Module Code:CHE2141

Module Title: CHEMICAL THERMODYNAMICS AND KINETICS

Lecturers: Dr.Wellars Utetiwabo and

Mr Joseph Nkundumukiza

Academic year: 2021-2022

1
 ORGANIZATION OF THE MODULE
• Chemical Thermodynamics will be taught by
Mr Joseph Nkundumukiza (0788689972)

while
• Chemical kinetics will be taught by
Dr.Wellars Utetiwabo (0788832080).

2
Chemical kinetics is the branch of physical chemistry that is
concerned with understanding the rates of chemical reactions.
It provides evidence for the mechanism of chemical reactions. 3
 Overview of the module
This module revolves on chemical thermodynamics and chemical kinetics.

The purpose of thermodynamics is to explain certain aspects of physical transformations of

compounds and chemical reaction.

The main goals of chemical kinetics is to understand the steps by which a reaction takes
place. This series of steps is called the reaction mechanism.

We will consider the main ideas of chemical kinetics and we will explore rate laws, reaction
mechanisms, and simple models for chemical reactions.

4
 References
Steven S. Zumdahl and Susan S. Zumdahl (2010). Chemistry, Eighth edition. Publisher:
Brooks/Cole.
https://books.google.rw/books/about/Chemistry.html?id=RqWpPwAACAAJ&redir_esc=y
Wolfgang Schärtl, (2014). Basic Physical Chemistry: A Complete Introduction on Bachelor of
Science Level 1st edition. ISBN 978-87-403-0669-9.
http://dspace.bhos.edu.az/xmlui/bitstream/handle/123456789/840/basic-physical-
chemistry.pdf?sequence=1

Peter W. Atkins and J. de Paula (2010). Physical Chemistry, 9th Ed., Oxford University Press.

5
6
 1.1. General introduction
➢ Chemical kinetics is the study of the rates or velocity, at which a
chemical reaction occurs, and also the factors affecting the
rates.
➢ The word “kinetic” means the movement or change; here it
refers to the speed or rate of reaction under various conditions.
➢ The kinetic study provides the valuable information about the
rate and mechanism of chemical reaction, which helps out in
running a chemical reaction successfully by selecting optimum
reaction conditions.

7
 Introduction ctn’d
• The study of rate yields information on the mechanism by which a
reaction occurs at molecular level.
• In industry, the importance is given to speed up the rate of a
reaction and also to increase the productivity.
• Practically, a good understanding of reaction rates is useful, in
waste water treatment, in pollution control, in drug design and in
food processing.
• For example, some phenomena, like photosynthesis, hydrocarbon
combustion and nuclear reactions, take place on a time scale as
short as pico seconds to micro seconds.

8
 Introduction ctnd
• Other processes such as the transformation of graphite to
diamond or the rusting of iron is a slow process that takes place
over many days, even over the years.
• A study into the kinetics of a chemical reaction is usually carried
out with one or both of two main goals in mind:
i. Analysis of the sequence of elementary steps giving rise to the
overall reaction. i.e. the reaction mechanism.
ii. Determination of the absolute rate of the reaction and/or its
individual elementary steps.

9
 1.2. Chemical Reaction - The Rate
❑ What is reaction rate?
 The rate of a chemical reaction refers to the reactant
consumption or the product formation per unit time.
 It is a quantitative measure of how fast a reaction can
proceed.
➢some reactions proceed very fast, other reactions may
proceed very slow
❑ Why study the reaction rate?
 in industry we need to know how long do we need to produce
a certain product
➢the size and type of a reactor
 we also need to know what is the best reaction conditions we
should apply
➢using proper conditions such as T, P, concentration etc. to
speed up the desired reaction
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 ➢to suppress undesired side reactions
➢when apply a catalyst how effective it is on the desired/
undesired reaction
 A study of reaction rate often reveal information on the
reaction mechanism
➢A good understanding of reaction mechanism helps us to
find a more effective way to carry out a reaction and
sometimes leads to discovery of new means of reaction .

Investigating the rate of a real reaction reveals an important point:

not only the concentration, but the rate itself varies with time as the
reaction proceeds.

11
 Rate of chemical reaction ctnd
• When we talk about the rate of a chemical reaction, what we
mean is the rate at which reactants are used up, or equivalently
the rate at which products are formed.
• To measure a reaction rate, we simply need to monitor the
concentration of one of the reactants or products as a function of
time.
• There is one slight complication to our definition of the reaction
rate so far, which is to do with the stoichiometry of the reaction.
• The stoichiometry simply refers to the number of moles of each
reactant and product appearing in the reaction equation (see
later).
• The rate of reaction is the change in concentration of a reactant
(or a product) within a period of time.
12
 Rate of chemical reaction ctn’d
Reaction Rate is expressed as: Δ in amount of Reactant or Product
Δ in Time
▪ Δ means change

State of Reactant Amount Unit

(s) mass g

(g) volume mL, or L

(aq) concentration M or mol/L

13
 Rate of reaction ctn’d
• In general, the rate is expressed as the change in concentration
with time.
• Therefore, a rate must be specified with a specific time unit
(Mole/L. sec or M.s-1).
Concentration in M or mol/L and time in seconds or s.
• Other units of time can be used such as minutes, hours, days,
months, or years.
• The rate of reaction does not depend on the choice of
substance, but it does depend on the way in which the
chemical reaction is written.

