ANALYSIS THE CONTENT OF JARAK KEPYAR (RICINUS COMMUNIS, L.

) BIODIESEL
BY GAS CHROMATOGRAPHY MASS SPECTROPHOTOMETER (GC-MS)
Ni Kadek Wahyuni Antari (1213031002/A)
Chemistry Education Department, Faculty of Mathematics and Natural Sciences
Universitas Pendidikan Ganesha
INTRODUCTION
Separation is an important process in the analytical procedures. Separation method that
usually used to separate many complex component of mixture in little amount of sample is
called chromatography. The basic principle of chromatography is separation method for
complex components of mixture based on interaction of the components mixture with static
phase and mobile phase. There are many types of chromatography; one of them is gas
chromatography.
Gas chromatography is the components of vaporized sample are separated as a
consequence of being partitioned between a mobile gaseous phase and liquid or solid stationary
phase held in the column. In performing a gas chromatographic separation, the sample is
vaporized and injected into the head of a chromatographic column. Elution is brought about by
the flow of an inert gaseous mobile phase. In contrast to most other type of chromatography,
the mobile phase does not interact with molecules of the analyte, its only function is transport
the analyte through the column [3]. There are two kinds of gas chromatography, such as gassolid chromatography (GSC) and liquid-gas chromatography (GLC).
Liquid-gas chromatography based on partition of analyte between mobile phase (gas)
and stationary phase (liquid) mobilized on inert solid surface (Muderawan, 2009). Solid-gas
chromatography (GSC) based on solid stationary phase whereas analyte retention occurred as
consequence from adsorption physically by solid stationary phase. Solid-gas chromatography
has limit application because of semi active molecule and polar molecule will strongly interact
with stationary phase therefore tailing is occurred when the peak are eluted, as consequence
from process adsorption non linier. This technique is used to separate gas molecule with low
molecular molecule weight.
Basic Principle of Gas Chromatography
The effectivity of coulomb chromatography in separating two solute substances depends
on the relative rate of two elusion species. This rate is determined by equilibrium constant
distribution of solute substance in mobile phase and stationary phase. Quantitatively, GC-MS
data can be calculated by considering retention factor (migration rate of solute substance),
selectivity factor (relative migration rate), coulomb efficiency and coulomb resolution.
Retention factor
Retention factor is an important parameter used for describing migration rate of solute
substance in coulomb. The retention factor of kA is as follow:

=

Selectivity Factor
Selectivity factor of a coulomb for two species A and B is defined as the following equation:

Coulomb Efficiency
To find the number of N (plate number) can be used the following equation:
2
= 16 ( )

Coulomb Resolution
Resolution column provide quantitatively measure the ability of the column to separate
analytes. Resolution column is defined as follows:
2[( ) ( ) ]
=
+
Gas chromatography can also be combined with a mass spectrometer, in this case the
mass spectrometer can be considered as a detector, known as the Gas Chromatography Mass
Spectrometry (GC-MS). Gas Chromatography-Mass Spectrometry is analysis method based on
chromatography by using detector of mass spectrometer. Result of the analysis is in form of
chromatogram and mass spectrum of a compound. GC-MS analysis method is common used
for determining composition of chemical of sample such as composition of crude oil,
composition of pesticide in fruits, composition of cholesterol in plant oil and so on [1].
GC-MS is a combination of two different analytical techniques, Gas Chromatography
and Mass Spectrometry. GC-MS, with the use of internal standards, provides a
multidimensional drug identification and quantitation procedure that is the leading
confirmation method for forensic drug testing. Composition of methyl ester in biodiesel which
is made from plant oil through transferification also can be determined by GC-MS. The purpose
of this experiment is to determine methyl ester contained in biodiesel of Jarak Kepyar (Ricinus
communis, L.) oil.
Castor (Ricinus communis L, Euphorbiaceae) is a versatile plant species. Castor bean has a
high oil rendemen, which could reach 56%. Castor oil contains fatty acids such as palmitic acid
1.3%, 5.5% oleic acid, linoelat acid 7.3%, 1.9% stearic acid, ricinoleic acid and 84% (Salimon in
Sinarsih, 2010). All of the fatty acids contained in the castor oil is a long-chain of fatty acids.
Generally the characteristic of castor oil can be seen on the picture below:
Table 1. The Characteristic of Castor Oil

