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Chemical Equilibrium

 Marked questions are recommended for Revision.

This Section is not meant for classroom discussion. It is being given to promote self-
study and self testing amongst the Resonance students.

PART - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))


Max. Time : 1 Hr. Max. Marks : 120
Important Instructions
1. The test is of 1 hour duration.
2. The Test Booklet consists of 30 questions. The maximum marks are 120.
3. Each question is allotted 4 (four) marks for correct response.
4. Candidates will be awarded marks as stated above in Instructions No. 3 for correct response of each
question.
¼ (one fourth) marks will be deducted for indicating incorrect response of each question. No deduction
from the total score will be made if no response is indicated for an item in the answer sheet.
5. There is only one correct response for each question. Filling up more than one response in any question
will be treated as wrong response and marks for wrong response will be deducted accordingly as per
instructions 4 above.

1. 1 mole of N2 and 2 moles of H2 are allowed to react in a 1 dm 3 vessel. At equilibrium, 0.8 mole of NH3 is
formed. The concentration of H2 in the vessel is :
(1) 0.6 M (2) 0.8 M (3) 0.2 M (4) 0.4 M

[R]
2. For the following mechanism , P + Q PQ R at equilibrium is :
[P][Q]
[ k represents rate constant ]
K A .K B K A .K D K B .K D K A .K C
(1) (2) (3) (4)
K C .K D K B .K C K A .K C K B .K D

3. Select the reaction for which the equilibrium constant is written as [MX 3]2 = Keq. [MX2]2 [X2]
1
(1) MX3 MX2 + X2 (2) 2MX3 2MX2+ X2
2
1
(3) 2MX2 + X2 2MX3 (4) MX2 + X2 MX3.
2

4. 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?
(1) 64 (2) 0.30 (3) 42 (4) 8.5

5. The equilibrium constant (Kp) for the reaction PCl5(g) PCl3(g) + Cl2(g) is 16. If the volume of the
container is reduced to one half its original volume, the value of K p for the reaction at the same
temperature will be :
(1) 32 (2) 64 (3) 16 (4) 4
6. 4.5 moles each of hydrogen and iodine heated in a sealed ten litre vessel. At equilibrium 3 moles of HI
were found. The equilibrium constant for H2(g) + I2(g) 2HI(g) is :
(1) 1 (2) 10 (3) 5 (4) 0.33
7. In a 20 litre vessel initially each have 1 – 1 mole CO, H2O CO2 is present, then for the equilibrium of
CO + H2O CO2 + H2 following is true :
(1) H2, more then 1 mole (2) CO, H2O, H2 less then 1 mole
(3) CO2 & H2O both more than 1 mole (4) All of these

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8. At 1000 K, the value of Kp for the reaction A(g) + 2B(g) 3C(g) + D(g) is 0.05 atmosphere. The
value of KC in terms of R would be :
(1) 20000 R (2) 0.02 R (3) 5  10–5 R (4) 5  10–5  R–1
9. In which of the following reactions is Kp < Kc ?
(1) CO(g) + Cl2(g) COCl2 (g) (2) CH4(g) + H2O(g) CO(g) + 3H2(g)
(3) 2BrCl(g) Cl2(g) + Br2(g) (4) I2(g) 2(g)
10. K for the synthesis of HI is 50. K for dissociation of HI is :
(1) 50 (2) 5 (3) 0.2 (4) 0.02

11. The equilibrium constant of the reaction H 2(g) + I2(g) 2HI(g) is 64. If the volume of the container
is reduced to one fourth of its original volume, the value of the equilibrium constant will be
(1) 16 (2) 32 (3) 64 (4) 128

12. In equilibrium CH3COOH + H2O CH3COO– + H3O+


The equilibrium constant may change when
(1) CH3COO– is added (2) CH3COOH is added
(3) Catalyst is added (4) Mixture is heated
13. In the gaseous reaction, N2 + O2 2NO, the moles/litre of N2, O2 and NO respectively are 0.25,
0.05 and 1.0 at equilibrium. The initial concentration of N2 and O2 will be respectively : (Assume that
initially, only N2 and O2 are present)
(1) 0.75 mol/litre, 0.55 mole/litre (2) 0.50 mole/litre, 0.75 mole/litre
(3) 0.25 mole/litre, 0.50 mole/ litre (4) 0.25 mole/litre, 1.0 mole/litre

14. In the following reaction started only with A8, 2A8(g) 2A3(g) + 3A2(g) + A4(g) mole fraction of A2 is
found to 0.36 at a total pressure of 100 atm at equilibrium. The mole fraction of A8(g) at equilibrium is :
(1) 0.28 (2) 0.72 (3) 0.18 (4) None of these
15. In a 0.25 litre tube dissociation of 4 moles of NO is take place. If its degree of dissociation is 10%. The
value of Kp for reaction 2NO N2 + O2 is :
1 1 1 1
(1) (2) (3) (4)
18  2
8 2 16 32

16. For the given reaction at constant pressure,


n A (g) An (g)
Initial moles 1 0
Moles at equilibrium 1   /n
Then the correct relation between initial density (di) & final density (df) of the system is
 n  1  d f  di  n  df  di 
(1)    =  (2) =  
 n   df  n1 df
 n  1  di  d f  1  di  d f 
(3)    =  (4)   = 
 n   di  (n  1)  di 

17. 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
(1) P atm (2) P2 atm2 (3) P2 / 4 atm2 (4) 2P atm

18. At room temperature, the equilibrium constant for the reaction P + Q R + S was calculated to be
4.32. At 425°C the equilibrium constant became 1.24 × 10–2. This indicates that the reaction
(1) is exothermic (2) is endothermic
(3) is difficult to predict (4) no relation between H and K

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19. Calculate G° for conversion of oxygen to ozone 3/2 O 2(g)  O3(g) at 298 K, if Kp for this conversion
is 2.47 × 10–29
(1) 163 kJ mol–1 (2) 2.4 × 102 kJ mol–1 (3) 1.63 kJ mol–1 (4) 2.38 × 106 kJ mol–1
20. For the reaction, 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O() , H = positive .
At equilibrium which factor will not effect the concentration of NH3 is :
(1) change in pressure (2) change in volume (3) catalyst (4) None of these
21. The effect of adding krypton (Kr) gas on position of equilibrium, keeping the volume of the system
constant is
(1) If n = 0, backward reaction is favoured. (2) If, n = +ve, forward reaction is favoured
(3) If n = –ve, forward reaction is favoured (4) No effect whatever be the value of n
22. Le-Chatelier’s principle is applicable only to a
(1) System in equilibrium (2) Irreversible reaction
(3) Homogeneous reaction (4) Heterogeneous reaction
23. 'a' moles of PCl5, undergoes, thermal dissociation as : PCl5 PCl3 + Cl2, the mole fraction of PCl3 at
equilibrium is 0.25 and the total pressure is 2.0 atmosphere. The partial pressure of Cl 2 at equilibrium
is:
(1) 2.5 (2) 1.0 (3) 0.5 (4) None
24. The value of Gº for the phosphorylation of glucose in glycolysis is 15 kJ/mole. Find the value of Kc at
300 K.
6 2.303
 1
(1) e6 (2) 10 2.303 (3) (4) 10 6
e6
25. Which of the following statements is correct for a reversible process in a state of equilibrium ?
(1) G = 2.30 RT log K (2) G° = –2.30 RT log K
(3) G° = 2.30 RT log K (4) G = –2.30 RT log K
26. For the following isomerisation reaction
cis-butene-2 trans-butene-2 KP = 1.732
A
P(trans-butene-2)

60º
P(cis-butene-2)
Which of the following statement is true at point ‘A’ ?
(1) Q > KP (2) Q < KP (3) Q = K = 1 (4) Q = K = 1.732
27. The following equilibrium exists in a saturated solution of NH4CI.
NH4CI(S) NH4+ (aq) + CI-(aq) ; H25°C = 3.5 kcal mol-1
A change that will shift the equilibrium to the right is
(1) decrease in temperature
(2) increase in temperature
(3) addition of NH4CI crystals to the reaction mixture
(4) addition of NH4OH solution to the reaction mixture.
28. For the reaction : PCl5 (g) PCl3 (g) + Cl2 (g)
The backward reaction at constant temperature is favoured by
(1) introducing chlorine gas at constant volume
(2) introducing an inert gas at constant pressure
(3) increasing the volume of the container
(4) introducing PCl5 at constant volume

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29. Find out lnKeq for the formation of NO2 from NO and O2 at 298 K
1
NO(g) + O2 NO2 g
2
Given : Gºf (NO2) = 52.0 KJ/mole
Gºf (NO) = 87.0 KJ/mole
Gºf (O2) = 0 KJ/mole
35  10 3 35  10 3 35  103 35  103
(1) (2) – (3) (4)
8.314  298 8.314  298 2.303  8.314  298 2  298

30. If a reaction vessel at 400ºC is charged with equimolar mixture of CO and steam such that
PCO = PH2O = 4 bar what will be that partial pressure of H2 at equilibrium
CO + H2O CO2 + H2 KP = 9
(1) 0.3 bar (2) 0.4 bar (3) 0.2 bar (4) 0.1 bar

Practice Test-1 (IIT-JEE (Main Pattern))


OBJECTIVE RESPONSE SHEET (ORS)

Que. 1 2 3 4 5 6 7 8 9 10

Ans.

