CH3

Interpretation of Batch Reactor Data

• A rate equation characterizes the rate of reaction, and its form may either be
suggested by theoretical considerations or simply be the result of an empirical
curve-fitting procedure.
• All that has to be determined is the extent of reaction at various times, and this
can be followed in a number of ways,
• 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.

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 Cont..
• two procedures for analyzing kinetic data
1. integral method- 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.
2. differential method- test the fit of the rate expression to the data directly and
without any integration.

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 Constant-volume Batch Reactor
• referring to the volume of reaction mixture, and not the volume of reactor.
• means a constant-density reaction system

or for ideal gases, where C = p / RT

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Analysis of Total Pressure Data Obtained in a
Constant-Volume System

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Cont..

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 Integral Method of Analysis of Data
• 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 expression is guessed and tasted
1. Irreversible unimolecular (1st order rxn)

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 Cont..
2. Irreversible bimolecular (2nd order rxn)

Letting M = CBo/CAo

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 Cont..
• for the second-order reaction with equal initial concentrations of A and B, or for
the reaction - If the rxn,

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 Cont..
3. Irreversible Trimolecular-Type Third-Order Reactions

- On separation of variables, breakdown into partial fractions, and integration,

we obtain after manipulation

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 Cont..
• For a rxn;

• where M = CBo/CAo. On integration this give

Or
• For the rxn;

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 Empirical Rate Equations of nth Order

• reactions with order n > 1 can never go to completion in finite time.

• for orders n < 1this rate form predicts that the reactant concentration will fall to
zero and then become negative at some finite time
• Zero-Order Reactions- a reaction is of zero order when the rate of reaction is
independent of the concentration of materials;

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 Overall Order of Irreversible Reactions
from the Half-Life t1/2
• half-life of the reaction- the time needed for the concentration of reactants to drop
to one-half the original value,

• for reactants A and B at any time CB/CA= α/β

• Integrating for n≠1 gives

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 Fractional Life Method tF
• The concentration of reactant drops to any fractional value F = CA/Cao in time tF.

• Irreversible Reactions in Parallel- Consider the simplest case, A decomposing

by two competing paths, both elementary reactions:

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 Autocatalytic Reactions
• A reaction in which one of the products of reaction acts as a catalyst is called an
autocatalytic reaction.

• the total number of moles of A and R remain unchanged as A is consumed

• integration gives;
M= CRo/CAo

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 Irreversible Reactions in Series
• Consider consecutive unimolecular type first-order reactions such as
whose rate equations for the three components are

, which is a first-order linear differential

equation of the form
By multiplying through with the integrating factor the solution is

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 Cont..
• substituting the value of C

• The constant integration is found from

initial conditions, CRo=0 @ t=0

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 Cont..

• maximum concentration of R
setting dCR/dt = 0
• The time at which the maximum
concentration of R occurs is thus

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 First-Order Reversible Reactions
• Consider a reaction;

• , M= CRo/CAo

at equilibrium dCA/dt = 0, & XA=XAe ;

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 Second-Order Reversible Reactions
• For the bimolecular-type second-order reactions

with the restrictions that CAo= CBo, and CRo= Cso = 0,

the integrated rate equations for A and B are all identical,
as follow

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 Reactions of Shifting Order
• In searching for a kinetic equation it may be found that the data are well fitted by
one reaction order at high concentrations but by another order at low
concentrations.
Consider the reaction;

• To apply the integral method, separate variables and integrate

, linearize to give

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 Differential Method
• deals directly with the differential rate equation to be tested, evaluating all terms
in the equation including the derivative dC/dt, and testing the goodness of fit of
the equation with experiment.

• Three methods to determine the derivative dCA/dt from data giving the
concentration as a function of time
1. graphical differentiation
2. numerical differentiation
3. differentiation of a polynomial fit to the data
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 Graphical differentiation
• To find dy/dx- use equal area graphical differentiation. ( look at Fogler Example
7.2)

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 Numerical Differentiation
• Numerical differentiation formulas can be used when the data points in the
independent variable are equally spaced, such as
( look at Fogler Example 7.2)

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 Varying-volume Batch Reactor
V0 = initial volume of the reactor
V = the volume at time t
• for isothermal constant pressure operations

where ,is the fractional change in volume of the system between no conversion
and complete conversion of reactant A.

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 Cont..
• The rate of reaction (disappearance of component A), is, in general

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 Differential Method
• he procedure for differential analysis of isothermal varying volume data is the
same as for the constant-volume situation except that we replace

• This means plot In V vs. t and take slopes.

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 Integral Method of Analysis
• Zero-Order Reactions

• First-Order Reactions

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 Cont..
• Second-Order Reactions; For a bimolecular-type second-order reaction,

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