Thiocarbonic acid

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Trithiocarbonic acid
Trithiocarbonic acid.svg
Names
IUPAC name
Carbonotrithioic acid
Systematic IUPAC name
Trithiocarbonic acid
Other names
Thiocarbonic acid
Sulfocarbonic acid
Trisulfocarbonic acid
Dithiocarbon sulfide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.008.931 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 209-822-6
MeSH C013321
PubChem CID
UNII
  • InChI=1S/CH2S3/c2-1(3)4/h(H2,2,3,4) X mark.svgN
    Key: HIZCIEIDIFGZSS-UHFFFAOYSA-N X mark.svgN
  • C(=S)(S)S
Properties
H2CS3
Molar mass 110.21 g·mol−1
AppearanceRed oily liquid, yellow solid
Density 1.483 g/cm3 (liquid)
Melting point −26.8 °C; −16.3 °F; 246.3 K
Boiling point 58 °C; 136 °F; 331 K
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Thiocarbonic acid is an inorganic acid with the chemical formula H2CS3 (or S=C(SH)2). It is an analog of carbonic acid H2CO3 (or O=C(OH)2), in which all oxygen atoms are replaced with sulfur atoms. It is an unstable hydrophobic red oily liquid. [1]

Contents

It is often referred to as trithiocarbonic acid so as to differentiate it from other carbonic acids containing sulfur, such as monothiocarbonic O,O-acid S=C(OH)2, monothiocarbonic O,S-acid O=C(OH)(SH), dithiocarbonic O,S-acid S=C(OH)(SH) and dithiocarbonic S,S-acid O=C(SH)2 (see thiocarbonates).

Discovery and synthesis

It was first reported in brief by Zeise in 1824 and later in more detail by Berzelius in 1826, [2] in both cases it was produced by the action of carbon disulfide on a hydrosulfide salt (e.g. potassium hydrosulfide). [3]

CS2 + 2 KSH → K2CS3 + H2S

Treatment with acids liberates the thiocarbonic acid as a red oil

K2CS3 + 2 HX → H2CS3 + 2 KX

Both the acid and many of its salts are unstable and decompose via the release of carbon disulfide, particularly upon heating:

H2CS3 → CS2 + H2S

An improved synthesis involves addition of barium trithiocarbonate to hydrochloric acid at 0 °C. This method provided samples with which many measurement have been made. [1]

Despite its lability, crystals of thiocarbonic acid have been examined by X-ray crystallography, which confirms the anticipated molecular structure of a trigonal–planar central carbon atom. The C-S bond lengths range from 1.69 to 1.77 Å. [4]

Reactions and derivatives

Thiocarbonic acid is acidic, with the first pKa being around 2. The second pKa is near 7. It dissolves S8, but does not react with it. [1]

Salts and esters of trithiocarbonic acid are called trithiocarbonates, and they are sometimes called thioxanthates.

Thiocarbonic acid reacts with bifunctional reagents to give rings. 1,2-Dichloroethane gives ethylene trithiocarbonate (S=CS2(CH2)2). Oxalyl chloride gives oxalyl trithiocarbonate (S=CS2(C=O)2).

Applications

Thiocarbonic acid currently has no significant applications. Its esters find use in RAFT polymerization.

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Thiol</span> Any organic compound having a sulfanyl group (–SH)

In organic chemistry, a thiol, or thiol derivative, is any organosulfur compound of the form R−SH, where R represents an alkyl or other organic substituent. The −SH functional group itself is referred to as either a thiol group or a sulfhydryl group, or a sulfanyl group. Thiols are the sulfur analogue of alcohols, and the word is a blend of "thio-" with "alcohol".

<span class="mw-page-title-main">Carbon disulfide</span> Neurotoxic compound with formula S=C=S

Carbon disulfide is an inorganic compound with the chemical formula CS2 and structure S=C=S. It is a colorless, flammable, neurotoxic liquid that is used as a building block in organic synthesis. Pure carbon disulfide has a pleasant, ether- or chloroform-like odor, but commercial samples are usually yellowish and are typically contaminated with foul-smelling impurities.

Sulfide (British English also sulphide) 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.

<span class="mw-page-title-main">Bisulfide</span> Inorganic anion containing one sulfur and one hydrogen atoms

Bisulfide is an inorganic anion with the chemical formula HS. It contributes no color to bisulfide salts, and its salts may have a distinctive putrid smell. It is a strong base. Bisulfide solutions are corrosive and attack the skin.

Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature is abound with organosulfur compounds—sulfur is vital for life. Of the 20 common amino acids, two are organosulfur compounds, and the antibiotics penicillin and sulfa drugs both contain sulfur. While sulfur-containing antibiotics save many lives, sulfur mustard is a deadly chemical warfare agent. Fossil fuels, coal, petroleum, and natural gas, which are derived from ancient organisms, necessarily contain organosulfur compounds, the removal of which is a major focus of oil refineries.

<span class="mw-page-title-main">Xanthate</span> Salt that is a metal-thioate/O-esters of dithiocarbonate

A xanthate is a salt or ester of a xanthic acid. The formula of the salt of xanthic acid is [R−O−CS2]M+. Xanthate also refers to the anion [R−O−CS2]. The formula of a xanthic acid is R−O−C(=S)−S−H, such as ethyl xanthic acid, while the formula of an ester of a xanthic acid is R−O−C(=S)−S−R', where R and R' are organyl groups. The salts of xanthates are also called O-organyl dithioates. The esters of xanthic acid are also called O,S-diorganyl esters of dithiocarbonic acid. The name xanthate is derived from Ancient Greek ξανθός (xanthos) meaning 'yellowish' or 'golden', and indeed most xanthate salts are yellow. They were discovered and named in 1823 by Danish chemist William Christopher Zeise. These organosulfur compounds are important in two areas: the production of cellophane and related polymers from cellulose and for extraction of certain sulphide bearing ores. They are also versatile intermediates in organic synthesis.