Que. 11 12 13 14 15 16 17 18 19 20

Ans.

Que. 21 22 23 24 25 26 27 28 29 30

Ans.

PART - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I


1. If the equilibrium constant for the reaction 0.125. [NSEC-2000]
P4(g) + 6CI2(g) 4 PCI3(g)
The value of equilibrium for this reaction 4PCI3(g) P4(g) + 6CI2(g).
(A) 0.25 (B) 8 (C) 0.125 (D) 6
2. The free energy change for a reversible reaction at equilibrium is : [NSEC-2000]
(A) very large positive (B) positive (C) zero (D) negative
3. Pure ammonia is placed in a vessel at a temperature where its dissociation constant is appreciable. At
equilibrium : [NSEC-2001]
(A) concentration of ammonia does not change with pressure.
(B) its degree of dissociation, a does not change with pressure.
(C) Kp does not change significantly with pressure.
(D) concentration of hydrogen is less than that of nitrogen.
4. One mole of ethyl alcohol was treated with one mole of acetic acid at 25ºC. Two-third of the acid
changes into ester at equilibrium. The equilibrium constant for the reaction will be : [NSEC-2001]
(A) 3 (B) 2 (C) 1 (D) 4
5. The relationship between equilibrium constants Kp and Kc for a gaseous reaction is : [NSEC-2001]
(A) Kp = Kc.R(T)n (B) Kc = Kp.(RT)n (C) Kp = Kc.(RT)n (D) Kp = Kc/RTn
6. For the gaseous reaction, C2H4 + H2 C2H6, the equilibrium constant has the units : [NSEC-2001]
(A) mol2dm–3 (B) dm3mol–1 (C) dm3mol–2 (D) mol.dm–3

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7. The equilibrium constant for the reaction H2 + Br2 2HBr is 67.8 at 300ºK. The equilibrium
constant for the dissociation of HBr is : [NSEC-2001]
(A) 0.0147 (B) 67.80 (C) 33.90 (D) 8.349
8. The equilibrium constant (K) for the reaction, A + 2B 2C + D is : [NSEC-2001]
[C]2 [D] [2C][D] [C][D] [C]2 [D]
(A) (B) (C) (D)
[A][2B] [A][2B] [A][B] [A][B]2

9. The following pictures represents the equilibrium state for three different reactions of the type
[NSEC-2002]
A2 + X2 2AX ( X = B, C or D)

[A2 + B2 2AB] [A2 + C2 2AC] [A2 + D2 2AD]


Which reaction has the largest equilibrium constant ?
(A) A2 + B2 2AB (B) A2 + C2 2AC
(C) A2 + D2 2AD (D) none of these
10. Methanol (CH3OH) is manufactrued by reaction of carbon monoxide with hydrogen in the presence of
ZnO/Cr2O3 catalyst. [NSEC-2002]
CO(g) + 2H2(g) CH3OH (g) ; [Ho = – 91 kJ]
What happen to the amount of methanol when an equilibrium mixtrue of reactants and products is
subjected to rise in temperature ?
(A) Amount of methanol will increase
(B) Amount of methanol will decrease
(C) Amount of methanol remain the same
(D) None of these
11. For the reversible reaction, A + B C, the specific reaction rates for forward and reverse reactions
are 1.25 × 10–3 and 2.75 ×10–5 respectively. The equilibrium constant for the reaction is : [NSEC-2002]
(A) 45.45 (B) 0.022 (C) 2.20 (D) 0.4545
12. The equilibrium constant for the gaseous reaction H2 + CI2 2HCI is given by [NSEC-2002]
[H2 ][CI2 ] [H ][CI ] [HCI]2 2[HCI]
(A) K = (B) K = 2 2 (C) K = (D) K =
[HCI]2 2[HCI] [H2 ][CI2 ] [H2 ][CI2 ]

13. For the reaction, N2 + 3H2 2NH3, the units of Kc and Kp respectively are : [NSEC-2003]
(A) mol–2 L2 and bar-2 (B) mol–2 L2 and bar–1 (C) mol–1 L and bar–2 (D) mol–1 L–1 and bar–1
14. The equilibrium constant for the reaction N2 + 3H2 2NH3 is 70 at a certain temperature. Hence,
1 3
equilibrium constant for the reaction NH3 N2 + H2 of the same temperature will be
2 2
approximately [NSEC-2004]
(A) 1.4×10–2 (B) 1.2 × 10–1 (C) 2.0 × 10–4 (D) 2.9 × 10–2.
15. For the reaction 4NH3 (g) + 7O2(g) 4NO2(g) + 6H2O(g), Kp is related to Kc by [NSEC-2005]
(A) Kp = Kc (RT) (B) Kp = Kc (C) Kp = Kc (RT)3 (D) Kp = KcI (RT)–1.
16. When Kc > 1 for a chemical reaction, [NSEC-2005]
(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.

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17. Increased pressure shifts the equilibrium of the reaction : N2(g) + 3H2(g) 2NH3(g) so as to
[NSEC-2006]
(A) form more ammonia gas
(B) produce more N2(g) and H2(g)
(C) keep the conversion to ammonia unaltered
(D) produce more H2(g).
18. In which of the following reactions will an increase in volume of the reaction system favor the formation
of the products ? [NSEC-2007]
(A) C(s) + H2O(g) CO(g)+ H2(g) (B) H2(g) + I2(g) H2(g)
(C) 4NH3(g)+ 5O2(g) 4NO(g)+ 6H2O() (D) 3O2(g) 2O3(g)
19. Which of the following changes the value of the equilibrium constant? [NSEC-2007]
(A) change in concentration (B) change in pressure
(C) change in volume (D) none of these
20. Consider the equilibrium reaction: [NSEC-2007]
4NH3(g) + 3O2(g) 2N2(g) + 6H2O(g) (H = –1268 KJ)
Which change will cause the reaction to shift to the right?
(A) Increase the temperature
(B) Decrease the volume of the container.
(C) Add a catalyst to speed up the reaction.
(D) Remove the gaseous water by allowing it to react and be absorbed by KOH.
21. At a given temperature the equilibrium constants of the gaseous reactions
K1
NO(g) + 1/2 O2(g) NO2(g)
K2
2NO2(g) 2NO(g) + O2(g) are related as : [NSEC-2008]
(A) K1 = 2K2 (B) K1 = 1/K2 (C) K1= K2 (D) K1 =1/ K2

22. For the reaction 2HI(g) H2(g) + I2(g) [NSEC-2009]


(A) Kp = Kc (B) Kp > Kc (C) Kp < Kc (D) Kc = K p

23. If the equilibrium constants of the reactions, [NSEC-2009]


1
2SO3 2SO2 + O2 and SO2 + O2 SO3
2
are K1 and K2 respectively, the correct relation between the two equilibrium constant is,
2
1  1
(A) K2 = (K1)–1 (B) K2 = (C) K2 =   (D) K1
K1  K1 

