Kajian tentang penentuan kinetika hydrodealkilasi mesitylene telah dilakukan oleh Samuel E.Shull, 1966
[1] secara analitik. Hasilnya diperoleh tiga konstanta kecepatan reaksi untuk tiga reaksi yang merupakan fungsi
suhu sesuai persamaan Arrhenius dengan orde reaksi sebesar 1.5. Fogler, 2006 {2] telah melakukan simulasi
berdasarkan data tersebut dengan menggunakan Polymath dengan hanya melibatkan dua reaksi saja untuk
mengetahui waktu reaksi optimum dari hasil grafik yang diperoleh. Kajian pertama yang dilakukan oleh penulis
adalah mensimulasi data dari Samuel E.Shull sehingga diperoleh hubungan konsentrasi zat sebagai fungsi waktu
yang dibatasi maksimal 0.5 jam. Hubungan konsentrasi dan waktu ini kemudian dianggap sebagai data yang
akan digunakan untuk menentukan konstanta kecepatan reaksi dengan optimasi sum square error (SSE)
menggunakan Hooke-Jeeve dan penyelesaian persamaan differensial menggunakan metode Rungge-Kutta.
Optimasi pertama dilakukan dengan menggunakan QuickBasic (QB) dan optimasi kedua dilakukan dengan Scilab
5.3.3.
Suhu reaksi yang dipilih 1500R dan 35 atm dalam reaktor packed-bed (fixedbed reaktor) dengan umpan
66.7% mol hydrogen dan 33.3% mol mesitylene.
Persamaan reaksi kimia:
CH3
CH3
+ H2
CH3
CH3
(mesitylene)
CH4
CH3
(m-xylene )
CH3
..(1)
CH3
+ H2
CH4
CH3
(m-xylene)
(toluene )
(2)
CH3
+ H2
(toluene)
simoehch.blogspot.com 1
(benzene )
CH4
(3)
k1 = 55.20 (ft3/lbmol)0.5.j-1
= 0.015334 (ft3/lbmol)0.5.det-1
k2 = 30.16 (ft3/lbmol)0.5.j-1
= 0.008378 (ft3/lbmol)0.5.det-1
k3 = 13.12 x (ft3/lbmol)0.5.j-1
= 0.003646 (ft3/lbmol)0.5.det-1
, lbmol/j.ft3
, lbmol/j.ft3
, lbmol/j.ft3
, lbmol/ ft3
, lbmol/ ft3
, lbmol/ ft3
, lbmol/ ft3
(ft3/lbmol)0.5. j-1
(ft3/lbmol)0.5. j-1
(ft3/lbmol)0.5. j-1
dCM
- r1
d
hidrogen :
dCH
- r1 - r2 - r3
d
m-xylene :
dC X
r1 - r2
d
toluene :
dCT
r2 - r3
d
r3
> B + me
y HO . P
(0.667) . (35)
0.021 lbmol/ft 3
R.T
(0.73) . (1500)
V
238 ft 3
0.5 h
vo 476 ft 3 / h
Ada 4 persamaan differensil dan harga awal
konsentrasi reaktan mesitylene dan hydrogen
diketahui. Menggunakan Scilab 5.3.3 dapat
diselesaikan PD di atas dengan programnya di
bawah ini. Hasil run berupa grafik dan 10 titik
simoehch.blogspot.com 3
=============================================
t (jam)
cM
cH
cX
cT
=============================================
0.05
0.00741
0.01762
0.00279
0.00028
0.10
0.00521
0.01466
0.00430
0.00094
0.15
0.00377
0.01230
0.00492
0.00166
0.20
0.00280
0.01038
0.00507
0.00233
0.25
0.00213
0.00879
0.00499
0.00291
0.30
0.00166
