Sulfoxylic acid (H2SO2) (also known as hyposulfurous acid or sulfur dihydroxide[1]) is an unstable oxoacid of sulfur in an intermediate oxidation state between hydrogen sulfide and dithionous acid. It consists of two hydroxy groups attached to a sulfur atom.[2] Sulfoxylic acid contains sulfur in an oxidation state of +2. Sulfur monoxide (SO) can be considered as a theoretical anhydride for sulfoxylic acid, but it is not actually known to react with water.[3]
The complementary base is the sulfoxylate anion SO2− 2 which is much more stable. In between these states is the HSO− 2 ion, also somewhat stable.
Sulfoxylate ions can be made by decomposing thiourea dioxide in an alkaline solution.[4] To do this, thiourea dioxide first forms an amidine-sulfinic acid tautomer, H2NC(=NH)SO2H, which then breaks apart.[5] Sulfoxylate reacts with formaldehyde to yield a hydroxymethanesulfinate called rongalite:
Sulfoxylic acid has been detected in the gas phase. It is likely to be formed as an intermediate when hydrogen sulfide is oxidised by living organisms, or in the atmosphere, or anywhere else in the natural environment. It may also exist in circumstellar disks.[6] When H2S is oxidised it starts from oxidation state −2, and should then pass through intermediate values of 0 and +2 before getting to well known sulfite at +4 and sulfate at +6.[7] When sulfide in alkaline conditions is oxidised by air in the presence of nickel ions, sulfoxylate concentration first increases to around 5% and then decreases over several days. Polysulfide concentration also grows and then shrinks on a slower timescale reaching about 25% of the sulfide. The sulfur ends up forming thiosulfate.[7]
Sulfoxylic acid has been made by ultraviolet irradiation of a mixture of solid H2S and H2O, followed by warming. This is a possible natural process in comets or circumstellar disks.[8]
Fender et al. claimed to make "sulfinic acid" (an isomer of sulfoxylic acid) by ultraviolet irradiation on solid sulfur dioxide and hydrogen sulfide in a solid argon matrix, measuring the infrared vibrational spectrum. However the assignment of the lines in the spectrum is doubtful, so this may not be the substance produced.[8]
Sulfoxylic acid can be made in the gas phase in an electric discharge through a neon, H2, SO2 mixture. This also yields some sulfhydryl hydroperoxide.[8]
Properties
Sulfoxylic acid is an isomer of sulfinic acid, which has a hydrogen atom bonded to the sulfur, and the oxygen connected with a double bond (HS(O)OH). Other isomers are thiadioxirane (a ring of two oxygen atoms and a sulfur), dihydrogen sulfone (a sulfur atom linked to two hydrogen and two oxygen atoms), sulfhydryl hydroperoxide (HSOOH),[6] and dihydrogen persulfoxide H2SOO. Sulfoxylic acid has the lowest energy of any of these isomers.[9]
The pKa1 of sulfoxylic acid is 7.97. The pKa2 of bisulfoxylate (HSO− 2) is 13.55.[4]
Calculations of the molecule suggest there may be two alignments termed C2, and Cs. The H−O distance is 96.22 (or 96.16) pm, S−O distance is 163.64 (or 163.67) pm, ∠HOS = 108.14° (108.59°), ∠OSO = 103.28° (103.64°) HOSO twist is 84.34° (+90.56 and −90.56) (Cs dimensions in parentheses).[8]
The microwave spectrum has absorption lines at 10.419265, 12.2441259, 14.0223698, 16.3161779GHz and many others for the Cs and 12.8910254, 19.4509030, 21.4709035, 24.7588445, 29.5065050, 29.5848250, 32.8772050GHz for the C2 form.[8]
The sulfoxylate ion apparently has an X-ray absorption near edge structure at 2476.1eV. With sulfur the X-ray absorption edge changes with oxidation state as per Kunzl's law. The edge corresponds to the energy needed to excite and inner 1S electron to a 3P orbital.[7] Sulfoxylate has an infrared absorption peak at 918.2cm−1.[7]
Reactions
Sulfoxylic acid disproportionates into sulfur and hydrogensulfiteHSO− 3. Some of this in turn reacts to form thiosulfateS 2O2− 3.
