Lecture 12

Reaction Rate

1
Introduction

Time

Concentration

Copyright © 2007 by The McGraw-Hill Companies, Inc

As time elapses, reactant (purple) decreases and product (green) increases

The reaction rate at which reactant becomes product is the underlying

theme of chemical kinetics.

2
Reaction Rate
Chemical kinetics (động hóa học) is the study of reaction
rates:
• how reaction rates change under varying conditions, and
• what molecular event occur during the overall reaction

The reaction rate is the increase in molar

concentration of product of a reaction per unit time
Reactant
or the decrease in molar concentration of reactant
per unit time
Usual unit: moles per liter per second [mol/(L•s)]

Reaction rate depends on:

 Concentration of reactants
(often increases with the reactant increase) Product
 Temperature at which the reaction occurs
 Catalyst (Concentration of catalyst)
 Surface area of a solid reactant or catalyst
Copyright © 2007 by The McGraw-Hill Companies, Inc

3
Reaction Rate Calculation
AB
∆
𝑅𝑎𝑡𝑒 𝑜𝑓𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 =
∆
∆
∆

∆𝑡 → 0: Instantaneous rate
(tốc độ tức thời)
∆𝑡 ≫ 0: Average rate over ∆𝑡
(tốc độ trung bình)

Q: What type of rate is at line (a)

and (b)?

4
Rate Law

A rate law is an equation that relates the rate of a reaction to the

concentrations of reactants (and catalyst) raised to various powers

catalyst
aA + bB cC + dD

𝑅𝑎𝑡𝑒 𝑘 A 𝑚 B 𝑛 [catalyst]p

• [X] denotes concentrations of species X

• The exponents m, n and p must be determined experimentally
(not always integers)
• k (called rate constant) is a proportionality constant in the
relationship between rate and concentrations

Rate constant/coefficient: hằng số tốc độ

5
Reaction Order

The reaction order with respect to a given reactant species equals the
exponent of the concentration of that species in the rate law, as
determined experimentally

The overall order of a reaction equals the sum of the orders of the
reactant species in the rate law

2NO(g) + 2H2(g)  N2(g) + 2H2O(g)

Rate law: 𝑅𝑎𝑡𝑒 𝑘 𝑁𝑂 2 𝐻2 (determined experimentally)

• Reaction order with respect to NO : second

• Reaction order with respect to H2 : first
• Overall reaction order : third

6 (Overall) Reaction order: bậc phản ứng (tổng quát)

Integrated Rate Laws (Concentration-Time Eqs)

aA  products

 Zero-order reactions:
𝑅𝑎𝑡𝑒 𝑘 𝐴 𝑜 𝑘.
 𝐴𝑡 𝑘𝑡 𝐴𝑜

 First-order reactions:
𝑅𝑎𝑡𝑒 𝑘 𝐴1
 𝑙𝑛 𝑘𝑡

 Second-order reactions:
𝑅𝑎𝑡𝑒 𝑘 𝐴2
 𝑘𝑡

7
Half-life of a Reaction
The half-life, t1/2, of a reaction is the time it takes for the reactant
concentration to decrease to one-half of its initial value

 Zero-Order Reactions:
𝑅𝑎𝑡𝑒 𝑘 𝐴 𝑜 𝑘.
 𝑡1/2

 First-Order Rate Law:

𝑅𝑎𝑡𝑒 𝑘 𝐴1
.
 𝑡1/2

 Second-Order Rate Law:

𝑅𝑎𝑡𝑒 𝑘 𝐴2
 𝑡1/2

8
Graphing of Kinetic Data

aA  products

 Zero-Order Reactions: 𝑅𝑎𝑡𝑒 𝑘 𝐴 𝑜 𝑘.

 𝐴𝑡 𝑘𝑡 𝐴𝑜
Y = mX + b

 First-Order Rate Law: 𝑅𝑎𝑡𝑒 𝑘 𝐴 1

 𝑙𝑛 𝑘𝑡 OR
ln 𝐴 𝑡 𝑘𝑡 ln 𝐴 𝑜
Y = mX + b

 Second-Order Rate Law: 𝑅𝑎𝑡𝑒 𝑘 𝐴 2

 𝑘𝑡
Y = mX + b

9
Graphical determination of the reaction order for the decomposition of N2O5

N2O5  products

 Q: Reaction order?

A: First-order reaction

10
Overview

11
Reaction rate

aA + bB  cC + dD

Prove this relationship!

