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磷化氢

磷化氫
IUPAC名
Phosphane
别名
识别
CAS号 7803-51-2  checkY
PubChem 24404
ChemSpider 22814
SMILES
 
  • P
InChI
 
  • 1/H3P/h1H3
InChIKey XYFCBTPGUUZFHI-UHFFFAOYAP
Gmelin 287
UN编号 2199
EINECS 232-260-8
ChEBI 30278
RTECS SY7525000
性质
化学式 PH3
摩尔质量 34.00 g·mol⁻¹
外观 無色氣體
氣味 纯品无臭,有杂质时有鱼腥味或大蒜味[1]
密度 1.379 g/L(25 °C,气态)
熔点 -132.8 °C(140 K)
沸点 -87.7 °C(185 K)
溶解性 31.2 mg/100 ml(17 °C)
蒸氣壓 41.3 atm(20 °C)[1]
折光度n
D
2.144
黏度 1.1×10−5 Pa⋅s
结构
分子构型 三角錐體
偶极矩 0.58 D
热力学
ΔfHm298K 5 kJ/mol[2]
S298K 210 J/mol⋅K[2]
热容 37 J/mol⋅K
危险性
欧盟危险性符号
极易燃极易燃 F+
剧毒剧毒 T+
危害环境危害环境N
警示术语 R:R12-R17-R26-R34-R50
安全术语 S:S1/2-S28-S36/37-S45-S61-S63
GHS危险性符号
《全球化学品统一分类和标签制度》(简称“GHS”)中易燃物的标签图案 《全球化学品统一分类和标签制度》(简称“GHS”)中有毒物质的标签图案 《全球化学品统一分类和标签制度》(简称“GHS”)中腐蚀性物质的标签图案 《全球化学品统一分类和标签制度》(简称“GHS”)中对环境有害物质的标签图案
NFPA 704
4
4
2
 
闪点 可燃气体
自燃温度 38 °C
爆炸極限 1.79–98%[1]
PEL TWA 0.3 ppm(0.4 mg/m3[1]
致死量或浓度:
LD50中位剂量
3.03 mg/kg(大鼠,口服)
LC50中位浓度
11 ppm(大鼠,4小时)[3]
LCLo最低
1000 ppm(哺乳动物,5分钟)
270 ppm(小鼠,2小时)
100 ppm(豚鼠,4小时)
50 ppm(猫,2小时)
2500 ppm(兔子,20分钟)
1000 ppm(人类,5分钟)[3]
相关物质
相关氮族元素的氢化物
砷化氢
锑化氢
铋化氢
相关化学品 三甲基膦
三苯基膦
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

磷化氢又名[a],是无色、可燃、剧毒的气体,分子式PH
3
,属于氮族元素的氢化物。纯磷化氢无臭,但工业生产的磷化氢含有其它衍生物和联膦(P
2
H
4
)杂质,因此有很臭的腐烂鱼腥味。有痕量P
2
H
4
杂质的PH
3
在空气中会自燃,放出明亮的火焰。磷化氢有剧毒,浓度50 ppm时就会立即危及生命或健康英语immediately dangerous to life or health。它有三角锥形分子构型

历史

拉瓦锡的学生菲利普·冈冈布勒德语Philippe Gengembre于1783年通过在碳酸钾水溶液里加热白磷,首次合成磷化氢。[5][b]因为磷化氢和单质的关联,它曾被认为是气态磷,直到1789年拉瓦锡才发现它是磷和氢组成的化合物。[8]

1844年,法国化学家路易·雅克·泰纳尔的儿子保罗·泰纳尔德语Paul Thénard冷阱英语Cold trap磷化钙产生的磷化氢中分离出了联膦,发现它是PH
3
会自燃的原因。[9]

製取

磷化氢有多种制备方法。[10]工业上,磷化氢可以用白磷氢氧化钾氢氧化钠共热制取:[11]

3 KOH + P
4
+ 3 H
2
O → 3 KH
2
PO
2
+ PH
3
3 NaOH + P
4
+ 3 H
2
O → 3 NaH
2
PO
2
+ PH
3

实验室制法

实验室常通过亚磷酸在200 °C下的歧化产生磷化氢:[11]

