9

Chemical Equilibr

Chemical Equilibrium Characteristics of chemical equilibrium

Ifthe process involves only chemical
is called chemical
change, the equilibrium The important characteristics of chemical equilibrium.
equilibrium. It is dynamic in nature.
Reversible reaction: A reaction in which the reactants
The observable properties of
are formed back by the reaction of
products with each the system becomecume
other at the given conditions of the reaction. These equilibrium and remain unchanged thereafter
at

reactions if carried out in a closed vessel do not The equilibrium can be approached fYom
go to
either directi
The equilibrium can be attained only
completion. closed one.
if the system
eg.. CHCOOH+CH,OH=CH,CoOC,H, +H0 The free energy change at constant
3H2)2NH3g temperature is zero. In other words, free
pressure g
energ
Irreversible reaction: These are the reactions in reactants=free energy of products.
which products do not react back to give the reactants, Addition of a catalyst does not change the
ie.. reaction can not be retraced at
equilibie-
state, it only helps in attaining the equilibrium fastet
any point.
e.g., AgNO3 +NaCl>AgCl J+NaNO
The Law of Mass Action
SnCl+2FeCl3> SnCl, +2FeCl2
State of equilibrium : Chemical equilibrium is that This law was given by
to this law
Guldberg and Waage. Accori
state of a reaction at which the rate of forward "At constant temperature the rate
becomes equal to rate of backward reaction.
reaction of chem.-
reaction is directly proportional to the product of at
mass or molar concentration of the reacting substances.
Dynamic nature of chemical equilibria raised to the power equal to its stoichiometric coefficien
In chemical equilibrium represented by the balanced chemical equation.
both forward and backward r(Rate of forward reaction) Applying this law to a reversible reaction of the type.
reactions do not stop but
r (At equilibrium) aAg+ bBg)cCtdDg)
proceed at equal rates, Now, rate of forward reaction «
[A]" [B
x

and the concentrations

of reactants and products
rKAA}"x [B°
remain constant. Therefore
Where &y= rate constant for forward reaction, [4]an
r,(Rate of backward reaction) represent molar concentration of A and B respecthe
the equilibrium is called
Time- Law of
dynamic equilibrium. of dynamic
chemical equilibrium
Let us consider a reversible g State equilibrium
in a reversible reaction Using the law of mass
action, we can derive an
reaction. for reversible reaction at equilibrium, wnhe
a
A +BC+D as law of
chemical equilibrium. It is defineuhe
In the beginning the rate of the forward reaction will be between molar concentrations
greater, which will decrease gradually because of the fall in
of the producis
concentrations of the reactants, with each concentrall coethe
concentration of A and B. On the other hand, the rate of the IS raised to the power
backward reaction will increase due to the increase in the in the balanced
equal to its stoichiomen
chemical equation.
concentration of C and D. Finally a stage is reached when aAt bB)cCt dDg
the rate of the forward reaction is exactly equal to the rate At equilibrium, r=r, = K,4" x[B K,JCT
of the backward reaction. At this stage the concentrations of
reactants and products remain constant. This state is called IC x[D
K
chemical equilibrium. K 4 x[BT A" x[B]
Chemical
Equilibria

109
Wher i sc a l l e
alled as equilib constant, which depends
rature only. The above expression is known TTYr
y p o nt e m p e n

expression or lawW of chemical and K,= * ',G.

(lor g a s e o u s reaction)
um constant

41B p p
ibrium,
eg.. N(e)
+
3H2()2NH( For ideal gases, PV= nRT

Re
=
INH or P concentration in moles L')
For
this
reaction,

INIH RT

Equilibrium c o n s t a n t
Concentration of A. [A] =

RT
librium constant may be defined as the ratio of rate
Similarly for [B]= X]= RT and [Y]= P
RT
c q u i l i b r

of forward reaction and rate constant

constante
of backward
It may be represente as K when concentrations Substituting these values:
R C t i o n .

in moles/litre.

Te
expressed
IC x[D R =RT
it, K [4] x[B] PA P
When oncentrations of reactants
and products are RT
C p r e
ressed in terms of partial pressure, it is denoted by K,. a+b)

PA x[Pa (x+y)- (a + b) = An (difference in number of moles of

When concentrations
of reactants and products are gaseous products and reactants)
,
expressed in terms of mole fraction, it is denoted by K. An
or K, = K (RT)"
Ke= KpRT
K, xFsl If An = 0, K,=R¢

