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18/01/2018

REACTION KINETICS
A variety of chemical and biochemical reactions take place in the
environment that are of importance to environmental engineers
MODULE 3 and scientists. These include reactions between various elements of
the air, water, and soil, as well as with microorganisms.
Reaction Kinetics and Chemical Reactors A number of these reactions are dependent on:

ILOs: a) Time
1. Recall Reaction Kinetics b) Temperature
2. Discuss principles about Chemical c) Pressure
Reactors d) Concentration
3. Derive necessary equations for the types of
reactors
For example: biodegradation of organic matter, bacterial growth
4. Solve complex problems about kinetics and
and decay, and chemical disinfection.
reactors

REACTION KINETICS REACTION KINETICS


Reaction kinetics can be defined as the study of the effects of The rate of reaction, ri , is used to describe the rate of formation
temperature, pressure, and concentration of reactants and products of a product, or rate of disappearance of a reactant.
on the rate of a chemical reaction (Henry and Heinke, 1996).
For homogeneous reactions, ri is calculated as the moles or mass
produced or consumed per unit volume per unit time.
Reactions that occur within a single phase (solid, liquid, or
gaseous) are called homogeneous reactions, e.g. nitrification in
Let us consider the following homogeneous reaction:
wastewater.
aA + bB → cC
Reactions that involve two or more phases are called heterogeneous
reactions, e.g. gas adsorption on activated carbon where:
C = product
A, B = reactants
a, b, c = stoichiometric coefficients

REACTION KINETICS REACTION KINETICS


The rate equation for the above reaction is: The order of a reaction is the sum of the empirically determined
exponents, e.g. the order is (α + β) with respect to the reactants A
rA = –k [A]α[B]β = k[C]γ and B, while the order is γ with respect to its product C. The order
of a reaction can be a whole number (e.g. 0, 1, 2) or a fraction.
Where:
α, β, γ = empirically determined exponents For a homogeneous, irreversible, elementary reaction that occurs in
[A], [B], [C] = molar concentrations of A, B, and C, respectively a single step, the empirically determined exponents are equal to the
k = reaction rate constant stoichiometric coefficients.

In that case, the previous equation becomes a power of c:

rA = –k [A]α [B]β = k[C]c

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HOW TO FIND THE ORDER OF A REACTION


HOW TO FIND THE ORDER OF A REACTION
Consider the following irreversible elementary reaction
where reactant A is converted to a product C:

A→C

The rate equation can be written as follows:

rA = –k[A]α or loge(–rA) = loge(k) + α loge[A]

Where:
α = order of the reaction (e.g. 0, 1, 2, etc.)
k = reaction rate constant

An experiment is conducted where the above reaction is allowed to


proceed. The concentration of A ([A]) at various time intervals (t) is
measured. Plot [A] versus t. Calculate slope (rA) of the tangent at
various points along the curve. Plot loge(–rA) versus loge[A]. Slope of
the best fit line is equal to the order of reaction.

ZERO ORDER REACTION ZERO ORDER REACTION


A zero order reaction proceeds at a rate that is independent of Where:
the concentration of the reactants or products. Consider the 𝑑𝐴
= rate of change of concentration of A with time
following irreversible elementary reaction where reactant A is 𝑑𝑡
converted to product C: k = reaction rate constant, time-1

A→C Integrating the equation from initial values to values after time t
[𝐴𝑡 ] 𝑡

If this reaction is zero order, the rate expression can be written as: 𝑑 𝐴 = −𝑘 𝑑𝑡
[𝐴0 ] 0
rA = –k
[𝐴𝑡 ] – [𝐴𝑜 ] = – 𝑘𝑡
𝑑[𝐴] 0 Where:
= −𝑘 𝐴 = −𝑘 1 = −𝑘
𝑑𝑡 [Ao] = initial concentration of reactant A at time zero, mg/L
[At ] = concentration of A after time t, mg/L

SECOND ORDER REACTION


FIRST ORDER REACTION
If the reaction is second order with respect to concentration of A,
If the reaction is first order with respect to concentration of A, the the rate expression becomes:
rate expression becomes: 𝑑[𝐴]
𝑑[𝐴] = −𝑘 𝐴 2
= −𝑘 𝐴 𝑑𝑡
𝑑𝑡
Integrate equation between initial values and values after time t
Integrate equation between initial values and values after time t,
[𝐴𝑡 ] 𝑡 [𝐴𝑡 ] 𝑡
𝑑[𝐴] 𝑑[𝐴]
= −𝑘 𝑑𝑡 = −𝑘 𝑑𝑡
[𝐴] 𝐴2
[𝐴0 ] 0 [𝐴0 ] 0

