CHEMICAL EQUILIBRIA

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10.1 State whether the following statements are true or false. If false, explain why.

(a) A reaction stops when equilibrium is reached. (b) An equilibrium reaction is not

affected by increasing the concentrations of products.(c) If one starts with a higher

pressure of reactant, the equilibrium constant will be larger. (d) If one starts with

higher concentrations of reactants, the equilibrium concentrations of the products

will be larger.

Answer:

(a) False. Equilibrium is dynamic. At equilibrium, the concentrations of reactants

and products will not change, but the reaction will continue to proceed in both

directions.

(b) False. Equilibrium reactions are affected by the presence of both products and

reactants.

(c) False. The value of the equilibrium constant is not affected by the amounts of

reactants or products added as long as the temperature is constant.

(d) True

10.5 The following flasks show the dissociation of a diatomic molecule, X2, over

time. (a) Which flask represents the point in time at which the reaction has reached

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equilibrium? (b) What percentage of the X2 molecules have decomposed at

equilibrium? (c) Assuming that the initial pressure of X2 was 0.10 bar, calculate the

value of K for the decomposition.

Answer

(a)Flask 3 represents the point of reaction equilibrium

(b) % decomposition = (6/11) ×100 = 54.5%

(c) Decomposition: X2 = 2X

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10-7 Balance the following equations using the smallest wholenumber coefficients,

then write the equilibrium expression Kc for each reaction:

Answer:

10.9 A 0.10-mol sample of pure ozone, O3, is placed in a sealed 1.0-L container and

the reaction 2O3 (g) 3O2(g) is allowed to reach equilibrium. A 0.50-mol sample

of pure ozone is placed in a second 1.0-L container at the same temperature and

allowed to reach equilibrium. Without doing any calculations, predict which of the

following will be different in the two containers at equilibrium. Which will be the
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same? (a) Amount of O2; (b) concentration of O2; (c) the ratio [O2]/[O3]; (d) the ratio

[O2]3/[O3]2; (e) the ratio [O3]2/[O2]3. Explain each of your answers.

Answer:

(a) Because the volume is the same, the number of moles of O, is larger in the second

experiment, (b) Because Kc is a constant and the denominator is larger in the second

case, the numerator must also be larger; so the concentration of O2 is larger in the

second case. (c) Although [O2]3/[O3]2 is the same, [O2 ]/[O3] will be different, a

result seen by solving for Kc in each case, (d) Because Kc is a constant, [O2]3/[O3]2

is the same, (e) Because [O2]3/[O3]2 is the same, its reciprocal must be the same.

10.11 Use the following data, which were collected at 460.°C and

are equilibrium partial pressures, to determine K for the reaction

H2(g) + I2(g) 2 HI(g):

Answer:

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10.15 (a) Calculate the reaction Gibbs free energy of I2(g) 2 I(g) at 1200. K

(K=6.8) when the partial pressures of I2 and I are 0.13 bar and 0.98 bar, respectively.

(b) What is the spontaneous direction of the reaction? Explain briefly.

Answer:

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10.17 (a) Calculate the reaction Gibbs free energy of N2(g)+3H2(g) 2 NH3(g)

when the partial pressures of N2, H2, and NH3 are 4.2 bar, 1.8 bar, and 21 bar,

respectively, and the temperature is 400.K. For this reaction, K =41 at 400.K. (b)

Indicate whether this reaction mixture is likely to form reactants, is likely to form

products, or is at equilibrium.

Answer:

10.19 Calculate the equilibrium constant at 25°C for each of the following reactions,

using data in Appendix 2A: (a) the combustion of hydrogen:

2 H2(g) O2(g) 2H2O(g) (b) the oxidation of carbon monoxide:

CaCO3(s) 4 CaO(s) +CO2(g)

Answer:

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10.21 Calculate the standard Gibbs free energy of each of the following reactions:

(a) I2(g) 2I(g), K =6.8 at 1200. K

(b) Ag2CrO4(s) 2 Ag(aq) CrO42-(aq), K =1.1×10-12 at 298 K

Answer:

10.23 If Q=1.0 for the reaction N2(g)+O2(g) 2NO(g) at 25°C, will the reaction

have a tendency to form products or reactants or will it be at equilibrium?

