Lecture 2.

2
Chemical Kinetics
CH117 Physical Chemistry
Contents
• Chemical Reaction Rates
• Analysis of Reaction Kinetics
• Rates of Reaction
• Integrated Rate Laws
• The Arrhenius Equation
• Temperature Dependence of Reaction Rates
• The Arrhenius Parameters

2
Chemical Reaction Rates

3
Reaction Progress
Chemical kinetics is the study of reaction rates. Reaction rates are known to depend on the
concentration of reactants (and in some cases, of products).
These dependences can be expressed in terms of differential equations known as rate laws.
In a kinetic analysis, the first step is to establish the stoichiometry of the reaction and identify any
side reactions. Thus, the basic data of chemical kinetics are reactant and product concentrations at
different points in time in the course of a reaction.
In addition, the temperature is held constant during kinetic analyses as the rates of most chemical
reactions are sensitive to temperature.

4
Reaction Progress
Measuring the amounts of reactants and/or products taken from a reaction mixture at different
points in time can be accomplished using several analytical techniques, such as:
• absorption spectroscopy
• emission spectroscopy
• conductimetry
• mass spectrometry
• gas chromatography
• nuclear magnetic resonance
• electron paramagnetic resonance
Simpler techniques can also be used. For example, if a reaction that consists of at least one gaseous
component may undergo an overall change in pressure in a system of constant volume. Its progress
may be monitored by recording p(t).
In a real-time analysis, the composition of the system is analyzed while the reaction is in progress.
In these analyses, special techniques are required.

5
Rates of Reaction
Consider a reaction of the form
𝐴 + 2𝐵 → 3𝐶 + 𝐷. At some instant,
the molar concentration of a
component J is [J], and the volume
of the system is kept constant.
On a plot of component
concentration versus time, the
rate of consumption of one of the
reactants at a given time is
− 𝑑 𝑅 /𝑑𝑡, where R is A or B.
The rate of formation of one of
the products is 𝑑 𝑃 /𝑑𝑡, where P is
either C or D.
Both rates are positive.

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Rates of Reaction
For the reaction 𝐴 + 2𝐵 → 3𝐶 + 𝐷, it follows that:

and so there are several rates connected to the reaction. Recall that to generalize the progress of any
single reaction without making use of different rates, we use the extent of reaction 𝝃.
For any species J in a reaction, the change in amount of J, 𝑑𝑛𝐽 , is:

where 𝜈𝐽 is the stoichiometric number of the species (negative for reactants, positive for products).
The unique rate of reaction, 𝑣, is then defined as:

7
Rates of Reaction
Then, for any component J, since 𝑑𝑛𝐽 = 𝜈𝐽 𝑑𝜉,

For a homogeneous reaction in a constant-volume system, the volume V can be taken inside the
differential to give:

For a heterogeneous reaction, the constant surface area, A, occupied by the species is used in place of
V. Then, defining the surface concentration 𝜎𝐽 = 𝑛𝐽 /𝐴,

8
Rates of Reaction
Reaction rates of homogeneous reactions are commonly reported in moles per volume per unit
time:

For heterogeneous reactions, rates are expressed in moles per area per unit time:

9
Rate Laws
Reaction rates are often found to be proportional to the concentrations of the reactants raised to a
power. This is known as the power law model.
For example, the rate of a reaction between reactants A and B might be found to be:

The constant of proportionality 𝑘𝑟 is called the rate constant for the reaction. It is also called the
specific reaction rate.
An experimentally determined equation of this kind is called the rate law of the reaction. It is an
equation that expresses the rate of reaction in terms of the concentrations of all the species present
in the overall chemical equation for the reaction at the time of interest:

For homogeneous gas-phase reactions, it is also convenient to express the rate law in terms of
partial pressures:

10
Rate Laws
The rate law of a reaction is determined experimentally, and cannot in general be inferred
from the chemical equation for the reaction.
For example, the reaction of hydrogen and bromine has a very simple stoichiometry:

but its rate law is complicated:

The units of kr are always such as to convert the product of concentrations, each raised to the
appropriate power, into a rate expressed as a change in concentration divided by time.
Thus, the units of the rate constant can always be determined for rate laws of any form.

