Professional Documents
Culture Documents
Sulfur Compounds
Sulfur Compounds
1. Introduction
1.1. Carbon Suldes. The only commercial carbon sulde is carbon di-
sulde (qv) [75-15-0], CS
2
, which is covered in a separate article. There are sev-
eral unstable carbon suldes. Carbon subsulde [12976-57-2], C
3
S
2
, is a red
liquid [mp 0.58C, bp 60708C at 1.6 kPa (12 mmHg)] produced by the action
of an electric arc on carbon disulde (14). The structure has been shown to be
S
[NH
2
R
2
]
+
O
With amines, such as those used in gas sweetening, it reacts forming mainly
ureas:
COS + 2 HOCH
2
CH
2
OCH
2
CH
2
NH
2
(HOCH
2
CH
2
OCH
2
CH
2
NH)
2
CO + H
2
S
2 SULFUR COMPOUNDS Vol. 23
The kinetics of reaction of COS with aqueous amines have been studied (29).
The photolysis of carbonyl sulde is a laboratory method for the production
of monoatomic sulfur, a short-lived species (30).
Occurrence and Preparation. Carbonyl sulde is formed by many high
temperature reactions of carbon compounds with donors of oxygen and sulfur.
Usually, as forming COS as a byproduct, the principal route is the following reac-
tion (31):
CO + S
0
COS
This equilibrium favors COS up to ~5008C. At higher temperatures, COS
dissociates increasingly, eg, to 64% at 9008C. The reaction may be run at 65
2008C to produce carbonyl sulde if an alkaline catalyst is used (32). A Rhodia
patent describes the manufacture of carbonyl sulde by the reaction of methanol
with sulfur at 5008008C (33). However, the preferred route both for laboratory
and commercial production is the reaction of either alkali metal thiocyanate or
ammonium thiocyanate with strong (~50%) sulfuric acid:
NH
4
SCN + 2 H
2
SO
4
+ H
2
O 2 NH
4
HSO
4
+ COS
To make pure COS, the evolved gas that may contain CO
2
, SO
2
, H
2
S, CS
2
,
HCHO, and HCN as byproducts, is scrubbed with copper sulfate solution, alkali
solution, ethanolic aniline, and concentrated sulfuric acid. This thiocyanate
route is believed to have been commercially practiced to make COS for large-
scale thiocarbamate herbicide production.
Other important reactions yielding carbonyl sulde follow (34,35):
Reaction Remarks
CO
2
H
2
SCOSH
2
O in Claus furnace and over various catalysts
CO
2
CS
2
O
RNHCNH
O
+ H
2
S
+
n
Monoureas can also be prepared using COS and an alkylamine, or an arylamine
in the absence or presence of a catalyst, where R=H, alkyl, or aryl (51):
RNHCNHR 2 RNH
2
+ CO + S
0
O
4 SULFUR COMPOUNDS Vol. 23
The above reaction produces COS as an intermediate, which can be isolated
when a catalytic amount of selenium is present (52).
COS shows promise as a stored product fumigant, as an alternative to
methyl bromide or phosphine. It is effective in killing insects, mites (53), and
fungi (54).
2. Thiophosgene
2.1. Physical Properties. Thiophosgene [463-71-8] (thiocarbonyl chlor-
ide ), CSCl
2
, is a malodorous, red-yellow liquid (bp 73.58C, d
15
20
1.509, n
20
D
1.5442). It is only slightly soluble with decomposition in water, but it is soluble
in ether and various organic solvents.
2.2. Chemical Properties. Thiophosgene is more resistant to hydroly-
sis than its oxygen analogue, phosgene, but it is slowly hydrolyzed to carbon
dioxide, hydrogen sulde, and hydrochloric acid. It can be oxidized to a lacrima-
tory thiophosgene S-oxide (55). Its utility in organic synthesis has been reviewed
(56,57). Its photochemical properties have been studied and reviewed (58).
Thiophosgene reacts with alcohols and phenols to form chlorothionofor-
mates or thiocarbonates. The most studied reactions of thiophosgene are with
primary amines to give isothiocyanates and with secondary amines to give thio-
carbamyl chlorides:
RN C S RNH
2
+ CSCl
2
+ 2 HCl
2 R
2
NH + CSCl
2
R
2
NCCl + R
2
NH HCl
S
Because of the toxicity of thiophosgene, alternative methods for making
organic isothiocyanates have been developed (59).
The reaction of thiophosgene with various bisphenols using phase-transfer
catalysis gives polythiocarbonates (60):
C HO OH
CH
3
CH
3
C O O
CH
3
CH
3
C
S
+ CSCl
2
Bu
4
NBr
CH
2
Cl
2
n
+
C) :
30 40 50 102 159 191
K =
[pSO
2
[[pCl
2
[
[pSO
2
Cl
2
[
:
2.92 5.13 8.34 240 902 1330
where p=pressure inkPa (to convert to atm, divide by 101.3).
The decomposition of sulfuryl chloride is accelerated by light and catalyzed
by aluminum chloride and charcoal. Many of the reactions of sulfuryl chloride
are explainable on the basis of its dissociation products. Sulfuryl chloride reacts
with sulfur at 2008C or at ambient temperature in the presence of aluminum
chloride producing sulfur monochloride. It liberates bromine or iodine from bro-
mides or iodides. Sulfuryl chloride does not mix readily with water and hydro-
lyzes rather slowly.
SO
2
Cl
2
+ 2 H
2
O H
2
SO
4
+ 2 HCl
The reaction of sulfuryl chloride with a stoichiometric amount of sulfuric
acid produces chlorosulfuric acid [7790-94-5] (chlorosulfonic acid):
SO
2
Cl
2
+ H
2
SO
4
ClSO
3
H
This latter reaction is reversible. Sulfuryl chloride can be fractionally distilled
from boiling chlorosulfonic acid in the presence of a catalyst, eg, a mercuric salt.
Iodine reacts with sulfuryl chloride in the presence of aluminum chloride as
catalyst-forming iodine chlorides. Sulfuryl chloride reacts with anhydrous
ammonia yielding a series of sulfamides of the general formula NH
2
SO
2
(NH-
SO
2
)
n
NH
2
, where n is 1 or higher. A cyclic compound of the formula (SO
2
NH)
3
[13954-94-4] is also produced.
The organic chemistry of sulfuryl chloride involves its use in chlorination
and sulfonation (222,251,252). As a chlorinating agent, sulfuryl chloride is
often more selective than elemental chlorine. The use of sulfuryl chloride as a
chlorinating agent often allows more convenient handling and measurement as
well as better temperature control because of the lower heat of reaction as com-
pared with chlorine. Sulfuryl chloride sometimes affords better selectivity than
chlorine in chlorination of active methylene compounds (253255):
SO
2
Cl
2
+ CH
3
COCH
2
COOC
2
H
5
CH
3
COCHClCOOC
2
H
5
+ HCl + SO
2
Alkanes can be simultaneously chlorinated and chlorosulfonated. This commer-
cially useful reaction has been applied to polyethylene (256258). Aromatics can
be chlorinated on the ring. In the presence of a free-radical initiator, alkylaro-
matic compounds can be chlorinated selectively in the side chain. Methane can
be chlorosulfonated to methanesulfonyl chloride at low temperature in the pre-
sence of a free-radical initiator, such as urea plus hydrogen peroxide, and in the
presence of a promoter, such as rhodium chloride, using sulfuric acid as solvent
(259). Ring chlorination can be selective. A patent shows chlorination of 2,5-
dichloro- to 2,4,5-trichlorophenoxyacetic acid free of the toxic tetrachlorodibenzo-
dioxins (260). The selectivity to the p-isomer in chlorination of toluene can be cat-
alyzed by zeolite, and sulfuryl chloride is somewhat more selective than chlorine
Vol. 23 SULFUR COMPOUNDS 29
(261). With alkenes, depending on conditions, the chlorination can be additive or
substitutive. The addition of sulfuryl chloride can occur to form a 2-chloroalka-
nesulfonyl chloride (262).
RCH CH
2
+ SO
2
Cl
2
RCHClCH
2
SO
2
Cl
However, whensulfur monochlorideisusedas thecatalyst, chlorosultes form.
RCHClCH
2
OSCl SO
2
Cl
2
+ RCH CH
2
O
S
2
Cl
2
Sulfuryl chloride can be reacted with some alcohols to produce mixtures of
sulfate esters, said to be useful as dyeing auxiliaries (263). With alkylamines,
sulfuryl chloride can produce alkylsulfamoyl chlorides, which are useful inter-
mediates in herbicide syntheses.
RNHSO
2
Cl + 2 HCl RNH
2
HCl + SO
2
Cl
2
Manufacture. The preparation of sulfuryl chloride is carried out by feed-
ing dry sulfur dioxide and chlorine into a water-cooled glass-lined steel vessel
containing a catalyst, eg, activated charcoal. Alternatively, chlorine is passed
into liqueed sulfur dioxide at ~08C in the presence of a dissolved catalyst, eg,
camphor, a terpene hydrocarbon, an ether, or an ester. The sulfuryl chloride is
puried by distillation; the commercial product is typically 99 wt% pure, as mea-
sured by ASTM distillation method D850.
Shipment and Storage. To harmonize the DOT regulations with the UN
regulations, sulfuryl chloride must be shipped in pressure-rated vessels. A dou-
ble-wall disposable drum is required for drum shipments. With caution, dilute
alkali can be used to hydrolyze and dispose of residual sulfuryl chloride. Dry
steel tanks can be used to store sulfuryl chloride, but some corrosion may
occur; lead, nickel, glass, Teon, 310 stainless steel, or baked phenolics (tested
for this service) are preferred. It is important to prevent exposure to atmospheric
moisture and vent any hydrogen chloride pressure that builds up. Sulfuryl chlor-
ide should also be protected from prolonged exposure to strong light.
Economic Aspects. The truckload price of sulfuryl chloride in 2005 was
~$2.50/kg. Occidental Chemical Company (Niagara Falls, N.Y.) was the last
U.S. merchant producer. Lanxess (former Bayer) produces it in Leverkusen, Ger-
many. It may be made and used captively by DuPont for manufacture of their
chlorosulfonated Hypalon elastomer.
Health and Safety Factors. Sulfuryl chloride is both corrosive to the skin
and toxic upon inhalation. The TLV suggested by the manufacturer is 1ppm. The
vapors irritate the eyes and upper respiratory tract, causing prompt symptoms
ranging from coughing to extreme bronchial irritation and pulmonary edema.
The DOT label is Corrosive, Poison.
Uses. Uses of sulfuryl chloride include the manufacture of chlorophenols,
eg, chlorothymol for use as disinfectants. It is also used in the manufacture of a-
chlorinated acetoacetic derivatives, eg, CH
3
COCHClCOOC
2
H
5
, which are pre-
cursors for important substituted imidazole drugs, phosphate insecticides, and
30 SULFUR COMPOUNDS Vol. 23
fungicides (253,254). Other herbicide synthesis uses of sulfuryl chloride in which
compounds with SO
2
N linkages are produced have been reported. Sulfuryl chlor-
ide is believed to be used captively by DuPont in the manufacture of chlorosulfo-
nated polyethylene [9008-08-6]. Process improvements have been the subject of
DuPont and Toyo Soda patents (256258).
Lithium sulfuryl chloride batteries have been developed for uses similar to
the lithium thionyl chloride batteries (qv), but they have higher energy density
due to higher voltage, and higher current capability due to higher conductivity.
10. Sulfur Nitrides
The sulfur nitrides have been the subject of several reviews (264266). Although
no commercial applications have as yet been developed for these compounds,
some interest was stimulated by the discovery that polythiazyl, a polymeric sul-
fur nitride (SN)
x
, with metallic luster, is electroconductive in the metallic range
(see INORGANIC HIGH POLYMERS) (266268). Other sulfur nitrides are unstable. Tet-
rasulfur nitride is explosive and shock sensitive.
11. Sulfur Oxides
Numerous oxides of sulfur have been reported and those that have been charac-
terized are SO [13827-32-2], S
2
O [20901-21-7], S
n
O (n=610), SO
2
, SO
3
, and
SO
4
[12772-98-4]. Among these, SO
2
and SO
3
are of principal importance. Sulfur
oxide chemistry has been reviewed (269271). Sulfur trioxide, SO
3
, is discussed
elsewhere in this Encyclopedia (see SULFURIC ACID AND SULFUR TRIOXIDE).
12. Sulfur Dioxide, Sulfurous Acid and its Salts
12.1. Sulfur Dioxide. Physical Properties. Sulfur dioxide [7446-09-5],
SO
2
, is a colorless gas with a characteristic pungent, choking odor. Its physical
and thermodynamic properties are listed in Table 8. Heat capacity, vapor pres-
sure, heat of vaporization, density, surface tension, viscosity, thermal conductiv-
ity, heat of formation, and free energy of formation as functions of temperature
are available (272,273), as is a detailed discussion of the sulfur dioxidewater
system (274).
Liquid sulfur dioxide expands by ~10% when warmed from 20 to 608C
under pressure. Pure liquid sulfur dioxide is a poor conductor of electricity,
but high conductivity solutions of some salts in sulfur dioxide can be made
(275). Liquid sulfur dioxide is only slightly miscible with water. The gas is solu-
ble to the extent of 36 volumes per volume of water at 208C, but it is very soluble
(several hundred volumes per volume of solvent) in a number of organic solvents,
eg, acetone, other ketones, and formic acid. Sulfur dioxide is less soluble in non-
polar solvents (274,276,277). The use of sulfur dioxide as a solvent and reaction
medium has been reviewed (275,278).
Vol. 23 SULFUR COMPOUNDS 31
Inorganic Chemistry. Sulfur dioxide is extremely stable to heat, even up
to 20008C. It is not explosive or ammable in admixture with air. The oxidation
of sulfur dioxide by air or pure oxygen is a reaction of great commercial impor-
tance and is commonly conducted at 4007008C in the presence of a catalyst, eg,
vanadium oxide. The oxidation of sulfur dioxide to sulfur trioxide for manufac-
ture of sulfuric acid has been discussed (see SULFURIC ACID AND SULFUR TRIOXIDE).
For oxidation of sulfur dioxide at low levels, eg, in smelter off-gases, various cat-
alysts as well as chemical oxidants such as Caros acid, H
2
SO
5
, are used (279). In
certain sulfur dioxide recovery processes, oxidation of sulfur dioxide is carried
out on activated carbon (qv), which also serves as an adsorbent for the sulfur tri-
oxide and sulfuric acid produced (280). The oxidation of sulfur dioxide to sulfuric
acid and sulfates in the atmosphere is important with regard to air pollution stu-
dies (281283). Radicals, eg, HO, HO
2
, and CH
3
O
2
, appear to be the principal
species responsible for the homogeneous oxidation of sulfur dioxide in the atmo-
sphere, which can occur at rates as high as 4%/h (283).
Oxidation of sulfur dioxide in aqueous solution, as in clouds, can be cata-
lyzed synergistically by iron and manganese (284). The oxidation kinetics in aqu-
eous slurry of calcium sulte and sulfate with manganous sulfate catalyst have
been studied (285). Ammonia can be used to scrub sulfur dioxide from gas
streams in the presence of air. The product is largely ammonium sulfate formed
by oxidation in the absence of any catalyst (286). The oxidation of SO
2
catalyzed
by nitrogen oxides was important in the early processes for manufacture of sul-
furic acid (qv). Sulfur dioxide reacts with chlorine or bromine forming sulfuryl
chloride or bromide [507-16-4].
SO
2
+ Cl
2
SO
2
Cl
2
Reduction of sulfur dioxide to sulfur includes an industrially important
group of reactions (287). Hydrogen sulde reduces sulfur dioxide even at ambient
temperature in the presence of water, but in the dry state and in the absence of a
catalyst, a temperature of ~3008C is required.
SO
2
+ 2 H
2
S 3/x S
x
+ 2 H
2
O
This reaction is catalyzed by bauxite, and various metal suldes. The usual cat-
alyst is activated alumina, which also catalyzes the reduction by methane (288).
Molybdenum compounds on alumina are especially effective catalysts for the
hydrogen sulde reaction (289).
The Claus process, which involves the reaction of sulfur dioxide with hydro-
gen sulde to produce sulfur in a furnace, is important in the production of sulfur
from sour natural gas or by-product sulfur-containing gases (see SULFUR REMOVAL
AND RECOVERY).
When the Claus reaction is carried out in aqueous solution, the chemistry is
complex and involves polythionic acid intermediates (131,270). A modication of
the Claus process (by Shell) uses hydrogen or a mixture of hydrogen and carbon
monoxide to reduce sulfur dioxide, carbonyl sulde, carbon disulde, and sulfur
mixtures that occur in Claus process off-gases to hydrogen sulde over a cobalt
32 SULFUR COMPOUNDS Vol. 23
molybdate catalyst at ~3008C (290). Reformed natural gas reduces sulfur diox-
ide in a process developed by Asarco (291).
Reduction of sulfur dioxide by methane is the basis of an Allied process for
converting by-product sulfur dioxide to sulfur (292). The reaction is carried out in
the gas phase over a catalyst. Reduction of sulfur dioxide to sulfur by carbon in
the form of coal has been developed as the Resox process (293). The reduction,
which is conducted at 5508008C, appears to be promoted by the simultaneous
reaction of the coal with steam. The reduction of sulfur dioxide by carbon mon-
oxide tends to give carbonyl sulde [463-58-1] rather than sulfur over cobalt
molybdate, but special catalysts, eg, lanthanum titanate, have the ability to
direct the reaction toward producing sulfur (294).
With hot metals, sulfur dioxide usually forms both metal suldes, as well as
metal oxides. In aqueous solution, sulfur dioxide is reduced by certain metals or
by borohydrides to dithionites.
Sulfur dioxide dissolves in water, forming a weak acid solution of sulfurous
acid, H
2
SO
3
; however, the pure substance H
2
SO
3
has never been isolated. At
101.3 kPa (1 atm) sulfur dioxide pressure, the solubility of sulfur dioxide is
18.5% at 08C and 5.1% at 408C. Lower solubilities are observed when other dilu-
ent gases, eg, air, are present. At 258C, the hypothetical H
2
SO
3
has a rst ioniza-
tion constant of 1.72 10
2
and a second ionization constant of 1.1 10
9
. At low
temperatures, concentrated sulfurous acid affords a crystalline hydrate,
SO
2
6H
2
O [24402-69-5].
The absorption of sulfur dioxide in alkaline (even weakly alkaline) aqueous
solutions affords sultes, bisultes, and metabisultes. The chemistry of the
interaction of sulfur dioxide with alkaline substances, either in solution, slurry,
or solid form, is also of great technological importance in connection with air pol-
lution control and sulfur recovery (25,287,295301). Even weak bases, such as
zinc oxide, absorb sulfur dioxide. A slurry of zinc oxide in a smelter can be
used to remove sulfur dioxide and the resultant product can be recycled to the
roaster (302).
The anaerobic reaction of sulfur dioxide with aqueous ammonia produces a
solution of ammonium sulte [10192-30-0]. This reaction proceeds efciently,
even with a gas stream containing as little as 1 wt% sulfur dioxide. The sulfur
dioxide can be regenerated at a high concentration by acidulation or by stream
stripping of the ammonium sulte solution, or the sulte can be made to preci-
pitate and the ammonia recovered by addition of lime (303). The process can
also be modied to produce ammonium sulfate for use as fertilizer (304) (see
FERTILIZERS). In a variant of this process, the use of electron-beam radiation
catalyzes the oxidation of sulfur dioxide in the presence of ammonia to form
ammonium sulfate (305).
Organic Chemistry. The organic chemistry of sulfur dioxide, particularly
as it relates to food applications, has been discussed (306). Although no reaction
takes place with saturated hydrocarbons at moderate temperatures, the simulta-
neous passage of sulfur dioxide and oxygen into an alkane in the presence of a
free-radical initiator or ultraviolet light affords a sulfonic acid, such as hexane-
sulfonic acid [13595-73-8]. This is the so-called sulfoxidation reaction (307):
Vol. 23 SULFUR COMPOUNDS 33
2 C
6
H
14
+ 2 SO
2
+ O
2
2 C
6
H
13
SO
3
H + H
2
O
Simultaneous treatment of an alkane with sulfur dioxide and chlorine affords a
sulfonyl chloride, eg, hexylsulfonyl chloride [14532-24-2], and is referred to as
chlorosulfonation or the Reed reaction (307,308).
C
6
H
13
SO
2
Cl + HCl C
6
H
14
+ SO
2
+ Cl
2
Isomer mixtures are generally obtained. Chlorosulfonation is used to pro-
duce chlorosulfonated polyethylene, a curable thermoplastic. Preformed sulfuryl
chloride may also be used.
The reaction of sulfur dioxide with olens under free-radical-catalyzed con-
ditions produces copolymers which, in most cases, are of an alternating 1:1 type
(309,310):
C
4
H
9
CHCH
2
SO
2
SO
2
+ C
4
H
9
CH CH
2 x
Although these polymers have inadequate stability and processibility for
most plastics applications, the ability to undergo scission back to the gaseous
monomers has afforded some utility in fabrication of electron-beam resists for
photolithography. Polybutene sulfone (311) and polyhexene sulfone (312) have
been proposed for this small volume, but high value, application.
Sulfur dioxide acts as a dienophile in the Diels-Alder reaction with many
dienes (313,314) and this reaction is conducted on a commercial scale with buta-
diene. The initial adduct, sulfolene [77-79-2] is hydrogenated to a solvent, sulfo-
lane [126-33-0], which is useful for selective extraction of aromatic hydrocarbons
from
CH CH
CH CH
CH
2
CH
2
SO
2
CH
2
H
2
SO
2
CH
2
+
CH
2
CH
2
CH
2
CH
2
SO
2
a renery stream and as a dipolar aprotic reaction solvent with good thermal and
chemical stability. Sulfur dioxide reacts with Grignard reagents forming sulnic
acid salts.
(RSO
2
)
2
Mg + MgCl
2
2 RMgCl + 2 SO
2
Other reactions of sulfur dioxide forming sulnic acids or sulfones have been
reviewed (314).
Manufacture. Combustion of Sulfur. For most chemical process appli-
cations requiring sulfur dioxide gas or sulfurous acid, sulfur dioxide is prepared
by the burning of sulfur or pyrite [1309-36-0], FeS
2
. A variety of sulfur and pyrite
burners have been developed for sulfuric acid and for the pulp (qv) and paper (qv)
industries, which produce and immediately consume ~90% of the captive sulfur
dioxide produced in the United States. Information on the European sulfur-to-
sulfuric acid technology (with emphasis on Lurgi) is available (315).
