Chemistry Sem I

PROGRAMME: THREE-YEAR B.Sc. (B.
Sc Chemistry)
SEMESTER – I
Subject: Chemistry
Course I (Inorganic & Physical Chemistry)
Semester-wise Syllabus under CBCS (w. e. f. 2020-21)
Course out comes:
At the end of the course, the student will be able to;
1. Understand the basic concepts of p-block elements
2. Explain the difference between solid, liquid and gases in terms
of intermolecular interactions
3. Apply the concepts of gas equations, pH and electrolytes while
studying other chemistry courses
INORGANICCHEMISTRY
UNIT–I
Chemistry of p-block elements
Group 13: Preparation & structure of Diborane, Borazine

Group 14: Preparation, classification and uses of silicones
Group 15: Preparation & structures of Phosphonitrilic halides
{(PNCl2)nwhere n=3, 4
Group 16: Oxides and Oxoacids of Sulphur (structures only)
Group 17: Pseudohalogens, Structures of Interhalogen
compounds.
UNIT-II
1. Chemistry ofd-block elements:
Characteristics of d-block elements with special reference to
electronic configuration, variable valence, magnetic properties,
catalytic properties and ability to form complexes.Stability of
various oxidationstates.
2. Chemistry off-block elements:
Chemistry of lanthanides - electronic structure, oxidation states,
lanthanide contraction, consequences of lanthanide contraction,
magnetic properties. Chemistry of actinides - electronic
configuration, oxidation states, actinide contraction, comparison
of lanthanides and actinides.
3. Theories of bondinginmetals:
Valence bond theory andFree electron theory, explanation of
thermal and electrical conductivity of metals based on these
theories, Band theory- formation of bands, explanation of
conductors, semiconductors and insulators.
PHYSICAL CHEMISTRY
UNIT-III
Solid state
Symmetry in crystals.Law of constancy of interfacial angles.The
law of rationality of indices.The law of symmetry. Miller indices,
Definition of lattice point, space lattice, unit cell. Bravais lattices
and crystal systems.X-ray diffraction and crystal structure.Bragg’s
law.Powder method.Defects in crystals.Stoichiometric and non-
stoichiometric defects.
UNIT-IV
1. Gaseousstate
Vander Waal’s equation of state.Andrew’s isotherms of carbon
dioxide, continuity of state.Critical phenomena.Relationship
between critical constants and vander Waal’s constants.Lawof
corresponding stat es.Joule- Thomson effect .Inversion
temperature.
2. Liquidstate
Liquid crystals, mesomorphicstate.Differences between liquid
crystal and solid/liquid.Classification of liquid crystals into
Smectic and Nematic.Application of liquid crystals as LCD
devices.
UNIT-V
Solutions, Ionic equilibrium& dilute solutions
1. Solutions
Azeotropes-HCl-H2O system and ethanol-water system. Partially
miscible liquids-phenol- water system. Critical solution
temperature (CST), Effect of impurity on consolute temperature.
Immiscible liquids and steam distillation.Nernst distribution
law.Calculation of the partition coefficient.Applications of
distribution law.
2. Ionicequilibrium
Ionic product, common ion effect, solubility and solubility
product. Calculations based on solubility product.
3. Dilutesolutions
Colligative properties- RLVP, Osmotic pressure, Elevation in
boiling point and depression in freezing point. Experimental
methods for the determination of molar mass of a non-
volatilesolute using osmotic pressure, Elevation in boiling point
and depression in freezing point. Abnormal colligative properties.
Van’t Hoff factor.
Suggested Co-curricular activities and Assessment Methods

1. Continuous Evaluation: Monitoring the progress of student’s
learning
2. ClassTests, Worksheets and Quizzes
3. Presentations, Projects and Assignments and Group
Discussions: Enhances critical thinking skills and personality
4. Semester- end Examination: critical indicator of student’s
learning and teaching methods adopted by teachers throughout
the semester.
List of Reference Books
1. Principles of physical chemistry by Prutton andMarron
2. Solid State Chemistry and its applications by Anthony R.West
3. Text book of physical chemistry by K LKapoor
4. Text book of physical chemistry by SGlasstone
5. Advanced physical chemistry by Bahl andTuli
6. Inorganic Chemistry byJ.E.Huheey
7. Basic Inorganic Chemistry by Cotton andWilkinson
8. A text book of qualitative inorganic analysis by A.I.Vogel
9. Atkins, P.W. &Paula, J.de Atkin’s Physical Chemistry Ed.,
Oxford University Press 10thEd(2014).
10. Castellan, G.W. Physical Chemistry 4th Ed. Narosa (2004).
11. Mortimer,R.G. Physical Chemistry 3rd Ed. Elsevier: NOIDA,
UP (2009).
12. Barrow,G.M. Physical Chemistry
CONTENTS
Unit Chapter
Chapter Name Page No
No No.
Inorganic chemistry
Chemistry of p-block elements
1 Group 13 elements 1 – 21
1
1 Chemistry of d-block elements 80 – 105
2 2 Chemistry of f-block elements 106 – 131
3 Theories of bonding in metals 132 – 153
Physical Chemistry
3 Solid state 154 – 201
Gaseous state and Liquid state
4 1 Gaseous state 202 – 245
2 Liquid state 246 – 263
Solutions, Ionic equilibrium& dilute solutions
1 Solutions 264 – 329
5
2 Ionic equilibrium 330 – 363
3 Dilute solutions 364 – 425
APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 1
Chemistry - 1
 p
   
      
 s,p,df 
 s  
p 
 p   
 
   P
  (Atomic numbers),
 
 Unit p-  
  
(structures)

Chemistry Curiosity Corner
Is there any liquid metal at room temperature?
Yes. The only metal liquid at room temperature is mercury.

In fact, mercury stays a liquid until it is cooled down below –39ºC.
Gallium is also a fun metal. Its melting point is 30 ºC, so it stays
solid at room temperature but it melts at the 37 ºC of your hands.

Chemistry of
UNIT - 1 p-block elements
Learning outcomes
After studyingthis chapter, student shall be able to
1. Understand the position of different elements of p-block
2. Understand the classification of boranes with examples
3. Understand about the preparation and properties of diborane
4. Explain the structural aspects of diborane
5. Understand the preparation, properties and structure of borazine.
6. Know the methods of preparation and applications of silicones
7. Know about the preparation and structures of phosphonitrilic halides
8. Understand the structural aspects of oxides and oxoacids of sulphur
9. Know about pseudohalogens and their properties
10. Understand the structural aspects of interhalogen compounds
Introduction
The elements of long form of periodic table have been classified

into four blocks viz. s, p, d and f blocks. This classification was done on
the basis of type of sublevel into which the differentiating electron
progressively enters. S-block includes group 1 and group 2 elements
and they are all metals. P block includes group 13 to group 18 elements.
In these elements the differentiating electron enters into p-sublevel of the
outer most shell. They are located at the right side of the periodic table
after the d-block elements. p block contains all the non-metallic elements,
metalloids and few metals.
Chemistry - 1

Chapter - 1


(B),(Al),
(Ga)(In)(Tl)
       

    ns2np1   

by mass10B11B
isotope

     

chapter
   

Alfred Stock

 BnHn+4 BnHn+6 
  B2H6  B5H9   B6H10
B4H10
 B5H11  B6H12  
 BnHn+4BnHn+6
p-block elements
The elements belonging to p-block along with their atomic
numbers, general electronic configurations have been furnished in the
table 1.1. for quick reference.
Table 1.1-List of p-block elements
P-block elements
Period
number Group Group group Group Group Group
13 14 15 16 17 18
He
1
(2)
B C N O F Ne
2
(5) (6) (7) (8) (9) (10)
Al Si P S Cl Ar
3
(13) (14) (15) (16) (17) (18)
Ga Ge As Se Br Kr
4
(31) (32) (33) (34) (35) (36)
In Sn Sb Te I Xe
5
(49) (50) (51) (52) (53) (54)
Tl Pb Bi Po At
6 Rn (86)
(81) (82) (83) (84) (85)
Nh Fl Mc Lv Ts Og
7
(113) (114) (115) (116) (117) (118)
G.E.C ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 ns2np6
In this unit we will discuss the methods of preparation, properties,

structural aspects and uses of certain significant compounds of p-block
elements excluding the compounds of Xenon.

Chemistry - 1


           
  BnHn+4
     
chapter
 (B2H6)
  
 
                  

Ether 2B2H6 + 3Li[AlF4]
4 BF3 + 3Li[AlH4]
Ether 2B2H6 + 3Na[AlF4]

4 BF3 + 3Na[BH4]
 


2BCl3 + 6NaH B2H6 + 6NaCl
 B2H6 + 3CaCl2
2BCl3 + 3CaH2
  Cu-Al 

  

Cu-Al Catalyst or
2BCl3 + 6H2 B2H6 + 6HCl
Silent electric discharge
    

p-block elements
UNIT - 1 Group 13 Elements

Chapter - 1 (Boron family)
Introduction
Boron (B), aluminium (Al), gallium (Ga), indium (In) and
thallium(Tl) constitute group 13 elements of the long form of the
periodic table. The first elementof this group boron is a non metal and
the remaining elements are all metals. All these elements have three valence
electrons with the general configuration ns2np1. Among these elements
boron occurs in trace amounts in earth crust to an extent of about
0.0001% by mass. It is available in nature in the form of two isotopes.
viz., 10B (19%) and 11B(81%). Aluminium is the most abundant element
of this group and third most abundant element among all the elements, of
course next to oxygen and silicon.
In this chapter we shall discuss chemistry of certain
compounds of boron, which have industrial importance. These
compounds include the diborane and borazine.
Hydrides of boron-Boranes
Boron does not combine directly with hydrogen to form its
hydrides. However a number of hydrides of boron are known in
literature. The binary compounds of boron and hydrogen are
commonly called boranes, by analogy with alkanes (hydrocarbons).
Alfred Stock did a lot of work on the chemistryofboranes. There
are several types of boranes. For convenience sake all the boranes were
classified mainly into two series. They are 1.BnHn+4 series and
2.BnHn+6series. Some examples of boranes which come under BnHn+4
series are B2H6 (diborane), B5H9 (pentaborane -9), B6H10 (hexaborane-
10), some boranes which come under BnHn+6 series include B4H10
(tetraborane), B5H11 (pentaborane-11), B6H12(hexaborane-12).Between
these two series of boranes BnHn+4 type of boranesare known to
berelatively more stable than BnHn+6 type.

Chemistry - 1

2NaBH4 + I2 B2H6 + 2NaI + H2
    


2LiBH4 + 2HCl B2H6 + 2LiCl + 2H2
2NaBH4 + 2HCl B2H6 + 2NaCl + 2H2
 
 
 

  
  
       
  

B2H6 + 3O2 B2O3 + 3H2O H = -2165 kJ.mol-1
 
B2H6 + 6H2O 2H3BO3 + 6H2
Boric acid
B2H6 + 2KOH +2H2O 2KBO2 + 6 H2

Potassium metaborate
 
B2H6 + HCl B2H5Cl + H2
 K BCl3

p-block elements
Boranes are known to be electron deficient compounds. This is
because they have less number of valency electrons than actually required
to form the normal covalent bonds with all the available atoms. Among
the BnHn+4type of boranes diborane is the simplest and widely studied
borane. So we shall discuss about its structure, properties and uses in
order.
Diborane (B2H6)
Methods of preparation of diborane
Diborane is prepared
1. By the reduction of boron trifluoride with lithium aluminium hydride

or sodium borohydride in the presence of ether medium.
Ether 2B2H6 + 3Li[AlF4]

4 BF3 + 3Li[AlH4]
Ether 2B2H6 + 3Na[AlF4]

4 BF3 + 3Na[BH4]
2. By the reduction of boron trichloride with ionic hydrides like sodium

hydride, calcium hydride etc.

2BCl3 + 6NaH B2H6 + 6NaCl
 B2H6 + 3CaCl2
2BCl3 + 3CaH2
3. By the reduction of boron trichloride with hydrogen either in the

presence of Cu-Al catalyst or by subjecting the mixture to silent
electric discharge.
Cu-Al Catalyst or
2BCl3 + 6H2 B2H6 + 6HCl
Silent electric discharge
4. By the reduction of sodium borohydride with iodine in the presence

of ether.

Chemistry - 1
K   B2H5Br (bromo diborane)

298K
B2H6 + Cl2 2BCl3+ 6HCl
373K
B2H6 + Br2 B2H5Br + HBr
 
 metal boro hydride complex 
B2H6 + 2 LiH 2Li[BH4]
B2H6 + 2 NaH 2Na[BH4]
        

 
 0 C
    (B2H6.2NH3)  
    ([(NH3)2BH2]+ [BH4]-) 

[(NH3)2BH2]+and [BH4] -.
Low temp
B2H6 + NH3 B2H6.2NH3
Excess -1200C
 C

Low temp 0
B2H6 + NH3 B2H6.2NH3 200 C B3N3H6
Excess Borazine
   boron ni-
tride
High temp
B2H6 + NH3 (BN)x
Excess Boron nitride

p-block elements
2NaBH4 + I2 B2H6 + 2NaI + H2
5. By the action of hydrochloric acid on alkali metal borohydrides.
2LiBH4 + 2HCl B2H6 + 2LiCl + 2H2
2NaBH4 + 2HCl B2H6 + 2NaCl + 2H2
Physical Properties:
1. Diboraneis a colourless inflammable gas and is highly toxic.
2. It is stable at low temperatures in the absence of moisture and grease.

However at high temperatures it decomposes to other higher boranes.
Chemical properties:
1. Diboraneon reaction with dry air or oxygen forms boron trioxide. It

is highly exothermic reaction. For this reason it is used as a rocket
fuel.
B2H6 + 3O2 B2O3 + 3H2O H= -2165 kJ.mol-1
2. Diborane undergoes hydrolysis readily with water or aqueous alkali.
B2H6 + 6H2O 2H3BO3 + 6H2

Boric acid
B2H6 + 2KOH +2H2O 2KBO2 + 6 H2

Potassium metaborate
3. Diborane on reaction with hydrogen chloride forms chloro diborane,

a substitution product.
B2H6 + HCl B2H5Cl + H2
4. Diborane on reaction with chlorine at 298K forms boron

trichloride,while with bromine at 373K it forms bromodiborane.

Chemistry - 1
 THFtrialkyl borane
H2O2/NaOH

THF
1/2B2H6 + 3R-CH=CH2 (R-CH2CH2)3B
 


  



Ht o Hb Ht
3A Ht= terminal hydrogen
1.3
o
A B 97o B 122o Hb= bridged hydrogen
1.19
Ht Hb Ht
BH2


 B2H6 B-H
p-block elements
298K
B2H6 + Cl2 2BCl3+ 6HCl
373K
B2H6 + Br2 B2H5Br + HBr
5. Diborane forms complex metal borohydrides with lithium

hydride, sodium hydride in the presence of ether.
B2H6 + 2 LiH 2Li[BH4]
B2H6 + 2 NaH 2Na[BH4]
6. Diborane on reaction with ammonia form different products under

different conditions.
a) Diborane with excess of ammonia at low temperature forms an

addition compound, B2H6.2NH3, also called diammoniate of
diborane. It is an ionic compound with the ions,
[(NH3)2BH2]+and [BH4] -.
Low temp
Excess -1200C
b) B2H6.2NH3 at high temperatures forms a cyclic compound called
borazole or borazine.
Low temp 2000C
B2H6 + NH3 B2H6.2NH3 B3N3H6
Excess Borazine
c) Diborane with excess of ammonia at higher temperature forms a
graphite like compound called boron nitride.
High temp
B2H6 + NH3 (BN)x
Excess Boron nitride
7. Diborane on reaction with alkenes in the presence of tetrahydrofuran
(THF) forms trialkyl boranes (hydroboration), which on oxidation
with alkaline H2O2 forms alcohols.
THF
1/2B2H6 + 3R-CH=CH2 (R-CH2CH2)3B

Chemistry - 1
B-H-B

(B2H2(CH3)4)


   

sp3
B sp3 
sp3
sp3
     1s  
sp3-s(B-H)
   sp3  
sp31s
sp3-s-sp3(B-H-B
B-H-B
Banana
  

 

propellants


p-block elements
Structure of Diborane
Diborane is an electron deficient compound. It has only 12 valence

electrons (6 from two boron atoms and 6 from six hydrogen atoms)
against 14 electrons actually required for forming conventional covalent
bonds with all the atoms. So it cannot have the ethane like structure.
H H H H
H B  B H H C C H
H H H H
Ethane
In order to explain the bonding with the available 12 valence

electrons the following bridge structure was proposed for diborane,
in confirmation with the results of electron difraction and IR
spectroscopic experiments.
Ht o Hb Ht H t= terminal hydrogen
3A
1 .3
o B B
97 o 122o Hb= bridged hydrogen
. 19A
1
Ht Hb Ht
Diborane is a non-planar molecule. In this two BH2 groups lie in

one plane and the two bridging hydrogen atoms are perpendicular to the
plane of the molecule. This structure has four terminal hydrogens and
two bridged hydrogen atoms. The four B-H bonds are considered as
two centred two electron bonds (normal covalent bonds). The two B-
H-B bonds are special bonds where in two electrons are shared between
three atoms. So they are considered as three centred two electron bonds.
Diborane on methylation forms tetra methyl diborane [B2H2(CH3)4]. This
reaction supported the presence of two bridged hydrogens and four
terminal hydrogens in diboran.

Chemistry - 1


 LiBH4, NaBH4, Al(BH4)3    


  (B3N3H6)

borazole
 
A). Borazine

 C       
    (B2H6.2NH3)   

 C
B). 

   C 


        


p-block elements
Bond characteristics in diborane:
B–H–B bond length = 1.33ÅÐBHbB = 97°
B–H bond length = 1.19 Å Ð HtBHt = 122°
Molecular Orbital Structure of B2H6
In diborane both the boron atoms are in the sp3 hybridised state.
Each boron therefore forms 4sp3 hybrid orbitals, out of which three of
them contain one electron each and one sp3 hybrid orbital is vacant. The
four sp3hybrid orbitals of two borons overlap axially with is orbitals of
four hydrogen atoms and form 4 sp3-s sigma bonds, i.e., B–H bonds.
sp3 hybrid orbital of one boron atom having one electron and vacant sp3
hybrid orbital of other boron atom overlap with s orbital of hydrogen
atom and forms sp3–s–sp3 molecular orbital, (B–H–B bond). The vacant
sp3 hybrid orbital of first boron atom and sp3 hybrid orbital having one
electron of the second boronatom, overlap with s orbital of hydrogen
atom and forms sp3-s-sp3 molecular orbital (B–H–B bond). These
bonding molecular orbitals have three nuclei and two electrons and
resemble the shape of banana, hence they are also called banana bonds.
The bonding molecular orbital picture of diborane is shown in

fig. 1.1.1.
Fig. 1.1.1 Molecular orbital picture of diborane

Chemistry - 1

 
 
 

 HClB3N3H9Cl3





(planar Hex-
agonal)      B, N   sp2
                   
(delocalised)      
B-N
EN 
(localised) 
HCl

B-NAo.
Resonance
 

hexagonal boron nitride thin films

p-block elements
Uses of diborane:
Diborane is used
1. As a rocket fuel
2. For the preparation of high energy fuels and propellants
3. As a reducing agent in organic chemistry
4. As a catalyst in polymerization reactions
5. In the preparation of alcohols, ketones, carboxylic acids through
hydroboration reaction.
6. For the preparation of metallic borohydrides like LiBH4 NaBH4,
Al(BH4)3 etc.
7. For the preparation of higher boranes.
Borazine (B3N3H6)
Borazine is a colourless liquid, with characteristic aromatic smell.

It is thermally a very stable compound. It is also called borazole. It is
prepared by the following methods.
A) From diborane and ammonia
The preparation of borazine from diborane and ammonia involves

two steps.
1. Reaction of diborane with excess of ammonia at a low temperature

of –120°C to form an addition compound B2H6.2NH3, also called
diammoniate of diborane.
2. Heating of diammoniate of diborane to 200°C to get borazine.

Low temp
Excess -1200C
3[ B2H6.2NH3] 200°C 2B3N3H6 + 12 H2

Chemistry - 1
B) Now a days borazine and substituted borazines are prepared by the

following reactions.
1. Borazine is prepared by the reduction of chloroborazine with sodium

borohydride. The chloroborazine required for this reaction can be
obtained by the reaction of boron trichloride and ammonium chloride
at 140°C
NH4Cl + BCl3 140°C B3N3H3Cl3 NaBH4 B 3 N3 H6

Chloroborazine
2. Borazine is also obtained by the reaction of ammonium chloride with

sodium borohydride.
3 NH4Cl + 3NaBH 4 B 3N 3 H6 + 3NaCl + 9H2
Properties
1. The physical properties of borazine are very much similar to benzene.
2. Borazine is relatively more reactive than benzene.
3. Borazine undergoes hydrolysis slowly when heated with water to

form boric acid and ammonia.
B3N3H6 + 9H2O 3H3BO3 + 3NH3 + 3H2
4. Borazine reacts with HCl readily and forms an addition compound,

B3N3H9Cl3
B3N3H6 + 3HCl B3N3H9Cl3
Structure of Borazine
The structure of borazine is identical to that of benzene. Sometimes

it is also known as ‘Inorganic benzene’, since it is not only isostructural
but also isoelectronic with benzene. Like benzene it has a planar hexagonal

p-block elements
structure containing six membered ring with boron and nitrogen atoms in
alternate positions. In borazine both boron and nitrogen atoms are in
sp2 hybridised state. So it has six delocalised p electrons. Unlike in
benzene the B-N bonds are polar and hence the p electron density is
more localised on the more electronegative nitrogen atoms. This partial
localisation of electron density on nitrogen atoms weaken the p bonding
in the ring. So it forms an addition compound readily with HCl.
The bond angle in borazine is 120°. In borazine all B-N bond

lengths are same. i.e 1.44 Å.which is intermediate between the B-N
(1.54 Å) and B=N (1.36 Å) bond lengths.
The resonance structures of borazine are shown in fig 1.1.2.
Fig 1.1.2 Resonance structures of borazine
Uses of borazine
Borazine is used
1. As a starting material for the synthesis of ceramic materials.
2. In the preparation of hexagonal boron nitride thin films.
Why diborane is used as a fuel for rocket ?

Diborane has a higher heat of combustion per unit weight of
fuel than most other fuel. It is therefore, used as a rocket fuel.

Chemistry - 1

- 
Chapter

2     

(C),Si
Ge Sn Pb 
 C Si, Ge  Sn, Pb 
  C Pb
ns2np2. 
H, O,
Si, P, S, X       


chapter 

Silicones
(-R2SiO-) repeating units   ---O-Si-O---

 (R2SiO)n. (R=(CH3, C2H5, or C6H5 etc.)
    





p-block elements

Chapter - 2 (Carbon family)
Introduction
The elements carbon(C), silicon (Si), germanium (Ge), tin
(Sn) and lead (Pb), constitute group 14 of the long form of periodic
table. In this group carbon is a non metal, silicon and germanium are
metalloids. i.e., they show properties of both metals and non-metals
and lead is a metal. These elements are relatively less reactive but
reactivity increases down the group.All these elements have four
valence electrons with two electrons in s-sublevel and two electrons
in the p–sublevel (ns2np2). In this group carbon is having unique
property of catenation which makes it to form millions of organic
compounds with elements like hydrogen, oxygen, silicon, nitrogen,
phosphorous, sulphur, halogens. In this group silicon is the most
abundant element next to oxygen in earth’s crust. Silicon occurs in
nature in the form of silica and silicates.
Thecarboncompoundsaremanyin numberandtheyhavetheir own

characteristic properties. So carbon compounds can be studied separately
under the branch, organic chemistry. In this chapter an attempt is made
to study the chemistry of silicones, which are known to have wide
industrial applications in day to day life.
Here we in this chapter shall discuss the classification, preparation

of different types of silicones, their properties and industrial applications.
Silicones
The organo-silicon polymers with (–R2SiO–) as the basic

repeating unit or which contain—O–Si–O— bonds are called
silicones. Silicones can be represented by the general formula

Chemistry - 1





  
 
 Cross-linked 


 
 
 

a 0C  Cu  
    
   
(distillation ) 
b) SiCl4   

c 0CBF3



R3SiCl + H2O ®R3Si(OH) + HCl

p-block elements
(R2SiO)n, R may be alkyl (CH3, C2H5 etc.) or aryl (C6H5 etc.) groups.
The silicones can be obtained in the form of oils, viscous liquids,
resins, greases, rubber like solids etc.
Now a days silicones are gaining much importance in view

of following special and desirable properties, they have
1. They are very stable even at high temperatures.
2. They are chemically inert towards weak acids, alkalies salt

solutions and are nontoxic in nature.
3. They do not become viscous even at low temperatures.
4. They are water repellent.
5. They have good insulating properties and can withstand to high

temperatures without any charring.
Classification of silicones
Silicones can be classified into three types.
1. Linear silicones
2. Cyclic silicones
3. Cross linked silicones
Methods of preparations of silicones
The preparation of any silicone involves three stages.
1. Preparation of alkyl or aryl substituted chlorosilanes, which are

the starting materials
2. Hydrolysis of chlorosilanes
3. Polymerization of silanols

Chemistry - 1
R2SiCl2 + 2H2O R2Si(OH)2 + 2HCl
RSiCl3 + 3H2O R3Si(OH)3 + 3HCl
      

       
Cross-linked 
a



b

tris cyclodialkyl siloxane
(Trimer), tetrakis cyclodialkyl siloxane (Tetramer) 
 
R R
Si
O O
R R
Si Si
R O R
c cross-linked   

      
 cross-linked silicones


p-block elements
1. Preparation of alkyl chlorosilanes
a) A mixture of methyl chlorosilanes like trichloro methyl silane,

dichloro dimethyl silane, chloro trimethyl silane are prepared
by heating methyl chloride with silicon in the presence of
copper catalyst at 300°C.
Cu (CH3)2SiCl 2, (CH3)3SiCl, CH 3SiCl3
CH3Cl + Si
300°C
Major product
+ Other compounds
The above silanes can be separated by careful fractionation.
b) They are also prepared by the action of Grignard reagent on

silicon tetrachloride.
SiCl4 + CH3MgCl CH3SiCl3 + MgCl2
SiCl4 + 2CH3MgCl (CH3)2SiCl2 + 2MgCl2
SiCl4 + 3CH3MgCl (CH3)3SiCl + 3MgCl2
c) Phenyl trichlorosilane is prepared by heating benzene with

trichloro silane in the presence of BF3 or AlCl3 catalyst at
230-300°C.
BF 3
C6H6 + HSiCl3 C6H5SiCl 3 + H2
230-300°C Phenyl trichloro silane
2. Hydrolysis of alkyl chlorosilanes
Hydrolysis of alkyl chlorosilanes formthe respective silanols.
R3SiCl + H2O R3Si(OH) + HCl
R2SiCl2 + 2H2O R2Si(OH)2 + 2HCl

Chemistry - 1
 
 
i) dielectric insulating media, heat transfer media, hy-
draulic fluids 
ii  anti foaming agents  

iii 

 Car polish, lubricants, lip sticks

   cable insulations, electric tapes, gas-
kets, medical tubings, static and rotatory tubes 

   printing circuit board  lamination
paints, enamels 
 non-sticking coat-
ings cars, bread 
(moulds)
Do you know the difference between marble and granite?
The composition of marble is 38-42% lime, 20-25% SiO2, 2-

4% alumina, 1.5-2.5% oxides of sodium and megnesium and 30-32%
MgCO3. Chemically calcium corbonate. Granite is typically 70 - 77%
silica, 11 - 13% alumina, 3 - 5% potasium oxide, 3 - 5% soda, 1% lime,
2 - 3% total iron and less than 1% magnesia and titania. The biggest
difference between marble and granite is their porosity.

p-block elements
RSiCl3 + 3H2O R3Si(OH)3 + 3HCl
3. Polymerization of silanols
Depending on the nature of the silanols, linear, cyclic or two

dimensional cross linked silicones are formed.
a) Preparation of linear silicones
Condensation Polymerization of two or more dialkyl silane

diols give a linear silicone called polydialkyl siloxane. It is a thermo
plastic polymer.
R R R R
n HO Si OH Po lymerizatio n O Si O Si O Si O + (n-1) H2O
R R
R nR
Polydialk yl siloxane polyme r
b) Preparation of cyclic silicones
Condensation polymerization of three molecules of dialkyl silane

diolsgive a cyclic silicone called tris cyclodialkyl siloxane (trimer). With
four such molecules tetrakis cyclodialkyl siloxane is formed (tetramer).
R R
Si
O O
R R
Si Si
R O R
Tris cyclo dimethyl siloxane

Chemistry - 1
R R
R Si O Si R
O O
R Si O Si R
R R
Tetrakis cyclo dimethyl siloxane
c) Preparation of cross-linked silicones
Condensation polymerization of many molecules of alkyl silane

triol give a cross-linked two dimensional silicone.
R R O
O Si O Si O Si R
O O O
R Si O Si O Si R
O R O
Two dimensional cross linked silicone
Uses of silicones
Silicones have wide variety of applications based on their

characteristic properties.
1. Silicone oils are used as dielectric insulating media, heat transfer

media and hydraulic fluids.
2. Silicon oils are also used as anti foam agents in textile industry,
since they have low surface tension.
p-block elements
3. Silicone oils are added to cooking oils to prevent froathing, since
they are non-toxic.
4. Silicone greases are used in car polishes, lubricants and in lipsticks.
5. Silicone rubbers are used in cable insulations, electric tapes, gaskets,

medical tubings, static and rotatory tubes.
6. Silicone rubbers are also used to make moulds for dentures.
7. Silicone resins are used as laminates for printing circuit boards.
8. Silicone resins are used in the manufacture of paints and enamels.
9. Silicone resins are also used as non-stick coatings for pans and for
making moulds for cars and bread.

Chemistry - 1

    
Chapter - 3

 

 (N) P As
Sb  Bi        
s
P
 ns2np3
N2by vol-
umeNaNO3, KNO3

Ca3(PO4)2
As, Sb, Bi


  chapter      
  

fire proofwater proof
fibres

                     poly(amino
phosphazenes
p-block elements

Chapter - 3 (Nitrogen family)
Introduction
The elements nitrogen (N), phosphorous (P), arsenic (As),

antimony (Sb) and bismuth (Bi) with atomic numbers 7, 15, 33, 51and
83 represent group 15 elements of the long form of the periodic table.
They are p-block elements with five valence electrons, out of which two
are present in the s-sublevel and three electrons with parallel spins in p–
sublevel as per Hund’s rule of maximum multiplicity. Hence they were
placed under VA group of the Mendeleev’s periodic table. The general
configuration of these elements is ns2np3.
In atmosphere,nitrogen occurs as dinitrogen gas to an extent of

78% by volume. It also occurs in the earth’s crust in the form of several
compounds, such as NaNO3, KNO3 etc. In plants and animals it is
present in the form of amino acids and proteins. Phosphorous is available
in nature in the form of phosphates. eg. Ca3(PO4)2, which is the main
component of phosphate rocks. It is also an essential component of
plant and animal matter. Milk and eggs contain phosphoproteins. Arsenic,
antimony and bismuth are occurring in the form of Sulphides.
The trends in physical properties, chemical properties were

already dealt in lower classes. So an attempt is made to study the
preparation and structural aspects of some inorganic polymers containing
nitrogen and phosphorous namely phosphazenes in view of the wide
applications they have. They are used i) as structural materials for
construction of heart and blood vessels. ii) as fire proof and water proof
fibres, which are unaffected by petrol, oil and solvents, iii) as thin films
[poly(amino phosphazenes)] in hospitals to cover severe burns and
wounds as they prevent the loss of body fluids and free from attack of
germs, iv) as flexible plastics which are used in making gaskets, fuel
hoses, etc., which retain the elasticity even at high temperature.
Chemistry - 1
flexible plas-
tics N, P
1.3: Phosphazenes:

(NPX2)
   (NPX2)n, X= F, Cl, Br, SCN, CH3,
C6H5  
++

 
X = F, ClBr

P-NP=N
 
   

1. (NPCl2)3 
or P3N3Cl6 
Tri phospho
hexa (chloro cyclo
nitrilic chloride
triphosphazene).


sp2, sp3.

p-block elements
1.3: Phosphazenes
Phosphazenes are also called Phosphonitrilic compounds.

Phosphazenes are inorganic polymers with –(NPX2)– as the repeating
units. The general formula of these compounds is (NPX2)n, where X= F,
Cl, Br, SCN, CH3, C6H5 etc. In these polymers nitrogen is trivalent and
phosphorous is pentavalent. Among phosphonitrilic compounds,
phosphonitrilic halides are industrially important compounds.
Phosphonitrilic halides
Phosphonitrilic compounds in which X is F, Cl and Br are called

phosphonitrilic halides. These are the compounds in which P-N and
P=N bonds present in alternate positions. They may be either linear or
cyclic polymers. Some cyclic phosphonitrilic halides with their structures
and salient aspects are furnished in table. 1.3.1.
Table 1.3.1: Structural aspects of some phosphonitrilic halides

1. (NPCl2)3 It is a cyclic trimer. The
systematic name of it
or P3N3Cl6
ishexa(chloro cyclo
Tri phospho triphosphazene).It is a
nitrilic chloride planar molecule.
Hybridization of nitrogen
atom is sp2 and that of
phosphorous is sp3.
2. (NPCl2)3 or It is a cyclic tetramer.

The systematic name if it
P3N3Cl6 isocta (chloro cyclo tetra
Tetra phosphazene). It is a
phosphonitrilic non planar molecule.
chloride Hybridization of nitrogen
atom is sp2 and that of
phosphorous is sp3. It
exists in chair or boat
conformations.
Note: (NPF2)4 is a
planar molecule.
Chemistry - 1
2. (NPCl2)3 or 
P3N3Cl6Tetra
phosphonitrilic
octa
chloride (chloro cyclo tetra
phosphazene).
               
  
sp2, sp
non
planar molecule. 
NPF2)4 
(planar molecule).
Tetra phosphonitrilic chloride

Tri phosphonitrilic chloride

      

    
 C  PCl5, 

 PBr5

 

 C

p-block elements
The structure of cyclic tetra phosphonitrilic chloride is more flexible than
the cyclic triphosphonitilic chloride. The stable form of cyclic tetra
phosphonitrilic chloride exists in chair form and the metastable form of it
exists in boat form, as shown below.
Cl Cl Cl
P
Cl N N Cl Cl N Cl
P Cl
P P Cl N N
Cl Cl P
N P P
N Cl P
Cl Cl N Cl
Cl
Boat form
Chair form
List of some linear phosphonitrilic halides
S.No Formula Structure
1 P2NCl 7 Cl Cl
Cl
Cl P N P
Cl
Cl Cl
2 P3N 2Cl9 Cl Cl Cl
Cl
Cl P N P N P
Cl
Cl Cl Cl
3 P 4N 3Cl 11 Cl Cl Cl Cl
P Cl
Cl N P N P N P
Cl
Cl Cl Cl Cl
4 P 5N 4Cl 13 Cl Cl Cl Cl Cl
Cl P N Cl
P N P N P N P
Cl
Cl Cl Cl Cl Cl
Methods of preparation of phosphonitrilic halides:
1. Triphosphonitrilic chloride and tetraphosphonitrilic chloride are

prepared by the reaction of PCl5 with ammonia at 120-150°C

Chemistry - 1
120-150°C
3PCl5 + 3NH3 [NPCl2]3 + 9HCl
120-150°C [NPCl2]4 + 12HCl

4PCl5 + 4NH3
2. Triphosphonitrilic bromide is prepared by heating phosphorous

pentabromide with ammonium chloride in excess of bromine.
PBr5 + NH4Cl Excess Br2 [NPBr2]3
3. Triphosphonitrilic fluoride is prepared indirectly by the fluorination

of triphosphonitrilic chloride with sodium fluoride.
[NPCl2]3 + 6 NaF [NPF2]3 + 6NaCl
4. They are also prepared by heating phosphorous nitride with excess

of chlorine at 700°C
°
[P3N5]n + nCl2 700 C [NPCl2]n + Other compounds
Additional Information
Nature of bonding
The nature of bonding in phosphazenes is still not understood

completely. The structure of trimer and tetramersare studied by X-ray
diffraction experiments.Phosphazenes haveplanar rings in which P and
N are alternatively arranged have equivalent P-N and P=N bonds. Their
bond lengths are 1.56–1.59Å,which is much shorter than the usual single
bond distance of 1.77Å. Thus the structure can neither be explained by
the alternate single and double bonds, nor by pp–pp bonding and
delocalisation similar to benzene or graphite. It has been suggested that
coordinate bond is formed between a filled sp2 orbital on N atom andthe

p-block elements
empty3dx2–Y2 orbital on phosphorus.The size and energy of 3dx2–Y2
orbital are also not favourable for dative bond formation.
But the pbondsin phosphorous are delocalised over the whole

molecule resulting in pseudo aromatic character.As suggested by ‘Craig
and paddock’ nodes (with opposite sign) are present at each phosphorus
atom which reduces the stability of delocalised molecular orbitals.
Dewar and his co-workers offered the ‘Island model’ with

alternative view. In their model the dxy and dyz orbitals are hybridized to
give two hybrid orbitals. These hybrid orbitals are directed towards the
adjacent nitrogen atom results in the formation of three centred-two
electron bonds about each nitrogen atom. This indicates the delocalisation
over selected three atom segments of the ring.
Chemistry - 1

Chapter - 4

  
(S)SSeTe
Po


 
       
ns np . 2 4


moderate 
   
H SO 
2 4


SO , SO 
2 3
     


  

   SO 
2

p-block elements

Chapter - 4 (Chalcogens)
Introduction
The elementsoxygen (O), sulphur (S), selenium (Se), tellurium

(Te) and polonium (Po) constitute group 16 elements of the long form of
the periodic table. Polonium is the only radioactive element of this group.
Except polonium the remaining elements of this group are non metals
and are collectively called chalcogens or ore forming elements. This is
because most of the ores occur in nature either in the form of oxides or
sulphides. All these elements have six electrons in the valence shell with
two electrons ins-sublevel and four electrons in the p-sublevel. Therefore
the general configuration of these elements is ns2np4.
Oxygen is the most abundant element of this group in earth’s

crust. This element is a very important element as it reacts with almost all
the elements. Sulphur, selenium and tellurium are moderately reactive
and burn in air to form dioxides. They directly react with the metals and
non metals though less readily than with oxygen. It is estimated that
oxygen is produced nearly 100 million tonnes per year and widely used
in the manufacture of iron and steel. Most of the sulphur produced is
used in the manufacture of sulphuric acid.
Sulphur has great tendency to form chains and rings compared

to the other elements of this group. On the basis of chemical nature
oxides may be acidic, basic, amphoteric or neutral. In this chapter we
shall discuss in detail the structural aspects of oxides and oxoacids of
sulphur.
Oxides of sulphur
The two important oxides of sulphur are 1. Sulphur dioxide and

2. Sulphur trioxide.
Chemistry - 1
        

5 ppm

  
V

SO 
2
SO sp 
2
2
sp 
2

sp 
2
psp - 2
p S-O 

 3p  3d    
z xz
2p  p- p, d- p

z


 
p-
p S dp
O 119.50 O
 


SO2

p-block elements
Sulphur dioxide (SO2)
Sulphur dioxide is a colourless gas with burning sulphur smell. It

is highly soluble in water.
Sulphurdioxide is generally prepared either by burning sulphur

in air or oxygen or by roasting the iron pyrites.
S + O2  SO2
4FeS2 +11O2  2Fe2O3 + 8SO2
It is an acidic oxide. SO2 above 5ppm is harmful to human beings

and plant kingdom.
Structure
Ingas phase or solid phase SO2 molecule has bent or V shape

with a bond angle of 119.5°. The bonding in SO2 can be explainedby
considering the first excited state configuration of sulphur atom. In this
sulphur is the central atom and is in sp2 hybridised state.
3s 3p 3d
Electronic structure of Sulphur
in excited state
sp2 hybridization
3p 3d
in sp2 hybridization state
Three sp2 hybrid Unhybridized orbitals
orbitals
Among three sp2 hybrid orbitals of sulphur two of them contain

one electron each and third one contains a pair of electrons (lone pair).
These two sp2 hybrid orbitals overlap axially with half filled p orbitals of
two oxygen atoms and form sp2–p or S-O sigma bonds. The half filled
3pz orbital which is unhybridised overlap laterally with unhybridised
2pzorbital of oxygen to form a pp-pp bond between sulphur and oxygen.

Chemistry - 1
  SO  3
SO 
2
V O 400-450 C

2 5
0
SO 
3

sulphonating agent SO3
SO 3 
SO3
       
 SO3      sp2
 

Pysp2-
pS-O
   3Pz   3d   
 2Pz
p-p,d-p
 

p-block elements
Another p bond is formed due to lateral overlapping of 3dxz
orbital of sulphur and 2pz orbital of oxygen. This is called dp-pp bond.
Thus in SO2 two sigma bonds and two pi bonds are present.
p-
p S dp
O 119.50 O
The slight decrease in bond angle from 120°to 119.5° can be
attributed to the greater repulsions of lone pair- bond pair over the bond
pair-bond pair repulsions.
Uses
SO2 is used in the manufacture of sulphuric acid,as a refrigerant,as

a germicide, in the refining of sugar cane juice in the sugar industry, as a
bleaching agent, in the preparation of sulphites which act as food
preservatives for food and wine etc.
Sulphur trioxide (SO3)
SO3 is more acidic than SO2. It is prepared by the oxidation of

sulphur dioxide with oxygen in the presence of Pt or V2O5 catalyst
activated with K2O at 400-4500C. It is a reversible and exothermic
reaction.
V2O5
2SO2(g) + O2(g) 2SO 3 (g)  H= -98 kJ.mol -1
400-450°C
It is widely used in the manufacture of sulphuric acid (contact

process), acts as sulphonating agent for organic compounds.
Structure
SO3 molecule in gas phase has planar triangular shape. The

bonding in SO3 molecule can be explained by considering the electronic

Chemistry - 1
3s 3p 3d
Electronic structure of Sulphur atom
in its Second excited state
sp2 hybridization
3p 3d
orbitals
SO33,3 
ASO  3

SO -SO , -SO -
3 3 3
SO . -SO 

3 3

 


      
  (dibasic)  

 
 
 
 
    

i H SO     
2 3
a 
p-block elements
structure of sulphur in its second excited state. In this state sulphur
undergoes sp2 hybridization and forms three sp2 hybrid orbitals with one
electron each. Sulphur is also left with three unhybridised orbitals namely
3pz and two 3d orbitals.
3s 3p 3d
Electronic structure of Sulphur atom
in its Second excited state
sp2 hybridization
3p 3d
orbitals
The three sp2 hybrid orbitals having one electron each

independently overlap with half filled 2py orbitals of three oxygen atoms
axially and form three sp2-p or S–O sigma bonds. The half filled 3pz
andtwo 3d orbitals of sulphur which are unhybridised overlap laterally
with unhybridised 2pz orbital of oxygen to form three p bonds, out of
which one is pp–pp and other two are dp-pp bonds between sulphur
and oxygen atoms.
Thus SO3 moleculecontainsthree s bonds and three p bonds.

The bond angle in SO3 is 120°and the S–O bond length is 1.42Å. The
structure of SO3 is shown in figure 1.4.3.
O
d p
1.42Å
p-p
overlapping
p
 S
d
p
p

O 120°
O p-doverlapping

Chemistry - 1
b +4.
c sp 
3
d 
e p-d 
f 
ii H S O :      
2 2 2
a -2, +4.
b sp 
3
c.  p-d
iii. H S O :     
2 2 4
a. sp 
3
b. p-d 
c. 
iv. H S O :    
2 2 5
a. 
b. 
 

c. +5    p-d  +3
 p-d

V   

i H SO :    
2 4
a +6.
b sp 
3

p-block elements
The structure of solid SO3 is complex. It exists in three different
forms, viz., a-SO3, b-SO3 and g-SO3, which exists as a cyclic trimer.
O O
S
O O
O O
S S
O O O
Cyclic trimer of SO3
Oxoacids of sulphur
Sulphur has many oxoacids and are more important than the
oxoacids of selenium and tellurium. Many of the oxoacids of sulphur
exist as anions and salts but not in the form of free acids. All the oxoacids
of sulphur are dibasic (except peroxomono sulphuric acid, which is mono
basic) and these oxoacids can be classified into four series on the basis
of structural similarities.
1. Sulphurous acid series
2. Sulphuric acid series
3. Thionic acid series
4. Peroxoacid series.

Chemistry - 1
c 
d  p-d
e  
ii H2S2O3:     

a  -2, +6.
b sp 
3
c 
d  p-d  s-s 

e 
iii H S O       
2 2 7
a 

b +6 
c sp 3
d SO 
4

e p-d 
f 
vi    
i H S O :   
2 2 6
a +5, +5.
b sp 
3
c 
d  p-d 
p-block elements
1. Sulphurous acid Series- Structural features
Structural Structures O. S of sul phur

Feat ures
O +4
H2SO 3
Sulphurous acid HO S OH
1.Unstable in free state
2. Its salts are called sulphites
3. Hybridization of sulphur is sp3
4. Pyramidal shape
5. The  bond is p-d type -2
-2, +4
H2S 2O2
S
Thiosulphurous acid
HO S OH
Sulphurous acid series
1. Hybridization of sulphur is sp3

2. The  bond is p -d type
H2S 2O 4
O O +3, +3
Dithionous acid HO S S OH
(Hyposulphurous acid)
1. Salts are called hyposulphites

Ex: ZnS2O4, CaS2O4,
2.Hybridization of sulphur is sp3
3. The  bonds are p-d type
+3 +3, +5
O O
H2S 2O 5 HO S S OH
Disulphurous acid
(Pyrosulphurous acid) O
1.Does not exist as f ree acid but
exists as di sulphite or meta bisulphites
2. S in +5 state has two p -d bonds
and in +3 state has one p -d bond

Chemistry - 1
ii H2(S)n-2O6   n = 3 
a  
b 

c p-d
vii     
i H SO      
2 5
a 
b +6.
c sp 
3
d 
e 
f  p-d 
g M2SO5 

ii. H2S5O8:      
a 
b +6.
c sp 
3
d 
e p-d

f 

p-block elements
2. Sulphuric acid series- structural features
Structural f eatures Structures O.S of sulphur

O
H 2SO4 +6
Sulphuric acid HO S OH
(Oil of Vitriol)
1. Hybridization of sulphur is sp3 O
2. Tetrahedral shape
3. The  bonds are pd type
Sulp huric acid series
4. Forms bisulphates and sulphates..

O
H2S 2O3 -2, + 6
Thiosulphuric acid HO S OH
1.Hybridizationof sulphur is sp3 -2
2. Tetrahedral shape S
3.It is a thio acid, since it has S-S bond
4. Exists in the form of salts
Ex: Sodium thiosuphate (Hypo)
Na2 S 2O 3.5H 2O
5.The  bonds are pd type +6,+6
O O
H2S2O7
Pyrosulphuric acid
or Oleum or HO S O S OH
Fuming sulphuric acid
O O
1.Hybridizationof sulphur is sp3
2. Shape is two SO 4 tetrahedral units are linked
together by sharing one oxygen atom.
3. No S-S bond.
4. Its salts are called pyrosulphates
Ex: Sodi um pyrosulphate
Na 2S2 O7

Chemistry - 1
3. Thionic acid series- structural features
Structural features Structures O.S.of sulphur
O O
H2S 2O6
Thionic acid series
Dithionic acid HO S S OH
1. Hybridization of sulphur, sp3 + 5, +5
2. Exists in the form of salts O O
O O + 5, +5
H2(S)n-2O6 for terminal
HO S (S)n S OH
Polythionic acid sulphur atoms
O O
1. n = 3 to 6
2. Oxidation state of central
sulphur atom/s is zreo
3. Free acids are unstable but
salts are known
Structural features Structures O.S.of sulphur
H 2SO 5 O
Peroxomono +6
sulphuric acid HO S O OH
or Caro's acid
Peroxo sulphuric series
O
1.Hybridization of sulphur, sp3
2.Fairly stable
4. It has a peroxy linkage
5.Basicity is one. It does not form
M2 SO5 type of salts
H 2 S2 O8 O O
+ 6, +6
Peroxodi HO S O O S OH
sulphuric acid
or Marshall's acid O O
3
1.Hybridization of sulphur, sp
2. Stable acid, salts are welknown
4. It has a peroxy linkage
5. Basicity is two
W hy do onions m ake yo u cry?

