CIE 596Z/CIE728 – Fate and Transport of Pollutants

Presentation 3
Chemical Reaction Kinetics

1
 Reaction Kinetics
• The rate of which a reactant disappears or a product is formed in any given
stoichiometric reaction is defined as the rate of reaction.

• Knowing the rate of reactions is important because a treatment process may be

designed on the basis of the rate of which the reaction proceed, rather than the
equilibrium position of the reaction, because the reaction usually takes too long
to go to completion.

2
 Reaction Kinetics
Classes of Reactions

• There are two principal classes of reactions that occur in nature, homogeneous
reactions and heterogeneous reactions.

• Homogeneous reactions occur within a single phase (i.e., liquid, solid, or gas).

• Heterogeneous reactions occur at surfaces between phases

• In a homogeneous reaction, the reactants are distributed continuously but not

necessarily uniformly, throughout the fluid, so that the potential for reaction
exists at all points in the fluid.

• Homogeneous reactions may be either irreversible or reversible. 3

 Reaction Kinetics
Classes of Reactions

• Examples of single irreversible reactions:

𝐴𝐴 → 𝑃𝑃
𝐴𝐴 + 𝐴𝐴 → 𝑃𝑃
𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 → 𝑃𝑃
• Examples of multiple irreversible reactions are:
B
A (Parallel)
C

𝐴𝐴 → 𝐵𝐵 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑜𝑜𝑜𝑜 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠

• Examples of reversible reactions:
𝐴𝐴 ↔ 𝑃𝑃
𝐴𝐴 + 𝐵𝐵 ↔ 𝐶𝐶 + 𝐷𝐷
4
 Reaction Kinetics
Rate and Order of Reactions

• The rate of reaction ri is the term used to describe the disappearance or

formation of a particular substance or chemical species i

• For homogeneous reactions, the units of ri would be moles (or mass) per unit
volume and unit time (mol/L.t), and for heterogeneous reactions the rate of
formation would be moles (or mass) per unit area and unit time (mol/m².t)

• Reactants have negative rates of reaction, and products have positive rates of
reaction.

• At constant temperature, it has been observed that the rate of reaction typically
is some function of the concentration of the reactants.
5
 Reaction Kinetics
Rate and Order of Reactions

At constant temperature, it has been observed that the rate of reaction typically is some
function of the concentration of the reactants. For example:

𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 → 𝑐𝑐𝑐𝑐 + 𝑑𝑑𝑑𝑑

𝑟𝑟 = 𝑘𝑘 𝐴𝐴 𝛼𝛼 𝐵𝐵 𝛽𝛽

Where,
r = overall rate of reaction, mol/ L.t
k = reaction rate constant
[ ] = molar concentration of reactants, mol/ L
α, β = empirical exponents.
The constants α and β are used to define the order of the reaction with respect to the
individual reactants A and B.
The overall order of the reaction is defined as (α + β )
The units of the reaction rate constant k are a function of the reaction order.
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 Reaction Kinetics
Rate and Order of Reactions

The overall rate of reaction is defined on the basis of the stoichiometric

coefficients and the individual reaction rates. For example, for the reaction:

𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 → 𝑐𝑐𝑐𝑐 + 𝑑𝑑𝑑𝑑

𝑟𝑟𝐴𝐴 𝑟𝑟𝐵𝐵 𝑟𝑟𝐶𝐶 𝑟𝑟𝐷𝐷

𝑟𝑟 = = = =
𝑎𝑎 𝑏𝑏 𝑐𝑐 𝑑𝑑

Where,
r = overall rate of reaction, mol/ L.t
a, b, c, d = stoichiometric coefficients
rA, rB, rC, rD = rates of reaction for individual reactants and products.
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 Reaction Kinetics
Types of Reactions and Rates

• The most common types of reactions encountered in the field of environmental

engineering are: irreversible, reversible, saturation, and autocatalytic.

