Chemical Kinetics

Factors that Affect Reaction

Rates
• Kinetics is the study of how fast chemical reactions
occur.
• There are 4 important factors which affect rates of
reactions:
– reactant concentration,
– temperature,
– action of catalysts, and
– surface area.
 Reaction Rates

• Speed of a reaction is measured by the change in

concentration with time.
• For a reaction A  B
change in concentration of B
Average rate 
change in time
 B

t
• Suppose A reacts to form B. Let us begin with 1.00 M A.
Reaction Rates
 Reaction Rates

– At t = 0 (time zero) there is 1 M A and no B present.

– At t = 20 sec, there is 0.54 M A and 0.46 M B.
– At t = 40 sec, there is 0.30 M A and 0.70 M B.
– Calculating,

concentration of B
Average rate 
t

M of B at t 20 M of B at t 0 
20 sec  0 sec
0.46 M  0 M
 0.023 M/sec
20 sec  0 sec
 Reaction Rates

• For the reaction A  B there are two ways of measuring

rate:
– the speed at which the products appear (i.e. change in
molarity of B per unit time), or
– the speed at which the reactants disappear (i.e. the change in
molarity of A per unit time).

 A 
Average rate with respect to A 
t
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

In this reaction, the

concentration of butyl
chloride, C4H9Cl, was
measured at various
times.
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

The average rate of the

reaction over each
interval is the change
in concentration
divided by the change
in time:

[C4H9Cl]
Average rate =
t
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• Note that the average

rate decreases as the
reaction proceeds.
• This is because as the
reaction goes forward,
there are fewer
collisions between
reactant molecules.
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• A plot of [C4H9Cl] vs. time

for this reaction yields a
curve like this.
• The slope of a line tangent
to the curve at any point
is the instantaneous rate
at that time.
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• All reactions slow down

over time.
• Therefore, the best
indicator of the rate of a
reaction is the
instantaneous rate near
the beginning of the
reaction.
 Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• In this reaction, the ratio

of C4H9Cl to C4H9OH is 1:1.
• Thus, the rate of
disappearance of C4H9Cl is
the same as the rate of
appearance of C4H9OH.

-[C4H9Cl] [C4H9OH]
Rate = =
t t
 Reaction Rates
2N2O5(g) 4NO2(g) + O2(g)

decrease increase
 Reaction Rates
2N2O5(g) 4NO2(g) + O2(g)
 Reaction Rates
2N2O5(g) 4NO2(g) + O2(g)

Rate of decomposition of N2O5:

[N2O5] -(0.0101 M - 0.0120 M)

=
t (400 s - 300 s)

M
= 1.9 x 10-5
s
 Concentration and Rate

NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

If we compare Experiments 1 and 2, we see that

when [NH4+] doubles, the initial rate doubles.
 Concentration and Rate

NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Likewise, when we compare Experiments 5 and 6,

we see that when [NO2−] doubles, the initial rate
doubles.
 Concentration and Rate
• This means
Rate  [NH4+]
−
Rate  [NO2 ]
Therefore, Rate  [NH+] [NO2−]
which, when written as an equation, becomes
Rate = k [NH4+] [NO2−]
• This equation is called the rate law, and k is the rate
constant.
 Rate Laws
• A rate law shows the relationship between the
reaction rate and the concentrations of
reactants.
• The exponents tell the order of the reaction with
respect to each reactant.
• Since the rate law is
Rate = k [NH4+] [NO2−]
the reaction is
First-order in [NH4+] and
First-order in [NO2−].
 Rate Laws
−
Rate = k [NH ] [NO2 ]
4
+

• The overall reaction order can be found by

adding the exponents on the reactants in the
rate law.
• This reaction is second-order overall.
 Concentration and Rate
Using Initial Rates to Determines Rate
Laws
• A reaction is zero order in a reactant if the change in
concentration of that reactant produces no effect.
• A reaction is first order if doubling the concentration causes the
rate to double.
• A reaction is nth order if doubling the concentration causes an
2n increase in rate.
• Note that the rate constant does not depend on concentration.
 Rate Laws and Reaction Order
Rate Law: An equation that shows the dependence of the
reaction rate on the concentration of each reactant.

aA + bB products
rate  [A]m[B]n

rate = k[A]m[B]n

k is the rate constant

 Rate Laws and Reaction Order
The values of the exponents in the rate law must be
determined by experiment; they cannot be deduced from
the stoichiometry of the reaction.
 Experimental Determination of a Rate
Law
2NO(g) + O2(g) 2NO2(g)
rate = k[NO]m [O2]n

Compare the initial rates to the changes in initial concentrations.

