UNIT II: EQUILIBRIUM / CHAPTER 2: CHEMICAL EQUILIBRIUM

1. What things must be true at equilibrium?

2. Water is boiling in a kettle at 100oC. Is the system at equilibrium? Explain

3. In the equilibrium 2 NH3 (g) ⇌ N2 (g) + 3 H2 (g) why does the [N2] remain unchanged even though the
forward reaction continues to occur?

4. In the reaction 3 C2H2 (g) ⇌ C6H6 (g) will the ratio of [C2H2 (g)] to [C6H6 (g)] at equilibrium be 3:1?

5. An equilibrium exists when a reaction’s forward rate equals its reverse rate. Answer the questions below for the
following equilibrium:
2 NO(g) + Cl2 (g) ⇌ 2 NOCl(g)
(a) Do the moles of NO consumed per second equal the moles of NO produced per second?
(b) Do the moles of NO consumed per second equal the moles of NOCl consumed per second?
(c) Do the moles of NOCl produced per second equal the moles of Cl2 consumed per second?
(d) Do the grams of NO consumed per second equal the grams of NO produced per second?
(e) Do the grams of NO consumed per second equal the grams of NOCl consumed per second?

6. Nitrogen dioxide gas is placed in a sealed flask.

2 NO2 (g) → N2O4 (g)
orange colourless
(a) What would you see as the reaction approaches equilibrium?
(b) Describe the change in the concentrations of reactants and products as the reaction approaches
equilibrium.
(c) Describe the change in the forward and reverse rates as the reaction approaches equilibrium.

7. Assume you have the reaction X(g) ⇌ Y(g) and that you start with pure X and allow the reaction to
come to equilibrium. Plot a graph of rate versus time which shows how the forward and reverse reaction rates
change from the time the reaction starts until equilibrium is attained.

8. A system at equilibrium has all of its reactants suddenly removed. Describe how the system would restore
equilibrium in terms of its forward and reverse reaction rates and its reactant and product concentrations.

9. Consider the following equilibrium system: 2 NO(g) + O2 (g) ⇌ 2 NO2 (g)

(a) Explain in terms of forward and reverse reaction rates how the system responds to removing some O2.
(b) Compare the rates of the forward and reverse reactions when equilibrium is reestablished with the rates
before some O2 was removed.

10. Explain in terms of forward and reverse reaction rates how this system responds to an increase in volume.
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)

11. Explain in terms of forward and reverse reaction rates how the equilibrium below responds to a decrease in
temperature:
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) ΔH = –92.4kJ/mol

12. State whether each of the following reactions will achieve equilibrium with a reasonable amount of reactants
and products, go almost to completion, or virtually not occur.
(a) 4 NH3 (g) + 5 O2 (g) → 4 NO(g) + 6 H2O(g) ΔH = –907.2kJ/mol
(b) N2 (g) + 2 O2 (g) → 2 NO2 (g) ΔH = +68kJ/mol
(c) PCl3 (g) + Cl2 (g) → PCl5 (g) ΔH = –92.5kJ/mol
(d) S(s) + O2 (g) → SO2 (g) ΔH = –297kJ/mol
 13.

Use Le Chatelier’s Principle to describe the effect of the following changes on the position of the equilibrium
14. The equilibrium is: N2O3 (g) ⇌ NO(g) + NO2 (g)
(a) Increase the [NO]
(b) Increase the [N2O3]
(c) Increase the pressure by decreasing the volume
(d) Add a catalyst

15. The equilibrium is: 2 H2 (g) + 2 NO(g) ⇌ N2 (g) + 2 H2O(g)

(a) Decrease the [N2]
(b) Decrease the [NO]
(c) Decrease the pressure by increasing the volume

16. The equilibrium is: 2 CO(g) + O2 (g) ⇌ 2 CO2 (g) + 566kJ

(a) Increase the temperature (b) Increase the [O2]
(c) Introduce a catalyst
 17. The equilibrium is: I2 (g) + Cl2 (g) ⇌ 2 ICl(g) ; ΔH = 35.0kJ
(a) Decrease the temperature
(b) Decrease the [Cl2]
(c) Increase the pressure by decreasing the volume

18. Consider the following equilibrium system: 2 NO(g) + Cl2 (g) ⇌ 2 NOCl(g)
(a) What does Le Châtelier’s principle say will occur if some NO is added to the system?
(b) In which direction will this system shift in response to the stress?
(c) Compare the [Cl2] when equilibrium is reestablished to its concentration before the NO was added.

