Journal of Sulfur Chemistry

ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: http://www.tandfonline.com/loi/gsrp20

Determination of sulfur content in petroleum

products – an overview

Subhash Chandra Bajia, Ram Janam Singh, Birbal Bajia & Sudesh Kumar

To cite this article: Subhash Chandra Bajia, Ram Janam Singh, Birbal Bajia & Sudesh Kumar
(2017) Determination of sulfur content in petroleum products – an overview, Journal of Sulfur
Chemistry, 38:4, 450-464, DOI: 10.1080/17415993.2017.1289530

To link to this article: https://doi.org/10.1080/17415993.2017.1289530

Published online: 17 Feb 2017.

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JOURNAL OF SULFUR CHEMISTRY, 2017
VOL. 38, NO. 4, 450–464
http://dx.doi.org/10.1080/17415993.2017.1289530

REVIEW

Determination of sulfur content in petroleum products – an

overview
Subhash Chandra Bajiaa , Ram Janam Singha , Birbal Bajiab and Sudesh Kumarc
a Quality Control laboratory, Indian Oil Corporation Limited, Barauni Refinery, Begusarai, India; b Quality
Control laboratory, Indian Oil Corporation Limited, Panipat, India; c Department of Chemistry, Banasthali
University, Jaipur, India

ABSTRACT ARTICLE HISTORY

Sulfur is invariably present in petroleum products, feedstock and Received 26 October 2016
crude oil. Several analytical methodologies are available to deter- Accepted 11 January 2017
mine the sulfur content from trace level to percentage level. KEYWORDS
Analytical techniques being employed for sulfur determination in Sulfur; petroleum product;
petroleum products, feedstock and crude oil are briefly described in oxidative microcoulometry;
this review article. ultraviolet fluorescence;
non-dispersive infrared; X-ray
fluorescence spectroscopy;
gravimetrically; colorimetry

1. Introduction
Sulfur is always present in petroleum products and feedstock including crude oil which
is the raw material used in the petroleum refining process [1]. The quantity and amount
of sulfur compound in different petroleum samples vary with crude source and refinery
processing technology [2–6]. Sulfur compounds are present in different forms such as
hydrogen sulfide, sulfides, sulfur dioxide, mercaptans, thiophenes, benzothiophenes and
dibenzothiophenes [2–6]. These sulfur compounds are detrimental for refinery processing
due to catalytic poisons [7], plant corrosion and atmospheric pollution [8,9].
Environmental agencies reduce the maximum allowable sulfur content in petroleum
products around the world [10–12]. This trend of reducing sulfur limits will continue
over the coming years. To achieve the stringent sulfur content specifications for petroleum
products, convenient sulfur measurement technology is essential for use by the entire
petroleum industry from the analysis of the incoming crude oil throughout the refin-
ing process to the monitoring of transportation, storage and distribution procedures.
Analytical methodologies [13–39], such as oxidative microcoulometry [13,14], ultraviolet
fluorescence [15–17], non-dispersive infrared, X-ray fluorescence spectroscopy [21–26],
titration methods [27–30], gravimetric methods [31], rateometric colorimetry [32,33],
potentiometric methods [34] and gas chromatography [35–39], are being used for sul-
fur determination. Sulfur speciation (molecular species determination) [35–39] provides

CONTACT Subhash Chandra Bajia subhashbajia@gmail.com Quality Control laboratory, Indian Oil Corporation
Limited, Barauni Refinery, Begusarai, Bihar, India

© 2017 Informa UK Limited, trading as Taylor & Francis Group

 JOURNAL OF SULFUR CHEMISTRY 451

additional input for mitigating the sulfur content problems of the petroleum refining
industry, providing greater insight than measuring total sulfur content alone.
The concise details of the testing methods, including range, accuracy, measurement
chemistry and advantages and limitations of each analytical technique being used for sulfur
determination, are presented in this article. This article will be helpful to college students,
researchers, analytical chemists, process engineers and policy-makers.

2. Conclusion
In this review article, most of the available analytical techniques used for sulfur determina-
tion in petroleum samples have been described. The analytical techniques, their respective
test method number, detection mechanism, chemical reactions, testing range, accuracy,
advantages and limitations are given in the form of tables. For sulfur determination at trace
levels (sub ppm), the oxidative microcoulometry, ultraviolet fluorescence and rateometric
colorimetry techniques can be used. The average range (ppm) of sulfur can be measured by
using X-ray fluorescence spectroscopy, non-dispersive infrared and titration methods. The
X-ray fluorescence techniques are mostly being used for sulfur determination in a broad
testing range (ppm to %) and applicable for all petroleum sample. In X-ray fluorescence
technique, the sample matrix plays vital roles in sulfur determination, hence for particular
sample determination the calibration should be performed with the same matrix calibra-
tion sample. The other manual analytical techniques have less accuracy, but due to their low
cost and they may be used for proximate analyses. This review article may help in policy-
making, refinery process control and quality control for sulfur determination, selection of
test method, testing range and in accuracy.