34 SULFUR COMPOUNDS Vol. 23
The production of sulfur dioxide gas by combustion of Frasch-process sulfur
and sulfur recovered from natural gas or oil-renery gases is relatively simple
and is the preferred method, except in cases in which economic considerations
favor the use of pyrite, such as in some European countries. For most applica-
tions, with the exception of sulfuric acid manufacture, as high a sulfur dioxide
content as possible is desired. For sulfur burners utilizing air, the theoretical
maximum is 21 vol% SO
2
, and under satisfactory conditions 1420vol% can be
achieved. The various sulfur burners commercially available are rated by their
manufacturers as capable of producing gas in the range of 518 wt% sulfur diox-
ide. In the upper range of sulfur dioxide concentration, theoretical ame tem-
peratures for the combustion of sulfur in air are 120016008C. One kilogram
of sulfur requires 1kg of oxygen for its complete combustion. This is the amount
contained in 3.35 m
3
air. The reaction produces 4500 kJ/kg (1942 Btu/lb) of sulfur
dioxide from sulfur. The types of burners used are also dependent on scale, with
typical usages as follows: high pressure spray (multiple units), 35,000 kg/h; mul-
tiuid atomization (multiple units), 35,000 kg/h; spinning cup (single unit),
35,000 kg/h; rotary kiln (single unit), at or <900 kg/h; and pan-type burner (sin-
gle unit), at or <610 kg/h.
Large sulfuric acid plants are based on spray burners, where the sulfur is
pumped at 10301240 kPa (150180 psig) through several nozzles into a refrac-
tory-lined combustion chamber. An improved nozzle, resistant to plugging or
fouling, has been introduced (316). The combustion chambers are typically hor-
izontal bafe-tted refractory-lined vessels. The largest plants in fertilizer com-
plexes burn up to 50 t/h of sulfur.
Spinning-cup atomizers are used in some plants to provide ner atomiza-
tion, allowing smaller burner chambers and easier turndown, but with the bur-
den of added rotating equipment. Rotary kiln burners were once popular to burn
lower quality sulfur, but few are still in operation. Spray burners can be operated
intermittently and used at higher rates than rotary burners.
Pan and cascade burners are generally more limited in exibility and are
useful only where low sulfur dioxide concentrations are desired. Gases from sul-
fur burners also contain small amounts of sulfur trioxide, hence the moisture
content of the air used can be important in achieving a corrosion-free operation.
Continuous operation at temperatures above the condensation point of the pro-
duct gases is advisable where exposure to steel (qv) surfaces is involved. Pressure
atomizing-spray burners, which are particularly suitable when high capacities
are needed, are offered by the designers of sulfuric acid plants.
Air-atomizing sulfur burners can use smaller combustion chambers at the
expense of requiring more power to compress the air. Air is preheated in a jacket,
permitting faster combustion. The combustion volume can be as low as 0.085 m
3
(3 ft
3
) to burn 900 kg/d of sulfur (317). These burners can deliver high strength
gases of 1719 vol% SO
2
and are used in plants that produce liquid SO
2
and in
pulp mills. Enriched airoxygen can be used as the atomizing uid in sprays that
use external mixing at the point of atomization. A particularly efcient and clog-
resistant spray nozzle uses a combination of air atomization and effervescent ato-
mization (317).
The spinning-cup sulfur burner is suitable for very large capacities, ie, up to
39 t/h of sulfur in a single spinning cup. It is similar to spinning-cup oil burners,
Vol. 23 SULFUR COMPOUNDS 35
except that it is modied to prevent solidication of sulfur. The spinning cup pro-
vides centrifugal motion to the sulfur, which is then atomized by a ow of air in
an annular space surrounding the cup. This burner also sprays the sulfur into a
brick-lined combustion chamber.
Lurgi, Monsanto, and others have developed substoichiometric sulfur bur-
ners. The use of pure or enriched oxygen for burning sulfur is advocated by var-
ious oxygen suppliers, who provide burner and chamber designs for this purpose.
With the improvements in hollow-ber separation of air, the economic advantage
of enriched oxygen for burning sulfur is increasing. Submerged combustion of
molten sulfur with oxygen has been in use since 1989, and ts well into renery
Claus unit operation (318).
Other burners are used for low capacity operations. A cascade or checker
burner, in which molten sulfur ows down through brick checkerwork counter-
current to a ow of air, is used in small units with a sulfur trioxide converter to
condition gases entering electrostatic precipitators at boiler plants operating on
low sulfur coal. A small pan burner, which is fed with solid, low carbon sulfur, is
used to produce sulfur dioxide for solution in irrigation water to control the pH
and maintain porosity in the soil. The same type of burner is used to disinfect
wastewater; in this case sulfur dioxide is used instead of chlorine.
It has been proposed that the excess sulfur production from sour gas and tar
sands be burned to sulfur dioxide for energy recovery (avoiding carbon dioxide
production from carbon-based fuels) and the sulfur dioxide reinjected into sour
gas strata. This process is under study in Alberta (319). A very high purity sulfur
dioxide can be produced by the relatively recent Calabrian SO
2
Clean process
where in a specially designed burner, molten sulfur is burned by pure oxygen
to produce 99.99% pure SO
2
(320). This is convenient for the user because no
moisture, sulfur trioxide or inert gases are involved. Calabrian also produces
and ships high purity SO
2
made by this process on a large scale.
Burning Pyrites. This source of sulfur dioxide for fertilizer production has
recently been replaced at Europes largest acid plant in Spain by direct burning
of sulfur (321), which now has a cost advantage.
The burning of pyrite is considerably more difcult to control than the burn-
ing of sulfur, although many of the difculties have been overcome in mechanical
pyrite burners. A number of plants burn pyrite or zinc, lead, copper, and nickel
suldes in uid-bed roasters. The pyrite is fed onto a grate where it and its cal-
cines are kept as a uid by an upward ow of air through openings in the grate
(see FLUIDIZATION). Use of oxygen instead of air in a specially designed uidized-
bed apparatus makes possible the manufacture of high strength sulfur dioxide
from sulde ore (322).
A technique known as ash roasting was developed in the 1920s. Finely
ground pyrites or other sulde ores fall through a chamber in which air is intro-
duced countercurrently from the bottom. The particles burn at 100011008C
yielding sulfur dioxide free of sulfur trioxide at a concentration suitable for mak-
ing sulfuric acid or for sulte pulping (323).
A basic research study on combustion of sulfur led to the postulation that
sulfur trioxide may actually be the primary combustion product and that sulfur
dioxide may then be produced by the further reaction of sulfur trioxide with sul-
fur vapor in the oxygen-decient region of the ame (324).
36 SULFUR COMPOUNDS Vol. 23
Recovery from Flue Gases. Recovery of sulfur dioxide from ue gases
has been described (25,112,287). The stack gas from smelting often contains suf-
cient sulfur dioxide (~6wt%) for economic conversion to sulfuric acid; the lower
concentration in power plant stack gases generally requires some method for
concentrating the sulfur dioxide.
Production from Oleum. Production of SO
2
from oleum was developed at
Stauffer Chemical Company and is used commercially to produce liquid sulfur
dioxide. It can be integrated with an existing oleum operation or with a concen-
trated sulfuric acid-consuming operation.
3 SO
2
2 SO
3
+ S
0
A ow diagram of the plant is shown in Fig. 1. Approximately 30 wt% oleum is
pumped into a reboiler; 2, and SO
3
is evolved. The resultant 20 wt% oleum is
returned to the oleum towers of an acid plant. For heat conservation, the
oleum streams are interchanged in a heat exchanger, 1. The SO
3
stream passes
through molten sulfur in reactor 3, where the reaction takes place, and molten
sulfur is continuously fed to reactor 3. Periodically, sludge is withdrawn from the
reactor; this occurs every six to eight months if bright sulfur is used. The SO
2
vapors pass through a sulfuric acid tower for removal of trace SO
3
. Cooling, 9;
gas cleaning, 10; compressing, 11; and water condensation, 13, complete the pro-
cess of producing liquid SO
2
for storage. The reactor, 3, is cooled and/or heated
for startup by a closed-water circulation loop, 46. The sulfur dioxide produced is
99.99% pure. Rhodia operates commercial plants of this type. Development of
gas-cleaning techniques and proper economical materials of construction has
resulted in over 96% on-stream time.
The NEAT SO
2
process has been developed by Navdeep Industrial and
Technical Services, India, wherein the oxidation of sulfur by sulfur trioxide is
carried out at 501108C in a pressurized water-jacketed continuous reactor
(320). This process ts well into an existent sulfuric acid plant where sulfur tri-
oxide is available, and it can be adapted to dispose of sulfur lter cake, a proble-
matic waste generated in sulfuric acid plants.
Another method of handling sulfur dioxide is to collect, store and ship it in
an amine solvent, the patented SO
2
SAFE system, from which it can be regener-
ated by heating (320,326). This is an extension of the CANSOLV scrubbing sys-
tem Safety advantages must be balanced off against the cost of transport.
Another version of the regenerable scrubber approach, the LABSORB process,
uses aqueous sodium phosphate (327).
Production from Spent Sulfuric Acid. Spent sulfuric acid recovered from
petrochemical and renery processes can be fed to a high temperature furnace at
87012608C, where it is transformed into sulfur dioxide, water, and oxidative
destruction of the contaminants. After suitable scrubbing and drying, the
gases are passed to a conventional contact sulfuric acid plant (328). Improved
regeneration processes use oxygen to gain higher yields, lower energy consump-
tion and less byproduct nitrogen oxide production (329).
Corrosivity. Almost all common materials of construction are resistant to
commercial dry liquid sulfur dioxide, dry sulfur dioxide gas, and hot sulfur diox-
ide gas containing water at above the dew point (330,331). These include cast
Vol. 23 SULFUR COMPOUNDS 37
iron, carbon steel, copper, brass, and aluminum. Where hot gases or hot solutions
are involved, the temperature resistance, particularly for plastics and resins, and
the resistance to thermal shock, particularly for ceramic, glass, and stone, should
be taken into account. The latter materials are inert to wet gas, sulfurous acid,
and sulte solutions. Carbon, graphite, and impregnated carbon are suitable for
practically all types of sulfur dioxide service. Lead is also resistant to sulfur diox-
ide and sultes under most conditions. Aluminum is resistant under a variety of
conditions and is favored in some food-industry applications involving wet sulfur
dioxide. Organic coatings are generally resistant but may fail if gas diffusion
through the lm is appreciable. Among the organic materials, hard rubber has
been satisfactory in sulfurous acid at moderate temperatures, and butyl rubber
may perform similarly.
Iron, steel, nickel, coppernickel alloys, and Inconel NiCrFe are satis-
factory for dry or hot sulfur dioxide, but are readily corroded below the dew
point or by wet sulfur dioxide gas, sulfurous acid, and sultes. Inconel is espe-
cially resistant to very hot sulfur dioxide gas. Metals best suited to a wide variety
of wet, dry, and hot sulfur dioxide, sulfurous acid, and sulte service are nickel
chromium alloys, eg, Worthite and Durimet 20, and several of the austenitic
stainless steels. Type 304 may be satisfactory for mild conditions, but types
316 and 317 are usually required for more severe applications at high tempera-
tures. When sulfuric acid is also present, the 20-grade stainless steels may be
needed. Crucible SC-1 stainless steel is said to be useful for sulfur dioxide scrub-
bers (332).
Liquid sulfur dioxide discolors iron, copper, and brass at ~300 ppm moist-
ure and produces light scale at ~0.1 wt% moisture and serious corrosion at ~0.2
wt% or higher moisture content. Copper and brass can be used to handle wet sul-
fur dioxide where some corrosion can be tolerated, or where the moisture level is
low. Wooden tanks are widely used for sulfurous acid preparation, handling, and
storage. Sulte pulp digestors are made of steel lined with acid-resistant brick.
Corrosion by atmospheric sulfur dioxide should be considered in the devel-
opment and evaluation of protective coatings (333,334). Sulfur dioxide and sulfu-
ric acid therefrom are highly damaging to carbonate building stones (335).
Shipment and Storage. Liquid sulfur dioxide is commonly shipped in
North America using 55- and 90-t tank cars, 20-ton tank trucks, 1-ton cylinders,
and 150-lb cylinders. Cylinders made of specied steel are afxed with the green
label for nonammable gases. The DOT classication is Poison Gas, Inhalation
Hazard. Purchasers of tank-car quantities are required to have adequate storage
facilities for prompt transfer.
All shipping containers for liquid sulfur dioxide are arranged so that with-
drawal or transfer of the contents can be effected either as a gas or as a liquid. In
general, the pressure of the sulfur dioxide in its container is used for the transfer.
The most convenient method for attaining the required pressure differential in
the case of cylinders and drums is heating. Because these containers are
equipped with fusible plugs, it is recommended that the temperature never be
allowed to exceed 528C either in storage or during heating for transfer. In
order to minimize the danger of a container of sulfur dioxide becoming full of
liquid and failing as a result of the development of hydrostatic pressure with ris-
ing temperature, the maximum allowable sulfur dioxide capacity by weight of
38 SULFUR COMPOUNDS Vol. 23
any container has been set by DOT at 1.25 times the water capacity by weight. It
is common practice to ll containers to only 1.15 times the water capacity.
Economic Aspects. A market prole of sulfur dioxide as of January 2004
is available (336). Merchant sulfur dioxide is produced by North American man-
ufacturers; the total capacity excluding captive production in the United States
is in the area of 176,000300,000 short tons (numbers vary with source). The lar-
gest producer in the United States may be Rhodia (from sulfur trioxide reduction
by sulfur, ie, spent sulfuric acid regeneration). There is also a larger captive pro-
duction by sulfuric acid producers. In the 2004 report, list price for merchant sul-
fur dioxide was given as $230/ton and spot pricing as $130150/ton. No growth of
merchant sulfur dioxide was projected since large users tend to burn sulfur
onsite. The use in water treatment to reduce residual chlorine is expected to
decline in areas that move away from water chlorination.
Uses (besides captive use for making sulfuric acid) are estimated (336) to be
manufacture of hydrosultes (25%), other chemicals, 20%; pulp and paper, 15%;
food and agriculture (mainly corn syrup and other sugar processing, preserva-
tion of fruits, vegetables wine and beer), 15%; water and waste treatment,
10%; metal and ore rening (as a sulde depressant in otation), 6%; oil recovery
and rening (as oxygen scavenger to retard corrosion), 4%; and miscellaneous,
including sulfonation of oils and as a reducing agent or antioxidant, 5% (336
338). The pulp and paper industry is expected to have the greatest growth
because of increased paper recycling, requiring bleaching.
Grades and Specications. The main grade of liquid sulfur dioxide is
known as the technical, industrial, or commercial grade. This grade contains a
minimum of 99.98 wt% sulfur dioxide and is a water-white liquid free of sulfur
trioxide and sulfuric acid. It contains only a trace at most of nonvolatile residue.
Its most important specication is the moisture content, which is generally set at
100 ppm maximum. The only other grade sold is the refrigeration grade of liquid
sulfur dioxide, a premium grade having the same purity and specications as the
industrial grade, except for the moisture content, which is specied as 50 ppm
maximum. At least one manufacturer sells a single grade for which specications
have been established as follows: color, APHA 25 max; nonvolatile residue,
25 ppm max; and moisture, 50 ppm max.
Analytical Methods. The ofcial NIOSH recommended method for deter-
mining sulfur dioxide in air consists of drawing a known preltered volume of air
through a bubbler containing hydrogen peroxide, thus oxidizing the sulfur diox-
ide to sulfuric acid. Isopropyl alcohol is then added to the contents in the bubbler
and the pH of the sample is adjusted with dilute perchloric acid. The resultant
solution is then titrated for sulfate with 0.005 M barium perchlorate, and Thorin
is used as the indicator; in the range 6.626.8 mg/m
3
this method is useful for
compliance with the OSHA standard (339).
A method suitable for analysis of sulfur dioxide in ambient air and sensitive
to 0.0035 ppm involves aspirating a measured air sample through a solution of
potassium or sodium tetrachloromercurate, with the resultant formation of a
dichlorosultomercurate. Ethylenediaminetetraacetic acid (EDTA) disodium
salt is added to this solution to complex heavy metals that can interfere by oxi-
dation of the sulfur dioxide. The sample is also treated with 0.6 wt% sulfamic acid
to destroy any nitrite anions. Then the sample is treated with formaldehyde and
Vol. 23 SULFUR COMPOUNDS 39
specially puried acid-bleached rosaniline containing phosphoric acid to control
pH. This reacts with the dichlorosultomercurate to form an intensely colored
rosanilinemethanesulfonic acid. The pH of the solution is adjusted to
1.6 0.1 with phosphoric acid, and the absorbance is read spectrophotometrically
at 548 nm (340).
The Reich test is used to estimate sulfur dioxide content of a gas by measur-
ing the volume of gas required to decolorize a standard iodine solution (341).
Equipment has been developed commercially for continuous monitoring of
stack gas by measuring the near-ultraviolet (uv) absorption bands of sulfur diox-
ide (342344). The determination of sulfur dioxide in food is conducted by distil-
ling the sulfur dioxide from the acidulated sample into a solution of hydrogen
peroxide, followed by acidimetric titration of the sulfuric acid thus produced
(345). Analytical methods for sulfur dioxide have been reviewed (346).
Interest in trace determination of sulfur dioxide in the atmosphere has led
to a number of instrumental methods, such as chemiluminescence in a hydrogen-
rich ame (347), matrix isolation and Fourier transform infrared (FTir) spectro-
scopy (348), colorimetric determination (349), conductimetric sensing after pas-
sage through a special membrane (350), and high pressure chemical ionization
mass spectrometry (351). Continuous monitoring methods have been compared
using uv, ir, and electrochemical methods (352,353). Other continuous monitor-
ing means have been described using chemiluminescence (354) and solid electro-
lyte sensors, said to be rugged enough for stack gas monitoring (355). In
continuous monitoring as much as 30% of the sulfur dioxide may be lost in con-
densed moisture (356).
Health, Safety, and Environmental Factors. Sulfur dioxide has only a
moderate acute toxicity (357). A review of its toxicology is available (357,358).
The lowest published human lethal concentration is 1000 ppm for
10 months. The lowest published human toxic concentration by inhalation is
3ppm for 5 days or 12ppm for 1 h. The lowest published human lethal concentra-
tion is 3000 ppm for 5 months. In solution (as sulfurous acid), the lowest pub-
lished toxic dose is 500 mg/kg causing gastrointestinal disturbances.
Considerable data are available by other modes of exposure and to other species;
NIOSH standards are a time-weighted average of 2 ppm and a short-term expo-
sure limit of 5ppm (357).
Sulfur dioxide is a severe eye irritant (eye irritation level 10 ppm) and skin
irritant in humans (358360). Inhalation of vapor may lead to irritation of the
respiratory tract, cough, sore throat, increased salivation, nausea, vomiting,
bronchoconstriction, chronic respiratory disease, and pulmonary edema. Expo-
sure to very high concentrations may induce acute and chronic bronchitis, che-
mopneumonia, asphyxia, and death. Respiratory effects have been attributed to
workplace exposure. Concentrations even as low as 2ppm can have a respiratory
irritant, choking, and sneeze/cough inducing effect, but some persons can accli-
matize to 2030 ppm. Human subjects have reported 50ppm to be intolerable.
ACGIH has set a threshold limit value-time weighted average of 2ppm
(5.2 mg/m
3
) and the threshold limit value: short-term exposure limit (TLV-
STEL) of 5 ppm (13 mg/m
3
) due to its irritation potential (361). Additionally,
NIOSH has assigned an immediately dangerous to life or health (IDLH) concen-
tration of 100 ppm.
40 SULFUR COMPOUNDS Vol. 23
Lung tumors were reported in mice following long-term inhalation expo-
sure, but sulfur dioxide is not classied as a human carcinogen (361).
Sulfur dioxide shows some mutagenic effects in microorganisms and fruit
ies. Human lymphocyte DNA damage has been observed. It is an equivocal
tumorigenic agent by RTECS criteria (234,357). Sulfur dioxide occurs in indus-
trial and urban atmospheres at 1 ppb1 ppm and in remote areas of the earth at
50120 ppt. Plants and animals have a natural tolerance to low levels of sulfur
dioxide (362). Some plants have a detoxication route for sulfur dioxide. Living
species have had exposure to sulfur dioxide over geologic times from natural
sources that include volcanoes and volcanic vents, decaying organic matter,
and solar action on seawater (363,364). Sulfur dioxide is believed to be the
main sulfur species produced by oxidation of dimethyl sulde that is emitted
from the ocean.
The status of knowledge regarding sourcereceptor relationships, climato-
logical factors, and atmospheric chemistry as a background for regulatory policy
has been reviewed (365). The 1990 Clean Air Act Amendments are intended to
cut annual sulfur dioxide emissions 40% from 1980 levels, and thus minimize
the potential effects of acid rain, which can occur even at great distances from
the source. The program formulated under this legislation allows market-
based trading of emission allowances and exibility in choice of technologies to
reduce emissions, so as to ameliorate lake and stream acidication and damage
to plants, structures, and humans. Estimated emissions of sulfur dioxide in the
United States declined from 25.7 10
6
t in 1980 to ~ 2010
6
t in 2004, ~65% of
which is attributable to electric utilities according to the EPA. Downward trends
in atmospheric sulfate have been noted. However, acidication continues to
effect sensitive forest, soil, and aquatic ecosystems. Human health data appear
inconclusive at other than extreme levels. Regulatory action to limit sulfur emis-
sions has already had a signicant impact on the capital and operating costs of
power generation (qv), the selection of fuel, and the coal mining, gas, and petro-
leum industries. The benets of proposed regulation must be weighed against
high costs and economic disruptions.
Benecial and Harmful Effects on Plants. At low levels, sulfur dioxide in
the atmosphere is not harmful to crops, but damage can occur at excessive levels
(366370). Crops differ greatly in their sensitivity. The physicological, biochem-
ical and molecular effects of sulfur dioxide in plants have been studied (371).
Forest damage attributed to acid rain is often cited, but the observed symp-
toms seem to have multiple causes and the contribution of sulfur acids is unspe-
cied. The sulfur in precipitation is, up to a point, benecial to plant growth
because sulfur is an essential nutrient. Lessening the sulfur content of the atmo-
sphere requires that supplementary sulfur be provided in fertilizer to some
crops; some crops already require supplementary sulfur. Sulfur dioxide itself
has been found useful in drip irrigation systems (372,373) and in calcareous
soils (368). Small eld generators have been developed for this purpose.
