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Nigerian Journal of Basic and Applied Science (June, 2012), 20(2): 87-92 ISSN 0794-5698

Comparative Studies of Gasoline Samples Used in Nigeria

*1U.Z. Faruq, 2M. Runde, 3B.G. Danshehu, 3H.N. Yahaya, 1A.A. Zuru and 1A.B. Muhammad
1Departmentof Pure and Applied Chemistry, Usmanu Danfodiyo University Sokoto
2C/o
V. H. Bamaiyi and Associates, No. 17, Yola Road, Adamawa State
3Sokoto Energy Research Centre, Usmanu Danfodiyo University Sokoto

[*Corresponding Author: E-mail: uzfaruq@udusok.edu.ng; : +2347031934949, +2348091640852]

ABSTRACT: Comparative analysis was carried out on five samples of gasoline in the Nigerian market based
on octane number, sulphur content, Reid vapour pressure, specific gravity, boiling point characteristics and
chemical content. The result revealed that, Nigerian and Kuwait gasolines have low octane numbers in
comparison to others. The Nigerian sample has the least sulphur content while the Holland has the highest. The
specific gravities were all within the acceptable range of 0.75-0.85. Likewise the boiling point characteristics of
all the samples were within suitable values in favour of Nigerian weather conditions. Chemical composition
analysis shows high proportion of aromatics, above acceptable limits and low oxygenated compounds. The
findings revealed that the quality of some gasolines being sold in Nigeria is below the international standard.
Keywords: Gasoline, hydrocarbons, octane number, sulphur content, specific gravity and API gravity

INTRODUCTION Over the years, the advocacy on human health and

Gasoline is obtained from crude oil through blending general environmental concern has forced the
of atmospheric distillation naphtha and products from refineries to balance the composition of gasoline to
other complex refinery processes (Handwerk, 2001). meet the high engine performance requirements
Refinery processes have developed in response to without jeopardizing human and environmental
changing market demand and stricter environmental safety. Yet some sub-standard gasolines still find
laws. With the advent of the internal combustion their way into the market. For example, in Nigeria,
engine production of gasoline have dominated the where most of the gasoline being consumed is
refining processes (Hinks, 2004). This is because the imported through independent marketers, there is the
quantities of gasoline obtainable from distillation temptation of profit maximization through either
alone were insufficient to satisfy consumer demand. adulteration or importation of substandard products.
Therefore, to meet the gasoline demand some In view of the above, this paper presents
petroleum fractions must be converted to gasoline by compositional study on different gasoline samples in
processes like Cracking, Hydroprocessing, Alkylation Nigerian market with the view of assessing the level
and catalytic reforming (Handwerk, 2001). of compliance to international specifications on
gasoline products.
The typical composition of gasoline hydrocarbons (%
volume) is: 4-8% alkanes; 2-5% alkenes; 25-40% iso- MATERIALS AND METHODS
alkanes; 3-7% cycloakanes; 1-4% cycloalkenes; and Collection of Gasoline Samples
20-50% total aromatics (0.5-2.5% benzene) Two litters each of Nigerian produced gasoline and
(Hoekman, 1992). Additives and blending mixture are those imported from Kuwait, Brazil, Holland, and
also added to improve its performance and stability. Russia were collected from designated deports in
These compounds include anti-knock agents, anti- Lagos in July 2009 and kept in tightly closed clean
oxidants, metal deactivators, lead scavengers, anti- and dry metallic containers at laboratory temperature
rust agents, anti-icing agents, upper-cylinder until needed for analysis. The imported samples were
lubricants, detergents and dyes. At the end of the identified by the Vessels Managers of the Deports in
production process, finished gasoline typically Nigeria.
contains more than 150 separate compounds
although as many as 1,000 compounds have been Determination of Reid Vapour Pressure (ASTMD-
identify in some blends (Hoekman, 1992). Hence, in 323, Liptak 2003)
spite of the fact that gasoline is solely used in internal The liquid chamber of the RVP kits apparatus was
combustion engine, its chemical composition varies filled with a gasoline sample that has been pre-chilled
depending on the crude oil used, the refinery to 40C and the liquid chamber was connected to the
processes available, the overall balance of product vapour chamber fitted with a pressure gauge. The
demand and the product specifications. entire assembly was immersed in the pre-heated
water bath at 37.8oC. After 5 mins., the assembly was
removed, shaken and the pressure gauge was read.

