铼:修订间差异
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{{NoteTA |
{{NoteTA |
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|G1= |
|G1 = Chemistry |
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|G2 = Unit |
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{{CJK-New-Char|28A0F|2CB5B}} |
{{CJK-New-Char|28A0F|2CB5B}} |
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{{全局僻字|𬭛|⿰钅波|𨨏|⿰金波}} |
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{{Elementbox |
{{Elementbox |
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|name=铼 |
|name=铼 |
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|right=[[鋨]] |
|right=[[鋨]] |
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|above=[[锝]] |
|above=[[锝]] |
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|below=[[𨨏]] |
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|below=[[𨨏|-{zh-hans:{{僻字|𬭛|左“钅”右“波”}}; zh-hant:{{僻字|𨨏|左「金」右「波」}};}-]] |
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|series=過渡金屬 |
|series=過渡金屬 |
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|period=6 |
|period=6 |
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|image name=Rhenium_single_crystal_bar_and_1cm3_cube.jpg |
|image name=Rhenium_single_crystal_bar_and_1cm3_cube.jpg |
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|appearance=銀白色 |
|appearance=銀白色 |
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|atomic mass=186.207 |
|atomic mass=186.207(1){{CIAAW2021}} |
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|electron configuration=[[[氙|Xe]]] 4f<sup>14</sup> 5d<sup>5</sup> 6s<sup>2</sup> |
|electron configuration=[[[氙|Xe]]] 4f<sup>14</sup> 5d<sup>5</sup> 6s<sup>2</sup> |
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|electrons per shell=2, 8, 18, 32, 13, 2 |
|electrons per shell=2, 8, 18, 32, 13, 2 |
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|vapor pressure comment= |
|vapor pressure comment= |
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|crystal structure=六方密堆積 |
|crystal structure=六方密堆積 |
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|oxidation states=''' |
|oxidation states=−3、−1、[[十羰基二铼|0]]、+1、+2、+3、'''+4'''、+5、+6、'''+7'''<ref>{{Greenwood&Earnshaw|page=28}}</ref><br />(弱[[酸性]]氧化物) |
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|electronegativity=1.9 |
|electronegativity=1.9 |
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|number of ionization energies=4 |
|number of ionization energies=4 |
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|Brinell hardness=1320 |
|Brinell hardness=1320 |
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|CAS number=7440-15-5 |
|CAS number=7440-15-5 |
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|isotopes= |
|isotopes={{infobox rhenium isotopes}} |
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{{Elementbox_isotopes_stable|mn=185|sym=Re|na=37.4%|n=110}} |
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{{Elementbox_isotopes_decay|mn=187|sym=Re |
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|na=62.6%|hl=4.12×10<sup>10</sup>年 |
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|dm1={{衰變|α}}|de1=1.653|pn1=183|ps1=鉭 |
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|dm2={{衰變|β-}}|de2=0.0026|pn2=187|ps2=鋨}} |
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|isotopes comment= |
|isotopes comment= |
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|discovered by=[[小川正孝]] |
|discovered by=[[小川正孝]] |
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|named date=1922 |
|named date=1922 |
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⚫ | '''{{zy|錸|lái|ㄌㄞˊ|loi4}}'''({{lang-en|Rhenium}};源于{{lang-la|Rhenus}}),是一種[[化學元素]],其[[化學符號]]为'''{{化學式|錸}}''',[[原子序數]]为75,[[原子量]]為{{val|186.207|u=[[原子質量單位|u]]}}。錸是種銀白色的[[重金屬]],在[[元素週期表]]中屬於[[第6週期元素|第6週期]][[過渡金屬]]。它是地球[[地殼]]中最稀有的元素之一,平均含量估值為十億分之一,同時也是熔點和沸點最高的元素之一。錸是[[鉬]]和[[銅]]提煉過程的副產品。其[[化學性質]]與[[錳]]和[[鍀]]相似,在[[化合物]]中的[[氧化態]]最低可達−3,最高可達+7。 |
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早在1908年,{{link-ja|小川正孝|小川正孝}}就发现了铼,但他错误将其当作43号元素。[[沃爾特·諾達克]]、[[伊達·諾達克]]、[[奧托·伯格]]于1925年重新發現了它,<ref>{{Cite journal |date=1925-06-01 |title=Die Ekamangane |url=https://doi.org/10.1007/BF01558746 |journal=Naturwissenschaften |language=de |volume=13 |issue=26 |pages=567–574 |doi=10.1007/BF01558746 |bibcode=1925NW.....13..567. |s2cid=32974087 |issn=1432-1904}}</ref>并以[[歐洲]]的[[萊茵河]]将其命名为Rhenium。<ref>{{cite web|title=From Hydrogen to Darmstadtium & More|page=144|url=https://books.google.com/books?id=YWkvAQAAIAAJ|publisher=American Chemical Society|date=2003|access-date=2023-12-27|archive-date=2023-06-03|archive-url=https://web.archive.org/web/20230603102154/https://books.google.com/books?id=YWkvAQAAIAAJ|dead-url=no}}</ref> |
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⚫ | |||
⚫ | [[鎳]]錸[[高溫合金]]可用於製造[[噴氣發動機]]的[[燃燒室]]、[[渦輪葉片]]及[[排氣噴嘴]]。這些合金最多含有6%的錸,這是錸最大的實際應用,其次就是作為化工產業中的[[催化劑]]。錸比[[鑽石]]更難取得,所以價格高昂,2011年8月平均每[[公斤]]售4,575美元(每金衡盎司142.30美元)。由於錸可應用在高效能噴射引擎及火箭引擎,所以在軍事戰略上十分重要。<ref>{{cite web |url=http://www.metalprices.com/FreeSite/metals/re/re.asp |title=Rhenium |work=MetalPrices.com |accessdate=2012-02-02 |archive-date=2012-01-15 |archive-url=https://web.archive.org/web/20120115004912/http://www.metalprices.com/FreeSite/metals/re/re.asp |dead-url=no }}</ref> |
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科學家在1925年發現了錸元素,因此它成為了最後被發現的穩定元素。其名稱(Rhenium)取自[[歐洲]]的[[萊茵河]]。 |
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⚫ | [[鎳]]錸[[高溫合金]]可用於製造[[噴氣發動機]]的[[燃燒室]]、[[渦輪葉片]]及[[排氣噴嘴]]。這些合金最多含有6%的錸,這是錸最大的實際應用,其次就是作為化工產業中的[[催化劑]]。錸比[[鑽石]]更難取得,所以價格高昂,2011年8月平均每[[公斤]]售4,575美元(每金衡盎司142.30美元)。由於錸可應用在高效能噴射引擎及火箭引擎,所以在軍事戰略上十分重要。<ref>{{cite web |url=http://www.metalprices.com/FreeSite/metals/re/re.asp |title=Rhenium |work=MetalPrices.com |accessdate=2012-02-02}}</ref> |
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==歷史== |
==歷史== |
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錸(Rhenium)的名稱源自拉丁文{{lang|la|Rhenus}},意為[[萊茵河]]。<ref>{{cite book|language=de|title=Forschen Suche und Sucht|first=Hans Georg|last=Tilgner|publisher=Books on Demand| year=2000|isbn=978-3-89811-272-7|url=http://books.google.com/?id=UWBWnMOGtMQC}}</ref>錸是擁有穩定同位素的元素中最後一個發現的(之後在自然界發現的其他元素都是不具有穩定同位素的放射性元素,如[[鎿]]和[[鈈]]等)。<ref name="usgs">{{cite web|publisher=[[United States Geological Survey]]|url=http://minerals.usgs.gov/minerals/pubs/commodity/rhenium/|work=Minerals Information|title=Rhenium: Statistics and Information|year=2011|accessdate=2011-05-25|language=en}}</ref>[[德米特里·門捷列夫]]在發佈[[元素週期表]]時,就預測了這一元素的存在。英國物理學家[[亨利·莫塞萊]]在1914年推算了有關該元素的一些數據。<ref>{{cite journal|first=Henry|last=Moseley|title=The High-Frequency Spectra of the Elements, Part II|doi=10.1080/14786440408635141|journal=Philosophical Magazine|year=1914|pages=703–713|volume=27|issue=160|url=http://www.chemistry.co.nz/henry_moseley_article.htm|language=en|deadurl=yes|archiveurl=https://web.archive.org/web/20100122022821/http://www.materials.manchester.ac.uk/research/facilities/moseley/biography/|archivedate=2010-01-22}}</ref>[[德國]]的[[ |
