بحث جدا مهم مركبات الكبريت العضوية في البترول

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ORGANIC SULFUR COMPOUNDS OF

PETROLEUM
a
G. F. BOLSHAKOV
a
Institute of Petroleum Chemistry, Siberian Branch of the USSR
Academy of Sciences , SU-634055 , Tomsk , USSR
Published online: 31 May 2012.
To cite this article: G. F. BOLSHAKOV (1986) ORGANIC SULFUR COMPOUNDS OF PETROLEUM,

Sulfur reports, 5:2, 103-393, DOI: 10.1080/01961772.1986.10462153
To link to this article: http://dx.doi.org/10.1080/01961772.1986.10462153
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Sulfur Reports
Volume 5(2), August 1986, pp. 103-393
© 1986 harwood academic publishers OmbH
Printed in the United Kingdom
ORGANIC SULFUR COMPOUNDS

OF PETROLEUM
G. F. BOLSHAKOV
Institute of Petroleum Chemistry
Siberian Branch of the USSR Academy of Sciences
SU-634055 Tomsk, USSR
(Received March 25, 1985)
This monograph summarizes the present-day knowledge of the variety of organic sulfur compounds in
petroleum and petroleum products and outlines the methods for their isolation and removal. The
Downloaded by [University of Arizona] at 17:10 19 April 2015
chemical and physical properties of these organic sulfur compounds and their effect on the service
characteristics of petroleum products are considered. Recent ideas concerning the genesis and
transformation of petroleum sulfur compounds in the interior of the Earth are discussed. Consideration
is given to some properties of sulfur-organic compounds which make them rather promising for practical
application.
This monograph is intended for specialists working in the fields of petroleum chemistry. geochemistry,
and refining.
CONTENTS
I. INTRODUCTION 105
·············~~~············································· ..
11. CONTENT OF ORGANIC SULFUR COMPOUNDS IN OILS AND

DISTILLATES THEREOF . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . • • • . . . . . . ... 106
II. I. Total Sulfur Content of Petroleum ............................................. . 106
11.2. Sulfur Content of Petroleum Fractions ......................................... . 112
11.3. Characteristic Composition of Organic Sulfur Compounds in Crude Oils ............ . 120
I/.4. Characteristic Composition of Organic Sulfur Compounds in Oil Distillates ......... . 148
1/.5. On the Genesis of Organic Sulfur Compounds of Petroleum .............•. , •...... 166
Ill. ISOLATION AND REMOVAL OF ORGANIC SULFUR COMPOUNDS FROM CRUDE
PETROLEUM AND ITS DISTILLATES .................................••.••...... 173
II/.1. Sulfonation .............................................................. . 173
III.2. Adsorption and Rectification ................................................ . 174
II/.3. Selective Extraction ........................................................ . 182
III.4. Isolation with Alkalies ..................................................... . 194
II/.5. Isolation with Heavy-Metal Oxides and Salts .... ~ .............................. . 196
Il/.6. Oxidation ... 197
Ill. 7. Complexing . : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : 200
Ill. B. Hydrogenative Refining ...............................................•...•. 208
IV. CHEMICAL AND PHYSICAL PROPERTIES .....•••.••.......•............•.•.•..• 222

N.l. Structure ................. . 222
N.l.l. Thiols . . . . . . . . . . ..............•............••..........••.••..
........................ ' ... ' ••••••••••••• ~ ~ ••• t t • ' ••• 224
103
104 G. F. BOLSHAKOV
W.1.2. Sulfides ........................... · ........... · · · · · · · · ..... · · · · · · · 224

W.l.J. Disulfides ........................................................ . 225
W.1.4. Thiophenes ....................................................... . 227
JV.2. Chemical Properties ...........•....•...............................•....... 228
W.2.1. Thiols ........................................................... . 228
W.2.2. Sulfides .................................•......................... 230
W.2.3. Disulfides ........................................................ . 233
W.2.4. Thiophenes ....................................................... . 252
IV.3. Physical Properties ........................................................ . 254
W.3.1. Density .......................................................... . 254
W.3.2. Boiling Point ..................................................... . 256
IV.3.3. Melting Point ....................•................................. 256
W.3.4. Dipole Moments .................................................. . 259
IV.4. Thermodynamic Properties ................................................. . 261
W.4.1. 1/eatCapacity .•....•.......................•...................... · 261
W.4.2. Entropy, Enthalpy, Isobar Potential .................................. . 262

IV.S. Optical Properties ..............................................•..... · · · · · 264
VI.S.l. Refractive Index ................................................... . 264
W.5.2. IR Spectra .....•......................•........•..•.....•... · · · · · · · 265
W.5.3. Electronic Spectra ..............•..................•.....•.......... 271
W.5.3.1. Thiols ..............•.................................•.. 271
JV.5.3.2. Sulfides ......•....•...............................•...... 271
IV.5.3.3. Disulfides .......................................... · • · · · · 272
W.5.3.4. Thiophenes .............................................. . 272
IV.5.4. 111 NMR Spectra ..................................................• 273
V. MAIN SYNTHETIC ROUTES TO ORGANIC SULFUR COMPOUNDS

OF PETROLEUM 274
V.l. Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . • . . 274
V.2. Acyclic Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
V.3. Cyclic Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
V.4. Di- and Polysulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
V.5. Thiophenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
VI. APPLICATION OF ORGANIC SULFUR COMPOUNDS OF PETROLEUM . . . . . . . . . . . . . 298

VI. I. Vulcanization of Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
Vl.2. Modification of Inorganic Sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
VI.3. Extraction of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
V/.4. Floatation of Ores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
V/.5. Physiologically Active Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . 305
VI.6. Exogenic Regulators of Cereal Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
VI. 7. Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
VII. EFFECT OF ORGANIC SULFUR COMPOUNDS ON SERVICE PROPERTIES

OF PETROLEUM PRODUCTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
VII. I. Formation of a Solid Phase in the Oxidation of Sulfur-Containing Fuels . . . . . . . . . . . . 334
Vll.2. Chemical Composition and Structure of the Sediments and Deposits Formed
in Aviation and Automobile Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
VII.3. Chemical Composition and Structure of Deposits Formed in the Cooling Systems
of Rocket Engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Vl1.4. Mechanistic Aspects of Sediment Formation in Metal-Free Oxidation
of Hydrocarbon Sulfur Compound Mixtures . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . . 353
VII.S. Interaction of Sulfur·Organic Compounds with Metal Surfaces and the
Anti wear Properties of Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
ORGANIC SULFUR COMPOUNDS OF PETROLEUM 105
I. INTRODUCTION
The total geological resources of petroleum in the Earth are approximately 9.5 • 10 10
tons 1 • The average sulfur content of petroleum is about 1%. This means that
the petroleum in the Earth's interior contains approximately 109 t of sulfur or
(4-7) ·10 10 t of various organic sulfur compounds, such as mercaptans, sulfides, di-
sulfides, thiophenes, and other more complicated species.
The present methods for the oil production allow as little as 40-50% of the oil to be
recovered from the Earth's interior. Thus, mankind has available no more than
4.5 ·10 11 t of recoverable oil resources today. Along with oil, about (4-7) ·109 t of
sulfur compounds will be brought to the Earth's surface.
At present about 4 • 107 t of sulfur is burnt with oil products annually in the world.
Recalculated as the combustion products this gives about 8 • 107 t of sulfur dioxide or
1.2 • 108 t of sulfur~c acid. This presents a great ecological hazard to the environment.
The presence of sulfur compounds causes a considerable loss of performance of
petroleum products.
At the same time sulfur compounds may be recovered from petroleum and used in
different fields of industry. 2 Sulfur compounds are rather valuable raw materials
for the preparative, synthetic, and industrial chemistry. Aromatic polysulfides are
thermo-, light and radiation resistant, polysiloxanes with thiophene rings are char-
acterized by a high viscosity and good antitear and antiwear properties, cephalothin is
a broad-spectrum antibiotic, sulfides and sulfoxides are efficient metal extractants,
sulfoxides are active repellents, sulfones are solvents and antifungal agents, mercap-
tans can be used in the production of rubber.
The exte~sion of t?e fields of application of petroleum sulfur compounds will
increase their production. The manufacturing methods and scales will determine the
cost. One ~an assume t.hat the refining of petroleum distillates by sulfur compounds
isolation without changi~g the composition will be cheaper or, at least, comparable in
cost with hydrogen refimng.
The isolation of sulfur compounds from petroleum and its distillates makes it
possible to obtain commercial oil products of a quality no worse or even better than
that of those obtained by hydrogen refining. The cost of refining of petroleum
distillates by sulfur compound removal is balanced by the higher maintenance cost
of facilities using sulfur-containing fuel. Extra costs due to consumption and
production of fuels from sulfur and sulfur-rich petroleum can be judged by the data
below (roubles per 1000 t of fuel):
Fuels
Sulfur-poor Normal Sulfur-rich
Maintenance costs 2130 2980 3650

Capital investment 3900 4500 5095
Trapping of sulfur oxides from the fuel combustion products of thermal power
plants will enable the requirements for sulfuric acid to be nearly completely satisfied.
106 G. F. BOLSHAKOV
At present, commercial plants for the catalytic refining of waste gases have been built,
which makes it possible to recover from the smoke up to 99% of sulfur dioxide, to
oxidize it to S0 3 , and to convert this to sulfuric acid. It is rather difficult to use the acid
thus obtained in industry since it contains impurities and is diluted. However, this acid
can be widely applied in agriculture as a chemical meliorant for soils with carbonate
salinity.
One finds it most efficient to recover sulfur compounds from petroleum in the
native form and to use them further as valuable chemical feed-stock.
11. CONTENT OF ORGANIC SULFUR COMPOUNDS IN PETROLEUM

AND ITS FRACTIONS
11.1. Total Sulfur Content of Petroleum
The sulfur content of petroleum ranges from some hundredths of a percent to 8%. 3-S
In rare cases, the sulfur content may reach 9.6%6 and even 14%.7 1n this case sulfur
compounds account for 70-80% of the petroleum. After gr_ouping oils according to
stratigraphic, gypsometric, and lithologic data and corresponding statistical analysis,
the sulfur content of petroleum turns out to lie within a much narrower range. 4 Table
1 contains statistically analyzed data for two thousand oils from different regions of
the Earth. 4 Oils from carbonate deposits contain considerably greater amounts of
sulfur compounds than oils from terrigenous collectors. The sulfur compound
contents of concomitant or natural gases varies in a similar way (Table 2). The data
are based on the analysis of 2500 samples of concomitant and natural gases.
TABLE I
Effect or Geologo-Geochemical Factors on Changes in the
Average Sulfur Content or Oils, Wt.%
Sulrur content or oils from collectors

Depth of
Agt of deposits occurrence, m terrlgenous c.:arbonac.:eous average
1 l 3 4 s
Neogene 0-1000 0.77 2.74 1.17
1000-2000 0.45 2.00 0.59
2000-3000 0.33 2.34 0.61
3000-4000 0.23 0.23
4000 0.26 0.26
Paleogene 0-1000 0.65 2.64 1.35

1000-2000 0.82 3.08 1.92
2000-3000 0.39 1.26 0.67
3000-4000 0.40 0.41 0.40
TABLE 1 (Continued)
1 l 3 4 5
Cretaceous 0-1000 0.73 2.83 1.65

1000-2000 0.66 3.11 1.42
2000-3000 1.14 2.54 1.22
3000-4000 0.31 1.46 0.69
4000 0.39 0.39
Jurassic 0-1000 0.34 0.63 0.40

1000-2000 0.38 2.30 0.87
2000-3000 0.36 1.66 0.62
3000-4000 0.15 0.78 0.63
4000 0.17 0.17
Triassic 0-1000 0.75 0.75

1000-2000 1.12 1.12
2000-3000 0.07 1.02 0.66
3000-4000 0.61 0.61
Permian 0-1000 0.36 1.83 1.02

1000-2000 0.49 1.32 1.26
2000-3000 0.43 1.02 0.72
3000-4000 1.10 0.54 0.36
4000 0.20 0.20
Carbonic 0-1000 0.27 2.51 1.25

1000-2000 1.91 2.49 2.22
2000-3000 0.83 1.59 1.17
3000-4000 0.10 0.83 0.34
Devonian 0-1000 0.34 0.58 0.42

1000-2000 1.66 0.77 1.46
2000-3000 0.84 0.73 0.78
3000-4000 0.55 0.38 0.44
4000 0.10 0.10
Silurian 0-1000 0.14 0.14

1000-2000 0.27 0.27
2000-3000 0.14 0.14
3000-4000 0.10 -• 0.10
Ordovician 1000-2000 0.24 1.41 0.91

2000-3000 0.28 0.33 0.31
3000-4000 0.16 0.16
4000 0.09 0.09
Cambrian 0-1000 0.27 0.2.7

1000-2000 0.18 0.17 0.17
2000-3000 0.09 0.45 0.29
3000-4000 0.'21 0.21
TABLEl
Etl'ect of Geologo-Geoc:hemical Factors on the Hydrogen Sulfide Content, Vol. %,
in Concomitant (Dissolnd) and Natural (Free) Gases
In dissolved gases In rree gases

from deposits from deposits
Age or Depth or terrlgenous c:arbonaceous terrlgenous carbonaceous

deposits occurrence rocks rocks rocks rocks
1 l 3 4 5 6
Neogene 0-1000 0.00 3.12 0.002 0.00

1000-2000 0.008 0.002 0.00
2000-3000 0.00 0.00 0.00
3000-4000 0.00 0.00
4000-5000 0.00 O.OOt

5000 0.00
average 0.002 0.002 0.00
Paleogene 0-1000 0.003 0.28 0.00 0.14

1000-2000 0.008 0.15 0.00 0.19
2000-3000 0.00 0.00
3000-4000 0.00 0.00 0.02
4000 0.00
average 0.006 0.25 0.00 0.15
Cretaceous 0-1000 0.00 1.71 0.001 0.02

1000-2000 0.023 0.60 0.010 0.08
2000-3000 0.00 0.19 0.001 0.01
3000-4000 0.00 0.13 0.00 2.80
4000 0.00 15.2
average 0.005 0.73 0.005 0.39
Jurassic 0-1000 0.00 0.00

1000-2000 0.00 0.001 0.36
2000-3000 0.00 0.028 1.69
3000-4000 0.00 0.00
4000-5000 0.00 4.55
5000 0.00 2.43
average 0.00 0.009 1.01
Triassic 0-;-1000 0.00 0.001 8.40

1000-2000 0.00 0.00 0.35
2000-3000 0.00 0.00 0.24
3000-4000 0.00 0.00 2.00
4000 0.00 2.45
average 0.00 0.00 1.37
Permian 0-1000 0.00 0.00 0.00

1000-2000 0.00 0.37 0.00 1.40
2000-3000 0.00 1.17
3000-4000 0.00 0.00 1.53
4000 0.00 8.45
average 0.00 0.00 1.65
TABLE 2 (Continued)
1 2 3 4 5 6
Carbonic 0-1000 0.00 0.00 0.00 0.04

1000-2000 0.12 1.71 0.004 0.18
2000-3000 1.05 0.00 0.07
3000-4000 0.00 0.50 0.00 0.012
4000-5000 0.05 0.32
5000 0.90
average 0.11 1.25 0.003 0.15
Devonian 0-1000 0.00 0.00 0.15

1000-2000 0.00 0.08 0.00 0.04
2000-3000 0.00 0.004 0.00
3000-4000 0.00 0.00
4000 0.00
average 0.00 0.00 0.05
Silurian 0-1000 0.00 0.00 0.00

1000-2000 0.02 4.10
2000-3000 0.00
3000-4000 0.00
4000-5000 0.05
5000 0.03
average 0.02 0.34
Ordovician 0-1000 0.00 0.00 0.00 0.00

1000-2000 0.00 1.10 0.00
2000-3000 0.00 0.00 0.00
3000-4000 0.00 0.00
4000-5000 0.00 0.00 0.014
5000 0.009
average 0.00 0.37 0.00 0.009
Cambrian 0-1000 0.00 0.00

1000-2000 0.00 0.00
2000-3000 0.00 0.00 0.010
3000-4000 0.00 0.00
average 0.00 0.00 0.09
The highest sulfur compound contents are observed in oils occurring at a depth
of 1.5-2 km (Figs. 1 and 2). Oils from smaller depths display a lower sulfur
compound content. With increasing depth temperature and pressure increase, the
catagenic processes become more intense and the petroleum undergoes gradual
desulfurization. The sulfur compound destruction is accompanied by hydrogen
sulfide evolution. This is supported by the higher hydrogen sulfide contents of natural
10 G. F. BOLSHAKOV
SULFUR CONTENT, wt.%

0 , 0 , 2 J 0 , 2 ~
2 NEOGENE
4
(N)
0
2 PALEOGENE
...0 (P)
2 CENOZOIC
(Kz)
CRETACEOUS
(K)
JURASSIC t/.1
E-4
(I) H
t/.1
0
TRIASSIC ~
....
Mo
0
(T) 1=1
~
ffi2 MESOZOIC 0
~., (Mz) fil
C!)
c=::o
::;, <
oz
0
PERMIAN
(P) H
0~
<
0
~ H
Ol CARBONIC C!)
0
:.X:4 (C) H
e-to 0
r4
~~ DEVONIAN ~
r::::l
4
(D)
0
2 SILURIAN
4
(S)
,
0
4
ORDOVICIAN
(0)
0
2 CAMBRIAN
4
(Cm)
D
PALEOZOIC
I (Pz)
•
11) •
~'Cf
t
as
s::: .....
11)
(l)b:)
I
.,.;mo I
.r.::as t.Ot.Oc.
.,.; Ol'lllll oasm
Hill ..o::so +»H
11)
r-1 't:llll
H::S HOC. Or-1 +»
(I)O GSI1>11> S:::l> (I)QS'-4.,.;
e-tS::: O()'tf Od ~()Oill
FIGURE 1. Effect of the geochemical characteristics of enclosing rocks on the average sulfu
content of oils. r
Pg
K
Cm
0 1 2 J
SULFUR CONTENT, wt. %
FIGURE 2. Generalized correlation between the average sulfur content of oils and the geochemical
characteristics of enclosing rocks. Designations are listed in Fig. 1.
112 G. F. BOLSHAKOV
gases at greater depths, especially in Mesozoic and Late Paleozoic deposits. The oils
with the lowest sulfur contents are most likely to occur in the oldest deposits, although
exceptions are known.
The sulfur compound content increases with rising boiling points of oil fractions.
Oil distillates may contain up to 70% sulfur compounds. The remaining sulfur
compounds are present in the tar-asphalt fraction of oiL This distribution is not
invariable, of course, and in some oils most sulfur compounds are concentrated in the
heavy tar-asphalt fraction.
11.2. Sulfur Content of Petroleum Fractions
In order to recognize general patterns in the sulfur compound distribution in

petroleum fractions a statistical treatment of experimental data for all known oil fields
in the USSR and other countries has been performed.s-25 The oils occurred in
terrigenous and carbonate collectors of different age, divided into sections 500 m
deep. 22 The Cenozoic and Mesozoic oils were obtained from terrigenous and the
Paleozoic oils from carbonate productive strata.
The average sulfur content of petroleum fractions increases as the boiling point of
the fraction rises (Table 3). Only in oils from the Cambrian carbonate deposits the
sulfur content in residues is lower than that in heavy vacuum distillates (400-500 °C).
Such cases are quite rare for certain oils of other groups and do not distort the general
statistical picture.
An increase in the total sulfur content of petroleum raises also the amount of sulfur
compounds in fractions. 22 Independent of age, depth, and lithology of collectors,
the increase in the sulfur content in fractions depends on the total sulfur content
(Fig. 3). A relative deviation of the experimental data from the calculated values
increases as the boiling point rises.
The shape of average lines reproducing these relationships changes from concave
for the gasoline-kerosine fractions through nearly linear for the 300-400 oc distillate
to convex for higher distillates and residues. ,
The line slope increases with rising boiling point, being approximately 0.14%,
0.70%, 0.95%, and 1.10% for a 1% increase in the sulfur content of petroleum for the
fractions IBP-200, 200-300, 300-400, and 400-500 °C, respectively. This means that
with an increase in the sulfur content of oils (upon their secondary sulfurization in the
Earth interior, for example) the high-boiling fractions are enriched in sulfur consider-
ably faster than the low-boiling oils.
The influence of the depth of occurrence on the sulfur content in oil fractions is
differently manifested in oil fields of varying geological age (Table 3, Fig. 4).
At nearly all the gypsometric levels, the lowest sulfur content is typical of fractions
of the youngest, i.e. Cenozoic oils, represented in our selection by predominantly
Neogenic oils (45 samples out of 53) and the highest sulfur content is characteristic of
fractions of Paleozoic oils (without Cambrian oils).
The average sulfur content increases slowly in gasoline fractions and decreases in
high-boiling distillates and residues of Cenozoic oils with plunging the oil fields from
200 to 5000 m deep.
TABLE3
Average Sulfur Content, Wt. %, in Crudes and Petroleum Fractions Depending on Geologo-Geochemical Factors
Average sulfur content, wt. %

Fractions, cc 0
!:1:'
0
Age or deposits Depth or occurrence Crude oil IBP-200 .100-300 300-400 400-500 IBP-300 IBP-500 >500 >
z
.....
()
I 2 3 4 5 6 7 8 9 10 tn
c
r
Cenozoic 0-500 0.58 0.000 0.145 0.39 0.64 0.126 0.40 1.03 ;:!
!:1:'
500-1000 0.29 0.011 0.065 0.22 0.44 0.034 0.15 1.30
1000-1500 0.26 0.019 0.117 0.30 0.52 0.073 0.23 0.39 8
1500-2000 0.28 0.026 0.112 0.24 0.36 0.073 0.19 0.67 .,::
0
2000-2500 0.27 0.023 0.086 0.28 0.50 0.056 0.18 0.95 c
2500-3000 0.21 0.030 0.096 0.17 0.23 0.060 0.13 0.53 z
0
3000-3500 tn
0.17 0.021 0.059 0.13 0.21 0.041 0.12 0.30
average 0
0.30 0.020 0.072 0.27 0.45 0.060 0.20 0.78
.,
"!j
Mesozoic 0-500 0.87 0.076 0.172 0.45 0.77 0.156 0.47 1.59 !:1
!:1:'
500-1000 0.86 0.054 0.211 0.51 0.73 0.154 0.42 1.70 0
r
1000-1500 0.95 0.039 0.235 0.64 1.26 0.133 0.49 3.10 lTI
c::
1500-2000 0.70 0.052 0.270 0.79 1.06 0.139 0.48 1.47 ~
2000-2500 1.04 0.037 0.309 0.88 1.47 0.152 0.61 2.36
2500-3000 0.43 0.038 0.120 0.37 0.64 0.072 0.25 1.07
3000-3500 0.14 0.004 0.032 0.15 0.22 0.016 0.09 0.42
3500-4000 0.12 0.001 0.017 0.15 0.25 0.007 0.07 0.71
4000-4500 0.08 0.006 0.019 0.08 0.16 0.012 0.05 0.39
average 0.76 0.036 0.219 0.62 0.98 0.119 0.44 1.81
........
.....
-.,.
TABLE 3 (Continued)·
2 3 4 6 8
1 5 7 7 9 10
Paleozoic* 0-500 1.11 0.100 0.314 0.81 0.97 0.310 0.76 1.44
(terrigeneous rocks) 500-1000 0.50 0.037 0.140 0.37 0.57 0.095 0.27 1.52
1000-1500 2.42 0.182 1.446 2.47 2.89 0.716 1.65 4.11
1500-2000 1.53 0.132 0.867 1.51 1.86 0.431 0.97 3.09
2000-2500 1.47 0.091 0.863 1.50 1.81 0.388 0.91 3.18
2500-3000 0.84 0.034 0.427 0.86 1.08 0.178 0.48 2.56
3000-3500 0.58 0.014 0.226 0.62 0.85 0.102 0.35 1.95
3500-4000 0.38 0.072 0.155
,.,p
0.38 0.65 0.108 0.32 0.52
average 1.68 0.129 0.958 1.69 2.04 0.471 1.08 3.37
500-1000 2.07 0.274 1.150 2.03 2.76 0.686 1.48 3.48

=
0
PaJeozoic* ~
(carbonaceous deposits) 1000-1500 2.52 0.327 1.593 2.43 2.79 0.848 1.65 4.53
1500-2000 2.74 0.296 1.624 2.63 3.25 0.858 1.81 4.62
$:
~
2000-2500 1.45 0.090 0.644 1.44 1.80 0.304 0.81 3.97 0
2500-3000 0.80 0.067 0.256 0.56 0.86 0.149
<
0.39 2.00
3000 0.69 0.044 0.146 0.30 0.57 0.086 0.24 1.64
average 2.16 0.228 1.261 2.03 2.48 0.678 1.40 3.90
Cambrian 1000-2000 0.14 0.004 0.050 0.10 0.23 0.021 0.08 0.39
(terrigenous deposits) 2000-3000 0.022 0.006 0.047 0.11**) 0.02***) 0.57
Cambrian 1900-2200 0.46 0.375 0.437 0.67 0.80 0.400 0.54 0.06
( carbonaceous deposits)
*) Without Cambrian; .. ) 300-360 °C; ... ) IBP-360 CC

FIGURE 3. Generalized correlation between the sulfur content in oils and in oil fractions and residues.
e oils from terrigenous rocks;
0 oils from carbonaceous rocks.
Distillates: 1: IBP·200 oc, 2:200-300 oc, 3:300-400 oc, 4:400-500 °C, 5: residue >500 oc.
With increasing the depth of occurrence the gasoline fractions of Mesozoic oils
become poorer in sulfur. The sulfur compound quantity in heavier fractions
changes with submerging in a quite different manner: at first it reaches some
maximum value that corresponds to a depth of about 2200 m for distillates and about
1200 m for residues and then begins to fall rapidly.
116 G. F. BOLSHAKOV
0
J
2
lR
• 1
E-t
~
..
E-t
0
Ea
E-4
z0 2
u
p::
~:::> 1
Cll
0
f.4 2
t2
08
1
Q2
at L..:~~~~~s:::..o::Ao==,.J
, 2 j 4
DEPTH OF OCCURRENCE, KM
FIGURE 4. Variation in average sulfur content in distillates IDP-200 •c (1), 200-300 •c (2),
300-400 •c (3), 400-500 •c (4), and residues >500 •c (5), depending on the depth of occurrence and
the geological age of the enclosing rocks.
oils
J;. from Cenozoic terrigenous rocks
• oils from Mesozoic terrigenous rocks
e oils from Paleozoic terrigenous rocks (without Cambrian)
0 oils from Paleozoic carbonate rocks (without Cambrian)
An analogous change in the sulfur content passing through a maximum is common

in all the fractions of Paleozoic oils. Unlike the Mesozoic oils, the Paleozoic oil
fractions are richest in sulfur when the oil field occurs at depths of 1200-1600 m. The
maximum concentrations of sulfur in fractions of oils from the Paleozoic carbonate
deposits are always higher than those in the corresponding fractions of oils occurring
in terrigenous rocks.
The Cambrian oils, especially those from terrigenous collectors, differ from other
Paleozoic oils (Table 3, Fig. 1) in their considerably lower sulfur content of all the
fractions as well as in some characteristic features of the relative distribution of sulfur.
The content of sulfur in distillates increases with higher boiling points, being 0-3,
2-10, 5-26, and 11-36% for the distillates IBP-200, 200-300, 300-400, and
400-500 °C, respectively (Figs. 5, 6).
The sulfur content of distillates of oils from slightly submerged Phanerozoict
terrigenous collectors increases and that of the residues decreases with increasing
depth of occurrence to 1200-1800 m which corresponds to the beginning of the main
zone of oil formation (Figs. 5, 6). The 500 oc distillates of Cenozoic oils contain up to
74% of a total amount of sulfur compounds in the oil, the corresponding values for
the Paleozoic and Mesozoic oils being 52 and 46%, respectively.
Upon further plunging and a gradual increase of the role of catagenetic processes
the relative distribution of sulfur in the fractions of oils from terrigenous deposits
becomes more dependent on the time of the oil field formation.
The average sulfur content of the distillate portion of Cenozoic oils occurring at
depths from 1200 to 300 m gradually decreases to approximately 50% of the total
sulfur compound amount in petroleum mainly on account of heavy vacuum
fractions.
After reaching a maximum at a depth of 1800 m and on passing to the mesoca-
tagenesis zone (1800-2800 m deep), the distillate fractions of Mesozoic oils show a
slightly lower average sulfur content* which further increases up to 55% based on the
total 500 oc distillate.
In oils of terrigenous Paleozoic, at depths of about 1400 m, the relative distribution
of sulfur remains nearly invariable upon plunging to 3000 m. After that the sulfur
content of the 400-500 °C fraction begins to increase rapidly. At a depth of 3800 m
the sulfur content of the 500 oc distillate reaches 61% of its total amount.
Thus, at depths of 1200-1800 m the sulfur content in the distillate part of petroleum
decreases, that in the residues increasing from Cenozoic to Paleozoic oils. Upon
further submerging, the above sequence reverses at depths exceeding 3-4 km due to
the development of catagenic processes.
These phenomena can be explained by a more rapid decomposition of higher-
molecular sulfur compounds compared to low-molecular sulfur compounds upon
catagenic destruction. The sulfur compound destruction is accelerated by the
t With the possible exception of Predevonian deposits for which no information is available
.*Evidently .this. lowering ~emonstrates ?~ly a local regional feature of Low Cretaceous and Ju~assic
oils of West S1bena accountmg for a prevadmg number of samples of oils of this gypsometric interval of
the Mesozoic strata section.
118 G. F. BOLSHAKOV
A
40 60 80 100
SULFUR CONTENT, % OF TOTAL SC
FIGURE s. Variation in the relative distribution of sulfur between fractions of Cenozoic (a) and
Mesozoic (b) oils depending on the depth of occurrence of the enclosing rocks.
~ IBP-200 "C IIIIIIliil200-300 oc
~ 300-400 °C c::::J 400-500 oc
~ residues > 500 oc
temperature elevation upon submerging and the catalytic properties of clay minerals
of terrigenous deposits. The destruction depth is increasing in time.
The situation is quite different in carbonate collectors. The carbonate rocks are far
from being active in the free-radical thermal destruction occurring in catagenesis Of
oil, but they catalytically accelerate the reaction of elemental sulfur with hydrocar..
bans and reduce it to hydtogen sulfide 26.27 which is also involved in oil sulfurization
The maximum sulfur content in the distillates of oils from these collectors (about SO%
of the total sulfur compounds for the broad 500 oc
fraction, Fig. 6) is revealed at as
A
0 20 40 60 80 100
SULFUR COUTENT, % OF TOTAL SC
FIGURE 6. Variation in the relative distribution of sulfur between fractions of oils from Paleozoic
terrigenous (a) and carbonaceous (b) collectors (without Predevonian) depending on the depth of
occurrence. Designations are given in Fig. 5.
small a depth as about 800 mt). With increasing depth the sulfur content of the
distillates decreases; at a depth of about 4400 m over 80% sulfur is contained in heavy
residues.
The Cambrian oils, distinguished from oils of the Late Paleozoic by a much lower
sulfur compound content, (Table 3) deserve special consideration.
The distribution of sulfur in the fractions of Upper and Middle Cambrian oils or
Pribaltics from terrigenous deposits at depths of 1500-2000 m is similar to that in
other oils of the Paleozoic from the same depth interval (Fig. 6).
The oils from the overlying (about 2000 m deep) Osa horizon composed of
t Data regarding superposed deposits of the carbonate Paleozoic are not available.
120 G. F. BOLSHAKOV
carbonate rocks belonging to the same deposits, are distinguished by high sulfur
contents of the distillate fractions (23% in 200 oc, and 18%, 25%, and 32% in the
successively higher boiling 100 °C distillates, respectively). The 500 oc residues
constituting over 16% of these oils contain only slightly more than 2% of the total
sulfur content of petroleum. These peculiarities in distribution may be regarded as
evidence for a high degree of metamorphic (catagenetic) transformation of oils which
is in agreement with a longer existence of the enclosing sedimentary rocks.
Thus, all the regularities in the sulfur distribution of the petroleum fractions
considered above are consistent with the concept of secondary sulfurization and
catagenetic thermal-destructive transformations of oil components.
II.3. Group Chemical Composition of Organic Sulfur Compounds in

Crude Oils
The sulfur compound chemical composition in oils is determined by the type of

occurrence, geological age, initial organic matter, and other factors. Depending upon
different sulfur compounds present in oils, i.e. on the group chemical composition
of sulfur compounds, the oils can be conventionally divided into three types: (i)
Mercaptan oils in which mercaptans are present in amounts prevailing or comparable
with those of sulfides and thiophenes. Hydrogen sulfide, disulfides, and elemental
sulfur may also be present in these oils. (ii) Sulfide oils where sulfides are present in
predominant amounts, thiophenes in comparable or lower amounts, and the mercap-
tan content does not exceed 5%. (iii) Thiophene oils with predominant amounts of
thiophenes and no more than 10% of sulfides, other sulfur compounds being absent.
The hydrogen sulfide content of oils is not constant and depends on selection,
storage, and transportation. The sulfide oils are most abundant in nature. Each type
of oil is characterized not only by differences in the group hydrocarbon composition,
but also by sulfur compound thermal stability which presents an important
technological parameter. 8 In the process of oil refining, sulfur compounds undergo
destruction due to the action of temperature and catalytic and other factors.
Therefore, the group chemical composition of sulfur compounds in refined oil
products differs from that in native oil. This·should be taken into account when the
sulfur compound group chemical composition of distillates and residues of oil
refining is considered. The sulfur compound thermal stability decreases from oils of
type Ill to oils of type I. For oils of type Ill and 11, the sulfur compound content of
all the successively boiling fractions increases with increasing the sulfur compound
content of the initial oil. In mercaptan oils the sulfur compound content in light
distillates may be higher than in heavy distillates and dependent mainly upon the
sulfur compound thermal stability. Therefore, the group chemical composition of
the straight·run, especially light, distillates differs much in oils of different types. With
rising boiling point of the distillates this difference becomes smaller. Elemental sulfur,
hydrogen sulfide, mercaptans, and disulfides which most strongly deteriorate the
useful properties of petroleum products, are normally concentrated in light fractions.
Let us consider the results of systematization of the file of experimental data
concerning the sulfur compound group composition of 256 oils (Table 4,
TABLE 4
Chemical Composition of Organic Sulfur Compounds in Crude Oils
A) Content in Petroleum, Wt. %; B) Content, Wt. % of Total Sulfur Compound Contents
0
Sulfur content :;d
0
Lithology of Age of Depth or

total sulfur elemental mercaptan sulfide residual
-
>
z
(":)
ell
c:
collectors deposits occurrence. m a a b a b a b a b !""'
~
:;d
I 2 3 4 s 6 7 8 9 10 11 12 (":)
0
Terrigenous Cretaceous 0-500 1.320 0.000 0.0 0.005 0.4 0.360 27.3 0.955 72.3
..,a:
0
1500-2000 1.095 0.000 0.0 0.000 0.0 0.253 23.1 0.840 76.9 c:
2000-2500 1.509 0.000 0.0 0.000 0.243 16.1 1.266 83.9
z
0.0 0
ell
average 1.441 0.000 0.0 0.000 0.0 0.249 17.3 1.191 82.7
..,.,
0
Jurassic 2500-3000 0.87 0.000 0.0 0.000 0.0 0.07 8.0 0.80 92.0 m
;I
Mesozoic average 1.420 0.000 0.0 0.000 0.0 0.243 17.1 1.177 82.9 0
!""'
m
c:
Carbonic 500-1000 1.676 0.000 0.0 0.018 1.1 0.366 21.8 1.292 77.1 a:
1000-1500 2.232 0.000 0.0 0.026 1.2 0.410 18.4 1.804 80.4
1500-2000 1.353 0.000 0.0 0.023 1.7 0.276 20.4 1.054 77.9
2000-2500 1.590 0.000 0.0 0.004 0.3 0.168 10.6 1.418 89.3
average 1.908 0.000 0.0 0.017 0.9 0.351 18.4 1.538 80.3
-
.....
N
TABLE 4 (Condnued)
0
1 2 3 4 5 6 7 8 9 10 11 12 ;t1
Devonian 1000-1500 1.644 0.000 0.0 0.004 0.2 0.349 21.2 1.291 78.6
=
0
&;
1500-2000 1.358 0.000 0.0 0.003
2000-2500 1.303 0.000 0.0 0.004
0.2
0.3
0.274
0.285
20.2
21.9
1.081
1.014
79.6
77.8
~
~
2500-3000 1.009 0.000 0.0 0.006 0.6 0.141 14.1 0.862 85.3 ~
3000-3500 0.19 0.000 0.0 0.001 0.5 0.007 3.7 0.182 95.8
average 1.312 0.000 0.0 0.004 0.3 0.258 19.7 1.050 80.0
Paleozoic 500-1000 1.676 0.000 0.0 0.018 1.1 0.366 21.8 1.292 77.1
Total 1000-1500 2.077 0.000 0.0 0.020 1.0 0.394 19.0 1.663 80.0
1500-2000 1.356 0.000 0.0 0.011 0.8 0.275 20.3 1.071 78.9
2000-2500 1.389 0.000 0.0 0.004 0.3 0.250 18.0 1.135 81.7
25!)0--3000 1.009 0.000 0.0 0.006 0.6 0.141 14.1 0.862 85.3
3000-3500 0.19 0.000 0.0 0.001 0.5 0.007 3.7 0.182 95.8
average 1.598 0.000 0.0 0.010 0.6 0.303 19.0 1.284 80.4
Carbonic Paleogene 0-500 4.03 0.000 0.0 0.010 0.2 0.25 6.2 3.77 93.6
1000-1500 5.15 0.000 0.0 0.017 0.3 0.27 4.7 5.463 95.0
average 4.89 0.000 0.0 0.014 0.3 0.26 5.5 4.617 94.2
Permian 500-1000 3.030 0.035 1.2 0.161 5.3 0.339 11.2 2.495 82.3
1000-1500 2.889 0.010 0.3 0.107 3.7 0.578 20.0 2.194 76.0
1500-2000 2.336 0.000 0.0 0.081 3.5 0.423 18.1 1.832 78.4
average 2.852 0.018 0.6 0.124 4.3 0.459 16.1 2.251 79.0
Carbonic 500-1000 2.422 0.000 0.0 o.06o 2.5 0.353 14.6 2.009 82.9
1000-1500 2.064. 0.002 0.1 0.025 1.2 0.391 18.9 1.646 79.8
1500-2000 2.218 0.006 0.3 0.042 1.9 0.308 13.9 1.862 83.9
2000-2500 1.480 0.029 2.0 0.060 4.1 0.305 20.6 1.086 73.3
average 2.114 0.005 0.2 0.038 1.8 0.351 16.6 1.720 81.4 0
::t1
0
Devonian 1000-1500 3.72 0.010 0.3 0.023 0.6 0.720 19.4 2.977 19.1 >
z
.....
1500-2000 0.680 0.004 0.6 0.044 6.5 0.117 17.2 0.515 15.1 (")
Cl)
2000-2500 0.795 0.002 0.3 0.058 7.3 0.120 15.1 0.660 77.3 C!
0.974 I'""
average 1.225 0.004 0.3 0.045 3.7 0.218 17.8 78.7
~
::t1
Paleozoic 500-1000 2.749 0.019 0.7 0.114 4.1 0.345 12.6 2.271 82.6 (")
0
1000-1500 2.314 0.004 0.2 0.045 1.9 0.446 19.3 1.819 78.6 a:
'"d
1500-2000 2.040 0.005 0.2 0.047 2.3 0.298 14.6 1.690 82.9 0
2000-2500 1.252 0.020 1.6 0.059 4.1 0.243 19.4 0.944 74.3 C!
average 2.218 0.008 0.4 0.059 2.7 0.366 16.5 1.786 ' 80.4
z
t:1
Cl)
0
'Tl
'"d
~
0
I'""
"'
C!
3:::
12-' G. F. BOlSHAKOV
-.....
E~
. :~~
. '
''
i·
'· c
' ' ,........ -- --
'· ~ ,,
B '·---''
...... ... _
A~
FIGURE 7. Variation in the concentration of sulfur: total (a), elemental (b), mercaptan (c), sulfide (d),
and residual (e) in oils from terrigenous (solid lines) and carbonaceous (dotted lines) Paleozoic rocks
depending on the depth of occurrence of the horizons.
Figs. 7, 8). The systematization has been carried out using a recognized principle
of oil classification according to geologo·geochemical characteristics. 4 •8•22 •28
Elemental sulfur occurs most frequently in oils of Paleozoic carbonate collectors.
Its concentration does not exceed 0.1 %, being on average ea. 0.008%. Sporadic
traces of elemental sulfur in oils of terrigenous deposits (up to 0.013% of oil) seem to
be associated with hydrodynamic contact between oils and fluids from adjacent
carbonate strata. The average elemental sulfur content of oils from terrigenous
collectors is less than w- 3 %.
The oils studied are practically free from hydrogen sulfide.
Mercaptans occur in varying quantities. Some oils, for example Low Cretaceous
and Jurassic oils, are practically free from mercaptans. These oils occur, as a rule, in
terrigenous collectors and show on average as little as 0.01% mercaptan sulfur. In
some rare samples of these oils, usually in those which show a higher elemental sulfur
content, the mercaptan sulfur content may reach 0.2% of the oil and higher. The
average mercaptan sulfur content of oils from terrigenous collectors decreases
smoothly with increasing age and depth of occurrence. In Devonian oils occurring
below 2000 m thiols are present in amounts as small as 0.3-0.6% of the total sulfur
compounds.
Low contents and sometimes the absence of mercaptans are common for some
Dcvonian and Carboniferous oils in the Ural·Volynsk districts of the USSR. In spite
of low mercaptan content the total sulfur content of these oils is rather high reaching
3-5%, which corresponds to a 15-25% sulfur compound content of the oil.
100 B
-
.- -
20- ~ ,~ I
. r
/
' '-.i
...
'ID·
n~~ 111111®.
fO
1 2 ~
DEPTH OP OCCURRENCE, KM
FIGURE 8. Sulfur compound average ~roup composition of oils from terrigenous (a) and carbo-
naceous (b) Paleozoic collectors dependmg on the depth of occurrence.
lffiTII elemental
sulfur 1I1I1I1II1 sulfides
~ mercaptans CJ "residual sulfur"-containing sulfur compounds
In many oils of West Siberia no mercaptans have been found. These oils occur
mainly in Low Cretaceous sandstones.
Oils displaying high mercaptan contents are usually characterized by methane
contents and associated with carbonate deposits. 8 •29 Oils of Permian limestones
contain over 0.12% mercaptan sulfur on average. In some oil samples collected at
depths below 1000 m, the mercaptan sulfur concentration approaches 0.45%. \Vith
increasing depth of strata, the mercaptan sulfur concentration and the content of
thiols among the sulfur compounds gradually decreases. In oils of Prepermian
carbonate rocks, i.e., Carboniferous and Devonian, the average mercaptan sulfur
126 G. F. BOI.SHAKOV
content changes with depth in a more complicated fashion. It is minimal at a depth of

1000-1500 m and rises with both increasing and decreasing depth of oil occurrence.
Similarly, the average content of thiols among the sulfur compounds of these oils
changes, accounting for 0.6-1.2% at a depth of 1000-1500 m and 4.1-7.3% in
horizons deeper than 2000 m.
In East Siberia an Old Cambrian oil field with an unusually high mercaptan content
was discovered near the settlement of Markovo. Along with this extremely high
mercaptan content, a unique characteristic of this oil is also the absence of elemental
sulfur, sulfides, and disulfides. With a total sulfur content of 0.96-1.08%, mercaptans
and residual sulfur constitute only 0.500-0.707 and 0.460-0.373%, respectively.
Thus, the organic sulfur compounds of Markovo oil consist of mercaptans and
thiophenes.
Among oils occurring in the Ural-Volga region, the largest amounts of mercaptans
are observed in sulfur-rich oils of the Ishimbai deposit and the Kuibyshev area (up to
0.3 and 0.448% mercaptan sulfur, respectively) but these amounts of mercaptans are
considerably lower than in Markovo oil.
At the present time, few· mercaptans have been identified in oils.
As is evident from the data of Table 5 and Refs. 29 •30 some mercaptans contain
secondary and tertiary structures. The primary mercaptan contents of oils is consider~
ably lower. In Libyan oil, for example, the 2- and 3-thiol substituted isomers consist
of 37% mercaptans C4H 9SH and 63% mercaptans C6H 11 SH. 30 The authors 31 have
established that the mercaptans of the kerosine fractions of four oils contain 5, 75, and
20% of primary, secondary, and tertiary structures, respectively. The C4 and Cs
mercaptans of Libyan oil mainly possess linear structures whereas the related
hydrocarbons are branched.
TABLES
Individual Mercaptans Identified in Oils30 •41 • 173
Boiling Content or
Compounds point, °C oil, wt. %·to-' Oil
1 l 3 4
Methanethiol 5.95 2.40 Wasson, USA

Methanethiol 5.95 0.029. Libyan
Ethanethiol 35.00 5.30 Wasson
Ethanethiol 35.00 0.231· Libyan
1-Propanethiol 67.6 0.41 Wasson
1-Propanethiol 67.6 0.274* Libyan
2-Propanethiol 52.56 1.99 Wasson
2-Propanethiol 52.56 1.789• Libyan
1-Butanethiol 98.46 traces Wasson
1-Butanethiol 98.46 0.159* Libyan
TABLE S (Continued)
1 2 3 4
2-Butanethiol 84.98 3.86 Wasson

2-Butanethiol 84.98 1.377* Libyan
2-Methyl·1·propanethiol 88.72 0.03 Wasson
2-Methyl-1-propanethiol 88.72 0.072* Libyan
2-Methyl-2-propanethiol 64.22 o.S5* Wasson
2-Methyl-2-propanethiol 64.22 0.159* Libyan
1·Pentanethiol 126.64 0.375* Libyan
1-Pentanethiol 126.64 0.105* Arabian, Saudi Arabia
2-Pentanethiol 112.9 1.40 Wasson

2-Pentanethiol 112.9 0.719* Libyan
3-Pentanethiol 105 0.57 Wasson
3-Pentanethiol 105 0.779* Libyan
2-Methyl-1-butanethiol 118.2 0.043* Libyan
3-Methyl-1-butanethiol 118 0.173* Libyan
2-Methyl-2-butanethiol 99 1.26 Wasson
2-Methyl-2-butanethiol 99 0.144* Libyan
3-Methyl-2-butanethiol 0.101* Libyan
2,2-Dimethyl-1-propanethiol 64.22 0.047* Arabian
2-Hexanethiol 138.9 2.80 Wasson
2-Hexanethiol 138.9 1.140* Libyan
2-Hexanethiol 138.8 0.769* Arabian
2-Methyl-2-pentanethiol 0.384* Arabian
2-Methyl-3-pentanethiol 135 0.101* Libyan
1·Heptanethiol 176.2 0.361* Libyan
1-Heptanethiol 176.2 0.338* Arabian
2-Heptanethiol 163.6 0.851* Libyan
2· Heptanethiol 163.6 1.048* Arabian
2-0ctanethiol 186.4 0.303* Libyan
2-0ctanethiol 186.4 0.396* Arabian
Cyclohexanethiol 158.8 1.20 Wasson
• Concentration, mg/1
128 G. F. BOLSHAKOV
Mercaptans from the high-molecular part of oil present a rather complicated

problem for research and that is why they are the least studied compounds up to now.
The thiols in the high-boiling fractions of oil are most likely alkylthiophenols,
32
including polycyclic alkyltiophenols. This suggestion is supported by some data
providing evidence for the presence in the 280-440 oc fraction of Kuwait oil of
alkylthiophenols of not exactly identified structure, which contain 10-15 carbon
atoms in side chains. More complete data concerning the contents and identification
of thiols in the high-boiling fractions are not available.
Sulfides are found in almost all oils. Their contents amount to 50-70% of the total
sulfur compounds, although sometimes sulfides are contained in small quantities.
As noted above, the unique Markovo oil contains no sulfides.
It has been established by many scientists that acyclic sulfides are present in large
quantities in methane oils, whereas cyclic sulfides occur in oils with a predominant
content of cyclic structures. 29 •33 •34 Thus, the hydrocarbon skeletons of the sulfides
correspond to those of the bulk of the hydrocarbons of petroleum. A correlation
between the group chemical composition of sulfides and the general cyclicity of
petroleum has been established. For example, in mercaptan-free naphthene oils of
Wilmington (USA) and South Uzbekistan35 , the content of aliphatic sulfides is never
higher, if present at all, than 3% of the total sulfides. In methano-naphthene
mercaptan Wasson oil (USA) thiophanes reach 23% of the sum of all sulfides, while
in high-mercaptan methane oil from the Middle East acyclic sulfides are
predominant. 36 The aliphatic sulfide content of gas condensates of Tadzhikistan
(USSR) increases with the depth of occurrence in line with the content of mercaptans
and disulfides. 37 The general cyclicity of petroleum decreases in an analogous way. 38
A relative increase in the content of aliphatic mercaptans and sulfides in going from
West-Surgut oil to more methane-rich Arian oil (USSR) has been noted. 39
The highest concentrations of sulfides have been found in oils occurring at depths to
1000-1500 m, in terrigenous and carbonate oil fields (up to 0.41 and 0.72%,
respectively) independent of their age. The change in the sulfide sulfur concentration
in oils of terrigenous collectors with increasing depth is similar to the change in the
total sulfur content. Oils of Paleozoic carbonate deposits are somewhat richer in
sulfide sulfur than oils of terrigenous rocks. The maximum in the 100-1500 m range is
even more distinct in spite of a smooth decrease in the total sulfur content with depth
(Fig. 7).
Of 100 sulfur atoms contained in oils of Mesozoic and Paleozoic terrigenous
deposits, 4 to 27 occur in sulfides. This amount decreases with the depth of occurrence
in all the stratigraphic complexes (Fig. 8).
The contribution of sulfide sulfur to the composition of the investigated sulfur-rich
oils of Paleogene carbonate rocks is not high (5-6%). The portion of sulfides in sulfur
compounds of the carbonate Paleozoic oils varies within a narrow range {11-21% ).
The highest quantities of sulfides are contained in oils occurring at a depth below
1000 m. So, the sulfide content of oils from carbonate oil fields does not decrease with
increasing depth (Fig. 8).
About 100 individual aliphatic sulfides have been identified up to now. This
research was started by C. Mabery40 who isolated from oil, but did not identify th
aliphatic sulfides C3-C 12 • ' e
Some aliphatic sulfides isolated from oils are listed in Table 6. Among the aliphatic
sulfides, diprimary and disecondary compounds dominate. 30 •41 Hydrocarbon frag-
ments with more than three carbon atoms are bound to sulfur more often via
secondary than via primary C-atoms. Therefore isomers with a-substituents are
TABLE6
Aliphatic Sulfides Identified in Oils30•41 •173
Boiling Content in
Sulfides point, oc oil, wt. % • 103 Oil
I 2 3 4
2-Thiapropane 37.34 0.88 . Wasson, USA

2-Thiapropane 37.34 0.928* Libyan
2-Thiabutane 66.65 2.22 Wasson
2-Thiabutane 66.65 2.20 Agha J ary, Iran
2-Thiabutane 66.65 0.303* Libyan
2-Thiapentane 95.54 0.30 Wasson
2-Thiapentane 95.54 1.34 Agha Jary
2-Thiapentane 95.54 0.187* Libyan
3-Thiapentane 92.10 0.75 Wasson
3-Thiapentane 92.10 5.71 AghaJary
3-Thiapentane 92.10 0.043* Libyan
3-Thiapentane 92.10 0.116* Arabian, Saudi Arabia
3-Methyl-2-thiabu tane 84.75 0.64 Wasson
3-Methyl-2-thiabutane 84.75 0.74 AghaJary
3-Methyl-2-thiabutane 84.75 0.195* Libyan
3-Methyl-2-thiabutane 84.75 0.070* Arabian
2-Thiahexane 123.2 0.077 Wasson
2-Thiahexane 123.2 0.043* Libyan
2-Thiahexane 123.2 0.035* Arabian
3-Thiahexane 118.50 0.12 Wasson
3-Thiahexane 118.50 0.043* Libyan
3-Thiahexane 118.50 0.186* Arabian
3-Methyl-2-thiapentane 112 0.476* Libyan
4-Methyl-2-thiapentane 112.5 0.159* Libyan
4-Methyl-2-thiapentane 112.5 0.093* Arabian
2-Methyl-3-thiapentane 107.38 0.43 AghaJary
130 G. F. BOLSHAKOV
TABLE 6 (Continued)
1 2 3 4
2-Methyl-3-thiapentane 107.38 0.101• Libyan

2-Methyl-3-thiapentane 107.38 0.070* Arabian
4-Methyl-2-thiahexane 138 o.OS8* Libyan
4-Methyl-2-thiahexane 138 0.035* Arabian
2-Methyl-3-thiahexane 132.05 0.078 Wasson
2-Methyl-3-thiahexane 132.05 0.130* Libyan
2-Methyl-3-thiahexane 132.05 o.OS8* Arabian
4-Methyl-3-thiahexane 132.05 0.50 Wasson
4-Methyl-3-thiahexane 133.65 0.43* Libyan

4-Methyl-3-thiahexane 133.65 0.070* Arabian
5-Methyl-3-thiahexane 134.22 '0.43* Libyan
5-Methyl-3-thiahexane 134.22 0.070* Arabian
3,3-Dimethyl-2-thiapentane 0.043* Libyan
2,2-Dimethyl-3-thiapentane 120.41 0.058 Wasson
2,4-Dimethyl-3-thiapentane 120.02 0.53 Wasson
2.4-Dimethyl-3-thiapentane 120.02 0.023* Arabian
2-Thiaoctane 171 0.707* Libyan
2-Thiaoctane 171 0.478* Arabian
2-Methyl-3-thiaheptane 0.043* Libyan
2-Methyl-4-thiaheptane 0.012* Arabian
3-Methyl-4-thiaheptane 0.070* Arabian
2,2,4-Trimethyl-3-thiapentane o.OS8* Libyan
3-Methyl-4-thiaoctane 0.260* Libyan
3-Methyl-4-thiaoctane 0.175* Arabian
3,5-Dimethyl-4-thiaheptane 165 0.245* Libyan
3,5-Dimethyl-4-thiaheptane 165 0.012* Arabian
3-Thianonane 193 0.011* Rumelan
5-Thiaundecane 235 0.017* Rum elan
Cyclohexyl 1-pentyl sulfide 128 0.028* Rumelan
• Concentration mg/1
TABLE 7
Composition (Wt. %) of Sulfide Fractions of Kerosine Distillate (240-350 °C)
from Emba Oils41
Fractions
Characteristic
Sui fides peaks, m/e 3 s 7 9 10
Alkyl sulfides 47 3.8 5.4 4.60 10.70 8.7

Cycloalkyl sulfides 68 80.9 81.4 65.9 64.1 70.6
Monocyclic thiacycloalkanes 87 12.90 9.65 0.20 0.3 2.34
Bicyclic thiacycloalkanes 127 1.78 2.6 17.1 8.3 2.20
Tricyclic thiacycloalkanes 167 0.54 0.96 10.4 8.1 2.97

Tetracyclic thiacycloalkanes 207 1.8 4.30 8.30
Pentacyclic thiacycloalkanes 247 4.25 4.90
predominant among the aliphatic sulfides. In Libyan oil, for example, the number of
sulfide isomers with a different position of substituents is as low as 7%. Unbranched
hydrocarbon fragments are the most important structural elements of the acyclic
sulfides. Thus, diethyl, ethyl propyl, methyl propyl, dipropyl, ethyl butyl, propyl
butyl, butyl amyl, butyl hexyl, diallyl, butyl octyl, ethyl decyl, and dihexyl sulfide
have been identified in the kerosine fraction of Emba oils. 42 The relative content
of these sulfides is not high, reaching 3-10% of all sulfur compounds isolated (Table
7). Sulfur compounds were isolated from the 240-350°C fraction of Emba crude oil by
two-step sulfuric acid extraction. 43 The concentrates of sulfur compounds isolated
were distilled in vacuo into 10 fractions. Table 7 shows mass spectroscopic data of
sulfur compound fractions with the highest concentrations of sulfides.
As with thiols, the ratio of linear to branched fragments is higher for the aliphatic
sulfides than for the corresponding hydrocarbons of the same petroleum. 4
A few alkyl cycloalkyl sulfides have been found in oils of Wasson (USA) 4\ West
Siberia,45 and Emba42 (USSR). These compounds are mainly alkyl cyclohexyl
sulfides. Normally, their concentration is considerably lower than that of the aliphatic
sulfides, but when the oils contain predominantly thiophanes, the content of alkyl
cycloalkyl sulfides equals the content of thiaalkanes. 46 In the kerosine fraction of
Emba oil, however, the cycloalkyl sulfides dominate (Table 7).
Alkyl aryl sulfides are present in oils in approximately the same quantities as alkyl
cycloalkyl sulfides. Phenyl s-butyl sulfide (I), o-, m-, p-tolyl isopropyl sulfide (11, Ill,
IV) have been identified in Wasson oil. 47 Secondary aliphatic hydrocarbon fragments
are most common in alkyl aryl sulfides. The content of the isomers (I-IV) has not
been established, but the IR spectrum of the isolated concentrate corresponds best to
a I: 11: Ill: IV ratio of 49: 11: 32:8. It is of interest that these ratios correlate with the
corresponding ratios of dialkylbenzenes in gasoline fractions. 48 This also indicates a
common genesis of the sulfur compounds and the hydrocarbons of oils.
132 G. F. BOLSHAKOV
The alkyl phenyl sulfides, their naphthenologs, C 0 Hzn-zS (z = 6, 8, 10) and

polynaphthenoalkyl thienyl sulfides, ~n-zS (Z = 10, 12, 14) have been found in a
quantity of about 4% in a concentrate isolated from the 350-530 oc fraction of
Recluse oii. 49 Oils may possibly still contain unidentified dicycloalkyl, cycloalkyl aryl,
and diaryl sulfides. Five- and six-membered sulfur-containing heterocycles and their
homologs constitute a major part of sulfides in many oils. Their content is especially
high in intermediate-boiling oil distillates. The heterocycle may add up to 7 fused
cycloalkane rings. 4 The greater part of the thiacycloalkanes boiling at temperatures
below 400 oc possesses monocyclic structures, the concentration of the polycyclic
compounds decreasing as the number of rings in the molecule increases. In the
intermediate-boiling distillates of Arian, Iranian, Arabian, and Libyan oils, as well as
oils of South Uzbekistan and some oils of the United States, thiacyclopentanes and
thiacyclohexanes constitute 60-70 and 30-40% of the total amount of thiamonocy-
cloalkanes, respectively. Six- and five-membered rings without sulfur occur in about
30 and 70% of thiabicycloalkanes, respectively, in the Arian oil fractions. The
approximate sulfur compound ratio of Arian oil is as follows (according to mass
spectrometric data): 50
In the fractions 140-240 oc of West Siberian oi1, 51 190-360 oc and 200-275 oc of

Arian oi1, 52 68-115 °C/6 mm Hg of Kyzyl-Tumshuk and 50-98 °C/3 mm Hg of
Khaudag oils 53 the molecular-mass distribution of thiamono-, thiabi- and thiatricy-
cloalkanes is unimodal, with the maxima corresponding to sulfur compounds
possessing 10, 10-11, and 12-13 carbon atoms.
The composition and structures of the thiacycloalkanes of oils of West Siberia, the
Ural-Volga region, and Middle Asia of the USSR are of the same type. 24 In the cyclic
sulfides, the sulfur atom is, as a rule, in the a-position to a neighboring ring. In
Romashkinskaya oil (USSR), however, sulfur compounds with the sulfur atom in a
{3-position with respect to the ring have been found. 4
c2-w-c5
a1 = H; c1-c 5
R2; R3 = H; c,-cs
The Arian oil thiamonocycloalkanes contain three and the thiabicycloalkanes tw
alkyl substituents, one of which possesses a linear structure of fairly high molecula~
mass, the others being C 1 and ~. This is supported by the fact that C 10-~0
hydrocarbons of normal and isoprenane structure have been found among the
products of the desulfurization of sulfides isolated with TiC14 from the 300-325 oc
distillate off West Siberian oil. The hydrogenative sulfurization conditions and
chromatographic procedures have been reported. 4 Analogous results have been
obtained in a similar study of aromatic-sulfur concentrates from the 270-340 oc
fraction of Low Cretaceous West Siberian oil of the Fedorovo deposit. The ratios of
normal alkane and isoprenoid skeletons in the hydrocarbon and thiamonocycloalkane
fractions of the distillate are fairly similar, but the isoprenoid structure content in
sulfides is almost 1.5 times as large as in alkanes. Thus, the (i-C 19 + i-~0): (n-C 1, +
n-C 18 ) ratios are 0.67 for the sulfides and 0.47 for the hydrocarbons. lt is obvious that
normal alkanes and isoprenes Cto-Czo a~e formed only by elimination of su\hn
either from a-a)kyl- or a-,a'-dia)kyJ substituted thfamonocycloalkanes of the ty
(VIII-X).4,s4 pe
a,, R2 - unhrRnched
alkyl structures
Up till now a considerable amount of cyclic sulfides has been identified in

petroleum (Table 8). These compounds form a single homologous series in which the
positions of the substituents R 1 and R 2 are strictly regular. In compounds VII and
VIII it is most likely that R 1 = H, R 2 = CH3 , the molecular mass in the homologous
series increasing with the length of R 2 •
TABLE 8
Cyclic Sulfides Identified in Oils30 •41 •173
Boiling Content in
Cyclic sulfides point, °C oil, wt. % 103 Oil, Country
1 2 3 4
Thiacyclopentane 121.117 0.077 Wasson, USA
2-Methylthiacyclopentane 133.23 0.46-2.30 Wasson, USA
2-Methylthiacyclopentane 133.23 0.678-0.764. Libyan, Libya
2-Ethylthiacyclopentane 157
3-Ethylthiacyclopentane 165
134 G. F. BOLSHAKOV
TABLE 8 (Continued)
1 2 3 4
2,2-Dimethylthiacyclopentane 0.30J• Libyan, Libya

2,3-Dimethylthiacyclopentane 1.515* Ubyan, Libya
2,4-Dimethylthiacyclopentane 147-148
2,5·Dimethylthiacyclopentane 142.14 0.40-3.50 Wasson, USA
2,5-Dimethyltbiacyclopentane 142.16 0.764• Libyan, Libya
3,4-Dimethylthiacyclopentane 155.4-156.0
2-Propylthiacyclopentane 179.3-179.8
2-Methyl-5-ethylthiacyclopentane 58-59/15**
2,3,5·Trimethylthiacyclopentane 162-163
3-Butylthiacyclopentane 210
2-Methyl-5-propyltbiacyclopentane 78/17 ..
2,4-Dimethyl-5-ethyltbiacyclopentane 170/744**
Thiacyclohexane 141.75 0.33 Wasson, USA.
2-Methylthiacyclohexane 153.04 2.90 Wasson, USA.
2-Methylthiacyclohexane 153.04 0.635• Libyan, Libya
3-Methylthiacyclohexane 158.04 0.034 Wasson, USA.
3-Methylthiacyclohexane 158.04 1.183* Libyan, Libya
4-Methylthiacyclohexane 158.64 0.048 Wasson, USA..
2-Ethylthiacyclohexane 107.7/45..
3- Ethylthiacyclobexane 92.2/43 ..
4-Etbylthiacyclohexane
2,3-Dimethylthiacyclohexane 163.5/766..
* Concentration, mg/1; **pressure, mm Hg

The following cyclic sulfides have been qualitatively determined in oils: 3,3-dimethyl-; 2-methyl-3-ethyl-; 2-methyt.4 _
ethyl; 3-ethyl-; 2,4-dimethyl-; 2,2,3·; 2,2,4-; 2,2,5-; 2,3,4-; 2,3,5-; 2,4,4-trimethyl-; 2,5-diethyl-; 2-methyl-5-propyt••
3-butyl-; 3-methyl-4-propyl-; 4 methyl-2-isopropyl-; 2,3-dimethyl-5-ethyl-; 2,2,3,5-; 2,2,4,5-; 2,2,5,5-; 2,3,4,5 .:
3,3,4,5-; 2,2-dimethyl-5-propyl-; 2,2-dimethyl-4-isopropyl-; 2,2-dimethyl-5-isopropyl-; 2,3,4-trimethyl-5-ethyl-; 2,3,s:
trimethyl-5-ethyl-; 2,2,3,~,5-pentamethylt~iacyclopentane~ 4-ethyl-; 2,3-; 2,4; 2,6-dimethyl-; 2-methyl-6-ethyl-; :2.-
methyl-6-ethyl-; 2,3,6-tnmethyl-; 2,4,5-tnmethyl·; 2,5-dlmethyl-2-ethyl-; 2,3,3,6-tetramethyl-; 2,2,5-trimethyl-s
ethylthiacyclohexane. •
The following compounds have been isolated55 from Iranian oil:

These compounds are thia analogs of the hydrocarbons present in the oils.
The thiabicycloalkanes of intermediate-boiling fractions of Romashkinskaya oil
have been suggested56 to possess the following structure: where R1 and Rz are CH3 or
R:Bs/l(cH )ncH3 :ti)(cH )ncH 3 2 2

I II
R1{1l ~
l~CH 2 )m (CH2 )PCHJ
R2 S
III
CzH 5 , n = 2-6, p and m being 0-4.

