1.

Total Ion Chromatogram of Petrol (Gasoline)

Figur
e 1: Total ion chromatogram (TIC) of standard gasoline (G2)

Table 1: Retention time(min) and the compounds present in the standard gasoline (G2)

Volatile compounds of standard gasoline, G2

RT (min) Compound RT (min) Compound
3.81 Heptane 14.835 2-ethyl-1,4-dimethylbenzene
4.185 Cyclohexane 15.035 1-ethyl-3,5-dimethylbenzene
4.535 Undecane 15.65 1,3-diethylbenzene
4.965 Toluene 15.065 1,2,4,5-tetramethylbenzene
5.34 1-chloroundecane 16.165 1-methyl-3-1-methylethylbenzene
5.535 3-methylheptane 16.655 1-methylindane
6.275 2,4-dimethylhexane 16.95 2-methylindane
7.375 2,5-dimethylheptane 17.12 p-cymene
7.63 Ethylbenzene 17.245 1-methylbutylbenzene
7.93 p-xylene 17.785 napthalene
8.125 m-xylene 19.2 tetradecane
8.615 o-xylene 21.7 Heptacosane
9.435 decane 22.145 2,6-dimethylundecane
9.705 1-methylethylbenzene 24.915 Octadecane
10.68 propylbenzene 27.23 3,5-bis(1,1-dimethylethyl)phenol
10.945 1-ethyl-4-methylbenzene 27.595 2,6,11-trimethyldodecane
11.005 1-ethyl-2-methylbenzene 28.755 Diethyl Phthalate
11.21 1,2,3-trimethylbenzene 32.785 Heneicosane
11.505 1-ethyl-3-methylbenzene 34.59 Heptadecane
12.02 1,3,5-trimethylbenzene 37.035 Dibutyl phthalate
(mesitylene)
12.795 dodecane 37.425 Pentatriacontane
12.89 1,2,4-trimethylbenzene 38.255 Hexadecane
13.225 indane 38.735 Hexacosane
13.88 1,4-diethylbenzene 40.02 1-Docosene
13.965 1-methyl-3-propylbenzene 41.62 2,6,10-trimethyldodecane
14.09 1-methylpropylbenzene 42.36 2-hexyl-1-Decanol
14.2 1-ethyl-2,4- 42.52 Tetratetracontane
dimethylbenzene
14.44 1-methyl-4-propylbenzene 43.91 (Z)-9-Tricosene
14.795 4-ethyl-1,2- 46.08 tetrapentacontane
dimethylbenzene

2. Total Ion Chromatogram of Kerosene

 Figure 2 : Total ion chromatogram (TIC) of standard kerosene (K2)

Table 2: Retention time(min) and the compounds present in the standard kerosene (K2)