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 Faruq et al.: Comparative Studies of Gasoline Samples Used in Nigeria

The assembly was then re-immersed and removed such that the temperatures of the injection port, ion
after another two minutes, shook and the pressure source and interface were at 240, 200 and 250 oC,
guage read again. The procedure was repeated until respectively. Helium was used as the mobile phase at
two successive readings are within 0.35 kPa. The flow rate of 1.64 ml/minute. The ovum, housing DB-
gauge reading was corrected to obtain the Reid MS-1 capillary column of 30m nominal length and
vapour pressure. 250 m internal diameter was set at initial
temperature of 45 oC and programmed at heating rate
Determination of Octane Number (RON) of of 15oC/min to 210oC which was maintained for 10
Gasoline (ASTM D-38) minutes.
RON was determined using single cylinder test
At the end of each run the total ion chromatogram
engine knock meter at Kaduna Refining and
(TIC) and mass spectrum of each of the separated
Petrochemicals (KRPC) according to ASTM D-38 compounds was produced and printed out. The mass
standard procedure. spectrum of each peak was compared with 2004
NIST e-library to bring out compounds with identical
Octane Number Sulphur Determination by Energy or similar spectrum for easy identification.
Dispersive X-Ray Fluorescence Spectrometry
(ASTM D-4294) IR Analysis
The sample cell of the machine was filled with the The Shimadzu 4800S FTIR machine was turn on and
gasoline sample above a minimum depth. The cell allowed to worm for 30mins. The machine was
containing the sample was placed in the sample programmed to scan between 400 and 4000 cm-1 at
compartment along the path of beam emitted by X- resolution of 4 cm-1. The background spectrum was
ray source. The resultant characteristics X-ray then scanned and saved. The sample was smeared
fluorescence from the sample was measured and the on one pre-prepared KBr window and covered by
accumulated count was compared with that of another so that a thin film of the sample liquid was
calibration sample to obtain the sulphur concentration formed between the two KBr windows. The KBr
in mass percentage. windows containing the sample were transfer into the
sample compartment and attached to the sample
Determination of Specific Gravity and API Gravity holder. The sample was then scanned and the
spectrum was produced and display on the computer
(ASTMD - 1298)
screen. The spectrum was smoothen to remove noise
Hydrometer cylinder containing the sample was
signals with the help of IR solution software installed
cooled to constant temperature of 28 0C. The into the system. The smoothened spectrum was then
hydrometer was inserted and allowed to come to rest printed. The same procedure was followed for the
floating freely away from the walls and bottom of the other samples.
cylinder and the specific gravity value was read
directly from the calibration of the hydrometer. RESULTS AND DISCUSSIONS
The results of the experiments are presented in
Determination of Initial and End Boiling Point of Tables 1-5. Table 1 above shows the result of the
Gasoline (ASTMD-86) Reid Vapour Pressure (RVP) and Research Octane
100 ml of the gasoline sample was transferred into a Number (RON) analyses. From the result it can be
distillation flask. The flask was stoppered and a seen that Kuwait gasoline has the highest value of
thermometer was inserted vertically into the 0.56 while Hollandian gasoline has the least value of
distillation flask. The flask was then heated and the 0.44. The relatively high RVP of Kuwaiti and Russian
distillate was condensed in a brass tube condenser, gasolines indicates that they contains higher amounts
surrounded by water bath kept at 0 0C by ice water of volatile hydrocarbons which may not be very good
mixture. The temperature at which the first drop of for hot weather experienced in Nigeria because of the
distillate was obtained was recorded as the initial tendency of such fuels to cause vapour locks when
boiling point of the gasoline. The distillation was use in internal combustion engine (Finlayson-pitt and
continued and the temperatures at which 5, 20, 30, Pitt-jnr 1993). Such gasolines also have high
tendency of being lost to vapourisation (Schuetzle et
40, 50, 60, 70, 80, 90, 95 cm3 and the last drop of the
al 1994) in addition to fire hazard. On the other hand,
distillate were received and recorded. the Hollandian sample with low RVP (low volatile
components) may have its own problems especially
Compositional Analysis Using Gas during the cold season where such fuels cause
Chromatography/Mass Spectrometry (GC/MS) difficulty in cold ignition. However, since the
The machine (SHIMADZU QP2010) was warmed for difference in temperature between summer and
recommended period of time and then programmed winter is not very wide in the tropical climates found

