REVIEW ARTIKEL ILMIAH

JUDUL: First Order Kinetic of Biodiesel Syhnthesis Using Used Frying Oil Through
Transesterification Reaction

DOSEN PENGAMPU:
Prof. Dr. Dani Supardan, S.T., M.Eng

Nama Anggota (Kelompok 3):

1. Mazaya Amajida /1804103010015
2. Farhana Zakiah /1804103010052
3. Rini Lailatul Kadri /2004103010034
4. Rani Hastuti /2004103010036
5. Radika Putri /2004103010037
6. Dini Hayatul Nufus /2004103010039
7. Nava Resi BR Sembiring /2004103010041
8. Muammar Khadafi /2004103010045

JURUSAN TEKNIK KIMIA FAKULTAS TEKNIK

UNIVERSITAS SYIAH KUALA
DARUSSALAM, BANDA ACEH
2022
 KATA PENGANTAR

Puji dan syukur penulis panjatkan kehadirat Allah Subhanahu wata'ala atas berkat dan
rahmat, serta kesempatan yang telah diberikan-Nya sehingga penulis dapat menyelesaikan
penulisan review artikel ilmiah yang berjudul “First Order Kinetic of Biodiesel Syhnthesis Using
Used Frying Oil Through Transesterification Reaction”. Tak lupa pula shalawat dan salam
penulis ucapkan kepangkuan Nabi Besar Muhammad Shallallahu 'alaihi wasallam beserta
keluarga dan para sahabatnya sekalian.
Penulisan makalah ini bertujuan untuk memenuhi salah satu tugas pada mata kuliah
Matematika Teknik yang merupakan mata kuliah wajib untuk mahasiswa di Jurusan Teknik
Kimia, Fakultas Teknik, Universitas Syiah Kuala. Dalam penulisan ini penulis banyak mendapat
bimbingan dan bantuan dari berbagai pihak, terutama dosen pengampu mata kuliah Matematika
Teknik. Oleh karena itu penulis mengucapkan banyak terima kasih kepada :
1. Ibu Prof. Dr. Ir. Sri Aprilia, M.T., selaku Ketua Jurusan Teknik Kimia Universitas Syiah
Kuala.
2. Bapak Prof. Dr. Dani Supardan, M.Eng., selaku Ketua Prodi S1 Teknik Kimia,
Universitas Syiah Kuala dan dosen pengampu mata kuliah Matematika Teknik yang telah
memberikan tunjuk ajar terkait materi mata kuliah dan panduan penulisan makalah ini.
3. Teman-teman yang telah memberikan masukan dalam penulisan makalah ini.
Penulis menyadari dalam penulisan review artikel ilmiah ini mungkin masih terdapat
kekurangan. Oleh karena itu penulis mengharapkan kritik dan saran yang bersifat membangun
demi kesempurnaan penulisan review ini di masa yang akan datang. Semoga penulisan ini
dapat bermanfaat bagi kita semua. Amin.

Darussalam, 18 April 2022

Penulis

i
 DAFTAR ISI
KATA PENGANTAR ..................................................................................................................... i
DAFTAR ISI ................................................................................................................................... ii
ABSTRAK....................................................................................................................................... 1
BAB I. PENDAHULUAN .............................................................................................................. 1
BAB II. METODE .......................................................................................................................... 2
i) Bahan-bahan ........................................................................................................................ 2
ii) Prosedur Penelitian .............................................................................................................. 2
iii) Kinetika Transesterifikasi .................................................................................................... 3
iv) Validasi Model ..................................................................................................................... 3
BAB III. HASIL.............................................................................................................................. 3
i) Karakteristik UFO ............................................................................................................... 3
ii) Yield Biodiesel..................................................................................................................... 4
iii) Parameter Kinetika .............................................................................................................. 4
BAB IV. PEMBAHASAN .............................................................................................................. 5
i) Karakteristik UFO ............................................................................................................... 5
ii) Yield Biodiesel..................................................................................................................... 5
iii) Parameter Kinetika .............................................................................................................. 5
iv) Validasi Model .................................................................................................................... 6
BAB V. KESIMPULAN ................................................................................................................. 6
PERTANYAAN DAN JAWABAN ............................................................................................... 8
DAFTAR PUSTAKA ................................................................................................................... 10
LAMPIRAN .................................................................................................................................. 11

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Judul Artikel: First Order Kinetic of Biodiesel Syhnthesis Using Used Frying Oil Through
Transesterification Reaction
Nama Penulis: Agus Haryanto, Amieria Citra Gita, Tri Wahyu Saputra, dan Mareli Telaumbanua.

ABSTRAK (Nava Resi BR Sembiring)

1. Penelitian ini bertujuan untuk mempelajari kinetika orde satu produksi biodiesel dari
minyak goreng bekas (UFO) melalui transesterifikasi dengan metanol.
2. Variabel yang diuji adalah pengaruh rasio molar minyak dan metanol (1:4, 1:5, dan 1:6),
temperatur reaksi (30-55°C dengan interval 5°C), dan waktu reaksi (0,25; 0,5; 1; 2; 3; 6; 8;
dan 10 menit).
3. Hasil biodiesel meningkat dengan meningkatnya waktu reaksi, rasio molar, dan suhu. Yield
biodiesel tertinggi didapatkan sebesar 78,44% dengan variabel suhu 55°C pada rasio molar
minyak:metanol 1:6.
4. Nilai k meningkat dengan meningkatnya suhu reaksi dan rasio molar.
5. Penggunaan model kinetika orde satu sesuai digunakan untuk memprediksi yield biodiesel
pada reaksi ini dikarenakan persentase RMSE yang kecil yaitu 3,39% dan nilai R2 sebesar
0,8454.

