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At constant temperature,
n
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]
So, equation (1) can be rewritten as
PCc PDd
Kp
PAa PBb
(2)
Relationship Between Kp and Kc
From the above, for the same general reaction at constant
temperature.
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[C]c [D]d
Kc
[A]a [B]b
(1)
PCc PDd
and, Kp
PAa PBb
(2)
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
Kp
[A]a (RT)a [B]b (RT) b
[C]c [D]d (RT)(c d)
or Kp
[A]a [B]b (RT)(a b)
or K p K c (RT)
n
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
Illustration 1: Calculate the Kc and Kp for the following
reactions and also deduce the relationship
between Kc and Kp
i) 2SO2(g) + O2(g) 2SO3(g)
1 3
ii) 2
N 2(g) + H 2(g) NH 3(g)
2
Solution: i) 2SO2(g) + O2(g) 2SO3(g)
Applying law of mass action,
[SO3 ]2
Kc
[SO 2 ]2 [O 2 ]
(i)
2
PSO
Kp 2
PSO
3
PO2
(ii)
2
We know that
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K p K c (RT) n
Kc
n = 2 (2+1) = 1 Kp
RT
1 3
ii) 2
N 2(g) H 2(g) NH3(g)
2
[NH 3 ]
Kc
[N 2 ]1/ 2 [H 2 ]3/ 2 (i)
PNH
K p 1/ 2 3 3/ 2
PN 2 PH2 (ii)
Now, K p K c (RT) n
3 1
n 1 1
2 2
Kc
Kp
RT
Illustration 3: At 400K for the gaseous reaction
2A + 3B 3C + 4D
the value of Kp is 0.05. Calculate the value of K c (R
= 0.082 dm3 atm K1 mol1)
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. K1 mol1, we shall take
P = 1 atm.
7
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Reversible reactions: The reactions which never go to completion and that can occur in either
direction i.e. both possibilities are there in reversible reaction (products can give reactants and
reactants can give products).
In chemical equilibrium, we will analyse reversible chemical reaction, consider the following
reactions.A chemical reaction is never complete. This is due to the reversible nature of it.
Reversible means reaction taking place both in the forward and backward directions. The
reaction between reactants yielding product(s) is the forward reaction while the reaction between
products giving back reactants is the backward reaction. As the reaction progresses, a state of
equilibrium is reached when the rate of forward reaction becomes equal to that of the backward
reaction. After this there is no progress in the reaction although reactions are taking place in both
the directions. This is called the state of chemical equilibrium. It is due to the attainment of a
chemical equilibrium that chemical reaction does not go to completion. However, in some
chemical reaction equilibrium is attained when the reaction is almost complete. Such reversible
reactions are called irreversible reactions. The reversibility of a reaction is denoted by the
symbol
as shown below:
i) N 2 3H 2 2NH3
ii) H 2 I 2 2HI
A reversible reaction may be made irreversible if one of the products is allowed to escape away
from the reaction mixture. For example the reaction
CaCO3(s)
CaO (s) CO 2(g)
will be reversible in a closed container but it would become irreversible in an open container
due to escaping of CO2(g). That is CaCO3 CaO(s) + CO2(g) (open container)
Each reversible reaction consists of two reactions: one is forward reaction i.e. reactants combine
to give products and other is backward reaction i.e. product reaction recombine to give back
reactants.
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At one stage during reversible reactions, two reactions i..e forward and backward reactions
proceed with the same speed, the reaction is said to be in equilibrium.
Law of Mass Action: In 1863 two Chemistry Guldberg and Waage stated that, at constant
temperature, the rate at which a substance reacts is directly proportional to its active mass and
rate of a chemical reaction is directly proportional to the product of active masses (raised to
power their stoichiometric coefficients) of reactants.
Suppose,
A Products
R [A]
or A B Products
R [A][B]
Now if we consider the reversible reaction.
m1A m 2 B n1C n 2 D
Forward reaction: m1A m 2 B
n1C n 2 D
where k f is know as rate constant or velocity constant or specific reaction rate for forward
reaction.
Backward reaction: n1C n 2 D
1A m 2 B
m
Rate of backward reaction (rb ) (k b ) [C]n1 [D]n 2
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10 CHEMISTRY : CHEMICAL EQUILIBRIUM
or rb K b [C]n1 [D]n 2
where Kb is rate constant for backward reaction.
At equilibrium rf rb
k f [A]m1 [B]m 2 K b [C]n1 [D]n 2
Kf [C]n1 [D]n 2
K eq
Kb [A]m1 [B]m2
Initially A and B are mixed and they react. When they react, the rate of forward reaction
decreases since concentration of A and B decrease. As C and D are formed, they react to form A
and B. The rate of backward reaction increases with time because there is an increase in the
concentration of C and D. When the two rates are equal, we say that system is in equilibrium.
At equilibrium state
i) Rate of forward reaction = Rrate of backward reaction.
ii) Equilibrium is dynamic in nature i.e. reaction does not stops at equilibrium but two
reactions have equal rate.
iii) Once equilibrium is achieved the relative concentrations of reactants and products will
remain constant.
iv) External change in pressure, temperature and concentration at equilibrium causes
disturbance in equilibrium state. Again a new equilibrium will be reached after some
adjustment (in detail this is to be discussed in Le-Chatliers principle).
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vi) For gaseous reactions, the activities are expressed in terms of partial pressure
(total pressure mole fraction) the equilibrium constant Keq is denoted as Kp.
Suppose a reaction
N 2(g) 3H 2(g) 2NH 3(g)
P
2
NH3
Kp
P P
3
N2 H2
vii) Only a change in temperature can change the value of equilibrium constant Kp or
Kc. There is no effect of change in pressure or concentrations on the value of
equilibrium constant (exact variation of equilibrium constant with temperature
will be discussed latter).
viii) A very large value of Kc or Kp signifies that reaction is going in forward direction
i.e. the equilibrium largely lies towards forward direction or we can say reaction
almost goes to completion.
ix) The equilibrium constant of a reaction and its reverse reaction are reciprocal of
each other.
If A B C D (Equilibrium constant = K)
1
Then C D A B (Equilibrium constant K )
K
11
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ix) If a reaction is obtained by adding two reactions then its equilibrium constant
will be equal to the product of the equilibrium constants of two reactions. If K1
and K2 are step-wise equilibrium constant for
A B (i)
B C (ii)
Then for A C K K1 K 2
At any point in a reversible reaction, ratio of the concentration terms in the same form as in the
expression of equilibrium constant can be formulated. This ratio is referred to as reaction
quotient (Q). Consider a general reaction.
m1A m 2 B n1C n 2 D
[C]n1 [D]n 2
Q (in terms of concentration)
[A]m1 [B]m2
PC PD
n1 2n
Comparing the value of Q with the standard value of K eq at a given temperature, one can
comment on the status of reversible system. If
Q K eq It means equilibrium has not yet reached. The system is moving in forward
direction increasing product concentration i.e. at this instant forward reaction is
dominant over backward reaction.
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Q K eq
It means equilibrium is established and concentrations of reactants and
products will remain constant.
Q K eq It means equilibrium has not yet established. The reaction must proceed in
backward direction for the attainment of equilibrium.
DRILL EXERCISE I
1. Three moles of N2 react with 2 moles of O2 in a two litre container to form one mole of
NO. What will be the number of mole of N2 per litre at equilibrium.
(A) 0.75 (B) 1.50
(C) 1.25 (D) None of these
1. 0.75
2. For the reaction A + 2B
2C + D, initial concentration of A is a and that of B is
1.5 times that of A. concentration of A and D are same at equilibrium. What should be
the concentration of B at equilibrium.
a a
(A) (B)
4 2
3a
(C) (D) All of the above
4
a
2.
2
3. Under similar conditions
K P1
2NH 3
N 2 3H 2
K P2 1 3
NH 3
N 2 H 2
2 2
Which of the following is true for K P1 ?
K P2
(A) K P2 (B)
2
2 2
(C) (K P2 ) (D) (K P1 )
3. (K P2 ) 2
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Illustration 1: Consider the reaction SO2 Cl2 (g) SO 2 (g) Cl 2 (g) ; at 37C the value of
equilibrium constant for the reaction is 0.0032. It was observed that concentration of the three
species is 0.050 mol/lt each at a certain instant. Discuss what will happen in the reaction vessel?
Solution: In this question, concentration of three species i.e. SO2 Cl2 , SO2 and Cl2 (g) each
is given, but is is not mentioned that whether the system is at equilibrium or not.
So first check it. Find reaction coefficient for given equation.
As Q > K, the concentrations must adjust till Q = K for equilibrium. This can
happen only if reaction shifts backwards, and products recombine to give back
reactants. Hence in the reaction vessel, the system will move backward so that it
can achieve equilibrium state.
Kp c m (i)
PA PB n
1 2
15
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[C]n1 [D]n 2
Kc (ii)
[A]m1 [B]m2
PV = nRT
n
P RT
V
or P = CRT
Where C is molarity
PA CA RT ; PB C B RT
PC CC RT ; PD C D RT
CA RT m CB RT m
1 2
RT
n n
CCn C nD
1 2 1 2
= m
CA CmB RT m m
1 2 1 2
= K c (RT)(n1 n 2 ) (m1 m2 )
K p K c (RT) n
If Case I n 0
K p Kc
e.g. H 2(g) I2(g) 2HI(g)
N 2(g) O 2(g) 2NO(g)
Gaseous equilibria are of two types
Type I: In which n 0
to K p K c
e.g. H 2(g) I2(g) 2HI(g)
N 2(g) O 2(g) 2NO(g)
Type II In which n 0
Case - II n 0
So K p K c
e.g. PCl5(g) PCl3(g) Cl 2(g) ; n=1+1-1=1
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Kp = Kc(RT)1
Kp Kc
Case III n 0
N 2(g) 3H 2(g)
2NH3(g) n 2 (3 1) 2
Kp = Kc(RT)2
Kp Kc
N 2(g) 3H 2(g) 2NH 3(g) ; n 0
Solution: Since pressure is to be calculated, so first find K p using the relation between
K c and K p ,
K c 0.35, R 0.0821, T 473, n 1 3 2
K p K c (RT) n 0.35 (0.0821 473) 2 2.32 10 4
pZ
The expression for K p is : K p
p X (p Y ) 2
Moles X Y Z
Initially 1 1 0
At equilibrium 1x 2 2x X
total moles n T 3 2x
Let P = equilibrium pressure
17
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1 x 2 2x x
PX P, PY P, Pz P
3 2x 3 2x 3 2x
X
P
3 2X x(3 2x) 2
Kp 2
1 x 2 2x P 2 (1 x)(2 2x) 2
P P
3 2x 3 2x
x = 0.6 (given)
0.6(3 1.2) 2
Kp 2 2.32 10 4
P (1 0.6) 2 1.2) 2
P 2 (1.8 102 ) 2
P = 180 atm
DRILL EXERCISE II
1. A mixture of hydrogen and iodine (molecular ratio is 2 : 1) is reacted to form HI. The
total moles at equilibrium will be:
(A) 3 x (B) 3
(C) 2 2x (D) 3 4x
1. 3
2. In the reaction, A + B
C + D in a one-litre container, concentration of B at fixed
temperature was n mole and initial concentration of A was 3n mole. If the concentration
of C at equilibrium is equivalent to that of B, the concentration of D will be
n
(A) (B) n
4
n n
(C) (D)
3 2
n
2.
4
3. Which of the following should be added in the equilibrium reaction 2SO2 + O2
2SO3 for generation of heat, if the forward reaction is exothermic and the backward
reaction is endothermic?
(A) SO3 (B) SO2 and O2
(C) SO2, O2 and SO3 in equal amount (D) None of these
3. SO2 and O2
BRAIN TEASER 1:
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i) The vapour density of a mixture consisting of NO 2 and N2O4 is 38.3 at 26.7C. 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) 2NH 3(g) CO 2(g) H 2 O(g)
Let us consider that 1 mole of PCl 5 has been taken in a container of volume V litre and at
equilibrium x moles of PCl5(g) dissociates. Thus
PCl5(g) PCl3(g) + Cl2(g)
1
Initial concentration (mol L )1 0 0
1 x x x
Equilibrium concentration(mol L1)
V V V
According to law of mass action, at constant temperature,
[PCl3 ][Cl 2 ]
Kc = (1)
[PCl5 ]
PPCl3 PCl2
and Kp = (2)
PPCl5
Substituing the values of equilibrium concentration, in equation (1), we have
x x
V V
Kc = 1 x
V
x2
or Kc
V(1 x)
Now, total number of moles at equilibrium = 1 x + x + x = 1 + x
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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
1 x
P
1 x
x 2P K 1
or Kp 2 x 1 K p x 2 P x p x
(1 x ) P P
Similarly, we can apply law of mass action on any reaction at equilibrium.
BRAIN TEASER 2:
Derive an expression for Kc and Kp for the reaction
2NH3(g)
N2(g) + 3H2(g)
Assuming that in a container of volume V, initially 1 mole of N 2 and 3 moles of H 2 were taken and at
equilibrium 2x moles of NH3 is formed.
Illustration 3: For the chemical equilibrium
2NO(g) + O2(g)
2NO2(g)
2
Kp = 1.3 10 at 1000K. What is the value of Kc at 1000K?
21
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2. The equilibrium constant KC for A(g) B(g) is 1.1. Which gas has a molar
concentration greater than 1?
2. If [B] = 1; [A] = 0.91
3. 0.1 mole of N2O4(g) was sealed in a tube under atmospheric conditions at 25C.
Calculate the number of mole of NO 2(g) present, if the equilibrium N 2O4(g)
2NO2(g), (Kp = 0.14) is reached after some time.