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• Reaction rate is measured in terms of the changes in
concentrations of reactants or products per unit time.
1.2.1. Expressing the Reaction Rate
• For the general reaction A → B, we measure the concentration
of A at t1 and at t2:
change in concentration of A conc A2 - conc A1 D[A]
Rate = =- =-
change in time Dt
t2 - t1
D[A] ∆[A] = change in concentration of A over time
rate = - Dt
period ∆t
D[B] ∆[B] = change in concentration of B over time
rate = Dt
period ∆t
• The negative sign is used because the concentration of A is
decreasing with time. This gives the rate a positive value. 15
Note the minus sign.
By convention, reaction rate is a positive number, but conc. A2 will
always be lower than conc.A1, so the change in (final-initial)
concentration of reactant A is always negative.
We use the minus sign simply to convert the negative change in
reactant concentration to a positive value for the rate.
Example:
Assume that the concentration of A changes from 1.2 mol/L (conc.
A1,) to 0.75 mol/L (conc A2) over a 125 seconds period.
The average rate is:

16
 1.2.2. Reaction Rate and stoichiometry
1. Consider: A → B

One mole of A disappears for each mole of B that is formed.

D[A] D[B]
rate = - rate =
Dt Dt

2. Consider: 2C → D

Two moles of C disappear for each mole of D that is formed.

D[C] D[D] 1 D[C]

rate = rate = -
2 x rate = -
Dt Dt 2 Dt
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 1.2.3. Plots of [reactant] and [product] vs. time
• Consider the reaction : C2H4(g)+O3(g)⇋C2H4O(g)+O2(g)
[O2] increases just as fast as [C2H4] decreases.
D[C2H4] D[O3]
Rate = - =-
Dt Dt

D[C2H4O] D[O2]
Rate= =
Dt Dt

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Concentration of O3 at Various Times in Its Reaction with C2H4 at 303K
The rate over the entire 60.0 s is the total
change in concentration divided by the
change in time:

This calculation gives us the average rate over that period; that is,
during the first 60.0 s of the reaction, ozone concentration decreases
an average of 3 .50 X 1 0- 7 mol/L each second.
However, the average rate does not show that the rate is changing,
and it tells us nothing about how fast the ozone concentration is
decreasing at any given instant. 19
The shorter the time period we opt, the closer we come to the
instantaneous rate, the rate at a particular instant during the
reaction.
The slope of a line tangent to the curve at a particular point gives
the instantaneous rate at that time.

20
 Plots of [reactant] and [product] vs. time ctn’d

• Consider the reaction: H2+I2 → 2HI

[HI] increases twice as fast as [H2] decreases
D[H2] D[I2] D[HI]
Rate = - =- = 1
Dt Dt 2 Dt

D[IH] D[H2] D[I2]

Rate = = -2 = -2
Dt Dt Dt

The expression for the rate of a reaction and its

numerical value depend on which substance serves
as the reference.

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 1.2.4.General Reaction Rate Expression
• For the general reaction: a A+b B ⎯→ c C +d D
where a, b, c, and d are coefficients of the balanced equation. In
general, the rate is related to reactant or product concentrations as
follows:
1 D[A] 1 D[B] 1 D[C] 1 D[D]
Rate = − =− = =
a Dt b Dt c Dt d Dt

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 Summary
✓ The average reaction rate is the change in reactant (or product)
concentration over a change in time, M.
✓ The rate slows as reactants are used up. The instantaneous rate
at time t is obtained from the slope of the tangent to a
concentration vs. time curve at time t.
✓ The initial rate, the instantaneous rate at t=0, occurs when
reactants are just mixed and before any product accumulates.
✓ The expression for a reaction rate and its numerical value
depend on which reaction component is being monitored.

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 A B

D[A]
rate = -
Dt

D[B]
rate = +
Dt

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 1.2.5. Examples

1. Write the rate expressions for the following reactions in

terms of the disappearance of the reactants and the
appearance of the products:

25
 Example 2
• Consider the reaction: 4NO2(g)+O2(g) ⎯→ 2N2O5(g)

Suppose that, at a particular moment during the reaction,

molecular oxygen is reacting at the rate of 0.024 M/s.
(a)At what rate is N2O5 being formed?
(b)At what rate is NO2 reacting?

1) Write the reaction rate for each species:

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 Ex.2 ctn’d

2. Knowing the rate of oxygen:

For [N2O5]:

For [NO2]: 1 D[ NO2 ] D[O2 ]

− =−
4 Dt Dt
D[ NO2 ]
 = 4(0.024M / s ) = 0.096M / s
Dt
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3. Given the following reaction of formation of nitrogen monoxide
and bromine:

The rate of formation of NO in this reaction is 1.6 x 10-4 mol/L.s.

Find the rate of consumption of NOBr.
d[NOBr]
Rate = - = 1.6 x 10-4mol/L.s
dt
4. Given the reaction of recombination of the radicals CH3.:

If the rate of consumption of CH3.is 1.2 mol/L.s, find the rate of

formation of CH3-CH3.
.
d(C2H6) - 2d[CH3 ] 1.2 mol/L.s
Rate = + dt = dt = 2 = 0.6 mol/L.s
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 1.2.6. Exercises
1. Hydrogen gas has a nonpolluting combustion product (water
vapor), the reaction is: H2(g) + O2(g) → H2O(g)
(a) Express the rate in terms of changes in [H2], [O2], and [H2O] with
time.
(b) When [O2] is decreasing at 0.23 mol/L·s, at what rate is [H2O]
increasing?
We choose O2 as the reference because its coefficient is 1. For
every molecule of O2 that disappears, two molecules of H2
disappear, so the rate of [O2] decrease is ½ the rate of [H2]
decrease. Similarly, the rate at which [O2] decreases is ½ the rate at
which [H2O] increases.
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2. Consider the reaction: N2 +3H2 ⎯→ 2NH3 which proceed in a
closed autoclave of the volume V = 5 dm3.
During 1s, 0.01 mole of nitrogen reacted.
a.Estimate the rates of consumption of nitrogen and hydrogen, the
rate of formation of ammonia and the rate of the reaction.
b.Find out how these rates will change if we write the reaction in
the form: ½ N2 +3/2 H2 ⎯→NH3

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3. Given the reaction:4NH3(g)+5 O2(g) → 4NO(g)+6 H2O(g)
• If the rate of consumption of NH3(g) measured after a
certain period of time is 0.24 mole.(L.s)-1,
Find:
a.The rate of consumption of oxygen
b.The rate of formation of water

31
 Exercises ctnd
4. Consider the reaction, C2H6(g) +7O2 (g)→4 CO2 (g) + 6 H2O (g).
If the ethane is burning at the rate of 0.20 M/s, at what rates are
CO2 and H2O being formed?