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 Nigerian Journal of Basic and Applied Science (June, 2012), 20(2): 87-92

in countries like Nigeria, the little difference in the above the minimum value of 35C quoted as the
RVP between the samples may not cause any standard. This could be deliberately designed in
significant problem. consideration of the Nigerian climate where normal
atmospheric temperature is commonly above 30C.
The results of the Octane Number analysis (Table 1) Therefore Nigerian gasoline should have high IBP to
show that Nigerian gasoline has the lowest octane avoid significant looses of the volatile components to
number of 86.5. This is lower than the minimum evaporation which could cause vapour locks in
desired value of 91 for internal combustion engine engines.
(Mustafa, 2004). This means that Nigerian gasoline
has the tendency to cause engine knock especially in The IR analysis indicated the presence of alkanes
modern improved engines. All other samples have and aromatics compounds through appearance of
octane number within the standard range. peaks that corresponding to these. However, the IR
results (Table 3) indicate the presence of oxygenated
The low octane number of the locally refined gasoline compounds in the Russian sample where absorption
is an indication of poor product regulation. Low for alcohols were observed in all the expected
octane number gasoline is an issue of high concern regions. This serve to confirm that the sample contain
particularly to the new improved high compression some alcohols the quantity of which may be ascertain
engines vehicle being imported into the country. in the GC/MS result.

The result of the sulphur content analyses (Table 1) The GC/MS analysis (Table 4) shows that Nigerian
shows that Hollandian gasoline has the highest and Hollandian gasoline do not contain any cyclo-
sulphur concentration of 0.081%wt, followed by alkanes, while Brazilian, Kuwaiti and Russian
Brazilian gasoline (0.04%wt) and Nigerian gasoline gasoline contain 21.74, 8.08 and 4.12% cyclo-
has the lowest (0.025%wt). The maximum alkanes, respectively. However, all the gasoline
concentration allowed in any gasoline sample is samples contain aromatic compounds in very high
0.05%wt (Assi 2008), but some European countries concentration. Kuwaiti gasoline has the highest
have mandated that sulphur in gasoline should be concentration with 85.61% while Russian gasoline
kept as low as 10ppm (0.001%). However Nigerian has the lowest aromatics concentration with 65.51%.
refineries still allows sulphur content to be as high as Nigerian, Brazilian and Hollandian gasoline contain
0.2%wt (KRPC). Therefore, the sulphur contents of 71.77, 71.26 and 80.52 % of aromatics, respectively.
all the fuels fall within the Nigerian standard. It is
nevertheless worrisome to notice that while other Similarly, all the gasoline samples contain n-alkanes.
countries are lowering the tolerable sulphur contents Nigerian gasoline has significant amounts of
of their gasolines to protect people and environment, branched-alkanes (14.56%) although lower than the
Nigeria still allows high sulphur content with the Russian gasoline (19.46%). The Hollandian and
implication that the gasolines that are not acceptable Kuwaiti gasoline have no branched-alkanes. On the
in other countries due to their high sulphur contents other hand Brazilian and Kuwaiti gasoline do not
are being imported into the country at the detriment of contain branch alkanes. Looking at the result, it is
the citizens and the environment. Sulphur content in clear that the main Octane Number enhancers in all
gasoline is kept low because it is toxic, causes the samples are the aromatics (Calingaert, 1998).
corrosion of metals and its combustion products are This is another point of concern because aromatics
environmentally hazardous (Wormsbecher et al, are known to be toxic (Fishbien et al., 1987). This is
1993). why their concentration in gasoline is usually limited
to 50% and the octane number, is raised to
Table 1 gives results of specific gravity (S.G.) specification using oxygenated compounds like
analysis. All the values obtained also fall within the ethers and alcohols. Siu (2005) has shown that
standard range of 0.749 to 0.850. Nevertheless, the oxygen containing compounds are added to gasoline
Russia gasoline has the highest specific gravity value to improve performance and reduce exhaust
of 0.7620 and the Kuwaiti gasoline has the lowest emission. In some countries, oxygenates, particularly
value of 0.7493. Therefore, from the SG result the alcohols constitute about 20% of the gasoline blend
gasolines are not expected to cause any problem in to ensure safety, environmental friendliness and
usage. quality. Amazingly none of the samples analyzed was
found to have any oxygenated components not even
Result of the boiling point characteristics of the the Nigerian sample. The absence of alcohol in the
samples (Table 2) shows all the samples have initial GC/MS result in contrast to the IR may be that the
boiling points (IBP) of around 40C which is 5C alcohol content is very small.

