Carbon Disulfide

MANCHIU D. S. LAY, Stauffer Chemical Co., Dobbs Ferry, New York 10522,
United States
MITCHELL W. SAUERHOFF, Stauffer Chemical Co., Dobbs Ferry, New York 10522,
United States
DONALD R. SAUNDERS, Stauffer Chemical Co., Dobbs Ferry, New York 10522,
United States

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . 667 6. Quality Specifications and Analytical

2. Physical Properties . . . . . . . . . . . . . . . . . . . 667 Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
3. Chemical Properties . . . . . . . . . . . . . . . . . . 668 7. Storage and Transportation . . . . . . . . . . . . 673
4. Production . . . . . . . . . . . . . . . . . . . . . . . . . . 669 8. Uses and Economic Aspects . . . . . . . . . . . . . 673
4.1. Thermodynamics and Rates of Reaction . . . 670 9. Toxicology and Occupational Health . . . . . . 675
4.2. Production from Charcoal and Sulfur . . . . . 670 10. Carbonyl Sulfide . . . . . . . . . . . . . . . . . . . . . 676
4.3. Production from Methane and Sulfur . . . . . 671 References . . . . . . . . . . . . . . . . . . . . . . . . . . 676
4.4. Other Processes . . . . . . . . . . . . . . . . . . . . . . 672
5. Environmental Aspects . . . . . . . . . . . . . . . . 672

1. Introduction used as rubber chemicals, flotation agents, and

pesticides.
Carbon disulfide [75-15-0], CS2, is an important
industrial chemical with an extensive and well-
developed chemistry. LAMPADIUS discovered car- 2. Physical Properties
bon disulfide in 1796 while heating a mixture of
iron pyrite and carbon. Industrial interest in this Carbon disulfide is a volatile, dense liquid with
compound dates back to 1839, when it was a wide flammability range in air (1 – 50 vol %)
prepared by SCHRO¨ TTER using charcoal and sulfur [2]. It has an unusually low autoignition point
in a heated retort [1]. Its solvent power was (100 ○C) and a low flash point ( 30 ○C). Its
recognized early, and for some time carbon —
evaporation rate into air is 1.6 times that of
disulfide was widely used for the extraction of diethyl ether [3]. It is an excellent solvent for
fats and oils. It was, however, not until introduc- many organic compounds and readily dissolves
tion in the early 1900s of the viscose rayon sulfur, phosphorus, iodine, waxes, rubber, and
process, which uses carbon disulfide to solubilize resins. The commercial product has a pungent
cellulose, that it began to assume the role of a odor characteristic of sulfur compounds.
large-scale industrial chemical. By the late Some of the most useful physical, thermo-
1960s, competition from petroleum-based syn- chemical, and transport properties of carbon
thetic fibers began to affect the earlier rapid disulfide are as follows (also see Table 1) [1],
growth of rayon; the 1970s witnessed a decline [4–13]:
of the rayon market and correspondingly that of
carbon disulfide. Usage of carbon disulfide has
since stabilized, and a small market growth is Mr 76.13
projected for the future. fp — 111.6 ○ C
Of the 1.1×106 t of carbon disulfide produced bp at 101.3 kPa 46.23 ○ C
worldwide in 1984, over 75 % was used by the Density,
regenerated cellulose industry. The rest was liquid at 25 ○ C 1260 kg/m3
con- sumed in production of carbon saturated gas at 20 ○ C 8.07 kg/m3
Critical temperature 273 ○ C
tetrachloride and miscellaneous organosulfur Critical pressure 7600 kPa
compounds

© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a05_185
668 Carbon Disulfide Vol. 6
○
Surface tension at 20 C 32.3 mN/m
Refractive index, liquid at 20 ○ C 1.62546 Carbon disulfide reacts with sulfides, alco-
Electrical conductivity at 18 ○ C 78×10—19 W—1 cm—1 hols, ammonia and amines, and chlorine to give
Dielectric constant at 20 ○ C 2.63 industrially important derivatives and intermedi-
Interfacial tension, CS2– H2O 48.2 mN/m ates. Aqueous alkalies react slowly with carbon
Heat of combustion at 25 ○ C 1032 kJ/mol disulfide to give the trithiocarbonate and
Heat of formation,
gas at 25 ○C, 101.3 kPa 117.1 kJ/mol
carbon- ate:
Heat of fusion 4.390 kJ/mol 3 CS2þ6 NaOH ! 2 Na2CS3þNa2CO3þ3 H2O
Heat of vaporization at 25 ○ C 27.41 kJ/mol
Specific heat, liquid at 25 ○ C 76.45 J mol—1 K—1
Specific heat, Trithiocarbonates are also formed with metal
gas at 25 ○C, 101.3 kPa 46.2 J mol—1 K—1 sulfides:
Entropy, gas at 25 ○C, 101.3 kPa 237.83 J mol—1 K—1
Free energy of formation, K2S ðaqueousÞþCS2 ! K2CS3
gas at 25 ○C, 101.3 kPa 66.9 kJ/mol
Thermal conductivity,
liquid at 25 ○C, 101.3 kPa 0.162 W m—1 K—1 Carbon disulfide reacts with alcoholic
gas at 25 ○C, 101.3 kPa 0.0078 W m—1 K—1 alkalies to produce xanthates (salts of
Viscosity, dithiocarbonates) [17]:
liquid at 25 ○C, 101.3 kPa 0.36 mPa · s
gas at 25 ○C, 101.3 kPa 0.0098 mPa · s ROHþNaOH!RONaþH2 O
Diffusivity,
gas at 0 ○C, 101.3 kPa
RONaþCS2 !ROCSSNa
self-diffusion 0.0472 cm2/s
diffusion in air 0.0892 cm2/s
diffusion in CO2 0.063 cm2/s This reaction is the basis for the viscose
liquid at 25 ○C, 101.3 kPa process in which cellulose is converted to the
self-diffusion 4.1×10—5 cm2/s xanthate and regenerated as fibers and films:
ðcelluloseÞONaþCS2 ! ðcelluloseÞOCSSNa

Vapor pressure 2ðcelluloseÞOCSSNaþH2 SO4 ! 2ðcelluloseÞOH

t, ○ C —10 0 10 20 30 46.22 (bp) 60 80 þ2 CS2þNa2SO4
p, kPa 10.48 16.95 26.41 39.76 58.03 101.3 155.7 272.2
t, ○ C 100 125 150 175 200 225 250 273 (tcrit)
p, kPa 450.0 785.8 1247 1930 2854 4108 5693 7615 (pcrit)
Carbon disulfide reacts with ammonia and,
depending on ammonia concentration and on
temperature, forms ammonium dithiocarbamate
(1) [513-74-6], ammonium trithiocarbonate (2)
3. Chemical Properties [13453-08-2], and ammonium thiocyanate (3)
[1762-95-4] [14]:
The chemistry of carbon disulfide is extensive
and well-investigated [1], [5], [14–16].
Compre- hensive surveys of the inorganic
chemistry of carbon disulfide have appeared [1],
[5]. A de- tailed review of the organic reactions
of carbon disulfide is given in reference [15].

Table 1. Mutual miscibilities of carbon disulfide – water [6] In the vapor phase and at higher temperature
CS2in H O,
2 H2O in CS2, (150 – 160 ○C), thiourea [62-56-6] is obtained
Temperature, ○C g/100 g g/100 g via decomposition of the thiocyanate [14]:
0 0.242 – NH4 ðSCNÞ ! SCðNH2 Þ2
10 0.230 0.0086
20 0.210 0.012
30 0.185 0.017 Reactions with primary and secondary
40 0.111 0.022 amines produce principally the dithiocarbamate
salts [18]: In the presence of alkalies, many commercial-
ly important salts of dithiocarbamic acid are
2 RNH2 þCS2 !RNHCSSNH3 R obtained:

2 R2 NHþCS2 !R2 NCSSNH2 R2 R2NHþCS2þNaOH ! R2NCSSNaþH2O

Sodium methyldithiocarbamate [137-42-8],

CH3NHCSSNa, an important soil fumigant, is
Vol. 6
produced by the reaction of carbon disulfide
with methylamine and an aqueous solution of
caustic soda. In a similar reaction with
ethylenediamine, the fungicide sodium ethylene
bis(dithiocarba- mate) [142-59-6] is the
reaction product:
Two important vulcanization accelerators are
products in the reaction of aniline with carbon
disulfide. In the absence of sulfur,
thiocarbanilide [102-08-9] is obtained:
With sulfur, 2-mercaptobenzothiazole [149-
30-4] (MBT) is produced:
Thiurium disulfides, a family of compounds
used as fungicides and vulcanization accelera-
tors, are formed by oxidizing dithiocarbamates
[18]:
2 R2NCSSNaþH2O2þH2SO4 ! ðR2NCSS—Þ2
þNa2SO4þ2 H2O
Chlorination of carbon disulfide gives rise to
a host of chlorinated products [19]. At tempera-
tures between 5 and 30 ○C and in the absence of
iron, iodine-catalyzed chlorination of carbon
disulfide gives good yields of trichloromethane-
sulfenyl chloride [594-42-3]:
2 CS2þ5 Cl2 ! 2 Cl3CSClþS2Cl2
Carbon Disulfide 669
Depending on the degree of chlorination,
some carbon tetrachloride [56-23-5], sulfur
dichloride [10545-99-0], and thiophosgene
[463-71-8] are also formed.
In the presence of iron and metal chlorides
and at higher temperature (70 – 100 ○C),
carbon tet- rachloride and sulfur chlorides are
exclusively obtained [14]:
CS2þ3 Cl2 ! CCl4þS2Cl2
Further reaction of the sulfur monochloride
[10025-67-9] with carbon disulfide produces
more carbon tetrachloride and sulfur:
CS2þ2 S2Cl2 = CCl4þ4S
These two reactions are the basis for the
commercial production of carbon tetrachloride
from the chlorination of carbon disulfide [20].
The reaction with chlorine is very fast and pro-
ceeds to completion. Carbon disulfide and sulfur
(I) chloride react more slowly. The stoichiomet-
ric reaction is equilibrium limited at about 70 %
at 90 ○C.
Carbon disulfide reacts readily with water in
the presence of alumina and oxide catalysts
above 150 ○C to form carbon dioxide and
hydro- gen sulfide:
CS2þ2 H2O ! CO2þ2 H2S
Carbonyl sulfide is an intermediate in this
hydrolysis reaction:
CS2þH2O ! COSþH2S
COSþH2O ! CO2þH2S
At 200 – 300 ○C, equilibrium conversion of
carbon disulfide is nearly complete [21].
At temperatures above 150 – 200 ○C and in
the presence of metal sulfide catalysts, notably
molybdenum and nickel sulfides, carbon disul-
fide is reduced by hydrogen to give various
amounts of methanethiol, dimethyl sulfide,
methane, and hydrogen sulfide [22].
4. Production
Carbon disulfide is commercially manufactured
by the reaction of sulfur with charcoal or
670 Carbon Disulfide
methane. Ethane, propane, and propene have
been used to a limited extent. Since the methane
process was first introduced in the early 1950s,
it has steadily supplanted the older charcoal
pro- cess, which is no longer a factor in carbon
disulfide manufacture in the United States, Eur-
ope, and Japan. In areas where natural gas or
methane is not readily available or when plant
size is relatively small, the charcoal process still
supplies local viscose rayon requirements.
4.1. Thermodynamics and Rates
of Reaction
The reactions of sulfur with either carbon or
methane have been evaluated for the following
equations [23]:
CðsÞ þ2 SðgÞ ! CS2ðgÞ
CH4ðgÞ þ4 SðgÞ ! CS2ðgÞ þ2 H2 SðgÞ
The maximum yield from carbon was found
to be 91 % at 720 ○C. For the methane reaction,
complete conversion was attained at 300 ○C. In
practice, higher temperature is required to pro-
vide economic reaction rates. The reactions are
endothermic over most of the temperature range
practiced commercially; the energy supplied is
taken up mainly by vaporization and superheat-
ing of sulfur [23–25].
The thermodynamics of sulfur dissociation
[7], [23], [24] determine the concentration of
the reactive diatomic sulfur molecule, S 2; high
tem- perature and low pressure favor high S 2
concen- trations [7]. Equilibration rates of the
vapor species, Sn (n 1 – 8), are relatively fast
¼ values of S 2 may be used in
so that equilibrium
rate equation formulation.
Homogeneous and heterogeneous rate data
for the reaction of methane and sulfur have been
obtained for temperatures between 500 and
700 ○C [26], [27–30]. The rate equation that
best fits these data is one that is first order with
respect to methane and S2:
rate ¼ k cCH4 cS2
where k is the reaction rate constant.
The following are the Arrhenius equations
for the rate constants, based on reference [26].
For the homogeneous reaction:
reason. The charcoal is normally precalcined at
500 ○C to remove volatiles that could result in
formation of objectionable byproducts. Thermal
