EXPERIMENT 5

ANALYSIS OF HYDROCARBON IN COMMON

FUELS BY SPME (SOLID PHASE
MICROEXTRACTION) AND GC-MS (GAS
CHROMATOGRAPHY-MASS SPECTROMETER)

NAME

: MOHD IQBAL BIN NORAZMAN

STUDENT ID

: 2015840192

GROUP

: AS2452s

PARTNERS NAME

: 1. AKMAL ARSYAD BIN MOHD. RAFFI

2. MUHAMMAD RAHIMI BIN ZAHURI
3. SYARAFUDDIN BIN MOHD SHAMSIBY

DATE OF EXPERIMENT :
DATE OF SUBMISSION

Introduction
In the analysis of the solid phase microextraction (SPME) Gas Chromatography /
mass spectrometry (Gc/Ms) was developed for the identification of volatile components
(hydrocarbon) in fuel. Sample used were petrol, diesel, thinner and unknown. After the
analyte was extracted by SPME for 20 minutes, it directly injected to GC/MS with desorption
time 80 seconds. After analysis was done, result was stated and unknown was identified
because the hydrocarbon presence in the unknown was the same with hydrocarbon compound
in standard.
Solid Phase Microextraction, a simple effective adsorption/desorption technique, eliminate
the need for solvents or complicated apparatus for concentrating volatile or non volatile
compound in liquid samples or headspace. SPME was compatible with analyte
separation/detection by gas chromatography or HPLC (High Performance Liquid
Chromatography), and provide linear results for wide concentration of analytes. By
controlling the polarity and thickness of the coating on the fibre, maintaining consistent
sampling time, and adjusting several other extraction parameters. An analyte can ensure
highly consistent quantifiable results from low concentration of analytes.
Analytes of volatile or semi volatile organic environmental pollutants, flavour or fragrance
components, and many other samples usually begin with concentrating the analytes of
interest through liquid-liquid extraction, purge and trap headspace or various other
techniques. These procedures typically require excessive time, complicated equipment and/or
extravagant use of organic solvents. SPME on adsorption/desorption technique developed at
the University of Waterloo (Ontario, Canada), eliminates the need for solvents in an
experiment. SPME is microextraction technique, which means amount of extraction solvent
is very small compared to the sample. As a result, exhaustive removal of analytes to the
extracting phase doesnt occur rather an equilibrium, is reached between sample matrix and
the extracting phase.
SPME passively extracts organic compound and concentrates them onto a thin, fused silica
fiber coated with a stationary phase material. The component in a sample was identified by
comparing with the mass spectra library. The quality of a component must been taken 90%
and above. The purpose of this experiment is to perform sample preparation by SPME and to
identify the components of hydrocarbon in common fuel using SPME-GC-MS.

Method
The fiber (PDMS) was conditioned in the GC injection port at 250 oC for at least 10 minutes
to removed contaminants. Sample used in this analysis were petrol, diesel, thinner and an
unknown compound. First sample used was unleaded petrol where approximately 5mL of it
was added in a glass vial and place the vial on a hot plate and sample was heated to 50 0C
while agitate it by using magnetic stirrer. Then, the SPME fiber was exposed to the headspace
of the vial for 20 minutes. After that, the fibre was withdraw into the needle and pulled out
from the vial and immediately injected into GC-MS with desorption time 80 seconds. After
desorption period, the needle was withdrawn from the injection port and chromatography
process continued. After the chromatogram was obtained, the major compounds in each
sample were identified by using the mass spectra library. Four compounds that have higher
quality were selected. All the steps were repeated for the next three samples.

Results
Compounds

Quality (%)

Retention Time (min)

Toluene
Ethylbenzene
P-xylene
Benzene, 1,2,3-trimethyla) Petrol

94
91
97
95

2.59
3.71
3.87
5.82

Compounds

Quality (%)

Retention Time

Tridecane

92

10.34

Naphtalene, 1-methyl-

93

10.42

Naphtalene, 1,6-dimethyl-

96

12.16

Cycloheptasiloxane,

90

12.86

Compounds

Quality (%)

Retention Time (min)

Toluene

91

2.63

Compounds

Quality (%)

Retention Time (min)

Toluene

91

2.52

P-xylene

95

3.76

Benzene, 1,2,4-trimethyl-

95

5.72

Naphthalene, 1,6-dimethyl-

96

12.16

b) Diesel

tetradecamethylc) Thinner

d) Unknown

Compound of unknown that match with compound in petrol.