3. Experimental procedure
3.1. Sampling
Sampling of natural gas, LPG [40], other petroleum products and feedstock [41] is being
done by manual and automatic sampling methods [42]. Sampling of petroleum products,
feedstock and crude oil should be conducted using containers made of plastics, glass or
metal with suitable corks or plastic stoppers. The LPG and other gaseous samples should
be collected in metallic bombs of high-pressure-bearing capacity. After sampling, these
petroleum samples should be mixed properly to make the representative sample and these
samples should be handled with care [43]. National legislative guidelines on health and
safety should be followed during sampling and testing.

3.2. Analysis
Sulfur in petroleum samples is present in different forms and several analytical techniques
are being used for their detection, determination and speciation. Details of individual ana-
lytical techniques are given below in different sections. Concise details of the analytical
technique, detection and test methods, testing range and accuracy level are given in Table 1.
Details of analytical technique and their chemical reactions, advantages and limitations are
presented in Table 2.
 452
Table 1. Various test methods for sulfur determination in petroleum sample.
S. N. Technique Detection Samples type Test method Test range Accuracy References

S. C. BAJIA ET AL.
1 Oxidative microcoulometry Total sulfur Light petroleum product D 3120 3.0–1000 mg/kg r = 0.2802 X(0.7901) [13]
R = 0.5793 X(0.7901)
2 Oxidative microcoulometry Total sulfur Petroleum gas sample D 3246 1.5–100 mg/kg r = X ± 0.4 mg/kg; R = X ± 5 mg/kg [14]
(X = 0–10 mg/kg)
3 Ultraviolet fluorescence Total sulfur All petroleum product D 5453 1.0–8000 mg/kg r = 50 ± 3.4 mg/kg; R = 50 ± 10.9 mg/kg [15]
4 Ultraviolet fluorescence Volatile sulfur Gaseous sample and LPG D 6667 1.0–196 mg/kg r = 50 ± 5.8 (gaseous sample); r = 50 ± 4.2 [16]
(LPG) R = 50 ± 16 (gaseous sample);
R = 50 ± 36 (LPG)
5 Ultraviolet fluorescence Volatile sulfur LPG and natural gas D 7551 1.0–200 mg/kg r = 50 ± 0.18 (LPG); r = 40 ± 0.036 [17]
(methane)
6 IR detection Total sulfur Petroleum product D 1552 more than 0.06 wt% r = X ± 0.12 wt%; R = X ± 0.38 wt% [18]
(X = 2–3 wt%)
7 IR detection Total sulfur Coal and coke D 4239 0–10 wt% r = 0.053 + 0.019X (coal); r = 0.0510.01X [19]
(coke); R = 0.125 + 0.053X
(coal); R = 0.089 + 0.017X (coke)
(X = 0.37–5.48 (coal); X = 0.6–6.71
(coke)
8 IR detection Total sulfur Coal and coke combustion D 5016 0.7–3.8 wt% r = 0.06X + 0.06, R = 0.2 X + 0.2 [20]
residue
9 ED X-ray fluorescence Total sulfur Petroleum product D 4294 17 mg/kg to 4.6 wt% r = 100 ± 7.8 (gasoline); 100 ± 7.6 (diesel); [22]
spectrometry R = 100 ± 38 (gasoline); 100 ± 41 (diesel)
mg/kg
10 ED X-ray fluorescence Total sulfur Lubrication oil D 6481 0.05–1.0 wt% r = 0.10 ± 0.003; R = 0.10 ± 0.018 wt% [24]
spectrometry
11 ED X-ray fluorescence Total sulfur Petroleum product D 7212 7.0–50 mg/kg r = 50 ± 2.3; R = 50 ± 5.3 mg/kg [26]
spectrometry
12 WD X-ray fluorescence Total sulfur Petroleum product D 2622 3 mg/kg to 4.6 wt% r = 50.0 ± 3.4; R = 50.0 ± 9.8 mg/kg [21]
spectrometry
13 WD X-ray fluorescence Total sulfur Gasoline D 6334 15.0–940 mg/kg r = 50 ± 5.9; R = 50 ± 12.4 mg/kg [23]
spectrometry
14 Monochromatic WD-XRF Total sulfur Petroleum product, D 7039 3.2–2822 mg/kg r = 50 ± 4.1; R = 50 ± 6.1 mg/kg [25]
biodiesel and gasoline-
ethanol blend
15 Titration with barium chloride Total sulfur Fuel gas D 1072 25–700 mg/m3 r = X ± 0.06 to X ± 0.42 [27]
(continued).
Table 1. Continued.
S. N. Technique Detection Samples type Test method Test range Accuracy References
16 Acidimetrically or Total sulfur Petroleum product D 1266 0.01–0.4 wt% r = X ± 0.005; R = X ± (0.010 + 0.025X) [28]
gravimetrically
17 Titration with barium Total sulfur LPG D 2784 > 1.0 mg/kg Not determined [29]
perchlorate or turbidimetric
18 Hydrogenolysis and Total sulfur Petroleum product D 4045 0.02–10.0 mg/kg r = 1.0 ± 0.16; R = 1.0 ± 0.26 mg/kg [32]
rateometric colorimetry
19 Hydrogenolysis and Total sulfur Gaseous fuel D 4468 0.001–20 mg/kg r = 1.0 ± 0.16; R = 1.0 ± 0.28 mg/kg [33]
rateometric colorimetry
20 Oxidative combustion and Total sulfur Petroleum product and D 6920 1.0–100 mg/kg r = 0.3395 × 0.7739 (gasoline); [30]
electrochemical detection biodiesel r = 0.1960(X + 0.61789)0.9022 (diesel);
R = 1.6384 X0.7739 (gasoline);
R = 1.3028(X + 0.61789)0.9022 (diesel)
21 Gravimetrically as barium Total sulfur Petroleum product D 129 more than 0.1 wt% r = X ± 0.08; R = X ± 0.15 (X = 1.0–1.5 [31]
sulfate wt%)
22 Potentiometric method Mercaptan sulfur Petroleum product D 3227 0.0003–0.01 wt% r = 0.00007 + 0.027x wt% [34]
R = 0.00031 + 0.042x
23 Gas chromatography and Total sulfur Gaseous fuel D 5504 0.01–1000 mg/m3 r = 20.37 ± 1.98; R = 20.37 ± 6.73 [35]
chemiluminescence
24 Gas chromatography with Total sulfur Light petroleum liquid D 5623 0.1–100 mg/kg r = 0.11 × X; R = 0.42 × X [36]
sulfur selective detector
25 Gas chromatography with FPD Sulfur compound Natural gas and gaseous D 6228 0.02–20 mg/m3 r = 2.00 ± 60.06 (DMDS) [37]
fuel

