Chemical Kinetics

References: Brady/Jespersen/Hyslop, Chemistry, 7 ed, 2015, John Wiley & Sons, Inc.
Raymond Chang, Chemistry, 10 ed, 2010, McGraw Hill.
Petrucci et.al, 9ed, 2007, Prentice-Hall ©

Learning Outcomes
• Describes factors that affect reaction rates
• Calculates the relative rate of reactant reduction
and the addition of product from the experimental
data
• Determines rate laws of zero, 1st, and 2nd order
• Describes collision theory
• Calculates activation energy from Arrhenius
equation
• Write the reaction mechanism and decide which the
most possible mechanism using experimental data

1
Outline (Teaching Plan)
1. Factors that Affect Reaction Rates
2. Measuring Rate of Reaction
3. Rate Laws
4. Integrated Rate Law
5. Collision Theory
6. Activation Energy, Ea
7. Reaction Mechanism
8. Catalyst

INTRODUCTION

Kinetics:
• Study of factors that govern
• How rapidly reactions occur and
• How reactants change into products
• How long it takes to reach equilibrium

Rate of Reaction:
• Speed with which reaction occurs
• How quickly reactants disappear and products
form

2
I. Factors that Affect Reaction Rates
1. Chemical nature of reactants
• What elements, compounds, salts are involved?
• What bonds must be formed, broken?
• What are fundamental differences in chemical reactivity?

2. Ability of reactants to come in contact

Reactants must meet in order to react
• Homogeneous reaction
• All reactants in same phase
• Occurs rapidly
• Heterogeneous reaction
• Reactants in different phases
• Reactants meet only at interface between phases
• Surface area determines reaction rate
• Increase area, increase rate; decrease area, decrease rate

I. Factors that Affect Reaction Rates

3. Concentrations of reactants
• Rates of both homogeneous and heterogeneous reactions
affected by [X ]
• Collision rate between A and B increase if we increase [A] or
increase [B ].

4. Temperature
• Rates are often very sensitive to temperature
• Raising temperature usually makes reaction faster :
a. Faster molecules collide more often and collisions have more energy
b. Most reactions, even exothermic reactions, require energy to occur

3
I. Factors that Affect Reaction Rates

5. Presence of Catalysts
• Catalysts
• Substances that increase rates of chemical reactions
without being used up
• Rate-accelerating agents
• Speed up rate dramatically
• Chemicals that participate in mechanism but are
regenerated at the end
• e.g. Enzymes and zeolites

II. Measuring Rate Reaction

Rate of change of concentration with time.

2 Fe3+(aq) + Sn2+ → 2 Fe2+(aq) + Sn4+(aq)

Given data:
t = 38.5 s [Fe2+] = 0.0010 M
Δt = 38.5 s Δ[Fe2+] = (0.0010 – 0) M

Δ[Fe2+] 0.0010 M
Rate of formation of Fe2+= = = 2.610-5 M s-1
Δt 38.5 s

4
II. Measuring Rate Reaction
In General : aA+bB→cC+dD
Rate of reaction = rate of disappearance of reactants
1 Δ[A] 1 Δ[B]
=- =-
a Δt b Δt
= rate of appearance of products

1 Δ[C] 1 Δ[D]
= =
c Δt d Δt
2 Fe3+(aq) + Sn2+ → 2 Fe2+(aq) + Sn4+(aq)
Δ[Sn4+] 1 Δ[Fe2+] 1 Δ[Fe3+]
= = -
Δt 2 Δt 2 Δt
Rate reaction Always positive Whether [X ] is
increasing or decreasing 10

Your Turn!

Based on the reaction

2CO(g) + O2(g) → 2CO2(g)
the rate of disappearance CO is measured to be
2.0 M/s. What would be the rate of disapperance
O 2?

A.The same
B.Twice as great
C.Half as large
D.You cannot tell from the given information
11

5
Your Turn!

In the reaction
2 NO(g) + Cl2(g) → 2NOCl(g)
What is the rate of reaction with respect to NO?
D[NO]
A. Rate = -1/2 DT
B. Rate = +1/2 D[NO]
DT
D[NO]
C. Rate = -2
DT
D. Rate = 2 D[NO]
DT

12

II. Measuring Rate Reaction

(Experimental Data)
Determining and Using an Initial Rate of Reaction.