4 H
3
PO
3
→ PH
3
+ 3 H
3
PO
4

它也可通过磷化钙与水反应产生:[11]

Ca
3
P
2
+ 6 H
2
O → 3 Ca(OH)
2
+ 2 PH
3

不含P
2
H
4
的纯磷化氢则可通过氢氧化钾碘化鏻的反应产生:[12]

[PH
4
]I + KOH → PH
3
+ KI + H
2
O

性質

磷化氢是无色、可燃、剧毒的气体,难溶于水,更易溶于二硫化碳非极性溶剂。PH
3
三角锥形分子构型分子对称性C3v。它的P−H键长为1.42 Å,H−P−H键角为93.5°偶极矩为0.58 D。[13]磷化氢的氢键弱。[14]

反应

磷化氢在水中呈两性。它既难以被质子化离子(PH+
4
),也难以去质子化成PH
2
离子,所以不管是酸性还是碱性都很弱。[13]

PH
3
+ H
2
O ⇌ PH
2
+ H
3
O+
Ka = 1.6×10−29
PH
3
+ H
2
O ⇌ PH+
4
+ OH
Kb = 4×10−28

盐酸可以质子化磷化氢,生成[PH
4
]+
Cl
,而液氨则可以去质子化磷化氢,生成[NH
4
]+
[PH
2
]
。磷化氫是路易斯鹼,可与BF3路易斯酸反应生成配合物。[13]

磷化氢还具有强还原性,可把多种金属化合物还原成金属单质,与PCl
5
反应则会得到PCl
3
[13]磷化氢在高温高压下与水反应,生成磷酸和氢气:[15][16]

PH
3
+ 4H
2
O 高温高压H
3
PO
4
+ 4H
2

磷化氢在超过600℃时才会分解为氢气,但催化剂可降低分解温度:[17]

4 PH
3
→ P
4
+ 6 H
2

磷化氢在空气中燃烧,生成五氧化二磷 (P2O5),后者与水反应生成磷酸[18][15]

2 PH
3
+ 4 O
2
→ P
2
O
5
+ 3 H
2
O
P
2
O
5
+ 3 H
2
O → 2 H
3
PO
4

总反应如下:

PH
3
+ 2 O
2
→ H
3
PO
4

存在

磷化氢在地球大气层中的浓度极低且多变。[19]这些磷化氢最有可能来自生物分解中磷酸盐还原。由于自然界中没有足以直接把磷酸盐还原成磷化氢的强还原剂,所以它们应该是通过多步还原及歧化反应产生的。[20]有机物分解过程产生的磷化氢自燃时,便会产生鬼火[20]

磷化氢也存在于木星的大气层中。[21]2020年有报告称通过光谱分析发现金星大气层中的磷化氢含量多到无法用非生物因子解释,[22][23][24]不过后来重新分析该研究时发现有插值错误,用已修正的算法重新分析数据后发现并没有在金星大气层中探测到磷化氢。[25][26]

应用

合成有机磷化合物

磷化氢是合成多种有机磷化合物的前体。它和甲醛在氯化氢存在下反应,生成四羟甲基氯化𬭸[27]它可通过氢膦化反应英语hydrophosphination加成到双键上产生膦,例如和丙烯腈反应生成三(氰乙基)膦[28]

PH
3
+ 3 CH
2
=CHCN → P(CH
2
CH
2
CN)
3

在酸催化下,磷化氢可与异丁烯反应:[28]

PH
3
+ (CH
3
)
2
C=CH
2
→ (CH
3
)
3
CPH
2

此外,磷化氢和醛在加热下(100℃)可得到叔膦化合物:[29]

PH
3
+ 3 RCHO → (RCH(OH))
3
P

半导体工业

磷化氢在半导体工业中用作掺杂剂[30]

