e., perfectly ordered; arrangement is much less random and the solid more ordered.
probable than the totally disordered state in which heads and tails (iii) A gas has a higher entropy than the liquid from which it is
come up randomly. The perfectly ordered state of 10 heads can be formed. When vaporization occurs, the particles acquire
achieved in only one Way and the totally disordered state can be greater freedom to move about.
achieved in 210 (l 024) ways, i. e. , the totally disordered state is
(iv) Increasing temperature of a substance increases its
2 10 times more probable than the perfectly ordered state. If the entropy. Raising the temperature increases the kinetic
box contained 1 mol of coins, the, perfectly ordered state would energy of the molecules (atoms or ions) and hence their
be only one, but the disordered states would be much higher freedom of motion. In the solid, the molecules vibrate
23 '
(2 NA = 2 6,.02 x 10 ). It is thus, concluded that a change which with a greater amplitude at higher temperatures. In a
brings about randomness is more likely to occur than one that liquid or a gas, they move about more rapidly.
brings about order. The extent of disorder or randomness is In other words, the more heat the system absorbs, the
expressed by a property known as entropy. more disordered it becomes. Furthermore, if heat is
absorbed at low temperature, it becomes more disordered
Entropy is a thermodynamic state quantity which ·jsa
than when the same amount of heat is added at higher
measure of randomness or disorder of the molecules of the
temperature.
system.
Entropy is represented by the symbol'S'. It is difficult to Units of Entropy and Entropy Change
define the actual entropy of a system. It is more convenient to
define the change of entropy during a change of state. The change Since, entropy change is expressed by a heat term divided by
in entropy from initial to final state of a system is represented by temperature, it is expressed in terms of calories per degree, i. e. ,
AS. The entropy is a state function and depends only on the initial cal K- 1 • In SI units, the entropy change is expressed in terms of
and final states of the system. joules per degree, i.e., J K- 1• Entropy is an extensive property,
i. e., it depends on the mass of the substance; hence units of
AS = S final - S initial entropy are expressed as cal deg -\ mol-I (cal K -1 mol-I) or
jouledeg- l mol-I (JK- I mol-I).
When S final > S initial' AS is positive.
For a chemical reaction, Spontaneity in Terms of Entropy Change
AS S (products) - S (reactants) In an isolated system, such as mixing of gases, there is no
exchange of energy or matter between . the system and
surroundings. However, the mixing of gases is accompanied by
randomness, i. e. , there is increase in entropy. Therefore, it can be
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 457
stated that for a spontaneous process in an isolated system, the q
change in entropy is positive, i.e., llS > o. ASsystem :::; +
T
However, if a system is not isolated, the entropy changes of On the other hand, surroundings lose the same amount of heat at
both the system and surroundings are to betaken into account the same temperature. The decrease in the entropy of the
because system and surroundings together constitute the isolated surroundings will
system. Thus, the total entropy change (AS total) is sum of the
q
change in entropy of the system (ASsystem) and the change in ASsurroundings :::; - T
entropy of the surroundings (ASsurroundings), i. e.,
AS total = ASsystem + ASsurroundiQgs ... (ii) Total change in entropy:::; entropy change in system + entropy
For a spontaneous process, AS total must be positive, i. e., of the process change in surroundings
AS total =AS system + AS surroundings > 0 ... (iii) AS total = ASsystem + ASsurroundings
AS total is also termed as AS universe q -~=O
During a spontaneous process, the entropy of the system goes T T
on increasing till the system attains the equilibrium state, i. e. ,
When the reversible process is adiabatic, there will be no heat
entropy of the system becomes maximum and, therefore, no more
exchange between system and surroundings, i. e., q = 0
increase in the entropy of the system is possible. The
mathematical condition for equilibrium is, ASsystem =0, ASsurroundings =0
AS =o(at equilibrium for an isolated system) '" (iv) AS total = ASsystem + ASsurroundings =0
If AS total is negative, the direct process is non-spontaneous Entropy Change in Irreversible Processes
whereas the reverse process is spontaneous. Consider a system at higher temperature 1j and its
This can be illustrated by considering the entropy changes in surroundings at lower temperature Tz. 'q' amount of heat goes
the conversion of water to ice at three different temperatures. The irreversibly from system'to surroundings.
relevent entropy changes for the system and surroundings and
total change are given in the following table: ASsystem =-~
T.
I
Temperature Msystem M surrounding MlOtal
IlS = 2.303nR log [ ~: J but its value depends on mass of the substance present in
the system.
(ii) Entropy of a system is a state function. It depends on the
(iii) Entropy change for isobaric process (at constant state variables such as T,P,Vand n which govern the
pressure): . state of the system.
IlS = 2.303n Cp log (i. ) (iii) The change in entropy taking place in going from one
state to another state does not depend on the path
adopted. It actually depends on the final and initial states
IlS = 2.303n Cp log (~ ) of the system.
Change in entropy, M = S final - Sinitial
(iv) Entropy change for isochoric process (at constant (iv) The entropy change for a cyclic process is zero.
volume): (v) The entropy change in the equilibrium state is zero
Characteristics of Entropy For example, when ice melts, the change in entropy is given by
The important characteristics of entropy are summarised M S S Mlfusion 6000 J mol-I
below: fusion (ice) = water - ice
Tf 213
(i) Entropy is an extensive property. It is difficult to
determine the absolute value of entropy of a substance = 21.98J K- 1 mol- l
•
Example 69. Oxygen gas weighing 64 g is expanded from I [Hint: 65;otol = Msystem
+ Msurrounding
atm to 0.25 atm at 30°C. Calculate entropy change, assuming the =+ ve for spontaneous process]
gas to be ideal. 38. Melting point of a solid is x K and its latent heat of fusion is
Solution: n=~ 64=2 600 cal mol-I. The entropy change for fusion of 1 mol solid
mwt. 32 is 2 cal mol-I K- 1• The value ofxwill be:
;~)
(a) 100 K (b) 200 K (c) 300 K (d) 400 K
AS = 2.303nR log ( [Ans. (e)]
[Hint: MIfusion -
--r-- - M fusion
2.303 x 2x 8.314 log (_1_) mp
0.25
600 =2
= 23.053 J K-
I
T
Example 70. Calculate the change in entropy when I mole T = 300 K]
nitrogen gas expands isothermally and reverSibly from an initial 39. The entropy change involved in the conversion of 1 mole of
volume ofllitre to a final volume ofl 0 litre at 27° C. liquid water at 373 K to vapour at the same temperature will
be:
Solution: AS 2.303 nR log (~ ) Mivap = 2.257 kJ I g
(a) 0.119 kJ (b) 0.109 kJ
34. For a liquid, enthalpy of fusion is 1.435 kcal mol- I and molar 7L~~. SECOND LAW OF THERMODYNAMICS
entropy change is 5.26 cal mol- I K- I. The melting point of
The second law of thermodynamics tells us whether a given
the liquid is:
process can occur spontaneously and to what extent. It also helps
(a) O°C (b) 273°C
us to calculate the maximum fraction of heat that can be
(c) 173 K (d) 100°C converted into work in a given process.
[Ans. (a)]
The second law ofthermodynamics like first law is a postulate
[Hint: 6Sfusion = --""""'- and has not been derived from any prior concepts. It is stated in
Tmp various forms. However, all the statements of second law have
1.435 x 1000 the same meaning.
5.26 1. Clausius statement: "It is impossible to construct a
Tmp
machine that is able to convey heat by a cyclic process from a
Tmp = 1435 273 K, i.e,O°C] colder to a hotter body unless work is done on the machine by
5.26 some outside agency. n
35. Latent heat of vaporisation of water is 540 cal g-I at 100°C. It means that work can always be completely converted into
Calculate the entropy change when 1000 g water is converted heat but heat cannot be converted completely into work without
to steam at 100°C. leaving some permanent change in the system or surroundings.
(a) 1447 cal (b) 2447 cal (c) 3447 cal (d) 4447 cal For example, heat produced in heat engine is never fully utilized,
[Ans. (a)] as part of it is always lost to surroundings or in overcoming
friction, etc. Thus, it can be said that the complete conversion of
[Hint: Mvap = Mlvap 540 x 1000 = 1447 cal] heat into work is impossible without leaving some effect
T 373
elsewhere.
36. Enthalpy of fusion of water is 6.01 kJ mol-I. The entropy
change of 1 mole of ice at its melting point will be: Or
(a) 22 kJ mol- I (b) 109 kJ mol-I It is not possible to convert heat into work without
compensation.
(c) 44 kJ mol-I (d) 11 kJ mol-I
Or
[Ans. (a)]
All forms ofenergy can be converted into heat energy but heat
[Hint: 68.. = Mlfusion = 6.01 x 1000 22 kJ mor l ] cannot be converted into other forms of energy fully by any
fusion r mp 273
process.
37. For spontaneous process: The other similar statements are:
(a) AStotal = 0 (b) AS total > 0 2. Thomson statement: The heat of the coldest body
(c) AStotal < 0 (d) none ofthese among those participating in a cyclic process cannot serve as a
(Ans. (b)] source of work.
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 461
3. Kelvin-Planck statement: It is impossible by means of dq
inanimate material agency to derive mechanical work or effort dS>-
T
from any portion ofmatter by cooling it below the temperature of
the coldest ofthe surrounding objects. dS ~ dq
4. It is impossible to construct a heat engine ofl 00 % thermal T
efficiency. This is the mathematical statement of second law of
thermodynamics.
5. Lud~g Boltzmann statement: In 1886, Ludwig
Boltzmann gave a most useful statement of the second law of dq dE + P dV This is the mathematical statement of
thermodynamics. Nature tends to pass from a less probable to first law of thermodynamics
more probable state. Combining both the laws of a reversible process,
The connection between entropy and the spontaneity of a TdS =dE+PdV
reaction or a process is exWessed by the second law of
thermodynamics in a number of ways. 7.2' GIBBS FREE ENERGY, (G), CHANGE IN
6. All spontaneous processes or naturally occurring FREE ENERGY AND SPONTANEITY
processes are thermodynamically irreversible. Without the help
ofan external agency, a spontaneous process cannot be reversed. As discussed earlier, there are two thermOdynamic quantities that
For example, the mixing of non-reacting gases is a affect reaction spontaneity. One of these is enthalpy, H; the other
spontaneous process. But these cannot be separated from the is the entropy, S. The problem is to put these two quantities
mixture without tqe application of special methods. together in such a way as to arrive at a single function whose sign
Heat energy can flow from a hot body to a cold body of its will ddermine whether a reaction is spontaneous. This problem
own (spontaneously) but not from a cold body to a hot body was fITst solved more than a century ago by J. WiUard Gibbs,
unless the former is heated. who introduced a new quantity, now called the Gibbs free
energy and given the symbol, G. Gibbs showed that for a reaction
7. The entropy of the universe increases in a spontaneous
taking place at constant pressure and constant temperature, AG
" process and remains unchanged in an equilibrium process.
represents that portion of the total energy change that is available
Since, the universe is made up of the system and the
surroundings, the entropy change in the universe (t.!.S universe) for
If:
0. e. ,free) to do useful work. tor example, AG for a reaction is
- 300 kJ, it is possible to obtain 300 kJ of useful work from the
any process is the sum of the entropy changes in the system
reaction. Conversely, if AG is + 300 kJ, at least that much energy
( t.!.Ssystem) and in the surroundings ( ASsurroundinglJ. in the form of work must be supplied to make the reaction to take
Mathematically, the second law of thermodynamics can be
place. Gibbs free energy of a system is defined as:
expressed as:
'The thermodynamic quantity of the system, the decrease il>
A spontaneous process: whose value during a process is equal to useful work done by the
system. ,.
AS universe = t.!.S system + t.!.Ssurroundings > 0
An equilibrium process: Mathematically, it may be defined as:
t.!.S universe = t.!.SsYStem + ASsurroundings = 0 G=H - TS ... (i)
For a spontaneous process, the law says that t.!.S universe must be " where, H"" enthalpy; S entropy and T absolute temperature.
greater than zero, but it does not place a 'restriction on either
We know that, H = E + PV ... Oi)
ASsystem or ASsurroundings' Thus, it is possible for either t.!.Ssystem or
t.!.Ssurroundings to b...: negative, as long as the sum of these two From eqs. (i) and (ii),
quantities is greater than, zero. For an equilibrium process, G=E+PV -TS
t.!.S universe is zero, i. e. , t.!.Ssystem and t.!.Ssurroundings must be equal in Free energy change at constant temperature and pressure can be
magnitude but opposite in sign. given as:
Thus, the entropy of the universe is continuously increasing. AG AE + P AV T AS
The main ideas of the first and second law of thermodynamics AG=AN T AS .•• (iii)
may be summarised as: (Gibbs-Helmholtz equation)
First law states that the energy of the universe is constant Here, AN AE + P AV
whereas the second law states that the entropy of the universe is Gibbs-Helmholtz equation is used to discuss the driving force,
continuously increasing and tends to a maximum. i.e., the overall criterion of spontaneity.
First law deals with the conservation of energy whereas the
[Note: Since,' H' and'S' are extensive property hence 'G' will also be
second law tells the direCtion of flow of energy.
an extensive property. Moreover, Gibbs function 'G' is a state
For a reversible process, function.] .
dS= dq or dq=T{IS Free Energy Change and Spontaneity
T
For an irreversible process, Let us consider a system which is not isolated from its
surroundings. In this case, total entropy change can be calculated
as:
I
462 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
A5'total ASsystem + .ASSWTOIUldings ... (i) On adding, 2Fe203 (s) + 6CO(g ) ~ 4Fe(s) + 6C02 (g);
Let us consider the process at constant temperature and pressure. AGO =-52.2kJ/mol
Let qp amount of heat be given by the system to the
sUlToundings. Thus, both reactions proceed simultaneously.
The free energy of a reaction is the chemical analogue of
( qp ) surroundings - Mlsystem potential energy of mechanical systems. A body moves in the
_ _ _ _-""- = - Mlsystem direction in which there is decrease in potential energy. Similarly,
ASsurroundings ... (ii) in chemical system, the substance moves in a direction in which
T T
there is decrease in free energy, i. e. , AG is negative.
From equations (i) and (ii), In a chemical reaction, AG = Gproducts - Greactants. Thus,
Mlsystem spontaneous changes occur with a decrease in free energy, i. e. ,
AS total = AS system - - - ' - - AG is negative.
T
To sum up, the criteria for spontaneity of a process in terms of
or AG is as follows: '
or -T AS total = Mlsystem - T ASsystem ... (iii) (i) If AG is negative, the process is spontaneous .
(ii) If AG is zero, the system is in equilibrium. The process
According to Gibbs-Helmholtz equation,
does not occur.
AG=MI-TAS (iii) If AG is positive, the process does not occur in the
.. AGsystem = Mlsystem - T ASsystem ... (iv) forward direction. It may occur in the backward
direction.
From equations (iii) and (iv),
Conditions for AG to be negative or the process to be
AGsystem = - T AS total spontaneous
We know that for spontaneous process, AS total > 0 We know that, AG MI-TAS
.. AG = - ve for spontaneous process. MI TM Conditions !J.G
Thus,Jor spontaneous process T AStotal should be positive or AG
should be negative. -ve +ve (any) -ve spontaneous
(favourable) (favourable)
Case I: Let entropy and energy, both factors are favourable
'A process, i. e., MI = - ve and T AS = + ve
C'" -ve -ve I tili I> (T llS) -ve spontaneous
(favourable) (unfavourable)
AG MI-TAS
= (-ve)- (+ve) =-ve
+ve +ve IT!J.S 1>ltiliI -ve spontaneous
(unfavourable) (favourable)
Thus, AG Vt:_ )/' spontaneous process.
Case II: Let both energy and entropy factors oppose a Role of Temperature on Spontaneity
process, i. e., MI = + ve, T AS = - ve. In Gibbs-Helmholtz equation:
:. From AG MI T AS AG=MI-TAS,
=+ve (-ve) +ve not only MI and AS but also temperature 'T' is a determining
factor for spontaneity, i. e., for AG to be -ve. Let us discuss
Thus, AG is positive for a non-spontaneous process.
exothermic and endotherrriic reactions to show the influence of
Case III: Let both tendencies be equal in magnitude but temperature.
opposite, i. e. ,
1. Exothermic processes: In exothermic reactions,
MI=+ve and T AS +ve and MI=T AS MI = - ve (favourable condition)
.. From AG MI T AS Case I: When T AS is positive, i.e., favourable, then flG
will be negative and the process will be spontaneous at all
=0
temperatures.
In this condition, the process is said to be at equilibrium. Case II: When T AS is negative, i.e.,unfavourable, then flG
Coupled Reactions will be negative when IMIl > IT AS ~ To reduce the magnitude
We know that the reactions which have AG = + ve are of T AS,the temperature should be low. Thus, exothermic
non-spontaneous. However. such reactions can be made reactions can be made favourable (when T AS =- ve) by
spontaneous when coupled with a reaction having very large lowering the temperature.
negative free energy of reaction, 2. Endothermic reactions; In endothermic reactions,
MI = + ve (unfavourable conditions).
e.g., 2Fe203(s) 4Fe(s) + 302 (g); AGO = + 1487kJ/moi
In case of endothermic reactions, AG will be negative when
6CO(g) + 30 2 (g) 6C0 2 (g ); AG ° = -1543.2 kJ/mol IAH I< IT AS f To increase the magnitude of T AS, temperature
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 463
(T) should be increased. Thus, endothermic reactions can be Calculate AG at 700 K when enthalpy and entropy changes are
made favourable by increasing the temperature. -1l3.0kJ marl and -145J K- l mor l respectively.
Thus, temperature also plays an important role in deciding the Solution: We know that, AG AlI- T AS
spontaneity of a reaction. A reaction which is non-spontaneous at Given, All -113 kJ111Ol- 1
low temperature becomes spontaneous at high temperature and
vice-versa. 113000 J 11101-1
AS = -145 J K~I 11101-1
Sign of MI, AG and AS and prediction of spontaneity
T=700K
Ml AS /1G Remarks Substituting these values in the above equation,
-ve +ve -ve i Spontaneous at all we get AG 113000-700x (-145)
temperatures
11500J111Ol-1
-ve. -ve -ve (at low temperature) Spontaneous
= -11.5 kJ 11101- 1
+ve (at high temperature) Non-spontaneous
+ve +ve +ve (at low temperature) Non-spontaneous Example 73. In the reaction A + + B ---7 A + B+, there
-ve (at high temperature) Spontaneous is no entropy change. If enthalpy change is 22 kJ ofA +, calculate
+ve -ve +ve Non-spontaneous at all AG for the reaction.
•temperatures Solution: For the given reaction,
MI All 22 kJ, AS =0
.. From, AG=AlI TAS
+ -
AG = 22- T x 0 22kJ11101- 1
+ Spontaneous at high tem- Spontaneous at all temper-
perature and non-sponta- atures Example 74. All and AS for the reaction
neous at low temperatures Br2 (I) + Cl2 (g) -'I 2BrCI(g) are 29.37 kJ and 104.0J K -I
- Non-spontaneous at all Non-spontaneous at high respectively. Above what temperature will this reaction become
temperatures temperatures and sponta- spontaneous?
neous at low temperatures Solution: According to Gibbs-Helmholtz equation,
AG =All - T AS
:::::::_SOME SOLVED EXAMPLES\ ::::: : : For spontaneous process, AG < 0
Example 71. MI and AS for the reaction, i. e., All T AS < 0
. 1
Ag 2 0(s)---72Ag(s)+-02 (g) TAS>AlI
2 All
are 30.56kJ marl and 66.0J K- I marl respectively. Calculate T>-
AS
the temperature at which free energy change for the reaction will
be zero. Predict whether the forward reaction will be favoured T> 29.37 x 1000
T > 282.4 K.
above or below this temperature. 104
Solution: We know that, .Example 75. Calculate the temperature at which liquid
AG = MI T AS water will be in equilibrium with water vapour.
At equilibrium, AG=O AlIvap = 40.73kJ marl and AS vap 0.109kJ mor l K- 1
so that 0== All T AS
All Solution: Given, All = 40.73 kJ 11101-1
or T=-
AS
AS == O. 109 kJ 11101-1 K- I
Given that, All 30.56 kJ 11101- 1
and AG=O
=30560 J mol-1
Applying AG=AlI TAS
AS = 66.0JK- 1 mol- l
0= 40.73 Tx 0.109
T = 30560 463 K
66 T = 40.73 = 373.6K
0.109
Above this temperature, AG will be negative and the process will
be spontaneous in forward direction. Example 76. Zinc reacts with dilute hydrochloric acid to
give hydrogen at 17° C. The enthalpj/ofthe reaction is -12.55 kJ
Example 72. For the reaction,
marl ofzinc and entropy change equals 5.0J K-,I marl for the
2NO(g) + O 2(g) ---7lN02 (g)
reaction. Calculate the free energy change and predict whether
the reaction is spontaneous or not.
464 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Solution: Given, Mf = -12.55 kJ mol- l Calculate K p at each temperature and predict the direction of
reaction at 300 K and 1200 K, when Peo = Peo2
!:J.S = 5.0JK- 1 mol- l
= PH 2 = PH20 = 1atmat initial state.
= 0.005 kJ K- l mol- l Solution: At 300 K: !:J.Go = Mfo - T !:J.S 0
T = 17 + 273 = 290 K = - 41.16 - 300 x (- 4:24 x 10-2 )
Applying !:J.G=Mf-T !:J.S
= -28.44 kJ
= -12.55 - 0.005 x 290
Since, !:J.G ° is negative hence reaction ,is spontaneous 10
= -12.55 -1.45 = -14.00 kJ mol- l forward direction,
Since, !:J.G is negative, the reaction will be spontaneous. !:J.Go = -2.303RT log Kp
Example 77. Mf and !:J.S for the system -28.44 = - 2.303 x 8.314 x 10-3 x 300 log Kp
H 20 (I) ~ H 20(g) at 1 atmospheric pressure are 40.63 kJ
mol- l and 108.8 J K -I mol- l respectively. CalcuLate the Kp = 8.93x 104
temperature at which the rates of forward and backward At 1200 K: !:J.Go = Mfo - T!:J.S °
reactions will be the same. Predict the sign offree energy jor this
transformation above this temperature. = - 32.93 - 1200(- 2.96 x 10-2 ) = + 2.59 kJ
Solution: Given, Mf = 40.63 kJ mol- l Positive value of !:J.G ° shows that the reaction is spontaneous
!:J.S = 108.8 J K- l mol- l = 0.1088 kJ K- l mol- l in backward direction
(when the system is in equilibrium) !:J.Go = - 2.303RT log Kp
!:J.G=O
..' ..
.~
Applying !:J.G=Ml-T !:J.S 2.59 = - 2.303 x 8.314 x 10-3 x 1200 log K p
0= 40.63 - T x 0.1088 Kp =0.77
T = 40.63 = 373.4 K .. Example 80. The standard Gibbs free energies for the
0.1088 reactions at 1773 K are given below:
The sign of !:J.G above 373 K, i.e., say 374 K, may be C(s) + 02 (g) -----t CO 2 (g); !:J.Go = - 380 kJ mol- l
..:alculated as follows: 2C(s) + 02 (g)~2CO(g); !:J.Go = - 500kJ mol- l
\gain applying !:J.G = Mf - T !:J.S
Discuss the possibility of reducing Al20 3 and PbO with
= 40.63 - 374 x 0.1088 carbon at this temperature,
= 40.63 - 40.69 = - 0.06 kJ 4AI + 302 (g)-----t 2AI20 3 (s); !:J.Go = -22500kJ mol- l
!:J.U will be negative; hence, the reaction will be spontaneous. 2Pb + 02 (g) -----t 2PbO(s); !:J.Go = -120 kJ mol- l
. Example 78. Fl.,' the reaction, Solution: Let us consider the reduction of Al 20 3 by carb?n:
SOCl 2 + Hp -----t S02 + 2HCI,
2Al 20 3 + 3C(s) -----t 4Al(s) + 3C0 2 (g);
the enthalry of reaction is 49.4 kJ and the entropy of reaction is
336 J K - . Calculate!:J.G at 300 K and predict the nature of the !:J.Go = - 380 x 3 + (22500) = + 21360 kJ
reaction. 2Al 20 3 + 6C(s)-----t4Al(s) + 6CO(g);
Solution: !:J.G = Mf - T !:J.S
!:J.Go = - 500 x 3 + 22500 = + 21000 kJ
= 49.4 - (300 x 336 x 10'-3 )
Positive values of !:J.G ° show that the reduction of Al2 0 3 is
=-51.4kJ not possible by any of the above methods.
Since, the free energy change is negative, the given reaction is Now, let us consider the reduction ofPbO.
spontaneous. 2PbO(s) + C -----t 2Pb + CO 2;
Example 79. The standard enthalpy and entropy changes !:J.GO = + 120+ (-380)= -2GOkJ
for the reaction in equilibriumfor the forward direction are given
below: 2PbO(s) + 2C-----t 2Pb + 2CO;
CO(g) + H20(g)~C02 (g)+ H2 (g) !:J.Go = + i20+ (-500)= -380kJ
l
Mt{OOK = -41.16kJ mor Negative value of!:J.G ° shows that the process is spontan(:olls
and PbO can be reduced by carbon.
!:J.S~OOK = -4.24 X 10-2 kl mor l
Example 81. In a fuel cell, methanol is used as fuel and
l oxygen gas is used as an oxidiser. The reaction is:
11ll7200K = - 32.93 kJ mor
3
2
!:J.S7200K = -2.96x 10- kJ mor
l '2
CH pH(I) + O2 (g) -----t CO 2 (g) + 2H 20(1)
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 465
Calculate standard Gibbs free energy change for the reaction The values of /),.S and t1G for conversion of ice into liquid
that can be converted into electrical work. Ifstandard emhalpy of water at O°C are:
combustion jar methanol is -726 kJ mol -I;. calculate the (a) -21.9 J K- 1 mol- I and 0 (b) 0.219 J K- 1 mol-I and 0
efficiency ofconversion of Gibbs energy into usiful work. (c) 21.9 J K-1 mol- l and 0 Cd) 0.021'::1 J K- 1 mo]-l and 0
[Ans. (e»)
/),.G; for CO 2 , H 20, CHPH, O 2 are -394.36; -237.13;
[Hint: t1G 0,
-166.27 and zero respectively.
;'. lili TIlS 0
Solution: The reaction for combustion of methanol is:
3 tJ.S == lili = 6000 = 21.9 J K- 1 mor i ]
CH 3 OH(l) + 02 (g ) ~ CO 2 (g) + 2H 2 0(l) T 273
2
44. For a reaction:
/),.o;eaclion = [/)"Gj CO 2 (g) + 2 /)"Gj H20(l)] I
Ag20(S)~2Ag(s)+ 2 O 2 (g)
[/)"{7[ CH3 0H(l)+ 3 /),.G;.Ol(g)]
2 MI,t1S and Tare 40.63 kJ mol-I; 108.8 J K- 1 mol-I and
= [-394.36 + 2 (-237.13)] [-166.27 + 0] 373.4 K respectively. Predict the feasibility of the reaction.
:::= -702.35 kJ mol- 1 (a) feasible (b) non-feasible
(c) remains at equilibrium (d) not predicted
Efticiency of conversion of Gibbs free energy into useful work [Ans. (c»)
x 100 [Hint: t1G IV{ - T IlS
== -~="-----
o = 40.63 x 1000 373.4 x 108.8 == 0]
/),.fl reaction
45. For the homogeneous reactions:
= -702.35 X 100:::= 96.7% xA + yB~IY +mZ
-726 t1H = - 30 kJ mol-I, /),.S = -100 J K-1 mol-I.
,UUSTtATfONS .Ofc'OB1ECTIVE QUlmONS . At what temperature the reaction is at equilibrium?
(PMT (Kerala) 2006)
40. The tree energy for a reaction having Mf == 31400 cal, (a) 50°C (b) 250°C (c) 100 K (d) 27°C
1 1 (e) 500 K
t1S = 32 cal K- mol- at 1000°C is: IJEE (Orissa) 2005)
[Ans. (d)]
(a) -9336 cal (b) -7386 cal tc) -1936 cal (d) +9336 cal
[Hint: t1G lili - T t1S
[Ans. (a»)
[Hint: t1G == IV{ - T 1lS= 31400 -1273 x 32 == 9336 cal] At equilibrium, t1G == 0
.. T == lili = -30 x 1000 = 300 K, i.e., 27° C]
41. F2C=CF-CF=CF2 ~ F2C--CF2 AS -100
I
CF 46. For the reaction CO(g) + .! O2(g ) ~ CO2(g 1 t1H and
2
For this reaction (ring closure), t1H = 49 kJ mol-I, are 't"283,:kJi,~d T$1-J;,K~\ tnoF!;:rtlspectively. It was
/),.S
t1S = -40.2 J K- I mol-I. Upto what temperature is the intended;td ~out this~reaW0n!atl'l'OO<i; 1500, 3000 and
forward reaction spontaneous? 3500 K. At which of these temperatures would this reaction
(a) 1492°C (b) 1219°C (c) 946°C (d) I080°C be thermodynamically spontaneous? (PMT (Kerala) 2006)
[Ans. (e)] (a) 1500 and 3500 K '. (b) 3000 and 3500 K
[Hint: For spontaneousproeess, (c) 1000, 1500 and 3000 K (d) 1500,3000 and 3500 K
(e) At all ofthe,:above temperatures
t1G = MI. -fIlS (should be negative)
[Ans. (e)]
T > lili [Hint: t1G = Mi - T IlS
IlS
At 1000 K, t1G =- 283 - (-1000 x 0.087) (Spontaneous)
T > -49 x 1000
=-196
-40.2
At 1500 K, t1G = - 283 (-1500 x 0.087) (Spontaneous)
T > 1219 K, i.e., 946°C] 152.5 kJ
42. For the equilibrium reaction, the value of Gibbs free energy At 3000 K, tJ.G 283 - (-3000 x 0.087) (Spontaneous)
change is: (DeE 2005) = -22 kJ
(a) > 0 (b) < 0 (c) 0 (d):1: 0
At 3500 K, t1G = - 283 (-3500xO.087) (Non~ontaneous)
[Ans. (e)]
== + 21.5 kJ]
LHint: tJ.G 0 at equilibrium]
47. For a reaction,
43. At O°C, ice and water are in equilibrium and t1H = 6kJ mol- I. MI = + 29kJ mol-I; M = - 35 JK- I mo(1
For this process:
at what temperature, the reaction will be spontaneous?
H20(S)~ H 2 0(l) (PMT (Haryana) 20071
466 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
=
Sum of standard free 1
[Suniofstandard free
energies of formation - energies of formation
1 reaction at 27° C for the combustion of methane using the given
data:
[ of products . of reactants . CH4 (g) + ']()2 (g) ------'? CO2(g) + 2H20 (I)
Species CH 4 02 CO2 H 20
Let us consider a general reaction:
. . " n; A + n2B------'? n3L + n4M Mi; / (kJ mor1 ) 74.8 - 393.5 285.8
AGO =, '2..G;(products) - '2..G; (reactants) SO/(J K- 1 mor1 ) 186 205 214 70
=[n3G;(L)+ n4 Gj(M)] - [n\ G;(A)+ n2 Gf(B)] Solution: Mio::; Mi; (C0 2) + 2Mil (H;P) Mij (CH 4)
-
f)
The standard free energy of formation (A G may be defined as
the free energy change when 1mole ofa compound is formed from =
393.5 + 2 x (-285.8) - (.;..74.8)
890kJmol-1
its constituent elements in their standard state. The standardfree
energy offormation ofan element in its standard state is assumed
AS ° S (~02) +' 2S (~;P) - S (~H 4) - 2S t
0 2)
the standard Gibbs free energy of reaction (at 1000K ) is [Hint: 13.Go = - 2.303RT log Kr
- 8.1 kJlmol. Calculate its equilibrium constant.
=- 2.303 x 8.314 x 29810g (4.42 x 104 )
Solution: We know that,
= -26.5 kJ mol- i ]
-llGo \
K = antilog (
2.303RT
j ... (i) 49. What is the sign of 13.0° and the value of K for an
Given that, llGo=-8.lkJ/mol electrochemical cell for which Ec~1l = 0.80volt?
R = 8.314 X 10-3 kJ K~l mol- 1 llGo K
T=looOK (a) >I
Substituting these values in eq. (i), we get (b) + >1
K = antilog
" -(" -81)
.
[ 2.303 x 8.314 x 10-3
1 (c) +
(d)
<1
<1
X 1000 [Ans. (a)]
[Hint: 13.GO nFE"; 13.Go =- 2.303RT log K]
.,K =2.65
Example 89. Calculate llG ° for the conversion of oxygen 50. The free energy of formation of NO is 78 kJ mol- 1 at the
to ozone, (3/2)0 2 (g) ~ 0 3 (g) at 298 K, if K p for this temperature of an automobile engine (1000 K). What is the
conversion is 2.47 x 10-29 • • equilibrium constant for this reaction at 1000 K?
Solution: We know that, ..! N 2(g)+ I 02(g)~NO(g)
llG 0 = - 2.303RT log K p
2 2
(a) 8.4 x 10- 5
(b) 7. I X 10-9
= 2.303 x 8.314 x 298 log 2.47 x 10-29
(c) 4.2 X 10- 10 (d) 1.7 X 10- 19
::::; 163228 J 1 mol
[Ans. (a)]
" . = 163.228kJI mol [Hint: K = antilog -13.GO J
Example 90. Acetic acid CH 3COOH can form adimer [ 2.303RT
(CH 3COOH}z in the gas phase. The dimer is held together by
two H-bonds with a total strength of66.5 kJ per mol ofdimer anti'1og [ -78xlOOO ]
0- lh 2.303 x 8.314 x 1000
~O .... H-O,
"
= 8.4 x 10-5 ]
CH3-C~ /-CH3
"O-H.... O " 51. Equilibrium constant for the reaction:
0+ 0-
H2 (g) + 12 (g)~ 2H1(g)
If at 25° C, the equilibrium constant for the dimerization is
1.3 x 10 3 . Calculate MO for the reaction: is K c 50 at 25°C.
2CH3COOH(g)~(CH3COOHh(g)
The standard Gibbs free energy change for the reaction will
be:
Solution: llGo =- 2.303 RT log K" (a) - 6.964 kJ (b) - 9.694 kJ
(c) ~ 4.964 kJ (d) - 6.496 kJ
= 2.303 x 8.314 x 29810g (1.3 x 103 ) [Ans. (b)]
[Hint: log K = - AGo AG and emf of the cell (E) are related by the following
p 2.303RT relation:
- (-115 x 1000) AG -nFE
2.303 x 8.314 x 298 where, F =faraday = 96500coulomb
20.16] E = emf of the cell
.. ST = f: C p d In T
.From the graph it is clear that entropy of a substance increases
with increase in temperature; there is sudden change in entropy at
the stage of phase transformation.
When entropy ofone mole ofa substance is expressed at 298K
and 1 aim pressure, it is called standard entropy of that Example 93. Calculate /).G °for the folloWing reaction:
substance. It is denoted by S 0. The standard entropy change M ° 1
for a chemical reaction can be calculated as CO(g) + (- ) 02 (g) ~ CO 2 (g); MfO = - 282.84 kJ
2
MO = LS~produc~) - ~S~reactants) Given,
S~2 = 205.0J K
-I
-I
mo/- I , S~o(g) = 197.9J K
mol -I.
-1 mol-I,
e. g. , in the reaction:
C 2H6 (g ) ~ H2 (g) + C 2H4 (g)
Solution: /).SO = ~S ~products) - LS ~reactants)
° -
= [Se02] ° + -1·So° ]
/).SO = ~S~products) - ~S~reactants) [Seo
2 2
= [S~2 + S~H4]"- [S~2H6] = 213.8- [197.9+.! 205]
2
I
Standard molar entropies in JIK mol at 298 K = - 86.6JK-
A = 130,B 203,C= 152 volume V3 (point C). In this operation, no heat is absorbed and
o 0 thus, the work, wz, is done by the system at the expense of
Solution: .'ES (products) - ~~ (reactants) internal energy, i. e., the temperature of the system falls from
temperature T2 to temperature TI .
[S~ +S~]-[S~],
11E=-w2 =-CV (T2 -Td ... (ii)
=[203 + 152] [130]
=225JK- I Third operation-Isothermal reversible
compression
7.32 CONVERSION OF HEAT INTO WORK- The gas at point C is subjected to reversible isothermal
THE CAR NOT CYCLE compression at temperature TI •The path followed is CD when the
volume decreases from V3 to V4 (point D). In this operation work
Carnot, a French engineer, in 1824, employed merely theoretical is done on the system and heat ql is given out by the system to
and an imaginary reversible cycle known as Carnot cycle to surroundings.
demonstrate the maximum convertibility of heat into work.
The system consists of one ~ole of an ideal gas enclosed in a .... (iii)
cylinder fitted with a piston which is subjected to a series of four
successive operations. The four operations are:
(i) Isothermal reversible expansion Fourth operation-Adiabatic reversible· .
compreSSion
(ii) Adiabatic reversible expansion
(iii) Isothermal reversible compression Finally, the gas at point D is subjected to reversible aqiabatic
compression through the path DA at temperature TI . The volume
(iv) Adiabatic reversible compression
changes from V4 to VI , i. e. , the original volume is restored. The
The four operations have been shoWn in Fig. 7.25.
temperature increases from TI to T2 (original temperature). The
(Pl, V1) work done increases the internal energy of the system as q ::: Q .
---- W4 Cv(T2 -T1 ) ... (iv)
The net heat absorbed, q, by the ideal gas in the cycle is given
by
V V
., q = q2 + (-ql) RT2 loge - 2 + R1I loge - 4
VI V3
V V3
=RT2 loge - 2 RTI loge- ... (v)
·VI · V4
According to the expression governing adiabatic changes,
expansion
Similarly, net work done by the gas is given by
The gas is now allowed to expand reversibly and adiabatically
through BC path. The volume increases from V2 (point B) to
G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
W=q2 .-=--..:..
T2
=R(T2 -11 ) log e V. ... (vii)
=1897.86 x (373 - 283)
I
373
Thus, q == w. For cyclic process, the essential condition is that
net work done is equal to heat absorbed. This condition is 1897.86 x 90 457.92 kJ
satisfied in a Camot cycle. 373
Solution: Efficiency
T2 11 q= W =PdV
T2 dS =!1. = PdV
T T
Tz 100+273= 373K dV
dS=nR-
11 = 25+ 273 298K V
.
EffilCiency =
373 - 298 75
=- 0.20 20% On integration, ~S =nR In ( ~~ )
373 373
= - 41.4 kcal
fj,G (for reaction) =
o
G~02 - G~o G)G~2
Example 14. Calculate Q, W, I1E and AH for the
isothermal reversible expansion of 1 mole ofan ideal gas from an 394.4 -(- 137.2) 0
initial pressure of 1.0 bar to a final pressure of 0.1 bar at a
= 257.2 kJ mol-I
constant temperature of273 K. (liT 2000)
Solution: In isothermal process as temperature remains I1G = f1HO - TI1S o
o
constant both I1E and AH are zero. 257.2 = f1HO - 298 x (0.094 )
11E=0; AH 0
or f1HO = 288.2 kJ
Applying first law of thermodynamics,
I1G ° is ve, hence the process is spontaneous, and AH ° is
I1E=W+Q
also -ve, hence the process is also exothermic.
O=W+Q Example 17. Diborane is a potential rocket foel which
undergoes combustion according to the reaction,
476 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
when 5 mole ofeach are taken and temperature is kept at 298 K, K = [C] = Keq [A] = 256.31 x 13 = a037
the total pressure was found to be 20 bar. 2 [B] [8]2 (95.2)2
Given: AGf NP4 = 100kJ
AG; = - 2.303RT log K 2
AGf NOz =50 kJ = 2.303 x 8.314 x 448 log 0.037
(i) Find AG Qfthe reaction at 298 K.
= 12282J = 12.282kJ
(ii) Find the direction of the reaction.
lIlT 2004 (Memory based)] Stability will lie in the order
Solution: The reaction is: B>C>A
N 2 0 4 (g)~ 2N02 (g) ',Example 21. Two moles of a perfect gas undergo the
Since, number of moles of both N Z0 4 and NO z are same following process:
hence their partial pressure will also be same. (a) A reversible isobaric expansionfrom (latm 20 L)to (latm
20 40L).
PN:P4 = PN0 2 = 2: =lObar
(b) A reversible isochoric change ofstate from (1 atm 40 L) to
(0.5atm 40L).
(c) A reversible isothermal compression from (0.5atm 40 L )to
(latm 20L).
(i) Sketch with labels each of the process on the same P-V
diagram.
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 477
(ii) Calculate the total work (W ) and the total heat change =- 1x 20 x 101.3 + 0
( q ) involved in the above process.
(iii) What will be the value of AU,!J.H and AS for the overall
+ 2.303 x 2x 8.314 x T log (~~) ... (1)
process? (lIT 2002)
PV = nRT (At A)
Solution:
Ix 20= 2x 0.0821 x T
T= 20 =121.8K
2xO.0821
i!!! 1 atm
AB Fromeq. (1),
J 0.5 atm
:::::::::::::rS;lI
,
I
I
,
I
I
I
Total work = 2026 + 2.303 x 2 x 8.314 x 121.8 log 2
= -622.06J
W q -622.06J
I
,
I
I In cyclic process:
, I
AU =O,!J.H =oand AS = 0
20L 40L
Volume ---to-
';-. ...SUMMARY
,., ,.. AND IMPORTANT POINTS TO REMEMBER
'~l )-. .....,,Ie ....
1. Thermodynamics: It is the branch of science which boiling points, etc. (ii) Extensive properties are those whose
deals with all changes in energy or transfer of energy that magnitude depends upon the quantity of matter present 111 .be
accompany physical and chemical processes. It is not concerned system such as volume, total energy, enthalpy, entropy, etc.
with the total energy of body but only with energy changes taking (d) State variables: The fundamental properties which
place. The laws of thermodynamics apply only to matter in bulk, determine the state of the system are termed state variables. The
i.e., to macroscopic system· and not to individual atoms or change in state property depends only upon the initial and final
molecules. states of the system, i.e., do not depend on the path followed.
2. Terms used in thermodynamics: Pressure, volume, temperature, internal energy, enthalpy, entropy,
(a) System, surroundings and boundary: A system is force, energy and number of moles are the state variables.
defmed as a specified part of the universe which is under (e) Thermodynamic equilibrium: A system in which the
experimental investigation and the rest of the universe which can fundamental properties do not undergo any change with time is
interact with the system is surroundings. Anything which said to be in thermodynamic equilibrium. Actually the system
separates system and surroundings is called boundary. It may be should be in thermal equilibrium, mechanical equilibrium and
real or imaginary, conductor or non-conductor. chemical equilibrium.
(b) Types of system: There are three types of system: (1) Thermodynamic processes: When the system changes
(i) Isolated system is one which has no interaction with its from one state to another, the operation is called a process. The
surroundings. The boundary is sealed and insulated. Neither various types of processes are:
matter nor energy can be exchanged with surroundings. (0 Isothermal: Temperature remains fixed, i.e., dT 0.
(ii) Closed system is one which can exchange energy but not This is achieved by placing the system in a thermostat.
matter with surroundings. (iii) Open system is one which can (ii) Adiabatic: When no exchange of heat occurs between
exchange matter as well as energy with surroundings. A system is the system and surroundings, i.e., the system is thermally isolated
said to be homogeneous if it is rrutde of one-phase only. A system (dq = 0).
is said to be heterogeneous when it consists of two or more (iii) Isobaric: Pressure remains constant throughout the
phases. change, i.e., dP O.
(c) Thermodynamic properties: These are of two types:
(iv) Isochoric: Volume remains constant throughout the
(i) Intensive properties are'those which do not depend upon the
change. i.e., dV =O.
quantity of matter present in the system such as pressure,
temperature, specific he.~:surface tension, viscosity, melting and
.,-:'l
478 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(v) Cyclic: When a system undergoes a number of different When heat energy ( q ) is given to a system and work ( w) is also
processes and finally returns to initial state, dE = 0 and dH 0 done on it, its energy increases from E I to E 2 .
(vi) .Reversible: A process which occurs infinitesimally E2 =EI +q+w or E2 -El =q+w or M:::q+w
slowly and at every small change it is virtually in a state of
In case heat energy (q) is given to a system and .work (w) is
eqUilibrium. It takes infinite time.
done by the system then
(vii) Irreversible: When the process goes from initial to
final state in single step in fmite time. All natural processes are M = q + (-w) = q w
irreversible. 6. Enthalpy or heat content: .The' quantity E + PV is
3. Nature of work and heat: Work is a mode of transfer known as entluilpy or heat .content. Jt is denoted by H. It
of energy to or from a system with reference to surroundings. If represents the total energy stored i~ a system.
an object is displaced through a distance dx against a constant M = q -P(V2 ViJ or E2 - EI =-q - PV2 + PVI
force F , then the amount of work which has to be done is equal to
F x dx. The mechanical work or pressure volume work is equal to or (E2+P2V2)-(EI+PIVI)=q or H 2 -HI :::q
P ext (V2 ~ VI ) or P x dV. The work done on the system increases or !lH =q or M + P IlV !lH qp
its energy while work done by the system decreases its energy. when V2 =VI' i.e., Il V::: 0, M ::: qv
On this basis, the work done has the sign convention. qv +llnRT qp in the case of gases
Work done by the system = - w
where, Iln ::: total number of moles of products total number
Work done on thesystem=+ w
The unit of work is erg. It is very small. The bigger unit is . of moles of reactants
joule or kilojoule. . 7. Heat capacity: . It is the quantity of heat required to
7
1 joule = 10 ergs; 1kJ (kilojoule) = 1000 J .raise the temperature of the system by one degree.
Heat is the quantity of energy which flows between system dq
Heat capacity ::: -
and surroundings on account of temperature' difference. It is equal dT
to m x s x At where m is the mass, s is the specific heat and Ilt is
the temperature difference. The sign convention for heat is: In the case of gases;
Heat gained by system = + q
Heat lost by system = -' q
C v (at constant volUll)e) :::( ~~) V
The unit of heat is calorie (cal). Since, heat and work are
.;!::elated the SI unit of heat is joule. ::: Molar heat capacity at constant volume
1 joule = 0.2390cal .
and C p (at constant pressure) =
(aH)
- ..
1calorie = 4.184 J . .. . aT p
'L I kcal =4.184 kJ
::: Molar heat capacity at.constant pressure
1litre-atm = 101.3 J =·1.013 x 109 erg = 24.206cal
C p -Cv:::R
4. Internal energy: Sum of all forms of energy that a
8. Isothermal expansion of an ideal gas:. The expansion
system possesses is termed internal energy. It is denoted by E.lt is
in an ideal gas at constant temperature can be done reversibly or
an extensive property. It is also a state property.
irreversibly. .
E ::: E translational +. E rotational + E vibrational + E bonding
w Work done by gas in reversible expansion
+ E electronic + ...
. V . P
The internal energy of a particular system is a defInite quantity ::: - 2.303nRT log ...1.. 2.303nRT log _I
but it is impossible to determine its exact value. It is a state VI . P2
function. In thermodynamics, one is concerned only with energy
q =Heat abS()rbed from surroundings
change which occurs when the system moves from one state to . '. . V
ancitherJe., M ::: Ej - Ei. M is +ve if E f > E; andnegativeif =- w 2.303nRT
.
log ...1..
. VI
E f < E i' M does not depend on the path by which final state is
achieved. For a cyclic process, MO. W = Work done by gas in irreversible expansion
5. First law of thermodynamics: Energy can neither be
created nor destroyed but it can be converted from one form to = - Pext (V2 - VI )
another. Maximum work i~ done in reversible isothermal expansion. In
isothermal process, M =,.oand IlH= O. . '. '.. . .
.Or Adiabatic expansion of an ideal' gas: q in the process is
The energy of the Universe is constant. zero, hence M = w. Work is done by the gas during expansion at
Or the expense of internal energy. In expansion, M decreases while
Total energy of an isolated system remains constant, though it in.compression M increases. .
may change from one form to another.
M = w = C v x IlT
I
The value of !:!.T depends upon the process whether. carried 13. Heat offormation or enthalpy offormation: It is the
reversibly or irreversibly. The following relationships are amount of heat evolved or absorbed when one gram mole of
followed by an ideal gas under adiabatic conditions: substance is directly obtained from its constituent elements. It is
represented as !:!.H f.
PV Y = constant If all the substances of the chemical reaction are in their
standard states (i.e., at 25° Cor 298 K and one atmospheric
pressure), the heat of reaction or fonnation is called standard heat
of reaction or fonnation respectively. These are denoted as Mfo
or Mt;- respectively. The enthalpies of free elements at standard
9. Joule-Thomson effect: . The phenomenon of producing conditions are taken arbitrary as zero.
lowering of temperature when a gas is made to expand The compounds which have positive enthalpies of fonnation
adiabatically from a region of high pressure into a region of low are called endothermic compounds (less stable) and which have
pressure, is known as Joule-Thomson effect. This effect is negative enthalpies of fonnation are called exothermic
observed below the inversion temperature ofa gas. The inversion compounds (stable).
temperature ofa gas depends upon the van der Waals' constants .14. Heat of combustion or enthalpy of combustion: It is
of a gas. It is expressed in tenns of vap der Waals' constants 'a' the amount of heat evolved when one mole of the substance is
and 'b' as: completely oxidised. It has a number of applications:
2a (i) Detennination of calorifIc values of foods and fuels.
r. =Rb
I
- (ii) Enthalpy of fonnation can be determined by application
of Hess's law.
10. Thermochemistry: It is concerned with heat changes (iii) Structural problems can be evaluated.
accompanying physical and chemical transfonnations. It is also 15. Enthalpy of hydrogenation: The enthalpy change
tenned as chemical energetics. It is based on the fIrst law of associated when one mole of an unsaturated organic compound is
thennodynamics. If E J and E2 represent total energies associated fully hydrogenated.
with reactants and products respectively, three cases may arise: 16. Enthalpy of solution: The amount of heat evolved or
Case I: E J = E 2 . Neither heat is evolved nor absorbed. Such absorbed when one mole of the substance is dissolved in excess
reactions are very rare. of water so that further dilution does. not bring any heat change.
Case II: E J > E 2. The difference (E J - E2 ) of energy will be 17. Enthalpy or heat of neutralisation: The amotmtof
evolved, i.e., heat is evolved. heat evolved when one gram equivalent of an acid is neUli'ah",.::d
Case III: E J < E 2 . The difference (E2 - E J )ofenergywill be by one gram equivalent of a base in dilute solution. Heat of
neutralisation of a strong acid against· a strong· base is always
absorbed, i.e., heat is absorbed.
constant, i.e., 13.7 kcal or 57.1 kJ. It is due to common reaction
11. Exothermic reactions: Reactions which o~cur with
between H + and OH - ions. The heat offonnation of water from
evolution of heat
these ions is 13.7 kcal.
H productS < H reactants' i. e. , !:!.H = - ve
H+ +OW ~H20; !:!.H = - 13.7 kcal
Endothermic reactions: Reactions which occur with
absorption of heat In the case of weak acids and weak bases,the heat of
neutralisation is always less than 13.7 kcal because some ofthe
H products > H reactants' i.e., !:!.H = + ve evolved heat energy is utili~ed in bringing about complete
Sign conventions q !:!.E !:!.H ionisation of acid or base in solution.
18. Enthalpy of fusion: Heat absorbed in converting one
Exothennic (-) (-) (-) mole of solid into liquid at its melting point.
Endothennic (+) (+) (+) 19. Enthalpy of vaporisation: Heat absorbed in
12. Heat of reaction or enthalpy of reaction: The converting one mole of a liquid into its vapours at its boiling
amount of heat evolved or absorbed when quantities of the point.
substances indicated by chemical equation have completely Enthalpy of sublimation: Heat absorbed in converting one
reacted, it is represented as !:!.H. mole of solid directly into its vapour.
Enthalpy of reaction = L H products - L H reactants
(ii) Hess's law (the lawof constant heat summation): If a value of entropy cannot be determined. The change in entropy is
chemical reaction can be made to take place in a number of ways denoted by flS.
in one or in several steps, the total change is always the same, i.e.,
heat change depends upon the initial and final stages only and IlS == q reversible
independent of intermediate steps, The thermochemical T
equations can be added, subtracted or multiplied by a number to where, q is the heat supplied at temperature T.
obtain a desired equation. flS + indicates increase in randonmess whereas, t:.S ==
21. Bond energy: The energy required to break one mole indicates the decrease in randonmess',
of bond of a particular type is termed bond dissociation energy. It
depends upon the nature of bond and also the molecule in which flS S final - S initial'
the bond is present. The bond energies can be used for 24. Free energy: Free energy change, t:.G, was introduced
determining heats of reactions. '
by Gibbs. The Gibbs-Helmholtz equation is:
[Heat of reaction"" Sum of bond energies of reactants
Sum of bond energies of products] flG == IlH - T IlS or G==H-TS
The bond energies can also be used for determining resonance
energy. and flG"" G products - G reactants
Resonance energy Observed heat of formation where, G is known as free energy. This is the maximum energy
- Calculated heat of formation available to a system during a process which can be converted
22. Experimental determination of heat of into useful work.
reaction: The apparatus used is called calorimeter. Two of the Negative value of !J.G· indicates that the proces~ is
common types of calorimeters are: (i) Water calorimeter (ii) spontaneous. Zero value means that there is a state of
Bomb-calorimeter. The principle of, measurement is that heat equilibrium.
given out is equal to heat taken, i.e., 25. Second law of thermodynamics: It is impossible to
construct a machine that is able to convey heat by a cyclic process
Q""(W+m)xsx(T2 -Td
from a colder to a hotter body unless work is done on the machine
where, W == Water equivalent of the calorimeter, m mass of the by some outside agency.
liquid, s == its sp. heat, T2 =fmal temperature and Tl == initial Or
temperature. Work can always be converted into heat but the conversion of
23. Spontaneous process: A process which proceeds of heat into wor)c does not take place under all conditions.
its own accord without any outside help is termed spontaneous 26. Carnot· cycle: It demonstrates the maximum
process. All natural processes' proceed spontaneously and are convertibility of heat into work in a theoretical and an imaginary
thermodynamically irreversible. cycle.
Driving force: It is the force which makes the process to W
occur by itself. It is the resultant of two basic tendencies: Thermodynamic efficiency ==--=-_.:0..
(i) Tendency to attain a state of minimum energy.
(ii) Tendency to attain a state of maximum randonmess. The efficiency of a heat engine is always le:;>s than 1.
The disorder 9r randonmess in a system is measured in terms 27. Third law of thermodynamics: The entropy of all
of a thermodynamic property known as entropy. The absolute pure crystals is zero at the absolute zero of temperature.
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 481
~l!tilINifj
l. Matrix-Matching Problems (For lIT Aspirants); [E] Match the reactions in Column-I with relations of
[A] Match the List-I with List-II: Column -II:
List-I List-II Column-I Column-II
(a) (P) Spontaneous (Reaction) (Relation)
flSsy&em > 0
(Isolated system) (a) H2(g) + CI 2(g) ~ 2HCl(g) (P) MI == ~U + RT
(b) ~G<O (q) Non-spontaneous
(b) N 2(g)+ 02(g)~ 2NO(g) (q) MI= ~U
photochemical reaction
(c) (r) Equilibrium (c) Hz(g)+ I2(g)~ 2HI(g) (r) MI == ~U 2RT
flSTotal == 0
(d) (~G)TP > 0 (s) Non-spontaneous (d) N2 (g ) + 3Hz(g ) ~ 2NH3 (g) (s) Forward shift by
increasing pressure
[B] Match the Column-I with Column-II:
Column-I Column-II [F] Match the processes of Column-I with entropy or,~J.lthalpy
= 2.303nRT log (~)
changes in Column-II:' .
(a) Isothermal process (P) W
(reversible) Column-I Column-II
(b) Adiabatic process (q) PV Y =constant (a) Nz(g) + 02(g) ~ 2NO(g) (P) ~S 0
(b) 2KI(aq.) + HgIz(aq.)~
(c) W = nR (Tz 1\) (r) W == 2.303nRT log (V~ \J K 2 [HgI4](aq. )
(q) ~ < 0
r-I
(c) PCI 3 (g)+ CI2(g)~ PCldg) (r) MI > 0
(d) Irreversible i~otherrnal (s) W == - Pext (V2 - Vi )
process (d) NH3(g)+HCI(g)~NH4Cl(s) (s) MI<O
[C] Match the physical properties ill,tList-I with their relations [0] Match the List-f\lvith List-II: .
in List-II:
List-I List-II
List-I List-II (Reaction) .' (Process)
(Quantity) (Relation)
I .
(a) ~G (P) -nFE or - nFE O (a) C(s)+ '2 ~(g)~ CO(g) (P) Combustion
[D] Match the Column-I with Column-II: (d) Hz(g) + I 02(g) ~ H20(I) (s) Reaction of apollo
Column-I Column-II 2 fuel cell
(Gas) (Thermodynamic property)
[H] Match the relations of Column-I with their names in
(a) °2 (p) Y = 1.4 Column-II:
Column-I Column-II
7
(b) N2 (q) Cp =-R
2 (a) Mlz MIl =~Cp (P) Trouton equation
(c) CO2 ,CH4 (r) 23 R -1\
6 (b) =~Cy (q) Effect of temperature
(d) I mol 0z + 2 mol 0 3 (s) Y = 1.33 T2 -1\ on the heat of
reaction
Here: C p = Heat capacity at constant pressure
y CplCy (c) MI fusion _ ~ (r) Kirchhoff's equation
T - fusion
mp
[I] Match the Column-I with Column-II: [J] Match the Column-I with Column-II :
Column-I Column-IJ Column-I Column-II
(a) Amount of heat required (P) Specific heat x molar
(a) Mf = + ve,I1S + ve (P) Spontaneous at all
to raise the temperature mass
temperature
of I mol substance by
laC (b) Mf = - ve, I1S = + ve (q) Non-spontaneous at all
temperature
Mf I1U
(b) - o r - (q) Heat capacity C,Cp or (c) Mf + ve, I1S =- ve (r) Non-spontaneous at high
I1T I1T Cv temperature
(c) Heat evolved in the (r) Electron gain enthalpy (d) Mf = ve, I1S - ve (s) Spontaneous at high
combustion of I g of a temperature
substance
(d) Heat evolved when an (s) Calorific value
extra electron is added to
valence shell of an
isolated gaseous atom
. . --:' .
[,~l,tr-?;Cf..·'\',c';i>h;fd-~:}~;t{ii~i~____________ ------------------------i
1. [A] (a-p); (b-p, q); (c-r); (d-s) [G] (a-p, r); (b-p); (c-q); (d-p, r, s)
[B] (a-p, r);(b-q); (c-q); (d-s) [H] (a-q, r); (b-q, r); (c-p); (d-s)
[C] (a-p, q); (b-p, r); (c-p); Cd-s) [1] (a-p, q); (b-p, q); (c-s); (d-r)
[D] (a-p, q); (b-p, q); (c-s); (d-r) . [J] (a-s); (b-p); (c-q); (d-r)
[E] (a-q); (b-q); (c-p); (d-r, s)
[F] (a-p, r); (b-q, s); (c-q, r); (d-q, s)
•. RACTICE PROBLEMS.
1. Write 'yes' if heat, work or matter are able to cross the from the state A ~ B (ii) Work done in taking the gas from
boundary of the corresponding system and 'no' if passage is B ~ C (iii) Work done in a complete cycle. (1 litre == 10-3 mC)
forbidden: [Ans. (i) -60 XI02 J (ii) zero (iii) 36 x 102 J, i.e" network is
done by the gas]
Close Isolated Adiabatic
Property
system system system 4. A sample of a gas contracts 200 cm 3 by an average of 0.5
atmosphere while 8.5 J heat flows out into the surroundings.
Heat YesfNo YesfNo YesfNo YesfNo What is the change in energy of the system?
Work YesfNo YesfNo YesfNo YesfNo (1 litre-atm 101.3 1)
[Ans. Energy of the system increases by 1.63 J]
Matter YesfNo YesfNo YesfNo YesfNo
5. Calculate the pressure-volume work done by the system when
2. Which of the following are state functions? the gas expands from 1.0 litre to 2.0 litre against a constant
(i) Q (ii) W (iii) Q + W (iv) Q - W (v) Qv(vi) Qp external pressure of 10 atmospheres. Express the answer in
calorie and joule.
(vii) fL (viii) fL (ix) Mf (x) E + PV (xi) E
PV [Ans. -10 litre-atm, -242.2 cal, -1013.28 J]
W T T .
[Ans.. (iv), (v), (vi), (viii), (ix), (x).] 6. A sample of a gas in a cylinder contracts by 7.5 litre at a
3. In the adjoining diagram, the P -V graph of an ideal gas is constant pressure of 5.0 atmosphere. How much work is done
shown, Find out from the graph (i) Work done in taking the gas on the gas by the surroundings?
[Ans. 37.5litre-atm or 3801.75 J]
i
c:J 15
f=
"'§ 12
ic:
<fl
0
9
6
DB
.... ----
iD C:
7. A sample of a gas expands from 200 cm3 to 500 cm3 against an
average pressure of 750 torr while 1.5 J h~at flows into the
system. What is the change in energy of the system?
(1 litre-atm == 10 1.3 J)
[Ans. Energy of the system is decreased by 28.5 J;
tlE 28.5 J 1
..- 3 I I
it I
I ,
I 8. Calculate the work done when 65.38 g of zinc dissolves in
0 hydrochloric acid in an open beaker at 300 K. (At. mass of .
2 3 4 5 6 7
Zn 65.38)
V (litre) -
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 483
[Ans. - 2494.2 J, i.e., work is done by the system] 19. Calculate M and Mwhen lOdm 3 of helium atNTPis heated
9. 6 moles of an ideal gas expand isothermally and reversibly in a cylinder to 100° C, assuming that the gas behaves ideally.
from a volume of 1 dm 3 to a volume oflOdm3 at 27°C. What (C v = 3/ 2R)
is the maximum work done? Express your answer in joule. [Ans. till = 556.74 J
[Ans. - 34464.8 J, work is done by the system] /lli = 927.9 J]
10. 1 mqle of an ideal gas at 25° C is allow\!d to expand reversibly [Hint: till = n· Cv . I'l.T and /lli = n· C p . I'l.T
at constant temperature from a volume of 10 litre to 20 litre.
Calculate the work done by the gas in joule and calorie.
=~X~X8.314 x 100 =~ x~ x 8.314 x 100
22.4 2 22.4 2
[Ans. - 1717.46 J or -4 n cal, i.e., work is done by the gas] = 556.74 J = 927.9 J]
11. Find the work done when 1. mole of the gas is expanded 20. For the conversion of 1 mole of S02 (g) into S03 (g) the
reversibly and isothermally from 5 atm to 1 atm at 25° C. enthalpy of reaction at constant volume, M, at 298 K is
[Ans. - 3984 J] -97.027 kJ. Calculate the enthalpy of reaction, /j.Jf, at constant
[Hint: Use w = - 2.303 nRT log PI ] pressure.
P2 [Ans. /lli = - 98.267 kJ]
12. How much energy is absorbed by 10 moles of an ideal gas if it [Hint: . Use the reaction,
expands from an initial pressure of 8 atmosphere to 4 1 3 1
S02(g) + - o/g) ~ S03(g), I'l.n = 1- - = - -]
atmosphere at a constant temperature of 27° C? 2 2 2
(R = 8.3lJ mol- I K-!) 21. The heat liberated on complete combustion of7.8 g benzene is
[Ans. 1.728 x 104 J] 327 kJ. This heat has been measured at constant volume and at
[Hint: In isothermal process, till = 0, 27 ° C. Calculate the heat of combustion ot benzene at
so q (heat absorbed) = - w. Thus, apply the equation constant pressure. (R = 8.3 JK-1 mol-I) (lIT 1996)
q = 2.303nRT log...l. ]
P, [Ans. -3273.7 kJ mor l ]
P2 22. ,1 mole of naphthalene (ClOHg) was burnt in oxygen gas at
13. A given mass of a gas at 0° C is compressed reversibly and 25 ° C at· constant volume. The heat evolved was found to be
adiabatically to a pressure 20 times the initial value. Calculate 5138.8 kJ. Calculate the heat of reaction at constant pressure.
(R = 8.3 JK- l mol-I)
the final temperature of the gas. [~~ = 142]
[Ans. 5l43.8kJ]
[Ans. T2 = 662.2 K] [Hint: Water is present in liquid state at 25° C and naphthalene
in solid state.]
[Hint: Apply the formula [~J y =[ ~J I - y] 23. The enthalpy of formation of methane at constant pressure and
300 K is -75.83 kJ. What will be the heat of formation at
14. 3 moles of hydrogen are compressed isothermally and constant volume? (R = 8.3 J K -I mol -I)
reversibly from 60 dm 3 to 20 dm 3 and 8.22 kJ of work is done [Ans. -73.34 kJJ
on it. Assuming ideal behaviour, calculate. the temperature of 24. The heat change for the reaction,
the gas.
N 2(g) + 3H2(g) -----7 2NH3I(g)
[Ans. 300 K]
is - 92.2 kJ. Calculate the heat of formation of ammonia.
15. To what pressure must a certain ideal gas(y = 1.4) at 373 K
[Ans. - 46.1 kJ mol-I]
and 1 atmospheric pressure be compressed adiabatically in
25. /j.Jf0 for the reaction,
order to raise its temperature to 773 K?