Volatile compounds of standard kerosene, K2

RT (min) Compound RT Compound
(min)
3.800 3-methylhexane 17.020 pentylcyclohexane
4.175 methylcyclohexane 17.120 1,2,4,5-tetramethylbenzene
(durene)
4.940 methylbenzene (toluene) 18.115 tetradecane
5.330 2-methylheptane 19.200 pentadecane
5.530 1,1-dimethycyclohexane 19.675 6-ethylundecane
5.570 1,3-dimethylcyclohexane 20.465 3-methyl-1-phenyl-2-butene
6.050 1,2-dimethylcyclohexane 20.975 2,6,10-trimethyldodecane
6.135 tetrachloroethylene 21.115 2-methyldodecane
6.265 4-methyloctane 21.305 11,20-didecyltriacontane
6.970 3-bromohexane 21.435 2,6,10,14-
tetramethylpentadecane
7.085 2-methylpropylcyclohexane 22.145 hexadecane
7.170 3-ethyl-3-metylheptane 22.700 2-methylcyclohexanol
7.255 cis-1,1,3,4-Tetramethylcyclopentane 22.975 heptacosane
7.315 1,1,3-trimethylcyclohexane 23.235 octylcyclohexane
7.365 3,5,5-trimethyl-1-hexanol 23.945 tetracosane
7.620 1,4-dimethylbenzene (p-xylene) 24.120 3,7,11,15-tetramethyl-2-
hexadecan-1-ol (phytol)
7.720 1,2,4-trimethylcyclohexane 24.350 2,6,10,14-
tetramethylhexadecane
(phytane)
7.900 1,3-dimethylbezene (m-xylene) 24.915 heptadecane
8.295 decane 26.625 4-methyldodecane
8.510 3-ethylheptane 27.230 3,5-ditertbutylphenol
8.600 1,2-dimethylbenzene (o-xylene) 27.400 aminomethylcyclohexane
8.855 cis-1-ethyl-4-metylcyclohexane 27.535 octadecane
8.930 trans-1-isopropyl-4- 27.590 2,6,11-trimethyldodecane
methylcyclohexane
9.435 Nonane 27.830 2,6-dimethylundecane
9.705 1-ethyl-2-methylbenzene 28.480 3-ethyl-2-methylheptane
9.790 cyclohexanepropanol 28.590 heptacosane
9.875 isopropylcyclohexane 28.705 bis(7-methyloctyl)ester-1,2-
benzenedicarboxylic acid
(phthalic acis)
10.065 2-noneneol 28.745 didecyl ester-1,2-
bendicarboxylic acid
10.245 propylcyclohexane 30.010 hexacosane
10.395 cyclododecane 32.785 2,6,10,14-
tetramethylhexadecane
10.605 3-methylnonane 33.730 Heneicosane
10.830 3-ethylheptane 34.590 nonadecane
10.940 1-ethyl-3-methylbenzene 37.035 dipropyl ester-1,2-benzene
(m-ethyltoluene) dicarboxylic acid
11.000 1-ethyl-4-methylbenzene 37.425 nonacosane
(p-ethyltoluene)
11.105 2,6-dimethyloctane 38.145 naphthalane dechaydro
11.205 1,2,3-trimethylbenzeen 38.255 tetracosane
 (hemimellitene)
11.525 4-methylnonane 38.735 2-methyldodecane
11.620 undecane 40.020 docosene
12.010 1,3,5-trimethylbenzene (mesitylene) 41.615 pentatriacontane
12.795 dodecane 42.355 11,20-didecyl triacontane
13.600 3,3,5-trimethylheptane 42.520 octacosane
13.965 1-methyl-2-propylbenzene 43.905 1-hexacosene
(o-propyltoluene)
14.200 1-ethyl-2,3-dimethylbenzene 44.295 2-hexyldecanol
(3-ethyl-o-xylene)
14.825 1-isopropenyl-4-methyl-1,3- 46.065 tetrapentacontane
cyclohexadiene
14.945 2,6,11-trimethyldodecane 47.235 tetratetracosane
15.040 1-isopropyl-3-methylbenzene 47.350 11-cyclopentylheneicosane
16.080 tridecane 49.065 bis(trimethylsilyl) ester
methylbutanoic acid
16.650 2-methyldecahydronaphthalene

3. Total Ion Chromatogram of Diesel

 F
igure 3: Total ion chromatogram (TIC) of standard diesel (D2)

Table 3: Retention time(min) and the compounds present in the standard diesel (D2)

Volatile compounds of standard diesel (D2)

RT (min) Compound RT (min) Compound
4.38 methyl cyclohexane 10.98 carbonic acid
5.23 toluene 11.32 tridecane
5.63 3-ethyl heptane 11.665 farmesane
5.825 1,3 dimethyl cyclohexane 12.425 dodecane
6.475 2,4 dimethyl hexane 13.22 1-methyl-napthalene
7.46 ethylbenzene 13.42 tetradecane
7.64 p-xylene 14.155 phytane
8.065 o-xylene 14.34 pentadecane
8.545 acetic acid 14.4 barbituric acid
8.51 undecane 14.44 1,7-dimethyl napthalene
8.665 acetophenone 15.12 3,5-di-tert-butyl-phenol
 8.83 trans-2-undecen-1-ol 15.2 heptadecane
8.945 propylcyclohexane 15.65 diethyl phthalate
9.09 3-methyl nonane 16.01 octadecane
9.15 carbamic acid 16.775 heneicosane
9.27 p-ethyltoluene 16.855 2,6,10,14-tetramethyl
hexadecane
9.3 m-ethyltoluene 17.505 docosane
9.395 mesitylene 16.94 heptacosane
9.52 4-methylnonane 18.195 tetracosane
9.645 2,6-dimetyloctane 18.255 palmitic acid
9.76 1,2,4 trimethyl benzene 18.355 dibutyl phthalate
9.98 eicosane 19.33 cis-linoleic acid
10.055 n-decane 19.38 oleic acid
10.14 1,2,3-trimetylbenzene 19.485 pentacosane
10.38 3-ethyloctane 19.545 methyl melissate
10.45 1-octylnonyl cyclohexane 20.09 hexacosane
10.725 decahydro-napthalene 20.665 nonacosane
10.815 5-methyldecane 21.23 pentriacotane

Discussion:

Petrol, or also known as Gasoline, Kerosene and Diesel are the three types of ignitable liquid
residue (ILR) that are commonly present in fire debris found in arson cases. According to the
UK classification system of ignitable liquids, petrol (gasoline) with the carbon range of C4-
C12 is categorised in Class 2, whereas kerosene with C8-C17 is in Class 4, and diesel with
C8- C>25 belongs to Class 5.

