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Chapter 2

Kinetics of Homogeneous
Reactions
Kinetics of homogeneous reactions, rate of reaction, batch reactors, continuous stirred tank reactor (CSTR),
plug flow reactor, single and multiple ideal reactors, residence time distribution and measurement, isothermal
reactors with multiple reactions, effect of temperature and pressure, reactor design for homogeneous reactions,
optimization, introduction to heterogeneous reactions.

Dr. Enshirah Da'na 1

Simple Reactor Types

It is simple to find their performance equations.

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Batch Reactor
Uniform composition everywhere in the reactor,
but the course of composition changes with time.

Mixed Flow Reactor

Uniformly mixed, same composition everywhere
in the reactor and at the exit.

Dr. Enshirah Da'na 3

Plug flow Reactor

Fluid passes through the reactor with no
mixing of the earlier and later entering fluid.

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The Rate Equation

For single-phase reaction:

𝒂𝑨 + 𝒃𝑩 → 𝒓𝑹 + 𝒔𝑺

The rate of disappearance of reactant A is then:

𝟏 𝒅𝑵𝑨 𝒂𝒎𝒐𝒖𝒏𝒕 𝒐𝒇 𝑨 𝒅𝒊𝒔𝒂𝒑𝒑𝒆𝒂𝒓𝒊𝒏𝒈 𝒎𝒐𝒍

−𝒓𝑨 = − 𝑽 𝒅𝒕
= 𝒗𝒐𝒍𝒖𝒎𝒆 𝒕𝒊𝒎𝒆
, 𝒎𝟑.𝒔

The minus sign means disappearance.

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The rates of reaction of all materials are related by:

𝒂𝑨 + 𝒃𝑩 → 𝒓𝑹 + 𝒔𝑺
7𝒓𝑨 7𝒓𝑩 𝒓𝑹 𝒓𝑺
= = =
𝒂 𝒃 𝒓 𝒔

Factors affecting the rate of reaction:

• The composition
• The energy of the material.

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Energy sources:
• The temperature (Kinetic energy of the molecules)
• The light intensity within the system (this may affect the bond
energy between atoms)
• The magnetic field intensity
Only temperature will be considered:

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CONCENTRATION-DEPENDENT TERM OF A RATE EQUATION

Single and Multiple Reactions

• If single stoichiometric equation and single rate represent the progress

of reaction, it is single reaction.

• If more than one stoichiometric equation represent the observed

changes, then more than one kinetic expression is needed to follow the
changing composition of all reaction components, it is multiple
reactions.

Multiple reactions may be classified as:

• series reactions
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parallel reactions

complicated schemes

Here, reaction proceeds in parallel with respect to B, but in series with

respect to A, R, and S.
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Elementary and Nonelementary Reactions

For a single reaction with a stoichiometric equation :

the rate of disappearance of A is:

𝒎𝒐𝒍
−𝒓𝑨 = 𝐤 𝑪𝑨𝑪𝑩,
𝒎𝟑.𝒔

• Reactions in which the rate equation corresponds to a stoichiometric

equation are called elementary reactions.

• When no direct correspondence between stoichiometry and

rate, then we have nonelementary reactions.
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An example of a nonelementary reaction is,

• Explained by assuming that the observed single reaction is a

sequence of elementary reactions.
• Only a single reaction is observed rather than two or more
elementary reactions since the intermediates formed is very small
and can not be detected.

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Molecularity and Order of Reaction

• The molecularity of an elementary reaction is the number of
molecules involved in the reaction.

• It have the values of one, two, or three.

• The rate of reaction involving A, B, . . . , D, can be approximated as:

−𝒓𝑨 = 𝐤𝑪𝒂𝑨𝑪𝒃𝑩 … … … … 𝑪𝒅𝑫

𝒏 = 𝒂 + 𝒃 + 𝒄 + ⋯+ 𝒅
a, b, . . . , d are not necessarily related to the stoichiometric coefficients.
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The powers to which the concentrations are raised is the order of the
reaction.
−𝒓𝑨 = 𝐤𝑪𝒂𝑨𝑪𝒃𝑩 … … … … 𝑪𝒅𝑫

ath order with respect to A

bth order with respect to B
nth order overall
Since the order refers to the empirically found rate expression, it can
have a fractional value and need not be an integer.
However, molecularity of a reaction must be an integer because it refers
to the mechanism of the reaction, and can only apply to an elementary
reaction. Dr. Enshirah Da'na 13

