BACHELOR OF SCIENCE ( HONS) APPLIED CHEMISTRY

(AS245)
LABORATORY REPORT
ANALYTICAL SEPARATION METHODS
CHM510
EXPERIMENT 5: ANALYSIS OF HYDROCARBONS IN COMMON FUELS
BY SOLID-PHASE MICROEXTRACTION (SPME) AND GAS
CHROMATOGRAPHY- MASS SPECTOMETRY (GC-MS)

NAME MUHAMMAD AMIRUL AFIFI BIN MAT YAKI

STUDENT ID 2018287232
PARTNER’S NAME 1. SITI SARAH BINTI ABDUL AZIZ
2. NURHIDAYAH BINTI MOHAMAD
3. NUR AFIQAH BINTI RUSMAN
4. ANWAR

GROUP AS2452S2
LECTURER’S NORAINI
NAME
DATE OF
EXPERIMENT
DATE OF
SUBMISSION
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, kerosene, unleaded petrol, diesel and
one unknown. After the analyte was extracted by SPME in 20 minutes, it directly injected to
the GC-MS with desorption time 80 seconds. After the analysis was done, the unknown was
identifies as mixture of diesel and petrol because the hydrocarbon presence in the unknown is
the same with the hydrocarbon compound in the petrol and diesel sample.

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.

INTRODUCTION

Modern gas chromatography-mass spectrometry (GC-MS) methods and equipment, with the
sensitivity and structural information these methods provide, make GC-MS an excellent
choice for field detection and identification of a range of organic chemicals. Numerous
sampling techniques allow detection of GC-MS analytes in environmental matrices, although
multiple sample-handling steps and use of extraction solvents increase the complexity and
time needed to complete analyses. Solid phase microextraction (SPME) has been shown to be
suitable for sampling environmental contaminants from air, water and soil for GC-MS
analysis.

Solid phase microextraction is simple and effective adsorption or desorption technique,

eliminates the need for solvents or complicated apparatus for concentrating volatile or non-
volatile compounds in liquid samples or headspace. SPME is compatible with analyte
separation by gas chromatography and provides linear results for wide concentrations of
analytes.

Gasoline, diesel and kerosene are all created from crude oil by variety of refining and
distillation process. Each product is produced by the combination of multiple individual
hydrocarbon compounds all of which have slightly different vaporization and boiling
temperatures. Gasoline is the combination of many lower boiling ranges while the middle
boiling range compounds are used in differing proportions to create kerosene and diesel. The
profile of hydrocarbons in oil may hence be used to characterize the oil. This enables the
identification of the candidate source of oil spill cases.

SAMPLE

Accelerants : Unleaded petrol, diesel, thinner and kerosene.

APPARATUS

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

2. Glass vial with septum.

INSTRUMENT

Gas chromatography equipped with mass selective detector(MSD) and a 30 m x 250 µm x

0.25 µm HP5-MS capillary column.

ANALYTICAL PROCEDURE

a. Instrument set-up
Injector temperature: 250 °C
Detector temperature: 300 °C
Carrier gas flow rate: 30 mL/s
Column temperature: 60 ֯C to 170 °C at 10 °C/min

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.

RESULT AND CALCULATION

a) Major compounds presence in petrol sample:

Retention time, Area,

Quality Compound
min %

2.77 16.90 90

Toluene

4.07 18.66 97

p-Xylene

6.02 5.13 95

Benzene, 1,2, 3-trimethyl-

6.93 1.31 91

Benzene, 1-methyl-3-propyl
 b) Major compounds presence in diesel sample:

Retention time, Area,

Quality Compound
min %

10.66 13.77 94
Tetradecane

7.67 4.42 94

Undecane

12.47 8.96 96

Naphthalene, 2,6- dimethyl

13.27 4.56 97

Pentadecane

c) Major compounds presence in thinner sample:

Retention time, Area,

Quality Compound
min %

2.73 89.01 94

Toluene
 d) Compound of unknown that match with samples:

Retention
Area,
time, Quality Compound
Samples %
min

4.07 10.34 97

p-Xylene
Petrol

6.05 4.69 94

Benzene, 1,2, 4-trimethyl-

7.70 2.61 94

Diesel Undecane

11.00 2.06 94

Naphthalene, 2- methyl
DISCUSSION

In this experiment, the sample preparation used solid phase microextraction (SPME) reduces
the time necessary for sample preparation, decreases purchases and disposal costs of solvents
and 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 thermally
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.

The first chromatogram obtained was petrol. A lot of components were found in this samples
which were 16 components. Four of the major components were toluene with 90 quality and
the retention time was 2.27 and has area% of 16.90, p-Xylene with 97 quality and its retention
time was 4.07 with area% of 18.66, benzene, 1,2, 3-trimethyl- with 95 quality and its retention
is 6.49 with area % are 5.13 and Benzene, 1-methyl-3-propyl with 91 quality and its retention
time is 6.93 with area % of 1.31. The second sample was injected was diesel which had 17
components. The four highest quality components were heptadecane with 97 quality and its
retention time was, naphthalene, 2,6- dimethyl with 96 quality and its retention time was,
undecane with 94 quality and its retention time was and for the retention time and tetradecane
with 94 quality and its retention time was . The third sample was thinner which had only one
component which is toluene the major compound in the thinner sample with 94 quality.
Unknown was the last sample injected. There were 29 components in the sample. However
only the four highest qualities component were taken and the structures were taken from the
mass spectrometer’s library. The components taken were p-Xylene with 97 quality and its
retention time was , benzene, 1,2, 4-trimethyl-with 94 quality and its retention time was ,
undecane with 94quality and for the retention time and naphthalene, 2- methyl with 94
quality and its retention time was .

From this component, the result was compared with the other three standards. It was found
that in the unknown contained mixture of petrol and diesel. This was due to the components
of benzene and undecane as well as the compound of naphthalene in the unknown. The
existent of the petrol compound in the unknown was shown by the detection of compound of
1,2,4-trimethyl benzene which had 6.02 minutes in retention time for petrol and 6.04 minutes
for unknown. Other than that, the compound of undecane had 7.67 minutes in retention time
for diesel and 7.70 minutes for unknown.

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 S., Ruziyati T., Mardiana S. (2012), Analytical Separation Methods

Laboratory Guide (2nd edition)
2. Prof. Rozita, Lecture notes: Gas Chromatography (GC) and sample preparation for
chromatographic Analysis.
3. Analysis of Hydrocarbons in Common Fuels
https://studymoose.com/analysis-of-hydrocarbon-essay , Retrieved on 20th May 2019.
4. Solid Phase Microextraction Phase(SPME)-Sample preparation
https://www.sigmaaldrich.com/analytical-chromatography/analytical-
products.html?TablePage=9644384 , Retrieved on 20th May 2019.
5. Gas Chromatography / Mass spectrometry (GC-MS)
http://www.cpeo.org/techtree/ttdescript/msgc.htm , Retrieved on 20th May 2019.