ADDIS ABABA SCIENCE AND

TECHNOLOGY UNIVERSITY

CHEMICAL ENGINEERING DEPARTMENT

Reaction Engineering I
Lecture 3
Lecturer Assefa A.(M.Sc.)
Date 04-11-19
 Chemical Reaction Kinetics
Chemical kinetics is the study of the rates of chemical reactions, the factors that affect these rates,
and the reaction mechanisms by which reactions occur.
(I) Rate of Reaction/Speed of Reaction
 Rate of reaction tells us how fast a number of moles of one chemical species are being consumed to form
another chemical species.

 It can be expressed in terms of either rate of disappearance of reactants(-rj) or formation of products(rj)

–rj is the number of moles of j reacting (disappearing) per unit time per unit volume

1 𝑑𝑁𝑗
−𝑟𝑗 = −
𝑉 𝑑𝑡
rj is the number of moles of species j generated per unit volume per unit time

1 𝑑𝑁𝑗
𝑟𝑗 =
𝑉 𝑑𝑡
 The rate of reaction has the units of moles per (units of) volume per (unit of) time.
eg. mol L-1 s-1 or Ms-1, mol/dm3⋅s
 Reaction rate is independent of the type of reactor(Batch, Plug flow, CSTR etc.)
Cont…
Relative Rates
 Relative Rates tell us how fast one species is disappearing or appearing relative to the other
species in the given reaction
 The general definition of rate of reaction, r, is given by
1 𝑑𝜑 𝑁𝑗 − 𝑁𝑗0
𝑟= , 𝑤ℎ𝑒𝑟𝑒 𝜑 =
𝑉 𝑑𝑡 ν𝑗
 After substituting and differentiating
1 1 𝑑𝑁𝑗
𝑟=
ν𝑗 𝑉 𝑑𝑡
𝑟𝑗 1 𝑑𝑁𝑗
𝑟= where 𝑟𝑗 =
ν𝑗 𝑉 𝑑𝑡

 This tell us relationship between rate of reaction and relative rates

1 𝑑𝑁𝑗
Where 𝑟𝑗 = is Relative rates of reaction
𝑉 𝑑𝑡
Consider a reaction 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
 The relationship between rate of reaction and relative rates are:
𝑟𝑗
𝑟=
ν𝑗

𝑟𝐴 𝑟𝐵 𝑟𝐶 𝑟𝐷
𝑟= = = =
−𝑎 −𝑏 𝑐 𝑑
−𝑟𝐴 −𝑟𝐵 𝑟𝐶 𝑟𝐷
𝑟= = = =
𝑎 𝑏 𝑐 𝑑
 The relative rates of reaction of the various species involved in a reaction can be obtained from the ratio
of the stoichiometric coefficients.
For example:The relationship between the rates of formation of C and D is
𝑐
𝑟𝐶 = 𝑟𝐷
𝑑

The relationship between the rate of formation of C and disappearance of A is

𝑐
𝑟𝐶 = (−𝑟𝐴 )
𝑎
Example1: Consider the decomposition reaction
2N2O5 → 2N2O4 + O2
what is relationship b/n rate of reaction, rate of disappearance of N2O5, rate of
formation of N2O4 and O2?

Example2: The rate of change of molar concentration of CH3 radicals in the reaction
2CH3(g)→ CH3CH3(g) was reported as −𝑟𝐶𝐻3 = 1.2 moldm−3s−1 under particular
conditions. What is a) the rate of reaction and b) the rate of formation of CH3CH3.
 In homogeneous systems, the volume of fluid(V) in the reactor is often identical to the
volume of reactor(Vr).
In such a case V and Vr are identical and are used interchangeably
 Based on unit volume of reacting fluid

1 𝑑𝑁𝑗 𝑚𝑜𝑙𝑒𝑠 𝑗 𝑓𝑜𝑟𝑚𝑒𝑑

𝑟𝑗 = =
𝑉 𝑑𝑡 (𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑓𝑙𝑢𝑖𝑑)(𝑡𝑖𝑚𝑒)

 Based on unit volume of reactor, if different from the rate based on unit volume of
fluid.

1 𝑑𝑁𝑗 𝑚𝑜𝑙𝑒𝑠 𝑗 𝑓𝑜𝑟𝑚𝑒𝑑

𝑟 ′′′′𝑗 = =
𝑉𝑟 𝑑𝑡 (𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑜𝑟)(𝑡𝑖𝑚𝑒)
Cont...
Rate law/Power law /Kinetic expression
- States that rate of reaction is directly proportional to the product of
concentrations raised by their respective exponents

 Consider a 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷 takes place in the reactor

