Equi
Equi
Equi
CHEMICAL EQUILIBRIUM
Law of mass Aciton
1. One mole of SO3 was placed in a vessel of 1 L capacity at a certain temperature constant Kc for the
following equilibrium was established.
2SO3 (g) 2SO2 (g) + O2(g)
At equilibrium, 0.6 moles of SO2 were formed. The equilibrium constant Kc for the reaction will be
(A) 0.36
(B) 0.45
(C) 0.54
(D) 0.675
o
2. At 27 C Kp value for reaction CaCO3 (s) + CO2 (g) is 0.1 atm, calculate its Kc value.
(A) 4 x 10-3
(B) 6 x 10-3
(C) 2 x 10-3
(D) 9 x 10-3
3. Solid NH4l dissolves to the reaction at 400 K
NH4(s) NH3(g) + Hl(g) ; Kp = 16 atm. In presence of catalyst, Hl dissociates into H2 and l2 as
2Hl H2 + l2. If partial pressure of H2 at this temp is 1 atm in the container when both the
equilibrium exist simultaneously, calculate Kp value of second equilibrium (for the dissociation of Hl).
4. A vessel at 1000 K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted into CO
on addition of graphite. What is the value of Kp if the total pressure at equilibrium is 0.8 atm?
Exercise 1
1. Write the expression for Kp and Kc for the following reactions
N2 + 3H2 2NH3
2. select the heterogeneous equilibrium from the following reaction
(A) CaCO3 (s) CaO(s) + CO2 (g)
(B) H2(g) + l2(g) 2Hl (g)
Exercise 2
1. what is the value of equilibrium constant for the following reaction
If A D
A B
K1 = 2
B C
K2 = 5
C D
K3 = 3
(A) 60
(B) 40
(C) 20
(D) 30
2. In an equilibrium A + B C + D ; A and B are mixed in a vessel at temperature T. the initial
concentration of A was twice the initial concentration of B. After the equilibrium has established,
concentration of C was thrice the equilibrium concentration Of B. Calculate Kc.
Exercise - 3
1. Ammonium hydrogen sulphite dissociates as follows
NH4HS(s) NH3(g) + H2S(g)
If solid NH4HS is placed in an evacuated flask at certain temperature it will dissociate until the total
pressure is 600 torr.
(A) calculate the value of equilibrium constant for the dissociation reaction
(B) Additional NH3 is introduced into the equilibrium mixture without changing the
temperature until partial pressure of NH3 is 750 torr. What is the partial temperature of
H2S under these conditions? What is the total pressure in the flask?
2. At 700 K hydrogen and bromine react to form hydrogen bromide. The value of equilibrium
constant for this reaction is 5 x 108. Calculate the amount of H2, Br2 and HBr at equilibrium, if a
mixture of 0.6 mole of H2 and 0.2 mole of Br2 is heated to 700 K.
(A) 1.4, 1, 1.4
(B) 2.2, 0, 0.4
(C) 0.4, 0, 04
(D) 2.3, 1, 2.4
- = {4 x 10-4 [A] [B] 1.33 x 10-5 [C] [D]} mol L-1 min-1
Predict whether the reaction will be spontaneous in the direction as written in reaction mixture in
which each A, B, C and D is having a concentration of 1 molL-1?
Le chateliers Principle
1. N2 + 3H2 2NH3:
H = negative
What are the conditions of temperature and pressure favourable for this reation?
(A) Low temperature, low pressure
(B) high temperature, low pressure
(C) high temperature, high pressure
(D) low temperature, high pressure
2. under what conditions will the following reactions go in the forward direction?
(i) N2(g) + 3H2(g) 2NH3(g) + 23 k cal.
(ii) 2SO2(g) + O2(g) 2SO3(g) + 45 k cal.
(iii)N2(g) + O2(g) 2NO(g) 43.2 k cal.
(iv)2NO(g) + O2(g) 2NO2(g) + 27.8 k cal.
(v) C(s) + HO2(g) CO2(g) + H2(g) + X k cal.
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Exercise - 5
1. How much PCl5 must be added to a one litre vessel at 250o C in order to obtain concentration of
0.1 mole of Cl2? Kc for PCls PCl3 + Cl2 is 0.0414 mol/litre.
PLOBLEMS
1. in an experiment 5 moles of Hl were disclosed in a 5 liters container. At 717 K equilibrium constant
for the gaseous reaction 2HL (g) H2 (g) + l2 (g) is 0.025. Calculate the equilibrium concentrations of
Hl, H2 and l2. What is the fraction of Hl that decomposes?