24. The equilibrium constant Kc for the reaction, [NSEC-2009]


2NaHCO3 (s) Na2CO3 (s) + CO2 (g) + H2O (l)
[Na2CO3 ][CO 2 ][H2O] [Na 2CO 3 ]
(A) Kc = 2
(B) Kc =
[NaHCO 3 ] [NaHCO 3 ]2
(C) Kc = [CO2][H2O] (D) Kc = pCO2 × pH2O
25. For the following reaction, the value of K changes with [NSEC-2010]
N2(g) + O2(g) 2 NO(g) H = + 180 kJ mol–1
(A) change in pressure (B) change in concentration of oxygen
(C) introduction of NO(g) (D) change in temperature
26.* The formation of ammonia from nitrogen and hydrogen gases can he written by the following two
equations
1 3 1 2
(a) N2(g) + H2(g) NH3(g) (b) N2 (g) + H2(g) NH3(g)
2 2 3 3
The two equations have equilibrium constants K1 and K2, respectively. The relationship between the
equilibrium constants is [NSEC-2010]
(A) K1 = K22 (B) K13 = K22 (C) K12/3 = K2 (D) K1 = K23/2
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27. For the reaction PCl3(g) + Cl2(g) PCl5(g), Kc is 26 at 250°C. Kp at the same temperature is
(R = 8.314 JK–1mol–1) [NSEC-2011]
(A) 4.6 × 10–3 (B) 5.7 × 10–3 (C) 6.0 × 10–3 (D) 8.3 × 10–3
28. At 445ºC, Kc for the following reaction is 0.020.
2HI(g) H2(g) + I2(g)
A mixture of H2, I2 and HI in a vessel at 445º C has the following concentrations : [NSEC-2011]
[HI] = 2.0M, [H2] = 0.50M and [I2] = 0.10M. The statement that is true concerning the reaction quotient,
Qc is:
(A) Qc = Kc ; the system is at equilibrium
(B) Qc is less than Kc; more H2 and I2 will be produced
(C) Qc is less than Kc; more HI will be produced
(D) Qc is greater than Kc; more H2 and I2 will be produced
29. The oxidation of SO2 by O2 is an exothermic reaction. The yield of SO3 can be maximized if :
(A) temperature is increased and pressure is kept constant [NSEC-2012]
(B) temperature is decreased and pressure is increased
(C) both temperature and pressure are increased
(D) both temperature and pressure are decreased

30. In which of the following reaction is Kp > Kc [NSEC-2012]


(A) H2 + I2 2 HI (B) N2 + 3H2 2 NH3
(C) 2SO3 2SO2 + O2 (D) PCl3 + Cl2 PCl5

31. The KP/KC ratio for the reaction 4NH3(g) + 5O2(g) 4 NO(g) + 6 H2O(g), at 127ºC is: [NSEC-2013]
(A) 0.0301 (B) 0.0831 (C) 1.0001 (D) 33.26
32. KP for the reaction given below is 1.36 at 499 K. Which of the following equaitons can be used to
calculate Kc for this reaction ? [NSEC-2013]
N2O5(g) — N2O3(g) + O2(g)
[(0.0821) (499)] [(1.36) (0.0821)]
(A) Kc = (B) Kc =
[1.36] [499]
[1.36] [(1.36) (499)]
(C) Kc = (D) Kc =
[(0.0821)  (499)] [0.0821]

33. At 700 K, for the reaction 2SO2(g) + O2(g) 2SO3(g) the Kp is 3.2 × 104. At the same temperature
the KP for the reaction SO3(g) SO2(g) + 0.50O2(g) is : [NSEC-2014]
(A) 3.125 × 10–5 (B) 5.59  103 (C) 1.79  104 (D) 1.79  102
34. For the following reaction, formation of the product is favored by [NSEC-2015]
A2(g) + 4B2(g) 2AB4(g), H < 0
(A) Low temperature and high pressure (B) High temperature and low pressure
(C) Low temperature and low pressure (D) High temperature and high pressure
35. The equilibrium constant of the following isomerisation reaction at 400K and 298 K are 2.07 and 3.42
respectively.
k1
cis-butene trans-butene
k–1
Which of the following is/are correct ? [NSEC-2017]
I. The reaction is exothermic
II. The reaction is endothermic
III. At 400K 50% of cis-butene and 50% of trans-butene are present of equilibrium
IV. Both at 298K and 400K, k1 =k–1
(A) I and IV (B) II and IV (C) I and III (D) I only
36. Acetic acid (CH3COOH) is partially dimerised to (CH3COOH)2 in the vapour phase. At a total pressure
of 0.200 atm, acetic acid is 92.0% dimerized at 298 K.
The value of equilibrium constant of dimerisation under these conditions is [NSEC-2017]
(A) 57.5 (B) 9.7 (C) 97 (D) 194
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Chemical Equilibrium

PART - III : HIGH LEVEL PROBLEMS (HLP)


SUBJECTIVE QUESTIONS
1. In a vessel, two equilibrium are simultaneously established at the same temperature as follows:
N2(g) + 3H2 (g) 2 NH3 (g) ...(1)
N2(g) + 2H2 (g) N2H4 (g) ...(2)
Initially the vessel contains N2 and H2 in the molar ratio of 9 : 13. The equilibrium pressure is 7P 0, in
which pressure due to ammonia is P0 and due to hydrogen is 2P0. Find the values of equilibrium
constants (KP’s) for both the reactions

ONLY ONE OPTION CORRECT TYPE


2. For the following gases equilibrium, N2O4(g) 2NO2(g), Kp is found to be equal to Kc. This is
attained when :
(A) 0ºC (B) 273 K (C) 1 K (D) 12.19 K
3. Consider the following reversible gaseous reactions (at 298 K) :
(a) N2O4 2NO2 (b) 2SO2 + O2 2SO3
(c) 2H H2 +  2 (d) X + Y 4Z
Kp
Highest and lowest value of will be shown by the equilibrium
Kc
(A) d, b (B) a, c (C) a, b (D) b, c7
4. For a container containing A(g), B(g), C(g) & D(g) with rigid walls, an experiment is carried upon. This
experiment involves increase in temperature of container in steps of 1ºC and system is allowed to attain
equilibrium, followed by calculation of K1 & K2 at each step, where K1 & K2 are equilibrium constants for
reaction (1) & (2) respectively.
A(g) + 2B(g) C(g) + D(g) ...(1)
C(g) + D(g) A(g) + 2B(g) ...(2)
Select the graph showing correct relationship –

(A) (B) (C) (D)

5. If CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g) KP = 4 × 10–4 atm2


at 25ºC. The efflorescent nature of CuSO4.5H2O can be noticed when vapour pressure of H 2O in
atmosphere is
(A) > 15.2 mm (B) < 15.2 mm (C) < 15.2 mm (D) = 15.2 mm

6. At a temperature T, a compound AB4(g) dissociates as 2AB4(g) A2(g) + 4B2(g) with a degree of


dissociation x, which is small compared with unity. The expression of KP in terms of x and total pressure
P is :
(A) 8P3x5 (B) 256P3x5 (C) 4Px2 (D) None of these.

7. The equilibrium, SO2Cl2(g) SO2(g) + Cl2(g) is attained at 25ºC in a closed container and inert gas
helium is introduced isothermally. Which of the following statement(s) is/are correct ?
I. Concentrations of SO2, Cl2 and SO2Cl2 change
II. More chlorine is formed
III. Concentration of SO2 is reduced
IV. More SO2Cl2 is formed.
(A) I, II, III (B) II, III, IV (C) III, IV (D) None

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8. C(s) + CO2(g) 2CO(g) KP = 1 atm
CaCO3(s) CaO(s) + CO2(g) KP = 4 × 10–2
Solid C, CaO and CaCO3 are mixed and allowed to attain equilibrium. Calculate final pressure of CO.
(A) 0.4 atm (B) 0.2 atm (C) 8 atm (D) 0.01 atm
9. Ammonia gas at 15 atm is introduced in a rigid vessel at 300 K. At equilibrium the total pressure of the
vessel is found to be 40.11 atm at 300ºC. The degree of dissociation of NH3 will be :
(A) 0.6 (B) 0.4 (C) Unpredictable (D) None of these
10. Two solid A and B are present in two different container having same volume and same temperature
following equilibrium are established :
In container (1) A(s) D(g) + C(g) PT = 40 atm at equilibrium
In container (2) B(s) E(g) + F(g) PT = 60 atm at equilibrium
If excess of A and B are added to a third container having double the volume and at same temperature
then, the total pressure of this container at equilibrium is :
(A) 50 atm (B) 100 atm (C) 200 atm (D) 70 atm