JOURNAL OF SULFUR CHEMISTRY

26 Gas chromatography and Sulfur compound Natural gas and gaseous D 6968 0.04–200 mg/m3 r = 4.0 ± 0.30 mg/m3 (DMS) [38]
atomic emission detection fuels
27 Gas chromatography with FPD Sulfur compound Light hydrocarbons, motor D 7041 0.5–100 mg/kg r= ± 0.53 mg/kg (gasoline); ± 0.2070 X0.2594 [39]
fuels and oils (diesel); R = 0.0657(X + 28.626) (gasoline);
1.9771 × 0.2594 (diesel)
28 Doctor method Hydrogen sulfide Petroleum product D 4952 Qualitative test Nil [44]
29 Lead acetate method Hydrogen sulfide LPG D 2420 Around 4 mg/m3 Nil [45]
30 Cadmium sulfate method Hydrogen sulfide LPG, gaseous and D 4084 0.03–1.0 wt% Not determined [46]
petroleum product
31 Extraction and sulfur specific Hydrogen sulfide Residual fuel D 6021 0.01–100 mg/kg r = 0.24 ± 0.07 [47]
detection
32 Stain detector method Mercaptan sulfur Gas sample D 1988 0.5–160 mg/Kg r = X ± 25% [48]
Note: Here, r = Repeatability, R = Reproducibility and X = average test result.

