Chemical Kinetics:

Rates of Chemical Reactions &

Factors that Affect Rates of Reactions
Chapter 13 How fast does a chemical reaction occur?
rates of reactants consumed
rates of products formed
define and calculate rates
Rates of Reaction relationship between rate & concentration
rate law & experimental determination of rate law
relationship between concentration & time
integrated rate law & half-life of reaction
dependence of rate on temperature & catalyst
Arrhenius equation
reaction mechanisms

Reaction Rates Reaction Rates

typically a plot of [X] vs. time will not yield a straight
concentration line, but instead a curve;
rate of chemical reaction =
time concentration vs. time curve

|[X]| |[X]2 [X]1| consider the difference in shape of concentration vs.

rate = =
t2 t 1 time curve for reactants & products
t

[X] = molar concentration of reactant or product

if reactant: [X]2 < [X]1 [react] [prod]
rate of consumption of reactant
if product: [X]2 > [X]1
rate of formation of product time time
example:
example:
Consider the decomposition of hydrogen peroxide:
Consider the reaction:
2 H2O2 (aq) 2 H2O (l) + O2 (g)
4 NH3 (g) + 5 O2 (g) ! 4 NO (g) + 6 H2O (g)
If the initial concentration of H2O2 is 1.000 M, and
The initial concentration of NH3 is 4.000 M; after 25
the concentration of H2O2 decreases to 0.983 M
seconds, [NH3] has decreased to 2.560 M.
after 10 seconds of reaction, calculate the rate of
decomposition of H2O2 over this time interval.
Determine the following:
[H2O2]0 = 1.000 M at t = 0 s a. the rate of consumption of NH3
[H2O2] = 0.983 M at t = 10 s b. the rate of consumption of O2
c. the rate of formation of H2O.

a closer look at some experimental data:

Page #1 - H2O2 decomp data Sunday, February 9 2:21 PM 2014
2 H2O2 (aq) ! 2 H2O (l) + O2 (g) Concentration vs. Time Curve for Decomposition of H O
2 2

2.5

Time, s [H2O2], M Change in [H2O2], M Rate, M/s E F G H I J

0 0.0000 2.3200
2
1 400.00 1.7200 0.60000 0.001500
2 800.00 1.3000 0.42000 0.001050
3 1200.0 0.98000 0.32000 0.0008000 1.5

[H O ], M
4 1600.0 0.73000 0.25000 0.0006300

2
2
5 2000.0 0.54000 0.19000 0.0004800
6 2400.0 0.39000 0.15000 0.0003800 1

7 2800.0 0.28000 0.11000 0.0002800

things to note: 0.5

[H2O2] decreases over time b/c it is a reactant consumed

rate of reaction is not constant over time 0

as [H2O2] decreases, so does rate

0 400 800 1200 1600 2000 2400 2800 3200
Time, s
 to calculate an instantaneous rate of reaction, draw a line tangent to
Average vs. Instantaneous Reaction Rates the concentration vs. time curve at the point of interest
average rate of reaction - rate of reaction over slope of tangent line = rate at time, t; units Ms1
some time interval
ex. What is the rate of decomposition of
H2O2 between 1200 and 1600 seconds?
instantaneous rate of reaction - rate of reaction at
a specific time point
ex. What is the rate of decomposition of
H2O2 at 1400 seconds?

initial rate of reaction - instantaneous rate of

reaction at t = 0 s

to calculate an initial rate of reaction, draw a line tangent to Rate Laws

the concentration vs. time curve at t = 0
slope of tangent line = initial rate of reaction; units Ms1
rate law equation that shows the dependence of
a reactions rate on concentration

for a reaction: A + B ! C + D
Rate = k[A]m[B]n

*** for a reaction, the rate law must

be determined experimentally ***
 Rate = k[A]m[B]n
Rate = k[A]m[B]n
m and n order of reaction with respect
some rate law terminology:
to A & B
typically small, positive, whole if m = 1, the reaction is 1st order in A
numbers if n = 2, the reaction is 2nd order in B
negative numbers and fractions overall order of the reaction = m + n
are possible
reactions of the same overall order will have
k rate constant similar characteristics
dependent on specific reaction
specifically we will discuss 0, 1st, and 2nd order
dependent on temperature
overall reactions
independent of concentration
units are variable; depend on orders of reaction

Reaction Order & Rate Change with Concentration Reaction Order & Rate Change with Concentration
consider the reaction: A ! B+C consider the reaction: A ! B + C

if 1st order overall: if 1 order overall:

