Integral Method of Analysis of Data

Fair Use Notice
The material used in this presentation i.e., pictures/graphs/text, etc. is solely

intended for educational/teaching purpose, offered free of cost to the students
for use under special circumstances of Online Education due to COVID-19
Lockdown situation and may include copyrighted material - the use of which
may not have been specifically authorized by Copyright Owners. It’s
application constitutes Fair Use of any such copyrighted material as provided
in globally accepted law of many countries. The contents of presentations are
intended only for the attendees of the class being conducted by the presenter.
Chemical Engineering Department
Chemical Reaction Engineering (CH314)
Lecture-10
Interpretation of Batch
Reactor Data
Dr. Imran Nazir Unar

Lecture Objectives
Discussion on:
• Integral Method of Analysis of Data
• Irreversible Reactions in Parallel.
• Homogeneous Catalyzed Reactions.
• Autocatalytic Reactions.
• Irreversible Reactions in Series.
INTERPRETATION OF BATCH REACTOR DATA
Irreversible Reactions in Parallel
 Consider the simplest case, A decomposing by two competing paths, both
elementary reactions:
 The rates of change of the three components are given by

(34)
(35)
(36)
 This is the first time we have encountered multiple reactions.
 For these in general, if it is necessary to write N stoichiometric equations to

describe what is happening, then it is necessary to follow the decomposition of N
reaction components to describe the kinetics.
 Thus, in this system following CA, or CR, or CS, alone will not give both k1 and k2.
At least two components must be followed.
 Then, from the stoichiometry, noting that CA + CR + Cs is constant, we can find

the concentration of the third component.
 The k values are found using all three differential rate equations.
 First of all, Eq. 34, which is of simple first order, is integrated to give:
(37)
 When plotted as in Fig. 1, the slope is k1 + k2.
 Then dividing Eq. 35 by Eq. 36 we obtain the following (Fig. 3.6).
 which when integrated gives simply • This result is shown in Fig.1.

• Thus, the slope of a plot of CR
(38) versus CS gives the ratio k1/k2.
• Knowing k1/k2 as well as k1 + k2
gives k1 and k2.
Fig. 1: Evaluation of the rate constants for two competing elementary first-order reactions of the type
Homogeneous Catalyzed Reactions
 Suppose the reaction rate for a homogeneous catalyzed system is the sum of
rates of both the uncatalyzed and catalyzed reactions:
 with corresponding reaction rates
 This means that the reaction would proceed even without a catalyst present and
that the rate of the catalyzed reaction is directly proportional to the catalyst
concentration.
Homogeneous Catalyzed Reactions
 The overall rate of disappearance of reactant A is
then:
(39)
 On integration, noting that the catalyst

concentration remains unchanged, we have:
(40)
 Making a series of runs with different catalyst
concentrations allows us to find k1 and k2.
 This is done by plotting the observed k value Fig. 2: Rate constants for a homogeneous
against the catalyst concentrations as shown in catalyzed reaction from a series of runs with
different catalyst concentrations.
Fig.2.
 The slope of such a plot is k2 and the intercept k1.
Autocatalytic Reactions
 A reaction in which one of the products of reaction acts as a catalyst is called an
autocatalytic reaction. (41a)
 The simplest such reaction is:
 for which the rate equation is (41b)
 Because the total number of moles of A and R remain unchanged as A is

consumed, we may write that at any time
 Thus, the rate equation becomes
 Rearranging and breaking into partial fractions, we obtain

Autocatalytic Reactions
 which on integration gives
(42)
 In terms of initial reactant ratio M = CRo/Cao and fractional conversion of A, this can
be written as
(43)
 For an autocatalytic reaction in a batch reactor some product R must be present if

the reaction is to proceed at all.
 Starting with a very small concentration of R, we see qualitatively that the rate will
rise as R is formed.
Irreversible Reactions in Series
 We first consider consecutive unimolecular type first-order reactions such as
 whose rate equations for the three components are:
(44)
(45)
(46)
 Let us start with a concentration CA0 of A, no R or S present, and see how the
concentrations of the components change with time.
 By integration of Eq. 44 we find the concentration of A to be
(47)
 To find the changing concentration of R, substitute the concentration of A from Eq.
47 into the differential equation governing the rate of change of R, Eq. 45; thus:
(48)
 which is a first-order linear differential equation of the form

 By multiplying through with the integrating factor the solution is
 Applying this general procedure to the integration of Eq. 48, we find that the
integrating factor is .
 The constant of integration is found to be –k1CA0/(k2-k1) from the initial conditions
CR0 = 0 at t = 0, and the final expression for the changing concentration of R is
(49)
 Noting that there is no change in
total number of moles, the
stoichiometry relates the
concentrations of reacting
components by
 which with Eqs. 47 and 49 gives
(50)
 Thus, we have found how the
concentrations of components A, R,
and S vary with time. Fig. 3: Typical concentration-time curves
for consecutive first-order reactions
Thank You
15

Integral Method of Analysis of Data

Uploaded by

Copyright:

Available Formats

Integral Method of Analysis of Data

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Integral Method of Analysis of Data

Uploaded by

Copyright:

Available Formats

Fair Use Notice

The material used in this presentation i.e., pictures/graphs/text, etc. is solely

Dr. Imran Nazir Unar

 The rates of change of the three components are given by

 For these in general, if it is necessary to write N stoichiometric equations to

 Then, from the stoichiometry, noting that CA + CR + Cs is constant, we can find

 When plotted as in Fig. 1, the slope is k1 + k2.

 Then dividing Eq. 35 by Eq. 36 we obtain the following (Fig. 3.6).

 which when integrated gives simply • This result is shown in Fig.1.

 with corresponding reaction rates

 On integration, noting that the catalyst

 The simplest such reaction is:

 for which the rate equation is (41b)

 Because the total number of moles of A and R remain unchanged as A is

 Rearranging and breaking into partial fractions, we obtain

 For an autocatalytic reaction in a batch reactor some product R must be present if

 whose rate equations for the three components are:

 which is a first-order linear differential equation of the form

 which with Eqs. 47 and 49 gives

You might also like