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BKF2453

Chemical Reaction Engineering


Chapter 5:
Collection and Analysis of Rate Data

Objectives

Determine the reaction order and specific reaction


rate from experimental data obtained from either
batch or flow reactors.

Describe how to use equal-area differentiation,


polynomial fitting, numerical difference formulas
and regression to analyze experimental data to
determine the rate law.

Use regression software to evaluate the rate law


parameters given experimental data.

Describe how the methods of half lives, and of


initial rate, are used to analyze rate data.

Describe two or more types of laboratory reactors


used to obtain rate law data along with their
advantages and disadvantages.
#

Notes
Graphical method
Numerical method
Polynomial Fit
Differential Method
Half Life
Initial rate

Case Study
Consider the following reaction that occurs in a constant
volume batch reactor

Mole
Balance:

Rate Law:

Stoichiomet
ry:

Combine:

Integral Method

Zero order

First order

Second order

dC A

rA k
dt

dC A

rA kC A
dt

dC A
2

rA kC A
dt

CA

CA

CA

dC

C A0

k dt
0

C A C A0 kt
C A C A0 kt

dC A
C C A k 0 dt
A0

ln C A CC

A
A0

kt

ln C A ln C A0 kt
ln C A0 ln C A kt
C A0
ln
kt
CA

dC A
C C A 2 k 0 dt
A0
1

C
A

CA

kt
C A0

1
1

kt
C A C A0
1
1

kt
C A C A0

Finally we should also use the formula to plot reaction rate data in
terms of concentration vs. time for 0, 1st, and 2nd order reactions.
These types of plots are usually used to determine the values k for
runs at various temperatures and then used to determine the
activation energy.
Zero Order
First Order
Second Order

Differential Method (p. 224-232)


Taking the natural log of

The reaction order can be found from a ln-ln plot


of:

However, we are usually given concentration as a function of


time from batch reactor experiments
time (s)

t1

t2

t3

concentration (mol/dm3)

CAo

CA1

CA2

CA3

Three Ways to Determine (-dCA/dt) from Concentration-Time Data


Graphical,
Polynomial,
Finite Difference (Non-Linear Least Squares Analysis)

1. Graphical

This method accentuates measurement error!


#

2. Polynomial (using Polymath)


. using Polymath, MS Excel, Spreadsheet, MATLAB

CA = ao + a1t + a2t2 + a3t3 +a4t4

l Point

or point

st point

3. Numerical method (pg 258-259)


dC A 3C A0 4C A1 C A 2
1.

2t
dt

1
dC A
2.

C A(i 1) C A( i 1)

dt 2t
1
dC A
C A4 C A2
e.g.,

dt t 3 2t

dC A
3.e.g .,

dt

t5

1
C A3 4C A4 3C A5

2t
#

SELF TEST
The reaction AB is carried out in a constant volume batch
reactor. Determine the reaction order and specific reaction rate
from the following data.
t(min)

10

20

30

CA(mol/dm3)

0.6

0.4

0.3

Finite Difference

Non-Linear Least-Squares Analysis (p. 252)


We want to find the parameter values (alpha, k, E) for which the
sum of the squares of the differences, the measured rate (rm), and
the calculated rate (rc) is a minimum.

That is we want 2 to be a minimum.


For concentration-time data, we can integrate the mole balance
equation for -rA=kCA to obtain

We find the values of and k which minimize S2

Method of Initial Rates


Used to determine reaction rates with
possibilities of reverse order.
Overcome disadvantages of the differential
method
But in Example 5-4 no reverse kinetics can
be seen.

Method of Half-Lives

Half life, t1/2 time takes for the concentration of the reactant to fall to
half of its initial concentration.

Rate Law:

Combine:

By integrating with the initial condition of CA=CA0 and t=t0, thus

1 1
1
1 1
t
k ( 1) C A
C A0

t 1
kC A0 ( 1)

C A0

CA

When CA=CA0 and t=t, thus

t1

2 1 1 1
1

k ( 1) C A0

Taking the natural log of both sides,

ln t 1

2 1
ln
(1 ) ln C A0
( 1)k

Slope = 1-

ln t1/2

ln CA0
#

Differential reactors

Most commonly used catalytic reactor to obtain experimental data

Inert filing
FA0

FAe
L

Catalyst

Moles balance equation for differential reactors

rA '

FA0 X v0C A0 vC Ae
F

P
W
W
W

See example 5-5 pg 284 (Fourth Edition)


#

For constant volumetric flow rate:

rA '

v0 (C A0 C Ae ) v0C Ae

W
W

Reaction rate can be determined by measuring the product concentration

See example 5-5 pg 284 (Fourth Edition)

Weight Least Square


Analysis
Both the linear and nonlinear least-squares analyses

presented assume that the variance is constant throughout


the range of the measured variables.
For example, in a first-order decay reaction
(CA=CA0 e-kt ),
if the error in concentration measurement is 0.01 CA0, the
relative error in the concentration measurement [0.01 CA0/CA(t)
] will increase with time.
When this error condition occurs the sum to be minimized
for N measurements is

where 2 is a weighting factor.

For parameter estimation involving exponents, it has been


shown that a weighted least-squares analysis is usually
necessary. For example:

In general, these equations are of the form

Linearizing,

For a semilog arithmetic transformation, the


weighting function is just the square of the
independent variable itself3 (i.e., yi2). The
function to be minimized is

There are also strategies available that


suggest the experimental conditions to be
used for each succeeding data point in
order to converge most rapidly to the best
values of the rate law parameters (Box et
al.).

The End