User:Yinweichen/Testpage2:修订间差异
Yinweichen(留言 | 贡献) 无编辑摘要 |
Yinweichen(留言 | 贡献) 无编辑摘要 |
||
第1行: | 第1行: | ||
{{Elementbox |
{{Elementbox |
||
|number= |
|number=96 |
||
|symbol= |
|symbol=Cm |
||
|name= |
|name=鋦 |
||
|enname= |
|enname=Curium |
||
|left=[[ |
|left=[[鋂]] |
||
|right=[[ |
|right=[[錇]] |
||
|above=[[ |
|above=[[釓]] |
||
|below=( |
|below=(Uqo) |
||
|series= |
|series=錒系元素 |
||
|period=7 |
|period=7 |
||
|block=f |
|block=f |
||
<includeonly>|image name= curium.jpg</includeonly> |
|||
|appearance=銀白色 |
|||
|appearance= 銀白色 |
|||
|image name=Californium.jpg |
|||
|atomic mass= (247) |
|||
|image alt= 一小塊圓碟形的鉲元素 |
|||
|electron configuration= [[[氡|Rn]]] 5f<sup>7</sup> 6d<sup>1</sup> 7s<sup>2</sup> |
|||
|image size = 176 |
|||
|electrons per shell= 2, 8, 18, 32, 25, 9, 2 |
|||
|atomic mass= (251) {{sfn|CRC|2006|p=4.56}} |
|||
|phase= 固體 |
|||
|electron configuration= [[[氡|Rn]]] 5f<sup>10</sup> 7s<sup>2</sup> {{sfn|CRC|2006|p=1.14}} |
|||
|density gpcm3nrt= 13.51 |
|||
|electrons per shell= 2, 8, 18, 32, 28, 8, 2 |
|||
|melting point K=1613 |
|||
|phase= 固體 |
|||
|melting point C=1340 |
|||
|Mohs hardness=3–4{{sfn|CRC|1991|p=254}} |
|||
|melting point F=2444 |
|||
|density gpcm3nrt= 15.1{{sfn|CRC|2006|p=4.56}} <!-- {{sfn|O'Neil|2006|p=276}} --> |
|||
|boiling point K=3383 |
|||
|melting point K=1173 <!-- {{sfn|Greenwood|1997|p=1263}} --> |
|||
| |
|boiling point C=3110 |
||
| |
|boiling point F=5630 |
||
|heat fusion= ? 15 |
|||
|boiling point K=1743<ref>{{cite book|author1=Joseph Jacob Katz|author2=Glenn Theodore Seaborg|author3=Lester R. Morss|title=The Chemistry of the actinide elements|url=http://books.google.com/books?id=UuPvAAAAMAAJ|accessdate=11 July 2011|year=1986|publisher=Chapman and Hall|isbn=9780412273704|page=1038}}</ref> |
|||
|vapor pressure 1= 1788 |
|||
|boiling point C=1470 |
|||
|vapor pressure 10= 1982 |
|||
|boiling point F=2678(估值) |
|||
|vapor pressure 100= |
|||
|crystal structure= 六方 |
|||
|vapor pressure 1 k= |
|||
|crystal structure ref= |
|||
|vapor pressure 10 k= |
|||
|crystal structure comment= |
|||
|vapor pressure 100 k= |
|||
|oxidation states= 2, '''3''', 4 {{sfn|Greenwood|1997|p=1265}} |
|||
|vapor pressure comment= |
|||
|electronegativity= 1.3 {{sfn|Emsley|1998|p=50}} |
|||
|crystal structure= 六方密堆積 |
|||
|oxidation states= 4, '''3'''([[兩性 (化學)|兩性]]氧化物) |
|||
|electronegativity= 1.3 |
|||
|number of ionization energies=1 |
|number of ionization energies=1 |
||
|1st ionization energy= |
|1st ionization energy= 581 |
||
|atomic radius= 174 |
|||
|CAS number= 7440-71-3 {{sfn|CRC|2006|p=4.56}} |
|||
|covalent radius= 169±3 |
|||
|magnetic ordering= 51 K時從反鐵磁性變為順磁性<ref name=res>{{cite journal|last1=Schenkel|first1=R|title=The electrical resistivity of 244Cm metal|journal=Solid State Communications|volume=23|pages=389|year=1977|doi=10.1016/0038-1098(77)90239-3|issue=6 |bibcode = 1977SSCom..23..389S }}</ref> |
|||
|electrical resistivity= 1.25<ref name=res/> µ |
|||
|CAS number= 7440-51-9 |
|||
|isotopes= |
|isotopes= |
||
{{Elementbox_isotopes_decay2 | mn= |
{{Elementbox_isotopes_decay2 | mn=242 | sym=Cm |
||
| na=[[放射性同位素| |
| na=[[痕量放射性同位素|痕量]] | hl=160 d |
||
| dm1=[[ |
| dm1=[[自發裂變|SF]] | de1=- | pn1= | ps1=- |
||
| dm2=[[ |
| dm2=[[α衰變|α]] | de2=6.1 | pn2=238 | ps2=[[鈈|Pu]]}} |
||
{{ |
{{Elementbox_isotopes_decay3 | mn=243 | sym=Cm |
||
| na= |
| na=痕量 | hl=29.1 y |
||
| dm1= |
| dm1=α | de1=6.169 | pn1=239 | ps1=Pu |
||
| dm2= |
| dm2=[[電子捕獲|ε]] | de2=0.009 | pn2=243 | ps2=[[鋂|Am]] |
||
| dm3=SF | de3=- | pn3= | ps3=-}} |
|||
{{Elementbox_isotopes_decay2 | mn=250 | sym=Cf |
|||
{{Elementbox_isotopes_decay2 | mn=244 | sym=Cm |
|||
| na=痕量 | hl=13.08 y |
|||
| na=痕量 | hl=18.1 y |
|||
| dm1=α(99.92%)| de1=6.129 | pn1=246 | ps1=Cm |
|||
| |
| dm1=SF | de1=- | pn1= | ps1=- |
||
| dm2=α | de2=5.8048 | pn2=240 | ps2=Pu}} |
|||
{{Elementbox_isotopes_decay | mn=251 | sym=Cf |
|||
{{Elementbox_isotopes_decay2 | mn=245 | sym=Cm |
|||
| na=痕量 | hl=898 y |
|||
| |
| na=痕量 | hl=8500 y |
||
| dm1=SF | de1=- | pn1= | ps1=- |
|||
{{Elementbox_isotopes_decay2 | mn=252 | sym=Cf |
|||
| |
| dm2=α | de2=5.623 | pn2=241 | ps2=Pu}} |
||
{{Elementbox_isotopes_decay2 | mn=246 | sym=Cm |
|||
| dm1=α(96.91%)| de1=6.217 | pn1=248 | ps1=Cm |
|||
| na=痕量 | hl=4730 y |
|||
| dm2=SF(3.09%)| de2=– | pn2= | ps2=–}} |
|||
| dm1=α | de1=5.475 | pn1=242 | ps1=Pu |
|||
{{Elementbox_isotopes_decay2 | mn=253 | sym=Cf |
|||
| |
| dm2=SF | de2=- | pn2= | ps2=-}} |
||
{{Elementbox_isotopes_decay | mn=247 | sym=Cm |
|||
| dm1=[[β衰變|β<sup>−</sup>]](99.69%) | de1=0.29 | pn1=[[鑀的同位素|253]] | ps1=[[鑀|Es]] |
|||
| |
| na=痕量 | hl=1.56{{e|7}} y |
||
| dm=α | de=5.353 | pn=243 | ps=Pu}} |
|||
{{Elementbox_isotopes_decay2 | mn=254 | sym=Cf |
|||
{{Elementbox_isotopes_decay2 | mn=248 | sym=Cm |
|||
| na=syn | hl=60.5 d |
|||
| na=痕量 | hl=3.40{{e|5}} y |
|||
| dm1=SF(99.69%) | de1=– | pn1= | ps1=– |
|||
| |
| dm1=α | de1=5.162 | pn1=244 | ps1=Pu |
||
| dm2=SF | de2=- | pn2= | ps2=-}} |
|||
|isotopes comment=同位素參考資料:{{sfn|CRC|2006|p=11.196}}<ref name="NNDC2008">{{cite web |
|||
{{Elementbox_isotopes_decay3 | mn=250 | sym=Cm |
|||
|url = http://www.nndc.bnl.gov/chart/ |
|||
| na=[[放射性同位素|syn]] | hl=9000 y |
|||
|author = NNDC contributors |
|||
| dm1=SF | de1=- | pn1= | ps1=- |
|||
|editor = Sonzogni, Alejandro A.(數據庫管理員) |
|||
| dm2=α | de2=5.169 | pn2=246 | ps2=Pu |
|||
|title = Chart of Nuclides |
|||
| dm3=[[β衰變|β<sup>−</sup>]] | de3=0.037 | pn3=250 | ps3=[[錇|Bk]]}} |
|||
|publisher = National Nuclear Data Center, Brookhaven National Laboratory |
|||
|isotopes comment= |
|||
|accessdate = 2010-03-01 |
|||
|discovered by=[[格倫·西奧多·西博格]]、[[Ralph A. James]]、[[阿伯特·吉奧索]] |
|||
|year = 2008}}</ref> |
|||
|discovery date=1944 |
|||
|discovered by=[[勞倫斯伯克利國家實驗室]] |
|||
|discovery date=1950 |
|||
}} |
}} |
||
'''Curium''' is a [[transuranic element|transuranic]] [[radioactive decay|radioactive]] [[chemical element]] with the symbol '''Cm''' and [[atomic number]] 96. This element of the [[actinide]] series was named after [[Marie Curie|Marie Skłodowska-Curie]] and her husband [[Pierre Curie]] - both were known for their research on radioactivity. Curium was first intentionally produced and identified in July 1944 by the group of [[Glenn T. Seaborg]] at the [[University of California, Berkeley]]. The discovery was kept secret and only released to the public in November 1945. Most curium is produced by bombarding [[uranium]] or [[plutonium]] with [[neutron]]s in [[nuclear reactor]]s – one [[tonne]] of spent [[nuclear fuel]] contains about 20 grams of curium. |
|||
'''鉲'''('''Californium''')是一種[[放射性]]金屬[[化學元素]],符號為'''Cf''',[[原子序]]為98。[[伯克利加州大學]]於1950年以[[α粒子]]([[氦-4]]離子)撞擊[[鋦]],首次產生了鉲元素。鉲屬於[[錒系元素]],是人們[[人工合成元素|合成]]的第六個[[超鈾元素]]。繼[[鑀]]之後,鉲是產量能以肉眼可見的元素中原子量第二高的。該元素是以[[美國]][[加利福尼亞州]]及[[加州大學]]命名的。它也是地球上自然產生的元素中質量最高的。更重的元素必須通過人工合成才能產生。 |
|||
Curium is a hard, dense, silvery metal with a relatively high melting point and boiling point for an actinide. Whereas it is [[paramagnetism|paramagnetic]] at [[Standard conditions for temperature and pressure|ambient conditions]], it becomes [[antiferromagnetism|antiferromagnetic]] upon cooling, and other magnetic transitions are also observed for many curium compounds. In compounds, curium usually exhibits [[valence (chemistry)|valence]] +3 and sometimes +4, and the +3 valence is predominant in solutions. Curium readily oxidizes, and its oxides are a dominant form of this element. It forms strongly [[fluorescence|fluorescent]] complexes with various organic compounds, but there is no evidence of its incorporation into [[bacteria]] and [[archaea]]. When introduced into the human body, curium accumulates in the bones, lungs and liver, where it promotes [[cancer]]. |
|||
在一般壓力下,鉲擁有兩種[[晶體結構]]:其一存在於900 °C以上,另一存在於900 °C以下。高壓下,鉲還有第三種晶體結構。在室溫下,鉲會在空氣中緩慢地失去光澤。鉲的化合物主要包含鉲(III),處於這一形態的鉲能夠形成3個[[化學鍵]]。已知的20個[[鉲的同位素]]中,鉲-251是最為穩定的,[[半衰期]]有898年。由於半衰期非常短,所以在地球的地殼中不存在大量的鉲元素。<ref group="注">地球大約在[[地球年齡|45億年前形成]],而在地球中自然放射的中子不足以從較穩定的元素產生出大量的鉲。</ref>鉲-252是最常見的同位素,半衰期約為2.64年。該同位素是在美國的[[橡樹嶺國家實驗室]]及[[俄羅斯]]的[[核反應器研究所]]合成的。 |
|||
All known [[isotope]]s of curium are radioactive and have a small [[critical mass]] for a sustained [[nuclear chain reaction]]. They predominantly emit [[alpha radiation|α-particles]], and the heat released in this process can potentially produce electricity in [[radioisotope thermoelectric generator]]s. This application is hindered by the scarcity, high cost and radioactivity of curium isotopes. Curium is used in production of heavier actinides and of the <sup>238</sup>Pu [[radionuclide]] for power sources in [[artificial pacemaker]]s. It served as the [[alpha radiation|α-source]] in the [[alpha particle X-ray spectrometer]]s installed on the [[Mars Pathfinder|Sojourner]], [[Mars rover|Mars]], [[Mars 96]], [[Mars Exploration Rover|Athena]], [[Spirit rover|Spirit]] and [[Opportunity rover]]s as well as the [[Mars Science Laboratory]] to analyze the composition and structure of the rocks on the surface of [[Mars]] and the [[Moon]]. Such a spectrometer will also be used by the [[Philae lander]] of the [[Rosetta (spacecraft)|Rosetta]] spacecraft to probe the surface of the [[67P/Churyumov-Gerasimenko]] [[comet]]. |
|||
鉲是少數具有實際用途的超鈾元素之一。人們主要利用某些[[鉲的同位素|鉲同位素]]釋放[[中子]]的能力。比如,鉲能夠用於發動[[核反應爐]],也可以使用在[[中子散射]]和[[中子譜學]]中對材料進行研究。鉲還能用於製造更重的元素:[[Uuo]](第118號元素)就是以[[鈣-48]]離子撞擊鉲-249合成的。在處理鑀的時候,必須考慮到它的放射性。當[[生物累積|累積]]在骨骼組織時,鉲可以破壞[[紅血球]]的形成。 |
|||
== |
==History== |
||
[[File:Glenn Seaborg - 1964.jpg|thumb|left|upright|Glenn T. Seaborg]] |
|||
[[File:Berkeley 60-inch cyclotron.gif|thumb|left|upright|The {{convert|60|in|cm|adj=on}} cyclotron at the Lawrence Radiation Laboratory, University of California, Berkeley, in August 1939.]] |
|||
Although curium had likely been produced in previous nuclear experiments, it was [[discoveries of the chemical elements|first intentionally synthesized]], isolated and identified in 1944, at the [[University of California, Berkeley]] by [[Glenn T. Seaborg]], Ralph A. James, and [[Albert Ghiorso]]. In their experiments, they used a {{convert|60|in|cm|adj=on}} [[cyclotron]].<ref>{{cite book|title = The New Chemistry: A Showcase for Modern Chemistry and Its Applications|first = Nina|last = Hall|publisher = Cambridge University Press|year = 2000|pages = 8–9|isbn = 978-0-521-45224-3|url = http://books.google.com/books?id=U4rnzH9QbT4C&pg=PA8}}</ref> |
|||
Curium was chemically identified at the Metallurgical Laboratory (now [[Argonne National Laboratory]]) at the [[University of Chicago]]. It was the third [[transuranium element]] to be discovered even though it is the fourth in the series – the lighter element [[americium]] was unknown at the time.<ref name="E96">Seaborg, G. T.; James, R. A. and Ghiorso, A.: "The New Element Curium (Atomic Number 96)", NNES PPR ''(National Nuclear Energy Series, Plutonium Project Record)'', Vol. 14 B, ''The Transuranium Elements: Research Papers'', Paper No. 22.2, McGraw-Hill Book Co., Inc., New York, 1949; [http://www.osti.gov/cgi-bin/rd_accomplishments/display_biblio.cgi?id=ACC0049&numPages=13&fp=N Abstract]; [http://www.osti.gov/accomplishments/documents/fullText/ACC0049.pdf Full text (January 1948)].</ref><ref name="Morrs"/> |
|||
=== 物理特性 === |
|||
鉲是一種銀白色的[[錒系元素|錒系]]金屬{{sfn|Jakubke|1994|p=166}},[[熔點]]為900 ± 30 °C,估計的[[沸點]]為1745 °C。{{sfn|Haire|2006|pp=1522–1523}}處於純金屬態時,鉲是具延展性的,可以用刀片輕易切開。在真空狀態下的鉲金屬到了300 °C以上時便會氣化。{{sfn|Haire|2006|p=1526}}在51 [[開氏度|K]](−220 °C)以下的鉲金屬具[[鐵磁性]]或[[亞鐵磁性]],在48至66 K時具[[反鐵磁性]],而在160 K(−110 °C)以上時具[[順磁性]]。{{sfn|Haire|2006|p=1525}}它與[[鑭系元素]]能夠形成[[合金]],但人們對其所知甚少。{{sfn|Haire|2006|p=1526}} |
|||
The sample was prepared as follows: first [[plutonium]] nitrate solution was coated on a [[platinum]] foil of about 0.5 cm<sup>2</sup> area, the solution was evaporated and the residue was converted into plutonium dioxide (PuO<sub>2</sub>) by [[annealing (metallurgy)|annealing]]. Following cyclotron irradiation of the oxide, the coating was dissolved with [[nitric acid]] and then precipitated as the hydroxide using concentrated aqueous [[ammonium hydroxide|ammonia solution]]. The residue was dissolved in [[perchloric acid]], and further separation was carried out by [[ion exchange]] to yield a certain isotope of curium. The separation of curium and americium was so painstaking that the Berkeley group initially called those elements ''[[wikt:pandemonium|pandemonium]]'' (from Greek for ''all demons'' or ''hell'') and ''[[wikt:delirium|delirium]]'' (from Latin for ''madness'').<ref name=radio/><ref>Krebs, Robert E. [http://books.google.com/books?id=yb9xTj72vNAC&pg=PA322 The history and use of our earth's chemical elements: a reference guide], Greenwood Publishing Group, 2006, ISBN 0-313-33438-2 p. 322</ref><ref>{{OEtymD|pandemonium}}</ref><ref>{{OEtymD|delirium}}</ref> |
|||
在一個大氣壓力下,鉲有著兩種[[晶體結構]]:一種是雙層[[六方密排]]結構(α),另一種為[[面心立方]]結構(β)。{{#tag:ref|雙層六方密排結構(dhcp)的[[晶胞]]由位於同一個六邊形平面上的兩個六邊形密排結構組成,因此dhcp結構的順序為ABACABAC。{{sfn|Szwacki|2010|p=80}}|group="注"}}其中α型在900 °C下出現,密度為15.10 g/cm<sup>3</sup>;β型在900 °C以上出現,密度為8.74 g/cm<sup>3</sup>。{{sfn|O'Neil|2006|p=276}}在48 [[帕斯卡|GPa]]的壓力下,β型會轉變為[[正交晶系]]結構。這是由於其原子中的[[電子層|5f電子]]在此壓力下會[[離域電子|離域]],並能夠參與鍵合。{{sfn|Haire|2006|p=1522}}<ref group="注">質量較低的三種超鈈元素([[鎇]]、[[鋦]]、[[錇]])要使5f電子離域所需的壓力更低得多。{{sfn|Haire|2006|p=1522}}</ref> |
