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Reactor Lec 4

The lecture discusses the experimental determination of rate equations in reactor engineering, emphasizing the importance of both concentration and temperature dependencies. It outlines the types of reactors used for data collection, including batch and flow reactors, and details methods for monitoring reactions and analyzing kinetic data. The integral and differential methods for kinetic data analysis are compared, highlighting their respective advantages and disadvantages.

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6 views28 pages

Reactor Lec 4

The lecture discusses the experimental determination of rate equations in reactor engineering, emphasizing the importance of both concentration and temperature dependencies. It outlines the types of reactors used for data collection, including batch and flow reactors, and details methods for monitoring reactions and analyzing kinetic data. The integral and differential methods for kinetic data analysis are compared, highlighting their respective advantages and disadvantages.

Uploaded by

ibtihal esam
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Lecture 4

ChE41102
Reactor Engineering I
Dr. Mustafa Abbas Mustafa
Email: mamustafa@UofK.edu
The value of the constants for the rate

equation can only be found experimentally.

Predictive methods are inadequate at present.


Procedure for Determining Rate
Equation
This is usually a 2 step procedure
• Concentration dependency is found at fixed
temperature.
• And then the temperature dependence of the
rate constants is found, yielding the complete
rate equation.
Types of Equipment Used for Data
Collection
• Batch reactor
– Experiment usually operated isothermally and at constant
volume, since it is easy to interpret the results.
– Is used whenever possible for obtaining homogenous kinetic
data.
• Flow reactor
– Used primarily in the study of kinetics of heterogeneous
reactions.
– Reactions which are difficult to follow, reactions which yield
a variety of products, very rapid reactions, and gas-phase
reactions are examples of cases which are more easily
followed in flow reactors.
Batch Reactors: Monitoring Extent of
Reaction
This can be achieved through a number of ways:
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 (Constant-Volume batch reactor).
4. By following the change in volume of a constant-pressure
system (Variable-Volume batch reactor).
Kinetic Data Analysis
There are 2 procedures for analysis
• Integral Method
Here we guess a particular form of rate equation, and after
integrating, we predict that the plot of a certain concentration
function versus time should yield a straight line.
• Differential Method
The fit of the rate expression to the data is tested directly.
However, since the rate expression is a differential equation,
one must first find (1/V)(dN/dt) from the data.
Pros and Cons of both Methods
Integral Method Differential Method

Pros Pros
 Easy to use  Useful in complicated situation
 Can be used to develop or build
up a rate equation to the data
Cons
Cons
 Can only be used to test
 Requires lots of accurate or
one or another particular
mechanism or rate form larger amounts of data
Constant-Volume Batch Reactor
An assumption of constant density is usually acceptable for liquids
and for gas reactions in which there is no change in the total
number of moles on either side of the stoichiometric equation.

Thus rate is function of concentration or partial pressure.


Analysis of Total Pressure Data Obtained
in a Constant-Volume System
Please note: Moles of A reacting with B to give R and S is related by ax, bx, rx, sx.
One part is variable (x) and the other fixed and is linked to the stoichiometry (a, b, r, s).
e.g. x=1 --- a mole + b mole + Inert  r mole + s mole + Inert
x=2--- 2a mole + 2b mole + Inert  2r mole + 2s mole + Inert
Thus moles reacted/produced are a function of
stoichiometric coefficients a, b, r, s, etc

Therefore total number of moles at time (N) = NA+NB+NR+NS+…


Substitute values of NA+… to get
Analysis of Total Pressure Data Obtained in a Constant-
Volume System

Or x= (N-N0)/n

Levenspiel
Analysis of Total Pressure Data Obtained in a Constant-
Volume System
Remember
x= (N-N0)/n

Levenspiel
Please note
The previous “total pressure” procedure can not
be used if
• The precise stoichiometry is not known.
• Or if more than one stoichiometric equation is
needed to represent the reaction (i.e. non-
elementary).
Conversion
Given an initial amount of A equal to NAO at time t=0,
the conversion for A is defined (at a constant volume)
as follows
Integral Method of Analysis of Data
General Procedure
The integral method of analysis tests a particular
rate equation by integrating and comparing the
predicted Concentration Vs Time curve with the
experimental data.
Integral Method
• A trial-and-error procedure to find reaction order.
• Guess the reaction order Integrate the differential
equation.
• Look for the appropriate function of concentration
corresponding to a particular rate law that is linear with
time.
For the reaction A  products
dC A
For a zero-order reaction - rA = k  k
dt
CA

C A C A0  kt
t
dC A
For a first-order reaction - r A = k CA  kC A
dt
ln (CA0/CA)

C A0
ln kt
t CA
dC A 2
For a second-order reaction - rA = k CA 2
 kC A
dt
1/CA

1 1
 kt
t C A C A0
Empirical Rate Equations of nth order

1 n 1 n
C A
 C A0
(n  1)kt , n 1
What is the relationship in terms of
conversion (X) for a second order
reaction?
dC A 2
For a second-order reaction - rA = k CA 2
 kC A
dt
1/CA

1 1
 kt
t C A C A0

Solution Remember CA=CA0(1-X)

For a second-order reaction - rA = k CA2


Integral Method Example
Gas-phase decomposition of di-tert-butyl peroxide:
O
||
(CH3)3COOC(CH3)3  C2H6 + 2CH3CCH3

A  B + 2C

Please notice that as the reaction progresses, the total pressure increases
since 1 mole decomposes to give 3 moles of product
At t=0, pA0=0
substitute  =P and
EQ 1 0 = pA0=P0 pA=k1(3P0-P)

Note: Capital P for total pressure


dP For  = 1
and small p for partial pressure
k (3P0  P ) & dpA= - k3dP (Equation 1)
1 dp A
r A RT dt k 2 p A 
dt

Integral
method

2 P0
ln( ) k t ln [2P0/(3P0-P)]
3P0  P Assumption
is correct

t
Irreversible bimolecular 2nd order
reaction
A + B  Products

Where M = CB0/CA0
Levenspiel
Caution
1. If M = 1, the equation becomes similar to a
second order reaction in A

2AProducts
Home work:
Examine the following reactions
• Reversible 1st order
• Reversible 2nd order
• Reactions of shifting order
• Autocatalytic
• Irreversible reactions in parallel
• Irreversible reactions in series
• Homogeneous catalyzed reactions

Please note that you have to cover the derivation of up to 2 nd order reversible reactions.
Questions

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