Answer:

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10.25 Use the information in Table 10.2 to determine the value of K at 300 K for the

reaction 2 BrCl(g) +H2(g) Br2(g) +2 HCl(g).

Answer:

10.29 In a gas-phase equilibrium mixture of PCl5, PCl3, and Cl2 at 500. K, PPCl5= 1.18

bar, PCl2= 5.43 bar. What is the partial pressure of PCl3, given that K =25 for the

reaction PCl5(g) PCl3(g) +Cl2(g)?

Answer:

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10.33 A 0.500-L reaction vessel at 700.K contains 1.20 mmol SO2(g), 0.50 mmol

O2(g), and 0.10 mmol SO3(g). At 700 K, Kc =1.7 ×10-6 for the equilibrium

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

(a) Calculate the reaction quotient Qc.

(b) Will more SO3(g) tend to form?

Answer:

10.35 Determine Kc for each of the following equilibria from the value of K:

(a) 2 NOCl(g) 2 NO(g)+Cl2(g), K=1.8×10-2 at 500. K

(b) CaCO3(s) CaO(s) +CO2(g), K =167 at 1073 K

Answer:
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10.37 For the reaction N2(g) +3H2(g) 2NH3(g) at 400. K, K=41. Find the

value of K for each of the following reactions at the same temperature:

(a) 2 NH3(g) N2(g) +3 H2(g)

(b) 1/2N2(g) +3/2 H2(g) NH3(g)

(c) 2 N2(g) +6 H2(g) 4 NH3(g)

Answer:

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10.39 When 0.0172 mol HI is heated to 500. K in a 2.00-L sealed container, the

resulting equilibrium mixture contains 1.90 g of HI. Calculate K for the

decomposition reaction 2 HI(g) H2(g)+I2(g)

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Answer:

10.41 A 25.0-g sample of ammonium carbamate, NH4(NH2CO2), was placed in an

evacuated 0.250-L flask and kept at 25°C. At equilibrium, 17.4 mg of CO2 was

present. What is the value of Kc for the decomposition of ammonium carbamate into

ammonia and carbon dioxide?

The reaction is NH4(NH2CO2)(s) 2NH3(g)+CO2(g)

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10.45 (a) A sample of 2.0 mmol Cl2(g) was sealed into a 2.0-L reaction vessel and

heated to 1000. K to study its dissociation into Cl atoms. Use the information in

Table 10.2 to calculate the equilibrium composition of the mixture. (b) If 2.0 mmol

F2 was placed into the reaction vessel instead of the chlorine, what would be its

equilibrium composition at 1000. K? (c) Use your results from parts (a) and (b) to

determine which is thermodynamically more stable relative to its atoms at 1000. K,

Cl2 or F2.

Answer:

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10.47 For the reaction PCl5(g) PCl3(g)+Cl2(g), Kc =1.1×10-2 at 400.K

(a) Given that 1.0 g of PCl5 is placed in a 250.-mL reaction vessel, determine the

molar concentrations in the mixture at equilibrium.

(b) What percentage of the PCl5 has decomposed at equilibrium at 400. K?

Answer:

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10.49 When solid NH4HS and 0.400 mol NH3(g) were placedin a 2.0-L vessel at

24°C, the equilibrium NH4HS(s) NH3(g) H2S(g), for which Kc=1.6×10-4, was

reached. What are the equilibrium concentrations of NH3 and H2S?

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Answer:

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10.51 The equilibrium constant Kc for the reaction N2(g)+O2(g) 2 NO(g) at

1200°C is 1.00×10-5. Calculate the equilibrium molar concentrations of NO, N2, and

O2 in a 1.00-L reaction vessel that initially held 0.114 mol N2 and 0.114 mol O2.

Answer:

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10.53 A reaction mixture that consisted of 0.400 mol H2 and 1.60 mol I2 was

introduced into a 3.00-L flask and heated. At equilibrium, 60.0% of the hydrogen

gas had reacted. What is the equilibrium constant K for the reaction

H2(g)+I2(g) 2 HI(g) at this temperature?

