Chemistry Chemical Ionic Equilibrium and Chemical Thermodynamics

XI MODULE - VI
CHEMICAL & IONIC EQUILIBRIUM

AND
CHEMICAL THERMODYNAMICS
Modus Operandi for Practice
(Suggested Ideal Approach)
Step – I CatalyseR 's Practice Sheets & NCERT

{while Chapter is running in Class-Room}
(Mandatory)
Step – II
CatalyseR 's Module
(Mandatory)
Step – III Previous Years’ JEE Subjective & Objective Questions,

R C Mukherjee solved and unsolved questions
(Mandatory)
Step – IV After Completion of Step – III, if time permits, students can

solve questions from previous year’s INCHO, NCHO, KVPY
(Optional) papers, Physical chemistry books by Atkins, Bruce H. Mahan
This Study Package is Prepared by

d`fr
o f Ca talyseR
on te nt Wing
C
ELECTROSTATICS 1
CHEMICAL EQUILIBRIUM
INDEX
 CONCEPTS IN BRIEF (Chemical Equilibrium) 1 – 23
 EXERCISE # 01 OBJECTIVE EXERCISE 24 – 29

 EXERCISE # 02 ADVANCED EXERCISE 30 – 33
 EXERCISE # 03 SUBJECTIVE EXERCISE (LEVEL # 01) 34 – 35

 EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS 36
 EXERCISE # 06 JEE (MAIN) CORNER 37
 EXERCISE # 07 JEE (ADVANCED) CORNER 38 – 39
 ANSWER KEYS 40 – 41
WEIGHTAGE OF ‘CHEMICAL EQUILIBRIUM’ IN JEE (MAIN & ADVANCED) in Last Three Years
JEE (MAIN) Formely known as AIEEE
MARK /
YEAR No. Of Qs.
CHEMISTRY TOTAL MARKS
2014 1 4/120
2015 0 0/120
2016 0 0/120
JEE (ADVANCED)
MARK /
YEAR No. Of Qs.
2014 0 0/120
2015 1 4/168
2016 2 6/124
Nothing is impossible, the word itself says ‘I’m possible’!

CHEMICALEQUILIBRIUM 1
CHEMICAL EQUILIBRIUM
INTRODUCTION
In this chapter, the extent of completion of the reaction is studied

i.e. ” How far a reaction will go” can be predicted.
Practically it is observed that many reactions never go to completion i.e. Product is formed and
some unreacted reactant is left. The resulting mixture contains both reactant and product.
When such a stage is reached during the reaction where composition of the system is fixed then
it is said in chemical language that the reaction has attained the state of equilibrium.
At equilibrium both the forward and backward reactions occur at equal speeds. The study of equi-
librium has great application in industrial processes for those chemical reactions which attain
equilibrium during the course of reaction.
Pt-gauge
eg. 2SO2 + O2 2SO3
V 2O5
[Contact Process for manufacture of H2SO4]
Equilibrium
Physical Chemical
Equilibrium Equilibrium
Equilibrium in physical Equilibrium in chemical
process is called physical process is called chemical
equilibrium. equilibrium.
For example For example

phase changes like H2 (g) + Cl2(g) 2HCl(g)
H2 O(l) H2O(g) ;
Solvation like
H2 O
NaCl(s) NaCl(aq)
excess
TYPE OF CHEMICAL REACTION
Irre ve rsi bl e re a ctio n Re ve rsib le re a ctio n

1 The reac tion whic h proc eeds in one direc tion (forward 1 The reac tion whic h proc eed in bot h the direc t ion under the
direc tion) only . s am e s et of ex perim ental c onditions .
2 Reac tants are alm os t c om plet ely c onverted into 2 Reac t ants form produc ts and produc ts als o reac t t o form
produc ts . P roduc t s do not reac t to form reac t ants again. reac tants in bac k ward direc tion. Thes e are pos s ible in
c los ed ves s els .
3 Do not attain equilibrium s t ate. 3 A t tain the equilibrium s tate and never go to c om plet ion.
4 S uc h reac t ion s are repres ented by s ingle arrow { } 4 Repres ented by double arrow ( ) or ( )
5 E x am ples – 5 E x am ples :–
(a) P rec ipitation reac tions e.g. (a) Hom ogeneous reac t io ns - only one p has e is pres ent
NaCl(aq) + A gNO 3 (aq)  NaNO 3 (aq) + A gCl  (i) G as eo us p has e–
(b) Neutraliz ation reac tions e.g H 2 (g ) + I2 (g ) 2HI(g )
HCl(aq) + N aO H (aq)  NaC l(aq) + H 2 O N 2 (g ) + O 2 2NO (g ) [ B irk lan d ey d e p ro c es s (HN O 3 )]
(c ) N 2 (g ) + 3H 2 (g ) 2NH 3 (g ) (Haeb er’s p ro c es s )
2K ClO 3   2K Cl + 3O 2
(ii) Liq uid p has e
(d) Reac tions in open ves s el : – CH 3 C O O H( ) + C 2 H 5 O H(l) CH 3 CO O C 2 H 5 ( )+ H 2 O (
E ven a revers ible reac tion will bec om e irrevers ible if it is
(iii) S o lid p has e
c arried out in open ves s el. E x .
C (D iam o nd ) C (G rap hite)
CaCO 3 (s ) CaO (s ) + CO 2 (g) Open Het ero g eneo us reac tio ns – M o re t han o ne p has es are p res ent
NH 4 HS (s ) N H 3 (g) + H 2 S (g) v e ss e l (b) CaC O 3 (s ) C aO (s ) + CO 2 (g )
NH 4 H S (s ) NH 3 (g ) + H 2 S (g )
C lo se d
ve s s e l
“Don’t quit, Suffer now & live the rest of your life as a Champion!”
STATE OF EQUILIBRIUM
It has generally been observed that many changes (physical and chemical) do not proceed
to completion when they are carried out in a closed container. Consider for example vapourisation
of water,
Water Vapour
At any temperature, vapourisation of water takes place, initially the concentration of water is
much greater than the concentration of vapour, but with the progress of time, concentration
of vapour increases whereas that of water remains constant and after a certain interval of time,
there is no change in concentration of vapour, this state is known as state of physical equilibrium.
In a similar way, this has also been found for chemical reactions, for example, when PCl5(g)
is heated in a closed container, its dissociation starts with the formation of PCl3(g) and Cl2(g).
Initially, only PCl5(g) was taken, but with the progress of reaction, PCl3(g) and Cl2(g) are formed
due to dissociation of PCl5(g). After a certain interval of time, the concentration of PCl5(g), PCl3(g)
and Cl2(g) each becomes constant. It does not mean that at this point of time, dissociation
of PCl5(g) and its formation from PCl3(g) and Cl2(g) has been stopped. Actually the rate of dissociation
of PCl5 and the rate of formation of PCl5(g) becomes equal. This state is called the state of
chemical equilibrium. So, the state of chemical equilibrium is dynamic.
PCl5  g  PCl 3 g   Cl 2 g 
This can be shown graphically.
Equilibrium
Forward
reaction
Rate of reaction
Concentration
State of equilibrium
Backward
reaction
Reactant
Time Time
So, “state of chemical equilibrium can be defined as the state when the rate of forward reaction
becomes equal to rate of reverse reaction and the concentration of all the species becomes
constant”.
LAW OF MASS ACTION
Guldberg and Waage in 1807 gave this law and according to this law, “At constant
temperature, the rate at which a substance reacts is directly proportional to its active mass
and the rate at which a chemical reaction proceeds is directly proportional to the product
of active masses of the reacting species”.
The term active mass of a reacting species is the effective concentration or its activity (a)
which is related to the molar concentration (C) as
a = f C
where f = activity coefficient. f  1 but f increases with dilution and as V   i.e. C 
0, f 1 i.e., a  C. Thus at very low concentration the active mass is essentially the
same as the molar concentration. It is generally expressed by enclosing the formula of the
reacting species in a square bracket.
To illustrate the law of mass action, consider the following general reaction at constant
temperature,
aAg   bB g  cCg   dDg 
Applying law of mass action,

Rate of forward reaction,
Rf  [A]a [B]b
or Rf = kf[A]a[B]b …(i)
Where kf = rate constant of forward reaction
Similarly,
Rate of reverse reaction
Rr  [C]c [D]d
or Rr = kr[C]c [D]d …(ii)
where kr = rate constant of reverse reaction.
At equilibrium,
Rate of forward reaction = Rate of reverse reaction
i.e., Rf = Rr
So, from equations (i) and (ii), we get
kf[A]a [B]b = kr[C]c[D]d
k f [C]c [D]d
or, 
k r [A]a [B]b
kf [C]c [D]d
or  Kc 
kr [A]a [B]b
Where, Kc is the equilibrium constant in terms of molar concentration.
Equilibrium Constant (Kp) in terms of Partial Pressures: Consider the same general
reaction taking place at constant temperature,
aA(g) + bB(g) cC(g) + dD(g)
[C]c [D]d
From law of mass action, K c  …(1)
[A]a [B]b
n
From ideal gas equation, PV = nRT or, P RT
V
n
At constant temperature, P 
V
Thus, we can say in a mixture of gases, Partial pressure of any component (say A)
PA  [A]
Similarly, PB  [B]
PC  [C]
PD  [D]
PCc  PDd
So, equation (1) can be rewritten as, Kp  …(2)
PAa  PBb
RELATIONSHIP BETWEEN KP AND KC
From the above, for the same general reaction at constant temperature.
[C]c [D]d
Kc  …(1)
[A]a [B]b
PCc  PDd
and, Kp  …(2)
PAa  PBb
From the ideal gas equation, PV = nRT
n
P RT
V
So, PB = [B]RT ; PD = [D]RT
Similarly, PA  [A]RT; PC  [C]RT
Substituting the values of PA, PB, PC and PD in equation (2), we get
[C]c (RT)c  [D]d (RT)d [C]c [D]d (RT)(c d)

Kp  or Kp   or K p  K c  (RT) n
[A]a (RT)a  [B]b (RT) b [A]a [B]b (RT)(a  b)
Where, n = (c + d) – (a + b)
i.e., n = sum of no. of moles of gaseous products – sum of no. of moles of gaseous
reactants.
If n  0, Kp  Kc
If n = 0, Kp = Kc
and if n  0, Kp  Kc
REACTION QUOTIENT (Q) :
At each point in a reaction, we can write a ratio of concentration terms having the same form as the
eqbm constant expression. This ratio is called the reaction quotient denoted by symbol Q.
It helps in predicting the direction of a reaction.
[C]c [D] d
The expression Q = at any time during reaction is called reaction quotient.
[ A ]a [B]b
eg. 2A + B C+D
[C][D]
Q C = Reaction quotient in terms of concentration QC =
[ A ]2 [B]
[C] e [D] e
KC = [Here all the conc. are at equilibrium]
[ A ] 2e [B] e
IMPORTANT :
(i) if Q > Kc reaction will proceed in backward direction until equilibrium in reached.
(ii) if Q < Kc reaction will proceed in forward direction until equilibrium is established.
(iii) if Q = Kc Reaction is at equilibrium.
CHARACTERISTICS OF EQUILIBRIUM CONSTANT & FACTORS AFFECTING IT:
(i) Equilibrium constant does not depend upon concentration of various reactants, presence
of catalyst, direction from which equilibrium is reached
(ii) Equilibrium constant is only dependent upon the temperature.
It means kp and kc will remain constant at constant temperature no matter how much changes are
made in pressure, concentration, volume or catalyst.
But kx depends on pressure provided Dn ¹ 0, i.e. even at constant temperature, kx will undergo a
change by the change in total pressure at equilibrium.
For example, (i) PCl5 PCl3 + Cl2, Dn = 1
Dn
kp = kx(P) = kx(P)
Now at constants temperature, if pressure is increased,
kx decreases [Since, kp remains constant]
Similarly,
(ii) N2 + 3H2 2NH3 ; Dn = 2 – 1 – 3 = –2
 Kp = Kx (P)–2
In this case, if pressure is increased, keeping temperature constant, kx will increase. Then only kp
remains same.
* However if temperature is changed,
k2 H 1 1
log =    ; DH = Enthalpy of reaction
k1 2.303 R  T1 T2 
If T2 > T1 then K2 > K1 provided DH = +ve (endothermic reaction)
K2 < K1 if DH = –ve (exothermic reaction)
In the above equation, the unit of R and DH should be same.
(iii) K depends on the stoichiometry of the reaction also.
If two chemical reactions at equilibrium having equilibrium constants K1 and K2 are added
then the resulting equation has equilibrium constant K = K1 . K2
Equation constant
A B K1
B C K2
On adding A C K = K1 . K 2
(b) If the reaction having eq. constant K1 is reversed then resulting equation has eq. constant
1
K1
A+B C+D
1
On reversing, C+D A+B K= K
1
(c) If a chemical reaction having equilibrium constant K1 is multiplied by a factor n then the
resulting equation has equilibrium constant K = (K1)n , n can be fraction
Eg. D2 2A K1
 1 1
Multiplying by   , D A K = (K1)1/2 = K1
2 2 2
HOW TO USE NEGLECTION IN THE PROBLEM:
[Pr oduct]
K=
[Re ac tan t]
Case .I
If K is large (k > 103) then product concentration is very very larger than the reactant
([Product] >>[Reactant]) Hence concentration of reactant can be neglected with respect to the
product. In this case, the reaction is product favourable and equilibrium will be more in forward
direction than in backward direction.
Case.II
If K is very small (K < 10–3)
[Product] << [Reactant]
Hence concentration of Product can be neglected as compared to the reactant.
In this case, the reaction is reactant favourable.
Example 1:
Calculate the Kc and Kp for the following reactions and also deduce the relationship
between Kc and Kp
1 3
(i) 2SO2(g) + O2(g) 2SO3(g) (ii) N 2 g   H 2  g  NH3 g 
2 2
Solution:
(i) 2SO2(g) + O2(g) 2SO3(g)
Applying law of mass action,
[SO3 ]2
Kc  …(i)
[SO2 ]2 [O 2 ]
2
PSO 3
Kp  2 …(ii)
PSO 2
 PO2
We know that
K p  K c (RT)n
Kc
n = 2 – (2+1) = – 1  K p 
RT
1 3
(ii) N 2 g   H 2 g  NH3 g 
2 2
[NH3 ]
Kc  …(i)
[N 2 ]1/ 2 [H 2 ]3/ 2
PNH3
Kp  …(ii)
PN1/22  PH3/2 2
n
Now, K p  K c (RT)
3 1
n  1      1
2 2
Kc
Kp 
RT
Example 2:
At 400K for the gaseous reaction
2A + 3B 3C + 4D
the value of Kp is 0.05. Calculate the value of Kc (R = 0.082 dm3 atm K–1mol–1)
Solution:
From the given data
For the reaction 2A + 3B 3C + 4D
n = (3 + 4) – (2 +3) = 2
Since R is given in dm3 atm. K–1 mol–1, we shall take P = 1 atm.
Substituting these values in the equation
n 2
 CRT   1  0.082  400 
K p  Kc   , we get 0.05  K c  
 P   1 
0.05
Kc  Kc = 4.648 × 10–5
0.082  0.082  400  400
Example 3:
(i) The vapour density of a mixture consisting of NO2 and N2O4 is 38.3 at 26.7°C.
Calculate the number of moles of NO2 in 100 gm mixture.
(ii) Establish a relationship between Kc and Kp for the following reactions.
(a) N2(g) + O2(g) 2NO(g)
(b)  NH 4 2 CO3s  2NH3 g   CO2 g   H2Og 
Solution:
Dd
(i) N2O4 2NO2 =
d
46  38.3
t=0 1.087 0 = = .2 (20%)
38.3
t = teq 1.087 (1 –) 1.087 × 2
 n NO = 1.087 × 0.4 = 0.435

2
(ii) (a) ng = 0  Kp = Kc

(b) ng = 4  Kp = Kc (RT)4
APPLICATION OF LAW OF MASS ACTION
1. Synthesis of Hydrogen Iodide:

Suppose ‘a’ moles of H2 and ‘b’ moles of I2 are heated at 444°C in a closed container of
volume ‘V’ litre and at equilibrium, 2x moles of HI are formed.
H2(g) + I2(g) 2HI(g)
a b
Initial concentration (mol L–1) 0
V V
ax bx 2x
Equilibrium concentration(mol L–1)
V V V
[HI]2
Kc  …(i)
[H 2 ][I 2 ]
Substituting the equilibrium concentrations of H2, I2 and HI in equation (i), we get
2
 2x 
  4x 2
Kc   V 
 a  x  b  x  (a  x)(b  x) …(ii)
  
 V  V 
2
PHI
Kp  …(iii)
PH 2  PI2
Suppose the total pressure of the equilibrium mixture at 444°C is P, then

PHI = mole fraction of HI × Total pressure
2x
PHI = P
ab
Similarly,
(a  x) bx
PH2   P and PI2  P
(a  b) (a  b)
Substituting these values in equation (iii) we get
2
 2x  2
  P
Kp  ab
ax bx
 P  P
ab  ab
4x 2
 Kp  …(iv)
(a  x)(b  x)
So, one can see from equations (iii) and (iv), that
Kp = Kc
This is so, because n= 0 for the synthesis of HI from H2 and I2.
2. Thermal Dissociation of Phosphorus Pentachloride
PCl5(g) dissociates thermally according to the reaction,

PCl5(g) PCl3(g) + Cl2(g)
Let us consider that 1 mole of PCl5 has been taken in a container of volume V litre and at
equilibrium x moles of PCl5(g) dissociates. Thus
Initial concentration (mol L–1) 1 0 0
1 x x x
Equilibrium concentration(mol L–1)
V V V
According to law of mass action, at constant temperature,
[PCl3 ][Cl2 ]
Kc = …(1)
[PCl5 ]
PPCl3  PCl2
and Kp = PPCl5 …(2)
Substituing the values of equilibrium concentration, in equation (1), we have

x x

x2
Kc = V V or Kc 
1 x V(1  x)
V
Now, total number of moles at equilibrium = 1 – x + x + x = 1 + x
x
Mole fraction of PCl3 = Mole fraction of Cl2 =
1 x
1 x
and mole fraction of PCl5 =
1 x
Suppose total pressure at equilibrium is P, then we have from equation (2),
x x 2
 P
Kp  1  x 1  x x2P
1 x or Kp 
P (1  x 2 )
1 x
Similarly, we can apply law of mass action on any reaction at equilibrium.
Example 4:
Derive an expression for Kc and Kp for the reaction
N2(g) + 3H2(g) 2NH3(g)
Assuming that in a container of volume V, initially 1 mole of N2 and 3 moles of H2
were taken and at equilibrium 2x moles of NH3 is formed.
Solution:
N2 + 3H2 2NH3
t=0 1 3 –
t = teq 1–x 3 – 3x 2x = 4 – 2x
(2x) 2 x 2V 2
 Kc = 2
×V =
(1  x) (3  3x)3 27(1  x ) 4
(2 x)2 (4  2 x) 2 16 x 2 (2  x ) 2
Kp = × =
(1  x) (3  3x)3 P2 27(1  x ) 4 P 2
Example 5:
The degree of dissociation at a certain or given temperature of PCl5 at 2 atm is
found to be 0.4. At what pressure, the degree of dissociation of PCl5 will be 0.6 at
the same temperature? Also calculate the equilibrium constant for the reverse
reaction.
Solution:
The dissociation of PCl5 takes place according to the equation,
PCl5 PCl3(g) + Cl2(g)
Let 1 mole of PCl5 is taken in a closed container. Then
Mole(s) before dissociation 1 0 0
Mole(s) at equilibrium 1 –   
As degree of dissociation() is given at 2 atm
1 –  = 1.0 – 0.4 = 0.6
 Total moles at equilibrium = 1 –  +  +  = 1 – 0.4 + 0.4 + 0.4 = 1.4
0.4 0.4
PPCl3  PCl2  2 2
Kp  1.4 1.4
Now, =
PPCl5 0.6
2
1.4
0.4  0.4  4  1.4 0.32
Kp  
0.6  2  1.4  1.4 0.84
Now, as temperature remains the same, Kp will also remain the same. So for
 = 0.6
Mole before dissociation 1 0 0
Moles at equilibrium 1 – 0.6 0.6 0.6
0.6 0.6
  P2 0.6  0.6  1.6
Again, K p  1.6 1.6  Kp  P
0.4 0.4  1.6  1.6
P
1.6
32 9 32  4 128
 P  P =  = 0.677 atm
84 16 9  21 189
Example 6:
(i) Calculate the percentage dissociation of H2S(g), if 0.1 mole of H2S is kept
in 0.4 litre vessel at 1000K. For the reaction,
2H2S(g) 2H2(g) + S2(g), the value of Kc = 1.6 × 10–6
(ii) A sample of HI was found to be 22% dissociated when equilibrium was
reached. What will be the degree of dissociation if hydrogen is added in
the proportion of 1 mole for every mole of HI originally present, the
temperature and volume of the system being kept constant?
Solution:
(i) 2H2S(g) 2H2 + S2(g) Kc = 1.6 × 10–6
t=0 0.1 – –
t = teq 0.1 – x x x/2
value of Kc suggest that (0.1 – x) ~
= 0.1
x3 1
 
2 0.4
= 1.6 × 10–6  x = 2.34 ×10–3
2(0.1)
2.34 10 3
 = × 100 = 2.34%
0.1
(ii) 2HI H2 + I2
t=0 1 – –
t = teq 1–  /2 /2 since  = 0.22
(0.11) 2 1
 Kc = 2 = 64
(0.88)
now 2HI H2 + I2
t=0 1 1 0
t = teq 1–  /2 /2
1 (1   / 2).( / 2) 2   2
= =
64 (1   ) 2 4(1   ) 2
 4 + 42 – 8 = 128 + 642
 602 + 136 – 4 = 0   = 0.29
EQUILIBRIUM CONSTANT FOR HETEROGENEOUS EQUILIBRIA
The equilibrium which involves reactants and products in different physical states. The law
of mass action can also be applied on heterogeneous equilibria as it was applied for
homogeneous equilbria (involving reactants and products in same physical states).
(i) Thermal Dissociation of Solid Ammonium Chloride:
The thermal dissociation of NH4Cl(s) takes place in a closed container according to the
equation:
NH4Cl(s) NH3(g) + HCl(g)
Let us consider 1 mole of NH4Cl(s) is kept in a closed container of volume ‘V’ litre at
temperature TK and if x mole of NH4Cl dissociates at equilibrium, then
NH4Cl(s) NH3(g) + HCl(g)
Initial moles 1 0 0
Moles at equilibrium 1 – x x x
[NH3 ][HCl]
Applying law of mass action, K c 
[NH 4 Cl]
As NH4Cl is a pure solid, so there is no appreciable change in its concentration. Thus,
Kc = [NH3] [HCl]
x x x2
Kc   
V V V2
and K p  PNH3  PHCl
(ii) Thermal Dissociation of Ag2CO3:

Ag2CO3(s) dissociates thermally according to the equation.
Ag2CO3(s) Ag2O(s) + CO2(g)
Applying law of mass action, at constant temperature, we get,
[Ag 2O][CO2 ]
Kc 
[Ag 2 CO3 ]
Now, let us consider that 1 mol of Ag2CO3(s) is heated in a closed container of volume V
and x mol of Ag2CO3(s) dissociates at equilibrium, then
Ag2CO3(s) Ag2O(s) + CO2(g)
Initial moles 1 0 0
Equilibrium moles 1 – x x x
Now, as Ag2CO3 and Ag2O are solids, so their concentration can be assumed to be constants
thus
x
K c  [CO 2 ] 
V
K P  PCO2
THE LE - CHATELIER’S PRINCIPLE
This principle, which is based on the fundamentals of a stable equilibrium, states that
“When a chemical reaction at equilibrium is subjected to any stress, then the
equilibrium shifts in that direction in which the effect of the stress is reduced”.
Confused with “stress”. Well by stress here what we mean is any change of reaction conditions
e.g. in temperature, pressure, concentration etc.
This statement will be explained by the following example.
Let us consider the reaction: 2NH3 (g) N2 (g) + 3H2 (g)
Let the moles of N2, H2 and NH3 at equilibrium be a, b and c moles respectively. Since
the reaction is at equilibrium,
3 3
 
PN 2  PH 2 X N 2 .PT  X H 2 .PT 
2 = Kp = 2
P NH 3 X NH3 .PT 
Where,
X terms denote respective mole fractions and PT is the total pressure of the system.
3
 a   b 
  PT    PT 
abc  a bc  K
 2 p
 c 
  PT 
a bc 
a
Here, = mole fraction of N2
a bc
b
= mole fraction of H2
a bc
c
= mole fraction NH3
a bc
2
ab3  PT 
 2
 2 = Kp
c a  b  c
 a  b  c  RT
Since PT = ( assuming all gases to be ideal)
V
2
ab3  RT 
   = KP …(1)
c2  V 
Now, let us examine the effect of change in certain parameters such as number of moles,
pressure, temperature etc.
If we increase a or b, the left hand side expression becomes QP ( as it is disturbed from
equilibrium) and we can see that QP > KP
The reaction therefore moves backward to make QP = KP.
If we increase c, Q P < K P and the reaction has to mov e f orward to rev ert
back to equilibrium.
If we increase the volume of the container (which amounts to decreasing the pressure), QP
< KP and the reaction moves forward to attain equilibrium.
If we increase the pressure of the reaction, then equilibrium shifts towards backward direction
since in reactant side we have got 2 moles and on product side we have got 4 moles. So
pressure is reduced in backward direction.
If temperature is increased, the equilibrium will shift in forward direction since the forward
reaction is endothermic and temperature is reduced in this direction.
However from the expression if we increase the temperature of the reaction, the left hand
side increases (QP) and therefore does it mean that the reaction goes backward (since QP
> KP)?. Does this also mean that if the number of moles of reactant and product gases are
equal, no change in the reaction is observed on the changing temperature (as T would not
exist on the left hand side)?. The answer to these questions is No. This is because KP
also changes with temperature. Therefore, we need to know the effect of temperature on
both QP and KP to decide the course of the reaction.
EFFECT OF ADDITION OF INERT GASES TO A REACTION AT EQUILIBRIUM

1. Addition at Constant Pressure:
Let us take a general reaction
aA + bB cC + dD
c d
 n   n 
 C  PT   D  PT 
 n    n 
We know, Kp    
a

b
 n   n 
 A  PT   B  PT 
 n    n 
   
Where,
nC nD, nA, nB denotes the no. of moles of respective components and PT is the total pressure
and n = total no. of moles of reactants and products.
n
n c  n dD  PT 
Now, rearranging , K P  ac  
n A  n bB  n  
Where n = (c + d) – (a + b)
Now, n can be = 0,  0 or  0
Let us take each case separately.
(a) n = 0 : No effect (b) n = ‘+ve’ :
n
 P   P 
Addition of inert gas increases the n i.e.  T  is decreased and so is  T  . So
 n    n 
  
products have to increase and reactants have to decrease to maintain constancy of Kp.
So the equilibrium moves forward.
(c) n = ‘–ve’ :
n
 P   P 
T

In this case    T 
  decreases but  n 
increases. So products have to decrease
 n   
and reactants have to increase to maintain constancy of Kp. So the equilibrium moves
backward.
2. Addition at Constant Volume:
Since at constant volume, the pressure increases with addition of inert gas and at the same
n
 P 
T
time n also increases, they almost counter balance each other. So  
 can be
 n  
safely approximated as constant. Thus addition of inert gas has no effect at constant volume.
Dependence of Kp or Kc on Temperature
Now we will derive the dependence of KP on temperature.

Starting with Arrhenius equation of rate constant
 E af / RT
kf  Af e … (i)
Where, kf = rate constant for forward reaction, Af = Arrhenius constant of forward reaction,
E af = Energy of activation of forward reaction
 E a r / RT
k r  A re …(ii)
Dividing (i) by (ii) we get,
 E a r  E af 
k f Af RT
 e
k r Ar
kf
We know that  K (equilibrium constant )
kr
 E a r  E af 
k f Af RT
 K =  e
k r Ar
At temperature T1
 E a r  Ea f 
A RT1
K T1  f e …(iii)
Ar
At temperature T2
 Ea r Ea f 
A RT2
K T2  fe … (iv)
Ar
Dividing (iv) by (iii) we get

 Ea r  E a f   1 1
K T2 
R
 
T

T
 K T2 E E  1
ar af 1
    log K  2.303 R  T  T 
   2 1
e
K T1 T1  2 1
The enthalpy of a reaction is defined in terms of activation energies as

E a f  E a r = H
K T2 H  1 1
 log    
K T1 2.303 R  T2 T1 
KT ΔH 1 1 
log K = 2.303 R  T - T 
2
 …(v)
T1  1 2
For an exothermic reaction, H would be negative. If we increase the temperature of the
system (T2>T1), the right hand side of the equation (V) becomes negative.
 K T2 < K T1 , that is, the equilibrium constant at the higher temperature would be less
than that at the lower temperature.
Now let us analyse our question. Will the reaction go forward or backward?
Before answering this, we must first encounter another problem. If temperature is increased,
the new KP would either increase or decrease or may remain same. Let us assume it
increases.
Now, Q P can also increase, decrease or remain unchanged. If K P increases and Q P
decreases, then Q PT2  K PT2 , therefore the reaction moves forward. If KP increase and QP
 
remains same, then Q PT2 Q PT1  K PT2 . Again, the reaction moves forward. What, if KP
increase and QP also increases?
Will Q PT2  K PT 2 or Q PT2  K PT2 or Q PT2  K PT2 ? This can be answered by simply looking
at the dependence of QP and KP on temperature. You can see from the equation that KP
depends on temperature exponentially. While Q’s dependence on T would be either to the
power g,l,t…….. Therefore the variation in KP due to T would be more than in QP due to
T.
 KP would still be greater than QP and the reaction moves forward again.
Therefore, to see the temperature effect, we need to look at KP only. If it increases, the
reaction moves forward, if it decreases, reaction moves backward and if it remains fixed,
then no change at all.
Example 7:
Under what conditions will the following reactions go in the forward direction ?
1. N2(g)+ 3H2(g) 2NH3(g) + 23 k cal.
2. N2(g) + O2(g) 2NO(g) - 43.2 k cal.
3. C(s) + H2O(g) CO2(g) + H2(g) + X k cal.
4. N2O4(g) 2NO2(g) - 14 k cal.
Solution:
1. Low T, High P, excess of N2 and H2.
2. High T, any P, excess of N2 and O2
3. Low T, Low P, excess of C and H2O
4. High T, Low P, excess of N2O4.
Example 8:
Under what conditions will the following reactions go in the forward direction?
1. 2SO2(g) + O2(g) 2SO3(g) + 45 k cal.
2. 2NO(g) + O2(g) 2NO2(g) + 27.8 k cal.
3. PCl5(g) PCl3(g) + Cl2(g)- X k cal.
Solution :
(i) Low T, high P, excess of O2 and SO2
(ii) Low T, high P, excess of NO and O2
(ii) High T, low P, excess of PCl5
LE - CHATELIER’S PRINCIPLE AND PHYSICAL EQUILIBRIA
Le Chatelier’s principle, as already stated, is applicable to all types of equilibria involving

not only chemical but physical changes as well. A few examples of its application to physical
equilbria are discussed below.
1. Vapour pressure of a liquid: Consider the equilibrium

Liquid Vapour
It is well known that the change of a liquid into its vapour is accompanied by absorption of
heat whereas the conversion of vapour into liquid state is accompanied by evolution of heat.
According to Le Chatelier’s principle, therefore, addition of heat to such a system will shift
the equilibrium towards the right. On raising the temperature of the system, liquid will
evaporate. This will raise the vapour pressure of the system. Thus, the vapour pressure of
a liquid increases with rise in temperature.
2. Effect of pressure on the boiling point of a liquid: The conversion of liquid into vapour,
as represented by the above equilibrium, is accompanied by increase of pressure (vapour
pressure). Therefore, if pressure on the system is increased, some of the vapours will change
into liquid so as to lower the pressure. Thus, the application of pressure on the system
tends to condense the vapour into liquid state at a given temperature. In order to counteract
it, a higher temperature is needed. This explains the rise of boiling point of a liquid on the
application of pressure.
3. Effect of pressure on the freezing point of a liquid (or melting point of a solid): At
the melting point, solid and liquid are in equilibrium:
Solid Liquid
Now, when a solid melts, there is usually a change, either increase or decrease, of volume.
For example, when ice melts, there is decrease in volume, or at constant volume, there is
decrease in pressure. Thus, increase of pressure on ice water system at a constant
temperature will cause the equilibrium to shift towards the right, i.e., it will cause the ice
to melt. Hence, in order to retain ice in equilibrium with water at the higher pressure it will
be necessary to lower the temperature. Thus, the application of pressure will lower the melting
point of ice.
When sulphur melts, there is increase in volume or at constant volume, there is increase
in pressure. From similar considerations, it follows that if the pressure on the system,
sulphur (solid) sulphur (liquid) is increased, the melting point is raised.
4. Effect of temperature on solubility: In most cases, when a solute passes into solution,
heat is absorbed, i.e., cooling results. Therefore according to Le Chatelier’s principle, when
heat is applied to a saturated solution in contact with solute, the change will take place in
that direction which absorbed heat (i.e., which tends to produce cooling). Therefore, some
more of the solute will dissolve. In other words, the solubility of the substance increases
with rise in temperature.
Dissociation of a few salts (e.g., calcium salts of organic acids) is accompanied by evolution
of heat. In such cases, evidently, the solubility decreases with rise in temperature.
FEE ENERGY AND CHEMICAL EQUILIBRIUM
For a general reaction, mA + nB pC + qD, DG is given by-

0
G =  G + 2.303 RT log 10Q
where  G = Gibb's Free energy
G0 = Standard Gibb's Free energy
Q = reaction
Since, at equlibrium, Q = K
Here K is thermodynamic equilibrium constant replacing K c or Kp
(a C )p (a D ) q
K=
(a A )m ( a B )n
Here aX denotes the activity of X.

In fact, ‘ax’ is the ratio of the activity of substance at equilibrium and its activity in standard
condition. That is why it is unitless and K is also unitless.
Note :
(i) Themodynamics equilibrium constant is unitless since activity is unitless.
(ii) For pure solids & pure liquids, activity is unity.
(iii) For gases (ideal behaviour), the activity is its partial pressure in atm.
(iv) For components in solution, activity is molar concentration.
At equilibrium, DG = 0
 DG 0 = – 2.303 RT log10K
Now since, DG 0 = DH0 – TDS0

where DH0 = Standard enthalpy of the reaction
DS° = Standard entropy change
 – 2.303 RT log10K = DH0 – TDS0
H0 1 S 0
 log10K = – . +
2.303 RT 2.303R
1
If plot of lnk vs is plotted then it is a straight line with slope
T
H S
=– , and intercept =
R R
log K
log K
0 T – 1 or 1/T 0 T – 1 or 1/T
 H0 S 0
Slope = = tan  y intercept =
2.303R 2.303R
If at temperature T 1, equilibrium constant is K 1 and at T 2, it is K2 then ;
 H0 1 S 0
log10K1 = .T + ........... (i)
2.303R 1 2.303R
 H0 1 S 0
log10K2 = . T + ........... (ii)
2.303R 2 2.303R
[Assuming  H0 and  S0 remains constant in this temperature range.]
Subtract eq. (ii) from (i) we get Vant Hoff equation-
 K1  H0  1 1
log  K  =  
T  T 
 2 2.303R  2 1
Note :
H0 should be substituted with sign.
Unit of  H0 and gas constant R should be same.
* For endothermic (H > 0) reaction value of the equilibrium constant increases with the rise in
temperature
* For exothermic (H < 0) reaction, value of the equilibrium constant decreases with increase in
temperature
Condition for Spontaneity:
 G0 < 0 for spontaneous process or reaction.

Since,  G =  H – T  S
 H – TS < 0
 T >  H/  S
* G > 0 for non - spontaneous process or reaction
* G = 0 for equilibrium.
Example 9:
Kc for the reaction N2O4 2NO2 in chloroform at 291 K is 1.14. Calculate the
free energy change of the reaction when the concentration of the two gases are
0.5 mol dm–3 each at the same temperature. (R = 0.082 lit atm K–1 mol–1.)
Solution:
From the given data
T = 291 K; R = 0.082 lit atm K–1 mol–1
Kc = 1.14; C NO2  C N2 O4 = 0.5 mol dm–3
The reaction quotient Qc for the reaction N 2 O 4 2NO 2 ,

2
[NO 2 ] 0.5  0.5
Qc    0.5
[N 2 O 4 ] 0.5
Since Qp = Qc(RT)n and n = 2 – 1 = 1 in this case
Qc = 0.5 (0.082 × 291) = 11.93
Kp = Kc(RT)n = 1.14 (0.082 × 291) = 27.1
Substituting these values in the equation
G = G0 + RTlnQp = – RT ln Kp + RT ln Qp, we get
= – 2.303 RT (log Kp – log Qp)
G = – (0.082 × 291 × 2.303) [log 27.2 – log 11.93]
= – 54.95 (1.4346 – 1.0766) = – 19.67 lit atm
Example 10:
Calculate the pressure of CO2 gas at 700K in the heterogeneous equilibrium reaction
CaCO3(s) CaO(s) + CO2(g) if  G0 for this reaction is 130.2 kJ mol–1.
Solution:
Here Kp = PCO2
Also, G 0   RT ln K p
G 0 130.2  103 Jmol1

 ln K p    pCO2  K p  1.94  1010 atm
RT (8.314JK 1mol 1 )(700K)
Example 11:
For t he equi l i bri um Ni O (s) + CO (g) Ni (s) + CO 2(g) ,   G 0 (Jmol –1 )
= – 20,700 – 11.97 T. Calculate the temperature at which the product gases at
equilibrium at 1 atm will contain 400 ppm (parts per million) of carbon monoxide.
Solution: For the given reaction K p  pCO2 / p CO
Since pCO  pCO2 , hence
1 1
Kp    2,500
pCO 400  106
G 0   RT ln K p
G 0 20,700  11.97T
 ln K p  
RT RT
The equation when solved for T using R = 8.314 K–1 mol–1, gives T = 399K.
Example 12:
i) Calculate the partial pressure of HCl gas above solid a sample of NH4Cl(s) as a result
of its decomposition according to the reaction:
NH4Cl(s) NH3(g) + HCl(g) Kp = 1.04 × 10–16
ii) Calculate the equilibrium constant of a reaction at 300 K if  G0 at this temperature
for the reaction is 29.29 kJ mol–1.
Solution :
(i) NH4Cl(s) NH3(g) + HCl(g) Kp = 1.04 ×10–16

Kp = PNH × PHCl  P2 = Kp P= Kp
3
 P= 1.04  10 16 = 1.02 × 10–8 atm.

