C H A P T E R 3 6

SULFUR COMPOUNDS

36.1. GC SEPARATIONS
A. Capillary columns
1. Hydrogen sulfide, carbonyl sulfide, sulfur dioxide, and
methylmercaptan: 25-m GS-Q column or 25-m Poraplot Q
column, 50–120 °C at 5 °C min�1.
2. Hydrogen sulfide, methane, carbon dioxide, ethane, and propane:
25-m Poraplot Q column or 25-m GS-Q column at 60 °C.
3. Carbon dioxide, carbonyl sulfide, hydrogen cyanide, propylene,
butadiene, and furan: 25-m GS-Q column or 25-m Poraplot Q
column, 60–200 °C at 6 °C min�1.
4. Carbonyl sulfide, carbon disulfide, tetrahydrofuran, and toluene:
25-m DB-1 column, room temperature to 200 °C at 10 °C min�1.
5. Methane, ethene, ethane, propene, acetaldehyde, methyl formate,
butene, acetone, furan, dimethyl sulfide, isoprene, isobutyraldehyde,
diacetyl, methylfuran, and isovaleraldehyde: 25-m Poraplot Q
column or 25-m GS-Q column, 60–200 °C at 8 °C min�1.
6. 2-Propanethiol, 1-propanethiol, 1-methyl-1-propanethiol,
2-methyl-1-propanethiol, 1-butanethiol, 1-pentanethiol, allyl
sulfide, propyl sulfide, and butyl sulfide: 25-m GS-Q column or
25-m Poraplot Q column, 150–230 °C at 10 °C min�1.
7. n-Propyl disulfide, and n-propyl trisulfide: 25-m DB-FFAP column
at 100 °C.
8.
Cl Cl Cl
N C N C N C
, , and
C C C C C C
Cl S Cl Cl S Br Br S Br

25-m DB-210 column at 120 °C.

9. Phenanthrylene sulfide and pyrene: 30-m DB-210 column,
150–225 °C at 5 °C min�1.

Gas Chromatography and Mass Spectrometry � 2010 by Academic Press. Inc.

DOI: 10.1016/B978-0-12-373628-4.00036-8 All rights reserved.

411
412 Chapter 36

36.2. MASS SPECTRA OF SULFUR COMPOUNDS

A. Aliphatic thiols (mercaptans)
1. General formula: RSH.
2. Molecular ion: The presence of sulfur can be detected by the 34S
isotope (4.4% per atom of S) and the large mass defect of sulfur in
accurate mass measurements. In primary aliphatic thiols, the M+•
peak’s intensities range from 5% to 100% of the base peak.
3. Fragment ions: Loss of 34 (H2S) m/z units from the molecular ion of
primary (1°) thiols is characteristic. In the mass spectra of secondary (2°)
and tertiary (3°) thiols, a loss of 33 rather than a loss of 34 is observed
from the M+• peak. If m/z 47 and 61 are reasonably represented by
reasonably intense peaks and the m/z 61 peak is approximately 50% of
the intensity of the m/z 47 peak, then the mass spectrum represents a
primary thiol (see Figure 36.1). If the intensity of the peak at m/z 61 is
much less than 50% of the intensity of the peak at m/z 47, then the mass
spectrum represents a secondary or tertiary thiol. Also, remember that
saturated sulfur compounds generally undergo α cleavage (breaking of
the C1–C2 bond) to lose the largest alkyl group—analogous to the
fragmentation of aliphatic alcohols.
B. Thioethers (sulfides)
1. General formula: R–S–R′.
2. Molecular ion: M+• peaks usually have reasonably intensities. The
mass spectra of cyclic thioethers exhibit intense M+• peaks and
an intense fragment ion peak due to a double homolytic cleavage
(e.g., m/z 60 [CH2–S–CH2]+) (See Scheme 36.1).
3. Fragmentation: The mass spectra of thioethers can be distinguished
from those of 1°, 2°, and 3° thiols by the absence of the losses of

56
100

41
HS

70

50 84
29

146
47
27
61 112
39 89
35 49 97
73 79 87 91 94 103
0
20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

Figure 36.1 EI mass spectrum of 1-octanethiol.

Sulfur Compounds 413

+
+ + S
S S
H2C CH2
CH2 m/z 60
CH2
and
H2C CH2

Scheme 36.1

either 33 Da or 34 Da from molecular ions. Fragmentation also

occurs alpha to the sulfur atom with dominant loss of the larger
alkyl group. Fragmentation can occur on either side of the sulfur
atom with the rearrangement of a hydrogen atom. Fragmentation of
thioethers is analogous to the fragmentation of aliphatic ethers
(Chapter 16).
C. Aromatic thiols
1. General formula: ArSH.
2. Molecular ion: The mass spectra of aromatic thiols exhibit intense
M+• peaks as would be expected for the mass spectra of any aromatic
compound (see Figure 36.2).
3. Fragmentation: Characteristic losses from the molecular ion include
26 Da, 33 Da, and 44 Da (CS analogous to the loss of CO from the
molecular ions of phenols). Ions characteristic of the phenyl group
are also observed. Like the mass spectra of the corresponding
aminophenols, there is an observed ortho effect. However, the
spectrum of the meta-isomer differs considerably from the spectra of
both the para- and ortho-isomers by a significant increase in the
intensity of the peaks at m/z 80 and 81 and in the fact that the
intensity of these two peaks are about equal in the spectrum of the

125
100

SH

50

80
93 NH2
97
53 63
39 45 69 108
78 84
0
30 40 50 60 70 80 90 100 110 120 130 140

Figure 36.2 EI mass spectrum of 4-aminothiophenol.

414 Chapter 36

100 125

SH

80
50
NH2

93
39 65
53 97
45 63 69
27 41 57
15 18 33 47 74 78 108 122
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140

Figure 36.3 EI mass spectrum of 3-aminothiophenol.

meta-isomer, whereas the intensity of the m/z 80 peak is clearly

dominant in the spectra of the other two isomers. This difference
in the intensities of the peaks at m/z 80 and 81 along with retention
index data may be sufficient for an unambiguous identification of the
meta-isomer (see Figure 36.3).
D. Thioesters
1. General formula: RC(O)SR′.
2. Molecular ion: The M+• peak in the mass spectra of thioesters is more
intense than that of the corresponding oxygenated esters.
3. Fragmentation: Peaks representing R+ and RCO+ are frequently the
most intense observed. Peaks representing RCOS+, SR′+, and R′+
are also usually observed.
E. Isothiocyanates
1. General formula: RNCS.
2. Molecular ion: M+• peaks are usually observed.
3. Fragmentation: A peak representing a characteristic fragment ion is
observed at m/z 72 (H2C=N=C=S). For R > n-C5, the peak at m/z
115 is prominent.