Reaction Kinetics

Some examples in Environmental Engineering:

i) Oxidation of carbon on the surface of a burning
coal particle.
ii) Consumption of O2 and radioactive decay in
sediment.
iii) Reaction of NO2 with surfaces in a house.
iv) Consumption of Cl2 in water and biofilms.
v) Biological oxidation of organics in natural
water
vi) Hydrolysis, complexation of natural organic
and inorganic matter in aquatic systems such as
river, lake, groundwater.

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First order reactions
A →B
Stoichiometry: 1 mole of A is converted to 1
mole of B, rates of A and B are respectively,

rate: -rA = dCA/dt =- k CA

and rB = dCB/dt = k CB

where CA, CB = concentrations of A and B

k = rate constant
concentration units are molar, mass, number
concentration, partial pressure or aerosol
number concentration in air. From the above
two equations,

-rA = rB or, rA = - rB
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• Reactions in which the kinetics are determined by the
stoichiometry are called elementary reactions.

• Integrating 1st order rate equation with initial conditions

of CA = CA0 at t =0,

• Thus, CA = CA0 exp (-kt)

• At time t=0, CB0=0,

• at any other time t, CB = CA0 - CA = CA0 [1- exp(-kt)]

t 3
Examples of 1st order reactions:

a) Rate of birth and death are proportional to the

population.
b) Rate of disinfection of pathogenic organisms,
dN/dt = -kN (Chick’s law)
where N is the number of organism, k is the Chick’s law
constant.
c) Radioactive decay of atom. Half life of an atom is the
time required to reach its concentration by half. From
the 1st order reaction;

ln [CA / CA0 ] = -kt

ln C
at t= t1/2, CA = CA0 /2
Substituting, ln 2 = kt
t1/2 = 0.693/k
t
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Second order reaction:
A + B →C
rate:
-r A = d CA /dt =- k CA CB = dCB /dt = -rB
let x is the amount of A or B reacted, then
CA = CA0 - x; CB = CB0 - x
Substituting: 1 C (C − x)
ln B 0 A0 = kt
C A0 − C B 0 C A0 (C B 0 − x )
dx / {(CA0- x)( CB0 - x)} = kdt
at t=0, x =0, the solution is:
limiting case:
when CA0= CB0 then CA= CB 1/CA
Then kinetics of second order rate:
dCA/dt = -k CA2
plot 1/CA vs. t ; slope = k, rate constant. t 5
Pseudo-first-order reactions
If in second order reaction, the concentration of one reactant (B) is
much greater than (A), then the rate is no more dependent on B, and
the reaction is pseudo-first order with respect to A.
Zero-order reactions
The rate of reaction is independent of concentration of the reactants.
Zero order reactions are very common in catalysis. The rate is:
rA = dCA/dt =- k
Reversible Reactions
A → B, rate of forward reaction,
rf = k1 CA
and the backward reaction,
rb = k2 CB
at equilibrium, rf =rb, and the equilibrium constant
Keq = CBeq / CAeq = k1 / k2
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Arrhenius Law and effect of temperature

Reaction rate doubles for each 10 0C increase in temperature.

k = Af exp (-Ea/RT)
Here R= is the universal gas constant
Af = Arrhenius frequency factor
Ea= Activation energy

Activation energy is the barrier that must be surmounted for

the reaction to occur.
Reactors
There are different types of Reactors of relevance in
environmental application
1. Completely mixed batch reactor (CMBR)
2. Completely mixed flow reactor (CMFR) or completely stirred
tank reactor (CSTR)
3. Plug flow reactor (PFR) or plug flow tube reactor (PFTR).
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Completely mixed batch reactor (CMBR): Conditions are:
a) CMBR is a closed system.
b) composition and the relative distribution of reactants and
products change with time.
c) mixing is provided to insure that no concentration gradient
exists.
d) application for small quantities, or expensive, toxic materials.
e) un-steady state operation
Mass balance:[ rate of accumulation or decay of the reactant]
= [ rate of reaction within reactor]
t C dC
d (CV)/dt = V r (C); ∫
0
dt = ∫
C0 r (C )

if the reaction is first order, r(C) = -kC

Integrating with boundary condition, at t=0, C= C0
C = C0 e-kt

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 2) CMFR/CSTR
in, Q, Co Out, Q, C

Applications:

a) Bench scale experimentation and testing

b) Coagulation, extended aeration biological treatment.

