UITM ARAU PERLIS

Experiment 4

Analysis of Hydrocarbonsin Common Fuels using Solid-Phase Microextraction

(SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)

Name : Nur Izzati Binti Othman Basri

Group : RAS2452C
Matrix No. : 2020991379
Date Of Experiment : 19 May 2020
Date of Submission : 9 June 2020
Lecturer’s Name : En Mohd Lias
OBJECTIVE

The objective of this experiment is to perform sample preparation by SPME and to

identify the major hydrocarbons components in common fuel as (diesel, petrol,
thinner and an unknown) by using SPME-GC-MS.

ABSTRACT

In the analysis the solid-phase miroextraction (SPME) and capillary gas

chromatography or mass spectrometry (GC-MS) was developed for the identification
of volatile compounds (hydrocarbon) in fuel. The samples was used is thinner,
unleaded petrol, diesel andone unknown. After the analyte was extracted by SPME in
20 minutes, it directly injected tothe GC-MS with desorption time 80 seconds. After
the analysis was done, the unknown wasidentifies as mixture of diesel and petrol
because the hydrocarbon presence in the unknown isthe same with the hydrocarbon
compound in the petrol and diesel sample.

INTRODUCTION

Sample preparation is an essential step in analysis, greatly influencing the reliability

and accuracy of analysis. SPME is an alternative to the conventional liquid-liquid
extraction (LLE) technique. It is a rapid, inexpensive and solventless technique for the
isolation of organic compounds from gaseous, liquid or aqueous and solid samples. It
is based on the enrichment of analytes on a polymer or adsorbent-coated fused-silica
fibre by exposing the fibre either directly to the sample or to its headspace and
thermal desorption of the analytes in the GC injector.

SPME Apparatus

The SPME apparatus consists of a fibre holder and a fibre assembly, the latter
containing a 1 to 2 cm long retractable SPME fibre. The SPME fibre is a thin
fused-silica optical polydimethylsiloxane (PDMS). PDMS fibre is non-polar, thus
suitable for non polar analytes (hydrocarbons).
SAMPLE

Accelerants : Unleaded petrol, diesel, paint thinner, kerosene and unknown.

APPARATUS

a. SPME holder with 100 µm polydimethylsiloxane (PDMS) fibre

b. Glass vial with septum

INSTRUMENT

Gas chromatography (Agilent Technologies 5890 Series II) equipped with HP 5971A
mass spectrometry detector (MSD) and a 30 m x 250 µm x 0.25 µm HP5-MS
capillary column.

ANALYTICAL PROCEDURE

a. Instrument set-up (may vary depending on instrument) :

Injector temperature : 250℃
Detector temperature : 300℃
Carrier gas flow rate : 30 cm sec-1
Column temperature : 60℃ to 170℃ at 10℃ min-1

b. SPME procedure
1. The fibre (100 μm polydimethylsiloxane (PDMS)) was conditioned in the GC
injector port for 10 minutes at 250 °C to remove any contaminants.
2. Diesel sample in vial at 50 °C was heated constantly while the fibre was
exposed to the headspace of the vial for 20 minutes.
3. The fibre was withdraw into the needle and was pulled out from the vial and
was immediately injected into the GCMS with desorption time of 80 seconds.
4. Step 1 until 3 were repeated for petrol, thinner and an unknown sample.
5. Petrol sample was run for 15 minutes and thinner sample was run for 10
minutes, while the unknown sample was run for 26 minutes depending on the
completion of separation.
6. By using the mass spectra library, the major compounds (4 spots) in each
sample were identified.
 RESULTS

A. Major compounds presence in diesel sample

Retention Time of Peak Retention Time Library Area Quality Compound

Sample (min) (min) (%)
14.378 20 14.378 4.31 97 Naphthalene,
2,3,6-trimethyl-
7.924 5 7.924 3.78 92 Undecane
12.318 15 12.318 8.73 95 Tetradecane
10.949 11 10.949 7.85 93 Tridecane

B. Major compounds presence in Petrol sample

Retention Time of Peak Retention Time Library Area Quality Compound

Sample (min) (min) (%)
5.064 4 5.064 9.19 55 Toluene
3.595 2 3.595 18.02 53 2,3,5-Trioxabicyclo
[2.1.0]pentane,1,4-bi
s(phenylmethyl)-
2.876 1 2.876 29.98 70 Toluene