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 Reaction Kinetics
Types of Reactions and Rates: Irreversible
• In multiple irreversible reactions, more than one • then:
reactions step must be considered, for example:
1 2
𝑎𝑎𝑎𝑎→𝑏𝑏𝑏𝑏→𝑐𝑐𝑐𝑐 𝑟𝑟𝐴𝐴 = 𝑎𝑎𝑟𝑟1
• For the purpose of analysis the above reaction 𝑟𝑟𝐵𝐵 = 𝑟𝑟𝐵𝐵𝐵 + 𝑟𝑟𝐵𝐵𝐵 = 𝑏𝑏𝑟𝑟1 + 𝑏𝑏𝑟𝑟2
can be treated as being made of two steps:
𝑟𝑟𝐶𝐶 = 𝑐𝑐𝑟𝑟2
1
𝑎𝑎𝑎𝑎→𝑏𝑏𝑏𝑏

2
• If both of the rates of reaction are first
𝑏𝑏𝑏𝑏→𝑐𝑐𝑐𝑐 order, then:
• If the overall rates of reaction r1 and r2 are
known, then the rate of reaction of any reactant
or product can be defined: 𝑟𝑟𝐴𝐴 = 𝑎𝑎𝑘𝑘1 𝐴𝐴
𝑟𝑟𝐴𝐴 𝑟𝑟𝐵𝐵𝐵 𝑟𝑟𝐵𝐵 = 𝑏𝑏𝑘𝑘1 𝐴𝐴 + 𝑏𝑏𝑘𝑘2 𝐵𝐵
𝑟𝑟1 =
𝑎𝑎
=
𝑏𝑏
𝑟𝑟𝐶𝐶 = 𝑐𝑐𝑘𝑘2 𝐵𝐵
𝑟𝑟𝐵𝐵𝐵 𝑟𝑟𝐶𝐶
𝑟𝑟2 = =
𝑏𝑏 𝑐𝑐
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 Reaction Kinetics
Types of Reactions and Rates: Reversible
For reversible reactions:
•
• If both of the rates of reactions are
2 1 first order, then:
𝑎𝑎𝑎𝑎← →𝑏𝑏𝑏𝑏 =>

1
𝑎𝑎𝑎𝑎→𝑏𝑏𝑏𝑏 𝑟𝑟𝐴𝐴 = 𝑎𝑎𝑘𝑘1 𝐴𝐴 + 𝑎𝑎𝑘𝑘2 𝐵𝐵
2
𝑏𝑏𝑏𝑏→ 𝑎𝑎𝑎𝑎
𝑟𝑟𝐵𝐵 = 𝑏𝑏𝑘𝑘1 𝐴𝐴 + 𝑏𝑏𝑘𝑘2 𝐵𝐵
𝑟𝑟𝐴𝐴𝐴 𝑟𝑟𝐵𝐵𝐵
𝑟𝑟1 = =
𝑎𝑎 𝑏𝑏
𝑟𝑟𝐵𝐵𝐵 𝑟𝑟𝐴𝐴𝐴
𝑟𝑟2 = = =>
𝑏𝑏 𝑎𝑎

𝑟𝑟𝐴𝐴 = 𝑟𝑟𝐴𝐴𝐴 + 𝑟𝑟𝐴𝐴𝐴 = 𝑎𝑎𝑎𝑎1 + 𝑎𝑎𝑎𝑎2

𝑟𝑟𝐵𝐵 = 𝑟𝑟𝐵𝐵𝐵 + 𝑟𝑟𝐵𝐵𝐵 = 𝑏𝑏𝑏𝑏1 + 𝑏𝑏𝑏𝑏2

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 Reaction Kinetics
Types of Reactions and Rates: Saturation
Saturation-type reaction has a maximum rate, that is, Other saturation-type reactions
a point at which the value becomes independent of
concentration. encountered in environmental engineering
modeling:
A typical saturation rate function for the reaction:

𝑎𝑎𝑎𝑎 → 𝑏𝑏𝑏𝑏 𝑘𝑘 𝐴𝐴 𝐵𝐵
𝑟𝑟 =
Is given as: 𝐾𝐾 + 𝐴𝐴
𝑘𝑘 𝐴𝐴
𝑟𝑟 =
𝐾𝐾 + 𝐴𝐴
𝐴𝐴 𝐵𝐵
Where, 𝑟𝑟 = 𝑘𝑘
r = rate of reaction (mol/ L.t) 𝐾𝐾1 + 𝐴𝐴 𝐾𝐾2 + 𝐵𝐵
k = reaction constant (mol/ L.t)
[A] = concentration of reactant A (mol/ L)
K = half-saturation constant (mol/L)
When k « [A] => r → k
When [A] « k => r → k[A] 11
 Reaction Kinetics
Types of Reactions and Rates: Autocatalytic

Autocatalytic reaction rates are function of First order autocatalytic:

the product concentration.
𝑟𝑟 = 𝑘𝑘 𝐵𝐵
Autocatalytic reactions can be first order, 𝑟𝑟𝐴𝐴 = 𝑎𝑎𝑎𝑎 𝐵𝐵
second order, or saturation type, or they 𝑟𝑟𝐵𝐵 = 𝑏𝑏𝑏𝑏 𝐵𝐵
can be partially autocatalytic: a function of
a reactant and a product. Examples for Second order partially autocatalytic:
autocatalytic reaction:
𝑟𝑟 = 𝑘𝑘 𝐴𝐴 𝐵𝐵
𝑎𝑎𝑎𝑎 → 𝑏𝑏𝑏𝑏 𝑟𝑟𝐴𝐴 = 𝑎𝑎𝑎𝑎 𝐴𝐴 𝐵𝐵
𝑟𝑟𝐵𝐵 = 𝑏𝑏𝑏𝑏 𝐴𝐴 𝐵𝐵

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 Reaction Kinetics
Effects of Temperature on Reaction-Rate Constants

The rate of reaction dependence on To compare the reaction rate constant at

temperature is described by the following two different temperatures, the above
reaction: equation is usually written as:
𝑘𝑘 𝑇𝑇 = 𝐴𝐴𝑒𝑒 −𝐸𝐸⁄𝑅𝑅𝑅𝑅
𝑘𝑘 𝑇𝑇1 𝐸𝐸
= 𝑒𝑒𝑒𝑒𝑒𝑒 𝑇𝑇1 − 𝑇𝑇2
kT = reaction rate constant, variable units 𝑘𝑘 𝑇𝑇2 𝑅𝑅𝑇𝑇1 𝑇𝑇2
E = activation energy, J/mol
R = universal gas constant, 8.314 J/mol. K
T = temperature, K Assuming E/RT1T2 is approximately
constant, the above equation becomes:

𝑘𝑘 𝑇𝑇1 = 𝑘𝑘 𝑇𝑇2 𝜃𝜃 𝑇𝑇1 −𝑇𝑇2

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 Reaction Kinetics
Analysis of Experimental Data

• Commonly used methods to determine the order of a reaction from

experimental data:

• The method of integration

• The differential method

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 Reaction Kinetics
Analysis of Experimental Data- Method of Integration

• The order of a reaction can be determined by plotting the experimental data

functionally, based on the integrated form of the rate expression. If a straight
line plot is obtained, it is assumed that the order of the reaction corresponds to
the reaction plotted.

• Typically, rate expression are conducted in vessels in which there is no inflow or

outflow, and where the following relationship holds:

𝑑𝑑 𝐴𝐴
𝑟𝑟𝐴𝐴 =
𝑑𝑑𝑑𝑑

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 Reaction Kinetics
Method of Integration-Irreversible Zero-Order Reactions

• For the following reaction carried out in a batch reactor:

𝐴𝐴 → 𝑃𝑃

𝑑𝑑 𝐴𝐴
𝑟𝑟𝐴𝐴 = = −𝑘𝑘
𝑑𝑑𝑑𝑑
𝐴𝐴 𝑡𝑡
𝑑𝑑 𝐴𝐴 = −𝑘𝑘𝑘𝑘𝑘𝑘 => � 𝑑𝑑 𝐴𝐴 = −𝑘𝑘 � 𝑑𝑑𝑑𝑑 =>
𝐴𝐴0 0

𝐴𝐴 − 𝐴𝐴0 = −𝑘𝑘𝑘𝑘 => 𝐴𝐴 = 𝐴𝐴0 − 𝑘𝑘𝑘𝑘

• If the experimental data plots linearly according to the above equation, then k can be
obtained from the slope of the plot. 16
 Reaction Kinetics
Method of Integration-Irreversible First-Order Reactions
• For the following reaction carried out in a batch reactor:

