ChE 4127

Interpretation of Batch
Reactor Data

Instructor:
Shuvashish Mondal
Lecturer,
Department of Chemical Engineering, KUET
Khulna-9203
The determination of the rate equation is usually a two-step procedure;
1. first the concentration dependency is found at fixed temperature and
2. then the temperature dependence of the rate constants is found

Equipment by which empirical information is obtained can be divided into

two types-
― batch reactor
▪ Usually homogeneous kinetic data
― flow reactor
▪ Usually heterogeneous kinetic data

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Determination of Extent of Reaction:
1. By following the concentration of a given component.
2. By following the change in some physical property of the fluid, such as
the electrical conductivity or refractive index.
3. By following the change in total pressure of a constant-volume system
4. By following the change in volume of a constant-pressure system.

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There are two procedures for analyzing kinetic data-
1. Integral method: In the integral method of analysis, we guess a
particular form of rate equation and, after appropriate integration and
mathematical manipulation, predict that the plot of a certain
concentration function versus time should yield a straight line. The data
are plotted, and if a reasonably good straight line is obtained, then the
rate equation is said to satisfactorily fit the data.
2. Differential method: In the differential method of analysis we test the fit
of the rate expression to the data directly and without any integration.
However, since the rate expression is a differential equation, we must
first find (l/V)(dN/dt)from the data before attempting the fitting
procedure.

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 CONSTANT-VOLUME BATCH REACTOR

Conversion

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 Integral Method of Analysis of Data
Procedure
• Test a particular rate equation 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.

The integral method is especially useful for fitting simple reaction types
corresponding to elementary reactions.

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1. Irreversible Unimolecular-Type First-Order Reactions

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2. Irreversible Bimolecular-Type Second-Order Reactions

CA = CA0 – CA0XA

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• If CB0 >> CA0, then CB = CB0 – CB0XA ≈ CB0

k’t

k’

Pseudo first-order reaction

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3. Irreversible Trimolecular-Type Third-Order Reactions

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Now, if the stoichiometry is

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4. Empirical Rate Equations of nth Order

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Overall Order of Irreversible Reactions from the Half-Life t1/2

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Overall Order of Irreversible Reactions from the Half-Life t1/2

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Fractional Life Method tF

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Irreversible Reactions in Parallel

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Irreversible Reactions in Parallel

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Homogeneous Catalyzed Reactions

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Autocatalytic Reactions

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Irreversible Reactions in Series

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in general, for any number of reactions in series, it is the slowest step that has the greatest
influence on the overall reaction rate.

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• The time at which the maximum concentration of R occurs

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First-Order Reversible Reactions

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Second-Order Reversible Reactions

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Reactions of Shifting Order

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• Find the integral forms of-

Do it yourselves!!!!!

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Find A Rate Equation Using The Integral Method

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SOLUTION
1. Guess First-Order Kinetics:

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2. Guess Second-Order Kinetics:

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3. Guess nth-Order Kinetics:

• Let’s take F = 80%, then the above equation becomes

• Taking logarithms

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 Differential Method of Analysis of Data
1. Plot the CA vs. t data, and then by eye carefully draw a smooth curve to
represent the data. This curve most likely will not pass through all the
experimental points

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2. Determine the slope of this curve at suitably selected concentration
values. These slopes dCA/dt = rA, are the rates of reaction at these
compositions

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3. Now search for a rate expression to represent this rA vs. CA data, either
by-
a. picking and testing a particular rate form, -rA = kf (CA),
b. testing an nth-order form -rA = k𝐶𝐴𝑛 by taking logarithms of the rate
equation

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 Other way of finding dCA/dt
1. Numerical Method
• Numerical differentiation formulas can be used when the data points in the
independent variable are equally spaced
2. Equal Area Graphical Differentiation

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Find A Rate Equation Using The Differential Method

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• Step 1: Plot CA vs. t

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• Step 2: Now carefully draw a smooth curve to represent the data, and at
CA= 10, 8, 6, 5, 3, 2, 1 draw tangents to the curve, and evaluate them

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• Step 3: Take logarithms of the rate expression calculate their values

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• Step 4: Calculate the slope and intercept of the best line which gives n
and k

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Problem: Determining the rate law

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Solution: Part (1)- Find the reaction order with respect to trityl
Step 1: Postulate a rate law.

Step 2: Process your data in terms of the measured variable, which in this
case is CA.
Step 3 Look for simplifications.
• Because the concentration of methanol is 10 times the initial concentration of triphenyl methyl
chloride, its concentration is essentially constant

• Substituting for CB in Equation (E7-2.1)

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Solution: Part (1)- Find the reaction order with respect to trityl
Step 4: Apply the CRE algorithm.

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Solution: Part (1)- Find the reaction order with respect to trityl
Step 4: Apply the CRE algorithm (cont’d).

Step 5: Find [─dCA/dt] as a function of CA from concentration–time data.

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Step 5A: Graphical Method.

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Step 5A: Graphical Method (cont’d).

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Step 5A: Graphical Method (cont’d).

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Step 5A: Graphical Method (cont’d).

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Step 5B: Finite Difference Method.

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Step 5B: Finite Difference Method (cont’d).

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Step 5B : Finite Difference Method (cont’d).

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Step 6: Logarithmic plot of –dCA/dt vs. CA
Finding order:
Slope = 1.99 ≈ 2 → second order reaction

Finding rate constant, k’

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Solution: Part (2) The reaction was said to be first order with respect
to methanol, β = 1

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