BAB I. PENDAHULUAN (Rani Hastuti)

1. Biodiesel didefinisikan sebagai bahan bakar yang terdiri dari mono-alkil (metil, propil, atau
etil) ester asam lemak rantai panjang yang berasal dari minyak nabati atau lemak hewani
sehingga merupakan bahan bakar yang ramah lingkungan karena terurai secara biologis.
2. Produksi biodiesel dengan menggunakan minyak nabati dan lemak hewani mengakibatkan
harga biodiesel tinggi karena tingginya biaya bahan baku.
3. UFO dapat dijadikan sebagai bahan baku utama dalam pembuatan biodiesel. Memproduksi
biodiesel dari UFO merupakan solusi tepat karena biaya yang murah.
4. UFO dapat dikonversi menjadi biodiesel melalui reaksi transesterifikasi dengan metanol
dan katalis natrium hidroksida (NaOH) seperti persamaan berikut : Minyak + Alkohol →
Biodiesel + Gliserol
5. Transesterifikasi merupakan reaksi kesetimbangan sehingga lebih banyak yield biodiesel
yang dapat terbentuk dengan menggunakan metanol berlebih. Kerugian dari reaksi ini

1
 adalah terbentuknya sabun yang dapat menonaktifkan katalis sehingga dapat menurunkan
yield biodiesel, terutama jika kandungan asam lemak bebas dalam minyak cukup tinggi.
6. Kinetika reaksi tranesterifikasi umumnya menggunakan model persamaan orde satu.
7. Kinetika reaksi ini ditentukan oleh faktor temperatur dan waktu reaksi, sedangkan rasio
molar minyak terhadap metanol berpengaruh terhadap yield biodiesel.
8. Tujuan dari penelitian ini adalah untuk mengetahui parameter kinetika reaksi
transesterifikasi UFO terhadap rasio molar minyak terhadap metanol.

BAB II. METODE (Rini Lailatul Kadri)

i) Bahan-bahan:
1. Minyak bekas diperoleh dari pedagang makanan gorengan, dimana minyak tersebut berasal
dari minyak sawit. Minyak bekas ini disaring terlebih dahulu menggunakan filter teh untuk
memisahkan partikel padatan.
2. Metanol teknis dan NaOH didapatkan dari pasar lokal.
3. Kandungan asam lemak bebas, bilangan asam dan viskositas UFO ditentukan melalui
penelitian sebelumnya.

ii) Prosedur Penelitian

1. Perlakuan dalam percobaan ini yaitu adanya kombinasi antara variasi rasio molar minyak
terhadap metanol, temperatur, dan waktu reaksi.
2. Penelitian ini menggunakan variasi rasio molar minyak terhadap metanol sebesar 1:4, 1:5
dan 1:6 dengan didasarkan atas penelitian sebelumnya yang menyebutkan bahwa
peningkatan rasio molar lebih dari 1:6 tidak berpengaruh terhadap yield biodiesel.
3. Temperatur reaksi terdiri dari 6 variabel, yaitu 30°C hingga 55°C dengan interval suhu
5°C.
4. Waktu reaksi maksimum 10 menit, dengan delapan variasi (0,25, 0,5, 1, 2, 3, 6, 8, dan 10
menit)
5. Tahapan pertama adalah membuat larutan metoksi dengan mencampurkan katalis NaOH
0,5% dan metanol berdasarkan variasi rasio molar yang ditentukan.
6. UFO dipanaskan pada temperatur tertentu, kemudian larutan metoksi dicampurkan ke
dalam minyak dan diaduk dengan kecepatan 300 rpm selama waktu tertentu.

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 7. Setelah dilakukan pemisahan dan pencucian, diperoleh yield biodiesel yang dapat dihitung
dengan persamaan :
Yield = [Bt/O0] × 100%
dimana Bt adalah massa biodiesel pada waktu tertentu dan O0 adalah massa umpan minyak.
iii) Kinetika Transesterifikasi (Farhana Zakiah)
1. Umumnya reaksi tranesterifikasi merupakan reaksi orde 1.
𝑑 [0]
2. Persamaan kinetika reaksi orde 1 dapat ditulis sebagai berikut: Laju Reaksi = - = 𝑘[𝑂]
𝑑𝑡

Persamaan di atas diintegral sehingga didapatkan persamaan berikut:

[Ot]/[O0] = exp(-kt)
3. Konversi reaksi biodiesel dihitung sebagai yield biodiesel sehingga didapatkan persamaan
berikut untuk mendapatkan persamaan reaksi:
1 – Yield = exp(-kt)
4. Untuk mengetahui nilai konstanta laju reaksi (k), diplotkan grafik waktu (t) melawan
1Yield, kemudian nilai k tersebut akan digunakan untuk menentukan Energi Aktivasi (Ea)
dan faktor frekuensi tumbukan (A) dengan menggunakan persamaan Arrhenius seperti
berikut:
𝐸𝑎
𝑘 = 𝐴 𝑒𝑥𝑝 (− 𝑅𝑇 )

dimana A adalah faktor frekuensi terjadinya tumbukan, T adalah temperatur (K), R adalah
konstanta gas universal (8,314472 J/mol.K).
iv) Validasi Model (Muammar Khadafi)
1. Model persamaan yang diperoleh menggunakan data kumpulan biodisel yang diukur pada
waktu 8 menit
2. Prediksi hasil yang baik dinilai dari R2 dan prediksi pengamatan dan %RMSE
3. Residu di definisikan sebagai pembeda hasil yang di amati
4. Semakin rendah %RSME semakin baik prediksinya.

BAB III. HASIL

i) Karakteristik UFO (Dini Hayatul Nufus)
1. Komposisi yang mendominasi pada minyak goreng bekas adalah komponen palmitat
(42,84%), oleat (35,71%, dan linoleat (12,43%).

