Faculty of Chemical Engineering

Department of Inorganic Technology

General Chemistry

Chapter 5
Kinetic Chemistry

PhD. Đặng Văn Hân

Office: 112B2 or 804H3 Building
Email: dvhan@hcmut.edu.vn
Outline
1. Chemical Thermodynamics vs. Kinetics
2. Reaction Rate (rrxn)
3. Reaction Rate Constant (k)
4. Reaction Orders
5. Main Effects on the Reaction
Rate
6. Catalyst and Mechanism
2
Thermodynamics vs. Kinetics
Domain of
thermodynamics
(Initial & Final States) ❑ THERMODYNAMICS
Predicts direction and ‘driving force’ of
Domain of
kinetics
chemical reactions based ONLY on the
properties of reactants and products.

❑ KINETICS
Energy

Predicts rate of chemical reaction

Reactants depend on the pathway from reactants
to products.
Products
- The rate of chemical reactions;
- How to control or influence the rate (lower –
faster);
Reaction progress - The mechanism of reaction.
Reaction Rate
Consider rxn: A →
Reaction Rate: is expressed as the
B
t= t= t= concentration of reactant consumed or
0s 30 s 60 s
the concentration of product formed
per unit time
❖ UNIT of Reaction Rates: M/s or
mol.l-1s-1
❖ Determination of Reaction

Rates:
Con. Law of
Change in Mass
the time Action
Coefficients
❖ 4 major factors strongly affect on the
reaction rate:
✔ Concentration of reactant
✔ Temperature
✔ Surface area

❖ ✔ Catalyst
Coefficients in a chemical equation: are the simplest
numbers used to balance chemical equations and are placed
in front of a chemical symbols or formula.
Example: 2H2 + 1O2 →
2H2O 5
The average rate
Definition: Is the concentration change of reactants or
products that occurs in the unit of time. aA + bB =
τ↑ cC
CA ↓ CB ↓ CC↑
ΔCA < 0 ΔCB < 0 ΔCC > 0
α
C [mol L-1]

The average rate of A, B, C:

The average reaction rate:

The instantaneous Rate
Definition: Is the reaction rate at any given point in time.
aA + bB =
τ↑ cC
CA ↓ CB ↓ CC↑
α
dCA < 0 dCB < 0 dCC > 0
C [mol L-1]

Instantaneous rate of A, B,
C:

The instantaneous rate at a The instantaneous rate of

given time corresponds to the reaction:
slope of a line tangent to the
Reaction Rate Based on Mass-Action Law
Law of Mass Action (M. Guldberg and P. Waage)
At T = const., consider the simple homogeneous
reaction:
aA (g) + bB (g) = cC (g) + dD
(g)
Reaction r= Correct solution
rate: a
k[A] [B] b
With ▪ r: reaction rate for simple
:
▪ k: reaction rate constant reactions or for
each step of a
2. 3.
1. Reaction nature complex reaction
Temperature Catalysts 8
Simple vs. Complex Reaction
Simple Reaction: only undergoes 1 stage (step)
H2 (g) + I2(g) = 2HI(g)
k1
Complex Reaction: undergoes many
stages (steps)
Each step is called a simple reaction
∑ Steps (simple reactions): reaction
In complex
mechanism reaction, the
CH 4 + Cl* → CH3* + HCl k2 overall reaction rate is
CH 3* + Cl2 → CH3Cl + Cl* k3 determined by the lowest rate of
CH 3* + Cl* → CH3Cl k4 simple rxn.
Complex reaction
Example 1: Choose the CORRECT statement. The mechanism
of complex reaction describes:
2NO2 (g) + F2 (g) → 2NO2F
(g)
Can be explained through 2 simple
reactions:NO (g) + F (g) → NO F (g) + F (g)
2 2 2

(low)
NO2 (g)of+this
The rate formula F (g) → NO2will
reaction F (g) (fast)
be depicted as:

1
Complex reaction
Example 2N2O5 (g) = 4NO2 (g) + O2 (g)
2:
There are two successive
stages:
N O =N O +O (1); low reaction rate
2 5 2 3 2

