Department of Chemical and Biomolecular Engineering

CN2105 Reaction Engineering

Unit 1:
Fundamentals of Chemical
Kinetics

Prof. Ning Yan, 2023/2024 Sem 2

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Learning Objectives (Unit 1)

1. Understand the differences between homogeneous and heterogeneous
reactions
2. Definitions of reaction rates, extent of reaction, rate laws and reaction orders
3. Reaction mechanisms and elementary vs non-elementary reactions
4. Thermodynamic consistency of rate laws for reversible reactions
5. Activation energy & Temperature effect on reaction rates
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1. Homogeneous and Heterogeneous Reactions

• Homogeneous reactions occur in only one phase.
▪ E.g. gas phase reactions, liquid phase reactions
▪ Feature: reagents are freely available to react (no mass transfer limitation)
(mainly discussed in Part 1).
• Heterogeneous reactions have at least
one participant (reactant, product or
catalyst) in a different phase.
▪ E.g. gas-solid, gas-liquid, liquid-solid, liquid-
liquid, solid-solid, gas-liquid-solid reactions
▪ The overall rate of heterogeneous reactions
can be limited by mass and/or heat transfer
and is not only dependent on intrinsic
chemistry (more in Part 2).

Design heterogeneous reactor is far more complex than

design homogeneous reactor
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2. Reaction Rates
• The rate of reaction is proportional to the rate of change of the amount of a
reactant or product:
𝑑𝑁𝑖
𝑟𝑖 ∝
𝑑𝑡

• Rates are positive for products and negative for reactants.

• For a fair comparison between systems of different sizes, reaction rates are
normalised by a system property, V which reflects the size of the system (e.g.
volume, surface area, mass):
1 𝑑𝑁𝑖
𝑟𝑖 =
𝑉 𝑑𝑡

Similar to extensive and intensive properties in thermodynamics

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2. Reaction Rates
• Consider reaction: aA + bB → cC + dD
• Stoichiometry dictates that:
𝑟A 𝑟B 𝑟C 𝑟D
− =− = = =𝑅
𝑎 𝑏 𝑐 𝑑
where ri is the reaction rate of species i and R is the rate of the reaction
represented by the chemical equation (> 0).

• If a species is involved in multiple independent reactions, the rule of addition

applies:
𝑟𝑖 = ෍ 𝑟𝑖𝑗
𝑗
where rij is the reaction rate of species i in reaction j.
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2. Molar extent of Reaction

• The molar extent of reaction is defined as:
Δ𝑁𝑖
𝜉= >0
𝜈𝑖
where ΔNi is the change in the amount of species i due to the reaction.

Example
2H2 + O2 → 2H2O
At the start of the reaction, there were 10 mol H2 and 3 mol O2. One hour later, 6
mol H2, 1 mol O2 and 4 mol H2O were present. After a very long time, 4 mol H2, 0
mol O2 and 6 mol H2O were left.
Δ𝑁𝑖 6−10 1−3 4−0
• After 1 hour, 𝜉𝑡=1h = = = = = 2 mol
𝜈𝑖 −2 −1 2
Δ𝑁𝑖 4−10 0−3 6−0
• At the end of the reaction, 𝜉𝑡→∞ = = = = = 3 mol
𝜈𝑖 −2 −1 2
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Practice Questions
1. What are the units of the reaction rate if it is normalised by the catalyst
surface area?
1 𝑑𝑁𝑖
𝑟𝑖 =
𝐴 𝑑𝑡 -2 -1
mol m s

2. In the Example on Slide 6, what is the limiting reactant?

3. For the following reactions:
𝑟A′ 𝑟B′ 𝑟C′ 𝑟D′ 𝑟A′′ 𝑟C′′ 𝑟E′′
A + 2B → 3C + D (1) −
1
=−
2
=
3
=
1
= 𝑅1 −
1
=−
1
=
1
= 𝑅2

