Professional Documents
Culture Documents
Lecture Seven 2020
Lecture Seven 2020
2
Integral Method
Consider the following reaction that occurs in a constant
volume Batch Reactor: (We will withdraw samples and
record the concentration of A as a function of time.)
A → Products
dNA
Mole Balances: = rAV
dt
at t = 0, CA = CA 0 at t = 0, CA = CA 0 at t = 0, CA = CA 0
CA 0
CA = CA 0 − kt ln = kt
1
−
1
= kt
4 CA CA CA 0
Integral Method
Guess and check for α = 0, 1, 2 and check against
experimental plot.
=0 =1 =2
C A0 1 1
rA = C A0 − kt ln = kt − = kt
CA C A C A0
CA ln(CA0/CA) 1/CA
5
t t t
Differential Method
dC A
Taking the natural log of − = kC A
dt
dC A
ln − = ln k + ln C A
dt
dCA
The reaction order can be found from a ln-ln plot of: − vs CA
dt
dC A ln
−
dt
dC A
dC A
−
−
Slope = α dt p
dt P
k=
C Ap
ln
6 C AP CA
Methods for finding the slope of log-log and semi-log
graph papers may be found at
http://www.physics.uoguelph.ca/tutorials/GLP/
time (s) 0 t1 t2 t3
concentration CA0 CA1 CA2 CA3
(moles/dm3)
7
Three ways to determine (-dCA/dt) from concentration-time data
Graphical differentiation
Numerical differentiation formulas
Differentiation of a polynomial fit to the data
1. Graphical
CA
−
t
8
t
CA
−
t
dC A
−
dt 0
dC A
−
dt t1
dC A
−
dt t 2
t
0 t1 t2
9 The method accentuates measurement error!
Example – Finding the Rate Law
t(min) 0 1 2 3
C A
− 0.3 0.2 0.15
t
t
1 2 3
10
Example – Finding the Rate Law
C A
Find f(t) of − using equal area differentiation
t
CA 1 0.7 0.5 0.35
-dCA/dt 0.35 0.25 0.175 0.12
dCA/dt
Slope = α
ln
11 CA
Example – Finding the Rate Law
Choose a point, p, and find the concentration and
derivative at that point to determine k.
ln dCA/dt
dC A
−
dt p dC A
− Slope = α
k= dt p
C Ap
ln CA
CA p
12
Non-Linear Least-Square Analysis
We want to find the parameter values (α, k, E) for
which the sum of the squares of the differences, the
measured rate (rm), and the calculated rate (rc) is a
minimum.
2 =
n
(Cim − Cic )
2
=
S2
i =1 N −K N −K
13
Non-Linear Least-Square Analysis
For concentration-time data, we can combine the
mole balance equation for−rA = kCA to obtain:
dC A
= −kC A
dt
t = 0 C A = C A0
C1A−0 − C1A− = (1 − )kt
14
Non-Linear Least-Square Analysis
Now we could use Polymath or MATLAB to find the values of α and k
that would minimize the sum of squares of differences between the
measured (CAm) and calculated (CAc) concentrations.
That is, for N data points,
and compare it with the measured time, tm, at that same concentration.
That is, we find the values of k and α that minimize:
15
Non-Linear Least Squares Analysis
Guess values for α and k and solve for measured
data points then sum squared differences:
CAm 1 0.7 0.5 0.35
CAc 1 0.5 0.33 0.25
(CAc-CAm) 0 -0.2 -0.17 -0.10
(CAc-CAm)2 0 0.04 0.029 0.01 0.07
for α= 2, k = 1 → s2 = 0.07
for α = 2, k = 2 → s2 = 0.27
16 etc. until s2 is a minimum
Non-Linear Least Squares Analysis
17
Non-Linear Least Squares Analysis
( )
N N
1 1− 2
s = (CAmi − CAci ) = CAmi − C − (1 − )kti
2 2 1−
A0
i=1 i=1
18
Minimum Sum of Squares
20
21
Residuals
22
23
End of Lecture 7
24