ChE 452 Lecture 08

Analysis Of Data From A Batch Reactor

1
Objective
Data analysis from indirect measurements
Essens method (learned in p-chem)
Does not usually work
Vant Hoffs method
Accurate but amplifies errors in data
2
Background: Kinetic Data After
Measuring







Indirect method a method where you measure
some other property (i.e. concentration vs time)
and infer a rate equation.
3
0 5 10 15 20 25 30 35
10
100
Time, Hours
P
r
e
s
s
u
r
e
,

x
2
,

t
o
r
r
Figure 3.8 Typical batch data
for reaction (3.7). Data of
Tamaru[1955].
Objective For Today:
Analysis Of Rate Data

Derive basic equations
Essens method
Vant Hoffs method
4
Derivation Of Performance
Equation For A Batch Reactor
5
For A B, the moles of A
reacted/volume/time will equal the reaction
rate, i.e.





A
A
dC
=r
d
(1)
C
A
is the concentration of A, t is time,
and r
A
is the rate of reaction per unit
volume.
Figure 3.11 A batch reactor
Integration Yields The
Following
6
(3.31)


Memorize this equation
0
A
f
A
C
A
A
C
dC
=
(-r )
}
For A First Order Reaction
r
A
= -k
1
C
A

(3.38)
Substituting equation (3.38) into equation
(3.31) and integrating yields:


7
t =
|
|
.
|

\
|
f
A
0
A
1
C
C
Ln
k
1
Memorize this equation
(3.39)
Derivation
For An nth Order Reaction:
( )
n
A n A
C k r =
9
(3.41)
Substituting equation (3.41) into equation (3.31),
integrating, and rearranging yields:
( ) ( )
t =
(
(

|
|
.
|

\
|

1
C
C
C k 1 n
1
1 - n
f
A
o
A
1 n
o
A n
(3.42)
Memorize this equation
Derivation
Plots Of Equations
0% 20% 40% 60% 80% 100%
conversi on
0
2
4
6
8
10
T
i
m
e
First Order
Second
Order
11
Table 3.4 Rate Laws For A
Number Of Reactions
12
Rate Laws for a number of reactions
Reaction Rate Law Differential Equation Integral Equation
A Products
A+B Products
r
A
=k
A

A Products
A+B Products
r
A
=k
A
[A]

A Products
A+B Products
r
A
=k
A
[A]
n


A+B Products r
A
=k
A
[A][B]

A+2B Products r
A
=k
A
[A][B]
A B r
A
=k
1
[A]-
k
2
[B]
A
A
k
d
dX
=
t
A A
A
X k
d
dX
=
t
n
A
1 n n
A
A
A
X ) C ( k
d
dX

=
t
) X C C )( X 1 ( k
d
dX
A
0
A
0
BA A A
A
=
t
) X C 2 C )( X 1 ( k
d
dX
A A
0
B A A
A
=
t
A 2 A A
A
X k ) X 1 ( k
d
dX
=
t
t
=
A
A
X
k
|
|
.
|

\
|
t
=
A
A
X 1
1
Ln
1
k
(
(

|
|
.
|

\
|

t
=

1
X 1
1
) C )( 1 n (
1
k
1 n
A
1 n 0
A
A
|
|
.
|

\
|

t
=
0
A A
0
B
A
0
B
0
B
0
A
A
C X C
) X 1 ( C
Ln
C C (
1
k
|
|
.
|

\
|

t
=
0
A A
0
B
A
0
B
0
B
0
A
A
C X 2 C
) X 1 ( C
Ln
C C 2 (
1
k
|
|
.
|

\
|
t
= +
A e
2 1
X X
1
Ln
1
) k k (
Fitting Batch Data To A Rate
Law
Steps
Start with a batch reactor and measure
concentrations vs time.
Fit those data to a first order and a
second order rate law and see which
equation fits better.
Whichever rate equation fits best is
assumed to be the correct rate equation
for the reaction.
13
Key Challenge: First And Second Order
Data Does Not Look That Much Different
14
0 0 . 5 1 1 . 5
0
0 . 2
0 . 4
0 . 6
0 . 8
1
Time
C