If An= +ve, Kp Ac
Characteristics of equilibrium constant If An =-ve, K, < K
In heterogeneous equilibrium (reactants and products
For areaction, A +BC+D, are in different phases), to determine An only gaseous
=CD]
Equilibrium constant, K products and reactants are considered.
[A][B] Active masses of pure solids or pure liquids are always
) Ifreaction is reversed. taken as unity.
Reaction: C+D2A +B Units of K, and K, :
Equilibrium constant: K'= 1/K Unit of K,= (unit of pressure) e.g., (atnm)
(i)lfreaction is divided by factor n. Unit of K(unit of concentration)", e.g., (mol L)
IfAn= 0, K, or K, have no units.
Reaeton:A+B c+p
n Prediction of the extent and direction of a reaction can
Equilibriumconstant: K' = {K be made from values of equilibrium constant.
(m) If reaction is multiplied by factor n. If K>> 1, equilibrium lies to the right, i.e., product
Reaction: nA + nB =nC+ nD formation is favoured.
Equilibrium constant :K' = K" I fK< < 1, equilibrium lies to the left, i.e., reactant
formation (reverse reaction) is favoured.
i reaction is written in n number of steps.
Reaction: Le Chatelier's Principle
It explains the effect of change of pressure, temperature and
BX+ Y; X+ Y p+. C+D concentration on the system in equilibrium. It states that , if
Equilibrium constant: K' =
Kj x
K2 X.. n a system in equilibrium is subjected to a change of pressure.
Reaction quotient temperature or concentration, then the equilibrium will shift
At any condition of a ersible reaction other than
in such a direction of that reaction so as to reduce the effect
of change, i.e.,
and mcondition, the ratio of rate constants of forward (a) Increase in concentration of any substance favours the
r a reaction is known as reaction quotient (2). reaction in that direction in which the added substance
NetAequilibrium
iforward condition, Ke= Q is used up.
reaction takes when Q<Ke (b) High pressure shifts the equilibrium in the direction of
Net
backwa reaction takesplace,
place, when Q>Ke decrease in gaseous volume.
(c) A rise in temperature favours the endothermic reaction
For
onship between Kp and K and a fall in temperature favours the exothermie
Feaction:
aA + bB xX + yY reactions.
110 wutG Chapterwise WB JEE
molecules is equal to the number of product
EXPLOR
Applications of Le-Chatelier's principle hence pressure has no eftect on the equilibrium molec
Le-Chatelier principle is very useful in predicting the Effect of concentration: Addition of HI or ren
Of Temoval
conditions of temperature, pressure and concentration to get favours the forward reaction.
H, I,
or
higher yiclds in certain industrial reaction. A few examples
are given below:
Reactions Favourable condition
for forward direction
) PCls PClg +C2g: AH= +ve High pressure, low
Effect of temperature: The dissociation of PCi5 is
Ng)t 3Hg)2NH()
endothermic. Hence increase of temperature increases
temperature and isolation
of NH3 by
the rate of formation of PCl; and Cl2.
2S02(0+02(g2S03(e)
liquefaction,
High pressure, low
Effect ofpressure: Increase of pressure will favour the
temperature and isolation
backward direction, as it is accompanied by an increase of SO.
in the number of molecules.
N2(g+O2g)2NO( High temperature and
Effectof concentration:AdditionofPClh or Clh orremoval isolation of NO.
of PCls will shift the equilibrium in forward direction. Low pressure, high
Effect of adding an inert gas
PCls()PCl3(g) +Cl2g)
In a reaction at equilibrium, n, = 1 if an inert gas is
temperature and isolation
of PCl and
added at constant volume or constant pressure, there is Cl
no change in
2HgH2(g)* l2g) High temperature and
equilibrium isolation of H, and ,.
In a reaction where n,> n, addition of an inert gas has
no effect at constant volume but, at constant pressure, Significance of AG and AG°
the equilibrium shifts in the forward direction, e.g, Free energy change (AG) is related to AG°
dissociation of PCl5 : as folloe
AG AG° +2.303 RT log Q
PCl5PCl3 +Clh At equilibrium, Q= K and AG = 0
i) 2H1) =H+h) AH=+ve AG° =-2.303 RT log K
Effect of temperature : The dissociation of HI is an
endothermmic reaction hence increase of temperature IfK>1, then AG°=-ve, i.e., reaction is spontaneous i
forward direction.
favours the formation of H2 andl2.
Effect of pressure : As the number IfK<1, then AG°=+ve, i.e., reaction is spontaneous i
of reactant backward direction.

WB JEE WORKOUT
CATEGORY 1:Single Option Correct The
Type (1 Mark) equilibrium constant of the reaction
1 In what manner
following equation?
will increase of pressure affect the 2NH+0, 2NO+3H,0
in terms of Ki, K2 and K3 is
C+H,Og CO+Hag (a) K,K2K3 (b) K&2/kK
(a) Shift in the forward direction
(b) Shift in the reverse direction
(c) K,K3/K2 () KK/K,
(c) Increase in the yield of hydrogen The reaction N2(e 2g)2NO() is endotherm
The forward reaction is
(d) No effect
(a) favoured by decrease in temperature
2. For a chemical reaction 24 + B C, (6) favoured by increase in pressure
the thermodynamic equilibrium constant K, is (c) unchanged on changing
pressure
(d) in equilibrium point shifts by adding catalyst.
(a) in atm2 (b) in atm*
6. An
(c) in atm (d) dimensionless. equilibrium mixture for the reaction
3. k and ka are the velocity constants of forward and 2H 2H2(+S2 had one mole of hydro
backward reactions. The equilibrium constant Kof the sulphide, 0.2 mole of H, and 0.8 mole of S, in a
reaction is vessel. The value of K, in mole litre is
(a) 0.004 (b) 0.016 (c) 0.080 (d) 0.032