In this experiment, Gas Chromatography-Mass Spectrometry (model GCMS QP2010 plus

Shimadzu, Japan) was used as the instrument to analyse the ILRs. Passive headspace
concentration was also carried out in order to extract the ILRs from the fire debris provided,
by using the procedures as recommended by ASTM E-1412 (Separation of Ignitable Liquid
Residues from Fire Debris Samples by Passive Headspace Concentration with Activated
Charcoal).

After the samples were analysed using GCMS, the total ion chromatogram (TIC) of each
ignitable liquid residue were obtained. Visual pattern recognition of the chromatogram’s
peaks and comparison with the NIST mass spectral library were used to identify the volatile
compounds that are present in our group’s standard petrol (gasoline).
Based on the analysis of gasoline using GC-MS by Shimadzu, Japan, the total ion
chromatogram(TIC) for gasoline is showed below:

Figure 4: Total ion current chromatogram of regular gasoline by Shimadzu, Japan

Meanwhile,the TIC for our group’s standard petrol (gasoline) is as below:

 Figure 1: Total ion chromatogram of standard gasoline for Group 2 (G2).
The same figure in result section above.

Among the target compounds identified based on the TIC of our group’s standard gasoline
sample include, toluene (C7), p-xylene (C2) and 1,2,4-dimethylbenzene (alkylbenzenes). By
comparing the TIC of Figure 1 and 5, both figures show an almost similar chromatographic
distribution pattern for gasoline. The peaks of the TIC for our group’s standard gasoline
sample were mainly centralized between retention time of 5 min to 15 min, whereas for that
conducted by Shimadzu, Japan the peaks were mainly centralized between 4 min to 15 min.
The slight difference could be attributed to the different brand gasoline used, temperature and
GCMS parameters that could influence the elution rate of the compounds.
Figure 5: Total ion chromatogram (TIC) of standard gasoline (G2) with main peaks labelled.

Furthermore, based on the labelled Figure 5 above (same figure extracted from question 3
below), the volatile compounds, toluene, p-xylene, 1,2,4-trimethylbenzene and indane that
are identified from the TIC of our groups standard gasoline (G2), the carbon range of these
compounds was within C12 (as seen in Table 4 below).This is consistent with the UK
classification system, which states that Class 2: petrol (gasoline) consists of C4-C12 carbons.

Table 4: Carbon number of the main compounds detected in standard gasoline (G2)

Compounds of gasoline Carbon number

toluene C7
p-xylene C8
1,2,4-trimethylbenzene C9
indane C9

By using the same method for standard kerosene (K2), the main compounds identified
include a range of alkanes from nonane to heptadecane (C9-C17). The figure with labels can
be seen in the question part below. This characteristic also matches the carbon number range
of C8-C17 according to the UK ignitable liquid classification for kerosene, which belongs to
Class 4.

Table 5: Carbon number of some of the main compounds detected in standard kerosene (K2)
 Compounds of kerosene Carbon number
Nonane C9
Dodecane C12
Tridecane C13
Pentadecane C15
Heptadecane C17

Next, by comparing the TIC of standard diesel of our group with the TIC of diesel from
research by Suppajariyawat, P., et al. (2019), the target compounds for our group’s standard
diesel consist of undecane, farnesane, phytane, tetracosane which are similar with the target
compounds of the standard diesel obtained from the online research conducted.

Figure 6: TIC of Diesel obtained from research by Suppajariyawat, P., et al. (2019)
 Figure 3: Total ion chromatogram of standard diesel for Group 2 (D2).
The same figure in result section above.

Similarly, the carbon numbers of the identified carbon number matches with that of Class 5
Diesel (C8- C>25).

