Thermochemistry, Chemical Kinetics, Electrochemistry Phase Transition, Colloids in Food

COLLEGE OF AGRICULTURE
DEPARTMENT OF FOOD TECHNOLOGY
Course note
(Thermochemistry, Chemical Kinetics, Electrochemistry

Phase transition, Colloids in food )
Lecturer: Assoc. Prof. TRAN THANH TRUC
1
2021 - 2022
2
Output of the course
➢ Physical chemistry is quantitative chemistry and is active at the

overlap of physics, biology, medizine and chemistry.
3
➢ It is one of the traditional sub-disciplines of chemistry and is concerned
with the application of the concepts and theories of physics to
the analysis of the chemical properties and reactive behaviour of matter.
Knoweleges
Establishes and develops the principles that are used to explain and
interpret the observations made in chemistry.
BULK INDIVIDUAL RATES
Quantum mechanics Chemical reaction

Thermodynamics
& spectroscopy
Equilibrium Structure Changes

Electrochemical → Electrophoresis 4
Surface Phenomena → Colloids
Knoweleges
An overview of the importance of thermochemistry,

chemical kinetics, electrochemical processes and colloids
in Food Technology.
The knowledges about rate and mechanism of some
basic chemical processes related to food.
Chemical reactions in the presence of an interphase
boundary (normally) a 'liquid-gas' system.
Problems in colloidal system related to food (elmusion,
dispersions, foam).
5
CÁC YÊU CẦU CƠ BẢN CHO MÔN HỌC
Skills
Basic principles of physical chemistry and their relationship to

foods and their processing
Understanding, analyzing and partical applying the
knowleges of equilibrium, chemical kinetics, surface
phenomena in food technology.
To understand and predict changes occurring in a food
during processing, storage, and handling, since such
changes affect food quality
Ability to solve problem and work in group based on group

exercises. 6
Content
Lecture 1: Definitions and some basic laws
Lecture 2: Thermochemistry Thermodynamics
Lecture 3 Lecture 4 Lecture 5

Chemical kinetics Catalyzed reaction Electrochemistry
Lecture 6: Overview of colloidal properties

Phase
balance Lecture 7: The stability of colloidal system
7
Lecture 8: Application of colloidal properties in
Food Technology
Recommended readings
1. Walstra, P., 2003. Physical Chemistry of Food. Marcel Dekker,
Inc. , New York, USA.
2. Atkins, P. and J. de Paula, 2010. Physical Chemistry, (Ninth

Edition). W. H. Freeman and Company, New York, USA.
3. Whittaker, A.G., A.R.Mount & M.R.Heal, 2000. Physical

Chemistry. BIOS Scientific Publisher.
4. Castellan, G.W., 1983. Physical Chemistry (Third edition).

Addison-Wesley Publishing Company.
5. Dickinson, E. and R. Miller, 2000. Food Colloids –

Fundamental of Formulation. MPG Book Ltd, Bodmin,
Cornwall, UK 8
Teaching methods
✓ Done by means of computer ppt presentations,
available to the students before classes.
✓ General topics related to the use of chemico-physical

models for studying food and biological systems will be
discussed.
✓ Lectures will be implemented by means of problem

solving and “question time” like activities in order to
maximize the understanding level of the students.
9
Assessment methods and criteria
✓ Midterm examination (20%): written examination on
the whole syllabus during scheduled examination
sections.
✓ Final examination (60%): written examination consist

of open questions and problem solving in such a way that
the students can prove knowledge and understanding of
the module subjects.
✓ Practice test (20%): based on Laboratory practice and

summary report in group.
✓ Attending class: required (absence maximum: 20%) 10

Lecture 1
Definitions and some basic laws
1. Object and value of Physical Chemistry
Object of Physical Chemistry in Food Technology

Value of Physical Chemistry
2. Necessary conditions to occur chemical reactions
Thermodynamic conditions
Chemical kinetic conditions

11
Catalytic conditions
Chương 1
3. Some types of chemical reactions
Chemical systems
Simple and complex reaction
Complete and incomplete reaction
Homogeneous, hetetogeneous reaction

12
Chương 1
4. Rate of reaction
Definition
Formula of rate of reaction
5. Law of mass action
6. Classification of reaction kinetics
Molecularity 13
Order of reaction
1. Object and value of Physical Chemistry
Object of Physical Chemistry – Food Technology
- Study about food chemistry issues that has the
interaction between physics and chemistry.
- The physicochemical principles of reactions and
transitions occur during food production, processing
and storage.
Value of Physical Chemistry
- Theory: Understanding the laws, kinetics characteristics
and mechanisms of chemical reactions.
- Practice: Determining the optimal working regime of

reactive systems and equipments → Improve labor
productivity. 14
2. Conditions required in chemical reactions
Thermodynamics
✓Investigate the initial and final state of the system.

✓ Condition to occur the reaction: G = H - T.S <0
→ The energy difference resulting from the free energy (ΔG) given off
during a chemical reaction—the stability of the products relative to
the reactants.
→ only gives information regarding the equilibrium conditions of
products after the reaction takes place, but does not explain the rate
of reaction
Thermodynamic conditions:
- GT,P = H - TS  0 : The process is spontaneous
- GT,P > 0 : The process is non-spontaneous 15
- GT,P = 0 : The process is at equilibrium
Chemical kinetic: related to reactivity.
➢ Intermediate reaction : reaction mechanism
➢ The reaction is fast or slow: rate of reaction
➢ Factors that affect rate of reaction: enough activation

energy
Catalytic conditions:
- Increasing the rate of reaction by reducing
Catalysts the activation energy of the system.
- Increasing the rate of reaction but does not
16
change the equilibrium of reaction.
Intermidiate
Activation
energy
Reactants
Products
17
18
Chemical systems
Surrounding Chemical system