Describe the effect on the concentration of the bold substance by the following changes. Write INC for increase, DEC for
decrease or NC for no change.
19. The equilibrium is: N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) ; ΔH = -92kJ
(a) Increase the [N2] (b) Increase the temperature
(c) Increase the volume (d) Add a catalyst

20. The equilibrium is: 2 HF(g) ⇌ F2 (g) + H2 (g) ; ΔH = 536kJ

(a) Decrease the temperature (b) Decrease the [H2]
(c) Decrease the volume

21. The equilibrium is: SnO2 (s) + 2 CO(g) ⇌ Sn(s) + 2 CO2 (g) ; ΔH = 13kJ
(a) Increase the temperature (b) Add a catalyst
(c) Increase the [CO]

22. Complete the following table using the words “decrease,” “same,” or “increase” to indicate how the equilibrium
concentrations are affected by the stated stress. “Increase” means that when equilibrium is restored, the
chemical’s concentration is greater than it was before the stress.
2 NH3 (g) ⇌ N2 (g) + 3 H2 (g)
Add NH3 Remove some H2 Add N2
Equilibrium N2
Concentration H2
NH3

23. Complete the following review table.

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) ΔH = –92.4kJ/mol
Stress Le Chatelier Predicts Chemical Kinetics Explains
Response Shift Effect Net Rx
Add H2 some of the added
H2 removed
Add NH3 left
Remove N2 rf decreases
Decrease volume net forward rx
(compress)
Decrease rr decreases more
temperature than rf

24. The following equilibrium exists in an aqueous solution of copper(II) chloride:

CuCl42− (aq) + 4 H2O(l) ⇌ Cu(H2O)42+ (aq) + 4 Cl− (aq)
green blue
(a) Some Cl− is removed by adding some silver nitrate to the solution. The Ag+ in the silver nitrate precipitates
with the Cl− to produce AgCl(s). In what direction will the equilibrium shift?
(b) If the initial equilibrium mixture was blue, what would you observe as a sodium chloride solution was added
dropwise to the equilibrium mixture?
Show the following situations graphically.
25. The equilibrium is: H2 (g) + I2 (g) ⇌ 2 HI(g) + 52kJ
(a) Increase the temperature (b) Inject some H2 (g)
(c) Decrease the volume (d) Add a catalyst

26. The equilibrium is: 2 SO2 (g) + O2 (g) ⇌ 2 SO3 (g) ; ΔH = -197kJ
(a) Inject some SO2 (g) (b) Increase the volume
(c) Decrease the temperature (d) Increase the [SO3]

27. The equilibrium is: CO(g) + H2O(g) ⇌ CO2 (g) + H2 (g) ; ΔH = -41kJ
(a) Inject some CO2 (g)
(b) Remove some of the H2O(g) with a very rapidly acting drying agent
(c) Increase the temperature
(d) Decrease the pressure by increasing the volume

Interpret the following graphs in terms of the changes which must have been imposed on the equilibrium.
28.

29.
30. Co(H2O)62+ (aq) + 2 Cl− (aq) ⇌ Co(H2O)4Cl2 (aq) + 2 H2O(l)
pink purple
A flask containing the above equilibrium turns from purple to pink when cooled. State whether the forward
reaction is endothermic or exothermic. Explain how you arrived at your answer.

31. Why is an equilibrium’s endothermic direction more sensitive to temperature changes than its exothermic
direction?

32. N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) + 92kJ

(a) In order to get the highest yield of NH3 (g), should you use high or low pressure?
(b) In order to get the highest yield of NH3 (g), should you use high or low temperature?
(c) In order to have the fastest reaction rate, should you use high or low temperature?
(d) Look at your answers to parts (b) and (c). What problem now exists? Suggest a suitable way to resolve the
problem
(e) What else can be done to speed up the reaction rate? (Industry uses iron oxide for this purpose, in the form
of ground up, rusted automobile bodies.)

33. CaCO3 (s) + 175kJ ⇌ CaO(s) + CO2 (g)

(a) Should high or low temperatures be used to get the greatest yield of CaO?
(b) Should high or low pressures be used to get the highest yield of CaO? How would you accomplish this in
actual practice?
(c) Should high or low temperatures be used to obtain the fastest reaction rate? Is there a conflict between the
answers for parts (a) and (c)?

