Chemical Kinetics

By

Arunasish Layek
 Chemical Kinetics
Kinetics: The study of speed of chemical reactions

Not Limited to the speed at which reactions occur, kinetics also sheds
light on the reaction mechanism (exactly how the reaction occurs)

Speed of a reaction: is measured by the change in Conc. with time.

Important factors which affect rates of reactions:

reactant concentration
temperature
action of catalysts
surface area
pressure of gaseous reactants or products
 Outline: Kinetics
Reaction Rates How we measure rates.

How the rate depends on amounts

Rate Laws of reactants.
How to calculate amount left or
Integrated Rate Laws time to reach a given amount.
How long it takes to react 50% of
Half-life reactants.
How rate constant changes with
Arrhenius Equation temporature.
Link between rate and molecular
Mechanisms scale processes.
 Reaction Rates

Rates of reactions can be determined by

monitoring the change in concentration of
either reactants or products as a function of
time t.
[A] = concentration of reactant A
 Reaction Rate
• For the reaction A  B there are two ways of measuring rate:
(1) the speed at which the reactants disappear
(2) the speed at which the products appear
• Reactions are reversible, so as products accumulate they can begin
to turn back into reactants.
• Early on the rate will depend on only the amount of reactants
present. We want to measure the reactants as soon as they are
mixed.
• The most useful (and general) way of measuring the rate of the
reaction is in terms of change in concentration per unit time…
Rate = ∆[A]/∆t limits to d[A]/dt
Most Common Units… Rate = M/s
Where Molarity (M) = moles/Liter
 Chemical Kinetics

Thermodynamics – does a reaction take place?

Kinetics – how fast does a reaction proceed?

Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).

A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.
Factors Affecting Reaction Rate
Constants
Factors that Affect the Reaction Rate Constant
1. Temperature: At higher temperatures, reactant molecules have more kinetic
energy, move faster, and collide more often and with greater energy
• Collision Theory: When two chemicals react, their molecules have to
collide with each other with sufficient energy for the reaction to take
place.
• Kinetic Theory: Increasing temperature means the molecules move
faster.
2. Concentrations of reactants
• As the concentration of reactants increases,
so does the likelihood that reactant molecules will collide.
3. Catalysts
• Speed up reactions by lowering activation energy
4. Surface area of a solid reactant
• Bread and Butter theory: more area for reactants to be in contact
5. Pressure of gaseous reactants or products
• Increased number of collisions
Concentration Affects Reaction Rate Constant
• Here’s another way of looking at reaction rates…
2N2O5(g)  4NO2(g) + O2(g)
• Notice that for every 1 mole of O2 that appears, 4 x as many moles
of NO2 will also appear. In the meantime, twice as many moles of
N2O5 will be disappearing as moles of O2 forming.
• Changes in concentrations of the reactants and/or products is
inversely proportional to their stoichiometric proportions.
• This means that the rate of the reaction could be written like this…
Rate = −½ ∆ [N2O5]/∆t = ¼ ∆[NO2]/∆t = ∆[O2]/∆t

* (Notice the negative sign on the rate of [N2O5] reminds us that it is disappearing.)

•In general, for a reaction that looks like this… aA + bB cC + dD

Rate = −1 ∆[A] = −1 ∆[B] = 1 ∆[C] = 1 ∆[D]
a ∆t b ∆t c ∆t d ∆t
Reaction Rate Laws
 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.
 A B

time

D[A]
rate = -
Dt

D[B]
rate =
Dt
 Rate Laws

• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2] 1
 Rate Law
• In general, rates of reactions increase as concentrations increase
since there are more collisions occurring between reactants.
• The overall concentration dependence of reaction rate is given in a
rate law or rate expression.
• Here’s what a general rate law for a reaction will look like…
Rate = k [A]m [B]n
- [A] & [B] represent the reactants.
- The exponents m and n are called “reaction orders”.
- The proportionality constant k is called the rate constant.
- The overall reaction order is the sum of the reaction orders:
m+n
Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

 The Rate Law
The rate law expresses the relationship of the rate of a reaction
to the rate constant and the concentrations of the reactants
raised to some powers.
aA + bB cC + dD

Rate = k [A]m[B]n

reaction is mth order in A

reaction is nth order in B
reaction is (m+n)th order overall

•Rates come from experiment data, not stoichiometry!