H2O2(aq) → H2O(l) + ½ O2(g) -Δ[H2O2]

Rate =
-(-2.32 M / 1360 s) = 1.7  10-3 M s-1 Δt

 Measured in three
-(-1.7 M / 2600 s) = ways:
• Instantaneous
6  10-4 M s-1
rate
• Average rate
• Initial rate

14

6
Learning Check
How much concentration of H2O2 at 100 s?
Use initial rate.
- Δ[H2O2]
[H2O2]i = 2.32 M Rate = 1.7 10-3 M s-1 =
Δt

-Δ[H2O2] = -([H2O2]f - [H2O2]i) = 1.7  10-3 M s-1  Δt

[H2O2]100 s – 2.32 M = -1.7  10-3 M s-1  100 s

[H2O2]100 s = 2.32 M - 0.17 M

= 2.15 M
15

Your Turn
2 HI(g) → H2(g) + I2(g)
[HI] (mol/L) Time (s)
0.100 0
0.0716 50 Calculate how much the
0.0558 100 rate of dissappearance
0.0457 150 of HI at :
0.0387 200  initial rate,
0.0336 250  t = 100 s and
0.0296 300  t = 300 s
0.0265 350
16
Given Data at 508 oC

7
Answer : Initial Rate
2 HI(g) → H2(g) + I2(g) Initial rate
[HI] Time ▪ Average rate between first
(mol/L) (s) two data points
0.10
0.100 0 0.09 rate = -
(0.0716 - 0.100) M
(50 – 0) s
0.0716 50 0.08
–(–0.0284 M )
=
[HI] (mol/L)
0.0558 100
0.07
50 s
0.06
= 5.68 ´ 10-4 M / s
0.0457 150 0.05

0.0387 200
0.04

0.03

0.0336 250 0.02

0 50 100 150 200 250 300 350
0.0296 300 time (s)

0.0265 350 Given Data at 508 oC 17

Answer : rate at 100 s

0.10
Dy rise
0.09 Rate = -slope = =
Dx run
0.08 (0.044 - 0.068)M
=-
[HI] (mol/L)

0.07 (150 - 50) s

-0.024M
0.06 =- = 2.4 ´ 10-4 M / s
(50,0.068) 100 s
0.05

0.04

0.03 (150,0.044)

0.02
0 50 100 150 200 250 300 350
time (s) 18

8
Answer : rate at 300 s
0.10 (0.0265 - 0.0296) M
Rate = -
0.09 (350 - 300) s
0.08 0.0031 M
=
[HI] (mol/L)

0.07 50 s
0.06 = 6.20 ´ 10-5 M / s
0.05

0.04

0.03

0.02 (350,0.0265)
(300,0.0296)
0 50 100 150 200 250 300 350
time (s) 19

Answer at 300 s

[HI] (mol/L) Time (s) 2 HI(g) → H2(g) + I2(g)

0.100 0 Rate of dissapearance HI =
0.0716 50 tangent of curve at 300 s
0.0558 100 (0.0265 - 0.0296) M
0.0457 150 Rate = -
(350 - 300) s
0.0387 200
0.0031 M
0.0336 250 =
50 s
0.0296 300
= 6.20 ´ 10-5 M / s
0.0265 350
20

9
Your Turn
A reaction for the decomposition of NO2 was
studied. The concentration of NO2 was found to be
0.0258 M at 5 minutes and at 10 minutes the
concentration was 0.0097 M. What is the average
rate of the reaction between 5 min and 10 min?
A. 310 M/min
B. 3.2 × 10–3 M/min
C. 2.7 × 10–3 M/min
D. 7.1 × 10–3 M/min

(0.0258 M - 0.0097 M ) = 3.2 ´ 10-3 M / min

10 min - 5 min 21

III. Rate Laws

Effect of concentration on reaction rates
a A + b B …. → g G + h H ….
Rate law of reaction = k [A]m [B]n ….
Rate constant = k
• m and n = exponents found experimentally
• No necessary connection between stoichiometric
coefficients (a, b) and rate exponents (m, n)
• Usually small integers
• Sometimes simple fractions (½, ¾) or zero

Overall order of reaction = m + n + ….