[Ans. 7.89 atm] 4S( s) + 60 2(g ) -----7 4S0 3(g )
16. 1 mole of an ideal gas (C v = 12.55 J K-! moe!) at 300 K is is -1583.2 kJ. Calculate /j.Jf; of sulphur trioxide.
compressed adiabatically and reversibly to one-fourth of its [Ans. - 395.8 kJ]
original volume. What is the final temperature of the gas? 26. Calculate the heat change in the reaction,
[Ans. 752 K] 4NH3 (g ) + 302 (g) -----7 2N2 (g) + 6H20( I)
17. Calculate q, w, M and M for the reversible isothermal
at 298 K given that heats of formation at 298 K for NH3 (g )
expansion of 1 mole of ideal gas at 27° C from a volume of 10 and H 2 0(I) are - 46.0 and- 28{).0 kJ mol- I respectively.
dm 3 to a volume of 20 dm 3 .
[Ans. /lli 0 =: -1532 kJ] ''',
[Ans. q= -W= 1729 J] 27. Calculate the heat of combustion of 1 mole of C2H 4 (g) to
18. Calculate the internal energy change for the process in which
form CO2(g) and HzO(g) at 398 K and 1 atmosphere, given
1.0 kcal of heat is added to 1.2 litre of O2 gas in a cylinder at
that the heats of formation of CO 2(g ), H 20(g ) and CZH 4 (g)
constant pressure of 1.0 atm and the volume changes to 1.5 litre.
are - 94.1, - 57.8 and + 12.5 kcal mol-! respectively.
[Ans. 0.993 kcal]
[Ans. - 316.3 kcal]
484 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
28. The heats of combustion of CH4 (g ) and ~H6 (g ) are -890.3 36. The standard enthalpy of combustion at 25° C of hydrogen,
and - 1560 kJ mol- 1 respectively. Which has higher calorific cyclohexene (C6HlO ) and cyclohexane (C6H12 ) are - 241,
value? - 3800 and - 3920 kJ mol-' respectively. Calculate the heat of
[Ans. Methane has higher calorific value.] hydrogenation of cyclohexene. [ISM (Dhanbad) 19921
29. The heat of combustion of butane is 2880 kJ mol- t . What is [Ans. -121 kJ mol-I]
the heat liberated by burning 1 kg of butane in excess of [Hint:
oxygen supply? 1
H2(g) + '2 °2(g) ---7 HzO(g); ... (i)
[Ans. 49655 kJ]
30. The heat of formation of CH4 (g ), ~H6 (g ) and C4 HlO (g ) are (M! =-241kJmor-')
- 74.8, - 84.7 and - 126.1 kJ mol-I respectively. Arrange them C6H 10 (g) + -17 02(g) ---7 6C02 (g ) + 5HzO(g); ...(11
.. )
in order of their efficiency as fuel per gram. Heats of 2 (M! 3800 kJ mort)
formation of CO2(g ) and H2 0(l) are - 393.5 and - 285.8 kJ C6H I2 (g) + 90 2(g) ---7 6C02(g) + 6H 20(g); ... (iii)
1
morl respectively. (Mf = 3920 kJ mor )
[Ans. CH 4 > C2~ > C4H IO ] Adding eqs. (i) and (ii) and subtracting eq. (iii),
[Hint: First determine heat of combustion in each case and then ~HIO(S) + H2 (g) ---7 C6Hds);
find the calorific value.] M! == - 241- 3800 - (-3920) = -121 kJ mor' ]
31. The heat of combustion of carbon to CO2(g ) is 37. From the following data of heats of combustion, find the heat
- 393.5 kJ mol-'. Calculate the heat released upon formation offormation ofCH3 0H(l):
3
of 35.2 g of CO 2(g) from carbon and oxygen gas. CH30H(I) + 02(g) ~ CO2 (g)+ 2H20(I);
[Ans. - 315 kJ] 2
AH -726kJ
32. Calculate LVI;ofC6 H12 0 6 (S) from the following data: . C(s) + O2 (g ) ~ CO2 (g); AH = - 394 kJ
I
LVIcomb of C6 H I2 0 6(s) == - 2816 kJ mOrl , LVI; of CO2(g) . H2 (g)+ - 02(g)~ H2 0(l); AH = 286kJ
2
'= - 393.5kJ mor' and LVI; (Hpj - 285.9 kJ mol-I. {BIT (Ranchi) 19911
[Ans. 1260 kJ mOrl] [Ans.. :"'240kJmor']
33. Calculate the amount of heat released when: 38. Calculatp the heat;offQrmation of methane, given that
(i) 100 mL of 0.2 MHCl solution is mixed with 50 mL of 0.2 . heat of formation of water - 286 kJ mol-I
MKOH. heat of c6'inbustion of methane == 890 kJ morl
(ii) 200 mL of 0.1 MH zS04 is mixed with 200 mL of 0.2 M
KOH solution.
.
\
hea~ of
'.-
combustion of carbon - 393.5 k1 morl
([SM (DhanbacO ! 9931
[Ans. (i) 0.57 kJ (ii) 2.18 kJ]
[Ans. 75.5 kJmorl]
34. When 100 mL each of HCI and NaOH solutions are mixed,
5.71 kJ of heat was evolved. What is the molarity of two 39. Calculate the standard heat of formation of ~OH8
solutions? The heat of neutralisation ofHCI is 51.1 kJ. (naphthalene) if standard heat of combustion of naphthalene is
[Ans. 1M] 1231.0 kcal at 298 K and standard heat of formation of
CO2 (g) and H20( l) are - 94.0 kcal and - 68.4 kcal
35. Determine the enthalpy of the reaction,
respectively.
C3 Hg(g) + H2(g)~ ~H6(g)+ CH4 (g)
[Ans. 17.4kcal]
at 25° C, using the given heat of combustion values under
40. The heat of combustion of liquid ethanol is 327.0 kcal.
standard conditions.
Calculate the heat offormation of ethanol, given that the heats
. Compound H 2 (g) CH4 (g) ~H6(g) C(graphite)
offormation of CO2 (g ) and H2 0(l) are -94.0 kcal and 68.4
!1l-F' (kJ mol-I) --285.8 -890.0 -1560.0 -393.5 kcal respectively.
The standard heat offormationofC3 Hg (g )is-103.8 kJ mol-I. . [Ans. 66.2 kcal]
nn 1992) 41~ .C;aLculate heat of formation of cane sugar from following data:
'.' ,",'
[Ans. 55.7 kJ] ,,~: I
I H2 (g) + - O2 (g) ~ H2 0(g); LVI = 68.4 kcal
[Hint: H2(g) + - 02(g) H 20; (LVI - 285.8 kJ) ...(i) 2
2
... (ii) C(g) + O2 (g ) ~ CO 2(g); LVI:= - 94.4 kcal
(Mf 890.0 kJ)
~2H22011 (s) + 1202 (g) ~ I2C02(g) + IIHz0(l);
7
C2~(g) + - 0z(g) ---7 2C0 2(g) + 3H zO; ... (iii)
LVI - 1350.0 kcal
2 .
(Mf == 156u.0 kJ) [Ans. 535.2 kcal] .
C + O2 (g) ---7 CO 2 (g); (LVI - 393.5 kJ) ... (iv) 42. The heats of formation of C6~(l), H2 0(l) and CO2 (g) are
3C+ 4H2(g)---7C 3H g (g); (M! =-103.8kJ) ... (v) 11.70, - 68.4 and 94.0 kcal respectively. Calculate the heat
MUltiplying eq. (i) by' 5 and eq. (iv) by 3 and adding both the of combustion of benzene (I) .
.equations and subtracting eqs. (ii), (iii) and (v).]
.. [Ans. -780.9 kcal]
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 485
[Hint: c;H6(I) + 1; Gig) ~ 6C0 2 (g) + 3HzO(I); tili = ? 51. Use the bond energy data and calculate the enthalpy change
for:
!:JH = 6 x tilif (C0 2) + 3 x tilif (H2 0 ) - tilif (C6H 6)] H
43. Calculate the heat of hydrogenation ofc;H2 to C2H4 . I
2C(g) + 2H(g) + 2Cl(g)~ H- C-CI
H 2 (g) + ..!. O2(g) ~ H 20(l); AH = - 68.32 kcal . I
2 Cl
The bond energies of C-H and C-Cl are 413 and 328 kJ
mol-I respectively.
AH = - 310.61 kcal [Ans. -1482kJ mor l ]
C;~ (g) + 302 (g ) ~ 2CO z(g) + 2H2 0(l); 52. Calculate the heat of formation of ammonia from the
following data:
AH = - 337.32 kcal
Nz(g)+ 3H2(g)~ 2NH3 (g)
[Ans. - 41.61 kcal]
44. Calculate the heat of hydrogenation,
==
The bond energies of N N, H - H and N - H bonds are
226, 104 and 93 kcal respectively.
c;H4 (g) + H2(g) ~ c;H6(g) [Ans. -10 kcal]
given that, the heat of combustion of ethylene, hydrogen and 53. Use the following bond dissociation energies to compute the
ethane are - 337.0, - 68.4 and - 373.0kcal respectively. C-H bond energy in methane:
[Ans. -324 kcal] (i) CH4(g)~ CH (g) + H(g); 3 AH = 475 kJ mor l
45. Ifthe heat offormation of A1 2 0 3 (s)and Cr203(s)~ 1596 kJ (ii) CH3 (g ) ~ CH z(g) + H(g ); AH = 470 kJ mol-I
and 1134 kJ (both exothermic) respectively. Calculate AH of
(iii) CH2(g) ~ CH(g) + H(g ); AH = 416 kJ mol-I
the thermite reaction.
(iv) CH(g) ~ C(g) + H(g); AH = 335 kJ mol-I
Cr203(s) + 2A1(s) ~ 2Cr(s) + A1 2 0 3(s)
[Ans. 424 kJ mol-I]
[Ans. - 462 kJ] o .
46. Calculate the enthalpy of transition of rhombic sulphur to 54. Calculate AHf for chloride ion from the following data:
monoclinic sulphur from the following data:
S(rhombic) + 02 (g ) ~ S02 (g); AH = - 297.5 kJ
'21 H2 (g) + '21 Cl 2 (g ) ~ HC1(g ); AH = - 92.4kJ morl
S(monocliriic) + O 2(g ) ~ SOZ (g ); AH = - 299.9 kJ HCI(g) + nH20 ~ H +(aq.) + cr (aq.);
[Ans. + 2.4 kJ] AH = - 74.8 kJ mol-I
47. Calculate AH forthe reaction, AH C _ -I
f (H + aq.) - 0.0 kJ mol (III 19'1L)
H 2 (g)+ Yz02(g)~ H 20(g)
given that bond energies of H-H and = ° °
bond and O-H
bond are 433 kJ mol-I, 492 kJ mol- I and 464 kJ mol-I.
[Hint: Required equation is
YzCI 2(g) + nHzO ~ CI+ (aq.); tili =?
[Ans. - 249 kJ] Adding both equations.
48. Using the bond enthalpy data, calculate AH of the following Yz H 2(g) + Yz Clz(g) + nHzO ~ H+ (aq.) + C1-(aq.);
reaction: tili =-167.2
2Cl 2 (g) + 2HzO(g ) ~ 4HCI(g) + 0z (g) Yz H 2(g) ~ H+ (aq.); tili =0
given that, bond energies ofCl-Cl; H-Cl, O-H and 0=0
are 242.8, 431.8, 464 and 442 kJ morl respectively.
So, Yz CI 2 (g) + nHzO ~ Cqaq.); tili =-167.2 kJ mol-I]
[Ans. 172.4 kJ mol-I] 55. The heat of ionisation of formic acid is 1.5 kJ / mol. 9.2 g
formic acid on reaction with 7 g ainmonium hydroxide gives
49. Calculate the enthalpy of the reaction,
10.8 kJ of heat. Calculate the heat of ionisation of ammonium
Sn02(S)+ 2H z(g) ~ Sn(s) + 2H20(l) hydroxide. (1 cal = 4.2 J)
[Ans. 2.04 kJ / mol]
given that, enthalpy of formation of Sn02(S) and H 20(l) are
580.7kJ and - 285.8 kJ respectively. 56. Assuming that 50% of the heat of useful, how many kg of
water at 15 0 C can be heated to 95.00 C by burning 200 litre of
[Ans. +9.1 kJ]
methane measured at NTP? The heat of combustion of
50. Calculate the enthalpy change for the reaction,
methane is 211 kcal mol-I.
H 2 (g)+ Clz(g)~ 2HCl(g) [Ans. 11.76 kg]
57. The standard potential for the reaction,
given that, bond energies of Cl-Cl and H-Cl are
436, 243 and 432 kJ mol-I. Ag +(aq.)+ Fe2+(aq.) ~ Fe 3+ (aq.) + Ag(s)
[Ans. -185 kJ mol-I] is 0.028 V What is the standard free energy change for this
reaction?
[Ans. 2.702 kJ mol-I]
486 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
58. Calculate the theoretical maximum efficiency of a heat engine 67. An engine operating between 150°C and 25°C takes 500 J
operating between 373 K and 173 K. heat from a high temperature reservoir. Assuming there is no
. [Ans. 0.$36 or 53.6%] frictional loss, calculate the work that can be done by the
59. The standard free energy of formation in the gaseous state of engine.
methanol, dimethyl ether and water are - 38.7, - 27.3 and [Ans. 148 J]
-54.6 kcal respectively. Is the transformation of methanol to 68. At 300 K, the standard enthalpies of formation of
dimethyl ether and water in gaseous state possible? C6 H sCOOH(s), COz(g ) and Hz0(l) are -408, -393 and -286
2CH~OH CH3 0CH3 + H 2 0 kJ mol- 1 respectively. Calculate the heat of combustion of
[Hint! t:..G'" for the transformation benzoic acid at (i) constant pressure and (ii) constant volume.
1 I
= L t:..G(;roductS) L t:..G(:eactants) (R =8.3IJmol- K- ) (lIT 1995)
= ve (the transformation is possible)] [Ans. (i)!:..H =- 3201 kJ mol-I;
(ii) t:..E = - 3199.75 kJ mol-I]
60. Ethanol boils at 78.4° C and standard enthalpy of vaporization
of ethanol is 42.4 kJ morl. Calculate the entropy of 69. For the reaction,
vaporization of ethanol. Brz (I) + CI 2 (g) ----+ 2BrCI(g)
[Ans. 120.9 J K- l mol-I] Mf 29.37 kJ mor 1 and t:..S = 104 J K-1 mol-I. Find the
6t. The following data is known about the melting ofKCl: temperature above which the reaction would become
Mf 7.25 kJ mOrl and t:..S = + 0.007 J K- 1 mor 1 spontaneous.
[Ans. Above 282.4 K]
Calculate its melting point.
70. For the synthesis of ammonia,
[Ans. 1035.7 K]
N z(g ) + 3Hz(g) ----+ 2NH3 (g)
[Hint: At melting point t:..G =0] Calculate. MfO ,t:..S ° and t:.Go at 300 K using the following
62. For the reaction,
data:
Ag20~ 2Ag(s) + ..!. 02(g) Species H2 NH3
2
Calculate the temperature at which free energy change is zero. Mf; I (kJ mol-I) o 46.2
At a temperature lower than this, predict whether the forward SO/(JK- 1 mol-I) 130.6 192.5
or the reverse reaction will be favoured. Give reason.
(t:.H = + 30.56 kJ and t:..S = + 0.066 kJ K- 1 mol-I at one
[Ans. !:..H0 = - 92.4 kJ mol-I, t:..so = :"198.3 J K- I mol- I
t:..Go = 32.91 kJ mol-I]
atmosphere)
71. How much heat is required to change 15.6 g of benzene from
[Hint: Calculate T by applying tfie formula liquid into vapour at its boiling point of 80°C? Entropy of
t:..G = !:..H T t:..S and t:..G = O. vaporization of benzene is 87 J K- I morl.
Then find the value of t:..G at lowertemperature than T. The value of
t:..G com"s positive; hence, the reverse reaction will be favoured. At [Ans. 6142.2 J]
temperature higher than T, the reaction is spontaneous.] 72. Calculate the standard free energy change for the combustion
63. Calculate the boiling point of the liquid if its entropy of of glucose at 298 K, using the given data.
vaporization is 110 J K- 1 mol- 1 and the enthalpy of C6 H 12 0 6 + 60 2 ----+ 6C02 + 6H 20
74. The polymerisation of ethylene to linear polyethylene is 78. For the reaction,
represented by the reaction, 4C (graphite) + 5H2 (g) nC4HIO (g );
nCH 2 CH2 CH2 - CHdii !::..H0 124.73 kJ mol- 1
where, n has a large integral valu~. Given that the average lJ.So - 365.8 J K- 1 mol-I
enthalpies of bond dissociation for C = C and C-C at 298 K
are +590 and + 331 kJ mol-I respectively, calculate the 4C (graphite) + 5H2 (g ) iso-C4 H IO (g)
enthalpy of polymerisation per mole of ethylene at 298 K.
!::..H 0
131.6 kJ mol~l
(lIT 1994)
[Hint: nCH 2 CH 2 CH 2 CHdii t:..s o 381.079 J K- 1 mol-I
There are equal number of C-H bonds on both sides but on
reactant side there are nC C bonds and on product side Indicate whether normal butane can be spontaneously
(2n + l)C-'-Cbonds. converted to iso-butane or not.
Enthalpy of polymerisation [ATls, Yes, t:..Go == - 2.32 kJ]
(2n + 1)6H(c_C) [Hint: For nC4H IO ,
590n (2n + 1)(331) t:..Go = 6H o - T6S o
590n 662n [2n + .I-t 2n as n is very large] 124.73 298(-365.8 x 10-3 ) = 15.72 kJ
72n kJ For iso-butane (iso-C 4H IO ),
Enthalpy of polymerisation per mole 6GO 131.6 298(-:- 381.079 x 10-3 )
6H 72n _ 72 kJ mor l ] 18.04 kJ
n n
For conversion of nC4H 10 iso-C4H 10 ,
73. An athlete is given 100 g of glucose (C6H I2 0 6 ) of energy t:..Go = 18.04 (-15.72) = 2.32 kJ
equivalent to 1560 kJ. He utilises 50% of this gained energ-f in Negative value shows that the process is spontaneous.]
the event. In order to avoid storage of energy in the body,
'79. The temperature of a bomb calorimeter was found to rise by
calculate the mass of water he would need to perspire. The 1.617 K, when a current of 3.20 amp was passed for 27 sec
enthalpy of evaporation of water is 44 kJ mol-I. from a 12 V source. Calculate the calorimeter constant.
[Hint: Unused energy 1560 =780 kJ [Hint: Energy absorbed by the calorimeter
2 \ = I x t x V 3.2 x 27 x 12 = 1036.8 J
Mass of water needed for perspiration = 18 x 780 = 318.96 g] Calorimeter constant (ms) can be calculated as,
44 q ms!::"t
76. Calculate the entropy of ideal mixing when 2 moles of N z, 3 1036.8 = ms X 1.617
moles of H2 and 2 moles of NH3 are mixed at constant ms 641.187 kJ]
temperature, assuming no chemical reaction is occurring.
80. 1 mole of an ideal gas is allowed to expand isothermally at
[Ans. 62.80 J K- 1] 27 ° C until its volume is tripled. Calculate t:..S sys and t:..S univ
[Hint: Use the relation, under the following conditions:
6S R :E nj loge Xi (a) the expansion is carried out reversibly.
when ni =no. of moles of component (b) the expansion is a free expansion.
x; = mole fraction ofthe component] [A'TIs. (a) IJ.Ssys 9.135 J K- i rnol- 1
n. Calculate free energy change for the reaction: 6S surr = 9.135 J K- 1 rnor 1
H2(g)+ CI 2(g)-t 2H-Cl(g)
t:..Suniv 0
by using the bond energy and entropy data.
Bond energies Cl-CI and H-CI bonds are 435 kJ (b)6Suniv =6Ssys=9.135JK- 1 mor l ]
mol-I, 240 kJ mol-I and 430 kJ mol- 1 respectively. Standard [Hint: (a) In isothermal reversible process:
entropies of Hz, Cl2 and HCl are 130.59,222.95 and 186.68
J K- 1 mol-I respectively. . 'T
[ATls. 190.9 kJ] q W = 2.303RT log V2
[Hint: 6Go can be calculated by using: VI
6Go 6Ho TIJ.S° 2.303 x 8.314 x 300 log 3 = 2740.6 J mol-I
6H o :E (BE\.eactants - :E (BE)products
= 2740.6 = 9.135 J K- 1 rnol- 1
=435 + 240 - 2 x 430 -185 kJ T 300
t:..so == :E S;roducls :E S ;eactants t:..S surr = - t:..Ssystem = - 9.135 J K- 1 mol-I
2 x 186.68 130.59 - 222.95
!::,.Suniv = 0
19.82 J K- 1 19.82 X 10-3 kJ K- 1 (b) In case offree expansion:
t:..Go 6Ho Tt:..S o
185 298 x 19.82 x 10- 3 = -190.9 kJ]
!::"S r
2.303nR log V2 J == 9.135 J K- 1 mol-I
\V1
488 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
VD ---------H = 0.3362 kJ K- 1 ]
84. What amoimt of ice will remain when 52 g ice is added to
!
100 g of water at 40" C?
VB
VA
--------1;:71"!
--------A:
Specific heat of water is I callg and latent heat of fusion of ice
is 80 caUg.
[Ans. 2 g ice]
I I [Hint: At the stage of thermal equilibrium at 0° C,
I I
I I
Heat lost by water Heat absorbed by ice to melt.
TA TB ms~T =mL
Temp_ looxlx40=mx80
m==50g
(a) the temperature of gas at B. Remaining ice = 52 - 50 =2 g]
(b) heat absorbed or evolved in each process. 85. Calculate the Mi~ of C6HI2 0 6(s) from the following data:
(c) total work done in cyclic process. MiCOnID [C6HI2 0 6 (s)]:= - 2816 kJ I mol
[Hint: A ~ B: (It is isobaric process)
Mi~ of CO2 (g) == - 393.5 kJ I mol
VA = VB Mi~of H 20(1) == - 285.9 HI mollBCECE 2006]
TA TB
V [Ans. -1260 kJ/mol]
TB == -I!.. X TA == 2 x 300:= 600 K
VA 86. A liquid freezes into solid (Mi := - 500 J mol-I ) at 100 K and
·5 I atm. Find the values of:
qAB = nCp ~T =2x- R ~T
2 (i) Gibbs free energy change
. 5 (ii) entropy change. rCBSE (Mains) 20061
== 2 x- x 2 x 300 = 3000 cal
2 [Hint: Liquid ~ Solid
r (Isothermal process) (i) ~G =0, at equilibrium
~U==O (11") ~
A" -
_ Mf _ -500 _ 5 J K- 1
------ mo1-1]
T 100 .
•
. CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 489~~
=~ OBJECTIVE UESTIONS
13. A thermodynamic quantity is that:
Set-1: Questions with single correct answer
(a) which is used in thermochemistry
1. Thermodynamics is concerned with: (b) which obeys all laws of thermodynamics
(a) total energy ofa system (c) quantity whose value depends only upon the state of the
(b) energy changes in a system system
(c) rate ofa chemical change (d) quantity which is. used in measuring thermal change
(d) mass changes in nuclear reactions 14. Thermodynamic equilibrium involves: [CET (Ph.) 19911
2. An isolated system is that system in which: (a) chemical equilibrium (b) thermal equilibrium
[PET (MP) 19931 (c) mechanical equilibrium (d) all the three
(a) there is no exchange of energy with the surroundings 15. For the reaction of one mole zinc dust with one mole sulphuric
(b) there is exchange· of mass and energy with the acid in a bomb calorimeter, L\U and w correspond to:
surroundings (AIIl\IS 200S)
(c) there is no exchange of energy and mass With the (a) L\U < 0, w = 0 (b) L\U < 0, w < 0
surroundings (c) L\U > 0, W = 0 (d) L\U> 0, W > 0
(d)· there is exchange of mass with the surroundings [Hint: In bomb calorimeter, W = 0, L\U = q( -ve)]
3. Identify the intensive property from the following: 16. A system is provided with 50 joules of heat and the work done
(a) volume (b) mass on the system is 10 joules. What is the change in internal
(c) enthalpy (d) temperature energy of the system in joules? rEAMCET (Engg.) 2()10]
4. Which one of the following is an extensive property? (a) 60 (b) 40 (c) 50 (d) 10
(Corned (Karnataka) 2008] 17. During an isothermal expansion o(an ideal gas, its:
(a) Enthalpy (b) Concentration (CBSE 1991)
(c) Density (d) Viscosity (a) internal energy increases
5. For an adiabatic process, which of the following relations is (b) enthalpy decreases
correct? (CPMT 1990) (c) enthalpy remains unaffected
(a) I1E == 0 (b) P L\V == 0 (c) q == 0 (d) q == + w (d) enthalpy reduces to zero
6. Which one is true from the following for isobaric process? 18. The work done in ergs for a reversible expansion of one mole
. fCET (Gujar~t) 2008] of an ideal gas from a volume of 10 litre to 20 litre at 25" Cis:
(a) ~:: 0 (b) L\q = 0 ICMC (Vellore) 19911
(c) MI== 0 (d) I1E = 0 (a) 2.303 x 8.31 x 107 x 298 log 2
7.· Foran ideal gas, the value of (dE)
dV T
is:
[PET (MP) 19931
(b) 2.303 x 0.0821 x 298 log 2
(c) 2.303 x 0.0821 x 29~ log 0.5
(a) positive (b) zero (d) 2.303 x 2 x 298 log 2
(c) negative (d) interchangeable 19. When an ideal gas is compressed adiabatically and reversibly,
8. A process, in which pressure remains constant, is called: the final temperature is:
(a) isochoric process (b) isothermal process (a) higher than the initial temperature
(c) adiabatic process (d) isobaric process (b) lower than the initial temperature
9. A process in which volume remains constant, is called: (c) the same as initial temperature
(a) isoehoric process (b) isothermal process (d) dependent upon the rate of compression
r-1
(c) adiabatic process (d) isobaric process 20. Adiabatic reversible expansion of a gas is represented by:
11.
(c) I1E > Oand MI> 0
(a) Heat
(c) Internal energy
(d) both I1E == oand MI = 0
Which one of the following is a state property?
(b) Work
(d) Potential energy
(c) (~ r=( ~r I (d) all are correct
(a) Hess's law 33. Under which of the following conditions is the relation,
(b) first law of thennodynamics M! = IJ.E + P I1V valid for a closed system?
(c) Kirchhoff's law (a) Constant pressure
(d) second law ofthennodynamics (b) Constant temperature
23. The heat content of the system is called: (c) Constant temperature and pressure
(a) internal energy (b) enthalpy (d) Constant temperature, pressure and composition
(c) free energy (d) entropy 34. Which of the following is an endothennic reaction?
24. If one mole of ammonia and one mole of hydrogen chloride (a) 2H2 (g)+ 02(g)~ 2H2 0(l)
are mixed in a closed container to fonn ammonium chloride (b) N 2 (g)+ 02(g)~ 2NO(g)
gas, then: (KCET 2008) (c) NaOH(aq.)+ HCl(aq.)~ NaCl(aq.)+ H 2 0(l)
(a) M! < I1U (d) C2H sOH(aq.)+ 302(g)~ 2C0 2 (g)+ 3H2 0(l)
(b) M! > I1U
(c) I1H =IJ.U 35. Which ofthe following reactions is endothennic?'
(d) there is no relationship between M! and tiU (a) CaC03(s)~ CaO(s)+ CO2 (g)
25. An exothennic reaction is one in which the reacting (b) Fe(s) + S(s)~ FeS(s)
substances: (c) NaOH(aq.) + HCl(aq.) ~ NaCI(aq.) + H 20(l)
(a) have same energy as products (d) CH4 (g) + 202 (g) ~ CO2 (g)+ 2H2 0(I)
(b) have less energy than the products 36. The fonnation of water from H2 (g) and O2 (g) is an
(c) have more energy than the products exqthennic process because:
(d) are at higher temperature than the products
(a) the chemical energy of H2 (g ) and O2 (g ) is more than that
26. In endothennic reactions, the reactants: of water
(a) have more energy than products
(b) the chemical energy of H2 (g) and O2(g ) is less than that
(b) have as much energy as the products
of water
(c) are at lower temperature than products
(e) the temperature ofH2 (g) and 02(g) is higher than that of
Cd) have less energy than the products
water
27. IdentifY the reaction in which the heat liberated corresponds to
the heat of fonnation (M!): (EAMCET 2006) (d) the temperature of H2 (g) and 02 (g) is lower than that of
water
(a) C (diamond) + 02(g) -7 cO 2(g) + heat
(b) 2H2 (g ) + 02 (g) -7 2H2 0(g) + heat
37. Which one of the following reactions is an exothennic
reaction? .
(c) C (diamond) + 2H 2 (g) -7 CH 4 (g) + heat
(a) CaC03(s) ~ CaO(s) + CO2(g)
(d) S (rhombic) + O2(g ) -7 S02 (g) + heat
28. In an exothennic reaction, M! is: (b) N 2 (g) + 02(g) ~ 2NO(g)
(a) positive (b) negative tc) 2HgO(s)~ 2Hg(s)+ 02(g)
(c) zero (d) may be positive or negative \d) C(s) + 02(g) ~ CO2 (g)
29. Evaporation of water is: 38. Which one of the following is not applicable for a
(a) a process in which neither heat is evolved nor absorbed thermochemical equation?
(b) a process accompanied by chemical reaction (a) It tells about physical state of reactants and products
(c) an exothennic change (b) It tells whether the reaction is spontaneous
(d) an endothennic change (c) It tells whether the reaction is exothermic or endothennic
30. An endothermic reaction is one in which: (d) It tells about the allotropic fonn (if any) of the reactants
(a) heat is converted into electricity "9. The enthalpies of all elements in their standard state at 25° C
(b) heat is absorbed and one atmospheric pressure are:
(c) heat is evolved (a) same (b) always positive
(d) heat changes to mechanical work
(c) always negative (d) zero
31. If total enthalpy of reactants and products is H Rand H p
respectively, then for exothennic reaction: 4U. The heat of reaction does not depend upon:
(a) HR Hp (b) HR < Hp (a) physical state of the reactants and products
(c) HR >Hp (d) HR Hp 0 (b) whether the reaction has been carried at constant pressure
32. Calculate the work done when I mol of an ideal gas is or constant volume
compressed reversibly from 1 bar to 4 bar at a constant (c) the manner by which the reaction has been carried
temperature of 300 K : (DPMT 2009) (d) the temperature at which the reaction has been carried
(a) 4.01 kJ (b) -8.02 kJ 41. The value of M! I1U for the following reaction at 27°C will
(c) 18.02 kJ (d) -14.01 kJ be:
42. Since, the enthalpy of the elements in their standard states is which one of the following statements is correct?
taken to be zero, the heat of formation (!J.H f) of compounds: (a) x - y> 0 (b) x y < 0
(a) is always negative (b) is always positive (c) x y = 0 (d) None of these
(c) is zero (d) may be positive or negative 53. According to the equation,
43. The difference between heats of reaction at constant pressure 15
C6 H6 (I) + - 02 (g ) ------t 6C0 2(g ) + 3H2 0(1);
and constant volume for the reaction, 2
2C6 H6 (I) + 1502(g ) ------t 12C02(g) + 6H 20(l) at 25" C in !J.H - 3264.4 kJ mol- i
kJ is: (liT 1991)
the energy evolved when 7.8 g benzene is burnt in air will be:
(a) +7.43 (b) +3.72 (c) -7.43 (d) -3.72
IPET (MP) 1990)
44. For a gaseous reaction, A (g)+ 3B (g) -,0 3C (g) + 3D (g 1
(a) 163.22 kJ (b) 32.64 kJ (c) 3.264 kJ (d) 326.4 kJ
IJ..E is 17 kcal at 27°C. Assuming R 2cal K- I mol-I, the
54. !J.Hf (x), !J.Hf (yl' !J.Hf (Rl and !J.Hf (S) denote the enthalpies of
value of 6H for the above reaction is:
formation of x, y, R and S respectively. The enthalpy of the
(a) 15.8 kcal (b) J8.2 kcal
reaction, x + y ------t R + S is given by:
(c) 20.0 kcal (d) 16.4 kcal
(a) !J.Hf (xl + !J.Hf (Yl
45. Which of the following statements is correct for the reaction,
(b) !J.Hf(R) + !J.Hf(S)
CO(g ) + -1 O 2 (g ) ------t CO 2( ' temperature and
g) at constant (c) !J.Hf(x) + !J.Hf(y) - !J.Hf(R) AHf(S)
2 '
(d) AHr (R) + !J.Hf (S) - !J.Hf (x) !J..Hf (y)
pressure?
55. The enthalpy change for the reaction,
(a) !J.H = IJ..E (b) !J.H < IJ..E
CzH4 (g) + 302 (g) ------t 2C02 (g ) + 2H20(g ) is called:
(c) !J.H> IJ..E (d) None ofthese
(a) enthalpy offormation (b) enthalpy of combustion
46. For the reaction, Ag 2 0(s) ------t 2Ag(s) + I 02(g ) which one (c) enthalpy of vaporisation (d) enthalpy of sublimation
2
56. The heat of combustion of methane is -880 kJ mor l . If 3.2 g
of the following is true? of methane is burnt ........... of heat is evolved.
(a) !J.H = IJ..E (b) !J.H < IJ..E (a) 88 kJ (b) 264 kJ (c) 176 kJ (d) 440 kJ
(c) !J.H > IJ..E (d) AH I IJ..E 57. The enthalpy change for the r('-action,
2
2C(graphite} + 3H 2 (g} C2~(g}
47. Thelmochemistry is the study of relationship between heat is called:
energy and:
(a) enthalpy offormation (b) enthalpy of combustion
(a) chemical energy (b) activation energy
( c) enthalpy of hydrogenation (d) enthalpy of vaporisation
(c) friction energy (d) none of these
58. The enthalpy of formation of water from hydrogen and
48. Assume each reaction is carried out in an open container. For oxygen is - 286.0 kJ mol-I. The enthalpy ofdecomposition of
which reaction will!J.H = AU? reBSE (Med.) 2006) water into hydrogen and oxygen is ...... kJ mol-I:
(a) H2 (g) + Br2 (g) ------t 2HBr(g) ('1) -286.0 (b) -143.0 (c) 286.0 (d) 143.0
(b) C( s) + 2H20(g) ------t 2H2 (g ) + CO2 (g ) 59. The heat of combustion of C(graphite) is -393.5 kJ mol-I. The
+
(c) PCIs(g) ------t PCI 3 (g) CI 2 (g) heat of formation of CO2 from graphite is ..... kJ mor l :
(d) 2CO(g) + 0z (g ) ------t 2COz (g ) (a) 393.5 (b) -393.5 (c) -787.0 (d) 787.0
49. The enthalpy change in the reaction, 2CO + 02 ------t 2C02 is 60. The enthalpies of formation of organic compounds are
termed as: conveniently determined from their:
(a) enthalpy of reaction (b) enthalpy of fusion (a) boiling points
(c) enthalpy offormation (d) enthalpy of combustion (b) melting points
50. Reaction, H2 (g ) + 12 (g ) ------t 2HI; !J.H = 12.40 kcal ( c) enthalpies of neutralization
According to this, heat of formation of HI will be: (d) enthalpies of combustion
/pET (MP) 1991)1 61. !J.H combustion of a compound is always:
(a) 12.40 kca! (b) -12.4 kcal (a) positive (b) negative (c) zero (d) uncertain
(c) - 6.20 kcal (d) 6.20 kcal 61. The apparatus used for measuring the heat changes of a
S1. For the reactions, reaction is called:
(i) H2 (g)+ Clz(g) == 2HCl(g) + x kJ (a) a thermometer (b) a colorimeter
(ii) H2 (g) + Clz(g) = 2HCI(l) + y kJ (c) a calorimeter (d) none of these
which one of the foUowing statements is correct? 63. The heat of neutralization of any strong acid and strong base is
IPET (MP) 2007) always constant and AH = 57.3 kJ. This is because:
(a) x>y (b) x<y (c) x-y=O (d) x=y (Corned (Karnataka) 2008)
52. For the reactions, (a) both the acid and base undergo complete ionization.
(i) Hz (g) + Clz(g) = 2HCI(g) + x kJ (b) during neutralization, salt and water are formed.
(ii) 2HCI(g) == H2(g) + CI 2 (g) y kJ (c) I mole of water is formed from Wand OH- ions.
(d) the reaction is exothermic.
492 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
83. If S+ 02 ~ S02; Ml= 298.2kJ 91. The bond dissociation energy of C-H in CH4 from the
I equation
,S02 + - 02 -----t S03; Llli = -98.7 kl
2 C(g)+ 4H(g)~ CH4 (g); Ml 397.8kcal
S03 + H20 -----t HZS0 4; Llli = -130.2 kl is:
I (a) + 99.45 kcal (b) -99.45 kcal
HZ + - 02 -----t HzO; Llli = - 227.3 kl
2 (c) + 397.8 kcal (d) + 198.9 kcal
the heat offonnation of HZS04 will be: 92. The dissociation energy ofCH4 is 400 kcal morl and that of
(a) -754.4 kJ (b) + 320.5 kJ(c) 650.3 kJ (d) - 433.7 kJ ethane is 670 kcal mori. The C-C bond energy is:
84. Which of the following units represents the largest amount of (a) 270kcal (b) 70kcal (c) 200kcal (d) 240kcal
energy? 93. Heat of reaction at constant volume is measured in the
(a) Electron-volt (b) Erg apparatus:
(c) Joule (d) Calorie (a) bomb calorimeter (b) calorimeter
85. IfMl~ for H20 2(l) and Hz0(l)are-188 kJ mol- I and-286kJ (c) pyknometer (d) pyrometer
mor l , what will be the enthalpy change of the reaction 94. When 10 mL of a strong acid is added to 10 mL of an alkali,
2HzOz(/) ~ 2Hz°(l) + 02(g)? [PMT (lVIP) 19921 the temperature rises by 5° C. If 100 mL of the same acid is
mixed with 100 mL of the same base, the temperature rise
(a) 146 kJ mol- l (b) -196 kJ mol- i
would be:
(c) - 494 kJ mol- l (d) -98 kJ mol- l (a) 5°C (b) 50°C
86. The bond dissociation energies for C1 2, 12 and ICI are 242.3, (c) 20°C (d) cannot be predicted
151 and 211.3 kJ/mol respectively. The enthalpy of
95. Energy required to dissociate 4 g of gaseous hydrogen into
sublimation of iodine is 62.8 kJ I mol. What is the standard
free gaseous atoms is 208 kcal at '25 0 C. The bond energy of
enthalpy offormation ofICI(g)?
H-H bond will be:
(a) -211.3kJ/mol (b) 14.6kJ/mol
(a) 1.04 cal (b) 10.4 kcal
(c) 16.8kJ/mol (d) 33.5 kJ/mol
(c) 104 kcal (d) 1040 kcal
[Hint: CI 2(g) -----t 2C1(g); Llli I = 242.3 kl/mal
96. The heat of neutralisation of strong base and strong acid is
12(g) -----t 2I(g); Llli 2 = lSI kl/mal 57.0 kJ. The heat released when 0.5 mole ofHN0 3 solution is
ICl(g) -----t l(g) + Cl(g); Llli3 = 211.3 kl/mal added to 0.20 mole ofNaOH solution is: (KCET 1993)
12(s) -----t 12(g); Llli4 = 62.8 kl/mal (a) 57.0 kJ (b) 28.5 kJ
Required equation: (c) 11.40 kJ (d) 34.9 kJ
1 1 97. The enthalpy of combustion of cyclohexane, cyc10hexene and
Zlz(s)+ZClz(g) -----tICI(g); Llli=?
H2 are respectively -3920, -3800 and -241 kJ morl. The heat
Llli=62.8+151+242.3 211.3 of hydrogenation of cyclohexene is: (AHMS 2007)
2 (a) -121 kJ mol-I (b) 121 kJ morl
= 16.75 kl I mal] (c) -242 kJ morl (d) 242 kJ morl
87. Standard heat of formation for CCI 4, H20, CO2 and HCI at
98. If C(s) + 0z(g)~ CO2 (g); Ml = r
298K are - 25.5, - 57.8, 94.1 and 22.1 kJl mol respectively.
For the reaction, and CO(g) + I O2(g ) ~ CO2 (g); Ml = s
CCl4 + 2H20 ~ CO2 + 4HCI 2
what will be Ml? (SCRA 2007) then the heat of formation of CO is:
(a)36.4kJ (b)20.7kJ (c)-20.7kJ (d) 4l4kJ (a) r+ S (b) r s (c) S - r (d) r x S
88. Heat of combustion of CH4 , Cz~, CzH4 and CzHz are -212.8, 99. Given that,heat of neutralisation of strong acid and strong
-373.0, -337.0 and -310.5 kcal respectively at the same base is 57.1 kJ. Calculate the heat produced when 0.25 mole of
temperature. The best fuel among these gases is: HCl is neutralised with 0.25 mole of NaOH in aqueous
(a) C~ (b) CzH6 solution: (CPMT 1990)
(c) CzH4 (d) CzH z (a) 22.5 kJ (b) 57 kJ
89. Given, C(s) + 02 (g) ~ CO2 (g); Ml := - 395 kJ (c) 14.275 kJ (d) 28.55 kJ
S(S) + 0z(g)~ SOz(g); Ml:= -295 kJ 100. Which one of the following values of MIo represents that the
product is least stable?
CS z(I) + 302 (g ) ~ CO2(g ) + 2S0z(g); Ml =- 1110 kJ
(a) 94.0 kcal mol- 1 (b) -231.6 kcal mol- l
The heat offormation ofCS 2 (l ) is: IeEE (Bihar) 1992J
(c) +21.4 kcal morl (d) + 64.8 kcal morl
(a) 250 kJ (b) 62.5 kJ (c) 31.25 kJ (d) 125;':
90. The heats of combustion of rhombic and monoclinic sulphur 101. The value of MlO-H is 109 kcal mol-I. The formation of one
are -70960 and -71030 calorie respectively. What will be the mole of water in gaseous state from H(g) and O(g) is
heat of conversion of rhombic sulphur to monoclinic sulphur? accompanied by: (eBSE 1990)
(a) -70960 cal (b) -71030 cal" '," (a) 218 kcal (b) -109 kcal
(c) 70 cal (d) -70 cllI (c) -218 kcal (d) unpredictable
494 G.R.B. PHYSICALCHEMISTRY FOR COMPETITIONS
102. Heat of neutralisation of a strong dibasic acid in dilute solution (a) 750 K (b) 1000 K
by NaOH is nearly: (c) 1250 K (d) 500 K
(a) -27.4 kcalleq (b) -13.7 kcaiJeq [Hint: IJ.S L S Products - L S Reactants
(c) +13.7 kcalleq (d) -13.7 kcallmol
103. The enthalpy changes at 298 K in successive breaking of =50-[~X 60+~ X 40J
O-H bonds of water are
H2 0(g) ---7 H(g) + OH(g ); MJ:::: 498 kJ mort = 50- (30+ 60) = -40 J r i mol- t
At equilibrium, IJ.G = MJ - TIJ.S = 0
and OH(g) ---7 H(g) + O(g ); MJ 428 kJ mol- 1
i.e., MJ TIJ.S
The bond enthalpy of O-H bond is:
T = MJ = -30x 1000 = 750 K]
(a) 498 kJ mol- 1 (b) 428 kJ mol- t
IJ.S -40
(c) 70 kJ mort (d) 463 kJ mol- 1 113. 'At absolute zero the entropy of a perfect crystal is zero.' This
104. MJ and till for the reaction, S(s) + ~ O2 (g ) ---7 SO} (g) statement corresponds to which law of thermodynamics?
are related as: (a) First law (b) Second law
(a) MJ till - 0.5RT (b) MJ till 1.5RT (c) Third law (d) None of these
(c) MJ till+RT (d) MJ=till+1.5RT 114. Unit of entropy is: (PMT (Punjab) 2007]
105. A spontaneous change is one in which the system suffers: (a) J K- 1 morl (b) J mol- 1
(VITEEE 2008)
(c) rl K- 1 morl (d) JKmol- 1
(a) an increase in internal energy -
(b) lowering in entropy 115. Given that MJf(H) = 218 kJ/mol, express the H-H bond
( c) lowering in free energy energy in kcallmol: (EAMCET 2009)
. (d) no energy change (a) 52.15 (b) 911
106. The free energy change for a reversible reaction at equilibrium (c) 109 (d) 5.2153
is: 116. For which reaction from the following, IJ. S will be maximum?
(a) zero (b) positive (a) Ca(s)+~02(g)---7CaO(s)
(c) negative (d) none of these (b) CaC03 (s) ---7 CaO(s) + CO2 (g)
107. In the evaporation of water, the entropy: (c) C(s) + 02(g) ---7 CO2 (g)
(a) decreases (b) increases (d) N2 (g) + 02(g) ---7 2NO(g)
(c) does not change 117. A particular reaction at 27°C for which MJ > oand IJ.S > 0 is
(d) sometimes increases, sometimes decreases found to be non-spontaneous. The reaction may proceed
108. In which of the following change entropy decreases? spontaneously if:
(a) Crystallisation of sucrose from solution (a) the temperature is decreased
(b) Dissolving sucrose in water (b) the temperature is kept constant
(c) Melting ofice (c) the temperature is increased
(d) Vaporisation of camphor (d) it is carried in open vessel at 27° C
109. For the precipitation reaction of Ag + ions with NaCI which of 118. The least random state of water system is:
the following statements is true? (a) ice '(b) liquid water
(a) MJ is zero for the reaction (c) steam (d) randomness is same in all
(b) IJ.G is zero for the reaction 119. Although the dissolution of ammonium chloride in water is an
( c) IJ.G is negative for the reaction endothermi<; reaction, even then it is spontaneous because:
(d) IJ.G should be equal to MJ (a) MJ is positive, IJ.S is -ve
110. If enthalpy of vaporisation of water is 186.5 kJ/mol, the (b) MJ is +ve, IJ.S is zero
entropy of its vaporisation will be: (c) MJ is positive, T IJ.S < MJ
(a) 0.5 (b) 1.0 (c) 1.5 (d) 2.0 (d) MJis +ve, IJ.S is positive and MJ < T IJ.S
111. A reaction is non-spontaneous when: [AMU (Medical) 2006] 120. For an exothermic reaction to be spontaneous:
(a) Mi is +ve, IJ.S is -ve (a) temperature must be high
(b) both MJ and IJ.S are -ve (b) temperature must be zero .
(c) MJ is -ve and IJ.S is +ve (c) temperature may have any magnitude
(d) none of the above (d) temperature must be low
112. Standard entropies of X 2' Y2 and XY3 are 60, 40 and 50 121. . For the reversible process, the value of IJ.S is given by the
JK-1mor1 respectively. For the reaction: expression:
~X2+2Y2
2 . 2
~ XY3 ; MJ -30kJ
(a) T (b) T-qrev
to be at equilibrium, the temperature should be : (c) qrev X T (d) qrev - T
[CBSE (PMT)2010]
I
L--
= lO- llG '/2.303 RT
(c) I:!.Go RT log K (d) K
t R",
1/
(aIH~
1
(e) I:!.Go=RlnK
(b) H R
124. The value of entropy in the universe is:
(a) constant
(c) increasing
(b) decreasing
(d) zero --
Reaction coordinate Reaction coordinate
(Clll~
125. Which of the following thermodynamic relation is correct?
(H =U +PV) 1
S02 + "2 O 2 -----7 S03 + Y kcal
and dU TdS -PdV
dG (TdS - PdV)+ PdV + VdP TdS SdT The heat offormation of80 2 is:
dG VdP SdT] (AIIMS 1997; PET (Kerala) 2008]
126. If enthalpies of formation for ~H4 (g ), CO2 (g) and H2 0(l) (a) y 2x (b) 2x+ y (c) x+ y (d) 2x! y
at 25°C and 1 atm pressure be 52, -394 and -286 kJ mol- 1 134. Given,
respectively, enthalpy of combustion of ~H4 (g) will ge: NH3 (g ) + 3CI 2 (g ) ~ NCl 3 (g ) + 3HCI(g );
(CBSE 1995) N 2 (g)+ 3H2(g)~ 2NH3 (g);
1
(a) +141.2 kJ mol- (b) +1412 kJ rhol- 1 H2 (g) + Cl z (g ) ~ 2HCI(g ); !:!.H3
1
(c) -141.2 kJ mol- (d) -1412 kJ mol- 1 The heat of formation of Nel 3 (g ) in terms of !:!.HI' !:!.H2 and
127. Identify the correct statement regarding entropy: (CBSE 1998) lli3 is: (EAMCET 1998)
(a) at absolute zero, the entropy of a perfectly crystalline 1 3
( a) !:!.Hf - !:!.HI + - !:!.H2 - !:!.H3
substance is + ve. 2 2
(b) at absolute zero, the entropy of a perfectly crystalline 1 3
substance is zero. (b) !:!.H f = !:!.HI +"2 !:!.H2 - 2 !:!.H3
(c) at O°C the entropy of a perfectly crystalline substance is 1 3
taken to be zero. ( c) !:!.Hf !:!.HI - - !:!.H2 - - !:!.H3
(d) at absolute zero of temperature the entropy of all 2 2
crystalline substances is taken to be zero. (d) none of the above
128. The enthalpy and entropy change for a chemical reaction are 135. The word 'standard' in standard molar enthalpy change
- 2.5 x 10-3 cal and 7.4 cal deg- 1 respectively. Predict implies:
(a) temperature 298 K
whether the nature of reaction at 298 K is: (AFMC 1998)
(a) spontaneous (b) reversible (b) pressure 1 attn
(c) irreversible (d) non-spontaneous (c) temperature 298 K and pressure 1 atm
129. One mole of an ideal gas at 300 K is expanded isothermally (d) all temperatures and all pressures
from an initial volume of 1 litre to 10 litre. The M for this 136. The heat of formation (!:!.H~ ) of H2 0 (I) is equal to:
process is: (R 2 cal K- 1 mol-I) (CBSE 1998) (a) zero
(a) 163.7 cal (b) 1381.1 cal (b) molar heat of combustion of Hz (I)
(c) 9 litre-attn (d) zero (c) molar heat of combustion of Hz (g)
130. The latent heat of vaporisation of a liquid at 500 K and I atm (d) sum of heat offormation ofH2 0(g ) and 0z(g)
pressure is 10 kcaVmoL What will be the change in internal 137. An example of extensive property is:
energy (M ) of3 moles ofliquid at the same temperature? (a) temperature (b) internal energy
(CBSE 1998) (c) viscosity (d) molar heat capacity
(a) 13.0 kcal (b) -13.0 kcal 138. For a diatomic molecule AB, the electronegativity difference
(c) 27.0 kcal (d) -27.0 kcal between A and B == 0.2028.fi. [where, I:!. bond energy of
I
AB - ~eometric mean of the bond energies of A2 and B 2]. The (a) 29.8 kJ (b) -11.8 kJ
electronegativities of fluorine and chlorine are 4.0 and 3.0 (c) -20.6 kJ (d) -29.4 kJ
. I
respectively and the bond energies are ofF-F: 38 kcal mo.- 147. For the reaction,
and ofCI-Cl: 58 kcal mo.-I. The bond energy ofCI-F is: A(g) + 2B(g) ~ 2C(g) + 3D(g)
(a) ~ 71 kcal/mol (b) - 61 kcal/mol the value of MI at 27°C is 19.0 kcal. The value of AE for the
(c) - 48 kcal/mol (d) -75 kcallmol reaction would be: (Given, R 2.0cal K- 1 mo.-I): (lIT 1998)
139. The value of MIo for the reaction Cu + (g) + 1- (g) ~ Cul(g) (a) 20.8 kcal (b) 19.8 kcal (c) 18.8 kcal (d) 17.8kcal
is - 446 kJ mol-I. If the ionisation energy of Cu(g) is 745 kJ 148. In thermodynamics, a process is called reversible when:
mol-I and the electron affmityof I(g) is -295 kJ mo.-I, then [liT (Screening) 2000, 01 J
the value of MIo for the formation of one mole of CuI(g ) from
(a) surroundings and system change into each other
Cu(g) and I(g ) is:
(b) there is no boundary between system and surroundings
(a) 446 kJ (b) 450 kJ (c) 594 kJ (d) 4 kJ
(c) the surroundings are always in equilibrium with the system
140. If the enthalpy change for the reaction,
(d) the system changes into the surroundings spontaneously
CH4 (g ) + CI 2(g ) ~ CH3Cl{g ) + HC1{g ); l:J{ = - 25 kcal,
149. The heat liberated when 1.89 g of benzoic acid is burnt in a
Bond energy of C-H is 20 kcal mol-1 greater than the bond
bomb calorimeter at 25°C increases the temperature of 18.94
energy of C-Cl and bond energies of H-H and H-Cl are
kg of water by 0.632°C. If the specific 'heat of water at25°e is
same in magnitude, then for the reaction Hz (g) + Cl z (g ) ~
0.998 calg-Jdeg- I ,the val~$'ofheat of combustion ofbenzoic
2HC1(g 1l:J{ ?
acid is: ' '(AFMC 2010)
(a) -22.5 keallmol (b) -20.5 kcallmol
(a) 881.1 kcal (b) 771.4 kcal
(c) -32.5kcal/mol (d) -12.5kcal/mol
(c) 981.1 kcal (d) 871.2 kcal
141. The standard heat of formation of sodium ions in aqueous
[Hint: Heat liberated by 1.89 g of benzoic acid,
solution from the following data:
q = msllT
Heat of formation ofNaOH{aq.) at 25° C =- 470.7 kJ
= 18940x 0.998 x 0.632
Heat of formation ofOIr(aq.) at 25°C = - 228.8 kJ
11946.14 cal
is: Heat liberated by the combustion of
(a) -251.9kJ (b) 241.9kJ (c) -24L9kJ(d) 251.9kJ 1 mol benzoic acid, i.e.,
142. AB, A z and .B z are diatomic molecules. If the bond enthalpies 122 g benzoic acid
of A z , AB and B2 are in the ratio 1: 1: 0.5 and the enthalpy of
formation of AB from A2 and B2 is -100 kJ mol-I, what is the = 11946.14 x 122 == 771126.5 cal
189
bond enthalpy of A2 ?
771-.12 kcal mol-I]
(a) 400 kJ mol-I (b) 200 kJ mol-1
150. One mole of a non-ideal gas undergoes a change state (2 attn,
(c) 100 kJ mo.-I (d) 300 kJ mol-I
3 L, 95 K) to (4 atm, 5 L, 245 K) with a change of internal
143. The lattice energy of solid NaCl is 180 kcal per mol. The energy, IlU = 30 L atm. The change in enthalpy (MI) of the
dissolution of the solid in water in the form of ions is process in L atm.: lilT (8) 20021
endothermic to the extent of 1 kcal per mol. If the solvation
(a) 40.0 (b) 42.3
energies ofNa + and Cl- ions are in the ratio 6 : 5, what is the
(c) 44.0
enthalpy of hydration of sodium ion? (d) not defined, because pressure is not constant
(a) - 85.6kcallmol (b) - 97.5 keallmol 151. Which of the following reactions defines MI~ ,?
(c) 82.6kcal/mol (d) +100kcallmol lilT (8) 20031
144. Which one of the following statements is false? (a) C(diarnond) + 02 (g )~ COz (g )
[liT (Screening) 2000, 01 J 1 1
(a) Work is a state function '2
(b) H2(g)+ 2 F2(g)~ HF{g)
(b) Temperature is a state function (c) Nz{g) + 3H2 (g) ~ 2NH3(g)
(c) Work appears at the boundary of the system
(d) Change in the state is completely defined when the initial (d) CO(g) +..!. 02{g) ~ CO2(g)
2
and final states are specified 152. If the enthalpies offormation of Ai 20 3 and Cr203 are -1596 kJ
145. AGO for the reaction x + y ~ z is -;- 4.606 kcal. The value and -1.134 kJ respectively, then the value of l:J{ for the
of equilibrium constant of the reaction at 227° Cis: reaction;
(lIT 1999) 2Ai + Cr203 ~ 2Cr + Ai 20 3 is: (AIlMS 2004)
(a) 100 (b) 10 (c) 2 (d) 0.01 (a) -462kJ (b) -1365kJ
(R == 2.0eal K- I mol-I) (c) -2530kJ (d) +2530kJ
[Hint: AG ° = - RT x 2.303 x log K ] 153. Which of the following is true for spontaneous process?
146. The enthalpy of solution of BaCl2 (s) and BaC1 2 . 2HzCXs) are [PMT (Himachal) 20061
-20.6 and 8.8 kJ mol-I ,respectively. The enthalpy change for (a) AG> 0 (b) t.G < (l (c) 6.G = 0 (d) 6.G T t.S
the reaction is: (liT 1998)
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 497
(a) Isothermal process q=- w 160.2 JK- I mo1- 1 respectively at 298 K and 1 bar. Assuming
(b) Cyclic process . q=- w that, /:,.H0 and /:,.S ° do not change with temperature;
(crI~ochoric proces's', /:,.U = q temperature above which conversion of limestone to lime will
(d) . Ad,iabatic process /:,. U = - w be spontaneous is: . (AIEEE2007)
(eY
'Expansion of gasit:tto vacuum /:,.U = q (a) 1118 K (b) 1008 K (c) 1200 K (d) 845 K
[mnti In adiabatic process q=0
178. Assuming that, water vapour is an ideal gas, the internal energy
:. Froni/:,.U=q-w' change (/:,. U) when 1 mp1 of water is vaporised at 1 bar pressure
Work is done by the system, and 100°C, (given: molar enthalpy of vaporisation of water at 1
. '. /:,.U = -w ' . for adiabatiC process] bar and 373K = 41 kJ mo1- 1 and R = 8.3 J K- I mol-I) will be:
171. The,enthalpy and e~tr:opy changes for the reaction:
(AIEEE 2007)
.' , Bril)+Clig)~2BrCl(g) 1
(a) 41.00kJmol- (b) 4.l00kJmol- 1
are 30. kJ mol-land 105 J K- I mol- I respectively. The
temperature at which the reaction will be in equilibrium is: (c) 3.7904 kJmo1- 1 (d) 37.904 kJmol- 1
'. [CBSE(Med.) 2006] ,[Hint: I1U = Ml - /:"~RT
(a) 285.1 K (b) 273 K (c) 450 K (d) 300 K = 41000 - 1 x 8.314 x 373
172. (/:,.H - /:,.U) for the formation of carbon monoxide (CO) from = 37898.878 J mo1- 1
its .element at 298K is:(R = 8.314 J K- 1 mol-I) = 37.9 kJ mol-I]
(AIEEE 2006) 179. For the process,
(a) "":1238,78 Jmol- I (b) 1238.78 J mol- I H20(l) (1 bar, 373K) ~ H20(g)(1 bar, 373K).
! (c) -2477.57 J mol-I. (d) 2477.57 J mol- I The correct set of thermodynamic parameters is: (lIT 2007)
,' 1· 1 1
[Hink C(s) + - 02(g)~ CO(g) I1ng .= 1- - =- (a) /:,.G=O,/:,.S=+ve (b) /:,.G=O,/:,.S=-ve
. '." 2" ,,' 2 2 (c) /:,.G=+ve,/:"S=O (d) /:,.G=-ve,/:,.S=+ve
JiH - /:,.U = I1nRT 180. For the reaction,
." .' 1 , " ,
= - x 8.314 x 298 = 1238.786 J mol-I] 2H2 (g) + 02 (g) ~ 2H20(g ); /:,.H0 = - 573.2 kJ
2. ' ,
The heat of decomposition of water per mol is:
173. For a phase change: (MHT-CET 2007)
. H 2 0(l) ~ H 2 0(s) (a) 286.6 kJ (b) 573.2 kJ (c) - 28.66 kJ (d) zero
O°C, 1 bar (AnMS 2006) 181. The free energy change /:"G = 0, when: [CET (J&K) 2007]
(a)/:"G = 0 (b) /:,.S = 0
(a) the reactants are completely consumed
(c) /:,.H = 0 (d) /:,.U = 0
(b) a catalyst is added
174., We can drive any thermodynamically forbidden reaction in the
(c) the system is at equilibrium
desired direction bycol,lpling with: . [PET (Kerala) ,2006]
. (a) highly exothermic reaction (d) the reactants are initially mixed
(b) highly endothermic reaction 182. In a closed container, a liquid is. stirred with a paddle to
increase the temperature, which of the following is true?
(c) .h,ighly exergonic reaction
[PMt (Pb.) 2007]
(d) "highly endergonic reaction
(e) reaction with large positive /:,.S values
*
(a) /:,.U = /:,.W 0, q = 0 (b) /:,.U = W = 0, q 0 *
.175•. Given that; bond energies of H - Hand Cl - Cl are
(c) /:,.U = 0, W = q 0 *
(d) W = 0, /:,.U = q 0 *
183. For the gas phase reaction,
.A30kJ/mol and 240 kJ/mol respectively. /:,.HI for HCI is PCls (g)'~ PCl 3 (g ) + Cl 2(g )
- 90 kJ/mo!. Bond enthalpy ofHCl is: ICBSE (Med.) 2007]
Which of the following conditions are correct?
('1),380 kJ mol- I (b) 425 kJ mol- I [CBSE-PMT (Pre) 2008]
(c) 245kJmol- 1 (d) 290kJmol- 1 (a) /:,.H < 0, /:,.S < 0 (b) /:,.H > 0 and /:,.S < 0
d~. The ~in6uitt .of heat rel!!ased, when 20mL 0[0.5 M NaOH is (c) /:,.H = 0, /:,.S < 0 (d) /:,.H > oand /:,.S > 0
mixed with 100 mLaf 0.1 M HCl;is x kJ. The heat of 184. Which of the following is correct? :[BHU (Screening) 2008]
neutralization (in kJJrK;r~l) is:
(~) -100x (b) - 50x
.. ~ f(M:alns))~OD'7]
(c) + 100i Cd) + 50x ' (a)Cv = (~~]p (b)C
p=(~~]v
, MV 0.5x 20
[Hmt~ Number of moles ofNaOH = - - =
' . 1000 1000
= 0.01 (c) Cp - Cv = R (d) (au] -a
" .' MV 0.1 x 100 V av:.t 2
Number of moles ofHCl = - - , = = 0.01 (Internal pressure in van dar Waals' equation)
" 1000 1000
. -x lti. Which of the following represents total kinetic energy of one
Heat of'neUtralization = - = - 1OOx ] mole of gas?I[HEE«(Orissap,n08]
. . ", 0.01
lifil.. LIl,J4~i~qJ1version of limestone to lime, (a).!RT (b)~RT (c)(Cp-Cv)RT (d)~RT
, ., CaC03 (s) ~ CaO(s) + CO2(g) 2 2 3
the \,alues of /:,.H0 and !:,.So are +179.1kJmol- 1 and
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY +--499
186. Standard entropy of X 2' Y2 and XY3 are 60, 40 and 50 JK - I
I "
(a) Na(s)+ H20(l) - - - t NaOH(aq)+-H2 (g)1'
1
mol- respectively. For the reaction: """ 2
I 3 (b) Ag+(aq)+Cnaq) AgCI(s)
- X 2 +- Y2 -----? XY3 , Ml 30 kJ,
2 2 I .
(c) H2(g)+2:02(g)---t H20(l)
to be at equilibrium, the temperature will be: (AIEEE 2008)
[Cu(NH3 )4]t~.)
(a) lOOOK (b) 1250K (c) 500K (d) 750K 2
(d) Cu + (aq)+ 4NH3 (g)
[Hint: .!.X2 + ~12 --7 XJ3 191. The species which by defmition has zero standard molar
2 2 enthalpy of formation at 298 K is: (UT 2010)
MO Reaction =MO XlS3 -.!.2 MO X 2 - ~2 MO l'1 (a) Br2 (g) (b) Clz(g)
(c) H 2 0(g) (d) CH4 (g)
= 50 - .!. X 60 - ~ X 40 = - 40 JK- 1 mol- 1 192. The standard enthalpy of formation' of NHj is -46 kJ morl. If
2 2
AG = I:l1f - T M = 0 at equilibrium. the enthalpy offormation ofH2 from its atoms is -436 kJmorl
.. T = I:l1f = - 30 X 1000 750 K ] and that ofN2 is -712 kJ mor l , the average bond enthalpy of
M 40 N-H bond in NH3 is: (AIEEE WI:O)
187. 4.48 L of an ideal gas at S.T.P requires 12 calories to raise its (a) + 1056 kJ mor l " (b) -1l02 kJ mor l
temperature by 15Co at constant volume. The C p of the gas is : (c) -:964 kJ mol- 1 (d) +352 kJ mol- 1
[PMT (Kerala) 2009]
(a) 3 cal
(e) 9 cal
(b) 4 cal (c) 7 cal (d) 6 cal [Hint: ~ (N N)+ ~ H) H~N<:
[Hint.. Cv- - 4.48 -
- AU , n - - 0.2 I:l1f -46 kJ mol-1
nAT 2.24 BE (N N) =-712 kJ mol- 1
12 H) -436 kJ mol-1
= - - = 4 cal
0.2 x 15 Let RE. H) x kJ mol- I
C p = C v + R = 4 + 2 = 6 cal] I:l1f L(B. E. )Rcactants - L(B. E. )Products
[~(712)+~(436)J-3X
188. On the basis offollowing thermochemical data :
-46
[A JGo H+ (aq) = 0]
."
HzO(l)---t W(aq)+ Of1(aq); Ml = 57.32kJ x 352 kJ mol-I]
1 193. A 1 g sample of substance A at 100°C is added to 100 mL of
H2(g)+2: 02 (g)---t H2°(l) Ml -286.2kJ H20 at 25°C. Using separate 100 mL portion of H20, the
procedure is repeated with substance B and then with substance
The value of enthalpy of formation of OH- ion at 25°C is: C. How will the final temperatures of the water compare?