Sulfur Dioxide Emissions and Control. A substantial part of the sulfur
dioxide in the atmosphere is the result of burning sulfur-containing fuel, notably
coal, and smelting sulde ores. Methods for controlling sulfur dioxide emissions
have been reviewed (374376) (see also AIR POLLUTION CONTROL METHODS; COAL CON-
Vol. 23 SULFUR COMPOUNDS 41
VERSION PROCESSES, CLEANING AND DESULFURIZATION; EXHAUST CONTROL, INDUSTRIAL;
SULFUR REMOVAL AND RECOVERY).
Some newer methods of adsorbing sulfur dioxide to prevent emissions
involve use of supported magnesia or hydrotalcite (327). Reviews of sulfur diox-
ide scrubbing technologies are available (377379).
Uses. The dominant use of sulfur dioxide is as a captive intermediate for
production of sulfuric acid. There is also substantial captive production in the
pulp and paper industry for sulte pulping, and it is used as an intermediate
for on-site production of bleaches, eg, chlorine dioxide or sodium hydrosulte
(see BLEACHING AGENTS SURVEY). There is a substantial merchant market for sulfur
dioxide in the paper and pulp industry. Sulfur dioxide is used for the production
of chlorine dioxide at the paper (qv) mill site by reduction of sodium chlorate in
sulfuric acid solution and also for production of sodium dithionite by the reaction
of sodium borohydride with sulfur dioxide (380). This last application was grow-
ing rapidly in North America as of the late 1990s.
A smaller, but important, use for sulfur dioxide is for stabilization of pulp
(qv) brightness after hydrogen peroxide bleaching of mechanical pulps. Sulfur
dioxide neutralizes the alkalinity and destroys any excess hydrogen peroxide,
which if left in the pulp would cause it to lose brightness.
In food processing (qv), sulfur dioxide has a wide range of applications
(381,382) as a fumigant, preservative, bleach, and steeping agent for grain and
dried fruit. Because of the sensitivity of some persons to sulfur dioxide, it (also its
salts) has been banned for use on fresh produce by the U.S. Food and Drug
Administration (FDA). In the manufacture of wine (qv), a small amount of sulfur
dioxide is added to destroy bacteria, molds, and wild yeasts without harming
yeasts needed for the desired fermentation. Wine casks are also sterilized by sul-
fur dioxide. The formation of nitrosamines in beer is prevented by sulfur dioxide
treatment in the malting process (383). In molasses manufacture, sugar rening,
and soy protein processing, sulfur dioxide is used for bleaching as well as for the
prevention of microbial growth (384). In making high fructose corn syrups,
sodium bisulte from sulfur dioxide is added to the enzymatic isomerization
step to prevent undesired microbial action. In the earlier stages, where corn is
steeped in preparation to wet milling, a 0.10.2 wt% sulfur dioxide solution is
used to swell and soften kernels and prevent growth of microorganisms. Sulfur
dioxide is used throughout corn syrup processing to prevent microbial growth
and retard nonenzymatic development of color by the Maillard reaction (see
FOOD PROCESSING; SYRUPS).
The FDA Center for Food Safety and Applied Nutrition (CFSAN) studies
sulfur dioxide in their program for Priority-based Assessment of Food Additives
(PAFA). Sulfur dioxide is cited in 21CFR172.892 as a food additive permitted for
direct addition to food for human consumption when used as a bleach treatment
for food starch not to exceed 0.05%. Also in 21CFR 182.3862, this substance is
generally recognized as safe (GRAS) when used in accordance with good manu-
facturing practice, except that it cannot be used in meats, in food recognized as a
source of vitamin B1, on fruits or vegetables intended to be served raw to consu-
mers or sold raw to consumers, or to be presented to consumers as fresh.
In water treatment, sulfur dioxide is often used to reduce residual chlorine
from disinfection and oxidation (385). This technology is used in potable water
42 SULFUR COMPOUNDS Vol. 23
treatment, in sewage treatment, and especially in industrial wastewater treat-
ment (see WATER, INDUSTRIAL WATER TREATMENT; WATER, MUNICIPAL WATER TREATMENT;
WATER, SEWAGE). Although sodium metabisulte [7681-57-4] and sodium sulte
[7757-83-7] may be used, the use of liquid sulfur dioxide has convenience and
cost advantages and lends itself to automation. Therefore, the larger plants
tend to use sulfur dioxide rather than sulte or bisulte salts. Sulfur dioxide
is also employed as a reducing agent for conversion of chromates to less toxic
chromic compounds in plating-shop efuents.
In petroleum technology, sulfur dioxide, sodium bisulte, or sodium sulte
are used as oxygen scavengers (386). This use is particularly important in sec-
ondary and tertiary oil recovery processes involving ooding of underground
oil formations using water or aqueous solutions (see ENHANCED OIL RECOVERY). To
prevent corrosion in piping and storage systems it is important to lower the oxy-
gen concentration of the water to 50100ppb. The rate of oxygen reduction is
increased by adding a cobalt compound as catalyst and maintaining a pH of
8.510 (387). Sulfur dioxide and sodium sultes are also used in oil rening
and other industrial processes, notably in boiler waters, as oxygen scavengers.
Basic studies have been done on the catalysis of sulte or bisulte oxidation
(388,389).
Another sulfur dioxide application in oil rening is as a selective extraction
solvent in the Edeleanu process (390), wherein aromatic components are
extracted from a kerosene stream by sulfur dioxide, leaving a puried stream
of saturated aliphatic hydrocarbons that are relatively insoluble in sulfur diox-
ide. Sulfur dioxide acts as a cocatalyst or catalyst modier in certain processes
for oxidation of o-xylene or naphthalene to phthalic anhydride (391,392).
In mineral technology, sulfur dioxide and sultes are used as otation
depressants for sulde ores. In electrowinning of copper from leach solutions
from ores containing iron, sulfur dioxide prereduces ferric to ferrous ions to
improve current efciency and copper cathode quality. Sulfur dioxide also initi-
ates precipitation of metallic selenium from selenous acid, a by-product of copper
metallurgy (393).
In kaolin (clay) processing, sulfur dioxide reduces colored impurities, eg,
iron compounds. In the bromine industry, sulfur dioxide is used as an antioxi-
dant in spent brine to be reinjected underground. In agriculture, especially in
California, sulfur dioxide is used to increase water penetration and the availabil-
ity of soil nutrients by virtue of its ability to acidulate salinealkali soils (394). It
is also useful for cleaning ferric and manganese oxide deposits from tile drains
(395).
In magnesium casting, sulfur dioxide is employed as an inert blanketing
gas. Another foundry application is as a rapid curing catalyst for furfuryl resins
in cores. Surprisingly, in view of the many efforts to remove sulfur dioxide from
ue gases, there are situations where sulfur dioxide is deliberately introduced. In
power plants burning low sulfur coal and where particulate stack emissions are a
problem, a controlled amount of sulfur dioxide injection may improve particulate
removal.
Sulfur dioxide is useful as a solvent for sulfur trioxide in sulfonation reac-
tions; eg, in the large-scale production of alkylbenzenesulfonate surfactant (396).
Vol. 23 SULFUR COMPOUNDS 43
A newer use for sulfur dioxide is in cyanide detoxication in connection with cya-
nide leaching of precious metals from mine dumps.
13. Sulfur Oxygen Acids and Their Salts
Sulfuric acid, H
2
SO
4
, the most important commercial sulfur compound (see
SULFURIC ACID AND SULFUR TRIOXIDE), and peroxymonosulfuric acid [7722-86-3]
(Caros acid), H
2
SO
5
, are discussed elsewhere (see PEROXIDES AND PEROXIDE COM-
POUNDS, INORGANIC OXIDES). The lower valent sulfur acids are not stable species
at ordinary temperatures. Dithionous acid [15959-26-9], H
2
S
2
O
4
, sulfoxylic
acid [20196-46-7], H
2
SO
2
, and thiosulfuric acid [13686-28-7], H
2
S
2
O
3
are
unstable species. A discussion of efforts to isolate and characterize the unstable
sulfur acids is given (397).
13.1. Sodium Sulte. Physical Properties. Anhydrous sodium sulte
[7757-83-7], Na
2
SO
3
, is an odorless, crystalline solid and most commercial grades
other than by-product materials are colorless or off-white (398401). It melts
only with decomposition. The specic gravity of the pure solid is 2.633
(15.48C). Sodium sulte is quite soluble in water. It has a maximum solubility
of 28 g/100 g sol at 33.48C; at higher and lower temperatures, it is less soluble
in water. Below this temperature, the heptahydrate crystallizes; above this tem-
perature, the anhydrous salt crystallizes. Sodium sulte is soluble in glycerol,
but insoluble in alcohol, acetone, and most other organic solvents.
Chemical Properties. Anhydrous sodium sulte is stable in dry air at
ambient temperatures or at 1008C, but in moist air it undergoes rapid oxidation
to sodium sulfate [7757-82-6]. On heating to 6008C, sodium sulte disproportion-
ates to sodium sulfate and sodium sulde [1313-82-2]. Above 9008C, the decom-
position products are sodium oxide and sulfur dioxide. At 6008C, it forms sodium
sulde upon reduction with carbon (399).
Aqueous solutions of sodium sulte are alkaline and have a pH of ~9.8 at
1wt%. The solutions are oxidized readily by air. The redox potential is a function
of pH, as would be expected from the following equation:
SO
3
+ 2 OH
2
SO
4
+ H
2
O + 2 e
2
E
0
= +0.90 V
Although the usual product of oxidation of sulte by air is sulfate, at high
pH substantial amounts of the strong oxidant Na
2
SO
5
can form (402).
Sodium sulte undergoes addition of sulfur to form sodium thiosulfate. At
acidic pH, the chemistry of sodium sulte is that of bisulte, metabisulte, and
sulfur dioxide.
Manufacture. In a typical process, a solution of sodium carbonate is
allowed to percolate downward through a series of absorption towers through
which sulfur dioxide is passed countercurrently. The solution leaving the towers
is chiey sodium bisulte of typically 27wt% combined sulfur dioxide content.
The solution is then run into a stirred vessel where aqueous sodium carbonate
or sodium hydroxide is added to the point where the bisulte is fully converted
to sulte. The solution may be ltered if necessary to attain the required product
44 SULFUR COMPOUNDS Vol. 23
grade. A pure grade of anhydrous sodium sulte can then be crystallized >408C
because the solubility decreases with increasing temperature.
In a patented process, a stirred suspension of sodium sulte is continuously
treated with aqueous sodium hydroxide and a sulfur dioxide-containing gas at
60858C, and 96% pure anhydrous sodium sulte is removed by ltration
(403). In another continuous one-step process, substantially anhydrous sodium
carbonate and sulfur dioxide are concurrently introduced into a saturated solu-
tion of sodium sulte at pH6.57.6 and >358C with continuous removal of anhy-
drous sodium sulte by ltration (404).
Various processes have been disclosed wherein moist solid sodium pyrosul-
te [7681-57-4] is stirred in a steam-heated vessel with sodium carbonate. The
exothermic reaction at 801108C results in the drying of the product. A lower
grade of sodium sulte is produced commercially in the United States by Indspec
Chemical Corp. as a by-product of the sulfonationcaustic cleavage route to
resorcinol (400).
Shipment and Storage. Anhydrous sodium sulte is supplied in 22.7-
and 45.4-kg moistureproof paper bags or 45.4- and 159-kg ber drums. Most
sodium sulte is shipped by rail in hopper cars. Sodium sulte should be pro-
tected from moisture during storage. When dry it is quite stable, but when wet
it is oxidized by air.
Economic Aspects. According to U.S. data from 2002, sodium sulte is
produced for merchant sales by General Chemical at ~36,000-t capacity (Clay-
mont, Del.), Calabrian Corp. (Port Netches, Tex.), Solvay at ~55,000-t capacity
(Green River, Wy.; mostly anhydrous grade), Olympic at about 8,000-t capacity
(Tacoma, Wash., 20% solution and food grade only), and Southern Ionics (three
plants in Gulf region, anhydrous grade only). Indspec (Petrolia, Pa.) makes
sodium sulte at ~50,000-t capacity as a coproduct of resorcinol manufacture
by the benzenedisulfonic acid route; this off-color product is mostly used in
pulp and paper. There are other large (mostly captive) producers; many pulp
mills produce their own sulte and try to recycle as much as possible. Uses for
sodium sulte are 60% pulp and paper; water treatment, 15%; photography,
10%; and miscellaneous, including textile bleaching, food, chemical intermedi-
ates, ore otation, and mineral recovery, 15%. Some growth is expected as a
reductant for hydrogen peroxide in nonchlorine bleaching of pulp (qv). The
price for the technical-grade solid sodium sulte in 2005 was $0.26/lb
(405,406). Exports have become signicant in recent years.
Grades and Specications. The commercial grades of sodium sulte
available in the United States are (1) photographic grade: white crystalline mate-
rial, typically 97.0 wt% minimum Na
2
SO
3
assay, 0.5 wt% maximum insoluble
matter, 0.15 wt% maximum alkalinity as Na
2
CO
3
, 20ppm maximum iron,
20 ppm maximum heavy metals (as Pb), 0.01 wt% maximum thiosulfate (as
S
2
O
2
3
); (2) anhydrous technical grade: white granular material, typically
95.097.5 wt% Na
2
SO
3
minimum assay; (3) anhydrous Food Chemicals Codex
grade: 95wt% minimum (typically 98.6 wt%) Na
2
SO
3
assay, 3ppm mixture
arsenic, 10 ppm maximum heavy metals (as Pb), 30 ppm maximum selenium;
(4) anhydrous technical (by-product) grade: pink to red-brown powder, 91 wt%
Na
2
SO
3
minimum, 5 wt% sodium sulfate, and ~3wt% sodium carbonate (used
in sulte pulping and oxygen scavenging from boiler and process water); and
Vol. 23 SULFUR COMPOUNDS 45
(5) aqueous solution: 22 wt% minimum Na
2
SO
3
, pH 8.8, specic gravity (25/258C)
1.27. The aqueous solution is a convenient form for use under conditions, where
there are no facilities for handling and dissolving solid salt (398401).
Analytical Methods. A classical and still widely employed analytical
method is iodimetric titration. This is suitable for determination of sodium sul-
te, eg, in boiler water (407). Standard potassium iodatepotassium iodide solu-
tion is commonly used as the titrant with a starch or starch-substitute indicator.
Sodium bisulte occurring as an impurity in sodium sulte can be determined by
addition of hydrogen peroxide to oxidize the bisulte to bisulfate, followed by
titration with standard sodium hydroxide (346).
Health and Safety Factors. Although sodium sulte has no detectible
odor, its dust and solutions are irritating to the skin, eyes, and mucous mem-
branes. The ingestion of sodium sulte causes gastric irritation resulting from
the liberation of sulfurous acid. Large doses can cause violent colic and diarrhea
as well as disturbance of the circulatory and nervous system. Sodium sulte has
an acute oral LD
50
(mouse) of 820 mg/kg. It is weakly mutagenic in some test
microorganisms and mammalian cells. There is inadequate evidence of any car-
cinogenicity (234). Some persons are very sensitive to sultes in food and drink,
so that the FDA has set limits on its use as a preservative (406).
Uses. Many of the applications of sodium sulte are also applications in
which sulfur dioxide may be used, and are discussed under the latter compound.
Pulp Manufacture. Sodium sulte is utilized in neutral semichemical
pulping, acid sulte pulping, and some kraft pulping processes (408). Many
pulp mills prepare their own sulte and recycle as much as possible, but use of
merchant sodium sulte by pulp mills is substantial. New developments in ther-
momechanical pulping make use of sulte pretreatment; various versions have
been described (409). Other advantageous versions of sulte and kraft pulping,
particularly a new hybrid process, have been recently described (410).
Much of the by-product sodium sulte from resorcinol manufacture goes
into pulp applications, as well as a substantial fraction of the lower assay man-
ufactured sodium sulte.
Water Treatment. Sodium sulte is an agent in the reduction of chlorine
or oxygen in water. Dissolved oxygen in boiler water tends to enhance pitting and
other types of corrosion. In boilers operated at <4.82 MPa (700psi), a residual
concentration of 30 ppm of sodium sulte is generally effective. Catalytic
amounts of cobalt are often added to accelerate the reaction of oxygen with sulte
(386,387) (see WATER, INDUSTRIAL WATER TREATMENT).
In waterooding of oil elds, oxygen dissolved in the water can contribute to
pitting of pipes and clogging of injection wells and the oil-bearing rock with iron
corrosion products. A residual concentration of ~10 ppm sodium sulte is
usually effective in preventing these problems. Sodium sulte is also used to
remove oxygen from drilling muds (see PETROLEUM COMPOSITION; DRILLING FLUIDS).
In removing excess free chlorine from municipal or industrial water, from
pulp bleaching plant vent gas scrubbers, and from wastewater, sodium sulte
competes with bisulte, sulfur dioxide or thiosulfate. The considerations involved
in choosing the reductant have been reviewed (411). Other commercial applica-
tions of sodium sulte in wastewater treatment include the reduction of hexava-
46 SULFUR COMPOUNDS Vol. 23
lent chromium to the less toxic Cr
3
salts, as well as the precipitation of silver
and mercury.
Photography. Sodium sulte is useful as a reducing agent in certain
photographic xing baths, developers, hardeners, and intensiers (401). How-
ever, the principal use is as a lm preservative and discoloration preventative
(see PHOTOGRAPHY).
Miscellaneous. In ore otation, sodium sulte functions as a selective
depressant. In textile processing, sodium sulte is used as a bleach for wool
(qv) and polyamide bers and as an antichlor after the use of chlorine bleach.
Synthetic applications of sodium sulte include production of sodium thiosulte
by addition of sulfur and the introduction of sulfonate groups into dyestuffs and
other organic products. Sodium sulte is useful as a scavenger for formaldehyde
in aminoplast-wood compositions, and as a buffer in chrome tanning of leather.
13.2. Sodium Bisulte. Sodium bisulte, NaHSO
3
, exists in solution,
but is not a stable compound in the solid state. The anhydrous sodium bisulte
of commerce consists of sodium metabisulte, Na
2
S
2
O
5
. Aqueous sodium bisulte
solution, having specic gravity 1.36 and containing the equivalent of 2627 wt%
SO
2
, is a commercial product. Its price in 2005 is ~$0.32/lb. Most of the uses are
the same as for sodium sulte or sulfur dioxide.
13.3. Sodium Metabisulte. Physical Properties. Sodium metabi-
sulte (sodium pyrosulte, sodium bisulte (a misnomer)), Na
2
S
2
O
5
, is a white
granular or powdered salt (specic gravity 1.48) and is storable when kept dry
and protected from air. In the presence of traces of water, it develops an odor
of sulfur dioxide and in moist air it decomposes with loss of part of its SO
2
con-
tent and by oxidation to sodium sulfate. Dry sodium metabisulte is more stable
to oxidation than dry sodium sulte. At low temperatures, sodium metabisulte
forms hydrates with 6 and 7 mol of water. The solubility of sodium metabisulte
in water is 39.5 wt% at 208C, 41.6 wt% at 408C, and 44.6 wt% at 608C (412).
Sodium metabisulte is fairly soluble in glycerol and slightly soluble in alcohol.
Chemical Properties. The chemistry of sodium metabisulte is essen-
tially that of the sultebisultemetabisultesulfurous acid system. The rela-
tive proportions of each species depend on the pH. The pH of a sodium bisulte
solution obtained by dissolving 10 wt% sodium metabisulte in water at 208C is
4.9; at 30 wt%, the pH is 4.4.
Manufacture. Aqueous sodium hydroxide, sodium bicarbonate, sodium
carbonate, or sodium sulte solution are treated with sulfur dioxide to produce
sodium metabisulte solution. In one operation, the mother liquor from the pre-
vious batch is reinforced with additional sodium carbonate, which need not be
totally in solution, and then is treated with sulfur dioxide (413,414). In some
plants, the reaction is conducted in a series of two or more stainless steel vessels
or columns in which the sulfur dioxide is passed countercurrent to the alkali. The
solution is cooled and the sodium metabisulte is removed by centrifuging or
ltration. Rapid drying, eg, in a stream-heated shelf dryer or a ash dryer,
avoids excessive decomposition or oxidation to which moist sodium metabisulte
is susceptible.
Shipment and Storage. Sodium metabisulte can be stored under air at
ambient temperatures, but under humid conditions the product cakes and the
available SO
2
content decreases as a result of oxidation. Therefore, storage
Vol. 23 SULFUR COMPOUNDS 47
should be under cool, dry conditions. The product is shipped in 22.7- and 45.4-kg
polyethylene-lined (moistureproof) bags and 45.4- and 181-kg ber drums. Steel
drums are used for export. The solution is shipped in tank cars and trucks. Dry
sodium metabisulte can be handled in iron or steel equipment. Sodium bisulte
solutions can be handled in 316 and 347 stainless steels, lead, rubber, wood,
Haveg, glass-reinforced polyester, or cross-linked polyethylene.
Economic Aspects. U.S. production of sodium metabisulte is estimated
to be well in excess of 45,000t, but statistics are confused by some commingling
with sodium sulte. The principal U.S. producers are Rhodia and General Che-
mical. The price in mid-1995 was $0.63/kg for anhydrous sodium bisulte.
Grades and Specications. Sodium metabisulte is available in photo-
graphic, food and NF, and technical grades (340). Typical analyses for the food
and NF grade are 99 wt% Na
2
S
2
O
5
, 0.6 wt% Na
2
SO
4
; 0.4 wt% Na
2
SO
3
, 3ppm
iron, 0.2 ppm arsenic, 0.1 ppm lead, and 2ppm selenium. Typical analyses for
the technical grade are 98 wt% Na
2
S
2
O
5
, 1.1 wt% Na
2
SO
4
, 0.8 wt% Na
2
SO
3
,
and 4ppm iron. An aqueous solution typically assaying 2042% NaHSO
3
is
sold in tank trucks.
Health and Safety Factors. Sodium metabisulte is nonammable, but
when strongly heated it releases sulfur dioxide. The oral acute toxicity is slight
and the LD
50
(rat, oral) is 2 g/kg. Sodium bisulte appears to be weakly muta-
genic to some bacteria, in rodent embryos, and in a human lymphocyte test.
There is inadequate evidence for carcinogenicity (234,415).
