Article No : a05_185

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 a
compound dates back to 1839, when it was wide flammability range in air (1 – 50 vol %)
prepared by SCHRÖTTER 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
Density,
worldwide in 1984, over 75 % was used by the
liquid at 25  C 1260 kg/m3
regenerated cellulose industry. The rest was con- saturated gas at 20  C 8.07 kg/m3
sumed in production of carbon tetrachloride Critical temperature 273  C
and miscellaneous organosulfur compounds Critical pressure 7600 kPa

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
1019 W1 cm1 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
Heat of formation,
disulfide to give the trithiocarbonate and carbon-
gas at 25  C, 101.3 kPa 117.1 kJ/mol ate:
Heat of fusion 4.390 kJ/mol
Heat of vaporization at 25  C 27.41 kJ/mol 3 CS2 þ6 NaOH ! 2 Na2 CS3 þNa2 CO3 þ3 H2 O
Specific heat, liquid at 25  C 76.45 J mol1 K1
Specific heat, Trithiocarbonates are also formed with metal
gas at 25  C, 101.3 kPa 46.2 J mol1 K1
Entropy, gas at 25  C, 101.3 kPa 237.83 J mol1 K1
sulfides:
Free energy of formation,
K2 S ðaqueousÞþCS2 ! K2 CS3
gas at 25  C, 101.3 kPa 66.9 kJ/mol
Thermal conductivity,
liquid at 25  C, 101.3 kPa 0.162 W m1 K1 Carbon disulfide reacts with alcoholic alkalies
gas at 25  C, 101.3 kPa 0.0078 W m1 K1
to produce xanthates (salts of dithiocarbonates)
Viscosity,
liquid at 25  C, 101.3 kPa 0.36 mPa  s [17]:
gas at 25  C, 101.3 kPa 0.0098 mPa  s
Diffusivity, ROHþNaOH!RONaþH2 O
gas at 0  C, 101.3 kPa
self-diffusion 0.0472 cm2/s RONaþCS2 !ROCSSNa
diffusion in air 0.0892 cm2/s
diffusion in CO2 0.063 cm2/s
liquid at 25  C, 101.3 kPa This reaction is the basis for the viscose
self-diffusion 4.1
105 cm2/s process in which cellulose is converted to the
xanthate and regenerated as fibers and films:
ðcelluloseÞONaþCS2 ! ðcelluloseÞOCSSNa
Vapor pressure
t,  C 10 0 10 20 30 46.22 (bp) 60 80 2ðcelluloseÞOCSSNaþH2 SO4 ! 2ðcelluloseÞOH
p, kPa 10.48 16.95 26.41 39.76 58.03 101.3 155.7 272.2 þ2 CS2 þNa2 SO4
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
3. Chemical Properties (1) [513-74-6], ammonium trithiocarbonate (2)
[13453-08-2], and ammonium thiocyanate (3)
The chemistry of carbon disulfide is extensive [1762-95-4] [14]:
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
CS2 in H2O, 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
Vol. 6 Carbon Disulfide 669

salts [18]: Depending on the degree of chlorination,

some carbon tetrachloride [56-23-5], sulfur
2 RNH2 þCS2 !RNHCSSNH3 R
dichloride [10545-99-0], and thiophosgene
[463-71-8] are also formed.
2 R2 NHþCS2 !R2 NCSSNH2 R2
In the presence of iron and metal chlorides and
at higher temperature (70 – 100  C), carbon tet-
In the presence of alkalies, many commercial- rachloride and sulfur chlorides are exclusively
ly important salts of dithiocarbamic acid are obtained [14]:
obtained:
CS2 þ3 Cl2 ! CCl4 þS2 Cl2
R2 NHþCS2 þNaOH ! R2 NCSSNaþH2 O
Further reaction of the sulfur monochloride
Sodium methyldithiocarbamate [137-42-8], [10025-67-9] with carbon disulfide produces
CH3NHCSSNa, an important soil fumigant, is more carbon tetrachloride and sulfur:
produced by the reaction of carbon disulfide with
methylamine and an aqueous solution of caustic CS2 þ2 S2 Cl2
CCl4 þ4 S
soda. In a similar reaction with ethylenediamine,
the fungicide sodium ethylene bis(dithiocarba- These two reactions are the basis for the
mate) [142-59-6] is the reaction product: 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 %
Two important vulcanization accelerators are at 90  C.
products in the reaction of aniline with carbon Carbon disulfide reacts readily with water in
disulfide. In the absence of sulfur, thiocarbanilide the presence of alumina and oxide catalysts
[102-08-9] is obtained: above 150  C to form carbon dioxide and hydro-
gen sulfide:
CS2 þ2 H2 O ! CO2 þ2 H2 S