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 2. Total dari kontribusi ketiga komposisi asam lemak tersebut adalah sebesar 91%

ii) Yield Biodiesel (Farhana Zakiah)

Suhu 55°C
90
80
70
60
50 1:4
40
30 1:5
20
10 1:6
0
0 2 4 6 8 10 12
t (min)

(a) (b)
Gambar 1. Perbandingan data yield biodiesel di antara (a) data eksperimen dengan (b) data teoritis
1. Berdasarkan gambar di atas, dapat dilihat adanya perbedaan pada yield biodiesel di antara
data eksperimen dengan data teoritis sesuai persamaan yang didapatkan pada Gambar 2.
2. Semakin lama waktu reaksi, maka yield yang diperoleh semakin besar.

iii) Parameter Kinetika (Mazaya Amajida)

(a) (b)

Gambar 2. Perbandingan parameter kinetika di antara (a) data eksperimen dan (b) data teoritis
1. Berdasarkan gambar di atas, dapat dilihat adanya perbedaan koefisien regresi (R2) pada
persamaan konstanta laju reaksi antara data eksperimen dengan data teoritis.

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 2. Gambar 2 menunjukkan hubungan waktu reaksi (t) vs [Ot]/[O0] = 1-Yield pada berbagai
suhu dan rasio molar (1:4; 1:5; dan 1:6). Hubungan tersebut disajikan secara eksponensial
pada semua rasio molar.

BAB IV. PEMBAHASAN

i) Karakteristik UFO (Dini Hayatul Nufus)
1. Berdasarkan parameter komposisi yang mendominasi UFO, dapat disimpulkan bahwa
minyak goreng yang umum digunakan oleh masyarakat berasal dari minyak sawit.
2. UFO dari minyak sawit memiliki persentase berat yang cukup besar yang terdiri dari 3
asam lemak yaitu palmitat, oleat dan linoleat.

ii) Yield Biodiesel (Radika Putri)

1. Semakin lama waktu reaksi maka semakin besar peluang terjadinya tumbukan antara
minyak dan metanol, dan produk yang dihasilkan akan semakin banyak
2. Transesterifikasi merupakan suatu reaksi kesetimbangan, yang berarti laju reaksi maju
akan sama dengan laju pada saat kondisi setimbang.
3. Untuk memperoleh produk biodiesel yang semakin banyak maka dapat dilakukan dengan
menambahkan jumlah metanol. Semakin banyak metanol yang ditambahkan maka produk
biodiesel yang dihasilkan akan semakin banyak.
4. Menurut Majid dkk, 2012 dan Venkateswarulu dkk, 2014, produk biodiesel tertinggi
dihasilkan pada perbandingan molar minyak dan metanol 1:6.
5. Semakin tinggi suhu maka produk biodiesel yang dihasilkan juga semakin meningkat. Pada
perbandingan molar 1:6 dengan waktu 10 menit, biodiesel akan naik dari 66,19% pada
suhu 30°C menjadi 78,44% pada suhu 55°C.
6. Kenaikan suhu reaktan akan mengakibatkan pergerakan partikel yang lebih cepat sehingga
tumbukan yang terjadi antara partikel juga akan semakin sering terjadi.

iii) Parameter Kinetika (Mazaya Amajida)

1. Persamaan 1-Yield = exp(-kt) menunjukkan bahwa [Ot]/[O0] = 1-Yield berhubungan dengan
fungsi eksponensial dari -kt.

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 2. Grafik waktu reaksi (t) vs [Ot]/[O0] dengan koefisien regresi (R2) yang tinggi (mendekati
0,9) menunjukkan bahwa asumsi orde satu untuk reaksi transesterifikasi UFO
menggunakan metanol dapat diterima dengan baik.
3. Plot Arrhenius antara nilai k vs 1/T dengan R2 yang tinggi menunjukkan bahwa suhu yang
semakin tinggi akan meningkatkan tumbukan antar molekul dan meningkatkan laju reaksi.
4. Nilai slope pada k vs 1/T digunakan untuk menghitung konstanta frekuensi tumbukan
molekul (A) dan dengan persamaan Arrhenius nilai energi aktivasi (Ea) juga dapat
ditentukan.
5. Pada rasio molar minyak dan metanol, semakin banyak metanol yang diberikan maka
semakin tinggi kemungkinan terjadinya tumbukan antar molekul.

iv) Validasi Model (Muammar Khadafi)

1. Dari gambar 4, dapat dipastikan bahwa hasil produksi berdasarkan prediksi mendekati nilai
yang telah diukur dengan persentase RMS (%RMSE) adalah sebesar 3,39% (dibawah
10%). Dengan nilai RMSE yang demikian, hasil produksi ini diklasifikasikan sangat baik.
2. Berdasarkan Gambar 4 yaitu Predicted Yield vs Observed Yield, dapat dikatakan bahwa
model persamaan kinetika ini sangat baik digunakan untuk memprediksi hasil biodiesel.
Hal ini dikarenakan besarnya koefisien determinasi (R2) sebesar 0,8454 (mendekati 1).
Nilai R2 ini menunjukkan hubungan/korelasi yang signifikan dengan Observed Yield
dikarenakan nilai R2 yang diperoleh berada dalam kisaran 0,81-0,99.
3. Gambar 4 juga menampilkan 16 poin data (dari 18 data) berada di daerah hasil yang
diamati (Observed Yield) sebesar ± 5% yang menunjukkan indikasi kuat bahwa model
persamaannya sesuai/cocok untuk memprediksikan hasil daripada biodiesel.

BAB V. KESIMPULAN (Nava Resi BR Sembiring)

1. Yield biodiesel tertinggi yang diperoleh sebesar 78,44% pada kondisi optimum dengan
suhu 55°C, rasio molar minyak:metanol sebesar 1:6, dan waktu reaksi selama 10 menit.
2. Nilai konstanta laju reaksi, k pada reaksi transesterifikasi UFO cenderung meningkat
dengan bertambahnya suhu dan rasio molar.

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3. Penggunaan model kinetika orde satu sesuai digunakan untuk memprediksi yield biodiesel
pada reaksi ini dikarenakan persentase RMSE yang kecil yaitu 3,39% dan nilai R2 sebesar
0,8454.