11. For equilibrium ZnSO4.7H2O(s) ZnSO4.2H2O(s) + 5H2O(g), KP = 56.25 × 10–10 atm5 and vapour
pressure of water is 22.8 torr at 298 K. ZnSO 4.7H2O(s) is efflorescent (lose water) when relative
humidity is [ 5 56.25 = 2.23]
(A) more than 80.60% (B) less than 74.60%
(C) Above than 74.60% (D) Above than 70.60%
12. Solid A and B are taken in a closed container at a certain temperature. These two solids decompose
and following equilibria are established simultaneously
A(s) X(g) + Y(g) K P1 = 250 atm 2
B(s) Y(g) + Z(g) K P2 = ?
If the total pressure developed over the solid mixture is 50 atm. Then the value of KP for the 2nd
reaction.
(A) 375 (B) 625 (C) 225 (D) 250

13. X(s) Y(g) + 2Z(g)


A(s) Y(g) + B(g)
Consider both these equilibrium to be established simultaneously in a closed container.
At equilibrium, pressure of Z and B were found to be same and sum of pressure of Z & B is 10 atm
more than that of species Y. Find ratio of standard gibb’s energy of two reactions.
3  log12
(A) 20 (B) 2.303 log1020 (C) log10 3 144 (D)
2  log6

14. In one experiment, certain amount of NH4I(s) was heated rapidly in a closed container at 375ºC. The
following equilibrium was established :
NH4I(s) NH3(g) + HI(g)
Excess of NH4I(s) remained unreacted in the flask and equilibrium pressure was 304 mm of Hg. After
some time, the pressure started increasing further owing to the dissociation of H I.
2HI(g) H2(g) + I2(g) KC = 0.010 calculate final pressure.
(A) 328 mm Hg (B) 331 mm Hg
(C) 662 mm Hg (D) 151 mm Hg

15. A(s) B(g) + C(g) K P1 = 36 atm2


E(s) B(g) + D(g) K P2 = 64 atm2
Both solids A & E were taken in a container of constant volume at a given temperature. Total pressure
in the container after equilibrium is
(A) 6 atm (B) 5 atm (C) 10 atm (D) 20 atm

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16. In a closed container following equilibrium will be attained –
A(s) + B(g) AB(g)
B(g) + C(g) BC(g)
On adding He gas (inert) to the above system at constant pressure & temperature
(A) Amount of AB(g) will be increased surely. (B) Amount of BC(g) will be decreased surely.
(C) Amount of C(g) will be decreased surely. (D) both (A) and (B).

17. 2NH3(g) N2(g) + 3H2(g) in a V lit container total x mol at eq.


N2H4(g) N2 + 2H2(g) in V lit (other) container total y mol at eq.
If both are taken in same container (V lit) then at new equation total mols will be
(A) x + y (B) > x + y (C) < x + y (D) No prediction is possible.

SINGLE AND DOUBLE VALUE INTEGER TYPE


1
18. The equilibrium SO2(g) + O2(g) SO3(g) is established in a container of 4L at a particular
2
temperature. If the number of moles of SO2, O2 and SO3 at equilibrium are 2, 1 and 4 respectively then
find the value of equilibrium constant.

19. If the equilibrium constant of the reaction 2HI(g) H2(g) + I2(g) is 0.25, find the equilibrium
1 1
constant of the reaction H2 (g) + I2 (g) HI(g).
2 2

20. A2(g) and B2(g) having partial pressures 60 mm of Hg & 42 mm of Hg respectively, are present in a
closed vessel. At equilibrium, partial pressure of AB(g) is 28 mm of Hg. If all measurements are made
under similar condition, then calculate percentage of dissociation of AB (g).
(Round of answers to nearest integer).

21. NH4HS(s) NH3(g) + H2S(g) K P1


1 3
NH3(g) N2(g) + H2(g) K P2
2 2
K P22
2 mol NH4HS(s) is taken & 50% of this is dissociated till at equilibrium in 1 litre container. Find if
K P6
1

0.25 moles of N2 are found finally.

7
22. Consider : (I) C(s) + O2 CO2(g) Kp 
1 8
(II) 2 C(s) + O2 2 CO(g) Kp  12.5 atm
2

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 CO 2 in the final
equilibrium mixture.
23. Two solid compounds A and C dissociate into gaseous product at temperature T as follows :
(i) A(s) B(g) + D(g) Kp1 = 625 (atm)2
(ii) C(s) E(g) + D(g) Kp2 = 975 (atm)2
Both solid are present in same container then calculate total pressure over the solid mixture.
24. If a mixture 0.4 mole H2 and 0.2 mole Br2 is heated at 700 K at equilibrium, the value of equilibrium
constant is 0.25 × 1010 then find out the ratio of concentrations of (Br 2) and (HBr) (Report your answer
Br2
as × 1011)
HBr

25. 2 mole of PCl5 were heated in a 5 liter vessel. It dissociated. 80% at equilibrium find out the value of
equilibrium constant. Report your answer as KC × 50.

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26. Two solids A and D dissociates into gaseous products as follows
A(s) B(g) + C (g) ; KP1 = 300 ; D(s) E(g) + C (g) K P2 = 600
at 27ºC , then find the total pressure of the solid mixture.

ONE OR MORE THAN ONE OPTIONS CORRECT TYPE


27. (i) N2(g) + O2(g) 2NO(g), K1
 1  1
(ii)   N2(g) +   O2(g) NO(g) ; K2
2 2
(iii) 2NO(g) N2(g) + O2(g) ; K3
 1  1
(iv) NO(g)   N2(g) +   O2(g) ; K4
2 2
Correct relation between K1, K2, K3 and K4 is/are :
(A) K1 × K3 = 1 (B) K1 K4 = 1 (C) K3 K2 = 1 (D) None

28. A 2 lit vessel is filled by 1 mole of each gas A & B. If K C for reaction
A(g) B(g) is 1.5 at temp. T. [Atomic mass of A is 40 & B is 20].
Which are correct option.
(A) [A] vs time is graph I (B) [B] vs time is graph I
(C) [A] vs time is graph II (D) [B] vs time is graph II

29. The equilibrium constant for some reactions are given below against each of the reaction
(i) 2N2 + 5O2 2N2O5 ; K = 5 × 10–27
(ii) N2 + O2 2NO ; K = 2 × 10–15
(iii) N2 + 2O2 2NO2 ; K = 1.5 × 10–29
Which of the following statement is correct
(A) The least stable oxide is NO2
(B) The most stable oxide is NO
(C) The stability order is N2O5 > NO2 > NO
(D) The stability order is NO2 > NO > N2O5
30. Sufficient amount of a solid X is taken in a rigid vessel at T°C where it attained the equilibrium :
X (s) Y(g) + 2Z(g)
Total pressure was measured. Now the vessel is evacuated and filled with sufficient amount of another
solid V under same conditions where it attained theequilibrium :
V(s) W (g) + 2Z(g)
Total pressure measured now is found to be double that of previous value. Now, if both X & V solids
are allowed to attain their respective equilibrium together in the same vessel at same temperature,
select the correct statement(s) :
(A) KP for decompostion reaction of V (s) = 8 × KP for decomposition reaction of X (s).
1
(B) In the 3rd case (when both solids are simultaneously estabilishing their equilibrium), PY = PW .
8
1
(C) PY in 3rd case = 3 × PY in 1st case.
3 3
rd
(D) In the 3 case, Pw : PZ = 4:9

31. CaCO3(s) CaO(s) + CO2(g)


1
CO2(g) CO(g) + O2 (g)
2
For above simultaneous equilibrium if CO2 is added from out side at equilibrium then :
(A) PCO 2 will increase (B) PCO 2 will decrease
(C) No shift in 2nd equilibrium (D) Backward shift in 1st equilibrium

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Chemical Equilibrium
32. For the reaction SnO2(s) + 2H2(g) 2H2O(g) + Sn(s). If at 900 K, equilibrium mixture contains 45%
H2 by volume and at 1100 K it contains 24% H2 by volume then which of the statements is/are correct.
(A) Reaction is endothermic in nature
(B) At higher temperature, the efficiency of reduction of tin oxide will increase
(C) Reaction is exothermic in nature
(D) At lower temperature, the efficiency of reduction of tin oxide decreases.