<span class="mw-page-title-main">Calcium sulfide</span> Chemical compound of formula CaS

Calcium sulfide is the chemical compound with the formula CaS. This white material crystallizes in cubes like rock salt. CaS has been studied as a component in a process that would recycle gypsum, a product of flue-gas desulfurization. Like many salts containing sulfide ions, CaS typically has an odour of H2S, which results from small amount of this gas formed by hydrolysis of the salt.

<span class="mw-page-title-main">Sodium sulfide</span> Chemical compound

Sodium sulfide is a chemical compound with the formula Na2S, or more commonly its hydrate Na2S·9H2O. Both the anhydrous and the hydrated salts in pure crystalline form are colorless solids, although technical grades of sodium sulfide are generally yellow to brick red owing to the presence of polysulfides and commonly supplied as a crystalline mass, in flake form, or as a fused solid. They are water-soluble, giving strongly alkaline solutions. When exposed to moist air, Na2S and its hydrates emit hydrogen sulfide, an extremely toxic, flammable and corrosive gas which smells like rotten eggs.

<span class="mw-page-title-main">Phosphorus pentasulfide</span> Chemical compound

Phosphorus pentasulfide is the inorganic compound with the formula P2S5 (empirical) or P4S10 (molecular). This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in carbon disulfide but reacts with many other solvents such as alcohols, DMSO, and DMF.

<span class="mw-page-title-main">Dithiocarbamate</span> Chemical group (>N–C(=S)–S–)

In organic chemistry, a dithiocarbamate is a functional group with the general formula R2N−C(=S)−S−R and structure >N−C(=S)−S−. It is the analog of a carbamate in which both oxygen atoms are replaced by sulfur atoms.

<span class="mw-page-title-main">Thiophosphoryl chloride</span> Chemical compound

Thiophosphoryl chloride is an inorganic compound with the chemical formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.

Thiocarbonate describes a family of anions with the general chemical formula CS
3−x
O2−
x
(x = 0, 1, or 2):

<span class="mw-page-title-main">Sulfenyl chloride</span> Chemical group (R–S–Cl)

In organosulfur chemistry, a sulfenyl chloride is a functional group with the connectivity R−S−Cl, where R is alkyl or aryl. Sulfenyl chlorides are reactive compounds that behave as sources of RS+. They are used in the formation of RS−N and RS−O bonds. According to IUPAC nomenclature they are named as alkyl thiohypochlorites, i.e. esters of thiohypochlorous acid.

In organic chemistry, thiocarboxylic acids or carbothioic acids are organosulfur compounds related to carboxylic acids by replacement of one of the oxygen atoms with a sulfur atom. Two tautomers are possible: a thione form and a thiol form. These are sometimes also referred to as "carbothioic O-acid" and "carbothioic S-acid" respectively. Of these the thiol form is most common.

<span class="mw-page-title-main">Thiosulfurous acid</span> Chemical compound

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" or "sulfurothioites". The ion is S=SO2−
2
.

In chemistry, a thioxanthate is an organosulfur compound with the formula RSCS2X. When X is an alkali metal, the thioxanthate is a salt. When X is a transition metal, the thioxanthate is a ligand, and when X is an organic group, the compounds are called thioxanthate esters. They are usually yellow colored compounds that often dissolve in organic solvents. They are used as precursors to some catalysts, froth flotation agents, and additives for lubricants.

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.

<span class="mw-page-title-main">Dimethyl trithiocarbonate</span> A methyl ester of trithiocarbonic acid.

Dimethyl trithiocarbonate is an organic compound with the chemical formula S=C(SCH3)2. It is a methyl ester of trithiocarbonic acid. This chemical belongs to a subcategory of esters called thioesters. It is a sulfur analog of dimethyl carbonate O=C(OCH3)2, where all three oxygen atoms are replaced with sulfur atoms. Dimethyl trithiocarbonate is a yellow liquid with a strong and unpleasant odor.

<span class="mw-page-title-main">Ethyl xanthic acid</span> Ethyl xanthic acid

Ethyl xanthic acid is an organic compound with the chemical formula CH3CH2−O−C(=S)−SH. It can be viewed as an O-ethyl ester of dithiocarbonic O,S-acid. Ethyl xanthic acid belongs to the category of thioacids, where the prefix thio- means that an oxygen atom in the compound is replaced by a sulfur atom.

References

  1. 1 2 3 Gattow, Gerhard; Behrendt, Werner (1977). Carbon Sulfides and their Inorganic and Complex Chemistry. Stuttgart: Georg Thieme. p. 154-6. ISBN   3135262014.
  2. Berzelius, J. J. (1826). "Ueber die Schwefelsalze" [About the sulfur salts]. Annalen der Physik (in German). 82 (4): 425–458. Bibcode:1826AnP....82..425B. doi:10.1002/andp.18260820404.
  3. O'Donoghue, Ida Guinevere; Kahan, Zelda (1906). "CLXXIV.—Thiocarbonic acid and some of its salts". J. Chem. Soc., Trans. 89: 1812–1818. doi:10.1039/CT9068901812.
  4. Krebs, B.; Gattow, G. (1965). "Über Chalkogenocarbonate. XIV. Das Kohlenstoffsulfid-bis-(hydrogensulfid) SC(SH)2 und das System H2SCS2 6. Die Kristallstruktur der Trithiokohlensure bei -100 ″C". Zeitschrift für anorganische und allgemeine Chemie. 340 (5–6): 294–311. doi:10.1002/zaac.19653400508.