A+C→E (2)
Express the reaction rates of the species (rA, rB, rC, rD and rE) in terms of the
rates of the reactions (R1 and R2).
4. Consider the following cyclic reactions. If we start with only A, what can we
expect to find after some time?
A→B
C
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2. Factors Affecting Reaction Rates

• Chemical structures of the reactants and products
• Concentrations of reactants and products
• Temperature
• Types of contact between reactants and products
• Catalytic activity (if applicable)
• Strength of auxiliary effects (e.g. electric fields, magnetic fields) (if applicable)

For most homogeneous reactions:

𝑹 = 𝒇 𝒄, 𝑻
where 𝑐Ԧ is the concentration vector involving the reactants and products as well
as possibly other species (e.g. catalysts) and T is temperature.
• The exact mathematical form of function f is the rate law.
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2. Rate Laws
• The power law:
𝛼 𝛽
𝑅= 𝑘𝑐A 𝑐B …
where k is the specific rate constant (a function of temperature) and α, β… are the
orders of reaction with respect to each species.

• Specific rate constant is positive and independent of concentrations.

• It can be defined with respect to any species or the reaction:
• If 𝑅 = 𝑘𝑐A , k is the rate constant with respect to the reaction.
• If 𝑟𝑖 = 𝑘𝑖 𝑐A , ki is the rate constant with respect to species i, and 𝑘𝑖 = |𝜈|𝑘.

• Orders of reaction are often not equal to the stoichiometric coefficients and can
be any real number (positive or negative, integers or fractions).
For example: A + 2B → C does not mean the rate law is 𝑅 = 𝑘𝑐A1 𝑐B2
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2. Rate Laws: simpler examples

• For reaction A + B → C, write down rate laws based on the given
information.
▪ First order for A and first order for B: 𝑅 = 𝑘𝑐A 𝑐𝐵

▪ First order for A and zero order for B: 𝑅 = 𝑘𝑐A

1/2
▪ Second order for A and half order for B: 𝑅 = 𝑘𝑐𝐴2 𝑐𝑏

▪ Reversible reaction, where the reaction orders for A, B and C are 1, 2 and 1,
respectively:
𝑅 = 𝑘f 𝑐A 𝑐𝐵2 − 𝑘r 𝑐C
 11

2. Rate Laws: more complex examples

Do rate laws always follow power
law? NO!
only the eqm constant will always follow power law

Do reaction order of reagent

always a constant? NO!

For example, Michaelis-Menten kinetics:

𝑉m 𝑐
𝑅= Why not R = kc ?
𝐾M + 𝑐
Reaction order shifts depending on the
concentration:
• At low concentrations (where c << KM),
𝑉 𝑐
𝑅 ≈ m (a first order reaction).
𝐾M
• At high concentrations (where c >> KM),
𝑅 ≈ 𝑉m (a zeroth order reaction).
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2. Rate Laws: more complex examples

 1−
 p 3
 p 2
 Ways to find out k:
= k1 pN2   − k2  
H2 NH 3
rNH3
p 2  3
 NH 3   p H2  0<α<1
Arrhenius equation
−𝐸𝐴
𝑘 = 𝐴 exp
𝑅𝑇
Fe
n CO + (2n + 1) H2 → CnH2n+2 + n H2O

𝑘 𝑃𝐻2 𝑃𝐶𝑂 Eyring equation ⱡ

𝑟𝐶𝑛𝐻2𝑛+2 = 𝑘𝑏 𝑇 −∆𝐺
𝑃𝐶𝑂 + 𝑎𝑃𝐻2𝑂 𝑘= exp
ℎ 𝑅𝑇

How are C and T reflected in these rate laws?

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2. Rate Laws vs. Reaction equilibrium constants

You cannot predict rate

Rate Laws
law/reaction order from the
 1−
 p 3
 p 2
 balanced equation. Reaction
= k1 pN2   − k2  
H2 NH 3
rNH3 order comes from experimental
p 2  3
 NH 3   p H2  0<α<1 data, or derivation based on
reaction mechanism.