H2 and O2 (gas)
19
Chemical systems
- System in which chemical reactions occur
- Include reactants, product, intermediate
Surrounding Chemical system

H2 and O2 (gas)
20
Chemical systems
Open system Closed Isolated system 21
system
Chemical system
- System in which chemical reactions occur
- Include reactants, product, intermediate
Simple and complex reaction

Simple reaction is a one-way reaction that only
occurs in a single state.
NO + O3 → NO2 + O2
Complex reaction: 2N2O5 → 4NO2 + O2
Include 2 steps: N2O5 → N2O3 + O2
N2O3 + N2O5 → 4NO2 22
3 Complete and incomplete reaction

- Complete reaction: is one where all of at least one of
the available reactants is used up and converted into
products.
- Incomplete reaction: The reactants are not used up
when the reaction stopped.
Example:
C6H6 + HNO3(đ) → C6H5NO2 + H2O
When H2O was produced → HNO3 was no longer
sufficiently dense.
→ The reaction stopped even the reactants still remain.
23
Phase
➢ Phase is a distinct and homogeneous state of a system
with no visible boundary separating it into parts.
➢Similar in chemical compositions and physical chemistry
properties.
➢ Separate from other phases by surface phase separation.
1 phase system:
Homogeneous system
24
2 or more phase:
Heterogeneous system
3 Homogeneous & Heterogeneous reaction

- Homogeneous system: System that has one or same phase such
as liquid or gaseous
- Homogeneous reaction: Reactions in which reactants and
products are in the same phase of matter.
- Heterogeneous system: The system that has more than one
phase.
- Heterogeneous reaction:
- Chemical reactions in which the reactants and products are in two
or more phases → lack the uniformity
- Take place on the surface of a catalyst of a different phase.
- Homo – Heterogeneous reaction:
- Complex reaction 25
- 2 stages: first step → Homogeneous; second step: Heterogeneous
-BaCl2 + Na2SO4 → BaSO4 + 2NaCl

-NH3 + HCl → NH4Cl
-NaOH + HCl → NaCl + H2O
-2CO + O2 → 2CO2
-C + O2 → CO2
-Fe + H2SO4 → FeSO4 + H2
26
Adiabatic system – Do not transfer matter and heat.

- Transfer work
Homogeneous system - Do not have interface.
Uniform system– Compositions and properties are the same
Heterogeneous system - - Have interface 27

28
4. Rate of reaction
Reaction: aA → bB
Reactant Product
CM
CA1
CB2
CA2
CB1 = 0
0 t (s) 0 t (s)
t1 = 0 t2 t1 = 0 t2
Concentration of the Concentration of the

reactant changes over time product changes over time
29
4. Rate of reaction
Reaction: A + B → C
Reactants Product
At t = 0 At t = 15 At t = 30 At t = 60
A=7 A=3 A=1 A=0 30
B=7 B=3 B=1 B=0
C=0 C=4 C=6 C=7
4. Rate of reactions
Definition
Rate of reaction is the change in

concentration of the reactants or products
over the change in time.
31
4. Rate of reaction
- At constant temperature, a chemical reaction occurs

like below:
A + B + ... → X + Y + ... (1)
- At t, concentration of substances in the reaction:
CA, CB, CX, CY or [A], [B], [X], [Y]
- Concentration of substances at t + t is:
CA + CA, CB + CB, CX + CX, CY + CY
32
or [A] + [A], [B] + [B],...
4. Rate of reaction
- Average rate of reaction was determine by formula:

∆CA
vA = −
∆t
∆CX
vX =
∆t
- In general:
∆𝐂𝐢
𝐯ഥ𝐢 = ±
∆𝐭 (i = A, B, X, Y)
33
4. Rate of reaction

- When t → 0, rate of reaction is called Instantaneous
rate, is represented by an expression:
𝐝𝐂𝐢
𝐯=±
𝐝𝐭
- Can determine the rate of reaction (1) according to the
formula:
dCA dCB dCX dCY
v=− =− = =
dt dt dt dt
Or:
34
dA dB dX dY
v=− =− = =
dt dt dt dt
4. Rate of reaction
- For general reaction:

aA + bB + ... → xX + yY + ... (2)
(a, b, x, y is ratio coefficient of the substances)
- The reaction rate is often found to have the form:
−𝟏 𝐝 𝐀 −𝟏 𝐝 𝐁 𝟏 𝐝𝐗 𝟏 𝐝𝐘
𝐯(𝐫) = . = . = . = .
𝐚 𝐝𝐭 𝐛 𝐝𝐭 𝐱 𝐝𝐭 𝐲 𝐝𝐭
35
Formula of law of mass action (rate law):
- General expression:
𝐯=𝐤𝐀 𝐦. 𝐁 𝐧
(rate equation or kinetic equation of chemical reaction)

- At the constant temperature, rate equation is an equation
that links the reaction rate with the concentrations or
pressures of the reactants and constant parameters
(normally rate coefficients and partial reaction orders).
- k: reaction rate constant or reaction rate coefficient
36
When [A] = [B] = 1 mol/L → v = k
Formula of law of mass action:

- General expression: 𝐯 = 𝐤 𝐀 𝐦. 𝐁 𝐧
➢ The exponents m and n are called partial orders of reaction

and are not generally equal to the stoichiometric coefficients
a and b.
➢ Instead they depend on the reaction mechanism and can be
determined experimentally.
Example:
N2O5 → 2NO2 + 1/2O2 v=k[N2O5]
2NO + O2 → 2NO2 v=k[NO]2.[O2]
H2 + I2 → 2HI v=k[H2].[I2] 37
Molecularity
The number of molecules that come together to react in an
elementary (single-step) reaction and is equal to the sum of
stoichiometric coefficients of reactants in this elementary
reaction.
Depending on how many molecules come together, a reaction
can be unimolecular, bimolecular or trimolecular.
3 levels of reactions
1 Unimolecular: I2 → 2 I
1
2 Bimolecular: 2HI → I2 + H2
38
1
3 Trimolecular : 2NO + O2 → NO2
Order of reaction
Order of reaction is an empirical quantity determined by
experiment from the rate law of the reaction.
It is the sum of the exponents in the rate law equation
- With general reaction:

aA + bB + ... → xX + yY + ...
Kinetic equation is:
𝐯=𝐤𝐀 𝐧𝟏 . 𝐁 𝐧𝟐
When [A] = [B], the expression can be described as:

39
𝐧𝟏 . 𝐧𝟐 𝐧𝟏 +𝐧𝟐 𝐧
𝐯=𝐤𝐀 𝐁 =𝐤 𝐀 =𝐤𝐀
Order of reaction
𝐧𝟏 𝐧𝟐 𝐧𝟏 +𝐧𝟐 𝐧
𝐯=𝐤𝐀 . 𝐁 =𝐤 𝐀 =𝐤𝐀
➢ n: overall reaction order (sum of the exponents)
➢ n1: partial orders of reaction with respect to A
➢ n2: partial orders of reaction with respect to B
Note:
- In general case, n1  a, n2  b; with simple reaction, n1 = a, n2 = b
- Order of reaction (n1, n2,...) is the value only determined by 40

experiment, after the reaction mechanism is known.
7 Revision
1. Answer the questions

a) What is rate of reaction, rate constant?
b) Explain how kinetics relate to thermodynamics.
c)Why would it be beneficial for a thermodynamically-stable
reaction to use an energy input in the form of an enzyme or a
catalyst even if it does not require energy to proceed?
c) Rate of reaction and rate constant depend on which factor?
d) How is the rate constant k related to equilibrium? How does the
rate constant change if heat is added to the reaction?
e) If the difference in energy between the reactants and products is
negative, is the reaction spontaneous or nonspontaneous?
f) Difference between molecularity and order of reaction 41
7 Revision
2. Writing of rate equation of simple reaction. Determination of

overall reaction order and partial orders of reaction
✓ H2 + I2 → 2HI
✓ 2NO + O2 → 2NO2
✓ 2NO + Cl2 → 2NOCl
✓ 2NO + Br2 → 2NOBr
✓ 2FeCl3 + SnCl2 → 2FeCl2 + SnCl4
✓ RCOOR' + NaOH → RCOONa + R'OH
✓ CH3COOH + C2H5OH → CH3COOC2H5 + H2O
42
Chapter 3
CHEMICAL KINETICS
1. Expression of rates.
2. Kinetics of simple, homogeneous reactions
3. Method to determine order of reaction
4. Elementary steps and reaction mechanism
43
1. Expression of rates
Chemical Kinetics
➢The study of reaction rates

• How fast does a reaction proceeds and what factors
affecting it;
• A measure of the change of the concentration of a
reactant (or a product) as a function of time.
➢The study of rate yields information on the mechanism

by which a reaction occurs at molecular level.
44
Types of Rates
• Initial Rates
• Rates measured at the beginning of the reaction,
which is dependent on the initial concentrations of
reactants.
• Instantaneous Rates
• Rates measured at any point during the reaction.
• Average Rates
• An overall rate measured over a period or time
interval.
45
Types of Rates
Example: Rate of reaction between phenolphthalein with excess base.
Experimental Data for the Reaction Between Phenolphthalein and Base
Concentration of
Phenolphthalein (M) Time (s)
0.0050 0.0
0.0045 10.5
0.0040 22.3
0.0035 35.7
0.0030 51.1
0.0025 69.3
0.0020 91.6
0.0015 120.4
0.0010 160.9
0.00050 230.3 46
0.00025 299.6
0.00015 350.7
0.00010 391.2
Types of Rates
Instantaneous Rate: 47
Rate of decrease in [Phenolphthalein]

Types of Rates
Instantaneous Rate
• Value of the rate at a particular time.
• Can be obtained by computing the slope of a line
tangent to the curve at that point.
48
Types of Rates
Instantaneous Rate
49
Types of Rates
Instantaneous Rate
50
The Decomposition of Nitrogen Dioxide

Types of Rates
Average Rate
• Consider the following reaction at 300oC:

2 NO2(g) → 2 NO(g) + O2(g)
• The initial concentration of NO2 is 0.0100 mol/L and its

concentration after 150 s is 0.0055 mol/L. What are the
average rates of this reaction during the first 150 s and
during the second 150 s?
51
Types of Rates
Average Rate
Average rate during the first 150 s
• Solution:
- [NO 2 ]
Average rate =
t
- (0.0055 mol/L - 0.0100 mol/L)
=
150 s
0.0045 mol/L
=
150 s
= 3.0 x 10-5 mol/(L.s) 52

Types of Rates
Average Rate
Average rate during the second 150 s

• Solution:
- [NO 2 ]
Average rate = t
- (0.0038 mol/L - 0.0055 mol/L)
=
150 s
0.0017 mol/L
= = 1.1 x 10-5 mol/(L.s)
150 s
Average rate decreases as reaction progresses
because the reactant concentration has decreased 53
Types of Rates
Rate Order
• The power or exponent of the concentration of a given reactant
in the rate law. It indicates the degree in which the rate
depends on the concentration of that particular reactant.
• The sum of the powers of the concentrations is referred to as
the overall order for the reaction.
54
Types of Rates
Expressions of Reaction Rates and Their Stoichiometric Relationships
Consider the reaction: 2N2O5 → 4NO2 + O2