∆𝐴 ∆𝐵 ∆𝐶 ∆𝐷
𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒
𝑎∆𝑡 𝑏∆𝑡 𝑐∆𝑡 𝑑∆𝑡

12
Temperature and Rate of Collision
Collision theory of reaction rates: for reaction to occur, reactant
molecules must collide with an energy greater than some minimum
value and with the proper orientation

 No collision → No reaction

 The minimum energy of collision required for two molecules to react is

called the activation energy, Ea, which depends on the particular reaction

 Proper orientation Improper orientation

Copyright @ Houghton Mifflin Company. All rights reserved

O-N + O-N-N => O-N-O + N-N

13 Collision theory: thuyết va chạm

Temperature and Rate of Collision

𝑬𝒂/𝑹𝑻

 Z : the collision frequency (≡number of collisions per unit of time)

 p : the fraction of collisions that occur with the reactant molecules properly oriented

𝑬𝒂/𝑹𝑻
 𝒆 : the fraction of collisions having energy greater than the activation energy

14
Transition-State Theory

Transition-state theory explains the reaction resulting from

the collision of two molecules in terms of an activated complex

An activated complex (transition state) is an unstable

grouping of atoms that can break up to form products

O=N + Cl2 [O=N----Cl---Cl]‡ O=N-Cl + Cl

reactants activated complex products

activated complex: phức chất được hoạt hóa

15 transition state: trạng thái chuyển tiếp
Potential-Energy Diagrams

Copyright © 2007 by The McGraw-Hill Companies, Inc

16 Potential-Energy Diagram: giản đồ năng lượng (thế năng)

Arrhenius Equation

expresses the dependence of the rate constant on temperature

A (assumed to be a constant) is called the frequency factor or A-factor

(A = pxZ as in the collision theory)
ln(A)

Take the natural logarithm

ln[k(T)]
𝑬𝒂 𝟏
𝒍𝒏𝒌 𝒍𝒏𝑨
𝑹 𝑻 𝐸𝑎
𝑅
𝑘2 𝐸𝑎 1 1
𝑙𝑛
𝑘1 𝑅 𝑇1 𝑇2

1/T

17
Reaction Mechanisms

An elementary reaction is a single molecular event,

such as a collision of molecules, resulting in a reaction.

The set of elementary reactions whose overall effect is

given by the net chemical reaction/equation

A reaction intermediate is a species produced during a

reaction that does not appear in the net equation
because it reacts in a subsequent step in the mechanism

elementary reaction: phản ứng cơ bản

18 Intermediate: hợp chất trung gian
Reaction Mechanisms
Net chemical reaction
H2 + 1/2O2 = H2O

Elementary reactions A n Ea 𝑘 𝑇 𝐴 𝑇𝑛 𝑒 /
H+H+M=H2+M 7.000E+17 -1.0 0.0
O+O+M=O2+M 1.000E+17 -1.0 0.0
O+H+M=OH+M 6.750E+18 -1.0 0.0
H2O+M=H+OH+M 6.06E+27 -3.3 120770.
H2O+H2O=H+OH+H2O 1.E+26 -2.4 120160.
H+O2 (+M) =HO2 (+M) 4.660E+12 0.44 0.0
H+O2(+AR)=HO2(+AR) 4.660E+12 0.44 0.0
H+O2(+O2)=HO2(+O2) 4.660E+12 0.44 0.0
H+O2(+H2O)=HO2(+H2O) 9.060E+12 0.2 0.0
OH+OH(+M)=H2O2(+M) 1E+14 -0.37 0.0
OH+OH(+H2O)=H2O2(+H2O) 1E+14 -0.37 0.0
O+H2=OH+H 5.060E+04 2.67 6290.0
H+O2=OH+O 2.06E+14 -0.097 15022.
H2+OH=H2O+H 2.140E+08 1.52 3450.0
OH+OH=H2O+O 3.34E+04 2.42 -1930.
HO2+O=OH+O2 1.630E+13 0.0 -445.0
H+HO2=OH+OH 1.900E+14 0.0 875.0
H+HO2=H2O+O 1.45E+12 0. 0. 0.0
H+HO2=H2+O2 1.05E+14 0.0 2047.
H2+O2=OH+OH 2.040E+12 0.44 69155.0
HO2+HO2+M=H2O2+O2+M 6.84E+14 0.0 -1950.
H2O2+H=HO2+H2 1.700E+12 0.0 3755.0
H2O2+H=H2O+OH 1.000E+13 0.0 3575.0
H2O2+O=HO2+OH 9.55E+6 2.0 3970
H2O2+OH=HO2+H2O 2.000E+12 0.0 427.0

Intermediate
O, H, HO2, ....