(AIEEE 2009) Substance $pecific heat
(a) -22.88 kJ (b) -228.88 kJ A 0.6 J g-I 0 C- 1
(c) +228.88 kJ (d) -343.52 kJ
B O.4J 0C- I
[Hint: The equation for the formation ofOf1(aq) is:
I
C 0.2 J 0C- (DUMET 2010)
H2(g)+.!.02(g) ~ H+ (aq) + Of1(aq)
2 (a) Tc > TB > TA (b) > TA > Tc
It is obtained by adding the two given equations : (c) > TB > (d) TA TB Tc
I:l1f = 57.32 + (-286.2) = -228.88 kJ] [Hint: q msl:J.T
189. The values of Ml and AS for the reaction, 1
sOC
C(graphite) + CO2 (g)---t 2CO(g) are 170 kJ and 170 AT
JK- 1 respectively. This reaction will be spontaneous at : Higher is the temperature of given solution, lesser is the
temperature so higher is the specific h~t. Order of
[CRSE (PMT) Pre 2009]
specific heat is A > B > C. Hence order of temperature will be :
(a) 510K (b) 710K (c) 910K (d) IIIOK '" "-~'i
TA >TB ]
[Hint: AG = I:l1f - TM, AG should be negative for spontaneous
process. 194. For vaporisation of water at 1 atmospheric pressure, the values
of Ml and I:J.S are 40.63 kJ mol-I and 108.8 J r1mor l
I:l1f -TM < 0
respectively. The temperature when Gibbs free energy change
I:l1f <TM
(I:J.G) for transformation will be zero, is:rCBSEi(pMl'~ 2010]
I:l1f T> 170x 1000
or T>- (a) 273.4 K (b) 393.4 K
M' 170
(c) 373.4 K (d) 293.4 K
T > 1000K]
[Hint: AG I:l1f - TM
190. In which reaction, there will be increase in entropy?
(DCE2009)
o 40.63xlOOO-TxlO8.8
T 373.4 K]
500 G.R.B. PHYSICAL CHEMISTRY FOR COMPET1TIONS
Set·2: The questions given below may have more (a) YzMf;(N2) - Mf;(NaN 3)
than one correct answers
(b) - Mf; (NaN 3)
I. Which is intensive property?
(a) Mass (b) Mass/volume (c) Mf;(NaN 3) -[Mf;(Na) + Yz
Mf;(N z)]
(c) Volume (d) Volume/mass
2. Which is an irreversible process?
(d) Mf; (Na) + Yz Mf; (Nz) Mf; (NaN3 )
(a) Mixing of two gases by diffusion 10. The lattice energy of KCI is 202 kcal/mol. When KCI is
(b) Evaporation of water at 373 K and 1 attn pressure dissolved in water 2 kcal/mol is absorbed. If the sol energies of
K+ and Cl- are in the ratio 2 : 3; then Mfhydration ofK+ is:
(c) Dissolution ofNaCI in water
(d) All of the' above (a) -80 kllmol (b) -120 kllmol
3. One mole of anhydrous MgCl2 dissolves in water and liberates (c) -150 kllmol (d) 133.3 kllmol
25 cal/mol of heat. Mf hydration of MgCl2 = - 30 cal/mol. Heat 11 •. Which is a correct relationship?
of dissolution of MgCl2 . H 20 is:
(a) +5 cal/mol (b) -5 cal/mol
(a) [dH] _[dE] = (+ve) '.
dT p dT T
(c) 55 cal/mol (d) -55 cal/mol
4. Following enthalpy changes are given: (b) [dE] 0 (for ideal gas)
a-D g\ucose(s) ----7 a-D g\ucose(aq.); Mi = 10.72 kJ dV T
~ -D glucose(s) ----7 J3 -D glucose(aq.); Mi = 4.68 kJ
a - D glucose(s) ----7 J3 - D glucose(aq.); Mi 1.16 kJ (c) [dV] = nR (for ideal gas)
Calculate the enthalpy change in, dT p P
a-D glucose(s)----7J3-D glucose(s) (d) All of the above
(a) 14.24 kl (b) 16.56 kl (c) -7.2 kl (d) 4.88 kl 12. The standard Gibbs free energy 6.G ° is related to eqUilibrium
5. If x and yare arbitrary extensi.ve variables, then: constant K pas:
(a) (x + y) is an extensive variable (a) Kp RT log 6.G o (b) Kp = [el RT ]I'.G
(b) x/ y is an intensive variable (c) Kp = -6.GoIRT (d) Kp = e-l'.GolRT
(c) dx/ dy is an intensive variable
13. For the two equations given below:
(d) both (b) and (c)
H 2(g) + .x02(g) ----7 H 20(l) + Xl kJ
6. If x and yare arbitrary intensive variables, then:
(a) xy is an intensive variable
.x
Hz(g) + 02(g) ----7 H 20(g) + x 2 kJ
Select the correct answer:
(b) xl y is an intensive variable
(a) Xl > X2 (b) x 2 > Xl
(c) (x + y) is an extensive property
(c) Xl =x2 (d) Xl + X z o
(d) dx/ dy is an intenSive property
1 14. M = 0, for which process?
7. H 2(g) + "2 02(g) H 20(g); Mi = x (a) Cyclic process (b) Isothermal expansion
1 (c) Isochoric process (d) Adiabatic process
H 2(g) + 2 °2(g) ----7 HP(I); Mi = Y 15. For a reaction to be spontaneous in neither direction, which of
Heat of vaporization of water is: the following is/are correct regarding the closed system?
(a) x+ y (b) x- Y (c) y-x (d) (x+ y) IBHU (Mains) 2007]
8. Which is correct about 6.G? (1) (6.G)r.p = 0 (2) (6.G)T,P < 0
(a) 6.G = Mf - T 6.S (b) At equilibrium, 6.G 0 = 0 (3) (6.S)u.v 0 (4) (M)u,v >0
(c) At eq. 6.G RT logK (d) 6.G 6.G ° + RT log K Codes:
9. Dissociation of sodium azide is given by, (a) 1,2 and 3 are correct (b) 1 and 2 are correct
NaN 3 ----7 Na + 312N2; (c) 2 and 4 are correct (d) 1 and 3 are correct
Mi for this is:
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 501
11. (A) Enthalpy offormation ofHCI is equal to the bond energy 17. (A) There is noreaction known for which I1G is positive, yet it
ofHCI. .. is spontaneous.
(R) Enthalpy of formation and bond energy both involve (R) For photochemical reaction, I1G is negative.
formation of one mole of HCI from the elements. 18. (A) A reaction which is spontaneous and accompanied by
ll. (A) Pressure, volume and temperature are all extensive decrease of randomness must be exothermic.
properties. (R) All exothermic reactions are accompanied by decrease of
(R) Extensive properttes depend upon the amount and nature randomness.
of the substance. 19. (A) Molar entropy of vaporization of water is different from
13. (A}When a gas at high pressure expands against vacuum, the ethanol.
work done is maximum. (R) Water is more polar than methanol.
(R) Work done in expansion depends upon the pressure inside 20. (A) Heat of neutralization for both HN0 3 and HCI with NaOH
the gas and increase in volume. is 53.7 kJ/mol.
14. (A) When a real gas is allowed to expand adiabatically (R) NaOH is a strong electrolytelbase.
through a fine hole from a region of high pressure to a 21. (A) In the following reaction:
region of low pressure, the temperature of the gas falls. C(s) + 02(g) ~ CO 2 (g); Ml = I1U - RT
(R) Work is done at the cost of internal energy ofthe gas. (R) MI is related to I1U by the equation,
15. (A) Internal energy change in a cyclic process is zero. Ml = au I1ngRT
(R) Internal energy is a state function. 22. (A) Enthalpy of graphite is lower than that of diamond.
16:.- (A) An exothermic process, non-spontaneous at high (R) Entropy of graphite is greater than that of diamond.
temperature, may become spontaneous at low
23. (A) For a reaction
tempemture.
2NH3(g)~ N 2 (g)+ 3H2 (g); MI > AE
(R) With decrease in temperature, randomness (entropy)
(R) Enthalpy change is always greater than internal energy
decrease.
change. (ADMS 2008)
I
CHEMICAL THERMODYNAMICS AND THERMOCHEMiSTRY
Set-1 . ;;':r';':.·~';;',.~,·.
"
9. (a) 10.. (d) ,1. (c) 12. (d) 13. (c) 14. (d) . ; 15,. (a) . i6.,;(a)
:,,,'oc.
17. (c) 18. (a) 19. (a) 20.. (a) 21. (b) 22. (d) 23. (b) 'l'4,;r(a)
25. (c) 26. (d) 27. (d) 28. (b) 29. (d) 3~. (b) 31: (e) '3~!/(a .
""'V' )
"J.';:' "
33. (c) 34. (b) 35. (a) 36. (a) 37. (d) . ~8. (b) 39. (d) .4Q. (c)
; ." "
~
: ..-- '
41. (d) 42. (d) 43. (c) 44. (b) 45. (b) 46. (c) 47. (a) . '•.:.(a)
·'i,f! .. ·:,
49. (a) 50.. (d) 51. (b) 52. (c) 53. (d) 54. (d) 55. (b) 5(;'''(c )
'1 t·
57. (a) 58. (c) 59. (b) 60.; (d) 61. (b) 62. (c) 63. (a) . _~~.(b)
65. (c) 66. (d) 67. (b) 63. (a) 69. (d) 70.. (a). 71. (d) 7~da)
73. (b) 74. (b) ·75. (c) 76. (d) 77. (d) 78. (c) 79. (c) 80. (b)
81. (a) 82. (c) 83. (a) 84. (d) 85. (b) 86. (c) 87. (d) 8ft. (a)
89. (d) 90.. (c) JJ1. (a) "92. (b) 93•. (a) 94. (a)
j:;'- :.. ',' ':
95.
f
(c)
j' , ~ . 2~~M'"
99. :·:t~f(d) .. ~~~/\~)
1~'
97. (a) !}8. (b) (c) 10.0.. (d) Un~(c) to':!. (b) '","
10.5..
':','!~,~
(c) 1~6. (a) W7. (b) 10.8. (a) ..,9.(c) 1!~•.. <a) .J,!.(a) . )
'.
t'i
t':
~
"·"'1."0;" ,
119. (d) 130. (c) 13.1. (c) 132. (a) 133. (a) ,<l.~;-.(a) '(b) ) ,-- ~
'<' ',: ,'. ',' '/.,1 ~
"~~')
~
137. (b) 138. (a) 139. (d) 14~. (a) 141. (c) '142; (a) 0'»
~
"':'
'fn~'(b)
"
145. (a) 146. (a) 147. (d) 148. (e) Hf:,;t(b) 'l~i"(c) 'lf~L(a)
I
. "" "";.i',
153. (b) 154. (a) 155. (a) 156. (e) l~f(b) 15& (b) 15': (a) l~~\;i4).
161. (b) 161. (d) 163. (e) 164. (a) 16i(c) 166. (e) 107. (d) 168. (0)---
II
III
169. (b) 170. (d) 171. (a) 1'n~" .(b) 173. (a) 174. (e) 17~. (b) 179~(a) t~
~j
..
177. (a) 178. (d) 179. (a) l$Oj(a) IS1> (c) tS2~ (a) UU. (d)
.,
iiU:\c)
I
t~.~-(b) i~~~;(~l)
, (" 1-",
185. (b) 1~. (d) ~87~ (d) 189. (d) 190. (a) ~9t. (b)
193. (e) 194. (c)
~. ,. , ...
Set-2
1. (b, d) 2. (a, e) J. (a) 4~ (d) 5. (a, b, c) 6. (a, b, d) 7. (b) 8. (a, d)
9. (b) 10.. (a) n. (d) 12. (d) . 13. (a) 14• (a, b) 15. (d)
f'
.
. Set-1
1. (d) 2. (b) 3. (d) '4. (e) 5. (a) 6. (d) 7. (a) 8. (a)
,Set-2
1. (b) 2. (e) 3. (b) 4. (e) 5. (b) 6. (a) 7. (d) . II. (d)
9. (a) to. (b) . 11. (d) 12. (d) 13. (d) 14. (a) 15. (a) te. (b)
17. (d) 18. (e) 19. (b) 20. (a) 21. (d) 22. (b) 23. (e)
, .-
°
(Common bonds of reactants and products are rejected.)]
4. Standard enthalpies of formation of 3, CO2 , NH3 and HI are [Iliac 2Fe(s) + 3 CO2 (g) ---7 FeP3(s) +
2. 2
~C(s) ... (i)
142.2, -393.2, 46.2 and +25.9 kJ mol- l respectively. The (t:.W = - 234.1kJ)
order of their increasing stabilities will be: C(s) + 0z(g) ---7 COz(g) (AW:= - 393.5 kJ) ... (ii)
(a) 03'COZ ' NH3 ,HI (b) CO2 , NH3 ,HI'03 MUltiplying eq. (i) by 2 and eq. (ii) by 3 and on adding both
(c) 03' HI, NH 3 , CO2 (d) NH 3 , HI, CO2 , 0 3 equations, we get:
[llial: (i) Exothermic compounds are more stable than 4Fe(s) + 30 2 (g) ---7 2FeP3(s);
endothermic compounds. MIo = (-234.1 x 2) + (-3 x 393.5)
(ii) Greater is the amount of heat evolved in the formation of a = 1648.7 kJ]
compound, more will be its stability.] 11. Consider this equation and the associated value for MI 0:
S. Combustion of octane takes place in an automobile engine. 2H2 (g) + 2C1 2 (g) ---7 4HCI(g); mo = -92.3 kJ
The homogeneous equation of combustion is:
Which statement about this information is incorrect? .
CSHlS(g) + ¥02(g) ---7 8C02 (g} + 9H 20(g) (a) If the equation is reversed, the MIO value equals + 92.3 kJ
The signs of MI, t:.S and t:.G for the reaction will be: (b) The four HC] bonds are stronger than four bonds in H2 and
(a) +ve, -ve, +ve (b) -:-ve; +ve, -ve Cl 2
(c) -ve, +ve, +ve (d) +ve, +ve, -ve (c) TheMIO value will be -92.3 kJ if HC! is produced as a
6. Which among the following represents the reaction of liquid
formation of the product? (d) 23.1 kJ of heat will be evolved when 1 mole of HCI(g ) is
(a) C(diamond) + 02(g)~ CO2 (g) produced
(b) S(monoclinic) + 02(g) ~ S02(g) 11. If the internal energy of an ideal ~as decreases by the same
(c) 2N2 (g)+ 02(g)~ 2N20(g) amount as the work done by the system, the process is:
(d) None of the above (a) cyclic (b) isothermal (c) adiabatic (d) isolated
7. How much energy must be supplied to change 36 g of ice at 13. The enthalpy of neutralization of a strong acid by a strong base
0° C to water at room temperature 25°C? is -57.32 kJ mol-I. The enthalpy of formation of water is
Data for water -285.84 kJ mol-I. The enthalpy of formation of hydroxyl
MI~on 6.01 kJ/mol ion is:
C p liquid 4.18 J K- l g-: (a) +228.52 kJ mol-I (b) -114.26 kJ mol-I
(c) -228.52 kJ mol-I (d) +114.2 kJ mo]-l
(a) 12 kJ (b) 16 kJ (c) 19 kJ (d) 22 kJ
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 505
23. Under which circumstances would the free energy change for
a reaction be relatively temperature independent?
C. Mfo enthalpy change of a (iii) R T 2 rd In K J
reaction in standard state \ dT p
(a) 1::Jf0 is negative
(b) 1::Jf0 is positive D. Standard free energy change (iv) _ {d t1G} .
(c) MO has a large positive value (t1GO) dT p
. W 155.8 x 1000 39. For the reaction shown, which is closest to the value of W?
For spontaneous reactIOn, T > - ; T > ----
!1S 161.65 2Cr 3+(aq.) + 3Ni(s) ----7 2Cr(s) + 3Ni 2+(aq.)
T >966K]
35. Which of the following equations haslhave enthalpy changes
W; (kJ mol-I)
14:: B
---------A
G =H +T
OR
!1G
!1T
G =H + T ( dG J
Il..
GC 1
I
I
I
I
1
1
I
I
I
aT p
-;z =- :2 + t (~~ J p
(a) 12~fJ (b) 6~fJ (c) 3~fJ . (d) ~fJ
= [ a(G/T) ]
[Hint: Work done in the cyclic process
aT p
= Area bounded (ABCA)
H = _T2 [ a(G/T)] ] I
=-x AC xAB
aT p 2
38. When a bomb calorimeter is used to determine the heat of 1
= "2 x 2 VI X 3PI = 3PI Vd
reaction, which property of the system under investigation is
most likely to remain constant? 44. One gram mole of graphite and diamond were burnt to form
(a) Number of molecules (b) Pressure CO 2 gas.
(c) Temperature (d) Volume C(graphite) + O2(g) ~ CO2(g); wo = - 399.5 kJ
C(diamond) + 02(g) ----7 CO 2(g); wo = - 395.4 kJ
I
508 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(a) graphite is more stable than diamond ~ x (1500 1000) x (250 - 150)
(b) diamond is more stable than graphite ~----~~-------------------------xl00
(c) graphite has greater affinity with oxygen x (1500-1000) x (250 -150) + (1500-1000) x (150 - 0)
2
(d) diamond has greater affinity with oxygen
[Hint: Thermal stability of one isotope is directly proportional .!. x 500 x 100
to the heat of combustion.] = I 2 x 100
45. Which among the following is not an exact differential? - x 500 x 100 + 500 x 150
2
.(a) Q (dQ heat absorbed)
500 x 50x 100 = 25]
(b) U (dU change in internal energy) 500 x 50 + 500 x 150
(c) S (dS entropy change)
49. In Haber's process of ammonia manufacture:
(d) G (dG = Gibbs free energy change)
N 2 (g) + 3H 2 (g) ----4 2NH 3(g);
[Hint: Heat' Q' is a path dependent function, hence its exact
differentiation is not possible; however, internal energy, entropy lili;soc - 922 kJ
and Gibbs free energy are state functions, hence can be Molecules H 2 (g) NH3(g)
differentiated exactly.] Cp J K- I mol-I 28.8 35.1
46. A gas expands adiabatically at constant pressure such that:
If C p is independent of temperature, then reaction at 100c C as
1
T=- compared to that of25°C will be:
.JV (a) more endothermic (b) less endothermic
The value ofy, i.e., (C p I Cv ) of the gas will be: (c) more exothermic (d) less exothermic
(a) 1.30 . (b) 1.50 (c) 1.70 (d) 2
[Hint: Use: lili2 lili I == t.cp ]
I . T2 T1
[Hint: T oc-
.Jv SO. Consider the following statements:
TV 1/2 = constant I. Change in enthalpy is always smaller than change in
For adiabatic process, TV Iff TV Y- 1 == constant internal energy.
1 3 II. The variation in enthalpy of a reaction with temperature is
y-l=2,y==2"] given by Kirchhoff's equation.
III. The entropy change in reversible adiabatic process is equal
47. 2Zn + 0z ----42ZnO; t.GO = 616 J ... (i)
to zero.
2Zn + 8 ----42Zn8; t.Go = 293 J ... (ii) Select the correct answer:
2S+ 202 ----4 2802(g); t.Go = -408 J ... (iii) (a) I and II (b) II and III
t.Go for the following reaction: ( c) III and I (d) all are correct
2ZnS + 302 ----4 2ZriO + 2802 51. In CzH4 , energy offormation of(C C)and (C-C) are -145
would be: kJ/mol and 80 kJ/mol respectively. What is the enthalpy
(a)-731J (b)-l317J (c)+731J (d) +1317 J change when ethylene polymerises to form polythene?
[Hint: t.GO == 28.G~no + 2t.G;02 -2t.G~ns [JEE (Orissa) 2006]
(a) +650 kJ/mol (b) +65kJ/mol
[-616-408] [-293]
(c) 650 kJ mol- 1 (d) -65 kJ mol- 1
-1024 + 293
=-731J] [Hint: Po\ymerisation of ethene may be given as:
48. The efficiency of the reversible cycle shown in the figure will nCH 2 ----4 -+
CH 2 - CHzin
be: lili ~(BE)reaetants ~ (BE)producls
(a) 33.33% (b) 56% (c) 66% (d) 25% = (+145) (+80) = + 65 kJ/mo!]
[Note: C-H bonds are common in both reactants and prodUcts.]
t 250 ---------~
52. If 150 kJ of energy is needed for muscular work to walk a
distance of I km, then how much of glucose one has to consume
to walk a distance of 5 km, provided only 30% of energy is
[Hint: /j,G ° = Mlo - T/'o"S° Following questions may have more than one correct options:
= - 54.07 x 1000 - 298 x 10 1. Which of the following are correct about irreversible
= -57050 J isothermal expansion of ideal gas?
/j,Go = -2.303 RT loglOK (a) W = - q (b) /j,U = 0
p,
- 57050 = - 5705 logtoK (c) I1T =0 (d) W =- nRT In --.l..
P2
loglO K = 10]
54. The lattice enthalpy and hydration enthalpy of four 2. The work done during adiabatic expansion or compression of
compounds are given below : an ideal gas is given by :
[,,f.~(HtfIA)
• Single correct option
1. (c) 2. (d) 3. (c) 4. (c) 5. (b) 6. (d) 7: (b) 8. (a)
9. (c) 10. (a) il. (c) 12. (c) 13. (c) 14. (a) 15. (d) 16. (b)
17. (b) 18. (c) 19. (e) 20. (c) 21. (b) 22. (b) 23. (d) 24. (b)
25. (a) 26. (a) 27. (a) 28. (c) 29. (b) 30. (d) 31. (b) 32. (d)
33. (a) 34. (c) 35. (d) 36. (a) 37. (b) 38. (d) 39. (a) 40. (b)
41. (a) 42. (d) 43. (c) 44. (a) 45. (a) 46. (b) 47. (a) 48. (d)
49. (d) 50. (b) 51. (b) 52. (d) 53. (b) 54. (e)
• One or more tllan ·GRe correct ,options
1. (a,b,e,d) 2. (a,b,e) 3. (b)
•
510 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
1.0
4. Standard Gibbs Free energy change I1Go for a reaction is zero.
0.5 -------~-----------
The value of equilibrium constant of the reaction will be: . b
., 5. 6Go for the reaction x + y ~ z is 4.606 kcaL The value of 0.0 i .1
equilibrium constant of the reaction at 227°C is (x x 102 ). The 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 '4.5' 5.0 5.5 6.0
value of' x' is : V (lit.)
6. 4.48 L of an ideal gas at STP requires 12 cal to raise the
temperature by 15°C at constant volume. The Cp of the gas is (liT 2010)
........... cal. [Hint: wd = work done along dotted line
7.
'LP6V
4 x L5 + I x 1+ 25 x ~ 8.65 L atm
3
i
p
Ws :;:: It is reversible isothermal process
I == 2303nRT IOg[ ~~ J
= 2.303 x (PV) log ( ~: J
V-
= 2.303 x 2 log 5.5 = 4.79 L atm
In the present graph, the area of circle A and B are 25 unit and 0.5
20 unit respectively. Work done will be ........... unit. Wd = 8.65 "" 2 ]
'8•. For the reaction, Ws 4.79.
N2 (g ) + 3H2 (g) ----7 2NH3 (g )
Heat of reaction at constant volume exceeds the heat of
reaction at constant pressure by the value of xRT. The value of
x is:
Heat of reaction at constant pressure is measured using simple or (a) lOoC (b) 25°C (c) 20°C (d) 35°C
water calorimeter.' " 5. The enthalpy of fusion of ice is 6.02 kJ mol-I. The heat
qp=M capacity of water is 4.18 J g-l C-!. What is the smallest
number of ice cubes at DoC, each containing one mole of
qp :::: qv + P flV water, that are needed to cool 500 g ofliquid water from 20 0 e
M flU + flnRT to DOC?
The amount of energy released during a chemical change (a) I (b) 7 (c) 14 (d) 125
depends ',011 the physical state of reactants and products, the [Hint: Heat released to cool 500 g water from 20 0 e to O°C,
condition ofpressure, temperature and volume at which the reaction q=msflT
is carried out. The variation of heat ofreaction with temperature and 500 x 4.18 x 20 = 41800 J = 41.8 kJ
pressure is given by Kirchhoff's equation: Number of moles of water (ice) that will melt to absorb 41,8 kJ
_-"-_--'- == flC p flU 2 - flU! ==,flC =41.8", 7
v
T2 11 T2 -11 6.02
(At constant pressure) (At constant volume) :. Number of cubes of ice that will'melt = 7]
Answer the following questions: 6. The enthalpy change (M) for the reaction,
1. Match the List-I with List-II and select the answer from the N2 (g) + 3H2 (g) ---7 2NH3(g)
given codes: is -92.38 kJ at 298 K. The internal energy change flU at 298 K
List-I List-II is: ' ( A l I M S 2006)
(a) -92.38 kJ (b) -87.42 kJ (c) -97.34 kJ (d) -89.9 kJ
A. C(s)+ 02(g) CO2 (g) 1. M = flU + RT
[Hint: 2- 4 - 2
B. N 2 (g)+3H z(g) 2NH3(g) 2. M=flU
C. NH4HS(s) NH3 (g ) + H 2 S(g) 3. M = flU - 2RT 6H = flU + AngRT
flU 6H - flng RT
D. PCI 5 (g) PCI 3(g) + CI 2 (g) 4, M = flU + 2RT
92.38 x 1000 - (-2) x 8.314 x 298
E. 2S02 (g)+ 02(g) 2S03 (g) 5. M = flU - RT
87424 J = - 87.424 kJ]
Codes: ABC D E 7: The specific heat of 12 in vapour and solid state are 0.031 and
(a) I 2 3 4 5 0.055 caVg respectively, The heat of sublimation of iodine at
(b) 5 2 3 4 I e
200 0 is 6.096 kcal mol-I. The heat of sublinlation offodine
(c) I 3 4 2 5 at 250°C will be:
(d) 2 3 ;4 5 (a) 3.8 kcal mol- l (b) 4,8 kcal mol- 1
2. The heat capacity of a bomb calorimeter is 500JIK. When (c) 2.28 kcal mol-I (d) 5.8 kcal mol-I
0.1 g of methane was burnt in this calorimeter, the temperature [Hint: 12 (s) ~ 12 (g)
rose by 2°e. The value of flU per mole will be: Aep (0.031- 0.055) x 10-3 x 254
(a) +1 kJ, (b)-l kJ (c)+l60kJ (d)-160kJ
3. For which reaction will M = flU? Assume each reaction is -'-"'----" =flCp
Tz Tl
carried out in an open container:
(a) 2CO(g) + 02(g) 2C02 (g) --,--",--_6,_09_6 = (0,031 _ 0.055) x 10-3 x 254
50
(b) H2 (g) + Br2(g) 2HBr(g)
6H z = 5.79 kcal mol-!]
(c) C(s) + 2H zO(g) 2H 2 (g) + CO2 (g) ,
(d) PCIs(g) PCI 3(g) + CI 2 (g)
••
512 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
( a;J.
\ '
Answer the following qnestions on the basis of the given IlS = In the reversible adiabatic process, however, ilS will
diagram:
1. The heat of formation of glucose is: be zero. The rise in temperature in isobaric and isoc/Joric conditions
(a)-x (b)-y (c)x-y (d)-x+z is found to increase the randomness or entropy ofthe ,frstem.
2. In the given diagram z refers to: IlS = 2.303C log (1j / T2 )
(a) 6 x Ml fco2 (b) ANf~H IP6 ' C=Cp orCv
(c) AlI'::ombustion ~H rA f H P(I)
(d) AN':.orrIJustion C{s) +l:Jf Answer the following questions:
1. The entropy change in an adiabatic process is:
3. The quantity y is equal to:
(a) zero
(a) ANcorrIJustionC{s) + ANcombustion H 2(g) (b) always positive
(b) x + z (c) always negative
(c) x - z (d) sometimes positive and sometimes negative
(d) AN/ CO2 + AliHp , 2. If, water in an insulated vessel at-lOOC, suddenly freezes, the
4. Select the incorrect statement(s): entropy change of the system will be: I
,'
• Passage 5 fullion is 600 cal mol-I. The entropy change for the fusion of 1
mole of the solid (in cal K -I) at the same temperature would
be:
20 L '--:-----:--A ~' (a) 200 (b) 2 (c) 0.2 (d) 20
i
~'
~
,
10 L --------- V
c:
I
I
I
,
,
' I
!:
I
I
I
I
I
4: For which of the following cases IlS ==
• Passage 7 The net work done during the com~ .. cycle is given by the
area:
The pressure-volume behaviour of various thermodynamic
(a) cycle ACBDA
processes is shown in graphs~'
(b) AA1B1BDA
(c) AA2B2B
(d) half of area bounded by curve
r------- Isobaric 3. P - V plots for two gases during adiabatic processes are given
1 in the given figure:
Isothermal
Isochoric
Adiabatic
1
Volume -
Work is the mode oftransference ofenergy. If the system involves
gaseous substance and there is difference ofpressure between system
and surroundings, such a work is referred to as pressure-volume
work (wpv = - Pext b.V). It has been observed that reversible work Volume -
done by the system is the maximum obtainable work. Plot A and plot B should correspond to:
wrev > wirr (a) He and 02 (b)HeandAr (c) O2 and He (d)02andF2
[Hint: Slope of the adiabatic curve oc y
The works of isothermal and adiabatic processes are different
from each other. Slope of B > Slope of A
He (y =:: 1.66); O 2 (y =:: 1.44)
W isotherm,,1 reversible - = 2.303nRT logw (~)
"2.303nRT loglO (V2) - Thus, correct answer will be (c).]
, ,~ ~ 4. The q value and work done in isothennal reversible expansion
W"diabatic reversible =Cv (11 - T2 ) of one mole of an ideal gas from initial pressure of 1 bar to
final pressure of 0.1 bar at constant temperature 273 K are:
Answer the following questions:
(a) 5.22 kJ, -5.22 kJ (b) -5.22 kJ, 5.22 kJ
1. If WI' W2' W3 and w4 are work done in isothermal, adiabatic,
(c) 5.22 kJ, 5.22 kJ (d) -5.22 kJ, -5.22 kJ
isobaric and isochoric reversible processes, then the correct
sequence (for expansion) would be: [Hint: w:: 2.303nRT log (~)
(a) WI > W2 > w3 > w 4 (b) w3 > w2> WI > w 4
(c) w3 > w2 > W4 > WI (d) w3 > WI > w2 > W4 = - 2.303 x I x 8.314 x 273 log (~)
,[Hint: W = Work done = Area undercurve.] OJ
2. A thennodynamic system goes in acyclic process as = 5.227 kJ
represented in the following P-V diagf~_ q =- w =+ 5.227 kJ for isothermal process]
5. Calculate work done when 1 mole of an ideal gas is expanded
reversibly from 20 L to 40 L at a constant temperature of
300K.
(a)7.78kJ (b)-1.73kJ (c) 11.73kJ (d)-4.78kJ
.
CHEMICAL THERMODYNAMICS AND THERMOCHEMISTRY 515
Passage 1. 1. (d) 2. (d) "'3. (b) 4. (c) 5. (b) " 6. (b) 7. (d)
Passage2~ 1. (a) 2~ (b) 3. (a) 4. (b) 5. (a) 6. (a)
-.- .......
Passage 3. 1. (a) 2. (a) 3. (a) 4. (c) 5. (d) 6. (d) .. 7. (a) 8.' (b)
Passage 4. 1. (a) 2~ ,(c) 3. (b) 4. (c, d)
PassageS. 1. (b) 2~ (b) . 3. (b) 4. (c) 5. (a)
Passage 6. 1. (a) 2. (c) 3. (b) 4. (d) 5~ (b)
Passage 7. 1. (d) 2. (a) ,3•. (c) 4. (a) 5. (b)
~.
'SEtFAssESSMENT
~, '\.,. ':','. ,,,
.' ', C~
(:p .'
~ ..
ASSIGNMENT NO.7
a
e®0 e ,from the given codes:
List-I List-II
b
d
®e 0
ee0 0
®®0
•e (Thermodynamic properties)
(I)~G
(II) Afr
(III)M
(N)AG o
'
(Expression) .
(A)- RT loge K
(B)RT 2 (d In
(C)nFE
. (D)_[dAG] .
dT. /"
K) .
oT /'
List-I List-II Codes:
(a) I-C,II-B, III-D, IV-A
(a) (dT) (P) V
dP H, (b) I-B, II-C, III-D, IV-A
(c) I-A, II-B, III-C, IV-D
(b) (dG) (q) T (d) 1-0, II-A, III-B, IV-C
dP T 26. Match the List-I with List-II:
(c) (dH)
. " , ' ......,">.
-. > . ".-'
(r)-S 'Ust~1I
dS /' List-I
(a) Perfectly crystaliine solid (P) AU =()
(d) (dG) . I(S)~jT
dT /' (b) Reversible reaction at (q) T = constant
equilibrium
( c) Isothermal process (r) Lim S --+ ()
T~OK
(d) (dG)
dP = -S
, . . (s) Muniv~ = 0
. ,., "......
[~ ,.---~----------I
~, ., ... ·.:'i"~'''''';''·----~-----------------------.......
1. (b) 2. (d) 3. (a) 4. (b) 5. (b) 6. (c) 7. (b) 8. (c)
9. (a) 10. (c) 11. (a, b) 12. (a, b, d) 13. (a, c) 14. (a, b, d) 15. (a, c, d) 16. (a, b, c)
17. (a,b, c) 18. (a, b, c) 19. (a) 20. (a) 21. (c) 22. (c) 23. (b)
24. (a-s) (b-p) (c-q) (d~r) 25. (a) 26. (a-r) (b-s) (c-p, q) (d-q)
/
INTRODUCTION (iii) Neutralisation of an acid with a base when their aqueous
solutions are mixed.
Thermodynamics deals with the feasibility of a chemical change.
The fre~ energy change, aG, of a reaction helps us to understand HCI + NaOH ----*NaCI + H 20
Acid Base Salt
whether the reaction will occur or not. Even though there may be (b) Very slow reactions: There are certain reactions which
decrease in free energy but reactants do not always form the are extremely slow. They may take months together to· show any
products instantaneously and actual rate of the reaction may vary measurable change at room temperature. It is also difficult to
from extremely slow to very fast. Thermodynamics is concerned study the kinetics of such reactions.
only with initial and final states of reacting systems but offers no Some examples are:
explanation about the various stages through which the reactants (i) Reaction between hydrogen and oxygen at room
pass to reach the final state. This leads to following questions temperature.
concerning chemical changes. Room temperature
(i) How fast do the chemical reactions go? 2H2 + O 2 ) 2H 20 (Very slow reaction)
(ii) How can the speed of the reaction change? (ii) Reaction of atmospheric H 2S on basic lead acetate.
(iii) What intermediate steps, the reactants follow to reach the Atmospheric
final state of products, i.e., the mechanism of the reaction. White basic lead acetate paint -----» Blackening
The branch of physical chemistry which deals with the rate at H2 S
which the chemical reactions occur, the mechanism by which the of paint occurs very slowly
chemical reactions take place and the influence of various factors (due to formation of PbS.)
such as concentration, temperature, pressure, catalyst, etc., on the (iii) Reaction between carbon and oxygen.
reaction rates, is called the chemical kinetics.
Room temperature
Different ,chemical reactions occur at different rates. On the C+02 ) CO 2
basis of rates, the chemical reactions are broadly divided into
three categories: Carbon and oxygen are thermodynamically less stable than
(8) Very fast or instantaneous reactions: These reactions CO 2 at 298 K, yet coke does not spontaneously catch fire in air
are so fast that they occur as soon as the reactants' are brought and remains unreacted even for years.
together. Generally, these reactions involve ionic species and thus (iv) Reaction between carbon monoxide and hydrogen.
known as ionic reactions. These reactions take about 10- 14 to Room temperature
10-16 seconds for completion. It is almost impossible to CO+ 2H2 ----~) CH)OH
determine the rates of these reactions. Some such examples are:
The reaction is thermodynamically feasible at 298 K but in
(i) Precipitation of AgCI when solutions of silver nitrate and
actual practice the reaction proceeds infinitesimally slowly;
sodium chloride are mixed.
(v) Rusting of iron occurs very slowly.
AgN0 3 + NaCl ----* AgCI + NaN0 3 (c) Moderate reactions: Between the above two extremes,
(ii) Precipitation ofBaS04 when solutions of barium chloride there are a number of reactions which take place at moderate and
and sulphuric acid are mixed. . measurable rates at room temperature and it is these reactions
which are studied in chemical kinetics. Mostly these reactions are
BaC1 2 + H 2S04 ----*BaS04 +2HCl
,- .,;
molecular in natl:lre. Some. common examples of s4<:h type ,are destination. The odometer reading at destination is y miles. The·
given below: rate of his travel can be calculated as: ~~
(i) Decomposition of hydrogen peroxide.
2H2 O 2 ---t 2H20 + O 2
Rate =d( distance) =---""-'------
distance (j) - distance (in)
d(time) time(j) - time(in)
(ii) Decomposition of nitrogen pentoxide.
=
y-x 'I hr-I
y-x =--mtes .
2N 20 S ---t 2N 20 4 + O 2 11.0- 9.0 2
(iii) Hydrolysis of an ester. . The above example indicates that the car hns been driven with
CH 3 COOC 2Hs + NaOH ---t CH3 COONa + C 2HsOH unifonn rate but actually it has been driven sometimes faster and
Ester Sodium acetate sometimes slower depending upon the conditions of the road.
(iv) Inversion of cane sugar in aqueous solution. Thus, the overall rate is an average rate and the rate at which the
car was moving at any instant, i. e., instantaneous rate was
C 12 H22 0 11 + H 20---t C 6 H I2 0 6 + C 6 H I2 0 6 changeable.
Cane sugar Glucose Fructose
Tbe rate measured over a long time interval is called
(v) Reaction between nitrogen dioxide and carbon monoxide. average rate and tbe rate measured for an infinitesimally
N0 2 + CO ---t NO + CO2 small time interval is called instantaneous rate.
(vi) Reaction between ferric chloride and stannous chloride. In a chemical change, reactants and products are involved. As
the chemical reaction proceeds, the concentration of the reactants·
2FeCI 3 (aq.) + SnCI 2 (aq.) ---t 2FeCl 2 (aq.) + SnCI 4 (aq.) decreases, i. e., reactants are consumed and the concentration of
(vii) Decolourisation of acidified potassium pennanganate products increases, i. e., products are produced. Tbe rate of
with sodium oxalate. reaction (average rate) is defined as tbe cbange .of
(viii) Reaction between nitric oxide and chlorine. concentration of anyone of its reactants (or products) per
NO+ Cl 2 ---tNOC1 2 unit time.
Average rate of reaction,
The chemical reactions can be slowed down or speeded up by
Change of concentration of one of the reactants or products
changing conditions under which they occur. For example, very ~v =-~~--------------~---
slow reaction, CO + 2H2 ---t CH 3 0H, can be speeded up by Time taken for the change
maintaining temperature around 400°C, pressure about 300 Consider a common hypothetical reaction,
atmospheres and using a catalyst containing ZnO and Cr2 3 , The ° A~B
decay of food articles can be slowed down by preserving them in
The average rate of reaction may be expressed either in tenns'
refrigerators. There are two principal reasons for studying
of decrease in concentration of A (reactants) or in tenus of
chemical kinetics. .
increase in concentration of B (product).
(i) To predict tbe rate of a particular reaction under
· Decrease in concentration of A
specified conditions: The conditions can be adjusted to make Average rate 0 f reactIOn =------,-.- - - - - - -
the reaction to go at a desired rate, either rapidly or slowly or Time taken
moderately. The field of chemical kinetics is useful in industry as · concentration of B
the conditions for maximum yields of industrial products can be or Average rate 0 f reactIOn =Increase inTime taken .
.
ascertained.
(ii) To predict the mechanism of tbe reaction: The The concentrations of reactants or products are expressed as
intelligent guess regarding various elementary processes number of moles per litre. The symbol for the molar
responsible for the formation of products can be made which concentration consists of the fonnula of the substance enclosed in
should be consistent with experimental data, bracket. The symbol [A] stands for the molar concentration of A.
The symbol d[A], therefore, stands for the change in molar
8.2 RATE OF REACTION (Average and concentration of A.
The rate of decrease or increase in the concentration of
Instantaneous Rate)
reactants or products may also be expressed in terms of change in
We are all familiar with processes in which something changes their concentration during the time interval, M, as:
with time. Rate is usually expressed as the ratio of the amount of
change in some quantity to the time required to produce that Average rate of reaction = _ d[A]
M
change.
Change in some quantity t:.X or ' Average rate of reaction = + d[ B]
Rate = =- M
Time taken for the change !1t
(A negative sign placed before a reaction rate symbol signifies
The tenn t:.X means X final - X initial and !1t is the amount of a decrease in concentration of tile reactant with increase of time
time elapsed. For example, a car driver starts his journey at 9.0 and a positive sign before the rate symbol signifies that the
a.m. with odometer reading x miles. At 11.0 a.m. he reaches his concentration of the product increases with increase in time. The
520 I, G.R.B. PHYSICAL CHEMISTRY FOR GpMPETITIONS
"'" '
_---[8]
" :.::::::_SOME SOLVED EXAMPLES\a:::,:::,
Example 1. Ina reaction, the concentration of a reactant
(A) changes from 0.200 mol litre-I to 0.150 molUtre- 1 in 10
i minutes. What is the average rate of reaction during this
interval?
Solution: A[A] = [A]flnal- [A]initial
=[0.150- 0.200] = ":'O~050mollitre-1
At = 10 minutes
,[A]
, 'f " . -A[A] -[- 0.050]
Average rate 0 reaction ='-'- =~--...::
, At 10
Time - = 0.050 0.005 mol litre -\ min-I
"
,,
\1"1.J~J'" n"
',Fi'g: 8:1
~: ~·<;·.r,·
' 10
concentration"change may. be PQsitive or negative but therate,of Expression of Rate
reaction is .f!.l~ays positive. The minus sign ,is, always written Consider the following reaction between CO and N02 :
whenrequi~jbut the plus sign is usually not mentioned.)
Figure 8.1 shows thech~l1ge of concentrations of reactant (A) , CO+N02 ~C02 +NO
and product (B -) ~s the chemiclll reaction A -4 B progresses with The, equation shows that when one mole of CO reacts with one
time, Let [A]II aQd [A]IZ ,be the, concentrations of A at. time mole of N0 2 • one mole each of CO2 and NO are formed; The
I, and t2,re~ectively. " ' ',", ',,' average rate of reaction can, beexpres~d either by decrease of
concentration of anyone ofthe reactants (CO or N02) or by the
A[A] = [ALz ,- [A]II increase in concentration of anyone of the products (C02 or
,and ,At == t2 :- I, , NO);
, A[A] [A112 - [A]II Thus _ AlCO] = _ A[N02']=A[C02 ] = A[NO] ,
r. =- - - = - ~'---'=-----.!.. , At At At At,
av At ' t 2 -t,
However, for the reaction,
Over the same time interval t, to 12 , the concentration of B 2H202'~ 2H 2 0 + O 2
changes from[B]11 to[BJI2' it is observed that when 2 nlOles of H 2 0 2 decompose, one,
, A[B] [R]IZ - [B]II' mole of O 2 is formed in the same time interval. The rate of
r. = - - =--=---..;... increase in the concentration of O 2 , therefore, is half that of the
av At "t2 - I, ,"
disappearance of the ,concentration of H2 O2 in the same time
Since, 'one mole of A produces one mole of B, the rate of in~erval; ,
decrease in concentration of A should be equal to the rate of
increase in concentration of B. Thus, '
ray = r;v ,In general, for a reaction,
A[A] A[B]
---=-- n,A +n2B ~m!C+m2D
At At
the rate expression may be expressed as:
Reaction rate has' the units of concentration or 'molarity
1 A[A] 1 MB} 1 A[e] I' &[D]
divided by time. Therefore; the units ohate of reaction may be - --=---- ----=---
expressed as: ' nl At nz At m, At mz At
rinlellitre sec (mol L-, s-')
Thus, for the reaction,
imlellitre min (rilOl L-' min:-') H2 +I z ~ 2HI
or molellitre hour(mol L -I, h -I,) the rate may be expressed as:
or molellitre day (Illol L-I d -I) A[H 2 ] , A[1 2 ] 1
---=---==-
or molellitre year (mol L-' y-') At At 2At
Note: In case of gaseous reaction, pressure may be taken in place of concentration. Thus, rate will have the unit of attn sec-lor attn min -I,
PV =nRT ,or P =[fJRT or P=CRT '
Similarly, for the decomposition of N 20 S in CCl 4 medium, Experimental Determination of Instantaneous Rate of
the rate may be expressed as: Reaction
2N 2 0 S ~ 4N0 2 + O 2 \ In order to determine changes in concentration of reactants or
1 A[N20 s ] l' A[N0 2 ] A[02 1 products, it is customary to take small portions of the reaction
-- =- =-- mixture at suitable intervals of time and freeze them rapidly to
2 At 4 At At
about O°C as to stop the reaction. The concentration is then
Example.:!. Decomposition of N 20S is expressed by the measured with the help of a suitable method. In several cases,
equation, concentration changes are measured by observing changes in
N 20 S ~2N02 + X02 certain physical properties which are proportional to it such as
q during a certain time interval, the rate ofdecomposition of optical densities, electrical conductivity, optical rotation, etc. A
N 2 0 5 is 1.8 X 10-3 mol litre-I min-I, what will be the rates of curve is plotted between concentration and time. A tangent is
formation ofN02 and02 during the same inierval? . drawn to the curve at the point corresponding to time interval' t'.
Solution:. The rate expression for the decomposition ofN 2Os is: The slope of this tangent gives the instantaneous rate of reaction.
This is shown in Fig. 8.2 (a). .'
_ A[N 20sl =1 A[N02 ] = 2. A[02l Instantaneous rate of reaction =Slope of curve
At At 2 At
Intercept along ordinate Ax
So, A[N0 2 l = 2A[N 20s1 =2x1.8 x 10-3 = Intercept along abscissa =-
At
At At
= 3.6 X 10-3 mol litre -I min-I Since, the concentrations of the reactants keep on decreasing
with time, the r.ate of reaction correspondingly decreases with
and A[02l =.!. A[N 20 s ] =.!. x 1.8 X 10- 3 time. Thus, the rate of reaction will depend on the stage
At 2 At 2
considered during progress of the reaction. The rate of reaction is
=0.9 x 10-3 mol litre -I
min-\
maximum at the . initial stage and decreases with time.
'. A[NO]
(Rate is always positive and hence - 2 . s is taken Theoretically, infinite time wpuld be required for a reaction to
At complete. But the reaction rate becomes so slow after a certain
positive.) time that for all practical purposes, the reaction can be considered
to be completed. It is evident from Fig. 8.2 (b) that the rate of
Instantaneous Rate reaction is varying from'moment to moment.
In chemical kinetics, the rate at any particular instant, i. e. ,
instantaneous rate rather than the average rate over a time interval
has much more practical application and importance. It is defined
as the rate of cbange of concentration of anyone of the
reactants or products over a very small interval of time.
If we take infinitesimal small interval of time dt, it may be
assumed that the rate is uniform through this interval; then if dx is
amount of substance A transformed to B during this interval, the
rate of reaction at that instant is given as _ dx .
dt
[In differential calculus, when At becomes very small and
-t- Time -
Fig.8.2(a) Determination
Time --.-+
, 1 £[1-:- 0.002
(a) HzO z + 2H + + 31 ------" 13 +. 2HP; _ d[l ] = ? Rate of appearance ofIz =- = --
dt ., 2 At 2
d[H+] =0.001 mol L- I min-I
---=?
dt
='1 x 10-3 mol L -I min-I
(b) 1611+ +2MnO:; +101 ------"2Mn 2+ +8H20+5/ 2 ;
_ d[MnO:; ] _? -'Example 5. The reaction between CrzO~- and HN0 2 in an
dt -. acidic medium is:
, . d[NH] Crp~- + 5H+ + 3HN02 -; 2Cr 3+ + 3N0'3 + 4H2 0
(c) 4NH3 + 50z ------,,4N02 + 6Hp; - 3 =?
, dt The rate of disappearance of Cr20~- is found to be
Solution: We have, 2.4 x 10-4 mol rl s-I during a measured time interval. Find the
(a) HzOz + 2H+ + 3r ------" 1:3 + 2H zO rate of disappearance of HN02 and the rate of appearance of
Cr 3+ during this time interval.
The equality in this case is:
Solution: The equality in this case is:
d[H z 02] 1 d[ H+ ] 1 d[r d[I:3 ] I d[H20]
- A[Cr20~-] =.- I A[HN0 2 ] = 1 A[Cr +]
3
-' =-- =- =--
dt 2 dt 3 dt dt 2 dt
At 3 At 2 At
So,- d[r] =_3 d[H20 2] = _ ~ d[ H+] = 3 d[I:3] = ~ d[H20] It is given that,
dt dt 2dt dt 2 dt
~ A[Cr20~-] := 2.4 X 10-4 mol L- I S-1
°
and _ d[H+] = _ 2 d[H2 2 ] = _ ~ d[ r ] = 2 d[ 1'3 ] = d[H20] 'At
dt dt 3 dt dt dt So, - A[HN0 2 ] = 3 x 2.4 X 10-4 = 7.2 X 10-4 mol L- 1 S- I
(b) 16H+ +2Mn04 +IOr -;2Mn2+ +8H 20+5I 2 At
3
The equality in this case is: and A[Cr +] = 2 x 2.4 X 10-4 =4.8 X 10-4 mol L-1 S-I
1 d[W] I d[Mn04 ] 1 d[r] At
----=-- =---
16 dt 2 dt 10 dt fUUSTfATrON$ OF OBJECTIVE QUEmONS"
1 d[Mn 2+ 1 d[H 20] I d[Iz]
=- - =---
2 dt 8 dt 5 dt 1. For the reaction, 2N20 S ~ 4NOz + Oz rate of reaction is:
So, _ d[MnO;j] = _ 1 d[H+ I d[1 (AIIMS 2006)
=-- 1d
dt 8 dt 5 dt (a) - - [N20 S ] (b) 2 ~ [N 20s]
2 dt dt
d[Mn 2+] 1 d[H20] = 2 d[1 2 ]
= -"'-~--=-
dt 4 dt 5dt
. (c) 1 ~ [NOz]
4 dt
(d) 4 ! [N0z]
The initial concentration of 1 was 0.25 mol L- I and the min-I. What is the value of -d[B] in mol litre-I min-I?
dt
concentration after I ominutes 0.23 mol rl. Calcuiate the rate of
(EAMCET 2006)
disappearance of1 - and appearance ofI z .
, (a) 3 x 10-3 (b) 9 x 10-3 (c) 10-3 (d) 1.5 x 10-3
Solution: A[r] =[r ]finaJ - [r ]initisl
[Ans. (b)]
0.23 - 0.25 = - 0.02 mol L- 1 -d[A] 1 d[B]
[.Hint: --=
At = 10- 0= 10 min dt 3 dt
0002'moI L. . I nun
A[r =- (- 0.02) =. ·-1 -d[B] = 3 r-d[A]} 3 x 3 X 10-3
At 10 dt 1 dt
= 9 x 10-3 mol litre- 1 ~in-l]
CHEMICAL KINETICS 523
3. For the reaction, 2A + B ----+ 3C + D, which of the Active mass =molar concentration of the substance '
following does not express the reaction rate? =number of gram moles of the substance
[CBSE (Med.) 2006)
volume in litres
(a) -d[C] (b) -d[B] (c) d[D] (d) -d[A]
3 dt dt dt 2 dt w/M n
=--=-
[Ans. (a)] V V
[Hint! ...,.!. d[A] = -d[D]: +.!. d[C]:;: +d[D] =Rate] where, w = mass of substance and •M' is the molecular mass in
2 dt dt 3 dt dt gram, • n' is the number of gram moles and V is volume in litre.
4. Consider the, reaction, N2(g) + 3H2(g) ----+ 2NH3(g). The .',~ .. _~~ample 6. 4 g of hydrogen and 128 g of hydrogen iodide
are present in a 2 litre flask. What are their active masses?
· "1 ".' h"Ip between'
d[NH
. .3 ] an d - -
d[H 2 ]·,
equaIIty
•
Fe atIons
••• '- IS:
d[12] 10-
Rate=+--=-'=
5
10- 6 mo I d m- When [A] =[B] =1mol/litre, then
dt ' 10 Rate =k
8~9; LAW OF MASS ACTION Rate of a reaction at unit concentration of reactants is
(Guldberg and Waage, 1864) called rate constant.
This law relates rate of reaction with active mass or molar The value of rate constant depends on:
concentration of reactants. (i) Nature of reactant
"At a given temperature, the rate of a reaction at a (ii) Temperature
particular instant is proportional to the product of the active (iii) Catalyst
masses of the reactants at that instant raised to powers which
are numericaUy equal to the numbers of their respective Unit of Rate Constant
molecul~ in the stoichiometric equation describing the Rate constant has different units for reactions of different
reactio,,:? order. General rule for rate of reaction may be given as:
524 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
-- A +B---7C+D;
Rate == k [A][B]
Rate of the above reaction
i
A A decreases with the passage of time ~
A---A A r---------1A
I
I
I
I
because the concentration of a:
I I
I
I
I
I
reactants A and B will decrease as
6---6 6 '----------'6 time passes on.
6 6 Time-
Products Let us consider the following
Reactants reversible reaction: Fig.8.S
.. / A+B~C+D
-Ll
. . . . '. ' Rate offorward reaction =k f [A][B]
8
f
No product
formation i Equilibrium
Let temperature coefficient of a reaction be 'J1' when Logarithmic Arrhenius equation is:
temperature is raised from Tj to T2 ; then the ratio of rate constants
or rate may be calculated as: log 10 k log 10 A [..!.]
2.303R T
= (J..t.)(T2 TI)1I0=J1 AT11O Y=C+M X
kTI It is the equation of straight line with negative slope. On
plotting log 10 k against [1/ T ] we get a straight line as shown in
log 10 l'_k1'_2] Fig. 8.8. The graph gives two kinetic parameters.
kTI The slope gives activation energy and intercept gives
frequency factor.
=antilog [ ~~ log 10 J1 ] The dependence of rate constant on temperature for two
kTI reactions is shown in the Fig. 8.9.
Its value lies generally between 2 and 3.
When the temperature is increased, heat energy is supplied
which increases the kinetic energy of the reacting molecules.
This will increase the number of collisions and ultimately the rate
of reaction will be enhanced. Arrhenius suggested an equation
-. i
. 10910 k
which describes k as a function of temperature, i. e. ,
k =Ae-EaIRT
®
1._
T
l Fig. 8.9
log(~)
rI
t).
1ii
a:
.45"C
1._ T- Temperature - - Temperature - - Temperature __
T (Normal reactions) (Explosive reactions) (Biological reactions)
Fig. 8.8 (a) (b) (c)
1
/
-f----;:~;?--',~\
E; \
loglo ~: =R x 2.303 [T~I~; ]
I
Reaction \
; path with \
Given:~=3;R=8.314JK-l mol- I ;TI =20+273=293K
'------:~·l~;;~~~ , -
kl
Reacta;;';- and T2 = 50+ 273 = 323 K
reaction
The effect of a ________ _______________
'I ___ Substituting the given values in the Arrhenius equation,
catalyst is to lower Products
the energy of activation 10 3- Eo [323- 293]
glO - 8.314 x 2.303 323 x 293
Collision number -
2.303 x 8.314 x 323 x 293 x 0.477
Fig. 8.11 A catalyst changes the Ea =~-------------------
30
reaction path (Positive catalyst)
:::: 28811.8J mor l
\
\
\
Catalyst
present or
E
_a
RT
.
logee
\
\
;., \
Catalyst
or 2.303 log 10 k = 2.303 log 10 A - RT
~
Q) \ absent
c: \
Q) \ . 98.6x 103
iii \ or 2.303 log (1.1 x 10-3 ) = 2.303 log (4 X 1013 ) - - - -
:e
Q)
\
\
\
8.314 x T
o
0..
\
\ , T= 98.6x 10
3
K
~
8.314 x 2.303 x 16.56
Products
= 31O.96K
Collision number -
Example 9. The rate constant is given by Arrhenius
Fig.8.12 Negative catalyst equation,
\
Let' p' denote presence of.catalyst and 'a' denote absence of k Ae-EaIRT
1j :::: 273 K andT2 = 293 K As the things being equal in presence or absence of a catalyst,
Substituting the values in Arrhenius equation, k2 must be = rate in,presence of catalyst.
Exa.uple 11. "i' 407 K, the rate constant of a chemical 7. For a reaction Ea= 0 and k:::: 3.2 X 104 s-I at 300 K.The
reaction is 9.5 x 10-5 s -I and at 420 K, the rate constant is value of k at 310 K would be:
1.9 x 10-4 S -I. Calculate the frequ~ncy factor of the reaction. (a) 6.4 x 104 s-I (b) 3.2 X 104 S-I
Solution: The Arrhenius equation is, (c)3.2 X 108 s-, (d) 3.2 x 105 s-I
[Ans. (b)]
k2
k; : : 2.303 x R 1j T2
log 10
[T2 -T1 ] [Hint: k =Ae-Eo IRT
WhenEa =0, k = A = constant
Given: k, =9.5xlO-5 s-';k2 =1.9 x 10-4 s-I; k310 = k300 = 3.2 X 104 S-I]
8. For a gaseous reaction, following data is given:
R:::: 8.314 Jmorl K- 1 ;
. A ~B,kl :::: 1015 e-2OOOIT
T( ::::407KandT2 = 420K
C
Substituting the values in Arrhenius equation Jb.e tempel1lture at which k, :::: k2 is:
log L9x 10-4 :::: [420- 407] . (a) lOOQ K (b) 2000 K (c) 868.82 K (d) 434.2 K
, 10 9.5 X 10-5 2.303 x 8.314 420 x 407 . [Ans. (d)]
[Hint: When k, =k2'
Ea :::: 75782.3 J J;DOr( 1Ols e-2ooolT =1014 e-IOOOIT
E 10 = e1OOO/ T
Applying now log k, :::: log A _ ,a
2.303R1j
2303 log 10 = 1000
I 9 5 10-5 I A 75782.3 T
og . x :::: og - 2.303 x 8.314 x 407 T =434.2 K]
CHEMICAL KINETICS 529
(b) log 10 ( ~: ) = 2.;3 R [ ;2 ;. ] In the ftrst reaction, molecularity seems to be '5' and in the
second reaction molecularity seems to be '23'. Such reactions
530 G .RB. PHYSICAL CHEMISTRY FOR COMPETITIONS
involve two or more steps; each step has its own molecularity not Step 1: H Z02 -----7 H 20+ [0] (slow)
greater than three, e. g. , in first reaction,
HBr + 02 -----7 HOOBr Step 2: [0] + [0] -----7 0z (fast)
HOOBr + HBr -----7 2HOBr dx
Actual rate - = k[H 2 0 2 ]
[HOBr + HBr -----7 H 20 +Br2 ] x 2 dt
4HBr + 0z -----7 2H 20 + Br2 Thus, order of reaction is unity..
Molecularity of each of the above steps is 2. (ii) 2NO z + F2 -----72N02F
(a) Reaction between Br- and 8 2 0 2 in acidic Rate law from law of mass action:
medium: The overall reaction is: dx 2
- - k [N02 ] [Fz]
2Br- + H 20 2 + 2H + -----7 Brz + 2H 20 dt
The proposed mechanism is: Experimentally observed rate law:
Br- + H 20 2 + H + -----7 HOBr + H 20 (slow)
- dx = k [N0 2 ][F2 ]
HOBr + H + + Br- -----7 Br2 + H 20 (fast) dt
Rate =k [Br- ][H20 2 ][H+] Slowest step is N0 2 + F2 -----7 N0 2F + [F]
The reaction is trimolecular. Thus, order of reaction 1+ 1= 2
(b) Reaction between N0 2 andFz : The overall reaction is: (iii) CH 3 CH0-----7CH 4 + CO
2N0 2 + F2 -----72N0 2F The rate equation derived from experimental data is found to be
The proposed mechanism is:
_ dx = k[CH 3 CHO]1.5
NO z + F2 -----7 N0 2F + F (slow) dt
N0 2 + F -----7 N0 2F (fast)
The order of reaction is 1.5.
=
Rate k [N0 2 ] [F2 ]
Some typical linear plots for the reactions of different
The reaction is bimolecular. orders:
irs;' V. ipe,
(c) Decomposition of 8 2 0 2 : The overall reaction is: (a) Plots of rate vs concentrations [Rate k(conc. t]
°
2H 2 0z -----7 2Hz + 0z
~~d.'
The proposed mechanism is:
H Z 02 -----7 H 20+
H 20z + 0-----7 HzO+ 02
° (slow)
(fast) . :$.
t1 d ord. er
ga _g> "[Ai [A)2
Rate =k [H 2 02 ]
The reaction is unimolecular. U t- t- t- t-
(b) Plots from integrated rate equations:
8i7 ORDER OF REACTION
Let us consider a general reaction:
ml A + mzB + m3C -----7 Product
i Zero order
!l/e, !L/' !V e
,
Let active moles of 'A', 'B' and 'e' be 'a', '[3' and 'y'
respectively. Then, rate of reaction may be given as:
Rate = k[A](l[B]f3 [C]Y
*
a:
Conc.-
iii
a: ..
Conc.-
iii
a:
(Conci-
~
(Conc.)3_
Sum of powers of concentration terms involved in rate law From the study of the kinetics of many simple reactions, it is
expression is called order of reaction. observed that for a large number of reactions, the molecularity
a + ~ + y == order and order are the same. Some examples are given below to justifY
When a + ~ + Y mJ + m2 + m3 , then this point.
Order of reaction = molecularity of reaction. L Dissociation ofN 20 s ,
Order is an experimentally determined quantity. It may be equal I
N 2 0 S -----7 N 20 4 + - 02
to zero, positive, negative, fractional and greater than three. 2
Infinite and imaginary values are not possible. Order = 1, Molecularity = 1
Examples:
(i) 2H 20 2 -----7 2H zO + 02
2. Dissociation of H2 ° 2,
1
dx . z H 20 2 -----7 H 20+ - 02
-=k[HzO z ] 2
dt Order 1, Molecularity = 1
(observed from law of mass action)
CHEMICAL KINETICS 531
.
~
~
From expt. (4), k[1.0Y[2.0Y == 0.15 ... (iii) k = 1.2 X 10-4 = 1.2 X 102 mol-2 L2 s-1
Dividmg eq. (iii) by eq. (i), [0.010]3
Dividing eq. (ii) by eq. (i), FiQ in the blanks:' Substituting the values of expt. (1) in the
rate eqiIation,
2.4 X 10-4 =[0.020Y
3 x IO z = k[0.10][0.20]2
1.2 x [0.0 lOy
2
or 2 (2)Y or k= 3 X 10 7.5 X 104 L2 mol-z S":I
. [0.1O][0.20f
y=1
Expt. (4): Rate k[O.lO][0.40]2
, FrOtilexpt. (2), 2.4 x 10-4 = k[O.OIOY [0.020Y ... (ii) 4
= 7.5 X 10 x O.lOx 0.40 x 0.40
From expt. (3),9.6 x 10-4 = k[0.020Y [0.020Y ... (iii)
= 1.2 x 103 mol L -1 s-I
Dividing eq. (iii) by eq. (ii),
Expt. (5): Rate = k[0.20][0.60]2
9.6x 10-4 _ [0.020Y
2.4 x 10-4 - [O.OlOy =7.5 X 104 x 0:20 x 0.60 x 0.60
or 4=2X = 5.4 x 10 3 mol L- 1 S-l
Rate = k[NO]z [CI 2 ] Example 17. The table given below gives kinetic data for
the following reaction at 298 K:
Considering eq. (i) again,
1.2 x 10-4 =k[0.01O]2 [0.010] ocr +! -.....,0/ - +CI
CHEMICAL KINETICS 533
[OCr] [r] [OH'"] 10- 4 xd[IQ-]/dt Example 18. The rate law for the reaction,
Expt.
No. moldm-J mol d",-J r:.ol dnt-J moldm~3s-1 2ClzO -----? 2Clz + O2
1. 0.0017 0.0017 1.0 1.75 at 200°C is founa to be: rate =k[ ClzO] 2 •
2. 0.0034 0.0017 1.0 3.50 (a) How would the rate change if [Cl 20] is reduced to
0.0017 0.0034 1.0 3.50 one-third of its original value?
3.
0.5
(b) How should the [ClzO] be changed in order to double the
4. 0.0017 0.0017 3.50
.' rate? -
What is the rate law and what is the value of rate constant? (c) How would the rate change if[CI 20] is raised to threefold
=
Solution: Let the rate law be k[OCl- U- Y[OH-]Z r of its original value?
From expt. (1), 1.75 x 10-4 k[0.0017Y[0.0017]Y [l.O]Z ... (i) Solution: (a) Rate equation for the reaction,
Fromexpt. (2), 3.50 x 10-4 = k[0.OO34l" [O.0017]Y [l.O]Z ... (ii)
ri
r= k[CI 2 0]2
or y = 1, i. e., first order w. r. t. r (c) New rate = k[3CI 2 0]2 = 9k[CI 20]2 = 9r
From expt. (1),1.75 x 10-4 = k[O.OOI7]x [O.OOI7]Y [1.0]Z ... (i) i. e. , nine times of the original rate.
t~~IExalllple 19. For a reaction in which A and B form C. the
From expt. (4), following data were obtained from three experiments:
3.50 x 10-4 = k[O.OO I 7]x [O.OOI7]Y [0.5]Z ... (iv)
Dividing eq. (i) byeq. (iv), &pi.
.No.
/1fiIitd COliC. (M r')
1'",.
