CHEMICALEQUILIBRIUM_CR (1)

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CHEMICAL EQUILIBRIUM
KEY CONCEPTS
TYPES OF REACTION:
(i) Reversible :
(ii) Irreversible
STATE OF EQUILIBRIUM
Most of the chemical reaction do not go to completion in a closed system and attain a state of
equilibrium.
There are two approaches to understand nature of equilibrium. The One stems from
thermodynaics. Equilibrium criteria is explained on the basis of thermodynamic function like DH
(change in enthalpy), DS (change in entropy) and DG (change in Gibb's function). At equilibrium
macroscopic properties of the system like concentration, pressure ect. become constant at constant
temperature.
Other approach comes from kinetics as developed by Guldberg and Waage (1863). Equilibrium is
said to have reached in a physical or chemical system when rate of forward and reverse processes
are equal.
At equilibrium
Rate of forward reaction = Rate of backward reaction.
rf
rate
State of
equilibrium
rb
time
Example:
N2(g) + 3H2(g) ¾® 2NH3(g)
Starting with pure H2 and N2 as reaction proceeds in forward direction. Ammonia is formed. At
initially conc. of H2 and N2 drops and attain a steady value at equilibrium. On the others hand conc.
of NH3 increases and at equilibrium attains a constant value.
Concentration time graphs for
concentration.
[H2]
[N2]
[NH3]
t
fig (1)
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IMPORTANT CHARACTERISTIC OF EQUILIBRIUM
(i) Equilibrium is possible only in closed system.
(ii) The rate of forward process at equilibrium is equal to rate of backward process.
(iii) All measurable properties of system remain constant over time.State of chemical equilibrium
is characterised by equilibrium constant. Equilibrium constant have constant value at a given
temperature.
(iv) At equilibrium entropy of universe is maxmized.
(v) Both, Kinetic and Thermodynamics theories can be invoked to understand the extent to
which a reaction proceed to forward direction. e.g. If extent of reaction is too large for forward
direction (equilibrium is tilted heavily to forward direction) than
(a) Specific rate of forward reaction >>> specific rate of backward reaction
(b) Gibb's function of product is vary small as compared to Gibb's function of reactant.
LAW OF CHEMICAL EQUILIBRIUM OR MASS ACTION (By Guldberg and Waage)

A general equation for a reversible reaction may be written
mA + nB l xC + yD
rate of reaction in inforward direction(rf) µ [A]m [B]m ; rf = kf [A]m [B]m
rate of reaction in inforward direction(rb) µ [C]x [D]y ; rb = kb [C]x [D]y
At equilibrium, rf = rb
[C]x [D]y
Keq or Kc = where Kc = kf / kb
[A]m [B]m
where we use [ ] to indicate "molar concentration."
Note : We should calculate the value of K from the activities of the reactants and products rather than
from their concentrations. However, the activity of a dilute solute is usefully approximated by its molar
concentration, so we will use molar concentrations. However, for gases we can use molar concentrations
of gases and partial pressure in our equilibrium calculations, The activity of a pure solid or pure liquid
is constant , and the activity of a solvent in a dilute solution is also constant.Thus these species (solids,
liquids, and solvents) are omitted from reactions quotients and equilibrium calculations.
o o
UNIT OF EQUILIBRIUM CONSTANT (K C , K C , K P & K P )
We have already noted that the value of an equilibrium constant has meaning only when we give
the corresponding balanced chemical equation. Its value changes for the new equation obtained by
multiplying or dividing the original equation by a number. The value for equilibrium constant, KC is
calculate substituting the concentration in mol/L and for KP by substituting partial pressure in Pa,
kPa, etc. in atm. Thus, units of equilibrium constant will turn out to be units based on molarity or
pressure, unless the sum of the exponents in the numerator is equal to the sum of the exponents in
the denominator. Thus for the reaction:
H2(g) + I2(g) l 2HI, KC and KP do not have any unit
N2(g) + 3H2(g) l 2 NH3 , KC has unit (mol/L)–2 and KP has unit bar–2 or
N2O4 (g) l 2NO2, KC has unit mol / L and KP has unit bar
However, these days we express equilibrium constants in dimensionless quantities by deviding
concentration by 1 M and partial pressure by 1 bar.
* Relationship between KP & KC
KP = KC (RT) Dng
TYPE OF EQUILIBRIUM
(a) Homogeneous chemical equilibria
A homogeneous equilibrium is equilibrium with in a single phase i.e. when physical state of all the
reactants and product are same.
(ii) Liquid phase homogeneous equilibrium
Example : (i) I2 (aq) + I - (aq) l I3- (aq)
[I 3- (aq)]
Eq. constants is K=
[I 2 (aq)][I - (aq)]
(iii) Homogeneous equilibria in gases

Example : (i) C2H6(g) l C2H4(g) + H2(g)
Eq. constants is
[C 2 H 4 O)][H 2 ] [PC2H 4 ][PH 2 ]
KC = [C H (g)] KP = [P ]
2 6 C2 H 6
[ ] represents concentration PC2H 4 & other are partial pressure at equilibrium

in mol/ litre at equilibrium
(ii) 3O2(g) l 2O3(g)

Eq. constants is
[O 3 ]2 PO23
KC = KP =
[O 2 ]3 PO3 2
(b) Hetrogeneous equilibria
If reactants and product are found in two or more phases, the equilibria describing them is called
hetrogeneous equilibrium.
Example: CaO(s) + CO2(g) l CaCO3(s)
1 1
Eq. constants is KP = KC =
PCO [CO 2 (g)]
2
CHARACTERSTICS OF EQUILIBRIUM CONSTANT

(i) The expression for equilibrium constant, K is applicable only when concentrations of the reactants
and products have attained their equilibrium values and do not change with time.
(ii) The value of equilibrium constant is independent of initial concentration of the reactants and product.
(iii) Equilibrium constant has one unique value for a particular reaction represented by a balanced equation
at a given temperature.
(iv) The equilibrium constant for the reverse reaction is equal to the inverse of the equilibrium constant
for the forward reaction.
H2(g) + I2(g) 2HI(g)
PHI 2
Kp = P .P ; 2HI(g) H2(g) + I2(g)
H2 I2
1
KP' = K
P
(v) The equilibrium constant K, for a reaction is related to the equilibrium constant of the corresponding
reaction whose equation is obtained by multiplying or dividing the equation.
1 1
H2(g) + I2(g) 2HI(g) ; H2(g) + I2(g) HI(g)
2 2
PHI
KP" = P 2 .P1/ 2 = K p
1/
H2 I2
(vi) If reaction is performed is steps
A B ; overall reaction
Step-1 : A(g) C(g) + D(g) K p1
Step-2 : C(g) E(g) K p2
Step-3 : D(g) + E(g) B(g) K p3
A(g) B(g) Kp then Kp = K p1 . K p2 . K p3
APPLICATION OF EQULIBRIUM CONSTANT.
Now we will consider some applications of equilibrium constant and use it to answer question like:
(i) predicting the extent of a reaction on the basis of its magnitude.
(ii) predicting the direction of the reaction, and
(iii) calculating equilibrium concentration.
(i) Predicting the extent of a reaction
The magnitude of equilibrium constant is very useful especially in reactions of industrial importance.
An equilibrium constant tells us whether we can expect a reaction mixture to contain a high or low
concentration of product(s) at equilibrium. (It is important to note that an equilibrium constant tells
us nothing about the rate at which equilibrium is reached). In the expression of KC or KP, product of
the concentrations of products is written in numerator and the product of the concentrations of
reactants is written in denominator. High value of equilibrium constant indicates that product(s)
concentration is high and its low value indicates that concentration of the product(s) in equilibrium
mixture is low.
For reaction, H2 (g) + Br2(g) l 2HBr(g), the value of
(PHBr ) 2
KP = 18
(PH )(PBr ) = 5.4 × 10
2 2
The large value of equilibrium constant indicates that concentration of the product, HBr is very high
and reaction goes nearly to completion.
Similarly, equilibrium constant for the reaction H2(g) + Cl2(g) l 2HCl(g) aty 300 K is very high
and reaction goes virtually to completion.
[HCl]2
KC = = 4.0 × 1031
[H 2 ][Cl 2 ]
Thus, large value of KP or KC (larger than about 103), favour the products strongly. For intermedicate
values of K (approximately in the range of 10–3 to 103), the concentrations of reactants and products
are comparable. Small values of equilibrium constant (smaller than 10–3), favour the reactants strongly.
At 298 K for reaction, N2(g) + O2(g) l 2NO(g)
[NO]2
KC = = 4.8 × 10–31
[N 2 ][O 2 ]
The very small value of KC implies that reactants N2 and O2 will be the predominant species in the
reaction mixture at equilibrium.
(ii) Predicting the direction of the reaction.
The equilibrium constant is also used to find in which direction an rabidity reaction mixture of
reactants and products will proceed. For this purpose, we calculate the reaction quotient, Q. The
reaction quotient is defined in the same way as the equilibrium constant ( with molar concentrations
to give QC, or with partial pressure to give QP) at any stage of reaction. For a general reaction:
aA + bB l cC + dD
[C]c [D]d
QC =
[A]a [B]b
Then, if QC > Kc , the reaction will proceed in the direction of reactants (reverse reaction).
if QC < Kc, the reaction will move in the direction of the products
if QC = Kc, the reaction mixture is already at equilibrium.
In the reaction, H2(g) + I2(g) l 2Hl(g), if the molar concentrations of H2 , I2 and HI are 0.1 mol L–
1 respectively at 783 K, then reaction quotient at this stage of the reaction is
[HI]2 (0.4) 2
QC = = =8
[H 2 ][I 2 ] (0.1)(0.2)
KC for this reaction at 783 K is 46 and we find that QC < KC. The reaction, therefore, will move to
right i.e. more H2(g) and I2(g) will react to form more HI (g) and their concentration will decrease
till QC = KC.
(iii) Calculating equilibrium concentration.

(a) A + B ¾® C
at time t = 0 a b
at equlb. a–x b–x x
æ x ö
ç PT ÷
(x / V) èa +b-x ø
Kc = ; Kp =
æ a - x öæ b - x ö æ a-x öæ b - x ö
ç ÷ç ÷ ç PT ÷ ç PT ÷
è V øè V ø è a + b - x øè a + b - x ø
(b) Equilibrium constant expressions in term of 'a'

PCl5(g) ¾® PCl3(g) + Cl2(g)
Initial partial pr. 1 – –
At. Eq. 1–a a a
[p PCl3 (g) ][p Cl 2 (g) ] a2 æ 1 ö

KP = ; KC = ç ÷
p [PCl5 (g)] 1- a è V ø
a.a PT
KP = ×
1- a (1+ a)
a2
KP = P
1- a 2 T
(IV) Degree of dissociation in terms of molar mass and vapour density
(a) A(g) l nB(g)

M T - MO DT - DO
a= or a=
M O (n -1) D O (n -1)
MT = Theoretical molar mass of reactant
MO = Observed molar mass of mixture
MT MO
DT = and DO =
2 2
(b) nA (g) l An (g)
Initial conn a 0
aa
at eqm 1(1–a)
n
MT - MO
a=
æ1 ö
M O ç - 1÷
èn ø
FACTOR'S AFFECTING EQUILIBRIA (Le-chatelier's principle)

(i) Effect of change in concentration on equilibrium
A chemical system at equilibrium can be shifted out of equilibrium by adding or removing one
more of reactants or products. Shifting out of equilibrium doesn't mean that value of equilibrium
constant change. Any alteration of concentration of reactant or product will disturb the equilibrium
and concentration of reactant and product one readjust to one again attain equilibrium concentration.
In other word, as we add or remove reactant (or product) the ratio of equilibrium concentration
become 'Q' (reaction quotient) and depending upon.
Q<K : equilibrium will shift in forward direction.
Q >K : equilibrium will shift in backward direction.
Example : Fe3+ (a) + SCN– (aq) l Fe (SCN)2+(aq)
[Fe(SCN) 2+ ]
(i) adding Fe3 or SCN– will more = Q less then KC and equilibria will shift in forward
[Fe3+ ][SCN - ]
direction.
(ii) Removing Fe(SCN)2+will have same effect
(iii) Adding Fe(SCN)2+from outside source in equilibrium mixture will have effect of increasing 'Q'
hence reaction shift in backward direction.
(ii) Effect of change in pressure

Sometimes we can change the position of equilibrium by changing the pressure on a system. However,
changes in pressure have a measurable effect only in system where gases are involved – and then
only when the chemical reaction produces a change in the total number of gas molecules in the
system.
As we increase the pressure of a gaseous system at equilibrium, either by decreasing the volume of
the system or by adding more of the equilibrium mixture, we introduce a stress by increasing the
number of molecules per unit of volume. In accordance with Le Chatelier's principle, a chemical
reaction that reduces the total number of molecules per unit of volume will be favored because this
relieves the stress. The reverse reaction would be favoured by a decrease in pressure.
Consider what happens when we increase the pressure on a system in which NO, O2 and NO2 are
in equilibrium.
Example : 2NO(g) + O2 (g) l 2NO2(g)
The formation of additional amounts of NO2 decreases the total number of molecules in the system,
because each time two molecules of NO2 form, a total of three molecules of NO and O2 react. This
reduces the total pressure exerted by the system and reduces, but does not completely relieve, the
stress of the increased pressure. On the other hand, a decrease in the pressure on the system favors
decomposition of NO2 into NO and O2 which tends to restore the pressure.
Let us now consider the reaction
N2(g) + O2 (g) l 2NO(g)
Because there is no change in the total number of molecules in the system during reaction, a change
in pressure does not favor either formation or decomposition of gaseous nitric oxide.
(iii) Effect of change in temperature on equilibrium
Changing concentration or pressure upsets an equilibrium because the reaction quotient is shifted
away from the equilibrium value. Changing the temperature of a system at equilibrium has a different
effect: A change in temperature changes the value of the equilibrium constant. However, we can
predict the effect of the temperature change by treating it as a stress on the system and applying Le
Chatelier's principle. When hydrogen reacts with gaseous iodine, energy is released as heat is evolved.
H2(g) + I2(g) l 2I(g) DH = – 9.4 kJ (exothermic)

Because this reaction is exothermic, we can write it with heat as a product.
H2(g) + I2(g) l 2HI(g) + 9.4 kJ

Increasing the temperature of the reaction increases the amount of energy present. Thus, increasing
the temperature has the effect of increasing the amount of one of the products of this reaction. The
reaction shifts to the left to relieve the stress, and there is an increase in the concentration of H2 and
I2 and a reduction in the concentration of HI. When we change the temperature of a system at
equilibrium, the equilibrium constant for the reaction changes. Lowering the temperature in the HI
system increases the equilibrium constant from 50.0 at 400°C to 67.5 at 357°C. At equilibrium at
the lower temperature, the concentration of HI has increased and the concentrations of H2 and I2
have decreased. Raising the temperature decreases the value of the equilibrium constant from 67.5
at 357°C to 50.0 at 400°C.
van't Hoff equation
d(lnK) DH °
(a) =
dT RT 2
æ K2 ö ° æ 1 1ö
ln çç ÷÷ = - DH ç - ÷
è K1 ø R è T2 T1 ø
(iv) Effect of catalyst on equilibrium
A catalyst has no effect on the value of an equilibrium constant or on equilibrium concentrations.
The catalyst merely increase the rates of both the forward and the reverse reactions to the same
extent so that equilibrium is reached more rapidly.
All of these effects change in concentration or pressure, change in temperature, and the effect of a
catalyst on a chemical equilibrium play a role in the industrial synthesis of ammonia from nitrogen
and hydrogen according to the equation.
N2 + 3H2 l 2NH3
One way to increase the yield of ammonia is to increase the pressure on the system in which N2, H2
and NH3 are in equilibrium or are coming to equilibrium.
N2 (g) 3H2(g) l 2NH3(g)
The formation of additional amounts of ammonia reduces the total pressure exerted by the system
and somewhat reduces the stress of the increased pressure.
Although increasing the pressure of a mixture of N2 , H2 and NH3 increase the yield ammonia, at
low temperatures the rate of formation of ammonia is slow. At room temperature, for example, the
reaction is so slow that if we prepared a mixture of N2 and H2, no detectable amount of ammonia
would form during our lifetime. Attempts to increase the rate of the reaction by increasing the
temperature are counterproductive. The formation of ammonia from hydrogen and nitrogen is an
exothermic process:
N2(g) + 3H2(g) ¾® 2NH3(g) DH = – 92.2 kJ
Thus increasing the temperature to increase the rate lowers the yield. If we lower the temperature to
shift the equilibrium to the right to favour the formation of more ammonia, equilibrium is reached
more slowly because of the large decrease of reaction rate with decreasing temperature.
Part of the rate of formation lost by operating at lower temperatures can be recovered by using a
catalyst to increase the reaction rate. Iron powder is one catalyst used. However, as we have seen, a
catalyst serves equally well to increase the rate of a reverse reaction in this case, the decomposition
of ammonia into its constituent elements. Thus the net effect of the iron catalyst on the reaction is to
cause equilibrium to be reached more rapidly.
A THERMODYNAMIC RELATIONSHIP :
DG = DG° + RT lnQ [Q = Reaction quotient]