A relatively c omplex process ta kes place when you cut an
onion. This results on the relea se of propanethial -S-oxide,
which is an irritant of the la chrymal glands, which relea se
tears.
Propanethial-S-oxide
It was repo rted that, upon cutting, onions relea se an
enzyme called lachrymatory-fa ctor synthase. T his enz yme
transforms sulfoxides present in the onion into su lfenic
acid. Sulfe nic ac id gets spontaneously rearra nged into
propa nethial-S -oxide , w hich through the air, g oes in to
yo ur eye and irritates your lachrymal glan ds.
Can you cool pure liquid water below zero degrees?
We have seen that adding other compounds to
water, such as salts, allow us to decrease its freezing point.
But what about pure water?
Yes, you can cool liquid water below zero degrees
Celsius if you increase the pressure.
Water phase diagram

As you can see in the diagram, as soon as you go up from
1 atm of pressure, the melting point of water decreases.
Chemistry - 1

Chapter - 5

   F Cl
BrIAt

       
  
      
  
            super halogen   
 AgF  
 CaF  
2

  CaF  Na AlF 
2 3 6
(3Ca (PO ) . CaF );

3 4 2 2
 ((NaCl)  (KCl),   (AgCl) 

(KCl.MgCl .6H O); NaCl
2 2
NaBr, NaI,NaIO 

3

       
(pseudo
halogens)(interhalogen com-
pounds)


p-block elements

Chapter - 5 (Halogens)
Introduction
The elements fluorine (F), chlorine (Cl), bromine (Br), iodine (I)
and astatine (At) with atomic numbers 9,17,35,53 and 85 constitute
group 17 elements of the long form of the periodic table. Astatine is the
only radioactive element of this group. These elements are known for
their high reactivity, so they do not occur in nature in elementary state.
These elements are generally called halogens, which means sea salt
producers. Among these elements fluorine is the most reactive element
and its compounds are different to the compounds of other elements in
properties. Thus fluorine is considered as super halogen. For instance
AgF is water soluble but other silver halides are water insoluble. Similarly
CaF2 is water insoluble but other halides of calcium are highly soluble in
water.
Fluorine occurs in nature in the form of compounds like fluorospar

(CaF2), Cryolite (Na3AlF6), Fluorapatite (3Ca3(PO4)2.CaF2). Chlorine
occurs as rock salt (NaCl), sylvine (KCl), Hornsilver (AgCl), carnalite
(KCl.MgCl2.6H2O). Sea water contains sodium chloride along with other
dissolved salts. Bromine occurs as NaBr in sea water, iodine is available
in the form of sodium iodide and sodium iodate.
The trends in atomic properties, physical properties, chemical

properties, anomalous behaviour of fluorine were dealt in lower sections.
In this chapter we specially emphasise on the chemistry of pseudohalogens
and structural aspects of interhalogen compounds.
Pseudohalogens and pseudohalides
The univalent anions with two ormore atoms of which one is

nitrogen atom and which are similar to those of the halide ions (F–, Cl–,
Br– and I–) are called pseudohalide ions or pseudohalides. The molecules
Chemistry - 1
Pseudohalogens and pseudohalides
      
(F , Cl , Br ,I )  - - - -

  
(F , Cl , Br , I ) 
2 2 2 2


  CN    
-

 HCl, HBr, HIHCN 
 F , Cl , Br , I (CN) 
2 2 2 2 2
 Ag , Pb , Hg   

+ 2+ +
CN 
-
 AgCl, AgBr, AgIAgCN 


   (NaCl, NaBr)
(NaCN, KCN)
 ClF, ClF , BrF ClCN,
3 5
BrCN
 [CuCl ] , [CoCl ] [ZnCl ] 
4
2-
6
3-
, 4
2-
[Cu(CN) ] , [Co(CN) ] [Zn(CN) ]       

4
2-
6
3-
, 4
2-

 
   
 Cl2, Br2, I2

p-block elements
formed by the dimerisation of these pseudohalides and which resemble
the halogens (F2, Cl2, Br2 and I2) in properties are called pseudohalogens
or halogenoids. The list of pseudohalides and pseudohalogens are given
in table 1.5.1.
Table 1.5.1: pseudohalides and pseudohalogens
Pseudohalide
Formula Pseudohalogen Formula
ions
–
Cyanide CN Cyanogen (CN)2
–
Thiocyanide SCN Thiocyanogen (SCN)2
Selenocyanide SeCN– Selenocyanogen (SeCN)2
Cyanate OCN– Oxycyanogen (OCN)2
–
Azide ion N3 -- --
Among the pseudohalides the best known pseudo halide is

cyanide ion. It resembles the halide ions Cl–, Br– and I– in the following
aspects.
1. It forms hydrocyanic acid, HCN similar to hydrogen halides HCl,

HBr and HI.
2. It gets oxidized to form the dimer called cyanogen, (CN)2 similar to

F2,Cl2, Br2 and I2.
3. It forms insoluble salts with Ag+, Pb2+, Hg+ similar to halides of these
cations.
4. AgCN is insoluble in water similar to AgCl, AgBr and AgI.
5. It forms soluble salts such as (NaCN, KCN etc) with alkali metals,
similar to NaCl, NaBr etc.
6. Similar to interhalogen compounds (ClF, ClF3, BrF5 etc.) it forms

pseudointer halogen compounds such as ClCN, BrCN etc.
7. It forms complexes such as [Cu(CN)4]2-, [Co(CN)6]3-, [Zn(CN)4]2-

similar to halide complexes [CuCl4]2-, [Co(Cl)6]3-,[Zn(Cl)4]2-.
Chemistry - 1
(disproportionation)
 PbCl Pb(SCN) 
4, 4
       


   
      

 
 
 
Which are the only elements liquid at room temperature?
The only pure elements that are liquids at room temperature

are Br2 (fuming orange liquid), and mercury (a metal).
Why car airbags are filled with sodium azide, a very toxic
substance?
Airbags are actually not filled with some compressed gas. Chemistry
takes action when airbags inflate. They are filled with around 100 grams
of sodium azide (NaN3), which upon heating (which is triggered by an
igniter that goes off upon collision detection) decomposes to give N2 gas
(more than 50 L, enough to fill a typical airbag) and sodium (Na) metal.
Since sodium metal is potentially explosive, the airbags also contain several
compounds that would react quickly with sodium, to avoid any danger.

p-block elements
8. Like halides, cyanide can act as bridging group,
Cl R R
Eg: R R
Au Au R Au N C Au R
R Cl R N
dialkyl gold (III) chloride C
N C
R Au C N Au R
R R
dialkyl gold (III) cyanide
Similarities between pseudohalogens and halogens
1. Like Cl2, Br2 and I2, cyanogen undergoes disproportionation reaction

in the presence of alkali.
Cl2 + 2NaOH  NaCl + NaOCl + H2O
(CN)2 + 2NaOH  NaCN + NaOCN + H2O
2. Similar to PbCl4, Pb(SCN)4 undergo thermal decomposition.
PbCl4  PbCl2 + Cl2
Pb(CN)4  Pb(CN)2 + (CN)2
3. Similar to chlorine, (SCN)2 undergo addition with unsaturated

hydrocarbons.
CH2 = CH2 + Cl 2 H2C CH2
Cl Cl
CH2= CH2 + (SCN)2 H2C CH2
Uses of pseudohalogens
NCS SCN
1. Cyanogen is used as a poisonous gas in warfare and in organic
synthesis. 2. Thiocyanogen is used as an oxidising agent.
3. Azides are used as organic intermediates. 4. Lead azide is
used as a detonator.

Chemistry - 1
  

(Interhalogen Compounds)
  
   
       
       
 ClF, BrF , IF etc.,
3 5
AX, AX , AX , AX 
3 5 7
A 
XA, X 


  
IF 
7
RT



      
 

 EN

                  
 
p-block elements
Interhalogen Compounds
Introduction
The special compounds which are formed when two different

halogens react with each other are called interhalogen compounds. These
compounds are formed due to difference in their atomic sizes and
electronegativity values. Eg. ClF, BrF3, IF5 etc.,
All the interhalogen compounds can be divided into four types.
1. AX type, 2. AX3 type, 3.AX5 type, 4.AX7 type.
In these compounds A is the larger halogen and X is the smaller

halogen. As the ratiobetween radii of A and X increases, the number of
atoms per molecule increases. For example,IF7 has a maximum of eight
atoms since the ratio of radii between iodine and fluorine is maximum.
The examples for different types of interhalogen compounds along with
their physical states at room temperature are listed in table 1.5.2.
Table 1.5.2: Interhalogen compounds and their physical states
at 25°C
AX AX3 AX5 AX7
ClF
colourless gas
BrF ClF3
pale brown gas colourless gas
BrCl BrF3 ClF5
red-brown gas pale yellow colourless gas
liquid
ICl (ICl3 )2 BrF5
ruby red solid bright yellow colourless liquid
solid
IBr (IF3)(unstable) IF5 IF7
black solid yellow solid colourless liquid colourless gas
(IF)* (unstable)

Chemistry - 1
       


 
  A-X X-X 

 
    
 AX         
Ex: ClF, BrF, BrCl, IF, ICl, IBr
    (ICl):


I (53): 5s 5p 5d .
2 5 0
sp sp 

3 3
      

sp 
3
3p sp -p

z
3
I-Cl ICl 



I Cl

p-block elements
Interhalogen compounds are generally prepared by the reaction
of two different halogens or by the reaction of lower interhalogen
compounds with halogens under suitable conditions.
200°C
Cl2 + F2 (1:1 ratio) 2ClF
°
Cl2 + 3F2 (excess F2) 300 C 2ClF3
20°C 2IF5
I2 + 5F2
90°C BrF5
BrF3 + F2
300°C
IF5 + F2 IF7
Properties
1. They are generally either volatile solids or liquids.

2. They are all covalent molecules, because of small difference in EN
values.
3. They are diamagnetic in nature, since they have even number of
halogen atoms.
4. The physical properties of these compounds are intermediate
between those of the constituent halogens. However, their melting
points and boiling points are somewhat higher than expected. This is
because of polarity associated with the bonds.
5. They are more reactive than the halogens except fluorine. This is
because of weaker A-X bond energy compared to X-X bond
energy. However F2 is an exception.
6. All these compounds undergo hydrolysis.
ClF + H2O  HF + HOCl
ClF3 + 2H2O  3HF + HClO2
IF5 + 3H2O  5HF + HIO3
IF7 + 4H2O  7HF + HIO4

Chemistry - 1
 AX     
3
Ex: ClF3, BrF3, IF3
   (ClF ) 

3


Cl (17): 3s2 3p4 3d1
sp dsp d
3 3
      



> ·\ e TÖ&ƒT 2p 3sp d-p
z
3
Cl-FClF 
3

T- 87 40 . ClF 
0 ’
3
  

 

  AX    

5
Ex: ClF5, BrF5 and IF5.
  (IF ) 

5
   

 I (53): 5s 5p 5d . 
2 3 2
sp d 6sp d 

3 2 3 2

p-block elements
Structures of Interhalogen Compounds
1. AX Type of interhalogen compounds

Ex: ClF, BrF, BrCl, IF, ICl, IBr
Structure of iodine monochloride
In iodine monochloride (ICl) iodine is the central atom. The

ground state valence shell configuration of iodine is
Iodine (Z=53):5s2 5p
Electronic 5s5 5d0 5p 5d
configuration
in ground
state sp3 hybridization
In its ground state iodine undergoes sp3 hybridization and form

four equivalent sp3 hybrid orbitals. Three of them contain one lone pair
of electrons each and the fourth sp3 hybrid orbital contains one electron.
The sp3hybrid orbital having one electron overlapsaxially with 2pz orbital of
chlorine atom having one electron and forms sp3–p or I-Cl sigma bond.
Thus, in ICl the arrangement of electron pairs is tetrahedral and shape is
linear.
I Cl
2. AX3 Type of interhalogen compounds

Ex: ClF3, BrF3,IF3

Chemistry - 1


      2p z
5sp d -pI-F
3 2
IF 
5
(square pyramidal)

  AX     
7
Ex: IF7
   (IF ) 

7


I (53): 5s 5p 5d .     sp d  
1 3 3 3 3
7 sp d 
3 3

2p 7sp d -p 
z
3 3
I-F IF   

7
(pentagonal, bypyramidal) 

   
 
 
     

 ClF BrF propellants oxidizers 
3, 5
 BrF , ClF , ICl 

3 3 3

p-block elements
Structureof ClF3:
In chlorine trifluoride (ClF3) chlorine is the central atom. The

valence shell configuration of chlorine in its first excited state is
Chlorine (Z = 17): First excited state 3s2 3p4 3d1
Electronic 5s 5p 5d
configuration
in ground
state sp3 hybridization
In its first excited state chlorine undergoes sp3d hybridization and

forms five equivalent sp3d hybrid orbitals. Two of them contain one lone
pair of electrons each and the other three sp3d hybrid orbitals contain
one electron each. The three sp3d hybrid orbitals having one electron
each, overlap axially with 2pz orbital of three fluorine atoms having one
electron each and form three sp3d-p or Cl-F sigma(ó) bonds. In ClF3
the arrangement of electron pairs is trigonal bipyramidal and the molecule
has slightly bent T-shape with the bond angle of 87°40'. The three
possible structures for ClF3 are shown below. Microwave spectroscopic
studies confirmed the structure (3) for ClF3, wherein the repulsions of
lone pairs and bond pairs are minimum.
F F F
F Cl
Cl Cl
F F
F F
(1) (2) (3)

Chemistry - 1
Possible structures of chlorine trifluoride
1.698Å 40'
87°1.598Å
Cl F
87°
40
'
1.698Å
3. AX5 Type of interhalogen compounds

Ex: ClF5, BrF5 and IF5.
Structureof IF5
In iodine pentafluoride (IF5) iodine is the central atom. The valence

shell configuration of iodine in its second excited state is
2
Iodine (Z = 53): 5s5s
Electronic 5p3 5d2 5p 5d
configuration
in second
excited state
sp 3d2 hybridization
In its second excited state iodine undergoes sp3d2 hybridization and forms
six equivalent sp3d2 hybrid orbitals. Out of them one sp3d2 orbital contains
a lone pair of electrons and the other five sp3d2 hybrid orbitals contain
one electron each. The five sp3d2 hybrid orbitals having one electron
each, overlap axially with 2pz orbital of five fluorine atoms having one
electron and form five sp3d2-p or I-F sigma(ó) bonds. In IF5 the
arrangement of electron pairs is octahedral and the shape is square
pyramidal.

p-block elements
F F
81 .9°
.869Å I
1
F F
4. AX7type of interhalogen compounds

Ex: IF7
Structureof IF7
In iodine heptafluoride (IF7) iodine is the central atom. The valence

shell configuration of iodine in its third excited state is
Iodine (Z = 53): 5s1 5p3 5d3
Electronic 5s 5p 5d
configuration
in third
excited state sp 3d3 hybridization
In its third excited state iodine undergoes sp3d3 hybridization and

forms seven equivalent sp3d3 hybrid orbitals. All the seven sp3d3 orbitals
having one electron each, overlap axially with 2pz orbital of seven fluorine
atoms having one electron each and form seven sp3d3-p or I-F sigma(ó)
bonds. The shape of IF7 molecule is pentagonal bipyramidal. The bond
angle in it is 72°.

Chemistry - 1
F
F F
I
F F
The summary of structural aspects of interhalogen compounds

is shown in table 1.5.3
Table1.5.3: Summary of structural aspects of interhalogen

compounds
No. of
Type of Hybridization electron
interhalogen of central pairs Shape
compounds atom Bond Lone
pairs pairs
3
AX (ICl) sp 1 3 Linear
Slightly bent T-
AX 3(ClF 3) sp3d 3 2
Shape
Square
AX 5 (IF5) sp3d2 5 1
Pyramid
Pentagonal
AX 7(IF7) sp3d3 7 0
bipyramid
Uses of Interhalogen compounds
They are used
1. as non-aqueous solvents.

p-block elements
2. as good fluorinating agents. BrF3 and ClF3 are used for the production
of UF6 in the enrichment of U235
U + 3ClF3® UF6 + 3ClF
3. for the estimation of iodine number, solution of ICl in glacial acetic
acid is used. Iodine number is a measure for the unsaturation of oils
and fats.
4. ClF3, BrF5 are used as oxidizers for propellants.
5. BrF3, ClF3, ICl3 are used in the preparation of polyhalides.
SUMMARY
The elements in which the differentiating electron enters into
outermost p-sublevel are called p-block elements. They are present at
the right side of the periodic table after the d-block elements. Hydrides
of boron are called boranes. Boranes are electron deficient compounds.
Diborane is the simplest borane, which has bridge structure. It has 4 B-
H bonds which are normal covalent bonds. In addition to this it has two
bridge bonds each one having three atoms and two electrons. Borazine
is a compound formed by heating diammoniate of diborane to about
200°C.It is structurally similar to benzene. Hence some times also called
inorganic benzene. It is more reactive than benzene. It has planar
hexagonal structure.
The organo silicon polymers with –(R2-SiO-) as the basic

repeating unit are called silicones. These are very stable, chemically inert,
water repellent and have good insulating properties. Silicones may exist
as linear or cyclic or cross linked polymers. Silicone oils are used as
antifoam agents, as dielectric insulating media, heat transfer media and
hydraulic fluids. Silicon greases are used in car polishes lubricants etc.
Silicone rubbers are used in cable insulations, electric tapes, gaskets
etc.,
Phosphonitrilic compounds are inorganic polymers with (-NPX2-)

as the repeating units. Phosphonitrilic compounds with X as F, Cl, Br
are called phosphonitrilic halides. In these we find P–N and P=N in
alternate positions. They may be linear or cyclic. These compounds are
Chemistry - 1
used as water proof and fire proof materials. The films of poly(amino
phosphazenes) are used in hospitals to cover severe burns and wounds.
Group 16 elements are commonly called Chalcogens or ore

forming elements. In nature most of the ores occur either as oxides or as
sulphides. The two important oxides of sulphur are SO2 and SO3. In
both these oxides sulphur is in sp2 hybridised state. SO2 has angular
shape while SO3 has planar trigonal shape. g- form of SO3 is a cyclic
trimer. Sulphur is a only element which forms a large number of oxoacids.
All oxoacids are dibasic except peroxomono sulphuric acid, which is a
mono basic acid.
Group 17 elements are commonly called halogens or sea salt

producers. These are the most reactive non-metals. Fluorine is the most
electronegative element in the periodic table and it always exhibits -1
oxidation state in all it compounds. Pseudohalides are the univalent anions
with two or more atoms of which one is nitrogen atom, similar to halide
ions. The dimeric forms of pseudohalides are called pseudohalogens,
since they resemble the halogens in properties. As halogens differ in their
atomic sizes and electronegative values, they are forming some special
compounds called interhalogen compounds. They are of four types
namely AX, AX3, AX5 and AX7. They are used as non aqueous solvents,
good fluorinating agents etc.
GLOSSARY
Analogy or analog Similar or comparable

Banana bond A bent bond, found in diborane where
hydrogen atom is shared by two boron
atoms to form a three centred two
electron bond
Basicity The number of replaceable hydrogen
atoms present in an acid

p-block elements
Bridged hydrogen The hydrogen atom which is

simultaneously bonded to two atoms
through partial sigma bond
Detonator A chemical substance or a device used

to trigger an explosive device
Differentiating The electron by which an element

electron differs from its previous element
Disproportionation Simultaneous oxidation and reduction

of a substance in a reaction to give two
different products
Electron deficient Compound having less number of

compound valence electrons than actually
required for bonding
Fluorinating agent A substance used to introduce fluorine

into an organic compound
Inorganic benzene It is the other name given to Borazine

(as it resemble benzene in structure)
Iodine number A measure for the degree of

unsaturation of oils and fats
(the number of grams of iodine
absorbed by 100 g of fat )
Isoelectronic Having same no of electrons
Oxidation state Total number of electrons gained or

lost by an atom in order to form a
chemical bond with other atom/s
Phosphazenes Inorganic polymers having –(NPX2)–

as repeating units
Silanols –OH substituted alkyl chloro silanes

Silicones Organo silicon polymers having (–
R2 Si–O–) as repeating units

Chemistry - 1
Sulphonating agent A compound used to introduce –SO 3H
group in organic reactions
Terminal hydrogen The hydrogen atom which is present at

the end of a molecule
INTERACTIVE LINKS
https://chem.libretexts.org/Bookshelves/Inorganic_Chemistry/
Book:_Chemistry_of_the_Main_Group_Elements_%28Barron%29/
06:_Group_13/6.04:_Boron_Hydrides
https://www.chemeurope.com/en/encyclopedia/Borazine.html
https://en.wikipedia.org/wiki/Borazine
https://www.chemicalsafetyfacts.org/silicones-post/
https://en.wikipedia.org/wiki/Silicone
https://www.brainkart.com/article/Silcones_38591/
https://pubchem.ncbi.nlm.nih.gov/compound/Phosphonitrilic-
chloride-trimer
https://cnx.org/contents/9G6Gee4A@25.9:8mElP1-L@1/Oxides-
and-Oxyacids-of-Sulfur
https://www.embibe.com/exams/oxoacids-of-sulphur/
https://www.schulz.chemie.uni-rostock.de/forschung/
halogenpseudohalogen-chemistry/
Multiple Choice Questions

p-block elements
ple Choice Qu
1. Which of the following is 1. sp, sp2 2. sp2, sp2

an electron deficient molecule?
3.sp3, sp3 4. sp2d, sp2
1. B2H6 2. C2H6
7. Identify the compounds which
3.SiH4 4. PH3 produce borazine
1. NH2OH + BCl3 2. N2 + BCl3
2. Which of the following is given
the name as inorganic benzene? 3. NaBH4+ B2O3 4. NH3+B2H6
1. Borazine
8. The correct form of
2. Boron nitride diammoniate of diborane is
1. [(NH3)2BH2]+[BH4]–
3. Tetra borane
2. [(NH3)3BH]+[BH3]–
4. Diborane
3. [(NH3)4BH]-[BH4]+
3. The number of 2 centered-2
electron bonds present in 4. [(NH3)2BH4]+[BH2]–
diborane molecule is
1. 2 2. 6 9. The total number of p-electrons
present in silicon atom
3. 3 4. 4 1. 2 2. 6
4. Which of the following boranes 3. 8 4. 14
come under the BnHn+4 type of
boranes? 10. The possible compound/s
1. B4H10 2.B2H6 formed in the reaction of
Grignard reagent with SiCl4
3. B5H10 4. B6H12 CH3SiCl3(I)
(CH3)2SiCl2 (II)
5. Diborane on reaction with X
(CH3)3SiCl (III)
forms boric acid. What is X ?
1. I & II only 2. II & III only
1. O2 2. H2O
3. I&III only 4. I, II, III
3. O2 + H2O 4. NaOH
11. Poly dialkyl siloxane is an
6. Hybridization of two boron example of
atoms in diborane respectively
are
Chemistry - 1
1. Cyclic polymer 1. NO 2. V2O5
2. Thermo setting polymer 3. W2O3 4. Fe2O3
3. Cross linked polymer 17. The oxidation state of terminal

sulphur in H2S2O2 is
4.Thermo plasticpolymer 1. +6 2.+4
12. The correct repeating units 3. –2 4. +2
with respect to silicones and
phosphazenes are respectively 18. Which of the following are
1.(–R2SiO–),–(N2PX)– peroxoacids of sulphur
1. H2SO5& H2S2O8
2.(–R2SiO–),–(NPX2)–
2. H2SO5& H2S2O7
3.(–R2SiO–),–(NPX3)–
3. H2S2O7& H2S2O8
4. R–Si–O,–(NP2X)–
4. H2S2O6 & H2S2O7
13. Which of the following is a
planar compound 19. Peroxy mono sulphuric acid is
1. (NPCl 2)3 2.(NPCl 2) 4 also called
1. Marshall’s acid
3. (NPBr2)4 4. (N2PCl)3
2. Caro’s acid
14. The hybridization of P and N in
tetra phosphonitrilic chloride 3. Oleum
respectively are
1. sp2, sp3 2. sp3, sp2 4. Oil of vitriol
3. sp2, sp 4. sp3, sp3 20. The common element in all the

pseudo halogens is
15. Number of p-p, d-p and 1. C 2. O
sigma bonds present in SO3
molecule are respectively 3. N 4. Cl
1. 1,3,2 2. 1,3,3 21. Identify the peroxo acid from
3. 1,2,3 4. 1,1,1 the following oxoacids.
1.Thiosulphuric acid
16. In the manufacture of sulphuric
acid in contact process the 2. Disulphurous acid
catalyst used is
p-block elements
3. Marshall’s acid 3. overlap of two p orbitals
along their axes.
4. Pyro sulphuric acid 4. sidewise overlap of two
22. Which of the following is not a parallel p orbitals.
pseudo halide ion? 26. A molecule of the type AB3 has
1. OBr – 2. SCN– two unshared pair of electrons
on A. What is the hybridization
3. CN - 4. SeCN- of A?
1. sp2 2. sp3
23. The hybridization of iodine and
shape of IF 5 molecule ar e 3. sp3d 4. sp3d2
respectively
27. The valence shell electronic
1. sp3-pyramidal
configur ation of the most
electronegative element is
2. sp3d-T-shape
1. 2s22p5 2. 3s23p5
3. sp3d2-square.pyramidal
3. 4s24p5 4. 5s25p5
4.sp3d3–pentagonal bi
KEY:
pyramid
1. 1 2. 1 3. 4 4. 2 5. 2
24.Match the following
6. 3 7. 4 8. 1 9. 3 10. 4
List –I List-II (B.P.&L.P)
11. 4 12. 2 13. 1 14. 2 15. 3
1. AX a. 3, 2
16. 2 17. 3 18.1 19. 2 20. 3
2. AX3 b. 5, 1
3. AX5 c. 7, 0 21. 3 22. 3 24. 1 25. 4 26. 3
4. AX7 d. 1, 3
27. 1
1. 1a, 2c, 3d, 4b
2. 1d, 2a, 3b, 4c
3. 1c, 2a, 3d, 4b
4. 1d, 2a, 3c, 4b
25. A  (pi) bond is the result of the
1. overlap of two s orbitals.
2. overlap of an s and a p
orbital.
Chemistry - 1
 d
Chapter - 1 

sp
d(n-
1)d d
 3d, 4d, 5d, 6d  

    

   Zn, Cd, Hg, Cn     d   

s
p
       

(n-1)d 
d
(n-1)d 

Cu, Ag, Au 
     (n-1)d            
      (n-1)d
d

UNIT - 2 d - block Elements
Chapter - 1 (Transition elements)
Learning outcomes
After studying this chapter, the student shall be able to
 Understand the position of d-block elements in the long form of

periodic table
 Know the reasons for the anomalous electronic configurations
of certain transition elements
 Understand the reasons for variable oxidation states of transition
elements
 Describe the magnetic properties of transition elements
 Calculate the magnetic moments of transition metal ions
 know the catalytic properties of transition elements and their
compounds
 Explain the ability of transition metal ions to form complex
compounds
 Have awareness about the stability of certain oxidation states of
transition elements.
Introduction
The elements which are placed between s- and p- blocks of the

long form of the periodic table in long periods (4, 5, 6 and 7) are called
d-block elements. In these elements the differentiating electron
progressively enters into penultimate d–orbitals i.e., (n–1) d orbitals,
hence the name d–block elements.The d-block elements are 40 in
number and are arranged in four series viz., 3d, 4d, 5d and 6d series.

Chemistry - 1
V, Cr, Mn, Fe (steels) 
B



    ns (n-1)d   0-2 1-10
 

(n-1)d 3d, 4d, 5d, 6d
        

d

d

      
4dNb 4d 5s 4d 5s 
3 2 4 1
 Pd  4d 5s  4d 5s 

8 2 10 0

5d 
Pt 5d 6s 5d 6s 6dDs 6d 7s
8 2 9 1 8 2
6d 7s 
9 1

 (n-1)d   


d-block elements
Each series consists of ten elements and they come under the groups 3
to 12, as shown in the table 2.1.1:
Table 2.1.1: d-block elements with their atomic numbers
Groups
Period
3 4 5 6 7 8 9 10 11 12
n =4 Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d –
21 22 23 24 25 26 27 28 29 30
Series
n =5 Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
4d–
Series 39 40 41 42 43 44 45 46 47 48
n =6 La* Hf Ta W Re Os Ir Pt Au Hg
5d –
57 72 73 74 75 75 77 78 79 80
Series
n =7 Ac** Rf Db Sg Bh Hs Mt Ds Rg Cn
6d –
89 104 105 106 107 108 109 110 111 112
Series
*
Ce – 71Lu- Lanthanoids, **90Th – 103 Lr –Actinoids.
58
Except group 12 elements i.e., Zn, Cd and Hg, the remaining d-

block elements are also called transition elements. This is because, these
elements bring gradual transition from the more metallic s-block elements
to more non- metallic p-block elements. The d-block elements, which
have incompletely filled (n–1) d orbitals either in the atomic state or
chemically significant oxidation state/s are called transition elements.
Group 12 elements are not considered to be the transition

elements, since they have completely filled (n-1)d orbitals either in atomic
state or chemically significant oxidation states. Group 11 elements i.e.,
Cu, Ag and Au are typical transition elementssince they have incompletely
filled (n-1) d orbitals in their chemically significant oxidation state/s.
Most of the d-block elements and their compounds are widely

used as catalysts in industrial field. V, Cr, Mn, Fe etc., are used in the
manufacture of variety of steels.Most of the complex compounds
including hemoglobin, vitamin-B12 are known to contain d-block

Chemistry - 1


(interstitial compounds)

(Variable oxidation states) 
s
ns, (n-1)d 

 ns  
(n-1)d 
   
        
3d, 4d, 5d 

d
Cr, CuMn
(KMnO ), 5dRu, 5d
4
Os   (RuO , OsO ) 

4 4
  Fe
Ru, Os
   CO, dipyridyl   

      



       
d-block elements
elements only. In view of wide range of applications it is necessary to
discuss on the chemical behaviour of these elements. Hence in this chapter
an attempt is made to describe some of the characteristic properties of
these elements in terms of their electronic configurations.
2.1. 1. Electronic configuration
The general electronic configuration of d-block elements is ns0–

2
(n–1)d1–10. The outer electronic configuration is same for all these
elements and hence they exhibit same properties.
The electronic configuration of d-block elements
Table 2.1.2: 3d series (or) First transition series
Atomic Electronic
Element Symbol
number configuration
1 2
Scandium Sc 21 [Ar] 3d 4s
Titanium Ti 22 [Ar] 3d2 4s2
3 2
Vanadium V 23 [Ar] 3d 4s
5 1
Chromium Cr 24 [Ar] 3d 4s
Manganese Mn 25 [Ar] 3d5 4s2
Iron Fe 26 [Ar] 3d6 4s2
7 2
Cobalt Co 27 [Ar] 3d 4s
Nickel Ni 28 [Ar] 3d8 4s2
Copper Cu 29 [Ar] 3d104s 1
10 2
Zinc Zn 30 [Ar] 3d 4s
These elements also exhibit some characteristic properties due to the

presence of unpaired (n–1) d electrons. The electronic configuration of
3d, 4d, 5d and 6d series of elements are shown in table 2.1.2 to 2.1.5.

Chemistry - 1

d

3d, 4d, 5d    3d
4d, 5d 





CuO,
CuS  Cu O, Cu S 
2 2
 CuCl , CuBr 

2 2
 CuCl, CuBr     



3d    5d   

FeO 
4
2-
4d, 5dMo, W, Os, Ir etc. 

  
Cr W 
     
 (MoO ) (WO ) 
4
2-
4
2-
     

MnO 
4
-

d-block elements
Table 2.1.3: 4d series (or) Second transition series
Atomic Electronic
Element Symbol
1 2
Yttrium Y 39 [Kr] 4d 5s
Zirconium Zr 40 [Kr] 4d2 5s2
Niobium Nb 41 [Kr] 4d4 5s1
5 1
Molybdenum Mo 42 [Kr] 4d 5s
Technetium Tc 43 [Kr] 4d5 5s2
Ruthenium Ru 44 [Kr] 4d7 5s1
8 1
Rhodium Rh 45 [Kr] 4d 5s
10 0
Palladium Pd 46 [Kr] 4d 5s
Silver Ag 47 [Kr] 4d105s 1
Cadmium Cd 48 [Kr] 4d105s 2
Table 2.1.4: 5d series (or) Third transition series
Atomic Electronic
Element Symbol
1 2
Lanthanum La 57 [Xe] 5d 6s -----
Hafnium Hf 72 [Xe] 4f145d2 6s 2
Tantalum Ta 73 [Xe] 4f145d3 6s 2
14 4 2
Tungston W 74 [Xe] 4f 5d 6s
Rhenium Re 75 [Xe] 4f145d5 6s 2
Osmium Os 76 [Xe] 4f145d6 6s 2
14 7 2
Iridium Ir 77 [Xe] 4f 5d 6s
14 9 1
Platinum Pt 78 [Xe] 4f 5d 6s
Gold Au 79 [Xe] 4f145d106s1
Mercury Hg 80 [Xe] 4f145d106s2

Chemistry - 1
(TcO4-) (ReO4-)
(Magnetic properties) 



(spin magnetic moment)
(orbital magnetic moment) 






  
     
         (paramagnetic substances)
(diamagnetic substances)
(ferro magnetic substances)
     


     



 
d-block elements
Table 2.1.5: 6d series (or) Fourth transition series
Atomic Electronic
Element Symbol
1 2
Actinium Ac 89 [Rn] 6d 7s -----
Rutherfordium Rf 104 [Rn] 4f146d2 7s 2
Dubnium Db 105 [Rn] 4f146d3 7s 2
14 4 2
Seaborgium Sg 106 [Rn] 4f 6d 7s
14 5 2
Bohrium Bh 107 [Rn] 4f 6d 7s
Hassium Hs 108 [Rn] 4f146d6 7s 2
Meitnerium Mt 109 [Rn] 4f146d7 7s 2
Darmstadtium Ds 110 [Rn] 4f146d9 7s 1
14 9 2
Roentgenium Rg 111 [Rn] 4f 6d 7s
Copernicium Cn 112 [Rn] 4f14 6d107s2
The anomalous configurations (irregular configurations) of certain

d-block elements are shown in the table 2.1.6. These anomalies are due
to the unusual stability achieved by the atoms, when all the d-orbitals of
a sublevel are either exactly half filled or completely filled. In 4d-series
Nb has a configuration 4d45s1 instead of 4d35s2. Similarly Pd has 4d105s0
configuration instead of 4d85s2. The irregularities associated with the
electronic configuration of these elements can be attributed to the
electron-electron repulsions and nucleus electron attractions. In 5d series
platinum has the configuration 5d9 6s1 instead 5d8 6s2 and in 6d series
Darmstadtiumhas a configuration 6d9 7s1 instead of 6d8 7s2.

Chemistry - 1
Where, S = total spin of the electrons, L = orbital angular mo-
mentum quantum number
     
      


spin only formula
n  S  n ( n  2)
( S  L )  4S ( S  1)  L( L  1)



      
  (diamagnetic substances)
      
  Sc , Ti , V , Cu   
3+ 4+ 5+ +


      
  
 

     3d  
4d, 5d
  

d-block elements
Table2.1.6 : Anomalous configurations of certain d–block elements
Electronic
d–series Atomic configuration Anomalous
Element
number as per Aufbau configuration
rule
3d- Cr 24 [Ar] 3d45s2 [Ar] 3d 55s1
series Cu 29 [Ar] 3d95s2 [Ar] 3d 105s1
4d- Mo 42 [Kr] 4d45s2 [Kr] 4d 5 5s1
series Ag 47 [Kr] 4d95s2 [Kr] 4d10 5s1
5d-
Au 79 [Xe] 4f14 5d9 6s2 [Xe] 4f 14 5d10 6s1
series
6d-
Ds 110 [Rn] 4f14 6d8 7s2 [Rn] 5f 146d9 7s1
series
Characteristic properties of Transition elements
In addition to normal properties of metals, transition metals are

known to exhibit some characteristic properties due to the presence of
one or more unpaired (n-1)d electrons. These properties include1)
Variable oxidation states2) Magnetic properties 3) Formation of coloured
compounds 4) Formation of alloys 5) Catalytic properties 6) formation
complexes 7) formation of interstitial compounds. Some of the
characteristic properties have been discussed under the following
headings.
1.1.2. Variable oxidation states

Unlike s-block elements, transition elements are exhibiting two
or more oxidation states called variable oxidation states. This is due to
the involvement of both ‘ns’ and unpaired (n–1) d electrons in bond
formation. Furthermore, it is due to the slight difference of energy between
‘ns’ and (n–1) d sublevels.
If ‘ns’ electrons alone involve in bond formation, they exhibit a

common oxidation state of +2. In addition to ns electrons if unpaired (n–

Chemistry - 1
(Catalytic Property) 

      d

     


         




(activated com-
plex theory)
(activated
complex) 

(Complex Formation abil-
ity) 

  
(NH , H O, CN , C O ,
3 2
-
2 4
2
Cl etc.,)
-
     K [Fe(CN) ],

4 6
[Co(NH3)6]Cl 3, [Ag(NH3) 2]Cl, [Ni(H2O) 6]Cl 2, [Pt(NH3) 4]Br2,
[Ni(CO)4].
d-block elements
1)d electrons involve in bond formation, the number of oxidation possible
gradually increases up to group 7 elements. There onwards the number
of oxidation states possible gradually decreases due to decrease in
number of unpaired (n–1)d electrons and successive increase of nuclear
charge, leading to high ionization enthalpy values. The various oxidation
states possible for 3d, 4d and 5d series of elements with reference to
their electronic configurations are shown in table 2.1.7.
Table 2.1.7: The oxidation states of 3d, 4d and 5d-series
Sc Ti V Cr Mn Fe Co Ni Cu Zn
(+2) (+2) +2 (+1) +2 +2 +2 +2 +1 +2
+3 +3 +3 +2 (+3) +3 +3 (+3) +2
+4 +4 +3 +4 +4 (+4) (+4)
+5 (+4) +5 (+5) (+5)
+5 (+6) (+6)
+6 +7
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
+3 +4 +3 +3 +4 +2 +3 +2 +1 +2
+5 +4 (+6) +3 +4 (+3) (+2)
+5 +7 (+5) (+6) +4 (+3)
+6 +6
(+7)
(+8)
La Hf Ta W Re Os Ir Pt Au Hg
+3 +4 +4 (+2) (+3) (+2) (+2) +2 +1 +1
+5 (+3) +4 (+3) +3 (+3) +3 +2
+4 (+5) +4 +4 +4
+5 +6 +6 (+6)
+6 +7 +8
The common oxidation state of these elements is +2. In 3d-series

Cr and Cu have lowest oxidation state of +1, since they utilise only
one‘s’ electron in bonding. In this series Mn exhibits highest oxidation

Chemistry - 1

 
 
 d

 
How long can gold wires go?

Gold is universally used as an electricity conducting material. It’s
electric conductivity is not as high as copper, but it finds many uses
thanks to being much more difficult to corrode (oxidize) than other
metals. Besides, gold is extremely ductile. Only one ounce of metallic
gold can be elongated into very thin wires of gold can be drawn into
80 km of wire. This makes the wire only five microns thick.
What are Olympic Gold Medals made of?
The Olympic gold medals are not completely made of gold. In fact,
they are made of at least 95% of silver, containing a minimum of 6 g
of gold.
Chemical composition of Olympic medals.
Gold is around 100 times more expensive than silver, enough amount
of gold is added to give the medal the characteristic golden color. A
bronze medal, made of cheap copper and zinc.

d-block elements
state of +7 in KMnO4. The Ru of 4d-series and Os of 5d-series exhibit
highest oxidation state of +8 in the compounds RuO 4 and
OsO4respectively. But iron exhibits highest oxidation state of +6 only.
This difference between iron and other two elements Ru and Os is
attributed to the increased size. In these elements the successive oxidation
states of an element differ by one unit only.
In the elementary state they have zero oxidation state. However,

several of these elements exhibit zero or low oxidation states in metal
complexes. Low oxidation states mainly occur in the presence of certain
bonding ligands, such as CO, dipyridyl. In lower oxidation states these
elements are known to form ionic compounds, while in higher oxidation
states they form covalent compounds.
1.1.3. Stabilities of various oxidation states

A compound is said to be stable if
1) it exists at room temperature,

2) it is not oxidised by the air,
3) it is not hydrolysed by water vapour,
4) it neither disproportionatesnor decomposes.
The difference in stabilities of various compounds of d-block

elements depend on the oxidation states of the elements. For 4d and 5d
series of elements the higher oxidation states are more stable than the
corresponding 3d series of the elements of the same group. This can be
observed in the oxides and halides of the 3d, 4d, 5d series of elements.
Stability of the oxidation state of an element may be correlated

with electron configuration of the element in that state. For example i)
for manganese +2 state is more stable than +3 state, ii) for iron +3 state
is more stable than +2 state, iii) for copper +1 state is more stable than
+2 state in many circumstances. For example CuO and CuS on heating
undergo decomposition to give Cu2O and Cu2S respectively. Similarly
CuCl2 and CuBr2 on heating decompose to CuCl and CuBr respectively.

Chemistry - 1
The stability of these oxidation states canbe explained in terms of the
stable electronic configurations. However, in aqueous solution Cu2+ is
more stable than Cu+ in terms of hydration energies.
From 3d series of elements to 5d series of elements the stability

of lower oxidation states decreases and that of higher oxidation states
increases. In 3d series iron exhibits highest oxidation state of +6 in FeO42-
, which is very rare. Among 4d and 5d series higher oxidation states ate
more stable for Mo, W, Os, Iretc. For example in chromium group
(Group6) stability of +6state increases form Chromium to tungsten. Thus
chromate, dichromate acts as good oxidizing agents but molybdate
( MoO 24  ) and tungstate (W O24  ) are stable and cannot act as oxidising
agents. Similarly in group7, MnO4- is a strong oxidizing agent but
pertechnate (Tc O4 ) and perrhenate (Re) ions do not act as oxidising
agents.
1.1.4. Magnetic Properties

Any particle which is extremely small, carries a charge and is moving
behaves like a small bar magnet. The electron fulfils all these three criteria.
The electron is associated with two types of motion. i) the electron spins
on its own axis and the magnetic moment resulting from this type of
motion is called spin magnetic moment ii) The electron revolves around
the nucleus and the magnetic moment resulting from this type of motion
is called orbital magnetic moment. Thus the magnetic properties of the
substances can be determined by the sum of spin and orbital magnetic
moments of the electron.
If an orbital has a pair of electrons, the spin magnetic moment of

one electron is exactly cancelled by that of the other electron. So does
the orbital magnetic moment. Thus, the magnetic properties are significant
only, if there are one or more unpaired electrons in the atoms/ ions/
compounds.

d-block elements
Based on the behaviour of the substances in the external magnetic
field, we can classify the substances mainly into three types.
i)paramagnetic substances, ii) Diamagnetic substances and iii) Ferro
magnetic substances.
The substances which are weakly attracted by the external

magnetic field are called para magnetic substances. Paramagnetism is
due to the presence of one or more unpaired electrons. Transition metal
atoms or ions or compounds containing one or more unpaired electrons
exhibit Paramagnetism. The degree of paramagnetic character increases
with increase in number of unpaired (n–1)d electrons. The total magnetic
moment associated with the substances is calculated by the formula,
 ( S  L )  4S (S 1)  L( L  1)BM
Where, S =total spin of the electrons, L= orbital angular momentum

quantum number.
For the compounds of first series of transition elements the

contribution of the orbital magnetic moment is quenched and hence is of
no significance. So, for these elements or ions the magnetic moment is
calculated using spin magnetic moment only. In such cases the above
equation is reduced to
s  4S( S 1)
or
s  n(n  2) BM
(Where n= no. of unpaired electrons)
The above formula is called spin only formula. The calculated

and experimental magnetic moments of certain transition metal ions are
shown in table 2.1.8.

Chemistry - 1
Table 2.1.8: Calculated and Observed Magnetic Moments (BM)
of some transition metal ions
No. of Magnetic moment

Ion Configuration Unpaired
electrons Calculated Experimental
3+ 1
Ti 3d 1 1.73 1.75
2+ 2
Ti 3d 2 2.84 2.76
V 2+ 3d3 3 3.87 3.86
Cr2+ 3d4 4 4.90 4.80
Mn 2+ 3d5 5 5.92 5.96
Fe2+ 3d6 4 4.90 5.3 _ 5.5
Co2+ 3d7 3 3.87 4.4 _ 5.2
Ni2+ 3d8 2 2.84 2.9 _ 3.4
Cu2+ 3d9 1 1.73 1.8 _ 2.2
The substances which are weekly repelled bythe external magnetic

field are called dia magnetic substances. Diamagnetism is due to the
presence of all paired electrons. Transition metal ions with no unpaired
electrons such as Sc3+, Ti4+, V5+, Cu+, etc., exhibit diamagnetism. They
have zero magnetic moment.
The substances which are strongly attracted by the external magnetic

field are called ferro–magnetic substances. In the presence of these
substances the external magnetic field strength increases abnormally.
These substances can be permanently magnetised. In these substances
the magnetic moments of all atoms, ions or molecules are aligned in the
same direction.
Examples: Fe, Co, Ni etc. The details of the different types of magnetic
substances are shown in table 2.1.9.

d-block elements
Table 2.1.9: Different types of magnetic substances
Magnetic
behaviour
Alignment of
Type of Species with Examples Reason
magnetic moments
external
field
Sc3+, Ti4+,
Absence
Dia magnetic Weakly Cu+,
of
repelled Zn+2,
unpaired
Cd+2,
electrons
Hg+2
Presence
Para magnetic weakly Sc2+, Ti3+,
2+ 2+ of
attracted Cu ,Fe ,
unpaired
Fe3+
electrons
Alignment
Ferromagnetic of all
Strongly
Fe, Co, magnetic
attracted
Ni moments
in one
direction
The magnetic behaviour of 3d series of elements can easily be

interpreted,while with respect to 4d and 5d series of elements it is quite
complex and cannot be interpreted easily.
1.1.5. Catalytic Property

The chemical substance which can alter the rate of a chemical
reaction without itself being consumed and without undergoing any
chemical change at the end of the reaction is called a catalyst. A catalyst
is assumed to loosen the bonds present in the reactants. Most of the d-
block elements and their compounds show catalytic properties. Thusthey
are used as catalysts in various industrial fields. Some of the industrially
important catalysts along with the processes are shown in table.2.1.10.

Chemistry - 1
Table 2.1.10: Industrially important catalysts and processes
Process Catalyst employed
Haber’s Process of
Iron, (Mo, promoter)
manufacturing ammonia
Contact process of Platinum or vanadium
manufacturing sulphuric acid pentoxide
Ostwald’s process of Platinum gauge or
manufacturing nitric acid Rhodium gauge
Manufacture of chlorine by
CuCl2
Deacon process
Manufacture of silicones Copper
Hydrogenation of oils Nickel
Manufacture of high density
TiCl4
polythene
Manufacture of methyl alcohol ZnO /Cr 2 O3
Decomposition of KClO3 MnO2
Dehydrogenation of alcohols Cu/Ag
The catalytic properties of these elements can be explained by the

following reasons
1) The ability of these elements to exhibit two or more oxidation states.