The solid product and its aqueous solutions are mildly acidic and irritate
the skin, eyes, and mucous membranes. The solid material when moist generates
the pungent, irritating odor of sulfur dioxide. Food-grade sodium metabisulte is
permitted in those foods that are not recognized as sources of vitamin B
1
, with
which sulfur dioxide reacts (381) (see VITAMINS, THIAMINE B1).
Uses. Sodium metabisulte is extensively used as a food preservative and
bleach in the same applications as sulfur dioxide. Because sodium metabisulte
is most effective at low pH, the active agent is probably sulfur dioxide or sulfur-
ous acid (412). Sodium bisulte (sodium metabisulte) is used in photography
(qv), as a reductant, and as a preservative for thiosulfate xing baths. Other
reducing agent applications include reduction of chromate in plating efuents
to less toxic chromium salts, which can then precipitate upon addition of lime
(416,417). Sodium metabisulte is also used to reduce chlorine in industrial pro-
cess water and wastewater. In the textile industry, sodium bisulte containing
metabisulte is used as a bleach, especially for wool (qv); as an antichlor after
bleaching of nylon, for reducing vat dyes; and in rendering certain other dyes
soluble. It is a less powerful reductant than sodium dithionite [7775-14-6].
Aqueous sodium bisulte has been shown to be very effective for removing
contaminants, such as sulfur trioxide, dioxide, and hydrogen halides from
exhaust gases from coal- or oil-red burners. The sulfur dioxide can then be
removed downstream by a wet scrubber (418). In tanneries, sodium bisulte is
used to accelerate the unhairing action of lime. It is also used as a chemical
reagent in the synthesis of surfactants (qv). Addition to alpha-olens under
radical catalyzed conditions yields sodium alkylsulfonates (wetting agents).
The addition of sodium bisulte under base-catalyzed conditions to dialkyl mal-
eates yields the sulfosuccinates.
48 SULFUR COMPOUNDS Vol. 23
The reversible addition of sodium bisulte to carbonyl groups is used in the
purication of aldehydes. Sodium bisulte also is employed in polymer and syn-
thetic ber manufacture in several ways. In free-radical polymerization of vinyl
and diene monomers, sodium bisulte or metabisulte are frequently used as the
reducing component of a so-called redox initiator (see INITIATORS). Sodium bisul-
te is also used as a color preventative and is added as such during the coagula-
tion of crepe rubber.
13.4. Sodium Thiosulfate and Other Thiosulfate Salts. (See THIO-
SULFATES).
13.5. Sodium Dithionite [7775-14-6]. Physical Properties. Sodium
dithionite (sodium hydrosulte, sodium sulfoxylate), Na
2
S
2
O
4
, is a colorless
solid and is soluble in water to the extent of 22 g/100 g of water at 208C. It is
sold commercially as both the dry solid and as an aqueous solution (such as
Olins Hydrolin).
Chemical Properties. Anhydrous sodium dithionite is combustible and
can decompose exothermically if subjected to moisture. Sulfur dioxide is given
off violently if the dry salt is heated above 1908C. At room temperature, in the
absence of oxygen, alkaline (pH 912) aqueous solutions of dithionite decompose
slowly over a matter of days. Increased temperature dramatically increases the
decomposition rate. A representation of the decomposition chemistry is as fol-
lows:
2 S
2
O
4
+ H
2
O
2
2 HSO
3
+ S
2
O
3
2
The decomposition of dithionite in aqueous solution is accelerated by thio-
sulfate, polysulde, and acids. The addition of mineral acid to a dithionite solu-
tion produces rst a red color that turns yellow on standing; subsequently, sulfur
precipitates and evolution of sulfur dioxide takes place (419). Sodium dithionite
is stabilized by sodium polyphosphate, sodium carbonate, and sodium salts of
organic acids (420).
Sodium dithionite is most stable and effective as a reducing agent in alka-
line solutions, although with excess strong alkali the following reaction occurs:
3 Na
2
S
2
O
4
+ 6 NaOH 5 Na
2
SO
3
+ Na
2
S + 3 H
2
O
Dithionite is a stronger reducing agent than sulte. Many metal ions, eg, Cu
2
,
Ag
, Pb
2
, Sb
3
, and Bi
3
are reduced to the metal, whereas TiO
2
is reduced to
Ti
3
(346). Dithionite readily reduces iodine, peroxides, ferric salts, and oxygen.
Some of the decolorizing applications of dithionite, eg, in clay bleaching, are
based on the reduction of ferric iron.
Addition of sodium dithionite to formaldehyde yields the sodium salt of
hydroxymethanesulnic acid [79-25-4], HOCH
2
SO
2
Na, which retains the useful
reducing character of the sodium dithionite although somewhat attenuated in
reactivity. The most important organic chemistry of sodium dithionite involves
its use in reducing dyes, eg, anthraquinone vat dyes, sulfur dyes, and indigo,
to their soluble leuco forms (see DYES, ANTHRAQUINONE). Dithionite can reduce var-
ious chromophores that are not reduced by sulte. Dithionite can be used for the
reduction of aldehydes and ketones to alcohols (421). Quantitative studies have
Vol. 23 SULFUR COMPOUNDS 49
been made of the reduction potential of dithionite as a function of pH and the
concentration of other salts (422,423).
Manufacture. A review of older manufacturing processes is available
(424). Commercial processes for production of sodium dithionite are based on
reduction of sulte or bisulte. In order of approximate worldwide production,
commercial processes are reduction by sodium formate, zinc, sodium amalgam
(425427), and electrochemical reduction in a membrane cell. The formate pro-
cess (428430) was commercialized during the 1970s and has become the predo-
minant manufacturing technology. The zinc process (431) continues to decrease
in popularity because of environmental concerns regarding zinc. The amalgam
process was commercialized in the late 1960s, but has limited growth because
it must be tied to a sodium amalgam source. The electrochemical process, com-
mercialized in the late 1980s, is the newest available technology and utilizes only
caustic and sulfur dioxide as raw materials (432). Anhydrous or solution product
can be manufactured by all processes; however, the formate and zinc processes
typically produce dry product, the amalgam and electrochemical processes typi-
cally produce solution product.
Sodium dithionite solution can be produced on-site utilizing a mixed sodium
borohydridesodium hydroxide solution to reduce sodium bisulte. This process
has developed, in part, because of the availability of low cost sulfur dioxide or
bisulte at some paper mills. Improved yields, >90% dithionite based on borohy-
dride, can be obtained by the use of a specic mixing sequence and an optimized
pH prole (433,434). Electrochemical technology is also being offered for on-site
production of sodium hydrosulte solution (435).
Shipment and Storage. Anhydrous sodium dithionite is shipped in
sealed, water-tight containers and must be stored in dry and cool locations. Stan-
dard containers are metal drums and semibulk containers. A double inner plastic
liner is recommended to prevent access of both water and air. Properly stored dry
product can have an effective shelf-life of at least 612 months. Dissolving dry
product should be accomplished by adding the dry product to the solution to
avoid potential ignition of the dry product. In the event of a re, water in
large amounts is recommended. Several designs for automated mixing have
been developed to minimize problems with dry dissolving.
The solution product has grown signicantly because of health, ammabil-
ity, storage, and handling issues of the dry product. Dithionite solution can be
stored in dedicated, insulated tanks that may be refrigerated for longer term sto-
rage. Commercial solution product is stored with an inert atmosphere or vapor
barrier.
Economic Aspects. U.S. demand for merchant sodium dithionite (solids
basis) was estimated at 104,000 short tons in 2002, projected 110,000t by 2006.
Net imports were 9000 short tons in 2002. There are four North American pro-
ducers of sodium dithionite. Chemtrade Logistics is the largest producer (45,000-
t capacity) with two locations, believed to be mainly using the formate process,
Olin (36,000-t capacity), Celanese (30,000-t capacity) and Vulcan (4000-t capa-
city), in a small solution plant in Wisconsin using the Olin electrochemical pro-
cess. In addition, it was estimated in 1992 that 13,000 t/year is produced at U.S.
pulp mills using the Borol process from sulfur dioxide and sodium borohydride.
50 SULFUR COMPOUNDS Vol. 23
Growth is estimated at 23%/year. The list price in mid-2003 was ~$0.76/lb
(436438) with substantial discounting for large volume users.
Grades. There are several commercial solid sodium dithionite grades,
>90, >88, >85, and ~70 wt% dry product (often blended with other stabilizers
or additives), and 125-g/L stabilized solution. It is stabilized by ~4 g/L of sodium
hydroxide.
Analytical Methods. Various analytical methods involve titration with
oxidants, eg, hexacyanoferrate (ferricyanide), which oxidize dithionites to sulte.
Iodimetric titration to sulfate in the presence of formaldehyde enables dithionite
to be distinguished from sulte because aldehyde adducts of sulte are not oxi-
dized by iodine. Reductive bleaching of dyes can be used to determine dithionite,
the extent of reduction being determined photometrically. Methods for determin-
ing mixtures of dithionite, sulte, and thiosulfates have been reviewed (439).
Analysis of dithionite particularly for thiosulfate, a frequent and undesirable
impurity, can be done easily by liquid chromatography (440).
Health and Safety Factors. Dry sodium dithionite, when exposed to
moist air, heats and can ignite spontaneously. In case of re, the burning mate-
rial must be deluged with water, as too little water may be worse than none at
all. Carbon dioxide and dry extinguishers are ineffective because dithionite pro-
vides its own oxygen for combustion. Large amounts of sulfur dioxide are liber-
ated, further complicating re-ghting efforts. Self-contained breathing units
should be worn by all re ghters.
Sodium dithionite is considered only moderately toxic. The solution is
reported to have an LD
50
(rat, oral) of ~5 g/kg. Another report gives the LD
50
(rat) as 25 mg/kg (441). It is slightly irritating to skin, but strongly irritating
to eyes (rabbit tests). As with sultes, fairly large doses of sodium dithionite
can probably be tolerated because oxidation to sulfate occurs. However, irritation
of the stomach and respiratory tract by the liberated sulfurous acid or sulfur
dioxide is expected, and as a food additive, sodium dithionite is generally recog-
nized as safe (GRAS) (442).
In 21CFR182.90 sodium dithionite is considered generally recognized as
safe (GRAS) for its intended use as a substance that may migrate to food from
paper and paperboard products used in food packaging.
Uses. Textile applications have historically been primary uses for dithio-
nite, including dye reduction, dye stripping from fabric, bleaching, and equip-
ment cleaning. These applications have not grown as rapidly and in 2002
consume ~24% of the North American consumption (436). Indigo dyeing of cot-
ton denims has been an important application. Conditions have been discussed
for efcient use of sodium hydrosulte in commercial vat dyeing processes (443).
Pulp and paper bleaching applications have grown and by 2002 represented
~56% of the North American dithionite usage, mainly to brighten mechanical
pulps (436). There has also been signicant growth in color stripping of second-
ary bers and some use in polish bleaching of chemical pulps. The factors control-
ling bleaching with hydrosulte have been described (444446). Hydrogen
peroxide competes somewhat. Clay (kaolin) bleaching applications represent
~16% of North American consumption (436). Bleaching by ozone has made
some inroads.
Vol. 23 SULFUR COMPOUNDS 51
Miscellaneous uses include reductive bleaching of glue, gelatin, leather,
soap, oils, food products, photographics, and oxygen scavenging in water (used
for high pressure boilers or for synthetic rubber polymerization). Because the
toxicity of sodium dithionite is only slight, it is permitted in various food-contact
applications. Users of dithionites have largely converted from zinc to sodium
dithionite, to avoid water pollution problems.
13.6. Zinc Dithionite. Zinc dithionite [7779-86-4], ZnS
2
O
4
, is a white,
water-soluble powder. Although it exhibits somewhat greater stability in aqu-
eous solution compared to sodium dithionite at a given temperature and pH, it
is no longer used in the United States because of regulatory constraints on pollu-
tion of water by zinc.
13.7. Sodium and Zinc Formaldehyde Sulfoxylates. Although free
sulfoxylic acid [20196-46-7], H
2
SO
2
, has not been isolated and its salts are in
doubt, organic derivatives, which may be viewed as adducts of sulfoxylic acid,
are commercially made. The latter are mainly sodium formaldehyde sulfoxylate
[149-44-0], HOCH
2
SO
2
Na (commercially sold as the dihydrate) and zinc formal-
dehyde sulfoxylate [24887-06-7] (424). These compounds are water-soluble redu-
cing agents with uses similar to the dithionites but are more stable. They can be
used in reducing and bleaching applications at lower pH values and at somewhat
higher temperatures than the dithionites. For example, the formaldehyde sulfox-
ylates are useful at pH 3.4 as compared to an optimum pH of ~6 for zinc dithio-
nite and ~9.5 for sodium dithionite. The most stable compound of this series is
basic zinc formaldehyde sulfoxylate, which can be used as a reductant at
~1008C, compared to ~508C for sodium dithionite.
In addition to applications in dyeing, sodium formaldehyde sulfoxylate is
used as a component of the redox system in emulsion polymerization of
styrenebutadiene rubber recipes.
13.8. Dithionic Acid [14970-71-9] and Metal Dithionates. The
dithionate anion is S
2
O
6
2
and is symmetrical with a
O
3
SSO
3
structure. Con-
centrated free dithionic acid [14970-71-9], a strong acid, is unstable. Most of its
salts are water soluble. Five dithionate metal salts (Na
2
S
2
O
6
(anhydrous [14970-
71-9]; dihydrate [7631-94-9]), CaS
2
O
6
, BaS
2
O
6
, MgS
2
O
6
, K
2
S
2
O
6
) are commer-
cially available on a small scale. Note that because of errors in nomenclature, lit-
erature references to dithionates often actually pertain to the much more
common dithionites. Moreover, dithionic acid is sometimes confused in the litera-
ture with pyrosulfuric acid.
Preparation and Analysis. Manganese dithionate was prepared in the
nineteenth century via the reaction of MnO
2
with aqueous SO
2
. This reaction
remains the best known method for producing dithionic acid and its salts
(447449). The major impurities are manganese sulte and manganese sulfate.
The procedure of Carpenter, based on the reaction of ferric oxide and SO
2
, does
not represent an improved method because sulte is also produced (450). Pre-
parative metathesis reactions starting with manganese dithionate via mem-
brane-based methodologies represent the best current method for the general
manufacture of the other dithionate salts.
One of the unique features of the dithionate anion is its relative instability
with respect to hydrolysisdisproportionation at low pH, to form bisulfate and
52 SULFUR COMPOUNDS Vol. 23
sulfurous acid (451). The analytical method of Soffer permits distinguishing
amongst these species (452).
Because of incomplete oxidation of sulte, liquors from alkaline scrubbing
of sulfur dioxide sometimes contain some dithionate. Where it is essential to
destroy the dithionate, acidication and heating is effective (453).
Uses. The potential for commercial use of dithionate salts in metal nish-
ing formulations has recently been shown by researchers at Atona (now
Arkema) (454). The good water solubility of the dithionate salts provides an
advantage. Plating on steel using copper dithionate plus ammonium dithionate
allows higher current density, faster plating, better throwing power, and reduc-
tion of cell voltage compared to the conventional plating baths. Nickel plating
using dithionate shows better tensile quality and reduction of cell voltage. As a
cleaner for removal of rust from steel, ammonium dithionate shows much faster
action than ammonium sulfate.
Health and Safety Factors. Very little is known about the specic toxicol-
ogy of dithionic acid and metal dithionates. The dithionate anion is chemically
inert and not expected to be more toxic than comparable neutral sulfur oxide
anions, but the specic toxicological properties of the anion are not known.
14. Thiocyanic Acid and its Salts
Free thiocyanic acid [463-56-9], HSCN, can be isolated from its salts, but is not
an article of commerce because of its instability, although dilute solutions can be
stored briey. Commercial derivatives of thiocyanic acid are principally ammo-
nium, sodium, and potassium thiocyanates, as well as several organic thiocya-
nates. The chemistry and biochemistry of thiocyanic acid and its derivatives
have been reviewed extensively (455457).
14.1. Ammonium Thiocyanate. Physical Properties. Ammonium
thiocyanate [1762-95-4], NH
4
SCN, is a hygroscopic crystalline solid that deli-
quesces at high humidities (375,376). It melts at 1498C with partial isomeriza-
tion to thiourea. It is soluble in water to the extent of 65wt% at 258C and
77 wt% at 608C. It is also soluble to 35 wt% in methanol and 20wt% in ethanol
at 258C. It is highly soluble in liquid ammonia and liquid sulfur dioxide, and
moderately soluble in acetonitrile.
Chemical Properties. Ammonium thiocyanate rearranges upon heating
to an equilibrium mixture with thiourea: 30.3 wt% thiourea at 1508C, 25.3 wt%
thiourea at 1808C (456,458). At 1902008C, dry ammonium thiocyanate decom-
poses to hydrogen sulde, ammonia, and carbon disulde, leaving guanidine
thiocyanate [56960-89-5] as a residue. Aqueous solutions of ammonium thiocya-
nate are weakly acidic; a 5 wt% solution has a pH 46.
Thiocyanates are rather stable to air, oxidation, and dilute nitric acid. Of
considerable practical importance are the reactions of thiocyanate with metal
cations. Silver, mercury, lead, and cuprous thiocyanates precipitate. Many
metals form complexes. The deep red complex of ferric iron with thiocyanate
[Fe(SCN)
6
]
3
, is an effective indicator for either ion. Various metal thiocyanate
complexes with transition metals can be extracted into organic solvents.
Vol. 23 SULFUR COMPOUNDS 53
The organic chemistry of thiocyanates is notably that of nucleophilic displa-
cement of alkyl halides by thiocyanate anion to form alkyl thiocyanates:
RCH
2
Cl + SCN
RCH
2
SCN + Cl
2
, into a wide range of sub-
strates. MSC undergoes free-radical-initiated addition to olens to produce
chloro-substituted sulfones (460462) (eq. 1). With strong bases, MSC can
undergo dehydrochlorination to a transitory reactive intermediate, CH
2
SO
2
,
which can dimerize or undergo various addition reactions (463465). MSC
undergoes reactions with alcohols, amines, active methylene compounds (in
the presence of bases), and aromatic hydrocarbons (in the presence of Friedel-
Crafts catalysts) to replace, generally, a hydrogen atom by a methanesulfonyl
group (466484).
The CH
3
SO
2
O group in methanesulfonate esters is a good leaving group,
facilitating nucleophilic displacements. The utility of MSC for methanesulfonyla-
tion is well known in the agricultural, pharmaceutical, and specialty chemical
industries. Methanesulfonyl chloride is a product of Elf Atochem North America
(469471).
C C CH
3
SO
2
C CCl CH
3
SO
2
Cl +
peroxide or
Cu
1
, R
3
N
(1)
Manufacture. Methanesulfonyl chloride is made commercially either by
the chlorination of methyl mercaptan or by the sulfochlorination of methane.
The product is available in 99.5% assay purity by Elf Atochem NA (now Arkema)
in the United States or by Elf Atochem SA in Europe.
Shipment and Storage. The weight per gallon is 5.6 kg. MSC is shipped
and stored in 55-gal (0.208 m
3
) steel drums or 5-gal (0.02 m
3
) steel pails with a
polyethylene liner. Anhydrous MSC is also corrosive toward titanium,
titaniumpalladium, and zirconium as measured in metal strip tests at 508C.
It is classied as a corrosive liquid.
Health and Safety Factors. MSC has a vapor toxicity on mice of LD
50
4.7 mg/L. It is a lachrymator and in order to prevent contact with eyes, goggles
should be worn. It is also corrosive to skin and therefore chemically resistant
gloves and protective clothing should be worn to prevent contact with skin. Con-
tainers should only be opened where there is adequate ventilation.
Uses. Most applications of MSC are for intermediates in the pharmaceu-
tical, photographic, ber, dye, and agricultural industries. There also are miscel-
laneous uses as a stabilizer, catalyst, curing agent, and chlorination agent.
Some important applications of MSC are shown in equations 24 (471,483).
A pharmaceutical intermediate, 2-azabicyclo[2.2.1]hept-5-en-3-one is produced
by equations 3 and 4.
Vol. 23 SULFUR COMPOUNDS 57
CH
3
C H CH
3
SO
2
Cl + HO
C O
OC
2
H
5
CH
3
C H CH
3
SO
3
C O
OC
2
H
5
CH
3
C Nu H
C O
OC
2
H
5
MSC for asymmetric synthesis
pyridine
acetone
Nu
CH
3
SO
3
(S) (R) (S)
(2)
Methanesulfonyl cyanide as a dienophile
Na
2
SO
3
NaHCO
3
CH
3
SO
2
Cl CH
3
SO
2
Na
ClCN
CH
3
SO
2
CN
(3)
N
SO
2
CH
3
NH
O
(4 + 2) CH
3
COOHH
2
O
+ CH
3
SO
2
CN
(4)
15.2. Methanesulfonic Acid. Physical Properties. Methanesulfonic
acid [75-75-2] (MSA), CH
3
SO
3
H, is a clear, colorless, strong organic acid avail-
able in bulk quantities from Elf Atochem North America as a 70% solution and
on an anhydrous basis (100%). MSA is soluble in water and in many organic sol-
vents. Its physical properties are described in Table 10.
Chemical Properties; Uses. Methanesulfonic acid combines high acid
strength with low molecular weight. Its pK
a
(laser Raman spectroscopy) is
1.9, about twice the acid strength of HCl and half the strength of sulfuric
acid. MSA nds use as catalyst for esterication, alkylation, and in the polymer-
ization and curing of coatings (485,487,488). The anhydrous acid is also useful as
a solvent.
The metal salts of MSA are highly soluble in water as well as in some
organic solvents, making MSA useful in electroplating operations. For example,
lead sulfate is insoluble in water, whereas lead methanesulfonate (lead mesylate)
is water soluble.
Methanesulfonic acid also nds use in preparing biological and agricultural
chemicals, textile treatment chemicals, and for plastics and polymers. Various
high molecular weight polymers are soluble in MSA, it is biodegradable and can
be recycled, it has an advantage in many applications in that it is a nonoxidizing
acid which results in no charring and minimal byproducts, and because of this it is
a preferred acid for catalyzing esterications to give low color ester products.
Specically MSA has been found to be more effective than p-toluenesulfonic
acid and sulfuric acid in preparing dioctyl phthalate (488). A U.S. patent also dis-
closes its use to prepare light-colored fatty esters (489). It is also important as a
catalyst to prepare acrylates, methacrylates, adipates, phthalates, trimellitates,
thioglycolates, and other esters.
