1. Kinetics (Ch 15) 1. For the reaction: A + 3B  2C a. Express the rate in terms of concentrations of A, B and C. b. The following data was collected for this reaction at 25 ˚C. What is the differential rate law? Expt [A] 0 [B] 0 Initial rate (M/s) 1 0.10 0.10 1.2 x 10 -4 2 0.10 0.20 4.8 x 10 -4 3 0.20 0.10 2.4 x 10 -4 c. What is the overall order of the reaction? d. What is the rate constant?

2. Kinetics (Ch 15) 2. Given the following data for the reaction: 2A + B + C  D + 3E Determine the differential rate law. Expt [A] 0 [B] 0 [C] 0 Initial rate (mol/L s) 1 0.020 0.010 0.020 0.0050 2 0.040 0.010 0.020 0.0100 3 0.020 0.010 0.060 0.0050 4 0.040 0.040 0.020 0.160

3. Kinetics (Ch 15)

4. 3. The decomposition of nitrogen dioxide, 2 NO 2  2NO + O 2, obeys the rate law rate = k[NO 2 ] 2. For this reaction the rate constant, k = 1.8 x 10 -2 L/mol s at 500 K. If the initial concentration of NO 2 is 1.2 M, how long will it take for the concentration to decrease by 25%?

5. Kinetics (Ch 15) 4. The thermal decomposition of phosphine, PH 3, into phosphorous and hydrogen is a first order reaction. The half-life for this reaction is 35 sec at 680 ˚C. a. Calculate the time required for 95% of the phosphine to decompose. b. What fraction of phosphine remains after 70 sec?

6. Kinetics (Ch 15) 5. The successive half-lives for a certain reaction were measured to be 10, 20 and 40 minutes. If the initial concentration of the reactant was 1.0 M, how much was left after 80 min of reaction time?

7. Kinetics (Ch 15) 6. Given the following mechanism: H 2 O 2  H 2 O + O O + CF 2 Cl 2  ClO + CF 2 Cl ClO + O 3  Cl + 2O 2 Cl + CF 2 Cl  CF 2 Cl 2 a. Write the overall reaction. b. Identify any intermediate(s). c. Identify any catalyst. d. Write the rate law for each step.

8. Kinetics (Ch 15) 7. For the following reaction, the rate law was determined to be r = k [NO] 2 [O 2 ] 2 NO + O 2  2 NO 2 Determine whether or not the following mechanisms are consistent with this rate law. a. NO + O 2  NO 2 + O slow O + NO  NO 2 fast b. NO + O 2  NO 3 fast equilibrium NO 3 + NO  2NO 2 slow

9. Kinetics (Ch 15) 8. The forward activation energy for a reaction is 60 kJ/mol. If ΔE for the reaction is 45 kJ/mol, what is the activation energy for the reverse reaction?

10. Kinetics (Ch 15) 9. What factors affect the rate constant for a reaction?

11. Kinetics (Ch 15) 10. The rate constants for a certain second order reaction are 3.20 x 10 -2 1/M s at 24 ˚C and 9.45 x 10 -1 1/M s at 150 ˚C. a. Calculate the activation energy for the reaction. b. What is the rate constant at 100 ˚C?

12. Kinetics (Ch 15) Bonus Q: How would the addition of a catalyst change the energy values in #8?