Sulfoxylates are sensitive to air, and will be oxidised by the oxygen in it.[10]
The known sulfoxylate salts include cobalt sulfoxylate CoSO2·3H2O.[10] This can dissolve in an ammoniacal solution. However cobalt sulfide will precipitate if sulfide is formed during a reaction.[10]
Sulfoxylate in solution reacts with thiosulfate to form sulfides and sulfites.[10]
Sulfoxylate reduces nitrite to hydronitrite radical dianion NO•2− 2. This in turn reacts with water forming hydroxide ions and nitric oxide (NO). Nitric oxide and nitrous oxide N2O in turn are further reduced by sulfoxylate.[11]
Dithionite is unstable in a pH 4 solution, decomposing to sulfoxylic acid and hydrogen sulfite. This sulfoxylic acid reacts with more dithionite to yield more hydrogen sulfite, and some kind of sulfur, and a small amount of thiosulfate.[11]
S 2O2− 4 + H+ → H2SO2 + HSO− 3
S 2O2− 4 + H2SO2 → 2HSO− 3 + S
S 2O2− 4 + H2SO2 → HSO− 3 + S 2O2− 3 + H+
By reducing sulfur dioxide, hydrogen sulfoxylate forms as an intermediate, and this is much more reactive. Hydrogen sulfoxylate reacts with organic compounds with a double bond (vinyls) to make an organic sulfinate. Hydrogen sulfoxylate reacts with divinyl sulfone to make 1,4-dithiane 1,1,4,4-tetroxide.[11] Perfluorophenyl iodide is reduced to pentafluorobenzene.[11]
Salts of sulfoxylic acid that have been claimed to have been made include cobalt, thallium and zinc. Cobalt sulfoxylate is made from sodium hyposulfite, cobalt chloride and ammonia. Zinc sulfoxylate is produced by reacting zinc metal with sulfuryl chloride. Thallous sulfoxylate is made by allowing oxygen onto thallous sulfide. This is olive brown in colour. When heated to 250°C it recrystallizes to another yellow form.[12] Cuprous sufoxylate Cu2SO2 can be made as a solid or liquid by heating cuprous sulfide and copper sulfate. Cu2SO2 melts at 610K (337°C) and is stable as a liquid phase to over 680K. There are also solid phase transitions at 382K (109°C) and 423K (150°C).[13]
Derivatives
Sulfoxylic acid forms a wide variety of organic esters of the form R–O–S–O–R′.
The nomenclature for these molecules is not entirely standardized, and a wide variety of IUPAC-acceptable names are possible. For substances with the −OSOH group, one can use suffixes ‑oxysulfanol (preferred), ‑hydrogen sulfoxylate, or ‑oxysulfenic acid; or prefixes hydroxysulfanyloxy- (preferred) or sulfenooxy-. The ionic group –OSO− can use the preferred suffix ‑oxysulfanolate or ‑sulfoxylate; or preferred prefix oxysulfanolato- or sulfenatooxy-. The R-OSO-R' can be suffixed with ‑dioxysulfane or ‑sulfoxylate; or prefixed with oxysulfanyloxy- or sulfenooxy-.[14]
In general, sulfoxylate esters are synthesized from sulfur dichloride and a primary or secondary alcohol, to give a diorganyl sulfoxylate (ROSOR) compound. Because sulfur dichloride unavoidably forms some disulfur dichloride and chlorine in solution, this technique also forms di(organyloxy) disulfides and dialkyl sulfites. The yield of sulfoxylates is maximised at low temperatures (around -75°C) and with dilute reactants. Successfully synthesized compounds include the methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, and cholesterol esters, as well as the hemiester para‑(hydroxysulfanyl)cresol (i.e., 1‑hydroxysulfanyloxy-4‑methylbenzene). With 1,2‑diols, SCl2 forms polymeric sulfoxylates; for 1,3-diols, SCl2 reaction creates cyclic oligomers (typically, a six-member 1,3,2-dioxathiane or a twelve-membered cyclic sulfoxylate dimer).[15] Allylic, propargylic, or benzylic sulfoxylate esters are generally unstable, rearranging to give a sulfinate ester; although they are stable at −18°C if chloride is promptly removed from the solution.[15][16] The rearrangment appears to develop a temporary positive charge on the organyl group, as it is inhibited at the benzyl position of electron-poor arenes.[17]
Diethylsulfoxylate can be made by reacting diethoxydisulfide with sodium ethoxide.[15]