33. Consider equilibrium H2O() H2O(g). Choose the correct direction of shifting of equilibrium with
relative humidity.
(A) R.H. > 1, rightward (B) R.H. < 1, rightward
(C) R.H. > 1, leftward (D) R.H. < 1, leftward
34. An industrial fuel, ‘water gas’, which consists of a mixture of H2 and CO can be made by passing steam
over red-hot carbon. The reaction is
C(s) + H2O(g) CO(g) + H2(g), H = +131 kJ
The yield of CO and H2 at equilibrium would be shifted to the product side by :
(A) raising the relative pressure of the steam (B) adding hot carbon
(C) raising the temperature (D) reducing the volume of the system

PART - IV : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))


Max. Time : 1 Hr. Max. Marks : 60
Important Instructions :
A. General %
1. The test is of 1 hour duration.
2. The Test Booklet consists of 20 questions. The maximum marks are 60.
B. Question Paper Format
3. Each part consists of five sections.
4. Section-1 contains 7 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out of
which ONE is correct.
5. Section-2 contains 4 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out of
which ONE OR MORE THAN ONE are correct.
6. Section-3 contains 6 questions. The answer to each of the questions is a single-digit integer, ranging from
0 to 9 (both inclusive).
7. Section-4 contains 1 paragraphs each describing theory, experiment and data etc. 2 questions relate to
paragraph. Each question pertaining to a partcular passage should have only one correct answer among
the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 : 1, 2,
3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY ONE
is correct.
C. Marking Scheme
9. For each question in Section 1, 4 and 5 you will be awarded 3 marks if you darken the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus one
(– 1) mark will be awarded.
10. For each question in Section 2, you will be awarded 3 marks. If you darken all the bubble(s)
corresponding to the correct answer(s) and zero mark. If no bubbles are darkened. No negative marks will
be answered for incorrect answer in this section.
11. For each question in Section 3, you will be awarded 3 marks if you darken only the bubble corresponding
to the correct answer and zero mark if no bubble is darkened. No negative marks will be awarded for
incorrect answer in this section.

SECTION-1 : (Only One option correct Type)


This section contains 7 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

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Chemical Equilibrium
1. Which of the following is correct for the equilibrium of the reaction
C(s) + H2O(g) CO(g) + H2(g)
2
pH 2O
(A) pH2  pH2O (B) pH2  pH2O (C) pH2  pH
2
2O
(D) pH2 
pCO

2. For the reaction PCl5 PCl3 + Cl2; supposing at constant temperature, if the volume is increased
to 16 times the initial volume, the degree of dissociation for this reaction will becomes : ( <<< 1)
1 1
(A) 4 times (B) times (C) 2 times (D) times
4 4

3. A vessel of 10 L was filled with 6 mole of Sb2S3 and 6 mole of H2 to attain the equilibrium at 440oC as :
Sb2S3(s) + 3H2(g) 2Sb(s) + 3H2S(g)
After equilibrium the H2S formed was analysed by dissolving it in water and treating with excess of Pb 2+
to give 708 g of PbS as precipitate. What is value of Kc of the reaction at 440ºC ? (At. weight of
Pb = 206).
(A) 1 (B) 0.8 (C) 0.4 (D) 0.04
1
4. Variation of log10 K with is shown by the following graph in which straight line is at 45°, hence H° is :
T

(A) + 4.606 cal (B) – 4.606 cal (C) 2 cal (D) – 2 cal
5. aA + bB cC + dD
In above reaction low pressure and high temperature, conditions are shift equilibrium in back direction
so correct set :
(A) (a + b) > (c + d), H > 0 (B) (a + b) < (c + d), H > 0
(C) (a + b) < (c + d), H < 0 (D) (a + b) > (c + d), H < 0
6. The value of kp for the reaction at 27ºC
Br2() + 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() is also 0.1 atm. Then what will be minimum moles of Br 2() to
be added to 1 mole of Cl2, initially, to get above equilibrium situation :
10 5 15
(A) moles (B) moles (C) moles (D) 2 moles
6 6 6

7. C(s) 2A(g) + B(s)


If the dissociation of C(s) is ‘’ and d is the density of the gaseous mixture in the container. Initially
container have only ‘C(s)’ and the reaction is carried at constant temperature and pressure.

(A) (B) (C) (D)

Section-2 : (One or More than one options correct Type)


This section contains 4 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.
Kp
8. For which reaction at 298 K, the value of is maximum and minimum respectively :
Kc
(A) N2O4 2NO2 (B) 2SO2 + O2 2SO3
(C) X + Y 4Z (D) A + 3B 7C

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9. For the equilibrium 2SO2(g) + O2(g) 2SO3(g), H = –198 kJ, the equilibrium concentration of SO 3
will be affected by
(A) doubling the volume of the reaction vessel
(B) increasing the temperature at constant volume
(C) adding more oxygen to the reaction vessel
(D) adding helium to the reaction vessel at constant volume

10. AB(s) A(g) + B(g) Kp = 4, H = +ve


In a container, A (g) and B (g) are filled to partial pressure of 1 atm each. Now AB (s) is added (in
excess quantity). Which of the following is CORRECT ? (No other gas is present in container) :
(A) At equilibrium, the total pressure in the container is 4 atm.
(B) Equilibrium pressure decreases uniformly on increasing the volume by container.
(C) At equilibrium, the total pressure in the container is more than 4 atm, if temperature is increased.
(D) None of these
11. Following two equilibria are established seperately in 2 different containers of unequal volume.
PCl5(g) PCl3(g) + Cl2(g)
COCl2(g) CO(g) + Cl2(g)
Now the containers are connected together by a thin tube of negligible volume.
Select incorrect statement(s). (Assume T constant)
(A) Degree of dissociation of both PCl5(g) & COCl2(g) will decrease
(B) Degree of dissociation of both PCl5(g) & COCl2(g) will increase
(C) Degree of dissociation of PCl5(g)may increase ; decrease or remain the same irrespective of effect
on degree of dissociation of COCl2(g).
(D) Degree of dissociation of PCl5(g) may increase, decrease or remain the same, but the effect would
be same as that on degree of dissociation of COCl2.

Section-3 : (One Integer Value Correct Type.)


This section contains 6 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)

12. If 1 mole of CH3COOH and 1 mole of C2H5OH are taken in 1 litre flask, 50% of CH3COOH is converted
into ester as ;
CH3COOH() + C2H5OH() CH3COOC2H5() + H2O()
There is 33% conversion of CH3COOH into ester, if CH3COOH and C2H5OH have been taken initially in
molar ratio x : 1, find x.
13. Solid ammonium carbamate (NH2COONH4) was taken in excess in closed container of volume 5 Litre
according to the following reaction NH2COONH4(s) 2NH3(g) + CO2(g). If equilibrium partial
pressure of ammonia is 4 atm, it’s equilibrium constant K p is x atm3. If the above equilibrium mixture is
transferred to another vessel of volume 10 Litre, total equilibrium pressure is y atm. Calculate the value
of (x + y). Assuming temperature is constant during the whole experiment.
14. Find the percentage dissociation of ammonia into N 2 and H2 if the dissociation is carried out at constant
pressure and the volume at equilibrium is 20% greater than initial volume. (Initially, equal moles of NH3
and N2 are present with no hydrogen)
15. A2B(g) is introduced in a vessel at 1000 K. If partial pressure of A2B(g) is 1 atm initially and KP for
reaction A2B(g) 2A(g) + B(g) is 81 × 10–6 then calculate percentage of dissociation of A2B.
16. Consider the following two equilibrium established together in a closed container
A(s) 2B(g) + 3C(g) ; KP1
A(s) 3D(g) ; K P2
Starting with only A(s), molar ratio of B(g) & D(g) at equilibrium is found to be in a ratio 1 : 6. If partial
KP2
pressure of B at equilibrium be 1 atm, determine .
8KP1

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Chemical Equilibrium
17. 0.1 mol each of ethyl alcohol and acetic acid are allowed to react and at equilibrium the acid was
exactly neutralised by 100 ml of 0.75 N NaOH. If no hydrolysis of ester is supposed to have undergo
1
find KC. Report your answer as .
KC

SECTION-4 : Comprehension Type (Only One options correct)


This section contains 1 paragraphs, each describing theory, experiments, data etc. 2 questions
relate to the paragraph. Each question has only one correct answer among the four given
options (A), (B), (C) and (D)

Paragraph for Question Nos. 18 to 19


There are different types of equilibria depending on the composition of equilibrium mixture.
Homogenous equilibrium contains all the species in same phase and heterogeneous equilibrium
contains different phases. If heterogeneous equilibrium involves pure solid or liquid, then their
concentration or pressure term is not included in KC or KP respectively.