− − +
5. For the reaction: 5Br (aq) + BrO3 (aq) + 6H (aq) → 3Br 2 ( g ) + 3H 2 O(l )

It was found that at a particular instant, bromine was being formed

at the rate of 0.039 M/s.
a.What is the rate of water being formed at that instant?
b.At what rate bromide ion is being oxidized?
c.At what rate hydrogen ion is being consumed?

32
6. In the nuclear industry, chlorine is used to prepare uranium
hexafluoride, a volatile compound of uranium used in the
separation of uranium isotopes. Chlorine trifluoride is prepared by
the reaction: (g) + (g) →
Cl 2 3F 2 2ClF (g)
3

• Write the equation that relates the rate expressions for this
reaction in terms of the disappearance of chlorine and fluorine and
the formation of ClF3.

33
 1.2.7. Initial and average rates
• The initial rate is the rate of a reaction measured at the beginning
of the reaction. It is the change in concentration of a reactant, or
product, per unit time at the start of reaction.
• The initial rate is simply the instantaneous rate at time equal to
zero, or at the beginning of the reaction.
• The average rate is defined as the change in concentration of a
reactant or product of a chemical reaction in a given interval of
time.

34
 1.2.8. Instantaneous rate
• The instantaneous rate is the change in concentration of a
reactant or product of a chemical reaction at a given instant. This
rate is measured when the reaction is in progress at any point of
time.
• It is obtained when we consider the average rate at the smallest
time interval dt (i.e. when Δt approaches zero).
• This rate is measured when the reaction is in progress at any point
of time.
• It is obtained when we consider the average rate at the smallest
time interval dt (i.e. when Δt approaches zero).

35
 Instantaneous rate ctn’d
• Mathematically, for an infinitesimally small dt, the instantaneous
rate is given by:
d [ R] d [ P]
Rate, R = − =
dt dt
• Where d[R]=small change in concentration of R and dt=small
change in time.
• If we plot the concentration of a product forming against time,
we will get a curve.
• The tangential slope at any point on that curve would be the
instantaneous rate at that moment in time.
• The following Figure shows the instantaneous rate at any point of
the curve.
36
 1.2.9. Instantaneous rate and stoichiometry
• If we plot the concentration of a product forming against time,
we will get a curve.
• The tangential slope at any point on that curve would be the
instantaneous rate at that moment in time.

Instantaneous rate = rate for specific instance in time

• The following Figure shows the instantaneous rate at any

point of the curve.

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38
 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.
 Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)
• The reaction slows down with time
because the concentration of the
reactants decreases.
 1.2.10. Factors affecting rate of reaction
• The determination of how quickly or slowly reactants turn into
products is a measure of the reaction rate.
• Some conditions can be used to speed or to slow down the rate
of a chemical reaction.

• The factors that influence rate of chemical reaction are:

(a) Nature of reactants
(b) Concentration
(c) Temperature
(d) Pressure
(e) Catalyst
(f)Radiation, etc.
41
 (a) Nature of reactants

• (i) Physical state of reactants: Some reactant molecules react

quickly while others react slowly.
• This may be due to the phase of matter, solids will react much
more slowly than liquids or aqueous solutions. (Gaseous state >
Liquid state > Solid state) or (Decreasing rate of reaction)

• Similarly in a heterogeneous system, collision is not effective as in

homogenous system. Thus, reactions in liquid phase or solution
phase will be faster in comparison to heterogeneous conditions
when the same concentrations of the reactants are engaged.

42
(ii) Physical size of the reactants (surface area of reactants)
• Except for substances in the gaseous state or solution, reactions
occur at the boundary, or interface, between two phases. In other
words, at the exposed surface of the substance.

• Therefore, the greater the surface area exposed, the greater

chance of collisions between particles, hence, the reaction should
proceed at a much faster rate.

• Among the solids, rate increases with decrease in particle size. In

powdered state, rate of reaction is maximum because in
powdered state, surface area is maximum.
43
 (b) Concentration of reactants
• Two substances react when they collide each other.

• If there is no contact, the reaction rate will be zero.

• Conversely, the more reactant particles that collide per unit

time, the more often a reaction between them can occur.

• Consequently, the rate of chemical reaction is directly

proportional to the concentration of the reactants. The more
molecules present, the more collisions occur, the faster the
reaction proceeds and the greater its rate.
44
Let us consider the reaction: A + B → C + D; Rate = k [A][B]
Rate of the above reaction decreases with the passage of time
because the concentration of reactants A and B will decrease as
time pass on.
• At the beginning of a reaction, when the concentration of
reactants is maximum, the rate of reaction is also maximum.
• The rate of the reaction decreases as the reactants are
consumed and it increases when the products are formed

45
 (c) Temperature effect
• In general, the rate of most chemical reactions increase as the
temperature rises.
• When the temperature of a reaction is increased, the heat is
supplied to the particles involved in the reaction which enables
them to move more quickly, and they collide with each other
more frequently and with more energy.
• Conversely, the reaction rate of almost all reactions decreases
with decreasing temperature.