C. Major compounds presence in Thinner sample

Retention Time of Peak Retention Time Library Area Quality Compound

Sample (min) (min) (%)
5.358 4 5.358 10.49 52 Ethanol, 2-butoxy-
2.982 2 2.982 45.09 38 2, Beta-dinitrostyrene
3.760 3 3.760 31.63 37 2, Beta-dinitrostyrene
1.994 1 1.994 12.79 12 Hydrazine,
(1-methylpropyl)-
2.689 1 2.689 100.0 94 Toluene

D. Compound of unknown that match with compound in hydrocarbons

Retention Retenti Area Quality Compound Hydrocarbons

Time on time (%)
Unknown Library
sample (min)
(min)
6.332 6.332 5.36 90 Benzene,
1,2,3-trimethyl-
5.844 5.844 6.12 90 1,3-Cyclopentadiene,5-( Diesel
1-methylpropylidene)-
12.818 12.818 6.52 95 Naphthalene,
2,6-dimethyl-
2.951 2.951 18.61 81 Toluene Petrol
DISCUSSION

Solid phase microextraction (SPME) was used in this experiment on sample

preparation to reduce the time necessary for sample preparation, decreases purchases
and disposal costs of solventsand can improve detection limits. That is why the SPME
was choosing in this analysis. From the experiment, there are four chromatogram
obtain which are petrol, diesel, thinner and unknown. The method used was SPME
where it used fiber to absorb the sample. Needle with fiber was put into the sample by
head space method. The sample was volatile and thermall stable. So it does not need
to dip it into the sample. The sample was volatile when it heated and the fiber absorbs
the sample volatile and keeps it in the fiber.
Based on the analysis that have been done, 3 major compounds presence in petrol
sample. There are 2 compound of toluene at different retention time an quality which
is 5.064 minutes and 2.876 minutes and its quality at 55 and 70 respectively. The next
compound is 2,3,5-Trioxabicyclo[2.1.0]pentane,1,4-bis(phenylmethyl) that lie at
retention time of 3.595 minutes of analysis. Diesel sample show the trend of major
compound peaks that respond to tridecane at 10.949 minutes, undecane at 7.924
minutes, tetradecane at 12.318 minutes and Naphthalene, 2,3,6-trimethyl- at 14.378
minutes based on the mass spectra library.
The unknown sample analysis shows that the unknown sample is the combination
of diesel and petrol based on the similarities of some of the major compounds
presence in diesel and petrol. The major compounds presence in the unknown are
Benzene,1, 2, 3-trimethyl-, 1,3-Cyclopentadiene,5-(1-methylpropylidene)-, and
Naphthalene, 2,6-dimethyl- that is presence in diesel while toluene presence in petrol.
The advantage of using SPME is that the extraction is simple, fast and can be done
without any solvents. If the samples are properly stored, it can be analyzed days later
without much loss of volatiles.
CONCLUSION

In conclusion, since hydrocarbon is volatile compound, the extraction procedure

by placing the SPME fiber in the headspace above the sample can be extract the
analyte and directly injected to the GC-MS. The components in the sample can be
identified using the GC-MS where we can compare the obtained spectra with the mass
spectra library. From this experiment, the objective of this experiment was achieved
to determine the major compounds that present in the thinner, diesel, kerosene and
petrol. The hydrocarbon that present in unknown are mixture of diesel and petrol.

REFERENCES

1. Nor’ashikin Saim, Ruziyati Tajuddin., Mardiana Saaid, Rozita Osman, (2019),

Analytical Separation Methods Laboratory Guide (3nd edition).
2. Analysis of Hydrocarbons in Common Fuels, 2019.
Retrieved from
https://studymoose.com/analysis-of-hydrocarbon-essay

3. Solid Phase Microextraction Phase(SPME)-Sample preparation, 2019.

Retrieved on from
https://www.sigmaaldrich.com/analytical-chromatography/analytical-products.ht
ml?TablePage=9644384

4. Gas Chromatography / Mass spectrometry (GC-MS), 2019.

Retrieved on from
http://www.cpeo.org/techtree/ttdescript/msgc.htm