Chemical Reaction Engineering 8

Collection and Analysis

of Rate Data
 Objectives
• Determine the reaction order and specific reaction rate
from experimental data obtained from either batch or flow
reactors.
• Describe how to use equal-area differentiation, polynomial
fitting, numerical difference formulas and regression to
analyze experimental data to determine the rate law.
• Use regression software to evaluate the rate law
parameters given experimental data.
• Describe how the methods of half lives, and of initial rate,
are used to analyze rate data.
• Describe two or more types of laboratory reactors used to
obtain rate law data along with their advantages and
disadvantages.
Prof. Saleh Rawadieh 2
The Algorithm for Data Analysis for Homogenous systems

• Suppose that we have concentration time data:

– From this data we need to obtain the reaction rate and
order
• To analyse our data we should follow the following algorithm
1. Postulate the rate law
• Power law models for homogeneous reactions
 rA  kCA ,  rA  kCA CB
2. Select reactor type and corresponding mole balance.
• For Batch reactor (use mole balance on reactant A)
dC A
 rA  
dt

Prof. Saleh Rawadieh 3

The Algorithm for Data Analysis for Homogenous systems

• For PFR (use mole balance on product P (A→P)

FP CP vo
r  
'

W W
A

3. Process your data in terms of measured variable (e.g. NA, CA,

PA).
• If necessary, verite your mole balance in terms of the
measured variable
4. Look For simplifications.
• For example if one of the reactants in excess. assume its
concentration constant. If the gas phase mole fraction
of reactant is small set ε=0.

Prof. Saleh Rawadieh 4

The Algorithm for Data Analysis for Homogenous systems

5. For batch reactor calculate –rA as a function of concentration C,

to determine reaction order.
– Use differential analysis:
• Combine the mole balance with the power law model
 dC A
 rA  kCA ,   kCA
dt
• Take the integral

 dC A 
ln     ln( rA )  ln( k )   ln( C A )
 dt 
• Find (dCA/dt) from CA vs t data (graphical method, finite
deferential method, polynomial method)

Prof. Saleh Rawadieh 5

The Algorithm for Data Analysis for Homogenous systems
• Plot (-dCA/dt) vs lnCA to find reaction order α which is
the slope of the line
• Find k
– Use Integral analysis:
• Guess α and integrate dC A 
  kCA
dt
• Rearrange in terms of CA, and plot CA vs time. If the plot
is linear then your guess is correct, if not, guess again new
value
• If non of your guesses fit the data then go to the next
step
• Use non linear regression in polymath

Prof. Saleh Rawadieh 6

Batch Reactor Data
• Batch reactor used to determine rate law parameters for
homogenous systems
• This is done by recording concentration data with time and using
of the following methods to determine rate order and rate
constant:
– Differential method
– Integral method
– Polynomial regression method
• If other reaction parameter other than concentration is
monitored (pressure), then the mole balance should be written
in terms of the monitored parameter

Prof. Saleh Rawadieh 7

Batch Reactor Data
• For irreversible reaction A → P, we have
dC A
 rA    k AC A
dt
• For irreversible reaction A + B → P, we have
 rA  k ACA CB
• Here α and β are unknown, this can be simplified by
running the reaction with execs of B, so that CB remains
almost constant and the rate becomes
 rA  k 'C A k '  k ACB  k ACBo


• After determining α, the reaction can be run with execs of A

so that CA is constant

Prof. Saleh Rawadieh 8

Batch Reactor Data
• After determining α, the reaction can be run with execs of A
so that CA is constant, hence the rate law becomes

 rA  k ''CB k ''  k AC A  k AC Ao

• Once α and β are known, kA can be calculated from

measurements of –rA at known concentrations of A and B

 rA
k A     (dm3 / mol)   1 / s
C A CB
• Both α and β can be determined by using the method of excess,
coupled with a differential analysis of data for batch systems.