58 SULFUR COMPOUNDS Vol. 23
The use of MSA as catalyst to prepare 2-alkylphenols and 2,6-dialkylphe-
nols has been described (490).
Methanesulfonic acid and other lower alkanesulfonic acids are useful for
plating of lead, nickel, cadmium, silver, and zinc (491,492). It also nds use in
plating of tin, copper, lead, and other metals and is used in printed circuit
board manufacture. In metal nishing the metal coating can be stripped chemi-
cally or electrolytically with MSA. It also nds use in polymers, as a polymer sol-
vent and as a catalyst for polymerization of monomers such as acrylonitrile.
Methanesulfonic acid nds use in ion-exchange resin regeneration because of
the high solubility of many metal salts in aqueous solutions.
The popularity of MSA as an electrolyte in electrochemical applications has
developed as a result of the following unique physical and chemical properties:
(1) exhibits low corrosivity and is easy to handle, (2) nonoxidizing, (3) manufac-
turing process yields a high purity acid, (4) exceptional electrical conductivity, (5)
high solubility of metal salts permits broad applications, (6) MSA-based formula-
tions are simpler, (7) biodegradable, and (8) highly stable to heat and electrical
current.
Health and Safety Factors. Methanesulfonic acid is a strong toxic acid
and is corrosive to skin. The acute oral toxicity of the sodium salt in mice LD
50
is 6.2 g/kg. The 1976 edition of the NIOSH Registry of Toxic Effects of Chemical
Substances lists certain reaction products of MSA as having suspected muta-
genic, teratogenic, and carcinogenic activity (493).
Manufacture. Methanesulfonic acid is made commercially by oxidation of
methyl mercaptan by chlorine in aqueous hydrochloric acid to give methanesul-
fonyl chloride that is then hydrolyzed to MSA.
Shipping and Storage. Methanesulfonic acid is shipped in tank trucks
and in plastic 55-gal drums or smaller containers with polyethylene inserts.
The freight classication is Alkyl Sulfonic Acid, Liquid; 8 Corrosive Material,
UN 2586, Chemical N01BN.
15.3. Methanesulfonamide and N-Alkyl Methanesulfonamides.
Physical Properties. Methanesulfonamide [3144-09-0] is available commer-
cially in the United States and China. The product from Arkema Group, Inc.
has been sold under the name of MSAM in a pure crystalline form, mp 89.5
918C (494,495). It is low in volatility, having a vapor pressure of 3mm at
1058C and 20 mm at 1808C. It is very soluble in water, to ~50% by weight at
258C, and moderately soluble in isopropyl alcohol.
N-Methylmethanesulfonamide (494) has been available from Arkema as a
water-miscible liquid, bp 1171188C at 0.3 mm, refractive index 1.4508 at
238C, density 1.277g/cm
3
at 308C.
Chemical Properties. Methanesulfonamides are quite stable hydrolyti-
cally, but the N-hydrogens are more acidic than those of a carboxamide, and
are removable by moderately strong bases. The resultant anion can be readily
alkylated or arylated. Other chemistry of methanesulfonamide, mostly substitu-
tion on the nitrogen, has been described, using alkyl halides, acyl halides, epox-
ides, aldehydes, isocyanates, cyanates, carbon disulde and thionyl chloride
(494498).
Vol. 23 SULFUR COMPOUNDS 59
Manufacture. Methanesulfonamide is produced commercially by the reac-
tion of methanesulfonyl chloride and ammonia by a patented process (499501).
N-Methylmethanesulfonamide is produced analogously using methylamine.
Uses. Methanesulfonamide is reacted with a substituted benzoyl chlor-
ide, to produce 5-[2-chloro-4-(triuoromethyl)phenoxy]-N-(methylsulfonyl)-2-
nitrobenzamide (fomesafen) [72178-02-0], a herbicide used for postemergence
weed control in soybeans (502).
N-Methyl methanesulfonamide is a pharmaceutical intermediate.
Health and Safety Factors. Information from the manufacturer indicates
that methanesulfonamide is of very low toxicity, with LD
50
(rat, oral) >4000 mg/
kg. Although skin contact should be minimized, it has only slight dermal toxicity.
BIBLIOGRAPHY
Sulfur CompoundsStructures and Sulfur Compounds, Inorganic in ECT 1st ed., Vol.
13, pp. 374430, by P. Macaluso, Stauffer Chemical Co.; Sulfur Compounds in ECT 2nd
ed., Vol. 19, pp. 367424, by P. Macaluso, Stauffer Chemical Co.; in ECT 3rd ed., Vol. 22,
pp. 107167, by E. D. Weil, Stauffer Chemical Co.; in ECT 4th ed., Vol. 23, pp. 267340,
by E. D. Weil, Polytechnic University, and S. R. Sandler, Elf Atochem North America, Inc.,
Sulfur Compounds in ECT (online), posting date: December 4, 2000.
CITED PUBLICATIONS
1. G. Gattow and W. Behrendt, in A. Senning, ed., Topics in Sulfur Chemistry, Vol. 2,
Georg Thieme Verlag, Stuttgart, Germany, 1977, pp. 197206.
2. Gmelins Handbuch der Anorganischen Chemie, 8th ed., System No. 14, Pt. D4,
Springer-Verlag, Berlin, Heidelberg, 1977, pp. 128.
3. E. M. Strauss and R. Steudel, Z. Naturforsch, B: Chem. Sci. 42(6), 682 (1987).
4. W. Stadlbauer and T. Kappe, Chem. Ztg. 101(3), 137 (1977).
5. A. O. Diallo and J. H. Dixmier, C. R. Acad. Sci. Ser. C 263, 375 (1966).
6. A. P. Ginsberg, J. L. Lundberg, and W. E. Silverthorn, Inorg. Chem. 10, 2079 (1971).
7. M. Herberhold, Nachr. Chem. Tech. Lab. 29, 365 (1981).
8. M. P. Kramer, Diss. Abstr. Int. B 47(2), 623 (1986); E. K. Moltzen, A. Senning, M. P.
Kramer, and K. J. Klabunde, J. Org. Chem. 49, 3854 (1984).
9. J. B. Hyne, Understanding Sulphur, paper presented at Sulphur 81, International
Conference, Calgary, Alberta, Canada, May 2528, 1981.
10. A. R. Shirley, Jr., and R. S. Meline, Adv. Chem. Ser. 140, 38 (1975).
11. U.S. Pat. 4,143,214 (Mar. 6, 1979), C. H. Chang and J. M. Longo (to Exxon Research
and Engineering Co.).
12. J. P. Wibaud, Recl. Trav. Chim. Pays-Bas 41, 153 (1922).
13. R. Ciusa, Gazz. Chim. Ital. 55, 385 (1925), and references cited therein.
14. D. D. Wagman, W. H. Evans, V. B. Parker, I. Halow, S. M. Bailey, and R. H.
Schumm, Selected Values of Chemical Thermodynamic Properties, NBS Technical
Note 270-3, National Bureau of Standards, U.S. Dept. of Commerce, Washington,
D.C., 1968.
15. Ref. 2, Pt. D5, pp. 2140.
16. R. L. Rowley and co-workers, DIPPR Data Compilation of Pure Compound Proper-
ties, Design Institute for Physical Properties, AIChE, New York, 2001.
60 SULFUR COMPOUNDS Vol. 23
17. P. D. N. Svoronos and T. J. Bruno, Ind. Eng. Chem. 41, 5321 (2002).
18. D. B. Robinson and N. H. Senturk, J. Chem. Thermodyn. 11, 461 (1979).
19. R. D. Miranda, D. B. Robinson, and H. Kalra, J. Chem. Eng. Data 21(1), 62 (1976).
20. M. B. Mick, Hydrocarbon Proc. 55(7), 137 (1976).
21. S. Weber and G. McClure, The Cosden/Malaprop Process for Light Hydrocarbon
Desulfurization, Annual Meeting Paper AM-81-49, National Petroleum Reners As-
sociation, Washington, D.C., 1981.
22. R. J. Ferm, Chem. Rev. 57, 621 (1957).
23. T. A. Gens, Ind. Eng. Chem. Res. 33, 1654 (1994).
24. Anon., Sulphur 281, 31 (2002).
25. A. Kohl and F. Riesenfeld, Gas Purication, 2nd ed., Gulf Publishing Co., Houston,
Tex., 1974, pp. 607633.
26. K. Nelson and L. Wolfe, Oil Gas J. 183 (July 27, 1981).
27. P. J. Crutzen, L. E. Heidt, J. P. Krasnec, W. H. Pollock, and W. Seller, Nature
(London) 282, 253 (1979).
28. T. E. Graedel, G. W. Kammlot, and J. P. Franey, Science 212, 663 (1981).
29. S. C. Lee, M. J. Snodgrass, M. K. Park, and O. C. Sandall, Environ. Sci. 35, 2352
(2001).
30. O. P. Strausz, in A. Senning, ed., Sulfur in Organic and Inorganic Chemistry, Vol. 2,
Marcel Dekker, New York, 1972, pp. 112.
31. S. M. Kluczewski and co-workers, J. Labelled Compounds Radiopharm. 21(5), 485
(1984).
32. U.S. Pat. 3,235,333 (Feb. 15, 1966), E. A. Swakon and E. Field (to Standard Oil Co. of
Indiana).
33. U.S. Pat. 4,007,254 (Feb. 8, 1977), R. Buathier, A. Combes, F. Pierrot, and H. Guer-
pillon (to Rhone-Poulenc Industries).
34. A. Attar, Fuel 57, 201 (1978).
35. R. Steudel, Z. Anorg. Allg. Chem. 346, 255 (1966).
36. W. C. Andersen and T. J. Bruno, Ind. Eng. Chem. Res. 42, 963 (March 2003).
37. P. D. Clark, Ind. Eng. Chem. Res. 40(2), 497 (2001).
38. M. Chin and D. D. Davis, J. Geophys. Res. 100, 8839 (1995).
39. Carbon Disulde, Carbonyl Sulde: Literature Review and Environmental Assess-
ment, NTIS Report No. PB-257947, report for Environmental Protection Agency,
U.S. Dept. of Commerce by Stanford Research Institute, Menlo Park, Calif., 1976.
40. S. F. Watts, Atmos. Environ. 34, 761 (2000).
41. O. R. Flock and M. O. Andreae, Mar. Chem. 64, 11 (1996).
42. P. S. Weiss, J. E. Johnson, R. H. Gammon, and T. S. Bates, J. Geophys. Res. 100,
23083 (1995).
43. J. Kesselmeier, N. Teusch, and U. Kuhn, J. Geophys. Res. D: Atmos. 104, 11577
(1999).
44. Blexinger, C. Wilhelm, and J. Kesselmeier, Biogeochemistry 48, 185 (2000).
45. G. Protoschill-Krebs and J. Kesselmeier, Bot. Acta 105, 206 (1995).
46. R. G. Confer and R. S. Brief, Am. Ind. Hyg. Assoc. J. 843 (Nov. 1975).
47. W. C. Andersen, A. I. Abdulagatov, and T. J. Bruno, Energy Fuels 17, 120 (2003).
48. C. P. Changelis and R. A. Neal, Toxicol. Appl. Pharmacol. 55, 198 (1980).
49. N. I. Sax, Dangerous Properties of Industrial Materials, 5th ed., Van Nostrand
Rheinhold Co., New York, 1979, p. 470; Dangerous Prop. Ind. Mater. Rep. 12(3),
349 (1992).
50. Jpn. Kokai Tokkyo Koho JP 57,026,657 (Feb. 12, 1982) (to Ihara Chemical Industry,
Co., Ltd.).
51. S. R. Sandler and W. Karo, Organic Functional Group Preparations, 2nd ed., Vol. II,
Academic Press, Inc., New York, 1986, pp. 152, 167170.
Vol. 23 SULFUR COMPOUNDS 61
52. T. Mizuno, I. Nishiguchi, T. Hirashima, and N. Sonoda, Heteroat. Chem. 1(2), 157
(1990).
53. J. L. Zettler, J. G. Leesch, R. F. Gill, and B. E. Mackey, J. Econ. Entomol. 90, 832
(1999).
54. R. Plarre and C. Reichmuth, Nachrichtenbl. Dtsch. Pfanzenschutzdienstes 48, 105
(1996).
55. B. Zwanenburg, L. Thijs, and S. Strating, Tetrahedron Lett. 51, 4461 (1969).
56. H. Tilles, in N. Kharasch and C. Y. Meyers, eds., The Chemistry of Organic
Sulfur Compounds, Vol. 2, Pergamon Press, Oxford, U.K., 1966, pp. 311336;
H. Maegerlein, G. Meyer, and H. D. Rupp, Synthesis 1, 26 (1974).
57. S. Sharma, Synthesis 11, 803 (Nov. 1978); S. Sharma, Sulfur Rep. 5(1), 1 (1986);
A. Jackson, Spec. Chem. 14(3), 210, 214 (1994).
58. D. C. Moule, F. Takashige, and E. C. Lim, in Advances in Photochemistry 28, D. C.
Neckers, W. S. Jenks, and T. Wolff, eds., John Wiley & Sons, Inc., Hoboken, N.J.,
2005, pp. 2878.
59. X.-H. Du, Y.-S. Xu, and Y.-F. Fu, Pesticides 43(2), 78 (2004).
60. L. H. Tagle, F. R. Diaz, J. C. Vega, and P. F. Alquinta, Makromol. Chem. 186(5), 915
(1985); L. H. Tagle, F. R. Diaz, and R. Ruenzalida, J. Macromol. Sci., Pure Appl.
Chem. A31(3), 283 (1994).
61. WO Pat. Appl. 02,079,176 (2002), M. J. Mulville, D. V. Nguyen, and B. S. MacDou-
gall (to Dow Agrosciences).
62. S. J. Tavener, D. J. Adams, and J. H. Clark, J. Fluorine Chem. 95(1), 171 (1999).
63. U.S. Pat. 6,225,505 (May 1, 2001), Y. Kimura, H. Hiyoshi, K. Toriyabe, and N. Wada
(to Ihara Chem. Ind. Co. and Kumiai Chem. Ind. Co.).
64. Registry of Toxic Effects of Chemical Substances, U.S. Dept. of Health and Human
Services, Public Health Service, Center for Disease Control, National Institute for
Occupational Safety and Health, Cincinnati, Ohio, Sept. 1980.
65. Thiophosgene, MSDS, No. T9136, Aldrich Chemical Co., Milwaukee, Wis., May 11,
1995.
66. Perchloromethyl Mercaptan, Product Report, Stauffer Chemical Co., New York,
1966.
67. Perchloromethyl Mercaptan, Stauffer Chemical Co., Agricultural Chemical Division,
Chemical Intermediates Data Sheet, Westport, Conn., Nov. 1978.
68. R. J. Lewis, Sr., Hanleys, Condensed Chemical Dictionary, 12th ed., Van Nostrand-
Reinhold Publishers, New York, 1993, p. 1171.
69. R. C. Weber, P. A. Parker, and M. Bowser, Vapor Pressure Distribution of Selected
Organic Chemicals, USEPA No. 600/2-81-021, U.S. EPA, Washington, D.C., 1981,
p. 39.
70. F. A. Drahowzal, in N. Kharasch, ed., Organic Sulfur Compounds, Vol. 1, Pergamon
Press, Oxford, U.K., 1961, pp. 361374.
71. J. Silha nek and M. Zbirovsk, Collect. Czech. Chem. Commun. 42, 2518 (1977).
72. J. Silha nek and M. Zbirovsk, Int. J. Sulfur Chem. 8, 423 (1973).
73. E. Kuhle, Synthesis 561 (Nov. 1970).
74. H. Kloosterziel, Q. Rep. Sulfur Chem. 2, 353 (1967).
75. H. Senning, Chem. Rev. 65, 385 (1965).
76. Jpn. Pat. 61229861A2 (Oct. 14, 1986), K. Tsuzuki and T. Uotani (to Toyo Soda Mfg.
Co.).
77. Jpn. Pat. 61233662A2 (Oct. 17, 1986), K. Tsuzuki and T. Uotani (to Toyo Soda Mfg.
Co.).
78. U.S. Pat. 3,673,246 (June 27, 1972), G. Meyer and H. Ma gerlein (to Glanzstoff A.-G.);
H. Ma gerlein, G. Meyer, and H. Rupp, Synthesis 478 (Sept. 1971).
62 SULFUR COMPOUNDS Vol. 23
79. U.S. Pat. 3,808,270 (Apr. 30, 1974), H. Rupp, G. Meyer, H. Zengel, and H. Ma gerlein
(to Akzo NV).
80. U.S. Pat. 4,092,357 (May 30, 1978), C. C. Greco and E. N. Walsh (to Stauffer Chemi-
cal Co.); U.S. Pat. 4,093,651 (June 6, 1978), M. L. Honig, C. C. Greco, and E. N.
Walsh (to Stauffer Chemical Co.); U.S. Pat. 4,100,190 (July 11, 1978), V. C. Martines
and R. G. Campbell (to Stauffer Chemical Co.); U.S. Pat. 4,101,446 (July 18, 1978),
M. L. Honig (to Stauffer Chemical Co.).
81. U.S. Pat. 3,993,693 (Nov. 23, 1976), S. K. Bhutani (to Olin Corp.).
82. L. Kremer and L. D. Spicer, Anal. Chem. 45, 1963 (1973).
83. A. Hellwig and D. Hempel, Z. Chem. 7, 315 (1967).
84. Documentation of TLVS, 5th ed., ACGIH, Cincinnati, Ohio, 1986, p. 466.1.
85. E. H. Vernot, J. D. MacEwen, C. C. Haun, and E. R. Kinkaid, Toxicol. Appl. Phar-
macol. 42, 417 (1977).
86. Hazard Information Review No. IR-216, prepared by Enviro Control, Inc., for TSCA
Interagency Testing Committee, Washington, D.C., Nov. 25, 1980; Fed. Reg. 54,
2920 (Nov. 19, 1989).
87. M. Sittig, Pesticide Manufacturing and Toxic Materials Control Encyclopedia, Noyes
Data Corp., Park Ridge, N.J., 1980, pp. 399400.
88. F. Kuhle, E. Klauke, and F. Grewe, Angew. Chem. 76, 807 (1964).
89. U.S. Pat. 3,296,302 (Jan. 3, 1967), E. D. Weil, K. J. Smith, and E. J. Geering (to Hoo-
ker Chemical Corp.).
90. U.S. Pat. 3,200,146 (Aug. 10, 1965), E. D. Weil, E. J. Geering, and K. J. Smith (to
Hooker Chemical Corp.).
91. Belg. Pat. 613,887 (Feb. 28, 1962), (to California Research Corp.).
92. U.S. Pat. 3,259,653 (July 5, 1966), E. D. Weil, E. J. Geering, and K. J. Smith (to Hoo-
ker Chemical Corp.).
93. U.S. Pats. 3,144,482; 3,144,483 (Aug. 11, 1964), R. B. Flay (to California Research
Corp.).
94. U.S. Pat. 3,178,447 (Apr. 13, 1965), G. K. Kohn (to California Research Corp.).
95. B. Meyer, Sulfur, Energy, and Environment, Elsevier Scientic Publishing Co.,
Amsterdam, The Netherlands, 1977.
96. P. Kamoun, Amino Acids 26, 243 (2004).
97. J. B. Hyne, Recent Developments in Sulfur Production from Hydrogen Sulde Con-
taining Gases, paper presented at 181st National Meeting, ACS, Atlanta, Ga., Mar.
29Apr. 3, 1981.
98. M. Schmidt and W. Siebert, in J. C. Bailar, Jr., H. J. Emeleus, R. Nyholm, and A. F.
Trotman-Dickenson, eds., Comprehensive Inorganic Chemistry, Pergamon Press,
Oxford, U.K., 1973, pp. 826837.
99. Selective Values of Properties of Chemical Compounds, Thermodynamics Research
Center Project, Texas A&M University, College Station, Tex., Dec. 31, 1970.
100. J. J. Lagowski, The Chemistry of Nonaqueous Solvents, Inert Aprotic and Acidic
Solvents, Vol. 3, Academic Press, Inc., New York, 1970; see also Chapt. 4.
101. Gmelins Handbuch der Anorganischen Chemie, 8th ed., System No. 9, Pt. B1, Verlag
Chemie, Weinheim/Bergstrasse, Germany, 1953, pp. 1125.
102. J. C. Bailer, H. J. Emeleus, R. Nyholm, and A. F. Trotman-Dickenson, Comprehen-
sive Inorganic Chemistry, Vol. 2, 1973, Pergamon Press, Oxford, U.K., pp. 826883;
D. Ambrose, NPL Rep. Chem. 107 (Feb. 1980).
103. Hydrogen Sulde, Product Safety Information Sheet, Stauffer Chemical Co., Indus-
trial Chemical Division, Westport, Conn., 1973.
104. H. J. Neuberg, J. F. Atheriey, and L. G. Walker, Girdler-Sulde Process Physical
Properties, Atomic Energy of Canada Report AECL-5702, Chalk River Nuclear
Laboratories, Chalk River, Ontario, Canada, 1977.
Vol. 23 SULFUR COMPOUNDS 63
105. G. J. Besserer and D. B. Robinson, J. Chem. Eng. Data 20, 157 (1975).
106. H. Kalra, T. R. Krishnan, and D. B. Robinson, J. Chem. Eng. Data 21, 222 (1976).
107. D. B. Robinson, G. P. Hamaliuk, T. R. Krishnan, and P. R. Bishnoi, J. Chem. Eng.
Data 20, 153 (1975).
108. M. P. Burgess and R. P. Germann, AIChE J. 15, 272 (1969).
109. D. K. Judd, Hydrocarbon Proc. 57, 122 (Apr. 1978).
110. C. Ouwerkerk, Hydrocarbon Proc. 57, 89 (Apr. 1978).
111. F. C. Vidaurri and L. C. Kahre, Hydrocarbon Proc. 56, 333 (Nov. 1977).
112. B. L. Crynes, Chemical Reactions as a Means of Separation, Marcel Dekker, Inc.,
New York, 1977, pp. 155197.
