Kinetika Reaksi Week 2:

Analisis dan Interpretasi Data

Reaktor Batch
Semester Genap 2020/2021

Dr. Hary Sulistyo

(hary@ugm.ac.id)

Program Magister Teknik Kimia

Departemen Teknik Kimia,
Fakultas Teknik,
Universitas Gadjah Mada
Learning Outcome
Level of Bloom Taxonomy
No Learning Outcome 1 2 3 4 5 6
M1 Mengembangkan persamaan kinetika reaksi berdasarkan √
mekanisme reaksi homogen.
M2 Mengembangkan bentuk umum dari kecepatan reaksi 
kimia berdasarkan pada mekanisme reaksi untuk sistem
heterogen dengan katalis dan tanpa katalis.
M3 Mengembangkan bentuk umum dari persamaan 
kecepatan reaksi kimia berdasarkan tahapan yang
mengontrol pada sistem heterogen dengan katalis dan
tanpa katalis.
M4 Mengembangkan kinetika reaksi gas-cair dan gas-padat 
dengan katalis dan tanpa katalitis.
M5 Menganalisis data eksperimen untuk menentukan √
kinetika reaksi.
M6 Memformulasikan model pada reaktor bio: batch dan 
kontinyu (chemostat).
M7 Memformulasikan model pada reaktor fixed bed satu 
dimensi pada berbagai kondisi.
Agenda:
• Analisis data percobaan: Metode Integral
• Analisis data percobaan dengan mencari derivatif:
❑ Metode Graphical
❑ Finite Difference
❑ Polinomial
• Non-Linear Least Square Analysis
Learning Outcome:
• M5 Menganalisis data eksperimen untuk menentukan kinetika
reaksi
Referensi:
Fogler, H. S., 2016, “Elements of Chemical Reaction Engineering”,
5th ed. Pearson Education, Inc. Boston.
Rangkaian Reaktor Batch
Penentuan kinetika umumnya dilakukan dalam reaktor batch

Keterangan gambar:
1. Labu leher tiga
2. Motor pengaduk
3. Termometer
4. Pendingin
5. Water bath
6. Klem
7. Statif
8. Pengaduk

Rangkaian alat penelitian dengan reaktor batch

Jenis data yang diperoleh umumnya berbentuk:

CA
t (min) t1 t2 t3 t4 t5 t6
CA CA1 CA2 CA3 CA4 CA5 CA6
t
Analisis Data: Integral Method
Consider the following reaction that occurs in a constant
volume Batch Reactor: (We will withdraw samples and
record the concentration of A as a function of time.)
A → Products

dNA
Mole Balances: = rAV
dt

Rate Laws: −rA = kCA


Stoichiometry: V = V0 Ditebak nilai k dan α
yang terbaik berdasar
dCA data percobaan
Combine:  − = kCA
dt

Analisis Data: Integral Method

Finally we should also use the formula to plot reaction rate

data in terms of conversion vs. time for 0, 1st and 2nd order
reactions.
Derivation equations used to plot 0th, 1st and 2nd order
reactions.
These types of plots are usually used to determine the
values k for runs at various temperatures and then used to
determine the activation energy.
Analisis Data: Integral Method
Dicoba dengan orde 0,1 dan 2:

Zeroth order First Order Second Order

dCA dCA dCA
= rA = −k = rA = −kCA = rA = −kCA2
dt dt dt

at t = 0, CA = CA 0 at t = 0, CA = CA 0 at t = 0, CA = CA 0
 CA 0  
 CA = CA 0 − kt  ln  = kt 
1
−
1
= kt
 CA  CA CA 0
 

 
Analisis Data: Integral Method
Guess and check for α = 0, 1, 2 and check against
experimental plot.
 =0  =1  =2
 C A0  1 1
CrAA = C A0 − kt ln   = kt − = kt
intercept  CA  C A C A0
slope slope intercept slope

CA ln(CA0/CA) 1/CA

t t t
Analisis Data: Differential Method
 dC A 
Taking the natural log of − = kC A 
 dt 
 dC A 
ln  −  = ln k +  ln C A
 dt 
 dCA 
The reaction order can be found from a ln-ln plot of:  −  vs CA
 dt 
dC A ln
−
dt

  dC A 
dC A − 
−
Slope = α  dt  p
dt P
k=
C Ap
ln
C AP CA
Analisis Data: Differential Method

We are usually given concentration as a function of time

from batch reactor experiments:

time (s) 0 t1 t2 t3
concentration CA0 CA1 CA2 CA3
(moles/dm3)

−𝑑𝐶𝐴
How to determine from this kind of data set?
𝑑𝑡
Analisis Data: Differential Method
Three ways to determine (-dCA/dt) from concentration-time data
• Graphical differentiation
• Numerical differentiation formulas
• Differentiation of a polynomial fit to the data
1. Graphical CA
−
t Equal size

t
 CA
−
t

dC A 
− 
 dt  0
dC A 
− 
dt  t1
dC A 
− 
dt  t 2

t
0 t1 t2
The method accentuates measurement error!
Analisis Data: Differential Method
2. Numerical differentiation formulas
Finite Difference Approximation