0.00746
0.00479
0.00339
0.35
0.00132
0.00633
0.00454
0.00379
0.40
0.00107
0.00536
0.00428
0.00410
0.45
0.00088
0.00453
0.00403
0.00435
0.51
0.00073
0.00381
0.00379
0.00454
=============================================
10
20
CLS
COLOR 3
PRINT " "
PRINT "
k1
"
PRINT "
A + B
>
D + E
"
PRINT "
k2
"
PRINT "
D + B
>
F + E
"
PRINT "
k3
"
PRINT "
F + B
>
G + E
"
PRINT " "
SLEEP
nn = 11: Dt = 1
DIM CAdat(nn), CBdat(nn), CDdat(nn), CFdat(nn)
DIM waktu(nn), CA(nn), CB(nn), CD(nn), CF(nn), ral(nn)
PRINT
PRINT " HASIL PENELITIAN"
PRINT " ----------------"
PRINT
FOR i = 1 TO nn
READ waktu(i), CAdat(i), CBdat(i), CDdat(i), CFdat(i)
NEXT i
'-------------------------------------------------' waktu (j)
CAdat
CBdat
CDdat
CFdat
'-------------------------------------------------DATA 0
, 0.01050 , 0.02100 , 0.00000 , 0.00000
DATA 180 , 0.00717 , 0.01732 , 0.00298 , 0.00033
DATA 360 , 0.00507 , 0.01445 , 0.00437 , 0.00099
DATA 540 , 0.00369 , 0.01215 , 0.00494 , 0.00171
DATA 720 , 0.00276 , 0.01027 , 0.00507 , 0.00237
DATA 900 , 0.00211 , 0.00872 , 0.00498 , 0.00294
DATA 1080 , 0.00165 , 0.00741 , 0.00478 , 0.00341
DATA 1260 , 0.00131 , 0.00629 , 0.00453 , 0.00380
DATA 1440 , 0.00106 , 0.00534 , 0.00428 , 0.00411
DATA 1620 , 0.00087 , 0.00452 , 0.00402 , 0.00435
DATA 1800 , 0.00073 , 0.00381 , 0.00379 , 0.00454
'-------------------------------------------------k1opt = .02:
k2opt = .008:
k3opt = .005
delk1 = .001:
delk2 = .001:
delk3 = .001
TOLk1 = .00001:
TOLk2 = .00001:
TOLk3 = .00001
RATIO = .6
'
PRINT " "
PRINT "
NO waktu(det)
CA
CB
CD
CF
"
PRINT "
-- ---------- -------------------------"
b$ = "
##
#####
#.#####
#.#####
#.#####
#.#####"
FOR i = 1 TO nn
PRINT USING b$; i; waktu(i); CAdat(i); CBdat(i); CDdat(i);
CFdat(i)
NEXT i
PRINT " "
PRINT
SLEEP
PRINT " Harga awal k1 = "; k1opt
PRINT " Harga awal k2 = "; k2opt
PRINT " Harga awal k3 = "; k3opt
PRINT " Delta k1
= "; delk1
PRINT " Delta k2
= "; delk2
PRINT " Delta k3
= "; delk3
PRINT " Toleransi k1 = "; TOLk1
PRINT " Toleransi k2 = "; TOLk2
PRINT " Toleransi k3 = "; TOLk3
PRINT " Perbandingan delta baru dan delta lama = "; RATIO
SLEEP
PRINT
PRINT " ---------------------------------------"
PRINT "
k1
k2
k3
sse
ralat %
"
PRINT " ---------------------------------------"
A$ = " #.######
#.######
#.######
##.####^^^^
###.#####"
REM program pokok minimasi Hooke-Jeeves
m = k1opt: n = k2opt: p = k3opt
GOSUB 100: Fopt = F
PRINT USING A$; k1opt; k2opt; k3opt; Fopt; Ralat
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30