DG° = –RT ln Keq (At eqm. (DG)T,P = 0)
DG° = DH° – TDS°
For Exothermic reaction
- D r H° D S°
ln Keq = + r
RT R
D S° D r H°
ln K1 = r – RT
R 1 ln K
D r S° D r H°
ln K2 = – KT
R 2
1/T
æ K 2 ö DH° æ 1 1 ö
ln çç K ÷÷ = çç - ÷÷
è 1ø R è T1 T2 ø
EQUILIBRIUM CONSTANT AS PER KINETICS :

Kf
A(g) Kb B (g) + C(g)
- d(A)
= Kf [A] – Kb [B] [C]
dt
- d[A] K f [B][C]
At eqm =0 = = Kc
dt Kb [A]
where k = A · e-Ea / RT ; A : pre-expotential factor
- Ea (f ) / RT
kf = Af · e Ea : activation energy
- Ea ( b) / RT
kb = Ab · e
Ea(f) Ea(b)
-E / RT P.E.
kf A f .e a (f )
Keq = k = -E / RT
b A b .e a (b)
DH
Reaction Coordinate
k = A · e–DH/RT
where DH = Ea(f) – Ea(b)
DH
ln K1 = ln A – RT
1
DH
ln K2 = ln A – RT
2
K 2 DH é 1 1 ù
ln = ê - ú
K1 R ë T1 T2 û
SIMULTANEOUS EQUILIBRIA :
X(s) l A(g) + B(g) K P1 = (x + y)x
(x + y) x
Y(s) l A(g) + C(g) K P2 = (x + y)y
(y + x) y
K P1 x
= Ptotal = 2x + 2 y
K P2 y
SEQUENTIAL EQUILIBRIUM :
A(s) ¾® B (g) + C(g) K C1 = (x)(x - y)
a–x x x–y
y
C(g) ¾® D(g) K C2 =
x-y
x–y y
PHASE DIAGRAM FOR WATER:
P
Solid Liquid
O Gas
EXERCISE # S-I
Properties of equilibrium and equilibrium constant
1. The initial concentrations or pressure of reactants and products are given for each of the
following systems. Calculate the reaction quotient and determine the directions in which each
system will shift to reach equilibrium.
(a) 2NH3(g)  N2(g) + 3H2(g) K = 17
[NH3] = 0.20 M ; [N2] = 1.00 M ; [H2] = 1.00 M
(b) 2NH3 (g)  N2 (g) + 3H2 (g) Kp = 6.8 × 104 atm2
Initial pressure : NH3 = 3.0 atm ; N2 = 2.0 atm ; H2 = 1.0 atm
(c) 2SO3(g)  2SO2 (g) + O2 (g) Kp = 16.5 atm
Initial pressure : SO3 = 1.0 atm ; SO2 = 1.0 atm ; O2 = 1.0 atm
(d) 2NO(g) + Cl2 (g)  2NOCl (g) K = 4.6 × 104
[NO] = 1.00 M ; [Cl2] = 1.00 M ; [NOCl] = 0 M
2. Benzene is one of the compounds used as octane enhancers in unleaded gasoline.

It is manufactured by the catalytic conversion of acetylene to benzene.
3C2H2  C6H6
Would this reaction be most useful commercially if K were about 0.01, about 1, or about 10?
Explain your answer.
Nucleus Education-(NURTURE_(UNACADEMY)
Application of equilibrium constant (Homogeneous equilibrium)

3. Consider the gas-phase hydration of hexafluoroacetone, (CF3)2CO:

(CF3)2 CO (g) + H2O (g)   (CF3)2 C(OH)2 (g)
k
kr 
f
At 76°C, the forward and reverse rate constants are kf = 0.15 M–1 s–1 and kr = 6 × 10–4 s–1.
What is the value of the equilibrium constant Kc?
4. Consider the reaction of chloromethane with OH– in aqueous solution


CH3Cl (aq) + OH– (aq) 
kf
 CH3OH (aq) + Cl– (aq)
k  r
At 25°C, the rate constant for the forward reaction is 6 × 10–6 M–1 s–1, and the equilibrium
constant Kc is 1 × 1016. Calculate the rate constant for the reverse reaction at 25°C.
10 10
5. The progress of the reaction
A  nB with time, is presented in figure. Determine
0.5
0.3
0.1
1 3 5 7
(i) the value of n.
(ii) the equilibrium constant K.
6. If Kc = 0.5 × 10–9 at 1000 K for the reaction N2 (g) + O2 (g)  2NO (g), what is Kc at 1000 K
for the reaction 2NO (g)  N2 (g) + O2 (g)?
7. At 700 K, Kp = 0.2 for the reaction ClF3 (g)  ClF (g) + F2(g). Calculate the equilibrium
partial pressure of ClF3, ClF, and F2 if only ClF3 is present initially, at a partial pressure of
0.150 atm.
8. An equilibrium mixture of PCl5, PCl3 and Cl2 at a certain temperature contains

0.5 × 10–3 M PCl5, 1.5 × 10–2 M PCl3, and 3 × 10–2 M Cl2.
Calculate the equilibrium constant Kc for the reaction PCl5(g)  PCl3(g) +Cl2(g).
9. A sample of HI (9.6 × 10–3 mol) was placed in an empty 2.00 L container at 1000 K. After
equilibrium was reached, the concentration of I2 was 4 × 10–4 M. Calculate the value of Kc at
1000 K for the reaction H2 (g) + I2 (g) . 2HI (g).
10. The vapour pressure of water at 27°C is 0.2463 atm. Calculate the values of
Kp and Kc at 27°C for the equilibrium H2O (l)  H2O (g).
11. Which of the following reactions goes almost all the way to completion, and which proceeds
hardly at all?
(a) N2(g) + O2(g)  2NO (g); Kc = 2.7 × 10–18
(b) 2NO(g) + O2(g)  2NO2 (g); Kc = 6.0 × 1013
12. The value of Kc for the reaction 3O2 (g)  2O3 (g) is 8 × 10–55 at 25°C. Do you expect pure
air at 25°C to contain much O3 (ozone) when O2 and O3 are in equilibrium? If the equilibrium
concentration of O2 in air at 25°C is 8 × 10–3 M, what is the equilibrium concentration of O3 ?
11 11
13. 2 moles of A & 3 moles of B are mixed in 1 litre vessel and the reaction is carried at 400°C
according to the equation; A + B  2C. The equilibrium constant of the reaction is 4. Find the
number of moles of C at equilibrium.
14. At 1400 K, Kc = 2.5 × 10–3 for the reaction CH4 (g) + 2H2S  CS2(g) + 4H2(g). A 10.0 L
reaction vessel at 1400 K contains 2.0 mol of CH4, 3.0 mol of CS2,
3.0 mol of H2 and 4.0 mol of H2S. Is the reaction mixture at equilibrium?
If not, in which direction does the reaction proceed to reach equilibrium?
15. The first step in the industrial synthesis of hydrogen is the reaction of steam and methane to
give water gas, a mixture of carbon monoxide and hydrogen.
H2O (g) + CH4(g)  CO (g) + 3H2 (g) Kc = 4.7 at 1400 K
A mixture of reactants and product at 1400 K contains 0.03 M H2O, 0.050M CH4, 0.15 M CO,
and 0.20 M H2. In which direction does the reaction proceed to reach equilibrium?
16. An equilibrium mixture of N2, H2, and NH3 at 700 K contains 0.036 M N2 and 0.15 M H2.
At this temperature, Kc for the reaction N2(g) + 3H2(g)  2NH3(g) is 0.29. What is the
concentration of NH3?
17. The air pollutant NO is produced in automobile engines from the high temperature reaction
N2(g) + O2(g)  2NO (g) ; Kc = 16 at 2300 K. If the initial concentrations of N2 and O2 at
2300 K are both 1.5 M, what are the concentrations of NO, N2, and O2 when the reaction
mixture reaches equilibrium?
18. At a certain temperature, the reaction PCl5(g)  PCl3(g) + Cl2(g) has an equilibrium constant
Kc = 10–2. Calculate the equilibrium concentrations of PCl5, PCl3 and Cl2 if only PCl5 is present
initially, at a concentration of 0.1 M.
19. Following equilibrium is established at temperature T.

A(g)  B(g) + C (g)
at eq. 1M 2M 2M.
If volume of the vessel is doubled then find the equilibrium concentration of each species.
(Given that : 40 = 6.324)
Degree of dissociation ()
20. The degree of dissociation of N2O4 into NO2 at 1.5 atmosphere and 40°C is 0.25. Calculate its
Kp at 40°C. Also report degree of dissociation at 10 atmospheric pressure at same temperature.
12 12
21. At 46°C, Kp for the reaction N2O4(g)  2NO2(g) is 0.667 atm. Compute the percent
dissociation of N2O4 at 46° C at a total pressure of 380 Torr .
22. 2 NOBr (g)  2 NO (g) + Br2 (g). If nitrosyl bromide (NOBr) is 33.33% dissociated at 25° C
& a total pressure of 0.28 atm. Calculate Kp for the dissociation at this temperature.
23. When 36.8g N2O4 (g) is introduced into a 1.0-litre flask at 27°C . The following equilibrium
reaction occurs :
N2O4 (g)  2NO2 (g) ; Kp = 0.1642 atm.
(a) Calculate Kc of the equilibrium reaction.
(b) What are the number of moles of N2O4 and NO2 at equilibrium?
(c) What is the total gas pressure in the flask at equilibrium?
(d) What is the percent dissociation of N2O4?
24. At some temperature and under a pressure of 4 atm, PCl5 is 10% dissociated . Calculate the
pressure at which PCl5 will be 20% dissociated, temperature remaining same.
25. PCl5 dissociates according to the reaction PCl5  PCl3(g) + Cl2(g). At 523 K, Kp = 1.78 atm.
Find the density of the equilibrium mixture at a total pressure of 1 atm.
26. The system N2O4  2 NO2 maintained in a closed vessel at 60º C & a pressure of 5 atm has
an average (i.e. observed) molecular weight of 69, calculate Kp. At what pressure at the same
temperature would the observed molecular weight be (230/3) ?
27. The vapour density of N2O4 and NO2 mixture at a certain temperature is 30. Calculate the
percentage dissociation of N2O4 at this temperature. N2O4(g)  2NO2 (g)
Application of equilibrium constant (Heterogenuous equilibrium)

28. At 90°C, the following equilibrium is established :
H2(g) + S(s)  H2S(g) Kp = 6.8 × 10–2
If 0.2 mol of hydrogen and 1.0 mol of sulphur are heated to 90°C in a 1.0 litre vessel, what will
be the partial pressure of H2S at equilibrium?
29. The equilibrium constant for the reaction is 9 at 900°C S2(g) + C(s)  CS2(g). Calculate the
pressure of two gases at equilibrium, when 2 atm of S2 and excess of C(s) come to equilibrium.
30. A sample of CaCO3(s) is introduced into a sealed container of volume 0.821 litre & heated to
1000K until equilibrium is reached. The equilibrium constant for the reaction
CaCO3(s)  CaO(s) + CO2(g) is 4 × 10–2 atm at this temperature. Calculate the mass of CaO
present at equilibrium.
13 13
31. 20.0 grams of CaCO3(s) were placed in a closed vessel, heated & maintained at 727º C under
equilibrium CaCO3(s)  CaO(s) + CO2(g) and it is found that 75% of CaCO3 was
decomposed. What is the value of Kp? The volume of the container was 15 litres.
32. Consider the equilibrium

Ni(s) + 4CO(g)  Ni(CO)4(g) ; Kp = 0.125 atm–3.
If equal number of moles of CO and Ni(CO)4 (ideal gases) are mixed in a small container fitted
with a piston, find the maximum total pressure (in atm) to which this mixture must be brought
in order to just precipitate out metallic Ni ?
33. Anhydrous calcium chloride is often used as a dessicant. In the presence of excess of CaCl2,,
the amount of the water taken up is governed by Kp = 6.4 × 1085 for the following reaction at
room temperature, CaCl2(s) + 6H2O(g)  CaCl2 . 6H2O(s). What is the equilibrium vapour
pressure of water in a closed vessel that contains CaCl2(s) ?
34. Equilibrium constant for the following equilibrium is given at 0ºC.

Na2HPO4 . 12H2O (s)  Na2HPO4 . 7H2O (s) + 5H2O(g) KP = 31.25 × 10–13
At equilibrium what will be partial pressure of water vapour :
35. For the equilibrium CuSO4.5H2O(s)  CuSO4.3H2O(s) + 2H2O(g)

Kp = 2.25 × 10–4 atm2 and vapour pressure of water is 22.8 Torr at 298 K.
CuSO4.5H2O(s) is efflorescent (i.e., loses water) when relative humidity is :
Le-chatelier's principle
36. Consider the reaction, 2Cl2(g) + 2H2O(g)  4HCl(g) + O2(g) ; Hº = + 113 kJ
The four gases, Cl2, H2O, HCl and O2, are mixed and the reaction is allowed to come to
equilibrium. Each operation is to be considered separately. Temperature and volume are
constant unless stated otherwise. Report the number of operations in the left column which lead
to increase in the equilibrium value of the quantity in the right column.
(a) Increasing the volume of the container Number of moles of H2O
(b) Adding O2 Number of moles of H2O
(c) Adding O2 Number of moles of HCl
(d) Decreasing the volume of the container Number of moles of Cl2
(e) Decreasing the volume of the container Partial pressure of Cl2
(f) Decreasing the volume of the container KC
(g) Raising the temperature KC
(h) Raising the temperature Concentration of HCl
(i) Adding He Number of moles of HCl
(j) Adding catalyst Number of moles of HCl
14 14
37. Using Le Chatelier's principle, predict the effect of
(i) decreasing the temperature and
(ii) increasing the pressure on each of the following equilibria :
(A) N2(g) + 3H2(g)  2NH3(g) + Heat
(B) N2(g) + O2(g)  2NO(g) + Heat
(C) H2O(g) + Heat  H2 (g) + O2 (g)
(D) 2CO (g) + O2 (g)  2CO2 (g) + Heat
38. Suggest four ways in which the concentration of hydrazine, N2H4, could be increased in an
equilibrium described by the equation
N2 (g) + 2H2 (g)  N2H4 (g) H = 95 kJ
39. Find the direction of reaction if temperature is increased.