Equilibrium constants

(𝐶𝑁𝐻3 )2𝑒𝑞 (𝑃𝑁𝐻3 )2𝑒𝑞 You can calculate the

𝐾= = equilibrium constant from the
(𝐶𝐻2 )3𝑒𝑞 (𝐶𝑁2 )1𝑒𝑞 (𝑃𝐻2 )3𝑒𝑞 (𝑃𝑁2 )1𝑒𝑞
balanced equation

We come back to this later

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3. Elementary Reactions vs. Non-Elementary Reactions

Chemical Reactions

Elementary Reactions Non-Elementary Reactions

An elementary reaction is a reaction that occurs in a Reaction that do not occur in a single-step as per the
single step, exactly as per the reaction stoichiometry. reaction stoichiometry, but via multiple elementary steps
that are not reflected by the overall reaction.
OH- + CH3Br → CH3OH + Br- H2 + Br2 → 2HBr

Reaction mechanism: Reaction mechanism:

Br2 ⇌ 2Br•
Br• + H2 ⇌ HBr + H•
H• + Br2 → HBr + Br•

𝑅 ≠ 𝑘𝑐𝐻2 𝑐𝐵𝑟2
1
𝑅 = 𝑘𝑐𝐶𝐻3𝐵𝑟 𝑐𝑂𝐻ˉ 𝑘1 H2 Br2 2
𝑟HBr =
𝑘2 + HBr /[Br2 ]
15
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3. Elementary Reactions vs. Non-Elementary Reactions

Why can’t we predict rate law/reaction order from the balanced equation?
Because most chemical reactions are not elementary reactions!

For a given chemical reaction, are we able to judge whether or not it is an

elementary reaction?
NO!

However, a tip is that an elementary reactions rarely involve 3 or more

reacting particles (atoms/molecules/ions).

Elementary reaction or not?

5Br− + BrO3− + 6H+ → 3Br2 + 3H2O
𝑅 = 𝑘 Br − 5 BrO− 3 H
+ 6
?
 17

Quiz
1. For the following reaction with power law kinetics, how many specific rate
constants can be defined?
2A + 3B → 4C
𝑅 = 𝑘𝑐A 𝑐B

2. What is the order of reaction with respect to each reacting species and the
overall order of reaction for the following reaction?
A + 2B → C

3. What if the reaction in 2 is elementary?

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4. Thermodynamics vs Kinetics
• For the reaction aA + bB → cC + dD, the equilibrium constant can be calculated:
[C]𝑐eq [D]𝑑eq
𝐾=
[A]𝑎eq [B]𝑏eq
• If K < 0.1, the reaction does not proceed, i.e. aA + bB ↛ cC + dD
• If 0.1 < K < 10, the reaction is reversible, i.e. aA + bB ⇌ cC + dD
• If K > 10, the reaction is irreversible, i.e. aA + bB → cC + dD

• The Gibbs free energy change can also be calculated:

Δ𝐺 o = −𝑅g 𝑇ln𝐾
• Spontaneous reactions require ΔGo < 0 (or large K).

• Kinetics determines how “fast” a reaction goes, while thermodynamics dictates

how “far” the reaction can go.
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4. Thermodynamic Consistency of Rate Laws

• The rate law for a reversible reaction must be thermodynamically consistent,
i.e. at equilibrium (where R = 0), the rate law must be consistent with the
implication of the law of mass action:
𝐾 = 𝑓 𝑇 only

Example: Formation and decomposition of phosgene

CO + Cl2 ⇌ COCl2
3
The 1st engineer proposed rate law for forward reaction: 𝑅f = 𝑘f Cl2 [CO], rate law
2
1
for reverse reaction: 𝑅r = 𝑘r Cl2 [COCl2 ]
2

3
The 2nd engineer proposed rate law for forward reaction: 𝑅f = 𝑘f Cl2 , rate law for
2
1
reverse reaction: 𝑅r = 𝑘r Cl2 [COCl2 ]
2

Who must be wrong?