3. NO2 = 0.017 2 = 0.034 mole
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0.6 0.6
P2
1.6 1.6
Again, K p 0.4
P
1.6
[Ag 2 O][CO 2 ]
Kc
[Ag 2 CO3 ]
Now, let us consider that 1 mol of Ag 2CO3(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 1x x x
Now, as Ag2CO3 and Ag2O are solids, so their concentration can be assumed to be
constants. tThus
x
K c [CO 2 ]
V
K P PCO2
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M
-
C
E
-
C
H
-
2
5
Confused with stress. Well by stress here what we mean is any change of reaction conditions
e.g. in temperature, pressure, concentration etc.
Let the moles of N2, H2 and NH3 at equilibrium be a, b and c moles respectively. Since the
reaction is at equilibrium,
X X
3 3
PN 2 PH 2 N 2 .PT H 2 .PT
= Kp =
P X
2 2
NH3 NH3 .PT
Where,
X terms denote respective mole fractions and PT is the total pressure of the system.
3
a b
a b c PT a b c PT
Kp
2
c
a b c PT
a
Here, = mole fraction of N2
abc
b
= mole fraction of H2
abc
c
= mole fraction of NH3
abc
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PT
2
ab3
2 = Kp
c a b c 2
Since PT =
a b c RT
( assuming all gases to be ideal)
V
3 2
ab RT
2 = KP (1)
c V
Now, let us examine the effect of change in certain parameters such as number of moles,
pressure, temperature etc.
If we increase the volume of the container (which amounts to decreasing the pressure), Q P < 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 Q P and KP to decide
the course of the reaction.
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M
-
C
E
-
C
H
-
2
7
c d
n nD
C
PT PT
We know, K p
n
n
a b
n nB
A
PT PT
n
n
Where,
nC nD, nA, nB denotes the no. of moles of respective components and P T is the total
pressure and n = total no. of moles of reactants and products.
Now, rearranging,
n
n c n dD PT
K P ac
n A n bB n
Where n = (c + d) (a + b)
Now, n can be equal to = 0, 0 or 0
Let us take each case separately.
a) n = 0 : No effect
b) n = +ve :
n
PT PT
Addition of inert gas increases the n i.e. is decreased and so is . 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 :
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n
PT PT
In this case decreases but increases. So products have to decrease
n
n
and reactants have to increase to maintain constancy of Kp. So the equilibrium moves
backward.
Dependence of Kp or Kc on Temperature
Where, kf = rate constant for forward reaction, Af = Arrhenius constant of forward reaction,
E a r / RT
k r Are (ii)
Ea r Eaf
k f Af
e RT
k r Ar
kf
We know that K (equilibrium constant )
kr
Ea r Eaf
K = k f Af e RT
k r Ar
At temperature T1
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H
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2
9
Ea r Eaf
A RT1 (iii)
K T1 f e
Ar
At temperature T2
Ear Eaf
A RT2 (iv)
K T2 fe
Ar
K T2 E a r E a f 1 1
log
K T1 2.303 R T2 T1
energies as E a f E a r = H Ear E
Energy
K T2 H 1 1
log
K T1 2.303 R T2 T1
H
K T2 H 1 1 Reaction co-ordinate
log = - (v)
K T1 2.303 R T1 T2
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K T2 < K T1 ,
that is, the equilibrium constant at the higher
temperature would be less than that at the lower
temperature.
K A.e Ea / RT
K = rate constant
A = frequency factor
E a Energy of activation
so for forward reaction
K f A f .e Eaf / RT
similarly for backward reaction
K b A b .e Eab / RT
E ab E af
Kf A
K eq f e RT
Kb Ab
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Notes: i) If T2 T1 and reaction is endothermic (H 0) then right hand side is +ve so K 2 K1 i.e.
for endothermic reactions increase in temperature increases the value of equilibrium constant and
decrease in temperature will decrease the value of equilibrium constant.
ii) For exothermic reactions ( H 0) and increase in temperature decreases the value of
equilibrium constant and decrease in temperature increases the value of equilibrium constant.
Illustration 4: 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.
DRILL EXERCISE IV
2. At 298 K, the equilibrium between N2O4 and NO2 may be represented by the following
equation N2O4(g)
2NO2(g). If the total pressure of the equilibrium mixture is P
and the degree of dissociation of N2O4(g) at 298 K is x, which one of the following is
the pressure of N2O4(g) under this condition:
(1 x) P 2x P
(A) (B)
(1 x) (1 x)
2x P 2 P
(C) (D)
(1 x) 3
(1 x) P
2.
(1 x)
3. One mole of SO3 was placed in one litre vessel at a certain temperature. The following
equilibrium was established 2SO3 2SO2 + O2. At equilibrium 0.6 moles of SO2
were formed. The equilibrium constant of the reaction will be:
(A) 0.36 (B) 0.45
(C) 0.54 (D) 0.675
3. 0.675
4. 2 moles of PCl5 were heated in a closed vessel of 2 litre capacity. At equilibrium, 40%
of PCl5 dissociated into PCl3 and Cl2. The value of equilibrium constant is:
(A) 0.267 (B) 0.53
(C) 2.63 (D) 5.3
4. 0.267
5. For reaction: PCl3(g) + Cl2(g)
PCl5(g)
the value of KC at 250C is 26. The value of Kp at this temperature will be:
(A) 0.61 (B) 0.57
(C) 0.83 (D) 0.3
5. 0.61
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Illustration 4: 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.
BRAIN TEASER 4:
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.
Le-Chateliers Principle and Physical Equilibria: Le Chateliers 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 Chateliers 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.
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M
-
C
E
-
C
H
-
3
5
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.
G = G(products) G(reactants)
When G = 0, there is no net work obtainable. The system is in a state of equilibrium. When G
is positive, net work must be put into the system to effect the reaction, otherwise it cannot take
place. When G is negative, the reaction can proceed spontaneously with accomplishment of the
net work. The larger the amount of this work that can be accomplished, the farther away is the
reaction from equilibrium. For this reason G has often been called the driving force of the
reaction. From the statement of the equilibrium law, it is evident that the driving force depends
on the concentration of the reactants and products. It also depends upon the temperature and
pressure which determine the molar free energies of the reactants and products.
G = H + TS
The driving force is made up of two parts, H term and TS term. The H term is the heat of
reaction at constant pressure and TS is heat involved when the process is carried out reversibly.
The difference is the amount of heat of reaction which can be converted into net work (G),
i.e., total heat minus unavailable heat.
If the reaction is carried out at constant volume, the decrease in Helmholtz function G = E
+ TS would be the proper measure of affinity of the reactant or the driving force of the reaction.
Now we can see why Berthollet and Thompson were wrong in assuming that driving force of the
reaction was the heat of reaction. They neglected the TS term. The reasons for the apparent
validity of their principle was that for many reactions, H term far outweighs the TS term. This
is especially true at low temperature, since at higher temperature, TS term increases.
The fact that driving force for a reaction is large (G is large negative quantity) does not mean
that the reaction will necessarily occur under any given conditions.
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M
-
C
E
-
C
H
-
3
7
Standard Free Energy and Equilibrium Constant: The change in free energy for a
reaction taking place between gaseous reactants and products represented by the general
equation.
aA bB cC dD
According to Vant Hoff reaction isotherm
pcC pdD
G G 0 RT ln = G0 + RTlnQp
paA p Bb
the condition for a system to be at equilibrium is that
G = 0
Thus at equilibrium
pcC pdD
0 G 0 RT ln a b
G 0 RT ln K 0p
p
A B p
Whence G0 = RTlnK0p
G 0
Hence ln K 0p
RT
Note: 1. In the reaction, where all gaseous reactants and products; K represents Kp
2. In the reaction, where all solution reactants and products; K represents Kc
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Also, G 0 RT ln K p
Illustration 67: For the equilibrium NiO(s) + CO(g) Ni(s) + CO2(g), G0 (J mol1)
= 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.
Illustration 8: Equilibrium constants are given (in atm) for the following reactions at
0C
a) SrCl26H2O(s)
SrCl22H2O(s) + 4H2O(g), Kp = 6.89 1012
b) Na2HPO412H2O(s)
Na2HPO47H2O(s) + 5H2O(g), Kp = 5.25 10
13
c) Na2SO410H2O(s)
Na2SO4(s) + 10H2O(g) Kp = 4.08 1025
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4
Solution : (a) KP = PH2 O = 6.89 10-12 PH2O = 1.62 10-3 atm
5
KP = PH2O = 5.25 10-13 PH2O = 3.5 10-3 atm
10
KP = PH2O = 4.08 10-25 PH2 O = 3.6 10-3 atm
(b) SrCl2.2H2O, Since it has lowest vapour pressure water in equilibrium
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M
-
C
E
-
C
H
-
4
1
The equilibrium constant KP for the reaction N2(g) + 3H2(g) 2NH3(g) is 1.6 10-4 atm at
400oC. What will be the equilibrium constant at 500 oC if heat of the reaction in this
temperature range is 25.14 k cal?
D
Note: y is the number of moles of products from one mole of reactant. is also called Vant
d
Hoff factor.
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Illustration 89: Vapour density of the equilibrium mixture of NO 2 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
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M
-
C
E
-
C
H
-
4
3
DRILL EXERCISE V
1. An equilibrium mixture for the reaction: 2H2S(g) 2H2(g) + S2(g) has 0.5 mole
H2S, 0.1 mole of H2 and 0.4 mole S2 in a one litre vessel. The equilibrium constant of
this reaction is given by:
(A) 0.004 mole litre1 (B) 0.08 mole litre1
1
(C) 0.016 mole litre (D) 0.160 mole litre1
1. 0.016 mole litre1
2. Mole percentage of CO in vapour state is 50 at equilibrium at constant temperature and
pressure for the reaction, C(Graphite) + CO2(g) 2CO(g). What will be degree of
dissociation.
(A) 0.33 (B) 0.25
(C) 0.033 (D) 0.50
2. 0.33
3. The volume occupied by 3.6 g of PCl5 is 1 litre on complete vaporization at 1
atmospheric pressure and 200C. Partial dissociation of PCl 5 gives PCl3 and Cl2. What
should be the percentage of dissociation of PCl5 at the same temperature
(A) 4.9% (B) 0.49%
(C) 49% (D) 0.049%
3. 49%
4. If x, y and z are the initial moles of PCl5, PCl3 and Cl2 for PCl5
PCl3 + Cl2 and a
is amount of dissociation and P is total pressure, the mole fraction of PCl3 will be
y ax x az
(A) (B)
x y z ax x y z ax
x y ax z ax
(C) (D)
x y z ax x y z ax
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y ax
4.
x y z ax
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Solved Problems
Objective
Problem 1: For the reaction, A(g) + 2B(g) 2C(g), the rate constants for the forward and
the reverse reactions are 1 104 and 2.5 102 respectively. The value of
equilibrium constant, K for the reaction would be
(a) 1 104 (b) 2.5 102
(c) 4 103 (d) 2.5 102.
kf 1104
Solution: Apply the formula, K = 4 103.
k b 2.5 102
(c)
Solution: When the equation is reversed, the equilibrium constant for the reaction is
reciprocal of the K for the forward reaction
1 1
K2 = 5 102 or 0.05.
K1 20
(c)
Problem 32: At a certain temperature, the equilibrium constant K c is 16 for the reaction,
SO2(g) + NO2(g) SO3(g) + NO(g). If 1.0 mol each of all the four gases is
taken in a one litre container the concentration of NO2 at equilibrium would be
(a) 1.6 mol L1 (b) 0.8 mol L1
1
(c) 0.4 mol L (d) 0.6 mol L1.
Problem 43: HI was heated in sealed tube at 400C till the equilibrium was reached. HI was
found to be 22% decomposed. The equilibrium constant for dissociationis
(a) 1.99 (b) 0.0199
(c) 0.0796 (d) 0.282
Solution: 2HI H2 + I2
1 0 0
x x
1x
2 2
1 0.22 = 0.78 0.11 0.11
22
x = 22% of 1 mole = 1 0.22
100
[H ][I ] 0.11 0.11
K 2 22 = 0.0199
[HI] (0.78) 2
(b)
N 2(g) O 2(g)
2NO(g) ; H 53.5kcal / mol
(c)
Problem 64: When ich sulphur in the form of S8 is heated at 900K, the initial pressure of one
atm falls by 29% at equilibrium. This is because of conversion of some S 8 to S12.
Find the value of equilibrium constant for this reaction
(a) 1.16 atm3 (b) 0.71 atm3
3
(c) 2.55 atm (d) 5.1 atm3
Solution: S8(g)
4S2(g)
At start 1 0
At eqbm 1 0.29 4 10.29
= 0.71 atm = 1.16 atm
4 4
[pS2 ] (1.16)
Kp 2.55atm3
[pS8 ] (0.71)
(c)
Problem 75: The following reactions are known to occur in the body
CO2 + H2O
H2CO3
+
H + HCO3
1
Problem 86: For which of the following reactions, the degree of dissociation cannot be
calculated from the vapour density data
I. 2HI(g) H2(g) + I2(g)
II. 2NH3(g)-
N2(g) + 3H2(g)
III.2NO(g)
N2(g) + O2(g)
IV. PCl5(g)
PCl3(g) + Cl2(g)
(a) I and III (b) II and IV
(c) I and II (d) III and IV
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Solution: The degree of dissociation cannot be calculated from the vapour density data.
Becaluse here it the number of moles remains unchanged before and after
reaching equilibrium
(a)
Problem 79: X2 + X
X3 (x = iodine)
This reaction is set up in aqueous medium. We start with 1 mol of X 2 and 0.5
mol of X in 1L flask. After equilibrium is reached, excess of AgNO 3 gave 0.25
mol of yellow ppt. equilibrium constant is
(a) 1.33 (b) 2.66
(c) 2.00 (d) 3.00
Solution: X2 + X
X 3
1 0.5 0
(1 x) (0.5 x) x
(0.5 x) = unreacted X
X Ag + 0.25
x = 0.25
[X3 ] 0.25
Kc
1.33
[X 2 ][X ] 0.75 0.25
(a)
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D
2E (ii)
Given KP1 : KP2 :: 9 : 1
If the degree of dissociation of A and D be same then the total pressure at
equilibrium and (2) are in the ratio
(a) 3 : 1 (b) 36 : 1
(c) 1 : 1 (d) 0.5 : 1
Problem 811: A reaction mixture containing H2, N2 and NH3 has partial pressures 2 atm,
1 atm and 3 atm respectively at 725 K. If the value of K p for the reaction, N2(g) +
3H2(g)
2NH3(g) is 4.28 105 atm2 at 725 K, in which direction the net
reaction will go ?