(ii) G0 = –2.303 RT log Kp
 29.29 ×103 = –2.303 × 8.31 × 300 log Kp
 Kp = 7.91 × 10–6
Example 13:
For the formation of ammonia the equilibrium constant data at 673K and 773K
respectively are 1.64 × 10–4 and 1.44 × 10–5 respectively. Calculate heat of the
reaction. Given R = 8.314 JK–1 mol–1.
Solution: Substituting the values in the equation
K p2 H  T2  T1 
ln    , we get
K p1 R  T2 T1 
1.44  105 H  773  673 

2.303log 
1.64  10 4
8.314  773  673 
H(100)
2.303log(0.0878) 
8.314  773  673
100H = 2.303 (–1.0565) × 673 × 773 × 8.314
673  773  2.303  1.0565  8.314

whence, H  = – 105216J = – 105.216kJ
100
Example 14:
The equilibrium constant KP for the reaction N2(g)+3H2(g) 2NH3(g) is 1.6  10-4
o o
atm at 400 C. What will be the equilibrium constant at 500 C if heat of the reaction
in this temperature range is 25.14 k cal?
Solution: N2(g) + 3H2(g) 2NH3(g)
–4
Kp = 1.6 × 10 at T1 = 673 K
Kp = ? at T2 = 773 K
 Kp   25.14  103

log  = log [673 – 773]
4  2.303  2
 1 .6  10 
Kp = 1.43 × 10–5
Relation between Vapour Density and Degree of Dissociation

In the following reversible chemical equation
A yB
Initial mol 1 0
At equilibrium (1 –x) yx x = degree of dissociation
Number of moles of A and B at equilibrium = 1 – x + yx = 1 + x(y –1)
If initial volume of 1 mole of A is V, then volume of equilibrium mixture of A and B is
= [1 + x(y – 1)]V
molecular weight m
Molar density before dissociation, D 
volume V
m
Molar density after dissociation d 
[1  x(y  1)]V
D
  [1  x(y  1)]1
d
Dd
 x
d(y  1)
D
Note: y is the number of moles of products from one mole of reactant. is also called Van’t
d
Hoff factor.
Thus for the equilibria
I: PCl5  g  PCl 3 g   Cl 2g  , y  2
II: N2O4 g  2NO2g  , y  2
1
III: 2NO2 N2O4 , y 
2
Dd
 x
d
2(d  D)
x
d
Also D × 2 = Molecular weight (theoretical value)
d × 2 = Molecular weight (abnormal value) of the mixture
Example 15:
Vapour density of the equilibrium mixture of NO2 and N2O4 is found to be 40 for the
equilibrium
N2O4 2NO2
Calculate (i) abnormal molecular weight
ii) degree of dissociation
iii) percentage of NO2 in the mixture
Solution: (i) N2O4 2NO2
Observed value of vapour density (d) = 40
Hence, abnormal molecular weight = 40 × 2 = 80
(ii) D × 2 = theoretical molecular weight = 2
92
 D  46
2
D  d 46  40
 x   0.15
d 40
(iii) N2O4 2NO2

Initial mol 1 0
At equilibrium (1 – x) 2x
0.85 0.30
Total moles at equilibrium = (1 + x) = 1 + 0.15 = 1.15
2x 0.30
 Percentage of NO2 =  100   100 = 26.08%
1 x 1.15
Example 16:
N2O4(g) 2NO2(g). In this reaction, NO2 is 20% of the total volume at equilibrium.
Calculate (i) Vapour density
(ii) abnormal molecular weight
(iii) percentage dissociation of N2O4
Solution : N2O4 2NO2

t=0 1 –
t = teq 1–x 2x =1+x
2x 1
 NO = = 0.2  x=
2
1 x 9
1 46  d
(i) =  10d = 46 × 9
9 d
92
(ii) M=  d = 41.4
1 x
1
(iii) = × 100 = 11.1%
9
EXERCISE # 01 OBJECTIVE EXERCISE

1. The equilibrium constant for the reaction H2(g) + I2(g) 2HI(g) is 64. If the volume of the container
is reduced to half of the original value, the value of the equilibrium constant will be
(A) 16 (B) 32 (C) 64 (D) 128
2. Consider the reaction: HCN(aq) H+(aq) + CN–(aq). After the equilibrium is established, if CN–
(aq) is added to the reaction mixture, it will
(A) reduce the concn. of HCN(aq) (B) reduce the concn. of H+ (aq)
(C) increase the value of K (D) decrease the value of K
3. If dil.HCl is added to the equilibrium CH3COOH CH3COO– + H+

(A) the value of K will change
(B) the concentration of CH3COO– will increase
(C) the concentration of CH3COO– will decrease
(D) nothing will happen
4. If the mixture containing the equilibrium N2O4 2NO2 is compressed, this will mean
(A) an increase in the concentration of N2O4
(B) an increase in the formation of NO2
(C) an increase in the value of K
(D) no change in the concentration of NO2 or N2O4
5. For the reaction PCl5(g) PCl3(g) + Cl2(g), the total pressure at equilibrium is 2.0 atm. One
mole of He is now introduced into the same vessel. The equilibrium constant
(A) will increase (B) decrease
(C) remain unchanged (D) will depend on the amount of He added
6. When pressure is applied to the equilibrium system

Ice Water
which of the following phenomena will take place?
(A) water will evaporate (B) more ice is formed
(C) more water is formed (D) equilibrium is not disturbed
7. Which of the following reactions is favoured at a low pressure?

(A) H2 + I2 2HI (B) PCl5 PCl3 + Cl2
(C) N2 + 3H2 2NH3 (D) N2 + O2 2NO
8. The equilibrium constant for the reaction N2 + 3H2 2NH3 is ‘K’ and that for the reaction
1 3
N 2 + H 2  NH3 is ‘K’. Then, K and K is related as
2 2
(A) K = K (B) K = K (C) K = K (D) K  K
9. The decomposition of N2O4 to NO2 is carried out at 280°C in chloroform. At equilibrium, 0.2 mol of
N2O4 and 2  10–3 mol of NO2 are present in 2 L of solution. The equilibrium constant for the reaction
N2O4 2NO2 is
(A) 1  10–3 (B) 2  10–3 (C) 1  10–5 (D) 2  10–5
10. The equilibrium N2 + O2 2NO is established in a vessel with a capacity of 2.5 L. The initial
amount of N2 is 2 mol and that of O2 is 4 mol. Half a mole of N2 is used up at the equilibrium. The
molar concentration of NO is
(A) 0.2 (B) 0.4 (C) 0.6 (D) 0.1
11. 2 mol of HI was heated in a sealed tube at 440°C till equilibrium was reached. HI was found to be
22% decomposed. The equilibrium constant for the dissociation is
(A) 0.282 (B) 0.0796 (C) 0.0199 (D) 1.99
12. XY2(g) dissociates as XY2(g) XY(g) + Y(g). When the initial pressure of XY2 is 600 mm of Hg,
the total equilibrium pressure is 800 mm of Hg. Assuming that the volume remains unchanged, the
value of K is
(A) 50 (B) 100 (C) 166.6 (D) 400.0
13. A quantity of PCl5 was heated at 250°C in a vessel with a capacity of 10 L. It dissociates as
PCl5 PCl3+ Cl2 . At equilibrium, the vessel contains 0.1 mol of PCl5, 0.20 mol of PCl3, and
(g) (g) (g)
0.20 mol of Cl2. The equilibrium constant for the reaction is
(A) 0.02 (B) 0.05 (C) 0.04 (D) 0.025
14. At a certain temperature, only 50% of HI is dissociated into H2 and I2 at equilibrium. The
equilibrium constant is
(A) 1.0 (B) 3.0 (C) 0.5 (D) 0.25
15. For the reaction PCl3(g) + Cl2(g) PCl5(g), the value of KC at 250°C is 26. The value of Kp at this
temperature is
(A) 0.61 (B) 0.83 (C) 0.57 (D) 0.46
16. The reaction x 2y is taking place in a flask with a capacity of 2 L. If the degree of dissociation
of X is 0.4, the equilibrium constant is
(A) 2 (B) 10.6 (C) 0.53 (D) 5.3
17. The vapour density of N2O4 at a certain temperature is 30. What is the percentage dissociation of
N2O4 at this temperature?
(A) 53.3 % (B) 106.6%
(C) 26.7% (D) none of the above
18. Consider the reaction

CaCO3(s) CaO(s) + CO2(g) in a closed container at equilibrium. What will be the effect of
adding CaCO3 on the equilibrium concentration of CO2?
(A) it increases
(B) it decreases
(C) it remains unchanged
(D) it cannot be predicted
19. At a certain temperature, 2 mol of CO and 3 mol of Cl2 were allowed to reach equilibrium according
to the reaction CO + Cl2  COCl2 in a vessel with a capacity of 5 L at 305°C. If one mole of CO is
present at equilibrium, what is the value of K ?
(A) 2.0 (B) 2.5 (C) 3.0 (D) 4.0
20. Given the reactions
CuO(s) + H2(g) Cu(s) + H2O(g) KC1 = 2  1015
H2(g) + 1/2O2(g) H2O(g) KC2 = 5  1022

Then, KC for the reaction
1
CuO(s) Cu(s) + O (g) is
2 2
KC 2  1015
1
(A) (B) (C) 4  10–8 (D) all of the above
reciprocalK C2 5  1022
21. For the reaction
1
SO2(g) + O (g) SO3(g) K1
2 2
2SO3(g) 2SO2(g) + O2(g) K2
K1 and K2 are related as
1
(A) K 2  (B) K2 = [K1]2 (C) K2 = 2K1 (D) K1 = [K2]2
K12
1
22. KP/Kc for the reaction CO + O CO2 is
2 2
1 RT
(A) RT (B) (C) (D) 1
RT 2
23. The reactions 2SO2 + O2 2SO3 H = –ve

N2 + 3H2 2NH3 H = –ve
are favoured by
(A) low temperature and high pressure (B) high temperature and high pressure
(C) low temperature and low pressure (D) high temperature and low pressure
24. 1.2 mol of SO3 is allowed to dissociate in a vessel with a capacity of 2 L. The reaction is
2SO3(g) 2SO2(g) + O2(g). 0.20 mole of O2 is present at equilibrium. Which of the following
statements is false?
(A) the value of K is 2.5  10–2 (B) percentage dissociation of SO2 is 40%
(C) in the equilibrium mixture, [SO3] = 0.4 M (D) total moles present at equilibrium are 1.4
25. In which of the following cases will the least time be required to arrive at an equilibrium?
(A) KC is very small (B) KC ~ 1.0
(C) KC is very large (D) cannot be predicted
26. The equilibrium constant for the reaction H2 + I2 2HI at 700 K is 56. If 0.5 mol of H2 and 1.0 mol
of iodine are added to the system at equilibrium, the value of equilibrium constant will be
(A) 25 (B) 100 (C) 56 (D) 0.25
27. In what manner the increase of pressure will affect the following equation?
C(s) + H2O(g) CO(g) + H2O (g)
(A) a shift in the forward direction (B) a shift in the reverse direction
(C) an increase in the yield of water (D) no effect
28. One mole of SO3 was placed in a vessel with a capacity of 1.0 L at a certain temperature when the
following equilibrium was established.
2SO3 2SO2 + O2
At equilibrium, 0.6 mol of SO2 was formed. The equilibrium constant of the reaction is
(A) 0.36 (B) 0.45 (C) 0.54 (D) 0.675
29. A vessel with a capacity of 1 L initially contains 2.0, 0.5, and 0.0 moles of N2, H2, and NH3 respectively.
At equilibrium, 0.2 mole of NH3 is formed. The number of moles of H2 in the vessel at equilibrium is
(A) 0.3 (B) 0.4 (C) 0.2 (D) 1.8
30. Consider the reaction: A + B C + D. The reaction initiates with an equal concentration of A and
B. At equilibrium, it is found that the moles of C are twice that of A. What is the equilibrium constant
of the reaction?
1 1
(A) (B) (C) 4 (D) 2
4 2
31. A 1.0 M solution of glucose reaches dissociation equilibrium according to the equation
6HCHO C6H12O6. What is the concentration of HCHO at equilibrium, if equilibrium constant is
22
6  10 ?
(A) 1.6  10–8 M (B) 3.2  10–6 M (C) 3.2  10–4 M (D) 1.6  10–4 M
32. AB2 dissociates as

AB2 (g) AB(g) + B(g)
If initial pressure of AB2 is 500 mm Hg, the total pressure is 700 mm of Hg. Calculate equilibrium
constant of the reaction, assuming that the volume of the system remains unchanged.
(A) 100 mm Hg (B) 133.3 mm Hg (C) 200 mm Hg (D) 214.6 mm Hg
33. 2.2 mol of PCl5 was taken in a closed vessel and dissociated into PCl3 and Cl2. At equilibrium, the
total number of moles of the reactants and products was 2.53. The degree of dissociation is
(A) 0.33 (B) 0.165 (C) 0.15 (D) 0.30
34. In the reaction A(s) + B(g) + Heat 2C (s) + 2D (g), equilibrium is established. The pressure of
B is doubled to re-establish the equilibrium. The factor by which D is changed is
(A) 2 (B) 3 (C) 2 (D) 3
35. Ammonium carbamate decomposes as

NH2 COONH4 (s) 2NH3 (g) + CO2 (g)
Kp for this reaction = 2.9  10–5 atm3. If the reaction initiates with 1 mole of the compound, the total
pressure at equilibrium is
(A) 0.0766 atm (B) 0.0582 atm (C) 0.0388 atm (D) 0.0194 atm
36. If  fraction of HI dissociates at equilibrium at 527°C, then starting with 2 moles of HI at 527°C, the
total number of moles of reactants and products is
(A) 1 +  (B) 2 + 2 (C) 2 (D) 2 
37. In a closed vessel of volume ‘v’, ‘a’ moles of N2 and ‘b’ moles of O2 are made to react to give NO at
420° C. If 2x moles of NO are obtained at equilibrium, then
x2 4x 2
(A) kc  .V (B) kc  .V
 a  x  b  x   a  x  b  x 
4x 2 4x 2
(C) kc  (D) kc 
V  a  x  b  x   a  x  b  x 
38. The equilibrium constant for the reaction W + X Y + Z is 9.0. If one mole each of W and X are
mixed, and there is no change in volume. The number of moles of Y formed is
(A) 0.10 (B) 0.50 (C) 0.75 (D) 0.90
39. In the equilibrium reaction X2 (g) + 2Y2 (g) 2 XY2 (g), the partial pressures of X2, Y2, and XY2
are P1, P2, and P3 respectively at equilibrium. The value of Kp is
2 2
2P3 P1P2   P3   P1  P2 
(A) P P (B) (C) 2 (D) 2
1 2 P3 P1  P2   P3 
40. The equilibrium constant at 323°C is 1000. What will be the value in the presence of a catalyst for the
following reaction:
A+B C + D + 38 K cal
(A) 1000 X (concentration of catalyst) (B) 1000
(C) 1000 / catalyst weight (D) none of the above
41. In the reaction C(s) + CO2 (g) 2CO(g), the following amounts of substances were found in a
flask with a capacity of 2 L at equilibrium: C = 0.1 mole, CO = 0.05 mole, and
CO2 = 0.006 mole. The equilibrium constant is
(A) 0.208 (B) 9.16 (C) 0.33 (D) 0.416
42. Kp for the reaction CO2 (g) + H2 (g) CO(g) + H2O (g) is found to be 16.0 at a given temperature.
Originally, an equal number of moles of H2 and CO2 was placed in the flask. At equilibrium, the
pressure of H2 is 1.20 atm. What is the partial pressure of CO and H2O?
(A) 4.80 atm. (B) 9.60 atm. (C) 2.40 atm. (D) 1.20 atm.
43. If N2O4 is 25% dissociated at 275° C in a vessel with a capacity of 4.0 L, the Kc of the reaction
(N2O4 2NO2) is
1 1 1 1
(A) (B) (C) (D)
16 4 6 12
44. At 730°C, the vapour density of iodine under a pressure of 1 atm is 97.45 % of the theoritical value
on the assumption that molecules of gaseous iodine are diatomic. The degree of dissociation of I2 is
(A) 0.0131 (B) 0.0262 (C) 0.082 (D) 0.0324
45. Consider the equilibrium 2A(g) + B(g) C(g) + 3D(g). If the concentrations are [A] = 2.0 M, [B] =
0.50 M, [C] = 0.25 M [D] = 1.5 M, the value of Kc is
(A) 0.21 (B) 0.42 (C) 0.84 (D) 42
46. Kc for the reaction SO2 (g) + NO2 (g) SO3(g) + NO(g) is 1.0 at a given temperature. If
2.0 mol of SO2 and 4.0 mol of NO2 are placed in a flask with a capacity of 1.0 L, what is the
concentration of SO3 at equilibrium?
(A) 1.8 M (B) 2.2 M (C) 1.3 M (D) 2.6 M
47. For the reaction I2(g) 2I(g), at 290°C, the value of Kc = 4  10–3. If the equilibrium concentration
of atomic iodine is 4  10–2 M, what is the concentration of molecular iodine?
(A) 0.8 M (B) 0.4 M (C) 0.3 M (D) 0.2 M
48. For the reaction 2NO2 N2O4, if the original concentration of NO2 is 0.90 M and its equilibrium
concentration is 0.26 M, the equilibrium constant of the reaction is
(A) 4.7 (B) 3.7 (C) 2.7 (D) 5.7
49. The position of equilibrium will not be affected by changes in the container volume for
(A) 2SO2 (g) + O2 (g) 2SO3 (g) (B) N2 (g) + O2 (g) 2NO (g)
1
(C) N2 (g) + 3H2 (g) 2NH3 (g) (D) H2O2 (l) H2O (l) + O (g)
2 2
50. Equimolar quantities of HI, H2, and I2 are brought to equilibrium. If the total pressure in the vessel is
1.5 atm and Kp for 2HI(g) H2(g) + I2(g) is 49, which of the following is the correct value for the
partial pressure of iodine?
(A) 0.4 (B) 0.9 (C) 0.7 (D) 0.5
EXERCISE # 02 ADVANCE LEVEL EXERCISE

COMPREHENSION TYPE, MULTIPLE TYPE, MATRIX MATCH TYPE, INTEGER TYPE
MULTIPLE ANSWER CORRECT TYPE

1. Which of the following statements are incorrect?
(A) For a closed system, S is always maximum at equilibrium.
(B) The addition of a reactant gas to an ideal-gas reaction mixture shifts the equilibrium in such a
way that some of the added gas is used up
(C) In any closed system, G is always minimum at equilibrium.
(D) In the limit T 0, Gº approaches Hº.
2. The expression for the equilibrium constant for an ideal-gas reaction mixture is given by
d ln K 0c U 0   ln K 0x  S0
(A)  (B)    2
dT RT 2   T  RT
  ln K 0  n / mol
x d ln K 0p H 0
(C)   T
 
 p (D) 
 T dT RT 2
3. The condition for spontaneity in a chemical reaction is
(A) (G)T, p 0 (B) (U)S, V 0 (C) (H)S, p 0 (D) (S)U, V 0
4. In which of the following reactions is Kp < Kc ?
(A) CO(g) + Cl2(g) COCl2(g) (B) CO(g) + 3H2(g) CH4(g) + H2O(g)
(C) 2BrCl(g) Cl2(g) + Br2(g) (D) I2(g) 2I(g)
5. The dissociation of phosgene, which occurs according to the reaction
COCl2(g) CO(g) + Cl2(g)
is an endothermic process. Which of the following will increase the degree of dissociation of COCl2?
(A) Adding Cl2 to the system
(B) Adding helium to the system
(C) Decreasing the temperature of the system
(D) Reducing the total temperature of the system
6. The equilibrium of which of the following reactions will not be disturbed by the addition of an inert gas
at constant volume ?
(A) H2(g) + I2(g) 2HI(g) (B) N2O4(g) 2NO2(g)
(C) CO2(g) + 2H2(g) CH3OH(g) (D) C(s) + H2O(g) CO(g) + H2(g)
7. A box contains CO(g), Cl2(g) and COCl2(g) in equilibrium at 1000 K. The removal of CO(g) will
(A) decrease the concentration of COCl2
(B) increase the concentration of Cl2
(C) increase the concentration of COCl2
(D) reduce the concentration of CO as well as Cl2
8. An industrial fuel, ‘water gas’, which consists of a mixture of H2 and CO can be made by passing
steam over red-hot carbon. The reaction is
C(s) + H2O(g) CO(g) + H2(g) , H = +131 kJ
The yield of CO and H2 at equilibrium would be shifted to the product side by
(A) raising the relative pressure of the steam (B) adding hot carbon
(C) raising the temperature (D) reducing the volume of the system
9. For the equilibrium 2SO2(g) + O2(g) 2SO3(g), H = -198 kJ, the equilibrium concentration of
SO3 will be affected by
(A) doubling the volume of the reaction vessel
(B) increasing the temperature at constant volume
(C) adding more oxygen to the reaction vessel
(D) adding helium to the reaction vessel at constant volume
10. The following reaction attains equilibrium at high temperature
N2(g) + 2H2O(g) + heat 2NO(g) + 2H2(g)
The yield of NO is affected by
(A) increasing the nitrogen concentration (B) decreasing the hydrogen concentration
(C) compressing the reaction mixture (D) none of these
Catalyst
11. N2(g) + 3H2(g) 500°C
2NH3 + heat
In this reaction, the direction of equilibrium will be shifted to the right by
(A) increasing the concentration of nitrogen (B) compressing the reaciton mixture
(C) removing the catalyst (D) decreasing the concentration of ammonia
12. The dissociation of ammonia carbonate may be represented by the equation
NH4CO2NH2(s) 2NH3(g) + CO2(g)
Gº for the forward reaction is negative. The equilibrium will shift from right to left is there is
(A) a decrease in pressure
(B) an increase in temperature
(C) an increase in the concentration of ammonia
(D) an increase in the concentration of carbon dioxide
13. For which of the following reactions is the equilibrium constant called an acidity constant?
(A) 2H2O H3O+ + OH– (B) H2S + H2O H3O+ + HS–
– + +
(C) HONO + H2O ONO + H3O (D) H3O + CH3NH2 CH3NH3 + H2O
14. Which of the following statements about the reaction quotient Q are correct?
(A) the reaction quotient, Q and the equilibrium constant always have the same numerical value.
(B) Q may be >, < , = Keq .
(C) Q(numerical value) varies as reaction proceeds
(D) Q = 1 at equilibrium
15. Which of the following factors will increase solubility of NH3(g) in H2O?
NH3(g) + H2O(aq) NH4OH(aq)
(A) increase in pressure (B) addition of water.
(C) liquefaction of NH3 (D) decrease in pressure
16. Which of the following factors will affect solubility of CaO in H2O?
(A) pressure (B) temperature (C) addition of water (D) volume
17. For the following equilibrium
NH4HS(s) NH3(g) + H2S(g)
partial pressure of NH3 will increase
(A) if NH3 is added after equilibrium is established
(B) if H2S is added after equilibrium is established
(C) temperature is increased
(D) volume of the flask is decreased
18. Formation of Y from X is through the graph. It can be concluded:
B
D
E
Y
A
C
temperature
(A) reaction A to B is endothermic
(B) reaction A to B as well as C to D is exothermic
(C) reaction B to C is exothermic
(D) H = 0 for the stage D to E
19. Which are true statements for the following equilibrium?

H2O(l) H2O(g)
(A) increase in pressure will result in the formation of more liquid water
(B) increase in pressure will increase b.p.
(C) decrease in pressure will vaporise H2O(l) to a greater extent
(D) increase in pressure will liquefy steam.
20. Which is/are correct relation (s) for thermodynamic equilibrium constant
(A) Gº = –2.303 RT log K (B) G = Gº + 2.303 RT log K
0.0591 0.0591
(C) Eºcell = log K (D) E = Eº – logK
n n
21. Which is/are correct relation (s) for equilibrium constant K?
2.303 RT log K
(A) Gº = – 2.303 RT log K (B) Ecellº =
nF
Σ [product] H
(C) K = (D) log K = log A –
Σ [reactant] 2.303 RT
22. Volume of the flask in which species are transferred is double of the earlier flask. In which of the
following cases, equilibrium constant is
(A) N2(g) + 3H2(g) 2H3(g) (B) N2(g) + O2(g) 2NO(g)
(C) PCl5(g) PCl3(g) + Cl2(g) (D) 2NOBr(g) N2(g) + O2(g)
23. For the gas phase reaction carried out in a vessel,

C2H6 C2H4 + H2
the equilibrium concentration of C2H4 can be increased by -
(A) increasing the temperature (B) decreasing the pressure
(C) removing some H2 (D) adding some C2H6
24. For the reaction

2A(g) + B(g) 2C(g) ; H = +13.6 kJ
which of the following will increase the extent of the reaction at equilibrium
(A) increasing the temperature (B) increasing the pressure
(C) addition of catalyst (D) removing C
25. The reactions in which the yield of the products cannot be increased by the application of high
pressure
(A) 2SO2(g) + O2(g) 2SO3(g) (B) NH4HS(s) NH3(g) + H2S(g)
(C) N2O4(g) 2NO2(g) (D) N2(g) + 3H2(g) 2NH3(g)
MATRIX MATCH TYPE
26. Match the following
List I List II
(a) N2(g) + 3H2(g) 2NH3 (P) KP = KC
(b) H2(g) + S(s) H2S(g) (Q) KP > KC
(c) H2(g) + I2(g) 2HI(g) (R) KP < KC
(d) 2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
(A) a-Q, b-P, c-P, d-R (B) a-P, b-P, c-Q, d-R
(C) a-Q, b-R, c-P, d-R (D) a-R, b-P, c-P, d-Q
List I List II
(a) Keq < 1 (P) Affected by temperature
(b) Degree of dissociation (Q) Affected by pressure
(c) Equilibrium constant (R) Kf < Kb
(d) Melting of ice (S) Kf > Kb
(A) a-R, b-P, c-S, d-Q (B) a-R, b-P,Q, c-P, d-P,Q
(C) a-R, b-S c-P, d-Q (D) a-Q, b-R, c-S, d-P
List I (Reaction List II (units)
(a) N2 + O2 2NO (P) Kc = m/l
(b) N2 + 3H2 2NH3 (Q) no unit
(c) PCl5 PCl3 + Cl2 (R) kp = atm–2
(d) A(l) B(g) (S) Kp = atm
(A) a-Q, b-R,c-P,S, d-P,S (B) a-Q, b-R,c-P, d-S
(C) a-S, b-Q,c-P,R, d-P,S (D) a-R, b-Q,c-P,S, d-S
List I (Reaction) List II (degree of dissociation)
Dd
(a) 2NH3 2N2 + 3H2 (P)
2d
Dd
(b) N2 O4 2NO2 (Q)
d
Dd
(c) 4PH3 P4 + 6H2 (R)
3d
4( D  d )
(d) 5A 6B + 9C (S)
3d
(A) a-Q, b-P, c-R, d-S (B) a-P, b-Q, c-R, d-S
(C) a-Q, b-Q, c-S, d-P (D) a-S, b-R, c-Q, d-P
30. match List I with List II
(P is partial pressure of prdouct having stiochiometric coefficient unity)
List I (Reaction) List II (expression of Kp)
(a) NH4Cl(s) NH3(g) + HCl(g) (P) 6P6
(b) NH2COONH4(s) 2NH3(g)+ 2CO2(g) (Q) P2
(c) A(s) 2B(g) + C(g) + 3D(g) (R) 4P3
(d) A(s) B(g) + C(g) (S) 108P6
(A) a-Q, b-R, c-S, d-Q (B) a-P, b-Q, c-R, d-S
(C) a-S, b-R, c-Q, d-P (D) a-S, b-P, c-R, d-Q
EXERCISE # 03 SUBJECTIVE EXERCISE (LEVEL # 01)
1. N2O4 gas is 25% dissociated at 37°C and 1 atm. pressure. Calculate

(i) Kp of the reaction
(ii) the percentage dissociation at 0.1 atm and 37°C.
CO + 2H CH 3 OH
2. 0.15 mole of CO is taken in a flask of 2.5 L at 705 K to perform the reaction (g) (g)2 (g) .
Hydrogen is introduced in the reaction mixture till the total pressure of the system was 8.5 atmosphere
at equilibrium and 0.08 moles of methanol were formed. Calculate the values of Kp and Kc of the
reaction.
3. A compound AB2(g) dissociates at temperature T according to the reaction
1
 2K p  3
2AB2(g) 2AB(g) + B2(g). Deduce the expression x =   , where x is the degree of
 P 
dissociation and P is the total pressure.
4. For the reaction Ag(CN)2– Ag+ + 2CN–, the equilibrium constant at 25°C is 4.0  10–19.
+
Calculate the [Ag ] in a solution which has 0.10 M KCN and 0.03 M AgNO3.
5. Carbonyl chloride gas dissociates according to the equation COCl2(g) CO(g) + Cl2(g). When
the gas was heated to a temperature of 724 K and at a pressrue of 1.0 atm., the density of gas
mixture at equilibrium was found to be 1.162 g L–1. Calculate the degree of dissociation and Kp of the
reaction.
6. When 0.578 g of N2O4 was introduced into a one-litre flask at 308 K, the equilibrium pressure was
0.238 atm. Calculate the degree of dissociation and Kp of the reaction N2O4(g) 2NO2(g).
7. A sample of air hav ing N 2 and O 2 was heated to 2500 K until the equilibrium
N2(g) + O2(g) 2NO(g) was established. Kc of the reaction was 2.18  10–3 and mole percent of
NO at equilibrium was 1.8. Estimate the initial composition of air in mole fractions of N2 and O2.
8. For the reaction N2O5(g) 2NO2(g) + 0.5 O2 (g), calculate the mole fraction of N2O5(g) which
decomposed at a constant volume and temperature, if the initial pressure was 600 mm Hg and
pressure at any time was 960 mm Hg. Assume ideal behaviour for gases.
9. A mixture of NO gas at 0.373 atm. pressure and Cl2 gas at 0.310 atm pressure was kept in a flask
at 500 K temperature. The gases reacted as 2 NO(g) + Cl2(g) 2NOCl(g). The total pressure at
equilibrium was 0.544 atm. Calculate the equilibrium constant of the reaction.
10. CaCO3 dissociates in a container of volume 0.654 L at 1000 K. The equilibrium constant for the
reaction CaCO3(s) CaO(s) + CO2 (g) is 3.9  10–2 atm. at this temperature. Calculate the
mass of CaO present at equilibrium.
11. Kc for the dissociates of PCl5 (g) is equal to 4.15  10–12 at 250°C. If the reaction takes place in a
two-litre flask initially having 0.01 moles of PCl5, what will be the total pressure of all gases at 250°C
when equilibrium is achieved.
12. For the equilibrium Ag 2CO 3(s) Ag 2O(s) + CO 2(g), the equilibrium constants are
–4 –2
3.98  10 and 1.41  10 respectively at 350 K and 400 K. Calculate H° of the reaction.
13. Acetic acid was evaporated in a container of volume 21.45 cm3 at 437 K and an external pressure of
764.3 Torr. The container was then sealed. The mass of acid present in the sealed container was
0.0519 g. Calculate the equilibrium constant of dimerisation of the acid.
14. The equilibrium constant for the reaction cis-2-butene trans-2-butene is 2.07 at 400 K
temperature. Calculate the standard reaction Gibbs function.
EXERCISE # 04 ADVANCE SUBJECTIVE EXERCISE (LEVEL # 02)
1. The equilibrium constant Kp of the reaction

2SO2(g) + O2(g) 2 SO3(g) is 900 atm–1 at a temperature of 800 K. A mixture containing SO3
and O2 at initial partial pressures of 1 atm. and 2 atm. respectively is heated at a constant volume to
equilibrate. Calculate the partial pressure of each gas at 800 K.
2. Ammonium hydrogen sulphide (NH4HS) solid when kept in an evacuated flask at a certain temperature
dissociates into H2S gas and NH3 gas and the total gas pressure was 500 Torr. Calculate the value
of Kp for the dissociation reaction. If an additional amount of ammonia is introduced in the mixture
without changing the temperature until the partial pressure of ammonia becomes 700 Torr, what is
the partial pressure of H2S and total gas pressure in the flask?
3. CaCO3 solid dissociates to give CaO and CO2 gas at 298 K. What will be the pressure of CO2 at
equilibrium state of the reaction?;
0
Given G 0f (CaCO3s) = –1129 KJ mol–1 ; G f (CaOs) = –604.2 KJ mol–1 and
G 0f (CO2 g) = –395 KJ mol–1
4. Br2 gas and NO gas were reacted at 300 K to produce NO Br gas. At equilibrium, the total pressure
was 110.5 Torr. If the initial pressure of NO was 98.4 Torr and Br2 was 41.3 Torr, calculate the value
of equilibrium constant and the standard free energy change of the reaction at 300 K.
5. A saturated solution of iodine in water has 0.330 g of iodine per litre. Larger amounts of iodine can be
dissolved with the help of KI and the following reaction takes place
KI + I2 KI3
When 0.100 M KI solution dissolves 12.5 g of iodine per litre, most of it is converted to KI3. If the
concentration of I2 in all saturated solutions is the same, calculate the equilibrium constant of the
above reaction.
6. At 817°C Kp, for the reaction between CO2 and excess of hot graphite to form CO(g) is 10.
CO2(g) + C(s) 2CO(g)
(a) What are the partial pressures of CO(g) and CO2(g) at equilibrium at 817°C and a total pressure
of 4 atm.?
(b) At what total pressure will the gas mixture have 6% CO2 by volume?
7. H° of Zn(s) + H2O(g) ZnO(s) + H2(g) is + 224 KJ mol–1 from 920 K to 1280 K. G° is +33 KJ
mol–1 at 1280 K. Assuming that both quantities remain constant, estimate the temperature at which
the equilibrium constant becomes greater than 1.0.
8. The equilibrium constant for the reaction

H3 BO3 + glycerine H3 BO3 –glycerine is 0.75. How much glycerine should be added per litre
to 0.20 M H3 BO3 so that 60% of the H3 BO3 is converted to H3BO3 –glycerine complex?
9. A 0.01 M solution of a weak acid HA has an osmotic pressure of 0.293 atm at 25°C. A 0.01 M
solution of another weak acid HB has an osmotic pressure of 0.345 atm under the same conditions.
Which acid has a larger equilibrium constant for ionisation?
10. In a vessel with a volume of one litre, the following gases are at equilibrium at 400°C and the
equilibrium concentrations of the same are given below:
[N2] = 1.00M ; [H2] = 0.50 M ; [NH3] = 0.25 M.
How many moles of H2 must be removed from the vessel to increase the concentration of nitrogen to
1.1 M?
EXERCISE # 05 KVPY, OLYMPIOD QUESTION

1. Consider the equilibria (1) and (2) with equilibrium constatns K1 and K2, respectively.
[KVPY 2013]
SO2  g   1/ 2O2  g  SO3  g  ....(1)
2SO3  g  2SO2  g   O2  g  .......(2)

2. For the reaction, A nB the concentration of A decreases from 0.06 to 0.03 mol L-1 and that
of B rises from 0 to 0.06 mol L-1 at equilibrium. The values of n and the equilibrium constant for
the reaction, respectively, are [KVPY 2013]
(A) 2 and 0.12 (B) 2 and 1.2 (C) 3 and 0.12 (D) 3 and 1.2
3. The equilibrium constant Kc of the reaction, 2A B+C is 0.5 at 25°C and 1 atm. The reaction
will proceed in the backward direction when concentrations [A], [B] and [C] are, respectively
[KVPY 2014]
(A) 10-3, 10-2 and 10-2 M (B) 10-1, 10-2 and 10-2 M
(C) 10-2, 10-2 and 10-2 M (D) 10-2, 10-3 and 10-3 M
4. The equilibirum constants  Kc  of two reactions H2  I 2 2HI and N2  3H2 2NH3 are 50
and 1000, respectively. The equilibrium constant of the reaction N2  6HI 2NH3  3I2 is
closest to [KVPY 2014]
(A) 50000 (B) 20 (C) 0.008 (D) 0.005
5. The equilibrium constats for the reactions X = 2Y and Z = P + Q are K1 and K2, respectively. If the
initial concentrations and the degree of dessociation of X and Z are the same, the ratio K1/K2 is
[KVPY 2015]
(A) 4 (B) 1 (C) 0.5 (D) 2
EXERCISE # 06 JEE (MAIN) CORNER
1. The Haber’s process for the formation of NH3 at 298K is: [2006]
N2 + 3H2 2NH3; H = – 46.0 kJ; Which of the following is the correct statement
(A) The condition for equilibrium is G N + 3G H = 2G NH where G is Gibbs free energy per mole
2 2 3
of the gaseous species measured at that partial pressure.
(B) On adding N2, the equilibrium will shift to forward direction becasue according to IInd law of
thermodynamics the entropy must increasse in the direction of spontaneous reaction.
(C) The catalyst will increase th rate of forward reaction by 2 times and that of backward reaction by
1.5 times
(D) None of these
2. A vessel at 1000 K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted into CO
on the addition of graphite. If the total pressure at equilibrium is 0.8 atm, the value of K is
[2011]
(A) 3 atm (B) 0.3 atm (C) 0.18 atm (D) 1.8 atm
3. The equilibirum constant  KC  for the reaction N2  g   O2  g   2NO  g  at temperature T is 4  104 .
The value of KC for the reaction, NO  g   1/ 2 N2  g   1/ 2O2  g  at the same temperature is:
[2012]
(A) 0.02 (B) 2.5  10 2 (C) 4  10 4 (D) 50.0
1
4. For the reaction, SO2g   O2 g  SO3  g  , if K P  KC  RT  X where the symbols have usual
2
meaning then the value of x is: (assuming ideality) [2014]
1 1
(A) (B) 1 (C) 1 (D)  .
2 2
EXERCISE # 07 JEE (ADVANCE) CORNER
1. The dissociation constant of a substituted benzoic acid at 25C is 1.0  104. The pH of a
0.01M solution of its sodium salt is [2009]
2. Amongst the following, the total number of compounds whose aqueous solution turns red litmus
paper blue is [2010]
KCN K 2 SO4
 NH 4 2 C2O4 NaClZn  NO3  2
FeCl3 K 2CO3
NH 4 NO3 LiCN
3. The total number of diprotic acids among the following is: [2010]
H 3 PO4 H 2 SO4 H 3 PO3 H 2CO3
H 2 S 2O7 H 3 BO3 H 3 PO2 H 2CrO4
H 2 SO3
4. The thermal dissociation equilibrium of CaCO3  s  is studied under different conditions
CaCO3  s  CaO  s   CO 2  g  . For this equilibrium, the correct statement(s) is(are)

[2010]
(A) H is the dependent on T
(B) K is independent of the intial amount of CaCO3
(C) K is dependent on the pressure of CO2 at a given T

(D) H is independent of catalyst, if any
5. The equilibrium 2Cu I Cu   Cu II in aqueous medium at 25°C shifts towards the left in the
presence of [2011]
(A) NO3 (B) Cl  (C) SCN  (D) CN  .
6. The % yield of ammonia as a function of time in the reaction [2015]

N2  g   3H2  g  2NH3  g  , H  0
at (P, T1) is given below:
If this reaction is conducted at (P, T2), with T2 > T1, the % yield of ammonia as a function of time
is represented by
(A) (B)
(C) (D)
7. The equilibrium constant KP for this reaction at 298 K, in terms of  equilibrium , is [2016]
2 2 2 2
8 equilibrium 8 equilibrium 4 equilibrium 4 equilibrium
(A) 2   (B) 4   2 (C) 2   (D) 4   2 .
equilibrium equilibrium equilibrium equilibrium
8. The INCORRECT statement among the following, for this reaction is [2016]
(A) Decrease in the total pressure will result in formation of more moles of gaseous X
(B) At the start of the reaction, dissociation of gaseous X2 takes place spontaneusly
(C)  equilibrium  0.7 .
(D) KC < 1.
ANSWER KEY EXERCISE # 01 OBJECTIVE EXERCISE
1. C 2. B 3. C 4. A 5. C
6. C 7. B 8. B 9. C 10. B
11. C 12. B 13. C 14. D 15. A
16. C 17. A 18. C 19. B 20. D
21. A 22. B 23. A 24. B 25. C
26. C 27. B 28. D 29. C 30. C
31. D 32. B 33. C 34. C 35. B
36. C 37. D 38. C 39. C 40. B
41. A 42. A 43. D 44. B 45. B
46. C 47. B 48. A 49. B 50. C
ANSWER KEY EXERCISE # 02 ADVANCE LEVEL EXERCISE

1. A,B,C 2. A,C,D 3. A,B,C,D 4. A,B
5. B,D 6. A,B,C,D 7. A,B 8. A,C
9. A,B,C 10. A,B,C 11. A,B,D 12. B,C,D
13. B,C 14. B,C 15. A,B 16. B,C
17. A,C,D 18. A,C,D 19. A,B,C,D 20. A,C
21. A,B,D 22. A,C 23. A,B,C,D 24. B,C,D
25. B,C 26. D 27. B 28. A
29. C 30. A
1. Kp = 0.267 atm. and 63% dissociation at 0.1 atm pressure and 37°C
2. Kc = 150.85 (mol L–1)–2 and Kp = 0.04513 atm–2
4. 7.5  10–18 M 5.  = 0.433 and Kp=0.231

6.  = 0.5 and Kp = 0.319 7. N2 = 0.79 and O2 = 0.21
8. 0.407 9. 50.08 atm–1 10. 0.0174 g
11. 0.408 atm. 12. 83.06 KJ 13. K = 0.704
14. G° = –2.42 KJ mole–1
ANSWER KEY EXERCISE # 04 ADVANCE SUBJECTIVE EXERCISE (LEVEL # 02)

1. PSO = 0.023 atm, PO = 2.0115 atm, PSO = 0.977 atm.
2 2 3
2. Kp = 62, 500 Torr, PH 2S = 89.3 Torr, Ptotal =789.3 Torr
3. 1.776  10–23 atm 4. Kp = 132.41 atm–1 and G = –12.188 KJ mol–1

5. K = 707.0
6. PCO = 3.062 atm and PCO 2 = 0.938 atm. P = 0.679 atm
7. T2 = 1501.2 K 8. 2.0 moles
9. HA – Ka = 5  10–4 and HB – Ka = 3  10–3

10. 0.0156 moles
ANSWER KEY EXERCISE # 05 KVPY, OLYMPIOD QUESTION
1. 2. A 3. A 4. C 5. A
ANSWER KEY EXERCISE # 06 JEE (MAIN) CORNER

1. A 2. D 3. D 4. D
ANSWER KEY EXERCISE # 07 JEE (ADVANCE) CORNER

1. 8 2. 3 3. 6 4. ABD
5. BCD 6. B 7. B 8. C
ELECTROSTATICS 1
IONIC EQUILIBRIUM
INDEX
 CONCEPTS IN BRIEF (Ionic Equilibrium) 43 – 61
 SOLVED EXAMPLES 62 – 72
 EXERCISE # 03 SUBJECTIVE EXERCISE (LEVEL # 01) 81

 EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS 84

 EXERCISE # 06 JEE (MAIN) CORNER 85
 EXERCISE # 07 JEE (ADVANCED) CORNER 86
WEIGHTAGE OF ‘IONIC EQUILIBRIUM’ IN JEE (MAIN & ADVANCED) in Last Three Years
MARK /
YEAR No. Of Qs.
2014 0 0/120
2015 0 0/120
2016 1 4/120
JEE (ADVANCED)
MARK /
YEAR No. Of Qs.
2014 0 0/120
2015 2 8/168
2016 0 0/124

IONIC EQUILIBRIUM 43
IONIC EQUILIBRIUM
Electrolytes: Whose aqueous solution conduct electricity.
Electrolytes are classified into two groups.
1. Strong Electroytes: Are those whose ionization is almost 100%, in aqueous solution generally
all ionic compounds are strong electrolytes e.g. NaCl, NaNO3, HCl, KCl.
2. Weak Electrolytes: Whose degree of dissociation is < 10-15%. Generally covalent compounds
are weak electrolytes. e.g. NH 4OH,CH3COOH .
Strong and Weak electrolytes is a value term it only depends upon degree of ionization.
Some times covalent compounds acts as a strong electrolytes in highly diluted solution.
Ka ionized molecules
K a  C2    KaV       Total molecules
C
“The fraction of total no. of molecules of electrolytes dissolved, that ionizes at equilibrium is
called degree of ionization or degree of dissociation.”
For: unionized molecules ionized molecules  << 1
Generally strong and weak electrolyte property depends upon nature of solvent NaCl in H2O
acts strong electrolyte whereas CH3COOH is weak electrolyte in water. But in liquid NH3, the
dissociation of NaCl and CH3COOH both are same.
OSTWALD’S DILUTION LAW

Ostwald pointed out that like chemical equilibrium, in ionic equilibrium we can apply law
of mass action. An equilibrium between ionized and unionized molecules.
Consider a binary electrolyte having conc. C and degree of dissociation is .
AB A   B
At. time = 0 C 0 0
At time = t C(1 – ) C  C
 A B   2
K eq     C  C  C 
, for a weak electrolyte 1    1
 AB  C 1    1  
K eq
K eq  C  2 ,  
C
If 1 mole of AB is present in ‘V’ litre of solution.
1
C    K eq  V
V
Keq
Conc. of [A+] = Conc. [B–] = C   C  KeqC
C
Limitation
(i) This is only for weak electrolytes not for strong electrolytes.
(ii) This law is not applicable for strong electrolytes because strong electrolytes are almost completely
C
ionized at all dilution and hence does not give accurate results.

