KEY

Practice Problems: Kinetics

CHEM 1B

1. Based on the data and graph below:

React. A Prod. B Prod.C

Time (s) Reaction of Species A at 300°C
(mol/L) (mol/L) (mol/L)
0.0300
0. 0.0250 0.0000 0.0000

Concentration (mol/L)
Reactant A
50. 0.0149 0.0101 0.0050 0.0250 Product B
Product C
100. 0.0106 0.0144 0.0072 0.0200
150. 0.0083 0.0167 0.0084
200. 0.0068 0.0182 0.0091 0.0150
250. 0.0057 0.0193 0.0096 0.0100
300. 0.0050 0.0200 0.0100
350. 0.0044 0.0206 0.0103 0.0050
400. 0.0039 0.0211 0.0105 0.0000
450. 0.0035 0.0215 0.0107 0 100 200 300 400 500
500. 0.0032 0.0218 0.0109 Time (s)

2A  2B + C
a) Write the balanced equation for the reaction of A: _____________________________________

b) What evidence did you use to determine the coefficients in the balanced equation?
 Reactant A is disappearing at the same rate as Product B is appearing, so they must have the same
stoichiometric coefficient (notice that for any t, [A]t + [B]t = [A]0 + [B]0)
 Product B is appearing twice as fast as Product C, so B must have a coefficient twice as large as C
(notice that for any t, [B]t – [B]0 = 2 × ([C]t – [C]0), for example: look at t = 500.s)
c) Write a general rate equation relating the average rates with respect to each reactant and product.
1 [A] 1 [B] [C]
rate = − = =
2 t 2 t t
d) Calculate the average rate for Reactant A from 100s to 400s, and then use the relationship from
Part c) to calculate the average rate for Product C over the same time interval.
[A] (0.0039 M – 0.0106 M)
= = – 2.2 x 10–5 mol/L∙s
t (400.s – 100.s)

[C] 1 [A] –5
= − = − ½ (– 2.233 x 10–5 mol/L∙s) = 1.1 x 10 mol/L∙s
t 2 t
a)0 A
Concentration

2. Sketch on the graph to the right: 0

(mol/L)

a) the initial rate 0

B
b) the instantaneous rate at Point C c)
0
c) the average rate from Points B to G C G
0 b)
0
0 100 200
Time (s) 300
 3. Based on the following experimental data:
Overall Reaction:
2 I– + S2O82–  I2 + 2 SO42–

Trial [I–]o [S2O82–]o Initial Rate

Number (mol/L) (mol/L) (mol/L·min)
1 0.080 0.040 12.5 x 10–6
2 0.040 0.040 6.23 x 10–6
3 0.080 0.020 6.27 x 10–6

a) Determine the rate law (show work). rate1 12.5 x 10 –6 mol/L·min

ln ln
OR rate2 6.23 x 10 –6 mol/L·min
m = = = 1.0
rate = k [I–]m [S2O82–]n [I–]1 0.080 mol/L
ln ln
trial 1 ÷ 2 2.01 = – (2.0) m
– m=1 [I–]2 0.040 mol/L
trial 1 ÷ 3 1.99 = – – (2.0)n n=1
rate1 12.5 x 10 –6 mol/L·min
ln ln
– 2– rate3 6.27 x 10 –6 mol/L·min
rate = k [I ] [S2O8 ] n = = = 1.0
[S2O82–]1 0.040 mol/L
ln ln
[S2O82–]3 0.020 mol/L
]1

b) Using data from trial 1, determine the rate constant (k)

rate = k [I–] [S2O82–]
12.5 x 10–6 mol/L·min = k (0.080 mol/L) (0.040 mol/L)
k = 0.00390625 L/mol·min = 0.0039 L/mol·min

c) Determine the initial rate if [I–]o = 0.120 mol/L and [S2O82–] o = 0.150 mol/L
rate = k [I–] [S2O82–]
rate = (0.00390625 L/mol·min) (0.120 mol/L) (0.150 mol/L)
–5
rate = 7.03125 x 10–5 mol/L·min = 7.0 x 10 mol/L·min

d) Could the overall reaction above be an elementary step? Yes or No (circle one)
Explain.
The orders in the experimentally derived rate law do not match the stoichiometric
coefficients in the overall reaction.
e) How many particles collide in the RDS, and what are they?
Two particles collide in the RDS, one I– and one S2O82–.
 1.0
4. Based on the following experimental data:

[H2O2] (mol/L)
0.8
[H2O2] 1 / [H2O2]
Time (s) ln [H2O2] 0.6
(mol/L) (L/mol)
0 1.0 0.00 1.0 0.4
120 0.91 -0.09 1.1
0.2
300 0.78 -0.25 1.3
600 0.59 -0.53 1.7 0.0
1200 0.37 -0.99 2.7 0 1000 2000 3000 4000
1800 0.22 -1.51 4.5
2400 0.13 -2.04 7.7 Time (s)
3000 0.082 -2.50 12
3600 0.050 -3.00 20.
0.0
-0.5
-1.0
a) What is the order of this reaction with respect

ln [H2O2]
to the reactant H2O2, and how do you know? -1.5
-2.0
-2.5
The reaction is 1st order with respect to H2O2,
-3.0
because the ln [H2O2] versus time graph is linear.
-3.5
0 1000 2000 3000 4000

Time (s)
b) What is the form of the integrated rate law?
20.0

ln [H2O2]t = –kt + ln [H2O2]o 15.0

1 / [H2O2]

10.0

c) What is the rate constant (k)? 5.0

rise –3.00 – 0.00 0.0

–k = slope = = = –8.333 x 10–4 s–1 0 1000 2000 3000 4000
run 3600 s – 0 s
Time (s)
–4 –1
k = 8.3 x 10 s

d) What would the concentration of H2O2 be at 4500 seconds?

ln [H2O2]t = –kt + ln [H2O2]o = –(8.333 x 10–4 s–1) (4500 s) + ln (1.0) = –3.75

[H2O2]t = e–3.75 = 0.0235177459 mol/L = 0.02 mol/L

Note:
Reviewing significant figure rules for
logs and exponents would be useful
(CHEM 1A Class Handouts, Chapter 0)
5. The half-life of a first-order reaction is found to be 28.25 min.

a) Using the definition of a half-life, approximately how long would it take for 95.0% of the
original amount of reactant A to disappear? Give a range of possible times in multiples of t½ and
in minutes.

95.0% disappeared = 5.0% remaining

4 t½ to 5 t½ (6.25% to 3.125% remaining)
113.0 min to 141.2 min
Note:
5 t½ = 5 (28.25 min) = 141.25 min
which rounds DOWN according to
the last digit 5, even/odd rounding rule
b) What is the rate constant (k) for this reaction?
ln (2)
t½ =
k

ln (2) ln (2) –1
k = = = 0.0245361834 min–1 = 0.02454 min
t½ 28.25 min

c) Using the integrated rate law for a first-order reaction, how long would it take for 95% of the
original amount of reactant A to disappear?
ln [A]t = –kt + ln [A]o
[A]t Note: 5.0%
ln remaining
[A]o ln (0.050) –2.995732274
t = = = = 122.0944687 min = 120 min
–k –0.0245361834 min–1 –0.0245361834 min–1

d) If the initial concentration of reactant A is 2.50 M, what is the concentration after exactly 3
hours?
ln [A]t = –kt + ln [A]o = –(0.0245361834 min–1) (180 min) + ln (2.50 M)
ln [A]t = –4.416513009 + 0.9162907319 = –3.500222277
[A]t = e–3.500222277 = 0.030190672 mol/L = 0.0302 M

e) What is the reaction rate at exactly 3 hours? Assume the reaction is not reversible.
rate = k [A]
rate = (0.0245361834 min–1) (0.030190672 mol/L) = 7.407638643 x 10–4 mol/L·min
–4
rate = 7.41 x 10 mol/L·min
6. Without a catalyst, the activation energy of a reaction is 367.8 kJ/mol. With a catalyst, the activation
energy is 187.2 kJ/mol. Assuming the frequency factor (A) and the initial concentrations of all
reactants are the same for each reaction, how many times faster is the initial rate of the catalyzed
reaction at 26.88°C? Hint: Start with the ratio of the rate laws for the two reactions, with the faster
reaction in the numerator.

rate = k[react.]m[react.]n 26.88°C

+ 273.15
k = Ae (–Ea/RT) 300.03 K

rate (cat) k (cat) [react.]m [react.]n A e (–Ea cat /RT) [react.]m [react]n e (–Ea cat /RT)
= = =
rate (uncat) k (uncat) [react.]m [react]n A e (–Ea uncat /RT) [react.]m [react]n e (–Ea uncat /RT)

(– 187.2 kJ/mol)(103 J/kJ)  –75.04245088

(8.314462 J/K·mol) (300.03 K)

e (–Ea cat /RT)
e 2.56730622 x 10−33
(–Ea uncat /RT)
= = −65
= 2.763742014 x 1031
e 9.28923978 x 10
(– 367.8 kJ/mol)(103 J/kJ)
(8.314462 J/K·mol) (300.03 K)  – 147.4391743
e

3 x 1031
Answer: The catalyzed reaction is ________________ times faster than the uncatalyzed reaction