[N 2 O 5 ]
• Rate of disappearance of N2O5 = −
[ NO 2 ] t
• Rate of formation of NO2 =
t
[O 2 ]
• Rate of formation of O2 =
t
• Stoichiometric relationships of these rates
1 [N 2 O5 ] 1 [ NO 2 ] [O 2 ] 55
(− )= ( )=
2 t 4 t t
Homogeneous reaction
- The substances is in the same phase (physical state)
- Example:
CH3COOC2H5 + NaOH → CH3COONa + C2H5OH
CO + O2 → CO2
Simple reaction
One-way reaction, there is only one phase going
directly from the initial to the final substance.
Complete reaction
When the reaction occurs, at least one of the reactants
(initial substance) is used up and converted into 56
product.
First-order reactions
Example: CH3-CO-CH3 → CO + H2 + C2H4
General reaction: A → Product

At t = 0 [A]o = a 0
At t [A] = (a-x) x
With: [A]o: Initial concentration of A

[A]: Concentration of A at t 57
x: Decomposition of A to product
As definition and law of mass action, we have:
dA d a−x dx
v=− =− = = k1 A = k1 a − x
dt dt dt (2.1)
dx dx
= k1 a − x = k1 dt
dt (a − x)
dx
Take the integral 2 sides: න = න k1 dt
a−x
− 𝐥𝐧 𝐚 − 𝐱 = 𝐤 𝟏 𝐭 + 𝐜𝐨𝐧𝐬𝐭
(const: integral constant) (2.2)
58
First-order reaction: the rate is proportional to the
concentration of one of the reactants.
• At the initial time: t = 0, x = 0 → -lna = const
• Expression (2.2) become:
Or (2.3)
Dimension of k1 : t-1
Half-life of reaction (time taken for one-half of a
reactant to be consumed)
(2.4)
59
Half-life of first-order reaction does not depend on the initial
concentration of reactants, only depends on rate constant.
Second-order reactions
Common one-way second-order reaction:

2NO2 → 2NO + O2
→ Rate = k[NO2]2
H2 + I2 → 2HI
→ Rate = k[H2][I2]
CH3COOC2H5 + NaOH → CH3COONa + C2H5OH
→ Rate = k[CH3COOC2H5][NaOH ]
In a second order reaction: the rate is proportional to the 60

second power of the concentration of one of the reactants.
General reaction: A + B → products

At t = 0 a b 0
At t a–x b–x x
With: a, b: Initial concentration of A, B
(a-x), (b-x): concentration of A, B at t
x: concentration of decomposition A, B
Rate (2.5)
61
(2.6)
If a = b
(The initial concentration of 2 reactants are equal)
dx
Expression (2.6) become: න 2 = න k 2 dt
a−x
1
= k 2 t + const (2.7)
a−x
At the initial time: t = 0, x = 0 → 1/a = const
- Dimension of k2 : t-1.(C)-1
- Half-life of reaction: 𝟏 𝟏
𝟏 𝟏 𝟏 𝟏 − = 𝐤𝟐𝐭 62
𝛕𝟏ൗ = − = (2.9) 𝐚−𝐱 𝐚
𝐤𝟐 𝐚 𝐚 𝐚. 𝐤 𝟐
𝟐
𝟐 (2.8)
If a  b
(The initial concentration of 2 reactants are different)
From (2.6):
1 a−x b
. ln . = k2t (2.10)
a−b b−x a
1 1 a−x b
k2 = . . ln . (2.11)
t a−b b−x a
(Kinetic equation of one-way second-order reaction, 63

when a  b)
Decreasing order of reaction rate
In case where the concentration of a substance is very large
compared to the other substance, suppose b >> a, then: a-b 
-b, b-x  b, expression(2.10) can be rewritten:
1 a−x b
. ln . = k2t
−b b a
a−x
−b. k 2 t = ln 𝐚−𝐱
a 𝐤′𝐭 = 𝐥𝐧 (2.12)
𝐚
k’ = -b.k2
Expressions take the form of a 1-
dimensional, first-order reaction: 64
pseudo first-order reaction
Third-order reactions
Third-order reaction is very rare, some reactions:
2NO + O2 → 2NO2
2CO + O2 → 2CO2
General reaction: A + B + C → Product

At t = 0 a b c
At t a-x b-x c-x x
With:
a, b, c: The initial concentration of A, B, C
65
(a-x), (b-x), (c-x): Immediate concentration of A, B, C at t
x: Concentration of decomposition A, B, C
The rate law for this reaction takes the form:
𝐝𝐱
𝐯= = 𝐤𝟑 𝐚 − 𝐱 𝐛 − 𝐱 𝐜 − 𝐱 (2.13)
𝐝𝐭
a=b=c a=cb abc