2) The ability to provide large surface area for the reactant/s to adsorb
and involve in the formation of bonds between the reactants.
The catalyst is known to provide an alternate path of low
activation energy for the reaction, so that it facilitates large number of
reactant molecules to cross the energy barrier, resulting in fastening of
the reaction.
According to an activated complex theory, an intermediate

compound (activated complex) is formed, when the reactant/s combine
with the catalyst. The intermediate compound has a momentary existence.
So it decomposes simultaneously to give the product and the catalyst.

d-block elements
C (catalyst)
A+B AB
Mecahnis m:
Step 1. A + B + C (ABC)
or A + B + C (AC + B)
Step 2: (ABC) AB + C
or (AC + B) AB + C
This mechanism can be applied for the formation of sulphur

trioxide from sulphur dioxide and oxygen in the presence of vanadium
pentoxide catalyst as follows.
V2 O 5
2 SO2 (g) + O2 (g) 2SO 3 (g)
Mechanism
Step 1: 2SO2 + 2 V2O5 2SO3 + 2 V 2O4
In this step oxidation state of vanadium decreases from +5 to +4
Step 2: 2 V2O4 + O2 2V2O 5
In this step oxidation state of vanadium increases f rom +4 to +5
1.1.3. Complex formation ability

Most of the transition elements are known to form a large number
of stable complexes. A complex compound is the one in which a metal
atom or ion is bound with definite number of molecules or ions such as
NH3, H2O, CN–, C2, Cl– etc., through coordinate covalent bonds. Such
molecules or ions, which are bound to the central metal atom or ion are
called ligands. Ligands are also regarded as electron pair donors or
Lewis bases.
Some of the stable complexes formed by transitional metal atoms

or ions are

Chemistry - 1
K4[Fe(CN) 6], [Co(NH 3) 6]Cl3, [Ag(NH 3) 2]Cl, [Ni(H 2O) 6]Cl2,

[Pt(NH3)4]Br2, [Ni(CO)4]
The ability of the transition metal atoms or ions to form complexes

may be attributed to the following reasons.
1) Small size of the transition metal atoms or ions

2) High nuclear charge
3) Presence of sufficient number of available vacant d- orbitals.
4) Exhibiting variable oxidation states
5) Feebly electropositive character.
CoCl3 + 6NH3 [Co(NH3)6] Cl3
Transition metal atom (e- pair acceptor) Lewis acid
-
Ligand (e pair donor) Lewis base
[Co(NH3)6]Cl3 Ionisation sphere
Coordination number
Coordination sphere
List of some d-block elements which generally form complexes are shown
in table 2.1.11.
2.1.11: d-block elements which generally form complexes
Group/
5 6 7 8 9 10 11 12
Series
3d V Cr Mn Fe Co Ni Cu Zn
4d Mo - Ru Rh Pd Ag -
5d W Re Os Ir pt Au Hg

d-block elements
Do you Know
Do you know the central metal ions in natural m etal
complexes 1. Haemoglobin and 2. V itamin B 12 ?
SUMMARY
The elements in which the differentiating electron progressively
fills the (n-1)d sublevel are called d-block elements. They are arranged
in four series in long periods between s and p-block elements. Except
Zinc family the remaining d-block elements are called transition elements.
In these elements partially filled (n-1)d orbitals are present either in their
atomic forms or chemically significant ionic forms. They are metals. Unlike
normal metals these metals are exhibiting some characteristic properties
like variable oxidation states, catalytic properties, formation of coloured

Chemistry - 1
compounds and formation of complexes. The compounds of most of
these elements are paramagnetic in nature, due to the presence of one or
more unpaired d electrons. Unlike s-bock metals they show two or more
different oxidation states due to the involvement of ns and (n-1)d electrons
in bonding. The oxidation states possible are related to the electronic
configurations of the atoms of these elements. Some elements like Cr,
Cu, Pd, Ag etc., exhibit anomalous configurations since either half or
completed filled d-orbitals provide additional stability to these atoms.
Paramagnetism is due to the presence of one or more unpaired electrons.
Paramagnetism is with respect to these elements is obtained due to spin
and orbital motion of the electrons. Most of the transition metals can
form complexes with certain molecules or ions called ligands. Most of
the d-block elements and their compounds are widely used as catalysts.
The catalytic properties of these elements are due to the fact that they
have the ability to variable oxidation states and provide large surface
area for the reactants to adsorb.
INTERACTIVE LINKS
https://thechemistryguru.com/neet/d-block-elements-general-properties/

1. Which is not a naturally occurring 5. The highest oxidation states of
d–block element ? Mn, Ru and Os respectively are
1. Sc 2. Cu 3. Ti 4. Tc 1. +8, +7, +8
2. The number of (n-1)d electrons
in iron in its +3 state is 2. +7, +8, +8
1. 3 2. 4 3. 5 4. 6
3. +8, +8, +8
3. The transition metal present in
4. +7, +7, +8
haemoglobin is
1. Mg 2. Fe 3. Co 4. Zn 6. Which of the following element
Multiple Choice Questions exhibits +1 oxidation state?
4. The transition element with the
1. Mn 2. Sc 3. Cr 4. Co
valence configuration (n-
1)d10ns0 (where n=5) is 7. In which of the following iron is
Fill1.inPtthe2.blanks
Au 3. Pd 4. Ag in +6 oxidation state
d-block elements
1. FeO42- 2. [Fe(CN)6]4- 10. Identify the isoelectronic
pair in the following
3. Fe3O4 4.F2 O3
1. Ni2+,Co2+ 2. Mn2+,Fe3+
8. Which of the following has more
3. Ni2+,Mn2+ 4. Ti3+,Co2+
no. of unpaired d-electrons ?
1. Zn2+ 2. Fe2+ 11. Number of unpaired
3. Ni2+ 4. Cu+ electrons in the valence shell of
Co2+, Ni2+, Fe2+ is
9. The catalyst employed in the 1. 4,2,3 2. 2,2,4
manufacture of silicones is
1. Fe 2. Cu 3. 3,2,4 4. 2,3,4
3. Ti 4. V
Fill in the blanks
12. In a complex compound ligands act as _____

13. The metal in liquid state at room temperature is _____
14. The central metal in vitamin B12 is _____
15. In +3 state electronic configuration of an element is [Ar] 3d4.
The electronic configuration of that element is_____
16. In the complex K3[Fe(CN)5Cl], the number of coordinate covalent
bonds is _____
KEY
Multiple choice questions
1. 4 2. 3 3. 2 4. 3 5. 2 6. 3
7. 1 8. 2 9. 2 10. 2 11. 3
Answers of Fill in the Blanks

12. Lewis base 13. mercury 14. cobalt
15. [Ar] 4s2 3d5 16. 6

Chemistry - 1
 f
Chapter - 2  

(n-2)f
(sub level)f-block


      1) 4f- 
5f-

(z = 57)
 (z = 72)   

Ce (z=58) Lu (z=71)
(rare earths)


2.1. Electronic Configuration:
          [Xe]6s 25d 1-04f 1-14. 

 5d, 4f 

Pr Eu, Tb 
Yb  5d
UNIT - 2 f - block Elements
Chapter - 2 (Innertransition elements)
Learning outcomes
 Locate the position of f-block elements in the periodic table

 Write the electronic configurations of lanthanoids and actinoids
 Understand the oxidation states of lanthanoids and actinoids
 Distinguish the oxidation states of actinoids and lanthanoids
 Know the reasons for lanthanoid and actinoid contractions
 Calculate the magnetic moments of different lanthanoids
 Know the similarities and differences between lanthanoids and
actinoids.
Introduction
The elements in which the differentiating electron progressively

enters into antepenultimate f- sublevel i.e (n-2) f-sublevel in the long
form of the periodic table are called f-block elements. As these elements
are appearing between the transition elements, they are also called inner
transition elements. These elements were placed at the bottom of the
main periodic table in two horizontal rows, just for the sake of
convenience. The f-block elements or inner transition elements are again
divided into two types based on the type of (n-2)f-sub level into which
the differentiating electron enters. They are (i) 4-f series of elements,
also called lanthanoids, (ii) 5-f series of the elements, also called actinoids.

Chemistry - 1
   4f  
Gd  4f  5d  
Gd4f 

2.1 Oxidation states:
      
     
                  
     
       
eg : Ce4+ (f0)f-
  eg : Eu2+ and Tb4+ (f7) 3) f-
 eg:Yb2+(f14)+2, +4 

Ce4+     
       
(E0 of Ce4+ / Ce3+ = 1.74V). Pr, Tb, Dy 
    Eu, Yb    

(Lanthanoid
contraction - causes and consequences
  

   
      

f - block elements
f-block elements
4f series Ce Pr Nd Pm Sm Eu Gd
(Lanthanoids) Tb Dy Ho Er Tm Yb Lu
5f series Th Pa U Np Pu Am Cm
(Actinoids) Bk Cf Es Fm Md No Lr
Lanthanoids
The fourteen chemically similar elements which appear between
lanthanum (Z=57) and Hf (72), the transition elements are called
lanthanoids. They are present in 6th period under group 3 of the long
form of the periodic table. The lanthanoids include the elements from Ce
(Z = 58) to Lu (Z = 71). Earlier these elements were referred to as the
rare earths. But, it is a misnomer as they are not particularly rare except
promethium.
2.2.1. Electronic configuration

The general electronic configuration of these elements is
[Xe]6s25d1-04f1-14. The 6s2 configuration is common for all the elements
and there is no much difference in energy between 4f and 5d-sublevels.
Hence, they resemble closely in their properties. The electronic
configurations of these elements are shown in table 2.2.1.
From the above electronic configurations we can observe that

from Pr to Eu and from Tb to Yb the differentiating electron prefers to
occupy the lower energy 4f-orbitals instead of 5d orbital. However, in
Gd the differentiating electron prefers to enter into 5d orbital instead of
4f-orbital. This is because of the additional stability achieved by Gd due
to the exactly half filled f-sublevel.

Chemistry - 1

     

E u, Yb 



Eu, Yb


 
4f-
4f-
  




(Consequences):

 EN
 
   
Ce(OH)3Lu(OH)3

    Ce  Lu 
f - block elements
Table 2.2.1: Electronic configuration of lanthanoids
Element Symbol At. No. Configuration
1 2
Lanthanum La 57 [Xe]5d 6s
Cerium Ce 58 [Xe]4f15d16s 2
Praseodymium Pr 59 [Xe]4f 3 6s 2
4 2
Neodymium Nd 60 [Xe]4f 6s
5 2
Promethium Pm 61 [Xe]4f 6s
Samarium Sm 62 [Xe]4f 6 6s 2
7 2
Europium Eu 63 [Xe]4f 6s
Gadolinium Gd 64 [Xe]4f75d16s 2
Terbium Tb 65 [Xe]4f9 6s2
10 2
Dysprosium Dy 66 [Xe]4f 6s
11 2
Holmium Ho 67 [Xe]4f 6s
Erbium Er 68 [Xe]4f126s 2
Thulium Tm 69 [Xe]4f136s 2
14 2
Ytterbium Yb 70 [Xe]4f 6s
Lutetium Lu 71 [Xe]4f145d1 6s2
2.2.2. Oxidation states
The various possible oxidation states of lanthanoids are shown
in Table: 2.2.2.
Table 2.2.2: The various possible oxidation states of lanthanoids
La Ce Pr Nd Pm
(+2) (+2)
+3 +3 +3 +3 +3
+4 (+4)
Sm Eu Gd Tb Dy
(+2) +2
+3 +3 +3 +3 +3
(+4) (+4)
Ho Er Tm Yb Lu
(+2) +2
+3 +3 +3 +3 +3

Chemistry - 1

 Ce 3+   Lu3+                    

    5d   
4d Zr,
Hf; Nb, Ta; Mo, W 
         


 Y3+
Y3+
      


Magnetic properties of lanthanoid ions :


[Xe]4f7Gd3+
 
       
     
      
5s, 5p
4f 
spin contri-
bution (s) and orbital contribution (L)
f - block elements
All the lanthanoids exhibit the most stable and most common
oxidation state of +3. In addition to the +3 oxidation state, some elements
do exhibit, +2 and +4 oxidation states either in aqueous solutions or
solid compounds,under the conditions, (i) when they get noble gas
configuration. eg: Ce4+ (f0) (ii) when they have half filled f-sublevel eg: Eu
2+
and Tb4+ (f7) and (iii) when they have completely filled f-sublevel eg:
Yb2+ (f14).
Even though the formation of Ce4+ is favoured by its noble gas

configuration i.e. xenon configuration, but it acts as a strong oxidizing
agent in aqueous solution, reversing its oxidation state to the common
+3 state. (Eo value of Ce4+ /Ce3+ = 1.74V). However, the rate of reaction
is very slow and hence Ce4+ acts as a good analytical reagent. Pr, Tb
and Dy also exhibit +4 oxidation state only in their oxides. Eu and Yb in
+2 oxidation state, act as good reducing agents and their oxidation state
increases to common +3 state. Furthermore, the lanthanoids are known
to resemble each other very closely when compared to the horizontal
row of the transition elements. This is because the former elements have
only one stable and common oxidation state of +3.
2.2.3 Lanthanoid contraction - causes and consequences
In general atomic and ionic radii in a group increases from top to

bottom. However, in lanthanoids the atomic radius and ionic radius with
respect to +3 oxidation state continuously decreases with increase in
atomic number.
This decrease in atomic and ionic radii observed in lanthanoids, is referred

to as the lanthanoid contraction. The decrease in ionic radius is more
significant with respect to tri positive lanthanoid ions than the decrease in
atomic radii, shown in table 2.2.3. and in figure 2.2.1.

Chemistry - 1
Russell-Saunders Cou-
pling J), (total angular
momentum quantum number) J

 J=L-S (f 
 J=L-S (f 
J lanthanoid ions 

  g J ( J  1)BM
g Lande Splitting Parameter.

3 S ( S  1)  L( L  1)
g 
2 2 J ( J  1)


Sm3+ , Eu3+ 

      
Sm3+
Eu3+
        
J
   
  Lu3+
(4f14) 

f - block elements
Table 2.2.3: Atomic and ionic radius (Ln3+) of lanthanoids
ion ic
A tom ic A tom ic
L anth an oid r adius
n umb e r rad iu s
(Ln 3 +)
La 57 1.877 1.061
Ce 58 1.820 1.034
Pr 59 1.828 1.013
Nd 60 1.821 0.995
Pm 61 - 0.979
Sm 62 1.802 0.964
Eu 63 2.042 0.950
Gd 64 1.802 0.938
Tb 65 1.782 0.923
Dy 66 1.733 0.908
Ho 67 1.766 0.894
Er 68 1.757 0.881
Tm 69 1.746 0.869
Yb 70 1.940 0.858
Lu 71 1.734 0.848
Figure 2.2.1. Decrease in the radii of lanthanoid ions

Chemistry - 1

5f 
5f-d-
Ac (z =89)

Ac,Rf d

 Th (z =90) Lr (z =103)
     
      
      



  
[Rn] 7s26d1-0 5f 1-14
 5f, 6d  



 Cm   [Rn] 5f87s2 
[Rn] 5f76d17s2 


Am 

f - block elements
The atomic radii of europium and ytterbium are however known
to have higher values than expected. This anomalous increase in the
atomic radii of these two elements can be explained in terms of the metallic
bonding involved. In case of these two elements only two valence
electrons involve in metallic bonding, while in all the other elements three
valence electrons involve in metallic bonding. This leads to loose packing
in these two elements resulting in unexpected increase in atomic radii.
Further this is supported by the observation that, the enthalpy of
sublimation of these two elements is small compared to other lanthanoids.
Cause of lanthanoid contraction
In lanthanoids, the differentiating electron enters into 4f-orbitals.

Because of the imperfect shielding effect of one electron by the other in
the same sublevel, the attraction of the nucleus over the valence electrons
gradually increases with increase in atomic number. Therefore valence
electrons are pulled closer to the nucleus causing shrinkage in size. The
net decrease in size from La to Lu is therefore known as lanthanoid
contraction. It is better reflected in trivalent ions than in neutral atoms of
lanthanoids.
2.2.4 Consequences of lanthanoid contraction
1. There is a slight increase in the electronegativity of trivalent ions.

2. There is a steady decrease in the ionic size.
3. The basicity of the oxides and hydroxides decreases and acidity
increases. Thus Ce(OH)3 is the most basic and Lu(OH)3 is the least
basic hydroxide.
4. The hardness, melting point and boiling points of lanthanoids increases
from Ce to Lu. This is because, the attraction between the atoms in
the metallic lattice increases with decrease in their sizes.
5. Ability to form complexes increases from Ce3+ ion to Lu3+ ion.
6. The sizes of 4d and 5d series of elements of the same group are
identical, since 5d series of elements appear after lanthanoids. Thus
Zr and Hf; Nb and Ta; Mo and W have similar atomic and ionic

Chemistry - 1
 GdCm

       
5f, 6d, 7s


Pa  Pu 
Pu 



Th, Pa, U, Np 
       

 Np  
Pu 

Am, 
        


5f 
5f 
      

      
f - block elements
radii as shown in table 2.2.4. As a result of this they occur together
and form same type of compounds, leading to difficulty in their
separation.
Table:2.2.4. Ionic radii of different ions of transition series
3d-series Ti4+ (0.68 Å) V 5+ (0.59 Å) Cr6+ (0.52 Å)
4d-series Zr 4+ (0.79 Å) Nb5+ (0.69 Ao) Mo6+ (0.62 Å)
5d series Hf4+ (0.78 Å) Ta5+ (0.68 Å) W 6+ (0.62 Å)
7. The ionic radius of Y3+ is comparable to that of heavier lanthanoids.

So Y3+ occurs along with heavier lanthanoids.
8. The degree of hydrolysis of the lanthanoid ions increases.
2.2.5 Magnetic properties of lanthanoid ions
The lanthanoid ions with one or more unpaired electrons exhibit

para magnetic property, while the ions with nounpaired electrons exhibit
diamagnetic property. The electronic configuration of Gd3+ is [Xe]4f7
and it has seven unpaired electrons. Therefore it should exhibit the highest
magnetic moment of 7.9 BM calculated as per the spin only formula
applied for first transition series of elements. Further it is not in accordance
with the total magnetic moment associated with both the spin and orbital
motion of the electrons, applied for the second and third transition series
of elements. Thus the magnetic properties of lanthanoid ions are basically
different from those of the transition metal ions. This is perhaps due to
the fact that, the 4f electrons are well shielded from external fields by the
overlying 5s and 5p electrons.
In order to explain the experimentally determined magnetic

moments of the lanthanoid ions, the spin contribution (S) and orbital
contribution (L) must be integrated with each other. This integration is
called Russell-Saunders Coupling. This gives rise to a new quantum
number called the total angular momentum quantum number. It is denoted
by ‘J’ and can be calculated as follows,

Chemistry - 1
     
  

  
figure 2.2.1. 



4f5f
      (n-2)f

 
    

 f-f 

      

   

      



4f, 5f 

f - block elements
Case (i) when the f-sublevel is less than half filled, J= L–S
Case (ii) when the f-sublevel is more than half filled, J = L+S
Therefore, the magnetic moment for lanthanoid ions in terms of

J, can be calculated by the equation
  g J ( J  1)BM
where, g is called Land Splitting parameter and is given by the
equation,
3 S (S  1)  L( L  1)
g 
2 2 J ( J  1)
The calculated magnetic moments and experimentally determined

magnetic moments of the lanthanoid ions are shown in the table
2.2.5.From this table it is evident that there is good agreement between
the theoretical and experimental magnetic moment values for all tri positive
lanthanoid ions, except for Sm3+ and Eu3+. This anomaly can be explained
as follows; In Sm3+ the first excited is sufficiently closure to the ground
state and in Eu3+ the second and third excited states also closure to the
ground state. So, all these levels are populated at room temperature, as
the excited states have higher J values than that of the ground state.Thus,the
experimentally determined magnetic moments of Sm3+ and Eu3+ are higher
than the expected values. Among the lanthanoid ions only Lu3+ (4f14) is
diamagnetic.

Chemistry - 1
Table 2.2.4 : 
 
              4f 5f
  
2. 4f   5f

3. 4f               5f
 5f  

      
 
 
                  

  (UO22+,UO2+,
NPO2+)
  

 
    
 

                
 
Pm      
 

f - block elements
Table 2.2.5: Calculated and experimental magnetic moments of
lanthanoid ions
No. of Magnetic moment

Electronic unpair (BM)
Lanthan
configurat ed
oid ion Calculat Experimen
ion electro
ed tal
ns
3+ 1
Ce [Xe]4f 1 2.54 2.3-2.5
Pr3+ [Xe]4f 2 2 3.58 3.4 – 3.6
Nd3+ [Xe]4f 3 3 3.62 3.5 – 3.6
Pm3+ [Xe]4f 4 4 2.68 2.7
Sm3+ [Xe]4f 5 5 0.84 1.5–1.6
Eu3+ [Xe]4f 6 6 0.00 3.4 – 3.6
Gd3+ [Xe]4f 7 7 7.94 7.8 – 8.0
3+ 8
Tb [Xe]4f 6 9.72 9.4 – 9.6
Dy3+ [Xe]4f 9 5 10.63 10.4 – 10.5
3+ 10
Ho [Xe]4f 4 10.60 10.3-10.5
Er 3+ [Xe]4f 11 3 9.57 9.4 – 9.6
Tm3+ [Xe]4f 12 2 7.63 7.1-7.4
Yb3+ [Xe]4f 13 1 4.50 4.4-4.9

Chemistry - 1
Introduction
The inner transition elements in which the differentiating electron

progressively enters into 5f orbitals i.e., (n-2)f orbitals are called actinoids.
These elements are following the d-block element actinium (Z=89) and
resemble the actinium in properties. Hence they are called actinoids.
They appear in 7th period between actinium and rutherfordium, the d-
block elements. They come under the group 3 elements of the long form
of the periodic table. They are placed below the lanthanoids. Actinoids
are also called 5f series of elements. They are from thorium (Z=90) to
Lr (Z=103). Among actinoids uranium is the heaviest naturally occurring
element. The elements which follow the uranium are man-made elements
and also called transuranic elements. Most of these elements are
radioactive in nature.
In this chapter the electronic configurations, oxidation states,

actinoid contraction and comparison of lanthanoids and actinoids have
been discussed in order.
2.2.6 Electronic configuration
The general electronic configuration of these elements is

[Rn]7s26d1-05f1-14. As the energy difference between 5f and 6d orbitals
is not much, the exchange of electrons between these two orbitals occur
quite commonly in the early part of the actinoids. The electronic
configurations of actinoids are shown in table 2.2.6.

f - block elements
Table: 2.2.6: Electronic Configuration of Actinoids
Name of the Atomic Electronic

Symbol
actinoid number configuration
1 2
Actinium Ac 89 [Rn]6d 7s
2 2
Thorium Th 90 [Rn]6d 7s
Protactinium Pa 91 [Rn]5f26d17s2
Uranium U 92 [Rn]5f36d17s2
4 1 2
Neptunium Np 93 [Rn]5f 6d 7s
Plutonium Pu 94 [Rn]5f67s2
Americium Am 95 [Rn]5f77s2
7 1 2
Curium Cm 96 [Rn]5f 6d 7s
9 2
Berkelium Bk 97 [Rn]5f 7s
Californium Cf 98 [Rn]5f107s2
11 2
Einsteinium Es 99 [Rn]5f 7s
12 2
Fermium Fm 100 [Rn]5f 7s
Mendelevium Md 101 [Rn]5f137s2
14 2
Nobelium No 102 [Rn]5f 7s
14 1 2
Lawrencium Lr 103 [Rn]5f 6d 7s
Among actinoids curium has the configuration

[Rn]5f 6d 7s instead of [Rn]5f87s2. This is because of the stability
7 1 2
achieved by the exactly half filled f-sublevel in curium. Lanthanoids

resemble the second half of the actinoids more closely in properties. For
example Cm closely resembles Gd and both have the common electronic
configuration f7d1s2.
2.2.7 Oxidation states
Compared to lanthanoids these elements are known to exhibit

greater range of oxidation states due to the involvement of 5f, 6d and 7s
electrons in bonding, as the energy difference between them is not much.
The various known oxidation state of actinoids are shown in table 2.2.7.

Chemistry - 1
Table 2.2.7: The various possible oxidation states of actinoids
Ac Th Pa U Np Pu Am Cm
+2
+3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5 +5 +5
+6 +6 +6 +6
+7 +7
Bk Cf Es Fm Md No Lr
+2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3
+4
From the table 2.2.7.it is evident that, the number of oxidation

states possible for these elements increases from Pa to Pu. After the
element Pu, the number of oxidation states possible gradually decreases,
due to successive increase of nuclear charge and ionization energy values.
Like lanthanoids, all actinoids exhibit the common oxidation state

of +3. However, +3 state is not always the most stable oxidation state
for the actinoids. For the first four elements i.e. Th, Pa, U and Np, +3
state is not the most stable oxidation state. For example uranium in +3
state, readily undergoes oxidation in air and in solution. The most stable
oxidation states for the elements Th, Pa, U and Np are +4, +5, +6 and
+5 respectively.
For Np even though +7 stateis possible, it immediately gets

reduced to stable +5 state. Pu shows all oxidation states from +3 to +7,
but +4 is the most stable oxidation state for it. Am has oxidation states
from +2 to +6. For Am and the remaining elements the most stable
oxidation state is +3. In lower oxidation actinoids they are ionic and
higher oxidation states they are covalent in nature.

f - block elements
2.2.8 Actinoid Contraction
In actinoids the differentiating electron enters into 5f-orbitals.

Because of the imperfect shielding effect of one electron by the other in
the same sublevel, the attraction of the nucleus over the valence electrons
gradually increases with increase in atomic number. Therefore valence
electrons are pulled closer to the nucleus causing shrinkage in size. The
net decrease in the sizes of theseions either in +3 state or +4 state, with
increase atomic number is known as actinoid contraction. The actinoid
contraction is however greater from one element to other element
compared to lanthanoid contraction. The decrease in ionic radii of these
elements in +3 and +4 states is shown in the figure 2.2.2. and values of
ionic radii of these elements in +3 and +4 states are shown in table
2.2.7.
Table 2.2.7: Ionic radii of actinoid ions in +3 and +4 states
Actinoid ion Ionic Actinoid ion Ionic

(M 3+ ) radius (Å) (M 4+ ) radius (Å)
Ac3+ 1.11 Ac4+ 0.99
3+ 4+
Th 1.08 Th 0.96
Pa3+ 1.05 Pa4+ 0.93
U3+ 1.03 U4+ 0.92
3+ 4+
Np 1.01 Np 0.91
3+ 4+
Am 1.00 Am 0.90
3+ 4+
Cm 0.99 Cm 0.89
3+ 4+
Bk 0.95 Bk 0.86
Cf3+ 0.97 Cf4+ 0.86
Es3+ 0.92 Es4+ -

Chemistry - 1
Figure. 2.2.2 Ionic radii of lanthanoids and actinoids
2.2.9 Comparison of Lanthanoids and Actinoids
Similarities
i. In the atoms of both lanthanoids (4f series) and actinoids (5f

series) the differentiating electron enters into (n-2)f orbitals.
ii. In both the series the oxidation state of +3 dominates.
iii. Like lanthanoid contraction observed in lanthanoids, there is
actinoid contraction in actinoids. Both these contractions are
due to improper shielding of (n-2)f electrons.
iv. In the absorption spectra of the elements of both the series
confirm sharp line like bands, due to f-f transitions.
v. Elements of both the series are very reactive.
vi. Most of the lanthanoid ions and actinoid ions are paramagnetic
in nature.
vii. The nitrides, per chlorates and sulphates of trivalent lanthanoid
and actinoid ions are soluble in water; while the chlorides,
hydroxides and carbonates of these ions arte insoluble in water.

f - block elements
Differences between lanthanoids and actinoids
The lanthanoids and actinoids also show some differences due

to the difference in the nature of 4f and 5f orbitals and are shown in table
2.2.8.
Table 2.2.8.The differences between lanthanoids and actinoids
Lanthanoids (4f-series) Actinoids (5f-series)

1. The differentiating electron The differentiating electron
enters into 4f orbitals enters into 5f orbitals
2. Binding energies of 4f orbitals Binding energies of 5f orbitals
are higher. are lower.
3. 4f electrons have relatively 5f electrons have relatively
greater shielding effect than 5f poor shielding effect than 4f
electrons electrons
4. They exhibit +2,+3,+4 They exhibit +2,+3,+4, +5,+6
oxidation states and the and +7 oxidation states and the
highest oxidation state is +4 highestoxidation state is +7
5. They do not form oxocations Some of them form oxocations,
2+ + +
such as UO2 UO2 , NpO2 .
6. The compounds of these are The compounds of these are
less basic more basic.
7. They do not form complexes They form complexes more
readily. easily, even with  bonding
ligands
8. They are paramagnetic and They are paramagnetic and
magnetic properties can be magnetic properties cannot be
explained easily. explained easily.
9. They are non-radioactive They are all radioactive
elements except promethium. elements.

Chemistry - 1
SUMMARY
In these elements the differentiating electron enters into (n-2)f
orbitals. These are also called inner transition elements as they appear
between the transition elements. These are of two types (i) 4f series of
elements or lanthanoids and (ii) 5f series of elements or actinoids.
Lanthanoids are 14 in number and they appear after the element La, a
d-block element. In lanthanoids we can observe lanthanoid contraction.
This is the decrease in atomic or ionic radius in their tripositive ions with
increase in atomic number and due to poor shielding effect of 4f electrons.
These elements exhibit a common and stable oxidation state of +3.
However some elements do exhibit +2 and +4 oxidation states.
Lanthanoid atoms or ions are mostly paramagnetic n nature. The 14
chemically similar elements which follow actinium are called actinoids.
The actinoid contraction from one element to other element is more
compared to lanthanoid contraction. Compared to lanthanoids these
elements exhibit more number of oxidation states. Actinoids have strong
tendency to form complexes than lanthanoids. Magnetic properties of
lanthanoids can be explained easily compared to actinoids.
INTERACTIVE LINKS
www.toppr.com/ask/question/f-block-elements-ae-known-as-
elements
https://www.priyamstudycentre.com/2019/09/f-block-
elements.html

f - block elements
What Is the first element ever created?
The first Nature-made elements were helium and hydrogen. They

formed after Big Bang, within an extremely hot environment, as a
result of combination of subatomic particles. Quarks combined,
originating protons and neutrons, which got together giving nuclei.
Then, electrons eventually combined with nuclei, creating the first
hydrogen and helium atoms. As for the first human-made element,
the answer would be technetium.
Which is the heaviest element in the world?

In terms of density, the heaviest element is osmium (22.59 g/cm3),
followed closely by iridium (22.56 g/cm3).
In terms of highest atomic number, it is something that changes

every time a new, heavier element is discovered. The natural element
with the largest atomic number is uranium (with an atomic number
of 92).

Chemistry - 1

Chapter - 3




    
 
 
 

 
 
 (CCP)
(HCP),  (BCC)
         
     

 
 
 
  
    
            
                     

UNIT - 2 Theories of bonding
Chapter - 3 in metals
Learning outcomes
· List out the general properties of metals
· Understand the concept of free electron theory and applications
· Know about the Valence bond theory of metals and limitations
· Understand the band theory of solids
· Define conductors, insulators and semi conductors with respect

to band gap
· Understand the concept of doping in semiconductors
Introduction
We know that all the elements of the periodic table can be

categorized into three types. viz., are metals, non-metals and metalloids.
Non-metals and metalloids are very few in number, while the remaining
are all metals. Metals have their own characteristic physical properties.
Some of the general properties of metals are
i) they are good conductors of heat and electricity,
ii) they are bright, shiny and highly reflective,
iii) they are malleable and ductile,

Chemistry - 1
       
 


      
     





  
 

 

     


 

 
     

 
(Tensile
Theories of bonding in metals
iv) they possess large cohesive forces in their lattices,
v) they form alloys readily,
vi) they have cubic close packed, hexagonal close packed and body
centred cubic crystal structures.
In view of these properties, metals are known to have very good

number of applications in our day to day life. In order to understand and
explain the physical characteristics of the metals, in terms of number of
valence electrons one should understand the theories of bonding in metals.
The three theories of bonding in metals which we discuss in this chapter
are,
1) free electron theory of bonding in metals,
2) valence bond theory of bonding in metals,
3) molecular orbital theory of bonding in metals (or) band theory

of solids.
2.3.1 Free electron theory of bonding in metals
This theory was first introduced by Drude (1900) and later refined
by Lorentz (1923). According to this theory, metals because of their low
ionization energies readily lose one or more valence electrons and form
the positive metal ions called kernels. Thus, metallic lattice consists of
rigid positive ions, which are assumed to be immersed in a sea of valence
electrons or gas of electrons, which are in delocalised state. Hence it is
also referred to as electron sea theory or electron gas theory. The force
of attraction which binds a metal ion to a number of electrons within its
sphere of influence is known as metallic bond. The pictorial representation
of this model is shown in figure 2.3.1.

Chemistry - 1
Strength)
 
      

 C
33000C
     

 Na,K

    



     








   Li   
 Li 

Figure 2.3.1 Electron gas model
Explanation of the metallic properties
The metallic properties such as electrical and thermal conductivity,

metallic lustre, malleability and ductility, high tensile strength etc., can be
explained on the basis of this theory as follows,
1. The electrical conductivity of metals can be explained on the basis

of the presence of mobile valence electrons. In the presence of applied
electric field these electrons move from end to the other end of the
metal and thus conduct electricity
2. The thermal conductivity of the metals is also due to the presence of

mobile electrons. When one part of the metal is heated the electrons
in that part acquire a large amount of kinetic energy. These electrons
move rapidly throughout the metal lattice and thus conduct heat to
the other part of the metal.
3. Metallic lustre is due to the to and fro oscillations of the valence

electrons of the metals when the light falls on the surface of the metals.
4. Malleability and ductility associated with metals can be explained by

the fact that, when the metals are hammered the metal ions change
their lattice positions.

Chemistry - 1
                  Li

 Li      


 
      

Li
      

      


      

      
  
     

        

      
     


5. High tensile strength of metals (resistance to stretch without breaking)
is due to the existence of strong electrostatic attraction present
between the metal ions and sea of electrons surrounding them.
Limitations
The free electron theory could not explain the vast variations in
properties of certain metals.
i. Melting point of mercury is –39° C and that of tungsten is

3300°C.
ii. The electrical conductivity of copper is 50 times more than that

of bismuth.
iii. Sodium and potassium are soft metals and can be cut easily with
a knife, but osmium is hard metal and even it can scratch the
glass.
2.3.2 Valence bond theory of bonding in metals
This theory was proposed by Linus Pauling. It is also called

resonance theory. According to this theory metallic bond is covalent in
nature and the structure of metal involves resonance of covalent bonds
between each atom and its nearest neighbour.
To explain this theory, let us consider the crystal lattice of the

lithium, the simplest metal. It has body centred cubic structure. In this
structure each lithium atom is surrounded by eight nearest lithium atoms
and at a slightly greater distance it has six next nearest neighbours. Each
lithium atom has one valence electron (2s1). So it can form a normal
covalent bond with one of its nearest Li atoms. As Li is surrounded by
eight Li atoms, there should be sixteen electrons to form the covalent
bonds among all the atoms. However, only nine electrons are available

Chemistry - 1
LiLi (Z=3)
 1S22S1. Li2     Li 
2S

Li

Li3Li 2S
    

Li       

 Li4   Li  2S 


     Lin   ‘n’ Li
  2S  ‘n’     
n/2n/2
n/2

Lin
      (Continuous band)

Li(n)


Li2p
from the nine Li atoms. Thus the bonding in Li metal is considered to be
electron deficient.
To overcome this problem Pauling suggested that, the bonding

in metals is delocalised. The true state is a hybrid of several possible
resonance structures, arising forms either synchronised resonance or
unsynchronised resonance. In synchronised resonance, each Li atom
forms only one covalent bond, as shown in the figure 2.3.2
Li Li Li Li
Li Li Li Li
Structure I Structure II
Fig:2.3.2 Synchronised resonance in non-ionic forms
As Li atom has only one valence electron, it cannot form two

bonds simultaneously. When the bond between two Li atoms shifts,
simultaneously, the other bond present between other two Li atoms shifts.
Non-synchronised resonance is the one in which Li atom can form two
bonds. This is possible only in the ionic forms as shown in figure2.3.3.
Li Li Li Li
Li Li Li Li
Structure III Structure IV
Fig:2.3.3 Unsynchronised resonance in ionic forms
In structure (III) an electron shifts from lower covalent bond

leaving a positive charge on the lower right Li atom and developing
negative charge on the upper left Li atom. Thus Li atom with negative
charge forms two bonds with two other Li atoms. Because of the large

Chemistry - 1
2p
2s, 2p2s
2p


 
      
       
    Li   

   



  


    


  
        107ohm-1m-1   
107ohm-1m-1

Gap

number of resonance structures possible for any crystal, the resonance
energy and cohesive energy are high. For example the cohesive energy
of Li metal is about three times greater than that of Li2 molecule. The
alkaline earth metals with two valence electrons per atom have a larger
cohesive energy than the alkali metals, because they are capable of
forming two bonds per atom in any resonance structure. This trend
continues with increase in number of unpaired electrons.
This theory explains the electrical conductivity of the metals, due

to the existence of ions.
Limitations: This theory does not explain
i) the conduction of heat in metals,
ii) metallic lustre
iii) retention of metallic properties in the liquid state or in solution.
2.3.3 Molecular orbital theory of bonding in metals (or ) Band

theory of solids
It is the modern theory of bonding in metals and is based on the

molecular orbital concept. According to this, the number of molecular
orbitals formed is always equal to the number of atomic orbitals combined.
When two atomic orbitals combine two molecular orbitals are formed.
Out of these two the one having lower energy than the combining atomic
orbitals is called bonding molecular orbital, while other having higher
energy is called anti bonding molecular orbital. This concept can be
extended to explain the metallic bonding and properties of metals.
Let us consider the bonding in Li metal (one dimensional lattice

involving a chain of Li atoms). The valence shell configuration of Li is 1s2
2s1. In the formation of Li2 molecule the two 2s orbitals of two Li atoms
form two molecular orbitals, one bonding and one anti bonding. The
two valence electrons occupy the bonding molecular orbital.

Chemistry - 1


 
 10-10ohm-1m-
1

Gap


  
    104ohm-1m-1  

 Gap 
       

   

‘OK’
       

(Intrinsic Semicon-
ductors))            
(Extrinsic Semiconductors)


n- p-

In the formation of Li3 molecule, three 2s orbitals of three Li
atoms form three molecular orbitals, one bonding, one non-bonding and
one anti bonding. Out of three valence electrons two of them occupy the
bonding molecular orbital and the remaining electron occupies the non-
bonding molecular orbital.
Figure 2.3.4. Molecular orbitals if Li2, Li3, Li4 molecules
In a similar way if four Li atoms are forming Li4 molecule, four 2s

orbitals form four molecular orbitals, two of them are bonding and two
of them are anti bonding. The four valence electrons occupy all the boding
molecular orbitals. Likewise in the formation of Lin molecule, ‘n’ number
of 2s orbitals of Li atoms interact and form ‘n’ number of molecular
orbitals. Out of these n/2 are bonding and n/2 are anti bonding molecular
orbitals. The valence electrons of all the Li atoms (n), occupy all the n/2
bonding molecular orbitals as shown in the figure 2.3.4.
Thus, in Lin molecule,a series of closely spaced molecular orbital

levels are formed giving rise to a continuous band (band related to 2s
orbitals), hence molecular orbital theory is also called band theory. Half

Chemistry - 1

n      
Si,Ge

PAs
   Si  Ge    

SiGe
   Si,Ge     

n
p-    
Si, Ge       

BAl
      Si  Ge  


(hole)

       
Si, Ge
p

of the band is filled by the valence electrons of all Li atoms (n) and the
remaining half of the band is vacant as shown in figure. 2.3.5.
Many closely
spaced molecular
orbital levels
constituting a band.
(Note:
there are n energy
levels and n
Figure 2.3.5. Molecular orbitals of Lin electrons, so the
band is only half
filled)
Similarly, if the vacant 2p orbitals of Li atoms interact, they result in

the formation of another continuous band called 2p band. As the difference
in energy between 2s and 2p orbitals is not much, the upper part of the
2s band and lower part of the 2p band merge to some extent as shown
in figure2.3.6. The partially filled band or completely filled band that
overlaps with an empty band is designated as valence band. The band
into which the electrons jump is called conduction band.
Figure 2.3.6. Methods of conduction

(a) metallic molecular orbitals for lithium showing half filled bands
(b) metallic molecular orbitals for beryllium showing overlapping
bands

Chemistry - 1
This model of bonding in metals readily explains the metallic

properties. For example, when a crystal of lithium is placed in an electric
field, a few electrons absorb energy and promote to the higher vacant
molecular orbitals. These electrons are responsible for the flow of current
through them. The excited electrons while returning to the ground state
give off the light, causing metallic lustre. The bonding electrons are not
localised at any particular atom in the metal crystal, so the lattice can be
deformed easily. This explains the properties of metals namely malleability
and ductility.
2.3.4 Conductors, semiconductors and insulators
On the basis of electrical conductivity solids can be divided into

three types 1. Conductors, 2.Insulators and 3.Semiconductors.
1. Conductors
The solids with conductivities ranging from 104 to107 ohm-1 m-1
are called conductors. Metalshaving conductivities in the order of 107
ohm-1 m-1 are good conductors. Metallic conduction is due to the
movement of electrons. In metals there is no significant gap between
valence band and conduction band. So electrons can flow easily from
valence bad to conduction band under an applied electric field.
2. Insulators
The solids with very low conductivities ranging from 10–20 to10–
10
ohm–1 m–1 are called insulators. In these substances the gap between
filled valence band and conduction band is very large. So electrons cannot
jump from valence band to conduction band easily.
3. Semiconductors
The solids with conductivities ranging from 10-6 to 104 ohm–1 m–

1
are called semiconductors. In these, the gap between the valence band
and the conduction and is intermediate between that of conductors and
insulators.Therefore some electrons may jump to conduction band and
show some conductivity. With increase in temperature electrical
conductivity of semiconductors increases. This is because more number
of electrons can jump from valence band to the conduction band.
Silicon and germanium crystals act as insulators at low

temperature of 0 K. However, they can be made to behave as
semiconductors either by heating or by adding appropriate amount of
suitable impurity. Asemiconductor which is obtained by heating an insulator
is called intrinsic semiconductor, while the one which is obtained by adding
suitable impurity is called extrinsic semiconductor. The process of adding
impurities is known as doping. Doping can be done with an impurity
which is electron rich (n- type semiconductor) or electrondeficient (p–
type semiconductor).
n-type semiconductors
Silicon and germanium have four valence electrons each. So

each atom forms four covalent bonds with its neighbours. When doped
with P or As, having five valence electrons, they occupy some of the
lattice points in silicon or germanium crystal. Out of five valence electrons
four are involved in the formation of four covalent bonds with the four
neighbouring Si or Ge atoms. The fifth electron which is extra becomes
delocalised. These delocalised electrons are responsible for the increase
of conductivity of doped Si or Ge crystals. Thus Si or Ge doped with
electron rich impurity is called n-type semiconductor.
p-type semiconductors
Silicon and germanium have four valence electrons each. So

each atom forms four covalent bonds with its neighbours. When doped
with B or Al, having three valence electrons, they occupy some of the
lattice points in silicon or germanium crystal. The three valence electrons
are involved in the formation of three covalent bonds with the three

Chemistry - 1
neighbouring Si or Ge atoms. The place where the fourth valence electron
is missing is called an electron vacancy or electron hole. An electron
from a neighbouring atom can come and fill the electron hole. In doing
so it leaves an electron hole at its original position. It gives an impression
that electron hole is moving in the direction opposite to that of the electron
that filled it. Thus Si or Ge doped with electron deficient impurity is
called p-type semiconductor.
Positive hole
Mobile electron
Silicon atom (no electron)
n-type
Perfect crystal p-type
semiconductor
semiconductor
SUMMARY
Most of the elements in the periodic table are metals only. Metals
have some unique properties like metallic lustre, showing good electrical
and thermal properties, malleability and ductility, ability to form alloys,
etc. The bonding in metals in terms of valence electrons can be explained
by free electron theory, valence bond theory and molecular orbital theory.
Molecular orbital theory clearly distinguishes the substances into
conductors, insulators and semiconductors. Conductivity in
semiconductors can be enhanced by adding impurities in the form of a
technique called doping.

GLOSSARY
Catalytic Which enhances the efficiency of a
Promoter catalyst
Cohesive forces Intermolecular attractive forces existing
between the adjacent molecules
Conduction band The vacant band into which electrons can
jump from valence band
Coordination The number of coordinate covalent bonds
nu mb er formed betw een metal and ligands in a
complex compound
Coordination A group in which ligands are directly
sph ere attached to metal in a complex compound,
generally show n in square brackets.
Doping Proces s of adding impurities to enhance
conductivity of a semiconductor
Du ctility Ability of a metal to stretch into nice wire
or thread like shape
Ionization sp here The molecular or ionic species present
outside the coordination sphere.
Kernels The part of atom other than valence shell,
which includes inner orbital electrons and
nucleus
Ligan d A chemical species which donates electron
pair/s and form coordinate covalent bond/s
with the metals in a complex compounds
Malleability Ability of a metal to spread into thin sheets
when hammered
Penultimate shell Last but oneshell of an atom i.e.,(n–1)
shell
Radioactive An element which emits radioactive rays
element from its nucleus
S hielding effect Protection given by the inner shell
electrons over the valence electrons form
the nuclear attraction
Su blimation The heat required to change the state of a
enth alpy substance from solid state to gaseous state

Chemistry - 1
Synchronised Resonance structures those with covalent

resonance structures
Unsynchronised Ionic Resonance structures

Resonance
Valence band The outer most band with electrons
INTERACTIVE LINKS
https://chem.libr etexts.or g/Bookshelves/Gener al_Chemistr y/

Map%3A_General_Chemistry_(Pet rucci_et _al. )/
11 % 3 A _ C h emi ca l _ B o n d in g _ I I % 3 A_ A d d i t i on a l _ A s p ec t s /
11.7%3A_Bonding_in_Metals
https://courses.lumenlearning.com/boundless-chemistry/chapter/crystals-
and-band-theory/
Multiple Choice Quest

ions
1. In which of the following metal 1. Ionic 2. Covalent
pair one is a soft metal and other
one is hard metal 3. Resonance 4. Coordinate
4. The number of covalent bond/s

1. Sc, Ti 2. W, Pt
formed by one Li atom in
3. K, Os 4. Cu, Zn Synchronised resonance form
is
2. Free electron theory is also
1. One 2. Two
called
3. Three 4. Four
1. Electron gas theory
5. A perfect conductor has
2. Electron sea theory
1. Zero conductivity
3. Resonance theory 4. 1&2
2. Unity conductivity
3. The nature of metallic bonding
as per free electron theory is 3. Infinite Conductivity

4. Average conductivity be immersed in a “sea”
of_____
6. Solids with the conductivity
range 10-6 to 104 ohm-1 m-1 are 1. electrons.
called
2. positive ions.
1. Conductors 2. Insulators
3. negative ions.
3. semiconductors 4. 1 & 2
4. both2&3.
7. At 0 K Germanium acts as
10. Because of metallic bonds,
1. Insulator 2. Semiconductor
metals
3. Conductor 4. Gold
1. are good conductors of
8. Which type of semiconductor is electricity.
formed, if silicon is doped with
electron rich impurity 2. can change shape without
breaking.
1. P-type 2. n- type
3. are ductile and malleable.
3. pn-type 4. o-type
1. 1&2 only 2. 2&3 only
9. According to free electron
theory Kernels are imagined to 3. 1&3 only 4. 1, 2&3
KEY
1. 3 2. 1 3. 1 4. 1 5 3
6. 3 7. 1 8. 2 9. 1 10. 4

Chemistry - 1
 
  


       


 


  

  
    


        
 


      
anisotropic
      

UNIT - 3 Solid State
Learning outcomes
After studyingthis Unit, student shall be able to
1. Understand the characteristics of solids and differences between

crystalline and amorphous solids
2. know about the law of constancy of interfacial angles, law of
symmetry and law of rationality of indices
3. know about the terms lattice point, space lattice, unit cell
4. Understand the seven crystal systems and their characteristics
5. Have the idea about the Bravais lattices
6. Understand the use of Miller indices in designating the planes
7. Derive the Bragg’s equation
8. Know the methods of determination of crystal structures
9. Know about the various types of crystal defects
3.1. Introduction
A substance can exist in three physical states. viz., solid state,
liquid state and gaseous state depending on the temperature at which the
substance is present. With increase in temperature solid converts into
liquid and liquid converts into gas.
A solid is nearly incompressible state of matter with well-defined

state, rigidity and a definite volume. In solid state the atoms or molecules
or ions making up the solid are in close contact and are in fixed positions.
Solids have their own characteristic properties. Some of them are
(i) they have definite volume irrespective of the size of the container

Chemistry - 1

isotro-
pic
 

  


 
 
 

     



        face
   
  

 NaCl    

        



Solid State
(ii) they are rigid and have definite shape
(iii) they are almost incompressible
(iv) they are mostly crystalline in nature
(v) they have relatively higher densities than liquids or gases
(vi) they diffuse very slowly, when compared to liquids and gases
(vii) most of them melt on heating and become liquids.
All the solids can broadly be classified into two types. i)
Crystalline solids, ii) Amorphous solids.
In crystalline solids there is complete regularity in the arrangement

of atoms or molecules of which it is made of. They have sharp melting
point; they possess symmetry and they have definite interfacial angle. In
amorphous solids like glass and pitch, the arrangement atoms or molecules
is not of long-range order and they have no sharp melting points and
they do not possess interfacial angles. In crystalline solids certain physical
properties like, refractive index, density etc., have definite values in
different directions (anisotropic) while in amorphous solids those certain
properties have same value in all the directions (isotropic). Crystalline
solids may also be classified into molecular solids, covalent network
solids, metallic solids and ionic solids on the basis of nature of the
constituent particles and inter particle forces.
In this chapter an attempt is made to describe certain aspects of

crystalline solids.
Laws of crystallography
The study of geometry, properties and structure of crystalline

substances is known as crystallography. It is based on three fundamental
laws. (i) the law of constancy of interfacial angles (ii) the law of symmetry
and (iii) the law of rational indices.
3.1.1 Law of constancy of interfacial angles
The crystals of a substance can be obtained either by cooling

the melt or the solution of that substance. The size of the crystal formed
Chemistry - 1
 


       

a b c
a  


NaCl   
iii
i

ii  (diagonal)



b




c



Solid State
depends on the rate of cooling. If cooling is done slowly crystals of large
size are formed, because the constituent particles get sufficient time to
arrange themselves in proper position. Further shape of the crystals of
the substances also depend on the condition of crystallization.
Even though the sizes of the faces and shapes of the crystals of
a substance may vary widely yet the interfacial angles between any two
corresponding faces of the crystals are always constant. This is known
as the law of constancy of interfacial angles. For example, the interfacial
angles in all the NaCl crystals are found to be same i.e., 90° irrespective
of the size and shapes of faces. Depending on the interfacial angles of a
crystal we can easily predict the type of crystal. The instrument used to
measure the interfacial angles is called goniometer. The measurement of
crystal angles is important in the study of crystals.
Figure 3.1.1: Different shapes of crystals of the same substance with same
interfacial angle
3.1.2 The law of symmetry
The crystals of a particular substance always possess the same

elements of the symmetry and crystals of different substances exhibit
different elements symmetry. This is known as law of symmetry. The
three important elements of symmetry are (i) plane of symmetry (ii) centre
of symmetry and(iii) axis of symmetry.
i) Plane of symmetry
An imaginary plane passing through the crystal, which can divide

the crystal into two parts such that one is the exact mirror image of the
other is called plane of symmetry. The planes of symmetry are also called
mirror planes. A cubic crystallike sodium chloride possesses two types
Chemistry - 1
‘n’   ‘n’n-fold
 n 

2-fold

        
 

       
  
  

(interfacial crystal edge) 


  

 


   (Hauy)    
       
(a : b: c)
     
        

Solid State
of planes of symmetry. They are a) Rectangular planes of symmetryb)
Diagonal planes of symmetry.
a) Rectangular planes of symmetry: The planes which are situated

midway and parallel to the opposite faces are called regular
planes of symmetry. As a cubic crystal has six faces, it has three
rectangular planes of symmetry as shown in the figure 3.1.2.
b) Diagonal planes of symmetry: These are the planes touching

the opposite edges. As they lie on the diagonal of the opposite
faces these are called diagonal planes of symmetry. In a cubic
system, there are twelve edges or six pairs of opposite edges.
Therefore, a cubic crystal has six diagonal planes of symmetry.
One plane passing diagonally through the cubic crystal is shown
in the figure 3.1.2.
(a) (b)
Figure 3.1.2: Types of planes of symmetry a) Rectangular Plane of Symmetry

b) Diagonal Plane of Symmetry
(ii) Centre of symmetry
It is defined as an imaginary point within a crystal such that any

line passing through this point intersects the opposite faces of the crystal
at equal distances. It is also called centre of inversion.
(iii) Axis of symmetry or axis of rotation
It is an imaginary line passing through the crystal such that when

the crystal is rotated about this line, it presents the same appearance
more than once in one complete revolution i.e. in a rotation through
Chemistry - 1

x, y, z
A, B, COC = a, OB = bOC = c

a : b : c

x, y, z
K L M
OK = 2a, OL = 2bOM = 3c
OK : OL : OM = 2a : 2b : 3c
      


a



     
Unit intercepts
   Whole number multiples

2a, 2b,
3cX, Y, Z
a, b, c

 ‘  ’
Solid State
360°. Suppose the same appearance of the crystal is repeated on rotating
it through an angle of 360°/n around the imaginary axis, the axis is called
an n-fold axis of symmetry, where n is called order of axis.
If a cube is rotated about an axis passing perpendicularly through

the centre, so that the similar appearance occurs four times in one
revolution then axis is called a four-fold axis (tetrad axis). If similar
appearance occurs twice in one complete revolution, i.e., after 180° the
axis is called two-fold axis of symmetry or diad axis. If the original
appearance is repeated three times in one revolution i.e., rotation after
120°, the axis is called threefold axis of symmetry or triad axis. If the
original appearance is repeated after an angle of 60° as in the case of a
hexagonal crystal the axis is called six fold axes of symmetry. The various
axis of symmetry is shown in figure 3.1.3.
Figure 3.1.3: The types of axis of symmetry
Table 3.1.1: various types of elements of symmetry associated

with a cubic crystal
Types of elements of symmetry

Centre of
Plane of symmetry Axes of symmetry
symmetry
Rectangular planes Four-fold axes of Centre of
3 3 1
of symmetry symmetry symmetry
Diagonal plane of Threefold axes of
symmetry 6 symmetry 4
Two-fold axes of
6
symmetry

Chemistry - 1

  


 

    2b, c
  a : 2b : c
   
1 1 1
  : :
2 1
2 2 2
  : :
2 1




 
dhklhkl 
a
d hkl 
 h2  k 2  l 2
a    h, k, l


  


Solid State
3.1.3 Law of rational indices (Hauy’s Law)
This law was proposed by Hauy. According to him if the

intercepts of any a face of the crystal on the three axes are measured,
the following generalization is observed, this is called the law of rational
indices.
The intercepts made by any face of the crystal on the

crystallographic axes are either:
(i) same as those of the unit plane or
(ii) simple whole number multiples of those of the unit plane or
(iii) one or two intercepts may be infinity, if the face is parallel to one
or two axes i.e., the face does not cut one or two axes.
Explanation of law of rational indices

Consider a crystal plane intersecting the x, y, z axes at A, B, C
respectively such that OC = a,OB = b and OC = c, as shown in figure
3.1.4. The ratio of the intercepts is a : b : c. Considering one and half
times larger crystal, the same plane intersects the x, y, z axes at K, L, M
respectively, such that OK = 2a, OL = 2b and OM = 3c. Therefore OK
: OL : OM = 2a : 2b : 3c. Hence the ratio of the intercepts, OK : OL :
OM for larger crystal is same as the intercept of a smaller crystal on the
three coordinate axes.
The law of rational indices may also be stated that, it is possible

to choose along the three coordinate axes, unit distances (a,b,c) are not
necessarily of the same length, such that the ratio of the three intercepts
of any plane in the crystal is given by ma : nb : pc. Where, m, n and p
are either integral whole numbers including infinity or fractions of whole
numbers. When a plane is parallel to a particular axis, the coefficient
corresponding to that axis takes a value of infinity.

