Chemical Equilibria Lecture Notes Examples

Ex 1 Write the equilibrium expression (Kc) for each of the following: (a) 2 H2(g) + O 2(g)
2 2

2 H2O (g)

KC = [H 2O] / [H2] [O 2] (b) 2 C 6H6(g) +

12

15 O2(g)
6

12 CO2(g) +
15

6 H2O (g)

KC = [CO 2] [H 2O] / [C6H6] [O 2] Ex 2 For the equilibrium 2 SO3(g)

3

2 SO2(g) + O 2(g) at a temperature of 1000 K,

Kc has the value 4.08 10 . Calculate the value for Kp. KP = K C (RT) Ex 3
n

= (4.08 10 ) (RT)

32

= 0.335

The equilibrium constant for the reaction H2(g) + I2(g)

2 HI(g) varies with temperature in

the following way: K c = 794 @ 298 K; Kc = 54 @ 700 K. Is the formation of HI favored more at higher or lower temperatures? KC decreases as temperature increases. Since KC is the ratio of products to reactants, when KC gets smaller the amount of product is getting smaller. So the formation of HI is favored at lower temperatures. Ex 4 Write the equilibrium expressions for Kc and Kp for the reaction 3 Fe(s) KC = [H 2] / [H2O] KP = K C (RT) Ex 5
4-4 4 4

4 H2O (g)

Fe3O 4(s)

+ 4 H2(g)

= KC

An experiment is run at 425C to determine the equilibrium constant for the reaction H2(g) + I2(g)

2 HI(g)

at that temperature. H2(g) and I2(g), both at the same initial partial pressure of 5.73 atm, are mixed. When the reaction comes to equilibrium, the partial pressure of HI is measured to be 9.00 atm. Compute the equilibrium constant, assuming that no side reactions occur. H2(g) Initial Change Equilibrium 5.73 x 5.73 x + I2(g) 5.73 x 5.73x

2 HI (g) 0 +2x 9.00

x = 4.50 atm, so PH2 = PI2 = 5.73 atm 4.50 atm = 1.23 atm KP = (PHI) / (P H2)(P I2) = (9.00) / (1.23) = 53.5
2 2 2

Ex 6

The reaction 2 NO(g)

Br2(g)

2 NOBr(g)

has an equilibrium constant of 116.6 at 25C. In each of the following mixtures, compute the reaction quotient Q and use it to decide the direction the reaction takes (right to left) to come to equilibrium. The initial partial pressures (all in atm) in the gas mixture are (a) PNO = 0.188;
2 2

PBr2 = 0.300;
2

PNOBr = 1.203
2

Q = (P NOBr) / (P NO) (P Br2) = (1.203) / (0.188) (0.300) = 136 Q > K so the reaction will proceed to the left (toward reactants) to reach equilibrium. (b) PNO = 0.300;
2 2

PBr2 = 0.188;
2

PNOBr = 1.203
2

Q = (P NOBr) / (P NO) (P Br2) = (1.203) / (0.300) (0.188) = 85.5 Q < K so the reaction will proceed to the right (toward products) to reach equilibrium.

Ex 7

The progress of the reaction H2(g) + Br2(g) 2 HBr(g) can be monitored visually by following changes in the color of the reaction mixture (Br 2 is reddish brown, and H2 and HBr are colorless). A gas mixture is prepared at 700 K, in which 0.40 atm is the initial partial pressure of both H2 and Br2 and 0.90 atm is the initial partial pressure of HBr. The color of this mixture fades as the reaction progresses toward equilibrium. What condition must K satisfy (for example, it must be greater than or smaller than a given number)? Q = (P HBr ) / (P H2) (P Br2) = (0.90) / (0.40) (0.40) = 5.1 As the reaction moves toward equilibrium the color of the mixture fades. This tells us that the reaction is moving to the right toward the formation of more colorless product. If the reaction is not yet at equilibrium and we need to move to the right to make more products, then Q < K. Therefore, K must be greater than 5.1.
2 2

Ex 8

Consider the following equilibrium 2 BrCl (g) Br2(g) + Cl 2(g) K = 32 @ 500K Calculate the partial pressure of BrCl that is in equilibrium with a mixture of 0.182 atm of bromine and 0.0876 atm of chlorine at 500K. KP = 32 = (PBr2) (PCl2) / (PBrCl) = (0.182) (0.0876) / (PBrCl) 2 4 (P BrCl) = 4.98 x 10 P BrCl = 0.022 atm
2 2

Ex 9

Given the following exothermic reaction: 2 SO 2(g) + O2(g) 2 SO 3(g) Which direction will the equilibrium shift when the following changes are made? (a) Add more O2? Right (b) (c) (d) (e) Remove some SO3? Remove some SO2? Increase the temperature? Decrease the volume (constant T)? Right Left Left Right