Prof. Saleh Rawadieh 9

Batch Reactor Data: Differential Method of Analysis
• Consider isothermal reaction carried out in constant
volume batch reactor, and concentration is recorded as a
function of time
• By combining the mole balance with rate equation we have

dCA
  k AC A
dt
 dC A 
ln     ln( k A )   ln( C A )
 dt 

• Here –dCA/dt should be calculated (we will learn that later)

Prof. Saleh Rawadieh 10

Batch Reactor Data: Differential Method of Analysis
• Methods for calculating (–dCA/dt)
– Graphical differentiation
– Numerical differentiation formulas
– Differentiation of a polynomial fit to the data
• Graphical differentiation: this method involves
• Plotting ΔCA/Δt vs time
• Using equal area differentiation to obtain (dCA/dt)

Prof. Saleh Rawadieh 11

Batch Reactor Data: Differential Method of Analysis

• Tabulate CA and time as shown below

• For each interval calculate ΔCA and Δt
• ΔCA = CAn – CA(n-1), and Δt = Δtn – Δtn-1
• For more information see Appendix A2 in Fogler

Prof. Saleh Rawadieh 12

Batch Reactor Data: Numerical Method of Analysis
• Numerical differentiation formulas can be used when the data
points in the independent variable are equally spaced.
such as t1 –to = t2 –t1 = Δt
Time (min) to t1 t2 t3 t4 t5
Concentration (mol/L) CAo CA1 CA2 CA3 CA4 CA5

Use The three-point differentiation formulas

First Point  dC A   3C Ao  4C A1  C A2
   .......1
 dt to 2t
 dC A  (C A(i 1)  C A(i 1) )  dC A  (C A2  C Ao )
Interior Points  dt   2t
,   
 dt t1 2t
....2
ti

Prof. Saleh Rawadieh 13

Batch Reactor Data: Numerical Method of Analysis
Last Point

 dC A  C A3  4C A4  3C A5
   ......3
 dt t 5 2t

Equation 1 is used to calculate the first dCA/dt

Equation 2 is used to calculate all intermediate data points
Equation 3 is used to calculate the last dCA/dt

Prof. Saleh Rawadieh 14

Batch Reactor Data: Polynomial Fit Analysis
• Another technique to differentiate the data is to first fit the
concentration-time data to an nth-order polynomial:

C A  ao  a1t  a2t 2  a3t 3      ant n

dC A
 a1  2a2t  3a3t 2      nant n1
dt

Prof. Saleh Rawadieh 15

Batch Reactor Data: Polynomial Fit Analysis
• Another technique to differentiate the data is to first fit the
concentration-time data to an nth-order polynomial:
3
CA = 0.0008t4 - 0.0141t3 + 0.052t2 + 0.2974t + 0.0102
2.5

2
Concentration

1.5

0.5

0
0 2 4 6 8 10 12 14
Prof. Saleh Rawadieh 16
Time
Batch Reactor Data: Polynomial Fit Analysis
• For this example we have:
dCA/dt = 0.0032t3 – 0.042t2 + 0.104t + 0.297
1.2

0.8
dCA/dt

0.6

0.4

0.2

0
0 2 4 6 8 10 12 14
Time
Prof. Saleh Rawadieh 17
Finding the Rate Law Parameters
• Now, using either the graphicaI method, differentiation
formulas, or the polynomial derivative, the following table can
be set up
Time (min) to t1 t2 t3 t4 t5
Concentration (mol/L) CAo CA1 CA2 CA3 CA4 CA5
Derivative (dCA/dt)o (dCA/dt)1 (dCA/dt)2 (dCA/dt)3 (dCA/dt)4 (dCA/dt)5

• The plot of ln(–dCA/dt) vs ln(CA) gives straight line with

slope equal to α and intercept equal to ln(kA)

 dC A 
ln     ln( k A )   ln( C A )
 dt 

Prof. Saleh Rawadieh 18

Finding the Rate Law Parameters: Example 5-1
• The reaction of triphenyl methyl chloride (trityl) (A) and
methanol (B) was carried out in a solution of benzene and
pyridine at 25°C. Pyridine reacts with HCI that then precipitates
as pyridine hydrochloride thereby making the reaction
irreversible

• The concentration-time data In was obtained in a batch reactor

Time (min) 0 50 100 150 200 250 300
Concentration (mol/dm3) x 103 50 38 30.6 25.6 22.2 19.5 17.4

Prof. Saleh Rawadieh 19

Finding the Rate Law Parameters: Example 5-1
• The initial concentration of methanol was 0.5 mol/dm3.
• Part (I) Determine the reaction order with respect to triphenyl
methyl chloride.
• Part (2) In a separate set of experiments, the reaction order wrt
methanol was found to be first order. Determine the specific
reaction rate constant.

