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Chemical Reaction

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)

Rate Laws from Lab Reactor Data


Measurement of concentrations
Methods of Data Analysis to obtain Rate Laws of
homogeneous reactions

Integral method
Differential method (using Batch and CSTR)
Method of initial rates
Method of half-lives.

Reaction Kinetics & Rate Law


(Recap)

Factors affecting rate of reaction


Concentrations
Temperature
Pressure

Rate law is an algebraic expression of the


rate of a reaction.
Rate law is a function of concentration and
temperature (through the rate constant, k)
-rA= [k(T)] [f(CA, CB, ...)]
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Rate Law Elementary Reactions


(Recap)

A reaction follows an elementary rate law if and


only if the stoichiometric coefficients are the
same as the individual reaction order of each
species.
For example, if the reaction aA+bB cC + dD, is
elementary, the rate law would be: -rA=kACAaCBb
a order with respect to A
b order with respect to B

If 2NO+O2 2NO2
then -rNO = kNO C 2 NO CO2 if it is elementary!
f(CA) is determined experimentally.
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Rate Laws from Lab Reactor Data


Weve seen how to write rate laws once we have a
reaction mechanism for elementary reactions.
It is important to check whether the proposed rate
law agrees with the experimentally-determined
rate law.
Now, well learn the methods for determining rate
laws from batch experiments using
Concentration versus time data from a constant volume
batch reactor.

Batch Reactors are primarily used for determining


rate laws of homogeneous reactions.
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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:

Direct measurement (GC, MS, etc)


Pressure measurements
Spectroscopic measurements (IR, UV, Vis)
Electrical measurements (conductivity, etc)

The concentration vs. time data obtained from


these measurements is mathematically analyzed
to determine the kinetics i.e. rate law.
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Methods of Data Analysis to obtain


Rate Laws from Batch Reactor Data
Various methods of analysis of data are:
Integral method
Differential method
Method of initial rates
Method of half-lives

All these methods also use Method of


Excess if the reaction has multiple
reactants.
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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.
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Integral Method Steps


1. General Mole Balance
2. Rate Law

dNA
(rA ) V
dt

(rA ) k CA

3. Stoichiometry

V=Vo

For constant density


system

4. Combine 1 dN A dC A (r )
A
with -rA

V dt

dt

CA

CA0

5. Assume zero, 1st or 2nd order


and carry out the integration
and plot the data.
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t t

dC A
dt

kCA t 0

Integral Method zero order


assumption

( 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
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Integral Method first order assumption


( rA ) k C A k C A

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
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Integral Method second order


assumption
( rA ) k C A k C A2

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

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Summary of Integral method


assuming 0th , 1st and 2nd order
Zero-order

First-order

Second-order

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Example - Integral Method


Data acquired from batch reactor experiment
t [min]
CA

2.0

1.60 1.35

15

22

1.10 0.87

30

40

0.70 0.53

60
0.35

[mol/L]

Determine the order of reaction and rate constant k


Start with zero-order

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Example - Integral Method - 0th Order


Zero-order: CA=CAO-kt
t [min]
CA

0 5

15

22

30

2 1.60 1.35 1.05 0.80 0.68

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

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Example - Integral Method 1st Order


First-order ln C A 0 kt
CA

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

Integral Method-1st order


2.50

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

Example - Integral Method 2nd Order


1
1
kt
CA
CA0

Second-order
t [min]
1 / CA

15

22

30

0.5 0.63 0.74 0.95 1.25 1.47

40

60

1.89

2.70

Integral Method- 2nd order


3.00
2.50

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

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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)

Suitable only for irreversible reactions, where


the rate is essentially a function of the
concentration of only one reactant.
aA products
Assume that the rate law is of the form:
-rA= kA CA
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Differential Method Steps 1-4


1. General Mole Balance

2. Rate Law

(rA ) k CA

3. Stoichiometry V=Vo
4. Combine

dNA
(rA ) V
dt

1 dNA
(rA )
V dt

For constant density system

dC A

k CA
dt
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Differential Method Steps 5-7


dCA

k CA
dt

dC A
ln(
) ln(k ) ln(C A )
dt

6. Plot: ln (-d CA/dt) vs. ln


(CA).

ln (-d CA/dt)

5. Taking the logarithms on both sides


of the above equation,

ln (CA).

7. Obtain from slope, k


from intercept
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Differential Method Alternative Steps 6-7


Alternatively, Reaction order
dCA
ln(

) 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
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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

We will go through all these methods now.


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Graphical Method
Determination of Derivative
Derivative by building tangents is prone to errors.
CA
time

A better method is as follows:


Determine CA for each time interval and calculate CA /
t.
Plot this CA / t against time.
Read - dCA/dt at t for which corresponding CA has
been measured.
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Determination of Derivative from


[CA vs t] data Graphical Method
Step 1: Calculate CA & t
Step 2: Plot - CA / t vs t

Step 3: Read - dCA/dt at t


for which corresponding
CA has been measured

1.6
1.4

-dC/dt

1.2
1
0.8
0.6
0.4
0.2
0
0

10

15

20

t [min]

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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
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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
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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.