efficiency of retorts is ca. 25 %; carbon and
sulfur yields are generally below 90 % [34–
36].
Electrical resistance heating in brick-lined
electrothermal reactors provides an alternative
heat source for the reaction of charcoal with
Vol. 6
k ¼ 1:9 × 106
expð—52000=RTÞmolh—1 cm—3 kPa—2
For the silica gel catalyzed reaction:
k ¼ 7:7 × 102
expð—28000=RTÞmolh—1 g—1 catal·kPa—2
Other values for these rate constants as well as
space velocities for the catalyzed reaction have
been reported [27–31]. At 600 ○C, the
homoge- neous rate is about 1 % that for the
silica gel catalyzed reaction.
4.2. Production from Charcoal and
Sulfur
The basic process for the reaction of charcoal
with sulfur has changed little since its inception
in the mid 1840s. Externally heated retorts are
still being used, although equipment design has
undergone much improvement as better materi-
als of construction have become available. De-
tails on retort design are available in references
[32], [33].
In retort plants [34], [35], molten sulfur is
vaporized and superheated either before or after
addition to the retort. Reaction between the
superheated sulfur vapor and a stationary bed of
charcoal at 850 – 900 ○C takes place inside the
retort at slightly above atmospheric pressure.
The product gas, consisting of carbon disulfide,
some sulfur, hydrogen sulfide, carbonyl sulfide,
and inerts, passes through a train of condenser,
scrub- ber, and oil absorber where the crude
carbon disulfide is recovered; the pure product
is ob- tained by further treatment in distillation
col- umns. The tail gas, made up primarily of
hydro- gen sulfide, carbonyl sulfide, and inerts,
is either incinerated and scrubbed with a caustic
solution or routed to a sulfur recovery plant.
Typically, each retort can produce 1 – 3 t/d
of carbon disulfide. High-temperature corrosion
of the cast iron retorts limits their useful life to
less than 1 year. The raw materials used in the
retorts should be low in ash and residue to
minimize the frequency of reactor cleanouts.
Fouling of the retorts also restricts heat transfer
and shortens retort life. Charcoal quality is
extremely impor- tant because less reactive
material requires higher temperature for
satisfactory operation; charcoal derived from
hardwood is preferred for this
sulfur [37]. Where cheap power is available, the
electrical method may be more economic. Power
consumption as a function of carbon disulfide
produced is ca. 1200 kW h/t. Other advantages
offered by electrothermal reactors are a larger
capacity per reactor (up to 10 t/d) and a longer
reactor life; furthermore, a wider range of solid
carbon feed can be used because electrothermal
reactors can generate higher temperatures.
Vol. 6
4.3. Production from Methane and
Sulfur
As demand for carbon disulfide rapidly
increased in the 1940s, limitations of the
charcoal processes provided the incentive for
development of a more efficient large-scale
method for its manufacture. Readily available
cheap natural gas and favor- able
thermodynamics [21], [23], [31] led to the
successful development of the process based on
the catalyzed reaction of methane and sulfur
[21], [27–31], [38], [39]. During the period
1943 –
Figure 1. Methane process for CS 2 production a) Reaction furnace; b) Catalytic reactors; c) Sulfur condenser; d) CS 2 scrubber;
e) CS2 condenser; f) CS2 absorber; g) Oil interchangers; h) CS2 stripper; i) Stabilizer column; j) Purification column; k)
Caustic wash column; l) Water wash column
Carbon Disulfide 671
1965, many patents were issued that covered
various aspects of the process [38–54].
The commercial methane process [35], [55],
[56] is based primarily on work described by
the patents issued to the Pure Oil Co. [41–45].
The rights to these patents were acquired by the
Food Machinery Corp. and Stauffer Chemical
Co., and in 1953, the first methane process plant
was built by FMC in South Charleston, West
Virginia. This was followed by a Stauffer plant
at LeMoyne, Alabama, three years later. By the
mid 1960s all carbon disulfide in the United
States was man- ufactured by this method;
many similar plants soon followed in Europe
and elsewhere [35]. Over 85 % of the world’s
production capacity is based on methane.
Figure 1 shows a typical methane process
flow sheet. Purified natural gas containing over
95 % methane and low concentrations of propane
and heavier hydrocarbons is preheated to about
250 ○C in the convection section of the reaction
furnace. The furnace is a typical box-type
pyrolysis furnace commonly used in the
petrochemical industry, with radiant and
convection sections [57]. The hot methane gas is
mixed with liquid sulfur and intro- duced into the
horizontal heating coil located in the radiant