錸(Rhenium)的名稱源自拉丁文{{lang|la|Rhenus}},意為[[萊茵河]]。<ref>{{cite book|language=de|title=Forschen Suche und Sucht|first=Hans Georg|last=Tilgner|publisher=Books on Demand| year=2000|isbn=978-3-89811-272-7|url=http://books.google.com/?id=UWBWnMOGtMQC}}</ref>錸是擁有穩定同位素的元素中最後一個發現的(之後在自然界發現的其他元素都是不具有穩定同位素的放射性元素,如[[鎿]]和[[鈈]]等)。<ref name="usgs">{{cite web|publisher=[[United States Geological Survey]]|url=http://minerals.usgs.gov/minerals/pubs/commodity/rhenium/|work=Minerals Information|title=Rhenium: Statistics and Information|year=2011|accessdate=2011-05-25|language=en|archive-date=2013-06-23|archive-url=https://www.webcitation.org/6HZyjjkB4?url=http://minerals.usgs.gov/minerals/pubs/commodity/rhenium/|dead-url=no}}</ref>[[德米特里·門捷列夫]]在發佈[[元素週期表]]時,就預測了這一元素的存在。英國物理學家[[亨利·莫塞萊]]在1914年推算了有關該元素的一些數據。<ref>{{cite journal|first=Henry|last=Moseley|title=The High-Frequency Spectra of the Elements, Part II|doi=10.1080/14786440408635141|journal=Philosophical Magazine|year=1914|pages=703–713|volume=27|issue=160|url=http://www.chemistry.co.nz/henry_moseley_article.htm|language=en|deadurl=yes|archiveurl=https://web.archive.org/web/20100122022821/http://www.materials.manchester.ac.uk/research/facilities/moseley/biography/|archivedate=2010-01-22}}</ref>[[德國]]的[[瓦尔特·诺达克]]、[[伊達·諾達克]]、[[奧托·伯格]]在1925年表示在鉑礦和[[鈮鐵礦]]中探測到了此元素。他們後來也在[[硅鈹釔礦]]和[[輝鉬礦]]內發現了錸。<ref name='Ekamangane'>{{cite journal|last=Noddack|first=W.|author2=Tacke, I. |author3=Berg, O.|title=Die Ekamangane|url=https://archive.org/details/sim_naturwissenschaften_1925-06-26_13_26/page/n1| journal=Naturwissenschaften| year=1925|volume=13|issue=26 |pages=567–574|doi=10.1007/BF01558746 |bibcode=1925NW.....13..567.|language=de}}</ref>1928年,他們在660公斤輝鉬礦中提取出了1克錸元素。<ref name="1g">{{cite journal|last=Noddack| first=W.|author2=Noddack, I.|title=Die Herstellung von einem Gram Rhenium |journal=Zeitschrift für anorganische und allgemeine Chemie|year=1929|volume=183|issue=1|pages =353–375|doi=10.1002/zaac.19291830126|language=de}}</ref>估計在1968年美國75%的錸金屬都用在科研以及[[難熔金屬]]合金的研製當中。幾年之後,高溫合金才得到廣泛使用。<ref>{{cite book| pages =4–5| url =http://books.google.de/books?id=oD8rAAAAYAAJ&pg=PA4| title =Trends in usage of rhenium: Report| author1 =Committee On Technical Aspects Of Critical And Strategic Material| first1 =National Research Council (U.S.)| year =1968| language =en| access-date =2014-01-01| archive-date =2014-01-02| archive-url =https://web.archive.org/web/20140102194425/http://books.google.de/books?id=oD8rAAAAYAAJ&pg=PA4| dead-url =no}}</ref><ref>{{cite book |
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| url = http://books.google.com/?id=Wd9GAAAAYAAJ |
| url = http://books.google.com/?id=Wd9GAAAAYAAJ |
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| title = Rhenium alloys |
| title = Rhenium alloys |
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| language=en}}</ref> |
| language=en}}</ref> |
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1908年,[[日本]]化學家{{link-ja|小川正孝|小川正孝}}宣佈發現了第43號元素,並將其命名為「Nipponium」(Np),以紀念其本國日本(Nippon)。然而,後來的分析則指出,他所發現的是75號元素,而非43(即[[鍀]])。<ref>{{cite journal|doi=10.1016/j.sab.2003.12.027|title=Discovery of a new element 'nipponiumʼ: re-evaluation of pioneering works of Masataka Ogawa and his son Eijiro Ogawa|year=2004|last=Yoshihara|first=H. K.|journal=Spectrochimica Acta Part B Atomic Spectroscopy|volume=59|pages=1305–1310|bibcode=2004AcSpe..59.1305Y|issue=8|language=en}}</ref>Np在今天是第93号元素[[錼]]的化學符號,得名於海王星 |
1908年,[[日本]]化學家{{link-ja|小川正孝|小川正孝}}宣佈發現了第43號元素,並將其命名為「Nipponium」(Np),以紀念其本國日本(Nippon)。然而,後來的分析則指出,他所發現的是75號元素,而非43(即[[鍀]])。<ref>{{cite journal|doi=10.1016/j.sab.2003.12.027|title=Discovery of a new element 'nipponiumʼ: re-evaluation of pioneering works of Masataka Ogawa and his son Eijiro Ogawa|year=2004|last=Yoshihara|first=H. K.|journal=Spectrochimica Acta Part B Atomic Spectroscopy|volume=59|pages=1305–1310|bibcode=2004AcSpe..59.1305Y|issue=8|language=en}}</ref>Np在今天是第93号元素[[錼]]的化學符號,而其得名於海王星(Neptune)。 |
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==性質== |
==性質== |
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錸是一種銀白色金屬,其[[熔點]]在所有元素中是繼[[鎢]]和[[碳]]之後第三高的,[[沸點]]則 |
錸是一種銀白色金屬,其[[熔點]]在所有元素中是繼[[鎢]]和[[碳]]之後第三高的,[[沸點]](5596 °C)則仅次于[[钨]](5660 °C)。其[[密度]]在元素中排第四位,前三位分別為[[鉑]]、[[銥]]和[[鋨]]。錸具[[六方密排]]晶體結構,晶格常數為''a'' = 276.1 pm和''c'' = 445.6 pm。<ref>{{cite journal |title=Effect of pressure and temperature on lattice parameters of rhenium|first1=L.G. |last1=Liu |last2= Takahashi|first2= T. |last3=Bassett |first3=W. A. |year=1970 |volume=31 |pages=1345–1351|doi = 10.1016/0022-3697(70)90138-1 |journal=Journal of Physics and Chemistry of Solids |issue=6|bibcode = 1970JPCS...31.1345L |language=en}}</ref> |
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商業用的錸一般呈粉末狀,可在真空或[[氫]]氣中經壓制或[[燒結]]製成高密度固體,其密度為金屬態的90%以上。錸金屬在[[退火]]時延展性很高,可彎曲和捲起。<ref name=CRC>{{cite book| first=C. R.|last=Hammond |chapter=The Elements|title=Handbook of Chemistry and Physics |edition=81st |
商業用的錸一般呈粉末狀,可在真空或[[氫]]氣中經壓制或[[燒結]]製成高密度固體,其密度為金屬態的90%以上。錸金屬在[[退火]]時延展性很高,可彎曲和捲起。<ref name=CRC>{{cite book| first=C. R.|last=Hammond |chapter=The Elements|title=Handbook of Chemistry and Physics | url=https://archive.org/details/crchandbookofche81lide|edition=81st| publisher =CRC press| isbn=0-8493-0485-7| year=2004}}</ref>錸﹣鉬[[合金]]在10 [[開爾文|K]]時是[[超導體]],鎢﹣錸合金的超導溫度則在4至8 K。<ref>{{cite journal|title=Superconductivity of Some Alloys of the Tungsten-rhenium-carbon System|journal=Soviet Physics JETP|volume=27|page=13|year=1968|bibcode=1968JETP...27...13N|last=Neshpor|first=V. S.|author2=Novikov, V. I.|author3=Noskin, V. A.|author4=Shalyt, S. S.|language=en}}</ref>錸金屬在1.697 ± 0.006 K時成為超導體。<ref>{{cite book | editor= Haynes, William M. | year = 2011 | title = CRC Handbook of Chemistry and Physics | url= https://archive.org/details/crchandbookofche0000unse_e9l0 | edition = 92nd|page=12.60 | publisher = CRC Press | isbn = 1439855110|language=en}}</ref><ref>{{cite|title=The Properties of Superconducting Mo-Re Alloys|author=Daunt, J. G.; Lerner, E.| publisher=Defense Technical Information Center|language=en}}</ref> |
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錸金屬塊在[[標準溫度和壓力]]下能抵抗鹼、[[硫酸]]、[[鹽酸]]、稀[[硝酸]](非濃硝酸 |
錸金屬塊在[[标准状况|標準溫度和壓力]]下能抵抗鹼、[[硫酸]]、[[鹽酸]]、稀[[硝酸]](非濃硝酸)。<ref>{{cite web |url=http://www.espimetals.com/index.php/technical-data/191-rhenium |title=Rhenium |publisher=EPI Metals |accessdate=2014-12-28 |language=en |archive-date=2014-12-28 |archive-url=https://web.archive.org/web/20141228212127/http://www.espimetals.com/index.php/technical-data/191-rhenium |dead-url=no }}</ref> |
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但铼会被过氧化氢溶解产生[[高铼酸]]。 |