When multiple reactants are involved, use Method of


Excess to find reaction order for each.
To be done: Method of Initial Rates and Method of Half-Lives

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Tutorial #8
1. Integral method
t [min]

CA [mol/L] 10.0 5.00 3.33

12

2.50 2.00

15

18

21

1.67 1.43 1.25

For the above set of data, determine the rate law


(order & rate constant) of the reaction.

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

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Differential Method for Obtaining


Rate Law using a CSTR
FA0

1. General Mole Balance

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

For constant density system

v0 [C A0 C A ]
(rA )
V
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Example: Rate Law from CSTR data


A CSTR is being used to determine the kinetics of
a reaction whose stoichiometry is A R.
For this purpose, various flow rates of an aqueous
solution of 100 mmol/L of A are fed to a 1.0 L
reactor, and
For each run the outlet concentration of A is
measured.
Find a rate expression to represent the following
data. (Assume that reaction is irreversible.)
v0 (L/min)
CA (mmol/L)

1
4.5

6
19

24
53
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Example: Rate Law from CSTR data


Data Treatment
v0 (L/min)
CA (mmol/L)

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

ln( rA ) ln( k ) ln( C A )


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Example: Rate Law from CSTR data


8.0
7.0
ln (-rA)

6.0
5.0

y = 1.009x + 3.092
R2 = 0.993

4.0
3.0

Slope = = 1

2.0
1.0

Intercept = ln(k) = 3.092

0.0
0.0

1.0

2.0

3.0

4.0

ln (CA)

k = exp(3.092) min-1
= 22.021 min-1
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5.0

Method of Initial Rates


Differential method is the most simple, but could
be ineffective if the reaction is reversible.
Unlike differential and integral methods, the
method of initial rates requires a series of
experiments instead of just one.
Carry out experiments at different initial
concentrations CAO and determine the initial rate
of reaction -rAO. Then plot to find rate law.
e.g. -rAO= (-d CA0/dt) = kCAO
ln (-rAO)= ln (-d CA0/dt) = ln (k) + ln(CAO)
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ln (-d CA0/dt)

Method of Initial Rates

ln (CA0)

The slope of this plot= order of the reaction and


Intercept = ln (k)
Similar to differential method.
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Method of Initial Rates (Example)


The dissolution of dolomite (calcium magnesium
carbonate) is a reaction important in the acid
stimulation of dolomite oil reservoirs.
4HCl + CaMg(CO3)2 Mg2+ + Ca2+ + 4Cl- + 2CO2 + 2H2O

The concentration of HCl was determined at


various times from AAS of the calcium and
magnesium ions.
The rate law for the initial rate can be written as

dCHCl

dt

(rHCl )0 kCHCl
,0
0
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Method of Initial Rates


(Example)
Determine the reaction order with respect to HCl
from the data presented below !
1M HCl

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]

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Method of Initial Rates (Example)


Taking logarithms of both sides of the rate law equation, we
have

dCHCl

dt

(rHCl )0 kCHCl
,0
0

dCHCl
ln

dt

ln k ln CHCl,0
0

The derivative at t = 0 can be found from the slope of the


plot of concentration versus time at t = 0. Or, by using the
formula for initial point as in the differential method.
3C A 0 4C A 1 C A 2
dC A
(
)t 0
dt
2 t

CA
time

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Method of Initial Rates


(Example)
For a set of 4 experiments, using 4 different initial
concentrations, we would generate the following data set:
time [min]

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
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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

Integrating the above equation:

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
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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

Half-life (t1/2) is the time it takes for the concentration to drop to


1/2 of the initial value.
i.e. CA = CA0 /2 when t = t . Substituting this in the eqn above,
1

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

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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 t is plotted against ln CA0. This means several experiments


at different initial concentrations have to be conducted.
Slope = 1-. From the Intercept, k can be found. Not suitable
for 1st order.
ln t 1/ 2

ln CA0

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Method of Excess

What if there are multiple reactants?


Method of excess can be used with all methods.
e.g. A + B products
-rA=kACACB
We run our reaction twice
First with excess B, so CB=CBO=constant through entire
reaction.
Then -rA=k CA where k=kACBO

Second, with excess A, so CA=CAO=constant through


entire reaction..
Then -rA=k CB where k=kACAO

Then, can calculate

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

Design of Experiment (DOE)

Perform experiment

Analyze results
Act on results

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PDCA
PLAN

Step 1 Select topic


Step 2 Plan activity schedule

DO

CHECK
ACTION

Step 3 Establish the present


situation
Step 4 Set target
Step 5 Identify causes & propose
solutions
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