453
Table 2. Analytical techniques, test method, chemical reactions, advantage and limitation.

454
S.N. Technique Test method Chemical reaction Advantage Limitation
1 Oxidative D 3120 In oxidative pyrolysis sulfur converts to sulfur dioxide Easy analyses Covers boiling range from 26°C to 274°C
microcoulometry In titration cell the triiodide ion consumed Covers wide sulfur range Required costly equipment and utility

S. C. BAJIA ET AL.
I3- + SO2 + H2 O → SO3 + 3I− + 2H+ from 3.0 to 1000 mg/kg gases
These triiodide ion is generated coulometrically: High sulfur sample can
3I− → I3− + 2e− be tested after dilution
Microequivalents of triiodide ion are equal to High accuracy and reliability
the number of microequivalents of SO2 ion titration
cell
2 Oxidative D 3246 Same as above Easy analyses Covers narrow sulfur range
microcoulometry Applicable for low sulfur determination from 1.5 to 100 mg/kg
High accuracy and reliability Applicable for sample which are
gaseous at normal room temperature and
pressure
3 Ultraviolet D 5453 At high-temperature sulfur is oxi- Easy analyses Required costly equipment and utility
fluorescence dized to sulfur dioxide (SO2 ) Covers wide range of sul- gases
The SO2 absorbs UV light and fur from 1.0 to 8000 mg/kg
is converted to excited (SO2 *) Cover a wide boiling range from 25°C to 400°C
Fluorescence emitted from excited High accuracy and reliability
SO2 * as it returns to a stable state No matrix effect
SO2 , is detected by a PMT
4 Ultraviolet D 6667 Same as above Easy analyses Applicable only for gaseous and LPG
fluorescence High accuracy and reliability sample
Cover sulfur range from 1.0 to 196 mg/kg
No matrix effect
5 Ultraviolet D 7551 Same as above Easy analyses Applicable only for gaseous and LPG
fluorescence High accuracy and reliability sample
Cover sulfur range from 1.0 to 200 mg/kg
No matrix effect
6 IR detection D 1552 At high temperature the sulfur is combusted to SO2 Easy analyses Applicable for sulfur more than 0.06 wt%
This is measured with an infrared detector Sulfur in petroleum products and boiling above 177°C
Microprocessor calculates the mass percent sul-
fur in sample, the integrated detector signal and a
predetermined calibration factor
7 IR detection D 4239 Same as above Easy analyses Applicable only for sulfur in coal and coke
Cover a wide range from 0 to 10 wt%
8 IR detection D 5016 Same as above Easy analyses Applicable only for sulfur in coal and coke
Cover a wide range from 3.8 to 0.7 combustion residues
wt%
(continued).
Table 2. Continued.
S.N. Technique Test method Chemical reaction Advantage Limitation
9 ED X-ray fluorescence D4294 Sample is placed in the beam Easy analyses Expensive equipment
spectrometry emitted from an X-ray source Cover a wide range from Matrix effect
The resultant excited characteristic X radiation is 17 mg/kg to 4.6 wt% Requires safety from X-ray
measured, and the accumulated count is compared Applicable for all petroleum products
with counts from previously prepared calibration
standards
10 ED X-ray fluorescence D6481 Same as above Easy analyses Expensive equipment
spectrometry Cover a wide range from 0.05 to 1.0 wt% Applicable for sulfur in lubrication oils
Applicable for all petroleum products Matrix effect
Requires safety from X-ray
11 ED X-ray fluorescence D7212 Same as above Easy analyses Expensive equipment
spectrometry Cover a wide range from 7 to 50 mg/kg Matrix effect
Applicable for all petroleum products Requires safety from X-ray
12 WD X-ray flu- D2622 Sample is placed in the X-ray beam, and peak inten- Easy analyses Expensive equipment
orescence sity of the sulfur Kα line at 5.373 Å is measured. Cover a wide range from Matrix effect
spectrometry Background intensity, measured at wave- 3 mg/kg to 4.6 wt% Requires safety from X-ray
length of 5.190 Å (5.437 Å for a Rh target Applicable for all petroleum products
tube) is subtracted from the peak intensity
The resultant net counting rate is compared to a
previously prepared calibration curve
13 WD X-ray flu- D6334 Same as above Easy analyses Expensive equipment
orescence Cover a wide range from 15 to 940 mg/kg Applicable for sulfur in gasoline

JOURNAL OF SULFUR CHEMISTRY

spectrometry Applicable for all petroleum products Matrix effect
Requires safety from X-ray
14 Monochromatic D7039 Sample is placed in the X-ray beam, and peak Easy analyses Expensive equipment
WD-XRF intensity of the sulfur Kα line at 5.373 Å Cover a wide range from 15 to 940 mg/kg Requires safety from X-ray
Fluorescent Kα radiation at 5.373 Å emitted by Applicable for petroleum product,
sulfur is collected by a fixed monochromator (analyzer) biodiesel and gasoline-ethanol blend
The intensity (counts per second) of the sulfur
X-rays is measured using a suitable detector and
converted to the concentration of sulfur (mg/kg)
in a test specimen using a calibration equation
Excitation by monochromatic X-rays reduces back-
ground, simplifies matrix correction, and increases the
signal/background ratio compared to polychromatic
excitation used in conventional WDXRF techniques