𝑟 = 𝑘𝐶𝐴 𝛼 𝐶𝐵 𝛽 𝐶𝐶 𝛾 𝐶𝐷 𝛿

 For gas phase reaction, concentration can be related in terms of pressure

𝑟 = 𝑘𝑃𝑃𝐴 𝛼 𝑃𝐵 𝛽 𝑃𝐶 𝛾 𝑃𝐷 𝛿

𝑘
where 𝑘𝑃 =
(𝑅𝑇)𝛼+𝛽+𝛾+𝛿

l
Cont...
 The overall order of reaction is the sum of all orders with respect to each species
𝑜ver all order = 𝛼 + 𝛽 + 𝛾 + 𝛿
 Values of order of reaction must be determined experimentally (can not be
predicted from chemical equation).
 Order of reaction can be any real number
 Order of reaction can be integer (…-2,-1,0,1,2…) or fraction (1/2)
e.g 2HI H2 + I2 𝑟 = 𝑘𝐶𝐻𝐼 2
3
CH3CHO CH4 + CO 𝑟 = 𝑘𝐶𝐶𝐻3𝐶𝐻𝑂 2

1
CO + O CO2 𝑟 = 𝑘𝐶𝐶𝑂2 −1
2 2
Cont…
Law of Mass Action of kinetics
 Law mass action states that rate of reaction is only the dependant of reactant concentrations, not on product
concentrations
 Or the rate of reaction increases with increasing concentration of reactants owing the corresponding increase
in the number of molecular collisions.
Consider a reaction 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

𝑟 = 𝑘𝐶𝐴 𝑞1 𝐶𝐵 𝑞2 𝐶𝐶 𝑞3 𝐶𝐷 𝑞4 = 𝑘𝐶𝐴 𝑞1 𝐶𝐵 𝑞2

1
𝑞𝑗 = ( 𝝊𝑗 − 𝝊𝑗 )
2

Example: CO + 2H2 CH3OH

A B C
1 1
𝑟 = 𝑘𝐶𝐴 𝑞1 𝐶𝐵 𝑞2 𝐶𝐶 𝑞3 𝑞1 = −1 − −1 = 1+1 =1
2 2

1 1
𝑟 = 𝑘𝐶𝐴1 𝐶𝐵 2 𝐶𝐶 0 𝑞2 = −2 − −2 = 2+2 =2
2 2

1 1
𝑟 = 𝑘𝐶𝐴 𝐶𝐵 2 𝑞3 = 1 −1 = 1−1 =0
2 2
Cont...
 A reaction follows an elementary rate law if the reaction orders just happens to agree
with the stoichiometric coefficients for the reaction as written.
Exapmle: If the reaction below follows an elementary, rate law

2 A  B  3C

 rA  k AC A2CB

 It is 2nd order wrt A, 1st order B, overall 3rd order

Cont...
2.Variables affecting the rate of reaction
For homogeneous reaction, rate of reaction is dependent of
 Concentrations of reactants: As the concentrations of the reactants increase, reaction
rate generally increases
 Pressure : For gas phase reaction, rate of reaction increases as pressure increases
 Temperature: Reaction rates generally increase rapidly as the temperature is increased. .
 Catalyst: Catalysts speed up reactions and inhibitors slow them down.
For heterogeneous reaction, beside reaction rate, mass and heat transfer rates are considered.
In addition to above variables, other variables has effect on overall rate
 Surface area: For reactions that occur on a surface rather than in solution like solid-gas,
solid-liquid reactions, the rate increases as the surface area is increased
Cont….
i. Concentration dependence of the rate of a reaction
Rate law is an equation that expresses the rate of a reaction as a function of the concentrations of
all species present in the overall chemical equation at some time.

rjα f([A],[B],….)

rj = f(T) * f([A],[B],….)

rj = k[A]α[B]β…… or

rj = kCAαCBβ…..
ii. Pressure dependence of the rate of a reaction
 For homogenous gas-phase reactions, pressure is often used:
rjα f(PA, PB, ….)
rj = f(T) * f(PA, PB, ….)

rj = k(PA/RT)α(PB/RT)β….= kpPAαPBβ
kp=k/[(RT)α(RT)β]=k/[(RT)α+β]
Cont...
iii.Temperature dependence of the rate of a reaction
 Rate(constant)s increase when temperature increases.
𝑟𝑗 = 𝑘. [𝐴]𝑥 [𝐵]𝑦 … .
𝑟𝑗 = 𝑘. 𝐶𝐴 𝑥 𝐶𝐵 𝑦 …
 Arrhenius equation:

 A and Ea are called Arrhenius parameters.