Sulfoxylic acid dimethyl ester (also called dimethylsulfoxylate or dimethoxysulfane) (S(OCH3)2) has been studied using electron diffraction, X-ray crystallography, Raman spectroscopy, and infrared spectroscopy. Studying this molecule is much easier than the unstable sulfoxylic acid. It is a liquid at standard conditions that boils at 74°C and freezes at -67° In the gas state the molecular bond angle ∠OSO is 103°, with the oxygen-sulfur distance 1.625Å. The oxygen-carbon distance is 1.426Å and carbon-hydrogen distance 1.105Å with ∠COS 115.9° and ∠COS 109°. The molecule as C2 symmetry with one methyl group rotated above the plane determined by the OSO atoms, and the other below. The C−O−S−O dihedral angle is about 84°. The energy barrier to moving one methyl group to the other side of the plane is 37kJ/mol and it would be in a 12kJ/mol higher energy state in this Cs symmetry state.[18]
Related Research Articles
Sulfur dioxide or sulphur dioxide is the chemical compound with the formula SO 2. It is a colorless gas with a pungent smell that is responsible for the odor of burnt matches. It is released naturally by volcanic activity and is produced as a by-product of copper extraction and the burning of sulfur-bearing fossil fuels.
Sulfuric(IV) acid, also known as sulfurous (UK: sulphurous) acid and thionic acid, is the chemical compound with the formula H2SO3.
Sulfide (also sulphide in British English ) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. Sulfide also refers to large families of inorganic and organic compounds, e.g. lead sulfide and dimethyl sulfide. Hydrogen sulfide (H2S) and bisulfide (SH−) are the conjugate acids of sulfide.
Sodium thiosulfate is an inorganic compound with the formula Na2S2O3·(H2O)x. Typically it is available as the white or colorless pentahydrate, which is a white solid that dissolves well in water. The compound is a reducing agent and a ligand, and these properties underpin its applications.
Sulfate-reducing microorganisms (SRM) or sulfate-reducing prokaryotes (SRP) are a group composed of sulfate-reducing bacteria (SRB) and sulfate-reducing archaea (SRA), both of which can perform anaerobic respiration utilizing sulfate (SO2− 4) as terminal electron acceptor, reducing it to hydrogen sulfide (H2S). Therefore, these sulfidogenic microorganisms "breathe" sulfate rather than molecular oxygen (O2), which is the terminal electron acceptor reduced to water (H2O) in aerobic respiration.
In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation state. The reverse of disproportionation, such as when a compound in an intermediate oxidation state is formed from precursors of lower and higher oxidation states, is called comproportionation, also known as symproportionation.
In horticulture, lime sulfur (lime sulphur in British English, see American and British English spelling differences) is mainly a mixture of calcium polysulfides and thiosulfate (plus other reaction by-products as sulfite and sulfate) formed by reacting calcium hydroxide with elemental sulfur, used in pest control. It can be prepared by boiling in water a suspension of poorly soluble calcium hydroxide (lime) and solid sulfur together with a small amount of surfactant to facilitate the dispersion of these solids in water. After elimination of residual solids (flocculation, decantation, and filtration), it is normally used as an aqueous solution, which is reddish-yellow in colour and has a distinctive offensive odor of hydrogen sulfide (H2S, rotten eggs).
Sodium dithionite is a white crystalline powder with a sulfurous odor. Although it is stable in dry air, it decomposes in hot water and in acid solutions.
The bisulfite ion (IUPAC-recommended nomenclature: hydrogensulfite) is the ion HSO− 3. Salts containing the HSO− 3 ion are also known as "sulfite lyes". Sodium bisulfite is used interchangeably with sodium metabisulfite (Na2S2O5). Sodium metabisulfite dissolves in water to give a solution of Na+HSO− 3.
