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Zaineb - Chapter5 2223006

The document discusses methods for collecting and analyzing rate data from chemical reactions, focusing on batch and differential reactors. It details various analytical techniques such as the method of excess, differential and integral methods, nonlinear regression, and initial and half-life methods to determine reaction orders and rate constants. Examples illustrate the application of these methods in determining reaction kinetics for specific chemical reactions.

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7 views19 pages

Zaineb - Chapter5 2223006

The document discusses methods for collecting and analyzing rate data from chemical reactions, focusing on batch and differential reactors. It details various analytical techniques such as the method of excess, differential and integral methods, nonlinear regression, and initial and half-life methods to determine reaction orders and rate constants. Examples illustrate the application of these methods in determining reaction kinetics for specific chemical reactions.

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زينب فرج
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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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COLLECTION AND ANALYSIS OF RATE

DATA
Zaineb Farag Abdallah

Dr. Hadi Elaktami

2024
Types of Reactors for obtaining Rate Date
■ Batch Reactor Date Analysis is to collect concentration time data, which we then use
to determine the rate law, the homogeneous reactions is most often obtained in a batch
reactor. The rate law is combined with mole balance.

We next use any methods to process the data and arrive at the reaction orders and
specific reaction rate constants
( power law model ) , (mole balance)

■ Differential Reactor Date Analysis (Analysis for PBR) of heterogeneous reactions is


For gas-solid heterogeneous reactions, the differential reactor are made during steady-
state operation.
(Hinshelwood model) , mole balance on Product P (A P)
Batch Reactor (methods for analyzing rate date)
■ Method of excess for irreversible reaction (A+B P)
the rate law is
CB, remains essentially unchanged during the course of the reaction and the rate
law becomes
,(reaction is carried out in an excess of A).
which the rate law is approximated as

■ Differential Method of Analysis


■ Integral Method
■ Nonlinear Regression
■ Initial rate Method
■ Half -lives Method
Differential Method of Analysis
■ we consider a reaction carried out isothermally in a constant-volume batch reactor and
the concentration recorded as a function of time. By combining [the mole balance with
the rate law and taking the natural logarithm of both sides we get:

the slope of a plot of as a function of is the reaction order(

These methods are:


■ Graphical differentiation
■ Numerical differentiation formulas concentration-time data
■ Differentiation of a polynomial fit to the data
Example(Differential Method)
The reaction of triphenyl methyl chloride (trityl) (A) and methanol (B) was carried out in a
solution of benzene and pyridine at 25°C

The initial concentration of methanol was 0.5 mol/dm3


A. Determine the reaction order with respect to triphenyl methyl chloride.
B. In a separate set of experiments, the reaction order methanol found to be first order.
Determine the specific reaction rate constant
Example(Differential Method)
By using execs method (combine: mole balance, rate law) we get equation 1,
than plot as a function of to get the slop(), now we need to find :
Graphical Method
Example(Differential Method)
Finite Difference Method:
We now calculate using the finite difference formula

Polynomial Method Here we first choose the polynomial degree (in this case, fourth
degree)
Example(Differential Method)

A) Slop =2.06 and


B) The reaction was said to be first order
Integral Method
The integral method uses a trial-and error procedure to find reaction order
It is important to know how to generate linear plots of functions of CA vs t for zero –first ,
and second –order reactions.

From Example 1 Use the integral method to confirm that the reaction is second order
(A)methyl chloride
EXAMPLE
A plot of (l/CA) versus t should be linear (date from table)

Slop =0.124 and k


(Integral method normally used to find k when order is known)
Nonlinear Regression
■ We want to find the parameter values (α, k) for which the sum of the squares of the
differences, the measured rate (), and the calculated rate () is a minimum.

■ That is we want to be a minimum


■ Where
N = number of runs
K = number of parameters to be determined
= measured reaction rate for run i
=calculated reaction rate for run i
Nonlinear Regression
■ combined rate law-stoichiometry-mole balance for a constant-volume batch reactor is

■ We now integrate, and than obtaining the concentration as a function of time

■ To find the values of and k that would minimize the sum of squares of the differences
between the measured and calculated concentrations
Nonlinear Regression
■ To solve for the parameter values is to use time rather than concentrations

■ From Example 1 using nonlinear regression by polymath :


Initial and half lives methods
■ The method of initial rate could be used to determine the reaction order and specific rate
constant here use the different initial concentration and initial rate of reaction for each
run .Then (converting rate per unit area ) plotting the slop is

■ The half-life of a reaction is defined as the time it takes for the concentration of the
reactant to fall to half of its initial value. By determining many experiment half-life of a
reaction as a function of the initial concentration. the reaction order and specific reaction
rate can be determined. if two reactants , involved in the chemical reaction, the
experimenter will use the method excess.
Differential Reactors Date Analysis
■ A differential reactor is normally used to determine the rate of reaction as a function of
either concentration or partial pressure.
■ It consists of a tube containing a very small amount used of catalyst, As a result, the
reactant concentration through the reactor is essentially constant and approximately qual
to the inlet concentration.
■ The reactor is considered to be gradientless (spatially uniform) and the reaction rate is
considered uniform within the bed.
■ The analysis is done on the product rather than the reactants:
■=
Differential Reactors (Example)
The formation of methane from carbon monoxide and hydrogen, was carried at 50OF in n
differential reactor where the effluent concentration methane was measured, Relate the rate
of reaction to the exit methane concentration.

Solution
Differential Reactors (Example)
The rate for runs 2 through 6 can be calculated in a similar manner

Now we determine the Rate Law Dependence in CO


For constant hydrogen concentration, the rate law
can be written as
We now plot )versus ln() for runs 1, 2, and 3
Differential Reactors (Example)
Determining the Rete Law Dependence on( )
(Hinshelwood model)
We now use the Polymath regression program to find the parameter values a, b, , 2
Reference

Elements of Chemical Reaction Engineering 4th , H. SCOTT FOGLER

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