Table 6: Carbon number of some of the main compounds detected in standard diesel (D2)

Compounds of diesel Carbon number

undecane C11
farnesane C15
phytane C20
tetracosane C24

Just that our group’s standard diesel lack of pristane which is one of the important natural
markers for diesel which is a Class 5 heavy petroleum distillate. This could also be due to the
error when we handling the sample during the sample preparation process which leads to
some of the volatiles are evaporated to the surrounding.

However due to different parameters was used and considering the presence of external
factors that are unavoidable, the volatile compounds present and the TIC might differ from
that of standard ILRs from our group.

Questions
1. Explain the extraction process that you have used to extract diesel, petrol and
kerosene from the cotton ball. Elaborate the adsorption process and give reasons as
to why you think specific parameters (temperature, activated carbon tablet, nylon
bag) were used.

For the extraction process, passive headspace concentration with activated charcoal was
used to extract the ignitable liquid residues (ILR) in this lab session, by referring to the
recommended standards of ASTM E-1412 (Separation of Ignitable Liquid Residues from
Fire Debris Samples by Passive Headspace Concentration with Activated Charcoal).

Passive headspace concentration is a process that involves the migration of volatile target
compounds onto the adsorbent material by diffusion at ambient or heated temperatures at
specific time intervals. The volatile target compounds here are the ILRs which are petrol,
kerosene and diesel whereas the adsorbent material used is activated carbon tablet.
(Sandercock et al., 2016)

Firstly, three cotton balls were used to dipped into the three ignitable liquids which were
petrol(gasoline), kerosene and diesel respectively. The entire process was carried out in
the fume hood.

Next, the cotton balls soaked with ILRs were then placed inside three separate nylon
bags. This is due to the nylon bags are made from nylon 11, where non-polar compounds
such as hydrocarbon-based liquids, only can diffused through it at low rates. Relating to
that, all three petrol, kerosene and diesel are hydrocarbon-based liquids.

A piece of activated carbon tablet was placed near the neck region of the nylon bag and
was sealed with cable ties by using the swan neck technique. It is important to ensure that
the nylon bag is correctly sealed in order to retain the hydrocarbon-based liquids (petrol,
kerosene and diesel). Moreover, it is also crucial to ensure that the activated carbon tablet
is put at another edge of the nylon bag from the soaked cotton balls. This is to prevent
direct contact of the ignitable liquids with the activated carbon tablet, which might affect
the GC-MS analysis results later.

According to ASTM E-1412, the headspace vapours were adsorbed under a closed
system. The activated charcoal used in this lab session was in the form of activated
carbon tablet. Activated carbon tablet was used here because it is an effective adsorbent
that is made up of highly porous materials. This characteristic provides a large surface
area facilitating the adsorption of a wide range of hydrocarbons of the volatile ILRs to the
activated carbon tablet.

After that, the nylon bag which contains both the activated carbon tablet on one edge and
soaked cotton ball with ILRs on the other edge, was placed horizontally into the oven
(Thermo Scientific Heratherm Oven) at 80°C for 30 minutes. Consequently, the volatiles
adsorb on the activated carbon tablet was desorbed using a solvent wash. For petrol and
kerosene, the solvent used was n-pentane, whereas for diesel, hexane was used as the
solvent. This is due to petroleum-based fuels like petrol, gasoline and diesel are highly
soluble in non-polar solvents such as pentane and hexane. Furthermore, these solvents
would not interfere the main chromatographic peaks.

Later, the solution which contain the solvent and desorbed ILRs from the activated carbon
tablet was transferred into a GC vial by using a syringe with filter. The cap of the GC vial
was covered quickly to prevent evaporation of the samples and was labelled before being
inserted into the injection port of GC-MS.

Regarding the specific parameters used in this experiment, the justifications are as below.

Parameters Justifications (Reasons)

A. Temperature
i) Injection temperature: 250°C This is to ensure the temperature is hot
enough to enable instantaneous
evaporation of the entire ILR sample upon
injection.
ii) Detector temperature: 300°C The column used is a DB-1MS Capillary
column which is 100%
methylpolysiloxane. The upper
temperature limit for this non-polar
column is 300°C. At 300°C, it also
ensured that all supplied gases are
optimised.
iii) Oven temperature programme: 2  Oven temperature is set at 80°C as
minutes at 80 °C and ramped at 4 it is recommended by ASTM E-
°C / min up to 160 °C and held 1618 standards. This will enable a
for 5 minutes. more distinct separation of the
components of the samples.
  Ramping temperature will help the
compounds that would otherwise
elute later to move through the
column faster.
 The oven programme is important
in the separation of different
components depending on their
boiling points and interaction with
the stationary phase.