|||
The curium-242 isotope was produced in July–August 1944 by bombarding <sup>239</sup>Pu with [[alpha radiation|α-particles]] to produce curium with the release of a [[neutron]]: |
|||
物質的[[體積模量]]指的是該物質抗衡均勻壓力的強度。鉲的體積模量為50 ± 5 GPa,這與三價的鑭系金屬相似,但比一些常見的金屬低(如[[鋁]]:70 GPa)。{{sfn|Haire|2006|p=1522}} |
|||
: <math>\mathrm{^{239\!\,}_{\ 94}Pu\ +\ ^{4}_{2}He\ \longrightarrow \ ^{242}_{\ 96}Cm\ +\ ^{1}_{0}n}</math> |
|||
Curium-242 was unambiguously identified by the characteristic energy of the α-particles emitted during the decay: |
|||
=== 化學特性及化合物 === |
|||
: <math>\mathrm{^{242}_{\ 96}Cm\ \longrightarrow \ ^{238}_{\ 94}Pu\ +\ ^{4}_{2}He}</math> |
|||
The [[half-life]] of this [[alpha decay]] was first measured as 150 days and then corrected to 162.8 days.<ref name="nubase"/> |
|||
Another isotope <sup>240</sup>Cm was produced in a similar reaction in March 1945: |
|||
: <math>\mathrm{^{239}_{\ 94}Pu\ +\ ^{4}_{2}He\ \longrightarrow \ ^{240}_{\ 96}Cm\ +\ 3\ ^{1}_{0}n}</math> |
|||
The half-life of the <sup>240</sup>Cm α-decay was correctly determined as 26.7 days.<ref name="nubase"/> |
|||
The discovery of curium, as well as americium, in 1944 was closely related to the [[Manhattan Project]], the results were confidential and declassified only in 1945. Seaborg leaked the synthesis of the elements 95 and 96 on the U.S. radio show for children, the [[Quiz Kids]], five days before the official presentation at an [[American Chemical Society]] meeting on November 11, 1945, when one of the listeners asked whether any new transuranium element beside plutonium and [[neptunium]] had been discovered during the war.<ref name=radio>{{cite web|url = http://pubs.acs.org/cen/80th/americium.html|title = Chemical & Engineering News: It's Elemental: The Periodic Table – Americium|accessdate = 07-12-2008| first = Rachel Sheremeta|last = Pepling|year = 2003}}</ref> The discovery of curium (<sup>242</sup>Cm and <sup>240</sup>Cm), their production and compounds were later patented listing only Seaborg as the inventor.<ref>Seaborg, G. T. {{US patent|3161462}} "Element", Filing date: 7 February 1949, Issue date: December 1964</ref> |
|||
{{double image|left|Marie Curie (Nobel-Chem).png|150|Curie-pierre.jpg|150|Marie and Pierre Curie}} |
|||
The new element was named after [[Marie Curie|Marie Skłodowska-Curie]] and her husband [[Pierre Curie]] who are noted for discovering [[radium]] and for their work in [[radioactivity]]. It followed the example of [[gadolinium]], a [[lanthanide]] element above curium in the periodic table, which was named after the explorer of the [[rare earth element]]s [[Johan Gadolin]]:<ref>Greenwood, p. 1252</ref> |
|||
::''"As the name for the element of atomic number 96 we should like to propose "curium" , with symbol Cm. The evidence indicates that element 96 contains seven 5f electrons and is thus analogous to the element gadolinium with its seven 4f electrons in the regular rare earth series. On this base element 96 is named after the Curies in a manner analogous to the naming of gadolinium, in which the chemist Gadolin was honored."<ref name="E96"/>'' |
|||
The first curium samples were barely visible, and were identified by their radioactivity. Louis Werner and [[Isadore Perlman]] created the first substantial sample of 30 µg curium-242 hydroxide at the University of California in 1947 by bombarding [[americium]]-241 with neutrons.<ref name=CRC>Hammond C. R. "The elements" in {{RubberBible86th}}</ref><ref>L. B. Werner, I. Perlman: "Isolation of Curium", NNES PPR (''National Nuclear Energy Series, Plutonium Project Record''), Vol. 14 B, ''The Transuranium Elements: Research Papers'', Paper No. 22.5, McGraw-Hill Book Co., Inc., New York, 1949.</ref><ref>{{cite web|url=http://www.nap.edu/readingroom.php?book=biomems&page=iperlman.html |title=National Academy of Sciences. Isadore Perlman 1915–1991 |publisher=Nap.edu |date= |accessdate=2011-03-25}}</ref> Macroscopic amounts of [[curium fluoride]] were obtained in 1950 by W. W. T. Crane, J. C. Wallmann and B. B. Cunningham. Its magnetic susceptibility was very close to that of GdF<sub>3</sub> providing the first experimental evidence for the +3 valence of curium in its compounds.<ref name=CRC/> Curium metal was produced only in 1951 by reduction of curium fluoride with [[barium]].<ref name="CM_METALL">{{cite journal|first = J. C.|last = Wallmann|coauthors = Crane, W. W. T.; Cunningham, B. B.|title = The Preparation and Some Properties of Curium Metal|journal = [[Journal of the American Chemical Society]]|year = 1951|volume =73|issue =1|pages = 493–494|doi = 10.1021/ja01145a537}}</ref><ref>{{cite journal|author =Werner, L. B.; Perlman, I.|title =First Isolation of Curium| journal = Journal of the American Chemical Society|year = 1951| volume =73|issue =1|pages = 5215–5217|doi = 10.1021/ja01155a063}}</ref> |
|||
==Characteristics== |
|||
===Physical=== |
|||
[[File:Closest packing ABAC.png|thumb|Double-hexagonal close packing with the layer sequence ABAC in the crystal structure of α-curium (A: green, B: blue, C: red)]] |
|||
[[File:Cm-Fluoreszenz.GIF|thumb|Orange [[fluorescence]] of Cm<sup>3+</sup> ions in a solution of tris(hydrotris)pyrazolylborato-Cm(III) complex, excited at 396.6 nm.]] |
|||
A synthetic, radioactive element, curium is a hard dense metal with silvery-white appearance and physical and chemical properties resembling those of [[gadolinium]]. Its melting point of 1340 °C is significantly higher than that of the previous transuranic elements neptunium (637 °C), plutonium (639 °C) and americium (1173 °C). In comparison, gadolinium melts at 1312 °C. The boiling point of curium is 3110 °C. With a density of 13.52 g/cm<sup>3</sup>, curium is significantly lighter than neptunium (20.45 g/cm<sup>3</sup>) and plutonium (19.8 g/cm<sup>3</sup>), but is heavier than most other metals. Between two crystalline forms of curium, the α-Cm is more stable at ambient conditions. It has a hexagonal symmetry, [[space group]] P6<sub>3</sub>/mmc, lattice parameters ''a'' = 365 [[picometer|pm]] and ''c'' = 1182 pm, and four [[formula unit]]s per [[unit cell]].<ref name="Milman">{{cite journal|last1=Milman|first1=V|title=Crystal structures of curium compounds: an ab initio study|journal=Journal of Nuclear Materials|volume=322|issue=2–3|page=165|year=2003|doi=10.1016/S0022-3115(03)00321-0|bibcode=2003JNuM..322..165M}}</ref> The crystal consists of a double-[[Close-packing of spheres|hexagonal close packing]] with the layer sequence ABAC and so is isotypic with α-lanthanum. At pressures above 23 [[Pascal (unit)|GPa]], at room temperature, α-Cm transforms into β-Cm, which has a [[Cubic crystal system|face-centered cubic]] symmetry, space group Fm{{overline|3}}m and the lattice constant ''a'' = 493 pm.<ref name = "Milman"/> Upon further compression to 43 GPa, curium transforms to an [[Orthorhombic crystal system|orthorhombic]] γ-Cm structure similar to that of α-uranium, with no further transitions observed up to 52 GPa. These three curium phases are also referred to as Cm I, II and III.<ref>Young, D. A. [http://books.google.com/books?id=F2HVYh6wLBcC&pg=PA227 Phase diagrams of the elements], University of California Press, 1991, ISBN 0-520-07483-1p. 227</ref><ref>{{cite journal|last1=Haire|first1=R|last2=Peterson|first2=J|last3=Benedict|first3=U|last4=Dufour|first4=C|last5=Itie|first5=J|title=X-ray diffraction of curium-248 metal under pressures of up to 52 GPa|journal=Journal of the Less Common Metals|volume=109|issue=1|page=71|year=1985|doi=10.1016/0022-5088(85)90108-0}}</ref> |
|||
Curium has peculiar magnetic properties. Whereas its neighbor element actinium shows no deviation from [[Curie–Weiss law|Curie-Weiss]] [[paramagnetism]] in the entire temperature range, α-Cm transforms to an [[Antiferromagnetism|antiferromagnetic]] state upon cooling to 65–52 K,<ref>{{cite journal|last1=Kanellakopulos|first1=B|title=The magnetic susceptibility of Americium and curium metal|journal=Solid State Communications|volume=17|issue=6|page=713|year=1975|doi=10.1016/0038-1098(75)90392-0|bibcode = 1975SSCom..17..713K }}</ref><ref>{{cite journal|last1=Fournier|first1=J|title=Curium: A new magnetic element|journal=Physica B+C|volume=86–88|page=30|year=1977|doi=10.1016/0378-4363(77)90214-5|bibcode = 1977PhyBC..86...30F }}</ref> and β-Cm exhibits a [[Ferrimagnetism|ferrimagnetic]] transition at about 205 K. Meanwhile, curium pnictides show [[Ferromagnetism|ferromagnetic]] transitions upon cooling: <sup>244</sup>CmN and <sup>244</sup>CmAs at 109 K, <sup>248</sup>CmP at 73 K and <sup>248</sup>CmSb at 162 K. Similarly, the lanthanide analogue of curium, gadolinium, as well as its pnictides also show magnetic transitions upon cooling, but the transition character is somewhat different: Gd and GdN become ferromagnetic, and GdP, GdAs and GdSb show antiferromagnetic ordering.<ref>Nave, S. E.; Huray, P. G.; Peterson, J. R. and Damien, D. A. [http://www.osti.gov/bridge/purl.cover.jsp;jsessionid=ECF73C70531D64E8B663048ECE8C10F9?purl=/6263633-jkoGGI/ Magnetic susceptibility of curium pnictides], Oak Ridge National Laboratory</ref> |
|||
In accordance with magnetic data, electrical resistivity of curium increases with temperature – about twice between 4 and 60 K – and then remains nearly constant up to room temperature. There is a significant increase in resistvity over time (about 10 µOhm·cm/h) due to self-damage of the crystal lattice by alpha radiation. This makes uncertain the absolute resistivity value for curium (about 125 µΩ·cm). The resistivity of curium is similar to that of gadolinium and of the actinides plutonium and neptunium, but is significantly higher than that of americium, uranium, [[polonium]] and [[thorium]].<ref name=res/><ref>{{cite journal|last1=Schenkel|first1=R|title=The electrical resistivity of 244Cm metal|journal=Solid State Communications|volume=23|issue=6|page=389|year=1977|doi=10.1016/0038-1098(77)90239-3|bibcode = 1977SSCom..23..389S }}</ref> |
|||
Under ultraviolet illumination, curium(III) ions exhibit strong and stable yellow-orange [[fluorescence]] with a maximum in the range about 590–640 nm depending on their environment.<ref name="denecke">{{cite journal|last1=Denecke|first1=Melissa A.|last2=Rossberg|first2=André|last3=Panak|first3=Petra J.|last4=Weigl|first4=Michael|last5=Schimmelpfennig|first5=Bernd|last6=Geist|first6=Andreas|title=Characterization and Comparison of Cm(III) and Eu(III) Complexed with 2,6-Di(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine Using EXAFS, TRFLS, and Quantum-Chemical Methods|journal=Inorganic Chemistry|volume=44|issue=23|page=8418|year=2005|pmid=16270980|doi=10.1021/ic0511726}}</ref> The fluorescence originates from the transitions from the first excited state <sup>6</sup>D<sub>7/2</sub> and the ground state <sup>8</sup>S<sub>7/2</sub>. Analysis of this fluorescence allows monitoring interactions between Cm(III) ions in organic and inorganic complexes.<ref name=plb>Bünzli, J.-C. G. and Choppin, G. R. ''Lanthanide probes in life, chemical, and earth sciences: theory and practice'', Elsevier, Amsterdam, 1989 ISBN 0-444-88199-9</ref> |
|||
===Chemical=== |
|||
Curium ions in solution assume the [[oxidation state]] of +3, which is the most stable oxidation state for curium.<ref>Penneman, p. 24</ref> The +4 oxidation state is observed only in a few solid phases, such as CmO<sub>2</sub> and CmF<sub>4</sub>.<ref>{{cite journal|last1=Keenan|first1=Thomas K.|journal=Journal of the American Chemical Society|volume=83|issue=17|page=3719|year=1961|doi=10.1021/ja01478a039}}</ref><ref name = "asprey"/> Chemical behavior of curium is different from actinides thorium and uranium, and is similar to that of americium and many [[lanthanides]]. In aqueous solution, the Cm<sup>3+</sup> ion is colorless to pale green,<ref name=g1265>Greenwood, p. 1265</ref> and Cm<sup>4+</sup> ion is pale yellow.<ref name="HOWI_1956">Holleman, p. 1956</ref> The optical absorption of Cm<sup>3+</sup> ions contains three sharp peaks at 375.4, 381.2 and 396.5 nanometers and their strength can be directly converted into the concentration of the ions.<ref>Penneman, pp. 25–26</ref> Curium ions are [[HSAB theory|hard Lewis acids]] and thus form most stable complexes with hard bases.<ref>{{cite journal|last1=Jensen|first1=Mark P.|last2=Bond|first2=Andrew H.|title=Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations|journal=Journal of the American Chemical Society|volume=124|issue=33|page=9870|year=2002|pmid=12175247|doi=10.1021/ja0178620}}</ref> The bonding is mostly ionic, with a small covalent component.<ref>{{cite journal|author=Seaborg, G. T. |title=Overview of the Actinide and Lanthanide (the ''f'') Elements|journal=Radiochimica Acta|year=1993|volume=61|pages=115–122}}</ref> Curium in its complexes commonly exhibits a 9-fold coordination environment, within a tricapped [[trigonal prismatic geometry|trigonal prismatic]] geometry.<ref>Greenwood, p. 1267</ref> |
|||
===Isotopes=== |
|||
<div style="float:right; margin:0; font-size:85%;"> |
|||
{| class="wikitable" |
{| class="wikitable" |
||
