Chemical Kinetics

The study of reaction rates, the changes in concentrations of

reactants (or products) as a function of time

Quantitative relationships through the derivation of a rate law

Kinetics can reveal much about the mechanism of a reaction.

Chemical
Kinetics
 Outline: Kinetics
Reaction Rates How we measure rates.

How the rate depends on amounts

Rate Laws of reactants.
How to calc amount left or time to
Integrated Rate Laws reach a given amount.
How long it takes to react 50% of
Half-life reactants.

Arrhenius Equation How rate constant changes with T.

Link between rate and molecular

Mechanisms scale processes.

Chemical
Kinetics
 Kinetics

• Studies the rate at which a chemical

process occurs.
• Besides information about the speed at
which reactions occur, kinetics also
sheds light on the reaction mechanism
(exactly how the reaction occurs).

Chemical
Kinetics
Reaction rate: the central focus of chemical kinetics

Chemical
Kinetics

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The wide range of reaction rates

Chemical
Kinetics
 Factors Influencing Reaction Rates

Reactant Concentration: molecular collisions are required for

reactions to occur
reaction rate a collision frequency a concentration
Physical State: molecules must mix to collide
When reactants are in different phases, the more finely divided
a solid or liquid reactant, the greater the surface area per unit
volume, the more contact it makes with other reactants,
and the faster the reaction.
Temperature: molecules must collide with sufficient energy to rea
Higher T translates into more collisions per unit time and
into higher-energy collisions
Chemical
reaction rate a collision energy a temperature Kinetics
 The effect of surface area on reaction rate
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Chemical
Figure steel nail in O2 steel wool in O2 Kinetics

16.3
 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Collision energy
and reaction rate

Other factor: reaction

trajectory (not all collisions
with sufficient energy
are productive)

Chemical
Figure Kinetics

16.4
 Expressing Reaction Rate

reaction rate = the changes in [reactants] or [products] per unit time;

[reactant] decreases, [product] increases

A B
Measure [A1] at t1, then measure [A2] at t2
Average rate of reaction = - ([A2] - [A1]) / (t2 - t1)
rate is always = - D[A] / Dt
expressed as a
positive value
rate units = mol/L/s
Also, reaction rate = + D[B] / Dt
Chemical
Kinetics
Factors That Affect Reaction Rates
• Concentration of Reactants
 As the concentration of reactants increases, so does the
likelihood that reactant molecules will collide.
• Temperature
 At higher temperatures, reactant molecules have more kinetic
energy, move faster, and collide more often and with greater
energy.
• Catalysts
 Speed rxn by changing
mechanism.

Chemical
Kinetics
 Reaction Rates

Rxn Movie

Rates of reactions can be determined by

monitoring the change in concentration of
either reactants or products as a function of
time. D[A] vs Dt
Chemical
Kinetics
 Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
[C4H9Cl] M
In this reaction, the
concentration of
butyl chloride,
C4H9Cl, was
measured at various
times, t.

Chemical
Kinetics
 Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
Average Rate, M/s
The average rate of
the reaction over
each interval is the
change in
concentration divided
by the change in time:

Chemical
Kinetics
 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.

Chemical
Kinetics
 Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

• A plot of concentration
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.

Chemical
Kinetics
 Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

• The reaction slows

down with time because
the concentration of the
reactants decreases.

Chemical
Kinetics
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.

-D[C4H9Cl] D[C4H9OH]
Rate = =
Dt Dt Chemical
Kinetics
Reaction Rates and Stoichiometry

• What if the ratio is not 1:1?

H2(g) + I2(g) 2 HI(g)
• Only 1/2 HI is made for each H2 used.

Chemical
Kinetics
Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

Chemical
Kinetics
 Concentration and Rate

Each reaction has its own equation that

gives its rate as a function of reactant
concentrations.

this is called its Rate Law

To determine the rate law we measure the rate
at different starting concentrations.

Chemical
Kinetics
 Concentration and Rate

Compare Experiments 1 and 2:

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

Likewise, compare Experiments 5 and 6:

when [NO2-] doubles, the initial rate doubles.
Chemical
Kinetics
 Concentration and Rate

This equation is called the rate law,

and k is the rate constant.