(a) Forward
(b) Backward
(c) No net reaction
(d) Direction of reaction cannot be predicted.
P
2
NH3 (3) 2 9
Solution: Qp = atm 2 = 1.125 atm2.
P P
3 3
(1)(2) 8
N2 H2
Since value of Qp is larger than Kp (4.28 105 atm2), it indicates net reaction will
proceed in backward direction.
(b)
Problem 12: An equilibrium system for the reaction between hydrogen and iodine to give hydrogen
iodide at 765 K in a 5 litre volume contains 0.4 mole of hydrogen, 0.4 mole of iodine
and 2.4 moles of hydrogen iodide. The equilibrium constant for the reaction is:
H2(g) + I2(g) 2HI(g), is
(a) 36.0 (b) 15.0
(c) 0.067 (d) 0.028.
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C
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H
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1
Problem 913: 2.0 mol of PCl5 were introduced in a vessel of 5.0 L capacity at a particular
temperature. At equilibrium, PCl5 was found to be 35% dissociated into PCl 3
and Cl2. The value of Kc for the reaction is
(a) 1.89 (b) 0.377
(c) 0.75 (d) 0.075.
2 35
Solution: Moles of PCl5 dissociated = = 0.7
100
Moles of PCl5 left undissociated = 2 0.7 = 1.3 mol
1.3 0.7 0.7
[PCl5] = M, [PCl3] = M, [Cl2] = M
5 5 5
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0.7 0.7
[PCl3 ][Cl 2 ] 5
K 5
0.75
[PCl5 ] 1.3
5
(c)
Problem 14: K1 and K2 are equilibrium constant for reactions (1) and (2)
N2(g) + O2(g) 2NO(g) (1)
1 1
NO(g) N2(g) + O2(g) (2)
2 2
Then,
2
1
(a) K1 (b) K1 K 2
2
K 2
1
(c) K1 (d) K1 (K 2 ) .
0
K2
Solution:
N2 + O2 2NO K1
1
2NO N2 + O2
K1
1/ 2
1 1
NO N 2 O2 K2
2 K1
1/ 2
1 1
or K 2
2
K2
K1 K1
1
K1
(K 2 ) 2
(a)
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M
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C
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C
H
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3
2K p
(c)
1 2K p
2 2K p
(d)
1 2 K p
Solution: 2HI(g)
H2(g) + I2(g)
1
2 2
2
PT
Kp
2
(1 ) PT
2 2
2 Kp
1
2 Kp
1 2 K p
(d)
Problem 16: In a reversible reaction, study of its mechanism says that both the forward and reverse
reaction follows first order kinetics. If the half life of forward reaction (t 1/2)f is 400 sec
and that of reverse reaction (t1/2)r is 250 sec. The equilibrium constant of the reaction is
(a) 1.6 (b) 0.433
(c) 0.625 (d) 1.109
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0.693 0.693
Solution: Kf sec 1 ; K r sec 1
400 250
k 250
K f 0.625
k r 400
(c)
Problem 117: At temperature T, a compound AB2(g) dissociates according to the reaction
2AB(g) + B2(g) with degree of dissociation , which is small
2AB2(g)
compared with unity. The expression for Kp, in terms of and the total
pressure, PT is
PT 3 PT 2
(a) (b)
2 3
P 3 P 2
(c) T (d) T .
3 2
Solution: For the given equilibrium, the equilibrium concentration are
2AB2(g) 2AB(g) + B2(g)
c
Equilib. conc. c(1 ) c
2
c
(PB2 )(PAB ) 2 (c) 2 PT 3 PT
2 K
KP ; P
(PAB2 ) 2
2(1 ) 2 1
[c(1 )]2 [c(1 )] 2
2
Since, is small compared to unity, so 1 ; 1 and 1 + ; 1 .
2
PT
3
KP
2
(a)
Solution: NH2COONH4(s)
2NH3(g) + CO2(g)
Moles initially 1 0 0
Moles at equib. (1 x) 2x x
Total moles of gaseous substances at equilibrium = 3x
Equilibrium pressure = PT
2 P
PNH3 PT , PCO2 T
54
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K P (PNH3 ) 2 PCO2
4(PT )3
2.9 105
27
PT = 0.058 atm
(c)
Problem 129: In equilibrium reaction, x moles of the reactant A decompose to give 1 mole
each of C and D. If the fraction of A decomposed at equilibrium is independent
of initial concentration, then the value of x would be
(a) 1 (b) 2
(c) 3 (d) 4
c2 2 2
KC
4[c(1 )]2 4(1 ) 2
(b)
Solution: (d) Suppose 1 mole of A and B each taken then 0.8 mole/litre of C and D each
formed remaining concentration of A and B will be (1 0.8) = 0.2 mole/litre each.
Kc
C D 0.8 0.8 16.0
A B 0.2 0.2
Problem 14: 4 moles of A are mixed with 4 moles of B. At equilibrium for the reaction A + B
C + D, 2 moles of C and D are formed. The equiibrium constant for the
reaction will be
(a) 1/4 (b) 1/2
(c) 1 (d) 4
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C
E
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C
H
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7
Solution: (c) A + B C + D
Initial conc. 4, 4 0 0
After T time conc. (4-2) (4-2) 2 2
C D 2 2 1
Equilibrium constant =
A B 2 2
Problem 15: On a given condition, the equilibrium concentration of HI, H2 are 0.80, 0.10
and 0.10 moe/litre. The equilibrium constant for the reaction
H2 + I2
2HI will be
(a) 64 (b) 12
(c) 8 (d) 0.8
Kc
H 2 I 2 0.10 0.10
Problem 16: In which of the following, the reaction proceeds towards completion
(a) K = 103 (b) K = 10-2
(c) K = 10 (d) K = 1
Solution: (a) Those reaction which have more value of K proceeds towards completion.
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Problem 17: A reversible chemical reaction having two reactants in equilibrium. If the
concentration of the reactants are doubled, then the equilibrium constant will
(a) Also be doubled (b) Be halved
(c) Become one-fourth (d) Remain the same
Problem 19: Pure ammonia is placed in a vessel at temperature where its dissociation
constant ( ) is appreciable. At equilibrium
Solution: (b) A + 2B C + 3D
pC pD 0.30 0.50 0.50 0.50 18.75
3
K
pA pB 0.20 0.10 0.10
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Problem 21: 2 moles of PCl5 were heated in a closed vessel of 2 litre capacity. At
equilibrium, 40% of PCl5 is dissociated into PCl3 and Cl2. The value of
equilibrium constant is
Problem 22: Which of the following factors will not disturb the equilibrium state of the
reaction,
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Solution: (a, c)
Pressure does not disturb equilibrium state in this reaction because np = nR or
n = 0.
Solution: (a, c)
Problem 24: For which of the following reactions at equilibrium at constant temperature
doubling the volume will cause a shift to the right ?
(a) N2O4 (g)
2NO2 (g) (b) CaCO3 (s)
CaO(s) + CO2(g)
(c) 2CO(g) + O2(g)
2CO2(g) (d) N2(g) + O2(g) 2NO (g)
Solution: (a, b)
Doubling the volume would reduce the pressure and shift the equilibrium in the
direction where there is more number of moles of gases. In choices (a) and (b),
the equilibrium will shift to the right.
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Solution: (a, b)
Problem 27: Match the List I, List II and select the answers from the given codes:
Column I (Mixture) Column II (pH)
(a) Keq < 1 (p) may be affected by temperature
(b) Degree of dissociation (q) affected by pressure
(c) Equilibrium constant (r) Kf < Kb
(d) Melting of ice (s) Kf > Kb
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KC
C D
A B
where KC is equilibrium constant when the ratio of the concentrations of the product to
reactants
P P
KP C D
PA PB
where KP is the equilibrium constant for the ratio of partial pressure & of products to
reactants. The relation between KP and KC is as follows
KP = KC(RT)n
1 1 1
2. KC for the reaction N 2 (g) O 2 (g) Br2 (g ) NOBr(g) from the following
2 2 2
information at 298 K
2 NO( g ) N2(g) + O2(g) K1 = 2.4 1030
1
NO( g ) Br2( g ) NOBr(g) K2 = 1.4
2
(a) 3.15 109 (b) 6.35 5 1018
(c) 9.03 1016 (d) 17 1017
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H
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3
3. The equilibrium constant for the reaction 2 SO 2 + O2 2 SO3 at 1000 K is 3.5. What
would the partial pressure of oxygen gas have to be to give equal moles of SO2 and SO3 ?
(a) 0.29 atm (b) 3.5 atm
(c) 0.53 atm (d) 1.87 atm
Solution :
1. (b) Since n = 0, so Kc = Kp = Kx
X 4H 2 (2 / 2) 4
Kx = 4 4
184 1.05 105
X H 2O (1/18)
1/ 2
1 1 1
2. (c) N 2 ( g ) O 2 ( g )
NO( g ) Kc = 30
2 2 2.4 10
1
NO (g) + Br2 ( g ) NOBr (g) K2 = 1.4
2
1 1 1
N 2 ( g ) O2 ( g ) Br2 (g)
NOBr( g ) K = KC K2 = 9.03 10-16
2 2 2
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2
PSO3
3. (a) Kp =
PSO2 .PO2
2
1 1
PO2 atm 0.29 atm
K P 3.5
2
4. (c) Kp = PNH 3 .PCO2 (2 p ) 2 P 4p3
1/ 3
K
P = P 0.0667 atm
4
Write-up II
A chemical reaction in the laboratory is carried out under the condition of constant
temperature and pressure. The condition of spontaneity in terms of enthalpy and entropy
are, respectively, H 0 and S 0 whereas condition of equilibrium are, respectively,
H = 0 and S = 0. An endothermic reaction is driven by increase in entropy i.e. increase
in disorderness. The two criteria combined together, the condition of reversibility and
irreversibility are as follows:
GP, T = H TS 0, where equal to sign refers to reversibility and less than sign refers
to irreversibility. Reversibility is the condition of equilibrium whereas irreversibility is
the condition of spontaneity. A reversible reaction is characterised by equilibrium
constant (K), the magnitude of which measures the position of equilibrium i.e. how far a
chemical reaction will go to completion before attainment of equilibrium. The position of
equilibrium constant of a reaction with temperature is given by Vant Hoff equation of
thermodynamics which is as follows:
d ln K H
dT RT 2
This equation can be integrated assuming H to be independent of temperature. Within
the short interval of temperature.
For a gaseous equilibria k can be expressed Kc and Kp related as
n g
K p K c (RT)
Where the symbols have their usual meanings. ng of a reaction can be found out from
the unit of equilibrium, though it is not customary to write unit of equilibrium constant.
Another way of finding ng of a reaction is to use the equation
H = E + ng RT
Where the terms have their usual meanings.
Knowing K and reaction quotient it is possible to calculate free energy change of a
reaction using the equation:
G = G0 + RTlnQ
At equilibrium Q = K and GP, T = 0
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C
E
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C
H
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5
So, G0 = RTlnK where G0 is the free energy change of the reaction in the standard
state.
The standard state of a substance is defined as the state of unit activity at 25C. In the
case of solution of a substance the activity is taken to be molar concentration while for a
gas it is pressure in atm.
The standard free energy of an element is taken to be zero.
1. At 27C the heat of reaction at constant pressure is 600 cals more than that at constant
volume. The ratio of Kp to Kc of the reaction is:
(a) 24.63 (b) (24.63)2
(c) 0.6 (d) 0.36
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4 4
(c) (d)
(0.0821 300) 2 atm 2 (2 300) 2 atm 2
Solution :
1. From question,
H - E = 600 cals. = n 2 300 cals.
n = 1
Q KP = KC (RT)n
KP/KC = (RT)n = (0.821 300)1 = 24.63
Subjective
Moles equilibrium 1 /2 3 /2 1+
1 3
Partial pressure p p p
1 2(1 ) 2(1 )
[ N 2 ]1 / 2 [ H 2 ]3 / 2
Kp
[ NH 3 ]
1/ 2 3/ 2
3
p p
2 (1 ) 2 (1 ) p 2 27
1 4(1 2 )
1 p
Solving for ` we get :
1/ 2
3 3 p
1
4 K p
We know,
K p K C ( RT ) n
78.1 = K C (0.0821 673)1
KC = 1.413 moles litre1
Problem 21: At 700 K, CO2 and H2 react to form CO and H2O. For this process K is 0.11. If a
mixture of 0.45 mole of CO2 and 0.45 mole of H2 is heated to 700 K, then
i) Find out the amount of each gas at equilibrium.
ii) After equilibrium is reached, another 0.34 mole of CO 2 and 0.34 mole of H2
are added to the reaction mixture. Find the composition of the mixture at
the new equilibrium state.
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M
-
C
E
-
C
H
-
6
9
2
p NO2 4 2 PT 4 2 0.5
Kp =
p N 2O 4 1 1 1 2
= 0.5 i.e., 50% dissociation
Hence, partial pressure of N2O4 = 0.167 atm.
and partial pressure of NO2 = 0.333 atm.
Method (2) Let the partial pressure of NO2 at equilibrium be p atm, than the
partial pressure of N2O4 at equilibrium will be (0.5p)atm.
p2
Kp = 0.66
0.5 p
p2 + 0.66 p0.33 = 0
On solving p = 0.333 atm.
p NO 2 = 0.333 atm and p N2O4 = 0.167 atm.
Problem 4: The value of Kc for the reaction: H2(g) + I2(g) 2HI(g) is 45.9 at 773 K. If
one mole of H2, two mole of I2 and three moles of HI are taken ina 10 L flask,
find the concentrations of I2 and HI at equilibrium at 773 K.
