php/teknik
TEKNIK, 43 (1), 2022, 17 - 24
Abstrak
Singkong manis (Manihot esculanta) merupakan ubi-ubian dengan kandungan pati yang tinggi sehingga
dapat diolah untuk menghasilkan gula reduksi melalui proses hidrolisis. Salah satu jenis proses hidrolisis
adalah hidrolisis enzimatis. Penambahan ion logam pada hidrolisis enzimatis dapat meningkatkan
aktivitas enzim sehingga berpengaruh pada peningkatan konsentrasi gula reduksi. Tujuan penelitian ini
adalah menganalisis penambahan ion Na dan ion Ca terhadap konsentrasi gula reduksi sekaligus
mempelajari kinetika hidrolisis. Percobaan dilakukan pada berbagai konsentrasi substrat pati (100, 200,
dan 300 g/L), konsentrasi enzim (1 dan 1,5% (b/b)), penambahan ion Na dan Ca masing-masing 60 ppm.
Metode hidrolisis yang digunakan pada suhu rendah yaitu 30°C dengan enzim StargenTM 002 pada pH 4,
selama 24 jam. Hasil penelitian menunjukkan konsentrasi pati 100-200 g/L mampu meningkatkan
produksi gula reduksi secara signifikan pada konsentrasi enzim 1,5% (b/b). Penambahan ion Ca
meningkatkan konsentrasi gula reduksi 64% sedangkan penambahan ion Na meningkatkan konsentrasi
gula reduksi 18,9%. Konsentrasi gula reduksi terbaik (68,79 g/L) diperoleh pada kondisi konsentrasi pati
200 g/L dan konsentrasi enzim 1,5% (b/b) dengan penambahan ion Ca. Studi kinetika menunjukkan
fenomena hidrolisis ini mengikuti persamaan Michaelis-Menten dengan nilai Km 99,183 g/L dan nilai
Vmaks berturut-turut 6,053; 8,881; 15,106 g/L.jam sehingga penambahan ion Na dan Ca mampu
meningkatkan aktivitas enzim.
Kata kunci: singkong; hidrolisis enzimatis; penambahan ion Na; penambahan ion Ca; studi kinetika
Abstract
[Title: The Analysis of Na and Ca Ions Addition on Cassava Hydrolysis on Reducing Sugar
Concentration to Increase Enzyme Activity: Hydrolysis Kinetics Study] Sweet cassava is tuber that
contains large amount of starch so that it can produce reducing sugars. The addition of metal ions can
increase enzyme activity. The purpose was to study the addition of Na and Ca ions on reducing sugars
concentration and to study the hydrolysis kinetics. Experiments were carried out at various concentrations
of substrates (100, 200, and 300 g/L), enzyme concentrations (1 and 1.5% (w/w)), addition of Na and Ca
ions of 60 ppm. The hydrolysis method was conducted at temperature of 30°C with the enzyme Stargen TM
002 at pH 4, for 24 hours. The results showed that starch concentrations of 100-200 g/L were able to
significantly increase the reducing sugars at enzyme concentration of 1.5% (w/w). The addition of Ca ions
increased the concentration of reducing sugar by 64% while the addition of Na ions increased it by
18.9%. The best reducing sugar concentration (68.79 g/L) was obtained at starch concentration of 200
g/L and enzyme concentration of 1.5% (w/w) with the of Ca ions. Kinetic studies show that phenomenon
follows Michaelis-Menten equation with Vmax valued of 6.053; 8,881; 15.106 g/L.hour, respectively. So
that, addition of Na and Ca ion can increase the enzyme activity.
Ca. Prosentase kenaikan dihitung menggunakan dilakukan tanpa pre-treatment dan dengan pre-
Persamaan 3. treatmentpenambahan ion Na dan Ca. Pengaruh
konsentrasi pati dan penambahan ion Na dan Ca pada
Ci C0 konsentrasi enzim 1% (b/b) ditunjukan pada Gambar 2.
