EXPERIMENT 7: GAS CHROMATOGRAPHY MASS SPECTROSCOPY (GC-MS)

OBJECTIVE
I. To prepare sample for GC-MS.
II. To learn how does the GC-MS works.
III. To differentiate hydrocarbons in the samples.

MATERIALS AND APPARATUS

SPME holder with 100 um polymethylsiloxane (PDSM) fibre.

SAMPLE
Unleaded petrol, diesel, paint thinner and kerosene.

INTRODUCTION

Gas chromatography (GC) is used to separate mixtures of chemicals into individual

components. In GC, the mobile phase is an inert gas such as helium and it carries the sample
mixture through a stationary phase. The stationary phase is usually contained in a tube called
column. The mixture of compounds in the mobile phase interacts with the stationary phase
and it interacts at a different rate.

Mass spectrometry is an analytical technique used to quantify known materials, to

identify unknown compounds within a sample, and to elucidate the structure and chemical
properties of different molecules. The complete process involves the conversion of the
sample into gaseous ions, with or without fragmentation, which are then characterized by
their mass to charge ratios (m/z) and relative abundances.
 Figure 1: Schematic layout of a GCMS instrument

Gas chromatography – mass spectroscopy (GC-MS) is one of the hyphenated

analytical techniques. It is actually two techniques that are combined to form a single method
of analyzing mixtures of chemicals. Gas chromatography separates the components of a
mixture and mass spectroscopy characterizes each of the components individually.
Combining the two techniques can both qualitatively and quantitatively evaluate a solution
containing number of chemicals. GC-MS are widely used in the medical, pharmacological,
environmental and law enforcement fields.
PROCEDURE
I. INSTRUMENT SETUP
1. Injection temperature : 250 C
2. Detector temperature : 300 C
3. Carrier gas flow rate : 30 ml/s
4. Column temperature : 60 C to 170 C at C/ min

II. SPME PROCEDURE

1. The fiber was conditioned in the GC injection port at 250 C for at least 10 min
in order to remove contaminants.
2. 5 ml of the sample was add approximately in glass vial and then placed on a
hot plate. The sample was heated at 50 C and agitated with magnetic stirrer.
3. The fiber was then exposed to the headspace of vial for 20 minutes.
4. The fiber was withdrawn into the needle and the vial was pulled off. It was
then immediately injected into the GCMS with desorption time of 80 seconds.
5. The major compound in each sample was then identified using mass spectra
library.

III. STANDARD OPERATION PROCEDURE

1. The GCMS model was operated through steps with the supervision of lab
assistant.
RESULT

SAMPLE COMPOUND RT COMPOUND QUALITY M/Z

DETECTED (min) ID RATIO
UNLEADED Benzene, 2 – ethenyl - 1, 3, 9.933 22220 87 131.0
PETROL 5 - trimethyl 000769-25-5
1H - Indene, 2, 3 - dihydro- 10.138 22226 89 131.0
5, 6 - dimethyl 001075-22-5
Naphthalene, 2 - methyl 10.825 19725 95 142.0
000091-57-6
Hexadecane 14.573 89842 95 226.0
000544-76-3
DIESEL Benzene, 4 - (2-butenyl) – 11.002 32041 70 145.0
1, 2 – dimethyl-, E - 054340-86-2
1 - Acenaphthenol 14.327 39944 83 170.0
006306-07-6
Hexadecane 14.695 89839 87 226.0
000544-76-3
Pentadecane, 2, 6, 10 - 15.528 115565 91 239.0
trimethyl 003892-00-0

Table 1: Tabulation data of GCMS for Unleaded Petrol and Diesel

DISCUSSION AND ANALYSIS

GCMS is an experimental technique that incorporates two widely used techniques in

one method as a whole. The GC portion is the Gas Chromatography used for separating
components in a mixture and the MS portion is the Mass Spectrometry used in the qualitative
and quantitative analysis of each component that was separated by the GC.