!colspan="7"| [[Thermal neutron]] [[Neutron cross-section|cross section]]s ([[Barn (unit)|barns]])<ref>Pfennig, G.; Klewe-Nebenius, H. and Seelmann Eggebert, W. (Eds.): Karlsruhe [[nuclide]], 6th Ed. 1998</ref> |
|||
|+ 鉲的某些化合物{{sfn|Jakubke|1994|p=166}}{{#tag:ref|其他+3氧化態還包括硫化物及[[茂金屬]]。{{sfn|Cotton|1999|p=1163}}具+4態的化合物是強[[氧化劑]],具+2態的則為強[[還原劑]]。{{sfn|Jakubke|1994|p=166}}|group="注"}} |
|||
! 氧化態 !! 化合物 !! 公式 !! 顔色 |
|||
|- |
|- |
||
| ||<sup>242</sup>Cm||<sup>243</sup>Cm||<sup>244</sup>Cm||<sup>245</sup>Cm||<sup>246</sup>Cm||<sup>247</sup>Cm |
|||
| +2 || 二溴化鉲 || CfBr<sub>2</sub> || 黃色 |
|||
|- |
|- |
||
|Fission||5||617||1.04||2145||0.14||81.90 |
|||
| +2 || 二碘化鉲 || CfI<sub>2</sub> || 深紫色 |
|||
|- |
|- |
||
|Capture||16||130||15.20||369||1.22||57 |
|||
| +3 || 三氧化二鉲 || Cf<sub>2</sub>O<sub>3</sub> || 黃綠色 |
|||
|- |
|- |
||
|C/F ratio||3.20||0.21||14.62||0.17||8.71||0.70 |
|||
| +3 || 三氟化鉲 || CfF<sub>3</sub> || 鮮綠色 |
|||
|- |
|- |
||
!colspan="7"| [[low enriched uranium|LEU]] [[spent fuel]] 20 years after 53 MWd/kg [[burnup]]<ref>{{cite journal|doi=10.1080/08929880500357682|last1=Kang|year=2005|page=169|issue=3|volume=13|journal=Science and Global Security|url=http://www.princeton.edu/sgs/publications/sgs/pdf/13_3%20Kang%20vonhippel.pdf|first1=Jungmin|last2=Von Hippel|first2=Frank|title=Limited Proliferation-Resistance Benefits from Recycling Unseparated Transuranics and Lanthanides from Light-Water Reactor Spent Fuel}}</ref> |
|||
| +3 || 三氯化鉲 || CfCl<sub>3</sub> || 翠綠色 |
|||
|- |
|- |
||
|colspan="2" |3 common isotopes ||51||3700||390|| || |
|||
| +3 || 三碘化鉲 || CfI<sub>3</sub> || 檸檬色 |
|||
|- |
|- |
||
!colspan="7"| [[Fast reactor]] [[MOX fuel]] (avg 5 samples, [[burnup]] 66-120GWd/t)<ref>{{cite journal|doi=10.3327/jnst.38.912|url=http://wwwsoc.nii.ac.jp/aesj/publication/JNST2001/No.10/38_912-914.pdf|format=PDF|title=Analysis of Curium Isotopes in Mixed Oxide Fuel Irradiated in Fast Reactor|journal=Journal of Nuclear Science and Technology|volume=38|year=2001|issue=10|pages=912–914|author=Osaka, M. ''et al.''}}</ref> |
|||
| +4 || 二氧化鉲 || CfO<sub>2</sub> || 棕黑色 |
|||
|- |
|- |
||
|colspan="2" |Total curium 3.09{{e|-3}}% ||27.64%||70.16%||2.166%||0.0376%||0.000928% |
|||
| +4 || 四氟化鉲 || CfF<sub>4</sub> || 綠色 |
|||
|} |
|} |
||
{| Class = "wikitable" |
|||
鉲的[[化合價]]可以是4、3或2,也就是說一個鉲原子能夠形成2至4個[[化學鍵]]。{{sfn|O'Neil|2006|p=276}}其化學屬性預計將會類似於別的三價錒系元素,以及在[[元素週期表]]中位於鉲以上的[[鏑]]。{{sfn|Seaborg|2004}}{{sfn|CRC|2006|p=4.8}}鉲在室溫下會在空氣中緩慢地失去光澤,速度隨著濕度的提高而加快。{{sfn|O'Neil|2006|p=276}}鉲可以和[[氫]]、[[氮]]和任何[[氧族元素]]加熱進行反應,其中與不含濕氣的氫或與水溶[[無機酸]]反應的速度極快。{{sfn|O'Neil|2006|p=276}} <!--請補充解釋鉲-249是唯一一種可以用於化學研究的同位素。<ref name="Emeleus">{{cite book|last=Emeleus|first=H. J.|title=Advances in Inorganic Chemistry|page=33|year=1987|publisher=Academic Press | isbn = 978-0-12-023631-2 }}</ref> /請解釋 --> |
|||
|- |
|||
| Isotope||<sup>242</sup>Cm||<sup>243</sup>Cm||<sup>244</sup>Cm||<sup>245</sup>Cm||<sup>246</sup>Cm||<sup>247</sup>Cm||<sup>248</sup>Cm||<sup>250</sup>Cm |
|||
|- |
|||
|[[Critical mass]], kg|| 25|| 7.5||33||6.8||39||7||40.4||23.5 |
|||
|} |
|||
</div> |
|||
{{see also|Isotopes of curium}} |
|||
About 20 [[Radionuclide|radioisotopes]] and 7 [[nuclear isomer]]s between <sup>233</sup>Cm and <sup>252</sup>Cm are known for curium, and no stable [[isotope]]s. The longest half-lives have been reported for <sup>247</sup>Cm (15.6 million years) and <sup>248</sup>Cm (348,000 years). Other long-lived isotopes are <sup>245</sup>Cm (half-life 8500 years), <sup>250</sup>Cm (8,300 years) and <sup>246</sup>Cm (4,760 years). Curium-250 is unusual by that it predominantly (about 86%) decays via [[spontaneous fission]]. The most commonly used curium isotopes are <sup>242</sup>Cm and <sup>244</sup>Cm with the half-lives of 162.8 days and 18.1 years, respectively.<ref name="nubase">{{cite journal|last1=Audi|first1=G|doi=10.1016/S0375-9474(97)00482-X|title=The N? evaluation of nuclear and decay properties|year=1997|page=1|issue=1|volume=624|journal=Nuclear Physics A|url=http://www.nndc.bnl.gov/amdc/nubase/Nubase2003.pdf|bibcode=1997NuPhA.624....1A}}</ref> |
|||
[[File:Sasahara.svg|thumb|325px|Transmutation flow between <sup>238</sup>Pu and <sup>244</sup>Cm in LWR.<ref>{{cite journal|url=http://www.jstage.jst.go.jp/article/jnst/41/4/448/_pdf|title=Neutron and Gamma Ray Source Evaluation of LWR High Burn-up UO2 and MOX Spent Fuels|journal=Journal of Nuclear Science and Technology|volume=41|issue=4|pages=448–456|year=2004|doi=10.3327/jnst.41.448|author=Sasahara, Akihiro|last2=Matsumura|first2=Tetsuo|last3=Nicolaou|first3=Giorgos|last4=Papaioannou|first4=Dimitri}}</ref><br>Fission percentage is 100 minus shown percentages.<br>Total rate of transmutation varies greatly by nuclide.<br><sup>245</sup>Cm–<sup>248</sup>Cm are long-lived with negligible decay.]] |
|||
鉲[[水溶液|水溶]]時處於鉲(III)[[正離子]]狀態。科學家未能[[氧化還原反應|還原或氧化]]溶液中的+3離子。{{sfn|CRC|2006|p=4.8}}鉲能夠形成能溶於水的[[氯化物]]、[[硝酸鹽]]、[[高氯酸鹽]]及[[硫酸鹽]],沉澱後形成[[氟化物]]、[[草酸鹽]]或[[氫氧化物]]。{{sfn|Seaborg|2004}} |
|||
All isotopes between <sup>242</sup>Cm and <sup>248</sup>Cm, as well as <sup>250</sup>Cm, undergo a self-sustaining [[nuclear chain reaction]] and thus in principle can act as a [[nuclear fuel]] in a reactor. As in most transuranic elements, the [[nuclear fission]] cross section is especially high for the odd-mass curium isotopes<sup>243</sup>Cm, <sup>245</sup>Cm and <sup>247</sup>Cm. These can be used in [[thermal-neutron reactor]]s, whereas a mixture of curium isotopes is only suitable for [[fast breeder reactor]]s since the even-mass isotopes are not fissile in a thermal reactor and accumulate as burn-up increases.<ref name="irsn">Institut de Radioprotection et de Sûreté Nucléaire: [http://ec.europa.eu/energy/nuclear/transport/doc/irsn_sect03_146.pdf "Evaluation of nuclear criticality safety. data and limits for actinides in transport"], p. 16</ref> The mixed-oxide (MOX) fuel, which is to be used in power reactors, should contain little or no curium because the neutron activation of <sup>248</sup>Cm will create [[californium]]. This is strong [[neutron]] emitter, and would pollute the back end of the fuel cycle and increase the dose to reactor personnel. Hence, if the [[minor actinides]] are to be used as fuel in a thermal neutron reactor, the curium should be excluded from the fuel or placed in special fuel rods where it is the only actinide present.<ref>{{cite book|author=National Research Council (U.S.). Committee on Separations Technology and Transmutation Systems|title=Nuclear wastes: technologies for separations and transmutation|url=http://books.google.com/books?id=iRI7Cx2D4e4C&pg=PA231|accessdate=19 April 2011|year=1996|publisher=National Academies Press|isbn=978-0-309-05226-9|pages=231–}}</ref> |
|||
The table to the right lists the [[critical mass]]es for curium isotopes for a sphere, without a moderator and reflector. With a metal reflector (30 cm of steel), the critical masses of the odd isotopes are about 3–4 kg. When using water (thickness ~20–30 cm) as the reflector, the critical mass can be as small as 59 gram for <sup>245</sup>Cm, 155 gram for <sup>243</sup>Cm and 1550 gram for <sup>247</sup>Cm. There is a significant uncertainty in these critical mass values. Whereas it is usually of the order 20%, the values for <sup>242</sup>Cm and <sup>246</sup>Cm were listed as large as 371 kg and 70.1 kg, respectively, by some research groups.<ref name="irsn"/><ref>{{cite journal|author=Okundo, H. and Kawasaki, H. |url=http://www.jstage.jst.go.jp/article/jnst/39/10/1072/_pdf |title=Critical and Subcritical Mass Calculations of Curium-243 to −247 Based on JENDL-3.2 for Revision of ANSI/ANS-8.15|journal=Journal of Nuclear Science and Technology|year=2002|volume=39|pages=1072–1085|doi=10.3327/jnst.39.1072|issue=10}}</ref> |
|||
=== 同位素 === |
|||
{{main|鉲的同位素}} |
|||
目前已知的鉲同位素共有20個,都是[[放射性同位素]]。其中最穩定的有鉲-251([[半衰期]]為898年)、鉲-249(351年)、鉲-250(13.08年)及鉲-252(2.645年)。<ref name="NNDC2008">{{cite web |
|||
| url = http://www.nndc.bnl.gov/chart/ |
|||
| author = NNDC contributors |
|||
| editor = Sonzogni, Alejandro A. (Database Manager) |
|||
| title = Chart of Nuclides |
|||
| publisher = National Nuclear Data Center, Brookhaven National Laboratory |
|||
| accessdate = 2010-03-01 |
|||
| year = 2008 }}</ref>其餘的同位素半衰期都在一年以下,大部分甚至少於20分鐘。<ref name="NNDC2008" />鉲同位素的[[質量數]]從237到256不等。<ref name="NNDC2008" /> |
|||
Currently, curium is not used as a nuclear fuel owing to its low availability and high price.<ref>[http://bundesrecht.juris.de/atg/__2.html § 2 Begriffsbestimmungen (Atomic Energy Act)] (in German)</ref> <sup>245</sup>Cm and <sup>247</sup>Cm have a very small critical mass and therefore could be used in portable [[nuclear weapon]]s, but none have been reported thus far. Curium-243 is not suitable for this purpose because of its short half-life and strong α emission which would result in excessive heat.<ref>{{cite book|author1=Jukka Lehto|author2=Xiaolin Hou|title=Chemistry and Analysis of Radionuclides: Laboratory Techniques and Methodology|url=http://books.google.com/books?id=v2iRJaO3SMIC&pg=PA303|accessdate=19 April 2011|date=2 February 2011|publisher=Wiley-VCH|isbn=978-3-527-32658-7|pages=303–}}</ref> Curium-247 would be highly suitable, having a half-life 647 times that of plutonium-239. |
|||
鉲-249是在錇-249進行[[β衰變]]後形成的。大部分其他的鉲同位素是在[[核反應爐]]中對錇進行強烈的中子輻射後產生的。{{sfn|CRC|2006|p=4.8}}雖然鉲-251的半衰期最長,但是由於容易吸收中子(高[[中子捕獲]]率)以及會與其他粒子產生反應(高[[中子截面]]),所以其產量只有10%。{{sfn|Haire|2006|p=1504}} |
|||
===Occurrence=== |
|||
鉲-252是個強[[中子]]射源,因此其[[放射性]]極高,非常危險。<ref>{{cite journal|author = Hicks, D. A. |title = Multiplicity of Neutrons from the Spontaneous Fission of Californium-252|journal = Physical Review|year = 1955|volume = 97|issue = 2|pages = 564–565|doi = 10.1103/PhysRev.97.564|last2 = Ise|first2 = John|last3 = Pyle|first3 = Robert V.|bibcode = 1955PhRv...97..564H }}</ref><ref>{{cite journal|author = Hicks, D. A. |title = Spontaneous-Fission Neutrons of Californium-252 and Curium-244|journal = Physical Review |year = 1955|volume = 98|issue = 5|pages = 1521–1523|doi = 10.1103/PhysRev.98.1521|last2 = Ise|first2 = John|last3 = Pyle|first3 = Robert V.|bibcode = 1955PhRv...98.1521H }}</ref><ref>{{cite journal|author =Hjalmar, E.; Slätis, H.; Thompson, S.G. |title = Energy Spectrum of Neutrons from Spontaneous Fission of Californium-252| journal = Physical Review| year = 1955| volume = 100|issue =5|pages = 1542–1543| doi = 10.1103/PhysRev.100.1542|bibcode = 1955PhRv..100.1542H }}</ref>鉲-252有96.9%的機率進行[[α衰變]](損失兩顆[[質子]]和兩顆中子),並形成[[鋦]]-248,剩餘的3.1%機率進行[[自發裂變]]。<ref name="NNDC2008" />一[[微克]](µg)的鉲-252每秒釋放230萬顆中子,平均每次自發裂變釋放3.7顆中子。<ref name="osti">{{cite journal|author = Martin, R. C.; Knauer, J. B.; Balo, P. A.| title = Production, Distribution, and Applications of Californium-252 Neutron Sources| year = 1999|url = http://www.osti.gov/bridge/purl.cover.jsp?purl=/15053-AE6cnN/native/ |doi = 10.1016/S0969-8043(00)00214-1|journal = Applied Radiation and Isotopes |volume = 53|issue = 4–5|pages = 785–92|pmid = 11003521 }}</ref>其他大部分的鉲同位素都以α衰變形成鋦的同位素([[原子序]]為96)。<ref name="NNDC2008" /> |
|||
[[File:Ivy Mike - mushroom cloud.jpg|thumb|Several isotopes of curium were detected in the fallout from the ''Ivy Mike'' nuclear test.]] |
|||
The longest-lived isotope of curium, <sup>247</sup>Cm, has a half-life of 15.6 million years. Therefore, all [[primordial nuclide|primordial]] curium, that is curium present on the Earth during its formation, should have decayed by now. Curium is produced artificially, in small quantities for research purposes. Furthermore, it occurs in spent [[nuclear fuel]]. Curium is present in nature in certain areas used for the atmospheric [[nuclear weapons testing|nuclear weapons tests]], which were conducted between 1945 and 1980.<ref name="lenntech">[http://www.lenntech.de/pse/pse.htm Curium] (in German)</ref> So the analysis of the debris at the testing site of the first U.S. [[hydrogen bomb]], [[Ivy Mike]], (1 November 1952, [[Enewetak Atoll]]), beside [[einsteinium]], [[fermium]], [[plutonium]] and [[americium]] also revealed isotopes of berkelium, californium and curium, in particular <sup>245</sup>Cm, <sup>246</sup>Cm and smaller quantities of <sup>247</sup>Cm, <sup>248</sup>Cm and <sup>249</sup>Cm. For reasons of military secrecy, this result was published only in 1956.<ref>{{cite journal|last1=Fields|first1=P.|last2=Studier|first2=M.|last3=Diamond|first3=H.|last4=Mech|first4=J.|last5=Inghram|first5=M.|last6=Pyle|first6=G.|last7=Stevens|first7=C.|last8=Fried|first8=S.|last9=Manning|first9=W.|title=Transplutonium Elements in Thermonuclear Test Debris|journal=Physical Review|volume=102|issue=1|page=180|year=1956|doi=10.1103/PhysRev.102.180|bibcode = 1956PhRv..102..180F }}</ref> |
|||
Atmospheric curium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 4,000 times higher concentration of curium at the sandy soil particles than in water present in the soil pores. An even higher ratio of about 18,000 was measured in [[loam]] soils.<ref name=LA2/> |
|||
== 歷史 == |
|||
[[File:Berkeley 60-inch cyclotron.gif|thumb|left|首次合成鉲時所用的1.5米直徑[[迴旋加速器]]]] |
|||