• For example, refrigeration retards the rate of growth of bacteria in

foods by decreasing the reaction rates of biochemical reactions
that enable bacteria to reproduce.
46
 (d) Effect of pressure
• The pressure affects the rate of chemical reactions when the
reactants or products are in gaseous state.
• This is because solids and liquids cannot be compressed, they do
not change in volume when pressure is reduced or increased.
• Pressure has a similar effect as concentration on the reaction rate.
When the pressure increases in the gaseous system, the number of
collisions between reactants also increases.
Consequently, the rate of reaction is increased.
• At high pressure, the gas particles are closer together which can
increase the collision.

47
Catalyst Effect on energy diagram profile.
▪ Catalyst is a substance that increases or
decreases the rate of a chemical
reaction by lowering the activation
energy without itself being consumed
by the reaction.
▪ Catalysts reduce the amount of energy
required to break and form bonds
during a chemical reaction.

48
For example, the decomposition of hydrogen peroxide (H2O2) is
relatively slow; however, exposure to light accelerates this process
and in the presence of MnO2 as a catalyst, the reaction goes very
fast.

49
50
Catalysts Effect on Rates of
Reactions
Working Principle of Catalysts and their Effects on Reaction
Rates
Catalysts alter the rates of reaction,
1. but remain chemically unchanged at the end of the reaction
2. by providing new, alternative reaction pathways with
different activation energies.
3.A catalyst speeds up a reaction by providing a set of elementary
steps with more favorable kinetics than those that exist in its
absence.
Example: The gas-phase decomposition of nitrous oxide(N2O) is
believed to occur via two elementary steps:
Step 1: N2O → N2+O and Step 2: N2O+O→ N2+O2
 Working Principle of Catalysts and their Effects on Reaction
Rates
Positive catalyst:
• Provides an alternative reaction pathway with a lower
activation energy
Greater fraction of molecules with kinetic energy (K.E.)greater
than or equal to activation energy (Ea). Thus, reaction
proceeds faster.
Working Principle of Catalysts and their Effects on Reaction
Rates
Negative catalyst:
• Provides an alternative reaction pathway with a higher
activation energy
Smaller fraction of molecules with kinetic energy (K.E) greater
than or equal to activation energy (Ea).Therefore, reaction
proceeds slower.
Working Principle of Catalysts and their Effects on Reaction Rates

With catalysts, the contour diagrams

and thus the energy profiles are totally
different from those without
 Catalyst

Homogeneous Catalyst Heterogeneous Catalyst

Reactants & catalyst are in the same Reactants & catalyst are NOT in the
phase same phase
 Homogeneous catalysis
Homogeneous catalysis takes places when the reactants and
catalysts are dispersed in a single phased, usually liquid.
Acid catalysis and base catalysis are the most important types of
homogeneous catalysis in liquid solution.
For example, the reaction between ethyl acetate with water to
form acetic acid and ethanol normally takes place too slowly to be
measured: CH3COOCH2CH3+ H2O →CH3COOH +CH3CH2OH
The reaction, however, can be catalyzed by an acid. In the
presence of hydrochloric acid , the rate is faster.
Homogeneous catalysis can also take place in the gas phase.
Example manufacturing sulfuric acid. Starting from sulfur.
57
 Characteristics of Catalysts

1. For a given reversible reaction,

k1
Reactants Products
K-1
catalysts affect the rates of forward reaction and backward
reaction to the same extent.
 Example

Without k1
catalyst Reactants Products
k-1
With k1'
catalyst Reactants Products
k-'1

k '
1 k '
−1
Show =
that k1 k−1
 Characteristics of Catalysts
2. Catalysts are chemically unchanged at the end of reactions but
may undergo physical changes.
E.g. MnO2 used in the decomposition of H2O2 become powdered
at the end of the reaction.

3. Only small quantity is sufficient to catalyze a reaction because

catalysts can be regenerated.
However, if the catalysts are involved in the rate equation, higher
concentrations may affect the rate more.
 Characteristics of Catalysts
4. The effect of heterogeneous catalysts depends on the surface
area available for the catalytic action.
Surface area of solid catalyst 
 number of reaction sites 
 catalytic activity
Example: Finely divided Fe powder is used as the catalyst in Haber
process.
5. Catalytic actions are specific especially in biological systems.
Example: Enzymatic actions are highly specific.
6. The efficiency of a catalyst is often enhanced by adding
promoters. Promoters have no catalytic actions on their own.
E.g. Fe2O3, KOH, Al2O3 in Haber process
 Characteristics of Catalysts
7. The efficiency of a catalyst can be lowered by adding poisons or
inhibitors. Catalyst poisons are specific in action.
E.g. Arsenic impurities may poison Pt but not V2O5 in Contact
process

8. Transition metals or compounds/ions containing transition

metals show marked catalytic activities.
Examples: Pt, Ni, Fe, V2O5, MnO2, Mn2+ Fe3+

The catalytic actions are due to the presence of low-lying partially

filled d-orbitals.
 Heterogeneous Catalysis – Adsorption
Heterogeneous catalysis happens when the reactants and catalyst
are in different phases.
Occur on the surface of the catalyst.
1. Reactants are adsorbed on the surface, forming new bonds with
the catalyst while weakening bonds in reactants.
2. Products, once formed, are desorbed from the surface,

For example: in the Haber process, the reactants (Nitrogen &

Hydrogen are in the gaseous phase while the catalyst which is iron
(Fe) is solid phase).
Examples of heterogeneous catalysis

MnO2(s)
2H2O2(aq) ⎯⎯⎯⎯→ 2H2O(l) + O2(g)

Fe(s)
3H2(g) + N2(g) ⎯⎯→ 2NH3(g)

Al2O3/SiO2(s)
C8H18(g) ⎯⎯⎯⎯⎯⎯→ C4H10(g) + C4H8(g)

Ni(s)
CH2=CH2(g) + H2(g) ⎯⎯→ CH3–CH3(g)
The metal-catalyzed hydrogenation of ethylene.