B. Activated Carbon Tablet It is made up of highly porous materials

which facilitates the adsorption of wide
range of hydrocarbons of the ILRs on the
activated carbon tablet.
C. Nylon bag The nylon bag is made up of Nylon 11
which is capable to retain hydrocarbon-
based liquids (petrol, kerosene and diesel)

2. Explain the process that the sample undergoes when it has been injected into the
GC-MS?
The sample contained in the vials were still in liquid form initially, there were then
introduced and volatized into gas form in the injection port of the gas chromatograph part
of GC-MS. The injection port is heated up to 250°C where the sample vaporizes
immediately. The sample then pass through the DB-1MS capillary column with the help of
inert carrier gas such as helium, hydrogen and nitrogen. These carrier gases act as the mobile
phase and carries the sample through the stationary phase. The non-polar column provides a
surface for the compounds to interact. In the column, the sample undergo separation based on
their different affinity and polarity towards the stationary phase.

Apart from stationary phase interaction, temperature also plays an important role in the
separation of compounds. The column is held in an oven that can be programmed to increase
the temperature gradually (ramped), which helps in separation as well. The compounds that
have lower boiling points will elute first as compared to compounds with higher boiling
points as the temperature increases.
 The separated components of the sample were then eluted from the column to the detector.
The detector is capable of creating an electronic signal whenever the presence of compound is
detected. The computer will then generate a graph from the signal, which is known as
chromatogram. Proportional peaks of each chemical component that ertr being recorded on a
chromatogram are also known as total ion chromatogram (TIC). Each peak within the
chromatogram corresponds to a hydrocarbon in the ignitable liquid.

After that, the molecules will be vaporized and then ionized before passing through the
quadrupole rods. The detector used was quadrupole mass spectrometer. The ions were
accelerated through a magnetic field and sorted out based on molecular weight. After the ions
were being sorted, they were detected, and the data tabulated.

3. What were the peaks that were identified from the chromatogram of the petrol,
diesel and kerosene? Insert your chromatogram for each of the sample and label the
peaks in the chromatogram for your GC-MS output. Derived a table containing
retention time (min) and name of compound.

a) Petrol/Gasoline (G2)
 Toluene

p-xylene

m-xylene

1,2,4-trimethylbenzene

Indane

Figur
e 7: Total ion chromatogram (TIC) of standard gasoline (G2) with main peaks labelled.

Table 7: Retention time (min) and name of compound for standard Gasoline (G2). The main
compounds corresponding to the peak is labelled in green.

Volatile compounds of standard gasoline, G2

RT (min) Compound RT (min) Compound
3.81 Heptane 14.835 2-ethyl-1,4-dimethylbenzene
4.185 Cyclohexane 15.035 1-ethyl-3,5-dimethylbenzene
4.535 Undecane 15.65 1,3-diethylbenzene
4.965 Toluene 15.065 1,2,4,5-tetramethylbenzene
5.34 1-chloroundecane 16.165 1-methyl-3-1-methylethylbenzene
5.535 3-methylheptane 16.655 1-methylindan
6.275 2,4-dimethylhexane 16.95 2-methylindan
7.375 2,5-dimethylheptane 17.12 p-cymene
7.63 Ethylbenzene 17.245 1-methylbutylbenzene
7.93 p-xylene 17.785 napthalene
8.125 m-xylene 19.2 tetradecane
8.615 o-xylene 21.7 Heptacosane
9.435 decane 22.145 2,6-dimethylundecane
9.705 1-methylethylbenzene 24.915 Octadecane
10.68 propylbenzene 27.23 3,5-bis(1,1-dimethylethyl)phenol
10.945 1-ethyl-4-methylbenzene 27.595 2,6,11-trimethyldodecane
11.005 1-ethyl-2-methylbenzene 28.755 Diethyl Phthalate
11.21 1,2,3-trimethylbenzene 32.785 Heneicosane
11.505 1-ethyl-3-methylbenzene 34.59 Heptadecane
12.02 1,3,5-trimethylbenzene 37.035 Dibutyl phthalate
(mesitylene)
12.795 dodecane 37.425 Pentatriacontane
12.89 1,2,4-trimethylbenzene 38.255 Hexadecane
13.225 indane 38.735 Hexacosane
13.88 1,4-diethylbenzene 40.02 1-Docosene
13.965 1-methyl-3-propylbenzene 41.62 2,6,10-trimethyldodecane
14.09 1-methylpropylbenzene 42.36 2-hexyl-1-Decanol
14.2 1-ethyl-2,4- 42.52 Tetratetracontane
dimethylbenzene
14.44 1-methyl-4-propylbenzene 43.91 (Z)-9-Tricosene
14.795 4-ethyl-1,2- 46.08 tetrapentacontane
dimethylbenzene