𝐴𝑜 1 1
log 𝑒 = 𝑘𝑡 − = 𝑘𝑡
𝐴𝑡 [𝐴𝑡 ] 𝐴0

𝐴𝑡 = 𝐴0 𝑒 −𝑘𝑡

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REACTORS REACTORS
A reactor is a tank or vessel where chemical, biological, or There are three (3) types of ideal reactors:
biochemical reactions take place, usually in a liquid medium. (1) batch reactor,
(2) plug flow reactor (PFR), and
Reactions can also take place in solid or gaseous medium or in a (3) continuous-flow stirred tank reactor (CSTR).
combination.
The hydraulics and conversion efficiencies of these reactors can be
Chemical reactors are used in a water treatment plant in determined using mathematical models.
coagulation–flocculation, lime softening, taste and odor control,
disinfection, and other unit processes that involve chemical Models developed for ideal reactors can be further modified to
reactions. represent real-life processes and flow conditions for reactors used
at treatment plants.
Reactors used in wastewater treatment plants involve mostly
biochemical and biological reactions, e.g. activated sludge reactor,
membrane bioreactor.

Conversion of a reactant Detention time in reactor


The conversion or removal of a reactant is calculated as follows: The theoretical detention time or residence time of the fluid
particles in a reactor is given by:
𝑉
𝐴0 − [𝐴𝑡 ] 𝐴𝑡 𝑡=
𝑓= =1− 𝑄
[𝐴0 ] 𝐴0
Where:
t = detention time in reactor
Where:
V = volume of reactor
f = conversion or removal efficiency
Q = volumetric flow rate, volume/time
[Ao] = initial concentration of reactant A at time zero, mg/L
[At ] = concentration of A after time t, mg/L
The actual detention time in a reactor can be determined by adding
a tracer or dye to the influent during steady state flow and then
measuring the concentration of the tracer in the effluent over a
period of time.

Detention time in reactor BATCH REACTOR


In a batch reactor, reactants are added to the reactor and mixed
for a requisite amount of time for the reactions to occur.

At the end of the reaction time, the contents are removed from the
reactor.

One characteristic of the batch reactor is that all fluid particles have
the same residence time in the reactor.

Homogeneous mixing is assumed, so that the composition of the


mixture is the same throughout the reactor.

The concentration varies with time as the reaction proceeds.

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BATCH REACTOR Design equation


Batch reactors are generally used for bench scale experiments and 𝑅𝑖𝑛 = 𝑅𝑜𝑢𝑡 + 𝑅𝑎𝑐𝑐 − 𝑅𝑐𝑜𝑛
liquid phase reactions. They are useful in determining the effects of Where:
variables on a reaction process. Rin/out – Rate of input/output
Racc – Rate of accumulation
Rcon – Rate of consumption
A number of experiments can be conducted at the same time in
batch reactors, thus facilitating the study of process variables. They For a batch reactor, the time period for reaction begins just after the
are used extensively in pharmaceutical and other industries. reactor is filled and ends just before contents are emptied. So, rate of input
and output becomes zero. Thus, the above equation becomes:
Batch reactors are not suitable for gas phase reactions or large-
𝑅𝑎𝑐𝑐 = 𝑅𝑐𝑜𝑛
scale commercial applications.
So, the design equation is written as follows:
Labor costs and materials handling costs can run high, due to the
time and effort involved in filling, emptying, and cleaning the 𝑑[𝐴]
𝑟𝐴 =
reactors. 𝑑𝑡

Design equation PLUG FLOW REACTOR (PFR)


where: In a Plug Flow Reactor, fluid particles flow through the tank and
rA = rate of consumption of limiting reactant A, concentration/time are discharged in the same sequence as they entered. The fluid
[A] = concentration of limiting reactant A particles move through the reactor tube as plugs moving parallel to
the tube axis.
When the order of the reaction is known, an expression for rA can
be substituted into the left side of equation, and the resulting The plug flow reactor is suitable for gas phase reactions that take
differential equation can be integrated to obtain the design place at high pressure and temperature. The average reaction rate
expression. is usually higher in a PFR as compared with a CSTR of similar
volume, for the same feed composition and reaction temperature.

The PFR makes more efficient use of reactor volume, which makes
it suitable for processes that require large volumes. With
sufficiently high recycle rates, the behavior of the PFR becomes
similar to that of a CSTR.

Design equation Design equations for batch, PFR, CSTR

𝑅𝑖𝑛 = 𝑅𝑜𝑢𝑡 + 𝑅𝑎𝑐𝑐 − 𝑅𝑐𝑜𝑛

For steady state conditions, the design equation is written as


𝑑[𝐴]
𝑟𝐴 =
𝑑𝑡
which is the same as the design equation for a batch reactor.

