Chemical Kinetics

The rate of a reaction

•  Chemical kinetics is the area of chemistry concerned

with speeds, or rates, at which a chemical reaction
occurs.
•  Reaction rate is the change in [ ] of a reactant or a
product with time(M/s).
•  Kinetics is the study of how fast chemical reactions
occur.
•  There are 3 important factors which affect rates of
reactions:
–  reactant concentration [molarity or pressure]
–  temperature
–  action of catalysts
•  Goal: to understand chemical reactions at the molecular
level.
Reaction Rates
•  Speed of a reaction is measured by the change in
concentration with time [brackets means concentration,
units of molarity, M]
•  For a reaction A → B

change in conc. of B Δ[B]

Average rate = =
change in time Δt

At the beginning of the reaction (t = 0), let us

assume that
[A] = 1.0 M and [B] = 0.
Reaction Rates A B
Concentration of reactant and product as function of time

[ ]
Conc (M)

[ ]
 Reaction rates
The rate for this reaction depends on the time.
At beginning of reaction, rate is fast, and the rate slows down
as the reaction proceeds.
At any time, the rate is given by either:
(a) change in [A] with change in time, or…
(b) change in [B] with change in time.

change in conc. of B Δ[B] - Δ[A]

Average rate = = =
change in time Δt Δt

There are two ways of calculating rates:

(a) average rate (rough and imprecise)
(b) instantaneous rate (more exact)
Average rate is rate between two time intervals
What is rate between 10 min and 30 min?
At t=10 min, [B]=0.26 M; at t=30 min, [B]=0.60 M
Average rate = Δ[B]/ Δt = (0.60-0.26)/(30-10)
= (.34 M / 20 min) = 0.017 M/min

[ ]
conc(M)

[ ]
The instantaneous rate is more precise than the average rate.
It is the rate at some specific instance in time; the concept
is derived from the calculus.
It is the slope of a curve at a specific instance in time.
This is obtained by constructing a tangent to the curve at
the indicated point.

“rise” = Δy
M

“run” = Δx
time

Slope = Δy
Δx
What is instantaneous rate at t = 20 min?
Conc (M)

0.6 M

38 min

Δ[B] = 0.6 M = 0.016 M/min = 0.96 M/s

Rate = Δ t 38 min
Reaction Rates A B
When do we use (+) and (-) signs for rate?
[ ]
Conc (M)

[ ]

Slopes for reactants (A) are always negative (-)

Slopes for products (B) are always positive (+)
But, all rates are positive (+). Therefore….
If slope is (-), then Rate = - slope = (-)(-) = +
If slope is (+), then Rate = +slope = (+)(+) = +
 Reaction Rates
Reaction Rate and Stoichiometry

In general for
aA + bB → cC + dD

1 Δ[A ] 1 Δ[B] 1 Δ[C] 1 Δ[D]

Rate = − =− = =
a Δt b Δt c Δt d Δt
 The Rate Law

•  The rate of a reaction is proportional to the [ ] of

reactants and the proportionality constant k is called the
rate constant. The rate law expresses the relationship of
the rate of a reaction to the rate constant and the [ ] of the
reactants raised to some powers.
aA + bB → cC + dD

rate = k[A]x[B]y
 The Rate Law
rate = k[A]x[B]y

•  The exponents x and y specify the relationships between

the concentrations of reactants A and B and the reaction
rate. Added together, they give us the overall reaction
order, defined as the sum of the powers to which all
reactant [ ] appearing in the rate law are raised.
•  The exponents in a rate law must be determined by
experiment. They are not derived from the
stoichiometric coefficients in an overall chemical
equation
 The Rate Law

•  Reaction order enables us to understand how the reaction

depends on reactant [ ]. Suppose, that for
•  aA + bB → cC + dD
•  we have x = 1 and y = 2. The rate law =
•  rate = k[A][B]2
•  this reaction is 1st order in A,
•  2nd order in B, and (1 + 2 = 3) third order overall.
 Summarize;

•  Rate laws are always determined experimentally. From the

[ ] of reactants and the initial reaction rates we can
determine the reaction order and then the rate constant of
the reaction.
•  Reaction order is always defined in terms of reactant [ ]’s.
•  the order of a reactant is not related to the stoichiometric
coefficient of the reactant in
Zero-Order Reactions
A → products

Rrxn = k [A]0

Rrxn = k

[k] = mol L-1 s-1

Integrated Rate Law
-Δ[A] Move to the -d[A]
= k infinitesimal
= k
Δt dt
And integrate from 0 to time t