22

10
Learning Check (Order Reaction)

The following rate law has been observed:

Rate = k [H2SeO][I–]3[H+]2. The order with
respect to I– and the overall reaction rate is:
A. 6, 2
B. 2, 3 Exponent for I- is 3

C. 1, 6 Sum of all exponents is 6

D. 3, 6

23

You Turn (Order Reaction)

For the following reaction 2 A + 5 B ➔3 Z the
Rate = k[A]2[B]1. What is the overall order of
the reaction?
A. 7
B. 2 Sum of all exponents is 3

C. 3 We do not use coefficients from

D. 10 balanced reaction

24

11
How to Calculated the Order of a
Reaction by Initial Rates (1)
• Use the data provided establish the order of
the reaction with respect to HgCl2 and C2O22-
and also the overall order of the reaction.

25

How to Calculated the Order of a

Reaction by Initial Rates (2)
Notice that concentration changes between reactions are by a
factor of 2.
Write and take ratios of rate laws taking this into account.
R3 = k[HgCl2]3m[C2O42-]3n

R2 = k[HgCl2]2m[C2O42-]2n = k(2[HgCl2]3)m[C2O42-]3n

R2 k(2[HgCl2]3)m[C2O42-]3n
=
R3 k[HgCl2]3m[C2O42-]3n
R2 k2m[HgCl2]3m[C2O42-]3n 2mR3
= = = 2.0
R3 k[HgCl2]3m[C2O42-]3n R3
2m = 2.0 therefore m = 1.0

12
How to Calculated the Order of a
Reaction by Initial Rates (3)
Notice that concentration changes between reactions are by a
factor of 2.
Write and take ratios of rate laws taking this into account.

R2 = k[HgCl2]21[C2O42-]2n = k(0.105)(0.30)n

R1 = k[HgCl2]11[C2O42-]1n = k(0.105)(0.15)n
R2 k(0.105)(0.30)n
=
R1 k(0.105)(0.15)n
R2 (0.30)n 7.110-5
= n
= 2n = = 3.94
R1 (0.15) 1.810-5
2n = 3.94 therefore n = 2.0

How to Calculated the Order of a

Reaction by Initial Rates (4)

R2 = k[HgCl2]21 [C2O42-]22

First order + Second order = Third Order

28

13
Your Turn
2 SO2 + O2 ⎯→ 2 SO3
Rate = k[SO2]m[O2]n
Expt [SO2] [O2] Initial Rate, M s–1
# M M
1 0.25 0.30 2.5  10−3
2 0.50 0.30 1.0  10−2
3 0.75 0.60 4.5  10−2
4 0.50 0.90 3.0  10−2

Define the Rate Laws of Reaction!

Your Turn Solution (1)

m n
m
k éëSO 2 ùû éëO 2 ùû
n
Rate 4 k éëSO 2 ùû éëO 2 ùû
Rate 2 = 4 4
= 2 2
m n
Rate 1 m n Rate 2 k éëSO 2 ùû éëO 2 ùû
k éëSO 2 ùû éëO 2 ùû
1 1 2 2
m n m n
k éë0.50ùû éë0.30ùû k éë0.50ùû éë0.90ùû
4 = m n
3 =
k éë0.25ùû éë0.30ùû
m n
k éë0.50ùû éë0.30ùû
m
é0.50ù é0.90ù
n
ë û m
ë û
4 = =2
é0.25ù
m 3 = n
= 3n
ë û é0.30ù
ë û
4 = 2m or m=2
3 = 3n or n=1

14
Your Turn Solution (2)
Rate = k[SO2]2[O2]1
• 1st order in [O2]
• 2nd order in [SO2]
• 3rd order overall
• Can use any experiment to find k

rate 3.0 ´ 10-2 M / s

k= = = 0.13 M –2s-1
[SO2 ]2 [O2 ]1 (0.50 M )2 (0.90 M )

Rate = 0.13 M-2s-1 [SO2]2[O2]1

31

Your Turn (Rate Law)

The rate law for the reaction 2A +B → 3C is
rate= 0.045 M–1s–1 [A][B]
If the concentration of A is 0.2 M and that of B is
0.3 M, what will be the reaction rate?
Answer:
rate=0.045 M–1 s–1 [0.2][0.3]
rate=0.0027 M/s  0.003 M/s

15
Concentration and Time

• Rate law tells us how speed of reaction varies with

concentrations.