[HI]2 32 9
Solution: Calculate Q. Q =
[H 2 ][I 2 ] 1 2 2
Note: When = 0, not only Kp = KC, but volume terms always cancels in the
expression of K.
Q K (= 45.9). Hence the reaction proceeds to forward direction to achieve
equilibrium. Let x mole of H2 and I2 combine to produce 2x mole of HI.
Moles H2 I2 2HI
Initially 1 2 3
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PI 2p
2 2
Kp =
PI2 0.074 p
Substituting value of p Kp = 0.16 atm
Problem 26: For the reaction: CO2(g) + H2(g) CO(g) + H2O(g), K is 0.63 at 700 C and
1.66 at 1000 C
a) What is the average H for the temperature range considered?
b) What is the value of K at 800 C
Solution: a) T1 = 700 + 273 = 973 K,
T2 = 1000 + 273 = 1273 K
K1 = 0.63, K2 = 1.66
Using the Vant Hoff equation
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M
-
C
E
-
C
H
-
7
1
K2 H 0 T2 T1
log
K1 2.303R T1T2
K H0 T2 T1 H o 1273 973
log
1.66
log 2
K1 2.303R T1T2 0.63 1273 973
2.303(1.99)
H = 8.0 103 cal = 8.0 kcal
Note: The units of R and H must be same
b) Let K2 be the equilibrium constant at T2 = 1073 K, T1 = 973 K and then
K1 = 0.63
K2 8.0 103 1073 973
log
0.63 2.303(1.99) 1073 973
K2 8.0 103 1073 973
log K2 = 0.93
0.63 2.303(1.99) 1073 973
Problem 137: The equilibrium constant for the reaction H2 + I2 2HI; is found to be
64 at 450C. If 6 mole of hydrogen are mixed with 3 mole of iodine in a litre
vessel at this temperature; what will be the concentration of each of the three
components, when equilibrium is attained ?
If the volume of reaction vessel is reduced to half; then what will be the effect
on equilibrium?
Solution: The given equilibrium reaction is :
H2 + I2 2HI
At t = 0 6 3 0
At equilibrium 6x 3x 2x
concentration at 6x 3 x 2x
equilibrium 1 1 1
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(2x) 2
KC
(6 x)(3 x)
4x 2
64
x 2 18 9x
16(x 2 9x 18) x 2
On solving x = 2.84
2x 2 2.84
[HI] = 5.68
1 1
6 x 6 2.84
[H2] = 3.16
1 1
3 x 3 2.84
[I2] = 0.16
1 1
In the present reaction n = 0 hence, volume change will not affect the
equilibrium.
Problem 428: 5 gm of PCl5 were completely vaporized at 250C in a vessel of 1.9 litre
capacity. The mixture at equilibrium exerted a pressure of one atmosphere.
Calculate the degree of dissociation KC and Kp for this reaction.
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M
-
C
E
-
C
H
-
7
3
2
0.0202
[ PCl 3 ][Cl 2 ] 1.9 4.08 10 4
Kc = = 0.0565 mole/litre
[PCl 5 ] 0.0038 1.9 0.0038
1 .9
Kp = Kc (RT) n
Where Kc = 0.0565
n=21=1
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74 CHEMISTRY : CHEMICAL EQUILIBRIUM
Problem 6410: 16 moles of H2 and 4 moles of N2 are sealed in a one litre vessel. The
vessel is heated at a constant temperature until the equilibrium is established, it
is found that the pressure in the vessel has fallen to 9/10 of its original value.
Calculate
KC for the reaction
N2(g) + 3H2(g) 2NH3(g)
At t = 0
At equilibrium
Total gaseous moles at equilibrium
= 4 x + 16 3x + 2x = (20 2x)
Since, pressure has fallen to 9/10 of its original value, hence no. of mole will also
fall up to the same extent.
9
(20 2x) = 20 18
10
x=1
4 x 4 1
[N2] = 3 mole/litre
1 1
16 3x
[H2] = = 13 mole/litre
1
2x
[NH3] = = 2 mole/litre
1
[NH3 ]2 22
KC = = 6.07 104
[N 2 ][H 2 ]3 (3)(13)3
Solution: We have,
K2 H 0 (T2 T1 )
log
K1 2.303R T1T 2
1.4 H 0 373 298
log
0.096 2.303 8.314 373 298
H0= 33025J
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M
-
C
E
-
C
H
-
7
5
Now the temperature above which the forward reaction will be spontaneous is
actually the temperature at which the reaction attains equilibrium, that is, when
K = 1 or log K = 0
G0 = 2.303 RT log K = 2.303 RT log 1.0 = 0
From thermodynamics, we get
G0 = H0 TS0
0 = 33025 T 10.296
or T = 320.75 K
Problem 6712: A mixture of SO3, SO2 and O2 gases is maintained in a 10.0 litre flask at a
temperature at which equilibrium constant Kc for the reaction
2SO2(g) + O2(g) 2SO3(g) is 100.
i) If the number of mole of SO2 and SO3 in the flask are equal how many mole
of O2 are present ?
ii) If the number of mole of SO3 in the flask is twice the number of mole of
SO2,how many mole of O2 are present ?
Solution: If 2x is the partial pressure of SO3 that is decreased at equilibrium, we would have
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M
-
C
E
-
C
H
-
7
7
Solution : We have
2H2S (g)
2H2 (g) + S2(g)
n(1 - ) n + n(/2)
Total amount of gases = n(1 + /2)
1 /2
Hence, pH 2 S p; p H 2 p; p S 2 p
1 / 2 1 / 2 1 / 2
2
/2
p p
( pH 2 ) ( ps2 ) 1 / 2 1 / 2
2 3 p
Thus, K p
( pH 2 S ) 2 1
2
2(1 ) 2 (1 / 2)
p
1 / 2
Substituting the given value of , we get
(0.31)3 (1atm)
Kp 2.71102 atm
2(1 0.31) 2 (1 0.31/ 2)
(0.31)3 (1atm)
Kp 2.71102 atm
2(1 0.31) 2 (1 0.31/ 2)
For the given reaction, vg = +1
Hence, Kc = Kp(RT)-vg
= (2.71 10-2 atm) {(0.0821 L atm K-1 mol-1) (1380 K)}-1
= 2.39 10-4 mol L-1
Solution : (a) Let n be the initial amount of COCl2 and be its degree of dissociation. We
will have
COCl2 CO + Cl2
t=0 n
teq n(1-) n n
Total amount of gases = n(1 - ) + n + n = n(1 + )
Now, the volume of the flask would be
n(1 ) RT
V
p
The density of the mixture would be
nM COCl2 nM COCl2 p pM COCl2
V n(1 ) RT (1 ) RT
pM COCl2
or = 1
RT
Substituting the given values, we get
(1atm)(99 g mol 1 )
1 1.433 1 0.433
(1.162 g L1 )(0.0821 L atm K 1mol 1 )(724 K )
(b) The partial pressures of the species involved in the reactions are
1
pCOCl2 p; pCO p; pCl2 p;
1 1 1
pCO pCl2 2
Hence, p K p
pCOCl2 1 2
(0.433) 2
Which gives K p (1atm) 0.231
1 (0.433) 2
Problem 11: The density of an equilibrium mixture of N2O and NO2 at 1 atm and 348 K is
1.84 g dm-3. Calculate the equilibrium constant of the reaction
N2O4 (g)
2NO2 (g)
Solution: Let n be the amount of N2O4 at t = 0 and let be the degree of dissociation of
N2O4 at equilibrium. Then
N2O4 (g)
2NO2 (g)
t=0 n 0
teq n(1 - ) n(2)
Total amount at equilibrium = n(1 + )
Using the ideal gas equation, we get
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M
-
C
E
-
C
H
-
7
9
m
pV = n(1 + )RT = (1 ) RT
M
or pM = (1 + )RT
pM
or = 1
RT
Substituting the given data, we get
(1 atm)(92 g mol 1 )
= 1 1.752 1 0.752
(1.84 g dm 3 )(0.082 dm3 atm K 1mol 1 )(348K )
p 2 NO2 [2 p /(1 )]2 4 2 4(0.752) 2
Hence, K p p (1atm) 5.206atm
pN 2O4 (1 ) p /(1 ) 1 2 1 0.752 2
Problem 12: For the reaction, N2O5(g) = 2NO2 (g) + 0.5O2 (g), calculate the mole fraction
of N2O5(g) decomposed at constant volume and temperature, if the initial
pressure is 600 mmHg and the pressure at any time is 960 mm Hg. Assuming
ideal gas behaviour.
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Problem 13: When 3.06 g of solid NH4HS is introduced into a two-litre evacuated flask at
2700C, 30% of the solid decomposes into gaseous ammonia and hydrogen
sulphide. (i) Calculate Kc and Kp for the reaction at 270C. (ii) What would
happen to equilibrium when more solid NH4HS is introduced into the flask?
SECTION - I
LEVEL - I Objective Single Choice
Problem 713: A saturated solution of iodine in water contains 0.33g of I 2 per litre of
solution. More than this can dissolve in KI solution because of the following
equilibrium.
I2(aq) + I I3
A 0.1 M KI solution actually dissolves 12.5g of I 2/litre, most of which is
converted to I3. Assuming that the concentration of I2 in all saturated solutions
is the same, calculate the equilibrium constant for the above reaction.
Solution: I2 + I I3
12.5
Initially M 0.1M 0.1M
254
0.33 12.17 12.5 0.33
At equb. M 0.1 254 M 254 254 M
254
Thus,
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M
-
C
E
-
C
H
-
8
1
12.17
[I3 ] 254
K 708
[I 2 ][I ] 0.33 13.23
254 254
Problem 814: For the reaction Ag(CN)2 Ag+ + 2CN, the KC at 25C is 4 1019.
Calculate [Ag+] in solution which was originally 0.1 M in KCN and 0.03 M in
AgNO3.
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M
-
C
E
-
C
H
-
8
3
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1/ 2
3 3 p
1
4 K p
We know,
K p K C (RT ) n
78.1 = K C (0.0821 673)1
KC = 1.413 moles litre1
OBJECTIVE
Problem 1: A reaction mixture containing H2, N2 and NH3 has partial pressures 2 atm, 1
atm and 3 atm respectively at 725 K. If the value of K p for the reaction, N2(g) +
3H2(g)
2NH3(g) is 4.28 105 atm2 at 725 K, in which direction the net
reaction will go ?
(a) Forward
(b) Backward
(c) No net reaction
(d) Direction of reaction cannot be predicted.
P
2
NH3 (3) 2 9
Solution: Qp = atm 2 = 1.125 atm2.
P P
3 3
(1)(2) 8
N2 H2
Since value of Qp is larger than Kp (4.28 105 atm2), it indicates net reaction will
proceed in backward direction.
(b)
Problem 2: An equilibrium system for the reaction between hydrogen and iodine to give
hydrogen iodide at 765 K in a 5 litre volume contains 0.4 mole of hydrogen, 0.4
mole of iodine and 2.4 moles of hydrogen iodide. The equilibrium constant for
the reaction is:
H2(g) + I2(g)
2HI(g), is
(a) 36.0 (b) 15.0
(c) 0.067 (d) 0.028.
2 35
Solution: Moles of PCl5 dissociated = = 0.7
100
Moles of PCl5 left undissociated = 2 0.7 = 1.3 mol
1.3 0.7 0.7
[PCl5] = M, [PCl3] = M, [Cl2] = M
5 5 5
0.7 0.7
[PCl3 ][Cl 2 ] 5
K 5 0.75
(c)
[PCl5 ] 1.3
5
Problem 4: K1 and K2 are equilibrium constant for reactions (1) and (2)
N2(g) + O2(g)
2NO(g) (1)
1 1
NO(g)
N2(g) + O2(g) (2)
2 2
Then,
85
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2
1
(a) K1 (b) K1 K 2
2
K 2
1
(c) K1 (d) K1 (K 2 ) .
0
K2
Solution: N2 + O2
2NO K1
1
2NO
N2 + O2
K1
1/ 2
1 1
NO
N2 O2 K2
2 K1
1/ 2
1 1
or K 2
2
K2
K1 K1
1
K1 (a)
(K 2 ) 2
Problem 5: For the reaction
2HI(g)
H2(g) + I2(g)
The degree of dissociation ( ) of HI(g) is related to equilibrium constant, K p by
the expression
1 2 Kp 1 2K p
(a) (b)
2 2
2K p 2 2K p
(c) (d)
1 2K p 1 2 K p
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M
-
C
E
-
C
H
-
8
7
Problem 6: In a reversible reaction, study of its mechanism says that both the forward and
reverse reaction follows first order kinetics. If the half life of forward reaction
(t1/2)f is 400 sec and that of reverse reaction (t1/2)r is 250 sec. The equilibrium
constant of the reaction is
(a) 1.6 (b) 0.433
(c) 0.625 (d) 1.109
0.693 0.693
Solution: Kf sec 1 ; K r sec 1
400 250
k f 250
K 0.625
k r 400
(c)
c
(PB2 )(PAB ) 2 (c) 2 PT 3 PT
2 K
KP ; P
(PAB2 ) 2
2(1 ) 2 1
[c(1 )]2 [c(1 )] 2
2
Since, is small compared to unity, so 1 ; 1 and 1 + ; 1 .
2
PT
3
KP
2
(a)
5 4(PT )3
2.9 10
27
PT = 0.058 atm (c)
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M
-
C
E
-
C
H
-
8
9
c c
Conc. at. equil. c(1 )
x x
c c
[C][D] x x (c) 2
KC
[A]x [c(1 )]x x 2 [c(1 )]x
The expression of KC would be free from concentration term only when value of
x is 2. Putting x = 2, gives
c2 2 2
KC
4[c(1 )]2 4(1 ) 2
(b)
Level - I
1. In a vessel containing SO3, SO2 and O2 at equilibrium, some helium gas is introduced so
that the total pressure increases while temperature and volume remains constant.