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===同位素=== |
===同位素=== |
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{{Main|錸的同位素}} |
{{Main|錸的同位素}} |
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錸只有一種穩定同位素錸-185,存量亦極低。自然產生的錸當中有37.4%的<sup>185</sup>Re以及62.6%的[[放射性]]<sup>187</sup>Re。後者的[[半衰期]]長達10<sup>10</sup>年。錸原子的電荷狀態可影響這一壽命。<ref>{{cite web|work=math.ucr.edu|url=http://math.ucr.edu/home/baez/physics/ParticleAndNuclear/decay_rates.html|title=How to Change Nuclear Decay Rates|year=1993|first=Bill|last=Johnson|accessdate=2009-02-21|language=en}}</ref><ref name="Bosch1996">{{cite journal|last1=Bosch|first1=F.|last2=Faestermann|first2=T.|last3=Friese|first3=J.|last4=Heine|first4=F.|last5=Kienle|first5=P.|last6=Wefers|first6=E.|last7=Zeitelhack|first7=K.|last8=Beckert|first8=K.|last9=Franzke|first9=B.|last10=Klepper|first10=O.|last11=Kozhuharov|first11=C.|last12=Menzel|first12=G.|last13=Moshammer|first13=R.|last14=Nolden|first14=F.|last15=Reich|first15=H.|last16=Schlitt|first16=B.|last17=Steck|first17=M.|last18=Stöhlker|first18=T.|last19=Winkler|first19=T.|last20=Takahashi|first20=K. |
錸只有一種穩定同位素錸-185,存量亦極低。自然產生的錸當中有37.4%的<sup>185</sup>Re以及62.6%的[[放射性]]<sup>187</sup>Re。後者的[[半衰期]]長達10<sup>10</sup>年。錸原子的電荷狀態可影響這一壽命。<ref>{{cite web|work=math.ucr.edu|url=http://math.ucr.edu/home/baez/physics/ParticleAndNuclear/decay_rates.html|title=How to Change Nuclear Decay Rates|year=1993|first=Bill|last=Johnson|accessdate=2009-02-21|language=en|archive-date=2013-06-23|archive-url=https://www.webcitation.org/6HZykYbZX?url=http://math.ucr.edu/home/baez/physics/ParticleAndNuclear/decay_rates.html|dead-url=yes}}</ref><ref name="Bosch1996">{{cite journal|last1=Bosch|first1=F.|last2=Faestermann|first2=T.|last3=Friese|first3=J.|last4=Heine|first4=F.|last5=Kienle|first5=P.|last6=Wefers|first6=E.|last7=Zeitelhack|first7=K.|last8=Beckert|first8=K.|last9=Franzke|first9=B.|last10=Klepper|first10=O.|last11=Kozhuharov|first11=C.|last12=Menzel|first12=G.|last13=Moshammer|first13=R.|last14=Nolden|first14=F.|last15=Reich|first15=H.|last16=Schlitt|first16=B.|last17=Steck|first17=M.|last18=Stöhlker|first18=T.|last19=Winkler|first19=T.|last20=Takahashi|first20=K.|title=Observation of bound-state ''β''<sup>–</sup> decay of fully ionized <sup>187</sup>Re: <sup>187</sup>Re-<sup>187</sup>Os Cosmochronometry|year=1996|journal=[[Physical Review Letters]]|volume=77|issue=26|pages=5190–5193|doi=10.1103/PhysRevLett.77.5190|bibcode=1996PhRvL..77.5190B|pmid=10062738|language=en}}</ref><sup>187</sup>Re的[[β衰變]]可用於[[錸鋨定年法]],以測量礦石的年齡。這一β衰變的能量為2.6 [[電子伏特|keV]],是衰變能量最低的[[放射性核素]]之一。錸-186m是壽命最長的[[同核異構體]]之一,半衰期長達20萬年左右。其他已知放射性錸同位素還有25種。<ref name="Audi">{{cite journal|first=Audi|last=Georges |title=The NUBASE Evaluation of Nuclear and Decay Properties|journal=Nuclear Physics A|volume=729|pages=3–128|publisher=Atomic Mass Data Center|year=2003|doi=10.1016/j.nuclphysa.2003.11.001|bibcode=2003NuPhA.729....3A|last2=Bersillon|first2=O.|last3=Blachot|first3=J.|last4=Wapstra|first4=A.H.|language=en}}</ref> |
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===化合物=== |
===化合物=== |
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{{Category see also|錸化合物}} |
{{Category see also|錸化合物}} |
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⚫ | 錸在化合物中的[[氧化态|氧化態]]可以在−3至+7之間,−2除外。+7、+6、+4和+2氧化態最為常見。<ref name="HollemanAF">{{cite book|publisher = Walter de Gruyter|year = 1985|edition = 91–100|pages = 1118–1123|isbn = 3-11-007511-3|title = Lehrbuch der Anorganischen Chemie|first = Arnold F.|last = Holleman|author2= Wiberg, Egon|author3=Wiberg, Nils|chapter = Rhenium| language = de}}</ref>商業用錸一般以[[高铼酸盐|高錸酸鹽]]出售,如白色水溶的[[高铼酸钠|高錸酸鈉]]和[[高铼酸铵|高錸酸銨]]等。<ref name=Brauer>Glemser, O. (1963) "Ammonium Perrhenate" in ''Handbook of Preparative Inorganic Chemistry'', 2nd ed., G. Brauer (ed.), Academic Press, NY., Vol. 1, pp. 1476–85.{{en}}</ref> |
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⚫ | 錸在化合物中的[[氧化態]]可以在−3至+7之間,−2除外。+7、+6、+4和+2氧化態最為常見。<ref name="HollemanAF">{{cite book|publisher = Walter de Gruyter|year = 1985|edition = 91–100|pages = 1118–1123|isbn = 3-11-007511-3|title = Lehrbuch der Anorganischen Chemie|first = Arnold F.|last = Holleman| |
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====鹵化物與鹵氧化物==== |
====鹵化物與鹵氧化物==== |
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最常見的氯化錸有ReCl<sub>6</sub>、[[五氯化 |
最常見的氯化錸有ReCl<sub>6</sub>、[[五氯化铼|ReCl<sub>5</sub>]]、ReCl<sub>4</sub>和[[三氯化铼|ReCl<sub>3</sub>]]。<ref name=G&W>{{Greenwood&Earnshaw2nd}}</ref>這些化合物的結構一般含有錸﹣錸鍵,這在+7態以下十分常見。[Re<sub>2</sub>Cl<sub>8</sub>]<sup>2-</sup>鹽中含有[[四重鍵|四重]]金屬﹣金屬鍵。氯化錸的最高氧化態可以是+6,而[[七氟化铼|七氟化錸]]則是各種氟化錸中氧化態最高的。錸還擁有溴化物和碘化物。<ref name="HollemanAF" /> |
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錸的化學性質與鎢和鉬相似,因此可以形成各種[[鹵氧化物]],包括ReOCl<sub>4</sub>和ReO<sub>3</sub>Cl等。<ref name="HollemanAF" /> |
錸的化學性質與鎢和鉬相似,因此可以形成各種[[卤氧化物|鹵氧化物]],包括ReOCl<sub>4</sub>和ReO<sub>3</sub>Cl等。<ref name="HollemanAF" /> |
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====氧化物與硫化物==== |
====氧化物與硫化物==== |
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[[File:Perrhenic-acid-3D-balls.png|left|thumb|120px|高錸酸的結構特殊]] |
[[File:Perrhenic-acid-3D-balls.png|left|thumb|120px|高錸酸的結構特殊]] |
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[[七氧化二錸]](Re<sub>2</sub>O<sub>7</sub>) |
[[七氧化二錸]](Re<sub>2</sub>O<sub>7</sub>)是錸最常見的氧化物,為揮發性黃色結晶,其分子結構與大部份金屬氧化物不同。紅色的[[三氧化錸]](ReO<sub>3</sub>)為不完整[[鈣鈦礦]]結構。其他錸氧化物還包括Re<sub>2</sub>O<sub>5</sub>、[[二氧化铼|ReO<sub>2</sub>]]及Re<sub>2</sub>O<sub>3</sub>。<ref name=G&W/>錸的[[硫化物]]有[[二硫化铼]](ReS<sub>2</sub>)和[[七硫化二铼]](Re<sub>2</sub>S<sub>7</sub>)。錸的獨立礦物[[輝錸礦]]最早是在庫德里亞維火山(Kudriavy)上被發現的,其主要成份就是二硫化錸。[[高錸酸鹽]]可經[[硫氫化銨]]轉換為[[四硫代高錸酸鹽]]。<ref>{{cite journal|last =Goodman|first=J. T.|author2=Rauchfuss, T. B.|title=Tetraethylammonium-tetrathioperrhenate [Et<sub>4</sub>N] [ReS<sub>4</sub>]|journal=Inorganic Syntheses|year=2002|volume=33|pages=107–110|doi=10.1002/0471224502.ch2|language=en}}</ref> |
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====其他化合物==== |
====其他化合物==== |
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[[二硼化錸]](ReB<sub>2</sub>)的硬度極高,與[[碳化鎢]]、[[碳化硅]]、[[二硼化鈦]]和[[二硼化鋯]]相近。<ref>{{cite journal| first=Jiaqian|last=Qin|author2=He, Duanwei |author3=Wang, Jianghua |author4=Fang, Leiming |author5=Lei, Li |author6=Li, Yongjun |author7=Hu, Juan |author8=Kou, Zili |author9= Bi, Yan |
[[二硼化铼|二硼化錸]](ReB<sub>2</sub>)的硬度極高,與[[碳化鎢]]、[[碳化硅]]、[[二硼化鈦]]和[[二硼化鋯]]相近。<ref>{{cite journal| first=Jiaqian|last=Qin|author2=He, Duanwei |author3=Wang, Jianghua |author4=Fang, Leiming |author5=Lei, Li |author6=Li, Yongjun |author7=Hu, Juan |author8=Kou, Zili |author9= Bi, Yan |title=Is Rhenium Diboride a Superhard Material?| journal= Advanced Materials |volume=20|year =2008| pages=4780–4783| doi=10.1002/adma.200801471| issue=24|language=en}}</ref> |