113. J. I. Lee, F. D. Otto, and A. E. Mather, J. Chem. Eng. Data 20, 161 (1975).
114. J. D. Lawson and A. W. Garst, J. Chem. Eng. Data 21, 20 (1976).
115. E. E. Isaacs, F. D. Otto, and A. E. Mather, J. Chem. Eng. Data 22, 317 (1977).
116. J. L. Martin, F. D. Otto, and A. E. Mather, J. Chem. Eng. Data 23, 163 (1978).
117. J. J. Smith, D. Swenson, and B. Meyer, J. Chem. Eng. Data 15(1), 144 (1970).
118. T. K. Wiewiorowski and F. J. Touro, in A. V. Tobolsky, ed., The Chemistry of Sul-
des, Interscience Publishers, a division of John Wiley & Sons, Inc., New York, 1968.
119. M. E. D. Raymont and R. K. Kerr, Alberta Sulphur Res. Quar. Bull. 12(4), 38 (1976).
120. M. E. D. Raymont, Alberta Sulphur Res. Quar. Bull. 8(1), 24 (1971).
121. M. E. D. Raymont, Alberta Sulphur Res. Quar. Bull. 10(4), 1 (1974); M. E. D.
Raymont and J. B. Hyne, Alberta Sulphur Res. Quar. Bull. 12(2), 3 (1975); 12(3),
1 (1975).
122. E. Plasari, P.-M. Marquaire, and M. Huang, Ind. Eng. Chem. Res. 42(17), 3943
(2003).
123. R. Slimane and co-workers, in Proceedings of the 2002 U. S. DOE Hydrogen Program
Review, NREL/CP-610-32405, 2002, p. 15.
124. J. B. Hyne, Sulphur MayJune 280, 46 (2002).
125. A. T-Raissi, Technoeconomic Analysis of Area II Hydrogen ProductionPart 1,
Proceedings of the 2001 DOE Hydrogen Program Review, NREL/CP-570-30535.
126. U.S. Pat. 3,962,409 (June 8, 1976), Y. Kutera, N. Todo, and N. Fukuda (to Agency of
Industrial Science and Technology).
127. M. Gra tzel, Chem. Eng. News 59(30), 40 (July 27, 1981); N. G. Vilesov, J. Appl.
Chem. USSR (Engl. trans. ed.) 53, 1763 (1981).
128. W. Kensell and D. Leppin, Review of the H
2
S Direct Oxidation Processes, Seventh
GRI Sulfur Recovery Conference, Sept. 95, Austin, Tex.
129. D. Banks, Claus Plant Combustor Survey, 2000. Available at http://www.banksengi-
neering.com/claus.htm.
130. A. Pieplu, O. Saur, J. C. LaValley, O. Legendre, and C. Nedez, Catal. Rev.: Sci. Eng.
40(4), 409 (1998).
131. D. Lyons and G. Nickless, in G. Nickless, ed., Inorganic Sulphur Chemistry, Elsevier
Publishing Co., Amsterdam, The Netherlands, 1968, pp. 509533.
132. P. Clark, Sulphur 279, 22 (2002).
133. P. Clark, Sulphur 285, 23 (2003).
134. L. Connock, Sulphur 285, 31 (2003).
135. L. Connock, Sulphur 266, 31 (2000).
136. S. Parkash, chapter on Sulfur Recovery and Pollution Control Processes, in Ren-
ing Process Handbook, Gulf Professional Publishing (Elsevier), 2003, pp. 220241.
137. M. J. Ledoux and co-workers, Sulphur 269, 41 (2000).
138. P. D. Clark, N. I. Dowling, and M. Huang, Catal. Commun. 5(12), 743 (2004).
139. L. Swinney and P. Clark, Sulphur 290, 36 (2004).
140. R. A. Ross and M. R. Jeanes, Ind. Eng. Chem. Prod. Res. Dev. 13(2), 102 (1974).
141. H. M. Castrantas, J. Pet. Technol. 914 (May 1981).
64 SULFUR COMPOUNDS Vol. 23
142. E. E. Reid, Organic Chemistry of Bivalent Sulfur, Vol. 1, Chemical Publishing Co.,
Inc., New York, 1958, pp. 1821.
143. A. Schoberl and A. Wagner, Houben-Weyl, Methoden der Organischen Chemie, 4th
ed., Vol. 5, Georg Thieme Verlag, Stuttgart, Germany, 1962, pp. 2021; S. R. Sand-
ler and W. Karo, Org. Funct. Group Prep. 1, 586, 592 (1983); Y. Labat, Phos., Sulfur
Sil. 74(14), 173 (1993); R. V. Srinivas and G. T. Carroll, in G. R. Lappin and J. D.
Sauer, eds., Alpha Olens Applications Handbook, Marcel Dekker, Inc., New York,
1989, Chapt. 14, pp. 375398.
144. U.S. Pat. 4,568,767 (Feb. 4, 1986), E. J. Dzierza and B. Buchholz (to Elf Atochem
NA).
145. U.S. Pat. 4,937,385 (June 26, 1990), B. Buchholz, E. Dzierza, and R. B. Hager (to Elf
Atochem NA).
146. Can. Pat. 902,113 (June 6, 1972), D. J. Martin and E. D. Weil (to Stauffer Chemical
Co.).
147. U.S. Pat. 4,140,604 (1979), D. A. Dimmig (to Elf Atochem NA).
148. U.S. Pat. 5,026,915 (June 25, 1991), J. R. Baltrus, B. Buchholz, and E. J. Dzierza (to
Elf Atochem North America).
149. M. G. Voronkov and E. N. Deryagina, Phosphorus Sulfur 7, 123 (1979).
150. R. F. Bacon and E. S. Boe, Ind. Eng. Chem. 37, 469 (1945); U.S. Pat. 5,089,246 (Feb.
18, 1992), G. R. Schatz (to Elf Atochem NA).
151. R. N. Tuttle and R. D. Kane, eds., H
2
S Corrosion in Oil and Gas Production, Na-
tional Association of Corrosion Engineers, Houston, Tex., 1981.
152. Sulde Stress Cracking Resistant Metallic Material for Oil Field Equipment, NACE
Standard MR-01-75, 1980 rev., Technical Practices Committee, National Association
of Corrosion Engineers, Houston, Tex., 1980.
153. A. I. Asphahani, Corrosion (Houston) 37, 327 (1981).
154. M. C. Manderson and C. D. Cooper, Sulfur Supply and Demand and Its Relationship
to New Energy Sources, in Ref. 59, Apr. 2, 1981.
155. B. Heydorn, M. Anderson, Y. Yoshida, and F. P. Kalt, Chemical Economics Hand-
book, No. 780.0000, SRI International, Menlo Park, Calif., Mar. 1992, p. 780,0002 K.
156. NIOSH Manual of Analytical Methods, Method No. P & CAM 296, Publication No.
80-125, Vol. 6, U.S. Dept. of Health and Human Services, Washington, D.C., 1980.
157. NIOSH Manual of Analytical Methods, Method No. 54, Vol. 2, U.S. Dept. of Health
and Human Services, Washington, D.C., 1977.
158. Anon., Sulphur 124, 47 (MayJune 1976); 128, 43 (Jan.Feb. 1977).
159. D. Potter, Sulphur 288, 35 (2003).
160. Occupational Exposure to Hydrogen Sulde, Criteria Document, Dept. of Health,
Education, and Welfare (NIOSH) Publication No. 77-158; National Technical Infor-
mation Service Publication No. PB274196, National Institute of Occupational Safety
and Health, Washington, D.C., May 1977.
161. Hydrogen Sulde, Report of the Subcommittee on Hydrogen Sulde, Committee of
Medical and Biologic Effects of Environmental Pollution, Division of Medical
Science, National Research Council, University Park Press, Baltimore, Md., 1979.
162. Draft Toxicological Prole for Hydrogen Sulde: Existing Information on Health
Effects of Hydrogen Sulde, Sept. 2004. Available at http://www.atsdr.cdc.gov/
toxproles/tp114-p.pdf.
163. M. N. Bates, N. Garrett, and P. Shoemack, Arch. Environ. Health 57, 405 (2002).
164. S. R. Armstrong, M. R. Ames, and L. C. Green. Is ambient hydrogen sulde a risk to
human health? Paper presented at the Water Environment Foundation and Air &
Waste Management Association Odors and Air Emissions Speciality Conference,
Bellevue, Wash., 2004.
165. Hydrogen Sulde, MSDS, Matheson Gas Products, Montgomeryville, Pa., 1994.
Vol. 23 SULFUR COMPOUNDS 65
166. H. Linga, E. Nilsen, and F. P. Nilsen, Selective H
2
S removal for the rening indus-
try. Available at http://www.eptq.com/Pages/Articles/Su0107.htm.
167. Gas Treats
TM
- Scavengers to Control H
2
S in the Oileld, bulletin of Champion Tech-
nologies, Houston, Tex.
168. R. B. Nielsen, Treat LPGs with amines, Hydrocarbon Process. 76(9), 49 (1997).
169. I. J. De Kok, C. E. E. Stuiver, S. Westerman, and I. Stulen, 2002. Elevated levels of
hydrogen sulde in the plant environment: nutrient or toxin. Chapt. 10, in K.
Osama, H. Saji, S. Youssean, and N. Kondo, eds., Air Pollution and Plant Biotech-
nology, Prospects for Phytomonitoring and Phytoremediation, Springer Verlag,
Tokyo, 2002, pp. 201219.
170. S. H. Roth, Toxicological and Environmental Impacts of Hydrogen Sulde, in R.
Wang, ed., Signal Transduction and the Gasotransmitters; NO, CO, and H
2
S in Biol-
ogy and Medicine, Humana Press, Totowa, N.J., 2004, pp. 293314.
171. K. W. C. Burton and P. Machmer, in Ref. 131, pp. 336366.
172. H. J. Moeckel, Fresenius Z. Anal. Chem. 318, 116 (1984).
173. P. Mittler, K. M. T. Yamada, G. Winnewisser, and M. Birk, J. Mol. Spectrosc. 164,
390 (1994).
174. H. F. Meissner, E. R. Conway, and H. S. Mickley, Ind. Eng. Chem. 48, 1347 (1956).
175. E. Muller and J. B. Hyne, Can. J. Chem. 46, 2341 (1968).
176. J. Hyne, Sulphur 289, 47 (2003).
177. U.S. Pat. 5,188,179 (Feb. 23, 1993), R. J. Gay, C. C. Gay, V. M. Matthews, F. E. M.
Gay, and V. Chase.
178. J. B. Hyne, Chem. Can. 26 (May 1978).
179. T. H. Ledford, Anal. Chem. 53, 908 (1981).
180. Sulfur Chlorides, Bulletin B-11317-75, Stauffer Chemical Co., Industrial Chemical
Division, Westport, Conn., 1975.
181. Gmelins Handbuch der Anorganischen Chemie, Vol. 9, Pt. B(3), Verlag Chemie,
Weinheim/Bergstrasse, 1963, pp. 17481790.
182. G. A. Takacs, J. Chem. Eng. Data 23, 174 (1978).
183. K. C. Mills, Thermodynamic Data for Inorganic Sulphides, Selenides, and Tellur-
ides, Butterworths, Ltd., London.
184. Sulfur Products Handbook on Sulfur Monochloride and Sulfur Chloride, Bulletin
SPE-SUL-HB 10/9, Oxychem Basic Chemicals Group, Occidental Chemical Corp.,
Dallas, Tex., 1993, p. 3.
185. L. A. Wiles and Z. S. Ariyan, Chem. Ind. (London) 2102 (Dec. 22, 1962).
186. M. Muhlstadt and D. Martinetz, Z. Chem. 14, 297 (1974).
187. G. A. Tolstikov, R. G. Kantyukova, L. V. Spirkhin, L. M. Khalilov, and A. A. Pana-
senko, Zh. Org. Khim. 19, 48 (1983).
188. U.S. Pat. 4,594,274 (1990), E. F. Zaweski and J. G. Jolly.
189. U.S. Pat. 4,966,720 (Oct. 30, 1990), D. J. DeGonia and P. G. Grifn (to Ethyl Petro-
leum Additives, Inc.).
190. W. Hofmann, Vulcanization and Vulcanizing Agents, Palmerton Publishing Co.,
New York, 1965, p. 79.
191. S. M. Erhan and R. Kleiman, J. Am. Oil Chem. Soc. 67, 670 (1990).
192. P. V. Zamotaev, O. P. Mityukhin, and A. A. Usenko, Vysokomol. Soedin., Ser. B
34(6), 18 (1992).
193. Jpn. Kokai Tokkyo Koho JP 5918740A2 (Jan. 31, 1984) (to Sumitomo Chem. Co.
Ltd.).
194. Sumitomo Chem. Co. Ltd., Jpn. Kokai Tokkyo Koho JP 5918729A2 (Jan. 31, 1984);
Chem. Abstr. 100, 193369.
195. JP 04317401 A2 (Nov. 9, 1992), Y. Ida, K. Hamada, H. Kodu, and K. Kato.
196. U.S. Pat. 3,884,985 (May 20, 1975), K. P. Hoffman (to Stauffer Chemical Co.).
66 SULFUR COMPOUNDS Vol. 23
197. U.S. Pats. 3,919,171 (Nov. 11, 1975) and 3,992,362 (Nov. 10, 1976), L. M. Martin (to
Pennwalt Corp., now Elf Atochem NA).
198. U.S. Pats. 5,925,424 (July 20, 1999), 6,303,746 (Oct. 16, 2001) and 6,312,774 (Nov. 6,
2001), J. C. Goswami, J.-L. Lin, and A. K. Doyle (to Akzo Nobel).
199. J. Goswami, A. Abramson, R. Buff, D. Nicholas, and T. Schultz, Update on Lab and
Field Test Results for Polymeric Alkylphenol Polysulde Treated Wood, paper at In-
ternational Research Group on Wood Preservation, 33rd Annual Meeting, Cardiff,
Wales, 2002, published by IRG Secretariat, Stockholm, Sweden.
200. E. R. Braithwaite, ed., Lubrication and Lubricants, Elsevier Publishing Co., New
York, 1967.
201. U.S. Pat. 2,708,199(May10, 1955), H. H. Eby(toContinental Oil Co.); U.S. Pat. 3,346,549
(Oct. 10, 1967), J. F. Ford and E. S. Forbes (to British Petroleum Co., Ltd.); U.S. Pat.
3,471,404 (Oct. 7, 1969), H. Myers (to Mobil Oil Corp.); U.S. Pat. 4,204,969 (May 27,
1980), A. G. Papay and J. P. OBrien (to Edwin Cooper, Inc.); U.S. Pat. 4,225,488 (Sept.
30, 1980), A. G. HorodyskyandP. S. Landis (to Mobil Oil Corp.); U.S. Pat. 4,240,958(Dec.
23, 1980), M. Braid (to Mobil Oil Corp.) are representative patents.
202. N. I. Sax and R. J. Lewis, Sr., eds., Danger. Prop. Ind. Mater. Rep. 5(6), 90 (1985).
203. Disulfur dichloride. Health-based Reassessment of Administrative Occupational Ex-
posure Limits, No. 2000/15OSH/119, The Hague, June 8, 2004; http://www.gr.nl/
pdf.php?ID=571 - Supplemental Result.
204. American Conference of Government Industrial Hygienists (ACGIH). 2001. Sulfur
Monochloride. Documentation of the Threshold Limit Values and Biological Expo-
sure Indices. ACGIH, Cincinnati, Ohio, 7th ed.
205. NIOSH Pocket Guide to Chemical Hazards, January 2003.
206. J. N. Ruth, Am. Ind. Hyg. Assoc. J. 46(A): 142 (1986).
207. Sulfur Dichloride, Product Safety Information Data Sheet, Stauffer Chemical Co.,
Industrial Chemical Division, Westport, Conn., 1973.
208. Chem. Mark. Rep. 245(16), 19 (Apr. 18, 1994).
209. E. J. Corey and E. Block, J. Org. Chem. 31, 1663 (1966); E. D. Weil, K. S. Smith, and R.
Gruber, J. Org. Chem. 31, 1669 (1966); F. Lautenschlaeger, J. Org. Chem. 31, 1679
(1966).
210. F. Lautenschlaeger, in Ref. 118, pp. 7381.
211. A. V. Fokin, A. I. Rapkin, and V. I. Matveenko, Izv. Akad. Nauk. SSSR, Ser. Khim. 6,
1455 (1985).
212. U.S. Pat. 3,219,413 (Nov. 23, 1965), K. E. Kunkel and D. S. Rosenberg (to Hooker
Chemical Corp.).
213. R. J. Rosser and F. R. Whitt, J. Appl. Chem. 10, 229 (1960).
214. U.S. Pats. 3,071,441 and 3,071,442 (Jan. 1, 1963), J. H. Schmadebeck (to Hooker
Chemical Corp.).
215. J. C. Caporossi, Chem. Eng. News 66(32), 2 (1988).
216. Eur. Pat. Appl. EP 311450A2 (Apr. 12, 1989), D. J. Martella and J. J. Jaruzelski.
217. Y. Ohshiro and M. Komatsu, Kagaka Zokan (Kyoto) 115, 33 (1988).
218. Thionyl Chloride, Product Information Bulletin, Bayer Corp., Inorganic Chemicals
Division, Pittsburgh, Pa., 1995.
219. Ref. 181, pp. 17911802.
220. L. F. Fieser and M. Fieser, Reagents for Organic Synthesis, John Wiley & Sons, Inc.,
New York, 1967, pp. 11581163.
221. M. Davis, H. Skuta, and A. J. Krusback, in N. Kharasch, ed., Mechanisms of Reac-
tions of Sulfur Compounds, Vol. 5, Gordon & Breach, Ltd., London, 1970, p. 1.
222. F. J. Dinan and J. F. Bieron, A Survey of Reactions of Thionyl Chloride, Sulfuryl
Chloride, and Sulfur Chlorides, Occidental Chemical Corp., Niagara Falls, N.Y.,
1990.
Vol. 23 SULFUR COMPOUNDS 67
223. S. S. Pizey, Synthetic Reagents, Vol. 1, John Wiley & Sons, Inc., New York, 1974, pp.
321357.
224. T. G. Squires, W. W. Schmidt, and C. S. McCandlish, Jr., J. Org. Chem. 40, 134
(1975).
225. PCT Pat. WO 03091199 (publ. Nov. 6, 2003), H. Buschmann, W. Hell, and M. Kegel
(to Gruenenthal GmbH).
226. U.S. Pat. 2,362,057 (Nov. 7, 1944), J. P. Edwards (to Hooker Electrochemical Co.).
227. U.S. Pat. 2,431,823 (Dec. 2, 1947), A. Pechukas (to Pittsburgh Plate Glass Co.).
228. Ger. Pat. 939,571 (Feb. 23, 1956), H. Jonas and P. Lueg (to Farbenfabriken Bayer A-G).
229. U.S. Pat. 5,498,400 (Mar. 12, 1996), J. E. Hill (to Great Lakes Chemical).
230. U.S. Pat. 3,156,529 (Nov. 10, 1964), D. S. Rosenberg and H. Flaxman (to Hooker
Chemical Corp.).
231. U.S. Pat. 3,155,457 (Nov. 3, 1964), K. E. Kunkel (to Hooker Chemical Corp.).
232. W. Czerwinski and W. Gromotowicz, J. Chromatogr. 520, 163 (1990).
233. S. Konichezky, A. Schnattner, T. Ezri, P. Bokenboim, and D. Geva, Chest 104(3), 971
(1993).
234. Registry of Toxic Effects of Chemical Substances, National Institute for Occupational
Safety and Health, Washington, D.C., Issue 95-1, Feb. 1995; CD-ROM U.S. database
provided by Canadian Centre for Occupational Health and Safety, Ottawa.
235. G. Eichinger, J. Power Sources 43(13), 259 (1993).
236. A. M. Ducatman, B. S. Ducatman, and J. A. Barnes, J. Occup. Med. 30(4), 309
(1988).
237. U.S. Pat. 4,229,565 (Oct. 21, 1980), H. C. Gardner and M. Matzner (to Union Carbide
Corp.).
238. Brit. Pat. Appl. 2,222,827 (Mar. 21, 1990), R. A. Khan, G. H. Sankey, P. J. Simpson,
and N. M. Vernon (to Tate and Lyle PLC).
239. U.S. Pat. 4,977,254 (Dec. 11, 1990), N. J. Homer, G. Jackson, G. H. Sankey, and P. J.
Simpson (to Tate and Lyle PLC).
240. U.S. Pat. 4,826,962 (May 2, 1989), E. B. Rathbone, K. S. Mufti, R. A. Khan, P. S. J.
Cheetham, A. J. Hacking, and J. S. Dordick (to Tate & Lyle).
241. U.S. Pat. 3,272,854 (Sept. 13, 1966), R. A. Covey, A. E. Smith, and W. L. Hubbard
(to Uniroyal Corp.).
242. U.S. Pat. 4,172,852 (Oct. 30, 1979), W. F. Ark, J. H. Kawakami, and U. A. Steiner
(to Union Carbide Corp.).
243. C. R. Schlaikjer, J. Power Sources 26(12), 161 (1989).
244. G. E. Blomgren, J. Power Sources 26(12), 51 (1989).
245. S. Jacobs, Electronic Prod. 45(7), 24 (2002).
246. S. Jacobs, Machine Design 75(5), 72 (2003).
247. S. Jacobs, Sensors 21(3), 42 (2004).
248. Sulfuryl Chloride, data bulletin, Occidental Chemical Corp., Basic Chemicals Group,
Dallas, Tex., 1994.
249. Ref. 181, pp. 18021821.
250. I. Tabushi and H. Kitaguchi, in J. S. Pizey, ed., Synthetic Reagents, Vol. 4, Ellis Hor-
wood, distributed by John Wiley & Sons, Inc., Chichester, U.K., 1981, pp. 336396.
251. Ref. 220, pp. 11281131.
252. R. Stroh and W. Hahn, in Ref. 143, Vol. 5/3, pp. 873890.
253. U.S. Pat. 3,399,214 (Aug. 27, 1968), M. Kulka, D. S. Thiara, and W. A. Harrison (to
Uniroyal, Inc.).
254. T. F. Kozlova, G. B. Shaklova, V. F. Belugin, V. G. Zhelonkin, and N. V. Sedov, Sov.
Chem. Ind. 6, 394 (1971).
255. D. Masilamani and M. M. Rogic, J. Org. Chem. 46, 4484 (1981).
68 SULFUR COMPOUNDS Vol. 23
256. U.S. Pat. 4,871,815 (Oct. 3, 1989), T. Nakagawa, M. Narui, and Y. Sakanaka (to Toyo
Soda Manufacturing Co., Ltd.).
257. U.S. Pat. 4,663,396 (May 5, 1987), T. Nakagawa, M. Narui, and Y. Sakanaka (to
Toyo Soda Manufacturing Co., Ltd.).