2.Calculate the volume percent of chlorine at equilibrium in PCl5 under a total pressure of 1.5 atm.
(Kp = 0.202 atm)
3. in a mixture of N2 and H2 initially in a mole ratio of 1 : 3 at 30 atm and 300o C, the equilibrium
constant (Kp) of the mixture, for the reaction
N2(g) + 3H2(g) 2NH3(g)
4. 256 g of Hl was heated in a sealed bulb at 444o C till the equilibrium was attained. The acid was
found to be 22% dissociated at equilibrium. Calculate equilibrium constants for synthesis and
dissociation of Hl?
5. Variation of equilibrium constant K with temperature T is given by Vant Hoff equation
0
Objective
1. At a certain temperature 2 moles of carbonmonoxide and 3 moles of chlorine were allowed to
reach equilibrium according to the reaction CO + Cl2 COCl2 in a 5 lit vessel. At equilibrium if one
mole of CO is present then equilibrium constant for the reaction is:
(A) 2
(B) 2.5
(C) 3.0
(D) 4
2. Kp for the reaction: CO2(g) + H2(g) CO(g) + H2O(g) is found to be 16 at a given temperature.
Originally equal numbers of moles of H2 and CO2 were placed in the flask. At equilibrium, the
pressure of H2 is 1.20 atm. What is the partial pressure of CO and H2O?
(A) 4.80 atm each
(B) 9.60 atm each
(C) 2.40 atm each
(D) 1.20 atm each
3. Kcfor the reaction N2(g) + O2(g) 2NO(g) is 4.0 x 10-6 at 400 K. Kp for the above reaction is
(A) 2.4 x 10-3
(B) 4. 0 x 10-6
-6
2
(C) 4.0 x 10 x (RT)
(D) none of these
4. Kcfor the reaction
A(g) + B(g) C(g) + D(g), is 20 at 25o C if a container contains 1,2,4,5 moles per litre of A(g), B(g), C(g)
And D(g) respectively at 25o C, then the reaction shall
(A) proceed form left to right
(B) proceed from right to left
(C) be at equilibrium
(D) None of the above
5. When a sulphur in the form of S8osjeated at 900 K, the initial pressure of one atm falls by 29% at
equilibrium.
(A) 1.16 atm3
(B) 0.71 atm3
(C) 2.55 atm3
(D) 5.1 atm3
6. for the reversible reaction
N2 (g) + 3H2 (g) 2NH3 (g)
At 500o C, the rate of Kp is 1.44 x 10-5,when partial pressure is measured in atmosphere. The
corresponding value of Kc with concentration in mol/L is
1.44 10 5
1.44 10 5
0.082 773 2
(B)
(D)
1.44
8.314
1.44
0.082
10 5
773 2
10 5
773 2
2 1/3
2 1/2
(B) x =
(D)
1/3
(A) 1 =
(B) 1>2
2
1
1 2
(C) >
1
14. The equilibrium constant at 323o C is 1000. What would be its value in the presense of a catalyst
for the forward reaction?
A + B C + D + 38 Kcal
(A) 1000 x concentration of catalyst
(B) 1000
1000
(C)
(D) impossible to tell
15. A schematic plot of the Keqvs inverse of temperature for a reaction is shown in the figure. The
reaction must be
(A) exothermic
(B) endothermic
(C) one with negligible enthalpy change
(D) highly spontaneous at ordinary temperature
Assignments
Section 1
Part A( Level I)
1. Why sealed soda water bottle on opening shows the evolution of gas with effervescence?
2. for a gas phase reaction for which = 2. Unit of Kp is .
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3. High pressure is favourable for those revesible reactions in which there is .. in the number of
molecules.
4. Suggest four ways in which the concentration of hydrazine, N2H4, could be increase in an N2 (g) +
2H2 (g) N2H2 (g)
= 95 kJ
5. Explain why an equilibrium between Br2() Br2(g) would not be established if the bottle cap were
removed from the bottle containing both these components.
6. Higher the activation energy of a reaction, slower is the rate of reaction. [True/ false]
7. Low pressure is favourable for melting of ice. [True/ False]
8. The reactions having higher value of Kc are faster than the reactions having lower value of Kc,
[True/ false]
9. ice melts slowly at higher altitude, why?
10. Under what vapour pressure of moisture in atomospheric conditions CuSO4, 5H2O will be
efflorescent if CuSO4 . 5H2O(s) + 2H2O(g), Kp = 62.73 mm2 of Hg.
