Lecture 11 Thursday 2/7/08

Determining the Rate Law from Experimental Data

Integral Method
Graphical Method
Nonlinear Least Regression

Multiple Reactions
The Four Types
Whats New to Our Algorithm
Reactions in Series





Levenspiel Plot

F
A0
r
A

X

Two steps to get

Step 1: Rate Law


Step 2: Stoichiometry


Step 3: Combine to get



r
A
= f X
( )

r
A
= g C
i
( )

C
i
( )
= h X
( )

r
A
= f X
( )
Finding Rate Laws, Multiple Reactions
( ) | |
A
A
A
A
A Ai
C k
dt
dC
kC
dt
dC
kt C C
ln ln ln
1
1
1
1
0
o
o
o
o
o
+ =
|
.
|

\
|

=
=

Slope =
C
A

dC
A
/dt
ln
ln
o
Ap
p
A
C
dt
dC
k
|
.
|

\
|

=
t(min) 0 1 2 3
C
A
(mol/L) 1 0.7 0.5 0.35
0.3 0.2 0.15
t
C
A
A
A

Find the f(t) of using equal area differentiation

t
C
A
A
A

t
C
A
A
A

.1
.2
.3
t
1 2 3
Areas equal for both sides
of the histogram
C
A
1 0.7 0.5 0.35
-dC
A
/dt 0.35 0.25 0.175 0.12
Plot dC
A
/dt as a function of C
A

= slope o
Ap
p
A
C
dt
dC
k
|
.
|

\
|

=
ln
C
A

Slope =
dC
A
/dt
Regression Method
C
meas
1 0.7 0.5 0.35
C
Calc
1 0.5 0.33 0.25
(C
c
-C
m
) 0 -0.2 -0.17 -0.10
(C
c
-C
m
)
2


0 0.04 0.029 0.01
Guess values for and k and solve for measured data
points then sum squared differences
for = 2, k = 1 S
2
= 0.079
for = 2, k = 2 S
2
= 0.27
etc. until S
2
is a minimum
4 Types of Multiple Reactions
Series: A B C
Parallel: A D, A U
Independent: A B, C D
Complex: A + B C + D, A + C E
With multiple reactors, either molar flow or number of moles must be used
(no conversion!)
Flow Batch




Rates: rate law for each reaction
net rates:
the sum of rates for each reaction given

B
B
A
A
r
dV
dF
r
dV
dF
=
=
V r
dt
dN
V r
dt
dN
B
B
A
A
=
=
A A
i
iA A
r r r r
2 1
1
+ = =

=
example: 1) A + B C + D -r
1A
= k
1A
C
A
C
B
-r
2A
= k
1A
C
A
C
C
2) A + B E etc.
relative rates:

only applied to a given reaction
Stoich:

example: A B C (1) A B k
1

(2) B C k
2

1) mole balance: 2) rates:




i
iD
i
iC
i
iB
i
iA
d
r
c
r
b
r
a
r
= = =
|
.
|

\
|
|
|
.
|

\
|
=
T
T
P
P
F
F
C C
A
A
T A
0
0 0
0
A
C
A
B
A
A
C
C
B
B
A
A
r
dt
dC
r
dt
dC
r
dt
dC
V r
dt
dN
V r
dt
dN
V r
dt
dN
=
=
=
=
=
=
V=V
0
(constant batch)
B B B
A A
B B B
A A A
r r r
r r
C k r
C k r
2 1
1
1 1
1 1
+ =
=
=
=
laws
net rates