455
 456
15 Titration with barium D1072 Gas sample oxidized in to sulfate Easy analyses Applicable only for fuel gas
chloride The sulfate in the absorbent solution is subse- Low-cost equipment
quently determined by titration with standard barium Cover a wide range from 25 to 700 mg/m3
chloride solution, using tetrahydroxyquinone as an

S. C. BAJIA ET AL.
indicator
16 Acidimetrically or D1266 Sample is burned in a closed Easy analyses Covers sulfur range from 0.01 to 0.4
gravimetrically system, using a suitable lamp Low-cost equipment wt%
Oxides of sulfur are absorbed
and oxidized to sulfuric acid
Sulfur as sulfate in the absorbent is determined
acidimetrically by titration with standard sodium
hydroxide solution, or gravimetrically by precipitation
as barium sulfate
17 Titration with barium D2784 Sample oxidized to oxides of sulfur Easy analyses Applicable only for LPG
perchlorate or Oxides of sulfur are absorbed and oxidized to Low-cost equipment
turbidimetric sulfuric acid in a hydrogen peroxide solution
The sulfate ions are then determined by barium
perchlorate titration using a thorin-methylene blue
mixed indicator or turbidimetric
18 Hydrogenolysis D4045 Sample with hydrogen is pyrolyzed at a temperature Easy analyses Expensive equipment
and rateometric to convert sulfur compounds to hydrogen sulfide (H2 S) High accuracy and precision Applicable for low-sulfur
colorimetry Readout is by the rateometric detection of the Covers all petroleum products content
colorimetric reaction of H2 S with lead acetate Cover range from 0.02 to10 mg/kg
19 Hydrogenolysis D4468 Same as above Easy analyses Applicable only for gaseous fuel
and rateometric High accuracy and precision
colorimetry Covers all petroleum products
Cover range from 0.001 to 20 mg/kg
20 Oxidative com- D6920 Sulfur compounds are converted to Covers all petroleum products including, Required chemical preparation
bustion and sulfur dioxide (SO2 ) at ( > 900°C) reformulated gasoline and biodiesel Costly equipment and utility gases
electrochemical R-S + O2 → CO2 + H2 O + SO2 + oxides Pooled limit of quantitation requirement
detection This SO2 reacts with sensing electrode in elec- is very low 3 mg/kg for gaso-
trochemical cell and produces a measurable current line and < 0.5 mg/kg for diesel
that is directly proportional to sulfur amount Covers a wide range (1–100 mg/kg
SO2 + 2H2 O → H2 SO4 + 2H+ + 2e− (Electrolyte) Good accuracy and precision
21 Gravimetrically as D129 Sulfur compounds are converted to sulfate (SO− 4) Applicable for lube oil and greases having Lengthy analyses method
barium sulfate R-S + O2 → CO2 + H2 O + SO− 4 + oxides
sulfur more than 0.1 wt%
SO−4 + BaCl2 → BaSO4 (gravimetrically)
(continued).
Table 2. Continued.
S.N. Technique Test method Chemical reaction Advantage Limitation
22 Potentiometric D 3227 Silver nitrate reacts with mercaptan sulfur in sodium Easy analyses Interference with H2 S
method acetate solution. At end point the mercaptan sulfur Applicable all petroleum products in
is precipitated as silver mercaptide and end point wide range (3–1000 mg/kg) of mercaptan
potentiometrically
23 Gas chromatog- D5504 Sulfur compounds are converted to sulfur dioxide (SO2 ) Easy analyses Applicable for sulfur in gaseous
raphy and R-S + O2 → SO2 + CO2 + other oxidation products Covers a wide range fuels only
chemiluminescence Hydrogen reacts with SO2 and form from 0.01 to 1000 mg/m3
H2 S and other reduced sulfur species Good accuracy and precision
SO2 + H2 → H2 S + other reduced sulfur species
H2 S, other reduced sulfur species reacts with
O3 and form sulfur dioxide (excited state)
H2 S + other reduced sulfur
species + O3 → SO2 * + H2 O
Emitted light form excited state sulfur diox-
ide when it relaxation is measured by a PMT
SO2 * → SO2 + hν (detection by a PMT)
24 Gas chromatography D5623 Easy analyses Applicable for sulfur speciation in
with sulfur Covers a wide range from 0.1 to 100 mg/kg gaseous sample
selective detector Good accuracy and precision
25 Gas chromatography D6228 Sample is injected into a gas Easy analyses Applicable for sulfur in natural gas
with FPD chromatograph capillary column Covers a wide range from 0.02 to 20 mg/m3 and gaseous fuels
After column elution sample is combusted in Good accuracy and precision

