Practice Problems Chemical Kinetics 1.

. The gas reaction N2O5 2NO2 + 1/2O2 follows the Arrhenius equation k = Ae(-Ea/RT) where R = 8.314J K-1 mol-1 and 1 calorie = 4.184J. At the temperature T=273K, k = 3.46 x 10-5 s-1, whereas at T = 298K, k = 8.87 x 10-3 s-1. a. What is the value of the activation energy Ea in kcal/mol 2. The reaction between bromate ions and bromide ions in acidic aqueous solution is BrO3-(aq) + 5Br- (aq) + 6H+ (aq) 3Br2(l) + 3H2O(l) Using the data from 4 experiments shown below determine the orders of the rate of reaction for all three reactants, the overall reaction order, and the value of the rate constant k. Experiment [BrO3-] (M) [Br-] (M) [H+] (M) rate (M/s) 1 2 3 4 0.10 0.20 0.20 0.10 0.10 0.10 0.20 0.10 0.10 0.10 0.10 0.20 8.0 x 10-4 1.6 x 10-3 3.2 x 10-3 3.2 x 10-3

3. Given the following experimental data, find the rate law and the rate constant for the reaction: NO (g) Run 1 2 3 4 + NO2 (g) + O2 (g) N2O5 (g) [NO2[o , M 0.10 M 0.10 M 0.30 M 0.10 M [O2]o , M 0.10 M 0.10 M 0.20 M 0.20 M Initial Rate, Ms-1 2.1 x 10-2 4.2 x 10-2 1.26 x 10-1 2.1 x 10-2

[NO]o , M 0.10 M 0.20 M 0.20 M 0.10 M

4. The half-life of a radioisotope is found to be 4.55 minutes. If the decay follows first order kinetics, what percentage of isotope will remain after 2.00 hours? 5. The mechanism of a reaction is shown below. a) What is the overall reaction? b) Which compounds are intermediates? c) Predict the rate law based on this mechanism. d) What is the overall order of the reaction? HOOH + I HOI + OH HOI + I I2 + OH 2OH + 2H3O+ 4 H2O (slow) (fast) (fast)

6. For the reaction A + B C, the rate constant at 215 oC is 5.0 x 10-3 and the rate constant at 452o C is 1.2 x 10-1. a) What is the activation energy in kJ/mol? b) What is the rate constant at 100o C.

Answers: 1. 35.9 kcal/mol 2. Rate = k[BrO3-] [Br-] [H+]2 Overall order = 4th order k = 8.0 L3/mol3s 3. Rate = k[NO] [NO2] k = 2.1 M-1s-1 4. k = 0.152 min-1 At = 1.15 x 10-6 % (not much!!) 5. a) Overall reaction: HOOH + 2 I + 2 H3O+ I2 b) Intermediates: OH and HOI c) Predicted mechanism: Rate = k [HOOH][I ] d) Overall order: 2nd order 6. a) 39.4 kJ/mol b) 2.50 x 10-4 s-1

+ 4 H2O

Answers: 1. 35.9 kcal/mol 2. Rate = k[BrO3-] [Br-] [H+]2 Overall order = 4th order k = 8.0 L3/mol3s 3. Rate = k[NO] [NO2] k = 2.1 M-1s-1 4. k = 0.152 min-1 At = 1.15 x 10-6 % (not much!!) 5. a) Overall reaction: HOOH + 2 I + 2 H3O+ I2 b) Intermediates: OH and HOI c) Predicted mechanism: Rate = k [HOOH][I ] d) Overall order: 2nd order 6. a) 39.4 kJ/mol b) 2.50 x 10-4 s-1

+ 4 H2O

Answers: 1. 35.9 kcal/mol 2. Rate = k[BrO3-] [Br-] [H+]2 Overall order = 4th order k = 8.0 L3/mol3s 3. Rate = k[NO] [NO2] k = 2.1 M-1s-1 4. k = 0.152 min-1 At = 1.15 x 10-6 % (not much!!) 5. a) Overall reaction: HOOH + 2 I + 2 H3O+ I2 b) Intermediates: OH and HOI c) Predicted mechanism: Rate = k [HOOH][I ] d) Overall order: 2nd order 6. a) 39.4 kJ/mol b) 2.50 x 10-4 s-1

+ 4 H2O