Unknown Compound
Compounds
Quality

Toluene
P-xylene
Benzene, 1,2,4-

Retention

(%)

Time

91
95
95

(min)
2.52
3.76
5.72

Compounds

Petrol
Quality

Toluene
P-xylene
Benzene, 1,2,3-trimethyl-

Retention

Time (min)

94
97
95

2.59
3.87
5.82

trimethyl-

Compound of unknown that match with compound in diesel.

Unknown Compound
Compound
Qualit

Naphthalene, 1,6-dimethyl-

Diesel
Retention

y (%)

Time

96

(min)
12.16

Compound

Naphthalene, 1,6-

Quality

Retention

(%)

Time

96

(min)
12.16

dimethyl-

Discussion
Based on the objective, major compound must been identified in each sample that were
petrol, diesel, thinner and unknown sample. In order to identify the compound in the sample,
firstly the solid-phase microextraction (SPME) technique was applied followed by gas
chromatography-mass spectrometry (GC-MS) for a separation. Microextraction means that

the amount of extraction solvent was very small compared to the sample volume. The SPME
fibre was exposed to the headspace of the vial for 20 minutes before it was injected into GC.
Since the compounds were volatile, headspace technique was chosen for extraction because it
much clean than the fibre place directly into the sample. In this experiment, fibre used was
polydimethylsiloxane (PDMS) for the extraction of non polar compounds. The film in PDMS
acts like a sponge, concentrating the analytes on its surface during adsorption from the
sample matrix. After the extraction time was completed, the SPME fibre was introduced into
the gas chromatography injector for desorption for about 80 seconds. Then, fibre was
transferred immediately as it did not want any of sample components collected to be
disappeared into surrounding. Purpose of desorption was to transfer analytes from the SPME
fibre to the column chromatography. The first sample injected was petrol. There were a lot of
components found in the sample. However, only components with high quality were chosen
and the structures were taken from the library of the mass spectrometer. For good selection
compounds, the quality must be 90 and above. The components taken in petrol were toluene,
ethylbenzene, P-xylene, and benzene, 1,2,3-trimethyl-. The quality of toluene, ethylbenzene,
p-xylene, and benzene, 1,2,3-trimethyl- were 94,91,97, and 95 respectively. Based on the
chromatogram, 10 out of 15 compounds of benzene was discovered in the petrol. It can be
deducted that major compound in the petrol was benzene. Compounds that contain in petrol
more volatile than diesel and thinner sample since the retention time was shorter that was
1.97 min compared to diesel (2.52 min) and thinner (2.63 min). For the second sample, diesel
there were 20 compounds found in diesel. The major compounds identified were tridecane,
naphthalene,

1-methyl-,

naphthalene,

1,6-dimethyl-,

and

Cycloheptasiloxane,

tetradecamethyl-. The quality for tridecane and 1,6-dimethyl- were 92 and 96 respectively
while, cycloheptasiloxane, tetradecamethyl- and naphthalene, 1-methyl- were shared the
same quality which 93. Major content in diesel were naphthalene since it was find in majority
in the compounds. The retention time of diesel was about 20 minutes. Next sample was
thinner. There was only one component detected which was toluene with 91 quality and 2.63
min of tR. Lastly, the sample injected was an unknown sample. The unknown sample analysis
shows that the unknown sample was the combination of diesel and petrol based on the
similarities of some of the major compounds present in diesel and petrol. The major
compounds presence in unknown were Toluene with 91 quality, p-xylene with 95 quality, and
benzene, 1,2,4-trimethyl- with 95 quality that also presence in petrol while naphthalene, 1,6dimethyl- with quality 96 has exactly the same analysis as in diesel. The advantages of using

SPME was that the extraction was simple and fast, also can be done without any solvents. If
the sample properly stored, it can be analysed days later without much loss of volatiles.

Conclusion
The major compound presence in petrol were toluene, ethylbenzene, p-xylene, and benzene,
1,2,3-trimethyl-. The major compounds in diesel were tridecane, naphthalene, 1-methyl-,
naphthalene, 1,6-dimethyl- and cycloheptasiloxane, tetradecamethyl-. Thinner only show a
single peak that corresponds to toluene. It can be concluded that the unknown sample was the

mixture of diesel and petrol since there were some major compounds of petrol and diesel
presence in the unknown.

References
1. Norashikin S., Ruziyati T., Mardiana S. (2014), Analytical Seperation Methods
Laboratory Guide (2nd edition),
2. Solid-Phase Microextraction, 12/7/2015,
http://en.wikipedia.org/wiki/Solid-phase_microextraction.
3. Mardiana Saaid, 12/7/2015, SPME sample preparation notes