Germane

Germane has been detected in the atmosphere of Jupiter.{{cite journal | title = The tropospheric gas composition of Jupiter's north equatorial belt (NH₃, PH₃, CH₃D, GeH₄, H₂O) and the Jovian D/H isotopic ratio |author1=Kunde, V. |author2=Hanel, R. |author3=Maguire, W. |author4=Gautier, D. |author5=Baluteau, J. P. |author6=Marten, A. |author7=Chedin, A. |author8=Husson, N. |author9=Scott, N. | journal = Astrophysical Journal | volume = 263 | year = 1982 | pages = 443–467 | doi = 10.1086/160516 | bibcode = 1982ApJ...263..443K }}

Germane is typically prepared by reduction of germanium oxides, notably germanates, with hydride reagents such as sodium borohydride, potassium borohydride, lithium borohydride, lithium aluminium hydride, sodium aluminium hydride. The reaction with borohydrides is catalyzed by various acids and can be carried out in either aqueous or organic solvent. On laboratory scale, germane can be prepared by the reaction of Ge(IV) compounds with these hydride reagents.W. L. Jolly "Preparation of the Volatile Hydrides of Groups IVA and VA by Means of Aqueous Hydroborate" Journal of the American Chemical Society 1961, volume 83, pp. 335-7.{{Cite web |url=http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&p=1&u=%2Fnetahtml%2FPTO%2Fsearch-bool.html&r=1&f=G&l=50&co1=AND&d=PTXT&s1=russotti.INNM.&s2=germane.TI.&OS=IN/russotti+AND+TTL/germane&RS=IN/russotti+AND+TTL/germane |title=US Patent 4,668,502 |access-date=2008-10-22 |archive-date=2017-07-14 |archive-url=https://web.archive.org/web/20170714100501/http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&p=1&u=%2Fnetahtml%2FPTO%2Fsearch-bool.html&r=1&f=G&l=50&co1=AND&d=PTXT&s1=russotti.INNM.&s2=germane.TI.&OS=IN/russotti+AND+TTL/germane&RS=IN/russotti+AND+TTL/germane |url-status=dead }} A typical synthesis involved the reaction of sodium germanate with potassium borohydride.{{ cite book |author1=Girolami, G. S. |author2=Rauchfuss, T. B. |author3=Angelici, R. J. | title = Synthesis and Technique in Inorganic Chemistry | publisher = University Science Books | location = Mill Valley, CA | year = 1999 }}

:NaHGeO₃ + KBH₄ + H₂O → KGeH₃ + KB(OH)₄

: KGeH₃ + HO₂CCH₃ → GeH₄ + KO₂CCH₃

Other methods for the synthesis of germane include electrochemical reduction and a plasma-based method.[http://www.freepatentsonline.com/7087102.html US Patent 7,087,102 (2006)] The electrochemical reduction method involves applying voltage to a germanium metal cathode immersed in an aqueous electrolyte solution and an anode counter-electrode composed of a metal such as molybdenum or cadmium. In this method, germane and hydrogen gases evolve from the cathode while the anode reacts to form solid molybdenum oxide or cadmium oxides. The plasma synthesis method involves bombarding germanium metal with hydrogen atoms (H) that are generated using a high frequency plasma source to produce germane and digermane.

Germane is weakly acidic. In liquid ammonia GeH₄ is ionised forming NH₄⁺ and GeH₃⁻.{{Greenwood&Earnshaw}} With alkali metals in liquid ammonia GeH₄ reacts to give white crystalline MGeH₃ compounds. The potassium (potassium germyl or potassium trihydrogen germanide KGeH₃) and rubidium compounds (rubidium germyl or rubidium trihydrogen germanide RbGeH₃) have the sodium chloride structure implying a free rotation of the trihydrogen germanide anion GeH₃⁻, the caesium compound, caesium germyl or caesium trihydrogen germanide CsGeH₃ in contrast has the distorted sodium chloride structure of TlI.

The gas decomposes near 600K (327°C; 620°F) to germanium and hydrogen. Because of its thermal lability, germane is used in the semiconductor industry for the epitaxial growth of germanium by MOVPE or chemical beam epitaxy.{{cite journal | title = Epitaxy of germanium using germane in the presence of tetramethylgermanium |author1=Venkatasubramanian, R. |author2=Pickett, R. T. |author3=Timmons, M. L. | journal = Journal of Applied Physics | year = 1989 | volume = 66 | issue = 11 | pages = 5662–5664 | doi = 10.1063/1.343633 | bibcode = 1989JAP....66.5662V }} Organogermanium precursors (e.g. isobutylgermane, alkylgermanium trichlorides, and dimethylaminogermanium trichloride) have been examined as less hazardous liquid alternatives to germane for deposition of Ge-containing films by MOVPE.{{cite journal | author = Woelk, E. | author2 = Shenai-Khatkhate, D. V. | author3 = DiCarlo, R. L. Jr. | author4 = Amamchyan, A. | author5 = Power, M. B. | author6 = Lamare, B. | author7 = Beaudoin, G. | author8 = Sagnes, I. | title = Designing Novel Organogermanium MOVPE Precursors for High-purity Germanium Films | journal = Journal of Crystal Growth | year = 2006 | volume = 287 | issue = 2 | pages = 684–687 | doi = 10.1016/j.jcrysgro.2005.10.094 | bibcode = 2006JCrGr.287..684W }}

