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Engineering
Interpretation of Lab Reactor
Data (to obtain Rate Laws)
Dr Veluri VPS Murthy, Professor
Phone: +606 7989 271 (preferred)
Mobile: +601116672959
e-mail: vvpsnm@gmail.com
Chemical Reaction Engineering
2014
Contents
Reaction Kinetics & Rate Law (Recap)
Integral method
Differential method (using Batch and CSTR)
Method of initial rates
Method of half-lives.
If 2NO+O2 2NO2
then -rNO = kNO C 2 NO CO2 if it is elementary!
f(CA) is determined experimentally.
4
Measurement of concentrations
In a batch reactor, the concentrations change with
time continuously. Hence, concentrations of
reactants have to be measured.
Some of the techniques to measure concentrations are as follows:
Integral Method
In this method, we integrate the design equation.
It is a trial and error method.
Most often used when reaction order is known
and we need to find k.
This method is considered for zero, first and
second order reactions.
Method: Integrate the design equation assuming
the order and rearrange to a linear form.
Use the concentration Vs. time data to calculate
the variables in the rearranged form and plot.
If the data fit shows linearity, it confirms the order
assumption and k is determined from the slope.
8
dNA
(rA ) V
dt
(rA ) k CA
3. Stoichiometry
V=Vo
4. Combine 1 dN A dC A (r )
A
with -rA
V dt
dt
CA
CA0
t t
dC A
dt
kCA t 0
( rA ) k C k C k
0
A
dC A
k
dt
t t
CA
dC A
dt t 0 t
k t 0
C A0
CA
1
1
1
CA
C A C A 0 C A C A0 t
dC A
k C A0
k
k
C A C A0 kt
C A C A0 kt
10
CA
C A0
dC A
k CA
dt
t t
dC A
dt t 0 t
kCA t 0
CA
1
dC A
1
1
CA
ln C A C A0 ln C A ln C A0 t
k C A0 C A
k
k
ln C A / C A0 kt
ln C A0 / C A kt
11
dC A
2
k CA
dt
t t
CA
dC A
dt t 0 t
2
C A 0 kCA
t 0
CA
1
dC A
1
1
k CA0 C A
k CA
CA
C A0
1 1
1
t
k C A C A0
1
1
kt
C A C A0
1
1
kt
C A C A0
12
First-order
Second-order
13
2.0
1.60 1.35
15
22
1.10 0.87
30
40
0.70 0.53
60
0.35
[mol/L]
14
0 5
15
22
30
40
60
0.53
0.37
[mol/L]
Integral Method- zero order
2.50
CA (mol/L)
2.00
y = -0.026x + 1.6508
2
R = 0.8621
1.50
1.00
0.50
0.00
0
10
20
30
40
time, min
50
60
15
70
t [min]
0 5
ln CA0 / CA 0 0.22
15
22
0.39
0.64 0.92
30
40
60
1.05
1.33
1.69
y = 0.032x
2
R = 0.9638
ln(CA0/CA)
2.00
1.50
1.00
0.50
0.00
0
10
20
30
40
time, min
50
60
16
70
Second-order
t [min]
1 / CA
15
22
30
40
60
1.89
2.70
1/CA
2.00
1.50
y = 0.039x + 0.3793
2
R = 0.9852
1.00
0.50
0.00
0
10
20
30
40
time, min
50
1760
70
Differential Method
It is called differential method, because we
differentiate the concentration versus time data.
Determines reaction order directly
no trial and error (like integral method)
2. Rate Law
(rA ) k CA
3. Stoichiometry V=Vo
4. Combine
dNA
(rA ) V
dt
1 dNA
(rA )
V dt
dC A
k CA
dt
19
k CA
dt
dC A
ln(
) ln(k ) ln(C A )
dt
ln (-d CA/dt)
ln (CA).
) ln(k ) ln(C A )
() can be found from slope of
dt
log-log plot of - dCA/dt and CA
(- dCA/dt)
1000
100
dCA
dt p
10
CA
1
1
10
100
1000
CA
21
dCA
dt
CA
Determination of Derivative
In order to carry out the Differential Method, it is
necessary to calculate the derivatives from the
concentration Vs. time data.
There are 3 different methods to determine the
derivative.
Graphical method
Numerical Method
Polynomial Method
Graphical Method
Determination of Derivative
Derivative by building tangents is prone to errors.
CA
time
1.6
1.4
-dC/dt
1.2
1
0.8
0.6
0.4
0.2
0
0
10
15
20
t [min]
24
Numerical Method
Determination of Derivative
Can be used, when data points are equally spaced
such as t1 - t0 = t2 - t1= t
The three point differentiation formulas can be used.
