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|Section2= |Section3= |Section4= |Section7= |Section8= }} Phosphine (IUPAC name: phosphane) is the compound with the chemical formula PH3. It is a colorless, flammable, toxic gas. Pure phosphine is odorless, but ''technical grade'' samples have a highly unpleasant odor like garlic or rotting fish, due to the presence of substituted phosphine and diphosphane (P2H4). With traces of P2H4 present, PH3 is spontaneously flammable in air, burning with a luminous flame. Phosphines are also a group of organophosphorus compounds with the formula R3P (R = organic derivative). Organophosphines are important in catalysts where they complex to various metal ions; complexes derived from a chiral phosphine can catalyze reactions to give chiral, enantioenriched products. ==History== Philippe Gengembre (1764-1838), a student of Lavoisier, first obtained phosphine in 1783 by heating phosphorus in an aqueous solution of potash (potassium carbonate).〔Gengembre (1783) ("Mémoire sur un nouveau gas obtenu, par l'action des substances alkalines, sur le phosphore de Kunckel" ) (Memoir on a new gas obtained by the action of alkaline substances on Kunckel's phosphorus), ''Mémoires de mathématique et de physique'', 10 : 651-658.〕〔For further information about the early history of phosphine, see: * ''The Encyclopaedia Britannica'' (1911 edition), vol. 21, p. 480: (Phosphorus: Phosphine. ) * Thomas Thomson, ''A System of Chemistry'', 6th ed. (London, England: Baldwin, Cradock, and Joy, 1820), vol. 1 , (p. 272. )〕 Perhaps because of its strong association with elemental phosphorus, phosphine was once regarded as a gaseous form of the element, but Lavoisier (1789) recognised it as a combination of phosphorus with hydrogen and described it as ''phosphure d'hydrogène'' (phosphide of hydrogen).〔Note: * (On p. 222 ) of his ''Traité élémentaire de chimie'' … , vol. 1, (Paris, France: Cuchet, 1789), Lavoisier calls the compound of phosphorus and hydrogen ''"phosphure d'hydrogène"'' (hydrogen phosphide). However, (on p. 216 ), he calls the compound of hydrogen and phosphorus ''"Combinaison inconnue."'' (unknown combination), yet in a footnote, he says about the reactions of hydrogen with sulfur and with phosphorus: ''"Ces combinaisons ont lieu dans l'état de gaz & il en résulte du gaz hydrogène sulfurisé & phosphorisé."'' (These combinations occur in the gaseous state, and there results from them sulfurized and phosphorized hydrogen gas.) * In Robert Kerr's 1790 English translation of Lavoisier's ''Traité élémentaire de chimie'' … — namely, Lavoisier with Robert Kerr, trans., ''Elements of Chemistry'' … (Edinburgh, Scotland: William Creech, 1790) — Kerr translates Lavoisier's ''"phosphure d'hydrogène"'' as "phosphuret of hydrogen" ((p. 204 )), and whereas Lavoisier — on p. 216 of his ''Traité élémentaire de chimie'' … — gave no name to the combination of hydrogen and phosphorus, Kerr calls it "hydruret of phosphorus, or phosphuret of hydrogen" ((p. 198 )). Lavoisier's note about this compound — ''"Combinaison inconnue."'' — is translated: "Hitherto unknown." Lavoisier's footnote is translated as: "These combinations take place in the state of gas, and form, respectively, sulphurated and phosphorated oxygen gas." The word "oxygen" in the translation is an error because the original text clearly reads ''"hydrogène"'' (hydrogen). (The error was corrected in subsequent editions.)〕 In 1844, Paul Thénard, son of the French chemist Louis Jacques Thénard, used a cold trap to separate diphosphine from phosphine that had been generated from calcium phosphide, thereby demonstrating that P2H4 is responsible for spontaneous flammability associated with PH3, and also for the characteristic orange/brown color that can form on surfaces, which is a polymerisation product.〔Paul Thénard (1844) ("Mémoire sur les combinaisons du phosphore avec l'hydrogène" ) (Memoir on the compounds of phosphorus with hydrogen), ''Comptes rendus'', 18 : 652-655.〕 He considered diphosphine’s formula to be PH2, and thus an intermediate between elemental phosphorus, the higher polymers, and phosphine. Calcium phosphide (nominally Ca3P2) produces more P2H4 than other phosphides because of the preponderance of P-P bonds in the starting material. The name "phosphine" first appeared in combined form in 1857.〔In 1857, August Wilhelm von Hofmann announced the synthesis of organic compounds containing phosphorus, which he named "trimethylphosphine" and "triethylphosphine", in analogy with "amine" (organo-nitrogen compounds), "arsine" (organo-arsenic compounds), and "stibine" (organo-antimony compounds). See: A.W. Hofmann and Auguste Cahours (1857) ("Researches on the phosphorus bases," ) ''Proceedings of the Royal Society of London'', 8 : 523-527. From page 524: "The bases Me3P and E3P, the products of this reaction, which we propose to call respectively trimethylphosphine and triethylphosphine, … "〕 The gas PH3 was named "phosphine" by 1865 (or earlier).〔William Odling, ''A Course of Practical Chemistry Arranged for the Use of Medical Students'', 2nd ed. (London, England: Longmans, Green, and Co., 1865), (pp. 227 ), 230.〕 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「phosphine」の詳細全文を読む スポンサード リンク
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