34. Write the equilibrium expressions for the following

(a) 2 ICl(g) ⇌ I2 (g) + Cl2 (g) (b) N2 (g) + O2 (g) ⇌ 2 NO(g)
(c) 3 O2 (g) ⇌ 2 O3 (g) (d) 2 Bi3+(aq) + 3 H2S(g) ⇌ Bi2S3 (s) + 6 H+(aq)
(e) CaCO3 (s) ⇌ CaO(s) + CO2 (g) (f) CaC2 (s) + 2 H2O(l) ⇌ C2H2 (g) + Ca(OH)2 (s)
(g) C6H6 (l) + Br2 (l) ⇌ C6H5Br(l) + HBr(g) (h) Cu(s) + 2 Ag+(aq) ⇌ Cu2+(aq) + 2 Ag(s)
(i) 4 NH3 (g) + 5 O2 (g) ⇌ 6 H2O(g) + 4 NO(g) (j) H2 (g) + ½ O2 (g) ⇌ H2O(l)

35. Rearrange the following equations to solve in terms of the concentrations indicated in bold
[𝑯𝟑 𝑶+ ][𝐹 − ] [𝐻3 𝑂 + ][𝐹 − ]
(a) 𝐾𝑒𝑞 = [𝐻𝐹]
(b) 𝐾𝑒𝑞 = [𝑯𝑭]
[𝑵𝑶𝟐 ]2 [𝑁𝑂2 ]2
(c) 𝐾𝑒𝑞 = [𝑁𝑂]2 [𝑂2 ]
(d) 𝐾𝑒𝑞 = [𝑵𝑶]2 [𝑂 ]
2
[𝑁𝐻3 ]2 [𝑁2 𝑂4 ]
(e) 𝐾𝑒𝑞 = [𝑁2 ][𝑯𝟐 ]3
(f) 𝐾𝑒𝑞 = [𝑵𝑶 ]2
𝟐
[𝑵𝑯𝟑 ]2 [𝑃𝐶𝑙 ]4
(g) 𝐾𝑒𝑞 = [𝑁2 ][𝐻2 ]3
(h) 𝐾𝑒𝑞 = [𝑃 ][𝑪𝒍3 ]6
4 𝟐

36. Consider the following equilibria

i) 2 NO2 (g) ⇌ N2O4 (g) ; Keq = 2.2
2+ +
ii) Cu (aq) + 2 Ag(s) ⇌ Cu(s) + 2 Ag (aq) ; Keq = 1x10-15
2+ -
iii) Pb (aq) + 2 Cl (aq) ⇌ PbCl2 (s) ; Keq = 6.3x104
iv) SO2 (g) + ½ O2 (g) ⇌ SO3 (g) ; Keq = 110
(a) Which equilibrium favours products to the greatest extent?
(b) Which equilibrium favours reactants to the greatest extent?

37. How would each of the following stresses affect the equilibrium constant, Keq, for:
2 CO(g) + O2 (g) ⇌ 2 CO2 (g) ΔH = –31kJ/mol
(a) Add some CO2 (g)?
(b) Decrease the volume of the reaction vessel (at a constant temperature)?
(c) Increase the temperature?
(d) Add a catalyst?
38. If the value of Keq DECREASES when the temperature DECREASES, is the reaction EXOTHERMIC or
ENDOTHERMIC?

39. In the equilibrium KCl(s) + 17kJ ⇌ K+(aq) + Cl-(aq) which way will the equilibrium shift and what is the
effect on the value of Keq when
i) More K+(aq) is added? ii) The temperature is decreased? iii) More KCl(s) is added?

40. 2 NOCl(g) ⇌ 2 NO(g) + Cl2 (g) Keq = 8.0×10−2 at 462°C

For each of the following, what is the Keq at 462°C?
(a) NOCl(g) ⇌ NO(g) + ½ Cl2 (g)
(b) 2 NO(g) + Cl2 (g) ⇌ 2 NOCl(g)
(c) NO(g) + ½ Cl2(g) ⇌ NOCl(g)

41. A 2.0L flask contains 0.38mol CH4 (g), 0.59mol C2H2 (g), and 1.4mol H2 (g) at equilibrium. Calculate the equilibrium
constant, Keq, for the reaction:
2 CH4 (g) ⇌ C2H2 (g) + 3 H2 (g)

42. A closed flask contains 0.65mol/L N2 and 0.85mol/L H2 at equilibrium. What is the [NH3]?
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) Keq = 0.017

43. Keq = 35.0 for the reaction PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) If you have [PCl5] = 1.34x10-3 M and [PCl3] = 0.205M at
equilibrium in a certain vessel, what is the equilibrium concentration of Cl2 (g)?