1950年2月9日前後,物理學家[[Stanley Gerald Thompson|Stanley G. Thompson]]、[[Kenneth Street, Jr.]]、[[阿伯特·吉奥索]]及[[格倫·西奧多·西博格]]在[[伯克利加州大學]]首次[[化學元素發現年表|發現]]了鉲元素。{{sfn|Cunningham|1968|p=103}}鉲是第六個被發現的[[超鈾元素]]。研究小組在1950年3月17日發佈了該項發現。<ref>{{cite journal|author = Thompson, S. G.|coauthors = Street, Jr. K.; Ghiorso, A.; Seaborg, G. T.|title = Element 98 |journal = Physical Review|year =1950| volume = 78|issue = 3|page = 298| doi = 10.1103/PhysRev.78.298.2| url = http://escholarship.org/uc/item/44g7z6hk|bibcode = 1950PhRv...78..298T }}</ref><ref name="E98">{{cite journal|author =Thompson, S. G.|coauthors = Street, Jr. K.; Ghiorso, A.; Seaborg, G. T.| title = The New Element Californium (Atomic Number 98)|journal = Physical Review|year =1950|volume =80|issue =5| page = 790| doi = 10.1103/PhysRev.80.790| url = http://www.osti.gov/accomplishments/documents/fullText/ACC0050.pdf|format=PDF|bibcode = 1950PhRv...80..790T }}</ref><ref>{{cite journal|author =Street, K., Jr.; Thompson, S. G.; Seaborg, G. T.| title= Chemical Properties of Californium|journal = Journal of the American Chemical Society|year = 1950| volume = 72|issue =10|page = 4832| doi = 10.1021/ja01166a528|url = http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA319899&Location=U2&doc=GetTRDoc.pdf|format=PDF }}</ref> |
|||
A few atoms of curium can be produced by [[Neutron capture|neutron capture reactions]] and [[beta decay]] in very highly concentrated [[uranium]]-bearing deposits.<ref name="emsley">{{cite book|last=Emsley|first=John|title=Nature's Building Blocks: An A-Z Guide to the Elements|edition=New|year=2011|publisher=Oxford University Press|location=New York, NY|isbn=978-0-19-960563-7}}</ref> |
|||
美國加州[[伯克利]]的1.5米直徑[[迴旋加速器]]將[[α粒子]]({{Nuclide|helium|4}})加速至35 MeV能量,射向一微克大小的鋦-242目標,以此產生了鉲-245({{Nuclide|californium|245}})和一顆[[自由中子]]({{SubatomicParticle|neutron}})。{{sfn|Cunningham|1968|p=103}} |
|||
:{{Nuclide|curium|242}} + {{Nuclide|helium|4}} → {{Nuclide|californium|245}} + {{su|b=0|p=1}}{{SubatomicParticle|neutron}} |
|||
此次實驗只產生了大約5千顆鉲原子,{{sfn|Seaborg|1996|p=82}}半衰期為44分鐘。{{sfn|Cunningham|1968|p=103}} |
|||
==Synthesis== |
|||
該新元素以加州和[[加州大學]]命名。這和95至97號元素的命名方式有所不同。第95至97號元素是利用類似於對上的元素之命名方式而命名的。{{sfn|Weeks|1968|p=849}}{{#tag:ref|[[銪]](Europium)是以發現時所在的大陸(歐洲,Europe)命名的,因此對下的95號元素[[鎇]](Americium)以美洲命名(America);[[釓]](Gadolinium)是以科學家、工程師[[約翰·加多林]](Johan Gadolin)命名的,所以96號元素[[鋦]](Curium)以[[瑪莉·居禮]](Marie Curie)和[[皮埃爾·居禮]](Pierre Curie)命名;[[鋱]](Terbium)是以發現地[[伊特比]](Ytterby)命名的,所以97號元素[[錇]](Berkelium)以發現地[[伯克利]](Berkeley)命名。{{sfn|Weeks|1968|p=848}}|group="注"}}但是,98號元素以上的[[鏑]](Dysprosium)的意思是「難取得」,所以研究人員決定打破此前的非正式命名常規。{{sfn|Heiserman|1992|p=347}} |
|||
===Isotope preparation=== |
|||
[[愛達荷國家實驗室]]通過對[[鈈]]目標體進行輻射,首次產生了重量可觀的鉲元素,並於1954年發佈了研究結果。<ref>{{cite journal|journal=[[Physical Review]]|volume=94|issue=4|pages=1083|year=1954|author=Diamond, H. ''et al.''|title=Identification of Californium Isotopes 249, 250, 251, and 252 from Pile-Irradiated Plutonium|doi = 10.1103/PhysRev.94.1083|bibcode = 1954PhRv...94.1083D }}</ref>產生的樣本中能夠觀察到鉲-252的高自發裂變率。1958年,科學家首次對濃縮鉲進行了實驗。{{sfn|Cunningham|1968|p=103}}在對[[鈈-239]]進行中子輻射連續5年之後,科學家在樣本中發現了從鉲-249到鉲-252的各個同位素。{{sfn|Jakubke|1994|p=166}}兩年後的1960年,勞倫斯伯克利國家實驗室的[[Burris Cunningham]]和[[James Wallman]]把鉲置於蒸汽與鹽酸中,第一次製成了鉲的化合物——三氯化鉲、[[氯氧化鉲]]及氧化鉲。<ref>{{cite journal|journal = Science News Letters|volume = 78|issue = 26|month = December|year = 1960|title = Element 98 Prepared }}</ref> |
|||
Curium is produced in small quantities in [[nuclear reactor]]s, and by now only kilograms of it have been accumulated for the <sup>242</sup>Cm and <sup>244</sup>Cm and grams or even milligrams for heavier isotopes. This explains the high price of curium, which has been be quoted at 160–185 [[United States dollar|USD]] per milligram,<ref name=CRC/> with a more recent estimate at 2,000 USD/g for <sup>242</sup>Cm and 170 USD/g for <sup>244</sup>Cm.<ref name=lect/> In nuclear reactors, curium is formed from <sup>238</sup>U in a series of nuclear reactions. In the first chain, <sup>238</sup>U captures a neutron and converts into <sup>239</sup>U, which via [[beta decay|β<sup>–</sup> decay]] transforms into <sup>239</sup>Np and <sup>239</sup>Pu. |
|||
:<math>\mathrm{^{238}_{\ 92}U\ \xrightarrow {(n,\gamma)} \ ^{239}_{\ 92}U\ \xrightarrow [23.5 \ min]{\beta^-} \ ^{239}_{\ 93}Np\ \xrightarrow [2.3565 \ d]{\beta^-} \ ^{239}_{\ 94}Pu}</math> <small>(the times are [[half-life|half-lives]])</small>. |
|||
1960年代,位於美國[[田納西州]][[橡樹嶺 (田納西州)|橡樹嶺]]的[[橡樹嶺國家實驗室]]利用其[[高通率同位素反應爐]](HFIR)產生了少量的鉲。<ref>{{cite web|url=http://web.ornl.gov/sci/rrd/pages/hfir.html|title=The High Flux Isotope Reactor|publisher=Oak Ridge National Laboratory|accessdate=2010-08-22|archiveurl=http://web.archive.org/web/20100527164346/http://web.ornl.gov/sci/rrd/pages/hfir.html <!--Added by H3llBot-->|archivedate=2010-05-27 }}</ref>到1995年為止,HFIR的實際鉲年產量為500毫克。{{sfn|Osborne-Lee|1995|p=11}}在《[[英美共同防禦協約]]》下[[英國]]向美國提供的鈈元素曾用於製造鉲。<ref>{{cite web |archiveurl=http://web.archive.org/web/20061213032416/http://www.mod.uk/NR/rdonlyres/B31B4EF0-A584-4CC6-9B14-B5E89E6848F8/0/plutoniumandaldermaston.pdf|format=PDF |archivedate=2006-12-13 |url=http://www.mod.uk/NR/rdonlyres/B31B4EF0-A584-4CC6-9B14-B5E89E6848F8/0/plutoniumandaldermaston.pdf |title=Plutonium and Aldermaston – an Historical Account |publisher=UK Ministry of Defence |date=2001-09-04 |accessdate=2007-03-15|page=30 }}</ref> |
|||
Further neutron capture followed by β<sup>–</sup>-decay produces the <sup>241</sup>Am isotope of [[americium]] which further converts into <sup>242</sup>Cm: |
|||
[[美國原子能協會]]在1970年代初起向工業及學術機構銷售鉲-252同位素,每微克價格為10美元<ref name="osti" />,從1970至1990年每年一共售出150微克鉲-252。{{sfn|Osborne-Lee|1995|p=6}}{{#tag:ref|《1974年能源組織改組法》實施後,[[美國核能管理委員會]]取代美國原子能協會,並提高了鉲-252的價格。到了1999年,每微克鉲-252的售價為60美元。這價格不包括封裝及運輸的費用。<ref name="osti" />|group="注"}}Haire和Baybarz於1974年用鑭金屬還原了氧化鉲(III),首次製成數微克重、厚度小於1微米的鉲金屬薄片。{{sfn|Haire|2006|p=1519}}<ref>{{cite journal|last1=Haire|first1=R.G.|last2=Baybarz|first2=R.D.|title=Crystal Structure and Melting Point of Californium Metal|journal=Journal of Inorganic and Nuclear Chemistry|volume=36|issue=6|pages=1295|year=1974|doi=10.1016/0022-1902(74)80067-9 }}</ref>{{#tag:ref|1975年的另一篇論文指出,前一年製成的鉲金屬實際上是六方型化合物Cf<sub>2</sub>O<sub>2</sub>S及面心立方型化合物CfS。<ref>{{cite journal|doi=10.1016/0022-1902(75)80787-1|journal=Journal of Inorganic and Nuclear Chemistry|year=1975|pages=1441–1442|volume=37|issue=6|title=On Californium Metal|last=Zachariasen|first=W. }}</ref>科學家在1976年證實了1974年的實驗結論,並繼續對鉲金屬進行研究。{{sfn|Haire|2006|p=1519}}|group="注"}} |
|||
:<math>\mathrm{^{239}_{\ 94}Pu\ \xrightarrow {2(n,\gamma)} \ ^{241}_{\ 94}Pu\ \xrightarrow [14.35 \ yr]{\beta^-} \ ^{241}_{\ 95}Am\ \xrightarrow {(n,\gamma)} \ ^{242}_{\ 95}Am\ \xrightarrow [16.02 \ h]{\beta^-} \ ^{242}_{\ 96}Cm}</math>. |
|||
For research purposes, curium is obtained by irradiating not uranium but plutonium, which is available in large amounts from spent nuclear fuel. Much higher neutron flux is used for the irradiation that results in a different reaction chain and formation of <sup>244</sup>Cm:<ref name = "Morrs">Morss, L. R.; Edelstein, N. M. and Fugere, J. (eds): ''The Chemistry of the Actinide Elements and transactinides'', volume 3, Springer-Verlag, Dordrecht 2006, ISBN 1-4020-3555-1.</ref> |
|||
== 存量 == |
|||
:<math>\mathrm{^{239}_{\ 94}Pu\ \xrightarrow {4(n,\gamma)} \ ^{243}_{\ 94}Pu\ \xrightarrow [4,956 \ h]{\beta^-} \ ^{243}_{\ 95}Am\ \xrightarrow {(n,\gamma)} \ ^{244}_{\ 95}Am\ \xrightarrow [10.1 \ h]{\beta^-} \ ^{244}_{\ 96}Cm}</math> |
|||
[[File:Operation Crossroads Baker Edit.jpg|thumb|核試驗已將少量的鉲散落在環境當中。]] |
|||
:<math>\mathrm{^{244}_{\ 96}Cm\ \xrightarrow [18.11 \ yr]{\alpha} \ ^{240}_{\ 94}Pu}</math> |
|||
地球上有著極少量的鉲,主要出現在含[[鈾]]量很高的[[鈾礦]]中。鈾在[[中子捕獲|捕獲中子]]之後進行[[β衰變]],從而形成鉲。<ref name="ANL2005">{{cite web|url=http://www.evs.anl.gov/pub/doc/Californium.pdf|title=Human Health Fact Sheet: Californium|date=August 2005|publisher=Argonne National Laboratory|author=ANL contributors|format=PDF }}</ref><ref name="emsley">{{cite book|last=Emsley|first=John|title=Nature's Building Blocks: An A-Z Guide to the Elements|edition=New|year=2011|publisher=Oxford University Press|location=New York, NY | isbn = 978-0-19-960563-7 }}</ref>在使用鉲進行探礦或醫學治療的設施附近也可以發現鉲。{{sfn|Emsley|2001|p=90}}鉲不易溶於水,但會黏附在泥土上,所以泥土中鉲的濃度可以比泥土粒子周圍的水高出500倍。<ref name="ANL2005" /> |
|||
Curium-244 decays into <sup>240</sup>Pu by emission of alpha particle, but it also absorbs neutrons resulting in a small amount of heavier curium isotopes. Among those, <sup>247</sup>Cm and <sup>248</sup>Cm are popular in scientific research because of their long half-lives. However, the production rate of <sup>247</sup>Cm in thermal neutron reactors is relatively low because of it is prone to undergo fission induced by thermal neutrons.<ref name=haire/> Synthesis of <sup>250</sup>Cm via [[neutron absorption]] is also rather unlikely because of the short half-life of the intermediate product <sup>249</sup>Cm (64 min), which converts by β<sup>–</sup> decay to the [[berkelium]] isotope <sup>249</sup>Bk.<ref name=haire/> |
|||
1980年之前大氣層[[核試驗]]的[[輻射落塵]]散落在環境中,其中含有少量的鉲。<ref name="ANL2005" />從空氣中採得的核爆輻射落塵中曾被發現含有[[質量數]]為249、252、253和254的鉲同位素。<ref>{{cite journal|author = Fields, P. R. ''et al.''|title = Transplutonium Elements in Thermonuclear Test Debris|journal = Physical Review|year = 1956|volume = 102|issue = 1|pages = 180–182|doi = 10.1103/PhysRev.102.180|bibcode = 1956PhRv..102..180F }}</ref> |
|||
<!-- Curium-250 is obtained instead from the α-decay of <sup>254</sup>Cf. For this however, the production rate is low as <sup>254</sup>Cf decays mainly by spontaneous fission, and only slightly by emission of α-particles into <sup>250</sup>Cm.{{Citation needed|date=May 2012}} --> |
|||
:<math>\mathrm{^{A}_{96}Cm\ +\ ^{1}_{0}n\ \longrightarrow \ ^{A+1}_{\ \ 96}Cm\ +\ \gamma}</math> <small>(for A = 244–248)</small> |
|||
The above cascade of (n,γ) reactions produces a mixture of different curium isotopes. Their post-synthesis separation is cumbersome, and therefore a selective synthesis is desired. Curium-248 is favored for research purposes because of its long half-life. The most efficient preparation method of this isotope is via α-decay of the [[californium]] isotope <sup>252</sup>Cf, which is available in relatively large quantities due to its long half-life (2.65 years). About 35–50 mg of <sup>248</sup>Cm is being produced by this method every year. The associated reaction produces <sup>248</sup>Cm with isotopic purity of 97%.<ref name=haire>{{cite book |
|||
科學家曾認為[[超新星]]會產生鉲,因為超新星物質的衰變符合<sup>254</sup>Cf的60天半衰期。<ref name=super1>{{cite journal|last=Baade|first=W.|coauthors=Burbidge, G. R., Hoyle, F., Burbidge, E. M., Christy, R. F., & Fowler, W. A.|title=Supernovae and Californium 254|journal=Publications of the Astronomical Society of the Pacific|year=1956|month=August|volume=68|issue=403|pages=296–300|doi=10.1086/126941|url=http://authors.library.caltech.edu/6553/1/BURpr56.pdf|accessdate=26 September 2012}}</ref>不過,之後的研究未能探測到鉲譜線,<ref name=super2>{{cite journal|last=Conway|first=J. G.|coauthors=Hulet, E.K.; Morrow, R.J.|title=Emission Spectrum of Californium|journal=Journal of the Optical Society of America|date=1 February 1962|volume=52|url=http://www.osti.gov/energycitations/product.biblio.jsp?osti_id=4806792|accessdate=26 September 2012}}</ref>現在人們也一般認為超新星的[[光變曲線]]是符合[[鎳的同位素|鎳-56]]的特徵的。{{sfn|Ruiz-Lapuente1996|p=274}} |
|||
| title = The Chemistry of the Actinide and Transactinide Elements |
|||
| editor1-last = Morss|editor2-first = Norman M. |
|||
| editor2-last = Edelstein |
|||
| editor3-last = Fuger|editor3-first = Jean |
|||
| last = Haire|first = Richard G. |
|||
| chapter = Curium|url=http://radchem.nevada.edu/classes/rdch710/files/curium.pdf|page=1401 |
|||
| publisher = [[Springer Science+Business Media]] |
|||
| year = 2006 |
|||
| isbn = 1-4020-3555-1 |
|||
| location = Dordrecht, The Netherlands |
|||
| edition = 3rd |
|||
}}</ref> |
|||
:<math>\mathrm{^{252}_{\ 98}Cf\ \xrightarrow [2.645 \ yr]{\alpha} \ ^{248}_{\ 96}Cm}</math> |
|||
== 產生 == |
|||
{{see also|核燃料循環}} |
|||
鉲可以在[[核反應爐]]和[[粒子加速器]]中產生。{{sfn|Krebs|2006|pp=327–328}}錇-249({{nuclide|Bk|249}})受中子撞擊([[中子捕獲]](n,γ))後立即進行[[β衰變]](β<sup>−</sup>),便會形成鉲-250({{nuclide|Cf|250}})。反應如下:{{sfn|Heiserman|1992|p=348}} |
|||
:{{nuclide|Bk|249}}(n,γ){{nuclide|Bk|250}} → {{nuclide|Cf|250}} + β<sup>−</sup> |
|||
鉲-250在受中子撞擊後會產生鉲-251和鉲-252。{{sfn|Heiserman|1992|p=348}} |
|||
Another interesting for research isotope <sup>245</sup>Cm can be obtained from the α-decay of <sup>249</sup>Cf, and the latter isotope is produced in minute quantities from the β<sup>–</sup>-decay of the [[berkelium]] isotope <sup>249</sup>Bk. |
|||
對[[鎇]]、鋦和鈈元素進行中子輻射可以製成數毫克的鉲-252和數微克的鉲-249。{{sfn|Cunningham|1968|p=105}}直到2006年,科學家利用特殊的反應爐對鋦-244至248進行中子輻射,主要產生出鉲-252,另有較少的鉲-249至255。{{sfn|Haire|2006|p=1503}} |
|||
:<math>\mathrm{^{249}_{\ 97}Bk\ \xrightarrow [330 \ d]{\beta^-} \ ^{249}_{\ 98}Cf\ \xrightarrow [351 \ yr]{\alpha} \ ^{245}_{\ 96}Cm}</math> |
|||
===Metal preparation=== |
|||
經過[[美國核能管理委員會]]可以購得微克量的鉲-252作商業用途。{{sfn|Krebs|2006|pp=327–328}}世界上僅有兩處生產鉲的設施:位於美國的橡樹嶺國家實驗室以及位於俄羅斯的核反應器研究所。到2003年為止,兩座設施分別每年生產0.25克和0.025克的鉲-252。{{sfn|NRC|2008|p=33}} |
|||
[[File:Elutionskurven Tb Gd Eu und Bk Cm Am.png|thumb|[[Chromatography|Chromatographic]] [[elution]] curves revealing the similarity between Tb, Gd, Eu lanthanides and corresponding Bk, Cm, Am actinides.]] |
|||