Initial point
3C A 0 4C A 1 C A 2
dC A
)t 0
dt
2 t
Intermediate points
(
Last point
dC A
1
)ti
dt
2 t
A ( i 1)
C A (i 1)
C A (n2 ) 4C A (n1) 3C A (n )
dC A
(
)tn
dt
2 t
25
Polynomial method
Determination of Derivative
Step 1: Fit CA vs t data using a polynomial of
n th order: (many software packages can do that)
CA = ao +a1t +a2t2+ an tn
Step 2: After determining the polynomial, it has to
be differentiated with respect to time
i.e. Calculate dCA /dt
dCA /dt = a1 + 2 a2t+ (n) an tn-1
26
Summary
Rate laws can be determined experimentally in many ways.
Integral Method
Integrate the design equation and rearrange.
Determine whether the data fits the proposed line.
Trial and error.
Differential Method
Suitable to irreversible reactions with one reactant only.
Must find the derivative, dCA/dt
Not trial and error.
27
Tutorial #8
1. Integral method
t [min]
12
2.50 2.00
15
18
21
2. Differential method
Determine the rate law of reaction using the
numerical method and the polynomial method
t [min]
12
15
CA
[mol.L-1]
15
11.0
8.0
6.0
4.5
3.5
28
CA0
FA0 FA (rA ) V 0
2. Rate Law
3. Stoichiometry
FA
CA
(rA ) k C A
v = vo
4. Combine
v0 [C A0 C A ] ( rA ) V
v0 [C A0 C A ]
(rA )
V
29
1
4.5
6
19
24
53
30
1
4.5
CA
v0
(L/min) (mmol/L)
1
4.5
6
19
24
53
6
19
24
53
CA0-CA
(mmol/L)
95.5
81
47
v0 [C A0 C A ]
(rA )
V
(-rA)
(mmol/L-min)
95.5
486
1128
6.0
5.0
y = 1.009x + 3.092
R2 = 0.993
4.0
3.0
Slope = = 1
2.0
1.0
0.0
0.0
1.0
2.0
3.0
4.0
ln (CA)
k = exp(3.092) min-1
= 22.021 min-1
32
5.0
ln (-d CA0/dt)
ln (CA0)
dCHCl
dt
(rHCl )0 kCHCl
,0
0
35
4M HCl
Run 2
4.0000
1.0000
3.9990
0.9990
C (HCl)
C (HCl)
Run 1
3.9980
0.9980
3.9970
0.9970
3.9960
0.9960
t [m in]
t [m in]
36
dCHCl
dt
(rHCl )0 kCHCl
,0
0
dCHCl
ln
dt
ln k ln CHCl,0
0
CA
time
37
C(A)
C(A)
C(A)
C(A)
4.00
1.00
2.00
0.1000
3.86
0.965
1.93
0.0960
3.75
0.93
1.87
0.0935
3.65
0.90
1.81
0.0915
3.55
0.87
1.75
0.0900
38
Method of
Half-life (t1/2) is the time taken for the concentration to
drop to 1/2 of the initial value.
We can find and k by finding t1/2 as a function of CAO.
rA k A C
t t
CA
CA 0
CA
CA
dC A
k A C A
dt
dCA
dt t 0 t
kC A
t 0
dCA
1
1 C
t
C A dC A
kC
k
k
(
1
)
A
CA 0
CA 0
1
A
CA
CA 0
1
1
k( 1) CA1
39
CA
CA 0
Method of Half-Lives
1
1
t
k( 1) CA1
CA
CA 0
1
1
1
1 1
k( 1) C A
CA0
C
1
t
kCA01( 1) C
1
A0
1
A
1
1
C
1
A0
kC A 0 ( 1) C A
CA0
1
t 1/ 2
1
1
kC A 0 ( 1) (1/ 2)C A 0
t 1/ 2
1
2 1
1
2 1
1
kC A 0 ( 1)
k( 1)CA01
40
Method of Half-Lives
Taking logarithms of both sides of the equation, we have
t 1/ 2
k( 1)CA01
ln t 1/ 2
2
ln
1
(1 )lnC A 0
k( 1)
ln CA0
41
Method of Excess
rA
kA
C A CB 42
Experimental Planning
4 to 6 weeks in the lab can save you 1 hour in the
library G.C. Quarderer, Dow Chemical
Examine the need for the experiment
Define objectives
Choose responses you measure
Identify important variables
Perform experiment
Analyze results
Act on results
43
PDCA
PLAN
DO
CHECK
ACTION