Disulfur dioxide

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Disulfur dioxide
Disulfur-dioxide-2D-dimensions.png
Disulfur-dioxide-3D-vdW-A.png
Names
Other names
disulfur(II)oxide
SO dimer
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1/O2S2/c1-3-4-2
    Key: AXYLJRYHRATPSG-UHFFFAOYNA-N
  • O=[S][S]=O
Properties
S2O2
Molar mass 96.1299 g/mol
Appearancegas
Structure
bent
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
toxic
Related compounds
Related compounds
 tetrasulfur
SO,
S3O
S2O
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Disulfur dioxide, dimeric sulfur monoxide or SO dimer is an oxide of sulfur with the formula S2O2. [2] The solid is unstable with a lifetime of a few seconds at room temperature. [3]

Contents

Structure

Disulfur dioxide adopts a cis planar structure with C2v symmetry. The S−O bond length is 145.8 pm, shorter than in sulfur monoxide. The S−S bond length is 202.45 pm and the O−S−S angle is 112.7°. S2O2 has a dipole moment of 3.17 D. [4] It is an asymmetric top molecule. [1] [5]

Formation

Sulfur monoxide (SO) converts to disulfur dioxide (S2O2) spontaneously and reversibly. [4] So the substance can be generated by methods that produce sulfur monoxide. Disulfur dioxide has also been formed by an electric discharge in sulfur dioxide. [5] Another laboratory procedure is to react oxygen atoms with carbonyl sulfide or carbon disulfide vapour. [6]

Although most forms of elemental sulfur (S8 and other rings and chains) do not combine with SO2, atomic sulfur does so to form sulfur monoxide, which dimerizes: [7]

S + SO2 → S2O2 ⇌ 2 SO

Disulfur dioxide is also produced upon a microwave discharge in sulfur dioxide diluted in helium. [8] At a pressure of 0.1 mmHg (13 Pa), five percent of the result is S2O2. [9]

Disulfur dioxide is formed transiently when hydrogen sulfide and oxygen undergo flash photolysis. [10]

Properties

The ionization energy of disulfur dioxide is 9.93±0.02 eV. [6]

Disulfur dioxide absorbs at 320–400 nm, as observed of the Venusian atmosphere, [11] and is believed to have contributed to the greenhouse effect on that planet. [12]

Reactions and decomposition

Although disulfur dioxide exists in equilibrium with sulfur monoxide, it also reacts with sulfur monoxide to form sulfur dioxide and disulfur monoxide. [8] [13]

Decomposition of S2O2 proceeds via the following disproportionation reaction:

S2O2 → SO2 + 1/8 S8

Complexes

S2O2 can be a ligand with transition metals. It binds in the η2-S–S position with both sulfur atoms linked to the metal atom. [14] This was first shown in 2003. The bis(trimethylphosphine) thiirane S-oxide complex of platinum, when heated in toluene at 110 °C loses ethylene, and forms a complex with S2O2: (Ph3P)2Pt(S2O2). [15] Iridium atoms can also form a complex: cis-[(dppe)2IrS2]Cl with sodium periodate oxidizes to [(dppe)2IrS2O] and then to [(dppe)2IrS2O2], with dppe being 1,2-bis(diphenylphosphino)ethane. [16] [17] This substance has the S2O2 in a cis position. The same conditions can make a trans complex, but this contains two separate SO radicals instead. The iridium complex can be decomposed with triphenylphosphine to form triphenylphosphine oxide and triphenylphosphine sulfide. [16]

Anion

The S
2O−
2 radical anion has been observed in the gas phase. It may adopt a trigonal shape akin to SO3. [18]

Spectrum

Microwave

TransitionFrequency (MHz) [5]
21,1−20,211013.840
41,3−40,414081.640
11,1−00,015717.946
40,4−31,316714.167
31,3−20,226342.817
42,2−41,326553.915
22,0−21,128493.046
60,6−51,530629.283
52,4−51,535295.199
51,5−40,435794.527

In the Solar System

There is some evidence that disulfur dioxide may be a small component in the atmosphere of Venus, and that it may substantially contribute of the planet's severe greenhouse effect. [11] It is not found in any substantive quantity in Earth's atmosphere.

Related Research Articles

<span class="mw-page-title-main">Oxide</span> Chemical compound where oxygen atoms are combined with atoms of other elements

An oxide is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– ion with oxygen in the oxidation state of −2. Most of the Earth's crust consists of oxides. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 that protects the foil from further oxidation.

<span class="mw-page-title-main">Sulfur dioxide</span> Chemical compound of sulfur and oxygen

Sulfur dioxide or sulphur dioxide is the chemical compound with the formula SO
2. It is a toxic gas 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. It was known to alchemists as "volatile spirit of sulfur" since at least 16th century.

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

Sulfur monoxide is an inorganic compound with formula SO. It is only found as a dilute gas phase. When concentrated or condensed, it converts to S2O2 (disulfur dioxide). It has been detected in space but is rarely encountered intact otherwise.