66
If a = b = c
dx
(2.13) = k3 a − x 3
dt
𝟏 𝟏 𝟏
𝐤𝟑𝐭 = . 𝟐
− 𝟐 (2.14)
𝟐 𝐚−𝐱 𝐚
Half-life of the reaction:

1 1 1 3
τ1ൗ = . 2
− 2 = (2.15)
2 2k 3 aΤ2 a 2. a2 . k 3 67
If a = c  b
dx
v= = k 3 a − 2x b − x
dt
𝟏 𝟐𝐛 − 𝐚 . 𝟐𝐱 𝐛(𝐚 − 𝟐𝐱)
𝐤𝟑𝐭 = 𝟐
. + 𝐥𝐧 (2.16)
𝟐𝐛 − 𝐚 𝐚 − 𝟐𝐱 . 𝐚 𝐚 𝐛−𝐱
68
Third-order reactions:
If a  b  c
dx
v= = k3 a − x b − x c − x
dt
𝟏 𝐚 𝟏 𝐛
𝐤𝟑𝐭 = 𝐥𝐧 + 𝐥𝐧
𝐚−𝐛 𝐚−𝐜 𝐚−𝐱 𝐛−𝐚 𝐛−𝐜 𝐛−𝐱
𝟏 𝐜
+ 𝐥𝐧 (2.17)
𝐜−𝐛 𝐜−𝐚 𝐜−𝐱
69
Third-order reactions:
Decreasing order of reaction rate
In case c >> a, c >> b, then: a-c  -c, c-a  c, c-x  c,
expression (2.17) can be rewritten:
1 a 1 b
k3t = − ln − ln +0
a −b .c a − x b − a .c b − x
𝟏 𝐚−𝐱 𝐛
𝐜. 𝐤 𝟑 𝐭 = 𝐥𝐧 . (2.18)
𝐚−𝐛 𝐛−𝐱 𝐚
Expressions take the form of second-order reaction:
pseudo second-order reaction 70
2. Kinetic of simple, homogeneous reaction
n-order reaction:
With n-order reaction has the initial concentration of the

substances are the same, we have:
1 1 1
knt = . n−1
− n−1 (2.19)
n−1 a−x a
Half-life:
1 2n−1 − 1
τ1ൗ = . (2.20)
2 n − 1 k n . an−1
71
1. Kinetic of simple, homogeneous reaction
Zero-order reaction:
Example: Hydrolysis reaction of ester: Ester
R-COO-R’ + H2O → R-COOH + R’-OH Ester in water
[H2O]o = [H2O] = const

We have: [R-COO-R’]o = [R-COO-R’] = const
dx d R − COO − R′
v= =− = k H2 O R − COO − R′ = k. const = k′
dt dt
2 HI(g) → H2(g) + I2(g) → Rate = k[HI]0 = k
→ The rate is independent on the concentration of HI
▪ Rate of reaction does not change by time.

72
▪ In a zero order reaction the rate does not depend on
the concentration of reactant
Determination of Rate Law using Initial Rate

• Consider the following reaction:
S2O82-(aq) + 3I-(aq) → 2SO42-(aq) + I3-(aq)
The following data were obtain
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
Expt. [S2O82-] [I-] Initial Rate,
# (mol/L) (mol/L) (mol/L.s)
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
1 0.036 0.060 1.5 x 10-5
2 0.072 0.060 2.9 x 10-5
3 0.036 0.120 2.9 x 10-5 73
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯

Reaction: S2O82-(aq) + 3I-(aq) → 2SO42-(aq) + I3-(aq)
(a) Determine the order of the reaction w.r.t. each

reactant. Write the rate law for the above reaction.
(b) Calculate the rate constant, k, and give its
appropriate units.
(c) Calculate the reaction rate when each reactant
concentration is 0.20 M
74
Solution: The rate law = Rate = k[S2O82-]x[I-]y,

here x and y are rate orders.
(a) Calculation of rate order, x:

2- x y
k [S 2 O8 ]2 [I - ]3 k (0.072 M ) x (0.060 M ) y
2- x y
= = 2 x
k [S 2 O8 ]1 [I - ]1 k (0.036 M ) x (0.060 M ) y
2.9 x 10 -5 mol/L.s
= -5
~ 2 = 2 x
= y = 1
1.5 x 10 mol/L.s
75

(b) Calculation of rate order, y:
2- x - y
k [S 2 O8 ] [I ]3 k (0.036 M ) x (0.120 M ) y
2- x - y
= x y
= 2 y
k [S 2 O8 ] [I ]1 k ( 0.036 M ) ( 0.060 M )
2.9 x 10 -5 mol/L.s
= -5
~ 2 = 2 = y = 1
y
1.5 x 10 mol/L.s
This reaction is second order w.r.t. [S2O82-] and [I-]

Rate = k[S2O82-][I-] 76

Calculating rate constant and rate at different concentrations
of reactants
1.5 x 10 -5 mol/L
Rate constant, k =
(0.038 mol/L)(0.0 60 mol/L)
= 6.6 x 10-3 M-1.s-1
If [S2O82-] = 0.20 M, [I-] = 0.20 M, and

→ k = 6.6 x 10-3 M-1.s-1
Rate = (6.6 x 10-3 L.mol-1.s-1)(0.20 mol/L)2 77
= 2.6 x 10-4 mol/(L.s)

Integrated Rate Law

Graphical method to derive the rate law of a reaction:
• Consider a reaction with single reactant:
R → Products
Graphical Method for Zero-Order Reaction
- [R]
• If the reaction is zero-order w.r.t. [R] Rate = =k
t
[R] = -kt, and [R]t = [R]0 = kt;
A plot of [R]t versus t yields a straight line with k = -slope.