RELATIVE STRENGTH OF ACIDS AND BASES
For weak acids
Strength of I acid
Relative strength =
Strength of II acid
For Acids HA1 if concentration is C1 and degree of dissociations 1
HA1 H+ + A1–  [H  ]  C11

For HA 2 if concentration is C 2 and degree of dissociation is  2
HA2 H+ + A2–  [H  ]  C2  2
[H  ] furnished by I acid C11

Then, Relative strength  
[H  ] furnished by II acid C2  2
C1  K a C2   K a C1 
R.S.    1   1 
C2  K a C1   K a C2 
 2   2 
If C1 and C 2 are same, then
 Ka 
R.S.   1 
 Ka 
 2 
COMMON ION EFFECT

The degree of dissociation of a weak electrolyte is suppressed by the addition of another
electrolyte containing the common ion.
Quantitative Aspect
HA H+ + A– its degree of dissociation be .
Ka

C
BA (another electrolyte) added whose molarity is M, due to this the new degree of dissociation
becomes  .
BA B+ + A–
0 M M
HA H+ + A–
C(1 –  ) C  C 
H    A  C  'C ' M 
K a  HA       
HA C 1   '  
K a  HA   C  '2  M  ' 1    1
C '2 Neglecting because    1
Ka
' 
M
As a result of common ion effect, the conc. of the ion, which is not common changes to
make the Ka constant, because K only depends upon temperature not on concentration.
Note: The use of this phenomenon is made in quantities analysis to adjust the conc. of
S– – ions in second group (reagent H2S and HCl) and OH– ion conc. in third group (NH4Cl
+ NH4OH).
IONIZATION OF WATER
Water is a weak electrolyte. It does not dissociate completely, the undissociated water and the
dissociated H+, OH– remain in the equilibrium. Let us take pure water whose density is 1 gram/c.c.
and hence its concentration would be (1000/18 = 55.55 M). Let the degree of dissociation of water
be .
2H2O(  ) H3O+ + OH–
C C
H3O   OH  
K eq   
H2O
K eq  H2O      H3O   OH  

Since conc. of pure water remain constant
K eq k  H3O   OH  
kw  H3O   OH  
K w  dissociation constant of water at 25°C, Kw comes out to be 1  10–14.

Kw depends upon temperature dissociation of water gives equal no. of H3O+ and OH– ions.
2 2
1 10 14  H3O    OH  
So H3O    OH    107 mole/litre

   
pH = –log [H3O ] = – log [10–7] = 7.
+
pOH = – log [OH–] = – log 10–7 = 7.

Note: In case of water
[H3O+]w [OH–]w = 10–14.
But in case of acidic or basic solution.
[H3O+]T [OH–]T = 10–14, where [H3O+]T and [OH–]T are the conc. of [H3O+] and [OH–] totally present
in the solution.
pH CALCULATION
The pH of a solution is the negative logarithm (to the base 10) of the concentration (in moles per
litre) of hydrogen ions which it contains.
pH = –log10 [H3O+]
pOH = –log10 [OH–]
pkw = –log10 [Kw]
kw = [H+] [OH–]
taking –ve log10 both side
–log Kw = –log [H3O+] + [– log (OH–)]
pKw = pH + pOH
at 25°C, Kw = 1  1014 , pKw = 14
pH + pOH = 14
Kw = is also called as auto protolysis constant, it increases with temperature.
Since with increase in temperature dissociation of water increases, therefore the value of Kw

increases as the temperature is increased, however at all temperature H3O  remain equal to
[OH – ] in pure water..

pH DETERMINATION FOR WEAK ACIDS
Weak acids do not dissociate completely in the water their % degree of dissociation is very less.
e.g. lets takes CH3COOH (C mole/litre and having degree dissociation ).
CH3COOH CH3COO– + H+
C(1–) C C
CH3COO   H  
K aCH       C  C
3COOH   3
CH COOH  C 1   
C2
Ka 
1 
if   0.1 , then we can neglect 1   1
Ka
K a  C2  
C
K
H    C  C a  K aC
  C
pH = –log [H+] = – log10  K aC 
C 2
Note: For calculating the pH of a weak acid first of all we calculate  from the equation K a  ,
1 
if  comes out to be  0.1 then 1 –  will be taken as one and we use formula K a  C  2
otherwise we would be use the formula
C 2
Ka  for all calculation.
1 
DETERMINATION OF pH OF ACIDS OR BASES

For strong acid
HCl   H+ + Cl–
pH = –log [H+]
If conc. of HCl is less than 10–6M than we take conc. of H+ from water into accounts i.e. 10–7.
Otherwise we would neglect the conc. of H+ from water.
e.g. find the pH of 10–8 M HCl
According to rule
pH = –log [H+] = –log [10–8] = 8
But pH of an acid can’t be 8 so we have to take contribution of H+ from water
Total H+ ion in solution = H+ (from HCl) + H+ (from H2O) = 10–8 + 10–7 = 1.1 107 mole/litre
and hence
pH = –log [H+] = – log [ 1.1 107 ] = 7 – log 1.1 = 7 – 0.0414
pH = 6.9586 (Acidic).
Same rule applies for pH of 10 –8 M NaOH.
pH FOR THE MIXTURE OF WEAK ACID AND STRONG ACID
Let strong acid be HB whose conc. is C1
HB   H+ + B–
0 C1 C1
and weak acid whose conc. is C2 and degree of dissociation is 
HA   H+ + A–
C2(1 –) C2 C2
Total (H ) conc. = C1 + C2
+
pH = – log [C1 + C2]
H    A  C C  C  
K a HA        1 2 2
 
HA  2
C 1   
pH CALCULATION OF SOLUTION OF A MIXTURE OF TWO WEAK ACIDS IN WATER
Let two weak acids be HA and HB and their conc. are C1 and C2, 1 is the degree of dissociation
of HA in presence of HB (due to common ion effect) and 2 be degree of dissociation of HB in
presence of HA. In aqueous solution of HA and HB following equilibrium exists.
HA + H2O(l) H3O+ + A–
conc. at equi. C1(1 – 1) C11 + C22 C11
HB + H2O(l) H3O+ + B–
C2(1 – 2) (C1 1 + C2 2) C22
H3O    A   C   C  C  
K aHA       1 1 1 2 1 2
HA C1 1  1 
H3O   B   C   C  C  
K aHB       1 1 2 2 2 2
HB  C2 1   2  
pH   log H     log C11  C2 2 
pH OF A DIBASIC ACIDS AND POLYPROTIC ACID

Let’s take the eg. of a dibasic acid H2A. Assuming both dissociation is weak. Let the initial conc.
of H2A is C and 1 and 2 be degree of dissociation for first and second dissocation.
H2A HA– + H+
C(1 –1) C1 (1 – 2) C1 + C12
HA– H+ + A– –
C1 (1 – 2) C1 + C1 2 C1 2.
HA   H  
K a1    
H2 A
C 1 1   2   C 1  C 12 
K a1  
C 1  1 
H    A  C   C   C   
   1 1 2 1 2
K a2  
HA   C1 1  2  
 
After solving for 1 and 2. We can calculate the H+ conc.
[H+] = C1 + C1 2
pH = – log [C1 + C1 2]
pH OF MIXTURE
Let one litre of an acidic solution of pH 2 be mixed with two litre of other acidic solution of pH 3. The
resultant pH of the mixture can be evaluated in the following way.
Sample 1 Sample 2
pH = 2 pH = 3
[H+] = 10–2 M [H+] = 10–3 M
V = 1 litre V = 2 litre
M1V1 + M2V2 = MR(V1 + V2)
10–2  1 + 10–3  2 = MR(1 + 2)
12 103
 MR
3
4  103  M R (Here, MR = Resultant molarity)
pH R  – log[4 10 –3 ]  2.3980
pKa and pKb for a conjugate acid-base pair

For an acid HX
HX H  X 
H    X  
 Ka     
… (A)
HX 
For conjugate base X – of acid HX
X   H2O HX  OH 
HX  OH  
Kb  … (B)
X  
 
By eqs. (A) and (B),
K a  K b  [H  ][OH – ]  K w
or pK a  pK b  pK w  14
Note : 1. Stronger is acid, weaker is its conjugate base.
2. Higher is the value of pK a of an acid, lower is acid strength and higher is basic
strength of its conjugate base.
BUFFER SOLUTION
A Buffer solution is that which resist the pH change by addition of small quantity of acid or alkali.
There are three types of buffer
(i) Acidic Buffer (ii) Basic Buffer (iii) Salt Buffer
Mechanism of Buffer Action:

Let us see why CH3COONH4 is a Buffer while NaCl is not. CH3COONH4 exists almost entirely in
form of it’s ion CH3COO– or NH 4 if an acid is added to that solution, the H+ ion furnished by the
acid combine with CH3COO– ions to form feebly dissociated molecule of CH3COOH.
CH3COO– + H+ CH3COOH
Since most of the H+ ions added are taken up by CH3COO– to form CH3COOH which itself slightly
dissociated, the pH of CH3COONH4 changes only slightly.
Now, suppose a base is added to CH3COONH4 solution the OH– furnished by the base will be
taken up by NH 4 ion to form feebly dissociated NH4OH.
NH 4  OH  NH4OH
Since most of the OH– ions are taken up by NH 4 ions to form feebly dissociated NH4OH. Due to
this very little change in the pH of CH3COONH4 solution occurs.
Now let us see why a solution of NaCl is not a Buffer. In aqueous solution it is almost entirely
dissociated into Na+ and Cl–. If H+ ions are added to this solution the H+ combines with Cl– to form
HCl which completely dissociated due to strong electrolyte hence pH falls.
If OH– ions are added to the solution, it will combine with Na+ to form NaOH which will almost
completely dissociated. Hence pH will rise.
ACID BUFFER
A very common acidic buffer is prepared by mixing equimolar solutions of acetic acid and sodium
acetate. Acetic acid is very slightly dissociated while sodium acetate, being a salt, is almost
completely dissociated. The mixture thus contains CH3COOH molecules as well as CH3COO 
and Na  ions. Let us consider the buffer action of this mixture.
Suppose a strong acid is added to the above mixture. The H  ions added will be taken up
immediately by CH3COO  ions to form very slightly dissociated CH3COOH
:
H   CH3COO   CH3COOH
Feebly dissociated
Thus, the H ions added are neutralized by the acetate ions present in the mixture. There is very

little change in the pH of the mixture.

If, on the other hand, a strong base is added, the OH  ions added are neutralized by the acetic
acid present in the mixture :
OH   CH3COOH  CH3COO   H2O
Thus, again, there is very little change in the pH of the mixture.
CALCULATION OF pH OF ACIDIC BUFFER SOLUTION

e.g. Mixture of (CH3COOH + CH3COONa)
CH3COOH CH3COO– + H+
CH3COO   H  
Ka    
CH3COOH 
Since most of CH3COO– comes from salt (CH3COONa) and hence conc. of CH3COO– will be conc.
of CH3COONa.
Salt  H  
Ka 
 Acid 
Ka  Acid 
 H   
  Salt 
Taking (–ve) log both side
[Acid]
–log [H+] = – log Ka – log
[Salt]
Handerson’s equation
[Salt]
pH = pK a  log
[Acid]
BASIC BUFFER
A mixture containing equimolar solutions of ammonium hydroxide and its almost completely
dissociated salt, ammonium chloride, constitutes another good basic buffer. The mixture contains
undissociated NH4OH as well as NH 4 and Cl  ions. The buffer action of this mixture may now be
considered.
If a strong acid is added, the H  ions added are neutralized by the base NH4OH :
H   NH4OH  H2O  NH4

If a strong base is added, the OH  ions added are neutralized by NH 4 ions forming very slightly
dissociated NH4OH .
CALCULATIO OF pH OF BASIC BUFFER SOLUTION

e.g. Mixture of (NH4OH + NH4Cl)
NH4OH NH 4 + OH–
NH 4  OH  
Kb    
.
NH4OH 
Since most of NH 4 ions comes from salt (NH4Cl) so we take NH 4 conc. as conc. of salt (NH4Cl).
Salt  OH  
Kb 
Base 
K b  Base 
OH   
  Salt 
Taking (–log10) both side
Base 
–log [OH–] = – log 10 Kb – log
Salt 
pOH  pK b  log
Salt 
Base 
Hence pH = 14 – pOH at 14°C,
K w  1 10 –14 mol/litre
SALT BUFFER
A salt buffer is a solution of a salt which itself can act as a buffer. Such salt is the salt of a weak
acid and weak base.
For example, CH3COONH 4 CH3COO  NH4
When an acid is added, it reacts with CH3COO  to produce CH3COOH and when a base is added,
it reacts with NH 4 to produce NH4OH .
BUFFER CAPACITY OR BUFFER INDEX
Buffer capacity of a solution is defined in terms of buffer index which is the change in the concentration
of Buffer acid (or base) required for change of it’s pH value by one, keeping Csalt  Cacid  or
Cbase  Csalt  constant.

Let there be a buffer solution of volume 1 litre with ‘x’ mole of acid and ‘S’ moles of ‘salt’.
S
pH  pK a  log10
x S
1 S
pH  pK a  loge
2.303 x S
  pH  1 1 1 
 
S 2.303  S x  S 

  pH  1 x S S
  
S 2.303  S  x  S  
S 1 S  x  S  
  
  pH  2.303  x 
Maximum value of Buffer Index
1 S x  S
B.I. 
2.303 x
d 1 1
 B.I.   x  2S 
dS 2.303  x 
for maximum value of Buffer index
d
 B.I.  0 .
dS
After solving S = x/2
Salt  S x/2
Thus Acid  x  S  x  x / 2  1 .
 
Salt 
Hence max. value of Buffer index occurs when Acid  1 .
 
BUFFER RANGE
It is difficult to give an exact limit upto which a buffer can be used it in generally accepted that a
solution has useful buffer capacity provided that the value of [Salt]/[Acid] lie within the range of 10
to 0.1.Hence from Henderson equation
pKa  log0.1  pH  pK a  log10 10
pK a  1  pH  pK a  1
Outside this range the Buffer capacity is too small to be of any practical application.
HYDROLYSIS OF SALT
Salts are strong electrolytes when dissolved in water, they dissociated almost completely into
cations or anions. If anion reacts with water it is called as anionic hydrolysis.
A– + H2O   HA + OH–
Alkaline solution (pH increases).
If cation reacts with water it is called as cationic hydrolysis.
B+ + 2H2O 
 B(OH) + H3O+
Acidic solution (pH lowers down).
“The phenomenon of the interaction of anions and cations of the salt with H+ and OH– ions furnished
by water yielding acidic or alkaline solution is known as salt hydrolysis.
For the study of hydrolysis salts are divided into 4 groups.
Hydrolysis of salt of strong Acid or weak base:

NH4Cl is a salt of weak base (NH4OH) and strong acid (HCl). After hydrolysis resultant solution will
be acidic due to presence of strong acid HCl.
NH 4Cl  H2O NH4OH  HCl
NH 4  Cl   H2O NH 4OH  H   Cl 
NH4  H 2O NH 4OH  H 
 acidic 
NH4OH  H  
Kh  .
NH4 
 
Relation B/w K h , K b and K w :

NH4OH NH 4  OH 
NH 4  OH  
Kb    
… (1)
NH4OH 
H 2O H   OH 
KW  H   OH   … (2)
Dividing (2)  (1)
KW H   OH  
     NH OH
 4 
Kb NH 4  OH  
  
KW
 Kh
Kb
Degree of hydrolysis
NH 4  H2O NH4  OH 
C 1 h  Ch Ch
Ch  Ch
Kh   Ch2 (1 – h  1)
C 1  h 
Kh KW
h  h
C K bC
KW KW  C
H    Ch  C  H   
  K bC   Kb
Taking –log10 both side
1 1 1
pH 
2
 pKW  pK b  logC   pH  7 
2
pK b  logC
2
Hydrolysis of salt of weak acid and strong base:

CH3COONa is a salt of weak acid (CH3COOH) and strong base (NaOH). After hydrolysis resultant
solution will be basic due to presence of strong base (NaOH).
CH3COONa  H2O    CH3COOH  NaOH
CH 3 COO   Na   H 2O    CH3COOH  Na   OH 
CH3COOH  OH  
Kh 
CH3COO  
 
Relation between, K h , Kw and Ka
CH3COOH CH3COO   H 
CH3COO   H  
Ka    
… (1)
CH3COOH 
H 2O H OH 
K W  H   OH   … (2)
Dividing equation (2) ÷ (1)
KW H   OH    CH3COOH  OH   CH3COOH 

    
   Kh
Ka CH3COO   H   CH3COO  
    
Degree of Hydrolysis
CH3COO   H2O    CH3COOH  OH 
at time = 0 C 0 0
at time = t C(1 – h) Ch Ch
Ch  Ch
Kh   Ch2 (1 – h
C 1  h   1) h should be smaller than 0.1 than 1 – h = 1.
Kh KW
h  h
C KaC
KW KW C
 OH   C 
OH   Ch KaC Ka
KW Ka K a  KW
H3O    KW 
OH  KW C C
 
Taking (–ve) log both side
1 1 1 1
 log H    log KW  log Ka  log C   pKW  pKa  logC 
  2 2 2 2
1 1
pH  7  pKa  logC
2 2
pH will be more than 7, hence resultant solution will be basic in nature.
Hydrolysis of salt of Weak Acid and Weak Base:

Let’s take the salt CH3COONH4 made of salt of weak acid (CH3COOH) and Weak base (NH4OH).
CH3COONH4  H2O CH3COOH  NH 4OH
CH3COO   NH 4  H2O CH3COOH  NH 4OH
CH3COOH NH 4OH 

Kh 
CH3COO   NH 4 
  
Relation between, K h , Kw ,Ka ,& K b
CH3COOH CH3COO   H 
CH3COO   H  
Ka    
… (1)
CH3COOH 
NH4OH NH 4  OH 
NH 4  OH  
Kb    
… (2)
 4 
NH OH
H 2O H   OH 
K w  H   OH   … (3)
Kw H   OH    CH3COOH NH 4OH 

  
 Kh 
Ka  K b CH3COO   H   NH4  OH  
    
Kw
 Kh .
Ka  K b
Degree of Hydrolysis
CH3COO   NH 4  H2O CH3COOH  NH 4OH
at time = 0 C C 0 0
at time = t C(1 – h) C(1 – h) Ch Ch
Ch  Ch h2
Kh  
C 1  h  C 1  h  1  h 2
if h  0.1, 1  h  1
h Kw

1 h KaKh
The acetic acid formed would partially decompose to give CH3COO  and H  . But because of
common ion effect (that is, due to the unhyrolysed CH3COO  ) it is possible to neglect the acetate
ion coming from CH3COOH .
Therefore CH3COOH CH3COO   H 
C C(1– )
C  1    H  
Ka   
C
H  
Ka    (1–   1)

Kw Kw Ka 1
H    Ka   Ka  or pH  pKw  pK a  pK b .
  Ka K b Kb 2
This expression is independent of conc. of the salt.
(i) if Ka = Kb, pH = 7 solution will be neutral
(ii) if Ka > Kb, pH < 7, acidic solution
(iii) if Ka < Kb then pH > 7, alkaline solution
In the hydrolysis of salt of weak acid and a weak base such as NH4CN, CH3COONH4. Both the
ions are hydrolysied, if we assume K a  K b , then the hydrolysis of the cation and anion of the salt
occur approximately to equal extent for a salt which has K a  Kb , it would be expected at the first
glance that CN  ions hydrolysed to a much greater extent than NH 4 ions. However, the hydrolysis
of CN– ions produced OH– ions according to the equation.
CN   H2O HCN  OH 
which can react with NH 4 ions as
OH   NH4 NH4OH
This latter reaction causes equilibrium in the from reaction to be displaced to the right. Because
OH– ions are removed from the solution. Also the production of OH– by the former reaction displaces
the latter reaction to the right. Therefore the hydrolysis of one ion drags the hydrolysis of the other
ion along so that both the hydrolysis are fairly extensive not too far in extant from each other so it
is fairly safe to assume that [HCN] = [NH4OH], even in the case of the salt where K a  K b .
CASE IV: SALTS OF STRONG ACID + STRONG BASE

e.g., NaCl, KNO3 , … etc.
This category of salts does not undergo salt hydrolysis
SOLUBILITY AND SOLUBILITY PRODUCT

A solution which remain in contact with excess of the solute is said to be saturated. The amount
of a solute, dissolved in a given volume of a solvent (in 1 litre) to form a saturated solution at a given
temperature, it termed as the solubility of the solute in the solvent at that temperature.
Molar Solubility:
No. of moles of solute dissolved in per litre of solution
Solubility Product:
In a saturated solution of a salt, there exists a dynamic equilibrium between the excess of the
solute and ions furnished by that parts of the solute which has gone in solution. The solubility
product of a sparingly soluble salt is given as product of the conc. of the ions raised to the power
equal to the no. of times the ion occur in the equation after the dissociation of the electrolyte.
AxBy xAy+ + yBx–
x y
K sp   A y   Bx  
Let the solubility of AxBy is S then
x y
K sp   xS   yS 
K sp  x x .y y S x  y  .
The principle of solubility product is applicable for sparingly soluble salt.
COMMON -ION EFFECT ON SOLUBILITY
The common ion present in the solution decrease the solubility of a given compound e.g. The
solubility of BaSO4 in Na2SO4 solution is smaller than that in an aqueous solution.
Consider saturated solution of AgCl. If a salt having either of the ion common to AgCl say KCl is
added to it, then
AgCl  s   aq. Ag   Cl 
KCl  aq.  K   Cl 
For AgCl K SP   Ag   Cl   .
Cl   Increases in solution due to presence of KCl and thus to have K  Ag   will
  SP constant,  
decrease or AgCl will precipitate out from solution, i.e., solubility of AgCl will decrease with increasing
concentration of KCl in solution.
–1
Let 0.1 M KCl aq. solution with AgCl  aq. . If solubility of AgCl is s mol litre , then,
For AgCl K SP   Ag   Cl  
KSP  s  s  0.1 .
s being small in comparison to 0.1 and thus may be neglected therefore,
K SP
KSP  s  0.1 or s AgCl  .
0.1
where s is solubility of AgCl in presence of 0.1 M KClaq .
IONIC PRODUCT
For a solution of a salt at a specified concentration, the product of the concentration of the ions,
each raised to the proper power, is called as the ionic product for a saturated solution in equilibrium
with excess of solid, the ionic product is equal to solubility product.
At equilibrium, ionic product = solubility product
If ionic product is less than solubility product it means solution is unsaturated means more salt
can be dissolve in it.
If ionic product greater than solubility it means solution is holding more salt than can dissolve in it,
therefore ppt started till, until or unless ionic product becomes equal to Ksp.
PREFERENTIAL PRECIPITATION OF SALTS
Frequently, a solution contains more than one ion capable of forming a ppt. with another ion which
is added to the solution. e.g., in a solution containing Cl–, Br– and I–, if Ag+ ions are added then out
of the three, the least soluble silver salt is ppt first. If the addition of Ag+ ions is continued, eventually
a stage is reached when the next lesser soluble salt starts ppt along with the least soluble salt and
so on if the stocihiometry of the ppted salts is the same, then the salt with the minimum Ksp or
minimum solubility will ppted first followed by higher Ksp.
If the stoichiometry of the ppted salts is not the same, then with Ksp alone, we can’t predict which
ion will ppted first. e.g. a solution containing Cl– and CrO42 both of these ions form ppt with Ag+
though the Ksp (AgCl) > Ksp (Ag2CrO4). Yet it is AgCl (less soluble) which ppted first when Ag+ ions
2
added to the solution. In order to predict which ion (Cl– or CrO4 ) ppt first. We have to calculate
the conc. of Ag+ ion needed to start ppt through the Ksp and given conc. of Cl– and CrO42 if the
2
conc. of Ag+ ions needed to start the ppt of CrO4 is larger than that of Cl–. Hence as AgNO3 is
added to the solution, the minimum of the two conc. of Ag+ to start the ppt will be reached first and
thus the corresponding ion (Cl– in this case) will be ppted in preference to the other. During the
course of ppt conc. of Cl– decreases and conc. of Ag+ increases when its’s conc. become equals
to the conc. required (of Ag+) for CrO42 . At this stages the whole of Cl– ions have been ppted the
addition of more of AgNO3 causes the ppt of both the ions together.
(i) Solubility of a salt of weak acid and strong base in Basic Buffer suppresses than pure
water due to common ion effect. But in acidic buffer solution soubility increase than pure
water.
(ii) Solubility of salt of weak acid and weak base in pure water: Let the solubility of salt be S,
and y mol/litre is the amount of salt getting hydrolysed.
CH3COONH4 CH3COO– + NH 4 … (1)
S–y S–y

CH3COO– + NH 4 + H2O CH3COOH + NH4OH
S–y S–y y y … (2)
2
K sp   S  y  S  y    S  y 
Due to hydrolysis of salt from equation (2)
CH3COOH NH4OH  y .y
Kh  
CH3COO

 
 NH 4 
 S  y S  y  .
2
 y 
Kh    .
S  y 
Kw
and we also know that Kh  .
Ka Kb
SOLUBILITY OF A SALT OF WEAK ACID AND WEAK BASE IN ACIDIC BUFFER
Let the solubility of salt be S and y be the amount of weak acid being formed.

CH3COONH4 CH3COO– + NH 4
S–y y
CH3COO– + H+   CH3COOH … (2)
S–y (from Acidic Buffer) y
K sp  CH3COO   NH 4   S  y  y   y S  y  = [S – y] [y] = y [S – y]
for equation (2)
1 CH3COOH  y
 K a'  
K aCH
3COOH 
 
CH3COO  H   S  y  H
 
 
Solubility of CH3COONH4 in acidic buffer would be higher than in pure water
SOLUBILITY OF A SALT OF WEAK ACID AND WEAK BASE IN BASIC BUFFER
Similarly CH3COONH4 CH3COO– + NH 4
y S – y
NH 4  OH  NH4OH
S – y (from buffer) y
K sp CH  CH3COO   NH 4   K sp  y  S  y 
3COONH 4 
1 NH4OH  y
 K b'  
Kb  
NH 4  OH   S  y  OH 
    
The solubility of CH3COONH 4 in basic buffer would be higher than pure water..
SOLUBILITY OF AgCl IN AN AQUEOUS SOLUTION CONTAINING NH3
Let the amount of NH3 initially be ‘a’ M. if the solubility of salt be ‘b’ mole/ litre.
AgCl (s) Ag+ + Cl–
At time = 0 b 0 0
at time = t b–y y

Ag+ + 2NH3 Ag  NH3 2 (aq.)
b–y a –2y y
where y is the amount of Ag+ which reacted with NH3.
K sp   Ag   Cl     b  y  y .
 Ag  NH  
 3 2
 y
Kf  

 Ag  NH3  2
 b  y  a  2y  .
 
After knowing the value of Ksp and Kf the value of solubility can be calculated.
ACID - BASE INDICATORS

An acid & base indicator are substance which changes it’s colour within limits with variation in pH
of the solution to which it is added. Indicators, in general are either organic weak acid or weak
bases with a characteristics of having different colours in the ionized and unionized form e.g.
phenophthalein is a weak acid (ionized form is pink and unionized form is colourless).
Acidic Indicator Action (e.g. HPh)

HPh (Phenolpthalein) is a colourless weak acid
HPh H   Ph 
colourless  Pink 
H   Ph  
K IN    
.
HPh 
If the solution is acidic, the H+ by the acid increases and since Kin is constant and it does not
depend upon the concentration so HPb also increases mean equilibrium will shift towards left
means solution remain colourless. By addition of alkali, OH– will be furnished and that OH– will
combines with H+ of HPh to form water and equilibrium will moves towards right and therefore
solution becomes pink. Thus HPh appears colourless in acidic and pink in alkaline solution pH
range of HPh is (8.3 –10).
In  
pH  pK IN  log   .
HIn 
The colour of the indicator changes from colour A to colour B at a particular point known as end

point of indicator. At this point  HIn   In  means pH  pKIn (at this point half of indicator is in
the acid form and half in the form of its conjugate form.
INDICATION (BASIC) ACTION OF MeOH (METHYL ORANGE)

When MeOH is dissolved in water and undergoes dissociation to a small extent. The undissociated
molecules are yellow while dissociated Me+ are red in colour.
MeOH Me   OH 
yellow red colourless
If the solution is acidic, the H+ furnished by the acid combines with OH– ions furnished by the
indicators to form undissociated water. This shifts the equilibrium towards right giving red coloured
solution. Therefore in acid solution, this indicator gives red colour. In the presence of alkali, OH–
increases and due to common ion effect the dissociation of MeOH surpress means equilibrium will
shifts towards left. Hence the solution in alkaline medium remains yellow in colour.
Colour of solution depends upon relative amount of ionized form to unionized form (ratio of Me+/
MeOH).
In general pH range of indicator lies B/w pK ln  1 to pK ln  1
Case 1 : pH = pK ln  1
In 
Means HIn  0.1  10% .
 
Percentage ionization of indicator would be
In  0.10 HIn
 100%   100%

In    HIn  0.10 HIn   HIn 
 
1
 100  9.1% .
11
In fact, pH = pKIn – 1 is the maximum pH upto which the solution has a distinct colour characteristic
of HIn. At pH smaller than this value, more of the indicator is present in the unionized form.
Thus at pH  pKin –1, the solution has a colour characteristic of HIn.
Case 2 : at pH = pK In  1
In  
   10
Mean .
HIn 
Percentage of ionization of indicator is
In   10 HIn 
  1000
 100%   100%   91%

In   HIn  10 HIn    HIn  11
 

Thus most of the indicator is present in the ionized form In and solution gets the colour
characteristic. Infact pH = pKIn + 1 is the minimum pH upto which the solution has a distinct
characteristic of In  . At pH greater than this value, still more of the indicator is present in the

ionized form. Thus at pH  pK In  1 , the solution has a colour characteristics of In .
OSTWALD’S THEORY
According to this theory:
(a) The colour change is due to ionization of the acid-base indicator. The unionized form has different
colour than the ionized form.
(b) The ionization of the indicator is largely affected in acids and bases as it is either a weak acid or
a weak base. In case, the indicator is a weak acid, its ionization is very much low in acids due to
common H+ ions while it is fairly ionized in alkalies. Similarly if the indicator is a weak base, its
ionization is large in acids and low in alkalies due to common OH– ions.
Considering two important indicators phenophthalein (a weak acid) and methyl orange (a weak
base), Ostwald theory can be illustrated as follows:
Phenolphthalein: It can be represented as HPh. It ionizes in solution to a small extent as:
HPh H   Ph 
Colourless Pink
H   Ph  
K    
Applying law of mass action, .
HPh 
The undissociated molecules of phenolphthalein are colourless while Ph– ions are pink in colour. In
presence of an acid, the ionization of HPh is practically negligible as the equilibrium shifts to left
hand side due to high concentration of H+ ions. Thus, the solution would remain colourless. On
addition of alkali, hydrogen ions are removed by OH– ions in the form of water molecules and the
equilibrium shifts to right hand side. Thus, the concentration of Ph– ions increases in solution and
they impart pink colour to the solution.
HIn  H 2 O H 3 O  In 
`Acid form ' `Base form '
Conjuage acid-base pair
In   H3O 
H3O   K In 
HIn 
K In     
; K In  Ionization constant of indicator,,   In   .
HIn   

HIn 
pH = – log10 H3 O  = – log10 [KIn] – log10 .
In  
 
In  
 
pH = pKIn + log10 (Handerson equation for indicator)
HIn 
At equivalence point; In     HIn  and pH = pK
  In
Methyl orange: It is a weak base and can be represented as MeOH. It is ionized in solution to
give Me+ and OH– ions.
MeOH Me   OH 
Yellow Red
Me   OH  
K    
Applying law of mass action .
 MeOH 
In presence of an acid, OH– ions are removed in the form of water molecules and the above
equilibrium shifts to right hand side. Thus, sufficient Me+ ions are produced which impart red colour
to the solution. On addition of alkali, the concentration of OH– ions increases in the solution and
the equilibrium shifts to left hand side (due to common ion effect), i.e., the ionization of MeOH is
practically negligible. Thus, the solution acquires the colour of unionized methyl orange molecules,
i.e., yellow.
This theory also explains the reason why phenolphthalein is not a suitable indicator for titrating a
weak base against strong acid. The OH– ions furnished by a weak base are not sufficient to shift
the equilibrium towards right hand side considerably, i.e., pH is not reached to 8.3. Thus, the
solution does not attain pink colour. Similarly, it can be explained why methyl orange is not a
suitable indicator for the titration of weak acid with strong base.
Quinonoid Theory: According to this theory:
(a) The acid-base indicators exist in two tautomeric forms having different structures. Two forms are in
equilibrium. One form is termed benzenoid form and the other quinonoid form.
HO OH O O
(b) The two forms have different colours. The colour change is due to the interconversion of one
tautomeric form into other.
(c) One form mainly exists in acidic medium and the other in alkaline medium.
Thus, during titration the medium changes from acidic to alkaline or vice-versa. The change in pH
converts one tautomeric form into other and thus, the colour change occurs.
Phenolphthalein has benzenoid form in acidic medium and thus, it is colourless while it has
quinonoid form in alkaline medium which has pink colour.
OH O
OH 
C C
H
O
OH OH
C COO
Methyl orange has quinonoid form in acidic solution and benzenoid form in alkaline solution. The
colour of benzenoid form is yellow while that of quinonoid form is red.
CH3

O3S NH N N
CH3
Quinonoid form — Acidic solution (red)
OH-
H
CH3

O3S N N N
CH3
SOLVED EXAMPLES
Example 1:
Calculate the degree of ionization of 0.01 M solution of HCN, K a of HCN is 4.8  10 –10 .
Also calculate hydronium ion concentration.
Solution:
The ionization of HCN may be represented as,
HCN  aq   H2O    CN   aq   H3O   aq 
If degree of ionization of HCN is  then equilibrium concentration of various species are
HCN   C 1    , CN    C  , H3O    C 

   
where C = concentration of HCN.
Applying law of chemical equilibrium
CN   H3O   C  C  
C 2
Ka     
HCN  C 1    1   
Since  is very small as compared with unity therefore , 1 –  in the denominator may be
taken as 1.
K a  C 2
Ka 4.8  1010
    2.2  10 4 .
C 0.01
H3O    C  0.01 2.20  104  2.2  10 6 mol L1 .
 
Example 2:
Calculate the concentration of fluoroacetic acid which is required to get
[ H  ]  1.50  10 –3 M . [ K a . of acid  2.6  10 –3 ].
Solution:
FCH2COOH FCH2COO– + H+
[FCH2COO–] = [H+] = 1.5 × 10–3
(1.5 10 3 ) 2
 2.6 × 10–3 =
C  1.5 10 3
 C – l.5 × 10–3 = 8.65 ×10–4
 C = 2.365 × 10–3
Example 3:
Calculate the degree of ionization of 0.02 M acetic acid if its K a  1.8  10 –5 . What would
be the degree of ionization if the solution also contains 0.01 M sodium acetate ?
Solution:
CH3COOH  aq  CH3COO   aq   H   aq 
The degree of ionization of this weak acid can be calculated by the approximate relation
:
Ka 1.8  10 –5
   0.03  3  10 –2 .
C 0.02
Now let us calculate the degree of ionization when the solution also contains 0.01 M sodium
acetate. Sodium acetate being a strong electrolyte would be completely ionized in solution.
Let x mol L–1 of acetic acid be ionized.
CH 3COOH(aq) CH 3COO – (aq)  H  (aq)

(0.02– x )M xM xM
 CH 3COO – (aq)  Na  (aq)

CH 3COONa(aq) 
0.01 M 0.01 M
[H  ]  x mol L–1
[CH 3COO – ]  (x  0.01) mol L–1  0.01 mol L–1
[ x is very small as compared to 0.01]
[CH 3COOH]  (0.02 – x) mol L–1  0.02 mol L–1
H   CH3COO  
Ka     
.
CH3COOH 
1.8  10 5 
 x  0.01
  0.02  .
1.8  10 5  0.02
x  3.6  105 M .
0.01
Degree of ionization,
x 3.6  105
   1.8  10 3 .
0.02 0.02
Thus, it may noted that the degree of ionization of acetic acid has decreased from 3  10 –2 to
1.8 10 –3 due to the presence of sodium acetate.

