Practice Problems Chpt. 12, 13

Practice Problems Chpt. 12, 13

Chpt. 12

1. Given the following reaction,

A + 2 B→C + 2 D

And the following data,

Where the rate is defined,

Rate = -[A]/ t .

(a)What is the rate law?

(b)What is the value of the rate constant?

2. The rate constant for the decomposition of gaseous azomethane,

C2 H6 N2 (g)N2 (g) + C2 H6 (g)

Is 40.8 min-1 at 425OC. Find the number of moles azomethane and the number of moles of nitrogen 0.0500 minutes after 2.00 g of azomethane is introduced. Assume that the decomposition reaction is first order and that the reverse reaction can be ignored (Note that the first order integrated rate equation can be expressed in terms of the number of moles of the reacting species instead of the concentration).

3.Phosphine, PH3 (g), decomposes according to the following equation,

4 PH3 (g) → P4 (g) + 6 H2 (g)

The decomposition of phosphine was studied at 950 K by measuring the total gas pressure in the system as a function of time. The following results were obtained. Assume that initially (t=0) there was pure phosphine at a pressure of 100 torr.

Determine the rate law and the associated rate constant for this reaction.

4. The rate constant of a certain reaction is tripled when the temperature is increased

from 10.0OC to 30.0OC. Calculate the activation energy for this reaction.

5.Consider the following reaction.

2 N2O5 (g)2 N2O4 (g) + O2 (g)

Given that,

Ea = 103 kJ/mol

and,

k = 0.0900 min-1 at 328 K

calculate the value of k at 338 K.

6. Consider the decomposition of NH3 (g).

2 NH3 (g)→N2 (g) + 3 H2 (g)

The reaction is catalyzed on a surface of either tungsten or osmium. The activation energies for the catalyzed and uncatalyzed reactions are given below.

WEa = 163 kJ/mol

OsEa = 197 kJ/mol

No catalystEa = 335 kJ/mol

(a)Which surface is a better catalyst for the decomposition of NH3?

(b)Assuming a temperature of 298 K, how many times faster is the reaction on the W surface compared to when the reaction is uncatalyzed?

(c)The reaction is first order in NH3 at low concentrations of NH3 but ultimately becomes 0 order in NH3 as the concentration of NH3 is increased. Provide an explanation for this observation.

7. Consider the following reaction.

A (g) + B (g)→C (g) + D (g)

In one experiment the concentration of A (g) was monitored in the presence of a large excess of B (g) ( [B]o = 0.750 M ) .

In a second experiment the concentration of B (g) was monitored in the presence of a large

excess of A (g) ( [A]o = 1.50 M ) .

(a)Determine the differential rate law for this reaction.

(b)Determine the value of the rate constant for this reaction.

8.Consider the following reaction,

2 A + B + 2DE + F

with the following mechanism,

(1)2 A + BC

(2)C + 2 DE + F

(a)Derive a general rate law for this reaction using the steady state approximation.

(b)Write a simpler rate law that is valid when [D] is sufficiently small so that,

k2[D]2 < k –1 .

(c)Write a simpler rate law that is valid when [D] is sufficiently small so that,

k2[D]2 > k –1 .

9.Consider the reaction for the decomposition of ozone

2 O3 (g) 3 O2 (g)

The mechanism for the reaction is,

(1)O3 >O2 + O

(2)O3 + O 2 O2

(a)Use the steady state approximation to derive a general rate law for this reaction.

(b)Derive a simpler rate law that is valid when k-1[O2] > k 2[O3]

(c)How is the rate of decomposition of ozone affected by an increase in the concentration of oxygen?

10. Consider the following reaction.

NO2 (g) + CO (g) → CO2 (g) + NO (g)

The mechanism is as follows.

(1)2 NO2 NO3 + NO

(2)NO3 + CO >NO2 + CO2

(a)Derive the general rate law for this reaction using the steady state mechanism.

(b)Derive a simpler rate law that is valid during the initial phase of the reaction when it can be assumed that [NO] is negligible. Which is step is the rate limiting step during the initial phase of the reaction?

11.Consider the following reaction.

CO(g) + Cl2 (g) > COCl2 (g)

The mechanism is believed to be,

(1) Cl2 > 2Cl (fast equilibrium)

(2)Cl + CO > COCl (fast equilibrium)

(3)COCl + Cl2 > COCl2 + Cl(slow)

(4)2 ClCl2(fast)

Assuming that the mechanism is correct, derive the rate law for this reaction.

12. Consider the following reaction.

2 NO2 (g) + F2 (g) >2 NO2F (g)

The mechanism is,

(1)NO2 + F2 > NO2F + F(slow)

(2)NO2 + F > NO2F (fast)

What is the rate law for this reaction?

(a)Rate = k[NO2]2[F2]

(b)Rate = k[NO2][F2]

(c)Rate = k[NO2][F]

(d)Rate = [ NO2F]/ t

Chpt. 13

13.Consider the following reactions.

Na2O (s) → 2 Na (l) + ½ O2 (g)K = 2 x 10-25

Na2O2 (s) → 2 Na (l) + O2 (g)K = 5 x 10-29

Calculate the equilibrium constant for the following reaction.

Na2O (s) + ½ O2 (g)→Na2O2 (s)

14.An evacuated chamber is filled with NOCl gas. The NOCl decomposes according to the

following equation.

2 NOCl(g) 2 NO (g) + Cl2 (g)

If the initial pressure of the pure NOCl is 0.7500 atm and the final pressure in the chamber after the gases have reached equilibrium is 0.7860 atm calculate Kp for the reaction.

15. Antimony pentachloride decomposes according to the following equation.

SbCl5 (g) → SbCl3 (g) + Cl2 (g)

Suppose that 10.0 g of antimony pentachloride is placed in a 5.00 L container and allowed to establish equilibrium. Calculate the concentration of all species at equilibrium.

K = 2.51 x 10-2

16. Consider the following reaction,

H2 (g) + Br2 (g) < > 2 HBr (g) , Kp= 2.4 x 108 at 425OC

Suppose that H2 (g) and Br2 (g) are pumped into a container at 425 OC. Given that the initial partial pressure of H2 (g) is 1.00 atm and that the initial partial pressure of Br2 (g) is 2.00 atm calculate the partial pressure of all species once equilibrium is attained. Assume that the temperature is maintained at 425 OC.

17. Consider the following reaction

2 NOCl (g) 2 NO (g) + Cl2 (g) ,K= 1.6 x 10-5

Suppose that 0.050 mol of NOCl is pumped into a 50.0 L container. Calculate the concentration of all species (to two significant figures) once the system has come to equilibrium. (You will need to use the method of successive approximations)

For problems 18-20 consider the following reaction.

CO2 (s) CO2 (g)

Assume that the volume of the container is constant and that the volume of the solid is negligible compared to the volume of the gas.

18. If the system is at equilibrium and some additional CO2 (s) is added,

(a)the concentration of CO2 (g) will increase.

(b)the concentration of CO2 (g) will decrease.

(c)the concentration of CO2 (g) will remain the same.

19. If the system is at equilibrium and some additional CO2 (g) is added,

(a)the mass of CO2(s) will increase.

(b)the mass of CO2(s) will decrease.

(c)the mass of CO2(s) will remain the same

20. Given that the reaction is endothermic, an increase in temperature will cause

(a)the concentration of CO2(g) to increase.

(b)the concentration of CO2(g) to decrease

(c)no change in the concentration of CO2(g)