section. There the liquid sulfur is vaporized, and
the temperature of the mixture is raised to 550 –
650 ○C. Operating pressure is typically 400 –
700 kPa. Alternatively, the methane and sulfur
may be introduced separately and at differ- ent
locations of the coil. A slight excess of sulfur
6 Carbon Disulfide
(5 %) is used to ensure good methane conversion
and to minimize carbon and tar formation.
To withstand the high-temperature corrosive
environment, cast high-alloy stainless steel is
used as tube material. Tube life is normally
2 – 3 years. Packed, brick-lined reactors are
connected to the heating coil to provide
addition- al residence time and housing for
catalyst beds. Reaction takes place both in the
tubes and in the reactors; almost all the
hydrocarbons are con- verted by the time the
gas leaves the last reactor. Gas exiting the
reaction furnace system passes through the
sulfur condenser where most of the excess
sulfur is separated. Next the cooled gas goes
through a sulfur scrubber and then to the CS2
scrubber in which the remaining sulfur is re-
moved. The relatively sulfur-free gas then enters
water-cooled condensers for bulk separation of
carbon disulfide. The remaining carbon
disulfide is finally removed from the hydrogen
sulfide gas in the oil absorber. The hydrogen
sulfide gas exiting the oil absorber contains 1
– 2 % meth- ane and less than 1000 ppm
carbon disulfide.
This gas is routed to a Claus sulfur recovery
plant where it is converted back to sulfur.
Crude carbon disulfide from the condensers,
including that recovered in the stripper, is sent to
the stabilizer column for removal of low-boiling
impurities. The bottoms from the stabilizer
column are next processed in the purification
column where high-boiling contaminants are
separated from the product. A caustic and water
wash complete the product purification
operations, and the finished product is pumped to
check tanks and storage.
4.4. Other Processes
The use of different feedstocks for the manufac-
ture of carbon disulfide is a subject of much
economic interest. Raw materials evaluated in-
clude the following: methane and hydrogen sul-
fide [58], [59]; coke and coal with sulfur
dioxide and hydrogen sulfide [60–62]; liquid
hydrocar- bons with sulfur [63–65];
hydrocarbons with sulfur and sulfur dioxide
[66], [67]; chlorinated hydrocarbons and sulfur
[68]; carbon monoxide and sulfur [36]; and
organosulfur compounds with sulfur [69]. Most
of these alternatives are unattractive because of
poor yield, undesirable byproducts, or
difficulties in processing due to tar and polymer
formation [70].
Vol. 6
Important refinements to the basic methane
process include the use of high-pressure
(2000 kPa) condensation and fractionation for
product recovery and purification [54], and
mod- ifications to the reaction furnace system to
allow the use of olefinic feedstocks [71], [72].
5. Environmental Aspects
Carbon disulfide in the atmosphere is of
biogenic as well as industrial origin [73].
Tropospheric concentrations of carbon disulfide
have been reported as 3 10—5 ppm in remote
areas and ×
7×10 – 30×10—5 ppm in urban and industrial
—5
locations [74]. Natural release includes diffuse
emission from soil [75] and volcanic eruption
[73]. Industrial sources consist mainly of
release from gasification and pyrolysis of
carbonaceous fuel in the presence of sulfur
compounds, from sulfur recovery (Claus) plant
tail gas, and from industrial users of carbon
disulfide [73], [74].
Investigations on the fate of carbon disulfide
in the atmosphere show that the principal oxida-
tion products are sulfur dioxide, carbonyl
sulfide, and carbon monoxide [73], [76], [77].
Eventually these compounds degrade to carbon
dioxide and sulfates.
Carbon disulfide may be removed from gas
streams by oil absorption or adsorption with
activated carbon [78], [79]. A common method
used in the treatment of carbon disulfide and
carbonyl sulfide in sulfur recovery plant tail gas
involves hydrogenation and hydrolysis of these
compounds to carbon dioxide and hydrogen sul-
fide. The hydrogen sulfide is then recovered by
absorption in alkanolamine solutions [78], [80].
6. Quality Specifications and
Analytical Methods
Carbon disulfide produced commercially in
mod- ern plants is generally of high purity and
meets most of the specifications listed in Table
2.
Analytical methods for detecting carbon di-
sulfide are detailed in references [83], [84]. A
common procedure, sensitive to 1 ppm, is based
on the reaction of carbon disulfide with diethy-
lamine in the presence of a cupric salt to give
the characteristic yellow cupric
diethyldithiocarba- mate. Infrared
spectrophotometry is sensitive to
Table 2. Carbon disulfide specifications [81–83]