(a) k xkz (b) k-k (c) k,lkz (d) . Which of the illbetk

k-k2 following oxides of nitrogen wu

most stable one?
4. The following equilibria are given
Na +3H2 2NH3; Ki (a) 2NO2 N(+202(g ;K=6.7 x 10moll
(b) 2NO( N()+O2gK K=2.2 x10 mol
N2+O2 2NO; K2
(c) 2N,Os( 2N2)t502gi
K=1.2x10 mol
H 2
0 1,0;K, (d) 2N,O)2N2+OgK 3.5 x10 mo
emical tquilbria
111
to react
reaction 17. 5 moles of SO, and 5 moles of O, are allowed
ilibrium ot the given equilibrium
7hee
SO,Ce) SO2e)*Cl2(g) to form SO, in a closed vessel. At the
of moles
25°C in a closed container and an inert stage,60% is used up. The total number
SO,
inedat introduced. Which of the following in the vessel now is
is of SO2, O, and SO3
g 8 S h e l i u

(c) 8.5 (d) 10.0

statement i s c o r r e c t
ect? (a) 3.9 (b) 10.5
is formed
More
chlorine
18. For the reaction, 2H2()+O24g)2H,(e)
(a) of SO2 is reduces
Concentration
Which of the following fact holds good?
is tormed.
More
SO,Ch
of SO2Cl, SO2 and Clh do not
(a) K,= K
c)
(b) R,> Kc
C o n c e n t r a t i o n

change. (c) K,< Ke

which
(d) K, and K, cannot be correlated
substance
is a
A catalyst
(a) increases the equilibrium constant of the reaction 19. If the equilibrium constants of the following equilibria
librium
(b) increases equilit concentration of products

() notalter
does
activation energy of the reaction.
the reaction mechanism
SO2+O2S0g and 2s0, 2S02 +O2
changes the which of the
are given by Kj and K2 respectively,
constar (K) of a reaction may be
The
equilibriu following relation is correct?
IA
Witten as
(8)K=eAGRT b ) K=e-A©°RT

c ) K = e d H / R T
(d) K=e-ART (a)K =|
11. For the reaction: CO* C2) COCl2(g)» K, IK. ( ) K - (K
aqual to

a 1/RT (b) RT ()RT d ) 1.0 20. Calculate K, for the equilibrium,

which change will shift the reaction
I2 0f the following NH,HS NH3() t HS(
towards the product? if the total pressure inside the reaction vessel is
=+150 kJ
e 2 g AHp(298 K) 1.12 atm at 105°C.
(2) Increase in concentration ofI (d) 0.63
(a) 0.56 (b) 1.25 () 0.31
b) Decrease in concentration of l2
21. In areversible chemical reaction at equilibrium, if the
(c) Increase in temperature
concentration of any one of the reactants is doubled,
() Increase in total pressure
then the equilibrium constant wil
the
8n the reaction +
0.4
PClsg) PCl3g) Chg (a) also be doubled (b) be halved
equihbrium concentrations of PCl; and PCl3 are
(d) becomes one-fourth.
and 0.2 mole/litre respectively. If the value of Ke is (c) remains the same

05, what is the concentration of Cl, in moles/litre? 22. For the reaction, Pa) +3Qg) 4R
(a) 2.0 b) 1.5 (c)1.0 (d) 0.5 Initial concentration of P is equal to that of O. The
4. Calculate K, for the reversible process given below, if concentration of P and R are equal. K is
equilibrium
K167 and T= 800°C. equal to

CaCOyCaO+CO2g)
(a) 1.95 b) 1.85 (c) 1.89 (d) 1.60 (a) 0.08 (b) 0.8 (c) 8 (d)
8
The reaction quotient ()) for the reaction 23. 1 mole of N2 and 2 moles of H2 are allowed to react
*3Hag 2NH%) in a 1 dm vessel. At equilibrium, 0.8 mole of NH, is
is given by = N NH, formed. The concentration of H2 in the vessel is
(a) 0.6 mole b) 0.8 mole
The N(H,
reaction will proceed from right to left if (c) 0.2 mole (d) 0.4 mole.

