氫硫基自由基

氫硫基自由基是一種自由基,具有一顆氫原子和一顆硫原子。

氫硫基自由基
系统名
Sulfanyl[1] (取代法)

Hydridosulfur(•)[1](加合法)

别名 λ1-Sulfane[2]
一氫化硫
识别
CAS号 13940-21-1  ✓
PubChem 5460613
ChemSpider 4574111
SMILES
InChI
InChIKey PXQLVRUNWNTZOS-UHFFFAOYSA-N
Gmelin 299
ChEBI 29312
性质
化学式 HS
摩尔质量 33.073 g mol−1 g·mol⁻¹
外观 黃色氣體[3]
溶解性 產生反應
热力学
ΔfHmo298K 139.33 kJ mol−1
So298K 195.63 J K−1 mol−1
相关物质
相关自由基 羥基自由基英语Hydroxyl radical
相关化学品 硫化氫

二硫化氫

若非注明,所有数据均出自一般条件(25 ℃,100 kPa)下。

產生编辑

於1939年加利福尼亞大學瑪格麗特·N·劉易斯及約翰·U·懷特首次發現其存在。[4]他們對硫化氫進行射頻放電以取得氫硫基自由基,[5]從中觀察到對應其2Σ+2Πi躍遷的325 nm吸收線

它亦可於硫化氫以紫外線產生,吸收峰值為190 nm波長的輻射。[6]

硫醇(如乙硫醇)的熱分解會產生氫硫基自由基。[7]其亦可由硫酸鈰(IV)氧化硫化氫離子(HS)產生。[8]

其在生物的代謝作用中對硫化氫的反應,如進行解毒時也會出現。人體中的SOD1酶英语SOD1可將HS轉為HS[9]硫酸鹽還原細菌中的黃色素c硫化物脫氫酶英语Flavocytochrome c sulfide dehydrogenase亦能催化硫化氫離子的氧化作用,移除電子並產生該自由基。[10]

當含硫礦物被三價鐵離子溶濾時會產生氫硫基自由基離子:

 

該離子其後便讓水吸收氫離子而成為氫硫基自由基。上述的M為一種金屬,例如銅或鋅。[11]此反應亦有發展以生物濾化提煉金屬礦物的潛在可能。

自然界的存在编辑

氫硫基自由基由山村一誠等首次於星際空間發現,他們在2000年發表其於仙女座R觀測到相關吸收線的文章。[12]它被觀測到的紫外譜線分別為:326.0459、327.5468、328.9749、330.0892及330.1112 nm。[13]

它預計是在氣態巨行星(如木星)及棕矮星存在的三大含硫氣體之一,[14]亦很可能於已冷卻恆星中存在。它已在星際氣體中探測到,[15]亦可能存在於彗星中。[16]

在地球的大氣層中亦有該自由基,由自然發生的(例如光分解作用[17])及由人為除臭引致的硫化氫降解形成。[18]另外,當地球大氣層中的羥基自由基英语Hydroxyl radical與硫化氫、二硫化碳羰基硫反應亦會產生氫硫基自由基、二氧化碳和水。這自由基在大氣層中有多種反應,如與NO2產生HSNO2及HSONO,後者分解為HSO及NO;亦會與氧氣及一氧化二氮反應。[19]其與氯氣反應會產生HSCl及Cl自由基;[20]與臭氧反應則產生HSO及氧。[21]

理論上在含有硫化氫的行星大氧層在足夠溫度及壓力下便能分解成自由基。在特定溫度及壓力下兩者比例為:

 

在一個以氫氣為主的氣態巨行星或恆星,在以下情況氫硫基自由基與硫化氫為同一水平:

 

而在更高溫度中自由基會分解成氣態硫及氫氣,在以下情況它與氣態硫為同一水平:

 .

這兩條方程會於1509 K及1.51 Pa處相交,在更低的度及壓力下該自由基被排除在外。[14]

特性编辑

氫硫基自由基中氫與硫的原子間距為0.134 nm。[22]電離能為10.4219 eV;[23]成為HS的還原電位為0.92 eV。[24]

正如其它自由基,它亦是頗活躍。它在水中可電離為S•−及H+,前者能催化脂類的順反變換;[25]但它亦與水中的氧氣反應產生SO2及H+,前者繼續與氧氣反應產生超氧離子二氧化硫[26]它與羧酸反應產生羰基硫,這更可能是地球大氣層中存在的羰基硫的最大源頭。[8]除此之外也包括與乙烯反應;與氧氣反應產生羥基自由基及一氧化硫;與自身反應成氫及硫,或二硫化氫[27]後者再與自由基反應產生硫化氫及二硫化一氫自由基。[11]