[A]t t

- ∫ d[A] = ∫ k dt
[A]0 0

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

[A]t = [A]0 - kt
 First-Order Reactions
H2O2(aq) → H2O(l) + ½ O2(g)

d[H2O2 ]
= -k [H2O2] [k] = s-1
dt
[A]t t
d[H2O2 ]
∫ = - ∫ k dt
[A]
0
[H2O2] 0

[A]t
ln = -kt ln[A]t = -kt + ln[A]0
[A]0
First-Order Reactions
ln[A ]t = − kt + ln[A ]0
 Half-Life
•  Half-life is the time taken for the concentration of a
reactant to drop to half its original value.
•  For a first order process, half life, t½ is the time taken for
[A]0 to reach ½[A]0.
•  Mathematically,

t1 = −
( )= 0.693
ln 12
2 k k
•  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
 Half-Life
ButOOBut(g) → 2 CH3CO(g) + C2H4(g)
Some Typical First-Order
Processes
 Second-Order Reactions
•  Rate law where sum of exponents m + n +… = 2.
A → products

d[A]
= -k[A]2 [k] = M-1 s-1 = L mol-1 s-1
dt
[A]t
d[A] t

∫ = - ∫ k dt
[A]0 [A]2 0

1 1
= kt +
[A]t [A]0
Second-Order Reaction
•  For a second order reaction with just one reactant

1 1
= kt +
[A]t [A]0
•  A plot of 1/[A]t versus t is a straight line with slope k and
intercept 1/[A]0
•  For a second order reaction, a plot of ln[A]t vs. t is not
linear.
 1 1
= kt +
[A]t [A]0
Half-Life
•  For a second order reaction, half-life depends in the
initial concentration:
1
t1 = −
2 k [A ]0
 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.
Testing for a Rate Law

Plot [A] vs t.

Plot ln[A] vs t.

Plot 1/[A] vs t.
 Reaction Kinetics: A Summary

•  Calculate the rate of a reaction from a known rate law

using: Rate of reaction = k [A]m[B]n ….

•  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.

 Summary of Kinetics
•  Determine the order of reaction by:
Using the method of initial rates.

Find the graph that yields a straight line.

Test for the half-life to find first order reactions.

Substitute data into integrated rate laws to find

the rate law that gives a consistent value of k.
 Summary of Kinetics

•  Find the rate constant k by:

Determining the slope of a straight line graph.

Evaluating k with the integrated rate law.

Measuring the half life of first-order reactions.

•  Find reactant concentrations or times for certain

conditions using the integrated rate law after
determining k.
 Temperature and Rate
The Collision Model
•  Most reactions speed up as temperature increases. (E.g.
food spoils when not refrigerated.)
•  When two light sticks are placed in water: one at room
temperature and one in ice, the one at room temperature
is brighter than the one in ice.
•  The chemical reaction responsible for
chemiluminescence is dependent on temperature: the
higher the temperature, the faster the reaction and the
brighter the light.
Temperature and Rate
The Collision
Model
•  As temperature
increases, the rate
increases.
 Temperature and Rate
The Collision Model
•  Since the rate law has no temperature term in it, the rate
constant must depend on temperature.
•  Consider the first order reaction CH3NC → CH3CN.
–  As temperature increases from 190 °C to 250 °C the rate
constant increases from 2.52 × 10-5 s-1 to 3.16 × 10-3 s-1.
•  The temperature effect is quite dramatic. Why?
•  Observations: rates of reactions are affected by
concentration and temperature.
 Temperature and Rate
The Collision Model
•  Goal: develop a model that explains why rates of
reactions increase as concentration and temperature
increases.
•  The collision model: in order for molecules to react they
must collide.
•  The greater the number of collisions the faster the rate.
•  The more molecules present, the greater the probability
of collision and the faster the rate.
 Temperature and Rate
The Collision Model
•  The higher the temperature, the more energy available to
the molecules and the faster the rate.
•  Complication: not all collisions lead to products. In fact,
only a small fraction of collisions lead to product.
The Orientation Factor
•  In order for reaction to occur the reactant molecules must
collide in the correct orientation and with enough energy
to form products.
 Temperature and Rate
The Orientation Factor
•  Consider:
Cl + NOCl → NO + Cl2
•  There are two possible ways that Cl atoms and NOCl
molecules can collide; one is effective and one is not.
Temperature and Rate
The Orientation Factor
 Temperature and Rate
Activation Energy
•  Arrhenius: molecules must posses a minimum amount of
energy to react. Why?
–  In order to form products, bonds must be broken in the
reactants.
–  Bond breakage requires energy.
•  Activation energy, Ea, is the minimum energy required to
initiate a chemical reaction.
 Temperature and Rate
Activation Energy
•  Consider the rearrangement of methyl isonitrile:
N
H3C N C H3C H3C C N
C
–  In H3C-N≡C, the C-N≡C bond bends until the C-N bond breaks
and the N≡C portion is perpendicular to the H3C portion. This
structure is called the activated complex or transition state.
–  The energy required for the above twist and break is the
activation energy, Ea.
–  Once the C-N bond is broken, the N≡C portion can continue to
rotate forming a C-C≡N bond.
 Temperature and Rate
Activation Energy
•  The change in energy for the reaction is the difference in
energy between CH3NC and CH3CN.
•  The activation energy is the difference in energy between
reactants, CH3NC and transition state.
•  The rate depends on Ea.
•  Notice that if a forward reaction is exothermic (CH3NC
→ CH3CN), then the reverse reaction is endothermic
(CH3CN → CH3NC).
 Temperature and Rate
Activation Energy
•  How does a methyl isonitrile molecule gain enough
energy to overcome the activation energy barrier?
•  From kinetic molecular theory, we know that as
temperature increases, the total kinetic energy increases.
•  We can show the fraction of molecules, f, with energy
equal to or greater than Ea is
E
− a
f =e RT