When the order of the reaction is known, an expression for rA can


be substituted into the left side of the above equation, and the
resulting differential equation can be integrated to obtain the
design expression.

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CONTINUOUS-FLOW STIRRED TANK REACTOR CONTINUOUS-FLOW STIRRED TANK REACTOR


Continuous-flow stirred tank reactors (CSTRs) are used A tracer molecule in the influent has equal probability of being
mainly for liquid phase reactions at low or atmospheric pressures. located anywhere in the reactor after a small time interval, within
the limit of complete mixing (Hill, 1977).
In this reactor, the reactant flows continuously into the reactor, the
product effluent flows out continuously, and the reactor contents Thus all fluid elements in the reactor have equal probability of
are mixed on a continuous basis. leaving the reactor with the effluent in the next time increment. As
a result, there is a broad distribution of residence times for various
This type of reactor is also called back mix reactor or completely fluid particles.
mixed reactor. The basic assumption for an ideal CSTR is that the
reactor contents are completely mixed and homogeneous Lower conversion of reactant is achieved in a CSTR as compared
throughout. with a PFR, at the same operating temperature and feed
composition. This is mainly due to the variation of particle
When a reactant [Ao] enters the reactor, it is subjected to residence times within the reactor and the inability to achieve
instantaneous and complete mixing, resulting in immediate complete mixing. As a result, a CSTR of larger volume is required
reduction to the final effluent concentration [At ]. to achieve the same conversion as a PFR.

Design equation
REACTORS IN SERIES
𝑅𝑖𝑛 = 𝑅𝑜𝑢𝑡 + 𝑅𝑎𝑐𝑐 − 𝑅𝑐𝑜𝑛
One method of increasing the removal efficiency of a process is to
use a number of reactors in series. This is usually applicable for
At steady state conditions, rate of accumulation = 0. So the design
equation can be written as: CSTRs, though a combination of CSTR and PFR can also be used.
When a series or cascade of CSTRs are used, the effluent from one
𝐴𝑡 − [𝐴0 ] reactor serves as the influent to the next reactor.
𝑟𝐴 =
𝑡
There is a stepwise decrease in the composition of reactant and
where all the terms have the same meanings as defined in the temperature as the flow travels from one reactor to the next one.
previous sections. Assuming that the conditions in any individual reactor in the series
are not influenced by downstream conditions, and conditions of the
When the order of the reaction is known, an expression for rA can inlet stream and those prevailing in the reactor are the only
be substituted into the left side of the above equation to obtain the variables that influence reactor performance (Hill, 1977), the
design expression. following design equation can be written for steady state
conditions:

REACTORS IN SERIES REACTORS IN SERIES


𝐴𝑖− 𝐴 𝑖−1
𝑟𝐴𝑖 =
𝑡𝑖

Where:
rAi = rate of consumption of A in ith reactor
ti = detention time in ith reactor
[A]i = concentration of A in effluent from ith reactor
[A](i–1) = concentration of A in effluent from (i–1)th reactor
= concentration of A in influent to ith reactor

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REACTORS IN SERIES SEMI-BATCH OR SEMI-FLOW REACTORS


The detention time in the ith reactor is given by: Reactors used in actual treatment plants and processes may be
operated somewhere in between ideal reactor modes. Reactor
𝑉𝑖 operation can be semi-batch or semi-flow.
𝑡𝑖 =
𝑄
Where: A few examples are:
Vi = volume of reactor 1. A reactor where all the reactants are added at the same time as
Q = volumetric flow rate, volume/time a batch, but the products are discharged continuously;
2. A reactor where the reactants are added at different time
In a series of n reactors, the overall conversion is given by intervals;
𝐴0 − [𝐴𝑛 ] 3. A reactor where the products are removed at different time
𝑓=
[𝐴0 ] intervals;
Where: 4. A batch reactor partially filled with one reactant, with
[Ao] = concentration of A in influent to 1st reactor progressive addition of other reactants until the reaction is
[An] = concentration of A in effluent from nth reactor completed.

SAMPLE PROBLEMS
SAMPLE PROBLEMS
Solution-01:
Assuming that the section of the curve between each time interval
Problem-01: The following data were obtained from a batch is a straight line, the rates could be calculated from the slope of that
experiment for the reaction A → P. Determine the order of the section.
reaction.
So, if rA = dA/dt:
𝑑𝐴 ∆𝐴 100 − 74
Point A B C D E F G = = = −2.59
𝑑𝑡 ∆𝑡 0 − 10
Time(min) 0 10 20 40 60 80 100
For first interval and so on.
A (mg/L) 100 74 55 30 17 9 5
Plotting of ln(–rA) versus ln(A) will yield a slope that we can use for
the best fit line, which is 0.935, and can be rounded-off to 1. So the
reaction is first order.

