Problem 8 Parameter estimation in polymer degradation kinetics

The mechanism of polymer degradation reaction kinetics is suspected to follow Avrami or

random nucleation reaction,
( T −T 0 ) −E
f ( α )= A . exp ⁡( )
b RT

where f ( α )=−ln ( 1−α ) , T is the absolute temperature (K), b is the heating rate in K/min, A is the
frequency factor with units of rate constant, R is the gas constant (8.314 kJ/kmol-K) and T0 is the
activation temperature. Given that T0 = 338.75 K, b =10 K/min and conversion, α, at different
temperatures are as given in the table below.

Temp (K) 360 370 380 390 400 410

Conversion, 0.105 0.2010 0.342 0.5146 0.675 0.8026
α 5 5 7

By performing non-linear regression analysis, estimate the values of A and E from the
experimental data !
Pembahasan:

(ylabel grafik masih salah)

Gambar 1. Pengaruh Suhu terhadap Konversi
Pada kasus 8 dicari nilai factor frekuensi (A) dan Energi Aktivasi (E) yang
mengikuti persamaan Avrami mengenai kinetikam reaksi degradasi polimer. Dengan
menggunakan non-linier regression analysis, dilakukan penebakan pada nilai parameter
optimumnya , sehingga didapatkan nilai A dan E yang dapat dilihat dari table 1. Pada
gambar 1. Menunjukkan perbandingan data kalkulasi dan data eksperimen. Dari grafik
tersebut dapat dilihat bahwa error yang didapat dari perbandingan data kalkulasi dan
eksperimen kecil, yang artinya model persamaan kinetika sesuai dengan penelitian
tersebut.

Tabel 1. Hasil Simulasi nilai A dan E dengan fungsi lsqnonlin

Fungsi A E SSE
lsqnonlin 4.697 x 103 3.3829 x 104 0.0020
LAMPIRAN MATLAB
Problem 9 Combination of MOL and parameter estimation: tracer test
An undergraduate student wants to do a dispersion study on a laminer flow in an pipe with the
length of L. In this experiment, the pipe is continuously flowed with water. At a certain time, a
specific amount of tracer (pulse tracer) was injected at the front of the pipe (z = 0) with a
concentration of CA0. The tracer also undergoes a degradation reaction which follows the second
order reaction. If radial dispersion is neglected (due to the small diameter of the pipe), show that
the unsteady state equation that describes the concentration of the tracer in the pipe as a
function of distance and time is:

C  2C C
 Da 2  U  k C2
t z z
The concentration of the tracer at the inlet of the pipe (C A0 at z = 0) fluctuates with time
following the parabolic function of:
1
C A0  C A0,init 
900
 60  t  t 2 
Initial Conditions (IC):
t=0, hence C(z,0)=0
Boundary Conditions (BC):
1
C (0, t )  C A0,init 
900
 60  t  t 2 
z=0, hence
C
0
z=L, hence z
Data for modeling (all units are already assumed to be consistent):
L=1; dz=L./Nz k=1;
Nz=100; Da=2e-1; tspan=linspace(0,60,61);
CA0init=0.1; U=2e-1; IC=zeros(1,Nz);
TASK 1.
Run a simulation that illustrates the concentration of tracer in the pipe at various axial positions
(z) and time (t)! Draw the concentration distribution with imagesc!
TASK 2.
In another experiment, a student wants to find the value of Da from another tracer with the
same experiment. For this reason, he managed to measure the concentration of exit (z = L) as a
function of time. The results of measuring the concentration of the pipe’s exit as a function of
time are presented in the dataC.mat file. Calculate the Da values based on the available data!
Compare the plot concentration of pipe’s exit (z = L) based on experimental data and
modeling results! For optimization, use: initial guess Da use the value of Da in task 1, lower
bound (lb) = 0, upper bound (ub) = 1;

Jawab:
1. Penurunan Persamaan Permodelan

F,in F,out

Δz
Gambar 1. Elemen Volume pada Pipa
- Elemen volume (∆ v ¿= A . ∆ z

2. Neraca Massa pada Elemen Volume

∂C A ∂CA ∂ CA
[
−D A . A .
∂z z |
+U . A . C A|z − − D A . A .][∂z |z +∆ z
]
+U . A . C A|z+∆ z +k . C A 2 . A . ∆ z = A . ∆ z .
∂t

1
Persamaan diatas dikali dengan sehingga,
A .∆z
∂C A ∂C A

lim
DA .
∂z |
z+∆ z
−D A .
∂z |
z
=D A .
∂2C A
∆ z →0 ∆z ∂ z2

U . C A|z .−U . C A|z +∆ z ∂CA

lim =U .
∆ z →0 ∆z ∂z

Jadi,
2
∂ CA ∂CA 2 ∂C A
DA . 2
−U . −k . C A =
∂z ∂z ∂t