Chemical Engineering

Department
CDB 2043 REACTION ENGINEERING

CHAPTER 5: Collection and Analysis

of Rate Data
Failing to plan is planning to fail
-Effie Jones-

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 LEARNING OUTCOMES

At the end of the chapter, student should be able to

apply the concept of CRE algorithm in solving design
problems related to:
1. Determine the reaction order and specific
reaction rate from experimental data
2. Decide the most suitable type of analysis
technique for a particular problem

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Recap from Chapter 4

MOLE BALANCE & DESIGN EQUATION

RATE LAW
STOICHIOMETRY
COMBINE INFORMATION
EVALUATE
GRAPHICAL METHOD
NUMERICAL METHOD
ANALYTICAL METHOD
SOFTWARE
 Topics

Analysis of data to find rate law:

1) Integral method of analysis
2) Differential method of analysis
 Analysis of Data to find Rate Law
2 common reactors used to obtain rate data:
Batch reactor
For homogeneous reactions
By measuring CA as f(t)

Differential reactor

FA0 FAe

L Catalyst
 Analysis of Data to find Rate Law
Methods used to analyze rate data:
1. Integral method (try and error - reaction order)

2. Differential method ( ) (Fogler: page 258-259)


Methods of finding

Graphical
Finite Different Method (Numerical Method)
Polynomial

3. Half live method

4. Initial rate method
5. Linear regression
6. Non-linear regression
 Integral method analysis

1. Need to guess reaction order

2. Integrate the differential form of equation used to model the
reactor used.
3. If the right reaction order is assume, the plot of
concentration time data should be linear

3 examples will be considered:

Zero order
Y First order
Second order

X
 Analysis of Data to find Rate Law
Consider the following reaction:
A Products

Step 1: Mole balance: =

Step 2: Rate Law: =

Step 3: Stoichiometry: V=V0, =
0

Step 4: Combine: =

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 Integral method analysis
Zero order reaction:

= rA = k

Integration gives:

= CA0
0 0
x Slope = -k

= 0 CA

y C m
t
 Integral method analysis

First order reaction:

= =

Integration gives:

1
=

0 0
x
0

0
=
Slope = k

y m
t

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 Integral method analysis

Second order reaction:

= = 2

Integration gives:

1
2 =

0 0
x
1
1 1 Slope = k
=
0

m
y C CA0

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 Example 5.2
The reaction of trityl (A) and methanol (B)
O
||
(C6H5)3CCl + CH3OH (C6H5)3CCH3 + HCl
A B C D
Time (min) 0 50 100 150 200 250 300

CA
0.0500 0.0380 0.00306 0.00256 0.00222 0.00195 0.00174
(mol/dm3)

It was reported that the reaction is second order w.r.t A.

Given,
CB0 = 0.5 mol/dm3
Mission:
1. Using the data, confirm that the reaction is second order.
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 Example 5.1


1 1 1
= 2 = +
2 = 0
0 0

70
Time CA 1/CA
(min) (mol/dm3) (dm3/mol) y = 0.1248x + 20.118
60

0 0.0500 50
20.00
50 0.0380 1 40
26.32
100 0.00306
30 Slope = k
326.80
150 0.00256 20
390.63 1
10
200 0.00222
450.45 0
0
250 0.00195 0 50 100 150 200 250 300 350
512.82
300 0.00174
t
574.71 dm3
k= 0.1248 mol.min CA0= 0.0497 mol/dm3

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 Summary of Topic 1

1. Guess reaction order, integrate mole balance

equation.
2. Calculate the resulting function in term of
concentration data, and plot f(C) vs t
3. If the plot is linear, then you have guessed the
correct reaction order.
4. Otherwise, guess another order and repeat the
procedure.

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 Differential method analysis

Take natural log of: = x


= +

y C m

Plot graph of vs. give straight line graph with:

Slope =
Intercept = ln k
H ??

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Finding

Graphical Method

Finite Difference Method

30 +41 2
Initial point : =
0 2
1
Interior point : = +1 1
2
1
Last point : = 3 44 + 35
5 2

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 Example 5.2
The following reaction takes place in an isothermal constant volume batch reaction
system. The initial concentration of B is 0.5 mol/dm3. The concentration of A at
different time was recorded as shown in the table.
O
||
(C6H5)3CCl + CH3OH (C6H5)3CCH3 + HCl
A B C D

Time (min) 0 50 100 150 200 250 300

CA
0.0500 0.0380 0.00306 0.00256 0.00222 0.00195 0.00174
(mol/dm3)

Mission:

Determine reaction order w.r.t. A

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 Example 5.2
Time CA
= (min) (mol/m3)x103





0 50
0.24
= + 50 38

0.148
100 30.6
Using graphical method: 0.1
150 25.6
2 1 0.068
= 200 22.2
2 1
0.054
250 19.5
38 50 0.042
= = 0.24 300 17.4
50 0 3 .

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 Example 5.2
Time CA

(min) (mol/m3)x103
0.30
0 50 0.3
0.24
0.25 50 38 0.186
0.148
100 30.6 0.12
0.20 0.1
150 25.6 0.08

0.068
0.15 200 22.2 0.05
mol
0.054
dm3 . min 250 19.5 0.047
0.10
0.042
300 17.4
0.05

0
0 50 100 150 200 250 300
t (min)
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 Example 5.2
t CA ln CA ln [

]

= +

0 50 -0.6931 0.3 -1.20397

50 38 -0.9676 0.186 -1.68201 -2.0000 -1.5000 -1.0000 -0.5000 0.0000

0
100 30.6 -1.1842 0.12 -2.12026 -0.5
-1

150 25.6 -1.3626 0.08 -2.52573

-1.5

-2
200 22.2 -1.5051 0.05 -2.99573
y = 2.0868x + 0.2912 -2.5
250 19.5 -1.6348 0.047 -3.05761 -3
-3.5
300 17.4

= 2.0868

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 Summary of Topic 2

1. Find .

2. Plot

3. Slope is (reaction order).

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 END OF LECTURE

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