b) Kerosene (K2)
 Tridecane
Dodecane

p-ethyltoluene Pentadecane

Nonane

Hexadecane
1,3-dimethylbezene

Heptadecane
Toluene

Figure 8: Total ion chromatogram (TIC) of standard kerosene (K2) with main peaks labelled.

Table 8: Retention time (min) and name of compound for standard kerosene (K2). The main
compounds corresponding to the peak is labelled in yellow.

Volatile compounds of standard kerosene, K2

RT (min) Compound RT Compound
(min)
3.800 3-methylhexane 17.020 pentylcyclohexane
4.175 methylcyclohexane 17.120 1,2,4,5-tetramethylbenzene
(durene)
4.940 methylbenzene (toluene) 18.115 tetradecane
5.330 2-methylheptane 19.200 pentadecane
5.530 1,1-dimethycyclohexane 19.675 6-ethylundecane
5.570 1,3-dimethylcyclohexane 20.465 3-methyl-1-phenyl-2-butene
6.050 1,2-dimethylcyclohexane 20.975 2,6,10-trimethyldodecane
6.135 tetrachloroethylene 21.115 2-methyldodecane
6.265 4-methyloctane 21.305 11,20-didecyltriacontane
6.970 3-bromohexane 21.435 2,6,10,14-
tetramethylpentadecane
7.085 2-methylpropylcyclohexane 22.145 hexadecane
7.170 3-ethyl-3-metylheptane 22.700 2-methylcyclohexanol
7.255 cis-1,1,3,4-Tetramethylcyclopentane 22.975 heptacosane
7.315 1,1,3-trimethylcyclohexane 23.235 octylcyclohexane
7.365 3,5,5-trimethyl-1-hexanol 23.945 tetracosane
7.620 1,4-dimethylbenzene (p-xylene) 24.120 3,7,11,15-tetramethyl-2-
hexadecan-1-ol (phytol)
7.720 1,2,4-trimethylcyclohexane 24.350 2,6,10,14-
tetramethylhexadecane
(phytane)
7.900 1,3-dimethylbezene (m-xylene) 24.915 heptadecane
8.295 decane 26.625 4-methyldodecane
8.510 3-ethylheptane 27.230 3,5-ditertbutylphenol
8.600 1,2-dimethylbenzene (o-xylene) 27.400 aminomethylcyclohexane
8.855 cis-1-ethyl-4-metylcyclohexane 27.535 octadecane
8.930 trans-1-isopropyl-4- 27.590 2,6,11-trimethyldodecane
methylcyclohexane
9.435 Nonane 27.830 2,6-dimethylundecane
9.705 1-ethyl-2-methylbenzene 28.480 3-ethyl-2-methylheptane
9.790 cyclohexanepropanol 28.590 heptacosane
9.875 isopropylcyclohexane 28.705 bis(7-methyloctyl)ester-1,2-
benzenedicarboxylic acid
(phthalic acis)
10.065 2-noneneol 28.745 didecyl ester-1,2-
bendicarboxylic acid
10.245 propylcyclohexane 30.010 hexacosane
10.395 cyclododecane 32.785 2,6,10,14-
tetramethylhexadecane
10.605 3-methylnonane 33.730 Heneicosane
10.830 3-ethylheptane 34.590 nonadecane
10.940 1-ethyl-3-methylbenzene 37.035 dipropyl ester-1,2-benzene
(m-ethyltoluene) dicarboxylic acid
11.000 1-ethyl-4-methylbenzene 37.425 nonacosane
(p-ethyltoluene)
11.105 2,6-dimethyloctane 38.145 naphthalane dechaydro
11.205 1,2,3-trimethylbenzene 38.255 tetracosane
(hemimellitene)
11.525 4-methylnonane 38.735 2-methyldodecane
11.620 undecane 40.020 docosene
12.010 1,3,5-trimethylbenzene (mesitylene) 41.615 pentatriacontane
12.795 dodecane 42.355 11,20-didecyl triacontane
13.600 3,3,5-trimethylheptane 42.520 octacosane
13.965 1-methyl-2-propylbenzene 43.905 1-hexacosene
(o-propyltoluene)
14.200 1-ethyl-2,3-dimethylbenzene 44.295 2-hexyldecanol
(3-ethyl-o-xylene)
14.825 1-isopropenyl-4-methyl-1,3- 46.065 tetrapentacontane
cyclohexadiene
14.945 2,6,11-trimethyldodecane 47.235 tetratetracosane
15.040 1-isopropyl-3-methylbenzene 47.350 11-cyclopentylheneicosane
16.080 tridecane 49.065 bis(trimethylsilyl) ester
methylbutanoic acid
16.650 2-methyldecahydronaphthalene
c) Diesel (D2)
 1. 1,3-dimethylcyclohexane
2. ethylbenzene
Methyl cyclohexane 3. undecane
4. n-decane
5. farnesane
6. dodecane
7. tetradecane

