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RESEARCH ARTICLE

Analysis of Petrol: A Clarification for Purity of


Petrol

G. M. Ramteke , L.B. Revatkar, R.V. Phadke, N.L.Chutke*

Regional Forensic Science Laboratory, M.S. Nagpur-440012, India

*Corresponding author: Nitin Chutke, email: nitichutke@gmail.com

Abstract:

The samples of petrol are received by the forensic science laboratories for
testing its purity and adulteration. The purity of petrol is defined by various
physical and chemical properties. Those properties include its colour, smell,
density, distillation range and composition or the content of petrol. Interesting
results were obtained during examination of petrol samples in which there may
arise a question regarding its purity due to drastic change in the properties of
petrol. The present study investigates reasons for the drastic changes in the
properties of pure petrol to prove it to be genuine or pure one.
Open Access Article
Keywords: Petrol purity, Delayed analysis, Density
Citation: G. M. Ramteke , L.B. Revatkar,
R.V. Phadke, N.L.Chutke (2016) Analysis
of Petrol: A Clarification for Purity of
Petrol. ESR Journal 1(1):[link]

Academic Editor: Mahmoud Elsharafi


Pesl, Midwestern State University, United Introduction
States

Received: 11th January 2016 Petrol (Beerstech 1954, James 1990) is obtained from decay and
decomposition of plant and animal body. For transport the liquid fraction of
Accepted: 23th February 2016
petroleum (Bhaskara 2014), motor gasoline has become an inevitable part of our
Published: 30th March 2016 life (James 2002). Basically petrol is mixture of hydrogen and carbon and fuel
motor gasoline is volatile liquid fraction of it (Schobert, 1990). Petrol or
Copyright: 2016 This is an open
access article under the terms of the petroleum spirit is also known as gasoline consists essentially of C4 to C12
Creative Commons Attribution License, hydrocarbons (The Merck Index 2001). It is a toxic, translucent, highly
which permits unrestricted use, inflammable liquid and is primarily used as a fuel in spark/internal combustion
distribution, and reproduction in any
medium, provided the original author and engines (Laboratory Procedure Manual 2005). It consists mostly of organic
source are credited. compounds obtained by the fractional distillation of petroleum, with a variety of
additives to enhance various performance features related to the satisfactory
Data Availability Statement:
operation of engines as well as to minimize fuel handling storage and air pollution
Funding: The author(s) received no after combustion.
specific funding for this work Gasoline or petrol is a major transport fuel in India. Adulteration of fuel at
Competing Interests: The authors have the point of sale or during transportation has become acute problem in the
declared that no competing interests country. Adding low- taxed or subsidized kerosene to gasoline increases engine
exists. deposits and emissions. Also leading to loss of government fiscal revenue is
unlikely to have adverse environmental impacts (Gawande et al.2013).

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Analysis of Petrol: A Clarification for Purity of Petrol

Petroleum products, most frequently referred to the forensic science


laboratories for examination regarding their purity. As petrol is highly volatile as
compared to the other fuel such as diesel and kerosene, it requires proper
handling and storage for rapid checking of degree of adulteration. The analysis of
the petrol is a complex task and normal laboratory practice and routine analysis
of petrol include tests such as- colour, smell and density along with distillation
range. Variation in any one of these properties always questioned regarding the
sample being a pure one. In the present study petrol samples showing abnormal
properties in the range of kerosene were tested and purity of the sample was
explained with respect to the properties of pure and fresh petrol sample.

Significance of the study

In the present study, the results obtained and interpretations discussed for
the evaporated petrol samples are helpful to decide the purity of petrol sample in
following cases which fall under Essential Commodity Act (E.C. Act) in India
(The Essential Commodity Act is an act of the Parliament of India which was
established to ensure the delivery of certain commodities or products, the supply
of which if obstructed owing to handling or black marketing would affect the
normal life of the people. Petroleum products are one of the major products that
come under E. C. Act), 420 Indian Penal Code (cheating) or under unlawful
possession.
Possibilities for obtaining unexpected results are:
a) If the petrol samples received in the laboratory are stored for long
period before analysis
b) If the container of petrol sample is not packed properly.

Experiment

The properties of petrol such as colour, density, distillation range were


determined using standard analytical methods laid down by Indian standard
specification for motor gasoline/petrol IS 2796/2000.
a) Density- Density of the sample was found using Anton Paar Density
meter DMA 5000 having Anton Paar SP 1m sample changer.
b) Distillation range- Distillation range was analysed using AutoDist
Distillation Analyzer.
c) Colour/Dye identification- High Performance Thin Layer
Chromatography (HPTLC) technique was adapted to ascertain the
presence of dye. Petrol samples, kerosene sample and adulterated
samples were extracted in solvent N-N Dimethyl Formamide (DMF)
and were spotted on TLC Silica Gel (60F 254) plate. The plate was
developed in Hexane: Acetone (8:2) solvent system (after the
chamber is well saturated with solvent system). The plate was
developed to 10 cm. Then spots were observed visually as well as
under UV chamber.

