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ANALYTICAL SEPARATION METHODS

CHM 510
LABORATORY REPORT

EXPERIMENT 5:
ANALYSIS OF HYDROCARBONS IN COMMON FUELS BY
SOLID-PHASE MICROEXTRACTION (SPME) AND GAS
CHROMATOGRAPHY-MASS SPECTROMETRY (GC-MS)

NAME

NUR DIYANA BT SUZAIMI

STUDENT ID

2013201486

PARTNERS NAME

NUR SYAFIQAH BT MUSTAPHA KAMAL


(2013439346)
NOR SYAFIKA BT MOHAMAD (2013266746)

GROUP

AS202/3 MA

LECTURERS NAME

PN. HALIZA BT KASSIM

DATE OF EXPERIMENT

28th OCTOBER 2014

DATE OF SUBMISSION

10th DECEMBER 2014

OBJECTIVE

The objectives of this experiment are to perform sample preparation by SPME and to identify the
components of hydrocarbon in common fuel using SPME-GC-MS

INTRODUCTION
Sample preparation require an extraction technique before it is analyses using gas
chromatography. In this experiment the extraction technique used is called solid phase
microextraction. This technique is fast, simple, effective adsorption/desorption technique, and
the main advantage is solventless. SPME is compatible with analytes separation/detection by gas
chromatography or HPLC, and provides linear results for wide concentrations of analytes. By
controlling the polarity and thickness of the coating on the fiber, maintaining consistent sampling
time, and adjusting several other extraction parameters, an analyst can ensure highly consistent,
quantifiable results from low concentrations of analytes.
In SPME, analytes reach equilibria among the sample matrix, the headspace above the sample,
and a polymer-coated fused fiber, then are desorbed from the fiber to a chromatography column.
Because analytes are concentrated on the fiber, and are rapidly delivered to the column,
minimum detection limits are improved and resolution is maintained. Solid-phase
microextraction (SPME) parameters were examined on water contaminated with hydrocarbons
including benzene and alkyl benzenes, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs).
Sample preparation is an essential step in analysis as it affect the reliability and accuracy of
analysis. It is a rapid, inexpensive and solventless technique for the isolation of organic gaseous
and liquid sample.
There are factor that will affect this technique. One is during extraction and the other on is during
desorption. Types of fibers, thickness of coating on the fiber, extraction time, extraction
temperature, sample agitation and pH and salt content are the factors that will affect the
efficiency of extraction. Factors that affect desorption are boiling point of analyte, thickness of
coating on the fiber and temperature of the injection port.

SAMPLE

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


APPARATUS
b. SPME holder with 100 m polydimethylsiloxane (PDMS) fiber
c. Glass vial with septum
INSTRUMENT
Gas chromatograph (Agilent Technologies 5890 Series II) equipped with HP 5971A mass
selective detector (MSD) and 30 m x 250 m x 0.25 m HP5-MS capillary column.

PROCEDURE
a. Instrument set-up
Instrument was set-up. First, injection temperature was set at 250 oC. Detector
temperature was then set at 300oC. Next, carrier gas flow rate was set for 30 mLs-1.
Lastly, the column temperature was set 60oC to 170oC at 10oC min-1.
b. SPME procedure
The fiber (100 m polydimethylsiloxane (PDMS)) was conditioned in a GC injection
port at 250oC for 10 minutes to remove contaminants. A glass vial with septum contains
sample was placed on a hot plate. The sample was heated to 50 oC. The SPME fiber was
inserting into the vial by inject the needle through septum. The SPME fiber was exposed
to the headspace of the vial for 20 minutes. The fiber was withdrawn into the needle, was
pulled out from the vial and was immediately injected into the GC-MS with desorption
time 80 seconds. After desorption period, the needle was withdrawn from the injection
port and chromatography continued. After the chromatogram was obtained, the major
compounds in each sample were identified by using the mass spectra library. Four
compounds that have higher quality were selected. All the steps were repeated for the
next three more samples.
RESULT AND DATA