Level II
1. The reaction 2SO2 + O2 2SO3 is made to take place at to C in a closed vessel of 1 litre capacity
and allowed to attain equilibrium. The equilibrium mixture contains 48 g SO3, 12.8 g SO2 and 9.6 g of
O2. Determine Kc.
2. One mole of H2, 2 mol of l2 and 3 mol of Hl are injected in a 1 litre flask. What will be the
concentration of H2, l2 and Hl at equilibrium? Kc for the equilibrium, H2(g) + l2(g) 2Hl is 45.9.
3. 15 g sample of BaO2 is heated to 794o C in a closed evacuated vessel of 5 litres capacity. How
many g of peroxide are converted to BaO(s).
2BaO2(s) 2BaO(s) + O2(g), Kp= 0.5 atm.
4. Consider the vapour phase dissociation of an oxoacid HXO3 according to the equation:
4HXO3(g) 4XO2(g) + 2H2O(g) + O2(g). Derive the expression: Kp = ,
Where P is the total pressure and Po2 is partial pressure of O2.
5. PCl5(g) at 500o K at an initial pressure of 600 mm Hg dissociates as: PCl5 PCl3 + Cl2 and the
equilibrium pressure is 800 mm Hg at 500K. calculateKp for the reaction assuming that no change in
volume takes place.
6. sulphide ions in alkaline solution react with solid sulphur to form polyvalent sulphide ions. The
equilibrium constant for the formation of S2-2 and S3-2 from S and S2- ions are 1.7 and 5.3 respectively.
Calculate equilibrium constant Kc for the formation of S3-2 from S22- and S.
7. The Kc for A2(g) + B2(g) 2AB(g) at 100o C is 0. If one litre flask containing one mole of A2 is
connected with a two litre flask containing 2 mole of B2, how many moles of AB will be formed at
100o C?
8. At 90o C the following equilibrium is established, H2(g) + S(s) H2S(g) K = 6.8 x 10-2 if 0.20 mole of
hydrogen and 1.0 mol of sulphur are heated at 90o C in a 1.0 L vessel, what will be the partial
pressure of H2S at equilibrium?
9. Solid ammonium carbonate decomposed according to the equation:
(NH4)2 CO3(s) 2NH3(g) + CO2(g) + H2O(g)
At a certain elevated temperature, the total pressure of the gases generated was 0.42 atm. At
equilibrium. Calculate the equilibrium constant for the reaction.
10. if a given quantity of phosphorus pentachloride is heated at 250o C and allowed to come to
equilibrium at atmospheric pressure it is found to be dissociated to the extent of 80% into
phosphouroustri chloride and chlorine. If now, the pressure on this mixture is increased so that
finally the equilibrium mixture occupies only one half of its original volume (temperature maintained
costant).
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Part II
(Multiple Choice Question)
(single Option Correct)
1. For the reaction, 2Hl(g) H2(g) + l2(g), which of the following facts hold good?
(a) Kp = Kc
(B) Kp>Kc
(C) Kp<Kc
(D) Kp and KC can not be correlated unless pressure of the system is given.
2. For the reaction PCl3 (g) + Cl2(g) PCl5(g), the value of Kp at 250o C is 0.61 atm-1. The value of Kc at
this temperature will be
(A) 15 (mol/l)-1
(B) 26.19 (mol/l)-1
(C) 35 (mol/l)-1
(D) 52 (mol/l)-1
3. for the reaction
1
2NO2(g) + 2 O2(g) N2O5(g) if the equilibrium constant Kp, then the equilibrium constant for the
reaction 2N2O5 4NO2(g) + O2(g) would be
(A) K2
(B) 2/Kp
(C)1/K2
(D) 1/
4. For the reaction H2(g) + l2(g) 2Hl(g), the equilibrium constant Kp changes with
(A) total pressure
(B) catalyst
(C) the amount amounts of H2 and l2 present
(D) temperature
5. The equilibrium constant for the reaction
N2(g) + O2(g) 2NO(g) is 4x 10-4 at 200 K. in the presence of a catalyst the equilibrium is attained 10
times faster. Therefore the equilibrium constant In presence of the catalyst at 200 K is
(A) 4 x 10-3
(B) 4x 10-4
(C) 4 x 10-5
(D) None
+
2+
6. For the reaction Cu(s) + 2Ag (aq) Cu (aq) + 2 Ag(s) the equilibrium constant, Kc is given by
(A)
(C)
2+ []2
[ + ]2
[ 2+ ]
[ + ]2
(B)
(D)
[2]
2+ [2 + ]
[ + ]2
[ 2+ ]
7. In the gas phase reaction C2H4 + H2 C2H6, the equilibrium constant can be expressed in units
(A) 1 mole-1
(B) lit mole-1
(C) mole2 lit-2
(D) mole lit-1
8. for the reaction C(s) + Co2(g) 2CO(g) the partial pressure of CO2 and CO are 2.0 and 4.0 atm
respectively at equilibrium. The Kp for the reaction is
(A) 0.5
(B) 4.0
(C) 8.0
(D)32.0
9. CH3COOH + C2H5OH = CH3COOC2H5 + H2O. In this reaction one mole each of acetic acid and ethyl
alcohol are heated in presence of little conc. H2SO4. On equilibrium being attained the valu of Kc is 4.