258. U.S. Pat. 4,145,491 (Mar. 9, 1979), D. J. Ryan (to E. I. du Pont de Nemours &Co., Inc.).
259. S. Mukhopadhyay, M. Zerella, A. T. Bell, R. V. Srinivas, and G. S. Smith, Chem.
Commun. 4, 472 (2004).
260. U.S. Pat. 4,345,097 (Aug. 17, 1982), K. J. Howard and A. E. Sidwell (to Vertac Che-
mical Corp.).
261. B. W. Satterley, M. C. Hausladen, and C. R. F. Lund, Zeolites 19, 434 (1997).
262. U.S. Pat. 4,902,393 (Feb. 20, 1990), D. J. Muller (to Hu ls AG).
263. U.S. Pat. Appl. 2002/0017000 (Feb. 14, 2002), U. Vogt (to Bayer).
264. H. W. Roesky, Angew. Chem. Int. Ed. Engl. 18, 91 (1979).
265. M. Becke-Goehring, in Gmelins Handbuch der Anorganischen Chemie, 8th ed., Vol.
32, Part 1, Springer-Verlag, Berlin, 1977.
266. M. M. Labes, P. Love, and L. F. Nichols, Chem. Rev. 79, 1 (1979).
267. M. J. Cohen and co-workers, J. Am. Chem. Soc. 98, 3844 (1976).
268. A. J. Banister and I. B. Gorrell, Adv. Mater. 10(17), 1415 (1999).
269. P. W. Schenk and R. Steudel, in Ref. 131, pp. 369418.
270. R. Steudel, Phosphorus Sulfur 23(13), 33 (1985).
271. P. W. Schenk and R. Steudel, Angew. Chem. Int. Ed. Engl. 4, 402 (1965).
272. C. L. Yaws, K. Y. Li, and C. H. Kuo, Chem. Eng. 85 (July 8, 1974).
273. N. B. Vargaftik, Tables on the Thermophysical Properties of Liquids and Gases,
Halsted Press, a division of John Wiley & Sons, Inc., New York, 1975, p. 503.
274. Ref. 181, pp. 11311293.
275. D. F. Burow, in J. J. Lagowski, ed., Chemistry of Nonaqueous Solvents, Vol. 3, Aca-
demic Press, New York, 1970, pp. 137185.
276. Y. Xu, R. P. Schutte, and L. G. Hepler, Can. J. Chem. Eng. 70, 569 (1992).
277. G. H. Ha rtel, J. Chem. Eng. Data 30, 57 (1985).
278. L. F. Audrieth, Liquid Sulfur DioxideA Novel Reaction Medium, republished by
Rhone-Poulenc Basic Chemicals Co., Shelton, Conn., ~19551965.
279. Anon., Sulphur 29 (Mar.Apr. 1995).
280. G. N. Brown, S. L. Torrence, A. J. Repik, J. L. Stryker, and F. J. Ball, Sulfur Dioxide
Processing, reprint manual published by American Institute of Chemical Engineer-
ing, New York, 1975.
281. E. Altwicker, Adv. Environ. Sci. Eng. 3, 80 (1980).
282. J. O. Nriagu, ed., Sulfur in the Environment, John Wiley & Sons, Inc., New York,
1978.
283. J. G. Calvert, F. Su, J. W. Bottenheim, and O. P. Strausz, Atmos. Environ. 12, 197
(1978).
284. L. R. Martin and T. W. Good, Atmos. Environ. 25A(10), 2395 (1991).
285. W. Pasiuk-Bronikowska, Chem. Eng. Sci. 44(4), 915 (1989).
286. A. Saleem, K. E. Janssen, and P. A. Treland, Sulphur 230, 39 (Jan.Feb. 1994).
287. J. B. Pfeiffer, ed., Sulfur Removal and Recovery, Advances in Chemistry Series 139,
American Chemical Society, Washington, D.C., 1975.
288. J. Sarlis and D. Berk, Ind. Eng. Chem. Res. 27, 1951 (1988).
289. S. C. Paik and J. S. Chung, Appl. Catal. B 5(3), 233 (1995).
290. C. D. Swaim, Jr., in Ref. 227, pp. 111119.
291. J. M. Henderson and J. B. Pfeiffer, in Ref. 287, pp. 3547.
292. W. D. Hunter, Jr., J. C. Fedoruk, A. W. Michener, and J. E. Harris, in Ref. 287, pp.
2334.
293. P. Steiner, H. Juntgen, and K. Knoblauch, in Ref. 287, pp. 180191.
Vol. 23 SULFUR COMPOUNDS 69
294. J. Happel, M. Hnatow, L. Bajars, and M. Kundrath, Ind. Eng. Chem. Prod. Res. Dev.
14, 155 (1975).
295. Anon., Sulphur 153, 41 (Mar.Apr. 1981).
296. R. B. Engdahl and H. S. Rosenberg, Chemtech 118 (Feb. 1978).
297. C. G. Cornell and D. A. Dahlstrom, Chem. Eng. Prog. 69(12), 47 (1973).
298. W. J. Osborne and C. B. Earl, in Ref. 287, pp. 158163.
299. L. Korosy, H. L. Gewanter, F. S. Chalmers, and S. Vasan, in Ref. 287, pp. 192211.
300. U.S. Pat. 3,911,093 (Oct. 7, 1975), F. G. Sherif, J. S. Hayford, and J. E. Blanch (to
Stauffer Chemical Co.).
301. J. P. Hayford, L. P. VanBrocklin, and M. A. Kuck, Chem. Eng. Prog. 69(12), 54
(1973).
302. Sulphur 232, 59 (MayJune 1994).
303. Ref. 287, pp. 14, 16, 108110.
304. Ref. 25, pp. 267278.
305. N. W. Frank, Rad. Phys. Chem. 40(4), 267 (1992).
306. L. C. Schroeter, Sulfur Dioxide, Pergamon Press, New York, 1966.
307. F. Asinger, ParafnsChemistry and Technology, Pergamon Press, Oxford, U.K.,
1968, pp. 645668, 483571.
308. D. Estel, K. Mateew, W. Pritzkow, W. Schmidt-Renner, J. Prakt. Chem. 323, 262
(1981).
309. E. M. Fettes and F. O. Davis, in N. G. Gaylord, ed., Polyethers, III, Polyalkylene Sul-
des and Other Polythioethers, Interscience Publishers, New York, 1962, pp. 225
270.
310. C. S. Marvel and E. D. Weil, J. Am. Chem. Soc. 76, 61 (1954), and references cited
therein.
311. M. J. Bowden and L. F. Thompson, in Polymeric MaterialsScience and Engineer-
ing, Proceedings of the ACS Division of Polymeric Materials Science and Engineer-
ing, Vol. 68, ACS, Washington, D.C., 1993, p. 46.
312. H. Ito and co-workers, J. Electrochem. Soc. 135(6), 1504 (1988).
313. S. R. Sandler and W. Karo, Organic Functional Group Preparations, Vol. I, Aca-
demic Press, Inc., New York, 1983, pp. 632633.
314. B. Deguin and P. Vogel, J. Am. Chem. Soc. 114, 9210 (1992).
315. U. H. Sander, H. Fischer, U. Rothe, and R. Kola, in A. I. More, ed., Sulfur, Sulfur
Dioxide and Sulfuric Acid, English ed., British Sulphur Corp., Ltd., London, 1984.
316. Anon., Sulphur 226, 19 (May 1992).
317. A. H. Lefebvre, X. F. Wang, and C. A. Martin, J. Propulsion 4(4), 293 (1988).
318. R. L. Schendel, Oil Gas J. 91(39), 63 (1993).
319. Available at http://www.innovationalberta.com/article.php?articleid=29.
320. L. Connock, Sulphur 267, 32 (2000).
321. Anon., Sulphur 276, 45 (2002).
322. U.S. Pat. 3,632,312 (Jan. 4, 1972), W. W. Jukkola (to Dorr-Oliver, Inc.).
323. C. D. Jentz, Pulp Paper Can. 101 (1941).
324. A. Urbanek and M. Burgiell, Proceedings of the 5th International Sulphur Confer-
ence, Nov. 1981, British Sulphur Corp., Ltd., London, 1982.
325. Process for Production of Liquid Sulfur Dioxide, Bulletin of Stauffer Chemical Co.,
Licensing Administrator, Westport, Conn., 1970 (successor: Rhone-Poulenc Licen-
sing Dept., Shelton, Conn.).
326. U.S. Pat. 6,342,169 (Jan. 29, 2002), L. E. Hakka and P. J. Parisi (to Cansolv Tech-
nologies, Inc.).
327. Anon., Sulphur 293, 37 (2004).
328. U.S. Pat. 4,177,248 (Dec. 4, 1979), W. T. Richard (to Stauffer Chemical Co.).
329. Anon., Sulphur 270, 75 (2000).
70 SULFUR COMPOUNDS Vol. 23
330. N. E. Hamner, ed., Corrosion Data Survey, 5th ed., National Association of Corrosion
Engineers, Houston, Tex., 1975.
331. Anon., Mater. Eng. 14 (May 1979).
332. S. L. Sakol and R. A. Schwartz, Sulfur Dioxide Processing, reprint manual, Ameri-
can Institute of Chemical Engineers, New York, 1975.
333. L. Igetoft, Ind. Eng. Chem. Prod. Res. Dev. 24, 375 (1985).
334. M. J. Justo and M. G. S. Ferreira, Corrosion Science 29(1112), 1353 (1989); 34(4),
533 (1993).
335. F. Schuster, M. M. Reddy, and S. I. Sherwood, Mater. Perf. 33(1), 76 (1994).
336. M. Kirschner, Chem. Market Rep. 265(2), 27 (2004).
337. Anon., Chemical Prole on Sulfur Dioxide, Chem. Market Rep. 33 (Aug. 22, 1994).
338. R. A. Belbutowski, paper at Sulfur Markets Symposium, Sulfur Institute, Washing-
ton, D.C., Mar. 24, 1994.
339. NIOSH Manual of Analytical Methods, Method No. S308, Vol. 2, U.S. Dept. of
Health and Human Services, Public Health Service, Washington, D.C., 1977.
340. NIOSH Manual of Analytical Methods, Method No. P & CAM 160, Vol. 1, U.S. Dept.
of Health, Education, and Welfare, Public Health Service, Washington, D.C., 1977.
341. Anon., Sulphur 131, 52 (JulyAug. 1977); J. R. Donovan, E. D. Kennedy, D. R.
McAlister, and R. M. Smith, Chem. Eng. Prog. 89 (June 1977).
342. R. S. Saltzman, Challenges in Stack Sulfur Emissions Measurements, paper at 30th
Annual Petroleum Mechanical Engineering Conference, Tulsa, Okla., Sept. 2125,
1975.
343. C. J. Lang, R. S. Saltzman, and G. G. DeHaas, TAPPI Environmental Conference,
1975 preprints, Technical Association of the Pulp and Paper Industry, Atlanta,
Ga., May 1975, pp. 129145.
344. D. G. Barrett and J. R. Small, Chem. Eng. Prog. 69(12), 35 (1973).
345. Food Chemicals Codex, 3rd ed., National Academy of Sciences, Washington, D.C.,
1993.
346. F. D. Snell and L. S. Ettre, Encyclopedia of Industrial Chemical Analysis, Vol. 18,
John Wiley & Sons, Inc., New York, 1973, pp. 408ff.
347. J. M. Roberts, Chemtracts: Anal. Phys. Chem. 1(5), 328 (1989).
348. D. W. T. Grifth and G. Schuster, J. Atmos. Chem. 5(1), 59 (1987).
349. B. S. M. Kumar and N. Balasubramanian, J. AOAC Int. 75(6), 1006 (1992).
350. J. S. Symanski and S. Bruckenstein, Anal. Chem. 58(8), 1771 (1986).
351. F. L. Eisele and H. Berresheim, Anal. Chem. 64, 283 (1992).
352. J. R. Cochrane, A. W. Ferguson, and D. K. Harris, Chem. Eng. 4 (June 1993).
353. Anon., Sulphur 228, 37 (Sept. Oct. 1993).
354. D. E. Schorran, C. Fought, D. F. Miller, W. G. Coulombe, R. E. Keislar, R. Benner,
and D. Stedman, Environ. Sci. Technol. 28(7), 1307 (1994).
355. J. E. Jones, Poll. Eng. 38 (June 1985).
356. W. Freitag, in J. Jahnke, ed., An Operators Guide to Eliminating Bias in CEM Sys-
tems, U.S. EPA Contract Report 68-D2-0168, Washington, D.C., Nov. 1994, pp. 312.
357. R. Von Burg R, J. Appl. Toxicol. 16, 365 (1995).
358. ToxFAQs for Sulfur Dioxide, Agency for Toxic Substances and Disease Registry.
Available at http://www.atsdr.cdc.gov/tfacts116.html.
359. Hazardous Substance Data Bank. Database of the National Library of Medicines
Toxnet system. Aug 2005.
360. Agency for Toxic Substances and Disease Registry (ATSDR). 1998. Toxicological Pro-
le for Sulfur Dioxide.
361. American Conference of Government Industrial Hygienists (ACGIH). 2001. Sulfur
Dioxide. Documentation of the Threshold Limit Values and Biological Exposure In-
dices. ACGIH, Cincinnati, Ohio, 7th ed.
Vol. 23 SULFUR COMPOUNDS 71
362. U. Heber and K. Huve, Inter. Rev. Cytol.Sur. Cell Biol. 177, 255 (1998).
363. P. J. Wallace and T. M. Gerlach, Science 265, 497 (1994).
364. D. Moller, Atmos. Environ. 18(1), 29 (1984).
365. P. M. Irving, ed., U.S. National Acid Precipitation Assessment Program (NAPAP),
Acidic Deposition: State of Science and Technology, Vols. IIV, Integrated Assess-
ment Report, U.S. National Acid Precipitation Assessment Program, National Acad-
emy of Sciences, Supt. Documents, Government Printing Ofce, Washington, D.C.,
1991.
366. L. F. Pitelka, EPRI J. 50 (Apr. May 1987).
367. B. Rosenbaum, T. C. Strickland, and M. K. McDowell, Water, Air Soil Poll. 74(34),
307 (1994).
368. J. J. Mackenzie and M. T. El-Ashry, Technol. Rev. 92(3), 64 (1989).
369. M. A. Tabatatai, Sulfur in Agriculture, American Society of Agronomy, Madison,
Wisc., 1986.
370. W. E. Winner, H. A. Mooney, and R. A. Goldstein, eds., Sulfur Dioxide and Vegeta-
tion: Physiology, Ecology and Policy Issues, Stanford University Press, Palo Alto,
Calif., 1985.
371. C. M. Okpodu, R. G. Alscher, E. A. Grabau, and C. L. Cramer, J. Plant Physiol. 148,
309 (1996).
372. C. M. Burt and C. Hash, Proceedings of the 3rd International Drip/Trickle Irrigation
Congress, Nov. 1985, ASAE, St. Joseph, Mich., 1985.
373. J. M. Mee, M. Jahangir, M. Al-Mishal, I. Faruq, and S. Al-Salem, Environ. Chem.
25(1), 28 (1985).
374. J. Makansi, Power, 23 (Mar. 1993).
375. T. J. Manetsch, IEEE Trans. Power Sys. 9, 1921 (1994).
376. L. R. Roberts, K. N. T. Horne, A. Mann, and S. Keil, Chem. Eng. Prog. 22 (Oct. 1985).
377. K. Ravi, W. Srivastava, and W. Jozewicz, Environ. Prog. 20(4), 219 (2001).
378. J. E. Johnsson and P. Glarborg, Sulphur chemistry in combustion II. Flue gas desul-
phurization chapter in Pollutants from CombustionFormation and Impact on At-
mospheric Chemistry Proceedings, C. Vovelle, ed., Kluwer Academic Publishers,
Dordrecht, NL (1999).
379. Hot gas cleaning. Available at http://www.netl.doe.gov/publications/proceedings/02/
GasCleaning/gas_clean02.html.
380. J. W. Gerrie, in Proceedings of Canada Pulp and Paper Association 61st Annual
Meeting, Canada Pulp and Paper Association, Montreal, Quebec, 1975, pp. T251
T254.
381. B. L. Wedzicha, ed., Chemistry of Sulfur Dioxide in Foods, Elsevier Science, Inc.,
New York, 1984.
382. B. L. Wedzicha, Chem. Br. 27(11), 1030 (1991).
383. R. A. Scanlon, CRC Crit. Rev. Food Technol. 5, 357 (1975).
384. W. R. Junk and H. M. Pancoast, Handbook of Sugars, AVI Publishing Co., Inc.,
Westport, Conn., 1973, p. 110ff.
385. Dechlorination Using Sulfur Products, Technical Information Bulletin TIR-17,
Rhone-Poulenc Basic Chemicals Co., Shelton, Conn., 1992.
386. Sodium Sulte Solution 25-9 in Oxygen Scavenging, Technical Information Bulletin
TIR-13, Rhone-Poulenc Basic Chemicals Co., Shelton, Conn., 1991.
387. R. L. Miron, Mater. Perform. 45 (June 1981).
388. A. N. Yermakov and A. P. Purmal, Prog. React. Kinet. Mech. 28(3), 189 (2003).
389. A. N. Yermakov, G. A. Poskrebyshev, and A. P. Purmal, Prog. React. Kinet. 22(2),
141 (1997).
390. P. J. Bailes, C. Hanson, and M. A. Hughes, Chem. Eng. 83(10), 115 (1976).
391. Brit. Pat. 1,186,126 (Apr. 2, 1970), J. M. Maselli (to W. R. Grace & Co.).
72 SULFUR COMPOUNDS Vol. 23
392. C. N. Sattereld, Heterogeneous Catalysis in Practice, McGraw-Hill Book Co., New
York, 1980, p. 203.
393. F. Habashi, Sulphur Inst. J. 12(34), 15 (1976).
394. Treating Irrigated Arid-Land Soils with Acid-Forming Sulphur Compounds, Tech-
nical Bulletin No. 24, The Sulphur Institute, Washington, D.C., 1979.
395. L. R. Grass and A. J. MacKenzie, Sulphur Inst. J. 6(1), 8 (1970).
396. T. Niichiro, Synthesis 12, 639 (1971).
397. Gmelins Handbuch der Anorganischen Chemie, 8th ed., System No. 9, Pt. B2, Verlag
Chemie, Weinheim/Bergstrasse, Germany, 1960, pp. 373613.
398. Sodium Sulte, product brochure, General Chemical Co., Claymont, Del., 1993.
399. Sodium Sulte Anhydrous, Technical Grade and High Purity Grade, data sheets,
Solvay Minerals, Inc., Houston, Tex., 1995.
400. Sodium Sulte, Commercial Anhydrous, data sheet, Indspec Chemical Corp., Pitts-
burgh, Pa., 1992.
401. Sodium Sulte, product data sheet and product safety information sheets, Rhone-
Poulenc Basic Chemicals Co., Shelton, Conn., 1992.
402. E. A. P. Devuyst, V. A. Ettel, and M. A. Mosoiu, Chemtech 426 (July 1979).
403. Ger. Pat. 2,940,697 (Feb. 5, 1981), A. Metzger and G. Muenster (to Hoechst A-G).
404. U.S. Pat. 4,003,985 (Jan. 18, 1977), R. J. Hoffman, S. L. Bean, P. Seeling, and J. W.
Swaine, Jr. (to Allied Chemical Corp.).
405. Chem. Mark. Rep. 9 (Apr. 12, 1993).
406. Anon., Chem. Market Rep. 267(7), 18 (2005); C. R. Warner, G. W. Diachenko, and C.
J. Bailey, Food Testing Anal., Sept., 814 (2000).
407. Sulfate, Sulte, and Sulde, in Handbook of Water Analysis, L. M. L. Nollet, ed.,
Marcel Dekker, New York, 2000, Chapt. 11.
408. M. J. Kocurek, O. V. Ingruber, and A. Wong, Sulte Science and Technology, Vols.
14, 3rd ed., Technical Association of the Pulp and Paper Industry, Atlanta, Ga.,
1985.
409. E. C. Xu, TAPPI J. 2(8), 13 (2003).
410. H. Sixta, Inter. Papierwirtschaft IPW 5, 239 (1998).
411. Bleach Plant Vent Gas Scrubbing, Application Bulletin SENOCHLOR-T, Southern
Ionics, Inc., West Point, Miss. (1997).
412. Sodium Metabisulte, Solid SO
2
, Technical Information sheet, Rhone-Poulenc Basic
Chemicals Co., Shelton, Conn., 1991.
413. Can. Pat. 3,057,418 (July 23, 1992), W. H. Bortle, S. L. Bean, and M. D. Dulik (to
General Chemical Co.).
414. U.S. Pat. 4,844,880 (July 4, 1989), S. L. Bean, M. D. Dulik, and R. J. Wilson (to HMC
Patents Holding Co., Inc.).
415. Sodium Bisulte, CHRIS Hazardous Chemical Data, Coast Guard, U.S. Dept. of
Transportation, Washington, D.C., data sheet revised 1978.
416. Treatment of Chromium Waste Liquors, General Chemical Corp., Claymont, Del.,
1989.
417. J. Litt, Metal Finish. 52, 61 (Nov. 1971).
418. U.S. Pat. 6,126,910 (Oct. 3, 2000), J. H. Wilhelm, R. E. Moser, and F. B. Meserole.
419. D. Lyons and G. Nickless, in Ref. 84, pp. 199239.
420. L. W. Codd and co-workers, eds., Chemical Technology, An Encyclopedic Treatment,
Vol. 1, Barnes & Noble Books, New York, 1968, p. 461.
421. J. G. deVries and R. M. Kellogg, J. Org. Chem. 45, 4126 (1980).
422. G. Valensi, Cent. Belge. Etude Corros. Rapp. Tech. 121, 207/1 (1973).
423. A. Teder, Acta Chem. Scand. 27, 705 (1973).
Vol. 23 SULFUR COMPOUNDS 73
424. A. Janson and F. Scholtz, in W. Forst, ed., Ullmanns Encyklopadie Technischen Che-
mie, 3rd ed., Vol. 15, Urban & Schwartzenberg, Mu nchen-Berlin, Germany, 1964,
pp. 480488.
425. U.S. Pat. 3,523,069 (Jan. 29, 1969), C. W. Oloman (to British Columbia Research
Council).
426. M. S. Spencer, P. J. Carnell, and W. J. Skinner, Ind. Eng. Chem. Proc. Res. Dev. 8,
184 (1969).