(a) 2NH3 (g)  N2 (g) + 3H2 (g) H = 92 kJ
(b) N2 (g) + O2 (g)  2NO (g) H = 181 kJ
(c) 2O3 (g)  3O2 (g) H = – 285 kJ
(d) CaO (s) + CO2 (g)  CaCO3 (s) H = – 176 kJ
40. (a) Methanol, a liquid fuel that could possibly replace gasoline, can be prepared from water
gas and additional hydrogen at high temperature and pressure in the presence of a
suitable catalyst. Write the expression for the equilibrium constant for the reversible
reaction.
2H2 (g) + CO (g)  CH3OH (g) H = – 90.2 kJ
(b) Assume that equilibrium has been established and predict how the concentration of
H2, CO and CH3OH will differ at a new equilibrium if (1) more H2 is added.
(2) CO is removed. (3) CH3OH is added. (4) the pressure on the system is increased.
(5) the temperature of the system is increased. (6) more catalyst is added.
41. (a) Water gas, a mixture of H2 and CO, is an important industrial fuel produced by the
reaction of steam with red-hot coke, essentially pure carbon. Write the expression for
the equilibrium constant for the reversible reaction.
C(s) + H2O (g)  CO (g) + H2 (g) H = 131.30 kJ
(b) Assume that equilibrium has been established and predict how the concentration of
each reactant and product will differ at a new equilibrium if (1) more C is added.
(2) H2O is removed. (3) CO is added. (4) the pressure on the system is increased.
(5) the temperature of the system is increased.
15 15
42. Ammonia is a weak base that reacts with water according to the equation
NH3 (aq) + H2O (l)  NH4+ + OH– (aq)
Will any of the following increase the percent of ammonia that is converted to the ammonium
ion in water?
(a) Addition of NaOH. (b) Addition of HCl. (c) Addition of NH4Cl.
43. Suggest two ways in which the equilibrium concentration of Ag+ can be reduced in a solution
of Na+, Cl–, Ag+ and NO3–, in contact with solid AgCl.
Na+ (aq) + Cl– (aq) + Ag+ (aq) + NO3– (aq)  AgCl (s) + Na+ (aq) + NO3– (aq) H = –65.9 kJ
44. Listed in the table are forward and reverse rate constants for the reaction
2NO(g)  N2(g) + O2(g)
Temperature (K) kf (M–1s–1) kb (M–1s–1)
1400 0.29 1.1 × 10–6
1500 1.3 1.4 × 10–5
Is the reaction endothermic or exothermic?
45. From the following data :

(i) H2(g) + CO2(g) H2O(g) + CO(g) ; K2000K = 4.4
(ii) 2H2O(g) 2H2(g) + O2(g) ; K2000K = 5.31 x 10–10
(iii) 2CO(g) + O2(g) 2CO2(g) ; K1000K = 2.24 x 1022
State whether the reaction (iii) is exothermic or endothermic?
46. The decomposition of solid ammonium carbamate, (NH4)(NH2CO2), to gaseous ammonia and
carbon dioxide is an endothermic reaction.
(NH4)(NH2CO2) (s)  2NH3 (g) + CO2(g)

(a) When solid (NH4) (NH2CO2) is introduced into an evacuated flask at 25°C, the total
pressure of gas at equilibrium is 0.3 atm. What is the value of Kp at 25°C ?
(b) Given that the decomposition reaction is at equilibrium, how would the following
changes affect the total quantity of NH3 in the flask once equilibrium is re-established ?
(i) Adding CO2 (ii) Adding (NH4) (NH2CO2)
(iii) Removing CO2 (iv) Increasing the total volume
(v) Adding neon (at constant volume) (vi) Increasing the temperature.
Simultaneous equilibria
47. For given simultaneous reaction :
X(s)  A(g) + B(s) + C(g) K P1 = 500 atm
Y(s)  D(g) + A(g) + E(s) KP2 = 2000 atm
Find total pressure at equilibrium.
16 16
48. When NO & NO2 are mixed, the following equilibria readily obtained;
2NO2  N2O4 Kp = 6.8 atm–1
NO + NO2  N2O3 Kp = ?
In an experiment when NO & NO2 are mixed in the ratio of 1 : 2, the total final pressure was
5.05 atm & the partial pressure of N2O4 was 1.7 atm. Calculate
(a) the equilibrium partial pressure of NO.
(b) Kp for NO + NO2 N2O3
49. NH4HS(s)  NH3(g) + H2S(g) K P1
NH3(g)  N2(g) + H2(g) KP2
2 mol NH4HS(s)is taken & 50% of this is dissociated till at equilibrium in 1 litre container.
K 2P2
Find , if 0.25 moles of N2 are found finally.
K 6P1
50. Consider : (I) C(s) + O2  CO2(g)

(II) 2 C(s) + O2  2 CO(g) atm
As 100 L of air (80 % N2, 20% O2 by volume) is pased over excess heated coke to establish
these equilibrium the equilibrium mixture is found to measure 105 L at constant temperature &
pressure (105 atm). Assuming no other reaction, find the sum of partial pressure of CO and
CO2 in the final equilibrium mixture.
17 17
EXERCISE # S-II
1. One mole of N2O4 (g) at 300 K is left in a closed container under one atm . It is heated to 600 K
when 20 % by mass of N2O4 (g) decomposes to NO2 (g) . Calculate resultant pressure.
2. Solid Ammonium carbamate dissociates as: NH2 COONH4 (s)  2NH3(g) + CO2(g).
In a closed vessel solid ammonium carbamate is in equilibrium with its dissociation products.
At equilibrium, ammonia is added such that the partial pressure of NH3 at new equilibrium now
equals the original total pressure. Calculate the ratio of total pressure at new equilibrium to that
of original total pressure.
3. A definite amount of solid NH4HS is placed in a flask already containing ammonia gas at a
certain temperature and 0.50 atm pressure. NH4HS decomposes to give NH3 and H2S and at
equilibrium total pressure in flask is 0.84 atm. Calculate equilibrium constant for the reaction :
4. For the reaction A(g) + 2B(g)  C(g) + D(g) ; Kc = 1012 .

If the initial moles of A,B,C and D are 0.5, 1, 0.5 and 3.5 moles respectively in a one litter
vessel. What is the equilibrium concentration of B?
5. A mixture of hydrogen & iodine in the mole ratio 1.5 : 1 is maintained at 450º C. After the
attainment of equilibrium H2(g) + I2(g)  2 HI(g), it is found on analysis that the mole ratio
of I2 to HI is 1 : 18. Calculate the equilibrium constant and the number of moles of each species
present under equilibrium, if initially, 127 grams of iodine were taken.
6. At certain temperature (T) for the gas phase reaction

2H2O(g) + 2Cl2 (g)  4HCl(g) + O2(g) Kp = 12 × 108 atm
If Cl2, HCl & O2 are mixed in such a manner that the partial pressure of each is 2 atm and the
mixture is brough into contact with excess of liquid water. What would be approximate partial
pressure of Cl2 when equilibrium is attained at temperature (T)?
[Given : Vapour pressure of water is 380 mm Hg at temperature (T)]
7. Two solids X and Y dissociate into gaseous products at a certain temperature as follows:
X(s)  A(g) + C(g), and Y(s)  B(g) + C(g). At a given temperature, pressure over excess
solid X is 40 mm and total pressure over solid Y is 60 mm. When they are preset in separate
containers. Calculate
(a) the values of Kp for two reactions (in mm)
(b) the ratio of moles of A and B in the vapour state over a mixture of X and Y.
(c) the total pressure of gases over a mixture of X and Y.
18 18
8. When 1 mole of A(g) is introduced in a closed rigid 1 litre vessel maintained at constant
temperature the following equilibria are established.
A (g)  B(g) + C(g) : KC1
C(g)  D(g) + B(g) : KC2
K C2 Ceq 1
The pressure at equilibrium is twice the initial pressure. Calculate the value of if =
K C1  Beq 5
9. Equilibrium constants are given (in atm) for the following reactions at 0° C:
SrCl2 × 6H2O(s)  SrCl2 × 2H2O (s) + 4H2O(g) Kp = 5 × 10–12
Na2HPO4 . 12 H2O(s)  Na2HPO4 . 7 H2O (s) + 5H2O(g) Kp = 2.43 × 10–13
Na2SO4 . 10 H2O(s)  Na2SO4 (s) + 10 H2O (g) Kp = 1.024 × 10–27
The vapor pressure of water at 0°C is 4.56 torr.
Out of SrCl2 × 2H2O (s), Na2HPO4 . 7 H2O (s) and Na2SO4 (s),
Which is the most effective drying agent at 0°C?
10. The value of Kp for the reaction at 270C

Br2(l) + Cl2(g)  2BrCl(g)
is ‘1 atm’. At equilibrium in a closed container partial pressure of BrCl gas is 0.1 atm and at
this temperature the vapour pressure of Br2(l) is also 0.1 atm. Then what will be minimum
moles of Br2(l) to be added to 1 mole of Cl2 , initially, to get above equilibrium situation ?
19 19
EXERCISE # O-I
Only one is correct
Properties of equilibrium and equilibrium constant
1. A chemical reaction is at equilibrium when
(A) Reactants are completely transformed into products
(B) The rates of forward and backward reactions are equal
(C) Formation of products is minimised
(D) Equal amounts of reactants and products are present
2. Which of the following statement is incorrect :

(A) At equilibrium, vapour pressure of solution and refractive index of equilibrium mixture
becomes constant.
(B) Equilibrium can be attained in both homogenous and heterogeneous reaction.
(C) At equilibrium concentration of reactants and products becomes constant and equal.
(D) Equilibrium is dynamic in nature
3. Concentrations of reactants and products at equilibrium can be like :
(A) (B) (C) (D) All of these

4. Rate of reaction curve for equilibrium can be like :

[rf = rate of forward, rb = rate of backward]
(A) (B)
(C) (D)
20 20
5. Initially the reactions in the container a & b are at equilibrium when the products & reactants
are put together in a container c then at the equilibrium the total number of different chemical
compounds are –
(A) 5 (B) 7 (C) 6 (D) 8
6. In a chemical equilibrium, the rate constant for the backward reaction is 2 × 10–4 and the
equilibrium constant is 1.5. The rate constant for the forward reaction is:-
(A) 2 × 10–3 (B) 5 × 10–4 (C) 3 × 10–4 (D) 9.0 × 10–4
7. The equilibrium constant for the reaction ;

N2(g) + O2(g)  2NO(g) at temperature T is 4 × 10–4. The value of equilibrium constant for
1 1
the reaction NO (g)  N2(g) + O2(g) at the same temperature is : –
2 2
(A) 0.02 (B) 50 (C) 4 × 10–4 (D) 2.5 × 10–2
8. The equilibrium constant for the given reaction :

1
SO3(g)  SO2(g) + O2(g) ; K = 5 × 10–2
2
The value of Kc for the reaction
2SO2(g) + O2(g)  2SO3(g), will be
(A) 400 (B) 2.40 × 10–3 (C) 9.8 × 10–2 (D) 4.9 × 10–2
9. For the following three reactions 1, 2 and 3, equilibrium constants are given :
(1) CO(g) + H2O(g)  CO2(g) + H2(g) ; K1
(2) CH4(g) + H2O(g)  CO(g) + 3H2(g) ; K2
(3) CH4(g) + 2H2O(g)  CO2(g) + 4H2(g) ; K3
Which of the following relations is correct ?
(A) K1 K 2 = K3 (B) K2K3 = K1 (C) K3 = K1K2 (D) K3·K23K12
21 21
10. Equilibrium constant for following reactions respectively K1, K2 and K3
N2 + 3H2  2NH3 K1
N2 + O2  2NO K2
1
H2 + O2  H2O K3
2
5
2NH3 + O2  2NO + 3H2O K4
2
Which of the following relation is incorrect.
K2 ×(K3 )3 K ×K K2 ×(K3 )3
(A) K1 = (B) K4 = K1 × K2/(K3)3 (C) K2 = 4 3 1 (D) K4 =
K4 (K3 ) K1
11. Sulfide ion in alkaline solution reacts with solid sulfur to form polysulfide ions having formulas
S22–, S32–, S42– and so on. The equilibrium constant for the formation of S22– is 12 ( K1) & for
the formation of S32– is 132 (K2), both from S and S2–.What is the equilibrium constant for the
formation of S32– from S22– and S?
(A) 11 (B) 12 (C) 132 (D) None of these
12. For a reaction N2 + 3H2  2NH3, the value of KC does not depends upon :-
(a) Initial concentration of the reactants (b) Pressure
(c) Temperature (d) Catalyst
(A) Only c (B) a, b, c (C) a, b, d (D) a, b, c, d
13. For any reversible reaction if concentration of reactants increases then effect on equilibrium
constant:-
(A) Depends on amount of concentration (B) Unchange
(C) Decrease (D) Increase
14. If some He gas is introduced into the equilibrium PCl5(g)  PCl3(g) + Cl2(g) at constant pressure
and temperature then equilibrium constant of reaction:
(A) Increase (B) Decrease (C) Unchange (D) Nothing can be said
15. 
The equilibrium constant for the reaction : N2(g) + O2(g)   2NO(g) at 2000 K is 4  10 In
4
presence of a catalyst the equilibrium is established ten times faster at the same temperature.
What is the value of equilibrium constant in presence of catalyst :
(A) 40  104 (B) 4  10–4 (C) 4  104 (D) 2.5 10–5
16. The equilibrium constant (Kc)for the reaction 2X(g) + 2Y(g)  2Z(g) is given as :
[2 X][2Y] [X][Y] [Z]2 [Z]2
(A) (B) (C) (D)
[2 Z] [Z] [X]2 [Y]2 [X][Y]
22 22
17. For the reaction
CuSO4.5H2O(s)  CuSO4.3H2O(s)+ 2H2O(g)
Which one is correct representation :–
(A) KP = P(H O)2 (B) Kc = [H2O]2 (C) Kp = Kc (RT)2 (D) All
2
18. 
For hypothetical equilibrium, 4A(g) + 5B(g)   4X(g) + 6Y(g)
The unit of KC will be :
(A) litre mole–1 (B) mole litre–1 (C) litre mole–2 (D) mole2 litre–2
19. What is the unit of KP for the reaction ?

CS2 (g) + 4H2 (g)  CH4 (g) + 2H2S (g)
(A) atm (B) atm–2 (C) atm2 (D) atm–1
20. The equilibrium concentration of B[(B)e]for the reversible reaction A  B can be evaluated
by the expression :–
(A) KC Ae
1 kf
(B) [A]e1 (C) kf kb1 [A]e (D) kfkb [A]–1
kb
21. For which reaction is Kp = Kc :–

(A) 2NOCl  2NO(g) + Cl2(g) (B) N2(g) + 3H2(g)  2NH3(g)
(C) H2(g) + I2(g)  2HI (g) (D) 2SO2(g) + O2(g)  2SO3(g)
KP
22. log + log RT = 0 is true relationship for the following reaction :
KC
(A) PCl5  PCl3 + Cl2 (B) 2SO2 + O2  2SO3
(C) N2 + 3H2  2NH3 (D) (B) and (C) both
Kp
23. For which reaction at 298 K, the value of will be maximum and minimum respectively :
Kc

(a) N2O4(g)  2NO2(g) 
(b) 2SO2(g) + O2(g)  2SO3(g)

(c) X(g) + Y(g)  4Z(g) 
(d) A(g) + 3B(g)  7C(g)
(A) d,c (B) d,b (C) c,b (D) d,a
24. For the following gases equilibrium. N2O4 (g)  2NO2 (g)
Kp is found to be equal to Kc. This is attained when temperature is
(A) 0°C (B) 273 K (C) 1 K (D) 12.19 K
23 23
Application of equilibrium constant (Homogeneous equilibrium)
25. When Kc >> 1 for a chemical reaction,
(A) the equilibrium would be achieved rapidly
(B) the equilibrium would be achieved slowly
(C) product concentrations would be much greater than reactant concentrations at equilibrium
(D) reactant concentrations would be much greater then product concentrations at equilibrium.
26. Equilibrium constant of some reaction are given as under ;


(a) x y K = 10–1

(b) y z K = 2 × 10–2

(c) P Q K = 3 × 10–4

(d) R  S K = 2 × 10–3
Initial concentration of the reactants for each reaction was taken be equal :
Review the above reaction and indicate the reactions in which the reactants and products
respectively were of highest concentration :
(A) d, c (B) c, a (C) a, d (D) b, c
27. What should be the value of Kc for the reaction 2SO2(g) + O2(g)  2SO3(g), if the amount are
SO3 = 48 g, SO2= 12.8 g and O2 = 9.6 g at equilibrium and the volume of the container is one
litre?
(A) 64 (B) 30 (C) 42 (D) 8.5
28. A certain quantity of PCl5 was heated in a 10 litre vessel at 250ºC. At equilibrium the vessel
contains 0.1 mole of PCl5 0.20mole of PCl3 and 0.2 mole of Cl2; The equilibrium constant of

the reaction PCl5(g)   PCl3(g) + Cl2(g) is :
(A) 0.02 (B) 0.05 (C) 0.04 (D) 0.025
29. 
PCl5(g)   PCl3(g) + Cl2(g)
In above reaction, at equilibrium condition mole fraction of PCl5 is 0.4 and mole fraction of Cl2
is 0.3. Then find out mole fraction of PCl3