16. 4)Q-K b) <K. c) Q>K (d) - 0 24. In which of the following equilibrium, change in the
quantity of PCI, heated in 10 dm vessel at volume of the system does not alter the number of
250-C was a
moles?
PCsgPCl3(+Cl2(g (a) N2()+ Oz(g) 2NO
At
quilibrium,
2 mole
the vessel contains 0.1 mole of PCI5 (b) PCls)PCl +Cl2
Teaction is of Cl2. The equilibrium constant of (c) N2(0)t+ 3H2g)2NH3)
a) 0.04
(b) 0.025 (c) 0.02 (d) 0.05
(d) SO,Clh)SO2)t C)
 Mt& Chapterwise WB JEE
EE EXPU
EXPLOR
112
25. Ifequilibrium constant ofreaction, N, +3H22NH3
is K, then K for reaction, 2N, +6H2 4NH, is

(a) K (a) (b)

-NH3
(c) 1K (d) 1/2

26. One mole of S0, was placed invessel of 1 litre

a Time Time

capacity at a certain temperature when the following

equilibrium was established. NH3
-H2 -NH
28028O, +O2 (d)
formed. The N2
At equilibrium, 0.6 moles of SO2 were
will be
equilibrium constant of the reaction
0.45 (c) 0.54 (d) 0.675 Time Iime
(a) 0.36 (b)
33. If 0.2 mol of Hzig) and 2.0 mol of St are mixedin.
27. 2 mol of N,is mixed with 6 mol of H2 in a closed
1 dm' vessel at 90°C, the partial pressure of Hs
vessel of one litre capacity. If 50% of N, is converted
the formed according to the reaction
into NH3 at equilibrium, the value of K, for
H2+S H , S , Kp =6.8 * 1 0 would be
reaction
Na+3H22NH is (a) 0.19 atm (b) 0.38 atm
c) 0.6 atm (d) 0.072 atm.
(a) 4/27 b) 27/4 (c) 1/27 (d) 27
34. Formaldehyde polymerizes to form glucose accordio
28. Ammonium carbamate when heated to 200°C gives
to the reaction
a mixture of NH and CO, vapours with a density of
16.0. What is the degree of dissociation of ammonium
6HCHOCH1206
The theoretically computed equilibrium constantte
carbamate? (Given vapour density of ammonium this reaction is found to be 6 x 10. If1 M solutionci
carbamate is 48) glucose dissociates according to the above equilibrium
(a) 3/2 (b) 1/2 (c) 2 (d) 1 the concentration of formaldehyde in the solution will
29. Consider the follovwing equilibrium in a closed (a) 1.6x 10 M (b) 1.6 x 10* M
containerT: (c) 1.6x 10 M (d) 1.6 x 10-* M

NO4) 2NO2¢) 35. IfAg+2NH[Ag(NH)2J;K =1.7x 10'

At a fixed temperature, the volume of the reaction Ag +C AgCl; K, = 5.4 x 10
container is halved. For this change, which of the Then for AgCl +2NH3 =[Ag(NH;)l +C
following statements, holds true regarding the equihbrium constant will be
equilibrium constant (K,) and degree of dissociation (a) 0.31 x 102 b) 3.2 x 102
(a)? (c) 9.18 x 10l6 (d) 1.00x 10-17
(a) Neither K, nor o changes
36. 56 g of nitrogen and 8 g of hydrogen gas are heateda
b) Both K, and a change
a closed vessel. At
C) K, changes but o does not change
equilibrium, 34 g of ammonia
present. The equilibrium number of moles of nitog
d) K, does not change, but o changes hydrogen and ammonia are respectively
30. The rate of forward reaction is two times that of the (a) 1,2,2 (b) 2,2,1 () 1, 1,2 (d) 2,1,2
reverse reaction at a given temperature and identical 37. In the given reaction
concentration. Kequilibrium 1S
(a) 0.5 (b) 1.5
2+Ye)2Z (+80kcal,
(c) 2.5 (d) 2.0 which combination of pressure and temperature

CATEGORY 2: Single Option Correct Type (2 Marks) give the highest yield of Z at equilibrium?
(a) 1000 atm and 200°C (b) 500 atm and 500
31. The decomposition of N,O4 to NO, is carried out at (c) 1000 atm and 100°C (d) 500 atm and 100
280°C in chloroform. When equilibrium is reached, 38. For the following three reactions (), (i) and
0.2 mol of N,O4 and 2 x10 mol of NO2 are present equilibrium constants are given
in 2 litre solution. The equilibrium constant for the ) COtH,O CO2e t Hai
reaction, N,04 2NO, is (i) CHag +HO cO+3H2g;K2
(a) 1x 10 (b) 2 x 10 (c) 1« 10 (d) 2x 10 (m CHa + 2H,0 CO+4Ha
32. For the synthesis of ammonia by the reaction Which of the following relations is correct?
N+3H2NH, in theHaber process, the attainment (a) K3K=K2 b) KiK =K^
of equilibrium is correctly predicted by the curve (c) K2K=K, (d) K-KK
 M13
e m i c a E
l q u i l i b r i a

reaction for which the equilibriunm constant

r e a c t i c

the
Select CATEGORY 3:One or More than One Option
i s w r i t t e na s
9.
Correct Type (2 Marks)
46. The cquilibrium constant of the following reaction in