Characteristic
Liquid condition
Density
Saponification number
Fatty acid composition
Palmitate acid
Oleic acid
Linoleic acid

Composition
Viscous
9.31 x 10-1 g/cm3
182.9 mg/g
1.3%
5.5%
7.3%

Linolenate acid
Stearic acid
Ricinoleic acid

0.5%
1.2%
84.2%

Further research state that about 90% of the fatty acid content of castor oil is the
triglyceride formed from ricinoleic acid. Ricinoleic acid (12-hydroxy-9-cis-octadecenoic acid) is
unsaturated omega-9 fatty acid that naturally occurs in nature Castor plant (Ricinus communis L,
Euphorbiaceae) seeds or in sclerotium of ergot (Claviceps purpurea Tul, Clavicipitaceae).
Omega-9 fatty acid that naturally occurs in nature Castor plant (Ricinus communis L,
Euphorbiaceae) seeds or in sclerotium of ergot (Claviceps purpurea Tul, Clavicipitaceae).
Ricinoleic acid is a viscous yellow liquid, with a melting point of < 100C and boiling point of
4160C at 760 mmHg. It is insoluble in water but soluble in most organic solvents. It is prepared
by the hydrolysis of castor oil. It used in the textile finishing, in coating, inks and in making
soaps [4].
Ricinoleic acid which is the greatest composition of castor oil is a unique fatty acid that
is unique, because this fatty acid is oleic acid derivative in which has a hydroxyl group at = 12
and containing the bond at = 9. Ricinoleic acid having 18 carbon atoms with one hydroxyl
group on the carbon atom number 12 and double bond at carbon number 9 and 10 with cis
structure. Ricinoleic acid has molecular weight is 298.46. Due to the high content of ricinoleic
acid in castor oil, it makes the castor oil has high hydroxyl group, iodine and saponification
number compare to the other oil. Unlike other oils, castor oil mixed with alcohol and slightly
soluble in petroleum ether at room temperature. (Naughton, 1973). Figure 1 shows the
molecular structure of ricinoleic acid.
O
OH
OH

Figure 1. Structure of ricinoleic acid

The objectives of this experiment were to analyze the content of Jarak Kepyar (Ricinus
communis L.) biodiesel from GC-MS data.
METHODS
The content of methyl ester in biodiesel made from jarak kepyar (Ricinus communis L.) oil
was analyzed by GC-MS Agilent 6890N. The colum used was HP5-MS with length was 30 m
and ID was 0,32 mm. The injector was setted at temperature of 260oC and the volume of sample
was 1.0L. The temperature of oven was 260oC for 5 minutes and then increased 10oC/minutes
until 270oC. It is then keep for 270oC for 5 minutes. The bringing gas was helium with flowing
rate of 1 mL per minutes. The detector is MS (Mass spectrophotometer) [2].
RESULTS AND DISCUSSION
The content of methyl ester in biodiesel made from jarak kepyar (Ricinus communis L.) oil
was analyzed by GC-MS Agilent 6890N. The coloum used was HP5-MS with length was 30 m
and ID was 0,32 mm. The injector was setted at temperature of 260oC and the volume of sample

was 1.0L. The temperature of oven was 260oC for 5 minutes and then increased 10oC/minutes
until 270oC. It is then keep for 270oC for 5 minutes. The bringing gas was helium with flowing
rate of 1 mL per minutes. Then, the result of GC-MS of jarak kepyar biodiesel can be seen as
follows.

Figure 3. Chromatogram of Jarak Kepyar Biodiesel

The percentage of compound in jarak kepyar biodiesel was calculated by following equation.
%=

100%

The percentage of compound in jarak kepyar biodiesel was calculated in the following table.
Table 2. Result of Chromatogram Analysis Biodiesel Jarak Kepyar
No

RT

Area

Compound

1
2

19.94
21.58

2.17
8.61

3
4

21.63
21.68

7.65
1.35

5
6

21.84
23.38

2.11
77.57

7
8

23.60
24.99

0.44
0.10
= 100

Methyl hexadecanoate
Methyl 9, 12octadecadienoate
Methyl 9-octadecenoate
Methyl 11octadecenoate
Methyl octadecanoate
Methyl 12-hydroxy-9octadecenoate
Methyl eicosanoate
Not identified