Structures I, 11, and Ill seem to be the most probable. 37
In some oils (in Romashkinskaya, USSR, for example) the relative content of
thiamonocyclic compounds among the total cyclic sulfides decreases in going from
light fractions to vacuum gas oil. But the concentration of thiamonocycloalkanes
remains still higher in comparison with the content of their naphthenologs. The
relative ratio of cyclic sulfides with 1, 2, 3, 4, and 5 rings is 22: 14:7:4: 1.3. 57
In the polycyclic sulfides, the sulfur atom occurs, as a rule, in the terminal ring. A
significant increase in the content of thiapolycycloalkanes in the sum of saturated
sulfur compounds at a relatively high thiamonocycloalkane content has been
revealed58 in heavy (410-450 °C) distillate from West-Surgut oil. In lighter distillates
of these oils, the thiacycloalkanes are also present in considerable quantities (Table
9).
The condensed thiacycloalkanes contain a significant amount of aliphatic struc-
tures. As the number of condensed structures increases the content of aliphatic
carbon atqms decreases (Table 10). The largest amounts of aliphatic structures are
observed in Wilmington naphthene oil.
Benzothiacycloalkanes are present only in fractions boiling above 230 °C and
consist of thiaindanes and thiatetralines. Their concentration in intermediate-
boiling distillates is not high, usually not exceeding 10% of the total sum of sulfides
(Table 11). In Wasson oil, together with 1-thiaindane, the following derivatives have
been identified: 2-, 3-, 5-, (or 7-) methyl-, 2,2-, 2,3-, 2,4-, 2,5- (or 2,7-), 2,6-, 3,3-, 3,5-
(or 3,7-), and 3,6-dimethyl-, 2-ethyl-, 2-methyl-, 2-ethyl-3-ethyl, 2,2,4-, 2,3,4-, and
2,3,5- (or 2,3,7-) trimethyl-1-thiaindane. 29 Among them the compounds with alkyl
S.R.-B
136 G. F. BOLSHAKOV
TABLE9
Structural·Chemical Composition of Sulfides of West Surgut Oil
(% of distillate)14•76
Distillates, %C
Structures 190-360 360-410
RSR 0.56 0.37
Q 4.11 4.26
w 1.63 3.28
CXX) 0.46 2.88
cxxo 0.11 1.97
1.43
RS-o 0.62
RS-o 0.11
RS-g 0.22
substituents in the a-position are most abundant. No tetramine thia homologs have
been isolated and identified yet.
60
The same authors have found 3.2-10.5% of compounds CnH2n-zS with z = 8-20
in the 370-535 oc vacuum gas oils of various oils. These compounds contain one
benzene ring and up to seven saturated rings. A small amount of arenothia-
cycloalkanes with two benzene or naphthalene rings which also may involve the
corresponding thia analogs conjugated with arene moieties, have been found in the
same fractions. Besides, naphthenothiaindanes have been observed in the 350-450 oC
fraction of Romashkinskaya oil, USSR. 61
TABLE 10
Structural-Chemical Composition of Thiacycloalkanes from 370-535 °C
Fractions of Some Oils
Number of aliphatic C atoms

Number of rings Number ofC
in the molecule atoms In rings Gach Saran Swan llills Wilmington
1 4-5 19-30 14-33 18-36

2 7-9 9-28 10-28 14-31
3 10-13 8-24 9-30 10-30

4 13-17 1-22 5-28 6-27
5 16-21 0-19 2-25 2-24
6 19-24 0-17 3-22 0-22
7 22-26 0-14 0-9 0-19
TABLE 11
Group Chemical Composition of Sulfides in Some Oils
Content, % of sum of
sulfides thiacycloalkanes
Oil fields
Arian (Bashkiria, USSR) 190-360 14.3 77.5 8.2 63 22 11 4

West Surgut (West Siberia, USSR) 190-360 11.7 82.8 5.5 72 20 6 2
Samotlor (West Siberia, USSR) 190-360 7.2 88.2 4.6 63 2.f 10 3
Khaudag (Tadzhikistan, USSR) 150-350 1 0.5 95.9 3.6 61 26 11 2
Kyzyl-Tumshuk (Tadzhikistan) 150-350 7.2 90.0 2.8 59 27 10 4
Lyal-Mikar (Tadzhikistan) 200-400 16.8 80.5 2.7 66 22 10 2
Kokait (Tadzhikistan) 200-400 8.3 90.0 1.7 77 17 4
Wasson (USA) 150-220 22.8 66.5 10.7 84 10 6
Wilmington 150-250 0.0 84.4 15.6 64 21 9
138 G. F. BOLSHAKOV
The thiophene homologs are present in nearly all oils in amounts of 45-84% of
the total sulfur compound content in intermediate- and high-boiling
fractions. 29.37,41.42,62-64
Until now no disulfides have been identified in the oils considered or in other
erodes.
Mercaptans, sulfides, and disulfides represent no more than 27% of the total sulfur
in oil. The remaining sulfur, conventionally called "residual", includes compounds
with sulfur atoms in aromatic heterocycles (thiophenes, thiazoles) as well as, possibly,
higher members of other organic sulfur-containing functional series not amenable to
direct identification. Since no method is available for the independent determination
of aromatic sulfur functions, it is not possible to account for all sulfur atoms in
petroleum, a fact which makes the measurements of other sulfur compound
concentrations considerably less reliable. This disadvantage of the known procedures
of sulfur compound functional analysis requires the use in geochemical and other
considerations only of experimental data obtained by a self-consistent method.
The "residual" sulfur concentration in oils varies depending on the geological-
geochemical characteristics of the oil fields similarly to the total elemental sulfur
content (Fig. 7).
Since aromatic sulfur compounds are much more stable than other sulfur com-
pounds, the catagenic transformations of oils lead to a relative increase in the
"residual" sulfur content. In fact, as the catagenic processes are intensified with
increasing depth of occurrence, the "residual" sulfur portion in oils of terrigenous
enclosing rocks noticeably rises with decreasing total sulfur content, reaching 92% in
Jurassic West Siberian oil (2600 m) and 96% in deep-seated oil (3300 m) of the
terrigenous Devonian (Table 4).
No increase in the "residual" sulfur content with increasing depth is observed in oils
of carbonate collectors with catalytically inactive minerals.
A typical alkyl thiophene molecule of the 150-250 oc fraction of Arian oils contains
a short (~-C3 ) and a longer (C3-Cs) alkyl fragment and one or two methyl
groups. 65 According to spectral data and hydrodesulfurization data it has been
concluded that among these alkyl substituted thiophenes no monosubstituted deriva-
tives are present; about 10% of the compounds consist of 2-alkyl substituted
derivatives, with the alkyl substituents containing neither gem-dimethyl nor isopropyl
moieties66 •67 (Table 12). Among these thiophenes, 2-substituted compounds are
predominant in spite of the higher thermal stability of 3-substituted thiophenes. 68
If there are two or more alkyl groups in the thiophenes, one of the groups must
occupy rosition 2. Thiophenes with long aliphatic chains (C33-C36) have been
found 4 •4 in heavy straight-run oil fractions. Alkylthiophenes amounting to 3.5% have
been foun~ in the 320-530 "C fraction of the deparaffinate of Romashkinskaya oil. 62
Arenoth10phene fused compounds the concentration of which usually increase
with rising boiling point of the fractions are very abundant in oils. Of seven oils of th s
United States and the Middle East,69 the alkylthiophenes constitute as little as 1-6;
of the total amount of sulfur compounds. The benzo- and dibenzothiophen°
contents amount to 12-25 and 8-23%, respectively. 69 A similar distribution ~
arenothiophenes is common in 78 other oils. 3 Dibenzothiophenes are present in t~e
TABLE 12
Benzothiophenes Identified in Wasson Oi130•41 •173
Compounds Boiling point, oc mmHg Content wt. % • 103
Benzo[b]thiophene (benzothiophene) 217.5

2-Methylbenzothiophene 92.5/5 2.48
3-Methylbenzothiophene 128/25 0.95
4-Methylbenzothiophene
7-Methylbenzothiophene 0.10
2-Ethylbenzothiophene 221/10 0.37
3-Eth ylbenzothiophene 143/24 3.06

2,3-Dimethylbenzothiophene
2,4-Dimethylbenzothiophene 0.94
2,6-Dimethylbenzothiophene 100/9 0.13
2,7-and/ or 2,5-Dimethylbenzothiophene 134/11 1.01
3,5-and/ or 3,7-Dimethylbenzothiophene
3,6-Dimethylbenzothiophene 136.5/18 0.09
4,7-Dimethylbenzothiophene 0.04
2-Methyl-3-ethylbenzothiophene 145.5/17 0.06
2,4,7-Trimethylbenzothiophene 123.5/9
Note: Besides, 2-Methyl-4-ethyl- and/or 4-propylbenzothiophene; 2-methyl-5· and/or 2-methyl-7-ethyl- and/or S-

and/or 7-propylbenzothiophene; 2-ethyl-5- and/or 2-ethyl-7-methylbenzothiophene; 3-ethyl-5- and/or 3-ethyl-7-
methyl· and/or 2,3,5- and/or 2,3,7-trimethylbenzothiophene; 2,3,6-trimethyl· and/or 3-ethyl-6-methyl-benzo·
thiophene have been identified.
greatest amounts in the 300-450 oc fractions of Canadian oils.70 In the high-boiling

fraction polyarenothiophenes containing up to 5 condensed rings have been found.
The major part consists of triarenothiophenes.
The content of tetra- and penta-condensed arenothiophene derivatives is consider-
ably lower. Along with the arenothiophenes, their naphthenologs containing 1-3 and
sometimes up to 6 naphthene rings are present in oils. 33 •46 •69
The relative concentration of the naphthenologs in the corresponding series
decreases with increasing number of rings (Fig. 9). This conclusion is confirmed by
data on oils of the USSR, Venezuela, Algeria, and the Middle East. 4 •35 •57 •62 •63 •69 .71-77
In the deparaffinate of the 320-530 oc fraction of Romashkinskaya oil, for example,
the arenothiophenes are distributed as shown in Table 13.
It should be noted that the benzothiophene I dibenzothiophene ratio decreases
during the course of the petroleum evolution. 3 The aromatic sulfur compound
content also decreases whereas the amount of mercaptans sometimes increases.
140 G. F. BOLSHAKOV
Ra= 0.15 Ra= 0.25

Rn= 0.39 Rn= 0.76
R R
Ra= 0.27 Ra= 0.25

Rn= 0.45 Rn= 0.51
Ra= 0.33 R8 = 0.27 Ra= 0.35

Rn= 0.11 Rn= 0.18 Rn= 0.35
Scheme 1
~
0
H
E'·d.5
~
~
~
P-4 t.O
~
FIGURE 9. Arenothiophene content in 370-535 oc fractions of various oils. Oil fields: 1-Recluse
(Wyoming, USA); 2-Prudhoe Bay (Alaska, USA); 3-Wilmington (California, USA); 4-Gach
Saran (Iran).
TABLE 13
Structural-Chemical Composition of Thiophenes in the Deparaffinate of 320-530 °C
Vacuum Distillate in Romashkinskaya Oil
Thiophenes Empirical formula Content, %
Alkylthiophenes CnH2n-4S 3.5

Mononaphthenothiophenes CnH2n-6S 3.0
Dinaphthenothiophenes CnH2n-sS 2.5
Trinaphthenothiophenes CnH2n-lOS 1.0
Benzothiophenes CnH2n-10S 2.0
Dinaphthenobenzothiophenes CnH2n-14S 1.0
Trinaphthenobenzothiophenes CnH2n-16S 0.5
Dibenzothiophenes CnH2n-16S 1.5
Naphthenodibenzothiophenes CnH2n-IsS 1.0
Dinaphthenodibenzothiophenes CnH2n-2oS 0.5
Wilmington and Wasson oils (USA) contain benzothiophene, 2- and 3-methylben-

zothiophenes, and other benzothiophene homologs41 •78 •79 (Table 12). The ben-
zothiophenes identified in Wasson oil belong to the benzo[b]thiophenes.
142 0. F. BOLSHAKOV
Benzo[c]thiophenes
~
R --c.v~
have not been found in oils which may be explained by their instability. The
benzothiophenes identified are structurally similar to the thiaindanes with substi-
tuents occurring in position 2, more rarely in position 3, and still more rarely in
positions 7 and 4.
Arenothiophenes of different structures (Table 14) have been found in the
240-350 oc fraction, but in amounts far below those of the alkylthiophenes.
The structure of arenothiophenes with a larger number of rings has been poorly
studied. At the present time, dibenzothiophene and 1- or 4- methyl-

dibenzothiophene in Wasson oi1 41 and 1,2,7,8-tetramethyldibenzothiophene in
Kuwait oi1 80 have been identified. Naphtho[1,2,b]thiophenes as well as benzo-
naphthothiophenes and 11-thiabenzo[a]fluorenes have also been identified in oils. 1-.
4- and 10-methyl-11-thiabenzo[a]fluorene have been found in Kuwait oil:
s
Compound A has been isolated in pure form. 4
TABLE 14
Structural-Chemical Composition (Wt.%) of Thiophenes from Emba Oi141
Fractions
Thiophenes 3 s 9
Alkylthiophenes 82.0 62.2

'
58.6 44.7
10
53.7
Dinaphthothiophenes 3.5 11.8 21.0 19.9 17.s
Benzothiophenes 10.7 15.5 6.5 12.7
8.S
Naphthobenzothiophenes 1.24 2.4 4.0 0.9
2,4
Dibenzothiophenes 0.6 4.85 5.2 9.6
10.4
Thiophene areno homologs have been found in fairly large amounts in the
360-410 oc fractions of sulfur-containing mercaptan Orenburg oil,81 heavy Usinskaya
oil,s2 and West-Surgut14 oil (Table 15). The share of alkyl and cycloalkyl derivatives
of benzo- and dibenzothiophene exceeds 80% of the sulfur compounds studied.
TABLE 15
Arenothiophenes from 360-410 oc distillates of Orenburg (A), Usa (B), and
West-Surgut (C) Oils (wt. % in distillate)81 •229
Thiophenes A B c
0s 0.35 0.89 1.14
(sJC) 0.47 0.98 0.75
tOo 0.05 1.22 0.57
~ 0.28 1.18 2.04
ClsJO 0.42 0.82 1.82
cc9Y 0.65 1.07 1.13
~ 3.32 3.17 1.41
~ 2.59 2.26 1.58
0 0 2.42 2.30 2.01
~ 2.39
lOt:J 0.54 2.60 4.94

144 G. F. BOLSHAKOV
TABLE 15 (Continued)
Thiophenes A B c
~
0.87
0.52 0.62 0.79
0.17 0.08 0.09

0.18 0.19 0.46
1.08 0.49 0.38
Benzothiophene is present in the highest amount (4.94%). Dibenzothiophene has

been found in a fairly large quantity (3.32, 3.17% ). Considerable amounts of
benzothiophene and other arenothiophene alkyl homologs which account for a larger
part of sulfur compounds have been found 72 in the 190-360 oc fractions of West
Surgut, Orenburg, Yareg, Usinsk, and Samotlor oils. Besides benzothiophene alkyl
homologs, the distillates contain also their naphtheno homologs (3-6%) and
thiophene and benzothiophene alkyl homologs (Table 16).
Organic sulfur compounds of the 290-400 °C fraction of the unique Yareg oil have
been studied. 73 The oil in bedrocks is of high viscosity, contains almost no dissolved
gas and occurs at low pressure and temperature. It is a heavy, tarry, low paraffin oil
with a high boiling point; the sulfur content is 1.1 wt.%. The Yareg oil composition is
attributed73 to specific surroundings paleographically different from other areas of
Devonian sedimentation. Higher radioactivity of water and rocks, specific initial
material, the presence of titanium-containing minerals (Ti0 2), rock-weathering-all
this has accounted for the specific composition of the Yareg oil. The fraction under
consideration contains neither mercaptans nor sulfides. Thiacycloalkanes are also
absent, the content of thiaindanes (with sulfur in a saturated ring) amounting to about
6% of the total sulfur compounds. The distillate also contains about 6% Of
thiophcnes and 24% of dibenzothiophenes and approximately 65% of tri- and
ORGANIC SULFUR COMPOUNDS OF PETROLEUM l4S
TABLE 16
Structural-Chemical Group Composition or Thiophenes or 190-360 oc
Distillates from Oils74•76 •77
Structures Samotlor Usa West Surgut Orenburg Yareg
o-R
s
0.47 0.60 0.49 0.12 0.05
CcrR 0.17 0.23
WR 1.04 0.54
0.18 0.04
OvR 0.93 1.76 4.06 1.03 0.18
~ 0.36 0.83 0.88 0.33 0.12
C(9o 0.78 0.30 0.68 0.77
0.18 0.59
~ 0.10 0.88 0.19 1.25 0.12
OOo 0.23 0.17 0.06 0.16
~ 0.02 0.01
00=» 0.01
0.06
146 G. F. BOLSHAK.OV
polycyclic compounds. The following organic sulfur compounds have been found in
Yareg oil:
It should be mentioned that nearly always the content of sulfur compounds

identified correlates with the concentration and structure of the corresponding arenes.
Heterocyclic compounds with two sulfur atoms (other than disulfides) are present
in oils. Compounds with a larger number of sulfur atoms are encountered less
frequently. Methyl 3,4,5-trimethyl-2-thienyl sulfide (A) has been isolated from the
kerosine fraction of Iran oil. Isomeric methylthienothiophenes (B, C) have been
found in Wasson oiL
A B c
The concentration of polysulfur-containing sulfur compounds increases in high.
boiling fractions, reaching 3-4% of the total sulfur compounds in gas oils (370-
535 °C) and 6.5% in oil residues. 4 •49 •83 Thienothiophenes, thienothiacycloalkanes,
thienyl sulfides, their benzologs, naphthenologs, and so on have been found in oil
residues. The difficulty encountered in isolating these compounds from oil and its
high-molecular fraction should be mentioned.
Sulfur- and nitrogen-containing compounds have been found in numerous oils.
For example, 4,5-diethyl·, 5-ethyl-4-propyl-, 4-methyl-2-phenyl-, and 4,5-dimethyl-2-
phenylthiazole have been identified in oils of South Uzbekistan (USSR).
Alkylbenzothiazoles have been isolated from oils of Tadzhikistan and Baku a d

identified. n
ORGANIC SULFlJR COMPOUNDS OF PETROLEUM 147
Compounds containing sulfur and nitrogen atoms in different heterocycles are also
present in oi1: 84 •8'
R
~
~ R
~~s.!J
R
2-Thionoquinolines have been isolated from Californian oil (USA): 86
00~
.... s
H
Compounds containing sulfur and oxygen are present in oils in very small
quantities. A concentrate of high-boiling carboxylic acids has been isolated87 from
Californian oil and reduced. Apart from hydrocarbons the reduction products consist
of benzo- and dibenzothiophenes (0.001-0.01% of the oil), benzonaphthothiophenes
(up to 0.001% ), and their naphthologs. The compounds isolated have been assigned
the following structures:
R
~COOH COOH
~s.V R
R
~COOH
~
COOH
R~s~
COOH
148 G. F. BOL.SllAKOV
Among the 455-538 oc distillate heteroaromatic components of Californian oil

some substances of the empiric formula C0 H 2n-zOS have been found. Structure A ~~s
been suggested for a neutral compound with z = 26 and structures B and C for ac1d1c
compounds with z = 4 and 6: 84
R'(J(OH rArOH
s ~SH
A B c
Compounds containing sulfur, nitrogen, and oxygen are present in oil64 ' 88 beyond
any doubt; however, none of these compounds have been identified until now.
Thus, despite some uncertainty concerning the group chemical composition of
major sulfur compound containing atoms of so-called "residual" sulfur, it may be
concluded that thiophenes, saturated sulfides, and mercaptans are the most typical
organic sulfur compounds of oils in bedrocks. The above peculiarities in the change of
the group composition of sulfur compounds under the influence of geological factors
do not contradict modern ideas about the formation of most sulfur compounds due
to secondary sulfurization of oil components, and about the most important trends
and relative rates of the transformation of different sulfur compounds in the
processes of catagenesis.
II.4 Group Chemical Composition of Organic

Sulfur Compounds of Oil Distillates
The contents of hydrogen sulfide, elemental sulfur, thiols, sulfides, disulfides, and
compounds containing "residual" sulfur in light distillates obtained from 230 samples
of oils upon conventional distillation up to 300 oc were determined by Eolarography,
potentiometric and amperometric titration, and spectrophotometry. 11 ' 2 •28 The frac-
tions IBP-120 oc and 120-200 oc were distilled at atmospheric pressure and the
200-250 oc and 250-300 oc distillates at 10 mm Hg at the column top. Owing to the
lower average molecular weights of the components, the results of the analysis of the
distillates isolated should reflect the group chemical composition of the sulfur
compounds contained more correctly. In this case, "residual" sulfur may be more
reliably referred to thiophenes than in direct analysis of crude oils. The data obtained
do not reproduce directly the sulfur compound composition of native oils; these
compounds might undergo partial destruction during the distillation since the actual
temperatures in the still exceed the thermal stability threshold of saturated sulfur
comp~unds. Therefore, .t~e results of anal~sis o~ distillates are of less value for the
establishment of regulant1es of the change m nat1ve sulfur compounds in the Earth,
interior, but nevertheless of some importance from the viewpoint of refinin s
application, and forecasting the marketing properties of the products of the prima g,
distillation of oils. ry
The mean characteristics of the sulfur compound composition in oil fractions are
classified according to geologo-geochemical signs and listed in Tables 17 and 18 and
Figures 10 to 16.
TABLE 17
Sulfur Compound Group Chemical Composition in Benzene-Kerosine Fractions
of Oils from Terrigenous Deposits
Content, % or Sulphur Compound sum
•"Cl
<l'l
s ~
=
£ c =
8.
.2
.,
Cl)
=
t
e
~
.
:g
-g
.:: ae...
• .e:;
i'Q, ....~0
~
....
c --
'0
c
"'
rl
"Cl tl:l
...
-
~
.2 ~
.c:
= -
.!! <C
C> c -a
1 c. t:
~
e 0 <C
:;
~
.c:
t!i Q tl:l lhS s i: tl:l Q"' 0
1 2 3 4 s 6 7 8 9 10
IBP-120 oc Fraction
Cretaceous 0-500 1.0 0.2800 0.0 30.4 2.6 53.5 0.0 13.5
1500-2000 10.8 0.0280 0.0 0.0 0.4 48.2 17.5 37.5
2000-2500 9.0 0.0150 0.0 1.3 3.3 38.7 30.7 16.0
average 9.0 0.0277 0.0 13.0 2.5 46.3 16.2 22.0
Jurassic 2500-3000 11.2 0.0120 0.0 0.0 0.0 83.4 13.3 3.3
Mesozoic average 9.1 0.0270 0.0 12.5 2.5 46.9 16.2 21.9
Carbonic 500-1000 5.9 0.1625 0.0 3.7 39.1 29.5 0.0 27.7
1000-1500 7.4 0.0486 0.0 2.3 33.3 32.7 2.5 29.2
1500-2000 10.1 0.0532 1.1 6.0 50.6 26.1 3.0 13.2
2000-2500 8.4 0.0366 4.4 1.9 23.0 42.1 1.6 27.0
average 8.4 0.0530 0.6 3.8 39.3 30.6 2.3 23.4
Devonian 1000-1500 8.9 0.0570 0.0 0.2 4.4 13.7 0.0 81.7
1500-2000 10.7 0.0251 0.0 0.8 7.6 59.0 2.8 29.8
2000-2500 10.3 0.0384 0.3 6.5 3.4 68.4 2.9 18.5
2500-3000 12.3 0.0114 0.0 4.4 6.1 48.2 16.7 24.6
300)-3500 14.3 0.0014 0.0 42.9 57.1 0.0 0.0 0.0
average 10.6 0.0309 0.0 2.3 5.2 43.7 2.9 45.9
Paleozoic 500-1000 5.9 0.1625 0.0 3.7 39.1 29.5 0.0 27.7
1000-1500 7.9 0.0513 0.0 1.6 23.0 26.0 1.6 47.8
150 G. F. BOLSHAKOV
1 2 3 4 5 6 7 8 9 10
1500-2000 10.5 0.0367 0.5 3.8 33.2 39.2 3.0 19.9

2000-2500 9.8 0.0379 1.3 5.3 8.4 61.7 2.6 20.5
2500-3000 12.3 0.0114 0.0 4.4 6.1 48.2 16.7 24.6
3000-3500 14.3 0.0014 0.0 42.9 57.1 0.0 0.0 0.0
average 9.6 0.0407 0.2 3.2 25.1 36.1 2.5 32.9
120-200 oc Fraction
Cretaceous 0-500 2.6 0.3200 0.1 10.2 1.0 37.5 0.0 51.2
1500-2000 15.2 0.0450 0.0 1.1 1.8 77.8 5.3 13.8
2000-2500 11.6 0.0910 0.0 2.0 2.2 69.0 1.8 14.0
average 11.8 0.0928 0.0 3.0 1.9 65.3 1.8 28.0
Jurassic 2500-3000 14.4 0.0310 0.0 0.0 0.0 90.3 9.4 0.3
Carbonic 500-1000 11.2 0.5485 0.0 0.9 13.5 50.1 0.0 35.4
1000-1500 12.2 0.2961 0.0 2.0 5.0 80.4 0.3 12.3
1500-2000 14.5 0.1723 0.6 4.8 17.9 59.7 0.6 16.4
2000-2500 14.8 0.1220 1.6 4.3 8.3 61.1 0.7 24.0
average 13.2 0.2467 0.8 2.7 8.9 72.3 0.4 15.5
Devonian 1000-1500 14.3 0.1583 0.0 1.6 1.6 64.8 0.0 32.0
1500-2000 14.6 0.1627 0.0 1.3 1.2 74.3 0.3 22.9
2000-2500 14.9 0.1702 0.0 2.4 1.5 57.8 0.0 38.3
2500-3000 16.8 0.0763 0.0 3.0 1.3 68.9 2.0 24.8
3000-3500 18.3 0.0194 0.0 30.9 7.2 41.3 0.0 20.6
average 15.1 0.1442 0.0 1.9 1.4 68.0 0.3 28.4
Paleozoic 500-1000 11.2 0.5485 0.0 0.9 13.5 50.1 0.0 35.4
1000-1500 12.9 0.2524 0.0 1.9 4.3 77.3 0.0 16.5
1500-2000 14.6 0.1575 0.2 2.8 8.3 68.0 0.4 20.2
2000-2500 14.9 0.1575 0.3 2.8 2.9 58.4 0.1 35.4
2500-3000 16.8 0.0762 0.0 3.0 1.3 68.9 2.0 24.8
3000-3500 18.3 0.0194 0.0 30.9 7.2 41.3 0.0 20.6
average 14.2 0.1898 0.2 2.4 5.7 70.4 0.4 20.9
200-250 oc Fraction
Cretaceous 0-500 7.6 0.3600 0.0 5.6 0.3 36.1 0.0 58.0
1500-2000 9.5 0.3175 0.0 0.0 0.1 52.8 0.3 46.8
2000-2500 6.8 0.2600 0.0 0.2 0.4 81.7 0.4 17.3
average 7.3 0.2732 0.0 0.6 0.3 73.9 0.4 24.8
Jurassic 2500-3000 8.3 0.1600 0.0 0.0 0.0 68.8 1.4 29.8
1 2 3 4 5 6 7 8 9 10
Carbonic 500-1000 7.9 0.3910 0.0 0.9 2.1 65.8 0.0 31.2
1000-1500 7.2 0.8200 0.0 0.4 0.8 67.7 0.0 31.1
1500-2000 7.4 0.4404 0.0 0.9 3.7 71.0 0.1 24.3
2000-2500 7.2 0.4340 0.0 0.7 1.3 64.1 0.3 33.6
average 7.3 0.6288 0.0 0.5 1.6 68.2 0.1 29.6
Devonian 1000-1500 8.3 0.5993 0.0 0.1 0.2 58.5 0.0 41.2
1500-2000 7.9 0.5323 0.0 0.2 0.2 65.6 0.2 33.8
2000-2500 7.8 0.4268 0.0 0.6 0.6 48.2 0.1 50.5
2500-3000 9.2 0.3167 0.0 0.3 0.3 63.2 0.3 35.9
3000-3500 10.0 0.0340 0.0 2.6 2.6 57.7 0.0 37.1
average 8.2 0.4762 0.0 0.2 0.3 60.6 0.1 38.8
Paleozoic 500-1000 7.9 0.3910 0.0 0.9 2.1 65.8 0.0 31.2
1000-1500 7.6 0.7496 0.0 0.3 0.7 65.3 0.0 33.6
1500-2000 7.7 0.4945 0.0 0.4 1.5. 67.6 0.2 30.3
2000-2500 7.6 0.4287 0.0 0.7 0.8 52.4 0.2 46.0
2500-3000 9.2 0.3167 0.0 0.3 0.3 63.2 0.3 35.9
3000-3500 10.0 0.0340 0.0 2.6 2.6 57.7 0.0 37.1
average 7.8 0.5459 0.0 0.4 1.0 64.6 0.1 34.0
250-300 oc Fraction
Cretaceous 0-500 13.3 0.4900 0.0 0.3 0.8 32.6 0.0 66.3
1500-2000 10.0 0.7700 0.0 0.0 0.2 45.1 0.1 54.6
2000-2500 8.5 0.6515 0.0 0.0 0.2 60.2 0.1 39.5
average 8.9 0.6640 0.0 0.0 0.2 56.5 0.1 43.2
Jurassic 2500-3000 10.0 0.5500 0.0 0.0 0.7 50.9 G.O 48.4
Carbonic 500-1000 8.9 0.8780 0.0 0.1 0.8 42.6 0.4 56.1
1000-1500 8.2 1.7359 0.0 0.1 0.4 45.0 0.1 54.4
1500-2000 8.5 1.0866 0.0 0.3 1.3 37.3 0.1 61.0
2000-2500 8.6 1.1480 0.0 0.2 0.6 47.9 0.2 51.1
average 8.4 1.4047 0.0 0.2 0.7 43.1 0.1 55.9
Devonian 1000-1500 8.9 1.3500 0.0 0.1 0.1 39.2 0.0 60.6
1500-2000 8.2 1.0940 0.0 0.1 0.2 46 . .4 0.1 53.3
2000-2500 8.1 0.9527 0.0 0.2 0.2 48.3 0.1 51.2
2500-3000 8.9 0.9020 0.0 0.0 0.1 46.2 0.3 53.4
3000-3500 11.8 0.0530 0.0 0.0 1.7 39.6 0.0 58.7
average 8.5 1.0665 0.0 0.1 0.2 44.8 0.1 54.8
Pateozoic 500-1000 8.9 0.8780. 0.0 0.1 0.8 42.6 0.4 56.1
1000-1500 8.4 1.6127 0.0 0.1 0.4 43.5 0.0 56.0
1500-2000 8.3 1.0910 0.0 0.2 0.6 42.7 0.1 - 56.4
152 G. F. BOLSHAKOV
1 l 3 4 s 6 7 8 9 10
2000-2500 8.2 1.0041 0.0 0.2 0.3 48.1 0.2 51.2

2500-3000 8.9 0.9020 0.0 0.0 0.1 46.2 0.3 . 53.4
3000-3500 11.8 0.0530 0.0 0.0 1.7 39.6 0.0 58.7
average 8.5 1.2209 0.0 0.1 0.4 43.9 0.1 55.4
IBP-300 "C Fraction

Cretaceous 0-500 24.5 0.4231 0.0 3.3 0.7 34.5 0.0 61.5
1500-2000 46.5 0.2517 0.0 0.1 0.2 49.1 0.9 49.7
2000-2500 35.9 0.2367 0.0 0.3 0.5 65.4 0.9 32.9
average 37.2 0.2446 0.0 0.4 0.5 60.6 0.9 37.7
Jurassic 2500-3000 43.9 0.1688 0.0 0.0 0.5 57.0 1.1 41.4
Carbonic 500-1000 33.9 0.5311 0.0 0.7 7.4 48.5 0.2 43.2
1000-1500 35.0 0.6889 0.0 0.5 1.7 55.7 0.1 42.0
1500-2000 40.5 0.3835 0.1 1.3 6.2 47.5 0.3 44.6
2000-2500 39.0 0.3884 0.3 0.8 2.1 52.6 0.3 43.9
average 37.1 0.5411 0.1 0.6 2.3 52.9 0.2 42.8
Devonian 1000-1500 40.4 0.4895 0.0 0.3 0.4 46.3 0.0 53.0
1500-2000 41.4 0.3821 0.0 0.3 0.5 55.9 1),2 43.1
2000-2500 41.1 0.3401 0.0 0.9 0.6 50.6 0.1 47.8
2500-3000 47.2 0.2619 0.0 0.5 0.4 52.5 0.6 46.0
3000-3500 54.4 0.0246 0.0 9.3 4.1 43.9 0.0 42.7
average 42.5 0.3621 0.0 0.4 0.5 52.0 0.2 46.9
Paleozoic 500-1000 33.9 0.5311 0.0 0.7 7.4 48.5 0.2 43.2
1000-1500 36.7 0.6189 0.0 0.4 1.4 53.1 0.1 45.0
1500-2000 41.0 0.3827 0.1 0.7 2.8 52.5 0.2 43.7
2000-2500 40.5 0.3523 0.1 0.9 1.1 51.1 0.2 46.7
2500-3000 47.2 0.2619 0.0 0.5 0.4 52.5 0.6 46.0
3000-3500 54.4 0.0246 0.0 9.3 4.1 43.9 0.0 42.7
average 40.0 0.4378 0.0 0.6 2.0 52.4 0.2 44.8
• Corresponding to residual sulfur
The total sulfur content of distillates usually increases as the boiling point rises
(Fig. 10). The change in the total sulfur concentration in petroleum depending on the
depth of occurrence corresponds to the change in the total sulfur content of the
200-300 oc distillates of oils from both Paleozoic terrigenous oils fields at depths of
1000-1500 m and less deep carbonaceous horizons. The total sulfur content of the
gasoline fractions of all oils decreases with increasing depth of occurrence.
TABLE 18
Sulfur Compound Group Chemical Composition of Oil Fractions
from Carbonaceous Rocks
Content, % of Sulfur Compound sum

~
-.::=
.s
( ,i
~
tll
'Cl
=
=
E
or
(,i
=
......
~ ~
--=
'a
~
8.
E
Q
~
Q= u
...
~ =
(,i
::2
~
(,i
... .:::;
~
.... '>, .::
'ii "'
.s= = ~
·~
- "CC t:l)
Q
.:: -;"' "' "'
~
"CC IC ...
Q
(,i "'S :; ~
0~
t.:)
i
Q ~
0':1
~ lhS s :aEo- IC
:;
t:l)
"'
s
.I:
0
l 2 3 4 5 6 7 8 9 10
IBP-120 °C Fraction
Paleogene 0-500 3.2 0.120 10.0 7.5 30.2 33.3 0.0 19.0
1000-1500 1.3 0.910 3.6 1.4 1.2 38.5 0.0 55.3
average 2.2 0.515 4.4 2.1 4.6 37.9 0.0 51.0
Permian 500-1000 10.6 0.4360 1.1 0.8 44.0 36.7 0.0 17.7
1000-1500 9.4 0.4600 2.1 1.2 32.6 30.4 0.0 33.7
1500-2000 9.4 0.1977 0.0 1.2 43.2 13.7 1.7 40.2
average 10.0 0.3693 1.1 1.0 41.1 31.4 0.3 25.1
Carbonic 500-1000 7.1 0.1940 0.0 3.6 37.1 27.8 0.0 31.5
1000-1500 9.1 0.0524 3.1 8.0 43.3 34.7 0.2 10.7
1500-2000 9.8 0.1211 0.0 4.0 29.4 13.9 0.0 52.7
2000-2500 10.0 0.1598 0.0 0.4 61.1 31.9 0.6 6.0
average 9.2 0.0867 0.9 5.0 44.0 29.5 0.1 20.5
Devonian 1000-1500 9.3 0.1100 0.0 0.3 30.0 54.5 0.0 15.2
1500-2000 14.8 0.0450 0.0 2.9 1.6 37.8 3.3 54.4
2000-3000 16.1 0.0220 0.0 9.1 48.6 27.3 0.0 15.0
3000-3500 17.8 0.0060 0.0 0.0 0.0 50.0 0.0 50.0
average 14.8 0.0417 0.0 2.9 22.3 43.6 2.4 28.8
Paleozoic 500-1000 8.8 0.3150 0.7 1.7 41.9 34.0 0.0 21.7
1000-1500 9.1 0.0889 2.5 4.7 37.9 33.9 0.1 20.9
1500-2000 10.3 0.1254 0.0 3.3 31.9 14.8 0.6 49.5
2000-3000 11.7 0.1204 0.0 0.9 60.0 31.4 0.6 6.4
3000-3500 17.8 0.0060 0.0 0.0 0.0 50.0 50.0 0.0
average 9.9 0.1293 0.5 3.0 42.0 30.9 0.2 23.4
154 G. F. BOLSHAKOV
1 2 3 4 5 6 7 8 9 10
120-200 oc Fraction
Paleogene 0-500 11.0 1.5300 6.5 3.9 2.3 66.7 0.0 20.6
1000-1500 10.4 7.1000 0.4 0.5 0.3 33.2 0.0 65.6
average 10.7 4.3150 1.5 1.1 0.7 39.2 0.0 57.5
Permian 500-1000 15.5 1.0680 0.5 1.5 33.0 49.1 0.0 15.9
1000-1500 12.7 1.4050 1.8 1.0 30.1 23.8 0.0 43.2
1500-2000 13.3 0.6907 0.5 2.5 22.3 50.7 0.0 24.0
average 14.3 1.0182 0.8 1.6 30.2 42.6 0.0 25.2
Carbonic 500-1000 9.3 0.6720 0.0 3.0 12.3 45.5 0.0 39.2
1000-1500 13.5 0.3850 1.2 4.5 12.7 59.9 0.0 21.7
1500-2000 14.0 0.3052 0.3 6.2 13.1 61.5 0.1 18.8
2000-2500 16.9 0.2780 0.0 3.6 34.6 44.6 0.4 16.8
average 13.6 0.3818 0.6 4.6 14.5 58.9 0.1 21.3
Devonian 1000-1500 14.2 0.7400 0.0 0.6 6.2 83.8 0.0 9.6
1500-2000 19.5 0.1100 0.0 5.4 47.9 28.6 0.0 18.1
2000-3000 17.4 0.1350 0.0 5.6 22.4 63.0 0.0 9.0
3000-3500 20.6 0.0200 0.0 1.0 0.0 35.0 20.0 44.0
average 18.1 0.2083 0.0 2.5 16.9 68.8 0.3 11.5
Paleozoic 500-1000 12.4 0.8700 0.3 2.1 25.0 47.7 0.0 24.9
1000-1500 13.5 0.4848 1.3 3.4 16.5 52.7 0.0 26.1
1500-2000 14.5 0.3478 0.4 4.9 17.4 56.7 0.1 20.5
2000-3000 17.0 0.2371 0.0 4.0 18.3 47.6 0.3 29.9
3000-3500 20.6 0.0200 0.0 1.0 0.0 35.0 20.0 44.0
average 17.1 0.4705 0.7 3.4 20.3 53.5 0.1 22.0
200-250 oc Fraction
Paleogene 0-500 5.6 2.9300 0.0 1.9 0.9 72.0 0.0 25.2
1000-1500 1.4 9.5000 0.2 0.1 0.4 21.3 0.0 77.7
average 3.5 6.2150 0.1 0.5 0.5 33.3 0.0 65.6
Permian 500-1000 6.8 1.4340 0.0 0.6 9.8 56.1 0.0 33.5
1000-1500 8.3 1.0750 0.0 0.8 11.0 65.1 0.0 23.1
1500-2000 7.4 1.0667 0.0 0.6 9.9 68.7 0.0 20.8
average 7.3 1.2520 0.0 0.6 10.0 60.9 0.0 28.5
Carbonic 500-1000 7.8 1.2833 0.0 0.4 0.9 52.2 0.0 46.5
1000-1500 7.6 0.8384 0.0 1.2 3.8 60.6 0.0 34.4
~00-2000 6.6 0.7233 0.0 0.6 3.9 57.6 0.1 37.8
00-2500 7.4 0.4160 0.0 0.4 2.3 62.0 0.0 35.2
average 7.4 0.8185 0.0 0.9 3.2 58.3 0.0 37.7
1 2 3 4 5 6 7 8 9 10
Devonian 1000-1500 8.2 2.1000 0.0 0.1 0.2 63.3 0.0 36.4
1500-2000 6.6 0.2100 0.0 0.8 26.0 52.4 0.0 20.8
2000-3000 8.4 0.2250 0.0 2.0 12.5 54.0 0.0 31.0
3000-3500 9.5 0.0300 0.0 0.7 9.0 33.3 10.0 47.0
average 8.0 0.5000 0.0 0.5 5.7 60.1 0.1 31.2
Paleozoic 500-1000 7.3 1.3518 0.0 0.5 5.2 54.1 0.0 40.2
1000-1500 7.7 0.9051 0.0 0.6 4.1 61.2 0.0 33.5
1500-2000 6.7 0.7235 0.0 0.6 6.1 60.2 0.1 33.0
2000-3000 7.7 0.3614 0.0 0.7 4.1 60.6 0.0 34.5
3000-3500 9.5 0.0300 0.0 0.7 9.0 33.3 10.0 47.0
average 7.4 0.8570 0.0 0.6 5.2 59.0 0.0 35.2
250-300 oc Fraction
Paleogene 0-500 5.6 3.0000 0.0 0.2 0.2 65.7 0.0 34.0
1000-1500 4.9 9.6000 0.0 0.0 0.2 26.5 0.0 73.3
average 5.2 6.3000 0.0 0.1 0.2 35.8 0.0 63.9
Permian 500-1000 7.0 1.9080 0.0 0.6 7.9 48.3 0.0 43.2
1000...:1500 7.8 2.0000 0.0 0.9 6.3 40.5 0.0 52.3
1500-2000 8.1 1.8633 0.0 0.1 6.9 58.0 0.0 35.0
average 7.5 1.9130 0.0 0.5 7.3 49.5 0.0 42.7
Carbonic 500-1000 9.3 1.9233 0.0 0.4 0.6 45.1 0.0 53.9
1000-1500 7.6 1.3661 0.0 0.3 2.9 50.7 0.0 46.1
1500-2000 6.0 1.2062 0.0 0.3 3.0 50.1 0.1 46.5
2000-2500 7.9 0.8280 0.0 0.1 1.4 43.7 0.2 54.5
average 7.4 1.3357 0.0 0.3 2.4 49.0 0.0 48.3
Devonian 1000-1500 11.4 4.0700 0.0 0.1 0.1 35.4 0.0 64.4
1500-2000 9.2 0.5000 0.0 0.2 11.4 37.0 0.0 51.4
2000-3000 6.8 0.5250 0.0 0.6 7.7 28.9 0.0 62.8
3000-3500 10.5 0.0800 0.0 0.4 0.4 12.5 0.0 86.7
average 9.0 0.8625 0.0 0.3 6.5 30.0 0.0 63.2
Paleogene 500-1000 8.3 1.9163 0.0 0.5 3.9 46.6 0.0 49.0
1000-1500 7.8 1.5188 0.0 0.4 3.0 48.1 0.0 48.6
1500-2000 6.7 1.2372 0.0 0.3 4.4 51.5 0.1 43.8
2000-3000 7.6 0.7414 0.0 0.2 2.7 40.7 0.2 56.2
3000-3500 10.5 0.0800 0.0 0.4 0.4 12.5 0.0 86.7
average 7.6 1.0834 0.0 0.4 3.5 46.3 0.0 49.8
IBP·300 oc Fraction
Paleogene 0-500 25.4 1.9851 2.3 2.0 1.3 67.8 0.0 26.6
1000-1500 18.0 7.5202 0.2 0.3 0.3 29.8 0.0 69.4
average 21.7 4.7526 0.7 0.7 0.5 37.7 0.0 60.4
156 G. F. BOLSHAKOV
s 6 7 8 9 10
1 2 3 4
39.9 1.1098 0.3 1.0 21.5 49.0 0.0 28.2

Permian 500-1000
1000-1500 38.2 1.2222 0.9 0.9 18.8 37.9 0.0 41.5
1500-2000 38.2 0.8909 0.1 0.9 13.7 56".1 0.1 29.1
average 39.0 1.0676 0.4 0.9 19.0 48.3 0.0 31.4
Carbonic 500-1000 33.5 1.0604 0.0 1.0 4.2 46.5 0.0 48.3
1000-1500 37.8 0.5933 0.4 1.7 6.3 55.3 0.0 36.3
1500-2000 36.4 0.4800 0.1 2.1 7.5 52.5 0.1 37.7
2000-2500 42.2 0.3772 0.0 1.2 17.4 46.3 0.3 34.8
average 37.3 0.5903 0.2 1.6 7.0 52.1 0.1 39.0
Devonian 1000-1500 43.1 1.7436 0.0 0.2 1.4 48.8 0.0 49.7
1500-2000 50.1 0.1769 0.0 1.8 21.7 37.1 0.2 39.2
2000-3000 48.7 0.1676 0.0 2.7 14.8 44.5 0.0 38.0
3000-3500 58.4 0.0281 0.0 0.7 1.8 24.2 10.0 63.3
average 49.8 0.3706 0.0 0.8 6.6 45.9 0.2 46.5
Paleozoic 500-1000 36.4 1.0849 0.1 1.0 13.0 47.8 0.0 38.1
1000-1500 38.0 0.6920 0.4 1.5 7.4 52.2 0.0 38.5
1500-2000 38.2 0.5043 0.1 1.7 10.1 52.7 0.1 35.2
2000-3000 44.1 0.3110 0.0 1.5 16.9 46.0 0.2 35.4
3000-3500 58.4 0.0281 0.0 0.7 1.8 24.2 10.0 63.3
average 38.8 0.6397 0.2 1.4 10.2 50.7 0.1 37.4
Elemental sulfur is found in the distillates of all oils. The average elemental sulfur
content of the distillates decreases with increasing age and depth of occurrence of
petroliferous beds. The oil fractions from carbonate collectors are always richer in
elemental sulfur.
The gasoline distillates of oils from the deepest collectors of the Carboniferous age
contain dissolved hydrogen sulfide up to 0.002%. No hydrogen sulfide was observed
in the 200-300 oc fractions and in all distillation products of most oils from other
terrigenous oil fields of the Mesozoic and Paleozoic. Considerably greater amounts of
hydrogen sulfide have been found in the gasoline fractions of carbonate Devonian
oils. In this case, however, the highest concentrations of hydrogen sulfide are
observed in the distillates of young (Paleogenic) oils or of oils occurring no deeper
than 1500 m. No hydrogen sulfide has been found in the fractions of carbonaceous
Devonian oils.
Mercaptans are found in different amounts in the fractions of nearly all oils. 3 .4.s,ss
As a rule, the mercaptan content is higher in low-boiling fractions reaching 50% and
sometimes 70% of the total sulfur compounds. The maximum mercaptan content is
observed in the 120-200 oc fraction. As the boiling point of these fractions rises, the
mercaptan content decreases rapidly and in the fractions above 300 oc the concentra.
tion of thiols is usually low. The distillates of oils from carbonaceous oil pools are
considerably richer in mercaptans than the fractions of oils from terrigenous collector
of the same age. The maximum mercaptan concentrations are observed after th~
FIGURE 10. Effect of the depth of occurrence on the sulfurcontent: total (a), mercaptan (b), sulfide (c),
and ."residual" (d) in petroleum fractions.
Fractions: l:IBP-120 "C, 2:120-200 °C, 3:200-250 "C, 4:250-300 "C, S:IBP-300 "C. - • ----
fractions of oils from terrigenous and carbonaceous deposits, respectively.
distillation in the distillates of Permian oils; with increasing age of the enclosing
deposits, the mercaptan content of the distillates reduces quickly, being nearly one
order of magnitude lower in the Devonian oil fractions. The mercaptan concentration
decreases with increasing depth of occurrence of terrigenous and carbonate beds. In
this case, the thiol content of the fractions decreases sharply with deepening the oil
pool to 1500 m and increases again in the zone of the major phase of oil generation
(1500-2500 m). At greater depths, the mercaptan content decreases to 0.006% and
below.
158 G. F. BOLSHAKOV
UESOZOIC PALEOZOIC PALEOZOIC

( TERRIGEllOUS) (CARBONACEOUS)
FIGURE 11. Sulfur compound average group composition in fractions of various oils.
H 2S elemental sulfur
thiols sulfides
disulfides thiophenes
Mercaptans constitute no more than 3% of all sulfur compounds present in any of

Mesozoic oil distillates. In the broad fractions IBP-300 °C of oils from terrigenous
and carbonaceous Paleozoic pools mercaptans account on average for 2.0 and 10.0%
of the total sulfur compounds, while in the IBP-120 oc distillates their average
content increases to 25 and 42%, respectively (Fig. 11). Among sulfur compounds
in the Mesozoic oil distillates, the content of mercaptans does not change much With
depth (Fig. 12). In the oil distillates of terrigenous Paleozoic the content of thiols
decreases considerably with increasing depth of occurrence and increases consider-
ably in the fractions of oils of carbonaceous oil pools after passing a minimum for the
range 1000-1500 m (Fig. 13). The distillates IBP-300 oc contain 16-32 and 7-14%
of total mercaptans in crude oils of carbonaceous and terrigenous deposits of the
Paleozoic, respectively, although as little as 7-14% of their total amount in oil are
concentrated in these fractions.
ORGANIC SULFUR COMPOUNDS OF PETROLEUM
159
60
0~~~~
0 , 2
FIGURE U. Variations in the average group composition of sulfur compounds in a distillate
IBP-300 cc of Mesozoic oils depending on the depth of occurrence. Designations are given in Fig. 11.
The sulfide content increases with rising boiling point of distillates (Fig. 10),
reaching the largest share of the total sulfur compounds (up to 70% on average and
higher) in the 200-250 °C fractions of "young" oils of Paleogene, Mesozoic, and
Permian deposits or in the 120-200 °C distillates of older Carboniferous and
Devonian oils. The gasolines IBP-200 oc of erodes of carbonate deposits are richer in
sulfides than the corresponding fractions of oils of terrigenous collectors. The
kerosine fractions of oils of carbonate deposits show a higher sulfide content than
analogous fractions of oils of terrigenous rocks. This regularity holds at depths o(
occurrence up to 2500 m. At greater depths the concentration ratio is reversed and
higher sulfide concentrations are found in the 200-300 °C distillates of oils of
terrigenous deposits.
In the distillates IBP-300 °C of oils from terrigenous rocks sulfides account for
52-62% of the total; this value decreases to some extent with increasing age of
Downloaded by [University of Arizona] at 17:10 19 April 2015 160 G. F. BOLSHAKOV
1 2 J
FIGURE 13. Variations in the average group composition in broad distillates IBP-300 °C of oils from
terrigenous (a) and carbonaceous (b) Palelozoic deposits depending on the depth of occurrence.
Designations are given in Fig. 11.
deposits (Fig. 14). In analogous fractions of oils of carbonate rocks sulfides amount
on average to 46-52%. In the fractions IBP-300 oc of Mesozoic oils the sulfide
content increases with increasing depth of occurrence from 32% at 300 m to 58-67%
at depths exceeding 2000 m (Fig. 12). The share of sulfides varies within narrower
ranges depending on the depth of occurrence in the 300 oc light distillates of
Paleozoic oils. The sulfide content either increases from 49% to 52% or decreases
from 52% at a level of 1000-1500 m to 46~ with increasing. depth ~f ~it-bearing
terrigenous or carbonaceous rocks, respect1vely. A non-umform d1stnbution of
sulfides is also observed in the fractions of Iranian, Egyptian, and US oils (Fig. 15).3
ORGANIC SULRJR COMPOUNDS OF PETROLEUM
161
60
Mz C D P C D
GEOLOGICAL AGE OP DEPOSITS
FIGURE 14. Sulfur compound average group composition in distillates IBP-300 oc of oils from
terrigenous (I) and carbonaceous (11) rocks of varying geological age. Designations are given in Fig. 11.
A B c
fOO 200 JOO tOO 200 JOO 100 200

BOILING POINT, oc
FIGURE 15. Sulfur compound group composition of some oils from Iran, Egypt, and USA.
I-elemental sulfur, 11-sulfides, 111-mercaptans, IV-disulfides, V-sulfides, VI-thiophenes.
Downloaded by [University of Arizona] at 17:10 19 April 2015 162 G. F. BOLSHAKOV
J 5 7
NUMBER OF RINGS IN THE MOLECULE
FIGURE 16. Thiacycloalkane content in fractions 370-535 oc from oils: 1-Recluse (Wyoming,
USA), 2-Swan Hills (Alberta, Canada), 3-Prudhoe Bay (Alaska, USA); 4-Wilmington (Califor-
nia, USA), 5-Gach Saran (Iran).
Independent of the oil type the sulfide content of heavy fractions always decreases
due to an increasing share of arenothiophene compounds.
Cyclic sulfides account for a considerable part of the total amount of sulfides
(Table 19). The thiacycloalkane content of heavy distillates increases with increasing
sulfur compound concentration. The thiacycloalkanes in the fractions boiling below
535 oc contain up to eight rings. The bi-, tri-, and, less frequently, tetracyclic derivatives
are predominant (Fig. 16).
Upon conventional distillation of oils from terrigenous and carbonaceous rocks, the
fractions IBP-300 cc contain 14-69% and 13-21% of the sulfide sulfur found in
erodes, respectively (Table 20). The sulfide concentration in light distillates increases
with increasing depth of occurrence.
In the distillates of oils occurring within a depth interval of 100-3000 m, disulfide
sulfur was found in amounts of n • (10- 4-10- 3)%. The highest amounts (up to
0.005%, 16% of all the sulfur) are observed in the fractions IBP-120 cc of Low
Cretaceous oils in West Siberia (Fig. 11). As the boiling temperature rises the averag
disulfide content of the fractions decreases rapidly. The distillates of oils of te ~
rigenous rocks are considerably richer in disulfides than analogous fractions of oils r f
carbonaceous collectors. The influence of the depth on the disulfide content of t~
distillates is difficult to assess since the variations in concentrations with depth onle
slightly exceed the error of the determination. Y
TABLE 19
Sulfur Compound Group Composition from the 370-535 oc Fractions of Dilferent Oils
Content, wt. % of total Sulfur Compounds in different oils
Quantity of
Prudhoe Gach Swan saturated rings
Sulfur compound(s) Bay Saran Hills Wilmington Recluse• ln molecule
Alkyl aryl sulfides 0.1 14.4 0-5

Diaryl sulfides 5.2 5.7 0.1 12.0 0-3
Thiacycloalkanes 36.0 45.5 21.7 38.1 26.9 1-8
Benzothiacycloalkanes 6.0 3.2 4.6 4.3 10.5 1-7
Dibenzothiacycloalkanes 0.3 1.3 2.9 1.4 0.5 1-7

Thiophenes 2.2 0-2
Benzothiophenes 29.2 25.0 17.9 18.6 11.8 0-7
Dibenzo- and naphtha-
thiophenes 14.6 15.8 11.1 11.5 19.5 0-6
Other polyareno·
thiophenes 8.6 3.5 41.7 11.9 16.4
Total Sulfur
Compounds in fraction 10.09 19.29 3.08 16.61 1.48
• 370-530 oc fraction
The concentration of "residual" sulfur (thiophenes) in petroleum distillates in·

creases rapidly with rising boiling point, but even in the fraction 250-300 oc it still
remains much lower than in petroleum in general. No more than 6.5% thiophenes
pass over in the distillate IBP-300 oc upon conventional distillation. Thus, the
predominant part of these sulfur compounds are present in high-boiling and residual
fractions. The absolute concentration of "residual" sulfur in distillates decreases with
increasing depth of occurrence. This decrease is analogous to the change in the total
and sulfide sulfur content (Fig. 10). The influence of the litho logic composition of the
enclosing rocks on the "residual" sulfur concentration is manifested in different ways
depending on the depth. In oil fields occurring at a depth up to 1000-1200 m, higher
thiophene amounts are observed in light distillates of oils from carbonaceous rocks,
whereas in deep-seated oil fields, the thiophene-richest are those from terrigenous
rocks.
With increasing depth of oil occurrence in terrigenous Mesozoic rocks, from 500 m
to 2000 m, the thiophene sulfur content of the distillates IBP-300 oc decreases from
62 to 33-44% (Fig. 12). With further plunging of the oil-bearing beds the thiophene
content increases again.
The thiophene content of the distillates IBP-300 °C of Paleozoic oils in terrigenous
and carbonaceous rocks is 43-47 and 35-38%, respectively (Fig. 13). With increasing
~ve the thioohene content of li~ht fractions becomes higher (Fig. 14).
164 G. F. BOLSHAKOV
TABLE 20
Sulfur Compound Content of 300 oc Distillates
Sulfur content, % of the sum ln oil
Age of enclosing rocks Depth of occurrence, m total mercaptan sulfide residual
Conventional distillation
Cretaceous 0-500 7.8 11.1 1.5 5.1
1500-2000 10.7 20.6 6.3
2000-2500 5.6 15.1 1.5
average 6.3 15.3 2.0
Jurassic 2500-3000 8.5 69.4 4.4

Mesozoic average 6.4 15.8 2.0
Paleozoic 500-1000 10.7 44.2 14.2 3.6

(terrigenous deposits) 1000-1500 10.9 7.4 14.7 3.0
1500-2000 11.6 29.7 22.1 4.7
2000-2500 10.3 27.0 21.0 4.2
2500-3000 12.3 7.8 45.7 6.5
average 11.0 21.5 19.0 3.8
Paleozoic 500-1000 14.4 16.4 19.9 2.4

(carbonaceous deposits) 1000-1500 11.4 18.8 13.3 2.4
1500-2000 9.4 20.3 16.7 2.0
2000-2500 11.0 31.4 20.7 4.1
average 11.2 19.3 15.5 2.4
Mild distillation
Cretaceous 1500-2000 8.7 24.0 2.9
Paleozoic 1000-1500 8.4 2.7 11.3 2.4
(terrigenous deposits) 1500-2000 8.7 6.9 16.1 3.9
2000-2500 7.6 11.4 16.4 3.0
2500-3000 3.7 5.1 10.7 2.3
average 7.8 5.9 13.4 2.8
The above regularities in the change of the sulfur compound composition are
explained by the higher thermal stability of thiophene derivatives are compared with
sulfur compounds of other types, which leads to a predominant preservation of
"residual" sulfur in oils during long catagenesis. In order to prevent thermal
destruction of petroleum components upon distillation and to establish the composi·
tion of native sulfur compounds, 35 oils from terrigenous Paleozoic fields in the
Ural-Volga region and one Low Cretaceous oil of West Siberia were distilled in
vacuum. The temperature in the still was maintained below 160 °C, which is 20 oc
8
lower than the sulfur compound thermal stability threshold. The petroleum
distillates obtained are much poorer in sulfur than analogous products of conventional
distillation. Hydrogen sulfide is practically absent. Elemental sulfur is found in an
0
~
.
~
:<!'4
~ Q4
~
0
0
g;
~Cl2
::::::>
tf.)
0
4
t.2.
Q8
Q.4
0-4--....!..:.'i:=:=:-"""""i,._,....;;;;;::.....-a
tD
FIGURE 17. Effect of the depth of occurrence on the content of sulfur: total (a), sulfide (b) and
"residual" (c) in distillates IBP-120 "C (1), 120-200 oc (2), 200-250 oc (3), 250-300 <>c (4), and
IBP-300 oc (5), obtained by mild distillation of oils.
amount not exceeding 0.0001%. The total sulfur content of these distillates decreases
with submerging the oil-bearing beds to 3000 m (Fig. 17).
The mercaptan content of the distillates obtained under mild conditions is much
lower than in the products of conventional distillation. In contrast to the latter, the
mercaptan concentration increases as the boiling point rises, not exceeding, however,
0.005%, even in the 250-300 oc fraction. With increasing depth of occurrence and
166 G. F. BOLSHAKOV
age of the enclosing Paleozoic rocks, the concentration of mercaptans of all the
distillates decreases.
The disulfide sulfur content of gasolines does not exceed 0.002%, rising to up to
0.006 weight % in the kerosine fractions, and appreciably increases with ~he depth of
occurrence. In spite of low absolute concentrations, the disulfides contam up to one
third of all the sulfur present in the IBP-120 oc distillates of oils of the deepest
Carboniferous and Devonian rocks. The disulfide portion among the sulfur com-
pounds in broad IBP-300 oc fractions noticeably. increases upon plunging the
oil-bearing beds (Fig. 18). As the boiling point of the fraction rises ~he content of
mercaptans and disulfides increases more slowly than that of sulfides and thiophenes
and, consequently, of total sulfur. Therefore, the content of mercaptans and
disulfides among the total sulfur compounds of heavy distillates decreases (Fig. 19).
These results are in agreement with the data reported. 41 •89-91
The concentration of sulfide and thiophene sulfur in the distillates obtained by
fractionation under mild conditions is lower than in the products of conventional

distillation. This is especially true for oils from deeply submerged beds. The sulfur
content of the products of mild distillation is always higher than that in the fractions
obtained by conventional distillation.
With rising boiling point of the fractions the sulfide and thiophene content
increases, the thiophene concentration more rapidly. Sulfides, therefore, represent
the predominant sulfur compound type in the distillates boiling below 250 oc
whereas in the 250-300 oc and, possibly, heavier fractions this role is passed on to the
thiophenes (Fig. 19).
With increasing depth of occurrence, the relative sulfide content in the fraction
IBP-300 oc after mild distillation decreases and the relative thiophene content
increases (Fig. 18).
So, the low-boiling fractions obtained by mild distillation of oils from terrigenous
rocks contain practically no hydrogen sulfide and elemental sulfur, considerably
reduced amounts of mercaptans and disulfides and an increased amount of sulfides.
Thus, some new opposite trends in the change of mercaptan and disulfide sulfur
concentrations in fractions depending on the boiling point have been recognized after
mild distillation.
No tests of this kind with low temperature distillation of oils from carbonate rocks
have been reported. Upon conventional rectification of these oils, however, hydrogen
sulfide and lower mercaptans were frequently present in cuts collected already at
40-60 °C. These values, comparable with temperatures in bedrocks, evidently cannot
be regarded as "thermal stability threshold". Compounds capable to undergo
cleavage at so low temperatures must have decomposed completely in the Earth's
depths during the existence of the oil fields. The appearance of hydrogen sulfide and
mercaptans in low-boiling gasoline distillates should be considered as evidence for the
presence of these substances in the oil-bearing beds. 41
11.5. On the Genesis of Organic Sulfur Compounds
Sulfur compounds are present. i? all oils. It seemed natural, therefore, to suggest
that the sulfur compounds ongmate as a result of the transformation of organic
ORGANIC SULFUR COMPOUNDS OF PETROLEUM
167
40
20
0~--~~~~~==~~~
1 2 J
DEPTH OF OCCURRENCE, km
FIGURE 18. Effect of the depth of occurrence on the sulfur compound group composition in
distillates IBP-300 "'C obtained by mild distillation of oils from terrigenous Paleozoic rocks. Designations
are given in Fig. 11.
compounds that are precursors of oils. 92 Consequently, young oils should contain
more sulfur compounds than ancient oils. The sulfur content of biogenic ·precursors
is, however, not high enough, to allow the formation of a considerable amount of
sulfur compounds in caustobiolithes. 41 •93 •94 Most initial organic materials contain no
168
G. F. BOlSHAKOV
tOO
•
g
'?
~
H
FIGURE 19. Sulfur compound average group composition in various distillates of oils from
terrigenous Paleozoic rocks, obtained by mild distillation. Designations are given in Fig. 11.
sulfur. Thus, sulfur is absent in many proteins, lipids, most amino acids, carbohy-
drates (cellulose, hemicellulose, pectins), chitin, amino sugars, phenolic compounds
(lignin, tannin, lignan, lignite, etc.), and pigments (chlorophyll and carotenoids). No
sulfur is found in humic
-
acids and melanoids.- Sulfur is present in some amino acids ,
such as cysteine, HHSCH2CH(NHz)COOH, cystine [H--SCH2CH(NH )C00Hh
2
and methionine, H3CSCH2CH2CH(NHz)COOH. Brown algae protein contain~
taurine, H52 NCH 2CHzS020H. Sulfur compounds appear in appreciable quantities in
kerogene. Sulfur compounds are also present in coals. 95
Young oils, for example Caucasus oils, are very often poor in sulfur compounds
whereas old oils, for instance, those from the Ural-Volga region, are much
richert. 3 •4 •38 A major part of the sulfur compounds in young oils are cyclic, a feature
which is almost absent in the initial biogenetic matter. Characteristic features of the
sulfur compound group chemical composition of oils of varying age also speak in
favor of secondary insertion of sulfur into petroleum compounds. 3 •38 •41 •94 •96-98 The
cyclic sulfur compounds are most likely the result of the reaction of hydrocarbons of
the oil precursors with sulfur. This indicates the existence of a source of sulfur for
these reactions. The sulfur can be formed by reduction of sulfates which often
accompany oil-bearing rocks as gypsum. The reaction with hydrocarbons or oil
precursors may involve the reduction of sulfates to form gaseous carbon dioxide,
hydrogen sulfide, and water. These reactions, however, require high temperatures,
which is only possible at comparatively large depths.
Sulfate can be readily reduced at fairly low temperatures and pressures to sulfur,
sulfides, hydrosulfides, and hydrogen sulfide by different bacteria, such as Desulfovib-
rio which take up their essential oxygen from sulfate. Sulfides react with water to form
hydrogen sulfide and acidic sulfides (Fig. 20).
These reactions have been examined experimentally by many workers. Oil fields
are nearly always accompanied by the water necessary for bacterial growth. Specially
conducted tests38 have shown that sulfate introduced artificially disappears very soon.
No sulfate is present in oil strata water. The sulfate-reducing bacteria grow and
develop normally in oil-bearing beds even at temperatures as high as 90 °C.
When exposed to the action of oxygen, hydrogen sulfide is readily oxidized to
elemental sulfur which reacts with hydrocarbons with the possible formation of sulfur
compounds. This reaction proceeds comparatively smoothly at elevated tempera-
tures, especially in the presence of catalysts in the surrounding oil-bearing rocks.
The formation of hydrogen sulfide is also possible in an alkaline medium by the
reaction of hydrosulfides with carbonic acid (Fig. 20). The hydrogen sulfide is further
FeS
NaOH
Scheme 1
t Serious exceptions are possible. Cenozoic oils of California and Mexico, for example, contain much
sulfur which is nearly absent in Paleozoic oils of the northwestern states of the USA.
ff
fDil
!!" p
:-
q ~
tl'
- tc
/IIH~SJHR
0
~
::c
>
::-;
~
FIGURE 20. General scheme of organic matter evolution in the Earth's history and sulfur compound formation.
!-hydrocarbons, amino acids, lipids; 2-sulfonic acids; 3-huniin; 4-inherited bitumoid-hydrocarbons + heteroorganlc (N, 0, S)
compounds; 5-humic acids; 6-kerogen; 7-gas; 8-petroleum; 9-upper sedimentary layer, well or moderately aerated; 10-deep layer
devoid (at least in part) of oxygen; 11-zone of considerable transformation of molecules; 12-upper sedimentary layers, reducing
oxygen-free conditions.
oxidized to sulfur. Since the reducing medium containing hydrogen sulfide cannot
serve as an oxidizing medium this apparent contradiction can be due to the reaction of
ferric oxide with hydrogen sulfide.
Subsequently an insertion of sulfur into hydrocarbons takes place. Some of the
oil-bearing sedimentary rocks contain oxides of bivalent metals which react with
hydrogen sulfide without liberation of sulfur (Fig. 20). This could provide some
evidence as to the initial character of the sulfur compounds contained in petroleum,
and the medium might be both reducing and oxidizing, although the bivalent nature
of the sulfur compounds in the petroleum indicates clearly a reducing or, at least,
non-oxidizing medium.
The existence of an oxidizing medium at the expense of air oxygen does not
correlate with the presence of a gas free of nitrogen and of hydrogen sulfide in
petroleum. On the other hand the hydrogen sulfide occurs in varying concentrations.
There is no direct relationship between the age, type of petroleum, saline water
composition, and hydrogen sulfide content. Besides, the isotope composition of the
sulfur of oils is remarkably constant in oil fields of the same age over vast areas and
even regions, but differs much between oils of different age which occur in the same
region. 38
Thus, the formation of sulfur compounds proceeds parallel to the formation of
petroleum as a single process and is determined by the regional conditions of the
sedimentation basin. Practically any petroleum can undergo sulfurization under
appropriate external conditions. It should be noted that the processes of petroleum
sulfurization have not been studied sufficiently. There are some regions abundant in
hydrogen sulfide waters although the oils in these regions are poor in sulfur (western
regions of the USSR).
It has been established experimentally41.63 •99 that elemental sulfur can react with
hydrocarbons at 150-190 °C. The reactivity of hydrocarbons in this process enhances
with increasing molecular weight and aromaticity. Sulfur reacts most readily with
polycycloaromatic hydrocarbons, less readily with monocycloaromatics, and most
reluctantly with alkanes. Unlike terrigenous collectors, carbonaceous rocks act as
catalysts in these processes. 26 This may be responsible for the interrelation of the
sulfur content of oils with the litho logic features of adjacent rocks. However, no
thiacycloalkanes have been found among the products of the reaction of sulfur with
hydrocarbons, in spite of the fact that these compounds account for about half the
sulfur compounds occurring in oils. There is no reliable information concerning
possible ways of formation of thiacycloalkanes in petroleum. The thiacycloalkanes
appear to have been formed upon further destruction of thiacycloaromatic hydro-
carbons which has led to the formation of thiacycloalkanes and arenes. This
suggestion is supported by the fact that ancient oils are of low viscosity and
intermediate molecular weight.
Hydrogenation of thiophenes to thiophanes is also possible. This reaction is readily
carried out in the laboratory, but no isomerization of methylthiophane to thia-
cyclohexane occurred even upon prolonged reflux with aluminium chloride. 93
The thiophanes and thiophenes may be assumed to have been generated by
heteroatomic exchange with the corresponding oxygen- and nitrogen-containing
cyclic analogs at 400-450 oc in the presence of alumosilicates. These processes,
172 G. F. BOLSHAKOV
however, hardly could occur not only because of the high temperature requirement,
but also for want of obvious sources of nitrogen- and oxygen-containing analogs.
Furthermore, the presence of nitrogen- and oxygen-containing saturated six- and
five-membered heterocycles is not characteristic of petroleum.
The problem of the origin of thiophenes has not been studied in detail. In the initial
biogenic matter thiophenes are very rare. The origin of thiophenes can be explained
in terms of the reaction of sulfur with hydrocarbons and, less likely, the exchange with
furans and pyrroles in the dehydrogenation of thiacyclopentanes, occurring quite
rapidly at 160-170 °C. 100 An unlikely suggestion 101 that the thiophenes originate from
structurally related "thioporphyrines" should also be noted.
With increasing geological age of oils the amount of thiophenes increases. The ratio
of non-thiophene:thiophene compounds (a) decreases. So does the ratio of benzo-
thiophenes to dibenzothiophenes ({3): 3 organic matter--+ young oil--+ (a= 3.9,
f3 = 1.6) --+ oil of average age (a = 2.2, {3 = 0.8) --+ old oil (a = 1.27, f3 = 0.28).
These data have been obtained from studies of 78 oils from beds varying in age from
Cambrian to Pliocene. 3
Undoubtedly, the sulfur compound origin can be substantiated only by taking
into account the genesis of other petroleum components. The chemical composition
of oils shows clearly that the main structural features and genetic destructive changes
of sulfur compounds are very similar to the corresponding characteristics of
hydrocarbons. The most typical common features are:
1. The sulfur compound carbon skeletons correspond to the skeletons of
hydrocarbons in petroleum and its fractions. In young oils, for example, which belong
to the naphtheno-alkane type the major part of the sulfur compounds are represented
by thiacycloalkanes and aliphatic sulfur compounds.
2. With increasing geological age of petroleum the share of light fractions and the
aliphatic sulfur compound content of low-boiling fractions enhance. Increase in the
aromaticity of petroleum leads to higher contents of thiophene structures which
resemble arenes in their physico-chemical properties. The changes in the distribution
of polycyclic arenes and polyarenothiophenes are clearly correlated by the number of
fused aromatic rings.
3. The structure of naphtheno-aromatic hydrocarbons is consistent with that of bi-
and polycyclic sulfur compounds containing thiacyclopentane and thiophene struc-
tural fragments.
The available data suggest the following scheme for the sulfur compound
genesis. During the formation of petroleum at early stages up to the development of
catagenic processes sulfur is inserted in organic molecules without destructing them to
any considerable extent. This results in the formation of sulfur compounds with
saturated heterocycles and carbon skeletons analogous to the backbones of the initial
compounds. Biogenic structures cross-linked with sulfur atoms are also formed.
These compounds serve as the original material for the formation of some tar-asphalt
substances of petroleum. Young, poorly reworked oils are very rich in tar-asphalt
substances containing sulfur as sulfides. 4 Further development of the catagen·1
processes involves reduction of the average molecular weight, accumulation 0 ~
low-boiling fractions, increase in the arene content of petroleum heavy fractio
degradation of the least stable sulfur compounds. Some of the thiacycloalka:~
undergo decomposition and dehydrogenation to form thiophenes and other sulfur

compounds.
Since the destructive transformations of petroleum precursors follow a radical chain
mechanism, there always exists a possibility of the formation of thiols, sulfides, and
disulfides due to the reaction of hydrogen sulfide and elemental sulfur with hydrocar-
bon radicals. The direction of the above reactions is determined by the activity and
structure of the radicals. The amount of sulfur in the generating oils decreases
gradually, the aliphatic thiols are accumulated in light fractions and the thiophene-
thiols in residual and heavy fractions. The polyarenothiophenes are generated in
greater amount. 3 •4 Along with the thiols, other sulfur compounds such as aliphatic
sulfides, disulfides, and thiophanes can be generated, of course. The group chemical
composition of the sulfur compounds generated is governed by the catalytic
properties of the enclosing rocks, 29 •102 and the participation of additional sources of
sulfur and hydrogen sulfide in the catagenic processes. 3
Ill. ISOLATION AND REMOVAL OF ORGANIC SULFUR COMPOUNDS

FROM CRUDE PETROLEUM AND ITS DISTILLATES
III.l. Sulfonation
In the oil processing industry, concentrated sulfuric acid has long been used for
refining. distillates and residual products. In this process, acid asphalt consisting of
unreacted sulfuric acid, products of sulfonation, oxidation, condensation of unsatu-
rated and aromatic hydrocarbons, and heteroorganic compounds, is produced. Only a
minor part of the most stable compounds remains practically unchanged in this acid
asphalt. Due to the large quantity of wastes sulfonation with concentrated sulfuric
acid is being replaced by more promising techniques.
Concentrated sulfuric acid is a rather strong oxidant, therefore sulfur compounds
undergo both sulfonation and oxidation:
RSH + H2so 4 RSSR + H20 + so 2
RSR + H2so 4 RSR + H20 + so 2

11
0
~ + H SO
RX 5/ 2 4
Scheme 1
174 G. F. BOLSHAKOV
Some sulfur compounds can be recovered from acid asphalt by hydrolysis. For
this purpose acid asphalt is neutralized and the sulfur compounds are steam
distilled. In the treatment of petroleum distillates with concentrated sulfuric acid
some of the aromatic hydrocarbons and most sulfur, nitrogen, and oxygen com-
pounds, as well as sulfuric acid are lost.
A certain part of the sulfur compounds can be isolated from acid asphalt as an
aromatic sulfur concentrate according to a very complicated scheme (Fig. 21). Thus,
27 individual sulfur compounds have been isolated by this method 55 from the.
140-250 oc fraction of Iranian oil. These compounds were isolated as mercury acetate
complexes which were further decomposed. The sulfur compound structures have
been proved by their physico-chemical properties and spectral data. The IR spectra of
the hydrocarbons obtained by sulfur compound hydrogenolysis on Raney nickel have
been studied.
A multi-step sulfonation of sulfur compounds with acid of increasing strength
allows a more complete sulfur compound recovery. For example, the 150-325 °C
fraction of Arlan oil, from which all sulfur compounds except thiophenes were
previously removed, 2 was consecutively treated with 92 and 93% sulfuric acid at room
temperature and in an acid: fraction volume ratio of 1:5. 47 % thiophene sulfur was
removed in this way. Other sulfur compounds which cannot be extracted with
concentrated sulfuric acid should be regarded as highly stable compounds whose
structures require further investigation.
111.2. Adsorption and Rectification
Chromatography is widely applied for separating sulfur concentrates. Silica gels,

aluminium oxide, clay minerals, and other compounds are used as adsorbents. 103 •104
A petroleum fraction or a crude petroleum is spread over the adsorbent usually
placed in a column. Alkanes and cycloalkanes are separated with petroleum ether or
isopentane. Aromatic hydrocarbons are isolated together with the bulk of the sulfur
compounds. Some sulfur compounds are desorbed from the adsorbent with solvents
of increasing polarity.
Low-molecular sulfur compounds are more weakly adsorbed on silica gel than
nitrogen- and oxygen-containing compounds, but more strongly than hydrocarbons.
The sulfur compound adsorption activity increases in the following order:
thiophenes < aliphatic mercaptans < aliphatic disulfides < aromatic and cyclic
thiols < aromatic disulfides < aliphatic and cyclic sulfides.
For aliphatic sulfur compounds the adsorption activity decreases with increasing
molecular weight. The adsorption activity of sulfides increases with increasing number
of rings. The presence of 7T-electrons conjugated with lone pairs on the sulfur atom
facilitates the separation of mixture of sulfides with arene thiaheterocycles. The
possibility of enriching the sulfur compound chromatographic fractions by properly
chosen adsorbents, eluents, and separation conditions has been shown. 44 ,103,10S,l06
As an example of the application of adsorption techniques for the isolation of sulfu
compounds, the results of two inv~stigations 1 ~· 108 ~an be cited. The jet fuels TS-~
and RT-2 were chosen as the subJect of an mvesbgation. 119
The aromatic fractions were chromatographically separated from the fuels. Most
Kerosine 140°-250°0,
0.36 wt.% of total sulfur
t
Sulfonation with 98% H2S0 4 (0.4 vol.%)
t
I '
Acid asphalt Refined product,
0.25% of total sulfur
t
Dissolution in an equal volume (by weight) of water and decantation
'
Oil, 18.1 wt.%
of total sulfur
'
Sulfuric acid solution
t
Neutralization with alkali
Vacuum distillation
t
~--------------------------~
[ Distillate Residue boiling above 254°C,

7.5% of oil
I
Secondary sulfonation within -5•+5°C
range (9~ H2so 4 :d{stillate ratio=2:1)
Dilution, hexane washing, decantation

f t
~ ISulfuric acid solution I
I
Neutralization with alkali
f
(Oil, 18,9 wt.% of total sulfurj
Vacuum distillatiJn into 12 fractions

(column productivity 14 theoretical plates)
l
Vacuum distillation of fractions
with maximum sulfur content
(column productivity 100 theoretical plates)
l
27 Narrow fractions of aromatic
sulfur concentrate
FIGURE 21. Flow sheet of the isolation by sulfonation of petroleum fractions.
176 G. F. BOLSHAKOV
TABLE 21
Sulfur Compound Group Chemical Composition in Aromatic Fractions
of the Fuels TS-1 and RT
Parameters TS-1 RT
Total sulfur content, %, including sulfur in: 0.63 0.44

hydrogen sulfide none none
mercaptans 0.03 0.02
sulfides 0.28 0.18
disulfides 0.06 0.08
"residual" (thiophenic) 0.26 0.16
sulfur compounds were isolated together with these fractions. Data concerning the
sulfur compound group chemical composition are presented in Table 21.