Answer:

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10.57 At 500. K, the equilibrium constant for the reaction

Cl2(g)+Br2 (g) 2 BrCl(g) is Kc 0.031. If the equilibrium composition is

0.495 molL1 Cl2 and 0.145 molL1 BrCl, what is the equilibrium concentration of

Br2?

Answer:

10.59 A reaction mixture consisting of 2.00 mol CO and 3.00 mol H2 is placed in a

10.0-L reaction vessel and heated to 1200. K. At equilibrium, 0.478 mol CH4 was

present in the system. Determine the value of Kc for the reaction

CO(g)+3H2(g) CH4(g)+H2O(g) at 1200. K.

Answer:

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10.61 A reaction mixture is prepared by mixing 0.100 mol SO2, 0.200 mol NO2,

0.100 mol NO, and 0.150 mol SO3 in a 5.00-L reaction vessel. The reaction

SO2(g)+NO2(g) NO(g)+SO3(g) is allowed to reach equilibrium at 460.°C,

when Kc =85.0. What is the equilibrium concentration of each substance?

Answer:

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10.63 The equilibrium constant Kc=0.56 for the reaction

PCl3(g)+Cl2(g) PCl5(g) at 250.°C. On analysis, 1.50 mol PCl5, 3.00 mol PCl3,

and 0.500 mol Cl2 were found to be present in a 0.500-L reaction vessel at 250.°C.

(a) Is the reaction at equilibrium? (b) If not, in which direction does it tend to

proceed? (c) What is the equilibrium composition of the reaction system?

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10.65 At 25°C, K=3.2×10-34 for the reaction 2 HCl(g) H2(g)+Cl2(g). If a 1.0-

L reaction vessel is filled with HCl at 0.22 bar, what are the equilibrium partial

pressures of HCl, H2, and Cl2?

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10.69 The reaction 2 HCl(g) H2(g)+Cl2(g) has K=3.2×10-34 at 298 K. The

initial partial pressures are H2,1.0 bar; HCl, 2.0 bar; and Cl2, 3.0 bar. At equilibrium

there is 1.0 mol H2(g). What is the volume of the container? (Don’t be surprised at

the large size of the volume.)

Answer:

10.71 Consider the equilibrium CO(g)+H2O(g) CO2(g)+H2(g). (a) If the partial

pressure of CO2 is increased, what happens to the partial pressure of H2? (b) If the

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partial pressure of CO is decreased, what happens to the partial pressure of CO2? (c)

If the concentration of CO is increased, what happens to the concentration of H2? (d)

If the concentration of H2O is decreased, what happens to the equilibrium constant

for the reaction?

Answer:

10.75 State whether reactants or products will be favored by an increase in the total

pressure (resulting from compression) on each of the following equilibria. If there is

no change, explain why that is so.

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10.77 Consider the equilibrium 3NH3(g)+5O2(g) 4NO(g)+6H2O(g). (a) What

happens to the partial pressure of NH3 when the partial pressure of NO is increased?

(b) Does the partial pressure of O2 decrease when the partial pressure of NH3 is

decreased?

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10.79 Predict whether each of the following equilibria will shift toward products or

reactants with a temperature increase:

Answer:

10.81 A reactor for the production of ammonia by the Haber process is found to be

at equilibrium with 3.11 bar, P H2=1.64 bar, and PNH3= 23.72 bar. If the partial

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pressure of N2 is increased by 1.57 bar, what will be the partial pressure of each gas

once equilibrium is re-established?

Answer:

10.85 A gaseous mixture consisting of 2.23 mmol N2 and 6.69 mmol H2 in a 500.-

mL container was heated to 600. K and allowed to reach equilibrium. Will more

ammonia be formed if that equilibrium mixture is then heated to 700. K?

For N2(g)+3 H2(g) 2 NH3(g), K=1.7×10-3 at 600. K and 7.8×10-5 at 700. K

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Answer:

10.87 At 500.°C, Kc=0.061 for N2(g)+3H2(g) 2 NH3(g). If analysis shows that

the composition is 3.00 molL-1 N2, 2.00 molL-1 H2, and 0.500 molL-1 NH3, is the

reaction at equilibrium? If not, in which direction does the reaction tend to proceed

to reach equilibrium?