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 Faruq et al.: Comparative Studies of Gasoline Samples Used in Nigeria

Table 1: Results of Reid Vapour Pressure (RVP), Octane Number (RON), Sulphur Content and Specific
Gravity Determinations.
SOURCE RVP (PSI) at RON Sulphur Content Specific Gravity
O
37.8 C (%wt) at 25o C
Brazil 0.50 94.6 0.041 0.7542
Holland 0.44 91.7 0.081 0.7503
Kuwait 0.56 89.5 0.029 0.7493
Russia 0.55 93.2 0.032 0.7620
Nigeria 0.48 86.5 0.025 0.7571
ASTM Standard Variable 90-94 0.01-0.05 0.749-0.850

Table 2: Results of Boiling Point Range at Atmospheric Pressure Distillation.

Temperature of Recovery (oC)
% Recovery Brazil Kuwait Holland Russia Nigeria ASTM Standard
Initial Boiling Point 40 39 43 40 40 35-39
5% 55 50 59 54 56
10% 60 55 62 60 61 60
20% 71 66 75 71 70
30% 84 77 84 85 82
40% 97 89 93 95 99
50% 110 102 104 106 110 110
60% 123 117 111 125 123
70% 135 127 120 151 138
80% 149 145 134 167 150
90% 168 164 153 176 168 170
95% 184 179 174 183 184
End Boiling Point 194 192 186 198 201 195-204
Total Recovery (cm ) 3 96 98 97 97 96

Table 3: Results of IR Analysis

Absorption band (cm-1) Group Brazil Holland Russia Nigeria Kuwait
750-700 Monosubstituted benzene 720 720 720 - -
800-750 Disubstitute benzene - 760 760 760 760
1060-1040 Primary alcohol 1040
1470-1350 Alkanes 1400, 1440, 1440, 1440 1440
1440 1360 1360 1360 1360
1680-1040 C=C alkenes 1600
2820-2720 Aldehyde 2790 2720 2720
2960-2850 C-H alkane 2960 2880 2960
2960
3000 - 2500 OH Phenols alcohol 2500
3600-3200 Hydrogen bounded alcohols 3600 3560

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 Nigerian Journal of Basic and Applied Science (June, 2012), 20(2): 87-92

Table 4: Results of Compositional Analysis using GC/MS

Hydrocarbon type Concentration (%)
Nigeria Brazil Holland Kuwait Russia
Aromatics
Ethylbenzene 11.97 17.41 12.0 5.27
Proplybenzene 5.67
1-ethyl-3-methybenzene 9.79 19.74 17.41 19.15
3propyl-1-methylbenzene 6.78 7.99 12.56
Isopropylbenzene 5.12
2,4-dimethylstyrene 2.29 2.82 3.16
O-xylene 17.85 15.89 29.42 17.52 9.75
p-Xylene,2-ethyl 4.54
Toluene 19.45 22.50 21.76 22.99 18.78
1-ethyl-3-methylbenzene 15.09
Total Aromatics 71.77 71.26 80.52 85.61 65.51
Cyclo Alkanes
4,7methano1-H-octahydroindene, 5.89
4,7methano-1H-indene,3a,4,5,6,7,7a-hexahydro 12.50
1,3,5-cycloheptatriene 8.08
1,2 dimethylcyclohexane 4.12
9-methylene-tricycle (4.2.1. (95) decane 3.35
Total cycloalkanes 0.00 21.74 0.00 8.08 4.12
n-Alkanes
Octane 5.98 7.0 6.31 7.99
Undecane 7.69 2.91
2,4-dimethyheptane 9.51
4-methyloctane 6.42 9.03
2-methylhaptane 8.14 9.95 10.43
Total n - Alkanes 28.23 7.0 19.46 6.31 30.36

CONCLUSION AND RECOMMENDATION It is therefore necessary to call on the Nigerian

From the results obtained it can be generally authorities to ensure strict compliance to standards
concluded that all the samples are sub-standard with by both local producers and importers of gasoline for
each having one problem or the other. The Nigerian the welfare of the entire nation. Furthermore, the
refined gasoline has low octane number, the Holland environmental concern is rather global, therefore
sample has high sulphur content, and the Kuwaiti issues that affect the lager environment like sulphur
sample has high Reid Vapour Pressure. All these are emission is the concern of every one and every
in addition to the generally high aromatic content of nation.
the gasolines and absent of oxygenates.
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