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2. Reaction Engineering Lecture

reaction kinetics

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1 views

2. Reaction Engineering Lecture

reaction kinetics

Uploaded by

abdisa767
Copyright
© © All Rights Reserved
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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Chapter II

Methods of Analysis of
Rate Data
Collection And Analysis of Rate Data

Two techniques of data acquisition are presented: concentration-


time measurements in a batch reactor and concentration
measurements in a differential reactor.
Six different methods of analyzing the data collected are used:
 Differential method,
Integral method,
Method of half-lives,
Method of initial rates,
Linear and nonlinear regression (least-squares analysis)
Methods of analysis of rate data

Objective: Deal with techniques of obtaining and analyzing reaction rate data to
obtain the rate law for a specific reaction.
• Two types of reactors are considered in this chapter to apply the techniques to
obtain the rate data
– Batch reactor
• which primarily is used for homogeneous reactions
• The pressure, volume and concentration data are collected under
unsteady state condition
– Differential reactor
• which is used for solid-fluid reactions
• The data measurement is done under steady state condition
Methods of analysis…
Methods of data analysis
 Differential method Possible to carryout only one experiment to
 Integral method determine the specific rate and reaction order

It need multiple experiments at many different initial


 Initial rate method conditions to determine the reaction order and the
 Half life method specific reaction rate

Batch Reactor Data


– Used primarily to determine rate law parameters for homogeneous reactions
– This is achieved usually by measuring concentration as a function of time and then
use either the differential or integral method of data analysis using either
differential or integral method of data analysis to determine the reaction order
“α” and specific reaction rate constant, “k”
Methods of analysis…
Differential method of data analysis
Given the reaction is irreversible

“α” and “k” can be found by numerically differentiating Conc. Vs time data
There are two conditions to use the differential method
Condition 1 :
• This method is applicable if the reaction rate is a function of only one reactant

Condition 2:
By utilizing method of excess it is also possible to determine the relationship b/n and the conc. of other
reactants for irreversible reaction type of

with a rate law of

where α and β are both unknowns


First running the reaction in excess of “B” the rate equation will be reduced to
----------------------------- *
where,
After determining α, the reaction is carried out in an excess of A, for
determining β.
Then the reaction is run in excess of “A” where the reaction rate will be
reduced to
---------------------------- **
where,

From equation * and **, “α” and “β” can be determined using Numerical
or Graphical methods.
Combining the mole balance and the rate law is written as (refer previous classes)
---------------------- *1
Then taking the natural logarithm of both sides of equation *1
--------------*2

Then the slope of the plot of Vs is the reaction order “”


To plot this graph, the differential can be calculated using “Graphical technique or Finite
difference method or using computer programs (which develop equations of Vs t using
different mathematical techniques like application of series to approximate data in equation
form and then differentiate the approximation equation found at the given points analytically)
In here we will see
• Finite difference method
• Computer program approximation (using MS excel)
• Graphical technique refer ( H. Scott Fogler , 2004)
 Once “α” and “β” are determined, k, can be calculated from the
measurement of -rA at known concentration of A and B:
Finite Difference Method
• Finite difference method to solve has different approaches but for this class we can apply three-point
differentiation equation
• For a collected experimental data of concentration at different time intervals given by the following
format

Time
Concentration

Three – point differentiation equation


(used for the first data point)
(used for the all intermediate data points)
(used for the last data point)
• Then using these equations the final data table for equation “*2” is developed
as follows and the slope is determined.
Time
Concentration
Derivative

• Steps to follow in solving the rate equation using differential


method
1. Postulate a rate law
2. process your data in terms of the measured variable (re-write
the mole balance in terms of the measured variable)
3. Look for simplification
4. Calculate as a function of reactant conc. to determine the
reaction order
Example 5.1 : Differential method of analysis for Pressure- Time data
Integral Method
• To determine the reaction order by the integral method,
– We first guess the reaction order and integrate the differential equation used to
model the batch system
– If the order we assume is correct the appropriate plot (determined from this
integration) of the pressure- time data or concentration-time data should be linear.
• For a given reaction of

carried out in a constant-volume batch reactor the mole balance is given by


----------------------- **1

To solve for the reaction order we will look for the appropriate function of conc.
corresponding to a particular rate law that is linear with time.
Zero-Order rxn (with the rate equation of )
Integrating equation “**1”

The plot of “” Vs “” must be linear with a slop “–k”


First-Order rxn (with the rate equation of )
Integrating equation “**1”

The plot of “” Vs “” must be linear with a slop “k”

Linear line
Second-Order rxn

Linear line

Linear line

𝑨+ 𝑩→ 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔
Eq. 14

Example 5.2 Integral method of analysis of Pressure-Time data


Use the integral method to confirm that the reaction order for the
di-tert-butyl peroxide decomposition described in example 5.1 is
first order.
Eq. 16
Methods of Initial Rates
.

- Differential and integral techniques are easier since they require only one
experiment but occurrence of reverse reaction render the technique
ineffective.

- In this case the initial rate technique can be used as a solution.

- A series of experiments are carried out at different initial concentrations “CA0“


and the initial rate of reaction “–rA0 “ can be determined for each run. After
determining “–rA0 “ for each “CA0“ then using the rate law of the form

The slope of the plot of ln (–rA0 ) Vs ln(CA0 ) will give the reaction order α
- equation 5.6
Methods of Half-lives
• The half life of a rxn, t1/2, is defined as the time it takes for the concentration
of the reactant to fall to half of its initial value.
• By determining the half-life of a rxn as a function of the concentration the
reaction order and specific reaction rate can be determined.
• For an irreversible reaction

A→ Product and a rate law of


-
• Integrating with the initial condition at t= 0

At t= t ½ CA= ½ CA0 , Substituting this

Talking the natural log of both sides

• Then (1-α) will be the slope of the straight line and the order can be easily determined
• **** Reading assignment Least square technique
Article Presentation Assignment
• Find any scientific article related to Reaction Engineering concept
and prepare a presentation for 15 minutes.

• Submit both the article and your prepared ppt before the
presentation deadline.
 Prepared power point submission , Thursday 28 Nov, 2024
 Presentation , Monday 02 December, 2024
• Total mark 20%

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