With sulfur, 2-mercaptobenzothiazole [149- Carbonyl sulfide is an intermediate in this

30-4] (MBT) is produced: hydrolysis reaction:
CS2 þH2 O ! COSþH2 S

COSþH2 O ! CO2 þH2 S

Thiurium disulfides, a family of compounds
used as fungicides and vulcanization accelera- At 200 – 300  C, equilibrium conversion of
tors, are formed by oxidizing dithiocarbamates carbon disulfide is nearly complete [21].
[18]: At temperatures above 150 – 200  C and in
2 R2 NCSSNaþH2 O2 þH2 SO4 ! ðR2 NCSSÞ2 the presence of metal sulfide catalysts, notably
þNa2 SO4 þ2 H2 O molybdenum and nickel sulfides, carbon disul-
fide is reduced by hydrogen to give various
Chlorination of carbon disulfide gives rise to a amounts of methanethiol, dimethyl sulfide,
host of chlorinated products [19]. At tempera- methane, and hydrogen sulfide [22].
tures between 5 and 30  C and in the absence of
iron, iodine-catalyzed chlorination of carbon
disulfide gives good yields of trichloromethane- 4. Production
sulfenyl chloride [594-42-3]:
Carbon disulfide is commercially manufactured
2 CS2 þ5 Cl2 ! 2 Cl3 CSClþS2 Cl2 by the reaction of sulfur with charcoal or
670 Carbon Disulfide Vol. 6

methane. Ethane, propane, and propene have k ¼ 1:9
106

been used to a limited extent. Since the methane expð52000=RTÞmolh1 cm3 kPa2
process was first introduced in the early 1950s, it For the silica gel catalyzed reaction:
has steadily supplanted the older charcoal pro-
cess, which is no longer a factor in carbon k ¼ 7:7
102
disulfide manufacture in the United States, Eur- expð28000=RTÞmolh1 g1 catalkPa2
ope, and Japan. In areas where natural gas or Other values for these rate constants as well as
methane is not readily available or when plant space velocities for the catalyzed reaction have
size is relatively small, the charcoal process still been reported [27–31]. At 600  C, the homoge-
supplies local viscose rayon requirements. neous rate is about 1 % that for the silica gel
catalyzed reaction.

4.1. Thermodynamics and Rates of

Reaction
4.2. Production from Charcoal and
The reactions of sulfur with either carbon or Sulfur
methane have been evaluated for the following
equations [23]: The basic process for the reaction of charcoal
with sulfur has changed little since its inception
CðsÞ þ2 SðgÞ ! CS2ðgÞ in the mid 1840s. Externally heated retorts are
still being used, although equipment design has
CH4ðgÞ þ4 SðgÞ ! CS2ðgÞ þ2 H2 SðgÞ undergone much improvement as better materi-
als of construction have become available. De-
The maximum yield from carbon was found to tails on retort design are available in references
be 91 % at 720  C. For the methane reaction, [32], [33].
complete conversion was attained at 300  C. In In retort plants [34], [35], molten sulfur is
practice, higher temperature is required to pro- vaporized and superheated either before or after
vide economic reaction rates. The reactions are addition to the retort. Reaction between the
endothermic over most of the temperature range superheated sulfur vapor and a stationary bed of
practiced commercially; the energy supplied is charcoal at 850 – 900  C takes place inside the
taken up mainly by vaporization and superheat- retort at slightly above atmospheric pressure. The
ing of sulfur [23–25]. product gas, consisting of carbon disulfide, some
The thermodynamics of sulfur dissociation sulfur, hydrogen sulfide, carbonyl sulfide, and
[7], [23], [24] determine the concentration of the inerts, passes through a train of condenser, scrub-
reactive diatomic sulfur molecule, S2; high tem- ber, and oil absorber where the crude carbon
perature and low pressure favor high S2 concen- disulfide is recovered; the pure product is ob-
trations [7]. Equilibration rates of the vapor tained by further treatment in distillation col-
species, Sn (n ¼ 1 – 8), are relatively fast so that umns. The tail gas, made up primarily of hydro-
equilibrium values of S2 may be used in rate gen sulfide, carbonyl sulfide, and inerts, is either
equation formulation. incinerated and scrubbed with a caustic solution
Homogeneous and heterogeneous rate data or routed to a sulfur recovery plant.
for the reaction of methane and sulfur have been Typically, each retort can produce 1 – 3 t/d of
obtained for temperatures between 500 and carbon disulfide. High-temperature corrosion of
700  C [26], [27–30]. The rate equation that best the cast iron retorts limits their useful life to less
fits these data is one that is first order with respect than 1 year. The raw materials used in the retorts
to methane and S2: should be low in ash and residue to minimize the
frequency of reactor cleanouts. Fouling of the
rate ¼ k cCH4 cS2
retorts also restricts heat transfer and shortens
where k is the reaction rate constant. retort life. Charcoal quality is extremely impor-
The following are the Arrhenius equations for tant because less reactive material requires higher
the rate constants, based on reference [26]. For temperature for satisfactory operation; charcoal
the homogeneous reaction: derived from hardwood is preferred for this
Vol. 6 Carbon Disulfide 671

