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Interpretation of Batch Reactor Data: Conversion

The document discusses various methods for analyzing batch reactor data through integral analysis of rate equations. It describes determining conversion for reactions and obtaining linear plots to test rate equations. Rate laws for irreversible first and second order, as well as empirical nth order, zero order, parallel, series, and autocatalytic reactions are analyzed through integration. Determining reaction constants and the influence of sequential reaction steps is also addressed.

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erickhadinata
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172 views

Interpretation of Batch Reactor Data: Conversion

The document discusses various methods for analyzing batch reactor data through integral analysis of rate equations. It describes determining conversion for reactions and obtaining linear plots to test rate equations. Rate laws for irreversible first and second order, as well as empirical nth order, zero order, parallel, series, and autocatalytic reactions are analyzed through integration. Determining reaction constants and the influence of sequential reaction steps is also addressed.

Uploaded by

erickhadinata
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Interpretation of Batch Reactor Data

Conversion
• Conversion of A, XA, is the fraction of reactant A
converted to other compounds
• Suppose NAo is the initial amount of A in a reactor at time
t=0
• NA is the amount present at time t
• Then conversion of A in the constant volume system is
given by

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Integral Method of Analysis
• Integral method of analysis puts a particular rate
equation to test by integrating and comparing the
predicted C vs t curve with experimental data
• If the fit is unsatisfactory, another rate equation is
guessed and tested
• Irreversible Unimolecular-Type First-Order Reactions

• Suppose we wish to test the first-order rate equation

• Separating and integrating, we obtain

2
• In terms of conversion,

• On rearranging and integrating,

• A plot of ln(1 – XA) or ln(CA/CAo) vs t gives a straight line through the


origin for this form of rate 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

3
Irreversible Bimolecular-type Second-Order Reactions
• Consider the reaction

• The corresponding rate equation is

• The amounts of A and B that have reacted at any time t


are equal and given by CAoXA

• Letting M = CBo/CAo be the initial molar ratio of reactants

4
• On separation and integration,

• After breakdown into partial fractions, integration and


rearrangement, the final result in a number of different forms is

• Two equivalent ways of obtaining a linear plot between


concentration and time for this second-order rate law

5
• For second-order reaction with equal initial
concentrations of A and B or for the reaction

• The defining second-order differential equation becomes

• Which on integration yields

6
• For trimolecular reactions,

• In terms of conversion, the rate of reaction becomes

• Where M = CBo/CAo. On integration,

• Similarly, for the reaction


• Integration gives

7
Empirical Rate Equations of nth Order
• When the mechanism of reaction is not known, we often
attempt to fit the data with an nth-order rate equation

• Which on separation and integration yields

• The order n cannot be found explicitly, so a trial-and-


error solution must be made
• Select a value for n and calculate k, the value of n which
minimizes the variation in k is the desired value of n

8
Zero Order Reactions
• A reaction is zero order when the rate of reaction is
independent of the concentration of materials

• Integrating and noting that CA can never become


negative,

9
Irreversible Reactions in Parallel
• Consider A decomposing by two competing paths, both
elementary reactions

• The rates of change of the three components are

• The k values are found using all three differential rate


equations

10
• Dividing the second and third equations,

• When integrated,

• The slope of a plot of CR vs CS gives the ratio k1/k2


• Knowing k1/k2 as well as k1 + k2 gives k1 and k2

11
Autocatalytic Reactions
• An autocatalytic reaction is a reaction in which one of the products
of reaction acts as a catalyst

• The rate equation is

• Because the total number of moles of A and R remains unchanged


as A is consumed,

• Thus, the rate equation becomes

• Rearranging and breaking into partial fractions,

• On integration,
12
• In terms of initial reactant ratio M = CRo/CAo and fractional
conversion of A,

• 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, the rate will rise as R is
formed
• When A is almost totally consumed, the rate must drop to zero
• Thus, the rate follows a parabola with a maximum where the
concentrations of A and R are equal

13
Irreversible Reactions in Series
• Consider consecutive unimolecular-type first-order reactions

• The rate equations for the three components are

• By integration of the first equation, concentration of A is

• To find the changing concentration of R, substitute concentration of


A obtained into differential equation governing the rate of change of
R

14
• The final expression for the concentration of R is

• Noting that there is no change in total number of moles,


stoichiometry relates the concentrations of reacting components by

• Concentration of S is thus

• If k2 is much larger than k1,

• The rate is determined by k1 or the first step of the two-step reaction


• If k1 is much larger than k2,

• Which is a first-order reaction governed by k2, the slower step in the


two-step reaction
• In general, for any number of reactions in series, it is the slowest
step that has the greatest influence on the overall reaction rate
15
• k1 and k2 also govern the location and maximum concentration of R
• This may be found by setting dCR/dt = 0
• Time at which maximum concentration of R occurs is

• Maximum concentration of R is

• A decreases exponentially, R rises to a maximum and then falls, S


rises continuously
• The greatest rate of increase of S occurs where R is a maximum

16
Tutorial Questions
• Levenspiel book: 3.5, 3.9, 3.19, 3.23

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