Disulfur dioxide
Names | |
---|---|
Other names disulfur(II)oxide SO dimer | |
Identifiers | |
CAS Number |
|
3D model (JSmol) |
|
PubChem CID |
|
InChI
| |
| |
Properties | |
Chemical formula | S2O2 |
Molar mass | 96.1299 g/mol |
Appearance | gas |
Structure | |
Coordination geometry | 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). Infobox references |
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]
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
Transition | Frequency (MHz)[5] |
---|---|
21,1−20,2 | 11013.840 |
41,3−40,4 | 14081.640 |
11,1−00,0 | 15717.946 |
40,4−31,3 | 16714.167 |
31,3−20,2 | 26342.817 |
42,2−41,3 | 26553.915 |
22,0−21,1 | 28493.046 |
60,6−51,5 | 30629.283 |
52,4−51,5 | 35295.199 |
51,5−40,4 | 35794.527 |
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.
References
- ^ a b 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.
- ^ Holleman, Arnold F.; Wiber, Egon; Wiberg, Nils, eds. (2001). "Oxides of sulfur". Inorganic Chemistry. Academic Press. p. 530. ISBN 9780123526519.
- ^ Mitchell, Stephen C. (2004). Biological Interactions Of Sulfur Compounds. CRC Press. p. 7. ISBN 9780203362525.
- ^ a b 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.
- ^ a b c 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.
- ^ a b 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.
- ^ 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.
- ^ a b 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.
- ^ Sahoo, Balaram; Nayak, Nimai Charan; Samantaray, Asutosh; Pujapanda, Prafulla Kumar (2012). Inorganic Chemistry. PHI Learning. p. 461. ISBN 9788120343085. Retrieved 2013-05-16.
- ^ 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.
- ^ a b 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.
- ^ "Rare molecule on Venus may help explain planet's weather". CBC News. Retrieved 2016-11-11.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ a b 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.
- ^ 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.
- ^ Clements, Todd G.; Hans-Jürgen Deyerl; Robert E. Continetti (2002). "Dissociative Photodetachment Dynamics of S
2O−
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.
- v
- t
- e
- Antimony tetroxide (Sb2O4)
- Boron suboxide (B12O2)
- Carbon suboxide (C3O2)
- Chlorine perchlorate (Cl2O4)
- Chloryl perchlorate (Cl2O6)
- Cobalt(II,III) oxide (Co3O4)
- Dichlorine pentoxide (Cl2O5)
- Iron(II,III) oxide (Fe3O4)
- Lead(II,IV) oxide (Pb3O4)
- Manganese(II,III) oxide (Mn3O4)
- Mellitic anhydride (C12O9)
- Praseodymium(III,IV) oxide (Pr6O11)
- Silver(I,III) oxide (Ag2O2)
- Terbium(III,IV) oxide (Tb4O7)
- Tribromine octoxide (Br3O8)
- Triuranium octoxide (U3O8)
- Aluminium(I) oxide (Al2O)
- Copper(I) oxide (Cu2O)
- Caesium monoxide (Cs2O)
- Dicarbon monoxide (C2O)
- Dichlorine monoxide (Cl2O)
- Gallium(I) oxide (Ga2O)
- Iodine(I) oxide (I2O)
- Lithium oxide (Li2O)
- Mercury(I) oxide (Hg2O)
- Nitrous oxide (N2O)
- Potassium oxide (K2O)
- Rubidium oxide (Rb2O)
- Silver oxide (Ag2O)
- Thallium(I) oxide (Tl2O)
- Sodium oxide (Na2O)
- Water (hydrogen oxide) (H2O)
- Aluminium(II) oxide (AlO)
- Barium oxide (BaO)
- Berkelium monoxide (BkO)
- Beryllium oxide (BeO)
- Bromine monoxide (BrO)
- Cadmium oxide (CdO)
- Calcium oxide (CaO)
- Carbon monoxide (CO)
- Chlorine monoxide (ClO)
- Chromium(II) oxide (CrO)
- Cobalt(II) oxide (CoO)
- Copper(II) oxide (CuO)
- Dinitrogen dioxide (N2O2)
- Europium(II) oxide (EuO)
- Germanium monoxide (GeO)
- Iron(II) oxide (FeO)
- Iodine monoxide (IO)
- Lead(II) oxide (PbO)