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====有機化合物==== |
====有機化合物==== |
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有機錸化學中最常用的初始化合物是[[十羰基二錸]]。鈉[[汞齊]]可將它還原成Na[Re(CO)<sub>5</sub>],後者的錸氧化態為−1。<ref>{{cite journal|doi = 10.1002/cber.19901230103|title = Nucleophile Addition von Carbonylmetallaten an kationische Alkin-Komplexe [CpL2M(η2-RC≡CR)]+ (M = Ru, Fe): μ-η1:η1-Alkin-verbrückte Komplexe|year = 1990|author = Breimair, Josef|journal = Chemische Berichte|volume = 123|page = 7|last2 = Steimann|first2 = Manfred|last3 = Wagner|first3 = Barbara|last4 = Beck|first4 = Wolfgang|language=en}}</ref>[[溴]]可把十羰基二錸氧化成[[五羰基溴化錸]]:<ref>{{cite journal|journal=Inorganic Syntheses|title=Pentacarbonylrhenium Halides|first=Steven P.|last =Schmidt|author2=Trogler, William C. |author3=Basolo, Fred | volume=28|year=1990|pages=154–159|doi=10.1002/9780470132593.ch42|series=Inorganic Syntheses|isbn=978-0-470-13259-3|language=en}}</ref> |
有機錸化學中最常用的初始化合物是[[十羰基二錸]]。鈉[[汞齊]]可將它還原成Na[Re(CO)<sub>5</sub>],後者的錸氧化態為−1。<ref>{{cite journal|doi = 10.1002/cber.19901230103|title = Nucleophile Addition von Carbonylmetallaten an kationische Alkin-Komplexe [CpL2M(η2-RC≡CR)]+ (M = Ru, Fe): μ-η1:η1-Alkin-verbrückte Komplexe|year = 1990|author = Breimair, Josef|journal = Chemische Berichte|volume = 123|page = 7|last2 = Steimann|first2 = Manfred|last3 = Wagner|first3 = Barbara|last4 = Beck|first4 = Wolfgang|language=en}}</ref>[[溴]]可把十羰基二錸氧化成[[五羰基溴化铼|五羰基溴化錸]]:<ref>{{cite journal|journal=Inorganic Syntheses|title=Pentacarbonylrhenium Halides|first=Steven P.|last =Schmidt|author2=Trogler, William C. |author3=Basolo, Fred | volume=28|year=1990|pages=154–159|doi=10.1002/9780470132593.ch42|series=Inorganic Syntheses|isbn=978-0-470-13259-3|language=en}}</ref> |
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:Re<sub>2</sub>(CO)<sub>10</sub> + Br<sub>2</sub> → 2 Re(CO)<sub>5</sub>Br |
:Re<sub>2</sub>(CO)<sub>10</sub> + Br<sub>2</sub> → 2 Re(CO)<sub>5</sub>Br |
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[[鋅]]和[[乙酸]]可再將其還原為[[五羰基氫錸]]:<ref name=Urb>{{cite journal|author=Michael A. Urbancic, John R. Shapley|title=Pentacarbonylhydridorhenium|journal=Inorganic Syntheses|volume=28|pages=165–168|year=1990|doi =10.1002/9780470132593.ch43|series=Inorganic Syntheses|isbn=978-0-470-13259-3|language=en}}</ref> |
[[鋅]]和[[乙酸]]可再將其還原為[[五羰基氢铼|五羰基氫錸]]:<ref name=Urb>{{cite journal|author=Michael A. Urbancic, John R. Shapley|title=Pentacarbonylhydridorhenium|journal=Inorganic Syntheses|volume=28|pages=165–168|year=1990|doi =10.1002/9780470132593.ch43|series=Inorganic Syntheses|isbn=978-0-470-13259-3|language=en}}</ref> |
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:Re(CO)<sub>5</sub>Br + Zn + HOAc → Re(CO)<sub>5</sub>H + ZnBr(OAc) |
:Re(CO)<sub>5</sub>Br + Zn + HOAc → Re(CO)<sub>5</sub>H + ZnBr(OAc) |
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三氧化甲基錸(CH<sub>3</sub>ReO<sub>3</sub>,縮寫MTO)是一種揮發性無色固體,可作為某些化學反應的[[催化劑]]。該化合物有多種合成途徑,最常見的是使Re<sub>2</sub>O<sub>7</sub>與[[四甲基錫]]反應: |
三氧化甲基錸(CH<sub>3</sub>ReO<sub>3</sub>,縮寫MTO)是一種揮發性無色固體,可作為某些化學反應的[[催化劑]]。該化合物有多種合成途徑,最常見的是使Re<sub>2</sub>O<sub>7</sub>與[[四甲基锡|四甲基錫]]反應: |
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:Re<sub>2</sub>O<sub>7</sub> + (CH<sub>3</sub>)<sub>4</sub>Sn → CH<sub>3</sub>ReO<sub>3</sub> + (CH<sub>3</sub>)<sub>3</sub>SnOReO<sub>3</sub> |
:Re<sub>2</sub>O<sub>7</sub> + (CH<sub>3</sub>)<sub>4</sub>Sn → CH<sub>3</sub>ReO<sub>3</sub> + (CH<sub>3</sub>)<sub>3</sub>SnOReO<sub>3</sub> |
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也存在對應的烷基和芳基化合物。MTO可催化[[過氧化氫]]氧化反應。末端[[炔烴]]會產生對應的酸或脂,內在炔烴產生二酮類,而[[烯烴]]則產生[[環氧化合物]]。MTO還能催化[[醛]]和[[重氮甲烷|重氮烷烴]]至烯烴的轉換反應。<ref>Hudson, A. (2002) “Methyltrioxorhenium” in ''Encyclopedia of Reagents for Organic Synthesis''. John Wiley & Sons: New York, ISBN 978-0-470-84289-8, {{DOI|10.1002/047084289X}}.{{en}}</ref> |
也存在對應的烷基和芳基化合物。MTO可催化[[過氧化氫]]氧化反應。末端[[炔烴]]會產生對應的酸或脂,內在炔烴產生二酮類,而[[烯烴]]則產生[[环氧化合物|環氧化合物]]。MTO還能催化[[醛]]和[[重氮甲烷|重氮烷烴]]至烯烴的轉換反應。<ref>Hudson, A. (2002) “Methyltrioxorhenium” in ''Encyclopedia of Reagents for Organic Synthesis''. John Wiley & Sons: New York, ISBN 978-0-470-84289-8, {{DOI|10.1002/047084289X}}.{{en}}</ref> |
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====九氫合錸酸鹽==== |
====九氫合錸酸鹽==== |
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第143行: | 第140行: | ||
===存量=== |
===存量=== |
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[[Image:Molybdenit 1.jpg|thumb|right|輝鉬礦]] |
[[Image:Molybdenit 1.jpg|thumb|right|輝鉬礦]] |
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錸是地球[[地殼]]中[[地球的地殼元素豐度列表|最稀有]]的元素之一,平均含量為十億分之一;<ref name=G&W/>某些文獻記載的錸含量為十億分之0.5。[[地球的地殼元素豐度列表|地球地殼元素豐度]] |
錸是地球[[地殼]]中[[地球的地殼元素豐度列表|最稀有]]的元素之一,平均含量為十億分之一;<ref name=G&W/>某些文獻記載的錸含量為十億分之0.5。在[[地球的地殼元素豐度列表|地球的地殼元素豐度]]排名中錸位居第77位。<ref name="Emsley2001p358">{{cite book|title=Nature's Building Blocks: An A-Z Guide to the Elements|last=Emsley|first=John|publisher=Oxford University Press|year=2001|location=Oxford, England, UK|isbn=0-19-850340-7|chapter=Rhenium|pages=358–360|url=http://books.google.com/books/about/Nature_s_Building_Blocks.html?id=Yhi5X7OwuGkC|language=en|access-date=2014-12-28|archive-date=2015-10-07|archive-url=https://web.archive.org/web/20151007002528/https://books.google.com/books/about/Nature_s_Building_Blocks.html?id=Yhi5X7OwuGkC|dead-url=no}}</ref>自然中很可能沒有純態的錸金屬,但目前尚無定論。[[辉钼矿|輝鉬礦]]是錸最主要的商業開採來源,其主要由[[二硫化钼|二硫化鉬]]組成,但其中的錸含量可達0.2%,<ref name=G&W/>目前所發現錸含量最高的單一輝鉬礦樣本中含有多達1.88%的錸。<ref name="Rousch"/>[[智利]]擁有全球最大的錸礦藏(夾雜在銅礦藏中),截止2005年是世界最大的錸出產國。<ref>{{cite web|url=http://minerals.usgs.gov/minerals/pubs/country/2005/cimyb05.pdf|format=PDF|first=Steve T|last=Anderson|publisher=[[United States Geological Survey]]|title=2005 Minerals Yearbook: Chile|accessdate=2008-10-26|language=en|archive-date=2011-08-22|archive-url=https://www.webcitation.org/618Rtd4yi?url=http://minerals.usgs.gov/minerals/pubs/country/2005/cimyb05.pdf|dead-url=no}}</ref>1994年,科學家在[[俄羅斯]]与[[日本]]争议领土[[南千岛群岛|南千島羣島]]之一[[擇捉島]]上的庫德里亞維火山(Kudriavy)上首次發現錸的獨立[[礦物]]。該礦物名為[[輝錸礦]],在[[火山噴氣孔]]凝聚形成,成份主要為[[二硫化铼]]。<ref>{{cite journal|last=Korzhinsky|first=M.A.|author2=Tkachenko, S. I. |author3=Shmulovich, K. I. |author4=Taran Y. A. |author5= Steinberg, G. S. | date=2004-05-05|title=Discovery of a pure rhenium mineral at Kudriavy volcano|journal=[[自然 (期刊)|Nature]]|volume=369|pages=51–52|doi=10.1038/369051a0|issue=6475|bibcode = 1994Natur.369...51K |language=en}}</ref>庫德里亞維山每年主要以二硫化錸的形式噴出20至60公斤錸。<ref>{{cite journal| last1 = Kremenetsky| first1 = A. A.| last2 = Chaplygin| first2 = I. V.| title = Concentration of rhenium and other rare metals in gases of the Kudryavy Volcano (Iturup Island, Kurile Islands)| journal = Doklady Earth Sciences| volume = 430| page = 114| year = 2010| doi = 10.1134/S1028334X10010253|bibcode = 2010DokES.430..114K |language=en}}</ref><ref>{{cite journal | last1 = Tessalina | first1 = S | last2 = Yudovskaya | first2 = M | last3 = Chaplygin | first3 = I | last4 = Birck | first4 = J | last5 = Capmas | first5 = F | title = Sources of unique rhenium enrichment in fumaroles and sulphides at Kudryavy volcano | journal = Geochimica et Cosmochimica Acta | volume = 72 | page = 889 | year = 2008 | doi = 10.1016/j.gca.2007.11.015 | bibcode=2008GeCoA..72..889T | issue = 3 |language=en}}</ref>由於輝錸礦十分罕有,收藏價格很高。<ref>{{cite web|url=http://www.galleries.com/minerals/sulfides/rheniite/rheniite.htm|publisher=Amethyst Galleries|title=The Mineral Rheniite|language=en|accessdate=2014-01-01|archive-date=2013-01-05|archive-url=https://www.webcitation.org/6DQsobu7O?url=http://www.galleries.com/Rheniite|dead-url=yes}}</ref> |