Chemistry - 1
 a, bc

 h, k
l
(Space Lattice,
Lattice Point, Unit Cell)





      
               
      
   line   

      



    
 a, b, c      
replace

(Unit Cell)

Solid State
Figure 3.1.4: Rationality of indices
3.1.4 Miller Indices
a) Weiss Indices
The Weiss parameters, introduced by ‘Weiss’ (1817) are the
ancestors of the Miller indices. These indices give an approximate
indication of a face orientation with respect to the crystallographic axes
and are used as a symbol for the face.
According to law of rational indices, the intercepts of any face

of a crystal along the crystallographic axes either equal to the unit
intercepts a, b, c or their simple whole number multiples.
As shown in the figure 3.1.4 the plane has intercepts at distances

of 2a, 2band 3c on X, Y and Z axes respectively. The coefficients of a,
b and c, namely 2, 2 and 3 respectively are known as the Weiss indices
of a plane. Further, the Weiss indices may not be always an integral
number. They may contain fractional values including infinity.
Miller indices are the set of integers (h, k, l) which are used to
describe a given plane in a crystal. The Miller indices of a face of a
crystal are inversely proportional to the intercepts of that face on the
various axes. So Weiss indices have been replaced by ‘Miller indices’.
Miller indices of a plane are obtained by taking the reciprocals of Weiss
Chemistry - 1
 


a, b,c
 ,  ,  

(Lattice Points)
 
Cor-
nersFace centersBody Cen-
tre   

    


     


a,
b,c ,  ,  

 
           



Solid State
indices and then multiplying throughout by a smallest number to make all
these reciprocals as integers.
For illustration, consider a Weiss notation is given

by a : 2b : c then the Weiss indices of the plane are , 2 and 1. The
Miller indices of the plane may be calculated as reciprocals of the
1 1 1
coefficients of Weiss indices , , and multiplying by 2 in order to get
 2 1
whole numbers 0, 1 and 2. Thus, the Miller indices of the plane are 0, 1
and 2 and the plane is designated as (012) plane i.e., h = 0, k = 1 andl
= 2. The distance between the parallel planes in a crystal are designated
as . For different cubic lattices these interplanar spacings are given
by the given formula
Where, ‘a’ represents the length of the side of the cube, while h,
k andl are the Miller indices of the plane.
The steps to be followed for determining the miller indices for a plane
are
(i) Prepare a three-column table with the unit cell axis at the top of
the column.
(ii) Enter in each column the intercept (multiple of a, b or c) of the

plane with that axis.
(iii) Invert all numbers.
(iv) Clear fraction to obtain h, k and l
Importance of Miller indices
In material science it is very essential to have a notation system

for atomic planes since these planes influence optical properties, reactivity,
surface tension and dislocations.
Chemistry - 1


  

a
b

corners



(Face centered unit cell)
(Body centered unit cell)
(End centered unit cell)


        



X - 
X -
      
OrientationX -
X - 

Solid State
Problem .1
A crystal plane intercepts the three crystallographic axes

1 3
at a, b and c where a, b and c are the unit lengths along X, Y and
2 2
Z axes respectively. What are the Miller indices of this plane?
X Y Z
1 3
Intercepts = A b c
2 2
1 3
Weiss indices = 1
2 2
1 2 2
Reciprocals =
1 1 3
After multiplying with 3, we get

Miller indices = 3,6 and 2
Therefore the plane is designed as (362) plane.
Problem 2
Calculate the Miller indices of the crystal plane which cut through
the crystal axes at 2a, –3b and –3c.
X Y Z
Intercepts = 2a –3b –3c
Weiss indices = 2 –3 –3
1 1 1
Reciprocals =
2 3 3
Miller indices = 3, –2 and –2
Therefore, the plane is designed as (3, 2, 2 ) plane.

Chemistry - 1

X - 
   X -   
 X -  
X -
   

     
 X -      


d
 X -X -
  
         X -          
     

X -ABC
  X DEF
  

X -in phase


DEFcoincide
path length
Solid State
Problem 3.
Calculate the Miller indices when a plane cuts the three axes
1 2
at a , b and  c.
2 3
X Y Z
1 2
Intercepts = a b  c.
2 3
1 3
Weiss indices = 8
2 2
3
Reciprocals = 2 0
2
Miller indices = 4, 3 and 0
Therefore, the plane is designed as (430) plane.
3.1.5. Space lattice, Lattice points, Unit cell
The arrangement of geometrical points in a definite pattern in

space is called lattice. If the constituents of a crystal viz., atoms, molecules
or ions are denoted by points, then the lattice is regarded as an infinite
set of points, repeated regularly through space. The lattice may be one
dimensional, two dimensional or three dimensional.
If a set of points are repeated regularly along a line, it is called a

one-dimensional lattice. In this lattice the question of interfacial angle
does not arise. If a set of points are repeated regularly along any two
coordinate axes, it is called a two-dimensional lattice. This lattice contains
one interfacial angle. If the points are repeated regularly along the three
coordinate axes, it results in the formation of a three-dimensional lattice,
known as space lattice and is shown in figure 3.1.5. It is characteristic of
three interfacial angles and three edge lengths a,b,c. If the points in space
lattice are replaced by the constituents of the crystal, it is called crystal
lattice.

Chemistry - 1
  OL    OM

  LN + NM 

  
  LN + NM
LN + NM

 LN + NM  n 
OLM, OMN  
 LN = NM
 n  = 2LN .................... (3.1.1)
OLN 
LN
Sin 
ON
LN  ONSin 
LN  dSin  ( ON = d) .................... (3.1.2)
LN
n   2 dSin  .................... (3.1.3)
n n
n  
    n,  
‘d’
(Powdered method) 
 
        
Solid State
Figure 3.1.5: Three-dimensional lattice (space lattice)
Unit cell
The basic units of the space lattice are called unit cells. Thus, a
unit cell is the smallest repeating unit in space lattice, which when repeated
over and over again produces a crystal of the given substance. It possesses
all the structural properties of the given crystal. So, it is the essential
feature of the crystal structure.
In order to describe the unit cell, we should know the distances

a, b and c, which give the lengths of the edges of the unit cell and angles
a, b and g between the three imaginary axes.
Figure 3.1.6 Interfacial angles and edge lengths

Chemistry - 1
 





     X -





    X -  
       X -
    X -   
       
  


         
   


(Cubic)
      

Solid State
Lattice points
The points representing the atoms or molecules or ions in a unit

cell are known as lattice points. They include the corners, face centers,
body centre of the unit cells.
The lattice point that lies at the corner is shared by eight other
unit cells. So, the contribution of corner point to each unit cell is 1/8. The
lattice point that lies at the edge centre is shared by four other unit cells.
So, contribution if it to each unit cell is ¼. The lattice point that lies at the
face centre is shared by twounit cells. So, contribution of face centred
point to each unit cell is ½. The lattice point at the centre of the unit cell
is independent as it is not shared by any other unit cells.
Crystal systems
In space lattice each unit cell is characterized by lengths of the

edges a, b and c and angles between the edges a, b and g. These are
known as the parameters of the unit cell. On the basis of these parameters
there are a total of seven crystal systems.
The seven crystal systems along with edge length and interfacial
angles a, b and g are shown in table 3.1.2 and structures in figure 3.1.7.
Figure 3.1.7: Seven crystal systems

Chemistry - 1


     






       
        
intrinsic
extrinsic
     
 line defect  
Plane defects

  

        
        


 
   AB
NaCl, CsCl, KBr
Solid State
Table 3.1.2: Seven Crystal Systems-Characteristics
S. Name of the Edge

Axial angles Examples
No crystal system lengths
0
1 Cubic a =b=c  =β =  = 90 NaCl, ZnS, Cu
0 SnO 2, TiO2,
2 Tetragonal a = b c  =β =  = 90
White tin
BaSO4, KNO3,
3 Orthorhombic a b c  =β =  = 900 rhombic
sulphur
CaSO4 2H2O,
0
 == 90 , Na 2SO 4 10 H2O
4 Monoclinic a b c
β  900 Monoclinic
sulphur
0
 =β= 90 , CdS. ZnO,
5 Hexagonal a = b c 0
=120 graphite
Rhombohedral 0
6 a =b=c  =β =  = 90 CaCO3, HgS
or Trigonal
CaSO4 5H2O,
7 Triclinic a b c β 900
K2Cr2 O7
Bravais lattices
With the help of geometrical calculations Bravais showed that,
there can be 14 different ways in which similar points can be arranged in
a three-dimensional lattice. Thus, the total number of space lattices or
unit cells possible for 7 crystal systems is only 14. These 14 space lattices
possible for 7 crystal systems are referred to as the Bravais lattices. The
14unit cells /space lattices are shown in figure 3.1.8.

Chemistry - 1




       

ab

NaCl, CsCl, KBr,
KCl
  


AgClAg+
Na+
 NaCl  a
    b   

Ag+

      
       
AgBr



Solid State
Figure 3.1.8: Bravais lattices of seven crystal systems
Figure 3.1.8: Bravais lattices of seven crystal systems
Thus, the unit cells shown above are of two types. They are i)
primitive or simple unit cells ii) centered unit cells.
Primitive unit cells
Those unit cells in which constituent particles are present only at

the corners of the unit cells are called primitive unit cells. Every crystal
system has one primitive unit cell.
Centred unit cells
Those unit cells in which the constituent particles are not only
present at the corners but also present at other positions of the unit cells

Chemistry - 1
  



  


  
                 

     
        
         
      

             
 

                
               
         
         
 
     

NaCl,
 
CsCl 
Solid State
are called centred unit cells. These are of three types. (i) face centred(ii)
body centred and (iii) end centred unit cells.
(i). Face centred unit cells: In these unit cells, the constituent particles
are present at all the corners and centres of all the faces.
(ii). Body centred unit cells: In these unit cells constituent particles
are present at all the corners and one constituent particle at its
centre.
(iii). End centred unit cells: In these unit cells constituent particles are
present at all the corners and centre of any two opposite faces.
3.1.6 X-ray Diffraction and Crystal Structure

The phenomenon by which X-rays are reflected from the atoms
in a crystalline solid is called diffraction. The diffracted X-rays generate
a pattern that reveals structural orientation of each atom in a given
compound. X-ray diffraction is extensively used in chemistry for the
characterization of organic and inorganic compounds that are made for
pharmaceutical companies or making batteries of the cell phones. X-ray
difraction finds the geometry or shape of a molecule using X-rays. This
technique is based on the elastic scattering of X-rays from structures
that have long range order (crystalline solids).
Bragg’s law (Bragg’s equation)
Bragg observed that scattering of X-rays by crystals is considered

as reflection from successive planes of atoms in the crystal. But, unlike
reflection of ordinary light, the reflection of X-rays can take place only
at certain angles. These angles are determined by the wave length of the
X-rays and the distance between the planes in a crystal. The fundamental
equation which gives a simple relation between the wavelength of the X-
rays, the interplanar distance in the crystal and the angle of reflection, is
known as Bragg’s equation. This can easily be derived by considering
the following figure 3.1.9.

Chemistry - 1

  

      
FeS, CuS.
  

FeO 
FexO, (x = 0.93 to 0.96) V2O5
VOx (where x = 0.6 )
      



(Metal excess defect)
     a  
  b

      
     

F
FARBENZENTER
  


Solid State
Figure 3.1.9 X-ray reflection from crystals
From the above the horizontal lines indicate parallel planes in

the crystal structure, separated from one another by the distance ‘d’.
Suppose a beam of X-rays falls on the crystal at angle 5Øß, as shown in
the figure.Some of these rays will be reflected from the upper plane at
the same angle 5Øß while some others will be absorbed and get reflected
from the successive layers. ABC is the plane perpendicular to the incident
ray and DEF is that perpendicular to the reflected beam. The waves
reflected by different layers in a crystal will be in the phase with each
other only if the difference in the path lengths of the waves reflected from
the successive planes is equal to an integral number of wavelengths. By
constructing OL and OM perpendicular to incident and reflected beams
it is observed that the difference in path length (assume, ) of the waves
reflected from the two planes is given by
 = LN + NM
The value of  is equal to a whole number multiple of wave

length , i.e.,
n = LN + NM
From the figure 3.1.9 it is clear that the triangles ONL and OMN
are congruent, hence LN = NM i.e.,
n = 2LN ————(3.1.1)

Chemistry - 1
 NaCl Na     
NaCl  Na
NaCl     Cl-  Na
      


LiCl‘K’KCl




       


ZnO
 
1
 Zn 2 
ZnO  O2  2e 
2
  Zn2+   



(Metal deficiency defects)

  
missing
Solid State
From the right angled triangle OLN,
LN
sin  
ON
LN  ON sin 
LN  d sin  ( ON  d ) ————(3.1.2)
Substituting the value of LN from equation (3.1.2) in equation
(3.1.1) we get
or n  2 d sin  ————(3.1.3)
Where n = 1,2,3. If n=1, it is called first order difraction, if n=2 it is

called second order difraction and so on. The above equation is called
Bragg’s equation. By knowing the values of , n and wavelength ,
the distance between atomic planes d can be calculated.
Powder method (Deby – Scherrer – Hull method)
In Bragg’s method, a single crystal is required whose size is

much larger for experimental purpose. But, in the case of powder method,
the crystal sample may not be required in large quantity. For the
experimental study, even 1mg of the material is sufficient. The powder
method was devised independently by Debye,Scherrer and Hull.
Powder diffraction is one of the primary techniques used to

characterize various materials. This method provides structural
information even when they crystallite size is too small for analysis.
The powder method is more widely used particularly for crystals

with simple structures. The crystal under study is powdered and taken in
a capillary tube. The powder is exposed to monochromatic X-ray beam
of specific wavelength. The reflected beam is allowed to fall on a
photographic film surrounding the capillary tube like an arc. As the powder
contains a large number of small crystals and hence there is no need to
rotate the capillary tube. The powder, in fact, consists of many small
Chemistry - 1


FeO, FeSNiO

 
      
       

  







hole
       
      
doping
      



Solid State
crystals which are oriented in all possible directions. As a result of this,
X-rays are scattered from all sets of planes (e.g. 100, 110, etc). The
scattered rays are detected by using an X-ray sensitive film. The principle
of this method is illustrated in fig. 3.1.10. The two big spots around the
two holes correspond to the incident and out coming beam of X-rays.
Around each spot, there are lines with specific distances corresponding
to definite angle 5Øß. By using the value of 5Øß, the l value can be
calculated from the Bragg’s equation.
3.1.10 The powder method for X-ray diffractionApplications
i. This method is most useful for cubic crystals.

ii. It is also used for determining the complex structure of metals
and alloys.
iii. This method helps in distinguishing the different allotropic

modifications of the same substance.
3.1.8 Defects in Crystals

If the constituent particles in a crystal are arranged in an orderly
manner, then it is called an ideal crystal. But, no crystal is generally perfect
or ideal. In other words every crystal will suffer from some imperfections
or defects which are called crystal defects. These imperfections may be
due to deformation of the solid, rapid cooling from high temperature, or
Chemistry - 1
striking the solid with high-energy radiation etc. The defect may be a
point or along a line or over a surface.
The crystal defects may be classified into the three types: (i)
Stoichiometric defects (ii) Non-stoichiometric defects and iii. Impurity
defects.
(i) Stoichiometric Defects
If imperfections in the crystal are such that the ratio between the
cations and anions remains the same as represented by the molecular
formula, the defects are called stoichiometric defects. These are further
divided into two types
(1) Schottky defect: In an ionic crystal of the type A+B–, if equal

number of cations and anions are missing from their lattice sites
so that the electrical neutrality is maintained, it is called Schottky
defect. The Schottky defect containing one pair of holes due to
missing of one cation and one anion is shown in fig. 3.1.11. As
the number of ions decreases as a result of this defect, the mass
decreases whereas the volume remains the same. Hence, the
density of the solid decreases.
Figure 3.1.11 Schottky defect in a stoichiometric crystal
This type of defect is shown by highly ionic compounds which

have (i) High co-ordination number and (ii) Small difference in the size
of cations and anions.
APSCHE - I NaCl,
Examples: KCl,CHEMISTRY
SEMESTER TEXT BOOK
KBr, CsCl etc. 190
Solid State
(2) Frenkel defect
If an ion is missing from its lattice site causing a vacancy or a

hole there and if it occupies the interstitial site, electrical neutrality as well
as the stoichiometry of the compound are maintained. This type of defect
is called Frenkel defect. Since cations are usually smaller, it is more
common to find the cations occupying interstitial sites. The Frenkel defect
in whichone cation is missing from the lattice site and is occupying the
interstitial site is shown in fig. 3.1.12. Since no ions are missing from the
crystal as a whole, the density of the solid remains unchanged.
Figure 3.1.12 Frenkel defect in a stoichiometric crystal
This type of defect is observed in the compounds which have (i)

low coordination number and (ii) larger difference in the size of cation
and anions. Frenkel defects are found in silver halides due to small size
of Ag+ ion. They are not found in alkali metal halides as the alkali metal
ions cannot fit into the interstitial sites. There are some ionic solids which
show both Schottky and Frenkel defects e.g. AgBr.
Some other consequences of Schottky and Frenkel defects
(i) Solids with these defects conduct electricity to a small extent.

This is because if an ion moves from its lattice site to occupy a
‘hole’ it creates a new ‘hole’. In this way, a hole moves across

Chemistry - 1
the crystal, which as a result moves the charge in the opposite
direction.
(ii) Due to presence of holes, the stability (or the lattice energy) of
the crystal decreases.
In Frenkel defect since similar charges come closer, resulting in
the increase of dielectric constant of the crystals.
The differences between Schottky and Frenkel defects are shown

in table 3.1.3
SCHOTTKY DEFECT FRENKEL DEFECT
(i) It is due to missing of
It is due to missing of
ions (usually cations)
equal number of cations
from the lattice sites and
and anions from the
which occupy the
lattice sites
interstitial sites
(ii) This results in decrease
It has no effect on the
in the density of the
density of the crystal
crystal
(iii) It is found in highly ionic It is found in crystals
compounds with high co- where the difference in
ordination number and the size of cations and
having cations and anions is very large
anions of similar sizes
e.g., Silver halides.
eg. NaCl, CsCl etc.,
Non-stoichiometric Defects
As a result of the imperfections in the crystal, if the ratio of the

cations to the anions is different from that indicated by the ideal chemical
formula, the defects are called non-stoichiometric defects. For example,
it is difficult to prepare ferrous oxide with the ideal composition, FeO.
What we actually obtain is FexO, (x = 0.93 to 0.96). Similarly, vanadium
oxide has the composition VOX where x = 0.6 to 1.3. Non-stoichiometric

Solid State
compounds are generally formed by transition metals and to some extent
by lanthanoids and actinoids.
These defects result in either excess of the metal atoms or excess

of the non-metal atoms (or deficiency of the metal atoms).
(a) Metal excess defects: This may occur in either of the following
two ways:
(i) By anion vacancies
A negative ion may be missing from its lattice site, leaving a hole
which is occupied by an electron. The electrons thus trapped in the anion
vacancies are called F-centres (from the German word ‘Farbenzenter’
for colour centre) because they are responsible for imparting colour to
the crystals.
For example, when NaCl is heated in an atmosphere of Na

vapour, the excess of Na atoms deposit on the surface of NaCl crystal.
Cl– ions then diffuse to the surface where they combine with the Na
atoms which become ionized by losing electrons. These electrons diffuse
back into the crystal and occupy the vacant sites. Similarly excess of Li
in LiCl makes it pink and excess of K in KCl makes it violet.
This defect is similar to Schottky defect and is found in crystals

having Schottky defects.
(ii) By the presence of extra cations in the interstitial sites
Metal excess may also be caused by an extra cation occupying

the interstitial site. Electrical neutrality is maintained by an electron present
in another interstitial site. This defect is similar to Frenkel defect and is
found in crystals having Frenkel defects. For example, when ZnO is
heated, it loses oxygen and turns yellow due to the following reaction.
1
ZnO Zn2+ + O 2 + 2e–
2

Chemistry - 1
2+
The excess of Zn ions thus formed get trapped into the vacant
interstitial sites and the electrons in the neighbouring interstitial sites.
Crystals with either type of metal excess defects contain some

free electrons. Hence such materials act as semiconductors.
Figure 3.1.13 Metal excess defects
(b) Metal Deficiency defects
This defect occurs when the metal showsvariable valence i.e.

for transition metals. This defect usually occurs due to the missing of a
cation from its lattice site and the presence of the cation having higher
charge (e.g.,+2 instead of +1) in the adjacent lattice site. Examples :
FeO, FeS and NiO.
Figure 3.1.14 Metal deficiency defects

Solid State
(C) Impurity Defects
These defects arise when foreign atoms are present at the lattice
site (in place of host atoms) or at the vacant interstitial sites. In the former
case, we get substitutional solid solutions while in the later case, we get
an interstitial solid.
Introducing impurity defect in covalent solids
The group 15 elements have one excess valence electron

(compared to Si or Ge) after forming the four covalent bonds normally
formed by group 14 elements. The excess electrons give rise to electrical
conduction. A group 13 element which has only three valence electrons
forms an electron deficient bond or a hole. Such holes can move across
the crystal giving rise to electrical conductivity. Thus impuritydoped Si
and Ge are semi-conductors whose conductivity increases with increasing
temperature. This is unlike the metals whose conductivity decreases with
increase of temperature.
SUMMARY
Solids have definite volume and shape. Solids can be classified

into (i) crystalline solids (ii)amorphous solids, based on the arrangement
of their constituents. In a crystalline solid the constituents of it have an
orderly arrangement extending over a long range. A crystalline solid is
characterized by a definite orientation of atoms, ions or molecules, relative
to one another in a three-dimensional pattern. The regular arrangement
of these species throughout the crystal is called a crystal lattice. A crystal
may be considered to consist of large number of unit cells, each one in
direct contact with its nearer neighbour and all similarly oriented in space.
A unit cell is characterized by the three edge lengths or lattice

constants a, b and c and the angle between the edges á, â and ã. There
are seven primitive crystal systems, which differ in the arrangement of
Chemistry - 1
their crystallographic axes and angles. Corresponding to the seven crystal
systems, Bravais proposed 14 possible lattices.
X-Ray diffraction analysis is the most powerful tool for the

determination of crystal structure. The inter planar distance (d) between
two successive planes of atoms can be calculated using the Bragg’s
equation 2d sin  = n 
The structure of an ionic compound depends upon the

stoichiometry and the size of the ions. Generally, in ionic crystals the
bigger anions are present in the close packed arrangements and the cations
occupy the voids. Crystals always found to have some defects in the
arrangement of their constituent particles. The Schottky defect arises
due to the missing of equal number of cations and anions from the crystal
lattice. The Frenkel defect arises due to the dislocation of ions from its
crystal lattice. The ion which is missing from the lattice point occupies an
interstitial position. The metal excess defect arises due to the presence
of a greater number of metal ions as compared to anions. The metal
deficiency defect arises due to the presence of a smaller number of cations
than the anions.
GLOSSARY
Lattice Point: The position in the unit cell or in a crystal where the
probability of finding an atom or ion or molecule is
higher.
Space Lattice: An array of points showing how particles are
arranged at different sites in three dimensional
space.
Unit Cell: The smallest building block of crystal structure.
Repetition of the unit cell forms a solid crystal.
Crystalline solid: Solid with definite shape and interfacial angles.
Interfacial angle: The angle between two adjacent faces of a crystal.

Solid State
1. Repeatable entity of a crystal d. anions cannot be

structure is known as accommodated in voids
a. crystal b. lattice 5. In a Schottky defect
c. unit cell d. Miller indices a. an ion moves to interstitial
position between the lattice
2. The process of crystallization
points
involves
b. electrons are trapped in a
a. concentration of atoms into
lattice site
a highly structured form.
c. some lattice sites are
b. solidification of atoms into
vacant
a highly structured form.
d. some extra cations are
c. solidification of solution.
present in interstitial space
d. concentration of solution.
6. The space latt ice of
3. Which of the following is a graphite is
non-crystalline solid?
a. cubic b. tetragonal
a. diamond b. graphite
c. rhombic d. hexagonal
c. glass d. common salt
7. The crystal defect in which
4. Alkali halides do not show cations are present in the
Frenkel defect because interstitial sites is
a. cation and anions have a. Frenkel defect

almost equal size
b. Schottky defect
b. there is a large difference
c. Metal deficiency defect
in size of cations and
anions d. Metal excess defect
c. cations and anions have
low coordination number
Chemistry - 1
8. The correct set of interfacial a. cubic system
angles in a hexagonal crystal
b. tetragonal system
system is
c. orthorhombic system
a. á = â = g = 90o
d. monoclinic system
b. á = â = 90° g = 120o
13. The crystal planes which give
c. á = â = g ‘“ 90o
bright spots in primitive cubic
d. á ‘“ â ‘“ g ‘“ 90o lattice are
9. The ratio of the effective number a. 100 b. 110

of atoms present in a simple
cubic, body-centred cubic and c. 111 d. all
face-centred cubic unit cells, 14. Which of the following is not a
respectively are characteristic of a crystalline
a. 8:1:6 b. 1:2:4 solid?
c. 4:2:1 d. 4:2:3 a. definite and characteristic

heat of fusion
10. X-ray diffractometers are not
used to identify the physical b. isotropic nature
properties of which of the c. a regular periodically
following? repeat ed patt ern of
a. metals b. liquids arrangement of constituent
particles in the entire
c. solids d. none of the above crystal
11. Law of rational indices is mainly d. a true solid
based on the position of
15. Labeling of the lattice planes is
a. faces b. edges done by using ____________.
c. solid angles a. Miller indices
d. inter facial angle b. Bragg’s indices
12. In which system, majority c. both a & b
of minerals crystallizes
d. none of the above
Solid State
16. Frenkel defects are not
Answers
found in alkali halides because
1 c 2 b 3 c
a. halide ions are large in size
4 a 5 c 6 D
b. alkali metal ions have small
size 7 a 8 b 9 b
10 b 11 a 12 d
c. alkali metal ion has large
size 13 d 14 b 15 a
16 c
d. none of the above.
Fill in the Blanks

1. The crystal lattice has an is based upon the ______ of
_____ arrangement. lines and their relative
________.
2. Bravais lattice consists of
____________ space lattices. 8. The equation useful in the
crystal structure is written as
3. A unit cell that contains lattice
________.
points only at the corners is
known as _______________. 9. Defects in solid can be studied
using the technique called
4. The smallest portion of the
_____.
lattice is known as
______________. 10. The interplanar distance of ‘d’
of a cubic crystal of edge ‘a’ is
5. The axial relationship of a
related to the ‘Miller indices’
rhombohedral crystal system is of the plane h k l by the
given as ____________. equation _________.
6. The most common
11. NaCl crystal lattice belongs to
instrumentfor photographic
_____ cube.
recording of diffraction
patterns ________________. 12. A crystal system with axes a ‘“
b ‘“ c and angles á ‘“ ß ‘“ ã ‘“
7. The identification of a
90° corresponds to _____.
component of the sample from
its powder diffraction pattern

Chemistry - 1
13. The crystal planes are indicated 14. The h, k, l values of a plane
by h, k,l are the integer values whose intercepts on X, Y, Z
of the _____________ crystallographic axes are 2a,
2b, 2c ______.
Fill in the Blanks
1 2 3 4
three primitive unit
14 unit cell
dimensional cell
5 6 7 8
Debye – scherrer position,
a = b= c λ=2d sin? θ
powder camera intensity
9 10 11 12
x-ray a
d hkl  face centred triclinic
diffraction ( h2  k 2  l 2 )
13 14
reciprocals of
111
the intercepts
INTERACTIVE LINKS
1) Watch this video https://www.youtube.com/watch?v =ohtrnIODkAMto

learn about crystallization in a practical manner.
2) Watch this video to learn about crystal lattice and unit cell https:/
/www.youtube.com/watch?v=VPCDSmoomGK
3) Read this article ‘Crystallography: Atomic secrets’ (https://

www.nature.com/articles/505602a ) to know about interesting
topicsof crystallography.
4) Read this article ‘Miller Index’ (https://www.sciencedirect.com/

topics/ engineering/miller-index ) to get more familiar with Miller
indices.
5) Read this article ‘a new crystallography is born’ (https://

www.nature.com/articles/milecrystal04 ) to get more familiar with
Bragg’s law.

Solid State
What Is the difference between glass and crystal?

Although some people may use these words interchangeably, they
are not the same. In fact, both things are somehow opposite by
definition. A crystal is a solid substance that presents a highly ordered
arrangement of its microscopic components. On the other hand glass
is an amorphous non-crystalline solid, which are usually produced
by rapid cooling of melted amorphous materials, such as silica (SiO2).
What is Special About Vanadium Oxide?

Vanadium oxide is a weird material which is a conductor of electricity
but it is not a heat conductor. This was something completely
unprecedented in the world of physics until it was discovered.
What is structural difference between Daimond and Graphite?

Chemistry - 1

Chapter - 1


       


 


        
      

     
      







  

       
UNIT - 4
Chapter - 1
Gaseous State
Learning outcomes
After studying this chapter, student shall be able to

 Understand the necessity of derivation of van der Waals equation
for real gases.
 Understand the isotherms of CO2 continuity of state and critical
phenomenon.
 Understand the relationship between Van der Waals constants and
critical constants.
 Know about Joule – Thomson effect and its importance in liquefaction
of gases.
Introduction
Matter exists in three different physical states, solid, liquid and
gaseous forms. The differences between these three states of matter are
due to the difference in their intermolecular distance and inter molecular
forces. In addition to these, temperature and pressure are also play an
important role in deciding the state of matter. A gas can also flow in all
directions but differs from solids and liquids due to lack of any surface.
The properties of solids and liquids differ largely from substance to
substance which should be studied separately. Where as a gaseous state
is simplest state to understand the behaviour of the molecules of a
substance.
An understanding of gaseous behavior is a fundamental part of
physical chemistry. Further, many industrially important elements and
compounds are gases under the usage condition. Gases can undergo
expansion or compression. Both the pressure and temperature influence
the volume of a gas. The inter molecular distances in gases are very high.

Chemistry - 1

1
V (or ) PV  cons tan t
P
  P1    V1  

V2P2

P1V 1  P 2 V 2




V T P, n 
V
T

V1 V2
T1

T2





V  n P, T 
n 
 



Gaseous State
The influence of gravitational forces on the velocities of gas molecules is
least.
Gas laws
(a) Boyle’s law
It states that, at constant temperature, the volume of a given
mass of a gas is inversely proportional to its pressure. Thus, if V is the
volume of the gas at pressure P, then
1
V (or ) PV = constant (T, n are constants)
P
If V1 is the volume of the gas at pressure P1 and V2 is the volume
at pressure P2 then
P1V1 = P2V2
(b) Charles’ law

It states that at constant pressure, the volume of a given mass of
a gas is directly proportional to the absolute temperature of the gas.
Mathematically,
V
= constant, (P, n are constants)
T
V1 V2
or 
T1 T2
where V1 is the volume of the gas at the temperature T1 and V2 is the
volume at temperature T2.
(c) Avogadro’s law

It states that, equal volumes of all gases at the same temperature
and pressure contain equal number of molecules or moles.
Mathematically,
V  n ( P, T are constant)
where, n = the number of moles of gas present in the system.

Chemistry - 1
       

      
 
 



(Compressibility Factor)

       
Z

   
      


( PV ) observed ( PV ) observed
Z  
( PV )ideal nRT
   Z      
Z
                       
 
Z

 
Gaseous State
Ideal gas and non-ideal gas
(a) Ideal gas
A gas which obeys the three gas laws under all conditions of
temperatures and pressures is known as an ideal gas or a perfect gas. It
is observed that there is no gas which obeys the gas laws or the ideal gas
equation under all conditions of temperatures and pressures. However
gases obey these gas laws fairly well at low pressures and high tempera-
tures.
(b) Non-ideal gas or real gas
A non-ideal gas or real gas is the one which obeys the gas laws
only under low pressures and high temperatures. All gases are non-ideal
gases or real gases only. They show deviations from ideal behaviour
when the pressures are too high and temperatures are too low.
Compressibility factor (Z)

The compressibility factor is also called compression factor. This
factor describes the deviation of a real gas from the ideal behaviour. It is
denoted by ‘Z’. It is defined as the ratio of molar volume of a gas to the
molar volume of an ideal gas at the same temperature and pressure. It is
a useful thermodynamic property for modifying the ideal gas law to
account for the real gas behaviour. It is mathematically represented as
( PV )observed ( PV )observed
Z= 
( PV )ideal nRT
For an ideal gas, Z = 1 and is independent of temperature and

pressure. The deviations from ideality may be shown by a plot of the
compressibility factor Z against pressure, P as shown in figure 4.1.1.
The deviations of a real gas from ideal behaviour may change the value
of Z may be greater or lesser than 1. When these deviations become
large, then the gas is said to be a real or non-ideal gas. Thus, the
difference between unity and the value of the compressibility factor of a
gas is a measure of the degree of non-ideality of the gas.
Chemistry - 1
 

Z

Z
 

Z

Z
CO2
Z


PV - P
H2, He
PVCO,
CH4PV

       



         
1
    273     

Gaseous State
Variation of Compressibility Factor for Some gases
Figure 4.1.1: Variation of Compressibility Factor for Some gases

Deviations from Boyle’s Law (Effect of Pressure Variation on
Deviations)
From the figure 4.1.2, we can observe that at constant
temperature PV vs P curve for a real gas is not a straight line parallel to
Pressure axis. In the curves for H2, He as the pressure increases the
value of PV also increases. For the gases like CO and CH4 the PV
value decreases with increase in pressure and reaches to a minimum
value and then increases with pressure. Thus, real gases do not follow
the ideal gas equation perfectly under all conditions of pressure.
Figure 4.1.2: Plot of PV vs P for real gas and ideal gas

Chemistry - 1
1
   273      




      

a 

b 

       
        

   

a 

b 
 


   


Gaseous State
Deviation from Charles’ Law (Effect of Temperature on Devia-
tions)
According to Charles’ law, the coefficient of expansion of vol-
ume of every gas should be same i.e., 1/273 of its volume at at all
pressures. However, in practice this is found to be so only at low
pressures and considerable deviation sets in with the increase in
pressure.
Deviation of real gas from ideal behaviour

Real gases show deviations from ideal behaviour only under the
conditions of high pressures and low temperatures. These deviations are
due to two faulty assumptions that are made in the kinetic molecular
theory of gases. They are
(i) The volume occupied by the gas molecules is highly negligible as

compared to the total volume of the gas
(ii) The forces of attraction or repulsion among the gas molecules are
negligible.
The above two assumptions are true only if the pressure is low or
the temperature is high so that the distance between the molecules is
sufficiently large. However, if the pressure is high or the temperature is
low, the gas molecules come closer together. Under these conditions:
a. The forces of attraction or repulsion between the molecules are to

be considered.
b. The volume of the gas is so small that the volume occupied by the
gas molecules cannot be neglected.
4.1.1. van der Waals equation of state

van der Waals equation is particularly used to understand the
behaviour of real gases. This gives a simple physical picture for the dif-
ference between a real gas and an ideal gas.

Chemistry - 1


V
 
       
 (4V)b
b

V - b
V(V - b)


 A


B

        
  
       

 P + p
p



Gaseous State
van der Waals obtained the equation for real gases by applying
the corrections for volume and pressure as follows.
(a) Correction for the volume
Suppose v is the actual volume occupied by one mole of the gas
molecules. Since the gas molecules are in motion, it has been found that
the effective volume occupied by the gas molecules is four times the
actual volume (4v). Let it be represented by b. The volume b is called
co-volume or excluded volume. Thus, the free space available for the
movement of gas molecules is (V-b). Hence in the ideal gas equation V
should be replaced by (V-b).
(b) Correction for the force of attraction- pressure correction

A gas molecule present in the interior of the gas, say molecule A
in figure. 4.1.3 is attracted equally by all other gas molecules
surrounding it. Hence the net force of attraction exerted on such a
molecule by the other molecules is zero. However, for a molecule lying
near the wall of the container, say molecule B in figure 4.1.3, the
molecules lying inside the bulk of the gas exert some net inward pull.
Molecule A Molecule B
Figure 4.1.3: Location of molecules A and B

Chemistry - 1

d      
2
p  d

1
d 
V
V
1 a
p  (or) p 
V 2 V 2
‘a’
 
a
 P  V 2
     

PV = RT

 a 
 P  2  (V  b )  RT
 V 
‘a’, ‘b’

       

  ‘a’   
‘b’‘n’
n
 P 
V
nb
n

Gaseous State
Thus, the effect of such
inward pull is ‘dragging
back’ of the molecule.
Consequently the pressure
with which the gas molecule
strikes the wall of the vessel
is less than the pressure that
would have been exerted if
there were no such inward Johannes Diderikvan der
pull. Waals
(1837 – 1923)
Thus, the ideal pressure would be greater than the observed
pressure by a factor ‘p’.
Corrected pressure = P + p
Where, p is the correction factor due to the inward pull.
This inward pull on the gas molecules present near the wall
depends upon:
(i) Number of molecules surrounding the molecule,
(ii) Total number of molecules.
Each of these factors in turn depends upon the density (d) of the
gas.
Hence correction factor, p  d2
But for a given mass of the gas
1
d (where V is the volume of the gas)
V
1 a
p 2
(or ) p  2
V V
Where a is a constant and it depends on the nature of the gas.
a
Thus, corrected pressure = P +
V2
Substituting the corrected volume and corrected pressure in the
ideal gas equation PV = RT for one mole of the gas, the equation is
modified to

Chemistry - 1
 an 2 
 P   (V  nb )  nRT
 V 2 

‘a’ ‘b’ P, V

an 2
p 2
V
2
p x V 2 Pr essure x Volume
 a 
n2 Moles2

‘a’atm L2 mol-2 

‘b’V = nb
 b = v/n = L mol-1

 N2, O2, H2, He
SO2, NH3, H2S, CO2‘a’
      
    ‘a’  

 ‘a’
                

 b       
     ‘b’   

Gaseous State
 a 
 P  2  (V  b)  RT
 V 
This equation is known as van der Waals equation. The con-
stants a and b are called van der Waals constants. The values of a and b
depend upon the nature of the gas and are independent of the tempera-
ture and pressure.
van der Waals constant ‘a’ represents the magnitude of inter-
molecular forces of attraction and the constant ‘b’ represents the effec-
tive size of the molecules.
n
For n moles of the gas, p  and effective volume = n b
V
 van der Waals equation for n moles of a gas is
 an 2 
 P  2  (V  nb)  nRT
 V 
Units of van der Waals constants

Units of a and b depend on the units of P and V
an2
We know that, p 
V2
p  V 2 Pr essure  (Volume) 2
a  
n2 ( Moles ) 2
When pressure is expressed in atmospheres and volume in litres,
the units of
a = atm L2 mol-2
Units of b : V = nb
V
b= = L mol-1
n
Significance of van der Waals Constants

(i). It is observed that the values of ‘a’ for the easily liquefiable gases,
such as SO2, NH3, H2S, CO2 are greater than those for the perma-
nent gases like N2, O2 H2 and He. Moreover, the value of ‘a’ in-

Chemistry - 1
          
 a, b





a, b 





      

      
    

0C  
    A  CO2  
     AB   
  B   
 BC    
     
 C
      
Gaseous State
creases with the ease of liquefaction of the gas. It is observed that a
gas which is more easily liquefiable has greater intermolecular forces
of attraction. Hence ‘a’ is a measure of the intermolecular forces of
attraction in a gas.
(ii). The ‘b’ is the effective volume of the gas molecules. The con-
stancy in the value of b for any gas over a wide range of tempera-
ture and pressure confirms that the gas molecules are incompress-
ible. The values of a and b for some gases are shown in table 4.1.1
Table 4. 1.1: Values of van der Waals Constants

Gas a (atm L 2 mol-2) b (L mol-1)
He 0.034 0.0237
H2 0.245 0.0266
O2 1.360 0.0318
N2 1.390 0.0391
CH4 2.250 0.0428
CO2 3.592 0.0428
NH 3 4.170 0.0371
Cl2 6.493 0.0562
SO 2 6.710 0.0564
Limitations of van der Waals equation

Although van der Waals equation is much more accurate than
the ideal gas equation, appreciable deviations have been observed at
too low temperatures or too high pressures. This is due to the fact that
the values of ‘a’ and ‘b’ do not remain constant over the entire ranges of
temperature and pressure and hence the van der Waals equation is also
valid over the specific ranges of temperature and pressure.
Problem 1 :
One mole of carbon dioxide was found to occupy 1.32 litres at
48°C and 1.32 atmosphere. The van der Waals constant ‘a’ and ‘b’ are
3.59 and 4.27 × 10–2 respectively. Calculate the pressure of this gas.
Solution :

Chemistry - 1
CD
ABCO2
BC      
CDCO2
0C  EFGH   0C  
   

0C
  0C    
0C

0CCO2(TC)
0CCO2
atmCO2(PC)
       

  (parabola)   

(Continuity of States)
  



 

      
Gaseous State
 a 
 P  2  (V  b)  RT
 V 
a RT
P  2

v V b
RT a 0.082  321 3.59
P  2   18.5 atm
V b V (1.32  0.0427) (1.32)2
Problem 2 :
A vessel of 50 litre capacity contains 10 moles of steam under
5 atmospheres of pressure. Calculate the temperature of the steam.
(For water a = 5.46 atm (lit/mole)2, b = 0.031 lit/mol)
Sol: For ‘n’ moles, the van der Waals equation is

 n2a 
 P  2  (V  nb)  nRT
 V 
 n 2 a   V  nb 
T   P  2 
 V   nR 
P = 5 atm, n = 10 moles, V = 10 litres,
a = 5.46 atm. lit2.mol-2, b = 0.03 lit/mole
 102  5.46   50  10  0.031 
T  5 
 502   10  0.08  = 311.9K
4.1.2. Andrews Isotherms of Carbon Dioxide

Thomas Andrews was the first to study the effect of pressure on
the volume of carbon dioxide at different temperatures. The curves
representing the variations of volume and pressure at constant
temperature are called isotherms (Greek, iso = equal; thermos = warm)

Chemistry - 1


        








(Continuity of state)
CO2 
 0C  ‘a’    

 bab
CO2
CO2  bc
‘c’CO2abc


 


 

Gaseous State
Andrews measured the volume of carbon
dioxide at different pressures, at constant
temperature of carbon dioxide. The plot of
P vs V at constant T is called an isotherm.
A number of such isotherms were
obtained at different temperatures as
shown in Figure 4.1.4. Thomas Andrews
Figure 4.1.4: Experimental Isotherms of CO2
At the temperature of 13.1oC at low pressure, carbon dioxide

exists as a gas as shown at the point A. As the pressure is increased, the
volume of the gas decreases along the curve AB. At the point B, the
liquefaction of the gas starts. Hence the volume decreases rapidly along
BC because the liquid has much less volume than the gas. At the point
C, the liquefaction is complete. Now the increase of pressure has very
little effect upon the volume because liquids are hardly compressible.
Hence a steep curve CD is obtained. Thus, along the portion AB, car-
bon dioxide exists only as gas. Along the portion BC, the liquid and the
vapour are in equilibrium with each other. Along CD, carbon dioxide
exists only as liquid.
The isotherm EFGH at 21.5°C is similar to that at 13.1°C ex-
cept that the horizontal portion over which the liquefaction occurs is