PCl5(g)  PCl3(g) + Cl2(g)
(A) 0.3 (B) 0.7 (C) 0.4 (D) 0.6
30. In the reaction 2P(g) + Q(g)  3R(g) + S(g). If 2 moles each of P and Q taken initially in a 1
litre flask. At equilibrium which is true:-
(A) [P] < [Q] (B) [P] = [Q] (C) [Q] = [R] (D) None of these
24 24
31. 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 3a
(A) (B) (C) (D) All of the above.
4 2 4
32. The reaction A(g) + B(g)  C(g) + D(g) is studied in a one litre vessel at 250°C. The initial
concentration of A was 3n and that of B was n. When equilibrium was attained, equilibrium
concentration of C was found to the equal to the equilibrium concentration of B. What is the
concentration of D at equilibrium?
(A) n/2 (B) (3n – 1/2) (C) (n – n/3) (D) n
33. The figure show the change in concentration of species A and B as a fuctional of time . The
equilibrium constant KC for the reaction A(g)  2B (g) is :
(A) Kc > 1 (B) K < 1 (C) K = 1 (D) data insufficient
34. Kc = 9 for the reaction, A + B  C + D, If one mole of each A and B are taken, then amount
of C in equilibrium is :
(A) 1 (B) 0.25 (C) 0.75 (d) None of these
35. The equilibrium N2 (g) + O2 (g)  2NO (g) is estabilished in a reaction vessel of 2.5 L
capacity. The amounts of N2 and O2 taken at the start were respectively 2 moles and 4 moles.
Half a mole of nitrogen has been used up at equilibrium. The molar concentration of nitric
oxide is :
(A) 0.2 (B) 0.4 (C) 0.6 (D) 0.1
36. For the reaction 3 A (g) + B (g)  2 C (g) at a given temperature, Kc = 9.0 . What must be the
volume of the flask, if a mixture of 2.0 mol each of A , B and C exist in equilibrium ?
(A) 6L (B) 9L (C) 36 L (D) None of these
37. 
In the reaction A(g) + 2B(g)   2C(g) , if 2 mole of A, 3.0 moles of B and 2.0 moles of C
are placed in a 2L flask. If equilibrium concentration of C is 0.5 mole/L. The value of
equilibrium constant (KC) will be:
(A) 0.073 (B) 0.147 (C) 0.05 (D) 0.026
25 25
38. The equilibrium constant for the reaction
A(g) + 2B(g)  C(g)
is 0.25 dm6mol–2. In a volume of 5 dm3, what amount of A must be mixed with 4 mol of B to
yield 1 mol of C at equilibrium.
(A) 3 moles (B) 24 moles (C) 26 moles (D) None of these
39. A 20.0 litre vessel initially contains 0.50 mole each of H2 and I2 gases. These substances react
and finally reach an equilibrium condition. Calculate the equilibrium concentration of HI if
Keq = 49 for the reaction H2 + I2  2HI.
(A) 0.78M (B) 0.039 M (C) 0.033 M (D) 0.021 M
40. Equimolar concentrations of H2 and I2 are heated to equilibrium in a 2 litre flask. At equilibrium,
the forward and the backward rate constants are found to be equal, what percentage of initial

concentration of H2 has reacted at equilibrium for the reaction H2 + I2   2HI
(A) 33 % (B) 66 % (C) 50 % (D) 40 % (E) 20 %
41. When alcohol (C2H5OH (l)) and acetic acid (CH3COOH (l)) are mixed together in equimolar
ratio at 27ºC, 33% of each is converted into ester. Then the KC for the equilibrium
C2H5OH(l) + CH3COOH (l)  CH3COOC2H5 (l) + H2O(l) is :
(A) 4 (B) 1/4 (C) 9 (D) 1/9
42. In the reaction, PCl5  PCl3 + Cl2, the amount of each PCl5, PCl3 and Cl2 is 2 mole at
equilibrium and total pressure is 3 atmosphere. The value of Kp will be
(A) 1.0 atm. (B) 3.0 atm. (C) 2.9 atm. (D) 6.0 atm.
43. PCl5  PCl3 + Cl2 in the reversible reaction the moles of PCl5, PCl3 and Cl2 are a, b and c
respectively and total pressure is P then value of Kp is :

bc b bc.P c
(A) .RT (B) .P (C) (D) .P
a (a + b + c) a (a + b + c) (a + b + c)
44. The equilibrium constant, Kp for the reaction 2SO2(g) + O2(g)  2SO3(g) is 4.0 atm–1 at
1000 K. What would be the partial pressure of O2 if at equilibrium the amount of SO2 and SO3
is the same ?
(A) 16.0atm (B) 0.25 atm (C) 1 atm (D) 0.75 atm
45. For the reaction

A2(g) + 2B2  2C2(g)
the partial pressure of A2, B2 at equilibrium are 0.80 atm and 0.40 atm respectively. The
pressure of the system is 2.80 atm. The equilibrium constant Kp will be
(A) 20 (B) 5.0 (C) 0.02 (D) 0.2
26 26
46. N2 and H2 are taken in 1 : 3 molar ratio in a closed vessel to attained the following equilibrium
N2(g) + 3H2(g)  2NH3(g) . Find Kp for reaction at total pressure of 2P if PN2 at equilibrium
P
is
3
1 4 4P2 P
(A) (B) (C) (D)
3P2 3P2 3 3
47. A sample of pure NO2 gas heated to 1000 K decomposes : 2NO2(g)  2NO(g) + O2(g). The
equilibrium constant KP is 100 atm. Analysis shows that the partial pressure of O2 is 0.25 atm.
at equilibrium. The partial pressure of NO2 at equilibrium is:
(A) 0.03 (B) 0.25 (C) 0.025 (D) 0.04
48. The equilibrium constant KC for the reaction,

A(g) + 2B(g)  3C(g) is 2 × 10–3
What would be the equilibrium partial pressure of gas C if initial pressure of gas A & B are
1 & 2 atm respectively.
(A) 0.0625 atm (B) 0.1875 atm (C) 0.21 atm (D) None of these
49. At 675 K, H2(g) and CO2 (g) react to form CO(g) and H2O (g), Kp for the reaction is 0.16. If a
mixture of 0.25 mole of H2(g) and 0.25 mol of CO2 is heated at 675 K, mole % of CO(g) in
equilibrium mixture is :
(A) 7.14 (B) 14.28 (C) 28.57 (D) 33.33
[NH3 ]2
50. The reaction quotient Q for N2(g) + 3H2(g)  2NH3(g) is given by Q = . The
[N2 ][H2 ]3
reaction will proceed in backward direction, when

(A) Q = KC (B) Q < KC (C) Q > KC (D) Q = 10
51. N2O4(g)  2NO2(g), Kc = 4. This reversible reaction is studied graphically as shown in figure.
Select the correct statement.
(A) Reaction quotient has maximum value at point A

(B) Reaction proceeds left to right at a point when [N2O4] = [NO2] = 0.1 M
(C) Kc = Q when point D or F is reached :
(D) Both (B) and (C) are bcorrect
27 27
52. 2 mole each of SO3, CO, SO2 and CO2 is taken in a one lit. vessel. If KC for
SO3(g) + CO(g)  SO2(g) + CO2(g) is 1/9 then
(A) total no. of moles at equilibrium are less than 8
(B) n(SO3) + n(CO2) = 4
(C) [n(SO2)/n(CO)] < 1
(D) both (B) and (C).
53. A reaction mixture containing H2, N2 and NH3 has partial pressure 2 atm, 1 atm and 3 atm
respectively at 725 K. If the value of KP for the reaction, N2 + 3H2 2NH3 is 4.28  10–5 atm–2
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
Degree of dissociation ()

54. A3(g)  3A (g)
In the above reaction, the initial concentration of A3 is "a" moles/lit. If x is degree of
dissociation of A3. The total number of moles at equilibrium will be :
(A) a –
ax a
(B) – ax (C) 
 a  ax 
 (D) a + 2ax
3 3  2 
55. For the reaction : P  Q + R. Initially 2 moles of P was taken. Up to equilibrium 0.5 moles of
P was dissociated. What would be the degree of dissociation :-
(A) 0.5 (B) 1 (C) 0.25 (D) 4.2
56. 4 moles of PCl5 are heated at constant temperature in closed container. If degree of dissociation
for PCl5 is 0.5 calculate total number of moles at equilibrium :-

(A) 4.5 (B) 6 (C) 3 (D) 4
57. The degree of dissociation of SO3 is  at equilibrium pressure p0.

Kp for 2SO3(g)  2SO2(g) + O2(g)
p03 p0 3 p0 2
(A) (B) (C) (D) None of these
2 1     2   1   2 2 1   
3 2
58. For the reaction : 2Hl (g)  H2(g) + I2(g), the degree of dissociated () of Hl(g) is related to
equilibrium constant KP by the expression
2  2 Kp 1  2K p 2K p 2 Kp
(A) (B) (C) (D)
2 2 1  2K p 1 2 Kp
28 28
59. For the dissociation reaction N2O4(g)  2NO2(g), the degree of dissociation () in terms of Kp
and total equilibrium pressure P is:    
4p  Kp Kp Kp
(A)   (B)   (C)   (D) None of these
Kp 4p  Kp 4p
60. The degree of dissociation of PCl5 () obeying the equilibrium, PCl5 PCl3 + Cl2 , is
approximately related to the presure at equilibrium by (given  << 1) :
1 1 1
(A)  P (B)  (C) 2 (D)  4
P P P
61. For the reaction N2O4(g)  2NO2(g), if percentage dissociation of N2O4 are 20%, 45%, 65%
& 80%, then the sequence of observed vapour densities will be :
(A) d20 > d45 > d65 > d80 (B) d80 > d65 > d45 > d20
(C) d20 = d45 = d65 = d80 (D) (d20 = d45) > ( d65 = d80)
62. Two sample of HI, each of 5 gm. were taken separately into different vessels of volume 5 and
10 litres respectively at 27ºC . The extent of dissociation of HI will be :
(A) More in 5 litre vessel (B) More in 10 litre vessel
(C) Equal in both vessel (D) None of these
63. The vapour density of N2O4 at a certain temperature is 30. What is the % dissociation of N2O4
at this temperature?
(A) 53.3% (B) 106.6% (C) 26.7% (D) None
64. The equilibrium constant KP (in atm) for the reaction is 9 at 7 atm and 300 K.
A2 (g)  B2(g) + C2 (g)
Calculate the average molar mass (in gm/mol) of an equilibrium mixture.
Given : Molar mass of A2, B2 and C2 are 70, 49 & 21 gm/mol respectively.
(A) 50 (B) 45 (C) 40 (D) 37.5
65. Vapour density of the equilibrium mixture of the reaction

2NH3 (g)  N2 (g) + 3H2 (g) is 6.0
Percent dissociation of ammonia gas is:
(A) 13.88 (B) 58.82 (C) 41.66 (D) None of these
66. SO3(g)  SO2(g) + O2(g) ; If observed vapour density of mixture at equilibrium is 35 then
find out value of 
(A) 0.28 (B) 0.38 (C) 0.48 (D) 0.58
29 29
67. The degree of dissociation is 0.5 at 800 K and 2 atm for the gaseous reaction
PCl5  PCl3 + Cl2
Assuming ideal behaviour of all the gases.
Calculate the density of equilibrium mixture at 800 K and 2 atm.
(A) 4.232 g/L (B) 6.4 g/L (C) 8.4 g/L (D) 2.2 g/L
68. At 727°C and 1.23 atm of total equilibrium pressure, SO3 is partially dissociated into SO2 and
O2 according to SO3(g)  SO2(g) + 1/2O2(g). The density of equilibrium mixture is 0.9
g/litre. The degree of dissociation is:
(A) 1/3 (B)2/3 (C) l/4 (D) 1/5.
Application of equilibrium constant (Heterogenuous equilibrium)

69. On decomposition of NH4HS, the following equilibrium is established :
NH4HS(s)  NH3(g) + H2S (g)
If the total pressure is P atm, then the equilibrium constant KP is equal to
(A) P atm (B) P2 atm2 (C) P2 / 4 atm2 (D) 2P atm
70. What is the minimum mass of CaCO3 (s), below which it decomposes completely, required to
establish equilibrium in a 6.50 litre container for the reaction : CaCO3(s)  CaO(s) + CO2(g);
Kc = 0.05 mole/litre
(A) 32.5 g (B) 24.6 g (C) 40.9 g (D) 8.0 g
71. In the reaction C(s) + CO2(g)  2CO(g), the equilibrium pressure is 12 atm. If 50% of CO2
reacts then Kp will be :
(A) 12 atm (B) 16 atm (C) 20 atm (D) 24 atm
72. Solid ammonium carbamate dissociate to give ammonia and carbon dioxide as follows
NH2COONH4(s)  2NH3(g) + CO2(g)
which of the following graph correctly represents the equilibrium.
NH2COONH4(s) NH2COONH4(s)
8M NH2COONH4(s) 8M
8M 8M
7M 7M
7M 7M
6M
Conc.(mol/Lt.)
6M
Conc.(mol/Lt.)
Conc.(mol/Lt.)
6M
Conc.(mol/Lt.)
6M
NH3(g) 5M NH3(g)
5M 5M 5M
NH2COONH4(s) NH3(g)
4M 4M 4M
4M NH3(g)
(A) 3M
CO2(g)
(B) 3M (C) 3M
CO2(g)
(D) 3M
2M 2M 2M 2M
CO2(g) CO2(g)
1M 1M 1M 1M
1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5
Time (sec.) Time(sec.) Time (sec.) Time(sec.)
73. For NH4HS(s)  NH3(g) + H2S(g) reaction started only with NH4HS(s), the observed
pressure for reaction mixture in equilibrium is 1.2 atm at 106°C. What is the value of Kp for the
reaction ?
(A) 1.44 atm2 (B) 0.36 atm2 (C) 0.16 atm2 (D) 3.6 atm2
30 30
74. Consider the decomposition of solid NH4HS in a flask containing NH3(g) at a pressure of 2
atm. What will be the partial pressure of NH3(g) and H2S(g) after the equilibrium has been
attained ? KP for the reaction is 3.
(A) pNH3 = 4 atm, pH2S = 2 atm (B) pNH3 = 1.732 atm, pH2S = 1.732 atm
(C) pNH3 = 3 atm, pH2S = 1 atm (D) pNH3 = 1 atm, pH2S = 1 atm
Le-chatelier's principle
75. The equilibrium 2SO2(g) + O2(g)  2SO3(g) shifts forward if :–
(A) A catalyst is used.
(B) An adsorbent is used to remove SO3 as soon as it is formed.
(C) Small amounts of reactants are removed.
(D) None of these
76. In manufacture of NO, the reaction N2(g) + O2(g)  2NO(g), H +ve is favourable if :-
(A) Pressure is increased (B) Pressure is decreased
(C) Temperature is increased (D) Temperature is decreased
77. For the reaction PCl5  PCl3 + Cl2, the degree of dissociation varies inversely as the square
root of pressure of the system. Supposing at constant temperature If the volume is increased
16 times the intial volume, the degree of dissociation for this reaction will becomes :–
1 1
(A) 4 time (B) times (C) 2 time (D) times
4 2
78. In which of the following reactions, increase in the pressure at constant temperature does not
affect the moles at equilibrium :
1
(A) 2NH3(g)  N2(g) + 3H2(g) (B) C(g) + O2(g)  CO(g)
2
1
(C) H2(g) + O2(g)  H2O(g) (D) H2(g) + I2(g)  2HI(g)
2
79. Change in volume of the system does not alter the number of moles in which of the following
equilibrium
(A) N2(g) + O2(g)  2NO(g) (B) PCl5(g)  PCl3(g) + Cl2(g)
(C) N2(g) + 3H2(g)  2NH3(g) (D) SO2Cl2(g)  SO2(g) + Cl2(g)
80. Which of the following reaction will shift in backward direction. When the respective change is
made at equilibrium:
(A) N2(g) + 3H2(g)  2NH3(g) increase in pressure at eq.
(B) H2O(s)  H2O() addition of inert gas at constant volume
(C) PCl5(g)  PCl3(g) + Cl2(g) addition of inert gas at constant pressure
(D) CO2(g) + CaO(s)  CaCO3 increase in temperature
31 31
81. Consider the reactions
(i) PCl5(g)  PCl3(g) + Cl2(g)
(ii) N2O4(g)  2NO2(g)
The addition of an inert gas at constant volume
(A) will increase the dissociation of PCl5 as well as N2O4
(B) will reduce the dissociation of PCl5 as well as N2O4
(C) will increase the dissociation of PCl5 and step up the formation of NO2
(D) will not disturb the equilibrium of the reactions
82. The conditions favourable for the reaction :
2SO2(g) + O2(g)  2SO3(g) ; H° = – 198 kJ are :
(A) low temperature, high pressure (B) any value of T and P
(C) low temperature and low pressure (D) high temperature and high pressure
83. Densities of diamond and graphite are 3.5 and 2.3 gm/mL.
C (diamond) C (graphite) rH = –1.9 kJ/mole
favourable conditions for formation of diamond are
(A) high pressure and low temperature (B) low pressure and high temperature
(C) high pressure and high temperature (D) low pressure and low temperature
84. The equilibrium SO2Cl2(g)  SO2(g) + Cl2(g) is attained at 25°C in a closed rigid container
and an inert gas, helium is introduced. Which of the following statements is/are correct.
(A) concentrations of SO2, Cl2 and SO2Cl2 do not change
(B) more chlorine is formed
(C) concentration of SO2 is reduced
(D) more SO2Cl2 is formed
85. The yield of product in the reaction
2A(g) + B(g)  2C(g) + Q kJ

would be lower at :
(A) low temperature and low pressure (B) high temperature & high pressure
(C) low temperature and to high pressure (D) high temperature & low pressure
86. What is the effect of the reduction of the volume of the system for the equilibrium
2C(s) + O2(g)  2CO (g) ?
(A) The equilibrium will be shifted to the left by the increased pressure caused by the reduction
in volume.
(B) The equilibrium will be shifted to the right by the decreased pressure caused by the
reduction in volume.
(C) The equilibrium will be shifted to the left by the increased pressure caused by the increase
in volume.
(D) The equilibrium will be shifted to the right by the increased pressure caused by the
reduction in volume.
32 32
87. 2CaSO4(s)  2CaO(s) + 2SO2(g) + O2(g), H > 0
Above equilibrium is established by taking some amount of CaSO4(s) in a closed container at
1600 K. Then which of the following may be correct option.
(A) moles of CaO(s) will increase with the increase in temperature
(B) If the volume of the container is doubled at equilibrium then partial pressure of SO 2(g) will
change at new equilibrium.
(C) If the volume of the container is halved partial pressure of O2(g) at new equilibrium will
remain same
(D) If two moles of the He gas is added at constant pressure then the moles of CaO(s) will
increase.
88. For a system at equilibrium some changes are made which is reported by a graph (shown
below). Changes has been made at constant temperature.
Choose the correct options :
(A) (B)
(C) (D)
Physical Equlibrium
89. A liquid is in equilibrium with its vapour at its boiling point . On the average the molecules in
the two phases have equal :