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Rate Constant k
When the rate expression for a homogeneous chemical reaction is
written in the form of:

−𝒓𝑨 = 𝐤𝑪𝒂𝑨𝑪𝒃𝑩 … … … … 𝑪𝒅𝑫

the dimensions of the rate constant k for the nth-order reaction are:

𝑻𝒊𝒎𝒆 7𝟏 𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝟏7𝒏

which for a first-order reaction becomes simply:

𝑻𝒊𝒎𝒆 7𝟏
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Representation of an Elementary Reaction

In expressing a rate partial pressure can be used:
−𝒓𝑨 = 𝐤𝒑𝒂𝑨𝒑𝒃𝑩 … … … … 𝒑𝒅𝑫
This will not affect order of reaction, only the rate constant k.
𝒌𝟏
For example, 𝟐𝑨 → 𝟐𝑹
The rate of reaction is: −𝒓𝑨 = 𝒓𝑹 = 𝒌𝟏 𝑪𝟐
𝑨

It would not be proper to write it as:

𝒌𝟏
𝑨→ 𝑹
−𝒓𝑨 = 𝒓𝑹 = 𝒌𝟏 𝑪𝑨
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• We must distinguish between the equation that represents the

elementary reaction and the many possible representations of the
stoichiometry.

• It may be necessary to specify the component in the reaction to

which the rate constant is referred. For example:
𝑩 + 𝟐𝑫→ 𝟑𝑻
−𝒓𝑩 = 𝒌𝑩𝑪𝑩𝑪𝟐𝑫
−𝒓𝑫 = 𝒌𝑫𝑪𝑩𝑪𝟐𝑫
𝒓𝑻 = 𝒌𝑻 𝑪𝑩𝑪𝟐𝑫

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From stoichiometry:
𝟏 𝟏
−𝒓𝑩 = − 𝒓𝑫 = 𝒓𝑻
𝟐 𝟑
hence,
𝟏 𝟏
𝒌𝑩 = 𝒌𝑫 = 𝒌𝑻
𝟐 𝟑

v write the stoichiometric equation, rate expression, and give the units
of the rate constant.

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Representation of a Nonelementary Reaction

In none elementary rxn stoichiometry does not match its kinetics.

Stoichiometry: 𝑵𝟐 + 𝟑𝑯𝟐 ↔𝟐𝑵𝑯𝟑

Rate: 𝑵𝟐 𝑯𝟐 𝟑/𝟐 𝑵𝑯𝟑

𝒓𝑵𝑯𝟑 = 𝒌𝟏 − 𝒌𝟐
𝑵𝑯𝟑 𝟐 𝑯𝟐 𝟑/𝟐

We must develop a multistep rxn model to explain the kinetics.

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Kinetic Models for Nonelementary Reactions

• Assume a sequence of elementary rxns is occurring but we cannot
observe the intermediates because they present in very small quantities.
• We observe only the initial reactants and final products, which appears
to be a single rxn.
• If the kinetics of rxn is nonelementary, assume a series of elementary
steps :
𝑨𝟐 + 𝑩𝟐 ↔𝟐𝑨𝑩
𝑨𝟐 ↔𝟐𝑨∗ * refers to intermediates
𝑨∗ + 𝑩𝟐 ↔𝑨𝑩 + 𝑩∗

𝑨∗ + 𝑩∗ ↔𝑨𝑩
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Types of intermediates
Free Radicals.
Free atoms or stable molecules that contain unpaired electrons.
They are unstable and highly reactive, such as:

Ions and Polar Substances.

Molecules. 𝑨→𝑹→𝑺
• These are treated as multiple rxns.
• Intermediate R is highly reactive, and its mean lifetime is very small
and its concentration in the reacting mixture is too small to measure.
• R is reactive intermediate. Dr. Enshirah Da'na
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Transition Complexes.
Collisions between reactant molecules result in unstable forms of
molecules which can then either decompose to give products, or by
further collisions return to molecules in the normal state.
• Such unstable forms are called transition complexes.