The aromatic fractions were further repeatedly separated chromatographically on a
modified silica gel ShSM in cone columns 5 m high. All the eluates were subdivided
into three groups according to the sulfur content, up to 0.04, 0.04-1.0, and over 1%.
The group with a sulfur content of 0.04 to 1% was subjected to a secondary
chromatographic separation, and the resultant fractions with a sulfur content over 1%
were added to the third group. Thus gradual enrichment in sulfur compounds took
place in the third group of concentrates which was later again subjected to
chromatographic separation. Finally, concentrates with a sulfur compound content
of 2.94 and 3.48% (calculated from the sulfur contents) from the fuels RT-2 and
TS-1, respectively, were obtained. It should be noted that the sulfur compound
isolation is a very time-consuming procedure, where the yield of concentrates is
relatively low.
From the concentrates thus obtained the sulfur compounds were isolated by
complexation (Table 22). The sulfur compounds isolated mainly consist of sulfides
and "residual" sulfur. In sulfur compounds from RT aromatic fractions, apart from
sulfide and "residual" (thiophene) sulfur, a small amount of disulfides was found.
TABLE 22
Characteristics of Sulfur Compounds from Aromatic Fractions of Fuels
Parameters TS-1 RT
Content in fuel, % 0.520 0.430

3
Density, kg/ cm 0.9241 0.9342
Refractive index, n~ 1.4704 1.4878
Molecular weight 172.4 207.4
Elemental composition,%:
c 71.52 70.38
11 9.38 9.92
s 18.74 19.57
The IR spectra of sulfur compounds from the RT aromatic fractions show a

moderate absorption at 1290 cm- 1 (CH3-S) and 680 cm- 1 (C-S). An intense
absorption band near 1000 cm-I, uncommon in hydrocarbons, seems to be related to
sulfur bonds. The absorption bands at 626, 617, 600, 586, 578, 565, 559, 540, and
534 cm - 1 provide evidence for the presence of thiophane rings and mercaptans
(565 and 540-535 cm-1, respectively). The C-H bond absorption is observed as
a weak shoulder at 2622 cm - 1 . The intense band near 760 cm - 1 may be assigned to
monoalkyl substituted tiophanes. The intense doublet near 1600 cm- 1 and intense
bands at 810 and 750 cm- 1 indicate the presence of aromatic rings, including bi-
cyclic systems.
Thus, in fuels of the RT type the major part of the sulfur compounds are
predominantly aromatic sulfides and thiophenes. The alkylthiophenes seem to be
contained in the "residual" sulfur and cannot be determined by potentiometry,
though their presence can be detected in the IR spectra. Among the sulfur
compounds structures with two sulfur atoms in the molecule can occur (Table 22).
The sulfur compounds of the aromatic TS-1 fractions contain mainly aliphatic
compounds. This is confirmed by the IR spectra and by physico-chemical analysis
showing a mixture of aliphatic sulfur compounds, thiophanes, and thiophenes.
Strong absorption in the 1220-1240 cm- 1 region in the absence of oxygen
compounds is indicative of the presence of a sulfur atom in a five-membered ring. The
1247, 1209,930 cm- 1 bands characterize at-butyl group and the 1170 and 1920 cm- 1
bands correspond to an isopropyl group. A very intense band near 760 cm-• may be
related to 3-alkylthiophane derivatives. Absorptions near 567 and 559-550 cm -• give
evidence for the presence of considerable quantities of thiophanes and thiophenes,
respectively. The thio compounds observed can be characterized as predominantly a
mixture of 3-alkylthiophanes, alkyl being a branched structure (isopropyl, t-butyl).
The occurrence of aliphatic sulfides is shown by IR absorption in the 600, 587-
580 cm -• region and the presence of thiols is implied by a band near 540 cm -•, typical
for the thiol group (as first pointed out by the present author and E. A. Glebovskaya
in 1960) and by absorption at 2600-2550 cm. - l
The band intensity increases from aliphatic to aromatic thiols, reaching a maximum
in conjugated systems. Since the sulfur compounds from the fuel TS-1 were mainly
aliphatic, the absorption of the thiol groups is poorly expressed in the spectra.
The "residual" sulfur fraction contains predominantly thiophene homologs. In
order to substantiate this suggestion more strictly, special tests have been carried out.
Use of the unequal susceptibility to oxidation e~tablished by us previously has allowed
sulfur compounds to be selectively oxidized. Since thiophenes are more difficult to
oxidize than other compounds, the absorption bands of thiophenes in the IR spectra
of unoxidized sulfur compounds, taken after oxidation and chromatographic
separation of the oxidation products, must be more intense.
Indeed, there was a 1.5-2-fold increase in the intensity of the absorption bands in
the 559 and 550 cm-• region in the unoxidized part. More intense are also the
absorption bands in the 990-1000 cm- 1 region which indicates the presence of 3-alkyl
substituted thiophenes, and a doublet at 847-820 cm-•, characteristic of monoalkyl
substituted thiophenes. So is an absorption band near 1242 cm-• present in the
spectra of all the alkylthiophenes except 3,4-dimethylthiophene. These data provide
178 G. F. BOLSHAKOV
fairly convincing evidence for the occurence of thiophenes among the sulfur com-
pounds isolated.
The adsorbent structure affects much the mechanism and energy parameters of the
adsorption process. Fine-porous silica gels are more selective towards sulfur com-
pounds than coarse-porous ones, which is possibly due to a more developed surface
and to the presence of a hardening admixture, aluminum oxide. Therefore, fine-
porous silica gels permit high-sulfur chromatographic fractions to be obtained.
For a better understanding of the adsorption mechanism on silicas the influence of
the dehydroxylation of silica gel on sulfur compound adsorption processes was
studied by various methods. Contrary to a widely accepted opinion, it turned out that
the desorption of water from the silica gel surface with rising temperature is not a
continuous, but a discrete process. This is indicative of different forms of interaction
of water with silica gel. The thermal desorption curves of four zeolites studied at the
Tomsk Institute of Oil Chemistry (KSKG, ShSKG, ASK, and Silachrom-S-80)

contain five maxima near 340, 560, 868, 1180, and 1440 K (Fig. 22). It has been
established by IR spectroscopy that the first form corresponds to the removal of
physically adsorbed water. The interpretation of the mechanism of the disappearance
of form 11 is difficult and ambiguous. The removal of form Ill coincides with the
disappearance of the IR band at 3540-3550 cm- 1 , which indicates desorption of
hydrogen-bonded superficial OH groups. Form IV correlates with the absorption
band at 3640-3680 cm- 1, caused by bulky OH groups_Hl9 After this the spectrum
shows only the well-known narrow band at 3749 cm- 1, corresponding to superficial
non-bonded OH groups, the removal of which is responsible for the appearance of a
maximum near 1440 upon thermal desorption (form V).
The water forms recognized here have been shown to be removed during the course
of thermal desorption. If possible transition of one form to another during the thermal
desorption is neglected, integration of the curve shows the quantitative distribution of
"bound water" in the adsorbents. Thus, for silica gel KSKG, the distribution of the
dO
aT
.500 4111 ~ f11) 700 8f1D {1)() 1000 1200 1400 1800
K
FIGURE 22. Thermal desorption of water from silica gels: 1-KSKG, 2-ShSKG, 3-S-SO.
ORGANIC SULF1JR COMPOUNDS OF PETROLEUM 179
1
-375K
1180K
K
FIGURE 23. Content of "bound water" of various types in silica gel KSK-2.
1-before treatment, 2-after programmed thermal treatment up to 1050 K and cooling.
above water forms in 1 g of adsorbent is as follows:

1-3.9 mmole of H 20; 11-0.24 mmole of H 20, 0.49 mmole of OH; 111-2.1 mmole of
OH; IV-0.9 mmole of OH; V-0.3 mmole of OH. The good reproducibility of results
in repeated tests with silica gels of the same series shows that exposure of the samples
to ambient conditions prior to the test does not affect the distribution of different
water forms appreciably. The ratio of certain types of hydroxy groups can be
controlled by programmed thermal treatment (Fig. 23). This may be used for the
optimization of production processes for adsorbent silica materials.
Upon adsorption of low-molecular sulfur compounds on silica gel at 375 K large
heats of adsorption (over 120 k.J/mole) are observed, 40-70 and 20-30 kl/mole at
about 560 and 870 K, respectively. The energies of interaction of sulfur compounds
with the adsorbent depend both on the functional features of the sulfur atom and the
structure of the sulfur compound hydrocarbon backbone. With dehydroxylation of
the adsorbent the influence of the nature of the sulfur atom function on the sulfur
compound adsorption becomes more prominent.
To increase the adsorption activity with respect to sulfur compounds the silica
adsorbents are subjected to modification. Nickel-, nickel oxide- and nickel sulfide-
modified silica gels have been studied. The best results were obtained with nickel
180 G. F. BOLSHAKOV
sulfide as a modifier. The separation of mesitylene from sulfides on this adsorbent is

almost 3.5-fold better than with the unmodified silica gel. Upon modification of the
adsorbents with nickel and its compounds decomposition of sulfur compounds is
possible. As shown by spectral data part of the sulfur compounds adsorbed on a
Ni-modified adsorbent undergo decomposition to form the following structures: 110•111
SH CH2 - CH2 R H H
\
I~ I~ I ··.··a:·.··
~H2 s
Ni
Ni Ni
Ni
ll ;· \.Ni
Ni
The ability of sulfur compounds to complex with mercury and silver salts can be
utilized to modify adsorbents. It should be noted, however, that adsorbents modified
with mercury and silver salts are unstable since the modifiers are reduced to metals
during the adsorption. The effect of modifiers on the interaction of sulfur com-
pounds with sorbents has been studied. 103 The adsorption activity of aerosil
modified with aluminium, cadmium, boron, iron, and titanium oxides is essentially
different from that of pure aerosil. The shift of the v011 stretching is considerably
smaller for modified silica as compared with the unmodified varieties (Table 23). The
smallest shift is observed in the adsorption of thiophene and thiophenol, which is
possibly due to the presence of the arene system. The interaction of sulfur com-
pounds with a modified adsorbent involves the formation of coordinate linkages
with Si. ... OH groups and electron-deficient sites of the metals. Dehydrogenation
and hydrogenation of the compounds adsorbed and, correspondingly, rehydroxyla-
TABLE 23
Shift (cm- 1 ) of the v08 stretching of silicon and aluminum oxides and
modified silica relative to the 3760 cm-• band
Silica + modifiers
Compounds Alz03 Si01 CrO AhO, Ti01 Fe103 8103

Thiophanes 130 415 200 180 215 215 168
Ethyl 1-propyl sulfide 200 390 200 210 195 210 143
Diethyl disulfide 120 230 115 120 115 110 105
1\onylmercaptan 120 280 120 115 120 110 • 103
Thiophenol 116 200 125 100 115 115 100
Thiophene 100 116 135 100 104 115 103
G. F. BOLSHAKOV 181
tion of the modified silica surface are also possible. For example:
OH OH
SiOB/
'oH
+ HS
0 ~ SiOB/
"'-s-0
0
+ H20
The adsorption activity of modified silica is restored completely by removal of the

adsorbed molecules in vacuo at 700-800 K, which indicates that fairly stable
complexes are formed on the adsorbent surface.
The activity of silica gels can be increased by modification with organic compounds,
such as alkyltrichlorosilanes, phenyltrichlorosilane, etc. 103 Aluminium oxide is em-
ployed as an adsorbent in chromatographic separation. The interaction of sulfur
compounds with aluminium oxide is rather complicated because of the presence in
the latter of a large number (up to 5) of active site types with different acidity. 112 •113
The influence of the sulfur compound nature on the heats of adsorption on
aluminium oxide has been investigated. These data have been compared with those
reported for silica gel (Table 24). As seen from these data, the heats of adsorption
increase in the order: hydrogen sulfide-methanethiol-ethanethiol-dimethyl sulfide on
silica gel and methanethiol-hydrogen sulfide-ethanethiol-dimethyl sulfide on alumi-
nium oxide. The greater heat of adsorption of sulfur compounds on aluminium
y-oxide with equal surface occupation (1.4 mmol/m2 ) as compared with that on silica
gel is explained by the interaction of the sulfur compounds with surface hydroxyl
groups and Lewis acid sites of aluminium ')'-oxide.
TABLE 24
Heats of Adsorption of Sulfur Compounds (KJ /mole) on the Surface of
Silica Gel and Alumina Dehydroxylated at Different Temperatures
Silica gel Alumina
Compound 513 K 973K 973 K
Hydrogen sulfide 39.4 29.4 67.5

Methanethiol 46.2 42.2 66.2
Ethanethiol 49.4 46.9 73.9
Dimethyl sulfide 70.3 59.0 83.1
182 G. F. BOLSHAKOV
The modification of aluminium oxide makes it possible to diminish its "rigid" action
upon sulfur compounds. Thus, modification of tempered aluminium oxide with
2.5-3.0% water allows separation of sulfur compounds and hydrocarbons. 103
The sulfur compound concentration in sulfur-containing aromatic concentrates
can be increased by rectification. The rectification of sulfur-containing aromatic
concentrates is performed before or after the chromatographic separation. The
200-300 oc fraction of Tuimazinskaya oil, USSR, was distilled into fractions within
each 2 oc and then chromatographically separated. 114 The sulfur content of the 2 oc
fractions was 0. 96-2.8 wt.%. In the acetone-eluted aromatic sulfur concentrates the
sulfur content was 7.3-10.6 wt.%. The 2 oc fractions were further subjected to
rectification in vacuo to obtain 1 cc fractions. The secondary efficient rectification
raised the sulfur content to 7.6-11.1 wt.%, which corresponds to 40-60% sulfur
compounds.
Thus, the combination of fine rectification and adsorption purification makes it

possible to increase the sulfur compound content of aromatic concentrates. The
isolation of sulfur compounds from aromatic concentrates involves the application
of complexing agents such as heavy metal chlorides.
111.3. Selective Extraction
In 1925 the first attempt was made to isolate sulfur compounds from oil fractions
with selective extractants. 115 Sulfur compounds were extracted from the kerosine
fraction of Iranian oil by liquid sulfur dioxide at below-zero temperatures. From the
extract which represented a sulfur compound-arene mixture, the sulfur compounds
were isolated by complexing with mercury acetate. Later it was attempted 116 to
employ for this purpose aniline and ethylene glycol diacetate which proved, however,
to be less efficient than sulfur dioxide. From diesel fuel, sulfur compounds were
extracted with diethylene glycol in an extraction column. The highest yields were
obtained in an extractant:raw material ratio of 7:1, the temperature being 160 oc at
the column top and 135 cc at the bottom. The sulfur content of the diesel fuel was
reduced from 0.85 to 0.14%. The extract contained 20-24% sulfur compounds and
80-75% arenes. In the sulfur compound extraction with diethylene glycol the
maintenance costs for the production of 1 t of diesel fuel containing 0.2% sulfur are
half of those in hydrogen refining. Triethylene glycol was used to extract sulfur
compounds·from the kerosine-gas oil fraction of Arian oil and from gas oil obtained
by catalytic cracking of sulfur-rich oils of the USSR. Some characteristics of the
starting raw materials are given below:
Kerosine-gas oU fraction of Arian oil Catalytic cracking gas oil
Density, p'fkg/m3 875.6 883.8

Total sulfur content, wt.% 2.8 1.42
Boiling range, "C 220-370 200-380
For the sulfur compound isolation an efficient counter-current extractor with

Raschig ring packing was employed. The temperature was 185 and 155 oc at the
column top and bottom, respectively. The triethylene glycol:raw material ratio was
7: 1. The kerosine-gas oil fraction raffinate was a diesel fuel with a sulfur content of
0.21%. The raffinate of the gas oil of catalytic cracking was a high quality diesel fuel
with a sulfur content of 0.16 wt.%.
The possibility of sulfur compound selective extraction from petroleum fractions
with diethylene glycol, acetic acid, furfurol, phenol, N,N-dimethylformamide,
ethanol, aniline, acetic anhydride, and furfuryl alcohol was studied using the
cycloalkane fractions 117 with thiophane, ethyl propyl sulfide, diisopropyl sulfide,
dipropyl sulfide, diisobutyl sulfide, 2-propylthiophane, dibutyl sulfide, disobutyl
sulfide, and methyl phenyl sulfide as additives.
The sulfur compound extraction efficiency was evaluated by means of the
distribution coefficient
where Ce and Cr are the sulfur compound concentration in the extract and the
raffinate, respectively.
The maximum isolation of thiophanes is achieved only in a four-stage extraction
with furfuryl alcohol (K = 1.83). The distribution coefficient for other extractants was
lower (from 0.03 to 1.83). Thus, the selectivity of the extractants studied in sulfur
compound extraction has proved low and they should not be used in extraction
processes in the future.
The highest distribution coefficient was achieved when sulfur dioxide was
employed as the extractant. 118 Thus, beginning with Birch, numerous attempts to find
an extractant better than sulfur dioxide have not met with success. In a research on
phase equilibria the selectivity of sulfur dioxide relative to sulfur compounds in the
presence of aromatic hydrocarbons has been studied. 118 The fractions of sulfur Arian
oil with boiling ranges of 200-225, 275-350 and 190-360 cc were investigated.
Boiling range, °C
100-215 275-350 190-360
Density, p~0 , kg/m3 812 855 848

Refraction, ntjl 1.4537 1.4787 1.4735
Total sulfur content, wt.% 0.61 2.47 2.20
Sulfide sulfur content, wt.% 0.49 1.12 1.20
The phase equilibrium was studied at -24 cc and the extraction processes at
-13 cc. The amount of sulfur dioxide was 100 vol.%, mixing time 15 min, settling
time 90 min. The sulfur dioxide from the raffinate and the extract phases was removed
by nitrogen boiling. Then the raffinate and the extract were washed to neutral
184 G. F. BOLSHAKOV
TABLE25
Phase .Equilibria in a Thiophane-Xylene-Nonane-Sulfur Dioxide System
Thiophane content (m-xylene) of the starting mixture
Characteristics 18.5 25 29.8 34.8 37.5
Extraction phase composition, wt. %:

thiophane 7.6 10.0 13.0 15.0 16.5
m-xylene 7.3 8.5 12.0 14.0 15.5
nonane 2.5 3.5 5.8 7.0 9.5
Sulfur dioxide 82.6 78.0 69.2 64.0 58.5
Raffinate composition, wt. %:
thiophane 1.1 1.5 2.0 4.1 4.9

m-xylene 2.9 4.5 8.0 8.9 12.3
nonane 78.7 76.7 72.5 68.0 63.6
Sulfur dioxide 17.3 17.3 17.5 19.0 19.2
Distribution coefficient for
thiophane, K1 6.9 6.7 6.5 3.4 3.4
m-xylene, Kk 2.5 1.9 1.5 1.6 1.3
S 1 . . K, 2.8 3.5 4.3 2.3 2.7
e ecttv1ty, Kk
reaction. The phase equilibrium was studied with a model thiophene-xylene-nonane-

sulfur dioxide mixture (Table 25). The distribution coefficient of thiophane is higher
than that of xylene. The thiophane content of the extracts is 40-46%, the recovery
being 85-90%. The selectivity of sulfur dioxide for thiophane Kt/Kk is > 1 in all
cases. Thus, an extractive separation is possible. Sulfides and thiophanes are
extracted {Table 26) in approximately equal quantities. The degree of sulfur com-
pound extraction from low-boiling fractions is somewhat higher than that from
high-boiling fractions. A decrease in the extraction temperature to -60 °C increases
the sulfur compound .~xtraction from the 190-360 °C distillate from 28.4 to
39.8%, but has practically no effect on the extract composition (Table 27).
With a view to raising the extraction temperature the possibility of the application
of various solvents, such as diethylene glycol, acetic anhydride, nitrobenzene, and
methanol has been studied. Methanol proved to be the best solvent affording a stable
solution with a sulfur dioxide content of 40% at room temperature. With this solvent
the extraction can be performed at temperatures above zero. The composition of the
raffinates and extracts is close to those obtained by extraction with liquid sulfur
dioxide at -13 oc.
A process for extraction of sulfur compounds with diluted sulfuric acid has been
developed. 2 This method has been extended to high-sulfur straight-run fractions
boiling out within a range of 150-400 oc. Investigation of the extraction activity of
sulfuric acid has established that the latter dissolves readily the sulfides without
extracting other sulfur compounds and hydrocarbons. The best results are achieved
TABLE 26
Single Extraction (Wt. %) from Distillates of Arian Oil
Characteristics Starting solution Extract Raffinate
200-225 oc
Sulfur content
total 0.61 2.26 0.435
sulfide 0.49 1.60 0.373
Yield 100 9.5 90.5
190-360 °C
Sulfur content
total 2.2 6.25 1.75

sulfide 1.2 3.00 1.00
Yield 100 10.0 90.0
275-350 oc
Sulfur content
total 2.47 5.97 2.08
sulfide 1.12 2.90 0.92
Yield 100 10.1 89.9
TABLE 27
Sulfur Compound Extraction (Wt. %) from the 190-360 °C Fraction with
Sulfur Dioxide at -60 °C (A) and with a Sulfur Dioxide/Methanol Mixture at 180 °C (B)
Characteristics Extract Raffinate
A
Sulfur content
total 6.4 1.37
sulfide 3.14 0.80
Yield 13.7 96.3
B
Sulfur content
total 6.20 1.76
sulfide 2.90 1.01
Yield 10.0 90.0
186 G. F. BOLSHAKOV
in a two-stage extraction, with 86% acid used at the first stage and 91% acid at the
second stage. 2 The optimal extractant: raw material ratio ranges from 1:5 to 1:10
depending on the sulfur compound amount and composition.
The first extraction stage recovers nearly all the aliphatic and cyclic saturated
compounds which would decompose in stronger sulfuric acid. The second stage
involves the extraction of aromatic sulfides constituting 10-20% of the total content
of sulfides in the petroleum fraction. The phase mixing time is about 15 min under
normal conditions. The mixture is separated by settling during 3 hours. The
separation can be considerably accelerated by employing a high-speed centrifuge.
After mixing and settling, the solution of sulfuric acid with extracted sulfur com-
pounds and impurities of nitrogen and oxygen compounds and mineral contami-
nants is diluted with water to 55% strength. In this solution the sulfides are practically
insoluble and float up as a clearly separated layer. The sulfides thus obtained are
separated by chromatography, distillation, and rectification in vacuo. The sulfides

distilled are of straw-yellow color whereas high-molecular brown sulfides of rather
high viscosity are concentrated in the stillage residue. The sulfides isolated were of
85-87% purity. The purity of the sulfides can be increased up to 99-99.7% by a rather
simple technique (Fig. 24),
Recovery of sulfides by extraction with aqueous sulfuric acid solutions has been
performed at the Ishimbay oil processing factory in a periodically operating plant.
Sulfu:r compounds were extracted from the 170-310 cc diesel fraction of Arian oils.
The oil fraction is pumped with a crude oil pump (P-4) (Fig. 25) to the bottom of
extraction column 1. The 86% sulfuric acid is pumped to the top of this column by
pump P-2. The extraction is carried out at atmospheric pressure and ambient
temperature. From column 1 the hydrocarbon fraction flows by gravity to column 2 to
enter the second extraction stage. The 91% sulfuric acid is pumped into column 2
with pump P-2 for subsequent sulfur compound extraction. The raffinate phase is
passed through the top of column 2 into electric separator 6 for separating traces of
aqueous acid solutions and then into vessel3 where the raffinate is further refined with
an aqueous alkali solution using mixer M-3. The raffinate is further transferred to the
final product receivers.
The extractant with the sulfides from column 1 is diluted with water in mixer M-1
to a 55% sulfuric acid and fed into settler 5. In this settler the mixture is separated
into two phases, the upper phase representing crude sulfur compounds after the
first extraction stage and the lower phase being 55% sulfuric acid.
The extractant and the sulfides from column 2 are diluted with water in mixer M-2
to 55% sulfuric acid and transferred to settler 4 in which also two phases are formed.
The upper phase consists of crude sulfides after extraction stage 11, the lower phase is
55% sulfuric acid. The crude sulfides from settlers 4 and 5 are passed to collectors.
These sulfides can be used as commercial products after removal of traces of sulfuric
acid by washing with aqueous alkali solutions or in the electric separator to neutral
reaction. Purer sulfides (90-92% purity) are obtained by vacuum distillation of the
crude sulfur compounds. To obtain sulfides of 95-98% purity fractional re-
extraction is used. The crude sulfides are pumped with pump P-8 to the lower part of
extraction column 7 and 76-86% sulfuric acid is supplied to the column top. The
hydrocarbon mixture obtained in column 7 is refined in an electric separator (9) and
~etroleum distillate!
t
Extraction with
diluted H2so4
I
'
Crude sul!ides after
1st extraction stage
'
Crude sulfides after
2nd extraction stage
15.1% s, purity 86% 9.0% S, purity 5.3%
t
Extraction with 78% H2so
t
4
f ' t t
Fraction 1
17.1% S, purity 99.7%;
Residue
1.3.4% s,
'
Fraction 1
14.2% s, purity 82%
Residue
6.98% s,
yield 49% yield 59.9% yield 28.1% yield 70.5%
t
Fraction I I
6.4% S, purity 9.3.2%;
~----
Extraction
with 82 H2so
Fraction II
1.3.7% s
•
Extraction
with 84% H2 so4
yield .31. 1% 4
Residue
I
Residue
8 • .36% S; ).12% S;
yield 18.0% yield 4.3.4%
t
Fraction I I I
15.0% S, purity 97.7%;
yield 11.~
Extraction
with 84% H2so
4
Fraction III
12.5% S, purity 82.5%;
yild 10.2%
·--- Extraction
w ith 86% H2so
4
Residue
l l
Residue
1.28% S; 0.89% S;
yield 6.1% yield .32.2%
FIGURE 24. Scheme of purification of sulfides by fractional reextraction with aqueous sulfuric acid solutions.
-
00
00
I
'
I
,.--
I
I l
P-t P-2 P-.J P-4 P·.S

tQ
p-6 p-7 P·tO P·tf
FIGURE 25. Simplified flow chart of sulfide removal by extraction of high-sulfur petroleum fractions with aqueous sulfuric acid solutions.
1,2-extraction columns at the first and second stage, respectively; 3-vessel for fuel fraction neutralization with alkalies; 4,5,8-settlers for
separation of sulfides; 6,9-electric separators; 7-extraction column for crude sulfides; 10-vacuum column for sulfide distillation; P-1, P-2,
P-3-pumps for aqueous sulfuric acid solutions; P-4-pump for feedstock; P-5, P-6-pumps transferring the extract phase (aqueous sulfuric
acid + sulfides) to settlers; P-7-pump transferring the fuel fraction after isolation of sulfides to alkaline washing; P-8-pump for crude
sulfides to be refined by reextraction; P-9-pump for supplying alkali solution; P-10-pump for spent sulfuric acid; P-11-pump for
high-molecular sulfides (stillage residues); T-1, T-2, T-3-tanks for aqueous sulfuric acid solutions, 78-86, 86, and 91% strong, respectively;
T-4-feedstock tank; M-1, M-2, M-3, M-4-mixers with water and aqueous alkali solution; H-1-heater.
TABLE 28
Fuel Quality after Sulfur Compound Removal with Dilute HzS04
Parameters Starting fraction Fraction after refining stage 11
Yield,% 100 93.9

3 808 806
Density, p?f, kg/m
Fractional composition, "C
initial boiling 170 172
10% 182 187
50% 219 218
90% 273 274
end boiling 300 303
Viscosity at 20 °C, cps 2.32 2.21

iodine number, g of iodine per 100 g 3.0 1.7
Acidity, mg KOH/100 ml 1.5 1.0
Cetane number 48.4 49.8
Point, "C:
flash 51 53
half-boiling below -25 below -25
chilling below -35 below -35
Sulfur content, %
total 1.13 0.33
mercaptan traces none
sulfide 0.96 0.10
thiophene 0.17 0.23
Thermal stability (precipitate, 44.1 3.9
150 "C, 4 hours, mg/100 ml)
Bronze corrosion, g/m2 38.1 0.45
Tar deposition on bronze, g/m2 12.4 1.15
mixed with a refined fuel component. The extract from column 7 is diluted with water
in mixer M·4 to 55% concentration and passed to settler 8. The upper layer in the
settler represents very pure sulfides. After heating in heater H-1 the sulfides are
vacuum distilled in column 10. The resulting mixtures or narrow cuts of petroleum
sulfides are pumped into holding tanks for commercial products. After the sulfur
compound removal the fuel quality is considerably improved as to the sulfur
compound content, thermal stability, and corrosion activity (Table 28). Other
characteristics remain practically unchanged. The sulfides from the petroleum frac-
tion are nearly completely recovered. The remainder are thiophenes, the most stable
sulfur compounds. 64 •119 The time of contact in extraction was 30 min, the settling
time 2 hours. The raffinate was washed with 4% ammonia liquor in intermittent 30 ml
mixing tanks. The air stirring was performed at a pressure of 2.5 atm. The material
balance of the extraction process is shown in Table 29, the characteristics of the
sulfides isolated are listed in Table 30.
190 G. F. BOLSHAKOV
TABLE 29
2
Material Balance of Sulfur Compound Extraction
Crude Sulfur Compounds
Raw After extrac· After extrac· Tars and

Parameters material Raffinate tion I tion 11 losses
One-stage process
Quantity, rei. % 100 95.8 3.4 0.8
Sulfur content, wt. % 1.13 0.6 15.1
Two-stage processes
Quality, rei. % 100 92.0 1.9 2.7

Sulfur content, wt. % 1.13 0.2 8.9
The method was tested on diesel fuels produced at three different plants in the
USSR:
Fuels
I 11 Ill
Total sulfur content, wt.% in initial fuel 1.57 0.92 0.68

After extraction with 86% sulfuric acid 0.58 0.40 0.36
Sulfides obtained, wt.% of fuel 2.48 1.59 1.10
Sulfur content of sulfides, wt.% 14.0 12.1 9.3
From the above data it is evident that even a single extraction with 86% sulfuric
acid can reduce 2-3-fold the sulfur compound content and improve the quality of
commercial fuels. After a second treatment of fuels with 91% sulfuric acid the sulfur
content becomes as low as 0.2-0.15%. The composition of the sulfides extracted has
been examined. 2
The sulfur compound extraction process with dilute sulfuric acid has been
modified. 120 The characteristic feature of the modified method is sulfur compound
regeneration from the sulfuric acid solution by a combined method involving
reextraction with organic solvents in combination with partial hydrolysis. Use of spent
sulfuric acid from the alkylation process considerably reduces the cost of sulfide
removal from crude oil. The 190-360 oc distillate from an Arlan/Tyumen oil mixture
containing 1.57% total sulfur and 0.8 wt.% sulfide sulfur was employed as raw
material.
0
TABLE 30 ~
0
Characteristics of Sulfides >
z
......
()
V>
Vield, Total sulfur content, Sulfide content, Density at 20 OC, Boiling range, Refractive index, Molecular c:
kg/m3 n1f ~
Sulfides wt.% wt.% wt.% OC atl mm Hg weight
~
Sulfides after extraction stage I ()
0
Crude 100 15.1 936.8 1.4961 .,~
0
Distillate 93.6 15.3 84 926.3 25-166 1.4934 176 c:
z
Still residue 6.2 10.5 91 1005.2 >166 298 0
V>
Sulfides after extraction stage 11 .,~

Crude
Distillate
100
87.1
8.9
9.2 53
900.0
884.2 25-182
1.4941
1.4864 182
~
I""'
I:I1
Still residue 12.7 6.9 69 1013.1 >182 318 c:
~
......
10
192 G. F. BOLSHAKOV
The extraction was carried out with sulfuric acid from the alkylation process,
diluted to 79-80% strength. The optimal extraction conditions were found as follows:
temperature 20 oc, contact time 20 min, settling time 2.5 hours, acid co!'lsumpt~on
40% of raw material. The sulfur compounds were removed from the acid solution
by reextraction with light gasoline in combination with hydrolysis at 25-30 oc;
amount of reextractant 100 vol.%, consumption of water 10 wt.% with respect to the
extract solution, mixing time 20 min, followed by settling for 2.5 hours. After phase
separation the raffinate solution and the gasoline extract layer were neutralized with
1% ammonia or alkali solution and washed with hot water to neutral reaction. Then
the gasoline was distilled off. The process was carried out in a pilot plant (Fig. 26)
with periodical sulfur compound production and an acid capacity of 2m3 /h. The
stock is transferred by pump P-1 to the mixing tank M-5; simultaneously sulfuric acid
is pumped by another pump into a delivery pipeline. The mixing tank M-5 is equipped
with a level indicator, three valves controlling the extract phase level and a
temperature-controlling device. As the mixing tank is becoming filled and the phases
are separated, the refined diesel fuel enters the mixers M-1 and M-3 in which traces of
sulfuric acid are removed with 1% alkali solution. After filling M-5 with the extract up
to the upper control valve the stock and acid pumps are stopped. The extract solution
is transferred by P-2 from M-5 through cooler T-1 into mixers M-2 and M-4 with
preceding addition of water. At the same time, mixer M-2 is charged with an
extractant/gasoline mixture in a 1:1 ratio. If necessary, the solution is pumped in a
closed cycle M-2 _,. P-1-+ T-1-+ M-2 with some admixture of an inert gas. The
extract dilution with water is controlled by the acid concentration at the T-1 outlet.
An inert atmosphere is maintained in M-2 and M-4 in order to prevent extract-air
contact.
The phases are settled and separated for 2.5 h in mixer M-2. Spent sulfuric acid is
transferred from M-2 to an acid receiving tank. The interface level is controlled
through a watch window on passage to the receiver.
The upper layer, the sulfur compound concentrate and gasoline, is neutralized
with alkali solution from the traces of sulfuric acid, then washed with water and
allowed to settle for two hours. The gasoline is distilled off in a stiller, S-4. The
regenerated gasoline is recycled through a reflux exchanger and cooler T-1 section.
The sulfur compound concentrate is pumped by P-6 to a mixing tank M. The
material balance of the process is shown in Table 31.
The extraction with spent sulfuric acid allows isolation of 33-36% of the sulfur
compounds in the distillate. The sulfides are extracted to an extent of 50% (Table 32).
These data do not differ much from those obtained in the sulfur compound extraction
with 86% sulfuric acid in a pilot plant. According to the physicochemical characteris-
tics, the sulfur compound concentrates extracted with fresh and spent sulfuric acid are
very similar (Table 33).
The sulfur compounds separated consist mainly of thiacycloalkanes (70-80%)
alkyl substituted thiophenes, and benzothiophenes. '
The optimal acid concentration (79-80%) allows side-processes to be minimized
which leads to negligible losses (Table 34). '
4
8 0
~
0
>
z
()
C-4 tn
c:
M-1 M-j
~
~
8
::
"tl
0
c:
2 z
0
tn
.,0
"tl
8
7 ~
P-1 P-2 P-J P-4 P-5 P-6
0
r
rn
c:
FIGURE 26. Simplified flow chart of a pilot plant for the isolation of sulfides. ::
M-1-6-mixers-settlers; C-4-column for gasoline distillation; S-4-column still: V-6-vessel for spent sulfuric
acid; P-1-6-pumps; T-1-cooler. Flows: 1-diesel fuel, 2-sulfuric acid, 3-water, 4-gasoline, 5-alkali
solution, 6-refined diesel fuel, 7-sulfur compound concentrate, 8-inert gas.
194 G. F. BOLSHAKOV
TABLE 31
Material Balance of the Process
Products kg/h t/cycle wt.%
Starting material
Distillate 190-360 oc 8450 105.63 68.3
Spent 80% sulfuric acid 3560 44.5 28.3
Water 362 4.5 2.9
Total 12372 154.63 100
Obtained
Concentrate 338 4.23 2.75

Raffinate 7940 99.25 64.2
Spent 70% sulfuric acid 3854 48.15 31.2
Petroleum tars 34 0.42 0.25
Loss 206 2.58 1.6
Total 12372 154.63 100
111.4. Isolation with Alkalies
Alkaline solutions are chiefly employed for recovering mercaptans. The spent
alkaline solution is regenerated with atmospheric oxygen, sodium mercaptides being
converted to sulfides. To improve the recovery of mercaptans methanol, ethanol,
propionic or butyric acid, aromatic alcohols, sodium sulfide, etc. are added to the
alkaline solution. Copper chloride or cobalt, iron phthalocyanine sulfo derivatives are
used as oxidation catalysts. As an example, a simplified flow chart of the sweetening
of petroleum fractions at a pilot plant (Ishimbai) is shown in Fig. 27. The stock was
treated twice with aqueous-ethanolic alkali in mixer 6 and extraction column 7. The
TABLE 32
Comparative Data on Total and Sulfide Sulfur Content (Wt. %) in Concentrates Obtained
Under Laboratory (I) and Industrial (11) Conditions
Total sulfur Sulfide sulfur
Products I 11 I 11
Starting distillate 1.57 1.57 0.8 0.8
Concentrate 12.0 11.5 8.6 8.4
Raffinate 0.93 0.91 0.3 0.35
TABLE33
Characteristics of Sulfur Compound Concentrates Produced by Extraction with Fresh
Sulfuric Acid (I) and with Spent Acid from An Alkylation Process (11)
Parameters I 11
Density, p'f, kg/ m3 945.3 959.5

Refractive index, n~ 1.4987 1.5062
Average molecular weight 193 220
Boiling range, oc 195-350 235-355
Elemental composition, wt. %
Carbon 73.77 75.47
12.15 12.41
Hydrogen
Sulfur 13.9 12.0
Composition, %
Arenes 6 9
Alkanes + cycloalkanes 1 9 10
Sulfides 68 61
Thiophenes 17 20
solution consisted of one volume of 42-43% sodium hydroxide and two volumes of
92-93% ethanol, the solution: stock ratio being 1:4-1:6. The sodium mercaptide-con-
taining solution was \Yashed from hydrocarbons from the charge stock in column 12 by
using water and light hydrocarbons with an end boilding point not exceeding 70 °C.
The extract phase:isopentane:water ratio was 1:1.5:0.4. Ethanol was withdrawn from
the mercaptides in evaporator 9 at 85-90 °C. The sodium mercaptides were hydro-
lyzed by exposing them to the action of steam in column 20, the mercaptans being
steam-distilled and cooled in condenser 19. The final product, petroleum mercaptans
which can substitute synthetic t-dodecyl mercaptan employed in producing synthetic
rubber as an emulsion polymerization regulator, enters vessels 17 and 18.
TABLE34
Characteristics of Sulfur Compound Concentrates (%) Isolated from Diesel Fuels with a
Total and Sulfide Sulfur Content of 2.24 and 2.04%, respectively
Raffinate Extract Loss
Sulfur content Sulfur content Sulfur content

Extractant Yield Total Sulfide Yield Total Sulfide Yield Total Sulfide
86%H2S04 94.5 1.87 0.77I 4.0 81.4 8.1 1.5 1.0 1.2
80% spent H 2S04 92.5 1.82 0.66 5.25 11.3 7.95 1.75 1.0 0.8
86% spent H 2S04 84.5 1.09 0.09 7.9 10.1 6.2 7.6 23.4 37.3
196 G. F. BOLSHAKOV
FIGURE 27. F1ow chart of a pilot plant for mercaptan removal from petroleum fractions with
aqueous-ethanol alkali solutions. 1-pumps, 2-diesel fraction tank, 3-refined diesel fraction tank,
4-ethanol tank, 5-sodium hydroxide tank; 6,10,11-mixers, 7-extraction column; 9-evaporator,
12-washing column; 13,14-heat exchangers, 15-water tank; 16-isopentane tank; 17,18-mercap-
tan vessels; 19-condenser; mercaptan column.
1-ethanol to rectification and regeneration;
11-isopentane to rectification and regeneration,
III-water; IV-steam.
The mercaptans were separated nearly completely:
Contents,%
Total sulfur Mercaptan sulfur
Starting distillate 1.20 0.28

After mecaptan removal l.OS 0.003
Mercaptan concentrate 7.47 7.47
The mercaptans isolated were of rather high purity.

New improved methods of mercaptan isolation from hydrocarbon media have been
suggested. 121 - 123
III.5. Isolation with Heavy-Metal Oxides and Salts
Mercaptans readily form mercaptides with alkalies and oxides and salts thereof:
RSH + HgC)z-(RS)zHg + HCl

RSH + HgO-(RS)zHg + lhO
RSH + AgN0 3 - RSAg + HN03
Mercaptides are poorly soluble in hydrocarbons and readily separated. Mercapta

can be obtained from mercaptides by decomposition with hydrochloric acid follow~
by steam distillation. The mercaptans can be further purified by routine techniques.

Strict rectification can afford fairly narrow mercaptan fractions of slightly varying
molecular weight.
In laboratory practice low-molecular mercaptans are usually recovered with
mercury acetate solutions. Mercury acetate forms with aliphatic and aromatic
mercaptans water-insoluble complexes.
With mercury acetate, iodide, isocyanate, and chloride alkylthiophenes form
compounds insoluble in hydrocarbons:
R2 R1
+ [CH COO
3
12 Hg-
R
3
:0 S HgOOCCH
3
R2H1
R ~S)> + HgC12 + HCl

3
where R = alkyl or cyclic substituents.
Thiophenes are isolated by treatment with acids. In this way thiophene homologs
have been isolated from the cracking gasoline (30-250 °C) of California oi1. 116 The
sulfur content of the gasoline was 1%. The gasoline was fractionally extracted with
sulfur dioxide at -20- -30 °C, then with aniline and ethylene glycol diacetate at
-10- -20 °C. The mixture of extracts containing 5.5% total sulfur was vacuum
rectified at 50-146 °C into 1-2.5 oc fractions. Then the fractions were dissolved in
20% ethanol and aqueous 0.25 M HgC12 was added to the solution. A six-fold
quantity of 4 M sodium acetate was added to neutralize the hydrochloric acid
liberated. The mixture was allowed to stand for 40 hours. The white crystalline
precipitate was washed with ethanol and petroleum ether and then dried. Some
precipitate was extracted with hot ethanol. The precipitates both isolated and left
insoluble in ethanol were decomposed by distillation with 6 N hydrochloric acid.
111.6. Oxidation
This method consists of oxidation of sulfur compounds to sulfoxides which are

subsequently chromatographically separated from the hydrocarbons including aromat-
ics. The sulfides are then obtained by reduction of the sulfoxides.
The sulfur compounds in petroleum fractions are oxidized with hydrogen
peroxide or nitric acid solutions, organic hydroperoxides, oxygen, or by mild
ozonolysis. Optimal results were obtained upon oxidation of sulfur compounds
contained in the aromatic sulfur concentrate chromatographically separated from
petroleum fractions. The sulfides are oxidized most rapidly. The mercaptans are
oxidized to disulfides somewhat more slowly. The thiophenes are poorly oxidized
under conditions where considerable oxidation of the sulfides takes place. It has been
198 G. F. BOLSHAKOV
shown, however, that the thiophenes can be oxidized with hydrogen peroxide to
sulfones and then separated from the arenes. 43
20-30% hydrogen peroxide in acetic acid is usually employed. The oxidation
proceeds at room temperature during 1-3 hours. Then the mixture is diluted with a
three-fold volume of water and allowed to settle for 8 hours. Thereafter the mixture is
decanted, washed with water, and dried. After drying the mixture is chromatographi-
cally separated (Fig. 28). For this purpose a silica gel "ASK" with 0.07-0.16 mm
grain size was tested under experimental conditions in a ratio of silica gel weight to
organic matter weight of (2-3):1. The unoxidized part was separated with isopentane
and benzene, the sulfoxides with ethanol.
The sulfoxides can be separated with aluminium oxide and other types of silica gels.
Petroleum sulfides of intermediate distillate fractions can be isolated by oxidation
without preliminary recovery. For this purpose a mixture of 30% hydrogen peroxide
and 50-60% perchloric acid in approximately equivalent amounts is used. After

mixing for 30 min and settling for 3 hours the middle layer consisting of sulfoxide
perchlorates is separated and neutralized with 20% soda solution. The sulfoxides are
extracted with benzene, ether, or chloroform.
The sulfoxides are reduced to sulfides with hydrogen, lithium tetrahydroborate,
lithium tetrahydroaluminate, aluminium borohydride, lithium hydride, beryllium
hydride, and hydrogen iodide (Table 35). The yield of reduced sulfur compounds
increases as the molecular weight decreases in a homologous series, other things being
equal.
TABLE 35
Reduction of Sulfoxides
Sulfoxide Reducing agent Temperature, oc Reduction time, hrs Sulfoxlde yield, %
Isobutyl phenyl BeH2 50 27 65.3

LiH 60 31.2 58.4
LiAlH4 53 30 72.0
Al(BH4h 28 0.2 70.4
HI 52 0.4 53.0
Dibenzyl BeH2 60 21 78.5

LiH 45 32.4 58.8
LiAlH4 55 32 73.0
Al(BH4h 25 0.1 71.2"
HI 48 0.6 56.0
Diphenyl LiAIH4 57 34 74.0
Al(BH4h 20 0.2 72.3
HI 51 0.4 60.2
LiH 55 34 79.0
BeH2 55 30 75.0
Benzyl phenyl LiAIH4 55 36.2 72.1
Al(BH4h 23 0.1 76.3
HI 50 0.3 61.2
Aromatic sulfur concentrate
Oxidation
( Organic layer __.___________ L_E_t_h_e_r__e_x_t_r_a_c_t_i_o_n~-.-------------~~-A_q_u_e_o_u_s__a_c~e~t_i_c__l_ay__e_r~~

f t
Chromatographic separation Aqueous layer
on silir gel
Benzene dfsorption Aromatic hydrocarbons and Evaporation,

I
non-oxidized sul!ur compounds chloroform extraction
Ethanol
Reduction
Sulfoxides j Sulfoxides from aqueous

layer
I Sulfides I
FIGURE 28. Scheme of sulfur compound removal by oxidation.
200 G. F. BOLSHAKOV
Ill. 7. Comp/exing
Sulfur compounds form stable complexes with metal (titanium, cobalt, mercury,
palladium, aluminium, etc.) halides, halogens, halo derivatives, silver nitrate, etc.
The donor-acceptor bond most likely involves donation of the sulfur lone pair to an
unoccupied orbital of the metal. The RS-M(Cl)n complexes as a rule, are readily
soluble, in hydrocarbons and after separation undergo decomposition upon heating,
treatment with hot water and other solvents, or alkali solutions.
In their reaction with mercury acetate the disulfides form soluble complexes which
become insoluble when treated with sodium chloride solution. With increasing
molecular weight of the disulfides their complexing ability decreases. The same
phenomena are also observed with other sulfur compounds.
The reactions of alky sulfides and thiacycloalkanes with silver nitrate proceed in a
closely similar manner .103 The isotherms of silver distribution between 0.4 M sulfide
solution in hydrocarbons on one hand and water on the other hand show that it is not
possible to obtain a silver chloride:sulfide ratio larger than one upon saturation of the
organic phase with silver (Fig. 29), which may be explained in terms of the formation
of several solvates. 103 The solvate number is 1 for aliphatic sulfides and 2 for cyclic
sulfides (Fig. 30). The solvate number does not depend on the' sulfide concentration in
the solvent and is determined by the sulfide structure:
Ag;q + NO;q + qSorg- [qS·AgNOJ]org (1)

[qSAgNOJ)org;:::::: [qSAgNOJ]aq (2)
o ao~ 0.25 :r,M

FIGURE 29. Isotherms of silver extraction from nitric acid solutions with 0 5 M to!
cyclohexyl sulfide (1}, d~amyl sulfide (diheptyl sulfide) (2), 2-ethylcyclohexane (3}, pet.roleum s~~~eno(nyl
and 0.5 M dodecane/d1amyl sulfide (5). es 4),
x and y = equilibrium concentrations in the aqueous and organic phase, respectively.
--------------------~~~
tgKc
a& Q.4
tgCFREE SULFIDE
FIGURE 30. Solvate number determination by dilution of diamyl sulfide (1) and ethylthiocyclo·
hexane (2).
The substitution of toluene by dodecane suppresses the reverse process according

to Eq. (2), i.e. the complex transition from the organic to the aqueous phase
(distribution coefficient, Kh Table 36). According to Eq. (2), the silver extraction
decreases with increasing Kk. Therefore, when dodecane is used as a solvent the
sulfide-silver nitrate complex passes nearly completely into the aqueous phase. These
results are of great practical important. In the extraction of metals it is necessary to
employ arenes as solvents whereas in the extraction of sulfides from petroleum
distillates, on the contrary, normal alkanes are most suitable.
The concentration of hydrogen ions does not influence the silver extraction
(Fig. 31). Introduction of salts into the system increases the distribution coefficient.
The structure of the sulfides affects their reaction with silver nitrate (Table 37).
The thiacycloalkanes display the highest enthalpies of complexation. Introduction
of substituents in position 2 diminishes the enthalpy of complexing. This is especially
well manifested when the enthalpy of complexing is calculated per sulfur atom. If the
substituent is introduced in position 3 of thiacycloalkanes the enthalpy of complexing
is diminished less strongly. The melting points of aliphatic sulfide complexes are
approsimately half of those of thiacycloalkanes (Table 37). The reaction of sulfides
with silver nitrate involves an intermediate complex, [R2S·Ag]+. The better
TABLE 36
Distribution Constants of Sulfide~Silver Nitrate Complexes between Organic and Aqueous
Phase
Starting sulfide Complex ln toluene in dodecane
Dipentyl sulfide C10ll:uS • AgN03 0.37 5

Ethyl cyclopentyl sulfide CrH 14S • AgN03 0.20 11
KAg
20~-,~~---r~~~~---
f.O 2.0 CUNO/mole/1

cu
'·' cHNDs'mo1e/1
FIGURE 31. Effect of hydrogen (I) and demineralizer ions (11) on the silver distribution coefficient, KA
1-LiN03 , 2-KNOJ, 3-NH4NOJ
TABLE37
Enthalpies of Sulfide-Silver Nitrate Complexing
Melting point Sulfide

or complex, molecular Enthalpy of formation
Sulfide ·c weight kJ/mole kJ/S atom
Thiacyclopentane 125 88.2 39.2 14.3

Thiacyclohexane 144 102.2 45.7 14.3
Thiacycloheptane 116.2 37.9 10.4
2-Butylthiacyclopentane 114.3 25.2 7.1
3-B utylthiacyclopentane 134 114.3 45.0 12.6
2-(2-Methylbutyl-
thiacyclopentane) 158.3 22.6 4.6
2-Phenylthiacyclopentane 164.3 25.4 4.9
2-Ethyl-3-methyl-5-
propylthiacyclopentane 172.3 16.4 3.1
2-Heptylthiacyclopentane 186.4 18.9 3.2
4-Thiapentane 118.3 45.4 12.3
2,6-Dimethyl-4-thiapentane 146.3 32.8 7.2
5-Thianonane 68 146.3 34.0 7.4
3-Thiadecane 67 160.3 18.2 2.1
7-Thiatridecane 202.4 13.4 2.1
Methyl phenyl sulfide 124.2 12.2 3.14
Methyl benzyl sulfide 138.2 16.4 3.8
2-Ethylthiapyrane 126.3 38.2 9.7
3-Amylthiacyclopentane 145 128.4
TABLE 38
Separation of Sulfides by Complexing with Silver Nitrate
Sulfides in Molecular weight Boiling point, Initial Contents of components

mixture of sulfides oc content, wt. % after separation, wt. %
a b
Mixture I
6-Thiaundecane (a) 174.3 229 58.5 95.5 0.3

3-Amylthiacyclo-
hexane (b) 172.3 228 41.5 4.5 99.7
Mixture 11
2-Amylthiacyclo-
pentane (a) 158.3 224 45.0 95.0 2.8
3-Amylthiacyclo-
pentane 158.3 230 55.0 5.0 97.2
solubility of complexes of aliphatic and 2-substituted cyclic sulfides in arenes and

alcohols as compared with 3-substituted thiacycloalkanes can be used to separate
the sulfide isomers. 103 It was possible, for example, to completely separate
6-thiaundecane from 3-amylthiacyclohexane, and 2-amylthiacyclopentane from
3-amylthiacyclopentane (Table 38). A process for the separation of sulfides and
thiophenes which account for the bulk of sulfur compounds in petroleum has been
developed. 103 The sulfur compound isolation from petroleum fractions is better
carried out at low temperatures for a more complete sulfur compound recovery.
At the Tomsk Institute of Oil Chemistry, an efficient sulfur compound
separation is carried out on the basis of the theory of mixed complexes used
previously in simple aqueous systems. 124- 126 The main theses of this theory are as
follows:
-If the coordination number of an electron acceptor M is greater than 1 and the
system contains two or more different ligands, for example, A, B, .... , X, there is
always a possibility for the formation of a mixed complex of the type M· A· B .... X;
-If the initial concentration of the ligand A is much higher than that of the ligands
B .... X, the possibility of the formation of a simple complex M(B ..... X) is low and
the system is, in fact, a two-component system, i.e., predominantly M· A· B ..... X
contains a simple MA and mixed complexes. In the general case, the number of
possible variants of different coordinatively saturated complexes with monodentate
ligands is given by
(N + n- 1)!
N!(n- 1)!
where N is the coordination number of the electron acceptor and n the number of
different ligands.
204 G. F. BOLSHAKOV
When applied to petroleum and its distillates, this theory allows the following
conclusions to be drawn:
-If the concentration of one group of ligands in petroleum or its products is lower
than that of another group of ligands, the former will predominantly occur as mixed
ligands under equilibrium conditions of complexation;
-The composition of simple and mixed complexes and their ratio can be varied by
addition of synthetic ligands 'to the oil system;
-If the complexes are in solution they can be transferred to the heterogenous
phase by addition of the donor-acceptor bond to the system of a synthetic ligand
forming a mixed complex with a fairly high polarization, which results in a sharp
decrease of their solubility in hydrocarbons. In this case, a ligand exchange takes
place, in which the addition of stronger ligands B ..... X[NAn - mB + .... + yX
~ n(An - (m + ... + y) Bm ... x + mA + .... + xA] decreases the mixed-complex
solubility. As this complex is removed, the substituted ligand A will again be involved
in complexation.
Sulfur compounds have been isolated from the 125-350 oc fraction of
Kichik-Bel oil, USSR. Titanium tetrachloride (TIC), readily soluble in petroleum
products, was used as an inorganic electron acceptor. TIC forms stable complexes
with heteroorganic compounds. Quinoline was employed as a ligand. It can readily be
separated from the sulfur compounds by conversion to its hydrogen chloride salt.
The sulfur compound isolation technique was as follows (Fig. 32). TIC was
added to the fraction and the insoluble complexes formed were separated from the
hydrocarbons by centrifuging. Then, if necessary, some more TIC, and later
quinoline were added to the fraction. The complexes were also separated by
centrifuging. Quinoline was added until decoloration of the fraction (the complexes in
the solution possess a pink color). The complexes isolated at different steps were
decomposed with aqueous alkali according to Re£. 127 The organic layer was separated
in a separating funnel, washed with HCl solution to remove quinoline, then with water
up to neutral reaction. Two mols TIC were added per mol sulfur compounds.
The results of the sulfur compound isolation are shown in Table 39. The
concentrate Ko is obtained through the insoluble complex prior to the addition of
quinoline. The concentrates K 1-K, were obtained after the addition of 1 g of
quinoline. The method developed allows 74% sulfur compound recovery, 67%
thereof being sulfides. The high content of the ligands isolated with respect to
quinoline should be mentioned. 5.4 mols of ligand per mol of quinoline is isolated.
The composition of the compounds isolated is shown in Table 40. The major part
(84%) of the isolated sulfur compounds consists of sulfides and thiophenes.
Using mixed complexes and ligand exchange processes, a method for the isolation
and concentration of sulfur compounds and heteroorganic compounds in general
from oils has been developed 125 •126 at the Tomsk Institute of Oil Chemistry, Siberian
Division of the USSR Academy of Sciences. The method involves the extraction of
complexes with solvents or their mixtures with substances which are electron
a_cceptors. The solvents, S, sho~ld not mix with hydrocarbons, which permits the
hgands to be regenerated readtly from these solvents after decomposition of the
complexes.
'J?e solvent-coo!dinating is~lation. of sulfur compounds (as well as of heteroor.
game compounds m general) 1s earned out by extraction of ligands with a binary
Petroleum or its fraction
TTC dosage until cessation of heterogeneous

complex (HC) isolation
HC separation by centrifuging
~~----------t~---------~~~
addition I
Ligand addition (~ batch
or all at once until comp-
lete decolorization of the
solution)
Mixed complex decompositionl
+
I Aromatic "so concentrate!
FIGURE 32. Simplified scheme of sulfur compound removal with mixed complexes.
TABLE 39
Results of Sulfur Compound Extraction
Quinoline Yield, Sulfur content, wt %

Concentrate added, g wt.% total sulfide
Ko 0 11.0 10.3 6.5

Kt 1 7.1 9.9 8.0
K:z 1 5.0 7.6 6.1
K3 1 4.1 4.8 4.2
K4 1 12.5 2.8 1.8
Ks 1 2.8 2.5 1.6
206 G. F. BOLSHAKOV
TABLE40
Distribution of Sulfur Compound Main Types in Concentrates, % rei.
Concentrate RSR Q-sR

0 CO cx:D 0s
Ko 8.3 14.1 23.5 13.4 8.4 18.8
Kt 1.1 53.3 2.2 12.0 4.4 3.7
K2 9.9 24.5 22.6 5.4 1.5 24.4
K3 0 71.5 0 7.7 4.5 4.4
~ 1.6 18.0 11.4 16.1 9.4 13.0
Ks 3.6 33.5 0.1 11.2 5.9 19.7
Oo ono o-s-R 8-S-R OJ

6.7 3.1 2.6 5.3 3.8
3.2 5.5 6.4 1.4 6.8
3.5 0.9 0.3 1.8 2.8
4.4 0 6.5 0 0.9
13.8 5.1 2.9 5.8 2.8
3.2 1.2 7.4 3.3 10.8
mixture MX0 -S or by extraction of complexes by a coordinating solvent which

follows a preliminary addition of MXn to petroleum or petroleum product. The latter
is possible if the electron acceptor is soluble in the petroleum product.
In the first variant substitution of S in the coordination sphere is predominant:
[MXn • Sm]s + qL (MXnSm-qLq)s + qS

[MXn-z:Sm]+z + qL +==t [MXn-zSm-qj+z: - qS
(MXnSm)s + mL (MXnLm)s + mS
In the second case the ligands pass into the binary mixture due to:
-extraction of a simple complex
-formation and extraction of a mixed complex
-formation and extraction of an onium complex:
On the basis of the principles developed here a pilot plant for the solvent·
coordination isolation of heteroaromatic compounds from petroleum distillates has
been designed (Fig. 33). It consists of two 4·section thermostated unpacked mixing
and settling columns 1 and 3 for the separation of complexes from crude oil and
further decomposition with water; a packed column 2 in which reextraction of
heteroaromatic compounds forming weak complexes is performed using aliphatic
hydrocarbons (hexane, for example), and a film vaporizer 4 to withdraw water from
the aqueous salt solution. The plant is used for extracting heteroaromatic compounds
and refining the vacuum distillate boiling off within the 340-500 oc range. Propylene
carbonate (PC) and cobalt dichloride (CDC) were used as coordinating solvents.
The comprehensive material balance is shown in Table 41, and may serve as the
basis for designing larger-scale plants. The methods developed are industrially
11 c D
VDH WATER H
CDC + PC WATER
FIGURE 33 •. ~implified flow ch~rt of a pilot plant for the isolation of heteroorganic compounds from
petroleum d1stlllates. A-refimng assembly, B-reextraction, C-complex decomposition D-
regeneration. Material flows: '
VD-vacuum distillate, VDR-vacuum distillate refined, H-hexane R-reextract KG-solution of
heteroorganic compounds in hexane, CDC + PC-extractant. ' '
208 G. F. BOLSHAKOV
TABLE 41
Material balance of a pilot plant for refining a vacuum distillate (VD) with CDC·PC*
based on 100% product yield
Per 100 kg of VD
Processes Products charged obtained
Refining Vacuum distillate 100.0 90.0

Extractant 240.0
Extract 250.0
Re extraction Extract 250.0 244.7

Hexane 165.0
Hexane extract I
170.3
Complex Extract 244.7

decomposition Water 210.0
Hexane 161.5
Hexane extract 11 166.2
Aqueous extractant 450.0
Recovery Water solution of extractant 450.0

Hexane extract I 170.3
Hexane extract II 166.2
Extractant 240.0
Water 210.0
Hexane 326.5
Reextract 5.3
Concentrate of heteroorganic
compounds
• CDC-PC, cobalt dichloride + propylene carbonate
feasible since the solvents such as N,N-dimethylformamide, dimethyl sulfoxide, and

propylene carbonate are readily soluble in water, and after the addition of water the
heteroorganic compounds accumulate in a separate organic phase.
Ili.B. Hydrogenative Refining
Hydrogenative refining of petroleum fractions is widely used in industry. Catalytic

desulfurization by hydrogenation becomes more important when sulfur-rich oils
especially their heavy fractions, are involved in processing. The hydrogen desulfuriza:
tion of petroleum products is usually carried out with alumo-cobalt-molybdenum or
alumo-nickel-molybdenum catalysts which provide for a highly selective and rapid
sulfur compound hydrogenolysis. In commercial AhOrCoO-Mo0 3 catalysts the
Co/Mo ratio is 0.3-0.4, sometimes 0.5-1.0, the CoO and Mo03 weight contents
being 2-4 and 9-15% respectively. In the concomitant presence of cobalt and
molybdenum the catalyst becomes more active due to a well-defined synergistic effect.
This is illustrated by the following example of hydrogenative refining at 20 atm,

383 oc, volume feeding rate 2.1 h- 1 , hydrogen supply 620m3 /m 3 of feed stock (0 oc
and 760 mm Hg):
CoO,% Mo0 3 ,% Sulfur removal, %
19.1 0 33
5.0 15.6 94
0 19.8 40
The principal mechanism for the formation of primary products in sulfur compound
hydrogenolysis is known only for simple compounds. Mercaptans decompose at
the C-S bond:
RSH ....!!4 H2S + RH

2 RSH- H2S + RSR
These reactions are reversible since mercaptans, hydrocarbons, and hydrogen sulfide
are found among the products of the hydrogenolysis of sulfides:
RSR + H 2 - RSH + R'H

RSR + H 2 - RH+ H2S
RSH + H2 - RH+ H 2S
RSR + H 2S - RSH
RSH + H2 - RH + H2S
The primary products of the hydrogenolysis of disulfides are thiols, hydrocarbons,

and sulfides:
RSSR + H2 - 2 RSH
RSH + H2 - RSR + H2S
RSH + H2- RH+ H2S
Hydrogen sulfide, butane, butene, butadiene, and thiophene were found among
the primary products of hydrogenolysis of thiophane. The hydrogenolysis seems to
involve successive dedydrogenation steps. Then surface-adsorbed cyclic compounds
undergo decyclization with cleavage of a C-S bond to form acyclic sulfur-containing
fragments. This is followed by hydrogenation leading to hydrogen sulfide and the
corresponding hydrocarbons. Thiophene is most difficult to hydrogenate. Butane,
butene, and butadiene were found among the products of hydrogenolysiS'_of
thiophene over chromium and alumo-cobalt-molybdenum catalysts. 128 With increas-
ing degree of conversion in thiophene hydrogenolysis over molybdenum sulfide at
320 oc no butadiene is observed among the reaction products. 129 A possible scheme
210 G. F. BOLSHAKOV
of thiophene hydrogenolysis in its the first stages is as follows:
CH 2=CHC 2H5 .,. l