熏蒸剂

磷化铝(AlP)、磷化镁Mg
3
P
2
)、磷化锌Zn
3
P
2
)、磷化二氢钠NaPH
2
[31]会和空气中的水蒸气反应生成磷化氢,这一特性使其被用作粮食仓库的熏蒸剂英语Fumigant[32][33]它们和老鼠的胃酸反应也能产生磷化氢,从而毒死老鼠。[34]

毒性及危害

磷化氢是剧毒气体,可通过吸入皮肤吸收英语transdermal进入人体。[35]它会导致氧化应激、影响线粒体[36]和氧气的运输,以及干扰各种细胞使用氧气。[37]磷化氢主要影响呼吸道,[38]中毒的症状包括恶心、呕吐、腹痛、腹泻、口渴、胸闷、呼吸困难、肌肉痛、发冷、木僵、晕厥、肺水肿[39][40][41]没有解药。[42]目前已有意外接触含磷化铝或磷化氢的熏蒸剂而死的案例。[35][43][37][39]磷化氢气体比空气重,会聚集在地面。[44]

美国职业安全与健康管理局英语Occupational Safety and Health Administration(OSHA)把磷化氢的允许暴露极限英语Permissible exposure limit设为0.3 ppm,美国国家职业安全卫生研究所(NIOSH)设的建议暴露极限英语Recommended exposure limit同为这个值。磷化氢浓度达到50 ppm时就会立即危及生命或健康英语immediately dangerous to life or health[1]空气中微量的磷化氢可用硝酸银检测出来。[42]

爆炸性

磷化氢气体比空气重,会聚集在地面。它会和空气形成爆炸性混合物,也有可能自燃。[15]

大众文化

在《绝命毒师》的试播集中,沃尔特·怀特通过在沸水中加红磷产生磷化氢,使两个人中毒。现实中该反应要加的不是红磷而是白磷,而且水中要有氢氧化钠[45]

注释

  1. ^ 也指磷化氢分子中的氢原子部分或全部被烃基取代的一切衍生物,如甲膦[4]
  2. ^ 磷化氢早期历史的更多信息可见[6][7]

参考资料

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  5. ^ 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.
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SMA Negeri 17 JakartaInformasiDidirikan16 Oktober 1966JenisNegeriAkreditasiAKepala SekolahDrs. Hardi Kusdiat, M.SiJurusan atau peminatanIPA dan IPSRentang kelasX IPA, X IPS, XI IPA, XI IPS, XII IPA, XII IPSKurikulumKurikulum Tingkat Satuan PendidikanAlamatLokasiJl. Mangga Besar IV I No.27, RT.3/RW.1, Kota Tua, Taman Sari, 11150, Jakarta Barat, DKI JakartaTel./Faks.(021)6392046Situs webhttp://sman17jkt.sch.id/Surelsma17.jakarta@gmail.com info@sman17jkt.sch.idMoto SMA Negeri (SMAN) 17 Ja…

Arcadian nymph – daughter of Pan and Echo Detail of an earring showing a figure of Eros holding an iynx toy. Created in Northern Greece, c. 330–300 BC[1] In Greek mythology, Iynx (Greek: Ἴϋγξ, translit. Íÿnx) was an Arcadian Oread nymph; a daughter of the god Pan and Echo. In popular myth, she used an enchantment to cast a spell on Zeus, which caused him to fall in love with Io. In consequence of this, Hera metamorphosed her into the bird called iynx (Eurasian wryne…

Bagian dari seri artikel mengenaiPerang Sejarah Prasejarah Kuno Abad pertengahan Modern awal Industri Modern Perang generasi keempat Ruang pertempuran Udara Dunia maya Informasi Antariksa Darat Wilayah dingin Gurun Hutan Gunung Perkotaan Bawah tanah Laut Amfibi Biru Cokelat Hijau Permukaan Bawah air Siber Informasi Senjata Lapis baja Artileri Biologi Kavaleri Kimia Konvensional Dunia maya Elektronik Infanteri Nuklir Psikologi Nonkonvensional Taktik Udara Pertempuran Kavaleri Serbuan Serangan bal…