Rate = k[A]1 Rate = k[A]1
if [A] increases by factor of 2, rate will if [A] increases by factor of 2, rate will
increase by factor of 21 OR rate will double change by factor of 21 OR rate will decrease
by half
if 2nd order overall: if 0 order overall:
Rate = k[A]2 Rate = k[A]0
if [A] increases by factor of 3, rate will rate is constant; changes in [A] have no
increase by factor of 32 OR rate will effect on the rate as long as some A is
increase 9x present
 Reaction Order & Rate Change with Concentration Reaction Order & Units of k
in general, for the reaction: A ! B + C
Rate = k[A]m
order rate law k= k units
if [A] changes by a factor of x, the rate will change by
a factor of xm 1st Rate = k[A] k = Rate/[A] s1
when [A] is doubled: when [A] is tripled:
2nd Rate = k[A]2 k = Rate/[A]2 M1s1
rate rate
m= m=
multiplied by multiplied by
3rd Rate = k[A]3 k = Rate/[A]3 M2s1
1 21 = ! 1 31 =
0 20 = 1 0 30 = 1
0 Rate = k k = Rate Ms1
1 21 = 2 1 31 = 3
2 22 = 4 2 32 = 9
3 23 = 8 3 33 = 27

Determination of Rate Law from Experimental Data: a simple example:

Method of Initial Rates 2 N2O5 (g) ! 4 NO2 (g) + O2 (g)
reaction run multiple times at the same Rate = k[N2O5]m
temperature ( same k) with different initial
concentrations experiment [N2O5]0 initial rate
initial rates of reaction are determined 1 0.010 M 4.8 x 106 Ms1
analyze how rate changes as concentration 2 0.020 M 9.6 x 106 Ms1
changes
determine order with respect to each reactant [N2O5] increase by factor of 2
rate increases by factor of 2
write rate law reaction is 1st order in N2O5
m=1
do calculations
example: example (continued):

2 HgCl2 (aq) + C2O42 (aq) ! 2 Cl (aq) + 2 CO2 (g) + Hg2Cl2 (s)

comparing experiments 1 & 2:
determination of n
Rate = k[HgCl2]m[C2O42]n

experiment [HgCl2]0 [C2O42]0 initial rate Rate2 k[HgCl2]2m[C2O42]2n

=
Rate1 k[HgCl2]1m[C2O42]1n
1 0.105 M 0.15 M 1.8 x 105 Mmin1

2 0.105 M 0.30 M 7.1 x 105 Mmin1 7.1 x 105 k(0.105)m(0.30)n

=
1.8 x 105 k(0.105)m(0.15)n
3 0.052 M 0.30 M 3.5 x 105 Mmin1

compare experiments 1 & 2 to determine order with 4 = 2n

respect to C2O42; i.e. determine n so: n = 2
compare experiments 2 & 3 to determine order with respect
to HgCl2; i.e. determine m the reaction is 2nd order in C2O42

example (continued): example (continued):

comparing experiments 2 & 3: 2 HgCl2 (aq) + C2O42 (aq) ! 2 Cl (aq) + 2 CO2 (g) + Hg2Cl2 (s)
determination of m
Rate = k[HgCl2][C2O42]2

Rate2 k[HgCl2]2m[C2O42]22 experiment [HgCl2]0 [C2O42]0 initial rate

=
Rate3 k[HgCl2]3m[C2O42]32
1 0.105 M 0.15 M 1.8 x 105 Mmin1
7.1 x 105 k(0.105)m(0.30)2 2 0.105 M 0.30 M 7.1 x 105 Mmin1
=
3.5 x 105 k(0.052)m(0.30)2
3 0.052 M 0.30 M 3.5 x 105 Mmin1

2 = 2m Determine the value of k.

so: m = 1 Determine the rate of reaction when [HgCl2] = 0.050 M and
[C2O42] = 0.025 M.
the reaction is 1st order in HgCl2
example: example (continued):