~=CHC~H2
H3c , J HJC /CHJ
HC=\H '-cH=CH
CH)
The hydrogenation of the butenes to butane is the determining step of the process.
With a change in the reaction conditions an alternative mechanism for the hydro-
genolysis of thiophene is possible which involves elimination of hydrogen sulfide
with abstraction of H 2 from /3-carbon atoms as the initial step:
0s --- . . HC !5!5 C-C !:!:!CH + H2S
Then diacetylene undergoes hydrogenation. Benzo- and dibenzothiophenes are

hydrogenated according to the following schemes:
o-o
Various possible mechanisms of .the i~teraction of H 2 an~ su!fur compounds With
the catalyst surface have been mveshgated. The followmg mterpretation of the
reaction of sulfur compounds with sulfurized CoMo0 4 and Al-Co-Mo catalysts has
been offered at the Tomsk Institute of Oil Chemistry: 130 - 132
H,, ..H
H2 + 0 ~--.. H2 S +D
D+ RS [~----R] *
[~---R ]* + Hads 0 + R
where !Sl are sulfur atoms of the catalysts, 0 unoccupied catalyst sites.
Upon changing hydrogenation conditions (higher hydrogen pressure and catalyst
activity, changes in temperature) the sulfur compound hydrogenation proceeds

very efficiently to afford the corresponding hydrocarbons and hydrogen sulfide. At
temperatures of practical interest the reaction equilibrium is shifted toward the
formation of hydrogen sulfide and hydrocarbons (Table 42). For thiols, sulfides, and
disulfides a temperature increase decreases the Gibbs energy of hydrogenation more
drastically. For thiophanes this Gibbs energy decrease at elevated temperature is less
TABLE 42
Thermodynamic Characteristics of Sulfur Compound Hydrogenation
Heat elfect, Gibbs energy,

kJ/mole kJ/mole
Reactions lOOK 800K lOOK 800 K
n-C4H9SH + H2- C4H1o + H2S +58 +67 -61 -63

n-4H13SH + H2- n-C6Ht4 + H2S +59 +67 -62 -62
n·C12H2sSH + H2- n·C12H25 + H2S +59 +67 -61 -61
(n-C4H9):zS + H2- n·C4H9SH + n-C4Hto +46 +55 -55 -64
/ n-C4H9SH + n·CuH24 +46 +55 -53 -60
n·C4H11SCuH23·n + H2 ...........
n·C4Hto + n·CuH23SH +49 +55 -54 -60
(n-C3H1hS2 + H2- 2 n-C3H 7SH +18 +28 -31 -49
(n-CJ{13)zSz + H2- 2 n·C6H13Sll +17 +24 -32 -51
0s + 2Hz - n-C4H 10 + H2S +113 +122 -97 -63
0 s
+ 2H2 - n-C5H12 + H2S +104 +118 -98 -74
CH3
0s + 4 H2 - CH3CH2CH(CH3h + H2S +261 +278 -170 -9
212 G. F. BOLSHAKOV
pronounced; however, at 800 K .the equilib~um constants. exceed 104 and t~e
equilibrium is almost completely shifted to the nght. An especially strong decrease m
the equilibrium constants is observed with methylthiophene. For thiophenes the
degree of hydrogenation is thermodynamically limited:
Temperature, K Pressure, MPa
0.1 1.0 4.0 10.0

500 99.2 99.9 100 100
600 98.1 99.5 99.8 99.8
700 90.7 97.6 99.0 99.4
800 68.4 92.3 96.6 98.0

900 28.7 79.5 91.8 95.1
The sulfur compound hydrogenation rate increases in the following order: mer-
captans > disulfides > sulfides = thiophanes > thiophenes, which is consistent with
their stability. 55 ·90 With increasing the number of saturated and are ne rings in sulfur
compounds (thiophenes) the relative rate constant (K) decreases:
K = 2.9 K = 2.8 K • 1 • .3 K = 1.0

Scheme 1
Industrial flow sheets for hydrogenative refining of light and intermediate distillates
are in full operation and widely employed at present. 133 The greatest problems are
encountered in the hydrogenation of heavy fractions and petroleum residues. The
successful development of desulfurization processes involving hydrogenation of
residual raw material is mainly determined by the availability of catalysts.
There are a few modifications of the process of direct hydrogenative desulfurization
of residues which have already been used in industry or are under way to wide
industrial application.
Chevron company has developed a modified catalyst.ICP-105 for lsomax VRDS
processes, the reactivity of which remains unchanged during a long time, even after
precipitation of large quantities of nickel and vanadium. The catalyst can be
employed for 7-12 months depending on the sulfur content of the product.134
A catalyst RT-2 with an improved stability to metals and a longer service life has
been developed by Exxon for the Residfining process. The RT-2 catalyst and it
modification RT-3 are characterized by high hydrogenation activity at relatively lo~
pressure. 135 ·136
TABLE 43
Catalyst Characteristics
Parameters
Active components on Ah03, %

cobalt suboxide c:2.0
molybdenum trioxide c:6.0
Hazardous impurities, %
iron oxide :50.16
sodium oxide :50.08
Bulk density, kg/m3 550-650
Content of water removed at 650 °C, % :52.5
Cracking resistance, kg per 1 mm of granule diameter c:0.9

2
Specific surface, m /g 80-130
Relative activity in desulfurization (thiophene hydrogenolysis), % c:1.2
Dust and crumb content, % :52.5
Granule size, mm
diameter 1.8-2.2
length 3-5
Distribution of pore size, % of total pore volume
radius <50 A :515
>100A 20-30
Hydrogenation catalysts for desulfurizing petroleum residues have also been

offered by Shell, 137 British Petroleum, 138 Standard Oil Indiana, 139 French Petroleum
Institute,40 etc. Unfortunately, no exact information regarding the composition,
structure, and performance characteristics are presented by the firms. In the USSR
many institutions deal with the development of catalysts and processes for hydrogen
desulfurization. At the Bashkirian Research Institute of Petroleum Refining a
catalyst, KGDR-1, for hydrogenation of deasphaltate vacuum residues has been
developed (Table 43). 141 The catalyst is highly efficient under laboratory conditions
(Fig. 34). Further the catalyst has been tested in a pilot plant (Fig. 35). Two
deasphaltates were used as starting feedstock (Table 44): one of 23-24% tar of a
commercial mixture of West-Siberian oils (DARws) and one of 47% tar of Arian oil
(DARa)· The reactor was charged by an upward flow. The catalyst was sulfurized
prior to the experiment for 30 hours with a diesel fraction containing 2.0% sulfur at
380 oc and 14.7 MPa, volume rate of stock feeding 1 hr- 1 , hydrogen supply 500 nl/1
stock. After sulfurization the diesel fuel was replaced by vacuum oil gas which was
pumped over under the same conditions for 24 hours. Then the vacuum oil gas was
replaced with the starting deasphaltate and hydrogenative desulfurization was carried
out at 14 MPa, 370-380 °C, volume rate of stock feeding 0.5 hr- 1, hydrogen supply
1000 nl/1 stock. The aim of the experiments was to obtain commercial boiler fuel.
The quality of the hydrogenated product was controlled by daily sampling. The extent
214 G. F. BOLSHAKOV
STOCK FEEDING VOLUME RATE, hr-1

Q5 J.o 2.~ 2.0 1.~ t.o
~ ~~--~~~~~====~~-------------.
~~ _........-•
::> • / 0
tl) H 90 V
~~: 2 ~
~~so
~
r
L---~------~----~----------~--~~--~~--~~
~ D.2 O.J Q4 0..5 0.8 aJ 0.8 ~ f.O
FICTITIOUS TIME OF DISSOLUTION, hr
FIGURE 34. KGDR-1 catalyst activity.
1-diesel fraction, 2-vacuum gas oil of Arian oil.
B·t
.5 _ ___..
,__
4.,.__ _ __,~
FIGURE 35. Simplified flow chart of the hydrogen desulfurization of oil residues.
R-1-reactor; HPS-high-pressure separator; LPS-low-pressure separator; LRF-level regulator
(floating); B-1, B-2-fresh-hydrogen vessels; V-1, V-2-feedstock and solvent vessels; S-1, S-2-
alkaline scrubbers; C-1, C-2-coolers; V-3-hydrogenate receiver; F-1, F-7-filters.
of hydrogenative desulfurization was maintained by raising the temperature over the

whole run. During 7-11 months of the catalyst performance the content of sulfur and
coking substances was practically the same, the yield of fractions increasing slightly
(Fig. 36). The temperature rise affects both the material balance of the process and
the product quality (Table 45, Fig. 36).
In the commercial product the viscosity should meet the technical standards of
M-40 boiling fuel. This is achieved at a temperature as low as 370 oc for DAR and
not below 380 oc for DARws· In choosing the hydrogenation conditions not onl; the
TABLE 44
Quality or Hydrogenates in DAR Hydrogenation on a KGDR·I Catalyst
OAR. DARw•
Indices Duration, brs
2000 4000 5000 3000 6000 7000

Density at 20 °C, kg/m3 926 920 904 935 932 925
Coking ability, % 4.6 4.4 4.1 5.8 5.6 5.4
Sulfur content, % 0.93 0.95 0.95 0.97 0.98 0.98
Metal content, % • to-•
vanadium 8.3 4.1 3.4 3.0 2.7
nickel 4.1 4.4 3.7 2.3 2.6

Fraction yield, % distilled up to
350 oc 14.5 24.0 43 11.0 16.5 29.0
500 oc 61.5 71.0 84 49.5 55.0 70.0
Removal,%
sulfur 76.7 76.2 76.2 62.7 62.3 62.3
Coking materials 58.2 60.0 62.8 40.9 42.9 44.9
vanadium 94.8 97.4 97.9 96.3 96.6
nickel 93.2 92.7 93.8 88.5 87.0
TABLE 45
Material Balance or DAR Desulrurization at Different Stages of KGDR-1,
Long Duration Tests
Parameters DAR. DAR_
Time of run, hrs 2000 4000 5000 3000 6000 8000