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PERTANYAAN DAN JAWABAN
Nama : Kausar
Kelompok :5
Pertanyaan :
1. Apa yang membuat transesterifikasi dikategorikan sebagai reaksi kesetimbangan ?
Jawaban :
Transesterifikasi merupakan reaksi kesetimbangan (reversible) dimana reaksi pembentukan
minyak/lemak dan alkohol menjadi senyawa alkil ester (biodiesel) dan gliserol dapat kembali ke
bentuk awal reaktannya kembali. Penambahan katalis NaOH dapat mempercepat terjadinya
keadaan kesetimbangan tersebut. Hal ini sudah ditetapkan dari beberapa peneliti sebelumnya
dengan melakukan riset berdasarkan beberapa data lab sehingga reaksi transesterifikasi
dikategorikan sebagai reaksi kesetimbangan. Karakteristik reaksi kesetimbangan di antaranya
adalah reaksi berjalan dalam sistem tertutup, dimana tidak ada reaktan atau produk yang
meninggalkan sistem dan konsentrasi reaktan dan produk adalah sama ketika mencapai
kesetimbangan.

2. Mengapa ada tanda negatif (-) pada baris kedua perhitungan?

Jawaban :
Konsentrasi UFO ([O]) merupakan reaktan yang selalu bereaksi dan lama kelamaan akan habis
sehingga ditempatkan pada bagian konsumsi neraca massa dan bertanda negatif.

Nama : Muhammad Defan Akbar

Kelompok :1
Pertanyaan :
1. Hasil validasi model yang didapatkan dengan persamaan kinetika yaitu R2 = 0,84. Mengapa
model ini dikatakan baik dan cocok digunakan pada persamaan tersebut? Apakah ada model
lain yang bisa menggambarkan proses ini?
Jawaban :
Model validasi yang didapatkan sebesar R2 = 0,84 berada dalam kisaran 0,81-0,99 sehingga model
ini tergolong baik untuk memprediksi hasil biodiesel menggunakan model tersebut. Adanya
parameter lain yaitu RMSE sebesar 3,39% yang tergolong kecil ini juga memperkuat hasil validasi

8
model tersebut. Hasil validasi R2 = 0,84 pada penelitian ini menggunakan persamaan orde reaksi
1. Namun begitu, hasil validasi ini masih dapat ditingkatkan ketepatannya dengan menggunakan
model persamaan lain, oleh karenanya saran dari penulis yaitu dapat dilakukan percobaan
menggunakan persamaan orde yang lebih besar untuk mendapatkan nilai R2 yang lebih tinggi.

2. Mengapa penggunaan UFO (minyak goreng bekas) dapat menghemat biaya?

Jawaban :
Pengolahan minyak goreng bekas (UFO) menjadi biodiesel dapat menghemat biaya produksi 35%
dibandingkan dengan biodiesel dari CPO dan dapat mengurangi 91,7% emisi CO2 dibandingkan
solar. Penggunaan UFO ini juga merupakan energi terbarukan mengingat persediaan minyak bumi
lama kelamaan pasti akan habis. Adapun implementasi UFO sebagai biodiesel ini sendiri masih
sangat minim di Indonesia dikarenakan harga biodiesel jika tidak disubsidi akan lebih mahal
dibandingkan produksi diesel per liternya. Harga biodiesel yang tidak disubsidi ini disebabkan
harga produksinya yang lebih mahal, sehingga pemerintah turun tangan dengan cara
mencampurkan biodiesel 20-30% dengan diesel dari minyak bumi. Beberapa upaya yang dapat
dilakukan untuk menurunkan harga produksi biodiesel ini yaitu dengan cari bahan baku yang
murah dan cari proses produksi yang murah seperti menggunakan proses trans in situ.

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 DAFTAR PUSTAKA

Mahlinda, M. Dani Supardan, Husni Husin, dan Medyan Riza. 2016. Transesterifikasi In Situ Biji
Pandan Laut Menjadi Biodiesel Mneggunakan Gelombang Ultrasonik. Jurnal Teknologi
Industri Pertanian, 26 (3): 294-300.
Tim Riset dan Publikasi Katadata. 2022. Menakar Peluang Pemanfaatan Minyak Jelantah Untuk
Biodiesel. https://katadata.co.id/timrisetdanpublikasi/analisisdata/5ff67457daed7/menakar-
peluang-pemanfaatan-minyak-jelantah-untuk-biodiesel, diakses pada 18 Maret 2022.

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 LAMPIRAN

1. Contoh Perhitungan (Farhana Zakiah)

(Terlampir jurnal yang direview)

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 Aceh Int. J. Sci. Technol., 9(1) 1-11
April, 2020
doi: 10.13170/aijst.9.1.13297

First Order Kinetics of Biodiesel Synthesis Using Used Frying Oil through
Transesterification Reaction

Agus Haryanto1,*, Amieria Citra Gita1, Tri WahyuSaputra2, and Mareli Telaumbanua1
1Department of Agricultural Engineering, Faculty of Agriculture, the University of Lampung, Indonesia;
2Department of Agricultural Engineering, Faculty of Agricultural Technology, University of Jember, Indonesia
*Corresponding author email: agus.haryanto@fp.unila.ac.id

Received : March 9, 2019

Accepted : April 11, 2020
Online : April 30, 2020

Abstract – This research aims to study the first-order kinetics of biodiesel production from used frying oil
(UFO) through transesterification with methanol. Used frying oil was collected from fried peddlers around the
campus of the University of Lampung. Technical grade methanol and NaOH catalyst were purchased from a
local chemical supplier. The experiment was carried out with 100 ml of UFO at various combinations of oil to
methanol molar ratio (1:4, 1:5, and 1:6), reaction temperatures(30 to 55oC, the ramping temperature of 5o C), and
reaction time of 0.25 to 10 minutes. First-order kinetic was employed using 126 data pairs (87.5%). The acquired
kinetic model was validated using 18 data sets (12.5%) observed at a reaction time of eight min. Results show
that biodiesel yield was increased with reaction time, its molar ratio, and temperature. The maximum return of
78.44% was achieved at 55oC and molar ratio of 1:6. The kinetic analysis obtains the reaction rate constant (k)
in the range of 0.045 to 0.130. The value of k increases with the reaction temperature and molar ratio. The
analysis also reveals the average activation energy (Ea) of the UFO transesterification reaction with methanol
and NaOH catalyst to be 21.59 kJ/mol. First-order kinetic is suitable to predict biodiesel yield from UFO because
of low %RMSE (3.39%) and high R2 (0.8454).