65
 Catalysts

One way a catalyst can speed up a

reaction is by holding the reactants
together and helping bonds to
break.
 Some applications of Catalysts

Industrial Catalysts

1. Iron is used in the Haber process

Fe(s)
N2(g) + 3H2(g) 2NH3(g)

2. Platinum or vanadium(V) oxide is used

in the Contact process
Pt or V2O5
2SO2(g) + O2(g) 2SO3(g)
 Applications of Catalysts
3. Nickel, platinium or palladium is used in the hydrogenation
of unsaturated oils to make margarine
Applications of Catalysts

4. Use of Nickel and nickel(II) oxide in the

production of town gas in Hong Kong.
Ni or
NiO
C5H12(g) + 5H2O(g) ⎯→ 5CO(g) + 11H2(g)
2CO(g) + 2H2(g) ⎯→ CO2(g) + CH4(g)
 Applications of Catalysts
Catalytic Converters in Car Exhaust Systems

At the high temperature inside a running car engine, nitrogen and

oxygen gases react to form nitric oxide (NO).
When released in the atmosphere, NO rapidly combines with
oxygen to form NO2.
Nitrogen dioxide and other gases emitted by automobiles like CO
and various unburned hydrocarbons, make automobiles exhaust a
major resource of air pollution.
All new car are equipped with catalytic converters. An efficient
catalytic converter serves two purposes:
It oxidizes CO and unburned hydrocarbons to CO2 and H2O; it
reduces NO and NO2 to N2 and O2.
Hot exhaust gases into which air has been injected are passed
through the first chamber of one converter to accelerate the
complete burning of hydrocarbons and to decrease CO emissions.

71
72
 Applications of Catalysts

Rh
2CO(g) + 2NO(g) ⎯→ 2CO2(g) + N2(g)

Pt
CxHy(g) + ( x + y/4) O2(g) ⎯→ xCO2(g) + y/2 H2O(g)

Pt
2CO(g) + O2(g)⎯→ 2CO2(g)
 Applications of Catalysts
Enzymes are used in the Production of Alcoholic Drinks, fermentation
process
enzyme
C6H12O6(aq) ⎯⎯→ 2C2H5OH(aq) + 2CO2(g)
Glucose Ethanol or
Ethyl alcohol
 Enzyme catalysis

All intricates processes that have evolved in living systems, none is

more striking or more essential than enzyme catalysis. Hence,
Enzymes are biological catalysts.

✓ Enzymes can increase the rate of biochemical reactions by

factors ranging from 106 to 1018,

✓ Enzymes are highly specific,

75
✓ Enzymes act only on certain molecules, called substrate(that is,
reactants), while leaving the rest of the system unaffected.

✓ Enzyme catalysis is usually homogeneous because the substrate

and enzyme are present in aqueous solution of the cell.

✓ Enzyme is a large protein molecule that contains one or more

active sites where the interactions with substrates take place.

76
 • Enzymes are catalysts in biological systems.
• The substrate fits into the active site of the
enzyme much like a key fits into a lock.

The lock-and–key model of the specificity of

an enzyme for substrate molecules:
 Two models of enzyme action.

The lock-and-key model visualizes the enzyme active site having a

fixed shape. This shape matches the shape of its substrate(s).
The active site is therefore specific to its substrate.
 Two models of enzyme action.

The induced-fit model visualizes the enzyme active site changing

shape in order to bind its substrate(s) more effectively.
The active site is still selective towards certain substrates.
 Summary about Catalyst and Enzyme
A catalyst is a substance that increases the rate of a reaction without being
consumed. It accomplishes this by providing an alternative mechanism with a
lower activation energy.

Homogeneous catalysts function in the same phase as the reactants.

Heterogeneous catalysts act in a different phase from the reactants.
The hydrogenation of carbon-carbon double bonds takes place on a solid
catalyst, which speeds the breakage of the H-H bond in H2.

Enzymes are biological catalysts with spectacular efficiency and specificity.

Chlorine atoms derived from CFC molecules catalyze the breakdown of
stratospheric ozone.

80
 Activity

Discuss about enzyme kinetics

✓ Only three pages (Hand-writing)
✓ Group of 10 students

81
 1.3. The Rate law and order of reaction
• 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
(determined experimentally).
• For any general reaction occurring at a fixed temperature

aA + bB → cC + dD
Rate law = k[A]x[B]y
The values of x and y are not equal to the stoichiometric coefficients a and b;
they are determined experimentally
k is the rate constant which is specific for a given reaction at a given
temperature.
• The concentrations of the products do not appear in the rate law because
the reaction rate is being studied under conditions where the reverse reaction
does not contribute to the overall rate. 82
 Rate laws and order of reaction ctnd

Rate = k[A]x[B]y

where x and y are the orders of reaction with respect to A and B

x + y is the overall order of reaction.

Keep in mind that the coefficients a and b in the general balanced
equation are not necessarily related in any way to these reaction
orders x and y.
For single-step reactions (elementary reactions), x = a and y = b
 Rate Laws and order of reaction ctnd
• The order of a reactant is not related to the stoichiometric
coefficient of the reactant in the balanced chemical equation
as shown in the example below.

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

1
rate = k [F2][ClO2]
For the reaction aA + bB → cC + dD

Rate = k[A]x[B]y
x = 0 → zero order w.r.t. A
x = 1 → first order w.r.t. A
x = 2 → second order w.r.t. A

y = 0 → zero order w.r.t. B

y = 1 → first order w.r.t. B
y = 2 → second order w.r.t. B
 For the reaction aA + bB → cC + dD
Describe the reaction with the following rate law.