40
41
43
50
'SLEEP
REM --eksplorasi-TANDA1 = 0: TANDA2 = 0: TANDA3 = 0
m = k1opt + delk1: n = k2opt: p = k3opt
GOSUB 100
IF F >= Fopt THEN 20
Fopt = F: k1opt = m: TANDA1 = 1
PRINT USING A$; k1opt; k2opt; k3opt; Fopt;
'SLEEP
GOTO 30
m = k1opt - delk1
GOSUB 100
IF F >= Fopt THEN 30
Fopt = F: k1opt = m: TANDA1 = -1
PRINT USING A$; k1opt; k2opt; k3opt; Fopt;
'SLEEP
m = k1opt: n = k2opt + delk2: p = k3opt
GOSUB 100
IF F >= Fopt THEN 40
Fopt = F: k2opt = n: TANDA2 = 1
PRINT USING A$; k1opt; k2opt; k3opt; Fopt;
'SLEEP
GOTO 41
n = k2opt - delk2
GOSUB 100
IF F >= Fopt THEN 41
Fopt = F: k2opt = n: TANDA2 = -1
PRINT USING A$; k1opt; k2opt; k3opt; Fopt;
'SLEEP
m = k1opt: n = k2opt: p = k3opt + delk3
GOSUB 100
IF F >= Fopt THEN 43
Fopt = F: k3opt = p: TANDA3 = 1
PRINT USING A$; k1opt; k2opt; k3opt; Fopt;
'SLEEP
GOTO 50
p = k3opt - delk3
GOSUB 100
IF F >= Fopt THEN 50
Fopt = F: k3opt = p: TANDA3 = -1
PRINT USING A$; k1opt; k2opt; k3opt; Fopt;
'SLEEP
IF
IF
IF
IF
Ralat
Ralat
Ralat
Ralat
Ralat
Ralat
70
-"
--------
PRINT
REM--cetak hasil-m = k1opt: n = k2opt: p = k3opt
GOSUB 100
PRINT USING " k1 OPTimum = #.######"; k11
PRINT USING " k2 OPTimum = #.######"; k22
PRINT USING " k3 OPTimum = #.######"; k33
PRINT "
Sum of squares of errors = "; F
'SLEEP
PRINT : PRINT
PRINT " ==============================================="
PRINT " PERBANDINGAN HASIL SIMULASI DAN DATA PERCOBAAN "
PRINT " -----------------------------------------------"
PRINT
PRINT "
"
PRINT " NO CA data CA sim CB data CB sim CD data CD sim CF
data CF sim % error "
PRINT " -- ------- ------- ------- ------- ------- ------- ------ ------- --------"
b$ = " ## #.##### #.##### #.##### #.##### #.##### #.#####
#.##### #.##### ##.#####"
FOR i = 1 TO nn
PRINT USING b$; i; CAdat(i); CA(i); CBdat(i); CB(i); CDdat(i);
CD(i); CFdat(i); CF(i); ral(i) * 100
NEXT i
PRINT "
"
PRINT USING "
##.#####"; Ralat
PRINT "
"
END
Dan seterusnya
k1
A + B
>
D + E
k2
D + B
>
F + E
k3
F + B
>
G + E
HASIL PENELITIAN
---------------
NO waktu(det)
CA
CB
CD
CF
-- ---------- ------------------------1
0
0.01050
0.02100
0.00000
0.00000
2
180
0.00717
0.01732
0.00298
0.00033
3
360
0.00507
0.01445
0.00437
0.00099
4
540
0.00369
0.01215
0.00494
0.00171
5
720
0.00276
0.01027
0.00507
0.00237
6
900
0.00211
0.00872
0.00498
0.00294
7
1080
0.00165
0.00741
0.00478
0.00341
8
1260
0.00131
0.00629
0.00453
0.00380
9
1440
0.00106
0.00534
0.00428
0.00411
10
1620
0.00087
0.00452
0.00402
0.00435
11
1800
0.00073
0.00381
0.00379
0.00454
-------k2