Hubungan Brasil–Jepang Brasil Jepang Tanda persahabatan di Maringa, Brasil Distrik Liberdade, São Paulo adalah kota Jepang terbesar di dunia. Hubungan Brasil–Jepang merujuk kepada hubungan bilateral Brasil dan Jepang. Jepang pertama kali membangun hubungan diplomatik dengan Brasil pada 1895.[1] Jepang menggunakan hubungan luar negeri untuk mempromosikan perdagangannya dengan Brasil setelah PD2.[2] Investasi langsung digunakan untuk mengembangkan bisnis di Brasil.[3] …

Australian politician The HonourableIan RobinsonOAMMember of the Australian Parliamentfor CowperIn office30 November 1963 – 1 December 1984Preceded byFrank McGurenSucceeded byGarry NehlMember of the Australian Parliamentfor PageIn office1 December 1984 – 24 March 1990Preceded byNew seatSucceeded byHarry Woods Personal detailsBorn(1925-03-25)25 March 1925Coraki, New South WalesDied23 March 2017(2017-03-23) (aged 91)Grafton, New South WalesNationalityAustralianPolitical …

1999 novel by Jonathan Lethem For the film based on the novel, see Motherless Brooklyn (film). This article needs a plot summary. Please add one in your own words. (February 2021) (Learn how and when to remove this template message) Motherless Brooklyn AuthorJonathan LethemCountryUnited StatesLanguageEnglishGenreDetective novelPublisherDoubledayPublication date1999Media typePrintISBN0-385-49183-2OCLC40723751Dewey Decimal813.54 21LC ClassPS3562.E8544 M68 1999 Motherless Brooklyn is a no…

Pour les articles homonymes, voir Alain, Émile Chartier et Chartier. AlainNaissance 3 mars 1868Mortagne-au-PercheDécès 2 juin 1951 (à 83 ans)Le VésinetSépulture Cimetière du Père-Lachaise, Grave of Alain (d)Nationalité françaiseFormation École normale supérieureLycée Pierre-CorneilleInfluencé par Jules Lagneau, René Descartes, Emmanuel Kant, Platon, Aristote, Auguste Comte, Georg Wilhelm Friedrich Hegel, Baruch SpinozaAdjectifs dérivés alinien[1]Distinctions Concours géné…

American college football season 2017 Columbia Lions footballConferenceIvy LeagueRecord8–2 (5–2 Ivy)Head coachAl Bagnoli (3rd season)Offensive coordinatorMark Fabish (2nd season)Defensive coordinatorPaul Ferraro (3rd season)Home stadiumRobert K. Kraft Field at Lawrence A. Wien StadiumSeasons← 20162018 → 2017 Ivy League football standings vte Conf Overall Team   W   L     W   L   No. 24 Yale $   6 – 1   &#…

Questa voce sull'argomento calciatori argentini è solo un abbozzo. Contribuisci a migliorarla secondo le convenzioni di Wikipedia. Segui i suggerimenti del progetto di riferimento. Jerónimo Barrales Nazionalità  Argentina Altezza 186 cm Peso 82 kg Calcio Ruolo Attaccante Squadra  Kalamata Carriera Squadre di club1 2007-2009 Banfield20+ (10)2009-2010 Recreativo Huelva29 (2)2010 Banfield14 (0)2011→  Santiago Wanderers14 (4)2011-2012 Unión27 (2)2012-201…

Lilith, 1887 by John Collier To Sumerians, Babylonians, Assyrians, and Jews there were male and female demons (Jewish demons were mostly male, although female examples such as Lilith exist). In Christian demonology and theology there is debate over the gender and sexual proclivities of demons. These questions are referenced in Italian,[a] French,[b] Spanish and Portuguese phrases that imply that the question is pointless and unanswerable, akin to the English phrase How many angel…

Questa voce sull'argomento centri abitati dell'Illinois è solo un abbozzo. Contribuisci a migliorarla secondo le convenzioni di Wikipedia. Segui i suggerimenti del progetto di riferimento. Evanstoncity(EN) Evanston, Illinois Evanston – VedutaCentro cittadino LocalizzazioneStato Stati Uniti Stato federato Illinois ConteaCook AmministrazioneSindacoElizabeth Tisdahl TerritorioCoordinate42°02′28.11″N 87°41′24.21″W / 42.041141°N 87.690059°W42.041141; -87.6…