MX MX, +1/2X, cquilibrium at 27°C,

2M +X,
b) 2MX +z 2MX, A+BC+D is 10.
Which of the following statements for the given
) 2MX 1/24; MX reaction is/are correct?
d) MX+
(a) Free energy change of the reaction is zero.
if
r the reaction, SO(e)+0)SOg) we
(6) Standard free energy of the reaction is zero.
then x becomes (c) Standard free energy of the reaction is -5.74 kJ.
eK, =K (RT)", (d) Free energy change when all the reactants
and
Write
will be-5.74 kJ.
(d) 1 products are I molal each
a) )- 47. For which of the following reactions, K, = K?

reaction
For the
reversible
(a) Hzg+ 2)2He
Na+ 3H2g2NH( (6) 2N,04g)4NO2(e)
500°C, the
value
of Kp is 1.44 x
10 when
(c)Nag+3H22NHa)
At
measured in atmospheres. The
nartial pressure
1s
(d) Hat+Clag2HCl
value of Ke with concentration in
responding 48. For the dissociation equilibrium,
mole litre, is
N,O4(g) 2NO2(g» the variation of free energy

1.44 x 500)2
10/ (0.082 x
with the fraction of Ng04 dissociated under standard
(a)
1.44 10/ (8.314
x 773)2 x
conditions is shown in the figure :
(b)
1.44x 10/(0.082 773)2
x
C
c)
1.44x10/(0.082
773)2 x 2 moles of
() NO2
the equilibrium constant
. At constant temperature,
decomposition reaction, N,O4 2NO,
(K) forthe 1 mole +
=4P where P = pressure,
of N,O4
essed by
by K.
p
s expressed

Which
1-) one of the TO.84 k
x extent of decomposition.
=

true? Equilibrium point

following statements is
increases with increase of P Fraction of N,O4 dissociated
a) K,
increase ofx statements is/are correct?
(6) K, increases with Which of the following is
decrease of x for the forward reaction
c) K, increases with (a) The free energy change
in P and x
d) remains constant with change
K, negative.
for the backward reaction
and 5 moles (b) The free energy change
3. An equilibrium mixture contains 0.5, 0.12
litre vessel is negative.
in a one for the complete
of so, O, and SO, respectively, must (c) The net free energy change
moles of0,
a a certain temperature. How many reaction is positive.
order to increase spontaneous than
be forced into the reaction mixture in Forward reaction is
more
(d)
the conc. of SO; to 5.3 moles at the same
temperature? backward reaction.
is 800) the value of
+O,2S03 N,04(g)2NO2(g)»
(GvenK,forthe reaction, 2S0,
(b) 0.908
49. For the reaction, and 1700 at 500 K.
Which of the
a) 0.506 K is 50 at 400 K
is/are correct?
)0.74 (d) 0.45 following options endothermic.

4 but when heated

at
(a) The reaction is
4pour density of PCle is 104.16 to 62. The degree b) The reaction is
exothermic.
mixed at 400 K at
230°C its vapour « is reduced density are

will be (c) NO2g) and N04g) and 2 bar respectively,

If
OC1ation of PCl, at this temperature 20 bar
partial pressures be formed.
(a) 6.8% b) 68%
N,O4g)
more
will
remains constant.
c) 46% (d) 64% of the system
5. Ata of 10° Pa,
(d) The entropy constants of the reactions,
certain temperature and a total pressure iodine 50. The
equilibrium
1odine volume of =NH
vapours contain 40% by
aloms ie2g Ng 3H,+ 2NH, and ; N,tzH2
between
The relationship
1or the equilibrium Will be K and K2 respectively.
(a) 0.67 b) 1.5
are
and K2 is/are
) 2.67x 10 (d) 9.0 x10 K
 114 mtG Chapterwise WB JEE EXPl
53. In which of the following reactions, the value
(a) Ki = K2
will be equal to K,?
value of k
(c) K =K
(d) K- K (a) N2g) t+ O2(g)2NO(;

S1. In the presence of a catalyst, what happens to the (b) PCls=PClig+ Clag
(c) H2(g) + Br2(g)2HBr(
chemical equilibrium?
(a) Energy of activation of the forward and backward (d) 2S02g)+Oz(g) 2S03(g)
54. Le-Chatelier's is
principle
reactions is lowered by same amount.
(a) ifa system in equilibrium is subjected to ach
(b) Equilibrium amount is not disturbed. Change
(c) Rates of forward and reverse reactions increase of concentration, pressure or
temperature.
equilibrium shifts in the direction that tend he
by the same factor nds to
undo the effect of change
(d) More product is formed.
(b) applicable to all type of dynamic equilibrium
52. 138 g of N,O4e is placed in 8.2 L container at 300 K. (c) applicable to irreversible system
The equilibrium vapour density of mixture was found (d) applicable to all physical and chemical equilib
to be 30.67. Then (R = 0.082 L atm moll K-)
55. In which of the following reactions would the yield o
(a) the total pressure at equilibrium 4.5 atm the products be increased by the application of hich
(b) the degree of dissociation of N,O,= 0.25 pressure?
(c)the total number of moles at equilibrium is 1.5 (a) 2S02+O 2SO3 (b) N +3H,2NH,
(d) K, of N,O, 2NO2) will be 6 atm. (c) PCl PCl +Cl2 (d) H2 t+ l22HI