Most synthesis routines yield a mixture of different actinide isotopes as [[oxide]]s, from which a certain isotope of curium needs to be separated. An example procedure could be to dissolve spent reactor fuel (e.g. [[MOX fuel]]) in [[nitric acid]], and remove the bulk of the uranium and plutonium using a [[PUREX]] ('''P'''lutonium – '''UR'''anium '''EX'''traction) type extraction with [[tributyl phosphate]] in a hydrocarbon. The lanthanides and the remaining actinides are then separated from the aqueous residue ([[raffinate]]) by a diamide-based extraction to give, after stripping, a mixture of trivalent actinides and lanthanides. A curium compound is then selectively extracted using multi-step [[chromatographic]] and centrifugation techniques with an appropriate reagent.<ref>Penneman, pp. 34–48</ref> [[BTBP|''Bis''-triazinyl bipyridine]] complex has been recently proposed as such reagent which is highly selective to curium.<ref>{{cite journal|author = Magnusson D, Christiansen B, Foreman MRS, Geist A, Glatz JP, Malmbeck R, Modolo G, Serrano-Purroy D and Sorel C|journal = Solvent Extraction and Ion Exchange|year = 2009|volume = 27|issue = 2|page = 97|doi = 10.1080/07366290802672204|title = Demonstration of a SANEX Process in [[centrifugal extractor|Centrifugal Contactors]] using the CyMe4-BTBP Molecule on a Genuine Fuel Solution}}</ref> Separation of curium from a very similar americium can also be achieved by treating a slurry of their hydroxides in aqueous [[sodium bicarbonate]] with [[ozone]] at elevated temperature. Both americium and curium are present in solutions mostly in the +3 valence state; whereas americium oxidizes to soluble Am(IV) complexes, curium remains unchanged and can thus be isolated by repeated centrifugation.<ref>Penneman, p. 25</ref> |
|||
Metallic curium is obtained by [[Redox|reduction]] of its compounds. Initially, curium(III) fluoride was used for this purpose. The reaction was conducted in the environment free from water and oxygen, in the apparatus made of [[tantalum]] and [[tungsten]], using elemental [[barium]] or [[lithium]] as reducing agents.<ref Name="Morrs"/><ref name = "CM_METALL" /><ref name="cunning">{{cite journal|last1=Cunningham|first1=B.B.|last2=Wallmann|first2=J.C.|title=Crystal structure and melting point of curium metal|journal=Journal of Inorganic and Nuclear Chemistry|volume=26|issue=2|page=271|year=1964|doi=10.1016/0022-1902(64)80069-5}}</ref><ref>{{cite journal|last1=Stevenson|first1=J|last2=Peterson|first2=J|title=Preparation and structural studies of elemental curium-248 and the nitrides of curium-248 and berkelium-249|journal=Journal of the Less Common Metals|volume=66|issue=2|page=201|year=1979|doi=10.1016/0022-5088(79)90229-7}}</ref><ref>''Gmelin Handbook of Inorganic Chemistry'', System No. 71, Volume 7 a, transuranics, Part B 1, pp. 67–68.</ref> |
|||
設施還生產三個半衰期頗長的鉲同位素,這需要[[鈾-238]]捕獲中子15次,期間不進行[[核裂變]]或α衰變。{{sfn|NRC|2008|p=33}}從鈾-238開始的核反應鏈經過幾個[[鈈的同位素|鈈同位素]]、[[鎇的同位素|鎇同位素]]、[[鋦的同位素|鋦同位素]]、[[錇的同位素|錇同位素]]以及鉲-249至253(見圖)。 |
|||
:<math>\mathrm{CmF_3\ +\ 3\ Li\ \longrightarrow \ Cm\ +\ 3\ LiF}</math> |
|||
{{-}} |
|||
[[File:Cf 252 Produktion.png|center|600px|thumb|以中子輻射從鈾-238產生鉲-252的核反應路徑圖]] |
|||
Another possibility is the reduction of curium(IV) oxide using a magnesium-zinc alloy in a melt of [[magnesium chloride]] and [[magnesium fluoride]].<ref>{{cite journal|last1=Eubanks|first1=I|title=Preparation of curium metal|journal=Inorganic and Nuclear Chemistry Letters|volume=5|issue=3|page=187|year=1969|doi=10.1016/0020-1650(69)80221-7}}</ref> |
|||
== 應用 == |
|||
[[File:CfShield.JPG|thumb|橡樹嶺國家實驗室建造的50噸重運輸桶,可用於運載最多1克的<sup>252</sup>Cf。{{sfn|Seaborg|1994|p=245}}運輸此類高放射性物質必須用到重型容器,以避免可能的意外。<ref>{{cite web|url=http://rampac.energy.gov/PCN/EM-PCP-certified-pkgs-8808.pdf|title=DOE Certified Radioactive Materials Transportation Packagings|last=Shuler|first=James|year=2008|page=1|publisher=United States Department of Energy|format=PDF }}</ref>]] |
|||
==Compounds and reactions== |
|||
<!--來源請求:鉲是發現當時在實驗室外有實際用途的最重元素。[[鑀]]及以上的元素由於半衰期太短,因此只能用於製造更重的元素。-->鉲-252作為一種強中子射源,有著幾個應用的範疇。每微克的鉲每分鐘能夠產生1.39億顆中子。<ref name="osti" />因此鉲可以被用作核反應爐的[[中子啟動源]]{{sfn|O'Neil|2006|p=276}}或在[[中子活化分析]]中作為(非來自反應爐的)中子源。<ref name="Martin2000">{{cite conference|last = Martin|first = R. C.|title = Applications and Availability of Californium-252 Neutron Sources for Waste Characterization|date = 2000-09-24|url = http://www.ornl.gov/~webworks/cpr/pres/107270_.pdf|format = PDF|accessdate = 2010-05-02|conference=Spectrum 2000 International Conference on Nuclear and Hazardous Waste Management|location=Chattanooga, Tennessee }}</ref>{{#tag:ref|由於體積較小,產生的熱量和氣體也較少,所以鉲-252在1990年便已取代了鈈-[[鈹]]中子源。{{sfn|Seaborg|1990|p=318}}|group="注"}}在[[放射治療]]無效時,[[子宮頸癌]]和[[腦癌]]的治療目前用到了鉲所產生的中子。{{sfn|O'Neil|2006|p=276}}自從1969年薩瓦那河發電廠向[[佐治亞理工學院]]借出119 µg的鉲-252之後,鉲一直被用於教育範疇上。{{sfn|Osborne-Lee|1995|p=33}}在煤炭、水泥產業中,鉲也被應用在煤元素分析和粒狀物質分析機上。 |
|||
{{category see also|Curium compounds}} |
|||
===Oxides=== |
|||
由於中子能夠穿透物質,所以鉲也可以被用在探測器中,如[[燃料棒]]掃描儀,{{sfn|O'Neil|2006|p=276}}使用[[中子射線照相術]]來探測飛機和武器部件的[[腐蝕]]、問題焊接點、破裂及內部濕氣,{{sfn|Osborne-Lee|1995|pp=26–27}}<!--來源請求:機場裏用於探測爆炸品的中子活化探測器-->以及便攜式金屬探測器等。<ref>{{cite web|url=http://www.pnl.gov/news/2000/00-43.htm|title=Will You be 'Mine'? Physics Key to Detection|date=2000-10-25|publisher = Pacific Northwest National Laboratory|accessdate = 2007-03-21 |archiveurl = http://web.archive.org/web/20070218125029/http://www.pnl.gov/news/2000/00-43.htm <!-- Bot retrieved archive --> |archivedate = 2007-02-18 }}</ref>[[中子濕度計]]利用鉲-252來尋找油井中的水和石油,為金銀礦的實地探測提供[[中子源]],{{sfn|CRC|2006|p=4.8}}以及探測地下水的流動。<ref>{{cite journal|journal = Ground Water|volume = 18|issue = 1|pages =14–23|year = 2006|title =Ground-Water Tracers – A Short Review|author = Davis, S. N. |doi = 10.1111/j.1745-6584.1980.tb03366.x|last2 = Thompson|first2 = Glenn M.|last3 = Bentley|first3 = Harold W.|last4 = Stiles|first4 = Gary }}</ref>1982年鉲-252的主要用途按用量比例分別為:反應爐啟動源(48.3%)、燃料棒掃描儀(25.3%)及活化分析(19.4%)。{{sfn|Osborne-Lee|1995|p=12}}到了1994年,大部分的鉲-252都用於中子射線照相(77.4%),而燃料棒掃描儀(12.1%)和反應爐啟動源(6.9%)則成了次要的應用範圍。{{sfn|Osborne-Lee|1995|p=12}} |
|||
Curium readily reacts with oxygen forming mostly Cm<sub>2</sub>O<sub>3</sub> and CmO<sub>2</sub> oxides,<ref name="lenntech"/> but the divalent oxide CmO is also known.<ref name="HOWI_1972">Holleman, p. 1972</ref> Black CmO<sub>2</sub> can be obtained by burning curium [[oxalate]] (Cm<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>), nitrate (Cm(NO<sub>3</sub>)<sub>3</sub>) or hydroxide in pure oxygen.<ref Name="asprey"/><ref name=g1268>Greenwood, p. 1268</ref> Upon heating to 600–650 °C in vacuum (about 0.01 [[Pascal (unit)|Pa]]), it transforms into the whitish Cm<sub>2</sub>O<sub>3</sub>:<ref name="asprey">{{cite journal|last1=Asprey|first1=L. B.|last2=Ellinger|first2=F. H.|last3=Fried|first3=S.|last4=Zachariasen|first4=W. H.|journal=Journal of the American Chemical Society|volume=77|issue=6|page=1707|year=1955|doi=10.1021/ja01611a108}}</ref><ref>{{cite journal|last1=Noe|first1=M|title=Self-radiation effects on the lattice parameter of 244CmO2|journal=Inorganic and Nuclear Chemistry Letters|volume=7|issue=5|page=421|year=1971|doi=10.1016/0020-1650(71)80177-0}}</ref> |
|||
: <math>\mathrm{4\ CmO_2\ \xrightarrow {\Delta T} \ 2\ Cm_2O_3\ +\ O_2}</math>. |
|||
Alternatively, Cm<sub>2</sub>O<sub>3</sub> can be obtained by reducing CmO<sub>2</sub> with molecular [[hydrogen]]:<ref>{{cite journal|last1=Haug|first1=H|title=Curium sesquioxide Cm2O3|journal=Journal of Inorganic and Nuclear Chemistry|volume=29|issue=11|page=2753|year=1967|doi=10.1016/0022-1902(67)80014-9}}</ref> |
|||
鉲-251的[[臨界質量]]很低(約為5 kg)。<ref>{{cite web|publisher = Institut de Radioprotection et de Sûreté Nucléaire|title = Evaluation of nuclear criticality safety data and limits for actinides in transport|page = 16|url = http://ec.europa.eu/energy/nuclear/transport/doc/irsn_sect03_146.pdf|format = PDF|accessdate=2010-12-20 }}</ref>人們曾誇大其低臨界質量的可能用途。{{#tag:ref|1961年7月版的《[[科技新時代]]》一篇名為「第三次世界大戰的事實與謬論」一文中寫道:「一個由鉲做成的原子彈可以比一個手槍子彈更小。你可以自制一支含六發子彈的手槍,其射出的子彈在接觸目標後能夠釋放10噸TNT炸彈的力量。」<ref>{{cite journal|journal=[[Popular Science]]|pages= pp. 92–95, 178–181|date=July 1961|volume=179|issue=1|issn=0161-7370|title=Facts and Fallacies of World War III|url=http://books.google.com/books?id=OiEDAAAAMBAJ&pg=PA180|author1=Mann, Martin}}"force of 10 tons of TNT", p.180.</ref>|group="注"}} |
|||
: <math>\mathrm{2\ CmO_2\ +\ H_2\ \longrightarrow \ Cm_2O_3\ +\ H_2O}</math> |
|||
Furthermore, a number of ternary oxides of the type M(II)CmO<sub>3</sub> are known, where M stays for a divalent metal, such as barium.<ref>{{cite journal|last1=Fuger|first1=J|last2=Haire|first2=R|last3=Peterson|first3=J|title=Molar enthalpies of formation of BaCmO3 and BaCfO3|journal=Journal of Alloys and Compounds|volume=200|issue=1–2|page=181|year=1993|doi=10.1016/0925-8388(93)90491-5}}</ref> |
|||
2006年10月,位於俄羅斯[[杜布納]][[聯合核研究所]]的研究人員宣佈成功合成3顆[[Uuo]](118號元素)原子。他們利用[[鈣]]-48撞擊鉲-249,產生了這個目前最重的元素。該次實驗的目標體是一片面積為32 cm<sup>2</sup>、含有10 mg鉲-249的[[鈦]]薄片。<ref>{{cite journal|author=Oganessian, Yu. Ts. ''et al.''| title = Synthesis of the isotopes of elements 118 and 116 in the californium-249 and <sup>245</sup>Cm+<sup>48</sup>Ca fusion reactions|journal = Physical Review C|year = 2006|volume = 74|issue =4|pages = 044602–044611|doi = 10.1103/PhysRevC.74.044602|bibcode=2006PhRvC..74d4602O }}</ref><ref>{{cite news|author = Sanderson, K. |title = Heaviest element made – again|work = Nature News|publisher =Nature|date = 2006-10-17|doi=10.1038/news061016-4 }}</ref><ref>{{cite web|author = Schewe, P.|coauthors = Stein, B.|title = Elements 116 and 118 Are Discovered|work = Physics News Update|publisher = American Institute of Physics|date = 2006-10-17|url = http://www.aip.org/pnu/2006/797.html|accessdate = 2006-10-19 }}</ref> <!--請解釋:鉲的其他應用包括校準、[[劑量學]]和裂變碎片及半衰期研究。{{sfn|Osborne-Lee|1995|p=34}} -->其他用到鉲來合成的超鈾元素還包括1961年以[[硼]]原子核撞擊鉲所形成的[[鐒]]元素。<ref>{{cite journal|title = Element 103 Synthesized|journal = Science News-Letter|volume = 79|issue = 17|year = 1961|page = 259|month = April }}</ref> |
|||
== |
===Halides=== |
||
The colorless curium(III) fluoride (CmF<sub>3</sub>) can be produced by introducing fluoride ions into curium(III)-containing solutions. The brown tetravalent curium(IV) fluoride (CmF<sub>4</sub>) on the other hand is only obtained by reacting curium(III) fluoride with molecular [[fluorine]]:<ref name = "Morrs"/> |
|||
[[生物累積|累積]]在骨骼組織裏的鉲會釋放輻射,破壞身體製造[[紅血球]]的能力。{{sfn|Cunningham|1968|p=106}}由於放射性極強,在環境中的存量極低,所以鉲在生物體中沒有任何自然的用途。{{sfn|Emsley|2001|p=90}} |
|||
: <math>\mathrm{2\ CmF_3\ +\ F_2\ \longrightarrow\ 2\ CmF_4}</math> |
|||
A series of ternary fluorides are known of the form A<sub>7</sub>Cm<sub>6</sub>F<sub>31</sub>, where A stands for [[alkali metal]].<ref>{{cite journal|last1=Keenan|first1=T|title=Lattice constants of K7Cm6F31 trends in the 1:1 and 7:6 alkali metal-actinide(IV) series|journal=Inorganic and Nuclear Chemistry Letters|volume=3|issue=10|page=391|year=1967|doi=10.1016/0020-1650(67)80092-8}}</ref> |
|||
在進食受鉲污染的食物或飲料,或吸入含有鉲的懸浮顆粒之後,鉲就會進入體內。在身體裏,只有0.05%的鉲會進入血液裏,其中的65%會積累在骨骼中,肝臟25%,其餘的主要通過排尿排出身體。骨骼和肝臟中積累的鉲分別會在50年和20年後消失。鉲會首先附在骨骼的表面,之後會慢慢蔓延到骨骼的各個部分。<ref name="ANL2005" /> |
|||
The colorless [[curium(III) chloride]] (CmCl<sub>3</sub>) is produced in the reaction of [[curium(III) hydroxide]] (Cm(OH)<sub>3</sub>) with anhydrous [[hydrogen chloride]] gas. It can further be converted into other halides, such as curium(III) bromide (colorless to light green) and curium(III) iodide (colorless), by reacting it with the [[ammonia]] salt of the corresponding halide at elevated temperature of about 400–450 °C:<ref>{{cite journal|last1=Asprey|first1=L. B.|last2=Keenan|first2=T. K.|last3=Kruse|first3=F. H.|journal=Inorganic Chemistry|volume=4|issue=7|page=985|year=1965|doi=10.1021/ic50029a013}}</ref> |
|||
一旦進入體內,鉲會造成很大的損害。另外,鉲-249和鉲-251能釋放[[伽瑪射線]],對外表組織造成傷害。鉲所釋放的[[致電離輻射]]在骨骼和肝臟中可致癌。<ref name="ANL2005" /><!-- for the whole paragraph --> |
|||
: <math>\mathrm{CmCl_3\ +\ 3\ NH_4I\ \longrightarrow \ CmI_3\ +\ 3\ NH_4Cl}</math> |
|||
An alternative procedure is heating curium oxide to about 600 °C with the corresponding acid (such as [[hydrobromic acid|hydrobromic]] for curium bromide).<ref>{{cite journal|last1=Burns|first1=J|title=Crystallographic studies of some transuranic trihalides: 239PuCl3, 244CmBr3, 249BkBr3 and 249CfBr3|journal=Journal of Inorganic and Nuclear Chemistry|volume=37|issue=3|page=743|year=1975|doi=10.1016/0022-1902(75)80532-X}}</ref><ref>{{cite journal|last1=Wallmann|first1=J|title=Crystal structure and lattice parameters of curium trichloride|journal=Journal of Inorganic and Nuclear Chemistry|volume=29|issue=11|page=2745|year=1967|doi=10.1016/0022-1902(67)80013-7}}</ref> Vapor phase [[hydrolysis]] of curium(III) chloride results in curium oxychloride:<ref>{{cite journal|last1=Weigel|first1=F|last2=Wishnevsky|first2=V|last3=Hauske|first3=H|title=The vapor phase hydrolysis of PuCl3 and CmCl3: heats of formation of PuOC1 and CmOCl|journal=Journal of the Less Common Metals|volume=56|issue=1|page=113|year=1977|doi=10.1016/0022-5088(77)90224-7}}</ref> |
|||
== 備註 == |
|||
: <math>\mathrm{CmCl_3\ +\ \ H_2O\ \longrightarrow \ CmOCl\ +\ 2\ HCl}</math> |
|||
===Chalcogenides and pnictides=== |
|||