Keywords: biodiesel, used frying oil, kinetics, first order, transesterification.

Introduction
Biodiesel can be defined as a fuel comprised of mono-alkyl (methyl, propyl, or ethyl) esters of long-chain
fatty acids derived from vegetable oils or animal fats (Ahmad et al., 2013). Biodiesel has properties so similar to
diesel fuel that it can be used to substitute diesel fuel (Demirbas, 2007; Srivastava and Prasad, 2000; Javed Ali
and Anurag Semwal, 2014). The advantage of biodiesel is renewable compared to non-renewable diesel oil.
Therefore, the development of biodiesel is one way to reduce dependence on petroleum. Also, biodiesel
utilization may reduce greenhouse gas (GHG) emissions. A study in the United States revealed that GHG
emission associated with biodiesel production from soybean and its utilization is the lowest compared to that of
gasoline, diesel fuel, or corn grain ethanol (Hill et al., 2006). Biodiesel contains low sulfur and has better lubricity
that is good for engines (Hazrat et al., 2015). Biodiesel is made from organic feedstock so that it is an ecologically
friendly fuel due to its possibility to be decomposed biologically (Bajpai and Tyagi, 2006).
In Indonesia, biodiesel is used as a blend to diesel fuel and commercially marketed as BXX, with XX
represents the volume percentage of the biodiesel in the mix. Based on the regulation of Minister of Energy and
Mineral Resources No. 12/2015 on the Supply, Utilization, and Trade of Biofuels as Other Fuel, by 2016, diesel
fuel has to be marketed with a 20% biodiesel mixture or B20 for all sectors including PSO (public service

1
 Aceh Int. J. Sci. Technol., 9(1) 1-11
April, 2020
doi: 10.13170/aijst.9.1.13297

obligation) and non-PSO transportations. The blend will increase to 30% by 2020 (Berita Negara Republik
Indonesia No. 406, 2015).
Biodiesel production using vegetable oils or animal fats has resulted in high biodiesel prices due to high
feedstock cost. A model of medium-sized biodiesel industry based on continuous-transesterification of crude
degummed soybean oil with an annual capacity of 10 million gallons requires feedstock cost at US$17.507 million
or 87.35% of the total production cost of US$20.041 million (Haas et al., 2006). Other works reported feedstock
cost in a range of 61.2 to 77.4% depending on feedstock types and system capacity (Santana et al., 2010; Zhang
et al., 2003; Tasić et al., 2014). Therefore, the cheap feedstock is good for biodiesel production. It has been
recommended that UFO should be the primary feedstock for biodiesel, whereas fresh edible and non-edible oils
are used as a supplement for the feedstock deficit (Gui et al., 2008).
The used frying oil is a vegetable oil that has been used for food preparation and no longer suitable for human
consumption (Gui et al., 2008). During the deep-frying process, the oil undergoes some chemical and physical
changes (color, odor, and viscosity) that may cause health problems, such as gastrointestinal disorders (Raqeeb
and Bhargavi, 2015) and even cancer (Venkata and Subramanyam, 2016; Yuniwati and Karim, 2009). Therefore,
utilization of UFO for food and food-related stuff such as frying food and making chili sauce is not
recommended. Dumping the UFO directly into the soil can cause environmental problems due to its high value
of chemical oxygen demand. Producing biodiesel from UFO is an appropriate solution (Adhiatma et al., 2012)
because of its low cost. The development of biodiesel from UFO will provide a more acceptable option in using
used oil.
The potential of UFO in Indonesia increases with the increasing vegetable oil consumption. Fujita et al. (2013)
reported that a family in Bogor consumes cooking oil of 3 liters per month (36 L/y). UFO can be converted into
biodiesel through transesterification reaction with methanol and inexpensive sodium hydroxide (NaOH) catalyst
as simply presented in Equation (1).
Oil + Alcohol Biodiesel + Glycerol (1)
The transesterification is an equilibrium reaction so that the maximum biodiesel product is obtained with the
excess of methanol. The disadvantage of this reaction is that there may be a side reaction in the form of soap,
which will deactivate the catalyst so that it can reduce biodiesel yield, especially if the free fatty acid content in
the oil is reasonably high. Kinetics of transesterification reaction is essential to predict the biodiesel yield at
certain times and conditions. The kinetic parameters to be determined include the reaction rate constant, a factor
of collision frequency, and activation energy. Typically, transesterification reaction is performed at much higher
of alcohol mole than oil mole that the concentration of alcohol can be assumed constant, and the rate of reaction
is, therefore, dependent only on the concentration of oil (Turner, 2005). Hence, the first-order model is widely
applied to analyze the kinetics of transesterification reaction for biodiesel synthesis (Aisyah et al., 2012; Farag et
al., 2013; Emeji et al., 2015; Moradi et al., 2015; Mohadesi et al., 2018; Aniokete et al., 2019).
The factors used to determine the reaction kinetic are temperature and reaction time. The molar ratio of oil
to alcohol influence biodiesel yield. Therefore, the effect of the molar ratio on the reaction kinetic is also
important (Trejo-Zárraga et al., 2018) to determine the efficient operation of biodiesel production. The purpose
of this study is to determine the kinetic parameters of the UFO transesterification reaction to a molar ratio of
oil to methanol.