Chemistry - 1


        

(Critical Temperature)
   

               
P - V


P
- V 
0C

   
0C       
0C
C O2
(Critical Temperature)

                  (Characteristic Property)   
     
    

0CP - V
Gaseous State
shorter. In fact, as the temperature is raised this portion becomes smaller
and smaller and finally at 31.1°C, it is reduced only to a point. In the
isotherms above, 31.1°C the horizontal portion completely disappears.
This shows that above 31.1°C the liquefaction of the gas does not take
place at all, however high the applied pressure may be. Thus 31.1°C is
the critical temperature of carbon dioxide. The pressure required to liq-
uefy the CO2 gas at 31.1°C is found to be 72.9 atmospheres. This is
called critical pressure of CO2. It has been found that in case of all other
gases similar isotherms are obtained. However, lengths of the horizontal
portions and the peak of the dotted parabola are different depending
upon the nature of the gas.
4.1.3 Continuity of State

Intermixing of gaseous state into the liquid state and vice versa
is known as ‘Continuity of State’.
If the ends of the horizontal portions of the different isotherms
are joined together a parabolic curve (shown by dotted lines in Figure
4.1.4) is obtained. The peak of this parabola represents the critical point.
Within the parabola the liquid and the vapour exist together in equilib-
rium. Outside the parabola, the substance exists only as a gaseous under
the conditions represented on the right side and only as liquid under the
conditions represented on the left side. A careful reveal that below the
critical temperature it is possible to change a substance from gaseous
state to liquid state without having both the phases present together at
any stage. This behaviour is explained as follows.
Suppose the substance under consideration is CO2 as shown in
Figure 4.1.4, is referred once again. At 13.10C, if pressure and volume
correspond to the point ‘a’, the substance is gaseous. Keeping the vol-
ume constant, if the gaseous CO2 is heated till it has pressure corre-
sponding to that point ‘b’, the path ‘ab’ is followed. By keeping the
pressure constant, if the gas CO2 is cooled the volume decreases along
the path ‘bc’. Thus, at point‘c’, CO2 will exist as liquid. Hence, now
here along the path ‘abc’, there has been more than one phase exists.
This is expressed by saying that the change of state from gaseous to

Chemistry - 1
(Critical Isotherm)C(Criti-
cal Point)                   
     (Critical
Pressure)
(Criti-
cal Volume)
 



a ab
PV  bP    RT  0................4.1.1
V V2
v2P

3  RT  2  a   ab 
V  b 

v   V     0................4.1.2
P  P P

a,b
 V 
 (real values) 
(imaginary) 

V = Vc
 V - Vc = 0  ( V - Vc )3 = 0

Gaseous State
liquid state is continuous. Thus it is referred to as the continuity of
state.
4.1.4 Critical Phenomena

The term critical phenomenon refers to the peculiar behaviour
of a substance when it is at or near the point of a continuous phase
transition (critical point). A continuous phase transition, in turn, may be
defined as a point at which a substance changes from one state to
another without any discontinuity or jump in its density.
According to the kinetic theory of gases, the kinetic energy of
the molecules is directly proportional to the absolute temperature. As
the temperature decreases, the kinetic energy of the molecules decreases
and the molecules become closer to each other. At a particular
temperature the motion of the molecules becomes negligible and the gas
becomes liquid.
Constants like critical temperature, critical pressure and critical
volume of gas determine the condition and formula of liquefaction of real
and ideal gases.
The P – V curves presented in Figure 4.1.5 indicate that at a
particular or specific temperature the horizontal line depicting the gas –
liquid equilibrium is reduced to a point. Further, above this temperature
the P – V curve resembled the ideal gas isotherm. These facts suggest
that at this specific temperature or above this temperature, a gas cannot
be converted into liquid whatever high pressure is applied on the gas.
This temperature is called critical temperature (Tc) and the temperature
above which the gas cannot be converted into liquid even by application
of high pressure. This is explained earlier as critical temperature (Tc) and
is a characteristic property of a gas. So, if a gas is to be converted into
liquid, the gas must be cooled to below this temperature Tc and then only
high pressure is to be applied.
The minimum pressure required to convert gas into liquid at this
critical temperature is called critical pressure (Pc). Similarly, the volume
occupied by 1 mole of gas at critical temperature (Tc) and critical pres-
sure (Pc) is called critical volume (Vc). Therefore, every gas will have Tc,

Chemistry - 1
V 3
 3V c .V 2
 3V c2 .V  V c3  0 
T = Tc, P = Pc

3  RT  2 a  ab 
V   b  c V   V     0................4.1.4
 Pc  P  Pc 
 V

RT c
3V c  b 
Pc

2 a
3V c 
Pc

3 ab
Vc 
Pc


Vc
 b (or) Vc = 3b 
3

ab a
27b3  (or) Pc  
Pc 27b2
VcPc

RT c ( 27 b 2 )
9b  b 
a
RT c ( 27 b 2 )
(or) 8b 
a
8a
Tc  
27 Rb
Gaseous State
Pc and Vc. The volume occupied by 1 mole of gas or 1 mole of liquid at
Tc are therefore equal. Since, density is inversely proportional to volume
at Tc, the densities (d) of gas and liquid are also equal. Because of this it
is not possible to distinguish gas from liquid at Tc. Critical constants of
some gases are shown in figure 4.1.2.
Table Pc of gasesVc
Gas 4.1.2: Critical
Tc K Constants
(atm) (ml)
He 5.2 2.26 60.63
H2 33.2 12.8 64.51
N2 126.0 33.5 90.03
CO 134.4 34.6 90.03
Ar 150.7 48.2 78.43
O2 154.3 49.7 74.42
CH4 190.2 45.6 98.76
CO2 304.3 72.9 95.65
N2O 309.6 71.9 96.91
HCl 324.5 81.6 89.9
H2S 373.5 89.0 126.86
NH3 405.5 111.5 72.03
Cl2 417.1 76.1 123.9
SO2 430.3 77.6 124.75
Problem 3
The van der Waals constants for carbon dioxide are given
a = 3.61 atm litre2/mole2 and b = 4.27 × 10–2 litre/mole. Calculate the
critical constant VC, TC and PC of the gas.
Sol:
VC = 3b = 3 × 4.27 × 10–2 = 12.81 × 10–2 lit/mole
a 3.61
PC   = 73.33 atms
27b 2
27  0.0821  4.27  10 2
8a 8  3.61
TC   = 305.1 K
27 Rb 27  0.0821  4.27  10 2
Chemistry - 1



 
(Law of Corresponding States)
a, b
       
                        
   a, b  

     
   

P   Pc ;  V   V c and T   T c
  (PR)
(VR)(TR) 

P V T
  ;   ,  
Pc V c Tc

 a 
P   V  b  RT
 V 2 
 a2 
  Pc    V c  b   R  T c
 Vc 
We know that

Gaseous State
Problem 4
The van der Waals constants for 1 g molecule of oxygen are a
= 3.609 × 106 mL2 atm mole–2 and b = 42.75 mL mol–1. Calculate
the values of the three critical constants (R = 0.0821 litres K–1 mol–1).
Sol:
We know that, VC = 3b
 VC = 3 × 42.75 = 128.25 mL
a
Again PC 
27b 2
3.609  10 6
 PC  = 73.2 atm
27  (42.75) 2
8a
Also TC 
27 Rb
Here, R = 0.0821 L atm K–1 mol–1
= 0.082 × 1000 mL atm K–1 mol–1
Substituting the values of a, b and R, we get
8  3.609 106
TC  = 304.7 K
27  0.08211000  42.75
= 304.7 – 273 = 31.7 °C
Problem 5
Critical temperature and critical pressure of a gas are 304 K
and 73 atmospheres respectively. Calculate the value of a and b, the
two van der Waals constants.
Solution:
8a a
We know that, TC  , PC 
27 Rb 27b 2
TC 8a 27b 2 8b
  
PC 27 Rb a R
Given, TC = 304 K
PC = 73 atm
R = 0.082 L atm K–1mol–1

Chemistry - 1
a 8a
V c  3 b , Pc  2
, Tc 
27 b 27 Rb
Vc , Pc , Tc
 a a  8 Ra
  2
 2 2   . 3 b  b  
 27 b  9b  27 Rb
a  3  a
   2   . 3 b  b   8 .
27 b 2    27 b
 3 
    3   1   8 
  2 
      
      (Pc)  
(Vc)  (Tc), a, b
   

      
  
 






   
    

Gaseous State
Substituting the values of Tc, Pc and R in the above equation
we get
304 8b

73 0.082
304 0.082
b   = 0.4269 Lmol–1
73 8
Substituting the values of b, R and TC in equation,
8a
TC 
27 Rb
8 a
304 
27  0.082  0.4269
27  0.082  0.4269  304
a = 3.591 atm L2mol-2
8
4.1.5 Relationship between Critical Constants and van der Waals

constants
For one mole of a gas, the van der Waals equation is,
 a 
 P  2  (V  b)  RT
 V 
a ab
(or) PV  bp    RT  0 ———(4.1.1)
V V2
On multiplying both the sides of equation (4.1.1) by ‘V2’and
dividing by ‘P’ we get
 RT  2 a  ab 
V 3  b  V   V    = 0 ———(4.1.2)
 P   P  p
This is a third order cubic equation in terms of ‘V’ and it may
have three real roots or one real and two imaginary roots. In other words,
for any given value of ‘P’ and ‘T’ there will be three real or one real and
two imaginary values of ‘V’. However, at critical point the three roots
become identical and equal to the critical volume VC then V = VC
Hence, (V - VC) = 0 or (V - VC)3 = 0
Expanding the above equation, we have

Chemistry - 1
   



  

     


(H)
(P)

 dT 
  
 dP  H
   




      
(Ti)

2a
Ti 
Rb
Ti
a, b
Gaseous State
V 3  3VC .V 2  3VC2 .V  VC3 = 0 ———(4.1.3)
Under critical conditions T = TC, P = PC and substituting these
values in equation (4.1.2) we get
 RT  2  a   ab 
V 3  b  V   V    = 0 ———(4.1.4)
 PC   PC   PC 
On comparing and equating the coefficients of the equal powers
of V in equation (4.1.3) and (4.1.4), we get
RTC
3VC  b  ———(4.1.5)
PC
a
3VC2  ———(4.1.6)
PC
ab
VC3  ———(4.1.7)
PC
Dividing equation (4.1.7) by (4.1.6), we get
VC
 b or VC = 3b ———(4.1.8)
3
And on substituting the value of equation (4.1.8) in equation
(4.1.7), we get
ab a
27b3  or PC  ———(4.1.9)
PC 27b 2
And then finally insertion of these results for Vc and Pc in equa-
tion (4.1.5) we get
RTC (27b2 )
9b  b 
a
RTC (27b2 )
(or) 8b 
a
8a
TC  ———(4.1.10)
27 Rb

Chemistry - 1
  
   
       

C
C
C

          Linde          
               

 

     

 


Gaseous State
From the equations 4.1.8, 4.1.9 and 4.1.10 may be used to
calculate the critical constants of a particular substance from van der
Waals constants and vice versa.
4.1.6 Law of Corresponding States

In the van der Waals equation, the constants ‘a’ and ‘b’ cannot
be measured directly. Therefore, van der Waals equation is not
applicable to all gases. In order to make it applicable to all gases, these
constants must be removed.
If pressure, volume and temperature of a gas are expressed in
terms of critical pressure, critical volume and critical temperature
respectively then we can write,
P   PC ; V  VC and T   TC
Thus the quantities may be written as
P V T
 ;  ; 
PC VC TC
The quantities  ,  and  are known as reduced pressure
(PR), reduced volume (VR) and reduced temperature (TR) respectively.
Then we have
P   PC ; V  VC and T   .TC
Substituting these values in van der Waals equation,
 a 
 P  2  (V  b)  RT
 V 
 a 
2 
we get   PC   VC  b   R TC
  V  
 C 
a 8a
we know that VC  3b , PC  T 
2 and C Substitut-
27b 27 Rb
ing the VC, PC, TC values in the above equation we have
 a a  8 Ra
 2
 2 2  ( .3b  b) 
 27b  9b  27 Rb

Chemistry - 1
a  3 a
2 
  2  ( .3b  b)  8 .
27b    27b
 3 
   2  (3  1)  8
  
This equation is known as van der Waals reduced equation of
state as it involves the reduced pressure, reduced volume and reduced
temperature. Since this equation does not involve the constants a, b, PC,
VC and TC which are characteristic of a gas it is applicable to all liquids
and gases irrespective of their nature.
From the above equation it is clear that if two substances have
the same reduced temperature and pressure, they will have the same
reduced volume. This statement is called the law of corresponding states
or principle of corresponding states.
Importance of the Law of Corresponding States
While studying the relationship between physical properties and
chemical constitution of various liquids, their properties should be
studied at the same reduced temperature since pressure has practically
no effect on liquids. The boiling point of a liquid in absolute degrees is
about 2/3rd of its critical temperature TC. Therefore, we can say that the
various liquids at their boiling points are very nearly in corresponding
states. Hence various physical properties of liquids such as molecular
volume should be compared at their respective boiling points.
Problem 6 :
(1) Calculate the value of pressure for 1 mole of a gas at 313K
occupying 1.07 × 10–4m3 volume using the law of corresponding states.
105 m3
Given : TC  304K ,VC  9.75  ; PC = 73.97 bar
m
Solution:
P P
 
PC 73.97

Gaseous State
V 1.07 104 m3 / ml
  = 1.118
VC 9.57 105 m3 / ml
T 313
 
TC 304 = 1.03
Substituting these values in the law of corresponding states
 3 
   2  (3  1) = 8
  
8 3
  2
3  1 
P 8 1.03 3
  
73.94 (3 1.118  1) (1.118)2
P 8 1.03 3
  = 1.015
73.94 2.354 (1.118)2
4" P = 1.105 × 73.94 = 81.74 bar
4.1.7 Joule – Thomson effect

Joule and Thomson observed that when a gas under high
pressure is allowed to expand into a region of low pressure under
adiabatic conditions, the gas gets appreciably cooled. This phenomenon
is known as Joule – Thomson effect. The cooling in this effect is due to
the internal work done by the gas molecules in breaking the attractive
forces between molecules.
Joule – Thomson coefficient: It is the number of degrees of
temperature change produced by a drop of one atmospheric pressure
under the conditions of constant enthalpy.
 dT 
  H
 dP 
(a) The value of ì depends on the nature of the gas, temperature and
pressure of the gas before expansion.

Chemistry - 1
(b) For all real gases, it is equal zero at some point called the inversion
point. The effect is greater at lower temperature and takes place at
constant enthalpy.
4.1.8 Inversion Temperature (Ti)

According to Joule – Thomson effect, the gases become cooler
during the expansion process. This will happen only if they are below a
certain temperature called inversion temperature (Ti) and is represented
by the equation,
2a
Ti 
Rb
Where, Ti is known as the inversion temperature and is depen-
dent on the van der Waals constants ‘a’ and ‘b’ of the gas.
Most of the gases have positive Joule – Thomson coefficients
and hence they cool at room temperature.
Hydrogen and Helium when subjected to Joule – Thomson
effect at room temperature, they warm up instead of cooling on sudden
expansion. However, when hydrogen is first cooled to –80°C, it
behaves normally towards Joule – Thomson effect. Hence –80°C is the
inversion temperature of hydrogen. Helium has the inversion
temperature of –240°C.
Applications of Joule – Thomson Effect
 The cooling produced in the Joule-Thomson expansion has made it
a very valuable tool in refrigeration.
 The effect is applied in the Linde’s technique in the petrochemical
industry, where the cooling effect is used to liquefy gases.
 It is also used in many cryogenic applications, such as, for the
production of liquid nitrogen, oxygen and argon.
 This effect can also be used to helium which is used in air ships.
SUMMARY
The state of a gas is defined by a relationship between the four
independent variables pressure (P), volume (V), temperature (T) and
number of moles (n). The relationship between these parameters is gov-

Gaseous State
erned by different gas laws. Gases that obey the equation PV=nRT
under all conditions are called ideal gases. But in practice there is no
ideal gas. Gases tend to behave ideally at high temperatures and at low
pressures. For real gases, van der Waals modified the ideal gas equation
as
 a 
 P  2  (V  b)  RT
 V 
Critical temperature (Tc) of a gas is the temperature above which
it cannot be liquefied at any pressure. Critical pressure (Pc) of a gas is
the minimum pressure required to liquefy 1 mole of a gas at its critical
temperature. Critical volume (Vc) is the volume occupied by 1 mole of a
gas at its critical temperature and critical pressure. The critical constants
are related to Van der Waals constants as follows
a 8a
PC  T 
2 , C and VC  3b
27b 27 Rb
When a gas is made to expand adiabatically from a region of
high pressure into a region of low pressure, the temperature of the gas is
reduced rapidly and this is known as Joule-Thomson effect. This effect
is used in the liquefication of gases.
GLOSSARY
Continuity of The phenomenon of intermixing of
State: gaseous state into the liquid state and
vice versa.
Critical The isotherm passing through critical
Isotherm: point is called Critical Isotherm.
Critical Point: The point where there is no distinction
between the liquid and the vapour of a
gas.
Critical The pressure required to liquefy the gas
Pressure (PC): at the critical temperature (TC).
Critical The temperature above which, the gas
Temperature cannot be liquefied and how so ever
(TC): high the pressure may be.

Chemistry - 1
Critical Volume The volume occupied by 1 mole of the
(V C ): gas at its critical temperature and
critical pressure.
Isotherms: Pressure-volume curves at constant
temperature
1. The wrong assumption made in

the kinetic theory of gases is a.
a. Volume of gas molecules is b.
negligible. c. RT
b. Volume of gas molecules is
d.
half of the volume of gas
5. The temperature above which
(v).
a real gas cannot be liquefied is
c. Ther e are attractions
known as
between molecules of a
a. Critical temperature
gas.
b. Consolute temperature
d. Molecular attractions are
c. Boyle temperature
greater or lesser than
d. Inversion temperature
molecular repulsions.
6. The unit of van der Waals
2. The temperature below which
constant ‘a’ is
a gas is not liquefiable even
a. atm
with application of high
b. atm L2
pressure is called
c. atm L2 mol-1
a. Inversion temperature
d. atm L2 mol-2
b. Boyle temperature
7. In van der Waals equation of
c. Critical temperature
state of the gas law, the
d. Charles temperature
constant b is a measure of
3. The value of ‘b’ is terms of
a. intermolecular repulsions
critical volume is
b. intermolecular collisions
b. VC  2 c. volume occupied by the
a. VC  3
molecules
VC VC d. intermolecular attraction
c. d.
3 2 8. The units of ‘a’ is van der Waals
4. In van der Waals equation of equation are
state for real gases, the term a. atm lit2 mol–2
that accounts for the intermo- b. atm lit mol–1
lecular forces is c. atm lit mol–2
Gaseous State
d. atm–1 lit2 mol d. critical temperature
9. Which molecular property tends 15. The term ‘b’ in van der Waals
to produce large deviation from equation is related to
ideal gas behaviour? a. volume
a. small molecular weight b. pressure
b. weak inter – molecular at- c. temperature
traction d. none
c. high molecular speed 16. At high temperature and low
d. large molecular volume pressure, the van der Waals
10. The SI units of the van der equation is reduced to
Waals parameter ‘a’ are a. PV = RT
a. pa. m6 mol-2
b. n. m6. mol-2
b. P(V  b)  RT
c. pa. m-6. mol2
d. none  a 
c.  P   (V )  RT
11. The Joule Thomson coefficient  V2 
is zero at d. none
a. critical temperature 17. Which of the following equation
b. inversion temperature is known as the law of corre-
c. absolute temperature sponding states and hold for all
d. below gases?
12. The SI units of the van der
Waals b term are
8 3
a. m3/mole b. m2/mol a.   2
(3  1) 
c. m2.mol d. m3.mol
13. Intermolecular attraction and a
b. PC 
molecular size of a gas can be 27b 2
neglected at
a. high pressure and low tem-
RT a
perature c. P 
b. low pressure and high tem- (v  b) TV 2
perature
c. high pressure only  n2a 
d. at critical temperature d.  P    nRT
 V2 
14. The Joule – Thomson expan-
sion of an ideal gas is
a. an isothermal process
b. an isobaric process
c. an isoenthalpic process

Chemistry - 1
Fill in the Blanks
1. van der Waals constant ‘a’ is a 6. A gas at high pressures

correction term for _______ undergoes cooling on sudden
of the real gas. expansion into low pressure
2. van der Waals constant ‘b’ is region. The effect is known as
negligible in van der Waals _________________.
equation at ___________. 7. The term ‘b’ in van der Waals
3. Reduced equation of state of a equation is related to
gas makes use of _____ ________.
pressure terms in it. 8. In Joule–Thomson effect the
4. The value of TC in terms of van gas is heated up instead of
der Waals constants a, b is cooling in the case of ______
_______________ gas.
5. van der Waals equation of state 9. The temperature at which real
for ‘n’ moles of gas is gases obey the ideal gas laws
______________ . over a wide range of pressure
is called _______
ANSWERS
1 a 2 c 3 c 4 a 5 a 6 d
7 c 8 a 9 b 10 a 11 b 12 a
13 b 14 c 15 a 16 a 17 a
FILL IN THE BLANKS
P
1 pressure 2 Low 3
PC
 n2a 
 p  
8a  V2 
4 5 6 Joule–Thomson effect
27 Rb (V  nb)
= nRT
7 Volume 8 H2 9 Boyles temperature

Gaseous State
INTERACTIVE LINKS
1. Watch these videos by ‘Met Office – Learn about Weather’ to know

more about ‘Gas Laws’
a. https://bit.ly/gaslawspart1
b. https://bit.ly/gaslawspart2
2. Visit springer link’s article about ‘A new practical method to
evaluate the Joule – Thomson coefficient for natural gases’
https://bit.ly/joulethomsoneffect
Can we reach absolute zero temperature?
Absolute zero (0 K or –273.15 ºC) is a theoretical minimum, in

which atoms would stop moving, and cannot be achieved. However,
thanks to cryocooling refrigeration techniques, we can come close,
in the range of a billionth of 1 K. Surprisingly cold. But never absolute
zero. The idea of absolute zero was actually pioneered by Robert
Boyle himself.
Why does high air humidity make it feel hotter?

The natural mechanism of our body to cool itself down is sweating.
Evaporation of sweat from our skin takes up energy from our bodies,
cooling ourselves down. The more water there is already in the air
(higher humidity), the more difficult this evaporation process take
place. Therefore, higher concentration of water in air, makes us
feel hotter because we cannot cool down efficiently.

Chemistry - 1

Chapter - 2




 
      



     

     
      


 





 


UNIT - 4
Chapter - 2
Liquid State
Learning outcomes

 Understand basic concepts of liquids, structure of liquids,
intermolecular forces in liquids.
 Know the concept of liquid crystals and mesomorphic state.
 Understand classification of liquid crystals.
 Understand application of liquid crystals as LCD devices.
Introduction
Three different states of matter familiar to us are – solid, liquid
and gas. Liquids and gases flow while a solid under normal conditions
does not. A solid retains its shape while a fluid (a collective name for
gases and liquids) will take the shape of the container. Of the three states
of matter, the solid state exhibits a complete ordered arrangement of
atoms, ions and molecules. The gaseous state exhibits complete disor-
der. The liquids are in between the gases and solids.
The molecules in liquid state are relatively closer together. In the
total volume of the liquid, most of the part is occupied by its molecules.
So, only a small fraction of the total volume is available for their free
movement. Due to this, the liquid contains high density, incompressibility
than the gases.
We have learnt that, liquids can be obtained by cooling the gases
below their respective critical temperatures, followed by applying high
pressures. Effect of cooling is to decrease the thermal energies of mol-
ecules and the effect of pressure is to decrease the volume of the system

Chemistry - 1
      
   




 

 




a 
             
     


     

b 
 

      
                     
    

Liquid State
so as to allow the molecules to come closer, thereby increasing the force
of attraction amongst them. Alternatively, liquids can be obtained by
heating solids up to or beyond their melting points. Thus, we see the
properties of liquids lie in between those of solids and gases. For ex-
ample, liquids are less compressible than gases but a little more com-
pressible than solids. They are less dense than solids but denser than
gases. The two important properties of liquids are that they have fixed
volume but no definite shape. These properties are due to the following
two facts.
1. The energies binding the molecules are larger than their average ther-
mal energy.
2. Their binding energies are not strong enough to stop the motion of
the molecules altogether, as in the case of solids, with the result that
molecules can move from one place to another but cannot escape
from the liquid unless they are present at the surface.
Properties of liquids can be explained on the basis of their fol-
lowing characteristics:
(a) Appreciable forces of attraction exist between the molecules of a
liquid. These are about 106 times as strong as in gases. The forces
among the constituents of a liquid disallow them from separating
spontaneously from each other, but they are not strong enough to
hold the molecules in fixed positions. It is possible to explain sur-
face tension, viscosity, fairly high heat of vaporization and vapour
pressure of liquids in terms of these attractive forces.
(b) The molecules in a liquid are in a state of random motion although
the extent of randomness is appreciably much smaller in compari-
son to gases. The molecules are relatively close together. Most of
the space in the liquid gets occupied by its molecules and only a
small fraction of the space is available to them for their free move-
ment. This explains the higher density, incompressibility and slow
diffusion of liquids in comparison to gases.
(c) The average kinetic energy of the molecules in a liquid is propor-
tional to the absolute temperature. Increase in temperature would
increase the proportion of the energized molecules, lowers the at-

Chemistry - 1



 
 
C

    
X 
 
      

 
P
P

       

      

      


 
      

Liquid State
tractive forces between the molecules and consequently increases
the vapour pressure of the liquid.
Structure of Liquids
In a liquid, the molecules are not as rigidly fixed as in solid. They
have some freedom of motion which is much less than that in a gas.
Liquids resemble solids in being compact, incompressible and in having
a definite volume. These properties are indicative of a regular structure
in liquids similar to that in solids.
The difference between the structures of gases, liquids and sol-
ids can be best understood by comparing the densities of substances
that can exist in all three states. As shown in the table 4.2.1, the density
of a typical solid is about 20% larger than the corresponding liquid,
while the liquid is roughly 800 times as dense as the gas.
Solid (g/cm3) Liquid (g/cm3) Gas (g/cm3)
Ar 1.65 1.40 0.001784
N2 1.026 0.8081 0.001251
02 1.426 1.149 0.001429
The particles that form a liquid are relatively close together, but
not as close together as the particles in the corresponding solid. The
particles in a liquid have more kinetic energy than the particles in the
corresponding solid. As a result, the particles in a liquid move faster in
terms of vibration, rotation and translation. Because they are moving
faster, the particles in the liquid occupy more space and the liquid is less
dense than the corresponding solid. Differences in kinetic energy alone
cannot explain the relative densities of liquids and solids. This model
therefore assumes that there are small, particle-sized holes randomly
distributed through the liquid. Particles that are close to one of these
holes behave in much the same way as particles in a gas. While those
that are far away from a hole act more like the particles in a solid. The
structure of liquid is shown in figure 4.2.1.

Chemistry - 1

 






       


        

                
      
          
     




 
 
 

 
 
Liquid State
Figure 4.2.1: Structure of Liquid

Three factors determine whether a substance is a gas, a liquid or
a solid at room temperature and atmospheric pressure:
(a) The strength of the bonds between the particles that form the
substance
(b) The atomic or molecular weight of these particles
(c) The shape of these particles
When the forces of attraction between the particles are relatively
weak, the substance is likely to be a gas at room temperature. When the
forces of attraction are strong, it is more likely to be a solid. As might be
expected, a substance is a liquid at room temperature when the
intermolecular forces are neither too strong nor too weak.
4.2.1 Liquid Crystals - Mesomorphic State

There are certain solids which on heating undergo two sharp
phase changes one after the other. They first fuse sharply yielding turbid
liquids and again equally sharply at higher temperature yielding clear
liquids. These changes get reversed on cooling at the same temperature.
The turbid liquid show anisotropy i.e., they have different physical
properties from different directions. Anisotropy is particularly seen in
the optical behaviour of liquids. In an anisotropic substance, the physical
property is different in different direction. On the other hand, true liquids
are isotropic i.e., same physical properties in different directions. As
anisotropic properties are associated with crystalline state, the turbid
liquids are known as liquid crystals.

Chemistry - 1
 
 
 P
P       P    

       
    

LCD 
LCD 
     

 

 LCD  


 


Liquid State
When a solid melts, the vibrations of its constituent particles
acquire such magnitude that they lapse into translatory motions.
However, in some cases molecular or ionic clusters do not lose their
identity beyond the melting point of the solid. In such solids, the break-
down of cluster does not lose their identity beyond the melting point of
the solid. However, the breakdown of clusters in some directions is very
slow and they yield very viscous liquids at a more or less sharp
characteristic temperature, known as the transition point. If the
temperature is increased beyond the melting point of a solid, the
substance usually behaves as an ordinary liquid. Between the
temperatures, i.e., the transition point and melting point the cloudy liq-
uids show double refraction a behaviour usually exhibited by crystalline
solids. On this account the cloudy liquid state is sometimes called meso-
morphic state or regarded to be made up of liquid crystals.
4.2.2 Difference between liquid crystal and solid/liquid

Liquid crystals tend to occur in compounds where in the mol-
ecules are unsymmetrical in shape. In the crystalline state, long chain
molecules may be lined up as shown in figure. 4.2.2(a). On raising the
temperature, the kinetic energy may become sufficient to disrupt the
binding between the ends of the molecules.
Figure 4.2.2: Possible degrees of order in condensed states of long chain mol-
ecules: (a) crystalline – orientation and periodicity: (b) smectic – orientation and
arrangement in equispaced planes, but no periodicity with planes; (c) nematic –
orientation without periodicity; (d) isotropic fluid – neither orientation nor
periodicity.

Chemistry - 1
Further it is insufficient to overcome the strong lateral attractions
between the long chains. The two types of anisotropic melt thus
obtained are smectic, figure. 4.2.2(b) and nematic states figure. 4.2.2(c).
In the smectic state the molecules are orientated in well defined planes.
When a stress is applied, one plane glides over the other. In the nematic
state, (thread like), the planar structure is lost but the orientation is
preserved. On further heating an isotropic fluid is obtained, which has
neither orientation nor periodicity.
The differences between solid crystals, liquid crystals and iso-
tropic fluid are emphasized in table 4.2.3.
Table 4.2.2: Differences between Solid crystals, Liquid crystals

and Isotropic fluid
Liquid crystals
Solid crystals Isotropic fluid
Smectic Nematic
i Orientation i. Orientation i Orientation i. Orientation
ii Periodicity ii. Arrangement ii Absence of ii. No
of equispaced periodicity periodicity
planes but no
periodicity
with plane
4.2.4 Classification of Liquid Crystals into Smectic and Nematic

Based on the nature and structure of mesomorphic form the
liquid crystals can be classified into two types. (a) Smectic liquid
crystals (soap – like) and (b) Nematic liquid crystals (thread – like).
(a) Smectic liquid crystals
Smectic state is exhibited by common soap at high temperature
(  200C ) or in presence of water. The smectic liquid crystals do not
flow as normal liquids but they flow in layers. The X-ray studies have
suggested the existence of such parallel terrace-like planes in smectic
liquid crystals. These layers can slide over one another, because of the
weak forces existing between them. These crystals contain parallel planes,
but the spacing of the planes changes from that of the solid state.

Liquid State
This may be depicted in figure 4.2.3. Such smectic liquid transformation
has been observed in many cases such as ethyl–p–azoxy benzoate, ethyl–
p–azoxy cinnamate, ammonium oleate, etc.
Figure 4.2.3: Structure of Smectic liquid crystals
Properties
1. Smectic liquid crystals do not flow as normal liquids since they have
limited mobility.
2. In the case of different sheets gliding over one another, they flow in
layers. The distribution of velocity in different layers is different from
that found in true liquids.
3. The flow of these smectic crystals is non – Newtonian while the flow
in liquid is Newtonian.
4. The concept of viscosity does not apply to smectic liquid crystals.
5. These crystals produce X-ray diffraction patterns like solid crystals
but only in one direction. This appears in a fan-like structure in po-
larized light.
6. Smectic crystals are not affected by magnetic field because they are
uniaxial.
Table 4.2.4: Compounds yielding smectic type liquid crystals
Transition Melting
Compound
Point °C Point °C
Ethyl-p-azoxy
140 249
cinnamate
Ethyl-p-azoxy
114 121
benzoate
n-Octyl-p-azoxy
94 175
cinnamate

Chemistry - 1
(a) Nematic Liquid Crystals
Liquid crystals are anisotropic fluids, thermodynamically situ-
ated between normal isotropic liquid and three-dimensionally ordered
crystals. These are closer to true anisotropic liquids than are the smectic
phases.
Nematic liquid crystals possess properties similar to anisotropic
liquids. The properties are optical, diamagnetic, viscosity and elasticity.
Moreover, the molecules orient about a preferred axis. Thus, when these
crystals are viewed in the direction of a force of magnetic field, they
appear quite clear. But when the magnetic field is removed the liquid
crystals again reach into turbid state. When polarized light is passed
through these crystals, mobile thread-like structures are observed. The
molecules of liquid crystals are aggregated together into groups or swarms
with their axis parallel to each other. Each liquid crystal molecule can
rotate around its axis. The arrangement of molecules in the nematic type
of liquid crystals is given in the figure 4.2.4.
Figure 4.2.4: Nematic liquid crystals.
Properties
1. These liquid crystals flow quickly when compared to smectic liquid
crystals.
2. The flow of these crystals is Newtonian.
3. Nematic crystals possess low anisotropic properties when compared
to smectic crystals.
4. They exhibit normal flow behaviour of pure liquids.
Liquid State
5. The nematic state is less ordered than smectic state.
6. The viscosity of these crystals is less when compared to pure liq-
uids.
7. Nematic liquid crystals scatter the light and hence, they appear as
translucent.
8. In polarized light nematic crystals exhibit thread like structure.
9. The compounds that are having ability to form nematic liquid crys-
tals are p-azoxy phenetole, anisaldazie, p-Methoxy cinnamic acid,
p-Azoxyanisole, Dibenzal benzidine.
10. Pure nematic liquid crystals do not conduct electricity in pure state.
If they contain any ionic compounds as impurities, they conduct elec-
tricity.
Table 4.2.3: Compounds yielding nematic type liquid crystals
Transition Melting
Compounds
Point (°C) Point (°C)
p-azoxy phenetole 136.85 166.85
Anisaldazine 164.85 179.85
p-Methoxy cinnamic
169.85 185.85
acid
p-Azoxyanisole 115.85 134.85
Dibenzal benzidine 233.85 259.85
2.5 Application of liquid crystals as LCD Devices
1) They are used as displays in digital wrist watches, calculators, panel
meters and industrial products.
2) They can be used to record, store and display images which can be
projected onto a large screen.
3) Liquid-crystal displays (LCDs) are used as displays in several ar-
eas, such as office automation equipment, as laptop computers, in
television, teleconferencing systems, portable and high-definition
television (HDTV) and in video games.

Chemistry - 1
4) The LCD devices are used in electric bulbs, which consume less
electric power.
5) These are used as solvents in the determination of anisotropic solid
structure.
SUMMARY
At room temperature, substances occur in three physical states
namely solids, liquids and gases. Solids melt sharply at a temperature
(melting point) and give clear liquid (melt). Some of the solid substances
on heating at first, they produce a turbid liquid at a particular
temperature. On further heating they give a clear liquid known as liquid
crystal.
Liquid crystals are classified into two types namely (a) smectic
liquid crystals and (b) nematic liquid crystals. Nematic crystals possess
thread like structures where as smectic crystals have soap like structure.
The important properties of smectic crystal are (i) do not flow normally
(ii) the property of viscosity is not observed (iii) layers slide over one
another (iv) velocity of molecules of liquid is different in different layers.
The important properties of nematic liquid are (i) flows as normal liquids
(ii) appears as true liquids in magnetic field (iii) they flow with higher
speed compared to smectic liquids (iv) nematic liquids are anisotropic.
Liquid crystals are used as solvents in detecting anisotropic
arrangement, used in the construction of LCD displays and used as
displays in digital watches.
GLOSSARY
Crystal : Highly ordered microscopic structure,
forming a crystal lattice that extends
in all directions
Liquid: A substance that flows freely but is of
constant volume, having a consistency
like that of water or oil.
Liquid crystals : A state of matter which has properties
between those of conventional liquids
and solid crystals.
Liquid State
Liquid-crystal A flat-panel display or other
display (LCD) : electronically modulated optical
device
Mesomorphic A crystalline solid and an isotropic
state : liquid where the molecules are
separated in parallel layers of quasi
crystalline order.
Nematic phase : The simplest form of liquid crystal
and is the phase in which the crystal
molecules have no orderly position
and are free to move any way.
Newtonian fluid A fluid in which the viscous stresses
: arising from its flow, at every point
Non-Newtonian A Fluid that does not follow Newton's
fluid : law of viscosity,
Smectic phase : A slippery, thick residue found at the
bottom of soap dishes
1) Nematic is a type of liquid c) liquid

crystal which is based upon d) liquid crystal
a. ordering 3) Liquid crystal which flows like
b. molecules near normal flow behaviour of
c. surface area liquids
d. surface tension a) smectic liquid crystals
2) which type of molecules shows b) nematic liquid crystals
the molecular arrangement c) both a and b
shown in following figure d) none of the above
4) Mesomorphic state refers to
a. solid state
b. liquid state
c. liquid crystal state
d. gaseous state
5) Which of the following is not a
a) solid
property of liquid crystals?
b) gaseous
Chemistry - 1
a. long range order 9) Nematic phase posseses
b.flexible ends a. positional order
c. rigid centre region b. translational order
d.no functional groups c. orientational order
6) Liquid crystal state is also d. vibrational order
called 10) Layer structure is shown by
a. triple phase a) nematic
b. nematic phase b) smectic
c. mesomorphic state c) both a and b
d. all of the above d) none of the above
7) True liquid posseses 11) Which of the following is an
a. anisotropy example of liquid crystal?
b. orientational order a) sodium benzoate
c. isotropy b) silver oxide
d. positional order c) benzene
8) Flow of smectic liquid crystal d) potassium chloride
is
a. newtonanin
b. non – newtonain
c. far- newtonian
d. near – newtonian
Fill in the blanks
1. Smectic liquid is not affected 4. Smectic liquid crystal is also

by _______. known as _______ liquid
2. The temperature at which crystal.
turbid liquid changes to true 5. Liquid crystals posses the
liquid is called __________. properties of ____.
3. Anisotropic behaviour is 6. ________ liquid crystal which
shown by ______. shows.

Liquid State
KEY
1 a 2 d 3 b 4 c 5 d 6 C
7 c 8 b 9 c 10 b 11 a
FILL IN THE BLANKS

1. magnetic field
2. melting point
3. solid/liquid state
4. soap like
5. both solid and liquids
6. nematic/nematic liquid crystals
INTERACTIVE LINKS
1. Watch the preparing liquid crystals from ‘Scott Milam’

https://bit.ly/preparingliquidcrystal
2. Visit Clean Energy’s ‘Classification and Examples of Liquid

Crystals’ to know more about liquid crystal’s classification
https://bit.ly/classificationofliquids
3. Visit Springer Link’s article on ‘properties and applications of liquid

crystals’
https://bit.ly/applicationoflcs
4. Watch the building LCD display from ‘Applied Science’

https://bit.ly/buildinglcd

Chemistry - 1

Chapter - 1


   

      

 

 
       
     
   




    




 

UNIT - 5
Chapter - 1 Solutions
Learning outcomes

1. Understand the elementary concepts of different types of solutions.
2. Have idea about the methods of expressing the concentration of
solutions.
3. Distinguish the different types of liquid-liquid binary mixtures.
4. Understand the concept of vapour pressure and Raoult’s law
5. Know the application of Raoult’s law to ideal solutions and devia-
tions from Raoult’s law with respect to non-ideal solutions.
6. Understand the vapour pressure-composition (mole fraction) curves
for ideal and non-ideal solutions.
7. Understand the azeotropic mixtures and types.
8. Study the phenol–water system.
9. Understand the effect of impurity on CST.
10. Know the concept of steam distillation and its applications.
11. Understand the Nernst Distribution Law and applications.
Introduction
A solution is a homogeneous mixture of two or more compo-
nents whose composition may be varied within certain limits. In a solu-
tion the dissolved component, which is generally in smaller proportions
is called solute, the dissolving medium which is generally in larger pro-
portions is called solvent. Thus a solution is a binary mixture of a solute
in the solvent. For a given solution, the amount of solute dissolved in a
unit volume of solution is called concentration of solute. Solutions which
contain relatively low concentration of solute are called dilute solutions,
while those which contain relatively high concentration of solute are re-

Chemistry - 1
  
      


   
 (M) 

molL-1

n 
M  
VL 
 (N) 

      g.equi L-1

 e
N = 
 V L
 w
e = 
 E
 (m) 
Kg
 mol Kg-1 
 n
m = 
Kg W kg

Solutions
ferred to as concentrated solutions. A solution in which water is the sol-
vent is called aqueous solution and if alcohol is the solvent then it is
called alcoholic solution. If the solvent is other than water, then the solu-
tion is called non-aqueous solution. A solution whose concentration is
exactly known is called standard solution.
Based on the amount of solute present in a given volume of
solvent solutions are of three types. (i) A solution which dissolves some
more solute at a given temperature is called an unsaturated solution. (ii)
The solution which cannot dissolve any more solute at a given tempera-
ture is called a saturated solution and is the most stable solution. In this
solution an equilibrium exists between the dissolved solute and undis-
solved solute. (iii) A solution which has excess of solute than actually
required for its saturated solution is called super saturated solution and
is highly unstable solution.
Types of solutions
Depending on the physical state of the solute and the solvent,
we have nine types of solutions as shown in table 5.1.1.
Table 5.1.1: Types of solutions
Solute Solvent Example
Gas Gas Air
Gas Liquid Soda water (CO2 in water)(aerated
water)
Gas Solid H2 in Palladium metal
Liquid Gas Moisture in air
Liquid Liquid Ethyl alcohol in water
Liquid Solid Hg in gold, Jellies
Solid Gas Camphor in air
Solid Liquid Salt or sugar in water
Solid Solid Alloys like brass (Zinc in copper)
Among these solutions gas in liquid, liquid in liquid and solid in

liquid are much significant. In this chapter we shall discuss liquid in liquid
type of solutions only.

Chemistry - 1
  (X)
     



n
N
 n 
 X 1  
n  N 
 N 
 X 2  
n  N 
(Binary) X1  X 2  1 

 (S)
g 

(w)
S= x 100
(W)
 
Strength

 w/w% x 100


 w/v% x 100


Solutions
Methods of expressing the concentration of solutions
Molarity (M)
The number of moles of solute dissolved in a liter of solution at a
given temperature is called molarity (M). It is expressed in mol.L–1. It
decreases with increase in temperature. Mathematically,
n No. of moles of solute

Molarity, M = V  Volume of solution in litres
l
Weight of solute in grams (w)

n=
Gram Molecular Weight of solute (GMW )
W 1000
\M=
GMW

V
(where V is volume in mL)
Problem.1:
2.0 g of NaOH is present in 100 mL of solution. What is the
molarity of the solution?
Sol.: Weight of solute, w = 2.0 g
Volume of solution V = 100 mL

Gram molecular weight of NaOH = 40 g
 w  1000 2 1000
\ M=     = 0.5 M
 GMW  V 40 100
Normality: The number of gram equivalents of solute dissolved in a

liter of solution at a given temperature is called normality (N). It is ex-
pressed in g.equiv.L-1. It changes with temperature.
Mathematically,
No. of gm. equivalents of solute e
Normality, N = = Vl
Volume of solution in litre
Weight of solute(w) in grams w
e= 
Gram Equivalent Weight of solute E

Chemistry - 1
 





      
 
       
  



     
                             

 
 
 
     
       

eg. C2 H 5OH  H 2O

Solutions
Problem.2:
5.3 g of Na2CO3 is present in 100 ml of solution. Calculate the
Normality of the solution.
Sol.: weight of solute of Na2CO3, w = 5.3 g
Volume of solution in ml, V = 100 mL
106
Equivalent weight of Na2CO3 = = 53
2
 w   1000  5.3 1000
\ N =     =1N
 E   V  53 100
Molality (m): Molality is the number of moles of solute dissolved in a

kilogram (1000 g) of solvent. It is expressed in mol.kg–1
No. of moles of solute n
Molality (m) = Weight of solvent in ki log ram  W
kg
w
\ Molality (m) =  1000
GME  W (in grams )
Problem.3:
Find the molality of the solution when 3.65 g of HCl is dissolved
in 100 g of water.
Sol.: Weight of solute (w) = 3.65 g
Weight of solvent(W) = 100 g
GMW of HCl = 36.5g
w 3.65
Molality m =  1000 = × 1000 = 1 m
GME  W 36.5  100
Mole Fraction (X): The ratio of the number of moles of one compo-
nent of a solution to the total number of moles of all the components
present in the solution is called mole fraction of that component. Since it
is a ratio, it has no units. It is independent of temperature.
In a binary solution if ‘n’ moles of solute is dissolved in N moles
of solvent, then

Chemistry - 1
     


  

      





 

AB
A-A, B-BB-B
A,B 
      


    



Solutions
 n 
Mole fraction of solute, X1 =  
nN 
 N 
Similarly mole fraction of solvent, X2 =  
nN 
For a binary solution the sum of mole fractions of solute and
solvent is equal to one.
\ X1 + X2 = 1
Problem.4:
A gaseous mixture has 44 g of CO2 and 14 g of N2. Find the
mole fraction of CO2 in that mixture.
Sol.:
Weight of CO2 44
nCO2 =
Molecular Weight of CO2 44 = 1
=
Weight of N 2 14 1
n N2 = Molecular Weight of N  28  2
2
No. of moles of CO2

X CO2 = No. of moles of CO  No. of moles of N
2 2
1 1 2
 
= 1 1 3 3
2 2
Physical methods of expressing concentration
1. Solubility (S): The weight of solute in grams present in100 grams
of solvent in its saturated solution is called its solubility.
S= x 100
(where w = weight of solute, W = weight of solvent)

Chemistry - 1
T A B 

PB  X B .P 0 B 
PB  B 
P 0 B =B
X B = B 
 PA  X A .P0A 

 P  PA  PB 
 P  P0 A .X A  P 0 B .X B 

BXB
PB
 X B  P0 .........5.1.5
B

PA
XA  .........5.1.6
P0 A
A,B                  
PA  P0 A .X A , PB  P 0 B .X B    A,B
       


      

Solutions
2. Strength of solution (s): It is the amount of solute in grams
dissolved in one litre of the solution. If 4 g of NaOH is dissolved in
one litre solution then the strength of the solution is 4 gL-1.
Weight of solute
3. w/W % of solute: =  100
Weight of solution
Weight of solute in grams

4. w/V% of solute =  100
Weight of solution in mL
Vapour pressure of liquid

In a closed vessel the molecules steadily accumulate in the space
above the liquid. This process is called evaporation. As the number of
molecules increase, then the molecules show a tendency to return to the
liquid phase which is called condensation as shown in the fig. 5.1.1.
Figure 5.1.1: Vapour pressure

At each temperature a condition of equilibrium exists when the
number of molecules leaving the liquid to enter the space above is equal
to the number of molecules returning to the liquid has at a given time.
The space over the liquid is said to be saturated with the vapour of the
liquid. The pressure of the vapour developed is called the vapour

Chemistry - 1
 358 K
 323 K
 n-n-303 K
    
A, B 
      

 A-A, B-B, A-B 
       
A-B
A-A, B-B       
 
    
A, B      
A-BA-A, B-B 
A, B 

A, B 
       

PA  P 0 A .X A ; PB  P 0 B .X B
P  PA  PB ; P  P 0 A .X A  P 0 B .X B

Solutions
pressure of the liquid. Thus the vapour pressure of the liquid at a given
temperature is defined as the pressure exerted by the vapour on the
surface of the liquid, when the vapour and liquid are in the equilibrium
state. Vapour pressure is the characteristic property of a liquid. It in-
creases with increase in temperature.
Liquid-Liquid Binary Mixtures

Based on the miscibility of one liquid in other liquid, liquid-liquid
binary mixtures can be classified in to three types.
1. Completely miscible liquid-liquid binary mixtures
2. Partially miscible liquid-liquid binary mixtures and
3. Completely immiscible liquid-liquid binary mixtures.
1. Completely miscible liquid–liquid binary mixtures

The binary mixtures in which one liquid is completely miscible with the
other liquid in all proportions are called completely miscible liquid-liquid
binary mixtures.
eg: ethyl alcohol + water
2. Partially miscible liquid-liquid binary mixtures

The binary mixtures in which one liquid is partially miscible with
the other liquid are called partially miscible liquid-liquid binary mixtures.
eg: phenol + water; ether + water; aniline + water; carbon disulphide +
methanol
For example, at room temperature when some phenol is added
to water, phenol completely dissolves in water. If the addition of phenol
is continued in water, then a point is reached where no further phenol
dissolves in water. This results in the formation of two liquid layers. These
two layers correspond to a saturated solution of phenol in water and a
saturated solution of water in phenol respectively. These two layers will
be in equilibrium with each other and are called conjugate solutions.