Nonchain Reactions.
Intermediate is formed in the first rxn and then disappears as it reacts
further to give the product.
𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔→ 𝑰𝒏𝒕𝒆𝒓𝒎𝒆𝒅𝒊𝒂𝒕𝒆𝒔 ∗

𝑰𝒏𝒕𝒆𝒓𝒎𝒆𝒅𝒊𝒂𝒕𝒆𝒔 ∗ →𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
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Chain Reactions.
• Intermediate is formed in a chain initiation step:
𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔→ 𝒊𝒏𝒕𝒆𝒓𝒎𝒆𝒅𝒊𝒂𝒕𝒆𝒔 ∗
• It then combines with reactant to form product and more intermediate
in chain propagation step.
𝒊𝒏𝒕𝒆𝒓𝒎𝒆𝒅𝒊𝒂𝒕𝒆𝒔 ∗ + 𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔→ 𝒊𝒏𝒕𝒆𝒓𝒎𝒆𝒅𝒊𝒂𝒕𝒆𝒔 ∗ + 𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔

• Intermediate is destroyed in the chain termination step.

𝒊𝒏𝒕𝒆𝒓𝒎𝒆𝒅𝒊𝒂𝒕𝒆𝒔 ∗ →𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔
• In propagation step the intermediate is not consumed but acts as
catalyst for the conversion of material.
• Each molecule of intermediate can catalyze a long chain of rxns, before
being finally destroyed.
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1. Free radicals, chain reaction mechanism.

𝑯𝟐 + 𝑩𝒓𝟐 ↔𝟐𝑯𝑩𝒓

𝒌𝟏 𝑯𝟐 𝑩𝒓𝟐 𝟏/𝟐
𝒓𝑯𝑩𝒓 =
𝒌𝟐 + 𝑯𝑩𝒓 / 𝑩𝒓𝟐

Can be explained by the following scheme:

𝑩𝒓𝟐 ↔𝟐𝑩𝒓 • Initiation and termination

𝑩𝒓 • + 𝑯𝟐 ↔𝑯𝑩𝒓 + 𝑯 • Propagation
𝑯 • + 𝑩𝒓𝟐 ↔𝑯𝑩𝒓 + 𝑩𝒓 • Propagation
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2. Molecular intermediates, nonchain mechanism.

𝑬𝒏𝒛𝒚𝒎𝒆
𝑨 𝑹
𝒌 𝑨 𝑬𝟎
𝒓𝑹 = 𝑴G𝑨
𝑴 is constant

Proceed with intermediate (A. enzyme)* as follows:

𝑨 + 𝑬𝒏𝒛𝒚𝒎𝒆↔ 𝑨. 𝑬𝒏𝒛𝒚𝒎𝒆 ∗

𝑨. 𝑬𝒏𝒛𝒚𝒎𝒆 ∗ →𝑹 + 𝑬𝒏𝒛𝒚𝒎𝒆

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3. Transition complex, nonchain mechanism.

𝑨→𝑹 + 𝑺
Exhibits under various conditions first-order, second-order, or
intermediate kinetics.
• 𝑭𝒐𝒓𝒎𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝒆𝒏𝒆𝒓𝒈𝒊𝒛𝒆𝒅 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆
𝑨 + 𝑨→𝑨∗ + 𝑨
• 𝑹𝒆𝒕𝒖𝒓𝒏 𝒕𝒐 𝒔𝒕𝒂𝒃𝒍𝒆 𝒇𝒐𝒓𝒎 𝒃𝒚 𝒄𝒐𝒍𝒍𝒊𝒔𝒊𝒐𝒏
𝑨∗ + 𝑨→𝑨 + 𝑨
• 𝑺𝒑𝒐𝒏𝒕𝒂𝒏𝒆𝒐𝒖𝒔 𝒅𝒆𝒄𝒐𝒎𝒑𝒐𝒔𝒊𝒕𝒊𝒐𝒏 𝒊𝒏𝒕𝒐 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔
𝑨∗ →𝑹 + 𝑺
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Testing Kinetic Models

Two problems face the search for the correct mechanism of rxn:
• The rxn may proceed by more than one mechanism, such as free
radical and ionic, with relative rates that change with conditions.
• More than one mechanism can be consistent with kinetic data.

In these elementary rxns two types of intermediates are assumed:

Type 1. An unmeasured intermediate X usually present at small
concentration that its rate of change in the mixture can be zero.