/
C
0
A
A
H
a
l
f

O
r
d
e
r
F
i
r
s
t

O
r
d
e
r
Second Order
T
h
ir
d
O
r
d
e
r
0 0 . 5 1 1 . 5
0
0 . 2
0 . 4
0 . 6
0 . 8
1
Time
C


/
C
0
A
A
H
a
l
f

O
r
d
e
r
F
i
r
s
t

O
r
d
e
r
S
e
c
o
n
d

O
r
d
e
r
T
h
ir
d
O
r
d
e
r
Same
k(C
A
0
)
n-1

Vary k to fit
data

Essens Method
15
t =
|
|
.
|

\
|
f
A
0
A
1
C
C
Ln
k
1
( ) ( )
t =
(
(

|
|
.
|

\
|

1
C
C
C k 1 n
1
1 - n
f
A
o
A
1 n
o
A n
First order
nth order
(3.42)
(3.39)
Essens Method
16
(
C


/
C


)

-

1
0
A
A
l
n
(
C


/
C


)
0
A
A
0 0 . 5 1 1 . 5
0
0 . 2
0 . 4
0 . 6
0 . 8
1
Time
H
a
l
f

O
r
d
e
r
F
i
r
s
t

O
r
d
e
r
S
e
c
o
n
d

O
r
d
e
r
T
h
i
r
d

O
r
d
e
r
0 0 . 5 1 1 . 5
0
0 . 2
0 . 4
0 . 6
0 . 8
1
Time
H
a
l
f

O
r
d
e
r
F
i
r
s
t

O
r
d
e
r
S
e
c
o
n
d

O
r
d
e
r
T
h
i
r
d

O
r
d
e
r
Figure 3.15
Example: The Concentration Of
Dye As A Function Of Time
17
C
A
,m
moles
/Lit
t, Min
C
A
t
C
A
t
1 0 0.63 6 0.45 12
0.91 1 0.59 7 0.43 13
0.83 2 0.56 8 0.42 14
0.77 3 0.53 9 0.40 15
0.71 4 0.50 10 0.38 16
0.67 5 0.48 11 0.37 17
Table 3.5
Essen Plot For Example:
18
0 5 10 15
0
0.5
1
1.5
Time, Mins
0 5 10 15
0
1
2
3
4
5
6
Time, Mins
0 5 10 15
0
0.2
0.4
0.6
0.8
1
Time, Mins
l
n
(
C


/
C


)
0
A
A
(
C


/
C


)


-

1
2
A
A
(
C


/
C


)

-

1
0
A
A
0
r
2
=.984
r
2
=.999
r
2
=.981
No statistically significant difference between results.
Figure 3.16
Example Shows Essens Method
Does Not Distinguish Between Models

In the literature, Essens method is often used.
Useful for impressing your boss since it always
fits with good r
2
(given good data)
It often gives the incorrect answers.

19
Vant Hoffs Method

Take batch data as before.
Calculate kone (first order rate constant)
ktwo (second order rate).
kone should be constant for a first order
reaction, ktwo should be constant for a
second order reaction. (Use f test to
check).
20
Equations For kone And
ktwo Follow From Before
21

t =
|
|
.
|

\
|
A
0
A
1
C
C
Ln
k
1
|
|
.
|

\
|
t
=
A
0
A
1
C
C
Ln
1
k
(3.39) (3.51)
( )
(
(

|
|
.
|

\
|
t
=

1
C
C
C ) 1 n (
1
k
1 n
A
0
A
1 n
0
A
n
(3.52)
( ) ( )
t =
(
(

|
|
.
|

\
|

1
C
C
C k 1 n
1
1 - n
f
A
o
A
1 n
o
A n
(3.42)
Solve for k
1
Solve for k
n
Derived previously

Derived previously

Easy Solution: Define A VB
Module In Microsoft Excel
22
Public Function kone(ca0, ca, tau) As Variant
kone = Log(ca0 / ca) / tau
End Function

Public Function ktwo(ca0, ca, tau) As Variant
ktwo = ((1# / ca) - (1# / ca0)) / tau
End Function