Chemistry - 1


      



     
A, B      
A-BA-A, B-B
A, B
A, B 
 


PA  P 0 A .X A ; PB  P 0 B .X B
P  PA  PB ; P  P 0 A .X A  P 0 B .X B
    




  mix H  0  mixV  0
         H 2SO 4 ;            
Solutions
3. Completely immiscible liquid-liquid binary mixtures

The binary mixtures in which one liquid is completely immiscible
with the other liquid are called completely immiscible liquid-liquid binary
mixtures.
eg: carbon disulphide + water
The Ideal Solutions-Raoult’s law

A solution is said to be an ideal solution if the molecules in the
solution attract one another with equal force irrespective of their nature.
This means that if we have an ideal solution of B in A, then the forces
between A and A, B and B and A and B should be the same. Therefore,
in an ideal solution (i) the total volume of the solution = Volume of A +
Volume of B. (ii) No heat is evolved or absorbed on mixing the compo-
nents. For example if one litre of benzene and 1 litre of toluene are
mixed together at room temperature, the total volume of the resulting
solution is 2 litres because they form an ideal solution. Further, there is
no heat evolved or absorbed. On the other hand if 100 ml of sulphuric
acid is mixed with 100 ml of water in a beaker, a large amount of heat is
generated and an ordinary beaker breaks. The volume of the mixture
will be less and may be about 180 ml. This is because they form a non-
ideal solution. Ideal solutions obey Raoult’s law.
Raoult’s law applied to Ideal solutions

According to Raoult’s law, the partial pressure of any volatile
constituent of a solution at a given temperature is equal to the product of
the vapour pressure of the pure constituent and its mole fraction in the
solution. For example, in an ideal solution of B in A at room temperature T
PB = XB. ———(5.1.1)
where PB = Partial pressure of B in solution,
= Vapour pressure of pure B

Chemistry - 1
 
 HNO3  
    


Azeotropic
mixtures  


   


    
     
    

HCl - H2O
    °C  
% HCl
°CHCl
°C
(5.1.4) 

Solutions
and XB = Mole fraction of B.
Similarly PA = XA. ———(5.1.2)
Total pressure P of the vapour according to Dalton’s law of partial pres-
sures is
P = PA + P B ———(5.1.3)
i.e.; P = . XA + . XB ———(5.1.4)
From equation 5.1.1, we have,
Mole fraction of B,
Partial pressure of B(PB )

XB =
Vapour of pressure of pure B  PBO 
PB
i.e.; XB = PB0 ———(5.1.5)
Similarly from equation 5.1.2, we have

PA
XA = P 0 ———(5.1.6)
A
If a mixture of two liquids A and B behaves ideally, then accord-

ing to the equations PA = .XA and PB = .XB, the plot of the partial
pressures of each constituent A and B and the total pressure P against its
respective mole fractions in the liquid phase is a straight line as shown in
figure 5.1.2.

Chemistry - 1
M  M 
 M 
     

 A, B 

M, 100% A‘C’

A
      
M

   A

  D     
BM
     




C 
 
Solutions
Figure 5.1.2: Vapour pressure-Composition curves for Ideal solutions
But only a limited number of mixtures obey Raoult’s law over
the wide range of concentrations. Some examples of ideal solutions are:
1. Ethylene dibromide and propylene dibromide mixture at 358K.
2. Benzene and ethylene dichloride mixture at 323K.
3. n-hexane and n-heptane mixture at 303K.
Problem.5:
The vapour pressure of two pure liquids A and B are 110 and
220 mm Hg at 25°C. Calculate the mole fraction of A and B in the
vapour phase when an equimolar solution of the liquid is made.
Sol.: Given in the problem:

Vapour pressure of pure liquid A = = 110 mm Hg
Vapour pressure of pure liquid B = = 220 mm Hg
In equimolar solution, mole fraction of A and B are as follows:

1 1
XA=   0.5 ; XB = 1 – XA = 1 – 0.5 = 0.5
1  1 2
According to Raoult’s law of ideal solutions, we know that
0
P=P .X, we get the vapour pressure of the two components as:
PA= . XA = 110x0.5 = 55 mm Hg
PB= . XB = 220x0.5 = 110 mm Hg
Total pressure P of vapour according to Dalton’s law of partial

pressures
P = PA+ PB = 55+110 = 165 mm Hg

Thus in the vapour phase, mole fraction of A is
Partial pressure of A( PA ) 55
YA =  = 0.3333 or 33.33%
Total pressure (P ) 165
Similarly, the mole fraction of B is

Chemistry - 1

CC

(5.1.5)
M


M

      

A, M         
 A
B
D
      
B
A
    




Solutions
Partial pressure of B ( PB ) 110
YB=  = 0.6666 or 66.66%
Total pressure ( P ) 165
Or YB = 1- YA = 1-0.3333 = 0.6667 = 66.67%
Raoult’s law applied to Non-Ideal solutions

In an ideal solution formed between two components A and B,
the mixture remains unaffected by the pressure of each other and the
attractive forces between A-A, B-B and A-B are all the same. But such
ideal solutions are rare. On the other hand, when the attractions of A-B
between adjacent molecules of different types becomes greater than A-
A or B-B attraction then the solution becomes non-ideal. This effect
lowers the partial vapour pressure of A and B and the solution fails to
obey Raoult’s law.
Non-Ideal solution with Positive Deviation

Consider a solution formed by mixing the two liquids A and B. If
the interactions of A-B are weaker than those of A-A or B-B, then the
molecules A and B have more tendency to escape from the mixture. i.e.
solution than that of pure liquids. This results in the increase of total
vapour pressure of the solution than the corresponding vapour pressure
of the ideal mixture. Such solutions are non-ideal solutions with positive
deviation. For that solution we can write
PA> . XA and PB> . XB
and P> PA+ PB or P> . XA+ . XB
Ethyl alcohol and water, acetone and ethyl alcohol, acetone and
carbon disulphide, carbon tetrachloride and Toluene etc. are examples
of this type.
Hmix and Vmix are positive in these cases.

The figure for vapour pressure-mole fraction curve for non-ideal
solution with positive deviation is shown in figure 5.1.3, in which the
dotted lines indicate the ideal behavior. The practical curves obtained

Chemistry - 1


   
       
  




  

 
      
   





     
     

    
Solutions
for the non-ideal solution here are above the ideal values. So there is
positive deviation from ideal behavior.
Figure 5.1.3: Vapour pressure-composition curves for

non-ideal solutions with positive deviation
Non-Ideal Solution with Negative Deviation

If a mixture of two liquids A and B is considered in which A-B
interactions are stronger than those of A-A and B-B then the vaporiza-
tion of the molecules of A and B from the mixture or solution would be
less and so the total pressure of the mixture becomes lesser than the
corresponding vapour pressures for an ideal solution. As a result, it leads
to the formation of a non-ideal solution with negative deviation. For this
type of solutions we have
PA< PA0 . XA and PB < PB0 . XB
and P< PA+ PB or P< . XA+ . XB
The diagram normally obtained for such types of non-ideal so-

lutions with negative deviation is as shown in figure 5.1.4. The dotted
lines in the vapour pressure-mole fraction curves shown indicate the
ideal behavior. All the practical curves obtained are found to be below
the ideal curves. So there is negative deviation from ideal behavior or
Raoult’s law. Here Hmix , Vmix are negative. Examples of non-ideal solu-
tions with negative deviation are Water and sulphuric acid, acetone and

Chemistry - 1



 
 

 



        


    





  
       

    
Solutions
chloroform, ether and chloroform, benzene and chloroform, water and
nitric acid, water and perchloric acid etc.
Figure 5.1.4: Vapour pressure-composition curves for non-ideal solutions

with negative deviation
5.1.1 Azeotropic Mixtures or constant boiling mixtures

Azeotropic mixture is defined as a mixture of two or more liq-
uids of definite composition which boils at a constant temperature and
distills over completely at the same temperature without any change in
composition. Azeotropic mixture although boils at a constant tempera-
ture (at constant pressure), they are not regarded as compounds. It may
be noted that the boiling points as well as the composition of the
azeotropic mixture (azeotropes) change with pressure. Azeotropic mix-
tures are of two types namely:
(i) Maximum boiling point azeotropic mixtures and
(ii) Minimum boiling point azeotropic mixtures.
(i). Maximum boiling point azeotropic mixtures
Solutions of the type which distill unchanged at a constant tem-
perature and show a maximum boiling point are called maximum boiling
point azeotropic mixture. The best known example of this type is pre-
sented by hydrochloric acid and water which forms a constant boiling
mixture at 110 °C and containing 20.24% of the acid. The maximum

Chemistry - 1



0C 



C ST

     


   
  

                    




  


Solutions
boiling point of this mixture is higher than that of pure water (100 °C)
and hydrochloric acid (80 °C). If a mixture of any composition is dis-
tilled either hydrochloric acid or water will passover, the composition
will move to the point of minimum vapour pressure (Maximum boiling
point) when it distills without any change in composition as shown in
figure 5.1.5. The examples for maximum boiling point azeotropic mix-
tures are shown in table 5.1.2. along with constant boiling points and
composition of azetropes at 1 atm. Pressure.
Figure 5.1.5: Boiling point – composition diagram for maximum boiling point
azeotropic mixtures
For example if a mixture of composition C i.e., any point

between M and 100% A is distilled, the vapour will be containing more
of A than the original mixture and the residue is enriched in B. The boiling
point of the mixture rises. As the process is continued the residue will
approach the composition M. By taking the fractions from the mixture
and by a series of re-distillations we can eventually get a distillate of pure
A and a residue of azeotropic mixture M. Similarly we can separate a
mixture of composition D into a pure component B and the constant
boiling mixture M.

Chemistry - 1
       

 H2O

       

     




     

  
      


 CS2 -H2O; CCl4-H2O; H2O-Hg etc.
A, B
       PA, PB
P
nA, nB   V

Solutions
Thus, the fractional distillation of maximum boiling point mix-
tures give a distillate of azeotropic mixture, M and a residue of pure
component B.
Table 5.1.2: Examples of maximum boiling point azeotropic
mixtures at Pressure 1 atm
Component A Component B Constant
Composition
Boiling Boiling B.P of the
(Weight %
Name point Name Point mixture
of B)
(°C) (°C) (°C)
Water 100 HCl 80 110 20.24
Water 100 HNO3 86 120.5 68.0
Water 100 HCOOH 100.7 107.1 77.5
(ii). Minimum boiling point azeotropic mixtures

Solutions of this type, which distilled unchanged at constant tem-
perature and show a minimum boiling point are called minimum boiling
point azeotropic mixture. The best known example for this type is ethyl
alcohol and water, which forms a constant boiling mixture at 78.2°C and
containing 4.4% of water and 95.6% of ethyl alcohol. This temperature
is lower than that of water (100 °C) and ethyl alcohol (78.3 °C).
The boiling point composition diagram for this type azeotropic
mixture is shown in figure 5.1.6. The examples for minimum boiling
point azeotropic mixtures are shown in table 5.1.3. along with constant
boiling points and composition of azetropes at 1 atm. Pressure.
Figure 5.1.6: Boiling point-composition diagram

for minimum boiling point azeotropic mixture

Chemistry - 1

PAV = nA RT .................... 
PBV = nB RT .................... 
R =T


 
 

WA, WB, A, B



MA, MBA, B 


Solutions
Table 5.1.3: Examples of minimum boiling point azeotropes at
pressure 1 atm
Liquid A Liquid B
Minimum Composition
Boiling Boiling
B.P of the (Weight %
Name point Name Point
mixture(°C) of A)
(°C) (°C)
Water 100 Ethanol 78.3 78.2 4.4
n-
Water 100 97.2 87.7 28.3
propanol
Water 100 Pyridine 115.5 92.6 43.0
The upper curve represents the vapour curve and the lower curve
shows the liquid curve. The two curves meet at a point M which
represents the composition of the liquid mixture, with minimum boiling
point. The liquid and the vapour in equilibrium will have the same
composition at this temperature. The liquid represented by this point M
boils at constant temperature i.e.; distills over completely without change
in composition. Such system in which the composition of the distill is
unchanged is called azeotropic mixture.
5.1.2 Partially Miscible Liquid Mixtures

These are the binary liquid mixtures, in which two liquids are
partially miscible with each other. A large number of liquids are known
which dissolve in one another only to a limited extent such as ether and
water. Ether dissolves about 1.2% water and water dissolves about 6.5%
ether. Since their mutual solubilities are limited, they are only partially
miscible. When equal volumes of ether and water are shaken together,
two layers are formed namely (i) one larger is of the saturated solution of
ether in water and the (ii) other layer is of the saturated solution of water
in ether. These two solutions in equilibrium with each other are referred
to as conjugate solutions. Other examples include, phenol-water, aniline-
water etc. However, it is not necessary for one of the liquids to be water.
The examples for partially miscible systems with two organic liquids in-
clude aniline and hexane, carbon disulphide and methyl alcohol etc.
The effect of temperature on the mutual solubility of these
mixtures of conjugate solutions is of special interest. The two layers in a
Chemistry - 1
                       

   (Steam Distillation)
    






P1P2

 
P = P1 + P2
 P2= P -P1

        



0C
  
0C 
Solutions
partially miscible binary liquid mixture attain the same composition with
the raise in temperature. This means that the mutual solubility of the two
components increase with the increase in temperature. The two layers
become identical in composition and become completely miscible and
the two layers become one single layer only at a particular temperature
called the critical solution temperature (CST) or the consolute
temperature. Above this temperature the two partially miscible liquids
become miscible in all proportions and the composition outside this curve
will consist of one liquid layer only. Thus critical solution temperature is
defined as the temperature at which partially miscible liquids become
completely miscible in all proportions. The partially miscible systems on
the basis of their critical solution temperature can be classified into three
types:
(a) Systems with upper critical solution temperature.

Ex.: Phenol-Water system, aniline-water system, aniline-hexane
system, methanol-carbon disulphide system.
(b) Systems with lower critical solution temperature.
Ex.: Tri ethyl amine-water system.
(c) System with both upper and lower critical solution temperatures.
Ex.: Nicotine-water system.
5.1.3 Systems with Upper Critical Solution Temperature-

Phenol-Water system
Consider two liquids phenol and water. The two liquids are par-
tially miscible in each another. When a little phenol is added to water at
room temperature, it will dissolve completely. This means that phenol
and water form a miscible system when phenol is present in low per-
centage. But if addition of phenol is continued, then it is observed that
dissolution of phenol in water stops beyond a particular point by the
formation of two visible liquid layers. One of these layers is a saturated
solution of phenol in water and the other one is the saturated solution of
water in phenol. These two liquid systems are in equilibrium with each
other and are called conjugate solutions.

Chemistry - 1
     0C 
0C
0C 
mmmm
mm.
 
 



WA = 
WB = 
PA = 
PB = 
MA = 
MB = 
  (Nernst Distribution Law):

      

      
Solutions
The effect of temperature on the mutual solubility of these type
mixtures of conjugate solutions is of special interest. The effect of tem-
peratures on the mutual solubility of phenol-water system can be easily
understood from the graph shown in figure.5.1.7.
Figure 5.1.7: Phenol-water system

The curve shown in the figure represents the miscibility of phe-
nol and water with temperature. The left hand side of the parabolic curve
represents one of the conjugate solutions which indicate the percentage
of phenol dissolved in water at various temperatures. The solubility of
phenol increases with temperature. The right hand side of the curve shows
the other conjugate solution layer that gives the percentage of water in
phenol. The solubility of water in phenol also increases with increase of
temperature. The two solution curves meet at the maximum on the tem-
perature-composition curve of the system. This point here corresponds
to temperature 66 °C and composition of phenol as 33%. Thus at a
certain maximum temperature, the two conjugate solutions merge and
become identical and only one layer results. The temperature at which
the two conjugate solutions or layers merge into one another to form
one layer is called the critical solution temperature (CST) or Upper Critical
Solution Temperature (UCST). This is charateristic of a particular sys-
tem and is influenced very much by the presence of impurities.
The determination of critical solution temperature is therefore
used for testing the purity of phenol and other substances. At any tem-
perature above the critical solution temperature, phenol and water are
Chemistry - 1
       

     

 
   

 
 
      
C1, C2      


K      



CS2
    CS2 
  
CS2


Solutions
miscible in all proportions. Outside the curve there is complete homoge-
neity of the sytem i.e., one layer only. Some other examples of this type
along with their CST values and the percentage of first component are
shown in table 5.1.4
Table 5.1.4: Partially miscible liquid pairs with UCST values
CST % of component
Component A Component B
(°C) A
Methanol Cyclohexane 49 29
Hexane Aniline 59.6 52
Aniline Water 168 40
Carbon di
Methanol 49 80
sulphide
5.1.4 Effect of impurity on Consolute Azeotropic

If an impurity is added to the partially miscible liquid mixture,
then the mutual solubilities of the component liquids in the mixture are
affected. The mutual solubilities of the liquids also depend on the nature
and quantity of the added impurity. If the added impurity is soluble in
only one of the two liquids, then mutual solubilities of the two liquids
decrease and the added impurity raises the consolute temperature.
If potassium chloride is added to the phenol-water system, then
its consolute temperature rises considerably. This is because KCl is soluble
in water but not in phenol. Similarly, when an organic substance like
naphthalene is added as an impurity to the phenol-water system, here
also the consolute temperature is increased. In this case the rise in con-
solute temperature is because of the solubility of naphthalene in phenol
but not in water. In alcohol-hydrocarbon system, the addition of traces
of H2O as impurity causes a marked increase in consolute temperature.
This is because water is soluble in alcohol but not in hydrocarbon. Thus,
determination of consolute temperature sometimes is used as a method
of testing the purity of hydrocarbon.
In contrast to the above, if an added impurity is soluble in both
the liquids, then the consolute temperature is decreased. For example if

Chemistry - 1
i 

I
II
C1,
C2II
II     C2(1-)  

  

I
ii

I
     II  

C1, C2 

Solutions
succinic acid is added as an impurity to the phenol-water system, then
the consolute temperature of it is lowered because succinic acid is soluble
in phenol. The mutual solubility temperature varies almost linearly with
the amount of soluble impurities in any of the two liquids.
5.1.5 Completely Immiscible Liquid Mixtures

There are a number of pairs of liquids which do not exhibit any
mutual solubility either at room temperature or higher or lower than the
room temperature. Such pair of liquid mixtures are called completely
immiscible liquid mixtures. In these liquid mixtures each liquid behaves
independently of the other. Hence the properties of each liquid will be
unaffected by the presence of the other.
eg: CS2–H2O, CCl4–H2O, H2O–Hg etc.
Let A and B are the two completely immiscible liquids in the
mixture and their vapour pressures be PA and PB at a certain tempera-
ture. Then the total vapour pressure (P) of such a system is equal to
P = PA+PB
If nA and nB are the number of moles of liquids A and B in the
vapour phase, and V, the volume of the vapour, then from the ideal gas
equation we have
PAV = nART ———(5.1.7)
and PBV = nBRT ———(5.1.8)
where R is the gas constant and T is the absolute temperature. Dividing
eq (5.1.7) by eq (5.1.8), we get
PAV n ART
 or
PBV nB RT
PA n A or

PB n B
n A PA
 ———(5.1.9)
n B PB

Chemistry - 1
n


   n

Hit and TrialC1, C2
n
n =  nK
n
    

    



a 

Solutions
Thus the number of moles in each component in vapour form is
proportional to the vapour pressure of the pure liquid at that tempera-
ture. If WA and WB are the weights of A and B in the vapour, then we
have
W
nA = A or WA = nAMA ———(5.1.10)
MA
W
nB = B or WB = nBMB ———(5.1.11)
MB
where MA and MB are the molecular weights of A and B respectively.
Thus from the equation (5.1.11), we have
W A PA M A
 . ———(5.1.12)
WB PB M B
Thus, the weights of the two distillates depend upon the molar
masses and vapour pressures of the two components. Equation (5.1.12)
can be applied to steam distillation of the liquids.
5.1.6 Steam Distillation

This method is used for the purification of the substances, when
they contain non-volatile impurities, when they are insoluble in water
and volatile in steam.
A liquid boils at a temperature at which its vapour pressure
becomes equal to the atmospheric pressure. For example, aniline is
purified by steam distillation. In this a mixture of aniline and water is
heated. The mixture boils when the combined vapour pressure of water
(P1) and that of the aniline (P2) is equal to the atmospheric pressure.
Thus,
P = P1 + P2 or P2 = P – P1
Since the vapour pressure of the aniline is lower than the atmo-
spheric pressure, aniline in a mixture vaporizes at a temperature lower
than its boiling point. The distillation process which is used to separate
high boiling organic liquids obtained from a natural source by passing
steam through it is called steam distillation.

Chemistry - 1

C1
K  n = 
n C2
b 
 = 
K

  
      

S1, S2 K

S1, S2 
  

        
   




Solutions
For example, chlorobenzene has a boiling point of 132°C. When
steam passes through a source containing it, the mixture of water and
chlorobenzene distills over at about 90°C. The distillate contains about
70% of the chlorobenzene. Similarly a mixture of aniline (b.p.184°C
with decomposition) and water (b.p100°C) under atmospheric pres-
sure boils at 98.6°C. At this temperature the vapour pressure of aniline
is 43 mm and that of water is 717 mm. Hence the total pressure is 43 +
717 = 760 mm.
Thus in steam distillation, the liquid gets distilled at a lower tem-
perature than boiling point where it might decompose. Thus the main
purpose of steam distillation is to avoid the decomposition of the organic
liquid. The relative amount of the compound and water in the mixture
that distills over are expressed by the mathematical relation as
WA PA M A
 . ———(5.1.13)
WB PB M B
where WA = Weight of water distilled
WB = Weight of organic compound distilled
PA = Vapour pressure of water vapour
PB = Vapour pressure of organic compound
MA = Molecular weight of water = 18
MB = Molecular weight of organic compound
Problem. 6:
A mixture of water and aniline boils at a temperature of 98.5°C
at a pressure of 760mm. The vapour pressure of water at this tempera-
ture is 717 mm. Find the composition of the distillate.
Sol.: Boiling point of the mixture = 98.5°C
Vapour pressure of water at 98.5°C, PA = 717 mm
Vapour pressure of aniline =PB=760–717 = 43 mm
Molecular weight of water, MA = 18
Molecular weight of aniline (C6H5NH2), MB = 93
Substituting these values in the following equation:
W A PA M A
 .
WB PB M B

Chemistry - 1
  



     CS2 
  CS2    

  


  

     
    

 C6 H 5 NH 2  HCl
C6 H 5 NH 3Cl 

  HCl 
HCl        
      


Solutions
W A 717 18 12906
 . 
WB 43 93 3999
3999
% of Aniline = × 100 = 23.65
12906  3999
% of water = 100 – 23.65 = 76.35

Thus the composition of the mixture is 23.65% aniline and
76.35% water.
5.1.7 Nernst Distribution Law

Nernst carried out a large number of experiments to study the distri-
bution of many solutes between suitable immiscible solvents. He gener-
alized his observations in the form of a law known as Nernst distribution
law or Nernst partition law. According to this law, “at constant tempera-
ture the dissolved solute distributes itself between the two immiscible
solvents in contact with each other, in such a way that at equilibrium, the
ratio of concentration of the solute in the two solvents is constant.” How-
ever, the following conditions are to be followed for the validity of the
distribution law,
(i) The solute should dissolve in both the solvents in the same form
i.e., the substance should not undergo dissociation or associa-
tion in either of the solvents.
(ii) There should be no chemical combination between the solute
and either of the solvents and
(iii) The solution should be dilute.
If C1 and C2 are the concentrations of the solute at a given tem-

perature in the two immiscible solvents 1 and 2 of binary system, then
according to Nernst Distribution law, we have,
C1
= K (Constant)
C2

Chemistry - 1
where K is called the distribution or partition coefficient of the solute
between the two solvent. It is independent of the total amount of solute
distributing in the two immiscible solvents.
Let us consider the distribution of iodine (solute) in the two im-
miscible solvents water and carbon disulphide. When iodine solution in
CS2 is shaken for a long time with water, then iodine distributes itself
between water and CS2. This experiment is repeated with different
amounts of iodine with time and it is observed that the ratio of its
concentration in the two solvents remains constant at a given
temperature. It is shown in figure 5.1.8.
Concentration of iodine in CS2 layer C
K=  1
Concentration of iodine in water layer C 2
Figure 5.1.8: Distribution of solute between two immiscible solvents
Problem 7:
Succinic acid was distributed between water and ether layers at
T (K) and the following results were obtained per 10 cc of the solution.
(i) (ii) (iii)
Conc. in water layer 0.0244 0.071 0.121
Conc. in ether layer 0.0046 0.013 0.022
Calculate the partition coefficient of succinic acid between
water and ether. What is the molecular state of the acid in the ether
layer?

Solutions
Sol.: From the given data
C water
(i) = K = = 5.304
C ether
C water
(ii) = K= = 5.462
C ether
C
(iii) water = K= = 5.500
C ether
5.304  5462  5.500
Mean value of K = = 5.42
3
Within the experimental error range, the ratio is fairly constant.

This shows that succinic acid exists in the normal molecular state in both
the layers.
(i) Modified form of distribution law for the dissociation of sol-

ute in one of the solvents
The Nernst distribution law discussed above holds good in cases
where the solute exists as simple molecules in the two solvents.
However, this is not true for all the solutes. If there is any dissociation of
the solute in one of the solvents, then the distribution law is to be
modified as follows:
Let us consider a case where the solute is undergoing
dissociation in solvent II and no dissociation in solvent I. Let C1 and C2
be the total concentration of the solute (X) in solvent I and II
respectively. If á is the degree of dissociation of the solute in solvent II,
then the total concentration of the undissociated solute in solvent II would
be C2(1- á) as shown in the figure 5.1.9.

Chemistry - 1
Figure 5.1.9: Distribution of solute between two immiscible

solvents with molecular dissociation in solvent II
Applying the Nernst distribution law, the ratio of concentration
C1
of solute having same molecular mass is given by K =
C2  1   
Suppose, we have a case in which the solute is dissociated in

solvent I with á as degree of dissociation and the solute remains undis-
sociated in solvent II, then the partition coefficient is given by
C1 1   
K=
C2
The above case is illustrated by the following problem.
Problem.8:
An organic acid is distributed between 500 cm3 each of solvent

ether and water. In water it is dissociated. The amount of the acid in
aqueous layer was 6.0 g and ether layer it was 0.72 g. If the partition
coefficient of the acid between the solvents ether and water is 0.16, then

Solutions
calculate the degree of dissociation assuming that the acid has normal
molecular weight in ether layer.
Sol.: Concentration of acid in ether layer
0.72 g
C1 = = 1.44 gL–1
500 cc
Concentration of acid in water layer
6.0 g
C2 = = 12 gL–1
500cc
When the substance is dissociated in one of the solvents,we use the
equation,
C1
K= and the value of K is given as 0.16.
C2  1   
C1
Therefore we have K = = 0.16
C2  1   
Substituting the values of C1 and C2 in this equation, we have

1.44
12 1    = 0.16
or 1.44 = 1.92 – 1.92á
or 1.92 á = 1.92 – 1.44 = 0.48
0.48
or á= = 0.25
1.92
Therefore, the degree of dissociation of the acid is 25%.
(ii) Modified form of distribution law for the association of solute
in one of the solvents
Consider a solute (X) which distributes in the two immiscible
solvents. Suppose in solvent I it remains as such without any molecular
change as shown in the figure 5.1.10 and let its concentration in this
solvent I as C1. Suppose the solute X undergoes molecular association
Chemistry - 1
(nX Xn) in the solvent II and let its concentration here be C2. Then
the modified form of distribution law is given as
C1
K=
n C
2
Figure 5.1.10: Distribution of solute between two immiscible

solvents with molecular association in solvent II
To find the value of n the above expression can be written as

1
log K = log C1 – log C2
n
1
Or log C1 = log K + log C2
n
1
i.e., log C1 = log C2 + constant
n
If a graph is drawn between log C1 and log C2, a straight line is

1
obtained with a single value equal to , from which the value of n, the
n
complexity factor is calculated. The value of n may also be calculated by
the Hit and Trial method by substituting the experimentally determined

Solutions
C1
values of C1 and C2 in the equation n C = K and putting the values of
2
n as n = 1,2,3,…etc. The n value forwhich a nearly constant value of K

is obtained is equal to n. To illustrate the above, the distribution of ben-
zoic acid between water and benzene is studied and the results show
that benzoic acid exists as a dimer in benzene.
Problem 9 :
1. Benzoic acid distributes itself between water and benzene in such a
way that in a definite volume of water there are 1.50, 1.95 and 2.97
g of benzoic acid while in equal volume of benzene there are 24.2,
41.2 and 97.0 g of benzoic acid. What conclusion can be drawn
from these results considering the molecular condition of benzoic
acid in benzene?
Sol.: Method I: (Hit and Trial Method)
(A) From the given data in the problem, three cases are
C water 1.50
(i)  = 0.06198
C bengene 2.42
C water 1.95
(ii)  = 0.04733
Cbengene 41.2
C water 2.97
(iii)  = 0.03062
C bengene 97.0
Here all the values are not constant. Here benzoic acid is not
normal in the two liquids
Cwater 1.50 1.50
(B) (i) C = = = 0.3049
benzene 2.42 4.92
Cwater 1.95 1.95

(ii) C = = = 0.3036
benzene 41.2 6.42

Chemistry - 1
Cwater 2.97 2.97
(iii) C = = = 0.3016
benzene 97.0 9.85
The ratio values are found to be fairly constant. This shows that
benzoic acid exists as a dimer (C6H5COOH)2 in benzene.
Method II: The Logarithmic Method
(i) (ii) (iii)

log C1 (Water) 0.1761 0.2900 0.4728 Y –Axis
log C2 (Benzene) 1.3838 1.6149 1.9868 X – Axis
1
The general equation is log C1 = log C2 + log K
n
This is the y = mx + c type of straight line graph equation with slope
( 1 n ).
The slope is given by
y2  y1
m= x  x
2 1
1 y2  y1 0.2900  0.1761
Now we get for (i) = x x =
n 2 1 1.6149  1.3838
0.1139
= = 0.49
0.2311
1 y2  y1 0.4728  0.2900 0.1828

for (ii) = x x = = = 0.49
n 2 1 1.9868  1.6149 0.3719
1 y2  y1 0.4728  0.1761 0.2967
for (iii) = x x = = = 0.49
n 2 1 1.9868  1.3838 0.6030
1 1
Thus = 0.49 or n = H 2 which means that benzoic acid exists
n 0.49
as a dimer (C6H5COOH)2 in benzene.

Solutions
Problem 10:
Benzoic acid distributes in between water and benzene. Calcu-
late the molecular weight of benzoic acid in benzene from the following
data when C1 and C2 denote respectively the concentrations of acid in
gm/100 ml in aqueous and benzene layers.
Sol.: As per the data given in the problem
C1 0.3
(i) =
C2 1.0 = 0.3
C1 0.6
(ii) C2 = 4.0 = 0.15
C1 0.9
(iii) C2 = = 0.10
9.0
The ratios are not constant, hence benzoic acid does not exist
as single molecule in benzene layer.
Now let us assume that benzoic acid is associated in benzene,
then according to the data in the problem we have:
C1 0.3
(i) C2 = 1.0 = 0.3
C1 0.6 0.6
(ii) C2 = = = 0.3
4.0 2
C1 0.9 0.9
(iii) C2 = = = 0.3
9.0 3
C1
Since C2 is remaining constant, it shows that benzoic acid
exists as dimer in benzene. Hence the molecular weight of benzoic acid
in benzene will be twice the normal molecular weight.

Chemistry - 1
5.1.7 Applications of Nernst Distribution Law
1. Determination of Molecular Complexity and Molecular
Weight
The distribution law is useful in deciding whether a solute is associ-
ated or dissociated in a particular solvent. It also helps to know the
extent of association or dissociation.
(a) If the solute remains as single molecule in one phase and exists
as associated in the second phase, then at equilibrium, the
C1
distribution coefficient K = n C2 where n is the number of single
molecules which combine to form an associated molecule.
(b) If a solute dissociates in one of the solvents, then distribution
coefficient
C1
K = C (1   ) where α is the degree of dissociation of the
2
solute.
If degree of dissociation () of a solute is known at one con-
centration, then its value at some other concentration can be obtained
because K is constant.
2. Determination of solubilities
If two solvents which are saturated with a sparingly soluble salt
are in equilibrium, then according to distribution law
C1 S1
K= C = S
2 2
where S1 and S2 are the solubilities of the solute in the respective sol-
vents forming saturated solutions. Knowing the value of K and one of
the solubilities, it is possible to determine the solubility of the solute in a
solvent.
3. Solvent Extraction of substances from solution
It is an important application of the distribution law in the pro-
cess of extraction, in the laboratory as well as in industry. In the

Solutions
laboratory it is generally used for the removal of a dissolved organic
substance from aqueous solution with suitable organic solvents such as
benzene, ether etc. The advantage is taken of the fact that the partition
coefficient of most of the organic compounds is very largely in favour of
organic solvents.
4. Distribution Indicators
It is a well-known that iodine distributes itself considerably more
in carbon disulphide than in water when both the solvents are in contact
with each other.
Thus, an extremely dilute solution of iodine in water can be suc-
cessfully titrated by adding one or two drops of carbon disulphide. The
concentration of iodine in the carbon disulphide layer becomes large
enough to give a distinct violet colour.
5. Study of complexes
This law is also useful in determining the formula of the complex
ions between bromine and bromide ion as well as between iodine and
iodide ion.
6. To determine the degree of hydrolysis and hydrolysis con-
stant of salts of weak acids and weak bases
Suppose we want to determine the degree of hydrolysis of aniline
hydrochloride. On hydrolysis, it gives C6H5NH3Cl C6H5NH2 + HCl.
A known weight of the salt is shaken with benzene and the weight of
aniline is determined in benzene layer by passing dry HCl through it and
weighing the hydrochloride formed. Concentration of free aniline in aque-
ous layer is determined from the distribution coefficient and the concen-
tration of aniline in benzene.
SUMMARY
On the basis of the physical states of solute and solvent there
are nine types of solutions. A solution in which both solute and solvent
are liquids are called liquid-liquid mixtures. In these mixtures the com-
ponent liquids may be completely miscible, partially miscible or com-
pletely immiscible. For completely miscible liquid solutions Raoult’s law

Chemistry - 1
can be applied. For ideal solutions Raoult’s law is applicable. However
for non-ideal solutions deviations from Raoult’s law can be observed
due to the difference in the molecular interactions of the mixture and the
component liquids. Some liquid mixtures show positive deviations from
Raoult’s law and some show negative deviations. Azeotropic mixtures
are constant boiling mixtures. They distill completely at the same tem-
peratures without any change in composition. Phenol-water system is an
example of partially miscible liquid mixtures. Phenol and water are com-
pletely miscible at the temperature of 66°C, with the composition of
phenol as 33%. This temperature at which two conjugate solutions merge
in to one another is called critical solution temperature. Steam distillation
is employed for the purification of the substances when they contain
non-volatile impurities, insoluble in water and volatile in steam. Nernst
distribution law explains the distribution of a solute between two immis-
cible liquids.
GLOSSARY
Azeotropes: Mixture of two or more liquids of

definite composition which boil at
constant temperature and distill over
completely at the same temperature
without any change in composition.
Binary Liquid A mixture with two liquids.
Mixture:
Boiling Point: The temperature at which vapour
pressure of the liquid becomes equal
to the atmospheric pressure.
Conjugate When equal volumes of two solutions
Solutions: A and B are shaken together, two
layers are formed. One layer is a
saturated solution of A in B and the
other one is a saturated solution of B
in A. These two solutions in
equilibrium with each other are called
conjugate solutions.

Solutions
Critical Solution The temperature at which the two

Temperature layers of the partially miscible liquid
(CST): mixtures become identical in
composition and completely miscible
and the two layers become one single
layer. It is also called consolute
temperature.
Ideal Solution: Solution which obeys Raoult’s law in
which volume of mixing (  Vmix) and
enthalpy of mixing (  Hmix) are zero.
Nernst The solute distributes itself between
Distribution Law: two immiscible solvents in such a way
that the ratio of its concentration in the
two layers is constant at a given
temperature.
Non-Ideal Solutions which do not obey Raoult’s
solution: law under all conditions of
temperatures and concentrations.
Raoult’s Law: The partial pressure of any volatile
constituent of a solution at a given
temperature is equal to the product of
the vapour pressure of pure constituent
and its mole fraction in the solution.
Solvent The process which helps to extract the
Extraction: dissolved substance from the aqueous
solution into the organic liquids
Steam Distillation: A distillation process used to separate
high boiling organic components from
a natural source by passing steam
through it.
Vapour pressure: Pressure of the vapour in equilibrium
with the liquid at a given temperature.

Chemistry - 1
1. Which of the following pairs of temperature as though it were
solutions behave ideally a pure liquid is known as:
(a) Chlorobenzene + (a) Binary liquid mixture
Bromobenzene (b) Ideal mixture
(b) Benzene + Toluene (c) Azeotropic mixture
(c) n-hexane + n-heptane (d) Eutectic mixture
(d) All the above 6. Azeotropic mixture of two
2. The binary liquid mixture which liquids has boiling point lower
shows negative deviation from than either of the two liquids,
Raoult’s law is: when it:
(a) Chloroform + Acetone (a) shows no deviation from
(b) Chloroform + Benzene Raoult’s law
(c) Chloroform + Carbon Tet- (b) shows positive deviation
rachloride (d) None of these from Raoult’s law
3. For an ideal solution formed by (c) shows negative deviation
mixing the two liquids, we have: from Raoult’s law
(a) Hmix= 0 (d) is saturated
(b) Vmix= 0 7. Partial vapor pressure of a so-
(c) Molecular Interactions are lution component is directly
similar
proportional to its mole frac-
(d) All of these
tion. This statement is known
4. The enthalpy change of mixing
as:
(Hmix) of water and alcohol
(a) Henry’s Law
at room temperature is:
(b) Ostwald’s dilution law
(a) Positive
(c) Nernst distribution law
(b) Negative
(d) Raoult’s law
(c) Zero
(d) Depends on the proportion 8. The vapor pressure of pure
benzene is 640 mm at 298K.
of alcohol in the mixture
A solution of a solute in ben-
5. A mixture of the completely
zene shows a vapor pressure
miscible non-ideal liquids which
of 630 mm at the same tem-
distill as such without change
in its composition at a constant
Solutions
perature. The mole fraction of 12. The number of moles of solute
the solute is: present in 200 ml of 0.5M so-
(a) 0.25 (b) 0.20 lution of NaOH are:
(c) 0.18 (d) 0.016 (a) 1 (b) 0.5
9. Vapor pressures of liquids A (c) 0.1 (d) 0.2
and B at a particular tempera- 13. The weight of Na2CO3 present
ture are 120mm and 180 mm in 100 ml of 0.5N solution is:
Hg. If 2 moles of A and 3 moles (a) 2.65 gm
of B are mixed to from an ideal
(b) 5.3 gm
solution, then the vapor pres-
sure of the solution would be: (c) 1.06 gm
(a) 48 mm (d) None of the above
(b) 108 mm 14. Increasing the temperature of
(c) 156 mm an aqueous solution will cause:
(d) 160 mm (a) Decrease in Molality
10. If the molecular interactions of (b) Decrease in Molarity
two different liquid molecules (c) Decrease in Mole Fraction
are stronger than the molecu- (d) Decrease in %(W/w)
lar interactions of the same liq- 15. Azeotropic mixture are:
uid molecules, then the mixture (a) Mixtures of two solvents
shows:
(a) Positive Deviation (b) Those which boil at differ-
(b) Negative Deviation ent temperatures
(c) No deviation (c) Those which can be frac-
(d) may be positive or nega- tionally distilled
tive deviation (d) Constant boiling mixtures
11. A 10% solution of NaCl means 16. Saturated solution of NaCl on
that in 100 gm of solution there heating becomes:
is: (a) Super saturated
(a) 5.85 gm NaCl (b) Unsaturated
(b) 58.5 gm NaCl (c) remains saturated
(c) 10 gm NaCl (d)None of these
(d) 94 gm solvent 17. Which of the following solution
pairs can be separated by frac-
tional distillation:
Chemistry - 1
(a) Water-HNO3 tion of A) in the mixture is 1
(b) Water-HCl atm = 760 mm of Hg)
(c) Benzene-Toluene (a) 50 mol percent
(d) C2H5OH-Water (b) 52 mol percent
18. The mode of expression of (c) 34 mol percent
concentration of a solution that (d) 48 mol percent
remains independent of tem- [Hint: P = PA0. XA + PB0. XB =
perature: PA0. XA + PB0.(1-XA) or 760
(a) Molarity (b) Molality = 520 XA + 1000 (1–XA)
(c) Mole fraction Or XA = 0.50 i.e.; 50 mol per-
(d) Formality cent]
19. At 80°C, the vapor pressure 20. Which of the following is a di-
of pure liquid A is 520 mm of mensionless quantity:
Hg and that of pure liquid B is (a) Mole fraction
1000 mm of Hg. If a mixture (b) Percent by weight of solution
of solutions A and B boils at (c) Percent by weight of solvent
80°C and 1 atm pressure, then (d) All the above s
the amount ofA (i.e.; mole frac-
Fill in the blanks

1. If a solution contains more sol-
5. The ratio of the concentrations
ute than that in a saturated one, of the solute in the two immis-
it is called a _____ solution. cible liquids is called the
2. If a substance dissolves at ______.
saturation with the evolution of 6. The upper critical solution tem-
heat, the solubility ______ with perature is the temperature at
temperature. which the two liquids which
3. In an ideal solution, partial were ______ become
pressure of a component of a ______.
solution=Mole fraction X 7. If 100 ml of water is added to
____. 200 ml of water, the volume of
4. The constituents of ______ so- the mixture will be _____ml,
lution can be separated by frac- but if 100 ml of sulphuric acid
tional distillation while the con- is mixed with 100 ml of water,
stituents of ______ solution
form an
APSCHE - I azeotropic
SEMESTER mixture.
CHEMISTRY TEXT BOOK 324
Solutions
the final volume of the mixture I, then the modified Nernst distri-
will be _____ml. bution law is given as K = __.
8. Mixtures which distill without 14. The condition for an ideal
changing their composition are solution are ___ and ______.
called ______ mixtures or 15. When a solute is dissolved
______ mixtures. in a solvent, the vapor pressure of
9. A molal solution contains a the solution _______.
mole of the solute dissolved in 16. If the vapor pressure at a
______ of the solvent while a particular composition of the two
molar solution contains a mole liquids is the lowest, then its boiling
of the solute in ______ of so- point must be ______.
lution. 17. The system which has
10. Mole fraction of a constituent lower as well as upper critical so-
of a solution is the ratio of lution temperature is ____.
moles of that constituent to the 18. The temperature at which
______ moles present in the two conjugate solutions change
______. into one homogeneous solution is
11. If WA and WB are the called ______.
weights of water and the substance 19. If w gm of the solute is
and PA and PB are their partial pres- present in V1 ml of water and is
sures and their Molecular weights shaken with V2 ml of organic liq-
are MA and MB, then the valid uid, then the weight of solute left
equation for the distillate from the unextracted after the third extrac-
steam distillation is given by = tion is equal to ______.
____. 20. The partition coefficient of
12. If the solute A is dissoci- a substance between CHCl3 and
ated in solvent I and is normal in H2O is 5. The amount of substance
solvent II in the two immiscible sol- left unextracted in a solution of 800
vents, then the modified Nernst dis- mg in 500 ml, after shaking with
tribution law is given as K = 100 ml of CHCl3 is ______mg.
______.
13. In case the solute A exists
as An with molecular association in
solvent II and is normal in solvent

Chemistry - 1
Key: Multiple choice questions
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
d a d b c b d d c b
11. 12. 13. 14. 15. 16. 17. 18. 19. 20.
c c a b d b c b a d
Answers: Fill in the blanks
Vapour
Super pressure of Ideal,
1. 2. Decreases 3. 4.
saturated pure Non–ideal
component
Partially
Partition or Azeotropic,
miscible,
5. Distribution 6. 7. 300 , 180 8. Constant
completely
Coefficient Boiling
miscible
1000 gm or PA M A C1 (1   )
Total,
9. 1 Kg , 1000 10. 11. 12.
Solution PB M B C2
ml or 1 litre
C1  Vmix =
13. n C2 14. 0, ? H mix = 15. Decreases 16. Maximum
0
W3 =
Nicotine – 3
 KV1 
17. 300, 180 18. Water 19.   20. 400 mg
System  KV1  KV2 
.W

Solutions
1. Systems with lower critical solution temperature- Triethy-
lamine-water System (TEA-H2O)
The temperature-composition curve of mutual solubilities of tri-
ethyl amine and water is as shown in the figure below:
Figure 1.: Triethylamine – Water system (LCST)

Here in this system, the mutual solubility of the two components
increases with the decrease of temperature. If the temperature of such a
system is continuously decreased, the two liquids become completely
miscible. The left hand side of the curve indicates the solubility curve of
triethylamine in water and the right hand side of the curve shows the
solubility of water in triethylamine. Unlike phenol-water system, here the
solubilities decrease with the increase in temperature. The two conju-
gate solutions mix up and merge completely at or below 18.5°C. This
temperature is called the critical solution temperature or the lower criti-
cal solution temperature (LCST). The temperature lies at the minimum
of the curve. Thus any point above the temperature of 18.5°C corre-
sponds to heterogeneity of the system and two layers exist, while below
18.5°C temperature it is complete homogeneity and only one layer ex-
ists. Other examples of this type of system with their critical solution
temperatures and percentage of the first component are, i). Diethylamine-
Water system (43°C, 13), ii). 1-methyl piperidine -water system (48°C, 5).
Chemistry - 1
1. Systems with Lower and Upper Critical Solution
Temperatures -Nicotine-water system
In this type of system the mutual solubility of the two compo-
nents in the two layers increases with increase as well as decrease in
temperature. An important example which shows this unusual behavior
is the nicotine-water system.
Figure 2: Nicotine-Water system

The two liquids become completely miscible above a particular
temperature as well as below a particular temperature. This shows that
such systems have upper critical solution temperature (UCST) as well as
lower critical solution temperature (LCST). Thus we have a closed solu-
bility curve as shown in the figure 2.
The system has two critical solution temperatures, the upper
one as 208°C and the lower one as 60.8°C. With the change of external
pressure both the upper and lower critical solution temperatures changes
and approach each other. Ultimately at a particular pressure, the two
liquids become completely miscible. This means that the effect of pres-
sure on this system is that the lower critical temperature is raised while
the upper critical solution temperature is lowered gradually until they
become one. At this point the liquids are miscible at all temperatures.
Other examples of this type are shown in table 1.
Solutions
Table 1: Partially miscible liquid pairs with UCST & LCSTs
Component UCST
Component A LCST (°C)
B (°C)
Butanone water 133 -6.0
Glycerol m-toluidine 120 7.0
water β-picoline 153 49.0
3. Modified form of Distribution Law when the solute undergoes
dissociation in both the solvents with different degrees of dis-
sociation
From the figure shown below, it is evident that in case of solute
undergoing dissociation in both the solvents I and II with different de-
grees of dissociation, then the concentration of the solute in layer I will
be C1(1-α1) and that of layer II would be C2(1-α2). Here C1 and C2 are
the total concentrations and α1 and α2 are the degrees of dissociation of
the solute in the two layers respectively. In such cases the distribution
law applied in modified form is as follows:
C1 (1  1 )
K
C2 (1   2 )
Figure 3: Distribution of solute between two immiscible

solvents with molecular dissociation in both solvents to a different extent

Chemistry - 1


Chapter - 2

          
  


 (Electrolyte)


     

     


MA  M   A 



 M   A  
K
 MA
K=

UNIT - 5 Ionic
Chapter - 2 Equilibrium
Learning outcomes
After studying this unit, student shall be able to

1. Understand the basic idea about the electrolytic dissociation or
ionization theory.
2. Know the various factors which influence the degree of ionization.
3. Derive the Ostwald’s dilution law and the dissociation constant.
4. Understand the concept of ionic product of water
5. Able to know the concept of common ion effect.
6. Understand the solubility product and related problems
INTRODUCTION
Ionic equilibrium is an extension of chemical equilibrium. The
equilibria involving ions come under the title ionic equilibria. The
equilibria between ionic species in aqueous solutions deserve special
attention because of their importance in analytical, biological and
industrial chemistry.
Arrhenius Theory of Electrolytic Dissociation or Ionisation
In order to explain the behaviour of electrolytes in aqueous so-
lutions Arrhenius, (1884) proposed a theory called Arrhenius theory of
electrolytic dissociation or ionization. The postulates of the theory are:
(1) When an electrolyte is dissolved in polar solvents like water, it splits
up into two oppositely charged species, called ions.
(2) The ions formed in solution will be constantly reuniting to form the
undissociated molecules until the state of equilibrium is established.
The equilibrium so established between the ions and the undissoci-
ated molecules is called the ionic equilibrium. Thus, we have
MA M+ + A–
Chemistry - 1
                          
           

      
               


 
(Directive Effect)
 
      

 

  
         
      

       
 



       

Ionic equilibrium
Applying the law of mass of action to the above ionic equilib-
rium, we have
[ M  ][ A ]
K
[ MA]
where K is called the ionization constant.
(1) The total charge present on the cations is equal to the total charge
on the anions. The resultant solution thus is electrically neutral.
(2) When an electric current is passed through the solution of an
electrolyte, the positive ions move towards the cathode and the nega-
tive ions move towards the anode. Thus the ions are free to move
and under the influence of electricity they are directed towards
oppositely charged electrodes. It may be mentioned that current
does not produce ions but it has only directive effect.
(3) The properties of electrolytes in solution are the properties of the
ions such as depression in freezing point, elevation in boiling point,
lowering of vapor pressure and osmotic pressure.
(4) The electrolyte may not be completely ionized. The ratio of the
dissociated molecules to the total number of molecules is termed as
degree of dissociation (a).
Factors affecting the Degree of Dissociation
The degree of dissociation of an electrolyte depends on the
following factors:
(1) Nature of solute: If the solute is a strong electrolyte, then the
extent of dissociation is very considerable. It is almost completely
ionized in many cases. Weak electrolytes are dissociated to only a
small extent. Certain substances such as trichloro acetic acid exhibit
an intermediate behavior and are called intermediate electrolytes.
(2) Nature of solvent: Solvents with high dielectric constants favour
the ionization of electrolyte. Water has a very high dielectric con-
stant (80). So electrolytes in aqueous solutions have higher de-
gree of ionization than in solution of other solvents.