Materials and Methods

Materials
Used frying oil was obtained from fried food sellers around the campus of the University of
Lampung. The oil used for cooking food was originated from palm oil. The collected UFO was filtered
using a tea filter to separate solid particles. Technical grade methanol and NaOH were purchased from
a local supplier (CV Panca Mandiri, Bandar Lampung). Free fatty acid (FFA) content, acid number, and
viscosity of UFO were determined according to our previous work (Haryanto et al., 2015). Fatty acids
of oil were analyzed by gas chromatography-mass spectroscopy (GCMS-QP2010 Ultra, Agilent
Technologies Inc., Palo Alto, CA, U.S.A.) equipped with a capillary column (30m, 0.25 mm, 0.25 mm
film thickness). The GC-MS analyses were carried out in split mode injection with split ratio 1:200),

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using nitrogen as the carrier gas (1.31 mL/min flow rate) and the inlet pressure of 80.2 kPa. The sample
volume injected was 1μl. The injector temperature was fixed at 280 °C. The oven temperature was held
at 60 °C for 0 min and then programmed at 8 °C/min to a final temperature of 280 °C, where it was
maintained for 2 min.

Research procedure
The treatment in this study was a combination of variations in the molar ratio of oil to methanol (MR),
temperature, and reaction time. Lin and Hsiao (2012) reported that the optimal reaction for biodiesel synthesis
occurred at MR of 1:6 with an average yield of 97.49 %, and a further increase of MR to 1:9 did not influence
the yield. Kumar et al. (2011) also reported little difference in triglyceride conversion between the MR 1:6 and
1:10. Therefore, the variation of MR in our work consisted of three levels, namely 1:4, 1:5, and 1:6. The reaction
temperature consisted of six levels, namely 30 to 55 °C, with ramping of 5o. Kumar et al. (2011) reported that
almost complete conversion of jatropha oil transesterified with methanol is achieved in 10 minutes at 60oC.
Hence, in this work, we used a maximum reaction time 10 minutes consisted of eight levels (0.25, 0.5, 1, 2, 3, 6,
8, and 10 minutes).
Each experimental unit was carried out with 100 mL of UFO and NaOH of 0.5% of the oil weight. Hossain
& Mazen (2010) studied biodiesel production using waste soybean oil with methanol and NaOH catalyst (0.5,
1.0, and 1.5% of oil weight). The results show that the highest biodiesel yield is produced using 0.5% and 1%
catalyst with no significant difference. Initially, we prepared a methoxy solution by mixing 0.5 gram NaOH into
methanol and stirring until all NaOH particles dissolve. The amount of methanol is calculated based on the
predetermined MR, namely 14.9 mL for MR 1:4, 18.2 mL for MR 1:5, and 21.8 mL for MR 1:6. The UFO was
heated in an Erlenmeyer glass equipped with a reflux condenser to a specified temperature, and the methoxy
solution was then poured into it and stirred at 300 rpm using a magnetic stirrer for a specified duration. The
solution was then left to still for 24 hours. Biodiesel was separated from glycerol and washed using warm aqua
dest several times until clean (marked by clean wastewater). Biodiesel yield was calculated by Equation (2):
Yield = [Bt/O0] × 100% (2)

Transesterification kinetic
The following kinetics model was structured based on the assumption that transesterification is a first-order
reaction and is a function of reaction temperature and the concentration of oil. The assumption is based on the
fact that the reaction was performed using an excess of methanol. The kinetics equation is constructed in the
following (Kusdiana and Saka, 2001):
d [O]
Reaction rate =  = k [O] (3)
dt
Integrating Equation (3) results in:
[Ot]/[O0] = exp(–kt) (4)
The oil concentration at t = 0 is [O0] and at different t is [Ot], where [O0] > [Ot]. Noting that at any time the
conversion of oil into biodiesel is X, we will have X = 1 – [Ot]/[O0], and by substituting into Equation (4) and
dividing all terms by [O0] we have:
1 – X = exp(–kt) (5)
In this case, oil conversion to biodiesel (X ) is equal to biodiesel yield calculated by Equation (2). Therefore,
Equation (5) can be presented as:
1 – Yield = exp(–kt) (6)
Plotting of Equation (6) with t as abscissa and the negative value of natural logarithm (1 – X) as ordinate can
be used to determine the values of the reaction rate constant (k, mole/minute) at various temperatures. Values
of k are then used to determine the activation energy value (Ea) of the reaction using the Arrhenius equation:
k = A exp(-Ea/RT) (7)
where A is constant for molecular collision, T is the absolute temperature (K), and R is the universal gas constant
(8.314472 J/mol.K).

Model validation
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The acquired kinetic equation model was validated using the biodiesel yield data set measured at reaction time
8 minutes at all molar ratios and temperatures. The goodness of predicted yield was assessed from its
determination coefficient (R2) of prediction-observation plot and %RMSE (percentage root mean squared error):
n

e
1 2
i
n
i 1
%RMSE   100 (8)
y obs
where e is residuals defined as the difference of observed yield (yobs) and predicted yield (ypre), and bar sign over
the yobs mean average value. The lower %RMSE, the better the prediction will be.

Results
Characteristics of UFO
Used frying oil used in this study had characteristics as given in Table 1. Fatty acid composition of the UFO
was dominated by palmitate (42.84%), oleate (35.71%), and linoleate (12.43%), which all together contribute
91% of the total.

Table 1. Characteristics of the UFO used in the experiment.

Parameter Unit Value

Specific mass g/mL 0. 912
Viscosity at 30°C cSt 61.75
Free fatty acid (FFA) % 1.43
Acid number g KOH/L 0.720
Methyl Laurate % 0.75
Methyl Myristate % 1.58
Methyl Palmitate % 42.84
Methyl Linoleate % 12.43
Methyl Oleate % 35.71
Methyl Stearate % 5.15
Not known % 1.54

Biodiesel yield
Figure 1 shows the relationship between reaction time and reaction temperature to the biodiesel yield at three
different oil-to-methanol molar ratios. It reveals that biodiesel yield increases with reaction time.