44. Complete the following ICE tables.

(a) (b)
2 CH4 (g) ⇌ C2H2 (g) + 3 H2(g) N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)
I 6.0 0 0 I 5.0 0
C C
E 1.5 E 2.0 1.0

45. Complete the following ICE tables:

(a) (b)
Keq = 1.20 H2 (g) + C2N2 (g) ⇌ 2 HCN(g) Keq = 1.20 H2 (g) + C2N2 (g) ⇌ 2 HCN(g)
I 0 I 5.4 0
C C
E 5.0 1.5 E 3.6

46. During an experiment, 3.0mol of NO2 are injected into a 1.0L flask at 55°C. At equilibrium, the flask contains
1.2mol of N2O4.
2 NO2 (g) ⇌ N2O4 (g)
(a) What is the [NO2] at equilibrium?
(b) What is Keq for this reaction at 55°C?

47. A 1.0L reaction vessel contains 0.750mol of CO(g) and 0.275mol of H2O(g). After 1h, equilibrium is reached
according to the equation CO(g) + H2O(g) ⇌ CO2 (g) + H2 (g) Analysis shows 0.250mol of CO2 present at
equilibrium. What is Keq for the reaction?

48. A 5.0L reaction vessel was initially filled with 6.0mol of SO2, 2.5mol of NO2 and 1.0mol of SO3. After equilibrium
was established according to the equation SO2 (g) + NO2 (g) ⇌ SO3 (g) + NO(g) the vessel was found to contain
3.0mol of SO3. What is Keq for the reaction?

49. Some PCl5 is pumped into a 500mL flask. The [PCl3] = 1.50M at equilibrium. What was the initial [PCl5]?
PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) Keq = 2.14
50. A 500mL flask is injected with 0.72mol of C2N2 and 0.72mol of H2. What will the [HCN] be when the system
reaches equilibrium?
H2 (g) + C2N2 (g) ⇌ 2 HCN(g) Keq = 1.20

51. Consider the equilibrium N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

(a) At a certain temperature 3.0mol of N2 and 2.0mol of H2 are put into a 5.0L container. At equilibrium the
concentration of NH3 is 0.020M. Calculate Keq for the reaction.
(b) At a different temperature, 6.0mol of NH3 were introduced into a 10.0L container. At equilibrium 2.0mol of
NH3 were left. Calculate Keq for the reaction.

52. Keq = 1.00 for N2O2 (g) + H2 (g) ⇌ N2O(g) + H2O(g) If 0.150mol of N2O(g) and 0.250mol of H2O(g) were introduced
into a 1.00L bulb and allowed to come to equilibrium, what concentration of N2O2 (g) was present at equilibrium?

53. Keq = 49.5 for H2 (g) + I2 (g) ⇌ 2 HI(g) at a certain temperature. If 0.250mol of H2 (g) and 0.250mol of I2 (g) are
placed in a 10.0L vessel and permitted to react, what will be the concentration of each substance at equilibrium?

54. Keq = 125 for H2 (g) + I2 (g) ⇌ 2 HI(g) at a certain temperature. If 0.15mol of HI, 0.034mol of H2 and 0.096mol
of I2 are introduced into a 10L vessel, will the reaction proceed to the reactant side or product side as the
reaction attempts to reach equilibrium?

55. A 1.0L flask is injected simultaneously with 4.0mol N2, 3.0mol H2, and 8.0mol NH3. In what direction will the
reaction proceed to achieve equilibrium? Show your mathematical reasoning.
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) Keq = 1.0

56. At a certain temperature, Keq = 4 for the reaction 2 HF(g) ⇌ H2 (g) + F2 (g) Predict the direction in which
the equilibrium will shift, if any, when the following systems are introduced into a 5.0L bulb.
(a) 3.0mol of HF, 2.0mol of H2 and 4.0mol of F2
(b) 0.20mol of HF, 0.50mol of H2 and 0.60mol of F2
(c) 0.30mol of HF, 1.8mol of H2 and 0.20mol of F2

57. At a certain temperature, Keq = 75 for the reaction 2 O3 (g) ⇌ 3 O2 (g) Predict the direction in which
the equilibrium will shift, if any, when the following systems are introduced into a 10.0L bulb.
(a) 0.60mol of O3 and 3.0mol of O2 (b) 0.050mol of O3 and 7.0mol of O2
(c) 1.5mol of O3 and no O2

58. A cylinder contains 0.12M COBr2, 0.060M CO, and 0.080M Br2 at equilibrium. The volume of the cylinder is
suddenly doubled.
COBr2 (g) ⇌ CO(g) + Br2 (g)
(a) What is the molar concentration of each gas immediately after the volume of the cylinder is doubled?
(b) Explain, in terms of Le Châtelier’s principle, why the system shifts right to restore equilibrium.
(c) The system re-equilibrates by converting 0.010M COBr2 into CO and Br2. Verify that the original equilibrium
concentrations and the re-established equilibrium concentrations provide the same value when substituted
into the reaction’s equilibrium expression.