18. 0.5 mole of NH4HS(s) are taken in a container having N2. On warming the closed container to 50ºC the
pressure attained a constant value of 1.5 atm, with some NH4HS(s) remaining unreacted and partial
pressure of N2 being 1 atm. The KP of reaction NH4HS(s) NH3(g) + H2S(g) at 50°C is :
(A) 0.25 (B) 0.625 (C) 0.025 (D) 0.0625

19. How many moles of water are in vapour phase present inside 1 L vessel containing enough water after
25
sufficient time? (Vapour pressure of water at 27ºC = 3000 Pa, R = J/mol–K)
3
(A) 1.2 × 10–3 (B) 120 (C) 5 × 10–4 (D) None of these

SECTION-5 : Matching List Type (Only One options correct)


This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct

20. In given setup, container I has double the volume to that of container II. Container I & II are connected
by a narrow tube with two knobs.

Knob A : Closed – No gas is allowed to pass through


Open – All gases can pass
Knob B : Closed – A thin filter of Pd is introduced on complete cross section of tube
Open – All gases can pass.
Initially both knobs are closed. In container I, some amount of NH 3 gas is introduced which sets up
equilibrium according to following reaction :
2NH3(g) N2(g) + H2(g)
Match the actions in column I to corresponding value in column II and select the correct answer using
the code given below the column. Assume each action from initial stage.

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Chemical Equilibrium
Column I Column II
P. A & B are closed, p H 2 / p N 2 = ? 1. 1/3
Q. A is open & B is closed, nHI 2 / nNI 2 =? 2. 3
R. A is open & B is open, nNI 2 / nHII2 =? 3. 2
A & B are left open for long time;
S. now B is closed & volume of container II is halved. 4. 2/3
( nNI 2 + nNII2 )/( nHI 2 + nHII2 ) = ?
Code :
P Q R S P Q R S
(A) 4 2 3 1 (B) 2 3 4 1
(C) 2 1 3 4 (D) 1 2 3 4

Practice Test-2 (IIT-JEE (ADVANCED Pattern))


OBJECTIVE RESPONSE SHEET (ORS)

Que. 1 2 3 4 5 6 7 8 9 10

Ans.

Que. 11 12 13 14 15 16 17 18 19 20

Ans.

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Chemical Equilibrium

PART - I
1. (2) 2. (4) 3. (3) 4. (2) 5. (3)
6. (1) 7. (2) 8. (4) 9. (1) 10. (4)
11. (3) 12. (4) 13. (1) 14. (1) 15. (1)
16. (2) 17. (3) 18. (1) 19. (1) 20. (3)
21. (4) 22. (1) 23. (3) 24. (2) 25. (2)
26. (4) 27. (2) 28. (1) 29. (1) 30. (1)

PART - II
1. (B) 2. (C) 3. (C) 4. (D) 5. (C)
6. (B) 7. (A) 8. (D) 9. (B) 10. (B)
11. (A) 12. (C) 13. (A) 14. (B) 15. (D)
16. (C) 17. (A) 18. (A) 19. (D) 20. (D)
21. (D) 22. (A) 23. (B) 24. (A) 25. (D)
26. (CD) 27. (C) 28. (B) 29. (B) 30. (C)
31. (A) 32. (C) 33. (B) 34. (A) 35. (D)
36. (D)

PART - III
1 3
1. K P1 = , K P2 = 2. (D) 3. (A) 4. (C)
20P02 20 P02

5. (B) 6. (A) 7. (D) 8. (B) 9. (B)


10. (B) 11. (B) 12. (A) 13. (D) 14. (A)
15. (D) 16. (D) 17. (C) 18. 4 19. 2
20. 72 % 21. 27 22. 17 23. 60 atm 24. 80
25. 64 26. 80 atm. 27. (ABC) 28. (BC) 29. (AB)
30. (ABCD) 31. (CD) 32. (ABD) 33. (BC) 34. (AC)

PART - IV
1. (B) 2. (A) 3. (A) 4. (B) 5. (D)
6. (C) 7. (D) 8. (BD) 9. (ABC) 10.(AC)
11. (ABCD) 12. 2 13. 38 14. 40 15. 3
16. 8 17. 9 18. (D) 19. (A) 20. (B)

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Chemical Equilibrium

PART – I
1. N2 + 3H2 2 NH3
t=0 1 mole 2 mole 0
t = eq 1–x 2–3x 2x = 0.8
x = 0.4
mole of N2 = 0.6
mole of H2 = 0.8
KA [PQ]
2.  ..... (i)
KB [P] [Q]
KC [R]
 ..... (ii)
KD [PQ]
On multiply equation (i) and (ii) we get
K A .K C [R]
=
K B .K D [P][Q]

4. 2SO2(g) + O2(g) 2SO3(g)


2
[SO3 ]
KC = Concentration in gram mole/litre, therefore
[SO2 ]2 [O2 ]
48
[SO3] = (Where 80 is molecular weight of SO3)
80  1
128
[SO2] = (Where 64 is molecular weight of SO2)
64  1
9.6
[O2] = (Where 32 is molecular weight of O2)
32  1
Thus, KC = = 0.30
5. Since, Kp is temperature dependent only.
6. H2(g) + I2(g) 2HI(g)
t=0 4.5 4.5 0
t = teq. 4.5 – x 4.5 – x 2x
put x = 1.5
4.5 – 1.5 4.5 – 1.5 2 × 1.5 = 3
    
  3 3 3
(3)2
KC = =1
33

7. Co + H2O CO2 + H2
t=0 1 1 1 0
t = teq 1 – x 1 – x 1 + x x
at equilibrium, only CO2 has (1 + x) moles.
8. Kp = Kc (RT)n, n = 4 – 3 = 1
0.05 = Kc R × 1000
Kc = 5 × 10–5 × R–1
13. N2 + O2 2NO 2x = 1.0 mole/litre
a b 0 x = 1.0/2 mole/litre = 0.50 mole/litre
(a – x) (b–x) 2x
If a – x = 0.25, b – x = 0.05
[N2] = a = a – x + x = 0.25 + 0.50 = 0.75 mole/litre

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Chemical Equilibrium
14. 2A8 2 A3 + 3 A2 + A4
t=0 2 0 0 0
t = teq 2 – 2 2  3  
  nT = 2 + 4
given mole fraction of A2 is = 0.36.
3
0.36 =   = 0.46
2  4
2  2 2  2  0.46
Mole fraction of A8 = = = 0.28
2  4 2  4  0.46

15. 2NO N2 + O 2   = 10%


t=0 4 – .4 .2 .2
3.6 0.2 0.2
 n = 0,
(.2 / V)2 4
 KP = KC, KC = =
(3.6 / V)2 36  36

1 
16. Total moles at equilibrium = 1 + /n = 1 +   1 
n  
di 1 
So using = 1 +   1  .
df n 

17. NH4HS(s) NH3(g) + H2S(g)


Total pressure is P
P
So, PNH 3 = PH S =
2
2
P2
Kp = PNH3 × PH2S = .
4

18. At room temperature, K = 4.32 and at 425°C, equilibrium constant become 1.24 × 10 –4 i.e. it is
decreases with increase in temperature. So, it is exothermic reaction.
20. Catalyst can't disturb the state of the equilibrium.
23. PCl5 PCl3 + Cl2
at t = 0 a 0 0
t = teq a–xx x
PPCl3  XPCl3 PT = .25 × 2 = .5 atm
PPCl3  PCl2 = .5 atm

24. Gº = – RT ln Keq lnKeq = –6


25
15000 = – × 300 ln Keq Keq = e–6
3
15000
lnKeq = – =6
2500

25. G° = –2.303 RT log K


26. At point A, Q = tan 60ºC
Q = 1.732
 Q = K = 1.732
PPCl3 (g)  PCl2 (g) (nPCl3 (g) )eq.  (nCl2 (g) )eq.
28. According to KP = =
PPCl5 (g) V  (nPCl5 (g) )eq.
and on adding inert gas at constant pressure effect on equilibrium will be similar to as if volume of
container has been increased.