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 states. 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 synproportionation.

Sulfur oxide refers to many types of sulfur and oxygen containing compounds such as SO, SO2, SO3, S7O2, S6O2, S2O2, etc.

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

Tetrasulfur tetranitride is an inorganic compound with the formula S4N4. This gold-poppy coloured solid is the most important binary sulfur nitride, which are compounds that contain only the elements sulfur and nitrogen. It is a precursor to many S-N compounds and has attracted wide interest for its unusual structure and bonding.

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">Disulfur decafluoride</span> Chemical compound

Disulfur decafluoride is a chemical compound with the formula S2F10. It was discovered in 1934 by Denbigh and Whytlaw-Gray. Each sulfur atom of the S2F10 molecule is octahedral, and surrounded by five fluorine atoms and one sulfur atom. The two sulfur atoms are connected by a single bond. In the S2F10 molecule, the oxidation state of each sulfur atoms is +5, but their valency is 6. S2F10 is highly toxic, with toxicity four times that of phosgene.

<span class="mw-page-title-main">Thiosulfate</span> Polyatomic ion (S2O3, charge –2)

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, e.g. sodium thiosulfate Na2S2O3. Thiosulfate also refers to the esters of thiosulfuric acid. The prefix thio- indicates that the thiosulfate is a sulfate with one oxygen replaced by sulfur. Thiosulfate is tetrahedral at the central S atom. Thiosulfate salts occur naturally. Thiosulfate ion has C3v symmetry, and is produced by certain biochemical processes. It rapidly dechlorinates water and is notable for its use to halt bleaching in the paper-making industry. Thiosulfate salts are mainly used in dying in textiles and the bleaching of natural substances.

<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">Copper(I) sulfide</span> Chemical compound

Copper(I) sulfide is a copper sulfide, a chemical compound of copper and sulfur. It has the chemical compound Cu2S. It is found in nature as the mineral chalcocite. It has a narrow range of stoichiometry ranging from Cu1.997S to Cu2.000S. Samples are typically black.

<span class="mw-page-title-main">Dichlorotris(triphenylphosphine)ruthenium(II)</span> Chemical compound

Dichlorotris(triphenylphosphine)ruthenium(II) is a coordination complex of ruthenium. It is a chocolate brown solid that is soluble in organic solvents such as benzene. The compound is used as a precursor to other complexes including those used in homogeneous catalysis.

Sulfur mononitride is an inorganic compound with the molecular formula SN. It is the sulfur analogue of and isoelectronic to the radical nitric oxide, NO. It was initially detected in 1975, in outer space in giant molecular clouds and later the coma of comets. This spurred further laboratory studies of the compound. Synthetically, it is produced by electric discharge in mixtures of nitrogen and sulfur compounds, or combustion in the gas phase and by photolysis in solution.

<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 organometallic chemistry, metal sulfur dioxide complexes are complexes that contain sulfur dioxide, SO2, bonded to a transition metal. Such compounds are common but are mainly of theoretical interest. Historically, the study of these compounds has provided insights into the mechanisms of migratory insertion reactions.

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

Thiophosphoryl fluoride is an inorganic molecular gas with formula PSF3 containing phosphorus, sulfur and fluorine. It spontaneously ignites in air and burns with a cool flame. The discoverers were able to have flames around their hands without discomfort, and called it "probably one of the coldest flames known". The gas was discovered in 1888.

The chalcogens react with each other to form interchalcogen compounds.

<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.

<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.

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.

