Polythionic acid

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Skeletal formula of polythionic acid Polythionic acid 2-D structure.png
Skeletal formula of polythionic acid

Polythionic acid is an oxoacid which has a straight chain of sulfur atoms and has the chemical formula Sn(SO3H)2 (n > 2). Trithionic acid (H2S3O6), tetrathionic acid (H2S4O6) are simple examples. They are the conjugate acids of polythionates. The compounds of n < 80 are expected to exist, and those of n < 20 have already been synthesized. Dithionic acid (H2S2O6) does not belong to the polythionic acids due to strongly different properties.

Contents

Nomenclature

All polythionates anion contains chains of sulfur atoms attached to the terminal SO3H-groups. Names of polythionic acids are determined by the number of atoms in the chain of sulfur atoms:

History

Numerous acids and salts of this group have a venerable history, and chemistry systems, where they exist, dates back to the studies John Dalton devoted to the behavior of hydrogen sulfide in aqueous solutions of sulfur dioxide (1808). This solution now has the name of Heinrich Wilhelm Ferdinand Wackenroder, who conducted a systematic study (1846). Over the next 60–80 years, numerous studies have shown the presence of ions, in particular tetrathionate and pentathionate anion (S
4
O2−
6
and S
5
O2−
6
, respectively).

Preparation and properties

H
2
S
react with SO
3
or HSO
3
Cl
, forming thiosulfuric acid H
2
S
2
O
3
, as the analogous reaction with H
2
S
2
forms disulfonomonosulfonic acid HS
2
SO
3
H
; similarly polysulfanes H2Sn (n = 2–6) give HSnSO3H. Reactions from both ends of the polysulfane chain lead to the formation of polysulfonodisulfonic acid HO3SSnSO3H.

Many methods exist for the synthesis of these acids, but the mechanism is unclear because of the large number of simultaneously occurring and competing reactions such as redox, chain transfer, and disproportionation. Typical examples are:

H2S + H2SO3 → H2S2O2 + H2O
H2S2O2 + 2 H2SO3 → H2S4O6 + 2 H2O
H2S4O6 + H2SO3 → H2S3O6 + H2S2O3
SCl2 + 2 HSO
3
→ [O3SSSO 3]2− + 2 HCl
S2Cl2 + 2 HSO
3
→ [O3SS2SO3]2− + 2 HCl
SCl2 + 2 HS
2
O
3
→ [O3SS3SO3]2− + 2 HCl

Anhydrous polythionic acids can be formed in diethyl ether solution by the following three general ways:

HSnSO3H + SO3 → H2Sn+2O6 (n = 1, 2 ... 8)
H2Sn + 2 SO3 → H2Sn+2O6 (n = 1, 2 ... 8)
2 HSnSO3H + I2 → H2S2n+2O6 + 2 HI (n = 1, 2 ... 6)

Polythionic acids with a small number of sulfur atoms in the chain (n = 3, 4, 5, 6) are the most stable. Polythionic acids are stable only in aqueous solutions, and are rapidly destroyed at higher concentrations with the release of sulfur, sulfur dioxide and - sometimes - sulfuric acid. Acid salts of polythionic acids do not exist. Polythionate ions are significantly more stable than the corresponding acids.

Under the action of oxidants (potassium permanganate, potassium dichromate) polythionic acids and their salts are oxidized to sulfate, and the interaction with strong reducing agents (amalgam of sodium) converts them into sulfites and dithionites.

Occurrence

Polythionic acids are rarely encountered, but polythionates are common and important.

Polythionic acids have been identified in crater lakes. [2] The phenomenon may be useful to predict volcanic activity.

Related Research Articles

Acid Chemical compound giving a proton or accepting an electron pair

An acid is a molecule or ion capable of either donating a proton (i.e. hydrogen ion, H+), known as a Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis acid.

Acid–base reaction Chemical reaction

An acid–base reaction is a chemical reaction that occurs between an acid and a base. It can be used to determine pH. Several theoretical frameworks provide alternative conceptions of the reaction mechanisms and their application in solving related problems; these are called the acid–base theories, for example, Brønsted–Lowry acid–base theory.

Sulfuric acid Chemical compound

Sulfuric acid or sulphuric acid, known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formula H2SO4. It is a colorless, odorless and viscous liquid that is miscible with water.

Sulfate Oxyanion with a central atom of sulfur surrounded by 4 oxygen atoms

The sulfate or sulphate ion is a polyatomic anion with the empirical formula SO2−
4
. Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many are prepared from that acid.

In chemistry, an amphoteric compound is a molecule or ion that can react both as an acid and as a base. What exactly this can mean depends on which definitions of acids and bases are being used. The prefix of the word 'amphoteric' is derived from a Greek prefix amphi which means "both".