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Chemical Equilibrium
1
29. NO + O2 NO2
2
GR H = 52 – 87 = –35 kJ
º

Gº = –RTlnKeq
35000
lnKeq = .
8.314  298

30. CO + H2O CO2 + H2


0.4 0.4
0.4 – x 0.4 – x x x
x
=3
0.4  x
1.2 – 3x = x
1.2 = 4x
1.2
x= = 0.3
4
x = 0.3

PART - III
1. N2(g) + 3H2(g) 2NH3 (g)
9P – x – y 13P – 3x – 2Y 2x
N2(g) + 2H2(g) N2H4(g)
9P – x – y 13p – 3x – 2Y Y
given 9P – x – y + 13P – 3x –2y + 2x + y = 7Po
 22P – 2x – 2y = 7Po ........(1)
then 2x = Po ..........(2)
and 13P – 3x – 2y = 2Po .........(3)

Po
P=
2
9Po P 3Po 5P 13  7
9P – x – y = – o – = o 2y = Po = 3Po
2 2 2 2 2
13Po 3Po 6Po 3
13P – 3x – 2y = – – = 2Po y= Po
2 2 2 2
(2x)2 Po2 1
K1 = = =
(9p  x  y)(13p  3x  2y) 3 5 20Po2
Po .(2Po )3
2
3
Po 3
K2 = 2 =
5  2
 2 Po   2Po 
2 20P o
 

2. N2O4 2NO2(g)
n = 2 – 1 = 1, KP = KC (given)
We know, KP = KC (RT)n
1
1 = RT, T = = 12.19 K
.0821

1
4. K1 = for same value of T.
K2
 K1K2 = 1 similar to yx = const.

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Chemical Equilibrium
5. An efflorescent salt is one that loss of H2O to atmosphere.
CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g)
KP = ( PH' 2O )2 = 4 × 10–4
PH' 2O = 2 × 10–2 atm = 15.2 mm Hg
If PH' 2O at 25ºC < 15.2 mm only then reaction will proceed in forward direction.

3
6. 2AB4(g) A2(g) + 4B2(g)  n =1+ 2
 1

1– 2x 1-  1
2
4
    2 
 2 P  1 P
KP =     = 8P35
P  2

8. C(s) + CO2(g) 2CO(g)


2
(PCO )
KP = '
= 1.0
PCO2

At equilibrium, PCO 2 = KP = 4 × 10–2 remain constant


(PCO )2
=1
4 10–2
PCO = 4  10–2 = 0.2 atm

9. P1 = 15 atm ; T1 = 300 K.
Equilibrium temperature is 300ºC that is 573 K.
So first of all we have to calculate pressure of NH3 at 573 K.
P1 P 15 P
= 2 = = 2
T1 T2 300 573
P2 = 28.65 atm at 300ºC.
1 3
NH3 (g) N2(g) + H2(g).
2 2
t=0 28.65 atm 0 0
x 3
t = teq. [28.65–x] atm x
2 2
But according to question.
x 3
Ptotal = 28.65 – x + + x
2 2
Or 28.65 + x = 40.11.
x = 11.46.
11.46
Degree of dissociation of NH3 = = 0.4.
28.65

10. (1) A(s) D(g) + C(g) Kp = (20)2


20 atm 20 atm
(2) B(s) E(g) + F(g) Kp = (30)2
30 atm 30 atm
(3) container Kp is same so on doubling the volume partial pressure does not change but moles of C, D,
E, F will change to maintain their partial pressure. So total pressure = 40 + 60 = 100 atm.
11. KP = ( PH2O )5 = 56.25 × 10–10
( PH2O ) = (56.25 × 10–10)1/5 = (56.25)1/5 × 10–2 = 2.23 × 10–2 × 760 = 17.01 torr
Parital pressure 17.01
% Relative humidity = × 100 = × 100 = 74.60% (less than 74.60%)
Vapour pressure 22.8

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Chemical Equilibrium
12. A(s) X + Y
 +
B(s) Y + Z
 +  
 KP1 =  ( + )
K P2 =  ( + )
Ptotal = ( + ) +  +  = 2 ( + )
 2 ( + ) = 50   +  = 25
 250 25    = 10 ,  = 15
 K P2 =  ( + ) = 15 × 25 = 375

13. X(s) Y(g) + 2Z(g) A(s) Y(g) + B(g)


t = eq. (a+b) 2a t = eq. (a+b) b
Given pZ = pB
2a = b and pZ + pB = pY + 10
(2a + b) = (a + b) + 10
a = 10 atm  b = 20 atm
K P1 = (a + b) (2a)2 = (30) (400) = 12000
K P2 = (a + b) (b) = (30) (20) = 600
G = –RTlnK
G1 nK1 log12000 3  log12
= = =
G2 nK2 log600 2  log6

14. NH4I(s) NH3(g) + HI(g)


at eq. total pressure = 304 mm of Hg
304
pNH3 = pHI = = 152 mm of Hg = 0.2 atm
2
2HI(g) H2(g) + I2(g) NH4I(s) NH3(g) + HI(g)
t=0 0.2 0 0 eq. – 0.2+y 0.2+y–x
x x
t = eq. 0.2+y–x
2 2
We assumed that x atm of HI is used for dissociation which results formation of y atm of H I from
NH4I(s)
for NH4I(s) NH3(g) + HI(g) KC = 0.2 × 0.2
in other case KP = (0.2 + y) (0.2 + y – x)
(0.2 + y) (0.2 + y – x) = 0.2 × 0.2 ...(i)
For 2HI(g) H2(g) + I2(g)
(x / 2)(x / 2)
KC = KP = = 0.010 ...(ii)
(0.2  y – x)2
on solving the equation : x = 0.036 & y = 0.016
total pressure at eq. = pNH3 + pHI + p H 2 + p I 2
= 0.432 atm = 328 mm of Hg
15. A(s) B(g) + C(g) , E(s) B(g) + D(g)
(P1 + P2) P1 (P1 + P2) P2
Total pressure = 2(P1 + P2) = 2 Ksp1  Ksp2 = 20 atm

16. On addign inert gas at content temperature & pressure 2 nd reaction will be shifted in backward direction.
17. On mixing, P(N2) & P(H2) will add up. This will shift both the equilibrium backwards thereby decreasing
the number of moles.

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Chemical Equilibrium
1
18. SO2 (g) + O2 (g) SO3 (g)
2
No. of mole 2 1 4
2 1 4
conc. .
4 4 4
[SO3 ] 1 1
KC = = = = 4 Ans.
[SO2 ][O2 ]1/ 2 (1/ 2) (1/ 4)1/ 2 (1/ 2)  (1/ 2)

1
19. For reaction, H2(g) + I2(g) 2HI(g) K’ = =4
0.25
1 1
For reaction, H2 + I2 HI(g) K’’ = 4
2 2

20. A2(g) + B2(g) 2AB(g)


at t = 0 60 42 0
at eq. (60–x) (42–x) (2x)
(Partial pressures)
2x = 28  x = 14
2 2
(PAB ) (28) 14
Kp = = =
(PA2 )(PB2 ) (46)(28) 23
14
For ng = 0 ; Kp = KC =
23 1

Let degree of dissociation for AB is ‘x’ , then


 1 23 
2AB(g) A2(g) + B2(g)  K C2   
 K C1 14 

1 0 0
at t = 0 (1 – x) x x
 x  x 
 2  2 
   = 23   =0.719
(1– x)2 14
Hence percentage of dissociatin = 0.719 × 100 = 72 %
21. NH4HS(s) NH3(g) + H2S(g)
1–0.5 1
1 3
NH3(g) N2(g) + H2(g)
2 2
0.5 0.25 0.75
K P1 = 0.5

(0.251/ 2 ) (0.75) 3/2


K P2 =
0.5

22. Since (I) causes no change in volume due to reaction, change from 100 L is due to (II) only.
 V(CO) finally = 10 L
 10 
P(CO) finally =    105 = 10 atm
 105 
102 atm2
 P(O2) = PCO
2
/ K p2 = = 8 atm
12.5atm
PCO2 7
Also, K P1  = ×8 = 7 atm  P(CO2) = KP1. P(O2)
PO2 8
 P(CO) + P(CO2) finally is 10 + 7 = 17 atm

