5.

Kinetic parameters estimation from isothermal experimental data

Flow catalytic reactor Batch high pressure reactor

outlet inlet

reactor

catalyst

SiO2 porous plugs

oven

700oC
 Laboratory flow reactor for kinetic experiments

CO2
CH4

High pressure bottles

mixing unit
OVEN Ar

Inlet
+ He
REACTOR H2
AIR
Gas chromatograph
PC
Reaction rate evaluation from ideal reactors

CSTR PFR BATCH

+ Direct calculation of r.r. + Simple realization + Simple realization
- Temperature control + High range of VR/F - Temperature control
- Ideal mixing - Gradients of temperature - Ideal mixing
and composition

Fjo X j 1 dX j o
rV  rV  rV 
n
1 j dX j
 j VR  j d VR / Fjo   j VR dt
Fjo  Fj
Xj 
Fjo
Strategy of kinetic experiment
1. Choice of measured components
2. Choice of reactor
3. Formulation of kinetic model based on mechanism of reaction and mathematical
model of reactor r  f (T ). f (c ). f (catalyst activity)...
1 2 i
4. Choice of temperature, composition and flow rate range
5. Statistical method for kinetic parameter estimation NO
6. Experimental data measurement
7. Evaluation of kinetic parameters
8. Results analysis Does the kinetic model describe well our data ?

YES

HOURRAH, we can publish our

results or we can design our industrial
reactor, ….
Experimental methods
Methods “Ex-situ” and “In-situ”
> gas chromatography, mass spectrometry, UV-VIS spectrometry ...
> NMR, FTIR, electrochemical methods...
> volume variation, optical properties, temperature variation, mass variation, ...
Kinetic parameters estimation
Isothermal batch reactor, constant volume
Example:
A  products, rV  kc An

Differential method Integral method

 
t1 c A,1 rV ,1 1 n
rV 
1 dc A
 t2 c A,2 rV ,2 c1A n  c Ao  (n  1)kt (n  1), c A  c Ao e  kt (n  1)
 A dt
. . .
 1  dc  
ln   A    ln(rV ,i )  ln(k )  n ln(c A )
 A  dt i 
Example

Diazobenzenchloride is decomposed following stoechiometric equation:

C6H5N2Cl(l)  C6H5Cl(l) + N2(g)

1 l of solution containing 150 g C6H5N2Cl was placed in an isothermal batch reactor. The
volume of evolving nitrogen was measured as a function of time at 70oC and at 100 kPa:

t [min] 0 1 2 3 4 5 6 7
volume 0 1.66 3.15 4.49 5.71 6.81 7.82 8.74
N2 [litr]

We should

a) formulate a mathematical model of reactor,

b) determine a reaction rate at given interval of time by the differential method,
c) estimate a reaction rate constant and order of reaction with respect to C 6H5N2Cl
using differential method,
d) estimate a reaction rate constant and order of reaction with respect to C 6H5N2Cl
using inegral method.

We assume ideal gas, constant volume of liquid phase, negligible solubility of nitrogen in
liquid phase.
Molar weight of C6H5N2Cl is 140,572 kmol/kg.
Differential
method PVN2 1
dc1/dt[mol/l/
X1 
t [min] VN2 [l] X1 ln(c1) [mol/l] min] ln(dc1/dt)
RT n1o
0 0 0 0.064851
1
2
1.66
3.15
0.055101
0.104559
0.008174
-0.045589
0.058793
0.052772
-2.83373
-2.94177
c1  c1o (1  X1 )
3 4.49 0.149039 -0.096537 0.047459 -3.04788
4 5.71 0.189535 -0.145296 0.043209 -3.1417  dc1   c1 (ti )  c1 (ti 1 ) 
   
5 6.81 0.226048 -0.191394 0.038959 -3.24524
 dt ti  ti  ti 1 
6 7.82 0.259573 -0.235677 0.035772 -3.3306
7 8.74 0.290111 -0.277795 0.032584 -3.42393

ln(c1) -2.8
-0.3 -0.3 -0.2 -0.2 -0.1 -0.1 0.0 0.1
-2.9

y = 2.0591x - 2.8484 -3.0

R² = 0.9997
-3.1
ln(dc1/dt)
k=0.05794 (mol.l-1) (1-n) min-1 -3.2
n=2.0591
-3.3

-3.4

-3.5
 Integral method

Non linear weighted least squares - Gauss-Newton method

Objective function
NEXP 2

 ( k , n)   w  X
i 1
i
EXP
(ti )  X MODEL (ti , k , n) 

Model
dX MODEL
   
n 1 n
 k c1o 1  X MODEL
dt
t  0, X MODEL  0

X EXP (ti )  experimental values of conversion

at t  ti
X MODEL (ti , k , n)  calculated values of conversion
at t  ti and for given k , n.
1
wi weights 
 i2
Athena Visual Studio
http://www.athenavisual.com/
 Sum of squares of deviations as a function of parameters k and

Very flat objective

2.00 function in the direction
1.80 of parameter n
1.60 further experimental
1.40
data needed to obtain
reliable value of n
Sume osf squares

1.20

1.00

0.80

0.60

0.40

2.19
0.20

2.13
2.06
2.00
0.00 1.94
1.88
1.82

0.0541 0.0558 0.0574 0.0590 0.0606 0.0623 0.0639

n, order of reaction
k, reaction rate constant

Further reading
Yonathan Bard: Nonlinear Parameter Estimation, McGraw-Hill, 1967