{{reflist|group="注"}} |
|||
Sulfides, selenides and tellurides of curium have been obtained by treating curium with gaseous [[sulfur]], [[selenium]] or [[tellurium]] in vacuum at elevated temperature.<ref>Troc, R. [http://books.google.com/books?id=vkzx_t3zLR0C&pg=PA4 Actinide Monochalcogenides, Volume 27], Springer, 2009 ISBN 3-540-29177-6, p. 4</ref><ref>{{cite journal|last1=Damien|first1=D|title=Preparation and lattice parameters of curium sulfides and selenides|journal=Inorganic and Nuclear Chemistry Letters|volume=11|issue=7–8|page=451|year=1975|doi=10.1016/0020-1650(75)80017-1}}</ref> The [[Nitrogen group|pnictides]] of curium of the type CmX are known for the elements [[nitrogen]], [[phosphorus]], [[arsenic]] and [[antimony]].<ref Name="Morrs"/> They can be prepared by reacting either curium(III) hydride (CmH<sub>3</sub>) or metallic curium with these elements at elevated temperatures. |
|||
===Organocurium compounds and biological aspects=== |
|||
== 參考資料 == |
|||
[[File:Uranocene-3D-balls.png|thumb|120px|Predicted curocene structure]] |
|||
Organometallic complexes analogous to [[uranocene]] are known also for other actinides, such as thorium, protactinium, neptunium, plutonium and americium. [[Molecular orbital theory]] predicts a stable "curocene" complex (η<sup>8</sup>-C<sub>8</sub>H<sub>8</sub>)<sub>2</sub>Cm, but it has not been reported experimentally yet.<ref>Elschenbroich, Ch. Organometallic Chemistry, 6th edition, Wiesbaden 2008, ISBN 978-3-8351-0167-8, p. 589</ref><ref>{{cite journal|last1=Kerridge|first1=Andrew|last2=Kaltsoyannis|first2=Nikolas|title=Are the Ground States of the Later Actinocenes Multiconfigurational? All-Electron Spin−Orbit Coupled CASPT2 Calculations on An(η8-C8H8)2(An = Th, U, Pu, Cm)|journal=The Journal of Physical Chemistry A|volume=113|issue=30|page=8737|year=2009|pmid=19719318|doi=10.1021/jp903912q}}</ref> |
|||
Formation of the complexes of the type Cm(n-C<sub>3</sub>H<sub>7</sub>-BTP)<sub>3</sub>, where BTP stands for 2,6-di(1,2,4-triazin-3-yl)pyridine, in solutions containing n-C<sub>3</sub>H<sub>7</sub>-BTP and Cm<sup>3+</sup> ions has been confirmed by [[Extended X-ray absorption fine structure|EXAFS]]. Some of these BTP-type complexes selectively interact with curium and therefore are useful in its selective separation from lanthanides and another actinides.<ref name="denecke"/><ref>{{cite journal|last1=Girnt|first1=Denise|last2=Roesky|first2=Peter W.|last3=Geist|first3=Andreas|last4=Ruff|first4=Christian M.|last5=Panak|first5=Petra J.|last6=Denecke|first6=Melissa A.|title=6-(3,5-Dimethyl-1H-pyrazol-1-yl)-2,2′-bipyridine as Ligand for Actinide(III)/Lanthanide(III) Separation|journal=Inorganic Chemistry|volume=49|issue=20|page=9627|year=2010|pmid=20849125|doi=10.1021/ic101309j}}</ref> Dissolved Cm<sup>3+</sup> ions bind with many organic compounds, such as [[hydroxamic acid]],<ref name=pl1>{{cite journal|last1=Glorius|first1=M.|last2=Moll|first2=H.|last3=Bernhard|first3=G.|title=Complexation of curium(III) with hydroxamic acids investigated by time-resolved laser-induced fluorescence spectroscopy|journal=Polyhedron|volume=27|issue=9–10|page=2113|year=2008|doi=10.1016/j.poly.2008.04.002}}</ref> [[urea]],<ref name=pl2>{{cite journal|last1=Heller|first1=Anne|last2=Barkleit|first2=Astrid|last3=Bernhard|first3=Gert|last4=Ackermann|first4=Jörg-Uwe|title=Complexation study of europium(III) and curium(III) with urea in aqueous solution investigated by time-resolved laser-induced fluorescence spectroscopy|journal=Inorganica Chimica Acta|volume=362|issue=4|page=1215|year=2009|doi=10.1016/j.ica.2008.06.016}}</ref> [[fluorescein]]<ref name=pl3>{{cite journal|last1=Moll|first1=Henry|last2=Johnsson|first2=Anna|last3=Schäfer|first3=Mathias|last4=Pedersen|first4=Karsten|last5=Budzikiewicz|first5=Herbert|last6=Bernhard|first6=Gert|title=Curium(III) complexation with pyoverdins secreted by a groundwater strain of Pseudomonas fluorescens|journal=BioMetals|volume=21|issue=2|page=219|year=2007|pmid=17653625|doi=10.1007/s10534-007-9111-x}}</ref> and [[adenosine triphosphate]].<ref name=pl4>{{cite journal|last1=Moll|first1=Henry|last2=Geipel|first2=Gerhard|last3=Bernhard|first3=Gert|title=Complexation of curium(III) by adenosine 5′-triphosphate (ATP): A time-resolved laser-induced fluorescence spectroscopy (TRLFS) study|journal=Inorganica Chimica Acta|volume=358|issue=7|page=2275|year=2005|doi=10.1016/j.ica.2004.12.055}}</ref> Many of these compounds are related to biological activity of various [[microorganism]]s. The resulting complexes exhibit strong yellow-orange emission under UV light excitation, which is convenient not only for their detection, but also for studying the interactions between the Cm<sup>3+</sup> ion and the ligands via changes in the half-life (of the order ~0.1 ms) and spectrum of the fluorescence.<ref name=plb/><ref name=pl1/><ref name=pl2/><ref name=pl3/><ref name=pl4/> |
|||
{{reflist|colwidth=30em}} |
|||
Curium has no biological significance.<ref>{{cite web|url=http://umbbd.msi.umn.edu/periodic/elements/cm.html |title=Biochemical Periodic Table – Curium |publisher=Umbbd.msi.umn.edu |date=2007-06-08 |accessdate=2011-03-25}}</ref> There are a few reports on [[biosorption]] of Cm<sup>3+</sup> by [[bacteria]] and [[archaea]], however no evidence for incorporation of curium into them.<ref>{{cite journal|doi=10.1021/es0301166|last1=Moll|first1=H|last2=Stumpf|first2=T|last3=Merroun|first3=M|last4=Rossberg|first4=A|last5=Selenska-Pobell|first5=S|last6=Bernhard|first6=G|title=Time-resolved laser fluorescence spectroscopy study on the interaction of curium(III) with Desulfovibrio äspöensis DSM 10631T|journal=Environmental Science & Technology|volume=38|issue=5|pages=1455–9|year=2004|pmid=15046347}}</ref><ref>{{cite journal|author=Ozaki, T. ''et al.''|url=http://sciencelinks.jp/j-east/article/200305/000020030503A0110480.php|title=Association of Eu(III) and Cm(III) with Bacillus subtilis and Halobacterium salinarium|journal=Journal of Nuclear Science and Technology|year=2002|volume=Suppl. 3|pages=950–953}}</ref> |
|||
== 書目 == |
|||
<!--NOTE only add URLs to places where at least some preview of the book is available --> |
|||
* {{cite book |
|||
| last = Cotton | first = F. Albert |
|||
| coauthors = Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred |
|||
| title = Advanced Inorganic Chemistry |
|||
| edition = 6th |
|||
| year = 1999 |
|||
| publisher = John Wiley & Sons |
|||
| isbn = 978-0-471-19957-1 |
|||
| chapter = |
|||
| pages = |
|||
| ref = harv |
|||
}} |
|||
* {{cite book |
|||
| author = CRC contributors |
|||
| title = Handbook of Metal Etchants |
|||
| editor1-first = Perrin|editor1-last = Walker |
|||
| editor2-first = William H.| editor2-last = Tarn |
|||
| edition = |
|||
| year = 1991 |
|||
| publisher = CRC Press |
|||
| isbn = 978-0-8493-3623-2 |
|||
| ref = {{sfnRef|CRC|1991}} |
|||
}} |
|||
* {{cite book |
|||
| author = CRC contributors |
|||
| title = Handbook of Chemistry and Physics |
|||
| editor-first = David R.|editor-last = Lide |
|||
| edition = 87th |
|||
| year = 2006 |
|||
| publisher = CRC Press, Taylor & Francis Group |
|||
| isbn = 978-0-8493-0487-3 |
|||
| ref = {{sfnRef|CRC|2006}} |
|||
}} |
|||
* {{cite book |
|||
| title = The Encyclopedia of the Chemical Elements |
|||
| publisher = Reinhold Book Corporation |
|||
| year = 1968 |
|||
| editor-last = Hampel|editor-first = Clifford A. |
|||
| last = Cunningham |
|||
| first = B. B. |
|||
| coauthors = |
|||
| chapter = Californium |
|||
| pages= |
|||
| ref = harv |
|||
| lccn = 68-29938 |
|||
}} |
|||
* {{cite book |
|||
| title = The Elements |
|||
| last = Emsley |
|||
| first = John |
|||
| publisher = Oxford University Press |
|||
| year = 1998 |
|||
| isbn = 978-0-19-855818-7 |
|||
| pages = |
|||
| url=http://books.google.com/books?id=qgYpAAAAYAAJ |
|||
| ref = harv |
|||
}} |
|||
* {{cite book |
|||
| title = Nature's Building Blocks: An A-Z Guide to the Elements |
|||
| last = Emsley |
|||
| first = John |
|||
| publisher = Oxford University Press |
|||
| year = 2001 |
|||
| isbn = 978-0-19-850340-8 |
|||
| chapter = Californium |
|||
| pages = |
|||
| url=http://books.google.com/books?id=Yhi5X7OwuGkC&printsec=frontcover#v=onepage&q&f=false |
|||
| ref = harv |
|||
}} |
|||
* {{cite book |
|||
| last = Greenwood |
|||
| first = N. N. |
|||
| coauthors = Earnshaw, A. |
|||
| title = Chemistry of the Elements |
|||
| edition = 2nd |
|||
| publisher = Butterworth-Heinemann |
|||
| year = 1997 |
|||
| isbn = 978-0-7506-3365-9 |
|||
| page = |
|||
| chapter = |
|||
| ref = harv |
|||
}} |
|||
* {{cite book |
|||
| title = The Chemistry of the Actinide and Transactinide Elements |
|||
| editor1-first = Lester R. |
|||
| editor1-last = Morss|editor2-first = Norman M. |
|||
| editor2-last = Edelstein |
|||
| editor3-last = Fuger|editor3-first = Jean |
|||
| last = Haire|first = Richard G. |
|||
| chapter = Californium |
|||
| publisher = Springer Science+Business Media |
|||
| year = 2006 |
|||
| isbn = 978-1-4020-3555-5 |
|||
| edition = 3rd |
|||
| ref = harv |
|||
}} |
|||
* {{cite book |
|||
| last = Heiserman |
|||
| first = David L. |
|||
| year = 1992 |
|||
| title = Exploring Chemical Elements and their Compounds |
|||
| publisher = TAB Books |
|||
| isbn = 978-0-8306-3018-9 |
|||
| chapter = Element 98: Californium |
|||
| ref = harv |
|||
| url=http://books.google.com/books?id=24l-Cpal9oIC |
|||
}} |
|||
* {{cite book |
|||
| others = trans. rev. Eagleson, Mary |
|||
| editor1-first = Hans-Dieter | editor1-last = Jakubke |
|||
| editor2-first = Hans | editor2-last = Jeschkeit |
|||
| title = Concise Encyclopedia Chemistry |
|||
| publisher = Walter de Gruyter |
|||
| year = 1994 |
|||
| url = http://books.google.com/books?id=Owuv-c9L_IMC&printsec=frontcover |
|||
| isbn = 978-3-11-011451-5 |
|||
| ref = {{sfnRef|Jakubke|1994}} |
|||
}} |
|||
* {{cite book |
|||
| last = Krebs |
|||
| first = Robert |
|||
| title = The History and Use of our Earth's Chemical Elements: A Reference Guide |
|||
| year = 2006 |
|||
| publisher = Greenwood Publishing Group |
|||
| isbn = 978-0-313-33438-2 |
|||
| ref = harv |
|||
}} |
|||
* {{cite book |
|||
| title = Radiation Source Use and Replacement: Abbreviated Version |
|||
| author = National Research Council (U.S.). Committee on Radiation Source Use and Replacement |
|||
| year = 2008 |
|||
| publisher = National Academies Press |
|||
| ref = {{sfnRef|NRC|2008}} |
|||
| url = http://books.google.com/books?id=3cT2REdXJ98C&printsec=frontcover |
|||
| isbn = 978-0-309-11014-3 |
|||
}} |
|||
* {{cite book |
|||
| editor1-last = O'Neil|editor1-first = Marydale J. |
|||
| editor2-last = Heckelman|editor2-first = Patricia E. |
|||
| editor3-last = Roman|editor3-first = Cherie B. |
|||
| title = The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals |
|||
| edition = 14th |
|||
| publisher = Merck Research Laboratories, Merck & Co. |
|||
| year = 2006 |
|||
| isbn = 978-0-911910-00-1 |
|||
| url = http://books.google.com/books?id=kEYfRAAACAAJ |
|||
| ref = {{sfnRef|O'Neil|2006}} |
|||
}} |
|||
* {{cite journal |
|||
| title = Californium-252: A Remarkable Versatile Radioisotope |
|||
| last1 = Osborne-Lee|first1 = I. W. |
|||
| last2 = Alexander|first2 = C. W. |
|||
| journal = Oak Ridge Technical Report ORNL/TM-12706 |
|||
| year = 1995 |
|||
| url = http://www.osti.gov/bridge/product.biblio.jsp?query_id=1&page=0&osti_id=205871 |doi=10.2172/205871 |
|||
| ref = {{sfnRef|Osborne-Lee|1995}} |
|||
}} |
|||
* {{cite book |
|||
| last1 = Ruiz-Lapuente |
|||
| first1 = P. |
|||
| last2 = Canal |
|||
| first2 = R. |
|||
| last3 = Isern |
|||
| first3 = J. |
|||
| year = 1996 |
|||
| title = Thermonuclear Supernovae |
|||
| publisher = [[Springer Science+Business Media]] |
|||
| isbn = 978-0-7923-4359-2 |
|||
| url = http://books.google.com/books?id=I6Rl1VAAX3QC |
|||
| ref = {{sfnRef|Ruiz-Lapuente|1996}} |
|||
}} |
|||
* {{cite book |
|||
| last1 = Seaborg|first1 = Glenn T. |
|||
| last2 = Loveland|first2 = Walter D. |
|||
| title = The Elements Beyond Uranium |
|||
| publisher = John Wiley & Sons, Inc. |
|||
| year = 1990 |
|||
| isbn = 978-0-471-89062-1 |
|||
| ref = {{sfnRef|Seaborg|1990}} |
|||
| url = http://books.google.com/books?id=QFhRAAAAMAAJ |
|||
}} |
|||
* {{cite book |
|||
| last = Seaborg |
|||
| first = G. T. |
|||
| year = 1994 |
|||
| url = http://books.google.com/books?id=e53sNAOXrdMC&pg=PA245 |
|||
| title = Modern alchemy: selected papers of Glenn T. Seaborg |
|||
| publisher = World Scientific |
|||
| isbn = 978-981-02-1440-1 |
|||
| ref = harv |
|||
}} |
|||
* {{cite book |
|||
| last = Seaborg |
|||
| first = G. T. |
|||
| year = 1996 |
|||
| editor = Adloff, J. P. |
|||
| title = One Hundred Years after the Discovery of Radioactivity |
|||
| publisher = Oldenbourg Wissenschaftsverlag |
|||
| isbn = 978-3-486-64252-0 |
|||
| url = http://books.google.com/books?id=whGiCQywLi8C&printsec=frontcover#v=onepage&q&f=false |
|||
| ref = harv |
|||
}} |
|||
* {{cite encyclopedia |
|||
| last = Seaborg | first = Glenn T. |
|||
| encyclopedia = Concise Encyclopedia of Chemistry |
|||
| title = Californium |
|||
| editor = Geller, Elizabeth |
|||
| publisher = McGraw-Hill |
|||
| year = 2004 |
