MATE40005 Kinetics Notes (Andrew Cairns)

Dwayne Nobleza
March 13, 2025

Contents
1 Formula booklet 2

2 Introduction 3

3 Definition of Rate 3
3.1 Rate equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2 Measuring Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3 Further Rate Laws . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.4 Determining Reaction Orders . . . . . . . . . . . . . . . . . . . . 9

4 Modelling Rates 10
4.1 The Steady State Approximation . . . . . . . . . . . . . . . . . . 10
4.2 Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.3 Enzymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.4 Rates in Solution: . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.5 Molecular Motion in Liquids . . . . . . . . . . . . . . . . . . . . . 13

5 Activation Energy 14
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1
1 Formula booklet
Assume some derivations required

• Rate = (ν) = −( a1 ) d[A] 1 d[B] 1 d[C] 1 d[D]

dt = −( b ) dt = ( c ) dt = ( d ) dt

• Rate = 1 dξ
V dt

• Rate = k[A]x [B]y

[Activated Complex]
• K= [Reactants]

• f = e− RT
Ea

1
• A = σ( 8kπµ
BT 2
) NA2

• µ= mA mB
mA +mB

Ea − kEaT
• k = Ae− RT ⇐⇒ k = Ae B ⇐⇒ ln kk12 = − ERa ( T11 − 1
T2 )

• log II0t = ε(λ)lc

• J = −D dC
dx

• J= m
At
−Em
• Rj = R0 e kB T
Ea − kEaT Qd
• D = D0 e− RT ⇐⇒ D = D0 e B ⇐⇒ D = D0 e− RT

2
2 Introduction
Chemical reaction kinetics deals with the rates of chemical processes. The huge
variety of chemical species, types of reaction, and the accompanying potential
energy surfaces involved means that the timescale over which chemical reactions
occur covers many orders of magnitude, from very slow reactions, such as iron
rusting, to extremely fast reactions such as the electron transfer processes in-
volved in many biological systems or the combustion reactions in flames.

An important point is that many reactions that are written as a single reac-
tion equation are in actual fact, a series of elementary steps. Therefore, study
of the kinetics of a chemical reaction is usually carried out with one or both of
two main goals in mind:

• Analysis of the sequence of elementary steps giving rise to the overall

reaction. i.e. the reaction mechanism.
• Determination of the absolute rate of the reaction and/or its individual
elementary steps.

The aim of this course is to show you how these two goals may be achieved. El-
ementary processes involve a transition between two atomic or molecular states
separated by a potential barrier. The potential barrier is known as the activa-
tion energy; for low activation energies, the energy of the reactants will generally
be high enough to surmount the barrier and move over to products and the re-
action will be fast. However, when the barrier is high, only a few reactants will
have sufficient energy, and the reaction will be much slower. The presence of a
potential barrier to reaction is also the source of the temperature dependence
of reaction rates. To summarise:
• Thermodynamics is about the possibility of a reaction (whether or not
a process can occur, based on free energy).

• Kinetics is about the process of the reaction (how fast or slow it occurs
and overcoming energy barriers).

3 Definition of Rate
A rate of chemical reaction is defined as change in concentration of some
species with time e.g moldm−3 s−1

For a simple process A → B

Rate = = − d[A]
dt =
d[B]
dt

It is an experimental procedure and cannot be calculated from first principles.

3
 Factors affecting the rate of reaction
• Temperature
• Use of a catalyst
• Concentration of species present

• Surface area
• Frequency of collisions etc

3.1 Rate equation

For a common reaction aA + bB → cC + dD
Rate = ν = −( a1 ) d[A] 1 d[B] 1 d[C] 1 d[D]
dt = −( b ) dt = ( c ) dt = ( d ) dt (1)

For the reactions we will be dealing with, assume that there is no change in
volume of the system. A unique rate of reaction could be defined based on the
n −n
extent of the reaction ξ = J vJ J,0 , nj amount of species J present, vj is the
stoichiometric number of species J
1 dξ
∴ Rate = V dt