Chemical
Kinetics
 Rate Laws
• A rate law shows the relationship between the reaction
rate and the concentrations of reactants.
 For gas-phase reactants use PA instead of [A].

• k is a constant that has a specific value for each reaction.

• The value of k is determined experimentally.

“Constant” is relative here-

k is unique for each rxn
k changes with T (section 14.5)
Chemical
Kinetics
 Rate Laws
• Exponents tell the order of the reaction with
respect to each reactant.
• This reaction is
First-order in [NH4+]
First-order in [NO2−]
• The overall reaction order can be found by
adding the exponents on the reactants in the
rate law.
• This reaction is second-order overall.

Chemical
Kinetics
 Integrated Rate Laws
Consider a simple 1st order rxn: A B

Differential form:

How much A is left after time t? Integrate:

Chemical
Kinetics
 Integrated Rate Laws
The integrated form of first order rate law:

Can be rearranged to give:

[A]0 is the initial concentration of A (t=0).

[A]t is the concentration of A at some time, t,
Chemical
during the course of the reaction. Kinetics
 Integrated Rate Laws
Manipulating this equation produces…

…which is in the form y = mx + b

Chemical
Kinetics
 First-Order Processes

If a reaction is first-order, a plot of ln [A]t

vs. t will yield a straight line with a slope
of -k.

So, use graphs to determine rxn order.

Chemical
Kinetics
First-Order Processes
Consider the process in
which methyl isonitrile is
converted to acetonitrile.

CH3NC CH3CN

How do we know this

is a first order rxn?

Chemical
Kinetics
 First-Order Processes
CH3NC CH3CN

This data was

collected for this
reaction at
198.9°C.
Does
rate=k[CH3NC]
for all time intervals?

Chemical
Kinetics
 First-Order Processes

• When ln P is plotted as a function of time, a

straight line results.
 The process is first-order. Chemical

 k is the negative slope: 5.1  10-5 s-1.

Kinetics
 Second-Order Processes
Similarly, integrating the rate law for a
process that is second-order in reactant A:

Rearrange, integrate:

also in the form y = mx + b

Chemical
Kinetics
 Second-Order Processes

So if a process is second-order in A, a
plot of 1/[A] vs. t will yield a straight line
with a slope of k.

First order:

If a reaction is first-order, a plot of ln [A]t vs. t will yield

a straight line with a slope of -k. Chemical
Kinetics
 Second-Order Processes
A graph of 1/[NO2] vs. t
gives this plot.

Time (s) [NO2], M 1/[NO2] • This is a straight

0.0 0.01000 100
line. Therefore,
the process is
50.0 0.00787 127
second-order in
100.0 0.00649 154
[NO2].
200.0 0.00481 208 Chemical
Kinetics
300.0 0.00380 263
Half-Life
• Half-life is defined
as the time required
for one-half of a
reactant to react.
• Because [A] at t1/2 is
one-half of the
original [A],
[A]t = 0.5 [A]0.

Chemical
Kinetics
 Half-Life
For a first-order process, set [A]t=0.5 [A]0 in
integrated rate equation:

NOTE: For a first-order

process, the half-life
Chemical
does not depend on [A]0. Kinetics
 Half-Life- 2nd order
For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation.

Chemical
Kinetics
 Outline: Kinetics
First order Second order Second order

Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated

Chemical
Kinetics
Temperature and Rate

• Generally, as temperature
increases, so does the
reaction rate.
• This is because k is
temperature dependent.

Chemical
Kinetics
 The Collision Model

• In a chemical reaction, bonds are

broken and new bonds are formed.
• Molecules can only react if they collide
with each other.

Chemical
Kinetics
 The Collision Model

Furthermore, molecules must collide with the

correct orientation and with enough energy to
cause bond breakage and formation.

Chemical
Kinetics
 Activation Energy
• In other words, there is a minimum amount of energy
required for reaction: the activation energy, Ea.
• Just as a ball cannot get over a hill if it does not roll
up the hill with enough energy, a reaction cannot
occur unless the molecules possess sufficient energy
to get over the activation energy barrier.