Taken,%
deasphaltate 100 100 100 100 100 100
hydrogen 1.0 1.2 1.4 0.72 1.0 1.25
Total 101.0 101.2 101.4 100.72 101 101.25
Obtained,%
boiler fuel 91.5 89.8 87.5 95.4 92.8 90.15
gasoline 4.1 5.1 6.1 1.6 3.4 4.9
gas cl 0.5 0.7 1.2 0.11 0.65 ··t.t6
~ 0.28 0.5 0.7 0.50 0.65 0.88
c~ 0.34 0.6 0.9 0.34 0.88 1.44
'C4 0.28 0.6 1.1 0.40 0.42 0.52
Hydrogen sulfide + ammonia 3.3 3.2 3.2 1.77 1.6 1.6
Lo~s 0.6 0.6 0.6 0.6 0.6 0.6
216 G. F. BOLSHAKOV
•
OQS
00
~g4 ,
"E
J'z1Q2
Hg()
Cl)
~~~--------~~--~
*J
.
~ 2
*• 0
~96
..:
~Q4
~ ,
~92 , ..00 420 \'
FIGURE 36. Effect of temperature on the yield of deasphaltate hydrogen desulfurization products.
e DARa 0 DARws
sulfur content of the starting residue, but also the process temperature and other
factors should be taken into consideration. If the catalyst run exceeds 1000 hours the
conduct of the temperature is determined only by the sulfur content level since other
fuel quality characteristics conform to the All-Union standard (GOST). DARws are
more stable than DAR3 • The difference in stability influences the material balance of
the process. The boiler fuel yield in DARa processing is lower than that with DARw
(Fig. 36). The hydrogen consumption towards the end of the run increases b;
40-50% due to a decrease in temperature, degree of destruction, and saturation of
cleavage products. In the manufacture of a boiler fuel with a sulfur content not
exceeding 1%, the catalyst KGDR-1 provides for a fairly high hydrogenative refining
stability. The difference in the catalyst service life in hydrogenation of DARws and
DARa is explained by different metal content of the starting raw material. The metal
content of DARa (0.02%) is twice that of DARws· The KGDR catalyst performance
has been compared with that of other catalysts. 142
The KGDR Catalyst Performance as Compared With That of Foreign Catalysts141
Metal content Extent of sulfur removal, % Catalyst performance, m3 /kg

of the starting
raw material, % Catalyst141 KGDR Catalyst141 KGDR
0.01 62.0 62.3 2.4 6.7

0.02 75.0 76.2 1.4 4.6
The above data show that the catalyst KGDR-1 is fairly efficient.
The kinetics of the hydrogenative desulfurization of vacuum deasphaltized re·
sidues, DARa and DAR~'?, has been studied in order to find a function or a model
describing most .reliably the experimental data for the following models:
M 1 based on the assumption of simultaneous occurrence of two parallel first-

order reactions with different rate constants related to readily and hardly
removable sulfur, respectively 144- 146
M 2 a 1.5th-order model 147
M 3 a second-order model 148
M 4 an n-m-order model of the desulfurization reaction which changes depending
on the reaction temperature. 149 •150
The experimental data of the sulfur removal (Table 46) were treated using a special
program With algorithms of Steepest descent and random Search. 151 The SUm of the
squares of the relative deviation was taken as a minimization criterion:
where N is the number of measurements in the experiments and Sf and Sr the

experimental and calculated sulfur concentrations at the reactor outlet, respectively.
The following systems of equations reproducing the main kinetic models of hydro-
genation have been solved:
Ml
s = dexp (- KuT) + (1 - a) exp (- K2tr, n 1 = 1
So n2 = 1
1 1 Kt • 7
jS =-+-·
M2 n = 1.5
So 2 '
1 1
M3
s ==-+
So
Kr· n == 2.0
t '
1 1
M4 sn-1 = sg-1 + (n - 1) KtT; n ::f 1
218 G. F. BOLSHAKOV
TABLE46
Initial Data for Calculating the Kinetic Parameters or Hydrogenative Desulfurization
Sulfur content at the reactor outlet, %
Time, hrs 360 •c 370 oc 380 °C 400 •c 410 °C 420 °C hr- 1
DAR,..
2.0 1.05 0.80 0.62 0.40 0.26 0.20 0.5

1.0 1.55 1.25 1.05 0.80 0.51 0.42 1.0
0.5 1.93 0.90 1.50 1.35 1.00 0.83 2.0
0.33 2.10 1.85 1.75 1.60 1.30 1.15 3.0
0.25 2.20 1.95 1.90 1.80 1.50 1.30 4.0

0.20 2.26 2.00 1.95 1.85 1.60 1.43 5.0
0.125 2.40 2.25 2.18 2.10 1.94 1.75 8.0
DAR.
2.0 0.9 o.s 0.3 0.2 0.5

1.0 1.4 0.6 1.0
0.25 2.3 1.8 1.7 4.0
0.125 '2.9 1.4 2.2 8.0
where S and S0 are the sulfur concentrations (in %) at the reactor outlet and in the
initial feedstock, respectively
T is the fictititous time of contact, hr = v- 1

V volume feeding rate, hr- 1
a contents of readily removed sulfur in the starting feed stock
n reaction order
The pseudo-nth order in M 4 is a function of the temperature: ;:
n = noexp (!~)
The chemical reaction constants, K., in equations M 2, M 3, M 4 and K 1 and K2 in

M 1 are represented as
K, = Koexp (A- :T)'

where E is the activation energy, kcal/mole. fJ. is the absolute value (%} of the
average deviation of the calculated sulfur concentrations in the product at the reactor
outlet (Se) from the experimental data (Se):
se- se]
A= [ se ·lOO
The experimental data are most reliably described (Table 47) by equations M 1 and
M 4. M 2 gives large deviations from the measured data. At temperatures above
400 oc the deviation from the experiment does not exceed 6%, with a small degree of
conversion the error reaching 15% in some points. Thus, the use of the model M 2
over a wide temperature range does not seem reasonable. Model M 3 turned out to be
incorrect. M 1 and M 4 describe the experiment fairly well over wide temperature and
contact time ranges. It should be taken into account that M 4 is an artificial model
since it does not reflect the physical essence of the processes.
At low temperatures (360-380 °C) a major part of the sulfur compounds is readily
removed as the Ktt to K2t ratio in M 1 is 7-7.5 (Table 47). At high temperature the
Kit to K2t ratio reduces to 5-5.5, the activation energy increasing to 27.6 kcal/mole,
TABLE 47
Calculated Rate Constants (hr- 1) of the Desulfurization Reaction
MI Ml 1\13 M4
Temperature,
oc Ku
DAR.,.
360 0.907 0.122 0.941 0.279 0.306 1.937

370 1.375 0.203 1.513 0.469 0.494 1.892
380 1.573 0.240 1.790 0.555 0.576 1.826
400 2.639 0.451 3.422 1.061 1.042 1.731
410 3.380 0.610 4.665 1.447 1.384 1.687
420 4.296 0.817 5.281 1.955 1.822 1.646
E 22.6 27.6 28.3 28.3 25.9 2.34
A 5.1 9.8 9.5 4.5
DAR.
380 3.170 0.422 2.753 0.846 0.527 1.908

400 4.040 0.602 5.478 1.339 1.370 1.803
420 5.085 0.840 8.398 2.060 2.538 1.740
E 10.63 15.48 19.70 20.02 17.60 1.60
5.9 11.0 12.8 5.2
220 G. F. BOLSHAKOV
TABLE48
Sulfur Distribution in Deasphaltate, %
DARws DARa
Sulfur Sulfur
Components Yield content Yield content
Alkanes + cycloalkanes 15.0 0.06 13.5 0.11

Monoarenes 18.0 1.6 15.2 2.49
Di- and triarenes 34.7 3.2 37.2 4.9
Benzene tars 15.8 3.6 11.5 5.3
Alcohol-benzene tars
Tars 15.5 3.8 21.5 5.5

Asphaltenes 0.9 3.3 0.8 5.8
thus indicating a greater degree of hydrogenative refining due to the sulfur com-
pound fraction which is more difficult to remove. The sulfur compounds are
concentrated in arenes and tars (Table 48). Organic sulfur compounds most reluctant
to removal are likely to be concentrated in heavy tars. It may be concluded, therefore,
that m~del 1 gives the most comprehensive representation of the kinetics of the
hydrogenation process. To be certain about the parameter a in M 1 one needs
informfltion concerning the sulfur compound group chemical composition in the crude
and its' components.
The catalyst porosity influences considerably the results of hydrogenative refining
of heayy distillates. 152 With this aim in view, catalysts of various porosity have been
1
developed and tested. The catalysts were synthesized from four samples of active
alumin.a (Table 49). The active part of alumina I was obtained by decomposing
aluminium hydroxide precipitated prior to the test by treatment of aluminium nitrate
solution with aqueous ammonia. Other aluminium oxides were obtained in a similar
way with supplementary modification to produce a coarse-porous structure. Upon
modification the pores with a radius under 50 A disappear, those with a radius above
50 A increasing in number from 0.3 to 0.84 m3 /kg. The catalysts were produced by
successive impregnation of alumina with ammonium molybdate and cobalt nitrate
solutions and intervening drying between the impregnations. The intervening drying
permits the preservation of the porous structure formed. In the modified porous
structure the predominant micropore size increased approximately two-fold (Table
49). The micropore volume increases by 35-40% owing to intermediate pores with a
radius of 150-300 A. The macropores remain practically unchanged upon modifica-
tion. The modification improves greatly the catalyst activity in hydrogenative
desulfurization (Table 49, Fig. 37).
The influence of the nature of the active metal on the coarse-porous catalyst
efficiency of hydrogenative desulfurization of residues has been studied. 153 Alumo-
nickel-molybdenum (ANMC) and alumo-cobalt-molybdenum (ACMC) catalysts
TABLE49
Characteristics of Catalyst for Sulfur Compound Removal from Heavy .Residues
Metal content Relative desulfurization activity 0

:;..1
Mo03 +CoO per unit of 0
Bulk
Total
pore Specific
Predominant
micropore
specific
surface
total
active
-z>
(j
en
c:::
·to- 2,
~::0
density, volume, surface radius, catalyst metal catalyst catalyst
Catalyst Carrier kg/m3 m3/kg m2/g A Mo03 CoO g/m2 weight weight surface volume
(')
0
Industrial 680 620 181 27 13.00 4.40 0.96 1.00 1.00 1.00 1.00 a:
...,
alumocobalt 0
molybdenum c:::
catalyst for
z
0
en
hydrogenative
0
refining of "!j
...,
light-colored m
distillates ;!
0
KG-1 AI203-1 680 580 237 21 13.25 4.00 0.73 1.42 1.44 1.08 1.42 r
m
c::
KG-2 Ah03-2 620 100 211 36 12.00 3.90 0.76 1.58 1.74 1.34 1.44 a:
KG-3 AI203-3 640 690 104 50 6.80 2.35 0.90 1.32 2.53 2.28 1.24
KG-4 Al20l-4 580 700 128 15 7.37 2.45 0.77 1.46 2.60 2.04 1.25
222 G. F. BOLSIIAKOV
40~-----------r------------~----~----~--~
500 fOOD 1500 2000 2500 JOOO hr

FIGURE 37. Sulfur compound removal from deasphalted tar of Arian oil 1-commercial alumo-
cobalt-molybdenum catalyst (ACMC); 2-KG-1, 3-KG·2, 4-KG-3, S-KG-4.
have been synthesized according to the above technique. The catalyst characteristics
are as follows:
ANMC ACMC
Bulk density, kg/m 3 640 640
Specific surface, m1/ g 124 122
Total pore volume, m3 /kg 770 770
Average pore radius, A. 124 126
Content,%
Mo03 7.2 7.1
NiO 2.3 0
CoO 0 2.1
Granule, size, mm
Diameter 2.1 2.1
Length 3.5 3.5
The hydrogenation has established the catalyst ANMC to be more efficient than
ACMC (Fig. 38) when the metal contents reaches 9% (Fig. 39). The highest catalytic
activity is achieved with a metal content of 10-14%.
IV. CHEMICAL AND PHYSICAL PROPERTIES
IV.J. Structure
The sulfur atom in sulfur compounds possesses a number of features affecting the
character of bonds: (i) a 1r-bond formed with participation of sulfur 3p-electrons is
considerably weaker than corresponding bonds formed by carbon and oxygen;154
(ii) the resonance in sulfur compounds occurs due to overlapping 3d-orbitals of the
sulfur atom and 2p-electrons of the atom in the a-position to sulfur; (iii) the 3d-orbital
resonance has no angular dependence.
o395 .._,,..,.. __..-..,.,_,·~..

,........,_
0.300
.385
... QtJ
..... ..... ..
.Xxx 1
x "- 111
.
"xx'lr Xllrr•nnuxrrt 1lllu1.. rnrr1xrnrn"x 1
i ·~as ~""...,..,.,...._..-Jhflwtii-t-N.w-r.tn... ~.,..
~a4
.. 4.0 ...
A ,uv .,..•, -r I I
.r"i~ .•-: .::--.•. ,........,
~2.0
f.O ........
. ....
... ... • . . ...
'b'tQ8
.. a6
1:/l a4 I
I
1
.. . ...
I~~-
1 I I
IJ
• - " tpl I 1111
\• I
si' 11111 11 .. ~ .~ . . .
JJ
Q2
SDD
. 1000 f500 hr
FIGURE 38. Comparison of ACMC and ANMC catalytic efficiency.
e ACMC * ANMC
8 10 12 14 1B 18
TOTAL CONTENT OF ACTIVE
METAL OXIDES, %
FIGURE 39. The effect of the metal oxide content on the relative activity of ANMC (1) and ACMC (2).
Conjugation of divalent sulfur with £! neighboring carbon atom may be due to

electron donation, (a) and (b), and attraction, (c):
+ •• I +
a) -C-S- -C=S
I .. I ..
b) -c-s-
1 ••
-C=S-
1 ..
c) -c-s-
1 ..
224 G. F. BOLSHAKOV
TABLE SO
Energy of C-S and S-H Bond Cleavage (kcal/mole) in Thiols154
Tbiol c-s S-11
90.7
67 87.6 ± 3.0
74.3 ± 2.2
(72.5)
63 88.7
80.5
71.6 ± 2.2
i-C3H7SH 70.5 89.9
C4H8SH 72.8
CsHuSH 70.1
CJI13SH 69.9
~H 5 SH 84.9 76.2
CJ:15CH.zSH 56.9
The conjugation (a) is not common in sulfur compounds. In the conjugations (b)
and (c) expansion of the sulfur electron shell should take place. This conjugation is
possible only with participation of the sulfur 3d-orbitals. The conjugation involving
electron donation is the manifestation of the +M-effect of sulfur. Of course, this
effect does not lead to isomers with a true double::::C=S-bond; however, there is
some "double bonding" between sulfur and carbon.
Let us consider the structure of thiols, sulfides, disulfides, and thiophenes in some
more detail.
W.l.l. Thiols. The S-H bond in thiols is formed mainly by p-orbitals. This
accounts for the lower strength of this bond as compared with the C-H bondlS4
formed by sp3-hybridized orbital (Table 50). The angle between the bonds is nearly
right in the hydrogen sulfide molecule (92.2 ± 0.100) and slightly larger
(100.3 ± 0.2°) in methanethiol. These angles differ much from those in water and
methanol (104.45 ± 0.10° and 108.9 ± 2°, respectively). The distance between the
sulfur and hydrogen atoms in hydrogen sulfide and thiols is 1.35 A, the C-S bond
being 1.82 A. These bonds are considerably longer than the corresponding C-H,
C-0 and 0-H bonds (1.09, 1.42, and 0.96 A, respectively).
W.1.2. Sulfides. The C-S bond length in sulfides is 1.75-1.82 A. The calculated
double-bond character according to Pauling ranges from 8 to 10% depending on the
structure. The :::::::s angle in diphenyl sulfide is 113°. The dissociation energy of c-s
bonds is much lower than that of C-C bonds (Table 51). A significant decrease in the
dissociation energy of the Alk-S bond as compared with the Ar-S bond is observed
which seems to be caused by the effect of the arene 1r-electron system on the C-s
bond.
TABLE 51
Energy of C-S Bond Cleavage in Sulfides, kcai/Mole
Bond cleared Energy Bond cleaved Energy
CH 3S-CH3 73.1 ± 3.2 (CH3)JC-S~H 5 69.8
~H 5 S-CH3 73.8 C6HsS-CH3 61.4

~H 5 -SCH3 71.8 4Hs-SCH3 83.4
~Hs-S~Hs 70.9 4HsCH2-SCH3 55.9
CH3S-C3H7 70.6 4H,S-C2Hs 58.2
~HsS-C3H7 71.5 C~s-SC2Hs 84.0
(CH 3 hCH-S~H, 71.1 C6HsCH2-S~Hs 115.1
CH3S-C,Hu 68.2 4HsS-C6H 5 72.7

~H 5 S-C4H9 72.8
IV.J.3. Disulfides. At present, most scientists believe that polysulfides possess an

unbranched structure. 155 •156 The calculated S-S bond length is 2.01-2.08 A.
Disulfane exhibits the following structure:
90°37'
In some structures, however, the S-S bond is longer:
H3C m C H 3
s-s -s
s2 - s3 = 2.22l; S - S = 2.)6A0
According to the UV spectra the di-t-butyl disulfide conformation is as follows:

226 G. F. BOLSHAKOV
o: 1.3al
/c5-1~ c5 - s, = 1.671 c5 - o4 =
C-C4 2S s 1 - s2 = 2.04A 0
04 - 06 == 1.4al
6 ~3/
0
c
o3 - s2 = 1.72A o3 - s7 = 1.661
11
S7
c4 - c3 = 1.421
The dihedral angle between the substituents slightly exceeds 1000 due to steric
interactions and the molecule approaches the trans-form. Ring closure leads to the
cis-conformation. The four-membered cyclic dianion contains six 7T-electrons and
possesses a stability comparable to that of arenes. The 7T·electron system of the
thiophene type is also characteristic of 1,2-dithiolane-3-thione which is ther-
modynamically stable and displays a delocalization energy close to that of thiophene.
Therefore compounds of this type can be present in petroleum. The C5-S 1 and
C3-S2 bonds are shorter than the usual c-s bond (1.88 A) .
•. +
.. ..
R-S-S=R-
a b
Disulfides with electron attracting substituents should possess a structure of the

type a. Structures of the type b are unlikely.
Disulfides readily dissociate to radicals, therefore they may also be assigned a
resonance structure R-S-S-R. For disulfides, however, this structure cannot be
accepted as unambiguous. The most suitable structure appears to be that with
1r-bonds, in which 3d-orbitals are involved in the resonance. The S-S bond is
double-bonded to some extent. This is proven by the greater dissociation energy of
S-S bonds (Table 52) in disulfides as compared with the 0-0 bonds in peroxides
(32-48 kcal/mole) or the N-N bonds in hydrazines ( <40 kcal/mole). In disulfides
like in other divalent sulfur-containing compounds, the bonding orbitals are formed
by p-electrons, the two unpaired electrons being 3s- and 3pz·electrons.
If the standard bond length in disulfides is taken to be 2.08 A, the double-bond
character of an S-S bond 2.04 A long (CH3SSCH 3 , HSSH) is 15%. In 4-methyl-1,
s
3l\l
HO -9
"'"/s
s
TABLE 52
Energy or S-S Bond Cleavage in
Disulfides, kcai/Mole154
Disulfide Energy
HSSH 72
CH3SSCH3 65.8 ::t 6.0
CH3SSC2Hs 72
~HsSS~Hs 68.9
C3H1SSC3H1 105.9
4,H5SS4,H5 43.6
2-dithia-4-cyclopentene-3-thione (S-S bond length 2.03 A) the double-bond charac-

ter is 20%.
IV.1.4. Thiophenes. According to microwave spectral data thiophene is planar: 157
Length, A Angle, deg.
c-s 1.7140 c-s-c 92°10'

ct-c2} 1.3696 s-e-c
c3-C' 111°28'
c3-c2 1.4232 c-c-c 112°27'
C'-Hs} 1.0776 C-C-H
et-us 124°16'
c3-H~} 1.0805 S-C-H 119°51'

c2-H6
A comparison of the lattice parameters of thiophene at -55 oc with those of

benzene at 3 oc has shown these molecules to be of similar shape. Thiophene
molecules are randomly arranged in crystals at -55 °C. 158 The four molecules in the
228 G. F. BOLSHAKOV
unit cell occupy statistically any of four equivalent sites. Involvement of the thiophene
ring in strained polycyclic structures distorts the planarity of the ring.
IV.2. Chemical Properties
IV.2.1. Thiols are weak acids, stronger, however, than the corresponding alcohols.
The Ka value is 10- 11 for ethanethiol and 10- 17 for ethanol. Since sulfur is less
electronegative than oxygen, this may look strange, but it comforms with the facts
that H 20 is a weaker acid than H 2S, HF less acidic than HCl, and NH3 a weaker acid
than PH3 • The most important fact is, in this case, that the elements of the second
period are attached to hydrogen by stronger and considerably shorter bonds than the
elements of higher periods. Therefore, the energy of ionic dissociation for second-
period element hydrides turns out to be higher, although the bonds broken by this
dissociation are more ionic.
Thiols react with carboxylic acids and acyl chlorides to form sulfur analogs of esters.
Thiols also react with aldehydes and ketones to afford the corresponding dithioacetals
and dithioketals:
RSH + HOOCR' ----• RSOCR' + H20
RSH + Cl COR' - - • RSOCR • + HCl
. Un.li~e alcohols, the .oxidation of thiols proceeds in .a different manner since sulfur
1s ox1d1zed more read1ly than carbon. Compounds m which sulfur is in a higher
oxid~tion state are often rather stable. Besides, the S-H bond (80 kcal/mole) is
~ns1~erably weaker than the 0-H bond (111 kcal/mole). With thiols, therefore, it
1s qUite reasonable to expect reaction mechanisms impossible with alcohols. In fact
the oxidation of thiols with mild oxidants (atmospheric oxygen, halogens sulfuri'
acid, etc.) gives disulfides: ' c
RSH + [0]--+RS + H [0]

2 RS'--+ RSSR
RSH + [0]--+ RSOH
RSOH + Rs---+ RSSR + on-
Vigorous oxidation of thiols with nitric acid, ozone, potassium permanganate, or

hydrogen peroxide leads to sulfonic acids, possibly with or without intermediate
disulfide formation. 119 The formation of sulfenic or sulfinic acids, which can readily be
oxidized and are difficult to isolate, is also possible:
0 00
11 1111
RSSR - RSSR - RSSR \
/ 11 1111
0 00
RSH RS0 3H
0
~ RSOH - 11
RSOH _ _ _ __,/
Further oxidation can lead to sulfuric acid:
In the oxidation of thiophenol no carboxylic acids are formed:
0
11
C6H 5SOH - C6 HsSOH - C6 H 5S0 3H
0
11
C6HsS03H - H 2S04 + C6Hs0H - C6H 5 0SOC6 Hs
11
0
The hydrogen of the thiol group can be substituted by metal (M) which leads to
thiolates, RSM. Thiolates are fairly stable and, at low temperatures, weakly
hydrolyzed by water. Water-insoluble mercaptans are readily soluble in dilute
aqueous alkalies to form alkali salts such as RSNa. Mercury thiolates decompose
upon heating to give mercury and dialkyl disulfides:
(AlkShHg - AlkSSAlk + Hg
230 G. F. BOLSHAKOV
The reaction of thiols with carboxylic acid salts yields thiolates and the correspond-
ing acids:
1/0
AlkSH + Pb(AlkC02) 2 - Pb(SAlk)2 + AlkC-OH
W.2.2. Sulfides are readily cleaved by nucleophilic reagents. 159 Upon heating with
hexamethylphosphoramide alkali solutions, alkyl sulfides decompose to form unsatu-
rated compounds. When treated with sodium or lithium in ammonia, thienyl sulfides
undergo dealkylation to the corresponding thiols:
MaR•
s
Potassium, sodium, or lithium in 1,2-dimethoxyethane react with diphenyl sulfide

in the following way:
ArSAr + Na- 2[ArSC6 H$f- + Na+- 2 ArSNa+ + 2 C6H ; - 2 ArSNa + Ph-Ph
Aromatic sulfides decompose when treated with metallic potassium, sodium, or

lithium in ethers or hydrocarbons at 0-25 °C: 159
. . . . ==-------... C H 6 5"
1 W, oolvcot
C6H6
A study of the decomposition of sulfides with lithium in ammonia or methylamine

159
has shown the reactions to afford thiols, hydrocarbons, sulfinic acids, and some
other products. An empiric rule which governs the reaction course has been
established; 160 the decomposition of a sulfide leads to the formation of the least basic
anion of the p~ir with t~e greatest diffe~ence in basicity. If the difference in basicity
between Ar'S and ArS , for example, IS larger than that between Ar'- and Ar-, the
decomposition leads to the most acidic thiol. If the difference in basicity of two
possible carbanions is larger than that of two thiolate or sulfinate anions, the cleavage
proceeds toward the formation of the least basic carbanion. These premises are
supported by the observed fragmentation of alkyl aryl sulfides to form aromatic thiols,
as well as the fragmentation of sulfones to form aliphatic sulfinates.
Dialkyl sulfides are reduced with sodium, lithium, or beryllium in liquid ammonia
with ammonium salts added to give thiols and hydrocarbons:
AlkSAlk + M/NH3 (liquid) - AlkSH + AlkH
The hydrogen required for the reduction is obtained by the following reactions:
M + NH3 -M+ + e-(NH 3)l!.

2 NH4 + + 2 e-(NH3)l!.- H2 + (2x + 2) NH3
The reductive cleavage of aromatic and alkylaromatic sulfides occurs upon treatment
with etheric calcium ammonia solution at 0 °C;
R
oxidant
C6H5SC8H11 --+ C6HsSH + CsH 18

C6HsCH2SCsHa1- '4.HsCHJ + CsH 17SH
However,
The mechanism for the sulfide reduction with calcium hexammine can be repre-
sented by the following scheme:
C6HsSR + 2 e - [C6HsSR) 2- - [~H 5 St + R-

[C6Hssr + H+- C6HsSH
R- + H+-c6HsSH
R. +e-R-
R-+ H+-RH
232 G. F. BOLSHAKOV
Phenyl radicals cleave the C-S bond of sulfides. For example:
C6Hs + (CH3hCSC(CH3)J--+ C6Hs + + (CH3)2C=CH2 + (CH3)3CS'

_....-" (CH 3) 3CSH
(CH 3) 3CS' . . . . . . ._
~ (CH 3hCSSC(CH3h
These reactions take place upon heating of di-t-butyl sulfide with phenylazo-
triphenylmethane as the source of phenyl radicals.
The thermal stability of sulfides, as well as that of other sulfur compounds, is of
great practical importance, first of all, in petroleum processing. Sulfides are thermally
very stable in comparison with thiols and disulfides, only inferior to thiophenes.
Alkylaromatic sulfides do not change up to 300 oc,
while thiacyclohexane and
thiacycloheptane remain intact even at 450 °C. 159 1-Thiaindane is thermally stable at
temperatures up to 450 °C. At this temperature the degree of conversion is 10%,
hydrogen sulfide and mercaptans being the decomposition products. At 500 oc and
higher all sulfides decompose to form hydrogen sulfide, mercaptans, thiophene
homologs, unsaturated hydrocarbons, small quantities of hydrogen, carbon, carbon
disulfide, and elemental sulfur.
The thermal stability of neat sulfides differs from their stability in mixtures with
hydrocarbons and other sulfur compounds and in oils. Alkylthiophanes, for
example, in a mixture with alkylthiols decompose at a far lower temperature than in
the neat form. It has been established that in hydrocarbon media at 190-200 oc
aliphatic sulfides and mercaptans exchange their RS groups to liberate hydrogen
sulfide the source of which is sulfide and mercaptan. In this case, cleavage of the C-S
bond is observed in dialkyl sulfides, and alongside the reactions
RSR + R'SH--+ RSR' + RSH

RSR + R'SH --RH + R'SSR
take place.
When mixtures of aliphatic sulfides, thiols and 2-alkylthiophenes in hydrocarbons
are heated, the decomposition products of the less stable sulfides and mercaptans
react with the thiophenes to give resinous substances. 159 The decomposition of
sulfides proceeds more vigorously in the presence of some metals, such as copper
iron, platinum, nickel, tin, mercury, and lead. When p-tolyl sulfide is allowed to pas~
over a-Fe or 'Y-Fe203, for example, an elimination reaction occurs. The formation of
the ion radical [R2SHJ+' is most likely, followed by a homolytic reaction with
simultaneous cleavage of the two c-s bonds:
R 2S +Fe --+S=Fe + 2R'--+ R-R

R' + C6H6 - - RH+ C6Hs
C6H; + C6Hs - C6H5-C6Hs
The degree and the rate of thermal transformations of sulfides may be described by
the generalized equations: 159
ln D
n::ll
= a·~b
£M= (D-M) a·b·~b- 1
d~
where -r is the contact time; M denotes the extent of conversion, %; D stands for the
limiting M value when -r--. oo; a and b are kinetic parameters.
Vk273.2·P·3600
T = --------------
vH + VF
VK is the volume of reaction space not occupied by the catalyst, ml; (Vu + VF) is the
sum of hydrogen and feedstock volumes, reduced to normal conditions, ml;
T = temperature, K; P = pressure, atm. Mercaptans dominate among the conver-
sion products, at temperatures below 350 °C, being replaced by hydrogen sulfide with
further rise of the temperature. At high temperatures in the presence of metals
thiophanes decompose to afford significant amounts of hydrogen sulfide, mercaptans
being formed in considerably smaller quantities. 2-Decylthiophane, for example,
decomposes according to the following scheme:
Mixed sulfides decompose with either one or two C-S bonds breaking, depending
on the structure: 159
-(]
D-s
234 0. F. BOLSHAKOV
Sulfides are fairly strong Lewis bases which form with protons or alkylating agents
deep-colored R2SH+ ions in the absence of oxygen. Sulfides form with sulfuric acid
R2S • H2S04 complexes (energy of formation 4-8 kcal/mole).
In the reaction with perchloric acid or ferric chloride in the presence of hydro-
chloric acid, octahydrothiaxanthene undergoes disproportionation to form
thioxanthylium salts and perhydrothiaxanthen. 161
HClO\~+ ~
~y~ ~SA....)
cxo
+ HCl0 4 - - - - -
When heated with 70% HCI04 in alcohol, dialkyl sulfides are subject to scission of
the C-S bond to form sulfonium perchlorates, R 3s+cJ04 - • 132 The reaction of
diphenyl sulfide with nitrogen trichloride leads to a salt-like compound, bis-(diphenyl
sulfide)-nitride chloride, [C6H 5S-NS(C6Hs)]+cl- .162
Aliphatic sulfides and thiophanes form complexes with iodine, R 2S • 12 • Thiophenes
and aromatic sulfides fail to form stable complexes with iodine. Using this property
one can separate sulfides of various structure. The donor ability of cyclic sulfides
toward iodine decreases in the following order C5 > C6 > C4 > C 3 depending on the
number of methyl groups in the ring. 159
Sulfides from complexes with amines, nitro compounds, and urea. Benzyl sulfides
can be carboxylated with solid carbon dioxide in dimethyl sulfoxide to form
mercaptocarboxylic acids
I I
Rsc- + C02 ___,. RS-C-C02-
I I
Sulfide sulfur stabilizes a-carbanions.

Hydrogen fluoride initiates the reaction of sulfides with aromatic hydrocarbons:
Hydrochloric acid can induce ring expansion in some thiophane homologs:
HCl
g a C l HCl 0 Cl
HOH2C 0 S CH 0H
2
HOH C
2
; ' ,..
--CH
Cl-
HOH C
2
S
--
CH S
I 2
2 Cl
Analogously: 159
HC~
QCH
3
Hydrogen chloride causes ring opening of thiacyclopropane while acyl bromides

open five- and six-membered rings:
Dichlorocarbene reacts readily with alkyl aryl sulfides. About 25% of all sulfides
are involved in the reaction:
+====~ Arr+ -CHR

CHC1 2
+
~ ArS===CHR ArSCHR-CHC1 2
+ -cc1 3., -HCl

ArS=Clffi -- ArSCHR - - - • Ar-SCR
I 11
CClJ CC1 2
Thus, saturated sulfides can be converted to unsaturated sulfides which is of great

practical importance. For example, electrophilic agents such as dialkyl dithiophos-
phates or chlorocarbenes add to unsaturated sulfides:
236 G. F. BOLSHAKOV
(C 2H5o) 2ftSCB(CH 3)SR

s
00
Sulfides are brominated and chlorinated rather readily:
The chlorination of sulfides can be carried out with N-chlorosuccinimide in CC14 or

with sulfuryl chloride. Treatment of sui fides with halides often leads to cleavage of the
C-S bond. For instance:
Under these conditions the thiophene ring undergoes ring opening to form
alkanesulfonyl chlorides.
Thiophane and alkyl aryl sulfides react with t·butyl esters of perbenzoic acids in the
presence of copper(!) bromide to give sulfide acyloxy derivatives:
and further
These reactions constitute a variant of the Pummerer reaction:
-SOCHz- + (RCOhO - -SCII(OCOR)- + RCoo-
The reaction of primary alkyl sulfides with p-toluenesulfinic acid yields aldehydes
and thiosulfonates: 163
A possible mechanism of this reaction is as follows:
CH 2R
+ I
Arss: - - ArSOH +
Hb "'cHR
The limiting stage of the process is the elimination of water
Ion A hydrolyies immediately under these conditions
The mercaptan reacts readily with the sulfinic acid:
RCH 2SH + ArS0 2H - ArSOH + RCH2SOH
ArSOH + RCH 2SOH

1ArSOlll lArS0 2 H
ArS0 2SAr ArS0 2SCH 2R
Oxidation is one of the most essential reactions of sulfides. In the presence of

oxygen sulfides are oxidized fairly efficiently. The oxidation rate increases with rising
temperature. Let us consider some results obtained concerning the oxidation of
sulfides with oxygen at 150 °C. 119 The resulting sulfur compounds were studied by IR
spectroscopy and chemical analysis. The spectra of the oxidized products were
recorded against the background of the starting sulfur compounds by the com-
pensation method using a cell with variable thickness. t TheIR spectra are given in 119
t The IR spectra of dibenzyl sulfide were recorded relative to air.

238 G. F. BOLSHAKOV
The oxidation of butyl s-octyl sulfide for 30 minutes leads to small quantities of
species with double bonds of the type CHR 1=CHR2 (970 cm- 1, a very weak broad
band at 1600-1620 cm- 1 ), C=O groups (1720 cm- 1), and S=O bonds (1130,
1170 cm- 1). Some of the butyl s-octyl sulfide decomposes at the C-S bond as
evidenced by the maximum reversal in the 760-770 cm- 1 region.
During further oxidation (2 hours) these characteristic bands become more intense.
There are no signs in the spectrum indicating the presence of acids. The C=O band
(1720 cm- 1 ) seems to arise from aldehydes and ketones (2720 and 1420 cm- 1 ,
respectively).t There is a considerable increase in the number of both broken C-S
bonds (750 cm- 1 band reversal) and newly formed unsaturated bonds (970 cm- 1).
The formation of a small quantity of OH groups (weak band at 3500 cm- 1), evidently
related to sulfonic acids, is observed. Stronger S=O group bands occur at 1130 and
1170 cm- 1•
All the characteristic bands remain in the spectrum after oxidation for another
2-8 hours, but their intensities (including those of the reversed bands) enhance. Any
signs of esters and acids are still absent. It should be noted, however, that the
intensity of the aldehyde band (2720 cm- 1) is not higher after oxidation for 8 hours
whereas the ketone absorption (1420, 1920 cm- 1) becomes more intense. Thus, the
amount of C=O groups generated (1720 cm- 1) increases due to the formation of
ketones.
A probable mechanism for the thermal-oxidative conversions of butyl s-octyl
sulfide is presented in. 119
The products of the oxidation of dibenzyl sulfide display absorptions in the 900,
920, 970, 1000, 1160, 1200, 1295, 1460, 1660, 1715, 2730, and 3400-3500 cm-1
regions. After oxidation for 6 hours an absorption in the 1320 cm- 1 region appears
and becomes more intense with time.
The oxidation leads to the formation of CO groups (1715-1795 cm- 1). The
absorption at 2730 and 3400-3500 cm- 1 points to the formation of aldehydes and
hydroxyl-containing products. The formation of meta-substituted phenols may be
suggested since the spectrum shows some signs of mono- and trisubstituted aromatic
rings (900-860, 750-810, 680-725 cm- 1).
The spectra indicate no presence of sulrones and sulfoxides, the formation of
sulfonic acids and covalent sulfonates (1200, 1600 cm- 1) is quite evident. This shows
that some dibenzyl sulfide (5-6%) is oxidized with cleavage of C-S bonds.
The intense absorption at 900-890 cm- 1 cannot be assigned to unsaturated bonds
1
of the type CR R2=CH 2 (895-885, 1750-1800, 1410-1420 cm- 1) since there is no
strong absorption at 1420 cm- 1•
Thiophene is oxidized faster than butyl s-octyl sulfide and dibenzyl sulfide. The
0
oxt'd atton
. starts wtt
. h the f ormauon
. o f '_......S=O and '/S"-
.; groups. This is indicated
0
by the most intense bands in the spectrum at 1020, 1040, and 1090 cm- 1 • It should b
noted that the formation of sulfinic and sulfonic acid groups is accompanied by · e
. . h 1 . rtng
openmg smce t e spectra revea no stgns of sulfolane. The thiophene ring opening is
'In the 1420 cm-• range, however, aldehydes absorb as well.

also evident from the 1260 cm- 1 band reversal, the appearance of a band at 720 cm- 1
indicating the formation of a CH2 group chain (with more than three CH 2 groups) and
a band at 1630 cm- 1 due to unsaturation. The absorption at 780 cm- 1 might be
assigned to double bonds of the type CR 1 R2=CHR~ (the f~rmation of th~se
structures is unlikely) or to the presence of (CH 2)n<3 chams. The mtense absorptton
in the 3430 cm- 1 region is attributed to vibrations of OH groups, possibly of sulfonic
acids. The spectrum of the products formed after 30 min. oxidation exhibits intense
C=O group bands (1720, 1410 cm- 1) possibly corresponding to aldehydes and
ketones (2720 and 1410 cm-•, respectively). The presence of carboxylic acids
(3250-3600, 935, 1410 cm- 1) is quite possible.
Upon further oxidation of thiophane the same bands remain in the spectra, only
they become more intense. After exhaustive oxidation thiophane darkens and some
resinous substances and an insoluble precipitate appear in it. Polymerization of the
oxidation products is indicated by a decrease in the absorption intensity of double

bonds (1630 cm- 1) and OH groups (3430 cm- 1). A probable mechanism for the
thermooxidative conversions of thiophane has been suggested. 119
The oxidation of 2-hexylthiophane involves the oxidation of the side chain to afford
CO groups (1720, 1420, 940 cm- 1) and OH groups (3400-3500 cm- 1).
The 1260 cm- 1 maximum reversal and the C-S band (630 cm- 1) disappearance
provide evidence for the opening of the ring C2-S bond. A simultaneous oxidation
of the sulfur atom occurs, which results in the appearance of considerable amounts of
0
)S=O groups (1025, 1050 cm- ) after 70 minutes and ~S~ groups (1160 and
1
~0
0
o-
1
1290 cm- 1) and the moieties-O-S~ and O=S=O (1200, 1370, 1420 cm- 1)
l'o I
-0
after 4 hours of oxidation.
The sulfoxidcs initially formed seem to undergo further oxidation to sulfones and
sulfonic acids.
The c-s bond cleavage in thiophanes is due to the low strength of this bond
(56.7 kcal; CH bond = 98 kcal) 119 and is confirmed by the formation of multiple
bonds (1640-1630, 540 cm- 1). The sharp band at 700 cm- 1 and the band at 980 cm- 1 ,
the intensity of which increases with the time of oxidation, can be assigned to double
bonds in cis· and trans·isomers, CHR1=CHR2 , respectively.
The appearance of the band at 820 cm- 1 and the increase in its intensity with the
time of oxidation show the formation of double bonds of the tyr,e CR1R 2=CHRJ
and the absence of structures of the type CHR1=CH2 and CR R2=CH 2 • This is
indicative of the fact that no abstraction of a hydrocarbon radical from the thiophane
ring takes place during the oxidation.
The formation of C=O groups (1720 cm- 1) in high yield appears to occur at the
penultimate chain carbon atom. The number of CH2 groups in long chains decreases
very slowly (720 cm- 1 maximum reversal), which is quite understandable, taking into
account the two simultaneous opposite processes: the decrease in the number of CH 2
groups in the chain due to the oxidation and the increase in their number due to the
ring opening.
240 G. F. BOLSHAKOV
The fonnation of OH groups is not very pronounced. The major part of the
carbonyl groups seem to belong to aldehydes and ketones. A possible mechanism for
the thermooxidative transformations has been presented. 119
The oxidation of 2·(2-methylpentyl)-thiophane yields from the very beginning a
somewhat larger amount of C=O groups than the oxidation of 2-hexylthiophane
does. Evidently, the side chain is readily oxidized to form aldehydes and ketones,
which is confirmed by absorptions at 2720, 1410, and 1730 cm- 1• Upon further
oxidation the amount of these products increases.
The spectra of the 30 min oxidation products show intense bands at 1030 and
1060 cm- 1 attributed to S=O groups of sulfoxides; the intensity of these absorptions
increases further. No formation of sulfones and sulfonic acids takes place. There is a
gradual increase in the amount of OH groups (3400 cm- 1) which may be related to
alcohols. Of interest is the absence of any indications of ring opening: no maximum
reversal at 1260 cm- 1 and no changes of C-S-C bonds (630 cm- 1). There is no
absorption from double bonds of the type CR1R2=CHR3 (820 cm- 1). There is,
however, absorption at 1630 and 980 cm - t which indicates the presence of bonds of
the type CHR1=CHR2 (trans). The appearance of these bonds may be explained
only in terms of cleavage of the c-s bonds. Therefore, partial bond cleavage in the
thiophane ring is quite possible.
A mechanism for thermooxidativc transformations of 2·(2-methylpentyl)·
thiophane has been presented. 119
Thus, the oxidation of sulfur compounds yields a great variety of products
containing carbonyl, hydroxyl, carboxyl, ester, sulfinyl, sulfonyl and sulfono groups
as well as unsaturated structures. These intermediate products further serve as the
initial material for the solid-phase formation.
Mild ozonation of sulfides leads via sulfoxides to sulfones in a yield up to 90%.
Under more rigid conditions the C-S bonds break to afford unsaturated hydrocar-
bons, oxygen-containing species and sulfuric acid.
The rate of the cyclic sulfide oxidation with hydrogen peroxide in 94% alcohol with
0.1N HC104 added depends on the ring size:
D< <0
Sulfides can be oxidized with sodium metaperiodate:
a
R2S + NaJ04--. R2SO + Nal0 3
The oxidation of alkyl substituted thiacyclohexanes with t-butyl hypochlorite

dinitrogen. tetroxide, or sodium periodate gives sulfoxides of mainly cis:
configuration:
~sI
0 -
>s + 104 - - /s,
'/ '
' 0/
I~
/0 ___.,..
~0 ~~I + Io-
3
0
Sulfides are oxidized by t-butyl, isobutyl, or isopropyl hypochlorite (the reaction is

performed in methylene chloride at -78 °C):
s+ORCl - - >S=O + RCl
ROCl + Cl- ~ RO- + Cl 2
Cl 2 + >S --+ > SC1 2
>sc1 + no- - >so + RCl + cl-

2
The oxidation of sulfides with iodine in aqueous solutions in the presence of

catalysts such as HPOi-, for example, has been studied: 159
+
RSR' + I _ _..,.. RSR' + I'
2 I
I
+
R-S-R'
-0'-
'-... 0
'-p/
o~ 'oH
Oxidation of aromatic sulfides with nitric acid at 0 °C stops at the sulfoxide step:
Peracetic, monoperphthalic acid, and phthaloyl peroxide nearly quantitatively

oxidize sulfides to sulfoxides.
Aromatic sulfides and sulfoxides in sulfuric and polyphosphoric acid solutions are
oxidized to afford sulfonium cation radicals:
Ar s::o + H+ - A r s+(oH)
2 2
Ar s+oH- OH' + Ar s+
2 2
242 G. F. BOLSHAKOV
Diaryl sulfides are oxidized by N-bromosuccinimide:
0
11 :Br R
ArSAr + llr -NO- li
A~Ar + CN-H + H20
11
~
+
ArSAr + HBr
OH
0 0
Under the same conditions aliphatic sulfides decompose at the C-S bond.
N-Chlorosuccinimide smoothly oxidizes sulfides to sulfoxides.u9 This reagent chlorin-
ates sulfides in non-polar solvents.

Peroxides are widely used for the oxidation of sulfides:
R'OH + R2SO + HX
[R2S ~t· 0, -- ••
where HX = alcohol or acid.
In the oxidation with 6% hydrogen peroxide in ethanol, the activity of substituted
diphenyl sulfides and phenyl methyl sulfides decreases in the following order H >
m-CH 3 > p-CH3 > p-OCH 3 > m-Cl, > p-Cl > m-N02. In the same series the rate
of oxidation of benzyl and phenyl sulfides decreases with increasing alkyl radical
size and branching: CH3 > ~H.s > n·C3H7 > iso-C 3H, > n-C 4 H9 > iso-C 4 H 9 >
s-C4H9 > t·C4H9.
Chloramines react with sulfides according to one of the following schemes: t6s
R2S + ArS0 2NNaBr R2suso 2Ar + NaBr
R2S + RCONHCl [ R2SNHCOR) Cl
R2S + c6H5CONHC1 HCl + R2 SNCOC 6H

5
HCl + RCONH2 + R2so

NH2 Cl + -
{R2SNHNH2 )· HCl
Sulfamines can be obtained only under strictly controlled conditions. Even a slight
change in the reaction conditions can lead to chloro substituted products.
IV.2.3. Disulfides. A distinctive feature of sulfur is its ability to readily form fairly
stable disulfides and polysulfides. Mainly disulfides and, considerably less frequently,
polysulfides are present in petroleum.
Like polysulfides, disulfides are readily cleaved when exposed to the action of
electrophilic or nucleophilic reagents and free radicals.
Let us discuss, as an example, the reaction of eN- with an unsymmetric sulfide.
eN- attacks an Alk-S group: 155
RSCN +-SAr
This is a reversible second-order reaction. A reaction of eN- with a dialkenyl

disulfide in methanol at 80 oc has been reported: 166
The reaction mechanism is as follows:
~ + SCN
~-
~
Y+ SCN
Phosphorous acid esters cleave disulfides by an ionic mechanism:

244 0. F. BOLSHAKOV
The reaction proceeds also in the presence of radical inhibitors. Dialkyl disulfides are
more reactive than diallyl disulfides. Unsymmetrical disulfides react with phosphites
even at room temperature. Upon nucleophilic attack at the sulfur by phosphite the
disulfide bond is readily polarized. The polarization degree governs the disulfide
reactivity Disulfides with electron-attracting substituents should possess the struc-
ture R 1SS=R2 - rather than R1 S=S=R2 -. This accounts for the easy attack on
sulfur by electrophilic agents (peracids and sulfenyl halides) even when the sulfur
atom is fairly distant from the electron-attracting substituents.
Diethyl phosphonate reacts very fast with unsymmetrical disulfides (in tetrahydro-
furan):
further
where R = c;H 5 ; CH3 ; CONHc;H5

Primary and secondary phosphines react with disulfides 167
Rl'H 2 + R' SSR' - - + - RP(SR 1 ) 2 + 2R'SH
R2P - SR' + R'SH
RP(S)(SR') 2 or R2R(S)SR' are formed in the absence of radical inhibitors.

Another example can be given:
where R = alkyl, R' = allyl.

The reaction between hydroxide ion and unsymmetrical disulfides R'SSR whe
R , ·ts more e1ectronegatave
· than R has been studied. 168 In this case
' the disulfidre
undergoes polarization and ionization. This leads to R'SH and/or R'SSR as mai~
ORGANIC SUlFUR COMPOUNDS OF PETROLEUM 245
reaction products. Therefore, the R'S- anion is formed first:
R'SSR + -oH - R'SSR - R'S- + RSOH

I
OH
With an increase in the stability of the anion abstracted the S-S bond cleaves more
readily (Table 53). Alkyl disulfides react with acetylene: 169
KOH
The participation of two disulfide molecules in the reaction with acetylene can
afford 1,2-di-(alkylthio )-ethylene:
RSCH=CHSR
RSCH=CHSR + RSSR
The authors 170 of a series of papers dealing with the reaction of disulfides with
TABLE 53
Reactions of 0.1 M Solutions and Nucleophilic Reagents In 85% Aqueous Acetone
at 25-30 °C 168
Nucleophilic Yield Yield

R'SR agent R'SR,% R'SSR',%
(02N)2C6lhSSyH, eN- 70
(02N)z4H3SSCIIz411, on- 85 10
(OzN)24H3SSCII24H, on- 30
o1r
a~ssc,n,
98
N02 OH- 50 25
o-0 2NQI,.SSCzlls o1r 15 64
246 G. F. BOLSHAKOV
acetylenes have revised the reaction mechanism:
R'C=CH + -OH--~
The scheme suggested is in agreement with the following order of the reactivity of
acetylenes R'C::=;CH in the reaction:
Nucleophilic cleavage of diphenyl sulfide with sodium sulfide occurs readily. 155
Phenyllithium reacts with disulfides:
Lithium acetylide reacts with disulfides:
NH
HCCLi + RSSR -Li~' HCCSR + -SR _ . , RSCH:aCSR _ _,..,..
RSSR
RSCHC{SR) + SR
~~:
2
RSCHCHSR + -NH
2
The "thiophilicity" of nucleophilic agents y- in the reaction
R'SSR + y- --~ RSY + R'S-
-SCN,
>-oH 2,4-(0 2N) 2c
6H3s- > NJ-> I~ c6H
5
NH
2
has been discussed. 171
If y = thioanion, the thiophilicity is proportional to the xs- ion redox potential,

Eo:
2xs- xssx + 2e-
The nucleophilicity enhances with increasing E 0 (Table 54). The reactivity of

nucleophiles can be determined by the following equation: 155
where k,:/kup is the ratio of the rate constant of the nucleophile X and the standard
nucleophile, water; E stands for the nucleophilic electron-donating constant deter-
mined from the redox potential as E = E 0 + 2.6 where 2.6 is the oxidation potential
of water dimerization; H = pKa + 1.7; a and {3 are the substrate constants.

Disulfides are cleaved by electrophilic agents, i.e. halogens, metals, acids, ozone,
tetraethyllead and other oxidants. These reactions are often encountered and widely
applied.
The reactions of disulfides with chlorine and bromine in an aqueous medium lead to
chloro and bromo sulfonic acids. When reactions are carried out in non-polar solvents
the SCI or SBr derivatives are obtained.
In the reaction with iodine, bis-2-(2-naphthyl)ethyl disulfide undergoes cleavage at
the s-s bond and cyclization:
ethylene glycol
TABLE 54
Redox Potentials of Various Thioanions at 25 °C
According to the Reaction 2 xs- ~ XSSX + 2 e-
Eo relative to Eo relative to
xs- 111 electrode, V xs- H1 electrode, V
Ncs-
(CH30hP(O)s-
~HsS02S
-0.77
-0.56
-0.54
X>-s-
RO-C(S)s-
- +0.3
- +0.3
(n-C4H90)2P(O)S- -0.51 RC(O)s- - +0.3
(i-C3H,O)zP(O)S- -0.50 RC(S)S- - +0.3
(i-CsHuOhP(O)S- 0.48
S20l- 0.1
Rs- +0.3
248 G. F. BOLSHAKOV
When diaryl disulfides are treated with strong sulfuric acid the following reactions
take place:
R -vH + s-Qf
R
Sulfuric acid further oxidizes thianthrenes to thianthrene S,S-dioxides, the thian-

threne ion-radical being generated in this case.
Disulfides readily react with ozone to form sulfonic acid anhydrides, RS0 20S0 2R
and thiolsulfonates, RS0 2SR. The reaction mechanism is as follows:
- + -~ -/) - - 20
0-0=0- o-o-o~ o-o--- o-o 3
£(a 'J'
:s:s I o
: St: 'SR
2~/ o
S,.. 'SR
I I l I
RR R R
Disulfides are very active in their reaction with lead tetraacetate:
RSSR + 3Pb(OCOCH )
3 4 + 4R'OH- 2Rr0R' + 3Pb(OCOCH 3 ) 2 +
0
The mechanistic aspects of the reaction of disulfides with peracids have not been
extensively studied until now. The initial stage of the reaction is:
0
RCOOOH
RSSR R~SR + RCOOH
thiol-
sulfinate
This seems to be followed by the formation of thiolsulfonate, RS0 2SR.

Disulfides are oxidized by hydrogen peroxide:
The oxidation of disulfides in the presence of alkalies is as follows:
---~2~
0
RSSR + OH-
Dinitrogen tetroxide also oxidizes disulfides readily:
Disulfides undergo cleavage with some heavy metals, a reaction which is accom-
panied by desulfurization. Exposure to light leads to homolytic cleavage of disulfides:
h~ deactivation
RSSR --~ (RSSR]* RSSR
L:. 2Rs·
Rs• + solvent RSH
(l heA.ting (l + (l (l
s s s-s .N\.._ s s- s s_!\1\.
The decomposition of:disulfides in toluene when exposed to y-irradiation proceeds
according to the following mechanism:
activation C6HsCH3 ~ [C6H 5CH 3)*

k.l,
deactivation (C6HsCH3]• ~ Ct.H 5CH3
1
energy transmission [C6HsCl h]"' + RSSR ~ C6H5CH3 + RSSR
decomposition RSSR ~ RS + RS"'
deactivation RS"' 2!... RSSR
k
recombination 2RS --4 RSSR
250 G. F. BOLSHAKOV
k2 /k 1 ratio in disulfides:
C6H5CH2SSCH2C6H5 470
C6H5SSC6Hs 660
CH 3C6H.sSSC6HsCHJ 660
This ratio is also very high in mercaptans (C6H 5CH 2SH: 1160), but considerably
lower in sulfides. Thus, the k2 /k 1 value for dibenzyl, diphenyl, and ditolyl sulfide is 45,
3.5 and 1.4, respectively. Thus, thiols and disulfides strongly absorb energy.
The S-S bond cleavage can be mono- or bimolecular. When attacked by the
radical at the sulfur atom, disulfides are converted to a radical which is stabilized due
to a d-orbital assisted expansion of the valence electron shell and cannot initiate
further polymerization:
R" + R'SSR'--+ RS:-SR'

.. .
RS=SR'
.... .
RSSR'--+ R'SR + R'S, etc.
I I .. I
R R' R'
The presence of disulfides as well as mercaptans, sulfides and, to a lesser extent,

thiophenes inhibits oxidation and photochemical reduction. The photochemical
reduction of benzophenone with a-methylbenzyl alcohol, for example, affords the
radicals (C6H5hCOH and C6H5C(OH)CH 3 , readily trapped with disulfides:
ArSSAr
Ars• + ArSH +
Dialkyl disulfides react with phenyl radicals:
The ease of the hydrogen atom abstraction depends on the conformation of the
alkyl group in the disulfide. The attack on the sulfur atom occurs in 98 cases out of 100
in the reaction with dimethyl disulfide, for example, and in 45 cases of 100 in the re-
action with di-t-butyl disulfide. However, attack on disulfides is considerably more
difficult than on thiols. Hydrogen is abstracted from 2-propanethiol 1/22 times as
readily as from diisopropyl disulfide.
Disulfides serve as chain carriers in polymerization reactions. They can recombine
with a polymer radical, thus inhibiting the polymerization and promoting, at the same
time, the propagation of a new polymer chain:
M~ + RSSR--+ M8 SR + RS'
RS. + nM--+RSM~. etc.
The chain transfer constant, C, is equal to the ratio of the chain transfer rate
constant, kr. to the chain propagation rate constant; kP. An increase in C favors the
disulfide attack by radicals. Among disulfides the highest chain transfer constant is
observed with diary! derivatives wh.ich form stable radicals (Table 55).
Disulfides are subject to exchange reactions with other disulfides:
RSSR + R'SH RSSR' + RSH

RSSR' + R'SH .+=~ R'SSR' + RSH

RSSR + 2R'SH R'SSR' + RSH
RSSR + R'SSR'----- 2RSSR'
The substituent effect in these reactions is not large. Unsymmetrical dialkyl
disulfides, however, are relatively more stable while mixed diaryl disulfides are less
stable. The symmetrical/ asymmetrical disulfide ratio in the mixture is determined by
their structure. For example:
c2H5ssc 2H5 n-c 4H9ssc 4H9-n = 2:1
c2H5ssc 2H5 iso-c 4H9ssc 4H9-iao = 2: 1
CH 3SSCH.3 tert-C 4H9ssc 4H9-tert = 5: 1
CH 3SSCH.3 CH
3ssc 6H5 = .3:1
TABLE SS
Chain Transfer Constants for Disulfides in the Radical Polymerization of Styrene at 60 °C 155
Disulfides c ·104 Disulfide c ·104

(CH3Sh 94 (n-C4H9Sh 23.78
(CJH,Sh 23.4 (i-C4H9Sh 20.37
(i-CJH,Sh 6.6 (n-CH 3 ~H 4 Sh >1100
(t-C4H9Sh 1.42
(C6HsCOS)2 107
[0:)-s), >22000
252 G. F. BOLSHAKOV
The instability of di+butyl disulfide is mainly caused by rotation of the t-butyl

group. Since mixed diaryl sulfides are less stable, they cannot be readily isolated. The
formation of radicals upon cleavage is facilitated by stabilization due to resonance and
rearrangement:
s·-Q - s=Q - s-(J} R

R R
IV.2.4. Thiophenes. The sulfur atom in thiophene possesses a lone electron pair
conjugated with a carbon-carbon double bond. Besides, the sulfur atom has vacant
d-orbitals in the outer electron shell and can behave, therefore, as an electron
acceptor. The resonance structures with a negative charge on the sulfur atom are very
essential in thiophene. If the sulfur atom-carbon-carbon double bond conjugation is
considered as the appearance of two hybrid pd2 orbitals on the sulfur atom, the system
becomes formally analogous to benzene, since there are six atomic ?T·orbitals and 6
?T·electrons in both cases. In fact, thiophene is characterized by the same reactions as
aromatic hydrocarbons. From localization energy calculations it may be concluded
that the reactivity of thiophenes in position 3 should be close to that of benzene, and
in position 2 it is much higher than in position 3. The reactivity in positions 2 and 3 has
been studied in more detail. 172 In the protium-tritium exchange reaction in aqueous
sulfuric acid the k2 /k 3 ratio is 955 :t 140 whereas in the substitution of the silyl group
Si(CH3) 3 by a proton the k2 /k 3 value is 43.5. The partial rate factors calculated for
this reaction are 5000 and 115 for positions 2 and 3, respectively.
Thiophene undergoes halogenation, nitration, and sulfonation. A typical reaction
of thiophene is chloromethylation by the action of formaldehyde and hydrochloric
acid:
+
CH20H
0s UcHOH
s 2
G c H OH
s 2
+ HCl ~ 0s CH c1
2
+ H2°
Thiophene is alkylated at the heteroatom to form stable salts:
[[J
{CH ) o+BF - l
s..
3 3
CH2cl2
4
O NaPF 6
¥+BF ---H-_0__.,.
4 2
CHJ
Upon photolysis, 2·substituted thiophenes are subject to rearrangement to 3-

substituted derivatives:
Nucleophilic substitution and addition are not common in thiophene chemistry .158
Thiophene is reduced by sodium in liquid ammonia in the presence of platinum on
charcoal or molybdenum sulfide. In the presence of hydrogen and a nickel catalyst,
thiophene undergoes desulfurization:
R R
Ti-1(
R~SAR Ni
Some reactions involving thiophene ring expansion are known:
NC-C=C-CN
Thiophene readily reacts with acid chlorides and aluminium chloride:
0s ~
l( 8 A COCHJ
+ HCl
This acylation smoothly proceeds also in the presence of ZnCl2 , I2 , HI, TiHCl3 , etc.
Benzothiophene is less reactive than thiophene. Some reactions typical of
thiophene, such as chloromethylation, alkylation with methyl iodide, and the
Mannich reaction cannot be carried out with benzothiophene. In nitration or
bromination an acetylamino group in position 3 directs the nitro group and bromine
to position 2:
~COCHJ
~-.1(-.
S Br
Thiophene and its benzo homologs are considerably more stable to oxidants
than thiols, sulfides, and disulfides. When treated with chromium oxide 5·
methylbenzothiophene forms the corresponding uinone: '
254 G. F. BOLSHAKOV
Oxidation with oxygen under appropriate conditions leads to the formation of

quinone sulfones via the corresponding quinones.
0
11
HC
2'QJ
s 11 11 ~
0 0 0
Dibenzothiophene resembles in its chemical properties aromatic hydrocarbons.

Electrophilic substitution occurs first in position 3. If this site is occupied, the
substitution takes place in position 6. The o- and p-orienting effect of the sulfur atom
is of great importance in these reactions:
Thiophene, benzothiophene, and dibenzothiophene are readily metallated with

lithium derivatives.
IV.3. Physical Properties
IV.3.1. Density. The density of relatively low-molecular substances depends on

their molecular mass. This is due to an unlike degree of molecular packing in a unit
space. Thus, the density of n-alkanes increases greatly from C 3 to C~. The difference
in the density between propane and n-pentacosane is about 37% (Fig. 40). All the
more surprising is the almost complete independence of the density of 1- and
2-alkanethiols, and 2- and 3-thiaalkanes on their molecular mass which was first
recognized by the present author (Fig. 40). The density of 1-alkanethiols and
2-n-thiaalkanes is nearly the same from C3 to ~ 0 , increasing slightly with an increase
2____ _
--------
MOLECULAR UASS
FIGURE 40. The effect of the molecular mass on the sulfur compound density.
1-n-dithiaalkanes, AlkSAlkSAik: 2-n-dithiaalkanes, AlkSSAlk; 3-1-alkanethiols; 4-2-
thiaalkanes; CII3SA1k; 5-3-thiaalkanes, C211 5SAik; 6-2-alkanethiols, Cli 3CJI(SH)Alk; 7-ethers,
AlkOCH 3; 8-alcohols, AlkOII; 9-n-alkanes.
in the molecular mass. The difference in the density between C3S and ~0S and C20 is
about 0.8%. 2·Aikancthiols arc of somewhat lower density, but in this case again the
difference in the density between lower and higher representatives does not exceed
0.8-1.0%. Unlike n-alkanethiols and n-thiaalkanes, the density of n-dithiaalkanes
considerably decreases from C4 to C20 • The density difference between these
compounds is about 20%.
Since mercaptans and sulfides are alcohol and ether analogs, it is of interest to
compare the change in the density of these compounds with increasing molecular
mass.
The density of n-cthcrs changes with the molecular mass similarly to that of
n-hydrocarbons (Fig. 40). The density change of normal alcohols is smaller than that
of cthers. The difference in the density between 1-propanol and 1-undecanol is more
than 9%, i.e., ten times as large as that of thiols and sulfides. It should be noted
that with the mass exceeding 350, the density is approaching a certain limit close to
the density of high-molecular alkancs. The predicted density values for sulfur
compounds, hydrocarbons, ethers, and alcohols are shown with broken lines in
Fig. 40.
256 G. F. BOLSHAKOV
The density of thiaalkanes and alkanethiols (as well as that of their structural
isomers is within a fairly narrow region (820-845 kg/m 3) which narrows with
increasing molecular mass. Some exceptions, however, are possible. Thus, the density
of 4-methyl-2-pentanethiol, 3-hexanethiol, and 2,4,6,8-tetramethyl-5-thianonane is
1001.0, 920.6, and 893.6 kg/m 3 , respectively. This anomalous density increase is
related to the specific sulfur compound structure and the densest packing of these
compounds:
~ ~Lr
1001.0 kg/mJ 920.6 kg/mJ 89.3.6 kg/m3
The extremum in the density depression in 2-octanethiol is worthy of note

(Fig. 41). This extremum reappears with 2-nonanethiol in the refraction coefficient
depression. Again a strong divergence in the density change is observed with
2-alkanethiols and methyl substituted n-alkanes (Fig. 41). With an increase in the
molecular mass of aromatic sulfur compounds, thiophenes, and thiacycloalkanes by
virtue of the lengthening of the alkyl substituents, the sulfur compound density
diminishes. The remarkable ability of alkanethiols and thiaalkanes to change their
density negligibly with increasing molecular mass remains inexplicable. In these
compounds the distance between the molecules is possibly nearly equal to the mean
bond lengths, which permits retainment of nearly equal mass per unit volume for
sulfur compounds of various molecular mass. The coordination interaction between
the sulfur atoms seems to play the main role in the this effect.
W.3.2. Boiling point. The boiling points of sulfur compounds regularly rise with
increasing molecular mass with a curvilinear dependence. Clearly defined depend-
ences are revealed for normal1- and 2-alkanethiols (Figs. 41, 42). The boiling points
of 1· and 2-alkanethiols and 2-thiaalkanes arc very similar. The boiling point
depressions are also very close, decreasing regularly with increasing molecular mass.
With increasing molecular mass the ratio of the boiling temperature rise decreases.
The dependence of the sulfur compound boiling point on the molecular mass for
various homologous series is described by the following equation: 173
tb =to=---
c
no+ N
where to, c, and no are empirical constants (Table 56); n = number of carbon atoms in
the sulfur compound molecule.
IV.3.3. Melting point. With an increasing molecular mass, the melting point
n~turally, increases. Wit~ 1-alkanethiols a certain regularity is revealed. Beginnin~
wtth C3 the c_ompo~nds w1th an even ~umber of carbon atoms in the molecule display
a l~wer m~ltmg p01~t than the preced1~g me~ber of the homologous series (Fig. 42).
Thts gradtent, AT, ts at a maxtmum With thtols at the beginning of the homologous
e-o..!M:!
..,.
I
f..<r:'J
... 0
4
2 tCI ...
·«» .., d
0
NQ
.50 <I
·J)
28 11
'i'O
..,
•P
e Z& .,
14 t4 ?0
a
fZ 2t &0
·ll
m~~
t!)
ill
e ID «J
·!D
..., 6 t6 30
-50 • lt 20
l 10
-«)
M ·r.l
70
1'JO
..,
71)
60 «l
, 6i'O
~
.cJ
~
fl
~
?11
a & a m rz u 16 ta zo !10 t.e,
NWBER OF CARBON ATOMS
FIGURE 41, The effect of the molecular mass on the physical properties of normal 2-alkanethiols.
series and decreases with increasing molecular mass. The same effect, but less
pronounced, is observed with 2-alkanethiols (Fig. 42). A similar effect has been noted
174
for n-alkanes. With 2-thiaalkanes (n-AlkSCH3) the change in the melting point
with increasing molecular mass follows nearly the same pattern as with 2-alkanethiols
(Figs. 41, 42). It should be noted that the character of the change in the melting point
gradient, Tm for 1-alkanethiols (AlkSH), is analogous to that for 2-thiaalkanes
0 1.:1
-() 30
·20 20
-J) ll
-14)
t.'C
1---------------..,..-l l.'C0
·llil
-120
-m
-m
-m 2lJJ
.,.,
·20
Ill
0
o~------------------------~---J60
z ~ ' 1 ~ ~ ~ e ~ ~
NUMBER OF CARBON ATOMS
FIGURE 42. The effect of the molecular mass on the boiling and melting points of normal
1-alkanethiols (Tn) and 2-thiaalkanes (T~).
TABLE 56
Constants fo, C, n0 in the Sulfur Compound Boiling Point/Molecular Weight
Dependence Equation
Compound to c no
1-Alkanethiols 978 -28323 28.32

2· Alkanethiols 913 -23256 23.95
2-Thiaalkanes 1183 -43478 36.00
n-Thiaalkanes
Alk-S-Alk 655 -10416 14.45
(n-AlkSCH 3), but less clear-cut (Fig. 41). Data on other physical properties of sulfur
compounds are very scarce and do not allow elucidation of the change in their
properties depending on the molecular mass and the structure.
IV.3.4. Dipole moments. The dipole moments of sulfur compounds depend upon
the structure (Table 57). An increase in the molecular mass and the structural
asymmetry of n-alkanethiols raises, as a rule, the dipole moment significantly. The
TABLE 57
Sulfur Compound Dipole Moments226
Sulfur compound Temperature, •c Dipole moment, D

1 2 3
Thiols
Methanethiol 1.26 ± 0.05
Ethanethiol 15 1.38 ± 0.02
25 1.48
35-205 1.56
1-Propanethiol 20 1.33
25 1.51
2-Propanethiol 25 1.55
1-Butanethiol 20 1.32
25 1.48
1.53
so 1.49
2-Methyl-2-propanethiol 20 1.55
25 1.59
Cyclohexanethiol 25 1.73
Thiophenol 20 1.33
25 1.23
a-Toluenethiol 25 1.44
1,4-Toluenedithiol 20 1.85
1-Nap~thalenethiol 20 1.17
1,8-Naphthalenedithiol 20 1.69
1 ,4-Bis(mercaptomethyl)-nap hthalene 20 1.93
1,5-Bis(mercaptomethyl)-naphthalene 20 1.29
1,8-Bis(mercaptomethyl)-naphthalene 20 1.80
Tetrakis(mercaptomethyl)methane 70 0.50
260 G. F. BOLSHAKOV
1 l 3
Sulfides
Dimethyl sulfide 20 1.45
Diethyl sulfide 28-200 1.51
Dipropyl sulfide 20 1.55
Dibutyl sulfide 20 1.57
Diamyl sulfide 25 1.58
Methyl cyclohexyl sulfide 1.63
Ditetradecyl sulfide 2S 1.97
Dihexadecyl sulfide 30 1.47

Diphenyl sulfide 1.52
Dibenzyl sulfide 21 1.38
2,2'-Dimethyldiphenyl sulfide 20 1.08
2,3' ·Dimethyldiphenyl sulfide 20 1.44
Phenyl p-tolyl sulfide 25 1.75
Di-p·tolyl sulfide 25 1.92-1.94
Thiophane 20 1.87
Thiacyclopropane 1.84 ± 0.02
3,3-Dimethylthiacyclobutane 1.76
0 ligosuljides
Dimethyl disulfide 25 1.95
Diethyl disulfide 25 1.99
Dipropyl disulfide 25 1.98
Dibutyl disulfide 25 1.99
Diisobutyl disulfide 25 2.00
Dioctyl disulfide 25 1.99
Ditetradecyl disulfide 25 1.97
Dihexadecyl disultide 30 2.00
Dioctadecyl disulfide 2S 2.07
Diphenyl disulfide 20 1.90
Dibenzyl disulfide 25 1.90
Di-(p·tolyl) disulfide
1.97
1 1 3
Dimethyl trisulfide 25 1.66

Diethyl trisulfide 25 1.64
Dihexadecyl trisulfide 30 1.63
Dibenzyl trisulfide 25 1.67
Thiophenes
Thiophene 20-200 0.52-0.55
2-Methylthiophene 0.67
3-Methylthiophene 0.82
2,5-Dimethylthiophene 30 0.51
Benzothiophene 30 0.62
Dibenzothiophene 30 0.83
24 0
same is true for aromatic thiols. 1,5-Bis(mercaptomethyl)naphthalene of symmetric

structure, for example, displays a considerably lower dipole moment compared with
its 1,4- and 1,8-substituted analogs. The completely symmetric compound tetrakis-
(mercaptomethyl)methane, C(CH 2SH) 4 has a low dipole moment.
In symmetric sulfides the dipole moment increases with increasing molecular mass.
In aromatic sulfides, the insertion of a methylene group between the sulfur atom and
the aromatic ring leads to decreasing dipole moments.
A change in the position of methyl substituents in divinyl sulfides, leading to an
asymmetric structure, greatly enhances the dipole moment. The alkyl disulfides
~-C 8 possess remarkably similar dipole moments (Table 57) which enhance slightly
only upon a considerable increase in the molecular mass. Diaryl disulfides possess
dipole moments close to those of alkyl disulfides. The dipole moments for only four
trisulfides have been reported. Independent of the molecular mass they are close to
each other and considerably lower than the dipole moments of the corresponding
disulfides.
Thiophenes display low dipole moments which again confirms their similarity with
aromatic hydrocarbons.
IV.4. Thermodynamic Properties
IV.4.1. Heat Capacity. The heat capacity of sulfur compounds is lower than
that of the co~responding hydrocar?ons. 175 Beginning with c4 the heat capacity of
hydrocarbons ts nearly constant (Ftg. 43). In contrast, the heat capacity of sulfur
compounds rises with increasing molecular mass. With a considerable increase in
1
the molecular mass the sulfur i compound heat capacity approaches the heat
capacity of the corresponding hydrocarbons. The heat capacity of n-alkanethiols is
262 G. F. BOLSHAKOV
~'~----------------------~------~
--._~.....!
CU1
...... .._.. 1)===-Qo-"4....... t

2 4 a & w ~ u ~ M ~
NUMBER OP CARBON ATOMS IN TilE MOLECULE
FIGURE 43. The effect of the molecular mass on the sulfur compound heat capacity, kcal/(kg l<)
1-thiacycloalkanes (thiacyclopropane, thiacyctobutane, thiophane, thiacyclohexane} at 25 °C; 2-
symmetric n-dithiaalkanes at 0 oc; 3-1-alkanethiols at 0 cc; 4-1-alkanethiols at 27 cc; 5-n-alkane
vapors at 25 °C; 6-n-alkanes at 2S °C.
10-20% higher than that of dithiaalkanes, very close to the heat capacity of
n-thiaalkanes. The sulfur compound heat capacity increases with rising tem-
perature.
IV.4.2. Entropy, Enthalpy, and Isobaric Potential of l·alkanethiols and 2-

thiaalkanes change with increasing molecular mass according to the following
equation: 173
(X),= aM+ b
TABLE 58
Constants a and b in the Equation (X), = aM + b at 25 °C
Cp, -~H, ~z. S,
ca1/(mol· K) kcal/mol kcal/mol caJ/(mol· K)
Compound a b a b a b a b
1-alkanethiols 0.391 -7.02 0.352 4.64 0.138 18.98 0.674 28.73

2-thiaalkanes 0.383 -6.19 0.363 1.9 0.699 24.46
where (X), is the corresponding thermodynamic function at constant temperature,

M is the molecular mass, and a and b are constants. The change in the heat capac-
ity also obeys the above equation. The coefficients a and b are given in Table 58.
It follows from these data that the mole values of heat capacity, entropy, enthalpy,
and isobaric potential are subject to linear dependence. The bulk values of these
thermodynamic functions, however, which are of great practical importance,
change in a curvilinear fashion. There is a linear dependence between the change
in isobaric potential and enthalpy of 1-alkanethiols and 2-thiaalkanes at 25 °C. 173
llZ = -kllH +m
where k and m are constants (Table 59). The sulfur compound heat of evaporation
decreases with increasing molecular mass in the corresponding homologous series:
Sulfides Heat or evaporation, kcal/kg

2-Thiapropane 104.4
2-Thiabutane 93.6
2-Thiapentane 85.6
3-Thiapentane 86.1
3-Thiahexane 78.9
3-Thiaheptane 74.3
TABLE 59
K and m Constants in the Equation
4.Z = -k4.H +m
Compound k m
1-alkanethiols 0.40 -21.20

2-thiaalkanes 0.31 -15.50
When the sutfur atom moves to the molecular center in normal sulfides the heat of
evaporation increases somewhat.
JV.5. Optical Properties
/V.5.1. Refractive Index. The refractive index for sulfur compounds of various
structures increases with increasing molecular mass in a curvilinear dependence. The
refractive index depression decreases with increasing molecular mass. Normal alkanes
possess a considerably lower refractive index which varies greatly with increasing
molecular mass (Fig. 44).
Thiacycloalkanes are characterized by a high refractive index. A general tendency
typical of thiacycloalkanes is the increase in the refractive index on going from
thiacyclopropane to thiacyclohexane: 173
D D Q
1.490 1.50887 1.5048.3 1.5067
Thiacycloalkanes are characterized by a high refractive index which diminishes in

general with increasing number and length of alkyl substituents. The refractive index
increases, however, if the alkyl substituents contain multiple bonds:
1.5722 Occ:c 1.5879
Dibenzothiophenes display an even higher refractive index. In the case of ben-

zothiophene n~ = 1.6212, for example. Unlike other sulfur compounds, in di-
sulfides the refractive index diminishes with increasing molecular mass (Fig. 44).
An increasing number of sulfur atoms in aliphatic sutrur compounds leads to
an increasing refractive index:
e4ssse4 1.5320 esse 1.5259

e.sssse. 1.5722 cssse 1.6010
The mole refractiont depends on the sulfur compound molecular mass:
MR~ =AN+ B
1.41
1.455
1.445
1.4)5
L-.-~........-.r-r-~~__,.......,_,.~__,...... 1. 425
2 4 6 8 10 12 14 16 18 20
NUMBER OF CARBON ATOMS PER MOLECULE
FIGURE 44. The effect of the molecular mass on the sulfur compound refractive index:
1-2-thiaalkanes; 2-1-alkanethiols; 3-2-alkanethiols; 4-symmetric n-dithiaalkanes; 5-n-alkanes.
where N is the number of carbon atoms in the sulfur compound molecule. A and B
are constants (Table 60).
The refraction values for different sulfur compound groups differ much (Table 61).
The group refractions, R~ have been calculated using measured mole refraction
values.
W.5.2. Infrared Spectra. In the IR spectra of sulfur compounds one can identify
absorption bands due to vibrations of S-H, C-S, and S-S bonds as well as to
sulfur-containing heterocycles.
266 G. F. BOLSHAKOV
TABLE60
Coefficients A and B In the Equation MR~ =AN + B 173
Sulfur compounds Fonnula A B
1·Alkanethiols Alk.SH 4.6 9.9

2·Aikanethiols AlkCH(Sfi)Cll3 4.6 10.8
2·Thiaa!kanes AlkSCll3 4.0 13.2
n·Thiaalkanes Alk.SAik 4.6 9.2
Thiaalkenes Alk.SCli=-CH-R 14.0 32.2
Alkyl aryl sulfides ArSA!k 4.6 9.5
n·Dithiaalkanes Alk.SSA!k 4.6 12.1

i-Dithiaalkanes iso-A!kSSA!k-iso 4.6 18.4
2·Alkylthiopbanes 4.6 8.0
Q.A!k
3-A!k.ylthiophanes
OAlk 4.5 8.0
s
2,5-Dia!ky!thiophanes Alk-C:J-Aik 4.SS 8.5
Alk
2,3,5-Trialkylthiophanes 4.1 12.4
A!kDAik
s
2-Alkylthiopbenes 0-Aik 4.6 10.1
s
2,5-Dialkylthiophenes AlkDAik 4.1 11.5
s
Thiols are characterized by stretching vibrations of S-H and C-SH bonds.

Deformation vibrations of the S-H bond cannot be used for identification, since the
planar deformation S-H vibration does not manifest itself in the IR spectrum
whereas the non-planar vibration absorbs weakly within the 830-825 cm - 1 range
where the interpretation is difficult due to overlapping. The C-S deformation
vibrations should absorb in the frequency region below 400 cm - 1• This IR spectral
region of thiols has not been studied yet.
In the thiols investigated the symmetrical stretching vibrations of the S-H bond
give rise to absorption in the 2595-2538 cm-l region. 176 The absorption of c.-c
thiols lies within the fairly narrow region of 2567-2545 cm- 1• As the molecular mas:
of thiols increases, the S-H absorption is displaced toward a higher-frequency
region. Thus, the absorption frequency of symmetrical stretching depends on
TABLE 61
Group Refraction of Functional Groups, R~, for Calculating Sulfur Compound
Molar Refractions at 20 °C 173
Group R~ Group R~
R--{3=~
-CH 2SH 11.123
17.626
'CHSH/
./ .........
10.046 s
-CH2SCII3 15.800 e113GI 2- 7.986
12.654 ./
-CII 2SCIIz- eH 3eH......._ 6.934
20.567 /
-ei{zSSeiiz- eH 3- e - 6.388
-CH 2eHSSCIICII2-
I I /
19.025 -CJ12CII2- ' 4.645
./
18.299 -CII 2CII......._ 3.446
'cHCIISSCHCII . . . _
/ I -CH2C::: 2.793
~esse/ 17.568 -CHCH...,., 2.091
./ ......... ./ .........
'cue::::::: 1.352
c;J-R 17.361 ./
........
-C-C-
.........
./
0.506
./ .........
RD-R 17.506
s
inductive and mesomeric effects and conformational features of the hydrocarbon

skeleton structure. The inductive effects are most likely to be the main reason for
changes in the absorption frequency. Therefore, there is a linear dependence between
the precise frequency value and the sum of the electronegativities of the substituents
in the molecule.
For the unbranched primary thiols C,, 4, C 11 , C13 , and C15 , the S-H absorption
wave number is very close to 2596 cm - 1; in the Cs, C10, C 12 , C14 , and C 16 , thiols this
wave number is shifted towards a lower-wave number region, 2570 cm- 1 • The same
regularity is observed for lower-molecular thiols, but only in the lower-wave number
region. Thiols with an odd number of car?on atoms (C 1 , C3 , Cs) absorb in the
2567-2564 cm- 1 range, those with an even number(~, C4) absorb in the 2550-
2545 cm- 1 range. 1-Hexanethiol with its S-H group absorbing at 2591 cm- 1 is the
only exception. This systematic change of the absorption wave numbers with the
number of carbon atoms in unbranched, saturated thiols was recognized for the first
time in 1979. 154 The S-H bond of aromatic thiols c;-C 16 absorbs within a 8 cm- 1
range (2568-2560 cm- 1); in thiophenol, however, this wave number is higher
(2854 cm- 1).
The intensity of the S-H absorption in aliphatic thiols decreases regularly as the
molecular mass increases; the UV extinction coefficient diminishing accordingly .176
Primary, secondary, and tertiary aliphatic saturated thiols of the same molecular mass
display nearly the same S-H absorption intensity. Cyclic saturated thiols display
a more intense S-H absorption and thereby a greater UV extinction coefficient as
compared to aliphatic thiols. With increasing number of carbon atoms in the ring the
intensity of the S-H absorption decreases. Among cyclic saturated thiols, the highest
absorption intensity is observed with cyclopropanethiol. With an increase in the
length and number of hydrocarbon side chains the S-H absorption intensity
diminishes approaching the absorption intensity of atiphatic saturated thiols. The
highest S-H absorption intensity is observed with thiophenol which is quite natural
and explainable in terms of the specific electronic structure of the benzene ring.
Insertion of methyl groups into thiophcnol decreases greatly the S-H absorption
intensity (nearly 4-fold). The same regularity is also observed with thionaphthol and
its alkyl homologs, the S-H absorption intensity, however, being about half as large
as that of thiophenol and its alkyl homologs. It should be noted that the insertion of a
methylene group into thiophenol leads to a decrease of the S-H intensity to one
fifth. 176 It should be expected that as the number of methylene groups between the
sulfur atom and the carbon atom of the benzene ring increases, the S-H absorption
intensity is approaching that of the aliphatic thiols.

Unlike alcohols, acids, and amines, thiols form only weak hydrogen bonds. The
S-H absorption frequency does not change much in the spectra of thiols in solution
and the gaseous state as well as in neutral solvents. If the solvent is of basic character
the absorption wave number decreases considerably 176 indicating higher energy of
interaction between the functional group of the solvent and the S-H group of the
thiol. The energy of the hydrogen bond of thiols with polar solvents, determined
catorimetrically, does not exceed 1.5 kcal/mole.
The C-S stretchi~g vibrations of thiols arc known to occur as relatively weak
absorption in the 700-600 cm- 1 region. 177 On studying the C-H stretching it is
necessary to consider the 700-500 cm- 1 region. Investigation of a characteristic
absorption of thiols has shown that the C-S bonds of primary, secondary, and
tertiary saturated thiols absorb in the regions 655-645, 625-615, and 590-575 cm-t,
respectively. With increasing molecular mass of thiols from C1 to Cs, an essential
lowering of the absorption wave number occurs, amounting to approximately 60, 90,
and 130 cm- 1 for C1 - n-C5 , C 1 - s·Cs and C 1 - t-C5 , respectively. Some interest-
ing regularities of the C-S absorption in primary thiols should be noted. 176 The C-S
absorption wave number in normal thiols systematically decreases with increasing
molecular mass to about c.. , then increases to 4 and again increases and decreases.
For thiols, this regularity is most likely to persist. Unfortunately, a lack of thiols of
normal structure with a molecular mass exceeding 258 has prevented a check of this
hypothesis. It should also be mentioned that a greater branching of the carbon
skeleton of primary thiols leads to a higher C-S absorption wave number which is
welt illustrated by the Cs thiols. 176
The C-S absorption wave number of aromatic thiols is nearly coincident with the
corresponding wave number of secondary thiols.
The intensity of the C-S absorption of primary and secondary as well as monocy.
clic thiols is relatively low and does not differ much in value. 176 It is to be noted, how-
ever, that as the molecular mass decreases, the C-S absorption intensity of sec-
?ndary thiols grows hi~her as compared with primary thiols, and that of tertiary thiols
mcreases greatly. Thtonaphthols also show a higher C-S absorption inten 't
.h. . I I SI y
w1t mcreasmg mo ecu ar mass and branching of a neighboring (with respect to the
thio group) substitueht which is indicative of the C-S bond excitation due to redis-
tribution of the electron density in the molecule.
The questions concerning a possible C-S absorption in the 600-400 cm- 1 region
should be discussed separately.
No absorption of thiols below 600 cm- 1 has been studied. This region must show an
absorption caused by the skeletal vibrations of hydrocarbons. Introduction of the
thiol group affects significantly the skeletal vibrations and, consequently, the IR
spectrum. 176 The major feature of this effect is a considerable weakening or complete
disappearance of the main absorption bands of skeletal vibrations in the region under
consideration. This is clearly expressed also with cyclic saturated thiols to C5 • 176 For
example, an intense absorption of the cyclopentane ring near 540 cm- 1 disappears in
cyclopentanethiol. The influence of the thiol group on less strained rings is less
pronounced. In cyclohexanethiol and methylcyclohexanethiol the skeletal absorption
band remains in the same region, displaced only by 20-30 cm- 1 towards lower wave
numbers.
It is most likely that these phenomena can be explained in terms of the electron-
acceptor properties of carbon toward the sulfur atoms which are electron donors. Due
to this effect, the electronic structure of the carbon skeleton loosens and the wave
numbers are displaced to the low-wave number region. The displacement is expected
to be larger in low-molecular aliphatic and cyclic saturated thiols (methanethiol and
cyclopropanethiol).
The above peculiarities can bear no relation to aromatic thiols owing to the specific
7T-electron structure of the aromatic rings. Quantum-chemical calculations on aroma·
tic thiols may provide more complete information concerning this subject.
Thus, the research done has allowed one to establish for the first time the important
features and regularities of absorption of S-H and C-S bonds of thiols which may
be used for the identification and quantitative determination of saturated and
aromatic thiols.
Sulfides are characterized by the absorption region 700-800 cm- 1 .1 77 The absorp-
tion wave number also decreases regularly on going from primary to secondary and
tertiary sulfides. With aromatic sui fides the detection of C-S bonds is obscured by a
possible overlapping of frequencies of non-planar deformation vibrations arisen from
aromatic C-H bonds. The same absorption frequencies are also associated with
C-S bonds of disulfides; however, on going from mercaptans to disulfides the
corresponding bands are displaced to the lower-wave number region.
A C-S bond conjugation with a double bond lowers by 60 cm- 1 the C-S
vibration wave numbers, the absorption intensity increasing sharply. 177 It is to be
mentioned that conjugation of this kind also lowers the wave numbers of the C=C
stretching vibrations and of the olefinic CH deformation vibrations (by approximately
50 and 30 cm- 1, respectively). The C-S deformation frequencies are in the far IR
region and have not been studied.
The structure of sulfides can be defined more exactly from the data of Ref.117. The
limiting value of aliphatic sulfide concentrations allowing quantitative determination
using the c-s bond band, is 2-3%
The presence of c-s bonds can be determined, however' by the characteristic
vibrations of S-0 bonds after the oxidation of the substance studied. Upon selective
270 G. F. BOLSHAKOV
oxidation, not involving other fonns of sulfur bonds, sulfides can be determined fairly
exactly in rather complicated mixtures of organic sulfur compounds.
The compounds with a C-S bond in a five·membered ring show an absorption
corresponding to stretching vibrations of C-S bonds in sulfides as well as intense
absorption bands in the 1260-1225 cm -t region. These bands are indicative of the
five-membered ring sulfur atom (ring skeletal vibrations) and occur in the spectra of
all the thiophanes and thiophenes.tn The region 1260-1225 cm-• is characteristic,
however, only in the absence of oxygen compounds (C-O bonds). The deformation
vibrations of the sulfur-containing rings should be expected to be highly characteris-
tic. There are no literature data available concerning this question, but the present
author has observed in the spectra of the thiophanes studied a 568-565 cm- 1
absorption of constant frequency which appears to be characteristic of thiophanes
belonging to certain substitution types, which is also confirmed by the Raman spectra.
Disulfides and sulfides show a characteristic absorption in the range 1195-1170 and
1670 cm- 1 , respectively. 177

The thiophene group has been fingerprinted in detail by IR spectroscopy
(Table 62). 1n
The major vibration frequencies of the carbon skeleton of this five·membered
heterocycle and of its hydrogen atoms are not characteristic of the thiophenes only,
since they are similar for rings with different hetcroatoms, i.e., for thiophene, furan,
and pyrrole, thus indicating only the presence of a five-membered heterocycte.
The C=S vibrations can only be reliably identified on studying the IR spectra of
TABLE6l
Charaderistic Absorption Frequencies or Thiophene
Absorption region
Note
7.95-8.15 1260-1225 Five-membered ring sulfur

Absence of the band does not exclude the presence of a thiophene
structure
The band is known for all alkylthiophenes except 3 4-
dimethylthiophene '
10.1 990 3-Aikyl substituted thiophenes (overlapping with C==C at the chain
terminal)
11.8 847 Single band in thiophene;
12.2 820 Doublet in all monoalkyl substituted thiophenes
13.1 763 Strong band in 3-methyl- and 3-thiol derivatives
No band in 2-alkyl- and 2-thio derivatives
Evidently, indication of thiophene ring 3-substitution
18.2 549 Band is of low intensity
7.08 1411
9.21 1085
relatively large molecules, since the simple thioketones mainly exist as dimers in
which the thioketone structure disappears.
The characteristic wave numbers of the C=S stretching vibrations occur in the
1050-1200 cm- 1 region. The exact position depends on the substituents and, in
certain cases, is linearly related to the sum of their electronegativities. 177
For thiourea derivatives, the frequency is not constant and is confined to a higher
wave number range of 1400-1130 cm- 1 • In thioamides, the C=S absorption region
lies near ll20 cm- 1 .
A number of general ranges for C=S absorption wave numbers have been found
for thiocarbonyl compounds of various types:
cm- 1
Cl......_
C=S 1121
c("
R-S
'c=s ... .... ........ .......... ....... ......... ... ..... .. ........ ...... .. ..... 1058-1053
R-S/
R-0
'c=s ........................................................................ 1234-1212
R-0/
"'-c=C-C=S ... ................... ......................................... ......... 1156-1143

/ I I
C6Hs,
C=S ....... ....... .... ....... .... ........... ...... .. ... ........... . .. ....... 1226-1219
/
C6Hs
The absorption band corresponding to the S-S bond is of low intensity and occurs
in the 400-500 cm- 1 region. This band does not appear to be useful for analytical
purposes.
N.5.3. Electronic Spectra The absorption bands of sulfur-containing chromophores

occur in various spectral regions depending, naturally, upon the sulfur compound
structure.
N.5.3.1. Thiols. The absorption band of the thiols 178 is observed in the 228-
232 mJ.t range. The absorption band of the alkanethiols results from the excitement of
free 3p-electrons of the sulfur atom, i.e. it presents the n-.u• transition. In the
arylthiophenes the absorption is most likely to be caused by interaction of 7T-orbital
electrons of the arene ring and possibly, of 3d-orbital electrons of the sulfur atom.
The interaction of 3p-electrons of the sulfur atom with 7T-electrons of the arene ring
decreases in going from monoarenes to polycondensed arenes.
N.5.3.2. Sulfides. The dialkyl sulfides absorb near 186 and within the 210-216 mJ,t
range. An absorption maximum near 186 ffiJ.t is observed in the area adjacent to the
272 G. F. BOLSHAKOV
short-wave limit of the near-ultraviolet region. These absorption bands are of little
help due to low intensity and their occurrence in the spectral region is hardly
accessible for measurements.
Characteristic absorptions of cyclic sulfides occur, depending on the structure, at
275, 262-258, 255-250, 245-240, and 219-214 m~-t. Thus, dimethylene sulfide
absorbs at 261 and 245 mp., trimethylene sulfide, tetramethylene sulfide, and penta-
178
methylene sulfide at 275 and 218, 240 and 219, 229, and 210 mJ.L, respectively .
The long-wave absorption of sulfur-containing saturated heterocycles is caused by
excitation of lower lying u*-orbitals which indicates the poorly binding and loosening
character of the u- and u*-orbitals of C-H bonds. Sulfur-containing saturated
heterocycles and alkyl sulfides display two absorption bands. 178 The less intense
long-wave band seems to be due to excitation of unshared p-electrons of the sulfur
atom. The band in the shorter wave-length region is of higher intensity and arises by
excitation of s- and sp-hybridized electrons. Since the energy of p-electrons is higher

than that of the corresponding s-electrons, and the u-orbital is of p- rather than of
s-character, n5~u* transitions are more favorable and give rise to a stronger
absorption than nP~u* transitions do. This is also true for the alkyl sulfides: that is
why the alkyl sulfides and cyclic sulfides absorb in the same region, Amax =
210-219 m~-t.
W.5.3.3. Disulfides. Dialkyl disulfides normally absorb near 250 m~-t, i.e., at con-
siderably longer wavelengths than alkanethiols and, especially, dialkyl sulfides. 178 As
compared with open-chain disulfides, cyclic disulfides show a characteristic absorption
at much longer wavelengths.
In trimethylene disulfide the unshared p-electron orbitals of the sulfur atoms
overlap each other. This leads to the formation of bonding and loosening of orbitals
occupied with paired electrons. 178 The molecular (bonding) orbitals possess a greater
energy compared to the atomic orbitals of the unshared electrons of sulfur. This is
responsible for a zig-zag conformation with a dihedral angle of about 90°. In acyclic
dialkyl disulfides the overlap between atomic orbitals of unshared electrons is zero,
while it is of maximum value (0.129) in trimethylene disulfide.
In tetra- and pentamethylene disulfide the overlap between atomic orbitals is
somewhat smaller due to the conformational flexibility of six- and seven-membered
rings.
Owing to symmetry, the transition to the loosening u-orbital of the S-S bond is
allowed from the 71'-molecular orbital only which is occupied by an unshared electron
pair. This governs the characteristic absorption of disulfides of various structure. 178
With increasing number of sulfur atoms in polysulfides a bathochromic effect is
observed. In all dialkyl disulfides, for example, the absorption maximum occurs near
250 mp., being observed near 290 and 325 mp. in diethyl tetrasulfide and dicyclohexyl
hexasulfide, respectively.
IV.5.3.4. Thiophenes. Thiophenes display a rather intense absorption in the 230-

238 mp. region. Characteristic maxima of thiophene and its alkyl derivatives are
reported in 178 • The introduction of alkyl substituents into the thiophene ring causes a
slight bathochromic displacement of the absorption maximum. This displacement
increases with increasing number of substituents. The molar extinction coefficients

are approximately equal. Since the characteristic absorption of thiophenes differs
much from that of other sulfur compounds, their spectra can be of help in the
identification and quantitative assessment of thiophenes in mixtures and in other
studies.
A strong band ascribed to thiophenes in a vacuum UV region close to the
short-wavelength limit of quartz instruments has been reported occasionally.
The spectra of 1,3-cyclopentadiene and thiophene are very similar. This indicates
either the absence of homocyclic conjugation in thiophene or the presence of
conjugation in 1,3-cyclopentadiene. In this case hyperconjugation via the CH2 group
leads to the appearance of a quasi-cyclic chromophore. In the cyclic chromophore the
energy levels are more widely spaced than in the linear molecule. This results in a
higher transition energy between the levels in the cyclic chromophore.
JV.5.4. 1H NMR Spectra The 1H NMR spectra of thiols are characterized by signals
of the thiol protons which usually exchange slowly to undergo coupling (at room
temperature) with protons attached to neighboring carbon atoms (J - 8 Hz). The
absorption regions for aliphatic and aromatic thiol protons lie at 1.1-1.6 and
2.8-4.0 ppm, respectively, and change depending on the concentration, solvent, and
temperature. 179- 181 The thiol protons can be identified by the disappearance of the
signal upon shaking with heavy water for several minutes.
The chemical shifts of CH3 , CH 2 and CH protons in a-, [:3-, y- and subsequent
positions relative to the thiol group are characterized by the following values:
Shift 8, ppm
Group a f3 'Y and more distant
CH3 2.1 1.3 0.9

CH2 2.5 1.6 1.3
CH 3.1 1.65 1.3
In aliphatic sulfides the shifts of different groups in different positions practically

correspond to those in mercaptans. 179-182 Somewhat larger (by approximately
0.1 ppm) chemical shifts are observed in disulfides. 180 Analogously, in thiophenols
and aromatic sulfides the signals of the aromatic protons are close in value and occur
in the 6.6-7.3 pp m region. For diary I disulfides this region is shifted to 7.5 ppm.tso.tst
Slightly higher shift~ are observed for the aliphatic protons of alkyl aryl sulfides. Thus,
for phenyl propyl sulfides the shifts of the groups in the positions a, {:3, and y are 2.9,
1.7, and 1.08 ppm, respectively. 180
- - -- 1 •
In !?e H N.MR sp:ctra ?f thtacycloalkanes t:vo groups of signals (with the exception
of thnrane wtth a tnplet m the 2.27 ppm regiOn) can be recognized. These are the
signals of the groups attached to the sulfur atom (2.82 ppm for thiacyclobutane and
2.57 pp m for thiacyclohexane) and the signals of the groups two and more atoms
distant from sulfur (1.6 ppm for thiacyclohexane). The presence of two and more
sulfur atoms in the ring leads to an increase in the chemical shifts of the adjacent
groups up to 3.7-4.2 ppm. The substitution of a hydrogen atom in a thiacycloalkane
molecule by a phenyl substituent increases the CH group signal to 4 ppm. 180- 182 If a
thiacycloalkane is fused with an aromatic ring the chemical shifts of the alkyl groups
closest to the aromatic structure increase to 3.3-3.5 ppm, the shift value within this
range depending on the stereochemical features of compounds. 180 The shifts of signals
of aromatic protons of aromatic rings condensed with thiacycloakanes depend on the
number of the rings fused, being 7.2-7.4 ppm for monoaromatic compounds.
The chemical shifts of thiophene and mono-, di·, and trisubstituted thiophenes
change similarly as those of monoaromatic compounds 183 and decrease from 7.3-7.1
to 6.2 ppm as the degree of substitution increases. When thiophene is fused with an
aromatic ring, the chemical shifts of the thiophene protons decrease, the aromatic
proton shifts reaching 7.8 ppm. 179- 1H0
V. MAIN SYNTHETIC ROUTES TO ORGANIC SULFUR COMPOUNDS

V.J. Thiols. The synthesis of thiols does not present any difficulty. These com-
pounds can be obtained by one of the following methods.
Reaction of sodium or potassium hydrosulfides with alkyl halides, alkyl sulfates, or
alkyl sulfonates according to an SN2 mechanism:
Alkllal + NaSH- AlkSII + HalNa

Since the thiols are acids (Ka = 6 ·10- 8 ) comparable in strength to hydrogen sulfide
formation of sulfides is also possible:
AlkSH + NaSII - AlkSNa + H 2S

AlkSNa + Alkllal - Alk 2S + Nallal
The formation of sulfides can be minimized by using excess hydrogen sulfide ion.
The formation of dialkyl sulfides can be avoided by using thiourea and subsequent
hydrolysi~ of the S-substituted isothiouronium salt thus obtained:
AlkNal + S=C(NH 2h - AlkS+=C(NH 2hllal- ~

- IIlO
- AlkSH + NH 2CN (in polymeric form)
Using thiourea, a tertiary alcohol, and concentrated hydrobromic acid one can
obtain the corresponding thiol:
HBr + ROH + SC(NH 2h - H 2 N+=C(NH 2 )SR Br- - NaOll RSH
Reaction of sulfur with organomagnesium compounds. Treatment of aromatic

Grignard reagents with sulfur followed by hydrolysis affords thiophenols
ArSMgBr _2_. ArSMgBr H 20(W) ArSH

- Mg(OII)Dr
Addition of hydrogen sulfide to alkenes. In the presence of aluminium oxide, nickel

sulfide, sulfuric acid, or Lewis acids the reaction of alkenes with hydrogen sulfide
leads to thiols:
RCH(SH)CH3
This process proceeds also with a tertiary R group.

H 2S0 4
(CH3) 2C=CH2 + H2S (CH3hCSH
The main reaction product is formed according to the Markovnikov rule. Due to
the fact, however, that radical processes take place, an anti-Markovnikov product is
also formed. In the presence of Lewis acids hydrogen sulfide adds to tetra- and
trisubstituted ethylenes at 0-50 oc. Some commercial methods for the synthesis of
t-dodecyl mercaptan and other alkyl mercaptans from propylene oligomers and
hydrogen sulfide have been developed. 184
Reaction of alcohols with hydrogen sulfide occurs at 300-400 oc in the presence of

aluminium oxide:
Saponification of S-alkylisothiouronium salts. These salts can be readily prepared

from alkyl halides and thiourea. When an S-alkylisothiuronium salt is heated with an
alkali solution a thiol is formed:
+
NH2
11 ou-
RSC-NH2 - RSH + OC(NH 2h
No disulfides are formed in this case.

The reduction of sulfonyl chlorides, for example with lithium aluminium hydride,
beryllium boron hydride, or aluminium boron hydride leads to thiophenols:
ArS0 2CI
6 H [LiAIH.] s
Ar H +
H
Cl + 2 H2 0
Reaction of alkyl ha/ides with thiosulfate via Bunte salts.
AlkHal + Na 2S2 03 - AlkSS0 2 0Na Hzso. AlkSH
Reaction of hydrocarbons with COS upon UV irradiation. The reaction of cyclopro-

pane with COS when exposed to UV light affords cyclopropanethiol in 95% yield.1ss
hv , 225-229oc \ f SH
+cos V + CO
276 G. F. BOLSHAKOV
In the decomposition of COS singlet sulfur atoms are formed.
V.2. Acyclic sulfides.
Alkyl sulfides can readily be obtained by one of the following methods.
Reaction of alkanethiolates with alkyl ha/ides. Upon heating of a mixture of these

compounds nucleophilic substitution takes place to give sulfides:
Alk 1SNa + Alk2Hal --.!- Alk 1SAik2
When alkali sui fides are used symmetrical sulfides are formed: 2 AlkCI + Na 2 S (in
alcohol)-+ Alk 2S + 2 NaCI.
Instead of alkyl halides sulfonic acid esters or alkyl sulfate salts with alkali metals
can be employed:
AlkOS0 2K + K2S - Alk2S + K2S04

RSH + ArS03R - AlkSR + ArS0 3Na
Some commercial routes to dimethyl sulfide from hydrolysis lignin of spent liquors
of the sulfatc cellulose industry have been dcvcloped: 186
NaOH
2R -o- ON a
ONa + (CH )
3 2
Lignin is subjected to demethylation with aqueous sodium sulfide at 280 °C. In this
s
way, 70 kg of dimethyl sulfide is obtained from 1 t of commercial lignin.
Reaction ofthiols with alkenes under UV radiation in the presence ofperoxides or other
catalysts
AlkSH + Alk CH=CB _,...;;.h:...;'J_ _ AlkSA1k
1 2 1
OIJ + RSH
heptane.100°C
~SR
When catalyzed with boron trifluoride etherate, the reaction of thiophenol with
cyclohexane can afford cyclohexyl phenyl sulfide:
The yield is 75%.

Reaction of sulf~nyl ha/ides with arenes. In the presence of Lewis acids arenes undergo
electrophilic substitution by sulfenyl halides. In this manner diaryl sulfides can be
obtained:
AICh
ArH + ArSCl - ArSAr + HCI
2 ArH + SC12 AICIJ ArSAr + 2 HCI

AI Cl,
2 ArH + S2Cl 2 - Ar 2S + 2 HCI + S
Reaction of arenes with sulfur in the presence of Lewis acids can give diaryl
sulfides:
In this way, for example, diphenyl sulfide can be prepared.
Reaction of thionyl chloride with Grignard reagents. Under rigid conditions dimethyl
sulfoxide can be reduced with phenylmagnesium bromide. The reaction involves a
rearrangement affording methyl benzyl sulfide and ethyl phenyl sulfide:
31( c
-H+
CH 6H 5 )CH) ---=-=--..
OMgBr
Dry distillation of lead thiolates.
(ArShPb - Ar2S + PbS
Reaction of diazonium salts with thiols in alkali solutions. Asymmetric sulfides can
also be prepared in this way:
ArN 2Cl + RSNa - ArN 2SR + NaCl

ArN 2S R - ArSR + N2
This reaction is explosion hazardous.
Reaction of a diazonium salt with sodium sulfide.
2 C6HsN2Cl + Na2S - (C6H.shS + 2 N2 + NaCl
Reaction of O,O,S-trialkyl dithiophosphates with alkali alkoxides.

278 G. F. BOLSHAKOV
S (R0) 2PS0Na + R'SR''

11
(R0) 2PSR + NaOR'~
~
~ RO(R'O)PSONa + RSR''
Trialkyl dithiophosphates can readily be prepared by addition of O,S-dialkyl
dithiophosphoric acids to olefins. In this way the unpleasant handling of thiols can be
avoided. The starting O,S-dialkyl dithiophosphoric acids are prepared from alcohols
and P 2S5 • Symmetric sulfides can be obtained via disproportionation of asymmetric
aromatic sui fides. 187
Reaction of metal a/koxide ha/ides with thiophenol and aromatic a/cohols. 188 Excess
ethylmagnesium bromide is added to a mixture of ArCH 20H (or ArCHAr'OH) and
thiophenol and heated with ethyl formate or diethyl oxalate:
Ar(Ar')CHOMgBr + HCOO~H 5 - Ar(Ar')CHBr

Ar(Ar')CHBr + ArSMgBr - ArCH(Ar')SAr
Condensation of (arylthio)ketones with sodium nitromalonic dialdehyde. 195 This

process can afford diary! sulfides with functional groups in one of the aromatic rings:
Reaction of aryl thioxanthates with aliphatic amines. 190 Upon mixing phenylthio
xanthates with trimethyl- or triethylamine an exothermic reaction takes place:
CH30CS 2C6H5 - CH 3SC6115 + COS

to give sulfides in 93% yield through an intermediate Alk 3NCH3-SCOSC6 H
Treatment of this intermediate with alkyl iodide makes it possible to introduce th~
corresponding alkyl group in the sulfide.
V.3. Cyclic su/fides
Synthetic routes leading to cyclic sulfides have been well developed to date. Let us
consider the most important ones.
Reaction of cyclic ethers with carbon oxysulfide. 191 Ethylene oxide, propylene oxide
etc. react with carbon oxysulfide at 200-230 oc in the presence of lithium phosphate:
CH 2-cH 2Alk + COS - - - . .
'\ I
0
With increasing size of Alk the sulfide yield decreases.
Reaction of alkenyl ha/ides with thioacetic acid. 192 This approach allows three-, lour-,
and six-membered cyclic sulfides to be obtained. In the presence of light thioacetic
acid reacts with chloroalkenes to form thioacetates which, when heated with diluted
sodium hydroxide, form sulfides by cyclization:
CH :::aC(CH )cH 2Cl + CH COSH - - CH 3COSCH 2CH(CH )CH 2Cl
2 3 3 3
CH2-CH-CHJ CH 2 -CH-CH.3
I I I 1
S - CH Cl S --CH
2 2
0
yield 87%
The latter compounds undergo cyclization-induced demethylation leading to

thiacyclopropane in 30% yield.
Reaction of hydrogen sulfide (sulfides or hydrosulfides) with tetrahydrofurans and

tetrahydropyrans:
s
I
I l
(CHR)n S
._! -----~'
159
Preparation of 2-substituted thiophanes. Alkylfuryl carbinol; are obtained from
furfurol by Grignard reaction, dehydrated over Al 20 3 at 400 °C, the furylalkenes are
hydrogenated at 150 oc over palladium asbestos to 2-substituted tetrahydrofurans
which are subsequently converted to 2-alkylthiophanes:
RCH MgX -H 2o
a° CHO
2
01HCH2R 00 CHCHR
H
_2--+-
OH
H2 s
280 G. F. BOLSHAKOV
Another method involves the reaction of furfurol with carbonyl compounds to form
unsaturated carbonyl compounds. 193 The latter are hydrogenated to the hydroxyl
derivative of the corresponding tetrahydrofuran and then 2-substituted thiophanes
are obtained according to the following scheme:
[[Jl
0 CHO
Q 0
R
CH bHCOR
2 2
SOC1 2
0 0
R1
CH tHCH(R )0H
2 2
Mg
0 0
~1~2
CH CHCHMgCl
2
CH -cH R R Na2 S
2 2 1 2
I I I I
CH CHCH - CH-CH
2 2 2
I I
Br Br
A synthetic route to 2-substituted thiophanes has been developed. 194 In the

isolation and cleavage of secondary alcohols the reaction conditions should be strictly
observed since the secondary alcohols obtained from furfurol readily undergo
resinification and dehydration. Levulinic acid esters have been reduced with lithium
aluminium hydride to diols which were converted to dibromides with gaseous
hyiirogen bromide at 110-120 °C. When treated with aqueous-alcoholic sodium
sulfide the dibromides afford thiophanes:
RMgX
00 CHO Q
0 CH(R)OH
LiAlH4 TH2-yH2 HBr 1H2-TH2 Na2S

fH 2 yHCH 2R 110-12DtCH CH(Br)CH Br
2
OH OH
70-90%
65-95%
~CH 2R
. 2-Arylth~ophanes ~annot be obtain~d by the above scheme. They can be prepared
194
~:~~keto actds obtamed by the react10n of arenes with succinic acid anhydride in the
presence of aluminum chloride:
CH 2 -cH2
ArH + I I
Ar-CH CH 2 0H
I
OH 91-95%
HBr
110-120°C
2,4-Diphenylthiophane has been prepared in an analogous way from {3-(4-

phenylbenzene )propionic acid. 194
3-Substituted thiophanes can be prepared by two methods. It has been suggested to
synthesize alkyl and aryl substituted thiophanes by conversion over Al 2 0 3 of the
corresponding tetrahydrofurans obtained from 3-ketotetrahydrofuran:
0 R R 2 H
Q
9 RMgX
OOH
0
l)-
0
The relatively low yield of tetrahydrofurans should be mentioned.

A more convenient synthetic route to 3-alkylthiophanes starts with substituted
succinic acids. 194 The substituent is introduced by condensation of alkyl halides with
ethanetricarboxylic acid ester. The ester is made from sodium malonic ester and
chloroacetic acid. The synthetic route is as follows:
ClCH 2cooc 2H5 RHa.I

(H c ooc) 2CHNa -~ (C 2H ooc) 2 CHCH 2 cooc 2H
5 2 5 5
KOH(sol.)
t, °C R1HCH 2cooc 2H5
COOC 2H
5
HBr
RTH- ? H 2 - - R TH- TH2
HOCH 2 CH 2 0H BrCH 2 CH 2Br
R= iso-c 4H9 ; c5H 11 ; c5H11 , iso-c 8n

17 85-93%
75-85% 60-85%
282 G. F. BOLSHAKOV
Di- and trisubstituted thiophanes can be synthesized from the corresponding

tetrahydrofurans. A catalytic synthesis of polysubsti.tuted thio~hanes has been
suggested.I9.S Trialkylthiophanes were prepared from tnalkyl substituted tetrahydro-
furans synthesized from furfural and aldehydes or ketones:
-n' ~ACH=CCHO
R R'MgBr
H2 , Cu-Al
or
n'-'o~HCHCOR
H2 , Pt/C
200-220°C
The thiophanes obtained were steam distilled, extracted with ether, dried over
CaC1 2 , and distilled in vacuo after removal of the ether.
Since the above synthesis leads to the formation of both cis- and trans-isomers, the
problem of their separation and the stereospecific preparation of thiophane
stereoisomer$ is worth special consideration. The thiophane stereoisomers are
obtained after the separation of the stereoisomeric dibromides and the establishment
of their configuration according to J. Wislicenus.
When 2,5-dimethyltetrahydrofurans are treated with hydrobromic acid a mixture of
liquid and solid 2,5-dibromohexane stereoisomers is formed. The liquid stereoisomer
is isolated by distillation.
yH2-TH2
H3cfCH ?H-CHJ
Br Br
9% meso-form
fH2-TH2
H3C-CH CHBr
~r CH3
The configuration of dibromohexanes is determined by the reaction of the latter
with disodium malonic ester. The reaction products are subjected to saponification
and decarboxylation. meso-2,5-Dibromohexane gives cis-2,5-dimethylcyclopentane-

1,1-dicarboxylic acid which undergoes decarboxylation to form the cis- and tram-
acids. The racemate is converted to trans-2,5-dimethylcyclopentane-1,1-dicarboxylic
acid which affords 2,5-dimethylcyclopentanecarboxylic acid upon decarboxylation.
Acid B differs from acid A. The reaction of sodium sulfide with meso-2,5-
dibromohexane yields cis-2,5-dimethylthiophane whereas trans-2,5-dimethylthio-
phane is obtained from the 2,5-dibromohexane racemate.
Various methods for the synthesis ofpentamethylene sulfides have been developed.
A general preparative route to 2-substituted thiacyclohexanes has been suggested: 196
CH I Mg
3
HO(CH 2 ) 40H Na CH 0(CH 2 ) 0H
3 4 CH30(CH2)4Cl RCHO
HBr
---cH 0(CH2 ) 4cH(OH)R
3
Na2s. 0 R
R= C2H5; C5H9; C6H13; C6H11; C11H23; C6H5

2-Alkylpentamethylene sulfides can be prepared by exposing 2-substituted tetrahy-
284 G. F. BOLSHAKOV
dropyrans to the action of hydrogen sulfide as well as from dihydropyrans: 195
( " ) - I!Br (I - 0
"-oAc2H5 B/ J;c2H5 S C2H5
3-Butylpentamethylene sulfide is obtained by alkylation of sodium malonic ester;

the carbon atoms required for the ring formation are obtained by condensation of
alkylmalonic ester with acrylonitrile followed by saponification and decarboxylation
of the reaction products. The acids are reduced to diols which are cyclized with
hydrogen bromide and sodium sulfide:
c4u9cH(COOC 2H5 )
H 0
- (c 2a ooc) 2C(C H )cH 2 ) 2CN

5 4 9
2
L1AlH HBr
4
2,6-Dimethylpentamethylene sulfide can be prepared as follows: 19 ~
(CH 3co) 2 o MPt,200-220°C ~ HBr r"1

[[Jl I I Na 2S ~-A
0 CH 3 H3 0 H.3 u3c H.3 u3c S CH)
The reaction of phosphorus pentasulfide with tetrahydropyrans can lead to 2,2,6,6-
tetrasubstituted pentamethylene sui fides: 197
HBr
2,2,6,6-Tetrasubstituted pentamethylene sulfides are formed in the reaction of

hydrogen sulfide with terpenes, e.g. dihydromyrcene, geraniolene, and 2,6-
dimethyloctadiene.197 The reaction follows the Markovnikov rule in the presence of
sulfur or ammonium sulfide:
or
SH
I
(CH ) 2C=CH(CH 2 ) 2ycH 2R
3
CH)
2,3-Dimethyl-6-isopropylpentamethylene sulfide is formed by cyclization of an
. 1 upon uv .ura d'1at1on.
unsaturated t h10 . 198
Hc
3
(cH 3) 2cHTH(CH 2 ) 2y=CHCH 3
HPCH(CH3)2
SH CHJ
4-Alkylthiacyclohexanes have been synthesized from 4-thiacyclohexanone accord-
ing to the scheme:
0 R OH R
A
·6
11
0 s
RMgBr
0 ;. l_j
s
3-Alkyl substituted pentamethylene sulfides can be prepared in a similar fashion:
R
n0
R
RMgBr
R
D R
S
OH
-H20
R R
R
(l R
Polymethylcnc sultldcs can be obtained in the following way: 199
n
(H C) C~S~HO
Ag2o
J 2 Y.S y-CHO
LJJ
286 G. F. BOLSHAKOV
(H c) 2c
~COOH
3 '-y(SyCOOH
\L.JJ
LiAlH
4
/ (CH2)5'-.
(CH ) 2 S
3
'<eH
2 >5/
Polycyclic sulfides are accessible according to the following general principles. The
monocyclic compound with functional substituents is converted to the ditosylate or
dibromide which is cyclized with sodium chloride. The polycyclic sulfides may also be
prepared by condensation of the monocyclic compound to afford an unsaturated
bicyclic sulfone which is further reduced.
Another possibility is the cyclization of monocyclic unsaturated thiols.
Some schemes for the synthesis of polycyclic sulfidcs arc given below .1s9 •2oo
NaSH u(CH2)2SH
eo rn +
II 0:: COOH
L1Al!1 4 •
CH 20H
cc~
COOH GCH20H
H CH s• H
d C H2SH
etCH~ eh
H2 ,Raney ;a
III
CH2SH
H 2 H
OCCOOC2!15 H2 , Raney Ni aCOOC21!5

IV
160-215°C,26 mm Hg
COOC 2H COOC 2H
5 5
HBr
V ~~r-\ ----H_2_o_ _ _ _ _ ~ --:)>-

)r
~ ~ naphthalenesulfonic acid ~
-
OH
qSCOCH3
Cl
+ Q SCOCHJ
KOH/alc. 0
Cl
+
Cl Cl
OH OH OH
VI
Q H2 ,Raney Ni
Q L1AlH 4 ,.
Q HBr
isomerization
0
COOC 2H COOC 2H CH 20H
5 5
< D
Na2S
CH 2Br
so 2 __H_2__..., ~
VII
O 40 hr Raney Ni~
HBr
00
VIII H2· 126mm HgOO
0 Raney-Ni 0
200-230°C
(()
288 G. F. BOLSHAKOV
IX
HllrU . Br
(CH 2 ) 2Br
ex Br
Na2 S •
(CH 2 ) 2Br
Q)+ CJsJ
OH OH OH
Rane:r-_!1~
X
QH2' LiAlH4
QOH
Q:j
OOC 2H5
XI 0+
H c...,c~
3 CH2
-~) + ~ca,+mca3
CH.3
CH.3
CH
CH.3
CHJ
CH.3
CH2
('{ CHCH
V OH
NaHS
cc OH -H 0
-.:...2
C=CCH:.CH2
COCH:aCHCH 2 H S
~
2
liquid
eO an .3
0 0
XIV 0-
11 11
([{:0 LiAlH4 •
11 11
0 t 0
bY tlrodUC
({)to
pyrrolidine
~~ ~I'
_h_e_a_t_in_g_~ V,D ~
LB0:0
XVI
XVII
OcJ s
XVIII
0. F. BOLSliAKOV
XIX
XX
rAr---TR1
XXI
~SAR ,,
0 0
XXII
SCH2CHaCH 2
~ heating
XXIII
V quinoline
XXIV
XX.V
!QrS-CH?•CH
CH)
2
JQQOC
Or:-lcH 3
S CH
3
OCH K 2s
OV~s
XXVI 2Br Zn, HCl
CHBr
I
CH)
,., ''\
CHJ
Zn,HCl
t)O
c
Na(Hg)
11
0
Zn(Hg), HCl
Af'SNe.
XXVII ty.l.. + Br(CH2 ) 2COONe. - - -
CH.3
XXVIII
XXIX
XXX
XXXI
R1SH + RCH=CH 2
292 G. F. BOLSHAKOV
In this reaction, benzoyl peroxide and ethylene aluminium dichloride, a reactive

aluminium·containing catalytic complex, are also used as catalysts.
Cl
The reaction course and the product yield arc dependent upon the reaction
conditions. In CH0 3 at 20 oc with equimolar amounts of the reactants, for example.,
thiirane is formed in 80% yield.
Ia, II R' SA-BMR + E-x ·--..-

3
~ R 1 SA-B-E + :xMRJ
where A===B a rutCO, RNCS, R2CaCR 2 ,
R2C=C•O, RC:CR
la are salts of type la; 11 are complexes of type /l in CCI 4 and THF; M = Si, Sn.
V.4. Di· and Polysulfides
Some synthetic routes to di· and polysulfidcs arc known. Mild oxidation of thiols.
When treated with mild oxidants or upon long exposure to the action of atmospheric