HINTS &SOLUTIONS
1. (b):n, > n, (gaseous), correct option is (b) by | 12. (): The given reaction is endothermic. So n
LeChatelier's principle. increasing temperature, it will shift in the forward direction

2. (a):K,= == atm2 13. (c): K =PCIyICL]ie. 0.5 = 02x[Ch]

PA X PB P [PC1s1 0.4

3. (c): K=k;/k, =k; /k2 or, [Clh]=1.0 mol L-

14. (c): K, =K,(RTA
4 (d):K,= NH]F ,K2 = [NO] An =np-nR=1
N,] [H,P2N,110,1 K K0.0821 x 1073)

167
K=lH,0]
K l.89
K3H.]o,? 0.0821 x 1073
15. (c): The reaction proceeds from right to left when
NOF (H,Of ThusK= A2 Q>Ke, so that Q tends to decrease to become equalto A
KNH,1* NH,][O, K 16. (a): PCl PCl + Ch
5. (c)n,=n,, Therefore, pressure has no effect. Moles at eqm. 0.1 mole 0.2 mole 0.2 mole
Molar concs. 0.1/10 0.2/10 0.2/10
6. (b):K= (0.2/2 0.8/2)0.104) = 0.016 0.02 x 0.02
1/2) (0.5) K
0.01
-
0.04
7. (a):Lower the equilibrium constant, greater is the 17. (c): 2S02+ O2 2S0s
stability. Initial moles 5 5
8. (d): At constant volume, there is no change in At eqm. 5-X5
100
5-1.5
concentrations by addition of inert gas - 5 -3-2
3.5
9. (d): Catalyst is a substance which speeds up the Total 2+3.5+3 =8.5
rate of reaction by lowering the activation energy of the 18. (c): As we know, K, =K, (RT)"
reaction.
2H2tO2(g)21,0
10. (b):AG°
=
-RT InK or K=eAGRT An =2-(2+ 1)=-1
11. (a):An, =1-2 =-1 RT
/RT
K, =KRT =K{RT)=K, Hence, K,<R
or, KK= 1/RT
 Chemical Equilibria
115

19. ():SO+50,=So, (1) K (0.6) (0.3) = 0.675

(0.4)
[SO] 27. (a): N +3H22NH3
Theretore. so,]1O;1* Initial 2 mol 6 mol
At. cqm. mol mol
2s02SO, +O, .
(1) 2 mol L
Molar cone. 3

_ SO,F1O,1
Thus, K =

Ke (2) 4
SO, Ix(3) 27

or - 28. (d): NHCOONH4 2NH3 +CO2

Initial mole
Aftcr disso. - o.
20
20. (c): NHHS( NH3e)tH2S) Total = 1+20
Let initial moles

(1-)
At quilibrium
moles at equilibrium
=
x +x =
2r Theoretical, density (a)1+20.)V
Total gaseous
We know &p =PNH, * PH,s

mole fraction x total pressure (P) =1+20

butpartial pressure (P)=
r)-|)-(4) -03136 or, 1(48-16.0=1.0
volume
have number of 29. (d): K, is constant at constant temperature. As
7ad method Both NH3 and H,S same
will
have same mole fraction and thus is halved, pressure will be doubled. Hence equilibrium
so
moles at equilibrium shift in the backward direction i.e., degree of
dissociation
equal partial pressures.
decreases.
1.12
ie.. PNH = PH,s * 2
30. (d): Aeqm k
.121.12 =0.3136
2 K= [NO,1 (2x10/2)10 =105

21. (c): Equilibrium constant depends only

on temperature.
31. (c):K N,0,] (0.2/2) 10
and concentrations of H2 and
22. (c):Let initial concentration of P and Q
are equal 32. (a) : (a) is correct because
then decrease while that of NH increases
with time and after
at equilibrium x concentration of P reacts, N
equilibrium, all of them remain
constant.
Pg) 3Qc 4R)
have reacted, then at eqm.,
Initial conc. C C 0 33. (b): Suppose x moles of H2
(moles L-) [H]=(0.2-x), [H,S]=x
(C-3x)
A1 equilibrium C-)
But i is given that ( C - x ) = 4x 0.2 0.2-x P
C 5x
PH20.2-x+x 0.2

(4x)* 64x Pus

xP
K=R = 8
0.2-x +x 0.2
8x3
PIIQ (4x)(5x-3x)°
Pu,Sie., 6.8x 10 =

(0.2-x)
23. (b): Na +3H22NH3 PH2
=0.0127 mol
mole
3 of or, 0.068 (0.2 -x) =x or x

at 363 K in 1 L vessel,
rormation of 0.8 mole of NHa means thatx0.8 Pressure of 0.0127 mol of H2S
H, have reacted. nRT 0.0127x0.0821x363 - 0.38 atm