%Kenaikan = 100% (3) Gambar 2 (a,b dan c) menunjukkan fenomena
C0 yang sama dari masing-masing variabel. Konsentrasi
gula reduksi meningkat dengan bertambahnya waktu
Ci dan C0 secara berturut-turut adalah konsentrasi gula hidrolisis hingga 12 jam kemudian cenderung konstan.
reduksi dengan penambahan ion Na maupun ion Ca dan Hal ini disebabkan salah satunya karena telah tercapai
konsentrasi gula reduksi tanpa penambahan ion Na titik saturasi sehingga enzim sudah tidak mampu lagi
maupun ion Ca. mengkonversi pati menjadi gula reduksi (Daniel &
Danson, 2013).
3. Hasil dan Pembahasan Konsentrasi gula reduksi tertinggi yang diperoleh
3.1 Pengaruh Penambahan Ion Na dan Ca pada pada konsentrasi pati 100 g/L untuk tanpa penambahan
Berbagai Konsentrasi Pati dan Konsentrasi Enzim logam, dengan penambahan ion Na+, dan penambahan
terhadap Konsentrasi Gula Reduksi ion Ca2+ secara berturut-turut 18,84; 21,87; 25,92 g/L.
Hidrolisis enzimatis singkong manis (Manihot Konsentrasi gula reduksi tertinggi yang diperoleh pada
esculanta) dilakukan menggunakan berbagai konsentrasi konsentrasi pati 200 g/L untuk tanpa penambahan
pati singkong yaitu 100, 200, dan 300 g/L dan berbagai logam, dengan penambahan ion Na+, dan penambahan
konsentrasi enzim yaitu 1 dan 1,5% (b/b). Pada masing- ion Ca2+ secara berturut-turut 24,85; 28,30; 32,82 g/L.
masing konsentrasi pati dan konsentrasi enzim Berdasarkan data tersebut, kenaikan konsentrasi gula
(a) (b)
(c )
Gambar 2. Pengaruh penambahan ion Na dan ion Ca pada konsentrasi pati: a) 100 g/L, b) 200 g/L,c) 300 g/L
terhadap konsentrasi gula reduksi pada hidrolisis menggunakan StargenTM002, konsentrasi 1% (b/b), suhu 30°C
reduksi dari konsentrasi pati 100 g/L ke 200 g/L cukup penambahan logam dan dengan penambahan ion Na+
signifikan. Hal ini disebabkan semakin banyak dan Ca2+ menggunakan konsentrasi enzim StargenTM
konsentrasi pati maka semakin banyak substrat yang 002 sebesar 1,5% (b/b) seperti disajikan pada Tabel 1.
dikonversi menjadi gula reduksi. Hal ini menandakan Berdasarkan fenomena yang disajikan pada Tabel
bahwa situs aktif enzim masih mampu mengkonversi 1, pengaruh gula reduksi terhadap waktu hidrolisis dan
jumlah substrat yang lebih banyak (Mezule dkk., 2019). konsentrasi pati memiliki kecenderungan yang sama
Konsentrasi gula reduksi tertinggi diperoleh pada pada penelitian menggunakan konsentrasi enzim sebesar
konsentrasi pati 300 g/L untuk tanpa penambahan 1% (b/b). Namun demikian, konsentrasi enzim sebesar
logam, dengan penambahan ion Na+, dan penambahan 1,5% (b/b) menghasilkan peningkatan konsentrasi gula
ion Ca2+ secara berturut-turut 25,92; 28,82; 33,20 g/L. reduksi yang signifikan untuk masing-masing variabel
Berdasarkan data tersebut, kenaikan konsentrasi gula dibandingkan dengan konsentrasi enzim 1% (b/b).
reduksi dari konsentrasi 200 g/L ke 300 g/L tidak Krajang dkk. (2021) melakukan hidrolisis
menunjukkan perbedaan signifikan. Hal ini disebabkan enzimatis pada pati singkong menggunakan enzim
oleh peningkatan viskositas yang menghambat proses StargenTM 002 dengan variasi konsentrasi 0,1 hingga
difusi. Selain itu, terdapat kemungkinan terjadi inhibisi 0,4% (w/v). Hasil produk gula reduksi meningkat seiring
akibat konsentrasi substrat yang tinggi (Ruiz dkk., bertambahnya konsentrasi enzim yang digunakan yaitu
2011). mencapai 78,70 g/L pada konsentrasi enzim 0,4%(w/v).