References

  1. 1 2 Demaison, Jean; Vogt, Jürgen (2011). "836. O2S2 Disulfur dioxide" (PDF). Asymmetric Top Molecules, Part 3. Landolt–Börnstein: Group II Molecules and Radicals. Vol. 29D3. Springer. p. 492. doi:10.1007/978-3-642-14145-4_258. ISBN   9783642141454.
  2. ↑ Holleman, Arnold F.; Wiber, Egon; Wiberg, Nils, eds. (2001). "Oxides of sulfur". Inorganic Chemistry. Academic Press. p. 530. ISBN   9780123526519.
  3. ↑ Mitchell, Stephen C. (2004). Biological Interactions Of Sulfur Compounds. CRC Press. p. 7. ISBN   9780203362525.
  4. 1 2 Lovas, F. J. (1974). "Spectroscopic studies of the SO2 discharge system. II. Microwave spectrum of the SO dimer". The Journal of Chemical Physics. 60 (12): 5005. Bibcode:1974JChPh..60.5005L. doi:10.1063/1.1681015.
  5. 1 2 3 Thorwirth, Sven; Theulé, P.; Gottlieb, C. A.; Müller, H. S. P.; McCarthy, M. C.; Thaddeus, P. (2006). "Rotational spectroscopy of S2O: vibrational satellites, 33S isotopomers, and the submillimeter-wave spectrum" (PDF). Journal of Molecular Structure. 795 (1–3): 219–229. Bibcode:2006JMoSt.795..219T. doi:10.1016/j.molstruc.2006.02.055.
  6. 1 2 Cheng, Bing-Ming; Hung, Wen-Ching (1999). "Photoionization efficiency spectrum and ionization energy of S2O2". The Journal of Chemical Physics. 110 (1): 188. Bibcode:1999JChPh.110..188C. doi:10.1063/1.478094. ISSN   0021-9606.
  7. ↑ Murakami, Yoshinori; Onishi, Shouichi; Kobayashi, Takaomi; Fujii, Nobuyuki; Isshiki, Nobuyasu; Tsuchiya, Kentaro; Tezaki, Atsumu; Matsui, Hiroyuki (2003). "High Temperature Reaction of S + SO2 → SO + SO: Implication of S2O2 Intermediate Complex Formation". The Journal of Physical Chemistry A. 107 (50): 10996–11000. Bibcode:2003JPCA..10710996M. doi:10.1021/jp030471i. ISSN   1089-5639.
  8. 1 2 Field, T. A.; Slattery, A. E.; Adams, D. J.; Morrison, D. D. (2005). "Experimental observation of dissociative electron attachment to S2O and S2O2 with a new spectrometer for unstable molecules" (PDF). Journal of Physics B: Atomic, Molecular and Optical Physics. 38 (3): 255–264. Bibcode:2005JPhB...38..255F. doi:10.1088/0953-4075/38/3/009. ISSN   0953-4075. S2CID   122789729. Archived from the original (PDF) on 2015-09-24. Retrieved 2013-05-13.
  9. ↑ Sahoo, Balaram; Nayak, Nimai Charan; Samantaray, Asutosh; Pujapanda, Prafulla Kumar (2012). Inorganic Chemistry. PHI Learning. p. 461. ISBN   9788120343085 . Retrieved 2013-05-16.
  10. ↑ Compton, R. G.; Bamford, C. H.; Tipper, C. F. H. (1972). "Oxidation of H2S". Reactions of Non-Metallic Inorganic Compounds. Comprehensive Chemical Kinetics. Elsevier. p. 50. ISBN   9780080868011.
  11. 1 2 Frandsen, B. N.; Wennberg, P. O.; Kjærgaard, H. G. (2016). "Identification of OSSO as a near-UV absorber in the Venusian atmosphere" (PDF). Geophysical Research Letters. 43 (21): 11146–11155. Bibcode:2016GeoRL..4311146F. doi: 10.1002/2016GL070916 .
  12. ↑ "Rare molecule on Venus may help explain planet's weather". CBC News. Retrieved 2016-11-11.
  13. ↑ Herron, J. T.; Huie, R. E. (1980). "Rate constants at 298 K for the reactions SO + SO + M → (SO)2 + M and SO + (SO)2 → SO2 + S2O". Chemical Physics Letters. 76 (2): 322–324. Bibcode:1980CPL....76..322H. doi:10.1016/0009-2614(80)87032-1.
  14. ↑ Halcrow, Malcolm A.; Huffman, John C.; Christou, George (1994). "Synthesis, Characterization, and Molecular Structure of the New S2O Complex Mo(S2O)(S2CNEt2)3·1/2Et2O" (PDF). Inorganic Chemistry. 33 (17): 3639–3644. doi:10.1021/ic00095a005. ISSN   0020-1669. Archived from the original (PDF) on 2015-11-06. Retrieved 2013-05-13.
  15. ↑ Lorenz, Ingo-Peter; Kull, Jürgen (1986). "Complex Stabilization of Disulfur Dioxide in the Fragmentation of Thiirane S-Oxide on Bis(triphenylphosphane)platinum(0)". Angewandte Chemie International Edition in English. 25 (3): 261–262. doi:10.1002/anie.198602611. ISSN   0570-0833.
  16. 1 2 Schmid, Günter; Ritter, Günter; Debaerdemaeker, Tony (1975). "Die Komplexchemie niederer Schwefeloxide. II. Schwefelmonoxid und Dischwefeldioxid als Komplexliganden" [The complex chemistry of lower sulfur oxides. II. Sulfur monoxide and disulfur dioxide as complex ligands]. Chemische Berichte. 108 (9): 3008–3013. doi:10.1002/cber.19751080921. ISSN   0009-2940.
  17. ↑ Nagata, K.; Takeda, N.; Tokitoh, N. (2003). "Unusual Oxidation of Dichalcogenido Complexes of Platinum". Chemistry Letters. 32 (2): 170–171. doi:10.1246/cl.2003.170. ISSN   0366-7022.
  18. ↑ Clements, Todd G.; Hans-Jürgen Deyerl; Robert E. Continetti (2002). "Dissociative Photodetachment Dynamics of S
    2    O−
    2    "     (PDF). The Journal of Physical Chemistry A. 106 (2): 279–284. Bibcode:2002JPCA..106..279C. doi:10.1021/jp013329v. ISSN   1089-5639 . Retrieved 2013-05-13.
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