427. C. Oloman, J. Electrochem. Soc. 117, 1604 (1970).
428. Ger. Pat. 2,748,935 (May 3, 1979), W. Ostertag, G. Ertl, G. Wunsch, V. Kiener, E.
Voelkl, and S. Schreiner (to BASF A-G).
429. G. Ertl, V. Kiener, W. Ostertag, G. Wunsch, and K. Bittler, Angew. Chem. 91, 333
(1979).
430. U.S. Pat. 3,927,190 (Dec. 16, 1975), T. Kato, H. Okazaki, A. Sugio, and Y. Yushu-
kawa (to Mitsubishi Gas Chemical Co., Ltd.).
431. Brit. Pat. 1,145,824 (Apr. 21, 1965) (to Electric Reduction Co. of Canada, Ltd.).
432. U.S. Pat. 4,992,147 (Feb. 12, 1991), R. E. Bolick, II, D. W. Cawleld, and J. M.
French (to Olin Corp.).
433. U.S. Pat. 5,336,479 (Aug. 9, 1994), D. C. Munroe (to Morton International, Inc.).
434. D. Munroe, O. Bhatia, J. Westling, M. McCrary, A. Casassa, and S. Masse, Proceed-
ings of the TAPPI 1994 Pulping Conference, Book 1, TAPPI Press, Atlanta, Ga.,
1994, pp. 8386.
435. U.S. Pat. 4,892,636 (Jan. 9, 1990), R. E. Bolick, II, D. W. Cawleld, and K. E. Woo-
dard, Jr. (to Olin Corp.).
436. M. Kirschner, Chem. Market Rep. 263(10), 27 (2003).
437. Chemical Economics Handbook, Stanford Research Institute, Menlo Park, Calif.,
1992, pp. 780.4000 BC.
438. Chem. Market Rep. 49 (Oct. 10, 1994).
439. L. V. Hoff, in J. H. Karchmer, ed., The Analytical Chemistry of Sulfur and its Com-
pounds, Part 1, Interscience, division of John Wiley & Sons, Inc., New York, 1970,
pp. 245247.
440. K. J. Stutts, Anal. Chem. 59, 543 (1987).
441. Organization for Economic Co-Operation and Development (OECD) Screening Infor-
mation 2004. Initial Assessment Prole: Sodium Dithionite. Presented at SIDS In-
itial Assesement Meeting 19. Available at http://cs3-hq.oecd.org/.
442. Anon., Fed. Reg. 6117 (Jan. 25, 1980).
443. J. N. Etters, Am. Dyestuffs Rep. 78, 18 (1989).
444. A. R. Beaudry and N. R. Ducharme, Preprints of Annual Meeting, Technical Section,
Canadian Pulp and Paper Association, Pt. B, Canadian Pulp and Paper Association,
Montreal, 1993, pp. B13B26.
445. R. Barton, C. Tredway, M. Ellis, and E. Sullivan, in R. A. Leask, ed., Pulp and Paper
Manufacture, 3rd ed., Vol. 2, Mechanical Pulping, TAPPI, Atlanta, Ga., and CPPA,
Montreal, Quebec, 1986, Chapt. XIX, pp. 227237.
446. Two-Stage Bleaching with V-BRITE Bleach, and V-BRITE Bleaching Compounds,
Product Application Bulletins 10172 and 10174, Hoechst Celanese Corp., Charlotte,
N.C., 1992.
447. W. C. De Baat, Rec. Trav. Chim. Pays-Bas 45, 237 (1926).
448. R. Pfanstiel, Inorg. Synthesis 2, 170 (1946).
449. G. Brauer, ed., Handbook of Preparative Inorganic Chemistry, 2nd ed., Academic
Press, New York, 1963, pp. 395398.
450. H. C. H. Carpenter, J. Chem. Soc. (Trans.) 81, 1 (1902).
451. W. Y. W. Lew and R. E. Powell, Inorg. Chem. 12(4), 957 (1973).
452. N. Soffer, Analyst 86, 843 (1961).
74 SULFUR COMPOUNDS Vol. 23
453. Jpn. Kokai Tokkyo Koho JP 02052092 (1990), Y. Kimura and T. Ito (to Mitsubishi
Heavy Industries, Ltd.); Chem. Abst. 113: 45767 (1990).
454. U.S. Pat. Appl. 2004/0082489A1 (2004), M. D. Gernon and S. L. Bodar (Atona).
455. A. A. Newman, ed., Chemistry and Biochemistry of Thiocyanic Acid and Its Deriva-
tives, Academic Press, Inc., New York, 1975.
456. Ref. 2, Pt. D5, pp. 148209.
457. Ref. 313, pp. 369376.
458. Ammonium Thiocyanate, Potassium Thiocyanate, and Sodium Thiocyanate, Product
bulletins, Argus Chemical Division, Witco Chemical Co., Marshall, Tex.
459. C. K. Nmai, M. A. Bury, and H. Farzam, Concrete Int. 16(4), 22 (1994).
460. H. Goldwhite, M. S. Gibson, and C. Harris, Tetrahedron 21(10), 2743 (1965).
461. Fr. Pat. 1,409,516 (1965), H. W. Moore, F. F. Rust, and H. S. Klein.
462. M. Asscher and D. Vofsi, J. Chem. Soc. 4962 (1964).
463. I. J. Borowitz, J. Am. Chem. Soc. 86, 1146 (1963).
464. G. Opitz, M. Kleeman, D. Bucher, G. Walz, and R. Rieth, Angew. Chem. 78(11), 604
(1966).
465. E. Block, Reactions of Organosulfur Compounds, Academic Press, Inc., New York,
1978, p. 278.
466. W. E. Truce and C. W. Vriesen, J. Am. Chem. Soc. 75, 5032 (1953).
467. R. H. Wiley and H. Kraus, J. Org. Chem. 22, 994 (1957).
468. J. P. Horwitz, J. Chua, and M. Noel, J. Org. Chem. 29, 2076 (1969).
469. Methane Sulfonyl Chloride (MSC)Properties, Reactions and Applications, Techni-
cal Bulletin S-104, Elf Atochem North America, Philadelphia, Pa.
470. Concerning Methane Sulfonyl Chloride, Technical Bulletin, Elf Atochem North
America, Philadelphia, Pa.
471. Use of Methanesulfonyl Chloride (MSC) in the Synthesis of Chiral Compounds, Tech-
nical Bulletin A-70-11, Elf Atochem North America, Philadelphia, Pa., 1992.
472. U.S. Pat. 2,825,736 (Mar. 4, 1958), A. C. Cope and N. Burg (to Merck and Co.).
473. K. Weinges, Annalen 615, 203 (1958).
474. L. Toldy and I. Fabricius, Chem. Ind. (London) 665 (1957).
475. U.S. Pat. 2,703,808 (Mar. 8, 1955), E. R. Buchman (to Research Corp.).
476. R. F. Schwenker, Jr., and E. Pacsu, Ind. Eng. Chem. 50, 91 (1958).
477. Belg. Pat. 613,335 (Feb. 15, 1962), C. Gyogyszer and V. T. Gyara.
478. J. H. Looker and C. H. Hayes, J. Am. Chem. Soc. 79, 745 (1957).
479. J. H. Looker, C. H. Hayes, and D. N. Thatcher, J. Am. Chem. Soc. 79, 741 (1957).
480. U.S. Pat. 3,072,688 (Jan. 8, 1963), H.-J. E. Hess (to Chas. Pzer & Co.).
481. N. L. Wendler and D. Taub, J. Org. Chem. 25, 1828 (1960).
482. A. G. Kastava, Zhur. Obshchei Khim. 18, 729 (1948).
483. G. J. Grifths and F. E. Previdoli, J. Org. Chem. 58, 6129 (1993).
484. R. P. Glinski, M. S. Khan, and R. L. Kalman, J. Org. Chem. 38, 4299 (1973).
485. Methane Sulfonic Acid (MSA), Properties, Reactions and Applications, Technical
Bulletin PB-70-1A, Elf Atochem North America, Philadelphia, Pa., 1993.
486. D. B. Roitman, J. McAlister, and F. L. Oaks, J. Chem. Eng. Data 39, 56 (1994).
487. Methane Sulfonic Acid for Catalyzed Coatings, Technical Bulletin, Elf Atochem
North America, Philadelphia, Pa., 1993.
488. Preparation of DOP, Technical Bulletin, Elf Atochem North America, Philadelphia,
Pa.
489. U.S. Pat. 3,071,604 (Jan. 1, 1963), A. G. Mohan and W. Christian (to Nopco Chemical
Co.).
490. U.S. Pat. 3,116,336 (Dec. 31, 1963), J. L. Van Winkle (to Shell Development Co.).
491. U.S. Pat. 2,525,942 (Oct. 17, 1950), W. A. Proell (to Standard Oil Co. of Indiana).
Vol. 23 SULFUR COMPOUNDS 75
492. MSA Zinc Plating Process, Technical Bulletin, Elf Atochem North America, Phila-
delphia, Pa.
493. P. D. Lawley, in C. E. Searle, ed., Chemical Carcinogens, ACS Monograph 182,
American Chemical Society, Washington, D.C., 1984.
494. S. R. Sandler, G. T. Carroll, and G. Stringer, Elf Atochem (Now Arkema, Inc.)-
Organic Chemicals Div. Product Bulletin The Chemistry of Methanesulfonamide
(MSAM) & N-Alkyl Methanesulfonamides (R-MSAM) #A-70-23; QC 37 IM 2/95.
495. Atona (now Arkema, Inc.) Product Information: Brief Summary of Reactions
Using Methanesulfonamide, #A-70-20 (2000).
496. U.S. Pat. 5,455,377 (1995), N. Ronchi, E. Pallucca, D. Tarallo, and C. Ornati (to Oxon
Italia S.p.A.).
497. Eur. Pat. 0504,873 A1 (1992), S. Lachhein and K. Dehmer (to Hoechst AG).
498. PCT Pat. Appl. WO 98/25890 (1997), S. Brown, P. James, and D. Brian (to Pzer).
499. U.S. Pat. 4,970,339 (1990), S. R. Sandler, J. S. Perilli, and J. F. Kennoy (to Atochem
North America, Inc.).
500. U.S. Pat. 5,068,427 (1991), S. R. Sandler, S. G. Schon, and D. M. Gardner (to Ato-
chem North America, Inc.).
501. U.S. Pat. 5,599,983 (1997), G. S. Smith, R. Cordova, T. H. Overgard, and M. T.
Budrick.
502. U.S. Pat. 4,285,723 (1981), D. Cartwright, D. J. Collins (to Imperial Chemical Indus-
tries, Ltd.).
EDWARD D. WEIL
Polytechnic University of New York
STANLEY R. SANDLER
Delaware County Community College
MICHAEL GERNON
Arkema Group, Inc.
76 SULFUR COMPOUNDS Vol. 23
FRC
CM SM
PIC
TC
SM
TR
4
5
6
7
2
1
3
TC
FRC
Sulfur feed
30%
Oleum feed
20% Oleum return
Scrubbing
acid in
Scrubbing
acid out
PIC
WC
11
12
13
Product SO
2
10
9
8
2
Fig. 1. Flow diagram of production of sulfur dioxide from oleum: (1) 30% oleum exchan-
ger; (2) SO
3
vaporizer; (3) reactor; (4) coolant surge tank; (5) coolant circulating pump; (6)
coolant exchangers; (7) sludge and acid pump; (8) scrubber; (9) SO
2
cooler; (10) gas clea-
ner; (11) SO
2
compressor; (12) pulsation damper; and (13) SO
2
condenser. CM is the con-
densate; FRC, ow recording controller; PIC, pressure indicating controller; SM, steam;
TC, temperature recorder; and WC, cooling water (325).
Vol. 23 SULFUR COMPOUNDS 77
Table 1. Physical and Thermodynamic Properties of Carbonyl Sulde
Property Value References
mol wt 60.074 14
mp, 8C 138.8 15
bp, 8C 50.2 15
DH fusion, at 134.3 K, kJ/mol
a
4.727 15
DH vaporization, at 222.87 K, kJ/mol
a
18.57 15
density at 220 K, 101.3 kPa(=1 atm), g/cm
3
1.19 15
sp gr, gas at 298 K (air =1) 2.10 15
critical temperature, 8C 105 15
critical pressure, kPa
b
5946 15
critical volume, cm
3
/mol 138 15
triple point, K 134.3 15
DG formation, at 258C, kJ/mol
a
169.3 2
DH formation, at 258C, kJ/mol
a
142.1 2
S formation, at 258C, J/(molK)
a
231.5 2
C
p
, at 258C, J/(molK)
a
41.5 2
autoignition temperature in air, 8C ~250 15
ammability limits in H
2
O-saturated air
at 17.98C, vol%
upper limit 9.6
lower limit 33.2 15
solubility in water at 101.3 kPa(=1 atm), vol%
08C 0.356 15
108C 0.224
208C 0.149
a
To convert J to cal, divide by 4.184.
b
To convert kPa to psi, multiply by 0.145.
78 SULFUR COMPOUNDS Vol. 23
Table 2. Physical and Thermodynamic Properties of Hydrogen Sulde
Property Value References
mol wt 34.08 98
mp, 8C 85.53 99
bp, 8C 60.31 99
DH fusion, kJ/mol
a
2.375 98
DH vaporization, kJ/mol
a
18.67 98
density at 60.318C, kg/m
3
949.6 99
sp gr, gas (air =1) 1.182
b
101
critical temperature, 8C 100.38 102
critical pressure, kPa
c
9006 102
critical density, kg/m
3
346.0 102
DG formation, kJ/mol
a
33.6 14
DH formation, at 258C, kJ/mol
a
20.6 14
S formation, at 258C, J/(molK)
a
205.7 14
C
p
, at 278C, J/(molK)
a
34.2 14
autoignition temperature in air, 8C ~ 260 103
explosive range in air at 208C, vol%
upper limit 46 103
lower limit 4.3
vapor pressure, kPa
c
608C 102.9 99,104
408C 257.9 99
208C 562.0 99
08C 1049 99
208C 1814 99
408C 2937 99
608C 4480 99
solubility in water,
d
g/100 g soln 101
08C 0.710
108C 0.530
208C 0.398
a
To convert J to cal, divide by 4.184.
b
Based on air =79 mol % nitrogen plus 21 mol % oxygen.
c
To convert kPa to psi, multiply by 0.145; to convert kPa to bars, divide by 100.
d
At 101.3 kPa(=1atm) total pressure.
Vol. 23 SULFUR COMPOUNDS 79
Table 3. Oxidation Reactions of Hydrogen Sulde
Oxidizing agent Conditions Sulfur-containing products
O
2
ame SO
2
, some SO
3
ame or furnace, catalyst (Claus process) sulfur
aqueous soln of H
2
S, catalyst sulfur
H
2
O
2
neutral; alkaline solution sulfur; SO
2
3
, SO
2
4
Na
2
O
2
dry, elevated temperature Na
2
S, Na
2
S
x
O
3
aqueous sulfur, H
2
SO
4
SO
2
elevated temperature, catalyst sulfur
aqueous soln sulfur, polythionic acids
H
2
SO
4
concentrated acid sulfur, SO
2
HNO
3
aqueous H
2
SO
4
NO silica gel catalyst sulfur
NO
2
aqueous at pH 57 sulfur, NO
aqueous at pH 89 sulfur, NH
3
Cl
2
gaseous, excess Cl
2
SCl
2
gaseous, excess H
2
S sulfur
aqueous soln, excess Cl
2
H
2
SO
4
I
2
aqueous soln sulfur (quantitative)
Fe
3
aqueous soln sulfur, FeS
Table 4. Effects of Hydrogen Sulde Inhalation on Humans
a
Number of
people
exposed
Concentration,
mg/m
3
Duration of
exposure
Effect
1 17,000 death
1 28005600 <20 min death
10 1400 <1 min unconsciousness, abnormal
(electrocardiogram) ECG;
death of one person
342 14002800 <20 min hospitalization of 320, death
of 22 including 13 in hospital,
residual nervous system
damage in 4
5 1400 instant unconsciousness, death
1 1400 <25 min unconsciousness, low blood
pressure, pulmonary edema,
convulsions, hematuria
4 400760 unconsciousness
1 320 20 min unconsciousness, arm cramps,
low blood pressure
78 2035 burning eyes in 25, headache in
32, loss of appetite in 31,
weight loss in 20, dizziness
in >19
6500 1520 47 h conjunctivitis
population of
Terre Haute,
Indiana
0.00311 intermittent
air pollution
episodes over
a 2-month
period
nausea in 13, headache,
shortness of breath in 4,
sleep disturbance in 5,
throat and eye irritation in 5
a
Ref. 160.
80 SULFUR COMPOUNDS Vol. 23
Table 5. Physical and Thermodynamic Properties of Sulfur Monochloride, S
2
Cl
2
Property Value References
mol wt 135.03 180,181
mp, 8C
commercial 76 180,181
pure 76.1 180,181
bp, 8C 137.8 180,181
specic gravity, 208C 1.68 180,181
refractive index, n
20
D
1.670 180,181
ash point, Cleveland open cup, 8C 130 180,181
vapor pressure, kPa
a
180,181
08C 0.479 180,181
21.18C 1.513 180,181
37.78C 3.5 180,181
solubility in water insoluble 180,181
DH formation, at 258C, kJ/mol
b
liquid 32 182, 183
gas 58 182, 183
molar heat capacity, J/(molK),
b
8C 115 184
specic heat at 258C, J/g
b
0.92 184
heat of hydrolysis, J/mol
b
146.44 184
heat of vaporization, J/mol
b
36,401 184
a
To convert kPa to mmHg, multiply by 7.5.
b
To convert J to cal, divide by 4.184.
Table 6. Physical and Thermodynamic Properties of Thionyl Chloride
Property Value References
mol wt 118.98 218
mp, 8C 104.5 218
bp, 8C 76 218
specic gravity, 258C 1.63 218
molar heat capacity, J/(molK)
a
120.5 218
latent heat of vaporization, kJ/mol
a
31.0 218
viscosity, mPas(=cP)
08C 0.81 218
258C 0.60 218
refractive index, n
20
D
1.517 218
electrical conductivity at 258C, S/cm(=mho/cm) 2 10
6
218
vapor pressure, kPa
b
208C 1.5 219
08C 4.5
58C 5.9
208C 11.6
268C 14.7
DH formation at 258C, kJ/mol
a
liquid 246 14
gas 213 14
DG formation gas, at 258C, kJ/mol
a
198 14
S formation, J/(molK)
a
309 14
C
p
, at 258C J/(molK)
a
liquid 121 14
gas 66.5 14
a
To convert J to cal, divide by 4.184.
b
To convert kPa to mmHg, multiply by 7.5.
Vol. 23 SULFUR COMPOUNDS 81
Table 7. Physical and Thermodynamic Properties of Sulfuryl Chloride
Property Value References
mol wt 134.968 14
mp, last crystal point, 8C 54 248
bp, 8C 69.1 248
density, at 258C, g/cm
3
1.6570 249
latent heat of vaporization, kJ/mol
a
27.95 248
surface tension at 23.58C, mN/m(=dyn/cm) 35.26 249
viscosity, mPas(=cP)
08C 0.918 248
37.88C 0.595 248
refractive index, n
20
D
1.443 248
vapor pressure, kPa
b
08C 5.45 248
188C 12.69
68.78C 99.3
coefcient of expansion, 0388C, 8C-1 0.0012 248
electrical conductivity, S/cm 3 10
8
248
DH formation, at 258C, kJ/mol
a
liquid 394 14
gas 364 14
DG formation gas, at 258C, kJ/mol
a
320 14
S gas, at 258C, J/(molK)
a
311 14
C
p
, at 258C, J/(molK)
a
liquid 134 14
gas 77 14
a
To convert J to cal, divide by 4.184.
b
To convert kPa to mmHg, multiply by 7.5.
82 SULFUR COMPOUNDS Vol. 23
Table 8. Physical and Thermodynamic Properties of Sulfur Dioxide
Property Value References
mol wt 64.06 14
mp, 8C 72.7 272
bp, 8C 10.02 269
DH fusion, kJ/mol
a
7.40 269
DH vaporization, at 10.08C, kJ/mol
a
24.92 269
vapor density, at 08C, 101.3 kPa(=1 atm), air =1 2.263 269
liquid density, at 208C, g/cm
3
1.50 272
critical temperature, 8C 157.6 272
critical pressure, kPa
b
7911 272
critical volume, cm
3
/g 122.0 272
DG formation gas, at 258C, kJ/mol
a
300.19 14
DH formation gas, at 258C, kJ/mol
a
296.82 14
S formation gas, at 258C, J/(molK)
a
248.1 14
C
p
gas, at 258C, J/(molK)
a
39.9 14
dielectric constant at 16.58C 17.27 269
dipole moment at 258C, Cm
c
3.87 10
30
vapor pressure, kPa
b
108C 230 273
208C 330
308C 462
408C 630
solubility in water, at 101.3 kPa, g/100 g H
2
O 274
08C 22.971
108C 16.413
208C 11.577
308C 8.247
408C 5.881
a
To convert J to cal, divide by 4.184.
b
To convert kPa to psi, multiply by 0.145.
c
To convert Cm to D, divide by 3.33610
30
.
Vol. 23 SULFUR COMPOUNDS 83
Table 9. Physical Properties of MSC
Property Value
mol wt 114.6
bp, at 97.3 kPa (730 mmHg), 8C 161
refractive index, at 258C, n
20
D
1.45
freezing point, 8C 33
viscosity, at 258C, mm
2
/s (=cSt) 1.33
specic gravity
208C 1.475
308C 1.467
ash point, COC,
a
8C >230
coefcient of cubical expansion, 8C-1 0.00082
solubility in water insoluble (hydrolyzes)
latent heat of vaporization,
b
kJ/kg
c
349
a
Cleveland open cup.
b
Calculated value at the boiling point.
c
To convert kJ/kg to Btu/lb, multiply by 0.4303.
Table 10. Physical Properties of MSA
a
Value
Property 70% 99.5%
b
formula weight 96.1
MSA content, % 69.570.5 99.5
b
appearance clear clear
color, APHA 200 150
freezing point, 8C 60 19
boiling point,
c
8C 122
refractive index, at 258C 1.4308
density, at 258C, g/cm
3
1.471.483
a
Refs. 485 and 486.
b
Value is minimum.
c
At 0.133 kPa (1.0 mmHg).
84 SULFUR COMPOUNDS Vol. 23