• Sometimes want to know

• Concentrations of reactants and products at given time
during reaction
• How long for the concentration of reactants to drop below
some minimum optimal value

• Need dependence of rate on time

Integrated Rate Law!!

IV. Integrated Rate Law

(Zero Order Reaction)
A → products
Rrxn = k [A]0
Rrxn = k (k = mol L-1 s-1)

-Δ[A] Move to the -d[A]

Rrxn= = k = k
infinitesimal
Δt dt
And integrate from 0 to time t
[A]t t

-[A] d[A] =  k dt
0
0

-[A]t + [A]0 = kt

[A]t = [A]0 - kt

16
First Order Reaction
-D[A]
Rate = = k [A]
Dt
• Corresponding to reactions
• A → products
[ A ]0
• Integrating we get ln = kt
[ A]t
• Rearranging gives ln[A]t = -kt + ln[ A]0

• Equation of line y = mx + b
35

First Order Reaction

Plot ln[A]t (y axis) vs. t (x axis)
ln[ A]t = − kt + ln[ A]0

• Yields straight line

• Indicative of first
order kinetics
• Slope = –k
• Intercept = ln [A]0
• If we don't know
already
36

17
Second Order Reaction
D[B ]
Rate = k [B ]2 = -
Dt
• Corresponding to special second order reaction
• 2B → products
1 1
• Integrating we get - = kt
[B ]t [B ] 0
1 1
• Rearranging gives = kt +
[B ]t [B ] 0
• Equation of line y = mx + b

37

Second Order Reaction

Plot 1/[B]t (y axis) vs. t (x axis)

1 1
= kt +
[B ]t [B ]0

• Yields straight line

• Indicative of 2nd order
kinetics
• Slope = +k
• Intercept = 1/[B]0

18
Prentice-Hall
General
Slide 39 Chemistry:
of 61© 2007Chapter 14

Pseudo First-Order Reactions

• Simplify the kinetics of complex reactions.
• Rate laws become easier to work with.
CH3CO2C2H5 + H2O → CH3CO2H + C2H5OH

 If the concentration of water does not change

appreciably during the reaction.
• Rate law appears to be first order.
 Typically hold one or more reactants constant
by using high concentrations and low
concentrations of the reactants under study.

How to Determine Reaction

Order Using Graphs
Make two plots
1. ln [A] vs. time
2. 1/[A] vs. time
• If ln [A] is linear and 1/[A] is curved, then reaction is 1st
order in [A]
• If 1/[A] plot is linear and ln [A] is curved, then reaction is
2nd order in [A]
• If both plots give horizontal lines, then 0 th order in [A]

40

19
Prentice-Hall
General
Slide 41 Chemistry:
of 61© 2007Chapter 14

Testing for a Rate Law

Plot [A] vs t. Plot ln[A] vs t. Plot 1/[A] vs t.

Example :
SO2Cl2 ⎯→ SO2 + Cl2
Time, min [SO2Cl2], M ln[SO2Cl2] 1/[SO2Cl2] (L/mol)
0 0.1000 -2.3026 10.000
100 0.0876 -2.4350 11.416
200 0.0768 -2.5666 13.021
300 0.0673 -2.6986 14.859
400 0.0590 -2.8302 16.949
500 0.0517 -2.9623 19.342
600 0.0453 -3.0944 22.075
700 0.0397 -3.2264 25.189
800 0.0348 -3.3581 28.736
900 0.0305 -3.4900 32.787
1000 0.0267 -3.6231 37.453
1100 0.0234 -3.7550 42.735

20
Solution:

First Order Plot for SO2Cl2 Second order plot for SO2Cl2
Decomposition Decomposition
-2.2 45

-2.4 40

1/[SO2Cl2] (L/mol)
-2.6
35
ln[SO2Cl2]

-2.8
30
-3.0
25
-3.2
20
-3.4

-3.6 15

-3.8 10
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
time (min) time (min)

Reaction is 1st order in SO2Cl2

43

Your Turn (1)

For a first-order reaction what should be plotted

in order to observe a linear relationship?

A. ln[reactant] vs. time

B. [reactant] vs. time
C. 1/[reactant] vs. time
D. Not enough information

44

21
Your Turn (2)
The rate constant for the second order reaction 2A
→ B is 5.3 × 10–5 M–1 s–1. What is the original
amount present if, after 2 hours, there is 0.35 M
available?