Mezule dkk. (2019) melakukan hidrolisis dengan Hal ini disebabkanoleh semakin banyaknya situs aktif
konsentrasi substrat 1-10% (b/v). Peningkatan pada yang bekerja (Krajang dkk., 2021).
konsentrasi substrat hingga 5% (b/v) dapat Konsentrasi gula reduksi setelah diberikan
meningkatkan produk gula reduksi. Pada konsentrasi penambahan ion Na+ dan ion Ca2+ mengalami
substrat diatas 5% (b/v) tidak mampu meningkatkan peningkatan dibandingkan tanpa pemberian ion logam.
konsentrasi gula reduksi atau cenderung konstan. Hal ini Prosentase kenaikan konsentrasi gula reduksi terhadap
serupa dengan penelitian yang dilakukan. penambahan ion Na+ dan ion Ca2+ untuk masing-masing
Penelitian yang sama juga dilakukan dengan variabel disajikan pada Tabel 2.
menggunakan konsentrasi pati 100-300 g/L untuk tanpa Penambahan ion logam menunjukkan kenaikan
Tabel 1. Pengaruh penambahan ion Na dan ion Ca pada konsentrasi pati 100 g/L, 200 g/L, dan 300 g/L terhadap
konsentrasi gula reduksi menggunakan StargenTM 002, konsentrasi 1,5% (b/b), suhu 30°C.
Konsentrasi Gula Reduksi (g/L)
Waktu
Konsentrasi Pati 100 g/L Konsentrasi Pati 200 g/L Konsentrasi Pati 300 g/L
(jam)
Tanpa +Na +Ca Tanpa +Na +Ca Tanpa +Na +Ca
3 16,34 20,54 30,52 19,45 28,45 39,90 18,12 30,12 36,12
6 24,16 29,08 35,88 34,22 38,24 48,92 35,65 39,24 42,45
9 28,24 34,64 48,65 40,12 42,56 59,07 41,34 43,56 52,84
12 30,12 40,23 52,44 41,33 49,78 68,32 42,65 50,34 55,60
15 30,34 40,45 52,56 41,89 49,82 68,76 42,70 50,36 55,70
18 30,56 40,54 52,58 41,94 49,86 68,79 42,72 50,40 55,78
Tabel 2. Prosen kenaikan konsentrasi gula reduksi terhadap penambahan ion Na dan ion Ca pada berbagai konsentrasi
pati terhadap konsentrasi gula reduksi pada hidrolisis menggunakan StargenTM 002, konsentrasi 1,5% (b/b), suhu 30°C.
Kenaikan konsentrasi gula reduksi (%)
Waktu
Konsentrasi Pati 100 g/L Konsentrasi Pati 200 g/L Konsentrasi Pati 300 g/L
(jam)
+Na +Ca +Na +Ca +Na +Ca
3 25,7 86,8 46,3 105,1 66,2 99,3
6 20,4 48,5 11,7 43,0 10,1 19,1
9 22,7 72,3 6,1 47,2 5,4 27,8
12 33,6 74,1 20,4 65,3 18,0 30,4
15 33,3 73,2 18,9 64,1 17,9 30,4
18 32,7 72,1 18,9 64,0 18,0 30,6
konsentrasi gula reduksi yang cukup tinggi seperti tersebut. Peningkatan aktivitas enzim denganion Ca2+,
ditunjukkan pada Tabel 2. Penambahan ion Ca 2+ Zn2+, dan Fe2+ dapat didasarkan pada kemampuan
menghasilkan kenaikan konsentrasi gula reduksi yang berinteraksi dengan asam amino bermuatan negatif,
lebih tinggi dibandingkan penambahan ion Na+ untuk seperti asam aspartat dengan menstabilkan muatan
masing-masing variabel Na+ yang mampu meningkatkan negatif yang terbentuk di situs aktif (Carvalho dkk.,
konsentrasi gula reduksi dan mengaktivasi enzim 2014).