SAMPLE PROBLEMS SAMPLE PROBLEMS


Cont. Solution-01: Cont. Solution-01:

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SAMPLE PROBLEMS SAMPLE PROBLEMS


Cont. Solution-01:
Problem-02: Consider a first order reaction taking place in a
batch reactor. Develop an expression for the detention time in the
reactor.

Solution-02:
For a first order reaction, rA = –k[A] Substitute the expression for
rA in equation:
𝑑[𝐴]
= −𝑘 𝐴
𝑑𝑡

Upon integration between limits we obtain,


𝐴𝑜 1 𝐴𝑜
log 𝑒 = 𝑘𝑡 or 𝑡 = ln
𝐴𝑡 𝑘 𝐴𝑡

Sample Problems Sample Problems


Problem-03: A reaction takes place in a PFR, where reactant A is thus, we can say that:
converted to product P. The rate equation is rA = –0.38 [A]
mol/L·s. Determine the volume of PFR required for 95% 0.25
conversion of A. The initial concentration of A is 0.25 mol/L, and 0.38𝑡 = ln
0.0125
volumetric flow rate is 5 m3/s. Solving for time, t we’ll get:

Solution-03: The given reaction is first order with k = 0.38/s, 𝑡 = 7.88 𝑠𝑒𝑐𝑠.
[Ao] = 0.25 mol/L. With 95% conversion, [At] = (1 – 0.95) [Ao] =
0.05 × 0.25 = 0.0125 mol/L. We can now solve for the Volume of PFR,

First order design equation for a PFR is: 𝑚3


𝑉 = 𝑄𝑡 = 5 (7.88𝑠) = 𝟑𝟗. 𝟒𝟐 𝒎𝟑
𝑠
𝐴𝑜
𝑘𝑡 = ln
𝐴𝑡

SAMPLE PROBLEMS SAMPLE PROBLEMS


Problem-04: A chemical reaction takes place in a CSTR, where A Cont. Solution-04:
is converted to product P. The initial concentration of A is 45 mg/L. Thus, we can say that:
After 5 min, concentration of A is measured as 36 mg/L. 1 45
𝑘= − 1 = 𝟎. 𝟎𝟓/min
5 36
a. Calculate the rate coefficient assuming that the reaction is first
order. For the second order reaction, we’ll use the formula:
b. Calculate the rate coefficient assuming that the reaction is 1 𝐴𝑜
second order 𝑘𝑡 = −1
𝐴𝑡 𝐴𝑡

Solution-04:
Thus, we can say that:
For the first order reaction, we’ll use the formula: 1 45 𝑳
𝐴𝑜 𝑘= − 1 = 𝟎. 𝟎𝟎𝟏𝟒
𝑘𝑡 = −1 5 36 36 𝒎𝒈 ∙ 𝒎𝒊𝒏
𝐴𝑡

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SAMPLE PROBLEMS Sample Problems


Problem-05: Consider the same first order chemical reaction From Problem-04, Ao = 45 mg/L, A1 = 36 mg/L, kCSTR = 0.05/min.
from Problem-04. Two reactors are used in series, a CSTR followed Therefore, kPFR = 0.05/min
by a PFR for product formation. The detention time in the first
reactor (CSTR) is 5 min. The two reactors are operated at the same Use the design equation for PFR for first order reaction
temperature and have the same volume. What will be the effluent 𝐴1
concentration of A from the PFR? What is the conversion 𝑘𝑡 = ln
𝐴2
efficiency? 36
0.05 5 = ln
𝐴2
Solution-05: The two reactors are operated at the same 𝑨𝟐 = 𝟐𝟖. 𝟎𝟒 𝒎𝒈/𝑳
temperature: Therefore, kCSTR = kPFR
45 − 28.04
The two reactors have the same volume, and if the flow rate is the 𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = × 100% = 𝟑𝟕%
45
same, thus detention time, tCSTR = tPFR

Sample Problems
Problem-06: In Problem-05, if another CSTR was used as the
second reactor instead of the PFR, what would be the effluent
concentration of A? Calculate the conversion efficiency. Determine
the concentration of reactant A in the first and second reactors.

Solution-06:
Using the equation for CSTR for the first order reaction in reactor
#2:
𝑚𝑔 0.05
𝐴1 = 36 ; 𝑘𝐶𝑆𝑇𝑅 = ; 𝑡 = 5𝑚𝑖𝑛
𝐿 𝑚𝑖𝑛
𝐴1 36 𝒎𝒈
𝑘𝑡 = − 1; 0.05 5 = − 1; 𝑨𝟐 = 𝟐𝟖. 𝟖𝟎
𝐴2 𝐴2 𝑳
45 − 28.80
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = × 100% = 𝟑𝟔%
45

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