Answer:

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10.89 Calculate the equilibrium constant at 25°C and at 150.°C for each of the

following reactions, using data available in Appendix 2A:

Answer:

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10.91 By combining the relation for Kc in terms of K with the van ’t Hoff equation,

find the analog of the van ’t Hoff equation for Kc.

Answer:

10.93 Dissociation of a diatomic molecule, X2(g) 2X(g) occurs at 500 K.

Picture 1 shows the equilibrium state of the dissociation and picture 2 shows the
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equilibrium state in the same container after a change has occurred. Which of the

following changes will produce the change shown? (a) Increasing the temperature.

(b) Adding X atoms. (c) Decreasing the volume. (d) Adding a catalyst. Explain your

selections.

Answer:

10.97 The following plot shows how the partial pressures of reactant and products

vary with time for the decomposition of compound A into compounds B and C. All

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three compounds are gases. Use this plot to do the following: (a) Write a balanced

chemical equation for the reaction. (b) Calculate the equilibrium constant for the

reaction. (c) Calculate the value of Kc for the reaction at 25°C.

Answer:

10.99 At 1565 K, the equilibrium constants for the reactions

(1) 2H2O(g) 2H2(g)+O2(g) and (2) 2CO2(g) 2CO(g)+O2(g) are

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1.6×10-11 and 1.3×10-10, respectively. (a) What is the equilibrium constant for the

reaction (3) CO2(g)+H2(g) H2O(g)+CO(g) at that temperature? (b) Show that

the manner in which equilibrium constants are calculated is consistent with the

manner in which the ∆Gr° values are calculated when combining two or more

equations by determining ∆Gr° for reactions (1) and (2) and using those values to

calculate ∆Gr° and K3 for reaction (3).

Answer:

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10.101 0.020 mol NO2 was introduced into a 1.00-L flask and the reaction

2NO2(g) N2O4(g) was allowed to come to equilibrium at 298 K. (a) Using

information in Table 10.2 calculate the equilibrium concentrations of the two gases.

(b) The volume of the flask is reduced to half its original volume. Calculate the new

equilibrium concentrations of the gases.

Answer:

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10.105 (a) What is the standard Gibbs free energy of the reaction

CO(g)+H2O(g) CO2(g)+H2(g) when K=1.00? (b) From data available in

Appendix 2A, estimate the temperature at which K=1.00. (c) At this temperature, a

cylinder is filled with CO(g) at 10.00 bar, H2O(g) at 10.00 bar, H2(g) at 5.00 bar, and

CO2(g) at 5.00 bar. What will be the partial pressure of each of these gases when the

system reaches equilibrium? (d) If the cylinder were filled instead with CO(g) at

6.00 bar, H2O(g) at 4.00 bar, H2(g) at 5.00 bar, and CO2(g) at 10.00 bar, what would

the partial pressures be at equilibrium?

Answer:

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10.109 (a) Calculate K at 25°C for the reaction Br2(g) 2Br(g)from the

thermodynamic data provided in Appendix 2A. (b) What is the vapor pressure of

liquid bromine? (c) What is the partial pressure of Br(g) above the liquid in a bottle

of bromine at 25°C? (d) A student wishes to add 0.0100 mol Br2 to a reaction and

will do so by filling an evacuated flask with Br2 vapor from a reservoir that contains

only bromine liquid in equilibrium with its vapor. The flask will be sealed and then

transferred to the reaction vessel. What volume container should the student use to

deliver 0.010 mol Br2(g) at 25°C?

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Answer:

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10.111 The Claus process, which is used to remove sulfur found as sulfur dioxide in

petroleum, is based on the reaction 2H2S(g)+SO2(g) 3S(s)+2H2O(g). (a) Use

data from Appendix 2A to determine the equilibrium constant of this reaction at 25

C. (b) Certain changes (see the following table) are then made to this mixture.

Considering each change separately, state the effect (increase, decrease, or no

change) that the change has on the original equilibrium values of the quantity in the

second column (or K, if that is specified). The temperature and volume are constant

unless otherwise specified.

Answer:

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