reason. The charcoal is normally precalcined at 1965, many patents were issued that covered
500  C to remove volatiles that could result in various aspects of the process [38–54].
formation of objectionable byproducts. Thermal The commercial methane process [35], [55],
efficiency of retorts is ca. 25 %; carbon and sulfur [56] is based primarily on work described by the
yields are generally below 90 % [34–36]. patents issued to the Pure Oil Co. [41–45]. The
Electrical resistance heating in brick-lined rights to these patents were acquired by the Food
electrothermal reactors provides an alternative Machinery Corp. and Stauffer Chemical Co., and
heat source for the reaction of charcoal with in 1953, the first methane process plant was built
sulfur [37]. Where cheap power is available, by FMC in South Charleston, West Virginia. This
the electrical method may be more economic. was followed by a Stauffer plant at LeMoyne,
Power consumption as a function of carbon Alabama, three years later. By the mid 1960s all
disulfide produced is ca. 1200 kW h/t. Other carbon disulfide in the United States was man-
advantages offered by electrothermal reactors ufactured by this method; many similar plants
are a larger capacity per reactor (up to 10 t/d) soon followed in Europe and elsewhere [35].
and a longer reactor life; furthermore, a wider Over 85 % of the world’s production capacity is
range of solid carbon feed can be used because based on methane.
electrothermal reactors can generate higher Figure 1 shows a typical methane process flow
temperatures. sheet. Purified natural gas containing over 95 %
methane and low concentrations of propane and
heavier hydrocarbons is preheated to about 250  C
4.3. Production from Methane and in the convection section of the reaction furnace.
Sulfur The furnace is a typical box-type pyrolysis furnace
commonly used in the petrochemical industry,
As demand for carbon disulfide rapidly increased with radiant and convection sections [57]. The hot
in the 1940s, limitations of the charcoal processes methane gas is mixed with liquid sulfur and intro-
provided the incentive for development of a more duced into the horizontal heating coil located in the
efficient large-scale method for its manufacture. radiant section. There the liquid sulfur is vaporized,
Readily available cheap natural gas and favor- and the temperature of the mixture is raised to
able thermodynamics [21], [23], [31] led to the 550 – 650  C. Operating pressure is typically
successful development of the process based on 400 – 700 kPa. Alternatively, the methane and
the catalyzed reaction of methane and sulfur [21], sulfur may be introduced separately and at differ-
[27–31], [38], [39]. During the period 1943 – ent locations of the coil. A slight excess of sulfur

Figure 1. Methane process for CS2 production a) Reaction furnace; b) Catalytic reactors; c) Sulfur condenser; d) CS2 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
672 Carbon Disulfide Vol. 6