→ r1 = k1.[N2O5]
N2O5 + N2O3 = 4NO2 (2); high reaction rate
→ r2 = k2.[N2O5].[N2O3]
st
The 1 stage determines the overall rate → rrxn = v1 =
k1.[N2O5] st
→ The 1 reaction
Complex reaction
Example 3 (5.4): The chemical reaction, 2NO(g) + Br2(g) →
2NOBr(g) proceeds as the following elementary steps:

Step 1: NO(g) + Br2(g) ⇌ NOBr2(g) (fast)

Step 2: NOBr2(g) + NO(g) → 2NOBr(g) (low)
The rate law expression will be:
A. rate = k[NO][Br2] B. rate = k[NO] C. rate = k[Br2]2. D. rate =
k[NO]2[Br2]
Slow stage → rL = kL[NO][NOBr2]
Solutio unstable r=
n: k[NO]2[Br2]
D:
correct
The general reaction rate
Consider the homogeneous rxn: aA + bB = cC
+ dD m
The general reaction rate: r = k.CA .
n
▪
C
m: Bthe reaction order of A, m the reaction
order of B.
▪ m+n: the overall reaction order which can be a negative
value, integer, fraction or zero. Values of m & n are
calculated
n=a ; m by =experiments
Simple reactions
b
Complex n≠a ; m≠
▪ 1st and 2nd reactions
reaction orders b zero or 3rd
are common, whereas
reaction order is uncommon and reaction orders larger 3
13
Reaction Orders
3NO (g) → N2O (g) + NO2 r=
3
(g) k[NO]
The 3rd order respects to NO and the overall
rxn = 3
2NO2 (g) + F2 (g) → 2NO2F r = k[NO2]
(g) st [F2]
The 1 order respects to NO2 and F2; the overall rxn
order = 2
- + -
H2O2 (l) + 3I (l) + 2H (aq) → 2H2O (l) + I3
(l) r = k[H2O2] [I-
] H+; the overall
The 1st order for H O and I-; Zero order for
2 2
14
Reaction Orders

A. 2, 3 and 4 B. 1, 2 and 3 C. 1, 3 and 4 D. Only 1

and 3 15
The Effects of Reaction Order on Reaction Rate

Consider the simple rxn: A→B

+C
❑ Rxn order n = 0 → rrxn = k[A]0 = k → the rxn rate unchanges
as the concentration of reactant A change in time;

❑ Rxn order n = 1 → rrxn = k[A]1 = kA → the rxn rate doubles as

the concentration of reactant A increases double times;

❑ Rxn order n = n → rrxn = k[A]n → the rxn rate increases 2n

times as the concentration of reactant A doubles;
16
Determination of Reaction Orders and Rates
m
The general-reaction rate: r = k.CA .
n
CB overall reaction rate
The (m+n) must be
experimentally calculated even not only based on
1. CHEMICAL
reaction METHODS:
mechanism:
Using the quantative analysis: No. of analytic samples are large
→ PHYSICAL
2. titration METHODS:
Using some method to calculate the change of reactant com.
in times: spectrometer, pH, pressure, currency, turbidity
measurements, etc. 17
Reaction-Order Cal. based on [Reactant]
Change
In experiments: The change of reactant A or B

r1=k[A1]m[B1]n

r2=k[A2]m[B2]n

Example: A+B→C
m n
We rrxn = kCA CB
have:
Exp. 1 & r2/r1= 2 = [A2/A1]m[B2/B1]n = 1m 2n n=1
2: rrxn = kCA2CB
Exp. 2 & r3/r1 = 4 = 2m1n m=2
3:

18
The Rate Constant (k)
▪ Unit:

[k] = [mol/l](1-orders) .[s]-1 = M1-orders.

-1
s -1 -1 -1
The zero reaction order: k = M.s or mol.l .s

The 1st reaction order: k = s-1

The 2nd reaction order: k = M-1.s-1 or l.mol-1s-1

The nth reaction order: k = M1-n.s-1 or mol1-n.

ln-1.s-1 19
The Rate Constant (k)
The activation energy (J): is
the minimum energy
Arrhenius necessary for reaction
Equation: occurrence.
Frequency factor
(measure a favorable
collision)
▪ Nature of reaction and
Temp.
▪ The activation
k depends energy
▪ Catalys
on:
ts
▪ But, independent on concentration of
20
The Effect of Temperature on Rate Constant (k)
Based on Arrhenius Eq., At T1 → we had k1
T2 → What is the value of k2?