Rate = k[B]2
The reaction is zero order with respect to (w.r.t.) A and second
order with respect to (w.r.t.) B.
 Order of reactions
• All the concentrations of all reactants taking part in a reaction
cannot determine the rate of reaction. Therefore, let us introduce
a new term; the order of a reaction defined as follows:

‘‘The order of reaction is given by the total number of molecules or

atoms whose concentrations determine the velocity of the
reaction’’.

• In general, the powers to which the concentration terms are

raised in the rate law expression describes the order of the
reaction with respect to that reactant.
 1.4. Rate constant and its units
• Let us consider a general reaction: aA + bB→ products;
The rate R = dx/dt = k [A]a[B]b
• The units of the rate constant depend on the form of the rate law
in which it appears. Below are examples.

(i)Consider the rate law r = k [H2][I2]. If we substitute the units into the
equation, we obtain:
(mol. dm-3s-1) = [k] (mol. dm-3) (mol. dm-3)
[k] =(mol. dm-3s-1)/ (mol. dm-3) (mol. dm-3) = mol-1. dm3s-1

88
For the reaction aA + bB → cC + dD

Rate = k[A]0[B]0

units of k
= mol dm−3 s−1/(mol dm−3)0+0
= mol dm−3 s−1
= units of rate
 For the reaction aA + bB → cC + dD

Rate = k[A][B]0

units of k
= mol dm−3 s−1/(mol dm−3)1+0
= s−1
 For the reaction aA + bB → cC + dD

Rate = k[A][B]

units of k
= mol dm−3 s−1/(mol dm−3)1+1
= mol−1 dm3 s−1
The overall order of reaction can be deduced from the units of k

For the reaction : a A + bB + cC + … → products

Rate = k[A]x[B]y[C]z…
units of k : mol dm−3 s−1/(mol dm−3)x+y+z+…
Relationship between rate law, order & the rate constant k
Rate law Order Unit of k
Rate = k Zero M. s-1
Rate = k [A] First order with respect to A s-1
First overall order
Rate = k [A]2 Second order with respect to A L.mol-1.S-1
Second overall order

Rate = k [A] [B] First order with respect to A mol-1.L.s-1

First order with respect to B
Second overall order

Rate = k[A] [B] [C] First order with respect to A mol-2.L2s-1

First order with respect to B
First order with respect to C
Third overall order
92
 1.5. Methods used to determine the rate
law From the experimental data

Objective: Understanding on how to

determine the rate law and the order of the
reaction

93
1.5.1.Determination of Rate law
by using Initial Rate Methods
 Initial rate method
• The initial rate or isolation method is a technique used to simplify
the rate law in order to determine its dependence on the
concentration of a single reactant.

• Several experiments are carried out using different initial

concentrations of each of the reactants, and the initial rate is
determined for each run by making a simplification.

95
Ex: 5Cl−(aq) + ClO3−(aq) + 6H+(aq) → 3Cl2(aq) + 3H2O(l)

[Cl−(aq)] [ClO3−(aq)] [H+(aq)] Initial rate

Expt
/ mol dm−3 / mol dm−3 / mol dm−3 / mol dm−3 s−1
1 0.15 0.08 0.20 1.010−5
2 0.15 0.08 0.40 4.010−5
3 0.15 0.16 0.40 8.010−5
4 0.30 0.08 0.20 2.010−5

rate = k[Cl−(aq)]x[ClO3−(aq)]y[H+(aq)]z
 [Cl−(aq)] [ClO3−(aq)] [H+(aq)] Initial rate
Expt
/ mol dm−3 / mol dm−3 / mol dm−3 / mol dm−3 s−1
1 0.15 0.08 0.20 1.010−5
2 0.15 0.08 0.40 4.010−5
3 0.15 0.16 0.40 8.010−5
4 0.30 0.08 0.20 2.010−5

From experiments 1 and 2,

4.0  10−5 (0.15)x (0.08) y (0.40)z
= y = 2 z
1.0  10−5 (0.15)x (0.08) (0.20)z

4 = 2z  z = 2
 [Cl−(aq)] [ClO3−(aq)] [H+(aq)] Initial rate
Expt
/ mol dm−3 / mol dm−3 / mol dm−3 / mol dm−3 s−1
1 0.15 0.08 0.20 1.010−5
2 0.15 0.08 0.40 4.010−5
3 0.15 0.16 0.40 8.010−5
4 0.30 0.08 0.20 2.010−5

From experiments 2 and 3,

8.0  10−5 (0.15)x (0.16) y (0.40)z
= y = 2 y
4.0  10−5 (0.15)x (0.08) (0.40)z

2 = 2y  y = 1
 [Cl−(aq)] [ClO3−(aq)] [H+(aq)] Initial rate
Expt
/ mol dm−3 / mol dm−3 / mol dm−3 / mol dm−3 s−1
1 0.15 0.08 0.20 1.010−5
2 0.15 0.08 0.40 4.010−5
3 0.15 0.16 0.40 8.010−5
4 0.30 0.08 0.20 2.010−5