(5 %) is used to ensure good methane conversion Important refinements to the basic methane
and to minimize carbon and tar formation. process include the use of high-pressure
To withstand the high-temperature corrosive (2000 kPa) condensation and fractionation for
environment, cast high-alloy stainless steel is product recovery and purification [54], and mod-
used as tube material. Tube life is normally ifications to the reaction furnace system to allow
2 – 3 years. Packed, brick-lined reactors are the use of olefinic feedstocks [71], [72].
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 5. Environmental Aspects
reactors; almost all the hydrocarbons are con-
verted by the time the gas leaves the last reactor. Carbon disulfide in the atmosphere is of biogenic
Gas exiting the reaction furnace system passes as well as industrial origin [73]. Tropospheric
through the sulfur condenser where most of the concentrations of carbon disulfide have been
excess sulfur is separated. Next the cooled gas reported as 3
105 ppm in remote areas and
goes through a sulfur scrubber and then to the CS2 7
105 – 30
105 ppm in urban and industrial
scrubber in which the remaining sulfur is re- locations [74]. Natural release includes diffuse
moved. The relatively sulfur-free gas then enters emission from soil [75] and volcanic eruption
water-cooled condensers for bulk separation of [73]. Industrial sources consist mainly of release
carbon disulfide. The remaining carbon disulfide from gasification and pyrolysis of carbonaceous
is finally removed from the hydrogen sulfide gas fuel in the presence of sulfur compounds, from
in the oil absorber. The hydrogen sulfide gas sulfur recovery (Claus) plant tail gas, and from
exiting the oil absorber contains 1 – 2 % meth- industrial users of carbon disulfide [73], [74].
ane and less than 1000 ppm carbon disulfide. Investigations on the fate of carbon disulfide
This gas is routed to a Claus sulfur recovery in the atmosphere show that the principal oxida-
plant where it is converted back to sulfur. tion products are sulfur dioxide, carbonyl sulfide,
Crude carbon disulfide from the condensers, and carbon monoxide [73], [76], [77]. Eventually
including that recovered in the stripper, is sent to these compounds degrade to carbon dioxide and
the stabilizer column for removal of low-boiling sulfates.
impurities. The bottoms from the stabilizer column Carbon disulfide may be removed from gas
are next processed in the purification column where streams by oil absorption or adsorption with
high-boiling contaminants are separated from the activated carbon [78], [79]. A common method
product. A caustic and water wash complete used in the treatment of carbon disulfide and
the product purification operations, and the finished carbonyl sulfide in sulfur recovery plant tail gas
product is pumped to check tanks and storage. involves hydrogenation and hydrolysis of these
compounds to carbon dioxide and hydrogen sul-
fide. The hydrogen sulfide is then recovered by
4.4. Other Processes absorption in alkanolamine solutions [78], [80].

The use of different feedstocks for the manufac-

ture of carbon disulfide is a subject of much 6. Quality Specifications and
economic interest. Raw materials evaluated in- Analytical Methods
clude the following: methane and hydrogen sul-
fide [58], [59]; coke and coal with sulfur dioxide Carbon disulfide produced commercially in mod-
and hydrogen sulfide [60–62]; liquid hydrocar- ern plants is generally of high purity and meets
bons with sulfur [63–65]; hydrocarbons with most of the specifications listed in Table 2.
sulfur and sulfur dioxide [66], [67]; chlorinated Analytical methods for detecting carbon di-
hydrocarbons and sulfur [68]; carbon monoxide sulfide are detailed in references [83], [84]. A
and sulfur [36]; and organosulfur compounds common procedure, sensitive to 1 ppm, is based
with sulfur [69]. Most of these alternatives are on the reaction of carbon disulfide with diethy-
unattractive because of poor yield, undesirable lamine in the presence of a cupric salt to give the
byproducts, or difficulties in processing due to tar characteristic yellow cupric diethyldithiocarba-
and polymer formation [70]. mate. Infrared spectrophotometry is sensitive to
Vol. 6 Carbon Disulfide 673