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70 80
Temperature 30oC Temperature 35oC
60 70

50 60

Yield (%)
50
40
Yield (%)

40
30
Molar ratio 1:4 30 Molar ratio 1:4
20 20 Molar ratio 1:5
Molar ratio 1:5
10 Molar ratio 1:6 10 Molar ratio 1:6
0 0
0 2 4 6 8 10 0 2 4 6 8 10
t (min) t (min)

80 80
Temperature 40oC Temperature 45oC
70 70
60 60

Yield (%)
Yield (%)

50 50
40 40
Molar ratio 1:4
30 Molar ratio 1:4 30
Molar ratio 1:5
20 Molar ratio 1:5 20
Molar ratio 1:6
10 Molar ratio 1:6 10
0 0
0 2 4 6 8 10 0 2 4 6 8 10

t (min) t (min)

80 90
Temperature 50oC Temperature 55oC
70 80
60 70
60
Yield (%)
Yield (%)

50
50
40
Molar ratio 1:4 40 Molar ratio 1:4
30
30
Molar ratio 1:5 Molar ratio 1:5
20 20
Molar ratio 1:6 Molar ratio 1:6
10 10
0 0
0 2 4 6 8 10 0 2 4 6 8 10
t (min) t (min)

Figure 1. Effect of reaction duration (0 to 10 min), temperature (30 to 55 °C), and molar ratio (1:4 to
1:6) on the biodiesel yield.

Kinetic Parameters
Figure 2 shows the relationship of reaction time (t) to [Ot]/[O0] = 1 – Yield at various temperatures and molar
ratios. The relationship between t and [Ot]/[O0] can be satisfactorily presented exponentially for all treatments.

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0,80 0,80

Temperature 30oC Temperature 35oC

0,70 0,70

0,60 0,60

[Ot]/[O0] = 1 - Yield
[Ot]/[O0] = 1 - Yield

0,50 0,50

0,40 0,40
y = 0,7033e -0,045t
0,30 0,30 y = 0,6846e -0,055t
R² = 0,9055 y = 0,6777e -0,058t y = 0,6461e -0,061t y = 0,5749e -0,065t
y = 0,5949e-0,059t R² = 0,9066
R² = 0,9799 0,20 R² = 0,8773 R² = 0,891
0,20 R² = 0,9808

0,10 0,10 Molar ratio 1:4 Molar ratio 1:5 Molar ratio 1:6
Molar ratio 1:4 Molar ratio 1:5 Molar ratio 1:6

0,00 0,00
0 2 4 6 8 10 0 2 4 6 8 10

t (min) t (min)

0,80 0,80
Temperature 40oC Temperature 45oC
0,70 0,70

0,60 0,60
[Ot]/[O0] = 1 - Yield

[Ot]/[O0] = 1 - Yield
0,50 0,50

0,40 0,40
y = 0,6404e -0,065t y = 0,6248e -0,07t
0,30 y = 0,6416e -0,069t 0,30
R² = 0,9112 y = 0,6061e-0,07t R² = 0,9563 y = 0,6795e -0,077t
R² = 0,9812 R² = 0,9635
0,20 R² = 0,9278 0,20 y = 0,6528e -0,084t
R² = 0,8866
0,10 Molar ratio 1:4 Molar ratio 1:5 Molar ratio 1:6 0,10
Molar ratio 1:4 Molar ratio 1:5 Molar ratio 1:6
0,00
0,00
0 2 4 6 8 10
0 2 4 6 8 10
t (min) t (min)

0,80 0,90
Temperature 50oC 0,80 y = 0,6145e -0,092t Temperature 55oC
0,70
R² = 0,8666
0,70
0,60
y = 0,6626e -0,097t
[Ot]/[O0] = 1 - Yield

y = 0,6005e -0,089t 0,60

[Ot]/[O0] = 1 - Yield

0,50 R² = 0,9621
R² = 0,9199
0,50 y = 0,7516e -0,13t
0,40 R² = 0,9759
0,40
0,30 y = 0,7308e -0,086t y = 0,6415e-0,085t 0,30
R² = 0,9853 R² = 0,9113
0,20
0,20
0,10 0,10
Molar ratio 1:4 Molar ratio 1:5 Molar ratio 1:6 Molar ratio 1:4 Molar ratio 1:5 Molar ratio 1:6
0,00 0,00
0 2 4 6 8 10 0 2 4 6 8 10
t (min) t (min)

Figure 2. Reaction rate constants (k) and intercept at different temperatures and molar ratios.

Discussion
Characteristics of UFO
Based on fatty acid composition that is dominating the UFO (Table 1), it is a strong indication that the
cooking oil commonly used in Indonesia is originated from palm oil. Kheang et al. (2006) reported UFO derived
from palm oil is composed mainly of these three fatty acids with a weight percentage of 38.5 (palmitate), 45.7
(oleate), and 8.8 (linoleate). As a leader for a palm oil producer, it is not surprised that cooking oil consumed by
most peoples in Indonesia is produced from palm oil.

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Biodiesel yield
Figure 1 shows that initially, the yield of biodiesel obtained from the experiments increases sharply as the
reaction time increases. But, after practically one minute, the increase in biodiesel yield began to slope. Susilowati
(2006) reported that biodiesel yield from kapok seed oil increases with the increasing reaction time. The longer
the reaction time, the higher chance of collisions between oil and methanol, and the higher conversion will be
(Parhusip et al., 2012).
Biodiesel yield generally increases at more methanol mole. Transesterification is an equilibrium reaction,
which means the reaction rates of forward and will be the same rate at equilibrium condition. One way to shift
the attitude towards the product (right) is by increasing methanol. The results indicate that the more methanol
we add, the more biodiesel yield we get. In the molar ratio of oil to methanol 1:6, the highest biodiesel yield
(78.44%) was gained at 55oC and reaction time of 10 minutes. Other works reported that optimum biodiesel
conversion has resulted in the molar ratio of triglycerides to methanol 1:6 (Majid et al., 2012; Venkateswarulu et
al., 2014).
In general, biodiesel yield also increases with temperature. At a molar ratio 1:6 and reaction time of 10 min,
for example, biodiesel rises from 66.19% at 30oC to 78.44% at 55oC. Increasing the temperature of reactants
results in faster movement of the particles, and therefore they collide more frequently (Connors, 1990). This
process, in turn, will speed up the reaction.