(_1:"8-1)
1.75 x 10-4 [1.oy [A] [B]
=--
3.50 x [O.5]z
1. 0.03 0.03 0.3 x 10-4
or 2. 0.06 0.06 1.2 x 10-;4
3. 0.06 0.09 2.7x 10-4
or
z = -I, i.e., order w.r.t. OIr is-I. What is the rate equation ofthe reaction and what is the value of .
rate constant? . .
k[OCr ][1-]
Rate 1aw Solution: Let the rate equation be k[AY [BY.
[OH-]
From expt. (1), 0.3 x 10-4 = k[0.03Y[0.03]y ... (i)
From expt. (I) k =1.75 x 10- 4 [Oli- ] =1.75 X 10-4 x 1.0 From expt. (2), 1.2 x 10-4 = k[0.06Y [0.06]Y ... (ii)
[0Cl- ][1-] 0.0017 x 0.0017
=6O.55s- 1 1.2 x 10-4 = [0.06Y [0.06Y
0.3 x 10-4 [0.03Y[0.03]Y
... (iii)
•
534 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Similarly, from expt. (1) and expt. (3), increased by 1.5 times. The order of reaction with respect to A
x is:
2 x 3Y = 9 .. , (iv)
(a)1 (b) l.5 (c) 2 (d) -1
Solving eqs. (iii) and (iv), [Ans. (b)]
x =.0, y= 2 [Hint: Rate = k [A]n ... (i)
=
ICHf:0CH3) (Br2) (8+) H2 +1 H21 (fast) ... (ii)
Br2,Ms-1
5 H2I+I~2HI (slow) ... (iii)
0.30 0.05 0.05 5.7 x 10-
0.30 0.10 0.05 5.7 x 10- 5 Overall reaction: H2 + 12 ~
0.30 0.10 0.10 1.2 x 10- 4 • 2. The reaction of NO and Br2 is known-to be of second
0.40 0.05 0.20 3.1 x 10- 4 order in NO and first order in Br2'
ICBSE (PMT) 20081
2NO + Br2 ~ 2NOBr
Based on these data, rate equation is : . Rate k [NO]2 [Br2 ]
(a) Rate k[CH3 COCH3 ][Br2 ][Wf The likelihood of three molecules (2 molecules of NO and 1
molecule of Br2) colliding simultaneously is far less than the
(b) Rate k[CH 3 COCH3 ][Br2 ][W]
likelihood that two molecules will collide.
(c) Rate k[CH 3COCH 3 ][W] The mechanism is believed to be as under:
(d) Rate = k[CH 3 COCH 3 ] [Br2 ]
[Ans. (c)] (fast) ... (i)
;[~J.
measured.
1 i.e, 13 = 0 Concentration ofNOBr2 will be equal to
[NOBr2] == k' [NO][Br2]
ur
Dividing eq. (ii) byeq. (iii),
If this is substituted in the above equation, we get
~ i.e, y=1 Rate = k' k" [NO] 2 [Br2 ]
= k[NO] 2 [Br2 ]
Dividing eq. (i) by eq. (iv),
S.7x 10-
5=[~J£X X[.!Jl 3. Depletion of ozone takes place in the following steps:
Overall reaction:
3.1 x 4 4
a~l
Step 1: (fast)
Thus, rate law will be
(Equilibrium constant Kc )
rate k [CH3COCH 3]1 [H+ ]1)
k
8.9 REACTION MECHANISM Step 2: 03 +[O]~ 202 (slow)
Knowledge about involved steps in a reaction, and to determine Rate =k[03 ][0] ... (i)
which step is slowest or rate determining, is called mechanism. Nascent oxygen [0] is not present in overall reaction; thus it
The intelligent guess depending on the observed rates of should be i1iminated. .
reactions about the series of steps (known as elementary
processes) leading to the formation of products is called the K c == ][0]; [0] = Kc [0 3 ] ... (ii)
[0 3 ] [0 2 ]
reaction mechanism.
For illustration a few examples of reaction mechanisms are From eqs. (i) and (ii),
given below: Rate k[O]. K [0 3 ]
1. The reaction between H2 and 12 to form hydrogen iodide 3 c [0 2 ]
was originally postulated as a simple one step reaction.
k Kc [03]2[02r1
H2 +12 =2HI =K[03]2[02r 1
Rate = k[H 2 ][1 2 ]
K=kxK c
But, the formation of HI has been explained on the basis of the
following mechanism: Order =2 - 1= I
536 G.R.B. PHYSICAL CHEMISTRY FORCOMPEnTIONS
Iii REACTIONS OF VARIOUS ORDERS (b) The time required for the reaction to be cOnlplete, i. e. ,
time at which [A] is zero.
(i) Zero order reactions
[Alo Initial concentration
A reaction is said to be of zero order if its rate is independent t Completion ~ -k- = . Rate constant
of the concentration of the reactants, i. e., the rate is proportional
to the zeroth power of the concentration of the reactants. (c) T~e units of k ~e mol L- I time-I.
For the reaction (ii) First order reactions
A ----? Products
A reaction is said to be of first order if its rate is determined by
to be 'of zero order;
the change of one concentration term only:
_ dx k[A]o =k Consider the reaction,
, dt
A ----? Products
Some photochemical reactions and a few heterogeneous Let a be the concentration of A at the start and after time t, the
reactions are zero order reactions. Such reactions are not concentration becomes (a - x), i. e. ,x has been changed into",
common. products. The rate of reaction after time 't' is given by the .
Examples: expression
1. Photochemical reaction between hydrogen and chlorine: dx
hv -=k(a-x)
H2 (g ) + Cl 2 (g) ----? 2HCI(g ) .. . dt ...• , .' .
(/);",', ·,.t·" '
This photochemical' reaction' is zero order reaction. The or --'-"=ldt
(a-x)
reaction is studied by placing H2 and Cl 2 gases over water. The
rate of reaction is studied by noting the rate at which water rises upon integration of above equation,
in the vessel due to dissolution ofHCI formed. The rate of rise of
water is the same as the rate of disappearance of Hz and C1 2 , i.e.,
I dx =kldt
(a-x)
the concentration of the gases per unit volume in the gaseous or -loge (a x)=kt+c
phase will not change with time, although the quantities will where c is integration constant.
change. When t = 0, x =0,
2. Decomposition ofN 20 on hot platinum surface: c= loge a
1 Putting the value of' c',
NzO----?N z +-Oz
2 -loge (a x)=kt-Ioge a
Rate oc [NzO]o = k[NzO]o ::;! k or log e a - log e (a - x) = kt
d[N 2 0] ::;!k a
or or loge - - = k t
dt (a-x)
3. Decomposition of NH3 in presence of molybdenum or
or
2.303 I a
k = - - oglo--
tungsten is a zero order reaction.
I (a - x)
;
2NH3 N z +3H 2
This is known its· the kinetic equation for a reaction of the first
The surface of the catalyst is almost completely covered by order. The following two important conclusions are drawn from
NH3 molecules. The adsorption of gas on the surface cannot this equation: .
change by increasing the pressure or concentration ofNH3. Thus, (a) A change in concentration unit "ill not change the
the concentration of gas phase remains constant although the numerical value of k. Let the new unit be n times the frrst one.
product. -is formed. Therefore, this reaction shows zero order
2.303 na
kinetics. So, k = - - loglo - - -
Other examples of zero order are: I n(a x)
4. Decomposition of HI on the gold surface. 2.303 a
or k=--loglO--
S. Iodation of acetone in presence of H + ions, I (a - x)
H+
CH3 COCH3 + I z ----? ICH2COCH3 + HI Thus, for first order reactions, ai1Y quantity which is
proportional to concentration can be used in place of
The rate equation of this reaction does not include [12] concentration for evaluation of' k'.
factor, i. e. ,
(h) The time taken for the completion of same fraction of
- dx =k[CH3COCH 3 ][H + 1 change is independent of initial concentration. For example,
dt for half change,
Characteristics of zero order reaction x = O.Sa and t =11/2
(a) The concentration of reactant decreases linearly with time. 2.303 I a 2.303 I 2
So, k= oglo = - - oglO
[All::;! [A]o - kt. 1112 O.5a 11/2
CHEMICAL KINETICS 537
1
I:
kt -log - -
a
e(a+x)
.2
N
1::
k == - 2.303 log 10
t
(_a_)
a+x
~
I:
o
u This is the kinetics for first order growth kinetics.
Note: . (1) If volwnes of reagents are given in volumetric analysis
.3'----------
lime-
then we use the following equation to determine rate constant:
2.303 I V~ - Vo
k - - oglO---
t V.. - VI
Fig. 8.13
where, Vo =:: volume used at zero time,
Examples of first order reactions Vt :; volume used at time' t' ,
I. Decomposition ofH z0 2 in aqueous solution. V.. = volume used at infinite time
Case I: When Vo is not given, we use
HZ02 ~H20+.!.02 2.303)' V~
2 k : ; - - oglO--
t V.. - VI
2. Hydrolysis of methyl acetate in presence of mineral acids.
Acid Case II: When V.. is not given, then
CH 3COOCH3 +H20~CH3COOH+CH30H
3. Inversion of cane sugar in presence of mineral acids.
r
Vo
k -- 2.303 IoglO - )
t \ VI
Acid (2) If information is given in terms of angle of rotation of
C I2 H 22 0 11 +HZO~C6HIZ06 +C6H12 0 6 optically active compounds, measured by polarimeter with
respect to time, then
4. Decomposition of ammonium nitrite in aqueous solution.
NH4 NO z ~ N z + 2H zO - 2.303
k-
t
--S1
- - Iog10 { "... - ro
r,., - 'i
5. Hydrolysis of diazo derivatives.
where, ro :; angle of rotation at zero time,
C 6 HsN=NCI + H 20 ~ C 6 Hs0H + N2 + HCI 'i = angle of rotation at time' t' ,
Note: In case of gases, pressure can be used in place of concentration. r~ = angle of rotation at infinite time
538 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
k == 2.303 )OglO{ ~r_ ~}. (i) The value of k (velocity constant) depends on the unit of
conc~ntrlition.The unit:6fk is expressed as (IIlolllitre) -I ~ time~1
t r=-li
or litre mol-I time-I.
Case II: If r_ is not given, then
(ii) Half life period (t 1/2) == ~ . 0.5a = 1
- - IoglO fro}
- 2.303
k- - . k a x O.5a ka
t li
Thus, half life is inversely proportional to initial concentration.
(3) If pressure is given in gaseous reactions, then we use the
(iii) Second order reaction conforms to the first' order when
following kinetic equation:
one of the reactants is present in large excess.
k- - - 1oglO - -
- 2.303 {po} 111..1,' k 2.303 I b(a - x)'f b th
t Po-x i:U'..mg, o g l O ' 1 a »> en
tea-b) a(b-x)
where, Po = pressure of reactant at initial stage,
(a -x)= a and (a - b)"" a
( Po x) = pressure of such a reactant at 't' time.
Values of 'Po' and 'x' can be calculated using the following 2.3031 ba
Hence, k - - oglo---
examples: ta a(b -x)
A(g) ----t B(g) + C(g) + D(g)
At t = 0 Po 000 or - - Ioglo--
.ka =k ' =2.303 b
Pressure afteitime 't' (Po'-': x) x x x t (b - x)
Pressure after a long 0 Po Po Po (since, 'a' being very large, may be treated as constant after the
time or infinite time change). Thus, the reaction follows first order kinetics with
Case I: If total pressure of reaction mixture is given in place of . respect to the reactant taken relatively in small amount.
pressure of reactant, then
Examples of second order reactions
PI == (Po - x + x + x + x)
where, PI == pressure of vessel at time' t ' . 1. Hydrolysis of ester by an alkali (saponification).
Case II: Ifpressure of vessel after a long time or infinite time is CH 3 COOC 2Hs + NaOH ~ CH3 COONa + C 2HsOH
given, then 2. The decomposition of N02 into NO and O 2 ,
P- == Po + Po + Po 2N0 2 ~2NO+02
(iii) Second order reactions 3. Conversion of ozone into oxygen at 100°C.
A reaction is said to be of second order if its reaction rate is 203 ~302
determined by th~ variation of two concentration terms. 4. Thermal decomposition of chlorine monoxide.
The kinetics oNecond order reactions are given as follows:
2C120~ 2CI 2 + O?
(a) When concentrations of both reactants are equal or two
molecules of the same reactant are involved in the change, i. e., (iv) Third order reactions
A + B ~ Products A reaction is· said to be of third order if its rate is determined
or 2A ~ Products. by the variation of three concentration terms.
dx = k(a _ x)2 , When the concentration of all the three reactants is same or
dt three molecules of the same reactant are involved, the rate
On solving this equation, expression is given as:
1 x
k=-·--- 3A ~ Products
t a(a x)
A +B+C~Products
where, a initial concentration lof the reactant or reactants and
x =concentration of the reactant changed in time t. dx = k(a _x)3
(b) When the initial concentrations of the two reactants are dt
different, i. e. , On solving this equation,
A + B ~ Products
k=~. x(2a x)
Initial conc. a b
t 2a 2 (a _x)2
dx k(a -'x)(b - x)
dt
Characteristics of third order reactions
2.303 I b(a x)
k == og 10 --'---'- 1. Halflife period
tea-b) a(b-x)
1 0.5a(2a - O.5a) =: 1
=-.-,
0.5a x 1.5a
(a - x) and (b x) are the concentrations of A and B after time
interval, t. k 2a 2 (0.5ci)2 k x 0.5a x 0.5a
I
CHEMICAL KINETICS 539
3 Let after a definite interval x mol/litre of Band y mol/litre of C
::=--
2 are formed.
2a k
Thus, half life is inversely proportional to the square of initial x !f.L
concentration. y k'],
2. The change in the unit of concentration changes the
i. e., d [B]/d [C]:;::~
numerical value of k. dt dt k2
3. The unit of k is expressed as (molllitre)-2 time-lor
Variation of concentration A, Band C with time may be
litre 2 mol-2 time-I. graphically represented as,
2.
2NO + O 2 ~ 2NO z
2NO+CI 2 ~2NOCI
A
3. Reduction of FeCI 3 by SnCI 2 .
Time-
2FeCI 3 + SnCl 2 ~ SnCl 4 + 2FeCl 2 Fig. 8.14
A ~ Products
Order Rate laweqn. Expreulon for rate eon.t.
0 Rate =k k= ![[A]o-[A]]
OH kl ONO,
~I (Main) .
0"
A ~ Products Rate = k[A]
t g [A]
=H[~] -[1]J
. k2
2A ~ Products 2 Rate = k[ A ] 2 k
(Side)
A+ B~ _ k =2.303· 10 [Blo[A] I
Products 2 Rate -.k[A][B] t([Alo-[B]o) g [A]o[B]
3A ~ Products
-d [A] :;:: (k l + k2 )[A]::= kay [A] Examples: (i) Decomposition of ethylene oxide:
dt kl
(CH 2 hO~ CH3CHO
kl ::= fractional yield of B x kay k2
k2 :;:: fractional yield of C x kay CH3CHO~ CO+ CH 4
If kl »k2 then, (ii) The pyrolysis of acetone:
A~Bmain and
(CH3)2CO~CH4 +CH 2 =C=0
A ~ C is side reaction Ketene
540 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
1 First possibility :
CH 2 =C=O--7 C 2 H4 +CO
2 Step 1 A ----"7 A' ----"7 B
Step 2 B ----"7B' ----"7C
1
Potential
Energy
Tlme-
Fig. 8.15 c
Variation of concentration of various substances during the
progress of reaction (A ~ 8 ~ C ) Reaction coordinate -
''I kz
Fig. 8.17
A~B~C
Activation energy of step 1 is greater than that of step 2 thus
Let initially (t =0), [B] =0 and kl < k2 then maximum
step 1 will be slow and rate determining.
concentration of[B] may be calculated as,
Second possibility :
k ] kZlkJ kz
[B]max [A]O-1 s*
[ k2
where, [A]o =initial concentration of A
as,
Time in which B attains maximum concentration may be given 1
potential
Energy
t =k22.303 Iog - (k2)
max - k J kJ
c
Concentration of[B] after time 'f' may be calculated as,
Reaction coordinate -
[B]t k\ [A]o [e-kJt e-k2t]
Fig. 8.18
k2 k\
Activation energy of step 2 is greater than that of step 1 hence
Activation energy diagram of a composite reaction involves step 2 will be slow and rate determining
more than one peaks and number of peaks indicate the number of
different types of activated complexes involved. The numher of Reversible Reactions
valleys in the activation energy diagram indicates the number of The reactions in which the products of chemical change react
different types of reactive intermediates involved. together to form the original reactants, are called reversible
reactions. These are also called opposing or counter reactions .
.Let us consider a reversible reaction in which both forward
* and backward reactions are of fIrst order.
* ~ Activated complex kJ
1
Energy
I ~Intermediate
AH =+ve, endothermic
reaction
A~B
k2
Initial state (I = 0) a 0
Conc. at time (t) a-x x
Equilibrium conc. (a - Xe )xe
Reaction coordinate -
lV' lV'
Plots of half lives vs. concentration (t 112 ex: a 1- n) :
2.303
k=- - Iog 10 - -a . , fi d .
- ,~or lrst or er reactions;
k=
t
l[_I__ l]
(a - x)
k =I [ I _
2t (a-x)2 a
~] , for third order reactions. This relation can be used to determine order of reaction 'n'.
4. van't Hoff differential method
As we know that, the rate of a reaction varies as the nth power
2. Graphical method of the concentration of the reactant where' n' is the order of the
reaction. Thus, for two different initial concentrations C 1 and C 2'
A graphical method based on the respective rate laws can also
equations can be written in the form
be used.
If the plot of log (a - x) versus 't' is a straight line, the _ dC, =ken and _ dC 2 =kCn
dt I dt 2
reaction follows first order.
Taking logarithms,
If the plot of _1_ versus' t ' is a straight line, the reaction
d~l ) =log 10 k +n loglo CI
(a x)
loglo (- ... (i)
follows second order.
If the plot of I versus' t ' is a straight line, the reaction
(a-x)2 and ... (ii)
follows third order.
In general, for a reaction of nth \)rder, a graph Subtracting eq. (ii) from eq. (i),
Determine the order ofthe reaction with respect to A and w. r. t. -3 - 2.303 I 0.062
6 .2 x 10 - - - oglO
B. What is the half life ofA in the reaction? 100 PI
Solution: Let the rate of reaction be
6.2 x 10-3 x 100 . ,
R~te = k[AY[B]Y or 2.303 = log 10 0.062 - log 10 (PI)
From the data given, it is clear that by doubling the
concentration of A, the rate also becomes double when B is kept or 0.2692 = log 10 0.062 - log 10 (PI)
constant. Thus, the rate is directly proportional to concentration
ofA. or log 10 (~ ) =log 10 0.062 0.2692
Rate oc: [A], i.e., x 1 = (2.7924 - 0.2692)
Or the order of reaction w.r.t. A is 1.
When the concentration of A is kept constant and the PI =0.033 atmosphere
concentration of B is doubled, the rate does not change, i. e. , Pressure after 100 sec = 0.033 atm
y = 0; or the order of reaction w.r.t. B is zero.
dx Example 23. The half life of a first order reaction is 60
Thus, reaction rate, - ~ = k[ A] min. How long will it take to consume 90% of the reactant?
dt
Solution: For the first order reaction
Again k-..:. 0.005
- - -- 0 .5 mIn
. -I
0.01 k = 0.693 0.693 == 11.55 x 10-3 min- I
Half life of A := 0.693 0.693 = 1.386 min tl/2 60
k 0.5 Applying first order kinetic equation,
. Example 21. Thermal decomposition of a compound is of 2.303 a
t =--log 10 - -
the first order. If 50% of a sample of the compound is k (a-x)
decomposed in 120 minutes, how long will it take for 90% of the
compound to decompose? Given: a= 100,x== 90, i.e., (a-x)=(100-90) 10
Solution: Half life of reaction = 120 min Hence, t 2.303. log 10
We know that, 11.55 X 10-3 10
= 199 min
k -- 0.693 -_ -
0.693
-- :... 5. 77 x 10-3 mIn
·-1
tl/2 120 . Example 24. A first order reaction has a rate constant of
15 x 10-3 S -I. How long willS.O g ofthis reactant take to reduce
Applying first order reaction equation, to 3.0 g?
2.303 a Solution: Applying first order kinetic equation,
t = log 10
k a-x 2.303 a
1
k oglo(a_x)
Ifa=100, x 90or(a-x)=IO,
Given: k::::: 15x 10-3 sec- I ,a =-5 g,(a -x)::::: 3 g
S0, 2.303 . Iog 10 10 2.303 :::::
399'
mIn
5.77 x 10-3 5.77 x 10-3 2.303 5
So, t= 3 log 10 :::: 34.07 sec
15x 10-: 3
Example 22. The decomposition ofCl20 7 at 400K in the
gas phase to Cl 2 and 02 is a first order reaction. . Example 25. Catalytic decomposition of nitrous oxide by
(i) After 55 seconds at 400K, the pressure ofCl20 7 falls from gold at 900°C at an initial pressure of 200 mm was 50% in 53
0.062 to 0.044 atm. Calculate the rate constant. minutes and 73% in 100 minutes.
(ii) Calculate the pressure of Cl 20 7 after 100 seconds of (a) What is the order of reaction?
decomposition at this temperature. (b) How much it will decompose in 100 minutes at the same
Solution: (i) As pressure oc concentration, temperature but at an initial pressure of600mm? (lIT 1990)
. Solution: (a) Using first order kinetic equation and
- 2.303 1 Pi (initial pressure) substituting given values,
k - - - og 10 --'----=-----'----
PI (pressure after time t) In first case: k = 2.303 10 200 = 0.0131 min- I
53 glO 200-100
- -
- - . IoglO -
2.303 0.062
-- - 62
. x 10-3 s-1
55 0.044 In second case: k = 2.303 10 200 = 0.0131 min -I
100 glO 200-146
(ii) Again applying the first order kinetic equation,
As the values of k come out to be the same in both cases, the
2.303' Pi (initial pressure)
k= log 10 -.- - - - - - - - reaction is of first order.
t Pt {pressure after time t)
CHEMICAL KINETICS 543
(b) As in the first order reaction, the time required for the Example 28. In Arrhenius equation for a certain reaction,
completion of same fraction is independent of initial the values ofA andE a (activation energy) are 4 x 1013 sec- 1 and
concentration; the percentage decomposition in 100 minutes
98.6kJ mol- 1 respectively. If the reaction is of first order, at
when the initial pressure is 600 rum will also be 73%.
what temperature will its halflife period be 10minutes?
. Example 26. A substance reacts according to the first
order rate law and the specific reaction rate for the reaction is (liT 1990)
Solution: According to Arrhenius equation,
I x 10-2 S-I. Ifthe initial concentration is 1.0 M
k= Ae-Ea IRT
( a) What is the initial rate?
(b) What is the reaction rate after I minute? E
or loge k == loge A _ _
a
Solution: (a) Initial rate of a first order reaction kC RT
=IxI0-2 X 1.0= Ix 10-2 molL-1 S-I
. . Ea
or 2.303 log 10 k = 2.303 log 10 A - RT
(b) Concentration after 60 seconds is calculated by applying
.
first order kinetic equation, For a fiIrst ord er reactIOn t 112 = 0.693
k
k 2.303 1
60 1oglo (I-x) So, _,'
_,'1.
It --
0.693
sec
-I (
t 112 10min 600 sec)
.600
or 1x 10-2 = 2.303 log (1- x)] 1.1 x 10-3 sec-I
60 3
60x 10-2 Hence, Iog (l.lx.'.:10-3 ) == 1og (4 x 1013 ) - _ _
98_.6_x__
10__
or - - - = -log (I-x)= 0.2605 2.303 x 8.314 x T
2.303
T= 31O.95K
log (1- x) = - 0.2605 Example 29. A second order reaction, in which both the
= 1.7395 reactants have same concentration, is 20 % completed in 500
seconds. How much time it will take for 60% completion?
(1- x) antilog of (1.7395) = 0.5489 mol L- I
Solution: The second order equation when both the
Rate of reaction after 1 minute = k x C reactants have same concentration is
Again applying first order equation, . Example 33. The gas phase decomposition of dimethyl
2.303 100 ether follows first order kinetics.
t==-k- 1oglO (l00-80)
CH30CH3 (g) -----t CH4 (g ) + H 2 (g ) + CO(g)
-
t 800 sec [N 20 S ] = 1.45mo/L-I =[Ad Let the pressure of dimethyl ether after 12 minutes be p atm.
Applying first order equation,
t=1600sec [N 20 S ] = 0.88 mol L- l =[A 2 J 2.303
k=--loglo
t P
Solution: Applying the formula,
log 10 0.4 0.047'93 x 12 0.2490
'-
k-
2.303 I [Ad P 2.~03
oglo--
(t2 tl ) [A 2 ]
or 0.4 =1.7743
= 2.303 I 1.45 P
P = ~ = 0.2254 atm
(1600 800) og 10 0.88
or
1.7743
= 2.303 x 0.2169= 6.24 x 10-4 sec-I
800 Decrease in pressure, x = 0.4 - 0.2254 == 0.1746 atm
CH 3 0CH 3 (g) -----t CH 4 (g)+ H2(g)+ CO(g)
Example 32. The decomposition ofN 20 5 according to the
Po x x x x
equation, Total pressure = Po + 2x
N 20S (g) -----t 4N0 2 (g) + O 2 (g)
= 0.4 + 2x 0.1746
is a first order reaction. After 30 minutes from the start of the
=0.7492atm
decomposition in a closed vessel, the total pressure developed is
found to be 284.4 mm Hg and on completion, the total pressure is , . Example 34. The half life offirst order decomposition of
584.5 mm Hg. Calculate the rate constant of the reaction. nitramide is 2.1 hours at 15°C.
(lIT 1991)
Solution:
If6.2g ofNH2N02 is allowed to decompose calculate (i) time
On decomposition of2 moles ofN 2 0 s , 4 moles ofN0 2 and 1 taken for NH2 N0 2 to decompose 99% and (U) the volume ofdry
mole of O 2 are produced. Thus, the total pressure after N 20produced at this point, measured at STP. (lIT 1994)
completion corresponds to 5 moles and initial pressure to 2 . (.)
SoI ution. 1 k - 0.693
------- .
- 0.693 - 0 33 hr- I
moles. . t 112 2.1
Initial pressure ofN2 0 s , Po = ~ x 584.5= 233.8mmHg Applying kinetic equation of first order reaction,
5 2.303 a
k==--, log 10 - -
After 30 minutes, the total pressure = 284.5 mm Hg t (a-x)
2N 2 0 S -----t 4N02 + 02 2.303 I 100
or
PO-2P 4p P t = 0.33 oglO (100- 99)
or Po + 3p 284.5 =l3.96hrs
or 3p= 284.5 233.8= 50.7mmHg (ii) No. of moles ofNH 2N0 2 decomposed
- 2.303 I
k --30 233.8 - 5 2 10-3 ·-1
oglO - - - . x mm
Volume of N2 ° at ~TP =O.099'x 22400 mL
200.0 = 2217.6mL
I
CHEMICAL KINETICS 545
Hence, order w.r.t. A is 2nd and order w.r. t. B is 1st. The total pressure measured at constant temperature and
constant volume varies with time as follows:
(ii) Rate = k· [A]2[B]
t (min)
pi mm Hg 760
° 5
836
7.5
866.4
10
896.8
From expt. (I ) , 5 x 10-4 = k[2.5 x 10-4]2 [3.0 X 10-5 ]
Calculate therate constant assuming the reaction to follow the
. 5x10-4 , firs/order rate law.
or k= =2.67x10 8 L2 mol-2 S-1
[2.5 x 10-4]2 [3.0 X 10-5 ] Solution: For fITst order, the,rate equation is
Initially after time t
(iii) From Arrhenius equation,
2.303 1 [A]o 2.303,1
I 2.0x 10-3 , 20
k - - og--= og
t [A] t P
ogIO 5.0x 10-4 ::::; 2303 x 8.314 x 300x 320
given, Po == 760rrmi Hg.
2.3,03x8.314x300x320 I 4 The decomposition reaction is:
- - - . , . - - - - - - - - x og 10
20,
2AsH3 (g) --? As(s) + 3H2 (g)
=55.333 k1 mor l . Po o 0
3x
" PO-2x
(iv) Applying log 10k = log 10 A - --=-- Total pressure, PI Po - 2x+ 3x= Po +X
, , 2.303RT
,A ' 55.333 X=PI-PO
10glO ,- '" :::: 9.633
k' 2303 x 8.314 x 300 PAsH] (Po - 2x)= Po - 2Pt + 2po= 3po - 2pt
I
546 GR.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
After 5 minutes, PAsH) (3 x 760) (2 x 836) titrated with a standard alkali s.olution. The following results
were obtained:
==608mmHg
Time (min) 0 75 119 183 00
k == 2.303 log \0 760 0.0446 min- I Alkali used (mL) 19.24 24.20 26.60 29.32 42.03,
5 608 Show that the reaction follows first order kinetics.
After 7.5 minutes,PAsH) (3 x 760) - (2 x 866.4) Solution: In case the hydrolysis follows first order kinetics, then
2.303 2.303 I V= -
== 547.2 mm Hg k == 1oglO - - oglo - - " -
t [A] t V"" - VI
k 2.303 10 . 760 == 0.0438 min -I
7.5 glo 547.2 When, t == 75 min, V"" = 42.03, Vo == 19.24, VI 24.20
After)O minutes, PAsH 3 (3 x 760)(2 x 896.8) k 2.303 (42.03 - 19.24) = 2.303 10 22.79
10
486.4mmHg 75 glO (42.03-24.~o') 75 glO 17.83
Solution: Multiplying equation (ii) by 2 and adding (i), we 10 (4.5 x lO- J_'.
IO
Eo 1 I]
get: g 1.3 X 10- 11 - 2.303 .~ 8.314 x 10-3 543 623
Cl 2 + 2CO~ 2COCI
Ea =120 kJ]
K = [COClf ~26. The reaction of0 3 with chlorine atom is given as:
[Cl z][CO]2 0 3 (g) + CI(g) - - t 02(g) + CIO(g);
[COCI] = (K)1I2 [CI 2 ]V2 [CO] ... (i) " kl = 5.2x 10 9 L mol-I sec- I
Slowest step is rate determining, hence, C10(g) + O(g) ~ CI(g) + 02(g);
Rate k[COCl][C1 2 ] ... (ii) k2 ='2:6x 1010 Lmol- I sec- 1
From eqs. (i) and (ii), we.get Which of these values is closest to the rate constant of the
Rate = kK 112 [e1 2 ]lI2 [C1 2 ][CO] overall reaction?
Rate = k' [CI 2 ]3J2[CO] 03(g) + O(g)--t 20 2 (g)
., (a) 5.2 x 109 • (b) 2.6 x 1010
Thus, rate law is in accordance with the mechanism.
10
(c) 3.lx 10 (d) 1.4 x 1020
[Ans. (a)]
. if
22. A first order reaction has half life of 14.5' hrs .. What [Hint: Lowest value of k shows that the step is rate detennining.j
percentage of the reactant will remain after 24 hrs? 27. If a first order reaction takes 32 minutes for 75% completion,
(a) 18.3% (b)31.8% (c) 45.5% (d) 68.2% then time required for 500/0' completion is:
. [Ans. (b)] [A'VIU (Medic.al)
(a) 32 min (b) 16 min (c) 8 min (d) 4 min
[Hint: k = 2.303 log [_a_) [Ans. (b)]
0.693
t
2.303 I
a
100
x
. [Hint: k = 2.303 log
t a
(_a_) x
og
14.5 24 (a-x)
When, a = 100, x = 75, t = 32
On solving, (a":'x) 31.8%]
k - 2.303 I . (100.) -00433 ·-1
23. Half life of a first order reaction is 10 min. What % of reaction - 32 ogiO 2s -. mm
will be completed in 100 min?
(a) 25% (b) 99.9% (c)75% (d) 80% TIme lor 01/0 compIetlOn
· "50 ' (t1l2 ) = -
0.693 0.693 . ]
- = - - '" 16mm
[Aus. (b)] . k 0.0433
2
28. Rate constant of areaction is l751itre- mol- 2 sec-I. What is
[Hint:
0.693
- .-
2.303 I
- - oglO
[a
--I1 the order of reaction? reET (,~'; , ' , ' ; ' . [
tl/2 t a - x) (a) First (b) Second (c) Third (d) Zero
[Ans. (c)]
0.693 "" 2.303 10 (~)
10 100 g 100.,.. x . . [litre] n-I _
[Hmt: Dmt of k - x sec I ... (i)
x = 99.9%]
mol
24. A certain zero order reaction has k = 0.025 M s-I for the Given unit of k = litre2 mol- 2 sec- I ... (ii)
disappearance of A. What will be the concentration of A after Comparing theI1llit of litre,
15 seconds if the initial concentration is 0.5 M? I 2 n
(a)0.5M (b)0.32M (c)0.12M (d)0.06M
n = 3]
[Ans. (c)]
29. The half life of a fIrst order reaction having rate constant
[Hint: x = kt = 0.025 x 15 0.375 M 5 I
k = 1.7x 10- sec- is: (.J!PYIER 2006)
Remaining conc. = .0.5 - 0.375 0.125 M] (a) 12.1 hrs (b) 9.7 hrs (c) 11.3 hrs (d) 1.8 hrs
[Ai1S~ (c)]
25. A first order reaction:
2N zO(g) - - t 2N 2(g) + 02(g) . 0.693 0.693 4
[H mt:. tli2 = = 5 = 0764 sec =11.3 hrs]
has a rate constant of 1.3 x 10- 11 8- 1 at 270"C and . k 1.7 x 10-
4.5 x 10- 10 at 350°C. What is the activation energy for this 30. At500 K, the halflife period oJ a gaseous reaction at aninitial
reaction? pressure of80 kPais 350 sec. When the pressure is 40 kPa, the
(a) 15kJ (b) 30 kJ (c) 68 kJ (d) 120 kJ half life period is 175 sec; the order of the reaction is:
[Ans. (d)] !PET (Kerala) 201)71
(a) zero (b) one (c) two {J) three
[Hint: 'log (k 2 J =~ 1 1] (e) half
k1 2.303R TI T2 [Ans. (a)]
548 G.R~B. PHYSICAL CHEMISTRY FOR COMPETITIONS
[Hint:
(tli2)l _(Pz)n-l [Hint: k = 2.303 log a
t a-x
(tli2h Pi
2.303 1 100
350 f 40\"-1 70 og 100- 90
175 lso; . = 0.0329 min- ]
i
2=(~r-'1 . 32. The half life period of a first order reaction is 1 min 40
seconds. Calculate its rate constant. 2008)
n 1=-1 (a) 6.93 x 10- 3 min-I (b) 6.93 x 10- sec-I
n = 0 (zero order reaction)] (c) 6.93 x 10- 3 sec (d) 6.93 x 103 sec
31. 90010 of the first order reaction is corp.pleted in 70 minutes. The [Ans. (b)]
velocity constant of the reaction is: [Corned (Karnataka) ~{)i)81
(a)0.0329 (b) 0.329 (c) 3.29 (d) 0.0293 [Hint: k = 0.693 0.693 = 6.93 xlO- 3 sec-I]
t1l2 100
. [Ans. (a)]
MISCELLANEOUS
' .
NUMJ~CAL EXAMPLES~ H~
. ~
Example 1. Ammonia and oxygen react at .higher la) What is the energy ofactivation ofr rea~tiqn?
temperature as, (b) What is the value of kat 670 K? ~.
4NH3 (g) + 502 (g) -----7 4NO(g) + 6H 20(g) Solution: (a) We know that,
in an experiment, the. concentration of NO increases by E
log 10 k=log 10 A - - - - (i)
1.08x 10-2 moilitre- I in 3 seconds. Calculate:
1 ...
. . 2.303RT
(i) rate ofreaction, (tl) rate ofdis.appearance ofammonia,
loglO k (s-I )= 14.34 ~ 1.25 x 10
4
Example 5: Two reactions of the same order have equal SolutiQIl: We know that,
exponential factors but their activation energies differ by 24.9
kJ I mol. Calculate the ratio between the rate constants of these k --'- 2.303 Ioglo -a-
t a-x
l' J
reactions at 27 0 C. (R = 8.31J K -I mol-I) (Dhanbad1990)
Solution: We know that, At 298 K, x 10, a = 100,
E 2.303 100
loglO k - 10gIO A k298 = - - log 10 - .. ' (i)
2.303RT tl 90
Time (minute) 0 15 30 45 60
. Number of bacteria 50· 100 200 400 800
. 4 Show that the 'rate ofproduction of bacteria is offirst order. How
. lanty
Rate lmo ' I sec) :::: -
2.666
-- x-
10-- many bacteria will be there after 3 hours?
0.0821x 298 Solution: For bacterial growth,
:::: 1.09 X 10-5 mollitre- I
Example 10. A drop ofsolution (volume 0.05 mL) contains.
k =_ 2.30310glo
t
(_a_\j
\a+x
3x 10-6 mole H + ions. If the rate of disappearance o/the H +
io~ is I x 107 mol litre -I sec -I ,how long would it take for H + At 15 minutes: k= - 2.303 10 (~\J
15 glO 100
ions in the drop to disappear?
Solution: 0.0462 min- I
. mole 2.303 I ( 50 ']
Concentration of drop = x 1000 At 30 minutes: k=
. volume in mL 30 og1o 200)
3x10-6 . _ :::: 0.0462 min -I
= x 1000 = 0.06 mol htre 1
0.05
. cone. change
Rate of;"hsappearance = --.---"'---
At45 minutes: k - 2.30310glo (~) = 0.0462 min- 1
45 400 .
.. tIme
/ Ix 10 7 = 0.06 Same values of rate constants show that the process corresponds
time to first order.
Time 6 x 10-9 sec Let there be' n' bacteria after 3 hrs.
c [0 3 ] c [° ]
2
, (1) 0.0836 0.404 65 0,0068
putting the value in eq. (i) (2) 0.0836 0.202 120 0.0031
(3) 0.0418 00404 60 0.0032
From eq. (i), From these data calculate order ofthe reaction.
Rate k·[O]. K [03J k. K . [03 ]2 =K. [0 3 ]2 Solution: Rate::= k[HgC1 2 r'[K 2 C Z0 4 )r:;
3 c [° 2 ] c [° 2 ] [Oz]
0.0068 = k[0.0836]U[00404]Il; ... (i)
Here, 65 .
552 G.R.B. PHYSICAL CHEMiSTRY FOR COMPETITIONS
0.0031 = k[0.0836]<l [0.202]13 . ... (ii) Similarly, for 2nd reaction it becomes 3 times,
120 . . ' :. At 75°e
0',0 0032 = k[0.0418]<l[OA04]13 ••• (111
... ) rilte of reaction for 2nd (3)5 R2 '
6 rate of reaction for 1st = (2)5 Rl = 7.5937 (": Rl = R 2 )
Dividing eq. (i) by eq. (ii), we get 4 = 213 ; ~ =2
Example 22. The reaction, A + OH - ----t Products, obeys
Dividing eq. (i) by eq. (iii), we get
rate law expression as:
Thus, overall order =ex + ~ =3 -d[A] = k[A][OH -]
Example 20. The rate constant of the reaction A ----t B is dt
k = 0.5; the initial concentration of A bei/i;j, 1 mol/litre.
If initial concentrations of[A] and [OH -] are 0.002 Mand
Calculate the degree ofconversion ofsubstance 'A' within 1 hour
if the reaction is of zeroth, first and second order. How does the 0.3 M respectively and ifittakes 30 sec for 1%A to react at 25°C,
degree ofconversion depend on the order of reaction? calculate the rate constant for the reaction.
Solution: Zero order: ,
x=kt '
. Solution:
A + ----tProducts
t= 0 0.002
x = 0.5 x 1 = 0.5
t = 30 [0.002 _ 0.002 x 1] [0.3 _ 0.002 x 1]
2.303 a 100 . 100
k=--loglo - -
t a-x
· k 2.303 1 b(a-x)
k = 0.5; t = Ihr; a = 1M U smg = oglO ,
t(a-b) a(b-x)
0.5 = 2.303 10 _I_
I glO (1- x) 0.3 [0.002.!. 0.002 x 1]
k= 2.303 10' 100
x= 0.39
1 x 30x(0.002-0.3) glO O.002[0.3_0.002Xl].
Second order: k=:....--- 100
t a(a - x)
. 1 x k= 1.12x 10-3 litre mol-l S-l
0.5=-·--
1 1(1- x)
'E'timple 23. A hydrogenation reaction is carried out at
x = 0.33 500 K. If the same reaction is carried out in presence ofa catalyst
, Example 21. Two first order reactions proceed at 25° Cat at the same rate, the temperature required is 400 K. Calculate the
the same rate. The temperature coefficient of the rate of the first activation energy of the reaction if the catalyst lowers the
reaction is 2 and that ofsecond reaction is 3. Find the ratio ofthe activation barrier by 20 kJ mol -I. (liT 2000)
rates of these reactions at 75° C. Solution: Arrhenius equation may be given as,
Solution: For fIrst order reaction, 1j = k[A]1 k = Ae-EaIRT
•• 1j /1-2 == kl / k2 = temperature coeffIcient Let k500 and k 400 be the rate constants at temperatures 500 K
and 400 K (in presence of catalyst) respectively. E 500 and E 400 be
Let the rate of reaction for 1st at 25°e be Rl and the rate of the activation energi~s at temperatures 500 K and 400 K
reaction for lInd at 25°e be R 2 . respectively..
Also, Rl =·R 2 k 500 -- Ae- E500 IR x 500 ... (i)
Rates of reaction
k 400 -_Ae-E400IRx400 ... (ii)
.. At 25°e Rl R2
35°e 2Rl 3R 2 Given, k500 = k 400 (same rates in presence and absence -of a
45°e (2)2 Rl (3)2 R 2 . catalyst).
55°e (2)3 Rl (3)3 R2 On comparing eq. (i) with eq. (ii),
E500 _ E 400
65°e (2)4 Rl (3)4 R2
R x 500 R x 400
75°e (2)5 Rl (3)5 R2
E500 =' E 40'o "
or
:. Temperature coefficient for 1st reaction = k35 = R35 = 2 5 4
k25 'R25 E 400
or E500 E:O-- X 5 ... (iii)
i. e. , for each 10 0 e rise in temperature, rate becomes 2 times. 4
Given, E500 = E 400 + 20
CHEMICAL KINETICS 553
Substituting in eq. (iii), Solution: Let order with respect to A and B are a and fl
E 400 + ?-O= E 400 >< 1.25 respectively. Rate law expression may be given as,
Rate = k[A]ct [B] ~
or E 400 = 20 = SOkJ mol~1 ,i~:,f;' 0.05 = k[O.l]ct [0.2] ~ ... (i)
025 J ," ."',", ,""
..~ ," ,< ,;~~.
k[O.2]U [0.2] ~
• •
0.10 ... (ii)
So, Esoo = SO + 20 = 100 kJ mol/-I' ,
0.05 k[O.lt [0.1] ~ ... (iii)
. Example 24. Some PH3 (g) is introduced into a fask at r
600°C containing an inert gas, PH 3 proceeds to decompose into Dividing eq. (i) by eq. (ii), we get
P4 (g) and H2 (g) and the reaction goes to completion. Total
pressure is given below as a function of time. Find the order of ~ [~J u, i. e. , a::::: 1
the reaction and calculate the rate constant,
Time (sec) 0 60 120 00 Divi~ing eq. (i) by eq. (iii), we get
Pressure (mm Hg) 262.40 272.90 275.51 276.40
1 =[2] ~ , i. e. , f) =0
(Ill' 2001)
Rate=k[A]1 [B]o
Solution: 4PH 3 (g) + Inert gas ~ P4 (g) + 6H 2 (g) + Inert gas
Substituting the value of a and f) in eq. (i), we get
tOP P; 0 0 a
t=t (P x) P; x/4 6x/4 P; 0.05 k [0.1]1 [0.2]0
t = 00 OP; P/4 6P/4 P;
k = 0.5 sec-I
At t = 0, 262.40 = P + Pi ... (i)
t 60 sec 272.90 = PPH3(left) + PP4 (g) + PH2 (g) + Pi Example 26. A + 2B ~ 3C + 2D
The rate of disappearance of B is I x 10-2 mol litre -\ sec -I .
t 120 sec 275.51 ::::: PPH 3 (left) + PP4(g) + PH2 (g) + Pi
, What will be the (i) rate of the reaction and (if) rate ofchange in
t = 00 276.40 = PP4(g) + PH2 (g) + Pi concentration ofA and C? [CSSE (Mains) 200::;;1
P 6P 1 d[B]
276.40 = - + - + P Solution: (i) Rate = - -
4 4 I
2 dt
276.40 x 4 ::::: 7P + 4Pi ... (ii)
=- ~ [-Ix 10-2 ]
Att = 0, 262.40 P + Pi ... (iii) 2
On solving eqs. (ii) and (iii), we get 0.5 x 10-2 mol litre -I sec-\
4
. Example 28. For first order reaction, if rate constant at
17°Cis2.8xlO- 5 s-l andat27°Cis2.8xlO- 4 s-I.
1og
2.8><; 10- Ea [1
- I J.
2.8 X 10- 5 2.303 X 8.3 290 300
(i) Write the equation for calculation ofactivation energy. • •
. E = 2.303 X 8.3 X 290x 300
(ii) Calculate the activation energy. a 10
1
(R= 8.3 JmoZ- k-I) IAIPMT (Mains) 20081 =: 166299.6 J mol- 1
Solution. We know, 166.3 kJ mol- l
1og l(k;z ) = 2.303R [1Tl - T1]
k Ea
z
1. Chemical.kinetics: It is the branch of chemistry which masses of the reactants at that instant raised to powers which are
deals with the rates of reactions, the factors which influence it numerically equal to the numbers of their respective molecules in
and the mechanism by which the reactions occur. the stoichiometric'equation describing the reaction. Consider the
2. Rate of reaction: It is the speed with which the reactants following general reaction,
are converted into products. It may be expressed in terms of rate
ml Al + mz A 2 + m3 A 3 + ..: ~ Products
of disappearance of any of the reactants or rate of appearance of
any of the products. Rate of reaction ~ [AI ]m! [A 2 ]m2 [.43 ]m3 •••
The rate measured over a long time interval is called the
average rate. 4. Rate const~nt: It is equal to rate of reaction when
concentration of each reactant is unity, i. e. ,one m~-le litre -:-1 .It is
Decrease in conc. of reactant
Average rate of reaction = a constant for a particular reaction at a given temperature and also
Time taken known as. specific t:ate constant or specific reaction rate.
Consider a general reaction,
Increase in conc. of product
+---------=---- aA + bB + ... ~ Products .
Time t.aken
A -ve sign signifies a decrease in concentration of the reactant dx = k[At [B]b ...
dt
and +ve sign indicates ail increase in concentration of the
product. If CA=CB 1 or [A]=[B]
In general, for a reaction,
Then, dx k
nlA + nzB +n 3C + ... -->m1X + mzY + m3 Z +", dt
I 6.A 1 tlB· I AC
5. Collision theory of reaction rate: A chemical reaction
=--
n l At nz At n3 At occurs when the existing bonds of the reactants are broken down
AY I AZ
and new bonds come int0 existence in the molecules of products.
1 AX
-- The basic requirement for a reaction to occur is that there should
m1 At mz At m3 At be physical contact between reacting species, i. e., they must
Average rate is not very useful as it does not remain constant collide with one another. Effective collisions which bring
throughout its life span. It is more appropriate to express chemical change are fewinspite of large number of actual
instantaneous rate. collisions. For a collision to be effective, the following two
conditions must be satisfied:
Rate of reaction with reference to a particular instant of time is
called instantaneous rate of reaction. It is defined as the rate of (i) Reacting species must possess· adequate energy to
change of concentration of anyone of the reactant or product overcome the energy barrier.
species over a small interval of time. (ii) Reacting molecules must be properly oriented at the time
of collision.
. dx dx
R ate 0 f reactIOn =- - or + - The minimum amount of energy which the colliding particles
dt dt
must possess as to make the chemical reaction to occur is called
1
Units ofrate of reaction are conc. time- ,e.g.,mol L-1s- 1 or threshold energy. The excess energy (over and above the average
mol L- 1 hr- 1 , etc. energy of the reactllg species) required by the reacting species to
undergo chemical reaction is called activation energy (Ea ).
3. Law of mass action: It was presented by Guldberg and
W~ge in 1864. At a given temperature, the rate of a reaction at it Activation energy = Threshold energy Average kinetic
particular instant 'is proportional to the product of the active energy of the reacting molecules
CHEMICAL KINETICS 555
Every chemical reaction whether exothermic or endothermic involved in the balanced equation. There are number of reactions
has an energy barrier" which has to be overcome before the which are complex in nature and occur in several steps; the
reactants can be transformed into products. The reacting molecularity of "such reactions is determined by the slowest step.
molecules must have "Sufficient energy as to cross' this energy Thus, molecularity depends upon the mechanism of the reaction.
barrier. The effective collisions increase with increase of (ii) Order of reaction: Rate equation or rate law is an
temperature, i. e., rate of reaction increases with increase of experimentally determined mathematical expression relating the
temperature. molar concentrations of the reactants to the actual reaction rate.
6. Factors influencing the reaction rate: The chief factors Consider a general reaction,
which influence the rates of reactions are:
0) Nature of reactants: The reactants with weak bonds nl A + n2B + n3C + ... -7 Products
react quickly whereas the reactions involving reactants with The rate law or rate equation is"
strong bonds are slow. The molecular reactions are generaily
slow while ionic reactions are fast.
(ii) Concentration of reactants: The rate of reaction
increases with increase in concentration of reactants as the
Order of reaction is the sum of the exponents (powers) to
number of collisions increases.
which molar concentration terms are raised in the rate law.
(iii) Catalyst: Positive catalysts increase the reaction rate
Order of reaction = (x + y + z + ... )
by providing an alternative path involving lesser amount of
activation energy. The value of (x + y + z + ... ) usually ranges between 0 and 2
and even 3. It may have positive, negative, zero and fractional
(iv) Temperature: The rate of reaction increases with an
values. It is termed overall order. The reactions are classified as
increase in temperature. The number of effective collisions
zero, first," second, third order according as (x + y + z + ... ) is
" increases with increase" of temperature. The rates of many
zero, one, two or three respectively. The order can be expressed
reactions are approximately doubled or tripled for every
either in terms ofthe order oftM specific reactant or in terms of
10 0 C rise in temperature. The temperature coefficient is defined overall order of the reaction.
as the ratio of specific reaction rates of a reaction at two
The reactions which obey a first order rate equation, although
temperatures differing by 100 C.
they are not uriimolecular, are said to be pseudo first order.
k/ +10 '.
Temp. coefficient - - (value bes generally 8. Reactions of various orders: In such reactions, the
kt concentrations of various reactants except one remain practically
between 2 and 3)
constant during the course of reaction.
Arrhenius suggested an equation which describes k as a (i) Zero order reactions:. A reaction in which the rate is
function of temperature, i. e. , independent of the concentration of the reactant molecules, i. e. ,
k Ae-EaIRT the rate is proportional to the zeroth power of the concentration of
the reactants. .
where, k = rate constant, A = a frequency factor (constant), dx
E a energy of activation, R = gas constant and T = temperature. " k[Alo = k
dt
At two temp~ratur? ~ T~ a (1
and
J 1 J i. e., the reaction velocity remains constant throughOut the
progresS of the reaction. The concentration decreases linearly
agio lk; = 2.303R lTI - T2 with time. "
7~ Molecularity and order of reaction: [AL =[A]o kt
(i) Molecularity of ~action: The minimum number of [A]o ,Initial concentration
reacting particles (molecules, atoms or ions) that come together t completion = -k- Rate constant
or collide in a rate determining step to form product or products is
called the molecularity of the reaction. The "reactions are termed The units of k are mol L-I time -I.
as unimolecular, bimolecular or trimolecular, etc., depending (ii) First order reactions: The rate depends upon the
upon the number of reacting particles as 1,2,3, etc:, in the rate concentration of one reactant only.
determining step. Simultaneous collisiolls involving more than
"three molecules are very rare and hence reactions with dx = k[A]
molecularity more than three are also rare. dt .
proportional to concentration can be used in place of concentrations. . The experiments. are repeated with other
concentration in the integrated equation. reactants in a similar way. Likewise, the orders w.r.t. all reactants
The time taken for the completion of same fraction of change are determined. The overall order is the sum of the orders of all
is independent of initial' concentration. When x =. 0.5 a and the reactants.
t t 1l2 , (ii) Integration methOd: The quantities 'a,x and t are
k :;:: 2.303 log to ~ == 2.303 log to 2 = 0.693 detwmined and. substituted in the kinetic equations of various
t 112 O.5a t 112 t 112 orders. The equation which gives the most consistent values for
the specific rate constant (k) for a series of time intervals is the
0 ..693 one corresponding to order of reaction.
k 2.303 a
k == - - log 10 - - for first order reactions
Thus, t 112 is independent of initial concentration. t (a - x)
The equation. of the first order can also be written in the
following form when initial concentration is not known. k 1 [
t a(a-x)
a] for second order reactions
2.303' I (a xI) 2.303 I' [A]II
k == oglo = ogiO - -
, (t2 - t I ) (a- x 2') (t2 - t,). [A]t2 Rate =k for zero order reactions
The unit of k is time -I . (iii) Graphical method: If the plot oflog (a x) versus 't'
(iii) Second order reactions: Reaction rate depends upon is a straight line, the reaction follows first order.
the concentration of two reactants. If a plot of _1_ versus 't' is a straight line, the reaction·
.(a-x)
dx = k[A][B] = k[A]2 follows second order.
dt
2.303 1 b(a x) If a plot of 1 versus' t' is a straight line, the reaction
k= og to --'-----'- (a x)2
tea-b) a(b-x)
follows third order.
[(a - x) and (b - x) are the concentrations of A and B after time
interval t.] . (iv) Half life method: Starting with two different
concentrations al and a2 for the same reaction, the half lives
When concentrations of both the reactants are same,
(tIl2)1 and (til 2 )2 are determined.
k~. x
t a(a - x)
, (x is the concentration changed in time interval t)
Half life period, t 112 2. , i. e. ,inversely proportional'to initial n is the order of reaction:
lea
concentration. The units of k are litre mol- l time-I. (v) van't Hoff differential method: For two different
(iv) Third order reactions: Expression for third order initial concentrations C I and C 2 equations can be written in the
reactions of the type form
3A ~ Products _dCI == kCf and- dC 2 == kCi
. dt dt
dx = k[A]3
dt Taking logarithms of two equations and then subtracting .
x(2a - x)
k z
t 2a Z (a-x)2 log ( -. dt
dC I ) - log (dC
- dt )
The units of kareL2 mol-2 time-I. n:;:: --'-------~---
9. Methods for the determination of order of a reaction:
(i) Initial rate method: A number of experiments are 10. Mechanism: An intelligent guess depending upon the
carried out by varying concentration of a reactant w.r.t. which the observed rates of reactions about the series of steps (known as
order is to be determined. keeping the concentrations of all other elementary processes) leading to the formation of products is
reactants constant. The initial rate of the reaction at each . called the reaction mechanism. The overall reaction is the
concentration is determined by concentration-time curves. The summation of all elementary steps: The slowest step is taken as
order of the reactant is then c,alculated from the rates lit various the rate determining step.
CHEMICAL KINETICS 557
1. Matrix Matching Problems: [E] Match the reactions of List-I with the increase in rate when
. (According to the new pattern of lIT Screening) concentr~tion is raised two times in List-II:
[AJ Match the reactions of LisH with their orders in List-II: List~I List-II
List-I List-II (Reactions) (Increase in rate when
H+ cone. of reactant is
(a) C12 H22 0 11 + H20 ~ (P) Pseudo first order doubled)
C6 H12 0 6 + C6H l2 0 6
. HOH
(a) CH3CHO ---7 CH4 + CO (P) 2 times
(b) CH3COOC2H s 1 (q) Zero order
H+ orOH- 1- (b) SOzClz ---7 S02 + Cl 2 (q) 21.5 times
(c) 2H20 2 2H20 + 02 (r) 2 times in acid medium
CH3COOH + c;HsOH
hv HOH
(c) H2 + Cl 2 ---7 2HCI (r) Second order (d) CH3C00c;Hs ~ (s) 22 times in basic
(d) CH3CI + OH- ---7 (s) First order CH3COOH + C2HsOH medium
CH30H+Cr
[F] Match the List-I with Liwst-II and List-III:
[B) Match the reactions in Colump.-I with the units of their rate
constant in Column-II: List-I List-II List-UI
Column-I Column-II (a) x is plotted aga- (P) Slope= k!2.303 (u) Intercept = (,
(Reactions) (Unit of k) inst 't' in zero
order reaction
(a) SOzCl z ---7,S02 + Cl 2 (P) sec-~,
(b) log (a - x lis (q) Slope 2k (v) Intercept
(b) CH3COOCzHs + NaoH~ (q) min':" l plotted against 11 a
't' in first order
CH3COONa + CZH 50H reaction
(e) 2H20z ---7 2H20+ 02 (r) Lmol- I min- 1 , (c) (a-xr l is (r) Slope = - k (w)Intercept
(d) HzOz + 21 + 2W (s) Lmol- 1 s-I plotted against (when log is 11 a 2
, t' in second natural)
2H2 0+ 12
order reaction
(d) (a xi is (s) Slope k (x) Intercept
[C] Match the kinetic equations of Column-I with the units of
plotted against = loglo a
their rate ,constant in Column-II:
't' in second
Column-I Column-II
, order reaction
(Kinetic equations) (Units of rate constant)
where, a = Initial concentration of reactant
(a) x kt (P) sec':"!
x Extent of reaction in time 't' sec
(b) k = 2.303 logw r_a_) [G] Match the List-I with List-II:
[I] Match the Column-l with Column-II: . Here, tl12 half life
Column-I Column-II t314= 3/4th life
0.693 k = rate constant
(a) tll2 =-- (P) Zero order [K] Match the Column-1 with Column-II:
k
a (q) First order Column-I Column-U
(b) t1l2 = 2k
(a) First order reaction (p)Co O.lM; tl/2 25min
1 (r) Average life
(c) 'C Co = 0.05 M; = 12.5 min
tl/2
k
(d) (8) 75% completion (b) Second order reaction (q)Co = O.IM; til2 = 12 min
t3/4 = 2t1l2
Co = 0.05 M ; tl/2 = 24 min
(t) 25% completion
(c) Zero order reaction (r) Radioactive decay
[J] Match the Column-l with Column-II:
Column-I Column-II (d) tl12 varies inversely to (s) Co 0.1 M; t1l2 8 min
the concentration of the Co = 0.05 M; t1l2 8 min
3 reactants·
(a) t3/4 2 X'I·"
,- (p) 99% completion
1. [A] (a-p), (b-r, s), (c-q), (d-r) . [G] (a-s), (b-p, q, s), (c-r), (d--p)
[B] (a-p, q), (b-r, s), (c-p, q), (d-r, s) [H] (a-q), (b-p), (c-p), (d-r, s)
[C] (a-r), (b-p), (c-q, s), (d-q, s) [1] (a-q), (b-p), (c-q, r), (d-q, s)
[D] (a-p, q), (b-s), (c-r, s), (d-r, s) [J] (a-q), (b-r), (c-p, r), (d-r, s)
[E] (a-q),(b-p), (c-p), (d-~ s) [K] s), (b-q), (c-p), (d-q)
[F] (a-s-u), (b-p, r-x), (c-s-v), (d-q-w)
• CTICE PROBLEMS •
1. For the reaction A --t B, it was found that the concentration of d[NOCI]
(iii) 2NO +. Cl z --t 2NOCI; ?
B increased by 0.3 mol L- 1 in 2 hours. What is t:p.e average rate
of reaction? (iv) CO + N02 --t CO2 + NO;
[Ans. 0.15 mol L- 1 hr- I ]
2. It;l the reaction X --t Y, the initial concentration of X is 2.5 [Ans. (i) d[H z ) = - 3 . = + ~ -7'----"-':
1
dt dt 2 dt
moL and its concentration after 3 hours is 0.7 mol L- .
(ii) d[02l =_ 1 =..!. d[H20);
What is the average rate of the reaction? dt 2 . dt 2 dt
[*ns. 6.0 x 10-1 mol L-1hr- 1) (iii)d[NOCI) d[NO] = 2.
3. For the reaction 2A + B --t C, the rate offormation ofC is 0.25 dt dt dt
mol L- 1 hr-:-I. What is the rate of disappearance of A and B? _ d[COl d[e0 2 ] = d[NO] ]
(iv) -
[Ans. 0.5 mol L- 1 hr- I ; 0.25 mol L- I hr- 1] dt dt dt dt
4. For each of the following reactions express the given rate of 5. When annnonia is treated with O 2 at elevated temperatures,
2
change of the concentration of the reactant or product in terms the rate of disappearance of annnonia is found to be 3.5 x 10-
of the rate of change of concentration of the other reactants or 3
mol dm- S-1 during a measured time interval. Calculate the
products in that reaction. rate of appearance of nitric oxide and water.
_ d[H2]
(i) N2 + 3H2 --t 2NH3 ; ? [Ans. = 3.5x 10-2 rool dm-3 S-I;
dt dt
_ d[Oz]
(ii) Hz + ~ O 2 --t H2 O; ? Ll[H 20) = 5.3 x 10-2 mol dm-3
dt dt .
CHEMICAL KINETICS 559
[Hint: Consider the following equation: 15, The reaction,
4NH3 + 502 -7 4NO + 6H 20
2N20 S -7 2N 20 4 + O2
The equality in this case is
1 ~[NH3] = 1 ~[NO] =.!. ~[H20] ] occurs in carbon tetrachloride. The rate constant is
4 dt 4dt 6dt 2.35 x 10-4 sec-I at 20 0 C and 9.15 x 10-4 sec": J at 30°C.
6. In a reaction, N 20 S -7 2N0 2 + Yz 2 , ° Calculate the activation energy of the reaction.
the rate of disappearance of N 20 S is 6.5 X 10-3 mol L- 1 S-I. [Ans. 100,343 kJ mol-I]
Compute the rates offormation ofN0 2 and 02' 16. For the inversion of cane sugar,
[Ans. d[N°2] = 1.25 x 10-2 mol S-I. C12 H22 0 11 + H2 0 -7 C6 HI2 0 6 + C6 H12 0 6 ,
dt '
the rate constant is 2.12 x 10"""" L mol-I sec-I at 27° C. The
d[°2] 3.125 x 10-3 mol L- 1
dt activation energy of the reaction is 1.07 x lOs J mol-I. What is
7. For the reaction, the rate constant of the reaction at 37° C?
203 .....:.-.: 302 [Ans. 8.46 L mol- J sec-I]
- ~[03] was found to be 4.0 x 10"""" atrus-I. 17. From the data given below for the reaction 2A + B -7 3C at
dt 298 K, fInd out the rate law expression for the reaction.
Determine the value of ~[02 ] in atm s -I during this period of ~
28. In the hydrolysis of propyl acetate in presence of dilute HCI in would have changed into the product? What is the half life
aqueous solution, the following data were recorded: period of this reaction?
Time from start (in minute) 60 350 [AilS. tIl2::: 128.3 hours; 5.27%]'
% of ester decomposed 18.17 69.12 39. A first order reaction is 20% completed in 10 minutes.
Calculate the rate constant of decomposition and time in Calculate (i) the specific rate constant of the reaction and (ii)
which half of the ester was decomposed. the time taken for the reaction to go to 75% completion.
[Ans. 3.34 x 10-3 min -1; 207.6 min] [Ans. k 2.232 x 10-2 min -\ t =62.12 min]
. 29. In a first order reaction the concentration of the reactant is 40. The rate constant of a reaction with respect to reactant A is 6
reduced to one-fourth of its initial value in 50 seconds. min-I. If we stali with [A] 0.8moIL- I , when would [A]
Calculate the rate constant of the reaction.
reach the value of 0.08 mol L- I? '
[Ans. 2.77 x 10-2 S-I]
[Ans. 0.3838 min]
30. For a first order reaction, the rate constant is 0.1 S-I. How
41. What will be the initial rate of a reaction if the rate constant is
much time will it take to reduce the concentration from initial
10- 3 min -\ and the concentration is 0.2 11101 dm- 3 ? How much
value of 0.6 mol L-I to 0.06 mol C l ?
of the reactant will be converted into the product in 200
[Ans. 23.0 second] minutes?
31. A substance decomposes following first order reaction. If the [Ans. Initial rate 2 x 10-4 mol S-I; 0.036 mol]
half life period of the reaction is 35 minutes, what is the rate
constant of this reaction? . 42. A substance A decomposes by the first order reaction. Startinr
initially with [A] = 2.00 M, after 200 minutes [A] 0.25/,
[Ans. 1.98 x 10-2 min -lj
For this reaction what is tll2 and k?
. 32. For a certain first order reaction, it takes 5 minutes for the [Ans. tl12 66.66min,k 0.01039 min-I]
initial concentration of 0.6 mol L- I to become 0.2 mol L-1 .
43. The specific rate constant for the concentration of H2 and I z to
What is the rate constant for this reaction? [log 3 0.4771].
fonn HI is 0.0234 mol-I LSI at 400" Cand 750 mol-I L at
[Ans. 0.2197 min-I]
0
500 C. Calculate the activation energy of the reaction.
33. Find the two-thirds life (t213 )of a first order reaction in which
!eL
k = 5.48 X 10- 1 sec-I (log 3 = 0.4771; log 2 0.3010).