dengan mengikat air dan residu protein yang sesuai
(David dkk., 2016). Zohra dkk. (2016) telah melakukan 3.2 Parameter Kinetika Hidrolisis Pati Singkong
penelitian hidrolisisenzimatis dengan penambahan ion terhadap Penambahan Ion Na dan Ca
logam monovalen, divalen, dan trivalen. Penambahan Salah satu faktor yang berpengaruh terhadap
ion Ca2+ menghasilkan aktivitas enzim tertinggi diantara aktivitas enzim adalah konsentrasi substrat pati
ion logam lain. Hal ini disebabkan secara umum amilase singkong. Pada penelitian ini digunakan variasi
dikenal sebagai metaloenzim dan mengandung konsentrasi substrat sebesar 100, 150, 200, 250, 300,
setidaknya satu ion Ca2+ sebagai komponen integral 350, 400, dan 450 g/L. Kecepatan reaksi awal (Vo)
untuk meningkatkan aktivitas enzim. Selain itu, untuk ditentukan menggunakan tangen dari persamaan garis
menjagakestabilan dan memperpanjang waktu paruh polynomial hubungan waktu terhadap produksi gula
enzim, Ca2+ adalah kation yang disukai. -amilase reduksi seperti ditunjukkan pada Gambar 1. Kecepatan
termostabil menggambarkan stabilitas termo yang lebih reaksi awal (Vo) kemudian diplotkan pada grafik untuk
dengan adanya Ca2+(Zohra dkk., 2016). mengetahui hubungan antara konsentrasi substrat (So)
Penelitian serupa juga dilakukan oleh Wang dkk. terhadap kecepatan reaksi awal (Vo) seperti disajikan
(2018). Ia melakukan hidrolisis jerami gandum dengan pada Gambar 3.
penambahan ion logam. Hasil yang diperoleh bahwa Penambahan konsentrasi substrat meningkatkan
semakin tinggi muatan ion pada logam tersebut maka kecepatan reaksi awal kemudian pada konsentrasi
semakin tinggi pula aktivitas enzim yang dihasilkan. substrat setelah 300 g/L menghasilkan kecepatan reaksi
Namun tidak semua jenis logam dengan muatan yang awal yang cenderung konstan. Hal ini sesuai dengan
lebih tinggi dapat bertindak sebagai aktivator (Wang konsep Michaelis-Menten bahwa konsentrasi substrat
dkk., 2018). Salah satu contohnya adalah ion logam awal berpengaruh terhadap kecepatan reaksi. Pada
Mg2+. Pada konsentrasi 6-10 mM, ion Mg2+ dapat kenaikan konsentrasi substrat akan meningkatkan
menurunkan aktivitas enzim karena mampu mengikat kecepatan reaksi sampai titik tertentu kemudian tidak
sisi aktif enzim (Anggraini dkk., 2020). akan meningkat meskipun ditambahkan substrat yang
Ezugwu dkk. (2016) melakukan studi aktivitas lebih banyak. Hal ini disebabkanenzim sudah mencapai
enzim glukoamilase menggunakan beberapa ion logam titik jenuh terhadap substrat dan mencapai kecepatan
divalen yaitu Ca2+, Zn2+, dan Fe2+. Penggunaan ion reaksi maksimum (Vmaks) sehingga aktivitas enzim tidak
logam ini mampu menahan substrat untuk melakukan dipengaruhi konsentrasi substrat (Vitolo, 2020).
interaksi dengan enzim menggunakan bantuan ion Parameter kinetika hidrolisis singkong dapat
hidroksida nukleofilik yang dihasilkan oleh ion logam ditentukan menggunakan bantuan persamaan hasil
Gambar 3. Hubungan konsentrasi substrat awal (So) Gambar 4. Hubungan 1/So terhadap 1/Vo pada
terhadap kecepatan reaksi awal (Vo) pada penambahan ion Na dan ion Ca.
penambahan ion Na dan ion Ca.