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Chemical Equilibrium
23. A(s) B(g) + D(g) Kp1 = 625
P1 (P1  P2 )

C(s) E(g) + D(g) Kp2 = 975


P2 (P1  P2 )

Kp1 + Kp2 = ( p12 + p22 + 2p1p2) = (p1 + p2)2 = (625 + 975)  (p1 + p2) = 40
so total pressure = 2[p1 + p2] = 80 atm.
24. H2 + Br2 2HBr
t=0 0.4 0.2 –
t = teq. 0.2 y 0.4
= negligible = y
1 0.4  0.4
 × 1010 =
4 0.2  y
y = 3.2 × 10–10
Br2 3.2
× 1011 = × 10–10 × 1011 = 80
HBr 0.4

25. PCl5 PCl3 + Cl2


2 – – KC = a = 2 × 0.8 = 1.6
2–1.6
1.6
= 0.4 1.6 1.6
5
1.6 1.6
0.4 1.6 1.6

KC = 5 5
5 5 5 0.4
5
4  1.6 64 64
KC = = Ans. is × 50 = 64
5 50 50

26. A(s) B(g) + C(g) K P1 = 300


– P1 (P1+P2) K P1 = P1(P1+P2)
D(s) E(g) + C(g) K P2 = 600
P2 P1+P2 K P2 = P2(P1+P2)
 Kp1  P (P P )
  = 1 1 2
 2
Kp P2 (P1  P2 )

300 P 
=  1
600  P2 
P1 1
= P2 = 2P1
P2 2
K P1 = P1(P1+P2)  K P1 = P1 (P1+2P1)  300 = P1 (3P1)
P12 = 100 (P1 = 10)
P2 = 20 atm
Now Total pressure
PB + PE + PC
(P1+P2) + (P1+P2) = (10 + 20) + (30) = 60 atm.
27. From given reactions.
1 1
(i) = – (iii) ; (i) = – (iv) ; (iii) = – (ii)
2 2

29. Higher is the value of equilibrium const, higher will be the stability of products.
31. Second equilibrium will not be affected by CO2 addition only first will shift backward.

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Chemical Equilibrium
32. Since  in temperature results in shifting of equilibria in forward direction hence reaction is endothermic
in nature. Endothermic reaction is driven in forward direction upon increase in temperature.
33. R.H. > 1  > V.P.  Q>K leftward shift
R.H. < 1  < V.P.  Q<K Rightward shift
34. Addition of solids have no effect on equilibrium and temperature favours endothermic direction while
increasing pressure will shift equilibrium in backward direction as ng is +ve.

PART - IV
PCO(g).PH2 (g) (PH2 (g) )2
1. KP = = (as PCO(g) = PH2 (g) )
PH2O(g) PH2O(g)

3. Mole of PbS = 708 / 236 = 3 mole = mole of H2S


Sb2S3(s) + 3H2(g) 2Sb(s) + 3H2S(g)
initial 6 6 0 0
at eq. 5 3 2 3
(3 /10)3
KC = =1
(3 /10)3

4. K = A e–H/RT
H
log K = log A – .
2.303RT
H 1
log K = log A – × .
2.303 R T
 H  1
log K =  –  × + log A.
 2.303 R  T
– H
= 1.
2.303 R
H = – 2.303 R = – 4.606 cal.
5. aA + bB cC + dD
At high temp. & low pressure equilibrium is shifting in backward direction. It means (a + b) > (c + d) &
heat will reaction in the formation of producers is H < 0.
6. Br2() + Cl2(g) 2BrCl(g)
t=0 1 0
(1 – x) 2x
(PBrCl )2
kp = = 1 so, PCl2 = (PBrCl )2 = 0.01 atm
PCl2
nBrCl 0.1 2x
then at equilibrium, = = 10 =
nCl2 0.01 1 x
10 5
So, 10 – 10x = 2x or x= = moles
12 6
Moles of Br2() required for maintaining vapour pressure of 0.1 atm
5 10
moles = =2× moles = moles of BrCl(g).
6 6
5
Moles required for taking part in reaction = moles of Cl 2 used up = moles.
6
5 10 1 5
Hence total moles required =  = moles.
6 6 6

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Chemical Equilibrium
7. As in the gaseous mixture only A will be present so the molecular weight of the gaseous mixture will be
‘MA’
 PMA = dRT where R, P, T are const.
so d  MA
and hence it does not depend on ‘’
so ‘d’ will remain constant.
Option (D) is correct.
12. CH3COOH() + C2H5OH() CH3COOC2H5() + H2O()
1 – 0.5 1 – 0.5 0.5 0.5
0.5  0.5
So, KC = =1
0.5  0.5
Now let a moles of CH3COOH and b moles of C2H5OH are taken :
a a a a
a– b–
3 3 3 3
(a / 3)  (a / 3)  a a a 2
So, KC = or 2 b  = or 2b = a or =
 a  3 3 b 1
2a / 3   b  
 3

13. NH2COONH4(s) 2NH3(g) + CO2(g).


At eq. PNH3 = 4 atm
PCO2 = 2 atm
2
Kp = PNH3
× PCO = 32 atm3.
2
Therefore x = 32 & y = 6  x + y = 38.
14. 2NH3N2 + 3H2
t =0 a a 0
a 3a
a
teq a(1 – ) 2 2
3a
nT = 2a + a = a(2 + ) = 2a + 2 × 2a
2 +  = 2.4   = 0.4 Ans. 40%
15. A2B(g) 2A(g) + B(g)
at t = 0 1 0 0
at eq. (1–x) 2 
 (partial pressure)
Hence, (1 – ) ; 1
(2x)2  ()
= 81 × 10–6
(1)
= 3 × 10–2
percentage of dissociation = 3 ×10–2 × 100 = 3%
16. PB : PD = 1 : 6 Let the partial pressure of Beq. be P0
3
 3P 
K P1 = (P0)2  0 
 2 
K P2 = (6P0) 3

K P2 63
= 3
= 64
K P1 3
2
 
KP2 64
= =8
8KP1 8

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Chemical Equilibrium
17. CH3COOH + C2H5OH CH3COC2H5 + H2O
At t = 0 0.1 0.1 0 0
At equilibrium 0.1–x 0.1–x x x
Meq of acetic acid left = Meq. of NaOH used = 100 × 0.75 = 75
Milimoles of acetic acid left = 75 ( monobasic)
Moles of acetic acid left = 0.075
0.1 – x = 0.075
x = 0.025
x2 (0.025)2 1
KC = 2
= 2
=
(0.1– x) (0.075) 9

18. NH4HS(s) NH3(g) + H2S(g)


p p
2p = 1.5 – 1
2p = 0.5
p = 0.25
 Kp = 0.25 × 0.25 = 0.0625

PV 3000  10 3
19. n= = = 1.2 × 10–3 moles.
RT 25
 300
3
20. (P) Initially, only NH3 was present & according to reaction
2NH3(g) N2(g) + 3H2(g)
nN2 1
=
nH2 3
pN2 1 pH
Same volume for both gases  =  2 =3
pH2 3 pN2
(Q) When B is closed, only H2 diffuses through filter until partial pressure of H2 becomes equal.
nH2
total
=3 ...(1)
nN2
pHI 2 = pHII2 & VI = 2VII  nHI 2 = 2 nHII2
3
nHI 2 + nHII2 = nH2  nH2 / nHI 2 = ...(2)
total total
2
from eq.(1) & (2)
nHI 2 nHI 2 nH2
total
2
= × = ×3=2
nN2 nH2 nN2 3
total

(R) Again same volume for N2 & H2


1
nN2 / nH2 = ...(1)
total total 3
pNI 2 = pNII2 & VI = 2VII  nNI 2 = 2 nNII2 & nHI 2 = 2 nHII2
3 I
nN2 = nNI 2 + nNII2 = 3 nNII2 = nN
total
2 2
nH2 = nHI 2 + nHII2 = 3 nHII2
total

3 I 1 nNI 2 2
from eq.(1) nN / 3 nHII2 =  II
=
2 2 3 n H2
3
1
(S) ( nNI 2 + nNII2 )/( nHI 2 + nHII2 ) =
3

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Website : www.resonance.ac.in | E-mail : [email protected]
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