JOURNAL OF SULFUR CHEMISTRY

a hydrogen rich flame, sulfur compounds emit
light energy characteristic to all sulfur species
The light is detected by a PMT
The PMT response is proportional to the concentration
or the amount of sulfur
26 Gas chromatography D6968 Sample is injected into a gas Easy analyses Applicable for sulfur compounds
and atomic chromatograph capillary column Covers a wide range and in natural gas and gaseous
emission After column elution sample is from 0.04 to 200 mg/m3 fuels
detection detected by atomic emission detectors Good accuracy and precision
The atomic emission detector uses microwave-
induced helium plasma to disassociate molecules
and atomize/excite elements at high temperature
The characteristic emission lines from specific excited
atoms are detected by a photodiode array detector.
Sulfur emission is measured at 181 nm

457
 458
S. C. BAJIA ET AL.
27 Gas chromatography D 7041 Same as method D 6228 Easy analyses Applicable for sulfur in light
with FPD Covers a wide range from 0.05 to 100 mg/kg hydrocarbons, motor fuels and
Good accuracy and precision oils
28 Doctor method D 4952 Sample is shaken with sodium plumbite Easy analyses Qualitative test
solution and then small quantity of sul- Used for mercaptan sulfur Less accuracy and precision
fur added, and mixture shaken again Qualitative test
The presence of mercaptans or hydrogen sulfide Applicable for petroleum products
or both is indicated by discoloration of the sulfur
floating at the oil–water interface or by discoloration
of either of the phases
5 Lead acetate method D 2420 Vaporized gas is passed over a Easy analyses Applicable for H2 S in LPG
moist lead acetate filter paper Good sensitivity about 4 mg/m3
Hydrogen sulfide reacts with lead acetate to Good accuracy and precision
form lead sulfide and thus produces coloration on the
paper which will vary from yellow to black, depending
upon the amount of hydrogen sulfide present
6 Extraction and sulfur D 6021 Sample is heated in a headspace Easy analyses Applicable for hydrogen sulfide in
specific detection vial to collect the hydrogen sulfide Applicable for hydrogen sulfide residual fuels
This collected H2 S is determined by reaction determination in residual fuels
with lead acetate or by chemiluminescence detection Covers a wide range from 0.01 to
100 mg/kg
4 Stain detector D 1988 Sample is passed through a detector tube Easy analyses Applicable for mercaptan in the
method filled with a specially prepared chemical Covers a wide range of mercaptan gas sample
Mercaptan present in the sample reacts with from 0.5 to 160 mg/kg
the chemical to produce a color change, or stain
The length of the stain produced in the detector tube,
when exposed to a measured volume of sample, is
directly proportional to the amount of mercaptan
present in the sample
 JOURNAL OF SULFUR CHEMISTRY 459

3.2.1. Determination of hydrogen sulfide

Hydrogen sulfide in petroleum samples is detected (qualitative test) by the doctor test [44],
and determination was carried out (quantitative test) by the lead acetate method [45],
cadmium sulfide method [46] and multiple headspace extraction [47].
Hydrogen sulfide in petroleum products [44] is detected by shaking the sample (10 mL)
with sodium plumbite solution (5 mL) and observing the color change. The appearance of
black color indicates the presence of hydrogen sulfide. Sometimes, light to dark yellow color
is also observed which is due to interference by mercaptan sulfur. The hydrogen sulfide of
petroleum samples can attack many metallic and non-metallic materials. A negative result
(no black color appearance) ensures that the concentration of hydrogen sulfide is low and
is insufficient to cause problems in normal use.
Hydrogen sulfide of LPG samples [45] is determined by passing the LPG sample over
a filter paper which is moist with lead acetate solution. The hydrogen sulfide of the test
sample reacts with lead acetate to form lead sulfide and produces a coloration change on
the filter paper from yellow to black.
The changes in color of the filter paper depend on the amount of hydrogen sulfide in the
tested sample. If methyl mercaptan is present in the sample, it produces a transitory yellow
stained paper which fades completely in around 5 min. The sensitivity of this test method
is about 4 mg/m3 .
In the cadmium sulfide method [46], the hydrogen sulfide of the tested sample is
converted to cadmium sulfate by reaction with acidified cadmium sulfate solution. The
cadmium sulfate precipitate is filtered off and acidified in the presence of standard iodine
solution. The excess iodine is determined by titration with sodium thiosulfate solution. In
the multiple headspace extraction and sulfur detection methods [47], a specified quan-
tity of test sample is placed in a headspace vial and heated in an oven. The hydrogen
sulfide present in the headspace is measured by the lead acetate method [46], or by
chemiluminescence detection [35].