𝒅𝑿
𝑿 is very small ≅𝟎
𝒅𝒕
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Type 2. a homogeneous catalyst of initial concentration Co is present in

two forms, either as free catalyst C or combined to form intermediate X,

𝑪𝟎 = 𝑪 + 𝑿
then assume that either 𝒅𝑿
=𝟎
𝒅𝒕
or intermediate is in equilibrium with its reactants; thus,
𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝑪𝒂𝒕𝒂𝒍𝒚𝒔𝒕 𝑰𝒏𝒕𝒆𝒓𝒎𝒆𝒅𝒊𝒂𝒕𝒆
+ ↔
𝑨 𝑪 𝑿
𝒌𝟏 𝑿
𝑲= =
𝒌𝟐 𝑨 𝑪
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Example 1.

The irreversible rxn: 𝑨 + 𝑩→𝑨𝑩

has been studied kinetically, and the rate of formation of product has been
found to be well correlated by the following rate equation:

𝒓𝑨𝑩 = 𝒌𝑪𝟐𝑩 (1)

What rxn mechanism is suggested by this rate expression if the

chemistry of the rxn suggests that the intermediate consists of an
association of reactant molecules and that a chain rxn does not occur?

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Solution. 𝑨 + 𝑩→𝑨𝑩
If this is an elementary rxn, the rate is: 𝒓𝑨𝑩 = 𝒌𝑪𝟐𝑩 (1)
𝒓𝑨𝑩 = 𝒌𝑪𝑨𝑪𝑩 = 𝒌 𝑨 𝑩 (2)

Since Eqs. 1 and 2 are not the same, rxn is nonelementary.

Model 1.
Assume a two-step reversible scheme:

Intermediate 𝑨∗𝟐
presents in small
amounts.

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which involves four elementary rxs:

𝒌𝟏
𝟐𝑨 → 𝑨∗𝟐 (𝟑)
𝒌𝟐
𝑨∗𝟐 → 𝟐𝑨 (𝟒)
𝒌𝟑
𝑨∗𝟐 + 𝑩 → 𝑨 + 𝑨𝑩 (𝟓)
𝒌𝟒
𝑨 + 𝑨𝑩 → 𝑨∗𝟐 + 𝑩 (𝟔)
k refers to the components disappearing.

𝒓𝑨𝑩 = 𝒌𝟑 𝑨∗𝟐 𝑩 − 𝒌𝟒 𝑨 𝑨𝑩 (𝟕)

𝑨∗𝟐 is very small, replace it by concentrations that can be measured,
such as [A], [B], or [AB]:
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𝟏
𝒓𝑨∗𝟐 = 𝒌 𝑨 𝟐 − 𝒌𝟐 𝑨∗𝟐 − 𝒌𝟑 𝑨∗𝟐 𝑩 + 𝒌𝟒 𝑨 𝑨𝑩 (𝟖)
𝟐 𝟏
Because 𝑨∗𝟐 is extremely small, assume 𝒓𝑨∗𝟐 = 𝟎:
𝟏
𝒌 𝑨 𝟐 − 𝒌𝟐 𝑨∗𝟐 − 𝒌𝟑 𝑨∗𝟐 𝑩 + 𝒌𝟒 𝑨 𝑨𝑩 = 𝟎
𝟐 𝟏
𝟏
𝒌𝟏 𝑨 𝟐 + 𝒌𝟒 𝑨 𝑨𝑩
𝑨∗𝟐 = 𝟐 (𝟗)
𝒌𝟐 + 𝒌𝟑 𝑩
replacing in Eq. 9 in Eq. 7:
𝟏
𝟐 𝒌𝟏 𝑨 𝟐 + 𝒌𝟒 𝑨 𝑨𝑩
𝒓𝑨𝑩 = 𝒌𝟑 𝑩 − 𝒌𝟒 𝑨 𝑨𝑩
𝒌𝟐 + 𝒌𝟑 𝑩
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𝟏
𝟐 𝒌𝟏 𝑨 𝟐 + 𝒌𝟒 𝑨 𝑨𝑩 𝒌𝟐 𝒌𝟒 𝑨 𝑨𝑩 + 𝒌𝟑 𝒌𝟒 𝑩 𝑨 𝑨𝑩
𝒓𝑨𝑩 = 𝒌𝟑 𝑩 −
𝒌𝟐 + 𝒌𝟑 𝑩 𝒌𝟐 + 𝒌𝟑 𝑩
𝟏
𝒌𝟑 𝒌𝟏 𝑩 𝑨 𝟐 + 𝒌𝟑 𝒌𝟒 𝑩 𝑨 𝑨𝑩 𝒌𝟐 𝒌𝟒 𝑨 𝑨𝑩 + 𝒌𝟑 𝒌𝟒 𝑩 𝑨 𝑨𝑩
𝒓𝑨𝑩 = 𝟐 −
𝒌𝟐 + 𝒌𝟑 𝑩 𝒌𝟐 + 𝒌𝟑 𝑩
𝟏
𝒌𝟑 𝒌𝟏 𝑩 𝑨 𝟐 − 𝒌𝟐 𝒌𝟒 𝑨 𝑨𝑩
𝒓𝑨𝑩 = 𝟐 (𝟏𝟎)
𝒌𝟐 + 𝒌𝟑 𝑩