1 d[J]
It follows that Rate = vJ dt

Kinetic data in this course is presented as concentrations in solution or partial

pressures, and so we can assume there is no change in volume. Example

N2(g) + 3H2(g) → 2N H3(g) find the relative disappearance of N2 and H2 , given

that d[NdtH3 ] = 8 × 10−6 M s−1

Rate = − d[N 2] 1 d[H2 ] 1 d[N H3 ]

dt = −( 3 ) dt = ( 2 ) dt

∴ − d[N 2] 1 d[N H3 ]
dt = ( 2 ) dt
∴ − 12 × 8 × 10−6 M s−1 = −4 × 10−6 M s−1 , with respect to N2(g)

∴ −( 13 ) d[H 2] 1 d[N H3 ]
dt = ( 2 ) dt

d[H2 ]
∴ dt = − 23 × 8 × 10−6 = −1.2 × 10−5 M s−1
As concentration decreases, the probability of two reactants with sufficient ther-
mal energy colliding to overcome the activation energy will decrease. And a rate
law is an equation that expresses the rate of reaction as a function of concen-
trations of the species present in the overall chemical equation for the reaction
at some time.
For any reaction, the Rate Law will usually be represented in terms of a con-
stant times a function of the concentrations of reactants.

4
Rate = k[A]x [B]y (3) x + y is the sum of the partial orders which will give the
overall order.

Consider the reaction 2A + B → C + 2D

d[B]
Rate = dt = k[A]x [B]y
d[A]
∴ dt = k ′ [A]x [B]y

Since you know the ratio of rates of A and B

d[B]
∴ dt = ( 21 ) d[A]
dt ⇐⇒ k ′ = 2k
I.e, A dissapears twice as fast as B. The rate constant we should report is k, the
correctly normalised rate.

However, some rate laws are more complex which usually contains more than
one rate constant and non trivial dependence on the concentrations of the reac-
tants.

e.g
1
k[H2 ][Br2 ] 2
H2 + Br2 → 2HBr Rate = 1+k′ [HBr]/[Br2 ]

5
3.2 Measuring Rates

Techniques How it Works Advantages

Spectrophotometry Measures how much a chemical sub- Non-invasive, precise, and can continu-
stance absorbs light by quantifying the ously monitor the reaction.
intensity as a function of wavelength
Conductometry Measures the electrical conductivity of Simple and provides real-time monitor-
a solution ing without adding additional chemi-
cals.
Titration : Involves adding a reactant of known Accurate and ideal for reactions that
concentration to the reaction mixture are too slow for other methods
until a specified reaction occurs, indi-
cated by a color change or an electrode
potential change.
Gas Volumetry Measures the volume of gas produced Direct and easy to visualize the
or consumed in a reaction. progress of the reaction.
Gravimetry Measures the change in mass of the re- Direct and doesn’t require complex
action system equipment.
Pressure Measure- : Monitors the pressure change in a Good for fast reactions and provides
ment closed system where gases are involved. continuous data.
Chromatography Separates the components of a mixture Highly sensitive and provides detailed
and measures their individual concen- information about multiple components
trations. simultaneously.
Stopped-flow tech- Rapidly mixes reactants and measures Can provide insights into reaction
niques the reaction progress at very short time mechanisms and fast processes.
scales.

Table 1: Comparison of Various Techniques

Usually, The reaction mechanism is made up of a series of intermediate reactions

that are elementary. The rate law for an elementary reaction can be deduced
from chemical equation by inspection.
1st : A → products =⇒ Rate = k[A]

2nd : A + B → products =⇒ Rate = k[A][B]

3rd : A + B + C → products Rate = k[A][B][C]

In some cases the rate law does happen to reflect the reaction stoichiometry.
H2 + I2 → 2HI
Rate = k[H2 ][I2 ]

6
This might suggest this reaction proceeds by a single elementary step How-
ever, the reaction mechanism might include intermediates that do not
appear in the overall equation and will describe any transition states
Key rules:
• The elementary steps must add up to give overall balanced equation for
reaction.
• The rate law for the rate determining step must agree with the experi-
mentally derived rate law
• Intermediates may appear in the reaction mechanism. but not in the
overall rate law

• The slowest elementary step is called the rate determining step.