Grade

Property Commercial ACS reagent Viscose

Residue, % 0.002 0.002 0.01
Relative density d, 20 ○C 1.261 – 1.265 – 1.260 – 1.270
Color, APHA 20 10 colorless
Dissolved sulfides
lead acetate test negative – –
mercury drop test bright bright –
Sulfite and sulfate – 0.002 % SO2 –
Boiling range 46 – 47 ○C 1 – 95 mL < 0.5 ○C; 98.5 % should distill between 46 and 47 ○C
95 mL – dryness < 0.5 ○C
Water, % – 0.05 –

5 ppm, and gas chromatography can provide Class 1 flammable liquid (identification number
detection to 0.5 ppm. 1131). Use of the red label for flammable liquid
is required. Transport of this chemical should
fol- low DOT regulations [88].
7. Storage and Transportation [81],
[85], [86]
8. Uses and Economic Aspects
The toxicity and extreme flammability and vol-
atility of carbon disulfide make it one of the In 1984, an estimated 1.1×10 6 t of carbon disul-
most hazardous chemicals to handle. Facilities fide was produced worldwide in the following
using carbon disulfide must be designed to areas (production figures in 103 t/a):
operate, at
all times, as a closed system and above atmo-
spheric pressure to avoid the influx of air. North America 235
When- ever possible, these plants should be Western Europe 260
located outdoors or in open structures away Eastern Europe 250
from flames and other sources of ignition. Latin America 50
Equipment should be properly grounded to Asia 160
prevent accumulation of static electricity. Water Africa 10
deluge systems around processing and storage Former States of USSR 120
areas should be provided; enclosed units should Total 1085
be designed with proper ventilation of the
downdraft or lateral types. In 1991 1.3×106 t of carbon disulfide was
Areas where appreciable concentration of produced worldwide in the following areas
carbon disulfide may be present should be (pro- duction figures in 103 t/a):
desig- nated as Class 1 hazardous locations as
defined by the National Electrical Code [87];
electrical specifications should be in accordance
with the requirements of the code. North and Central America 190
Carbon disulfide is stored in properly diked South America 54
above-ground steel tanks or in tanks confined in Europe and Africa 822
open-top water-flooded concrete pits. Underwa- Asia 221
ter tanks are water padded, whereas water or Total 1287
inert gas padding is used in above-ground tanks.
Transfer of carbon disulfide from storage tanks
may be by padded pressure or pumps [81]. [89]
Carbon disulfide is classified by the United The regenerated cellulose industry is by far
States Department of Transportation (DOT) as a the largest user of carbon disulfide. Over 65 %
of world production is used in the manufacture
of rayon (ca. 0.32 kg of carbon disulfide is
 Table 3. Uses of carbon disulfide and its derivatives

Compound Application Reference

Carbon disulfide reaction and extraction solvent, catalyst presulfi-
dation agent, oil well solvent, cold vulcanization [33], [81]
additive for rubber, synthetic chemical
Sodium cellulose xanthate precursor for rayon, cellophane, and regenerated
cellulose products; chelating agent [17]
Alkyl xanthates flotation agent, lubricant additive, analytical reagent [17], [83]
Carbon tetrachloride fluorocarbon refrigerant, degreasing and cleaning [20]
solvent
Trichloromethanesulfenyl chloride intermediate for fungicide and pesticide [90], [20], [125]
manufacture
Sodium, potassium, and ammonium thiocyanate fungicide, electrolysis and electroplating solution [91]
additive, corrosion inhibitor, photographic emul-
sion stabilizer, metal complexing agent, fabric dye
enhancer, herbicide, insecticide, soil sterilant, in-
termediate for pharmaceuticals
Dithiocarbamates fungicide, insecticide, soil fumigant, herbicide and [33], [92], [93]
defoliant, rubber vulcanization accelerator
Thiocarbanilide rubber vulcanization accelerator [94], [95]
Benzothiazoles rubber vulcanization accelerator [94], [95]
Thiazolsulfenamides delayed rubber vulcanization accelerator [95]

consumed for each kilogram of rayon Table 5. World production capacity for carbon disulfide, 1000 t/a,
produced). Some 10 % is used in making 1984a
cellophane, and
another 10 % is chlorinated to form carbon
tetra-
chloride (about 25 % of world carbon tetrachlo- Area Charcoal Methane
ride is produced by this method). The process process
remaining
15 % is distributed among rubber chemicals, North America – 335
United States and Canada
flotation agents, pesticides, and miscellaneous
chemical reagents. Table 3 lists uses of carbon Western Europe – 360
disulfide and some of its derivatives. United Kingdom, France,
Historical production and price data in the Unit- Federal Republic of Germany,
ed States are shown in Table 4. Competitive pres- Belgium, Spain
sure from synthetic fibers and films will continue to
limit market growth in the regenerated cellulose Eastern Europe 40 260
Poland, Rumania, Bulgaria,
industry. Improvement in carbon disulfide usage will German Democratic Republic
be slow and must come from increased use in
USSR
agricultural and specialty chemicals manufacture. 40 120