Abstract : This study aims to examine the thermodynamic-related phenomena that occurred to the liquid smoke and
other products (e.g. acetic acid and solid residue) that resulted from the pyrolysis on three kinds of lignin-cellulosic
materials (i.e. teak wood, pine wood sawdust). The pyrolysis proceeded at five maximum temperatures, i.e. 110-500oC,
each for 5 hours. At 200oC, the liquid smoke yield from those two materials achieved the greatest, i.e. 17.05% (teak
wood), and 14.46% (pine wood). Acetic acid concentration as present in the liquid smoke varied, i.e. 5.09-9.78% (from
teak wood), and 3.63-5.29% (pine wood). The formation of acetic acid was not spontaneous due to the positive change in
Gibbs free energy with increasing pyrolysis temperature. Formation of solid residue from each of the three lignin-
cellulosic materials was accompanied with the positive changes (>0) in both enthalpy and entropy, indicating of its
endothermic process. The enthalpy/heat content of the solid residue increased with the pyrolysis temperature, suggesting
the carbonization occurred intensively (e.g. increasing the carbon content as well as charcoal portion). The heat
content/calorific value of the teak-wood’s solid residue was the greatest (18.89-28.36MJ/kg), followed in decreasing
order by those from teak wood’s residue (18.73-27.92 MJ/kg, as the second highest) Results of these thermodynamic-
related phenomena expectedly bring remarkable benefits, e.g. (1) understanding whether the formation of particular
pyrolysis products (e.g. organic acid, acetic acid, and charcoal) was endothermic, not-spontaneous, or something else;
INTRODUCTION
Production liquid smoke from waste wood has got attention during the last several years. One of its production
process is the pyrolysis process which contains decomposition of hemicellulose, cellulose and lignin occured in raw
materials. Pyrolysis produces liquid smoke, charcoal, chemicals, and tar. Previous research have been done using
various materials to produce liquid smoke by pyrolysis method such as pine wood [1]. natural lignin [2]. celluluce
micro crystalin [3]. and hibride wood [4]. Those raw materials contained hemicellulose, cellulose and lignin. Based
on this invention, it is known that there is relationship between type of materials and the composition of liquid
smoke produced by pyrolysis procces. Those components of teak sawdust pyrolysis product were used as composing
materials of biofuel [5]. In other research, liquid smoke from bamboo could be used as ingredients of cosmetics,
supplement and healthy drinks [6].
In general, pyrolysis of material which contain hemicellulose will produce furfural, furan, acetic acid and its
derivatives. Lignin will be decomposed into phenol and phenolic ether and its derivatives, and also carbonyl
compound, while cellulose will produce acetic acid compound and carbonyl compound. These pyrolysis compounds
have diverse function. Phenol and carbonyl are useful to make flavor and color, while phenol and organic acid
compounds are used as preservative due to their antibacterial and antioxidant. During the process, decomposition of
hemicellulose, cellulose and lignin was occurred on raw materials, and as the result liquid smoke, charcoal,
vegetable oil, and others were produced. Research model thermodynamic pyrolysis by the changes in Gibbs free
energy as a function of pyrolysis temperature has not been done. This method was used to thermodynamic studies
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for the formation of acetylene and coal [7]. This study is closely related to theories of the relationship between
Gibbs free energy generated by the temperature pyrolysis.
Main purpose of this research was to produce liquid smoke through pyrolysis process and to obtain the potential
chemical component fractions from wood waste, hence purpose of each research activity was as follows (1).To
increase product of pyrolysis by physical and Chemistry Properties (temperature, rate of reaction and time recidence.
(2). Makes product pyrolysis (liquid smoke and char) with model thermodynamic (3). Model kinetic reaction from
liquid smoke and charcoal integrated system to emission carbon reduce
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(a) (b)
Information : : DTG DTA : TG
FIGURE 1. Analysis thermal DTA/TGA product for two type raw material (a).Teak wood (b), Pine
Based on Fig 1, it showed thermal decomposition process in all samples of 3 steps. In case of teak wood
decomposition was occurred of 206.7, 281.3 and 349.7°C. In case pine sawdust, it was occurred 227, 320.2 and
349.7°C. At the first, hemicellulose was decomposed while at second step cellulose was decomposed. Lignin was
decomposed at third step. Degradation of three components were took place at temperature 200-350° C. Within in
this at temperature evaporation of water from hazardous materials and decomposition of other component were
occured. Biomass waste raw material analysis showed that The results of this research that the pod husks produce
ethanol of benzene of 1: 2 at 12.89%, content of hemicellulose 19.97%, cellulose 21.80% and lignin 47.96% [8].