3.3 Further Rate Laws

Molecularity is defined as the number of species involved in the individual molec-
ular process in which the reactants are transferred to products.
e.g Unimolecular =⇒ A → P roducts Bimolecular =⇒ A + B → P roducts
Also you know this from A-Level but the units of the rate constant depends on
the order of reaction. Just do dimensional analysis.
Integrated Rate Laws:
• Predict the concentration of a species at any time after the start of the
reaction
• Help find the rate constant and order of reaction

e.g

Reaction Order Differential Form Integrated Form

A→P 0th − d[A]
dt = k [A] = [A]0 − kt
A→P 1st − d[A]
dt = k[A] ln[A] = ln[A]0 − kt
1 d[A] 1 1
A+A→P 2nd −( 2 ) dt = k[A]2 [A] = [A]0 + kt
A+B →P 2nd − d[A]
dt = k[A][B] kt = 1 [B]0 [A]
[B]0 −[A]0 ln [A]0 [B]

Table 2: Integrated form of all orders

7
 0th Order
− k1 d[A] = dt
R [A] 1
Rt
− [A]0 k
d[A] = 0
dt

− [A]
k +
[A]0
k =t

∴ [A] = [A]0 − kt
First Order
1
− [A] d[A] = kdt
RA 1
Rt
∴ [A]0
− [A] d[A] = 0
kdt

∴ −ln[A] + ln[A]0 = kt

∴ ln[A] = ln[A]0 − kt
Second order case X

−( 12 ) d[A]
dt = k[A]
2

1
[A]2 d[A] = 2kdt
R [A] 1
Rt
∴ [A]0 [A]2
d[A] = 0
2kdt

2 2
∴ − [A] + [A]0 = 2kt

1 1
∴ [A] = [A]0 + kt

Second Order Case Y

You just have to remember it: it’s way too complicated to try and integrate.
1 [B]0 [A]
[B]0 −[A]0 ln [A]0 [B]

For a first order reactant, there is a constant half life property. It is independent
of concentration and is the same length of time throughout.
ln2
t 12 = k

E.g carbon-14 is a naturally occurring isotope of carbon formed by cosmic radi-

ation forming neutrons that collide with nitrogen-14. Radioactive decay follows
first order kinetics and the half life of C 14 is 5700 years. By finding the number
of half lives elapsed based on the ratio of C 14 compared to that in living things
we can determine the age of fossils.
For second order reactants, as concentration decreases, the half life of second
order reactant increases

8
For zero order kinetics, the rate is independent of the concentration of reactants
∴ Rate = k
They are usually found where the surface area of a heterogeneous catalyst is the
main factor controlling the rate.

3.4 Determining Reaction Orders

There are four methods to determine the reaction orders, these include:
• Using Integrated Rate Equations
• Using Fractional lifetimes
• Differential Methods
• Isolation Methods
Using Integrated Rate Equations Refer to the table, take logarithms and
arrange into the form y = mx + c We can always plot a straight-line graph for
for 0th , 1st , 2nd order reactions to find the rate constant. However,
• This method is not sufficiently accurate to distinguish between first and
second order reactants
• It is essential that the reaction is measured over several half lives
Using fractional lifetimes This is the same method as finding halflives
As before, the reaction order is assumed, and data is plotted according to the
corresponding rate law. The procedure is repeated until a line of best fit is
found. It is essential that the reaction is measured for several fractional life-
times.
Differential Methods Requires less guessing than the previous methods, but sig-
nificantly more work.
For a given reaction, the rate is determined as the reaction proceeds. For any
reaction: ν = k[A]n
∴ lnν = nln[A] + logk
This method is the most useful if lots of data is available but is very difficult
and time consuming.
Initial rates are more reliable as the initial concentrations are generally known:
e.g A + B → P roducts
Rate at(t = 0) = k[A]x0 [B]y0
Isolation Methods If one reactant is in great excess, we can assume that its con-
centration remains essentially constant throughout the course of a reaction.
Consider the reaction A + B → P
If the concentration of A is 1000 times greater than B, B will change by 0.1
percent.
This greatly simplifies the rate law since the (constant) concentrations of all re-
actants present in large excess may be combined with the rate constant to yield a
single effective rate constant. Rate = k[A]a [B]b ∼ k[A]a0 [B]b0 = kef f [A]a with kef f [B]b0

