INTRODUCTION

Solid phase microextraction (SPME) is a sample preparation technique where the sample
is incubated or agitated to equilibrate the headspace, while eliminating most drawbacks to
extracting organics, requiring no solvents or complicated apparatus.

It is able to concentrate volatile and nonvolatile compounds, whether in liquids or

gaseous samples, for subsequent analysis by gas chromatography or high performance liquid
chromatography. One of the advantages of SPME is that only a single step extraction needed,
and greatly reduces the sample preparation time. It is efficient and economical technique,
allowing 50 extractions per fiber. SPME is also able to adapt to any GC or HPLC systems.
There are three basic modes for SPME fiber, the direct extraction, headspace SPME and
membrane-protected SPME. For direct extraction, the fibre coating dipped into aqueous sample,
then allowing the analytes to partition between the coating and the matrix.Headspace extraction
places the fibre in the headspace above the aqueous matrix during extraction process, where
volatile analytes will be extracted. The method emphasize samples with high molecular weight
interferences. Samples having both nonvolatile target analytes and high molecular weight
interfering compounds will result in difficulty for the application of direct or headspace SPME.
This will resort to the usage of restricted access materials or membrane-protected SPME, that
will give better reproducibility and accuracy.

Mass spectrometry is an analytical tool used for measuring the molecular mass of a
sample in vapor phase. It is capable of providing information regarding elemental composition of
matter samples, structures of inorganic, organic and biological molecules. The technique is able
to analyze the quantitative and qualitative composition of complex mixtures, the structure and
composition of solid surfaces and finally the isotopic ratios of atoms in samples. For large
samples such as biomolecules, molecular masses can be measured to within an accuracy of
0.01% of the total molecular mass of the sample. This is sufficient to allow minor mass changes
to be detected, e.g. the substitution of one amino acid for another, or a post-translational
modification. For small organic molecules the molecular mass can be measured to within an
accuracy of 5 ppm or less, which is often sufficient to confirm the molecular formula of a
compound, and is also a standard requirement for publication in a chemical journal.
Gas chromatography-mass spectrometry works to identify and quantify volatile and semivolatile organic compounds in organic mixture while determination of molecular weights
structural determination of unknown organic compounds in complex mixtures. In this
experiment, the aim is to identify the components of hydrocarbons in common fuels are
identified using SPME-GC-MS. The common fuels includes petrol, diesel, thinner and unknown
sample.

PROCEDURE:
1. Instrument Set-up
Injector temperature: 250C
Detector temperature
: 300C
Carrier gas flow rate
: 30mL/s
Column temperature
: 60C to 170C at 10C min-1
2. SPME Procedure
a. The fiber (100L polydimethylsiloxane (PDMS)) is conditioned in a GC injection
port at 250C (10 minutes) to remove contaminants.
b. Approximately 5mL of sample is added in a glass vial with septum and the vial is
placed on a hot plate. The sample is heated to 50C. Using a magnetic stirrer, the
sample is agitated.
c. The SPME fiber is exposed to the headspace of the vial for 20 minutes.
d. The fiber is withdrawn into the needle, pull out from the vial and immediately
injected into the GC-MS with desorption time 80 seconds.
e. By using the mass spectra library, the major component in each sample is
identified.

RESULT:

1) Qualitative Analysis:
a)
Petrol

Compound

Retention Time(min)

Area (%)

Quality (%)

Benzene, 1-methyl-3-(1-

7.22

2.59

95

Toluene

2.56

15.44

94

p-Xylene

3.84

19.85

97

Benzene, 1,2,3- trimethyl

5.52

3.87

94

methylethyl)

b)

Thinner

Compound

Retention Time(min)

Area (%)

Quality (%)

Toluene

2.54

100.00

91

Compound

Retention Time(min)

Area (%)

Quality (%)

Tridecane

10.36

9.75

94

Tetradecane

10.36

9.75

74

Hexadecane

8.90

7.07

87

Napthalene, 1,6-dimethyl

11.94

4.82

96

Retention Time(min)

Area (%)

Quality (%)

c)

d)

Diesel

Unknown

Compound

Benzene, 1-ethyl-2-methyl

5.18

4.17

94

p-Xylene

4.11

5.30

97

p-Xylene

3.76

12.47

95

Benzene, 1,2,4-trimethyl

5.72

6.74

94

2) Mass Spectrum Analysis:

a) Petrol
Peaks

Qualit
y

Compounds

95

Benzene, 1methyl-3-(1methylethyl)

Structure

Functional
group

Base peak
(largest
abundance)

Molecular ion peak

(M+) (largest m/z
ratio)

Aromatic

119

120

Aromatic

92

92

Aromatic
Hydrocarbon

91

106

Aromatic
Hydrocarbon

105

120

C10H14
2

94

Toluene

C7H8
3

97

p-Xylene

94

Benzene, 1,2,3trimethyl-

C8H10

C9H12

b) Thinner

Peaks

Quality

Compounds

91

Toluene

Structure

Functional
group

Base peak
(largest
abundance)

Molecular ion peak,

(M+) (largest m/z
ratio)