(A) inter molecular forces (B) potential energy
(C) kinetic energy (D) none of these .
90. Au(s)  Au()

Above equilibrium is favoured at :
(A) High pressure low temperature (B) High pressure high temperature
(C) Low pressure, high temperature (D) Low pressure, low temperature
91. A gas 'X' when dissolved in water heat is evolved. Then solublity of 'X' will increase :
(A) Low pressure, high temperature (B) Low pressure, low temperature
(C) high pressure, high temperature (D) high pressure, low temperature
33 33
92. For an equilibrium H2O(s)  H2O() which of the following statements is true.
(A) The pressure changes do not affect the equilibrium
(B) More of ice melts if pressure on the system is increased
(C) More of liquid freezes if pressure on the system is increased
(D) The degree of advancement of the reaction do not depend on pressure
93. When the pressure is applied over system ice  water what will happen [USS]
(A) More water will form (B) More ice will form
(C) There will be no effect over equilibrium (D) Water will decompose in H2 and O2
94. Some quantity of water is contained in a container as shown in figure. As neon is added
to this system at constant pressure, the amount of liquid water in the vessel
(A) increases (B) decreases

(C) remains same (D) changes unpredictably
Simultaneous equilibria
95. The two equilibria, AB(aq)  A+(aq) + B (aq) and AB(aq) + B (aq)  AB2 (aq) are
  
simultaneously maintained in a solution with equilibrium constants, K1 and K2 respectively.

The ratio of concentration of A+ to AB2 in the solution is :
(A) directly proportional to the concentration of B– (aq.).
(B) inversely proportional to the concentration of B– (aq.).
(C) directly proportional to the square of the concentration of B– (aq.).
(D) inversely proportional to the square of the concentration of B– (aq.).
96. In the preceeding problem, if [A+] and [AB2] are y and x respectively, under equilibrium
produced by adding the substance AB to the solvents, then K1/K2 is equal to
y y2 (x + y) y2 (x + y) y
(A) (y – x)2 (B) (C) (D) (x – y)
x x x x
[Note: Use the information of the preceeding problem]
97. The reactions PCl5(g)  PCl3(g) + Cl2(g) and COCl2(g)  CO(g) + Cl2(g) are
simultaneously in equilibrium at constant volume. A few moles of CO(g) are 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
34 34
98. Consider the following two equilibria simultaneously established in a rigid vessel at a particular
temperature:
NH2COONH4(s)  2NH3 (g) + CO2(g)
CaCO3(s)  CaO(s) + CO2 (g)
Now, on adding some amount of NH3 to the reaction vessel, the orignal equilibrium is
disturbed and a new equilibrium state is obtained. On comparing the following at the initial &
final equilibrium states, select the CORRECT statement :
(A) Nothing can be said about the number of moles of CO2 gas in reaction vessel.
(B) Nothing can be said about the number of moles of NH3 gas in reaction vessel.
(C) Number of moles of NH3 gas would have definitely increased.
(D) Number of moles of CaCO3 solid gas would have definitely decreased.
35 35
EXERCISE # O-II
More than one may be correct
1. Following two equilibrium is simultaneously established in a container
PCl5(g)  PCl3(g) + Cl2(g)
CO(g) + Cl2(g)  COCl2(g)
If some Ni(s) is introduced in the container forming Ni (CO)4 (g) then at new equilibrium
(A) PCl3 concentration will increase (B) PCl3 concentration will decrease
(C) Cl2 concentration will remain same (D) CO concentration will remain same
2. For the reaction PCl5(g)  PCl3(g) + Cl2(g), 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) introducing PCl5 at constant volume.
3. When NaNO3 is heated in a closed vessel, oxygen is liberated and NaNO2 is left.
At equilibrium
(A) addition of NaNO2 favours reverse reaction
(B) addition of NaNO3 favours forward reaction
(C) increasing temperature favours forward reaction
(D) increasing pressure favours reverse reaction
4. For the gas phase reaction, C2H4 + H2  C2H6 (H = –32.7 kcal), carried out in a closed
vessel, the equilibrium moles of C2H4 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) removing some H2 (D) adding some C2H6
5. Phase diagram of CO2 is shown as following

73
Solid Liquid
67
P(atm) 5
1 Gas
195 217 298 304

T(K)
Based on above find the correct statement(s)

(A) 298K is the normal boiling point of liquid CO2
(B) At 1 atm & 190 K CO2 will exist as gas.
(C) CO2(s) will sublime above 195K under normal atmospheric pressure
(D) Melting point & boiling point of CO2 will increase on increasing pressure
36 36
6. The equilibrium between, gaseous isomers A, B and C can be represented as
Reaction Equilibrium constant
A (g)  B (g) : K1 = ?
B (g)  C (g) : K2 = 0.4
C (g)  A (g) : K3 = 0.6
If one mole of A is taken in a closed vessel of volume 1 litre, then
(A) [A] + [B] + [C] = 1 M at any time of the reactions
(B) Concentration of C is 4.1 M at the attainment equilibrium in all the reactions
1
(C) The value of K is
0.24
(D) Isomer [A] is least stable as per thermodynamics.
7. For the gas phase exothermic reaction, A2 + B2  C2, carried out in a closed vessel, the
equilibrium moles of A2 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) adding inert gas at constant pressure (D) removing some C2
8. Consider the equilibrium HgO(s) + 4I– (aq) + H2O () . HgI42– (aq) + 2OH– (aq), which changes
will decrease the equilibrium concentration of HgI42–
(A) Addition of 0.1 M HI (aq) (B) Addition of HgO (s)
(C) Addition of H2O (l) (D) Addition of KOH (aq)
9. Decrease in the pressure for the following equilibria : H2O (s)  H2O() result in the :
(A) formation of more H2O (s) (B) formation of more H2O()
(C) increase in melting point of H2O(s) (D) decrease in melting point of H2O(s)
Assertion Reason
10. Statement–1 : Total number of moles in a closed system at new equilibrium is less than the old
equilibrium if some amount of a substance is removed from a system
(consider a reaction A(g)  B(g) ) at equilibrium.
Statement–2 : The number of moles of the substance which is removed, is partially
compensated as the system reached to new equilibrium.
(A) Statement–1 is true, statement–2 is true and statement–2 is correct explanation for
statement–1.
(B) Statement–1 is true, statement–2 is true and statement–2 is NOT the correct explanation for
statement–1.
(C) Statement–1 is false, statement–2 is true.
(D) Statement–1 is true, statement–2 is false.
37 37
11. Statement–1 : Ammonia at a pressure of 10 atm and CO2 at a pressure of 20 atm are
introduced into an evacuated chamber. If Kp for the reaction
NH2COONH4 (s)  2NH3 (g) + CO2 (g) is 2020 atm3, the total pressure after a long time is
less than 30 atm.
Statement–2 : Equilibrium can be attained from both directions.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
Comprehension :
Paragraph for Question Nos. 12 to 15
In a 7.0 L evacuated chamber, 0.50 mol H2 and 0.50 mol I2 react at 427°C .
H2(g) + I2(g)  2HI(g). At the given temperature, KC = 49 for the reaction.
12. What is the value of Kp ?
(A) 7 (B) 49 (C) 24.5 (D) None
13 . What is the total pressure (atm) in the chamber?

(A) 83.14 (B) 831.4 (C) 8.21 (D) None
14. How many moles of the iodine remain unreacted at equilibrium?

(A) 0.388 (B) 0.112 (C) 0.25 (D) 0.125
15. What is the partial pressure (atm) of HI in the equilibrium mixture?

(A) 6.385 (B) 12.77 (C) 40.768 (D) 646.58
Paragraph for Question Nos. 16 to 18

Influence of pressure, temperature, concentration and addition of inert gas on a reversible

chemical reaction in equilibrium can be explained by formulating the expression for
equilibrium constant Kc or Kp for the equilibrium. On the other hand Le Chatelier principle can
be theoretically used to explain the effect of P, T or concentration on the physical or chemical
equilibrium both.
16. For the reaction : PCl5  PCl3 + Cl2 increase of pressure shows :
(A) An increase in degree of dissociation and a decrease in Kc
(B) A decrease in degree of dissociation and a decrease in Kc
(C) An increase in degree of dissociation but Kc remains constant
(D) A decrease in degree of dissociation but Kc remains constant
17. For the reaction : 2SO2 + O2  2SO3; H = –ve, An increase in temperature shows :
(A) More dissociation of SO3 and a decrease in Kc
(B) Less dissociation of SO3 and an increase in Kc
(C) More dissociation of SO3 and an increase in Kc
(D) Less dissociation of SO3 and an decrease in Kc
38 38
2
18. 
For the reaction : Fe3Yellow (aq.) + SCN–(aq).  Fe  NCS (aq.) ; in equilibrium if little
Red
more aqueous solution of FeCl3 is added, than :
(A) Forward reaction becomes more and red colours is deepened
(B) Backward reaction becomes more and red colour faintens
(C) Solution becomes colourless
(D) None of these
Match the column

19. Column I Column II
(A) KP < KC (P) N2 + 3H2  2NH3
(B) Introduction of inert gas at constant pressure (Q) PCl5 (g)  PCl3 (g) + Cl2 (g)
will decrease the concentration of reactants
(C) K°P is dimensionless (R) 2NO2 (g)  N2O4 (g)
(D) Temperature increase will shift (S) NH3 (g) + HI (g)  NH4I (s)
20. Column-I Column-II

(Reactions) (Favourable conditions)
(A) Oxidation of nitrogen (P) Addition of inert gas at constant
pressure
N2(g) + O2(g) + 180.5 kJ  2NO(g)
(B) Dissociation of N2O4(g) (Q) Decrease in pressure
N2O4(g) + 57.2 kJ  2NO2(g)
(C) Oxidation of NH3(g) (R) Decrease in temperature
4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
+ 905.6 kJ
(D) Formation of NO2(g) (S) Increase in temperature
NO(g) + O3(g) ......NO2(g) + O2(g) + 200 kJ
Matching list type

21. Column-I Column-II
(Reaction) (If a is negligiable w.r.t. 1, V = 1 litre)
(P) 2X(g)  Y(g) + Z(g) (1)  = 2 × Kc
(Q) X(g)  Y(g) + Z(g) (2) =3× Kc
(R) 3X(g)  Y(g) + Z(g) (3) = (2Kc)1/3
(S) 2X(g)  Y(g) + 2Z(g) (4) = Kc
Code:
P Q R S
(A) 4 1 3 2
(B) 2 4 1 3
(C) 1 4 2 3
(D) 2 3 1 4
39 39
EXERCISE # JEE-MAINS
1. One of the following equilibrium is not affected by change in volume of the flask
[AIEEE-2002]
(1) PCl5(g)  PCl3(g) + Cl2(g) (2) N2(g) + 3H2(g)  2NH3(g)
(3) N2(g) + O2  2NO(g) (4) SO2Cl2(g)  SO2(g) + Cl2(g)
1 Kp
2. Reaction CO(g) + O2(g)  CO2(g). The value of is – [AIEEE-2002]
2 Kc
1 1
(1) (B) RT (3) (4) RT
RT RT
3. Consider the reaction equilibrium [AIEEE–2003]

2SO2(g) + O2(g)  2 SO3(g) ; H° = – 198 kJ
On the basis of Le–Chatelier's principle, the condition favourable for the forward reaction is -
(1) Lowering the temperature and increasing the pressure
(2) Any value of temperature as well as pressure
(3) Lowering of temperature as well as pressure
(4) Increasing temperature as well as pressure
4. For the reaction equilibrium,

N2O4 (g)  2NO2(g) the concentration of N2O4 and NO2 at equilibrium are 4.8 × 10–2 and
1.2 × 10–2 mol L–1 respectively. The value of KC for the reaction is– [AIEEE-2003]
–3 –1 3 –1
(1) 3 × 10 mol L (2) 3 × 10 mol L
–1
2
(3) 3.3 × 10 mol L (4) 3 × 10–1 mol L–1
5. The equilibrium constant for the reaction

N2(g) + O2(g)  2NO(g) at temperature T is 4 × 10– 4. The value of KC for the reaction
1 1 1 1
NO(g)  N2(g) + O2(g)  N2(g) + O2(g) [AIEEE-
2 2 2 2
2003]
(1) 2.5 × 102 (2) 50 (3) 4 × 10– 4 (4) 0.02
6. What is the equilibrium expression for the reaction P4(s) + 5O2(g)  P4O10(s)?[AIEEE-2004]
(1) KC = [P4O10] / [P4] [O2]5 (2) KC = [P4O10] / 5 [P4] [O2]
5
(3) KC = [O2] (4) KC = 1 / [O2]5
Kp
7. For the reaction CO(g) + Cl2(g)  COCl2(g) the is equal to – [AIEEE-2004]
KC
1
(1) (2) RT (3) RT (4) 1.0
RT
40 40
8. For the reaction 2NO2(g)  2NO(g) + O2(g), (Kc = 1.8 × 10– 6 at 184° C) (R = 0.831 kJ(mol.K))
When Kp and kc are compared at 184°C it is found that [AIEEE-2005]
(1) KP is less than Kc
(2) Kp is greater than Kc
(3) Whether Kp is greater than, less than or equal to Kc depends upon the total gas pressure
(4) Kp = Kc
9. The exothermic formation of ClF3 is represented by the equation [AIEEE-2005]

Cl2(g) + 3F2(g)  2ClF3(g) ; Hr = – 329 kJ
Which of the following will increase the quantity of ClF3 in an equilibrium mixture of Cl2, F2
and ClF3?
(1) Removing Cl2 (2) Increasing the temperature
(3) Adding F2 (4) Increasing the volume of the container
10. A schematic plot of ln Keq verus inverse of temperature for a reaction is shown below.
The reaction must be [AIEEE-2005]
6.0
ln Keq
2.0
1.5×10–3 1/T(K–1) 2.0×10–3
(1) endothermic
(2) exothermic
(3) highly spontaneous at ordinary temperature
(4) one with negligible enthalpy change
11. Phosphorus pentachloride dissociates as follows, in a closed reaction vessel,

