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OBJECTIVE

To perform sample preparation by SPME and to identify the components of hydrocarbon in common
fuel using SPME-GC-MS.

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

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

94

2.59

Ethylbenzene

91

3.71

P-xylene

97

3.87

Benzene, 1,2,3-trimethyl-

95

5.82

a) Petrol

b) Diesel
Compounds

Quality (%)

Retention Time

Tridecane

92

10.34

Naphtalene, 1-methyl-

93

10.42

Naphtalene, 1,6-dimethyl-

96

12.16

Cycloheptasiloxane,
tetradecamethyl-

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

c) Thinner

d) Unknown

Compound of unknown that match with compound in petrol.

Unknown Compound

Petrol

Compounds

Quality
(%)

Retention
Time (min)

Compounds

Quality
%

Retention
Time (min)

Toluene

91

2.52

Toluene

94

2.59

P-xylene

95

3.76

P-xylene

97

3.87

Benzene, 1,2,4-trimethyl-

95

5.72

Benzene, 1,2,3-trimethyl-

95

5.82

Compound of unknown that match with compound in diesel.

Unknown Compound
Compound

Quality
(%)

Naphthalene, 1,6-dimethyl-

96

Diesel
Retention
Time
(min)
12.16

Compound

Quality
(%)

Retention
Time (min)

Naphthalene, 1,6-dimethyl-

96

12.16

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, 1,2,3trimethyl-. 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 t R. 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, 1,6-dimethyl- 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, 1,2,3trimethyl-. The major compounds in diesel were tridecane, naphthalene, 1-methyl-, naphthalene, 1,6dimethyl- 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