Time (min) 0 50 100 150 200 250 300

Concentration (mol/dm3) x 103 50 38 30.6 25.6 22.2 19.5 17.4

Prof. Saleh Rawadieh 20

Finding the Rate Law Parameters: Example 5-1
• Step 1: Rate law  rA  kCA CB
• Because the concentration of methanol (B) is 10 times the initial
concentration of triphenyl methyl chloride (A), its concentration is
essentially constant
CB  CBo

• Hence  rA  kCBoC A  k 'C A
• The combination of mole balance and rate law is
dC A
  k 'C A
dt
• Taking the natural logarithm gives

 dC A 
ln     ln k '
   ln C A 
 dt 
Prof. Saleh Rawadieh 21
• Step 2: Calculate  dC A 
 
 dt 

• Graphical method:
Time CA x 103 -(ΔCA/Δt) x 104 -(dCA/dt) x 104
0 50
2.4
50 38
1.48
100 30.6
1
150 25.6
0.68
200 22.2
0.54
250 19.5
0.42
300 17.4
Prof. Saleh Rawadieh 22
• Step 2: Calculate
• Graphical method. Now plot the third column versus time

• The values of -(dCA/dt) are

indicated by the arrows
• Now complete the table

dC A x10 4

dt
C A x10 4

t
mol
dm 3 min

Prof. Saleh Rawadieh 23

• Step 2: Calculate  dC A 
 
 dt 

• Graphical method:
Time CA x 103 -(ΔCA/Δt) x 104 -(dCA/dt) x 104
0 50 3.0
2.4
50 38 1.86
1.48
100 30.6 1.2
1
150 25.6 0.8
0.68
200 22.2 0.5
0.54
250 19.5 0.47
0.42
300 17.4
Prof. Saleh Rawadieh 24
• Step 2: Calculate  dC A 
 
 dt 
• Finite Difference Method
 dC A   3C Ao  4C A1  C A2  3(50)  4(38)  30.610
3
t 0      2.86 104
 dt to 2t 2(50)

t  50
 dC A  (C A2  C Ao )  dC A  30.6  50103
 1.94 104
     
 dt t1 2t  dt 50 2(50)

t  100
 dC A  (C A3  C A1 )  dC A  25.6  38103
 1.24 104
     
 dt t2 2t  dt 100 2(50)

t  150
 dC A  (C A4  C A2 )  dC A  22.2  30.6103
 0.84 104
     
 dt t3 2t  dt 150 2(50)

t  200
 dC A  (C A5  C A3 )  dC A  19.5  25.6103
 0.61104
     
 dt t4 2t  dt  200 2(50)

t  250
 dC A  (C A6  C A4 )  dC A  17.4  22.2103
 0.48 104
     
 dt t5 2t  dt  250 2(50)
Prof. Saleh Rawadieh 25
• Step 2: Calculate  dC A 
 
 dt 
• Finite Difference Method
• The last point
 dCA  C A4  4C A5  3C A6 22.2  4(19.5)  3(17.4)10
3
t  300      0.36 104
 dt t 6 2t 2(50)

• Polynomial Method.
– Plot Concentration vs time
– Use the Trendline option on excel to fit your
data
– Differentiate your polynomial and calculate
the derivative
Prof. Saleh Rawadieh 26
• Step 2: Calculate  dC A 
 
 dt 
• Polynomial Method.
C A  0.04999  2.978 104 t  1.343106 t 2  3.485 109 t 3  3.697 1012 t 4
 dCA  5 2 8 3
  10  0.2987  0.002687t  1.045 10 t  1.479 10 t
3
60
 dt 
50

40
Concentration

30

20

10

0
0 50 100 150 200 250 300 350
Prof. Saleh Rawadieh 27
Time (min)
• Step 2: Calculate   dC A 
 dt 

• Values from the three methods

Graphical Finite Polynomial

Time
 (dCA / dt ) 10  (dCA / dt ) 10
4 4
 (dCA / dt ) 10
4 C A 103
0 3.00 2.86 2.98 50

50 1.86 1.94 1.88 38

100 1.20 1.24 1.19 30.6

150 0.80 0.84 0.8 25.6

200 0.68 0.61 0.6 22.2

250 0.54 0.48 0.48 19.5

300 0.42 0.36 0.33 17.4

Prof. Saleh Rawadieh 28

• Step 3: Calculate the reaction order and k
• The plot (ln(dCA/dt) vs ln(CA ) normal graph