3.2.2. Determination of thiol/mercaptan sulfur

Thiol/mercaptan sulfur in petroleum samples is detected (qualitative test) by the doctor
method [44], and measured (quantitative test) by the stain detector [48], and potentiomet-
ric methods [34]. The presence of mercaptan sulfur (qualitative test) in petroleum samples
is determined by shaking the petroleum sample (10 mL) with sodium plumbite solution
(5 mL) and observing the color change [44]. Development of a dark color solution indi-
cates the presence of mercaptan sulfur. If the sample remains unchanged in color add a
pinch of elemental sulfur and shake it again. The discoloration of the sulfur layer indicates
the presence of mercaptan sulfur. If hydrogen sulfide is present in the test sample it inter-
feres with the color change and produces the black color. Hence prior to the doctor test, the
sample is checked for the presence of hydrogen sulfide by using lead solution and hydrogen
sulfide is removed, if present, by boiling the test sample. This is a qualitative test method
and indicates the presence or absence of active sulfur as mercaptan.
In the stain detector method [48], the gas sample is passed through a detection tube
which is filled with a special chemical. The mercaptan of sample reacts with this chemical
to produce a color change, or stain. The amount of mercaptan present in the tested sample
is determined by measuring the length of the stain produced in the detection tube. The
460 S. C. BAJIA ET AL.

system is designed for direct reading, easily portable and completely suited to making rapid
spot checks for mercaptan in a sub ppm to ppm level.
In the potentiometric method [34], sample is dissolved in alcoholic solution of sodium
acetate and titrated potentiometrically with silver nitrate solution. A glass electrode is used
as reference and a silver/silver-sulfide as an indicating electrode. The mercaptan sulfur is
precipitated as silver mercaptide and the end point is determined by the change in cell
potential. If hydrogen sulfide is present in the test sample, it interferes the test result and
should be removed prior to the potentiometric test.

3.2.3. Determination of total sulfur

In commonly used sulfur determination methods, the sample is combusted with the
presence of oxygen to convert the sulfur to sulfur dioxide, which is then collected and
subsequently determined by oxidative microcoulometry [13,14], ultraviolet fluorescence
[15–17], non-dispersive infrared [18–20], titration methods [27–30] and gravimetrically
[31]. Other test methods, namely, hydrogenolysis and rateometric colorimetry [32,33], X-
ray fluorescence spectroscopy [21–26] and gas chromatography [35–39], are also available
and are recently being used for sulfur determination in the petroleum sample.

3.2.4. Oxidative microcoulometry

In the oxidative microcoulometry method [13], the liquid or gas sample [14] is introduced
into a pyrolysis tube (900–1200°C), with a gas stream of oxygen and inert gas. The sulfur
is converted into sulfur dioxide that is then routed to a titration cell, which contains a
triiodide ion. The triiodide ion consumed in the titration cell is coulometrically replaced
and the current required to replace the triiodide ion is a measure of sulfur content in the
tested sample.

3.2.5. Ultraviolet fluorescence

Ultraviolet fluorescence test methods [15–17] are used for sulfur determination in the
gaseous sample [16,17], LPG [16,17], natural gas [17], and petroleum products and feed-
stock [15]. In these methods [15–17], the sample is injected either directly or through a boat
into a combustion tube of high temperature (around 1075°C). The gaseous hydrocarbon
and LPG samples are pre-heated prior to injection into a combustion tube. In the combus-
tion tube, sulfur is oxidized to sulfur dioxide (SO2 ) in the presence of oxygen. The oxidized
gas stream containing SO2 is then exposed to ultraviolet light. SO2 absorbs the ultraviolet
light and is converted to excited SO2 . The fluorescence emitted from excited SO2 when it
returns to a stable SO2 is detected by a photomultiplier tube (PMT). The SO2 concentra-
tion is compared with the calibration made using the standards and the resulting signal is
a measure of the sulfur contents in the sample.