Example 4:
Calculate the degree of ionization of pyridine (C 5 H5N) in its 0.1 M solution K b for
pyridine is 1.5  10 –9 . What would be the degree of ionization of pyridine if the solution
also contain 0.1 M in NaOH?
Solution:

C6H5N + H2O C6H5 N H + OH
Kb 1.5  10 9
   1.23  10 4
C 0.1
In presence of 0.1 M NaOH solution, common ion effect operates hence OH– ions are poduced
only by NaOH
1.5  109 
 0.1 0.1
  0.1
 = 1.5 × 10–8
Example 5:
The Kw for 2H2O H3O+ + OH– changes from 10–14 at 25°C to 9.62  10–14 at 60°C. What is
pH of water at 60°C ? What happens to its neutrality ?
Solution:
Kw for H2O at 25°C = 10–14
 [H+] [OH–] = 10–14 ( Kw = [H+] [OH–])
 [H+] = 10–7 M  pH = 7
Now Kw for H2O at 60°C = 9.62  10–14
 [H+] = [OH–] = 9.62  10–14
For pure water [H+] = [OH–]
 [H+]2 = 9.62  10–14
 [H+] = 9.62  10  = 3.10  10

14 –7
M
 pH = – log H+ = – log 3.10  10–7
pH = 6.51
Thus, pH of water becomes 6.51 at 60°C but the nature is neutral since calculation for pure water
has been made, i.e., pH scale at 60°C becomes in between 0 to 13.02.
Example 6:
Calculate pH for (a) 0.0008M Mg(OH)2, (b) 0.01 N Ca(OH)2
Solution:
(a) 0.0008M Mg(OH)2
Mg(OH)2  Mg+2 + 2OH–
 [OH–] = = 2 × 8 × 10–4 = 1.6 × 10–3  pOH = 2.8  pH = 11.2
(b) 0.01N Ca(OH)2
Ca(OH)2  Ca+2 + 2OH–
[OH–] = 0.01 N ( equivalents are always same)
 –
[OH ]= 0.01 M
 pOH = 2
 pH = 12
Example 7:
(a) pH of a solution is 10 in NaOH solution. What is concentration of NaOH ?
(b) What is molar concentration of Ca(OH)2 if its solution has pH of 12 ?
Solution:
(a) [H+] = 10–pH
[OH–] = 10–pOH
NaOH is strong base, hence [OH–] = [NaOH]
In pH = 10, pOH = 4
 [OH–] = 10–4 = [NaOH]
(b) pH of Ca(OH)2 = 12
 pOH = 2
 [OH–] = 10–2 M
102
 [Ca(OH)2] = M = 0.5  10–2 M
2
[Every Ca(OH)2 gives two OH– ions]
Example 8:
A solution of HCl has a pH = 5. If one mL of its is diluted to 1 litre, what will be pH of
resulting solution ?
Solution:
pH = 5
 [H+] = 10–5
 [HCl] = 10–5 M
now using dilution formla, M1V1 = M2V2
10–5 ×1 = M2 × 1000
 M2 = 10–8 M
At this low concentration, H+ ions are also produced from water
 [H+] = 1.05 × 10–7
 pH = 6.978
Example 9:
What concentration of HCOO– is present in a solution of 0.015 M HCOOH and 0.02 M HCl ?
Ka for HCOOH = 1.8  10 –4 .
Solution:
Given, [HCOOH]  0.015M
 [HCl] = 0.02 M
 [H  ] in solution = 0.02 M
The dissociation of HCOOH is suppressed due to common ion effect in presence of HCl. The
[H  ] is provided by HCl in solution.
HCOOH HCOO   H 
H   HCOO  
Ka     
HCOOH 
4
0.02 HCOO  
1.8  10 
0.015 
 HCOO    1.35  104 M
 
Example 10:

2

Calculate [H+] in a 0.20 M solution of dichloroacetic acid K a  5  10 that also contains
0.1 M sodium dichloroacetate. Neglect hydrolysis of sodium salt.
Solution:
CHCl2COOH CHCl2COO– + H+
CHCl2COONa  CHCl2COO– + Na+
CHCl 2COO   H  
 Ka    
CHCl 2COOH 
5  10 2 
 0.1  0.2  0.2 
 0.2 1   
1 1  2  
 
2 1 
 1 –  = 2 + 42
 42 + 3 –1 = 0
3  9  16
 
8
3  5
=
8
2
= = 0.25
8
 [H+] = 0.2  = 0.2 × 0.25 = 0.5
Example 11:
Calculate [H+] in a solution containing 0.1 M HCOOH and 0.1 M HOCN. Ka for HCOOH and
HOCN are 1.8  10 –4 and 3.3  10 –4 .
Solution:
In this problem both the acids contribute for [H  ] due to appreciable dissociation. Thus,
HCOOH H   HCOO 
0.1 – x x+y x 0.1 – x  0.1
 
HOCN H  OCN
0.1 – y x+y y 0.1 – y  0.1
Because [H  ] will remain common in solution. Thus,
H   HCOO  
K HCOOH      1.8  10 4
… (1)
HCOOH 
 H   OCN  
K HOCN      3.3  10 4
… (2)
 HOCN 
x  y  x
or K HCOOH   1.8  104 … (3)
0.1
x  y y
K HOCN   3.3  10 4 … (4)
0.1
Thus, by eqs. (3) and (4)
x 1.8
 or y = 1.83 x … (5)
y 3.3
From Eq. (3) (x  1.83x).x  1.8  10 –5  x  2.52 10 –3
Therefore, y  4.61 10 –3
Thus, [H  ]  x  y  2.52  10 –3  4.61 10 –3  7.13 10 –3 M

Example 12:
Find the concentrations of H  , HCO3– and CO3–2 in a 0.01 M solution of carbonic acid if
the pH of solution is 4.18. K 1  4.45  10 –7 , K 2  4.69  10 –11 .
Solution:
Given, pH = 4.18 = –log [H  ]  [H  ]  6.61 10 –5 mol litre –1
H2CO3 H   HCO3
H   HCO3 
 K1     
H2CO3 
6.61 105  HCO3 
or 4.45  107    
or HCO3   6.73  10 5 mol litre 1
 
0.01  
–
Again for dissociation of HCO3 , we have
HCO3 H   CO32
H   CO32 
  
K2 
HCO3 
 
[6.61 10 –5 ][CO3–2 ]
or 4.69  10 –11 
[6.73  10 –5 ]
 [CO3–2 ]  4.78  10 –11 mol litre –1
Example 13:
Calculate the pH of the resultant mixture
(a) 10 mL of 0.2 M Ca(OH)2 + 25 mL of 0.1 M HCl
(b) 10 mL of 0.01 M H2SO4 + 10 mL of 0.01 M Ca(OH)2
(c) 10 mL of 0.01 M H2SO4 + 10 mL of 0.1 M KOH.
Solution:
(a) Ca(OH)2 + 2HCl  CaCl2 + 2H2O
2 2.5
0.75 –
0.75
 [Ca(OH)2] =
35
0.75 1.5
 [OH–] = 2 × =
35 35
 pOH = 1.37
 pH = 12.63
(b) H2SO4 + Ca(OH)2  CaSO4 + 2H2O

millimoles at t = 0 0.1 0 .1
hence both will neutalise each other so solution will be neutrall, So pH = 7
(c) H2SO4 + 2KOH  K2SO4 + 2H2O
millimoles at t = 0 0.1 1
– 0.8
0. 8
 [KOH] = = 0.04
20
 [OH–] = 0.04
 pOH = 1.4
 pH = 12.6
Example 14:
Calculate the ratio of pH of a solution containing 1 mole of CH3COONa + 1 mole of HCl per
litre and of other solution containing 1 mole CH3COONa + 1 mole of acetic acid per litre.
Solution:
Case I: pH when 1 mole CH3COONa and 1 mole HCl are present.
CH3COONa + HCl 
 CH3COOH + NaCl
Before reaction 1 1 0 0
After reaction 0 0 1 1
 [CH3COOH] = 1 M
K
 H    C    C  a    Ka  C    Ka 
  C 
 C=1
1
 pH1 = – log Ka
2
Case II : pH when 1 mole CH3COONa and 1 mole of CH3COOH; a acidic buffer solution forms
 [Salt] = 1 M, [Acid] = 1 M
[Salt]
 pH2 = – log Ka + log
[Acid]
pH2 = –log Ka
pH1 1
 
pH2 2
Example 15:
Calculate pH change when 0.01 mol CH3COONa solution is added to one litre of 0.01 M
CH3COOH solution.
Ka (CH3COOH) = 1.8  10–5, pKa = 4.74.
Solution:
On addition of CH3COONa to CH3COOH solution resulting solution will be a buffer solution hence
on using Handerson eq. for acidic buffer.
[salt ]
pH = pKa + log
[acid ]
0.01
= 4.74 log = 4.74
0.01
 For initial pH,
H     Ka  C 
 
 1.8  105  0.01

= 4.24 × 10–4
 pH = 3.37
pH = 4.75 – 3.37
= 1.37
Example 16:
A buffer of pH 9.26 is made by dissolving x moles of ammonium sulphate and 0.1 mole of
ammonia into 100 mL solution. If pKb of ammonia is 4.74, calculate value of x.
Solution:
 NH4 2 SO4 2NH 4  SO42

Thus, every one mole of (NH4)2SO4 gives two moles of NH 4 .
 millimoles of NH3, (NH4OH) = 100  0.1 = 10 millimol
millimoles of (NH4)2SO4 = 100  x = 100 x millimol

millimoles of NH 4 = 200  x = 200 x millimol
 pH = 9.26  pOH = 14 – 9.26 = 4.74
NH4 
pOH  pK b  log  
NH4OH 
200x
4.74 = 4.74 + log
10
log 20x = 0
 20 x = 1
1
 x= = 0.05.
20
Example 17:
50 mL of 0.1 M NaOH is added to 75 mL of 0.1 M NH4Cl to make a basic buffer. If pKa of NH 4
is 9.26, Calculate pH.
Solution:
Using Handerson equation for basic buffer
pOH  pK b  log
salt 
base
 For NH 4OH,  pK a NH    pK b NH  14
4 4OH
  pKb  NH4OH = 14– 9.26 = 4.74

NH4Cl + NaOH  NH4OH + NaCl
t=0 7.5 5
t=t 2.5 – 5 5
2. 5
 pOH = 4.74 + log = 4.44  pH = 14 – 4.44 = 9.56
5
Example 18:
Calculate degree of hydrolysis and pH of 0.2 M solution of NH 4 Cl . Given K b for NH 4 OH
is 1.8  10 –5 .
Solution:
NH 4Cl  H 2 O NH4OH  HCl
Before hydrolysis 1 0 0
After hydrolysis 1 –h h h
Where h is degree of hydrolysis
K   K  1014
h  h  W   5
 5.27  105
 C  K
 b  C  1.8  10  0.2
From HCl, strong acid
K  KW   1014  0.2 
H    C  h  C  h   Kh  C   C     1.054  105 .
    C 

K  1.8  10 5 
 b   
 pH  – log[H  ]  – log1.054  10 –5 = 4.9771
Example 19:
Find out the amount of NH4Cl dissolved in 500 mL to have pH = 4.5. Kb for NH4OH is
1.8  10 –5 .
Solution:
Using salt hydrolysis formula
pK b log c 4.74 log c
pH  7    4.5  7    log c  0.26 .
2 2 2 2
 c =1.82 M
1.82
 WNH = × 53.5 = 48.7 gm
4Cl 2
Example 20:
Calcium lactate is a salt of weak organic acid and strong base, represented as Ca(Lac)2.
A saturated solution of Ca(Lac)2 contains 0.13 mole of this salt in 0.50 L solution. The pOH
of this solution is 5.60. Assuming a complete dissociation of the salt, calculate Ka of lactic
acid.
Solution:
Formula of calcium lactate suggests that lactic acid is dibasic acid. Each mole of salt furnishes
two moles of lactate ion
Ca(Lac)2 Ca2+ + 2 Lac–
0.50 L solution contains = 0.13 mol of salt = 0.26 mol of lactate ion
 1 L of solution contains = 0.52 mol of lactate ion
[lactate] = 0.52 M.
given pOH = 5.6
 pH = 8.4
using equation of pH for salt of weak acid and strong base
pK a logC
pH  7   .
2 2
pK a log0.52 pKa
8.4  7    7  0.14
2 2 2
pKa = 3.08
Ka = 10–3.08 = 8.3  10–4.
Example 21:
What is the pH of a 0.5 M aqueous NaCN solution? pK b of CN –  4.70 .
Solution:
1 1
PH = [14 + pKa + log c] = [14 + 9.3 + log 0.5] = 11.5
2 2
Example 22:
T he dissociation constants for aniline, acetic acid and water at 25°C are
3.83  10 –10 , 1.75  10 –5 and 1.008  10 –14 respectively. Calculate degree of hydrolysis
of aniline acetate in a deci normal solution. Also report the pH.
Solution:
 Aniline+ + Acetate– + H 2O Aniline + Acetic acid
Before hydrolysis 1 1 0 0
After hydrolysis 1– h 1–h h h
Let concentration of salt be C mol litre –1
Kh 
 Aniline Acetic acid   C.h.C.h
 
aniline  Acetate  C.  1  h  .C. 1  h 
h2
Kh 
 1  h 2
h h  K   1.008  10 14 
  Kh     w   
1 h  1.75  105  3.83  1010
1 h  K a .K b   
 h = 54.95%
Example 23:
Calculate the pH of an aqueous solution of 1.0 M ammonium formate assuming complete
dissociation. (pKa of formic acid = 3.8 and pKb of ammonia = 4.8)
Solution
1 1
pH = [pKw + pKa – pKb] = (14 + 3.8 – 4.8) = 6.5
2 2
Example 24:
A 100.0 mL sample is removed from a water solution saturated with CaSO4 at 25°C. The
water is completely evaporated from the sample and a deposit of 0.24 g CaSO4 is obtained.
What is Ksp for CaSO4 at 25°C ?
Solution:
CaSO4(s) Ca2+ (aq) + SO42 (aq), Ksp = ?
Data shows that the solubility of CaSO4 is 0.24 g per 100 mL.
0.24 1000
 [CaSO4] =  mol L1  0.01765 M .
100 136
 Ca2    SO42   0.01765 M .

   
2
 K sp  Ca 2  SO42    0.01765   3.115  10 4 .
  
Example 25:
Zn salt is mixed with (NH4)2S of molarity 0.021 M. What amount of Zn2+ will remain
unprecipitated in 12 mL of the solution? KSP of ZnS = 4.51  10–24.
Solution:
(i) Ksp = [Zn+2] [S–2]
4.51 × 10–24 = [Zn+2] × 0.021  [Zn+2] = 2.15 × 10–22 M
12
 amount = 2.15 × 10–22 × 65.4 × = 1.68 ×10–22 g
1000
Example 26:
Calculate the solubility of AgCN in a buffer solution of pH = 3. Given KSP of AgCN = 1.2 
10–16 and Ka for HCN = 4.8  10–10.
Solution:
AgCN Ag+ + CN– Ksp = 1.2 × 10–16 ......(1)
x x–y
Kw 1014
CN– + H2O HCN + OH– Kh   ......(2)
Ka 4.8  10 10
x–y y 10–11
Fom (1), x(x – y) = 1.2 × 10–16
1014 y  10 11
From (2) 
4.8  10 10 x  y 
1.2  10 16  1014
Multiplying both, xy × 10–11 =
4.8  1010
 xy = 2.5 × 10–11
now x2 – xy = 1.2 × 10–16  x2 = 1.2 × 10–16 + 2.5 × 10–11
 x2 = 2.5 × 10–10
x = 1.58 × 10–5 M
Example 27:
An indicator is a weak acid and pH range of its colour is 3.1 to 4.5. If the neutral point of
the indicator lies in the centre of the hydrogen ion concentrations corresponding to the
given pH range, calculate the ionization constant of the indicator.
Solution:
pH = – log [H3O+], or log [H3O+] = – pH
 [H3O+] = antilog of (–pH)
for pH = 3.1 [H3O+]1 = antilog of (–3.1) = antilog of (4.9)  7.94  104
for pH = 4.5 [H3O+]2 = antilog of (–4.5) = antilog of (5.5)  3.16  105

Since neutral point lies at the centre of the hydrogen ion concentration in the given pH range,
hence [H3O+] at the neutral point
H3O    H3O  
[H3O+]   1  2 .
2
7.94  104  3.16  105

  4.13  104 M .
2
Let indicator be HIn behaving as weak acid, then
HIn + H2O H3O+ + In–
H3O   In  
K In    
[ionization constant of indicator is KIn]
HIn 
= [H3O+] {since at neutral point [In–] = [HIn]} = 4.13  10–4.
Example 28:
Calculate the pH at which an acid indicator with Ka = 1  10–5 changes colour when the
indicator concentration is 1  10–3 M. Also report the pH at which coloured ion is 80%
present.
Solution:
In  
 
pH = pKIn + log .
HIn 
In  
  1
For colour change, .
HIn 
 pH = pKIn = – log (1 ×10–5) = 5
now [In–] = 80, [HIn] = 20
80
 pH = 5 + log = 5.6
20
1. 100 mL of 1 M HCl is mixed with 50 mL of 2 M HCl. Hence, [H3O+] is –
(A) 1.00 M (B) 1.50 M (C) 1.33 M (D) 3.00 M
2. At a temperature under high pressure
KW(H2O) = 1 × 10–10
A solution of pH 5.4 under these conditions is said to be :
(A) acidic (B) basic (C) neutral (D) amphoteric
3. Which has maximum pH ?
(A) 0.01 M H2SO4 (B) 0.01 M HCl (C) 0.01 M Ca(OH)2 (D) 0.01 M NaOH
4. We have acidic buffer of CH3COONa and CH3COOH. One or more of the following operations will
not change pH :
I : diluting the mixture ten times II : adding some HCl
III : adding some NaOH
IV : adding equal moles of CH3COONa and CH3COOH into the buffer
Select correct alternate :
(A) I, II, III, IV (B) II, III (C) I, IV (D) II, IV
5. Degree of ionisation of 1 M HCOOH is decreased to a maximum extent in presence of :
(A) 1 M HCHO (B) 1 M NaOH (C) 1 M HCOONa (D) equally in all
6. Buffer begins to lose its effectiveness when :
[Salt] [Salt]
(A)  0.1 (B)  10
[weak electrolyte] [weak electrolyte]
(C) both (A) and (B) (D) none of these
7. In what volume ratio should you mix 1.0 M solution of NH4Cl and NH3 to produce a buffer solution
of pH 9.80 ? [pKb (NH3)= 4.74]
(A) 1 : 3.5 (B) 3.5 : 1 (C) 2 : 1 (D) 1 : 2
8. Number of (OH–) in 1 mL solution of pH = 13 is –
(A) 1 × 10–13 (B) 6.00 × 107 (C) 6.00 × 1013 (D) 6.02 × 1019
9. pKa (CH3COOH) is 4.74. x mol of lead acetate and 0.1 mol of acetic acid in one L solution make a
solution of pH = 5.04. Hence, x is –
(A) 0.2 (B) 0.05 (C) 0.1 (D) 0.02
10. Some chemist at ISRO wished to prepare a saturated solution of a silver compound and they wanted
it to have the highest concentration of silver ion possible. Which of the following compounds would
they use ?
Ksp(AgCl) = 1.8 × 10–10 ; Ksp(AgBr) = 5.0 × 10–13 , Ksp(Ag2CrO4) = 2.4 × 10–12
(A) AgCl (B) AgBr (C) Ag2CrO4 (D) any of them
11. Lemon juice normally has a pH of 2. If all the acid in the lemon juice is citric acid and there are no
citrate salts present, then what will be the citric acid concentration [HCit] in the lemon juice ?
(Assume that only the first hydrogen of citric acid is important)
HCit H+ + Cit–, Ka = 8.4 × 10–4 mol L–1
(A) 8.4 × 10–4 M (B) 4.2 × 10–4 M (C) 16.8 × 10–4 M (D) 12.0 × 10–2 M
12. 10 mL of 10–6 M HCl solution is mixed with 90 mL H2O.pH will change approximately –
(A) by 1 unit (B) by 0.3 unit (C) 0.7 unit (D) by 0.1 unit
13. The solubility product of BaSO4 is 1.5 × 10–9. The precipitation in a 0.01 M Ba2+ ions solution will
start on adding H2SO4 of concentration –
(A) 10–9 M (B) 10–8 M (C) 10–7 M (D) 10–6 M
14. In a saturated solution of electrolytes, the ionic products of their concentration are constant at a
particular temperature. This constant for an electrolyte is known as –
(A) ionic product (B) ionisation constant
(C) dissociation constant (D) solubility product
15. 0.1 M acetic acid solution is titrated against 0.1 M NaOH solution. What would be the difference in
pH between 1/4 and 3/4 stages of neutralisation of acid ?
(A) 2 log 3/4 (B) 2 log 1/4 (C) log 1/3 (D) 2 log 3
16. When 0.4 g of NaOH is dissolved in one litre of solution, the pH of the solution is –
(A) 12 (B) 2 (C) 6 (D) 10
17. The hydrogen ion concentration and pH of the solution made by mixing 100 mL of 1.0 M HNO3 with
100 mL of 0.8 M KOH, are –
(A) [H+] = 0.1, pH = 1 (B) [H+] = 0.01, pH = 2
+ –12
(C) [H ] = 1 × 10 , pH = 12 (D) [H+] = 1 × 10–7, pH = 7
18. If the solubility of lithium sodium hexafluoro aluminate, Li3Na3(AlF6)2 is ‘s’ mol L–1, its solubility
product is equal to
(A) s8 (B) 12s3 (C) 18s3 (D) 2916s8
19. 10 mL of 0.1 N HCl is added to 990 mL solution of NaCl. The pH of the resulting solution is –
(A) zero (B) 3 (C) 7 (D) 10
20. 100 mL solution of pH = 6 is diluted to 1000 mL. Resulting solution has pH :

(A) 7.0 (B) 6.79 (C) 7.3 (D) 6.40
21. The Ka value for the acid HA is 1.0 × 10–6. What is the value of K for the reaction ?
A– + H3O+ HA + H2O
(A) 1.0 × 10–8 (B) 1.0 × 108 (C)1.0 × 10–3 (D) 1.0 × 106
22. At 25°C, [H3O+] = 1 × 10–7 M in water, hence, Ka is –
(A) 1 × 10–14 (B) 5.55 × 10–15 (C) 1.8 × 10–16 (D) 55.5 × 10–10
23. What is the value of Kw in 0.01 M NaOH ?
(A) 1 × 10–15 (B) 1 × 10–13 (C) 1 × 10–16 (D) 1 × 10–14
24. [H3O+] in 0.1 M H2SO4 at two stages H2SO4 H+ + HSO4–
–
HSO4 H+ + SO42– are :
(A) 0.1 M, 0.1 M (B) 0.1 M, > 0.01 M (C) > 0.1 M, > 0.1 M (D) 0.1 M, < 0.1 M
25. 20 mL of 0.2 M NaOH is added to 50 mL of 0.2 M CH3COOH. Hence (pH – pKa) is –
3 2
(A) log (B) log (C) log 2 (D) 2 log 2
2 3
26. pH of a mixture which is 0.1 M in CH3COOH and 0.05 M in (CH3COOH)2Ba is
[pKa of CH3COOH = 4.74]
(A) 4.74 (B) 5.04 (C) 4.44 (D) 7.00
27. In which case change in pH is maximum ?
(A) 1 mL of pH = 2 is diluted to 100 mL
(B) 0.01 mol of NaOH is added into 100 mL of 0.01 M NaOH solution
(C) 100 mL of H2O is added into 900 mL of 10–6 M HCl
(D) 100 mL of pH = 2 solution is mixed with 100 mL of pH = 12
28. Which buffer solution has maximum pH ?
(A) mixture which is 0.1 M in CH3COOH and 0.1 M in CH3COONa [pKa (CH3COOH) = 4.74]
(B) mixture which is 0.2 M CH3COOH and 0.2 M in CH3COONa
(C) mixture which is 0.1 M in NH4Cl and 0.1 M in NH4OH [pKa (NH4+) = 9.26]
(D) all the solution have equal pH which is 4.74
29. Ksp of CdS is 8.0 × 10–27 and that of H2S is 1 × 10–22, 1 × 10–14 M, CdCl2 solution is precipitated on
passing H2S when pH is about –
(A) 4 (B) 6 (C) 5 (D) 7
30. 100 mL of 0.02 M benzoic acid (pKa = 4.2) is titrated using 0.02 M NaOH. pH after 50 mL and 100 mL
of NaOH have been added are –
(A) 3.50, 7 (B) 4.2, 7 (C) 4.2, 8.1 (D) 4.2, 8.25
31. The solubility products of Al(OH)3 and Zn(OH)2 are 8.5 × 10–23 and 1.8 × 10–14 at room temperature.
If the solution contains Al3+ and Zn2+ ions, the ion first precipitated by adding NH4OH is –
(A) Al3+ (B)Zn2+ (C) both (D) none
32. To prepare a buffer of pH 8.26, amount of (NH4)2SO4 to be added into 500 mL of 0.01 M NH4OH
solution [pKa (NH4+) = 9.26] :
(A) 0.05 mol (B) 0.025 mol (C) 0.10 mol (D) 0.005 mol
33. If the equilibrium constant of the reaction of weak acid HA with strong base is 109, then pH of 0.1
M NaA is –
(A) 5 (B) 9 (C) 7 (D) 8
34. pH of mixture of HA and A– buffer is 5. Kb of A– = 10–10. Hence [HA]/[A–] will be :

(A) 1 (B) 10 (C) 0.1 (D) 100
35. pH of 0.01 M aqueous solution of NaX, NaY and NaZ are 8, 9 and 10 respectively. Strongest acid
among HX, HY and HZ is –
(A) HX (B) HY (C) HZ (D) can’t be predicted
36. How many grams of CaC2O4 dissolve in distilled water to make one litre of saturated solution
(Ksp = 2.5 × 10–9 and its molecular mass is 128)
(A) 0.0064 g (B) 0.0128 g (C) 0.0032 g (D) 0.0640 g
37. A certain buffer solution contains equal concentration of X– and HX. The Kb for X– is 10–10. The pH of
the buffer is –
(A) 4 (B) 7 (C) 10 (D) 14
38. When the pH changes from 4 to 2, the hydrogen ion concentration will increase by a factor –
(A) 2 (B) 1/2 (C) 102 (D) 100.5
39. pH of the buffer containing 0.6 g of acetic acid and 8.2 g of sodium acetate in 1 litre of water is (pKa
of acetic acid = 4.5)
(A) 7.5 (B) 4.5 (C) 5.5 (D) 6.5
40. The correct order of increasing [H3O+] in the following aqueous solution is –
(A) 0.001 M H2S < 0.01 M H2SO4 < 0.01 M NaCl < 0.01 M NaNO2
(B) 0.01 M NaCl < 0.01 M NaNO2 < 0.01 M H2S < 0.01 M H2SO4
(C) 0.01 M NaNO2< 0.01 M NaCl < 0.01 M H2S < 0.01 M H2SO4
(D) 0.01 M H2S < 0.01 M NaCl < 0.01 M NaNO2 < 0.01 M H2SO4
41. Which of the following statement/relationship is not correct ?
(A) Upon hydrolysis salt of strong base and weak acid gives solution with pH > 7
1
(B) pH = log
[ H ]
(C) only at 25°C, the pH of the pure water is 7
(D) the value of pKw at 25°C is seven
42. For a concentrated solution of a weak electrolyte AxBy the degree of dissociation is given as –
(A)   K eq / c(x  y) (B)   K eq c /(x y)
(C) = (Keq/cx+y–1xxyy)1/(x+y) (D)   K eq / xyc
43. The solubility of sparingly soluble electrolyte MmAa in water given by the expression –
m a 1/(m a)
 K sp   K sp 
(A) s   m a (B) s   m a
 m a   m a 
m a 1/(m a)
 K sp   K sp 
(C) s   a m  (D) s   a m 
 m a   m a 
44. If the salts M2X, QY2 and PZ3 have the same solubilities, their Ksp values are related as –
(A) Ksp (M2X) = Ksp(QY2) < Ksp (PZ3) (B) Ksp (M2X) > Ksp(QY2) = Ksp (PZ3)
(C) Ksp (M2X) = Ksp(QY2) = Ksp (PZ3) (D) Ksp (M2X) > Ksp(QY2) > Ksp (PZ3)
45. Four solutions of NH4Cl are taken with concentrations 1 M, 0.1 M, 0.01 M and 0.001 M. Their
degree of hydrolysis are h1, h2, h3 and h4. What is the gradation of degree of hydrolysis ?
(A) h1 > h2 > h3 > h4 (B) h1 = h2 = h3 = h4 (C) h4 > h3 > h2 > h1 (D) none of these
46. If 40 ml of 0.2 M KOH is added to 160 ml of 0.1 M HCOOH [Ka = 2×10–4], the pOH of the resulting
solution is
(A) 3.4 (B) 3.7 (C) 7 (D) 10.3
47. 1 M NaCl and 1M HCl are present in an aqueous solution. The solution is
(A) not a buffer solution and with pH < 7 (B) not a buffer solution with pH > 7
(C) a buffer solution with pH < 7 (D) a buffer solution with pH > 7
48. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous buffered solution of HA in which 50%
of the acid is ionized is :
(A) 4.5 (B) 2.5 (C) 9.5 (D) 7.0
49. The solubility of A2X3 is y mol dm–3. Its solubility product is

(A) 6 y2 (B) 64 y4 (C) 36 y5 (D) 108 y5
50. If Ksp for HgSO4 is 6.4 ×10–5, then solubility of this substance in mole per m3 is
(A) 8 ×10–3 (B) 6.4 ×10–5 (C) 8 × 10–6 (D) None of these
EXERCISE # 02 ADVANCED EXERCISE
1. An acid-base indicator has a Ka of 3.0 × 10–5. The acid form of the indicator is red and the basic
form is blue. then:
(A) pH is 4.05 when indicator is 75% red (B) pH is 5.00 when indicator is 75% blue.
(C) pH is 5.00 when indicator is 75% red (D) pH is 4.05 when indicator is 75% blue.
2. The equilibrium constant for the reaction
HONO(aq) + CN– (aq) HCN(aq) + ONO– (aq) is 1.1 × 10+6. From the magnitude of this Keq
one can conclude that
(A) CN– is stronger base than ONO– (B) HCN is a stronger acid than HONO
(C) The conjugate base of HONO is ONO– (D) The conjugate acid of CN– is HCN
3. The pH of a solution of 0.10 M CH3COOH increases when which of the following substances is
added?
(A) NaHSO4 (B) HClO4 (C) NH4NO3 (D) K2CO3
4. All of the following are acid-base conjugate pairs:
(A) HONO, NO2– (B) H3O+, OH–
+
(C) CH3NH3 , CH3NH2 (D) HS–, S2–
5. A 50.00 mL sample of 0.0100 M Ba(OH)2 is titrated with 0.0100 M HCl. The solution at the
equivalence point is:
(A) 3.33 × 10–3 M BaCl2 (C) 5.00 × 10–3 M BaCl2
–3
(C) 2.50 × 10 M BaCl2 (D) 1.00 × 10–2 M BaCl2
6. A flask contains 100.00 mL of 0.100 M HOAc. To prepare a buffer with pH = pKa which of the
followingsamples of barium acetate solution should be added to the flask?
(A) 50.00 mL of 0.400 M Ba (OAc)2 (B) 25.00 mL of 0.200 M Ba (OAc)2
(C) 50.00 mL of 0.200 M Ba (OAc)2 (D) 100.00 mL of 0.100 M Ba (OAc)2
7. A 50.00 mL sample of acetic acid was titrated with 0.01200 M KOH and 38.62 mL of base were
required to reach the equivalence point. What was the pH of the titration mixture when 19.31 mL of
base had been added? [pKa (acetic acid) = 4.74]
(A) 2.94 (B)3.54 (C) 4.74 (D) 5.74
8. In the following reaction:
[Cu(H2O)3 (OH)]+ + [Al(H2O)6]3+ [Cu(H2O)4]2+ + [Al(H2O)5(OH)]2+
A B C D
(A) A is an acid and B the base
(B) A is a base and B the acid
(C) C is the conjugate acid of A, and D is the conjugate base of B
(D) C is the conjugate base of A, and D is the conjugate acid of B
9. Which does not react with NaOH or which is not acid salt?
(A) NaH2PO2 (B) Na2HPO3 (C) Na2HPO4 (D) NaHCO3
10. pH of the following solution is not affected by dilution:
(A) 0.01 M CH3COONa
(B) 0.01 M NaHCO3
(C) buffer of 0.01 M CH3COONa and 0.01 M CH3COOH
(D) 0.01 M CH3COONH4
11. Which of the following mixtures constitute a buffer?
(A) CH3COOH + CH3COONa (B) Na2CO 3 + NaHCO 3
(C) NaCl + HCl (D) NH4Cl + (NH4)2SO 4
13. Which of the following mixtures constitute a buffer?
(A) Na2CO 3 + HCl (B) NaOH + CH3COOH
(C) NH3 + CH3COONH4 (D) NaOH + BaCl 2
13. In which of the following pairs of solutions is there no effect on the pH upon dilution?
(A) 0.1 M NH3 and 0.1M(NH4)2SO 4
(B) 0.1 M NaH2PO 4 and 0.1 M Na2HPO 4
(C) 0.1 M HCl and 0.01 M NaOH
(D) 0.1 M KCl and 0.1 M HCl
14. Which of the following will suppress the ionization of phthalic acid in an aqueous
solution.
(A) KCl (B) H2SO (C) HNO3 (D) NaOH
15. Which of the following will suppress the ionization of phthalic acid in an aqueous
solution?
(A) NaHCO 3 + Na2CO 3 (B) CH3COOH + CH3COONa
(C) Na3PO 4 + NaH2PO 4 (D) NH3 + (NH4)2SO 4
16. Which of the following mixtures can act as a buffer?
(A) NaOH + CH3COONa (1 : 1 molar ratio)
(B) CH3COOH + NaOH (2 : 1 molar ratio)
(C) CH3COOH + NaOH (3 : 1 molar ratio)
(D) CH3COOH + NaOH (1 : 1 molar ratio)
17. When HCl(g) is passed through a saturated solution of common salt, pure NaCl is
precipitated because
(A) HCl is highly soluble in water
(B) the ionic product [Na+] [Cl¯] exceeds its solubility product (Ksp)
(C) the ksp of NaCl is lowered by the presence of Cl¯ ions
(D) HCl causes precipitation
18. Which of the following statement(s) is/are correct?
(A) the pH of 1.0 × 108 M solution of HCl is 8
(B) the conjugate base of H2PO4 is HPO42
(C) autoprotolysis constant of water increases with temperature
(D) when a solution of a weak monoprotic acid is titrated again a strong base, at halfneutralization
point pH = (1/2) pKa .
19. A 2.5 gm impure sample containing weak monoacidic base (Mol. wt. = 45) is dissolved in 100 ml
th
 1
water and titrated with 0.5 M HCl when   of the base was neutralised the pH was found to be
5
9 and at equivalent point pH of solution is 4.5 . Given : All data at 25°C & log 2 = 0.3.
Select correct statement(s) .
(A) Kb of base is less than 10–6
(B) Concentration of salt (C) at equivalent point is 0.25 M
(C) Volume of HCl is used at equivalent point is 100 ml
(D) Weight percentage of base in given sample is 80%.
20. Select incorrect statement(s).

(A) Phenolphthalein is suitable indicator for the titration of HCl (aq) with NH4OH (aq).
(B) An acid-base indicator in a buffer solution of pH = pKIn + 1 is ionized to the extent of 90%.
(C) In the titration of a monoacidic weak base with a strong acid, the pH at the equivalent point is
1
always calculated by pH = [pKw – pKb – log C]
2
(D) When Na3PO4 (aq) is titrated with HCl (aq), the pH of solution at second equivalent point is
1 
calculated by pK a  pK a  .
2  1 2
COMPREHENSION # 01 (Q. 21 to 23)

1.2 g of a monoprotic acid HA, is titrated with 0.222 M NaOH solution. The pH of the solution is
monitored with pH meter. A portion of the titration curve is shown in the diagram.
Expanded titration
12.00 curve of
11.00 HA vs NaOH
10.00
pH 9.00
8.00
7.00
6.00
5.00
15 16 17 18 19 20
Volume of NaOH (mL)
21. How many mL of NaOH is required to bring about the titration to its equivalence point?
(A) 4.00 (B) 9.00 (C) 19.00 (D) None of these
22. What is the pH of solution at the equivalence point?

(A) 3.50 (B) 7.00 (C) 8.40 (D) 5.00
23. What is the molar mass of HA?

(A) 180 (B) 222 (C) 282 (D) None of these
COMPREHENSION # 02 (Q. 24 to 27)

Potash alum is K Al(SO4)2·12H2O. As a strong electrolyte, it is considered to be 100 % dissociated
into K+, Al3+ and SO42–. The solution is acidic because of the hydrolysis of Al3+, but not so acidic
as might be expected, because the SO42– can sponge up some of the H3O+ by forming HSO4¯.
Given a solution made by dissolving 11.85 gm of K Al(SO4)2·12H2O in enough water to make 100
cm3 of solution. What is [H3O+] of the solution if
24. None of the ion is hydrolysing.

(A) 10–7 M (B) less than 10–7 M
(C) More than 10–7M (D) 0.0
25. Only Al3+ is hydrolysing and its first hydrolysis constant is 1.4 × 10–5 M
(A) 1.87 × 10–3 M (B) 6.24 × 10–4 M (C) 0.09 M (D) None of these
26. Only SO42– is hydrolysing and acid dissociation constant of HSO4¯ in water is 1.25× 10–2.
(A) 1.26 × 10–3 M (B) 6.32 × 10–7 M (C) 1.58 × 10–8 M (D) None of these
27. Both Al3+ and SO42– are hydrolysing.

