Detection of Sulfur Compounds According
to ASTM D5623 in Gasoline with Agilent's
Dual Plasma Sulfur Chemiluminescence
Detector (G6603A) and an Agilent 7890A
Gas Chromatograph
Application
Hydrocarbon Processing
Authors
Wenmin Liu
Agilent Technologies Co. Ltd.
412 Ying Lun Road
Waigaoqiao Free Trade Zone
Shanghai, 200131
China
Mario Morales
Agilent Technologies, Inc.
2850 Centerville Road
Wilmington, DE 19808
USA
Abstract
Sulfur components in gasoline samples are detected uti-
lizing ASTM D 5623 with an Agilent 7890A GC configured
with Agilent 355 dual plasma sulfur chemiluminescence
detector (DP SCD). The 355 SCD response is linear,
equimolar, and provides a linear range from 0.1 to 10 ppm.
The coelution of hydrocarbon and sulfur peaks does not
present a problem for the detector. The detection limits of
sulfur compounds in gasoline are down to 20 ppb, while
no quenching was found in the gasoline sample analysis.
Introduction
Gas chromatography with sulfur chemilumines-
cence detection (SCD) provides a rapid and highly
specific means to identify and quantify various
sulfur compounds that may be present in petro-
leum feed stocks and products, such as gasoline.
Frequently, petroleum feeds and products contain
varying amounts and types of sulfur compounds.
Many sulfur compounds can be corrosive to equip-
ment, can inhibit or destroy catalysts employed in
downstream processing, and can impart undesir-
able odors to products. The ability to speciate
sulfur compounds in various petroleum liquids is
useful in controlling sulfur compounds in finished
products and is frequently more important than
the ability to simply measure total sulfur content
alone.
The SCD burner easily mounts on the 6890 and
7890A GCs, and incorporates features for easier
and less frequent maintenance. The DP technology
harnesses the power of dual flame plasma combus-
tion, optimizing combustion of the sample matrix
and formation of sulfur monoxide (SO).
The 355 DP SCD response is inherently linear,
equimolar, and far less susceptible to hydrocarbon
interference. These advantages eliminate the need
for linearizing data or determining separate
response factors for individual sulfur compounds.
Furthermore, hydrocarbons are virtually invisible
to the DP SCD. The coelution of hydrocarbon and
sulfur peaks does not show quenching. Frequent
column changes are required for analysis of vari-
ous hydrocarbon products by flame photometric
detectors (FPD) to avoid serious quenching and
inaccurate results. ASTM Method D5623 utilizes
the sulfur chemiluminescence detector (SCD) for
the detection of sulfur compounds in gasoline.
Experimental Experimental Conditions

An Agilent 7890A GC configured with split/split- 7890A GC Conditions

less inlet (Sulfinert-treated), 7683B autosampler, Front inlet Split/splitless (Sulfinert-treated
capillary inlet system)
and Agilent 355 DP SCD were used. The sulfur
standards in toluene and iso-octane (10:90) were Heater 275 C
purchased from Supelco (Bellefonte, PA). The com- Pressure 10.951 psi
ponent information is in Table 1.
Septum purge flow 3 mL/min
Mode Split
Table 1. Sulfur Standards Components
Gas saver 20 mL/min after 2 min
Concentration Split ratio 10 :1
Components Formula (ppm) (w/w)
Split flow 15 mL/min
1 Ethyl mercaptan CH3CH3SH 11.62
Oven 30 C (1 min) 10 C/min 250 C (1 min)
2 Dimethyl sulfide (CH3)2S 11.92
Column HP-1 30 m 0.32 mm 4 m
3 Carbon disulfide C2S 17.84
(P/N 19091Z-613)
4 Isopropyl mercaptan (CH3)2CHSH 34.32
SCD Conditions Agilent G6603A
5 T-butyl mercaptan (CH3)3CSH 11.28
Burner temperature 800 C
6 n-propyl mercaptan CH3CH2CH2SH 5.93
Vacuum of burner 372 torr
7 Methylethyl sulfide CH3CH2SCH3 11.87
Vacuum of reaction cell 5 torr
8 Thiophene C4H4S 14.81
H2 40 mL/min
9 Sec-butyl mercaptan CH3CH2CH(SH)CH3 23.26
10 n-butyl mercaptan CH3(CH2)3SH 5.89 Air 53 mL/min

11 Dimethyl disulfide CH3SSCH3 14.75

12 2-methyl thiophene C5H6S 14.29
Results and Discussion
13 3-metyl thiophene C5H6S 21.35 Several commercially available sulfur detectors are
14 Diethyl disulfide (C2H5)2S2 27.99 available for the determination of sulfur com-
15 Benzo(b)thiophene C8H6S 40.49 pounds in various matrices. When compared to
flame photometric detection (FPD), pulsed flame
NIST Standard Reference Material 2299, Sulfur in photometric detection (PFPD), atomic emission
Gasoline, was used. The total sulfur in gasoline is detection (AED), and inductively coupled plasma-
13.6 1.5 g/g based on analyses by isotope dilu- mass spectrometry (ICP-MS), the SCD shows the
tion thermal ionization mass spectrometry (ID- best performance based on stability, cost, and
TIMS). Homogeneity testing was performed using quantification. [2,3]
X-ray fluorescence spectrometry. With DP technology, the performance of Agilent
355 SCD has been further enhanced, for unsur-
passed stability, selectivity, and lack of quenching.
Table 2 lists the DP SCD stability at different sulfur
levels.