59. In a 2.00L flask, 3.00M H2, 3.00M Cl2, and 7.50M HCl coexist at equilibrium. A student removes 7.00mol of HCl
from the flask.
(a) What would the concentration of each gas be when equilibrium re-establishes?
H2 (g) + Cl2 (g) ⇌ 2 HCl(g)
Eo
I
C
Ef
(b) Describe how the system’s response is consistent with Le Châtelier’s principle.
60. Can you infer that reactants are favoured in the reaction below because Keq < 1? Explain.
C(s) + H2O(g) ⇌ CO(g) + H2 (g) Keq = 0.16

61. A 1.00L flask is injected with 0.600mol of each of the following four gases: H2, CO2, H2O, and CO.
H2 (g) + CO2 (g) ⇌ H2O(g) + CO(g) Keq = 1.69
(a) What is the [H2] at equilibrium?
(b) What is the [CO] at equilibrium?

62. Keq = 5.0 at a certain temperature for the reaction 2 SO2 (g) + O2 (g) ⇌ 2 SO3 (g) A certain amount of
SO3 (g) was placed in a 2.0L reaction vessel. At equilibrium the vessel contained 0.30mol of O2 (g). What
concentration of SO3 (g) was originally placed in the vessel?

63. Equal quantities of H2 (g) and I2 (g) are pumped into a flask. At equilibrium the [HI] = 1.0M. What was the initial
[H2]?
H2 (g) + I2 (g) ⇌ 2 HI(g) Keq = 4.0

64. Some SO3 is injected into a 500mL flask. At equilibrium the [O2] = 1.80M.
2 SO3 (g) ⇌ 2 SO2 (g) + O2 (g) Keq = 3.83×10−2
(a) What is the [SO3] at equilibrium?
(b) How many moles of SO3 were originally injected into the flask?

65. Keq = 7.5 for 2 H2 (g) + S2 (g) ⇌ 2 H2S(g) A certain amount of H2S was added to a 2.0L flask and allowed
to come to equilibrium. At equilibrium, 0.072mol of H2 was found. How many moles of H2S were originally added
to the flask?

66. The equilibrium constant for the reaction N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) is 3.0 at a certain temperature.
Enough NH3 (g) was added to a 5.0L container such that at equilibrium the container was found to contain 2.5mol
of N2 (g). How many moles of NH3 (g) were put into the container?

67. A reaction mixture at equilibrium, CO(g) + H2O(g) ⇌ CO2 (g) + H2 (g) contains 1.00mol of H2, 2.00mol of CO2,
2.00mol of CO and 2.00mol of H2O in a 2.00L bulb. If 1.00mol of H2 is added to the system, calculate the [CO]
which will exist when equilibrium is regained.

68. A reaction mixture at equilibrium, H2 (g) + I2 (g) ⇌ 2 HI(g) contains 0.150mol of H2 (g), 0.150mol of I2 (g) and
0.870mol of HI(g) in a 10.0L vessel. If 0.400mol of HI(g) is added to this system and the system is allowed to come
to equilibrium again, what will be the new concentrations of H2, I2 and HI?

69. *A reaction mixture contains 0.24mol of NO, 0.10mol of O2, and 1.20mol of NO2 at equilibrium in a 1.0L
container. How many moles of O2 would need to be added to the mixture to increase the amount of NO2 to
1.30mol when equilibrium is re-established?
2 NO(g) + O2 (g) ⇌ 2 NO2 (g)

70. *A reaction mixture, ICl(g) + H2 (g) ⇌ I2 (g) + 2 HCl(g) was found to contain 0.500mol of ICl(g), 0.0560mol of
H2 (g), 1.360mol of I2 (g) and 0.800mol of HCl(g) at equilibrium in a 1.00L bulb. How many moles of ICl(g) would have
to be removed in order to reduce the [HCl(g)] to 0.680M when equilibrium is re-established?

71. A reaction mixture at equilibrium, CO2 (g) + H2 (g) ⇌ CO(g) + H2O(g) contained 4.00mol of CO2, 1.50mol of
H2, 3.00mol of CO and 2.50mol of H2O in a 5.0L container. How many moles of CO2 would have to be removed
from the system in order to reduce the amount of CO to 2.50mol?

72. Keq = 100 at a certain temperature for CH4 (g) + 2 H2S(g) ⇌ CS2 (g) + 4 H2 (g) Some CH4 and H2S were
introduced into a 1.0L bulb and at equilibrium 0.10mol of CH4 and 0.30mol of H2S were found. What was [CS2] at
equilibrium?