(EXPERIMENT 5)

ANALYSIS OF HYDROCARBONS IN COMMON

FUELS BY SOLID-PHASE MICROEXTRACTION
(SPME) AND GAS CHROMATOGRAPHY- MASS
SPECTROMETRY (GC-MS)
NAME:

MOHAMAD NOR AMIRUL AZHAR BIN KAMIS

STUDENT ID:

2014647344

PARTNERS NAMES: 1.

MOHAMAD HAMIZAN BIN MOHD ISA

2.

MOHAMAD SHAFIQ BIN PARMAN

3.

MOHAMAD AZMIZAM BIN MOHAMAD

NOOR

DATE OF EXPERIMENT:
DATE OF SUBMISSION:

8/12/2014

INTRODUCTION:
Solid-phase microextraction is a sample preparation technique that use fibre
coated with extracting phase that extract different kinds of analytes for
different fibre coating. The analytes can be in the form of liquid or gas either
volatile or not. In this experiment, head space SPME is used where the fibre is
exposed in the vapour phase above a gaseous sample. Head space SPME is
suitable for the analysis of volatile organic compounds, and it is important to
keep the headspace volume constant and keep the fibre position at the same
depth for every analysis. The amount of analyte extracted by the fibre depends
on the concentration of the analyte in the sample as long as equilibrium
reached. After the extraction process was done, the fibre is transferred to the
injection port of GC where desorption of the analyte takes place and the
separation occur. The factors that affect the SPME performance are the
coating material, thickness of fibre, sample agitation, sample pH, salt addition
and the extraction procedure. The objective of this experiment is to identify
the major hydrocarbons components in common fuels (diesel, petrol, thinner
and an unknown) by using SPME-GC-MS.

EXPERIMENTAL:
a. Instrument set-up:
Injector temperature: 250C
Detector temperature: 300C
Carrier gas flow rate: 30mL/s
Column temperature: 60C to 170C at 10C/min
b. SPME procedure:
1. The fibre (100m polydimethylsiloxane (PDMS)) was conditioned in
the GC injector port for 10 minutes at 250C to remove any
contaminants.
2. Diesel sample in a vial at 50C 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 25 minutes
depending on the completion of separation.
6. By using the mass spectra library, the major compounds (4 spots) in
each sample were identified.

RESULT AND DISCUSSION:

A. Major compounds presence in petrol sample:
Retention time,
Area, %
Quality
min
2.57
16.95
90

Compound
Benzeneacetamide

3.83

17.41

97

p-xylene

5.25

8.34

94

Benzene,1-ethyl-3methyl-

5.78

10.69

97

Benzene,1,2,3trimethyl-

B. Major compounds in diesel sample:

Retention
Area, %
Quality
time, min
8.94
5.60
93

Compound
Dodecane

12.16

11.32

95

Naphthalene,1,4dimethyl-

13.01

5.23

97

Pentadecane

14.41

4.85

97

Hexadecane

C. Major compound in thinner sample:

Retention time,
Area, %
min
2.54
100

Quality

Compound

91

Toluene

D. Compounds of unknown that match with compound in petrol:

Retention time,
Area, %
Quality
Compound
min
5.21
6.91
93
Benzene,1-ethyl3-methyl-

5.73

9.89

93

Benzene,1,2,3trimethyl-

E. Compounds of unknown that match with compound I diesel:

Retention
Area, %
Quality
Compound
time, min
8.94
5.44
94
Dodecane
12.17

7.38

94

Naphthalene,1,4dimethyl-

13.01

8.96

96

Pentadecane

From the analysis done, 4 major compounds presence in petrol sample are
benzeneacetamide, p-xylene, benzene,1-ethyl-3-methyl-, and benzene,1,2,3trimethyl- that lie from retention time of 2 minutes to 11 minutes of analysis.
Diesel sample show the trend of major compound peaks from 8 minutes to 15
minutes that correspond to dodecane, naphthalene,1,4-dimethyl-,
pentadecane and hexadecane based on the mass spectra library.

It is outstanding result for the analysis of thinner that shows only one peak
that is the toluene peak at 2.54 minutes with 100% area at 91 qualities. 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-ethyl-3-methyl- and benzene,1,2,3-trimethyl- that is also
presence in petrol while dodecane, naphthalene,1,4-dimethyl-, and
pentadecane presence in diesel. There is a retention time that is presence in
thinner and the unknown that at 2.54 minutes, but since the quality is lower
that is 64, the assumption cannot be made because it has the possibilities to be
other compounds. The advantages of using SPME is that the extraction is
simple and fast, also can be done without any solvents. If the samples are
properly stored, it can be analysed days later without much loss of volatiles.

CONCLUSION:
The major compounds presence in petrol are benzeneacetamide, p-xylene,
benzene,1-ethyl-3-methyl-, and benzene,1,2,3-trimethyl-. The major
compounds presence in diesel are dodecane, naphthalene,1,4-dimethyl-,
pentadecane and hexadecane. Thinner only show a single peak that
corresponds to toluene. It can be concluded that the unknown sample is the
mixture of diesel and petrol since there are some major compounds of diesel
and petrol presence in the unknown.

REFERENCES:
1. Norashikin S., Ruziyati T., Mardiana S. (2012), Analytical Separation
Methods Laboratory Guide (2nd edition), 3/10/2014.
2. Solid-Phase Microextraction, 29/10/2014,
http://en.wikipedia.org/wiki/Solid-phase_microextraction.
3. Mardiana Saaid, 29/10/2014, SPME sample preparation notes.