where R is the gas constant (8.314 J/mol·K).

Temperature and Rate
Activation Energy
 Temperature and Rate
The Arrhenius Equation
•  Arrhenius discovered most reaction-rate data obeyed the
Arrhenius equation:
− Ea
k = Ae RT

–  k is the rate constant, Ea is the activation energy, R is the gas

constant (8.314 J/K-mol) and T is the temperature in K.
–  A is called the frequency factor.
–  A is a measure of the probability of a favorable collision.
–  Both A and Ea are specific to a given reaction.
 Temperature and Rate
Determining the Activation Energy
•  If we have a lot of data, we can determine Ea and A
graphically by rearranging the Arrhenius equation:
Ea
ln k = − + ln A
RT
•  From the above equation, a plot of ln k versus 1/T will
have slope of –Ea/R and intercept of ln A.
Temperature and Rate
 Temperature and Rate
Determining the Activation Energy
•  If we do not have a lot of data, then we recognize
Ea Ea
ln k1 = − + ln A and ln k2 = − + ln A
RT1 RT2
⎯ Ea ⎯ Ea
ln k1 − ln k2 = − + ln A √− − + ln A √
RT1 ↵ RT2 ↵
k1 Ea ⎯1 1
ln = − √
k2 R T2 T1 ↵
 Reaction Mechanisms

•  The balanced chemical equation provides information

about the beginning and end of reaction.
•  The reaction mechanism gives the path of the reaction.
•  Mechanisms provide a very detailed picture of which
bonds are broken and formed during the course of a
reaction.
Elementary Steps
•  Elementary step: any process that occurs in a single step.
 Reaction Mechanisms
Elementary Steps
•  Molecularity: the number of molecules present in an
elementary step.
–  Unimolecular: one molecule in the elementary step,
–  Bimolecular: two molecules in the elementary step, and
–  Termolecular: three molecules in the elementary step.
•  It is not common to see termolecular processes
(statistically improbable).
 Reaction Mechanisms
Multistep Mechanisms
•  Some reaction proceed through more than one step:
NO2(g) + NO2(g) → NO3(g) + NO(g)
NO3(g) + CO(g) → NO2(g) + CO2(g)
•  Notice that if we add the above steps, we get the overall
reaction:
NO2(g) + CO(g) → NO(g) + CO2(g)
 Reaction Mechanisms
Multistep Mechanisms
•  If a reaction proceeds via several elementary steps, then
the elementary steps must add to give the balanced
chemical equation.

•  Intermediate: a species which appears in an elementary

step which is not a reactant or product.
 Reaction Mechanisms
Rate Laws for Elementary Steps
•  The rate law of an elementary step is determined by its
molecularity:
–  Unimolecular processes are first order,
–  Bimolecular processes are second order, and
–  Termolecular processes are third order.
Reaction Mechanisms
Rate Laws for Elementary Steps
 Reaction Mechanisms
Rate Laws for Multistep Mechanisms
•  Rate-determining step: is the slowest of the elementary
steps.
•  Therefore, the rate-determining step governs the overall
rate law for the reaction.
Mechanisms with an Initial Fast Step
•  It is possible for an intermediate to be a reactant.
•  Consider
2NO(g) + Br2(g) → 2NOBr(g)
 Reaction Mechanisms
Mechanisms with an Initial Fast Step
2NO(g) + Br2(g) → 2NOBr(g)
•  The experimentally determined rate law is
Rate = k[NO]2[Br2]
•  Consider the following mechanism
k1
Step 1: NO(g) + Br2(g) NOBr2(g) (fast)
k-1
k2
Step 2: NOBr2(g) + NO(g) 2NOBr(g) (slow)
 Reaction Mechanisms
Mechanisms with an Initial Fast Step
•  The rate law is (based on Step 2):
Rate = k2[NOBr2][NO]
•  The rate law should not depend on the concentration of
an intermediate (intermediates are usually unstable).
•  Assume NOBr2 is unstable, so we express the
concentration of NOBr2 in terms of NOBr and Br2
assuming there is an equilibrium in step 1 we have
k1
[ NOBr2 ] = [ NO][Br2 ]
k−1
 Reaction Mechanisms
Mechanisms with an Initial Fast Step
•  By definition of equilibrium:
k1[ NO][Br2 ] = k−1[ NOBr2 ]
•  Therefore, the overall rate law becomes
k1 k1
Rate = k2 [ NO][Br2 ][ NO] = k2 [ NO]2[Br2 ]
k−1 k−1
•  Note the final rate law is consistent with the
experimentally observed rate law.
 Catalysis

