Chapter 1. Fundamental Definitions

INTRODUCTION
Lecturer: PhD. Nguyen Minh Quang

Email: nguyenminhquang@iuh.edu.vn
Phone: 0908.234.865
1
Announcement
Syllabus
Uploaded
LMS
Rubrics
Course Learning Outcomes
(CLOs)
Cognitive
CLOs Content
domain
1 Solve the kinetic parameters of simple
3 / knowledge
reactions
Solve the quantities affecting on reaction
2 3 / knowledge
rates
Solve the kinetic parameters of complex
3 3 / knowledge
reactions
Construct the rate equations of reactions
4 based on the principle of steady-state 3 / knowledge
concentration
Assessment Methods
20% n written
Regular assessment tests
30% 1 written
Mid-term examination
test
50% Final examination 1 written

test
Course contents
Chapter Topic Class hours

1 Fundamental definitions of chemical kinetics 4
2 Kinetics of simple reactions 4
3 Methods of determining reaction order 4
4 Effect of kinetic factors on reaction rates 4
5 Kinetics of complex reactions 10
6 Kinetics of catalytic reactions 4
Summary 30
5
Exam – CLOs – Content
Chapter CLOs Assessment

1 1,2 Mid-term examination
2 1,2 Mid-term examination
3 1 Mid-term examination
4 2 Mid-term examination
5 3,4 Final examination
6 3,4 Final examination
6
Text books and references
[1] Tran Khac Chuong, Mai Huu Khiem, Physical Chemistry Textbook.
Volume 2: Chemical Kinetics and Catalysis, Vietnam National
University, Ho Chi Minh City, 2015. [100060631]
[2] Nguyen Hanh. Theoretical Foundations of Chemistry. Part 2:
Thermodynamics, Chemical kinetics, and Electrochemistry,
Vietnam Education Publishing House, 2010. [100246991]
[3] Mai Huu khiem. Physical Chemistry Exercises, Vietnam National
University Ho Chi Minh City Press, Ho Chi Minh City. [100278047]
7
Chapter 1
Fundamental definitions of chemical

kinetics
8
Content
1.1. The rate of a chemical reaction

1.2. Reaction mechanisms
1.3. Methods for determining the rate of a reaction
1.4. The rate law
1.5. The molecularity of a reaction
1.6. The order of a reaction
9
1.1. The rate of a chemical reactions
Definition
10
Definition
It is determined by the change in the

amount of any substance (reactants or
products) per unit volume and after a unit
time.
11
The reaction rate r is defined as
1 dni
r 
V dt
12 Note: signs “”

Convention for the signs “”
 “+” : calculated for the products.

 “–” : calculated for the reactants.
Why???
13
V = const.
1 dni dCi
r  r
V dt dt
14
Consider the following reaction:

aA + bB  cC + dD
If we do not mention to the scale factor yet
dCA d [A] dCC d [C ]

r   r  
dt dt dt dt
dCB d [ B] dCD d [ D]
r   r  
dt dt dt dt
15
aA + bB  cC + dD
If we mention to the scale factor
1 dCA 1 dCB 1 dCC 1 dCD

r    
a dt b dt c dt d dt
We will usually write the concentrations of a species A by using square

brackets, i.e. [A], and understand that [A] is time dependent, i.e, [A(t)]
16
Example:
N2 + 3H2 = 2NH3
1 dCH2 1 dCNH 3
dCN2
r    
dt 3 dt 2 dt
17
The kinetic equation
A mathematical equation describes

the relationship between the rate and
the concentration (pressure) of the
reactants participating in it.
18
Review 1
1 dNi dCi
r   r 
V dt dt
Math expression?
r = f(x,y,z,…) r = f(Ci-Pi, T,…) = k.f(Ci-Pi)

19
1.2. Reaction Mechanisms
Example for complex reaction:
4Fe2+ + 4H+ + O2 = 4Fe3+ + 2H2O
20
This reaction goes through the following stages/steps:
Fe2+ + O2  Fe3+ + O2-


O2- + H+  H O2


Fe2+ + H O 2  Fe3+ + HO 2
HO 2 + H+  H2O2

H2O2 + Fe2+  Fe3+ + OH- + O H

Fe2+ + O H  Fe3+ + OH-
2OH- + 2H+  2H2O
21
Example of H2/O2 system
Reactions in
the H2/O2
systems
22
Mechanism of CH4 combustion (Warnatz 1996)
Chemical
reactions in a
CH4 flame
23
NOx in combustion processes (Warnatz 1996)
NOx
formation
and depletion
24
Note
 The sum of the stages in which a chemical reaction taking place is
called reaction mechanisms, and each stage of the reaction is
called the primary stage of the reaction.
 Substances participated in a chemical reaction are called
reactants.
 Substances produced during chemical metabolism and no
subjected to further transformation are called products.
 Substances produced in several stages are called intermediates.
25
1.3. Methods for determining a reaction rate
Determination of Experiment
the reaction rate
dCi
r
dt
26
Methods
Chemical method Physicochemical method
27
Chemical method
dCi
r 
dt
Determine the concentration of reactants (products) or