[Ans. 107.9 kcal]
[Ans. 2.005 s] 44. For a certain reaction it takes 10 minutes for the initial
[Hint: tiJ3:::
2.303
loglo
a] concentration of 2.0 mol to become 1.0 mol L-1 and
k a Jia another 10 minutes to become 0.5 mol L- I . Calculate the rate
34. A first order reaction has a specific rate of 10-3 sec-!. How constant of the reaction.
much time will it take from 109 of the reactant to reduce to [Ans. 0.0693 min -I]
7.5 g (log 2 = 0.3010; log 4 =0.6020 and log 6 0.7782)?
45. The catalytic decomposition of HzOz was studied by titrating
[Ans. 287.7 s]
35. In a reaction 5 g ethyl acetate is hydrolysed per litre in it at different intervals with KMn04 and the following data
presence of dilute HCI in 300 min. If the reaction is of first were obtained:
order and initial concentration is 22 g per litre, calculate the t (seconds) 0 600 1200
rate constant for the reaction. V ofKMn04 (rnL) 22.8 13.8 8.3
[Ans. k::: 8.59 X 10-4 min- 1 ] Calculate the velocity constant for the reaction assuming it to
..be a first order reaction.
36. talculate the half life of the reaction A -7 B, when the initial
[Ans. 8.4 x 10-3 S-1]
concentration of A is 0.01 mol C 1 and initial rate is 0.00352
[Hint: Volume of KMnO 4 used oc concentration of H 20 2
mol L-1 min -1. The reaction is of the first order.
2.303 Vo
[Ans. 1.969rnin] Hence, k = - - loglo-]
t VI
. d:x'
[Hint: Evaluate k from ~ = k[ A] ] 46. The half life of a first order reaction is 10 seconds. Calculate
dt
the time for completion of 99.9% of the reaction.
37. In a reaction, A -7 B + C, the following data were obtained:
[Ans. 99.7 sec"" 100 sec]
t in seconds 0 900 1800 47. A first order reaction is 40% complete after 8 min. How long
Concentration of A 50.8 19.7 7.62 will it'take before it is 90% complete? What is the value of the
Prove that it is a first order reaction. rate constant?
[Hint: Calculate the value of k in both cases by using first order [Ans. k 0.06386 min -I; t 36.06 min]
equation.]
48. The reaction S02Clz -7 S02 + C1 2 , is a first order gas
,38. The first order reaction has k = 1.5 x 10-6 per second at
reaction with k 2.2 x 10-5 s-I at 573 K. What per cent of
200 0 C. If the reaction is allowed to run for 10 hours at the
SOzCl z is decomposed on heating at 573 K for 90 min?
same temperature, what percentage of the initial concentration
[Ans. 11.2]
562 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
49. The decomposition of AB(g) ~ A (g) + B(g), is first order when tIS, k==0.0198
4 when t 20, k = 0.0196]
reaction with a rate constant k 4 x 10- at 318 K. If AB
has 26664.5 Pa pressure at the initial stage, what will be the 60. Optical rotation of sucrose in' 1 N HCI at various times was
partial pressure of AB after half an hour? found as shown below:
[Ans. 12981.7 Pa] Time (sec) 0 7.18 18.0 27.05 00
50. In the first order reaction A (g ) ~ B (g) + C(g), the initial Rotation (deg) + 24.09 + 21.7 + 17.7 +15.0 -10.74
Show that the inversion of sucrose is a first order reaction.
pressure of A is 11200 Pa and the total pressure at the end of
16 minutes is 14667 Pa. Calculate the half life period of [Hint: Initial concentration, [A 1 == '0 - r;"
reaction. At time t, [AL='i-I~
[Ans. 30 min] k == 11.8 X 10-3 S-I]
51. It was found that a solution of cane sugar was hydrolysed to
61. The rate law for the decomposition of gaseous N2 0 S
the extent of 25% in 1 hr. Calculate the time taken for the
sugar to be 50% hydrolysed assuming that the reaction is of N 20 S ~ 2N0 2 + 0 2 h
first order. is observed to be:
52.
[Ans. 2.408 hours]
A reaction is 20% complete in 20 minutes. How long will it
- dlN 2
dt
°sJ = k[N
2
°]
S
take for 80% completion if the order of reaction is (a) zero and A reaction mechanism which has been suggested to .be
(b) one? consistent with this is:
[Ans. (a) 80 minutes '(b) 144.27 minutes] K
N2 0 S ~ NOz + NO} (fast)
53. A second order reaction where a b is 20% completed in 500
kl
seconds. How long will the reaction take to be 60% complete?
NO z + NO} ~ N02 + NO + 02 (slow)
[Hint: Apply
k2
k == x 20 _1_ mol-I L S-l NO + NO) ~ 2N02 (fast)
ta(ti''-x) 500[100x(lOO 20)] 200000
Show that the mechanism is consistent with the observed law.
60
t = = - - - - 60 x 200000 3000 seconds] [Hint: r k l [NO z ][N0 3 ],
k x 100 x 40 100 x 40
K [NO z][NO)] or [NO, ] == --"--=-"-"
54. At a certain temperature, the half life periods of a reaction at
(Nps] 0 [N0 2 ]
different initial pressures were as follows:
p (kPa) 100 66.67 33.33 r kIK[NzOs]=k[NzOs]]
t (min) 105 235 950 62. Write the overall reaction and the rate law equation from the
Find out the order of the reaction. following elementary steps:
[Ans. 3] NO + Brz ~ NOBrz
55. The time for half change for a gaseous reaction was measured
NOBr2 + NO ~ 2NOBr
for various initial pressures and the following data were
obtained: [Hint: Adding both the steps, we get overall real'; ,'1,
p (kPa) 26.6 40 53.3 2NO + Brz ~ 2NOBr.
t (min) 150 99.8 75.3 The second step is slow and, therefore, a rate determining step.
Find out th.: order of the reaction. r k'[NOBrz ][NO]
[Ans. 2]
K or [NOBr2] = K[NO][Br2]
56. Show that for a first order reaction the time required for 99% [NO][Brz]
completion is twice the time required for the completion of
90% of the reaction. r k' K[NOY[Brz] ]
57. Show that for a first order reaction the time required to 63. The reaction, 2NO + 0z ~ 2N02 proceeds in two steps. If
complete 99.9% of the reaction is 10 times that required for one elemental), reaction is NO + O 2 ~ N0 3, write the second
half the reaction. elementary reaction. Write the rate law of the reaction.
58. Show that for a first order reaction, the time required for a . [Ans. NO + N0 3 ~ 2NO z, rate = k[NO] 2 [° 2 ] ]
50% reaction is half that for 75% reaction.' . 64. At 3800 C, the halflife period for the first order decomposition
59. 1
The decomposition of an aqueous solution of ammonium ofH2 0 z is 360 min. The energy of activation ofthe reaction is
nitrite was stl.1cied. The .volume of nitrogen gas collected at
200 kJ mol-I. Calculate the time required for 75%
different inteI;Vals of time was as follows:
Time (minutts) 10 IS 20 00
decomposition at 450 0 C. (HI' ] 995)
Vol. ofN2 (mL) 6.25 9.00 11.40 35.05 [Ans. 20.39 min]
From the above data prove that the reaction is of the first order. 65. Calculate the average rate of decomposition of NzOs by the
[Hint: [A]o == volume of nitrogen at 00 == 35.05 reaction,
2N 2 0 S (g ) ~ 4NOz (g ) + O 2 (g ).
[A],=V~ V,!
. During the time interval-from t = 600 s to t = 1200 s using the
when t == 10, k = 2.303 log 35.05 0.0196 following data:
10 (35.05 6.25)
CHEMICAL KINE1'ICS; II 563
_£OBJE~IIVE·QUESTIONS
Set-1: Questions with single correct answer (c)
2d[N0 2 ] =
dt dt dt
1. Chemical kinetics, a branch of physical chemistry, deals with: d[NO]
(d) - ---C'--"-" = -.- =
(a) heat changes in a reaction dt dt dt
(b) physical changes in a reaction 6. The rate of reaction that does not involve gases, is not
(c) tates of reactions dependent on:
(d) structure of molecules (a) pressure (b) temperature
2. The rate at which a substance reaGts depends upon its: (c) concentration (d) catalyst
(a) atomic mass (b) equivalent mass 7. For the reaction, A + B 2C + D, which one is, the
(c) molecular mass (d) active mass incorrect statement?
3. The rate of a chemical reaction: (a) Rate of disappearance of A Rate of disappearance.af B
(a) increases as the reaction proceeds (b) Rate of disappearance of A Rate of appearance of D
(b) decreases as the reaction proceeds (c) Rate of disappearance of B 2 x rate of ap}".'arance of C
(c) may increase or decrease during the reaction , I
(d) remains constant as the reaction proceeds (d) Rate of disappearance ofB = - x rate of appearance of C
. '2
4. For the reaction, N2 + 3H2 2NH3 , rate is expressed as: 8. In a reaction, 2Al + B2 2A 2 B, the reactant A will
d[H2] 3 d[NH3] disappear at:
(a)-3 dt dt 2 dt
(a) half the rate that B will decrease
(b) _ d[N2] I d[H 2 ] 1 d[NH3J (b) the same rate that B will decrease
dt 3 --;Jt = '2-;Ii
(c) double the rate that A2B will fonn
d[N2] ___ 3d[H 2 ] 2d[NH 3 ]
(c) (d) twice the rate that B will decrease
dt dt dt
(d) _ d[N2] d[H2] 9. In the reaction 3A ~ 2B, rate of reaction + is equal to:
dt .
dt dt dt
[JEE (WO) 10081
5. For the re!lction, 2N0 2 ----1 2NO + O2 , rate is expressed as:
(a) .!. d[A] (b) 2 d[A] (c) + 2 (d) _ ~ d[A];
(a) _ 1 d[N0 2 ] = 1 d[NO] = d[02] 3 dt 3 dt dt 2 dt"
, 2 dt 2 dt dt 10. For the reaction, 2NO ----1 N2 + O 2 , the expression
(b)_l _.!. =d[02]
_ .!. d[NO] represents:
2 dt 2 dt dt 2 dt
566 II
(a) the rate offormation of NO !t. In general, with every 10°C rise in temperature, the rate of
(b) the average rate (Jf the reaction reaction becomes approximately ........... .
(c) the instantaneous rate of the reaction (a) ten times (b) double
(d) all of the above (c) half (d) one tenth
itt. The term dx in the rate expression refers to the: 11. Activation energy of the reaction is:
dt (a) the energy released during the reaction
(a) instant.aneous rate of reaction (b) the energy evolved when activated complex is form(~d
(b) average rate of reaction (c) minimum amount of energy needed to overcome the
(c) in<::rease in the concentration of reactants potential barrier
(d) '.;oncentration of reactants (d) the energy needed to form one mole of the product
tf.2. According to collision theory of reaction rates: n. The temperature coefficient of most of the reactions lies
'. (a) every collision between reactant molecules leads to a between:
chemical reaction (a) 2 and 3 (b) I and 2
(b) rate of reaction is proportional to the velocity of the molecules (c) 2 and 4 (d) 3 and 4
(c) rate of reaction is proportional to the average energy of the According to Arrhenius equation, rate constant of a chemical
molecules reaction is equal to:
(d) rate of reaction is proportional to the number of collisions IRT (b) Ae E" IRT
(a)
per second (c) Ae
RT1E
" (d) Ae- NT / Ea
iJ'S. According to collision theory: .14. The correct expression for Arrhenhr - ,;t,r,' .ne
(a) all collisions are sufficiently violent effect of temperature on the rate constant is (T2 > 1\ ):
(b) all collisions are responsible for product fonnation !1'CE :::f'~H'
(c) all collisions are effective
(d) only a fraction of collisions are effective which have
enough energy to form products
a 10 k2 - [ 1\T2
() glo k) -2.303R T2 -1)
l~
n.. Which of the following has been used to explain the subject of
(b)
R
chemical kinetics?
(a) Collision theory of bimolecular reactions
(b) The activated complex theory (c) loglo k T.T
(c) Arrhenius equation ) 1 2
47. The unit of rate constant for a zero order reaction is: 59. The following data are for the decomposition of ammonium
(a) mol time-I (b) Ltime- I nitrite in aqueous solution:
1
(c) mol L- time- 1
(d) L mol-I time- 1 Vol. ofN2 incm3 6.25 9.0 11.42 13.65 35.02
48. Fora zero order reaction: IEAMeE! ;(90) Time (min) 10 15 20 25 00
1 1
(a) t1/2 0<: a (b) t1/2 oc;; (e) tll2 cc a 2
(d) tl/2 a2cc The order of reaction is:
Ca) 3 (b) 2 (c) (d) zero
.49. The rate of the first order reaction, A Products, is
[Hint: a 35.02, (a - x) = 35.02 VI
4
7.5 x 10- mol , when the concenlla,~,)fl of A is 0.2 mol = 2.303 10 35.02
Apply, k
L- 1 , The rate constant of the reaction is: t g (35.02 Vt)
(a) 2.5 x 10- 5 S-1 (b) 8.0 x 10~ S-1
60. In the first order reaction, the concentration of reactant
(c) 6.0x 10-4 S-I (d) 3.75 x 107'3 decreases from 1.0 M to 0.25 M in 20 minutes. The value of
specific rate is:
50. If the concentration is expressed in mole per litre and time in
second, the units of rate constant for a first order reaction is: (a) 69.32' . (b) 6.932 (c) 0.6932 (d) 0.06932
(a) mol L-1 (b) 6L The half life period of a first order reaction is 10 minutes. The
time required for the concentration of the reactant to change .'
(c) mol (d) mol-I from 0.08 M to 0.02 M is: (1fT i99i))
51. 'Which one of the following formula represents a first order
(a) 10 min (b) 20 min (c) 30 min (d) 40 min
reaction?
62. The rate constant for the hydrolysis reaction of an ester by
- - Iog
(a) ' k --2.303 (b) k = 1. x dilute acid is 0.6931 x 10-3 S-I. The time required to change
t [A]o t a(a x)
the concentration of ester from 0.04 M to 0.01 Mis:
(c) k = 2.303 log _a_ (d) k
2.303 I
- - og-
Ii
(a) 6931 sec (b) 4000 sec
t a- x t . x
(c) 2000 sec (d) 1000 sec
52. 75% of a first order reaction was completed in 32 minute;
63. The rate of a gaseous reaction is given by the expression
when was 50% of the reaction completed?
k[A][B]. Ifthe volume of reaction vessel is suddenly reduced
(a) 4 min (b) 8 min (c) 24 min Cd) 16 min to one-fourth of the initial volume, the reaction rate relative to
53. The first order rate constant for the decomposition ofN2 0 s is the original rate will be: (lIT 1992)
6.2 X 10-4 The half life period for this decomposition is:
• (a) 1/16 (b) 1/8 (c) 8 (d) 16
(;\iL'iR 19q i) 64. The velocity of a reaction is doubled for every 10°C rise in
(a) 1117.7 s (b) 1117 s (c) 223.4 s (d) 160.9 s temperature. If the temperature is raised to 50°C, the reaction
54. The half life period of a first order reaction is: velocity increases by about:
Ca) 0.693 (b) 0.693 (c) 0.69~ (d) 0.693 (a) 12 times (b) 16 times (c) 32 times (d) 50 times
a k t ak
65. If the rate expression for a reaction is dx = k[A]1I2[B]3i2, the
55. The specific rate constant of a first order reaction depends on: dt
Ca) concentration ofthe reactants overall order of the reaction is: [CEE (Bihar) 19921
. (b) concentration of the products (a) 2 (b) 112 (c) 3/2 (d) 1
(c) time 66. The rates of a certain reaction at different times are as follows:
(d) temperature Time (second) 0 10 20 30
56. For a given reaction of first order, it takes 20 minutes for the Rate 2.8 x ro- 2 2.78 x 10-2 2.81 x 10-22.79 x 10-2
concentration to· drop from 1.0 M to 0.6 M. The time required (mol L- 1
for the concentration to droP. from 0.6 M to 0.36 M will be:
(a) more than 20 minutes (b) less than 20 minutes The reaction is of:
(c) equal to 20 minutes (d) infinity (a) third order (b) second order
57. For the first order reaction A ------* Product, the half life is 200 (c) first order (d) zero order
. seconds. The rate constant of the reaction is: 67. The second order rate constant is usually expressed as:
(a) 3.46 x 10-2 S-I (b) 3.46 x 10-3 s-! (a) mol (b) mor l L- I S-I
(c) 3.46 x 10~ S-I (d) 3.46 X 10- 5 S-l (c) mol- 1 Ls- 1 (d) mol Ls- I
58. The following data were obtained for the thermal 68. The hydrolysis of ethyl acetate is a reaction of:
H+
decomposition of nitrous oxide on finely divided gold:
CH3 COOC2Hs + H 20 ------* CH3 COOH + C 2H sOH
t (minutes) 0 20 40 60 80
(a) zero order (b) first order
Concentrati{)n of N 20 (mol LI) 0.10 0.08 0.06 0.04 0.02
(c) second order (d) third order
The order of reaction is:
(a) zero (b) I (c) 2 (d) 3
CHEMICAL KINETICS 569
69. The inversion of cane sugar is represented by, [Hint: r k'[03][0] k'kllf~:i[03] k[Od[Ozr 1 ]
87. The reaction, (a) rate k[NOf[Cl z ] (b) rate = k[NO] [CI 2 ] 2
2N 20 5(g) 4NO z(g) + °2(g), (c) rate = k[NOCl z] . (d) rate = k[NOCI] 2
is first order with respect to N 2 0 5 . Which of the following
graph, would yield a straight line? [Hint:
(a) log (PN 20 S ) versus time ~ith -ve slope rate = k' [NO)[NOCl z ] k' K[NO][NO][Clzl k[NO:rrCI 2 ]l
(b) (PN 20 S rl versus time 94. The rate of a reaction can be increased in general by all the
following factors except:
(c) (PN 20 S ) versus time (a) by increasing the temperature
(d) log (PNzOs ) versus time with +ve slope (b) using a suitable catalyst
88. Consider the following statements: (c) by increasing the concentration of reactants
(i) increase in concentration of reactant increases the rate of a (d) by an increase in activation energy
zero order reaction
95. How will the rate r k[80 2 ][Oz] of reaction,
(ii) rate constant k is equal to collisionfrequency , A' if Eo 0
(iii) rate constant k is equal to collision frequency A if Ea 00 2S0 2 + 02 -----72S0 3 ,
(iv) log e k vs T is a straight line . change if the volume of the reaction vessel is tripled?
(v) loge k vs II T is a straight line (a) It will be '!rd of its initial value
. 3
Correct statement are: [PMT (Kcrala) 2010]
(a) (1) and (iv) (b) (ii) and (v) . (b) It will be 3 times of its initial value
(c) (iii) and (iv) (d) (ii) and (iii) (c) Jt will be 9 times of its initial value
(e) (i) and (v) (d) It will be .!th of its initial value
1 . . 9
89. Ifwe plot a graph between log k and T by Arrhenius equation, .. 96. Radioactive disintegration is an example of:
the slope is: IEAMCET (Engg.) 20101 (a) zero order reaction (b) first order reaction
(c) second order reaction (d) third order reaction
(a) -EaIR (c) (d) Ea·
2.303R + 2.303R 97. In .the formation of sulphur trioxide by the contact process,
90. The rate of the reaction, . 280 2 + O 2 2803' the rate of reaction was measured as
CC1 3CHO + NO CHC1 3 + NO + CO, d[02] 3.0x 10-4 mol L- I S·-I.
dt
is given by the equation, rate = k[CCI 3 CHO][NO]. If
The rate of reaction expressed in terms of 803 will be:
concentration is expressed in moll litre, the units of k are:
. [PMT (MP) 19931 (a) 3.0 x 10-4 mol (b) 6.0 x 10-4 mol S-I
(a) mol-2 L2 S-I (b) mol S-I (c) 1.5 X 10-4 mol L- I S-I (d) 4.5 x 10-4 mol L- I S-I
(c) L mo.-I S-I (d) S-I 98. The rate constant for a first order reaction is 6.909 min -I.
91. In a reaction, 24 + B ---; A2B, the reactant A will disappear Therefore, the time required in minutes for the participation of
75% of the initial reactant is: (PET (J&K) 2009)
at: !PMT (MP) 19931
2 2 3 3
(a) half the rate that B will decrease W-~2 ~-~4 W-~2 ~ ~4
(b) twice the rate that B will decrease 3 . 3 2 2
(c) the same rate that B will decrease 99. For the reaction, .
(d) the same rate that A2B will form A + 2B -----7C + D, d[A] k[A][BJ2
92. The rate of the reaction, 2NO + 02 ---; 2N0 2 , at 25°C is dt
0.028 mol L- I s -l. The experimental rate is given by . the expression for d[B] will be:
dt
r= k[NO]2[OZ]
If the initial concentrations of the reactants are O2 = 0.040 . (a) 2k[A ][Bf (b) .! k[A ][B]2
2
mol and NO = 0.0 I mol , the rate constant of the
(c) k[A][Bf (d) k[A][BI2f
reaction is:
100. Which of the following statements is not correct for the
(a) 7.0 x 10-2 L morl
reaction,
(c) 7.0 X 102 LZ mor2 S-I (d) 7.0 x 103 L2 mol-z s-l 4A + B 2C + 2D?
[Hint: 0.028 k[0.01Y[0.040]] (a) The rate of appearance of C is one-half the rate of
93. For the reaction, disappearance of B
2NO + Cl 2 2NOCI , (b) The rate of disappearance of B is one-fourth ofthe rate of
disappearance of A
the following mechanism has been proposed.
(c) The rate of formation of D is one-half of the rate of
NO + Cl z NOCl 2 (fast)
consumption of A
NOCl z + NO ---; 2NOCI (slow)
(d) The rates offormation ofC and D are equal
The rate law for the reaction is:
CHEMICAL KINETICS '1 571
101. The overall rate of a reaction is governed by: (b) d[Br2J _~ d[Br J
(a)
(a) the rate of the fastest intermediate step dt 5 dt dt 5 dt
(b) the sum total of the rates of all the intermediate steps
5 d[Br-]
(c) the average of the rates of all the intermediate steps (c) (d) :::::+----
(d) the rate of the slowest intermediate step
dt 3 dt dt 3 dt
102. The rate constant of a reaction does not depend upon: Ill. Given that k is the rate constant for some order of any reaction
(a) temperature at temp. T, then the value of lim log k, (where, A is the
Arrhenius constant) is: T -> =
(b) activation energy
(c) catalyst (a) A /2.303 (b) A (c) 2.303A (d) togA
(d) concentration of reactants and products 112. The curve depicts the change in
concentration of species X and
103. The half-life period of a first order chemical reaction is 6.93 . Y as a function of time. The ,g X
minutes. The time required for the completion of 99% of the
point of intersection of the two
chemical reaction will be: (log 2::::: 0.301) (AIEEE 2(09) ~
curves represents: 'E
(a) 230.3 minutes (b) 23.03 minutes
(c) 46.06 minutes (d) 460.6 minutes
(a) 1112 ~
104. For the chemical reaction x ~ y, it is found that the rate of
(b) t3/4 . 8 "--'--------
(c) t 2l3 lime-
reaction increases 2.25 times when the concentration of x is (d) data insufficient to predict
increased 1.5 times. What is the order ofreaction? 113. In gaseous reactions, important for the understanding of the-
(a) One (b) Two (c) Three (d) Zero upper atmosphere H2 0 and 0 react bimolecularly to form two
[Hint: r = k[x t and 2.25r = k[1.5x r OH radicals. Mf for this reaction is 72 kJ at 500 K and Ea is
So, 2.25 = (1.5t or a = 2] 77 kJ mol-I; then for the bimolecular recombination of two
105. The halflife period of a reaction is constant for: OH radicals to form H2 0 and 0 is:
(a) zero order (b) first order (a) 3 kJ mor l (b) 4 kJ mol-I
(c) second order (d) none ofthese (c)'5kJrnol- 1
(d) 7kJmol- 1
106. From different sets of data of tl12 at different initial
114. From the following data, the activation energy for the reaction
,?oncentrations say 'a' for a given reaction, the [11/2 X a] is (cal/mol) is:
found to be constant. The order of reaction is:
(a) zero (b) I (c) 2 (d) 3
107. Diazonium salt decomposes as
C6Hs~C1- ~ C6HsCI + N 2·
At O°C, the evolution ofN2 becomes two times faster when the
initial concentration of the salt is doubled. Therefore, it is:
(\IL\R i9 4 -i} (a)4xl04 (b) 2x 104
(a) a first order' reaction
(c) 8x 104 (d) 3 \10
4
(b) a second order reaction
(c) independent of the initial concentration of the salt 115. The hydrolysis of an ester was carried out separately with-
(d) a zero order reaction 0.05 NHCl and 0.05 NH2 S0 4 . Which of the following will be
108. For the reaction, N2(g)+3H2(g)~2NH3(g), under true?
certain conditions of temperature and pressure of the reactants, (a) k HC1 >kH2S04 (b) kH2S04 >kHCI
'. (c) KH 2S0 4 = 2kHC1 (d) kH2S04 = k HCI
the rate offormation of ammonia is 0.001 kg hr- I . The rate of
consumption of hydrogen under the same conditions is ...... kg 116. For an endothermic reaction, where, Mf represents the
hr- I . enth'ilJpy of the reaction in kJ/mol, the minimum value for the
energy of activation will be:
(a) 0.001 (b) 0.003 (c) 0.002 (d) 0.0015
(a) less than Mf (b) zero
109. The rate constant, the activation energy and the Arrhenius (c) more than Mf (d) equal to Mf
parameter of a chemical reaction at 25°C are 3.0 x 10-4
117. In the following first order competing reactions;
104.4 kJ mor l and 6.0 x 1014 S-I respectively. The value of . A + Reagent Product
rate constant at T ~ 00 is: (iIT 1996) B + Reagent Product
(a) 2.0xlOI8 s- J (b) 6.0 x 1014 S-I . The ratio of kl / k2 if onfy 50% of B will have been reacted
(c) infinity (d) 3.6xW30s-1 when 94% of A has been reacted is:
110. In the reaction (a) 4.06 (b) 3.06
(c) 2.06 (d) 0.06
BrO'3(aq.}+ 5Br-(aq.)+ 6ft' ~3Br2(l}+ 3H2 0(l}
118•. Two reactions A Products and B ~ Products, have rate
The rate of appearance of bromine (Br2 ) is related to rate of
constants k,4 and kB at temperature T and activation energies
disappearance of bromide ions as following:
EA and EB respectively. If kA > kB and EA < EB and
!CBSE. (Pi\1T) 200(11
assuming that A for both the reactions is same, then:
572 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(a) at higher temperatures k A will. be greater than kB (a) 2kl k2 4k3 (b) kl = k2 = k3
(b) at lower temperatures k A and kB will be close to each (c) 2kl 4k2 k3 (d) none of these
other in magnitude 127. The rate constant is numerically the same for three reactions of
(c) as temperature rises, k A and kB will be close to each other first, second and third order respectively. Which one is true for
in magnitude the rates of the three reactions if the concentration of the
(d) at lower temperature kB > kA reactant is than 1 M?
119. A substance undergoes first order decomposition. The (a) l'j 12 r3 (b) l'j > 12 > '3
decomposition follows two parallel first order reactions as: (c) l'j < 12 < 13 (d) All of these
A< kl
klB 128. In the Q.No. 127, if the concentration of the reactant is less
than 1 M, then:
= 1.26 X 10-4 S-l and k2 = 3.8 X 10-5 S-l
(a) l'j = 12 13 (b) l'j > 12 > 13
k2 C (c) l'j < 12 < lj (d) all of these
The percentage distributions of Band Care: 129. In the Q.No. 127, if the concentration of the reactant is 1 M,
(a) 80%B and 20%C (b) 76.83% B and 23.17% C then:
(c) 90% Band 10% C (d) 60% B and 40% C (a) l'j 12 13 (b) l'j >·rz > 13
120. Inversion of a sugar follows first order rate equation which can (c) 11 < r2 < 13 (d) all of these
be followed by noting the change in rotation of the plane of 130. For a first order reaction, A - - - t Product, the rate of reaction
polarisation of light in a polarimeter. If 1:", li and '0 are the at[A] O.2mol L- 1 is l.Ox 10-2 mol min-I. The halflife
fotations at t = 00, t = t and t = 0, then first order reaction can period for the reaction is: (liT 1999)
be written as: (a) 832s (b) 440s (cl416s. (d) 14 s
(a) k = ~ loge li - r= (b) k = ~ loge 10 - I';,.,
131. The rate constant of a first order reaction, A - - - t Products, is
t '0-1';,., t li-ro 60x 10-4 min -I. Its rate at [A] 0.01 mol would be:.
(lIT 1997)
(c) k ~ loge r~ - '0 (d) k = ~ loge 1:" -li (a) 60x 10-6 mol (b) 36x 10-4 mol L- 1 min-I
t r~-li t r~-rO
f. (c) 60 x 10-2 mol 36 x 10- 1 mol L:"! min-I
121. Rate ofa chemical reaction can be kept constant by:
132. For.a first order reaction, the half life is independent of: .
(BHU 1993)
(a) stirring the compounds (CBSE 1999)
(a) initial concentration
(b) keeping the temperature constant
(b) cube root of initial concentration
(c) both (a) and (b)
(c) first power of final concentration
. (d) none of the above (d) square root of final concentration
122. The number of molecules of the reactants taking part ·in a 133. Activation energy of a chemical reaction can be determined
single step of the reaction tells about: (AMU 1992) by: (CBSE 1998)
(a) molecularity of the reaction (a) changing concentration of reactants
(b) mechanism of the reaction (b) evaluating rate constant at standard temperature
(c) order of reaction (c) evaluating rate constants at two different temperatures
Cd) all of the above (d) evaluating velocities of reaction at two different tempera-
123. Number of moles of a substance present in 1 litre volume is tures
known as: [PMT (MP) 1993) 134. The experimenta~ d~ta for the reaction 2A + B2 ~ 2AB, is:
(a) activity (b) molar concentration
(c) active mass Cd) none of these
EIpt.No. (A) •.ad "("'S-I)
124. The inversion of cane sugar into glucose and fructose is: 1. 0.50 0.50 1.6 x 10-4
Ca) I order (b) II order (c) III order (d) zero order 2. 0.50 1.00 3.2 X 10-4
125. The unit of rate constant obeying the rate expression
3. 1.0 l.00 3.2 X 10-4
r k[AnBf!3 is:
(a) mol-213 litre 2f 3t irne:"I (b) moI 2!3litre-2f3 tirne- I The tate equation for the above data is: (CBSE 1997)
(c) mol-513
litre Sl3
time-I (a) rate = k[B 2 f (b) r.ate k[B2J
(d) none of these
126. For the reaction, (c) rate k[Af[Bf (d) rate k[Af[B]
N 20 S ---? 2N0 2 + 11202, 135. For the reaction A ~ B, the rate law is: rate k[A]. Whichof
- d[N 20 S ] ='k [N
dt 1 2
°]
5
the following statements is incorrect? IPMT (Ph.) 19981
(a) The reaction follows first order kinetics
d[N0 2 ]=k[NO ] (b) The of the reaction depends on initial concentration
dt 2 2 5
(c) k is constant for the reaction at a constant temperature
d[02] ~ k [N 0 ] (d) The rate law provides a simple way of predicting the con-
dt 3 2 S
centration of reactants at any time after the start of the re-
The relation in betWeen ki , k2 and k3 is: action
CHEMICAL KINETICS 573
136. Cyclopropane rearranges to fonn propene: (a) frequency factor (b) activation factor
!J,.---'t CH 3 CH CH 2 (c) pre-exponential factor (d) Boltzmann factor
] 43. Unit of frequency factor (A ) is:
This follows first order kinetics. The rate constant is
2.714 X lO-3 sec-I. The initial concentration of cyclopropane is (a) moles/lit (b) moles/lit/sec
0.29 M. What will be, the concentration of cyclopropane after (c) depends upon order (d) no unit
100 sec? IJEE (Orissa) 2009] 144. For the reaction A + B C + D, the variation of the
concentration of the products is given by the curve:
(a) 0.035 M (b) 0.22 M
(c) 0.145 M (d) 0.0018 M t
c::
137. The rate constantfor the reaction, o
1 ~
N20S(g)~ 2N0 2 (g)+ 2 02 (g), 'E
(l)
o w
c::
is 2.3 x 10-2 sec-I. Which equation given below describes the o
Q
""'-----~-""-
change of[N 2 0 s ] with time [N 2 0 s 1o and [N 20 S ] t correspond
Time-
to concentration ofN20 s initially and time 't'?(AIlMS 2004)
(a) [N 20 S ]o =[N2 0 s 1 it (a) x (b) y (c) z , (d) 111
(c)l~
, In 40 minutes, the concentration of X changes from 0.1 M to
0.025 M, then the rate of reaction when concentration of X. is
0.0 I M is: lilT (S) 20041
(a) 1.73xlO-4 M/min (b) 3.47xlO-s M/rnin Reaction-
4 5
(c) 3.47 x 10- M/min (d) 1.73 x 10- M/rnin ]46. EThreshold can never be:
139. In a first order reaction, the concentration of the reactant, (a) > ER (b) > Ep
decreases from 0.8 M to 0.4 Min 15 minutes. The time taken
(c) < Ep (d) > ER as well as >
for the concentration to change from 0.1 M to 0.025 Mis:
147. A reaction takes place in three steps; the rate constants are
(a) 30 min (b) 15 min (c) 7.5 min (d) 60 min k], k2 and k3. The overall rate constant k =: k]k3 . If energies
k2
140. A substance undergoes first order decomposition. The
of activation are 40, 30 and 20 kJ, the overall energy of
decomposition follows two parallel first order reactions as;
activation is:
A<klB k] = 1.26 X 10-4 sec-I (a) 10 (b) 15 (c) 30 (d) 60
148. For hypothetical reaction A ~ B takes place according to
k C k2 3.8 X 10-5 sec-] k2
2
A C, A +C~D(slow)
The percentage distribution of Band Care:
Rate. law will be:
IPMT (Kerala) 2004)
(a) k 2 [A][C] (b) k]k2[A] (c) k,k2[A]2 (d) klk2[AJ[C]
(a) 75% Band 25% C (b) 80% Band 20% C
149. If concentration of reactant is 'increased by .om'; then k
(c) 60% Band 40% C (d) 90% B and 10% C becomes:
(e) 76.83%Band23.l7%C (a) ek!m, (b) k (c) k/ m (d) mk
]41. For a reaction 2NH3 N2 + 3H2 , it is observed that 150. aA + bB ~ P; k[At . [Bt If conc. of A is
dx/ dt
doubled, rate is doubled. If B is doubled, rate becomes four
.:...d( NH3) = k (NH ), d(N 2 ) k (NH ), d(H 2 ) =: k (NH ).
dt I 3 dt 2 3 dt 3 3 times. Which is correct?
What is the relation between k] , k2 and k3 ? (a) -d[A] =: (b) -d[A]::=_-"---,,
dt dt dt dt
~"~'~l '" k2 =: k3 (b) 3k! 6k2 =: 2k3
(c) 2k! =: l,k =: 6k3 (d) 6k1 3k2 =: 2k3 (c) -2d[A] (d) None of these
dt dt
142. In Arrhenius equdti<)n k =: i RT, factor e - Ea ! RT is known
as:
574 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
151. A drop of solution (volume 0.05 mL) contains 3 x 10-6 mole of 158. ForX--7Y;k 10IOe-500IT,andforW--7Z;k 1012 e-IOOO!T
7 1
W. If the rate constant of disappearance ofH+ is 10 mol litre- at what temperature 'T' both reactions will have same value of
sec-I, how long would it take for W in the drop tel disappear? k?
(a) 6 x 10-8 sec (b) 6 x 10-9 sec (a) 500 K (b) 1500 K
(c) 6 X 10- 10 sec (d) 6 x 10-12 sec (c) 4.606 K (d) 2.303 K
500 5000
152. For the reaction, Hz + l z 2Hl. The rate law expression 159. For a reversible reaction where the forward reaction is
exothermic, which of the following statements is correct?
is: {JEE (WB) 20101
(a) - -1 -
d[RI]]
- :::: kl [H2 ][I2 ] (a) The backward reaction has higher activation energy than
[ 2 dt the forward reaction
(b). The backward and the forward processes have same
(b) [_ I = --'-''---''-_
activation energy
2 dt . k2 [H2 ][1 2 ] /
(c) The backward reaction has lower activation energy
(c) [- ~ d[RI]] k1 [H2 1[12 ] - k2 [RIf (d) No activation energy is required at all since energy is
2 dt '
liberated in the process
(d) [- ~2 d[RI]]
dt
= kl k2 [H, 1fT,]
..
160. For the reaction, A + 3B ---7 2C + D
which one of the following is not correct?
153: The chemical reaction, 203 ,~ 302 proceeds as; !EA;\,ICET (;vIed.) 2010j
0 3 ~ 02 + ° (fast), 0+ 0 3 --72°2 (slow) (a) Rate of disappearance of A = Rate of formation of D
The rate law expression will be:
(a) rate:::: k[O][03] (b) rate = k[03f (b) Rate of formation of C :::: ~ x Rate of disappearance of B
. 3,
1
, (c) rate:::: k[03f[02r (d) can't be determined
(c) Rate offormation of D = ~ x Rate of disappearance of B
154. For the reaction NH~ + OCN ~ NH2CONH Z' the 3
probable mechanism is, (d) Rate of disappearance of A :::: 2 x Rate of formation of C
NH:
+ OCN ~ NH 4 0CN (fast) 161. 2A ~ B + C, would be a zero order reaction when:
and NH40CN ~ NH1CONH2 (slow) !ellSE (PMT) 20021
The rate law will be: (a) the rate of reaction is proportional to square of concentra-
(a) rate:::: k[NH 2CONH2 ] (b) rate:::: k[NH4t[OCNr tion of' A'
(c) rate k[NH4 OCN] (d) none of these , (b) the rate of reaction is same at any concentration of 'A'
(c) the rate remains unchanged at any concentration of 'B' and
. 155. For a 1st order' decomposition,
'c'
kn
An~A
~'l I (d) the rate of reaction doubles if concentration of 'B' is
increased to double
k2
A2 162. Units of rate constants for first and zero order reactions in
overall k will be given by: , terms of molarity M unit are respectively: (AIEEE Z002}
(a) k kl + k2 + ... + kn (b) k= (k1 + k2 + .... + kll)ln Ca) sec-I, M ~C-l (b) sec-I, M
(c) k kl X k2 x ... X kll (d) none of these (c) M sec-I ,sec-I (d) M,sec- I
156. For a reaction A + 3B --7 P, Rate:::: , the expression for 163. Following is the graph between log and log a (a = initial
tll2
dt
the'rate of reaction in terms of change in the concentration of concentration) for a given reaction at 27°e. Hence, order is:
B, -d[B] will be:
dt I
(a) k[A]2[B]
(c) 3k[Af[B]
. (b) k[A f[3B]
(d) (~)k[A]2[B]
i
log tl/2
45°
157. Which ofthe following statements is correct?
. 'T-
(a) Rate of reaction oc
Eo loga--
(b) At lower temp., increase in temp. causes more change in
the value of k (a) 0 (b) 1 (c) 2 Cd) 3
(c) Both (a) and (b) are correct 164. Following is the graph between (a - xrl and time t for
(d) None is correct second order reaction. 8 tan-I (1/ 2);OA l
2 L mor , hence
rate at the start of reaction will be:
CHEMICAL KINETICS 575
(d) 1.25 mol L- 1 min- I concentration of A by 4 times, the order of reaction is:
(c) 0.125 mol L- 1 min- I
fCET (J&K) 2005]
165. Graph between concentration of the product' x' and time' t' for
(a) 2 (b) 1 (c) 112 (d) 4
A -7 B is given ahead:
170. For the reaction: 2N 20 5 (g) -----t 4N0 2(g) + O 2(g) if the
concentration of N0 2 increases by 5.2 x 10-3 M in 100 sec,
(a)
d[A)
---at
(b)
d[A)
---at
/ 172. An endothermic reaction with high activation energy for the
forward reaction is given by the diagram: (AIIMS 20(5)
t- t-
t
Potential
energy ~p t
Potential
energy
1\p
(c) (d)
_d[A)~
dt
Reaction -
coordinate
(a)
Reaction - +
coordinate
(b)
P pP
I
t- t-
Reaction - +
coordinate
(c) (d)
(a) rate = _ d[N2] =_~ d[H2] = + ~ d[ NH3]
dt 3 dt
dt 2
(b) rate';'; - d[N2] = _ 3 d[H2] = + 2 d[ NH 3] 173. For reaction aA -----t xP, when [A] =; 2.2 m-M, the rate was
dt dt dt found to be 2.4 m M S-I. On reducing concentration of A to
(c) rate = d[N21 = ~ d[H2] = ~ d[ NH 3] half, the rate changes to 0.6 m M s -I. The order of reaction
dt 3 dt 2 dt with respect to A is: (AJIMS 20(5)
(d) rate = _ d[N2] =_ d[H2] = d[ NH 3] (a) 1.5 (b) 2.0 (c) 2.5 (d) 3.0
dt dt dt [Hint: Rate = k [A]a
167. For the reaction, 2.4 = k [2.2 t ... (i)
Nz(g) + 3H2(g)-----72NH 3(g), if 0.6 = k [l.it ... (ii)
.:~~ffi, 1= 2 x 10-4 mol L-1s -I, the value "f -d[H2] would be: Dividing eq. (i) by eq. (ii), a =2 :. order = 2]
~ ~ )
rCBSE (PMT) 2009J 174. According to the law of mass action, rate of a chemical
reaction is proportional to: (AFMC 2005)
576 r A.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(a) concentration of reactants 181. The rate constant of a first order reaction at 27°C is 10-3 min -I.
(b) molar concentration of reactants The temperature coefficient of this reaction is 2. What is the rate
(c) concentration of products constant (in min -I) at 17°C for this reaction?
(d) molar concentration of products ;~T 2006\
(a) 10-3 (b) 5 x 10-4 (c) 2 X 10- 3 (d) 10-2 '
175. Consider the endothermic reaction X ~ Y with the activation
energies Eb and for backward and forward reactions, [Hint:
respectively. In general: (AIEEE lOGS)
(a) < Ef
(Il )10110 2
(b)Eb > E f
kTl
(c)Eb::: Ef
10-3
(d) there is no definite relation between Er and Eb ky; = - 0.5 X 10-3
1 2
176. Which one of the following statements for order of reaction is = 5 X 10-4 min-I]
not correct? lIlT (S) 2{)05]
182. In a chemical reaction, two reactants take part. The rate of
(a) Order can be determined experimentally
reaction is directly proportional to the concentration of one of
(b) Order of reaction is equal to sum of powers of them and inversely proportional to the concentration of the
concentration terms in differeIl.tial rate law "- other. The order of the reaction is: . [PMT (Raj.) 2G06j
(c) It is not affected by the stoichiometric coefficient-or-the (a) zero (b) 1 (c) 2 ' (d) 4 '
reactants
183. According to Arrhenius equation, the rate constant (k ) is
(d) Order cannot be fractional
related to temperature (T ) as:
177. The rate constant of a reaction is found to be 3 x 10-3 mol L- 1
min -1. The order of the reaction is: leET P&K) 20061 (a) In
( --.£)
k\ = (IIJ
- -
(a) zero (b) I (c) 2 (d) 1.5
k[ R, 11 12,
[Hint: Unit of rate 'and rate constants are same for zero order (b) --.£ =- rllJ
lnl\ikJ --
reaction.] kJ R ,,11 T2
178. In the first order reaction, the concentration of the reactants is
reduced to 25% in one hour. The half life period ofthe reaction (c) In [ k2
kl
J= R '( 11I + T2I J
is: jUGET (Manipal) 20051
:~ J= ~ +~ J
(a) 2 hrs (b) 4 hrs (c) 112 hr (d) 114 hr
[Hint: k = 2.303 log
t a
(_a_Jx
(d) In ( R (
(a) the energy above which all the colliding molecules will 186. Consider the reaction, 2A + B Products. When
react concentration of B alone was doubled, the half life did not
(b) the energy below which colliding molecules will not react change. When the concentration of A alone was doubled, the
(c) the total energy of the reacting molecules at a temperature T rate increased by two times. The unit of rate constant for this
reaction is:
(d) the fraction of molecules with energy greater than the
activation energy of the reaction (a) S-I (b) L mol-1s- 1 (c) unit less (d) mol
CHEMICAL KINETICS 577
-I
[Hint: Concentration change in 'B' does not change half life, it sec
0.5 0.5 mol- 1 dm 3 ]
means the reaction is fIrst order with respect to B. When ko mol dm- 3 sec-I
concentration of only' A' is doubled, the rate of reaction becomes
193~ The decomposition of HI on the surface of gold is :
double, thus order with respect to A will also be one.
Overall order of reaction 2 [Corned (Ktaroataka) 2008]
unit of rate constant'" L mol-Is- I ] (a) Pseudofrrst order (b) zero order
(c) fIrst order (d) second order
187. In a fIrst order reaction A --,--------7 B, if k is rate constant and
194. Consider following two reactions '
initial concentration of the reactant A is 0.5 M then halflife is:
[CBSE (Med) 2007] A ----7 Product, = k) [ A ]0
2 log 2 dt .
(a) (b) - - (c) In 2 (d) 0.693
k k.JUs k O.5k B ----7 Product, - 4[B] = k [B]
dt 2. 0
188. For the fIrst order reaction, halflife is 14 sec, the time required kr and k2 are expressed in terms of molarity (mol L- 1) and
for the initial conceritration to reduce to 118 of its value is: time (S-I) as: (BHU (Mains) 20081
[CET (J&K) 20071 (a)s-I,Ms-1L- 1 (b)M ,Ms- 1 •
(a) (14)3 sec (b) 28 sec (c) 42 sec (d) (14lsec
'(c)s-I,M-Is- 1 (d)M,
189. 75% of a fIrst order reaction was completed in 32 min, when
195. If a plot of log 10 C versus t gives a straight line for a given
was 50% of the reaction completed? (BHU (Mains) 20071
(a) 24 min (b) 16 min (c) 8 min (d) 48 min reaction, then the re~ction is : (VITEEE 2008f
(a) zero order (b) fIrst order (c) second oder (d) third order
190. For a zero order reaction,
A P [Hint:
t,X is: (k is rate constant) [BHU (Mains) 2007J
(a) (b) In 2 1 d In 2
2k k (C)k[A]o () [Alok
191. The rate constants kJ and k2 for two different reactions are
1016 e-20001T
, an d I v
hiS - I O O O I T ·
e "
, respectIvely. The temperature
at which kl = k2 is : ICBSE (PMT) 2008J
(a) 2000 K
[Hint: 10 15
(b) 1000 K
e-lOOOIT
2.303
=1016e-2000IT
(c) 1000 K (d) 2000 K
2.303 -
In first order reaction, 10glOC when plotted against time 't' then
we get straight line, Slope of the line (2.~03) gives the value of
e-2000IT 10 15
, ,e- 1000lT 10 16
e- I000/T = 10- I rate constant.]
196. For a zero order reaction the plot of concentration of reactant
loge e- )OOO/T = loge 10- 1
versus time is: (intercept refers to concentration axis)
1000 . _I fPET (Kerala) 20081
T = 2.303 10glO 10
(a) linear with +ve slope ,and zero intercept
2.303 (b) linear with -ve slope and zero intercept
T = 1000 K] (c) linear with -ve slope and non zero intercept
2.303 (d) linear with +ve slope and non zero intercept
192. Under the same reaction conditions, initial' concentration of (e) a curve asymptotic to concentration axis
1.386 mol dm - 3 of a substance becomes half in 40 seconds [Hint: '
and 20 seconds through fIrst order and zero order kinetics
respectiVely. Ratio ( :~) of the rate constant for fIrs.t o~der (kl ) . c:
o
i
and zero order (ko) of the reactiOn is :
(a) 0.5 mol-I dm3
(c) 1.5 mol dm-
'
[H mt : tl/2 =
.
3
0.693
kl
(b) I mol dm-3
(d) 2 mol-I dm 3
tl12 =
' 2ko
(liT 2008)
I L_'_,_ _ _ _ _ _.:....._
Tlme_
Linear with negative slope and non zero intercept.]
40 = 0.693 20 = 1.386 = 0.693
197. Tso of flist order reaction is 10 min. Starting with 10 mol
kl ' 2ko ko
rate· after 20 IIiin is: (AIIMS 2008)
20 0.693/ ko = ~ (a) 0.0693 mol L- I min-!
40 0.693/ kl ko (b) 0.0693 x 2.5 mol L- I min-I
578 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS •
(c) 0.0693 x 5 mol L- 1 min-I The pre exponential factor A and the activation energy Ea
(d) 0.0693 x 10moi L- 1 min-I respectively, are : (lIT 2009)
6
(a) Ix 10 s-I and 9.2 kJ mol- 1
[Hint: Remaining concentration of reactant after 20 min
= .!. x 10 = 2.5 mol L- I (b) 6 S-1 and 16.6 kJ mol- 1
4 (c) 1x 106 S-l and 16.6 kJ morl
Rate = k x [Reactant]
0.693 (d) IxIQ6 s-I and 38.3 kJ morl
= -- x [Reactant]
t1l2 [Hint: logk == 10glOA -~ xl
'2.303 T
== 0.693 x 2.5 = 0.0693 x 2.5 mol L-1 min-I] Comparing this equation with the given equation we get,
lO
198. For the decomposition of AB at 600 K, the following data A == l(f S-I, Ea == 38.3 kJ mor l ]
were obtained 201. The time for half-life period of a certain reaction,
Rate of deComposition of AB in A -} Product is I hour. When the initial concentration of the
mol dm-35-1 reactant' A' is 2 mol L- 1• How much time does it take for its
concentration to come from 0.50 to 0.25'moIL- 1 ifit is a zero
0.20 2.75 x 10-8 order reaction? (AIEEE 2010)
0040 llx 10-8 (a) 0.25 h (b) 1 h (c) 4 h (d) 0.5 h
0.60 24.75 x 10-8
The order of the decomposition of AB is :
[Hint: !l = [~
t2
fl
all
[eET (Karnataka) 2009)
(a) 0 (b) I (c) 2 (d) 1.5
..!. = (0.5Y-1
t2 \. 2 /
199. For a reaction between A and B, the initial rate of reaction is
measured for various initial concentrations of A and B. The, t2 =0.25 h]
data provided are: (DeE 2009) 202. Consider the reaction:
"I ~ ." IaitiaI ractioa CI 2 {aq)+ H 2 S(aq) - - } S(s)+ 2W (aq)+ 2cr (aq)
EIp.No. (A) (B)
rate (mol L-ls-I) The rate equation for this reaction is :
Rate = k [CI 2 ] [H2 S]
1. 0.2 M O.3M· 5 x 10-5
Which of these mechanisms is/are consistent with this rate
2. 0.2M 0.1 M 5 x 10-5 equation?
3. OAM 0.05M 7.5 x 10-5 A. Cl 2 + H2S ~ W + cr + CI+ + HS- (slow)
The overall order ofthe reaction is: (DeE 2009) CI+ + HS- ~ W + CI- + S (fast)
(a) one (1) (b) two (2) B. H2S~ U" +HS- (fast equilibrium)
(c) two and a half (2.5) (d) between 1 and 2 Cl z +HS- ~ 2CI- +W + S, (slow)
200. For a first order reaction A ----7 P, the temperature (T)
(AIEEE 2010)
dependent rate con",ant (k )was found to follow the equation: (a) neither A nor B . (b) Aonly
log k = -(2000)-1 + 6.0 (c) B only (d) both A and B
T
CHEMICAL KINETICS 579
[rl.'~ .. QUEStiONS
: OBJEOTIVE ' ~ " ,. _. ~., 0. ";",.. ' : ::,.: ";
[~
.~ : 'ASSi:RTION-REASON TyPE QUESTIONS
.'
; ,
I
1. (by 2. (b) 3. (a) 4~ (b) 5. (b) 6. (c) 7. (a) 8. (b)
9. (e) 10. (a) 11. (d) ]2. (b) 13. (b) 14. (b)
I
CHEMICAL KINETICS 581
(d) The frequency factor 'A" in Arrhenius equation For first order reaction,
(k Ae - Ea I RT ) increases with increase in temperature 2
,.. (ii)
2. The rate constant of the reaction, k
2H20 2 (aq.)-..? 2H 2°(l) + 0l(g), From eqs. (i) and (ii), a
is 3 x 10-3 min-I, ' 2k
a log" 4 M]
.At what concentration ofH20 2, the rate ofthe reaction will be
6. Which of the following is pseudo-unimolecular reaction?
2 x 10-4 M S-I?
(a) 2HzOl 2HzO + 0z
(a) 6.67 x 10-3 M (b) 2M '(b) C6HSN2Cl + HOH ~ C6 HsOH + N2 + HCI '
(c)4M (d) 0.08 M (c) CH3 C00CzHs + NaOH ~ CH 3COONa + CzHsOH,
[Hint: Rate k [H20 2 ]l (d) 203 ~ 302
-4 3 X10-3 7. The order and molecularity of the chain reaction,
2 x 10 = 60 X [HP2]
2HCI (g),
[H 20 l ]= 4 M] are:
3. The mechanism of the reaction,
2NO(g)+ 2H2(g)~ Nz(g)+ 2HzO(g),
(a)2,0 (b) 0, 2 (c)l,l
8. A reactant (A ) forms two products:
(d) 3, °
is:
kI
A ~ B Activation energy E a 1
fust k2
Step 2:, H 2 0 2 + Hz 2H zO
A ~ C Activation energy Ea2
(a) rate = k [N01l[Hlf
(b) rate = k [H 2 0 Z ][H l 1' If Eaz 2Eal , then kl and k z will be related as:
(c) on doubling the concentration of Hl , keeping the (a)kl kleEajlRT (b)kz=kleEazIRT
concentration of NO constant, the rate will become double
'(c)kl = Ak2eEaliRT (d)k =2kleEazlRT
(d) if the initial concentration of Hz and NO is Co and after 1
[Hint:
1 2.4 X 10-5 3 X 10-5 [NP5]
t 112 0<: d'-l
[NzOs]=0.8M]
1 15. Consider the following statements:
t 112 = k --;;-::t
a 1. The rate of reaction is always proportional to the
In t1l2 = In k - (n - 1) loge a] concentrations of reactants.
11. Half life of a reaction becomes half when initial concentrations 2. The order of an elementary chemical reaction step can be
of reactants are made double. The order of the reaction will be: determined by examining its stoichiometry.
(a) I (b) 2 (c) 0 (d) 3 3. The first order reactions follow an exponential time
1 , course.
[Hint: t1l2 O<:--;;-::t
a Of these statements:
1 (a) 1,2 and 3 are correct (b) land 2 are correct
1112 =
,a (c) 2 and 3 are correct (d) 1 and 3 are correct
where, ~ = order of reaction for second order reaction.] [Hint: Statement (1) cannotbe correct because the rate of zero
12. Arrhenius equation is: order reactions does not depend on concentration of reactant.]
k = Ae-E1RT 16. Two different first order reactions have rate constants kj and k2
Which of the following graphs represents the variation of rate at 11 (kt > kz ). If temperature is increased from 11 to Tz, then
constant k against temperature T ? (lIT 2010) new constants become k3 and k4 respectively. Which among
the fQllowing relations is correct?
!I~
(a) kt > k2 = k3 k4 (b) kl < k3 and k2 < k4
(c) kl k3 k4 ' (d) kl > k, > k, '> k4
i
k
17. In the reaction, A + B ~ C + 1), the rate l~) when
. dt
.... ~ J ,
i
k
t
k
the rate of appearance of NH3 is:
d[
NH
3] 2 x 10-4 mol L- 1 sec- 1
dt
The rates of the reaction expressed in termS ofN2 and H2 will
T- T ,,--. be:
(c) (d) Rates ill terms of HI , ~intennsofNI
13. If a homogeneous catalytic reaction follows three alternative
(mol L -I see-I) (mel L -1 see~I)
paths A, B and C, then which of the following indicates the 4
(a) 3 x 10- 2 X 10-4
relative ease with which the reaction moves?
(b) 3 x 10-4 I X 10-4
A
(c) 1 X 10-4 3 X 10-4
(d) 2 x 10-4 2 X 10-4
Location 1
(a) Activated complex
Reaction progress -
Location 2
Activated complex
t
>-
0.
(ij
..c:.
'E
w
Ap
t
>-
0.
(ij
..c:.
'E
w
f\-p
Reaction (I) - Reaction (11)-
(b) Reaction intennediate Activated complex
(c) Activated complex Intermediate (a) Reaction I forward . (b) Reaction I reversed
(c) Reaction II forward (d) Reaction II reversed
(d) Reaction intennediate Intennediate
23. Consider this reaction: 27. Which function of [X ], plotted against time, will give a
2N0 2(g)+ 03(g)~ NzOs(g)+ 02(g) straight line for a second order reaction?
The reaction of nitrogen dioxide and ozone represented is first X ~Product
order in N0 2 (g ) and in 0 3(g ). Which of these possible (a) [X] (b)[xf (c) In [X] (d)_l_
reaction mechanisms is consistent with the rate law? [X]
. Mecl1anism I: N0 2 (g ) + 0 3 (g ) ~ N03(g) + O 2(g) (slow) 28. Decomposition ofH 2 0 2 is a first ordeueaction. ~ 16 volume
N03(g)+NOz(g)~N20SCg) (fast) solution ofH2 0 2 ofhalflife 30 min is present at start. When
Mechanism II: 03(g) 02(g)+[0] (fast) will the solution become one volume?
NOz(g) + [0] ~ N03 (slow) (a) After 120 min (b) After 90 min
N03 (g) + N02 (g ) ~ NzOs (fast) (c) After 60 min (d) After 150 min
(a) I only (b) II only 29. What is the activation energy for the reverse of this reaction?
(c) Both land II (d) Neither I nor II N 20 4 (g) ~ 2N0 2 (g)
°
fHint: Mechanism I, Rate = k[NO z ][ 2 ], Slow step is rate Data for the given reaction is: t:.H + 54 kJ and
kJ:
= + 57.2
determining
(a) -54 kl (b) +3.2 kJ (c) +60.2 kJ (d) + 111.2 kJ
Mechanism II, Rate = k [NOz][O] ... (i)
30. The reaction between chlorofonn, CHCl 3 (g) and chlorine
K [0 2 ][0], [0] = K [0 3 ]
[0 3 ] [0 2 ] Cl 2 (g ) to fann CCl 4 (g) and HCl(g) is believed to occur by
this series of steps:
584 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
i~··
(a) A ) B; Ml = -lOkcal
Ea 50 kcal
(b) A ) B-, Ml= + tOkcal
~>. I
Ea 60 kcal
(c) A ) B-, Ml +20kcal ~~
!l..cn (. +B . . AB
(d) All of the above
[Hint: . Ml == (Ea)J (Ea}b Reaction _
Reactio.n _
(Ea)b (Ea}f - Ml = 50 + 10 == 60 kcal] coordinate coordinate
(a) (b)
42. For n th order reaction ~ dependson(n =/:. 1):
t3/4
( a) initial concentration only
(b) 'n' only AS
(c) initial concentration and 'n' both
(d) sometimes 'n' and sometimes initial concentration
[Hint: Time for fractional change oc }_ I ] Reaction _ . Reaction_
a coordinate coordinate
43. For a second order reaction, 2A Products, a plot of log (c) (d)
tl12 vs log a (where, a is initial concentration) will give an 46. A reaction takes place in three .steps with indIvidual rate
intercept equal to which one of the following? (SeRA 2007) constant and activation energy,
k l[ 1 1]
t (a x) a
···~~~~""""""~·\)verall activation energy of the reaction wHrbe :
(a) 140 kJ/mol (b) 150 kJ/mol
a (c) BOkJ/mol (d) 120kJ/moi
when x =2,t= tll2
1 1
- .
A. - EUj IRT A - E021 RT
[Hint: Ae-EaIRT = .. e .. e
1
213
[ - E031RT .
tll2 = k x~ . Ae .
== [Ae(- EUj- Ea} + Eo)}1 RT l213 .
log t1/2 = -log k log a]
44. ·For a reaction taking place in three steps, the rate constants are 2
Ea "3 [Eal + Ea2 - E. 3 ]
k], k2 and k3- The overall rate constant k = If the energy
k3 ="32 [180 + 80 50] '" 140 kJ/inol]
of activation values for the first, second and third stages are
586 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
[;4~' I
1. (d) 2. (c) 3. (c) 4.. (b) 5. (a) 6. (b) 7. (b) 8. (a)
9. (c) 10. (a) 11. (b) 12. (e) 13. (b) 14. (d) 15. (c) 16. (b)
. 17. (b) 18. (b) 19. (b) 20. (b) 21. (b) 22. (b) 23. (e) 24. (d)
25. (b) 26. (b) 27. (d) 28. (a) 29. (b) 30. (e) 31. (e) 32. (c)
33. (c) 34. (c) 35. (d) 36. (b) .37. (b) 38. (a) 39. (a) 40. (a, e)
41. (a) 42. (c) 43. (d) 44. (a) 45. (a) 46. (a)
C (t 1/2
.
= 12 brs)
The half-life for the decay of A is .................hrs.
8. The half-life period of a first order reaction is I hr. What is the
time in hour taken for 87.5% completion of the reaction?
will be:·'
9. The half-life of a reaction is doubled' when the initial
3.. The rate of a reaction at 10 sec intervals are as follows: .
concentration is doubled. The order of reaction is :
Rate . 10. For the reaction A2 + 2B ~ 2AB, the following data were
Time(~) . (mol L -1 sec-I) observed: .
o 4.8x 10-2.
Exp.No. IAll- (BI
Rate
(mol C-1 S"':I)
10. 4.79 x 10-2
l. 0.1 . 0.01 1.5 x 10-3
20 . 4.78 x 10-2
30 4.81 x 10-2
2. . 0.1 0.04 6.0 x 10-3
3. 0.2 0.01 3.0 x 10-3
What will be the order of the reaction?
4. How many times of the half-life will require to complete 75% The overall order of the reaction will be :
of a reaction of first order?
[·J14~.--------------1f.
1. (4) 2. (2) 3. (0) 4. (2) 5. (1)' 6. (4) 7. (3) . 8. (3)
9. (0) 10•. (2)
CHEMICAL KINETICS .
[/I~"--------------t
P~J. 1. (d) 2. (a) 3. (d) 4. (c) 5. (d) 6. (a)
P.....,..2. 1. (a) 2. (c) 3. (b) 4. (c)
~3. 1. (b) 2. (a) 3. (a) 4. (a) 5. (b)
·P.....,..4. 1. (a) 2. (h) . 3. (d) 4. (b) 5. (b)
P~5. 1. (c) 2. (b) 3. (d) , 4:. (b) 5. (a)
CHEMICAL KINETICS 589
i
~.
I
(a) 2m + n (b)m + n (c) n - m (d)i,,-m) .
1
Rate
a correct explanation for Statement-I.
(c) Statement-l is true; Statement-2 is false.
(d) Statement-l is false; Statement-2 is true.
16. Statement-I: If temperature does not affect the rate of
a- reaction, Ea = o.
(a) . (b) Because
Statement-2: Lesser is the activation energy, slower is the
rate.
1 1
.. tl/2
17. Statement-I: In the reaction:
N0 2 (g) + CO(g) ~ CO2 (g) + NO(g)
Rate k[N02f
tl/2
Th~ rate of reaction does not depend on the· concentration of
CO. \
11<1 - 1/a-
Because
(c) (d)
Statement-2: Carbon monoxide is involved in fast step.
Here 'a' denotes initial concentration of reactants. 18. Statement-I: The reciprocal of time in which 66% of the
12. Arrhenius equation may be given as: reactant is converted to product is equal to the rate constant of
first order reaction.
(a) In A = ~ . (b) log A = log k + Ea
k RT 2.303RT Because
Statement-2: The rate constant for first order reaction
(c) log [-Ea ] k (d) d In k depends on initial concentration of reactants.
RT a dt RT
13. WhiCh of the following is/are correct for second order reaction? .sEcTION-IV
(a) till is inversely proportional to initial concentration Matrix-Matching Type Questions
(b) k = ~ [_1__ .!.] Thi!> section contains 3 questions. Each question contains
t (a-x) a statement given in two columns which have to be matched.
Statements (a, b, c and d) in Column-I have to be matched with
(c) k = 2.303 log (-.a_J statements (p, q,rand s) in Column-II. The answers to these
t a-x
questions have to be appropriately bubbled as illustrated in the
(d) k = 1 [ 1· _~]
2
following examples:
2t (a - xi a If the correct matches are (a-p,s); (b-q,r); (c-p,q); and (d-s),
14. For a 1st order reaction: then correct bubbled 4 x 4 matrix should be as follows:
A ~ B, with initial concentration = a p q r s
. k .
. (a) t!12 =
a
0.693
(b) t3/4 = 2tl/2
a8@00
(c) tl/2
k
(d) tl12 k x 0.693
15. Select the correct statement for Arrhenius equation
b0_e0
. k = Ae-EaIRT
(a) 'A' maybe termed as the rate constant at very high
c8_0
temperature .