2,4-dimethylhexane
4.

5.
3.
6.

2.
7.

1. Phytane
Tetracosane

Figure 9: Total ion chromatogram (TIC) of standard diesel (D2) with main peaks labelled.

Table 9: Retention time (min) and name of compound for standard diesel (D2). The main
compounds corresponding to the peak is labelled in light blue.

Volatile compounds of standard diesel (D2)

RT (min) Compound RT (min) Compound
4.38 methyl cyclohexane 10.98 carbonic acid
5.23 toluene 11.32 tridecane
5.63 3-ethyl heptane 11.665 farnesane
5.825 1,3 dimethyl cyclohexane 12.425 dodecane
6.475 2,4-dimethyl hexane 13.22 1-methyl-napthalene
7.46 ethylbenzene 13.42 tetradecane
7.64 p-xylene 14.155 phytane
8.065 o-xylene 14.34 pentadecane
8.545 acetic acid 14.4 barbituric acid
 8.51 undecane 14.44 1,7-dimethyl napthalene
8.665 acetophenone 15.12 3,5-di-tert-butyl-phenol
8.83 trans-2-undecen-1-ol 15.2 heptadecane
8.945 propylcyclohexane 15.65 diethyl phthalate
9.09 3-methyl nonane 16.01 octadecane
9.15 carbamic acid 16.775 heneicosane
9.27 p-ethyltoluene 16.855 2,6,10,14-tetramethyl
hexadecane
9.3 m-ethyltoluene 17.505 docosane
9.395 mesitylene 16.94 heptacosane
9.52 4-methylnonane 18.195 tetracosane
9.645 2,6-dimetyloctane 18.255 palmitic acid
9.76 1,2,4 trimethyl benzene 18.355 dibutyl phthalate
9.98 eicosane 19.33 cis-linoleic acid
10.055 n-decane 19.38 oleic acid
10.14 1,2,3-trimetylbenzene 19.485 pentacosane
10.38 3-ethyloctane 19.545 methyl melissate
10.45 1-octylnonyl cyclohexane 20.09 hexacosane
10.725 decahydro-napthalene 20.665 nonacosane
10.815 5-methyldecane 21.23 pentriacotane

4. Were there any patterns that could be detected from the chromatograms of the
three ignitable liquids, that could be used to distinguish each one from the other? If
yes, explain how did you come to this conclusion? If no, explain how did you come to
this conclusion?
 Figure 1: TIC of standard gasoline for our group (G1), the chromatographic pattern was
shown in red. The same figure as result section above was used here.

For petrol(gasoline) due to it is a lighter petroleum distillate, the peaks of the TIC for
petrol will usually be eluted faster and located slightly in front as compared to the other
two heavier petroleum distillates like kerosene and diesel. The chromatographic pattern
based on the TIC of our group’s standard gasoline sample(G2) showed a skewed pattern,
where the height of the peaks is descending towards the right side. Moreover, 1,2,4-
trimethylbenzene, 1,2,4,5-tetramethylbenzene, and 1,3-dimethylnaphthalene are among
the commonly identified target compounds for petrol (gasoline) based on the research
conducted by other researchers. However, based on the TIC obtained for our group,the
only target compounds that was identified among these three was 1,2,4-trimethylbenzene
as shown in Table 7 above. 1,2,4,5-tetramethylbenzene, and 1,3-dimethylnaphthalene
were not detected.
 Figure 2: TIC of standard kerosene for our group (K2), which showed a bell-shaped
curve distribution as indicated by the red circle. The same figure as result section above.