In this experiment, two liquid samples, unleaded petrol (sample 1) and diesel (sample
2) were used. Both two samples give similar result for GC and MS. The mass spectrum of
each of these compounds is presented in Table 1. In full scan mode, the criteria for
identification of target analytes include the number of the retention times with those of the
standards to within 20 minutes. The result observed for a given compound is proportional to
its concentration in the gas stream. The mass spectra correspond to those of the standards
with any significant peaks are present in the result. Somehow, not all compounds are
ionizable or detectable with similar efficiencies. There are also an additional peaks present
due to overlap with other components. In this experiment, only the 4 highest peaks were
recorded for further discussion.

The two samples do not have equal retention times for all its compound substances as
those samples do not have the same substance. However, identical retention times for two
samples were also present which indicate a possibility that there are presences of the same
substance in the sample. The spectral peaks for both samples are seen to be in symmetrical,
narrow, separate (not overlapping).

For sample 1, it has recorded 18 different analytes. The compounds detected in the
sample are different at all retention time. It has been detected that the higher number of
compound found in the sample are Benzene, 2 – ethenyl - 1, 3, 5 – trimethyl, 1H - Indene, 2,
3 - dihydro-5, 6 – dimethyl, Naphthalene, 2 – methyl and Hexadecane. In this sample, both
Naphthalene, 2 – methyl and Hexadecane has the same highest quality value of 95. The m/z
ratio for Hexadecane is the highest of all which are 226.0 which represents the largest ion
going through the mass spectrometer is the heaviest ion that are obtained in an unleaded
petrol.
 For sample 2, it has recorded 28 different analytes. The compounds detected in the
sample are also different at all retention time. The 4 top higher compound present and found
in this sample are Benzene, 4 - (2-butenyl) – 1, 2 – dimethyl-, E - 1 – Acenaphthenol,
Hexadecane Pentadecane, and 2, 6, 10 –trimethyl. In this sample, the entire compound
detected has different quality value and thus giving the difference value of the m/z ratio for
all compound substances found. Since most of the ions formed in a mass spectrometer have a
single charge, so the m/z value is equivalent to mass itself and thus provide completely
accurate values for the molecular mass of a compound. In this sample, Pentadecane, 2, 6, 10
–trimethyl is found to be the heaviest ion that are obtained in a diesel.

CONCLUSION

GC and MS are useful tools for chemical analysis, especially when used together.
GCMS has been regarded as a powerful compound identification as it have a positively and
accurate result to identifies the presence of a particular substance. The GC instrument is
effective in separating compounds into their various components. However, the GC
instrument cannot be used for reliable identification of specific substances. The MS
instrument provides specific results but produces uncertain qualitative results.
QUESTIONS

1. Why does information on compounds in a sample obtained from gas

chromatography (GC) usually needed to be further analysed by mass
spectroscopy (MS)?
Mass spectrometry (MS) is an analytical technique that ionizes chemical species and
sorts the ions based on their mass-to-charge ratio. A mass spectrum measures the
masses within a sample. It is needed to be further analysed so that can enable the
comparing of the specimen's mass spectrum with known compounds.

2. List several precautions that should not be ignored in handling GCMS.

There are several safety precautions that should be kept in mind while using the GC-
MS. The machine is connected to a power source, and many of the internal parts carry
a dangerous voltage, even when the power switch is off. Many parts of the machine
get hot and should not be touched. Do not turn the mass spectrometer off, or bring
food/drinks into the instrument room, as they may damage it. It is also recommended
that the room is kept ventilated, and advisable to wear long sleeves, gloves, and safety
glasses, as some of the parts use refractory ceramic fibers. In general, do not mess
with or remove parts. When the machine is on, keep hands out of the plastic guard, as
this is where the auto sampler moves.

3. What are the limitations of GCMS?

The limitations of GCMS are response factor, worn septum, injection port,
temperature residual impurities carrier gas crucial factors
 REFERENCE

(n.d). Gas Chromatographic-Mass Spectrometry Is Olive Oil the healthiest oil? Retrieved
from http://courses.chem.indiana.edu/a315/documents/gcmshandout_000.pdf

Douglas,. F. (2018). GC/MS Analysis. Retrieved from

http://www.scientific.org/tutorials/articles/gcms.html

GCMS Analysis of Ethanol and Benzene in Gasoline. (2014). Retrieved from

https://aerosol.chem.uci.edu/AirUCI_summer/PDFs/labs/2014_GCMS_Lab.pdf