Germane is a highly flammable, potentially pyrophoric,Brauer, 1963, Vol.1, 715 and a highly toxic gas. In 1970, the American Conference of Governmental Industrial Hygienists (ACGIH) published the latest changes and set the occupational exposure threshold limit value at 0.2 ppm for an 8-hour time weighted average.[http://www.praxair.com/praxair.nsf/AllContent/9ACB6769F6CDBEE785257258006F2F39/$File/p4821e.pdf Praxair MSDS] {{Webarchive|url=https://web.archive.org/web/20120508124813/http://www.praxair.com/praxair.nsf/AllContent/9ACB6769F6CDBEE785257258006F2F39/$File/p4821e.pdf |date=2012-05-08 }} accessed Sep. 2011

The LC50 for rats at 1 hour of exposure is 622 ppm.[https://www.cdc.gov/niosh-rtecs/LY4AC4A0.html#VCVN1 NIOSH Germane] Registry of Toxic Effects of Chemical Substances (RTECS)accessed Sep. 2011 Inhalation or exposure may result in malaise, headache, dizziness, fainting, dyspnea, nausea, vomiting, kidney injury, and hemolytic effects.{{ cite journal | author = Gus'kova, E. I. | title = K toksikologii Gidrida Germaniia |trans-title=Toxicology of germanium hydride | language = Russian | journal = Gigiena Truda I Professionalnye Zabolevaniia | year = 1974 | volume = 18 | issue = 2 | pages = 56–57 | pmid = 4839911 }}[http://www.epa.gov/oppt/aegl/pubs/germane_interim_sep_09_v1.pdf US EPA Germane]{{ cite journal |author1=Paneth, F. |author2=Joachimoglu, G. | title = Über die pharmakologischen Eigenschaften des Zinnwasserstoffs und Germaniumwasserstoffs |trans-title=About the pharmacological characteristics of tin hydride and germanium hydride | language = German | journal = Berichte der Deutschen Chemischen Gesellschaft | year = 1924 | volume = 57 | issue = 10 | pages = 1925–1930 | doi = 10.1002/cber.19240571027 }}

The US Department of Transportation hazard class is 2.3 Poisonous Gas.

{{Reflist|30em}}

{{Wiktionary}}

• [http://www.metaloids.com/docs/ger_msds.pdf Metaloids (manufacturer) datasheet]
• [http://www.arkonic.com/products_download/Electronic_Gases/GERMANE_GeH4.pdf Arkonic Specialty Gases China (manufacturer) datasheet]
• [http://www.licenz.ru/eng/tech_german_en.html Licensintorg Russia (process technology sale)] {{Webarchive|url=https://web.archive.org/web/20130329035747/http://www.licenz.ru/eng/tech_german_en.html |date=2013-03-29 }}
• [http://www.honjo-chem.co.jp/e_naoshima.html Honjo Chemical Japan (manufacturer)] {{Webarchive|url=https://web.archive.org/web/20130120083034/http://www.honjo-chem.co.jp/e_naoshima.html |date=2013-01-20 }}
• [https://web.archive.org/web/20110715111928/http://www.praxair.com/praxair.nsf/0/de34b22763a901058525650700148c9e/$FILE/Geh4.pdf Praxair datasheet]
• [http://encyclopedia.airliquide.com/Encyclopedia.asp?GasID=31 Air liquide gas encyclopedia entry] {{Webarchive|url=https://web.archive.org/web/20130730113158/http://encyclopedia.airliquide.com/Encyclopedia.asp?GasID=31 |date=2013-07-30 }}
• [https://www.cdc.gov/niosh/npg/npgd0300.html CDC - NIOSH Pocket Guide to Chemical Hazards]
• [http://www.voltaix.com/images/doc/Msge000_Germane.pdf Voltaix (manufacturer) datasheet] {{Webarchive|url=https://web.archive.org/web/20110717231149/http://www.voltaix.com/images/doc/Msge000_Germane.pdf |date=2011-07-17 }}
• [http://www.cccme.org.cn/products/detail-8081589.aspx Foshan Huate Gas Co., Ltd. (manufacturer)]
• [http://horst.ru/english.php Horst Technologies, Russia (manufacturer)]

{{Germanium compounds}}

{{Hydrides by group}}

Category:Germanium(IV) compounds

Category:Metal hydrides

Category:Industrial gases

Category:Pyrophoric materials