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