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MODULE 1

EVALUATION OF RATE EQUATION


BT 303- CHEMICAL AND BIOLOGICAL REACTION ENGINEERING
FIFTH SEMESTER BIOTECHNOLOGY AND BIOCHEMICAL ENGINEERING
SREE CHITRA THIRUNAL COLLEGE OF ENGINEERING

REFERENCE: CHEMICAL REACTION ENGINEERING BY OCTAVE LEVENSPIEL


Chapter 3: Interpretation of Batch Reactor Data
Two step procedure: to determination of the
rate equation
1. The concentration dependency is found at fixed
temperature
2. The temperature dependence of rate constants, yielding
the complete rate equations

Equipment for Kinetic data measurement


1. Batch reactor- primarily used for homogeneous reaction
2. Flow reactor- primarily used for heterogeneous reaction
Determination of extent of reaction
• By following the concentration of a given component.
• By following the change in some physical property of the fluid, such as the
electrical conductivity or refractive index.
• By following the change in total pressure of a constant-volume system.
• By following the change in volume of a constant-pressure system.
Procedures for analysing kinetic data

Integral Method Differential Method


• We guess a particular form of rate • We test the fit of the rate expression
equation and after appropriate to the data directly and without any
integration and mathematical
manipulation integration.
• Predict the plot of a certain • However, since the rate expression is a
concentration function versus time differential equation,
should yield a straight line
• The data are plotted, and if a • we must first find (l/V)(dNldt) from
reasonably good straight line is the data before attempting the fitting
obtained procedure.
• The rate equation is said to
satisfactorily fit the data
Integral method Differential method

• It is easy to use • It is used in complicated


• It is recommended for testing situations
specific mechanisms or simple • It requires larger data set
rate expressions or when the • It is used to develop or build up
data are scattered that we a rate equation to fit the data
cannot find the derivatives
• It can only test particular rate
mechanism or form

INTEGRAL ANALYSIS IS ATTEMPTED FIRST, THEN ONLY DIFFERENTIAL ANALYSIS


CONSTANT VOLUME BATCH REACTOR
• Here we are referring to the volume of the reaction mixture and not
the volume of reactor.
• It means a CONSTANT- DENSITY REACTION SYSTEM
• Most liquid phase & all gas phase reaction occurring in constant
volume bomb fall in this class
In a constant volume system the measure of
reaction rate of component i
• The rate of reaction of any component is given by the rate of change
of its concentration or partial pressure
• For gas reactions with changing numbers of moles, a simple way of
finding the reaction rate is to follow the change in total pressure π of
the system
The conversion XA
• The fractional conversion or • Suppose that,
the fraction of any reactant, NA0 – initial amount of A in the
say A converted to something reactor at time t=0
else or the fraction of A
reacted away NA –amount present at time t
The conversion of A in constant
volume system
𝑁𝐴𝑜−𝑁𝐴
XA =
𝑁𝐴0
XA =
𝑁𝐴𝑜−𝑁𝐴
𝑁𝐴0
=
At time t= 0, the number of moles of A (NA0 )= 100 moles
At time t= 10s, the number of moles of A (NA ) = 60 moles

100−60
Then, the conversion of A after 10s = XA = = 0.4 ( 40% of A has been converted)
100

The fraction of A which is not converted after 10s = 1- XA = 0.6 (60% of A has not been converted)
Integral Method of Analysis of Data
Integral Method of Analysis of Data
• The integral method of analysis always puts a particular rate equation
to the test by integrating and comparing the predicted C versus t
curve with the experimental C versus t data.
• If the fit is unsatisfactory, another rate equation is guessed and
tested. This procedure is shown and used in the cases next treated.
• It should be noted that the integral method is especially useful for
fitting simple reaction types corresponding to elementary reactions
SOME EXAMPLES
Irreversible Unimolecular-Type First-Order
Reactions
• A plot of In (1 - XA) or In (CA/Cao) v
s. t, as shown in Fig. 3.1, gives a
straight line through the origin for
this form of rate of equation.
• If the experimental data seems to
be better fitted by a curve than by
a straight line, try another rate
form because the first-order
reaction does not satisfactorily fit
the data.
Irreversible Bimolecular-Type Second-Order
Reactions
Consider the reaction
Irreversible Trimolecular-Type Third-Order
Reactions.
• Consider the reaction
Develop the Integrated kinetic expression
using Integral method of analysis
CONSTANT VOLUME SYSTEM

1. Irreversible bimolecular type second order reaction (A+B P)


2.Irreversible bimolecular type second order reaction (2A P)
3.Irreversible bimolecular type second order reaction (A+2BP)
4.Irreversible trimolecular type third order reaction (A+B+DP)
5.Irreversible trimolecular type third order reaction (3AP)
6.Irreversible reactions in series ARS . The reaction rate constant k1
and k2 respectively
7.Irreversible reactions in parallel AR , AS. The reaction rate
constant k1 and k2 respectively
8. Homogeneous catalysed reaction AR and A+CR+C ,where the
reaction rate constant k1 and k2 respectively

9. Autocatalytic reactions A+RR+R

10. First order reversible reaction A R, where the forward reaction


rate constant are k1 and backward reaction rate constant are k2
respectively
Reactant A decomposes in a Batch reactor
A Products
REPORTED DATA

Time t,s Concentration Ca, mol/l


0 10
20 8
40 6
60 5
120 3
180 2
300 1
CALCULATED DATA

Time t,s Concentration Ca, ln Cao/Ca 1/Ca


mol/l
0 10 0 0.1
20 8 0.2231 0.125
40 6 0.511 0.167
60 5 0.6931 0.200
120 3 1.204 0.333
180 2 1.609 0.5
300 1 2.303 1
ln Cao/Ca vs t should give a straight line if it is
following first order kinetics
1/Ca vs t should give a straight line if it is
following second order kinetics
Differential Method of Analysis of Data
Differential Method of Analysis of Data
• The differential method of analysis deals directly with the differential
rate equation to be tested, evaluating all terms in the equation
including the derivative dCldt, and testing the goodness of fit of the
equation with experiment.
PROCEDURE
Further Exercises
Consider the reaction of 2AB+C, for which the rate equation is of the
general form –rA= f(k,Ca) and does not follow elementary kinetics. Based
upon the time versus concentration data below from a batch reaction
experiment, determine the complete kinetic rate form, that is, determine
the order for Ca, in the rate equation and determine the values of k
(kinetic rate constant). All rate data is at single temperature

Time (min) 0 15 30 40 50 70 100


Ca (mol/l) 0.1 0.063 0.05 0.045 0.041 0.035 0.03
OUTCOMES
• How to determine the rate expression from Concentration vs time data
• Understanding extent of reaction
• Integral and Differential method of analysis

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