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Analysis of Petrol: A Clarification for Purity of Petrol

d) Filter paper test- A drop of pure petrol and kerosene adulterated


petrol samples were taken on filter paper and tested for the purity.
Petrol is clean and highly volatile fuel and hence a drop of petrol
vaporizes more easily and quickly from the filter paper without
leaving any traces or patch of oil behind.

Evaporation of low volatile hydrocarbons was examined using Gas


Chromatographic (GC) technique. 1% solution of petrol was prepared in diethyl
ether and one microlitre (l) of this solution was used for analysis. GC System-
Nucon model 5765 having Nuchrom software was used for the analysis. GC
Operating conditions were as follows: Column- Stainless steel column, 1/8 Outer
Diameter, length 2 meter, packed with SE 30 on chromosorb-W, HP, 80/100
mesh ; Carrier gas-Nitrogen 40 mL / min; Detector: Flame Ionization Detector
(FID); Oven Temp program: Initial 500 C (hold time 1 min), @50C/min to
100oC hold for 2 min then @10oC/min final temp. 2200C (hold time 5 min);
Injector temp-2000C; Detector temp-2200C

Results and discussion

In the experiment pure petrol samples from petrol pump were purchased. The
colour, quantity, smell, density and percent recovery of the samples were
determined. Experiments were carried out at room temperature (260C). For the
study of the effect of evaporation of petrol on its properties freshly purchased 500
mL petrol sample was taken in a 1 liter glass bottle and the sample was allowed
to evaporate at room temperature. During experiment, colour, quantity, smell,
density and percent recovery of the samples were recorded as follows;

Effect on colour
Dyes are usually added for identification in solid or liquid form. Orange dyes
are added for regular petrol, red dyes are added for premium petrol and green
dyes are added for aviation gasoline to distinguish and specify the quality of
petrol or type of fuel. As per IS 2796/2000, normally oil orange dye (Phenyl azo
2-naphthol) is used for colouring petrol. It is an azo dye.
As the quantity of petrol samples reduce, the colour of samples was found to
be dark orange as compared to the initial fresh petrol sample. It was found that
as % evaporation of samples increases the orange dye present in the petrol also
get intensifies to dark orange. This increase in intensity of the colour is attributed
to the concentration of the orange dye in the evaporated petrol sample.

Effect on density
Determination of density is also an important parameter for getting an idea
about the type of fuel. As stated earlier the density of petrol was found out using
Anton Paar Density meter. The results in Table 1 indicate that the density of the
petrol sample found to increase as the % evaporation of sample increases. The
inverse relation of evaporation of petrol and its density can be satisfactorily
explained by considering the chemical composition of the petrol. Petroleum

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hydrocarbons/ petrol/ commercial motor gasoline is a blend mixture of


hydrocarbons which include paraffin of lowest density, iso-paraffins,
cycloparaffins and olefins of having intermediate density, naphthalenes and
aromatics of highest density. The density of petrol is average values of densities
of all these components present in it. The density at 15C of a typical standard
Petrol (Motor Gasoline) is 710-770 (Kg/m3). When sample of petrol is allowed to
evaporate, lower petroleum hydrocarbons fraction with lowest density get
evaporated leaving behind high density petroleum hydrocarbons. Hence the
density of the petrol was found to increase with the evaporation of petrol. The
density of petrol even reaches to the value resembling density of kerosene i.e.
about 0.791 and even 0.802. This situation gives rise to the doubt regarding the
purity of sample and hence further proper analytical investigations such as its
percent recovery, detection of high boiling petroleum hydrocarbons etc. become
necessary.

Table 1. Variation in properties of fresh, evaporated and adulterated petrol samples


Petrol/Petrol+Kerosene Density %Recovery
0 0 0 0 0
IBP ( C) 10% ( C) 50% ( C) 70% ( C) FBP ( C)
0
@26 C
Pure petrol 0.719 42 55 98 127 154
Up to 5% 0.725 44 63 103 130 165
Up to 20% 0.751 54 63 112 130 174
Up to 21-30% 0.768 57 67 112 132 174
Up to 31-40% 0.774 58 71 114 136 170
Up to 41-50% 0.783 72 93 127 136 186
Up to 51-55 % 0.791 89 100 124 137 183
Up to 56-60% 0.802 92 105 126 138 184
10% adulterated 0.725 46 55 103 136 206
20% adulterated 0.733 45 60 113 154 232
Kerosene 0.795 120 160 196 238 259
(The values are the average of three readings)

Effect on distillation range


Density of petrol lies in the range of 0.710-0.777 and boiling range is 400C-
2150C. However density of kerosene is 0.78-0.82 and boiling range is 1500C -
2500C. Thus petrol is highly volatile fuel as compared to the other fuels such as
kerosene and diesel (Laboratory Procedure manual, Petroleum Products, 2005).
In determination of the distillation range Initial Boiling Point (IBP) gives the
idea about volatility of the sample. The temperatures of IBP shows the ease of
starting, 10% to 90% gives the idea for rate of acceleration, smooth running and
complete combustion of fuel respectively (R. Krishnamurthy 2011). The values of
temperature corresponding to the density for pure petrol and evaporated petrol
are presented in Table 1.
It is seen from the table that, IBP of the sample increases with the density.
The reason is due to the loss of low boiling petroleum hydrocarbons. The values
of temperature for 50% recovery, 70% recovery and final boiling point also
increase. The values for maximum boiling point even of too high density petrol