PCl5(g)  PCl3(g) + Cl2(g) [AIEEE-2006]
If total pressure at equilibrium of the reaction mixture is P and degree of dissociation of PCl5 is
x, the partial pressure of PCl3 will be–
 2x   x   x   x 
(1)  P (2)  P (3)  P (4)  P
 1 x   x 1   1 x   x 1 
1
12. The equilibrium constant for the reaction SO3(g)  SO2(g) + O2(g) is Kc = 4.9 × 10–2.
2
The value of Kc for the reaction [AIEEE-2006]
2SO2(g) + O2(g)  2SO3(g) will be
(1) 2.40 × 10–3 (2) 9.8 × 10– 2 (3) 4.9 × 10– 2 (4) 416
41 41
13. The equilibrium constants Kp1 and Kp2 for the reaction X  2Y and Z  P + Q, respectively
are in the ratio of 1 : 9. If the degree of dissociation of X and Z be equal then the ratio of total
pressure at these equilibria is [AIEEE-2008]
(1) 1 : 36 (2) 1 : 1 (3) 1 : 3 (4) 1 : 9
14. A vessel at 1000 K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted into
CO on the addition of graphite. If the total pressure at equilibrium is 0.8 atm, the value of K is:
[AIEEE-2011]
(1) 0.3 atm (2) 0.18 atm (3) 1.8 atm (4) 3 atm
15. The equilibrium constant (KC) for the reaction N2(g) + O2(g) 2NO(g) at temperature T is
4×10–4. The value of KC for the reaction. NO(g) ½N2(g) + ½O2(g) at the same
temperature is : [AIEEE-2012]
(1) 50.0 (2) 0.02 (3) 2.5 × 10 2
(4) 4 × 10–4
16. The value of Kp for the equilibrium reaction N2O4(g)  2NO2(g) is 2. The percentage
dissociation of N2O4(g) at a pressure of 0.5 atm is [JEE-MAINS(online)-12]
(1) 71 (2) 50 (3) 88 (4) 25
17. 8 mol of AB3(g) are introduced into a 1.0 dm3 vessel. If it dissociates as 2AB3(g)  A2(g) +
3B2(g) At equilibrium, 2mol of A2 are found to be present. The equilibrium constant of this
reaction is :- [JEE-MAINS(online)-12]
(1) 36 (2) 3 (3) 27 (4) 2
18. One mole of O2(g) and two moles of SO2(g) were heated in a closed vessel of one litre capacity
at 1098 K. At equilibrium 1.6 moles of SO3(g) were found. The equilibrium constant KC of the
reaction would be [JEE-MAINS(online)-12]
(1) 60 (2) 80 (3) 30 (4) 40
19. K1, K2 and K3 are the equilibrium constants of the following reactions (I), (II) and (III),
respectively [JEE-MAINS(online)-12]
(I) N2 + 2O2  2NO2
(II) 2NO2  N2 + 2O2
1
(III) NO2  N2 + O2
2
The correct relation from the following is :
1 1 1 1 1
(1) K1 = K 2 = K3 (2) K1 = = (3) K1 = = K3 (4) K1 = =
K2 K3 K2 K2  K 3 2
42 42
20. In reaction A + 2B  2C + D, initial concentration of B was 1.5 times of |A|, but at
equilibrium the concentrations of A and B became equal. The equilibrium constant for the
reaction is : [JEE-MAINS(online)-13]
(1) 4 (2) 6 (3) 12 (4) 8
21. N2(g) + 3H2(g)  2NH3(g), K1 (1) [JEE-MAINS(online)-13]

N2(g) + O2(g)  2NO(g), K2 (2)
1
H2(g) + O2(g)  H2O(g), K3 (3)
2
The equation for the equilibrium constant of the reaction
5
2 NH3(g) + O2(g)  2NO (g) + 3H2O(g), (K4)
2
in terms of K1, K2 and K3 is :
K K2 K K3 KK
(1) 1 3 (2) 2 3 (C) 1 2 (D) K1 K2 K3
K2 K1 K3
1
22. For the reaction SO2(g) + O2(g)  SO3(g) , if KP = Kc (RT)x where the symbols have usual
2
meaning then the value of x is : (assuming ideality) [JEE-MAINS-14]
1 1
(1) (2) 1 (3) –1 (4) –
2 2
23. For the decomposition of the compound, represented as [JEE-MAINS(online)-14]

NH2COONH4(s)  2NH3(g) + CO2(g)
the KP=2.9 × l0–5 atm3.
If the reaction is started with 1 mol of the compound, the total pressure at equilibrium would be
(1) 38.8 × 10–2 atm (2) 1.94 × 10–2 atm (3) 5.82 × 10–2 atm (4) 7.66 × 10–2 atm
24. The equilibrium constants at 298 K for a reaction A + B  C + D is 100. If the initial
concentration of all the four species were 1 M each, then equilibrium concentration of D
(in mol L–1) will be : [JEE-MAINS-16]
(1) 1.182 (2) 0.182 (3) 0.818 (4) 1.818
25. Which of the following lines correctly show the temperature dependence of equilibrium
constant, K, for an exothermic reaction ? [JEE-MAINS-18]
(1) A and D (2) A and B (3) B and C (4) C and D

43 43
26. Consider the following reversible chemical reactions : [JEE-MAINS(Jan)-19]
A2(g) + B2(g) 2AB(g) .....(1)
6AB(g) 3A2(g) + 3B2(g) .....(2)
1
(1) K1K2 = 3 (2) K2 = K1–3 (3) K2 = K13 (4) K1K2 =
2
27. The value of Kp/KC for the following reactions at 300 K are, respectively :
(At 300 K, RT = 24.62 dm3 atm mol–1) [JEE-MAINS(Jan)-19]
N2(g) + O2(g)  2NO(g)
N2O4(g)  2NO2(g)
N2(g) + 3H2(g)  2NH3(g)
(1) 24.62 dm3 atm mol–1
606.0 dm6 atm2 mol–2
1.65 × 10–3 dm–6 atm–2 mol–2
(2) 1, 4.1 × 10–2 dm–3 atm–1 mol,
606.0 dm6 atm2 mol–2
(3) 1, 24.62 dm3 atm mol–1,
606.0 dm6 atm2 mol–2,
(4) 1, 24.62 dm3 atm mol–1,
1.65 × 10–3 dm–6 atm–2 mol2.
28. 5.1g NH4SH is introduced in 3.0 L evacuated flask at 327°C. 30% of the solid NH4SH
decomposed to NH3 and H2S as gases. The Kp of the reaction at 327°C is (R = 0.082 L atm
mol–1K–1, Molar mass of S = 32 g mol/–1, molar mass of N = 14 g mol–1)

[JEE-MAINS(Jan)-19]
–4 –4
2
(1) 0.242 × 10 atm (2) 0.242 atm 2
(3) 1 × 10 atm 2
(4) 4.9 × 10–3 atm2
29. Consider the reaction, [JEE-MAINS(Jan)-19]


N2 (g)  3H2 (g)  2NH3 (g)
The equilibrium constant of the above reaction is KP. If pure ammonia is left to dissociate, the
partial pressure of ammonia at equilibrium is given by (Assume that PNH3  Ptotal at
equilibrium)
3 1 1 1 3 1
2 2 2
2
3 K P 2
P K P 2
P K P 2
P 3 K P2
2 2
P
(1) (2) (3) (4)
4 16 4 16
44 44
30. Two solids dissociate as follows [JEE-MAINS(Jan)-19]
The total pressure when both the solids dissociate simultaneously is :-
(1) x2 + y2 (2) 2  x  y atm (3) (x + y) atm (4) x  y atm
31. In a chemical reaction, A + 2B 2C + D, the initial concentration of B was 1.5 times of

the concentration of A, but the equilibrium concentrations of A and B were found to be equal.
The equilibrium constant(K) for the aforesaid chemical reaction is : [JEE-MAINS(Jan)-19]
1
(1) (2) 4 (3) 16 (4) 1
4
32. For the following reactions, equilibrium constants are given : [JEE-MAINS(Apr.)-19]
S(s) + O2(g)  SO2(g); K1 = 10 52
2S(s) + 3O2(g)  2SO3(g); K2 = 10129

The equilibrium constant for the reaction,
2SO2(g) + O2(g)  2SO3(g) is :
(1) 1025 (2) 10154 (3) 10181 (4) 1077
Ans. (1)
33. For the reaction, 2SO2(g) + O2(g)  2SO3(g), H = –57.2 kJ mol–1 and KC = 1.7×1016.Which
of the following statement is INCORRECT ? [JEE-MAINS(Apr.)-19]

(1) The equilibrium constant is large suggestive of reaction going to completion and so no
catalyst is required.
(2) The addition of inert gas at constant volume will not affect the equilibrium constant.
(3) The equilibrium constant decreases as the temperature increases.
(4) The equilibrium will shift in forward direction as the pressure increases.
34. In which one of the following equilibria, Kp ≠ Kc ? [JEE-MAINS(Apr.)-19]

(1) 2HI(g)  H2(g) + I2(g) (2) NO2(g) + SO2(g)  NO(g) + SO3(g)
(3) 2C(s) + O2(g)  2CO(g) (4) 2NO(g)  N2(g) + O2(g)
45 45
EXERCISE # JEE-ADVANCED
1. The degree of dissociation is 0.4 at 400K & 1.0 atm for the gasoeus reaction
PCl5  PCl3 + Cl2(g). Assuming ideal behaviour of all gases. Calculate the density of
equilibrium mixture at 400K & 1.0 atm pressure. [JEE 1999]
2. For the reversible reaction : [JEE 2000]

–5
N2(g) + 3H2(g)  2NH3(g) at 500°C. The value of Kp is 1.44 × 10 , when partial pressure is
measured in atmospheres. The corresponding value of Kc with concentration in mol L–1 is :
(A) 1.44 × 10–5 /(0.082 × 500)2 (B) 1.44 × 10–5 /(8.314 × 773)2
(C) 1.44 × 10–5 /(0.082 × 500)2 (D) 1.44 × 10–5 /(0.082 × 773)–2
3. When two reactants A and B are mixed to give products C and D, the reaction quotient Q, at
the initial stages of the reaction : [JEE 2000]
(A) is zero (B) decrease with time
(C) independent of time (D) increases with time
4. When 3.06g of solid NH4HS is introduced into a two litre evacuated flask at 27°C, 30% of the
solid decomposes into gaseous ammonia and hydrogen sulphide. [JEE 2000]
(i) Calculate KC & KP for the reaction at 27°C.
(ii) What would happen to the equilibrium when more solid NH4HS is introduced into the
flask?
5. At constant temperature, the equilibrium constant (KP) for the decomposition reaction.
N2O4  2NO2 is expressed by KP = 4x2P/(1 – x2) where P is pressure, x is extent of

decomposition.
Which of the following statement is true ? [JEE 2001]
(A) KP increases with increase of P (B) KP increases with increase of x
(C) KP increases with decrease of x (D) KP remains constant with change in P or x
6. Consider the following equilibrium in a closed container : N2O4(g)  2NO2(g).

At a fixed temperature, the volume of the reaction container is halved. For this change, which
of the following statements holds true regarding the equilibrium constant (KP) and degree of
dissociation () : [JEE 2002]
(A) Neither KP nor  changes (B) Both KP and  change
(C) KP changes, but  does not change (D) KP does not change, but  changes
46 46
7. If Ag+ + NH3  [Ag(NH3)]+ ; K1 = 1.6 × 103 and [JEE 2006]
[Ag(NH3)] + NH3  [Ag(NH3)2] ; K2 = 6.8 × 10 .
+ + 3
The formation constant of [Ag(NH3)2]+ is :

(A) 6.08 × 10–6 (B) 6.8 × 10–6 (C) 1.6 × 103 (D) 1.088 × 107
8. The thermal dissociation equilibrium of CaCO3(s) is studied under different conditions.

CaCO3(s)  CaO(s) + CO2(g) [JEE 2013]
For this equilibrium, the correct statement(s) is(are)
(A) H is dependent on T
(B) K is independent of the initial amount of CaCO3
(C) K is dependent on the pressure of CO2 at a given T
(D) H is independent of the catalyst, if any
9. For the following reaction, the equilibrium constant KC at 298 K is 1.6 × 1017.

Fe2+ (aq) +S2–(aq)  FeS (s) [JEE Advanced-2019]
2+ 2–
When equal volumes of 0.06 M Fe (aq) and 0.2 M S (aq) solutions are mixed, the
equilibrium concentration of Fe2+(aq) is found to be Y × 10–17 M. The value of Y is________
47 47
ANSWER KEY
EXERCISE # S-I
1. (a) 25, shifts left, (b) 0.22, shifts right, (d) 1, shifts right, (e) 0, shift right
(b) 2NH3  N2 + 3H2
3 atm 2 atm 1 atm
Qp = 2/9 < Kp
 shifts in forward direction
2. K about 10 3. 250
–22
4. 6 × 10 5. (i) 2; (ii) 1.2 mol/L
9
6. 2 × 10 7. PCIF = PF2 = 0.1 atm, PClF3 = 05 atm
8. 0.9 9. KC = 100
10. Kp = 0.2463 11. (a) incomplete (b) almost complete
–32
12. 64 × 10 13. 2.4 mole
14. The reaction is not an equilibrium because Qc > Kc. The reaction will proceed from right to left
to reach equilibrium
15. Forward reaction. 16. 5.9 × 10–3 M
17. [NO] = 2M, [N2] = [O2] = 0.5M 18. [PCl3] = [Cl2] = 0.027 M, [PCl5] = 0.073
19. [A] = 0.34 M, [B] = 1.16 M, [C] = 1.16 M 20. KP = 0.4, a ~ 0.1
21. 50% 22. Kp = 0.01 atm
–3 –1
23. (a) 6.667 × 10 mol L ; (b) n (N2O4)=0.374 mol; n (NO2)=0.052 mol ; (c) 10.49 atm (d)
6.44 %
24. 0.97 atm 25. 2.7 g / lit
26. Kp= 2.5 atm, P = 15 atm 27. 53.33%

28. 0.379 atm
29. PCS2 = 1.8 atm, PS2 = 0.2 atm 30. 22.4 mg
31. 0.821 atm 32 4
–15
33. P = 5 × 10 atm 34. 5 × 10–3 atm.
35. Less than 50 %
36 5 (a) decrease (b) increase (c) decrease (d) increase (e) increase
(f)no change (g) increase (h) increase (i) no change (j) no change
37. (i) When decreasing temperature
(a) Forward (b) Forward (c) Backward (d) Forward
(ii) Increasing the pressure
(a) Forward (b) No change (c) Backward (d) Forward
48 48
38. add N2, add H2, increase the pressure , heat the reaction
39. (a) shift right (b) shift right (c) shift left (d) shift left
40. (a) K = [CH3OH]/[H2]2[CO] ,
(b) 1. [H2] increase, [CO] decrease, [CH3OH] increase ; 2. [H2] increase, [CO] decrease,
[CH3OH] decrease ; 3. [H2] increase, [CO] increase, [CH3OH] increase ; 4. [H2] increase, [CO]
increase,[CH3OH] increase ; 5. [H2] increase, [CO] increase, [CH3OH] decrease ; 6. no change
41. (a) K = [CO][H2]/[H2O] ;

