CHEM

301

Analytical Chemistry

Unit 3
Chemical
Kinetics:
Rate Laws
Integrated Rate Laws
Model for Chemical
Kinetics

CHEM
301

Analytical Chemistry

Chemical Kinetics
area of chemistry concerned with
reaction rates
understand the steps by which a
reaction takes place
the series of steps is called reaction
mechanism

CHEM
301

Analytical Chemistry

Reaction Rate
change in concentration of the reactant
or product per unit time
A

[A]
rate
[B]
[t]
[t]

p. 527, Table 12-1

p. 528, Fig. 12-1

CHEM
301

Analytical Chemistry

2NO2 (g) 2NO (g) + O2 (g)

CHEM
301

Analytical Chemistry

CHEM
301

Analytical Chemistry

CHEM
301

Instantaneous Rate
the rate is not
constant but
decreases with
time

Analytical Chemistry

CHEM
301

Analytical Chemistry

Rate Laws
chemical reactions are reversible
if the reverse reaction is neglected,
then the reaction rate depends only
on the concentration of the reactant
A

rate [A] [B]

[t]
[t]

CHEM
301

Analytical Chemistry

rate

Rate Laws

Conc.

rate =
k[reactant]X
k rate
constant

x order of the
reaction
* determined by
experiment

CHEM
301

Type of Rate Laws

differential
rate
lawdepends on
rate
concentration
integrated
rate
law
concentration
depends on
time

Analytical Chemistry

CHEM
301

Analytical Chemistry

Order of the Rate Law

rate = k[A]X
if x = 1, first order:

rate = k[A]1

if x = 2, second order: rate =

k[A]2
if x = 0, zero order:
rate = k[A]0

CHEM
301

Analytical Chemistry

CHEM
301

Analytical Chemistry

Method of Initial Rates

A. Involving a Single
Reactant

to determine the order of the reaction, start with

two different concentrations:

rate1 =
k[A]1x

rate1 [A]2

rate2 [A]1

rate2 =
k[A]2x
solve for x

CHEM
301

Analytical Chemistry

Method of Initial Rates

A. Involving a Single
Reactant
A
example:

products

[A], M

0.10

0.20

0.30

0.40

Initial rate,
M/s

0.36

0.72

1.08

1.44

ORDER:

1st order

CHEM
301

Analytical Chemistry

Method of Initial Rates

A. Involving a Single
Reactant
example:

[CH3CHO], M
Initial rate,
M/s

CH3CHO

CH4 + CO

0.10

0.20

0.30

0.40

0.085

0.34

0.76

1.4

ORDER:

2nd
order

CHEM
301

Analytical Chemistry

Method of Initial Rates

B. Involving More than One
Reactant
A + B

products

rate = k[A]X[B]Y
overall order = x + y

CHEM
301

Analytical Chemistry

Method of Initial Rates

B. Involving More than One
Reactant
example:

F2 (g) + 2ClO2 (g)

2FClO2 (g)

II

III

[F2], M

0.10

0.10

0.20

[ClO2], M

0.10

0.40

0.10

1.2 x 10-3

4.8 x 10-3

2.4 x 10-3

Initial rate,
M/s

CHEM
301

Analytical Chemistry

Method of Initial Rates

B. Involving More than One
Reactant
example:

F2 (g) + 2ClO2 (g)

2FClO2 (g)

II

III

[F2], M

0.10

0.10

0.20

[ClO2], M

0.10

0.40

0.10

1.2 x 10-3

4.8 x 10-3

2.4 x 10-3

Initial rate,
M/s

CHEM
301

Analytical Chemistry

Method of Initial Rates

B. Involving More than One
Reactant
example:

F2 (g) + 2ClO2

2FClO2 (g)

(g)

II

III

[F2], M

0.10

0.10

0.20

[ClO2], M

0.10

0.40

0.10

1.2 x 10-3

4.8 x 10-3

2.4 x 10-3

Initial rate,
M/s

CHEM
301

Analytical Chemistry

Method of Initial Rates

B. Involving More than One
Reactant

CHEM
301

Analytical Chemistry

Method of Initial Rates

B. Involving More than One
Reactant

CHEM
301

Analytical Chemistry

Method of Initial Rates

B. Involving More than One
Reactant
(CH ) CBr
+ OH
(CH ) COH
3 3

(aq)

(aq)

3 3

(aq)

+ Br (aq)

II

III

IV

[(CH3)3CBr ], M

0.50

1.0

1.5

1.0

1.0

[OH ], M

0.050

0.050

0.050

0.10

0.20

Initial rate, M/s

0.0050

0.010

0.015

0.010

0.010