Eq. 10 does not match Eq. 2, check if any of its simplified forms will.

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𝟏
𝒌𝟑 𝒌𝟏 𝑩 𝑨 𝟐 − 𝒌𝟐 𝒌𝟒 𝑨 𝑨𝑩
𝒓𝑨𝑩 = 𝟐 (𝟏𝟎)
𝒌𝟐 + 𝒌𝟑 𝑩
If 𝒌𝟐 , is very small, it reduces to:
𝟏
𝟐 𝒌𝟑 𝒌𝟏 𝑩 𝑨 𝟐 𝟏
𝟐
𝒓𝑨𝑩 = = 𝒌𝟏 𝑨
𝒌𝟑 𝑩 𝟐
If 𝒌𝟒 , is very small,
𝟏 𝒌𝟏 𝒌𝟑
𝒌𝟑 𝒌𝟏 𝑩 𝑨 𝟐 𝑩 𝑨𝟐
𝟐𝒌𝟐
𝒓𝑨𝑩 = 𝟐 =
𝒌𝟐 + 𝒌𝟑 𝑩 𝒌
𝟏+ 𝟑 𝑩
𝒌𝟐
None matches the experimentally found rate. Thus, the hypothesized
mechanism is incorrect, so another needs to be tried.

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Model 2.
𝒓𝑨𝑩 = 𝒌𝑪𝟐𝑩 (1)

𝒌𝟏
𝑩 + 𝑩 → 𝑩∗𝟐 (𝟏𝟏)
𝒌𝟑
𝑩∗𝟐 + 𝑨 → 𝑩 + 𝑨𝑩 (𝟏𝟐)
𝒌𝟒
𝑩 + 𝑨𝑩 → 𝑩∗𝟐 + 𝑨 (𝟏𝟑)

𝒓𝑨𝑩 = 𝒌𝟑 𝑩∗𝟐 𝑨 − 𝒌𝟒 𝑩 𝑨𝑩 (𝟏𝟒)

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𝒓𝑩∗𝟐 = 𝒌𝟏 𝑩 𝟐 − 𝒌𝟑 𝑩∗𝟐 𝑨 + 𝒌𝟒 𝑩 𝑨𝑩 (𝟏𝟓)

𝑩∗𝟐 is extremely small, assume that 𝒓𝑩∗𝟐 = 𝟎 :
𝒌𝟏 𝑩 𝟐 − 𝒌𝟑 𝑩∗𝟐 𝑨 + 𝒌𝟒 𝑩 𝑨𝑩 = 𝟎

𝒌𝟏 𝑩 𝟐 + 𝒌𝟒 𝑩 𝑨𝑩
𝑩∗𝟐 = (𝟏𝟔)
𝒌𝟑 𝑨

when replacing in Eq. 16 in Eq. 14:

𝒌𝟏 𝑩 𝟐 + 𝒌𝟒 𝑩 𝑨𝑩
𝒓𝑨𝑩 = 𝒌𝟑 𝑨 − 𝒌𝟒 𝑩 𝑨𝑩
𝒌𝟑 𝑨
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𝒌𝟏 𝑩 𝟐 + 𝒌𝟒 𝑩 𝑨𝑩
𝒓𝑨𝑩 = 𝒌𝟑 𝑨 − 𝒌𝟒 𝑩 𝑨𝑩
𝒌𝟑 𝑨