參考编辑

  1. ^ 1.0 1.1 sulfanyl (CHEBI:29312). Chemical entities of biological interest. UK: European Bioinformatics Institute. Main. 6 November 2006 [8 October 2011]. (原始内容存档于2017-12-27). 
  2. ^ Mercapto radical – Compound summary. PubChem Compound. USA: National Center for Biotechnology Information. Identification and related records. 16 September 2004 [12 October 2011]. 
  3. ^ Zahnle, Kevin; Mark S. Marley; R. S. Freedman; K. Lodders; J. J. Fortney. Atmospheric sulfur photochemistry on hot Jupiters. The Astrophysical Journal. 26 June 2009, 701 (1): L20–L24. Bibcode:2009ApJ...701L..20Z. arXiv:0903.1663v2 . doi:10.1088/0004-637X/701/1/L20. 
  4. ^ Lewis, Margaret; John U. White. The band spectrum of HS. Physical Review. 1939, 55 (10): 894–898. Bibcode:1939PhRv...55..894L. doi:10.1103/PhysRev.55.894. 
  5. ^ Harrison, Jeremy J.; Bryce E. Williamson. Magnetic circular dichroism of the mercapto radical in noble-gas matrices (PDF). Journal of the Indian Institute of Science. November 2005, 85: 391–402 [2019-11-30]. (原始内容 (PDF)存档于2012-04-15). 
  6. ^ Hollaender, Alexander; Livingston, Robert. 1. Radiation Biology. McGraw Hill. 1955: 27. 
  7. ^ Sehon, A. H.; B. deB. Darwent. The thermal decomposition of mercaptans. Journal of the American Chemical Society. October 1954, 76 (19): 4806. doi:10.1021/ja01648a011. 
  8. ^ 8.0 8.1 Pos, Willer H.; Daniel D. Riemer; Rod G. Zika. Carbonyl sulfide (OCS) and carbon monoxide (CO) in natural waters: evidence of a coupled production pathway. Marine Chemistry. 1998, 62 (1–2): 89–101. doi:10.1016/S0304-4203(98)00025-5. 
  9. ^ Lyons, Thomas J.; Edith Butler Gralla; Joan Selverstone Valentine. Biological chemistry of copper-zinc superoxide dismutase and its link to amyotrophic lateral sclerosis (PDF). Metal ions in biological systems (Basel, Switzerland: Marcel Decker Inc). 1999: 139 [10 October 2011]. ISBN 978-0-8247-1956-2. [永久失效連結]
  10. ^ Sorokina, Dimitry Yu; Govardus A.H de Jong; Lesley A. Robertson; Gijs J. Kuenen. Purification and characterization of sulfide dehydrogenase from alkaliphilic chemolithoautotrophic sulfur-oxidizing bacteria. FEBS Letters. 1 May 1998, 427 (1): 11–14. PMID 9613590. doi:10.1016/S0014-5793(98)00379-2. 
  11. ^ 11.0 11.1 Schippers, Axel; Wolfgang Sand. Bacterial leaching of metal sulfides proceeds by two indirect mechanisms via thiosulfate or via polysulfides and sulfur (PDF). Applied and Environmental Microbiology. January 1999, 65 (1): 319–321. PMC 91023 . PMID 9872800. 
  12. ^ Yamamura, Issei; Kawaguchi, K.; Ridgway, S. T. Identification of SH ∆v=1 Ro-vibrational Lines in R Andromedae. The Astrophysical Journal. 2000-1, 258 (1): L33–L36. doi:10.1086/312420. 
  13. ^ Sveta V. Berdyugina & W.C. Livingston. Detection of the mercapto radical SH in the solar atmosphere. Astronomy and Astrophysics. May 2002, 387: L6–L9. Bibcode:2002A&A...387L...6B. doi:10.1051/0004-6361:20020364. 
  14. ^ 14.0 14.1 Visscher, Channon; Katharina Lodders , and Bruce Fegley, Jr.; Fegley, Bruce. Atmospheric chemistry in giant planets, brown dwarfs, and low-mass dwarf stars. II. Sulfur and phosphorus. The Astrophysical Journal. 10 September 2006, 648 (2): 1181–1195. Bibcode:2006ApJ...648.1181V. arXiv:astro-ph/0511136 . doi:10.1086/506245. 