Kerosene consists different types of hydrocarbons such as alkanes, cycloalkanes and

aromatics. The carbon range for kerosene is from C7 to C16, which is from heptane to
hexadecane for alkanes. It is considered as medium heavy distillate and is categorised
under Class 4 of the UK classification system Meanwhile, kerosene also contains
alkybenzenes ranging from toluene to C6 alkyl benzenes. Based on Figure 2 above, the
chromatographic pattern of kerosene showed a bell-shape distribution curve.
Figure 3: TIC of standard diesel for our group (D2), which also showed a bell-shaped
curve distribution as indicated by the red circle. The same figure as result section above

For diesel, it also displayed a bell-shaped curve distribution similar to kerosene. Although
it is more typical to see a gaussian curve ( bell-shaped distribution) in the TIC for diesel.
In order to distinguish between kerosene and diesel, the important natural markers of
diesel like phytane and pristane plays an important role. This is due to diesel is a heavy
petroleum distillate under Class 5 of the UK classification system which contain these
important natural markers.

Moreover, according to Stephanie et al, the major components present in diesel are the
twelve dominant alkanes that peak at regular intervals over the chromatogram ranging
from n-C10 to n-C21 which are characteristic for diesel. Some of the n-alkanes include
dodecane and tetradodecane as shown in Figure 9 in Question 3 above.

Nonetheless, the characteristic target compounds are merely the results obtain from
research articles and journals, and may varies based on different conditions and
parameters employed by the researcher. Furthermore, the TICs are time dependent and
can differ greatly between different experiments depending on the column type and
instrument parameters used too. Thus, there will hardly be an exact match of the entire
volatile compounds found even though they might originate from the same ignitable
liquid. The best thing we can do within our limitations is to identify the target compounds
by comparing it with the NIST mass spectral library and also refer the standards from
journal articles regarding the respective ILRs of other researchers online.
5. What were the differences between the analysis from the GC-MS and GC-FID?

GC-MS has high selectivity due to it make use of the high separating capacity of
chromatography and the high identification characteristics of mass spectrometry. The
chromatogram result from the mass-spectrometry (MS) is based on the intensity of
fragments produced by the ionization. This give rise to a more definite qualitative
analysis. Moreover, GC-MS is capable to provide exact identification of the compounds
which enables the determination of structural difference between the molecules. As a
result, GC-MS is often used for the identification of single component ignitable liquids
and even for samples that contain high concentrations of interfering compounds.

On the other hand, GC-FID is based on the ions of the burning organic compounds which
measures the current in flame. When the compounds pass through the flame, it changes
the conductivity and generate the signal. Unlike GCMS that is capable to provide exact
identification of the compounds, for GC-FID it can only determine the total carbon
number of the compound. Thus, GC-FID is usually used as a preliminary test to identify
the compound present in the ignitable liquids.

Conclusion:

Passive headspace extraction can be used to extract the volatile compounds from
petrol(gasoline), kerosene and diesel samples. GCMS is capable to analyse the ignitable
liquid residue present in the fire debris samples by identifying the target compounds of
ILR present, via comparison of the TIC peaks obtained with the NIST mass spectral
library.

Reference:

1. Dhabbah, A. M. (2019). “Investigation of Kerosene used as Fire Accelerant

Remaining on Different Kinds of Fabrics.” Arab Journal of Forensic Sciences &
Forensic Medicine (AJFSFM), 1(10):1386.
2. Suppajariyawat, P., et al. (2019). "The Use Of Chemical Composition And Additives
To Classify Petrol And Diesel Using Gas Chromatography–Mass Spectrometry And
Chemometric Analysis: A UK Study." Open Chemistry 17: 183-197.
3. Gabriel, G., et al. (2017). "Malaysian Journal Of Analytical Sciences The Analysis of
Thermal Decomposition Products Generated from Porcine Tissues exposed to
Outdoor Burning Conditions." Malaysian Journal of Analytical Sciences 21: 585-596.
4. Sandercock, P. M. L. (2016). “Passive Headspace Extraction of Ignitable Liquids
using
Activated Carbon Cloth,” Canadian Society of Forensic Science Journal, Vol 49, No.
4, pp. 176-188.
5. Henry, C. L. (2008). “Study of Nylon Bags for Packaging Fire Debris,” CAC News,
Vol 4, 2008, pp. 30-32.
6. Shimadzu (2011) Analysis Gasoline using a GC-MS, LAAN-E-MS-E021