 20

4. Thermodynamic Consistency of Rate Laws

COCl2 eq
At eqm, net reaction rate = 0. = 𝐾 = 𝑓 𝑇 only
Cl2 eq CO eq
3 1
2 2
Based on engineer 1: 𝑅net = 𝑘f [Cl2 ]eq CO eq − 𝑘r [Cl2 ]eq COCl2 eq =0

COCl2 eq 𝑘f
Rearranging gives: = = 𝑓 𝑇 only
Cl2 eq CO eq 𝑘r

3 1
2 2
Based on engineer 2: 𝑅net = 𝑘f [Cl2 ]eq −𝑘r [Cl2 ]eq COCl2 eq =0

COCl2 eq 𝑘f
Rearranging gives: = ≠ 𝑓 𝑇 only
Cl2 eq 𝑘r

The first engineer’s proposal passed the thermodynamic consistency

 21

Revisit 1
• For reaction A + B → C, write down rate laws based on the given
information.
▪ First order for A and first order for B: 𝑅 = 𝑘𝑐A 𝑐𝐵

▪ First order for A and zero order for B: 𝑅 = 𝑘𝑐A

1/2
▪ Second order for A and half order for B: 𝑅 = 𝑘𝑐𝐴2 𝑐𝑏

▪ Reversible reaction, where the reaction orders for A, B and C are 1, 2 and 1,
respectively:
𝑅 = 𝑘f 𝑐A 𝑐𝐵2 − 𝑘r 𝑐C 𝑘f 𝑐A 𝑐𝐵2 = 𝑘r 𝑐C

Does the last case satisfy thermodynamic consistency? 𝑘f 𝑐C

= 2 ≠𝐾
𝑘r 𝑐A 𝑐𝐵
 22

Revisit 2

 1−
 p3
 p2

= k1 pN2   − k2  
H2 NH 3
rNH3
p2  3
 NH 3   p
H2  0<α<1

Revisit 2: does the rate law above satisfy thermodynamic consistency?

2
𝑝𝑁𝐻
( 3 3 )1−𝛼 2
𝑝𝐻3 2 𝑝 2
𝑁𝐻 𝑘1 𝑝𝐻2 𝑝𝑁𝐻
𝑘1 𝑝𝑁2 ( 2 )𝛼 = 𝑘2 ( 3 3 )1−𝛼 = = 3
=𝐾
𝑝𝑁𝐻3 𝑝𝐻2 𝑘2 𝑝𝐻3 2 𝛼 𝑝𝐻3 2 𝑝𝑁2
𝑝𝑁2 ( 2 )
𝑝𝑁𝐻3
 23

5. Activation Energy (which decide k)

• For the reaction to occur, the reactants must overcome an energy barrier,
known as the activation energy:
• As the reacting molecules come close together, they must overcome steric and
electronic repulsive forces.
• The molecules need energy to distort or stretch their bonds to break them and
subsequently form new bonds.
• The energy to overcome the barrier comes from the transfer of the kinetic
energy from molecular collisions to internal energy.
 24

5. Activation Energy (which decide k)

• The distribution of velocities of the reacting molecules is given by the Maxwell-
Boltzmann distribution:
3
𝑚 2 𝑚𝑈 2
−
𝑓 𝑈, 𝑇 = 4𝜋𝑈 2 𝑒 2𝑘B 𝑇
2𝜋𝑘B 𝑇
• where U is the relative velocity, T is the absolute temperature, f(U, T) is the
fraction of molecules with relative velocity U, m is the reduced mass of the
molecule and kB is the Boltzmann’s constant.

f(U, T) T1 T2 > T1
1. What is the integral of the Maxwell-Boltzmann curve
from 0 to infinity?

2. Must the Maxwell-Boltzmann curve pass through the

T2 origin?