World production capacity for carbon disul- Japan – 100

fide is shown in Table 5. Excess capacity will
India 50 –
continue in the United States and Europe.
China 20 –
Table 4. United States carbon disulfide production and price

Production, Latin America 60 15

Year $/t 103 t/a Argentina, Brazil, Mexico,
Columbia, Chile, Peru
1965 94 345
1970 97 330 Others 15 –
1975 145 220 Egypt, South Africa, Australia
1980 240 170 Total 225 1190
9. Toxicology and
1984 420 210 mental
* investigations on animals and many clin-
References [40], [96], and various trade sources
Occupational Health ical and epidemiological reports on humans.
Mutagenicity and Genotoxicity. The mu-
The toxicology data base on carbon disulfide is tagenic and genotoxic potential of carbon disul-
extensive. Citations include hundreds of experi- fide has been evaluated in vitro and in vivo [97–
100]. Carbon disulfide does not exhibit mu-
tagenic activity in bacteria (S. typhimurium and
E. coli) with or without the presence of an
activation system. Additional in vitro tests, in-
cluding host-mediated assay, unscheduled DNA
synthesis in human fibroblasts, and primary cul-
tures of human leukocytes, are inconclusive
[101], [102]. However, the significance of these
tests cannot be properly evaluated because of
methodological problems including the lack of
proper positive controls. Therefore, insufficient
data are available to evaluate the mutagenic and
genotoxic potential of carbon disulfide.
Human Health Effects. Carbon disulfide
toxicity in humans is well-documented in the
literature. It was first recognized as a workplace
hazard by the French in the 1850s. Subsequent
studies demonstrated effects on the central and
peripheral nervous systems and cardiovascular
system. Carbon disulfide can induce polyneuro-
pathy and encephalopathy. Poisoning may be
acute or chronic.
Symptoms of polyneuropathy include pares-
thesia, cramps, muscle weakness, pain, distal
sensory loss, and neurophysiological
impairment [103–110]. Exposure to high
levels of carbon disulfide for prolonged periods
is necessary to produce the polyneuropathy.
However, exposure at levels of 65 – 170 ppm
for less than 1 year are reported to result in
many of the symptoms described [103].
Symptoms of encephalopathy may include
headache, sleep disturbances, gen- eral fatigue,
loss of libido, impotence, organic dementia, and
Parkinsonism [103–110]. Onset of symptoms
range from several months to several years. The
early stage of encephalopathy is char- acterized
by depression with sudden attacks of
hallucinations. Visual disturbances that may re-
sult from high levels of carbon disulfide
exposure
Biochemical Mechanisms. Understanding
the mechanism of action of carbon disulfide
toxicity may lead to early clinical intervention
in cases of suspected poisoning. Although a
number of hypotheses have been proposed, the
biochemical mechanism(s) remain unknown. A
metabolite of carbon disulfide may be responsi-
ble for its hepatotoxic effects [117], [118].
Sulfur is liberated during conversion of carbon
disulfide to carbon dioxide. The liberated sulfur
include abnormal color vision, loss of visual
acuity, loss of accommodation, and retinopathy
[111].
Cardiovascular alterations in humans may
also result from carbon disulfide exposure. A
number of studies [112–114] reveal vascular
atherosclerotic changes following long-term ex-
posure to carbon disulfide (30 – 90 mg/m3).
Be- low 10 ppm, cardiovascular effects are not
apparent.
The toxic effects of carbon disulfide require
that precautions should be taken to limit
exposure in the workplace. In the United States,
the TLV- TWA as adopted by ACGIH for
exposure to carbon disulfide is 30 mg/m 3, 10
ppm [115]; the MAK value is the same. The
federal standard (OSHA, 1985) is 60 mg/m3.
Disposition. The primary route of human
carbon disulfide exposure is inhalation. Uptake
in the blood is rapid and carbon disulfide is
transported to tissues. Carbon disulfide
possesses significant lipophilicity while also
binding to proteins and amino acids. In
humans, most (> 70 %) of a systemically
absorbed dose is rapidly converted to
metabolites, followed by urinary excretion. Less
than 30 % of carbon disulfide is exhaled and
very small quantities are excreted unchanged
[116].
Subchronic Toxicity. A 90-d inhalation
toxicity study using Fischer 344 rats, Sprague-
Dawley rats, and B6C3F1 mice (exposed simul-