oxygen, thiols form dialkyt disulfides:
RSH + {0] - RS' + 11(0]

2 RS'- RSSR
.
In some cases, the oxidation evidently involves sulfenic acid derivatives:
RSH + (0] - RSOH

RSOH + Rs- - RSSR + ou-
Alkylation of potassium disulfide.

Reaction of acetylene with potassium disul.fide. 201
HC==CH + K2S2 H 2s CH2=CHSSCH=CH 2
Oxydation of thiols with halogens.
RSH .....!!... RSSR + HI
Reaction of olefins with hydrogen sulfide and sulfur. 155 1,2-Dithiolane-3-thiones are
readily obtained upon heating a mixture of an allylic hydrocarbon with sulfur at
170 oc.
+ H2s +polysul!ides
Dithiolanes are also formed by reaction of y-substituted 2-propenethiols with P 4S10

or when sulfur and a branched tertiary thiol, obtained by the action of hydrogen
sulfide upon the corresponding olefin in the presence of sulfur, are heated together to
190-200 oc:
190-200°C
Methylcyclohexane and sulfur afford benzotrithione, while limonene gives a

trithione containing a thiophene ring:
0
11
00
or
Reaction of polyketones with P2S6. 2,4,6-Heptatrione reacts with p 2S6 to form a

cyclic polysulfide, a 1 ,2-dithiolylidene-3-thione:
0. F. BOLSIIAKOV
Compound A is an a-(1,2-dithiolylidene-3)-thione with a 10 1r-electron system.
Preparation of trithiaadamantanes from hexanetriol tosyl esters:

The bridgehead attached to the three sulfur atoms can be metallated with
butyllithium. This allows various substituents (CH 3 , COOB, SH, etc.) to be
introduced. It was not possible to mctallatc other species in this way. 201
V.5. Thiophenes
Thiophenes can, inter alia, be obtained in the following ways:
The Paai·Knorr synthesis consists in the reaction of 1,4-dicarbonyl compounds with a
dehydrating agent and sulfide:
0s
The reaction of organic acids and salts thereof with phosphorus trisulfide upon
heating.
CH2 -cH2
I I P2S3
NaOOC COON a •
0s
CH2-cH2
I I P2S3
HOOC COOH •
0S CH
.3
CH2 -CH-R R
..
HOOC
I I
COOH
R-CH-CH-R' R
0 R'
HOOC
I I
COOH
CH 2 -cH-CH2
Ds
HOOC
I I I
OCOOH COOH
~ll]
s s
The reaction of mercapto acids with hexacyanoferrate:
~CH=CHCOOH_____h_e_xa_c_y_an_a_r_er_r_a_te-----+
VsH
o-mercaptocinnamic
acid
This method is one of the best routes to thianaphthenes.
Isomerization of monocyclic sulfides over acid catalysts. 203 Thiacyclohexane and

2-methylthiacyclobutane undergo Al 20 3-, AI-Si-, or ZnCI 2 (Al20 3)-catalyzed sk.eietal
isomerization and dehydroisomerization with ring contraction and expansion, respec-
tively:
-He
OcH J
e
~CH -H
\_/~H 3==:
s (
K~
Q
296 0. F. BOLSllAKOV
Ionic dehydrogenation and isomerization of cyclic sulfides. 204 The reaction of 2-

methylthiacyclobutane, thiophane, and thiacyclohexane with triphenylmethrt tetra-
fluoroborate, chloranil, or triphenylchloromethane in the presence of SnCI4 mvo!ves
dehydration and isomerization of cyclic sulfides with ring contraction or expanston:
/"-..vcH3 e
-n
"s f 11
(1
Reaction of halostyrenes with hydrogen sulfide. 2'XJ a· and p-bromostyrene react with
hydrogen sulfide in the liquid phase at 150-160 °C to form 2,4-diphenylthiophene:
c6H5CH=CHBr + H2S c6H5CHaCHSH + HBr

c6H5CBr•CH2 + H2S c6H5C{SH)•CH 2 + HBr
11 s0
c6H5CHaCHSH + HSHC•CH06H5 ------. 6 n
SH S c6H5
I
c6H5CaCH2 + CH2a1C6H5
SH
2,4-Diphenylthiophene is the product of the autohcterocyclization of the unstable

styryl mercaptan.
15
Thienothiophenes K can be prepared in different ways. These compounds have first
been prepared by cyclization of (thienyl-thio)-acetic acid in the presence of sulfurie
acid. Thienothiophene is obtained from 3-thiophenethiol as shown on p. 297
.Isomeric t~iop~ene~ have bee.n obtained by cydization of orthobifunctionai
58
th10p.hene denvat1ves. F~rmylatton of (5-ethyl-2-thienylthio )-acetic acid accordin
to Vllsmeyer gave good y1elds of (S-ethyl-3-formyl-2-thienylthio)-acctic acid este;
SCHCOOH s R sy R
ds
HSO
2 4 ~ lsj ""y
~~ ~ ~ ~
"o s ....
/
}l
0 S SH
lJL~
s s
rlj(B_r_ _,... rrcH_2_co_cn_3_~ lL lls ~

R~S.!J R S R s' 'cn
3
which, when heated with sodium alkoxide, forms 5-ethylthieno[2,3-b]thiophene-2-

carboxylic acid which undergoes decarboxylation to form 2-ethylthieno[2,3-b]-
thiophene:
298 G. F. BOLSHAKOV
R D S
Benzo[c]thiophene can be obtained by thermal decomposition of 1,3-dihydro-

benzo[c]thiophene sulfoxide. 158
VI. APPLICATION OF ORGANIC SULFUR COl\tl'OUNDS
The organic sulfur compounds of petroleum are used in different fields of

industry. 2•103 Sulfur compounds are employed as extractants of metals, floatation
agents, polyfunctional additives to fuel, oils, and polymers, thin-film coatings,
adsorbents for oxidative gases, insect repellents, vulcanizers, drugs and as oxidation
catalysts. Sulfur compounds are readily oxidized to sulfones and sulfoxides. The
sulfoxides are excellent extractants of rare-earth elements and acids; solvents for
phenols, resorcinol, pyrocatechol, hydroquinone, aromatic hydrocarbons, and acidic
oxides (S0 2, N0 2); they serve as plasticizers, foaming agents in floatation, and
herbicides; a sulfoxide-based extraction process for purifying sulfuric and acetic acid
has been developed. The sulfones can be applied as physiologically active com-
pounds, special solvents, antioxidants, oxidation and corrosion inhibitors. The fields
of application of mercaptans the annual production of which exceeds 1,000,000 tare
extremely diverse. 103 Methanethiol is used for manufacturing methionine, a food
additive. Low molecular mercaptans are employed as fuel gas odorants, the mercap-
tans of the Orenburg gas condensate field being most suitable for this purpose in the
USSR. The odorizing ability of these mercaptans is 1.5 times that of ethanethiol. The
light mercaptan resources are enormous in this gas-condensate field.
The mercaptans C8-C 16 are used as molecular weight regulators in the produc-
tion of polymers. The mercaptans C 10-C 18 are employed to obtain surfactants
solvents, and plasticizers of different kinds. '
VI./. Vulcanization of Rubber
Rubber is cured with vulcanization initiators among which sulfur compounds

such ~s 2,2' -di(benzothiazolyl) disulfide, tetramethylthiuram disulfide and
2-mercaptobenzothiazole,t for example, play an important role. 2 2' _
~i(benzothiazol~l) disulfide is ab~e to undergo decomposition by a radical mecha-
msm and vulcamzes rubber even m th~ absence of sulfur. In this case, very efficient
'.The two latter compounds require auxiliary substances, lauric acid and zinc salts of fatty acids, fo
cunng. r
curing accelerators, zinc thiolates of type A and B are formed. Carboxylate ions form
with compound A complexes A': 205
0(s/
~
C-S-Zn S\
')Q
1
(R C00) 2 zn
0
s
A R'
I
c
,(.··~
o· ·o .,N
0('\ ·. ..
)J-s-.~~-s - - - -
o:'\'••7.b
ctslf)
" JV
cI A'
R'
A zinc-dimethyldithiocarbamate complex (B) with amines affords compound B':
/.s.. ..s~
,t.· • • -~ R'NH
(CH ) N-c: 'zn·.
. .·. C-N(CH ) 2
3 2
'\s·· . ·. • • f ~
· s·
•
3 2
B
R'NH
2
/~·. I ..s.,
3
(CH ) 2N-C~·
'\'.
·.
. .. .·~C-N(CH
'/
·.t(
) 32
"-'s · .· ··s·/
B'
Compounds A' and B' are readily soluble in rubber; besides, in the reaction of zinc
with carboxylate ions or amines the Zn .... S bond weakens, thus facilitating
subsequent cleavage of the S-S bond in Ss under the action of the thiolate ion. Let us
denote compounds A' and B' as RSZn and SR. In this case, the Ss cleavage can be
represented as follows:
Compound C may be regarded as a very active vulcanizer with a polysulfide bond

which reacts with rubber:
300 G. F. BOLSHAKOV
-ZnS RSX+1-r-
C- ZnO
-&-
~
(saponification)
RSxR -H 20
The addition of sulfur to the allyl position of hydrocarbons leads to either dialkyl
sulfides or the following compounds:
Thus, any curing accelerators cleave the sulfur molecule and generate ions or
radicals which add to olefins and bring about vulcanization. It should be noted that
the vulcanization reactions have not been exhaustively studied.
The ability of sodium dialkylphosphonates to react nearly instantly with sulfur
compounds is used for rubber vulcanization control. Sodium di-n-butylphosphonate
solution in benzene, for example, is very efficient in the cleavage reaction of di- and
polysulfides, therefore it is widely used in controlling the vulcanization process. 16 1
Mercaptans and derivatives thereof are reported 2 to be used as accelerators in the
butadiene-styrene rubber polymerization. The mercaptans isolated from the kerosine
distillates of Terekli oil, USSR, have successfully substituted t-dodecyl mercaptan
usually employed as a divinylstyrene rubber polymerization regulator. A combination
of piperidine N-thiols, decahydroquinone with thiurane D accelerates curing of
low-molecular cis-polybutadiene at 80 °C.
V/.2. Modification of Inorganic Sorbents
Modified sulfur compound adsorbents are known to have found various fields of
application. 2 •103 •207 Modified adsorbents are highly efficient. Modified silicon oxide
can be prepared via reaction with organosilicon compounds:
I ~1 I I
-~i-OH + ClS~s/'.../ --. -SiOSi ~S~
I I
or by treatment of silica with sulfur compounds or sulfur compound solution i

c~-~ alkanes. Upon the reaction of sulfur compounds with inorganic sorbents ~
reactive sulfur-containing layer is formed which imparts the sorbents new properties,
such as increased reactivity toward heavy-metal salts. The sulfur compound
modified adsorbents are highly efficient in selective isolation of metals from aqueous
solutions. The sulfur-containing modified sorbent reactivity decreases in the following
order: mercury > silver > copper > cadmium > zinc. The sorptive power of mod-
ified sorbents increases with increasing pH of the medium from 2 to 8 and decreases
sharply with pH > 8.5. The capacity of modified silica gels is considerably greater.
The capacity for mercury, for example, on modified silica gels ASK and KSM is 18
and 31 times as high, respectively, as that of unmodified silica gels. The sulfur
compound modifying ability increases in going from thiophenes to sulfides, disulfides,
and mercaptans. An optimal concentration favoring the highest efficiency of the
adsorbents must be chosen for each sulfur compound type.
Metals are readily desorbed from modified adsorbents with increasing the acidity of
the medium to pH = 2-4. A change in the adsorption and desorption conditions

allows the separation of mercury, copper, and silver ions. The modified adsorbents
are subjected to regeneration after the operation. The regeneration involves a
complete sulfur compound desorption, calcination of the adsorbent, and repeated
sulfur compound modification. Various fields of application of sulfur compound
modified adsorbents are known. 2 •103 The chlorine industrial sewage, for example, can
be efficiently purified from mercury with sulfur compound modified sorbents. 207
V/.3. Extraction of Metals
Solutions of dialkyl sulfides and thiophanes in organic solvents readily extract silver,
mercury, platinum, gold, and palladium. Aromatic sulfides and thiophenes possess a
considerably lower extractive power. This is explained by a significant decrease in the
electron-donating ability of sutfur atoms in aromatic systems and, accordingly, by a
lower energy of the M .... SAr complexing. Thiophene and diphenyl sulfide, for
example, do not extract gold, palladium, and platinum. Gold and palladium in
hydrochloric acid solutions are extracted by sulfides independently of the aqueous
phase acidity and pass to the organic phase as AuC13 and PdCI2 • Gold is extracted by
sulfides as a monosolvate, which corresponds to the formation of the complex
non-electrolyte, AuCl3SR2 , in the organic phase. Palladium chloride is solvated with
~wo sulfide molecules, PdC1 2 (SR2h. Platinum is also extracted by sulfides, but
considerably more weakly so than palladium. Iridium is even more difficult to extract.
The distribution coefficients for these compounds in the extraction from 0.6 M
hydrochloric acid solution with 0.5 M sulfide solution in benzene are 0.5 and 2·10- 4 ,
respectively.
The sulfides are very efficient also in extracting gold and palladium from nitric acid
solutions. In this case, gold is more and palladium less reluctant to be extracted from
these solutions than from hydrochloric acid solutions. When gold is extracted with
0.4 M sulfide solution in benzene the distribution coefficient reaches 20 with 4 M
nitric acid. Under these conditions the distribution coefficient for palladium is 150
while for 0.1 nitric acid it becomes equal to 690.
The sulfides extract actively silver and mercury from mtric acid solutions. The
distribution coefficient for platinum in the extraction with 0.5 M diheptyl sulfide from
302 G. F. BOLSHAKOV
0.1-3.7 M nitric acid is 1.4-0.6. Iridium is extracted with difficulty, the distribution
coefficient being about 10-3.
The extraction of silver from nitrate media seems to be of greatest importance.
Silver is extracted with dialkyl sulfides as mono· and disolvates, AgN03 • SR2 and
AgN0 3• (SR2)z. The AgN03 distribution in the extraction with diluted sulfide
solutions from aqueous solutions of different strength is characterized by the
extraction constants, n = 1 and n = 2,
where n is the number of sulfide molecules in the complex, M the molarity, y the
average ionic molar coefficient of activity of AgN03 in the aqueous phase; CAgN03 ·ns
and Cs are equilibrium molar concentrations of the compound being extracted and of
the free extractant in the organic phase. The Kn value depends on the nature of the
diluent. In the extraction with sulfides in benzene solution K1 and R2 are 12.4 and 492,
respectively.
Palladium and gold are extracted with dialkyl sulndes from sulfuric acid solutions in
approximately the same manner as from hydrochloric acid solutions. With increasing
sulfuric acid strength the palladium distribution coefficient decreases slightly. At a
constant aqueous phase composition the palladium distribution coefficient in the
extraction from sulfuric acid solutions is proportional to the square of the sulfide
concentration. This indicates that the disolvate PdS0 4 • (SR2h has been extracted
into the organic phase. In contrast, when the sulfuric acid strength is raised, the
extraction of gold becomes slightly more efficient.
Depending on the medium, the extraction of platinum with sui fides increases in the
following order: HCl < HN03 < H 2S04 • The recovery of platinum into the organic
phase increases with increasing H 2S04 strength. Sulfide-based extraction from
sulfuric acid solutions can be employed, therefore, for the recovery of palladium and
platinum while the extraction from nitric and hydrochloric acid media is more suitable
for the separation of these two metals. An increase in the sulfide molecular weight
decreases slightly the extraction power.
The solvent nature affects much the extraction processes. Thus, in extracting silver
nitrate with di-n-hexyl sulfide the R2 value considerably increases in going from
heptane to chloroform:
Solvent CHC1 3
K2 17300
~n ana~ogous solvent .effect is observed in _the extraction of gold from hydrochloric

aetd soluttons. A very htgh value of the effictent extraction constant with chlorofo
shows the absence of coordinate bonds between the sulfide sulfur atom and tr~
chloroform hydrogen atom. e
. Silver i~ ~it~ic a~id solutions ~s ~resent as unstable complexes. Thus, in extractin
silver eqUthbnum ts reached wtthm a few minutes. Gold and palladium in hydro~
chloric solutions also form the unstable complexes (AuC1 4 and (PdC1 4] 2 -. In r
these complexes the substitution proceeds also very quickly, approximately within
30 minutes.
The platinum complexes are more stable and, therefore, more time-consuming.
The equilibrium is reached as late as after 8 hours in extracting platinum from
hydrochloric acid solutions and after 4 hours in the case of nitric and sulfuric acid
solutions. Disulfides efficiently extract gold and palladium. Other platinum group
metals cannot be extracted with disulfides. 2 Palladium is extracted in the form of
complexes:
CH 2
lH2-c~
Alk-S .I . .". .S-Alk Alk-S .S-Alk
. 'Pd.·
)~ /"-...
Cl Cl Cl Cl
The stability of disulfide compounds with platinum group metals increases in going
from three-membered to five-membered complexes (Table 63):
TABLE 63
Distribution Coefficients In Gold and Silver Extraction with 0.5 M
Disulfide Solutions In Benzene2
IICI concentration, mole/1
Extractant 0.1 0.79 1.98 3.60 6.00
Gold,.
(C,Ht~Sh 420 73 35 13 6
(C,Ht~ShCH2 3460 2280 1760 1050 710
(C,H 1 ~Sh(CH2h 3620 3080 2840 1970 1560
IIN03 concentration, mole/1
Silver"
(C,Ht~Sh 0.03 0.08 0.16 0.25
(C,Ht~ShCH2 2.8 11.7 25.2 6.7 1.6
(C,Ht~S)2(CH2)2 218 293 400 183 4.9
• Initial concentration 4 · 3 ·10- 3 mole/1
b Initial concentration 4 · w- 3 mole/1
/CH 2 , /CH 2-cH 2,

Alk-~:--:-p-Alk -
'Me
Alk-S..
·Me'
. S-Alk Alk-S. .··Me'· . ..s
G. F. BOLSHAKOV
TABLE 6-1
Extraction or Gold from Hydrochloric Acid Solutions wlth Petroleum Sulfides
in Polyalkylbenzene
Sulfur Extraction coefficients

Petroleum sulfide content,
fraction, •c 'if, [IICI), mole/1 =0.1 0.7 1.3 l.O 4.1
150-190 17.7 291 204 198 216 140

190-230 17.3 430 318 356 340 320
230-270 15.1 173 166 153 125
270-310 12.7 510 450 605 390 420
150-250 17.5 390 326 304 315 322
Gold, silver, palladium, mercury, and platinum are readily extracted with pet-
roleum sulfides (Table 64). 2•103 All the sulfides studied extract gold from aqueous
solutions almost completely. The palladium and platinum distribution coefficients in
the extraction with sui fides are 300 and 1.5-2, respectively, and do not depend on the
acidity of the aqueous phase. Iridium is practically not extracted with petroleum
sulfides under these conditions. The capacity of the extractant containing 30 g of
sulfur per 1 I of solution is 140 g of gold per litre. This corresponds to a 1: 1 molar
ratio of gold to sulfide. Dodecyl mercaptan can be successfully used for the selective
separation of gold and silver from hydrochloric and nitric solutions and the separation
of palladium and platinum from hydrochloric acid solutions. The extraction is of
cation exchange character:
RSH + Ag+ i=:! RSAg + u+

2 RSH + PdCl}- (RShPd + 2 u+ + 4 Cl-
Thus, the sulfides and mercaptans recovered from petroleum can efficiently be
employed for the extraction and concentration of noble metals.
V/.4. Floatation of Ores
Sulfides and disulfides are active floatation agents of copper-nickel and copper-
molybdenic sulfide ores. Diphenyl sulfide recovers 90% zinc blende from the ore
Under the same conditions 55% recovery of copper is achieved. Phenylpropyl:
thiophane and s-isohexyl phenyl sulfide are efficient floatation and foaming agents for
copper and zinc minerals. Dioctyl sulfide produces a depressing action on pyrite
chalcopyrite, and s.phalerite. The collecting and foaming properties of sulfides hav~
been compared wtth those of commercial floatation agents, potassium butylxan-
thogenate and frother T-66. It has been established that the petroleum sulfides are
close to xanthogenate in their main performance characteristics and better than
frother T-66 in foaming. Use of petroleum sulfides in polymetallic sulfide ore
processing increases the recovery of nonferrous and noble metals with a simultaneous
reduction of the cost of floatation agents. 2·103
·since the petroleum sulfide resources are enormous and the sulfides surpass
commercial floatation agents in their service properties, the application of sulfides in
floatation can be of great economic value.
V1.5. Physiologically Active Substances
Some sulfides, allyl1-naphthyl sulfide, for example, inhibit the acitivity of some fungi
causing vegetable diseases. 208 The antifungal, antimicrobial, and toxic properties of
petroleum sulfides as well as of their sulfoxides and sulfones have been studied. 208 The
sulfoxides display a high therapeutic effect in treating mange in horned cattle,
helminthosis in birds and animals, down and feather beetles in birds, and sheep
ticks. 103 The sulfoxides are excellent repellents. The sulfones are highly efficient in
treating horned cattle trichophytosis, mycodermatitis in animals, and psoropthosis in
horned cattle and rabbits. The sulfones produce a strong acaricidal effect towards
ticks. Treatment with sulfones accelerates epithalization and healing without recidiva-
tion.
The thiols and disulfides may be employed, analogously to cysteine and cystamine,
in elaborating protective measures against radioactive radiation. 2·155 Many mercap-
tans possess antidotal properties. 103 Unithiol and mercaptide are used as drugs in
pesticide poisoning. Some mercaptans are employed as insecticides. Methyl-
mercaptophos, for example, is a standard chemical against cotton pests.
The aromatic and aliphatic mercaptans isolated from sulfur-rich petroleum stimu-
late a 2-3 fold gain in hair growth in sheep with simultaneous improvement of wool
quality.
VI.6. Exogenic Regulators of Cereals Growth
A high efficiency of sulfides in spray nutrition of wheat and rye has been found.209
Sulfides increase the nitrogen intake of plants and accelerate the formation of protein
substances. Sulfide solution treatment of spring wheat and winter rye in the booting
phase increases the grain quality and yield. A 13-15% gain in the yield of some wheat
varieties was observed after petroleum sulfide nutrition.
VI. 7. Additives
At pres~nt much atte~tion is being paid to the ~evelopment of additives improving

the quahty of fuels, oils, and polymers. The mam requirements for additives are as
follows.
. The ad~itives should be readily soluble in fuels and oils at all temperatures and
msoluble m water. They should be well compatible with polymers.
306 G. F. BOLSHAKOV
The molecular weight of fuel additives should not differ much from the average
molecular weight of the fuel. Use of copolymers with a molecular weight of
10000-20000 for improving the fuel quality is not desirable. t
The additives should be multifunctional in order to improve, first of all, the
antioxidant, anticoagulating, antiwear, and anticorrosive properties. Other perfor-
mance characteristics should not be negatively affected by the additives.
The requirements for additives for prospective and for modern fuels are somewhat
different due to the different chemical composition of fuels. Prospective jet and diesel
fuels should be thoroughly refined and consist mainly of alkane-cycloalkane hydrocar-
bons. Cycloalkane fuels are the best ones for jets.u 9 In the oxidation of alkane-
cycloalkane fuels no deposit is formed, only soluble oxidation products are rather
intensely accumulated. The alkane-cycloalkane fuels contain no polar compounds
which could have improved the antiwear properties of the fuels. The additives for
prospective mid-distillate alkane-cycloalkane fuels should, therefore, be antioxidative

and antiwearing. If the antioxidant inhibits the autocatalytic oxidation, neither acids
nor water will form and the fuel will be non-corrosive. Thus, the additive for
prospective alkane-cycloalkane fuels must be a polar efficient antioxidant preserving
its activity up to 250-300°C
The search for additives for modern fuels requires quite a different approach. Apart
from saturated hydrocarbons, these fuels contain aromatic and unsaturated deriva-
tives as well as various heteroorganic compounds. It is very difficult to match this
complicated mixture of organic compounds with an efficient antioxidant which would
equally well protect both hydrocarbons and heteroorganic compounds from oxida-
tion. Therefore no efficient (up to 200-250 °C) additives for modern fuels have been
produced on a large scale until now. In this case it is more appropriate to speak of an
• antioxidative-anticoagulating additive which, along with a partial inhibition of the
oxidation of the fuel components, would prevent the oxidation products from
coagulation to the solid phase, insoluble deposits and gums. It is unnecessary to give
much attention to the antiwearing properties of additives for modern fuels since the
latter contain enough polar substances able to give the required antiwear effect.
The additives should not contain ash-producing elements since these, in the pro-
cess of burning, cause erosion of the turbine blades and other trouble in the
engine operation. An efficient additive should contain amino, thiol, and hydroxy
groups, i.e., N-H, N-C, C-S, S-H, C-0, and 0-H groups on a hydrocarbon
chain. 119•21 a- 212 The choice of an appropriate structure of heteroorganic compounds
which could be used as additives is of great importance. Below are given research
res~l~s of th~ present. author aimed at creating highly 7fficient sulfur-containing
addtttves to d1esel and Jet petroleum fuels. After a long prebminary study the author's
attention was attracted by amino thiols, amino sulfides, amino disulfides and ionol
derivatiy7s. Th~ thiol gro.up in ami~o thiols i~ responsible for the inhibiting effect of
the add1t1ve wh1le the ammo group IS respons1ble for the anticoagulating effect. If th
amino and thiol groups are in the a-position, they should also possess some anticor~
t High·l!lolecular additives increase the emulsifiability and electrolyzability of fuels as w 11

actual reStn content and carbonization in engines. These additives are poorly soluble in fuels~ as the
rosive properties due to the formation of metal complexes:
Being highly polar compounds, the amino thiols should exhibit good antiwear
properties.
A series of aliphatic and aromatic amino derivatives have been synthesized
{Table 65). 213
Besides amines, a large group of sulfur- and nitrogen-containing ionol derivatives
have been synthesized. Most ionol derivatives have been prepared for the first time
{Table 66). 214

Chemical and physical studies have been performed on the compounds ob-
tained177·178 and they were further examined as additives to hydrocarbon
fuels.2to-212,2ts The additives were employed in amounts of 0.01-0.05% by weight.
Data regarding the amino thiols tested under exacting conditions are listed in Table
65.
The aliphatic amino thiols with a mercapto group attached to a secondary or
tertiary carbon atom are not very efficient. A high efficiency has been found only in
the amino thiols with a primary mercapto group and the amino group at a tertiary
carbon atom.
The formation of a solid phase in fuels was considerably reduced in the presence of
the above compounds.
1-Mercapto-2-phenyl-2-aminobutane (MPAB), the most efficient compound, has
been studied in more detail (Fig. 45). The presence of MPAB considerably deceler-
ates the oxidation of fuels and increases the induction period. MPAB as an additive is
able to inhibit not only the starting period of the autocatalytic process. After
introducing the additive (the moment of the additive introduction is shown with
arrows in Fig. 45). the absorption of oxygen in the course of propagating oxidation
slows down instantly, the hydroperoxides undergoing decomposition. Therefore the
formation of acids and other oxidation products is greatly reduced. Since the
oxidation products are formed in considerably lower amounts, which is also evident
from the decreased optical density, the formation of the solid phase also proceeds
more slowly. The additive exhibits clearly pronounced anticorrosive and dispersant
properties. The fuel-induced corrosion of metals is reduced in the presence of the
amino thiol MPAB. This additive efficiently prevents the formation and coagulation
of the deposit. The average number of particles being formed in the oxidation is
(2-5) ·10-s per ml as compared with (3-11) •10- 8 in the absence of additive.
Furthermore, the particle size is much smaller in the former case.
Fuels with 0.05% MP AB and 0.3% of liquid "l"t were allowed to remain for a long
time in iron tanks. During the storage the optical density was periodically measured
t Liq~id "I", ethylene glycol monoethyt ether, used as an additive preventing the formation of ice
crystals m the fuel.
TABLE 65
Effect of Amino Thiols on the Thermai-Oxidative Stability of Jet Fuels

(160 °C, 0 2 , 4 hr, Copper)
Optical density
Sed[ment, Copper Gums on metal, = 4358 A,
Additives Concentration mg/100 ml corrosion g/mz layer 3.045 mm
"1. % g/mz
~
1 2 3 4 5 6 :""
c::l
0
Futl TS-1 !;;
::c
Initial fuel 26.4 1.9 1.6 0.184 >
~
0
(<:IJJ)2<:(SII)<:llz~llz 0.()..170 29.0 0.9 0.4 0.148 <
~II 5 (rnJ)C(SII)rnz~llz 0.()..183 13.7 0.7 0.8 0.100
~lls<:H(SH)rnz~llz 0.()..100 10.7 1.3 0.1 0.087
c,H19<:H(SH)<:II2~llz 0.048.5 14.2 1.2 0.4 0.127
rn3CIJ(SH)<:llz~Hz 0.0500 18.3 1.4 0.3 0.154
C3H1<:H(SH)rn2~llz 0.()..186 14.5 1.7 0.5 0.160
CJluCH(SH)<:llz~llz 0.()..150 15.3 1.8 0.4 0.166
0Cllz~ll2
0.462 10.2 1.0 0.6 0.170
SIJ
Ct.Hs<:H2<:H(SII)<:H2NH2 0.0482 15.3 1.2 0.6 0.127
CJ!5CHz(SH)C(CH3)CH2NH2 0.0400 20.9 1.3 0.7 0.098
CJ1s(NHz)C(C3H7)CHzSH 0.0505 2.9 0.3 0.2 0.017
CJ1s(NH2)C(C;zH.s)CH2SH 0.0410 4.6 0.6 0.6 0.048
Fuel RT
Starting fuel 20.8 1.6 1.8 0.203
Ct#s(NH;z)C(C3H7)CH2SH o.osoo 2.6 0.4 0.6 0.029
CJ1s(NHz)C(ClHs)CH2SH 0.0483 3.0 0.6 0.7 0.040

0
Fuel T-6 :00
0
Starting fuel
CtiHs(NH;z)C(C3H7)CH2SH 0.0468
21.4
2.3
1.4
0.3
1.9
0.2
0.187
0.018
-
>
z
n
(ll
CJ15(NH2)C(C2H.s)CH2SH 0.0499 4.1 o.s o.s 0.049 ~
Fuel D-3
~
Starting fuel 82.4 3.2 3.0 0.298
8:::
'"1:1
CJ1s(NH;z)C(C3H7)CH2SH 0.0526 8.3 0.7 0.6 0.029 0
c
0.0513 9.4 0.9
z
CJ1.s(NH2)C( C 2H 5 )CH2SH 0.8 0.042 0
(ll
0
'TJ
~
0
!""
trl
c
:::
TABLE 66
Effect or lonol Derivath·es (0.05 %) on the Thermai-Oxidative Stability or Fuels
(160°C, Copper, 0 2 , 4 hrs)
Additins
lkposit Corrosion Optical density,

R=IIO-P-CHi" Sediment, on copper, or copper, A= 4358 A,
0
:"'
Fuel mg/100 mJ g/mz g/mz layer 3.~5 mm c:l
0
[;;
I 2 3 4 5 6 ::
>
~
RH TS-1 5.3 0.3 0.4 0.060 0
RT-1 7.2 0.2 0.2 0.038
<
T-6 9.4 0.3 0.6 0.100
RCH2SH TS-1 2.6 0.1 0.2 0.003
RT 2.8 0.1 0.1 0.008
T-6 2.6 0.2 0.2 0.009
03 6.8 0.2 0.3 0.018
RCH2SCH2R TS-1 4.0 0.1 0 0.018
RT 4.6 0.1 0 0.020
T-6 4.2 0.1 0 0.028
03 8.2 0.3 0.1 0.049
RSR TS-1 4.3 0 0.1 0.028
RT 5.2 0 0.3 0.023
T-6 4.3 0 0.2 0.029
D3 9.6 0.1 0.4 0.067
(CH,),C*S*C(CH,),
OH OH
TS-1
RT
T-6
4.8
5.8
4.2
0.2
0.3
0.2
0.1
0.2
0.2
0.027
0.023
0.028
DJ 8.7 0.3 0.4 0.039
CH3 CH 3
RCH2NHCHzCHzSH TS·1 6.2 0.1 0.1 0.012

T-1 7.0 0.1 0.2 0.010
T-5 7.2 0.2 0.2 0.019 0
D3 10.4 0.5 0.3 0.062 :;c
0
(CH,),c*s-S*C(CH,),
OH OH
TS-1
RT
7.2
6.8
0.5
0.6
0.2
0.4
0.029
0.028
>
-z
(")
Cl}
c
7.0 0.6 0.028
~
T-6 0.4
D3 10.2 0.7 0.7 0.069
en~ CH3 (")
0
(RCH2NHCH2CH2Sh Ts-1 4.5 0.2 0.2 0.012 :::
RT 5.2 0.1 0.2 0.016 (3
T-6 5.8 c
DJ 9.2
0.1
0.3
0.2
0.4
0.022
0.062 e
Cl}
TS-1 4.5 0.2 0.2 0.029 0

....,
RT 5.8 0.4 0.3 0.042 "tl
RCH2S-o m
T-6 S.l 0.2 0.2 0.048 ;d
D3 9.4 0.4 0.4 0.072 0
~
c
s::
312 0. F. BOLSIIAKOV
D
\~ t.O
FIGURE 45. The effect of MPAB additive on the thermal-oxidative stability of fuels:
1-'fS..l· 2-GF· 3-0.0S% MPAB in TS-1; 4-GF; A,B,D-ox.idation by the PK method; F,E-
investiga;ion by light scattering; C,G,I,H-oxidation by the LSART method (a-heating to ISO °C at a
rate of 1°/min, b-oxidation at 150 oc, c-cooling).
and compared with that of the control samples (Fig. 46). The accumulation of gums
takes place considerably more slowly in the fuel with added MPAB than in the control
fuel. The additive is efficient not only in fresh fuels, but it improves the stability of
fuels after prolonged storage as well. This is very essential in stabilizing fuels which
should be kept for a long time.
Apart from amino thiols, the ionol derivatives synthesized have been studied in
detail. Table 66 shows the results of tests of the most efficient compounds. Other ionoi
~oJo~--------------~
,
o<
(X) i 2
U'\ 0
C""\ 0
.q- .....
11 0,020
~
1f
1 2 J 140 tso 220 •c

.,. STORAGE TIME, Y'
0.4 - - - - - - - - - - -
~
..
~ 0,2
Cf.l
0
1::::
~
0
u 0,1
2 4 6 140 t80 220 • c

OXIDATION TIME, hr
FIGURE 46. The effect of additives on the optical density in storage and on the thermal oxidative
stability after storage of RT + additive for three years:
1-RT; 2-RT + monoethylene glycol monoethyl ether (EME); 3-RT+ EME + 0.05% MPAB;
4-RCH2NH 2; S-RCH2N(CH 3)2; 6-RCH2.SH; 7-RT + 0.05% RCHzSH; 8-RCH2.NH2; 9-
MPAB.
derivatives are comparable with ionol in efficiency, some derivatives being less
efficient. As seen from the data presented the sulfur-containing ionol derivatives
considerably improve the thermal-oxidative stability of fuels and are more efficient
than ionol.
The ionol homologs reported have been further investigated in more detail in the
temperature range from 100 to 240 oc. The kinetics of the oxidation and the
mechanism of the solid phase formation were studied by light-dispersion technique
.. R i" . D N E! aJ
'S ,.~ .....
• - , 1:10
=J
0
'1"4
,...•
+" CfU
+"
f' l
0
Q)
s
0)
,Q c0
ct1
cQl
t4
0
~
.....1:10N 1
" £
0
aro e
~
CQ
•
Q)
'U
.....
HttQ5
0
s..
Q)
Po
0
h
'U
~
a
/
,_ ,·
.....
........... ~c I
Q)
...t fDO
0
.....
...
~.50 a 6
P4
uo 1so 2zo•c 120 24o J o t4o tso 220 •c

Oxidation time, min
FIGURE 47. The effect of ionol derivatives (0.05%) on the thermal-oxidative stability of the fuel
RT: 1-RT + ionol, 2-RCH2SH; 3-RCH2SC,H5; 4-RCII2NH2; S-RCII2N(CH ) ; 6-
3 2
RCH2N(C,H,)2; 7-RCII,NIIC,II,; 8- t 6 r S - ; 9- RCII 2NI!(CII,),SII;

CH, 2
10-[RCH2NH(ClhhSh; 11-RClhSClhR.
(Fig. 47). As seen from the data reported, the sulfur-containing ionol derivatives
improve greatly the thermal-oxidative stability of the fuel in a wide temperature
range. The oxygen absorption is considerably reduced. The above additives inhibit
the oxidation both at the start of the autocatalytic process and during the oxidation.
The additives when introduced during the oxidation immediately reduce the oxygen
consumption. The formation of hydroperoxides is sharply inhibited, the hydro-
peroxides already formed undergoing decomposition. This is especially clearly
expressed with (3,5-di+butyl-4-hydroxyphenyl)-methanethiol. It should be noted in
this case that ionol, when added to fuel during an already developed autocatalytic
phase, cannot inhibit the oxidation process. Ionol proves to be comparably efficient
only when added to the starting fuel before the oxidation. At temperatures above
140-160 oc the effect of ionol decreases rapidly, being negligible at higher tempera-
tures.
The above sulfur- and nitrogen-containing ionol homologs also possess clearly
displayed anticorrosive and anticoagulant properties (Fig. 47). The presence of the
additives considerably reduces corrosion of copper as well as the number and size of
particles formed as determined by light dispersion. The additives greatly improve fuel
stability upon prolonged storage and are fairly well compatible with another additive,
liquid "I" (Fig. 46).
The additives under consideration perfect efficiently the thermal-oxidative stability
of highly refined cycloalkane fuels (Fig. 48).
The effect of inhibitors is known to be closely associated with the chain mechanism
of the oxidation reaction. In most cases the inhibitor, In, reacts with peroxide radicals
or with hydroperoxides to form radicals p· of low reactivity:
ROi +In - p ·
R' +In-RH'+ p·
RO', HO', H0 2 + I n - ROH', H20, H20 2 + p·,
R02 (RO'; HO', H02) + p· - R02P (ROP, HOP, H0 2P)
If radicals p· are less reactive than the radicals ROi the process will be inhibited by
In. Besides, the inhibiting effect may be caused by binding prooxidants, metal ions of
varying valency.
The equation reproducing the oxidation rate in the presence of inhibitor can be
obtained by solving a kinetic equation system:
In .... +cu+ .... In}
In + cu++(Fe++) - (stable complex)
In .... +Fe+ .... In
d[RO;)
dT = Wi + nkt[ROOH][RH] - k2[InH] • [ROi];
d[ROOH] .
dT = k3(RH][R02] + k2[InH)[ROi] - k 1[ROOH][RH]
316 G. F. BOLSHAKOV
HO
t8o•c
t20 1,2
11100
•
a
..... 80
E-t
;;o,4
0
~ H
tll
g 60 gp::; 0,6
JQ
< 0
0
fa0 40 fa 0,4
>t P-4
><
0
A4
0
20 00,2
tBo•c
1,0 o< o,oto
\0
Lr'l
(""\
.q.
0.4 u
-<..
".. 0,8
tll
~
>t
E-t
H H
0 tll
~D,oo:J
< ~
0.4 ~
~
0
0,2 1-1
fof
P-4
0
60 120 ., UD 140 22o•c

OXIDATIOIJ TIME, hr
FIGURE 48. The effect of additives on the oxidation of cycloalkane fuels:
1-mixture of alkyl derivatives of cyclohexane (AC); 2-2-methyl-S-ethyl-6-cyclohexylheptane
(EC); 3-AC + 0.05% 3,5-di-t-butyl-4-hydroxybenzylamine; 4-(3,5-di-t-butyl-4-hydroxyphenyl)
methanethiol; 5-N,N-dimethyl-(3,5-di-t-butyl-4-hydroxybenzyl)-amine; 6-MPAB; 7-EC + 0.05%
MPAB; 8-N,N-dimethyl-(3,5-di-t-butyl-4-hydroxybenzyl)-amine. Introduction of additive in the oxida-
tion process is shown by an arrow.
where n is the probability of branching upon hydroperoxide decomposition according

to the reaction
ROOH + RH ~ RO' + H20 + R'
and k2 is the coefficient describing the ability of the inhibitor to form stable radicals in
the reaction with peroxide radicals.
kl •
R0·2 + lnH - - R0 2H + In
k3 stands for the coefficient characterizing the oxidation chain propagation:
. kl
R02 +RH -----+ R0 2H + R'
Solving this system gives the expression (ROOH] = Aexp(yT)'
_ { ] [ k 3{RH] + k 2(1n)]
where y - k1 RH n k (In) 2
lonol does not bind ions of varying valency, but phenols are widely used as
inhibitors. The mechanism for the inhibition of oxidation by ionol is most likely as
follows:
The phenoxyl radical formation has been confirmed by ESR and IR spectra. Four
triplet groups with relative intensities of 1:3:3: 1 in the spectrum of 2,6-di-t-butyl-4-
methylphenoxyl (Fig. 49) appear due to the interaction of an add electron with three
equivalent CH 3 protons.
.J.i..
FIGURE 49. ESR spectrum of 2,6-di-t-butyl-4-methylphenoxyl.
The appearance of three lines with a 1:2: 1 intensity ratio and a considerably lower,
splitting (than that on the methyl protons) in each group is related with two equivalent
protons in the meta-positions of the benzene ring. The 0-H bond absorption in the
IR spectrum of phenoxyl radical disappears, which supports a radical involving
mechanism.
Due to the interaction of an odd electron at the oxygen atom with rr-electrons of the
benzene ring phenoxyl radical stabilization occurs. In the course of the oxidation a
quinoid rearrangement takes place leading to dual reactivity of the phenoxy I radicals:
The formation of quinones is confirmed by theIR spectra of the oxidation products

(Fig. 50) which clearly show an absorption pattern in the 1680-1800 cm- 1 region,
11! I Ul ; I I e I
JD
ZD
10
ID
A
y
0
\\
r.i
u
ID"'
~11
~ID
lflJD
~ 41
~-<.so
20
10 w ID
5D
.fO
JD
2D
c
FIGURE SO. IR spectra of sulfur-containing ionol derivatives prior to and after oxidation (200 ac
2.5 hrs). •0 2,
a)* b)*s* CH1 CH1

1-initial, 2-post-oxidation
caused by the formation of conjugated C=O groups. This indicates a greater role of
C=O resonance structure in comparison with C=O. This marked lowering of the
reactivity of ionol at high temperatures is brought about, most probably, by the
formation of diquinones:
The formation of diquinones seems to be preceded by the formation of diphenol

radicals:
The ESR spectrum of the monoradical (Fig. 51) displays triplet splitting (8.2 G)
caused by the protons of the nearest CH 2 group. A weaker triplet (1.8 G) appears as
above at the expense of two protons of the benzene ring. A similar spectrum is typical
of a radical with one methylene group.
The formation of diquinones can be explained only by assuming isomerization of
the primary radical followed by recombination of the secondary radicals. Recombina-
tion takes place, probably, in the elemental act in approaching the methyl groups.
This is indicated by a low entropy of recombination as judged by the preexponential
·o-9-cH=Q=o
flGURE SI. ESR spectrum of the radical 'O*(CH,h-Q-011

factor in the reaction rate equation:

K = 5.6 • 10- 17 e-l900/kT cm3 /s
Radicals of this type are very stable, even in air. The g factor in the crystalline state
is characterized by slight anisotropy (2.005 and 2.007). The melting point of these
crystals is 151.2 °C. The ESR spectrum usually contains a doublet of quintets which is
due to four equivalent meta-protons (1.3 G) of the benzene rings and one a-proton
(5.7 G).
Similar diquinones have been synthesized and spectrally identified. 119 Due to the
lower CH3 group absorption intensity it is safe to assume that some ionol oxidation
products form diquinones. The formation of phenoxyl radicals and quinoid com-
pounds has also been reported. 45 •46•107
A methylphenoxyl radical readily reacts with hydroperoxides to break the oxida-
tion chain:
'0 * C H ) + ROOH
At 110-120 oc this peroxide decomposes to give radicals of low stability (Fig. 52).
The 1: 2: 1 triplet differs from that of the starting radical in smaller splitting (1.2 G).
The ESR spectrum may be assigned to the radical:
·oc~=o
5o
FIGURE 52. ESR spectrum of the radical • o-Q-cn-Q=O

The recombination of phenoxyl radicals is certain to afford diquinones. It is the

formation of diquinoid structures that accounts for the insufficient activity of ionol at
elevated temperatures.
The sulfur- and nitrogen-containing ionol derivatives possess antioxidant and
anticoagulative properties. The thermal-oxidative transformations of the additives
obtained have been studied in order to ascertain the mechanism by which these
additives act.
In disulfides no oxidation of sulfur atoms occurs, the IR spectra show no signs of
sulfur-oxygen bonds, which is evident from the absence of absorption in the regions
1030-1080, 1130-1170, and 1200 cm- 1 (Fig. 53). In the oxidation ofbis-(2-hydroxy-3-
t-butyl-5-methylphenyl) disulfide the quinoid structure undergoes rearrangement to a
considerably lesser extent than in the oxidation of ionol. This is indicated by a
shoulder at 1690 cm- 1 of the main band at 1720 cm- 1 • There is a strong absorption at
1720 cm- 1 which is indicative of a side chain oxidation to afford an unconjugated

C=O group. The oxidation occurs in the group with a tertiary carbon atom to give
structures of the type
JO~ ~ ~ ~ ~ ~~ ~ ~ ~
20
ID
0
4/J
JO
a 20
oo
ell
FIGURE 53. ESR spectrum of the radical '0_;=\_0

H3c"=.("-
322 G. F. BOl.SHAKOV
or more probably,
Two C(CH3h group absorption bands at 1365 and 1380 cm- 1 with a 1:2 intensity
ratio are replaced by the predominant absorption of one of the CH 3 groups
(1370 cm- 1). Some contribution to the absorption is from the initial C(CH 3) 3 moieties
and probably from ArC(CH 3 h. The 1600 cm- 1 band intensity does not change from
the starting material to the oxidation product. The OH group absorption maximum
changed from 3480 to 3420 cm- 1 and the band shape changed owing to the
appearance of hydrogen bonding with the carbonyl group formed.
The oxidation of N,N-bis(3,5-di-t-butyl-4-hydroxybenzyl)diaminodiethyl disulfide
does not lead to the formation of quinoid structures in any noticeable amounts. No
oxidation occurs at the sulfur atom, which is evident from the fact that the absorption
pattern in the 1000-1300 cm- 1 remains unchanged.
No C=O groups absorbing in the 1720 cm- 1 region are formed; the structure
does not appear either, judging by the persistence of the CH 3 groLip absorption
pattern. The spectrum displays, however, a 1670 cm- 1 absorption due to conjugated
C=O groups. The intensity of this absorption, as well as that at 1600 cm, -t, is
comparatively low and gives some ground to suggest the oxidation of the side chain to
form the product
In sulfides (Fig. 53) the oxidation involves the formation of a quinoid stru t
This is sho~n by the appearance of the absorption pattern 1600, 1650, and 1680 ~~~~·
Stable rad1cals . .
seem to be formed first. They are then transformed to the products:
(CH3 )3c 0
K
CH2-s-cH2
g\l ~
C(CH 3 ) 3 ; Oo)\=Ca-s-Q
'>=I
0 C(CH3)3 CH3SP C(CH3)3

It should be noted that the sulfur atom either remains unaffected or is only mildly
oxidized.
In the oxidation of bis-(3-t-butyl-4-hydroxy-5-methylphenyl) sulfide the sulfur atom
is specifically oxidized (1190 cm- 1), practically no quinoid rearrangement occurring.
These phenomena account for the low inhibitory activity of this compound.
The ESR spectra of some radicals (Table 67) indicate that the odd electron is
located in only one of the rings, producing no effect on {3-groups. The electron
delocalization in other radicals is much higher. Thus, the electron delocalization
/R
potential barrier created by the groups -s-, -s-s-, -CH2-N, ,
CH2-
-CH2-, and -(CH2h- is considerably higher than that due to the groups
-CH=CH-, -CH=, -CH=N-, and-N=. All these features are responsible
for an even greater inhibitory activity of the first group of phenoxyl radicals.
The ionol derivatives obtained not only efficiently inhibit the oxidation of fuels, but
also prevent coagulation of the gum particles being formed. 26 This is indicated by
results of research regarding the deposit coagulation monitored by light dispersion
and a detailed examination of the composition and structure of the deposits. The
elemental composition of the deposits formed in additive-improved fuels is shown in
Table 68.
The deposits are characterized by a low content of oxygen, nitrogen, and sulfur
compared to the solid phase formed in the oxidation of the starting fuel T -1. The IR
spectra of the deposits exhibit weaker OH and C=O group absorption. These spectra
are structurally different from those of the deposits formed in the starting fuel. The
most intense bands are those caused by sulfur-oxygen bonds (1050, 1170, and
1
630 cm- ). These bands are considerably less intense for the deposit formed in the
oxidation of T-1 with 3,5-di-t-butyl-4-hydroxybenzylamine. These bands are most
likely to be due to oxidation of the organic sulfur compounds in the fuel forming a
small amount of precipitate.
324 G. F. BOLSHAKOV
TABLE 67
Parameters of ESR Spectra of Heteroatom-Containing Phenoxyls
·o-9-• a8 (meta), G ux a 8 (para), G a (other nuclei), G
R=-CH3 1.8 -1.70 10.6

-SCH3 1.4 2.5
-SCH2CH3 1.3 1.8
-SC(CHlh 1.4
-SPh 1.4
-s-Q-oH 1.4
-s-s-Q-oH 1.6
OSH 2.1
OSCH3 2.0 2.0
-CSCH3 1.9
11
0
02SCH3 2.3 1.7
-NH2 0.5 -0.660 2.3 3.7
-HC=N- 2.2
-C=N 2.2 +0.628 1.3
-CHzNH2 1.8 11.0 1.8
In the oxidation of additive-containing fuels practically no crystalline phase is

formed. The X-ray patterns of all the deposits show a clearly defined amorphous halo
in the 8.05-8.20 Aregion. This shows that the oxidation of additive-containing fuels
does not lead to sulfates, sulfonic acid salts, or carboxylic acid salts, which are the
main crystalline components of deposits. The absence of these salts can be explained
in terms of passivation of metals and the absence of the corresponding acids. This
means that the additives possess anticorrosive properties. The decrease in the metal
activity seems to be caused by coordinate bonds between the additives and metal ions
of varying valency.
The complexing properties are especially evident in synthetic amino thiols which
have also been shown to be strong antioxidants and anticoagulants. These properties
are stipulated by the specific structure of amino thiols. The simultaneous occurrence
of acidic and basic groups in the amino thiols is responsible for their amphoteric
TABLE 68
Characteristics of Sediments in the Fuel T·l Containing 0.05% Synthetic Additives
(l40°C, Copper, 0 2 , 6 hrs)
011 011
(CII,),C *C(Cil,), (CII,),C *C(Cil,),
Characteristics Without
or sediments additives
CllzNIIz CII 2N I I - o
Element
composition,
wt.%
c 36.3 62.3 66.2

H 5.4 10.1 8.2
s 4.1 0.3 0.1
N 2.4 4.5 5.0
0 45.8 22.3 20.4
Cu 4.0 0.5 0.1
Amount of
sediments, 28.3 4.7 2.1
mg/100 ml
011 011
Czll.
(CIJ,),C*C(CIJ,), (CII,),C *C(CII,J, I .
o-~-SII
Nllz
CII 2SII CllzN(Czll 5)z
Element
composition,
wt.%
c 67.5 67.1 60.7
H 7.4 9.2 6.2
s 2.8 0.2 3.2
N 0.1 5.3 5.4
0 22.0 18.1 24.2
Cu 0.2 0.1 0.3
Amount of
sediments, 5.2 2.0 2.0
mg/100 ml
326 G. F. BOLSHAKOV
properties. Thus, J3-mercaptoethylamine exists as cation (I) in a strongly acidic

medium and as anion (II) in a highly alkaline medium:
+
(I) H NCH2CH 2SH
3
!1 +H+ pKaSH = 8.19
+
(II) H NCH 2CH 2S-
3
- a+ !1 pK~
2
= 10.75
CH cH NH
3 2 2
pKew • 10.63
2
The free base of J3-mercaptoethylamine exists as a zwitterion (11). Its two ionization
constants, pKas 11 = 8.19 and pKaNJ 12 = 10.75, have been determined by poten-
tiometric titration of J3-mercaptoethylamine hydrochloride. It should be noted that
the pKa values of similar zwitterions are often significantly different from the values
of analogous functional groups (SH and NH 2) present in simple thiols and amines.
Thus, the pKa 511 value for J3-mercaptoethylamine (8.19) is several orders of magni-
tude different from that of ethanethiol ( -10.50). The pKaN 11, values for J3-mer-
captoethylamine and ethylamine are more similar (10.75 and 10.63, respectively).
Potentiometric titration of amino thiol hydrochlorides gave SH and NH 2 group
TABLE 69
Ionization Constants of Amino Thlols (25 °C, 0.01 l\1)
Compound no. Amino thlol pKasu
1 HS(ClhhN11 2 ·IICI 8.19 10.75

2 CH 3(SH)CIICI hNH 2·I ICl 8.10 10.82
3 (CIIJ)zSIICCihNII2 ·IICI 8.07 10.77
4 ~Hs(SH)CIICII 2NH 2 ·Ha 8.19 10.91
5 (CH 3 )~11sC(SII)CII 2 NII 2 ·Ha 8.19 10.94
6 C3II,(SH)CIICII2NII2 ·Ha 8.32 11.05
7 411sCihCII(SII)CH2NH2 ·Ha 8.00 11.04
8 4HsCih(CHJ)C(SII)CII2NII 2 ·I ICl 8.00 10.86
9 C6H 11 CII(SII)CHzNih ·IICI 8.5
OCIIz-Nifz·IICl
10 8.21 11.06
Sll
11 Ct.lls(CJih)C(CII2SII)NII 2·Ha 7.61 10.15
TABLE70
Kinetics of Amino Thiol Alkylation with Chloroacetamide
k ·102, 1/mole•sec
Amino thiols pll = 9.50 8.50 7.50 6.50
HS(CH2hNll2 • HCl 12.7 8.35 2.43 0.32

Ct,H5CH2CH(SH)CH2Nlh • HCl 8.60 6.10 2.45 0.36
CH3CH(SH)CH2Nllz ·Het 6.70 4.50 1.53 0.21
~H 5 CH(SH)CH2NH2 • HCJ 6.80 4.40 1.27 0.17
Ct.HuCH(SH)ClhNII2 • HCI 6.40 4.23 1.15 0.137
C3H7CH(SH)CH2NH2 • HCI 1.08 0.112
CH3(C6HsCH2)C(SH)CH2Nll2 ·Het 2.40 1.63 0.55 0.077

(CH3hC(SH)CH2Nlh ·Het 2.20 1.43 0.45 0.062
CH 3 (~II 5)C(SH)Cli:!NII2 •IICI 2.00 1.33 0.32 0.042
C6Hto(Sli)CII:!Nlh ·Het 1.89 1.23
Ct,H 5 (~11 5 )CClhSII(NII 2 • HCl) 13.9 8.7 2.81 0.48
Ct,HsC(C3l17)ClhSH(Nll;z ·Het) 13.0 8.4 2.51 0.33
ionization constants closest to those of (3-mercaptoethylamine. This suggests that the

amino thiols studied also exist as zwitterions. According to the data of Table 69 the
SH ionization constants of amino thiols with the mercapto group at a primary,
secondary, or tertiary carbon atom are nearly the same, being considerably different
only in 1-mercapto-2-phenyl-2-aminobutane and 1-amino-2-phenyl-2-aminopentane.
It is these amino thiols which proved to be the most efficient additives (Table 65).
In this connection the reactivity of the mercapto group was studied in more detail
by alkylation with chloroacetamide according to a modification of Lindley's techni-
que. All measurements were performed in an automatic titrator TTT-1 with a glass
and a calomel electrode at certain pH values. The alkylation was studied at 30 oc in
0.1 M potassium chloride. The hydrochloric acid evolved in the reaction RSH +
CICH2CONH 2 - RSCH2CONH2 + HCI was neutralized with 0.1 N KOH and the
alkali consumption with time was registered.
As seen from Tables 69 and 70 the SH group reactivity in the reaction with
chloroacetamide is highest in the case of the primary mercapto group and lowest with
the tertiary mercapto group. The alkylation data are in agreement with the results of
the oxidation of these compounds with aqueous 2,6-dichlorophenolindophenol at
20 oc and pH= 7.0 (Fig. 54), in that the tertiary mercapto group-containing amino
thiols are considerably more difficult to oxidize than the compounds with a secondary
or, even more so, a primary mercapto group.
The oxidation of amino thiols with 0 2 in the presence of copper ions (2.5 • 10- 7
mole/1) at 25 oc and pH = 9.75 has revealed a certain dependence of the reaction
rate on the nature of the mercapto group. The half-oxidation time for the amino thiols
with a tertiary mercapto group turned out to be shorter than that for amino thiols with
328 G. F. BOLSHAKOV
.
~
H
~BOT--4~~-h~------~----~~
~
~
Pt..
~40~~~~~--------~------4
fi3
~
2 8
min
FIGURE 54. Rate of amino thiol oxidation with 2,6-dichlorophenolindophenol:
1-2-phenyl-2-amino-1-mercaptobutane; 2-1-amino-2-mercaptoethane; 3-1-phenyl-2-mercapto-3-
aminopropane; 4-2-mercapto-l·aminopropane; 5-l·amino-2-mercaptobutane; 6-1-amino-2-
mercapto-2-methylbutane; 7 -1-amino-3-mercapto-2-methylpropane; 8-1-amino-2-mercapto-2•
methyl-3-phenylpropane.
TABLE71
Half-Life or 0 1 Oxidation of Amino Thiols, Min.
Compounds Without Cu++, 37 "C
NH 2CH 2CHzSH 60 40
CH3CH(SH)CH2NH2 60 160
CzHsCH(SH)CH2NH2 65 170
C3li 7Cli(SH)CllzNll2 75 130
(CH3hC(SH)CH2NH2 so 43
(C2Hs)(CHl}C(SH)CH2NH2 65 36
(CH2lsC(SH)CH2NH2 80 56
4.HsC(C2Hs)(NH2)CH2SH 79 35
TABLE72
Instability Constants of Amino Thiol Complexes with zn++
= =
(25 °C, CAT 0.01 M, Czn(NO;J 1 0.005 M)
Ligand Kt K2 Ku.ta~
HSCH2CHaNH2 • HCl 1.74·10210 5.75 ·10- 9 1·10

CH3(SH)CHCI1zNHl ·HO 1.78·10-10 4.90·10- 8 8.71•10- 18
CzHs(SH)CHOI2NH2 • HCI 1.02·10- 10 4.47·10-9 4.57 ·10- 19
(CH3)zC(SH)CH2NH2 • HCI 1.32·10- 10 8.13 ·10- 10 1.07·10-19
11
CzH5(CH3)C(SH)CH2NH2 • HCI 5.50·10- 3.63 ·10- 10 2.00·10- 20
4,H5(CzHs)C(CH2SH)NH2 • HCI 1.85 ·10- 10 5.87 ·10- 9 2.00·10- 18
a secondary mercapto group and approaching the corresponding value for {3-mer-
captoethylamine (Table 71). This specific behavior of the amino thiols in the
oxidation with 0 2 in the presence of metal ions of varying valency is most probably
due to their strong complexing ability. In order to obtain certainty about this
assumption, the instability constants of amino thiol-metal ion complexes have been
potentiometrically determined. All amino thiols have been established to be ex-
tremely prone to complexing with copper, to an extent preventing any exact
determination of the instability constants. For this reason the instability constants of
amino thiol-zinc ion complexes have been determined. It has been shown that under
these conditions the maximum number of ligand molecules per zinc ion equals two.
The instability constants K1 and K2 , listed in Table 72, were calculat~d as ligand
equilibrium concentrations in solution with A. being 0.5 and 1.5, respectively.t
The stability of the amino thiol-zinc complexes with the mercapto group at a
tertiary carbon atom is considerably higher than in the case of amino thiols with a
secondary or a primary mercapto group. The differences observed seem insufficient to
explain unambiguously the anomalous order of the oxidation of amino thiols with 0 2 ;
however, it is beyond any doubt that the amino thiols, especially those with a primary
mercapto group, exhibit a very high complexing ability.
It was possible to isolate and investigate complexes formed by 1-mercapto-2-
phenyl-aminobutane and cu++. There are three metal ions per four amino thiol
molecules in these complexes. This suggests that the formation of these complexes
is due to the interaction of bis-(1-mercapto-2-phenyl-2-amino ethane)-copper with
excess copper ions:
2[(H 2N--yH-CH 2 -s-) 2 c~] + cu++

C6H5
I. r,~H 2N---cH-CH2 s-) 2Cu''] }\ ++
\Cu11
2
b6H5
t A. is the average number of liga~d molecules attached to one metal atom.

These complexes possess evidently a trinuclear structure:
~6H5 ~6H5
HSC:;/C-C~
H2N,, /S'
/CH2
/S"
-c"' ,,NH2
C2 H5
H N"
/
......
/
........
.,Cu
"'
,,
s/
' '
/,
1/
Cu
/
' ' ' s //

,/
Cu.....,
/
...........
'1rn
2 ""' / ""' / 2
H 5 c 2-~-cH 2 CH 2-~-C 2 H 5
C6H5 C6H5
This complex formation may be responsible for the lower corrosive activity of fuels
and the lower catalytic activity of metals in the presence of synthetic additives.
The mechanism of the dispersive action of synthetic additives most likely involves
the formation of a layer of oriented polar molecules on the surface of fine particles,
which promotes the orientation of other polar molecules. In this way charges of the
same sign preventing coagulation are generated on the particle surface. The forma-
tion of polar molecules of additives is facilitated by the presence in the particles of
structural moisture and acidic substances with functional groups such as -S0 3H,
,&:0
-C~ , and -S02H which dissociate and thus provide media with suitable pH.
OH
The fact that the basic properties of amino thiols are more pronounced than their
aci~ic _ properties may explain the generation of the zwitterions
H 3NC(R)C(RR')CH 2s- which then prevent coagulation.
Besides, the additives are capable of complexing with metals of varying valency
thus diminishing the role of these elements in substances presenting active coagula:
tion sites in the solid phase.
Some sulfur compounds are efficient antiwear additives for fuels and oils. It is
known that a certain increase in the sulfur compound content of transmission oils
considerably improves the antiscouring properties of the latter. The presence of
optimal sulfur compound amounts in lubricating oils also increases their antiwear
properties. During the latest years much attention has been given to improving the
antiwear properties of jet fuels by increasing the extent to which heteroorganic
compounds are removed.
Jet fuel additives must be highly effective since the jet fuel is consumed in enormou
quantities which requires the additives to be introduced in hundredths or thousandths
of one per cent. A high efficiency of the additives is also necessary due to the fact th s
the fuel is only once in contact with the lubricated surface. These strict requireme at
.
f or anhwear a dd'Ihves
. can b e satisfied
. provided that the mechanism of their actio nts
·
known. n 1s
The friction and wear process model is a complicated relationship of the composi-
tion and the properties of the lubricant and the materials of the friction-affected
surfaces. The interaction of friction surfaces with an external medium can conven-
tionally be subdivided into several stages.
The initial interaction is determined by the energy state of the metal and the
physical and chemical activity of the lubricant. Adsorption and chemisorption are the
primary processes at this stage. If friction and wear are assumed to be determined by
only physical processes, the lubricant antiwear effectiveness increases with increasing
the insulation between the bodies involved in friction against each other. Thus, the
antiwear effect is in this case governed by the thickness of the insulating layer between
the rubbing surfaces which is formed by the active components of the lubricant. This
layer thickness will increase with the surface activity and the polarity of the antiwear
components of the fuel. These properties are common to heieroorganic compounds
possessing considerably higher dipole moments than hydrocarbons. The high polarity
of the molecules of the additive in combination with the alternating micropolarity of
the metal crystal lattice 19 provides for the formation of a multimolecular oriented
boundary layer on the friction surface upon its primary exposure to the lubricant.
Parts under friction which are lubricated with jet fuel are subjected to high specific
loads and elevated temperatures. Therefore, the adsorptive boundary layer itself is
not able to protect the rubbing surfaces from wear. The friction raises the tempera-
ture and reduces the adsorption in the contact zone with a simultaneous intensifica-
tion of the additive-metal surface interaction. At this stage, the antiwear efficiency of
additives depends upon their influence on the structural mechanisms of plastic strain
and the ability to modify thin surface layers of the metal. The modification should be
an optimal one, devoid of the formation of loose boundary layers stripped readily
with an indenter and leading to rapid wear.
Spectral analysis of the metal wear products formed upon friction in jet fuel
admixed with sulfur- and nitrogen-containing compounds as antiwear additives has
provided some information on the character of additive-rubbing surface interaction.
The tests were performed on a specially designed friction machine. A friction
couple was represented by an authentic plunger of a jet engine pump regulator (XBH
steel) and an accessory plate of AMG alloy. The tests were conducted at 100 oc.
The average sliding rate in the friction zone was 1.8 m/ s. The additives were
introduced in amounts of 0.0125-0.050 wt. % into fuel F-7 detarred on silica gel.
As seen from Table 73, the antiwear effect of sulfur-containing addttives is higher
than that of the known admixture PMAM-2 and isopropyl-octadecylamine. 2-(2-
Aminoethylthio)-benzimidazole proved to be an extreme! y effective anti wear additive
in all the concentration ranges studied. At a concentration as low as 0.025% the wear
value is reduced to almost one seventh. It is noteworthy that the 0.025% concentra-
tion level completely prevents "setting" in friction, i.e. no residual deformation of
metal surface layers remains on the friction trail. No effect of this kind is observed in
the presence of other known additives.
To ascertain the mechanism of the antiwear effect of the additives the solid wear
products were isolated from the postexperimental fuel by centrifuging and studied by
IR spectroscopy.
The additive heteroatoms are the first to oxidize to so2 and so groups, the s-e
332 0. F. BOLSliAKOV
TABLE73
Etrect or SuiCur-Containing Additives on Antiwear Properties o£ Well-Refined Jet Fuel
Additive Wear
concentration,
Additives wt.% AGp1 G4 AWl
110-Q-5~011
9.4 7.7 17.1
0.050 6.2 0.5 6.7
0.025 5.3 0.1 5.4
0.0125 2.2 0.8 3.0
'.:11 3 Clll
OH 011
0.050 7.4 0.6 8.0

(C,II,),NCII,*S*CII,N(C,II,), 0.025 10.0 0.2 10.2
0.0125 3.5 1.7 5.2
C(CII,), C(CII,)J
o.oso 2.7 0 2.7

Oc:-1-S-(CII,),NII, 0.025 2.5 0 2.5
I 0.0125 5.6 0.6 6.2
11
PMAM·2 0.050 8.0 4.0 12.0
0.025 9.4 0.8 10.2
C 18Hl1NHCH(Clhh 0.050 8.1 4.1 12.2
0.025 8.1 4.2 12.3
Note: AGpl = change in plate mass, mg; Gd = quantity of deformed metal, mg; A WI = AGP1_
Gd = antiwear index, mg
and C-N bonds being broken. The sulfoxides have experimentally been found to
possess better antiwear properties than the sulfides. 216
The IR spectra (Fig. 55) of the wear products formed in the friction zone contain
some absorption bands indicating the presence of magnesium, aluminum and, to a
lesser extent, iron hydroxides (870, 1130, 1170, 1410, and 1630 cm- 1), sulfates
sulfites (1120-1180 cm- 1), and oxides (830-870 cm- 1). Besides, sulfides can also b~
expected to occur among the wear products. These data are also supported by X-ray
analyses.
In both the original and the PMAM-containing fuels only metal oxides
(-900 cm- 1) and considerably smaller amounts of metal hydroxides were found
among the metal wear products. The organic components of the wear products are
poorly manifested in the IR spectra.
Heteroatoms, and primarily sutfur, are very essential for the formation of low-
melting eutectic and plasticized layers. After friction sulfur atoms were found in the
metal boundary layers at a depth to 25-30 mJ.L .
. Thus,. heteroa.to?ts and first of all sulfur atoms, present in additives participate
directly m the fnct10n and wear processes. At higher additive concentrations in fuels
ORGANlC SULFUR COMPOUNDS OF PETROLEUM 333
211
tll
0
FIGURE SS. IR spectra of solid wear products in sulfur compound-modified fuel at 100 °C. (KBr
pellets; concentrations are shown in the spectra).
1) detarred fuel T-7
5) PMAM-2
the characteristic absorption bands in the IR spectra of the wear products become
more intense.
For a better under~tanding of the mechanism of the effect of sulfur-containing
additives, much attention should be given to the intermediate stages of fuel and
additive transformation in the friction zone and, in particular, to the organic
components of the wear products.
VII. EFFECT OF ORGANIC SULFUR COMPOUNDS ON SERVICE

PROPERTIES OF PETROLEUM PRODUCTS
The service properties of fuels and oils are known to be as follows: pumping,
volatility, inflammability and combustibility, stability, corrosiveness, resistance to
wear, and toxicity.
Sulfur co~p?~nds ha~e practicallr no effect on pumping, volatility, inflammability
and combust1b1hty. Dunng combustton of sulfur-containing fuels, however, the sulfur
oxides formed may increase the corrosion of the engine parts. Combustion-chamber
deposits become denser and harder to remove in the presence of sulfur compounds.
All sulfur compounds are considerably more toxic than hydrocarbons, therefore
sulfur-containing fuels are more hazardous. Sulfur compounds affect much the
stability, corrosiveness, and antiwear properties of fuels and oils. The author has been
studying the effect of sulfur compounds on these service properties since 1958. The
experimental results have been published in part. 64 •107,119,1 74·2t0,2t 7-222
VJJ.l. Formation of the Solid Phase in Oxidizing Sulfur-Containing Fuels
The amount of soluble and insoluble oxidation products formed in fuels and oils
depends on the chemical composition of the sulfur compounds and the hydrocarbon
medium, the sulfur compound concentration and the external conditions. The
amount of insoluble oxidation products increases with their increasing structural

differences 119 (Fig. 56). Table 74 summarizes data concerning the limiting sulfur
compound content of fuels at 100 and 150 °C. At higher concentrations a sharp
decrease of the fuel stability takes place.
402 tUU 40d llaJ 0.10 QJ2. 4Q2 404 40' aos a.to
n-NOUYUIERCAFTAN CONTENT, % PHENYLUERCAPTAN CONTENT, %
FIGURE 56. The ~ffect of 1-nonanethiol (A) and thiophenol (B} on the thermal-oxidative stabili
n-hexadecane (1), tsopropylbenzene (2), and hydrogenated fuel, 180-280 •c (3). ty Of
TABLE 74
Limiting Sulfur Compound Content (Recommended) of Jet Fuels
Temperature, Limiting sulfur compound content

Compounds oc calculated for sulfur, wt. %
Mercaptans 100 0.005

150 and higher 0.002
Thiophenes 100 0.20

150 0.10
Aromatic sulfides 100 0.07

150 0.05
Aliphatic sulfides 100 0.08
150 0.10
Disulfides 100 0.05

150 0.02
Complex oxidation products containing -OH,/C=O,

' .?'0
-c, ,-C~
~0 ,
OH ·O-
-S03H, -so-, -OS0 2- , and -OS0 20 - groups are formed by the oxidation
of medium distillate fuel. 119 After further oxidative condensation these products
precipitate. The elemental composition of sediments formed by the oxidation of fuels
is shown in Table 75.
The solid phase formed in fuels in contact with copper displays an increased ash
content and is poor in carbon and hydrogen. Numerous metals and non-metals which
accumulate in fuels from the oil in processing (sodium, magnesium, calcium,
vanadium, titanium, nickel, etc.), in storage and pumping (iron, zinc, copper,
aluminum), utilization (copper, iron, zinc, aluminium), and due to contamination of
fuels with atmospheric dust (silicon, calcium, aluminium, etc.) are present in the
ash. 123 Metalliferous compounds affect much the generation and coagulation of solid
particles in the fuel. This is confirmed by the following tests. At first the fuels were
thoroughly dried, then filtered 5 times through a double biological filter and the
filtrates ultracentrifuged for 12 hours. The chemical composition of the sediments
formed after the oxidation of the resulting fuels is presented in Table 76.
Preliminary removal of water and some micropollutants from the fuels leads to a
considerable change in the composition of the sediment ash. Only the copper content
remains practically constant. This is another indication of the presence of copper due
to corrosion of the metal exposed to heated fuel. Preliminary filtration and drying of
fuels reduces by 10-25% the amount of the sediments formed.
The IR spectra of deposits formed in heating the fuels in a metal-free environment
and in contact with copper differ much from each other. On the other hand the
spectra of sediments formed by the oxidation of different fuels, but under similar
conditions, are completely alike. 119
The insolu~le sediments formed in fuels in the presence of copper show weak CH
bond absorption (1385, 1460, 2870, 2930, and 2960 cm- 1) and intense OH group
absorption in the 3200-3470 cm- 1 region. There is also an absorption in the
.....
~
TABLE 75
Composition of Insoluble Sediments Formed in Fuels (160 •c, 4 hr)
RT TS-1 T-6 DS DL
Element
composition, % a b a b a b a b a b
c 66.8 38.8 63.1 35.1 60.2 37.0 62.0 37.2 63.2 36.2
H 6.3 6.0 5.9 5.8 6.0 5.9 6.2 5.5 6.3 5.4
s 2.8 4.7 4.5 9.3 1.6 2.3 1.7 2.0 1.2 2.4
N 0.9 2.8 0.2 1.0 1.6 2.9 1.1 2.3 1.2 2.4
46.1 2-1.4 41.8 22.0 41.0 23.0 42.4 20.8 43.2 Cl
0 25.8
:"'1
Fe 0.16 0.8 0.05 0.08 0.13 0.8 0.1 0.1 0.1 0.08 o:7
0
Si
AI
0.32
0.038
0.6
0.06
0.2
0.01
0.5
0.02
1.09
1.38
1.6
0.7
0.9
1.2
0.8
0.5
0.8
1.4
1.2
0.7
->r;;
~
0.1 0.2 0.31 0.8 0.2 0.2 0.4 0
Mg 0.17 0.3 0.3 <
Ca 0.56 0.6 0.3 0.4 0.67 1.2 0.5 0.9 0.6 1.2
Mn 0.003 0.01 0.01 0.02 0.08 0.6 O.o.t 0.2 O.o.t 0.3
Cu 0.27 4.2 0.1 4.2 0.2 3.9 0.3 3.6 0.4 3.9
n 0.03 0.02 0.001 0.01 0.08 0.08 0.02 0.02 O.o.t 0.06
V 0.22 0.8 0.15 0.21 0.8 0.8 0.2 0.2 0.8 0.9
Cr 0.2 0.7 0.2 0.2 0.08 0.08 0.02 0.02 0.07 0.09
Ni 0.3 0.4 0.3 0.3 0.07 0.07 0.04 0.09 0.09 0.12
• Without copper
"' With copper
TABLE 76
Composition of Sediments Formed in Fuels Free from l\licroimpurities (160 °C, 4 hrs)
RT TS·l T-6 DS DL
Element
composition, % a b a b a b a b a b
0
c 66.8 36.9 64.1 35.1 64.9 39.9 65.1 38.2 64.2 38.4
"z>
Cl
s
H 6.3
2.4
5.6
4.1
5.9
4.6
5.9
9.2
6.2
2.3
5.2
3.2
6.0
2.3
5.0
4.0
6.3
2.4
5.2
4.8
-
()
VI
c::
N 0.9 2.4 0.9 1.0 1.1 3.1 1.2 1.6 1.3 1.2 !""
24.2 42.1 24.3 43.4 20.0 44.3 22.4 43.3

2
0 23.4 46.1
Fe 0.01 0.02 0.01 0.03 0.06 0.01 0.01 0.01 0.02 0.03
"
()
0
::::
"1:1
Si 0.03 0.03 0.03 0.07 0.04 0.03 0.02 0.06 0.07 0.08 0
AI 0.01 0.01 0.01 0.09 0.03 0.07 0.02 0.07 0.03 0.04
~
VI
Mg 0.01 0.02 0.07 0.07 0.02 0.01 0.03 0.02 0.04 0.06 0
'T1
Ca 0.03 0.05 0.09 0.02 0.09 0.07 0.07 0.08 0.05 0.06 "1:1
m
Mn 0.001 0.002 0.01 0.001 0.01 0.01 0.02 0.04 0.03 0.04 ~
0
Cu 0.01 4.2 0.02 5.3 0.1 4.0 0.02 4.3 0.01 4.7 !""
m
0.001 0.001 0.02 0.01 0.001 0.002 0.003 0.001 0.03 c::
Ti 0.001 ::::
V 0.06 0.06 0.09 0.11 0.1 0.01 0.01 0.02 0.002 0.02
Cr 0.01 0.01 0.07 0.09 0.01 0.01 0.02 0.03 0.02 0.03
Ni 0.01 0.01 0.01 0.09 0.01 0.01 0.02 0.04 0.07 0.07
• Without metal
b With copper
....
(;..)
-..1
338 G. F. BOLSHAKOV
1080-1120-1200 cm- 1 region with a main maximum at 1120 cm- 1 , a sharp band at
690 cm- 1, a broad band of medium intensity in the 1610-1720 cm- 1 region and weak
absorption at 880 and 770 cm- 1• The intense absorption in the 1080-1120 region in
combination with the 630 cm- 1 band is in good agreement with the corresponding
characteristic bands of ionized sulfates (So~-: 1080-1130 and 680-610 cm -I; HS04:
1130-1160, 1080-1000, and 880-840 cm- 1) and ionized sulfonates (1080-1100 and
7()()-600 cm- 1). An especially close similarity is observed in the spectra of sediments
and ionized sulfates (1180-1130 and 680-610 cm- 1). The sulfates were also found by
analytical methods in aqueous extracts of deposits containing minor quantities of
compounds with C=O groups (1720-1740 cm- 1).
Apart from sulfur compounds, aromatic hydrocarbons (first of all those with
unsaturated side chains) contribute much to the formation of insoluble deposits. 119 •224
These sediments contain also some water formed in the oxidation of the starting dry
fuels (absorption bands at 1650 and 3400 cm- 1). This is confirmed by theIR spectra of
sediments consecutively dried at different temperatures. After drying for 3 hours at

120 oc the OH group bands in the RT fuel scdiments become noticeably weaker and
almost disappear after 3 hr drying at 300 °C. One can assume that drying at 120 °C
removes moisture absorbed by the sediment whereas drying at 300 oc leads to the
removal of water of crystallization. It should be noted that after drying the sediments
at 120 and especially at 300 °C, all the bands weaken, except those of the sulfates at
1120-1140 cm- 1 and 630 cm- 1 which become sharper and relatively more intense.
This is understandable since at 300 °C the organic part of the sediments changes much
whereas the sulfates only lose their water of crystallization. Unlike RS0 20Cu0S0 2R
and sulfo compounds, CuS04 decomposes at considerably higher temperatures.
The sediments formed in the oxidation of fuels not exposed to metals consist mainly
(98-99%) of amorphous compounds as indicated by an amorphous halo at 8.02 A.
The occurrence of a few weak lines in the spectrum shows the presence of small
quantities (1-2%) of crystalline compounds in the deposit. The latter seem to be
ashes concentrated in the sediments during the oxidation.
The sediments formed in fuels by oxidation in contact with copper consist of both
amorphous and crystalline compounds (Table 77). The spectrum of the crystalline
phase of the sediments is well consistent with the spectrum of copper sulfate
CuS04 • 5 H20. ,
Under regular service conditions fuels must operate at different temperatures.
therefore it is necessary to study the effect of the temperature on the formation of th~
solid phase in fuels (Fig. 57). The amount of the solid phase being formed is at its
maximum at 160-180 oc. Within the same temperature range maximal copper
corrosion i~ ?bserved. W~en the temperatur7 is raised to 180 oc the optical density
and the actdtty regularly mcrease whereas wtth further temperature elevation these
values decrease considerably. The maximum solid phase formation lies within th
equilibrium boiling range of the fuels, shifting toward higher temperatures for heave
fuels. This should account for the lower oxidation rate at temperatures exceeding thy
equilibrium boiling point of fuels. e
At 140, 150, and 160 oc sediments similar in composition and structure
& · of the spectra of these sediments has been presented
1ormed.119 . A n. ·mterp~etat10n are
above. Wtth mcreasmg temperature, however the characteristic l1'ne 1'nt ·
' enstty
TABLE77
X·Ray Patterns of Sediments Formed in Heating Fuels in the Presence of Copper
(150 oc, 4 hrs)
d..
I
d..
n
I
n
I -d..n I -d..n
TS·1
100 8.0 100 3.898 15 2.543 72 2.019
32 5.921 100 3.630 86 2.403 23 1.891
32 5.615 52 3.240 17 2.351 24 1.814
83 5.249 42 3.029 16 2.188 25 1.764
80 4.993 63 2.725 33 2.131 86 1.624

100 4.638 64 2.637 11 2.073
RT
100 8.1 28 5.019 88 3.240 72 2.428
12 5.942 100 4.649 85 3.021 66 2.076
22 5.668 98 3.863 • 89 2.792 92 2.018
21 5.418 16 3.888 94 2.740 68 1.683
26 5.238 100 3.643 98 2.631
T-6
100 8.3 66 4.627 45 2.796 29 2.189
24 5.485 41 3.886 48 2.718 51 2.023
28 5.482 48 3.623 49 2.653 28 1.888
36 4.985 48 3.236 69 2.483 24 1.835
46 3.013 38 1.684
os
100 8.2 67 4.603 45 2.785 28 2.183
27 5.436 48 3.882 49 2.721 52 2.020
29 5.278 35 3.632 47 2.632 28 1.898
38 4.999 62 3.013 62 2.404 27 1.826
42 1.625
changes thus indicating variations in composition and structure of the sediments. The
1
1200 cm- maximum, absent at 140 °C, appears at 150 °C and becomes the prevailing
one among suJfo compounds at higher temperatures. The absorption maximum
displace~ent from. the 1140 cm- 1 region to 1200 cm- 1 shows that the quantity of
sulfates m the sed1ments decreases sharply, the relative content of sulfonic acids,
....
,----, ,.------.
'd
•
..1:'
~
0
:
p
•
.. §»
~~
•. •
.'
CS
0
t1
•
• •
.....
!1,
...z.· ..::ru
!'I»
•
:...
.. 0
r·.
•a
oil
•an
...
.
!•
.. t ..
·~ ..
! ..
,.------."'~
~
.,.,
..
i;!llJ
~
1- .u
•
...
-;:eoo .:1
"::'
• ,"
. ~-
010 JDO -
..
0
~ ~~~-:-J
!•pera\ure, •c
FIGURE 57. The effect of temperature and time on the thermal-oxidative stability of the fuel TS-1
(A-heating at 1° /min; D-oxidation at 150 °C; C-cooling).
covalent sulfates, and sulfites increasing simultaneously. Based on experimental data

obtained with individual sulfur compounds, it can be stated that the maximum at
1200 cm- 1 is mainly due to the presence of aromatic sulfur compounds the oxidation
of which gives rise to compounds ArS0 3H, ArOS0 2Ar, and Ar02SAr, intensively
absorbing at 1200 cm-•.
The aliphatic compounds, a major source of copper sulfates, do not form
CuS04 • 5 H 20 at elevated temperatures and, therefore, the intensity of the bands at
1140 and 630 cm- 1 weakens. The same data could be obtained with model aliphatic
sulfur compounds. Starting at 180 oc a considerable amount of Cu 2S appears in the
sediment. The quantity of C=O groups {1720, 1740 cm- 1) and C-H bonds (1460,
1378, 2920, 2960 cm- 1) increases with rising temperature. An intense band near
1600 cm- 1 assigned to carboxylic acid salts and aromatic C=C bonds is observed.
The X·ray patterns allow one to conclude that the sediments contain both amorphous
and crystalline components. The largest amount of crystalline phase (15%) was found
in the sediments formed at heating to 160 °C. Further temperature rise from 180 to
200 oc leads to a sharp decrease of the crystalline phase which again increases at
240 °C. At this temperature the crystalline phase spectrum changes. The crystalline
phase of the sedimen~s formed at 140 and 160 oc is mainly represented by copper
sulfate CuS04 • 5 H20. Apart from these, the crystalline phase seems to contain
carboxylic acid salts in quantities increasing from fuel TS·1 to T-6.
The X-ray patterns of the two sediments formed at 180 and 200 °C, respectively, are
similar, but sharply different from the previous ones. The main crystalline phase
components are Cu 2S and Cu 20. The Cu 20 content is maximal in the sediments from
T-6 and minimal in the case ofTS-1. The amorphous portion ofthe sediments consists
of covalent sulfates, sulfites, sulfonic acids and their esters with alcohols and
hydroxy acids. Hydroxyl, carbonyl, carboxyl, and ester oxygen-containing groups and
aromatic rings are also present. No signs of nitrogen compounds occur in the spectra,
although their involvement in the sediment formation is beyond any doubt judging by
the elemental composition of the deposits.
The deposits formed on copper in contact with the fuel TS-1 during the oxidation
are structurally very close to the sediments. The most intense absorptions are found
near 3400, 1180, 1600, and 630 cm- 1 • The absorption at 1180 and 630 cm- 1 gives
evidence for the presence of sulfonic acids and their salts, the absorption at 1600 cm - 1
being indicative of a possible occurrence of carboxylic acid salts. In both the
sediments an.d the deposits formed above 160 oc the signs of the presence of sulfo
compounds gradually weaken, the amount of carboxylic acid salts slightly increasing.
The number of CH bonds is not large in the deposits, but their absorption gradually
becomes more intense.
The solid phase formed in pumping the fuel TS-1 in a plant simulating an aircraft
fuel system is close in composition and structure to the sediments obtained under
laboratory conditions. The organic portion of the sediments is characterized by a
similar content of heteroelements. In the IR spectra the most intense absorption
bands are those corresponding to oxygen- and sulfur-containing functional groups.
The content of ash-producing elements is fairly high.
For the ·utilization in aircraft the fuel is brought in contact with diifferent metals
acting as fuel oxidation catalysts. The experimental studies have shown that the
greatest amount of solid phase is formed in the oxidation of fuels in contact with
copper. In the presence of bronze and brass the solid phase is formed in considerably
lower amounts. Copper and its alloys are also the least corrosion-resistant substances.
Alloyed steel12XH3A and duralumin DIT produce the smallest effect on the stability
of fuels. An increase of the metal surface in contact with the heated fuel increases the
catalytic effect of the metals on fuels (Fig. 58).
Copper is not the only metal involved in the solid-phase formation when exposed to
the hot fuel (Table 78), the same is true of some other metals.
Num.erous ele~ents, the main component~ of ~he metal alloys employed, have been
found m the sed1ments formed by the ox1dat1on of fuels in contact with various
metals. Copper dominates in the deposit ash when fuel is oxidized in contact with
bronze, whereas in contact with steel and duralumin the predominant constituents are
iron and aluminium, respectively.
AJ! thes'~ metals are present in the crystalline parts of the sediments (formed within
the 150-Jl60 oc range) as CuS04 • 5 H20; CuS04; FeS0 4 • H 20; Fe(OH)z;
Fez(S04)J • n H20; Alz(S04h," n ~zO; AI(OHh, sulfonic acid salts and, in consider-
ably lower amounts, carboxylic aetd salts. and carbonates including basic carbo na t es.
Th e appearance o f th ese substances m the solid phase in the fuels and their
subsequent occurrence bet~een the rubbing precision parts of fuel system aggregates
leads, naturally, to extens1ve wear of the latter. Besides these substance
·
s1tes where fi ne part1c· 1es prec1p1tate
· · •
to coagulate into coarser ones. s serve as
10 5 2.5
S/V, cm- 1
FIGURE 58. The effect of metals on the formation of insoluble sediments in the fuel TS-1 (150 °C,
6 hrs}:
1. copper; 2. bronze, VB-24; 3. brass L-62; 4. duralumin DIT; S. steel 12XII3A.
TABLE 78
Composition of Insoluble Sediments Formed by Oxidation of TS·l
in contact with Different Metals, %
1\ldals In contact wllh rud TS·l
Elements VB-14 DIT llXIIJA
c 32.99 27JYJ 26.87

H 5.96 8.38 9.62
s 6.01 7.48 7.80
N 0.21 0.18 0.13
0 49 50 49
Si 0.6 0.7 0.7
At 0.2 3.0 0.003
Mg 0.2 0.07 0.3
Ca 0.7 0.2 0.07
Fe 0.007 0.7 4.2
Mn 0.003 0.002 0.007
n 0.002 0.2 0.02
Cu 4.2 0.02 0.03
VII.2. The Chemical Composition and Structure of the Sediments and Deposits
Formed in Aviation and Automotive Fuel Systems
Fuel-oil radiators intended for cooling the oil with cold fuel are the most important
assemblies of the jet fuel system. For a better heat transfer the radiator tubes are
made of copper alloys. While cooling the oil the fuel is heated to form the solid phase
which is deposited on the cooling surfaces or is partly drawn off the radiator and
trapped in fuel filters. The formation of sediments and deposits in the radiators can
cause serious trouble in jet engine performance.
Apart from in radiators deposits are formed and gradually accumulate in airplane
fuel tanks. In passing the fuel through the fuel system some sediments and deposits
are retained in filters at different filtration stages. In automotive vehicles gums and
deposits are formed in fuel tanks and fuel systems. In this connection it was of interest
to study the chemical composition and structure of sediments and deposits in the fuel
system and to compare the results with experimental data obtained in the laboratory.
The composition and structure of sediments and deposits formed in the fuel sys-
tems of the jet planes TU-134, TU-154, IL-18, IL-62, MIG-21, and MIG-21f and
of the heavy-duty diesel trucks MAZ-200B used both in central districts of the USSR
and under hot climatic conditions have been investigated. Data on the composition of
sediments from fuel tanks and 1st stage screen filters are presented in Table 79.
These data show that the sediments from fuel tanks and those taken from the 1st
stage screen filters are similar in composition. A major part of the sediments contains
ash-producing elements introduced into the fuel during storage, transportation,
pumping, and fueling. A considerable fraction of "ash" elements is introduced with
dust from the atmosphere, which was confirmed by special tests. 223 It is the
atmospheric dust pollution that is responsible for the 12-16% silica found in the
sediments. The fuel is also contaminated with corrosion products of storage,
transportation, pumping, and re-fucling facilities. Iron and other metal oxides get into
the fuel as very fine impurities and then act as coagulation sites for gums and solid
phase particles. The sediments contain up to 7-9% iron. X-Ray diffraction has
established that iron occurs in the sediments as Fe 20 3 , FeO, and, to a considerably
lesser extent, as Fe(OH)z and Fe(OHh. Silicon and sodium are mainly present as
Si0 2 and Na2S04 • 5 H20. The organic constituents of the sediments and deposits
represent only 20-40%.
The IR spectra of scdiments and deposits from aircraft fuel systems (Fig. 59) show
the presence of OH groups (3400-3500 cm- 1), aliphatic CH bonds (2850, 2920,
2960 cm- 1) and aromatic rings (3050 cm- 1). An intense band at 1700 cm- 1 indicates
that the relatively large concentrations of C=O groups, judged by a different pattern
of spectral absorption, are contained in esters, acids, and, to a lesser extent, carbonyl
compounds. Consecutive drying of the sediments at 150 oc and 300 oc led to gradual
weakening of the 3400 cm- 1 band, which is an indication of removal of adsorbed
water and water of crystallization. The IR spectra mentioned above did not provide
much information concerning the presence of sulfur-and oxygen-containing com-
pounds since the latter absorb in the same regions as silicas present in comparable
amounts.
TABLE 79
Composition o( Sediments in Fuel Tanks and 1st Stage Filters
Fuel tanks 1st stage filters

Element l\IIG-2llln MIG-ltr l\IIG·2Ir la 1\IIG-lU

rompositlon, moderate dimatlc la bot moderate dimatlc In bot
% TU-154 11...-18 belt, USSR climate l\IAZ-2008 TU-154 IL-62 belt, USSR cHmate
c 20.5 17.4 19.3 22.3 24.31 20.3 18.4 22.3 24.5

11 5.2 5.2 5.1 5.9 6.82 7.2 6.2 6.7 7.2 ~
s 0.46 0.42 0.12 0.21 0.81 0.58 0.78 0.52 0.62 :"'!
!l'
0.36 0.62 0.58 0.72 0.43 0.26 0.32 0.44 0.48 0
N
0 40.2 39.3 32.3 33.8 38.73 40.9 42.3 39.4 42.3 -
!;;
>
::-;:
Fe 8.2 8.3 6.9 7.0 6.81 8.3 8.7 7.3 8.4 0
<
ea 0.63 0.33 0.78 0.78 0.32 1.1 3.2 2.0 2.1
Si 12.0 14.4 16.1 15.1 16.22 13.1 14.2 17.4 16.2
Mg 1.9 1.8 2.4 1.9 0.88 2.0 2.2 0.9 0.8
Cu 0.06 0.03 0.02 0.01 0.03 0.01 0.02 0.3 0.4
Zn 0.08 0.03 0.06 0.02 0.04 0.04 0.02 0.03 0.08
Na 0.48 1.2 4.2 4.4 4.60 0.6 0.8 4.3 5.2
ote: AJ, Ni, Cr, Mn, 1), Sn, Pb, V are present in amounts ofO.OOl~.Ol%.
Co, W, Zr, Hf, Nb, Ta, Bi, Te, TI, Ge, In, Y, La, Sr, Li, P, Se, Be are absent.
FIG URE59. IR spectra of sediments formed in the fuel systems of the airplanes TU-114 (1), Ml G-21 f (2),
and IL-62 (3), and TU·104 (4,5) and IR spectra of deposits from TU-124 radiators (6,7).
Therefore, the organic portion of the sediments was further extracted in a Soxhlet
apparatus with a 1:1:1:1 mixture of ethyl ether, chloroform, acetone, and ben-
zene. The characteristics of the organic constituents of the sediments are given in
Table 80.
As seen from the data presented the organic portion of the sediments from fuel
systems of various aircraft and automobiles is close in composition. As compared with
the sediments formed at elevated temperatures the organic fraction contains some-
what lower amounts of oxygen and sulfur. In fact, these are the highly polar products
of the oxidation of heteroorganic compounds and unsaturated aromatic hydrocarbons
(Fig. 64), formed in storage and use at comparatively moderate temperatures (up to
70-80 °C). The IR and UV spectra show clearly the presence of aromatic species
(1600, 3050 cm- 1), OH (3400-3500 cm- 1), and C=O groups (1700-1680 cm- 1).
Intense absorption in the 1100-1300 cm- 1 region is an indication of the presence of
sulfones (1300-:-1160 cm- 1), sulfoxides (1050 cm- 1) and, in smaller quantities, sulfinic
'(1090 cm- 1) and sulfonic acids (1260, 1010, 630 cm- 1). Due to a greater polarity and
a considerable dipole moment in the presence of moisture (the collecting role of
which was mentioned earlier107) these gums are absorbed and coagulate on micro-
impurities deposited on tanks and retained in the 1st stage filters. Some of these
substances when exposed to higher temperatures quickly consolidate and form
sediments and deposits.
346 G. F. BOLSHAKOV
TABLE 80
Characteristics or the Organic Fraction or Alrplane and Automobile Fuel Tanks
Element composition IL-62 TU-154 MIG·2H TU·l34 MAZ.lOOB
c 69.44 67.20 69.30 69.88 68.31

11 8.30 8.35 8.98 8.98 7.38
s 5.32 4.55 4.02 3.77 4.25
N 0.81 0.87 1.20 1.26 2.06
0 16.13 19.03 16.50 16.11 18.00
Molecular mass, g 480.3 465.8 468.4 502.6 530.7
Passing through the aircraft fuel system prior to entering the combustion chamber,
the fuel comes in contact with fuel-oil radiators, air supply regulators, and propelling
nozzle regulators heated to high temperatures. Besides, the fuel is heated by dynamic
compression in pumps and automated fuel control units. Calculations and ex-
perimental studies have established that in subsonic airplancs the fuel, before it
reaches the injector, has a temperature of about 90-110 °C and 120-140 oc in the
MIG-21 and the MIG-2lf, respectively. The characteristics of the scdimcnts and
deposits formed in these airplanc fuel system arc given in Table 81.
TABLE 81
Composition or the Solid Phase Formed In Alrplane 1-·uel Systems (Average Data)
lkposlts In ruel Sedlments Inside

Element lkposlts In radiators control units Injector
composition,
% MIG-2U IL-62 TU·I24 MIG·2Ir IL-62 MIG·llr IL-62
c 12.4 14.3 18.4 16.3 11.5 50.3 48.4

H 2.4 2.3 3.4 2.8 3.2 5.3 5.0
s 10.4 12.4 2.2 9.4 12.3 8.9 7.2
N 0.9 0.7 0.07 0.8 0.6 0.4 0.3
0 41.3 39.4 30.1 42.3 40.0 31.1 26.3
Cu 22.4 28.3 18.3 12.3 13.4 0.9 1.2
Fe 0.7 0.6 2.3 7.8 8.6 0.7 0.9
Si 0.09 0.04 2.1 0.9 0.8 0.02 0.04
Ca 0.01 0.02 0.8 3.0 2.7 0.2 0.3
Mg 0.2 0.09 3.0 2.0 3.4 0.8 0.9
Na 0.4 0.7 6.2 4.0 2.3 0.6 0.5
AI 0.6 0.5 0.5 2.5 3.0 0.2 0.3
The deposits in radiators are characterized by a considerable copper and oxygen

content. The organic fraction of the deposits constitutes about 20-30%. Composi-
tionally similar deposits are also formed in automated fuel control units of the fuel , 1
system. The X-ray patterns of the deposits show unambiguously the presence of
copper sulfate, CuS0 4 • 5 H 2 0 {Table 82). Apart from copper sulfates which are the
main components of the crystalline phase the deposits have been found to contain
sodium and iron sulfates as well as iron and copper oxides. The crystalline phase
accounts for more than one half of the deposits.
Intense absorptions in the 110-1180 cm- 1 region, near 630 and 1020 cm- 1 (Fig. 64)
point to the presence of ionized sulfates RS03, i.e., sulfonic acid salts, and possibly
sulfonic acids RS0 3H, in the deposits. No sulfones have been found in the sediments
since the spectra display no absorption at 1300 cm - 1, corresponding to sulfones.
The sediments and deposits contain practically neither sulfonic nor sulfinic acids
since there is no absorption in the 1030-1070 and 1090 cm- 1 regions, respectively.
The absorption near 1400 and 1110-1190 cm- 1 should be assigned to the covalent
sulfates, R 10S020R2 , and sulfonates, R 10S0 2R 2 •
The absorption near 1110 and 1180 cm- 1 may be an indication of the presence of
sulfinic esters, R 1S02 R 2 , and sulfites, (RO)lSO.
Compounds of the type RSOj, RS0 3H, R 10S02R 2 , R 10S0 20R2 , R 1S02R 2 and
(RO)lSO occur in very small amounts since the spectra contain poorly defined
absorptions of C-H bonds of the hydrocarbon backbones of these compounds.
Thus, it is reasonable to assume that the strong absorption of sulfur- and
oxygen-containing functional groups is due to the presence of predominantly sulfates
in the sediments. The sulfates are characterized by a well-defined absorption pattern
in the 610-680 and 1110-1200 cm- 1 regions which is found in the spectra of the
sediments. Comparison of the spectra of individual sulfates and those of the
sediments (Figs. 59 and 60) allows the conclusion to be drawn that sulfates of various
metals such as Cu, Na, K, Fe, etc. are present in the sediments (Table 80). Along with
the sulfur- and oxygen-containing compounds mentioned above the sediments contain
carboxylic acid salts. This is evidenced by a rather intense absorption in the
1600-1620 cm- 1 region (asymmetric stretching vibration) which in combination with
moderate absorption near 1400 cm- 1 (symmetric stretching vibration) shows the
#0
presence of RC~ groups. The absorption near 1600 and 1400 cm- 1 is typical for
'a-
carbonates, but the absorption intensity ratios near 1600 and 1400 cm- 1 observed in
the spectra of the sediments imply a predominant content of carboxylic acid-salts.
The relative content of sulfates in the sediments seems to be higher than that of
carboxylic acids judging by the relative intensities of the absorptions in the corres-
ponding spectral regions.
In the spectra of the sediments the organic part is poorly expressed due to its
relatively low content. This required further isolation, separation, and study of the
organic substances. The latter were consecutively extracted with benzene ethanol
and acetone in a Soxhlet apparatus. ' '
~~ ben~ene fraction (Fig. 61) mai?ly consists of neutral aromatic compounds.
Tb1s 1s evtdenced by strong absorption of aromatic C=C bonds (1600 cm-1)
absorption of C-H bonds in aromatic structures (3050, 3070, 750, 820, 870 cm-1)
TABLE8l
X-Ray Patterns of Deposits In Alrplane Fuel Systems
Radiators Automated fuel control unit
MIG·%11 n..6l ~IIG·lll IJ....6l
I
da
D I -dan I -
da
n I -dan
100 8.200 so 8.01 53 8.12 52 8.20
18 5.947 32 5.900 22 5.942 20 5.426
28 5.650 31 5.612 23 5.600 23 5.271
29 5.408 83 5.200 28 5.412 24 5.204

28 5.249 83 4.903 29 5.250 80 4.904
20 5.008 100 4.628 32 5.009 100 4.820
100 4.629 100 3.821 100 4.628 100 3.842
90 3.892 100 3.622 93 3.823 100 3.620
10 3.820 52 3.270 100 3.820 52 3.200
100 3.628 42 3.060 100 3.629 44 3.083
80 3.242 20 2.911 82 3.428 22 2.971
82 3.022 28 2.700 84 3.022 42 2.710
90 2.793 60 2.628 92 2.798 62 2.621
92 2.700 10 2.543 90 2.628 10 2.380
90 2.632 12 2.471 73 2.400 18 2.472
72 2.407 20 2.304 32 2.382 23 2.358
12 2.182
30 2.072 40 2.131 40 2.073 40 2.132
23 2.018 22 2.011
so 1.968 15 2.073 70 2.000 15 2.080
68 1.868 70 2.018 82 1.968 40 2.019
20 1.725 100 1.967 12 1.832 23 1.968
23 1.620 12 1.868 14 1.760 24 1.828
23 1.765 25 1.768
24 1.600 80 1.624 80 1.620 82 1.625
23 1.500 20 1.510 23 1.515 83 1.5()()
20
BD
~ 60
~40
0
12; 20
-<
~ roo:=============:
60
40
FIGURE 60. IR spectra of individual sulfates:

1-Na2S04 ·10 H20; 2-SrS04; 3-Naz$04; 4-K3Na(S04)z
including monocyclic species (700 cm- 1). Saturated structures are implied by absorp-
tions of CH 3 groups (1380, 2960 cm- 1), CH2 groups (1460, 2920, 2850 cm- 1), and
-(CH2)n-chains (720 cm- 1).
The relative neutrality of the compounds isolated is indicated by the weak
absorption of OH groups (3400 cm- 1) and C=O groups (1720 cm- 1 ). The substances
extracted with alcohol and acetone are of clearly defined acidic character. They
consist mainly of compounds containing OH (3400 cm- 1), C=O (1720 cm- 1 ), C-0
~0
(1290, 1240, 1100-1300 cm- 1) and C-C groups (1240-1290 cm- 1).
"a-
The alcohol and acetone fractions reveal aromatic structures (near 1600 cm- 1)
which can be attributed to aromatic ethers. Acids are found in small amounts as
shown by weak absorption near 950 cm - 1 and a weak absorption region near
2700 cm- 1 • Alcohols (3400, 1000-1300 cm- 1), including phenols (1310-1410, 1140-
1230 cm- 1), are likely to be present in somewhat greater amounts.
The alcohol fraction isolated from the deposits for further investigation was then
separated with a complexing compound. This enabled consecutive isolation with ethyl
350 G. F. BOLSHAKOV
~ ~
80
60
40
20
t~ 90
.. 70
ril
0.50
~JO
< 10
E-1
E-1 90
H 70
::11 .50
f.')
~JO
FIGURE 61. IR spectra of fractions isolated with benzene (1), alcohol (2,3), and acetone (4) from the
deposits formed in TU·124 fuel-oil radiators; (5) deposits washed off with benzene, alcohol, and ethyl
ether. The alcohol fraction is separated with a complexing agent into ether and acetone fractions (2
and 3, respectively).
ether (Fig. 61, spectrum 2) and acetone (Fig. 61, spectrum 3) of the corresponding
finer fractions slightly differing in composition.
In the ether fraction the C=O groups occur in greater abundance and are present
in different functional groups (complicated absorption in the 1700 cm- 1 region,
1100-1300 cm- 1), whereas the OH groups are present in a considerably lower amount
1
than in the acetone fraction (3400 cm- ). The absorption of aromatic species is of
moderate intensity in both cases (1600, 1500, 750, 700 cm- 1), the monocyclic species
(700 cm-1) being predominant among them. Thus, the ether fraction contains mainly
acid esters, the acids occurring in smaller amounts, whereas the acetone fraction is
rich in alcohols, most likely phenols.
Having been freed of the organic substances with polar solvents the sediment is, as
should be expected, very similar to the initial solid phase. Judging by the spectrum
this sediment is a mixture of various sulfates and carboxylic acid salts, most probably
hydroxy acids.
The sediments formed in the airplane fuel system differ much in composition and
structure from the solids formed on the heated metal surfaces (radiators, automated
fuel control units, etc.) and are characterized by a considerably higher content of
organic matter.
Thus, the sediments and deposits formed in airplane fuel systems consist of
crystalline and amorphous phases. The crystalline phase accounts for 30-60% and
mainly consists of CuS0 4 • 5 H 2 0 and copper salts of sulfonic acids. Iron, silicon, and
aluminium oxides as well as sulfonic acid salts and sulfates of the above metals are
minor constituents of the crystalline phase. The penetration of the crystalline
substances into the rubbing precision couple may lead to rapid wear of the latter and
to blockage of the fuel system.
The amorphous phase consists of compounds containing C=O, 0-H, S0 3H,
OS0 20, S0 20, S02 , COO, COOH, and CH(OH)COOH groups. The sediments
and deposits contain aliphatic and aromatic species as well as adsorbed water and
water of crystallization.
VII.3. The Chemical Composition and Structure of Deposits Formed in the Cooling
Systems of Rocket Engines
At present hydrocarbon fuel is widely used as a cooling fluid in rocket engines. As the
fuel is moving in the rocket engine cooling system it is heated up to 200-250 oc and
oxidized with dissolved air to form gums and a solid phase. The gums and deposits
adhere to the walls of the cooling tracts and considerably deteriorate, due to poor
heat conduction, the heat transfer from the walls to the coolant. For a better heat
conduction the cooling tracts of most engines are made of copper which intensively
catalyzes the fuel oxidation.
Pertinent research has dealt with the sediments and deposits from the cooling
system of the full-scale rocket engines JRD and RD-107 intended for launching
satellites into space,225 which worked on hydrocarbon fuel and liquid oxygen under
both stand and regular service conditions. After operation in the test bed during 400
seconds the rocket engine cooling system was opened up and the sediments and
deposits were separated and examined after washing with isopentane. The sediments
and deposits formed in the cooling system under real service conditions were sampled
after the corresponding stage of the space rocket had landed. The characteristics of
the deposits are given in Table 83.
The IR spectra of the deposits are similar to those of the solid phase formed under
laboratory conditions and in the fuel system of airphanes. 131 The IR spectra show a
well-pronounced absorption of OH (3400 cm- 1) and C=O groups (1680-
1700 cm- 1). The positions, shapes, and relative intensities of the main absorption
bands at 630, 1030-1100, 1200, and 1300-1400 cm- 1 are indicative of the presence of
various sulfo compounds, among which sulfates, .covalent sulfonates and sulfates,
sulfonic acids, and sulfones are predominant. The intense band at 1610-1600 cm- 1
352 G. F. IJOLSIIAKOV
TABLE83
Composition or Deposits from a Rocket Engine Cooling Syslem
Element c:ompmition, ~ Afier taptlve test AOer satellite landing
c 25.1 24.1
ll 3.4 3.3
s 3.2 2.9
N 0.9 0.8
0 29.3 28.8
Cu 1\.l 9.8
7.3 6.2
Fe
Ca 2.1 1.5
AI 0.6 0.9
Mg 0.8 0.7
Si 3.2 3.4
Ti 0.04 0.08
V 0.6 0.7
Cr 0.6 0.4
Ni 0.9 0.3
Note: Sn, Mn, Co, Da, Cd, Di, De, P. Ag. Au, Sr, Pt are present in minor amounts (0.001-0.0001%).
gives evidence for the presence of aromatic species and ionized carboxyl groups, i.e.
salts of carboxylic acids. If RCOO were absent, the 1600 cm- 1 band intensity would
be considerably lower with the absorption pattern available. The IR spectra contain
absorption bands at 2850. 2920, and 2960 cm- 1 corresponding to C-H bonds of
aliphatic CH2 and CH 3 groups.
The con_lplicated UV absorption in the 250-280 m~t region indicates that some
aromatic species of different degree of saturation are present in the sediments.
The crystalline phase represents about 40-50% of the deposits. The main con-
stituents of the crystalline phase are copper sulfates (Table 84) as well as sulfonic acids
and carboxylic acids. Iron oxides and salts and silicates and oxides of other metals are
present in smaller amounts. The composition and structure of the amorphous part of
the sediments are in many respects analogous to those obtained under laboratory
conditions.
Thus, the composition and structure in the rocket engine cooling system are similar
to those in the sediments and deposits formed under laboratory conditions with
exposure to copper; they differ only in a higher content of ash-producing elements
which is due to contamination of the fuels with corrosion products and atmospheri~
dust in storage, transportation, pumping, and aircraft fueling.
TABLE 84
X·Ray Patterns or Deposits from Rocket Engine Cooling Systems
I -
da
n
I -dan I
d ..
-n I -da
n
Captive rocket engine

58 8.04 100 4.629 90 2.792 62 2.032
28 5.948 90 3.828 80 2.624 84 1.958
40 5.630 100 3.820 68 2.400 70 1.834
29 5.423 100 3.620 33 2.348 30 1.760
40 5.323 80 3.410 40 2.062 100 1.620
34 5.000 70 3.012 23 2.011 24 1.515
RD-107 rocket engine

100 8.210 100 4.628 92 2.782 53 1.928
23 5.930 92 3.830 83 2.700 62 1.832
29 5.600 10 3.812 70 2.622 24 1.708
40 5.399 100 3.620 73 2.408 28 1.607
42 5.250 82 3.240 32 2.073 25 1.600
30 5.080 80 3.012 23 2.009 30 1.498
Vl1.4. Mechanistic Aspects of Sediment Formation in Metal·Free Oxidation of

Hydrocarbon-Sulfur Compound Mixtures
The experimental and theoretical studies conducted 119 have allowed a better under-
standing of the mechanistic aspects of the formation of sediments in fuels representing
mixtures of alkane, cycloalkane, and aromatic hydrocarbons with sulfur compounds
of various structure.
All sulfur compounds inhibit the oxidation of hydrocarbons by reacting with
hydroperoxides which afford radicals in degenerative-branched reactions. As shown
above, the facility of the sulfur compound reaction with hydroperoxides and,
consequently, the inhibition efficiency depend on the sulfur compound structure and
therefore are governed by the sutfur compound reactivity. Mercaptans are the most
reactive sulfur compounds with respect to hydroperoxides. Since alcohols, sulfoxides,
and water have been found among the primary products of oxidation the reaction
most probably proceeds as follows:
ROOH + RSH- RO• + Rs· + H 20 + 2 kcal/mole
Ro· + RSH- ROH + Rs· + 31 kcal/mole
Rs· + Rs·- RSSR + 71 kcal/mole
It is easy to show that the enthalpy changes in these reactions are favorable. As
known, the energies of RO-OH and RS-H bond breakage are 32 and
82 kcal/mole, respectively, those of the H-OH, RO-H, and RS-SR bonds being
116, 103, and 71 kcal/mole. 154 Thus, these reactions are exothermal with a L\H of
3S4 G. F. BOLSHAKOV
100 kcal/mole and their energies of activation are rather small. The formation of
sulfoxides from mercaptans is also exothermal; however, this reaction fails to explain
the appearance of water among the primary oxidation products:
ROOH + RSH- ROH + RSH + 89 kcal/mole
11
0
The disulfides formed react readily with hydroperoxides:
RSSR + ROOH - RSSR + ROll + 89 kcal/mole
11
0
The reactions of hydroperoxides with other organic sulfur compounds, although
less facile, proceed in a similar way:
ROOH + RSR ROH + RFtR

0
ROOH + RSSR ---+- ROH + RffSR
0
ROH + l7JR
In the s~lfoxides the sulfur atom becomes tetravalent. However, owing to the
specific structure of the valence shell of sulfur atom electrons, t the sulfoxides are also
able to break the oxidation chain, though less readily than the starting sulfur
compounds. When sulfones are formed all lone electrons become shared and the
sulfones cannot inhibit the oxidation processes.
Let us compare the kinetics of oxygen consumption for oxidizing the fuel T.7
(Fig. 62) with and without sulfur compounds which decompose hydroperoxides.
The oxidation of the starting fuel T•7 takes place according to:
d[02] = d[ROOH] = k(RH]· J[ROOH] (1)

dt dt
[~J ,
obtain
Introducing the dimensionless variables 1r =
1 T = k1t, and l = l~~], we
dl
- = 2f;
d-r (2)
If all the oxygen is taken to be consumed in the formation of hydroperoxide, then
l = 1T = 'T2.
f The di-, tetra-. and hexava!ent st~te is known to correspond to 3s23p", 3s23pJ3d and 35 13 3 2
electron configurations, respectively, m the valence shell. P 3d
U«J
t:lo<
..
~-
-
~-
rz:l
...:!
~-
E-1
!!!j:l.j«<I
2 6
OXIDATION TIME, hr
l .
FIGURE 62. The effect of sulfur compounds on oxidation and formation of the solid phase in the fuel
T-7:
T-7 + diphenyl disulfide (1), diphenyl sulfide (2), thiophenol (3), di-s-octyl disulfide (4), 2-octane-
thiol (S), 2-decylthiophane (6).
- Oxidation without contact with metals.
--·Oxidation in the presence of copper. (The scale is on the right hand side.)
In the presence of sulfur compounds, the hydroperoxide accumulation rate is
d[ROOH] = k2{RH) - J[ROOH)- k3[ROOH]·[SC] (3)

dt
or
dw ~SC] 1 (1 -e -1)T)2 (4)

dt = 2 (Jw- f3w), f3 = J[RH) w=nl
f3
1
If sulfur compounds are added in sufficiently large amounts, w __,. Wmax = ,
132
f3 = const and the oxygen consumption rate in the presence of sulfur compounds is as
follows:
dT 2 2 (T/3- 1) + C-tJT
2 = 2wl/2
dT
= -{J (1 - e-131 or { = 2 (5)
With 13· T ~ 1 (6)
Since in the oxidation of hydrocarbon mixtures with sulfur compounds

[RH] = const, it may be assumed that &= k1Vo2 and thus
ktt 2
&= 213kl - 132kl = at +b (7)
kt 2
where a = 2 k1 and b = /32k1
13
can be obtained.
The "a" and ••b" values were obtained from the experimental data at the initial
stage of oxidation (Table 85). It is quite evident that the parameter "a" may serve as a
criterion for evaluating the sulfur compound inhibitory effect in the oxidation of
hydrocarbons since, with a close "b" value, this parameter determines the slope of the
oxygen consumption curve with respect to the ordinate axis. The sulfur compound
inhibiting effect in the hydrocarbon oxidation increases with increasing rate of its
reaction with hydroperoxides. This rate is maximal with mercaptans and minimal with
thiophenes, therefore aRsu ~ a 0s Other properties also provide evidence for the
high reactivity of mercaptans. Thus, the constant (k) of the reaction with isopropyl-
benzene hydroperoxide also turns out to be maximal in the case of mercaptans and
minimal with thiophenes (Table 86).
The irreversible oxidation potentials are maximal with thiophenes and minimal
with mercaptans. Thus, the irreversible oxidation potential (b) is 0.216 for 1-
nonanethiol, 0.328 for dioctyl disulfide, 0.348 for dioctyl sulfide, 0.390 for diphenyl
TABLE 85
Parameters a and b in Equation (7)
Sulfur compound(s) concentration

Compound added to fuel T-7 recalculated for sulfur, o/o a b
4Ht9SH 0.005 0.019 1.98

0.010 0.014 1.45
0.200 0.024 1.49
C6HsSH 0.005 0.017 1.93

0.010 0.018 1.82
0.200 0.065 3.16
C6HsSSC6Hs 0.100 0.042 2.03
0.200 0.098 1.96

C8H17SSCsHt7 0.100 0.038 2.00
0.200 0.069 2.07
C6HsSC6H5 0.200 0.049 2.34
CsH 17SCsH 11 0.200 0.053 2.02
G S C611u 0.200 0.119 1.49

f)(c,n,
"'s 0.200 0.432 2.28
sulfide, 0.416 for thiophene, and 0.408 for 2-methylthiophene. The c-s bond in
thiophene is the shortest one (1. 74 A) as compared to that in other sulfur com-
pounds (1.82 A), the C=C bonds (1.35 and 1.44 A, respectively) being close to the
aromatic ring C · · · C bonds (1.39 A).
TABLE 86
Effect of Sulfur Compound Structure on the Constant of Interaction
(k, 1/mole·min) with lsopropylbenzene llydroperoxide (150 oc, n-hexadecane)
Compound k Compound k
C8H17SH 560 . [Ct>HsCH2Sh 240

C6H5SH 230
C6HsCH2SH 420 Q-c6Hn 780
C8 H11SCsll11 120
C8Ht7SSCsHt7 230 Q-c6Hs 120
C6H,SC6H5 82
C6HsCH2SClhCt,H, 107 0- S C6HI3 30
358 G. F. BOLSHAKOV
On the basis of the experimental data concerning the inhibiting effect the organic
sulfur compounds can be arranged as the following increasing series: thio-
phenes -+ thiophanes -+ sulfides -+ disulfides -+ mercaptans.
The low reactivity of thiophenes can be explained by their specific structure. In
thiophene the sulfur atom is involved in the ring 1r-electronic system, and one of the
hybridization types gives two pd 2-hybrids which are not mutually orthogonal. The
symmetry and energy of these orbitals favor conjugation with 2pz carbon orbitals.
Owng to the "aromatic" sextet of electrons thiophene acquires an "aromatic"
character.
As a result of further thermal-oxidative transformations the oxidation products
contain sulfonic acids which can be formed only by C-S bond cleavage. Only from
mercaptans the formation of sulfonic acids is possible without C-S bond cleavage.
The C-S bond cleavage after the formation of sulfones can be explained by the fact
that the energy of C-S bond cleavage is considerably lower here than that in the
starting sulfur compounds (Table 87).
The experimental data concerning the composition of the intermediates point to the
most probable mechanism for the sulfur compound destructive transformations:
~~~ + o2 (ROOH) RS0 3H + CH 2aCH---R 1 + (R 10H)