- Magnesium oxide (MgO)
- Manganese(II) oxide (MnO)
- Mercury(II) oxide (HgO)
- Nickel(II) oxide (NiO)
- Nitric oxide (NO)
- Palladium(II) oxide (PdO)
- Phosphorus monoxide (PO)
- Polonium monoxide (PoO)
- Protactinium monoxide (PaO)
- Radium oxide (RaO)
- Silicon monoxide (SiO)
- Strontium oxide (SrO)
- Sulfur monoxide (SO)
- Disulfur dioxide (S2O2)
- Thorium monoxide (ThO)
- Tin(II) oxide (SnO)
- Titanium(II) oxide (TiO)
- Vanadium(II) oxide (VO)
- Yttrium(II) oxide (YO)
- Zinc oxide (ZnO)
- Actinium(III) oxide (Ac2O3)
- Aluminium oxide (Al2O3)
- Americium(III) oxide (Am2O3)
- Antimony trioxide (Sb2O3)
- Arsenic trioxide (As2O3)
- Berkelium(III) oxide (Bk2O3)
- Bismuth(III) oxide (Bi2O3)
- Boron trioxide (B2O3)
- Caesium sesquioxide (Cs2O3)
- Californium(III) oxide (Cf2O3)
- Cerium(III) oxide (Ce2O3)
- Chromium(III) oxide (Cr2O3)
- Cobalt(III) oxide (Co2O3)
- Dinitrogen trioxide (N2O3)
- Dysprosium(III) oxide (Dy2O3)
- Einsteinium(III) oxide (Es2O3)
- Erbium(III) oxide (Er2O3)
- Europium(III) oxide (Eu2O3)
- Gadolinium(III) oxide (Gd2O3)
- Gallium(III) oxide (Ga2O3)
- Gold(III) oxide (Au2O3)
- Holmium(III) oxide (Ho2O3)
- Indium(III) oxide (In2O3)
- Iron(III) oxide (Fe2O3)
- Lanthanum oxide (La2O3)
- Lutetium(III) oxide (Lu2O3)
- Manganese(III) oxide (Mn2O3)
- Neodymium(III) oxide (Nd2O3)
- Nickel(III) oxide (Ni2O3)
- Phosphorus trioxide (P4O6)
- Praseodymium(III) oxide (Pr2O3)
- Promethium(III) oxide (Pm2O3)
- Rhodium(III) oxide (Rh2O3)
- Samarium(III) oxide (Sm2O3)
- Scandium oxide (Sc2O3)
- Terbium(III) oxide (Tb2O3)
- Thallium(III) oxide (Tl2O3)
- Thulium(III) oxide (Tm2O3)
- Titanium(III) oxide (Ti2O3)
- Tungsten(III) oxide (W2O3)
- Vanadium(III) oxide (V2O3)
- Ytterbium(III) oxide (Yb2O3)
- Yttrium(III) oxide (Y2O3)
- Americium dioxide (AmO2)
- Berkelium(IV) oxide (BkO2)
- Bromine dioxide (BrO2)
- Californium dioxide (CfO2)
- Carbon dioxide (CO2)
- Carbon trioxide (CO3)
- Cerium(IV) oxide (CeO2)
- Chlorine dioxide (ClO2)
- Chromium(IV) oxide (CrO2)
- Curium(IV) oxide (CmO2)
- Dinitrogen tetroxide (N2O4)
- Germanium dioxide (GeO2)
- Iodine dioxide (IO2)
- Hafnium(IV) oxide (HfO2)
- Lead dioxide (PbO2)
- Manganese dioxide (MnO2)
- Neptunium(IV) oxide (NpO2)
- Nitrogen dioxide (NO2)
- Osmium dioxide (OsO2)
- Plutonium(IV) oxide (PuO2)
- Polonium dioxide (PoO2)
- Praseodymium(IV) oxide (PrO2)
- Protactinium(IV) oxide (PaO2)
- Rhodium(IV) oxide (RhO2)
- Ruthenium(IV) oxide (RuO2)
- Selenium dioxide (SeO2)
- Silicon dioxide (SiO2)
- Sulfur dioxide (SO2)
- Technetium(IV) oxide (TcO2)
- Tellurium dioxide (TeO2)
- Terbium(IV) oxide (TbO2)
- Thorium dioxide (ThO2)
- Tin dioxide (SnO2)
- Titanium dioxide (TiO2)
- Tungsten(IV) oxide (WO2)
- Uranium dioxide (UO2)
- Vanadium(IV) oxide (VO2)
- Zirconium dioxide (ZrO2)
- Antimony pentoxide (Sb2O5)
- Arsenic pentoxide (As2O5)
- Bismuth pentoxide (Bi2O5)
- Dinitrogen pentoxide (N2O5)
- Niobium pentoxide (Nb2O5)
- Phosphorus pentoxide (P2O5)
- Protactinium(V) oxide (Pa2O5)
- Tantalum pentoxide (Ta2O5)
- Vanadium(V) oxide (V2O5)
- Chromium trioxide (CrO3)
- Molybdenum trioxide (MoO3)
- Polonium trioxide (PoO3)
- Rhenium trioxide (ReO3)
- Selenium trioxide (SeO3)
- Sulfur trioxide (SO3)
- Tellurium trioxide (TeO3)
- Tungsten trioxide (WO3)
- Uranium trioxide (UO3)
- Xenon trioxide (XeO3)
- Dichlorine heptoxide (Cl2O7)
- Manganese heptoxide (Mn2O7)
- Rhenium(VII) oxide (Re2O7)
- Technetium(VII) oxide (Tc2O7)
- Iridium tetroxide (IrO4)
- Osmium tetroxide (OsO4)
- Ruthenium tetroxide (RuO4)
- Xenon tetroxide (XeO4)
- Hassium tetroxide (HsO4)