taneously in the same chambers) was conducted
with carbon disulfide vapor [117]. Evaluation of
the hematology examinations (Fischer 344 and
Sprague-Dawley rats) indicated effects on red
cells and platelets. In addition, high-dose
animals of both sexes exhibited a mild increase
in neu- trophils and a decrease in lymphocytes.
Serum chemistry examinations at the high dose
did not reveal dramatic changes. Organ weight
data re- vealed a depression of brain as well as
liver weight.
Histopathology studies revealed axonal
swell- ing of spinal cord nerve fibers in high-
dose males, high-dose females, and possibly
mid-dose males. In addition, males and females
from the high- dose group had segmental
degeneration of fibers in the sciatic nerve. Other
lesions that oc-curred were incidental and not
related to treatment.
may bind to cellular components or critical
enzymes, giv- ing rise to toxicity.
Research has also focused on related areas,
including the role of carbon disulfide in chelating
dithiocarbamates, binding and depleting essen-
tial trace elements, disturbing vitamin metabo-
lism [73], turnover of catecholamines [119], and
metabolizing lipids [120–122].
10. Carbonyl Sulfide
Carbonyl sulfide [463-58-1], carbon
oxysulfide, COS, is a colorless, flammable gas
that is spar- ingly soluble in water but very
soluble in alco- holic alkalies [123]. Selected
physical properties are:
Mr 60.07
mp — 138.8 ○ C
bp at 101.3 kPa — 50.2 ○ C
Heat of vaporization at 101.3 kPa 18.50 kJ/mol
Vapor density at 101.3 kPa, 25 ○ C 2.485 kg/m3
Critical temperature 105 ○ C
Critical pressure 6179.4 kPa
Heat of formation at 25 ○ C — 142.1 kJ/mol
Free energy of formation at 25 ○C — 164.3 kJ/mol
The chemistry of carbonyl sulfide has been
reviewed [14], [123], [124]. Production of car-
bonyl sulfide may be by the reaction of carbon
monoxide with sulfur [123], reduction of sulfur
dioxide with carbon [62], or hydrolysis of
carbon disulfide [21]. Small amounts of
carbonyl sulfide invariably are formed when
carbonaceous fuel is pyrolyzed in the presence
of oxygen, steam, and sulfur compounds [78];
the removal of carbonyl sulfide from these gas
streams is the subject of many studies [78],
[80].
Carbonyl sulfide is widely dispersed in the
earth’s atmosphere; concentrations between
4.7×10—4 and 5.3×10—4ppm have been reported
9 D. A. Stull, H. Prophet, JANAF Thermochemical
Tables, 2nd ed., NSRDS-NBS 37, U.S. Govt. Printing
Office, Washington, D.C., 1971.
10 R. W. Gallant: Physical Properties of Compounds,
vol. 2, Gulf Publishing Co., Houston, Tex., 1970,
pp. 178 – 184.
11 R. N. Perry, D. Green (eds.): Perry’s Chemical En-
gineers’ Book, 6th ed., McGraw-Hill, New York
1984, section 3, pp. 247 – 259.
12 D. R. Stull, Ind. Eng. Chem. 39 (1947) 517.
[74]. Carbonyl sulfide has been suggested as a
major causative agent in atmospheric sulfur cor-
rosion [74].
The commercial importance of carbonyl
sul- fide is limited; it is not produced in large
quantity, and is used principally for small-scale
syntheses and experiments. The use of carbonyl
sulfide as a raw material for chemical
manufacture has been proposed [126].
Carbonyl sulfide appears to play an impor-
tant role in mediating the toxicity of carbon
disulfide. Carbon disulfide is metabolized in
vitro [127] and in vivo [128] to carbonyl
sulfide. Carbonyl sulfide is further metabolized
by hepatic carbonic anhydrase to hydrogen
sulfide [128].
Death from acute inhalation of carbonyl sul-
fide can occur within 45 min [129] at
concentra- tions of 20 000 ppm. A single
intraperitoneal injection of 50 mg/kg resulted in
100 % mortali- ty. Presently, complete
subchronic toxicity stud- ies on carbonyl sulfide
are unavailable. There is one report, however,
describing effects following subchronic
administration. Rabbits [112] were continuously
exposed for 7 weeks to ca. 50 ppm COS.
Within five days, three rabbits died and two
were sacrificed in a moribund condition. There
were no further mortalities. Cholesterol (serum)
elevations were noted in exposed rabbits. Histo-
pathology did not reveal changes in the lungs or
in the intima of the arteries in the organs
evaluated.
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Further Reading
D. E. Smith, R. W. Timmerman: Carbon Disulfide,
‘‘Kirk Othmer Encyclopedia of Chemical
Technology’’, 5th edition, vol. 14, p. 490–529, John
Wiley & Sons, Hobo- ken, NJ, 2004, online: DOI: 10.1002/
0471238961.03011802191309.a01.pub2.