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Rate Laws
Exercise 2.2.1
The rate constant for a reaction 𝐴 + 𝐵 → 2𝐶 has a numerical value of 8.0 × 10−15 when the rate law
has the following form:
𝑣 = 𝑘𝑟 𝑁𝐴 𝑁𝐵
where 𝑁𝐴 and 𝑁𝐵 are the number densities of A and B (molecules per unit volume) and 𝑣 is in
molecules cm-3 s-1. Determine the units of 𝑘𝑟 , and convert it into a quantity using units of moles and
dm3.

12
Rate Laws
Exercise 2.2.1
The rate constant for a reaction 𝐴 + 𝐵 → 2𝐶 has a numerical value of 8.0 × 10−15 when the rate law
has the following form:
𝑣 = 𝑘𝑟 𝑁𝐴 𝑁𝐵
where 𝑁𝐴 and 𝑁𝐵 are the number densities of A and B (molecules per unit volume) and 𝑣 is in
molecules cm-3 s-1. Determine the units of 𝑘𝑟 , and convert it into a quantity using units of moles and
dm3.

13
Reaction Order
Many reactions are found to have rate laws of the form

The power to which the concentration of a species is raised in a rate law of this kind is the order of
the reaction with respect to that species.
The overall order of a reaction with a rate law of the power law form is the sum of the individual
orders, 𝑎 + 𝑏 + ⋯.
Thus, for the rate law 𝑣 = 𝑘𝑟 𝐴 𝐵 ,
• The reaction is first order in A.
• The reaction is first order in B.
• The reaction rate law is second-order overall.
A rate law does not need to have an integral order; many gas-phase reactions have fractions as
exponents in the rate law.

14
Reaction Order
Some reactions obey a zeroth-order rate law, therefore having a rate that is independent of the
concentration of the reactant, so long as some is present.
When a rate law is not of the power-law form, the reaction does not have an overall order
and might not even have definite orders with respect to each participant.
In chemical reaction kinetics, there are three important tasks:
1. to identify the rate law and obtain the rate constant from experimental data
2. to account for the values of the rate constants and explain their temperature dependence
3. to construct reaction mechanisms consistent with the rate law

15
Determining the Rate Law
The experimental determination of a rate law is simplified by the isolation method, also known as
the method of excess.
Here, all the reactants except one are present in large excess. The dependence of the rate on each of
the reactants can be found by isolating each reactant in turn—by having all other substances
present in large excess—and then coming up with an overall rate law.

16
Determining the Rate Law
Consider a reaction whose true rate law is 𝑣 = 𝑘𝑟 𝐴 𝐵 2 but is yet to be determined
experimentally.
If reactant B is in large excess, its concentration will be nearly constant throughout the reaction.
Then, the value of [B] at any time during the reaction can be approximated by 𝐵 0 , giving:

If, instead, reactant A is in large excess, its concentration at any time during the reaction can be
approximated by 𝐴 0 , so that:

In both cases, the effective rate law is pseudofirst-order overall and pseudosecond-order
overall, respectively.

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Determining the Rate Law
In the method of initial rates, which is often used in conjunction with the method of excess, the
instantaneous rate is measured at the beginning of the reaction for several different initial
concentrations of the isolated reactant.
If the initial rate is doubled when the concentration of the isolated reactant is doubled, the reaction
is first-order in that reactant. If the rate is instead quadrupled with the same change in
concentration, the reaction is second-order in that reactant.
Suppose that the rate law for a reaction with A isolated is 𝑣 = 𝑘𝑟 𝐴 𝑎 .
Then, the initial rate of the reaction 𝑣0 is given by the initial concentration of A:

Thus, a plot of the logarithms of the initial rates against the logarithms of the initial concentrations
of A should be a straight line, with slope a (order) and intercept ln 𝑘𝑟 .

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Determining the Rate Law
Exercise 2.2.2
The recombination of I atoms in the gas phase in the presence of argon was investigated and the
order of the reaction was determined by the method of initial rates. The initial rates of reaction of
2𝐼 𝑔 + 𝐴𝑟 𝑔 → 𝐼2 𝑔 + 𝐴𝑟 𝑔 were as follows:

The Ar concentrations are (a) 1.0 × 10−3 mol dm−3 , (b) 5.0 × 10−3 mol dm−3 , and
(c) 1.0 × 10−2 mol dm−3 . Find the orders of reaction with respect to I and Ar, and the rate constant.