2 NO (g) + O2 (g) ! 2 NO2 (g) comparing experiments 1 & 2:

determination of n
Rate = k[NO]m[O2]n

experiment [NO]0 [O2]0 initial rate Rate2 k[NO]2m[O2]2n

=
1 0.0010 M 0.0010 M 7.10 Ms1
Rate1 k[NO]1m[O2]1n

2 0.0010 M 0.0040 M 28.4 Ms1 28.4 k(0.0010)m(0.0040)n

=
3 0.0030 M 0.0040 M 255.6 Ms1 7.10 k(0.0010)m(0.0010)n
compare experiments 1 & 2 to determine order with
respect to O2; i.e. determine n 4 = 4n
so: n = 1
compare experiments 2 & 3 to determine order with respect
to NO; i.e. determine m
the reaction is 1st order in O2

example (continued): 1st Order Overall Reactions

comparing experiments 2 & 3: for a reaction: A ! products
determination of m
rate law: Rate = k[A]
rate law provides information about how
Rate3 k[NO]3m[O2]3 rate changes relative to changes in [A]
=
Rate2 k[NO]2m[O2]2 Other questions wed like to answer?
What is [A] at some time, t?
255.6 k(0.0030)m(0.0040) What % of A has been consumed after t?
=
28.4 k(0.0010)m(0.0040) How much time elapses before the reaction is
50% complete?
9 = 3m these questions all probe the relationship
so: m = 2 between [A] and time

the reaction is 2nd order in NO use the Integrated Rate Law to answer these questions
 1st Order Overall Reactions:
Integrated Rate Law example:
[A]t 2 H2O2 (aq) ! 2 H2O (l) + O2 (g)
ln = kt
[A]0 The decomposition of hydrogen peroxide is a 1st
order reaction with k = 7.30 x 104 s1.
ln [A]t ln[A]0 = kt
If [H2O2]0 = 2.32 M, determine [H2O2] after 1200
ln [A]t = kt + ln[A]0 seconds of reaction.

look at this as an equation for a straight line:

plot of ln[A] vs. t will yield a straight line
slope = k
y intercept = ln[A]0

example: Half-Life of a Reaction, t!

2 H2O2 (aq) ! 2 H2O (l) + O2 (g) The half-life (t!) of a reaction is the time required
for the [reactant] to decrease to half of its initial
The decomposition of hydrogen peroxide is a 1st order value.
reaction with k = 7.30 x 104 s1.
t = t!
What percent of H2O2 initially present has decomposed [A]t = ![A]0
after 500 s of reaction?
for a 1st order reaction:

ln 2 =
t! = 0.693
k k
At what time after the start of the reaction the sample
of H2O2 decomposed? note: for a 1st order reaction, t! is constant
t! is dependent on k but not on [A]0
 Half-Life of a 1st Order Reaction Half-Life of a 1st Order Reaction

2nd Order Overall Reactions Zero (0) Order Overall Reactions

for a reaction: A ! products for a reaction: A ! products
rate law: Rate = k[A]2 rate law: Rate = k[A]0; Rate = k
rate law provides information about how the rate of a 0 order reaction is constant and
rate changes relative to changes in [A] does not depend on [A]
integrated rate law: 1 = kt +
1 integrated rate law:
[A]t = kt + [A]0
[A]t [A]0

plot of 1/[A] vs. t will give a straight line plot of [A] vs. t will give a straight line

slope = k y intercept = 1/[A]0 slope = k y intercept = [A]0

half-life equation: half-life equation: [A]0

1
t! = t! =
k[A]0 2k
 example:
Consider a reaction with k = 0.0124 Ms1. After 180
seconds of reaction, [A] = 0.394 M.
What was the initial concentration of A?

example:
Consider the following 2nd order reaction:
2A ! B
For this reaction, k = 0.0250 M1s1. If [A]0 = 1.10 M,
what will be the [B] after 45.0 seconds?

Collision Theory of Reactions Energy Considerations

molecular collisions are successful (i.e. result in the

reactions occur when particles collide formation of product) when they occur with
not all collisions result in the formation of product enough energy to break bonds
minimum amount of E required for reaction to
2 factors influence whether or not product forms: occur is the activation energy, Ea, for the reaction
energy of collision Ecollision > Ea required for product formation
orientation of particle at collision
in general, the larger the Ea for a reaction, the
slower the rate
a smaller fraction of molecular collisions will
occur with sufficient energy to form products
 Energy Considerations Energy Considerations

energy of molecular collision is affected by

temperature
at higher Ts:
kinetic energy of particles is greater
speed is greater
force of collisions will be greater
frequency of collisions will be higher
fraction of collisions with E > Ea is greater

Orientation of Collisions Orientation of Collisions

consider the reaction: A2 + B2 ! 2 AB NO (g) + Cl2 (g) ! NOCl (g) + Cl (g)

favorable orientation:

A B A B A B
favorable
+ ! ! +
A B A B A B orientation:

unfavorable orientation:

A A + B B ! no reaction
unfavorable
orientation:
 consider the species in the middle of this reaction: Reaction Profile
track how energy changes as the reaction progresses
A B A B A B
from reactant ! transition state ! products
+ ! ! +
A B A B A B

reactants transition state products

a short-lived, transient species formed in between

reactants and products can be called:
transition state
activated complex
reaction intermediate

Temperature Dependence of Reaction Rates

reaction rates almost always increase with increasing
temperature
if rate increases while [A] is held constant, k must also
increase
temperature dependence of k is given by the
Arrhenius equation:
k = AeEa/RT
OR
Ea
ln k = ln A
RT
Ea = activation energy, kJ/mol
A = frequency factor, s1
R = 8.314 J/Kmol
 Arrhenius Equation
look at the logarithmic form of the Arrhenius example:
equation as a straight line equation: Consider the following 1st order reaction:
Ea + ln A
ln k = 2 N2O5 (g) ! 4 NO2 (g) + O2 (g)
RT
For this reaction at 50C, A = 4.0 x 1013 s1 and
plot of ln k vs. 1/T yields a straight line with: Ea = 88 kJ/mol.
slope = Ea/R y intercept = ln A
Determine the rate of this reaction at 50C if
this is called an Arrhenius plot [N2O5]0 = 2.68 M.
you can derive a 2-point equation:
k2 Ea 1 1 Determine the value of k at 30C.
ln() = ( )
k1 R T1 T2

Catalysts
example: A catalyst is a substance that increases the rate of a
chemical reaction without being consumed by it.
Consider a reaction with Ea = 35.7 kJ/mol.
Determine the factor by which the rate of a reaction
increases as temperature is increased from 50C to a catalyst provides an
alternate path from reactant
75C.
to product
path with lower Ea
frequently multiple step path
a catalyst participates in one
step of the mechanism, and is
regenerated in a later step
 Reaction Profile for a Catalyzed Reaction: Catalysts

heterogeneous catalyst catalyst is in a different

phase than the reacting species
usually a solid catalyst in contact with liquid or gas
phase reaction mixture
reactants adsorb onto catalyst surface
physical adsorption
chemisorption

homogeneous catalyst catalyst in the same phase as

reacting species

Catalytic Hydrogenation - Heterogeneous Catalysis Catalytic Converters - Heterogeneous Catalysis

conversion of CO (g), NO (g), and O2 (g) to

CO2 (g) and N2 (g) released into atmosphere
 Enzymes - Biochemical Catalysts Arrhenius Equation and Catalyst Considerations
for a reaction, the addition of a catalyst causes:
rate increase ratecat > rateuncat
k increase kcat > kuncat
Ea decrease Ea-cat < Ea-uncat

consider writing the Arrhenius equation in terms of

both a catalyzed and uncatalyzed reaction:
kcat = AeEacat/RT and kuncat = AeEauncat/RT
kcat AeEacat/RT
=
kuncat AeEauncat/RT

Elementary Processes
Reaction Mechanisms
individual steps in reaction mechanism
a collection of elementary steps that describe the rate law can be written by inspection;
path from reactants to products in a chemical orders equivalent to stoichiometric coefficients
reaction identified by their molecularity
for a mechanism to be plausible, it must meet 2 may be unimolecular, bimolecular, termolecular
criteria: may be fast, reversible (equilibrium) steps
match the overall or net chemical reaction Rateforward = Ratereverse
after steps are added together may be slow
produce a rate law that is consistent with rate determining step (RDS)
the experimentally determined rate law largest Ea
** determines the overall rate of reaction
Raterxn = RateRDS
 proposed mechanism for the depletion of ozone (O3) by Cl:
Reaction Intermediates & Catalysts in Mechanisms
step 1: Cl (g) + O3 (g) ! ClO (g) + O2 (g)
step 2: ClO (g) + O (g) ! Cl (g) + O2 (g)
reaction intermediates and catalysts are both
species that may be involved in a mechanism but overall rxn: O3 (g) + O (g) ! 2 O2 (g)
not appear in the overall chemical equation or its
rate law ClO is a reaction
intermediate b/c it is
reaction intermediate generated in one step, then formed in step 1 and
consumed in step 2
consumed in a later step
Cl is a catalyst
catalyst consumed in one step, then regenerated (homogeneous) b/c it
in a later step is consumed in step 1
and regenerated in
step 2

Consider the following reaction:

Consider the following reaction:
2 ICl (g) + H2 (g) ! I2 (g) + 2 HCl (g)
2 ICl (g) + H2 (g) ! I2 (g) + 2 HCl (g)
The experimentally determined rate law is:
The experimentally determined rate law is:
Rate = k[H2][ICl]
Rate = k[H2][ICl]
Is this a plausible mechanism?
Is this a plausible mechanism?
step 1: H2 (g) + ICl (g) ! HI (g) + HCl (g) (RDS)
step 1: H2 (g) + ICl (g) ! HI (g) + HCl (g) (slow) step 2: HI (g) + ICl (g) ! I2 (g) + HCl (g) (fast)
step 2: HI (g) + ICl (g) ! I2 (g) + HCl (g) (fast)
overall rxn: H2 (g) + 2 ICl (g) ! I2 (g) + 2 HCl (g)

rate law from mechanism: Raterxn = RateRDS

Rate = k[H2][ICl]
Consider the following reaction:
2 ICl (g) + H2 (g) ! I2 (g) + 2 HCl (g) example:

The experimentally determined rate law is: Ozone reacts with nitrogen dioxide to produce
oxygen and dinitrogen pentoxide by the following
Rate = k[H2][ICl] proposed mechanism:
Is this a plausible mechanism? step 1: O3 (g) + NO2 (g) ! NO3 (g) + O2 (g) (slow)
step 1: H2 (g) + ICl (g) ! HI (g) + HCl (g) (RDS) step 2: NO2 (g) + NO3 (g) ! N2O5 (g) (fast)
step 2: HI (g) + ICl (g) ! I2 (g) + HCl (g) (fast)
Determine the overall reaction & rate law consistent
overall rxn: H2 (g) + 2 ICl (g) ! I2 (g) + 2 HCl (g) with this mechanism.
rate law from mechanism: Raterxn = RateRDS
Rate = k[H2][ICl]
Yes this is a plausible mechanism.

example:
example:
Consider the following proposed mechanism for the
Ozone reacts with nitrogen dioxide to produce
reaction between F2 and N2O4:
oxygen and dinitrogen pentoxide by the following Ea, kJ/mol
proposed mechanism: step 1: N2O4 (g) 2 NO2 (g) 59
step 1: O3 (g) + NO2 (g) ! NO3 (g) + O2 (g) (RDS) step 2: NO2 (g) + F2 (g) ! F (g) + FNO2 (g) 83
step 2: NO2 (g) + NO3 (g) ! N2O5 (g) (fast) step 3: F (g) + NO2 (g) ! FNO2 (g) 9

overall rxn: O3 (g) + 2 NO2 (g) ! O2 (g) + N2O5 (g)

What is the overall reaction predicted by this

rate law from mechanism: Raterxn = RateRDS
mechanism?
Rate = k[O3][NO2]
Identify any reaction intermediates or catalysts.
 example:
example: Consider the following proposed mechanism for the
Consider the following proposed mechanism for the reaction between F2 and N2O4:
reaction between F2 and N2O4: Ea, kJ/mol
Ea, kJ/mol step 1: N2O4 (g) 2 NO2 (g) 59
step 1: N2O4 (g) 2 NO2 (g) 59 step 2: NO2 (g) + F2 (g) ! F (g) + FNO2 (g) 83
step 2: NO2 (g) + F2 (g) ! F (g) + FNO2 (g) 83 step 3: F (g) + NO2 (g) ! FNO2 (g) 9
step 3: F (g) + NO2 (g) ! FNO2 (g) 9
overall rxn: N2O4 (g) + F2 (g) ! 2 FNO2 (g)

overall rxn: N2O4 (g) + F2 (g) ! 2 FNO2 (g)

Which step {1, 2, or 3} is the fastest step?
NO2 and F are reaction intermediates
Which step {1, 2, or 3} is the rate-determining step?

example: example:
Consider the following proposed mechanism for the
For the proposed mechanism for the reaction
reaction between F2 and N2O4:
Ea, kJ/mol between F2 and N2O4, consider both the Ea values
step 1: N2O4 (g) 2 NO2 (g) 59 and H values for steps 1 3, and the overall
reaction to sketch the reaction profile.
step 2: NO2 (g) + F2 (g) ! F (g) + FNO2 (g) 83
step 3: F (g) + NO2 (g) ! FNO2 (g) 9 Ea, kJ/mol H, kJ

overall rxn: N2O4 (g) + F2 (g) ! 2 FNO2 (g) step 1: 59 +55.6

step 2: 83 20.0
Which step {1, 2, or 3} is the fastest step?
step 3: 9 207
step 3 because smallest Ea
overall rxn: --- 171
Which step {1, 2, or 3} is the rate-determining step?
step 2 because largest Ea