|||
| isbn = 978-0-07-143953-4 |
|||
| page = 94 |
|||
| url = http://books.google.com/books?id=Owuv-c9L_IMC&printsec=frontcover#v=onepage&q&f=false |
|||
| ref= harv |
|||
}} |
|||
* {{cite book |
|||
| last1 = Szwacki | first1 = Nevill Gonzalez |
|||
| last2 = Szwacka | first2 = Teresa |
|||
| title = Basic Elements of Crystallography |
|||
| publisher = Pan Stanford |
|||
| year = 2010 |
|||
| isbn = 978-981-4241-59-5 |
|||
| url = http://www.scribd.com/doc/39588027/Basic-Elements-of-Crystallography |
|||
| ref= {{sfnRef|Szwacki|2010}} |
|||
}} |
|||
* {{cite book |
|||
| last = Weeks |
|||
| first = Mary Elvira |
|||
| coauthor = Leichester, Henry M. |
|||
| year = 1968 |
|||
| title = Discovery of the Elements |
|||
| publisher = Journal of Chemical Education |
|||
| chapter = 21: Modern Alchemy |
|||
| pages = 848–850 |
|||
| ref = harv |
|||
| isbn = 978-0-7661-3872-8 |
|||
| lccn = 68-15217 |
|||
}} |
|||
== |
==Applications== |
||
===Radionuclides=== |
|||
[[File:Curium self-glow radiation.jpg|thumb|right|The radiation from curium is so strong that the metal glows purple in the dark.]] |
|||
Curium is one of the most radioactive isolable elements. Its two most common isotopes <sup>242</sup>Cm and <sup>244</sup>Cm are strong alpha emitters (energy 6 MeV); they have relatively short half-lives of 162.8 days and 18.1 years, and produce as much as 120 W/g and 3 W/g of thermal energy, respectively.<ref name=CRC/><ref name="Binder">Binder, Harry H.: ''Lexikon der chemischen Elemente'', S. Hirzel Verlag, Stuttgart 1999, ISBN 3-7776-0736-3, pp. 174–178.</ref><ref>''Gmelin Handbook of Inorganic Chemistry'', System No. 71, Volume 7a, transuranics, Part A2, p. 289</ref> Therefore, curium can be used in its common oxide form in [[radioisotope thermoelectric generator]]s like those in spacecraft. This application has been studied for the <sup>244</sup>Cm isotope, while <sup>242</sup>Cm was abandoned due to its prohibitive price of around 2000 USD/g. Curium-243 with a ~30 year half-life and good energy yield of ~1.6 W/g could make for a suitable fuel, but it produces significant amounts of harmful [[Gamma ray|gamma]] and [[Beta ray|beta]] radiation from radioactive decay products. Though as an α-emitter, <sup>244</sup>Cm requires a much thinner radiation protection shielding, it has a high spontaneous fission rate, and thus the neutron and gamma radiation rate are relatively strong. As compared to a competing thermoelectric generator isotope such as <sup>238</sup>Pu, <sup>244</sup>Cm emits a 500 time greater fluence of neutrons, and its higher gamma emission requires a shield that is 20 times thicker — about 2 inches of lead for a 1 kW source, as compared to 0.1 in for <sup>238</sup>Pu. Therefore this application of curium is currently considered impractical.<ref name=lect>[http://fti.neep.wisc.edu/neep602/SPRING00/lecture5.pdf Basic elements of static RTGs], G.L. Kulcinski, NEEP 602 Course Notes (Spring 2000), Nuclear Power in Space, University of Wisconsin Fusion Technology Institute (see last page)</ref> |
|||
A more promising application of <sup>242</sup>Cm is to produce <sup>238</sup>Pu, a more suitable radioisotope for thermoelectric generators such as in cardiac pacemakers. The alternative routes to <sup>238</sup>Pu use the (n,γ) reaction of <sup>237</sup>Np, or the [[deuteron]] bombardment of uranium, which both always produce <sup>236</sup>Pu as an undesired by-product — since the latter decays to <sup>208</sup>Tl with strong gamma emission.<ref>[http://www.kronenberg.kernchemie.de/ Kronenberg, Andreas], [http://www.kernenergie-wissen.de/pu-batterien.html Plutonium-Batterien] (in German)</ref> |
|||
Curium is also a common starting material for the production of higher [[transuranic elements]] and [[transactinides]]. Thus, bombardment of <sup>248</sup>Cm with oxygen (<sup>18</sup>O) or magnesium (<sup>26</sup>Mg) yielded certain isotopes of [[seaborgium]] (<sup>265</sup>Sg) and [[hassium]] (<sup>269</sup>Hs and <sup>270</sup>Hs).<ref name="HOWI_1980">Holleman, pp. 1980–1981.</ref> Californium was discovered when a microgram-sized target of curium-242 was irradiated with 35 MeV [[alpha particle]]s using the {{convert|60|in|cm|adj=on}} cyclotron at Berkeley: |
|||
:{{Nuclide|curium|242}} + {{Nuclide|helium|4}} → {{Nuclide|californium|245}} + {{su|b=0|p=1}}{{SubatomicParticle|neutron}} |
|||
Only about 5,000 atoms of californium were produced in this experiment.<ref>{{cite book|title=One Hundred Years after the Discovery of Radioactivity|editor=Adloff, J. P.|last=Seaborg|first=G. T.|page=82|year=1996|publisher=Oldenbourg Wissenschaftsverlag|isbn=978-3-486-64252-0}}</ref> |
|||
[[File:MER APXS PIA05113.jpg|thumb|Alpha-particle X-ray spectrometer of a Mars exploration rover]] |
|||
===X-ray spectrometer=== |
|||
The most practical application of <sup>244</sup>Cm — though rather limited in total volume — is as α-particle source in the [[alpha particle X-ray spectrometer]]s (APXS). These instruments were installed on the [[Mars Pathfinder|Sojourner]], [[Mars rover|Mars]], [[Mars 96]], [[Spirit rover|Spirit]], [[Mars Exploration Rover|Athena]] and [[Opportunity rover]]s, as well as the [[Mars Science Laboratory]] to analyze the composition and structure of the rocks on the surface of planet [[Mars]].<ref>{{cite journal|bibcode=1996DPS....28.0221R|title=An Alpha Proton X-Ray Spectrometer for Mars-96 and Mars Pathfinder|author=Rieder, R.; Wanke, H.; Economou, T.|journal=Bulletin of the American Astronomical Society|volume=28|page=1062|date=09/1996}}</ref> APXS was also used in the [[Surveyor Program|Surveyor 5–7]] moon probes but with a <sup>242</sup>Cm source.<ref name=LA2>[http://www.ead.anl.gov/pub/doc/curium.pdf Human Health Fact Sheet on Curium], Los Alamos National Laboratory</ref><ref>Leitenberger, Bernd [http://www.bernd-leitenberger.de/surveyor.shtml Die Surveyor Raumsonden] (in German)</ref><ref>{{cite book|url=http://history.nasa.gov/SP-480/ch9.htm |author=Nicks, Oran | |
|||
chapter=Ch. 9. Essentials for Surveyor|publisher=NASA|year=1985|title=SP-480 Far Travelers: The Exploring Machines}}</ref> |
|||
An elaborated APXS setup is equipped with a sensor head containing six curium sources having the total radioactive decay rate of several tens of [[curie|millicuries]] (roughly a [[Becquerel|gigabecquerel]]). The sources are collimated on the sample, and the energy spectra of the alpha particles and protons scattered from the sample are analyzed (the proton analysis is implemented only in some spectrometers). These spectra contain quantitative information on all major elements in the samples except for hydrogen, helium and lithium.<ref>[http://athena.cornell.edu/pdf/tb_apxs.pdf Alpha Particle X-Ray Spectrometer (APXS)], Cornell University</ref> An APXS will also be used by the [[Philae lander]] of the [[Rosetta (spacecraft)|Rosetta]] spacecraft to probe the surface of the [[67P/Churyumov-Gerasimenko]] [[comet]].<ref>{{cite web|url=http://www.bernd-leitenberger.de/philae.shtml |title=Der Rosetta Lander Philae |publisher=Bernd-leitenberger.de |date=2003-07-01 |accessdate=2011-03-25}}</ref> |
|||
==Safety== |
|||
Owing to its high radioactivity, curium and its compounds must be handled in appropriate laboratories under special arrangements. Whereas curium itself mostly emits α-particles which are absorbed by thin layers of common materials, some of its decay products emit significant fractions of beta and gamma radiation, which require a more elaborate protection.<ref Name="lenntech"/> If consumed, curium is excreted within a few days and only 0.05% is absorbed in the blood. From there, about 45% goes to the [[liver]], 45% to the bones, and the remaining 10% is excreted. In the bone, curium accumulates on the inside of the interfaces to the [[bone marrow]] and does not significantly redistribute with time; its radiation destroys [[bone marrow]] and thus stops [[red blood cell]] creation. The [[biological half-life]] of curium is about 20 years in the liver and 50 years in the bones.<ref Name="lenntech"/><ref name=LA2/> Curium is absorbed in the body much more strongly via inhalation, and the allowed total dose of <sup>244</sup>Cm in soluble form is 0.3 μ[[Curie (unit)|C]].<ref name=CRC/> Intravenous injection of <sup>242</sup>Cm and <sup>244</sup>Cm containing solutions to rats increased the incidence of [[bone tumor]], and inhalation promoted [[Lung|pulmonary]] and [[liver cancer]].<ref name="lenntech"/> |
|||
Curium isotopes are inevitably present in spent nuclear fuel with a concentration of about 20 g/tonne.<ref>Hoffmann, K. ''Kann man Gold machen? Gauner, Gaukler und Gelehrte. Aus der Geschichte der chemischen Elemente'' (Can you make gold? Crooks, clowns and scholars. From the history of the chemical elements), Urania-Verlag, Leipzig, Jena, Berlin 1979, no ISBN, p. 233</ref> Among them, the <sup>245</sup>Cm–<sup>248</sup>Cm isotopes have decay times of thousands of years and need to be removed to neutralize the fuel for disposal.<ref>Baetslé, L. H. [http://www.ictp.trieste.it/~pub_off/lectures/lns012/Baetsle.pdf Application of Partitioning/Transmutation of Radioactive Materials in Radioactive Waste Management], Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001.</ref> The associated procedure involves several steps, where curium is first separated and then converted by neutron bombardment in special reactors to short-lived nuclides. This procedure, [[nuclear transmutation]], while well documented for other elements, is still being developed for curium.<ref name="denecke"/> |
|||
== 參考資料 == |
|||
{{Reflist|30em}} |
|||
==書目== |
|||
{{Commons|Californium}} |
|||
*{{Greenwood&Earnshaw2nd}} |
|||
{{wiktionary|californium}} |
|||
*Holleman, Arnold F. and Wiberg, Nils ''Textbook of Inorganic Chemistry'', 102 Edition, de Gruyter, Berlin 2007, ISBN 978-3-11-017770-1. |
|||
* [http://www.nuclearweaponarchive.org/Nwfaq/Nfaq6.html#nfaq6.2 NuclearWeaponArchive.org – Californium](鉲在核武器檔案網上的資料){{en}} |
|||
*Penneman, R. A. and Keenan T. K. [http://www.osti.gov/bridge/purl.cover.jsp?purl=/4187189-IKQUwY/ The radiochemistry of americium and curium], Univsity of California, Los Alamos, California, 1960 |
|||
* [http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@rel+@na+californium,radioactive Hazardous Substances Databank – Californium, Radioactive](鉲在有害物質資料庫上的資料){{en}} |
|||
==外部鏈接== |
|||
{{Commons|Curium}} |
|||
{{wiktionary|curium}} |
|||
*[http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?dbs+hsdb:@term+@na+@rel+curium,+radioactive NLM Hazardous Substances Databank – Curium, Radioactive] |
|||
{{clear}} |
|||
{{元素週期表}} |
{{元素週期表}} |
||
[[Category:锕系元素]] |
[[Category:锕系元素]] |
||
[[Category:人工合成元素]] |
[[Category:人工合成元素]] |
||
[[Category:第7周期元素| |
[[Category:第7周期元素|7J]] |
||
[[Category:化学元素| |
[[Category:化学元素|7J]] |
||
{{ |
{{link FA|de}} |
||
{{ |
{{link GA|en}} |
||
{{Link FA|es}} |
2013年3月18日 (一) 21:10的版本
Curium is a transuranic radioactive chemical element with the symbol Cm and atomic number 96. This element of the actinide series was named after Marie Skłodowska-Curie and her husband Pierre Curie - both were known for their research on radioactivity. Curium was first intentionally produced and identified in July 1944 by the group of Glenn T. Seaborg at the University of California, Berkeley. The discovery was kept secret and only released to the public in November 1945. Most curium is produced by bombarding uranium or plutonium with neutrons in nuclear reactors – one tonne of spent nuclear fuel contains about 20 grams of curium.
Curium is a hard, dense, silvery metal with a relatively high melting point and boiling point for an actinide. Whereas it is paramagnetic at ambient conditions, it becomes antiferromagnetic upon cooling, and other magnetic transitions are also observed for many curium compounds. In compounds, curium usually exhibits valence +3 and sometimes +4, and the +3 valence is predominant in solutions. Curium readily oxidizes, and its oxides are a dominant form of this element. It forms strongly fluorescent complexes with various organic compounds, but there is no evidence of its incorporation into bacteria and archaea. When introduced into the human body, curium accumulates in the bones, lungs and liver, where it promotes cancer.
All known isotopes of curium are radioactive and have a small critical mass for a sustained nuclear chain reaction. They predominantly emit α-particles, and the heat released in this process can potentially produce electricity in radioisotope thermoelectric generators. This application is hindered by the scarcity, high cost and radioactivity of curium isotopes. Curium is used in production of heavier actinides and of the 238Pu radionuclide for power sources in artificial pacemakers. It served as the α-source in the alpha particle X-ray spectrometers installed on the Sojourner, Mars, Mars 96, Athena, Spirit and Opportunity rovers as well as the Mars Science Laboratory to analyze the composition and structure of the rocks on the surface of Mars and the Moon. Such a spectrometer will also be used by the Philae lander of the Rosetta spacecraft to probe the surface of the 67P/Churyumov-Gerasimenko comet.