19
Molecularity

Molecularity is the number of molecules on the

reactant side of an elementary reaction

• A unimolecular reaction is an elementary reaction

that involves one reactant molecule

• A bimolecular reaction is an elementary reaction

that involves two reactant molecules

• A termolecular reaction is an elementary reaction

that involves three reactant molecules.

20
Rate Equation for an Elementary Reaction

For an elementary reaction, the rate is proportional to the

product of the concentration of each reactant molecule

Unimolecular
𝑅𝑎𝑡𝑒 𝑘 𝐴

Bimolecular
𝑅𝑎𝑡𝑒 𝑘 𝐴 𝐵

Termolecular
𝑅𝑎𝑡𝑒 𝑘 𝐴 𝐵 𝐶

21
The Rate Law and the Mechanism
The rate-determining step is the slowest step in the reaction
mechanism

Because the rate-determining step limits the rate of the overall reaction,
its rate law represents the rate law for the overall reaction

Observed rate: 𝑅𝑎𝑡𝑒 𝑘 𝑁𝑂2 2  mechanism?

A proposed two-step mechanism is:

22
Catalysis

A catalyst is a substance that increase the rate of a

reaction but is not consumed by it

A catalyst has no effect on the equilibrium composition of

a reaction mixture. A catalyst merely speeds up the
attainment of equilibrium

23
Fact on Catalyst

 Plays a crucial role in daily activities (e.g., sugar

conversion in our body, pollutant control) and
chemical/petroleum industry.

 Accounts for ~20% of the US GNP

 Is the key to sustainability (the central point of green

chemistry)

24
Catalytic Converter
(Made of Pt, Pd and other metals
on a ceramic honeycomb)
25
A device that uses a catalyst to convert harmful
compounds (e.g., unburned HC, NOx and CO) in
car exhaust into harmless compounds (e.g.,
water and CO2).
CO conversion at low temperature
CO + O2 CO2
Pt
CO + O2 CO2
Observations (w the presence of Pt)
1. CO  CO2
2. The amount of Pt before and after
the reaction is unchanged
 Pt is called “catalyst”/catalysis
Types of catalysts

Homogenous acid catalysts

L-proline (organocatalyst)
Zeolite
(crystalline aluminosilicate)

(R,R)-DiPAMP-Rh (Organometallic complex) Enzyme (biocatalyst)

26
Classification
Homogeneous catalyst: the catalyst and reactant(s) are in the same
phase

triglycerides glycerol Fatty acid methyl esters (FAME)

used as biodiesels

Heterogeneous catalyst: the catalyst and reactant(s) are in different

phases
(Ni, Pd, or Pt)
CH3CH=CH2 + H2 CH3CH2CH3

Bio catalyst: somewhere between homo- and hetero-geneous catalysis

(catalyst ≡ enzyme)

acrylonitrile acrylamide

27
Heterogeneous Catalysis - Example

C 2 H 4 + H 2 = C2 H 6

28
How Catalyst Work?

Activation energy: minimum energy

required to get the reaction started.

A catalyst provides an
alternative route for the
reaction. That alternative route
has a lower activation energy.

From unknown source

29
How Catalyst Work?

Uncatalyzed reaction:

Catalyzed reaction:

30
End of lecture 12

Thank you!

31
Review - English
 Catalyst
 Reaction rate
 Rate law
 Rate constant
 Reaction order
 Integrated rate law
 Half-life
 Collision theory
 Activation energy
 Transition State Theory
 Activated complex
 Arrhenius equation
 Frequency factor
 Elementary reaction
 Reaction mechanism
 Reaction intermediate
 Molecular: uni, bi, ter
 Rate determining step
 Homogeneous catalysis
 Heterogeneous catalysis
 Chemisorption
 Substrate
32
Chất xúc tác
Tốc độ phản ứng
Định luật về tốc độ phản ứng
Hằng số tốc độ
Bậc phản ứng
Định luật kết hợp về tốc độ phản ứng
Bán chu kỳ (phân rã)
Thuyết va chạm
Năng lượng hoạt hóa
Thuyết trạng thái phức (hay trạng thái chuyển tiếp)
Phức hoạt hóa
Phương trình Arrihenius
Phản ứng cơ bản
Cơ chế phản ứng
Chất trung gian
Phản ứng đơn, nhị và tam phân tử
Phản ứng quyết định tốc độ phản ứng
Xúc tác đồng thể
Xúc tác dị thể
Quá trình hấp