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Chapter 5 Collection and Analysis of Rate Data

This chapter discusses methods for analyzing rate data from batch reactor experiments to determine the rate law and rate constants of reactions. The basic steps involve determining the reaction order with respect to each reactant by plotting concentration data versus time in different ways. Numerical differentiation, polynomial fitting, and graphical methods can be used to calculate reaction rates from concentration-time data. Non-linear regression can also fit parameters to minimize errors between measured and calculated reaction rates. An example determines the reaction order is 2 with respect to the limiting reactant from concentration-time data collected during the reaction.

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365 views23 pages

Chapter 5 Collection and Analysis of Rate Data

This chapter discusses methods for analyzing rate data from batch reactor experiments to determine the rate law and rate constants of reactions. The basic steps involve determining the reaction order with respect to each reactant by plotting concentration data versus time in different ways. Numerical differentiation, polynomial fitting, and graphical methods can be used to calculate reaction rates from concentration-time data. Non-linear regression can also fit parameters to minimize errors between measured and calculated reaction rates. An example determines the reaction order is 2 with respect to the limiting reactant from concentration-time data collected during the reaction.

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chiben
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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ERT 316 REACTION ENGINEERING

CHAPTER 5: COLLECTION AND ANALYSIS OF RATE DATA


BY
ANIS ATIKAH AHMAD

OBJECTIVE

to obtain the rate law for a specific reaction from


data collected in experiment (eg: concentrationtime for batch)

rA 0.24C

2
A

To find reaction
order

To find specific rxn


rate constant, k

BASIC STEPS IN ANALYSIS OF RATE


DATA

ALGORITHM FOR DATA ANALYSIS


If 1 of the reactant is in
excess, assume its
concentration is
constant.

BATCH REACTOR DATA


1. Differential method

BATCH REACTOR DATA

1. Determine

2. Determine

3. Determine kA :

rA
kA
CA CA

BATCH REACTOR DATA

How to find dC A since we only have data of


dt
concentration and time?
Time
(min)
CA
(mol/dm3)

3 Methods:

50

100

150

0.05

0.038

0.0306

0.0256

GRAPHICAL DIFFERENTIATION

Plot a histogram

Draw a smooth curve in such


a way that:
A=B
A+C=B+D

dC A

dt

NUMERICAL DIFFERENTIATION
FORMULAS

POLYNOMIAL FIT

Fit the concentration-time data to an nth-order


polynomial:

C A a0 a1t a2t 2 ...ant n

Find best value of ai

Differentiate Eq 1 wrt time:

dC A
a1 2a2t 3a3t 2 ...nant n 1
dt

Eq 1

BATCH REACTOR DATA


2. Integral method (linear plot)

Trial & error to find


reaction order. If the
order is correct, the plot
should be linear

BATCH REACTOR DATA


2. Integral method (linear plot)

BATCH REACTOR DATA


3. Non-linear regression
We want to find the parameter values (,k) for which
the sum of the squares of the differences, the
measured rate (rm), and the calculated rate (rc) is a
minimum.
For conc-time data, we can integrate the mole
balance equation to obtain:
N

s 2 C Ami C Aci C Ami C 1A0 1 kti


i 1

i 1

1 / 1

METHOD OF INITIAL RATES

Determine rA0
first

CA0 (mol/dm3)
-rA (mol/dm3.)s

METHOD OF HALF-LIVES

EXAMPLE 5-1
The reaction of triphenyl methyl chloride (trityl) (A) and methanol (B)
Trityl (A) + Methanol (B) Products
was carried out in a solution of benzene & pyridine at 25C. Pyridine
reacts with HCl that then precipitates as pyridine hydrochloride
thereby making the reaction irreversible.
The concentration-time data in table below was obtained in a batch
reactor:
Time (min)
0
50
100
150
200
250
300
CA (mol/dm3)

0.05

0.038

0.0306

0.0256

0.0222

0.0195

0.0174

(At t= 0, CA = 0.05 M

The initial concentration of methanol was 0.5 mol/dm 3


i.

Determine the reaction order with respect to triphenyl methyl


chloride.

EXAMPLE 5-1- SOLUTION


STEP 1

Postulate a rate law.

rA kC A C B
STEP 2

Select reactor type & corresponding mole balance.

Batch reactor
STEP 3

dN A
rAV
dt

Process your data in terms of measured variable (in this case: CA).

Since it is a liquid phase reaction, V=V0

dN A
rAV0
dt

d N A V0
rA
dt

dC A
rA
dt

EXAMPLE 5-1- SOLUTION


STEP 4

Look for simplication.

Because the concentration of methanol is 10 times the initial


concentration of trityl (excess), its concentration is essentially constant.

CB CB 0

rA kC A C B0
STEP 5

dC A
rA
dt

rA kC B0C A

Determine the reaction order.

dC A

k C A
dt
Taking the natural log;

dC A

ln
ln k ln C A

dt

The slope

rA k C A

FIND

(1)

dC A
dt

t (min)

CA (mol/dm3)

0.05

(2)

C A
dC A
10 4
10 4
t
dt

(mol/dm3.min)

(mol/dm3.min)
3.0

2.4
50

0.038

1.86
1.48

100

0.0306

1.2
1.00

150

0.0256

0.8
0.68

200

0.0222

0.5
0.54

250
GIVEN!

0.0195

0.47
0.42

From histogram/finite
difference method/polynomial

GRAPHICAL DIFFERENTIATION

dC A
10 43
dt
2.5
2
1.5
1
0.5

t (min)

PLOT

dC A
ln
vs ln C A

dt

dC A
ln
dt

Slope= order of reaction ( )

2.05
ln C A

FIND K

Substitute the value of C A ,

dC A
, into
dt

dC A

k C A
dt
eg,; CA = 22.2 x 10-3 mol/dm3,

k = 0.125 dm3/mol.min

dC A
0.5 10 4 mol / dm 3 min
dt

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