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No. Compound Level 1 Level 2 Level 3
1 Thiophene 103.7 98.3 104.8
2 Butyl mercaptan 93.7 74.8 81.4
3 2-Methylthiophene 107.9 99.5 104.5
4 tert-Butyl disulfide 100.6 100.9 98.1
5 Benzothiophene 90.5 98.5 92.9
6 Ethyl phenyl sulfide 107.4 120.2 113.1
7 Dibenzothiophene 96.2 108.0 105.1
No. Compound Level 1 Level 2 Level 3
1 Thiophene 103.5 98.4 106.3
2 Butyl mercaptan 104.5 93.5 100.2
3 2-Methylthiophene 105.5 95.1 103.0
4 tert-Butyl disulfide 94.3 97.8 94.7
5 Benzothiophene 89.7 99.2 90.8
6 Ethyl phenyl sulfide 109.1 114.7 106.7
7 Dibenzothiophene 93.3 101.3 98.3
First Edition: Mar. 2021 01-00026-EN
Table 2 Relative standard deviations at level 1 of the diesel matrix sample
for n = 6 consecutive measurements
Conclusion
Sulfur chemiluminescence detection using SCD-2030 enables
selective detection of sulfur compounds in high matrix load
petrochemical samples down to low concentration levels. Its
excellent selectivity and reproducibility ensure reliable results,
while equimolarity for different sulfur target species facilitates
the analysis of unknown sulfur compounds. Additionally,
providing good recovery independent of the sulfur component
concentration, SCD-2030 allows to accurately determine sulfur
target substances both in lower and higher concentrations
relevant for petrochemical samples.
every compound. For the samples diluted in hexane, RRF values
were between 90 and 115 for all compounds at all
concentration levels (Table 3); in the diesel matrix samples, RRF
values were between 75 and 120 (Table 4). This demonstrates
good equimolarity for not only the monosulfur compounds
belonging to different substance groups, but also for the
disulfide, independent of the chosen concentration level.
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y Reproducibility
Calculation of the relative standard deviation (%RSD) for
retention times and peak areas at level 1 revealed the reliability
of the setup (Table 2). Retention times were found to be highly
stable with a reproducibility below 0.05 % for all target
compounds. Area reproducibility was below 4 % for all spiked
components, ensuring reliable detection and quantitation of
the sulfur targets even at low concentrations.
No. Compound
Ret. Time
(min)
%RSD
Ret. Time
%RSD
Area
1 Thiophene 1.61 0.02 1.33
2 Butyl mercaptan 1.78 0.03 1.90
3 2-Methylthiophene 2.10 0.04 2.99
4 tert-Butyl disulfide 8.21 0.04 2.75
5 Benzothiophene 8.54 0.04 2.78
6 Ethyl phenyl sulfide 9.55 0.03 1.17
7 Dibenzothiophene 22.28 0.01 3.93
Table 3 Relative response factors (RRF) determined
for the hexane solvent samples at level 1, 2 and 3
y Equimolarity
Equimolarity of sulfur compound detection facilitates target
substance calibration by providing a response for different
compounds solely dependent on the amount of sulfur (in
moles) being present. To provide a measure for this, relative
response factors (RRF) can be used. The response factors (RF)
calculated from area and concentration S for each compound
are averaged over all compounds to determine values for the
single response factors relative to the average value (RRF). In a
perfectly equimolar detection, the response factors for all
components are the same, resulting in an RRF value of 100 for
Table 4 Relative response factors (RRF) determined
for the desulfurized diesel matrix samples at level 1, 2 and 3
y Recovery
The recovery of the sulfur compounds in diesel matrix was
investigated by comparing the response in the desulfurized
diesel matrix with the response in the hexane solvent matrix for
all three concentration levels. The resulting recovery values
were in the range 0.8 to 1.1 for all compounds at all levels
(Table 5), ensuring reliable recovery regardless the target
component concentration.
Table 5 Recovery determined at level 1, 2 and 3
No. Compound Level 1 Level 2 Level 3
1 Thiophene 1.03 1.01 1.01
2 Butyl mercaptan 0.92 0.81 0.83
3 2-Methylthiophene 1.05 1.06 1.04
4 tert-Butyl disulfide 1.09 1.04 1.06
5 Benzothiophene 1.03 1.00 1.05
6 Ethyl phenyl sulfide 1.01 1.06 1.08
7 Dibenzothiophene 1.06 1.08 1.09
The methodology reported in this application was developed in partnership
with Total Refining and Chemicals, Total Research & Technology Gonfreville,
Harfleur, France. eur , France .
<References>
(1) R. L. Tanner, J. Forrest, L. Newman, “Determination of atmospheric gaseous
and particulate sulfur compounds. [Atmospheric SO
2
sampling, calibration,
and data processing],” Brookhaven National Laboratory, Upton, NY, USA,
Tech. Rep. BNL-23103. Jan. 1977.
(2) X. Yan, “Unique selective detectors for gas chromatography: Nitrogen and
sulfur chemiluminescence detectors,” J. Sep. Sci., vol. 29, pp. 1931-1945,
Jun. 2006.