9
4 Modelling Rates
4.1 The Steady State Approximation
Examples of Reaction Mechanisms

• The Activated Complex Theory (ACT

• Enzyme Catalysis - The Michaelis0Menten Equation (MM)
• Diffusion vs Activation Control in Solution

• Linear Chain Reactions

Rate Determining Step - Slowest and ost crucial gateway for the formation of
products in a multistep reaction. Another (simpler) way of considering this
reaction is to assume that the first step is a pre-equilibrium (i.e k1 >>>
k2 . When considering a pre-equilibrium, we assume the pertubation of the
equilibrium by the second reaction is negligible, and the rates of forward and
backward reaction are equal.
2N O ⇌ N2 O2 + O2 → 2N O2
∴ Rate = ( 12 ) d[NdtO2 ] = k2 [N2 O2 ][O2 ]
When an equilibrium is reached:
[N2 O2 ]
K= [N O]2 so [N2 O2 ] = K[N O]2

∴ Rate = k2 K[N O]2 [O2 ]

As before. Note the rate is defined as ( 12 ) d[NdtO2 ]

Activated Theory Complex In collision theory, we assume no definitive structure
or composition. Activated theory complex - Involves the formation of an
’activated species’ which has a definite composition and for which the structure
is approximately known.
They fall under these conditions
• Pass on to form the products
• Collapse back to the reactants
IT IS NOT a reaction intermediate that can be isolated or studied.
We can assume that the transition state forms in equilibrium with the reactants.
Reactants ⇌ P roducts
[Activated Complex]
∴K= [Reactants]

∴ Rate ∝ [Activated Complex] and Rate ∝ K[Reactants]

10
So, the rate constant(k) is proportional to the equilibrium constant (K) for the
formation of the activated complex.
And for whatever reason, we wish to link this with thermodynamics, most no-
tably, the Gibb’s Free Energy
∆G
K = e− RT
(∆H−T ∆S) ∆S ∆H
∴ k ∝ e− RT ∝e R .e RT
This expression has the form of the Arrhenius expression and we can identify the
Enthalpy of activation (∆H) with the activation energy (Ea ), andentropy of activation, ∆Swiththepre
ACT is based on statistical thermodynamics

ACT has orientation requirements which constitutes to the ”Ac-

tivated” part of the Activated Complex Theory. These orienta-
tion requirements are governed by the entropy of activation. i.e
for a substrate molecule approaching an enzyme, entropy of ac-
tivation will be strongly negative which indicates feasibility.

Even for a complex series of events (not only a collisional en-

counter in the gas phase) displays Arrhenius-like behaviour and
that the concept of activation energy is applicable.

4.2 Catalysis
Catalyst - Compound that lowers Ea by providing an alternative reaction path-
way, therefore rate increases without being consumed.
There are two types of catalysts:
• Homogeneous - Same phase as the reactants (i.e dissoled in the same
solvent)
• Heterogeneous - A catalyst in a different phase (i.e a solid in a gas phase
reaction)
Key note: Homogeneous catalysts are easier to control. Examples of homogeneous catalysts:

• Acid catalysts
• Organometallic catalysts
• Enzymatic catalysts

4.3 Enzymes
The definition of an enzyme: A complex protein structure that catalyses
a chemical reaction by lowering the activation energy. They are specific to a
particular reaction or a set of very closely related reactions.
Enzyme kinetics:

11
 Ratemax [S]
Michaelis-Menten equation: Rate = KM +[S] =⇒ Ratemax = kcat [E]0

• Km is the Michaelis constant, Ratemax is the maximum rate, and kcat is

known as the turnover number (representing the number of molecules that
each enzyme molecule can convert into products per second.
Prof. Maud Menten showed the rate of an enzyme-catalyzed reaction is pro-
portional to the amount of the enzyme-substrate complex. The mechanism for
applying the steady state approximation to enzymes gives us
E + S ⇌kk1−1 ES →k2 P + E
Applying the steady state approximation to this equation will give us:
d[ES]
dt = 0 = k1 [E][S] − k−1 [ES] − k2 [ES]
k1 [E]0 [S]
∴ [ES] = k−1 +k2 +k1 [S]

d[P ] k2 [E]0 [S]