(A) 2.93 × 10–4 M (B) 0.0114 M (C) 5.43 × 10–6 M (D) None of these
MATCH THE COLUMN TYPE
List I List II
(a) CH3COOH (P) weak base
(b) H2SO4 (Q) weak acid
(c) NaOH (R) strong acid
(d) NH3 (S) Stronge base
(A) a-R, b-Q, c-P, d-S (B) a-Q, b-R, c-S, d-P
(C) a-P, b-S, c-R, d-Q (D) a-S, b-P, c-Q, d-R
List I List II
Concentraiton of HCl pH
(a) 10–6 M (P) 7.0
(b) 10–7 M (Q) 6.98
(c) 10–8 M (R) 6.0
(d) 10–9 M (S) 6.79
(A) a-R, b-S, c-Q, d-P (B) a-S, b-R, c-Q, d-P
(C) a-Q, b-R, c-S, d-P (D) a-P, b-Q, c-R, d-S
List I List II
Components present in solution Method of determination of pH
(a) CH3COOH + HCl (P) Basic buffer
(b) NH4OH + NH4Cl (Q) Stronge base
(c) NH4Cl (R) Strong acid
(d) NH4OH + NaOH (S) Salt hydrolysis
(A) a-Q, b-R, c-S, d-P (B) a-R, b-S, c-P, d-Q
(C) a-Q, b-S, c-P, d-R (D) a-R, b-P, c-S, d-Q
List I List II
Salt pH
(a) HCOONa (P) 7
(b) NH4Cl (Q) <7
(c) MgSO4 (R) >7
(d) CH3COONH4
(A) a–Q, b-P, c-R, d-P (B) a–P, b-Q, c-Q, d-R
(C) a–R, b-Q, c-P, d-P (D) a–R, b-R, c-Q, d-P
32. A weak acid HA having Ka = 10–4 is given 100 ml of 0.1 M acid is taken in container. Now 0.1 M
NaOH is added in the container List I contains volume of NaOH added and List II contains pH.
Match them.
List I List II
1
(a) 10 ml NaOH solution (P) [pKw + pKa + log c]
2
(b) 25 ml NaOH solution (Q) pKa + log3
(c) 75 ml NaOH solution (R) pKa – log3
(d) 100 ml NaOH solution (S) pKa – 2log3.
(A) a-S, b-R, c-Q, d–P (B) a-P, b-Q, c-R, d–S
(C) a-Q, b-R, c-S, d–P (D) a-S, b-P, c-Q, d–R

Q.1 The degree of dissociation of acetic acid in a 0.1 N solution is 1.32 × 10–2. At what concentration
of nitrous acid, its degree of dissociation will be same as that of acetic acid ? Ka (HNO2) = 4×10–4
Q.2 How many times is the H+ concentration in the blood (pH = 7.36) greater than in the spinal fluid
(pH = 7.53)?
Q.3 A 0.400 M formic acid solution freezes at –0.758°C. Calculate the Ka of the acid at that temperature.
(Assume molarity equal to molality). Kf (H2O) is 1.86° mol–1 kg.
Q.4 A sample of AgCl was treated with 5 mL of 1.5 M Na2CO3 solution to give Ag2CO3. the remaining
solution contained 0.00266625 g/litre Cl– ion. Calculate the solubility of AgCl in
(a) 0.1 M AgNO3 (b) 0.1 M BaCl2 (c) 0.2 M NaNO3..
Given that solubility of Ag2CO3 in 500 mL H2O = 13.8 mg.
Q.5 100 mL of solution S1 contains 0.17 mg of AgNO3. Another 200 mL solution S2 contains
0.117 mg of NaCl. On mixing these two solutions predict whether the precipitate of AgCl will
appear or not Ksp AgCl = 10–10 M2
Q.6 Calculate the value of Kh, h and pH of the following solution at 25°C.
(i) 0.1 M ammonium acetate Ka = Kb = 1.8 × 10–5 M
(ii) 0.1 M anilinium acetate Ka = 1.8 × 10–5 M; Kb = 4.6 × 10–10 M
(iii) 0.1 M ammonium carbonate Ka1 = 4.5 × 10–7 M, Ka2 = 4.7 × 10–11 M
Q.7 Calculate the pH of the following aqueous solutions :
(i) 5 × 10–8 M HCl (ii) 5 × 10–10 M HCl (iii) 10–8 M NaOH (iv)10–10 M NaOH
Q.8 A weak base BOH of concentration 0.02 mole/litre has a pH value of 10.45. If 100 ml of this base
is mixed with 10 ml of 0.1 M HCl, what will be the pH of the mixture ?
Q.9 A 0.02 M solution of CH3COONa in water at 25°C is found to have a H+ concentration of
3 × 10–9 g ionic weight per litre. What is the hydrolytic constant of the salt ?
Kw = 1.01 × 10–14, Ka(CH3COOH) = 1.75 × 10–5
Q.10 2.05 g of sodium acetate was added to 100 ml of 0.1 M HCl solution. Find the H+ ion concentration
of the resulting solution. If 6 ml of 1 M HCl is further added to it, what will be the new
H+ concentration ?
Q.11 An indicator is a weak acid and the pH range of its colour is 3.1 to 4.5. If the neutral point of the
indicator lies in the centre of the hydrogen ion concentrations corresponding to given pH range,
calculate the ionization constant of the indicator.
Q.12 Calculate the hydrolysis constant of NH4Cl ; determine the degree of hydrolysis of this salt in 0.01
M solution and the pH of the solution. Kb (NH4OH) = 1.8 × 10–5
Q.13 Calculate the pH of 0.1 M acetic acid solution if its dissociation constant is 1.8 × 10–5. If 1 litre of
this solution is mixed with 0.05 mole of HCl, what will be the pH of the mixture ?
Q.14 What is the solubility product of Ag2CrO4 if 0.0166 g of the salt dissolves in 500 ml of water at
18ºC?
Q.15 When a 40 mL of a 0.1 M weak base is titrated with 0.16 M HCl, the pH of the solution at the end
point is 5.23. What will be the pH if 15 mL of 0.12 M NaOH is added to the resulting solution.
Q.16 Equal volumes of 0.02 N solution of CaCl2 and Na2SO4 are mixed, Will there be a formation of CaSO4
precipitate ? Ksp (CaSO4) = 1.4 × 10–4.
Q.17 Find the solubility of CaF2 in 0.05 M solution of CaCl2 and water. How many times is the solubility
in the second case greater than in the first ? Ksp (CaF2) = 4 × 10–11.
Q.18 How will the concentration of Ag+ in a saturated solution of AgCl diminish if such an amount of HCl is
added to it that the concentration of the Cl– in the solution becomes equal to 0.03 mole/litre.
[Ksp (AgCl) = 1.8 × 10–10]
1. A chemist needs a buffer with pH 4.35. How many milliliters of pure acetic acid (density = 1.049 g/mL) must
be added to 465 mL of 0.0941 M NaOH solution to obtain such buffer ? (Ka = 1.8 × 10–5)
2. It is found that 0.1 M solution of three sodium salts NaX, NaY and NaZ have pHs 7.0, 9.0 and 11.0,
respectively. Arrange the acids HX, HY and HZ in order of increasing strength. Where possible,
calculate the ionisation constants of the acids.
3. Given a solution that is 0.5 M CH3COOH. To what volume at 25°C must one dm3 of this solution be
diluted in order to (a) double the pH; (b) double the hydroxide-ion concentration.
Given that Ka = 1.8 × 10–5 M.
4. The solubility of Mg(OH)2 is increased by addition of NH4+ ion. Calculate –
(a) KC for the reaction,
Mg(OH)2 + 2NH4+ 2NH3 + 2H2O + Mg2+
(b) Find solubility of Mg(OH)2 in a solution containing 0.5 M NH4Cl before addition of
Mg(OH)2 (Ksp of Mg(OH)2 = 1 × 10–11, Kb for NH4OH = 1.8 × 10–5)
5. A buffer solution was prepared by dissolving 0.05 mol formic acid and 0.06 mol sodium formate in
enough water to make 1.0 L of solution. Ka for formic acid is 1.80 × 10-4.
(a) Calculate the pH of the solution.
(b) If this solution were diluted to 10 times its volume, what would be the pH?
(c) If the solution in (b) were diluted to 10 times its volume, what would be the pH?
6. 20 ml of a solution of 0.1 M CH3COOH solution is being titrated against 0.1 M NaOH solution. The
pH values after the addition of 1 ml and 19 ml of NaOH are (pH)1 and (pH)2, what is pH?
7. (a) Determine the pH of a 0.2 M solution of pyridine C5H5N. Kb = 1.5 ×10-9
(b) Predict the effect of addition of pyridinium ion C5H5NH+ on the position of the equilibrium. Will
the pH be raised or lowered?
(c) Calculate the pH of 1.0 L of 0.10 M pyridine solution to which 0.3 mol of pyridinium chloride
C5H5NH+Cl–, has been added, assuming no change in volume.
8. How many moles of sodium hydroxide can be added to 1.0 L of a solution 0.1 M in NH3 and 0.1 M
in NH4Cl without changing the pOH by more than 1.00 unit? Assume no change in volume.
Kb(NH3) = 1.8 × 10-5.
9. To a solution of acetic acid, solid sodium acetate is gradually added. When x grams of the salt
have been added, the pH has a certain value. When y grams of the salt have been added, the pH has
been further raised by 0.6 units. What is the ratio of x : y? If now the second solution is diluted, what
happens to the pH?
10. A weak base BOH was titrated against a strong acid. The pH at 1/4th equivalence point was 9.24.
Enough strong base was now added (6 meq.) to completely convert the salt. The total volume was
50 ml. Find the pH at this point.
11. An unknown volume and unknown concentration of weak acid HX is titrated with NaOH of unknown
concentration. After addition of 10.0 cm3 of NaOH solution, pH of solution is 5.8 and after the
addition of 20.0 cm3 of NaOH solution, the pH is 6.4. Calculate the pH of aqueous solution of 0.1
M NaX.
12. A solution containing zinc and manganese ions each at a concentration of 0.01 mol dm–3 is
saturated with H2S. Calculate (i) pH at which the MnS will form a precipitate (ii) conc. of Zn+2 ions
remaining.
Given : [H2S] = 0.1 mol/lit, Ksp(ZnS) = 1 × 10–22 mol2lit–2, Ksp(MnS) = 5.6 × 10–16 mol2 lit–2.
K1 and K2 for H2S are 1 × 10–7 and 1.1 × 10–14.
13. For the indicator thymol blue, the value of pH is 2.0, when half of the indicator is present in the
unionised form. Calculate the percentage of the indicator in the unionized form in a solution of
–3
4.0  103 mol/dm hydrogen ion concentration.
14. One of the substances sometimes responsible for the hardness of water is CaSO4. A particular
water sample has 131 ppm CaSO4 (131 g CaSO4 per 106 g of water). If this water boiled in a tea
kettle, approximately what fraction of water must be evaporated before CaSO4(s) begins to deposit
? Assume that solubility of CaSO4 does not change with temperature in the range 0 to 100°C, Ksp
(CaSO4) = 9.1 × 10–6.
15. The indicator phenol red is half in the ionic form when pH is 7.2. If the ratio of the undissociated
form to the ionic form is 1 : 5, find the pH of the solution. With the same pH for solution, if indicator
is altered such that the ratio of undissociated form to dissociated form becomes 1 : 4, find the pH
when 50% of the new indicator is in ionic form.
16. A solution of 0.1 mol dm–3 in Cl–, 0.1 mol dm–3 in Br– and 0.1 mol dm–3 in I–. Solid AgNO3 is gradually
added to this solution. Assuming that the addition of AgNO3 does not change the volume. Answer
the following:
(a) What concentration of Ag+ ions will be required to start precipitation of each of the three ions ?
(b) Which ion will precipitate first ?
(c) What will be the concentration of this ion when the second ion starts precipitating ?
(d) What will be the concentration of both the ions when the third ion starts precipitating ?
Given : Ksp (AgCl) = 1.7 × 10–10 (mol dm–3)2
Ksp (AgBr) = 5.0 × 10–13 (mol dm–3)2
Ksp (AgI) = 8.5 × 10–17 (mol dm–3)2
17. When 40 g of NaOH reacts with a mixture of 1 mole each of acids HX and HY, it is found that 75%
HX is neutralised. If the value of Ka of HX is 9 × 10–6 then calculate pH of 1 M solution of HY in water
and its degree of ionisation.
18. A buffer solution is 0.25 M CH3COOH – 0.15 M CH3COONa, saturated in H2S (0.1 M) and has
[Mn2+] = 0.015 M. Ka = (CH3COOH) = 1.74×10–5, Ka(H2S)=1.1 × 10–21 and Ksp (MnS) = 2.5 × 10–13
(a) will MnS precipitate ?
(b) Which buffer component should be increased in concentration and to which minimum value to
just start precipitation of MnS ?
19. Given that 2 × 10–4 mole each of Mn2+ and Cu2+ was contained in one litre of a 0.003 M HClO4
solution, and this solution was saturated with H2S. Determine whether or not each of these ions,
Mn2+ and Cu2+ will precipitate as sulphide. The solubility of H2S, 0.1 mole per litre is assumed to be
independent of the presence of other materials in the solution.
Ksp (MnS) = 3 × 10–14, Ksp (CuS) = 8 × 10–37
K1 and K2 for H2S are 1 × 10–7 and 1.1 ×10–14 respectively. Also calculate % of Cu remaining
unprecipitated. Will MnS precipitate if the above solution is made neutral by lowering the [H+] to
10–7 M ?
20. A solution of weak acid HA was titrated with base NaOH. The equivalence point was reached when
36.12 ml of 0.1 M NaOH has been added. Now 18.06 ml of 0.1 M HCl were added to titrated
solution, the pH was found to be 4.92. What will be the pH of the solution obtained by mixing
10 ml of 0.2 M NaOH and 10 ml of 0.2 M HA.
EXERCISE # 05 KVPY, OLYMPIAD QUESTIONS
1. pH of a saturated solution of magnetisum hydroxide in water at 298K is 10.5. The solubility of the
hydroxide in water at 298 K is [NSEC 2014]
(A) 1.58  10 4 mol L1 (B) 1.58  1011 mol L1
(C) 3.16  104 mol L1 (D) 9.98  108 mol 1
2. Solubility products of silv er chloride and silv er thiocyanate are 1.2  10 10 and
7.1 1013 respectively. The equilibrium constant for the reaction [NSEC 2014]
AgCl  s   CNS 1  aq   AgCNS  s   Cl 1  aq  is
(A) 0.0625 (B) 169 (C) 13 (D) 1.40  104 .
3. A 50 mL solution of pH = 1 is mixed with a 50 mL solution of pH = 2. The pH of the mixture is

[NSEC 2015]
(A) 0.86 (B) 1.26 (C) 1.76 (D) 2.26
4. The solubility products (Ksp) of three salts MX, MY2 and MZ3 are 1 10 8 ,4  10 8 and 27  108 ,
respectively. The correct order for solubilities of these salts is [NSEC 2015]
(A) MX > MY2 > MZ3 (B) MZ3 > MY2 > MX
(C) MZ3 > MX > MY2 (D) MY2 > MX > MZ3
5. The pH of 1N aqueous solutions of HCl, CH3COOH and HCOOH follows the order[KVPY 2015]
(A) HCl > HCOOH > CH3COOH (B) HCl = HCOOH > CH3COOH
(C) CH3COOH > HCOOH > HCl (D) CH3COOH = HCOOH > HCl
1. If CO2 be passed into water, what will remain present in solution [2006]
(A) CO2, H2CO3, CO32 ,HCO3 (B) H2CO3, CO2
(C) HCO3 ,CO32 (D) CO2 ,HCO3 .

2. Given: [2006]
Ag+ + NH3 Ag(NH3)+; K1 = 1.6  103
Ag(NH3)+ + NH3 [Ag(NH3)2]+; K2 = 6.8  103

The equilibrium constant for the reaction
Ag+ + 2NH3 [Ag(NH3)2]+ is
(A) 6.8  103 (B) 1.088  107 (C) 1.088  106 (D) 1.6  103
 2  2 
3.
12

2.5 ml of   M weak monoacidic base K b  1 10 at 25 is titrated
5
  15  M HCl in water at
 

14
25°C.The concentration of H+ at equivalence point is K w  1 10 at 25C .  [2008]
(A) 3.7  10 14 M (B) 3.2  10 7 M (C) 3.2  10 2 M (D) 2.7  102 M
4.  
Solubility product constant Ksp of salts of types MX , MX 2 and M3 X at temperature T are

4.0  10 8 ,3.2  10 14 & 2.7  1015 respectively. Solubilities Mol dm
3

of the salts at temperature
‘T’ are in the order - [2008]
(A) MX  MX 2  M3 X (B) M3 X  MX 2  MX
(C) MX 2  M3 X  MX (D) MX  M3 X  MX 2
1
5. The initial rate of hydrolysis of methyl acetate (1M)by a weak acid (HA, 1M)is of that of a
100th
strong acid (HX, 1M), at 25°C.The Kaof HA is [2013]
(A) 1 10 4 (B) 1 10 5 (C) 1 10 6 (D) 1 10 3 .
6. The equilibrium constant at 298 K for a reaction A + B C + D is 100. If the initial concentration of all
four speicies were 1M each; then equilibrium concentration of D (in mol L-1) weill be: [2016]
(A) 0.818 (B) 1.818 (C) 1.182 (D)0.182
EXERCISE # 07 JEE (ADVANCED) CORNER
10
1. In 1 L saturated solution of AgCl K sp  AgCl   1.6  10  ,0.1mol of [2011]
CuCl K sp CuCl   1.0  106  is added. The resultant concentration of Ag  in the solution is
1.6  10 x . The value of “x” is
2.  3
The solubility product K sp ; mol dm
9

of MX 2 at 298 based on the information available the given
concentration cell is (take 2.303 × R × 298/F = 0.059 V) [2012]
(A) 1 10 15 (B) 4  10 15 (C) 1 10 12 (D) 4  10 12 .
3.  1

The value of G kJ mol for the given cell is (take 1F = 96500 C mol-1) [2012]
(A) -5.7 (B) 5.7 (C) 11.4 (D)-11.4
4. The K sp of Ag2CrO4 is 1.1 1012 at 298 K. The solubility (in mol/L)of Ag2CrO4 in a
0.1M AgNO3 solution is [2013]
(A) 1.1 1011 (B) 1.1 1010 (C) 1.1 1012 (D) 1.1 109 .
When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M NaOH in an insulated beaker at
constant pressure, a temperature increase of 5.7°C was measured for the beaker and its contents
(Expt. 1). Because the enthalpy of neutralization of a strong acid with a strong base is a constant
(-57.0 kJ mol-1), this experiment could be used to measure the calorimeter constant. In a second

deperiment (Expt. 2), 100 mL of 2.0 M acetic acid K a  2.0  10
5

was mixed with 100 mL of 1.0
m NaOH (under identical conditions to Expt. 1) where a temperature rise of 5.6°C was measured.
(Consider heat capacity of all solutions as 4.2J g 1K 1 and density of all solutions as 1.0 g mL1 )
5. Enthalpy of dissociation (in kJ mol-1) of acetic acid obtained from the Expt. 2 is [2015]
(A) 1.0 (B) 10.0 (C) 24.5 (D)51.4
6. The pH of the solution after Expt. 2 is [2015]

(A) 2.8 (B) 4.7 (C) 5.0 (D)7.0
1. C 2. B 3. C 4. C 5. C
6. C 7. A 8. D 9. C 10. C
11. D 12. C 13. D 14. D 15. D
16. A 17. A 18. D 19. B 20. B
21. D 22. C 23. D 24. D 25. B
26. A 27. D 28. C 29. C 30. C
31. A 32. B 33. B 34. C 35. A
36. A 37. A 38. C 39. B 40. C
41. D 42. C 43. B 44. A 45. C
46. D 47. A 48. C 49. D 50. D
ANSWER KEY EXERCISE # 02 ADVANCED EXERCISE
1. A, B 2. A, C, D 3. D 4. A, C, D 5. A
6. B 7. C 8. B,C 9. A, B 10. B, C, D
11. A,B 12. A,B 13. A, B 14. B,C 15. A, B
16. B, C 17. B, D 18. B, C 19. B, C 20. A, B, C
21. C 22. C 23. C 24. A 25. A
26. C 27. A 28. B 29. A 30. D
31. A 32. A
ANSWER KEY EXERCISE # 03 SUBJECTIVE EXERCISE (LEVEL # 01)
1. 2.3 mol/lit 2. 1.5 times 3. 1.44 × 10–4
4. (a) 1.76 × 10–4 mg/L, (b) 8.8 × 10–5 mg/L, (c) 1.588 mg/L 5. No
6. (i) = 0.5553 × 10 , Kh = 0.308 × 10 , pH = 7 (ii) = 0.52, Kh = 1.208 , pH = 4.71
–2 –4
(iii) = 0.775, Kh = 11.82 , pH = 9.79

7. 6.89, 7, 7.02, 7 8. 8.59 9. 5.68 × 10–10
10. 1.2 × 10–5 M, 3.2 × 10–5 M 11. 4.11 × 10–4 M 12. 5.6 × 10–10, 2.4 × 10–4, 5.63
13. 2.87, 1.3 14. Ksp (Ag2CrO4) = 4 × 10–12 15. pH = 9.168 16. No
1
17. 1.4 × 10–5, 2.15×10–4 mole/litre; 15.4 time 18. of its initial value
2230
1. 8.7 mL
2. HZ < HY < HX , Ka(HY) = 10–5 M, Ka(HZ) = 10–9 M
3. (a) 3.7 × 104 dm3 (b) 4 dm3 4. KC = 3.02 × 10–2, S = 0.123 M
5. (a) pH = 3.83 (b) pH = 3.85 (c) 3.99 6. pH = 2.558
7. (a) pH = 9.239 (b) lowered (c) pH = 4.699 8. 0.0818 moles
9. x : y = 1 : 3.98, unaltered 10. pH = 11.22 11. 9.55
12. (i) pH = 4.35 (ii) 1.79 × 10–9 mol/lit 13. (i) 28.57% (ii) 4.11 × 10–4 mol dm–3
14. 67% 15. pH = 7.3
16. (a) for Cl – = 1.7 × 10–9 mol dm–3, For Br – = 5 × 10–3 mol dm–3, For I– 8.5 × 10–16 mol dm–3
(b) AgI (c) 1.7 × 10–5 mol dm–3 (d) 5.0 × 10–8 mol dm–3, 3.0 × 10–4 mol dm–3
17. pH = 3; 0.1 % 18. (a) No (b) [CH3COO–] = 1.7 M
19. CuS precipitate; 3.27 × 10–14%, MnS precipitates 20. pH = 8.96
ANSWER KEY EXERCISE # 05 KVPY, OLYMPIAD QUESTION
1. A 2. B 3. B 4. B 5. C
1. A 2. B 3. D 4. D 5. A
6. B
ANSWER KEY EXERCISE # 07 JEE (ADVACNED) CORNER
1. 7 2. B 3. D 4. B 5. A
6. B
INDEX
 CONCEPTS IN BRIEF (CHEMICAL THERMODYNAMICS) 01 – 16

 SOLVED EXAMPLES 17 – 28
 EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS 65 – 67
 EXERCISE # 06 JEE (MAIN) CORNER 68 – 70
 EXERCISE # 07 JEE (ADVANCED) CORNER 71 – 74
WEIGHTAGE OF ‘CHEMICAL THERMODYNAMICS’ IN JEE (MAIN & ADVANCED) in

Last Three Years
MARK /
YEAR No. Of Qs.
2014 1 4/120
2015 2 8/120
2016 1 4/120
JEE (ADVANCED)
MARK /
YEAR No. Of Qs.
2014 2 8/120
2015 1 4/168
2016 1 4/124

CHEMICAL THERMODYNAMICS 1
INTRODUCTION:
The branch of science which deal with study of different forms of energy and the quantities
relationship between them is known as Thermodynamics. When the study of thermodynamics is
confined to chemical changes and chemical substances only, it is known as chemical
thermodynamics. Energetics. It is that branch of chemistry which deals with energy changes
taking place in a reaction.
SOME FUNDAMENTAL DEFINITIONS

1. System : That part of the universe which is chosen for thermodynamics considerations is
called system.
2. Surrounding : The remaining portion of the universe which is not chosen for thermodynamic
consideration is called surrounding.
3. Boundary : The imaginary line which separates the system from the surrounding is called
boundary.
4. Types of system :
(i) Open system : A system is said to be an open systems if it can exchange both matter and
energy with the surroundings.
(ii) Closed system : If a system can exchange only energy with the surrounding but not matter is
called closed systems.
(iii) Isolated system : If a system can neither exchange matter nor energy with the surrounding it is
called an isolated systems.
5. State of a System and state variable :

(i) The existence of a system under a given set of conditions is called a state of systems.
(ii) The properties which change with change in the state of system are called as state variables e.g.,
pressure, volume and temperature etc. The first and last state of a system are called initial state
and final state respectively.
6. State function and Path Function : A physical quantity is said to be state function if its value
depends only upon the state of the system and does not depend upon the path by which this
state has been attained.
7. Extensity and Intensive properties : An extensive property of a system is that which depends
upon the amount of the substance or substances present in the system. e.g., mass, volume,
energy etc. An intensive property of a system is that which is independent of the amount of the
substance present in the system e.g., temperature, pressure, density, velocity etc.
8. Thermodynamics Processes : The operation by which a thermodynamic system changes form

one state to another is called is thermodynamic process.
Don‘t ever get comfortable when you have the ability to achieve more.
2 CHEMICAL THERMODYNAMICS
(i) Isothermal process : A process in which although heat enters or leaves the system yet
temperature of the system remains constant throughout the process is called an isothermal
temperature of the system remains constant throughout the process is called an isothermal
process. For an isothermal process, change in temperature (  T) = 0. Change of state (e.g.,
freezing, melting, evaporation and condensation) are all examples of isothermal process.
(ii) Adiabatic process : A process during which no heats enters or leaves the system during any
step of the process is known as adiabatic process. A reaction carried out in an isolated system is
an example of adiabatic process. For an adiabatic process, change in heat (  q) = 0 or q remain
constant.
(iii) Isobaric process : A process during which pressure of the system remains constant throughout
the reaction is called as isobaric process. For example, heating of water to its boiling point, and
its vaporisation taking place at the same atmospheric pressure. Expansion of a gas in an open
system is an example of isobaric process. For an isobaric process  P = 0.
(iv) Isochoric process : A process during which volume of the system remains constant throughout
the reaction is known as isochoric processes. The heating of a substance is a non-expanding
chamber or change taking place in a closed system are examples of isochoric process. For an
isochoric process,  V = 0.
(v) Cyclic process : A process during which system comes to its initial state through a number of
different processes is called a cyclic process. For a cyclic process,  E = 0,  H = 0.
9. Internal energy (E) : The total energy stored in a substance by virtue of tis chemical nature and
state is called its internal energy, i.e., it is the sum of its translation, vibrational, rotational,
chemical bond energy, electronic energy, nuclear energy of constituent atoms and potential
energy due to interaction with neighbouring molecules. It is also called intrinsic energy.
E = Et + Er + Ev + Ee + En + EPE
Internal energy is a state property and its absolute value can‘t be determined. However, change
in internal energy (difference between the internal energies of the products and that of reactants)
can be determined experimentally using a bomb calorimeter. Internal energy of a system
depends upon :
(a) The quantity of substance (b) its chemical nature and
(c) Temperature, pressure and volume.
(i) For a given system, E is directly proportional to its absolute temperature. (E T)
(ii) At constant volume, the quantity of heat supplied to a system (isochoric process) is equal to the
increase in its internal energy, i.e., QV =  E
(iii) In the adiabatic expansion of a gas, it gets cooled because of decrease in internal energy.
(iv) In cyclic process the change in internal energy is zero (  E = 0) since E is a state function.
(v) For exothermic reactions, sign of  E is negative (ER > EP).
(vi) For endothermic reactions, sign of  E is positive (EP > ER).
10. Work : Work is expressed as the product of two factors, i.e.,

W = Intensity factor × capacity factor
Where, intensity factor is a measure of force responsible for work and capacity factor is a
measure extent to which the work is done. Thus,
CatalyseR Eduventures (India) Pvt. Ltd.

(a) Mechanical work = Force × Displacement = F × d

(b) Electrical work = Potential difference × Charge flown = V × Q = EnF
(c) Expansion work = Pressure × change in volume = P ×  V
(d) Gravitation work = Gravitational force × Height = mg × h
(i) Work done in irreversible process w = – PExt  V
(Expansion)
V2
(ii) Work done in isothermal reversible process w = – 2.303 nRT log
V1
P1
(iii) (maximum work) (Expansion) = – 2.303 nRT log
P2
nR
(iv) work done is adiabatic reversible process w= [T – T1]
 1 2
CP
 = = Poisson's ratio
CV
Note : (i) Work is not a state function because amount of work performed depends upon the path
followed.
(ii) Positive value of work signifies that the work has been done on the system by the
surroundings and it leads to an increase in the internal energy of the system. On the other hand,
negative value of work indicates that work has been done by the system and it leads to decrease
in the internal energy of the system.
ZEROTH LAW OF THERMODYNAMICS

It states that, two systems in thermal equilibrium with a third system, are also in thermal
equilibrium with each other.
FIRST LAW OF THERMODYNAMICS

It is law of conservation of energy. Mathematically, this law is written as :
 E = q + w, where  E is change in internal energy of the system and is a state function, q is the
transfer of heat from / to the system and w is the work involved (either done on the system or by
the system) .
According to IUPAC, heat, added to the system and work done on the system are assigned
positive values as both these Modes increase the internal energy of the system.
ENTHALPY :
Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it
has been found useful to define a new state function Enthalpy (H) as :
H = E + PV (By definition) or H = E + P V + VP
or  H =  E + P  V (at constant pressure) combining with first law. Equation (1) becomes
 H = qp
Hence transfer of heat at constant volume brings about a change in the internal energy of the
system whereas that at constant pressure brings about a change in the enthalpy of the system.
The difference between  H &  E becomes significant only when gases are involved
(insignificant in solids and liquids) and is given by:  H =  E + (  n) RT, where  n is the
INCREASE in the number of moles of the gases involved (i.e. Total number of moles of product
gases less the total number of moles of reactant gases).
FACTORS AFFECTING  H OF THE REACTIONS ARE :

(i) Temperature (ii) Physical states of reactants & products
(iii) Allotropic forms of elements & (iv) Pressure & volume (in case of gases)
TWO TYPES OF REACTIONS MAY BE DISTINGUISHED :

(i) Exothermic Reactions : For these  H is negative, which implies that
 H (products) <  H (reactants)
(ii) Endothermic Reactions : For these  H is positive, which implies that
 H (products) >  H (reactants)
HEAT CAPACITY OF A SYSTEM
It is the amount of heat required to raise the temperature of a system through 1ºC If ‗q‘ is the
amount of heat supplied to a system and as a result let the temperature rise from T 1 to T2 ºC.
q q
Then , heat capacity = C = =
T2  T1 T
When heat capacity varies with temperature then the value of C has to be considered over a
narrow range of temperature.
q
Then C=
dT
(a) Specific Heat and Molar Heat Capacity at Constant Volume

Specific Heat : It is the amount of heat required to raise the temperature of 1 gm of a gas
through 1º at constant volume. Molar heat capacity : It is the amount of heat required to raise the
temperature of one mole of a gas through 1º at constant volume
dq = dE + PdV
dq
Molar heat Capacity : C =
dT
dE
Cv 
dT
q = C (T2 – T1) for 1 mole; q = nC (T2 – T1) for n moles
Cv
Hence = SV = Specific heat at constant volume.
Molecular mass

(b) Heat Capacity at Constant Pressure :

It is defined as the amount of heat required to raise the temperature of one mole of gas through
1o keeping pressure constant
 H 
CP   
 T P
CP
= SP = Specific heat at constant pressure
M0
CP is always greater than CV
CP - C V = R
CALCULATION OF W, ΔE , ΔH ,
(A) for Isothermal Expansion of Ideal Gas
(i) E for an ideal gas E depends on temperatures. Since temperature is constant
 dE = 0  E = 0
(ii) According to law
dE = dq + dW; since dE = 0
 dq = -dW  q=-W
 Heat absorbed is equal to work done by the system during isothermal
expansion of ideal gas
(iii) Enthalpy change H = E + PV
 H = E + PV =  E +  (nRT)
 H =  E + nR  T (Because  T=0)
H = 0 + 0 Hence,  H = 0
(B) Adiabatic Reversible Expansion of ideal Gas :

 E or E2 – E1 = nCV (T2 – T1) Also q = 0
  E = – W = CV(T2 – T1) [Because expansion of gas takes place]
 W = –CV(T2 – T1)
W = –nCV(T2–T1) = –nCV  T
COROLLARY
(a) Adiabatic process
(i) Adiabatic compression
 E = W.,  E = + PV
(ii) Adiabatic expansion
E = –W
 E = – PV
Hence during adiabatic compression of an ideal gas internal energy of system increases and
during adiabatic energy of system decreases.
(b) Isochoric process  E = qv

(i) Isochoric absorption of heat
 E = +q  internal energy of system increase
(ii) Isochoric liberation of heat
 E = –q  nternal energy of system decreases
(c) Heat absorbed by system and work done by system

 E = +q – W
(d) Heat liberation by system and work done on the system

E = – q +W
(e) Isobaric process (expansion)

 E = +qP – P  V
(i) when no gases are involved in reaction
 E = +qP
(ii) When gases are involved but initial and final volumes are not given
  E = q –  ng RT where  ng = nP(g) – nR(g)
SECOND LAW OF THERMODYNAMICS

The essence of first law is that all physical and chemical processes take place in such a manner
that the total energy of the universe remain constant. However, it is observed that all processes
have a natural direction ,i.e. a direction in which they take place spontaneously. First law fails to
answer this. Another feature of the spontaneous processes is that they proceed only until an
equilibrium is achieved. The direction of a spontaneous process and that it eventually reaches
equilibrium, can be understood on the basis of entropy concept introduced through the second
law of thermodynamics.
ENTROPY AND SPONTANEITY:

Entropy (denoted by S) in s state function. When the state of a system changes, entropy also
qrev
changes. The change of entrops  S is defined by,  S = , where qrev means that the heat is
T
being supplied ―Isothermally ‖ and ―Reversibly‖ (JK–1).
One can think entropy as a measure of the degree of randomness or disorder in a system. The
greater the disorder, in a system, the higher is the entropy.
A useful form of 2nd law of thermodynamics is :
―The entropy of the universe increases in the course of every spontaneous (natural) change‖.
OR
―For a spontaneous process in an isolated system, the change in entropy is positive‖.
When a system is in equilibrium the entropy is maximum. So mathematically
 S = 0 (at equilibrium)

SECOND LAW :
STATEMENTS :
(a) No cyclic engine is possible which take heat from one single source and
in a cycle completely convert it into work without producing any change
in surrounding.
(b) Efficiency of Carnot engine working reversibly is maximum.

Carnot cycle
V2
AB – Iso. Rev.Exp. w AB = – nRT2 ln
V1
BC – Ada. Rev. Exp. w BC = CV (T1– T2)
V 
CD – Iso. Rev. Comp. w CD = – nRT1 ln  4 
 V3 
DA – Iso. Rev. Comp. w DA = CV (T2 – T1)
 w Total T1  T2 q1  q2
Carnot efficiency  = = 
q2 T2 q2
CARNOT CYCLE :
q1 q2
 = 0 for rev. cycle
T1 T2
q1 q2
Irreversible engine  <0
T1 T2
qrev q
 T
= 0  rev is a state function.
T
dqrev
S =  T
Also  Ssyt +  Ssurr = 0 for rev. process
 Ssyt +  Ssurr > 0 for irrev. process
  Ssyt +  Ssurr  0 ( In general )
ENTROPY CHANGE (GENERAL EXPRESSION ):

(i)  Suniverse =  Ssystem +  SSurrounding
qRe v(system) qRe v(surrounding)

 Ssystem = ,  Ssurrounding =
T T
Heat gained by system = heat lost by surrounding
  SRev(system)= QRev(surrounding)
qRe v(system) qRe v(surrounding)

  Suniverse = +
T T
qRe v(system) qRe v(system)

= -
T T
Hence  Suniverse(Rev)=0
(ii)  Suniv > 0 for irreversible process
T V
(iii)  S = nCV ln 2 + nR ln 2
T1 V1
Change in state function for various processes.
(a) Reversible irreversible isothermal expansion and contraction : (ideal gas )
V2
 E = 0;  H = 0;  S = nR ln
V1
(b) Isobaric heating or cooling :
 E = CV  T
 H = CP  T = qP
 T2 
 S = nCP ln  
 T1 
(c) Isochoric heating or cooling :
 E = CV  T = qV
 H = CP  T
 T2 
 S = nCV ln  
 T1 
(d) Adiabatic process :
 E = CV  T
 H = CP  T
T V
 S = nCV ln 2 + nR ln 2 for irreversible process
T1 V1
 S = 0 for reversible adiabatic compression and expansion.
(iv) Entropy change during mixing of ideal gas
 Smix = – R  n n x
= –R [n1 ln x1+ n2ln x2 + n3 ln x3 ......]
 Smix = – R n i n xi
ni = m  ni n xi no. of moles of the gas

ni = mole fraction of the gas
qRe v
(v) Entropy changes during phase transformation S =
T
(a) Entropy of fusion : The entropy changes taking place when 1 mole of a solid substance
change into liquid form, at the melting temperature.

Hfusion
 Sfusion =
Tfusion
(b) Entropy of vaporization is the entropy change when one mole of a liquid changes into vapours at
boiling point.
Hvapourisation
 Svap = Svap – Sliquid =
Tboiling point
(c) Entropy of sublimation is the entropy change when one mole of a solid changes into vapours at
Hsub
sublimation temperature.  Ssub =
Tsub
Htransition
(d) Hence for any physical transformation  Stransition =
Ttransition
GIBBS FREE ENERGY (G) AND SPONTANEITY:

It is defined as, the energy available in the system for conversion into useful work.
A new thermodynamic (state) function G , the Gibbs free energy is defined as :
G = H – TS or G = H – T S (at constant temperature and pressure)
For a spontaneous reaction  G must be negative. The use of Gibbs free energy has the
advantage that it refers to the system only (and not surroundings also as in entropy).
To summaries, the spontaneity of a chemical reaction is decided by two factors taken together:
(i) The enthalpy factor and
(ii) The entropy factor.
The equation  G =  H – T  S takes both the factors into consideration.
The most favorable situation for a negative value of  G is a negative value of  H and a
positive value of  S. However a large negative value of  H may outweigh an unfavorable  S
value and a large value of  S may outweigh an unfavorable value of  H.
STANDARD FREE ENERGY CHANGE (  G°) :

The standard free energy change  G° is defined as the free energy change for a process at a
specified temperature in which the reactants in their standard state are converted to the products
in their standard state. It is denoted by  G°.
Like the standard enthalpy of formation of an element ―the standard free energy of formation of
an element in its standard state is zero‖. And so ;
Gro   Gof (products) –  G o
f (reactants)
The standard free energy change.  G° is related to the equilibrium constant k eq by the relation;
 G° = – 2.303 RT log keq.
It can be shown that free energy change for a process is equal to the maximum possible work
that can be derived from the process i.e.
 G° = W max (for a reversible change at constant pressure and temperature)
In case of a galvanic cell, free energy change,  G is related to the electrical work done in the
cell.
 G = – nFEcell , where Ecell = e.m.f. of the cell ; F = Faraday constant and

n = number of electrons being transferred in the chemical process
So  G = – nF Eocell , where Eocell is the standard cell potential.
p2 H  1 1 
Clausius Claperyon‘s Equation : log =    (For liquid  gas equilibrium)
p1 2.303R  T1 T2 
p1 & p2 are vapour pressure at TI & T2
THIRD LAW OF THERMODYNAMICS

―At absolute zero, the entropy of a perfectly crystalline substance is taken as zero‖, which means
that at absolute zero every crystalline solid is in a state of perfect order and its entropy should be
zero.
By virtue of the third law, the absolute value of entropy (unlike absolute value of enthalpy) for any
pure substance can be calculated at room temperature.
The standard absolute entropy of, a substance‖ So, is the entropy of the substance in its standard
at 298K and 1 atm.
Absolute entropies of various substances have been tabulated and these value are used to
calculate entropy changes for the reactions by the formula;
 S° =  S (products) –  S (reactants)


THERMOCHEMISTRY
INTRODUCTION
Thermochemistry is the branch of physical chemistry which deals with the transfer of heat
between a chemical system and its surrounding when a change of phase or a chemical reaction
takes place with in the system. It is also termed as chemical energetics.
THERMOCHEMICAL EQUATIONS :
A chemical reaction which tells about the amount of heat evolved or absorbed during the reaction
is called a thermochemical equation. A complete thermochemical equation supplies the following
informations.
(i) It tells about the physical state of the reactants and products. This is done by inserting symbols
(s), (l) and (g) for solid, liquid and gaseous state respectively with the chemical formulae.
(ii) It tells about the allotropic from (if any) of the reactant.
(iii) The aqueous solution of the substance is indicated by the word aq.
(iv) It tells whether a reaction proceeds with the evolution of heat or with the absorption of heat, i.e.
heat change involved in the system.
EXOTHERMIC REACTIONS :
H  in these chemical reactions. It is possible when the bond energy of reactants is
Heat is evolved
less at constant pressure
P P
(HP – HR) = –ve i.e., HP < HR
At constant volume E   E  E R  = – ve i.e, E  E R
ENDOTHERMIC REACTIONS :
Heat is absorbed in these chemical reactions. It is possible when bond energy of reactants is
greater than the bond energy of products.
At constant pressure
H   HP  HR    ve i.e., H P > HR
At constant volume
E   E P  E R    ve i.e., EP > ER
Sign conventions :
H E
Exothermic –ve –ve
Endothermic +ve +ve
HEAT OF REACTION OR ENTHALPY OF REACTION

Enthalpy of reaction is the difference between the enthalpies of the products and the reactants
when the quantities of the reactants indicated by chemical reaction have completely reacted.
Enthalpy of reaction ( or heat of reaction )
H  HP  HR
For example, the equation

H2(g) + Cl2 (g) 
 2HCl (g) + 44.0 Kcal or H = – 44 kcal
C2H4(g) + 3O2(g) 
 2CO2 + 2H2O(l) ; E = – 335.8 kcal
This equation indicates that reaction has been carried between 1 mole of C 2H4 and 3 mole of
oxygen at constant volume and 25°C. The heat evolved is 335.8 kcal or the internal energy of the
system decreases by 335.8 kcal
FACTORS WHICH AFFECT THE HEAT OF REACTION

(a) Physical State of Reactants and Products : The heat of reaction varies for a given reaction
with the change in physical nature of reactants or products e.g.,
C 
O


 CO ; H=-94.3 kcal
For reactant
  diamond  2 2
having different 
C  O 
 CO ; H=-97.7 kcal
Physical state   Amorphous  2 2

(b) Reaction carried out a constant pressure or constant volume :

From 1st Law of thermodynamics q = E  W
at constant volume qV = E
and at constant pressure qp = H
Two values are related as H  E  PV

where P : Pressure at which the reaction is carried out
V : Change in volume during the course of reaction.
Alternatively H  E  nRT
n  No. of moles of products – No. of moles of reactant (only gas phases)
(c) Temperature : Heat of reaction also depends upon the temperature at which reaction is carried
out. The variation in H value with temperature are due to variation in heat capacities of system
with temperature.
Kirchoff’s equation H2  H1  CP  T2  T1 
and E 2  E1  CV  T2  T1  where
CP   Cp of products - CP of reactants 
Cv   CV of products - CV of reactants 

H2 , H1 are change in heat enthalpies at temperature T2 & T1 respectively
E 2 , E1 are change in heat internal energy at temperature T 2 & T1 respectively
(d) Enthalpies of Solution : Enthalpies of reaction differ when in one case dry substances react
and in another case when the same substance react in solution.
e.g., H2S g   I2  g  
 2HI  S ; H  172 Kcal

H2S g   I2  solution  
 2HI  solution   S; H  21.93 Kcal
 CuSO4 H2O  aq  ;
CuSO4  aq  H  15.8 Kcal
 CuSO4 .5H2O  aq. ;
CuSO4 .H2 O  aq  H  29 Kcal
TERMS USED FOR HEAT OF REACTIONS

(a) Heat of Formation or enthalpy of Formation : The amount of heat absorbed or evolved when 1
mole of the substance is directly obtained from its constituent elements is called ―Heat of
formation‖.
Standard Heat Enthalpy : The heat enthalpy of a compound at 25° C and 1 atm pressure is
known as standard heat enthalpy and represented by the symbol H . Thus the standard heat
of formation of 1 mole of CO2(g) and 1 mole of H2O(g) from their respective elements can be
represented as below :
C(g) + O2(g) 
 CO2(g) ; Hf  94 Kcal
H2(g) + 1 O (g)  H O(g) ; Hf  63 Kcal

2 2 2
the enthalpy change of any reaction is given as :
 H° =  H o
f (products) –  H
o
f (reactants)
 sum of standard enthalpies   sum of standard enthalpies 

i.e.  H° =   –  
 of formation of product   of formation of reactants 
(b) Heat of Combustion or Enthalpy of combustion : It is defined as the change in heat enthalpy
when one mole of a substance is completely burnt in oxygen.
 CO2 ; H  94.3 Kcal
C + O2 
C + 2S 
 CS2 ; H  22.0 Kcal
Calorific Value : The amount of heat produced in calorie or joule when one gram of a substance
(food or fuel) is completely burnt or oxidised.
(c) Enthalpy of Neutralisation : It is defined as the heat evolved or decrease in enthalpy when 1
gm equivalent of an acid is neutralised by 1 gm equivalent of a base-in solution.
Strong acid + strong Base 
 Salt + Water ; H  13.7 Kcal
HCl (aq.) + NaOH (aq.) 
 NaCl (aq.) + H2O(l) ; H  13.75 Kcal
1 1
H2SO4  aq.  NaOH  aq. 
 Na 2SO4  aq.  H 2 O  l  ; H  13.7 Kcal
2 2
Thus heat of neutralisation of a strong acid and a strong base is merely the heat of formation of
water from H+ and OH- ions. When strong acid and a weak base or a weak acid and a strong
acid or weak acid and weak base are mixed in equivalent amounts, the heat evolved or change in
enthalpy is less than 13.7 Kcal. eq.
HCl (aq.) + NH4OH (aq.) 
 NH4Cl (aq.) + H2O (l) ; H  12.3 Kcal
HCN (aq.) + NaOH (aq.) 