Public Function kthree(ca0, ca, tau) As Variant
kthree = ((1# / ca) ^ 2 - (1# / ca0) ^ 2) / tau
End Function
Microsoft Excel/Visual Basic
Return Types
23
As Variant General return type (can be an
integer, real, vector, matrix,
logical or text)
As Single Single precision real
As Double Double precision real
As Integer Integer
The Formulas In The
Spreadsheet For Vant Hoffs
Method
24
B C D E F
1 Ca0= 1
2 Essen's
Method
3 time conc first second third
4 ln(Ca0/Ca) (Ca0/Ca)-1 (CA0/CA)^
2-1
5 0 1
=kone(ca0,C5,B5) =ktwo(ca0,C5,B5) =kthree(ca0,C5,B5)
6 1 0.91
=kone(ca0,C6,B6) =ktwo(ca0,C6,B6) =kthree(ca0,C6,B6)
7 2 0.83
=kone(ca0,C7,B7) =ktwo(ca0,C7,B7) =kthree(ca0,C7,B7)
8 3 0.77
=kone(ca0,C8,B8) =ktwo(ca0,C8,B8) =kthree(ca0,C8,B8)
9 4 0.71
=kone(ca0,C9,B9) =ktwo(ca0,C9,B9) =kthree(ca0,C9,B9)
The Numerical Values For
Vant Hoffs Method
25
B C D E F
3 Time conc k1 k2 k3
4 0 1 ln(1/Ca
)/t
((Ca0/C
a)-1)/t
((CA0/CA)
^2-1)/t/2
5 1 0.91 0.094 0.099 0.104
6 2 0.83 0.093 0.102 0.113
7 3 0.77 0.087 0.1 0.114
8 4 0.71 0.086 0.102 0.123
9 5 0.67 0.08 0.099 0.123
10 6 0.63 0.077 0.098 0.127
Vant Hoff Plot
26
Vant Hoffs method is much more accurate than Essens method.
Essens is more common!
0 5 10 15
0.05
0.1
0.15
0.2
Time, Mins
R
a
t
e

C
o
n
s
t
a
n
t

K
3
K
2
K
1
Oxidation of
Red Dye
Figure 3.18 Vant Hoff plot of the data from tables 3.5 and 3.6
Discussion Problem: Use Vant Hoffs
Method To Determine The Order For The
Following Data
27
Table 4.1 Buchanans [1871] data for the reaction:
CICH
2
COOH + H
2
COOH + HCI at 100 C
Time Hours [CICH
2
COOH] gms/liter
0
2
3
4
6
10
13
19
28
34.5
43
48
4
3.80
3.69
3.60
3.47
3.10
2.91
2.54
2.26
1.95
1.59
1.39
Solution:
28
Ca0= 4
Van't Hoff's
time Conc first second third
ln(ca0/Ca) (Ca0/Ca)-1 (CA0/CA)^2-
1
0 4 =kone(cao,B5
,A5)
=ktwo(cao,B5
,A5)
=kthree(cao
,B5,A5)
2 3.8 =kone(cao,B6
,A6)
=ktwo(cao,B6
,A6)
=kthree(cao
,B6,A6)
3 3.69 =kone(cao,B7
,A7)
=ktwo(cao,B7
,A7)
=kthree(cao
,B7,A7)
4 3.6 =kone(cao,B8
,A8)
=ktwo(cao,B8
,A8)
=kthree(cao
,B8,A8)
6 3.47 =kone(cao,B9
,A9)
=ktwo(cao,B9
,A9)
=kthree(cao
,B9,A9)
Solution Continued:
29
ca0= 4
time conc first second third
ln(ca0/
Ca)
(Ca0/Ca
)-1
(CA0/CA
)^2-1
0 4 #VALUE! #VALUE! #VALUE!
2 3.8 0.026 0.007 0.003
3 3.69 0.027 0.007 0.004
4 3.6 0.026 0.007 0.004
6 3.47 0.024 0.006 0.003
10 3.1 0.025 0.007 0.004
13 2.91 0.024 0.007 0.004
19 2.54 0.024 0.008 0.005
25 2.26 0.023 0.008 0.005
34.5 1.95 0.021 0.008 0.006
43 1.59 0.021 0.009 0.008
48 1.39 0.022 0.01 0.009
Van't Hoff's
Vant Hoff Plot
30
0 10 20 30 40 50
0.02
0.03
0.04
0.05
Time, Mins
R
a
t
e