Integrated Reaction Rate Laws
 Integrated Rate Laws
Consider a simple 1st order reaction: A  B

Differential form:

How much A is left after time t? Integrate:

 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, during
the course of the reaction.
 Integrated Rate Laws
Manipulating this equation produces…

…which is in the form

y = ax + b
 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.
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• The reaction slows

down with time because
the concentration of the
reactants decreases.
 Reaction Rate
• Here’s an example of a reaction…
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)
• We can plot [C4H9Cl] versus time…
• The average rate of a reaction
decreases with time.

• The rate at any instant in time

(instantaneous rate) is the slope
of the tangent to the curve.

• Instantaneous rate is different

from average rate, so when we
refer to the rate of a reaction, we
will be assuming it’s the
instantaneous rate unless
otherwise told.
Order of Reactions
 Order of Reactions
• A reaction is zero order in a reactant if the change in
concentration of that reactant produces no effect.
• A reaction is 1st order if doubling the concentration
causes the rate to double.
• A reaction is 2nd order if doubling the concentration
causes a quadruple increase in rate.
-3rd order…doubling concentration leads to 23 (or 8 times) the rate.
• Note-- The rate constant, k, does not depend on concentration!
• Once we have determined the rate law and the rate constant, we
can use them to calculate initial reaction rates under any set of
initial concentrations
 Zero-Order Reactions
D[A]t
rate = - rate = k [A]0 = k
Dt
[A]t is the concentration of A at any time t
[A]t - [A]0 = -kt [A]0 is the concentration of A at time t=0

Half life for zero order t½ = t when [A]t = [A]0/2

[A]0
t½ =
2k
 First-Order Processes

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.
 Change of Concentration with Time
• Goal: to convert the rate law into a convenient equation to give
concentrations as a function of time…(the book has the derivation, and it
involves calculus, so we will skip to the conclusion)…

For 1st order reactions: ln[A]t = −kt + ln[A]0

where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of s-1
t= time in seconds
[A]o = initial concentration of A

• This equation has the general form for a straight line, y=mx+b, so
a plot of ln[A]t vs. t is a straight line with slope (-k) and intercept
ln[A]0.
(slope= −k)
ln[A]t

Time (s)
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
reaction?
 First-Order Processes
CH3NC CH3CN

This data was

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

If a reaction is first-order:
a plot of ln [A]t versus t will yield a straight
line with a slope of -k.
 First-Order Processes

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

a straight line results.
– The process is first-order.
– k is the negative slope: 5.1  10-5 s-1.
Second Order Reactions
 Second-Order Processes

So if a process is second-order in A, a
plot of 1/[A] versus t will yield a straight
line with a slope of k.
 Change of Concentration with Time
For 2nd order reactions: 1/[A]t = kt + 1/[A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of M-1s-1
t= time in seconds
[A]o = initial concentration of A

• This equation has the general form for a straight line, y=mx+b, so
a plot of l/[A]t vs. t is a straight line with slope (k) and intercept of
1/[A]0.

(slope= k)
1/[A]t

Time (s)
 Second-Order Reactions
D[A]
rate = -
Dt [A] t is the concentration of A at any time t

rate = k [A]t2 [A]0 is the concentration of A at time t=0

Half life for second order

1 1
- = kt
[A]t [A]0 t½ = t when [A]t =[A]0/2
1
t½ =
k[A]0
 Determining Reaction order
The decomposition of NO2 at 300°C is described by
the equation
NO2 (g) NO (g) + 1/2 O2 (g)
and yields these data:

Time (s) [NO2], M

0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
 Determining Reaction order
Graphing ln [NO2] versus t
yields:
• The plot is not a straight
line, so the process is not
first-order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 -4.610
50.0 0.00787 -4.845 Does not fit:

100.0 0.00649 -5.038

200.0 0.00481 -5.337
300.0 0.00380 -5.573
 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
300.0 0.00380 263
 Half-Life
Half-life is defined as the time required for
one-half of a reactant to react.
 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

t½= −ln(½) = 0.693 where k = the rate constant

k k (NOTE: For a first-order process, the half-
life does not depend on [A]0.)

• For a 2nd order reaction, half-life depends on the reactant

concentrations: t½ = 1/ k[A]0

• For Zero order reactions… t½ = [A]0 /2k

 Half-Life- 2nd order
For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation.
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] - [A]0 = - kt t½ =
2k
Ln 2
1 rate = k [A] ln[A] - ln[A]0 = - kt t½ =
k
1 1 1
2 rate = k [A]2 - = kt t½ =
[A] [A]0 k[A]0
 Summary of Kinetics
Second order
First order General Second order
(1 reactant)
Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated

k(T)
 Activation Energy
• There is a minimum amount of energy required for a
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.
 Activation Energy
• Molecules must possess a minimum amount of energy to
react. Why?
– In order to form products, bonds must be broken in the
reactants. Bond breakage requires energy.
– Molecules moving too slowly, with too little kinetic energy,
don’t react when they collide.