Resistant to shock loadings and responds well to time-variant input

volumes and concentrations because influent reactants are rapidly
diluted throughout the tank.
Mass balance:

dC
V = QC o − QC + Vr (C )
dt

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 At steady state:
QCo − QC + Vr (C ) = 0

For 1st order reaction:

QCo − QC − kCV = 0
Dividing by Q C,
Co
− 1 − kt = 0; t = V / Q
C
This time ‘t’ is the residence or detention time in the reactor.
Upon rearrangement we get,
C 1
=
C0 1 + k t
The detention time can be given as:
1 ⎡ C0 ⎤
t= ⎢ − 1⎥
k⎣C ⎦

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CMFR/CSTR in series:
For a ‘n’ number of CMFRs, with equal volume ‘V’ in series, the
steady-state concentration of the effluent coming out of the
second reactor, C2, may be expressed as:
C2 1
=
C1 1 + k t

The effluent concentration from reactor 2 can be expressed in

terms of the influent concentration, C0, as:
2
C 2 ⎛ C1 ⎞⎛ C 2 ⎞ ⎡ 1 ⎤
=⎜ ⎟⎜
⎟⎜ C
⎟=⎢
⎟ ⎥
C0 ⎜⎝ C0 ⎠⎝ 1 ⎠ ⎣1 + k t ⎦

In similar fashion, the effluent concentration from the last (nth)

reactor can be expressed in terms of the influent concentration,
C0, to the first reactor. n
Cn ⎡ 1 ⎤
=
C0 ⎢⎣ 1 + k t ⎥⎦

The performance of several mixed reactors in series is equal to

that of a plug flow reactor.
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 Plug flow reactors (PFR) / Plug flow tubular reactors (PFTR):

Ci0

x Δx x
In an ideal plug-flow reactor, bulk flow proceeds through the reactor in
an orderly uniform manner.
The fluid particles pass through the tank and are discharged in the same
sequence as they entered the tank.
The contents are uniform in the radial direction and there is no mixing
due to concentration gradient in the radial direction. Thus, in an ideal
PF reactor, composition varies along the flow.
Mass balance is written as: ∂C ∂C
= −v x + r (C )
∂t ∂x
At steady state: Ce
x=L
∫
Ce
∂C ∂C
L
=
LA V
= =t =
dC
+ r (C ) or ∫ ∫ r (C )
dx
0 = −v x = or vx vx A Q r (C )
∂x x =0
vx
C0
C0

This is analogous to the batch reactor equation. For a first- 12

order reaction, C = C0 e-kt
Plug-flow reactor models are useful for describing many water
quality control processes. For example, in a chlorine contact
chamber, care is taken to insure that each elemental fluid volume
is exposed some minimum time, and plug flow reactor is an
optimal design.

Other examples are sedimentation tanks and certain other types

of aeration basins. Because the influent end of a PF reactor is
characterized by regions of high reactant concentration, this type
of reactor does not respond well to time variant or shock inputs.

However, the volume of a plug flow reactor can be considerably

smaller than the volume of a CMFR to accomplish a given extent
of a particular reaction for which rate increases with increasing
concentration of the reactant.

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 Example 1

• Consider a first-order reaction requiring 50%

reduction in the concentration. Would a plug-
flow or a CMFR require the least volume?

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 Example 2
A river has the following dimensions, L= 5 km, W=10 m,
and D=5 m, with a volumetric flow rate of 100 L/s. A
toxic compound undergoes oxidation with a rate
constant, 0.15 day-1. Find the distance where the
concentration of the species is 5% of the original
concentration.
a) Model the reactor as plug flow reactor (PFR)
b) Model the reactor as CSTR/CFMR

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