•Approximation for first derivative •Approximation for second order derivative

forward
d2 f f ( x + x) − 2 f ( x) + f ( x − x)
df f ( x + x) − f ( x) = centered
 first order error dx 2 x 2
dx x
df − f ( x + 2x) + 4 f ( x + x) − 3 f ( x)
 second order error
dx 2x

backward
df f ( x) − f ( x − x)
 first order error
dx x
df 3 f ( x) − 4 f ( x − x) + f ( x − 2x)
 second order error
dx 2x

centered
df f ( x + x) − f ( x − x)
 centered
dx 2x

Source: Chapra & Canale, Numerical Methods for Engineers 6th ed, McGrawHill, 2010
Analisis Data: Differential Method
2. Numerical differentiation formulas
time t0 t1 t2 t3 t4 t5
CA CA0 CA1 CA2 CA3 CA4 CA5

centered .................. centered

𝑑𝐶𝐴 𝐶𝐴2 −𝐶𝐴0 𝑑𝐶𝐴 𝐶𝐴5 −𝐶𝐴3
ቤ = ቤ =
𝑑𝑡 𝑡1 2Δ𝑡 𝑑𝑡 𝑡4 2Δ𝑡

forward backward
𝑑𝐶𝐴 −3𝐶𝐴0 + 4𝐶𝐴1 −𝐶𝐴2 𝑑𝐶𝐴 𝐶𝐴3 − 4𝐶𝐴4 +3𝐶𝐴5
ቤ = ቤ =
𝑑𝑡 𝑡0 2Δ𝑡 𝑑𝑡 𝑡5 2Δ𝑡
Analisis Data: Differential Method
3. Metode Polinomial
𝐶𝐴 = 𝑎0 + 𝑎1 𝑡+𝑎1 𝑡 2 + ⋯ + 𝑎𝑛 𝑡 𝑛
𝑑𝐶𝐴
= 𝑎1 +2𝑎2 𝑡 + 3𝑎3 𝑡 2 + ⋯ + 𝑛𝑎𝑛 𝑡 𝑛−1
𝑑𝑡
Non-Linear Least-Square Analysis
For concentration-time data, we can combine the mole

balance equation for −r A = kC A to obtain:

dC A
= −kC A
dt
 t = 0 C A = C A0

C1A−0 − C1A− = (1 −  )kt

Rearranging to obtain the calculated concentration as a
function of time, we obtain:

C Ac = C A = [C 1−
A0 − (1 −  )kt ]
1/(1− )
Non-Linear Least-Square Analysis
Now we could use Polymath or MATLAB to find the values of α and k
that would minimize the sum of squares of differences between the
measured (CAm) and calculated (CAc) concentrations.
That is, for N data points,

Similarly one can calculate the time at a specified concentration, tc

and compare it with the measured time, tm, at that same concentration.
That is, we find the values of k and α that minimize:
Non-Linear Least-Square Analysis

( )
N N
1 1− 2
s =  (CAmi − CAci ) = CAmi − C − (1 −  )kti 
2 2 1−
A0
i=1 i=1

We find the values of alpha and k which minimize s2

Dengan MATLAB mudah!

Example-Finding the Rate Law
• Reaksi
(C6H5)3CCl + CH3OH → (C6H5)3 COCH3 + HCl
A + B → C + D
Data konsentrasi
t = waktu reaksi, men
CA = konsentrasi A, mol/L
CBo = konsentrasi B mula-mula, 0,5 mol/L
Carilah persamaan kecepatan reaksi dengan metode integral,
diferensial, regresi non linier
Example-Finding the Rate Law
Data hasil percobaan:

t, min 0 50 100 150 200 250 300

CA 50 38 30,6 25,6 22,2 19,5 17,4

(mol/L).103
Example-Finding the Rate Law
Metode Integral:
Example-Finding the Rate Law
Metode Integral:

Dari hasil observasi, jika dipandang reaksi orde 2 yang terbaik maka diperoleh kinetika data
percobaan:

𝑑𝐶𝐴
= 𝑟𝐴 = −0,1248. 𝐶𝐴2
𝑑𝑡
Example-Finding the Rate Law
Metode diferensial:
Plot ln(CA) vs ln(-dCA/dt)

 dC A 
ln  −  = ln k +  ln C A
 dt 

intercept

slope
Example-Finding the Rate Law
Metode diferensial:
Perbandingan perhitungan (-dCA/dt) dengan berbagai metode:

Chapter 7: Fogler, 5th ed. Elements of Chemical Reaction Engineering,

Prentice Hall, 2016
Example-Finding the Rate Law
Metode diferensial:

Intercept: ln k=-2.092
Maka, k=exp(-2.092)=0.1234

slope: α=1.9959 ≈ 2

Dari hasil evaluasi, diperoleh kinetika data percobaan:

𝑑𝐶𝐴
= 𝑟𝐴 = −0,1234. 𝐶𝐴2
𝑑𝑡
Non-Linear Least-Square Analysis
Example:
Guess values for α and k and solve for measured data points then
sum squared differences:

CAm 1 0.7 0.5 0.35

CAc 1 0.5 0.33 0.25
(CAc-CAm) 0 -0.2 -0.17 -0.10
(CAc-CAm)2 0 0.04 0.029 0.01 0.07

for α= 2, k = 1 → s2 = 0.07
for α = 2, k = 2 → s2 = 0.27 C Ac = C A = [C1A−0 − (1 −  )kt ]1/(1− )
etc. until s2 is a minimum
Non-Linear Least-Square Analysis
Example:

Ilustrasi ini hanya memuat contoh 4 titik saja

Non-Linear Least-Square Analysis

3D Plot to Obtain Minimum

Sum of Squares 28
TERIMA KASIH