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samples i.e. 0.791 and 0.801, increases but do not exceed certain final boiling
point temperature values (180-1850C).
Similar results (such as high values of IBP) may arise in the sample if the
samples are adulterated with high boiling petroleum hydrocarbons. Generally
kerosene is used for the adulteration of petrol. Adulteration of kerosene to the
petrol leads to the change in properties such as increase in density, change in
colour, and change in % recovery of sample. Adulteration of petrol with kerosene
are identified, studied and explained by different techniques such as TLC,
HPTLC, and GC methods [S. R Yadav et al 2005; M. K. Malve et al 2001, 2004,
2005; V.R. Dhole et al 1995 and S. K. Kapoor et al 1978]. Adulteration of petrol
with 10% or 20% kerosene does not lead to remarkable change in original colour
of the petrol sample. Hence the density and distillation range of 10% or 20%
kerosene adulterated petrol were found out. The IBP of 20% adulterated petrol
does not vary considerably from pure petrol but the value for final boiling point
for the same % adulterated petrol increases significantly and may reach up to
2060C & 2320C.
However the filter paper test i.e., petrol containing kerosene when placed on
filter paper, petrol get evaporated leaving behind kerosene, which looks like oily
patch with characteristic smell of kerosene. Thus the possibility of adulteration of
kerosene can be positively ruled out.

Thin layer chromatography


A solvent system Hexane: Acetone (8:2) was used for the development of
spot. Pure petrol sample and evaporated petrol sample shows the presence of
orange coloured spot, kerosene gives blue coloured spot at Rf 0.8 while orange as
well as blue coloured spots (Blue dye used in Public Distribution Supply (PDS)
kerosene in India) were observed for 10 and 20 % adulterated petrol and results
are presented in Table 2.

Table 2. Result of thin layer chromatography of fresh, evaporated and


adulterated petrol samples
Petrol/Petrol+Kerosene Dye by HPTLC
Orange Blue
Pure petrol ++ -
Up to 5% ++ -
Up to 20% ++ -
Up to 21-30% ++ -

Up to 31-40% ++ -
Up to 41-50% ++ -
Up to 51-55 % ++ -
Up to 56-60% ++ -
10% adulterated ++ ++
20% adulterated ++ ++
Kerosene - ++

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GC analysis
The results were further confirmed using GC technique as discussed in
section 3.0(e). The overlay in Fig. 1 shows standard petrol chromatogram with
density 0.721 and evaporated petrol sample chromatogram with density 0.774 and
0.792 respectively. The overlay of these chromatograms clearly shows the
depletion in peak height of the earlier peaks at low oven temperature. The GC
results further confirmed the presence of lower boiling point petroleum
hydrocarbon in fresh petrol sample that appear at retention time 1.22 min, 1.44
min, 1.66 min do not show their appearance in evaporated petrol with density
0.792. Similarly the peaks at retention time 2.11 min and 2.21 min shows reduced
peak height for the evaporated samples as compared to fresh samples. However
as the oven temperature increases, the peaks observed at those retention times
show more or less same peak height for evaporated and fresh petrol samples.
Thus the GC results confirm evaporation of lower petroleum hydrocarbons
fractions and help to correlate all the above studied properties.

Figure 1. Overlay of petrol samples (Fresh and evaporated)


(1. Petrol density -0.721; 2. Petrol density-0.774; 3. Petrol density-0.791)

Conclusion

Good quality gasoline should be stable almost indefinitely if stored properly.


Such storage should be in an airtight container, to prevent oxidation or water

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vapors mixing, and at a stable cool temperature, to reduce the chance of the
container leaking. When gasoline is not stored correctly, the lower petroleum
hydrocarbons get evaporated, gums and solids may accumulate resulting in "stale
fuel" resulting change in its original properties. It is concluded from the study
that, the quantity of petrol sample seized at the time of receiving to the
laboratory and at the time of analysis should be compared. Thus the present
experiment reveals that when all the possibilities of adulteration of petrol are nil,
the probable reason for unexpected drastic change in the properties of petrol
sample is only the evaporation of sample. Thus from the above detailed survey
of petrol analysis it was found that quantity of the petrol sample at the time of
receiving, and at the time of analysis should be considered to correlate the
properties of petrol.

Acknowledgement
The authors are thankful to Director, Directorate of Forensic Science
Laboratories, Mumbai, Government of Maharashtra, for his valuable guidelines
and encouragement for the preparation of this paper.

References

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Delhi, 2001.
4. G James, Speight and Oxum. Petroleum refining processes, Marcel Dekkar, New York 3 rd
Edition. 2002.
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Analysis of Petrol: A Clarification for Purity of Petrol

17. Dr. M.K. Malve S.A. Shinde and Dr. (Mrs) R. Krishnanmurthy, Determination of Adulteration
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