Molecular
Formula
C17H34O2
C19H34O2

Mr
(g/mole)
270
294

Rs

2.17%
8.61%

9.316

C19H36O2
C19H36O2

296
296

7.65%
1.35%

0.211
0.252

C19H36O2
C19H36O3

296
312

2.11%
77.57%

0.833
4.438

C21H42O2
-

326
-

0.44%
0.10%
= 100%

0.489
5.148

The molecular structures of each compound in Jarak Kepyar biodiesel were as follow:
1. Methyl Hexadecanoate
H3C

CH3

O
O

2. Methyl 9, 12-Octadecadienoate
O

CH3

H3C
O

3. Methyl 9-Octadecenoate
O

CH3

H3C
O

4. Methyl 11-Octadecenoate
O

CH3

H3C
O

5. Methyl Octadecanoate
O

CH3

H3C
O

6. Methyl 12-hydroxy-9-Octadecenoate
O

CH3

O
H3C

HO

7. Methyl Eicosanoate
O

CH3

H3C
O

Figure 4.The molecular structure of each component of Jarak Kepyar

Figure 5. The mass spectrums of component in Jarak Kepyar Biodiesel with retention time of 23.38
minutes

Then, the fragmentation of methyl ester with retention time 23.38 minutes in order to prove the
molecular structure of methyl 12-hydroxy-9-octadecenoate as follows.

Fragmentasi methyl 12-hydroxy-9-octadecenoate (Part 1)

O
O

HO

m/e=312
- H2O (18)

O
O

m/e=294
- CH3 (15)

O
O

m/e=279
Fragmentasi methyl 12-hydroxy-9-octadecenoate (Part 2)
O
O

m/e=279
- CH4 (16)

O
O

m/e=263
- CH6 (18)
O
O

m/e=245

Fragmentasi methyl 12-hydroxy-9-octadecenoate (Part 3)

O
O

m/e=245
- H2O (18)

m/e=227
- OCH (29)

m/e=198
Fragmentasi methyl 12-hydroxy-9-octadecenoate (Part 4)

m/e=198
- C2H8 (32)

m/e=166
- CH6 (18)

m/e=148

- C2H5 (29)

m/e=137

Fragmentasi methyl 12-hydroxy-9-octadecenoate (Part 5)

- CH(13)

m/e=124
m/e=137
- CH2 (14)

m/e=110

Fragmentasi methyl 12-hydroxy-9-octadecenoate (Part 6)

O

CH 3

H3 C
O

HO

m/e=312
- C16H16OH(225)

CH 3

- CH(13)
O

m/e=87

m/e=74

CH 3

Fragmentasi methyl 12-hydroxy-9-octadecenoate (Part 7)

- CH(13)

m/e=97

m/e=110

- C3H6 (42)
- CH2 (14)
CH3

- C(12)

- CH2(14)

m/e=15

m/e=29

m/e=41

m/e=55

Figure 6. Fragmentation of methyl 12-hydroxy-9-octadecenoate

CONCLUSIONS
Based on the result and discussion above, it can be concluded that Jarak Kepyar (Ricinus
communis, L.) biodiesel contains of eight compounds, namely: methyl hexadecanoate, methyl
9,12-octadecadienoate,
methyl
9-octadecenoate,
methyl
11-octadecenoate,
methyl
octadecanoate, methyl 12-hydroxy-9-octadecenoate, methyl eicosanoate. Then, the main
compound was methyl 12-hydroxy-9-octadecenoate that has retention time of 23.38 minutes
and its percentage was 77.57%.
REFERENCES
1. Muderawan, I. W. 2009. Analisis Instrumen. Undiksha Press: Singaraja.
2. Muderawan, I. W. Jurnal Praktikum Analisis Kimia Instrumen.
3. Pertiwi, L. L. 2013. Purification of Ricinoleic Acod from Castor Oil by Column Chromatography.
Thesis.
4. Sinarsih, K. 2012. Penentuan Waktu OptimumTransesterifikasi dan Komposisi Methyl Ester
Penyusunan Biodiesel Minyak Jarak Kepyar (Ricinicus Communis L.). Skripsi.