 NaCN (aq.) + H2O(l) ; H  2.9 Kcal
(d) Enthalpy of Hydration : It is the amount of heat evolved (i.e., change in enthalpy) when 1
mole of anhydrous or a partially hydrated salt combines with required number of moles of water to
form a hydrate. e.g.,
CuSO4 + 5 H2O (l) 
 CuSO4 . 5 H2O ;  H =  18.69 Kcal
CaCl2 (l) + 6 H2O (l) 

 CaCl2 . 6 H2O ;  H =  18.8 Kcal
(e) Enthalpy of ionization : It is defined as the amount of heat absorbed when 1 mole of an
electrolyte completely dissociates into ions.
 CH3CO O + H+
CH3COOH  ;  H = 3 Kcal
 H+ + CN 
HCN  ;  H = 10.8 Kcal
LAWS OF THERMOCHEMISTRY
LEVOISIER AND LAPLACE LAW :
According to this ―enthalpy of decomposition of a compound is numerically equal to enthalpy of
formation of that compound with opposite sign. e.g.,
C (s) + O2 (g) 
 CO2 (g) ;  H =  94.3 Kcal
CO2 (g) 
 C (g) + O2 ;  H = + 94.3 Kcal
HESS’S LAW OF CONSTANT HEAT SUMMATION :

For a chemical equation that can be written as the sum of two or more steps, the enthalpy change
for the overall equation is equal to the sum of the enthalpy changes for the individual steps. Thus,
Hess‘s law enables us to break down a reaction into so many intermediate steps and passing to
each step an individual enthalpy change. The sum of the individual changes must, of course,
equal the overall enthalpy change provided the initial and final states are the same in each case.
H° = - x kJ mol
-1
1
H2(g) + O2(g) H2O(l) + O2(g)
Route A 2
H1° = - y kJ mol H2° = - z kJ mol
-1 -1
H2O2(l)
Route B
For the above example
H  H1   H2 
An energy level diagram for the above reaction cycle is shown in figure

H2(g) + O2(g)
H1° = - 187.6 kJ mol

-1
H° = - 285.9 kJ mol

-1
H2O2(l)
H2° = - 98.3 kJ mol-1
1
H2O(l) + O2(g)
2
Fig. Energy level diagram to illustrate Hess’s Law
EXPERIMENTAL DETERMINATION OF HEAT OF REACTION

The apparatus used is called calorimeter. There are two types of Calorimeters :
(a) Bomb Calorimeter (b) Water Calorimeter
Bomb Calorimeter : The calorimeter used for determining enthalpies of combustion known as
the bomb calorimeter is shown in figure. This apparatus was devised by Berthelot (1881) to
measure the heat of combustion of organic compounds. A modified form of the apparatus shown
in figure consists of a sealed combustion chamber, called a bomb, containing a weighed
quantity of the substance in a dish along with oxygen under about 20 atm pressure.
Ignition Wires
+ _
 O2
Insulating
Container
Water
Sample
Steel Bomb
Bomb Calorimeter
BOND ENERGY
When bond is formed between the two free atoms in a gaseous state to form a molecular product
in a gaseous state, some heat is always evolved which is known as the bond formation energy
or the bond energy. The bond energy may be referred to as heat of formation of the bond.
Alternatively, bond energy may be defined as the average amount of energy required to
dissociate (i.e. break bonds) of that type present in one molecule of the compound. Thus bond
energy of C – H in methane (CH4) is the average value of the dissociation energies of the four
C – H bonds .
Bondenergy datausedfor formation  Bondenergy datausedfor dissociation 
 Hreaction =   +  
of bond(tobetakenas  ve)  of bond(tobetakenas  ve) 
 Hreaction = BE(R) - B.E.(P) taking Bond Energies as +ve values.
BOND ENTHALPY :
The average energy required to break a bond in gaseous molecule to produce gaseous species.
Enthalpy of Reaction :
 H =  (bond energy of bonds broken) -  (bond energy of bonds formed)
Bond dissociation Energy. The energy required to break a particular bond in gaseous molecule to
form gaseous species.
LATTICE ENERGY :
Enthalpy change when one mole of gaseous ions condense to form a solid crystal lattice.
eg. Na+(g) + Cl (g) 
 NaCl (s) .
Born - Haber's cycle is useful in determination of lattice energy & related problems.
RESONANCE ENERGY :
(observed heat of formation) - (calculated heat of formation) .


SOLVED EXAMPLES
Ex. 1 One mole of an ideal gas is put through a series of changes as shown in the graph in
which A, B, C mark the three stages of the system. At each stage the variables are shown
in the graph.
(a) Calculate the pressure at three stages of the system.
(b) Name the processes during the following changes:
(i) A to B (ii) B to C (iii) C to A, and (iv) overall change.
A
24.0 B
(L)
12.0
C
> (L)
300 600
KT K
Sol. (a) At stage A;
V = 24.0 L; T = 300 K;
n=1;
R = 0.0821 lit-atm K–1 mol–1
Substituting these values in the ideal gas eqation,
1 0.0821 300
P= = 1.026 atm
24.0
At stage B : Volume remains the same but temperature change from 300 K to 600 K . Thus,
according to pressure law, the pressure will be double at B with respect to A.
Pressure at B = 2 × 1.026 = 2.052 atm
At stage C : Temperature is 300 K and volume is half that of stage A. Thus, according to Boyle‘s
law, the pressure at C will be double with respect to A.
Pressure at C = 2 × 1.026 = 2.052 atm
(b) (i) During the change from A to B, volume remains constant, the process is
isochoric.
(ii) During the change from B to C the pressure remains constant, the process is isobaric.
(iii) During the change from C to A, the temperature remains constant, the process is
isothermal.
(iv) Overall, the process is cyclic as it returns to initial state.
Ex. 2 The diagram shows a P-V graph of a thermodynamic behaviour of an ideal gas. Find out
form this graph :
(i) work done in the process A  B, B  C, C  D and D  A
(ii) work done in the complete cycle A  B  C  D  A.
Sol.
12 A B
10
P(105Newton/m2)
8
6
4
2 D C
1 2 3 4 5 6
V (litre)
Work done in the process A  B (the process is expansion, hence work is done by the gas)
= – P ×  V = –12 × 105 × 5 × 10–3
= – 6000 J
Work done in the process B  C is zero as volume remains constant.
Work done in the process C  D (The process is contraction, hence work is one on the gas)
= P × dV = 2 × 105 × 5 × 10–3
= 1000 J
Work done in teh process D  A is zero a volume remains constant.
Net work one in the whole cycle = – 6000 + 1000 = – 5000 J
i.e. net work is done by the gas.
Ex. 3 Calculate w and  E for the conversion of 0.5 mole of water at 100ºC to steam at 1 atm
pressure. Heat of vaporisation of water at 100ºC is 40670 J mol–1.
Sol. Volume of 0.5 mole of steam at 1 atm pressure

nRT 0.5  0.0821 373
= = = 15.3 L
P 1.0
Change in volume = Vol. of steam – vol. of water
= 15.3 –negligible = 15.3 L
Work done by the system,
w = Pext × volume change
= 1 × 15.3 = 15.3 litre-atm
= 15.3 × 101.3 J = 1549.89 J
‗w‘ should be negative as the work has been done by the system on the surroundings.
w = –1549.89 J
Heat required to convert 0.5 mole of water in 100ºC to steam
= 0.5 × 40670 J = 20335J
According to first law of thermodynamics,
E = q + w
= 20335 – 1549.89
= 18785.11 J

Ex. 4 Calculate the work done when 50 g of iron is dissolved in HCl at 25ºC in :
(i) a closed vessel and
(ii) an open beaker when the atmospheric pressure is 1 atm.
Sol. (i) When the reaction is carried in a closed vessel, the change in volume is zero. Hence, the
work done by the system will be zero.
(ii) When iron dissolves in HCl, hydrogen is produces.
Fe + 2HCl FeCl2 + H2
56 g 1 mole
1
50 g × 50 mole
56
Volume of hydrogen produced at 25ºC
nRT
=
P
50 0.0821 298
= ×
56 1
= 21.84 L
This is equal to volume change when the reaction is carried in open beaker.
Work done by the system = – P  V = – 1.0 × 21.84
= – 21.84 litre–atm
= – 2212.39 J
Ex. 5 Calculate the amount of work done by 2 mole of an ideal gas at 298 K in reversible
isothermal expansion from 10 litre 20 litre.
Sol. Amount of work done in reversible isothermal expansion
V2
w = –2.303nRT log
V1
Given n = 2, R = 8.314 JK–1 mol–1, T = 298 K, V2 = 20 L and V1 = 10L.

Substituting the values in above equation
20
w = –2.303 × 2 × 8.314 × 298 log
10
= –2.303 × 2 × 8.314 × 298 ×0.3010
= –3434.9 J
i.e., work is done by the system.
Ex. 6 5 mole of an ideal gas expand isothermally and reversibly from a pressure of 10 atm to 2
atm at 300 K. What is the largest mass which can be lifted through a height of 1 metre in
this expansion ?
Sol. Work done by the system
P1 P
= – nRT loge = –2.303 nRT log10 1
P2 P2
10
= – 2.303 × 5 × 8.314 × 300 log = – 20.075 ×103 J
2
Let M be the mass which can be lifted through a height of 1m.
Work done in lifting the mass = M g h = M × 9.8 × 1J
3
So M × 9.8 = 20.075 × 10
M = 2048.469 kg
Ex. 7 The enthalpy of formation of methane at constant pressure and 300 K –75.83 kJ. What will
be the heat of formation at constant volume ? [ R = 8.3 JK –1 mol–1 ]
Sol. The equation for the formation of methane is
C(s) + 2H2(g) = CH4(g) ;  H = –75.83 kJ
2 mole 1 mole
 n = (1 – 2) = –1
Given  H = –75.83 kJ, R = 8.3 × 10–3 kJ K–1 mol–1

T = 300 K
Applying  H =  E +  nRT
–75.83 =  E + (–1) (8.3 × 10–3) (300)
 E = –75.83 + 2.49
So = –73.34 kJ
Ex. 8 A gas expands from a volume of 3.0 dm3 to 5.0 dm3 against a constant pressure of 3.0
atm. The work done during expansion is used to heat 10.0 mole of water of temperature
290.0 K. Calculate the final temperature of water.
[specific heat of water = 4.184 JK–1 g–1 ]
Sol. Work done = P ×dV = 3.0 × (5.0 – 3.0) = 6.0 litre–atm = 6.0×101.3 J= 607.8 J
Let  T be the change in temperature.
Heat absorbed = m × S ×  T = 10.0 × 18 × 4.184 ×  T
Given P × dV = m × S ×  T
P  dV 607.8
or T = = = 0.807
mS 10.0  18.0  4.184
Final temperature = 290 + 0.807 = 290.807 K
Ex. 9 How much heat is required to change 10 g ice 0ºC to steam at 100ºC? Latent heat of fusion
and vaporization for H2O are 80cal/g and 540cal/g respectively. Specific heat of water is 1
cal/g.
Sol. Total heat absorbed
=  Hfusion +  Htemp.rise +  Hvap.
= 10 × 80 + 10 × 1 ×100 + 10  540
= 7200 cal.

Ex. 10 The standard enthalpies of formation at 298 K for CCl 4(g), H2O(g), CO2(g) and HCl(g) are –
106.7, – 241.8, –393.7 and –92.5 kJ mol–1, respectively. Calculate for H298K the reaction,
CCl4(g) + 2H2O(g) 
 CO2(g) + 4HCl(g)
Sol. The enthalpy change of the given reaction will be given as
H  H0f  CO2 , g   4H0f  HCl,g   H0f  CCl4 , g   2H0f  H 2O,g 
= ( – 393.7 – 4 × 92.5 + 106.7 + 2 × 241.8 ) kJ mol–1 = – 173.4 kJ mol–1.
Ex. 11 Compute the resonance energy of gaseous benzene from the following data.
 (C — H) = 416.3 kJ mol–1
 (C — C) = 331.4 kJ mol–1
 (C = C) = 591.1 kJ mol–1
°
ΔΗ sub  C, graphite  = 718.4 kJ mol -1
°
ΔH diss  H 2 , g  = 435.9 kJ mol -1
ΔH °f  benzene, g  = 82.9 kJ mol -1
Sol. To compute resonance energy, we compare the calculated value of ΔH°f (benzene, g) with the
given one. To calculate ΔH°f (benzene, g), we add the following reactions.
6C(g)  6H(g)  C6H6 (g)
H    3CC  3CC  6CH 
6C(graphite)  C(g) H  6  718.4 kJ mol1

Add 3H2 (g)  6H(g) H  3  435.9 kJ mol1
6C(graphite) + 3H2(g) 
 C6H6(g)
The corresponding enthalpy change is
f H    3CC  3CC  6CH   6  718.4 + 3× 435.9 kJ mol 1
= [ – ( 3 × 331.4 + 3 × 591.1 + 6 × 718.4 + 3 × 435.9] kJ mol–1

The given H f is H f (benzene, g) = 82.9 kJ mol–1
0 0
This means benzene becomes more stable by (352.8 – 82.9) kJ mol–1,

i.e., 269.7 kJ mol–1 . This is its resonance energy.
Ex. 12 Calculate the heat of formation of acetic acid from the following data:
(i) CH3COOH(l) + 2O2(g) 
 2CO2(g) +2H2O(l) ;  H = –207.9 kcal
(ii) C(s) + O2(g) 

 CO2(g)  H = –94.48 kcal
(iii) H2(g) + 12 O2(g) 

 H2O(l)  H = –68.4 kcal
Sol. First method : The required eqation is

2C(s) + 2H2(g) + O2(g) = CH3COOH(l);  H = ?
This equation can be obtained by multiplying Eq. (ii) by 2 and also Eq. (iii) by 2 and adding both
and finally substracting Eq.(i)
[2C + 2O2 + 2H2 + O2 – CH3COOH(l) –2O2 = 2CO2 + 2H2O –2CO2 – 2H2O]
HCH COOH( l ) = 2 × (–94.48) + 2 (–68.4)– (–207.9)
3
= –188.96 – 136.8 + 207.9

= –325.76 + 207.9 = –117.86 kcal
Second method : From eq. (ii) and (iii)
Enthalpy of CO2 = – 94.48 kcal
Enthalpy of H2O = – 68.4 kcal
Enthalpy of O2 = 0 (by convention)
 H of Eq. (i) = Enthalphies of products - Enthalpies of reactants
–207.9 = 2 × (–94.48) + 2(–68.4) – HCH3COOH( l )
HCH COOH( l ) = –188.96 – 136.8 + 207.9 = –235.76 + 207.9 = –117.86 kcal

3
Ex. 13 How much heat will be required to make 2 kg of calcium carbide (CaC2) according to the
following reaction ?
CaO (s) + 3C(s) 
 CaC2(s) + CO(g)
The heats of formation of CaO (s), CaC2(s) and CO(g) are –151.6, –14.2 and –26.4 kcal
respectively.
Sol.  H =   H°f(products) –   H°f(reactants)
= [  H°f(CaC2) +  H°f(CO)] – [  H°f(CaO) + 3  H°f(C)]
= [–14.2 –26.4] – [–151.6 + 3 × 0]
= –40.6 + 151.6 = 111.0 kcal
For formation of 64 g of CaC2 111.0 ckal of heat is required.
So, heat required for making 2000 g of
111.0
CaC2 = × 2000 = 3468.75 kcal
64
Ex. 14 Calculate heat of combustion of ethene:

H H
C=C + 3O = O 
 2O=C=O + 2H –O–H
H H
From bond energy data : C=C C–H O=O C=O O–H
K.E. KJ mol–1 619 414 499 724 460
Sol.  H = sum of bond energies of reactants – Sum of bond energies of products
= [  H(C=C) + 4  H(C–H) + 3 ×  H(O=O)] – [4 ×  H(C=O) + 4 ×  H(O–H)]
= [619 + 4 × 414 + 3 × 499] – [ 4× 724 + 4 × 460]

= –964 kJ mol–1
Ex. 15 Calculate the lattice energy for the reaction

Li+ (g) + Cl–(g) 
 LiCl (s)
From the following data :
 Hsub(Li) = 160.67 kJ mol–1; 1
2  (Cl2) = 122.17 kJ mol–1
I.P. (Li) = 520.07 kJ mol–1; E.A. (Cl) = –365.26 kJ mol–1
and  Hºf (LiCl) = – 401.66 kJ mol–1

Sol. Applying the equation
– Q = H + 1
2 D + I.P. – E.A. + U
And substituting the respectrive values,
– 401.66 = 160.67 + 122.17 + 520.07 – 365.26 + U
U = – 839.31 kJ mol–1.
Ex. 16 Bond dissociation enthalpies of H2(g) & N2(g) are 436.0 kJ mol–1 and 941.8 kJ mol–1 and
enthalpy of formation of NH3(g) is – 46 kJ mol–1. What is enthalpy of atomization of

NH3(g)? What is the average bond enthalpy of N–H bond?
Sol. N2(g) + 3H2(g) 

 2NH3(g) ;  H = –2 × 46 kJ/mol
 H = S(B.E.)R – S(B.e.)P
= (941.8 + 3 × 436) – (6x) = –2 × 46 kJ/mol
(here x = B.E. of N–H bonds)
x = 380.3 kJ mol–1
NH3 
 N + 3(H)
Heat of automization = 3 × 390.3 = 1170.9 kJ mol–1
Ex. 17 A sample of argon gas at 1 atm pressure and 27 oC expands reversibly and adiabatically
from 125 dm3 to 250 dm3. Calculate the enthalpy change in this process. C V. for argon is
12.48 JK-1 mol-1.

Sol. For adiabatic expansion, we have
Cv T V2 V2
ln 2 = ln , =2
R T1 V1 V1
12.48 T 12.48 T
 ln 2 = ln2 ln 2 = 0.3010
8.314 300 8.314 300
T2 0.3010  8.314 T
ln = In 2 = 0.200
300 12.48 300
T2 = 300  1.586 =475.8 K or 202.8oC
 T = T2-T1 = 475.8 -300 =175.8K

CP = C V + R
CP = 12.48 + 8.314 = 20.794 JK-1

Now, PV = nRT
1  1.25 = n  0.0821  300  n=0.05
We know
 H = nCp  T = 0.05  20.794  175.8 = 182.77 J
Ex. 18 Calculate the heat of neutralization from the following data 200 ml of 1 M HCl is mixed with
400 ml of 0.5 M NaOH. The temperature rise in calorimeter was found to be 4.4 oC. Water
equivalent of calorimeter is 12 g and specific heat is 1 cal/ml/degree for solution.
Sol. The heat produced (  H1) during neutralization of 200 Meq. of NaOH and HCl each (Meq. =
N  V) is taken up by calorimeter and solution in it.
 H1 = Heat taken up by calorimeter + solution
  H1 = m1S1  T + m2S2  T
= 12
[ total solution = (200 + 400) ml.] =2692.8 cal
 Neutralization of 200 Meq. gives heat =-2692.8 cal
 Neutralization of 1000 Meq. gives heat = -2692  5
= -13464 cal
= -13.464 k cal
Ex. 19 The thermochemical equation for the combustion of ethylene gas, C 2H4, is
C2H4(g) + 3O2(g) 
 2CO2(g) + 2H2O(1) ;  H = -337 KCAL
Assuming 70% efficiency, calculate the weight of water at 20oC that can be converted
into steam at 100oC by burning 1 m3 of C2H4 gas measured at S.T.P. Heat of vaporization
of water at 20oC and 100oC are 1.00 kcal/kg and 540 kcal/kg respectively.
Sol. No. of moles in 1 m3 of ethylene = 44.6 mol
 H for 1 m3 of ethylene (44.6 mol of ethylene) = n(C2H4)   H (1 mole)
= –1.50  104 kcal

 The useful heat = 1.05  104 cal
For the overall process, consider two stages :
H2O (1) 20oC  H2O(l) 100oC ;  H = (1.00 kcal/kg, K) (80 K) =80 kcal/kg
H2O(1) 100oC  H2O(g) 100oC ;  H = 540 kcal/kg
  H (total ) =620 kcal/kg

Amount of heat available 1.05  10 4
 Wt. of water converted into steam = = = 16.9 kg
Heatrequired / kg 620

Ex. 20 Calculate the heat of formation of anhydrous aluminium chloride, Al 2Cl6, from the
following data.
(i) 2Al(s) + 6HCl(aq.) Al2Cl6(g); 3H2(g) ;  H =-240 kcal
(ii) H2(g) + Cl2(g) 2HCl(g) ;  H=-44.0 kcal
(iii) HCl(g) + aq . HCl(aq.) ;  H=-17.5 kcal

(iv) Al2Cl6(s) + aq. Al2Cl6 (aq) ;  H=-153.7 kcal
Sol. The required equation is

2Al(s) + 3Cl2(g) 
 Al2Cl6(s) ; H = ?
For obtaining this,

Multiply (ii) by 3, (iii) by 6 and add the resulting equations to (i)
(i) 2Al (g) + 6HCl(aq.)  Al2Cl6(aq.) + 3H2(g) ;  H = 240.0 kcal
Subtract (iv) from (v) and rearrange the product
2Al (s) + 3Cl2(g) + aq.  A2Cl6(aq.) ;  H = -477.0 kcal
-Al2Cl6(s) - aq.  -Al2Cl6(aq) ;  H = +153.7 kcal

2Al (s) + 3Cl2(g) - Al2Cl6(s)  ;  H = -323.3 kcal
or 2Al(s) + 3Cl2(g)  Al2Cl6 ;  H=-323.3 kcal
Hence the heat of formation of anhydrous aluminium chloride = -323.3 kcal
Ex. 21 10 g of argon gas is compressed isothermally and reversibly at a temperature of 27 oC

from 10L to 5 L. Calculate q, W and  E for this process. (At wt. of Ar =40)
10
Sol. No. of moles of argon = = 0.25 mole and V1 = 10 litre, V2 = 5 litres, T = 300 K
40
V2
For isothermal reversible compression W = – 2.303 nRT log
V1
10
= 2.302  2.5  2  300  log = 103.6 cal
5
Amount of heat absorbed =103.6 cal
Now we know that during isothermal reversible process, internal energy remains constant
throughout the process, hence the change in energy (  E) will be zero.
Ex. 22 Calculate the maximum work done when pressure on 10 g of hydrogen is reduced from 20
to 1 atm at a constant temperature of 273 K. The gas behaves ideally. Will there be any
change in internal energy. Also calculate Q.
P1 10 20
Sol. W = 2.303 nRT log = 2.303   2  273 log = 8180 calories
P2 2 1
Since the change is taking place constant temperature, internal energy will not change, i.e.
E = 0  Q = E +W = 0 + 8180 = 8180 calories
Ex. 23 The heat of combustion of glycogen is about 476 kJ/mol of carbon. Assume that average
heat loss by an adult male is 150 watt. If we were to assume that all the heat comes from
oxidation of glycogen, how many units of glycogen (1 mole carbon per unit) must be
oxidised per day to provide for this heat loss?
Sol. Total energy required in the day
 × 24× 60× 60
 kJ (1 watt = J sec–1)= 12960 kJ
1000
Units of glycogen required
12960
=  27.22 units.
476
Ex. 24 A constant pressure calorimeter consists of an insulated beaker of mass 92 g made up of

glass with heat capacity 0.75 J K –1 g–1. The beaker contains 100 mL of 1 M HCl of 22.6°C
to which 100 mL1 M NaOH at 23.4°C is added. The final temperature after the reaction is
complete is 29.3°C. What is  H per mole for this neutralization reaction? Assume that the
heat capacities of all solutions are equal to that of same volumes of water.
Sol. Initial average temperature of the acid and base
22.6  23.4
=  23.0C
2
Rise in temperature = (29.3 – 23.0) = 63°C
Total heat produced = ( 92 × 0.75 + 200 × 4.184) × 6.3
= (905.8) × 6.3 = 5706.54 J
57065.54
Enthalpy of neutralisation = –  1000  1
100
= – 57065.4 J = – 57 kJ
Ex. 25 Show that the reaction, CO(g) + ( 1/2 ) O 2(g) 

 CO2(g) at 300 K is spontaneous
and exothermic, when the standard entropy change is – 0,094 kJ mol–1 K–1. The standard
Gibb’s free energies of formation of CO2 and CO are – 394.4 and –137.2 kJ mol–1
respectively.
Sol. The given reaction is ,
CO(g) + (1/2) O2(g) 
 CO2(g)
1
G (for reaction) = G CO2  G CO    G O2
2
= – 394.4 – ( – 137.2 ) – 0
= – 257.2 kJ mol–1
 Gº =  Hº – TS
– 257.2 = H – 298 × (0.094)
or  Hº = –288.2 kJ
 Gº is –ve, hence the process is spontaneous, and H is also –ve.

Hence the process is also exothermic.
Ex. 26 Assume that for a domestic hot water supply 150 kg of water per day must be heated from
10°C to 65°C and gaseous fuel propane C3H8 is used for this purpose. What moles &
volume of propane (in litre at STP) would have to be used for heating domestic water. ΔH
for combustion of propane is – 2050 kJ mol–1 & specific heat of water is 4.184 × 10–3 kJ/g.
Sol. Heat taken up by water = m S  T
= 150 × 103 × 4.184 × 10–3 × 55
= 34518 kJ
 2050 kJ heat is provided by 1 mole C3H8
 34158 kJ heat is provided by = 34518/2050
= 16.838 mole of C3H8
 Volume of C3H8 at NTP = 16.838 × 22.4 litre
= 3.77 × 102 litre
Ex. 27 Using the data ( all values in k cal mol–1 at 25° C ) given below, calculate bond energy of
C – C & C – H bonds.
C(s) 
 C(g) ; ΔH = 172 kcal
H2  2H ; ΔH = 104 kcal
1
H2 + O 
 H2O(l) ; ΔH = -68.0 kcal
2 2
C(s) + O2 
 CO2 ; ΔH = -94.0 kcal
Sol. For C3H8 : 3C + 4H2 
 C3H8 ; H = ?
For C2H6 : 2C + 3H2 

 C2H6 ; H = ?
 H1   2  C  C  8  C  H   3Cs g  4  H  H  ..... (1)
H2   1 C  C  6  C  H   2Csg  3 H  H  ..... (2)
 CO2 ; H  94.0 k cal

Also given C + O2  ..... (5)
1
H2 + O2  H2O; H = – 68.0 k cal ..... (6)
2
C2 H6   7 / 2  O2  2CO2  3H2O ; H  530 kcal ..... (7)
C3H8 + 5O2 
 3CO2 + 3H2O ; H = – 530 kcal ..... (8)
By inspection method : 2 × (5) + 3 × (6) – (7) gives
2C + 3H2 
 C2H6 ; H2  20 k cal ..... (9)
and 3 × (5) + 4 × (6) – (8) gives
3C + 4H2 
 C3H8 ;   24 k cal .... (10)
 By equation (3), (4), (9) and (10)
a + 6b = 676
2a + 8b = 956
 a = 82 k cal and b = 99 k cal
Bond energy of C – C bond = 82 k cal and Bond energy of C – H bond = 99 k cal.



1. Out of boiling point (I), entropy (II), pH (III) and e.m.f. of a cell (IV) Intensive properties are:
(A) I, II (B) I,II, III (C) I, III, IV (D) All of these
2. Which has maximum internal energy at 298 K?

(A) helium gas (B) oxygen gas (C) ozone gas (D) equal
3. Ethyl chloride (C2H5Cl), is prepared by reaction of ethylene with hydrogen chloride:
C2H4(g) + HCl (g) 

 C2H5Cl (g)  H = – 72.3 kJ
What is the value of  E (in kJ), if 98 g of ethylene and 109.5 g of HCl are allowed to react at
300 K.
(A) – 64.81 (B) –190.71 (C) –209.41 (D) – 224.38
4. Two moles of Helium gas undergo a reversible cyclic process as shown in figure. Assuming gas
to be ideal, what is the net work involved in the cyclic process?
(A) –100 Rln4 (B) +100Rln4 (C) +200Rln4 (D) –200Rln4
5. Benzene burns according to the following equation

2C6H6(l ) + 15 O2 (g) 
 12 CO2 (g) + 6H2O(l )  H° = –6542 kJ
What is the  E° for the combustion of 1.5 mol of benzene

(A) –3271 kJ (B) –9813 kJ (C) – 4906.5 kJ (D) None of these
6. One mole of ideal gas is allowed to expand reversibly and adiabatically from a temperature of
27°C. If the work done by the gas in the process is 3 kJ, the final temperature will be equal to
(CV=20 J/K mol)
(A) 100 K (B) 450 K (C) 150 K (D) 400 K
5
7. Two moles of an ideal gas (CV = R) was compressed adiabatically against constant pressure
2
of 2 atm. Which was initially at 350 K and 1 atm pressure. The work involve in the process is
equal to
(A) 250 R (B) 300 R (C) 400 R (D) 500 R
8. The maximum efficiency of a heat engine operating between 100°C and 25°C is
(A) 20% (B) 22.2% (C) 25% (D) none
9. A heat engine operating between 227°C and 27°C absorbs 2 Kcal of heat from the 227°C
reservoir reversibly per cycle. The amount of work done in one cycle is
(A) 0.4 Kcal (B) 0.8 Kcal (C) 4 Kcal (D) 8 Kcal
10. A reversible heat engine A (based on carnot cycle) absorbs heat from a reservoir at 1000K and
rejects heat to a reservoir at T 2. A second reversible engine B absorbs, the same amount of heat
as rejected by the engine A, from the reservoir at T 2 and rejects energy to a reservoir at 360K.
If the efficiencies of engines A and B are the same then the temperature T 2 is
(A) 680 K (B) 640 K (C) 600 K (D) none
11. For the reaction at 300 K

A(g) + B(g) 
 C (g)
 E = –3.0 kcal ;  S = – 10.0 cal/K
value of  G is
(A) –600 cal (B) –6600 cal (C) –6000 cal (D) None
12. The entropy change when two moles of ideal monoatomic gas is heat from 200 to 300°C
reversibly and isochorically
3  300  5  573   573  3  573 
(A) R ln   (B) R ln   (C) 3R ln   (D) R ln  
2  200  2  273   273  2  473 
13. What is the free energy change (  G) when 1.0 mole of water at 100°C and 1 atm pressure is
converted into steam at 100°C and 1 atm pressure?
(A) 80 cal (B) 540 cal (C) 620 cal (D) zero
14. What is the free energy change (  G) when 1.0 mole of water at 100°C and 1 atm pressure is
converted into steam at 100°C and 2 atm pressure?
(A) zero cal (B) 540 cal (C) 515.4 cal (D) none
15. When two equal sized pieces of the same metal at different temperatures T h (hot piece) and
Tc(cold piece) are brought into contact into thermal contact and isolated from it's surrounding.
The total change in entropy of system is given by
Tc  Th T2
(A) Cvln (B) Cvln
2Tc T1
(Tc  Th )2 (Tc  Th )2
(C) Cvln (D) Cvln
2Th .Tc 4Th .Tc
16. Pick out the correct statement among the following.

(A) Sof {He(g)} > 0 at 298 K
(B) Sof {H2O(g)} > 0 at 298 K
(C) S° of H2 gas > 0 at 298 K
(D) G of {H2 (g)} > 0 at 298 K

17. What can be concluded about the values of  H and  S from this graph?
(A)  H > 0,  S > 0 (B)  H > 0,  S < 0

(C)  H < 0,  S > 0 (D)  H < 0,  S < 0
18. Which of the following statement(s) is/are incorrect:

Statement (a) : Reversible isothermal compression of an ideal gas represents the limiting
minimum value of the workdone (|w|) by the surrounding on the system.
Statement (b) : In an irreversible process, the cyclic integral of work is not zero.
 Cp ,m 
 
R 
Statement (c) : For thermodynamic changes in adiabatic process T   .P = constant
Statement (d) :  Ssystem is zero for reversible adiabatic expansion of an ideal gas.
(A) Statement c (B) Statement a, b, c (C) Statement a, b, d (D) All
19. Which is not correct ?

(A) in an exothermic reaction, the enthalpy of products is less than that of reactants
(B)  Hfusion =  Hsublimaiton –  Hvaporisation
(C) a reaction for which  Hº < 0 and  Sº > 0 is possible at all temperature
(D)  H is less than  E for the reaction C(s) + (1/2) O2(g) ¾® CO2(g)
20. The enthalpy change for a given reaction at 298 K is -x cal/mol. If the reaction occurs
spontaneously at 298 K, the entropy change at that temperature -
(A) can be negative but numerically larger than x/298 cal K-1
(B) can be negative, but numerically smaller than x/298 cal K-1
(C) cannot be negative
(D) cannot be positive
21. When one mole of monoatomic ideal gas at T K undergoes adiabatic change under a constant
external pressure of 1 atm changes volume from 1 litre to 2 litre.
The final temperature in Kelvin would be
T 2 2
(A) (B) T  (C) T (D) T 
22/3 3  0.0821 3  0.0821
22. For which of the following change  H   E?

(A) H2 (g) + I2 (g) 
 2HI (g)
(B) HCl (aq)+ NaOH(aq) 

 NaCl(aq) + H2O(l)
(C) C(s) + O2(g) 

 CO2(g)
(D) N2 (g)+ 3H2(g) 

 2NH3(g)
23.  rH of which of the following reactions is zero?
 2H+ (g) + 2e–

(A) H2(g)   2H+(aq) + 2e–
(B) 2H(g) + aq 
 2H+(g) + 2e–
(C) 2H(g)   2H+(aq) + 2e–
(D) H2(g) + aq 
24. H 0f of water is – 285.8 kJ mol–1. If enthalpy of neutralisation of monoacid strong base is –57.3
kJ mol–1, H 0f of OH– ion will be
(A) – 228.5 kJ mol–1 (B) 228.5 kJ mol–1 (C) 114.25 kJ mol–1 (D) –114.25 kJ mol–1
25. 50.0 mL of 0.10 M HCl is mixed with 50.0 mL of 0.10 M NaOH. The solution temperature rises by
3.0°C. Calculate the enthalpy of neutralization per mole of HCl.
(A) –2.5×102 kJ (B) –1.3×102 kJ (C) –8.4×101 kJ (D) –6.3×101 kJ
26. The enthalpy of neutralisation of a weak acid in 1 M solution with a strong base is – 56.1 kJ mol–1 .
If the enthalpy of ionization of the acid is 1.5 kJ mol–1 and enthalpy of neutralization of the strong
acid with a strong base is – 57.3 kJ equiv–1, what is the % ionization of the weak acid in molar
solution (assume the acid to be monobasic)?
(A) 10 (B) 15 (C) 20 (D) 25
27. For the allotropic change represented by the equation C (graphite) 

 C (diamond),  H = 1.9
kJ. If 6 g of diamond and 6 g of graphite are separately burnt to yield CO 2, the heat liberated in
first case is
(A) less than in the second case by 1.9 kJ (B) more than in the second case by 11.4 kJ
(C) more than in the second case by 0.95 kJ (D) less than in the second case by 11.4 kJ
28. If x1, x2 and x3 are enthalpies of H–H, O=O and O–H bonds respectively, and x4 is the enthalpy
of vaporisation of water, estimate the standard enthalpy of combustion of hydrogen
x2 x2
(A) x1+ –2x3+x4 (B) x1+ –2x3–x4
2 2
x2 x2
(C) x1+ –x3+x4 (D) 2x3–x1– –x4
2 2
29. NH3(g) + 3Cl2(g) 
 NCl3(g) + 3HCl (g); –  H1
N2(g) + 3H2(g) 
 2NH3(g);  H2
H2(g) + Cl2(g) 
 2HCl (g) ;  H3
The heat of formation of NCl3 (g) in the terms of  H1  H2 and  H3 is
(A)  Hf = –  H1 +  H3
(B)  Hf =  H1 +  H3
(C)  Hf =  H1 –  H3
(D) None

30. Ethanol can undergoes decomposition to form two sets of products
C2H5OH (g) 

if the molar ratio of C2H4 to CH3CHO is 8 : 1 in a set of product gases, then the energy involved
in the decomposition of 1 mole of ethanol is
(A) 65.98 kJ (B) 48.137 kJ (C) 48.46 kJ (D) 57.22 kJ
31. Reactions involving gold have been of particular interest to alchemists. Consider the following
reactions,
Au(OH)3 + 4 HCl 
 HAuCl4 + 3 H2O ,  H =  28 kcal
Au(OH)3 + 4 HBr 
 HAuBr4 + 3 H2O ,  H =  36.8 kcal
In an experiment there was an absorption of 0.44 kcal when one mole of HAuBr 4 was mixed with
4 moles of HCl . What is the percentage conversion of HAuBr4 into HAuCl4 ?
(A) 0.5 % (B) 0.6 % (C) 5 % (D) 50 %
32. (i) Cis  2  butene 

 trans  2  butene,  H1
(ii) Cis  2  butene 

 1  butene,  H2
(iii) Trans  2  butene is more stable than cis  2  butene.
(iv) Enthalpy of combustion of 1  butene,  H =  649.8 kcal/mol
(v) 9  H1 + 5  H2 = 0
(vi) Enthalpy of combustion of trans 2  butene,  H =  647.0 kcal/mol.
The value of  H1 &  H2 in Kcal/mole are
(A)  1.0 , 1.8 (B) 1.8, -1.0
(C) –5, 9 (D) –2, 3.6
33. The reaction CH4(g) + Cl2(g) 

 CH3Cl(g) + HCl(g) has  H = –25 kCal.
Bond
Bond Energy
kCal
 C—Cl 84
 H—Cl 103
 C—H x
 Cl—Cl y
x:y= 9 :5
From the given data, what is the bond energy of Cl—Cl bond
(A) 70 kCal
(B) 80 kCal
(C) 67.75 kCal
(D) 57.75 kCal
34. From the following data at 25°C

Reaction  rH° kJ/mol
H2(g) + O2(g) 
 OH (g) 42
H2(g) + O2(g) 
 H2O(g) –242
H2(g) 
 2H(g) 436
O2(g) 
 2O(g) 495
Which of the following statement(s) is/are correct:
Statement (a) :  rH° for the reaction H2O (g) 
 2H(g) + O(g) is 925.5 kJ/mol
Statement (b) :  rH° for the reaction OH(g) 

 H(g) + O(g) is 502 kJ/mol
Statement (c) : Enthalpy of formation of H(g) is –218 kJ/mol
Statement (d) : Enthalpy of formation of OH(g) is 42 kJ/mol
(A) Statement c (B) Statement a, b, d (C) Statement b, c (D) Statement a, d
35. The enthalpy of solution of BaCl2  s  and BaCl2 .2H2  s  are 20.6 and 8.8 kJmol1 respectively.
The enthalpy change for the reaction BaCl2  s  2H2O  is

(A) 29.4 kJ (B) – 11.8 kJ (C) – 20.6 kJ (D) – 29.4 kJ
36. When 50cm3 of a strong acid is added to 50cm3 of an alkali, the temperature rises by 5C . If
250cm3 of each liquid are mixed, the temperature rise would be
(A) 5C (B) 10C (C) 25C (D) 20C
37. H 2 ( g )  Cl2 ( g )  2HCl ( g ). H  44kcal

2 Na(s)  2HCl ( g )  2 NaCl (s)  H 2 ( g ), H  152 kcal
For the reaction Na( s)  1 Cl ( g )  NaCl ( s), H 
2
2
(A) – 108 kcal (B) – 196 kcal (C) – 98 kcal (D) 54 kcal
38. The following thermochemical reactions are given

1
M  O2  MO  351.4 kJ
2
1
X  O2  XO  90.8 kJ
2
It follows that the heat of reaction for the following process M  XO 
 MO  X is given by
(A) 422.2 kJ
(B) 268.7 Kj
(C) – 442.2 kJ
(D) 260.6 kJ

39. A cylinder of gas is assumed to contain 11.2 kg of butane  C4H10  . If a normal family needs
20000 kJ of energy per day. The cylinder will last: (Given that H for combustion of butane is –
-1
2658 kJmol )
(A) 20 days (B) 25 days (C) 26 days (D) 24 days
40. The enthalpy changes of the following reaction at 25ºC are
Na(s) + 1 Cl (g)  NaCl(s) ;  rH = –411.0 kJ mol–1

2 2
H2(g) + S(s) + 2O2(g) 
 H2SO4(l) ;  rH = –811.3 kJ mol–1
2Na(s) + S(s) + 2O2(g) 

 Na2SO4(s) ;  rH = –1382.3 kJ mol–1
1 H (g) + 1 Cl (g)  HCl(g) ;  rH = –92.3 kJ mol–1
2 2 2 2
From these data, find the heat change of reaction at constant volume at 25ºC for the process
2NaCl(s) + H2SO4(l) 
 Na2SO4(s) + 2HCl(g)
(A) 57.1 kJ mol–1 (B) –60.92 kJ mol–1

(C) 60.92 kJ mol–1 (D) –57.1 kJ mol–1

EXERCISE # 02 ADVANCED LEVEL EXERCISE

(COMPREHENSION TYPE, MULTIPLE TYPE, MATRIX MATCH TYPE, INTEGER TYPE)
1. One mole of an ideal monoatomic gas at 27 ºC expands adiabatically against a constant external
pressure of 1 atm from a volume of 10 dm 3 to a volume of 20 dm3 .
(A) W = – 1013 J
(B)  U = – 1013 J
(C)  H = – 1688 J
(D) The final temperature achieved is 291.8 K
2.  CO2(g)  H = q1
CO(g) + O2(g) 
C(g) + ½O2(g) 
 CO(g)  H = q2
Select correct statement from the above data
(A) heat of formation of CO2(g) is q1
(B) heat of formation of C is q2
(C) heat of formation of CO2 is q1 + q2
(D) heat of combustion of CO(g) is q1 and that of C is q1 + q2
3. 1 mole of HCN reacts with one mole of NaOH heat liberated is 8 Kcal/mole and heat liberated is
10 Kcal/mole when one mole of NH4OH reacts with one mole of HCl. Then
(A) heat of dissociation of HCN is 5.7 Kcal/mole
(B) heat of dissociation of NH4OH is 3.7 Kcal/mole
(C) HCN + NH4OH 
 NH4CN + H2O  H = –4.3 Kcal
(D) HCl + NaOH 
 NaCl + H2O  H = –13.7 Kcal
Porous plate
(I) (II)
T 1 P1 T 2 P2
4.
Insulation
The given system is completely thermally insulated. P 2 < P1 and T2 < T1 consider molar volume
at P1, T1 is V1 and molar volume at P2, T2 is V2 . 1 mole of gas is transferred from piston (I) to
piston (II) As per the given figure -
(A) work done on the gas in piston (I) is P1 V1 and work done by the gas in piston (II) is P2 V2
(B) Net work done,  w = P1 V1  P2 V2

(C) The given process is constant enthalpic process.
(D) For the given process the change in internal energy,  E  0

5. 10 moles of water at 27°C and 1 atmosphere pressure is converted to vapour at 500 K and 1 atm.
If specific heat of water = 1 cal/g, specific heat of water vapour = 0.40 cal/g and latent heat of
vapourisation of water = 540 cal/g then -
(A) Change in entropy when water is heated from 300 K to 373 K is 39.22 cal/deg.
(B) Change in entropy when water is vapourised at 373 K is 260.6 cal/deg.
(C) Change in entropy when water vapours are heated from 373 K to 500 K is 21.11 cal / deg.
(D) The total change in entropy of the process is 320.93 cal/deg.
6. N2 gas is assumed to behave ideally. A given volume of N 2 originally at 373 K and 0.1013 MPa
pressure is adiabatically compressed due to which its temperature rises to 673 K. Which of the
following statements is/are correct?
(A) The change in internal energy is 6235.5 J mol–1
(B) In this case the final internal pressure is equal to the external pressure
(C) The final pressure of N2 is approximately 0.38 MPa
(D) The final pressure of N2 is approximately 0.02 MPa
7. The work involved in a reversible adiabatic process of expansion of an ideal gas from P 1 and V1
to P2 and V2 is given by-
P2 V2  P1 V1
(A) W =
 1
  P  R / Cp 
(B) W = –nCVT1 1   2  
  P1  
(C) W = nCv (T2 – T1)
(D) W = [efficiency of carnot cycle × aabsorbed]
8. One mole of an ideal diatomic gas (Cv = 5cal) was transformed from initial 25°C and 1L to the
state when temperature is 100°C and volume 10L. Then for this process (R = 2 Calories/mol/K)
(take calories as unit of energy and kelvin for temp )
(A)  H = 525
373
(B)  S = 5 ln + 2 ln 10
298
(C)  E = 525
(D)  G of the process can not be calculated using given information.
9. Which of the following statements is/are false -

(A) Endothermic reactions are never spontaneous, at any temperature
(B) Exothermic reactions are always spontaneous at any temperature
(C) Exothermic reactions in which the entropy change for the system is negative are spontaneous
at any temperature
(D) Reactions in which the entropy change for the system is negative are never spontaneous at
any temperature
10. 180 gm of water are evaporated slowly under isothermal conditions at 100ºC. Assuming water
vapour to behave ideally (  Hv = 2260 J/g) -
1
(A)  U = 375.8 kJ (B)  S = 177.5 J/K
2
(C)  G = 0 (D) Q = 406.8 kJ
11. Which of the following expression (s) do not represent the enthalpy formation of NO (g) ?
1
(A) N2 (g) + O (g) 
 NO (g)
2 3
(B) N (g) + O (g) 
 NO (g)
1
(C) NO2 (g) 
 NO (g) + O (g)
2 2
1 1
(D) N2 (g) + O2 (g) 
 NO (g)
2 2
12. Enthalpy of atomisation of C2H6 (g) and C3H8 (g) are 620 kJ/mol and 880 kJ/mol. Therefore
(A) DC – H is 90 kJ/mol
(B) DC – C is 80 kJ/mol
(C) DC = C is 160 kJ/mol
(D) Enthalpy of atomisation of CH4 is approximately 360 kJ/mol.
13. In which of the following reaction  rSº > 0

1
(A)SO2 (g) + O (g) 
 SO3 (g) (B) 2O3 (g) 
 3O2 (g)
2 2
(C) NaCl (s) 
 NaCl (aq) (D) H2 (g) 
 2H (g)
14. In a reversible carnot cycle an ideal gas undergoes following changes.