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Determining the Rate Law
Exercise 2.2.2

20
Determining the Rate Law
Exercise 2.2.2

21
Determining the Rate Law
Exercise 2.2.2

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Integrated Rate Laws

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Zeroth-Order Reactions
Rate laws are differential equations, which can be integrated to predict how the concentrations of
the reactants and products change with time. Integrated rate laws are analytical solutions to these
differential equations, which are easily obtained and prove to be very useful.
For a zeroth-order reaction of the type 𝐴 → 𝑃, so long as some reactant remains, the rate is
constant:

Rearranging then integrating,

INTEGRATED ZEROTH-ORDER
RATE LAW

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First-Order Reactions
Consider the first-order rate law

INTEGRATED FIRST-ORDER
RATE LAW

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First-Order Reactions
From the result:

A plot of ln 𝐴 versus time for a

first-order reaction will give a straight
line whose slope is −𝑘𝑟 and intercept
is ln 𝐴 0 .
In a first-order reaction, the reactant
concentration decreases exponentially
with time, with a rate determined
by 𝑘𝑟 .

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First-Order Reactions
For first-order reactions, a useful indication of the rate is the half-life, 𝒕𝟏/𝟐 , of a substance. It is
defined as the time taken for the concentration of a reactant to fall to half its initial value.
From the integrated rate law, using 𝐴 1/2 = 0.5 𝐴 0 at 𝑡 = 𝑡1/2 ,

Thus, for a first-order reaction, the half-life of a reactant is independent of initial concentration.

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First-Order Reactions
Exercise 2.2.3
The variation in the partial pressure of azomethane with time was followed at 600K, with the
results given below. Confirm that the decomposition 𝐶𝐻3 𝑁2 𝐶𝐻3 𝑔 → 𝐶𝐻3 𝐶𝐻3 𝑔 + 𝑁2 𝑔 is first-
order in azomethane, and find the rate constant and half-life at 600 K.

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First-Order Reactions
Exercise 2.2.3

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Second-Order Reactions
For the second-order rate law:

The integrated rate law can easily be found:

INTEGRATED SECOND-ORDER RATE LAW

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Second-Order Reactions
From the integrated rate law:

A plot of 1/ 𝐴 versus time for a second-

order reaction will give a straight line with
slope 𝑘𝑟 and intercept 1/ 𝐴 0 .
For second-order reactions, the
(first-order)
concentration of A approaches zero more
slowly than in a first-order reaction with
the same initial rate.

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Second-Order Reactions
Another type of second-order reaction is one that is first order in each of the two reactants A and B:

Since the variable [B] is now present, its relationship to [A] must first be determined. This is found
from the reaction stoichiometry and the initial concentrations of A and B.
For example, for the reaction 𝐴 + 𝐵 → 𝑃, when the concentration of A has fallen to 𝐴 0 − 𝑥, the
concentration of B will also have fallen to 𝐵 0 − 𝑥. Then, the rate law becomes:

But, because 𝐴 = 𝐴 0 − 𝑥,

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Second-Order Reactions
Then,

The left integrand is first decomposed into partial fractions which are then integrated individually
to give:

Upon rearranging,

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Second-Order Reactions
Exercise 2.2.4
A second-order reaction of the type 𝐴 + 𝐵 → 𝑃 is carried out in a solution. Initially, the
concentrations of reactants are 𝐴 0 = 0.075 M and 𝐵 0 = 0.050 M. After 1.0 h the concentration of
B has fallen to 𝐵 = 0.020 M. Determine the rate constant for this reaction if it follows the rate law:

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35
Reactions at Equilibrium
In practice, most kinetic studies are made on reactions that are far from equilibrium and if products
are in low concentration the reverse reactions are unimportant.
Close to equilibrium, however, the products might be so abundant that the reverse reaction must be
taken into account.
Consider a reaction in which A forms B and both forward and reverse reactions are first order:

At any instant, the net rate of change of the concentration of A is:

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Reactions at Equilibrium
If initially, only A is present at 𝐴 0 , then at all times, 𝐴 + 𝐵 = 𝐴 0 .
Therefore,

Integrating with the use of an integrating factor, the resulting expression is:

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Reactions at Equilibrium
As 𝑡 → ∞,

It follows that the equilibrium constant

of the reaction is:

The same conclusion can be reached by

noting that, at equilibrium, the forward
and reverse rates must be the same.

