Chemical Reaction Engineering

Rate Laws
(Examples and Practice)

Dr Asad U. Khan
Overview
Objectives

• Relate the rates of reaction of species in a reaction to each other

• Write the rate law in terms of concentrations
• Use the Arrhenius Equation to find the rate constant as a function
of temperature
• Describe the energy barrier height (activation energy) and the
fraction of molecular collisions that have the energy to pass over
the barrier and react
 Rate Laws
Basic Definitions
• A homogeneous reaction is one that involves only one phase. A heterogeneous
• reaction involves more than one phase, and the reaction usually occurs at the
• interface between the phases.
• An irreversible reaction is one that proceeds in only one direction and
continues in that direction until one of the reactants is
• exhausted.
• A reversible reaction, on the other hand, can proceed in either direction,
depending on the temperature and on the concentrations of reactants and
• products relative to the corresponding equilibrium concentrations.
• An irreversible reaction behaves as if no equilibrium condition exists. Strictly
speaking, no chemical reaction is completely irreversible.
• For many reactions, the equilibrium point lies so far to the product side that
these reactions are treated as irreversible reactions.

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 Rate Laws
Basic Definitions
• The molecularity of a reaction is the number of atoms, ions, or molecules
• involved (colliding) in a reaction step.
• The terms unimolecular, bimolecular, and termolecular refer to reactions
involving, respectively, one, two, and three atoms (or molecules)
interacting or colliding in any one reaction step.
• The most common example of a unimolecular reaction is radioactive
decay, such as the spontaneous emission of an alpha particle from
uranium-238 to give thorium and helium

Rate of reaction

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 Rate Laws

2A  B  3C

A reactor follows an elementary rate law if the reaction

orders just happens to agree with the stoichiometric
coefficients for the reaction as written.
e.g. If the above reaction follows an elementary rate law

 rA k AC A2 C B
2nd order in A, 1st order in B, overall third order

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 Rate Laws

2A+B3C
2
If  rA kC A
›Second Order in A
›Zero Order in B
›Overall Second Order

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Elementary Rate Law Reactions

A reaction follows an elementary rate law if and only if (iff) the

stoichiometric coefficients are the same as the individual reaction order
of each species. For the reaction in the previous example
(A+B  C+D),
the rate law would be:

If 2NO+O2  2NO2

Then
-rNO = kNO (CNO)2 CO2

Example
Non-Elementary Rate Laws

If the rate law for the non-elementary reaction is A+BC+D

found to be

then the reaction is said to be 2nd order in A, 1st order in

B, and 3rd order overall.
Non-Elementary Rate Laws
Heterogeneous Reactions: In many gas-solid catalysed reactions
historically it has been practiced to write Rate law in terms of
partial pressure.

Rate law follows

Reversible Reactions

• The net rate of formation of any species is equal to its rate of

formation in the forward reaction plus its rate of formation
in the reverse reaction:

• ratenet = rateforward + ratereverse

• At equilibrium, ratenet and the rate law must reduce to an

equation that is thermodynamically consistent with the
equilibrium constant for the reaction.
• Example
Relative Rates of Reaction

aA  bB  cC  dD
b c d
A B  C  D
a a a
rA rB rC rD
  
a b c d

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 Reversible Elementary Reaction

Forward: Reverse:

Net:

At Equilibrium: Therefore:
Relative Rates of Reaction
2A  B  3C
mol
 rA 10
Given dm 3 s
rA rB rC
Then  
 2 1 3
 rA mol
 rB  5
2 dm 3 s
3 mol
rC  rA 15
2 dm 3 s
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Reversible Elementary Reaction
Reaction is:
kA First Order in A
A+2B
Second Order in B
3C k-A Overall third Order

moles moles
 rA   3 CA 
dm s dm3

  rA  mole dm 3 s dm 6
k   2   
 A B  mole dm mole dm 
2 2
C C 3 3 mole s
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15
Arrhenius Equation
k is the specific reaction rate (constant) and is given by the
Arrhenius Equation.
where:
 E RT
k  Ae

T kA
k T 0 k 0
13
A 10
T

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Arrhenius Equation
where:
E = Activation energy (cal/mol)
R = Gas constant (cal/mol*K)
T = Temperature (K)
A = Frequency factor (same units as rate constant k)
(units of A, and k, depend on overall reaction order)

Units of k

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 Reaction Coordinate
The activation energy can be thought of as a barrier to the reaction. One
way to view the barrier to a reaction is through the reaction
coordinates. These coordinates denote the energy of the system as a
function of progress along the reaction path. For the reaction:

A  BC  A ::: B ::: C  AB  C

The reaction coordinate is:

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Collision Theory

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 Why is there an Activation Energy?
We see that 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.

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 Distribution of Velocities

We will use the Maxwell-Boltzmann Distribution of Molecular

Velocities. For a species af mass m, the Maxwell distribution of
velocities (relative velocities) is:

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 m 
f U , T  dU 4   e  mU 2 2 k BT
U 2 dU
 2 k B T 
f(U,T)dU represents the fraction of velocities between U and
(U+dU).

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 Distribution of Velocities
A plot of the distribution function, f(U,T), is shown as a
function of U:
T1
T2 T2>T1

𝑓 (𝑈 , 𝑇 )

U
Maxwell-Boltzmann Distribution of velocities.
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 Distribution of Velocities
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 m 
Given f U , T  dU 4   e  mU 2 2 k BT 2
U dU
 2 k BT 
Let 1
E  mU 2
2
E
2
f  E , T  dE  1 2 k BT
E e dE
2 k BT 
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f(E,T)dE represents the fraction of collisions that have energy

between E and (E+dE)

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f(E,T)dE=fraction of molecules with energies between E+dE

One such distribution of energies is in the following figure:

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Temperature Dependence of Rate Constant, k

• k is the specific reaction rate (constant) and is given by the

Arrhenius Equation:
•

k  Ae  E RT
Excel: Fitting logarithmic data

Excel Calculations
Excel: Fitting logarithmic data
Excel: Fitting logarithmic data

Activation Energy
Excel: Fitting logarithmic data

Activation Energy
Different Graph papers

Semi Log Graph Paper Log-Log Graph Paper

Algorithm

How to find r A  f X 

Step 1: Rate Law  rA  g Ci 

Step 2: Stoichiometry Ci  hX 

Step 3: Combine to get  rA  f X 

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Thank you
 Rate Laws

• A rate law describes the behavior of a reaction. The rate of a

reaction is a function of temperature (through the rate constant) and
concentration.

• Relative Rates of Reaction

Example Relative Rates of Reaction

The Reaction:

is carried out in a reactor. If at a particular point,

the rate of disappearance of A is 10 mol/dm3/s,
what are the rates of B and C?
Species A, basic of calculation

The rate of disappearance of A, -ra, is

or the rate of formation of species A is

The relative rates are

 Species B

The rate of formation of species B is

The rate of disappearance of B, -rb, is

 Species C

The rate of formation of C, -rc, is