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 most In 1984, an estimated 1.1
106 t of carbon disul-
hazardous chemicals to handle. Facilities using fide was produced worldwide in the following
carbon disulfide must be designed to operate, at areas (production figures in 103 t/a):
all times, as a closed system and above atmo-
spheric pressure to avoid the influx of air. When- North America 235
ever possible, these plants should be located Western Europe 260
outdoors or in open structures away from flames Eastern Europe 250
and other sources of ignition. Equipment should Latin America 50
Asia 160
be properly grounded to prevent accumulation of Africa 10
static electricity. Water deluge systems around Former States of USSR 120
processing and storage areas should be provided; Total 1085
enclosed units should 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 (pro-
carbon disulfide may be present should be desig- duction figures in 103 t/a):
nated as Class 1 hazardous locations as defined
by the National Electrical Code [87]; electrical
specifications should be in accordance with the
North and Central America 190
requirements of the code. South America 54
Carbon disulfide is stored in properly diked Europe and Africa 822
above-ground steel tanks or in tanks confined in Asia 221
open-top water-flooded concrete pits. Underwa- Total 1287
ter tanks are water padded, whereas water or inert
gas padding is used in above-ground tanks. [89]
Transfer of carbon disulfide from storage tanks The regenerated cellulose industry is by far
may be by padded pressure or pumps [81]. the largest user of carbon disulfide. Over 65 %
Carbon disulfide is classified by the United of world production is used in the manufacture
States Department of Transportation (DOT) as a of rayon (ca. 0.32 kg of carbon disulfide is
674 Carbon Disulfide Vol. 6

Table 3. Uses of carbon disulfide and its derivatives

Compound Application Reference

Carbon disulfide reaction and extraction solvent, catalyst presulfi- [33], [81]
dation agent, oil well solvent, cold vulcanization
additive for rubber, synthetic chemical
Sodium cellulose xanthate precursor for rayon, cellophane, and regenerated [17]
cellulose products; chelating agent
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 produced). Table 5. World production capacity for carbon disulfide, 1000 t/a,
Some 10 % is used in making cellophane, and 1984a
another 10 % is chlorinated to form carbon tetra- Charcoal Methane
chloride (about 25 % of world carbon tetrachlo- Area process process
ride is produced by this method). The remaining
North America – 335
15 % is distributed among rubber chemicals,
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,
Belgium, Spain
ed States are shown in Table 4. Competitive pres-
sure from synthetic fibers and films will continue to Eastern Europe 40 260
limit market growth in the regenerated cellulose Poland, Rumania, Bulgaria,
industry. Improvement in carbon disulfide usage German Democratic Republic
will be slow and must come from increased use in
USSR 40 120
agricultural and specialty chemicals manufacture.
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.
Table 4. United States carbon disulfide production and price China 20 –

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
1984 420 210 *
References [40], [96], and various trade sources
Vol. 6 Carbon Disulfide 675

9. Toxicology and Occupational include abnormal color vision, loss of visual

Health acuity, loss of accommodation, and retinopathy
[111].
The toxicology data base on carbon disulfide is Cardiovascular alterations in humans may
extensive. Citations include hundreds of experi- also result from carbon disulfide exposure. A
mental investigations on animals and many clin- number of studies [112–114] reveal vascular
ical and epidemiological reports on humans. atherosclerotic changes following long-term ex-
posure to carbon disulfide (30 – 90 mg/m3). Be-
Mutagenicity and Genotoxicity. The mu- low 10 ppm, cardiovascular effects are not
tagenic and genotoxic potential of carbon disul- apparent.
fide has been evaluated in vitro and in vivo The toxic effects of carbon disulfide require
[97–100]. Carbon disulfide does not exhibit mu- that precautions should be taken to limit exposure
tagenic activity in bacteria (S. typhimurium and in the workplace. In the United States, the TLV-
E. coli) with or without the presence of an TWA as adopted by ACGIH for exposure to
activation system. Additional in vitro tests, in- carbon disulfide is 30 mg/m3, 10 ppm [115]; the
cluding host-mediated assay, unscheduled DNA MAK value is the same. The federal standard
synthesis in human fibroblasts, and primary cul- (OSHA, 1985) is 60 mg/m3.
tures of human leukocytes, are inconclusive
[101], [102]. However, the significance of these Disposition. The primary route of human
tests cannot be properly evaluated because of carbon disulfide exposure is inhalation. Uptake
methodological problems including the lack of in the blood is rapid and carbon disulfide is
proper positive controls. Therefore, insufficient transported to tissues. Carbon disulfide possesses
data are available to evaluate the mutagenic and significant lipophilicity while also binding to
genotoxic potential of carbon disulfide. proteins and amino acids. In humans, most
(> 70 %) of a systemically absorbed dose is
Human Health Effects. Carbon disulfide rapidly converted to metabolites, followed by
toxicity in humans is well-documented in the urinary excretion. Less than 30 % of carbon
literature. It was first recognized as a workplace disulfide is exhaled and very small quantities are
hazard by the French in the 1850s. Subsequent excreted unchanged [116].
studies demonstrated effects on the central and
peripheral nervous systems and cardiovascular Subchronic Toxicity. A 90-d inhalation
system. Carbon disulfide can induce polyneuro- toxicity study using Fischer 344 rats, Sprague-
pathy and encephalopathy. Poisoning may be Dawley rats, and B6C3F1 mice (exposed simul-
acute or chronic. taneously in the same chambers) was conducted
Symptoms of polyneuropathy include pares- with carbon disulfide vapor [117]. Evaluation of
thesia, cramps, muscle weakness, pain, distal the hematology examinations (Fischer 344 and
sensory loss, and neurophysiological impairment Sprague-Dawley rats) indicated effects on red
[103–110]. Exposure to high levels of carbon cells and platelets. In addition, high-dose animals
disulfide for prolonged periods is necessary to of both sexes exhibited a mild increase in neu-
produce the polyneuropathy. However, exposure trophils and a decrease in lymphocytes. Serum
at levels of 65 – 170 ppm for less than 1 year are chemistry examinations at the high dose did not
reported to result in many of the symptoms reveal dramatic changes. Organ weight data re-
described [103]. Symptoms of encephalopathy vealed a depression of brain as well as liver
may include headache, sleep disturbances, gen- weight.
eral fatigue, loss of libido, impotence, organic Histopathology studies revealed axonal swell-
dementia, and Parkinsonism [103–110]. Onset of ing of spinal cord nerve fibers in high-dose males,
symptoms range from several months to several high-dose females, and possibly mid-dose males.
years. The early stage of encephalopathy is char- In addition, males and females from the high-
acterized by depression with sudden attacks of dose group had segmental degeneration of fibers
hallucinations. Visual disturbances that may re- in the sciatic nerve. Other lesions that oc-curred
sult from high levels of carbon disulfide exposure were incidental and not related to treatment.
676 Carbon Disulfide Vol. 6