Kinetic Parameters
Equation (6) shows that [Ot]/[O0], which is equal to 1 – Yield, relates to an exponential function of –kt. The
graph shows that the plot of reaction time vs. [Ot]/[O0] can be represented satisfactorily by the exponential
Equation with a high regression coefficient (close to 0.9). It means that the first-order assumption for the
transesterification reaction of UFO using methanol can be adequately accepted. Figure 2 also shows that reaction
rates are greatly affected by temperature, which also demonstrated by other studies (Walas, 1989; Cornish-
Bowden, 2012). The significant effect of temperature on reaction rate is obvious from Arrhenius relation as
presented by Equation (7). Equation (6), however, has no intercept (the coefficient is 1), and some studies have
confirmed it (Moradi et al., 2015; Farag et al., 2013; Mohadesi et al., 2018). Our results (Figure 2), provided
intercept between 0.575 (at MR 1:6 and temperature 35oC) to 0.752 (at MR 1:6 and temperature 55oC). It could
have resulted from the temperature effect. The presence of intercept was also reported by other works (Aisyah
et al., 2012; Talebian-Kiakalaieh et al., 2013; Emeji et al., 2015; Aniokete et al., 2019).
Based on the reaction rate constants as collected from Figure 2, an Arrhenius plot was made to represent the
relation between the values of k with the inverse of absolute temperature (1/T) at three levels of the molar ratios
as presented in Figure 3. The figure shows that the relationship between 1/T to the natural logarithm values of
k can be well represented linearly, indicated by a high regression coefficient (> 0.90). Upadhyay (2006) explains
that raising the temperature will increase the collisions and hence increases the reaction rate. A further
implication of this is that increasing temperature also increases the value of k. The dependence of constant rate
k on temperature has already described by the Arrhenius expression. Based on the slope values obtained from
Figure 3 and referring to the Arrhenius equation, we calculated the global activation energy value (Ea) and the
constant of molecular collision frequency, and the results were presented in Table 2. We observe that the molar
ratio of oil to methanol slightly affected Ea values, which are 23.61, 17.33, and 23.83 kJ/mol, respectively, at a
molar ratio of 1:4, 1:5, and 1:6. The average value of Ea is 21.59 kJ/mol, which is in the range of values reported
by other works, i.e., 26.97 (Kwartiningsih et al., 2007), 30.2 (Issariyakul and Dalai, 2012), 41.94 (Buchori and
Sasongko, 2012), 38.46 (Said et al., 2010), 52.51 (Azizet al., 2016), 30.69 (Haryanto et al., 2017), and 23.69 (Jaya
and Selvan, 2014).

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0,14
Molar ratio:
0,12 1:4 1:5 1:6
0,10

k (mol/minute)
0,08

0,06

0,04 y = 54,359e-2084x
y = 545,65e -2840x R² = 0,9858 y = 708,12e-2866x
0,02
R² = 0,9838 R² = 0,9022
0,00
0,003 0,00305 0,0031 0,00315 0,0032 0,00325 0,0033 0,00335
1/T (K-1)

Figure 3. Linear plot of the Arrhenius equation at three different molar ratios.

Table 2. Activation energy (Ea) and molecular collision frequency constant (A) of UFO transesterification.

Molar ratio Ea (kJ/mol) A (min-1)

1:4 23.61 545.65
1:5 17.33 54.36
1:6 23.83 708.12

A part of the Arrhenius equation is the collision frequency factor (A), which is also known as the pre-
exponential factor. This factor represents the frequency of collisions between reactant molecules. From Table 2,
the value of the pre-exponential element is 545.65 min–1 at MR 1:4 and increases to 708.12 min–1 at MR 1:6. This
implies that the more methanol is given, the higher a chance that molecular collisions may occur. However, at
MR 1:5, the value of the pre-exponential factor drops considerably to 54.36 min–1. It is still unexplained yet as
to why this could have happened.

Model validation
Figure 4 shows a comparison between biodiesel yields measured at a reaction time of 8 minutes, and the
prediction yields calculated using the acquired kinetic parameters. We can confirm that the predicted yields are
close to the measured values with %RMSEof 3.39%. The expected return is classified as excellent because the
amount of %RMSE is less than 10% (Li et al., 2013; Despotovic et al., 2016). Furthermore, Figure 4 shows the
model can be satisfactorily used to predict the biodiesel yield with the determination coefficient (R2) of 0.8454.
According to Sugiyono (2008), the predicted values have a strong correlation with observed values at R2 values
of 0.81-0.99. The figure also shows that 16 data points (out of 18) fall in the area of the observed yield ± 5%.
Again, this is a strong indication that the equation model is appropriate to predict biodiesel yield.

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80

75 R2 = 0.8454

70

Predicted Yield (%)

65

60

55

50
50 55 60 65 70 75 80
Observed Yield (%)

Figure 4. Prediction vs. observation of biodiesel yield (the shaded area is in the range of ±5% of the return)

Conclusion
The highest biodiesel yield of 78.44% was achieved at the optimum condition of the oil-to-methanol molar
ratio of 1:6, temperature of 55oC, and reaction time of 10 min. The kinetics of transesterification reactions can
be suitably explained using a first-order reaction model with an intercept between 0.575 and 0.752. The values
of the reaction rate constant in the transesterification reaction of UFO tend to increase with increasing
temperature. The reaction rate constants also increase concerning the molar ratio of oil to methanol with the
lowest value of k = 0.045 (temperature of 30°C, the molar ratio of 1:4) and the highest k = 0.130 (temperature
of 55°C, molar ratio of 1:6). The activation energy in the transesterification reaction of UFO is, on average of
21.59 kJ/mol. The first-order kinetic model is suitable and can be satisfactorily used to predict biodiesel yield,
which is reflected in the low %RMSE (3.39%) and high R2 (0.8454).

Acknowledgment
The research was financially supported by the DGHE (Directorate General of Higher Education), Ministry
of Research, Technology, and Higher Education, through the FUNDAMENTAL Research program with
contract number 071/SP2H/LT/DRPM/IV/2017585 (June 2, 2017).

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