Sulfur compounds are chemical compounds formed the element sulfur (S). Common oxidation states of sulfur range from −2 to +6. Sulfur forms stable compounds with all elements except the noble gases.
In chemical nomenclature, the IUPAC nomenclature of inorganic chemistry is a systematic method of naming inorganic chemical compounds, as recommended by the International Union of Pure and Applied Chemistry (IUPAC). It is published in Nomenclature of Inorganic Chemistry. Ideally, every inorganic compound should have a name from which an unambiguous formula can be determined. There is also an IUPAC nomenclature of organic chemistry.
The dithionite is the oxyanion with the formula [S2O4]2−. It is commonly encountered as the salt sodium dithionite. For historical reasons, it is sometimes called hydrosulfite, but it contains no hydrogen and is not a sulfite. The dianion has a steric number of 4 and trigonal pyramidal geometry.
Thiosulfate is an oxyanion of sulfur with the chemical formula S2O2−3. Thiosulfate also refers to the compounds containing this anion, which are the salts of thiosulfuric acid, such as sodium thiosulfate Na2S2O3 and ammonium thiosulfate (NH4)2S2O3. Thiosulfate salts occur naturally. Thiosulfate rapidly dechlorinates water, and is used to halt bleaching in the paper-making industry. Thiosulfate salts are mainly used for dyeing in textiles, and bleaching of natural substances.
Sulfinic acids are oxoacids of sulfur with the structure RSO(OH). In these organosulfur compounds, sulfur is pyramidal.
A polysulfane is a chemical compound of formula H2Sn, where n > 1. Compounds containing 2 – 8 sulfur atoms have been isolated, longer chain compounds have been detected, but only in solution. H2S2 is colourless, higher members are yellow with the colour increasing with the sulfur content. In the chemical literature the term polysulfanes is sometimes used for compounds containing −(S)n−, e.g. organic polysulfanes R1−(S)n−R2.
A disulfite, commonly known as metabisulfite or pyrosulfite, is a chemical compound containing the ion S 2O2− 5. It is a colorless dianion that is primarily marketed in the form of sodium metabisulfite or potassium metabisulfite. When dissolved in water, these salts release the hydrogensulfite HSO− 3 anion. These salts act equivalently to sodium hydrogensulfite or potassium hydrogensulfite.
Thiosulfurous acid is a hypothetical chemical compound with the formula HS−S(=O)−OH or HO−S(=S)−OH. Attempted synthesis leads to polymers. It is a low oxidation state (+1) sulfur acid. It is the Arrhenius acid for disulfur monoxide. Salts derived from thiosulfurous acid, which are also unknown, are named "thiosulfites", "thionosulfites" or "sulfurothioites". The ion is S=SO2− 2.
Hydrogen chalcogenides are binary compounds of hydrogen with chalcogen atoms. Water, the first chemical compound in this series, contains one oxygen atom and two hydrogen atoms, and is the most common compound on the Earth's surface.
Dihydroxydisulfane or hypodithionous acid is a reduced sulfur oxyacid with sulfur in a formal oxidation state of +1, but the valence of sulfur is 2. The structural formula is HO−S−S−OH, with all atoms arranged in a chain. It is an isomer of thiosulfurous acid but is lower in energy. Other isomers include HOS(=O)SH, HOS(=S)OH, and HS(=O)2SH. Disulfur monoxide, S2O, can be considered as the anhydride. Unlike many of these other reduced sulfur acids, dihydroxydisulfane can be formed in a pure state by reacting hydrogen sulfide with sulfur dioxide at −70 °C in dichlorodifluoromethane.
'Potassium thiosulfate is an inorganic compound with the formula K2S2O3. This salt can form multiple hydrates, such as the monohydrate, dihydrate, and the pentahydrate, all of which are white or colorless solids. It is used as a fertilizer.
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↑ Tardif, SylvieL.; Harpp, DavidN. (2000) [26 May 2000]. "Preparation of 4-substituted benzyl sulfoxylates and related chemistry". Journal of Organic Chemistry. 65 (16). American Chemical Society: 4791–4795. doi:10.1021/jo991360b.
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