Trisulfur

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Trisulfur
Trisulfur.png Trisulfur schematic.svg
Trisulfur.png
Ball-and-stick model of trisulfur Thiozone-CRC-MW-3D-vdW.png
Ball-and-stick model of trisulfur
Names
IUPAC name
Trisulfur
Other names
Thiozone
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
  • InChI=1S/S3/c1-3-2
    Key: NVSDADJBGGUCLP-UHFFFAOYSA-N
  • Trisulfanidyl S3:InChI=1S/HS3/c1-3-2/h1H/p-1
    Key: WMXWXNVGXOWZRJ-UHFFFAOYSA-M
  • [S-][S+]=S
  • Trisulfanidyl S3:[S-]S[S]
Properties
S3
Molar mass 96.198 g/mol
AppearanceCherry-red
Structure
bent
Related compounds
Related compounds
Ozone
Disulfur monoxide
Sulfur dioxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

The S3 molecule, known as trisulfur, sulfur trimer, thiozone, or triatomic sulfur, is a cherry-red allotrope of sulfur. It comprises about 10% of vaporised sulfur at 713  K (440 °C; 824 °F) and 1,333  Pa (10.00  mmHg ; 0.1933  psi ). It has been observed at cryogenic temperatures as a solid. Under ordinary conditions it converts to cyclooctasulfur.

8 S3 → 3 S8

Structure and bonding

In terms of structure and bonding S3 and ozone (O3) are similar. Both adopt bent structures and are diamagnetic. Although represented with S=S double bonds, the bonding situation is more complex. [1]

The S–S distances are equivalent and are 191.70±0.01  pm , and with an angle at the central atom of 117.36°±0.006°. [2] However, cyclic S3, where the sulfur atoms are arranged in an equilateral triangle with three single bonds (similar to cyclic ozone and cyclopropane), is calculated to be lower in energy than the bent structure experimentally observed. [3]

The name thiozone was invented by Hugo Erdmann in 1908 who hypothesized that S3 comprises a large proportion of liquid sulfur. [4] However its existence was unproven until the experiments of J. Berkowitz in 1964. [5] Using mass spectrometry, he showed that sulfur vapour contains the S3 molecule. Above 1,200 °C (2,190 °F)S3 is the second most common molecule after S2 in gaseous sulfur. [5] In liquid sulfur the molecule is not common until the temperature is high, such as 500 °C (932 °F). However, small molecules like this contribute to most of the reactivity of liquid sulfur. [5] S3 has an absorption peak of 425 nm (violet) with a tail extending into blue light. [5]

S3 can also be generated by photolysis of S3Cl2 embedded in a glass or matrix of solid noble gas. [5]

Natural occurrence

S3 occurs naturally on Io in volcanic emissions. S3 is also likely to appear in the atmosphere of Venus at heights of 20 to 30 km, where it is in thermal equilibrium with S2 and S4. [6] :546 The reddish colour of Venus' atmosphere at lower levels is likely to be due to S3. [6] :539

Reactions

S3 reacts with carbon monoxide to make carbonyl sulfide and S2.

Formation of compounds with a defined number of sulfur atoms is possible:

S3 + S2O → S5O (cyclic) [7]

Radical anion

Lazurite contains
S-3. Lazurite.jpg
Lazurite contains S3.

Although S3 is elusive under ordinary conditions, the radical anion S3 is abundant. [8] It exhibits an intense blue colour. The anion is sometimes called thiozonide, [9] by analogy with the ozonide anion, O3, to which it is valence isoelectronic. The gemstone lapis lazuli and the mineral lazurite (from which the pigment ultramarine is derived) contain S3. International Klein Blue, developed by Yves Klein, also contains the S3 radical anion. [10] The blue colour is due to the C2A2 transition to the X2B1 electronic state in the ion, [9] causing a strong absorption band at 610–620  nm or 2.07  eV (in the orange region of the visible spectrum). [11] The Raman frequency is 523  cm−1 and another infrared absorption is at 580 cm−1. [5]