0.8
P= 1
ence, concentration of H, 2-x =

ofK for the given equilibrium

value
= 2-1.2 = 0.8 mole. 34. (b): A very high
shows that dissociation of glucose to form HCHO is very
Hence at equilibrium, we can
take
24. (a): Change the molar very small.
in volume change
in volume will not [CH20%1] I M
=

lalter theration. In (a), n. Change

=

n,

25. (a)
number of moles in this case K= IC,HiO,l
[HCHO°
ie. 6 x
10
HCHO
26. (d): 6
2S02 + OD2
Initial
2S03 0 or [HCHO- | nE =
1.6x 10 M
I mole
At eqm. 0.3
1-0.6 0.4 0.6
 116 wtG Chapterwise WB JEE EXPLOn

equilibrium, [SO,]
=
0.2 M
35. Hence at
(a): For reaction,
Ag +2NH, [Ag(NH,),T:K, =1.7 x 10 [O]=(x-0.03) M: [SO,] =5.3 M
SO, (5.3)
K=-
For Ag' +Cl= =AgCl; K, =5.4 x 10 SO,1 x [0,] (0.2) x (r-0.03) 0(give
Thus for, x-0.03 =
0.878 * = 0.908 moles
=
1
AgCl Ag' +Cl; KK54x 10 44. (b): PClsPCl +Cl2
Initial C

Nowfor the reaction, AgCl+2NH, [Ag(NH,),1 +C Al eqm. c(l - o) ca CO

Total moles at eq. = C(l - a) + Ca t c a =c(1 +a)

K=K, x K =1.7x10' x-5.41

x 10
= 0.31 x 102
For a reaction at equilibrium, vapour density is inve
36. (c): 56 g of N, = 56/28 = 2 moles, proportional to the number of moles, therefore, versely
8 gof H=8/2 =4 moles, Total moles at eq. Vapour density initial
34 g of NH; = 34/17 =2 moles. Initial total moles Vapour density at eq.
N +3H, 2NH3
Initial 2 moles
At eqm. 2-1 mole
4 moles
4-3 moles 2 moles
or c+-or 1+0=
C d
a--1
1 mole F1 mole
D-d 104.16 62= 0.68 = 68%
37. (c):As n, < ns higher the pressure, greater will 62
be yield of Z. As reaction is exothermic in the forward 45. (c): Partial pressure of I atoms (P)
direction. lower the temperature. greater is the yield of Z (as 40
x 10 Pa =0.40 x 10? Pa
at low temperature the reaction is slow, usually optimum
100
temperature is used).
60
38. (d): CO+HO Partial pressure of I2(Pi,)= 1 1 0 ° Pa= 0.60 x 10 Pa
COg)+H2)
[CO][H,] 0.4x10)
K1CO][HO K, 0.60x10 -

= 2.67 x 10
CH4g+HO)COe) 3H2)
46. (a, c, d): (a) Fora system to be in equilibrium, AG=0
[Co]HF (i) (c)AG°=-2.303 RTlog K
K2CHITH,O] -2.303 x 8.314 x 300 x log 10 = -5.74 kJ
CHg+2H,0 COg)+4H2g) (d) AG° is the free energy change when all the reactamts
K = CO]H, having unit concentrations, change into the products having
.11) unit concentrations.
[CH 1[HOF
From equations (i). (i) and (ii); K3 -Kj x K2 47. (a, d)
48. (a, b, c): AG° for conversion of 1 mole ofN,Og inta
39. (c): KK=- i s for 2MX + 2MX equilibrium mixture (forward reaction)
[MX21X21 =-0.84 kJ, i.e., -ve
AG° for conversion of 2 moles of into
40. (b):K, =KRTY,= An, = 1- NO2 equliDru
mixture (backward reaction)
=-5.40 +(-0.84) = - 6.24 kJ, i.e., -ve
41. (d): An, =2-4--2, K, =K,/(RT)an
=
1.44 x
10/(0.082 x 773)2 AC° for conversion of 1 mole of N,O, completelyin
2 moles of NO, = +5.40 kJ.
42. (b): k, is temperature dependent only. By changing P AG° for complete conversion is
or x equilibrium shifis as per Le Chatelier's principle, but positive therefore, compl
conversion is not possible.
after some time it establishes a new state of equilibrium at As AG° for backward reaction is more than
which K is maintained constant. negative
for forward reaction, i.e., formation of N,04 1S
43. (b):
Initial
2S01g)
0.5 moles
O2g)
0.12 moles
2S03(g)
moles
spontaneous.
49. (a, c) : (a) For an endothermic reaction, K inerea
reases

At equilibrium (0.5-0.3) moles (0.12 +x-0.15) moles 5.3 moles

with increase in
Suppose 'x' moles of O2 be introduced into the vessel in temperature.
order to increase the conc. of S03(g) to 5.3 moles/litre.
0 . 3 mole SO% and 0.15 mole O, will be consumed
()At 400 K, 0 =
Pso 20=200
according to the above equation. As
PN0 irection

Q>K, hence, reaction proceeds in backward aio

 emical Equilibria 117
2NH, n= No. of moles of products formed from the dissociation
+3H2
50. (b, e): Na of I mole of N,O4
[NH
[N1H, 46-30.67 = 0.4998 0.5
o2-1 30.67
NH 1 +0.5 1.5
of moles at equilibrium
=

Thus, total
=
no.