Si ce bandeau n'est plus pertinent, retirez-le. Cliquez ici pour en savoir plus. Cet article concernant le catch doit être recyclé (décembre 2009). Une réorganisation et une clarification du contenu paraissent nécessaires. Améliorez-le, discutez des points à améliorer ou précisez les sections à recycler en utilisant {{section à recycler}}. Nikolai VolkoffNikolai Volkoff en 2009.Données généralesNom de naissance Josip Nikolai PeruzovićNom de ring Bepo MongolNikolai VolkoffNationali…

Thermodynamic cycle ThermodynamicsThe classical Carnot heat engine Branches Classical Statistical Chemical Quantum thermodynamics Equilibrium / Non-equilibrium Laws Zeroth First Second Third Systems Closed system Open system Isolated system State Equation of state Ideal gas Real gas State of matter Phase (matter) Equilibrium Control volume Instruments Processes Isobaric Isochoric Isothermal Adiabatic Isentropic Isenthalpic Quasistatic Polytropic Free expansion Reversibility Irreversibil…

Art museum in Miami and Washington, D.C. Rubell MuseumFormer nameRubell Family CollectionEstablished1993 (1993)LocationMiami, Florida, and Washington, D.C.TypeArt museumCollectionsContemporary artCollection size7400FounderDon and Mera RubellDirectorJuan Roselione-ValadezArchitectSelldorf Architects (Miami)Beyer Blinder Belle (Washington, D.C.)Websiterubellmuseum.org The Rubell Museum, formerly the Rubell Family Collection, is a private contemporary art museum with locations in the Allapatta…

Islamist campaign of the Iraqi Ba'ath party Izzat al-Douri, supervisor of the Faith Campaign The Faith Campaign (Arabic: الحملة الايمانية, romanized: al-Ḥamla al-Īmāniyya) was an Islamist campaign conducted by the Iraqi Ba'ath Party, beginning in 1993. The campaign involved a variety of policies, including greater freedoms being granted to Islamist groups, greater resources being put into religious programmes, increased use of Islamic punishments, and a greater emphasis b…

American singer and actor (born 1969) Donnie WahlbergWahlberg in 2010BornDonald Edmond Wahlberg Jr. (1969-08-17) August 17, 1969 (age 54)Boston, Massachusetts, U.S.OccupationsSingersongwriteractorrecord producerfilm producerYears active1984–presentSpouses Kim Fey ​ ​(m. 1999; div. 2008)​ Jenny McCarthy ​ ​(m. 2014)​ Children2RelativesMark Wahlberg (brother) Rhea Durham (sister-in-law) Robert Wahlberg (…

Belgian footballer (born 2005) Arthur Vermeeren Vermeeren with Royal Antwerp in 2023Personal informationFull name Arthur Denis Vermeeren[1]Date of birth (2005-02-07) 7 February 2005 (age 19)[1]Place of birth Lier, BelgiumHeight 1.80 m (5 ft 11 in)[2]Position(s) MidfielderTeam informationCurrent team Atlético MadridNumber 18Youth career2018–2022 Royal AntwerpSenior career*Years Team Apps (Gls)2022 Royal Antwerp II 6 (1)2022–2024 Royal Antwerp 47 (2…

Douglas Claude Strathern EvillAir Marshal Sir Douglas Evill tahun 1943Lahir(1892-10-08)8 Oktober 1892Broken Hill, New South Wales, AustraliaMeninggal22 Maret 1971(1971-03-22) (umur 78)Winchester, Hampshire, InggrisPengabdianBritania RayaDinas/cabangRoyal Navy (1910–1918)Royal Air Force (1918–1947)Lama dinas1910–1947PangkatAir Chief MarshalKomandanWakil Kepala Staf Udara (1943–1946)Skuadron RAF No. 70 (1923–1925)Skuadron RNAS No. 202 (1916–1917)Perang/pertempuranPerang Dunia…

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