Biochemical Mechanisms. Understanding [74]. Carbonyl sulfide has been suggested as a

the mechanism of action of carbon disulfide major causative agent in atmospheric sulfur cor-
toxicity may lead to early clinical intervention rosion [74].
in cases of suspected poisoning. Although a The commercial importance of carbonyl sul-
number of hypotheses have been proposed, the fide is limited; it is not produced in large quantity,
biochemical mechanism(s) remain unknown. A and is used principally for small-scale syntheses
metabolite of carbon disulfide may be responsi- and experiments. The use of carbonyl sulfide as a
ble for its hepatotoxic effects [117], [118]. Sulfur raw material for chemical manufacture has been
is liberated during conversion of carbon disulfide proposed [126].
to carbon dioxide. The liberated sulfur may bind Carbonyl sulfide appears to play an impor-
to cellular components or critical enzymes, giv- tant role in mediating the toxicity of carbon
ing rise to toxicity. disulfide. Carbon disulfide is metabolized in
Research has also focused on related areas, vitro [127] and in vivo [128] to carbonyl
including the role of carbon disulfide in chelating sulfide. Carbonyl sulfide is further metabolized
dithiocarbamates, binding and depleting essen- by hepatic carbonic anhydrase to hydrogen
tial trace elements, disturbing vitamin metabo- sulfide [128].
lism [73], turnover of catecholamines [119], and Death from acute inhalation of carbonyl sul-
metabolizing lipids [120–122]. 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-
10. Carbonyl Sulfide ty. Presently, complete subchronic toxicity stud-
ies on carbonyl sulfide are unavailable. There is
Carbonyl sulfide [463-58-1], carbon oxysulfide, one report, however, describing effects following
COS, is a colorless, flammable gas that is spar- subchronic administration. Rabbits [112] were
ingly soluble in water but very soluble in alco- continuously exposed for 7 weeks to ca. 50 ppm
holic alkalies [123]. Selected physical properties COS. Within five days, three rabbits died and two
are: were sacrificed in a moribund condition. There
were no further mortalities. Cholesterol (serum)
elevations were noted in exposed rabbits. Histo-
Mr 60.07 pathology did not reveal changes in the lungs or
mp  138.8  C
bp at 101.3 kPa  50.2  C in the intima of the arteries in the organs
Heat of vaporization at 101.3 kPa 18.50 kJ/mol evaluated.
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 References
Free energy of formation at 25  C  164.3 kJ/mol

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