• Activation energy, Ea, is the minimum energy required to

initiate a chemical reaction.
− Ea will vary with the reaction.
 Activation Energy
• Consider the rearrangement of methyl isonitrile:

– 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.
* Here’s what the reaction looks like in terms of a graph of the
energies that are involved in the process…
 Activation Energy
• The change in energy, ∆E, for the reaction is the difference in
energy between CH3NC and CH3CN.
• The activation energy, Ea , is the difference in energy between
reactants, CH3NC, and the transition state.
• The rate depends on Ea. If the “hill” is taller, the reaction rate is
slower. If the “hill” is shorter the rate is faster.
• Notice that if a forward reaction is exothermic… (CH3NC  CH3CN),
then the reverse reaction is endothermic… (CH3CN  CH3NC).
• The methyl isonitrile molecule needs to gain enough energy to
overcome the activation energy barrier.
• From kinetic molecular theory, we know that as temperature
increases, the total kinetic energy increases and the number of
molecules with energy greater than Ea increases.
• So as long as the temperature is high enough, the reaction can
make it “over the hill” and proceed.
 A+B C+D

Exothermic Reaction Endothermic Reaction

The activation energy (Ea) is the minimum amount of

energy required to initiate a chemical reaction.
 Energy Diagrams

Exothermic Endothermic

(a) Activation energy (Ea) for the forward reaction 50 kJ/mol 300 kJ/mol
(b) Activation energy (Ea) for the reverse reaction 150 kJ/mol 100 kJ/mol
(c) Delta H -100 kJ/mol +200 kJ/mol
Temperature vs. Energy of Activation
Reaction Mechanisms
 Reaction Mechanisms
The sequence of events that describes the
actual process by which reactants become
products is called the reaction mechanism.
 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.
 Reaction Mechanisms

The overall progress of a chemical reaction can be represented

at the molecular level by a series of simple elementary steps
or elementary reactions.

The sequence of elementary steps that leads to product

formation is the reaction mechanism.

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

N2O2 is detected during the reaction!

Elementary step: NO + NO N 2O 2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
 Rate Laws and Rate Determining Steps

Writing plausible reaction mechanisms:

• The sum of the elementary steps must give the overall
balanced equation for the reaction.
• The rate-determining step should predict the same rate
law that is determined experimentally.

The rate-determining step is the

slowest step in the sequence of
steps leading to product formation.
 Reaction Mechanisms
• Up until now, we have only been concerned with the reactants and
products. Now we will examine what path the reactants took in
order to become the products.
• 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 & Molecularity
• Elementary step: any process that occurs in a single step.
• Molecularity: 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 uncommon to see termolecular processes…statistically improbable for an
effective collision to occur.)
 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.
 Reaction Intermediates

Intermediates are species that appear in a reaction

mechanism but not in the overall balanced equation.

An intermediate is always formed in an early elementary step

and consumed in a later elementary step.

Elementary step: NO + NO N2O2

+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
 Arrhenius Equation
Svante Arrhenius developed a mathematical
relationship between k and Ea:

where ……
k= rate constant
Ea = Activation Energy (in kJ/mole)
R = Gas Constant
T = Kelvin temperature
and
A is the frequency factor, a number that represents
the likelihood that collisions would occur with the
proper orientation for reaction.
 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.
Temperature Dependence of the Rate Constant

k = A • exp( -Ea/RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
A is the frequency factor

-Ea 1
Ln k = - + lnA
R T
Maxwell–Boltzmann
Distributions
Maxwell–Boltzmann Distributions

• Temperature is
defined as a
measure of the
average kinetic
energy of the
molecules in a
sample.
• At any temperature there is a wide
distribution of kinetic energies.
Maxwell–Boltzmann Distributions

• As the temperature
increases, the curve
flattens and
broadens.
• Thus at higher
temperatures, a
larger population of
molecules has
higher energy.
 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
barrier.
Catalysts
A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
Ea k

uncatalyzed catalyzed

ratecatalyzed > rateuncatalyzed

 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.
 Catalysts

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