INITIAL RATES PROBLEMS KEY

1. Given reaction rate data for: F2(g) + 2ClO2(g)  2FClO2(g)

Experiment [F2](M) [ClO2](M) Initial Rate (M/s)
1 0.10 0.010 1.2 x 10-3
2 0.10 0.040 4.8 x 10-3
3 0.20 0.010 2.4 x 10-3

A. Determine the order of each reactant and the overall reaction order.
From 1  3 [F2] doubles, ClO2 is constant, and Rate doubles:
2x = 2 x = 1 = order for [F2]
From 1  2 [ClO2] quadruples, F2 is constant, and Rate quadruples:
4y = 4 y = 1 = order for [ClO2]
Overall Reaction Order: 1 + 1 = 2
B. Write the rate law for the reaction.
Rate = k[F2][ ClO2]
C. Calculate the rate constant, k.

Rate 1.2x103 M/ s
k = [F2 ][ClO 2 = = 1.2 M-1s-1
] 0.10M0.010M

2. Given the rate data for: 2O3(g)  3O2(g)

Run [O3] (M) Rate (M/s)
1 0.00600 5.03 x 10-7
2 0.00300 1.28 x 10-7
3 0.00150 3.08 x 10-8
A. What is the rate law for the reaction?
Put larger concentrations and rates on top to avoid fractions!
From 2  1:
 0.00600M

 5.03x10 7  x = 2 = order for O3
x  1.28x10

7
 simplifies to 2x = 4
0.00300M 

   
Rate = k [O3]2
B. Calculate the rate constant, k.

Rate 5.03x107 M/ s
k = [O ]2= = 0.0140 M-1s-1
3
0.00600M 2

C. What is the rate of reaction when [O3] = 0.00500 M?

Kinetics 1
Problems
 Rate = k [O3]2 = 0.0140 M-1s-1(0.00500 M)2 = 3.50x10-7 M/s

Kinetics 2
Problems
 FIRST-ORDER KINETICS PROBLEMS KEY
1. The rate law for the decomposition of N2O5 is Rate = k[N2O5], where k = 5.0 x 10-4 s-1.
What is the concentration of N2O5 after 1900 s, if the initial concentration is 0.56 M?
[A]
ln [A] t = - kt [N2O5]0 = 0.56 M; k = 5.0 x 10-4 s-1; t = 1900 s
0
[N O ]
ln 2 5 t = - (5.0 x 10-4 s-1) (1900 s) = -0.95
(0.56 M )
[N 2 O5 ]t
Take anti ln both sides: = e-0.95 = 0.387
(0.56 M )
[N2O5]t = 0.560.387 = 0.22 M
2. The first order reaction, SO2Cl2  SO2 + Cl2, has a rate constant of 0.17 h-1.
If the initial concentration of SO2Cl2 is 1.25 x 10-3 M, how many seconds does it take for the
concentration to drop to 0.31 x 10-3 M?
k = 0.17 h-1 [SO2Cl2]t = 0.31 x 10-3 M [SO2Cl2]0= 1.25 x 10-3 M
 0.31x10 M 
3

[A]t  ln

 1.25x10
3
M    1.39 
ln [A] = - kt  t= 0.17h1 = -  = 8.18
1  h
0  0.17h 
 3600 s 
t = 8.18 h    2.9x104 s
 1hr 
3. Cobalt-60 is a radioisotope that decays by first-order kinetics and has a half-life of 5.26
years. The Cobalt-60 in a radiotherapy unit must be replaced when the concentration of Co
decreases to 75.0% of its initial value. When does this occur?

t1/2 = 5.26 yr k t1/2 = 0.693 k = 0.693

= 0.132 yr-1
5.26
yr

[A] 0.75[Co]0
ln [A] t = - kt [Co]t = 0.75[Co]0 ln = -(0.132 yr-1) t
0
[Co]0
ln 0.75 = -(0.132 yr-1) t  -0.288 = -(0.132 yr-1) t  t = 2.18 yr
4. The first order reaction, CH3NC  CH3CN, has a rate constant of 6.3x10-4 s-1 at 230 C.
A. What is the half-life of the reaction?

t1/2 =
0.693 0.693 1.1 x 103 s
k = 4
6.3x10 s =
1

B. How much of a 10.0 g sample of CH3NC will remain after 5 half-lives?

 1 5
10.0 g   = 0.313 g
2 
C. How many seconds would be required for 75% of a CH 3NC sample to decompose?
75% decomposed; 25% remains, so 2 half lives have passed.
21.1 x 103 s = 2.2 x 103 s
 ACTIVATION ENERGY AND REACTION MECHANISMS KEY
1. Draw the potential energy profile for a reaction with H = -150 kJ and Ea = 100 kJ.

Ea
E
H

2. A certain first order reaction has a rate constant of 1.75 x 10-1 s-1 at 20 °C. What is the
value of k at 60 °C if Ea = 55.5 kJ/mol?
k1 = 1.75 x 10-1 s-1 T1 = 293 K Ea = 55.5 kJ/mol
J  1kJ  -3
k2 = ? T2= 333 K  
R = 8.314 Kmol 1000 J = 8.314 x 10 kJ/(Kmol)
 
kJ
 k    55.5
1 1
  1 1 
ln  1  = Ea  1  1  1.75x10 s mol   
ln   =
 k 2 R  T 2 T1   k2  kJ  333 K 293 K 
8.314 x10
3 Kmo
l
 1.75x10 s 
1 1
3 -1
ln   = 6.68x10 K(-0.000410 ) = -2.74
 k2  K
1.75x10 1 s 1.75x10 1 s
1
= e-2.74 = 0.0646  k2 = 1

= 2.71 s-1
k2 0.0646

1. The following mechanism has been proposed for the reaction: 2SO 2 + O2  2SO3
Step 1: 2NO + O2  2NO2 slow
Step 2: 2NO2 + 2SO2  2NO + 2SO3 fast

A. Which is the rate determining step? step 1 is slow step

B. What is the molecularity of the rate determining step? termolecular

C. Identify the catalyst. NO

D. Identify the intermediate. NO2

E. Write the rate law for the reaction.

Rate = k[NO]2[O2]
F. What is the overall reaction order? 2 + 1 = 3