(b) in each of the following cases the mass of carbon will change, but its concentration
(activity) will not change. 1. [H2O] no change, [CO] no change, [H2] no change ; 2. [H2O]
decrease, [CO] decrease, [H2] decrease ; 3. [H2O] increase, [CO] increase, [H2] decrease; 4.
[H2O] increase, [CO] increase, [H2] increase ; 5. [H2O] decrease , [CO] increase , [H2] increase
42. 2
43. Add NaCl or some other salt that produces Cl– in the solution. Cool the solution.
44. kr increase more than kf, this means that Ea (reverse) is greater than Ea (forward). Hence
exothermic reaction.
45. Exothermic
46. (a) 4 × 10–3 (b) (i) decrease (ii) no change (iii) increase (iv) increase (v) no change (vi)
increase
47. 100 48. (a) 1.05 atm, (b) 3.43 atm–1
49. 27 50. 15
EXERCISE # S-II
1. 2.4 atm 2. 31/27
3. 0.11 4. 2 × 10–4
5. Kc=54, nHI=0.9 mol, nI2= 0.05 mol, nH2 = 0.3 mol
6. 3.6 × 10–3 atm
7. (a) 400mm2, 900mm2 (b) 4: 9, (c) 72.15 mm Hg
8. 4 9. SrCl2 × 2H2O
15
10.
6
49 49
EXERCISE # O-I
1. (B) 2. (C) 3. (D) 4. (A) 5. (D) 6. (C) 7. (B)
8. (A) 9. (C) 10. (B) 11. (A) 12. (C) 13. (B) 14. (C)
15. (C) 16. (C) 17. (D) 18. (B) 19. (B) 20. (C) 21. (C)
22. (B) 23. (B) 24. (D) 25. (C) 26. (B) 27. (B) 28. (C)
29. (A) 30. (A) 31. (B) 32. (A) 33. (A) 34. (C) 35. (B)
36. (A) 37. (D) 38. (C) 39. (B) 40. (A) 41. (B) 42. (A)
43. (C) 44. (B) 45. (A) 46. (B) 47. (C) 48. (B) 49. (B)
50. (C) 51. (D) 52. (D) 53. (B) 54. (D) 55. (C) 56. (B)
57. (B) 58. (D) 59. (B) 60. (B) 61. (A) 62. (C) 63. (A)
64. (C) 65. (C) 66. (A) 67. (A) 68. (B) 69. (C) 70. (A)
71. (B) 72. (C) 73. (B) 74. (C) 75. (B) 76. (C) 77. (A)
78. (D) 79. (A) 80. (D) 81. (D) 82. (A) 83. (C) 84. (A)
85. (D) 86. (A) 87. (B) 88. (B) 89. (C) 90. (C) 91. (D)
92. (B) 93. (A) 94. (B) 95. (D) 96. (A) 97. (C) 98. (D)
EXERCISE # O-II
1. (B) 2. (C,D) 3. (C,D) 4. (A,B,C,D)

5. (C,D) 6. (A,C,D) 7. (A,B,C) 8. (C,D)
9. (A,C) 10. (B) 11. (D) 12. (B)
13. (C) 14. (B) 15. (A) 16. (D)
17. (A) 18. (A)
Match the column :
19. (A)-P,R,S; (B)-P,Q,R,S; (C)-P,Q,R,S; (D)-Q;

20. (A)-S; (B)-P,Q,S; (C)-P,Q,R; (D)-R 21. (C)
EXERCISE # JEE-MAINS
1. (3) 2. (3) 3. (1) 4. (1) 5. (2) 6. (4) 7. (1)
8. (2) 9. (3) 10. (2) 11. (4) 12. (4) 13. (1) 14. (3)
15. (1) 16. (1) 17. (3) 18. (2) 19. (4) 20. (1) 21. (2)
22. (4) 23. (3) 24. (4) 25. (2) 26. (2) 27. (4) 28. (2)
29. (4) 30. (2) 31. (2) 32. (1) 33. (1) 34. (3)
50 50
EXERCISE # JEE-ADVANCED
1. 4.54 g dm–3 2. (D) 3. (D)
4. (i) Kc= 8.1 × 10–5 mol2 L2 ; Kp = 4.91 × 10–2 atm2 (ii) No effect;
5. (D) 6. (D) 7. (D) 8. (ABD) 9. 8.92 or 8.93
51 51
SOLUTION : CHEMICAL EQUILIBRIUM
EXERCISE # S-I
11 1
1. (a) QC = 2
= = 25
(0.2) 0.04
QC > KC , backward shift
2  (1)2 2
(b) QP = 2
=
(3) 9
QP < KP , forward shift
11
(c) QP = =
1
QP < KP , forward shift
(d) Since initially only reactants are present, so reaction will shift to forward
2. If K is large. Then tendency of reaction to convert in product will be more
Kf
3. KC =
Kb
Kf
4. KC =
Kb
5. (i) Amount if  formed = 2 × amount of A reacted

 n=2
 2B
(ii) A 
[B]2 (0.6) 2
K= = = 1.2
[A] 0.3
6.  2NO(g)
N2(g) + O2(g)  KC = 0.5×10–9
 N2(g) + O2(g) 1

2NO  KC = 9
= 2×109
0.5 10
7.  ClF(g) + F2(g)

ClF3(g) 
Pi 0.15 0 0
Peq 0.15 – x x x
x2
0.2 =
0.15  x
x = 0.01
8.  PCl3 (g) + Cl2 (g)
PCl5 (g) 
Ceq 0.5×10–3 1.5×10–2 3×10–2
1.5 102  3 102
KC = = 0.9
0.5 103
9.  2HI(g)
H2(g) + I2(g) 
Ci 0 0 4.8×10–3
–3
Ceq 0.4×10 0.4×10–3 4×10–3
(4 103 )2
KC = = 100
0.4 103  0.4 103
10. KP = PH O = 0.2463
2
KP = KC(RT)2
0.2463
KC = = 0.01
0.0821 300
11. If KC is very large, extent of reaction is almost 100%.
12.  2O3 (g) KC = 8×10–55

3O2 (g) 
Ceq 8×10–3 x
x2
8×10–55 =
(8 103 )3
x2 = 8×10–55 × (8)3 × 10–9
x2 = (8)4 × 10–64
x = 64 × 10–32
13.  2C
A + B 
ni 2 3 0
neq 2–x 3–x 2x
4x 2
4=
(2  x)(3  x)
x = 1.2
14.  CS2(g) + 4H2(g)

CH4(g) + 2H2S(g) 
3 4 3 3
0.3  (0.3) 4
QC =
0.3  (0.4) 2
8110 4 81
= 2
= ×10–2
16 10 16
15.  CO(g) + 3H2(g)
H2O(g) + CH4(g) 
0.03 M 0.05 M 0.15 M 0.2 M
0.15  (0.2) 3
QC = = 0.8
0.03  0.05
QC < KC , forward shift
16. N2(g) +  2NH3(g)

3H2(g) 
0.036 M 0.15 M x
2
x
0.29 =
0.036  (0.15)3
x = 5.9×10–3
17.  2NO(g)

N2(g) + O2(g) 
Ci 1.5 1.5 0
Ceq 1.5–x 1.5–x 2x
(2x) 2
KC = = 16
(1.5  x)(1.5  x)
2x
=4
(1.5  x)
x=1
18.  PCl3(g) + Cl2(g)

PCl5 (g) 
Ci 0.1 0 0
Ceq 0.1–x x x
x2
= 10–2
0.1  x
x = 0.027
2 2
19. KC = =4
1
 B(g) + C(g)
A(g) 
Ceq 0.5–x 1+x 1+x
(1  x) 2
=4
0.5  x
x = 0.16
4 2
20. KP = .P
1  2
 
2
4  14 4 2
2 × 1.5 = × 10
    2
1 41 1
4  0.01
= ×10 = 0.4
1  0.01
21.  2NO2(g)

N2O4 (g) 
2 4 2 1
= ×
3 1  2
2
 2
1
=
1  2 3
42 = 1
1
2 =
2
22.  2NO(g) + Br2(g)

2NOBr(g) 
ni a 0 0
2a a a
neq
3 3 6
Peq 0.16 0.8 0.4
(0.8) 2  0.4
KP = = 0.1
(0.16) 2
(0.1) 2 4
24. KP = ×4=
1  (0.1) 2
99
1
25 × P = 4
1  1 25 99
96
P= = 0.97 atm
99
25.  PCl3(g) + Cl2(g)

PCl5 (g) 
2
KP = ×P
1  2
2
0.178 = ×1
1  2
 = 0.8
208.5
Mmix = = 115.83
1.8
1115.83
d= = 2.7 g/L
0.0821 523
92
26. 69 =
1 
1
=
3
4 1 4
9 ×5 = 9 ×5
KP =
1  19 8
9
20
= = 2.5
8
230 92
=
3 1 
 = 0.2
1 4
20
= 25 .P
8 1  125
P = 15 atm
46
27. 30 =
1 
46
1+=
30
 = 0.53
28. KP = KC
 H2S(g)
H2(g) + S(s) 
ni 0.2 1 0
neq 0.2–x 1–x x
x
6.8×10–2 =
0.2  x
x = 0.0127
29.  CS2(g)

S2(g) + C(s) 
Pi 2 0
Peq 2–x x
x
=9
2x
11x = 18
18
x=
11
30.  CaO(s) + CO2(g)
CaCO3(s) 
KP + PCO = 4×10–2
2
4 102  0.521
n CO2 =
0.0821 1000
= 4×10–4
nCaO = n CO = 4×10–4
2
WCaO = 4×10–4× 56 g
= 0.4×56 g
= 22.4 mg
31.  CaO(s) + CO2(g)

CaCO3(s) 
neq 0.2×0.75
0.2  0.75  0.0821 1000
KP = PCO = 2
15
KP = 0.821
32.  NiCO(g)

Ni(s) + 4CO(g) 
x x
x
= 0.125
x4
1
= 0.125
x3
x=2
PT = 4 atm
1
33. KP = = 6.4×1085
(PH2O )6
1 1
(PH2O )6 = = 10–85 = ×10–84
6.4 64
1
PH2O = ×10–14 = 5×10–15
2
34. KP = (PH O )2 = 2.25×10–4

2
PH2O = 15×10–3 = 1.5×10–2

1.5 102
R.H. = ×760×100
22.8
= 50 %
If RH < 50% reaction will shift forward
36. (a) Forward shift

No of moles of H2O will decrease
(b) For ward shift  moles of H2O will decrease
(c) Forward shift  moles of HCl will increase
(d) Backward shift  moles of Cl2 will increase
(e) Backward shift  partical pressure of each goes will increase
(f) No change
(g) H > 0, T, KC
(h) T, forward shift [HCl]
(i) At constant volume – no change
37. On increasing temperature reaction will shift towards endothermic direction and on increasing
pressure reaction will more towards lesser number of gaseous moles.
38. Decreasing volume of container

Increasing temperature
Addition of N2
Addition of H2
40. (b)
(i)  CH3OH (g)
2H2(g) + CO(g) 
conc.    
(ii) conc.    
 (iii) conc.   
(iv) conc.   
(v) conc.    
0.29
44. Keq at 1400 K =
1.1106
2.9
= × 105
1.1
= 2.6×105
1.3
Keq at 1500 K =
1.4 105
1.3
= × 105
1.4
= 0.92×105
T, Keq e×0
45. Keq at 2000 K
(iii) = –[2(i) + (ii) ]
1
K=
(4.4)  5.311010
2
1010
=
(4.4)2  5.31
Keq at 1000 K
K = 2.24 × 22
T, K e×0
47.  A(g) B(s) + C(g)

X(s) 
P1 + P2 P1
 D(g) + A(s) + E(s)
Y(s) 
P2 P2 + P1
P1 (P1 + P2) = 500
P2 (P1 + P2) = 2000
P1 + P2 = 50
P1 = 2×50 = 100 atm
49.  NH3(g) + H2S (g)

NH4HS(s) 
1–x 1
  N2(g) + 3 H2(g)
NH3(g) 
2 2
x 3x
1–x
2 2
x
= 0.25  x = 0.5
2
EXERCISE # S-II
1. N2O4(g)  2 NO2(g)
ni 1 0
neq 0.8 0.4
P1 P
 2
n1T1 n 2T2
1 P2

1 300 1.2  600
P2 = 1.2 × 2
= 2.4 atm
2. NH2COONH4 (s)  2 NH3(g) + CO2(g)

nI, eq 2P P
nII, eq 3P P1
2 1 2
(3P) × P = (2P) × P
4P
P1 =
9
(PT )II,eq 31

(PT )I,eq 27
3. NH4HS (s)  NH3(g) + H2S(g)

0.5 + P P
0.5 + 2P = 0.84
P = 0.17
Kp = 0.67 × 0.17
= 0.1139
4. A(g) + 2B(g)  C(g) + D(g)

ni 0.5 1 0.5 3.5
neq x 2x 1 4
1 4
1012 =
4x3
–12
3
x = 10  x = 10–4
[B] = 2 × 10–4
5. H2(g) + I2(g)  2HI(g)

ni 1.5a a 0
neq 1.5 a–x a–x 2x
ax 1

2x 18
x = 0.9a
1.8 1.8
KC = = 54
0.6  0.1
6. 2H2O (g) + 2Cl2(g)  4HCl(g) + O2(g)
pi 2 2 2 2
peq 0.5 x 6 3
64  3
12 × 108 =
(0.5)2  x 2
x = 3.6 × 10–3
7. X(s)  A(g) + C(g) K P1 = 400

P1 P1 + P2
Y(s)  B(g) + C(g) KP2 = 900
P2 P1 + P2
(a) P1(P1 + P2) = 400 P2(P1 + P2) = 900
P1 + P2 = 10 13
n A PA 4
(b)  
n B PB 9
(c) PT = 2(P1 + P2) = 20 13 atm
8. A(g)  B(g) + C(g)

1–x x+y x–y
C(g)  D(g) + B(g)
x–y y y+x
nT at eq = 1 – x + x + y + x–y+y
=1+x+y
pi 1 ni 1 1
  
peq 2 n eq 1  x  y 2
1+x+y=2
[C]eq x  y 1
   5x – 5y = x + y
[B]eq x  y 5
4x = 6y
y = 0.4
x = 0.6
0.4 1
KC2
 0.5  4
KC1 1 0.2
0.4
EXERCISE # O-I
3. At equilibrium conc. Becomes constant.
4. rf = rb
5. NH3, ND3, NH2D, NHD2, N2, H2, H-D, D2
Kf
6. Keq =
Kb
1
7. K2 =
1
(K1 )
2
1
8. K2 =
K12
9. K3 = K1 × K2
(iii) = (i) + (ii)
11. S + S2–  S22– K1 – 12

2S + S2–  S32– K2 = 132
S + S22–  S32– K3
(iii) = (ii) – (i)
K
K3 = 2
K1
12. KC depends only only on temp
ng
 mol 
18. KC =  
 L 
1
 mol 
=  = mol L–1
 L 
19. KP = (a/m)ng
[B]
20. Keq =
[A]
[B]e K
KC = = f  [A]e = Kf Kb–1 [B]e
[A]e Kb
21. KP = KC(RT)ng
KP
22. log + log RT = 0
KC
KP
= (RT)–1  ng = – 1
KC
KP
23. = (RT)ng
KC
24. KP = KC(RT)1
1
RT = 1 T= K
R
2
 48 
 80  0.6  0.6
27. KC =   = = 30
2
 12.8   9.6 0.2  0.2  0.3
 64  32
 
28.  PCl3(g) + Cl2(g)

PCl5 (g) 
neq 0.1 0.2 0.2
0.2 0.2

KC = 10 10 = 0.04
0.1
10
29. PCl5(g)  PCl3(g) + Cl2(g)

X PCl3 = 1 – 0.4 – 0.3 = 0.3
30.  3R(g) + s(g)

2P(g) + O(g) 
ni 2 2
neq 2(1–x) 2–x
moles of Q > moles of P
[Q] > [P]
32.  C(g) + D(g)

A(g) + B(g) 
Ci 3n n 0 0
Ceq 3n–x n–x x x
n–x=x
n
x=
2
35. 
N2(g) + O2(g)  2 NO(g)
ni 2 4 0
neq 1.5 3.5 1
1
[No] = = 0.4
2.5
36. 
3A (g) + B(g)  2C (g)
neq 2 2 2
–2
1
2
2
9=  
2 2  V 
3
V = 9 × 22 V = 6 L
2
38. 
A(g) + 2B(g)  C(g)
ni a 4 0
neq a-1 2 1
1
0.25 = 5
a 1  2 
2

5  5 
1
0.25 =  25
(a  1)  4
a = 26
40. 
H2(g) + I2(g)  2HI(g)
Ci a a 0
Ceq a–x a–x 2x
(2 x)2
Kf = Kb Kc = 1 =1
(a  x)(a  x)
2x = a – x
a
x=
3
41. 
C2H5OH (l) + CH3COOH(l)  CH3COOC2H5(l) + H2O(l)
ni a a 0 0
2a 2a a a
neq
3 3 3 3
aa
· 1
KC = 3 3 =
2a 2a 4
·
3 3
44. 
2SO2(g) + O2(g)  2SO3(g)
nSO2 = nSO3  PSO2 = PSO3
2
PSO
4= 2 3
PSO2  PO2
1
PO2 =
4
46. 
N2(g) + 3H2(g)  2NH3(g)
ni a 3a 0
neq a–x 3(a–x) 2x
n H 2 = 3 n N2
P
PH2 = 3 PN2 = 3 × =P
3
2P
PNH3 = 2P – (P + P/3) =
3
48. KP = KC ng = 0