Liquid Smoke
Raw materials applied for making of liquid smoke in this research were wood and bamboo dust. Pyrolysis
temperature done was between 110-500°C. Yield is one of important parameter to know result from a process.
Liquid smoke in this research was resulted through condensation process of smoke released from pyrolysis reactor.
During pyrolysis process it happened evaporation of various chemical components of liquid smoke. Yield of liquid
smoke resulted from pyrolysis process of Teak and Pine wood dust during 5 hours with electrical reactor ranged
between 1.15 – 18.18%.
TABLE 1. Yield of pyrolysis process on Teak and Pine wood vinegar
Pyrolysis Yield (% w/w )
Temperature Teak Wood Pine Wood
(° C.) Vinegar Vinegar
110 8.27 10.92
200 17.05 14.46
300 9.10 11.99
400 8.35 11.32
500 1.02 0.92
Total 43.78 49.60
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Based on Table 1, teak wood vinegar at temperature of 200°C was produced the higher yield of pine wood . This
was caused because liquid smoke of teak wood was resulted from bamboo carbon obtained from pyrolysis process.
Liquid smoke of teak wood was compound having water content of 90% and added by other chemical components,
in which there were approximately 200 chemical components in liquid smoke [9]. One of them is acetic acid, and
other organic components. From these three liquid smoke resulted from pyrolysis of raw materials, that gave the
highest yield of liquid smoke was liquid smoke of pine wood sawdust by 49.60% and teak wood sawdust 43.78%
[10].
TABLE 2. Average ratio teak and pine wood of vinegar at reactor pyrolysis
Pyrolysis Temperature pH Acetic Acid concentration
(°C ) (% v/v)
Teak Pine Teak Pine
110 3.14 3.45 5.09 5.29
200 3.16 3.30 9.34 4.10
300 3.19 3.07 9.67 3.66
400 3.38 3.21 9.81 3.63
500 3.70 3.45 9.78 3.82
In Table 2, The pH value teak and pine wood vinegar relatively low, because pyrolysis process the raw materials
produced formic acid, benzoic acid and acetic acid which causes a low pH value. The results of GC-MS analysis
calculations for the concentration of acetic acid. The concentration of acetic acid entity increases between 110-
200°C. The temperature in the raw materials the pine feedstock, acid formation has reached the maximum at 110°C.
The difference amount of acetic acid is probably due to differences in the composition of wood waste containing
compounds as the principal constituent of acid component of the thermal degradation of cellulose, hemicelluloce
and lignin [11]. Another difference is teak, has a medium density (0.60-0.75 g/cm3), bond strength and
dimensionally stable [12].
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The calorific value of the two types charcoal tend to rise above the pyrolysis temperature increases. The
calculation result of the above results that the calorific value of identity ranged from 18.73-27.92 MJ/kg, pine ranged
between 18.89-28.36 MJ/kg. The calorific value is higher than pine calorific value of teak wood [10]. The calorific
value is influenced by moisture content, less as hand fly substances and other types of raw materials. These results
are consistent with the results of studies on the heating value of raw materials from the pyrolysis process has been
done by previous researchers. The calorific value for the pyrolysis of Maize Straw 16.9 MJ/kg and seaweed of 11.5
MJ/kg [13]. The calorific value of mixed municipal solid waste and industrial waste by pyrolysis of 19.87 MJ/kg
[14].
Changes in Enthalpy (ΔH ⁰), Entropy (ΔS ⁰) and Gibbs Free Energy (ΔG⁰)
Thermodynamics study for the pyrolysis process provides the data change in entropy, enthalpy and Gibbs free
energy. The rate of reaction changed completely when used in high pressure. Reaction rate depends on temperature,
kinetics constants and activation energy. Enthalpy change of activation energy obtained from the value to changes in
temperature and gas constant, can be seen in Figure 2.