𝒓𝑨𝑩 = 𝒌𝟏 𝑩 𝟐 + 𝒌𝟒 𝑩 𝑨𝑩 − 𝒌𝟒 𝑩 𝑨𝑩

𝒓𝑨𝑩 = 𝒌𝟏 𝑩 𝟐

So the mechanism that will match the second order rate equation is:

Dr. Enshirah Da'na 36

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Example 2.
Show that the following scheme:
𝒌𝟏
𝑵𝟐 𝑶 𝟓 →
← 𝑵𝑶𝟐 + 𝑵𝑶∗𝟑
𝒌𝟐

𝒌
𝑵𝑶∗𝟑 →𝟑 𝑶𝟐 + 𝑵𝑶∗
𝒌
𝑵𝑶∗ + 𝑵𝑶∗𝟑 →𝟒 𝟐𝑵𝑶𝟐
Proposed by Ogg (1947) is consistent with and can explain the observed
first-order decomposition of N2O5.

Dr. Enshirah Da'na 37

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From step 2: 𝒓𝑶𝟐 = 𝒌𝟑 𝑵𝑶∗𝟑 (𝟏)

From steps 1 - 3:

𝒓𝑵𝑶∗𝟑 = 𝒌𝟏 𝑵𝟐 𝑶𝟓 − 𝒌𝟐 𝑵𝑶𝟐 𝑵𝑶∗𝟑 − 𝒌𝟑 𝑵𝑶∗𝟑 − 𝒌𝟒 𝑵𝑶∗ 𝑵𝑶∗𝟑 (𝟐)

𝒓𝑵𝑶∗ = 𝒌𝟑 𝑵𝑶∗𝟑 − 𝒌𝟒 𝑵𝑶∗ 𝑵𝑶∗𝟑 = 𝟎 (𝟑)

𝒌𝟑
𝑵𝑶∗ = (𝟒)
𝒌𝟒
(4) In (2):
𝒌𝟑
𝒓𝑵𝑶∗𝟑 = 𝒌𝟏 𝑵𝟐 𝑶𝟓 − 𝒌𝟐 𝑵𝑶𝟐 𝑵𝑶∗𝟑 − 𝒌𝟑 𝑵𝑶∗𝟑 − 𝒌𝟒 𝑵𝑶∗𝟑 (𝟓)
𝒌𝟒 38
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𝒌𝟑
𝒓𝑵𝑶∗𝟑 = 𝒌𝟏 𝑵𝟐 𝑶𝟓 − 𝒌𝟐 𝑵𝑶𝟐 𝑵𝑶∗𝟑 − 𝒌𝟑 𝑵𝑶∗𝟑 − 𝒌𝟒 𝑵𝑶∗𝟑 (𝟓)
𝒌𝟒
𝒓𝑵𝑶∗𝟑 = 𝟎 :
𝒌𝟏 𝑵𝟐 𝑶𝟓 − 𝒌𝟐 𝑵𝑶𝟐 𝑵𝑶∗𝟑 − 𝒌𝟑 𝑵𝑶∗𝟑 − 𝒌𝟑 𝑵𝑶∗𝟑 = 𝟎
𝒌𝟏 𝑵 𝟐 𝑶 𝟓
𝑵𝑶∗𝟑 = (𝟔)
𝒌𝟐 𝑵𝑶𝟐 + 𝟐𝒌𝟑
(6) In (1):
𝒌𝟑 𝒌𝟏 𝑵 𝟐 𝑶 𝟓
𝒓𝑶𝟐 = 𝒌𝟑 𝑵𝑶∗𝟑 = (𝟕)
𝒌𝟐 𝑵𝑶𝟐 + 𝟐𝒌𝟑

Assume 𝒌𝟐 ≪< 𝒌𝟏 :
𝒌𝟏 𝑵 𝟐 𝑶 𝟓
𝒓𝑶𝟐 = (𝟖)
𝟐
Equation 8 is first order in term of 𝑵𝟐 𝑶𝟓 .
Dr. Enshirah Da'na 𝒓𝑶𝟐 = 𝒌𝟑 𝑵𝑶∗𝟑 (𝟏) 39