C
o
n
s
t
a
n
t

K
3
K
2
K
1
Hydration of
Chloracetic Acid
Figure 3.18 Vant Hoff plot of the data from tables 3.5 and 3.6
Discussion Problem 2
Ammonium-dinitramide, (ADN) NH
4
N(NO
2
)
2
, is a oxidant used in solid
fuel rockets and plastic explosives. ADN is difficult to process because it
can blow up. Oxley et. Al., J. Phys chem A, 101 (1997) 5646, examined
the decomposition of ADN to try to understand the kinetics of the
explosion process. At 160 C they obtained the data in Table P3.20.
31
time,
seconds
fraction of
the AND
remaining
time,
seconds
fraction of
the AND
remaining
time,
seconds
fraction of
the AND
remaining
0 1.0 900 0.58 2400 0.24
300 0.84 1200 0.49
600 0.70 1500 0.41
Table P3.20 Oxley's measurements of the decomposition of
dinitramide at 160 C
Discussion Problem 2
Continued:

a) Is this a direct or indirect measurement of the rate?

b) Use Vant Hoffs Method to fit this data to a rate
equation.

c) If you had to process ADN at 160 C, how long could
you run the process without blowing anything up?
Assume that there is an explosion hazard once 5% of
the ADN has reacted to form unstable intermediates.
32
This Is An Indirect Measurement! Use
Same Spreadsheet As Before To Fit
Data
33
Ca0= =b5
Van't Hoff's
time Conc first second third
0 1 ln(ca0/Ca) (Ca0/Ca)-1 (CA0/CA)^2-1
300 0.84 =kone(cao,B5
,A5)
=ktwo(cao,B5
,A5)
=kthree(cao,
B5,A5)
600 0.7 =kone(cao,B6
,A6)
=ktwo(cao,B6
,A6)
=kthree(cao,
B6,A6)
900 0.58 =kone(cao,B7
,A7)
=ktwo(cao,B7
,A7)
=kthree(cao,
B7,A7)
1200 0.49 =kone(cao,B8
,A8)
=ktwo(cao,B8
,A8)
=kthree(cao,
B8,A8)
1500 0.41 =kone(cao,B9
,A9)
=ktwo(cao,B9
,A9)
=kthree(cao,
B9,A9)
2400 0.24 =kone(cao,B1
0,A10)
=ktwo(cao,B1
0,A10)
=kthree(cao,
B10,A10)
Solution Cont.
34


Ca0=

1









Van't Hoff's




time

Conc

first

second

third





ln(ca0/Ca)

(Ca0/Ca)-1

(CA0/CA)^2-1

0

1

#VALUE!

#VALUE!

#VALUE!

300

0.84

0.000581

0.000635

0.001391

600

0.7

0.000594

0.000714

0.001735

900

0.58

0.000605

0.000805

0.002192

1200

0.49

0.000594

0.000867

0.002637

1500

0.41

0.000594

0.000959

0.003299

2400

0.24

0.000595

0.001319

0.006817

Solution Cont.
c) from equ 3.39

35
t =
|
|
.
|

\
|
f
A
o
A
1
C
C
Ln
k
1
k
k
1
=0.0006/sec (from spreadsheet)
o
A
C =1 (given)
f
A
C =0.95 (what's left if 5% converted)

sec 85
0.95
1
Ln
0.0006
1
C
C
Ln
k
1
f
A
o
A
1
=
|
.
|

\
|
=
|
|
.
|

\
|
= t
Summary: Two Methods To Fit
Rate Data
Essens Method
Most common method
Plots look the best
Gives great looking results even with incorrect rate
equation
Vant Hoffs Method
More accurate than Essen
Rare in literature
Plots noisier
Highlights weaknesses in rate equations
36
Class Question
What did you learn new today?
37