(b) , A' may be termed as the rate constant at zero activation
d®@0
. energy
(c) Ea is the activation energy of reaction 19. Match the Column-I with Column-II:
(d) k is rate of reaction at zero concentration Column-I Column-II
(a) Rate of reaction . (P) May be fractional
(b) Rate constant (q) Whole number
Assertion~Reason Type Questions (c) Order ofreactiOil (r) Independent of temperature
This section contains 3 questions. Each question of this (d) Molecularity of reaction (8) Increase with temperature
section contains Statement-l (Assertion) and Statement-2
CHEMICAL KINETICS I. 591
20. Match the Co1umn-I with Column-II: 21. Match the Co1umn-I with Column-II:
ColuMn-) ColuMn-II CoIUMn-) ColuMn-II
(Order of reaction) (Grapb) (a) First order (P) Unit of k sec-I
(L~
(b) Pseudo first order (q) Unit ofk = dm6 mor2s-1
(P) (c) Third order (r) t112 oc: 11 a 2
(a) First order
1
(d) Second order (s) tl12 ex:-
t- a
[A~· 11
Fig. 9.1
5941 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
This reaction can be graphically represented as, 9.3 THE LAW OF CHEMICAL EQUILIBRIUM
(Applicati9n of Law of Mass Action)
i
c
Equilibrium
region Consider a reversible homogeneous reaction which has attained
equilibrium state at a particular temperature.
o
----~----------H2
~C
A+B::;:::==:'=C+D
Ql
--+--------12 Let the active masses of A,B, C and D be [A], [B], [C] and [D]
u
U
C
o --11-------
1
HI respectively at equilibrium.
According to law of mass action,
1
1
'1
1
I' Rate of forward reaction oc [A][B]
---Time-- or Rate of forward reaction kf [A][B]
Fig. 9.2 (where, kf is the velocity constant for forward reaction).
Similarly, '
(iv) Equilibrium state can be attained in a lesser time by
Rate of backward reaction ex: [C][D]
the use of a positive catalyst, i. e., the relative concentrations
,of reactants and products' remain the same irrespective of or Rate of backward reaction kb[C][D]
the presence or absence of a catalyst. Thus,' a catalyst does (where, kb is the velocity constant for backward rel;lction).
not change the equilibrium state but it helps in attaining it rapidly. At equilibrium,
(v) It is dYnamic' in natunoj, i. e. , b()th-the reaction~ move with
same speed. However,the r~action seems to have come to stand Rate of forward reaction = Rate of backward reaction,
still because the concentrations of reactants and products do nQt
'change. ;
i. e., kf [A][B] = kb[C][D]
Reversible chemical reactions are classified into two types kf [C][D]
or
heterogeneous and homogeneous reactions. kb [A][B]
, Heterogeneous reactions: The reversible reaction in which
Since, kf and kb are both constants, the ratio kff kb is also a new
more than one-phase is present.
constant say K c' i. e. , \
" CaC0 3 (s) ::;:::==:'= CaO(s) + CO 2(g) [C][D]
Kc ... (i)
MgC0 3 (s)::;:::==:'= MgO(s) + cO 2 (g) [A][B] "
, 2Naz 0 2(s) + 2H 2 0(1) 4NaOH(l) +O 2 (g) Kc is known as equilibrium constant. Kc has a definite value
,3Fe(s) + 4f120(l) ::;:::==:'=Fe304(S) + 4H 2(g) for every chemical reaction at a given temperature regardless of
, "
the concentration of the reactants.
Homogeneous reactions: The reversible reaction in which
Considering a more general homogeneous reversible reaction
only one-phase is present, i. e., all the reactants and products are
at a particular temperature which is under chemical equilibrium,
in the same physical state.
mlA I +m2 A 2 +~A3 + ... ::;:::==:'=nIBl +n2 B 2 +n3 B 3 + ...
H2 (g) +I2(g) 2H1(g)
Rate of forward reaction k[ [AI ]ml [A2 ]m2 (A3 ]m3 •.•
CH 3 COOH(l) + C 2Hs OH(1) ----" CH 3 eOOC 2Hs (l) + H 2°(l)
Homogeneous reversible reactions are further classified into
Rate of backward reaction = kb[Bl tl {B 2] "2 [B 3 t 3 •••
three types: At equilibrium,
First type: When there is no change in number of kf [AI ]ml [A2 ]m2 [A3 ]"'3 ... = kb[BI ]nl [B2 t2 [B3 r 3 ...
molecules. Examples are:
kf [Bltl[B2t2[B3t3 ... =K
or ... (ii)
(iv H2 +12 ::;:::==:'=2H1 kb [Ad m1 [A2]~[A3]"'3 .:. c
(ii) , 2NO::;:::==:'=N2 +02 The equilibrium constant, at a given temperature,is the
ratio of the rate co.nstants of forward and backward
(iii) CH3COOH + C2HsOH::;:::==:'=CH3COOC2Hs + H 2 0
rea~tions.
Second, type: When there is .an increase in number of Or
molecules.
The equilibrium constant may be defined as the ratio.
PCl 5 ::;:::==:'=PC1h +C1 2 between the product of the molar concentrations of the
, 2NH3 ::;:::==:'=N 2 +3H 2 products to that of the product of the moiar concentratio.ns of
Third type: When there is a decrease In number of the reactants with each concentration term raised to a power
molecules. . equal to stoichiometric coeffiCient in the balanced chemical
equation.
N2 t 3H 2 2NH3
2S0 2 + O 2 ::;:::==:'= 2S0 3
I
CHEMICAL EQUILIBRIUM I 595
The value of equilibrium constant is independent of the '(b) Consider the following chemical equation,
following factors: Nz(g)+ 0z(g)+ Cil (g) 2NOCI(g)
1; Initial concentrations of the reactants involved.
, [NOCl] 2
2. The presence of a catalyst.
3. The direction from which the equilibrium has been
Kc =[N2 ][02 ][Cl z ] ... (i)
attained. Suppose the a\love equation is split into two as:
4. The presence of inert materials. [NO]z,
The value of equilibriUJ11 constant depends on the following N 2 (g)+ 02(g) 2NO(g); Kl = ..• (ii)
factors: ' [N2)[OZ]
1. The mode of representation of the reaction:
Conventionally, the concentrations of the products are put in the 2NO(g) +Cl z(g ) ~ 2NOCl(g); K
2
=' [NOG]2 ... (iii)
[No]2 [Cl z]
numerator and the concentrations oftbe reactants in denominator
in the equilibrium law equation. Consider the reversible reaction, Combining above two equations,
2
A+B C+D K xK - [NOf X [NOCI]z == [NOCI] =K
The equilibrium constant for the reaction, I 2 - [NzUOz) [NOf[Cl z] [N2][02][Cl z ] c
K = [C][D] ... (i) Thus, when an equation (having equilibrium constant, K c) ';"
c [AUB] written in two steps (having equilibrium constant k 1 and K2 )j--
Now, if the products are ,made reactants, i. e., the reaction is then K c :: K I X K 2: '
reversed, 3. U~e of partial pressures instead of concentrations:
C+D A+B When the reactants and products are in gaseous state, the partial
pressures can be used instead of concentrations at a definite
The equilibrium constant for the reaction is
temperature, as the partial pressure of a substance is proportional.
K' = [AUB] ... (ii) to its concentration in the gas phase .
C [CUD] Consider a general reversible homogeneous gaseous reaction
The equilibrium constant, K;, is actually the reciprocal of m1A 1 +miA2 +m3 A ).+... nlB I +n2 BZ +n3 B 3 + ...
K c ' i.e., Let the partial pressures of various reactants and products be
K,=_l_ pAl' pAz, pA3' ... , and pBI' pB 2, pB 3 , ••• respectively at
C Kc equilibrium. The equilibrium constant for the reaction,
2. Stoichiometric representation of the chemical Kp = (pBI tl(pB2)n2(p B 3)n3 ... ...(i)
equation:, (a) When a reversible reaction can be written with
( pAl )ml ( pA z )m2 (p A 3 )m3 .. .
the help of two or more stoichiometric equations, the value of . ' ' . ' .
equilibrium constant will be numerically different in these cases. The value of K c for the above reaction can be given as:
For example, the dissociation ofNOz can be represented as: n1
K= [Btl [B2r2[B3t3 ...
. .. (ii)
2NO z .,..:......: N z + 20z ... (i) c [Adm! [A z ]in2[A 3)1113 ...
I '
or NOz - Nz + 0z ... (ii)
, ,2, F or an ideal gas, pV=nRT
. . ' [Nz][Oz]z 'n
For equatIOn (I), the value of Kc = z' , ... (iii) or, p=-,RT,
ENOz ] V
[N ]1I2[0 ] = Active mass x RT
For equation (ii), the value of K; = z z ... (iv)
[NO z ] (wijere, n = number of moles and V =volume in litres. Thus,
Thus, the two constants are related to each other as: -Vn =moIar concentration
.'
. or actIVe
. mass) .
K;=.[K;c, ... (v)
Substituting the values of partial pressures in eq. (i),
In general, when a balanced' equation, having equilibrium
constant K e' is multiplied by a certain value n, the equilibnum K r
=. [BI tl (RT )nl . [B z )"2 '(R T t2 . [B3 3(RT )n3 .. .
constant for the new equation wjll be equal to (Ke t. P [Ad"!} (RT )m! . [A 2 ]"'2 (RT )m2 .[A3 ]m3 (RT) m3 .. .
A +B C +D, Kc = [C][D]
[A][B] HBtlnl(B'2rZ[B3)"3 ... }(RJ )nl +"2+ n3+'"
or Kp
{[A; )m} [A2 ]m2 [A3 )m3 .. .}(RT )mJ +mz +m3 +.. ,
nA+nB~nC+nD, it' :: [CY[Dt =(K )"
C [At[Bt c,
or K = K . (RT )Ln
p C (RT)Lnz
596 G.R.B. PHYSiCAL CHEMISTRY FOR COMPETITIONS
log
k2
k; ::: E [I IJ
2.303R T2 - T
J
... (ii)
T-- T--
when, T2 > TJ (a) Endothermic reaction (b) Exothermic reaction
(l 1j
for forw!'-d reaction,
kh
log -;;;: == - 2.303R T2 - T
[1 IJ J
... (iii)
(Plots of log K versus T)
Fig. 9.3
log
[ khlk~ 'j
kfl/kb l
- (E f Eb
2.303R
)[ 1 I]
---
T2 Tl
2NO~Nz +02
K 21 /ili [1 1]
or
log ( K: ; - 2.303R T2 - Tj
... (v)
K c will have units for a reaction in which the total number of
where, /ili is the heat of reaction at constant volume and
moles of reactants and products are different. For example, for
. K 1 and K 2 are the equilibrium constants of a reaction at
decomposition of PCI s , the K c has mol/litre units.
temperatures Tj and T2 (Tz > Tj ).
The effect of temperature can be studied in the following three PCl 3 + Cl z
cal"es: [PC1 3 ][C1 2 ]
First case: /ili == 0, i. e. ,neither heat is evolved, nor absorbed.
So, 1
or
log K 2 - log K I :::
log K 2 log K I
° In the formation of ammonia,
[PCl s ]
or Kz KJ N z + 3H 2 ---->. 2NH3
. Thus, equilibrium constant remains the same at all
-temperatUres. K = [NH 3 ]z
Second case: When, /ili = -+ veL e., heat is absorbed, the c [N 2 ][H 2 ]3
reaction is endothermic. The temperZture T2 is higher than TJ • K c has litre 2 mol-i units.
I
Thus,
( -T2 -I ' liS. negative.
. In general; unit of K c [M]Ll.n
Tj;
So, log K 2 log K j = + ve
I
CHEMICAL EQUILIBRIUM 597
where, M . mol litre -I and!1n number of gaseous moles of and for equation, ~N2 + 7i H2~ NH 3 ,
product or products number of gaseous moles of reactant or K' [NH 3 ]
reactants. ... (ii)
c [N2 ]112 [H2 ]312
Note: (i) The above relation can be used in homogeneous liquid system
also Squaring equation (ii),
!:>.n number of moles of product or products
number of moles of reactant or reactants
(K; )2 = [NH 3]2 3 ... (iii)
(ii) Similarly, the unit of Kp [atmjlln
[N 2 ][H 2 )
where, !:>.n number of gaseous moles of product or products Equations (i) and (iii) are same
- number of gaseous moles of reactant or reactants. Thus, Kc = (K~)2
Example 4'. Determine K c for the reaction,. Solution: Using the relation,
1 1" l'
-N2(g)+ -0 2(g) + - Br2(g) NOBr(g)
log KP2 =~[T2 Tl]
2 2 2, KPI 2303R T21i
Given, 0"
I K2 All [T2
"K; = 2.303R 11 T2
-lIj
.!.N2(g) + I °2 (g) ~ NO(g); .
og
2 2 ' 9.25 All 75
Io g - = x----
Eq~i1ibrium constant
18.5 2.303 x 8.314 925 x 1000
[ 1 30 )112
• 00 2.4 x 10 0.301 = All x 75
2.303 x 8.314 x 925 x 1000
= 0.6455 X 10- 15 or . . All:::: 71080.57 J mol- 1
1 1 .----"
- H 2(g) + -I2(g) ~ HI(g); AH = 1.35kcal
2 2
2HI(g) ~ H 2(g) + I 2(g); AH =2x 1.35 = 2.70kcal
. AH E a (f) - E a (b) .
2.70 44.3-Ea(b)
Ea (b)= (44.3 - 2.70)
or = 41.60kcal
Exam}1le 8. For a reaction X --? Y, heat of reaction is
+ 83.68 kJ, energy of reactant X is 167.36 kJ and energy of
activation is209.20kJ. Calculate (i) threshold energyJii) energy
._- 1
T .
ofproduct Yand (iiI) energy ofactivation for the reverse reaction Fig. 9.5
(Y --?X). (i) When, AGO = 0, then K c 1.
Solution: (i) Given, Ea (f) = 209.20 kJ (ii) When,AGo > 0, i.e.,+ve, thenK c < 1. In this case reverse
AE + 83..68kJ reaction is feasible, i.e., less concentration of products at
Energy of teactant; X 167.36 kJ equilibrium state ..
Threshold energy = Energy of reactant X + Activation energy (iii) When, AGO < 0 • i.e., - \Ie, then K c > 1. In thiscase~-~
for forward reaction forward reaction is feasible showing thereby a large
167.36 + 209.20 = 376.56 kJ concentrations of products till the equilibrium is reached.
(ii) Energy of reaction, AE = Energy of product Energy of Example 9. For the reaction,
reactant 2NOCI(g ----" 2NO(g ) + Cl2 (g ), ....,;;
Energy of product = 83.68 + 167.36= 251.04 kJ
(iii) Activation energy for backward reaction calculate the standard equilibrium constant at 298K. Given that
the values of AHO and AS ° of the reaction at 298 K are 77.2 kJ
= Threshold energy - Energy of product mol -\ and 122JK -1 morl.
= 376.56 - 251.04 = 125.52 kJ
Solution: Using the relation,
AGO = mo - TAS °
9.6 STANDARD FREE ENERGY CHANGE = 77200 - 298 x 122
OF A REACTION AND ITS = 40844 'J mo1-1
EaUILIBRIUM CONSTANT
... Let the equilibrium constant be K~. We know that,
Let AGO· be the difference in free energy of the reaction
·when all the reactants and· products are in the standard state AGO = - 2.303RTlog K~
· (1 atmospheric pressure and 298 K) and Kc or Kp be the or log K~ = _ AGO = 40844
thermodynamic equilibrium constant of the reaction. Both are 2.303 x 8.314 x 298 2.303 x 8.314 x 298
related to each other at temperature T by the following relation:
. AGO =-2.303RT log Kc = 7.158
and AGO - 2.303 RTlog Kp. (in case of ideal gases) KOc 6.95 x 10-8
This equation represents one of the most important results of
Example 10. AGO for 1 N z (g) + ~ H 2 (g) ---"'. NH 3 (g)
· thermodynamics and relates to the equilibrium constant of a 2 2
reaction tp a thermochemical property. It is sometimes easier to is -16.5.kJ mol-I. Find out Kp for the reaction at 25°C. Also
calculate the free energy in a reaction rathet than: to measure the
equilibrium constant. report Kp and AGO for N 2 (g)+3H z (g) 2NH3(g) at
Standard free energy change can be thermodynamically 25°C.
calculated as: Solution:
AGO == AHo - TAS ° AGO (- 16.5 X 10 3 )
Here, AHO =standard enthalpy change, log Kp = - 2.303RT =- 2.303 x 8.314 x 298 2.8917
AS ° standard entropy change. Kp = 779.41
-RTloge K p =IJJ:lO-TASO . Kp for reaction N 2 (g)+3H 2 (g) 2NH3(g) is equal to
. ASO IJJ:lO
log K = - - - (779.41): 6.07x10s
e p R RT
.~\G = - 2.303 x 8.314 x 298 log 6.07 x lOs joule
10 K _ ASo IJJ:lO
gJO p - 2.303R 2.303RT == - 32.998 kJ mol-I
CHEMICAL EQUILIBRIUM 601
PPC1s
a-
( a+x
xJ .P,' PPC13 (
x ) 'P; PCl
z
__x_.p
The effect of various factors at equilibrium is discussed here.
a+x (a +x)
(a) Effect of pressure: By increasing pressure; the volume
term decreases. The value of x must increase to maintain the
constant value of K c : In other words, the formation of ammonia
(a - x )(a+ x) , increases with increase of pressure.
(b) Effect of concentration: By increasing the
(units = atm) concentration of either nitrogen or hydrogen in the reaction
(a) Effect of pressure: In this case, K c == x 2 I (a - x) V. If mixture, the rate of forward reaction increases, i. e., the fonnation
pressure is increased, the value of' V' decreases, i. e. , the value of of annnonia increases.
denominator decreases. To maintain constant value of K c , x must (c) Effect of temperature: The synthesis of annnonia is an
also decrease. In other words, the dissociation ofPCl s decreases. exothennic reaction. The value of equilibrium constant d~creases ..
Thus, the increase of pressure would suppress the dissociation of with increase of temperature. Thus, high tempeniture is _~=,~_~~. ~.. _
PCIs· f!lvourable for the synthesis of ammonia: .
(b) Effect of concentration: If PCls is added to the Calculation of K p : Let the total pressure at equilibrium be P.
equilibrium mixture, the rate of forward reaction increases, i. e. ,
dissociation of PC Is increases. In case PCl 3 or Cl 2 is added, the Total number of moles at equilibrium
rate of backward reaction increases. This shall decrease the =(a-x)+(b-3x)+2x' (a+b-2x)
dissociation of PCIs . 2x
P NH 3 - xp· --'----"--'- x p.
(c) Effect of temperature: The dissociation of PCIs is an - (a + b - 2x) , (a+b-2x) ,
endothermic reaction. Thus, the value of equilibrium constant
increases with increase of .temperature. It is thus concluded that (b-3x) P
PH = X
dissociation increases with the increase of temperature. 2 (a + b 2x)
(d) Effect of adding an inert gas: When an inert gas is 2
added at constant volume the equilibrium state is not disturbed. 2x P
In case an inert gl\,s is added at constant pressure, the volume [ (a+ b- 2x) ]
increases, To maintain the constant value of K c , x must also 3
(a-x) P (b-)x) p
increase. Thus, the addition of an inert gas at constant pressure
increases the degree of dissociation of PCl s . [
(a+b-2x) J[(a+b-2x). ]
Case III: Homogeneous gaseous reaction when, t,n < O. 4x 2 (a + b 2x)2
Synthesis of ammonia: The formation .of ammonia from
(a - x)(b - 3x)3 p2
nitrogen and hydrogen is represented by the equation:
N 2 (g) +3H 2 (g) ~ 2NH3(g) Case IV: Homogeneous liquid system: Formation of
Let a start be made by mixing' a' moles ofN z and' b' moles of ethyl acetate:
hydrogen in a closed vessel of V litre capacity. By the time The reaction between .alcohol and acid to form ester is an
equilibrium is established 'x' moles of nitrogen have combined example ofhompgeneous equilibrium in liquid system.
with 3xmoles of hydrogen and produced 2xmoles of ammonia. CH3 COOH(l) + C 2 HsOH(l) ~CH3COOC2Hs(l) + H 2 0(l)
'l'b'
At eqUll num, [N ] (a-x) Let a start be made by mixing 'a' moles of an acid and 'b' moles
2
V of an alcohol. By the time equilibrium is established, x moles of .
[H J=(b-3x) ester and 'x' moles of water are formed, i. e., x moles of acid and x
2
V moles of alcohol have been consumed. Let V be the total volume.
2x At equilibrium, the active masses of reactants and products are:
[NH 3 J=--v (a-x) (b-x)
[CH 3 COOH]=,[C zHsOH1== ,
Applying law of mass action, V V
K == [NH 3]2 x x
[CH 3 COOC z Hs ] -and [H 2 0]=-
c [N2 ][H Z ]3 V· V
K == [ester][water]
x x
VV
x-
.(a;X)(b~3Xr
(a - x)(b - 3x)3 c [acid] [a1cohol]
CHEMICAL EQUILIBRIUM 603
(b) No. of moles OfI2 at equilibrium == (0.5 . 0.39) 0.11 mole Example 16. The equilibrium constant of the reaction,
Kp ==Kc(RT ),"n A 2 (g)+B 2 (g) 2AB(g)
As An 0 , K p == K c 50 at 100°C is 50. If a one litrejlask containing one mole of A2 is
Example 14. 25 mL of H 2 and 18 mL of I 2 vapours were connected to a two litre jlask containing two moles of B 2 • how
heated in a sealed glass tube at 465°C and at equilibrium 30.8 mL many moles ofAB will be formed at 373 K?
of HI was formed. Calculate the percentage degree of Solution: . A2(g)+ B2(g) 2AB(g)
dissociation ofHI at 465°C. Initial no. of moles I 2 o
Solution: Since, the number of moles in a gas under the No. of moles at equilibrium ~ 1 x) (2 x) 2x
same conditions of temperature and pressure are proportional to (Total volume ~ 3 litre)
volumes (Avogadro's Law), the volumes in mL of gases may be (I-x) (2-x) 2x
used instead of concentrations in the case of reversible reactions Active masses
3 3 3
in which there is no change in the number of molecules of Applying law of mass action,
reactants and products.
Given, 2x 30.8mL [ABf ( 3 )2
2x
Kc == -,-----'-,,---:;.,-----,-
So, x== 15.4 mL
Vol. of H2 at equilibrium =(25.;.;; 15.4)= 9.6 mL
z
[A ][B 21 C3 ~)(~; x) . (l-x)(2-x)
VoL OfI2 at equilibrium (I8 -15.4) 2.6 mL 4x 2
But, ----=50
[HI] 2 (30.8)Z (1 x)(2-x)
Kc 38.0 or 4x 2 = (2 - 3x + x 2 )50
[H2 ][I z ] 9.6 x 2.6
or 2x 2 = (2 3x + XZ )25
Consider the equation, 2
or 23x
2HI(g) ~ H 2 (g) + 12 (g)
Let the degree of dissociation be x 75±
2 x= - - ' - - - - - - - -
K' == _ _
x __ 2x 2.3
c 4(1- x = 2.317 or 0.934
The value of x cannot be more than 1, i. e., greater than the
x
or number of moles of A2 and hence x = 0.943.
38 6.1644 2(1 x)
No. of moles of AB = 2x (2 x 0.934)
or x = 0.245, i.e.• 24.5% dissociated
1.868
Example 15. 3.2 mole of HI were heated in a sealed bulb
at 444°C till the equilibrium state was reached. Its degree of Example 17. The vapour density of N Z0 4 at a certain
dissociation was found to be 20%. Calculate the number of temperature is 30. CalCJ,llate the percentage dissociation of
moles of hydrogen iodide, hydrogen and iodine present at the N 204 at this temperature.
equilibrium point and determine the equilibrium constant. Solution: N 2 0 4 (g) 2NO z(g)
Solution: The dissociation of HI is represented by the equation,'
Mol. mass of N20~ == (28 + 64) =92
2Hl(g) H 2 (g) +I2(g)
(I-x) x/2 x/2 Vapour density, D = 92 = 46
Degree of dissociation; x == 0.20 and initial concentration of 2
HI, a == 3.2 mole. Let the degree of dissociation be x
At equilibrium, Given, d = 30
No. of moles of HI a(l-x) 3.2xO.8 2.56 . Applying the relationship,
a·x
No. of moles of H2 3.2x 0.1 0.32 x= D- d = (46- 30) = 16 0.533
2
d 30 30
a·x
No. of moles of 12 == - == 3.2 x 0.1 == 0.32
. 2 Degree of dissociation 53.3%
2
K = x . == 0.2xO.2 =00156 Example 18. 3 g mole of phosphorus pentachloride is
c 2 .
4(I-x) 4x 0.8x 0.8 heated in a flask of 4 litre volume. At equilibrium it dissociates to
K = [Hz ][1 2 ] == 0.32 x 0.32 give 40% ofphosphorus trichloride and chlorine. Calculate the
Also, equilibrium constant. . -.
c [HI]2 2.56x 2.56
0.0156
CHEMICAL EQUILIBRIUM 605
Solution: Degree of dissociation =: 0.4 ~xample 20. 1.0 mole of nitrogen and 3.0 moles of PCl 5
PCl 5 (g) ~ PCI 3 (g) + Cl 2 (g) are placed in 100 litre vessel heated to 227°C. The equilibrium
a(I x) ax ax (at equilibrium) pressure is 2.05 atm. Assuming ideal behaviour, calculate the
degree of dissociation for PCl s and K p for the reaction,
Given, a =: 3, x =: 0.4 and V = 4.
PCl s (g ) ~ PCl 3 (g) + Cl2 (g)
So, at equilibrium,
Solution: PCls (g ) ~ PC1 3 (g) + Ci l (g)
[PCI
5
] = 3(1 0.4) = 3 x 0.6 mol L-1 Initial 3 0 0
4 4 At equilibrium 3(l-x) 3x 3x
[PCI ] =: 3 x 0.4 mol L-1 (x = degree of dissociation)
3
4
Total moles = 3(1 x) + 3x + 3x = 3(1 + x)
[CI 2 ] = 3 x 0.4 mol L-1
.4 1 mole of nitrogen is present, hence actual total number of
Applying law of mass action, moles at equilibrium 3(1 + x) + 1
According to gas equation,
. K = [PCI 3 ][Cl z] 3 x 0.4 x 3 x 0.4 = 0.2 mol L-1
c [PCIs] 4x 3x 0.6 PV=nRT
Given, P =: 2.05 atm, V = IOOlitres, R = 0.082
Example 19. N 204 is 25% dissociated at 37°C and one
atmospheric pressure. Calculate (i) K p and (ii) the percentage and T = (273 + 227) 500 K
dissociation at 0.1 atmosphere and 37°C. n 2.05x 100 5
So,
Solutibn: (i) N Z0 4 (g) ..--2NOZ(g) 0.082x 500
Initial 1 0 or 3(l+x)+ 1= 5
At equilibrium (I-x) 2x 3x= 1 or X= 0.333
Total moles = (1 x) + 2x (l + x) Thus, 3(1 + x) + 1=: 3 + 3 x 0.333 + 1 4 + 0:999
2X 0.25'jx 1 O.4atm
( 1+ 0.25
Z
9x x 2.05 3 X (0.333)2 x 2.05
0.4 x 0.4
0.267 atm 3(3x+ 4)(l-x) (4 + 0.999)(0.667)
0.6
= 0.204 atm
(ii) Let the degree of dissociation of N Z0 4 at 0.1 atm be 'a.',
. then, Example21. For a gas reaction, 3Hz (g).+N 2 (g)
2NH 3 (g), th~ partial pressures of H 2 and N 2 are 0.4 and 0.8
PN 0 = (~J x 0.1 and PNO =: 2a. x 0.1 atmosphere, respectively. The total pressure of the entire system
2 4 1+ a. 2 (1 + a. )
is 2.8 atmosphere.. What will be the value of K p' if all the
concentrations are given in atmospheres?
2a.J2 X (0.1)2 Solution: i'~1 (g) + 3Hz (g) ~ 2NH3 (g)
( 1+ a. 4a. 2 x 0.1 0.4a. 2
Kp Partial pressures 0.8 0.4 [2.8 - (0.8 + 0.4) 1.. 6]
( I +a.
~J' x 0.1 (1- a. )(1 + a.) (1- a. 2) at equilibrium
Applying law of mass action,
1
0.267 0.4a. or 0.267 =: 0.667a. 2 K = (PNH3 )2 1.6 x 1.6
or p 3
(1-0.. 2 ) .. ( PN 2)(PH 2 ) 0.8 x 0.4 x 0.4 x 0.4
a. = 0.632 50atm-2
Hence, dissociation ofN z0 4 63.2%
'606 I " G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
x [2.9XIO-
4
S
f
/
3
0.0194atm
8.
Since, t!.n 0, hence, Kp == Kc]
A (g ) + 3B (g ) ~ 4C (g 1 initial concentration of A is equal
to that of B. The equilibrium concentrations of A and Care
Total pressure 2x + x 3x 3 x 0.0194 0.0582 atm equaLKc of the reaction will be:
Example 28. In an experiment starting with 1mole ofethyl (a) 0.08 (b) 0.8 (c) 8 (d) 80
alcohol, 1mole of acetic acid and 1 mole of water at IOCPC, the (e) 1/8
equilibrium mixture on analysis shows that 54.3% of the acid is [Ans. (e)]
esterified. Calculate the equilibrium constant of this reaction. [Hint: A(g) + 3B(g) ~ 4C(g)
Solution: t 0 a a 0
CH 3 COOH(l) + C 2 Hs OH(l) ~ CH 3 COOC 2 H5 (l) + H 2 0(l) teq. a x a 3x 4x
Initial 1 1 0 1 a - x == 4x given
At Ix I-x x l+x a 5x
equilibrium
1 0.543 K == [C]4 [4X]4 256 = 8]
1- 0.543 0.543 1 +0.543
c, [A][B]3 [4x][2x]3 32
Given, x 0.543.
Applying law of mass action, 9. For a hypothetical reaction:
[ester] [water] 0.543 x 1.543 = 4.0 4A(g) + 5B(g)...- 4P(g) + 6Q(g)
Kc The equilibrium constant K c has units:
[acid][alcohol] 0.4571< 0.457
(a) mol L -1 (b) mol- 1 L
Example 29. The equilibrium constant for the reaction,
(c) (molL -1)-2 (d) unitless
CH3 COOH(l) + C2H50H(l)~CH3COOC2Hs (l) + Hp(l)' [Ans. (a)]
is 4. What will be the composition of the equilibrium mixture
[Hint: Unit of Kc (mol L-1 )illl
when one mole ofacetic acid is taken along with 4 moles ofethyl
alcohol? = (mol L- 1 i = mol L- 1 ]
Solution: . 10. Starting with 1 mol of 02; 2 mol of S02' the equilibrium for
CH 3COOH(l) + C 2 lL;OH(l) ~ CH 3COOC2 lL;(I) + H 2 °(l) the formation of 803 (g) was established at a certain
Initial 1 4 0 0 temperature. If V is the volume ,of the vessel and 2x is the
number of moles of S03 present, the equilibrium constant will
At equilibrium 1- x 4 x x x
be:
[esterJ[water] x2 2 2
Kc 4 (a) x V (b) 4x
[acid] [akohol] (l-x)(4-x) (1- (2-x)(l-x)
x
2
=4(1- x)( 4 x) 2
(c) -"--.:...... (d) x
4[45x+x2] 2V (2-x)(1-x)
2
= 16 2Ox+ 4x [Ans. (a)]
or 3x 2 20x + 16 = 0 [Hint: 2S0 2 (g) + 02(g) ~ 2S0 3(g)
20±
to '2 1 0
x =-----''---.-- =- - - -
6 6
20± 14.42
'I eq, [2/X] [l;X] [~]
x= 0.93 or 5.7366 2
The value 5.7366 is not possible, he~ce x = 0.93 ,K = [S0 3 f = /V == xV ]
Thus, the composition of mixture at equilibrium is •. c [SOd[Oz] [2 V2x J [1/ J (1 x)3
[CH 3 COOH] = (1 0.93) = 0.07 mole
[C 2 Hs OH] = (4 - 0,93),= 3.07 mole 11. For the reaction, H 2 (g) + 12(g) " . ' 2ID(g), K =47.6, if the
[CH3 COOC 2Rs] 0.93 .mole = initial number of moles of each reactant and product is 1 mole,
[H 2 0] =0.93 mole then at equilibrium: [JEE (Orissa) 20061
(a) [1 2 ]=[H2 J;[I2 ]>[ID] (b) [1 2 ] < [H2 ];[I 2 ] [ID]
~'OF08JECTIVEQUE$TIONS (c) [1 2 ] [H2 ];[I 2] < [ID] (d) [1 2 ] > [Hz];[I21 =[ID]
[Ans. (e)]
7. For the reaction, N 2(g) + 02(g) ~ 2NO(g), the value of
Kc at ;:;JO°C is O.L When the equilibrium concentrations of
both the ,_:!c~'ints is 0.5 mol, what is the value of Kp at the
same temperature'? . (KCET 200S) [H 2 ] '" [1 2 ] will be same at equilibrium, since. it is same at initial
(a) 0.5 (b),O.1 (c) 0.01 Cd) 0.Q25 . state.
.[Ans. (b)] [HI] 2
Kc
[Hint: Kp = KARTi'"
608 G ..R,B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Kc [1 2 ] 2 =[Hl1 2
47.6 [12 ] 2 [Ill] 2
.. [12] < [Ill]]
12. In a closed vessel of volume V, a mol of nitrogen and b mol of
oxygen are made to react to give nitric. oxide, according to the
reaction:
2x
N 2 (g) + O 2 (g) ~ 2NO(g) I-x
If at equilibrium, 2xmol of NO are obtained, then: x 0.33
.[BV (Pune) 2006J
2 % ofH2 reacted = 33 ]
4x I
(a)K - x-
c - (a - x)(b x) V
4x2 . 9.8 LE CHATELIER'S PRINCIPLE
-----xV
(a -x)(b-x) There are three main factors which can change the state of
X
2
. equilibrium in a reversible system. These are concentration,
(c) Kc = xV pressure and temperature. Le Chatelier, a French chemist,
(a-x)(b-x)
. presented a quaJitative principle known as Le Chatelier's
(d) Kc ~ (a _:~: x)
principle which can . describe theeffect..... ofchangein---
concentration, pressure and temperature on any reversible system
[Ans. (d)] whether physical or chemical.
[Hint: N 2 (g) + 02(g)~ 2NO(g) According to this principle, if a system at equilibrium is
t= 0 abO subjected to a 'change of concentration, pressure or
b-xi 2x temperature, the equilibrium shifts in the direction that tends
V ( V .J V to undo the effect of the change.
Or
4x 2 If a system at equilibrium is subjected to a change of any
----] . one of the factors su,-:h as concentration, pressure or
(a - x)(b -x)
temperature, the system adjusts itself in such a way as to
aunul the effect of that change.
13. Equivalent amounts of H2 and 12 are heated in a closed till
(a) Change in concentration: If an additional amount of
equilibrium is obtained. If 80% of the hydrogen, can be any reactant or product is added to the system, the stress is
converted to HI, the K c at this temperature is: (V IT E E.E 2Oil7) relieved as the reaction that consumes the added substance occurs
(a) 64 (b) 16 (c) 0.25 (d) 4 more rapidly than its reverse reaction, i. e. , if any of the reactants
[Ans. (a)] .
is added, the rate of forward reaction increases and if any of the
[Hint: H 2 (g) + I 2 (g) ~ 21ll(g) products is added, the rate of backward reaction increases.
t= 0 110
In general, in. a chemical equilibrium, increasing the
1 - 0.8 1 - 0.8 2 x 0.8
. teq. concentrations of the reactants results in shifting the equilibrium
V VV
in favour of products while increasing concentrations of the
[
1.6 J2 products results in shifting the equilibrium in favour of reactants.
K = [Illf = V = 64] (b) Change in pressure: If a system in equilibrium consists
c[H 2][I2] 0.2 x 0.2 of gases, then the concentrations of all the components can be
V V altered by changing the pressure. When the pressure on the
14. Equimolar concentration of Hz and 12 are heated. to system is increased, the volume decreases proportionately. The
equilibrium in a 2 litre flask. At equilibrium, the forward and t;)ta\ 11lJ.mber of moles per unit volume will now be more thari
backward rate constants are found to be equal. What beforelAccording to Le Chatelier's principle, the equilibrium
percentage of initial concentration of Hz has reacted at will shift in the direction in which there is decrease in number of
. equilibrium? WMT C';;:n!ia) ZUOl1j moles, i. e., towards the direction in which there is decrease in
(a) 33% (b) 66% volume.
(c) 50% (d) 40% In general, an increase in pressure applied to a system at
(e) 20% equilibrium, favours the reaction in the direction that
[Ans. (a)] produces smaller number of moles of gases and a decrease in
[Hint: H 2 (g) + 12 (g) ~ 2Hl(g) pressure favours the opposite reaction. If there is no change in
to 0 number of moles of gases in a reaction, a pressure change does
"l-x 1 x 2x not affect the eqUilibrium. .
teq. -
2 2 2 (c) Change in temperature: A chemical reaction
(reversible) involves two opposing reactions, forward and
CHEMICAL EQUILIBRIUM 609
backward. If one reaction is endothermic, the other will be absorption of heat. The formation of HI is an exothermic
exothermic in nature. When heat energy is added by raising reaction. Thus, the backward reaction moves faster when
temperature, the system can relieve itself from the stress if the temperature is increaSed.
reaction which, absorbs heat moves faster, i. e., endothermic In short, we can say that the favourable conditions for greater
reaction is always favoured with increase of temperature. yield ofE1 are: .
Conclusions: (i) High concentrations ofH2 and 12 and
.. '
(ii) Low tempenltur~ .
(i) Increase in concentration of any substance favours the
(b) formation of qitric oxide:
reaction in which it is used up.
(ii) High pressure is favourable for the reaction in which there
N 2(g) + O 2 (g) , ;. 2NO(g) - 43200 cal
is decrease in volume. Effect of concentration:' ' When concentrationofN2 or 02
(iii) A rise in temperature favours the endothermic reaction.
is increasetl, the system moves in a direction in which N 2 or 0 3 is·,"
used up, i. e., rate of forward reaction increases thereby
(d) Role of catalyst: Positive catalyst increases the rate of
increasing the concentration of NO·. . . ',.
both forward and backward reactions equally; the equilibrium
will be attained in less time, i. e. , same amount of pre juct will be Effect of pressure: In the formation: of nitric oxide, the
formed in less time. number of moles remains the sam\l, i. e. , no c:hange in volume
On the other hand, negative catalyst lowers the rate of both occurs. Consequently, the equilibrium state is not affected by any
forward and backward reactions equally. Same amount of change in pressure.
product will be formed in more time. Effect of temperature: The formation of NO is endother-
Catalyst does not affect equilibrium cOnstant and heat of reaction. mic in nature. If the temperature is raised, the equilibrium shifts
in the direction in which heat is absorbed. The concentration of
Summary of LeChatelier's Principle NO will, therefore, be higher at higher temperature.
Effect of inert gas addition Thus, favourable conditions;!or. gre,ater yield of nitric oxide are:
r'-,-~·",·''-:----'''''''----'------cI----'''''''-- (i) High concentrations ofN2 -an.d O2 and
'COndition . Effect
! ,"
<,,'
JLi'v-o~'V'=Coristant
(ii) High temperature
II tJ.n= 0, +- veor -ve No effect (c) Dissociation of pels:
I tJ.V '* 0, V '* Constant
1 tJ.n = 0 No effect
PCls (g) ~ PCl 3 (g) + 'cl 2 (g) -15000 cal
i tJ.V '* 0, V '* Constant 'I tJ.n> 0 Forward shift
I tJ. V '* 0, V '* Constant
r ...._«_'"
,tJ.n < 0 Backward shift Effect of concentration: When 'concentration of PCls is
increased at equilibrium, the rate of forward reaction increases as
where, An number of gaseous moles of product - number of
to decrease the added concentration. Thus, more ofPCl 3 and Cl 2
gaseous moles of reactant are formed., ,','
Effect of temperato,re and pressure Effecf,<:cof ,.pressure: The volume increases in the
Effect of Air, Side with " Effed of " dissochition of PCls . When preS!,lure is lrn;.reased, the system
~!'Iature of reaction' increased fewer mole of increase in P moves in the directiOn in which 'there is decrease in volume.
"' temperature .gas. Thus, ·high pressure does not favour disso()iation ofPC Is.
1. Exothennic backward shift 0; neither no shift Effect of temperature: The dissociation of PCIs is an
" " 2. 'Exothermic bac:cwardshift -ve; right forward shift , endothermic reaction. Thus, increase of temperature favours the
~::. ' 3: Et;ldothe~c forward shift -ve; right forward shift dissociation.
4. Endothermic forward shift +ve; left backward shift , Thus, favourable conditions for dissociation of PCIs are:
5. Exothermic backward shift +ve; left backward shift
(i) Higl, concentration of PCl s ,
6. Exothermic backward shift ..eve; right forward shift
7, Endothennic forward shift +ve; left backward shift
(ii) Low pressure and
8. Endothermic forward shift +ve; left backward shift (iii) High temperature.
(d) Formation of ammonia:
Application of Le Chatelier's Principle N2 (g) + ?H2 (g) 2NH3 (g); IlH =- 22.4 kcall mol
(a) Formation ofOI:
(i) At high pressure reaction will shift in forward direction
H 2 (g) +I2(g) ~ 2HI(g) +3000 cal
to form more product.
Effect ofconcentriltion: When concentration ofH2 orI2 is
(ii) When concentration of N2 and H2 is raised or
increas~d at eq~iiibriu:m,;,the ~ystem moves in a direction which concentration " of NH3 is lowered, then again the
decreases the, concentration, i. e., the rate of forward reaction equilibrium shifts in forward direction to form more
increases thereby increasing the'concentration of81. ammonia.
Effect of pressure: As there is no;'Change in the number or If concentration of only one reactant is raised, then again
moles in the reaction, the equilim.1um state remains unaffected by the equilibrium shifts in forward direction till the other
change of pressure. reactant is available for reaction.
Effect of temperature: By increasing temperature, the
equilibrium state shifts towards the reaction which -moves with
I
610 R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(iii) The reaction shifts in forward direction at low temperature. [Hint: Reaction is endothennic and t:.n> 0, hence, the
But at very low temperature the rate of reaction becomes fonnation of product will be favoured by increasing the
very low; thus moderate temperature is favourable for temperature and decreasing the pressure.]
this reaction. 16. The exothermic fonnation of ClF 3 is .represented by the
equation:
9.9 APPLICATION OF LE CHATELIER'S CI 2 (g) + 3F2(g) 2ClF)(g); I1H = - 329 kJ
Which of the following will increase the quantity ofClF 3 in an
PRINCIPLE TO PHYSICAL EQUILIBRIA
equilibrium mixture ofCl z, F2 and ClF)? 1,\1) '::. :;::d:,,
(i) Solid Liquid ~ Gas (a) Increasing the temperature
(b) Removing Cl 2
When temperature is raised, the above equilibrium shifts in
(c) Increasing the volume of the container
forward direction.
(d) Adding F2
(ii) Effect of pressure on boiling point: When pressure is [AIlS. (d)]
raised, condensation of vapour takes place. Thus, vapour [Hint: Equilibrium will shift in forward direction by increasing
pressure is lowered. Now more heat is required to equate vapour he concentration of reactant.]
pressure with atmospheric pressur:e as a resuit of which boiling
17. Which among the following reactions will be favouredat low
point increases. .
pressure?
(iii) Effect of pressut:'e on melting point: There are two ta) N 2 (g)+
. types of solids: b) H 2 (g) +
(a) Solids whose volume decreases' on melting, e. g., ice, tc) PCls(g)
diamond, carborundum, magnesium nitride and quartz. (d) Nig) + 3H2 (g)
Solid (higher volume) ~ Liquid (lower volume) [Ans. (c)]
[Hint: On lowering the pressure, equilibrium favours the
The process of melting is facilitated at high pressure, thus direction of higher volume.]
melting point is lowered. 18. At constant pressure, the addition of argon to:
(b) Solids whose volume increases on melting, e.g., Fe, Cu, N2(g) + 3H2 (g) ~ 2NH3 (g)
Ag, Au, etc. will:
Solid (lower volume) ~ Liquid (higher volume) (a) shift the equilibrium in forward direction
(b) shift the equilibriumin backward direction
In this case the process of melting become difficult at high
pressure; thus melting point becomes high. (c) not affect the equilibrium
(d) stop the reaction
(c) Solubility of substances: When solid substances are
[Ans. (b)]
dissolved in water, either heat is evolved (exothermic) or heat is
[Hint: If volume is not constant, the addition of inert gas
absorbed (endothermic).
favours the direction where volume is increasing.]
KCl + aq. ~ KCl(aq.) - heat 19. The equilibrium reaction that is not influenced by volume
In such cases, solubility increases with increase in change at constant temperature is: ICE'! (.l&~~) 2llU(d
temperature. Consider the case of KOH; when this is dissolved, (a) H2 (g) + 12 (g) 2HI(g)
heat is evolved. (b) N2(g)+3Hz(g) 2NH)(g)
(c) N204(g)~ 2N02 (g)
KOH+ aq. ---'" KOH(aq.) + heal
(d) 2NO(g) + 02(g) 2N0 2 (g)
In such cases, solubility decreases with increase In [Ans. (a)]
temperature. [Hint: When, t:.n 0, there is no effect of pressure and volume
(d) Solubility of gases in liquids: When a gas dissolyes in change on the equilibrium.]
liquid, there is decrease in volume. Thus, increase of pressure 20. N2 (g) + 3H z(g) 2NH3 (g ) + Heat
will favour the dissolution of gas in liquid. What is the effect of the increase of temperature on the
equilibrium of the reaction ? ~ j,( 'V! 2lj(17~)
fUl1mATfONS OF OIJECTIVE QUESTIONS
(a) Equilibrium is unaltered
15. Consider the following reversible reaction at equilibrium: (b) Reaction rate does not change
2B2 0(g) 2H 2(g) + 02(g); I1H = + 24.7 kJ (c) Equilibrium is shifted to the left
which one of the following changes in conditions will lead to (d) Equilibrium is shifted to the right
maximum decomposition ofH2 0(g)? [Ans.(c)] .
(a) Increasing both temperature and pressure [Hint: The given reaction is exothemlic, therefore, the equilibrium
(b) Decreasing temperature a~d increasing pressure will shift in backward direction by the increase of temperature.]
(c) Increasing temperature and decreasing pressure
(d) Increasing temperature at constant pressure
(e) Increasing pressure at constant temperature
[Ans. (c)]
CHEMICAL EQUILIBRIUM 611
I-x
_.p 0.045atm-2
P AB Partial pressure of AB
l+x (ii) SinGe, [(I1 H7 )0 2x] 0.217
Applying the law of mass action, or - (nH 2 )0=0.217+2xO.08
= 0.377 mole
(/leoh 0.15
Total moles (flO) 0.377 + 0.15 0.527
170RT 0.527 x 0.0821 x 705
Rence, Po =-V-= 2.5
2 == 12.20atm
So, 4P -x_ . p
I x
2 Example 10. The equilibrium constant for the reaction,
2 2
or 4 4x =x CO(g) + H 20(g)---" CO 2 (g) + H2 (g),
I
CHEMICAL EQUILIBRIUM 615
at 986°C is 0.63. A mixture oflOlnole olwater vapour and 3.0 POl 2 + 0.0115 = 2.0115 atm
mole of co is allowed to come to equilibrium. The equilibrium
pressure is 2.0 atm.
PS03 =1 2 x 0.0115 = 0.977 atm
(i) How many moles of H 2 are present al eqllilibrium? Example 12. What is the concentration of co in
(ii) Calculate the partial pressures of gases ill equilibrium equilibrium at 25°C in a sample of a gas originally containing
mixture. : l i ~ ']'::; l.OOmoi of CO 2 ? For the dissociation olC02 at 25°C,
Solution: (i) In the given reaction, fj,n 0, hence, K C' K p Kc 2.96 X 10-92 .
CO(g) + H 1 0(g) ~ CO 2 (g) + H 2 (g) Solution: 2C0 2 (g) ~ 2CO(g) + 02 (g)
At equilibrium (3 x) (1 x) x x Atequilibrium (\ 2x) (2x) (x)
Applying law of mass action, Applying law of mass action,
__x_x_x__ = 0.63 2
K:: :1[COI x x (2x-f~ =? 96 x 10-92
(3 x)(I- x) c _.
. [C0 2 (1- 2yt
x2 0.63(3 4x + x 1 )
It can be assumed that 1 2x '" 1.0 as K c is very small.
2
0.37x + 2.52x - l.89 = 0 So, 4x 3 = 2.96 x 10-92
or + 6.81x 5.1 0
or X l.95xlO- 31 mol L- 1 .
x = .-6.81±
.- - - - = - - -x6.81-4x(-5.
- - - - - - - - ' - ' ' - - - = 0.68 mole Hz [CO] = 2x 2 x 1.95 X 10 31
2
3.90x 10-31 mol L- 1
(ii) Partial pressure of CO 2 = partial pressure of H2
Example 13. Ammonia is heated at 15 atmfrom 27°Cjo
= mole fraetion x total pressure
347°C assuming volume conslallt. Tile new pressure becomes 50
0.68 x 2 =03
=-- . 4 atm atm at equilibrium. Calculate % ol NH 3 actually decomposed.
4
Partial pressure of CO(g) = (3 0.68) x 2 = 1.16 atm Solution: Pressure of NH 3 at 27°C == IS atm
4 Pressure of NH3 at 347 0 C P atm
Partial pressure of H" O(g) = (1- 0.68) x 2 = 0.16 atm P 15
- 4
300 620
Example 11. The equilibrium constant K p for the 31 atm P
reaction, Let a moles of ammonia be present. Total pressure at
2S0 2 (g ) + 02 (g) 2S0 3 (g) equilibrium = 50 atm
is 900atm- 1 at 800K. A mixture containing S03 and 02 having 2NH 3 (g) ~ Nz(g) + 3H 2 (g)
initial partial pressure of I and 2 atm respectively is heated at At equilibrium (a-2x) x 3x
constant volume to equilibrate. Calculate the partial pressure of Total moles a - lx + x + 3x = a + 2x
each gas at 800K. .
Initial number of moles Initial pressure
Solution: The system in the initial stage does not contain
S02' S03 wiIl, thus, decompose to fonn S02 and 02 until Moles at equilibrium Equilibrium pressure
equilibrium is reached. The partial pressure of S03 will decrease. a
Let the decrease in partial pressure be lx. .
(a +
2S0 2 (g) + 02(g) ----'- 2S0 3 (g) 19
At equilibrium (2x) (2 + x) (1- 2x) x -a
62
Applying law of mass action, 19
(l_2X)2 Amount of ammonia deeomposed = 2x 2 x 19 a -a
K p =--,--- 62 31
(2xt(2+x) . 19x a
% of ammo 111 a decomposed == x 100
900 -'-1_---.:._ 31 x a
8x 2 = 61.3
or . 1- 2x = 84.85 Example 14. Calculate the per cent dissociation of
x H 2 S(g )ifO.l mole ofH 2 S is kept il1 OAlitre vessel atlOOOKfor
or x==O.01l5atm the reaction,
Thus, the partial pressures at equilibrium are: 2H2S(g)~ 2H2(g)+ S2(g)
Pso} 2 x 0.0115 == 0.023 atm The value of K c is 1.0 X 10-6 . .
616 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
. .
2
. . -[
2x ] 2( x \\
-p --p
K =(PAB) (PB 2)= (2+x) 2+xJ_.
or p 2 . 2
0.8(0.1 ( PAB 2) (2(1 X)pJ
. l(2+x)
asx is very small; 0.1- x -? 0.1
with a degree of dissociation, x, which is small compared with Since, x is very small, (1- x 2 )-? 1
unity. Deduce the expression for x in terms of the equilibrium . ,,-'. x2 0.1285
So,
constant, K p and the total pressure, P mT 199-l) 40
or x= 0.0566
CHEMICAL EQUILIBRIUM 617
(~,pr
'.
or x 34% dissociated
Solving fora. w~ get a = [1 + 3.J3
4 Kp
Lj- [/2
-
show that degree of dissociation of NH 3 is given
I"
CIS:
10gKI' =7.282-
8500
r
a= 1+
[ j
3.J3L-
4 Kp log 1= 7.282 _ 8500
T
where, ' p' is equilibrium pressure. (f K p of the above reaction is
78.1 atm at 400°C, calculate K (" T == 8500 = 1167.26 K
7.282
Solution:
= 894.26°C
NH3 (g) ~ ~ N2 + ~ H2 (g) Total moles
Example 26. Equilibrium constant for the reaction of
t 0 0 0 iodine with propane according to the following equation was
1- a a/2 3a/2 l+a determined.
te'l'
Some results obtained at 545 K were as given ahead:
Pi U+:)p ( a
l2(1+a)P
J (P; ~ partial
pressure)
I
CHEMICAL EQUILIBRIUM I 619
Example 31. At 817°C, K p for the reaction between Solution: 2NO(g)+ Clz(g) ~ 2NOCI(g)
CO 2 (g )and excess hot graphite( s) is 10 atm. t= 0 0.02 o o
(a) What are the equilibrium concentrations of gases at 0.02x 99 0.02 x 1
p
817°C and a total pressure of 5 atm? 100 100
(b) At what total pressure, the gas contains 5% CO 2 by
volume? (liT 2000)
(0.02 X 0.01)2 = 10-3
Solution: (a) CO 2 (g)+ C(s)~2CO(g) (0.99 X 0,02)2 x P
Atequilibrium (S-x)atm xatm . p = 0.102 atm
2
K = [CO]2 x
PV= nRT
p [C0 2 ] (5 x)
2 0.102 x V =n x R x T ... (i)
. 10= x
5-x 1x V = 0.2 x R x T ... (ii)
x 2 = 50-lOx From eqs. (i) and (ii), n 0.0204 (no. ofmoiesofCl 2 at
equilibrium)
+ lOx- 50= 0
Pressure of Cl z involved in reactioll
-lOi ~100+200 . """1 "
x= . = 3.66 = - x pressure of NOCI
2 2
i.e., Peo = 3.66atm; Peo2 1.34 attn 1 0.02
=- x 0.0001 atm
Concentration of CO = _---.,.3_.6_6_ _ 0.041 mol litre -I 2 100
RT 0,0821 x 1090 PV nRT
Concentration ofC0 2 = 1.34 =0.015 mol litre- I 0,0001 x V n x RT ... (iii)
. RT 0.0821 x 1090
From eqs. (ii) and (iii), n 2 x 10-5 (moles of Cl 2 involved
(b) CO 2 (g) + C( s) ~ 2CO (g )
in reaction)
I'" 0 0 0
5
I a' 20. Initial moles ofC1 2 taken 0.0204 + 2 x 10-
1"'1"
1- a. 20. = 0.02042 .
Pi -P P
1+ a. 1 + a.
Example 33. In the following equilibrium,
. [I-a
--p1
... (i)
Kp = 298 K, the total pressure was found to be 20 bar.
l+a Given: I:lG°
f Ni0 4 100 kJ, I:lGf°N02 = 50 kJ
5 I-a
- (a) Find I:lG of the reaction at 298 K.
100 l+a (b) Find the .direction of the reaction. (111' lO1l4)
a 0.95
') 0 4 X (0.95)2 Solution: Reaction Quotient [ PN0 2 f -= 100 __ 10
.. From eq. (1, 1 xP PN 2 0 4 10
. 1- (0.95)2
0 0 0
P = 0.27atm I:lG r~action 21:l G f N02 -I:lG f N2 0 4
(c) When there is a decrease in the number of molecules, (iii) Use of partial pressures: When the reactants and
i.e.,An ve. products are in gaseous state, the partial pressures can be used
3. Law of chemical equilibrium (Application of law of instead of concentrations at a definite temperature.
mass action): Consider the general homogeneous reversible ml Al + m2 A 2 + m3 A 3 + ... ~ nlB I + n2 B 2 + n3 B 3 + ...
reaction in which equilibrium has been attained at a certain ( )nl ( (
temperature. K : ----'----=----=----
p (
PAl
)"'1 ( PA2 )m2 ( PA3')m3
mlA I +m2~2 +m3 A 3 + ... ~nIBI +n2 B Z +n3 B 3 + ...
Kp : K c (RT l',tJ
Rate of forward reaction = Rate of backward reaction
where, An total number of molecules of products - total
t
k/ [AI ]"'1 [A2 ]'112 [A3 ]'113 ... : kb [HI tl [B2 ]"2 [B 3 3 ... , number of molecules of reactants.
I
622 .1 c:; A.B. PHYSICAL CHEMISTRY
., FOR COMPETITIONS
When, An = 0, K p = K c; x x
-x- 2'
An = + ve, Kp >Kc; "----"-:..::-...::..:::. =L L =__x __
and An - ve, K p < K c; (a-x) (a-x)V
(iv) Temperature: The value of equilibrium constant V
changes with temperature. The values of equilibrium constants at
measuring density of the reaction mixture at equilibrium. Let d be Applications of Le Chatelier's Principle
the obserVed density at a particular temperature when degree of (i) Ice water system (melting of ice):
dissociation is x and D be the vapour density when there is no
dissociation. Ice + Heat ~ Water
'f:r0_~M%1'[I]W•.
1. Match List I (Equations) with List II (Type of Processes) and (r) atm
(C)Hz(g)+lz(g) 2HI(g)
select the correct option:
List~1 List-II (d)Nz(g)+ 3H2(g)~ 2NH)(g) (s)(atm)-z
(Equations) (Type of Processes) [C] Match the reactions of the Column-I with the factors in
(a)Kp>Q (i) Non-spontaneous Column-II:
(b)6.Go< RTlogeQ (ii) Equilibrium Column-I Column-II
(c)Kp=Q (iii) Spontaneous and (a) N2(g} + 3H2(g) ..-- 2NH3(g) (p) Forward shift by
endothennic (Exothermic) rise in pressure
. (d)T > 6.H' (iv) Spontaneous (b)2S02(g) + °2(g) 2S03 (g) (q) Unaffected by
!lS (Exothennic) change in pressure
(A) a = (i); b (ii); c (iii)~ d (iv)
(B) a = (iii); b= (iv); c= (ii); d (i) (c) N 2 (g) + 02(g) 2NO(g) (r) Forward shift by
(Endothennic) rise in temperature
(C) a = (iv); b = (i); c (ii); d (iii)
(D) a = (ii); b (i); c (iv); d=(iii) teBS.,.; (PMT) 2010] (d)PCI 3 (g) + Clz(g) pels (g ) (S)F orward shift· by'
[Hint: When Kp > Q; rate offorward reaction> rate of backward (Endothermic) lowering the
reaction, i.e., process is spontaneous. temperature
When 6.Go < RT loge Q, 6.Go is positive, thus reaction is non [D] Match the reactions of the Column-I with the relations in
spontaneous. Column-lI:
When Kp = Q, reaction is at equilibrium. Column-I - Column-II
When TM > 6.H, 6.G will be negative only when 6.H = +ve, thus
is spontaneous and endothermic.] (a)H2(g)'+ I2(g).--" 2m(g) (P)K p = Kc(RT)
2. Matrix-Matching Problems (For lIT Aspirants): (b)N2(g) + 3H2 (g) 2NH3(g) (q)K p = Kc(RT)2
[A] M!)tch the Column-I with Column-II: .
(c)PCl5(g)~ PCI 3 (g)+ CI 2 (g) (r)K p K c (RT)-2
Column-I
,- Column-II
(d)NH4HS(s) . NH 3 (g)+HzS(g)(s)K p =K c
2HI(g) (P) Unaffected by
. inert gas addition [E] Match the List-I with List-II:·
CaO( s) + CO2 (g) (q) Forward shift by
L.ist-I List-If
rise in pressure (a)Q= K (P) Reaction is nearer to completion
and backward
shift by inert gas (b)Q < K (q) Reaction is not at equilibrium
addition (c)Q > K (r) Reaction is fast in forward direction
2NH3 (g) (r) Unaffected by (d)K >>> I (s) Reaction at equilibrium
increase ir.
pressure [FlMatch the List-I with List-fL
PC1 3(g) + C1 2 {g) (s) Backward shiftb,; .List-I List-U
rise in pres~ur" •. (Reaction) (KpIK,,,]
and forward !Shift
by inert gas
(P)(RT r2
addition (q)(RT )0
[B] Match the reactions in the C.Qlumn-I with the units of (r) (RT i/2
equilibrium constant in Coluinn~II: ,-
(s) (RT rl/2
Column-I Column-II .
(a) CaC03 (s) CaO(s) + COz(g) (P)mol L
(b)PCls(g) PCI J (g) + Clz(g) (q) Unitiess
I
CHEMICAL EQUILIBRIUM 625
1. (C)(a = iv);(b = i);(c = ii);(d iii) [D] (a-s); (b-r); (c-p); (d:"'q)
2. [A] (a-p, r); (b-p, r); (c-q); (d-s) [E] (a-s); (b-q, r); (c--q);(d-p)
[B] (a-p, r); (b-p,r); (c-q); (d-s) [F] (a-p); (b-q); (c-s); (d-r)
[C] (a-p, s); (b-p, s); (c-q, r); (d-p, r)
-~:::"-*:.:-':. -;
~,'"~-~~PRACTICE PROBLEMS. ..~ "·~·,.·,;·e . '.' -1~o:~j:'~T .~~;r ';~:':
1. Kc for the reaction, NH3(g) ~ 1I2N2 (g) + 3/2 H 2 (g), at [Ans. (a) 23.2 (b) 11.45 kPa (c) 0.0337 kPa]
298 K is 5.2 x 10-5 . What is the value of K c at 298 K for the 8. From the following data at 1000 K:
reaetion, COCI 2 (g) CO(g) + CI 2 (g); K J = 0.329
N2 (g) + 3H2 (g) 2NH3(g)?
2CO(g) + 02(g) 2C02 (g); K2 := 2.24 X 1022
[Hint: K~ for reaction 1/2Nz(g)+3/2H2(g)~NH3 is~, Calculate the equilibrium constant for the following reaction:
Kc
. 1 2COCI 2(g) + 2C0:i(g) + C1 2 (g)
I.e., 5
5.2 x 10- [Ans. 2.43 x 102l]
K e forthereaction,Nz(g)+ 3Hz(g) ~ 2NH3(g), will be= (K~)2 9. For the reaction, S02(g) + Y;02(g).,-- S03\g), Kp is
=[ 1 .]23.7XI08]
5.2 x 10-)
32 (atm)-lIzat 800 K and Mf for the reaction is -187.9 kJ
mol-I. Calculate its value at 900 K, if it is assumed that Mf
2. The value of K p for the reaction, remains constant over this range of temperature.
[Ans. 1.387 atm- 112 ]
2H zO(g) + 2CI 2(g) ~ 4HCl(g) + 02(g),
is 0.035 atm at 400°C, when the partial press\lfes are expressed 10. The equilibrium constants for the reaction,
in atmosphere. Calculate the value of K c for the same reaetion. N2 (g) + 0z(g) 2NO(g), at 1727°C and 2227 C are Q
[Ans. 6.342 x 10-4 mol L- J ] 4.08 x 10-4 and 3.6 x 10-3 respectively. Calculate the enthalpy
3. For the reaction,
change for the reaction. (Given, R := 1.987 caL)
2S0 3 (g) ~ 2S02 (g) + °2(g),
[Ans. 43273 cal)
the equilibrium constant Kc = 2.52 X 10- 2 at 27°C; calculate
11. Calculate the equilibrium constant (Kp) for the reaction,
K p' (Given, R = 0.082 litre-atm deg- 1 mol-I)
C(s) + CO 2 (g) 2CO(g), at 1300 K from the following
[Ans. 61.99 x 10-2] data: C(s) + 2H 2 0(g) ~ CO2 (g) + 2H2 (g);
4. If Kp for the reaction, N2 (g) + 3H2 (g) ~ 2NH3 (g), is Kp (1300 K) 3.9 atm
1.64 x 10-4 atm -2 at 400°C. What will be the equilibrium H 2 (g) + COz(g) CO(g) + H 2 0(g);
constant at 500°C, if heat of reaetion in this temperature range Kp (1300K) 0.7 atm
is 105185.8joule? [Ans. 1.91 atm]
[Ans. 1.44 x 10-5 atm] [CO]2 K [CO]2[H 20)2 x [Hd[C0 2 1
[Hint:
5. For the reaction, NZ0 4 \g) 2NOz(g), K p = 0.157 atm at [C0 2 l p(net) [H 2 12[C0 2 l" [H 2 0f
300 K. Calculate the value of Kc for the same reaction at the
=(0.7f x3.9]
same temperature.
[Ans. 6.38 x 10-3 mol L- J ] 12. The standard equilibrium constant for the reaction,
Yz
6. For the reaction, S02(g) + 02(g) ...--c- S03(g), the value PCIs(g) ~ PC1 3 (g) + C1 2 (g),
of Kc is 1.7 X 10 12 at 300 K. Calculate the equilibrium is 1.8 x 10-7 at 298 K. Calculate its I1Go value.
constants for the following reaetions at 300 K: [Ans. 38.49 kJ mol- 1]
2S02 (g) + 02(g) 2S03 (g)
13. For the equilibrium, Ag 2C03(s) ~ AgzO(s) + CO2 (g),
and S03(g) S02(g) + lf20 2 (g)
equilibrium constants are 3.98 X 10-4 and 1. 41 x 10-2
[Ans. 2.89 x 1024 ,5.88 x 10-13]
respectively at 350 K and 400 K. Calculate the standard
7. Determine Kp for the following reactions: enthalpy of decomposition.
(a) CO(g) + HzO(g) COz(g) + H 2(g); [AilS. 83.06 kJ/mol]
. Kc 23.2 at 600 K 14. The equilibrium constant for the reaction,
(b) N2 0 4 (g) ~ 2N02(g); 4.62 x 10-3 M at 298 K Nz(g) + 3H2 (g) ~ 2NH3 (g),
(c) 2S02 (g) + 02(g) ~ 2S0 3(g);
Kc == 2.8 X 102 M -1 at 1000 K
626 G.A.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
at 715 K is 6.0 X 1O~2. If in a particular reaction, there are 0.25 23. In the dissociation of HI, it is found that 20% of the acid is
1 1
mol L- ofH2 and 0.06 mol L- ofNH 3 present, calculate the dissociated when equilibriilmis reached, Calculate the value
of K p for the equilibrium,
concentration ofN 2 at equilibrium.