  15. ^ Palca, Joe. Flying telescope makes an out-of-this-world find. NPR. 1 October 2011 [8 October 2011]. (原始内容存档于2020-08-08). 
  16. ^ The cosmic ice laboratory – Cometary molecules. [2019-11-30]. (原始内容存档于2016-12-31). 
  17. ^ Furones, Maikel Yusat Ballester. A theoretical study on the HSO2 molecular system (PDF). Coimbra: Universidade de Coimbra: 1, 37. 2008 [20 October 2011]. (原始内容 (PDF)存档于2012-04-19). 
  18. ^ Mercado-Cabrera, Antonio; B. Jaramillo-Sierra; S.R. Barocio; R. Valencia-Alvarado; M. Pacheco-Pacheco; R. Peña-Eguiluz; R. Lopez-Callejas; A. Muñoz-Castro; A. De la Piedad-Beneitez. Environmental odour control by atmospheric dielectric barrier discharge (PDF). ISPC. 29 April 2009 [20 October 2011]. (原始内容存档 (PDF)于2013-09-27). 
  19. ^ Resende, Stella M. The atmospheric oxidation of the HS radical: Reaction with NO2. Journal of Atmospheric Chemistry. 2007, 56 (1): 21–32. Bibcode:2006JAtC...56...21R. doi:10.1007/s10874-006-9040-z. 
  20. ^ Resende, Stella M.; Fernando R Ornellas. Atmospheric reaction between the HS radical and chlorine. Chemical Physics Letters. 25 February 2000, 318 (4–5): 340–344. Bibcode:2000CPL...318..340R. doi:10.1016/S0009-2614(00)00019-1. 
  21. ^ Yoshimura, Yasunori; Toshio Kasai, Hiroshi Ohoyama and Keiji Kuwata; Ohoyama, Hiroshi; Kuwata, Keiji. Nascent HF + and HSO(2A') formations in the elementary reactions of F + H2S and HS + O3 and the internal energy distributions. Canadian Journal of Chemistry. 1995, 73 (2): 204–221. doi:10.1139/v95-029. 
  22. ^ Ellingson, Benjamin A.; Donald G. Truhlar. Explanation of the unusual temperature dependence of the atmospheric important OH + H2S → H2O + SH reaction and prediction of the rate constant at combustion temperatures (PDF). J. Am. Chem. Soc. 1 August 2007, 129 (42): 12765–12771 [12769] [20 October 2011]. PMID 17910447. doi:10.1021/ja072538b. (原始内容 (reprint)存档于2012-04-25). 
  23. ^ Cheng, B. M.; E. P. Chew, W. C. Hung, J. Eberhard and Y. P. Lee; Hung, Wen-Ching; Eberhard, Jürg; Lee, Yuan-Pern. Photoionization studies of sulfur radicals and products of their reactions (PDF). Journal of Synchrotron Radiation. May 1998, 5 (3): 1041–3. PMID 15263738. doi:10.1107/S0909049597016075. 
  24. ^ Das, T. N.; R. E. Huie; P. Neta; S. Padmaja. Reduction potential of the sulfhydryl radical: pulse radiolysis and laser flash photolysis studies of the formation and reactions of SH and HS–SH•− in aqueous solutions. The Journal of Physical Chemistry A. 11 June 1999, 103 (27): 5221–5226. Bibcode:1999JPCA..103.5221D. doi:10.1021/jp9907544. 
  25. ^ Lykakis, Ioannis N.; Carla Ferreri; Chryssostomos Chatgilialoglu. The sulfhydryl radical (HS/S•−): A contender for the isomerization of double bonds in membrane lipids. Angewandte Chemie. 19 January 2007, 46 (11): 1914–1916. PMID 17450618. doi:10.1002/anie.200604525. 
  26. ^ Fang, Hao Jie; Dong Wen Bo, Zhang Ren Xi and Hou, Hui Qi. 水相中·HS 的光谱表征及其与氧气的反应研究 [Spectrum ofHS and its reactions with oxygen in aqueous solution]. Acta Physico-Chimica Sinica. June 2006, 22 (6): 761–763 [12 October 2011]. doi:10.3866/PKU.WHXB20060623. (原始内容存档于2020-08-07) (中文). 
  27. ^ Tiee, J.J. Spectroscopy and reaction kinetics of HS radicals. Kinetics Database (NIST). 1981, 82 (1): 80–84 [13 October 2011]. Bibcode:1981CPL....82...80T. doi:10.1016/0009-2614(81)85111-1. (原始内容存档于2017-11-07).