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Example 3.
Here, a reactant, called the substrate, is converted to product by the
action of an enzyme, a high molecular weight (mw > 10 000) protein-like
substance. An enzyme is highly specific, catalyzing one particular
reaction, or one group of rxns. Thus,
𝑬𝒏𝒛𝒚𝒎𝒆
𝑨 𝑹
Many of these rxns exhibit the following behaviour:
1. A rate proportional to the concentration of enzyme introduced into the
mixture [E0].
2. At low reactant concentration the rate is proportional to the reactant
concentration, [A].
Dr. Enshirah Da'na 40

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3. At high reactant concentration the rate levels off and becomes

independent of reactant concentration.
Propose a mechanism to account for this behavior.
Solution.
Michaelis and Menten (1913) guessed that the rxn proceeded as:

𝑿 = 𝑨. 𝑬𝒏𝒛𝒚𝒎𝒆 ∗

𝑬 = 𝑬𝒏𝒛𝒚𝒎𝒆
Dr. Enshirah Da'na 41

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with the two assumptions:

𝑬𝟎 = 𝑬 + 𝑿 (1)
𝒅𝑿
≅ 𝟎 (𝟐)
𝒅𝒕 𝑿 = 𝑨. 𝑬𝒏𝒛𝒚𝒎𝒆 ∗

First write the rates for the rxn components R:

𝒅𝑹
= 𝒌𝟑 𝑿 (𝟑)
𝒅𝒕
𝒅𝑿
= 𝒌𝟏 𝑨 𝑬 − 𝒌𝟐 𝑿 − 𝒌𝟑 𝑿 = 𝟎 (𝟒)
𝒅𝒕
𝒌𝟏 𝑨 𝑬
𝑿 = (𝟓)
Dr. Enshirah Da'na
𝒌𝟐 + 𝒌𝟑 42

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From Eq. 1 : 𝑬 = 𝑬𝟎 − 𝑿 (6)

Eliminating [E] from Eq. 5 by Eq. 6 gives:
𝒌 𝟏 𝑨 𝑬𝟎 − 𝒌 𝟏 𝑨 𝑿
𝑿 =
𝒌𝟐 + 𝒌𝟑 𝑿 =
𝒌𝟏 𝑨 𝑬
(𝟓)
𝒌𝟐 + 𝒌𝟑
𝒌𝟏 𝑨 𝑿 𝒌 𝟏 𝑨 𝑬𝟎
𝑿 + =
𝒌𝟐 + 𝒌𝟑 𝒌𝟐 + 𝒌𝟑
𝑿 𝒌𝟐 + 𝒌𝟑 + 𝒌𝟏 𝑨 𝑿 𝒌 𝟏 𝑨 𝑬𝟎
=
𝒌𝟐 + 𝒌𝟑 𝒌𝟐 + 𝒌𝟑
𝒌 𝟏 𝑨 𝑬𝟎
𝑿 = (𝟕)
𝒌𝟐 + 𝒌𝟑 + 𝒌𝟏 𝑨
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𝒌 𝟏 𝑨 𝑬𝟎 𝒅𝑹
𝑿 = (𝟕) = 𝒌𝟑 𝑿 (𝟑)
𝒌𝟐 + 𝒌𝟑 + 𝒌𝟏 𝑨 𝒅𝒕

Eq. 7 in Eq. 3:

𝒅𝑹 𝒌 𝟑 𝒌 𝟏 𝑨 𝑬𝟎 𝒌 𝟑 𝑨 𝑬𝟎
= =
𝒅𝒕 𝒌𝟐 + 𝒌𝟑 + 𝒌𝟏 𝑨 𝑴 + 𝑨

𝒌𝟐 + 𝒌𝟑
𝑴 =
𝒌𝟏
𝑴 Is called the Michaelis constant.
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By comparing with experiment, we see that this equation fits the three
reported facts:

𝒅𝑹 𝒌𝟑 𝑨 𝑬𝟎
=
𝒅𝒕 𝑴 + 𝑨

Dr. Enshirah Da'na 45

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TEMPERATURE-DEPENDENT TERM OF A RATE EQUATION

Temperature Dependency from Arrhenius' Law
For elementary rxns, the rate expression can be written as a product of a
temperature-dependent term and a composition-dependent term,
𝒓𝒊 = 𝒇𝟏 𝑻𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 . 𝒇𝟐 𝒄𝒐𝒎𝒑𝒐𝒔𝒊𝒕𝒊𝒐𝒏
𝒓𝒊 = 𝒌. 𝒇𝟐 𝒄𝒐𝒎𝒑𝒐𝒔𝒊𝒕𝒊𝒐𝒏
1𝑬R
𝒌 = 𝒌𝟎 𝒆 𝑹𝑻

𝒌𝟎 is pre-exponential factor and E is activation energy of rxn.