-------0.008000
0.008000
0.009000
0.010000
0.010000
0.009000
0.009000
0.009000
0.009000
0.008400
0.008400
0.008400
0.008400
0.008400
0.008400
0.008400
0.008400
0.008400
0.008383
0.008383
--------
-------k3
-------0.005000
0.005000
0.005000
0.005000
0.005000
0.005000
0.005000
0.004000
0.004000
0.004000
0.003400
0.003760
0.003630
0.003630
0.003630
0.003677
0.003660
0.003660
0.003660
0.003643
--------
k1 OPTimum = 0.015331
k2 OPTimum = 0.008383
k3 OPTimum = 0.003643
Sum of squares of errors =
----------sse
----------7.5225E-06
5.2849E-06
3.8264E-06
2.9811E-06
1.9341E-06
9.4642E-07
3.9202E-07
3.7205E-07
2.9274E-07
3.9719E-08
3.2978E-08
4.4995E-09
3.0820E-09
2.5861E-09
1.0244E-09
6.0202E-10
5.6288E-10
5.3618E-10
3.5361E-10
2.4488E-10
-----------
.6
--------ralat %
--------63.25762
53.09519
54.32685
53.80658
41.50533
30.61014
18.18442
17.62642
10.80501
3.00440
2.70682
1.63548
1.41756
1.18531
0.72519
0.71643
0.67142
0.58693
0.48790
0.43247
---------
2.44876E-10
===============================================
PERBANDINGAN HASIL SIMULASI DAN DATA PERCOBAAN
----------------------------------------------
NO CA data CA sim CB data CB sim CD data CD sim CF data CF sim % error
-- ------- ------- ------- ------- ------- ------- ------- ------- -------1 0.01050 0.01050 0.02100 0.02100 0.00000 0.00000 0.00000 0.00000
0.00000
2 0.00717 0.00717 0.01732 0.01732 0.00298 0.00298 0.00033 0.00033
1.02609
3 0.00507 0.00507 0.01445 0.01445 0.00437 0.00437 0.00099 0.00099
0.42199
4 0.00369 0.00369 0.01215 0.01215 0.00494 0.00494 0.00171 0.00171
0.20015
5 0.00276 0.00276 0.01027 0.01027 0.00507 0.00507 0.00237 0.00237
0.27489
6 0.00211 0.00211 0.00872 0.00872 0.00498 0.00498 0.00294 0.00294
0.28137
7 0.00165 0.00165 0.00741 0.00741 0.00478 0.00478 0.00341 0.00341
0.42566
8 0.00131 0.00131 0.00629 0.00629 0.00453 0.00453 0.00380 0.00380
0.20375
9 0.00106 0.00106 0.00534 0.00534 0.00428 0.00428 0.00411 0.00411
0.35942
10 0.00087 0.00087 0.00452 0.00452 0.00402 0.00402 0.00435 0.00435
0.64847
11 0.00073 0.00073 0.00381 0.00381 0.00379 0.00379 0.00454 0.00454
0.48293
0.43247
simoehch.blogspot.com 5
Penggunaan Scilab 5.3.3 untuk penyelesaian minimasi Hooke-Jeeve dan Runge-Kutta lebih menarik
karena adanya fasilitas grafik yang mendukung. Dari RUN program ini diperoleh ralat sebesar 6.92038%.
Ralat ini lebih besar dari hasil QB. Grafik 3 menunjukan konsentrasi hasil simulasi dan data yang sangat
mendekati meskipun ralat lebih besar dibandingkan hasil QB.
RUN Program 3.