0 0
RS02S02R + 02(R100H) RS0 H + CH 2aCH---R + (R 10H)

3
[cfQ~0 1 + o2 (R 100H) -
A small part of the alcohols and carbonyl compounds being formed are oxidized to
the acids and hydroxy acids which were found among the oxidation products. The
~0
primarily formed -so-, -so2-. -S03H, -S02H, -c, , OH, and
0-H
TABLE 87
Energy of Bond Cleavage (0, kcal/mole) In Sulfones and Initial Sulfur Compounds154 ·l30
Compound De-s Compound De-s Compound De s
CH 3-SCH1 73 ± 5 Ct,l15Clh-S02Cl13 49.3 ± 2.3 [C,:J]R 56± 1.5
CH3-S0 2CH1 60.6 ± 1.4 C3H7-SCH1 70 ± 2
C6H5CH2-SCH3 51± 2 C3llr-S02CH 3 45.7 ± 2.3 [r-1]

'-...... /
cl's~
R 37.5 ± 2.5
0
-C~ -containing monomolecular oxidation products are still readily soluble in
'-H(R)
the fuel. Due to the fact that sulfonic acids, hydroxy acids, and alcohols are very
prone to oxidative condensation the reactions proceed readil~ ~o affor~ acidic ?nd
intermediate covalent sulfonates and, to a lower extent, acidic and mtermedmte
esters:
0
11
R-Tt-OR 1 + H20;
0
0 R 0
11 1/ I
RS-0-CH-C + H20;
11 '
o 'oH
/;0 0
RCH---C + R10H RCH-C~
IOH ' OH OH
I ' OR 1
Further thermal-oxidative transformations of sulfonic acids and covalent sulfonates
lead to cleavage of a second C-S bond in sulfides, thiophanes, and disulfides to give
various products including sulfuric acid which readily forms covalent sulfates:
ROS0 2R1 + o 2 (ROOH) RO - so 2 -0H + CH 2 =CH2 -R 11 + (ROH);
HO /0
'//
/s~ + ROH;
HO 0
_f)
0
~ '0H
RCHOsobm . +
I 11
c 0
cf 'oH
An imp~rtant, expe~ime~tally established, fact is that covalent sulfates (and,
correspondmgly, sulfunc acid) are formed only in the oxidation of hydrocarbon
S.Jt.-J
mixtures with organic sulfur compounds where the sulfur atom is not attached to an
aromatic ring carbon. In the oxidation of hydrocarbon mixtures with diphenyl sulfide 9
thiophenol, diphenyl disulfide, and 3-methylbenzothiophene neither covalent sui-
fates, ROS0 20R1, nor sulfuric acid are formed by hydrolysis. This seems to be best
explained in terms of the stabilization of the second C-S bond in Cc,H 5-S · after
cleavage of the first C-S bond in sulfides and disulfides and abstraction of a highly
mobile proton in thiophenol as well as by interaction of the benzene ring 11-electrons
and the valence electrons of the sulfur atom to form the 1r-electrons of the aromatic
sextet.
Further oxidative condensation of bi- and monomolecular products leads to
compounds of molecular weight 500-800. Thorough investigations of the composition
and structure of the solid phase formed by the oxidation of individual aromatic and
aliphatic sulfur compounds in a medium of aromatic and aliphatic hydrocarbons
have made it possible to establish the composition and the structure of the functional
groups contained in these compounds and to suggest their structure.
Aliphatic sulfur compounds with saturated hydrocarbon parts are:
HOOCCI I(Alk)OS020CII(Alk)CII(COOII)OS02Alk
IIOOCCII(Aik)S020Cli(Aik)COOCII(COOli)Alk
AlkCII(COOli)OS020CJI(Aik)COOCII(Alk)AlkS03ll
AlkOS0 2AlkCH(Alk)OS0 20CII(Alk)COOll
Aromatic sulfur compounds with saturated hydrocarbon parts arc:
03SHArOS02ArOCOAlk; liOArS020ArS020Cli(Alk)COOll:
AlkCH(COOli)OS0 2ArCli(OH)AlkCli(Olf)ArS03ll
Aromatic sulfur compounds with aromatic hydrocarbon parts are:
Aliphatic sulfur compounds with aromatic hydrocarbon parts are:
AlkS020CH(COOH)ArOS02Aik:
HOAr(Aik)OS020C(Aik)2ArOS02Aik;
HOAr{Aik)OS020C(Alk)zArCH(Alk)S03H;
HOArOS0 20AlkArOS0 2Alk
The thermal-oxi~ative des.tru~tion of sulfur compounds and hydrocarbons leads

to unsaturated spectes (constltutmg Alk), which favors the oxidative condensation of
these compounds. If one takes for Alk the molecular mass values correspondin
those of the hydrocarbon oarts of the sulfur compounds and the hydrocarbons,gt~~
calculated composition of these compounds is in good agreement with the ex-

perimental data. The compounds resulting from the primary thermal-oxidative
condensation the structure of which is mentioned above are highly polar and display
high dipole moments; in collision they associate and precipitate as a secondary phase
to form a colloidal solution capable of intense light scattering.
The association of the oxidation products occurs due to (a) interaction between
particles U = U8 + Ui + Uo and (b) hydrogen bonding. The coagulability increases
much when aromatic species are present among the oxidation products. However, not
all the oxidized molecules are able to associate. The association occurs only in the
absence of steric hindrance and when the arrangement of functional hetero groups is
favored by steric factors.
The interaction of particles in the oxidation of a hydrocarbon-sulfur compound
mixture is considerably stronger than in the case of hydrocarbons alone. The
calculated energies of intermolecular interaction, U, of oxidized sulfur compounds
are given in Table 88. These are only tentative data since more precise calculations
are rather tabor-consuming and can be carried out only in terms of quantum concepts.
These data allow, however, the comparison of intermolecular interaction values for
different molecules and make it possible to obtain the interaction order in a first
approximation. The main contribution to the interaction between particles is from the
dipole moments.
The dipole moments of the starting sulfur compounds do not exceed 2 D, being
equal to 0.53, 0.67, 0.82, and 0.51 D for thiophene, 2-methylthiophene, 3-
methylthiophene, and 2,5-dimethylthiophene, respectively. 226 Due to this fact as well
as to the absence of either sulfonic acids or their esters among the oxidation products,
thiophene and its homologs contribute the least, compared with other sulfur
TABLE 88
Energy of Interaction Between Some Sulfur Compounds, kcal/rnole
Dipole y=SA y=sA

moment,
Molecular structure D Uo Ua u. u Uo Ua u. u
C6HsSO(OH) 3.23 720.3 103.4 432.9 1256.6 120.3 14.8 70.2 206.3
4HsSOJH 3.77 801.4 110.2 443.8 1355.6 132.8 11.0 44.3 188.1
IIJC:S02C6llsOII 5.32 1082.1 198.4 604.2 1884.7 153.2 21.2 60.1 234.5
lls~OS02C61IsCII3 5.01 1031.7 203.8 583.2 1738.7 148.0 19.9 58.2 226.1
C10H,S020~H 5 4.94 1020.1 200.3 602.3 1823.7 140.2 18.1 57.3 215.6
4HsS020C6HsCHJ 6.02 1380.2 232.1 702.3 2314.6 158.3 17.3 60.2 235.8
~HsS02C~Is 5.45 1120.3 182.3 503.2 1805.8 123.4 16.2 50.3 189.9
~HsOS02 ~Hs 5.28 1100.4 172.8 532.1 1805.3 132.4 17.2 48.2 197.8
CsHuS02Csllu 4.53 1030.2 158.2 432.1 1620.5 143.2 18.2 44.2 205.6
CsH a1S02CsH 11 4.50 983.2 148.2 400.2 1531.6 138.2 11.2 48.8 198.2
compounds, to the formation of the solid phase. With increasing oxidation number
of the sulfur atom the dipole moments enhance considerably. Especially high dipole
moments are observed in covalent sulfonates and sulfates (Table 87). Therefore, in
advanced stages of sulfur compound oxidation the solid phase formation becomes
more intense. It should be noted that the dipole moments in sulfur compounds are
significantly higher than in oxygen compounds with a similar hydrocarbon backbone.
The dipole moments of p-hydroxybenzoic acid and p-hydroxyphenyl methyl sulfone,
for example, are 2.73 and 5.32 D, respectively. Accordingly, the energy of sulfur
compound intermolecular interaction is higher (Table 87). At the same time, the
hydrogen bonding possible in species of the type S=O · · · · · HO-S and
S=O · · · · · HO-C is very essential for the coagulation processes. The energy of the
hydrogen bonding in benzenesulfonic acid measured by Raman spectroscopy is
approximately 5.7 kcal/mole.
Particles of a radius of about 200 A are the first to be formed with involvement of
hundreds and thousands of oxidized molecules, tens and hundreds of millions of

particles being formed in 1 ml of the fuel. Once the primary associates have been
formed the coagulability of the particles increases greatly at the expense of their
interaction. The contribution of different forces affecting the interaction between
particles varies depending on the distance. At distances of 5-10 At inductive,
.dispersive, or orientational interactions are operative. As the particles come nearer to
each other, the energy of interaction (U) enhances greatly and hydrogen bonding
begins to manifest itself at a distance of approximately 2.7 A. Simultaneously, in the
presence of aromatic rings, the coagulation of particles strengthens due to the
interaction of ring 7T·electrons. Thus, the process of coagulation acquires a spon-
taneous avalanche character. ·
The experimental results (Fig. 63) show that the formation of particles and the
increase of their radii in the oxidation of hydrocarbon-sulfur compound mixtures
can be described by the following equations: 119
dN
_ = C e-UN/RT. dN
_ = ce-UN/RT
dt t ' dt t (8)
dr = p e-U,/RT. dr
_ = Pe-U,/RT
dt ' ' dt t (9)
These relationships are analogous to the equations reproducing the formation of

deposit particles during the oxidation of fuels free from heteroorganic compounds. 119
Thus, from a physico-chemical viewpoint, the coagulation processes are of general
character in the oxidation of pure hydrocarbon fuels and hydrocarbon-sulfur com-
pound mixtures. In the oxidation of hydrocarbon-sulfur compound mixtures
however, the coagulation parameters are sufficiently different from those for the oxi:
dation of pure hydrocarbon fuels. Table 89 and Fig. 63 show, as an example, the
P,, C,, and U values experimentally defined in the oxidation of fuel T-7 in the
presence of added sulfur compounds. The energy of activation of the coagulation
t At these distances repulsion forces are not operative.

~
7,f
ID
FIGURE 63. The dependence of tg- ~and tg -!.on 1 1, tgCteu, U in the oxidation of the fuel T-7
t t
with added diphenyl disulfide (1), diphenyl sulfide (2), thiophenol (3), di-s-octyl sulfide (4), 2-octanethiol
(5), and 2-decylthiophane (6), (A-oxidation without metal; B-oxidation with copper).
TABLE 89
Parameters of Solid-Phase Particle Coagulation Processes in Oxidation of Sulfur
Compound Modified Fuel T•7
diphenyl diphenyl dioctyl 2· 2-decyl-

Parameters disulfide sulfide thiophenol sulfide octanethiol thiophane
no contact with metals

C., sec- 1 1.05·109 2.85·109 1.14 ·109 1.95 •107 1.38·10S 2.19 ·107
UN, cal/mole 3.85 ·to-' 4.64 ·1o-' 4.15 ·1o-' 1.82 ·1tP 3.78 ·lo-' 1.95 •1tP
P,, A/sec 3.94·tOZ 6.76·10Z 4.76·10Z 31.60 22.91 29.31
Uu cal/mole 3.36·ttP 4.23 ·1o-' 4.05 ·1o-' 2.09 ·to-' 2.t5 ·1o-' 2.28 ·to-'
in contact with copper
C., sec- 1 1.135 •10 10
t.567·1010 l.t22 •1010 5.t88 ·108 4.093•t08 4.093•108
UN, cal/mole 3.661o-' 4.17 t03 3.78 103 2.08 tal 2.36 to-' 2.t3 1o-'
processes is considerably higher in the oxidation of aromatic sulfur c~mpound

containing mixtures. In contrast to the oxidation of pure hydrocarbon fuels, the
presence of copper produces a rather smaller effect on the U value. It is noteworthy
that the U values calculated by equations (8) and (9) turned out to be rather close.
The minimal U value is obtained in the oxidation of T-7 in the presence of added
aliphatic sulfur compounds. When T-7 with added di-.s-octyl sulfide, 2-octanethiol,
and 2-decylthiophane is oxidized in the presence of copper (curves 4,5,6; Fig. 63), the
increase in the particle radius, r, on section A is described by experimental data using
the following equation:
r = u(T - To) + ro (10)
where u is the constant equal to the straight line slope to the abscissa axis, A/K; r0 is
the particle radius at T = T0 , in A; T0 and Tare the initial and working experimental
temperature, K, respectively. Equation (10) is a partial case of (9). In fact, if
r - ro = p r c RTu dt
JT (11)
(12)
then by expanding the subintegral function and integrating (11) we get
r - ro = p(T - T 0 ) (13)
It is quite evident that (13) and (10) are identical. This condition holds when
U~RT.
Thus, in the coagulation the solid particles overcome a potential barrier which is the
energy of activation of the coagulation processes (U in equations (8) and (9)). It is
most probable that the particles must overcome this potential barrier when they are
10-18 A apart. At these distances the van der Waals forces are still negligible since
they are proportional to r- 6 • Upon the coagulation of particles, however, the entropy
of the system increases, being considerably greater in the case of aromatic sulfur
compounds. Since C = Be4.SIR, the entropy gain in the coagulation of particles in
the process of oxidation of T-7 and d~henyl disulfide, for example, without contact
with metals is Sdiph - ST-7 = R In (Ct">ct /Cf'7) = 12.9 cal/degr mole, whereas that
for T-7 with dioctyl sulfide is Sdioc:t - ST·7 = R In (Ctioc:t /Cf'') = 58 cal/degr mole.
When the oxidation occurs in contact with copper, the AS values are 17.7 and 11.5
cal/degr mole, respectively. Analogous data have been obtained for other sulfur
compounds as well. This essential entropy gain can be explained in terms of greater
affin~ty of aromatic species to association in the process of oxidation in an aliphatic
medmm.
Sulfur c~mpou~d adsorption ~n copper-containing matter considerably reduces
the pote~ttal barner. for coagulatton created by copper compounds in the oxidation of
T-7. Thts fact requtres further thorough investigations.
Since the interaction between particles is governed, first of all, by the structure of
the sulfur compounds and the hydrocarbon medium, the coagulability of particles
depends greatly on the structure of the hydrocarbon medium, the hydrocarbon
backbone, and the sulfur- and oxygen-containing functional groups. In fact, the
maximal affinity to association, coagulation and, finally, to the formation of the solid
phase is manifested when the hydrocarbon backbone of the sulfur- and oxygen-
containing oxidation products is structurally opposite to the hydrocarbon medium,
i.e., when aromatic sulfur compounds are oxidized in an alkane or cycloalkane
medium. And, vice versa, the products of aliphatic sulfur compound oxidation
precipitate fast when they are oxidized in an aromatic medium. Hence, a very
important conclusion can be drawn. In mixing and subsequent refining of oils or
distillates for producing jet fuels one should avoid mixing fractions with hydrocarbons
structurally sharply different from the hydrocarbon backbone of the heteroorganic
compounds. Mixing of fractions and oils of the alkane and aromatic typest will lead to
fuels more prone to the formation of insoluble deposits and gums.

Based on the reactivity of the sulfur compounds and the tendency of their
oxidation products towards oxidative condensation all sulfur compounds should be
arranged in the following order: thiophene < alkylthiophenes < thiophane <
alkylthiophanes < sulfides < disulfides < mercaptans. It should be mentioned,
however, that, depending on the hydrocarbon medium structure, the effect of the
sulfur compound hydrocarbon backbone may prove to be considerably greater
than the effect of the corresponding functional groups of the sulfur compounds as
such.
It has been shown by X-ray diffraction that the sediments formed by the oxidation
of fuels free from microimpurities out of contact with metals are amorphous. On the
basis of all the relevant research carried out a reliable scheme for the formation of
the solid phase in the oxidation of sulfur compound-hydrocarbon mixtures can be
suggested (Fig. 64). A general kinetic equation and a mechanism for the formation of
colloid systems in the oxidation of fuels have been presented and discussed.l1 9
Under actual service conditions it is not possible to avoid all contact with metals.
This intensifies the formation of insoluble sediments in the oxidation of fuels which
then adhere to the metal surface.
VJJ.5. Interaction of Organic Sulfur Compounds with Metal Surfaces and Antiwear
Properties of Fuels
Most scientists believe that heteroorganic compounds interact with the metal surface
via functional groups alone such as SH, NH2 , CO, and COOH. It is also
227 228
assumed • that the hydrocarbon part of the molecule is located above the metal
surface and does not come in contact with it. However, the research carried out by the
present author for the latest years allows the statement that the molecules of sulfur
! As sh~wn ~hove, the fractions of the alkane type oon~ain heteroorganic compounds predominantly
wtth an ahphat1c hydrocarbon backbone whereas the fracttons of the aromatic type are characterized by
the presence of heteroorganic compounds possessing mainly an aromatic hydrocarbon backbone.
366 G. F. BOLSHAKOV
FIGURE 64. A simplified scheme of the solid-phase formation in the oxidation of sulfur
compound /hydrocarbon mixtures.
compounds as well as those of other heteroorganic compounds, when interacting

with metal, are oriented parallel to its surface.
The metal surface can be conventionally represented as an ionic lattice "submerged
in electronic liquid". This surface should be modelled in the first approximation as a
plane with regularly alternating positively or negatively charged sections. The
hydrocarbon part of sulfur compound molecules, especially one with 7T-bonds, also
is electrically non-uniform. Consequently, nothing prevents the hydrocarbon
part/metal surface interaction. This is confirmed by experimental data. In contact
with copper, hydrocarbon solutions of aromatic, unsaturated, and saturated sulfur
compounds form films of different thickness. At 160 oc during 8 hours diheptyl
sulfide, dihexyl sulfide, and diphenyl sulfide, for example, form films 10, 80, and
180 mp. thick, respectively .119
The dynamic contact potential differences (CPD) also indicate that 7T-bond-
containing compounds are more reactive towards metal surfaces. The CPD values of a
gold (standard) and a steel plate were measured prior to and after the treatment with
sulfur compounds (~PDt and CPD 2 , respectively). The difference, ACPD =
CPD2 - CPD 1 is proportional to a change in electron emission work (EEW) of
300 600 900 1200

r.min
FIGURE 65. The effect of sulfur compounds and hydrocarbons on CPD of steel. 1-diphenyl sulfide;
2-diheptyl sulfide, 3-diphenyl disulfide, 4-dibenzyl sulfide, 5-dibenzyl disulfide, 6-3,6-dimethyl·
benzenethiol, 7-hexadecane, 8-1-octanethiol, 9-1-methylnaphthalene.
opposite sign (ACPD = - AEEW). For comparison, 1-methylnaphthalene, n-

hexadecane, and ethanol were tested under analogous conditions. Sulfides and
disulfides considerably increase CPD. This is due, first of all, to the interaction of the
unshared 3p2 electron pairs of the sulfur atoms with the metal. Since the configuration
of the outer electron layers of iron and copper atoms is 3d64s2 and 3d104s 1 ,
respectively, complexes between sulfur atoms (2p63s23p4) and metals are formed
rather readily by sp-hybridization. This increases the electron density of the metal
atoms and the CPD and reduces the EEW.
The effect of mercaptans is highly specific. Unlike sulfides and disulfides, 1-
octanethiol is an electron acceptor which leads to a decreasing CPD. However, the
CPD increases after transformations of mercaptans on the metal surface. This is
especially pronounced in the case of aromatic mercaptans (Fig. 65).
Destructive transformations of mercaptans on the metal surface may lead to the
formation of various metal-containing compounds such as sulfides and thiolates as
well as of sulfur which can be found in metals at a depth to 30 mJ.L. Like metal oxides
metal sulfides reduce the CPD.
The sulfur compound hydrocarbon skeletal structure significantly affects the
interaction with a metal (Fig. 70). A saturated hydrocarbon fragment, for example,
S.R.-IC
368 G. F. BOLSHAKOV
/
/
FIGURE 66. The interaction of sulfur compounds with metal surfaces: a-diheptyl sulfide, b-
diphenyl sulfide, c-dihexyl sulfide.
displays electron-donor properties and increases the CPD whereas the aromatic and
unsaturated parts of the molecule act as acceptors and decrease the CPD. This is
clearly seen with n-hexadecane and 1-methylnaphthalene. In the C-H bonds the
bonding electron-pair shift towards a more electronegative carbon atom forms a
dipole of approximately 0.3 D. The increased CPD value of steel in contact with
hydrocarbons shows that the latter interact with the metal via predominantly carbon
atoms which are electron donors with respect to the steel. The scheme for the
interaction of unsaturated aliphatic and aromatic sulfur compounds with a metal
surface is depicted in Fig. 66.
In conjugated unsaturated and aromatic sulfur compounds the non-hybridized
p-electron orbitals are orthogonal to the molecular plane and rotate freely about the
molecule since in arenes all p-orbitals overlap.
In arenes and unsaturated compounds (with conjugated double bonds) the w-
electron delocalization should lead to formation of 7T-complexes with metals. The
7T-complexing is especially intense in metals with defects in their crystal lattice (iron,
copper, aluminium, etc.). A possible structure ofthese complexes is shown in Fig. 67.
The transmission of the inductive effect from the sulfur atom through the carbon
chain and transmission of the mesomeric effect in aromatic compounds intensify the
interaction of metal and carbon atoms, especially those located close to the sulfur
atoms, and, finally, facilitate the orientation of sulfur compound molecules parallel
to the metal surface. This orientation enhances the effect of the metal force field on
the second and subsequent molecular layers of heteroorganic compounds in the
lubricant boundary layer.
0 Fe
(}~
9s
J~
~Fe
o Cu {j
(}\)
FIGURE 67. Possible structures of complexes of unsaturated and aromatic sulfur compounds with
metals.
The donor-acceptor effects change the electronic density of the absorbed molecules
and the latter become capable of interacting more readily with the solution molecules.
If the surfactant molecules are arranged perpendicular to the metal surface the effect
of the metal force field on both the orientation of the second and subsequent lubricant
boundary molecular layers and their interaction with the solution molecules is
considerably reduced.
Chemical transformations of natural and individual sulfur compounds in jet fuels
in contact with rubbing metal surfaces have been studied from the viewpoint of
practical application.
The chemical transformations of sulfur compound-containing fuel have been
reproduced on a plant simulating precision units of an airplane fuel system.
Experimental conditions: bulk fuel temperature, 100 oc; average sliding rate,
1.8 m/ s; average load in the friction zone, 4 kg, contact rubbing surfaces, steel
XBH/bronze or steel/ Al-Mg alloy, AMG-SM.
The fuels T-7 and TS-1 were chosen as the subjects of the investigation. After
hydrorefining the fuel T-7 was additionally refined on a silica gel ASK in order to
remove heteroorganic compounds. Then individual sulfur compounds were added to
the fuel and the resulting mixtures examined.
~ J5
H
•
~
< J2
20
f6
12
8..~-.......----r---r_.,.._,..---,--,r---~L..-_,..-..,---.,r--r-~-1
o z 4 6 8·fo·Jo at 0.2 a.J
r.!ERCAPTAN SULFUR DISULFIDE SULFUR
COUTEUT, ~~ COllTENT, %
FlGURE 68. The effect of mercaptans and disulfides on the anti wear properties of the hydrorefined fuel
T-7.
1-phenylmethanethiol, 2-thiophenol, 3-ethylcyclohexanethiol, 4-2-octanethiol, 5-diphenyl
disulfide, 6-dihexyl disulfide, 7-dicyclohexyl disulfide.
The effect of mercaptans on the anti wear properties of T·7 depends on their
structure and concentration (Fig. 68). When the mercaptan sulfur content is about
0.001% the wear is minimal. Further increase in the mercaptan concentration
considerably deteriorates the antiwear properties of the fuel. The same effect is
observed with other sulfur compounds, but at consi~erably higher concentrations.
According to the effect on the antiwear properties the sulfur compounds can be
arranged in the following order: mercaptans > disulfides > sulfides > thiophenes.
The optimum of the sulfur compound anti wear effect follows the same order, shift-
ing towards higher concentrations (Fig. 69). With increasing molecular mass, the
sulfur compound antiwear properties are slightly improved. Some natural sulfur
compounds isolated from TS-1 have also been studied. These sulfur compounds
(mainly the sulfides) turned out to be nearly as efficient as individual sulfides.
The products of the lubricating medium transformation together with the products
of rubbing metal wear have been isolated from the fuel and studied by IR
spectroscopy and X-ray diffraction.
Independent of the material of the friction couples and the structure of the
mercaptans all the spectra (Fig. 70), along with the absorption bands of C-H (2960,
2920,2870, 1460, 1380, and 3100 cm- 1) and C=O bonds (1720 cm- 1) contain also an
H
.
~ 32
28
24
20
t2
0 at 0.2 0.3 OA 0 0.2 0.4 0.6 O.fJ

SULFIDE SULFUR THIOPHENE SULFUR
CONTENT, % CONTENT, %
FIGURE 69. The effect of sulfides and thiophenes on the antiwear properties of the hydrorefined fuel
TS-1.
1-diphenyl sulfide, 2-diheptyl sulfide, 3-sulfides isolated from fuel TS-1, 4-sulfides isolated from
fuel DL, 5-2-hexylthiophane, 6-2-phenylthiophene, 7-2-hexylthiophene, 8-ethylbenzothiophene.
t» ~
~
.411
~a)O
~0
~- 20
~-E-4
4J
60
40
aJ 20
0 0
FIGURE 70. IR spectra of wear products of steel XBH against alloy AMG-SM (1 2) and bronze (3 4) in
fuel T-7 with added thiophenol (2,4) and 2-octanethiol (1,3). ' '
372 G. F. BOLSHAKOV
absorption in the 1200 cm-• region, corresponding partly to C-0 and OH bonds
and, to a greater extent, to S=O bonds (HS04 , SOi-).
The difference in the spectra of the wear products (especially in those for the pair
steel-bronze) provides evidence for a direct participation of the added mercaptans in
the friction and wear processes. The spectrum of the wear products obtained in the
presence of thiophenol is similar in many features to the spectrum of thiophenol (e. g.
absorption at 700, 740, 940, 1000, and 1040 cm- 1 and in the region 1100, 1200, and
1400-1500 cm-•, assigned mainly to the aromatic part of the molecule). The absence
of the intense and sharp band at 2590-2550 cm- 1 is indicative of transformations of
thiophenol. The intense absorption in the 1100-1200 cm- 1 region is caused by the
appearance of S=O bonds.
In the presence of 2-octanethiol the wear products formed consist predominantly of
carboxylic acid salts and carbonates. No absorption bands of aromatic species occur in
the spectrum.
A fairly high intensity of absorption bands at 1200, 1400, and 1600 cm- 1 ,
incompatible with the absorption intensity of bands caused by organic molecules, is an
indication of the possible predominance of various sutfatcs in the wear products
(HS04 at 1180-1160, 1080-1000, 880-840 cm- 1), (Soi- at 1130-1080, 680-
610 cm- 1), and carbonates (Co~- in the region 1450-1410, 880-800 cm- 1).
The X-ray patt~rns of the transformation products from the friction couple
steel-bronze testify to the fact that, independent of the type of mercaptan added, the
crystalline phase contains copper sulfides and copper.
TheIR spectra of the products of metal wear in the detarred fuel TS-1 with natural
heteroorganic compounds added display for a friction couple steel XBH/ alloy
AMG-5M the presence of hydrated magnesium sulfates and, possibly, aluminium
sulfates in considerably smaller amounts.
Thus, the date obtained provide strong evidence for intense sulfur compound
transformations on the friction surfaces, for sulfur compound interaction with the
metals in contact, and the formation of secondary products which determine the wear
rate of rubbing parts.
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G. F. Bol'shakov, "A Study of Oxidized Jet Fuels at High Temperatures" (Leningrad: Izd. Voen.
Akad. Tyla i Transporta), 1966, 206 pp.
120. D. I. Kondakov, N. K. Lyapina, V. S. Nikitina, A. A. Smarkalov, and M. A. Parfenova,
"Extraction of organosulfur compounds from diesel fuel distillates with spent acid from the
alkylation process", Khim. i Fiz. Nefti i Neftekhim. Sintez, 1976, 224.
121. W. M. Douglas (UOP, Inc.), "Catalyst and its use", Ger. Olfen. 1,706,516; Chem. Abstr., 87, 378
(1977).
122. G. Asdigian (UOP, Inc.), "Mercaptan extraction with recycled alkaline solution", US 4,362,614;
Chem. Abstr., 98, 162 (1983).
123. Yu. F. Vysheslavtsev, V. L. Yaschenko, A. F. Molchanov, V. R. Grunvald, B. M. Gal'perin, V. I.
378 G. F. BOLSHAKOV
Latyuk, and T. I. Lysikova (Volga-Ural Scientific-Research Institute for the Ext~actin~. and
Processing of Hydrogen Sulfide Gas), "Isolation of mercaptans from a hydrocarbon nuxture , SU
1,027,156; Chem. Abstr., 99, 706 (1983).
124. L. D. Stakhina and A. N. Plyusnin, "Isolation and separation of oxidation products of high-boiling
hydrocarbon mixtures", lzv. Sib. Otd. Akad, Nauk SSSR, Ser. Khim. Nauk, 6, 138 (1981).
125. G. A. Safonov, V. M. Bembel, L. A. Tsoi, and A. N. Plyusnin, "A new method of isolation of
heteroatom compounds from high-boiling distillate fractions of petroleum", Neftekhim., 198~, 101.
126. V. M. Bembel, G. A. Safonov, and A. N. Plyusnin (Siberian Institute of Petroleum Chemistry},
"Removal of nitrogenous, resinous, and polycyclic aromatic compounds from petroleum products"
SU 941,401; Chem. Abstr., 91, 178 (1982).
127. V. A. Klimova, "Basic Micromethods for Analysis of Organic Compounds", 2nd ed. (Khimiya:
Moscow, USSR), 1975, 223 pp.
128. C. N. Satterfield and G. W. Roberts, "Kinetics of thiophene hydrogenolysis on a cobalt molybdate
catalyst", AIChE J., 14, 159 (1968).
129. C. H. Amberg, "Molybdenum in hydrodesulfurization catalysts," J. Less Common Metals, 36, 339
(1974).
130. V. I. Erofeev, L. M. Koval, and I. V. Kalechits, "Use of a thermodesorption technique to study
hydrogen chemisorption on sulfided Co- and Mo-containing and commercial AI-Co-Mo catalysts",
lzv. Akad. Nauk SSSR., Ser. Khim., 1980, 766.
131. V. I. Erofeev, and I. V. Kalechits, "Study of thiophene chemisorption on sulfided cobalt-
molybdenum and industrial industrial cobalt-molybdenum-alumina catalysts by thermal desorp-
tion", Izv. Akad. Nauk SSSR., Ser. Khim., 1981, SOS.
132. V. I. Erofeev and I. V. Kalechits, "Thiophene hydrogenolysis and catalytic activity of Al20 3-CoO-
Mo03 catalysts and components thereof', Geterogen. Kataliz v Khimii Geterotsikl. Soedin. Tezisy
Dokl. 3-ego Vses. Simpoz., Riga, 1981, 101.
133. R. Z. Magaril, 'Theoretical Principles of Chemical Petroleum Refining Processes" (Khimiya:
134. A. G. Bridge and J. W. Scott, "Resid hydroprocessing", Oil Gas J., 73, 94 (1975).
135. F. Stolfa, R. H. Jensen, and C. W. Selvidge, "Low-sulfur residual fuels by RCD lsomax", AIChB
Symp. Ser., 69, 105 (1973).
136. Anon., "Technology improves for processing sour residua" ,. Oil Gas J., 72, 62 (1974).
137. Anon., "Refiners get big dose of technology", Oil Gas J., 74, 93 (1976).
138. L. A. Godsave and M. K. Eyles, "New B process desulfurizes resid", Oil Gas J., 69, 75 (1971).
139. J. F. Mosby, G. B. Hoekstra, and T. A. Kleinhenz, "Pilot plant proves resid process",
Hydrocarbon Proc., 52, 93 (1973).
140. Inst. Franc. du Petrole, "JEP resid and vacuum gas oil hydrodesulfurization", Oil Gas J., 70, 92
(1972).
141. G. A. Berg, S. G. Khabibulin, A. Ya. Zaitova, Z. D. Putilova, L. A. Katincheva, N. A.
Kochetova, T. S. Kirillov, L. Ya. Skundina, and M. I. Kashina, "Results of long-term tests of the
catalyst KGD0-1 in the hydrodesulfurization of deasphalted vacuum residus", Gidroobesserivanie
Ostatochn. Neft. Syr'ya, 1978, 35.
142. W. L. Nelson, "Catalyst consumption required in desulfurizing residua", Oil Gas J., 74,72 (1976).
143. S. G. Khabibullin, A. S. Eigenson, and A. V. Balaev, "A study of hydrodesulfurization kinetics of
deasphalted vacuum residues", Gidroobesserivanie Ostatochn. Neft. Syr'ya, 1978, 45.
144. A. Voorhies, W. J. Metrailer, C. N. Kimberlin, and C. E. Jahnig, "Improvement in fuel oil quality.
11. Desulfurization of residual fuels", Mech. Corrosion Fuel Improvements, Proc. Intern. Conf.
Marchwood, near Southampton, Hampshire, Engl., 1963, 317.
145. R. A. flinn, H. Beuther, and B. K. Schmid, "Now you can improve residue treating", Petrol.
Refiner, 40, 139 (1961).
146. G. C. A. Schuit and B. C. Gates, "Chemistry and engineering of catalytic hydrodesulfurization"
AIChE J., 19, 417 (1973). '
147. M. L. Vestal and W. H. Johnson, "Chemistry and kinetics of the hydrodesulfurization of coal" in
Desulfurization of Fuels and Combustion Gases", Presentation and discus. of expert papers on
economic methods of fuel gasific. and on fluidized bed combustion, Paper 02, United Nations
Geneva, 16-20 Nov., 1970 (New York 1971), p. 265. '
148. G. A. Beiter and B. K. Schmid, "The mechanism and rates of reactions proceeding during
hydrofining of petroleum residues", Trudy 5-go Mezhdunar. Neftyan. Kongressa, Moscow 1965
(Izd. Tsentr. Nauchno-Issled. Inst. Informatsii i Tekhniko-Ekonom. Issledov. Neftepere'rab i
Neftekhim. Promyshlen. Moscow, 1965), pp. 106-23. ·
149. H. Ozaki, Y. Satomi, and T. Hisamitsu, "The kinetics and economics of hydrodesulphuris'
residual fuel oils", Proc. 9th World Petrol. Congr., 6, London, 1975, 97. mg
150. T. Hisamitsu, Y. Shite, F. M~n:yama, ~· Yamane, Y. S~tomi, and ~· O~aki~ ·:~tudies on

hydrodesulfurization of heavy dtsttllates. Hydrogen consumption and reactiOn kmetlcs , J. Japan
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151. G. F. Froment, "Model discrimination and parameter estimation in heterogenous catalysis",
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152 G. A. Berg. A. S. Eigenson, A. Ya. Saitova, L. I. Volkova, N. A. Kochetova, T. P.
· Andryushenko, V. I. Sokolova, A. A. Ioakimis, L. Ya. Skundina, and T. S. Kirillov, "Effect of
catalyst porous structure on the hydrodesulfurization of deasphalted tar", Gidroobesserivanie
Ostatochn. Neft. Syr'ya, 1978, 103.
153. A. Ya. Saitova, G. P. Andryushenko, G. A. Berg, N. A. Kochetova, L. I. Volkova, A. A.
loakimis, V. I. Sokotova, and F. M. Galiaskarov, "Effect of ratio and content of active metals on
the hydrodesulfurization activity of wide-pore catalyst''. ibid., 1978, 112.
154. L. V. Gurvich, G. V. Karachevtsev, Yu. A. Kondrat'ev, and V. A. Lebedev, "Rupture Energy of
Chemical Bonds. Ionization Potentials and Electron Affinity" (Nauka: Moscow, U~SR}, 1974,
351 pp.
155. C. C. Price and S. Oae, "Sulfur Bonding", Ronald Press, New York, 1962.
156. R. Rahman, S. Safe, and A. Taylor, "The stereochemistry of polysulphides", Quart. Revs. Chem.
Soc. (London), 24, 208 (1970).