From experiments 1 and 4,

2.0  10−5 (0.30) x (0.08) y (0.20)z
= y = 2 x
1.0  10−5 (0.15)x (0.08) (0.20)z

2 = 2x  x = 1
 [Cl−(aq)] [ClO3−(aq)] [H+(aq)] Initial rate
Expt
/ mol dm−3 / mol dm−3 / mol dm−3 / mol dm−3 s−1
1 0.15 0.08 0.20 1.010−5
2 0.15 0.08 0.40 4.010−5
3 0.15 0.16 0.40 8.010−5
4 0.30 0.08 0.20 2.010−5

rate = k[Cl−(aq)][ClO3−(aq)][H+(aq)]2
From experiment 1,
1.010−5 = k(0.15)(0.08)(0.20)2
k = 0.02 mol−3 dm9 s−1
 [Cl−(aq)] [ClO3−(aq)] [H+(aq)] Initial rate
Expt
/ mol dm−3 / mol dm−3 / mol dm−3 / mol dm−3 s−1
1 0.15 0.08 0.20 1.010−5
2 0.15 0.08 0.40 4.010−5
3 0.15 0.16 0.40 8.010−5
4 0.30 0.08 0.20 2.010−5

rate = k[Cl−(aq)][ClO3−(aq)][H+(aq)]2
From experiment 2,
4.010−5 = k(0.15)(0.08)(0.40)2
k = 0.02 mol−3 dm9 s−1
1.5.2.Determination of Rate law
by using integral methods
Rate law expressions allow to determine the reaction rate from the
rate constant and reactant concentrations.

Using calculus, the rate laws can be transformed by the process of

integration to provide integrated rate laws, which inform us the
concentrations of reactants at any time during the course of a
reaction.
 Integration methods
This is the commonest method used for the determination of the
reaction order.
It will be applied for zeroth, first, second and third order reactions
• From the integrated rate equation, the extent of a reaction in
terms of the concentration of the reactant can be measured, if
the rate constant is known.

103
 a. Zero Order Reactions
Independent of the concentration of starting material
A B
Reaction rate:
Rate Law:
D[A]
rate = - rate = k [A]0
Dt
rate = k

D[A] d[A 
-
Dt
=k = −k
dt
d[A  = −k dt
Calculus
Happens! [A t t

 d[A  = −k  dt
[ 
A 0
[A]t = -k • t + [A]0 0

[At − [A0 = −k (t - 0)
104
Zero Order Reactions ctn’d
[A]t = -k•t + [A]0

[A]t is the concentration of A at any time t

[A]0 is the concentration of A at time t=0
k is the rate constant
t is time
[A]t = -k • t + [A]0
y = m•x+ b
• Know [A]0 and t, predict [A]t
• Know [A]0 and [A]t, predict t
• Know [A]t and t, predict [A]0 105
 Half-life of zeroth order reactions
The time required for a reactant to reach half of its original
concentrations is called half-life of the reaction and is designated
t1/2.
Half-life is inversely related to the rate constant of a reaction: The
higher reaction rate, the shorter the half-life.
• For a zeroth order reaction, [A]t = [A]0- kt
• At a time, t = t1/2, [A]t = [A]0/2 and we have:
[A]0/2 = [A]0 - kt1/2
Then: [A]0 /2 - [A]0 = - kt1/2
- [A]0 /2 + [A]0 = kt1/2
- [A]0 /2 = - kt1/2 The half-life becomes: 106
 b. First-Order Reaction
A first-order reaction refers to the reaction whose rate depends on
the reactant concentration raised to the first power.
Consider the first-order reaction as A→ product

d[A]
The reaction rate is: - = k[A]1 (3)
dt

• In order to obtain the integrated rate for first order reaction, the
concentrations of A at the beginning of the reaction and at a
time t are mentioned below:

• At time = 0 (i.e., at the start), the initial concentration of A=[A]o

• At a certain time=t, the concentration of A = [A]t 107
• Using these limits of concentration and time, we can integrate
equation (3) after rearranging it as follows:
[ A ]t t
d [ A]

[ A ]0
−
[ A] 0
=  kdt (4)

[ A ]t
= − ln[ A] = k (t − 0) = −(ln[ A] − [ A] = kt (5)
[ A ]0 t 0

= ln[ A] − ln[ A] = kt (6)

0 t

ln(
[ A] ) = kt
0 (7)
• Hence, [ A] t
The equation (7) can be written in the exponential form as:
− kt
[ A] = [ A] e
t 0 (8) 108
 First-Order Reaction
• For a first order reaction, a log-linear plot reactant concentration
versus times provides a straight lines with a slope of –K and an
intercept of ln[A]o.

109
 Half-life of first order reactions
• The time taken for the concentration of a reactant to fall to half
its initial value is called the half-life (t1/2) of a reaction. The half-
life for a first order reaction is given from the relation:

ln(
[ A]0
) = kt
[ A]t
1
• At a time, t = t1/2, [ A]t1/ 2 = 2 [ A]0
• For first order reaction,ln(
[ A] ) = kt  ln(
0
2[ A] ) = kt 0

[ A] 0
[ A] 0
2
• As t = t1/2, the relation becomes: ln 2 = kt1/ 2  t1/ 2 =
ln 2 0.693
=
k k

110
 Example
A first order reaction is 35% complete at the end of 55
minutes. What is the value of k?
A0 100
ln = kt  ln = 55k
At 65
100
k = ln / 55min
65
k = 7.8  10 min
–3 –1

111
 c. Integrated rate laws for second order reactions
Second-order reaction is one whose rate relies on the concentration
of one reactant raised to the second power or on the
concentrations of two different reactants, each raised to the first
power.
There are two types of second order reactions:
(i) A single reactant could give rise to products through a second
order reaction. A → products

d[A]
Rate = - = k[A]2 (9)
The rate equation is: dt

Where k is the second order rate constant.

(ii) Two different reactant molecules could react to give products
through a second order reaction. A + B → products 112
The rate equation is given as: Rate = k [A][B] = k[A][A] = k [A]2 (10)
• Then, Eq. (10) takes the same form as Eq.(9)
• We use Eq.(10) as the rate law for both these two types. We
derive the integrated rate law for these two under case (i).
Case (i): Integrated rate law for a reaction that follows differential
rate law with respect to Eq. (9).
We start with the differential rate law:
d[A]
Rate = - = k[A]2
dt

113
 Integrated law for second order reaction
• The integrated form of the equation can be obtained using the
following limiting conditions: At time t=0 (i.e., at the start), the
concentration of A=[ A ]0.
At time= t, the concentration of A = [A]t.
• Applying these limits on the rearranged form of Eq. 9, we get:
d[A]
Rate = - = k[A]2  - d[A] = kdt
dt [A]2
We integrate between t = 0 (when x = 0) and t, the time of interest.