the total pressure of the gas system at different times.
28
Physicochemical
method
 Radioactivity
 Pole rotation
 The ability of light absorption
 Conductivity
 Electromotive force (EMF)
29
1.4. The rate law
The rate law (the rate equation)
The rate law for a chemical reaction is an

expression that provides a relationship between
the rate of the reaction and the concentrations
of the reactants participating in it.
30
1.4. The rate law

where a, b, c, and d
k are the stoichiometric
coefficients of the
aA + bB  products reactants or products
and k is the rate
constant
The rate equation for the reaction is given by:
Note that the
dCi
W  kC Ax CBy exponents x, y are not
dt usually equal to a, b
31
1.4. The rate law
The law of mass action
Law stating that the rate of any chemical reaction

is proportional to the product of the masses of the
reacting substances, with each mass raised to a
power equal to the coefficient that occurs in the
chemical equation.
Cato M. Guldberg and Peter Waage (1864-1879 )

32
1.4. The rate law
The rate of a simple (one step) reaction is directly

proportional to the concentration of the reacting
substances
33
1.4. The rate law
34
1.4. The rate law
Consider the following elementary reaction:
k
aA + bB  products
dCi
W  kC Aa CBb
dt
35
1.4. The rate law
Review 2
1 dNi dCi
Definition W  W
V dt dt
General W = f(x,y,z,…) W = f(Ci-Pi, T,…) = k.f(Ci)

Equation
The rate law dCi

W   kC Ax CBy (aA + bB  SP)
36 dt
Definition
The molecularity of a reaction is the number

of molecules in an elementary reaction
(single-step) at the microscopic (molecular)
level.
37
There are only possible cases for the molecularity (one example
for each case):
1. Monomolecular (= unimolecular) reactions:
CH3NC  CH3CN
2. Bimolecular reactions:
O + H2  OH + H
3. Termolecular reactions:
38 H + O2 + M  HO2 + M

k
aA + bB  products
x
dCi
W  kC ACB
x y
dt y
39 x+y
Definition
 x and y are called the partial reaction orders for

reactants A and B. We also say, the reaction is x-
th order in [A] and y-th order in B;
 The order of a reaction is defined as the sum of
the exponents in the rate law. It is n = x + y.
40
Caveats
 The order of a reaction is, in general, an empirical quantity,
it has to be determined by an experimental measurement;
 The order of a complex reaction cannot be determined by
simply looking at the overall reaction;
 The order of a reaction can be integer or non-integer or can
also be fractional.
 A negative order in a concentration means that the
respective species acts as an inhibitor.
 A positive order in a product concentration means that the
reaction rate is enhanced autocatalyst.
41
Example
42
Summary
n values Rate equation Reaction order

dC
0 W k Zero order reactions
dt
dC
1 W  kC First-order reactions
dt
dC
2 W  kC1 .C 2  kC 2 Second-order reactions
dt
dC
3 W  kC1 .C22  kC12 .C2  kC3 Third-order reactions
dt
dC
n W   kC n nth-order reactions
43 dt
Difference Between Molecularity

and Order of Reaction
Molecularity Order of Reaction

It can be a whole number or a
It is always a whole number
fraction.
It can be determined from the It must be determined
balanced chemical equation experimentally
Is only applicable in simple The reaction order is applicable
reactions in all chemical reactions
44

Chapter 1. Fundamental Definitions

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Chapter 1. Fundamental Definitions

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INTRODUCTION

Lecturer: PhD. Nguyen Minh Quang

50% Final examination 1 written

Chapter Topic Class hours

Chapter CLOs Assessment

Fundamental definitions of chemical

1.1. The rate of a chemical reaction

It is determined by the change in the

The reaction rate r is defined as

12 Note: signs “”

Convention for the signs “”

 “+” : calculated for the products.

Consider the following reaction:

If we do not mention to the scale factor yet

dCA d [A] dCC d [C ]

Consider the following reaction:

If we mention to the scale factor

1 dCA 1 dCB 1 dCC 1 dCD

We will usually write the concentrations of a species A by using square

The kinetic equation

A mathematical equation describes

r = f(x,y,z,…) r = f(Ci-Pi, T,…) = k.f(Ci-Pi)

Example for complex reaction:

4Fe2+ + 4H+ + O2 = 4Fe3+ + 2H2O

This reaction goes through the following stages/steps:

Fe2+ + O2  Fe3+ + O2-

Example of H2/O2 system

Mechanism of CH4 combustion (Warnatz 1996)

NOx in combustion processes (Warnatz 1996)

Chemical method Physicochemical method

Determine the concentration of reactants (products) or

The rate law (the rate equation)

The rate law for a chemical reaction is an

Consider the following reaction:

The law of mass action

Law stating that the rate of any chemical reaction

Cato M. Guldberg and Peter Waage (1864-1879 )

The law of mass action

The rate of a simple (one step) reaction is directly

The law of mass action

Consider the following elementary reaction:

The rate equation for the reaction is given by:

General W = f(x,y,z,…) W = f(Ci-Pi, T,…) = k.f(Ci)

The rate law dCi

The molecularity of a reaction is the number

1. Monomolecular (= unimolecular) reactions:

Consider the following reaction:

The rate equation for the reaction is given by:

 x and y are called the partial reaction orders for

n values Rate equation Reaction order

Difference Between Molecularity

Molecularity Order of Reaction

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