Integral Method

Guess
A A A
C k r =
Insert to design
equation
A
A
r
dt
dC
=
A A
A
C k
dt
dC
=
A A A
C k r =
Integral Method
Integrate and
linearize
Ao A
C kt C ln ln + =
Obtain
Experimental Data
EXPERIMENTAL DATA
Time C
A

Integral Method
Fit Data
time, t
l
n

C
A

Check goodness
of fit
Integral Method

1. Guess a rate equation for the reaction
2. Insert the assumed rate of reaction in the design
equation and integrate
3. Linearize the integrated equation and test
goodness of fit using experimental data
Integral Method
Fractional Conversion
Fraction of any reactant that is converted to
another form.
Another form of reporting the extent of
reaction
Simplifies analysis in some particular
situations
Denoted as X
A

Integral Method
Ao
A Ao
A
N
N N
X

=
Ao
A
N
N
=1
|
|
.
|

\
|
V
V
1
1
Ao
A
C
C
=1
Ao
A
A
dN
dN
dX =
Integral Method
Empirical Reactions of nth Order
When the reaction mechanism is unknown,
we often attempt to fit the data with an nth-
order rate equation of the form:




n
A
A
A
kC
dt
dC
r = =
( )kt n C C
n
Ao
n
A
1
1 1
=

Integral method
Overall Order Determination
Given the reaction with corresponding rate
law:



Design Equation:
products bB aA + + ...
| o
B A A A
C C k r =
| o
B A A
A
C C k
dt
dC
=
Integral Method
If reactants are present in their stoichiometric ratios,
they will remain at that ratio throughout the
reaction.
... = =
b
C
a
C
B A
( ) ...
|
o
|
.
|

\
|
=
A A A
A
C
a
b
C k
dt
dC
( ) ... ...
| o
|
+ +
|
.
|

\
|
|
.
|

\
|
=
A A
A
C
a
c
a
b
k
dt
dC
( ) ... '
n
A A
A
C k
dt
dC
=
Integral Method
General Strategy:
1. Guess a value of n
2. Fit experimental data to linearized plot
3. If fit is good, determine the value of k
A
from the
slope
Integral Method
Notes:
1. Equation is not valid for n = 1
2. For n > 1, complete conversion (C
A
=0) is
theoretically at t = .
3. For n < 1, complete conversion (C
A
=0) can be
predicted at some finite time, equal to:

( )
( )
A
n
Ao
k n
C
t
1
1

=

Integral Method
n
nth order integrated/ linearized
equation
time(t) for C
A
= 0 of for X
A

= 1
n<1
-1
0
n=1 1 Indeterminate from equation Not defined
n>1
2 Not defined
3 Not defined
2 2
2
Ao A A
C t k C + =
Ao A A
C t k C + =
1 1
+ =
Ao A A
C t k C
2 2
2

+ =
Ao A A
C t k C
A Ao
k C t 2
2
=
A Ao
k C t =
Integral Method
1. Half-life method
2. Fractional life method
Integral Method
Half-Life
For an nth order reaction not equal to 1:


Linearizing:
| |
( )
n
Ao
A
n
C
k n
t

=
1
1
2 1
' 1
1 5 . 0
( )
| |
( )
A
n
Ao
k n
C n t
' 1
1 5 . 0
ln ln 1 ln
1
2 1

+ =

Integral Method
Run:
C
Ao
t
1/2
1
C
Ao1
(t
1/2
)
1
2
C
Ao2
(t
1/2
)
2
3
C
Ao3
(t
1/2
)
3
4
C
Ao4
(t
1/2
)
4
C
Ao

C
Ao1/2

t
1/2

l
n


t
1
/
2

ln C
A

Integral Method
Fractional Life Method
Concentration of reactant drops to a certain
fractional value F = C
A
/C
Ao
.
| |
( )
n
Ao
A
n
F
C
k n
F
t

=
1
1
' 1
1
Integral Method
Variations of the method
Method of excess





Where: = k
A
C
Bo
(B, others in large excesses)
| o
B A A
A
C C k
dt
dC
=
o
A A
A
C k
dt
dC

=
A
k

Integral Method
Analysis of total pressure data




Applicability:
Exact stoichiometry is known
Only one equation is involved in the reaction
( )
n
a
P P
To T Ao A
A
= t t
( )
n
r
P P
To T Ro R
A
+ = t t