114
By integration, we have:

[ A ]t t [ A ]t t
d [ A] −2
−  2
=  kdt = −  [ A] d [ A] =  kdt (11)
[ A ]0 [ A] 0 [ A ]0 0

1 1 1 1
= − = kt (12) or = + kt (13)
[ A] [ A] t 0
[ A] [ A]
t 0

The second order rate constant can be calculated by plotting

1/[A]t against t. A straight-line curve must be obtained.
The slope of the straight line gives the second order rate constant.
k = slope and 1/[A]0 is the intercept.

115
 Second order reaction
For a second order reaction, a plot of 1/[A] vs. time (t) is linear with
a positive slope k. The slope of the straight line gives the second
order rate constant and 1/[A]0 is the intercept.

116
 (ii) If concentrations of the two
reactants are different
1. When the initial concentrations of the two reactants are
not equal. Let x be the concentration of each species
reacted at time t. [ A ]o and [ B ]o are different:
• Let [A]0 = a and [B]0 = b, then [A] = a – x; [B] = b – x.
The expression of rate law becomes:
-dx/dt = - k ([A]0 – x)([B]0-x) which can be rearranged to:

dx
= kdt
([ A] − x)([ B] − x)
0 0

117
We integrate between t=0 (when x=0) and t, the time of interest.
x t
dx
 ([ A]
0 − x)([ B] − x)
= k  dt
0
0 0

• To solve this integral, we use the method of partial fractions.

x
1 1 1 1
0 (a − x)(b − x)dx = b − a (ln a − x − ln b − x
Evaluating the integral gives us:
x
dx 1 [ A] [ B]
 ([ A]
0
=
− x)([ B] − x) [ B] − [ A]
(ln 0
− ln
[ A] − x [B] − x
0
)
0 0 0 0 0 0

118
Applying the rule of logarithm, the equation simplifies to:
x
dx 1 [ B][ A]
 ([ A]
0
= ln
− x)([ B] − x) [ B] − [ A] [ A][B]
0
)
0 0 0 0 0

We obtain the integrated rate equation (under the condition that

[A] and [B] are not equal).

1 [ B][ A]
ln 0
= kt
[B] − [ A] [ A][ B]
0 0 0

Upon rearrangement of the integrated rate equation, we obtain:

ln
[B][ A] 0
= k ([ B] − [ A] )t
[ A][B] 0
0 0

119
 2. If A0 = B0
A+ B → P
• Consider the reaction:
Since A and B react with a 1 to 1 stoichiometry,
[ A] = [ A] − x
0 [ B] = [ B] − x
0

and
At any time, t, [A] = [B] and the rate law will be:

2
Rate = k[ A][ B] = k[ A][ A] = k [ A]

120
 Half-life for second order reaction
• The half life of any reaction is the amount of time it takes to
consume half of the starting material.
• We can find an expression for the half-life of a second order
reaction by using the previously derived integrated rate
equation. 1 1
= + kt
[ A] [ A]
t 0

121
 1
• Since, [ A]t1/ 2 = 2 [ A]0
• When t=t1/2, the integrated rate equation becomes:
2 1
1 1 − = k t1 / 2
− = k t1/ 2
1 [ A] [ A] [ A]
2
[ A]0
0
0 0

1
= k t1 / 2
• After a series of algebraic steps,
[ A] 0

We obtain the equation for the half-life of a second order reaction:

1
t1 / 2 = k [ A]
0

122
The half-life of a second-order reaction is inversely proportional to
the reactant concentration.
This result makes sense because the half-life should be shorter in
early stage of the reaction when more reactant molecules are
present to collide with each other.
Because of its dependence on concentration, the half-life is much
less useful in describing second-order reactions than the first-
order reactions.
Measuring the half-lives at different initial concentrations is one way
to distinguish between a first-order and a second-order reaction.

123
 Example
Consider the following reaction aA → Products,
[A]0 = 5.0 M, and the first two half-lives are 25 and 50 minutes,
respectively.
a) Write the rate law for this reaction.
rate = k[A]2
b) Calculate k.
k = 8.0 × 10-3 M–1min–1
c) Calculate [A] at t = 525 minutes.
[A] = 0.23 M

124
 Summary
rate = k rate = k [A] rate = k [A]2
Zero Order Reaction First Order Reaction Second Order Reaction

[A]t = -k • t + [A]0 ln[A]t = -k • t + ln[A]0 1 = kt + 1

[A] [A]0

125
126
Summary of the kinetics of :

First order Second order Second order

Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated

k(T)
 Reversible Reactions
To study the kinetics of reversible reaction, it is necessary to consider
both the forward and the reverse rates.
Consider a reversible first-order reaction of molecule A to form
molecule B: A↔B with k1 and k-1
A is consumed in the forward reaction with rate constant k1 and
produced in the reverse reaction with a rate constant k-1, so the
net rate law is d[A]/dt= -k1[A]+k-1[B].
When the system reaches equilibrium, the concentration of A
becomes constant in time, and the rate of production of A, given
by d[A]/dt, will be equal to zero.
0=-k1[A]+k-1[B].
After rearranging this equation, we obtain [B]/[A]=k1/k-1 and k1/k-1= K
At equilibrium, the rates of forward reaction and reverse processes are equal.
128
CAT of CHE2141

June 24, 2022

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