1.5
6.9096x - 2.0608y =
Slope = 2, α = 2 (2nd order)
1
Graphical

Finite
0.5
Polynomial
ln(dCA/dt)

0
Polynomial)( ‫خطي‬
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

-0.5

-1

-1.5
ln(CA)

Prof. Saleh Rawadieh 29

• Step 3: Calculate the reaction order and k
• The plot (ln(dCA/dt) vs ln(CA ) normal graph  dC A 
 
 dt p
k'  2
C Ap
• Pick any two values from the table, say 0.54 and 19.5
0.5 104 mol / dm3 min
k 
'
3
 0.125dm 3
/ mol. min
(20 10 mol / dm ) 3 2

• The reaction was said to be first order wrt methanol, β= 1,

 k'
k  kCBo
'
 k  1  0.12 / 0.5  0.24
CBo

 rA  0.24(dm3 / mol) 2 CA2CB

Prof. Saleh Rawadieh 30

• Integral method
• In the integral method of analysis of rate data, we are looking for
the appropriate function of concentration corresponding to a
particular rate law that is linear with time
• Consider A → P occurring in a constant volume batch reactor
dC A
 rA
dt
• For zero order reaction
dC A
 k Integratio
n  C A  C Ao  kt
dt
• A plot of CA versus time should be
linear with slope = k

Prof. Saleh Rawadieh 31

• Integral method
• For first order reaction
dC A C Ao
  kCA  ln
Integration
 kt
dt CA
• A plot of ln(CAo/CA) vs. time should
be linear with slop = k and start
from origin

Prof. Saleh Rawadieh 32

• Integral method
• For Second order reaction
dC A 1 1
  kCA 
2 Integration
  kt
dt C A C Ao
• A plot of (1/CA) vs. time should be
linear with slop = k and start from
(1/CAo)

Prof. Saleh Rawadieh 33

• Example 5-2, redo example 5-1
• Assume second order with α = 2
dC A '  1 1
  k C A  k C A 
' 2 Integration
  k 't
dt C A C Ao
t 0 50 100 150 200 250 300
CA 0.05 0.038 0.0306 0.0256 0.0222 0.0195 0.0174
1/CA 20 26.31579 32.67974 39.0625 45.04505 51.28205 57.47126

70

60
20.118x + 0.1248y =
50

40

30

20

10

0
0 50 100 150 200 250 300 350
Prof. Saleh Rawadieh 34
• Example 5-2, redo example 5-1
• Assume second order with α = 2
• Slope = k’ = 1.24 dm3/mol. Min
2
k ' 3
0.12dm mol min1 1
 dm 
3
k   0.24  / min
CBo 0.5mol / dm3  mol 

See powerpoint solution to homework xxx2

Prof. Saleh Rawadieh 35

Differential Reactors

• A→P
• All calculation must be performed wrt the product P
• Experimental data may be in terms of concentration or pressure
• Mole balance on A yields

FAo  FAe
 rA  , e : exit
W
voC Ao  vCAe
 rA  , e : exit
W
Prof. Saleh Rawadieh 36
Differential Reactors
• A→P
• All calculation must be performed wrt the product P
• Experimental data may be in terms of concentration or pressure
• Mole balance on P yields FAo X FP
 rA  
W W
• For constant volumetric flow rate:
voC Ao  voC Ae voCP
 rA  
W W
• Rate of reaction is expressed as a function of product
concentration

Prof. Saleh Rawadieh 37

Differential Reactors
• In such reactor, the catalyst is small and the flow rate is high, this
results in almost no change in the concentration of A
C Ao  C Ae  0
C Ao  C Ae  C Ab
C  C Ae
C Ab  Ao
2
• CAb is the concentration in the catalytic bed

 rA  kCAb

Prof. Saleh Rawadieh 38

Differential Reactors
• In such reactor, the catalyst is small and the flow rate is high, this
results in almost no change in the concentration of A
C Ao  C Ae  0
C Ao  C Ae  C Ab
C  C Ae
C Ab  Ao
2
• CAb is the concentration in the catalytic bed

 rA  kCAb

• See example 5-5

Prof. Saleh Rawadieh 39