FIGURE 2 Enthalpy Tsamba acetic acid from teak, pine wood vinegar with thermodynamic model
Fig 2, shown the enthalpy value of two models [15]. It seen that entalphy decreased with increasing temperature,
where the enthalpy change for teak ranges between 15.86-12.61 kJ/mol, and value for pine wood ranged between
8.88-5.63 kJ/mol. This is caused by the influence of the activation energy, where the value of activation energy of
acetic acid teak 19.04k J/Mole, and acetic acid pine 12.06 kJ/Mol larger than the value of the multiplication
constants for the gas and pyrolysis temperature (3184-6426) kJ/Mole so that the enthalpy change is positive.
In this reserach to calculate the change in ΔH⁰ where Energy activation (Ea) depends on the temperature of
pyrolysis. Thermodynamic properties of a system is defined as ΔH⁰= Ea-RT. Enthalpy change is directly
proportional to the activation energy. If Ea > RT, then the enthalpy change is positive on the formation of acetic acid
teak, and pine. In general, the enthalpy change is affected by the value of activation energy and temperature
pyrolysis. If the enthalpy change is positive means that the reaction is endothermic. This is supported by research
[16]. that the enthalpy value for AMI, MNDO and PM3 at 250.66, 325.07, and 195.01 kJ/mol. Enthalpy change for
Cr(III) of 12.64 kJ/Mole with increasing temperature [17].
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FIGURE 3. Entropy change of acetic acid teak, and pine with Tsamba et al, 2006 models in thermodynamics.
Fig 3 shows that the overall entropy change for the three models Tsamba et al. (2006) of raw materials tend to
decrease. Tsamba model entropy values for acetic acid formation reaction form -243.54 - (-310.19) J/K.mol smaller
than the entropy of acetic acid pine ranged from -268.40 - (-314.18) J/K.mol This is caused by the influence of
process conditions (temperature pyrolysis) and the heating rate causes a decrease in enthalpy which the
decomposition of cellulose liquid smoke In order to calculate the entropy of the data required and the temperature of
pyrolysis kinetics constants in order to obtain the enthalpy change. If the enthalpy is negative, meaning that the
reaction takes places spontaneously and the reaction exothermal. The entropy is negative. It can be concluded that
the enthalpy change is positive indicates that the process takes places spontaneously and are endothermic.
Gibbs free energy changes in chemical thermodynamics in acetic acid identity. Pine and bamboo by calculating
the value of enthalpy and entropy changes of temperature on the pyrolysis process can be seen in Figure 4.
FIGURE 4. Gibbs free energy of acetic acid production form teak and pine wood
Fig 4, shows that the change in Gibbs free energy of acetic acid teak wood, and pine in thermodynamics model
tends to increase with rising temperature. Gibbs free energy change on Tsamba model for acetic acid identity ranged
from 142.11-310.81 kJ/mol higher than the Gibbs free energy for acetic acid of pine ranged between 142.46-304.31
kJ/mol. This is due to changes in temperature and entropy (TΔS⁰) was higher than the enthalpy change (ΔH⁰).
Factors affecting the value of Gibbs free energy is the heating rate and pyrolysis temperature. Other research [16].
Gibbs free energy for AMI, MNDO and PM3 at 251.09, 332.01, and 195.47 kJ/mol due to the mechanism of
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pyrolysis in a state of transition. Thermodynamic parameter values to calculate changes in enthalpy and entropy for
Sorption on process of 39.3 kJ/mol and 202 kJ/mol K [19], In fact, temperature of 150°C and under pressure of 2
MPa, with the addition of the catalyst can improve the yield of methanol is close to thermodynamic predictions [20].
Based on thermodynamic results indicated that the gasification process is more effective than the pyrolysis
process in the formation of hydrogen and syngas (CO, CO2, CH4 and H2) in a mixture of coal and biomass [21].
Gibbs free energy change is positive since , the higher the pyrolysis temperature increased, which indicated that the
pyrolysis process of biomass (wood teak, and pine ) does not take places spontaneously with the endothermic
reaction of acetic acid product in the pyrolysis result. Negative values in the Gibbs free energy change (ΔG°)
indicates that the absorption process is likely to occur (feasible) and spontaneous at all temperatures studied. ΔG°
values decrease with increase in temperature which proves that the reaction at high temperature [22]. Positive value
on the change in enthalpy for Cr (III) with end other mix process, and negative values in the Gibbs free energy
change indicates that the possibility of and the process of spontaneous [17]. This research, reactions can take place,
then ΔG < 0 and the thermodynamic equilibrium reaction at room temperature depending on the product acetic acid,
the reaction was very slow, where the reaction rate decreased with increasing pyrolysis time and yield more acetic
acid increased with increase in Gibbs free energy.
