1.

0 INTRODUCTION

Solid-phase microextraction (SPME), is a new sample preparation technique using a fused-

silica fibre that is coated on the outside with an appropriate stationary phase. The analyte in
the sample is directly extracted onto the fibre coating. This method saves preparation time,
solvent purchase and disposal costs, and can improve detection limits. It has been used
routinely in combination with gas chromatography (GC) and GC-mass spectroscopy (GC-
MS) and successfully applied to a wide variety of compounds, especially for the extraction of
volatile and semi volatile organic compounds in common fuels. The objective of this
experiment is to identify major hydrocarbons in common fuels (petrol, diesel, paint thinner
and unknown) by using SPME-GS-MS.
2.0 METHODOLOGY

The instrument used was Gas chromatograph (Agilent Technologies 5890 Series II)
equipped with HP 5971A mass spectrometry detector (MSD) and a 30 m x 250 m x 0.25
m HPS-MS capillary column. The reagents used in the experiment were the accelerants
which including unleaded petrol, diesel, paint thinner and an unknown sample. The
instrument was set-up as below:

Injector temperature : 250C

Detector temperature : 300C
Carrier gas flow rate : 30 cm sec-1
Column temperature : 60C to 170C at 10C min-1

In order to remove contaminants, the polydimethylsiloxane, PDMS fibre was

conditioned in a GC injection port at 250C at 10 minutes. 2.0 mL of sample was added
approximately in a glass vial with septum and the vial was placed in a water bath (in beaker)
on a hot plate. The sample was heated to 50C and agitated the sample using a magnetic
stirrer. The SPME fibre was exposed to the headspace of the vial for 20 minutes. the fibre
was withdrawn into the needle, pulled out from the vial and injected into the GC-MS
desorption time 80 seconds. The identification of major compounds in each sample were
identified using the mass spectra in NIST library.
3.0 RESULTS

Table 1. Major compounds presence in Petrol sample

Retention
Area (%) Quality Compound
time (min)

6.879 15.55 94

Benzene, 1-ethyl-3,5-dimethyl

8.195 7.05 93

1-Methyl-2-phenylcyclopropane

2.622 10.21 83

Toluene

5.352 18.00 72

Mesitylene
Table 2. Major compounds presence in Diesel sample

Retention
Area (%) Quality Compound
time (min)

10.478 16.42 95

Naphthalene, 1,2,3,4-tetrahydro-5-methyl

3.870 5.49 94

Benzene, 1,3-dimethyl-

13.071 8.31 93

Pentadecane

9.037 6.14 92

Dodecane
Table 3. Major compounds presence in Paint thinner sample

Retention
Area (%) Quality Compound
time (min)

5.826 1.06 97

Mesitylene

5.306 1.88 95

Benzene, 1-ethyl-3-methyl-

3.383 0.41 91

Cyclohexane, ethyl-

2.628 21.29 90

1,3,5-Cycloheptatriene
Table 4. Major compounds presence in Unknown sample

Retention
Area (%) Quality Compound
time (min)

7.314 6.76 97

Benzene, 1-ethyl-2,4-dimethyl

10.078 8.23 96

Naphthalene, 1,2,3,4-tetrahydro-6-methyl

11.829 7.92 93

1H-Indene, 2,3-dihydro-1,1,3-trimethyl

13.070 3.41 91

Pentadecane
5.0 DISCUSSION

From the analysis done, 4 major compounds present in petrol sample are toluene,
mesitylene, benzene, 1-ethyl-3,5-dimethyl- and 1-methyl-2-phenylcyclopropane that lie from
retention time of 1 minute to 11 minutes of analysis. Diesel sample show the major
compound peaks from 1 to 20 minutes that respond to benzene,1,3-dimethyl-, dodecane,
naphthalene, 1,2,3,4-tetrahydro-5-methyl- and pentadecane based on the mass spectra
library. Four major compounds from paint thinner sample are 1,3,5-cycloheptatriene,
cyclohexane, ethyl-, benzene, 1-ethyl-3-methyl- and mesitylene that lie from retention time
from 1 to 8 minutes.

The unknown sample analysis shows that the unknown sample has similarities of
some of the major compounds present in the diesel and other compounds in paint thinner.
The major compounds present in the unknown are naphthalene, 1,2,3,4-tetrahydro-5-methyl,
pentadecane and 1H-Indene, 2,3-dihydro-1,1,3-trimethyl that are present in diesel. However,
the peak result for 1H-Indene, 2,3-dihydro-1,1,3-trimethyl is not printed out as we only
decided to pick 4 major compounds from each sample during the analysis. In unknown,
there are compounds that has the similarities with paint thinner which are benzene, 1-ethyl-
3-methyl- and mesitylene with retention time at 5.308 and 5.827 respectively. The retention
time is quite differing from thinner. Though, we did not choose the two compounds as our
major compounds in unknown even when the quality is 95 and 91. The assumption can be
made that unknown is the combination of diesel and thinner based on the compounds found
in the sample.

6.0 CONCLUSION

The major compounds presence in diesel are naphthalenebenzene,1,3-dimethyl-, dodecane,

naphthalene, 1,2,3,4-tetrahydro-5-methyl- and pentadecane. The major compounds
presence in paint thinner are 1,3,5-cycloheptatriene, cyclohexane, ethyl-, benzene, 1-ethyl-
3-methyl- and mesitylene. Petrol only show a single peak that corresponds to toluene. It can
be concluded that the unknown sample is the mixture of diesel and paint thinner since there
are some compounds of diesel and petrol presence in the unknown.
7.0 REFERENCES

1. Kataoka, H., Lord, H.L., & Pawliszyn, J (2000). SOLID-PHASE MICROEXTRACTION |

Biomedical Applications. Encyclopedia of Separation Science, 4153-4169.
doi:10.1016/b0-12-226770-2/00971-6
2. Nor’ashikin S., Ruziyati T., Mardiana S., Rozita O. (2019), ANALYTICAL SEPARATION
METHODS Laboratory Guide 3rd Edition. UiTM Press*9/