157. B. Bak, D. Christensen, L. Hansen-Nygaard, and J. Rastrup Andersen, "The structure of
thiophene", J. Mol. Spectrosc., 1, 58 (1961).
158. L. I. Belen'kii, E. P. Zakharov, and N. A. Kalik, "New Trends in Thiophene Chemistry" (Nauka;
159. E. N. Karaulova, "Chemistry of Petroleum Sulfides" (Nauka, Moscow, USSR), 1970, 202 pp.
160. W. E. Truce, D. P. Tate, and D. N. Burdge, "The cleavage ofsulfides and sulfones by alkali metals
in liquid amines", J. Amer. Chem. Soc., 82, 2872 (1960).
161. V. G. Kharchenko, S. K. Klimenko, and T. I. Krupina, "New transformations of sym·
octahydrothioxanthenes", Zh. Org. Khim., 3, 1344 (1967).
162. R. Appel and G. Buechler, "Reaction of nitrogen trichloride with thioethers", Justus Liebigs Ann.
Chem., 684, 112 (1965).
163. J. L. Kice and K. W. Bowers, "The reaction of some dialkyl sulfides with p-toluenesulfinic acid",
J. Amer. Chem. Soc., 84, 2390 (1962). ..
164. Sh. Mishaui, B. Kumanova, K. Kaishev, and G. Angelova, "Identification of organosulfur
compounds in the 150-200 cc petroleum fraction from the Rum elan field", God. Vissh, Khim-.•
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165. M. V. Likhosherstov, "On the interaction of N-amido halides with thioethers", Zh. Obshch.
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166. G. G. Moore and B. R. Trego, "The reaction of dialkenyl and alkenyl alkyl disulphides
with triethyl phosphite and of dialkenyl disulphides with cyanide ion", J. Chem. Soc., 1962,
4205.
167. M. Grayson and C. E. Farley, "Organophosphorus thioesters from disulfides and primary and
secondary phosphines", J. Org. Chem., 32, 236 (1967).
168. A. J. Parker and N. Kharasch, "Derivatives of sulfenic acids. XXXVI. The ionic scission of the
sulfur-sulfur bond", J. Amer. Chem. Soc., 81, 3071 (1960).
169. M. F. Shostakovskii, B. A. Trofimov, A. S. Atavin, S. V. Amosova, and E. I. Kositsina,
·"Interaction of acetylene and organic sulfides", lzv. Akad. Nauk SSSR., Ser. Khim., 2, 454
(1967).
170. B. A. Trofimov,: 1. K. Gusarova, A. S. Atavin, S. V. Amosova, A. V. Gusarov, N. I. Kasantseva,
and G. A. Kalabin, "Reaction of organic sulfides and acetylene. IX. Effect of disulfide and
acetylene structure", Zh. Org. Khim., 9, 8 (1973).
171. W. A. Pryor, "Mechanism of Sulfur Reactions" (New York: McGraw-Hill Book Co.) 1962,241 pp.
172. K. Halvarson and L. Melander, "Acid-induced hydrogen exchange in thiophene", Arkiv Kemi 8,
29 (1955). •
173. B. V. Aivazov, S. M. Petrov, V. R. Khairullina, and V. G. Yapryntseva, "Physico-Chemical
Constants ?f Organ~sulfur Compounds", (Moscow: Khimiya) 1964, 279 pp.
174. G. F. Bol shakov, Recovery and Quality Control of Petroleum Products" 2nd Ed (Nedra
Leningr. Otd.: Leningrad, USSR), 1982, 350 pp. ' · '
175. N. F. Dubovkin, "Handbook of Hydrocarbon Fuels and Products of their Combustion" (Moscow:
Gos. Energy lzd.) 1962, 288 pp.
176. G. F. Bol'.shakov, "Infrared SpectraofThiols", lzv. Vysshykh Uchebn. Zaved. Neft. Gaz, 1980,39.
177. G. F. Bol sh~kov, E. A. Gl~?ovsk.ay~, and Z: G. Kaplan, "Infrared Spectra and X· Ray Patterns of
Heteroorgamc Compounds (Kh1m1ya: Lenmgrad, USSR) 1967, 168 pp.
380 G. F. BOLSHAKOV
G. F. Bol'shakov and E. A. Glebovskaya, ''Frequency Tables of Infrared Spectra of Heteroorga-

nic Compounds" (Khimiya: Moscow, USSR) 1968, 128 pp.
178. G. F. Bol'shakov, V. S. Vatago, and F. B. Agrest, "Ultraviolet Spectra of Heteroorganic
Compounds" (Khimiya, Leningrad. Otd.: Leningrad, USSR) 1969,. 499 PP·. • •
179. R. M. Silverstein, C. G. Bassler, and T.C. Morril, ''Spectrometnc Identdicatlon of Orgamc
Compounds", 3rd Ed. (Wiley: New York, N. Y.) 1974, 340 pp.
180. "Varian Associates High-Resolution NMR Spectra Catalogue", 2 Vs. Eds. M. G. Howell, A. S.
Kende, and I. S. Webb (National Press, New York, 1962, 1963).
181. H. A. Szymanski and R. E. Yelin, "NMR Band Handbook" (Plenum: New York) 1967, 500 pp.
182. A. J. Gordon and R. A. Ford, "A Chemist's Companion. A Handbook of Practical Data,
Techniques and References" (Wiley-Interscience: New York, N. Y.), 1972, 560 pp.
183. W. Emsley, J. Feeney, and L. 11. Sutcliffe, "High·Resolution Nuclear Magnetic Resonance
Spectroscopy", 2 Vs. (New York: Pergamon) 1966, 488 pp.
184. M. A. Korshunov, V. A. Bukhareva, I. V. Furaeva. and L. V. Khokholova. "Synthesis of tertiary
alkyl mercaptans based on propylene polymers IV", Khim. Seraorg. Soedin., Soderzh. Neftyakh
Nefteprod., 8, 5 (1968).
185. 11. A. Wiebe, A. R. Knight, 0. P. Strausz, and 11. E. Gunning", "The reactions of sulfur atoms. V.
Further studies on the reactions with olefins", J. Amtr. Chem. Soc., 87, 1443 (1965).
186. B. D. Bogomolov and G. F. Prokshin, "Preparation of dimethyl sulfide from hydrolysis lignin .. ,
Khim. Seraorg. soedin., soderzh. Neftyakh Nefteprod., 8, 19 (1968).
187. R. T. Hawkins (Phillips Petroleum Co.), "Symmetrical aromatic sulfide production" US 4,044,056.
188. I. I. Lapkin and N. I. Panova, "Reactions of halide alkoxides. XI. A new synthetic route to
aromatic thioethers", Zh. Obshch. Khim., Jl, 745 (1962).
189. T. R. Govindachari, S. Prabhakar, P. S. Santhanam, and V. Sudarsanam, ''Synthetic applications
of nitromalonaldehyde-syntheses of some diphenyl ethers and diphenyl sulphides", Indian J.
Chem .• 4, 433 (1966).
190. H. Yoshida, S. lnokawa, and T. Ogata, "A new method for the synthesis of alkyl aryl sulfides.. ,
Bull. Chem. Soc. Japan, 39, 411 (1966).
lJl. J. A. Durden, 11. A. Stansbury, and W. A. Gatlette, "Synthesis of ethylene and propylene
sulfides", J. Org. Chem., %6, 836 (1961).
192. F. G. Bordwell and M. A. Hewett, "Synthesis from thiolesters. 11. Synthesis of cyclic sulfides", J.
Org. Chem., 13, 636 (1958).
193. R. Onesta and A. Ferreti, "Preparation of some thiophanes", Gazz. Chim,lta/., 85, 1185 (1955).
194. R. D. Obolentsev and V. G. Bukharov, "Synthesis of a-substituted thiophanes", Khim. Sera-Org.
Soedinenii, Soderzhashch. v Nefti i Nefteprodukt. Aka d. Nauk SSSR, Bashkir. Filial, Doklady 3-ei
Nauchn. Sessii, Ufa 1957, 9-19 (Pub. 1959).
R. D. Obolentsev, V. G. Buk.harov, T. E. Pozdnyakova, L. A. Alalykina, L. A. Bakalo, and A. E.
Pototskaya, "Synthesis of monosubstituted thiophanes", Khim. Sery i Azotorganich. Soedin.,
Soderzhashch. v Neft. i Nefteprodukt. Akad. Nauk SSSR. Bashkirsk. Filial, 3, 9 (1960).
R. D. Obolentsev, V. G. Bukharov. and A. U. Baisheva, "Synthesis of cis-2,5-dibenzylthiophane",
Khim. Seraorgan. Soedin., Soderzhashch. v Neft. i Nefteprod., Akad. Nauk SSSR, Bashkirsk.
Filial, 4, 20 (1961).
195. N. I. Shuikin, I. F. Bel'skii, L. Ya. Barkovskaya, V.l. Dronov, and L. A. Alalykina, "Synthesis of
2,4,· and 2,5-dialkylthiophanes", Khim. Seraorgan. Soedin., Soderzhashch. v Neft. i Nefteprod.
Akad. Nauk SSSR, Bashkirsk. Filial, 6, 197 (1964).
I. F. Bel'skii and N. I. Shuikin, "A new method for the catalytic synthesis of tetrahydrofuran
homologs as intermediates for syntheses of thiophanes", Khim. Seraorg. Soedin., Soderzhashch. v
Neft. i Nefteprodukt., Akad. Nauk SSSR, Bashkirsk. Filial, 4, 17 (1961).
N. I. Shuikin, I. F. Bel'skii, L. Ya. Barkovskaya, and M. M. Gerasimov, "Synthesis of some cyclic
sulfides.. , Khim. Seraorgan. Soedin., Soderzhashch. v Neft. i Nefteprod., Akad. Nauk SSSR
Bashkirsk. Filial, 7, 58 (1964). '
196. N. P. Volynskii, G. D. Gal'pern, and V. V. Smolyaninov, "Synthesis of 2-substituted thiacyclohex-
anes", Neftekhim., 3, 482 (1963).
N. P. ,Volynskii, G. D .. Gal'pe~?· a~d V. V. Smolyaninov, "New scheme of synthesis of
2-substJtuted tetrahydroth10pyrans , Khrm. Seraorgan. Soedin., Soderzhashch. v Neft. i Nefteprod
Akad. Nauk SSSR, Bashkirsk. Filial, 7, 109 (1964). .
197. R. F. Naylor, ''Synthesis in the thiapyran series. I. Tetrahydro derivatives" J. Chem. Soc 1947
1106. ' ., '
R. F. Naylor, "The reaction of sulphur and sulphur compounds with olefinic substances.
II.Mechanism of the reaction of hydrogen sulphide with mono-olefins, di-isoprenes and rubber",
ibid., 1947, 1532.
198. L. Bateman, R. W. Glazebrook, and C. G. Moore, "IX. The reaction of sulfur with 2,6-
dimethylocta-2,6-diene", J. Chem. Soc., 1958, 2846.
199 p, Friedman and P. Alien, "Medium-ring thiacycloalkanes. 11. Long-chain dibromides and
· gem-dimethyl substituted ~ibromides", 1: Org. Chem.~ 30, 780 (1965). , .
200. "9th International Symposmm on Chem1stry of Orgamc Sulf~r Compounds , Tez. dokl., R1ga,
1980, Ed. by Freidlina, R. (Akad. Nauk SSSR, Inst. Organ. Smteza Akad. Nauk Latv. SSR: Riga
1980), 350 pp.
201. B. A. Trofimov, S. V. Amosova, N. I. Kazantseva, 0. A. Tarasova, V. V. Kryuchkov, V. V.
Nasyrova, and N. N. Skatova, "New reactions resulting in substituted divinyl sulfides", Khimiya i
Tekhnol. Organich. Soedinenii Sery i Sernistykh Neftei. Materialy 13-oi Nauchnoi Sessii, Riga,
1974, pp. 117-19.
202. L. Adolfson, A. Fr_edga, and K. Olsson, "Ne~ trithiaadamantanes", T.ez. dokl. at the 9th
International Symposium on Chemistry of Orgamc Sulf~r Compounds, R1ga, 1980, p. 91. ~d.
by Freidlina, R., Akad. Nauk SSSR, Inst. Organ. Smteza Akad. Nauk Latv. SSR: R1ga,
1980. . .
203. A. K. Yus'kovich, T. A. Danilova, and E. A. Viktorova, "IsomerizatiOn of mon?cychc s~lfides o~
acid catalysts", Khim. i Tekhnol. Organich. Soedinenii Sery i Sernistykh Neftet. Matenaly 13-m
Nauchnoi Sessii, Riga, 1974, p. 289. . .
204. E. A. Viktorova, A. A. Fregar, and L. M. Petrova, "Ionic dehydrogenation and isomenzat10n of
cyclic sulfides", ibid., 1974, p. 290.
205. "The Chemistry and Physics of Rubber-Like Substances", Edited by L. Dateman (New York:
Wiley), 1963, 784 pp.
206. C. G. Moore, "Chemistry of vulcanization", Proc. NRPRA (Natural Rubber Producers Research
Association), Jubilee Conf. Cambridge, 1964, Ed. by Mullins, z. (Publ. by MacLaren and Sons
Ltd., London, 1964), pp. 167-94. .
207. A. A. Vol'tsov, "Properties Study of Organic Sulfur Compounds on their Interaction with Zeohtes
and Modified Silicon Oxide", Kand. diss., Ufa, 1981, 153 pp.
208. R. G. Omarova, "Synthesis and Transformations of Unsaturated Sulfides of Naphthalene Series",
Kand. diss., Irkutsk, 1983, 160 pp.
209. G. E. Radtseva, N. K. Lyapina, N. M. Ryakovskaya, and K. B. Sakaeva, "Use of petroleum
sulfides as non-root fertilizer for food grains (Institute of Biology of the Bashkirian Department of
the USSR Academy of Sciences and Institute of Chemistry of the Bashkirian Department of the
USSR Academy of Sciences) SU 629,211; Otkrytiya, Jzobreteniya, Prom. obraztsy, Tovarnye
znaki, 39, 88 (1978).
210.'G. F. Dol'shakov, E. I. Gulin, and N. N. Torichnev, "Physicochemical Principles in the Use of
Motor, Jet, and Rocket Fuels" (Leningrad: Khimiya) 1965, 270 pp.
211. G. F. Dol'shakov, P. I. Davydov, T. G. Potapenko, F. Yu. Rachinskii, and N. M. Slavachevskaya,
"Effect of natural and synthetic sulfur- and nitrogen-containing compounds on straight-run fuels",
Seraorgan. Soedin., Soderzhashch. v Nefti i Neftprod., Akad. Nauk SSR, Bashkirsk. Filial, 5, 160
(1963).
212. G. F. Dol'shakov, Yu. A. Bruk, and F. Yu. Rachinskii, "Use of an additive to increase the
thermooxidative stability of hydrocarbon fuels", Khim. Technol. Top/. Masel, 3, 52 (1966).
213. F. Yu. Rachinskii and N. M. Slavachevskaya, "Chemistry of Amino Thiols and Some of Their
Derivatives", (Leningrad: Khimiya) 1965, 295 pp.
F. Yu. Rachinskii, N. M. Slavachevskaya, L. V. Pavlova, Yu. A. Bruk, and G. F. Bol'shakov,
"Synthesis and study of physico-chemical properties of aminothiols with primary, secondary, and
tertiary mercapto g.."ups", Materialy 10-oi Nauchnoi Sessii po Khimii Serasoderzhashchich
Soedinenii Neftei i t!fteproduktov, Ufa, 1966, pp. 39-40.
214. Yu. A. Druk, F. Yu. Rachinskii, and G. F. Bol'shakov, "N-substituted 3,5-di-t-butyl-4-
hydroxylamines". SU 192,215; Chem. Abstr., 69, 256 (1968).
Yu. A. Druk, F. Yu. Rachinskii, and G. F. Bol'shakov, "Sulfur- and nitrogen-containing
derivatives of ionol", SU 194,834; Chem. Abstr., 69, 969 (1968).
Yu. A. Bruk, F. Yu. Rachinskii, and G. F. Bol'shakov, "Sulfur-containing ionol derivatives" SU
197,579; Chem. Abstr., 69, 2509 (1968). '
215. G. F. Dol'sh?ko.v, "Expl~itational properties o~ react.ive fuels based on cycloalkanes", Ekspluatats.
Svoistva Av~atswn. Topl1v, Smazochn. Matmalov 1 Technich. Zhidkostei 1973 33
216. D. A. Trofimov, V. L. Lashkhi, F. N. Ermolov, A. N. Ermolaeva, and A.' B. Vi~pe;, "Antiwear
382 0. F. BOLSHAKOV
properties of symmetrically substituted sulfides and sulfoxides", Khim. Tekhnol. Top/. Masel, 3, 33
(1975).
217. P. I. Davydov and G. F. Bol'shakov, .. Role of mercaptans in the formation of fuel·insoluble
sediments at high temperatures", Khim. Tekhnol. Top/. Masel, 5, 48 (1961).
218. P. I. Davydov and G. F. Bol'skakov, "Effect of sulfur compounds on the thermal stability and
corrosion properties of fuels for compressors in jet engines", Bor'ba s Korroziei Dvigatelei Vnutr.
Sgoraniya i Gazoturbinnykh Ustanovok, Vses. Sov. Nauchn.-Tekhn. Obshchestv., 1962, 272.
219. G. F. Bol'shakov and P. I. Davydov, "lnt1uence of organic sulfur compounds on the properties of
simple distillate fuels", Khim. Seraorgan. Soedin., Soderzl1ashch. v Nefti i Nefteprod., Aka d. Nauk
SSSR, Bashkirsk. Filial, 5, 138 (1963).
220. G. F. Bol'shakov and E. A. Glebovskaya, "Thermooxidative conversions of sulfur compounds in
n-hexadecane", Vses. Neft. Nauchn..tssled. Geologorazved. Inst., 221, 37 (1964).
G. F. Bol'shakov and E. A. Glebovskaya, "Thermooxidative transformations of sulfides", Khim.
Seraorgan. Soedin., Soderzh. Neft. Nefteprod., 9, 145 (1972).
G. F. Bol'shakov and E. A. Glebovskaya, "Role of organic sulfur compounds in the oxidation of
petroleum hydrocarbons. Report 5. Study of the oxidation mechanism of cycloalkanes. in the
presence of sulfides", ibid., 9, 461 (1972).
221. F. Yu. Rachinskii, G. F. Bol'shakov, and Yu. A. Bruk, 'Effect of some ionol derivatives on the
oxidative-thermal stability of sulfur-containing jet fuels", Khim. Serarog. Soedin., Soderzh. Neft.
Nefteprod., 8, 654 (1968).
222. G. F. Bol'shakov, "Mechanism of deposits formation on metal surfaces in sulphurous hydrocarbon
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SUBJECT INDEX
Acyclic sulfides, 128, 131, 137, 276, 1150 3-methyl-4-propylthiopbane, 134

Adsorbents, 174-176,178-182,198,199,300, methylthiophanes, 171
301,331 2-methylthiophane, 133
Alkanes, 171, 256, 257, 264, 300 2,2,3,5,5-pentamethylthiophane, 134
Alkanethiolates, 276 2-propylthiophane, 134, 183
Alkyl aryl sulfides, 131, 163,231,232,235,236, 2,2,3,5-tetramethylthiophane, 134
266,273 2,2,4,5-tetramethylthiophane, 134
Alkylbenzothiophenes, 143 2,2,5,5-tetramethylthiophane, 134

Alkyl cycloalkyl sulfides, 131 2,3,4,5-tetramethylthiophane, 134
Alkyl cyclohexyl sulfides, 131 3,3,4,5-tetramethylthiophane, 134
methyl cyclohexyl sulfides, 260 2,3,4-trimethyl-5-ethylthiophane,~ 134
nonyl cyclohexyl sulfides, 200 2,3,5-trimethyl-5-ethylthiophane, 134
Alkyldibenzothiophenes, 143 2,2,3-trimethylthiophane, 134
Alkyl disulfides, 174,245,261 2,2,4-trimethylthiophane, 134
Alkyl phenyl sulfides, 132 2,2,5-trimethylthiophane, 134
a-Alkyl substituted thiamonocycloalkanes, 133 2,3,4-trimethylthiophane, 134
Alkyl sulfides, 128-131,135, 173, 174,200,201, 2,3,5-trimethylthiophane, 134
203,234,236,242,269,272,274,276 2,4,4-trimethylthiophane, 134
Alkyl sulfonates, 274 Alkylthiophenes, 138,141,142,177,192,197,365
Alkanesulfonyl chlorides, 236 3-alkyl substituted thiophenes, 177, 274
S-Alkylisothiouronium salts, 274,275 2-alkylthiophenes, 232, 266
2-Alkylpentamethylene sulfides, 283 Alkylthiophenols, 128
Alkylthiophanes (alkylthiacyclopentanes), 177, Alkyl1-naphthyl sulfides, 305
232,268,365 Amino disulfides, 306
2-alkylthiophanes, 266,279, 280 Amino sulfides, 306
3-alkylthiophanes, 232, 266, 281 2-(2-Aminoethylthio )-benzimidazole, 331
2-amylthiophane, 202,203 1-Amino-2-phenyl-2-aminopentane, 327
3-amylthiophane, 202, 203 Arenes, 171, 271
2-butylthiophane, 202 Arenothiacycloalkanes, 136
3-butylthiophane, 134 Arenothiophenes, 138, 139, 141-144, 162, 271
a-decylthiophane, 233, 364 Aromatic disulfides, 174
2,5-diethylthiophane, 134 Aromatic polysulfides, 105
2,3-dimethyl-5-ethylthiophane, 134 Aromatic sulfides, 131, 177, 186,230,231, 234,
2,2-dimethyl-4-isopropylthiophane, 134 241,269
2,2-dimethyl-5-isopropylthiophane, 134 Aryl thioxanthates, 278
2,2-dimethyl-5-propylthiophane, 134 (Arylthio)ketones, 278
2,4-dimethylthiophane, 134 Arylthiophanes(arylthiacyclopentanes), 280,281
3,3-dimethylthiophane, 134 2,4-diphenylthiophane, 281
2-ethylthiophane, 133 phenylpropylthiophanes, 304
3-ethylthiophane, 133, 134 2-phenylthiophane, 202
4-ethylthiophane, 134
2-heptylthiophane, 202 Benzonaphthothiophenes, 142, 147
a-hexylthiophane, 239,240 Benzothiacycloalkanes, 135, 137, 163
2-(2-methylbutyl)-thiophane, 202 Benzothiophenes, 138, 139, 141-144, 147, 163,
2-methyl-3-ethylthiophane, 134 172,192,210,253,254,261,264
2-methyl-4-ethylthiophane, 134 Benzo[b]thiophene, 139, 141
4-methyl-2-isopropylthiophane, 134 Benzo[c]thiophene, 142,298
a-(2-methylpentyl)-thiophane, 240 Benzotrithione, 293
2-methyl-5-propylthiophane, 134 Benzyl sulfides, 234, 242
383
384 SUBJECf lNDEX
Bis-(3-t-butyl-4-hydroxy-5-methylphenyl) butyl S-octyl sulfide, 238

sulfide, 323 diamyl(dipentyl)sulfide, 200, 201,230, 260
Bis-(2-hydroxy-3-t-butyl-5-methylphenyl) dibutyl sulfide, 260
disulfide, 321 diethyl sulfide, 131,260
N ,N-Bis(3 ,S-di·t-butyl-4-hydroxybenzyl) diheptyl sulfide, 200, 301,356,366
diaminodiethyl disulfide, 322 dihexadecyl sulfide, 260
1,4-Bis(mercaptomethyl)-naphthalene, 259,261 dihexyl sulfide, 131,302,366
l,S-Bis(mercaptomethyl)-naphthalene, 259,261 diisobutyl sulfide, 183, 232
1,8-Bis(mercaptomethyl)-napthalene, 259,261 diisopropyl sulfide, 183
Bis-( 1-mercapto-2-pheny1-2-aminoethane)· dimethyl sulfide. 181,260,276
copper, 329 dioctyl sulfide, 304, 364
Bis-2-(2-naphthyl)ethyl disulfide, 247 dipropyhulfide, 131, 260
Butylpentamethylene sulfide, 284 ditetradecyl sulfide, 260
3-Butylthiophane, 134, 202 ditoly1 sulfide, 250,260
ethyl butyl sulfide, 131
Calorimetry, 268
ethyl decylsulfide, 131
Carbon disulfide, 2.32
ethyl propyl sulfide, 131, 180, 183

Carbon oxysulfide, 284 methyl propyl sulfide, 131
Catagenesis, 109,117-120,138,148,164,172,173
propyl butyl sulfide, 131
Catalysts, 169,171,173,194,208-223,233,241,
tolyl isopropyl sulfide, 131
253,276-282,285,292,293,296,341
1.2-Di·(alkylthio)~thylene, 2~5
Chromatography, 133,174-182,186,197,198
Diallyl disulfide, 244
Complex formation, 174, 176, 180-182, 197-208, Diallyl sulfides, 131
234 Diary! disulfides, 2~8. 251,261,273
Cyclic disulfides, 272 Diary! sulfides, 132, 142, 163,242, 2n. 278
Cyclic sulfides, 128,132-135, 162, 174,200,272 Dibenzothiacycloalkanes, 163
Cycloalkanes, 174 2,2 1-Di(benzothiazolyl)disulfide, 298
Cycloalkyl aryl sulfides, 132 Dibenzothiophene, 138, 139, 141-144.147, 163,
Cycloalkyl benzothiophenes, 143
172,210,253,254,261,264
Cycloalkyl dibenzothiophenes, 143
Dibenzyl sulfide, 237.238, 250, 260
Cycloalkyl sulfides, 131
Dibenzyl trisulfides, 261
Cyclohexyl1-pentyl sulfide, 130
Dicycloalkyl sulfides, 132
Dehydrogenation, 171, 180,209 Dicyclohexyl hexasultides, 272
Depthofoccurrence, 106-110.112,115-121, Diethyl tetrasulfides, 272
124-126,128,138,149-167,169,170 Diethyl trisulfidcs, 261
Destruction, 109, 117-120, 148, 164, 171-173, Dihexadecyl trisulfides, 261
216,230-234 Dimethyl trisulfides, 261
Desulfurization, lOS, 109, 133, 138,208,212-215, 2,3-Dimethylbenzothiophene, 139
217-222 2,4-Dimethylbenzothiophene, 139
Dialkenyl disulfides, 243 2,6-Dimethylbenzothiophene, 139
Dialkyl disulfides, 229,244,251,272,292 2,7-Dimethylbenzothiophene, 139
dibutyl disulfide, 260 3,5-Dimethylbenzothiophene, 139
di-t-butyl disulfide, 225,250,252 3,7-Dimethylbenzothiophene, 139
diethyl disulfide, 180, 260 3,6-Dimethylbenzothiophene, 139
dihexadecyl disulfide, 260 4,7-Dimethylbenzothiophene, 139
diisobutyl disutfide, 260 1,8-Dimethylbenzothiophene, 142
diisopropyl disulfide, 250 Dimethylene sulfide, 272
dimethyl disulfide, 250,260 Dimethyl-6-isopropylpentamethylene
dioctadecyl disulfide, 260 sulfide, 285
dioctyl disulfide, 260, 256 2,6-Dimethylpentamethylene sulfide, 284
dipropyl disulfide, 260 3,3-Dimcthylthiacyclobutane, 260
ditetradecyl disulfide, 260 Dimethyl-1-thiaindane, 135
O,S-Dialkyl dithiophosphoric acids, 278 Dinaphthenobenzothiophene, 141
a,a' -Dialkyl substituted Dinaphthenodibenzothiophene, 141
thiamonocycloalkanes, 133 Dinaphthenothiophenes, 141, 142
Dialkyl sulfides, 231,232,234,271,272,300-302 Diphenyl disutfide, 260,364
butyl amyl sulfide, 131 Diphenyl sulfides, 224, 230, 234, 242, 246, 250,
butyl hexyl sulfide, 131 260,277,301,304,360,366
butyl octyl sulfide, 131 2,2'-dimethyldiphenyl sulfide, 260
SUBJECT INDEX 385
2,3'-dimethyldipbenyl sulfide, 260 Fuels, 105,174-177,182,183,186-190,195,

2,4'-dimethyldiphenyl sulfide, 260 213-216,305-307,312,313,315,323,330-341,
3,3'-dimethyldiphenyl sulfide, 260 343-372
3,4' -dimethyldiphenyl sulfide, 260
2,4-Diphenylthiophene, 296 Genesis, 103, 131, 166-173
Disubstituted thiophanes, 282 Geological age, 106-121,124-126,128,133,138,
2,5-dialkylthiophane, 266 144,149-173
2,2-dimethylthiophane, 134
2,3-dimethylthiophane, 134 Hydrogen sulfide, 108, 109, 112, 118, 120, 124,
2,4-dimethylthiophane, 134 148-156,158,164,166,169,171,173,176,181,
2,5-dimethylthiophane, 134 209,211,215,224,232,233,275,279,284,285,
cis-2,5-dimethylthiophane, 283 293,296
trans-2,5-dimethylthiophane, 283 Hydrogenation, 171, 174, 180,208-220,222
3,4-dimethylthiophane, 134 Hydrolysis, 174, 190, 192, 195, 196, 200,274, 360
2-ethyl-3-methyl-5-propylthiophane, 202 Hydrosulfide, 169,274, 279
2-methyl-5-ethylthiophane, 134
2-methyl-5-propylthiophane, 134 Infraredspectroscopy, ·131, 174,177,178,180,
Disubstituted thiophenes, 274 237-240,265-271,317,318,321-323,332,335,

2,5-dialkylthiophene, 266 338-341,343,345,347,349-352,370-372
2,5-dimethylthiophene, 261,361 Initial organic matter, 120,144,166-170,172,173
3,4-dimethylthiophene, 177 Isobutyl sulfide, 183
Disulfides, 105,120, 126, 128,137, 138,146,148, S-Isohexyl phenyl sulfide, 304
156,158,161,162,166,173,174,176,197,200,
209,211,212,224,226-229,232,243-253,261, Light-scattering investigation, 304-315,261
264,269,270,272,273,292,301,303,304,321, Lithologyofcollectors, 106-119,121-125,128,
354,358-360,365-367,370 138,149-168,171
Dithioacetals, 228
Dithioketals, 228 Mass spectral analysis, 131, 132, 138
1,2-Dithiolane-3-thione, 226, 293 Mercaptides, 194-196, 229, 230, 276, 277, 305
1,2-Dithiolylidene-3-thione, 293,294 2-Mercaptobenzothiazole, 298
a-(1,2-Dithiolylidene-3)-thione, 294 Mercaptocarboxylic acids, 234
Dithiophosphates, 235 Mercaptocinnamic acid, 295
Di(p·tolyl) disulfide, 260 p..Mercaptoethylamine, 326, 328
Divinyl sulfide, 261 1-Mercapto-2-phenyl-2-aminobutane, 307, 327,
329
3-Mercaptothiophene, 296
Elementalsulfur, 118, 120,121, 124-126, 138, Methyl benzyl sulfides, 277
148-156,158,161,164,166,169,171,173,232 Methyl phenyl sulfide, 183,202
ESR spectroscopy, 271-273,317-320,323 Methyl3,4,5-trimethyl-2-thienyl sulfide, 146
Ethyl cyclopentyl sulfide, 201 2-Methylbenzothiophene, 139, 141
2· Ethylbenzothiophene, 139 2-Methyl-5-benzothiophene, 139
3-Ethylbenzothiophene, 139 3-Methylbenzothiophene, 139, 141, 360
2-Ethyl-3-ethyl-1-thiaindane, 135 4-Methylbenzothiophene, 139
(5-Ethyl-3-formyl-2-thienylthio )-acetic acid 5-Methylbenzothiophene, 253
ester, 296 7-Methylbenzothiophene, 139
2-Ethyl-5-methylbenzothiophene, 139 Methylcyclohexanes, 293
2-Ethyl-7-methylbenzothiophene, 139 _1-Methyldibenzothiophene, 142
3-Ethyl-5-methylbenzothiophene, 139 4-Methyldibenzothiophene, 142
3-Ethyl-6-methylbenzothiophene, 139 4-Methyl-1 ,2-dithia-4-cyclopentene-3-thione, 226
3-Ethyl-7-methylbenzothiophene, 139 2-Methyl-3-ethylbenzothiophene, 139
Ethyl phenyl sulfide, 277 2-Methyl-4-ethylbenzothiophene, 139
2-Ethyl-1-thiaindane, 135 2-Methyl-7-ethylbenzothiophene, 139
2-Ethylthiapyrane, 202 2-Methyl-2-ethyl-1-thiaindane, 135
2-Ethylthieno[2,3-b}thiophene, 297 Methyl-11-thiabenzo[ a ]fluorenes, 142
5-Ethyl thieno[ 2,3-b-]thiophene-2-carboxylic 3-Methyl-2-thiabutane, 129
acid, 297 2-Methylthiacyclobutane, 295,296
(5-Ethyl-2-thienylthio)-acetic acid, 296 Methylthiacyclohexanes, 134
Ethylthiocyclohexanes, 134, 201 Methyl-1-thiaindane, 135
Extraction Mononaphthenothiophenes, 141
386 SUBJECf INDEX
Monosubstituted thiophenes, 138,253,274 185-195,197-202,204,209,211,212,224,225,

methylthiophene, 212 230,232,234,237,250,253-255,261,263,264,
2-methylthiophene, 261,357, 361 269-271,274,276,304,305,322,332,358-360,
3-methylthiophene, 261,361 365,367,370,372
1,8-Naphthalenedithiol, 259 Sulfinic acids, 229, 230,237,238, 345
Naphthenodibenzothiophenes, 141 Sulfites, 275,339,341
Naphthenothiaindanes,. 136 Sulfolane, 238
Naphthobenzothiophenes, 142 Sulfonates, 238,338,347,351, 359,362
Naphthothiophenes, 142, 163 Sulfonation, 173-175, 198,252
1 Sulfones, 105, 198, 231,236,238-240,298,305,
H NMR spectroscopy, 173,174
347,351,358
Octahydrothiaxanthene, 234 p·hydroxyphenyl methyl sulfone, 362
Oxidation, 169, 171, 173, 177,194, 197-199,228, quinone sulfones, 254
229,237-242,248-265,269,270,306-325,327, Sulfonic acids, 170,229,238,239,247,248,276,
334-341,343,344 341,345,351,358,359,361
Ozonolysis, 197, 240 benzenesulfonic acid, 362
bromosulfonic acid, 247
Pentacondensed arenothiophenes, 139 chlorosulfonic acid, 247

Pentacyclic thiacycloalkanes, 131 Sulfonium perchlorates, 234
Pentamethylene disulfide, 272 Sulfonyl chlorides, 275
Pentamethylene sulfides, 272, 283, 285 Sulfoxides, 105,197-199,238-242,298,305,332,
Pentanethiols, 126, 127 353,354
Perhydrothiaxanthene, 234 benzyl phenyl sulfoxide, 198
Phenyl sulfide, 242 dibenzyl sulfoxide, 198
phenyl s-butyl sulfide, 131 1 ,3-dihydrobenzo[c]thiophene sulfoxide, 298
phenyl p-tolyl sulfide, 260 dimethyl sulfoxide, 208, 234, 277
Phenyl methyl sulfide, 242 diphenyl sulfoxide, 298
Phenyl propylsulfide, 273 isobutyl phenyl sulfoxide, 298
Phenylthioxanthates, 278 perchlorate sulfoxides, 198
Polarography, 148 Sulfuroxides, 105,106,183-185,197,333
Polyarenothiophenes, 139,163, 172,173 Sulfuric acid, 105, 106, 131, 173-175, 184,
Polymethylene sulfides, 285 186-188,190,192,194,229,234,240,241,248,
Polynaphthenoalkyl thienyl sulfides, 132 252,275,296,302,359,360
Polysiloxanes, 105 Sulfurization, 133, 171
Polysubstituted thiophanes, 282 Sulfuryl chloride, 236
Polysulfides, 225,243,272
Potentiometry, 177 Tetracondensed arenothiophenes, 139
4-Propylbenzothiophene, 139 Tetracyclic thiacycloalkanes, 131, 137
5-Propylbenzothiophene, 139 Tetrakis(mercaptomethyl)methane, 259,261
7-Propylbenzothiophene, 139 1,2,7,8-Tetramethyldibenzothiophene, 142
Tetramethylene disulfide, 272
Tetramethylene sulfide, 272
Raman spectroscopy, 270, 362 2,4 ,6,8-Tetramethyl-5-thianonane, 256
Reduction, 169, 171,197,250,253 Tetramethylthiuram disulfide, 298
Refining, 105, 120, 173, 182,208, 209,212 2,2,6,6-Tetrasubstituted pentamethylene
sulfides, 284
Secondary sulfurization, 112, 118, 120, 148, 169, Thermal desorption, 178, 179
171 Thiaalkanes, 131,255-258,262,266
Sodium sulfide, 246, 276, 284 dithiaalkanes, 255, 262, 264, 266
Spectrophotometry, 148 2-thiaalkanes, 254,256-258,262-264,266
2-Substi tuted cyclic sui fides, 203 3-thiaalkanes, 254
3-Substituted thiacycloalkanes, 203 Thiaalkenes, 266
Sulfamines, 243 11-Thiabenzo[a)ftuorenes, 142
Sulfates, 169, 274, 338-340,347, 351, 359, 360, Thiabicycloalkanes, 131, 132,135, 136
362,372 2-Thiabutane, 129, 163
Sulfenic acids, 229 Thiacycloalkanes, 132, 133, 135, 137, 144, 162
Sulfenyl halides, 244, 277 163,171,172,192,200,201, •
Sulfides, 105,120, 121,124, 126, 128, 132, 133, 256,262,264,273,274
136-138,144,149-162,164-166,169,172,176, Thiacyclobutanes, 262, 273
SUBJECf INDEX 387
Thiacycloheptanes, 202, 232 Thiocarbonyl compounds, 271

Thiacyclohexanes, 132,134, 171,202,232, 240, Thiols, 105, 120, 121, 124-126, 128, 131, 138, 139,
262,264,273,274,295,296 143,144,148,156-158,161,164-166,164-166,
3-amylthiacyclohexane, 203 168,173,176,177,189,194-197,209,211,212,
2,5-dimethyl-2-ethylthiacyclohexane, 134 224,228,229,230,232-237,250,253,255-259,
2,3-dimethylthiacyclohexane, 134 266-269,271,273-277,285,286,292,293,298,
2,4-dimethylthiacyclohexane, 134 300,301,304-306,353,354,356,358,365,367,
2,6-dimethylthiacyclohexane, 134 370,372
2-methyl-6-ethylthiacyclohexane, 134 alkanethiols, 232, 254-264, 266, 271, 272, 275,
2-methylthiacyclohexane, 134 276
2-substituted thiacyclohexanes, 283 amino thiols, 306-309, 312, 324,326-330
2,3,3,6-tetramethylthiacyclohexane, 134 aromatic thiols, 174, 177,261,267,269,273
2 ,2,5-trimethyl-5-ethylthiacyclohexane, 134 butanethiol, 126
2,3,6-trimethylthiacyclohexane, 134 1-butanethiol, 126,259
Thiacyclopropane, 235, 260, 262, 264, 279 2-butanethiol, 127
3-Thiadecane, 202 cyclic thiols, 174, 267-269
3-Thiaheptane, 263 cyclohexanethiol, 127,259,269
Thiaheptanes (substituted), 130 cyclopentanethiol, 269

Thiahexanes, 139, 130, 263 cyclopropanethiol, 268, 275
Thiaindanes, 135, 142,144,232 (3 ,5-di+butyl-4-hydroxyphenyl )-
Thianaphthenes, 293 methanethiol, 315
Thianaphthols, 268 2,2-dimethyl-1-propanethiol, 127
Thianonanes, 130, 202 dodecanethiol (dodecyl mercaptan), 304
Thianthrene, 248 t·dodecanethiol (t-dodecylmercaptan), 195,
Thianthrene S,S-dioxides, 248 275,300
Thiaoctanes, 130 ethanethiol, 126, 181, 228,259,298, 326
Thiapentanes 1-heptanethiol, 127
2,2-dimethyl-3-thiapentane, 130 2-heptanethiol, 127
2,4-dimethyt-3-thiapentane, 130 hexanethiol, 126
2,6-dimethyl-4-thiapentane, 202 1-hexanethiol, 267
3,3-dimethyt-2-thiapentane, 130 2-hexanethiol, 127
2-methyl-3-thiapentane, 129, 130 3-hexanethiol, 256 •
3-methyl-2-thiapentane, 129 methanethiol, 126, 181,224,259,269,298
4-methyl-2-thiapentane,129 2-methyl-1-butanethiol, 127
2-thiapentane, 129, 263 2-methyt-2-butanethiol, 127
3-thiapentane, 129,263 3-methyl-1-butanethiol, 127
4-thiapentane, 202 3-methyl-2-butanethiol, 127
2,2.4-trimethyl-3-thiapentane, 130 methylcyclohexanethiol, 269
Thiapolycycloalkanes, 135 2-methyl-2-pentanethiol, 127
2-Thiapropane, 129,263 2-methyl-3-pentanethiol, 127
2-Thiaquinolines, 147 4-methyl-2-pentanethiol, 256
Thiatetralines, 135 1-methyl-1-propanethiol, 259
7-Thiatridecane, 202 2-methyl-1-propanethiol, 127,261
Thiaundecanes, 130, 203 2-methyl-2-propanethiol, 127, 259
Thiazoles, 138, 146 1-naphthalenethiol, 259
alkylbenzothiazoles, 146 2-nonanethiol, 256
4,5-diethylthiazole, 146 1-octanethiol, 367, 372
4,5-dimethyl-2-phenylthiazole, 146 2-octanethiol, 127, 256, 364
5,ethyl-4-propylthiazole, 146 pentanethiol (amylmercaptan), 180
4-methyl-2-phenylthiazole, 146 1-propanethiol, 1:.6, 259
Thienothiacycloalkanes, 146 2-propanethiol, 126,250,259,293
Thienothiophenes, 146,296 3-thiophenethiol, 296
Thienyl sulfides, 146, 230 1,4-toluenedithiol, 259
(Thienyl-thio )-acetic acid, 296 a·toluenethiol, 259
Thiirane, 273, 292 unithiol, 305
Thioacetates, 279 Thiolsulfonate, 248, 249
Thioacetic acid, 279 Thionaphthol, 268
Thioalkanes, 131 Thiophanes ( thiacyclopentanes), 128, 131-133,
Thioamides, 271 171-173,177,180,183,184,202,209,211,212,
388 SUBJECT INDEX
233,236,239,240,260,262,270,280,282,283, 2,3,5-trialkylthiophane, 266

296,301,358,359,364 2,3,5-trimethylthiophane, 134
Thiophenes, 105,120,126,138,139,141, Triarenothiophenes, 139
143-145,147,148,158,161,163,164,166, Tricyclic thiacycloalkanes, 131, 132, 137
171-174,176-178,180,189,192,195,197,203, 2,3,5-Trimethylbenzothiophene, 139
204,209,210,212,224.226-228,232,234,250, 2,3,6-Trimethylbenzothiophene, 139
252-254,256,261,264,270-274,294-298,301, 2,3,7-Trimethylbenzothiophene, 139
356-358,361,365,370 2,4,7-Trimethylbenzothiophene, 139
Thiophenols, 180,259,267,268,273-276,278 Trimethylene disulfides, 272
Thiourea, 271,274,275 Trimethylene sulfide, 272
Thioxanthylium salts, 234 Trimethyl-1-thiaindanes, 135
Titration, 148 Trinaphthenobenzothiophenes, 141
p-Toluenesulfinic acid, 236 Trinaphthenothiophenes, 141
Tolyl sulfide, 232 Trisulfides, 261
Total sulfur content, 105-121, 124-126, 128, 129, Trithiaadamantanes, 294
131,137,144,149-161,163-167,176,183,185,
189-191,194-197,212-216
Trialkyl dithiophosphates, 277
Trialkylthiophanes, 282 UV spectroscopy, 225-228,267,268,273,345,
2,4-dimethyl-5-ethylthiophane, 134 352
AUTHOR INDEX
Abdou,l. K., 166 Bogomolov, B. D., 276

Adol'fson, L., 294 Bol'shakov, G. F., 105,112,124, 138,148, 174,
Agrawal, B. B., 166,212 177,189,229,237-240,257,266-272,306,307,
Agrest, F. B., 271,272, 307 320,334,335,338,343,345,353,362,365,366
Ahmed, L., 166 Bordwell, F. G., 279 ·
Aivazov, B. V., 126,129, 133,174, 181,256, Botnikov, A. Ya., 136
262-264,266,267 Boulet, R., 139

Aksenov, V. S., 106,124,131-133, 138,139,142, Bowen, D. 0., 180
146,156,169,172,173 Bowers, K. W., 236
Alalykina, L. A., 280-282,284 Bridge, A. G., 212
Allen, P. J., 285 Brodskii, E. S., 128, 131, 132, 135, 136, 138, 139,
Allilueva, T. 1., 183 143,145,320
Amberg, C. H., 209 Bruk, Yu. A., 306, 307, 334
Amosova, S. V., 245,293 Buechler, G., 234
An, V. V., 112 Bukhareva, V. A., 275
Andryushenko, T. P., 220 Bukharov, V. G., 280,281
Angelova, G., 242 Burdge, D. N., 230
Appel, R., 234 Buyanova, N. S., 131, 138,142
Arich, G., 167, 171 Bykov, V. G., 181
Asdigian, G., 196
Ashumov, G. G., 112 Carruthers, W., 142
Atavin, A. S., 245
Castex, H., 139
Charkviani, T. N., 174
Badora, K., 138, 139 Chertkov, Ya. B., 105, 174, 184, 186,190,298,
Baikova, A. Ya., 112, 120, 124, 125, 148, 156, 300,301,303-305
164 Christensen, D., 227
Baisheva, A. U., 280,281 Coleman, H. J., 126, 129,131,133, 135, 138,141,
Bak, B., 227
142,146,166,167,169,171,174
Bakalo, L. A., 280,281
Copelon, E. C., 147
Balaev, A. V., 217
Costantinides, G., 167, 171
Bardina, T. A., 128, 135, 139 Cottrell, J. L., 358
Barkovskaya, L. Ya., 282, 284
Cullum, T.V., 134,174,212
Bassler, C. G., 273, 274
Bateman, L., 285
Bednyagina, N. P., 172 Danilova, T. A., 295
Beiter, G. A., 217 Davydov,P. I., 306,307,334,335,338
Belen'kii, L. I., 227,252, 296,298 Dean, R. A., 134, 174,212
Bel'skii, I. F., 282,284 Denyer, R. L., 134, 174,212
Bembel, V. M., 203,204 Dobryanskii, A. F., 128,169, 171
Benashvili, E. M., 174 Dooley, J. E., 132, 136,138,146
Ben'kovskii, V. G., 143 Douglas, A. G., 142
Bestougeff, M. A., 138, 139, 167, 169, 171 Douglas, W. M., 196
Berg, G. A., 213,220 Dragunskaya, V. S., 131
Beuther, H., 217 Driatskaya, Z. B., 112
Bhatia, V. K., 148, 156 Dronov, V.I., 282,284
Birch, S. F., 134, 167, 174, 182, 183, 212 Drozdova, T. V., 168
Blyholder, G., 280 Drushel, H. V., 106,138,139, 156,160,169,172,
Bobkova,E. N., 112 173
Bobruiskaya, T. S., 128, 135, 139 Dubovkin, N. F., 261
389
390 AUTHOR INDEX
Ourden, J. A., 278 Halvarson, K., 252

Dzhorbenadze, G. Sh., 174 Hansen-Nygaard, L., 227
Hawkins, R. T., 278
Hewett, W. A .• 279
Eardley, A. J., 106 Hirsch, D. E., 132, 136, 138, 146
Egiazarov, Yu. G., 112 Hisamitsu, T., 217
Eigenson,A. S., 217,220 Ho, T. Y., 106,138,139,156,160, 169, 172,173
Eletskii, N. P., 132 Hoekstra, G. B., 213
Emsley, J. W., 274 llopkins, R. L., 126,129,131, 133, 135, 138, 139,
Ermolaeva, A. N., 141,142,166,167,169,171,174
Ermolov, F. N., 332
Erofeev, V. I., 211,234,351 Ibragimova, F. I., 126
Eyles, M. K., 213 Inokawa, S., 278
Ioakimis, A. A., 220
Fal'ko, F. S., 128 lvchenko, E. G., 112, 132
Fartey, C. E., 244
Jahning, C. E., 217
Fattakhova, R. Sh., 183

Ferreti, A., 280 Jensen, R. H., 212
Flinn, R. A., 217 Johnson, W. 11., 217
Ford, R. A., 273, 274 Joly, D., 138,139,171
Fredga, A., 294
Freger, A. A., 296 Kaimai, T., 128
Kaishev, K., 242
Friedman, P., 285
Kalabin, G. A., 245
Friedman, W., 172
Kalechits, I. V., 211,234,351
Froment, G. F., 217
Kalik, N. A., 227,252,296,298
Funey, J., 274
Kalintcheva, L. A., 213
Furaeva, I. V., 275
Kam'yanov, V. F., 106, 112, 124, 131-133, 138,
139,142,146,148,156,169,172,173
Galeeva, G. V., 174, 183 Kaplan, Z. G., 268-271,307
Galiaskarov, F. M., 220 Karachevtsev, G. V., 222,224,227,267,353
Gal'perin, B. M., 196 Karaulova, E. N., 128, 135, 139,229,232-235,
Gal'pern, G. 0., 125, 126, 128, 135, 138,139, 241,242,279,286
173,283 Karazhigitova, R. K., 131, 138, 142
Garnovskii, A. D., 259, 361 Karmanova, L. P., 128, 136, 139, 143-145
Gates, B. C., 217 Kasantseva, N. I., 245,293
Gatlette, W. A., 278 Kashina, M. I., 213
Gazeeva, V. N., 174 Kaur, S., 148, 156
Gerasimov, M. M., 282,284 Kendall, R. F., 131
Gerasimova, V. G., 181 Khabibullin, S. G., 213,217
Glazebrook, R., 285 Khairullina, V. R., 126, 129, 133, 139,256,
Glebovskaya, E. A., 138,148,174,177,189, 262-264,266,267
268-271, 307 320, 334, 338,345 Khakhaev, B. N., 112
Godfrey, D., 365 Kharasch, N. J., 244,245
Godsave, L. A., 213 Kharchenko, V. G., 234
Gol'dberg, Yu. M., 132 Khmel'nitskii, R. A., 128, 139
Goncharov, I. V., 132 Khokhlova, L. V., 275
Gordon, A. J., 273,274 Khoroshko, S. I., 112
Govindachari, T. R., 278 Kice,J. L., 236
Grant, J. A., 128, 138, 139 Kimberlin, C. N., 217
Grayson, M., 244 Kirillov, T. S., 213,220
Grunvald, V. R., 196 Kleinhenz, T. A., 213
Gulati, I. B., 166,212 Klimenko, S. K., 234
Gulin, E. I., 306, 307, 334 Klimova, V. A.,204
Gunning, H. E., 275 Knight, A. R., 275
Gurvich, L. V., 222,224,227,267,353,1227 Koblova, A. Z., 112
Gusarov, A. V., 245 Kochetova, N. A., 213,220
Gusarova, N. K., 245 Kogan, L. 0., 132
Guseva, A. N., 112 Kondakov, D. 1., 190
Guthrie,G. B., 138 Kondrat'ev, Yu. A., 222,224,227,267,353
AUlltORINDEX 391
Konstantinova, I. A., 124, 148 Minoru, N., 126, 129, 133, 139
Koons, C. B., 106, 138, 139, 156, 160, 169, 172, Mishaui, Sh., 242
173 Moiseikov, S. F., 112
Korshunov, M. A., 275 Molchanov, A. F., 196,335
Kositsina, E. I., 245 Moore, C. 0., 243,285,300
Kotova, A. V., 131, 138, 142 Morril, T. C., 273, 274
Koval, L. M., 211 Mosby, J. F., 213
Kozlov, N. S., 112 Munir, M., 126, 129, 133, 139
Krizhanenko, 0., 181 Muszynski, J., 138, 139
Krol, B. B., 131, 198
Krupina, T.I., 234 Nadirov, N. K., 112
Kryuchkov, V. V., 293 Nasyrova, V. V., 293
Kryvolapov, R.S., 183 Naylor, R. F., 284,285
Kucheryavaya, N. N., 131,198,320 Nelson, W. L., 217
Kulikov, V. I., 112 Nikitin, Yu. E., 128, 136, 138
Kumanova, B., 242 Nikitina, T. S., 131, 139, 143, 145, 183, 320
Kurakolova, E. A., 133 Nikitina, V. S., 128, 135, 138, 139, 144, 183, 190
Kuznetsova, V. F., 172 Norris, W. S. G. P., 182

Kvasova, E. N., 128, 135, 138 Numanov, I. U., 132
Landa, E. M., 169 Oae, S., 225,243,246,247,251,293,305

Lapkin, I. I., 278 Obolentsev, R. D., 112, 120,124-126,128,148,
Larina, I. Ya., 105 156,164,174,182,183,280,281
Lashkhi, V. L., 332 Ogata, T., 278
Latham, D. R., 147 Ol'sson, K., 294
Latyuk, V. I., 196 Omarova, R. G., 305
Lazareva, I. S., 124, 148 Onesta, R., 280
Lebedev, A. K., 133, 353 Osipov, 0. A., 259,361
Lebedev, V. A., 222,224,227,267 Ozaki, H., 217
Levchenko, E. S., 112
Likhosherstov, M. V., 242 Panova, N. I., 278
Lohinska-Gasowska, A., 138, 139 Pape, D., 169
Lubopytova, N. S., 126,128,138 Parfenova, M. A., 128,131, 132,135,136, 138,
Lukoshenko, I. M., 136 139,143-145,174,180-182,190,200,203,298,
Lushina, N. N., 183 300,301,304,305,320
Lyapina, N. K., 128,131, 135, 136, 138, 139, Parker, A. J., 244, 245
143-145,174,180-183,190,200,203,298,300, Parubenko, I. A., 112
301,304,305,320 Patsigova, D., 135, 139
Lysikova, T. I., 196 Pavlova, L. V., 307
Peri,J.B., 181
Mabery, C. F., 128 Petrov, S. M., 126, 129,133,139,256,262-264,
Magaril, R. Z., 212 266,267
Mahmoud, B., 166 Petrova, L. M., 296
Makova, E. A., 126 Plankova, V. F., 183
Manskaya, S. M., 168 Plusnin, A. N., 133,203,204
Martin, R. L., 128, 138, 139 Podkletnov, N. E., 112
Maruyama, F., 217 Polyakova, A. A., 128, 132, 136, 139 ~
Masahiro, K., 126, 129, 133, 139 Ponomareva, E. A., 112
Masohan, A., 148, 156 Postovskii, I. Ya., 172
Matsunaga, A., 128 Potapenko, T. G., 306,307
McCay,J. F., 147 Pototskaya, A. E., 280, 281
McCullough, J. P., 138 Pozdnyakova, T. S., 280,281
McKittrick, D. S., 182, 197 Prabhakar, S., 278
Meisel, S. L., 141 Price, C. C., 225,243, 246, 247,251, 293, 305
Melander, L., 252 Prinzler, V. H. W., 169
Mel'nikova, L. A., 128, 136, 139, 143-145, 174, Prokshin, G. F., 276
180-182,200,203,298,300,301,304,305 Pryor, W. A., 246
Metrailer, I. R. W. T., 217 Pshenichnaya, N. A., 112
Minkin, V. I., 259,361 Putilova, Z. D., 213
392 AUTHOR INDEX
Rachinskii, F. Yu., 306,307,334 Stakhina, L. D., 203

Radtseva, G. E., 305 Stansbury, H. A., 278
Rahman, R., 225 Stolfa, F., 212
Rail, 11. T., 126, 129, 133, 135, 138, 139, 141, 142, Stramkovskaya, K. K., 112
166, 167' 169, 171 Strausz, 0. P., 275
Rastrup-Andersen, J., 227 Strelko, V. V., 178
Richter, F. P., 141 Sudarsanam, V., 278
Rizvi, S. A. A., 166 Sutcliffe, L. H., 274
Roberts, G. W., 209 Szymansky, H. A., 273,274
Robinzon, E. A., 112
Rochester,C. 11., 180
Rogers, M. A., 106, 138,139, 156, 160,169,172, Tarasova, 0. A., 293
173 Tate, D. P., 230
Rohatgi,ll. S., 166,212 Taylor, A., 225
RoucacM,J., 139 Teeter, R. M., 147
Rozanova, Z. N., 131,320 Teleshova, M. N., 112, 181
Rozhdestvenskaya, A. A., 131, 198 Terrell, R. J., 180
Ryabova, N. D., 174 Thompson. C. J., 106, 126, 129, 131-133, 135,
Ryakovskaya, N. M., 305 138,139,141,142,146,166,167,169,171,174
Tissot, B. P., 106
Safe, S., 225 Titov, V. I., 106, 124, 131-133, 138, 139,142,
Safonov, G. A., 203,204 146, 156, 169, 172, 173
Sagachenko, T. A., 133 Tolstenev, V. S., 112
Saitova, A. Ya., 220 Torichnev, N. N., 306,307,334
Sakaeva, K. B., 305 Trego, B. R., 243
Santhanam, P. S., 278 Trofimov, B. A., 245,293,332
Satomi, Y., 217 Trokhova, S. N., 131, 138, 142
Sattarova, F. G., 138 Truce, W. E., 230
Satterfield, C. N., 209 Tsoi, L. A., 203, 204
Schmid, B. K., 217 Turkov, 0. S., 112
Schuit, G. C. A., 217 Turov, Yu. 1., 132
Schulz, 11., 126, 129, 133, 139
Scott, J. W., 138,212
Seifert, W. K. 147 Uchaneshvili, T. G., 174
Selvidge, C. W., 212 Ulendeeva, A. D., 135, 136, 139, 143, 145, 183
Sergienko, S. R., 112 Urazgaliev, B. U., 112
Serikov, T. P., 112
Sevastyanov, G. V., 112, 132 Valibekov, Yu. V., 112, 128,135, 138
Shite, Y., 217 Valitov, I. B., 118, 171, 223
Shostakovskii, M. F., 245 Vasilenko, G. N., 132, 181
Shuikin, N. 1., 282,283 Vatago, V. S., 271,272,307
Silverstein, R. M., 273, 274 Vestal, M. L., 217
Siryuk, A. G., 131,320 Viktorova, E. A., 295, 296
Skatova, N. N., 293 Vinnikovskii, S. A., 112
Sklyarov, A. V., 365 Vogh,J. W., 132,138,146
Skobclina, A. I., 128, 132, 135, 138 Volkova, L. I., 220
Skundina, L. Ya., 213,220 Vol'tsov, A. A., 139, 14-1, 300,301
Slavachevskaya, N. M., 306, 307 Volynskii, N. P., 283
Smarkalov, A. A., 128, 136, 139, 14-1, 145, 190 Voorhies, A. V., 217
Smirnov, V. A., 135 Vysheslavtsev, Yu. F., 1Q6, 335
Smith, A. W., 128, 169, 171 Vysotskii, V. 1., 112
Smith, 11. M., 169, 171
Smolyaninov, S. I.. 112
Smolyaninov, V. V., 283 Waddington, G., 138
Smolyaninova, N. M., ll2 Ward, C. C., 136
Snyder, L. R., 147,148 Webcr,J. 11., 147
Sokolova, V. 1.• 220 Welte, D. 11., 106
Solodkov, V. K., 131 Wiebe, H. A., 275
Srirkin, V. G., 105. 174, 184, 186, 190,298 300 Williams, A. L., 141
301,304,305 • •
Wotfson, I. S., 112
AUTIIORINDEX
393
Yakovets, Yu. A., 112 Yuskovich, A. K., 295

Yamane, M., 217 Yusupova, N. A., 132
Yapryntseva, V. G., 126, 129, 133, 139
Yaschenko, V. L., 196,335 Zaitova, A. Ya., 213
Yelin, R. E., 273,274 Zakharov, E. P., 227,252,296,298
Yoshida, H., 278 Zimina, K. I., 138

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This article was downloaded by: [University of Arizona]

On: 19 April 2015, At: 17:10

ORGANIC SULFUR COMPOUNDS OF

To cite this article: G. F. BOLSHAKOV (1986) ORGANIC SULFUR COMPOUNDS OF PETROLEUM,

To link to this article: http://dx.doi.org/10.1080/01961772.1986.10462153

PLEASE SCROLL DOWN FOR ARTICLE

ORGANIC SULFUR COMPOUNDS

11. CONTENT OF ORGANIC SULFUR COMPOUNDS IN OILS AND

IV. CHEMICAL AND PHYSICAL PROPERTIES .....•••.••.......•............•.•.•..• 222

W.1.2. Sulfides ........................... · ........... · · · · · · · · ..... · · · · · · · 224

W.4.2. Entropy, Enthalpy, Isobar Potential .................................. . 262

V. MAIN SYNTHETIC ROUTES TO ORGANIC SULFUR COMPOUNDS

VI. APPLICATION OF ORGANIC SULFUR COMPOUNDS OF PETROLEUM . . . . . . . . . . . . . 298

VII. EFFECT OF ORGANIC SULFUR COMPOUNDS ON SERVICE PROPERTIES

Sulfur-poor Normal Sulfur-rich

Maintenance costs 2130 2980 3650

11. CONTENT OF ORGANIC SULFUR COMPOUNDS IN PETROLEUM

11.1. Total Sulfur Content of Petroleum

Sulrur content or oils from collectors

Paleogene 0-1000 0.65 2.64 1.35

Cretaceous 0-1000 0.73 2.83 1.65

Jurassic 0-1000 0.34 0.63 0.40

Triassic 0-1000 0.75 0.75

Permian 0-1000 0.36 1.83 1.02

Carbonic 0-1000 0.27 2.51 1.25

Devonian 0-1000 0.34 0.58 0.42

Silurian 0-1000 0.14 0.14

Ordovician 1000-2000 0.24 1.41 0.91

Cambrian 0-1000 0.27 0.2.7

In dissolved gases In rree gases

Age or Depth or terrlgenous c:arbonaceous terrlgenous carbonaceous

Neogene 0-1000 0.00 3.12 0.002 0.00

4000-5000 0.00 O.OOt

Paleogene 0-1000 0.003 0.28 0.00 0.14

Cretaceous 0-1000 0.00 1.71 0.001 0.02

Jurassic 0-1000 0.00 0.00

Triassic 0-;-1000 0.00 0.001 8.40

Permian 0-1000 0.00 0.00 0.00

Carbonic 0-1000 0.00 0.00 0.00 0.04

Devonian 0-1000 0.00 0.00 0.15

Silurian 0-1000 0.00 0.00 0.00

Ordovician 0-1000 0.00 0.00 0.00 0.00

Cambrian 0-1000 0.00 0.00

SULFUR CONTENT, wt.%

11.2. Sulfur Content of Petroleum Fractions

In order to recognize general patterns in the sulfur compound distribution in

Average sulfur content, wt. %

500-1000 2.07 0.274 1.150 2.03 2.76 0.686 1.48 3.48

*) Without Cambrian; .. ) 300-360 °C; ... ) IBP-360 CC

An analogous change in the sulfur content passing through a maximum is common

II.3. Group Chemical Composition of Organic Sulfur Compounds in

The sulfur compound chemical composition in oils is determined by the type of

Lithology of Age of Depth or

content changes with depth in a more complicated fashion. It is minimal at a depth of

Methanethiol 5.95 2.40 Wasson, USA

2-Butanethiol 84.98 3.86 Wasson

2-Pentanethiol 112.9 1.40 Wasson

Mercaptans from the high-molecular part of oil present a rather complicated

2-Thiapropane 37.34 0.88 . Wasson, USA

2-Methyl-3-thiapentane 107.38 0.101• Libyan