Chemistry - 1



     
(Common ions)


      
         1  



  


  (dynamic qualibrium)   
c AB

  
AB  A   B
 C O O
 C(1  )  c  c

 
A   B 
K   
A B 
Ionic equilibrium
(3) Effect of other solutes: Presence of other ions also affects the
degree of dissociation of a solute. Thus presence of similar ions
(common ions) from another solute lowers the degree of disso-
ciation of a given solute.
(4) Concentration: The extent of ionization of an electrolyte is in-
versely proportional to the concentration of its solution. Thus
degree of dissociation increases as the concentration decreases
and becomes maximum (equal to one) at very high dilution i.e.,
infinite dilution.
(5) Temperature: The higher the temperature, greater is the ion-
ization. Thus increased temperature results in an increased de-
gree of dissociation.
Ostwald’s Dilution Law

Arrhenius theory of electrolytic dissociation assumes a dynamic
equilibrium between ions and unionized molecule in solutions and hence
the law of mass action is applicable to such cases. Consider an electro-
lyte AB. Let us consider that ‘c’ moles of the electrolyte are dissolved
per litre of an aqueous solution. Let ‘’ be its degree of dissociation.
Thus, we have AB A+ + B–
Initial concentration c 0 0
Eq. concentration c(1–α) αc αc
Applying the law of mass action, we have

[ A ][ B  ] c .c c 2
K   ————(5.2.1)
[ AB ] c(1   ) (1   )
This equation is known as Ostwald’s dilution law and K is called
the ionization or dissociation constant.
In case of weak electrolytes, the value of  is comparatively
very small and hence may be neglected in the denominator of the equa-
tion 5.2.1. Then it becomes:

Chemistry - 1
K=
C  .C  C 2
K 
C (1   )

(1   )

           
    
       
K=  2C ---- (5.2.3)
K K
  2 = c
=
c
C,V 
   KV 
  


   
 

 KCl
     

BaCl2     CaSO4 
 

 KCl, NaCl(molten
state)

Ionic equilibrium
K = 2c ————(5.2.2)
K K
or 2 = or  = ————(5.2.3)
c c
Since c, the concentration term is reciprocal of dilution term V
i.e.; volume in dm3 containing one mole of the electrolyte i.e.;
dm3mole–1, therefore equation 5.2.3 can be written as
or = KV ————(5.2.4)
or  V ————(5.2.5)
Thus, the degree of ionization or dissociation of a weak
electrolyte is directly proportional to the square root of dilution. This is
Ostwald’s dilution law.
Problem 1:
0.01 M solution of a mono basic acid dissociates to an extent
of 10%. Calculate the dissociation constant of the acid.
Sol.: C = 0.01M and  = 10% or  = 0.1

Substituting these values in the Ostwald’s dilution law equation,
we have
C 2 (0.01)(0.1) 2 0.01  0.01

K  
(1   ) (1  0.1) 0.9
=1.11×10–4 mole.dm–3
Problem 2:
Calculate the hydronium ion concentration in 0.1 molar solution
of an acid HA, if the dissociation constant of the acid is 6 × 10–10.
Sol.: c = 0.1M, Ka = 6 × 10–10
From Ostwald’s dilution law
K 6 1010
   60 1010 = 7.745 × 10–5
c 0.1

Chemistry - 1
  
 


                  
       
     

   (KW) 
     

H 2O  H 2 O  H3O  OH  .....(5.2.6)
H O OH 
3
 
 K  H 2O 



  H 3O   OH   

H3O OH    KH2O2 
  H 3O   OH    Kw 
(or)  H  O H  Kw
 Kw     
 
H+, OH  
Ionic equilibrium
The acid dissociates as
HA H+ + A-
c(1–) c c
[H ] = c = 7.745 × 10 × 0.1 = 7.745 × 10–6M
+ –5
Problem 3:
The ionization constant of acetic acid at 298K is 1.8 × 10–5.
Calculate the degree of dissociation of the acid in0.01M solution. (Ans.:
 = 4.243 × 10–2 or 4.243%)
Limitations of Arrhenius theory of Ionization

There are many discrepancies and limitations in the Arrhenius
theory. Some of them are,
(1) The Ostwald’s dilution law which is based on Arrhenius theory
fails completely when it is applied to the strong electrolytes.
(2) For uni-univalent electrolytes such as KCl, the agreement between
the degree of dissociation obtained from colligative properties and
from conductance measurements is fairly good. But for bi-univa-
lent electrolytes like BaCl2 or bi-bivalent electrolytes like CaSO4 it
is not at all satisfactory.
(3) Strong electrolytes like KCl, NaCl conduct electricity even in
molten states. This shows that ionization has taken place even in
the absence of water.
(4) The values of equilibrium constants of strong electrolytes, vary with
the concentration of electrolytes. This leads to a doubt whether
ionic equilibrium assumed by Arrhenius exists at all in the solution.
(5) The Arrhenius theory assumes independent existence of ions but
does not take into account the possibility that mobility of the ions
can be altered or changed by attractive forces between oppositely
charged ions lying side by side.
5.2.1 Ionic Product of Water (Kw)

Water behaves both as Bronsted acid and Bronsted base. Dis-
sociation of water may be written as
Chemistry - 1
 H   OH     
+

250C [H+] = [OH-] = 1.0 x 10-7 mol L-1
250CKw = 1.0 x 10-14mol2 L-2
    



       

 CH 3COO   H 
CH 3COOH  H 2 O 

 CH 3COO    H  
Ka 
CH 3COOH 
Ka=HCl
 H+  Ka
C H 3 C O O    HCl
  (backward direction)   

   CH3COONa 

    S

     
 
Ionic equilibrium
H2O + H2O H3O+ + OH– ————(5.2.6)
The equilibrium constant expression for the above equilibrium
is given by the relation:
[ H3O ][OH  ]
K ————(5.2.7)
[ H 2O]2
Since the dissociation constant of water is very low,
concentration of undissociated water molecules i.e., [H2O] may be
considered to remain constant. Hence from equation 5.2.7, [H3O+][OH–
] is also a constant. Here [H3O+] is a hydrated proton which may be
written as [H+] for the sake of simplicity and convenience. Thus
equation 5.2.7 becomes
[H3O+][OH–]=K[H2O]2 or [H3O+][OH–]=Kw ————(5.2.8)
or [H+][OH–] = Kw
The constant Kw is called the ionic product of water.
Hence, in pure water or any aqueous solution, the product of
the concentration of H+ and OH– ions is a constant. In pure water, the
concentration of H+ is equal to OH–
[H+] = [OH-] = 1.0 × 10–7 mol L–1 at 25°C.
Kw = [H+][OH–] = (1.0 × 10–7)(1.0 × 10–7)
Ionic product of water at 25°C, Kw = 1.0 × 10–14 mol2L–2
5.2.2 Common Ion Effect

The dissociation of weak electrolyte (acid or base or salt) is
suppressed in the presence of solution of a strong electrolyte having a
common ion of it is called common ion effect.
For example, consider the dissociation of acetic acid, weak
electrolyte as,
CH3COOH + H2O CH3COO– + H3O+
Applying the law of mass action to the equilibrium, we have

Chemistry - 1


AB  A   B AB
A  ,B        

                     
K   A    B  
    Ksp

       

   Sparingly soluble salt 
   
 
Ag+, Cl-
 AgCl

       

 A g C l ( s )  A g C l  A g   C l 





Ionic equilibrium
[CH 3COO  ][ H 3O  ]
Ka 
[CH 3COOH ]
where Ka is called dissociation constant of acid. If we add a strong acid
like HCl to acetic acid, the concentration of H3O+ or H+ increases. To
maintain the value of Ka constant the concentration of acetate
[CH3COO-] should decrease. In other words the equilibrium will shift in
backward direction in the presence of HCl. Thus the dissociation of
acetic acid is suppressed.
In a similar manner the dissociation of acetic acid is be
suppressed in the presence of a strong electrolyte CH3COONa.
Problem 4:
The ionization constant of a weak acid HCN is Ka = 4 × 10–10
Calculate the concentration of hydrogen ions in:
(i) 0.2M solution of HCN and
(ii) 0.2M solution of HCN containing 1 mole.dm–3 of KCN
Sol.: From Ostwald’s dilution law formula for a dilute solution:

Ka
Degree of dissociation á =
c
(i) In 0.2M solution of HCN,
4 1010
á=  20 1010 = 4.47 × 10–5
0.2
[H3O ] = cá = 0.2 × 4.47 × 10–5
+
[H3O+] = 8.94 × 10–6 mole.dm–3

(ii) In the second case when 1 mole of KCN is present, then the
concentration of CN– = 1.0 M since the concentration of CN–
from HCN is neglected.
[HCN] = 0.2 M
We know the equilibrium expression as
HCN H+ + CN–

Chemistry - 1
 Ag   Cl 
K
[AgCl](s)
AgCl AgCl
        

 K  [AgCl(s)]  Ag  Cl   K sp   Ag   Cl 
(AgCl )
Ksp



Ksp
Ksp>
Ksp<



Ag2SO4

Ag2SO4 (s)  2Ag  SO42
2
 Ag   SO4 2 
K 
 Ag 2SO 4 
2
K  Ag 2SO 4 (s)    Ag   SO 4 2 

Ionic equilibrium
[ H  ][CN  ]
or Ka 
[ HCN ]
Substituting the values of Ka, [HCN] and [CN–] in the above expres-
sion, we have
–10
[ H  ][1.0]
4 × 10 =
[0.2]
0.2  4 10 10

or [H+] = = 8 × 10–11 mol.dm–3
1.0
Thus it is seen that concentration of [H+] ions fall considerably
in the presence of KCN in HCN solution. This explains the phenom-
enon of common ion effect.
5.2.3 Solubility (S)

Solubility of a substance is defined as the maximum amount of
the substance that dissolves in a given amount of the solvent to form a
saturated solution at a definite temperature. When an electrolyte is
dissolved in water, it partly ionizes into ions and the equilibrium is
established between the ions formed and the unionized molecule of the
electrolyte. For example AB A+ + B– where AB is the weak
electrolyte and A+ and B- are the ions formed in solution. Now the prod-
uct of the concentration of the ions in the solution at that dilution and
temperature is called the Ionic Product. Thus the ionic product
expression for the above equilibrium may be given as K = [A+][B–].
5.2.4 Solubility Product (KSp)

Every solid has a definite solubility in a particular solvent at con-
stant temperature and pressure. Thus solubility of the solid in a particular
solvent results in the formation of a saturated solution of the solid in the
solvent. The solid substances which have less solubility in the solvent are
called sparingly soluble salts.
When a sparingly soluble salt such as silver chloride is shaken
well with water, then it dissolves to a smaller extent resulting in the for-

Chemistry - 1
2
 Ksp   Ag   SO4 2 
  Ca3(PO4)2
3 2
 K sp  Ca 2  PO 4 3 
AmBn 

n m
A m B n  mA  nB
 Ksp = [An+]m [Bm-]n

      



  
    HCl  
NaCl
HCl  H   Cl
NaCl  Na   Cl
  Na   Cl 
 NaCl 

    
AB‘S’
 Ksp      
0C
Ionic equilibrium
mation of a saturated solution of the salt. There exists an equilibrium
between the solid phase of the sparingly soluble salt and the ions formed
namely A g+ and Cl- in the saturated solution. Since AgCl is a strong
electrolyte, so all the dissolved silver chloride will be present as ions.
Thus we have solid silver chloride in equilibrium with the silver and the
chloride ions present in the saturated solution. Thus, we have
Applying the law of mass action to the above equilibrium, we

get
[ Ag  ][Cl  ] [ Ag  ][Cl  ]
K or K
[ AgCl ] [ AgCl ( s )]
Since the concentration of solid AgCl in the solid phase is con-
stant irrespective its amount present in contact with the solution, we can
write the above equation as
K[AgCl(s)] = [Ag+][Cl–]
or Ksp = [Ag+][Cl–] (since [AgCl(s)] is a constant).
The constant Ksp in the above equation is called the solubility

product of silver chloride. Thus the solubility product is defined as the
product of the ionic concentrations of the sparingly soluble salt in its
saturated solution at a constant temperature.
In a saturated solution, Ksp = Ionic product
In an unsaturated solution, Ksp > Ionic product
In a super saturated solution, Ksp < Ionic product
If more than two ions of the same kind are obtained by the
ionization of a given sparingly soluble salt, then the concentration of this
particular ion is raised to the power of the concentration of the ion in the
balanced equation and the solubility product constant is expressed ac-
cordingly. For example, if the sparingly soluble salt is Ag2SO4 then the
following equilibrium exists:
Ag2SO4(s) 2Ag+ + SO42

Chemistry - 1
[ Ag  ]2 [SO42 ]
K
[ Ag2 SO4 (s)]
or K[Ag2SO4(s)] = [Ag+]2[ SO42 ]

or Ksp = [Ag+]2[ SO42 ]
Similarly for a sparingly soluble salt like Ca3(PO4)2, the solubility
product constant expression is given as Ksp = [Ca+2]3[P]2
For a sparingly soluble salt of the type AmBn, the equilibrium
reaction can be written as
AmBn mAn+ + nBm–
 Ksp = [An+]m [Bm–]n
Thus, the solubility product value for a given salt remains
constant at a given temperature irrespective of the source from which
the ion originates. This is known as the Solubility Product Principle.
The principle of solubility product is also applicable to cases of
saturated solution of soluble salts. When the product of ionic
concentration becomes greater than the solubility product of the
substance, precipitation takes place. For example, precipitation of NaCl
takes place on passing HCl gas through the saturated solution of sodium
chloride.
HCl H+ + Cl–
NaCl Na+ + Cl–
As the concentration of chloride ions increase, the product of
ionic concentration [Na+][Cl–] exceeds the solubility product of NaCl
and hence NaCl precipitates out.

Ionic equilibrium
Relation between solubility and solubility product
1. If the solubility of the sparingly soluble salt AB is S, then the solubil-
ity product Ksp is given as:
AB A+ + B–
S S
Ksp = [A ][B ] = S.S = S2
+ -
Ksp = S2
2. For a salt of the type A2B or AB2, we have
A2B 2A+ + B–2
2S S
Ksp = [A+]2[B–2] = (2S)2.S = 4S3
3. For salts of the type AB3 or A3B, we have
AB3 A3+ + 3B–
S 3S
Ksp = [A3+][B-]3 = S.(3S)3 = 27S4
or A3B 3A+ + B-3
3S S
Therefore, Ksp = [A+]3[B–3] = (3s)3.s = 27s4
4. For a type of salt AmBn we have
AmBn mAn+ + nBm–
ms ns
Ksp = [An+]m[Bm–]n = (ms)m.(ns)n
Ksp = mmnns(m+n)
The solubility product values of some sparingly soluble salts at

25°C are given in the table 5.2.1.

Chemistry - 1
Table 5.2.1: The solubility products of some sparingly soluble

salts at 298K
S. S.
Substance K sp Substance Ksp
No. No.
1 PbS 0.4 × 10–28 16 Ag2CO 3 6.15 × 10–12
2 CdS 3.6 × 10–28 17 Ag2S 1.6 × 10–50
3 CuS 8.5 × 10–36 18 HgBr 2 8.0 × 10–18
4 HgS 4.1 × 10–52 19 AgBr 7.7 × 10–13
5 MnS 1.4 × 10–18 20 PbI2 1.39 × 10–8
6 ZnS 1.2 × 10–28 21 HgI2 3.2 × 10–29
7 NiS 1.4 × 10–24 22 AgI 9.94 × 10–16
8 CoS 3.0 × 10–25 23 AgCl 1.56 × 10–10
9 Fe(OH)3 1.1 × 10–38 24 Ag2CrO4 9.0 × 10–12
10 Al(OH)3 8.5 × 10–32 25 BaSO4 1.08 × 10–18
11 Zn(OH)2 1.8 × 10–18 26 PbCl2 1 × 10–4
12 Mn(OH)2 4.0 × 10–14 27 PbSO 4 1 × 10–8
13 Mg(OH)2 1.4 × 10–11 28 CaSO4 2.4 × 10–5
14 CaCO3 4.8 × 10–9 29 Cr(OH)3 6.1 × 10–31
15 SrCO 3 1.1 × 10–10 30 BaCO3 8.1 × 10–9
Problem 5:
Determine the solubility product of AgCl if its solubility is
1.3 × 10–5 mole/dm3.
Sol.: solubility s = 1.3 × 10–5 mole/dm3 Ksp = ?

AgCl Ag+ + Cl–
Ksp = [Ag+][Cl–]
s = [Ag+] = [Cl–] = 1.3 × 10–5 mole/dm3
Ksp = s.s = s2 = (1.3 × 10–5)( 1.3 × 10–5)
Ksp = 1.69 × 10–10 mole2.dm–6

Ionic equilibrium
Problem 6:
Calculate the solubility product of PbCl2 if its solubility is 4.448
–3
g.dm .
Sol.: PbCl2 is a AB2 type of salt and the relation between solubility
and solubility product for this type of salt is given
PbCl2 Pb+2 + 2Cl–
s 2s
Ksp = [Pb ][Cl ] = s.(2s)2 = 4s3
+2 – 2
Given, s = 4.448 gm.dm-3

Gram molecular weight of PbCl2 = 207+71 = 278 g mole–1.
4.448
Molar concentration of PbCl2 = =1.6×10–2 mole.dm–3
278
Thus [Pb+2] = s = 1.6 × 10–2 mole.dm–3
[Cl-] = 2s = 2 × 1.6 × 10–2 = 3.2 × 10–2 mole.dm–3
Therefore, Ksp = [Pb+2][Cl–]2 = (1.6 × 10–2) (3.2 × 10–2)2
Ksp = 1.638 × 10–5 mole3.dm–9
or Ksp = 4s3 = 4 (1.6 × 10–2)3 = 4 × 4.096 × 10–6
Ksp = 16.384 × 10–6 = 1.6384 × 10–5 mole3.dm–9
Problem 7:
If the solubility of Ag2CrO4 is 8 × 10–5mole.dm–3 then find the
solubility product of Ag2CrO4.
Sol.: Ag2CrO4 is a A2B type of salt and the relation between solubility
product and solubility is given,
Ag2CrO4 2Ag+ + Cr O42
2s s
Ksp = [Ag ] [Cr] = (2s)2.s = 4s3
+ 2
Therefore, Ksp = 4s3

Given in the problem solubility as s = 8 ×10–5
Therefore, Ksp = 4(8 ×10–5)3 = 4(512 × 10–15) =2048 × 10–15
= 2.048 × 10–12 mole3.dm–9
(or) [Ag+] = 2s = 2×8×10–5=16×10–5 = 1.6×10–4 mole.dm–3
[Cr O42 ] = s = 8 × 10–5 mole.dm–3

Chemistry - 1
Ksp = [Ag ] [Cr] = (1.6 × 10 ) (8 × 10–5)
+ 2 –4 2
= (2.56 ×10–8)(8 × 10–5) = 20.48 × 10–13

or Ksp = 2.048 × 10–12 mole3.dm–9
Problem 8:
The solubility product of CaSO4 is 2.4×10–5mole2.dm–6. Determine
the molarity of CaSO4 in its saturated solution.
Sol.: CaSO4 dissociates as CaSO4 Ca+2 + SO4-2

s s
+2 2
Ksp = [Ca ] [S] = s.s = s
Given Ksp = 2.4 × 10–5mole2.dm–6, s = ?
Ksp = s2 or s2 = Ksp = 2.4 × 10–5
Therefore, s = 2.4  10 5 = 24  10 6
= 4.9 × 10–3mole.dm–3
Thus, the molarity of saturated CaSO4 is its solubility and is equal to
s = 4.9 × 10–3 mole.dm–3 or 0.0049M
SUMMARY
When an electrolyte is dissolved in polar solvent like water it disso-
ciates in to ions. This process is known as ionization or dissociation.
There exist an equilibrium between the ions and undissociated molecules.
According to the Ostwald’s dilution law degree of ionization of a weak
electrolyte is directly proportional to the square root of dilution. It is not
applicable for strong electrolytes. Water being a weak electrolyte still
under go ionization to a very very small extent giving H+ ions and OH-
ions. The product of molar concentrations of H+ and OH– ions in pure
water or in any aqueous solution of acid or base is always a constant at
a constant temperature. At 25°C the ionic product of water is
1.0 × 10-14. The dissociation of weak electrolyte decreases in the pres-
ence of solution of strong electrolyte having a common ion. This is called
common ion effect. This concept has great importance in the volumetric
and industrial analysis. At constant temperature the maximum amount of

Ionic equilibrium
the substance that dissolves in a given amount of the solvent to form a
saturated solution is called solubility. In case of sparingly soluble salts,
the dissolved salt undergoes ionization and form the ions. An equilibrium
exists between the ions and undissociated molecules of the dissolved
salt in its saturated solution. The product of the ions of the sparingly
soluble salt in its saturated solution at a given temperature is called
solubility product. By knowing the solubility product we can know the
conditions of precipitation. It has wide number of applications in
qualitative and quantitative analysis.
GLOSSARY
Degree of It is the fraction of the molecules

dissociation : ionized
Ionic The equilibrium between the ions
Equilibrium: obtained and the undissociated
molecules.
Ionic Product of The product of the concentrations of
sparingly soluble the ions formed from the sparingly
salt : soluble salt
Solubility : The maximum amount of the
substance that dissolves in a given
amount of the solvent to form a
saturated solution at a given
temperature.
Solubility The product of the ionic
Product (Ksp) : concentrations of the sparingly
soluble salt in a saturated solution at
constant temperature.

Chemistry - 1
1. The solubility of PbSO4 at 25°C (a) 108 × 10–25

is 1.1 × 10–4 mole/litre. Then its (b) 1.0 × 10–25
Ksp is: (c) 144 × 10–25
(a) 1.21 × 10-8 (d) 126 × 10–24
(b) 12.1 × 10–6 6. If x mole/litre is the solubility of
(c) 121 × 10–11 the salt KAl(SO4)2, then its Ksp
(d) 1.21 × 10–10 is equal to:
2. The solubility of CaF2 (Ksp = (a) x3 (b) 4x4
3.4 × 10–11) in 0.1M solution of (c) x4 (d) 4x3
NaF would be: (Hint: KAl(SO4)2 ! K+ + Al3+ +
(a) 3.4 × 10–12M 2S O42
(b) 3.4 × 10–10M
x x 2x )
(c) 3.4 × 10–9M
7. The solubility product of AgCl
(d) 3.4 × 10–13M
is 1.8 × 10–10. Precipitation of
3. The solubility product of spar-
AgCl will occur only when
ingly soluble salt Ag2CrO4 is 4
equal volumes of which of the
× 10–12. Then the molar solubil-
following solutions are mixed?
ity of the salt is:
(a) 10–4 M Ag+ and 10–4 M Cl–
(a) 1 × 10–4 mole/litre
(b) 10–7 M Ag+ and 10–7 M Cl–
(b) 2 × 10–6 mole/litre
(c) 10–5 M Ag+ and 10–5 M Cl–
(c) 1 × 10–5 mole/litre
(d) 10–10 M Ag+ and 10–10 M
(d) 2 × 10–12 mole/litre
Cl–
4. For which of the following
8. Which one of the following for-
sparingly soluble salt, the
mulae represents Ostwald’s di-
solubility (s) and the solubility
lution law for a binary electro-
product (Ksp) are related by
lyte whose degree of dissocia-
1
3
 K sp  tion is á and concentration is c?
the equation s =  
 4  (1   )c
(a) K =
(a) BaSO4 (b) Ca3(PO4)2 (c) 
Hg2Cl2 (d) Ag3PO4  2c
5. The solubility of Sb2S3 in water (b) K =
(1   )
is 1x10–5 mole/litre at 298K.
What will be its solubility prod-
uct?
Ionic equilibrium
(1   )c tate begins to form (K sp for
(c) K = BaCO3=5.1 × 10–9)
2
(a) 4.1 × 10–5M
 2c (b) 5.1 × 10–5M
(d) K =
(1   )c (c) 8.1 × 10–8M
9. Which one of the following is (d) 8.1 × 10–7M
the correct quadratic form of 14. The mass of CaC2O4 in grams
the Ostwald’s dilution law equa- that will dissolve in distilled
tion ? water to make one litre of un-
(a) á2c+ák–k = 0 saturated solution of it is,
(b) á2c–ák–k = 0 (Ksp for CaC2O4 = 2.5 × 10–9
(c) á2c–ák+k = 0 mol2.lit–2 )
(d) á2c+ák+k = 0 (a) 0.0064 (b) 0.1028
10. A monobasic acid in 1.0 M so- (c) 0.1280 (d) 0.2056
lution is 0.001% ionized. The 15. Three sparingly soluble salts
dissociation constant of the acid that have same solubility prod-
is: ucts are given below. I A2X II
(a) 1.0 × 10–3 (b) 1.0 × 10–6 AX III AX3. Their solubilities
(c) 1.0 × 10–8 (d) 1.0 × 10–10 in a saturated solution will be
11. Formic acid is 4.5% dissociated such that:
in a 0.1N solution at 20°C. Then (a) III > II > I (b) III > I > II
the ionization constant of for- (c) II > III > I (d) II > I > III
mic acid is, (Hint: For AX, s = K sp , For
(a) 21 × 10–4 (b) 21
1
–4
(c) 0.21 × 10 (d) 2.1 × 10–4  K sp 
3
12. The fraction of total molecules A2X, s=   and for AX3, s

 4 
which is ionized in a solution of
1
an electrolyte is known as:  K sp 
4
(a) degree association = 

(b) order of reaction  27 
(c) degree of ionization Therefore SII > SI > SIII)
(d) mole fraction of the elec- 16. The solubility of A2 X5 is S
trolyte mol.dm–3. Its solubility product
13. Solid Ba(NO3)2 is gradually dis- is:
solved in a 1.0 × 10 –4 M (a) 36s6 (b) 64 × 104 s7
Na2CO3 solution. At what con- (c) 126 s7 (d) 1.25 × 104 s7
centration of Ba+2 will a precipi-

Chemistry - 1
17. If the solubility product of (a) saturated
AgBrO3 and Ag2SO4 are 5.5 × (b) unsaturated
10–5 and 2 × 10–5 respectively, (c) super saturated and precipi-
then the relationship between tation of the salt occurs
the solubilities of these can be (d) Colloidal solution.
correctly represented as: 23. Among the following hydrox-
(a) > ides, the one which has the low-
est Ksp at ordinary temperature
(b) < (c) =
of about 250C is:
(d) None of these
(a) Mg(OH)2 (b) Ca(OH)2
18. The addition of HCl will not
(c) Ba(OH)2 (d) Be(OH)2
suppress the ionization of:
24. The following equilibrium exists
(a) Acetic acid
in aqueous solution
(b) Benzoic acid
CH3COOH CH3COO– + H+. If
(c) H2S
dilute HCl is added without
(d) Suphuric acid
change in temperature, the:
19. Which one of the following is
(a) Concentration of
the most stable: –
CH3COO will increase
(a) CuS (Ksp = 8 × 10–37) (b)
(b) Concentration of
MnS (Ksp = 7 × 10–16) –
CH3COO will decrease
(c) Bi2S3 (Ksp = 1 × 10–70) (d)
(c) Equilibrium constant will
Ag2S (Ksp = 6 × 10–51)
increase
20. H+ ion produces common ion
(d) Equilibrium constant will
effect in the wet analysis of:
decrease
(a) Group I Metals
25. The precipitate CaF2 (Ksp = 1.7
(b) Group II Metals
× 10–10) is obtained when equal
(c) Group III Metals
volumes of the following are
(d) Group IV Metals
mixed:
21. A compound is precipitated
(a) 10–4 M Ca+2+10–4M F–
when its ionic product is
(b) 10–2 M Ca+2+10–3M F–
______ its solubility product.
(c) 10–5 M Ca+2+10–3M F–
(a) Equal to
(d) 10–3 M Ca+2+10–5M F–
(b) more than
26. To prepare pure RbCl from
(c) less than
Rb2SO4, one might add the re-
(d) All the above
agent:
22. When the ionic product of a
(a) BaCl2 (b) BaSO4
solution exceeds the solubility
(c) NaCl (d) RbNO3
product, the solution becomes:
Ionic equilibrium
Fill in the blanks
1. The solubility of Calomel in 8. When HCl gas is passed

water at 20°C is x mole/litre. through a saturated solution of
Then its solubility product value NaCl the solubility of NaCl
is _______. _____.
2. Solubility product of a sparingly 9. The ionization constant of HCN,
soluble salt of the type AB at given that it is 0.0037% disso-
room temperature is 1.21 × 10– ciated in 0.3M solution is
6
M 2. Its molar solubility is ______.
______ mole/litre. 10. The ionization constant of
3. The solubility product of AgCl NH4OH, given that it is 3.0%
is 1.2 × 10–10 at 298K. Then the dissociated in 0.02M solution is
solubility of AgCl in a 0.1 M ______.
solution of NaCl is ______. 11. The ioinization constant of
4. The solubility products of aniline given that it is 0.02% dis-
Al(OH)3 and Zn(OH)2 are 8.5 sociated in 0.01M solution is
× 10–23 and 1.8 × 10–14 respec- ______.
tively. If both Al+3 and Zn+2 are 12. The ionization constant of HF
present in the solution, the cat- given that it is 11% dissociated
ion that will be precipitated as in 0.04M solution is ______.
hydroxide on adding NH4OH is 13. The degree of ionization of
______. NH4OH in its 0.02M solution,
5. Pure NaCl is prepared by satu- if the dissocia-tion constant is
rating a cold saturated solution Kb = 1.8 × 10–5 mole/litre is
of common salt in water with ______.
HCl gas. The principle used is 14. The degree of ionization of
called ______. CH3COOH in its 0.005M solu-
6. The solubility product expres- tion, if the dissociation constant
sion for As2S3 is given as Ksp = is 1.8 × 10 –5 mole/litre is
______. ______.
7. At certain temperature, the 15. The ionization constant of KCN
solubility of the salt A3B2 is x is Ka = 4 × 10–10 mole/litre. The
mole/litre. If the salt ionizes as concen-tration of hydroxide
A3B2 3A2+ + 2B–3, then ions in 0.2M solution of HCN
the solubility product of the is ______.
salt is given as ______.
Chemistry - 1
16. The solubility product of AmBn
is given as Ksp = ____.
KEY
1. A 2. C 3. A 4. C 5 A
6. B 7. A 8. B 9. A 10. D
11. D 12. C 13. B 14. A 15. D
16. D 17. C 18. D 19. B 20. B
21. B 22. C 23. D 24. B 25. B
26 A
Answers for fill in the blanks

1.1 × 10–3 1.2 × 10–9
1. 4x3 2. 3. 4. Al (OH)3
M mol L–1
Common [As+3]2
5. 6. 7. 108 x5 8. Decreases
ion effect [S–2]3
4.11×10–10 1.8 × 10–5 4 × 10 –10
5.5 × 10–4
9. 10. 11. 12.
mol L–1 Mole/litre Mole/litre mol L–1
[H+]=
α=6× Ksp=mmnn.
13. α =3 ×10–2 14. 15. 8.94 × 16.
10–2 S[m+n]
10–6 M
1. Applications of Solubility Product

The principle of solubility product finds numerous applications
as discussed below:
1. The principle of solubility product constant helps in the
determination of solubility of sparingly soluble salts using the relationship
between solubility product and solubility of the sparingly soluble salts.
For example, if the solubility of a sparingly soluble salt like AgCl or
BaSO4 etc. is s, then the solubility product of the salt is given by:
AB A+ + B–
s s
Ksp = [Ba+2][S O42 ] or Ksp = [Ag+][Cl–]
Ksp = s.s = s2 or Ksp = s.s = s2

Ionic equilibrium
Hence, the solubility of AgCl or BaSO4 or any sparingly soluble
salt of the type we have Ksp = s2 where s is solubility and the solubility s
can be calculated using the relation s = K sp
In general for the sparingly soluble salt of type AmBn, the relation
is given as
Ksp = mm . nn . sm+n
Thus the calculation of solubility of a sparingly soluble salt from
the solubility product value is one important application of solubility
product.
2. Prediction of precipitation of reactions
A substance gets precipitated when the ionic product i.e.; the
product of the concentration of its ions present in a solution exceed the
value of the solubility product of the substance. Thus knowing the
solubility product value of a substance and its ionic product value, it is
possible to predict whether precipitation of the substance occurs or not.
Suppose we have [Ag+] = 1 × 10–5 mole/litre and [Cr O42 ] = 1 × 10–2
mole/litre. Then the ionic product value of Ag2CrO4 would be
[Ag+]2[Cr O42 ] = (1 × 10–5)2 (1 × 10–2) = 1 × 10–12 M2.
But the solubility product value Ksp = 2 × 10–12 M2. Since the
ionic product value (1 × 10–12 M2) is less than the solubility product
value (Ksp) i.e.; 2 × 10–12 M2, No precipitation of Ag2CrO4 occurs.
3. Purification of common salt
In the purification of common salt, a saturated solution of
commercial NaCl is taken in which the following equilibrium exists
NaCl Na+ + Cl– (solid) In solution Ksp = [Na+][Cl–]. On passing
HCl gas, the concentration of Cl– ions is increased because HCl is
highly ionized. The ionic product [Na+][Cl–] thus increases considerably
and it exceeds the solubility product value of sodium chloride at the
given temperature. This results in the formation of a super saturated
solution of sodium chloride from which solid sodium chloride
precipitates out in order to restore the equilibrium. Thus the common
salt is purified using solubility product principle.
Chemistry - 1
4. Salting out of soap

The precipitation of soluble salts from their saturated solution in
pure state is called salting out. This principle is applied in the
precipitation of soap which is the sodium salt of higher fatty acid and can
be written as CnH2n+1COONa. It exists in the equilibrium state as:
CnH2n+1COONa CnH2n+1COO– + Na+

or Ksp = [CnH2n+1COO–] [Na+]
On the addition of a saturated common salt solution, the soap

precipitates out because the concentration of [Na+] ions increases and
the ionic product of [Na+][CnH2n+1COO–] far exceeds the solubility
product of soap at that temperature. Thus the salting out of soap occurs.
5. Solvay’s Ammonia-Soda Process
Sodium bicarbonate is manufactured by saturating aqueous
sodium chloride solution with CO2 and NH3 gases. The two gases first
combine to give ammonium bicarbonate (NH4HCO3) which then reacts
with NaCl to form sodium bi carbonate NH4HCO3 + NaCl ; NaHCO3
+ NH4Cl. All the substances are strong electrolytes and so remain in
solution as ions. The solution now contains the four ions namely
Na+, Cl–, NH4+, HC O3 which can form the above four salts. Out of
these salts the solubility product of sodium bi carbonate (NaHCO3) is
the lowest and it can easily be exceeded. Thus on concentration of the
solution, NaHCO3 precipitates out first.
6. Use of Excess of Reagent for precipitation
In quantitative inorganic analysis excess of the precipitating re-
agent is always used to ensure complete precipitation. For example, in
the precipitation of BaSO4, BaCl2 + H2SO4 ; BaSO4 + 2HCl, a little
excess of H2SO4 which is the precipitating reagent is employed so that
the ionic product [Ba2+][ S O42 ] value far exceeds the solubility product
value of BaSO4 and it is precipitated more completely.

Ionic equilibrium
7. Application of solubility product in inorganic qualitative
analysis of cations
The cations are divided into six groups in the qualitative
inorganic analysis on the basis of the concept of solubility product.
(A) Precipitation of First Group Cations
The first group cations are Ag+, Pb+2, Hg2+2 ions and the first
group precipitating reagent is dilute HCl. When dilute HCl is added to
the aqueous solutions of their salts, the cations Ag+, Pb+2, Hg2+2 are
precipitated and separated by HCl as their chlorides because the solu-
bility products of the chlorides of these ions are very low. Thus AgCl,
PbCl2 and Hg2Cl2 have the lowest solubility products out of all other
cation chlorides and so the chlorides of Ag+, Pb+2and Hg2+2 ions are
precipitated but not the chlorides of other cations.
(B) Precipitation of II and IV Group cations as their sulphides
In qualitative analysis, the II and IV group cations are precipi-

tated as their sulphides using H2S gas reagent. II group cations are pre-
cipitated in the presence of dilute HCl whereas the IV group cations are
precipitated as sulphides in the presence of a weak alkali NH4OH. The
principle in separating II group and IV group cations is based on their
respective solubility products.
II group sulphides have solubility products much lower than those
of the IV group cations. Therefore with sufficiently low concentration of
sulphide (S2–) ions, the II group cations are precipitated. This low
concentration of S2–ions is sufficient to exceed the solubility product of
II group sulphides but not sufficient to exceed those of the IV group
sulphides.
In the presence of HCl, the weak ionization of H2S is suppressed
due to the common H+ ions from HCl i.e;
H2S 2H+ + S2–, HCl ! H+ + Cl–

Chemistry - 1
2–
This [S ] concentration of H2S in presence of HCl is sufficient
to exceed the solubility product of II group sulphides only. If H2S gas is
passed in presence of NH4OH the dissociation of H2S increases and
results in the increase of [S2–] concentration. This excess [S2–] ion
concentration is required to cause the precipitation of IV group cations.
The III group cations such as Fe2+, Al3+, Cr3+ do not precipitate as FeS,
Al2S3 or Cr2S3 along with group II cations because their solubility prod-
ucts are much higher than those of group II cations.
Table 2.2: Solubility products of some sulphides at 18°C

S. II Group IV Group
Ksp Ksp
No. Sulphides Sulphides
1 PbS 3.4 × 10–28 MnS 1.4 × 10–16
2 CdS 3.5 × 10–29 ZnS 1.2 × 10–23
3 CuS 2.5 × 10–46 NiS 1.4 × 10–24
4 HgS 4.1 × 10–52 CoS 3.0 × 10–26
(C) Precipitation of III group cations as their hydroxides
The III group cations are Fe2+, Fe3+, Al3+ and Cr3+ and the third
group reagent is NH4Cl and NH4OH is used as group reagent, then the
hydroxides of Zn, Ca, Sr, Ba, Mn, Mg etc. will also be precipitated
along with III group hydroxides. But if NH4Cl is used with NH4OH, the
hydroxides of III group cations only will be precipitated. This is due to
the common NH 4 ions from highly ionized NH4Cl which suppress the
ionization of NH4OH to such an extent that the small concentration of
OH– ions formed is sufficient to exceed the solubility product of the
hydroxides of III group cations only.
NH4OH NH4+ + OH–, NH4Cl  NH4+ + Cl–
NH4Cl is added to avoid the precipitation of cations other than

III group cations as hydroxides. Therefore this much small concentra-
tion of OH– ions will not be sufficient to precipitate the hydroxides of Zn,

Ionic equilibrium
Mn, Ni, Co, Mg etc. but is sufficient to exceed only the solubility prod-
uct of the hydroxides of III group cations. Hence the [OH–] here cannot
precipitate the hydroxide of IV group, V group and VI group cations.
The solubility products of Group III hydroxide cations and other groups
cations hydroxides are given in the following table
Table: Solubility products of some hydroxides at 18°C

Other than
S. III Group
Ksp III Group Ksp
No. Hydroxides
Hydroxides
1 Fe(OH)3 11 × 10–36 Zn(OH)2 1.8 × 10–14
2 Al(OH)3 8.5 × 10–23 Mn(OH)2 4.0 × 10–14
3 Cr(OH)3 6.7 × 10–31 Mg(OH)2 3.4 × 10–11
(D) Precipitation of V group cations as their carbonates
The V group cations Ca+2, Ba+2, Sr+2and the V group reagent is

NH4Cl + NH4OH and ammonium carbonate. The cations of V group
are precipitated as their carbonates by adding ammonium carbonate
solution in alkaline medium. If ammonium hydroxide alone is added,
then the hydroxides of V group cations and the VI group Mg+2 cation
get precipitated. Hence NH4Cl is also added so that NH4+ ions from
NH4Cl suppress the ionization of ammonium carbonate and prevent the
precipitation of Mg+2 as MgCO3 and allow only the formation of V group
cations as their carbonates.
Therefore, NH4Cl is used with (NH4)2CO3 in V group
NH4Cl NH4+ + Cl–,

(NH4)2CO3 2NH4+ + C O32

Chemistry - 1

Chapter - 3

   

(interactions) 
      

        


   




  

 
non-electrolytic
     

 
UNIT - 5 Dilute
Chapter - 3 Solutions
Learning outcomes

1. Understand the meaning of colligative properties and their
importance
2. Know the terms vapour pressure, lowering of vapour pressure and
relative lowering of vapour pressure
3. Understand the Raoult’s law applicable for solutions containing
non-volatile solute and limitations of Raoult’s law
4. Calculate the molar mass of an unknown solute using Raoult’s
equation or simplified form of Raoult’s equation
5. Know the definitions of boiling point, elevation of boiling point and
its relation to molar mass of solute and experimental determination
of elevation of boiling point
6. Understand the definitions of freezing point, depression of freezing
point and its relation to molar mass of solute and experimental
determination of depression of freezing point
7. Know about the osmosis, osmotic pressure, relation to molar mass
of solute and experimental determination of osmotic pressure
8. Know the difference between isotonic, hypertonic and hypotonic
solutions
9. Know the reverse osmosis and its importance in desalination and
purification of water
10. Understand the abnormal colligative properties, abnormal molar
masses and van’t Hoff factor.

Chemistry - 1
  
  

  

 Lowering of Vapour Pressure):

°C
   mm Hg.     


    



 
      






Dilute Solutions
Introduction
The solutions which have relatively less amount of solute than
solvent are called dilute solutions. In these solutions the interactions be-
tween solute and solvent particles are considered to be negligibly small.
So, dilute solutions behave more or less as ideal solutions.
The dilute solutions containing non-volatile solutes are known to
exhibit some special properties called colligative properties (From Latin,
colligatus means tied together). These properties depend exclusively on
the number of particles of solute and independent of their chemical
nature and size. The four colligative properties of dilute solutions which
we discuss in this unit are 1. Lowering of vapour pressure 2. Elevation
of boiling point 3. Depression of freezing point and 4. Osmotic pressure.
These four properties are inter-related since all of them
basically depend on the number of solute particles present in definite
amount of solvent. Furthermore, if one colligative property is determined
experimentally, the other properties can be calculated. The
experimentally obtained values of colligative properties are very much
useful in the determination of molar masses of solutes.
In non-electrolytic solutions, the dissolved solute will be in the
same form as it exists in the solid form i.e., it neither undergoes
dissociation or association in solution. The colligative properties of such
dilute solutions so determined are referred to as the normal colligative
properties. In electrolytic solutions, on the other hand the dissolved
solute to certain extent may undergo either dissociation or association
depending on its chemical nature. In such solutions, the number of
particles of solute may be more or less than expected. In such a case the
colligative properties obtained are not normal and they need
modification.
In this unit, we shall discuss these properties one by one in the
following sections.
5.3.1 Lowering of Vapour Pressure
Vapour pressure is the characteristic property of a liquid. It
depends on the nature of the liquid and temperature. For instance, the
Chemistry - 1
 P° mm,P
mm HgP0-P mm Hg
    Relative Lowering of Vapour

Pressure):
   


Von Babo P°, P
       
  



      



n1, n2. 
n1
 n2
Dilute Solutions
vapour pressure of water at 100°C is 760 mm Hg. At a given
temperature, the vapour pressure of a liquid is defined as the pressure
exerted by the vapours of the liquid on its surface, when vapour and
liquid are in equilibrium state. When some non-volatile solute is
dissolved in a pure liquid (solvent), its vapour pressure is lowered. Thus,
the solution has lower vapour pressure than the pure solvent. This
decrease in vapour pressure of solvent in the presence of non-volatile
solute is known as lowering of vapour pressure of solvent. This can be
explained as follows. In the case of pure solvent, the surface contains
only solvent molecules, while in solution of non-volatile solute, the
surface has both solute and solvent molecules. As evaporation is a
surface phenomenon, the number solvent molecules, which can alone
vapourise are relatively lesser with respect to solution than in pure
solvent.
With the addition of some more amount of solute, the vapour
pressure of solvent further decreases due to increase in number of solute
particles in solution. Consequently the difference between vapour
pressure of pure solvent and solution i.e., lowering of vapour pressure
increases. Thus, the lowering of vapour pressure is a colligative
property. Let, the vapour pressure of pure solvent is, P0 mm and that of
solution is P mm Hg. Therefore, lowering of vapour pressure of the
solvent is equal to P0 – P mm Hg.
5.3.2 Relative Lowering of Vapour Pressure
The lowering of vapour pressure relative to the vapour pressure
of pure solvent is known as the relative lowering of vapour pressure.
P0  P
Relative lowering of vapour pressure =
P0
Von Babo showed that although both P0 and P increases with
the increase of temperature, yet relative lowering of vapour pressure is
same at all temperatures. After extensive experimentation on aqueous
solutions Raoult (1886) gave an empirical relation between the relative
lowering of vapour pressure and concentration of solute in solution in
the form of a law called Raoult’s law. It states that, the relative lowering

Chemistry - 1
 n2 
      


Derivation of Raoults Law:




P
P0
 X 1 
P0
1  1 X1
P
P0  P
P0
 X 2 (Since X2 = 1 - X1)
      


   





Dilute Solutions
of vapour pressure of a dilute solution is equal to the mole fraction of the
non-volatile solute dissolved in it.
Mathematically, it can be expressed as
P0  P n2
= n1  n 2 = mole fraction of solute ——-(5.3.1)
P0
Where, n1 and n2 are the number of moles of solvent and solute
respectively.
In dilute solutions, the number of moles of solute (n2) relative to
the number of moles of solvent or total number moles of solution is very
less. So, n2 can be neglected in the denominator of the above Raoult’s
law equation. In such a case, Raoult’s law equation reduces to
——-(5.3.2)
This equation is called the simplified form of Raoult’s law

equation and is applicable for dilute solutions only.
Derivation of Raoult’s Law
Raoult’s law for a solution containing non-volatile solute in a
volatile solvent can be stated as, at a given temperature, the vapour
pressure of a solution is directly proportional to the mole fraction of the
solvent. Mathematically it can be represented as
P = P0. X1 ——-(5.3.3)
P
= X1
P0
P
or 1 = 1 – X1
P0
P0  P
= X2 Since, X2 = 1 – X1
P0
This is Raoult’s law equation applicable for dilute solutions con-
taining non-volatile solute. Thus, the relative lowering of vapour

Chemistry - 1
   
    


W, Wm, M



n2, n1         

W
P0  P m

P 0
W W 

m M
W
0
P  P
 m
P0 W 
M
 w, W, M
m
       


Dilute Solutions
pressure depends only on the number of moles of solute and
independent of nature of the solute or solvent. From this equation we
can also say that, equimolar quantities of any two non- volatile solutes in
the same amount of same solvent produce same lowering of vapour
pressure. Experimentally the relative lowering of vapour pressure can
directly be obtained by Ostwald-Walker’s dynamic method.
Determination of molar masses of solute
The molar mass of a non-volatile, non-electrolytic solutes can
be determined by measuring the relative lowering of vapour pressure
produced by dissolving a known weight of solute in a known weight of
the solvent. If w, W are the weights of solute and solvent, m, M are their
molar masses respectively, then we can have,
w
number of moles of solute, n2 =
m
W
number of moles of solvent, n1 =
M
Substituting n2 and n1 in equations 5.3.1 and 5.3.2 we can have the
following expressions
w
P0  P
0
= w mW ——(5.3.4)
P 
m M
w
0
P P
0 = m ——-(5.3.5)
P W
M
P0  P
Knowing the value of from the experiment and w, W
P0
and M, the molar mass of an unknown solute, m can be determined

Chemistry - 1
  
 
 
 


   


      
                       
       

 

 C  



      
       
(T)
(T0)
 (  Tb)
  Tb TT0
 Tb      
Dilute Solutions
using equations 5.3.4 or 5.3.5 depending on the concentration of solute
in solution.
Limitations of Raoult’s Law

Raoult’s law is applicable to only
1. Very dilute solutions
2. The solutions containing non-volatile solutes and
3. The solutions of non- electrolytic solutes i.e., the solutes which can
neither dissociate nor associate in solution.
Problem 1 :
At 75°C 3.68 g of a solute is dissolved in 53 g of benzene. The
vapour pressure of solution at that temperature is 615 mmHg. Find the
molar mass of the solute. (Given Vapour pressure of pure benzene at
75°C is 640 mm).
Sol: Vapour pressure of benzene, P0 = 640 mm

Vapour pressure of solution, P = 615 mm
3.68
No. of moles of solute, n2 =
m
53
No. of moles of solvent (benzene) n1 =
78
P0  P n2
From Raoult’s law, we know = n1  n 2
P0
3.68
640  615 m

640 3.68 53

m 78
3.68
25 m

640 3.68
 0.679
m

Chemistry - 1

 
       
 

                     
 
     
     




    P0C   
T0,T1,T2 
P0,P1,P2 
  BD, CE
ACE, ABD 

AB AD
 
AC AE
T1  T0 P 0  P1
 T  T  P0  P
2 0 2
 Tb 1 P1
  T   P
b 2 2
 Tb  P 

Dilute Solutions
 3.68  3.68
0.039   0.679  
 m  m
0.1435 3.68
 0.0264 
m m
3.68 0.1435
  0.0264
m m
3.68  0.1435
 0.0264
m
0.264 m = 3.536
3.536
Molar mass of solute, m = = 134 g mol–1
0.0264
5.3.3 Elevation of Boiling Point
In the previous section we have learnt that, vapour pressure is
the characteristic property of a liquid and it increases with increase in
temperature. However, at a particular temperature the vapour pressure
of the liquid becomes exactly equal to the atmospheric pressure (usually
1 atmosphere). At this temperature, the liquid starts boiling. Thus,
boiling temperature or boiling point of a liquid is defined as the
temperature at which the vapour pressure of a liquid becomes equal to
atmospheric pressure. For example boiling point of water is 100°C at 1
atmosphere pressure. When, some non-volatile solute is dissolved in a
pure solvent, the vapour pressure of the solvent decreases. So, the
solution has lower pressure vapour pressure than the solvent. In order
to make the solution to boil, its vapour pressure must be increased to
atmospheric pressure by raising the temperature above the boiling point
of pure solvent. Thus, the boiling point of the solution is always higher
than that of the pure solvent in which the solution is prepared. Similar to
lowering of vapour pressure, the elevation of boiling point also depends
on the number of moles of solute. As the concentration of solute in
solution increases, elevation of boiling point also increases. Thus it is
also referred to as the colligative property.