78
Integrated Rate Law

79
Various Plots for Zero Order Reactions
Integrated Rate Law

• Plot of [R]t versus t:
slope = -k
[R]t
t
80
Graph of Zero-order Reactions

Integrated Rate Law

Graphical Method for First-Order Reaction
If the reaction: R → Products is a first order reaction, then
- [R]
Rate = = k [R]
t
[R]
Which yields: = - kt; ln[R] t = ln[R] 0 - kt
[R]
And a plot of ln[R]t versus t will yield a straight line with
slope = -k 81
y-intercept = ln[R]0
Integrated Rate Law

Plot of ln]R]t versus t:
ln[R]t slope = -k
t 82
Graph of First Order Reactions
Integrated Rate Law

83
Plots of [A] and ln[A] versus time for First Order Reactions
Integrated Rate Law

84
Various Plots for First Order Reactions
Integrated Rate Law

Graphical Method for Second-Order Reactions
If the reaction: R → Products follows second-order kinetics, then

- [R] [R]
Rate = = k [R]2 or 2
= k t
t [R]
1 1
and = kt +
[R] t [R]0
A plot of 1/[R]t versus t will yield a straight line with

slope = k
85
y-intercept = 1/[R]0
Integrated Rate Law

86
Various Plots for Second Order Reactions
Integrated Rate Law

Plot of 1/[R]t versus time:
1
[ R]t slope = k
time 87
Graph of Second-order Reactions
Integrated Rate Law
88
Plots of concentration versus time for first
and second order reactions
Integrated Rate Law
89
Plots of ln[Concentration] versus time

Integrated Rate Law
90
Plots of 1/[Concn.] versus time

Integrated Rate Law

Characteristics of plots for zero, first, and second order reactions
The graph that is linear indicates the order of the

reaction with respect to A (reactant):
• For a zero order reaction, Rate = k (k = - slope)
• For a 1st order reaction, Rate = k[A] (k = - slope)
• For a 2nd order reaction, Rate = k[A]2 (k = slope)
• For zero-order reaction, half-life, t1/2 = [R]0/2k;

• For first order reaction, half-life, t1/2 = 0.693/k; 91
• For second order reaction, half-life, t1/2 = 1/k[R]0;
Integrated Rate Law
Half-Lives of Reactions
• For zero-order reaction: t1/2 = [R]0/2k;
• For first-order reaction: t1/2 = 0.693/k;
• For second-order reaction: t1/2 = 1/(k[R]0)
Note: For first-order reaction, the half-life is independent of

the concentration of reactant, but for zero-order and second-
order reactions, the half-lives are dependent on the initial 92
concentrations of the reactants.
Integrated Rate Law

Summary of rate laws
93
Reaction Mechanism
• The detail pictures of how a given reaction occurs at

molecular level
• It consists of a set of elementary steps that shows
probable reactions involving molecular species –
including reaction intermediates.
• The sum of these elementary steps yields the overall
balanced equation for the reaction.
94
Elementary Steps
For example, the overall reaction: 2A + B → C + D

may involves the following elementary steps in its mechanism:
• Step-1: A+B → X;
• Step-2: X + A → Y;
• Step-3: Y→C+ D
• Overall reaction: 2A + B → C + D;
95
Elementary Molecularity in
Elementary Steps
Molecularity in the number of molecular species that react in

an elementary process.
Rate Law for Elementary Processes:
Elementary Reactions Molecularity Rate Law
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
A → product Unimolecular Rate = k[A]
2A → product Bimolecular Rate = k[A]2
A + B → product Bimolecular Rate = k[A][B]
96
2A + B → product Termolecular 2
Rate = k[A] [B]
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
Elementary Molecularity in
Elementary Steps
A Molecular Representation of the Elementary Steps in the Reaction

of NO2 and CO
NO2(g) + CO(g) → NO(g) + CO2(g)
97
Reaction Mechanism
• Step-1: NO2 + NO2 → NO3 + NO
• Step-2: NO3 + CO → NO2 + CO2
• Overall: NO2 + CO → NO + CO2
The experimental rate law is Rate = k[NO2]2
Which implies that the above reaction is second-order
w.r.t. NO2 , but is zero-order in [CO].
Reaction Mechanism Requirements
• The sum of the elementary steps must give the overall balanced
equation for the reaction.
98
• The mechanism must agree with the experimentally determined
rate law.
Reaction Mechanism
Decomposition of N2O5
2N2O5(g) → 4NO2(g) + O2(g)
Step 1: N2O5 ⇌ NO2 + NO3 (fast)
Step 2: NO2 + NO3 → NO + O2 + NO2 (slow)
Step 3: NO3 + NO → 2NO2 (fast)
99
Reaction Mechanism
A Model for Chemical Reactions

For a reaction to occur:
1. Reactant molecules must collide;
2. Molecular collisions must occur with proper orientations;
3. Collisions must be energetic and lead to the formation of the
transition-state complex;
4. The rate of formation of the transition-state complex is the rate
determining step;
5. The transition-state complex eventually leads to the formation
of products;
100
Reaction Mechanism
A Model for Reaction Kinetics
• All chemical reactions proceed through a transition-state complex;
• An energy barrier called activation energy (Ea) must be overcome
to change reactants to the transition-state.
• The rate of formation of transition-state is the rate-determining
step for the overall reaction;
• The rate of formation of transition-state is dependent:
• on the frequency of effective molecular collisions, which
depends on the reactants concentrations;
• on the fraction of molecules with sufficient kinetic energy to
overcome the energy barrier, and 101
• on the reaction temperature

Reaction Mechanism
102
Change in Potential Energy

Reaction Mechanism
For Reactants to Form Products
• Collision must involve enough energy to produce the reaction

(must equal or exceed the activation energy).
• Relative orientation of the reactants must allow formation of
any new bonds necessary to produce products.
103
Factors effects on reaction rate
Dependence of Rate on Concentration

• This is contained in the rate law – that is, for reaction:
aA + bB + cC → Products
Rate = k[A]x[B]y[C]z;
104
Dependence of Rate on Temperature

Rate depends on the fraction of “effective collisions”
per unit time.
• (Effective collisions are those with proper orientation and
sufficient energy to overcome activation energy Ea barrier.
Thus rate depends on the activation energy and
temperature, such that,
• Higher activation energy implies high barrier and fewer
reactant molecules will form the transition-state complex.
This leads to a slower rate of reaction;
• Higher temperature results in a larger fraction of reactant
molecules with sufficient energy to overcome the energy 105
barrier. This leads to a faster rate of reaction.

