Previous and Todays lecture

Rate law from batch reactor

Differential Method
Integral Method
Initial rate method
Half-lives method
Linear regression
Non-linear regression

Rate law from differential reactor

Brief description of other reactor types

employed for kinetics study
 Typical Experimental Data Available from
Batch Reactor Experiments

Time (min) t0 t1 t2 t3 t4 t5

Concentration (mol/L) CA0 CA1 CA2 CA3 CA4 CA5

OR

Time (min) t0 t1 t2 t3 t4 t5

Pressure (kPa) PT0 PT1 PT2 PT3 PT4 PT5

Collection and analysis of rate data
Batch reactor
for homogenous reactions
measurement during the unsteady-state
operation
Differential reactor
for solid-fluid reactions
measurement during steady state operation
product concentration is usually monitored
for different feed conditions.
Analysing methods
Differential method Batch reactors
Integral method
Initial rate method
Half-lives method
Differential reactor
Linear regression
Non-linear regression
 Least-squares analysis
If a rate law depends on the
concentration of more than one species
and it is not possible to use the method
of excess, we may choose to use a
linearized least-squares method.

Assuming a Find the linear

Run N
form of the least-squares
experiments
rate law solution
 Least-squares analysis example
The etching of semiconductors in the manufacture of computer chips is an
important solid-liquid dissolution reaction. The dissolution of the
semiconductor MnO2 was studied using a number of different acids and
salts.

The rate of dissolution was found to be a function of the reacting liquid

solution redox potential rate could be increased by a factor of 105 simply by
changing the anion of the acid.

From the data below, determine the reaction order and specific reaction
rate for the dissolution of MnO2 in HBr.

CA0 (mol HBr/dm3) 0.1 0.5 1.0 2.0 4.0

-rA0 (mol HBr/m2 h) x 102 0.073 0.70 1.84 4.86 12.84
We assume a rate law of the form r
HBr kC HBr
A = HBr Taking the ln of the both sides and
using the initial rate and concentration

ln(rA0 ) ln k ln C A0

Y a bX

Substituting the experimental data in the the equation and find the least squares
equation

0.0184C1.4 HBr
rHBr
Analysing methods
Differential method Batch reactors
Integral method
Initial rate method
Half-lives method
Differential reactor
Linear regression
Non-linear regression
Nonlinear least-squares analysis
In nonlinear least squares analysis we
search for those parameter values and
the calculated values for all the data
points.
Many software programs are available to
find these parameter values and all one
has to do is to enter the data.
 Nonlinear regression (read Fogler 5.2.3 P271-277)

N N
s (CAmi CAci ) CAmi C (1 )kti
2 2 1 1/(1 )
A0
i1 i1

or
2
N N
C1
C1
s2 (t Ami t Aci ) 2 t Ami A 0 Ai

i1 i1 k(1 )

- Want the values of and k that will make s2 a minimum

- Use Excel, Polymath or Matlab to find and k that minimize s2

Experimental planning
Evaluation of laboratory reactors

Also, See p.290 for the selection of lab reactors