Therefore, overall rate: Rate = dt = k2 [ES] = km +[S]

From this, we can deduce that the rate of enzymolysis depends linearly on
enzyme concentration, as noted before.
However, the rate dependence on [S] is more complex, but simplifies in the
following conditions:
• When [S] >> KM then Rate = k2 [E]0 and the overall rate is independent
of substrate concentration. Under these conditions the rate of reaction is a
maximum (Rate = Ratemax ) and the enzyme is saturated with substrate.
• When [S] << KM the reaction rate is Rate = ( KkM
2
)[E]0 [S] and the reac-
tion is first order in both [E]0 and [S]

4.4 Rates in Solution:

Rate determining step (gas phase) - slowest step in a multistep reaction
Rate determining step(solution) - Describes the distinction between diffusion
control and activation control.
Assume the reaction between solute molecules (A+B) occurs by:
• Step 1: A + B drifting into the vicinity of each other by diffusion, the
rate being proportional to their concentrations i.e Rate of formation of
AB = kd [A][B]
• Step 2: The AB species can stay together for some time, but may also
break apart, so we must also consider AB → A+B
Rate of loss of AB = k−d [AB], For now assume this is first-order in AB.
• Step 3: Competing with this process is the reaction between A and B. Ei-
ther Sufficient energy needed to react, or this could come from the thermal
motion of the solvent or can assume also first-order (pseudo first-order) as
solvent is involved but in huge excess.

12
Using the steady state approximation, we can derive the rate law for the forma-
tion of products:
Rate of formation of products = ka [AB]
kd [A][B]
[AB] = ka +k−d

ka kd [A][B]
∴ Rate = ka [AB] = ka +k−d

We can distinguish between two limits:

The rate of reaction is much faster than the rate at which AB breaks up. In
this case, ka >> k−d , thus we can neglect k−d in the denominator of the last
expression. The ka in the numerator and denominator cancel; thus, Rate of
formation of products = kd [A][B] - also known as diffusion-controlled limit.
The rate of the reaction is controlled by the rate at which the reactants diffuse
through the solvent, after this the reaction is so fast they will certainly go onto
form products - rather than diffuse apart. Radical and atom recombination
reactions are often diffusion-controlled because the combination of radicals in-
volves very little activation energy. If the reaction of the encounter pair is
much slower than the rate at which the unreacted molecules sperate
i.e the energy required to break up AB is small. The rate determin-
ing step is whether they have enough energy to react.
Here we can ee ka << k−d , thus
ka kd
Rate = k−d [A][B] = ka K[A][B]

In this limit, the reaction is said to be activation-controlled because this limit is

likely to occur when a substantial activation energy is involved in the reaction
AB → P . In the activation-controlled limit the reaction proceeds at a rate that
depends on the equilibrium concentration of encounter pairs and the rate at
which energy accumulates in these pairs from the surrounding solvent.

4.5 Molecular Motion in Liquids

Detailed analysis of the rates of diffusion of molecules in liquids shows that the
rate constant kd is related to the coefficient of viscosity, η of the medium
by:
8RT
kd = 3η

i.e the higher the viscosity of the solvent the smaller the diffusional rate con-
stant, and therefore the slower the rate of diffusion-controlled reaction.

• In liquids, molecular motion can be considered as a series of short steps of

constaly changing direction. The process of random jostling in liquids is
called diffusion and molecular motion occurs as a so-called random walk.

13
 • If there is initially a concentration gradient, the rate at which the molecules
spread out to make a homogenous solution is proportional to the concen-
tration gradient

Rate of diffusion = D × concentration gradient

D represents the diffusion coefficient (large value means rapid diffusion).

D is used to describe the probable location of a given molecule in a given solvent.