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Reactions at Equilibrium
In general, the overall equilibrium constant can be expressed in terms of the rate constants for all
the intermediate stages of the reaction mechanism:

where the 𝑘𝑓𝑜𝑟 are the rate constants for the individual steps and the 𝑘𝑟𝑒𝑣 are those for the
corresponding reverse steps.

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The Arrhenius Equation

40
Temperature Dependence
Chemical reactions usually go faster as temperature is raised—it is found experimentally that a plot
of ln 𝑘𝑟 versus 1/𝑇 gives a straight line with a negative slope, indicating that an increase in T (and
therefore a decrease in 1/T) results in an increase in ln 𝑘𝑟 .
This temperature dependence of rate is
expressed mathematically by the
Arrhenius equation:

ARRHENIUS EQUATION
The parameter A is called the frequency factor
(a.k.a. pre-exponential factor). 𝐸𝑎 is the
activation energy. These two parameters are
collectively known as the Arrhenius parameters.
A plot of ln 𝑘𝑟 versus 1/𝑇 is called an Arrhenius plot.

41
Temperature Dependence
Exercise 2.2.5
The rate of the second-order decomposition of acetaldehyde was measured over the temperature
range 700-1000 K, and the rate constants are reported below. Find 𝐸𝑎 and A.

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Temperature Dependence
Exercise 2.2.5
The rate of the second-order decomposition of acetaldehyde was measured over the temperature
range 700-1000 K, and the rate constants are reported below. Find 𝐸𝑎 and A.

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Temperature Dependence
Once the Arrhenius parameters are known, it is possible to predict the value of the rate constant at
another temperature given its value at one temperature.

Subtracting the first equation from the second,

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Temperature Dependence
The Arrhenius equation provides the following conclusions regarding the temperature dependence
of the rate of a reaction:
• A high activation energy means the rate constant depends strongly on temperature.
• If a reaction has zero activation energy, its rate is independent of temperature.
• A negative activation energy indicates that the rate decreases as the temperature is raised.

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The Activation Energy
When two reactant molecules collide, the reaction
proceeds: A and B come into contact, distort, and
begin to exchange or discard atoms.
The reaction coordinate summarizes the
collection of motions (e.g. changes in interatomic
distances and bond angles) that are directly
involved in the formation of products from
reactants.
The potential energy rises to a maximum and the
cluster of atoms that corresponds to the region
close to the maximum is called the activated
complex.

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The Activation Energy
The climax of the reaction is at the peak of the
potential energy curve: this corresponds to the
activation energy, 𝑬𝒂 .
At this point, the two reactant molecules have come
to such a degree of closeness and distortion that a
small further distortion will send them in the
direction of products.
This configuration is called the transition state of
the reaction.
Thus, the activation energy is the minimum
energy reactants must possess to form products.

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The Activation Energy
In a reaction mixture, there are numerous molecules
colliding each second, but only very few are sufficiently
energetic to lead to a reaction.
The fraction of close encounters between reactants
with energy in excess of 𝐸𝑎 is given by the Boltzmann
distribution as 𝑒 −𝐸𝑎 /𝑅𝑇 .
This is confirmed by comparing the expression with the
Arrhenius equation, rewritten without the logarithms:

ARRHENIUS EQUATION
(ALTERNATIVE FORM)

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Catalysis
The Arrhenius equation predicts two ways that the rate constant can be increased:
• increase the temperature
• decrease the activation energy
Changing the reaction temperature is easy, but reducing the activation energy is challenging.
Catalysts accomplish this second task by providing
an alternative path for the reaction, one in which
the activation energy is lowered significantly.

49
Lecture 2.2 Problems
1. The rate of the reaction 𝐴 + 2𝐵 → 3𝐶 + 𝐷 was reported as 2.7 mol dm-3 s-1. State the rates of
formation and consumption of the participants.
2. At 400 K, the rate of decomposition of a gaseous compound was 9.71 Pa s-1 when 10% had
reacted and 7.67 Pa s-1 when 20% had reacted. Identify the order of the reaction.
3. The data below apply to the reaction between tert-butyl bromide and water to form tert-butanol
and hydrobromic acid in an SN1 process. Identify the order of the reaction and calculate the rate
constant and the molar concentration of tert-butyl bromide remaining after 43.8 h.

4. The rate constant of a chemical reaction is found to triple when the temperature is raised from
24oC to 49oC. Evaluate the activation energy.

50
 Lecture 2.2
Chemical Kinetics
CH117 Physical Chemistry
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