•  A catalyst changes the rate of a chemical reaction.

•  There are two types of catalyst:
–  homogeneous, and
–  heterogeneous.
•  Chlorine atoms are catalysts for the destruction of ozone.
Homogeneous Catalysis
•  The catalyst and reaction is in one phase.
 Catalysis
Homogeneous Catalysis
•  Hydrogen peroxide decomposes very slowly:
2H2O2(aq) → 2H2O(l) + O2(g)
•  In the presence of the bromide ion, the decomposition
occurs rapidly:
–  2Br-(aq) + H2O2(aq) + 2H+(aq) → Br2(aq) + 2H2O(l).
–  Br2(aq) is brown.
–  Br2(aq) + H2O2(aq) → 2Br-(aq) + 2H+(aq) + O2(g).
–  Br- is a catalyst because it can be recovered at the end of the
reaction.
 Catalysis
Homogeneous Catalysis
•  Generally, catalysts operate by lowering the activation
energy for a reaction.
Catalysis
 Catalysis
Homogeneous Catalysis
•  Catalysts can operate by increasing the number of
effective collisions.
•  That is, from the Arrhenius equation: catalysts increase k
be increasing A or decreasing Ea.
•  A catalyst may add intermediates to the reaction.
•  Example: In the presence of Br-, Br2(aq) is generated as
an intermediate in the decomposition of H2O2.
 Catalysis
Homogeneous Catalysis
•  When a catalyst adds an intermediate, the activation
energies for both steps must be lower than the activation
energy for the uncatalyzed reaction. The catalyst is in a
different phase than the reactants and products.
Heterogeneous Catalysis
•  Typical example: solid catalyst, gaseous reactants and
products (catalytic converters in cars).
•  Most industrial catalysts are heterogeneous.
 Catalysis
Heterogeneous Catalysis
•  First step is adsorption (the binding of reactant molecules
to the catalyst surface).
•  Adsorbed species (atoms or ions) are very reactive.
•  Molecules are adsorbed onto active sites on the catalyst
surface.
Catalysis
 Catalysis
Heterogeneous Catalysis
•  Consider the hydrogenation of ethylene:
C2H4(g) + H2(g) → C2H6(g), ΔH = -136 kJ/mol.
–  The reaction is slow in the absence of a catalyst.
–  In the presence of a metal catalyst (Ni, Pt or Pd) the reaction
occurs quickly at room temperature.
–  First the ethylene and hydrogen molecules are adsorbed onto
active sites on the metal surface.
–  The H-H bond breaks and the H atoms migrate about the metal
surface.
 Catalysis
Heterogeneous Catalysis
–  When an H atom collides with an ethylene molecule on the
surface, the C-C π bond breaks and a C-H σ bond forms.
–  When C2H6 forms it desorbs from the surface.
–  When ethylene and hydrogen are adsorbed onto a surface, less
energy is required to break the bonds and the activation energy
for the reaction is lowered.
Enzymes
•  Enzymes are biological catalysts.
•  Most enzymes are protein molecules with large molecular
masses (10,000 to 106 amu).
 Catalysis
Enzymes
•  Enzymes have very specific shapes.
•  Most enzymes catalyze very specific reactions.
•  Substrates undergo reaction at the active site of an
enzyme.
•  A substrate locks into an enzyme and a fast reaction
occurs.
•  The products then move away from the enzyme.
 Catalysis
Enzymes
•  Only substrates that fit into the enzyme lock can be
involved in the reaction.
•  If a molecule binds tightly to an enzyme so that another
substrate cannot displace it, then the active site is blocked
and the catalyst is inhibited (enzyme inhibitors).
•  The number of events (turnover number) catalyzed is
large for enzymes (103 - 107 per second).
Catalysis
Enzymes