The S3 ion has been shown to be stable in aqueous solution under a pressure of 0.5  GPa (73,000  psi ), and is expected to occur naturally at depth in the Earth's crust where subduction or high pressure metamorphism occurs. [12] This ion is probably important in movement of copper and gold in hydrothermal fluids. [13]

Lithium hexasulfide (which contains S6, another polysulfide radical anion) with tetramethylenediamine solvation dissociates acetone and related donor solvents to S3. [14]

The S3 radical anion was also made by reducing gaseous sulfur with Zn 2+ in a matrix. The material is strongly blue-coloured when dry and changes colour to green and yellow in the presence of trace amounts of water. [15] Another way to make it is with polysulfide dissolved in hexamethylphosphoramide where it gives a blue colour. [16]

Other methods of production of S3 include reacting sulfur with partially hydroxylated magnesium oxide at 400 °C. [17]

Raman spectroscopy can be used to identify S3, and it can be used non-destructively in paintings. The bands are 549 cm−1 for symmetric stretch, 585 cm−1 for asymmetric stretch, and 259 cm−1 for bending. [18] Natural materials can also contain S2 which has an optical absorption at 390 nm and Raman band at 590 cm−1. [18]

Trisulfide ion

The trisulfide ion, S2−3 is part of the polysulfide series. The sulfur chain is bent at an angle of 107.88°. [5] Strontium trisulfide (SrS3) has a S–S bond length of 205 pm. [5] The bonds are single. It is isoelectronic to sulfur dichloride.

Related Research Articles

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.

<span class="mw-page-title-main">Dinitrogen pentoxide</span> Chemical compound

Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.

<span class="mw-page-title-main">Catenation</span> Bonding of atoms of the same element into chains or rings

In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring shape may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".

<span class="mw-page-title-main">Polysulfide</span> Molecules derived from sulfur chains

Polysulfides are a class of chemical compounds derived from anionic chains of sulfur atoms. There are two main classes of polysulfides: inorganic and organic. The inorganic polysulfides have the general formula S2−
n
. These anions are the conjugate bases of polysulfanes H2Sn. Organic polysulfides generally have the formulae R1SnR2, where R is an alkyl or aryl group.

<span class="mw-page-title-main">Triiodide</span> Ion

In chemistry, triiodide usually refers to the triiodide ion, I
3
. This anion, one of the polyhalogen ions, is composed of three iodine atoms. It is formed by combining aqueous solutions of iodide salts and iodine. Some salts of the anion have been isolated, including thallium(I) triiodide (Tl+[I3]) and ammonium triiodide ([NH4]+[I3]). Triiodide is observed to be a red colour in solution.

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.

<span class="mw-page-title-main">Ammonium tetrathiomolybdate</span> Chemical compound

Ammonium tetrathiomolybdate is the chemical compound with the formula (NH4)2MoS4. This bright red ammonium salt is an important reagent in the chemistry of molybdenum and has been used as a building block in bioinorganic chemistry. The thiometallate (see metallate) anion has the distinctive property of undergoing oxidation at the sulfur centers concomitant with reduction of the metal from Mo(VI) to Mo(IV).

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.

<span class="mw-page-title-main">Lower sulfur oxides</span>

The lower sulfur oxides are a group of inorganic compounds with the formula SmOn, where 2m > n. These species are often unstable and thus rarely encountered in everyday life. They are significant intermediates in the combustion of elemental sulfur. Some well characterized examples include sulfur monoxide (SO), its dimer S2O2, and a series of cyclic sulfur oxides, SnOx (x = 1, 2), based on cyclic Sn rings.

<span class="mw-page-title-main">Allotropes of sulfur</span> Class of substances

The element sulfur exists as many allotropes. In number of allotropes, sulfur is second only to carbon. In addition to the allotropes, each allotrope often exists in polymorphs delineated by Greek prefixes.