𝐴𝐴 → 𝑃𝑃

𝑑𝑑 𝐴𝐴
𝑟𝑟𝐴𝐴 = = −𝑘𝑘 𝐴𝐴 =>
𝑑𝑑𝑑𝑑

𝐴𝐴 𝑡𝑡
𝑑𝑑 𝐴𝐴 𝑑𝑑 𝐴𝐴 𝐴𝐴
= −𝑘𝑘𝑘𝑘𝑘𝑘 => � = −𝑘𝑘 � 𝑑𝑑𝑑𝑑 => 𝑙𝑙𝑙𝑙 𝐴𝐴 − 𝑙𝑙𝑙𝑙 𝐴𝐴0 = −𝑘𝑘𝑘𝑘 => 𝑙𝑙𝑙𝑙 = −𝑘𝑘𝑘𝑘
𝐴𝐴 𝐴𝐴0 𝐴𝐴 0 𝐴𝐴 0

Or

𝐴𝐴 −𝑘𝑘𝑘𝑘
𝐿𝐿𝐿𝐿𝐿𝐿 =
𝐴𝐴0 2.3

𝐴𝐴
• The reaction rate constant is obtained graphically by plotting 𝐿𝐿𝐿𝐿𝐿𝐿 𝐴𝐴0
versus t
17
 Reaction Kinetics
Method of Integration-Irreversible Second-Order Reactions

• For the following reaction carried out in a batch reactor:

𝐴𝐴 + 𝐴𝐴 → 𝑃𝑃
• If the reaction is second order, then:

𝑑𝑑 𝐴𝐴
𝑟𝑟𝐴𝐴 = = −𝑘𝑘 𝐴𝐴 2 =>
𝐴𝐴 𝑑𝑑𝑑𝑑𝑡𝑡
� 𝐴𝐴 2 𝑑𝑑 𝐴𝐴 = −𝑘𝑘 � 𝑑𝑑𝑑𝑑 => − 𝐴𝐴 −1 |𝐴𝐴𝐴𝐴0 = −𝑘𝑘𝑘𝑘 =>
𝐴𝐴0 0
1 1 1 1 1 1
− − = −𝑘𝑘𝑘𝑘 => − = 𝑘𝑘𝑘𝑘 => = 𝑘𝑘𝑘𝑘 +
𝐴𝐴 𝐴𝐴0 𝐴𝐴 𝐴𝐴0 𝐴𝐴 𝐴𝐴0

1
• The reaction rate constant is obtained graphically by plotting versus t
𝐴𝐴 18
 Reaction Kinetics
Method of Integration-Saturation Reactions
• For the following reaction carried out in a batch reactor:

𝑑𝑑 𝑆𝑆 𝑘𝑘 𝑆𝑆 𝑑𝑑 𝑆𝑆 𝑑𝑑 𝑆𝑆
𝑟𝑟𝑠𝑠 = =− => = −𝑘𝑘𝑘𝑘 => 𝐾𝐾𝑠𝑠 + 𝑆𝑆 = −𝑘𝑘𝑘𝑘𝑘𝑘 =>
𝑑𝑑𝑑𝑑 𝐾𝐾𝑠𝑠 + 𝑆𝑆 𝑆𝑆 𝑆𝑆
𝐾𝐾𝑠𝑠 + 𝑆𝑆