A(g) + 2B(g)  3C(g)
Pi 1 2 0
Peq 1–x 2(1–x) 3x
(3x)3
= 2 × 10–3
(1  x)  4(1 – x) 2
3x
= 2 × 10–1
1– x
x = 0.0625
49. 
H2(g) + CO2(g)  CO(g) + H2O(g)
ni 0.25 0.25 0 0
neq 0.25–x 0.25–x x x
KP = KC
x2
0.16 =
(0.25  x)2
x 1
= 0.4 x=
0.25  x 14
54. 
A3(g)  3A(g)
Ci a 0
Ceq a(1–x) 3ax
nT = a(1 – x) + 3ax
= a+ 2ax
56. 
PCl5  PCl3(g) + Cl2(g)
ni 4 0 0
neq 2 2 2
nT = 6
57.  2SO2(g) + O2(g)

2SO3(g) 
ni 1 0 0
neq 1–  
2
1
2 .  2  1 
KP = . 
(1  )2  1   
 2
3  2
= 2 .P
(1  ) 2 (2  )
3
Kp = .P
(1  ) 2 (2  )
58.  H2 (g) + I2 (g)

2HI(g) 
neq 1–  
2 2
 .
0
2 2 . P 
(1  )2  1 
KP =
2
KP =
4(1  ) 2
4 2
59. KP = .P
1  2
2
60. KP = .P
1  2
2 1
  << 1
1  2
P
1

P
46
63. 30 =
1 
46
= – 1 = 0.533
30
2
64. KP = .P
1  2
2
9= .7
1  2
7 2 = 9 – 9 2
3
16 2 = 9 = = 0.75
4
70 70
Mmix = = = 40
1  0.75 1.75
8.5
65. 6=
1 
8.5
1+=
6
 = 0.4166
40
66. 35 =
1  0.5
40
1 + 0.5 =
35
 = 0.28
208.5
67. Mmix = = 139
1.5
PMmix 2 139
dmix = =
RT 0.0821 800
= 4.23 g/L
P
69. PNH3 = PH2S =
2
P P P2
KP = . =
2 2 4
71.  2CO(g)
C(s) + CO2(g) 
Pi P 0
P
Peq P
2
PCO2 = 4 atm PCO = 8 atm
(8) 2
KP = = 16
4
73.  NH3(g) + H2S(g)

NH4HS(s) 
0.6atm 0.6atm
KP = 0.6×0.6
= 0.36 atm2
1
77. 
P
1 P
 2
2 P1
P
1 1 1
 16  =
2 P 2 4
83.  C(graphite)

C(diamond)  H = –ve
d d
High T and high pressure
85.  2C (g)

2A(g) + B(g)  H = –ve
On increasing pressure equilibrium will shift to forward direction low temperature high
pressure
89. KE depends only on temperature
90.  Au()

Au(s)  H = +ve
d d
92.  H2O()

H2O(s)  H = +ve
d d
high temperature and high pressure
97. If CO is introduced
 PCl5(g) 
  PCl3(g) + Cl2(g)
 COCl2(g) 
  CO(g) + Cl2(g)
98.  2NH3(g) + CO2(g)

NH2COONH4 (s)  K P1
 CaO(s) + CO2(g)
CaCO3 (s)  K P2
K P2 = K CO2
K P1 = (PNH3 )2 . PCO2
PCO2 and PNH3 remains constant at new equilibrium
EXERCISE # O-II
12. KP = KC (RT)ng
ng = 0
KP = 49
13. H2(g) + I2(g)  2HI(g)

neq 0.5–x 0.5–x 2x
2
(2x)
 49
(0.5 – x)(0.5  x)
2x
7
0.5 – x
x = 0.38
1 0.0821 700
P=
7
= 8.21 atm
14. mole of I2, eq. = 0.5 – 0.38

= .012
2  0.38  0.0821 700

15. PHI =
7
= 6.385 atm
EXERCISE # JEE MAINS
1. In this reaction the ratio of number of moles of reactants to products in same i.e., 2 : 2, hence
change in volume will not alter the number of moles .
3. The conversion of SO2 to SO3 is an exothermic reaction, hence there is no need to increase the
temperature. There is also a decrease in volume or moles in product side. Thus the reaction is
favoured by low temperature and high pressure. (Le-Chatelier’s principle).
4. C[ N2O4 ] = 4.8 × 10–2 mol L–1, C[ NO2 ] = 1.2 × 10–2 mol L–1
[ NO2 ]2 1.2 102 1.2 103
Kc   2
= 0.3 × 10–2 = 3 × 10–3 mol L–1
[ N2O4 ] 4.8 10
[NO]2
5. 
N2(g) + O2(g)  2NO(g) ; Kc =  4 104
[N 2 ][O2 ]
1 1 [N2 ]1/2 [O2 ]1/2 1 1 1 100
 N2(g) + O2(g) ; Kc 

NO(g)     2
  50
2 2 [NO] Kc 4 10 4 2 10 2
6. What is the equilibrium expression for the reaction P4(s) + 5O2(g)  P4O10(s)?[AIEEE-2004]
(1) KC = [P4O10] / [P4] [O2]5 (2) KC = [P4O10] / 5 [P4] [O2]
5
(3) KC = [O2] (4) KC = 1 / [O2]5
7. 
CO(g) + CI2(g)  COCI2(g)
Kp 1
n = 1 – 2 = – 1; Kp = Kc (RT)n   ( RT )1 
Kc RT
8. Kp = Kc (RT)n n = 3 – 2 = 1.
1
Kp = Kc (0.0821 × 457) . Kp > Kc.
9. 
Cl2(g) + 3F2(g)  2CIF3(g) ; H = – 329 kJ. Favourable conditions:
(i) Decrease in temperature, (ii) Addition of reactants, (iii) Increase in pressure i.e., decrease in
volume.
11. Given : 

PCI5(g)  PCI3(g) + CI2(g)
t=0 1 0 0
teq 1–x x x
Total number of moles = 1 – x + x + x = 1 + x
 x 
Thus partial pressure of PCl3 =   P.
 1 x 
12. 
SO3(g)  SO2(g) + O2(g)
[ SO2 ][O2 ]1/2
= KC = 4.9 × 10–2 ...........(i)
[ SO3 ]

SO3(g) + 1/25 O2(g)  SO3(g) ...........(ii)
[SO3 ] 1 
= K'C = For 2SO2(g) + O2(g)  2SO3(g)
[SO2 ][O2 ]1/2
4.9 10–2
[ SO3 ]2 1 10000
= KC2 = 4
= = 416.49
2
[ SO2 ] [O2 ] 4.9  4.9 10 24.01
13. X 
 2Y Z 
 P + Q
1– 2 1–  
2
 2α   α  α 
 1+ α PT1   1+ α PT2   1+ α PT2 
Kp =   Kp =   
1
 1- α  2
 1- α 
 1+ α PT1   1+ α PT2 
   
2
 2α   1- α 
 PT1   PT2 
K P1
= 
1+ α 
×  1+ α 
K P2  1- α   α  α 
 1+ α PT2   1+ α PT2   1+ α PT2 
    
1 4PT1 PT1 1
= ; =
9 PT2 PT2 36
14. 
CO2(g) + C(s)  2CO (g)
0.5 atm
0.5–p 2p
Total pressure = 0.5 – P + 2P = 0.8
P = 0.3
2
PCO (2P) 2 (0.6) 2
Kp = = =
PCO2 (0.5 - P) (0.5  0.3)
Kp = 1.8
Kp = Kc  RT
ng
22.
1
ng = –
2
24. A + B 
 C + D
t=0 1 1 1 1
teq 1–x 1–x 1+x 1+x
(1  x) 2
1 x
 = 100  = 10
(1  x)2 1 x
 1 + x = 10 – 10x  11x = 9
9
   x=
11
9
 [D] = 1 +
11
 [D] = 1.818
H 1
25. ln K = ln A – ·
R T
Reaction is exothermic (i.e. H = –ve) so slope
1
of the curve between lnK and will be positive .
T
[AB]2
26. K1 = ... (1)
[A 2 ][B2 ]
[A2 ]3[B2 ]3
K2 = ... (2)
[AB]6
 K2 = K1–3
27. 1. N2 + O2  2NO
ng = 0
Kp = Kc(RT)ng
Kp
=1
Kp
2. N2O4  2NO2
Kp
=(RT)1 = 24.62
Kc
Kp 1
3. = (RT)–2 = = 1.62 × 10–3
Kc (24.62) 2
28. 
NH4HS(s)  NH3(g)  H2S(g)
5.1
Number of mole of given NH4HS = = 0.1 mole
51
0.1 30
moles of NH3 formed = = moles of H2S
100
0.03  0.0821 600
pressure of NH3 = = pressure of H2S = 0.492
3
 Kp = PNH  PH S = 0.492 ×0.492 = 0.242 atm2
3 2
29. N2 + 3H2  2NH3

t=0   P
teq P 3p x
x2
Kp =
p  (3p)3
x = (Kp × 27 p4)1/2
x = (27)1/2 Kp1/2 P2
PT = 4P
PT
P=
4
33/2 K1/2 2
p PT
X=
16
30. A (s)  B(g) + C(g) K P1 = x atm2

P1 P1 + P2
D(s)  C(g) + E(g) KP2 = y atm2
P2+P1 P2
P1 (P1 + P2) = x
P2 (P1 + P2) = y
P1 + P2 = xy
Total pressure = 2 (P1 + P2)
= 2 x  y atm
31. A + 2B  2C + D
Ci a 1.5a 0 0
Ceq a–x 1.5a – 2x 2x x
[A]eq = [B]eq
a–x = 1.5a – 2x
x = 0.5a
[C]2 [D] a 2  0.5a
KC = = =4
[A] [B]2 0.5a  (0.5a) 2
1
32. Equation 1: S(s) + O2 (g)  SO2 (g) : K1 = 1052
2
Equation 2 : 2S(s) + 3O2(g)  2SO3(g) : K2 = 10129
Equation 2 – 2 × Equation 1 gives,
2SO2(g) + O2(g)  2SO3(g) : K
K 2 10129
  K= =  1025
(K1 )2 10104
33. On addition of catalyst value of equilibrium constant does not change.
34. As, Kp = Kc (RT)ng Kp Kc if ng  o

1. 2 HI(g)  H2 (s) + I2(g), ng = 0 kp = kc
2. NO2(g) + SO2(g)  NO(g) + SO3(g) , ng = 0 kp kc
3. 2C(s) + O2 (g)  2CO(g) , ng = 1  kp  kc
4. 2NO(g)  N2(g) + O2(g), ng = 0 kp = kc
EXERCISE # JEE ADVANCED
5. (D) With change of pressure, x will change in such a way that Kp remains a constant.
6. N2O4 (g) 2NO2.

moles t=0, 1 0
moles at eq. 1– 2
2
 2 
 (1  )  P 
 = 4 × P.
2
KP = 
1–  1 – 2
P
1 
Let total pressure at eq. = P.
4 2
or KP = × P.
1 – 2
When volume is halved, P is double.
 a will change as KP is independent of pressure change.
8. (A) H2 – H1 = CP (rxn) (T2 – T1)

and Cp depends on temperature. Hence enthalpy also depends on temperature.
(B) CaCO3(s) CaO(s) + CO2(g) Kp = ( PCO2 )at equlibrium
For a given reaction.
Keq. depends only on temperature.
(C) Keq depends only on temperature.
(D) Enthalpy of reaction is independent of the catalyst. Catalyst generaly changes activation
energy.
9. (8.92 or 8.93)
Sol. Equal volumes of both the reactant are taken so, initial concentrations will be halved.

Fe2+ (aq) +S2–(aq)   FeS (s)
t = 0 0.03M 0.1M
teq. x 0.07M since KC is very high
1 1
KC = 2
= = 1.6 × 1017
[Fe ][S ]2–
x  0.07
x = 8.928 × 10–17
So, Y = 8.92 (after truncate) or 8.93 (after round off).
2019
100 Percentile 99.99 Percentile 99.98 Percentile 99.98 Percentile 99.97 Percentile 99.97 Percentile 99.96 Percentile 99.96 Percentile
HIMANSHU GAURAV SINGH GAURAV KRISHAN GUPTA SARTHAK ROUT VIBHAV AGGARWAL RITVIK GUPTA BHAVYA JAIN AYUSH PATTNAIK SAYANTAN DHAR
2019 (*SDCCP) 2020 (DLP) 2020 (CCP) 2019 (CCP) 2020 (DLP) 2020 (CCP) 2019 (CCP) 2020 (DLP)
Child Help Line No. 1098, Hope Society Kota + 91-72443 33666

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AIR-1 AIR-3 AIR-6 AIR-8

JEE MAIN RESULTS 2020 (January Attempt) OF NUCLEUS EDUCATION

JEE ADVANCED RESULTS OF NUCLEUS EDUCATION

AIR-10 AIR-12 AIR-23 AIR-24 AIR-37 AIR-42 AIR-66 AIR-98

AIR-20 AIR-27 AIR-32 AIR-61 AIR-67 AIR-78 AIR-61 AIR-91

AIR-2 AIR-19 AIR-33 AIR-48 AIR-51 AIR-53 AIR-86

LAW OF CHEMICAL EQUILIBRIUM OR MASS ACTION (By Guldberg and Waage)

(iii) Homogeneous equilibria in gases

[ ] represents concentration PC2H 4 & other are partial pressure at equilibrium

(ii) 3O2(g) l 2O3(g)

CHARACTERSTICS OF EQUILIBRIUM CONSTANT

(iii) Calculating equilibrium concentration.

(b) Equilibrium constant expressions in term of 'a'

[p PCl3 (g) ][p Cl 2 (g) ] a2 æ 1 ö

(a) A(g) l nB(g)

(b) nA (g) l An (g)

FACTOR'S AFFECTING EQUILIBRIA (Le-chatelier's principle)

(ii) Effect of change in pressure

N2(g) + O2 (g) l 2NO(g)

H2(g) + I2(g) l 2I(g) DH = – 9.4 kJ (exothermic)

H2(g) + I2(g) l 2HI(g) + 9.4 kJ

DG = DG° + RT lnQ [Q = Reaction quotient]

EQUILIBRIUM CONSTANT AS PER KINETICS :

2. Benzene is one of the compounds used as octane enhancers in unleaded gasoline.

Application of equilibrium constant (Homogeneous equilibrium)

4. Consider the reaction of chloromethane with OH– in aqueous solution

8. An equilibrium mixture of PCl5, PCl3 and Cl2 at a certain temperature contains

19. Following equilibrium is established at temperature T.

Degree of dissociation ()

Application of equilibrium constant (Heterogenuous equilibrium)

32. Consider the equilibrium

34. Equilibrium constant for the following equilibrium is given at 0ºC.

35. For the equilibrium CuSO4.5H2O(s)  CuSO4.3H2O(s) + 2H2O(g)

39. Find the direction of reaction if temperature is increased.

45. From the following data :

State whether the reaction (iii) is exothermic or endothermic?

(NH4)(NH2CO2) (s)  2NH3 (g) + CO2(g)

49. NH4HS(s)  NH3(g) + H2S(g) K P1

NH3(g)  N2(g) + H2(g) KP2

50. Consider : (I) C(s) + O2  CO2(g)

CO2 in the final equilibrium mixture.

4. For the reaction A(g) + 2B(g)  C(g) + D(g) ; Kc = 1012 .

6. At certain temperature (T) for the gas phase reaction

C(g)  D(g) + B(g) : KC2

10. The value of Kp for the reaction at 270C

2. Which of the following statement is incorrect :

3. Concentrations of reactants and products at equilibrium can be like :

(A) (B) (C) (D) All of these

4. Rate of reaction curve for equilibrium can be like :

(A) 5 (B) 7 (C) 6 (D) 8

7. The equilibrium constant for the reaction ;

8. The equilibrium constant for the given reaction :

(C) Decrease (D) Increase

19. What is the unit of KP for the reaction ?

21. For which reaction is Kp = Kc :–

26. Equilibrium constant of some reaction are given as under ;

(A) Kc > 1 (B) K < 1 (C) K = 1 (D) data insufficient

respectively and total pressure is P then value of Kp is :

45. For the reaction

48. The equilibrium constant KC for the reaction,

reaction will proceed in backward direction, when

(A) Reaction quotient has maximum value at point A

Degree of dissociation ()