The net distance travelled is given by the the root-mean squared distance
1 1 1 1
e.g 1D: < x2 > 2 = (2Dt) 2 in 3D: < r2 > 2 = (6Dt) 2
Now we can assume there is an Arrhenius temperature dependence as increasing
the temperature increases the speed of each step
Ea
∴ D ∝ exp(− RT )
Diffusion is also related to viscosity (η) and one would expect such a high dif-
fusion coefficient for low viscosity fluids:
Ea
η ∝ exp( RT )

5 Activation Energy
5.1 Introduction
Arrhenius and van’t Hoff studied in detail the energetics of reactions with the
suggestion that molecules in the system existed in equilibrium with activated
molecules - and it was the activated molecules that reacted.
Collision theory - Reaction only occurs if two molecules collide with a certain
minimum kinetic energy along their line of approach. Collision frequency, the

Figure 1: Activated Complex: cluster of atoms close to the potential energy

maximum that may lead to formation of products. Transition state - cluster of
atoms at the potential energy maximum that any further distortion will lead to
the formation of products. Activation energy - Minimum kinetic energy that
reactants must have in order to form products.

14
rate of collisions between species A and B, is proportional to both their concen-
trations: if the concentration of B is doubled, then the rate at which A molecuels
collide with B molecules is doubled, and if the concentration of A is doubled,
the the rate a twhich B molecules colide with A molecules is also doubled.
It follows that the collision frequency of A and B molecules is directly propor-
tional to the concentrations of A and B, and we can write:
Collision f requency ∝ [A][B]
Molecules that approach with less than a kinetic energy Ea will behave elasti-
cally.
Overall, small fractions of molecules in the gas phase have very high speeds.
Reaction rates are very temperature dependent as kinetic energy increases as
the square of the speed.
i.e for a body of mass m moving at a speed v, the kinetic energy is: Ek = 12 mv 2 .
So, we expect taht, at higher temperatures, a larger fraction of molecules will
have a speed and kinetic energy that exceed the minimum values required for
collisions that lead to formation of products.
Ea
f = e− RT
This fraction increases from 0, when T = 0 to 1 when T is infinite.
At this stage we can conclude that the rate of reaction, which is proportional
to the collision frequency multiplied by the fraction of successful collisions, is
Ea
Rate ∝ [A][B]exp(− RT )
And by comparing this, compare this expression with a second-order rate law,
Rate = k[A][B]
Ea
Ea
It follows that k ∝ exp(− RT or k = Ae− RT
Collision theory therefore suggests that:
• The pre-exponential factor, A, is the constant of proportionality between
the concentrations of the reactants and the rate at which the reactant
molecules collide.
• The activation energy, Ea is the minimum kinetic energy required for a
collision to result in reaction.

A is calculated from kinetic theory of gases:

1
A = σ( 8kπµ
BT 2
) , where µ = mA mB
mA +mB

Once, the activation energy of a reaction is known, it is a simple matter to

predict the value of a rate constant k(T2 ) at a temperature T2 from its value
k(T1 ) at another temperature T1 . To do so, we write:
ln kk21 = − ERa ( T11 − 1
T2 )

15
It is often found that the experimental value of A is smaller than that calculated
from the kinetic theory. One explanation is that not only must the molecules
collide with sufficient kinetic energy, but they must also come together in a
sufficient relative orientation. It follows that the reaction rate is proportional
to the porbability that the encounter occurs in the correct relative orientation.
The pre-exponential factor A should therefore include a steric factor, P, which
usually lies between 0 and 1.
When p¿1, this is because the reaction proceeds via a ”harpooning mechanism”.
This is based on a model of the reaction where the K atom approaches the Br2
molecules, and when the two are close enough an electron (the harpoon) flips
across to the Br2 molecule. X-rays, high energy electrons and α particles are

Figure 2: Under its influence the ions move together the reaction takes place,
and KBr and Br emerge. The harpoon extends the cross-section for the reactive
encounter and we would greatly underestimate the reaction rate if we used for
the collision cross-section the value for simple mechanical contact between K
and Br2

typical high energy radiation types. We know (instinctively) that their effect on
molecules is drastic, often giving rise to electrons, ions, highly excited molecules
and radicals. Their energies are far higher than normally encountered in kinetics
and (thankfully) they will not be considered in this course.
Photochemical activation Einstein’s law of photochemical equivalence - ’one
quantum activates one molecule’.
∴ log II0t = ϵ(λ)cl

16