2
Table 2. Repeatability of Sulfur Compounds at Different Concentrations (Refer to Table 1 for peak identification.)
1 2 3 4 5 6 7 8 10 11 12 13 14 15
Con. ppm 1.16 1.79 1.78 3.42 1.13 0.59 1.19 3.80 0.59 1.47 1.43 2.14 2.80 4.0
RSD (%) 2.8 3.6 3.1 1.9 3.0 2.7 3.9 3.9 2.9 2.1 2.2 2.9 0.4 3.7
Con. ppm 0.12 0.18 0.18 0.34 0.11 0.06 0.12 0.38 0.06 0.15 0.14 0.21 0.28 0.4
RSD (%) 5.7 7.4 3.4 3.7 6.6 4.8 5.7 4.8 8.0 4.0 3.3 4.7 7.3 3.1

Correlation coefficients of the tested sulfurs over compound. Figure 1 shows the chromatogram of
three orders of magnitude were better than 0.99 sulfurs in a hydrocarbon matrix without interfer-
(R2). Table 3 shows the linearity of each sulfur ence (1 to approximately 2 g/kg).

Table 3. Linear Ranges of Tested Sulfurs (Refer to Table 1 for 34

8/9 11
14 15
13
peak identification.) 3500

Linearity (R2)
3000
Analytes Concentration Range 12
2500 7 12

1 0.1ppm to 10ppm 0.9975 2000

5
6
2 0.1ppm to 10ppm 0.9982 1500

10
1000

3 0.1ppm to 10ppm 0.9991 500

4 0.1ppm to 10ppm 0.9992 0

2.5 5 7.5 10 12.5 15 17.5 20 m in

5 0.1ppm to 10ppm 0.9995

Figure 1. Chromatogram of sulfur standard in hydrocarbon
6 0.1ppm to 10ppm 0.9996 matrix. (Refer to Table 1 for peak identification.)
7 0.1ppm to 10ppm 0.9998
8/9 0.1ppm to 10ppm 0.9998 The data in Table 4 illustrate the sensitivity (S/N)
10 0.1ppm to 10ppm 0.9994 of 355 SCD for trace-level analysis (approximately
20 ng/kg) of sulfurs in a hydrocarbon matrix.
11 0.1ppm to 10ppm 0.9999 Figure 2 shows the chromatogram of trace sulfurs,
12 0.1ppm to 10ppm 0.9997 which also indicates no interferences in the analy-
13 0.1ppm to 10ppm 0.9995 sis.
14 0.1ppm to 10ppm 0.9997
15 0.1ppm to 10ppm 0.9999

Table 4. Sulfur Sensitivity (Refer to Table 1 for peak identification.)

Peak No. 1 2 3 4 5 6 7 8/9 10 11 12 13 14 15
S/N 2.0 2.5 5.0 4.6 1.8 1.6 2.4 5.0 1.5 3.6 2.0 4.6 3.2 5.2

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800

600 15
400
3 4 8/9 11 1213 14
1 2 5 67 10
200

Figure 2. Chromatogram of sulfurs at trace levels (20 ng/g).

(Refer to Table 1 for peak identification.)

3

Gasoline Samples Analysis
NIST Standard Reference Material 2299 was
detected on an Agilent SCD and the mass concen-
tration of total sulfur in sample was calculated by
summing the sulfur content of all sulfur compo-
nents (known and unknown) in the sample to
arrive at its total sulfur value as recommended by
ASTM 5623.
Figure 3A shows the chromatogram of the sulfur
standard and Figure 3B shows the chromatogram
of the standard gasoline sample. The total amount
of sulfur is calculated by summing all the peak
areas in Figure 3B and quantitated as thiophene
11.8 g/g of total sulfur with an RSD 2.7% (n = 5)
was calculated in the gasoline sample. This was
within the specified range of 13.6 1.5 g/g.
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Conclusions
The Agilent DP SCD is used for the detection of
sulfur compounds in a complex hydrocarbon
matrix. The results show that the DP SCD has
linear response to sulfur compounds without
quenching, yielding MDLs down to 20 ng/g. This
solution is available as an Agilent preconfigured
system; please refer to Agilent SP1 7890-0365 for
ordering information.
References
1. ASTM 5623: Standard test method for sulfur
compounds in light petroleum liquids by gas
chromatography and sulfur selective detection
2. Roger L. Firor and Bruce D. Quimby, Analysis
of Trace Sulfur Compounds in Beverage-Grade
Carbon Dioxide, Agilent Technologies publica-
14
tion 5988-2464EN
15
3. Roger L. Firor and Bruce D. Quimby, A Com-

400
12 7 12
parison of Sulfur Selective Detectors for Low-
56
200
10
Level Analysis in Gaseous Streams, Agilent
0
0 2 4 6 8 10 12 14 16 18 min Technologies publication 5988-2426EN

Figure 3A. Chromatogram of sulfur standard.

For More Information
For more information on our products and services,
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visit our Web site at www.agilent.com/chem.
1000

800
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600
3 7 12 14
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Figure 3B. Chromatogram of gasoline standard sample. (Refer

to Table 1 for peak identification.)

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Information, descriptions, and specifications in this publication are subject to change

without notice.

Agilent Technologies, Inc. 2008

Printed in the USA

August 12, 2008
5989-9233EN