Step I : isothermal reversible expansion ;
P1 ,V1T1  P2, V2, T1
Step II : Adiabatic reversible expansion :
P2, V2 T1  P3, V3, T2
Step III : isothermal reversible compression :
P3, V3, T2  P4, V4, T2
Step IV : Adiabatic reversible comperssion :
P4, V4, T2  P1, V1, T1
Which of the following plot represent the changes in the carnot cycle.

3
2 1 2
V T
4 1
4 3
T S
(A) (B)
1,2 1,2
H H
3,4
3,4
(C) T (D) T
15. Which of the following correctly represent the variation of G
(A) (B)
Ga
G G s
liquid
solid liquid
solid
Ga
T s T
(C) (D)
16. For phase transition : involving 3 moles of benzene

C6H6(  , 80ºC, 1 atm) 
 C6H6(g, 80ºC, 0.5 atm)
If 80ºC is normal B.P. of benzene the true statment is -
(A)  S < 0 (B)  G = –0.49 k cal (C)  H > 0 (D)  G = 2.3 k cal
17. Which statements are correct ?

(A) A spontaneous chemical reaction which starts far from equilibrium always gives irreversible
process
(B) The entropy increases in an irreversible adiabatic process
(C) The entropy decreases in a reversible adiabatic process
(D) The entropy does not change in a reversible adiabatic process
18. If m1, m2 are masses of an ideal gas, then which of the graph represents m 2 > m1 :
I II
III VI
(A) I, II (B) II, III (C) I, IV (D) I, II, III
COMPREHENSION # 01 (Q.19 to 22)

9.0 gm ice at 0°C is mixed with 36 gm of water at 50°C in a thermally insulated container.
Using the following data, answer the question that follow
CP (H2O) = 4.18 Jg–1K–1 ;  Hfusion (ice) = 335 J g–1
19. Final temperature of water is
(A) 304.43 K (B) 296.97 K (C) 303.93 K (D) 287 K
20.  Sice is
(A) 11.04 JK–1 (B) 3.16 JK–1 (C) 14.2 JK–1 (D) 7.84 JK–1
21.  Swater is
(A) –12.64 JK–1 (B) –0.34 JK–1 (C) –5.42 JK–1 (D) 12.64 JK–1
22. What is the total entropy change in the process?

(A) –1.56 JK–1 (B) –1.60 JK–1 (C) 1.56 JK–1 (D) 1.60 JK–1

Liquid water freezes at 273 K under external pressure of 1 atm. The process is at equilibrium


H2O (l) 
 H2O (s) at 273 K & 1 atm.
However it was required to calculate the thermodynamic parameters of the fusion process
occuring at same pressure & different temperature. Using the following data, answer the question
that follow.
dice = 0.9 gm/cc ; d H2O (l) = 1 gm/cc ; CP [H2O (s)] = 36.4 JK–1mol–1 ;
CP [H2O (l)] = 75.3 JK–1mol–1 ;  Hfusion = 6008.2 Jmol–1.

23. The value of "  Hfusion" at 263 K & 1 atm will be
(A) +6008.2 J mole–1 (B) 5619.2 J mole–1 (C) –5619.2 J mole–1 (D) 6619.2 J mole–1
24. "  Sfusion" at 263 K & 1 atm will be
(A) 22.01 JK–1 mol–1 (B) 22.84 JK–1 mol–1 (C) 21.36 JK–1 mol–1 (D) 20.557 KJ–1 mol–1
25. At 1 atm & at differnt temperature given below. Match the conditions & the temperature for the
"fusion" process
Condition Temperature
(1) Spontaneous (a) 273 K
(2) At equilibrium (b) 260 K
(3) Not feasible (c) 280 K
(A) (1–c), (2–a), (3–b) (B) (1–b), (2–a), (3–c)
(C) (1–c), (2–b), (3–a) (D) (1–a), (2–b), (3–c)
26. For the fusion process at 263 K, match the conditions with the pressure
Conditions Pressure
(1) Spontaneous (a) 1 atm
(2) At equilibrium (b) 1054 atm
(3) Not feasible (c) 2000 atm
(A) (1–b), (2–c), (3–a) (B) (1–a), (2–b), (3–c) (C) (1–c), (2–b), (3–a) (D) (1–a), (2–c), (3–b)

A mixture of hydrogen gas and the theoretical amount of air at 25°C and a total pressure of 1
atm, is exploded in a closed rigid vessel. If the process occurs under adiabatic condition then
using the given datas answer the questions that follow :
Given CP(N2) = 8.3 cal deg–1 mol–1; CP[H2O(g)] = 11.3 cal deg–1 mol–1 ; H f [H2O(g)] = –57.8
Kcal
[Take air as 80% N2, 20% O2 by volume]
27. The value of CP of N2 & H2O in the order N2, H2O will be (in cal. deg.–1 mol–1)
(A) 8.3, 8.3 (B) 8.3, 11.3 (C) 11.3, 11.3 (D) 11.3, 8.3
28. What will be the maximum temperature attained if the process occurs in adiabatic container.
(A)  2940 K (B)  2665 K (C)  1900 K (D)  298 K
29. What will be the final pressure in atm.

(A)  8.5 (B)  7.6 (C)  5.46 (D)  0.85
30. If at initial temperature T1E1 is initial internal energy & at higher final temperature. T 2E2 is the
final internal energy, then which option is true
(A) E1 > E2 (B) E2 > E1
(C) E1 = E2 (D) can't be compared from the given data

The commerical production of "Water gas" utilises the endothermic reaction
C(s) + H2O(g) 
 H2(g) + CO(g)
The heat required for this reaction is generated by combustion of coal to CO 2 using
stoichiometric amount of air.(79% N2 by volume and 21% O2 by volume). The superheated
steam undergoes 75% conversion. Using the following data, answer the question that follows :
H f [CO(g)] = –110.53 kJ/mol ; H f [H2O(g)] = –241.81 kJ/mol ; H f [CO2(g)]=–314.0 kJ/mol
31. The amount of heat liberated when one litre of product gases are burnt at 373 K and one atm is
(A)  3.6 kJ
(B)  3.9 kJ
(C)  4.43 kJ
(D)  5.34 kJ
32. Match the gas and percentage of each gas in one litre product gases.
Gas Percentage
(I) N2 (a)  23.1
(II) CO2 (b)  36.4

(III) H2 (c)  7.7
(IV) H2O (d)  9.7
(A) (I-a), (II-b), (III-c), (IV-d)

(B) (I-b), (II-a), (III-d), (IV-c)
(C) (I-c), (II-d), (III-a), (IV-c)
(D) (I-b), (II-d), (III-a), (IV-c)

The integral enthalpy of solution in kJ of one mole of H2SO4 dissolved in ‗n‘ moles of water is
given by :
75.6  n
H =
n  1.8
33. 1 mole of H2SO4 dissolved in 2 mole of H2O, then  H for the solution will be :
(A) 39.79 kJ (B) 84 kJ
(C) 42 kJ (D) 37.8 kJ
34. If 5 moles of H2O is added in the solution which is obtained in part 1 of the question, then extra
heat change will be :
(A) 60.14 kJ (B) 55.59 kJ
(C) 20.35 kJ (D) 39.79 kJ
35. 1 mole of H2SO4 dissolved in excess of H2O, then  H will be :

(A) 21 kJ (B) 37.8 kJ
(C) 42 kJ (D) 75.6 kJ


S
The variation of equilibrium constant K with temperature is given by log K = –
2.303R
H
for a graph between log K and 1/T a straight line was observed as shown in the
2.303RT
figure. The OX value = 9 and  = tan–1 (0.6)
X
 Y
log K
O 1/T
36. The value of  H and  S for the above reaction is:
20.727 R
(A) 15 J mol–1 , (B) 30 J mol–1,
R 0.6
(C) 20 J mol–1, 0.6 R2 (D) 11.48 J mol–1 ,20.727 R
37. If the reaction is exothermic, the value of log K and the graph of log K vs 1/T would be:
0.6 0.6
(A) 9 – , log K (B) 10– , log K
298 298
1/T 1/T
0 .6 0.6
(C) 9 + 298 , log K (D) 10 + , log K
298
1/T 1/T
38. Thus it can be said that K

(A) always increases with T
(B) always decreases with T
(C) increases with increase in T for endothermic reaction
(D) decreases with increase in T for endothermic reaction.

The temperature dependence of the dissociation constant for the formic acid in aqueous is given
by
1400
log Ka = – + 5 – 0.01 T
T
The enthalpy of neutralisation between strong acid and strong base at 27°C is equal to
–56 kJ/equal.
39. What is the enthalpy of neutralisation of HCOOH against NaOH at 27°C ?
(A) –56 kJ/mol (B) + 56 kJ/mol (C) –46.427 kJ/mol (D) –9.573 kJ/mol
40. What is the standard entropy change for the dissociation of HCOOH at 300 K ?
(A) –19.147 J K–1 mol–1 (B) +19.147 kJ K–1 mol–1
(C) –73 J K–1 mol–1 (D) – 40 JK–1 mol–1
41. At what approximate temperature the dissociation for formic acid is maximum ?
(A) 300 K
(B) 374 K
(C) 474 K
(D)There is no maximum temperature for dissociation

H(g) + X(g) Enthalpy of ionizations H+(g) + X–(g)
+electron gain enthalpy
Enthalpy of dissociation
Enthalpy of hydration
HX(g) of H+& X–
Enthalpy of dehydration
ionisation H+(hydrated) + X–(hydrated)

HX (hydrated)
The relative acid strength is determined by the  G of the ionisation process

In the following table the above data are given in kJ/mol at the standard condition
Enthalpy Enthalpy Ionisation Electron Enthalpy of
Acid of of energy gain hydration
dehydration dissociation HH+ enthalpyXX-- H+ X–
HF 50 575 1300 –340 –1100 –500
HCl 20 425 1300 –360 –1100 –370
HBr 22 365 1300 –330 –1100 –360
HI 25 300 1300 –300 –1100 –400
In the following table for ionisation step T  S° are given in kJ/mol-
Acid TS°
HF –25
HCl 55
HBr 60
HI 63
42. The ionisation constant (Ka) is lesser than 1 for-
(A) HF (B) HCl
(C) HI and HBr (D) All of these
43. The order of acidic strength of the hydracids of halogen is-

(A) HI > HBr > HCl> HF (B) HF > HCl > HBr> HI
(C) HCl > HI > HBr> HF (D) HI > HF > HCl> HBr

44. The order of bond dissociation energies of halogen is-

(A) Cl2 > F2 > Br2 > I2 (B) Cl2 > Br2 > F2 > I2
(C) Cl2 > I2 > Br2 > F2 (D) F2 > Cl2 > Br2 > I2

For the substance X(g), molar specific heat at constant temperature, Cp, increases linearly with
the absolute temperature, T.
Informations regarding X(s)
Molar specific heat = 6.4 JK–1 mol–1
The latent heat of fusion of X (s) = 40 KJ/mol. at the melting point.
The melting point of X (s) = 100 K
Information regarding X(l)
Molar specific heat = 4.5 JK–1 mol–1
Boiling point of X (l) = 250 K
The latent heat of vapourisation of X(l) = 60 KJ/mol at the boiling point.
Information regarding X(g)
For X(g) at 1 atm,
when T = 200 K, Cp = 0.04 JK–1 mol–1
when T = 300 K, Cp = 0.05 JK–1mol–1
45. What is the molar enthalpy of sublimation of X(s) -
(A) 100 kJ/mol (B) 20 kJ/mol (C) 50 kJ/mol (D) – 20 kJ/mol
46. What is the molar enthalpy of vapourisation of X(l) at 400 K ?

(A) Slightly lesser than 60 kJ
(B) Double the enthalpy of vapourisation at 250 K
(C) Slightly higher than 60 kJ
(D) Equal to 60 kJ because enthalpy is a state function
47. In which of the following phase Transition change of entropy is maximum ?

(A) Heating of solid (B) Fusion of X (s)
(C) Vapourisation of X(l) (D) Heating of X (g)

Freezing point of a liquid is defined as that temperature at which it is in equilibrium with its solid
phase.
P = 1 atm
solvent
Vapour Solid T0 > T
Pressure
solution
Tf
T T0
Temperature
Phase diagram for a pure solvent and solution for depression in freezing point.
48. The freezing point of the solvent is -

H – G H G S
(A) T S (B) S (C) S (D) H
49. Freezing point of the solution is smaller than the freezing point of the solvent. Because -
(A)  H of solution and  H of solvent are almost same due to identical intermolecular forces
(B)  S of the solution is larger than  S of solvent
(C)  S of the solution is smaller than the  S of solvent
(D)  H of the solution is much higher than the  H of solvent but  S of solution is smaller than
that of the solvent
50. Which of the following statements is/are correct ?

(A) Solution has more molecular randomness than a pure solvent, hence the entropy change
between solution and solid is larger than the entropy change between pure solvent and solid
(B) Heats of fusion of solution and solvent are similar since similar intermolecular forces are
involved
(C) Sugar containing solution freezes at a lower temperature than pure water
(D) All of the above are correct

Refer to the diagram below to answer questions (52 to 56) The diagram below displays the
pressure and volume of a sample of ideal gas as it is taken very slowly through six states:
A,B,C,D,E and F, along the pathway shown.
(R = 8.314 JK–1 mol–1)
500
400 B C
Pressure 300
(Pa) D
200 A F
100
E
0 1 2 3 4 5 6 7
3 5 5
Volume (m 5)
51. Approximately what is the net work done on the gas as it goes directly from state F to state A-
(A) –400 J (B) 0 J (C) 400 J (D) 600 J
52. Approximately what is the net work done on the gas as it goes directly from state A to state B,
and then directly back to state A-
(A) –1200 J (B) 900 J (C) 0 J (D) 1200 J
53. Approximately what is the net work done on the gas as it goes from state A, through states
B,C,D, E, and F, and back to state A-
(A) –1600 J (B) – 912.5 J (C) 0 J (D) 900 J

54. Approximately what is the net work done on the gas as it goes from state A, through states F, E,
D, C and B, and back to state A-
(A) – 1600 J (B) – 950 J (C) 0 J (D) 912.5 J
55. As the gas is taken from A directly to F, the temperature of the gas-
(A) increases
(B) decreases
(C) remains constant
(D) depends upon the heat transfer
MATCH THE COLUMN TYPE

56. Match the column -
Column I Column II
(i) Exothermic (a)  H positive
(ii) Endothermic (b)   Hf(P) –   Hf(R)
(iii) Heat of reaction (c)  H negative

(iv) Change in free energy (d)  BER –  BEP
(v) Spontaneous process (e)  G negative

(f) H – TS
(A) i-c, ii-a, iii-bd, iv-f, v-e

(B) i-d, ii-c, iii-b, iv-e, v-a
(C) i-c, ii-e, iii-d, iv-b, v-a
(D) i-e, ii-d, iii-c, iv-a, v-b

Column –I Column -II
H2O (  , 1 atm, 263 K)
(A) (P)  rG > 0
 H2O (S, 1 atm, 263 K)
H2O (  , 1 atm, 363 K)
(B) (Q)  rS > 0
 H2O (g, 1 atm, 363 K)
H2O (  , 1 atm, 373 K)
(C) (R)  rH < 0
 H2O (g, 1 atm, 373 K)
H2O (S, 1 atm, 373 K)

(D) (S)  rE > 0
 H2O  , 1 atm, 373 K)

Column-I Column-II
1
(A) Endothermic reactions (P) H2(g)+ O (g)  H2O(l)
2 2
(B) Exothermic reaction (Q) NH3(g)  N(g) + 3H(g)
(C) |  H| = |  E| (R) CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)
1 1
(D) |  H|  |  E| (S) H2(g) + Cl2(g)  HCl (g)
2 2

Column-I Column-II
(Process) (Entropy change)
Molar entropy change for melting of ice at 0°C
(A) (P) 5.26 cal/K-mol
(  Hfusion = 1435 cal/mol)
 S for the vaporisation Of water at 100°C

(B) (Q) 109.1 J/K-mol
(  Hvaporisation = 40.7 KJ/mol)
(C) N2 (g) (10 atm)  N2 (g) (1 atm) (R) Decrease
(D) Desalination of sea- water (S) Increase

Column I Column II
1 Standard enthalpy of formation of

(A) CO(g) + O (g)  CO2 (g) (P)
2 2 CO2
C(graphite) + O2 (g)  CO2

(B) (Q) Enthalpy of reaction
(g)
1
(C) H2 (g) + O (g)  H2O (l) (R) Enthalpy of combustion of CO (g)
2 2
Standard enthalpy of formation of
(D) 2H2 (g) + O2 (g)  2H2O (g) (S)
H2O (l)


Column I Column II
(A) P (P) Temperature is increasing

A
P A B
(B) (Q) Isotherm
T
A
(C) P (R) Isochoric

B
(D) P A (S) Pressure is increasing

Column-I Column-II
(For a definite amount of an ideal gas) (Enthalpy change / work done)
P
1 12
2P0
(A) (P) H > 0
P0 2
V
V0 2V0
P
2
32P0
(B) Adiabatic (Q) H = 0
P0 1  = 5/4
V
V0 16V0
P
2
(C) 1 (R) W>0
T
P
1
(D) 2 (S) W<0

One mole of an ideal gas is subjected to the following process :
Column I Column II
(A) W = 0 (P) If the gas undergoes free expansion
If the gas is cooled reversibly at constant pressure

(B)  E = 75Cv (Q)
from 373 K to 298 K
If the gas is heated from 298 K to 373 K reversively
(C)  H = –75 Cp (R)
at constant pressure
If the gas is heated from 298 K to 373 K at

(D)  W = –75 R (S)
constant volume


Column I Column II
(A) Adiabatic reversible process (P)  Ssystem = 0
(B) Adiabatic irreversible process (Q)  Ssurr = 0
(C) Free expansion process (Q)  Snet < 0
(D) Non spontaneous process (S)  Snet = 0

Column I Column II
spontaneous reaction at any
(A) Endothermic reaction with  rS > 0 (P)
temperature
spontaneous reaction at lower
(B) Endothermic reaction with  rS < 0 (Q)
temperature
At higher temperature spontaneous
(C) Exothermic reaction with  rS > 0 (R)
reaction
Non spontaneous reaction at any

(D) Exothemic reaction with  rS < 0 (S)
temperature
INTEGER TYPE
66. The ‗‘heat of total cracking‘‘ of hydrocarobon,  HTC is defined as  H at 298 K and 1 atm for
the following process
 m
CnH2m +  2n   H2(g) 
 n CH4(g)
 2
Given: For C2H6,  HTC = – 70kJ/mol
For C3H8,  HTC = – 90 kJ/mol determine the magnitude of enthalpy change for the
following reaction in kJ in the nearest possible integers
CH4(g) + C3H8(g) 
 2C2H6(g)
67. At 27º C,  Hcombustion (sucrose) = – 6000 kJ/mol &  Gcombustion (sucrose) = – 6600 kJ/mol.
Calculate additional work (in kJ/mol ) that may be obtained by metabolism of sucrose in blood
when blood temperature is raised to 310 K.
68. 64 gram of methanol at a temperature of 60°C are poured into 128 gram of methanol kept at
20°C in an insulated vessel. Calculate the net change in entropy that occurs. (give your answer in
J/K and in the form of nearest whole number) [log(0.9198) = –0.036 ; log (1.045) =
0.0193]
69. Find change in internal energy, when 0.5 mole of Ar having a specific heat at constant pressure
of 20.814 J g–1 deg–1 is heated from 27°C to 31°C at constant volume.
(Atomic mass of Ar = 40) (give your answer in KJ)
70. When 10 litre of ozone gas at 1 atm is compressed adiabatically to 1/5th of its volume, the
pressure becomes 6.5 times of the initial. Find out the work done in the process. (Assuming ideal
behaviour for ozone, give your answer in L-atm)
71. One mole of benzene liquid is converted into vapour at its boiling point (80°C). Find out change in
internal energy  U for this process (in KJ).
(given   Hv = 3.0 KJ/mol, report your answer in the form of nearest integer)
72. An ideal gas is taken through the cycle A  B  C  A as shown in the figure. If net heat
supplied to the gas in the cycle is 5J, the work done on the gas in the process C  A is ………J-
C B
2
V
in m3 1 A
10
P  in N/m2
73. Heat supplied to a carnot engine is 2 × 103 J. If the engine work between 300 K to 600 K. The
useful work obtained form the carnot engine is ……… KJ
74. One mole of He is mixed with 2 mole of Ne, both at the same temperature and pressure.
Determine  S for the process in J/K in nearest possible integers, if the total volume remain
constant.
log 3 = 0.48 ; log 2 = 0.3
75. For the reaction ;

A (s)  B (g) + C (g)
 rGº =(1000 – 50 T ln T) in kJ/mol
Determine  rCpº of the above reaction in kJ/mol in nearest possible integer.


EXERCISE # 03 SUBJECTIVE EXERCISE # 01
1. In which of the following changes at constant pressure is work done by system on surrounding?
By the surrounding on system?
Initial state Final state
(i) H2O (g)  H2O (l)
(ii) H2O (s)  H2O (g)
(iii) H2O (l)  H2O (s)
(iv) 2H2(g) + N2(g)  2NH3 (g)
(v) CaCO3 (s)  CaO (s) + CO2 (g)
2. The enthalpy change for the reaction of 50 ml of ethylene with 50.0 ml of H2 at 1.5 atm pressure
is  H = – 0.31 KJ. What is the  E.
3. What is  E when 2.0 mole of liquid water vaporises at 100°C ? The heat of vaporisation ,  H
vap. of water at 100°C is 40.66 KJmol–1.
4. If 1.0 k cal of heat is added to 1.2 L of O 2 in a cylinder of constant pressure of 1 atm, the volume
increases to 1.5 L. Calculate  E and  H of the process.
5. Lime is made commercially by decomposition of limestone CaCO 3. What is the change in internal
energy when 1.00 mole of solid CaCO3 (V = 34.2 ml) absorbs 177.9 kJ of heat and decomposes
at 25°C against a pressure of 1.0 atm to give solid CaO. (Volume = 16.9 ml) and CO2 (g) (V =
24.4 L).
6. One mole of solid Zn is placed in excess of dilute H 2SO4 at 27 °C in a cylinder fitted with a
piston. Find the value of  E, q and w for the process if the area of piston is 500 cm 2 and it
moves out by 50 cm against a pressure of 1 atm during the reaction. The heat given to
surrounding is 36.5 KJ.
Zn(s) + 2H+ (aq) l Zn2+ (aq) + H2(g)
7. Two mole of ideal diatomic gas (CV,m = 5/2 R) at 300 K and 5 atm expanded irreversibly &
adiabatically to a final pressure of 2 atm against a constant pressure of 1 atm. Calculate q, w,
H &  V.
8. Five moles of an ideal gas at 300 K, expanded isothermally from an initial pressure of 4 atm to a
final pressure of 1 atm against a cont. ext. pressure of 1 atm. Calculate q, w,  U &  H. Calculate
the corresponding value of all if the above process is carried out reversibly.
9. Calculate the max. work done by system in an irreversible (single step) adiabatic expansion of 1
mole of a polyatomic gas from 300K and pressure 10 atm to 1 atm.(  = 1.33).
10. Three moles of a ideal gas at 200 K and 2.0 atm pressure undergo reversible adiabatic
compression until the temperature becomes 250 K for the gas C V is 27.5 JK–1 mol–1 in this
temperature range. Calculate q, w,  U,  H and final V and final P.
11. A sample of a fluorocarbon was allowed to expand reversibly and adiabatically to twice its
volume. In the expansion the temperature dropped from 298.15 K to 248.44 K. Assume the gas
behaves perfectly. Estimate the value of CV,m .
12. One mole of ideal monoatomic gas is carried through the reversible cyclic process as shown in
figure. Calculate.
(a) work done by the gas
(b) The heat exchanged by the gas in path CA and AB.
(c) Net heat absorbed by the gas in the path BC.
(d) The max. temperature attained by the gas during the cycle.
13. One mole of an ideal monoatomic gas is carried through the cycle of the given figure consisting of
step A, B and C and involving state 1,2 and 3.
Fill in the blank space in the table given below assuming reversible steps.
Table-1
State P V T
1
2
3
Step Name of process q w E H

A
B
C
14. One mole of NaCl (s) on melting absorbed 30.5 KJ of heat and its entropy is increased by 28.8
JK–1. What is the melting point of sodium chloride?
15. Calculate the free energy change at 298 K for the reaction ;
Br2 (l) + Cl2 (g)  2 BrCl (g). For the reaction  Hº = 29.3 kJ & the entropies of Br2 (l), Cl2 (g) &
BrCl (g) at the 298 K are 152.3, 223.0, 239.7 J mol-1 K-1 respectively.
16. 20.0 dm3 of an ideal gas (diatomic CV,m = 5R/2) at 673 K and 0.7 MPa expands until pressure of
the gas is 0.2 MPa. Calculate q, w,  U and  H for the process if the expansion is :
(i) Isothermal and reversible (ii) Adiabatic and reversible
(iii) Isothermal and adiabatic (iv) Against 0.2 MPa and adiabatic
(v) Against 0.2 MPa and isothermal.

17. One mole of an ideal monoatomic gas ( CV,m = 1.5 R) is subjected to the following sequence of
steps:
(a) The gas is heated reversibly at constant pressure of 101.325 kPa from 298 K to 373 K.
(b) Next, the gas is expanded reversibly and isothermally to double its volume.
(c) Finally, the gas is cooled reversibly and adiabatically to 308K.
Calculate q , w ,  U and  H for the overall process.
18. Calculate  Sfº at 298 K of ; (i) NaCl (s) , (ii) NH4Cl (s) & (iii) diamond.
The values of S º of Na, Cl2, NaCl, NH4Cl, N2, H2, diamond & graphite are 51, 223, 72, 95,
192, 131, 2.43 & 5.69 JK-1 mol-1 respectively.
19. 10 g of neon initially at a pressure of 506.625 kPa and temperature of 473 K expand adiabatically
to a pressure of 202.65 kPa. Calculate entropy change of the system and total entropy change for
the following ways of carrying out this expansion.
(i) Expansion is carried out reversibly.
(ii) Expansion occurs against a constant external pressure of 202.65 kPa.
(iii) Expansion is a free expansion.
20. Calculate the free energy change in the freezing of 18 gm of water at 263.15 K, given that the
vapour pressure of water and ice at 263.15 K are 0.287 Pa and 0.260 Pa, respectively.
21. When 2 moles of C2H6 are completely burnt 3120 kJ of heat is liberated . Calculate the heat of
formation,  Hfº for C2H6 . Given  Hfº for CO2(g) & H2O (l) are  395 &  286 kJ respectively.
22. The standard heats of formation of CH 4 (g) , CO2 (g) and H2O (l) are  76.2 ,  398.8 ,
 241.6 kJ mol -1 . Calculate amount of heat evolved by burning 1 m 3 of methane measured

under normal (STP) conditions.
23. Calculate the enthalpy change when infinitely dilute solution of CaCl 2 and Na2CO3 mixed  Hf°
for Ca2+(aq), CO32– (aq) and CaCO3 (s) are – 129.80, – 161.65, – 288.5 kcal mol–1 repectively.
24. The heat of solution of anhydrous CuSO4 is – 15.9 kcal and that of CuSO4.5H2O is 2.8 kcal.
Calculate the heat of hydration of CuSO4.
25. The enthalpy change for the reaction C3H8 + H2(g)  C2H6(g) + CH4(g) at 25º C is
 55.7 kJ/mol. Calculate the heat of combustion of C 2H6(g). The heats of combustion of
H2, CH4 & Cgraphite are  285.8,  890.0 &  393.5 kJ/mole respectively. Heat of combustion of
propane is  2220 kJ mol-1.
26. At 300 K, the standard enthalpies of formation of C 6H5COOH(s), CO2 (g) & H2O (l) are
 408,  393 &  286 KJ mol -1 respectively . Calculate the heat of combustion of benzoic
acid at:(i) constant pressure & (ii) constant volume.
27. The heat liberated on complete combustion of 7.8 g of benzene is 327 kJ . This heat has been
measured at constant volume & at 27º C. Calculate the heat of combustion of benzene at
constant pressure.
28. When 12.0 g of carbon reacted with oxygen to form CO & CO 2 at 25º C & constant pressure,
75.0 kcal of heat was liberated and no carbon remained . Calculate the mass of oxygen which
reacted.  Hfº (CO2) =  95 kcal mol-1,  Hfº (CO) =  24kcal mol-1.
29. If the enthalpy of formation of HCl (g) and Cl– (aq) are –92.3 kJ/mole and – 167.44 kJ/mol, find
the enthalpy of solution of hydrogen chloride gas.
30. 0.16 g of methane was subjected to combustion at 27º C in a bomb calorimeter. The temperature
of calorimeter system (including water) was found to rise by 0.5º C. Calculate the heat of
combustion of methane at (i) constant volume (ii) constant pressure .
The thermal capacity of calorimeter system is 17.7 kJ K-1 . (R = 8.313 mol-1 K-1)
31. The enthalpy of dissociation of PH 3 is 954 kJ/mol and that of P2H4 is 1.485 M J mol–1. What is
the bond enthalpy of the P–P bond?
32. The Born - Haber cycle for rubidium chloride (RbCl) is given below (the energies are in
k cal mol1 )
Find out the electron affinity of chlorine in kJ mol-1 .
33. Calculate the enthalpy of combustion of benzene (l) on the basis of the following data :
(i) Resonance energy of benzene(l) =  152 kJ/mol
(ii) Enthalpy of hydrogenation of cyclohexene(l) =  119 kJ/mol
(iii)  Hºf of C6H12(l) =  156 kJ/mol
(iv)  Hºf of H2O(l) =  285.8 kJ/mol
(v)  Hºf of CO2(g) =  393.5 kJ/mol

34. Calculate the heat produced when 3.785 litre of octane (C 8H18) reacts with oxygen to form CO &
water vapour at 25º C. The density of octane is 0.7025 gm/ml. Heat of combustion of C 8H18 is
 1302.7 k cal/mol .
 Hfº CO2(g) =  94.05 k cal mol-1 ;  Hfº CO(g) =  26.41 k cal mol-1
 Hfº H2O(l) =  68.32 k cal mol-1 ;  Hfº H2O(g) =  57.79 k cal mol-1
35. Calculate the enthalpy change for the reaction XeF 4  Xe+ + F- + F2 + F.
The average Xe-F bond energy is 34 kcal/mol, first I.E. of Xe is 279 kcal/mol, electron affinity of F
is 85 kcal/mol & bond dissociation energy of F2 is 38 kcal/mol.
36. By using the following data draw an appropriate energy cycle & calculate the enthalpy change of
hydration of (i) the chloride ion ; (ii) the iodide ion.
Comment on the difference in their values.
* enthalpy change of solution of NaCl(s) =  2 kJ/mol.
* enthalpy change of solution of NaI(s) = + 2 kJ/mol.
* enthalpy change of hydration of Na +(g) =  390 kJ/mol.
* lattice energy of NaCl =  772 kJ/mol.
* lattice energy of NaI =  699 kJ/mol.
37. The standard enthalpy of combustion of sucrose is - 5645 kJ mol-1 . What is the advantage (in
kJ mol-1 of energy released as heat) of complete aerobic oxidation compared to anaerobic
hydrolysis of sucrose to lactic acid ?  Hfº for lactic acid, CO2 and H2O is  694,  395.0 and
286.0 respectively.


EXERCISE # 04 SUBJECTIVE EXERCISE # 02
1. The enthalpy of combustion of glucose is – 2808 KJmol–1 at 25°C. How many grams of glucose
do you need to consume [Assume wt = 62.5 Kg].
(a) to climb a flight of stairs rising through 3M.
(b) to climb a mountain of altitude 3000 M?
Assume that 25% of enthalpy can be converted to useful work.
2. 1 mole of CO2 gas at 300 K is expanded under reversible adiabatic condition such that its volume
becomes 27 times.
(a) What is the final temperature. (b) What is work done.
Given  = 1.33 and CV = 25.08 J mol–1K–1 for CO2.
3. One mole of an ideal monoatomic gas is put through rev path as shown in figure. Fill in the balnk
in the table
given below:
State P V T
1
2
3

A
B
C
4. One mole of a perfect monoatomic gas is put through a cycle consisting of the following three
reversible steps :
(CA) Isothermal compression from 2 atm and 10 litres to 20 atm and 1 litre.
(AB) Isobaric expansion to return the gas to the original volume
of 10 litres with T going from T 1 to T2.
(BC) Cooling at constant volume to bring the gas to the original
pressure and temperature.
The steps are shown schematically in the figure shown.
(a) Calculate T1and T2.
(b) Calculate  E, q and W in calories, for each step and for the cycle.