===================================================
==== k1 ======= k2 ======== k3 ===== % Ralat ===== SSE ===
===================================================
0.020000
0.008000
0.005000
57.61624
1.439e-005
0.019000
0.008000
0.005000
48.42353
9.693e-006
0.019000
0.008000
0.004000
44.87128
7.884e-006
0.018000
0.008000
0.003000
35.38629
3.694e-006
0.017000
0.008000
0.003000
23.13393
1.407e-006
0.016000
0.008000
0.003000
14.61044
5.683e-007
0.016000
0.008000
0.004000
14.84130
5.450e-007
0.016000
0.008000
0.003400
12.87192
4.125e-007
0.016000
0.008600
0.003400
11.10264
4.085e-007
0.015400
0.008600
0.003400
6.70188
3.412e-007
0.015760
0.008600
0.003400
8.67116
2.968e-007
0.015760
0.008240
0.003400
8.47837
2.085e-007
0.015760
0.008456
0.003400
7.55055
2.016e-007
0.015760
0.008456
0.003616
7.11086
1.853e-007
0.015630
0.008456
0.003616
5.98596
1.804e-007
0.015630
0.008326
0.003616
6.31234
1.792e-007
0.015760
0.008326
0.003616
7.35693
1.674e-007
0.015760
0.008326
0.003538
7.39786
1.665e-007
0.015760
0.008373
0.003538
7.24431
1.654e-007
0.015760
0.008373
0.003585
7.19573
1.650e-007
0.015713
0.008373
0.003585
6.73996
1.638e-007
0.015730
0.008373
0.003585
6.89298
1.637e-007
0.015730
0.008356
0.003585
6.94843
1.637e-007
0.015730
0.008356
0.003568
6.96814
1.636e-007
0.015730
0.008366
0.003568
6.93174
1.635e-007
0.015730
0.008366
0.003578
6.92038
1.635e-007
==================================================
k1 optimum = 0.015730
k2 optimum = 0.008366
k3 optimum = 0.003578
Sum of squares of errors = 1.635e-007
Total kesalahan rata-rata = 6.92038
delk 1 = 0.0000060
delk 2 = 0.0000060
delk 3 = 0.0000060
===============================================
PERBANDINGAN HASIL SIMULASI DAN DATA PERCOBAAN
====================================================================================
=NO==CA data===CA sim===CB data==CB sim===CD data==CD sim===CF data===CF sim % error
====================================================================================
1 0.00717 0.00735 0.01732 0.01755 0.00298 0.00285 0.00033 0.00029 20.68806
2 0.00507 0.00512 0.01445 0.01455 0.00437 0.00437 0.00099 0.00095 5.65807
3 0.00369 0.00368 0.01215 0.01219 0.00494 0.00498 0.00171 0.00168 2.99538
4 0.00276 0.00272 0.01027 0.01027 0.00507 0.00512 0.00237 0.00236 2.91846
5 0.00211 0.00206 0.00872 0.00869 0.00498 0.00503 0.00294 0.00295 3.96989
6 0.00165 0.00159 0.00741 0.00737 0.00478 0.00483 0.00341 0.00343 5.52119
7 0.00131 0.00126 0.00629 0.00625 0.00453 0.00457 0.00380 0.00383 6.09005
8 0.00106 0.00101 0.00534 0.00529 0.00428 0.00430 0.00411 0.00414 6.54794
9 0.00087 0.00083 0.00452 0.00447 0.00402 0.00404 0.00435 0.00439 7.13093
10 0.00073 0.00069 0.00381 0.00377 0.00379 0.00380 0.00454
0.00459 7.79743
====================================================================================
Total kesalahan antara data percobaan dan hasil simulasi ============================ 6.92038
====================================================================================
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Grafik 3. Hubungan waktu reaksi dengan konsentrasi dari data dan hasil simulasi
simoehch.blogspot.com 7
Berdasarkan nilai k1. k2 dan k3 hasil simulasi yang nilai ralatnya relative kecil, penggunaan
optimasi Hooke-jeeve dan Runge-Kutta dalam penentuan nilai konstanta kecepatan reaksi bisa
diandalkan. Selain penentuan nilai k, juga bisa memperkirakirakan orde reaksi untuk berapapun reaksi
yang terjadi, dalam hal ini 3 reaksi atau 3 variabel yang dicari. Jika orde reaksi berbeda kita hanya perlu
merubah persamaan kecepatan reaksi saja dan program lainnya tetap.
SEMOGA TULISAN INI BERMANFAAT. TERIMAKASIH
LITERATUR
[1] Samuel E.Shull, and A.N. HIXSON, Kinetics of Thermal Hydrodealkylation of Mesitylene, m-Xylene
and Toluene, Ind. Eng. Chem. Process Des. Dev., 5, 2 (1966) 146-150.
[2] Fogler. H.Scott., Elements of Chemical Reaction Engineering , 4th ed., Prentice Hall Professional
Technical Reference., Boston (2006)
[3] Wahyudi Budi Sediawan., and Agus Prasetyo., Pemodelan matematis dan Penyelesaian Numeris
dalam Teknik Kimia., ANDI Yogyakarta (1997).
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