Arrhenius equation:
In general, rate of reaction increases when the temperature is increased.
The experiment showed that, when the temperature increased 10
degrees, the rate of reaction increased 2-4 times.
Temperature coefficient of rate of reaction

𝐤 𝐓+𝟏𝟎
𝛄= (2.21)
𝐤𝐓
- kT: rate constant of the reaction at the temperature T 106
- kT+10: rate constant of the reaction at the temperature T+10


Arrhenius equation:
From the Van’t Hoff equation, the relationship between the rate constant
and the temperature coefficient can be determined more accurately:
𝐝𝐥𝐧𝐊 ∆𝐇
=
𝐝𝐓 𝐑𝐓 𝟐
- K=k1/k2: equilibrium constant of reaction

- k1, k2: rate constant
- H: Enthalpy of reaction = E1 – E2
107
- R: is the gas constant with a value of 8.314 J/K mol
- T: temperature, K

Arrhenius equation:
k1
dln
Expression (2.22) can be rewritten: k 2 dlnk1 − dlnk 2 ∆H
= =
dT dT RT 2
Enthalpy of reaction can be rewritten: H = E1 – E2
dlnk1 E1
dlnk1 dlnk 2 E1 E2 = +B
− = − 2 dT RT 2
dT dT RT 2 RT or dlnk 2 E2
= 2
+B
dT RT
Experimental: B=0
𝐝𝐥𝐧𝐤 𝐄 Arrhenius equation,

= express the dependence of the rate 108
𝐝𝐓 𝐑𝐓 𝟐 constant on temperature,
(2.23) with E (EA) is activation energy

Arrhenius equation:
How to determine activation energy:
From (2.23):
dlnk E E E
= dlnk = . dT lnk = − + lnk 0
dT RT 2 RT 2 RT
(2.24)
𝐄 𝐄𝐀
(2.24) ➔ −𝐑𝐓 −𝐑𝐓 (2.25)
𝐤 = 𝐤𝟎. 𝐞 𝐤 = 𝐀. 𝐞
109
Relationships between rate, rate constant, activation energy,

& temperature
• Rate is dependent on rate constant, which is the
proportionality constant that relates rate to
concentrations (as depicted in the rate law).
• While rate constant is related to activation energy
and temperature by the Arrhenius equation:
• k = Ae-Ea/RT
• where A is Arrhenius collisional frequency factor, T is the Kelvin
temperature, and R is gas constant (R = 8.314 J/K.mol) 110
Graphical relationships of k, Ea, and T

• From Arrhenius equation: k = Ae-Ea/RT
ln(k) = ln(A) – (Ea/R)(1/T)
• The plot of ln(k) versus 1/T yields a straight line with the
slope = -(Ea/R), or Ea = -slope x R
• If k values are determined at two different temperatures,

such that at k1 at T1 and k2 at T2, then
Ea 1 1
ln(k2/k1) = − ( )( - ) (R = 8.314 J/K.mol)
R T2 T1 111

Energy Profile of Endothermic Reaction
112
Energy Profile for Exothermic Reaction
113
5. Exercises
Ex 1: Poloni after 14 days decreased by 6.85% compared to the
original. Determination of the rate constant and the half-life of Poloni.
This is first-order reaction.
Ex 2: The half-life of the 14C decomposition reaction is 5700 years.
The quantitative result of 14C in a sample is 25% compared to the
original sample. Determine the "age" of the sample.
Ex 3: Within 10 minutes, the reaction between the two substances
occurs 25% of the original amount. Calculate the half-life of the
reaction if the initial concentrations of the two substances in the
second order reaction are the same.
Ex 4: Within 10 minutes, both first and second order reactions have
40% of the initial substrate involved in the reaction. Calculate the
time for 2 reactions to use up 60% if the initial concentrations of the
two substances in the second order reaction are the same.
Ex 5: At 378C, the half-life of a first order reaction is 363 minutes. 114
Calculate the time to react at 75% of its initial concentration at 450C,
knowing that the activation energy of the reaction is 52,000cal/mol.
5. Exercises
Ex 6: Consider the reaction aA → Products.

[A]0 = 5.0 M and k = 1.0 x 10–2
(assume the units are appropriate for each case). Calculate [A] after 30.0
seconds have passed, assuming the reaction is:
a) Zero order 4.7 M
b) First order 3.7 M
c) Second order 2.0 M
Ex 7: Chemists commonly use a rule of thumb that an increase of 10 K in
temperature doubles the rate of a reaction. What must the activation
energy be for this statement to be true for a temperature increase from
25C to 35C? (Ea = 53 kJ)
Ex 8:Consider the reaction of gas NH3 and gas NO2 is second order
reaction. Calculation of activation energy and ko (in Arrhenius.
Equation, 2.25). At 327C, rate constant k = 0.385 M-1.s-1 and 115
k(443C) =16 M-1.s-1
5. Exercises
Ex 9: To formation of ethylene which using for ripening fruit,

CH3COCH3 was used as reactant: CH3COCH3 = C2H4 + CO + H2
The below table showed the change of total pressure followed
by time
Time (minutes) 0 6,5 13 19,9
Total P (N/m2) 41589.6 54386.6 65050.4 74914.6
Determine the order of the reaction and the reaction rate constant
Ex 10: If the first-order reaction has an activation energy of