According to Le Chateliers principle, the dissociation of SO3
3. The reaction in which the yield of the products cannot be increased by the application of
high pressure is
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M
-
C
E
-
C
H
-
9
1
5. Consider the reaction, PCl5 (g) PCl3 (g) + Cl2(g) in a closed container at
equilibrium at a fixed temperature. What will be the effect of adding more PCl5 on the
equilibrium concentration of Cl2 (g) ?
(a) it decreases
(b) it increases
(c) it remains unaffected
(d) it cannot be predicted without the value of Kp.
8. For which of the following systems at equilibrium at constant temperature, doubling the
volume will cause a shift to the right
(a) H2(g) + Cl2 (g)
2HCl(g) (b) 2CO(g) + O2 (g)
2CO2(g)
(c) N2 (g) + 3H2 (g)
2NH3 (g) (d) PCl5 (g)
PCl3(g) + Cl2 (g)
9. In a reaction, A + 2B 2C, 2.0 mole of A, 3.0 mole of B and 1.0 mole of C are
placed in a 2.0L flask and the equilibrium concentration of C is 1.0 mole/L. The
equilibrium constant (K) for the reaction is:
(a) 0.33 (b) 1.33
(c) 0.44 (d) 0.6
3. An acid reacts with glycerine to form complex and equilibrium is established. If the heat
of reaction at constant volume for above reaction is 1200 cal more than at constant
pressure and the temperature is 300 K, then which of the following expression is true ?
(a) K p K c (b) K c K p
(c) K p K c (d) none of these.
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8. Which of the following is not favourable condition for the formation of SO3?
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2SO2(g) + O2(g)
2SO3(g); H = 188 kJ
(a) High pressure (b) High temperature
(c) Decreasing [SO3] (d) Increasing [SO2].
PCl5(g)
PCl3(g) Cl2(g) and COCl2(g)
CO(g) Cl2(g)
are simultaneously in equilibrium in an equilibrium box at constant volume. A few moles
of CO(g ) are later introduced into the vessel. After some time, the new equilibrium
concentration of
(a) PCl5 will remain unchanged (b) Cl2 will be greater
(c) PCl5 will become less (d) PCl5 will become greater. A
vessel at 1000K contains CO2 with a pressure of 0.5 atm. Some of the CO 2 is converted
into CO on the addition of graphite. The value of K p if the total pressure at equilibrium is
0.8 atm is
(a) 1.8 atm (b) 3 atm
(c) 0.3 atm (d) 0.18 atm
.
1711. PCl5 is 50% dissociated into PCl3 and Cl2 at one atmosphere. It will be 40% dissociated
at :
(a) 1.75 atm (b) 1.84 atm
(c) 2.00 atm (d) 1.25 atm.
1812. One mole of N 2 O 4(g) at 300 K is kept in a closed container under one atmosphere. It is
heated to 600 K when 20% of N 2 O 4(g ) decomposes to NO 2(g) . The resultant pressure is
(a) 1.2 atm (b) 2.4 atm
(c) 2.0 atm (d) 1.0 atm.
1913. For the reversible reaction, N 2(g) 3H 2(g)
2NH 3(g) at 500C, the value of K p is
1.44 10 when partial pressure is measured in atmospheres. The corresponding value
5
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1 2 Kp 1 2K p
(a) (b)
2 2
2K p 2 Kp
(c) (d) .
1 2K p 1 2 Kp
105. Sulphide ions is alkaline solution react with solid sulphur to form polyvalent sulphide
ions. The equilibrium constant for the formation of S22- and S32- from S and S2- ions are
1.7 and 5.3 respectively. Equilibrium constant for the formation of S32- from S22- and S is:
(a) 1.33 (b) 3.11
(c) 4.21 (d) 1.63
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For which of the following reactions, the degree of dissociation cannot be calculated from the
vapour density data
I 2HI(g)
H 2(g) I 2(g) II 2NH 3(g)
N 2(g) 3H 2(g)
III 2NO(g)
N 2(g) O 2(g) IV PCl5(g)
PCl3(g) Cl2(g)
(a) I and III (b) II and IV
(c) I and II (d) III and IV.
Level - II
2. The oxidation of SO2 by O2 to SO3 is an exothermic reaction. The yield of SO3 will be
maximum if
(a) temperature is increased and pressure is kept constant
(b) temperature is reduced and pressure is increased
(c) both temperature and pressure are increased
(d) both temperature and pressure are reduced.
17. A vessel at 1000K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted
into CO on the addition of graphite. The value of K if the total pressure at equilibrium is
0.8 atm is
(a) 1.8 atm (b) 3 atm
(c) 0.3 atm (d) 0.18 atm
138. In the reaction PCl5 PCl3 + Cl2, the amounts of PCl5, PCl3 and Cl2 at equilibrium are
2 mole each and the total pressure is 3 atm. The equilibrium constant Kp is
(a) 1.0 atm (b) 2.0 atm
(c) 3.0 atm (d) 6.0 atm
149. When 20g of CaCO3 were put into 10 litre flask and heated to 800C, 35% CaCO3
remained unreacted at equilibrium, Kp for decomposition of CaCO3 is
(a) 1.145 atm (b) 0.145 atm
(c) 2.145 atm (d) 3.145 atm
520. The decomposition of N2O4 to NO2 is carried out at 280C in chloroform. When
equilibrium is reached, 0.2 mol of N2O4 and 2 103 mol of NO2 are present in 2 litre
solution. The equilibrium constant for the reaction, N 2 O 4 2NO 2 is
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21. In a reaction, A + 2B 2C, 2.0 mole of A, 3.0 mole of B and 1.0 mole of C are
placed in a 2.0L flask and the equilibrium concentration of C is 1.0 mole/L. The
equilibrium constant (K) for the reaction is:
(a) 0.33 (b) 1.33
(c) 1.66 (d) 0.6
23. In a reversible reaction, study of its mechanism says that both the forward and backward
reactions follow first order kinetics. If the half life of forward reaction (t1/ 2 )f is 400 sec.
and that of backward reaction (t1/ 2 ) b is 250 sec. The equilibrium constant of the
reaction is CO(g) NO 2(g)
CO 2(g) NO(g)
(a) 1.6 (b) 0.433
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24. The CaCO3 is heated in a closed vessel of volume 1 litre at 600 K to form CaO and CO 2
. The minimum weight of CaCO3 required to establish the equilibrium
CaO(s) CO 2(g) is (K p 2.25 atm)
CaCO3(s)
(a) 2g (b) 4.57 g
(c) 10g (d) 100 g.
8. A 2(g) B2(g) ; the degree of dissociation ( ) of HI(g) is
For the reaction: 2AB(g)
related to equilibrium constant K p by the expression
1 2 Kp 1 2K p
(a) (b)
2 2
2K p 2 Kp
(c) (d) .
1 2K p 1 2 Kp
10. In a reversible reaction, study of its mechanism says that both the forward and backward
reactions follow first order kinetics. If the half life of forward reaction (t1/ 2 ) f is 400 sec.
and that of backward reaction (t1/ 2 )b is 250 sec. The equilibrium constant of the
reaction is CO(g) NO 2(g)
CO 2(g) NO(g)
(a) 1.6 (b) 0.433
(c) 0.625 (d) 1.109.
11. Steam at pressure of 1 atm is passed through a furnace at 2000 K wherein the reaction
H 2 O(g)
H 2(g) 1 2 O 2(g) ; K p 6.4 10 5 occurs. The percentage of oxygen in the
exit stream would be
(a) 0.32 (b) 0.08
(c) 0.04 (d) 0.16
LEVEL - II More than one choice
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25. Steam at pressure of 1 atm is passed through a furnace at 2000 K wherein the reaction
H 2 O(g)
H 2(g) 1 2 O 2(g) ; K p 6.4 10 5 occurs. The percentage of oxygen in the
exit stream would be
(a) 0.32 (b) 0.08
(c) 0.04 (d) 0.16
Catalyst
22. N 2(g) 3H 2(g) 500
2NH 3 heat
C
In the above reaction, the direction of equilibrium will be shifted to the right by
(a) increasing the concentration of nitrogen
(b) compressing the reaction mixture
(c) removing the catalyst
(d) decreasing the concentration of ammonia
3. The equilibrium of which of the following reactions will not be disturbed by the addition
of an inert gas at constant volume
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(c) HONO H 2O
ONO H 3O
(d) H 3O CH 3 NH 2
CH3 NH 3 H 2 O
49. For 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
5. 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
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(a) increase in pressure will result in the formation of more liquid water
(b) increase in pressure will increase boiling point
(c) decrease in pressure will vaporize H2O(l) to a greater extent
(d) increase in pressure will liquefy steam.
15. Which is/are correct relation(s) for thermodynamic equilibrium constant?
(a) G = 2.303 RT logK (b) G = G + 2.303 RT logK
0.0591 0.0591
(c) E cell (d) E E
0 0
log K log K
n n
816. Which is/are correct relation(s) for equilibrium constant K?In presence of a catalyst, what
happens to the chemical equilibrium ?
(a) Energy of activation of the forward and backwards reactions are lowered by same
amount
(b) Equilibrium amount is not disturbed
(c) Rates of forward and reverse reaction increase by the same factor
(d) More product is formed.
2.303RT log K
(b) E cell
0
(a) G = 2.303 RT logK
nF
(c) K
[product] (d) log K log A
H
[reactant] 2.303RT
917. Volume of the flask in which species are transferred is double of the earlier flask. In
which of the following cases, equilibrium constant is affected?
(a) N 2(g) 3H 2(g)
2NH3(g) (b) N 2(g) O 2
2NO(g)
(c) PCl5(g)
PCl3(g) Cl2(g) (d) 2NO
N 2(g) O 2(g)
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1. AB2 dissociates as
AB2 (g)
AB(g) + B(g)
When the initial pressure of AB2 is 600 mm Hg, the total equilibrium pressure is 800 mm
Hg. Calculate K for the reaction assuming that the volume of the system remains
unchanged.
(a) 50 (b) 100
(c) 166.6 (d) 400.0
3. Consider the two gaseous equilibria involving SO 2 and the corresponding equilibrium
constants at 298 K
1
SO2 (g) + O 2 (g)
SO3 (g)
2
. . . . .K1
2SO3 (g)
2SO2 (g) + O2(g) . . . . K2
The values of the equilibrium constants are related by
(a) K2 = K1 (b) K2 = K12
1 1
(c) K2 = 2 (d) K 2
K1 K1
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5. The reaction, SO2 + Cl2 SO2 Cl2 is exothermic and reversible. A mixture of SO2
(g), Cl2(g) and SO2Cl2 (l) is at equilibrium in a closed container. Now a certain quantity
of extra SO2 is introduced into the container, the volume remaining the same. Which of
the following is true ?
(a) The pressure inside the container will not change
(b) The temperature will not change
(c) The temperature will increase
(d) The temperature will decrease.
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11. For the reaction C(s) + CO2(g) 2CO(g) the partial pressure of CO2 and CO are
2.0 and 4.0 atm respectively at equilibrium. What is the value of Kp for this reaction ?
(a) 0.5 atm (b) 4.0 atm
(c) 8.0 atm (d) 32.0 atm
14. A reaction is A + B
C + D. Initially we start with equal concentrations of A and
B. At equilibrium we find that the moles of C is two times of A. What is the equilibrium
constant of the reaction ?
15. 5 moles of SO2 and 5 moles of O2 are allowed to react to form SO3 in a closed vessel. At
the equilibrium stage 60% of SO2 is used up. The total number of moles of SO2, O2 and
SO3 in the vessel now is
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SECTION - II
LEVEL - I Subjective
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9. One mole of nitrogen is mixed with three moles of hydrogen in a 4-litre container. If
0.25% of nitrogen is converted to ammonia by the following reaction:
N2 (g) + 3H2 (g) 2NH3 (g)
calculate the equilibrium constant Kc. What will be the value of Kc for the following
equilibrium ?
1 3
N2(g) + H2(g)
NH3(g)
2 2
LEVEL - II Subjective
1*. To 500 mL of 0.150 M AgNO3 solution were added 500 mL of 1.09 M Fe 2+ solution and
the reaction is allowed to reach on equilibrium at 25C.
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Ag (aq) Fe2(aq) 3
Fe (aq) Ag (s)
For 25 mL of the solution, 30mL of 0.0832 M KMnO4 were required for oxidation.
Calculate equilibrium constant for the reaction at 25C.
2. One mole of N2 and 3 mol of PCl5 placed in a 100 litre vessel are heated to 2270C. The
equilibrium pressure is 2.05 atm. Assuming ideal behaviour, calculate the degree of
dissociation of PCl5 and Kp for the reaction
PCl5(g) PCl3 (g) + Cl2(g)
3. What is the vapour density of mixture of PCl 5 at 250C when it has dissociated to the
extent of 80%.
at 40C. A 5 litre vessel contains 0.1 mole of LiClNH3. How many mole of NH3 should
be added to the flask at this temperature to derive the backward reaction for completion?
5*. Consider the reaction SO 2 Cl 2 (g) SO 2 (g) Cl 2 (g) ; at 37C the value of
equilibrium constant for the reaction is 0.0032. It was observed that concentration of the
three species is 0.050 mol/lit. each at a certain instant. Discuss what will happen in the
reaction vessel?
6. In an experiment starting with 1 mole C 2H5OH, 1 mole CH3COOH and 1 mole of water,
the equilibrium mixture on analysis shows that 54.3% of the acid is esterified.
Calculate Kc.
7. 0.15 mol of CO taken in a 2.5 L flask is maintained at 750 K along with a catalyst so that
the following reaction can take place; CO(g) + 2 H 2 (g)
CH3OH(g) . Hydrogen is
introduced unitl the total pressure of the system is 8.5 atm. At equilibrium 0.08 mol of
methanol is formed. Calculate:
i) K p and K c
ii) The final pressure if the same amount of CO and H 2 as before are used but no
catalyst so that the reaction does not take place.