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==生產== |
==生產== |
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[[Image:Ammonium perrhenate.jpg|thumb|right|高錸酸銨]] |
[[Image:Ammonium perrhenate.jpg|thumb|right|高錸酸銨]] |
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在硫化銅礦石的提煉過程中,錸可以從含有鉬元素的焙燒煙氣中提取出來的。鉬礦石含有0.001%至0.2%的錸元素。<ref name=G&W/><ref name="Rousch">{{cite journal|doi = 10.1021/cr60291a002|title = Recent advances in the chemistry of rhenium|year = 1974|author = Rouschias, George|journal = Chemical Reviews|volume = 74|page = 531|issue = 5|language=en}}</ref>從煙氣物質中可用水淋洗出[[七氧化二錸]]和[[高錸酸]],再用[[氯化鉀]]或[[氯化銨]]使其沉澱為高錸酸鹽,最後以[[重結晶]]方法進行純化。<ref name=G&W/>錸的全球年產量在40至50噸之間,主要產國有[[智利]]、[[美國]]、[[秘魯]]和[[波蘭]]。<ref name="USGS_2012_summary">{{cite web|title=Rhenium|work=Mineral Commodity Summaries |
在硫化銅礦石的提煉過程中,錸可以從含有鉬元素的焙燒煙氣中提取出來的。鉬礦石含有0.001%至0.2%的錸元素。<ref name=G&W/><ref name="Rousch">{{cite journal|doi = 10.1021/cr60291a002|title = Recent advances in the chemistry of rhenium|year = 1974|author = Rouschias, George|journal = Chemical Reviews|volume = 74|page = 531|issue = 5|language=en}}</ref>從煙氣物質中可用水淋洗出[[七氧化二錸]]和[[高錸酸]],再用[[氯化鉀]]或[[氯化銨]]使其沉澱為高錸酸鹽,最後以[[重結晶]]方法進行純化。<ref name=G&W/>錸的全球年產量在40至50噸之間,主要產國有[[智利]]、[[美國]]、[[秘魯]]和[[波蘭]]。<ref name="USGS_2012_summary">{{cite web|title=Rhenium|work=Mineral Commodity Summaries|publisher=U.S. Geological Survey|date=January 2012|url=http://minerals.usgs.gov/minerals/pubs/commodity/rhenium/mcs-2012-rheni.pdf|format=PDF|first=Michael J.|last=Magyar|accessdate=2013-09-04|language=en|archive-date=2012-09-12|archive-url=https://web.archive.org/web/20120912170815/http://minerals.usgs.gov/minerals/pubs/commodity/rhenium/mcs-2012-rheni.pdf|dead-url=no}}</ref>另外,鉑﹣錸催化劑和某些錸合金的回收過程每年可產出10噸錸。每公斤錸價格從2003至2006年的1千至2千美元迅速升至2008年2月的1萬美元以上。<ref name="minormetals">{{cite web|title=MinorMetal prices|publisher=minormetals.com|url=http://www.minormetals.com/|accessdate=2008-02-17|language=en|archive-url=https://web.archive.org/web/20080515180506/http://www.minormetals.com/|archive-date=2008-05-15|dead-url=yes}}</ref><ref>{{cite web|url=http://in.reuters.com/article/oilRpt/idINL1037587920080710|first=Jan|last=Harvey|title=Analysis: Super hot metal rhenium may reach "platinum prices"|date=2008-07-10|accessdate=2008-10-26|publisher=Reuters India|language=en|archive-date=2009-01-11|archive-url=https://web.archive.org/web/20090111183605/http://in.reuters.com/article/oilRpt/idINL1037587920080710|dead-url=no}}</ref>要製成錸金屬,需在高溫下用[[氫氣]]還原[[高錸酸銨]]:<ref name=Brauer/> |
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:2 NH<sub>4</sub>ReO<sub>4</sub> + 7 H<sub>2</sub> → 2 Re + 8 H<sub>2</sub>O + 2 NH<sub>3</sub> |
:2 NH<sub>4</sub>ReO<sub>4</sub> + 7 H<sub>2</sub> → 2 Re + 8 H<sub>2</sub>O + 2 NH<sub>3</sub> |
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==應用== |
==應用== |
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[[Image:Engine.f15.arp.750pix.jpg|thumb|right|[[F100渦輪扇發動機]]使用第二代含錸高溫合金]] |
[[Image:Engine.f15.arp.750pix.jpg|thumb|right|[[F100渦輪扇發動機]]使用第二代含錸高溫合金]] |
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全球錸產量的70%都用於製造[[噴射引擎]]的[[高溫合金]]部件。<ref name="Naumov">{{cite journal|title=Rhythms of rhenium|journal=Russian Journal of Non-Ferrous Metals|volume=48|issue=6|year=2007|doi=10.3103/S1067821207060089|pages=418–423|first=A. V.|last=Naumov|language=en}}</ref>錸的另一主要應用是在鉑-錸[[催化劑]],可用於生產無[[鉛]]、高[[辛烷]]的[[汽油]]。<ref name="USGS_2009_yearbook">{{cite web|title=2009 Mineral Yearbook: Rhenium|date=April 2011|url=http://minerals.usgs.gov/minerals/pubs/commodity/rhenium/myb1-2009-rheni.pdf|format=PDF| |
全球錸產量的70%都用於製造[[噴射引擎]]的[[高溫合金]]部件。<ref name="Naumov">{{cite journal|title=Rhythms of rhenium|journal=Russian Journal of Non-Ferrous Metals|volume=48|issue=6|year=2007|doi=10.3103/S1067821207060089|pages=418–423|first=A. V.|last=Naumov|language=en}}</ref>錸的另一主要應用是在鉑-錸[[催化劑]],可用於生產無[[鉛]]、高[[辛烷]]的[[汽油]]。<ref name="USGS_2009_yearbook">{{cite web|title=2009 Mineral Yearbook: Rhenium|date=April 2011|url=http://minerals.usgs.gov/minerals/pubs/commodity/rhenium/myb1-2009-rheni.pdf|format=PDF|first=Michael J.|last=Magyar|publisher=United States Geological Survey|language=en|accessdate=2014-01-01|archive-date=2012-09-12|archive-url=https://web.archive.org/web/20120912170548/http://minerals.usgs.gov/minerals/pubs/commodity/rhenium/myb1-2009-rheni.pdf|dead-url=no}}</ref> |
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===合金=== |
===合金=== |
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加入錸會提升鎳[[高溫合金]]的[[蠕變]]強度。錸合金一般含有3%至6%的錸。<ref>{{cite web|title=Nickel Based Superalloys|first=H. K. D. H.|last=Bhadeshia|url=http://www.msm.cam.ac.uk/phase-trans/2003/Superalloys/superalloys.html|publisher=University of Cambridge|accessdate=2008-10-17|language=en|deadurl=yes|archiveurl=https://web.archive.org/web/20060825053006/http://www.msm.cam.ac.uk/phase-trans/2003/Superalloys/superalloys.html|archivedate=2006-08-25}}</ref>第二代合金的含錸量為3%,曾用在[[F-16]]和[[F-15]]戰機引擎中。第三代單晶體合金的含錸量則有6%,曾用在[[F-22]]和[[F-35]]引擎中。<ref name="USGS_2009_yearbook"/><ref>{{cite book |title=Aerospace Materials: An Oxford-Kobe Materials Text|first=B.|last=Cantor|author2=Grant, Patrick Assender Hazel|publisher=CRC Press| year=2001|isbn=978-0-7503-0742-0|url=http://books.google.com/?id=n09-HajhRHYC |pages=82–83|language=en}}</ref>錸高溫合金還用於工業[[燃氣輪機]]。高溫合金在加入錸後會形成拓撲密排相(TCP),因此其微結構會變得不穩定。第四代和第五代高溫合金使用[[釕]]以避免這一現象。<ref>{{cite journal|doi = 10.1007/s11041-006-0099-6|title = Effect of high-gradient directed crystallization on the structure and properties of rhenium-bearing single-crystal alloy|date = 2006|author = Bondarenko, Yu. A.|journal = Metal Science and Heat Treatment|volume = 48|page = 360|last2 = Kablov|first2 = E. N.|last3 = Surova|first3 = V. A.|last4 = Echin|first4 = A. B.|issue = 7–8}}</ref><ref>{{cite news| title=Fourth generation nickel base single crystal superalloy|url=http://sakimori.nims.go.jp/catalog/TMS-138-A.pdf}}</ref><ref>{{cite journal|author=Koizumi, Yutaka|display-authors=etal|title= |