CONCLUSIONS
The formation of acetic acid teak, and pine on the results of the experiment occurred seiringin optimal
temperature increase at 400-500° C. The highest yield of liquid smoke obtained from pine wood was 49.60% and
from teak wood was 43.78%.
ACKNOWLEDDGMENTS
This research in a part of research funded by ministry of Research, Technology and Higher Educational
(RISTEK DIKTI) Republic of Indonesia, Research Grant by PSNI I wish to thank you for facility Laboratorium
Wood Chemical and Biomass. Environmental and Forestry Ministry Republic of Indonesia, Gunung Batu Bogor
REFERENCES
1. P. Badger, S. Badger, M. Puettmann, P. Steele, J. Cooper, J.Biores. 6, 1, 34-47 (2011).
2. J. Y. Liu , S. B. Wu, R. J. Lou. Biores. 6, 2, 1079-1093 (2011).
3. Q. Chen , T. Endo and Q. Wang. J. Biores 11, 1, 159-173 (2016).
4. F. A. Agblevor, S. Beis, O. Mante, N. J. Abdoulmoumine, Ind. Eng. Chem. Res. 49, 8, 3533-3538 (2010).
5. I. Fatimah and J. Nugraha, Jurnal Ilmu Dasar. 6, 1, 41-47 (2005).
6. H. F. Jin. International Network of Bamboo and Rattan Beijing, PR China (2005).
7. W. Bao, F. Li, G. Cai, Y. Lu and L. Chang, J Energy sources. 31, 3, 244-254 (2009).
8. M. Wijaya and M. Wiharto, e-UNEJ Proceeding, 259-261 (2017).
9. D. Fengel, G. Wegener. Wood: Chemistry, Ultrastructure, Reactions. (Walter de Gruyter, Berlin-New York,
USA, 1984).
10. M. Wijaya, E. Noor, T. T. Irawadi and G. Pari. Ph.D. thesis, Sekolah Pascasarjana IPB Bogor, 2011.
11. P. Darmadji, Jurnal Teknologi dan Industri Pangan. 8, 3, 267 – 271 (2002).
12. Amoako AAO. ITTO Tropical Forest up Date-Yokohama Japan. 14, 1, (2004). http://www.itto.int
13. N. Ye, D. Li, L. Chen, X. Zhang, D. Xu. UlvaPertuza. PlOs One. 5, 9.e12641.(2010)
14. M. Paulucci, P. De Filippis, C. Borgianni, J. Biores. 14, 3, 739-746 (2010).
15. A. J. Tsamba, W. Yang, W. Blasiak, J. Fuel Proc. Technol. 87, 523-530 (2006).
16. I. A. Adejero, E. Ekeh, J. Chem. 7, 1, 271-274 (2010).
17. M. Mahdavi, M. B. Ahmad, M. J. Haron, M. Z. Abdulrahman, J Biores. 6, 1, 22-33. (2011)
18. K. Li, Z. Zheng, X. Huang, G. Zhao and J. Feng, J. Zhang, J. Hazardous Material, 16, 211-220.
19. K. L. Wasewar, S. Kumar, B. J. Prasad, Environ. Protect. Sci. 3, 41-52 .(2009)
20. I. D. Mahajjam, J. E. Wegryzyn. Symposium of Chemistry of Renewable Fuel and Chemical. 217 th ACS
National Meeting, USA (1999).
21. A. Franzoni, L. Galanti, A. Traverso, A. F. Massardo. Int. J. Thermodynamic. 12, 2, 97-104. (2009).
22. M. J. Haron, M. Tiansih, N. A. Ibrahim, A. Kasim, W. M. Z. Wan Yunus. J.Biores. 4, 1305-1318.(2009).
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