8*. At some temperature and under a pressure of 4 atm. PCl 5 is 10% dissociated. Calculate
the pressure at which PCl5 will be 20% dissociated, temperature remaining same.
9. When NO and NO2 are mixed, the following equilibria are readily obtained;
2NO2
N2O4 Kp = 6.8 atm
-1
In an experiment when NO and NO2 are mixed in the ratio of 1: 2, the final total pressure
was 5.05 atm and the partial pressure of N2O4 was 1.7 atm. Calculate:
(a) The equilibrium partial pressure of NO
(b) Kp for NO + NO2 N2O3
10*. NO and Br2 at initial pressures of 98.4 and 41.3 torr respectively were allowed to react at
300K. At equilibrium the total pressure was 110.5 torr. Calculate the value of equilibrium
constant , Kp and the standard free energy change at 300K for the reaction
2NO(g) Br2(g)
2NOBr(g)
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p q r s
This section contains 2 questions. Each question contains statements given in two
A p q r s
column which have to be matched. Statements (A, B, C, D) in Column I have to be
matched with statements (p, q, r, s) in Column II. The answers to these questions B p q r s
have to be appropriately bubbles as illustrated in the following example.
C p q r s
If the correct matches are Ap, As, Bq, Br, Cp, Cq and Ds, then the
correctly bubbled 4 4 matrix should be as follows : D p q r s
1. Match the chemical reaction in equilibrium (in List I) with the pressure dependent of
degree of dissociation of the reaction (in List II):
2. Column I Column II
(A) H = ve and S = +ve (p) Reaction feasible only low
temperature
` (B) H = ve and S = ve (q) Reaction feasible at any temperature
` (C) H = +ve and S = ve (r) Reaction will not occur at any
temperature
(D) H = +ve and S = +ve (s) Reaction feasible only at high
temperature
Comprehension - I
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Write-up I
For the reaction CaCO3(s) CaO(s) + CO2(g), KP(1000 K) = 0.059 and KP (1100 K)
= 0.08. Exactly 10 g of CaCO3 is placed in a 10 litre container at 1000 K. The equilibrium
is reached. Assume that air contains 10% by volume of CO2.
4. The value of H is
(a) 6699 cal (b) 2399 cal
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Write-up IIComprehension - II
Life at high attitudes and hemoglobin production: In the human body, countless
chemical equilibria must be maintained to ensure physiological well being. Transport of
oxygen by blood depends on the reversible combination of oxygen with haemoglobin. In
blood, haemoglobin, oxygen and oxyhaemoglobin are in equilibrium.
haemoglobin (Hb) + O 2 Oxyhaemoglobin [Hb(O 2 )]
[Hb(O 2 )]
The equilibrium constant is, K c
[Hb][O 2 ]
The pH of blood stream is maintained by a proper balance of H 2CO3 and NaHCO3
concentrations.
[salt]
According to Hendersons equation pH log K a log
[acid]
An important component of blood is the buffer combination of H 2 PO 4 ion and the
HPO 4 ion. Consider blood with a pH of 7.44. Given K a1 6.9 103 , K a 2 6.2 108
13
and K a3 4.8 10 .
2 2
7. What will be the pH, when 25% of the HPO 4 ions are converted to H 2 PO 4 ion?
(a) 7.16 (b) 8.16
(c) 9.16 (d) None
8. What will be the pH, when 15% of the H 2 PO 4 ions are converted to HPO 4 ions?
(a) 7.55 (b) 8.55
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(A) Statement 1 is True, Statement 2 is True; Statement 2 is a correct explanation for
Statement 1.
(B) Statement 1 is True, Statement 2 is True; Statement 2 is NOT a correct explanation for
Statement 1.
(C) Statement 1 is True, Statement 2 is False.
(D) Statement 1 is False, Statement 2 is True.
1. STATEMENT - 1
If Kp value for CaCO3(s)
CaO3 CO 2(g) be 8 atm at 500K, the final pressure
developed in 10 litre vessel on heating 50g of CaCO3(s) by enclosing in vessel at 500K
will be 8 atm.
STATEMENT - 2
This amount of calcium carbonate is insufficient to establish equilibrium under given set
of condition.
2. STATEMENT - 1
The positive catalyst enhances the rate of equilibrium reaction, but does not change the
value of equilibrium constant at constant temperature.
STATEMENT - 2
Because the catalyst increases the value Kf and Kb in the same proportion at constant
temperature.
3. STATEMENT - 1
Increasing the pressure formation of NH3 increases in the following equilibrium reaction
N 2 3H 2
2NH 3 H ve
STATEMENT - 2
The reaction is exothermic
4. STATEMENT - 1
Reaction (s)
2B(s) C(g) K c 0.28atm
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Will attain equilibrium soon if the reaction is carried out in an open vessel.
STATEMENT - 2
For the atoms reaction: Kp Kc
SECTION - IV
Previous IIT- JEE Problems Objective
H 2(g) I 2(g)
2HI(g)
The equilibrium constant kp changes with
(a) total pressure (b)
catalyst
(c) the amounts of H2 and I2 present (d)
temperature [1981]
2. Pure ammonia is placed in a vessel at a temperature where its dissociation constant (a) is
appreciable. At equilibrium
(a) kp does not change significantly with
pressure
(b) does not change with pressure
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116 CHEMISTRY : CHEMICAL EQUILIBRIUM
3. At constant temperature, the equilibrium constant (kp) for the decomposition reaction
N 2O 4
2NO 2 is expressed by kp = (4x2P)/(1-x2), where P = pressure, x = extent of
decomposition. Which one of the following statements is true?
(a) kp increases with increase of P
(b) kp increases with increase of x
(b) kp increases with decreases of x
(d) kp remains constant with change in P and x
SO 2 Cl 2(g)
SO 2(g) Cl 2(g)
Is attained at 25C in a closed container and an inert gas, helium is introduced. Which of
the following statements are correct?
(a) Concentration of SO2, Cl2 and SO2Cl2 do not
change
(b) More chlorine is formed
(c) Concentration of SO2 is reduced
(d) More SO2Cl2 is formed
[1991]
8. For the reaction
PCl5(g) 3(g) Cl2(g)
PCl
The forward reaction at constant temperature is favoured by
(a) introducing an inert gas at constant volume
(b) introducing chlorine gas at constant volume
(c) introducing an inert gas at constant pressure
(d) increasing the volume of the container
(e) introducing PCl5 at constant volume
[1991]
9. For the reaction CO(g) H 2O (g)
CO 2(g) H 2(g) at a given temperature the
equilibrium amount of CO2(g) can be increased by
(a) adding a suitable catalyst (b)
adding an inert gas
(c) decreasing the volume of the constant (d)
increasing the amount of CO(g)
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9. One mole of nitrogen is mixed with three moles of hydrogen in a 4-litre container. If
0.25% of nitrogen is converted to ammonia by the following reaction:
N2 (g) + 3H2 (g) 2NH3 (g)
calculate the equilibrium constant Kc. What will be the value of Kc for the following
equilibrium ?
1 3
N2(g) + H2(g)
NH3(g)
2 2
LEVEL II
1*. To 500 mL of 0.150 M AgNO3 solution were added 500 mL of 1.09 M Fe2+ solution and
the reaction is allowed to reach on equilibrium at 25C.
Ag (aq) Fe 2 (aq) 3
Fe (aq) Ag (s)
For 25 mL of the solution, 30mL of 0.0832 M KMnO4 were required for oxidation.
Calculate equilibrium constant for the reaction at 25C.
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2. One mole of N2 and 3 mol of PCl5 placed in a 100 litre vessel are heated to 2270C. The
equilibrium pressure is 2.05 atm. Assuming ideal behaviour, calculate the degree of
dissociation of PCl5 and Kp for the reaction
PCl5(g) PCl3 (g) + Cl2(g)
3. What is the vapour density of mixture of PCl 5 at 250C when it has dissociated to the
extent of 80%.
at 40C. A 5 litre vessel contains 0.1 mole of LiClNH3. How many mole of NH3 should
be added to the flask at this temperature to derive the backward reaction for completion?
6. In an experiment starting with 1 mole C 2H5OH, 1 mole CH3COOH and 1 mole of water,
the equilibrium mixture on analysis shows that 54.3% of the acid is esterified.
Calculate Kc.
7. 0.15 mol of CO taken in a 2.5 L flask is maintained at 750 K along with a catalyst so that
the following reaction can take place; CO(g) + 2 H 2 (g)
CH3OH(g) . Hydrogen is
introduced unitl the total pressure of the system is 8.5 atm. At equilibrium 0.08 mol of
methanol is formed. Calculate:
i) K p and K c
ii) The final pressure if the same amount of CO and H 2 as before are used but no
catalyst so that the reaction does not take place.
8*. At some temperature and under a pressure of 4 atm. PCl 5 is 10% dissociated. Calculate
the pressure at which PCl5 will be 20% dissociated, temperature remaining same.
9. When NO and NO2 are mixed, the following equilibria are readily obtained;
2NO2 N2O4 Kp = 6.8 atm
-1
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10*. NO and Br2 at initial pressures of 98.4 and 41.3 torr respectively were allowed to react at
300K. At equilibrium the total pressure was 110.5 torr. Calculate the value of equilibrium
constant , Kp and the standard free energy change at 300K for the reaction
2NO(g) Br2(g)
2NOBr(g)
[Ag+] in solution which was originally 0.1 M in KCN and 0.03 M in AgNO3.
2. A sample of air consisting of N2 and O2 was heated to 2500K until the equilibrium
N 2(g) O 2(g)
2NO(g)
was established with an equilibrium constant KC = 2.1 103. At equilibrium, the moles
% of NO were 1.8. Estimate the initial composition of air in mole fraction of N2 and O2.
3*. The degree of dissociation is 0.4 at 400K and 1.0 atm for the gaseous reaction
PCl5
PCl3 + Cl2. Assuming ideal behaviour of all the gases, calculate the density of
equilibrium mixture at 400K and 1.0 atmosphere. (Atomic mass of P = 31.0 and
Cl = 35.5)
6. A vessel at 1000K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted
into CO on addition of graphite. Calculate the value of K, if total pressure at equilibrium
is 0.8 atm.
7. At 817C, Kp for the reaction between CO2(g) and excess hot graphite(s) is 10 atm.
a) What are the equilibrium concentration of the gases at 817C and a total pressure
of 5 atm?
b) At what total pressure, the gas contains 5% CO2 by volume?
8. For the reaction, CO(g) + 2H2(g)
CH3OH(g); H2 is introduced into a five litre flask at
327C, containing 0.2 mole of CO(g) and a catalyst till the pressure is 4.92 atmosphere. At
this point 0.1 mole of CH3OH(g) is formed. Calculate the KC and Kp.
9*. The value of Kp is 1 103 atm1 at 25C for the reaction:
2NO + Cl2
2NOCl. A flask contains NO at 0.02 atm and at 25C. Calculate the
mole of Cl2 that must be added if 1% of the NO is to be converted to NOCl at
equilibrium. The volume of the flask is such that 0.2 mole of gas produce 1 atm pressure
at 25C. (Ignore probable association of NO to N2O2).
10. When 1-pentyne (A) is treated with 4N alcoholic KOH at 175C, it is converted slowly
into an equilibrium mixture of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5%, of 1-
2pentadiene (C). The equilibrium was maintained at 175C. Calculate G0 for the
following equilibria.:
B
A : G10 ?
B
C : G 02 ?
From the calculated value G1 and G 2 indicate the order of stability of (A), (B)
0 0
and (C).
24. Which of the following will favour the formation of products in the following reaction?
A (g) 2B(g) (g) D(g) heat
3C
(a) An increase in temperature (b) An increase in pressure
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Write-up I
A chemical reaction in the laboratory is carried out under the condition of constant
temperature and pressure. The condition of spontaneity in terms of enthalpy and entropy
are, respectively, H 0 and S 0 whereas condition of equilibrium are, respectively,
H = 0 and S = 0. An endothermic reaction is driven by increase in entropy i.e. increase
in disorderness. The two criteria combined together, the condition of reversibility and
irreversibility are as follows:
GP, T = H TS 0, where equal to sign refers to reversibility and less than sign refers
to irreversibility. Reversibility is the condition of equilibrium whereas irreversibility is
the condition of spontaneity. A reversible reaction is characterised by equilibrium
constant (K), the magnitude of which measures the position of equilibrium i.e. how far a
chemical reaction will go to completion before attainment of equilibrium. The position of
equilibrium constant of a reaction with temperature is given by Vant Hoff equation of
thermodynamics which is as follows:
d ln K H
dT RT 2
This equation can be integrated assuming H to be independent of temperature. Within
the short interval of temperature.
For a gaseous equilibria k can be expressed Kc and Kp related as
n g
K p K c (RT)
Where the symbols have their usual meanings. ng of a reaction can be found out from
the unit of equilibrium, though it is not customary to write unit of equilibrium constant.
Another way of finding ng of a reaction is to use the equation
H = E + ng RT
Where the terms have their usual meanings.
Knowing K and reaction quotient it is possible to calculate free energy change of a
reaction using the equation:
G = G0 + RTlnQ
At equilibrium Q = K and GP, T = 0
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So, G0 = RTlnK where G0 is the free energy change of the reaction in the standard
state.
The standard state of a substance is defined as the state of unit activity at 25C. In the
case of solution of a substance the activity is taken to be molar concentration while for a
gas it is pressure in atm.
The standard free energy of an element is taken to be zero.
1. At 27C the heat of reaction at constant pressure is 600 cals more than that at constant
volume. The ratio of Kp to Kc of the reaction is:
(a) 24.63 (b) (24.63)2
(c) 0.6 (d) 0.36
4 4
(c) (d)
(0.0821 300) 2 atm 2 (2 300) 2 atm 2
Write-up II
Life at high attitudes and hemoglobin production: In the human body, countless
chemical equilibria must be maintained to ensure physiological well being. Transport of
oxygen by blood depends on the reversible combination of oxygen with haemoglobin. In
blood, haemoglobin, oxygen and oxyhaemoglobin are in equilibrium.
haemoglobin (Hb) + O 2 Oxyhaemoglobin [Hb(O 2 )]
[Hb(O 2 )]
The equilibrium constant is, K c
[Hb][O 2 ]
The pH of blood stream is maintained by a proper balance of H 2CO3 and NaHCO3
concentrations.