加入錸會提升鎳[[高溫合金]]的[[蠕變]]強度。錸合金一般含有3%至6%的錸。<ref>{{cite web|title=Nickel Based Superalloys|first=H. K. D. H.|last=Bhadeshia|url=http://www.msm.cam.ac.uk/phase-trans/2003/Superalloys/superalloys.html|publisher=University of Cambridge|accessdate=2008-10-17|language=en|deadurl=yes|archiveurl=https://web.archive.org/web/20060825053006/http://www.msm.cam.ac.uk/phase-trans/2003/Superalloys/superalloys.html|archivedate=2006-08-25}}</ref>第二代合金的含錸量為3%,曾用在[[F-16]]和[[F-15]]戰機引擎中。第三代單晶體合金的含錸量則有6%,曾用在[[F-22]]和[[F-35]]引擎中。<ref name="USGS_2009_yearbook"/><ref>{{cite book |title=Aerospace Materials: An Oxford-Kobe Materials Text|first=B.|last=Cantor|author2=Grant, Patrick Assender Hazel|publisher=CRC Press| year=2001|isbn=978-0-7503-0742-0|url=http://books.google.com/?id=n09-HajhRHYC |pages=82–83|language=en}}</ref>錸高溫合金還用於工業[[燃氣輪機]]。高溫合金在加入錸後會形成拓撲密排相(TCP),因此其微結構會變得不穩定。第四代和第五代高溫合金使用[[釕]]以避免這一現象。<ref>{{cite journal|doi = 10.1007/s11041-006-0099-6|title = Effect of high-gradient directed crystallization on the structure and properties of rhenium-bearing single-crystal alloy|date = 2006|author = Bondarenko, Yu. A.|journal = Metal Science and Heat Treatment|volume = 48|page = 360|last2 = Kablov|first2 = E. N.|last3 = Surova|first3 = V. A.|last4 = Echin|first4 = A. B.|issue = 7–8}}</ref><ref>{{cite news| title=Fourth generation nickel base single crystal superalloy| url=http://sakimori.nims.go.jp/catalog/TMS-138-A.pdf| accessdate=2016-12-02| archive-date=2016-04-23| archive-url=https://web.archive.org/web/20160423201635/http://sakimori.nims.go.jp/catalog/TMS-138-A.pdf| dead-url=no}}</ref><ref>{{cite journal|author=Koizumi, Yutaka|display-authors=etal|title=Development of a Next-Generation Ni-base Single Crystal Superalloy|url=http://nippon.zaidan.info/seikabutsu/2003/00916/pdf/igtc2003tokyo_ts119.pdf|work=Proceedings of the International Gas Turbine Congress, Tokyo November 2–7, 2003|access-date=2016-12-02|archive-date=2019-01-26|archive-url=https://web.archive.org/web/20190126011442/http://nippon.zaidan.info/seikabutsu/2003/00916/pdf/igtc2003tokyo_ts119.pdf|dead-url=no}}</ref><ref>{{cite news| title=Joint Development of a Fourth Generation Single Crystal Superalloy|author=Walston, S.|author2=Cetel, A.|author3=MacKay, R.|author4=O'Hara, K.|author5=Duhl, D.|author6=Dreshfield, R.|url=http://gltrs.grc.nasa.gov/reports/2004/TM-2004-213062.pdf|archiveurl=https://web.archive.org/web/20061015113650/http://gltrs.grc.nasa.gov/reports/2004/TM-2004-213062.pdf |archivedate=2006-10-15}}</ref> |
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[[File:CFM56 P1220759.jpg|thumb|left|仍使用3%錸合金的CFM56噴射引擎]] |
[[File:CFM56 P1220759.jpg|thumb|left|仍使用3%錸合金的CFM56噴射引擎]] |
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錸在高溫下十分穩定,蒸氣壓低,耐磨損,且能夠抵禦電弧腐蝕,所以是很好的自動清洗電觸頭材料。開關時的電火花會對觸頭進行氧化耗損。不過,七氧化二錸(Re<sub>2</sub>O<sub>7</sub>)在360 °C左右昇華,所以會在放電過程中移去。<ref name ="Naumov"/> |
錸在高溫下十分穩定,蒸氣壓低,耐磨損,且能夠抵禦電弧腐蝕,所以是很好的自動清洗電觸頭材料。開關時的電火花會對觸頭進行氧化耗損。不過,七氧化二錸(Re<sub>2</sub>O<sub>7</sub>)在360 °C左右昇華,所以會在放電過程中移去。<ref name ="Naumov"/> |
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錸與[[鉭]]和鎢一樣具有高熔點和低蒸氣壓,所以用這些材料製成的燈絲在氧氣環境下穩定性較高。<ref>{{cite journal|doi=10.1021/j100873a513|year=1966|last=Blackburn|first=Paul E.|journal=The Journal of Physical Chemistry|volume=70|pages=311–312|title=The Vapor Pressure of Rhenium|language=en}}</ref>這類燈絲被廣泛用於[[質譜儀]]、[[電離壓力計]]<ref>{{cite journal|title=Tungsten-Rhenium Filament Lifetime Variability in Low Pressure Oxygen Environments|last= Earle|first=G. D.|author2=Medikonduri, R. |author3=Rajagopal, N. |author4=Narayanan, V. |author5= Roddy, P. A. |journal= IEEE Transactions on Plasma Science|volume=33|issue=5|pages=1736–1737|doi =10.1109/TPS.2005.856413|year=2005|bibcode = 2005ITPS...33.1736E |language=en}}</ref>及照相閃光燈等。<ref>{{cite book|title=The chemical element: a historical perspective|first=Andrew|last=Ede| publisher=Greenwood Publishing Group|year=2006|isbn=978-0-313-33304-0|language=en}}</ref> |
錸與[[鉭]]和鎢一樣具有高熔點和低蒸氣壓,所以用這些材料製成的燈絲在氧氣環境下穩定性較高。<ref>{{cite journal|doi=10.1021/j100873a513|year=1966|last=Blackburn|first=Paul E.|journal=The Journal of Physical Chemistry|volume=70|pages=311–312|title=The Vapor Pressure of Rhenium|language=en}}</ref>這類燈絲被廣泛用於[[質譜儀]]、[[電離壓力計]]<ref>{{cite journal|title=Tungsten-Rhenium Filament Lifetime Variability in Low Pressure Oxygen Environments|last= Earle|first=G. D.|author2=Medikonduri, R. |author3=Rajagopal, N. |author4=Narayanan, V. |author5= Roddy, P. A. |journal= IEEE Transactions on Plasma Science|volume=33|issue=5|pages=1736–1737|doi =10.1109/TPS.2005.856413|year=2005|bibcode = 2005ITPS...33.1736E |language=en}}</ref>及照相閃光燈等。<ref>{{cite book|title=The chemical element: a historical perspective|url=https://archive.org/details/chemicalelementh0000edea|first=Andrew|last=Ede| publisher=Greenwood Publishing Group|year=2006|isbn=978-0-313-33304-0|language=en}}</ref> |
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===催化劑=== |
===催化劑=== |
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錸﹣鉑合金是[[催化重整]]過程中的一種催化劑。這種石油加工過程能夠提高[[石腦油]]的[[辛烷值]]。用於催化重整的催化劑當中,30%含有錸。<ref>{{cite journal|title=Rhenium-containing catalysts in reactions of organic compounds|year=1998|journal=Russian Chemical Reviews|volume=67|pages=157–177|doi=10.1070/RC1998v067n02ABEH000390|first=Margarita A.|last= Ryashentseva|issue=2|bibcode = 1998RuCRv..67..157R |language=en}}</ref>在[[礬土]](氧化鋁)表面塗上錸,可作為[[烯烴複分解反應]]的催化劑。<ref>{{cite journal|journal=Catalysis Today |volume=51| issue=2|year=1999|pages=289–299|title=Olefin metathesis over supported rhenium oxide catalysts|first=Johannes C.|last=Mol|doi=10.1016/S0920-5861(99)00051-6|language=en}}</ref>含錸催化劑可抗禦氮、硫和磷的催化劑中毒現象,因此被用在某些氫化反應中。<ref name=CRC/><ref>{{cite journal|journal=Ind. Eng. Chem. Res.|volume=38|issue=5|pages=1830–1836|year=1999|title=Selective Rhenium Recovery from Spent Reforming Catalysts|doi= 10.1021/ie9806242|first=T. N. |last=Angelidis|author2=Rosopoulou, D. Tzitzios V.|language=en}}</ref><ref>{{cite journal|title=The Oxidation State of Rhenium and Its Role in Platinum-Rhenium|url=http://www.platinummetalsreview.com/pdf/pmr-v22-i2-057-060.pdf |
錸﹣鉑合金是[[催化重整]]過程中的一種催化劑。這種石油加工過程能夠提高[[石腦油]]的[[辛烷值]]。用於催化重整的催化劑當中,30%含有錸。<ref>{{cite journal|title=Rhenium-containing catalysts in reactions of organic compounds|year=1998|journal=Russian Chemical Reviews|volume=67|pages=157–177|doi=10.1070/RC1998v067n02ABEH000390|first=Margarita A.|last= Ryashentseva|issue=2|bibcode = 1998RuCRv..67..157R |language=en}}</ref>在[[礬土]](氧化鋁)表面塗上錸,可作為[[烯烴複分解反應]]的催化劑。<ref>{{cite journal|journal=Catalysis Today |volume=51| issue=2|year=1999|pages=289–299|title=Olefin metathesis over supported rhenium oxide catalysts|first=Johannes C.|last=Mol|doi=10.1016/S0920-5861(99)00051-6|language=en}}</ref>含錸催化劑可抗禦氮、硫和磷的催化劑中毒現象,因此被用在某些氫化反應中。<ref name=CRC/><ref>{{cite journal|journal=Ind. Eng. Chem. Res.|volume=38|issue=5|pages=1830–1836|year=1999|title=Selective Rhenium Recovery from Spent Reforming Catalysts|doi= 10.1021/ie9806242|first=T. N. |last=Angelidis|author2=Rosopoulou, D. Tzitzios V.|language=en}}</ref><ref>{{cite journal|title=The Oxidation State of Rhenium and Its Role in Platinum-Rhenium|url=http://www.platinummetalsreview.com/pdf/pmr-v22-i2-057-060.pdf|format=PDF|first=Robert|last=Burch|journal=Platinum Metals Review|year=1978|volume=22|issue=2|pages=57–60|language=en|access-date=2014-01-01|archive-date=2013-01-31|archive-url=https://web.archive.org/web/20130131030252/http://www.platinummetalsreview.com/pdf/pmr-v22-i2-057-060.pdf|dead-url=no}}</ref> |
