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Review article
Abstract
A sensitive method based on square wave voltammetry is described for the quantitative determination of elemental sulfur, disulde
and mercaptan in gasoline using a mercury lm electrode. These sulfur compounds can be quantied by direct dissolution of gasoline in a
supporting electrolyte followed by subsequent voltammetric measurement. The supporting electrolyte is 1.4 mol L1 sodium acetate and
2% acetic acid in methanol. Chemical and optimum operational conditions for the formation of the mercury lm were analyzed in this
study. The values obtained were a 4.3 lm thickness for the mercury lm, a 1000 rpm rotation frequency, 0.9 V applied potential and
600 s depositing time. Voltammetric measurements were obtained using square wave voltammetry with detection limits of the 3.0 109,
1.6 107 and 4.9 107 mol L1 for elemental sulfur, disulde and mercaptan, respectively.
2007 Elsevier Ltd. All rights reserved.
Keywords: Sulfur compounds; Square wave voltammetry; Mercury lm electrode; Gasoline
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Reagents and apparatus. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Preparation of the MFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Preparation of copper column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4. Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5. Elemental sulfur, mercaptan and disulfide analysis in commercial samples of gasoline . . . . . . . . . . . . . . . . . .
Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Formation of the mercury film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analytical performance of the procedure development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Analysis of gasoline samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Recovery of sulfur compounds in gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author. Tel.: +55 16 3301 6621; fax: +55 16 3322 7932.
E-mail address: nrstradi@iq.unesp.br (N.R. Stradiotto).
0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.07.012
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1008
1009
1009
1009
1009
1009
1009
1009
1009
1011
1011
1012
1012
1012
1012
1008
1. Introduction
Due to the importance of sulfur in chemical, biological
and industrial areas, sulfur compounds have been extensively studied for many years [15], especially the determination of sulfur and its compounds in drugs, cosmetics,
foodstu, and petroleum products [69].
Sulfur has been the most abundant element in petroleum
after carbon and hydrogen for many years [10]. Nowadays,
in the case of the products resulting from the degradation
of organisms, oxygen and nitrogen are more abundant
than sulfur. It has been demonstrated that sulfur penetrates
into organic matter before crude oil is extracted and also
after the sedimentation process [11]. For a long period,
reducing bacteria in sediments have made changes in sulfate salts and have altered the formation of sulfur reducing
compounds such as H2S, S0, sulte, mercaptan and polysulde. In other words, these sulfur species are produced
by anaerobic bacterial reduction of sedimentary sulfate
deposits (mainly anhydrite or gypsum). The anaerobic bacteria consume sulfur instead of O2 as a source of energy
and a hydrogen acceptor to produce these sulfur compounds [12]. Apparently the reactions of these sulfur species and the formation of CS bonds cause the
occurrence of organosulfur compounds in petroleum derivatives. In order to properly remove sulfur from petroleum
and its derivatives, such as LPG, naphtha, gasoline, kerosene, gas oil and lubricants, it is necessary to appropriately
design oil facilities and develop a methodology to determine sulfur compounds especially in quality-control units.
Because various metals can suer the corrosive eect of
the sulfur compounds remaining after the rening of petroleum, it is interesting to have analytical methods to detect
and determine the most common sulfur compounds in
the rening industry. Several methods for the determination of sulfur compounds have been reported, including
colorimetric [13], titration [14], chromatographic [15], iodimetric [16,17] and X-ray uorescence spectrometry [18,19].
These methods are accurate and sensitive for the determination of elemental sulfur and mercaptan, but they are
time-consuming and tedious. In contrast to these methods,
electrochemical procedures are highly promising for
obtaining high sensitivity at good speed, low cost and a
low detection limit.
The general application of the electrochemical methods
for the analysis of sulfur compounds include polarography
to determine inorganic and organic compounds in petrochemical analysis [2022]. Usually, the polarographic
methods have been applied to the determination of only
one kind of sulfur compound, using solvents such as methanol and pyridine. Some works targeting the determination
of total sulfur, hydrogen sulde, elemental sulfur [23],
organic sulfur compounds and elemental sulfur [24] in oil
fractions have been reported. On the other hand, elemental
sulfur in fuels [25] and mercaptan sulfur in synthetic samples [26] have been determined using dierential pulse
polarography.
1009
2. Experimental
2.4. Procedure
2.1. Reagents and apparatus
The support electrolyte consisted of 1.4 mol L1 sodium
acetate and 2% acetic acid in methanol. Standard solutions
of elemental sulfur, 1-butanethiol and phenyl-disulde
(Acros Organics) were prepared by diluting the samples
in n-heptane solvent (Acros Organics) giving a concentration of 5.0 102 mol L1 with successive dilutions all
being done using analytical-grade chemical reagents.
A conventional electrochemical cell was used containing
a (3.0 mm diameter) glassy-carbon mercury-lm electrode
as the working electrode. A reference electrode of Ag/AgCl
(KCl 3.0 mol L1) and a platinum plate as an auxiliary
electrode was also used. The glassy-carbon electrode was
polished with alumine (0.3 lm) and washed with water
before each stage of the mercury electrodeposition.
The voltammetric measurements were carried out in an
AUTOLAB PGSTAT 30 potenciostat/galvanostat. During
the deposition step, electrode rotation was achieved by
using a rotation generator from METROHM, model
628-10.
2.2. Preparation of the MFE
Electrochemical depositing of a mercury lm on the
glassy-carbon electrode surface was achieved according to
a conventional procedure reported in the literature [32].