[salt]
According to Hendersons equation pH log K a log
[acid]
An important component of blood is the buffer combination of H 2 PO 4 ion and the
HPO 4 ion. Consider blood with a pH of 7.44. Given K a1 6.9 103 , K a 2 6.2 108
13
and K a3 4.8 10 .
2 2
7. What will be the pH, when 25% of the HPO 4 ions are converted to H 2 PO 4 ion?
(a) 7.16 (b) 8.16
(c) 9.16 (d) None
8. What will be the pH, when 15% of the H 2 PO 4 ions are converted to HPO 4 ions?
(a) 7.55 (b) 8.55
(c) 9.55 (d) None
Write-up III
Let G be the difference in free energy of the reaction when all the reactants and
products are in the standard state (1 atmospheric pressure and 298K) and KC and KP be
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the thermodynamic equilibrium constant of the reaction. Both are related to each other at
temperature T by the following relation:
G = 2.303 RT log KC
and G = 2.303 RT log KP (incase of ideal gas)
This equation represents one of the most important results of thermodynamics and relates
to the equilibrium constant of a reaction to a thermodynamic property.
It is sometimes easier to calculate the free energy in a reaction rather than to measure the
equilibrium constant.
Standard free energy change can be thermodynamically calculated as
G = H TS
Here H = standard enthalpy change
S = standard entropy change.
11. Calculate the equilibrium concentration ratio of C to A if 2.0 mol each of A and B were
allowed to come to equilibrium at 300 K
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A + B
C + D G = 460 Cal
(a) 1.0 (b) 0.5
(c) 0.8 (d) 0.679
Write-up IV
The equilibrium constants (Kp and Kc) of a gaseous equilibria say
aA (g) bB(g)
cC(g) dD(g)
are interrelated as :
n
K p K c (RT) g
where ng = (c + d) (a + b
The heat of reactions : H and E are interrelated according to the equation:
H = E + ngRT.
12. H of a reaction is 600 cals more than E at 27C. What is the ratio of K p and Kc of a
reaction at 27C? (R = 1.987 2 cals K1 mol1) = 0.0821 L atm K1 mol1.
(a) 1.2 (b) 24.63
(c) 49.26 (d) 2.4
13. Solid A was heated in a sealed vessel when pressure developed 65.68 atm at 127C due to
the attainment of following equilibrium
A (s)
B(g) C(g)
Hence Kc of the reaction at 127C is:
1
(a) (b) 1.0
32.84
2
(c) (d) cant be calculated
32.84
Write-up V
Ammonia is manufactured by the Haber process represented by the equilibrium:
N 2(g) 3H 2(g)
2NH3(g) H0 = 184.4 kJ
The optimum conditions for the production of ammonia are a pressure of about 200 atm
and a temperature of around 700K. Iron oxide containing small amounts of K 2O and
Al2O3 is used as catalyst so as to increase the rate of attainment of equilibrium. Annual
world production of ammonia now exceeds 10 million tonnes.
14. According to Le-Chateliers principle the favourable condition for good yield of NH3
(a) Low pressure and low temperature (b) High pressure and low temperature
(c) Low pressure and high temperature (d) High pressure and high temperature
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LEVEL I
a) What is the value of the reaction quotient before any reaction occurs?
b) What is the value of the equilibrium constant?
LEVEL II
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1. To 500 mL of 0.150 M AgNO3 solution were added 500 mL of 12.09 M Fe 2+ solution and
the reaction is allowed to reach on equilibrium at 25C.
Ag (aq) Fe 2 (aq) 3
Fe (aq) Ag (s)
For 25 mL of the solution, 30mL of 0.0832 M KMnO4 were required for oxidation.
Calculate equilibrium constant for the reaction at 25C.
3. What is the vapour density of mixture of PCl 5 at 250C when it has dissociated to the
extent of 80%.
6. In an experiment starting with 1 mole C 2H5OH, 1 mole CH3COOH and 1 mole of water,
the equilibrium mixture on analysis shows that 54.3% of the acid is esterified.
Calculate Kc.
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7. 0.25 mol of CO taken in a 2.5 L flask is maintained at 750 K along with a catalyst so that
the following reaction can take place; CO(g) + H 2 (g) CH3OH(g) . Hydrogen is
introduced unitl the total pressure of the system is 8.5 atm. At equilibrium 0.08 mol of
methanol is formed. Calculate:
i) K p and K c
ii) The final pressure if the same amount of CO and H 2 as before are used but no
catalyst so that the reaction does not take place.
8. Equilibrium constants are given (in atm) for the following reactions at 0C
a) SrCl26H2O(s)
SrCl22H2O(s) + 4H2O(g), Kp = 6.89 1012
b) Na2HPO412H2O(s) Na2HPO47H2O(s) + 5H2O(g), Kp = 5.25 10
13
10. NO and Br2 at initial pressures of 98.4 and 41.3 torr respectively were allowed to react at
300K. At equilibrium the total pressure was 110.5 torr. Calculate the value of equilibrium
constant , Kp and the standard free energy change at 300K for the reaction
2NO(g) Br2(g)
2NOBr(g)
2. A sample of air consisting of N2 and O2 was heated to 2500K until the equilibrium
N 2(g) O 2(g)
2NO(g)
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was established with an equilibrium constant KC = 2.1 103. At equilibrium, the moles
% of NO were 1.8. Estimate the initial composition of air in mole fraction of N2 and O2.
3. The degree of dissociation is 0.4 at 400K and 1.0 atm for the gaseous reaction
PCl5
PCl3 + Cl2. Assuming ideal behaviour of all the gases, calculate the density of
equilibrium mixture at 400K and 1.0 atmosphere. (Atomic mass of P = 31.0 and
Cl = 35.5)
5. When S in the form of S8 is heated at 900K, the initial pressure of 1 atmosphere falls by
29% at equilibrium. This is because of conversion of some S8 to S2. Find the Kp for
reaction.
6. A vessel at 1000K contains CO2 with a pressure of 0.5 atm. Some of the CO 2 is converted
into CO on addition of graphite. Calculate the value of K, if total pressure at equilibrium
is 0.8 atm.
7. At 817C, Kp for the reaction between CO2(g) and excess hot graphite(s) is 10 atm.
a) What are the equilibrium concentration of the gases at 817C and a total pressure
of 5 atm?
b) At what total pressure, the gas contains 5% CO2 by volume?
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10. When 1-pentyne (A) is treated with 4N alcoholic KOH at 175C, it is converted slowly
into an equilibrium mixture of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5%, of 1-
2pentadiene (C). The equilibrium was maintained at 175C. Calculate G0 for the
following equilibria.:
B
A : G10 ?
B
C : G 02 ?
From the calculated value G1 and G 2 indicate the order of stability of (A), (B)
0 0
and (C).
The following questions (2to 10) consists of two statements, one labelled as ASSERTION (A)
and REASON (R). Use the following key to chose the correct appropriate answer.
(a) (A) and (R) both are correct and (R) is the correct explanation of (A)
(b) (A) and (R) both are correct but (R) is not the correct explanation of (A)
(c) (A) is correct but (R) is incorrect.
(d) (A) is incorrect but (R) is correct
ASSERTION (A) REASONING (R)
2. The endothermic reactions are favoured at When a system in equilibrium is
lower temperature and the exothermic disturbed by changing the temperature,
reactions are favoured at higher temperature. it will tend to adjust itself so as to
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4. Even at constant temperature, on changing the Because the equilibrium depends upon
stoichiometric coefficients of the reaction, the the ratio of concentration of product
equilibrium constant changes. and reaction in which the stoichiometric
coefficients becomes, thereby the
equilibrium constant depends upon the
stoichiometric coefficients.
6. for the physical equilibrium ice water Since forward reaction is endothermic
on increasing temperature and increasing in nature and volume of water is lesser
pressure more water will form. than that of the volume of ice.
7. The equilibrium remains undisturbed by the Since Kp remains constant at constant
addition of inert gas at constant volume. volume and at constant temperature by
the addition of inert gas at equilibrium.
8. The catalyst does not alter the equilibrium Because for the catalysed reaction and
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9. The addition of inert gas for the reaction N2(g) Because the addition of inert gas at
+ 3H2 2NH3(g) at constant pressure constant pressure favours the backward
reaction.
decreases the rate of formation of NH3.
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Answers to Assignments
SECTION - I
LEVEL - I
LEVEL - II
SECTION - I
1. (C)
2. (BC)
3. (AA)
4. (AB)
5. (CC)
6. (DA) 7
7. (C)
8. (DB) 8
9. (BC)
9
10. (CC)
101. (BA)
12. (B)
13. (D)
14. (D)
15. (A)
16. (C)
17. (A)
18. (A)
19. (A)
20. (C)
21. (B)
22. (B)
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23. (C)
24. (B)
25. (B)
SECTION - IILEVEL - II
4. (ba), (cb)
5. (ba), (b), (c), (d)), (c)
6. (a), (b), (c), (d)
1. (a)
2. (c)
3. (b)
4. (a)
5. (b)
6. (a)
7. (b, c)
8. (d)
9. (c)
10. (d)
11. (d)
12 (b)
13. (b)
14. (b)
15. (b)
SECTION - II
LEVEL I
LEVEL II
1. Kc = 3.1420
2. = 0.33; Kp = 0.205 atm
3. 57.92
4. 0.7833 mole
5. In this question, concentration of three species i.e. SO2 Cl2 , SO 2 and Cl2 (g) each is
given, but is not mentioned that whether the system is at equilibrium or not. So first
check it. Find reaction coefficient for given equation.
[SO 2 ][Cl 2 ] (0.05)(0.05)
Q 0.05
[SO 2Cl 2 ] (0.05)
Q K , so system is not at equilibrium state.
As Q > K, the concentrations must adjust till Q = K for equilibrium. This can happen
only if reaction shifts backwards, and products recombine to give back reactants. Hence
in the reaction vessel, the system will move backward so that it can achieve equilibrium
state.
6. Kc = 4.012
7. (i) Kc = 187.84, Kp = 0.0495
(ii) P = 12.438 atm
3 3 3
8. (i) PH2O 1.62 10 atm , PH2O 3.53 10 atm , PH2O 3.64 10 atm , (ii) SrCl2.2H2O
(iii) 60.5%; (iv) 60.5%
9. (a) PNO = 1.05 atm
(b) KP = 3.43 atm-1
10. 12.22 kJ mol-1.
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SECTION - IV
SECTION - IIIV
A B C
Match the following Write-up Assertion and Reasoning
1 (A) (r) 1. (c) 2. (b) 1. (A)
(B) (p) 3. (b) 4. (a) 2. (D)
(C) (q) 5. (a) 6. (a) 3. (B)
(D) (s) 7. (d) 8. (a) 4. (D)
2 (A) (q) 9. (a) 10. (a)
(B) (p)
11. (d)
(C) (r)
(D) (s)
1 (a - r), (b - p), (c - q), (d - s)
2 (a 2-q), (b 3 - r), (c 1 - p),
SECTION IV
1 (d) 2. (a)
3. (d) 4. (a)
5. (a), (b), (c), (d) 6. (c), (d)
7. (a) 8. (c), (d), (e)
9. (b), (c)
Previous IIT- JEE Problems Subjective
SECTION - V
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LEVEL I
SECTION - VI
LEVEL I
3. 100 mm/Hg
4. a) 0; b) 1.64.06M1
5. right to left
6. a) forward; b) backward; c) no
7. a) Kp = KcRT; b) Kp = KcRT; c) Kp = Kc
8. 3.02 105
LEVEL II
1. Kc = 3.1420
3. 57.92
4. 0.78337 mole
5. In this question, concentration of three species i.e. SO 2 Cl2 , SO 2 and Cl 2 (g) each is
given, but is not mentioned that whether the system is at equilibrium or not. So first
check it. Find reaction coefficient for given equation.
As Q > K, the concentrations must adjust till Q = K for equilibrium. This can happen
only if reaction shifts backwards, and products recombine to give back reactants. Hence
in the reaction vessel, the system will move backward so that it can achieve equilibrium
state.
6. Kc = 4.012
3 3 3
8. (i) PH2O 1.62 10 atm , PH2O 3.53 10 atm , PH2O 3.64 10 atm , (ii) SrCl2.2H2O
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LEVEL III
1/ 3
2K p
1. 7.5 10 -18
P
2. N2 = 79%, O2 = 21
3. 4.53 g/litre
4. 5.845
5. 4.53 g/L2.55 (atm)3
6. 1.8 atm
7. a) CO = 0.041 mole litre1, CO2 = 0.015 mol litre1,
(b) 0.145 atm
8. Kc = 279.64 litre2 mol2, Kp = 0.115 atm2
9. 0.02042
0 0
10. G1 = 16.178kJ, G2 = 12.282 kJ, B > A, B > C, B > C > A
SECTION - V
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Assignments
LEVEL I (CBSE LEVEL) Review Your Concept
1. The equilibrium constant of an equilibrium represented by A (g)
B(g) is 1.1 which of
the two gases A and B has a molar concentration greater than 1 atm at equilibrium?
2. Kc for the equilibrium N 2O 4(g)
2NO 2(g) at 298C is 5.7 109. Which species has a
higher concentration at equilibrium?
3. State whether the following statement is false or true. If the equilibrium constant for
1 1
2AB is K, the equilibrium constant for AB
A 2 B2 A 2 B2 is 1/K.
2 2
4. Would you expect the equilibrium constant for the reaction I 2(g)
2I(g) to increase or
decrease as temperature increases? Why?
5. The equilibrium constant expression for a gas reaction is
[NH3 ]4 [O 2 ]5
Kc
[NO]4 [H 2O]6
Write the balanced chemical equation corresponding to this expression.