Chemistry - 1
                  



w
0
P P m

P0 W
M
w W 0
 p0  p    p 
m M
P0,M 
w 1
p 0  p
m

W

w 1
 p  
m W


w 1
 Tb 
m

W

w 1
 Tb  K b 
m W

Kb
  ebullioscopic 
Kg
(Kb)
    Kg
Dilute Solutions
The difference between the boiling point of solution (T) and
boiling point of pure solvent(T0) is known as elevation of boiling point
and it is denoted as DTb.
 the elevation of boiling point, Tb = T – T0.
The value of DTb depends on the nature of solvent and
concentration of the solute in solution.
Relation between elevation of boiling point and lowering of vapour

pressure
The relationship between elevation of boiling point and lowering
of vapour pressure can be obtained from vapour pressure-temperature
curves of pure solvent, solution-1 and solution-2 of different
concentrations as shown in the figure 5.3.1.
Fig. 5.3.1: Vapour pressure-temperature curves

The curves related to solutions-1 and 2 always lie below the
curve of pure solvent, since they have lower vapour pressure than the
pure solvent. The line P°C represents the atmospheric pressure. T0, T1
and T2 represent the boiling points of pure solvent and solutions-1 and 2
and P0, P1 and P2 are the corresponding vapour pressures of pure
solvent and solutions-1 and 2 respectively. For dilute solutions the curves
BD and CE are approximately taken as straight lines. So the triangles
ACE and ABD are identical.
Chemistry - 1


Tb  K b  

 w W 
KbKg

      

K b  w  1000
m  Tb  W 
Kb

        
W

Kb 
 Tb  m  W
K b 
1000  w
Kb 
RT0 2
Kb 
1000L v
RT0 2 M
 K b  1000H
vap
R    T0       

Dilute Solutions
AB AD
 
AC AE
T1  T0 P 0  P1
or 
T2  T0 P0  P2
 Tb 1 P1
or 
 Tb 2 P2
 Tb P ——-(5.3.6)
Thus, the elevation of boiling point is directly proportional to the

lowering of vapour pressure.
Relation between elevation of boiling point and molar mass of

solute
Raoult’s law equation applicable for a dilute solution from
equation 5.3.5 is
w
P0  P
0 = m
P W
M
w M 0
P0 – P =   P ——-(5.3.7)
m W
For the pure solvent P0 and M(molar mass) of the solvent are constants.
Thus,
w 1
P0 – P   ——-(5.3.8)
m W
w 1
or P   ———(5.3.9)
m W
Comparing equations (5.3.6) and (5.3.9), we have
w 1
Tb   ——-(5.3.10)
m W

Chemistry - 1
L Jg) 
H vap 
Kb   K Kg mol1
Kb 

    

            
  









  T0     



T1



Dilute Solutions
Tb= Kb w  1 ——-(5.3.11)
m W
Kb is a proportionality constant called boiling point elevation
constant, molal elevation constant or ebullioscopic constant .When 1
mole of solute is dissolved in 1 kg of a solvent(1molal solution) the el-
evation of boiling point becomes equal to molal elevation constant Kb.
Therefore, molal elevation constant is defined as the elevation in boiling
point produced when 1 mole of solute is dissolved in 1 kg of solvent
i.e., due to 1 molal solution.
 Tb = Kb × molality of solution ——(5.3.12)
Determination of molar mass of solute

Knowing the weight of solute(w), weight of solvent(W) in grams,
Kb of the solvent given for kg (from tables) and elevation of boiling point
measured from experiment, molar mass of an unknown solute can be
calculated using the equation
1000  Kb  w
Molar mass of solute, m = ——(5.3.13)
Tb  W
Molal elevation constant (Kb)
It is characteristic of the solvent and it can be calculated by the

following two methods.
Method -1 :In this method a known weight of solute whose molar
mass(m)is already known, is dissolved in a fixed weight of solvent(W)
and elevation of boiling point is determined experimentally. By substitut-
ing this data in the equation given, Kb can be calculated.
Tb  m  W
Kb =
1000  w
Method-2 : In this method Kb can be calculated from thermodynami-
cally derived relationship.

Chemistry - 1
1000  Kb  w
 m  Tb  W
  


    


C




T0 T0
 Tf 
 Tf  T0  T
     


 





Dilute Solutions
RT02
Kb=
1000  Lv
RT02 M
or Kb= 1000  H
vap
Where R= gas constant,T0 =boiling point of pure solvent, Lv= latent

heat of vapourisation of solvent in Joules per gram,DHvap = heat of
vapourisation per mole.
The units of Kb are K kg mol–1. The Kb values of some common
solvents are given in Table.5.3.1.
Experimental determination of elevation of boiling point: The
elevation of boiling point is generally determined by Cottrell’s method
and is described below.
Cottrell’s Method
The experimental set up used in this method is shown in Fig. 5.3.2.

It consists of a tough glass tube, in which a known weight of the pure
solvent is taken.A sensitive thermometer is arranged in the tube in such a
way that the bulb is at some distance above the solvent.The tube also
consists of a side tube to fix the water condenser to condense the vapour
of the solvent. An inverted glass funnel with bifurcated stem is placed at
the bottom of the tube as shown in the figure 5.3.2.
The apparatus is kept under the burner and heated slowly. The
solvent along with its vapour is allowed to spray continuously around the
bulb of the thermometer till the temperature remains constant. At this
point of time the temperature is recorded. This is to be taken as the
boiling point of the pure solvent. The apparatus is then kept aside of the
burner to attain the room temperature. Now, a known weight of solute,
whose molar mass is to be determined is carefully dissolved in the sol-
vent and the experiment is repeated to get the boiling point of solution.

Chemistry - 1

  CFB
      
B,F,CT0,
T1, T2
 P0,P1,P2      
 FD, CE  
CB BCE, BDF

EC BE

DF BD
T0  T2 P0  P2

T0  T1 P 0  P1
 Tf 2 P2

 Tf 1 P1
 Tf  P 




W
P0  P
0
 m
P W
M
w M
 P 0  P  m  W  P0 
Dilute Solutions
Fig. 5.3.2 : Cottrell’s apparatus

The difference in boiling points of solution and solvent gives the
elevation of boiling point. Using this value, molar mass of solute can be
calculated from the expression given below.
1000  Kb  w
Molar mass of solute, m = Tb  W
Problem 2 :
A solution containing 0.5126 g of naphthalene (molar mass 128
g mol-1) in 50 g of CCl4 yields a boiling point elevation of 0.402 °C.
0.6216 g of unknown solute in the same mass of solvent gives a boiling
point elevation of 0.647°C. calculate the molar mass of the unknown
solute.
Sol. : We know that
1000  Kb  w
Tb =
m W
 Tb 1 w1 m2
 
 Tb 2 m1 W2

Chemistry - 1
P , M
0
w 1
 P0  P   
m W
w 1
(or) P  
m W


w 1
Tf  
m W

w 1
Tf  K f 
m W

Kf       
      
Kg

    Kg    


 Tf  K f x 

wW
(Kb) Kg 
      

1000 x K b x w
K b  
T f xW
APSCHE
 CHEMISTRY
- I SEMESTER Kf TEXT BOOK 388
Dilute Solutions
0.402 0.5126 m2
 
0.647 128 0.6216
0.402  128  0.6216
Molar mass of solute, m2 =
0.647  0.5126
m2 = 96.4 g mol–1
Problem 3 :
What should be the value of the molal boiling point constant of a
solvent if 0.5 g of a solute (molar mass 100 g mol-1) in 25 g of the
solvent elevates the boiling point by 1°C
Sol. : Elevation of boiling point, Tb = 1 °C
Weight of solute, w = 0.5 g
Molar mass of solute, m = 100 g mol–1
Weight of solvent, W = 100 g
Molal elevation constant, Kb = ?
1000  Kb  w
Tb =
m W
1000  Kb  0.5
1=
100  25
100  25
Kb = = 5.0 K.kg.mol–1
1000  0.5
5.3.4 Depression of freezing point
Like vapour pressure and boiling point, freezing point is another
characteristic property of a liquid. The freezing point of a liquid is
defined as the temperature at which the solid phase begins to separate
from the liquid. At this temperature both solid and liquid are in
equilibrium and have same vapour pressures. For example, the freezing
point of liquid water is 0°C when some non-volatile solute is dissolved in
a pure solvent the vapour pressure of solvent decreases. In other words,
the solution has lower vapour pressure than the pure solvent. So, the
solution undergoes freezing at a lower temperature than the pure

Chemistry - 1


m
wW
      
Kf 
Tf  m  W
Kf 
1000  w

Kf 
RT0 2
Kf 
1000L f
RT0 2  M
(or) K f 
1000  H f
R T0  Lf 
   Jg)  H f   

Kf   K . Kg mol1
Kf 






Dilute Solutions
solvent. The difference between the freezing point of the pure solvent
(T0) and solution (T) is referred to as the depression of freezing point.
Depression of freezing point, DTf = T0 – T

The addition of some more solute causes further increase in
number of solute particles in solution. This results in increase of
depression of freezing point. So it is also a colligative property of a dilute
solution.
Relation between depression of freezing point and lowering of

vapour pressure
To derive the relationship between depression of freezing point
and lowering of vapour pressure, let us consider the vapour pressure–
temperature curves of pure solvent, solution–1 and solution–2 of
different concentrations as shown in Fig. 5.3.3.
Fig. 5.3.3 : Relation between lowering of vapour–pressure and depression of

freezing point
The curves of solutions as expected run just below the curve of

pure solvent, since they have lower vapour pressures than the solvent.
CFB is a curve for the solid solvent. The vapour pressure–temperature

Chemistry - 1
 

 

     
 C

 


 
T0





      

1000  K f  w
 m  Tf  W
 
 0C
 
 
0C 
Dilute Solutions
curves of the solvent, solution-1 and solution-2 meet the CFB curve at
the points B,F and C respectively. T0, T1, T2 are the freezing points of
pure solvent, solution-1 and solution-2 and P0, P1 and P2 are their vapour
pressures respectively. For dilute solutions, FD and CE are almost straight
lines. CB is also nearly a straight line. Thus BEC and BDF are the similar
triangles. So,
EC BE
=
DF BD
T0  T2 P0  P2
T0  T1 = P0  P1
 Tf 2 P2
= P
 Tf 1 1
 Tf  P -——(5.3.14)
Hence, depression of freezing point is directly proportional to
the lowering of vapour pressure.
Relation between depression of freezing point and molar mass of

solute
Raoult’s law equation applicable for a dilute solution (from 5.3.5)
is
w
0
P P
= m
P0 W
M
w M
P0 – P =  × P0 -——(5.3.15)
m W
For the pure solvent P0 and M (molar mass) of the solvent are
constants.
w 1
P0 – P   -——(5.3.16)
m W

Chemistry - 1
   
 

       
   0C
0C



 
 



  
       


     

1000  K f  w
 m  Tf  W
     
 


Dilute Solutions
w 1
or P  ——(5.3.17)
m W
Comparing equations 5.3.14 and 5.3.17, we have
w 1
Tf  -——(5.3.18)
m W
Tf = Kf w  1 ——-(5.3.19)
m W
Where, Kf is a proportionality constant called freezing point depression

constant, molal depression constant or cryoscopic constant. When 1
mole of solute is dissolved in 1 kg of a solvent(1molal solution), the
depression of freezing point becomes equal to molal depression
constant Kf. Therefore, molal depression constant is defined as the
depression in freezing point produced when 1 mole of solute is
dissolved in 1 kg of solvent i.e., due to 1 molal solution.
Tf = Kf × molality of solution ——-(5.3.20)

Determination of molar mass of solute
Knowing the weight of solute(w), weight of solvent(W) in grams,
Kf of the solvent given for kg (from tables) and elevation of boiling point
measured from experiment, molar mass of an unknown solute can be
calculated using the equation
1000  Kb  w
Molar mass of solute, m = ——-(5.3.21)
Tf W
Molal depression constant (Kf)
It is characteristic of the solvent and it can be calculated by the
following two methods.
Method – 1 : In this method a known weight of solute whose molar
mass(m)is already known, is dissolved in a fixed weight of solvent(W)
and depression of freezing point is determined experimentally. By
substituting this data in the equation given under, Kf can be calculated.

Chemistry - 1



   
     

       
      

      

     

       




  
   
 
      




Dilute Solutions
T f  m  W
Kf = ——-(5.3.22)
1000  w
Method – 2 : In this method Kf can be calculated from thermodynami-
cally derived relationship.
RT02
Kf = 1000  L
f
RT02  M
or Kf = 1000  H
f
Where R = gas constant, T0 = freezing point of pure solvent, Lf = latent

heat of fusion of solvent in Joules per gram, DHf = heat of fusion per
mole.
The units of Kf are K kg mole-1. The Kf values of some common
solvents are given in Table 5.3.1.
Table 5.3.1: Molal Boiling Point Elevation and Freezing Point Depression
Constants for Some Solvents
Kb/K kg K1/K kg
Solvent b.p./K f.p/K
mol–1 mol–1
Water 373.15 0.52 273.00 1.86
Ethanol 351.50 1.20 155.70 1.99
Cyclohexane 353.74 2.79 279.55 20.00
Benzene 353.30 2.53 278.60 5.12
Chloroform 334.40 3.63 209.60 4.79
Carbon
350.00 5.03 250.50 31.80
tetrachloride
Carbon
319.40 2.34 164.20 3.83
disulphide
Dicthyl ether 307.80 2.02 156.90 1.79
Acetic acid 391.10 2.93 290.00 3.90
Experimental determination of depression of freezing point

The measurement of depression of freezing point can be done
by the following two methods. 1.Beckmann’s method 2. Rast’s
camphor method.

Chemistry - 1
        
     




        
       


     


       
    


  





       


Dilute Solutions
1. Beckmann’s method
The apparatus used in this method is shown in Fig.5.3.4. It
consists of a wide glass tube, called freezing tube in which the solvent is
taken. It is also provided with a side tube to introduce the known weight
of solute. The freezing tube is fitted with a cork through which, a
Beckmann’s thermometer and stirrer are introduced. This is also
surrounded by an outer jacket which prevents rapid cooling of the
solvent. The entire set up is then arranged in a trough containing freezing
mixture(ice and salt) to provide a temperature of about 5 °C, lower than
freezing point of the pure solvent.
Fig. 5.3.4 : Beckmann’s freezing point apparatus

A known weight of pure solvent is taken in the freezing tube and
the apparatus is kept in the trough containing freezing mixture. The
temperature of the solvent decreases rapidly below its freezing point
due to unavoidable super cooling. As the crystallization starts the
temperature slowly increases and attains a steady value and is recorded.
This is taken as the freezing point of solvent.
The apparatus is then taken out from thefreezing mixture and
slightly warmed to melt the solid. A known weight of solute is added to
the solvent through the side tube and completely dissolved by shaking
with the stirrer. The apparatus is again placed in the freezing mixture and
Chemistry - 1


 
 

 
 

    
   
     
   T      C

 
  CRT
 n 
 RT
V
R V
w m 
w
n 
m
w 
  x RT
mV
 w, TV


Dilute Solutions
freezing point of solution is measured in the same way as that of the
solvent.The difference in freezing points of pure solvent and solution is
taken as depression of freezing point.Knowing this value, the molar mass
of solute can be calculated using the expression,
1000  K f  w
Molar mass of solute, m = Tf  W
Precautions
1. The super cooling should not exceed 0.5 °C.
2. The stirring should be uniform.
3. The temperature of the freezing mixture should not be 5° below the
freezing point of the solvent.
2. Rast’s Method
This method is used for the determination of molar masses of
solutes which are soluble in molten camphor. The molal depression
constant of camphor is about 20 times more than that of water. A molal
solution in water thus shows a lowering of 1.86 °C, while in camphor it
is about 40 °C. Because of large lowering of freezing point of camphor
solvent, an ordinary thermometer is suitable to record the temperatures
with sufficient accuracy.Pure camphor is powdered and is taken into a
capillary tube sealed at one end. The tube is then tied up to the
thermometer and heated on a glycerol bath. The temperature at which
the camphor melts is recorded and is taken as the freezing point of
solvent.Now a known weight of solute whose molar mass is to be
determined is mixed with a known weight of camphor (about 10 to 15
times that of solute) and the mixture is melted to get a homogeneous
solution. The mixture is cooled, powdered and then taken into a
capillary tube sealed at one end. The melting point of the mixture is
recorded by adopting the same procedure used for the solvent. This is
taken as the freezing point of the solution. The difference between the
freezing point of solvent and solution is taken as the depression of
freezing point. Substituting this in the equation given under molar mass
of solute can be calculated.
Chemistry - 1
Isotonic   

   Isotonic 
       
        

 
 (m/v) NaCl  

(m/v) NaCl
      


m/vNaCl 


  Reverse Osmosis 
 



            
Reverse Osmosis (RO)
      


Dilute Solutions
1000  K f  w
Molar mass of solute, m = Tf  W
Problem 4 :
20 g of urea is dissolved in 250 g of water. Calculate under
standard pressure the freezing point and boiling point of the solution. Kf
and Kb for water are 1.86 and 0.52 respectively.
Sol. : Weight of solute, w = 20 g

Molar mass of solute (urea), m = 60 g mol–1
Molal elevation constant, Kb = 0.52 K kg mol–1
molal depression constant, Kf = 1.86 K kg mol–1
Boiling point of solution, T = ?
Boiling point of water, T° = 100 °C
1000  Kb  w
Tb =
m W
1000  0.52  20
T – 100 = = 0.693
60  250
Boiling point of solution, T = 0.693 + 100 = 100.693 °C
1000  1.86  20
T= = 2.48
60  250
Freezing point of solution T = –2.48 °C
Problem 5 :
1 g of non-electrolyte solute dissolved in 50 g of benzene
lowered the freezing point of benzene by 0.30 K . Find the molar mass
of the solute.
(given, Kf of benzene = 5.12 K kg mol-1)
Sol. : Depression of freezing point, Tf = 30°C
Molal freezing constant, Kf = 5.12 K kg–1mol–1
Weight of solute, w = 1 g
Chemistry - 1
     

  
       

          

     
     
  

   i
     
i


i


i



i



Dilute Solutions
K f  1000  w
Tf =
m W
5.12  1000  1
0.30 =
m  50
5.12  1000
molar mass of solute, m = = 341.3 g mol–1
0.30  50
5.3.5 Osmosis and Osmotic Pressure
Osmosis
The phenomenon of osmosis (Greek: Osmos means to push)
was first reported by Nollet(1748). It is a spontaneous process, in which
flow of solvent molecules takes place from a pure solvent to a solution
of a solute or a dilute solution to concentrated solution when they are
separated by a semipermeable membrane. This process occurs till the
concentrations of both solutions become equal.
Semipermeable membrane
A membrane that can permit only solvent molecules to pass
through the pores of it but not the solute particles which are relatively
bigger in size is called semipermeable membrane. The best semiperme-
able membrane for solutes of low molar masses in water is a film of
cupric ferrocyanide. It is prepared by contacting a solution of a cupric
salt with potassium ferrocyanide. Thin films of cellulose or cellulose ni-
trate are also used as semipermeable membranes for solutes of high
molar masses in organic solvents. When there is no semipermeable mem-
brane between two solutions of different concentrations then solute flows
from the concentrated solution to dilute solution and solvent flows from
dilute solution to concentrated solution. This kind of flow of solute and
solvent in opposite directions is known as diffusion.
Osmotic Pressure
The external or excess pressure that must be applied to a solu-
tion to stop the process of osmosis i.e., flow of solvent molecules from
pure solvent to a solution or from a dilute solution to a concentrated

Chemistry - 1
i

 
X2 =
  
  
    iCRT
KCl, NaCl, MgSO4, K2SO4,  

‘i’  MgSO4,
NaCl, KCl‘i’K2SO4i

i





, iAX, BY


Ax By 
y
 xA  yB
x
  

   x y

Dilute Solutions
solution when they are separated by a semipermeable membrane is re-
ferred to as the osmotic pressure of the solution. As the concentration of
solute in solution increases, the value of osmotic pressure also increases.
Thus, it also comes under the colligative properties.
The phenomenon of osmosis and osmotic pressure can be un-
derstood easily by the following simple experiment. The apparatus shown
in Fig.5.3.5.consists of a chamber which is divided into two compart-
ments by means of a semipermeable membrane. The left side compart-
ment is fitted with a water tight piston and the right side one with a flow
indicator. The left and right compartments are filled with a solution of a
solute and pure water respectively.
Fig.5.3.5: Osmotic Pressure apparatus
Water immediately tries to flow in to the solution side through

semipermeable membrane due to a phenomenon called osmosis. The
progress of osmosis is known noting decrease in level of water by flow
indicator. To restore the water level sufficient mechanical pressure is to
be applied on the solution.This external pressure applied on the solution
in order to stop the osmosis is equal to the osmotic pressure of the
solution.

Chemistry - 1
 =
  1    x  y
 1  x  y  
 1  (x  y  1)

i =

x+y = n
n =
    i      
 




 

Dilute Solutions
Experimental determination of Osmotic Pressure
Osmotic pressure of a solution is measured by the following
methods:
1. Pfeffer’s method 2.Morse and Frazer’s method 3.Berkeley and
Hartley’s method.
Among these methods let us describe the best method used for
the measurement of the osmotic pressure of the solution i.e., Berkley
and Hartley’smethod.
The apparatus used in Berkley and Hartley’s method is shown
in Fig.5.3.6. It consists of a porcelain tube with copper ferrocyanide
membrane deposited in its walls is enclosed in ametallic jacket. The
porcelain tube is fitted with a reservoir of pure water at one end and a
capillary tube at the other end. The metallic jacket is provided with an
arrangement for applying the external pressure which is measured with a
pressure gauge.
Fig.5.3.6: Measurement of osmotic pressure (Berkeley and Hartley)
The porcelain tube is filled with pure water and the metallic jacket
with the solution whose osmotic pressure is to be determined. Due to
osmosis, the level of the water in the capillary tube comes down.
External pressure is then applied on the solution so that the level of
water in the capillary tube is restored. The pressure recorded by the
pressure gauge gives the osmotic pressure of the solution.

Chemistry - 1
i,  n

  

  n
 
= 1–  + n =1+
n
–
1 
1 + α   1
n 
1 
1     1
i = n 
1
1 
i -1 =    1
n 
i 1
=
1
1
n

Dilute Solutions
Advantages
1. It is a quick and accurate method.
2. The concentration of solution does not change because flow of
solvent is not permitted in to solution; so the results obtained by this
method are reliable.
3. As the osmotic pressure is balanced by the external pressure, there
will be no strain on the membrane and the danger of its bursting is
eliminated. So, this method can be used for determining high
osmotic pressures.
Determination of molar masses of solutes
For dilute solutions, it has been found experimentally that, at a
given temperature osmotic pressure is directly proportional to the
molarity of the solution. If T is the temperature in Kelvin scale and C is
the concentration of solution in moles per litre i.e., molarity of the
solution, then
 = CRT ————(5.3.23)
n
or  = × RT T ————(5.3.24)
V
where, V is the volume of solution in litres containing n moles of solute
and R solution constant. (R value is same as that of the universal gas
constant).If w is the weight of solute in grams and m is its molar mass,
then n=w/m
w
= × RTT ————(5.3.25)
mV
Thus knowing p value from experiment, w, T and V the molar
mass of the solute, m can be calculated.
Problem 6 :
A solution of 0.4 g of a polymer in 1 dm3 of an aqueous solution
has an osmotic pressure of 3.74 torr at 300 K. calculate the molar mass
of the polymer.

Chemistry - 1
Sol. : Osmotic pressure = 3.74 torr
Weight of solute, w = 0.4 g
Volume of solution in litres, v = 1 L
Temperature, T = 300 K
 molar mass of polymer, m = ?
n
= RT
v
3.74 0.4
  0.0821  300
760 m  1
0.4  0.0821  300  760
m= = 2000 g mol–1 = 2 kg mol–1
3.74
Isotonic solutions
Two solutions which have same osmotic pressure at a given
temperature are called isotonic solutions. When such solutions are
separated by a semipermeable membrane osmosis does not occur
between them. If the membrane is completely semipermeable,isotonic
solutions are also called iso-osmotic solutions. The isotonic solutions
have same molar concentrations. For example, the osmotic pressure
associated with the fluid inside the blood cells is isotonic with 0.9%
(m/v)sodium chloride solution, called normal saline solution. In such a
case the cells neither enlarge nor contract as no osmosis takes place.
On the other hand, if we place the blood cells in a solution
containing more than 0.9% (m/v) sodium chloride, water flows out of
the cells. This would result in shrinkage of the cells. In such a case the
solution is said to be hypertonic. If we place the blood cells in a solution
containing less than 0.9% (m/v) sodium chloride solution, water flows in
to the cells. This would result in enlargement of the cells. In such a case
the solution is said to be hypotonic.

Dilute Solutions
Reverse Osmosis
When the pressure applied on the solution is greater than the
osmotic pressure, then the direction of osmosis can just be reversed. In
other words the pure solvent flows out of the solution through the
semipermeable membrane. This phenomenon is known as reverse
osmosis. This technique is of practical value and is very much useful in
the purification and desalination of ground water in the name RO plants
(Reverse osmosis plants).For this purpose a variety of polymer
membranes are available.A film of cellulose acetate placed over a
suitable support is one such membrane commonly used as a
semipermeable membrane, since the pressure required for reverse
osmosis is quite high. The schematic set up involving in reverse osmosis
is shown in Fig.5.3.7.
Fig.5.3.7: Reverse Osmosis occurs when a pressure larger than the osmotic
pressure is applied to the solution
5.3.6 Abnormal colligative properties of solutions

In our previous discussion, while arriving the values of
colligative properties of dilute solutions, it has been assumed that the
molecular form of the solute remains unchanged in the solution. For
solutions of such solutes, the experimentally determined colligative
property values are in good agreement with theoretically calculated
values. We also know that any colligative property value is inversely
related to the molar mass of the solute dissolved in the solution. So for
such solutes,the experimentally determined molar masses are same as

Chemistry - 1
that of theoretically calculated molar masses. However, there are some
solutes which undergo either dissociation or molecular association in
solutions. So, in such cases the number of particles in solutions may be
either higher or lower than expected. As colligative properties depend
on the number of particles in solution, the experimentally determined
colligative property values are not same as that of the theoretically
determined values. The colligative properties of solutes of such solutions
are known as abnormal colligative properties and the molar masses of
solutes obtained from these properties are called abnormal molar masses.
van’t Hoff Factor ( i )

In order to account for the abnormal behaviour of solutions
described above, van’t Hoff introduced a factor called van’t Hoff
factor, i. It is defined as the ratio of the experimental value of the
colligative property to the calculated value of that property when the
solution behaves ideally.
experimental value of colligative property
i=
calculated value of the property, when the solution behaves ideally
Since, the colligative property is directly proportional to the

number of moles of particles of solute in solution, van’t Hoff factor can
also be expressed as
actual number of solute particles in solution
i=
number of solute particles in solution if it behaves ideally
We also know that molar mass of solute is inversely proportional to the

colligative property value. Thus van’t Hoff factor can be expressed as
theoretically calculated molar mass of solute
i=
experimentally determined molar mass of solute
Applying the van’t Hoff factor in the colligative property expressions
already derived,we have

Dilute Solutions
P0  P
1. Relative lowering of vapour pressure, P0 = i × X2
2. Elevation of boiling point,  Tb= I × Kb × molality of solution
3. Depression of freezing point Tf= I × kf × molality of solution
4. Osmotic pressure,  = iCRT
Table 5.3.2 :
‘i’ value for incomplete ‘i’ value for
dissociation complete
Salt
dissociation of
0.1m 0.01m 0.001m
solute
NaCl 1.87 1.94 1.97 2.00
KCl 1.85 1.94 1.98 2.00
MgSO4 1.21 1.53 1.82 2.00
K2SO4 2.32 2.70 2.84 3.00
For strong electrolytes like KCl, NaCl, MgSO4, K2SO4etc.,

the van’t Hoff factor value increases as the concentration of the solution
decreases. The value of ‘i’ approaches to 2 in the case of MgSO4, KCl
and NaCl and for K2SO4 it approaches to 3 as the solution becomes
very dilute. This data is shown in table 5.3.2.
Relation between degree of dissociation (a) and van’t Hoff

factor (i)
The ratio of number of solute molecules dissociated to the total
number of molecules is called degree of dissociation (a).
No. of molecules dissociated
=
Total no. of molecules
To get the relationship between degree of dissociation () and
van’t Hoff factor (i) let us consider an electrolyte of the type AxBy un-
dergoing dissociation as

Chemistry - 1
A xB y xAy+ + yB x–
Initial moles 1 0 0
Number of moles at
1–α xα yα
equilibrium
Where a is the degree of dissociation.
 Total number of moles of particles at equilibrium
= 1–  + x + y
(or) = 1 + x + y –
(or) = 1 +  (x + y – 1)
We know that, van’t Hoff factor,
Total No. of moles of particles after dissociation
i=
No. of moles of particles before dissociation
1    x  y  1
i=
1
  x  y  1
i -1 =
1
i 1

x  y 1
i 1
If x + y = n, then  
n 1
where n = Total no. of ions formed by the electrolyte in solution.
Problem 7: Find the van’t Hoff factor (i) for the electrolyte calcium
nitrate, which is 70% dissociated in aqueous solution.
Solution:
Ca(NO3)2 Ca2++ 2NO3
Initial moles 1 0 0
Number of moles of
1–α α 2α
equilibrium

Dilute Solutions
Total No. of moles of particles after dissociation
= 1 –  +  + 2 = 1 + 2
1  2 1  2  0.7
i= = = 1 + 1.4
1 1
van’t Hoff factor, i = 2.4
Relationship between van’t Hoff factor (i) and degree of associa-
tion ()
The ratio of number of molecules associated to the total number
of molecules is called degree of association ()

Number of molecules associated
=
Total Number of molecules
To derive the relationship between degree of association and
van’t Hoff factor, let us consider n molecules of solute undergoing
association as,
2CH 3COOH (CH 3COOH)2

Initial moles 1 0
Number of moles at 
1–α
equilibrium 2
Total Number of moles of particles after association
  1 
= 1–  + =1+ –=1+α  n  1
n n  
1 
1     1
we know that, van’t Hoff factor, i = n 
1
1 
i -1 =    1
n 
i 1
=
1
1
n

Chemistry - 1
Problem 8:
Calculate the van’t Hoff factor, for the dimerisation of acetic
acid in benzene is 90% associated.
Solution:
2CH 3COOH (CH 3COOH)2
Initial moles 1 0
Number of moles at 
1–α
equilibrium 2

Total No. of moles of particles after association = 1–  +
2
 1 
=1+ –  = 1+    1
2 2 
1 
1     1
i= 2 
1
 1 1
i= 1 +0.9    = 1 – 0.9 × = 1 – 0.45 = 0.55
 2 2
SUMMARY
The properties of dilute solutions which depend on number of

particles of solute and independent of their chemical nature are called
colligative properties. They are lowering of vapour pressure, elevation
of boiling point, depression of freezing point and osmotic pressure. These
four properties of inter related and are very much useful in determining
the molar masses of solutes. The values related to these colligative
properties can be determined by suitable methods meant for them. The
colligative properties related to solutions containing non-volatile,
non-electrolytic solutes are called normal colligative properties. In these
solutions, the solutes do not undergo any change in molecular form.
However with respect to electrolytic solutes which undergo either

Dilute Solutions
dissociation or association the colligative properties are different than
expected. Such properties are called abnormal colligative properties.
As colligative property is inversely proportional to molar mass of a
solute, the molar masses obtained with respect to electrolytic solutes are
called abnormal molar masses. In order to apply colligative properties
to all types of solutes van’t Hoff factor, ‘i’ was introduced.
GLOSSARY
Colligative The properties of dilute solutions

properties: depending number of the particles of
solute
Cryoscopic It is a constant of a solvent. It is the
constant: depression of freezing point caused
due to one molal solution
Ebullioscopic It is a constant of a solvent. It is the
constant: elevation of boiling point caused due
to one molal solution
Freezing mixture: a mixture of ice and NaCl or any other
salt which can provide low
temperatures.
Hypertonic Solution which has more dissolved
solutions: particles (salt and other electrolyte)
Hypotonic Solution which has fewer dissolved
solutions: particles (salt and other electrolyte)
Isotonic solutions : Solutions of same osmotic pressure
Non-electrolyte: substance which does not conduct
electricity either in molten state or
solution state due to absence of ions

Chemistry - 1
Non-volatile solute: which cannot give the vapour readily
at room temperature
Osmosis: the spontaneous process of flow of
solvent molecules from solvent to
solution or form dilute solution to
concentrated solution, when they are
separated by a semipermeable
membrane.
Osmotic pressure: Excess pressure applied on the
solution to stop the osmosis.
Reverse osmosis: It is the flow solvent molecules from
concentrated solution to dilute
solution, when the applied pressure is
greater than osmotic pressure.
Semipermeable A membrane which can selectively
membrane: allow the solvent particles and
prevent solute particles through the
pores of it.
Van’t Hoff factor: It is a correction factor used to
correct the abnormal colligative
properties or abnormal molar masses
of solutes.
1. Which of the following is not 2. Solute particles in solvent

a colligative property? and nature of the solute
1. Lowering of vapour 3. Solute particles and nature
pressure of solute and solvent
2. Freezing point 4. Solute part icles,
3. Elevation of boiling point irrespective of the nature of
4. Osmotic pressure the solute and solvent
2. Colligative properties mainly 3. 1.8 g of glucose is dissolved in
depend on the relative number 180 g of water. The vapour
of pressure of the solution at
1. Solute particles in solution 100°C is
and nature of the solvent
Dilute Solutions
1. 760 mm 1. Kohlraush law
2. 767.6 mm 2. Raoult’s law
3. 759.24 mm 3. Henry’s law
4. 752.40 mm 4. Ostwald’s law
4. The mass of a non-volatile, non 8. The boiling point of ethanol is
electrolyte solute (molar mass 78 °C and molar heat of
50 g mol-1) needed to be dis- vapourisation Hvap is 39.42 kJ
solved in 114 g octane to re- mol-1. The ebullioscopic con-
duce its vapour pressure to stant for ethanol in K.Kg. mol-
1
75% is is
1. 75 g 2. 175 g 1. 1.195
3. 150 g 4. 100 g 2. 11.95
5. The vapour pressure of pure 3. 2.626
benzene at temperature T (K) 4. 0.52
is 640 mm Hg. A non-volatile, 9. Which of the following solu-
non electrolyte solid weighing tions boil at the highest tem-
20 g is added to 39 g of ben- perature?
zene. The vapour pressure of 1. 0.1 M urea
solution is 600 mm Hg. The 2. 0.1 M Ca (NO3)2
molar mass of solid substance 3. 0.1 M Al(NO3)3
in g mol-1 is 4. 0.1 M Sucrose
1. 64 2. 70 10. 13.44 g of freshly prepared
3. 56 4. 128 CuCl2 (molar mass 134.4 g
6. Identify the aqueous solution, mol-1) is added to 1 kg of wa-
which has lowest vapour pres- ter. The elevation in boiling point
sure from the following of water is around (Given Kb
1. 0.1 m BaCl2 of water = 0.52 K Kg mol-1)
2. 0.1 m urea 1. 0.1 2. 0.05
3. 0.1 m Na3PO4 3. 0.16 4. 0.21
4. 0.1 m Na2SO4 11. When 1.8 g of a non-volatile
7. The relative lowering of vapour solute is dissolved in 90 g of
pressure is equal to the mole benzene, the boiling point is
fraction of the non-volatile sol- raised to 354.11K. if Kb of
ute. This is called benzene is 2.53 K Kg mol-1,

Chemistry - 1
the molar mass of the solute in 15. The elevation in boiling point of
g mol-1 is water produced by dissolving
1. 38 2. 48 1.17 g NaCl in 100 g water (Kb
3. 58 4. 68 = 0.52 k Kg mol-1) is (Assume
12. 1 mole of glucose is dissolved that NaCl undergoes complete
in 1000 g of water. The change dissociation)
in boiling point of water is (Kb 1. 0.104 K
of water = 0.52 K Kg mol-1) 2. 0.208K
1. 100.51° C 3. 0.312 K
2. 100.52 °C 4. 0.416 K
3. 0.52 °C 16. Which of the following exhib-
4. 1.04 °C its the highest freezing point
13. 1.0 g each of urea, glucose, lowering?
glycol (molar mass 62 g mol-1) 1. 0.1 mol Kg-1 NaCl
and sucrose have been dis- 2. 0.1 mol Kg-1 CaCl2
solved in 0.1 kg H2O. Which 3. 0.1 mol Kg-1 CH3COOH
of the following solution will 4. 0.1 mol Kg-1 CH3COONa
have the highest boiling point? 17. Arrange the following aqueous
1. Urea solutions in the increasing or-
2. Glucose der of freezing point. I. 0.1
3. Glycol molal Ca3(PO4)2 II. 0.1 molal
4. Sucrose Na2SO4 III. 0.1 molal glucose
14. 5.0 g of a non-volatile 1. I > II > III
substance is dissolved in 250 g 2. I > III > II
of water. If the molar mass of the 3. II > III > I
substances is 140 gmol–1, the 4. III > II > I
elevation in boiling point of 18. The freezing point of a 0.05
water is(vapH = 40.66 kJ mol- molal solution of a non electro-
1
) lyte in water is (Kf of H2O) =
1. 0.0734°C 1.86KKgmol-1)
2. 0.734°C 1. –1.86°C
3. 7.34°C 2. – 0.93°C
4. 0.367°C 3. –0.093°C
4. 0.93°C

Dilute Solutions
19. Elevation in the boiling point of 3. M/10 BaCl2
1 molal solution of glucose is 4. M/10 glucose
2.0 K. The depression in the 23. The osmotic pressure of a so-
freezing point for 2.0 molal solution is given by the relation
lution of glucose in the same 1.  = RT/C
solvent is 2 K. The Kf and Kb 2.  = CT/R
is related as 3.  = RC/T
1. Kb = 1.5 Kf 4. /C = RT
2. Kb = 0.5 Kf 24. 0. 6 g of a solute is dissolved
3. Kb = Kf in 0.1 L of a solvent, which
4. Kb = 2 Kf develops an osmotic pressure
20. Camphor is used as a solvent of 1.23 atm at 27 °C. The
for determining the molecular molar mass of the solute is
weight of a non-volatile solute 1. 150 g mol-1
by Rast method because cam- 2. 120 g mol -1
phor 3. 430 g mol-1
1. Is readily available 4. 240 g mol-1
2. Is volatile 25. The molar mass of a solute ‘X’
3. has high molal depression in g mol-1, if it’s 1%(w/V) so-
constant lution is isotonic with a 5% (w/
4. Is a solvent for organic V) solution of sucrose is
substances 1. 68.4 2. 34.2
21. The inorganic precipitate which 3. 136.2 4. 171.2
acts as a semi permeable mem- 26. Osmotic pressure of the solu-
brane is — tion can be increased by
1. Calcium sulphate 1. increasing the volume of the
2. Barium oxalate vessel
3. Nickel sulphate 2. increasing the temperature
4. Copper ferrocyanide of the solution
22. Which one of the following 3. diluting the solution
solutions would have the high- 4. decreasing the temperature
est osmotic pressure? of the solution
1. M/10 NaCl 27. The degree of dissociation ()
2. M/10 urea of weak electrolyte AxBy is

Chemistry - 1
related to van’t Hoff factor (i), 29. The van’t Hoff factor for 0.1
by the expression: m Ba(NO 3) 2 solution is
i 1 2.74.The degree dissociation,
1.  =  x  y  1 () is
1. 91.3% 2. 87%
i 1 3. 100% 4. 74%
2. =
x  y 1 30. 2.0 g of benzoic acid dissolved
x  y 1 in 25 g of benzene shows a
3. = depression of freezing point
i 1
equal to 1.62 K. If the acid
x  y 1
4. = undergoes dimerisation in ben-
i 1
zene , it’s percentage associa-
28. K2HgI4 is 40% ionised in aque-
tion is approximately (Kf of
ous solution. The value of its
benzene = 2.53 K Kg mol-1)
van’t Hoff factor (i) is
1. 25% 2. 50%
1. 1.6 2. 1.8
3. 75% 4. 80%
3. 2.2 4. 2.0
True or False
1. Boiling point is a colligative

[ ]
property [ ]
5. Colligative property is inversely
2. The freezing point and boiling
proportional to the number of
point of solution are less as
solute particles [ ]
compared to that of a pure 6. 2% (w/v) solution of sucrose
solvent. [ ] and 2% (w/v) solution of
3. Out of 0.5M and 0.05 M glucose have same relative
lowering of vapour pressure.
solution, 0.05 M solution has [ ]
the least value of DTf [ ] 7. The value of observed
4. In case of association, the molecular weight is always less
than its normal value of the
van’tHoff factor, (i) for an
solute which undergoes
electrolyte is more than one
Dilute Solutions
dissociation in the solvent. BaCl2 solution has the highest
[ ] osmotic pressure. [ ]
8. Depression of freezing point is 10. Osmotic pressure is the excess
a colligative property but not pressure which is applied on
the freezing point. [ ] the solution side to check the
9. Out of 0.1 M BaCl2 and osmosis. [ ]
0.1M NaCl solution, 0.1M
KEY
Multiple choice Questions
1. 2 2. 4 3. 3 4. 3 5. 1 6. 3
7. 2 8. 1 9. 3 10. 3 11. 3 12. 3
13. 1 14. 1 15. 2 16. 2 17. 4 18. 3
19. 4 20. 3 21. 4 22. 3 23. 4 24. 2
25. 1 26. 4 27. 1 28. 2 29. 2 30. 2
True or False
1. F 2. F 3. T 4. F 5. F
6. F 7. T 8. T 9. T 10. T
Why do fresh eggs sink, and rotten eggs float?

A classical trick to know whether we can still eat an egg (if they are
fresh enough) is putting them in a bowl of water. If the egg sinks, it
means that it is still denser than water, which is the natural state if
they are still fresh. As decomposition takes place, solid and liquid
matter is transformed into gas. Gaseous pressure builds up, and
since the egg shell is porous, this gas starts escaping. This loss of
mass, eventually leads to the density of the egg being lower than
water’s. This makes the egg float. This represents an easy way to
tell if an egg has undergone too much decomposition to be eaten (if
it is rotten).

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PROGRAMME: THREE-YEAR B.Sc. (B.

Group 13: Preparation & structure of Diborane, Borazine

Suggested Co-curricular activities and Assessment Methods

Chemistry Curiosity Corner

Is there any liquid metal at room temperature?

Yes. The only metal liquid at room temperature is mercury.

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 2

The elements of long form of periodic table have been classified

     

Table 1.1-List of p-block elements

In this unit we will discuss the methods of preparation, properties,

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 5

Ether 2B2H6 + 3Na[AlF4]

  Cu-Al 

    

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 6

UNIT - 1 Group 13 Elements

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 7

    

2NaBH4 + 2HCl B2H6 + 2NaCl + 2H2

B2H6 + 2KOH +2H2O 2KBO2 + 6 H2

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 8

Methods of preparation of diborane

1. By the reduction of boron trifluoride with lithium aluminium hydride

Ether 2B2H6 + 3Li[AlF4]

Ether 2B2H6 + 3Na[AlF4]

2. By the reduction of boron trichloride with ionic hydrides like sodium

3. By the reduction of boron trichloride with hydrogen either in the

4. By the reduction of sodium borohydride with iodine in the presence

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 9

B2H6 + 2 NaH 2Na[BH4]

        

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 10

5. By the action of hydrochloric acid on alkali metal borohydrides.

2LiBH4 + 2HCl B2H6 + 2LiCl + 2H2

2NaBH4 + 2HCl B2H6 + 2NaCl + 2H2

1. Diboraneis a colourless inflammable gas and is highly toxic.

2. It is stable at low temperatures in the absence of moisture and grease.

1. Diboraneon reaction with dry air or oxygen forms boron trioxide. It

B2H6 + 3O2 B2O3 + 3H2O H= -2165 kJ.mol-1

2. Diborane undergoes hydrolysis readily with water or aqueous alkali.

B2H6 + 6H2O 2H3BO3 + 6H2

B2H6 + 2KOH +2H2O 2KBO2 + 6 H2

3. Diborane on reaction with hydrogen chloride forms chloro diborane,

B2H6 + HCl B2H5Cl + H2

4. Diborane on reaction with chlorine at 298K forms boron

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 11

5. Diborane forms complex metal borohydrides with lithium

B2H6 + 2 LiH 2Li[BH4]

B2H6 + 2 NaH 2Na[BH4]

6. Diborane on reaction with ammonia form different products under

a) Diborane with excess of ammonia at low temperature forms an

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 13

   

Diborane is an electron deficient compound. It has only 12 valence

In order to explain the bonding with the available 12 valence

Diborane is a non-planar molecule. In this two BH2 groups lie in

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 15

APSCHE - I SEMESTER CHEMISTRY TEXT BOOK 16