Table 1: Petrol sample

Compound

Quality

Retention time, min

Area percent, %

Toluene

91

2.56

14.51

o-Xylene

91

3.83

17.97

p-Xylene

87

4.16

7.83

Benzene, 1,2,3-trimethyl-

91

5.77

8.31

Table 2: Diesel sample


Compound

Quality

Retention time, min

Area percent , %

Octadecane

99

13.43

19.46

Hexadecane, 2,6,10,14
tetramethyl

94

13.75

3.94

Nonadecane

98

17.66

22.79

Pentadecanoic acid,
14-methyl-,methyl
ester

98

19.07

27.99

Table 3: Thinner sample


Compound

Quality

Retention time, min

Area percent, %

Toluene

91

2.49

100

Table 4: Unknown sample


Compound

Quality

Retention time, min

Area percent, %

Toluene

91

2.55

10.15

Eicosane

99

14.12

10.87

8- octadecenoic acid,
methyl ester, (E)-

92

23.30

12.48

Heneicosane

99

23.48

18.05

DISCUSSION

Based on the objective, we have to identify the major compounds in each sample which are
petrol, diesel, thinner and unknown sample. In order to identify the compound in the sample,
firstly the solid-phase microextraction (SPME) technique was applied follow by gas
chromatography-mass spectrometry (GC-MS) for a separation. Microextraction means that the
amount of extraction solvent is very small compared to the sample volume. The SPME fibre is
exposed to the headspace of the vial for 20 minutes before it was injected into GC. Since the
compounds are volatile, headspace technique is chosen for extraction because it is much clean
than the fiber place directly into the sample. In this experiment fiber used is
polydimethylsiloxane (PDMS) for the extraction of a non-polar compounds. The film in PDMS
acts like a sponge, concentrating the analytes on its surface during adsorption from the sample
matrix. After the extraction time was completed, the SPME fibre is introduced into the gas

chromatography injector for desorption for about 80 seconds. We transferred the fibre
immediately as we did not want any of sample components collected to be disappeared into
surrounding. Purpose of desorption is to transfer analytes from the SPME fibre to the column
chromatography.
The first sample injected was petrol. There are a lot of component found in the sample. However
only components with high quality were chosen and the structure were taken from the library of
the mass spectrometer. For good selection compounds, the quality must be 90 and above. The
components taken in petrol were toluene, o-Xylene, p-Xylene and. The quality of toluene, oXylene and benzene (1,2,3-trimethyl-) is 91 while p-Xylene has 87 quality. Based on the
chromatogram, 16 out of 22 compounds of benzene was discovered in the petrol. It can be
deduced that major compound in the petrol is benzene. Compounds contain in petrol is more
volatile than diesel sample since the retention time is shorter than sample 2 and 3.
For the sample 2 which is diesel, there are 13 compounds found in diesel. The major compounds
identified were octadecane, hexadecane, 2,6,10,14- tetramethyl-, nonadecane and pentadecanoic
acid, 14-methyl-,methyl ester. The quality for octadecane and hexadecane are 99 and 94
respectively. Nonadecane and pentadecanoic acid, 14-methyl-, methyl ester shared same quality
which is 98. Major content in diesel are hydrocarbon since there are 11 hydrocarbon compound
in diesel. The retention time of diesel is about 20 minutes.
Sample 3 is thinner. There was only one component detected which was toluene with 91 quality
and 2.49 min of TR. The fourth sample injected was unknown sample. There were 21 components
detected and the four main components identified were Toluene with 91 quality, 8- octadecenoic
acid, methyl ester, (E)-with 92 quality and the biggest quality of component to be read in library
were Eicosane and Heneicosane with 99 quality.
It was found that in the unknown contain the mixture of petrol, diesel and toluene. It was due to
existent of a few component found in the unknown sample, almost all the compounds are come
from the major sources which are petrol and diesel and thinner. For instance, component of oXylene, p-Xylene, toluene, benzene 1,2,3-trimethyl- in unknown same as in petrol. Besides there
also components of octadecane and nonadecane as in diesel and the present of toluene proved
that thinner was presence in the unknown. The retention time of the unknown sample is above 20
minutes. To improve the efficiency of this experiment, the SPME fiber is the most important. The
fiber must have thinnest coating which will provides acceptable sensitivity and also make
desorption become better.

CONCLUSION
By performing the SPME as the extraction method and the GC as separation method, unknown
sample was identified containing the mixture of petrol, diesel and thinner by referring to the
library f the mass spectrometer.
Recommendation
Washing the injector properly so that no contaminate will occur. Besides referring the quality,
area percent also can be used for selecting the major compound. Area percent represent the
percentage amount of the compound present in the sample.
REFERENCES

1. Nor'ashikin Saim, Ruziyati Tajuddin, and Mardiana Saaid. Analytical Separation


Methods Laboratory Guide. 2nd ed. Selangor: Press UiTM, 2014. Print.
2. Solid-phase

microextraction.

Retrieved

on

November

30th

2014

from

http://en.wikipedia.org/wiki/Solid-phase_microextraction
3. Gas Chromatography / Mass Spectrometry (GC/MS). Retrieved on November 30 th, 2014
from http://www.norchemlab.com/wp-content/uploads/2011/10/Principle-of-GCMS.pdf

4.

EXPERIMENT 4 : ANALYSIS OF HYDROCARBONS IN COMMON FUELS BY


SOLID-PHASEMICROEXTRACTION (SPME) AND GAS CHROMATOGRAPHY
MASSSPECTROMETRY. Retrieved on November 30th, 2014 from
https://www.scribd.com/doc/77107986/Experiment-4-510

Figure 1: Diagram for SPME Extraction procedure