6. In the following equilibrium A + B nC equilibrium constant is expressed in the
1
unit of L mol . Predict value of n.
7. Write the equilibrium constants for each of the following reactions:
a) CO2(g) + C(s)
2CO(g)
b) Hg(l) + Hg2+(aq) 2+
Hg2 (aq)
c) 2Fe(s) + 3H2O(g)
Fe2O3(s) + 3H2(g)
d) 2H2O(l)
2H2(g) + O2(g)
8. Consider the reaction SO2 Cl2 (g)
SO 2 (g) Cl 2 (g) ; at 37C the value of
equilibrium constant for the reaction is 0.0032. It was observed that concentration of the
three species is 0.050 mol/lit. each at a certain instant. Discuss what will happen in the
reaction vessel?
9. Gaseous NO2 forms N2O4 according to the reaction
2NO2(g)
N2O4(g)
when 0.10 mole of NO2 is added to 1.0 L flask at 25C, the concentration changes so that
at equilibrium, [NO2] = 0.016 M and [N2O4] = 0.042M.
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9. The activation energy of H2 + I2 2HI in equilibrium for the forward reaction is 167
kJ mol1 whereas for the reverse reaction is 180 kJ mol1. The presence of catalyst lowers
the activation energy by 80 kJ mol1. Assuming that the reactions are made at 27C and
the frequency factor for forward and backward reactions are 4 104 and 2 103
respectively, calculate KC.
10. In an evacuated vessel of capacity 110 litres, 4 moles of Argon and 5 moles of PCl5 were
introduced and brought to equilibrium at a temperature of 250oC. At equilibrium, the total
pressure of the mixture was found to be 4.678 atm. Calculate the degree of dissociation,
of PCl5 and KP for the reaction
PCl5 PCl3 + Cl2, at this temperature.
LEVEL III Check Your Skills
1. The value of K c for the reaction : H 2 (g) I 2 (g)
2HI(g) is 45.9 at 773 K. If one
mole of H 2 , two mole of I 2 and three moles of HI are taken in a 10 L flask, find the
concentrations of I 2 and HI at equilibrium at 773 K.
2. K p for the reaction PCl5
PCl3 Cl 2 at 250C is 0.82. Calculate the degree of
dissociation at given temperature under at total pressure of 5 atm. What will be the degree
of dissociation if the equilibrium pressure is 10 atm. at same temperature.
3. 0.25 mol of CO taken in a 2.5 L flask is maintained at 750 K along with a catalyst so that
the following reaction can take place; CO(g) + H 2 (g)
CH3OH(g) . Hydrogen is
introduced unitl the total pressure of the system is 8.5 atm. At equilibrium 0.08 mol of
methanol is formed. Calculate:
i) K p and K c
ii) The final pressure if the same amount of CO and
H 2 as before are used but no catalyst so that the reaction does not take place.
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4. If dt be the initial density and d0 be the density at equilibrium then derive expression for
degree of dissociation for following equilibria.
SO3(g) SO2(g) + 1/2O2(g)
5. Ammonia under a pressure of 15 atm. At 27C is heated to 347C is a closed vessel in the
presence of catalyst. Under these conditions, NH3 partially decomposes to H2 and N2. The
vessel is such that the volume remains effectively constant, whereas the pressure
increases to 50 atm. Calculate the % age of NH3 actually decomposed.
6. Solid NH4HS(s) (Ammonium hydrogen sulphide) dissociates to give NH3(g) and H2S(g) and
is allowed to attain equilibrium at 100C. If the value of Kp for its dissociation is found to
be 0.34. find the total pressure at equilibrium and partial pressure of each component.
7. 500 ml of 1.09 M Fe2+ solution were added to 500 ml of 0.150 M AgNO3 Solution and
the reaction is allowed to reach an equilibrium at 25C
Ag+ (aq) + Fe+2(aq) Fe+3 (aq) + Ag(s)
For 25 ml of the solution, 30 ml of 0.0832 M KMnO4 were required for oxidation.
Calculate equilibrium constant for the reaction at 25C.
8. Equilibrium constants are given (in atm) for the following reactions at 0C
a) SrCl26H2O(s)
SrCl22H2O(s) + 4H2O(g),
12
Kp = 6.89 10
b) Na2HPO412H2O(s) Na2HPO47H2O(s) +
13
5H2O(g), Kp = 5.25 10
c) Na2SO410H2O(s)
Na2SO4(s) + 10H2O(g) Kp =
25
4.08 10
The vapour pressure of water at 0C is 4.58 torr.
i) Calculate the pressure of water vapour in
equilibrium at 0C with each of (a), (b) and (c).
ii) Which is the most effect drying agent at 0C?
iii) At what relative humidities with Na2SO210H2O be
efflorescent when exposed to air at 0C?
iv) At what relative humidities will Na2SO4 be
deliquescent (i.e,. absorb moisture) when exposed to air at 0C?
9. For the reaction: CO 2 (g) H 2 (g)
CO(g) H 2O(g), K is 0.63 at 700C and 1.66 at
1000C.
What is the average H for the temperature range considered?
What is the value of K at 800C ?
10. NO and Br2 at initial pressures of 98.4 and 41.3 torr respectively were allowed to react at
300K. At equilibrium the total pressure was 110.5 torr. Calculate the value of equilibrium
constant , Kp and the standard free energy change at 300K for the reaction
2NO(g) Br2(g)
2NOBr(g)
LEVEL IV Judge yourself at JEE level
1. At temperature T, a compound AB2(g) dissociates according to the reaction:
2AB2(g)
2AB(g) + B2(g) with a degree of dissociation x which is small compared to
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unity. Deduce the expression for x in terms of the equilibrium constant Kp and the total
pressure P.
2. A sample of air consisting of N2 and O2 was heated to 2500K until the equilibrium
N 2(g) O 2(g)
2NO(g)
was established with an equilibrium constant KC = 2.1 103. At equilibrium, the moles
% of NO were 1.8. Estimate the initial composition of air in mole fraction of N2 and O2.
3. The degree of dissociation is 0.4 at 400K and 1.0 atm for the gaseous reaction
PCl5 PCl3 + Cl2. Assuming ideal behaviour of all the gases, calculate the density of
equilibrium mixture at 400K and 1.0 atmosphere. (Atomic mass of P = 31.0 and
Cl = 35.5)
4. Calculate the value of log Kp for the reaction
N 2(g) 3H 2(g)
2NH3(g)
at 25C. The standard enthalpy of formation of NH3(g) is 46kJ and standard entropies of
N2(g), H2(g) and NH3(g) are 191, 130, 192 JK1 mol1 respectively (R = 8.3 JK1 and mol1).
5. When S in the form of S8 is heated at 900K, the initial pressure of 1 atmosphere falls by
29% at equilibrium. This is because of conversion of some S8 to S2. Find the Kp for
reaction.
6. A vessel at 1000K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted
into CO on addition of graphite. Calculate the value of K, if total pressure at equilibrium
is 0.8 atm.
7. At 817C, Kp for the reaction between CO2(g) and excess hot graphite(s) is 10 atm.
a) What are the equilibrium concentration of the gases
at 817C and a total pressure
of 5 atm?
b) At what total pressure, the gas contains 5% CO2 by
volume?
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and (C).
Objective
LEVEL I
1. In a chemical reaction Kp is greater than Kc when
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2. Which of the following statements is not correct about the equilibrium constant ?
(a) Its value does not depend upon the initial conc. of
the reactants
(b) Its value does not depend upon the initial conc. of
the products
(c) Its value does not depend upon nature of the
reactants.
(d) Its value does not depend upon presence of catalyst.
3. An acid reacts with glycerine to form complex and equilibrium is established. If the heat
of reaction at constant volume for above reaction is 1200 cal more than at constant
pressure and the temperature is 300 K, then which of the following expression is true ?
(a) Kp Kc (b) Kc Kp
(c) Kp Kc (d) none of these.
4. The equilibrium constant for the reaction,
N2(g) + O2(g)
2NO(g) is 4 104
at 2000 K. In presence of a catalyst, equilibrium is attained ten times faster. Therefore,
the equilibrium constant, in presence of the catalyst, at 2000 K is
(a) 40 104 (b) 4 104
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LEVEL II
A
N 2O 4
2NO 2 , K c 4 . This reversible reaction is studied D E
Concentration
graphically as shown in figure. Select the correct C
statements out of I, II and III.
F G
I. Reaction quotient has maximum value at point A B Time
1. (b) 6. (a)
2. (d) 7. (d)
3. (a) 8. (a)
4. (a) 9. (a)
5. (a) 10. (a)
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7
5. When 20g of CaCO3 were put into 10 litre flask and heated to 800C, 35% CaCO3
remained unreacted at equilibrium, Kp for decomposition of CaCO3 is
(a) 1.145 atm (b) 0.145 atm
(c) 2.145 atm (d) 3.145 atm
6. The decomposition of N2O4 to NO2 is carried out at 280C in chloroform. When
equilibrium is reached, 0.2 mol of N2O4 and 2 103 mol of NO2 are present in 2 litre
solution. The equilibrium constant for the reaction, N 2 O 4 2NO 2 is
(a) 1 103 (b) 2 103
(c) 1 105 (d) 2 105
7. In a reaction, A + 2B 2C, 2.0 mole of A, 3.0 mole of B and 1.0 mole of C are
placed in a 2.0L flask and the equilibrium concentration of C is 1.0 mole/L. The
equilibrium constant (K) for the reaction is:
(a) 0.33 (b) 1.33
(c) 1.66 (d) 0.6
8. For the equilibrium, NH 4 HS(s) NH 3(g) H 2S (g)
the value of Kp is 0.109 atm2 at 300K. The vapour pressure of NH4HS at 300K would be
(a) 0.33 atm (b) 0.109 atm
(c) 0.66 atm (d) 1.0 atm
9. Two moles of an equimolar mixture of two alcohols, R1 OH and R 2 OH are
esterified with one mole of acetic acid. If 80% of the acid is consumed and the quantities
of ester formed under equilibrium are in the ratio of 3 : 2, the value of the equilibrium
constant for the esterification of R1 OH with acetic acid is
(a) : 3.3 (b) : 3.7
(c) : 3.5 (d) : 3.9 .
10. A 1 M solution of glucose reaches dissociation equilibrium according to the equation
given below: 6HCHO C6 H12 O6
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West Delhi Centre: 2/40, Adjacent Central Market, West Punjabi Bagh, New Delhi - 110 026. Ph.:
55479790, 30946351South Delhi Centre: 47B, Kalu Sarai, New Delhi - 110 016. Ph.: 41828300/01/02,
32001114/15/16
West Delhi Centre: 15, Central Market, West Punjabi Bagh, New Delhi - 110 026. Ph.: 55479790,
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160 CHEMISTRY : CHEMICAL EQUILIBRIUM
LEVEL I
1. B
2. N2O4
3. False
4. Increase, because for given reaction H 0
5. 4NO(g) + 6H2O(g) 4NH3(g) + 5O2(g)
6. n=3
7. While writing chemical equilibrium equation, molar concentration or partial pressure of
the reactants and products are taken as unity thus,
[CO]2 p2
a) Kc ; K p CO
[CO 2 ] p CO2
[Hg 22 ]
b) Kc
[Hg 2 ]
[H 2 ]3 p3H2
c) Kc , K p
[H 2O]3 p3H 2O
d) K c [H 2 ]2[O 2 ], K p p 2H2PO
2
8. In this question, concentration of three species i.e. SO 2 Cl 2 , SO 2 and Cl2 (g) each is
given, but is is not mentioned that whether the system is at equilibrium or not. So first
check it. Find reaction coefficient for given equation.
[SO 2 ][Cl2 ] (0.05)(0.05)
Q 0.05
[SO 2 Cl2 ] (0.05)
Q K , so system is not at equilibrium state.
As Q > K, the concentrations must adjust till Q = K for equilibrium. This can happen
only if reaction shifts backwards, and products recombine to give back reactants. Hence
in the reaction vessel, the system will move backward so that it can achieve equilibrium
state.
9. a) 0; b) 1.64.06M1
10. right to left
11. a) forward; b) backward; c) no
12. a) Kp = KcRT; b) Kp = KcRT; c) Kp = Kc
13. 3.02 105
14. 1.067
15. a) no effect; b) forward; c) backward
LEVEL II
1. H2 = 0.111 atm, I2 = 0.111 atm, HI = 0.778 atm
2. [H2] = 0.316 mole litre1, [I2] = 1.316 mol litre1, [HI] = 4.368 mol litre1
3. Kp = 50, 0.11 mole
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1
4. i) 0.681; ii) CO2 = 0.34 atm, CO = 1.16 atm; iii) H2O = 0.16 atm
5. a) CO2 = H2 = 0.338 mole, CO = H2O = 0.112 mole
b) CO2 = H2 = 0.593 mole, CO = H2O = 0.197 mole
6. a) 0.1 mole, (b) 0.4 mole
7. 480 mm
8. N2O4 = 0.095 atm, NO2 = 0.64 atm
9. Kp = 1.77 atm, KC = 4 102 mole litre1
10. 0.969 atm
LEVEL III
1/ 3
2K p
1.
P
2. N2 = 79%, O2 = 21
3. 4.53 g/litre
4. 5.845
5. 2.55 (atm)3
6. 1.8 atm
7. a) CO = 0.041 mole litre1, CO2 = 0.015 mol litre1, (b) 0.145 atm
8. Kc = 279.64 litre2 mol2, Kp = 0.115 atm2
9. 0.02042
10. G10 = 16.178kJ, G20 = 12.282 kJ, B > A, B > C, B > C >
Objective
LEVEL I
1. c 2. c
3. a 4. b
5. c 6. a
7. c 8. b
9. c 10. c
11. a 12. b
13. d 14. d
15. a
LEVEL II
1. b 2. c
3. a 4. a
5. a 6. c
7. b 8. c
9. b 10. d
11. c 12. b
13. b 14. b
15. b
6
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