The compound hydrogen chloride has the chemical formula HCl and as such is a hydrogen halide. At room temperature, it is a colourless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric water vapor. Hydrogen chloride gas and hydrochloric acid are important in technology and industry. Hydrochloric acid, the aqueous solution of hydrogen chloride, is also commonly given the formula HCl.

Sulfurous acid Chemical compound

Sulfurous acid (also Sulfuric(IV) acid, Sulphurous acid (UK), Sulphuric(IV) acid (UK)) is the chemical compound with the formula H2SO3. There is no evidence that sulfurous acid exists in solution, but the molecule has been detected in the gas phase. The conjugate bases of this elusive acid are, however, common anions, bisulfite (or hydrogen sulfite) and sulfite. Sulfurous acid is an intermediate species in the formation of acid rain from sulfur dioxide.

Nitrous acid Chemical compound

Nitrous acid is a weak and monoprotic acid known only in solution, in the gas phase and in the form of nitrite salts. Nitrous acid is used to make diazonium salts from amines. The resulting diazonium salts are reagents in azo coupling reactions to give azo dyes.

Neutralization (chemistry) Chemical reaction in which an acid and a base react quantitatively

In chemistry, neutralization or neutralisation is a chemical reaction in which acid and a base react quantitatively with each other. In a reaction in water, neutralization results in there being no excess of hydrogen or hydroxide ions present in the solution. The pH of the neutralized solution depends on the acid strength of the reactants.

Sodium thiosulfate Chemical compound

Sodium thiosulfate (sodium thiosulphate) is an inorganic compound with the formula Na2S2O3.xH2O. Typically it is available as the white or colorless pentahydrate, Na2S2O3·5H2O. The solid is an efflorescent (loses water readily) crystalline substance that dissolves well in water.

Sulfonic acid

A sulfonic acid (or sulphonic acid) refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound (with the organic substituent replaced by hydrogen) is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

Magic acid Chemical compound

Magic acid (FSO3H·SbF5) is a superacid consisting of a mixture, most commonly in a 1:1 molar ratio, of fluorosulfuric acid (HSO3F) and antimony pentafluoride (SbF5). This conjugate Brønsted–Lewis superacid system was developed in the 1960s by the George Olah lab at Case Western Reserve University, and has been used to stabilize carbocations and hypercoordinated carbonium ions in liquid media. Magic acid and other superacids are also used to catalyze isomerization of saturated hydrocarbons, and have been shown to protonate even weak bases, including methane, xenon, halogens, and molecular hydrogen.

An oxyacid, oxoacid, or ternary acid is an acid that contains oxygen. Specifically, it is a compound that contains hydrogen, oxygen, and at least one other element, with at least one hydrogen atom bonded to oxygen that can dissociate to produce the H+ cation and the anion of the acid.

Chlorosulfuric acid Chemical compound

Chlorosulfuric acid (IUPAC name: sulfurochloridic acid) is the inorganic compound with the formula HSO3Cl. It is also known as chlorosulfonic acid, being the sulfonic acid of chlorine. It is a distillable, colorless liquid which is hygroscopic and a powerful lachrymator. Commercial samples usually are pale brown or straw colored.

Thiosulfuric acid is the inorganic compound with the formula H2S2O3. It has attracted academic interest as a simple, easily accessed compound that is labile. It has few practical uses.

Thiosulfurous acid Chemical compound

Thiosulfurous acid (HS−S(=O)−OH) is a hypothetical compound with the formula S2(OH)2. Attempted synthesis leads to polymers. It is a low oxidation state (+1) sulfur acid. It is the equivalent acid for disulfur monoxide. Salts derived from thiosulfurous acid, which are also unknown, are named "thiosulfites" 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.

Sulfoxylic acid Chemical compound

Sulfoxylic acid (H2SO2) (also known as hyposulfurous acid or sulfur dihydroxide) 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. 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.

Polythionates

Polythionates are oxoanions with the formula Sn(SO3)22- (n≥0). They occur naturally and are the products of redox reactions of thiosulfate. Polythionates are readily isolable, unlike the parent polythionic acids.

Sodium trifluoroacetate Chemical compound

Sodium trifluoroacetate is a chemical compound with a formula of CF3CO2Na. It is the sodium salt of trifluoroacetic acid. It is used as a source of trifluoromethylations.

References

  1. Sarkar, Ramaprasad (2012). General and inorganic chemistry. New Central Book Agency. p. 483. ISBN   9788173817274.
  2. Takano, B. (1987). "Correlation of Volcanic Activity with Sulfur Oxyanion Speciation in a Crater Lake". Science. 235 (4796): 1633–1635. Bibcode:1987Sci...235.1633T. doi:10.1126/science.235.4796.1633. PMID   17795598. S2CID   19856265.