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===其他用途=== |
===其他用途=== |
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<sup>188</sup>Re和<sup>186</sup>Re同位素具有放射性,可用於治療[[肝癌]]。兩者在身體組織的穿透深度相近,分別為11毫米和5毫米,但<sup>186</sup>Re的半衰期較長(90小時,相比17小時),所以更為優勝。<ref name="Dilw">{{cite journal| first=Jonathan R.|last=Dilworth|author2 =Parrott, Suzanne J.|title=The biomedical chemistry of technetium and rhenium| journal=Chemical Society Reviews|year= 1998|volume=27|pages=43–55|doi=10.1039/a827043z|language=en}}</ref><ref>{{cite web|publisher=Oak Ridge National Laboratory|title=The Tungsten-188 and Rhenium-188 Generator Information|year=2005|url=http://www.ornl.gov/sci/nuclear_science_technology/nu_med/188info.htm|accessdate=2008-02-03|archiveurl=https://web.archive.org/web/20080109170105/http://www.ornl.gov/sci/nuclear_science_technology/nu_med/188info.htm|archivedate=2008-01-09|language=en|deadurl=yes}}</ref> |
<sup>188</sup>Re和<sup>186</sup>Re同位素具有放射性,可用於治療[[肝癌]]。兩者在身體組織的穿透深度相近,分別為11毫米和5毫米,但<sup>186</sup>Re的半衰期較長(90小時,相比17小時),所以更為優勝。<ref name="Dilw">{{cite journal| first=Jonathan R.|last=Dilworth|author2 =Parrott, Suzanne J.|title=The biomedical chemistry of technetium and rhenium| url=https://archive.org/details/sim_chemical-society-great-britain-chemical-society-reviews_1998-01_27_1/page/43| journal=Chemical Society Reviews|year= 1998|volume=27|pages=43–55|doi=10.1039/a827043z|language=en}}</ref><ref>{{cite web|publisher=Oak Ridge National Laboratory|title=The Tungsten-188 and Rhenium-188 Generator Information|year=2005|url=http://www.ornl.gov/sci/nuclear_science_technology/nu_med/188info.htm|accessdate=2008-02-03|archiveurl=https://web.archive.org/web/20080109170105/http://www.ornl.gov/sci/nuclear_science_technology/nu_med/188info.htm|archivedate=2008-01-09|language=en|deadurl=yes}}</ref> |
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<sup>188</sup>Re還被用於一種新型胰腺癌療法:用[[李斯特菌]]攜帶這一錸放射性同位素進入身體,針對性地對抗癌組織。<ref>{{cite web|last=Baker|first=Monya|title=Radioactive bacteria attack cancer|url=http://www.nature.com/news/radioactive-bacteria-attack-cancer-1.12841|work=Nature|date=2013-04-22|language=en}}</ref> |
<sup>188</sup>Re還被用於一種新型胰腺癌療法:用[[李斯特菌]]攜帶這一錸放射性同位素進入身體,針對性地對抗癌組織。<ref>{{cite web|last=Baker|first=Monya|title=Radioactive bacteria attack cancer|url=http://www.nature.com/news/radioactive-bacteria-attack-cancer-1.12841|work=Nature|date=2013-04-22|language=en|accessdate=2014-01-01|archive-date=2013-12-26|archive-url=https://web.archive.org/web/20131226111211/http://www.nature.com/news/radioactive-bacteria-attack-cancer-1.12841|dead-url=no}}</ref> |
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錸在元素週期表中位於[[鍀]]之下,所以根據週期規律,兩者的性質相近。含錸化合物可以很容易地轉換為對應的鍀化合物。這在放射性藥物學中非常有用,因為鍀(特別是醫學常用的鍀-99m同位素)價格高,半衰期短,所以很難直接使用。<ref name="Dilw"/><ref>{{cite journal|doi=10.1039/QR9621600299|title=An outline of technetium chemistry|year=1962|author=Colton, R.| |
錸在元素週期表中位於[[鍀]]之下,所以根據週期規律,兩者的性質相近。含錸化合物可以很容易地轉換為對應的鍀化合物。這在放射性藥物學中非常有用,因為鍀(特別是醫學常用的鍀-99m同位素)價格高,半衰期短,所以很難直接使用。<ref name="Dilw"/><ref>{{cite journal|doi=10.1039/QR9621600299|title=An outline of technetium chemistry|year=1962|author=Colton, R.|author2=Peacock R. D.|journal=Quarterly Reviews Chemical Society|volume=16|pages=299–315|issue=4|language=en}}</ref> |
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==安全== |
==安全== |
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由於用量一般很少,所以人們對錸以及錸化合物的毒性所知甚少。鹵化錸和高錸酸鹽等可溶鹽的有害性可能來自錸或者其他所含元素。<ref name="Emsley">{{cite book|title=Nature's Building Blocks: An A-Z Guide to the Elements|last=Emsley|first=J.|publisher=Oxford University Press|year=2003|location=Oxford, England, UK|isbn=0-19-850340-7|chapter=Rhenium| pages= |
由於用量一般很少,所以人們對錸以及錸化合物的毒性所知甚少。鹵化錸和高錸酸鹽等可溶鹽的有害性可能來自錸或者其他所含元素。<ref name="Emsley">{{cite book|title=Nature's Building Blocks: An A-Z Guide to the Elements|url=https://archive.org/details/naturesbuildingb0000emsl|last=Emsley|first=J.|publisher=Oxford University Press|year=2003|location=Oxford, England, UK|isbn=0-19-850340-7|chapter=Rhenium| pages=[https://archive.org/details/naturesbuildingb0000emsl/page/358 358]–361|language=en}}</ref>科學家只對極少數錸化合物作過毒性測試,包括高錸酸鉀和三氯化錸。試驗以老鼠作為對象,測得高錸酸鉀的7天[[半數致死量|LD<sub>50</sub>]]值為2800 mg/kg,三氯化錸的LD<sub>50</sub>值為280 mg/kg。<ref>{{cite journal|title=Pharmacology and toxicology of potassium perrhenate and rhenium trichloride|url=https://archive.org/details/sim_journal-of-pharmaceutical-sciences_1968-02_57_2/page/321|pages=321–323|first =Thomas J.|last=Haley|author2= Cartwright, Frank D.|doi=10.1002/jps.2600570218|journal=Journal of Pharmaceutical Sciences|volume=57|issue=2|year=1968|pmid=5641681|language=en}}</ref> |
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==參考資料== |
==參考資料== |
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==外部連結== |
==外部連結== |
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{{Elements.links|Rhenium}} |
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* [http://www.periodicvideos.com/videos/075.htm Rhenium] at ''The Periodic Table of Videos''(諾丁漢大學) |
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* {{cite web|url=http://n-t.ru/ri/ps/pb075.htm|title=Рений|publisher=Популярная библиотека химических элементов|accessdate=2013-08-17|archiveurl=https:// |
* {{cite web|url=http://n-t.ru/ri/ps/pb075.htm|title=Рений|publisher=Популярная библиотека химических элементов|accessdate=2013-08-17|archiveurl=https://web.archive.org/web/20130520204742/http://n-t.ru/ri/ps/pb075.htm|archivedate=2013-05-20|dead-url=yes}} |
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* {{cite web|url=http://www.metalprices.com/metal/rhenium/|title=MetalPrices.com is now part of Argus Metals|publisher=MetalPrices.com|language=en|accessdate=2013-08-17|archiveurl=https:// |
* {{cite web|url=http://www.metalprices.com/metal/rhenium/|title=MetalPrices.com is now part of Argus Metals|publisher=MetalPrices.com|language=en|accessdate=2013-08-17|archiveurl=https://web.archive.org/web/20130525114844/http://www.metalprices.com/metal/rhenium/|archivedate=2013-05-25|dead-url=yes}} |
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* {{cite web|url=http://www.toma-group.com/|title=Toma Group Rhenium and precious metals refining|publisher=Toma Group|language=en|accessdate=2013-08-17|archiveurl=https:// |