2HI(g) ~ H2(g) + I 2(g)
[Ans. [N 2 ] =3.84 mol L- 1]
[Ans. Kp == 1.56 x 10- 2]
15. One mole of H20 and one mole of CO were heated in a 10 litre
24. The equilibrium constant of the reaction,
closed vessel at 1260 K. At equilibrium, 40% of water was
found to react in the equation, A +B~C+D
H20(g) + CO(g) ~ H2(g) + CO 2(g) is unity. What per cent of A will be transformed ifthree moles
of A are mixed with 5 moles of B?
Calculate the equilibrium constant of the reaction.
[Ans. 0.44] . [Ans. 62.5%]
[Hint: H 2 0Cg) + CO(g) ~ C0 2 Cg) + H 2 Cg) [Hint: At equilibrium,
(1- 0.4) (1- 0.4) 0.4 0.4 A + B ~ C+D
(3 - x) (5 - x) x x
(at equilibrium)]
x
16. Two moles of PCI s were introduced in a 2 litre flask and Find the value of x. % of A transformed == .::... x 100]
3
heated at 600 K to attain equilibrium. PCl, was found to be 25. 2 moles of A and 3 moles of B are mixed and the reaction is
40% dissociated into PCI 3 and C1 2. Calculate the value of KG'
carried at 400°C according to the equation,
[Ans. KG = 0.267 mole L- 1]
A +B~2C
17. 0.1 mole of PC 15 is heated in a litre vessel at533 K. Determine
the concentration of various species present at equilibrium; if the equilibrium constant of the reaction' is 4. Find the
the equilibrium constant for the dissociation of PCIsat 533 K concentration of C at equilibrium.
is 0.414. [Ans. 2.4 mole]
[Ans. [PCIs ] = 0.0531 mol L- 1; [PCI 3 ] = 0.0469 mol L- 1; 26. A combination of hydrogen and iodine is carried out by
heating 60 mL of hydrogen and 42 mL of iodine in a closed
[CI 2 ] = 0.0469 mol L- 1 ]
vessel. At equilibrium 28 mLaf hydtoiodic acid is present in
18. At 1000 K, the equilibrium constant, Kc, for the reaction, the vessel. Calculate the degree of dissociation of HI.
CO(g) + Clig) ~ COCI 2 (g)
[Hint: H 2 Cg) + I2Cg) ~ 2HICg)
is equal to 3.04. If 1 mole of CO and 1 mole of CI 2 are At equilibrium (60 - 14) (42 -14) 28 mL
introduced into a 1 litre box at 1000 K, what will be the final
concentration of COCI 2 at equilibrium? K = 28 x 28 ==~
[Ans. [COCI 2] = 0.568 mol L- 1 ] c 46 x 28 23
19. Given, that KG = 13.7 at 546 K for 2HI(g) ~ H 2 (g) + Il(g)
1- x x/2 .1'/2 (.\ is ·he degree of 'iation)
PCIs(g) ~ PCI 3 (g) + CI 2(g), calculate what pressure will
develop in a 10 litre box at equilibrium at 546 K when 1.00 K' = .. /2 xx/2 =_ "
On mixing the two, the reaction sets in at a slow fate to form C K _ (3 + 2xi _
c - - 45.9,
andD. (I-x)(2 -x)
A+B~C+D
At equilibrium, concentration ofC was found to be 0.60 mol On solving, x = 0.684 mole]
L- 1. Calculate the· equilibrium constan!. 28. Four moles of hydrogen iodide were taken in a 10 litre flask
kept at 800 K. When equilibrium was attained, the mixture
[Ans. KG =9]
was found to contain 0.42 mole of iodine. Calculate the
22. IS moles of hydrogen rea~ting with 5.2 moles of iodine form
equilibrium constant for dissociation of HI.
109 mole of hydrogen.! iodide. Calculate the equilibrium
[Ans. Kc = 1.76 x 10-2]
constant of the reaction.
29. The equilibrium constant, Kc, for the reaction,
[Ans. Kc = 50]
H2(g) + 12(g) ~ 2HI(g)
is 56.8 at 800 K. When the mixture was analysed, it was found
CHEMICAL EQUILIBRIUM 627
to contain 0.316 moUL HI at 800 K. What are the 36. At 3000 K, chlorine gas dissociates into chlorine atoms in an
concentrations of H2 and 12 at equilibrium? (Assume that equilibrium reaction for which K = 0.37. What is the
initial concentrations ofH2 and 12 were the same.) concentration of chlorine atoms in a vessel that originally
[ADs. [H 2 ] = [12 ] = 0.0419 mol L- 1 ] contained 1.0 mol L -I of molecular chlorine?
30. At same temperature and under a pressure of 4 atm, PCI s is [ADS. [el] = 0.54 mol L- 1 ]
10% dissociation. Calculate the pressure at which PCI s will be 37. The equilibrium constant K p for the reaction,
20% dissociated, temperature remaining same. (lIT 1996)
[Ails. 0.96 atm]
N 2(g) + 02(g) ~ 2NO(g)
31. The reaction of the formation of phosgene gas from CO and at 1500°C is 120. IfN z and 02 at an initial pressure of 0.25 atm
CI 2 is as follows: each are maintained at 1500°C till equilibrium is established,
CO(g) + CI 2(g) ~ COCI 2(g) calculate the partial pressure.. of N 2, 02 and NO in the
In an experiment, starting with equimolecular CO and CI 2 in a equilibrium mixture. '
250 mL flask, the equilibrium mixture on analysis is found to [ADS. PN z = POz = 0.04; PNo = 0.42 atm]
contain 0.05 mole CO, 0.05 mole Cl z and 0.15 mole COCI 2.
38. Find K p for the following reaction,
Calculate the equilibrium constant of the reaction.
[ADs. Kc = 15 mol- 1 L] S02CI2(g) ~ S02(g) + CI 2(g)
32. At 35°C and I atmospheric pressure, N20 4 is 27.2% If sulphuryl chloride decomposes to the extent of 91.2% at
dissoCiated into N02. What is the value of Kp under these 102°C and total pressure 1. atmosphere.
conditions? [ADS. Kp = 4.94 atm]
[ADs. Kp = 0.3195 atm]
39. If carbon dioxide is 2% dissociated at 1800°C and I
33. Nitrogen and hydrogen are added to a 5 litre flask under
atmospheric pressure,
pressure. The flask was sealed and heated. The equilibrium
mixture contained 19.0 gofammonia, 0.16 g of hydrogen and 2C02(g) ~ 2CO(g) + 02(g)
304 g of nitrogen. Calculate the equilibrium constant, Kc, of Calcul~e K p for the reaction.
the reaction: [ADS. Kp = 4.12 X 10-6 atm]
N 2(g) + 3H2(g) ~ 2NH3(g) 40. At a certain temperature, Kc for the reaction,
[ADs. Kc = 5.02 X 105 mol-2L 2]
34. An equilibrium mixture at 300 K contains N20 4 and N02 at POC1 3(g) ~
POCI(g) + CI 2(g)
0.28 and 1.1 atm pressures respectively. If the volume of the is 0.30. If 0.6 mole ofPOCl 3 is placed in a closed vessel of3.0
container is doubled, calculate the new equilibrium pressure of litre capacity at this temperature, what percentage of it will be
the two gases. (lIT 199'1) dissociated when equilibrium is established?
[HiDt: N 2 0 4 (g) ~ 2N0 2 (g) [ADS. 68.5%]
Kp = %oj = (1.1i = 4 .32 atm 41. A reaction carried out by I mole of N2 and 3 moles of Hz
%2 04) 0.28 shows at equilibrium the mole fraction of NH3 as 0:012 at
500°C and total pressure 10 atmosphere; calculate K p' Also
When the volume is doubled, the pressure becomes half and the
report the pressure at which mole percentage of NH3 in
system again adjusts to achieve equilibrium.
equilibrium mixture increased to 1004.
N 2 0 4 (g) ~ 2N0 2 (g)
[ADS. Kp = 1.431 X 10-5 atm- 2 ; P = 105.41 atm]
0.28
( -2- - x
J(1.1
-+ 2 x J 42. The degree of dissociation of N 20 4 into N0 2 at one
2 atmosphere and 40°C is 0.310. Calculate its K p at 40°C. Also
report degree of dissociation at 10 atmospheric pressure at the
(0.14 - x) (0.55 + 2x)
2 same temperature.
K = (0.55 + 2x) = 4.32 [ADS. Kp = 0.425 atm; degree of dissociation = 0.1025]
p (0.14-x)
43. The vapour density of PCIs at 200°C and 252°C are 70.2 and
x = 0.045 57.2 respectively at one atmosphere. Calculate its value of
PN 20 = (0.14 - 0.045) = 0.095 atm dissociation constant at these temperatures.
4
PN0 = (0.55 + 2 x 0.045) = 0.64 atm]
2 [ADS. Kp = 0.307, 1.19]
35. At 21.5°C and a total pressure of 0.0787 atm, N20 4 is 48.3% 44. Some solid NH4 HS is placed in a flask containing 0.5 atm of
dissociated into N02. At what total pressure will the per cent NH 3. What would be the pressures of NH3 and H 2S when
dissociation be 1O.0%? . equilibrium is reached?
[ADS. 2.37 atm]
[HiDt: First calculate the value of Kp ~nd then evaluate the
_ N.JI4 HS(s) ~ NH3 (g) + H2 S(g); K p = 0.11
pressure by applying, [AilS. NH3 =0.83 atm; H2 S =0.33 atm] ("'lL~R 1994)
[Hint:
' ( 0.2 J2 p2
K = 1.1 = 0 0959] At equilibrium x+ 0.5 x
p (0.9J p . Kp = (x + 0.5)x = 0.11 J
1.1
628 G.R.s. PHYSICAL CHEMISTRY FOR COMPETITIONS
45. Sn02(s) + 2H2(g) .,.-- 2HZO(steamj + Sn(s) The value of x cannot be more than 0.2 as Brz is a limiting
For the above reaction find K P' if at 900 K, the equilibrium reactant. Thus, when reaction is complete,
mixture contains 45% Hz by volume. H2 =(0.6 - 0.2) = 0.4 mol; Brz 0; HBr 0.4 mol
[Ans. Kp 1.5] At this point some HBr will dissociate.
46. The equilibrium constant for the reaction is 9AO at 900°e. 2HBr(g) H 2 (g) + Br2(g)
At equilibrium (OA - 2x) (OA + x) (x)
S2(g) + C(s) ~ CS 2 (g)
Calculate the pressure of two gases at equilibrium, when 1.42
atm ofS2 and excess ofC(s) come to equilibrium.
[A,ns. == 1.28 atm; PS2 '" 0.14 atm] o.4x
or 2 x 1O-IO(since, x is very small)
47. For the'reaction, 0.4
. CaC0 3 (s) ~ CaO(s) + CO;(g)
or
K P 1.16atm at SOO°C. If20.0 g ofCaC03 were kept in a 10
litre container and heated up to 800°C, what percentage of [Br2 ] = 2 x 10- 10 mql; [H 2 ]= 0.4 mol; [HBr] = 0.4 mol]
CaC03 would remain unreacted at equilibrium? 52. One mole of H 2 , two moles OfI2 and three moles of HI are
[Ans. 34%] injected in a 1 litre flask. What will be the concentration of
[Hint: K p Pco 2 = 1.16 atm H 2 ,I 2 and HI at equilibrium at 490°C? The equilibrium
constant for the reaction at 490°C is 45.9. .
n= xV Ll6x 10 == O.132inol
RT 0.0821 x IOn [Ans. [Hz] = 0.316; [Iz ] l.316; [ID] =4.36 mol]
.. I 20.0 I
I mba amount of CaC0 3 =-- == 0.2 mo 53. Solid ammonium carbamate dissociates to give ammonia and
100 carbon dioxide as follows:
Unreacted CaC0 3 = 0.2 - 0.132 NH2 COONH4 (s) 2NH 3 (g) + CO 2(g)
= 0.068 mo\ At equilibrium, ammonia is added such that partial pressure of
0.068 NH3 now equals to the original total pressure. Calculate the
% unreacted CaCO, = - - x 100 34]
. 0.2 ratio of total pressure now to the original total pressure.
48. In the reaction, C(s) + CO 2 (g) ~ 2CO(g), the equilibrium [Ans. 3li7]
pressure is 12 atm. If 50% of CO2 reacts, calculate K p- 54. Two solid compounds A and C dissociate into gaseous product
[Ans. Kp 16 atm] at temperature T as follows:
49. A rnixture of 0.373 atm of NO(g) and 0.310 atm of (i) A(s)~B(g)+D(g)
(ii) C(s)~E(g)+D(g)
CI 2(g) is prepared at 500°e. The reaction,
2NO(g) + Cl 2 (g) ~ 2NOCI, occurs. The total pressure at At 20°C, pressure over excess solid A is 50 atm ' that over
excess solid Cis 68 atm. Find th", tote' nreSSUfC ~ gas""
equilibrium is 0.544 atm. Determine Kp of the reaction.
over the solid mixture.
[Ans. Kp 50.08 atm- I ]
[Ans. 84.38 atm]
50. For the reaction, 55. Variation of equilibriu' onstant K with temperature l' is
3A(g)+B(g)~ 2C(g) given by van't Hoff eqL. In,
at a given temperature, Kc is 9.0. What must be the volume of 1:Jf0
a flask if the mixture of 2.0 moles each of A, Band C is log K log A - -'----
2.303RT
obtained at equilibrium?
[Ans. V 6 litre 1 A graph between log K and T -1 was a straight line as shown
51. At 700 K hydrogen and bromine react to form hydrogen in the figure and having e
== tan -1 (0.5) and OP = 10.
bromide. The value of equilibrium constant for this reaction is . Calculate:
5 X 108 . Calculate the amount of Hz. Br2 and HBr 'at (a) 1:Jf0 (standard heat of reaction) when T == 298K,
equilibrium if a mixture of 0.6 mole of H2 and 0.2 mole of (b) A (pre-exponential factor),
bromine is heated to 700 K. (TIT 1995) p
[Hint: H2 (g) + Br2(g) ~ 2HBr(g)
Initial 0.6 0.2
Since, equilibrium constant is very high the reaction will be
complete and bromine is cO;Isumed.
Thus, 0.2 mole of Br2 and 0.2 mole of H2 will be consumed to
produce 0.4 mole ofHBr. This can be ¢alculated by applying law
of mass action. . o T-1
4x" ( c) Equilibrium constant K at 298 K,
Kor------
(0.6 - x)(0.2 x) (d) K at 798 K, if I1Ho is independent oftemperature.
x = 0.6 or 0.2 [Ans. (a) 9.574 J mol-I; (b) A = lOlO; (e) 9.96 x 109;
(d) 9.98 x 109 ]
CHEMICAL EQUILIBRIUM 629
/:;}f0
[Hint: (a) log K. log A - 2.303RT teq [O.1l~-2X] [0.1l~8-X] 2,X
It is equation of straight line of the type y = c + mx 2x 0.0824
/:;}f0
[NO] 0.112 - 2x
Slope'm' tan e=
2.303R 0.112 - 0.0824 = 0.0296 M
/:;}f0
0.5=---- [Br2 ] =0.1138 - 0.0824 '" 0.0726 M
2.303 x 8.314 2
!1H" = 9.574 J mor J [NOBd ~~=106.74]
(b) Intercept' c' = log A 10 (NO]2[BrzJ [0.0296]2[0.0726]
A = 10JO 57. Solid ammonium carbamate is put into a closed container and
allowed to come to equilibrium with the gaseous products at
(c) logK=IO 9.574 35°C, the total pressure is found to be 0.30 atmospheres. What
2.303 x 8.314 x 298 is the value of K p for tbis reaction at 35°C?
K = 9.96 X 109 [Ans. 4 x 10-3]
(d) IOgl~~J 2.~R (;J -;J 58. K p for the equilibrium of,
FeO(s) + CO(g) Fe(s) + COi(g)
atlOOO°CisOA03, if CO(g),at a pressure·of·l.Oatm arid-
9.574 .excess ofFeO(s) are placed in a container at 1000°C. What are
log-~"---;;-
9.96 x 2.303 x 8.314 the pressures of CO(g ) and CO2 (g) when the equilibrium is
attained?
On solving, K z =9.98xI09 ]
fAns. Pco 0.713 atm; Pco 2 = 0.287 atm]
56. When 0.1 12 mole of NO and lS.22g of bromine are placed in
59. A mixture of 1.0 mole qf sulphur and 0.2 mole of hydrogen is
a 1.00 L reaction vessel and sealed, the mixture is heated to
heated at 90°C in a one litre flask. The equilibrium constant
350 K and the following equilibrium is established:
for the formation of hydrogen sulphide,
2NO(g) + Br2(g) 2NOBr(g)
HzCg) + S(s) ~ H2S(g) is 6.8 x 10-2 . Calculate the partial
If the equilibrium concentration of nitrosyl bromide is 0.OS24
pressure ofH2 S at equilibrium.
11, what is Kc?
fAns. PH 2s 0.397 atm]
fAns. 106.74]
[Hint: [Hint: First determine the initial pressure of Hz by applying
18.22
2NO(g) + Brz(g) 2NOBr(g); nBr = - - 0.1138 n
2 160 Po = . RT = 5.953 atm]
t 0 0.1'2 0.1138 o V
ESTIONS
(b) The reactants are present in the initial stage but after that
8et-1: Questions with single correct answer the reactants and products are always present in the
1. A reversible reaction is one which: reaction mixture
(a) proceeds in one direction (c) At equilibrium only products are present
(b) proceeds in both directions (d) When the reaction is carried out in closed space, it attains
(c) proceeds spontaneously equilibrium state after suitable time
(d) all the statements are wrong 5. The law of mass action was proposed by:
2. An example of reversible reaction is: (a) Guldberg and Waage (b) Le Chatelier and Braun
(a) Pb(NO)h + 2NaI = Pbl z + 2NaNO) (c) Kossel and Lewis (d) van'tHoff
(b) AgNO) + HCl AgCI +. RNO) 6. The rate at which a substance reacts, depends on its:
(c) 2Na + 2H2 0 = 2NaOH + H2 (a) activemass (b) molecular mass
(d) KN03 + NaCI = KCl + NaN03 (c) equivalent mass (d) total volume
3. Which one of the following is not a reversible reaction? 7. Active mass is defined as:
(a) 2HI(g) = H2(g) + Iz(g) (a) number of g equivalent per unit volume
(b) PC!s(g) = PCI 3 (g) + CI 2 (g) . (b) number of g mol per litre
(c). 2KCI03(s) = 2KCl(s) + 302 (g) (c) amount of substance in gram per unit volume
(d) CaC03(s) = CaO(s) + CO2 (g) (d) number of g mole in 100 litre
4. ·Which one is not correct for a reversible reaction? 8. 8.50 g ofNH3 is present in 250 mL volume. Its active mass is:
(a) The reaction is never completed (a) LOM L- 1 (b) 0.5M (c) I.5M (d) 2.0ML- 1
630 G.R.B. PHYS1CAL CHEMISTRY FOR COMPETITIONS
9. Theqry of 'active mass' indicates that the rate of a chemical . are K 1 and K 2 respectively. The relationship between
'reaction is directly proportional to the: IPET (MP) 1990] K, and K2 is:
(a) equilibrium constant (b) properties of reactants (a) K, =K 2
(c) volume of apparatus (d) concentration of reactants (c) K,2 =K 2
10. The state of equilibrium refers to: jPMT \ Ph.} 19931
(a) state of rest (b) dynamic state 19. The equilibrium constant for the given reaction is 100.
(c) stationary state (d) state of inertness N 2 (g) + 202 (g) ~ 2N0 2(g)
.n.. In a reversible chemical reaction equilibrium is said to have What is the equilibrium constant for the reaction given below:
been established when the: 1
N0 2 (g) 2 N2 (g)+02(g)
(a) concentrations of reactants and products are equal
(b) opposing reactions cease (EAMCET 2009)
(c) speeds of opposing reactions become equal (a) 10 (b) 1
(d) temperatures of opposing reactions are equal (c) 0.1 (d) 0.01
12. A chemical reaction, A B, is said to be in equilibrium 20. For the reaction, 2N0 2(g) 2NO(g) + 02(g),
6
when: Kc 1.8 x 10- at 185°C. The value of Kc at 185°C for the
(a) rate of forward reaction is equal to rate of backward reaction;
reaction NO(g) + !.02(g),.....:.....::. N0 2(g) is: (MLNR 1993)
(b) conversion of A to B is only 50% complete (a) 0.9 x 106 2 (b) 1.95 x 10-3
... (c) complete conversion of A to 'Bhastakenplace
(d)' only 25% conversion of A to B has taken place (c) 1.95 X 103 Cd) 7.5 x 102
13. The reaction between barium chloride and sodium sulphate goes 21. The equilibrium constant for the synthesis of HI at 490°C is
to completion because: 50.0. The value of K for the dissociation of HI will be:
(a) barium sulphate is almost insoluble (liT 1990)
(b) the solubilityofbarium~hloride decreases (a) 0.02 (b) 50.0 (c) 0.50 (d) 0:20
(c) lattice energy of barium sulphate is very high 22. Consider the following cquilibrium,
(d) the reactIon is irreversible in nature
1
14. What is the equilibrium constant expression for the reaction, S02(g) + 202(g) S03 (g);
P4(S) + 502(g)~ P40 JO (s)?
K2
(.Illmia \Jillia Islamin Engg. Ent. 2007; l'PSEE 2(07) 2S03(g)~ 2S0 2 (g)+ 02(g)
(a) Kc [P4 0 IO ] (b) K = [P4 0 IO ]
What is the relation betwecn K\ and K 2? [PET (MP) 1993]
[P4 ] [02 ]5 c 5 [P4 ] [02]
1 1 1
(a)K\ = (b)K] ~(c)K] K2
(c) Kc = [02 ]5 (d) Kc = 1 K2 'ljK2
[°2
23. ·For the reaction AB(g)~ A(g)+ B(g1 AB is 33%,
15. Equilibrium constant for the reaction,
.clissoGiated ata,;tptal pressun: of?' Theryfor~, P is related to
H 2 (g) + I 2(g) ~ 2Hl(g), is correctly given by the
expression:
j( if bX·0-qe:~Qtt~~foI19wjngoptio.n>· .... 'JAl.\1iU (Med.) 2010]
(a) P = K p (b) P == 3K p
(c) P 4Kp (d) P 8K p
[Hint: '. AB(g) A(g) +B(g)
25. The equilibrium concentrations of x, yand yX2 are 4, 2 and 2 [Hint: Fe3- + SeN ~ FeSCN:+
. respectively for the equilibrium 2x + y ~ YXz, The value 3.1 3,2 0
of equilibrium constant, K (' is: (EAMCET 1990) OJ 0.2 3
(a) 0,625 (b) 6,25 (c) 0.0625 (d) 62.5
'26. 4 mole of A are mixed with 4 mole of B when 2 mole of Care 2
fOllned at equilibrium, according to the reaction,
K = [FeSCN + J
A+B C+D c [Fe3+ ][SCN]
the equilibrium constant is: . (CPMT 1992) 3
150]
(a) ..fi (b) 2 (c) I (d) 4 0.1 x 0.2
27. If the equilibrium constant of the reaction 2HI(g) ~ H 2 (g) 36. K p and K ~ are the equilibrium constants of the two reactions,
+ 12 (g). is 0,25, the equilibrium constant of given below:
H2 (g) + 12 (g) ~ 2HI(g), under similar conditions, will be: ~N?(g)+~H?(g)~
2 - 2-
NH3(g)
(a) 4.0 (b) 3.0 (c) 2.0 (d) 1.0
28. HI was heated in a sealed tube at 400°C till the equilibrium N2 (g) + 3H2 (g ) ~ 2NH3 (g )
was reached. HI was found to be 22% decomposed. The Therefore, K p and K~ are related by \AMU (PMT) 2009)
equilibrium constant for dissociation, is: (a) == K~2 (b) K p .JK;;
. (a) 1.99 (b) 0,0199 (c) 0.0796 Cd) 0.282
29. For a reversible reaction if the concentrations ohhereactants
are doubled at a definite temperature, then equilibrium
constant will: (CPMT 1990; MLNR 1992) 37. In which of the following equilibrium K c and K p are not
(a) also be doubled (b) be halved equal? rCBSE (PMT) 20)01
(c) become one-fourth (d) remain the same (a) 2NO(g) ~ N1 (g) + 02(g)
. 30. In a reversible gaseous system, molar concentrations (active (b) S02(g)+N02(g)~ S03(g) + NO(g)
. masses) of reactants and products are proportional to: (c) H 2 (g)+I 2 (g) 2HI(g)
(a) partial pressure (d) 2C(s) + 02(g) ~ 2C02 (g)
(b) total pressure 38. .select the COll'ect statement from the following:
i( a) equilibrium constant changes with addition of a catalyst
(c) amounts' of reactants and products
(b) catalyst increases the rate of forward reaction
(d) none of the above
(c) the ratio of mixture at equilibrium does not change by
31. At 3000 K, the equilibrium partial pressure of CO 2 , CO and
catalyst
O2 are 0.6, 0.4 and 0.2 atmospheres respectively. K p for the
(d) catalysts are active only in solution
reaction,
39. In which of the following, the reaction proceeds towards
2C0 2 (g ) 2CO(g ) + O2 (g ) is : completion? (MLNR 1990)
IBHU (Mains) 20101
(a) K=! (b) K=10-2
(a) 0.088 (b) 0.0533 (c) 0.133 (d) 0.177
32. Equilibrium constant depends on: (c) K = 10 (d) K 103
(a) the actual quantities of reactants and products 40. For the following reaction at 250°C, the value of K c is 26, then
(b) the presence of a catalyst the value of K p at the same temperature will be:
(c) temperature PCI 3(g) + CI 2 (g) ..-- PCI 5 (g) (MLNR 1990; CBSE 1993)
. (d) the presence of inert material . (a) 0.57 (b) 0.61 (c) 0,83 (d) 0.91
33. For the reaction, H2 (g) + 12(g) ..-- 2HI(g), the equilibrium 41. In the reaction, PCI5 (g) ~ PC1 3 (g) + CI 2 (g), the amounts
constant, K P' changes with: of PC Is, PCl 3 and Cl 2 are 2 mole each at equilibrium and the
(a) total pressure 'tota.l pressure is 3 atmospheres. The equilibrium constant, K p'
(b) catalyst is: (liT 1991)
(c) the amounts ofH 2 and 12 taken (a) 1 atm (b) 2 atm (c) 3 atm (d) 1.5 atm
(d) temperature
42. In which of the following K p is less than K c?
34. 2HI(g ) ~ Hz (g ) + 12 (g)
(a) N2 0 4 (g) --->. 2N0 2 (g)
The equilibrium constant of the above reaction is 6.4 at 300 K.
If 0.25 mole each of H2 and 12 are added to the system, the :(b) 2HI(g) ~ H 2(g) + 12(g)
equilibrium constant will be: (CET Karnataka 2009) (c) 2S0 2 (g) + 02(g) ~ 2S0 3 (g)
(a) 0.8 (b) 3.2 (c) 1.6 (d) 6.4 (d) PC15 (g) --->. PCl 3(g) + CI 2 (g)
35. 3.1 mol of FeCI 3 and 3.2 mol of NH4 SCN are added to one
43. For a reversible reaction, the rate constants for the forward and
litre of water: At equilibrium, 3.0 mol of FeSCN2+ an" formed.
backward reactions are 2.3'8 x 10-4 ,tr,;j 8.15 x 10-5
The equilibrium constant Kc of the reaction:
respectively. The equilibrium constant for the reaction is:
Fe3+ + SCN- ~ FeSCN2+
(a) 0.342 (b) 2.92
will be : IBHU (Screening) 20101
(c) 0.292 (d) 3.42
(a) 6.66x 10-3 (b) 0.30
44. The equilibrium constant, in a reversible reaction at a given
(c) 3,30 (d) 150 temperature:
I
632 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(a)
depends on the initial concentration of the reactants 51. For which of the following reactions does the equilibrium
depends on the concentration of products at equilibrium
(b) constant depend on the units of concentration?
it is not characteristic of the reaction
(c) 1 I
(a) NO(g) - - ' > . 2 N2 (g) + 2" 0 2(g)
(d)
does not depend on initial concentrations
45. LO g mole of ethyl alcohol and 1.0 g mole of acetic acid are (b) C 2Hs0H(l) + CH 3 COOH(l) ~ CH 3 COOC 2 Hs(l)
mixed. At equilibrium 0.666 g mole ofthe ester is present. The + H2°(l)
value of equilibrium constant is: [PET (MP) 1993) (c) 2HI(g) ~ Hz{g) + I 2 (g)
(a) ~ (b) ~ (c) 2 (d) 4 (d) COCl 1 (g) ~ CO(g) + ClzCg)
4 2 52. The units of K p in the following reaction are:
46. The equilibrium constant of the reaction, N2 (g) + 3H2 (g) 2NH3 (g)
2
. CH 3 COOH(l) + CJIs0H(l) ;;--" CH 3COOC 2Hs(l) + H 20(l) (a) atrn (b) atm- (c) atm2 (d) atm- 1
is 4. If one mole of each of acetic acid and ethyl alcohol are 53. The equilibrium of formation of phosgene is represented as:
heated in presence of a little concentrated H 2S04 , at CO(g) + CI 2 (g) ~ COCI 2 (g)
equilibrium the amount of ester present is: [PET (MP) 1992] The reaction is carried out in a 500 mL flask. At equilibrium
Ca) I mole (b) 2 mole 0.3 mole of phosgene, 0.1 mole of CO and 0.1 mole ofCl 2 are
2 I present. The equilibrium constant of the reaction is:
(c) mole (d) mole
3 2 (a) 10 (b) 15 (c).5 (d) 3
47. It different quantities of ethanol and acetic acid are used in the 54. In an equilibrium reaction, for which 6.G" = 0, the equilibrium
following reversible reaction, constant K should be equal to:
CH 3 COOH(l) + C2HsOH(l)~CH3COOC2Hs(l) + H 20(l)
(a) zero (b) ~O (c) 1 (d) 2
the equilibrium constant will have values which will be?
55. The equilibrium constant K p for the homogeneous gaseous
(a) Different in all cases
reaction is 10-3 . The standard Gibbs free energy change t:.Go
(b) Same in all cases for the reaction at 27°C (using R = 2 cal K- 1 mol-I) is:
(c) Higher in cases where higher concentration of ethanol is (a) zero (b) - 1.8 kcal
used
(c) - 4.154 kcal (d) + 4.154 kcal
(d) Higher in cases where higher concentration of acetic acid
56. At 500 K, the equilibrium constant for reaction
is used
cis-C 2 H zCl 2 trans-C 2 H 2Cl 2 is 0.6. At the same
48. The reaction, temperature, the equilibrium constant for the reaction
2A(g)+B(g)~ 3C(g)+D(g)
trans-C zH2Cl 2 ~ cis-C 2 H2 CI 2 , will be:
is begun with concentration of A and B both at initial value of
(a) 1.67 (b) 0.6 (c) 1.76 (d) 1.64
1M. When equilibrium is reached, the concentration of D is
. 57. Which one of the following oxides is most stable? The
measured and found to be 0.25 M. The value for the
equilibrium constants are given at the same temperature:
equilibrium constant for this reaction is given by the
expression: tCBSE (PMT) 2010] (a) 2N 2 0 5 (g) 2N2 (g) + 50 2(g); K 1.2 x 1034
(b) 2N,O(g) 2N 2 (g) + 02(g); K 3.5 x 1035
(a) [(0.75)\0.25)] + [(l.OOi (LOO)] - ~
(c) 2NO(g) ~ N2 (g) + 02(g); K = 2.2 x 10
(b) [(0.75)3 (0.25)] [(0.50i (0.75)] (d) 2N0 2 (g) - - ' > . N2 (g) + 20 2 (g); K = 6.71 X 1016
(c) [(0.75)3 (0.25)] + [(0.50)2 (0.25)] 58. In a chemical equilibrium, K c = K p when:
ICEE (Bihar) 19921
(d) [(0.75)3 (0.25)]':;' [(O.75i (0.25)] (a) the number of molecules entering into a reaction is more
[Hint: 2A(g) + B(g) ~ 3C(g) + D(g) than the number of molecules produced
o o (b) the number of molecules entering into the reaction is equal
0.50 0.75 0.75 0.25 to the number of molecules produced
(c) the number of molecules entering into the reaction is less
[C ]3[D J = (0.75ho.25) ]
K to the number of molecules produced
[Af[B] (0.50)2(0.75)
(d) none ofthe above
49. The decomposition of N2 0 4 to N02 is carried at 280 K in 59. In a general reaction, A + B ~ AB, which value of
chloroform. When equilibrium has been established, 0.2 mole equilibrium constant most favours the production Of AB?
of N2 0 4 and 2 x 10-3 mole of N02 are present in 2 litre
(a) 9.0 x 10- 3 (b) 3.5 x 10-3
solution. The equilibrium constant for the reaction,
7
N 2 0 4 (g) ;;--" 2N02 (g), is: ec) 4.0 x 10- (d) 4.0 x 10-12
(a) 1 x 10-2 (b) 2 x 10-3 60. During thermal dissociation of a gas, the vapour density:
(c) Ix 10- 5
(d) 2 x 10- 5 Ca) remains the same
(b) increases
50. The unit of equilibrium constant, K c' for the reaction (c) decreases
A +B ~ C would be:
(d) increases in some cases and decreases in others
(a) mol- 1 L (b) mol L- 1 (c) mol L (d) no unit
CHEMICAL EQUILIBRIUM 633
61. The vapour density of fully dissociated NH4 Cl would be: (a) First law of thermodynamics
(a) less than half of the vapour density of pure NH4 Cl (b) Le Chatelier's principle
(b) double of the vapour density of pure NH4 CI (c) Hess's law
(c) half of the vapour density of pure NH4 CI (d) Ostwald's law
(d) one-third of the vapour density of pure NH4 Cl 70. Le Chatelier's principle is applicable to:
62. In the dissociation of 2HI ~ Hz + 12 , the degree of (a) only homogeneous chemical reversible reactions
dissociation will be affected by: (b) 'only heterogeneous chemical reversible reactions
(a) increase of temperature (b) addition of an inert gas (c) only physical equilibria
(c) addition of H2 and 12 (d) increase of pressure (d) all systems, chemical or physical, in equilibrium
63. In lime kilns, the following reversible reaction, 71. In the melting of ice, which one of the conditions will be more
favourable?
CaC0 3 (s) ~ CaO(s) + cO 2 (g) (a) High temperature andhigh pressure
proceeds to completion because of: (CPMT 1990) (b) Low temperature and low pressure
(a) high temperature (c) Low temperature and high pressure
(b) CO2 escapes (d) High temperature and low pressure
(c) low temperature 72. Solubility of a gas in liquid increases on:
(d) molecular mass ofCaO is less than that ofCaC0 3 (a) additionofacatalyst (b) of pressure
64. The equilibrium constant for ~he reaction, (c) increasing of pressure (d) increasing oftemperature--
CaC0 3 (s) ~ CaO(s) + CO 2 (g), is: 73. When KOH is dissolved in water, heat is evolved. If the
temperature is raised, the solubility ofKOH:
1
(a) increases (b) decreases
[C0 2 ]
(c) remains the same (d) cannot be predicted
74. The yield of product in the reaction,
A2(g)+2B(g) C(g)+QkJ
65. For the reaction, C(s) + cO 2 (g) ~ 2CO(g), the partial would be higher at:
pressure of CO2 and CO are 2.0 and 4.0 atm, respectively, at (a) low temperature and high pressure
equilibrium. The K p of the reaction is: (lIT 1992) (b) high temperature and high pressure
(a) 0.5 (b) 4.0 (c) low temperature and low pressure
(c) 32.0 (d) 8.0 (d) high temperature and low pressure
66. Iron fillings and water were placed in a 5 litre vessel and 75. Manufacture of ammonia from the elements is represented by,
sealed. The tank was heated to 1000°C. Upon analysis the tank • N 2 (g) + 3H2 (g) -----' 2NH3(g) + 22.4 kcal
was found to contain 1.1 g of hydrogen and 42.5 g of water The maximum yield of ammonia will be obtained when the
vapour. If the reaction in the tank is represented by, process is made to take place:
3Fe(s) + 4H 2 0(g) ~ Fe 3 0 4 (s) + 4H2 (g) (a) at low pressure and high temperature
the value of equilibrium constant, K c' is: (b) at low pressure and low temperature
(a) 30 (b) 0.03 (c) at high pressure and high temperature
(c) 3 (d) 0.003 (d) at high pressure and low. temperature
67. Ammonium hydrogen sulphide is contained in a closed 76. In the reaction, 2S0 2(g) + 02(g) 2S0 3 (g) + X cal,
vessel at 313 K when total pressure at equilibrium is found most favourable conditions of temperature and pressure for
to be 0.8 atm. The value of K p for the reaction, greater yield of S03 are:
NH4 HS(s) NH3 (g) + H 2 S(g) is: (a) low temperature and low pressure
(a) 0.16 (b) 1.6 (c) 0.016 (d) 16 (b) high temperature and low pressure
68. Variation of K with temperature as given by van't Hoff (c) high temperature and high pressure
:u~::n;:n b, :~:'[;,
(d) low temperature and high pressure
:,1 77. What is the direction of a reversible reaction when one of the
products of the reaction is removed?
(b) log
K1
till
2.303R T2
[I 7JI] (a) The reaction moves towards right hand side
(b) The reaction moves towards left hand side
(c) The reaction moves equally on both the sides
79. A cylinder provided with a pistOFl has some PCl s which is in (a) amount of solid to decrease
equilibrium with PCi} and C1 2. The system is compressed with (b) amount of liquid to decrease
the help of piston. Indicate the correct statement: (c) temperature to rise
(a) some more PCi s wil1 decompose (d) temperature to fal1
(b) the system remains unaffected 88. For the reaction:
(c) PCl} and Cl 2 wil1 combine to form PCl s 2A(g)+B(g)~ 3C(g)+D(g)
(d) explosion occurs two moles each of A and B were taken into a flask. The
80. In the manufacture of nitric oxide, the forward reaction is fol1owing must always be true when the system attained
favoured by: equilibrium:
(a) high pressure (b) low pressure (a) [A] = [B] (b) [A] < [B]
(c) high temperature (d) low temperature (c) [B] = [C] (d) [A] > [B]
81. The reaction, 89. In a vessel containing S03' S02 and 02 at equilibrium, some
C 2H 4 (g) + H 2(g) ~ C 2H 6 (g); I'ili = - 32.7 kcal helium gas is introduced so that total pressure increases while
is carried out in a vessel. The equilibrium concentration of temperature and volume remain the -same. According to
C 2H4 can be increased by: Le Chatelier's principle, the dissociation of SO}:
(a) increasing the temperature (MLNR 1991)
(b) decreasing the pressure (a) increases (b) decreases
(c) removing some hydrogen; (c) remains unaltered - Cd) changes unpredictably ----~
(d) al1 of these 90. The equilibrium, S02CI2(g) ~ S02(g) + CI 2(g) is
82. In an exothermic reaction, a 10°C rise in temperature will: attained at 25°C in a closed container and an inert gas, helium,
[PMT (Bangalore) 1993] is introduced. Which of the following statements is correct?
(a) decrease the value of equilibrium constant (a) Concentrations of S02Ci2' S02 and Ci 2 do not change
(b) double the value of equilibrium constant (b) More Cl 2 is formed
(c) not produce any change in equilibrium 'constant (c) Concentration of S02 is reduced
(d) produce some increase in equilibrium constant (d) More S02Ci2 is fonned
83. If K J! for a reaction, 91. The vapour density of undecomposed N20 4 is 46. When
A (g ) + 2B (g ) ~ 3C(g) + D (g) heated," vapour density decreases to 24.5 due to its dissociation
to N02. The % dissociation ofN 20 4 is:
is 0.05 atm at 1000 K, its K c in terms of R wil1 be:
'(a) 40 (b) 57
(a) 20000 R (b) 0.02 R (c) 5 X lO-s R (d) 5 x lO-s (c) 67 (d) 87
R
84. Consider'the reaction, CaCO}(s) ~ CaO(s) + CO 2 (g) . 92. K/Kc for the reaction, CO(g) + ~02(g) ~ CO2(g) is:
in closed container at equilibrium. What would be the effect of
addition of CaCO} on the equilibrium concentration of CO 2? (a) RT (b) _1_ (c).fiT (d) 1
(AIIMS 1991) JRT
(a) Increases 93. For the reactions,
(b) Decreases A ~ B, Kc = 1; B ~ C, Kc = 3; C ~ D, K c = 5
(c) Remains unaffected K c for the reaction A ~ Dis:
(d) Data is not sufficient to predict it (a) 15 (b) 5 (c) 3 (d) 1
85. XY2 dissociates as: . ruint:[B]=l' ~=3' [D]=5
XY2(g)~ XY(g)+ Yeg) LU. [A ] ' [ B] , [C] ,
Initial pressure of XY2 is 600 mm Hg. The total pressure at
M~ltiplying all the three, [D] = 1 x 3 x 5]
equilibrium is 800 mm Hg. Assuming volume of system to . [A]
remain constant, the value of K pis: (BHU 1992) 94. The equilibrium constant of the reaction,
(a) 5.0 (b) 100 (c) 200 (d) 400 H 2 (g) + I 2(g) ~ 2H1(g) is 50. If the volume of the
[Hint: XJ2(g) ~ XY(g) + Y(g) container is reduced to one half of its original value, the
600 - x x x equilibrium constant wil1 be:
600 + x = 800 or x = 200 ] (a) 25 (b) 50
86. Which of the fol1owing reactions wil1 be favoured at low (c) 75 (d) 100
pressure? 95. C(s) + H 2 0(g) ~ CO (g) + H2 (g)
(a) H2 (g) + 12(g) ~ 2H1(g) The above equilibrium when subjected to pressure:
(b) N 2(g) + 3H 2(g) ~ 2NH}(g) [PMT (Raj.) 1997.)
(a) remains unaffected
(c) PCis(g) ~ PCi 3 (g) + Ci 2(g)
(b) proceeds in the backward direction
(d) N 2(g) + 02(g) ~ 2NO(g)
(c) proceeds in the forward direction
87. According to Le Chatelier's principle, adding heat to a solid
and liquid in equilibrium will cause the: (MLNR 1990) (d) none of the above
CHEMICAL EQUILIBRIUM 635
96. Reaction, A + B -----7 C + D + 38 kcal has activation energy (b) solid and liquids react slowly
20 kcal. Activation energy for the reaction, (c) solid and liquids at equilibrium do not interact with
C + D -----7 A + B is: [PMT (Pb.) 1993] gaseous phase
(a) 20 kcal (b) -20 kcal (d) the molecules of solids and liquids cannot migrate to the
(c) 18 kcal (d) 58 kcal gaseous phase
97. The equilibrium constant for the reaction, 105. For an equilibrium reaction involving gases, the forward
CaS04 ·5H2 0(s) ~ CaS0 4 ·3H2 0(s) + 2H 2 0(g), reaction is first order while the reverse reaction is second
is equal to: order. The units of K p for forward equilibrium is:
(a) [CaS04 ·3H2 0][H2 0f (b) [CaS04 ·3H2 0] (a) atm (b) atm 2 (c) atm- I (d) atm- 2
[CaS04 ·5H2 0] [CaS04 ·5H2 0] 106. At temperature T, a compound ABo (g) dissociates according·
t9 the reaction: •
(c) [H 20]2 (d) [H 2 0]
2AB2(g)~ 2AB(g)+B2(g)
9S. One mole ofN2 0 4(g) at 300 K is kept in a closed container
with a degree of dissociation 'x' which is small as compared to
under one atmosphere. It is heated to 600 K when 20% by
unity. The expression for K p' in terms of 'x' and total pressure
mass of N 2 0 4(g) decomposes to N02 (g). The resultant
'P'is
pressure is: 3 2
(a) 1.2 atm (b) 2.4 atm (c) 2.0 atm (d) 1.0 atm (a) Px (b) Px
99. The equilibrium constant for the reaction" 2 3
3 2
N 2 (g) + 02(g) ~2NO(g) is 4.0 x 10-4 at 2000 K. I~the (c) Px (d) Px
presence of a catalyst the equilibrium is attained ten times , 3 2
faster. Therefore, the equilibrium constant in presence of the 107. 40% mixture of 0.2 mole of N2 and 0.6 mole of H2 react to
catalyst at 2000 K is: (MLNR 1994) give NH3 according to the equation:
(a) 4 x 10-4 • N 2 (g) + 3H2 (g) ~ 2NH3(g)
(b) 4Cl x 10-4 at constant temperature and pressure. Then the ratio of the
(c) 4 X 10-2 final volume to the initial volume of gases is:
(d) difficult to compute without more data (a) 4: 5 (b) 5 : 4
100. The equilibrium constant for a reaction, A + B ~ C + D'is (c) 7: 10 ' (d) 8 : 5
I x 10-2 at 298 K and is 2 at 273 K. The chemical process lOS. Two systems,
resulting in the formation of C and Dis:
PCIs(g) ~ PCI 3 (g) + CI 2 (g)
(a) exothenuic
and COCI 2 (g) ~ CO(g) + CI 2 (g)
(b) endothermic
(c) unpredictable are simultaneously in equilibrium in a vessel at constant
(d) there is no relationship between Ml and K volume. If some CO(g) is introduced in the vessel at constant
101. The equilibrium constant for the reaction, A + B ~ C + D volume, then at new equilibrium, the concentration of:
is 2.85 at room 'temperature and 1.4 x 10-2 at 698 K. This (a) PCls is greater (b) PC1 3 remains unchanged
shows that forward reaction is: (c) PCls is less (d) CI 2 is greater ,
(a) exothermic 109. For the reaction, [Ag(CN}zr ~ Ag+ + 2CN-, the
(b) endothenn1c equilibrium constant Kc at 25°C is 4 x 10- 19 ; then Ag+
(c) unpredictable concentration in a solution which has 0.1 M KCN and 0.03 M
AgN0 3 is:'
(d) there is no relationship between I'1H and K
102. If Er and Er are the activation energies of forward and (a) 7.5x lOIS (b) 7.5 x 1O- lg
backward reactions and the reaction is known to be (d) 7.5 x 10- 19
exothermic, then:
110. When NaNO} is heated in a closed vessel, oxygen is liberated
(a) Er > Er and NaN0 2 is left behind. At equilibrium:
(b) E f < Er (a) addition of NaN0 2 favours reverse reaction
(c) E f = Er (b) addition of NaN0 2 favours forward reaction
(d) no relation can be given between Er and Er
(c) increasing temperature favours forward reaction
103. K p for a reaction at 25°C is 10 atm. The activation energy for
(d) decreasing pressure favours reverse reaction
forward and reverse reactions are 12 and 20 kJ/mol
111. For the reaction,
respectively. The K c for the reaction at 40°C will be:
CuS04 ·5H2 0(s) ~ CUS04 ·3H2 0(s) + 2H 2 0(g)
(a) 4.33 x 10- 1 M (b) 3.33 x 10-2 M
which one is the correct representation?
(c) 3.33 10- 1 M (d) 4.33 x 10-2 M
(~) K p = [ PH 2 0f
X
(b) Kc = [H 20]2
104. Concentration of pure solid and liquid is not included in the
expression of equilibrium constant because: (c) K p = K c CRT)2 (d) All of these
(a) solid and liquid concentrations are independent of their 112. Which one is the correct representation for,
quantities 2S0 2 (g) + 02(g) ~ 2S0 3(g)?
636 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(lIT 1999)
I CHEMICAL EQUILIBRIUM 63~
(a) 'Ix 102 atm (b) 2x 1()2 atm- I dM.IS +ve ..lor t E (0 , ) where, M is average molar
( c)
'dt
(c) 50 atm 2 (d) 5 x 10-3 atm 2
mass of the reaction mixture
131. 8 mole of a gas AB3 are introduced into a 1.0 dm 3 vessel. It
(d) total gaseous weight at equilibrium is less than 68 g
dissociates as:
136. A vessel (volume = 2 L) contains 60 g of water gas. When
2AB3(g)~ A2(g)+ 3B 2 (g)
steam is passed through the vessel, the reaction,
At equilibrium, 2 mole of A2 are found to be present. The
CO + H20~ COz + Hz occurs and equilibrium is attained:
equilibrium constant of the reaction is: (lIT 1997)
2
Ca) 2 mol L- 2 2
(b) 3 mol L- z (a) n(H z ) < I (at equilibrium)
n(CO)
(c) 27 mol 2 L -2 (d) 36 moe L-2
(b) n(H2 ) + n(CO) = 4 (at any instant)
132. At constant temperature, the equilibrium constant (K p ) for the dAf f .
decomposition reaction, (c) - dt > 0 (where, M is average molar mass 0 gas mixture
N204~2N02 before the attainment of equilibrium)
is expressed by:
(d) dM < 0
dt .
137. A vessel contains CO 2 and CO with pressures 2 atm and 3 atm
Where, P pressure, x = extent of decomposition. Which one respectively at 27°C. At a temperature of 2727°C, the reaction
of the following statements is true? (lIT (Screening) 20001 2CO(g) COz(g) + C(s) occurs and equilibrium -is~~
(a) K p increases with increase of P attained. If the eqUilibrium pressure is 45 atm, then:
(b) K p increases with increase of x (a) K p = 2/9 atm- 1
(c) K p increases with decrease of x
(b) Pea: Pea) = 4: 5 at equilibrium
(d) K p remains constant with change in P and x (c) K p 16 atm- I
133. 0'" ;der the reactions,
(d) % dissociation of CO = 0.333
N02(g)~ ~ N 2(g) + 02(g) KI 13.8. A vessel (volume 8.2 L) contains Hz (g) at 2 atm pressure.
2
, When H 2 S(g) at a pressure of 4 atm is introduced into the
N 20 4 (g) 2N0 2 (g) K2
vessel, the reaction, 8HzS(g) ~ 8Hz(g) +. S8 (s ) occurs at a
Give the equilibrium constant for the fonnation ofNz0 4 from
°
N z and 2 : . (DeE 2006)
temperature of 2000 K, It is found that:
I
(a)-x
1 1
(b)-+-(c)
I
(d)-
K2
[
n (Hz) J [n(H 2 S)]
Kj2
K2 2K) K2 K] n(H 2 S) at equilibrium n(H2) at 1=0
1 Ca) maximum weight of solid fonned is 32 g
[Hint: N0 2 (g) 2 N 2 (g) + 02(g) K j
(b) maximum weight of solid fonned is 0.32 g
.. N 2 (g) + 20 2 (g) ~ 2N0 2 (g) K = ~2 ••. 0) (c) Kp =Kc RT
I (d) Kc = 256
139. N2 (g) and H 2 (g) are taken in a vessel in inass ratio of 7 : 1.
The only reaction N2 + 2H2 --->. N2H4 (g) occurs. Pressure
.. 2N02(g)~N204(g) ... (ii)
due to N zH 4 at equilibrium is 0.2 times of total pressure' P'.
Adding eqs. (i) and (ii), Then at equilibrium:
N 2(g) + 202(g)~N204(g) (a) partial pressure ofN2 2P 115
(b) partial pressure of Hz 8PI25
134; Phosphorous pentachloride dissociates as follows: (c) 2PNz PH z
PCI5(g)~ PCI 3 (g) + CI2(g). (d) PN) =
If total pressure at equilibrium is P and the degree of 140. In the equilibrium, S02CI2 ~ S02 + CI 2 at 2000 K and 10
dissociation of PC Is is x, the partial pressure ofPCl 3 will be: atrn pressure, % Clz % S02 = 40 by volume. Then:
(AIEEE 2006)
(a) Kp = 2 atrn
(a) x \IP (b)
+1) \I-x
r~\Jp ec) (lx~]p
I)
(d)
I
x , n(S02 Cl ?)
(b) - = -1 at eqUl'l'b .
1 num
n(S02) 4
135. At t = 0 a vessel (volume 1 litre) contains 1 mole N z, 3 mole (c) Kp = 8atm
Hz and 2 mole NH3 . The value of K c for N z + 3H2 ~ 2NH) (d) n(SOCI 2 ) n(SOz)=n(CI 2 )
is 17.5 LZ mol-2 • Then: ,
141. A 20 litre box contains and O? at equilibrium at 202 K.
tal LUI,,1 ~aseous weight at equilibrium is more than 68 g 14
Kp = 2x 10 for 203 302' ~Assume that Po 2 » Po)
(b) total r.··m.:'er of moles (gaseous) at equilibrium are more and total pressure is 8 atm; the partial pressure of 0 3 IS:
than 6 moles (a) exactly 1.6 x 10-6 atm
(b) s~fficiently less than 1.6 x 10-6 atm
638 G R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(c) K p changes but '0:' does not 162. Partial pressure of 02 in the reaction,
(d) K p does not change but '0:' changes 2Ag 2 0(s) ~ 4Ag(s) + 02(g)
154. For the reaction, PCI 3(g) + CI 2 (g) PCls(g), the position is: (DCE 2005)
of equilibrium can be shifted to the right by: (a) K p (b)jK; (c) (d) 2K p
[PET (MP) 2004]
163. Two moles of PCls are heated in a closed vessel of 2 litre
(a) doubling the volume
capacity. When the equilibrium is attained 40% of it has been
(b) increasing the temperature 3
found to be dissociated. What is the value of Kc in mol/dm ?
(c) addition of equimolar quantities ofPCl 3 and PCIs
[PET (KeraJa) 201151
(d) addition of Cl z at constant volume
(a) 0.532 (b) 0.266 (c)0.133 (d) 0.174
155. The most favourable condition for th~ manufacture ofNH3 is:
(e) 0.25
[CECE (SibaI') 2004]
[Hint: PCls(g) ---'- PCI 3 (g) + CI 2 (g)
(a) high temperature and high pressure 1=0 2 0 0
(b) low temperature and low pressure 2 - 08 0.8 0.8
- 2
- 2 2
(c) high temperature and low pressure
(d) low temperature and high pressure
156. The chemical equilibrium of a reversible reaction is not K =[PCI 3 ][C1 2 ] 0.64 = 0.266]
influenced by: (KCET 2004) c [PCls] 2.4
(a) catalyst (b) pressw'e 2
(c) temperature (d) concentration _..... ,.... 164. For the reaction:
157. Which of the following change will shift the' r~'i2tion"in' 2NOzeg) 2NO(g) + 02(g)
forward direction? . Kc = 1.8 X 10-6 at 184°C
R = 0,0831kJ K- 1 mol- 1
Iz(g) ~ 2I(g); ARo + 150 kJ (AIlMS 2004)
(a) Increase in total pressure when, K p and K c are compared at 184°C it is found that:
(b) Increase in temperature (AIEEE 2005)
(c) Increase in concentration of 1 (a) K p. is greater than K c
(d) Decrease in concentration of 12 (b) K p is less than K c
K (c) K p = Kc
158. For the reaction, CO(g) + CI 2 (g) COCI 7 (g) , the ---E.. is (d) whether K p is greater than, ,less than or equal to K c
• Kc
depends upon the total gas pressure
equal to: (AIEEE 2004)
[Hint: Kp = Kc (RTl"
(a) II RT (b) RT (c) ill (d) 1
Lln=3-2=1
159. The equilibriwn constant for the reaction,
Kp = Kc (RT)l
Nz(g) + 0z(g) 2NO(g)
at temperature T is 4 x 10-4 . .. Kp >Kcl
The value of K c for the reaction, 165. NH 4 COONH,(s) ---->. 2NH 3(g) + CO,(g). If equilibrium
pressure is 3.~tm for the abo~e reactio~ K p will be:
NO(g) ~ .!. N2 (g) + I 02(g) (DPMT 2005)
2 2
at the same temperature is: (a) 4 (b) 27 (c) 4/27 (d) 1/27
(AlEEE 2004)
(a) 2.5 x 102 (b) 50 (c) 4 x 10-4 Cd) 0.02 [Hint: PNH 3 : Pe02 = 2 : I
160. 2 moles of N2 are mixed with 6 moles of H2 in a closed vessel .. PNHJ = 2 atm: PC02 1 atm
of one litre capacity. If 50% N2 is converted into NH3 at Kp = [ PNH) ]2[pC02 ] = 22 X 1 = 4]
equilibrium, the value of K c for the reaction, 1.66. A + B ~ C + D. If initially the concentration of A and B
N 2 (g) + 3Hz{g) 2NH3(g) are both equal but at equilibrium, concentration of D will be
IPMT (Kerala) 2004] twice of that of A, then what will be the equilibrium constant
(a) 4127 (b) 27/4 of the reaction? [BHU (Pre.) 2005; JIPMER 20061
4 9
(c) 1127 (d) 27 (a) 9 (I'» 4 (c) 9I (d) 4
(e) 9
161. For the reaction, H2(g) + CO?(g) ..,-- CO(g) + H,O(g), if [Hint: A + B ~C+D
'/ = 0 a a () ()
the initial concentration of [H 2] [C0 2 ] and x mol/litre of H2 t eq . a x a x x x
is consumed at equilibrium, the correct expression of K pis: .
IJEE (Orissa) 2005] x 2(a x)
? J
;c 3x 2a
(a) ---;;:- (d)~
(I 1- x· xxx
K =xxx=4]
(a x)(a x) ~ x::
2 2
640 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
167. 15 moles ofH? and 5.2 moles ofI? are mixed and allowed to 171. If the equilibrium constant for the reaction,
attain equilibri~m at 500°e. At eq~ilibrium, the concentration N2(g)+3H2(g)~ 2NH3(g)
of HI is found to be 10 moles. The equilibrium constant for the at 750 K is 49, then the equilibrium constant for the reaction,
formation of HI is: (KCET 2005)
(a) 50 (b) 15 (c) 100 (d) 25 NH3(g) ~ ~ N2(g) + ~ H1(g)
[Hint: H2 + I z ~2HI at the same temperature is: [PMT (Kerala) 2006)
1=0 15 5.2 o
t eq . 15 - 5 5.2 - 5 10 (a) 1149 (b) 49 (c) 7 (d) 49 2
(e) 117
K = [HIf =~-=50] 172. The equilibrium constant for the reaction,
c [H z ][I2] lOxO.2
168. For the reaction: 2NOCl(g) ~ 2NO(g) + CI 2(g), Kc at
S03(J!)~ SO?(g)
,~ - + ~2O;(g)
-
427°C is 3 x 106 L mol-I.. The value of K p is nearly: isKc =4.9x 10-2.
. (AIIMS 2005)
The value of K c for the reaction,
(a) 7.5 x 10-5 (b) 2.5 x 10- 5 (c) 2.5 X 10-4 (d) 1.75 x 10-4
2S0 2(g ) + O 2 (g ) ~ 2S03(g )
169. For the chemical equilibrium, will be: (AIEEE 2006)
CaC03(s) ~ CaO(s) + CO 2(g) (a) 416 (b) 2.40 x 10- 3
!JJi~ can be detelmined from which one ofthe following plots?
(c) 9.8 X 10-2 (d) 4.9 x 10-2
(AIIMS 2005)
[Hint: S03(g) ~ S02(g) + ~ 02(g); Kc = 4.9 10-2
r
X
t0'
u
c..
Q)
OJ
.Q
1/T-
/ T-
2S02(g) + °2(g) ~ 2S0 (g);
3 Kc = [ 4.9
0'
u
c..
OJ
OJ
.Q
10gT-
/ 1/T-
[Hint: . Equilibrium constant does not change on adding the
reactant.]
174. In the reaction, H2 (g) + 12 (g) ~ 2HI(g), in a 2 litre flask
0.4 mole of each Hz and 12 are taken. At equilibrium 0.5 mole
of HI are formed. What will be the value of equilibrium
constant Kc? [PMT (Raj.) 2006]
(c) (d)
(a) 20.2 (b) 25.4 (c) 0.284 (d) ILl
[Hint: CaC0 3(s) ~ CaO(s) + CO 2(g)
175. For the reaction, Hi (g) + 12 (g) ~ 2HI(g), the equilibrium
Kp = Peol constant K p changes with: (VITEEE 2007)
According to Anhenius equation: (a) total pressure (b) catalyst
(c) the amount ofH 2 and 12 (d) temperature
K = Ae-MJ,"IRT
176. Given the equilibrium system,
!JJi" NH4Cl(s)~ NH;t(aq.) + Cl-(aq.)
10gKp=logA- ,.
2.303RT . (!JJi 0 = + 3.5 kcall mol)
!JJi" 1 what change will shift the equilibrium to the right?
loa P, = log A - --'_. - ... (i) (VITEEE 2007)
'" CO2 2.303R T
(a) Decreasing the temperature
Y=C + MX
(b) Increasing the temperature
Graph (a) represents (i) and its slope will be used to determine the (c) Dissolving NaCI crystals in equilibrium mixture
heat of the reaction.] (d) Dissolving NH4 NO, crystals in the equilibrium mixture
170. In gaseous reversible reaction, 177. The equilibrium constant (K p) for the decomposition of
N2(g)+ 02(g)~ 2NO(g)+ Heat gaseous H20 :
If pressure is increased, then the equilibrium constant would
be: [UGET (Manipal, Medical) 2006) H 20(g ) ~ H1 (g ) + ~ 0 1(g) is related to degree of
(a) unchanged dissociation (CI. ) at a total pressure P is given by:
(b) increased [PMT (Kerala) 20071
(c) decreased
(d) sometimes increased, sometimes decreased
CHEMICAL EQUILIBRIUM 641
equilibrium:
1. For the gaseous reaction, the equilibrium can be establis!! :i
in open vessel.
2. The state of equilibrium is dynamic in nature.
3. If temperature is kept constant, the colour of the reacting
system changes with time.
(1 0.)(2 +
Which ofthe statements given above is/are correct?
178. The equilibrium constant for the reaction, ' 20(P9)
2N02(g)~ 2NO(g)+ 02(g)is2x 10-6 at 185"C (a) 1 < (b) 2 only
Then. the equilibrium constant for the reaction,
(c) 3 only (d) 2 and 3 only
4NO(g) + 202 (g ) ~ 4NO z(g) at the same temperature
]84. The dissociation constants for acetic acid and HCN at 25°C
would be: [PET (Kerala) 2007)
are 1. 5 x 10- 5 and 4.5 x 10- 10 respectively. The equilibrium
(a) 2.5 x 10-5 (b) 4 x lO- IZ (c) 2.5 X 1011 (d) 2 x 106 constant for the equilibrium:
(e) 5x lOS eN" +CH3COOH~ HCN + CH 3 COO-
179. 1 mole ofH2 and 2 mole oflz are taken initially in a 2 L vessel. would be : [eESE (PMT) 2(09)
4
The number of moles Hz at equilibrium is 0.2. Then, the (a) 3x 10 (b) 3x 105
number of moles OfI2 and HI at equilibrium are: (c) 3xlO-5 (d) 3xlO-4
[PMT (Raj.) 2007] [Hint: Given
(a) 1.2, 1.6 (b) l.8, l.0 (c) 0.4,2.4 (d) 0.8,2.0 (i) CH3COOH~CH3COO- +W KI === 1.5x 10-5
180. The dissociation equilibrium of a gas AB z can be represented
(ii)< HCN~ W +CW K2 =4.5xlO- 10
as,
1 1
2AB 2 (g) 2AB(g)+ Bz(g) (iii) W + Cw ~ HCN
The degree of dissociation is x and is small as compared to 1.
The. expression relating the degree of dissociation (x) with Adding (i) and (iii) we get
equilibrium constant K p and total pressure Pis: <
CH3COOH + CW~ CH3COO- + HCN
(a)(2Kplp)1I2 (b)K/P (c)2K/P' (d)(2K/P),13<
K1. 5 x 10-5 X --:----;-;::-
rCBSE (PMT) 20081 4.Sx
(Hint: 2AB2 (g) ~ 2AB(g) + B2 (g) = 3x 104]
to 2 0 0 185. One mole of N 2 0 4 is heated in a flask with a volume of 0.1
teq < 2x x Total moles 2+x . dm3 . At equilibrium, 1.708 mole ofNOz and 0.146 mole of
Partial 2x x NZ0 4 were found 134°C. The equilibrium constant will be:
pressure xP xP xP
2+x 2+x 2+x 20(l9)
(a) 250 mol dril-3 (b) 300 moldm-3
(c) 200 mol dm- 3 (d) 230 mol dm-3
186. What is the effect of a tenfold increase in pressure on K p in the
reaction?
N 2 (g)+ 3H2 (g) ~2NH3(g)
At equilibrium:
4 (2 + x)(l- x)2
I
642 I G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
(a) a tenfold increase (b) a tenfold decrease 10. Which of the following will not affect the value of equilibrium
(c) no change Cd) equal to Kc constant of a reaction?
(a) Change in the concentration ofthe reactants
Set-2: The Questions given below may have more (b) Change in temperature
than one correct answers (c) Change in pressure
(d) Addition of catalyst
1. Unit of equilibrium constant is: 11. Which ofthe following statements is/are wrong?
(a) (moIlL)1 -" (b) (moIlL)8n (a) At equilibrium, concentrations of reactants and products
(c) (atm}811 .(d) all of these become constant because the reaction stops
2. Which is/are correct? (b) Addition of catalyst speeds up the forward reaction more
(a) 2.303 log K - 6.1[O/RT + !:J.so/R than the backward reaction
(c) Equilibrium constant of an exothermic reaction decreases
(b) !:J.GO = - 2.303RT log K
with increase of temperature
(c) 2.303 log K = -!:J.H°/RT 2 + t:J,S°/R (d) K p is always greater than Kc
(d) 2.303 log K = (1/ RT )(!:J.H + !:J.SO)
0 12. For the gas phase reaction,
3. For the reaction, CaC03 (s) -7 CaO(s) + COz(g), which is C zH4 + Hz C 2 H6 ;!:J.H° = 136.8 kJ mol-I
correct representation? carried out in a vessel, the equilibrium concentration of C 2H 4
(a) K p =(Pco2 ) (b) Kp=KcCRT) can be increased by: ISHU ~i\'h.:.'·' 2008l
(c) Kc = (C02 )/1 (d) All of these (a) increasing the temperature
"",:- - .