5. The given figure shows a change of state A to state C by two paths ABC and AC for an ideal gas.
Calculate the:
(a) Path along which work done is least.
(b) Internal energy at C if the internal energy of gas at A is 10 J and amount
of heat supplied to change its state to C through the path AC is 200 J.
(c) Amount of heat supplied to the gas to go from A to B, if internal energy
change of gas is 10 J.
6. A monoatomic ideal gas of two moles is taken through a reversible cyclic process
VB V
starting from A as shown in figure. The volume ratios are = 2 and D = 4. If
VA VA
the temperature TA at A is 27°C, calculate:
(a) The temperature of the gas at point B.
(b) Heat absorbed or released by the gas in each process.
(c) The total work done by the gas during complete cycle.
7. The standard enthalpy of formation of water liquid is – 285.76 kJ at 298 K. Calculate the value of
373K. The molar heat capacities at constant pressure (Cp) in the given temperature range of H2
(g), O2(g) and H2O (l) are respectively 38.83, 29.16 and 75.312 JK–1mol–1.
8. Methane (Considered to be an ideal gas) initially at 25°C and 1 bar pressure is heated at
constant pressure until the volume has doubled. The variation of the molar heat capacity with
ansolute temperature is given by Cp = 22.34 + 48.1 × 10–3 T
where Cp is in JK–1 mol–1. Calculate molar (a)  H (b)  U.
9. Oxygen is heated from 300 to 600 at a constant pressure of 1 bar. What is the increases in molar
entropy? The molar heat capacity in JK–1 mol–1 for the O2 is
Cp = 25.5 + 13.6 × 10–3 T – 42.5 × 10–7 T2
10. A heat engine absorbs 760 kJ heat from a source at 380K. It rejects (1) 650 kJ, (ii) 560 kJ, (iii)
504 kJ of heat to sink at 280 K. State which of these represent a reversible, an irreversible and an
impossible cycle.
11. From the given T-S diagram of a reversible carnot engine, find
(i) work delivered by engine in each cycle
(ii) heat taken from the source in each cycle.
(iii)  Ssink in each cycle.
12. Using the data given below, establish that the vaporization of CCl4 (l) at 298 K to produce CCl4
(g) at 1 atm pressure does not occur spontaneously .
Given : CCl4 (l , 1 atm)  CCl4 (g , 1 atm) ;  S º = 94.98 JK -1 mol -1;
 H ºf (CCl4, g) =  106.7 kJ mol-1 &  H ºf (CCl4, l) =  139.3 kJ mol-1
13. From the given table answer the following questions:

CO(g) CO2(g) H2O(g) H2(g)
 H°298 (-KCal/mole) –26.42 –94.05 –57.8 0
 G°298 (-KCal/mole) –32.79 –94.24 –54.64 0
S°298 (-Cal/Kmole) 47.3 51.1 ? 31.2
Reaction: H2O(g) + CO(g) H2(g) + CO2(g)

(i) Calculate  r H 298 (ii) Calculate  r G 298 (iii) Calculate  r S298
(iv) Calculate  r E 298 (v) Calculate S298 [H2O(g)]
14. Calculate workdone in adiabatic compression of one mole of an ideal gas (monoatomic) from an
initial ressure of 1 atm to final pressure of 2 atm. Initial temperature = 300 K.
(a) If process is carried out reversible
(b) if process is carried out irreversible against 2 atm external pressure.
Compute the final volume reached by gas in two cases and describe the work graphically.
15. 1 mole of ice at 0°C and 4.6 mm Hg pressure is converted to water vapour at a constant
temperature and pressure. Find  H and  E if the latent heat of fusion of ice is 80 cal/gm and
latent heat of vaporisation of liquid water at 0°C is 596 cal per gram and the volume of ice in
comparison of that water (vapour) is neglected.
16. Two moles of an ideal gas (  = 5/3) are initially at a temperature of 27°C and occupy a volume of
20 litre. The gas is first expanded at constant pressure until the volume is doubled. It then
undergoes adiabatic change until the temperature returns to its initial value.
(a) Sketch the process on P – V diagram.
(b) What are final pressure and final volume of gas.
(c) What is the work done by the gas.
17. Pressure over 1000 ml of a liquid is gradually increases from 1 bar to 1001 bar under adiabatic
conditions. If the final volume of the liquid is 990 ml, calculate  U and  H of the process,
assuming linear variation of volume with pressure.
18. One mole monoatomic ideal gas was taken through process ABCD as shown in figure. Calculate
(i) wAB, wBC , wCD , wDA
(ii) qAB, qBC, qCD, qDA
(iii)  HAB,  HBC,  HCD,  HDA
[Use : ln (3/2) = 0.40 ; ln (4/3) = 0.29]
19. One mole of ideal monoatomic gas was taken through reversible isochoric heating from 100 K to
1000 K. Calculate  Ssystem ,  Ssurr, and  Stotal in
(i) when the process carried out reversibly
(ii) when the process carried out irreversibly (one step)

20. Calculate the entropy of a substance at 600 K using the following data.
(i) Heat capacity of solid from 0 K to normal melting point 200 K
CP,m(s) = 0.035 T JK–1mol–1.
(ii) Enthalpy of fusion = 7.5 KJ mol–1,

(iii) Enthalpy of vaporisation = 30 KJ mol–1.
(iv) Heat capacity of liquid from 200 K to normal boiling point 300 K
CP,m(l) = 60 + 0.016 T JK–1mol–1.
(v) Heat capacity of gas from 300 K to 600 K at 1 atm
CP,m(g) = 50.0 JK–1mol–1.
21. Compute  rG for the reaction H2O (l, 1 atm, 323 K)  H2O (g, 1 atm, 323 K)
Given that :  vapH at 373 K = 40.639 kJmol–1, CP(H2O, l ) = 75.312 J K–1mol–1,
Cp (H2O, g) = 33.305 J K–1mol–1.
22. The enthalpies of neutralization of NaOH & NH4OH by HCl are  13680 calories and  12270 cal
respectively. What would be the enthalpy change if one gram equivalent of NaOH is added to one
gram equivalent of NH4Cl in solution? Assume that NH4OH and NaCl are quantitatively obtained.
23. The heat of reaction ½H2(g)+ ½ Cl2(g)  HCl (g) at 27°C is  22.1 k cal . Calculate the heat
of reaction at 77° C . The molar heat capacities at constant pressure at 27°C for hydrogen ,
chlorine & HCl are 6.82, 7.70 & 6.80 cal mol -1 respectively.
24. A cylinder of gas supplied by a company contains 14 kg of butane . The heat of combustion of
butane is 2658 kJ/mol. A normal family requires 20 MJ of energy per day of cooking. If the
cylinder lasts for 26 days, what percentage of gas is wasted due to inefficient combustion.
25. A cylinder of gas is assumed to contains 11.2 kg of butane. If a normal family needs 20,000 kJ of
energy per day for cooking, how long will the cylinder last if the enthalpy of combustion,
H  – 2658 kJ / mole for butane.
26. The molar enthalpy of vaporization of benzene at its boiling point (353 K) is 30.84 kJmol –1. What
is the molar internal energy change? For how long would a 12 volt source need to supply a 0.5 A
current in order to vaporise 7.8 g of the sample at its boiling point ?
27. 1.00 l sample of a mixture of CH4(g) & O2(g) measured at 25º C & 740 torr was allowed to react
at constant pressure in a calorimeter which together with its contents had a heat capacity of 1260
cal/K. The complete combustion of the methane to CO 2 & H2O caused a temperature rise in the
calorimeter of 0.667 K. What was the mole percent of CH4 in the original mixture?
 Hºcomb (CH4) =  215 k cal mol-1 .
28. From the following data :

Enthalpy of formation of CH3CN = 87.86 KJ/mol, Enthalpy of formation of C2H6 = – 83.68 KJ/mol
Enthalpy of sublimation of graphite = 719.65 KJ/mol
Enthalpy of dissociation of nitrogen = 945.58 KJ/mol;
Enthalpy of dissociation of H2 = 435.14 KJ/mol
C–H bond enthalpy = 414.22 KJ/mol
Calculate the (i) C  C ; (ii) C  N
29. Calculate the heat of combustion of methyl alcohol at 298 K from the following data
Bond C  H C  O O  H O=O C=O
Energy kJ mol-1 414 351.5 464.5 494 711
Resonance energy of CO2 =  143 kJ mol-1
Latent heat of vaporisation of methyl alcohol = 35.5 kJ mol-1.

Latent heat of vaporisation of water = 40.6 kJ mol-1.
30. For reduction of ferric oxide by hydrogen, Fe2O3(s) + 3 H2(g)  2 Fe(s) + 3 H2O(l) ;
 Hº298 =  35.1 kJ . The reaction was found to be too exothermic to be convenient. It is
desirable that  Hº should be at the most  26 kJ . At what temperature is it possible ?

CP[Fe2O3] = 104.5, CP[Fe(s)] = 25.5, CP[H2O(l)] = 75.3, CP[H2(g)] = 28.9 (all in J/mol)
31. From the following data of  H of the following reactions

C(s) + 1/2O2(g)  CO(g) ;  H = –110 KJ
and C(s) + H2O(g)  CO(g) + H2(g) ;  H = 132 KJ
Calculate the mole composition of the mixture of steam and oxygen on being passed over coke at
1273 K, keeping the reaction temperature constant.
32. An intimate mix of ferric oxide & Al is used as solid rocket fuel . Calculate the fuel value per
gm & fuel value per CC of the mix . Heats of formation & densities are :
 Hfº (Al2O3) =  399 k cal/mole ;  Hfº (Fe2O3) =  199 kcal / mole,
density of Fe2O3 = 5.2 g/cc ; density of Al = 2.7 g/cc.
33. A person takes 15 breaths per minute . The volume of air inhaled in each breath is 448 ml and
contains 21% of oxygen by volume . The exhaled air contains 16% of oxygen by volume . If
all the oxygen is used in the combustion of sucrose, how much of the latter is burnt in the body
per day & how much heat is evolved .  Hcom of sucrose is =  6000 kJ mol-1. Take
temperature to be 300 K throughout.

34. The enthalpies of neutralization of a strong acid HA & a weaker acid HB by NaOH are
 13680 cal/equivalent &  2900 cal/equivalent respectively. When one equivalent of NaOH is
added to a solution containing one equivalent of HA & one equivalent of HB, the enthalpy change
was  6900 calories . In what ratio is the base distributed between HA & HB ?
35. Using the data (all values are in kJ/mol at 25º C) given below :
 Hºcombustion (ethane) =  1559.8 ;  Hºcombustion (ethene) =  1410.9
 Hºcombustion (acetylene) =  1299.7 ;  Hºcombustion (acetaldehyde) =  1192.3
 Hºf CO2(g) =  393.5 ;  Hºf of H2O(l) =  285.8
 Hº for C(s) (graphite)  C(g) = + 716.68 ; Bond energy of H  H = 435.94
Bond energy of O = O = 498.94
Calculate the following bond energies :
(i) C  C (ii) C  H (iii) C = O
(iv) C = C (v) C  C
36. Use the following data to calculate the enthalpy of formation of As 2O3 .
(i) As2O3(s) + [(3 H2O + aq)]  2 H3AsO3 (aq) ;  H = + 7550 cal
3
(ii) As(s) + Cl (g)  AsCl3 (l) ;  H =  71390 cal
2 2
(iii) AsCl3(l) + (3 H2O + aq)  H3AsO3 (aq) + 3 HCl(aq) ;  H =  17580 cal
(iv) HCl(g) + aq  HCl (aq) ;  H =  17315 cal

1 1
(v) H (g) + Cl2(g)  HCl (g) ;  H =  22000 cal
2 2 2
1
(vi) H2(g) + O (g)  H2O (l) ;  H =  68360 cal
2 2
37. Calculate the proton affinity of NH3(g) from the following data (in kJ/mole)
Hdissociation : H2(g) = 218 ; Hdissociation : Cl2(g) = 124

Hformation : NH3(g) = – 46 ; Hf : NH4Cl(s) = –314
Lattice energy of NH4Cl (s) = – 683
Ionization energy of H = 1310
Electron affinity of Cl = 348
38. The standard enthalpy of formation of FeO & Fe 2O3 is  65 kcal mol-1 and  197kcalmol-1
respectively. A mixture of two oxides contains FeO & Fe 2O3 in the mole ratio 2 : 1 . If by
oxidation, it is changed into a 1 : 2 mole ratio mixture, how much of thermal energy will be
released per mole of the initial mixture ?
39. The enthalpy of formation of C2H5OH(l) is  66 k cal/mol . The enthalpy of combustion of

CH3  O  CH3 is  348 k cal/mol . Given that the enthalpies of formation of CO 2(g) and H2O(l)
are  94 k cal/mol &  68 k cal/mol respectively, calculate  H for the isomerisation of ethanol to
methoxymethane. All data are at 25º C.
40. FexO4 a mixed oxide of iron consists of only Fe+2 & Fe+3 ions, with the ratio of Fe+2 : Fe+3 =
1:2 in the mixed oxide. From the data given below,
Enthalpy of formation,  Hf (FexO4) = –1092 kJ/mol.
Enthalpy of sublimation,  Hsub (Fe) = 390 kJ/mol.
B.D.E of O2 = 490 kJ/mol.
I.E1 of Fe = 760 kJ/ mol.
I.E2 of Fe = 1560 kJ/mol.
I.E3 of Fe = 2960 kJ/mol.
I.E1 of O2– = –844 kJ/mol.
I.E2 of O2– = 142 kJ/mol.

Lattice Energy of FexO4 = 18930 kJ/mol.
Prove that value of x is 3 with the help of given data.


EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS

1. The entropy change in the isothermal reversible expansion of 2 moles of an ideal gas from 10 to
100 L at 300 K is [KVPY 2013]
(A) 442.3 JK 1 (B) 35.8 JK 1 (C) 38.3 JK 1 (D) 32.3 JK 1
2. For the isothermal reversible expansion of an ideal gas [KVPY 2013]

(A) H  0 and U  0 (B) H  0 and U  0
(C) H  0 and U  0 (D) H  0 and U  0
3. The molar enthalpy change for H2O I 

 H2O  g at 373 K and 1 atm is 41 kH/mol. Assuming


ideal behavior, the internal energy change for vaporization of 1 mol of water at 373 K and 1 atm in
-1
kJ mol is [KVPY 2014]
(A) 30.2 (B) 41.0 (C) 48.1 (D) 37.9
Given that the bond energies of: N  N is 946 kJ mol , H  H is 435 kJ mol , N  N is 159
-1 -1
4.
kJ mol1 , and N  H is 389 kJ mol1 , the heat of formation of hydrazine in the gas phase in
kJ mol1 is [KVPY 2014]
(A) 833 (B) 101 (C) 334 (D) 1268
5. The latent heat of melting of ice at 0C is 6 kJ mol1 . The entropy change during the melting in
JK 1mol1 closest to [KVPY 2014]
(A) 22 (B) 11 (C) 11 (D) 22
6. Two smaples A and B of an ideal gas, initially at same temperature and pressure, are
compressed from volume V to V/2, isothermally for A and adiabatically for B. The final pressure of
A will be [INCHO 2014]
(A) greater than that of B (B) less tha that of B
(C) twice that of B (D) equal to that at B
7. The heat of formation of ethanol, from the following data is

C2H5OHl  3O2  g  2CO2  g  H2O l  1368 kJ
Hf CO2  g  393.5 kJ / mol; Hf H2O l  286 kJ / mol . [INCHO 2014]
(A) 277 kJ / mol (B) 1260.5 kJ / mol (C) 688.5 kJ / mol (D) 3013 kJ / mol
8. N2 gas stored in a cylinder, fixed with a movable piston, undergoes adiabatic expansion. The
statement that is true for the given situation is [INCHO 2014]
(A) q  w (B) U  w (C) U  0 (D) U  q
9. The enthalpy of vaporization of benzene is 35.3 kJ / mol at its boiling point of 80C . The entrpy
change in the transition of vapour to liquid at its boiling point is [INCHO 2014]
(A) 100 (B) 100 (C) 342 (D) 342
10. The process in which an ideal gas undergoes change from X to Y as shown in the following
diagram is [NSEC 2015]
X
A
T
(A) isothermal compression

(B) adiabatic compression
(C) isothermal expansion
(D) adiabatic expansion
11. Glucosewhen dissolved in water leads to cooling of the solution. Suppose you take 250 mL water
at room temperature in an open container (such as a bowl) made of thermally insulated material
and dissolve a spoonful of glucose in it if you are able to accurately measeur the heat absorbed
by this solution in reaching back to room temperature (assuming negligible changes in the
composition and the amount of solution during this process), you will be measuring [NSEC 2015]
(A) the enthalpy of dissolution of the lucose in water
(B) the Gibbs free energy of dissolution of the glucose in water
(C) the work done by the atmosphere on the system during the dissolution process
(D) the heat capacity of solution
12. An ideal gas taken in an insulated chamber is released into intersetellar space. The statement
that is nearly rue for this process is [NSEC 2015]
(A) Q  0, W  0 (B) W  0, Q  0 (C) U  0, Q  0 (D) Q  W  U  0
13. Standard molar enthalpy of formation of CO2  g is equal to [NSEC 2016]

(A) Zero
(B) The standard molar enthalpy of combustion of carbon (graphite)
(C) The standard molar enthalpy of combustion of C  g
(D) The standard molar enthalpy of combustion of CO  g
14. For the conversion CCl4     CCl4  g at 1 bar and 350 K, the correct set of thermodynamic
parameters is (Boiling point of CCl4 is 77C ) [NSEC 2016]
(A) G  0, S  ve (B) G  0, S  ve
(C) G  ve, S  0 (D) G  ve, S  ve

15. Which reaction is sponstaneous at all temperatures at standard pressure and concentration?
[NSEC 2016]
(A) exothermic reaction with a decrease in entropy
(B) exothermic reaction with an increase in entropy
(C) endothermic reaction with a decrease in entropy
(D) endothermic reaction with an increase in entropy
16. Given rH  54.08kJmol1 and r S  10.0Jmol1 at 25C , the value of log10 K fir the reaction


A 
 B is [NSEC 2016]
(A) 3.4 (B) 10 (C) 0.53 (D) 113


1. An ideal gas is allowed to expand both reversibly and irreversibly in an isolated system. If T i is the
initial temperature and Tf is the final temperature, which of the following statements is correct ?
[2006]
(A) Tf > Ti for reversible process but Tf = Ti for irreversible process
(B)  Tf rev =  Tf irrev
(C) Tf = Ti for both reversible and irreversible processes
(D)  Tf irrev >  Tf rev
2. ( H  U ) for the formation of carbon monoxide (CO) from its elements at 298 K is
(R = 8.314 J K-1 mol-1) [2006]
1 1 1
(A) 1238.78 Jmol (B) 2477.57 Jmol (C) 2477.57 Jmol (D) 1238.78 Jmol1
3. Identify the correct statement regarding a spontaneous process : [2007]

(A) Exothermic processes are always spontaneous.
(B) Lowering of energy in the reaction process is the only criterion for spontaneity.
(C) For a spontaneous process in an isolated system, the change in entropy is positive.
(D) Endothermic processes are never spotaneous.
4. In conversion of lime-stone to lime, CaCO3 (s)  CaO(s) + CO2 (g) the values of  H0 and 
S0 are + 179.1 kJ mol–1 and 160.2 J/K respectively at 298 K and 1 bar. Assuming that  H° and
 S° do not change with temperature, temperature above which conversion of limestone to lime
will be spontaneous is : [2007]
(A) 845 K (B) 1118 K (C) 1008 (D) 1200 K
5. Assuming that water vapour is an ideal gas, the internal energy change (  U) when 1 mol of
water is vapourised at 1 bar pressure and 100°C, (Given : Molar enthalpy of vapourization of
water at 1 bar and 373 K = 41 kJ mol–1 and R = 8.3 J mol–1 K–1) will be : [2007]
(A) 37.904 kJmol1 (B) 41.00 kJmol1 (C) 4.100 kJmol1 (D) 3.7904 kJmol1
6. The standard enthalpy of formation (  Hf°) at 398 K for methane, CH4(g) is 74.8 kJ mol–1. The
additional information required to determine the average energy for C - H bond formation would
be : [2007]
(A) the dissociation energy of H2 and enthalpy of sublimation of carbon
(B) latent heat of vapourisation of methane
(C) the first four ionization energies of carbon and electron gain enthalpy of hydrogen
(D) the dissociation energy of hydrogen molecule, H 2

7. Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1, respectively.
1 3
For the reaction, X2 + Y2  XY3  H = – 30 kJ. To be at equilibrium the temperature will
2 2
be : [2008]
(A) 500 K (B) 750 K (C) 1000 K (D) 1250 K
8. On the basis of the following thermochemical data : (  ƒGºH+(aq) = 0) [2009]
H2O(  )  H+ (aq) + OH– (aq.) ;  H = 57.32 kJ

1
H2(g) + O (g)  H2O (  ) ;  H = –286.20 kJ
2 2
The value of enthalpy of formation of OH– ion at 25ºC is :
(A) 228.88 kJ (B) 228.88 kJ (C) 343.52 kJ (D) 22.88 kJ
9. In a fuel cell methanol is used as fuel and oxygen gas is used as an oxidizer. The reaction is
3
CH3OH(  ) + O (g)  CO2(g) + 2H2O(  )
2 2
At 298 K, standard Gibb‘s energies of formation for CH 3OH(  ), H2O(  ) and CO2 (g) are –166.2,
–237.2 and –394.4 kJ mol–1 respectively. If standard enthalpy of combustion of methanol is

– 726 kJmol–1 , efficiency of the fuel cell will be : [2009]
(A) 87% (B) 90% (C) 97% (D) 80%
10. The standard enthalpy of formation of NH3 is – 46.0 kJ mol–1. If the enthalpy of formation of H2
from its atoms is – 436 kJ mol–1 and that of N2 is – 712 kJ mol–1, the average bond enthalpy of
N – H bond in NH3 is [2010]
(A) – 964 kJ mol–1 (B) + 352 kJ mol–1

(C) + 1056 kJ mol–1 (D) – 1102 kJ mol–1
11. For a particular reversible reaction at temperature T,  H and  S were found to be both +ve. If
Te is the temperature at equilibrium, the reaction would be spontaneous when. [2010]
(A) Te > T (B) T > Te (C) Te is 5 times T (D) T = Te
12. The entropy change involved in the isothermal reversible expansion of 2 moles of an ideal gas
3 3
from a volume of 10 dm to a volume of 100 dm at 27°C is:- [2011]
(A) 32.3 J mol–1 K–1
(B) 42.3 J mol–1 K–1
(C) 38.3 J mol–1 K–1
(D) 35.8 J mol–1 K–1
13. The incorrect expression among the following is: [2012]

H  TS
(A) lnK 
RT
 ΔG°/RT
(B) K  e
G system
(C)  T
Stotal
Vf
(D) In isothermal process, Wreversible  nRT ln
Vi
14. A piston filled with 0.04 mol of an ideal gas expands reversibly from 50.0 mL to 375 mL at a
constant temperature of 37.00C. As it does so, it absorbs 208J of heat. The values of q and w for
the process will be: (R = 8.314 J/mol K) (n 7.5 = 2.01) [2013]
(A) q = – 208 J, w = – 208 J (B) q = – 208 J, w = + 208 J
(C) q = + 208 J, w = + 208 J (D) q = + 208 J, w = – 208 J
15. For complete combutin of ethanol, C2H5OH    3O2  g  2CO2  g  H2O    , the amount of
heat produced as measured in bomb calorimeter, is 1364.47 kJ mol1 at 25C . Assuming

-1
ideality the Enthalpy of combustion, CH, for the reaction will be: (R = 8.314 kJ mol ) [2014]
-1 -1 -1 -1
(A) –1460.50 kJ mol (B) – 1350.50 kJ mol (C) – 1366.95 kJ mol (D) – 1361.95 kJ mol
16. The following reaction is performed at 298 K.

2NO  g  O2  g 
 2NO2  g


The standard free energy of formation of NO(g) is 86.6 kJ/mol at 298 K. What is the standard free
12
energy of formation of NO2(g) at 298 K? (KP = 1.6 × 10 ) [2015]
(A) 86600 + R(298) ln(1.6×10 )

12
(B) 86600 

In 1.6  1012 
R  298 
(C) 0.5 2  86600  R  298  In 1.6  1012 

   
(D) R  298  In 1.6  1012  86600
17. 

 B  C is 2494.2 J. At a
The standard Gibbs energy change at 300 K for the reaction 2A 
1 1
given time, the composition of the reaction m ixture is  A   ,B  2 and C  . The reaction
2 2
proceeds in the: [R = 8.314 J/K/mol, e = 2.718] [2015]
(A) reverse direction because Q > Kc (B) forward direction because Q < Kc
(C) reverse direction because Q < Kc (D) forward direction because Q > Kc
-1
18. The heats of combustion of carbon and carbon monoxide are –393.5 and –283.5 kJ mol ,
respectively. The heat of formation (in kJ) of carbon monoxide per mole is : [2016]
(A) 676.5 (B) –676.5 (C) –110.5 (D) 110.5



EXERCISE # 07 JEE (ADVANCED) CORNER

1. A process A  B is difficult to occur directly instead it takes place in three successive steps.
[2006]
 S (A  C ) = 50 e.u.
 S (C  D ) = 30 e.u.
 S (B  D ) = 20 e.u.
where e.u. is entropy unit.
Then the entropy change for the process  S (A  B) is
(A) +100 e.u. (B) –60 e.u. (C) –100 e.u. (D) + 60 e.u.
2. The molar heat capacity of a monoatomic gas for which the ratio of pressure and volume is one.
[2006]
(A) 4/2 R (B) 3/2 R (C) 5/2 R (D) zero
3. For the process H2O (l) (1 bar, 373 K)  H2O (g) (1 bar, 373 K), the correct set of
thermodynamic parameters is [2007]
(A)  G = 0,  S = +ve (B)  G = 0,  S = –ve
(C)  G = +ve,  S = 0 (D)  G = –ve,  S = +ve
4. Statement-1: There is a natural asymmetry between converting work to heat and converting
heat to work. and
Statement-2: No process is possible in which the sole result is the absorption of heat from a
reservoir and its complete conversion into work. [2008]
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-
1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
5. Among the following, the state function(s) is (are) [2009]

(A) Internal energy (B) Irreversible expansion work
(C) Reversible expansion (D) Molar enthalpy
6. Match the transformations in column I with appropriate options in column II [2011]

Column - I Column - II
(A) CO2  s   CO2  g  (P) phase transition
(B) CaCO3  s  CaO  s   CO2  g (Q) allotropic change
(C) 2H  H2  g  (R)  H is positive
(D) P white, solid   P red,solid  (S)  S is positive
(T)  S is negative
7. For an ideal gas, consider only P-V work in going from a initial state X to the final state Z. The
final state Z can be reached by either of the two paths shown in the figure. Which of the following
choice (s) is (are) correct ? [take DS as change in entropy and w as work done] [2012]
(A) ΔSx z = ΔSx y + ΔSyz (B) Wx z = Wx y + Wyz

(C) Wx y z  Wx y (D) ΔSx yz =ΔSx y
8. Using the data provided, calculate the multiple bond energy (kJ mol –1) of a C C bond in C2H2.
That energy is (take the bond energy of a C–H bond as 350 kJ mol–1)
2C(s) + H2(g)  C2H2(g)  H = 225 kJ mol–1
2C(s)  2C(g)  H = 1410 kJ mol–1
H2(g)  2H(g)  H = 330 kJ mol–1 [2012]

(A) 1165 (B) 837 (C) 865 (D) 815
9. The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown in
the figure. Which of the following statement(s) is are correct? [2012]
(A) T1 = T2 (B) T3 > T1

(C) W isothermal > W adiabatic (D)  Uisothermal >  Uadiabatic
10. The standard enthalpies of formation of CO 2(g), H2O(l) and glucose(s) at 25ºC are
–400 kJ/mol, –300 kJ/mol and –1300 kJ/mol, respectively. The standard enthalpy of combustion
per gram of glucose at 25ºC is [2013]
(A) +2900 kJ (B) –2900 kJ (C) –16.11 kJ (D) +16.11 kJ

11. Benzene and naphthalene form an ideal solution at room temeprature. For this process the true
statement(s) is (are) [2013]
(A)  G is positive (B)  Ssystem is positive
(C)  Ssurrounding = 0 (D)  H = 0
COMPREHENSION (Q. 12 & 13)

A fixed mass ‗m‘ of a gas is subjected to transormation of states from K to L to M to N and back to
K as shown in the figure. [2013]
12. The succeeding operations that enable this transformation of states are
(A) Heating, cooling, heating, cooling
(B) Heating, cooling, cooling, heating
(C) Cooling, heating, cooling, heating
(D) Cooling, heating, heating, cooling
13. The pair of isochoric processes among the transformatin of states is

(A) K to L and L to M (B) L to M and N to K
(C) L to M and M to N (D) M to N and N to K
14. An ideal gas in a thermally insulated vessel at internal pressure = P 1, volume = V1 and absolute
temperature = T1 expands irreversibly against zero external pressure, as shown in the diagram.
The final internal pressure, volume and absolute temperature of the gas are P2, V2 and T2,
respectively. For this expansion, [2014]
(A) q = 0
(B) T2 = T1
(C) P2V2 = P1V1
(D) P2 V2  P1V1
15. For the process

H2O    
H2O  g
at T = 100  C and 1 atmosphere pressure, the correct choice is [2014]
(A) Ssystem  0 and Ssurrounding  0 (B) Ssystem  0 and Ssurrounding  0
(C) Ssystem  0 and Ssurrounding  0 (D) Ssystem  0 and Ssurrounding  0
16. Match the thermodynamic processes given under Column I with the expression given under
Column II: [2015]
Column I Column II
(A) Freezing of water at 273 K and 1 atm (P) q = 0
(B) Expansion of 1 mol of an ideal gas into a (Q) w = 0
vacuum under isolated conditions
(C) Mixing of equal volumes of two ideal gases (R)  Ssys < 0
at constant temperature and pressure in an
isolated container
(D) Reversible heating of H2(g) at 1 atm from (S)  U = 0
300 K to 600 K, followed by reversible
cooling to 300 K at 1 atm
(T)  G = 0
17. One mole of an ideal gas at 300 K in thermal contact with surroundings expands isothermally
from 1.0 L to 2.0 L against a constant pressure of 3.0 atm. In this process, the change in entropy
-1
of surrounding (  Ssurr)in JK is (1L atm = 101.3 J) [2016]
(A) 5.763 (B) 1.013
(C) – 1.013 (D) – 5.763


ANSWER KEY
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. C C C A D C D A B C
Qs. 11 12 13 14 15 16 17 18 19 20
Ans. A C D C D C A A D B
Qs. 21 22 23 24 25 26 27 28 29 30
Ans. D D D A A C C B A B
Qs. 31 32 33 34 35 36 37 38 39 40
Ans. C A D D D A B D C B
ANSWER KEY EXERCISE # 02 ADVANCED LEVEL EXERCISE
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. ABCD CD ABCD ABCD ABCD ABC ABC ABD ABCD ACD
Qs. 11 12 13 14 15 16 17 18 19 20
Ans. ABC ABD BCD ABC AC BC ABD ABD B C
Qs. 21 22 23 24 25 26 27 28 29 30
Ans. A C B B A C B A A C
Qs. 31 32 33 34 35 36 37 38 39 40
Ans. A D A C D D A C C A
Qs. 41 42 43 44 45 46 47 48 49 50
Ans. B A A B A A B B B D
Qs. 51 52 53 54 55 56 57
Ans. C C B C A A (A)  R,(B)  PQS,(C)  QS,(D)  QS
Qs. 58 59
Ans. (A)  Q , (B)  PRS, (C)  S, (D)  PQR (A)  PS, (B)  QS, (C)  S, (D)  R
Qs. 60 61
Ans. (A)  RQ, (B)  PQ, (C)  SQ, (D)  Q (A)  PS, (B)  P, (C)  Q, (D)  PRS
Qs. 62 63
Ans. (A)  Q S, (B)  PR, (C)  PS, (D)  PS (A)  P S,(B)  S, (C)  Q, (D)  R
Qs. 64 65
Ans. (A)  PQS, (B)  Q, (C)  Q, (D)  R (A)  R, (B)  S, (C)  P, (D)  Q
Qs. 66 67 68 69 70 71 72 73 74 75
Ans. 50 20 1 1 9 6 5 1 16 50

Q.1 (i) w, (ii) – w, (iii) – w, (iv) w, (v) – w

Q.2 – 0.3024 kJ
Q.3  E =75.11 kJ
Q.4  E = 0.993 k cal,  H = 1 k cal
Q.5 q = 177.9 kJ, w = – 2.5 kJ ;  E = 175.4 kJ
Q.6 DE = – 39.03 KJ/mole; q = – 36.5 KJ;w = – 2.53 KJ
Q.7  U = w = –1247.1 ;  H = – 1745.94 J
Q.8 wirr= – 9353.25, wrev= –17288.47 J,  U =  H =0
Q.9 – 1.683 kJ
Q.10 q = 0; w =  U= 4.12 KJ;  H = 5.37 KJ; Vf = 11.8 dm3; P = 5.21 atm
Q.11 CV,m= 31.6 JK–1mol–1
5 1 25  PV 
Q.12 W = P0V0 ; qCA =  P°V° ; qAB = 3P°V° ; qBC = P°V° Tmax =
2 2 8  R 
Q.13
Table-1
State P V T
1 1 atm 22.4 273
2 2 atm 22.4 546
3 1 atm 44.8 546

A Isochoric 3/2 R(273) 0 3/2 R(273) 5/2 R(273)
B Isothermal R ln 2 R ln 2 0 0
C Isobaric –5/2 R (273) R (273) –3/2 R (273) –5/2 R (273)
Cyclic –R(273) + R ln 2 R(273)-R ln 2 0 0
Q.14 T = 1059 K
Q.15 - 1721.8 J
Q.16 (i) q = – w = 17.54 kJ ,  U = 0 and  H =0 ; (ii) q = 0 , w =  U = –10.536 kJ and  H = –
14.75kJ
(iii) q = 0 , w = 0 ,  U = 0 and  H =0 (iv) q = 0;  U = w = – 7.14 KJ;  H = – 9.996 KJ,
(v) q = –w = 10. 0 KJ,  U =  H = 0
Q.17 (a) q =  H = 1558.88,  U = 935.33 ; w = – P(  U) = – 623.55 J mol–1
(b) w = – 2149.7;  U &  H = 0, q = – w
(c) q = 0, w = – 810.62 ,  H = – 1351.03 Jmol –1
for overall process q = 3708.59 ; w = – 3583.88,  U = 124.71 ;  H = 207.85
Q.18 (i) - 90.5 (ii) - 374.5 (iii) - 3.26 (all in J mol-1 K-1)
Q.19 (i)  Ssys = 0 ;  Ssurr = 0 and  Stotal = 0, (ii)  Ssurr = 0 ;  Stotal =  Ssys = 0.957 JK–1
(iii)  S sys =  S total = 3.81 JK –1
Q.20 – 216.198 J mol–1 Q.21 -88kJ/mol

Q.22 35.973 MJ Q.23 2.95 kcal
Q.24 – 18.7 kcal Q.25 –1560.1 kJmol–1
Q.26 (i) - 3201 kJ/mol ; (ii) - 3199.75 kJ/mol Q.27 - 3273.77 kJ/mol
Q.28 27.43 g O2 Q.29 – 75.14 kJ/mole
Q.30 (i) - 885 kJ/mol (ii) - 889.980 kJ/mol Q.31 213 kJ / mol
Q.32 - 90.75 kcal mol-1
Q.33 Hfº(benzene) = 49 kJ mol-1, HCº(benzene) = - 3267.4 kJ mol-1]
Q.34 - 666.81 k cal mol-1, 15.55 Mcal Q.35 292 kcal/mol

Q.36 for Cl- - 384 kJ mol-1, for I- - 307 kJ mol-1 Q.37 advantage = 5396 kJ.mol-1
Q.1 (a) 0.47 gm, (b) 0.47 kg

Q.2 T2 = 100 K ; W = 5.016 KJ
Q.3
State P V T
1 1 atm 22.4 273
2 1 44.8 546
3 0.5 44.8 273

A Isobaric 5/2 R(273) – R (273) 3/2 R(273) 5/2 R(273)
B Isochoric –3/2 R (273) 0 –3/2 R (273) –5/2 R(273)
C Isothermal –R ln 2 R ln 2 0 0
Cyclic –R(273) + R ln 2 –R(273)–R ln 2 0 0
Q.4 (a) T1= 243.60 K; T2 = 2436.0 K, (b)  E = 0; q = –w = +3262.88 cal

Q.5 (a) AC, (b) 170 J, (c) 10 J
Q.6 (a) 600 K, (b) qAB = 3000 cal; qBC=1663 cal; qCD= –1800 cal; qDA=–1663 cal; Total Q = 1200
cal, (c) W = –1200 cal
Q.7 H373
o
(H2O (l) )= – 284.11 kJ
Q.8 (a) 13.064 kJ mol–1, (b) 10.587 kJ mol–1

Q.9 21.18 JK–1 mol–1
Q.10 (i) irreversible, (ii) reversible, (iii) impossible
Q.11 (i) 30 kJ, (ii) + 60 kJ, (iii) 100 J/K

Q.12  Gº = 4.3 kJ mol-1 > 0

Q.13 (i) – 9.83 Kcal/mole; (ii) – 6.81 Kcal/mole, (iii) – 10.13 Cal / Kmole, (iv) –9.83 Kcal/mole,
(v) + 45.13 Cal/ K mole
Q.14 (a) T2 = 395.8 ; V2 = 16.24 L; W rev = 1194.72 J,
(b) V21 =17.24 L ; T21 = 420 K , W irrev = 1496.52 J
Q.15  H = 12168 calories;  E = 11623 calories
Q.16 (a) , (b) P2 = 0.435 atm V1 = 113.13 litre, (c) W T = –3000 cal
Q.17  U = 501 J ;  H = 99.5 kJ

Q.18 (i) wAB= – 1496.52 J,wBC= – 1446.63 Joule, wCD = 0, wDA=1728.84 Joule ;
(ii) qAB= 5237.82 Joule, qBC= 1446.63 Joule, qCD= – 3741.3 Joule, qDA=1728.84 Joule;
(iii)  HAB= 6235.5 Joule,  HBC = 0 ,  HCD = – 6235.5 Joule,  HDA = 0 Joule
3 3
Q.19 (i) Rev. Process  Ssyst = R ln 10 ;  Ssurr = – R ln 10
2 2
3 3 3
(ii) Irr Process  Ssys = R ln 10 ;  Ssurr = R (0 – 9) ;  Stotal = R (1.403)
2 2 2
Q.20 205.08 JK–1 mol–1 Q.21  rG = 5.59 kJ mol–1
Q.22 - 1410 cal Q.23 -22.123 k cal
Q.24 18.95 % Q.25 25.66 days
Q.26  E= 27.91 KJ mol-1, t= 514 sec. Q.27 10.0 mol % CH4
Q.28 (i) 343.08 ; (ii) 891.2 Q.29 - 669.7 kJ mol-1

Q.30 404 K Q.31 mole % O2(g) = 37.5, H2O(g) = 62.5
Q.32 0.9346 k cal g-1, 3.94 kcal cm-3 Q.33 9.822 MJ/day evolved
Q.34 0.371 : 0.629
Q.35 C-C = 97.81 kJ, C-H = 454.64 kJ, C=O = 804.26 kJ, C = C = 434.3 kJ, C  C = 733.48 kJ
Q.36 - 154.68 k cal Q.37 – 718 kJ/mol
Q.38 Heat released = 13.4 kcal. per mol of initial mixture
Q.39 22 kcal mol-1
ANSWER KEY EXERCISE # 05 KVPY, OLYMPIADS QUESTIONS
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. C C D B A B A B A B
Qs. 11 12 13 14 15 16
Ans. A D B A B B
Qs. 1 2 3 4 5 6 7 8 9 10
Ans. D A C B A A B A C B
Qs. 11 12 13 14 15 16 17 18
Ans. B C A D C C A C
ANSWER KEY EXERCISE # 07 JEE (ADVANCED) CORNER
Qs. 1 2 3 4 5 6
Ans. D A A A AD (A)  PRS,(B ) RS,(C)  T,(D) PQT
Qs. 7 8 9 10 11 12 13 14 15
Ans. AC D AD C BCD B B ABC B
Qs. 16 17
Ans. (A)  RT,(B)  PQS,(C)  PQS,(D)  PQST C


Chemistry Chemical Ionic Equilibrium and Chemical Thermodynamics

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XI MODULE - VI

CHEMICAL & IONIC EQUILIBRIUM

Step – I CatalyseR 's Practice Sheets & NCERT

Step – III Previous Years’ JEE Subjective & Objective Questions,

Step – IV After Completion of Step – III, if time permits, students can

This Study Package is Prepared by

 CONCEPTS IN BRIEF (Chemical Equilibrium) 1 – 23

 EXERCISE # 01 OBJECTIVE EXERCISE 24 – 29

 EXERCISE # 03 SUBJECTIVE EXERCISE (LEVEL # 01) 34 – 35

 EXERCISE # 04 SUBJECTIVE EXERCISE (LEVEL # 02) 35 – 36

 EXERCISE # 06 JEE (MAIN) CORNER 37

 EXERCISE # 07 JEE (ADVANCED) CORNER 38 – 39

JEE (MAIN) Formely known as AIEEE

Nothing is impossible, the word itself says ‘I’m possible’!

In this chapter, the extent of completion of the reaction is studied

For example For example

TYPE OF CHEMICAL REACTION

Irre ve rsi bl e re a ctio n Re ve rsib le re a ctio n

This can be shown graphically.

LAW OF MASS ACTION

Applying law of mass action,

RELATIONSHIP BETWEEN KP AND KC

[C]c (RT)c  [D]d (RT)d [C]c [D]d (RT)(c d)

REACTION QUOTIENT (Q) :

CHARACTERISTICS OF EQUILIBRIUM CONSTANT & FACTORS AFFECTING IT:

HOW TO USE NEGLECTION IN THE PROBLEM:

(b)  NH 4 2 CO3s  2NH3 g   CO2 g   H2Og 

 n NO = 1.087 × 0.4 = 0.435

(ii) (a) ng = 0  Kp = Kc

APPLICATION OF LAW OF MASS ACTION

1. Synthesis of Hydrogen Iodide:

Suppose the total pressure of the equilibrium mixture at 444°C is P, then

2. Thermal Dissociation of Phosphorus Pentachloride

PCl5(g) dissociates thermally according to the reaction,

Substituing the values of equilibrium concentration, in equation (1), we have

EQUILIBRIUM CONSTANT FOR HETEROGENEOUS EQUILIBRIA

(i) Thermal Dissociation of Solid Ammonium Chloride:

and K p  PNH3  PHCl

(ii) Thermal Dissociation of Ag2CO3:

THE LE - CHATELIER’S PRINCIPLE

EFFECT OF ADDITION OF INERT GASES TO A REACTION AT EQUILIBRIUM

Now we will derive the dependence of KP on temperature.

Dividing (iv) by (iii) we get

The enthalpy of a reaction is defined in terms of activation energies as

Now, Q P can also increase, decrease or remain unchanged. If K P increases and Q P

LE - CHATELIER’S PRINCIPLE AND PHYSICAL EQUILIBRIA

Le Chatelier’s principle, as already stated, is applicable to all types of equilibria involving

1. Vapour pressure of a liquid: Consider the equilibrium

FEE ENERGY AND CHEMICAL EQUILIBRIUM

For a general reaction, mA + nB pC + qD, DG is given by-

Here aX denotes the activity of X.

Now since, DG 0 = DH0 – TDS0

Condition for Spontaneity:

 G0 < 0 for spontaneous process or reaction.

The reaction quotient Qc for the reaction N 2 O 4 2NO 2 ,

G 0 130.2  103 Jmol1

Since pCO  pCO2 , hence

(i) NH4Cl(s) NH3(g) + HCl(g) Kp = 1.04 ×10–16

 P= 1.04  10 16 = 1.02 × 10–8 atm.

1.44  105 H  773  673 

673  773  2.303  1.0565  8.314

Relation between Vapour Density and Degree of Dissociation

II: N2O4 g  2NO2g  , y  2

(ii) D × 2 = theoretical molecular weight = 2