* {{cite web|url=http://www.toma-group.com/|title=Toma Group Rhenium and precious metals refining|publisher=Toma Group|language=en|accessdate=2013-08-17|archiveurl=https://web.archive.org/web/20130719051758/http://toma-group.com/|archivedate=2013-07-19|dead-url=yes}} |
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* {{cite web|author=Режиссер: Д. Семибратов|title="Эффект рения" - HD (Effect of Rhenium) 2014г., документальный фильм - YouTube|url=https://www.youtube.com/watch?v=mY8C_dTdUOA&feature=share|language=ru}} |
* {{cite web|author=Режиссер: Д. Семибратов|title="Эффект рения" - HD (Effect of Rhenium) 2014г., документальный фильм - YouTube|url=https://www.youtube.com/watch?v=mY8C_dTdUOA&feature=share|language=ru|accessdate=2018-02-01|archive-date=2019-07-01|archive-url=https://web.archive.org/web/20190701195818/https://www.youtube.com/watch?v=mY8C_dTdUOA&feature=share|dead-url=no}} |
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{{元素週期表}} |
{{元素週期表}} |
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{{Authority control}} |
{{Authority control}} |
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[[Category:铼| ]] |
[[Category:铼| ]] |
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[[Category:化学元素|6U]] |
[[Category:化学元素|6U]] |
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[[Category:稀有金属]] |
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[[Category:耐火金屬]] |
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[[Category:自然元素礦物]] |
2024年12月18日 (三) 20:43的最新版本
早在1908年,小川正孝就发现了铼,但他错误将其当作43号元素。沃爾特·諾達克、伊達·諾達克、奧托·伯格于1925年重新發現了它,[4]并以歐洲的萊茵河将其命名为Rhenium。[5]
鎳錸高溫合金可用於製造噴氣發動機的燃燒室、渦輪葉片及排氣噴嘴。這些合金最多含有6%的錸,這是錸最大的實際應用,其次就是作為化工產業中的催化劑。錸比鑽石更難取得,所以價格高昂,2011年8月平均每公斤售4,575美元(每金衡盎司142.30美元)。由於錸可應用在高效能噴射引擎及火箭引擎,所以在軍事戰略上十分重要。[6]
歷史
[编辑]錸(Rhenium)的名稱源自拉丁文Rhenus,意為萊茵河。[7]錸是擁有穩定同位素的元素中最後一個發現的(之後在自然界發現的其他元素都是不具有穩定同位素的放射性元素,如鎿和鈈等)。[8]德米特里·門捷列夫在發佈元素週期表時,就預測了這一元素的存在。英國物理學家亨利·莫塞萊在1914年推算了有關該元素的一些數據。[9]德國的瓦尔特·诺达克、伊達·諾達克、奧托·伯格在1925年表示在鉑礦和鈮鐵礦中探測到了此元素。他們後來也在硅鈹釔礦和輝鉬礦內發現了錸。[10]1928年,他們在660公斤輝鉬礦中提取出了1克錸元素。[11]估計在1968年美國75%的錸金屬都用在科研以及難熔金屬合金的研製當中。幾年之後,高溫合金才得到廣泛使用。[12][13]
1908年,日本化學家小川正孝宣佈發現了第43號元素,並將其命名為「Nipponium」(Np),以紀念其本國日本(Nippon)。然而,後來的分析則指出,他所發現的是75號元素,而非43(即鍀)。[14]Np在今天是第93号元素錼的化學符號,而其得名於海王星(Neptune)。
性質
[编辑]錸是一種銀白色金屬,其熔點在所有元素中是繼鎢和碳之後第三高的,沸點(5596 °C)則仅次于钨(5660 °C)。其密度在元素中排第四位,前三位分別為鉑、銥和鋨。錸具六方密排晶體結構,晶格常數為a = 276.1 pm和c = 445.6 pm。[15]
商業用的錸一般呈粉末狀,可在真空或氫氣中經壓制或燒結製成高密度固體,其密度為金屬態的90%以上。錸金屬在退火時延展性很高,可彎曲和捲起。[16]錸﹣鉬合金在10 K時是超導體,鎢﹣錸合金的超導溫度則在4至8 K。[17]錸金屬在1.697 ± 0.006 K時成為超導體。[18][19]
錸金屬塊在標準溫度和壓力下能抵抗鹼、硫酸、鹽酸、稀硝酸(非濃硝酸)。[20]
但铼会被过氧化氢溶解产生高铼酸。
同位素
[编辑]錸只有一種穩定同位素錸-185,存量亦極低。自然產生的錸當中有37.4%的185Re以及62.6%的放射性187Re。後者的半衰期長達1010年。錸原子的電荷狀態可影響這一壽命。[21][22]187Re的β衰變可用於錸鋨定年法,以測量礦石的年齡。這一β衰變的能量為2.6 keV,是衰變能量最低的放射性核素之一。錸-186m是壽命最長的同核異構體之一,半衰期長達20萬年左右。其他已知放射性錸同位素還有25種。[23]
化合物
[编辑]錸在化合物中的氧化態可以在−3至+7之間,−2除外。+7、+6、+4和+2氧化態最為常見。[24]商業用錸一般以高錸酸鹽出售,如白色水溶的高錸酸鈉和高錸酸銨等。[25]
鹵化物與鹵氧化物
[编辑]最常見的氯化錸有ReCl6、ReCl5、ReCl4和ReCl3。[26]這些化合物的結構一般含有錸﹣錸鍵,這在+7態以下十分常見。[Re2Cl8]2-鹽中含有四重金屬﹣金屬鍵。氯化錸的最高氧化態可以是+6,而七氟化錸則是各種氟化錸中氧化態最高的。錸還擁有溴化物和碘化物。[24]
錸的化學性質與鎢和鉬相似,因此可以形成各種鹵氧化物,包括ReOCl4和ReO3Cl等。[24]
氧化物與硫化物
[编辑]七氧化二錸(Re2O7)是錸最常見的氧化物,為揮發性黃色結晶,其分子結構與大部份金屬氧化物不同。紅色的三氧化錸(ReO3)為不完整鈣鈦礦結構。其他錸氧化物還包括Re2O5、ReO2及Re2O3。[26]錸的硫化物有二硫化铼(ReS2)和七硫化二铼(Re2S7)。錸的獨立礦物輝錸礦最早是在庫德里亞維火山(Kudriavy)上被發現的,其主要成份就是二硫化錸。高錸酸鹽可經硫氫化銨轉換為四硫代高錸酸鹽。[27]
其他化合物
[编辑]二硼化錸(ReB2)的硬度極高,與碳化鎢、碳化硅、二硼化鈦和二硼化鋯相近。[28]
有機化合物
[编辑]有機錸化學中最常用的初始化合物是十羰基二錸。鈉汞齊可將它還原成Na[Re(CO)5],後者的錸氧化態為−1。[29]溴可把十羰基二錸氧化成五羰基溴化錸:[30]
- Re2(CO)10 + Br2 → 2 Re(CO)5Br
- Re(CO)5Br + Zn + HOAc → Re(CO)5H + ZnBr(OAc)
三氧化甲基錸(CH3ReO3,縮寫MTO)是一種揮發性無色固體,可作為某些化學反應的催化劑。該化合物有多種合成途徑,最常見的是使Re2O7與四甲基錫反應:
- Re2O7 + (CH3)4Sn → CH3ReO3 + (CH3)3SnOReO3
也存在對應的烷基和芳基化合物。MTO可催化過氧化氫氧化反應。末端炔烴會產生對應的酸或脂,內在炔烴產生二酮類,而烯烴則產生環氧化合物。MTO還能催化醛和重氮烷烴至烯烴的轉換反應。[32]
九氫合錸酸鹽
[编辑]九氫合錸酸鹽是一種特殊的錸化合物。九氫合錸酸負離子(ReH2−
9)原先被認為是錸負離子Re−。[33]該離子中錸的氧化態為+7。[24]
存量
[编辑]錸是地球地殼中最稀有的元素之一,平均含量為十億分之一;[26]某些文獻記載的錸含量為十億分之0.5。在地球的地殼元素豐度排名中錸位居第77位。[34]自然中很可能沒有純態的錸金屬,但目前尚無定論。輝鉬礦是錸最主要的商業開採來源,其主要由二硫化鉬組成,但其中的錸含量可達0.2%,[26]目前所發現錸含量最高的單一輝鉬礦樣本中含有多達1.88%的錸。[35]智利擁有全球最大的錸礦藏(夾雜在銅礦藏中),截止2005年是世界最大的錸出產國。[36]1994年,科學家在俄羅斯与日本争议领土南千島羣島之一擇捉島上的庫德里亞維火山(Kudriavy)上首次發現錸的獨立礦物。該礦物名為輝錸礦,在火山噴氣孔凝聚形成,成份主要為二硫化铼。[37]庫德里亞維山每年主要以二硫化錸的形式噴出20至60公斤錸。[38][39]由於輝錸礦十分罕有,收藏價格很高。[40]
生產
[编辑]在硫化銅礦石的提煉過程中,錸可以從含有鉬元素的焙燒煙氣中提取出來的。鉬礦石含有0.001%至0.2%的錸元素。[26][35]從煙氣物質中可用水淋洗出七氧化二錸和高錸酸,再用氯化鉀或氯化銨使其沉澱為高錸酸鹽,最後以重結晶方法進行純化。[26]錸的全球年產量在40至50噸之間,主要產國有智利、美國、秘魯和波蘭。[41]另外,鉑﹣錸催化劑和某些錸合金的回收過程每年可產出10噸錸。每公斤錸價格從2003至2006年的1千至2千美元迅速升至2008年2月的1萬美元以上。[42][43]要製成錸金屬,需在高溫下用氫氣還原高錸酸銨:[25]
- 2 NH4ReO4 + 7 H2 → 2 Re + 8 H2O + 2 NH3
應用
[编辑]全球錸產量的70%都用於製造噴射引擎的高溫合金部件。[44]錸的另一主要應用是在鉑-錸催化劑,可用於生產無鉛、高辛烷的汽油。[45]
合金
[编辑]加入錸會提升鎳高溫合金的蠕變強度。錸合金一般含有3%至6%的錸。[46]第二代合金的含錸量為3%,曾用在F-16和F-15戰機引擎中。第三代單晶體合金的含錸量則有6%,曾用在F-22和F-35引擎中。[45][47]錸高溫合金還用於工業燃氣輪機。高溫合金在加入錸後會形成拓撲密排相(TCP),因此其微結構會變得不穩定。第四代和第五代高溫合金使用釕以避免這一現象。[48][49][50][51]
2006年的錸消耗量分別為:通用電氣28%,勞斯萊斯股份有限公司28%,普惠公司12%,皆用於生產高溫合金。另有14%用作催化劑,18%作其他用途。[44]由於軍用噴射引擎需求持續增加,因此有必要研發含錸量更低的高溫合金,以維持供應。比如,新型CFM56高壓渦輪(HPT)葉片使用的合金含1.5%的錸,以取代含錸量為3%的合金。[52][53]
錸可增強鎢的物理性質。鎢﹣錸合金在低溫下可塑性更高,易於製造、塑形,且在高溫下的穩定性也得以提高。這一變化會隨錸的含量而增加,所以鎢﹣錸合金含有27%的錸,這也就是錸在鎢中的溶解極限。[54]X射線源是鎢﹣錸合金的其中一個應用。鎢和錸的熔點和原子量都很高,有助於抵抗持續的電子撞擊。[55]這種合金還用作熱電偶,可測量最高2200 °C的溫度。[56]
錸在高溫下十分穩定,蒸氣壓低,耐磨損,且能夠抵禦電弧腐蝕,所以是很好的自動清洗電觸頭材料。開關時的電火花會對觸頭進行氧化耗損。不過,七氧化二錸(Re2O7)在360 °C左右昇華,所以會在放電過程中移去。[44]
錸與鉭和鎢一樣具有高熔點和低蒸氣壓,所以用這些材料製成的燈絲在氧氣環境下穩定性較高。[57]這類燈絲被廣泛用於質譜儀、電離壓力計[58]及照相閃光燈等。[59]
催化劑
[编辑]錸﹣鉑合金是催化重整過程中的一種催化劑。這種石油加工過程能夠提高石腦油的辛烷值。用於催化重整的催化劑當中,30%含有錸。[60]在礬土(氧化鋁)表面塗上錸,可作為烯烴複分解反應的催化劑。[61]含錸催化劑可抗禦氮、硫和磷的催化劑中毒現象,因此被用在某些氫化反應中。[16][62][63]
其他用途
[编辑]188Re和186Re同位素具有放射性,可用於治療肝癌。兩者在身體組織的穿透深度相近,分別為11毫米和5毫米,但186Re的半衰期較長(90小時,相比17小時),所以更為優勝。[64][65]
188Re還被用於一種新型胰腺癌療法:用李斯特菌攜帶這一錸放射性同位素進入身體,針對性地對抗癌組織。[66]
錸在元素週期表中位於鍀之下,所以根據週期規律,兩者的性質相近。含錸化合物可以很容易地轉換為對應的鍀化合物。這在放射性藥物學中非常有用,因為鍀(特別是醫學常用的鍀-99m同位素)價格高,半衰期短,所以很難直接使用。[64][67]
安全
[编辑]由於用量一般很少,所以人們對錸以及錸化合物的毒性所知甚少。鹵化錸和高錸酸鹽等可溶鹽的有害性可能來自錸或者其他所含元素。[68]科學家只對極少數錸化合物作過毒性測試,包括高錸酸鉀和三氯化錸。試驗以老鼠作為對象,測得高錸酸鉀的7天LD50值為2800 mg/kg,三氯化錸的LD50值為280 mg/kg。[69]
參考資料
[编辑]- ^ Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. Standard atomic weights of the elements 2021 (IUPAC Technical Report). Pure and Applied Chemistry. 2022-05-04. ISSN 1365-3075. doi:10.1515/pac-2019-0603 (英语).
- ^ Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997: 28. ISBN 0-7506-3365-4.
- ^ [1] (页面存档备份,存于互联网档案馆), in Handbook of Chemistry and Physics 81st edition, CRC press.
- ^ Die Ekamangane. Naturwissenschaften. 1925-06-01, 13 (26): 567–574. Bibcode:1925NW.....13..567.. ISSN 1432-1904. S2CID 32974087. doi:10.1007/BF01558746 (德语).
- ^ From Hydrogen to Darmstadtium & More. American Chemical Society: 144. 2003 [2023-12-27]. (原始内容存档于2023-06-03).
- ^ Rhenium. MetalPrices.com. [2012-02-02]. (原始内容存档于2012-01-15).
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