The electrochemical cell contained 75 lL 1.0 102
mol L1 mercury nitrate solution diluted to a nal volume
of 15 mL with an aqueous solution of 1.0 102 mol L1
lithium chloride, resulting in a 2.0 105 mol L1 solution
of mercury ions. After deaerating this solution with a ow
of nitrogen for 15 min, a potential of 0.9 V vs. Ag/AgCl
was applied to the system for 20 min while rotating at
1000 rpm. After the lm had formed, the electrode was
rinsed with deionized water and stored in an aqueous supporting electrolyte solution.
2.3. Preparation of copper column
A copper column was used with the objective of eliminating the interference of the disulde in the voltammetric
analysis [42]. A column was used and the parameters were
optimized to: (a) the diameter of the column (U = 1.5 cm),
(b) the copper mass (mCu = 10 g), (c) the height of the column (h = 20 cm), (d) the volume of the gasoline sample
(5.0 mL) and (e) the ow of the gasoline sample in the column (at atmospheric pressure). The copper used was in a
ne powder (Merck), where the size of its particles was
In all the voltammetric studies, 10.0 mL of the supporting-electrolyte, 1.4 mol L1 sodium acetate and 2% acetic
acid in methanol was transferred to the voltammetric cell
and deaerated with nitrogen. When a sample of the sulfur
compound was added to the respective concentrations of
the sulfur compounds analyzed using the square-wave-voltammetric (SWV) techniques, the voltammograms were
reported.
After optimization of the experimental conditions, the
calibration curve was obtained using disulde, mercaptan
and elemental sulfur standard solutions in the concentration interval of 2.5 107 to 6.0 106 for disulde,
2.5 107 to 7.5 106 for mercaptan and 1.0 108 to
1.0 107 for elemental sulfur using the square-wave-voltammetry technique.
2.5. Elemental sulfur, mercaptan and disulde analysis in
commercial samples of gasoline
After optimization of experimental and voltammetric
conditions for the SWV technique, commercial samples
of gasoline from the gas stations in Araraquara city were
analyzed. Each 1 mL gasoline sample was added to
10 mL of the 1.4 mol L1 sodium acetate and 2% acetic
acid in methanol [42].
However, when elemental sulfur exists along with mercaptan and disulde present in gasoline, rst the total peak
height of the solution at 0.38 and 0.70 V vs. Ag/AgCl
was measured. Then the solution was slowly passed
through a redbrown copper column (mercaptan and elemental sulfur react with copper forming cuprous mercaptide) and the peak height of the ltrate was measured
again because the disulde was not removed. The peak
height of the ltrate corresponds to the amount disulde.
The amount of mercaptan can be calculated by the peak
height of the original solution.
To study the recovery of trace sulfur compounds in samples of gasoline, a 1.0 mL sample was added to the electrolyte solution along with subsequent addition of the specic
standards.
3. Results and discussion
3.1. Formation of the mercury lm
The deposit of the mercury lm onto the glassy-carbon
electrode in lithium chloride at 1.0 102 mol L1 is carried out using the chronocoulometric technique where the
1010
-600
-250
-200
-400
150
75
-150
I (A)
-300
I ()
Ip (A)
225
-500
-200
0
0
20
40
60
80
100
-1
-100
-100
-50
0
100
0
0.0
200
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
-0.2
-0.4
-1.2
-0.6
-0.8
-1.0
E (V) vs Ag/AgCl
E (V) vs Ag/AgCl
b
b
-250
500
450
-500
400
Ip ()
350
-200
300
-400
250
200
-150
I ()
I()
150
-100
-300
-1
-200
-50
-100
50
0
0.0
-0.2
-0.4
100
0.0
-0.2
-0.4
-0.6
-0.8
E (V) vs Ag/AgCl
-1.0
-1.2
60
-140
50
-100
-120
-100
40
30
I ()
-80
-80
I ()
-0.8
-120
Ip (A)
-0.6
E (V) vs Ag/AgCl
-1.0
20
10
-60
-60
-40
10
12
14
-1
-40
-20
-20
0.0
20
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
E (V) vs Ag/AgCl
40
0.0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
E (V) vs Ag/AgCl
1011
Table 1
Voltammetric data obtained from the analysis of elemental sulfur, disulde and mercaptan using SWV and a MFE
Elemental sulfur
Disulde
Mercaptan
2.9 10
9.1 107
4.9 106
As has been suggested by Davison et al. [45] the oxidation of elemental mercury occurs owing to the great anity
of elemental sulfur to chemical adsorption at the electrode
surface. Therefore in the cathodic scan, the mercury sulphide formed has a tendency to decompose by reducing
the elemental mercury and sulphide ions.
The disulde presents a well-dened reduction peak at
about 0.65 V vs. Ag/AgCl with characteristics of being
a reversible process as shown in Fig. 1b. The disulde is
reduced to sulde in the adsorption process and by the
transfer of two electrons, as shown in Eqs. (3) and (4):
3.0 0.5 10
1.6 0.7 107
4.9 0.2 107
5.5 0.3 10
5.5 0.5 107
1.6 0.6 106
RSD (%)
0.51 0.07
0.72 0.09
0.28 0.03
RSSR Hg ! RS2 Hg ads
RS2 Hg ads 2e 2H ! 2RSH Hg
3
4
-100
-80
I (A)
Sulfur compounds
S + SS
-60
SH
-40
-20
-0.2
-0.4
-0.6
-0.8
-1.0
E (V) vs Ag/AgCl
1012
Table 2
Determination of sulfur compounds in commercial fuel samples measured
using SWV and a MFE
Samples
Elemental sulfur
(mol L1)
Disulde
(mol L1)
Mercaptan
(mol L1)
1
2
1013
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