 Experimental Determination of a Rate
Law
2NO(g) + O2(g) 2NO2(g)
rate = k[NO]2 [O2]n
The concentration of NO doubles, the concentration of O2 remains
constant, and the rate quadruples.
2m = 4 m=2
 Experimental Determination of a Rate
Law
2NO(g) + O2(g) 2NO2(g)
rate = k[NO]2 [O2]
The concentration of O2 doubles, the concentration of NO remains
constant, and the rate doubles.
2n = 2 n=1
Experimental Determination of a Rate
Law
2NO(g) + O2(g) 2NO2(g)
rate = k[NO]2 [O2]
Reaction Order With Respect to a Reactant
• NO: second-order
• O2: first-order

Overall Reaction Order

• 2 + 1 = 3 (third-order)
Experimental Determination of a Rate
Law
2NO(g) + O2(g) 2NO2(g)
rate = k[NO]2 [O2]

Units for this third-order reaction:

M
rate s 1
k= = =
[NO] [O2]
2
(M ) (M)
2 M2 s
Experimental Determination of a Rate
Law
2NO(g) + O2(g) 2NO2(g)
rate = k[NO]2 [O2]
 Integrated Rate Laws
Using calculus to integrate the rate law for
a first-order process gives us

[A]t
ln = −kt
[A]0
Where
[A]0 is the initial concentration of A, and

[A]t is the concentration of A at some time, t,

during the course of the reaction.
 Integrated Rate Laws

Manipulating this equation produces…

[A]t
ln = −kt
[A]0
ln [A]t − ln [A]0 = − kt
ln [A]t = − kt + ln [A]0
…which is in the form
y = mx + b
 First-Order Processes

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

Therefore, if a reaction is first-order, a plot

of ln [A] vs. t will yield a straight line, and
the slope of the line will be -k.
Integrated Rate Law for a First-Order
Reaction
ln[A]t = -kt + ln[A]0

This is a plot of [A] versus time.

The best-fit is a curve and not a

line.
Integrated Rate Law for a First-Order
Reaction
ln[A]t = -kt + ln[A]0
Half-Life

• Half-life is defined as
the time required for
one-half of a reactant
to react.
 Half-Life for a First-Order Reaction

0.693
t1/2 =
k

For a first-order reaction, the

half-life is independent of
the initial concentration.

Each successive half-life is an

equal period of time.
 Second-Order Reactions
A product(s)
[A]
rate = k[A] 2
- = k[A]2
t
Calculus can be used to derive an integrated rate law.

[A]t concentration of A at time t

1 1
= kt +
[A]t [A]0
[A]0 initial concentration of A
y = mx + b
Second-Order Reactions
2NO2(g) 2NO(g) + O2(g)
Second-Order Reactions
2NO2(g) 2NO(g) + O2(g)

Plotting ln[NO2] versus time

gives a curve and not a
straight-line fit.

Therefore, this is not a first-

order reaction.
 Second-Order Reactions
2NO2(g) 2NO(g) + O2(g)

1
Plotting versus Slope = k
[NO2]

time gives a straight-line fit.

Therefore, this is a second-

order reaction.
 Half-Life
For a second-order process,
1 1
= kt1/2 +
0.5 [A]0 [A]0

2 1
= kt1/2 +
[A]0 [A]0

2 − 1 = 1 = kt
[A]0 [A]0
1/2

1
= t1/2
k[A]0
 Second-Order Reactions
1
t1/2 =
k[A]0

For a second-order
reaction, the half-life is
dependent on the initial
concentration.

Each successive half-life is

twice as long as the
preceding one.
 Reaction Mechanisms
The sequence of events that describes the
actual process by which reactants become
products is called the reaction mechanism.
Each of these processes is known as an
elementary reaction or elementary process.
 Reaction Mechanisms
Experimental evidence suggests that the reaction between NO2
and CO takes place by a two-step mechanism:

NO2(g) + NO2(g) NO(g) + NO3(g) elementary reaction

NO3(g) + CO(g) NO2(g) + CO2(g) elementary reaction

NO2(g) + CO(g) NO(g) + CO2(g) overall reaction

An elementary reaction describes an individual molecular
event.

The overall reaction describes the reaction stoichiometry and

is a summation of the elementary reactions.
Reaction Mechanisms
NO2(g) + NO2(g) NO(g) + NO3(g)

NO3(g) + CO(g) NO2(g) + CO2(g)

 Reaction Mechanisms
Experimental evidence suggests that the reaction between NO2
and CO takes place by a two-step mechanism:

NO2(g) + NO2(g) NO(g) + NO3(g) elementary reaction

NO3(g) + CO(g) NO2(g) + CO2(g) elementary reaction

NO2(g) + CO(g) NO(g) + CO2(g) overall reaction

A reactive intermediate is formed in one step and consumed

in a subsequent step.
 Catalysis
Catalyst: A substance that increases the rate of a reaction
without itself being consumed in the reaction. A catalyst is used
in one step and regenerated in a later step.

H2O2(aq) + I1-(aq) H2O(l) + IO1-(aq) rate-determining

step (slow step)

H2O2(aq) + IO1-(aq) H2O(l) + O2(g) + I1-(aq) fast step

2H2O2(aq) 2H2O(l) + O2(g) overall reaction

 Catalysis
The rate determining step or slow step determines the rate
law.
rate = k[H2O2][I1-]

H2O2(aq) + I1-(aq) H2O(l) + IO1-(aq) rate-determining

Step (slow step)

H2O2(aq) + IO1-(aq) H2O(l) + O2(g) + I1-(aq) fast step

2H2O2(aq) 2H2O(l) + O2(g) overall reaction

 Catalysis

Note that the presence of a catalyst does not affect the energy
difference between the reactants and the products