What amount of ethyl acetate is formed?
(A) 88 g
(B) 176 g
(C) 29.33 g
(D) 58.67 g
10. For N2 + 3H2 2NH3 + heat
(A) Kp = Kc
(B) Kp = KcRT
(C) Kp = Kc(RT)-2
(D) Kp = Kc(RT)-1
o
11. One mole of ethanol is treated with one mole of ethanoic acid at 25 C. One-fourth of the acid
changes into ester at equilibrium. The equilibrium constant for the reaction will be
(A) 1/9
(B) 4/9
(C) 9
(D) 9/4
12. Given the following reaction at equilibrium: N2(g) + 3H2(g) 2NH3(g)
Some inert gas is added at constant volume. Predict which of the following facts will be affected?
(A) more of NH3(g) is produced
(B) less of NH3(g) is produced
(C) noaffect on the degree of advancement of the reaction at equilibrium
(D) Kp of the reaction is increased
13. For which reaction high pressure and high temperature is helpful in obtaining a high equilibrium
yield;
(A) 2NF N2(g) + 3F2(g) 54.40 kcal
(B) N2(g) + 3H2 2NH3(g) + 22.08 kcal
(C) Cl2(g) + 2O2(g) 2ClO2(g) 49.40 kcal
(D) 2Cl2O7(g) 2Cl2(g) + 7O2(g) + 126.8 kcal
14. for the gas phase reaction C2H4(g) C2H6(g); = -32.7 kcal carried out in a vessel, the
equilibrium concentration of C2H4 can be increased by
(A) increasing temperature
(B) decreasing temperature
(C) removing some H2
(D) All of the above
15. For the reaction: N2(g) + 3H2(g) 2NH3(g); = -ve
The formation NH3 is favoured at
(A) High pressure and low temperature
(B) low pressure and high temperature
(C) low pressure and low temperature
(D) high pressure and high temperature
16. For the reaction CaCO3(s) CaO(s) + CO2(g), the pressure of CO2(g) depends on
(A) the mass of CaCO3(s)
(B) the mass of CaO(s)
(C) the masses of both CaCO3(s) and CaO(s)
(D) temperature of the system
17.for the decomposition reaction: NH2COONH4 (s) 2NH3(g) + CO2(g)
The Kp = 2.9 x 10-5 atm3. The total pressure of gases at equilibrium when 1 mole of NH2COONH4(s)
was taken to start with would be
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(D) Kc = Kp()
1
21. The equilibrium constant of the reaction SO2 + 2 O2 SO3 and 2SO2 + O2 2SO3 are K1 and K2
respectively. The relationship between K1 and K2 IS
(A) K1 = K2
(B) K2 = K21
(C) K1 = 2
(D) K2 = 1
22. Which of the following statement is/are correct for a reversible reaction?
(A) Reaction quotient (Q) is the ratio of the product of arbitrary molar concentrations of the
products to that of reactants
(B) Q may be K
(C) At a given temperature both Q and K vary with reaction progress
(D) When Q > K, the reaction proceeds to backward direction before coming to stand still.
23. Which of the following will not affect the value of equilibrium constant of a reaction?
(A) change in concentration of the reaction
(B) change in temperature
(C) change in pressure
(D) addition of catalyst
24. Which of the following statement(s) is (are) wrong?
(A) at equilibrium concentration of reactant and product become constant because the
reaction stops
(B) addition of catalyst speeds up the forward reaction more that the backward reaction
(C equilibrium constant of an exothermic reaction decreases with increase of temperature
(D) Kp is always greater than Kc
25. for the following two reaction equilibrium constants are given
(i) A (g) + B (g) C (g) + D (g)
K1 = 1/3
(ii) E (g) + 2B (g) C (g) + 4D (g)
K2 = 6
The equilibrium constant for the reaction
(iii) A (g) + 3B (g) + E (g) 2C (g) + 5D (g)
26. Compound X dissociates according to the reaction 2X (g) 2Y (g) + Z (g) with degree of
dissociation which is small compared with unity, if expression for in terms of equilibrium
constant Kp and total pressure P is given as =
2 1/
. The value of n is
COMPREHENSION TYPE
Read the paragraph carefully and answer the following questions
Bodenstein carried out the determination of equilibrium constant of phosgene equilibrium by
introduction CO and Cl2 at known pressure in a reaction bulb and measuring the equilibrium
pressure from the attached monometer. In one experiment, CO at 342 nm and Cl2 at 351.4 nm were
introduced. The equilibrium pressure was found to be 439.5 nm. At equilibrium if partial pressure of
COCL2 B x mm at 127o C.