21
Main effects on the reaction rate
n
The general reaction rate: rrxn = k.CA . wit
m h
CB Nature
reaction. ↑→
[Reactants]
rrxn ↑
Temperatu

rrxn depends re
Catalys
on ts
Surface area (homogeneous rxn):
S↑→ rrxn↑(solution
Solvent
reaction).
Stirring, light, …
22
The effects of concentration
0. THE ZERO REACTION
ORDER
Consider a simple rxn: A →
Products
Reaction rate:

23
Half-life Time of Reaction (t1/2)
HALF-LIFE TIME, t1/2, is the amount of time
required for the reactant to be reduced to exactly half
of its starting concentration ([A]t=1/2 = ½ [A]t=0 )

In the case of the zero

order:
an
d

24
The effects of concentration
1. THE 1ST REACTION
ORDER
Consider a simple rxn: A →
Products
Reaction rate:

Half-life
time:

The half-life time of 1st rxn order ONLY depends on rate 25

Determination of Rate Constant base on Graph
The GRAPH FORM of the 1st RXN
ORDER (*
)

k
Corresponds to the graph: y =
ax + b
k value is the slope this
equation (*)
The effects of concentration
2. The 2nd REACTION
ORDER
Consider a simple rxn: 2A →
Products
Reaction rate:

Half-life
time:
27
The effects of concentration
2. The 2nd REACTION
ORDER
Consider a simple rxn : A + B → Products

Reaction rate:

After integration:

28
The effects of concentration
3. The 3rd REACTION
ORDER
Consider a simple rxn: 3A →
Products
Reaction rate:

29
Short Summary

30
The effect of Temperature
❖ Based on Arrhenius
Eq.:At T1 → we had k1
T2 → What is the value of
k 2?
❖ Van’t Hoff
Principle
❑ As the temperature increase of 10oC, the rxn rate increases 2 -
4 times
General

❑ This principle is ONLY CORRECT in small or mediate

31
The effect of Temperature
Example 1: The decomposition rxn of
N2O5, given an .
d Calculate

We
have:

32
The effect of Temperature
Example 2: (5.31) A chemical reaction was terminated

after 3 hours at 20oC. At what temperature will the reaction be

terminated after 20 min? Given that the temperature coefficient of
the reaction is 3.
o
WeA. at 30 C B. at 40oC C. at 50oC D. at 60oC
have:

n = 2 ⇢ T2 = 20 + 2*10 = 40oC B: Correct

33
Reaction Mechanism
Once molecules collide they may react together
or they may not. So, the primary requirements for
Reaction: 2NOBr → 2NO +
a reaction to occur is that:

1. The reactants must collide Br2

and interact with each other.

2. The molecules must have
sufficient energy to initiate the
reaction.
3. The molecules must have the Reactio
n
proper orientation. ⇢No
Catalyst
Catalyst is a substance that change the rate of chemical rxn or
cause the rxn occurrence
Properties:
• Participate in chemical interactions in them intermediate steps
• After reaction, catalysts usually restores and remains the
similar amount as well as chemical properties;
• ONLY CHANGE rxn rate and times, UNCHANGES the
equilibrium constant
The roles of
catalysts:
Reduce the activation energy in reaction
through mechanism changes → increase the 35
Catalyst
1. Homogeneous Catalysts
▪ 2 common Catalysts & Reactants have same phases
types of
2. Heterogeneous Catalysis
catalysts:
Catalysts & Reactants have different phases

▪ Selective
properties:
Each catalyst is ONLY suitable for a specific
reaction
With the SAME REACTANT and DIFFERENT CATALYSTS, they
can form VARIOUS PRODUCTS

Examples:
36
Catalytic Mechanism
Example: Consider reaction: A + B =
AB a
❑ Without
catalyst:
A + B → A…B →
AB
❑ In presence of
catalyst K:
A + K → A…K →
AK
AK + B → AK-B → AB +
K
The overall A + B + K → AB + K
rxn:

37