Aromatic
Hydrocarbon

91

92

C7H8
c) Diesel
Peaks

Quality

Compounds

97

Tetradecane

94

Tridecane

Structure

Functional
group

Base peak
(largest
abundance)

Molecular ion peak,

(M+)(largest m/z
ratio)

alkane

57

198

Alkane

57

226

alkane

57

226

alkane

57

240

C14H30

C13H28
3

99

Hexadecane

96

Napthalene,
1,6dimethyl

C16H34

C17H36 = 240

d) Unknown
Peaks

Quality

Compounds

94

Benzene, 1ethyl-2methyl

95

o-Xylene

97

Tetradecane

96

pentadecane

Structure

Functional
group

Molecular ion peak

(M+) (largest m/z ratio)

aromatic

Base peak
(largest
abundance)
91

aromatic

91

106

alkane

57

198

alkane

57

212

92

C9H12

C8H10 = 106

C14H30 = 198

C15H32 =212

DISCUSSION
The objectives in this experiment are to conduct the SPME technique
and to identify the major compounds in each of the samples using mass
spectra library. The samples used are petrol, diesel, thinner and an unknown
sample.
To make simple understanding, SPME is a technique which we can
determine and identify what components are in a sample. In this experiment,
we use the SPME holder with 100m polydimethylsiloxane (PDMS) fibre and
the glass vial with septum, a 30m x 250m x 0.25m of capillary column
along the experiment conducted. It take about 30 to 40 minutes for each
injections to each samples. The time taken is too long is due to 20 minutes
for extraction of sample, 5 minutes to wash the sample and the time for
extraction is different for each smple such as, unknown sample need almost
24-26 minutes for extraction only.
The result obtained was divided to two analysis, qualitative analysis
and mass spectra analysis. The qualitative analysis is explaining about the
four most abundance peaks which have highest area in the sample and large
area percentage compared to other peaks. While the mass spectra analysis
is the details of each of the four most abundance peaks in each samples.
First, the qualitative analysis. For the petrol, the four most abundance
peaks are peak 7,peak 9, peak 10 and peak13. For diesel, the peaks are peak
7, peak 8, peak 11 and peak 12. While for thinner, are all the peaks obtained
from the chromatogram as it was only four peaks obtained. Lastly, for the
unknown, the peaks selected are the first four peaks come out, peak 1, peak

2, peak 3, and peak 4. The retention time, area and the percentage area for
each of the peaks can be refered to the table provided in result.
Next is the mass spectro analysis. In this analysis, the major compound
can be determined for each of the peaks. The details of the compound
actually can be read directly from the chromatogram result. It started as we
need to find the highest quality of the compound in each four peaks
selected. Then we can get the name, the base peak reading

and the

molecular ion peak(M+) of the compound. Lets get through each of the
samples, in the petrol, the compounds determined were toluene,o-xylene,
1,3-dimethylbenzene and 1-ethyl-3-methylbenzene.

But ,in

diesel the

compounds were undecane, dodecane, tridecane and tetradecane. While ,

compounds propanamide, benzene, toluene, and p-xylene were identified in
sample unknown and lastly for sample thinner, the compounds found were
toluene,1,3-dimethylbenzene, and ethylbenzene. The values of base peak,
molecular ion peak (M+), the structure and the functional group of each the
compounds in each peaks of each samples can be referred in the table given.
From the completed result, we had determined that the compounds
which in the unknown sample were same with the compounds in thinner and
petrol from the similarity or nearest of the retention time for the compounds
come out during the experiment. Therefore, the unknown actually was the
mixture of thinner and the petrol.
Even the experiment conducted very well, some error still occurred
such as the personal error. Each of the students or conductor of the
experiment are not highly pay attention to the procedure of the experiment.
Next, as the extraction time is quite long, the students does not be aware
when the time is finished and that is not a good attitude for a scientist. The
setting of the instrument also not been understand very well as sometimes,
the data been gone or cannot be find as do not know how to use the offline
mode.

Since the error somehow can affect the result, the experiment
conductor should be very aware about the precautions as to avoid the same
mistakes during conducting an experiment. Always ask anyone or lecturer or
laboratory staff on how to use the setting in both modes, online mode and
offline mode. Make sure that carefully handled the instrument especially the
fibre.

CONCLUSION
The identification of unknown hydrocarbon in fuel can be done by using GC-MS and
using Solid-Phase Micro Extraction (SPME) sample preparation and by comparing the quality of
analyte in the samples and in the unknown. It was found that the unknown consist of petrol since
it shared the common highest analyte quality.

REFERENCES
1. Douglas A. Skoog, F.James Holler, Stanley R. Crouch. (2007). Principle of
Instrumental Analysis, 6th edition ; Brooks/Cole Cenage Learning
2. http://www.ukm.my/mjas/v12_n1/8.pdf
3. http://www.leapwiki.com/mediawiki/index.php?title=SPME
4. http://employees.csbsju.edu/cschaller/Principles%20Chem/structure
%20determination/ms%20fragmentation.htm
5. http://www.elmhurst.edu/~chm/vchembook/514gasoline.html
6. http://en.wikipedia.org/wiki/Solid-phase_microextraction