Thiophosphates (or phosphorothioates, PS) are chemical compounds and anions with the general chemical formula PS
4−x
O3−
x
(x = 0, 1, 2, or 3) and related derivatives where organic groups are attached to one or more O or S. Thiophosphates feature tetrahedral phosphorus(V) centers.

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

Disulfur is the diatomic molecule with the formula S2. It is analogous to the dioxygen molecule but rarely occurs at room temperature. This violet gas is the dominant species in hot sulfur vapors. S2 is one of the minor components of the atmosphere of Io, which is predominantly composed of SO2. The instability of S2 is usually described in the context of the double bond rule.

<span class="mw-page-title-main">Disulfur monoxide</span> Chemical compound

Disulfur monoxide or sulfur suboxide is an inorganic compound with the formula S2O, one of the lower sulfur oxides. It is a colourless gas and condenses to give a roughly dark red coloured solid that is unstable at room temperature.

In chemistry, the amino radical, ·NH2, also known as the aminyl or azanyl, is the neutral form of the amide ion. Aminyl radicals are highly reactive and consequently short-lived, like most radicals; however, they form an important part of nitrogen chemistry. In sufficiently high concentration, amino radicals dimerise to form hydrazine. While NH2 as a functional group is common in nature, forming a part of many compounds, the radical cannot be isolated in its free form.

Sulfanyl (HS), also known as the mercapto radical, hydrosulfide radical, or hydridosulfur, is a simple radical molecule consisting of one hydrogen and one sulfur atom. The radical appears in metabolism in organisms as H2S is detoxified. Sulfanyl is one of the top three sulfur-containing gasses in gas giants such as Jupiter and is very likely to be found in brown dwarfs and cool stars. It was originally discovered by Margaret N. Lewis and John U. White at the University of California in 1939. They observed molecular absorption bands around 325 nm belonging to the system designated by 2Σ+2Πi. They generated the radical by means of a radio frequency discharge in hydrogen sulfide. HS is formed during the degradation of hydrogen sulfide in the atmosphere of the Earth. This may be a deliberate action to destroy odours or a natural phenomenon.

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

Sodium polysulfide is a general term for salts with the formula Na2Sx, where x = 2 to 5. The species Sx2−, called polysulfide anions, include disulfide (S22−), trisulfide (S32−), tetrasulfide (S42−), and pentasulfide (S52−). In principle, but not in practice, the chain lengths could be longer. The salts are dark red solids that dissolve in water to give highly alkaline and corrosive solutions. In air, these salts oxidize, and they evolve hydrogen sulfide by hydrolysis.

Tellurium compounds are compounds containing the element tellurium (Te). Tellurium belongs to the chalcogen family of elements on the periodic table, which also includes oxygen, sulfur, selenium and polonium: Tellurium and selenium compounds are similar. Tellurium exhibits the oxidation states −2, +2, +4 and +6, with +4 being most common.

<span class="mw-page-title-main">Sulfoxylic acid</span> 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.

<span class="mw-page-title-main">Spectroelectrochemistry</span>

Spectroelectrochemistry (SEC) is a set of multi-response analytical techniques in which complementary chemical information is obtained in a single experiment. Spectroelectrochemistry provides a whole vision of the phenomena that take place in the electrode process. The first spectroelectrochemical experiment was carried out by Theodore Kuwana, PhD, in 1964.

<span class="mw-page-title-main">Disulfidobis(tricarbonyliron)</span> Chemical compound

Disulfidobis(tricarbonyliron), or Fe2(μ-S2)(CO)6, is an organometallic molecule used as a precursor in the synthesis of iron-sulfur compounds. Popularized as a synthetic building block by Dietmar Seyferth, Fe2(μ-S2)(CO)6 is commonly used to make mimics of the H-cluster in [FeFe]-hydrogenase. Much of the reactivity of Fe2(μ-S2)(CO)6 proceeds through its sulfur-centered dianion, [Fe2(μ-S)2(CO)2]2-.

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