[t!~ .,::'~oeJEcTlvE
~.
~:'-~;r .. 'f
• Set-1
1. (b) 2. (d) 3. (e) 4. (e) 5. (a) 6. (a) 7. (b) 8. (d)
9. (d) 10. (b) 11. (e) 12. (a) 13. (d) 14. (d) 15. ,(b) 16. (a)
17. (b) 18. (e) 19. (e) 20. (d) 21. (a) 22. (b) 23. '(d) 24. (d)
25. (e) 26. (e) 27. (a) 28. (b) 29. (d) 30. (a) 31. (a) 32. (e)
33. (d) 34. (d) 35. (d) 36. (b) 37. (d) 38. (e) 39. (d) 40. (b)
41. (a) 42. (e) 43. (b) 44. (d) 45. (d) 46. (e) 47. (b) 48. (b)
49. (e) 50. (a) 51. (d) 52. (b) 53. (b) 54. (e) 55. (d) 56. (a)
57. (d) 58. (b) 59. (a) 60. (e) 61. (e) 62. (a) 63. (b) 64. (b)
65. (d)· 66., (d) 67. (a) . 68. (e) 69. (b) 70. (d) 71. (a) 72. (e)
73. (b) 74. (a) 75. (d) 76. (d) 77. (a) 78. (b) 79. (e) 80. (e)
81. Cd), '82. (a) 83. (d) 84. (e) 85., (b) 86. (e) 87.-(a) 88. (b)
89. (e) 90:;(a) 91. (d) 92. (b) 93. (a) 94. (b) 95. (b) . 96. (d)
97. (e) 98~ '(b) . 99. (a) 100. (a) 101. (a) 102. (b) 103. (e) 104. (a)
105. (a) 106. (a) 107. (a) 108. (e) 109. (b) no. (e) 111. (d) 112. (d)
113. (e) 114. (b) 115. (a) 116. (a) 117. (b) 118. (b) 119. (d) 120. (a)
121. (d) 122. (b) 123. (a) 124. (a) 125. (a) 126. (b) 127. (b) 128. (a)
129. (b) 130. (d) 131. (e) 132. (d) 133. (a) 134. (a) 135. (e) 136. (b)
137. (b) 138. (d) 139. (e) 140. (e) 141. (d) ·142. (b) 143. (d) 144. (e)
145. (e) 146. (a) 147. (b) 148. (d) 149. (b) 150. (a) 151. (a) 152. (e)
153; (d) 154. (d) 155. (d) 156. (a) 157. (b) 158. (a) 159. (b) 160. (a)
161. (a) 162. (a) 163. (b) 164. (a) 165. (a) .166. (d) 167. (a) 168. (d)
169-. (a) 170. (a) 171. (e) 172. (a) 173. (e) 174. (d) 175. (d) 176. (b)
177. (d) 178. (e) 179. (a) 180. (d) 181. (b) 182. (e) 183. (d) 184. (a)
185. (e) 186. (e)
['Jt~:::~ERTI()~..~SON·~P.Q~~--------------t
(a) RT (c) PV K
(b) RT (d) n RT K =--p-
P RT V c (RT)6n
[Hint: PV nRT
17. Match the List-I (equilibria) with List-II (conditions) and
n P . select the correct answer using the options given below~ _ _
v RT
List-I List-II
l P
:. Active mass (mol L- )
P Hz(g) + Iz(g) 2HI(g) 1. High temperature
RT ]
12. In the dissociation ofI2 (g) at 100'0' Kin i:1 ::::-"tdiner of 1 litre: Q. 2S0 z(g) + 0z(g) ~ 2S03 (g) 2. Low temperature
12(g)~ 2I-(g); Kc:::: 10'-6 R. 2NH3(g) ~ N2 (g) + 3H2(g) 3. High pressure
Select the correct relation: 4. Low pressure
(a)[I 2 ]>W] (b)[I21<W] (c)[Iz]=[r] (d)[I 2 ] ~W] 5. Independent of
pressure
[Hint: P Q R
(a) 1,3 2,3 2,4
(b) 2,3 1,4 1,3
10'-6 -2~3 .
(c) 1,5 2,4
I :. / [I2 ]>[r]]"
(d) 2,4 1,5 1,3
13. Acetic acid undergoes dimerisation, when dissolved in 18. At constant pressure, the presence of inert gases:
benzene (a) reduces the dissociation ofPC15
" .-::r0... H~ (b) increases the dissociation of PCJ s .
2CH3-COOH...-- CH 3 - C~ /./C - CH3 (c) does not affect the degree ofdissociation of PC Is
OH ... O~ (d) steps up the formation of PC Is
Molecular mass of acetic acid is found 120. Which among the [Hint: PCls(g) PCI 3(g) + CI 2 (g)
following relation is correct? On adding inert gas, the equilibrium will shift towards higher
d-D)
(c) a =2 (-
2d (a)Kp=Kc(~:J6n (b)Kp=Kx(~)M
d-
D-d
(d)a ::::--
p (P )-lln+l
where, d = Observed vapour density \M 1
[Hint:
Mo
(j;=._--
M
(n 1)M (b)J>oM
92 77.7 3D-M
0.184
(2-J)x77.7 (c) PoM (d) 2PoD
2D M
% Dissociation:::: 18.4]
28. S03 (g ) is heated in a closed vessel. An equilibrium:
23. Consider the following statements:
2S03(g) ~ 2S02(g) + °z(g)
In the Haber method of synthesis of ammonia
is established. The vapour density of the mixture, in which
l. Increase of pressure favours the formation ofNH3 S03 is 50% dissociated, is:
2. Decrease of pressure produces more NH3 (a) 26.5 (b) 35 (c) 42 (d) 55
3. Increase of temperature dissociates NH3 D d
4. Addition of inert gas favours the formation ofNH3 [Hint: a :::: - - -
(n l)d
Which of the statements given above are correct?
(SeRA 2009) 0.5 == 40-d
(a) 1 and 3 (b) 2and4 (c) 1 ~nd4 (d) 2and3 (2 -l)d
24. For the decomposition of PCls (g) in a <;losed vessel, the d 26.5]
degree of dissociation is (j; at totai pressure P. .
PCls(g) ~PC13(g) + Ch(g); Kp 29. When In K is plotted against ~ using the yan't Hoff equationE
Which among the following relations is correct?
a straight line is expected with a slope equal to:
f K IK +P
(a) a :::: ~Kp: P (b)a ~~ (a)AHoIRT. (b)-:-AHoIR (c)!1HoIR (d)RIAHo
30. AB z(g) dissociates as,
I AB2 (g )~ AB(g) + B(g)
(c)a::::~Kp+p (d)a= I
vKp+P The initial pressure of AB2 is 600 mm Hg and total pressure is
800 mm Hg. The equilibrium constant for the reaction will be:
25. In the decomposition reaction of ammonia: (a) 500 (b) 100 (c) 200 (d) 400
2NH 3(g) ~ Nz(g) + 3H2(g) 31. For the gaseous reaction,
2 moles of NH3 are introduced in the vessel of 1 litre. At
C2 H4 + H2 C 2 H6 ,
equilibrium, I mole NH3 was left, the value of K c will be:
the equilibrium constant has the units:
(a) 0.75 (b) 0.70 (c) 1.75 (d) 1.70
(a) mol 2 dm-J (b) drn 3 mol- I (c) dm-3 mol- I (d) mol dm- 3
[Hint: 2NH3(g) ~ N 2(g) + 3H 2(g)
32. The equilibrium constant for the reaction:
2 o
.112 31 :; H 2(g) + Br2(g) ~ 2HBr(g)
is 67.8 at 300 K. The equilibrium constant for the dissociation
ofHBr is:
(a) 0.0147 (b) 67.8 (c) 33.90 (d) 8.349
If 'D' is the vapour density of equilibrium mixture and Po is relationships for the values of !1Go and K eq?
the initial pressure of N 2 0 S (g), then its equilibrium pressure (a) !1Go > 0, Keq. < 1 (b) AGo> 0, Keq. > I
must not be (M is molecular mass ofN 20 s ): (c) AG~ < 0, Keq >1 (d) !1Go < 0, Keq < I
648 G. R. B. PHYSTGAL CHEMISTRY FOR C()MPETITIONS
37. The free energy of formation of NO is 78 kJ mol-I at the 44. Which of the following do not change the value of K for a
temperature of an automobile engine (1000 K). What is the reaction?
equilibrium constant for this reaction at 1000 K? (a) Addition of catalyst
1 I (b) Increase in temperature
2 N 2(g)+ 2 02(g)~ NO(g).
(c) Increase in pressure
, (a) 8.4 x 10-5 (b) 7.1 x 10-9 (c) 4.2 X 10- 10 (d) 1.7 x 10- 19 (d) Removal of one of the products
38. 2S0z(g) + 02(g)~ 2S0 3 (g) . 45. For which ofthe following reactions at equilibrium at constant
temperature doubling the volume will cause a shift to the
Given,that the equilibrium constant fv! c"e rew::tion above has
right?
a value of 278 at a particular temperature, what is the value of
(a) NZ0 4 (g) ~ 2N0 2(g)
equilibrium constant for the following reaction at same
temperature? (b) CaC03 (s) ~ CaO(s) + CO 2 (g)
(c) 2CO(g) + 0z(g) ~ 2CO~(g)
S03(g)~ S02(g)+ I02(g) Cd) Nz(g) + 02(g)~ 2NO(g)
. 2
46. In the reaction,
(a) 1.3 x 10-5 (b) 1.8 x 10-3 (c) 3.6 X 10-3 (d) 6 x 10-2
N Z0 4 (g) 2N02 (g) if D and d are the vapour
39. In which of the following reactions, the increase in volume of densities at iRitial stage and at eqUilibrium then what will be
the container will favour the formation of products?
(a) C(s) + H 2 0(g) CO(g) + H 2 (g) the value ofD at point A in the following graph?
.d .'
. (b) H2(g) + 12UD 2ID(g)
'. (c) 4~3(g) + 502 (g) ~ 4NO(g) + 6H20(l) i
(d) 302(g) ~ 203 (g)
40. Consider the reaction, whose K c =: 33,
S02(g) + N02(g)·~ S03(g) + NO(g)
If 0.1 mol each of SOz and NO z are placed in 1 L container,
what is the concentration of SOz at equilibrium?
(a) 0.003 M (b) O.oI5 M (c) 0.085 M (d) 0.097 M
(f-
o
41. Reaction K
(a) 0 (b) 1.5 (c) I (d) 0.5
~ N2 (g) + 02(g)~ N02 (g)
2 . D d
[Hint: \1.=--.-
2N02.(g)~ N Z04(g) (n -l)d
Using above equations, Wlite down expression for.Kof the For the given reaction, n = 2 and \I. = 0 at A
following reaction: .' '. D-d
--=0
. I . '. (2 -l)d
Nz0 4(g) . . .+
N 2 (g) ' -02(g)
2 . D
K2 'd=lJ
(b)_2 47. A schelTIatic plot ofln Keq. versus inverse of temperature for a
K) K 2K 1 . . reaction is shown below: .
42. Cu 2+ ions react with Fe 2+ ions accordill.gto the following
. reaction:
eu 2+ + 2fe 2 +
At equilibrium, the concentration pf Cu 2+ ions is not changed
by the addition of:
i
In Keq
(a)Cu 2+ (b) Fe 2 + (c)Cu (d) Fe 3 +
43. Consider this equilibrium, for which Mf < 0,
HgO(s) + 4r(aq.) + H2 0(l) ~ HgI~- + 20ll 1
Which changes will increase the equilibrium concentration of "T-
HgI~- ? The reaction must be:
1. Increasing the mass of HgO( s) present." (a) exothermic
II. Increasing [r]. (b) endothermic
III. Adding I MHCl. (c) one with negligible enthalpy change
(a) I only (b) II only (d) highly spontaneous at ordinary temperature
(c) II and III only (d) I, II and III
CHEMICAL EQUILIBRIUM 649
din 1'3H 0 50. The equilibrium constants K PI and K P2 for the reactions
[Hint: We ~ow that, dT RT 2
X ~ 2Y and Z ~ P + Q; respectively are in the ratio of
1 : 9. If the degree of dissociation of X and Z be equal then the
In Keq, ratio of total pressures at these equilibria is: . (AIEEE 2008)
(a) I : 9 (b) I : 36
The plot has positive slope, hence I1H 0 will be negative,]
(c) 1 : I (d) 1 : 3
48. The equilibrium: [Hint: X 2Y Z -:;;=:::: P + Q
NH4 HS(s) ~ NH3 (g) + H2 S(g), 0 o 0
to
is followed to set-up at 1270 C in a closed vessel. The total 1- a 2a I-a a a
teq.
pressure at equilibrium was 20 atm. The K c for the reaction is:
(a) 0.092 M2 (b) 0.085 M2 [~p,r
I+a
(c) 3.045 M2, (d) none of these
n = 2 and a =-
100
20,
0.2 i
In Kp
i
In Kp
D
d
46, initial vapour density
vapour density at equilibrium
I I
-·11T -+ 11T -+
D d
a= (a) (b)
(n l)d
46-d
0.2
d
(2 -l)d
38.3
i
In Kp
i.
In Kp
Molar mass equilibrium = 2 x 38.3 = 76.6 I I
Pm = dRT Here, d = density of gas mixture 11T --Ii- 11T -+
d(mix) = Pm = lx76.6 =3.12 IL] (c) (d)
RT 0.0821 x 300 g
Answer the following questions: when Q > K, reaction will favour backward direction and· whel1
1. Consider the reactions: Q < K, it will favour forward direction,
(i) CO(g) + H20(g) ~ COz(g) + H2 (g);K] Answer the following questions:
(ii) CH4 (g) + HzO(g) ~ CO(g) + 3H2(g);K 2 1. The reaction quotientQ for:
(iii) CH4 (g) + 2H2 0(g) ~ COt(g) + 4H2(g); K 3 N 2(g) + 3H2(g) ~ 2NH)(g)
Which of the following is correct? , , b Q = [ NH3]2 ) . Th·e reactIOn
, '11·proceed .,In
IS given y WI
(a)K:j~=K]IK2 (b)K) =K(IK; [Nz][H2 ] .
• PassageS Graph 3
In a reversible chemical reaction, the rate of f01ward reaction
decreases and that, of backward reaction increases with the passage
'0 '0
of time; at equilibrium the rate offorward and backward reactions >CI)
become same. ~~t 'I ,'5j~~"8
~o
C]):::l
"
~ SELF AsSESSMENT~'
ASSIGNMENT NO.9
Statement-2: The value of equilibrium constant does not 18. Match the List-I with List-II:
change when the equation is multiplied or divided by a List-I List-II
number. . Ir--K- -
14. Statement-I: K p :::: Kc for all reactions. (a) A(g) B(g)+C(g) (p)a::::.1 p
Because VKp + 4P
Statement-2: K p and Kc are interrelated by the equation
Kp (RT)D.n.
(b)A2(g)~ 2A(g) (q)a Jp ~~p
15. Statement-I: Catalyst does not change the position of
Mre.ctant
equilibrium.
Because l+a
Statement-2: Catalyst only changes the equilibrium time. (d)N204(g)~ 2N02 (g) (s) Forward shift on
16. Statement-I: Free energy of both reactants and products are decreasing the
minimum at equilibrium. . pressure
Because 19. Match the List-I with List-II:
Statement-2: The free energy of reactants and products List-I List-II
decreases with passage of time and become equal at (Mathematical process) (New equilibrium constant)
equilibrium. (a) Divided by n (P)K n
17. Statement-I: Addition of inert gases at equilibrium will
(b) Multiplied by n (q)~
support the dissociation of PCls at constant temperature. K
Because (c) Reaction is reversed (r)Kl xK 2 xK 3 x ... xKn
Statement-2: The addition of inert gas at constant volume will
not affect the equilibrium.
(d) n-equations are added (s) (K i 'n
20. Match the List-I with List-II for the following reaction:
SECTION-IV NH4HS(s) NH3(g) + H 2S(g)
Matrix-Matching Type Questions List-I List-II
This section contains 4 qJlestions. Each question contains
(a) Partial pressure of (P) PNH3 XPH2S
statement given in two columns which have to be matched.
NH4 HS(s)
Statements (a, b, c and d) in List-I have to be matched with
statements (p, q, rand s) in List-II. The answers to these (b)Kp (q) PNH3 + PH 2 S
questions have to be appropriately bubbled as illustrated in the (c) Total pressure at (r) ( PNH 3 x PH2) (RT r2
following examples: equilibrium
If the correct matches are (a-p,s); (b-q,r); (c-p,q) and (d-s),
(d) Kc (s) Zero
then correct bubbled 4 x 4 matrix should be as follows:
p q r s
a
G®0 0
b
®.e e G\
c
G e0 (0
d
®® 0 0
[ ,4~.-----------------I
1. (b) 2. (b) 3. (c) 4. (a) 5. (d) 6. (d) 7. (a) 8. (a, b, d)
9. (b. d) 10. (a, b) 11. (a, b, c) 12. (a, b) 13. (c) 14. (d) 15. (a) 16. (a)
17. (b) 18. (a-q,r,s) (b-p,q,s) (c-q, r,s) (d-p,s) 19. (a-s) (b-p) (c-q) (d-r)
20. (a-s) (b-p) (c-q) (d-r)
IONIC EQUILIBRIUM
Solutions (aqueous)
10.1 INTRODUCTION
The compounds which give ions either in molten state or in
I
solution are called electrolytes. In the solid state they are bad ! .1
Non-conducting (solutions of
Conducting (solutions of
conductors, but become good conductors either in the molten non-electrolytes such as urea,
electrolytes, i. e., acids, bases
state or in solution. and salts) glucose. sugar. glycerine, etc.)
There are two types of electrolytes:
(1) Strong electrolytes: These electrolytes are almost
completely ionised when dissolved in a polar medium like water.
r
Strongly conducting (solns. of
1
Weakly conducting (solutions
In solution they are excellent conductors, e.g., HN0 3 , HCI, strong electrolytes which of weak electrolytes which
KOH, NaOH, etc. Their degree of ionization is high and ionise almost completely in water slightly ionise in water such as
approaches unity. such as HCl, H2 S0 4 , HN0 3, CH 3COOH, NH4 0H, H 3P0 4 ,
NH4 Cl, NaCl, NaOH, KOH, etc.) HCN, etc.)
(2) Weak electrolytes: These are not completely ionized
when dissolved in a polar solvent and they behave as poor However, an electrolyte may behave as a strong one in aqueous
conductors of electricity, e.g., CH 3 COOH, H 3P0 4 , H 3B0 3 , solution, but it may behave as a weak one in another solvent. For
NH4 OR, etc. Equilibrium between ions and unionised molecules example, sodium chloride behaves as a strong electrolyte and
is established in solution; e.g., acetic acid as a weak electrolyte when dissolved ~n water but their
con9.ucting abilities are comparable in liquid ammonia solvent.
CH 3 COOH ~ ~H3 COO- + H+
The above equilibrium is termed as ionic equilibrium. Degree of 10.2 OSTWALD'S .DILUTION LAW
ioni~ation of weak electrolytes is much less than unity. According to Arrhenius theory of electrolytic dissociation, the
Degree of ionization 'a.' may be defined as a fraction of total molecules of an e'lectrolyte in solution are constantly splitting up
number of molecules of an electrolyte which dissociate into ions. into ions and the ions are constantly reuniting to form. unionized
% ionization molecules. Therefore, a dynamic equilibrium exists between ions
100 and unionized molecules of the electrolyte in solution. It was
Numberof molecules dissociated as ions pointed out by Ostwald that like chemical equilibrium, law of
Total number of molecules of electrolyte dissolved . mass action can be applied to such systems also.
Consider a binary electrolyte AB which dissociates into A +
The following classification of electrolytes is based on their
behaviour in a particular solvent, i. e., water. and B - ions and the equilibrium state is represented by the
equation:
IONIC EQUILIBRIUM 657
Solution: Degree of dissociation, In presence of strong electrolyte, the total CN- concentration
A 14 ~ comes from KCN which undergoes complete dissociation. It is
0 , = - = - = 3.58 x 10
further assumed that dissociation ofHCN is very-very sman and
A"" 391
the concentration of HCN can be taken as the concentration of
[1- a ---71 as a is very small] undissociated HCN.
Now applying Ostwald's dilution law,
Thus, [HCN] = 0.2 M and [CN- ] 1M
2
K _a__
a .(l-a)V Putting these values in the expression
10
[H+] = K b [HCN] = 4 x 10- x 0.2 = 8 x 10- 11 mol [;1
a = 3.58 x 10-2 and V = _1_ litre
[CN-] 1
0.0128
2 2 Note: When KeN is not present, the [H+ ] concentration is equal to
So, Ka =3.58xl0- x 3.58 x 10- x 0.0128 1.64xlQ-5
..[CK, i.e., ~O.2 x 4 X 10- 10 = 8.94 X 10-6 mol L- 1• This shows
that concentration of H+ ions falls considerably when KeN is
added to HeN solution.
Let AB be the weak electrolyte. Considering its dissociation, ~Jample 7. Determine the concentration of hydroxyl ions
AB A+ +B- in 0.4 M NH 4 OH solution having (i) no ammonilim c,hlorideqnd
. and applying law of mass action, we have (ii) 5.35 g ofN}/4Clin a Utreof the solution. Ionisation constant
ofNH4 0H is 1.8 x 10-5 .
[A+][B-]
K==-'---=-..... Solution: (i) Let 'a' be the degree of dissociation of
[AB]
NH4 OH in absence ofNH4 Cl.
The equilibrium constant, K, has a definite value 11t any given
temperature. If now another electrolyte furnishing the A + and B- a =J?. .
ions be added to the above solution, it will increase the So, [OW] = Co, == ~K bC == ~1.8 X 10-5 x 0.4
concentration of either A + ions or B - ions (whichever has been
2.68 x 10-3 mol L-1
added) and in order that K may remain constant, the
concentration of AB must increase, i.e., the equilibrium will shift (ii) In presence ofNH4C~
to the left hand side. + 5.35
[NH4]=-=0.IM and [NH 40H]=004M
In other words, the degree of dissociation of an electrolyte 53.5 . '
(weak) is suppressed by the addition of another electrolyte 5
So, [OW] K b [NH40H] == 1.8x 10- x 004
(strong) containing a common ion. This is termed as common
[NH~] 0.1
ion effect. Acetic acid is a weak electrolyte and its.ionisation is
suppressed in presence of a strong acid (H+ ion as common ion) =7.2xlO- 5 molL-I
or a strong salt like sodium acetate (acetate ion as common ion). if&W:~~:xample 8. When 0.100 mole of ammonia, NH 3 , is
Similarly, the addition of NH4 CI or NaOH to NH40H solution dissolved in sufficient water to make 1.0 L of solution, the
will suppress the dissociation of NH4 0H due to common ion solution is found to have a hydroxide ion concentration of
either NH~ or OH . 1.34 x 10-3 M. Calculate K b for ammonia.
As a result of common ion effect, the concentration of the Solution:
ion not in common in two electrolytes, is decreased. The use of
this phenomenon is made in qualitative analysis to adjust NH3' + H20~ NH!
At equilibrium (0.100 - 1.34 x 10-3 ) M 1.34 x 10-3 M
concentration of S2- ions in second group and OH- ion
concentration in third group of analysis. + OW
=O.09866M 1.34 x 10-3 M
K _ [NH~ ][OW]
3 3
1.34 X 10- x 1.34 X 10- = 1.8199x 10-5
!;:J{(;~.~xample 6. The ionisation constant of HCN is 4 x 10- 10 .
b - [ NH 3] 0.09866
Calculate the concentration ofhydrogen ions in 0.2 M solution of
HCN containing Imol rl ofKCN ;{Ci(cExainple 9. : K a for HA is 4.9 x 10-8 . After making the
Solution: The dissociation ofHCN is represented as necessary approximation, calculate for its decimolar solution
(a) % dissociation
, HCN~Hi +CW
(b) H+ ion concentration"
Applying law of mass action, Solution: (a) For a weak electrolyte,
[H+][CW]
~Ka ~4.9X 10-
8
K ,=----- or [H+]= Ka [HCN] a = 7x 10-4
a [HCN] [CN-] C 0.1
IONIC EaUIUBRIUM I 659
0.0145 == ~ 0.066
Ka ... (i) So,
(0.08+
, x)x
(OJ-x)
Let the degree of dissociation of the acid at 0.02 M
concentration be a I . As xis very small, (0.1 x) ----? 0.1 and neglecting x 2 ,
fK: , .. (ii) K == O.08x
V0.02 a 0,1
660 G.R. B. PHYSICAL CHEMISTRY FOR CoMPETITIONS
Ionic product of Ag 2 Cr0 4 [Ag + ]2[CrO~-] Let S mol litre -I be the solubility of AB 3'
= (Ix 10-2 )z (1 X 10-2 )' Ks =[A 3+][B-]3 SX(3S)3 ==27S 4
= 1 X 10-6 or S::::~KsI27
6 IZ
I X 10- is higher than 2 x 1O- and thus precipitation of The presence of common ion affects the solubility of a salt.
Ag 2CrO 4 occurs. Let AB be a sparingly soluble salt in solution and A' B be added to
it. Let Sand S' be the solubilities of the salt AB before and after
AeIaIionship ......... su....-, and SaIubIiI.J IIIocIua addition ofthe electrolyte A' B. Let c be the concentration of A' B.
Salts like Ag~ BaS04 , PbS0 4 , PbI z, etc., are ordinarily Before addition of A' B, K s == S 2 ... (i)
. considered insoluble but they do possess some solubility. These
are sparingly soluble electrolytes. A saturated solution of After addition of A' B, the concentration of A + and B - ions
sparingly soluble electrolyte contains a very small amount of the become S' and (S' + c),respectively.
dissolved electrolyte. It is assumed that whole of the dissolved So, Ks :::: S' (S' + c) ... (ii)
electrolyte is present in the form of ions, i. e., it is completely
dissociated. Equating eqs. (i) and (ii),
The equilibrium for a saturated solution of any sparingly S2 =S'(S' +c)
soluble salt may be expressed as: Caladatioa of rwnNing coneeatntion after precip~_ ...
.....: Sometimes an ion remains after precipitation if it isitf~
A B--:-"xA Y+ + yB X-
x y-V-
excess. Remaining concentration can be determined, e.g.,
Thus, solubility product, K s :::: [A Y+ Y [B x- Y
+ Ksp [AB]
(i) [A ]Ieft == [B-]
Let'S' mol litre -I be the solubility of the salt; then
AXBy ~xAY+ + yB X-
") [C 2+] _ K sp [Ca(OHh]
xS yS (11 a left -. - - - ' - - - -
[OH-]2,
So, Ks [xSnysy
";xx, yY(Sr+Y
(i) I: Ilftle aIts; Examples: AgCI, AgI, BaSO4' PbSO 4'
Percentage precipitation of an ion
A+ +B- Initial conc. - Left conc.] x 100
8 8
[ Initial conc. ,
Let solubility of AB be S mol litre -I .
So, Ks [A+][B-] SxS S2 SinUIaneaus SaIubIiI.J
or S=Ji(' , Solubility of two electrolytes having common ion; when they
(1)1:2 .. 2:t lftIe salls:: Examples: Ag 2 C0 3 , are dissolved in the same solution, is called simultaneous
solubility, e.g.,
Ag 2 CrO 4' PbCI 2 , CaF2 , etc.
(i) Solubility of AgBr and AgSCN, when dissolved together.
(ii) Solubility ofCaF2 and SrF2 , when dissolved together.
(iii) Solubility ofMgF2 and CaF2, when dissolved together.
Let solubility of AB2 be S mol litre -I. Calculation of simultaneous solubility is divided into two
SO, Ks =[A 2+][B-f :=SX(2S)2 ::::4S 3 cases:
or S VK s l4 c.e I: When the two electrolytes are almost equally strong
(having close solubility product), e.g.,
AgBr(Ksp 5xlO- 13 ); AgSCN(Ksp 10- 12 )
Let S be the solubility of A'2B. (See ........ 26.)
Ks [A+]2[B2-] Here, charge balancing concept is apr-lied.
:::: (2S)2 (S)== 4S 3 Charge of Ag + = Charge of Br - + Charge of SCN-
or S =VKJ4 [Ag+]= [Br-] + [SCW]
On the basis of this equation, the concentration ofCrO~- ions 4.4921 X 10- 12 0.02(S,)2
will be half of the concentration of Ag + ions. or (s')2 4.4921 x 10- 12
Thus, [Ag +] =:: 1.5 X 10- M and [CrO~-] = 0.75 X 10-4 M
4 0.02
S' 14.9868 X 10-6 mol L- 1 .
Ks [Ag + ]2[CrO~-] =(1.5 x 10-4 i (0.75 X 10-4) or
K sp = [Pb 2+][r]2
[NH: ] K NH40H X [NH 4 0H]
[OH-]
=S X (2S + 0.1)2
1.8 x 10,-5 x 0.05 = 0.067 M
=S X(4S2 +O.OI+O.4S) l.34x 10-5
4S 3 + O.OIS + 0.4S 2 i. e., [NH4 Cl] = 0.067 M
. Neglecting S 3 and S 2 , Example 24. The solubility product of Ag 2C 20 4 at 25°C
1.4 X 1O~8 =O.OIS is 1.29 x 10- 11 mol3 C 3. A solution of K 2C 20 4 containing
8
0.1520 mole in 500 mL of water is shaken with excess of Ag 2 C03
or S = 1.4 X 10- 1.4 X 10-6 mol L- 1 till the following equilibrium is reached.
0.01 Ag 2C0 3 +K 2C 20 4 ~Ag2C204 +K 2C03
Example 22. The solubility product of lead, bromide is At equilibrium, the solution contains 0.0358· mole of K 2C03'
8 x 10-5 . If the salt is 80% dissociated in saturated solution, find Assuming the degree of dissociation of K 2C204 and K 2C03 to
be equal, calculate the solubility product of Ag 2 C03 • (lIT 1991)
the solubility ofthe salt. Solution: . .,., ,.
Solution: Let S be the solubility of the salt.
Ag 2C0 3 + K 2C20 4 ~Ag2Ci04 + K 2 C0 3
Degree of dissociation of the salt = 0.8. Initial 0.1520 mole 0
PbBr2 ~ Pb 2+ + 2Br- At equilibrium (0.1520 0.0358)
0,1162 mole
0.0358 mole
. 0.8S 2 x 0,.8S Concentration
2 x 0,1.162 2 x 0.0358
= (0.8S) x (1.6S)2
= 2.048S 3
5
or S3 = 8x 10- = 3.906x 10-5
2.048
S = V3.906 X 10-5 = 3.39, X 10-2 mol L- 1
Mol. mass ofPbBr2 = 367
Solubility of PbBr2 ' 3.39 x 10-2 x 367 = 12.44 g L-1
Example 23. A solution has 0.05 M. Mg2+ and 0.05 M
NH 3' Calculate the concentration of NH 4 CI required to prevent
the formation of Mg( OHh in this solution. K sp of Mg( OH)z
= 9.0 X 10-12 and ionisation constant ofNH3 =1.8 X 10-5 .
(lIT 1993)
Solution: The maximum concentration of [OIr] ion~ that
will precipitate Mg(OHh is calculated by applying the equation
K sp = [Mg 2+ ][OH- f
12
[OIr]2= Ksp
9.0xlO- =1.8xl0-10
[Mg 2+] 0.05 .
or 5
[OH-] = 1.34 X 10- M
NH3 is present in solution in the form ofNH4 OH Solution: No. of moles of Ag + li120mL
NH3 +H20~NH40H.--"'NH: +OH- 20 x 0.001= 2x 10-5
0.05 0.05 1000
The ionisation of NH 40H is suppressed by the addition of No. of moles crO~- in one litre = 0.002 = 2 x 10-3
NH4 CI (Strong electrolyte).
After mixing, total vs:llume of the solution
= 1000 + 20 =1020 rnL =1.02 L
I
IONIC EaUILIBRIUM I 665
5
[Ag +] = 2 X 10- = 1.96 x 10-5 8 =0.0223 mol L- 1
1.02 After mixing the two solutions, the total volume becomes
3 1 litre.
[cr02- ] 2 x 10- = 1.96 X 10-3
4 1.02 [Ca 2+] = 0.0223 x 500 = 0.01115 mol L- 1
Ionic product =[Ag+]2[CrO~-] 1000
5 3
= (1.96 x 10- )2 (1.96 X 10- ) [OH- ] 0.0223 x 2 x 500 + 0.4 x 500 = 0.2223 mol L-1
= 7.53 X 10- 13 1000 1000
[From Ca(OHh] (From NaOH)
There will be no precipitation of Ag 2crO4 as ionic product is
less than solubility product. Under thl? high concentration of OH- ions, some Ca(OHh
. tiample 26. Calculate simultaneous solubility of AgCN8 will be precipitated.
and AgBr in a solution of water. K sp of AgCN8 1 x 10- 12 , [Ca 2+heft[OH-]2 =Ksp
Ksp of AgBr= 5x 10- 13 •
[Ca 2+] = 4.42 x 10- 5 =8.94 X 10- 4 mol L-1
,Solution: Let the solubility of AgCNS and AgBr in water be left (0.2223)2
a and b respectively. .
Moles of Ca(OHh precipitated = Moles of Ca 2+ precipitated
AgCNS·~ Ag + + CNS-
a a =[Ca 2+ ]initial - [Ca 2+ ] left
AgBr .----. Ag + + Br- = 0.01115 8.94 x 10-4
b b
[Ag+]=a+b,[CNS-]=a and [Br-] b 111.5 X 10-4 8.94 x 10-4
5 X 10-13 =b(a + b) ... (ii) 6. The solubility product of sparingly soluble salt Ag 2 Cr04 is
4 X10- 12 • The molar solubility of the salt is:
Dividing
, eq. (i) by (ii),
(a) I x 10-4 mol L- 1 (b) 2 x 1O~6 mol L- 1
Ix 10-12 a
13
=- (c) I X 10-5 mol L- 1 (d) 2 x 10- 12 mol L- 1
5 x 10- b
[Ans. (a)]
[Hint: Ksp = [Ag+ ]2[CrO~-]
2=~
. b or a=2b
IfsOlubility of Ag2Cr04 is'S', then [Ag+ ] 2S and[CrO~-] S.
Putting the value of a in eq. (i), K sp 4S 3
=
6h 2 I X 10- 12 ·4 X 10-12 =·4S 3
b 2 = ~ X 10- 12 S =I X 10-4 M]
6
7. The solubility ofPbS04 at 25°C is 1.1 x 10-4 moUL. Then its .
. b 4.08 X 10-7 mol L-1
Ksp is:
a = 2 x 4.08 X 10-7 (a) 1.21 x 10-8 (b) 12.1 X 10-6
- =8.l6x 10-7 molL-1 (c) 121 X 10~1l (d) 1.21 x 10-10
Exalllple 27. The K sp ofCa(OHh is 4.42 KIO- 5 at 25° C. [Ans. (a)]
[Hint: PbS0 4 is a binary electrolyte, hence its Ksp can be
500 mL of saturated solution ofCa(OH)2 is mixed with equal calculated as:
volume of 0.4 M NaOH. How much Ca(OHh in mg is
precipitated? . (lIT 1992)
. Ksp =S2 = [1.1 X 10-4]2 =1.21 X 10-8 ]
Solution: Let 8 be the solubility of Ca(OH)2 in saturated 8. The solubility ofCaF2 (K sp 3.4 x 10- 11 lin 0.1 M solution of
solution. NaP would be:
Ca(OHh Ca 2+ + 20Ir (a) 3.4 x 10-12 M (b) 3.4 X 10-10 M
8 28
(c) 3.4 X 10-9 M (d) 3;4·x 10-13 M
Ksp Ca(OHh =[Ca 2+ ][OH-]2 [Ans. (c)]
4.42 x 10-5 = S x 48 2 =48 3 [Hint: CaF2 :r== Ca 2+ + 2F-
x 2x
666 .1 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
[Ca +] = x,
2
[F-] = [2x + O.l] '" 0.1 M Ksp [Sb3+ ]2[S2-]3 :::: [2S ]2[3S]3 = 108 S5
Ksp = [Ca 2+ ][F-]2 = 108 X (10-5 )5 :::: 108 x 10-25 ]
3.4 X 10- 11 =x(O.l)2
Applications of Solubility Product
x:::: 3.4 x 10-9 M] (i) Purification of common salt
9. The solubility product of Agel is 1.8 x 10- 10 . Precipitation of Natural common salt consists of many insoluble and soluble
AgCl will occur only when equal volumes of which of the impurities. Saturated solution of common salt is prepared and
following solutions are mixed? insoluble impurities are filtered off. Hydrogen chloride gas (HCl)
(a) 10-4 M Ag+ and 10-4 MCl- is circulated through the saturated solution. HCl and NaCI
dissociate into their respective ions as:
(b) 10-7 M Ag+ and 10-7 MC1-
NaCI ~Na + + Cl-
(c) 10-5 M Ag+ and 10-5 MCI
HCl~H+ +CI-
(d) 10- 10 M Ag+ and 10-10 MCl-
The concentration of CI- ions increases considerably in·
[Ans. (a)]
solution due to ionisation of HC\; Hence,theionic product-
[Hint: After mixing, [Na + ][CI-] exceeds the solubility product of sodium chloride
[ Ag+ ] '" ~ X 10-4 = 5 X 10-5 M and, therefore, pure sodium chloride precipitates out from
2 solution.
[CI-] 1 x 10-4 = 5 X 10-5 M (ii) Salting out of soap
2
Soap is a sodium salt of higher fatty acids. From the solution,
Kip = [Ag+ ][Cl-] (5 x 1O-5i = 2.5 x 10-9
soap is precipitated by the addition of concentrated solution of
Since, ionic product is greater than solubility product, hence sodium chloride. Soap and sodium chloride are present in the
precipitation will take place.] form of ions.
10. If x mol L -I is the solubility ofKAl(S04 b then Ksp is equal C nH211 + 1 COONa ~ C nH 2n +! COO- + Na +
Soap
to:
(a) x 3 NaCI~Na+ +cr-
[Ans. (b)] Thus, the concentration ofNa + ions increases considerably on
[Hint: KAl(S04h ~ K+ + A1 3+ + 2S0~- addition of NaCl solution. Hence, the ionic product
x x 2x [CnHZn + 1COO- ] [Na +] exceeds the solubility product of soap
Ksp '" [K+ ][A1 + ][SO~-]2
3
and, therefore, soap precipitates out from the solution.
:::: X X X X (2x)z :: 4x4] (iii) Manufacture of sodium bicarbonate (baking soda)
11. For which of the following sparingly soluble salt, the In Solvay's soda process, CO 2 gas is passed through
solubility (S) and solubility product (Ksp) are related by the ammonical brine to precipitate out NaHC0 3.
expression: NH40H+C02 ~NH4HC03
NH 4HC0 3 + NaCl ~ NaHC0 3 + NH4 CI
IPET (Kerala) 2006]
NaHC0 3 is precipitated first because of its lower solubility
product as compared to those ofNH 4Cl, NH 4HC0 3 and NaCI.
(a) BaS04
(e) CuS Thus, baking soda (NaHC0 3 ) can be quantitatively estimated.
[Ans. (c)] (Iv) Application of solubility product in quantitative
analysis
[Hint: Hg2Cl z ~ H~+ + 2CI-
8 8 2S 1. Estimation of barium as barium sulphate: H2 S04 as
precipitating agent is added to the aqueous solution ofBaCl 2.
BaCl 2 + H2 S04 ~ BaS0 4 + 2HCI
Precipitation of BaSO 4 takes place when its ionic product
exceeds solubility product. H2 SO 4 is added in slight excess to
ensure complete precipitation. Large excess of H 2 S0 4 is harmful
12. The solubility of Sb 2S3 in water is 1 x 10-5 mollL at 298 K. for complex formation.
What will be its solubility product? IPMT (Raj.) 2006] 2. Estimation of silver as silver chloride: NaCI solution
(a) 108 x 10-25 (b) 1.0 x 10-25 is added to the silver nitrate solution; slight excess of NaCI is
(c) 144 X 10-25 (d) 126 x 10-24 added to ensure complete precipitation.
[Ans. (a)] AgN03 + NaCI ~ AgCI + NaN0 3
I
IONIC EQUILIBRIUM 667
Again, precipitation of AgCI takes place when ionic product (vi) PreCipitation of III group hydroxides
of AgCI exceeds its solubility product. When NH 40H is added in presence of NH4 Cl then
3. ' In a similar manner, we estimate lead as lead chromate, precipitation of III group hydroxides takes place, i.e., Al(OH)3 ,
calcium as calcium oxalate, etc. Fe(OHh and Cr(OHh are precipitated. Solubility product of III
group hydroxides is less than those of higher group hydroxides.
(v) Precipitation of the sulphides of group II and IV NH 4Cl ~ NH4+ + Cl-
Hydrogen sulphide is a weak electrolyte and is used for the NH40H~NH4+ + OW
precipitation of various sulphides of group II and IV in
qualitative analysis. . NH4+ ion furnished by NH 4CI lowers the ionisation of
NH 40H and hence the concentration of hydroxide ion OH- . At
It ionises to a small extent in water:
low concentration of hydroxide ion only III group hydroxides
H2S~2H + + S2-
precipitate.
Applying law of mass action,
[H+ ]2[S2-] Fractional Precipitation
K It is a technique of separating two or more ions from a
[H 2 S]
solution by adding a reagent that precipitates first one ion and
The concentration ofS 2- ions can be decreased by increasing then the second.
concentration of H+ ions and it can be increased by decreasing
Let us suppose 0.1 MBa2 + and OJ MSr 2+ in aqueous"<
concentration of H+ ions. In group II, lower concentration of
solution. K ZCr0 4 is added as precipitating agent. K sp ofBaCr04
sulphide ions is required as the solubility products of the
sulphides of group II are low while higher concentration of is 1.2 x 10- 10 andKsp ofSrCr04 is 3.5x 10-5 •
sulphide ions is required in group IV as the solubility products of [CrO~- ] concentration required to precipitate BaCrO 4
the sulphides of group IV are high. The values of solubility 10
products of various sulphides are given below: . =.Ksp 1.2 x 10- =1.2xlO-9
... ~
acid-base pairs. . , H~04 (Ortho- <1l H2 PO; (Dihydrogen ...
<1l
phosphoric 'E0 phosphate ion) 'E0
If in the above reaction, the acid CH 3COOH is labelled acid 1 acid) OIl OIl
and its conjugate base, CH3COO- as basel' H 2 0 is labelled as
CH3COOH(Acetic acid) = CH3COO-(Acetate ion)
';jl
~
=
';jl
basez and its conjugate acid H30+ as acid z, the reaction can be "~
~ RCO; (Hydrogen
written as:
H2 C0 3
H2 S
(Carbonic
acid)
(Hydrogen
- HS-
carbonate ion)
(Hydrosulphide
-g
sulphide) ion) .
Thus, any acid-base reaction involves two conjugate pairs,
i. e. , when an acid reacts with a base, another acid and base are NH! (Ammonium N1J3 (Ammonia)
ion)
formed. Some more examples are given below:
HCN (Hydrogen CN- (Cyanide ion)
Acid I + Base 2 ~ Acid 2 + Basel
cyanide)
HZO+NH 3 NH; + OW
C6HsOH (phenol) C6HsO- (Phenoxide ion)
HCN + H 2 0 H30+ + ~
H2 O (Water) OH- (Hydroxide ion)
HF+CH3COOH~CH3COOH; +F-
C2 HsOH (Ethyl alcohol) CzHsO- (Ethoxide ion)
CH 3COOH + NH3 ~NH; + CH3 COO-
NH3 (Ammonia) NH2" (Amide ion)
NH3 + NH3 ~NH; + NH2
CH4 (Methane) CHj (Methide ion)
H zO+H 20 H30+ +OH-
HC03' + H20~H30+ + CO~-
I
670 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
In acid-base strength series, all acids above H 30+ in aqueous explained by the fact that bond energies decrease. (H-F = 135
solution fall to the strength ofH3 0+. Similarly, the basic strength kcal/mol, HCl = 103, HBr 88 and HI = 71 kcal/mol)
(c) Oxyacids: (i) The acidic character of oxyacids of the
of bases below OH- fall to the strength of OH- in aqueous
same element which is in different oxidation states increases with
solution. This is known as levelling effect.
increase in oxidation number.
The strength of an acid also depends upon the solvent. The +1 +3 +5 +7
acids HCl0 4 , H 2S0 4 , HCI and HN0 3 which have nearly the HCIO< HCI0 2 < HCI0 3 <HCI0 4
same strength in water will be in the order of HCI0 4 > H2 SO 4 +4 +6 +3 +5
> HCI > HN0 3 in acetic acid, since, the proton accepting H 2S03 <H 2S04; HN0 2 <HN0 3
tendency of acetic acid is much weaker than water. So, the real
'Strength of acids can be judged by solvents. On the basis of But this rule fails in oxyacids of phosphorus.
:,roton interaction, solvents can be classified into four types: H 3P0 2 > H 3P0 3 > H 3P0 4
(i) Protophilic solvents: Solvents which have greater
tendency to accept protons, i. e. , water, alcohol, liquid ammonia, (ii) The acidic character of the oxyacids of different elements
which are in the same oxidation state decreases as the atomic
etc.
number increases. This is due to increase in size and decrease in
(ii) Protogenic solvents: Solvents which have the tendency
electronegativity.
to produce protons, i.e., water, liquid hydrogen chloride, glacial
acetic acid, etc. HCI0 4 > HBr0 4 >HI0 4
(iii) Amphiprotic solvents: Solvents which act both as
H2 S03 > H2 Se03
. protophilic or protogenic, e.g., water, ammonia, ethyl alcohol,
etc. Limitations: There are number of acid-base reactions in
(iv) Aprotic solvents: Solvents which neither donate nor which no proton transfer takes place, e.g.,
accept protons, e.g., benzene, carbon tetrachloride, carbon S02 + S02 ~ S02+ + SO~-
disulphide, etc. Acid I Base2 Acid 2 Basel
HCI acts as acid in H 20, stronger acid in NH 3 , weak acid in Thus, the protonic definition cannot be used to explain the
CH 3 COOH,neutral in C6H6 and a weak base in HF. reactions occurring in non-protonic solvents such as COCI 2 ,
HCI + HF --t H 2CI+ + F- S02,N204,etc.
Base Acid Acid·· Bilse
(3) Lewis concept
Periodic Variations of Acidic and Basic Properti,~' This concept was proposed by GN. Lewis, in 1939.
(a) Hydracids ofthe elements-of the same perio\l: Consider According to this concept, a base is defined as a substance
n
the hydracids of the elements of period, viz., CH4 , NH3 , H2
and HF. These hydrides become increasingly acidic as we move
° which can furnish a pair of electrons to form a coordinate
bond whereas an acid is a substance which can accept a pair
from CH4 to HF. CH 4 has negligible acidic properties while HF of electrons. The acid is also known as electron acceptor or
is a fairly stronger acid. The increase in acidic nature is due to the electrophile while the base is electron donor or nucleophile.
fact that the stability of their conjugate bases increases in the A simple example of an acid-base is the reaction of a proton
order
CH) <NH z <OH- <F-
with hydroxyl ion.
H++:O:Ir
.. H:O:H
The increase in acidic properties is supported by. the •• ••
Acid Base
successive increase in the dissociation constant.
Some other examples are:
CH 4 (=1O-58 )<NH3 (=10-35 )<H20 1O-14)<HF 10-4)
H3N: + BF3 H3N -t BF3
(b) Hydracids of the elements of same group: (i) Hydrides Base Acid
of V group elements (NH3' PH 3 , AsH 3 , SbH 3 and BiH3 ) show H+ + : NH3 =[Hf-NHd+
basic character which decreases due to increase in size and Acid Base
decrease in electronegativity from N to Bi. There is a decrease in
BF3 + [Fr =[F -t BF3 t
electron density in sp 3-hybrid orbital and thus electron donor Acid Base
capacity decreases.
Lewis concept is more general than the Bronsted Lowry
(ii) Hydracids of VI group elements (H 20, H 2S, H 2Se and concept.
H2 Te)act as weak acids. The strength increases in the order
According to Lewis concept, the following species can act as
H z O<H2S <H2Se <Hz Te Lewis acids:
The increasing acidic character reflects decreasing trend in the (i) Molecules in which the central atom bas incomplete
electron donor capacity of OH- , HS- , HSe- or HTe - ions .. octet: All compounds having central atom with less than 8
(iii) Hydracids of VII group elements (HF, HCI, HBr and HI) electrons are Lewis acids, e. g., BF3 , BCI 3 , AICI 3 , MgC12'
show acidic nature which increases from HF to HI. This is BeC1 2 , etc.
IONIC EQUILIBRIUM 671
(ii) Simple cations: All cations are expected to act as Lewis infinite dilution the dissociation of an acid is nearly complete and
acids since they are deficient in electrons. However, cations such all acids are equally strong at infinite dilution.
as Na + , K +, Ca 2+, etc., have a very little tendency to accept The concentration of H+ ions at all other dilutions of
electrons, while the cations like H+, Ag + , etc., have greater equimolar solutions of the acids may not be equal and depends on
tendency to accept electrons and, therefore, act as Lewis acids. their degree of dissociation. Thus, to measure the relative
strength of the two acids, the measurements of hydrogen ion
(iii) Molecules in which the central atom has empty
concentration, i. e. , degree of dissociation is made of equinormal
d-orbitals: The central atom of the halides such as SiX 4 ,GeX 4,
solutions of the two acids. Various methods are used for this
TiCI 4 , SnX 4, PX 3' PFs , SF4 , SeF4 , TeCI 4 , etc., have vacant purpose. Some are described below.
d-orbitals. These can, therefore, accept an electron pair and act as
(i) The conductivity method: The degree of dissociation
Lewis acids.
(iv) Molecules having a multiple bond between atoms of of a weak acid is equal to conductivity ratio A . Thus, the
dissimilar electronegativity: Typical examples of molecules A"" .
falling in this class of Lewis acids are CO 2 , S02 and S03' Under degrees of dissociation a 1. and a 2 for two equinorrnal acids are
the influence of attacking Lewis base, one 1t-electron pair will be given by:
shifted towards the more negative atom. For acid I,
OH
I and For acid II, a2 =
o LewisC= 0+ OH- ~ - 0 - C=O or HCO:3
A ""2
acid Lewis base
At infinite dilution, all weak electrolytes have almost the same
The following species can act as Lewis bases: value of A",,; hence,
(i) Neutral species having at least one lone pair of
electrons: For example, ammonia, amines, alcohols, etc., act as A""l = A""2
..
NH2 , R
..
Lewis bases because they contain a pair of electrons.
O-H
Strength of acid I =_a_
1 = =
1000 x sp. condo acid I
C
Strength ofacid II a 2 A2 1000 x sp. condo acid II
(ii) Negatively charged species or anions: For example, C
chloride, cyanide, hydroxide ions, etc., act as Lewis bases. Sp. condo acid I
CN-, CI-, OW Sp. condo acid II
It may be noted that all Bronsted bases are also Lewis bases
The relative strength of two acids is, thus, equal to the ratio of
but all Bronsted acids are not Lewis acids.
their equivalent conductance or specific conductance of
Limitations: Since, the strength of the Lewis acids and bases equinormal solutions which can be determined experimentally.
is found to depend on the type of reaction, it is not possible to
(ii) Comparing dissociation constants: Let K I and K 2 be
arrange them in any order of their relative strength.
The choice of which definition of acids and bases one wishes the dissociation constants of two acids and let a 1 and a 2 be their
to use in a particular instance depends largely on the sort of degree of dissociation in equinormal solutions.
chemistry that is studied. But Arrhenius concept is perfectly
satisfactory and simplest for dealing with reactions in aqueous
Applying Ostwald's dilution law, a I = f%. and a 2 = ~~
solutions. It explains satisfactorily the strength of acids and bases
Thus,.
Strength of acid I _ a I _ ~1
in aqueous solutions, neutralisation, salt hydrolysis, etc.
Strength of acid II a 2 K2
-jQ"~RELATIVE STRENGTH OF ACIDS Dissociation constants of some weak acids are given in the
tahle:
AND BASES
According to Arrhenius concept, an acid is a substance which Acid-ionization constants at 25 DC
furnishes H+ ions when· dissolved in water. All the acid
properties on an acid are due to H+ ions present in the solution.
Su-.stallql .aa
Fo......
Acetic acid HC2HP2
The extent to which an acid property is given by an acid is
a measure of its strength. The strength of the acid solution Benzoic acid HC 7H s0 2 6.3xlO-s
does not depend on its concentration but on the number of Boric acid H 3B03 5.9 x 10- 10
H+ ions present. The concentration of H+ ions depends on the
Carbonic acid H2C0 3 4.3 x 10-7
ionisation of an acid in solution. On dilution, the ionisation
increases and more of H+ ions come to solution with the result
HCOi 4.8 x 10-11
that the strength ofthe acid increases. Thus, str~ngth ofthe acid Cyanic acid HOCN 3.5 x 10-4
increases on dilution while its concentration decreases. At
I
::,...
each of the two acids is rnbc.ed and one gram equivalent ofNaOH
is added. Let the heat evolved in this case be 'z' calorie~ The two 14; In the reaction, .
acids will neutralise a fraction of the base proportional to their H~O; + po~- ~ HPO~- + ~o~-
relative strength.· Suppose n .gram equivalent Of NaOH is the Bronsted base are: (PET (Raj.) 2004]
neutralised by acid I and the rest (1- n ) by acid II. (a) P~- ,~O~- (b) PO!- ,~-
Total heat evolved, z::;: nx + (1- n)y (c) H~O;, HPO~- (d) H~O;, ~O~-
:::,nx+y-ny
[Ans. (a)]
or z-y=n(x-y)
(z y) [Hint: Acid H+ = Conjugate base]
or n=---
(x- y) 15. COnjugate base of HCO; is: . [PET (Raj.) 2005]
(a) CO2 (b) H 2C03 (c) H20 (d) coi-
Strength of acid I n (x":,,y) (z-y) [Ans. (d)]
So, ----==::..---- = - - ::;: ::;: - - - [Hint: Acid R"'; Conjugate base, HeO; - H~ COi-]
Strength of acid II (1- n) 1- (z - y) (x - z)
16; Four species are listed below: .
(x- y)
Relative strength of bases:. A base is a substance which
(i) HCO; (ii) H3°
+
(iii) HSO; (iv) HS03F
Which one of the following is the correct sequence of their
gives OH ions when dissolved in water. The strength of the acid strength? (AIEEE 2008)
base depends on OH - iori concentration. The above methods can (a) (iii) < (i) < (iv) < (ii) (b) (iv) < (ii) < (iii) < (i)
be used for measuring relative strengths of bases also. In the (c) (ii) < (iii) <0) < (iv) (d) (i) «iii) < (ii) «iv)
Thomson thermal method, the two bases and their mixtures will [Ans. (d)]
be neutralised by strong acid, say HCt.
The relative strengths of some of the acids are as follows: [Hint:
+ .
(i) HCI0 4 >HBr>HCl>HN03 > H 2S04 >H30+ >·H 2 S0 3 HS0 3F is super acid and it is most acidic. H3 0 is more acidic than
> H2 C0 3 > CH 3 COOH anions because . anions (HCO;, HSO;jJ do not release H+ ion
(ii) HCI04 > HCI0 3 > HCI02 > HClO easily. HSO~ is more acidic than HCO; becauSe sulphur is more
(iii) H~ > HBr > HCl > HF . e1ectronegativethan carbon.]
IONIC EOOIUBRIUM I 673
17. Identify Bronsted-Lowry acids in the reaction given: (iii) A weak acid plus a strong base gives a basic solution as
[AI(H20)6]3+ + HCOi ~ [AI (H 2 0)s (011 )]2+ + H2C03 the weak acid is not completely ionised. The reactnm does not go
(A) (B) (C) (D) to completion and there is an excess of hydroxyl ions in solution.
The correct answer is: (EAMCET (Med.) 2008) CH 3COOH+Na+ +OH- H 20+CH3COO- +Na+
(a) A, C (b) B, D (c) A, D (d) B, C
[ADs. (e)] (iv) A weak acid plus a weak base gives an acidic or a basic or
[Ilint : [Al(HPh;]3+ and H2CO) are proton donor or Bronsted a neutral solution depending on the relative strength of acid and
acids] base. In case, both have equal strength, the resulting solution is
neutral in nature.
18. Conjugate base ofH2PO:;- is: [Corned (Karnataka) 2008J
(a) HPO~- (b) PO~- (c) H3P04 (d) HPO:;- CH3COOH+NH40H~H20+NH; +CH 3 COO-
(ii) Usually, oxides of highly electropositive metals are basic. or [H+] = [OW ] = I X 10-7 mol litre-1
These oxides dissolve in water to form base and they form salt This shows that at 25° C, in 1 litre only 10-7 mole of water
with acids.
is in ionic form out of a total of approximately 55.5 moles.
e.g., Na 2 0, KzO, MgO, CaO, SC 20 3 , Ti02,Zr02
When an acid or a base is added to water, the ionic
Na20+ H z 0-----7 2NaOH concentration product, [H +] [OH- ], remains constant, i. e. , equal
(Sodium hydroxide, a base)
*pK value: p stands fot negative logarithm. Just as H+ and OH - ion cQucentrations range over many negative poWers of.1 0, iUs convenient to
express them as pH or pOH, the dissociation constant (K ) values also range over many negative powers of 10 and it is. convenient to write them as pK.
Thus; pK is the negative logarithm of dissociation constant. .
pKa =-logKa and pKb =-logKb
Weak acids l]ave higher pKa values. Similarly, weak bases have higher pKb values.
676 G.R.B. PHYSICAL CHEMISTRY FOR COMPETITIONS
Any method which can measure the concentration of H+ ions [H+] [A-]+[B-]+[OW]
or OH- ions in a solution can serve for finding pH value. = Ka[HA] + Kb[HB] + Kw
Limitations of pH Scale: (i) pH values of the solutions do [H+ ] [H+ ] [H+ ]
not give us immediate idea of the relative strengths of the
solutions. A solution of pH = I has. a hydrogen ion concentration [W] =.JKa [HA]+ Kb[HBJ+Kw
100 times that of a solution of pH 3 (not three times). A =~CKo +CK b +Kw
4 x 10-5 N HCI is twice concentrated. of a 2 x 10-5 N HCI
(vi) Let us consider mixture of two weak bases AOHandBOH
solution, but the pH values of these solutions are 4.40 and 4.70 with dissociation constant K 1 ,K 2 and concentration C1 , C 2
(not double). respectively
(ii) pH value of zero is obtained in I N solution of strong acid.
In case the concentration is 2 N, 3 N, 10 N, etc. The respective
pH values will be negative.
(iii) A solution of an acid having very low concentration, say ~t~: pH OF WEAK ACIDS AND BASES
10-8 N, cannot have pH 8, as shown by pH formula, but the
actual pH value will be less than 7. Weak acids and bases are not completely ionised; an equilibrium
[Note: (i) Nonnality of strong acid = [H30+ ] is found to have been established between ions and unionised
molecules. Let us consider a weak acid of basicity' n' ..
Normality of strong base = [OH- ]
AHn A n- + nH+
pH - log.[N ] for strong acids 1=0 COO
leq C(l a) Ca nCa
pOH = -log [N] for strong bases
(ii) Sometimes, pH of acid comes more than 7 and that of base [H+] =nCo.; pH=-logIO [nCo.] ... (i)
comes less than 7. It shows that the solution is very dilute; in For monobasic acid, n:= I
such cases, H + or OH - contribution from water is also pH= -log}O [Cql ... ,(ii)
considered, e.g., in 10-8 N Hel,
Dissociation constant of acid K a may be calculated as:
[H + homl = [10~ kid + [l0-71watcr [An-][H+]n [Ca][nCa]1I
Ko
= 11 X 10- 8 M :: 1.1 X 10-7 M [AHn] C(l-a)-
(iii) pH of mixture: Let one litre of an acidic solution of pH 2 be a[nCa]n
mixed with two litre of other acidic solution of pH 3. The
=~--=- [for weak acids, a «1
(I-a)
resultant pH of the mixture can be evaluated in the following
way: :.(1-«)= 1] .
:=a[nCat
~j~';":'$~1 ';: .Sampi.~'
pH::2 pH=3
nCK 0 = nCar nCa]n =[nCo. ](n + 1)
[nCal = [nCKa ]1/(n+ 1)
[W J= 10-2 M [H+] 10-3 M
[H+ ] == [nCK a ]"(n + I)
V = 1 litre v = 2 litre
1
MtVI + M 2V2 = MR(VJ + V2 ) pH=---loglO (nCKa) ... (iii)
(n + 1)
10:"2 xl + 10-3 X 2 = M R (1 + 2)
For monobasic acid, n =1
12 X 10-3 _ M
3 - R pH= -loglO ~CKa ... (iv)
4 X 10-3 = MR (Here, MR Resultant molarity)
Since, Ka a[nCat
3
pH = log (4 x 10- )
K
(iv) Total concentration of [H+ ] or [Hj 0] in a mixture of weak acid _0 =(nCat
a
and a strong acid
= C 2 + ~C; + 4KaCJ K ]"n =[H+]
2
[nCo.] =[ -:
where, C I is the concentration of weak acid (in mol litre -I) having
dissociation constantKa and C 2 is the concentration of strong acid.
... (v)
(v) Let us consider mixture of two weak acids HA and HB.
HA~H++A
HB~H++B
For n = 1, ... (vi)
On applying charge balance
I
IONIC EQUILIBRIUM 677
Ba(OHh ~ Ba 2+ + 20H-
One molecule on dissociation furnishes 20H- ions.
~::;V{~~!'Jnp.e28. The hydrogen ion concentration ofa solution So, [OIr] 2 x 10-3 M
is 0.001 M. What will be the hydroxyl ion concentration of pOH = -log [OH- ]
solution?
= -log (2 x 10-3 ) =2.7
Solution: We know that, [H+ ][OH- ] = 1.0 x 10-14
We know that, pH + pOH 14
Given that, [H+ ] = 0.001 M 10-3 M So, pH = (14- 2.7) = 11.3
14 14
So, [OIr] = LOx 10- Ix 10- =10- 11 M '?l~~~E:lample 31. Find the pH ofa o.002N acetic acid solution,
[H+] 10-3 ifi! is 2.3% ionised at a given dilution.
JLt':j;J.a~J1le 29. What is the pH of the following solutions? Solution: Degree of dissociation, a. = 2.3 =~.023
3 100
(a) 10- M HCI (b) O.OOOIM NaOH (c) O.OOOIM H 2 S04
Concentration of acetic acid, C = 0.002M
Solution: HCI is a strong electrolyte and is completely The equilibrium is,
ionised.
CH3COOH~CH3COO- + H+
HCI~H+ +C1- C(1-a) Ca Ca
So, [H+] = 10-3 M So, [H+]=Ca. =0.002 x 0.023
pH =-log [H+] log (10-3 )=3 = 4.6x 10-5 M
(b) NaOH is a strong electrolyte and is completely ionised. pH =-log [H+]
NaOH~Na+ +OH- =-log (4.6 x 10-5 ) = 4.3372
So, [OH+ ] = 0.000 1M = 10-4 M 't~~fe~~ain'Ple32. Calculate the pH value of a solution
obtained by mixing 50 mL of 0.2 N HCl with 50 mL of O.1N __
pOH - log (10-4 ) = 4
NaOH
As pH+pOH=14 Solution: Number of milli-equivalents of the acid
So,_ pH+4 14 orpH=1O 50x 0.2 10
Alternative method: [OH-] = 10- 4 M Number of milli-equivalents of the base
=50x 0.1=5
We know that, [H + ][OIr ] = 1.0 xlO- 14 Number of milli-equivalents of the acid left after the addition
14 of base
So, [H+ ] 1.0 X 10- = 10-10 M
10-4 = (10- 5)= 5
Total volume of the solution 50 + 50 = 100 mL
pH= log [H+] log(10-lo)=10
Thus, 5 milli-equivalents of the acid are present in 100 mL of
(c) H2 S04 is a strong electrolyte and is ionised completely. solution.
H 2 S04 2H+ + SO~- or 50 milli-equivalents of the acid are present in one litre of
solution.
One molecule of H 2S04 furnishes 2H + ions.
or 0.05 equivalents of the acid are present in one litre of
So, [H+] 2x1Q- 4 M solution.
. pH = - log [H+ ] The acid is monobasic and completely ionised in solution.
-log (2 x 10-4)= 3.70 0.05 N HCI 0.05 M HCI
So, [H+]=0.05M
!)ff~~li~.mP:i~30. Calculate the pH of the following solutions
assuming complete dissociation: pH =-Iog [H+] =-log 5 x 10-2 [log 5.0+ log 10-2 ]
(ii) pH';'; -log [H+ ] Thus, total [OW] = (I X 10-7 + 1.0 X 10-8 )M
Ux 10-7 M
or log [H+] 5.6
pOH=-log 1.1 x 10-7
or
= 6.9586
~";:·~;.~..mp.e 35. How many moles of calcium hydroxide must pH=(14 pOH)=(l4 6.9586) 7.0414
be dissolved to produce 250 mL Of an aqueous solution of