Reaction is: CI + Cl2 COCl2
(i) Value of x is
(A) 88.1 mm
(B) 97.5 mm
(C) 253.9 mm
(ii) The Kp for the above reaction is;
(A) 0.029 atm-1
(B) 760mm-1
(C) 22.5 atm-1
(iii) The volume of reacting vessel is decreased by 3 times, Kp changes by:
(A) 3 times increased
(B) remains constant
1
1
(C) 3times decreased
(D) 9 times increased
(D) 351.4 mm
(D) 29.5 atm
MATCHING
Match the following reaction in list 1 with the factors in list 2
List 1
List 2
(A) N2 (g) + 3H2 (g) 2NH3 (g) (Exothermic)
(p) Forward shift by rise in pressure
(B) 2SO2 (g) + O2 (g) 2SO3(g) (Exothermic)
(q) unaffected by change in pressure
(C) N2 (g) + O2 (g) 2NO (g) (Endothermic)
(r) Forward shift by rise in temperature
(D) PCl3 (g) + Cl2 (g) PCl5 (g) (Endothermic)
(s) Forward shift by lowering the temperature
(t) Backward shift by increasing the volume
Section - II
1. One mole of N2O4 (g) at 300 K is kept in a closed container under one atmosphere. It is heated to
600 K when 20% by mass of N2O4(g) decompose to NO2(g). the resultant pressure is
(A) 1.2 atm
(B) 2.4 atm
(C) 2.0 atm
(D) 1.0 atm
2. At constant temperature, the equilibrium constant (Kp) for the decomposition reaction
N2O42NO2 is expressed by
Kp= (4 x2 p )/(1-x2) , where P = pressure, the following statements is true?
(A) Kp increases with increase of P
(B) Kp increases with increases of x
(C) Kp increases with decreases of x
(D) Kp remains constant with change in P and x.
3. for which of the following reaction, Kp = Kc?
(A) 2NOCl(g) 2NO(g) + CL2(g)
(B) N2(g) + 3H2(g) 2NH3(g)
(C) H2(g) + Cl2(g) 2HCl(g)
(D) PCl3(g) + Cl2(g) PCl5(g)
4. The rate constant of a reaction depends on
(A) temperature
(B) Mass
(C) density
(D) time
5. for the chemical reaction
3X(g) + Y (g) X3Y (g), the amount of X3Y at equilibrium is affected by
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(D) 3,4,5
8. The equilibrium SO2Cl2(g) SO2(g) + Cl2(g) is attained at 25o C in a closed container and inert gas
helium is introduced, which of the following statements (s) is/are correct?
1. concentration of SO2, Cl2 and SO2Cl2 change
2. more chlorine is formed
3. concentration of SO2 is reduced
4. More SO2Cl2 is formed
(A) 1,2,3
(B) 2,3,4
(C) 3,4
(D) None
9. In what manner will increase of pressure affect the following equation?
C(s) + H2O(g) CO(g) + H2(g)
(A) shift in the forward direction
(B) shift in the reverse direction
(C) increase in the yield of hydrogen
(D) No effect
10. the decomposition of phosgene
COCl2 (g) CO(g) + Cl2 (g)
Is an endothermic process. Which of the following factors will cause the value of equilibrium
constant to increase?
(A) Adding Cl2
(B) Adding He(g)
(C) increasing the temperature
(D) Decreasing the total pressure
11. KNO3(s) dissociates on heating as
1
KNO3 (s) KNO2 (s) + 2 O2 (g) = -ve
At equilibrium in a closed container
(A) addition of KNO3(s) favoursfarward reaction
(B) addition of KNO2(s) favours reverse reaction
(C) increasing temperature favours forward reaction
(D) decreasing pressure favours reverse reaction
12. for the following three reaction (i), (ii) and (iii), equilibrium constants are given:
(i) CO(g) + H2O (g) CO2 (g) + H2 (g);
K1
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