Some problems to try on your own:

1. The value of the equilibrium constant for the following reaction is K1. 3 H2(g) + N2(g)

2 NH3(g)

How is K 1 related to the equilibrium constant K2 for the related equilibrium? 2 NH3(g) K2 = 1/K 1 2. The equilibrium constant (Kp) for the reaction 3/2 Fe(s) + 2 H2O (g)

3 H2(g) + N2(g)

1/2 Fe3O 4(s)

2 H2(g)

is 3.51 at 527C. 5.42 g of Fe and 7.88 g of H2O are placed in a closed, 5.0-L container and allowed to reach equilibrium. Calculate the pressure of H2(g) at equilibrium. mol H2O = (7.88 g)(1 mol / 18.0152 g) = 0.4374 mol P H2O = (0.4374 mol)R(800 K)/5.0 L = 5.74 atm Ignore the solids 3/2 Fe (s) Initial --Change --Equilibrium --2

2 H2O (g) 5.74 2x 5.742x

2 2

1/2 Fe 3O 4(s) ------2

2 H2(g) 0 +2x 2x

KP = 3.51 = (PH2) / (P H2O) = (2x) / (5.742x) 3.51 = 2x/(5.74 2x) x = 2.23 P H2 = 2x = 2(2.23) = 4.46 atm

3. Find the equilibrium partial pressure of N2O 4(g) and NO 2(g) in the reaction N2O 4(g) 2 NO 2(g) K = 0.98 @ 298K
if a flask is charged with enough N2O 4 to exert an initial partial pressure of 0.050 atm. N2O 4(g) 0.050 x 0.050 x
2 2

Initial Change Equilibrium

2 NO 2(g) 0 +2x 2x

KP = 0.98 = (PNO2) / (P N2O4) = (2x) / (0.050x) 0.98 = (2x) / (0.050x) 2 4x + 0.98x 0.049 = 0 x = 0.288, 0.0426 The negative root is impossible so x = 0.0426 P N2O4 = 0.050 0.0426 = 0.007 atm P NO2 = 2(0.0426) = 0.085 atm
2

4. For the reaction SO 2Cl 2 (g) (a)

SO 2(g)

Cl2(g)

K = 2.40 @ 100C

Initial partial pressure of SO2Cl 2 in a tank with rigid walls is 1.398 atm, no other species are present. Calculate the Q. Does total pressure increase or decrease as the rxn equilibrium? Q = 0 The total pressure will increase as the reaction approaches equilibrium.

(b)

Calculate the partial pressures of SO2Cl 2, SO 2, and Cl2 after equilibrium is reached. SO 2Cl 2 (g) 1.398 x 1.398 x

Initial Change Equilibrium

SO 2(g) 0 +x x

Cl2(g) 0 +x x

KP = 2.40 = (PSO2)(P Cl2) / (PSO2Cl2) = (x) / (1.398 x) 2.40 = (x) / (1.398 x) x + 2.40x 3.3552 = 0 x = 3.39, 0.990 Only the positive will work. P SO2Cl2 = 1.398 0.990 = 0.408 atm P SO2 = PSO2 = 0.990 atm 5. 0.500 atm of H2 and 0.500 atm of I2 are placed in a container. The reaction between the two to form HI is allowed to come to equilibrium. What are the equilibrium partial pressures of all compounds? H2(g) + I2(g) 2 HI(g) K = 54 @ 700K H2 (g) Initial Change Equilibrium
2 2 2

I2(g) 0.500 x 0.500 x

2

2 HI(g) 0 +2x 2x

0.500 x 0.500 x

KP = 54 = (PHI) / (P H2)(P I2) = (2x) / (0.500 x) 54 = 4x / (0.500 x)

2 2 2

x + 2.40x 3.3552 = 0 x = 0.687, 0.393 Only the smaller number will work. P HI = 2(0.393) = 0.786 atm P H2 = PI2 = 0.500 0.393 = 0.107 atm

6. Given the following data: N2(g) N2(g) + + 3 H2(g) O 2(g)

2 NH3(g) 2 NO (g)

K@25C = 3.5 10 K@25C = 1.7 10

8 3 2

2 NO2(g) N2O 4(g) K@25C = 1.7 10 Arrange the following reactions in order from most reactant-favored to most product-favored. (1) (2) (3) 1, 3, 2 2 NH3(g) 2 NO(g) 2 NO2(g)

N2(g) N2(g)

+ +

3 H2(g) O 2(g)

K = 2.9 10 K = 588 K = 1.7 10

10

N2O 4(g)