𝑑𝑑 𝑆𝑆 𝑆𝑆
𝐾𝐾𝑠𝑠 + 𝑑𝑑 𝑆𝑆 = −𝑘𝑘𝑘𝑘𝑘𝑘 => 𝐾𝐾𝑠𝑠 𝑙𝑙𝑙𝑙 + 𝑆𝑆 − 𝑆𝑆0 = −𝑘𝑘𝑘𝑘 =>
𝑆𝑆 𝑆𝑆0

𝑆𝑆0 𝑆𝑆0
𝐾𝐾𝑠𝑠 𝑙𝑙𝑙𝑙 + 𝑆𝑆0 − 𝑆𝑆 = 𝑘𝑘𝑘𝑘𝑘𝑘 => 2.3𝐾𝐾𝑠𝑠 𝐿𝐿𝐿𝐿𝐿𝐿 + 𝑆𝑆0 − 𝑆𝑆 = 𝑘𝑘𝑘𝑘𝑘𝑘 =>
𝑆𝑆 𝑆𝑆

2.3 𝑆𝑆0 1 𝑆𝑆0 − 𝑆𝑆 𝑘𝑘

𝐿𝐿𝐿𝐿𝐿𝐿 =− +
𝑡𝑡 𝑆𝑆 𝐾𝐾𝑠𝑠 𝑡𝑡 𝐾𝐾𝑠𝑠

2.3 𝑆𝑆 𝑆𝑆0 − 𝑆𝑆
• The reaction rate constant is obtained graphically by plotting 𝐿𝐿𝐿𝐿𝐿𝐿 0 versus
𝑡𝑡 𝑆𝑆 𝑡𝑡
19
 Reaction Kinetics
The Differential Method
The differential method of analysis is based on the assumption that the role of reaction is proportional to the
nth power of the concentration::

𝑑𝑑 𝐴𝐴
𝑟𝑟𝐴𝐴 = = −𝑘𝑘 𝐴𝐴 𝑛𝑛
𝑑𝑑𝑑𝑑
For two different concentrations of two different times, the following expression holds:

𝑑𝑑 𝐴𝐴1 𝑛𝑛
= −𝑘𝑘 𝐴𝐴1
𝑑𝑑𝑑𝑑

𝑑𝑑 𝐴𝐴2 𝑛𝑛
= −𝑘𝑘 𝐴𝐴2
𝑑𝑑𝑑𝑑

𝑑𝑑 𝐴𝐴1 𝑛𝑛
𝐿𝐿𝐿𝐿𝐿𝐿 − = 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 + 𝐿𝐿𝐿𝐿𝐿𝐿 𝐴𝐴1 = 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 + 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝐴𝐴1 =>
𝑑𝑑𝑑𝑑
𝑑𝑑 𝐴𝐴1
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 = 𝐿𝐿𝐿𝐿𝐿𝐿 − − 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝐴𝐴1
𝑑𝑑𝑑𝑑 20
 Reaction Kinetics
The Differential Method

Similarly,

𝑑𝑑 𝐴𝐴2
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 = 𝐿𝐿𝐿𝐿𝐿𝐿 − − 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝐴𝐴2
𝑑𝑑𝑑𝑑

𝑑𝑑 𝐴𝐴1 𝑑𝑑 𝐴𝐴2
=≫ 𝐿𝐿𝐿𝐿𝐿𝐿 − − 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝐴𝐴1 = 𝐿𝐿𝐿𝐿𝐿𝐿 − − 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝐴𝐴2
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑

𝑑𝑑 𝐴𝐴1 𝑑𝑑 𝐴𝐴2
=> 𝑛𝑛 𝐿𝐿𝐿𝐿𝐿𝐿 𝐴𝐴1 − 𝐿𝐿𝐿𝐿𝐿𝐿 𝐴𝐴2 = 𝐿𝐿𝐿𝐿𝐿𝐿 − − 𝐿𝐿𝐿𝐿𝐿𝐿 −
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑

𝑑𝑑 𝐴𝐴1 𝑑𝑑 𝐴𝐴2
𝐿𝐿𝐿𝐿𝐿𝐿 − − 𝐿𝐿𝐿𝐿𝐿𝐿 −
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
=≫ 𝑛𝑛 =
𝐿𝐿𝐿𝐿𝐿𝐿 𝐴𝐴1 − 𝐿𝐿𝐿𝐿𝐿𝐿 𝐴𝐴2 21