3.2.6. Non-dispersive infrared

Non-dispersive infrared methods [18–20] are used for sulfur determination petroleum
products [18], coke and coal samples [19,20]. In these test methods [18–20], a weighed
sample is introduced into a combustion furnace of high temperature (around 1300°C) in
the presence of oxygen. The sulfur present in the sample is combusted to SO2 which is fur-
ther measured with an infrared detector. The sulfur amount is calculated by comparing a
predetermined calibration graph.
 JOURNAL OF SULFUR CHEMISTRY 461

3.2.7. X-ray fluorescence spectroscopy

X-ray fluorescence spectroscopy [21–26] is a recent and widely used test method for sul-
fur determination for petroleum products and feedstock. Two types of X-ray fluorescence
instruments energy-dispersive X-ray fluorescence [24,26] and wavelength-dispersive X-
ray fluorescence [23,25] are being used. In these test methods, the sample in a specified
container is placed in the X-ray beam, and the peak intensity of sulfur Kα is measured and
compared with the previously prepared calibration curve.

3.2.8. Titration method

Sulfur of gaseous sample, LPG, petroleum products and feedstock including biodiesel is
determined by different titration methods [27–30]. The test sample is pyrolyzed at high
temperature, oxidized to oxides of sulfur and measured by titration with barium chloride
solution [27] and hydrogen peroxide solution [29]. In this test method [27], the gas sample
is burned in a closed system, the oxides of sulfur produced are absorbed in sodium carbon-
ate solution. In this solution, the oxides of sulfur are oxidized into sulfate and determined
by titration with barium chloride solution by using tetrahydroxyquinone as an indicator.
Petroleum products [28] and gaseous sample [29] are burned in a closed vessel by a
suitable lamp in gas stream of carbon dioxide and oxygen. The sulfur oxides formed are
absorbed and oxidized to sulfuric acid. Sulfur as sulfate in the absorbent is determined
acidimetrically by titration with standard sodium hydroxide or gravimetrically by precip-
itation as barium sulfate [28]. The sulfate ions are determined by titration with barium
perchlorate or turbidimetrically [29].
Sulfur in petroleum products including biodiesel is determined by oxidative combus-
tion and electrochemical detection [30]. In this method [30], sample is injected into a
combustion tube with a stream of inert gases. The sample is vaporized and carried into
a high-temperature combustion tube in an oxygen-rich environment. The sulfur present
in the test sample converted to sulfur dioxide. Sulfur dioxide is reacted with the sensing
electrode in an electrochemical cell. This reaction produces a measurable current that is
directly proportional to sulfur amount.

3.2.9. Gravimetric method

The sulfur contents in petroleum products can be determined using the gravimetric
method [31]. In this test method [31], the sample is oxidized by combustion in a high-
pressure decomposition device containing oxygen. The sulfur is determined gravimetri-
cally as barium sulfate.

3.2.10. Hydrogenolysis and rateometric colorimetry

Sulfur of petroleum products and feedstock at very low concentration (sub ppm to ppm)
is measured by the hydrogenolysis and rateometric colorimetry method [32,33]. In these
methods [32,33], the sample is injected into a hydrogenolysis unit with constant flow of
hydrogen and then the mixture of sample and hydrogen is pyrolyzed at high temperature
(around 1300°C). The sulfur compounds get converted into hydrogen sulfide (H2 S) and are
readout by the rateometric detection of the colorimetric reaction of H2 S with lead acetate.
462 S. C. BAJIA ET AL.

3.2.11. Sulfur speciation

Analysis of sulfur molecular species (speciation) provides useful data for mitigating sulfur
compound problems in petroleum products and feedstock, providing greater insight than
measuring total sulfur content alone.
Sulfur speciation of petroleum samples are being done by using gas chromatography
methods [33–39]. The sulfur compounds are first separated by specific gas chromatograph
columns and then detected by atomic emission detection [36,38], chemiluminescence
detection [35], flame photometric detection [37,39] and pulsed flame photometric detec-
tion [37]. The individual sulfur compound is identified by retention time and determined
by comparing the peak area with previously run calibration data.

Acknowledgements
Authors would like to express their gratitude to Dr Jagdish Chandra Sharma, Assistant Manager,
Indian Oil Corporation Limited, Mathura Lab, Uttar Pradesh for sharing his pearls of wisdom with
us during the course of this research.

Disclosure statement
No potential conflict of interest was reported by the authors.

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