U Not required by the module

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5. Temperature Effect on Specific Rate Constant

• The Arrhenius equation is the most common form describing the temperature
effect on specific rate constants:
𝐸
− a
𝑅g 𝑇
𝑘 = 𝐴𝑒
• where A is the pre-exponential factor and Ea is the activation energy.
𝐸a
• A plot of lnk against 1/T is a straight line with a slope of − and a y-intercept of
𝑅g
lnA.

The Arrhenius equation is only valid over

a limited temperature range. Deviations
often indicate complex rate laws or
changes in the rate law due to changes in
the reaction mechanism as temperature
varies.
 26

5. Temperature Effect on Specific Rate Constant

• A modified form of Arrhenius equation can be used:
𝐸
−𝑅 a𝑇
𝑘= 𝐴′ 𝑇 𝑚 𝑒 g
where Tm is a correction factor (0 ≤ m < 4).
1
• For elementary reactions, m = based on the collision theory or m = 1 based on
2
the transition state theory.
• Taking logarithm and differentiating gives:
𝐸𝑎 𝑑ln𝑘 𝑚 𝐸a 𝑑ln𝑘 𝑑ln𝑘 𝐸a
ln𝑘 = 𝑚𝑙𝑛𝑇 − = + = −𝑇 2
= −𝑚𝑇 −
𝑅𝑔 𝑇
𝑑𝑇 𝑇 𝑅g 𝑇 2 𝑑 1/𝑇 𝑑𝑇 𝑅g
𝐸𝑎
• Often, mT << , the correction factor is only significant at very high T.
𝑅g

1
If the collision theory is valid (m = 2), what are the units of A’ in the modified Arrhenius
equation when it is used to describe the specific rate constant of a second order
reaction? (Ans: mol-1 m3 s−1 K-1/2)
Try yourself!
 27

Summary: type of reactors

R Often, we also have

Content of leaving stream

= content in reactor
 28

Summary: type of reactors

No mixing in axial direction, perfect mixing in radial direction

Often, we also have

R
 29

Summary: kinetics
1 𝑑𝑁𝑖
Reaction rate 𝑟𝑖 =
𝑉 𝑑𝑡
• aA + bB → cC + dD
𝑟A 𝑟B 𝑟C 𝑟D
− =− = = =𝑅
𝑎 𝑏 𝑐 𝑑
If a species is involved in multiple independent reactions:
𝑟𝑖 = ෍ 𝑟𝑖𝑗
𝑗
where rij is the reaction rate of species i in reaction j.

The molar extent of reaction is defined as:

Δ𝑁𝑖
𝜉= >0
𝜈𝑖
where ΔNi is the change in the amount of species i due to the reaction.
 30

Summary: kinetics
For most homogeneous reactions:
𝑹 = 𝒇 𝒄, 𝑻
The exact mathematical form of function f is the rate law.

For elementary reactions, rate law is based on the reaction stoichiometry

If aA + bB → cC + dD is an elementary reaction: 𝑅 = 𝑘𝑐𝐴𝑎 𝑐𝐵𝑏

For non-elementary reactions, rate law has to be experimentally measured

Rate law may have very complex formula. It may change as a function of
concentration and temperature.
 31

Check your understanding

First order reaction: A → B. k = 1 h-1. c0 = 10 mol/L. xA = R
90%. For a batch and a CSTR of the same volume (100 L),
which one is more productive? R0 = kcA0 = 10 mol/L∙h 𝑡
How about 0 order reaction? R = -rA = kcA ∆𝑁𝐴 = න −𝑟𝐴 𝑉𝑑𝑡
Do not consider time required to change substrate in the 0

batch reactor

R = kcA = 1 mol/L∙h
R 0 Time
k R

∆𝑁𝐴 = −𝑟𝐴 𝑉𝑑𝑡

Time
c0 = 10 mol/L c = 1 mol/L
R = kcA = 1 mol/L∙h

c = 1 mol/L 0 Time