1 1
- = kt
[A ] [A 0]
1 1 5.3 ´ 10 - 5
- = ´ 7200 s
[0.35] [A 0] M s
A0=0.40 M
45

Your Turn (3)

A plot for a zeroth order reaction is shown. What is
the proper label for the y-axis in the plot ?
A. Concentration Zeroth Order Plot

B. ln of Concentration
C. 1/Concentration
D. 1/ ln Concentration

0 200 400 600 800 1000 1200

time (min)

46

22
 Next...

Half Life : First Order Reaction

• t½ is the time taken for
one-half of a reactant to
be consumed.
[A]t
ln = -kt
[A]0

½[A]0
ln = -kt½
[A]0

- ln 2 = -kt½

ln 2 0.693
t½ = =
k k
48

23
Half Life : First Order Reaction
Observe:
1. t½ is independent of [A]o
• For given reaction (and T)
• Takes same time for concentration to fall from
• 2 M to 1 M as from
• 5.0  10–3 M to 2.5  10–3 M
2. k1 has units (time)–1, so t½ has units (time)
• t½ called half-life
• Time for ½ of sample to decay

49

Half Life : First Order Reaction

Does this mean that all of sample is gone in
two half-lives (2 × t½)?
No!
• In 1st
t½, it goes to ½[A]o
• In 2nd
t½, it goes to ½(½[A]o) = ¼[A]o
• In 3rd
t½, it goes to ½(¼[A]o) = ⅛[A]o
• In nth
t½, it goes to [A]o/2n

24
Half Life : First Order Reaction

51

Half Life : Second Order Reaction

• How long before [A] = ½[A]o?
1
t 1/2 =
k [ A]0
• t½, depends on [A]o
• t½, not useful quantity for a second order
reaction

52

25
Learning Check
131I is used as a metabolic tracer in hospitals. It
has a half-life (first order), t½ = 8.07 days.
How long before the activity falls to 1% of the
initial value?

N -t ln2
ln = -kt =
No t 1
2

N æ 1 ö
t 1 ln (8.07 days)ln çç ÷÷
2 No è 100 ø
t =- =- = 53.6 days
ln 2 ln 2
53

Your Turn (1)

Which order has a half-life that is independent

of the original amount?
A. Zero
B. First
C. Second
D. None depend on the original quantity

54

26
Yurn Turn (2)
The radioactive decay of a new atom occurs by first
order reaction so that after 21 days, the original
amount is reduced to 33%. What is the rate
constant for the reaction in s–1?

æA ö
ln çç 0 ÷÷ = kt k = 0.0528 day–1
èAø k = 6.11 × 10–7 s–1
100
ln( ) = k (21 day)
33
55

Your Turn (3)

The half-life of I-132 is 2.295 h. What percentage
remains after 24 hours?

ln 2 ln 2
= t1/2 k= 0.302 h–1 = k
k 2.295 h
A 
ln o  = kt
 A 
æA ö
ln çç o ÷÷ = 0.302 h-1 ´ 24 h = 7.248
èAø
A =A o e −kt = Ao e −7.248 A = 0.0711% Ao
56

27
Your Turn (4)
A reaction is first order overall. For a given sample,
its initial rate is 0.0200 mol L-1 s-1 and 25.0 days later
its rate dropped to 6.25 x 10-4 mol L-1 s-1. What is its
half-life?
A. 25.0 days
B. 50.0 days
C. 12.5 days
D. 5.00 days

57

Summary
1. Calculate the rate of a reaction from a known rate
law using:
Rate of reaction = k [A] [B]
m n ….

2. Determine the instantaneous rate of the reaction

by:
Finding the slope of the tangent line of [A] vs t
or,
Evaluate –Δ[A]/Δt, with a short Δt interval.

58

28
Summary
3. Determine the order of reaction by:
a. Using the method of initial rates.
b. Find the graph that yields a straight line.
c. Test for the half-life to find first order reactions.

d. Substitute data into integrated rate laws to

find the rate law that gives a consistent value
of k.

59

Summary
4. Find the rate constant k by:
a. Determining the slope of a straight line graph.
b. Evaluating k with the integrated rate law.
c. Measuring the half life of first-order reactions.

5. Find reactant concentrations or times for certain

conditions using the integrated rate law after
determining k.

60

29
Next...

30