 For a homogeneous chemical reaction, the dimensions(units) of the rate constant k for the
nth- order reaction are (Time-1)(concentration)1-n
Determination of Arrhenius parameters
 Plot ln k vs 1/T
 A plot of lnk against 1/T is a straight line
 The slope gives –Ea/R and the intercept at 1/T = 0 gives lnA
Cont…

Example1: The rate constants of a reaction at 500K and 700K are 0.02s-1 and 0.07s-
1respeetively. Calculate the activation energy? Take gas constant R = 8.314J/mol.K

Answer: 28,312J = 28.312kJ

Cont…

Example2: How much does a reaction rate with an activation energy of 15,000
Cal/mol vary when the temperature is increased from 300 to 310 K? From 300 to 400
K? Take gas constant R = 1.986 cal/mol.K

Solutions
𝑟310 𝑘310 𝑟400 𝑘400
≈ = 2.24 ≈ = 517
𝑟300 𝑘300 𝑟300 𝑘300

 This shows that for this activation energy an increase of temperature by 10K
approximately doubles the rate and an increase of 100K increases it by more than a
factor of 500.
 This example shows why the temperature is so important in chemical reactions.
Cont…
Collision Theory of chemical reaction
 In a chemical reaction, molecules, atoms or ions can only react if they
collide with each other.
 During collision, old bonds are broken and new bonds are formed.
 Molecular collusion produce kinetic energy
 Further collision - kinetic energy can be transferred into vibrational energy
 A reaction cannot occur unless the molecules possess sufficient energy to get
over the activation energy barrier.
 The minimum energy that must be supplied by collisions for a reaction to
occur is called the activation energy, Ea.
Cont…
Why is there an Activation Energy?

 For the reaction to occur, the reactants must overcome an energy barrier or
activation energy EA.
 The energy to overcome their barrier comes from the transfer of the kinetic
energy from molecular collisions to internal energy (e.g. Vibrational
Energy).
1. The molecules need energy to disort or stretch their bonds in order to break
them and thus form new bonds
2. As the reacting molecules come close together they must overcome both
stearic and electron repulsion forces in order to react.
Cont…

Activation energy:
 Activation energy is the minimum kinetic energy that the
reactants must have in order to react.
Pre-exponential factor
 The exponential factor in the equation corresponds to the
fraction of all occurring collisions that have enough kinetic
energy to lead to reaction.
 A: rate of successful collisions.
Cont…
CO(g) + NO2(g) CO2(g) + NO(g)
Cont…
Consider a decomposition reaction
2HBr H2 Br2
A B + C
Cont.
3. Reaction Mechanism
A reaction mechanism: is the step by step sequence of elementary reactions involved in a
reaction leading to the overall chemical reaction

Example: H2 + Br2  2HBr

 Experimental rate

 This equation represents the specific process occurring to individual molecules.

Cont…
Non elementary Reactions
None-elementary reactions is one whose stoichiometry does not match with its kinetics
(stoichiometric coefficient does not match with order of reaction)

Two types of non elementary reaction

• Non-chain Reactions.

• Chain Reactions.

 Intermediates - Free Radicals, Ions and Polar Substances,Transition Complexes, Molecules

Cont…
Kinetic Models for Non elementary Reactions
• Multistep reaction model to explain the kinetics.

Example: The irreversible reaction A+B AB has been studied kinetically, and the rate
of formation of product has been found to be well correlated experimentally by the following
rate equation:

• What reaction mechanism is suggested by this rate expression if the chemistry of the
reaction suggests that the intermediate consists of an association of reactant molecules
and that a chain reaction does not occur?

Model1: Four elementary reactions

Cont…

• Because the concentration of A2* is always extremely small we may assume that its rate
is zero

• If k3 is very small, rAB reduces to

• If k2 is very small, this expression reduces to

Cont…

Model 2

• Just interchange A and B in Model 1, put k2= 0 and we will get rAB= k[B]2 = kCA2

Home work!!!
Cont…
Molecularity: the number of free atoms, ions, or molecules that involved in
the elementary reaction.

 The number of reacting species taking part in an elementary reaction

which must collide simultaneously in order to bring about a chemical
reaction is called molecularity of reaction.

Unimolecular reaction: an elementary reaction that involves one reactant

molecule
Bimolecular reaction: an elementary reaction that involves two reactant
molecules
Ter-molecular reaction: an elementary reaction that involves three reactant
molecules.
Cont…
Unimolecular:

𝑑𝐴 𝑑𝐶𝐴
 AP with − = − = 𝑘 𝐴 = 𝑘𝐶𝐴
𝑑𝑡 𝑑𝑡

Bimolecular:

𝑑𝐴 𝑑𝐶𝐴
 2A  P with − = − = 𝑘[𝐴]2 = 𝑘𝐶𝐴 2
𝑑𝑡 𝑑𝑡

or
𝑑𝐴 𝑑𝐶𝐴
 A+BP with − = − = 𝑘[𝐴][𝐵] = 𝑘𝐶𝐴 𝐶𝐵
𝑑𝑡 𝑑𝑡
Cont…

Molecularity vs. reaction order

 Reaction order: is an empirical quantity, and obtained from the

experiment.
 Molecularity: refers to an elementary reaction proposed as an individual
step in a reaction mechanism.
 In an elementary reaction, the order of reaction is equal to the molecularity.