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