Chemical
Kinetics
 Reaction Coordinate Diagrams

It is helpful to
visualize energy
changes
throughout a
process on a
reaction coordinate
diagram like this
one for the
rearrangement of
methyl isonitrile.
Chemical
Kinetics
 Reaction Coordinate Diagrams
• It shows the energy of
the reactants and
products (and,
therefore, DE).
• The high point on the
diagram is the transition
state.
• The species present at the transition state is
called the activated complex.
• The energy gap between the reactants and the
activated complex is the activation energy
Chemical
barrier. Kinetics
 Arrhenius Equation
Svante Arrhenius developed a mathematical
relationship between k and Ea:

where A is the frequency factor, a number that

represents the likelihood that collisions would
occur with the proper orientation for reaction.
Chemical
Kinetics
 Arrhenius Equation
Taking the natural
logarithm of both
sides, the equation
becomes
1
RT
y = mx + b
When k is determined experimentally at
several temperatures, Ea can be calculated
from the slope of a plot of ln k vs. 1/T. Chemical
Kinetics
 Outline: Kinetics
First order Second order Second order

Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated

k(T)
Chemical
Kinetics
 Reaction Mechanisms

The sequence of events that describes

the actual process by which reactants
become products is called the reaction
mechanism.

Chemical
Kinetics
 Reaction Mechanisms

• Reactions may occur all at once or

through several discrete steps.
• Each of these processes is known as an
elementary reaction or elementary
process.

Chemical
Kinetics
 Reaction Mechanisms

• The molecularity of a process tells how many

molecules are involved in the process.

• The rate law for an elementary step is written

directly from that step.
Chemical
Kinetics
 Multistep Mechanisms

• In a multistep process, one of the steps will

be slower than all others.
• The overall reaction cannot occur faster than
this slowest, rate-determining step.

Chemical
Kinetics
 Slow Initial Step
NO2 (g) + CO (g) NO (g) + CO2 (g)

• The rate law for this reaction is found

experimentally to be
Rate = k [NO2]2
• CO is necessary for this reaction to occur, but the
rate of the reaction does not depend on its
concentration.
• This suggests the reaction occurs in two steps.
Chemical
Kinetics
 Slow Initial Step
• A proposed mechanism for this reaction is
Step 1: NO2 + NO2 NO3 + NO (slow)
Step 2: NO3 + CO NO2 + CO2 (fast)
• The NO3 intermediate is consumed in the second step.
• As CO is not involved in the slow, rate-determining step, it does
not appear in the rate law.

Chemical
Kinetics
 Fast Initial Step

• The rate law for this reaction is found

(experimentally) to be

• Because termolecular (= trimolecular)

processes are rare, this rate law
suggests a two-step mechanism.
Chemical
Kinetics
 Fast Initial Step
• A proposed mechanism is

Step 1 is an equilibrium-
it includes the forward and reverse reactions.

Chemical
Kinetics
 Fast Initial Step

• The rate of the overall reaction depends

upon the rate of the slow step.
• The rate law for that step would be

• But how can we find [NOBr2]?

Chemical
Kinetics
 Fast Initial Step

• NOBr2 can react two ways:

With NO to form NOBr
By decomposition to reform NO and Br2
• The reactants and products of the first
step are in equilibrium with each other.
• Therefore,
Ratef = Rater
Chemical
Kinetics
 Fast Initial Step

• Because Ratef = Rater ,

k1 [NO] [Br2] = k−1 [NOBr2]

Solving for [NOBr2] gives us

k1
k−1
[NO] [Br2 ] = [NOBr 2 ]
Chemical
Kinetics
 Fast Initial Step

Substituting this expression for [NOBr2]

in the rate law for the rate-determining
step gives

Chemical
Kinetics
 Catalysts
• Catalysts increase the rate of a reaction by
decreasing the activation energy of the
reaction.
• Catalysts change the mechanism by which
the process occurs.

Chemical
Kinetics
 Catalysts

One way a
catalyst can
speed up a
reaction is by
holding the
reactants together
and helping bonds
to break.

Chemical
Kinetics
Enzymes
• Enzymes are
catalysts in
biological systems.
• The substrate fits
into the active site of
the enzyme much
like a key fits into a
lock.

Chemical
Kinetics