25,000 cal/mol and the Arrhenius equation has a constant (ko)
of 5.1013 s-1, at what temperature, the half-life of the reaction
is 1 minute and 30 days?
116
5. Exercises
Ex 11: Calculate the activation energy of the vitamin C

decomposition reaction, based on the determination of the
reaction rate k by experimentally
Temp, C 30 60 70 80 90 100
k.10-15, s-1 0.0787 3.46 13.5 47.44 250 578
Ex 12: The inactivation of lipase is defined as a first order

reaction.
At 27C, the lipase activity is reduced by half after 5000 s and
at 37C, the half-life of reaction is 1.000 s. Determine
activation energy of the reaction.
117
5. Exercises
Ex13: Given a reaction A + B → C has the order of each substances is 1
and the rate constant k = 0,01 mol-1.lit.s-1. The initial concentration
of each substances is 0,1M. Calculate the concentration of A remains
after 100s.
Ex 14: There is a first-order reaction has k = 2,6.10-10 s-1 at 300oC and at
500oC is 6,7.10-4 s-1. Calculate the activation energy of the reaction.
(272 kJ/mol)
Ex 15: The hydrolysis of CH3Cl is first-order reaction. Ar 20oC, the rate
constant k is 3,32.10-10 s-1 and at 40oC is 3,13.10-9.s-1. Calculate the
activation energy of the reaction. (85.535,8 J/mol)
Ex 16: At 10oC, a reaction ends after 95s and at 20oC is 60s. Calculate the
activation energy of the reaction. (318kJ/mol)
Ex 17: A second-order reaction has the activation energy is 45kJ/mol. At
800oC, the rate constant k = 5.10-3mol-1.l.s-1. Calculate k(875oC)
(7.10-3mol-1.L.s-1) 118
5. Exercises
Ex 18: With the experimental results of the following reaction:
Write down the expression for the above reaction rate, reaction order, and
reaction rate constant
Ex 19: The activation energy of the hydrolysis reaction of sucrose to

glucose and fructose is 108 kJ / mol. If an enzyme increased the reaction
rate by 106 times, how many times did the activation energy of the
reaction decrease?
Assume A is constant and the reaction temperature is 25°C.
119
5. Exercises
Ex20: Consider the reaction : 2 NO + O2 → 2 NO2.

Conducted 3 experiments at 25C with different initial concentrations of the
substance, obtained the following results: :
Initial concentration of substrate x 10-2 Initial rate x 10-3
Experiments (mol/L) (mol/L.s)
O2 NO
1 1,1 1,3 3,2
2 2,0 1,3 5,8
3 1,1 3,0 17,0
a) Determine overall reaction order

b) Formula of law of mass action
c) reaction rate constant at 25oC
d) Calculate the activation energy of the reaction if the temperature 120
coefficient of rate of reaction () is 2.18.

Thermochemistry, Chemical Kinetics, Electrochemistry Phase Transition, Colloids in Food

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Thermochemistry, Chemical Kinetics, Electrochemistry Phase Transition, Colloids in Food

Uploaded by

Copyright:

Available Formats

COLLEGE OF AGRICULTURE

DEPARTMENT OF FOOD TECHNOLOGY

(Thermochemistry, Chemical Kinetics, Electrochemistry

Lecturer: Assoc. Prof. TRAN THANH TRUC

➢ Physical chemistry is quantitative chemistry and is active at the

BULK INDIVIDUAL RATES

Quantum mechanics Chemical reaction

Equilibrium Structure Changes

An overview of the importance of thermochemistry,

Basic principles of physical chemistry and their relationship to

Ability to solve problem and work in group based on group

Lecture 2: Thermochemistry Thermodynamics

Lecture 3 Lecture 4 Lecture 5

Lecture 6: Overview of colloidal properties

2. Atkins, P. and J. de Paula, 2010. Physical Chemistry, (Ninth

3. Whittaker, A.G., A.R.Mount & M.R.Heal, 2000. Physical

4. Castellan, G.W., 1983. Physical Chemistry (Third edition).

5. Dickinson, E. and R. Miller, 2000. Food Colloids –

✓ General topics related to the use of chemico-physical

✓ Lectures will be implemented by means of problem

✓ Final examination (60%): written examination consist

✓ Practice test (20%): based on Laboratory practice and

✓ Attending class: required (absence maximum: 20%) 10

Definitions and some basic laws

1. Object and value of Physical Chemistry

Object of Physical Chemistry in Food Technology

2. Necessary conditions to occur chemical reactions

Chemical kinetic conditions

Definitions and some basic laws

3. Some types of chemical reactions

Simple and complex reaction

Complete and incomplete reaction

Homogeneous, hetetogeneous reaction

Definitions and some basic laws

5. Law of mass action

6. Classification of reaction kinetics

- Practice: Determining the optimal working regime of

✓Investigate the initial and final state of the system.

Chemical kinetic: related to reactivity.

➢ Intermediate reaction : reaction mechanism

➢ The reaction is fast or slow: rate of reaction

➢ Factors that affect rate of reaction: enough activation

Surrounding Chemical system

Surrounding Chemical system

Open system Closed Isolated system 21

Simple and complex reaction

3 Complete and incomplete reaction

3 Homogeneous & Heterogeneous reaction

3 Homogeneous & Heterogeneous reaction

-BaCl2 + Na2SO4 → BaSO4 + 2NaCl

3 Homogeneous & Heterogeneous reaction

Adiabatic system – Do not transfer matter and heat.

Homogeneous system - Do not have interface.

Uniform system– Compositions and properties are the same

Heterogeneous system - - Have interface 27

Concentration of the Concentration of the

Rate of reaction is the change in

Formula of rate of reaction

- At constant temperature, a chemical reaction occurs

Formula of rate of reaction

- Average rate of reaction was determine by formula:

Formula of rate of reaction