Arrhenius' law indicates that:
𝒓𝟐 𝒌𝟐 𝑬 𝟏 𝟏
𝒍𝒏 = 𝒍𝒏 = −
𝒓𝟏 𝒌𝟏 𝑹 𝑻𝟏 𝑻𝟐 46
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Activation Energy and Temperature Dependency

1. From Arrhenius' law a plot of Ink vs. 1/T gives a straight line,
with large slope for large E and small slope for small E.
2. Rxns with high activation energies are very temperature-sensitive;
rxns with low activation energies are temperature-insensitive.

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3. Any given rxn is much more T-sensitive at a low T than at a high T.

4. From the Arrhenius law, the value of the frequency factor 𝒌𝟎 , does
not affect the T sensitivity.

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Example 3.
Milk is pasteurized if it is heated to 63°C for 30 min, but if it is heated to
74°C it only needs 15 s for the same result. Find the activation energy of
this sterilization process.
Solution. t1 = 30 min at a T1 = 336 K
t2 = 15 sec at a T2 = 347 K
rate is inversely proportional to the reaction time, so
𝒓𝟐 𝒕𝟏 𝑬 𝟏 𝟏
𝒍𝒏 = 𝒍𝒏 = −
𝒓𝟏 𝒕𝟐 𝑹 𝑻𝟏 𝑻𝟐
𝟑𝟎 𝑬 𝟏 𝟏
𝒍𝒏 = −
𝟎. 𝟐𝟓 𝟖. 𝟑𝟏𝟒 𝟑𝟑𝟔 𝟑𝟒𝟕
Dr. Enshirah Da'na 𝑬 = 𝟒𝟐𝟐𝟎𝟎𝟎 𝑱/𝒎𝒐𝒍 49

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SEARCHING FOR A MECHANISM

• Three areas of rxn: stoichiometry, kinetics, and mechanism.
• Stoichiometry is studied first, then kinetics, then mechanism.
Clues used in such experimentation:
1. Stoichiometry can tell whether we have a single rxn or not.
a complicated stoichiometry 𝑨→𝟏. 𝟒𝟓𝑹 + 𝑺 or one that changes with
rxn conditions or extent of rxn is clear evidence of multiple rxns.

2. Stoichiometry suggest if a single rxn is elementary or not because no

elementary rxns with molecularity greater than three.

Thus, the rxn 𝑵𝟐 + 𝟑𝑯𝟐 →𝟐𝑵𝑯𝟑 is not elementary.

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3. A comparison of the stoichiometric equation with the experimental

kinetic expression can suggest if or not we elementary rxn.
4. A large difference in the order of magnitude between the experimental
frequency factor of rxn and that calculated from theory suggest a
nonelementary rxn.
5. Consider two alternative paths for a simple reversible rxn. If one of
these paths is preferred for the forward rxn, the same path must also be
preferred for the reverse rxn. This is called the principle of micro
reversibility.
• For example, the forward rxn of 𝟐𝑵𝑯𝟑 ↔𝑵𝟐 + 𝟑𝑯𝟐
• This could be an elementary biomolecular rxn with two molecules of
𝑵𝑯𝟑 combining to yield directly the four product molecules.
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• From the principle of micro reversibility the reverse rxn have to be

an elementary rxn involving the direct combination of three
molecules of hydrogen with one of nitrogen.
• This process is rejected (no elementary rxns with molecularity
greater than three), the bimolecular forward mechanism must be
rejected.
6. The principle of micro reversibility also indicates that changes
involving bond rupture, molecular syntheses, or splitting are likely to
occur one at a time, each being an elementary step in the mechanism.

Thus, the simultaneous splitting of the complex into the four product
molecules in the rxn 𝟐𝑵𝑯𝟑 → 𝑵𝑯𝟑 ∗𝟐 →𝑵𝟐 + 𝟑𝑯𝟐 is very unlikely.

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7. For multiple rxns a change in the observed activation energy with

temperature indicates a shift in the controlling mechanism of rxn.

for an increase in temperature

Eobs rises for rxns in parallel
and falls for rexns in series.

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