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Analysing Batch Reactor Data

This document discusses various methods for analyzing batch reactor data to determine the rate law and rate constant of a reaction. The main methods discussed are: 1) The differential method, which involves plotting the natural log of the derivative of concentration over time versus the natural log of concentration to obtain the reaction order and rate constant from the slope and intercept of the resulting straight line. 2) Integral methods, which involve integrating the rate law and plotting experimental data to determine if it fits the predicted linear relationship to obtain the reaction order and rate constant. 3) The method of initial rates, which determines rates at different initial concentrations and plots them versus concentration to obtain order and rate constant. 4) The method of half

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140 views3 pages

Analysing Batch Reactor Data

This document discusses various methods for analyzing batch reactor data to determine the rate law and rate constant of a reaction. The main methods discussed are: 1) The differential method, which involves plotting the natural log of the derivative of concentration over time versus the natural log of concentration to obtain the reaction order and rate constant from the slope and intercept of the resulting straight line. 2) Integral methods, which involve integrating the rate law and plotting experimental data to determine if it fits the predicted linear relationship to obtain the reaction order and rate constant. 3) The method of initial rates, which determines rates at different initial concentrations and plots them versus concentration to obtain order and rate constant. 4) The method of half

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utpalmtbi
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Analysing Batch Reactor Data

* One of the purposes for which batch reactors are used is rate law determination.
* Concentration (or any other convenient variable) measured as a function of time is the data typically available
* several methods are available for this analysis - differential, integral, initial rate, half life, etc.
Differential Method
* data is available as CA vs. t (where A is a reactant)
* for constant volume batch reactor with nth order reaction we can write
dCA
kCAn or
dt
A
ln dC
lnk nlnCA
dt
A
* Thus if we can plot ln dC
vs. lnCA from the data, we will get a straight line whose slope gives the order of the
dt
reaction and whose intercept gives the logarithm of the rate constant.
A
* But how to get dC
dt given data of CA vs. time?
* several methods exist for this as well - numerical differentiation, graphical method, and polynomial fit method

  



Numerical Differentiation
* in this method, the derivative is evaluated using finite difference formulas CA i CA i 1
dCA
dt i
ti ti 1 , where i refers to the number of the data point.
* such formulas can be forward or backward difference
* a three-point differentiation formula in general will give more accurate results than the above:

  
  

 


* the data should have been collected in equal time intervals


dCA
dt 0
dCA
dt 1
dCA
dt 2

3CA0 4CA1 CA2


2t
CA2 CA0
2t
CA0 4CA1 3CA2
2t

Graphical Method
* in this method, a smooth curve is drawn through the experimental data points on a C A vs. t graph.
* at each time instant of interest, tangents are drawn to this curve, the slope of the tangent line is the derivative value at
that time instant
* this method is attractive since we have a lot of control over the quality of results, and no assumptions regarding
uniformity of sampling time intervals, etc. are required.
* but it can be tedious, specially for large data sets or many experiments.
Polynomial Fit Method
* a polynomial of suitable order has to be fitted to the data
* the derivative can be then evaluated by differentiating the polynomial expression
* extreme care is necessary to make sure the fit is sensible - in general the best lower order polynomial that fits the data
reasonably should be chosen rather than a very high order polynomial that goes through all the data points
* a plot of the data and the fitted polynomial curve can be an important visual tool to ascertain that we doing the sensible
thing
Differential Method, non-constant volume batch reactor
* similar analysis is possible for non-constant volume batch reactor
* lets say that V (total volume) is the measured variable
A
kCAn V
* balance equation is written as dN
dt
dV
* this can be written in terms of volume as V yNA0
kCAn
A0V0 dt

  X


* since NA NA0 1
* furthermore,

CA
* thus

  

 y  1 V  V 
 y  1 V  V 
N  


1 X 
N
C
V
y V V
y V
  y  1 V  V 
C dlnV

k C
y
dt
y V

ln dlnV lnk  ln   C   nln   y  1 V  1
V 
dt 
y   
NA0 1

V V0
yA0 V0

A0

A0

A0

A0

A0 0

A0

A0

A0

* or

A0

A0

A0

A0

n 1
A0
n 1
A0

A0

* and thus a straight line plot can be obtained to get the order or reaction from V vs. t data

Integral Method
* an order of reaction has to be assumed
* then the batch reactor equation is integrated with the rate law of assumed order
* the quantities are bunched together in such a manner as to get a linear equation
* plot the data for this line
* the assumed order is correct if the data actually fall on this line, if not, another trial is required
* the slope and intercept of this straight line should give the rate constant value
Example:
* It can be shown that for first order reactions (Constant Volume Batch Reactor),
ln CA0 kt so, ln CA has to be plotted vs. time
ln CA
* For second order reactions,
1
1
kt so C1A has to be plotted vs. time, to get k
CA
CA0
1 n
* n-th order reaction (n 1): CA1 n CA0
k n 1 t so plot CA1 n vs. t to get k



  

 


* rate laws of even more complex nature can be used in this method
* however the assumption of order that has to be made a-priori makes integral method inconvenient at times
* judging whether the data actually fall on the prescribed line also tends to be an art, specially if the available data points
are not very numerous
Method of Initial Rates
* the reactor is operated using different initial concentrations.
* from the initial slope of the concentration vs. time data, the rates corresponding to these initial concentrations are
obtained.
* plotting ln rate vs. ln CA0 will give the order and the rate constant, just like in the differential method
* the big disadvantage of this method is that lot of experiments are required

Method of Excess
* this method is for rate laws having dependence on concentration of more than 1 species
* the concentration of all but 1 species is kept constant
* the order of reaction wrt the 1 species is determined by usual methods (perhaps the method of initial rates?)
* in some sense method of excess is a sub-method - a variation of the differential or integral or other methods, for a
special situation
Method of half-lives
2

* half-life is the time taken for the concentration of a reactant to fall to one-half its original value
* it is just the same half-life we have studied when we dealt with radioactivity
* the half-life is the measured variable in this method, typically as a function of the initial concentration

     
C  2






* thus t 
0  5
1





* if we have a set of data of half-life vs. the initial concentration, to get k and n, we have to plot ln t   vs. ln C  , the
slope will be 1  n. k can be obtained from the intercept
Example:
1 n
* consider CA1 n CA0
k n 1 t (nth order reaction, n is not 1)
* half-life is the time for the concentration to fall to half it original value, or time at which C A
1 2

1 n
CA0
k n 1

A0

1 n

1 2

A0

* note that for first order reactions the half-life is independent of the initial concentration, so one experiment at any
arbitrary initial concentraction can give the rate constant
* many experiments are necessary here also, and waiting to get to half-life may be expensive
* a fractional life method may easily be used, performing all calculations and experiments to the time when the concentration is something like 10% of the initial concentration

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