[NH NH =K K =K Total pressure =

1.5 x0.082 X500 4.5 atm
NH,T
=

8.2

51. (a, b, c)
2NO, So, K, 40 x 4.5 = 6 atm
N,O4
52. (a, c, d)
:

Initial moles
0
Eq. moles (1-) 20

equilibrium=l-a+20a =1+a 53. (a, c):K, =K_RTYA

Totalno. ofmoles at
where, D=
1heoretical vapour
Mol. mass
2 reaction.
d- Observed vapour density
when An0, K, =Ke
for
54. (a,b,d): Le-Chatelier's principle is applicable
density reversible system.
55. (a, b): Since in option (a) and (b) volume is decreasing,
thus high pressure will favour the forward

(8
2013-2020
WB JEE Previous Years Questions

NH to give NO is
CATEGORY1:Single Option Correct Type (1 Mark)
For the reaction 2S02(g)+O2(g
300 K, the value of AG° is - 690.9R. The equilibrium
2S0(g at (K
(2018)
constant value for the reaction at that temperature is
(R is gas constant) 4.
)KKK
In the equilibrium, H2 +lh 2H1, if at a given
a) 10 atmT (b) 10 atm
temperature the concentrations of the
reactants are
(c) 10 (d) (2015) increased, the value of the equilibrium constant, K,
for the following reactions at
2Equilibrium constants
will
1200 Kare given: (a) increase b) decrease
103
2H,0)2H2(g +O);Kj 6.4x
=

(c) remain the same

1.6 x 10
2g)2C0+O2c): K2 (2019)
=

(d) cannot be predicted with certainty.

The equilibrium constant for the reaction The equilibrium constant for the following reactions
5.
at 1200 K will be are given at 25 °C
)+CO2g)CO+H,O
(d) 5.0 2A B + C, Kj = 1.0
(a) 0.05 (b) 20 (c) 0.2
(2017) 2B C+D, K2 = 16

2 C + D = 2 P , K^ = 25
The following equilibrium constants are grven
The equilibrium constant for the reaction,
Ny +3H 2NH3:K1
N+O 2NO ; K2
P A+;B at 25 °C is
H,+0 H,0;K
he cquilibrium constant for the oxidation of 2 mol of )20 (b) 20 () (d) 21
(2020)
118 WutG Chapterwise WB JEE EXPLORE
(given, equilibrium cont. = 0.15, R= 8.314 J K-m
CATEGORY 2: Single Option Correct Type (2 Marks) mol
(a) 1.1 kJ (b) 4.7 kJ
6. The standard Gibbs free energy change (AG°) at 25°C (c) 8.1 kJ (d) 38.2 kJ
(2013)
for the dissociation of N,04 to
NO2g)is
HINTS & SOLUTIONS

1. (a): 2SO2() +O2g) 2503()

AG=- RT In K H+;0 H,0;K,
- 690.9 R =-RTIn K
K3 =
[H,O]
690. In K [H][O,12
300
Now, oxidation of NH3 takes places as below:
2.303 In K= 2.303 log K ; K= 10
4NH +50, 4NO0+6H,0
Ap
PsOg atm
atm or 2NH+02 2NO +3H,0
Pso Po, atm 2

2. (d): Given
K
NO H, oj
2H,0
2C02(g)
2Hg+O2)K, = 6.4 x 10%
2C0+O2(g K =1.6 x 10
i) NH, [O,P
)
Required equation is, K[NO?_JN,IH,PIJ
K= H,01
Ha+CO2c COtH,OK=? DN1O1[NH,T H,TTO,2
By reversing equation (1) and by multiplying it with 1/2,
we get

H O2g)H,O: Ki=64x
6.4x 10
10
.ii) 4. (): The value of equilibrium constant for a particulat
reaction is always constant depending only upon the
And by multiplying equation (i) with 1/2, we get temperature of reaction and is independent of concentration
of reactants.
cOgCO O Ki = yi6x10 iv) 5. (a): The givenreactions can be converted as
By adding equations (ii) and (iv), we get B+CA K =1
Hae+COe COtHO: K'=K]xK
K
1.6x10-6 =v25 =5
V 2 5 =5

V6.4 x10-
3. (b): N2+3H2 2NH3 ; K1 PC+p Ki =
[NH, 1
K =

N JH,F P K, =ix*
Na +O 2NO;K2 6. (b): AG° = - RTIn K
NOP =- 2.303 x 8.314 x log 0.15 =4.7 kJ

K2N1O,)