History
Although curium had likely been produced in previous nuclear experiments, it was first intentionally synthesized, isolated and identified in 1944, at the University of California, Berkeley by Glenn T. Seaborg, Ralph A. James, and Albert Ghiorso. In their experiments, they used a 60-英寸(150-厘米) cyclotron.[2]
Curium was chemically identified at the Metallurgical Laboratory (now Argonne National Laboratory) at the University of Chicago. It was the third transuranium element to be discovered even though it is the fourth in the series – the lighter element americium was unknown at the time.[3][4]
The sample was prepared as follows: first plutonium nitrate solution was coated on a platinum foil of about 0.5 cm2 area, the solution was evaporated and the residue was converted into plutonium dioxide (PuO2) by annealing. Following cyclotron irradiation of the oxide, the coating was dissolved with nitric acid and then precipitated as the hydroxide using concentrated aqueous ammonia solution. The residue was dissolved in perchloric acid, and further separation was carried out by ion exchange to yield a certain isotope of curium. The separation of curium and americium was so painstaking that the Berkeley group initially called those elements pandemonium (from Greek for all demons or hell) and delirium (from Latin for madness).[5][6][7][8]
The curium-242 isotope was produced in July–August 1944 by bombarding 239Pu with α-particles to produce curium with the release of a neutron:
Curium-242 was unambiguously identified by the characteristic energy of the α-particles emitted during the decay:
The half-life of this alpha decay was first measured as 150 days and then corrected to 162.8 days.[9]
Another isotope 240Cm was produced in a similar reaction in March 1945:
The half-life of the 240Cm α-decay was correctly determined as 26.7 days.[9]
The discovery of curium, as well as americium, in 1944 was closely related to the Manhattan Project, the results were confidential and declassified only in 1945. Seaborg leaked the synthesis of the elements 95 and 96 on the U.S. radio show for children, the Quiz Kids, five days before the official presentation at an American Chemical Society meeting on November 11, 1945, when one of the listeners asked whether any new transuranium element beside plutonium and neptunium had been discovered during the war.[5] The discovery of curium (242Cm and 240Cm), their production and compounds were later patented listing only Seaborg as the inventor.[10]
The new element was named after Marie Skłodowska-Curie and her husband Pierre Curie who are noted for discovering radium and for their work in radioactivity. It followed the example of gadolinium, a lanthanide element above curium in the periodic table, which was named after the explorer of the rare earth elements Johan Gadolin:[11]
- "As the name for the element of atomic number 96 we should like to propose "curium" , with symbol Cm. The evidence indicates that element 96 contains seven 5f electrons and is thus analogous to the element gadolinium with its seven 4f electrons in the regular rare earth series. On this base element 96 is named after the Curies in a manner analogous to the naming of gadolinium, in which the chemist Gadolin was honored."[3]
The first curium samples were barely visible, and were identified by their radioactivity. Louis Werner and Isadore Perlman created the first substantial sample of 30 µg curium-242 hydroxide at the University of California in 1947 by bombarding americium-241 with neutrons.[12][13][14] Macroscopic amounts of curium fluoride were obtained in 1950 by W. W. T. Crane, J. C. Wallmann and B. B. Cunningham. Its magnetic susceptibility was very close to that of GdF3 providing the first experimental evidence for the +3 valence of curium in its compounds.[12] Curium metal was produced only in 1951 by reduction of curium fluoride with barium.[15][16]
Characteristics
Physical
A synthetic, radioactive element, curium is a hard dense metal with silvery-white appearance and physical and chemical properties resembling those of gadolinium. Its melting point of 1340 °C is significantly higher than that of the previous transuranic elements neptunium (637 °C), plutonium (639 °C) and americium (1173 °C). In comparison, gadolinium melts at 1312 °C. The boiling point of curium is 3110 °C. With a density of 13.52 g/cm3, curium is significantly lighter than neptunium (20.45 g/cm3) and plutonium (19.8 g/cm3), but is heavier than most other metals. Between two crystalline forms of curium, the α-Cm is more stable at ambient conditions. It has a hexagonal symmetry, space group P63/mmc, lattice parameters a = 365 pm and c = 1182 pm, and four formula units per unit cell.[17] The crystal consists of a double-hexagonal close packing with the layer sequence ABAC and so is isotypic with α-lanthanum. At pressures above 23 GPa, at room temperature, α-Cm transforms into β-Cm, which has a face-centered cubic symmetry, space group Fm3m and the lattice constant a = 493 pm.[17] Upon further compression to 43 GPa, curium transforms to an orthorhombic γ-Cm structure similar to that of α-uranium, with no further transitions observed up to 52 GPa. These three curium phases are also referred to as Cm I, II and III.[18][19]
Curium has peculiar magnetic properties. Whereas its neighbor element actinium shows no deviation from Curie-Weiss paramagnetism in the entire temperature range, α-Cm transforms to an antiferromagnetic state upon cooling to 65–52 K,[20][21] and β-Cm exhibits a ferrimagnetic transition at about 205 K. Meanwhile, curium pnictides show ferromagnetic transitions upon cooling: 244CmN and 244CmAs at 109 K, 248CmP at 73 K and 248CmSb at 162 K. Similarly, the lanthanide analogue of curium, gadolinium, as well as its pnictides also show magnetic transitions upon cooling, but the transition character is somewhat different: Gd and GdN become ferromagnetic, and GdP, GdAs and GdSb show antiferromagnetic ordering.[22]
In accordance with magnetic data, electrical resistivity of curium increases with temperature – about twice between 4 and 60 K – and then remains nearly constant up to room temperature. There is a significant increase in resistvity over time (about 10 µOhm·cm/h) due to self-damage of the crystal lattice by alpha radiation. This makes uncertain the absolute resistivity value for curium (about 125 µΩ·cm). The resistivity of curium is similar to that of gadolinium and of the actinides plutonium and neptunium, but is significantly higher than that of americium, uranium, polonium and thorium.[1][23]
Under ultraviolet illumination, curium(III) ions exhibit strong and stable yellow-orange fluorescence with a maximum in the range about 590–640 nm depending on their environment.[24] The fluorescence originates from the transitions from the first excited state 6D7/2 and the ground state 8S7/2. Analysis of this fluorescence allows monitoring interactions between Cm(III) ions in organic and inorganic complexes.[25]
Chemical
Curium ions in solution assume the oxidation state of +3, which is the most stable oxidation state for curium.[26] The +4 oxidation state is observed only in a few solid phases, such as CmO2 and CmF4.[27][28] Chemical behavior of curium is different from actinides thorium and uranium, and is similar to that of americium and many lanthanides. In aqueous solution, the Cm3+ ion is colorless to pale green,[29] and Cm4+ ion is pale yellow.[30] The optical absorption of Cm3+ ions contains three sharp peaks at 375.4, 381.2 and 396.5 nanometers and their strength can be directly converted into the concentration of the ions.[31] Curium ions are hard Lewis acids and thus form most stable complexes with hard bases.[32] The bonding is mostly ionic, with a small covalent component.[33] Curium in its complexes commonly exhibits a 9-fold coordination environment, within a tricapped trigonal prismatic geometry.[34]
Isotopes
Thermal neutron cross sections (barns)[35] | ||||||
---|---|---|---|---|---|---|
242Cm | 243Cm | 244Cm | 245Cm | 246Cm | 247Cm | |
Fission | 5 | 617 | 1.04 | 2145 | 0.14 | 81.90 |
Capture | 16 | 130 | 15.20 | 369 | 1.22 | 57 |
C/F ratio | 3.20 | 0.21 | 14.62 | 0.17 | 8.71 | 0.70 |
LEU spent fuel 20 years after 53 MWd/kg burnup[36] | ||||||
3 common isotopes | 51 | 3700 | 390 | |||
Fast reactor MOX fuel (avg 5 samples, burnup 66-120GWd/t)[37] | ||||||
Total curium 3.09×10-3% | 27.64% | 70.16% | 2.166% | 0.0376% | 0.000928% |
Isotope | 242Cm | 243Cm | 244Cm | 245Cm | 246Cm | 247Cm | 248Cm | 250Cm |
Critical mass, kg | 25 | 7.5 | 33 | 6.8 | 39 | 7 | 40.4 | 23.5 |
About 20 radioisotopes and 7 nuclear isomers between 233Cm and 252Cm are known for curium, and no stable isotopes. The longest half-lives have been reported for 247Cm (15.6 million years) and 248Cm (348,000 years). Other long-lived isotopes are 245Cm (half-life 8500 years), 250Cm (8,300 years) and 246Cm (4,760 years). Curium-250 is unusual by that it predominantly (about 86%) decays via spontaneous fission. The most commonly used curium isotopes are 242Cm and 244Cm with the half-lives of 162.8 days and 18.1 years, respectively.[9]
All isotopes between 242Cm and 248Cm, as well as 250Cm, undergo a self-sustaining nuclear chain reaction and thus in principle can act as a nuclear fuel in a reactor. As in most transuranic elements, the nuclear fission cross section is especially high for the odd-mass curium isotopes243Cm, 245Cm and 247Cm. These can be used in thermal-neutron reactors, whereas a mixture of curium isotopes is only suitable for fast breeder reactors since the even-mass isotopes are not fissile in a thermal reactor and accumulate as burn-up increases.[39] The mixed-oxide (MOX) fuel, which is to be used in power reactors, should contain little or no curium because the neutron activation of 248Cm will create californium. This is strong neutron emitter, and would pollute the back end of the fuel cycle and increase the dose to reactor personnel. Hence, if the minor actinides are to be used as fuel in a thermal neutron reactor, the curium should be excluded from the fuel or placed in special fuel rods where it is the only actinide present.[40]
The table to the right lists the critical masses for curium isotopes for a sphere, without a moderator and reflector. With a metal reflector (30 cm of steel), the critical masses of the odd isotopes are about 3–4 kg. When using water (thickness ~20–30 cm) as the reflector, the critical mass can be as small as 59 gram for 245Cm, 155 gram for 243Cm and 1550 gram for 247Cm. There is a significant uncertainty in these critical mass values. Whereas it is usually of the order 20%, the values for 242Cm and 246Cm were listed as large as 371 kg and 70.1 kg, respectively, by some research groups.[39][41]
Currently, curium is not used as a nuclear fuel owing to its low availability and high price.[42] 245Cm and 247Cm have a very small critical mass and therefore could be used in portable nuclear weapons, but none have been reported thus far. Curium-243 is not suitable for this purpose because of its short half-life and strong α emission which would result in excessive heat.[43] Curium-247 would be highly suitable, having a half-life 647 times that of plutonium-239.
Occurrence
The longest-lived isotope of curium, 247Cm, has a half-life of 15.6 million years. Therefore, all primordial curium, that is curium present on the Earth during its formation, should have decayed by now. Curium is produced artificially, in small quantities for research purposes. Furthermore, it occurs in spent nuclear fuel. Curium is present in nature in certain areas used for the atmospheric nuclear weapons tests, which were conducted between 1945 and 1980.[44] So the analysis of the debris at the testing site of the first U.S. hydrogen bomb, Ivy Mike, (1 November 1952, Enewetak Atoll), beside einsteinium, fermium, plutonium and americium also revealed isotopes of berkelium, californium and curium, in particular 245Cm, 246Cm and smaller quantities of 247Cm, 248Cm and 249Cm. For reasons of military secrecy, this result was published only in 1956.[45]
Atmospheric curium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 4,000 times higher concentration of curium at the sandy soil particles than in water present in the soil pores. An even higher ratio of about 18,000 was measured in loam soils.[46]
A few atoms of curium can be produced by neutron capture reactions and beta decay in very highly concentrated uranium-bearing deposits.[47]
Synthesis
Isotope preparation
Curium is produced in small quantities in nuclear reactors, and by now only kilograms of it have been accumulated for the 242Cm and 244Cm and grams or even milligrams for heavier isotopes. This explains the high price of curium, which has been be quoted at 160–185 USD per milligram,[12] with a more recent estimate at 2,000 USD/g for 242Cm and 170 USD/g for 244Cm.[48] In nuclear reactors, curium is formed from 238U in a series of nuclear reactions. In the first chain, 238U captures a neutron and converts into 239U, which via β– decay transforms into 239Np and 239Pu.
- (the times are half-lives).
Further neutron capture followed by β–-decay produces the 241Am isotope of americium which further converts into 242Cm:
- .
For research purposes, curium is obtained by irradiating not uranium but plutonium, which is available in large amounts from spent nuclear fuel. Much higher neutron flux is used for the irradiation that results in a different reaction chain and formation of 244Cm:[4]
Curium-244 decays into 240Pu by emission of alpha particle, but it also absorbs neutrons resulting in a small amount of heavier curium isotopes. Among those, 247Cm and 248Cm are popular in scientific research because of their long half-lives. However, the production rate of 247Cm in thermal neutron reactors is relatively low because of it is prone to undergo fission induced by thermal neutrons.[49] Synthesis of 250Cm via neutron absorption is also rather unlikely because of the short half-life of the intermediate product 249Cm (64 min), which converts by β– decay to the berkelium isotope 249Bk.[49]
- (for A = 244–248)
The above cascade of (n,γ) reactions produces a mixture of different curium isotopes. Their post-synthesis separation is cumbersome, and therefore a selective synthesis is desired. Curium-248 is favored for research purposes because of its long half-life. The most efficient preparation method of this isotope is via α-decay of the californium isotope 252Cf, which is available in relatively large quantities due to its long half-life (2.65 years). About 35–50 mg of 248Cm is being produced by this method every year. The associated reaction produces 248Cm with isotopic purity of 97%.[49]
Another interesting for research isotope 245Cm can be obtained from the α-decay of 249Cf, and the latter isotope is produced in minute quantities from the β–-decay of the berkelium isotope 249Bk.
Metal preparation
Most synthesis routines yield a mixture of different actinide isotopes as oxides, from which a certain isotope of curium needs to be separated. An example procedure could be to dissolve spent reactor fuel (e.g. MOX fuel) in nitric acid, and remove the bulk of the uranium and plutonium using a PUREX (Plutonium – URanium EXtraction) type extraction with tributyl phosphate in a hydrocarbon. The lanthanides and the remaining actinides are then separated from the aqueous residue (raffinate) by a diamide-based extraction to give, after stripping, a mixture of trivalent actinides and lanthanides. A curium compound is then selectively extracted using multi-step chromatographic and centrifugation techniques with an appropriate reagent.[50] Bis-triazinyl bipyridine complex has been recently proposed as such reagent which is highly selective to curium.[51] Separation of curium from a very similar americium can also be achieved by treating a slurry of their hydroxides in aqueous sodium bicarbonate with ozone at elevated temperature. Both americium and curium are present in solutions mostly in the +3 valence state; whereas americium oxidizes to soluble Am(IV) complexes, curium remains unchanged and can thus be isolated by repeated centrifugation.[52]
Metallic curium is obtained by reduction of its compounds. Initially, curium(III) fluoride was used for this purpose. The reaction was conducted in the environment free from water and oxygen, in the apparatus made of tantalum and tungsten, using elemental barium or lithium as reducing agents.[4][15][53][54][55]
Another possibility is the reduction of curium(IV) oxide using a magnesium-zinc alloy in a melt of magnesium chloride and magnesium fluoride.[56]
Compounds and reactions
Oxides
Curium readily reacts with oxygen forming mostly Cm2O3 and CmO2 oxides,[44] but the divalent oxide CmO is also known.[57] Black CmO2 can be obtained by burning curium oxalate (Cm2(C2O4)3), nitrate (Cm(NO3)3) or hydroxide in pure oxygen.[28][58] Upon heating to 600–650 °C in vacuum (about 0.01 Pa), it transforms into the whitish Cm2O3:[28][59]
- .
Alternatively, Cm2O3 can be obtained by reducing CmO2 with molecular hydrogen:[60]
Furthermore, a number of ternary oxides of the type M(II)CmO3 are known, where M stays for a divalent metal, such as barium.[61]
Halides
The colorless curium(III) fluoride (CmF3) can be produced by introducing fluoride ions into curium(III)-containing solutions. The brown tetravalent curium(IV) fluoride (CmF4) on the other hand is only obtained by reacting curium(III) fluoride with molecular fluorine:[4]
A series of ternary fluorides are known of the form A7Cm6F31, where A stands for alkali metal.[62]
The colorless curium(III) chloride (CmCl3) is produced in the reaction of curium(III) hydroxide (Cm(OH)3) with anhydrous hydrogen chloride gas. It can further be converted into other halides, such as curium(III) bromide (colorless to light green) and curium(III) iodide (colorless), by reacting it with the ammonia salt of the corresponding halide at elevated temperature of about 400–450 °C:[63]
An alternative procedure is heating curium oxide to about 600 °C with the corresponding acid (such as hydrobromic for curium bromide).[64][65] Vapor phase hydrolysis of curium(III) chloride results in curium oxychloride:[66]
Chalcogenides and pnictides
Sulfides, selenides and tellurides of curium have been obtained by treating curium with gaseous sulfur, selenium or tellurium in vacuum at elevated temperature.[67][68] The pnictides of curium of the type CmX are known for the elements nitrogen, phosphorus, arsenic and antimony.[4] They can be prepared by reacting either curium(III) hydride (CmH3) or metallic curium with these elements at elevated temperatures.
Organocurium compounds and biological aspects
Organometallic complexes analogous to uranocene are known also for other actinides, such as thorium, protactinium, neptunium, plutonium and americium. Molecular orbital theory predicts a stable "curocene" complex (η8-C8H8)2Cm, but it has not been reported experimentally yet.[69][70]
Formation of the complexes of the type Cm(n-C3H7-BTP)3, where BTP stands for 2,6-di(1,2,4-triazin-3-yl)pyridine, in solutions containing n-C3H7-BTP and Cm3+ ions has been confirmed by EXAFS. Some of these BTP-type complexes selectively interact with curium and therefore are useful in its selective separation from lanthanides and another actinides.[24][71] Dissolved Cm3+ ions bind with many organic compounds, such as hydroxamic acid,[72] urea,[73] fluorescein[74] and adenosine triphosphate.[75] Many of these compounds are related to biological activity of various microorganisms. The resulting complexes exhibit strong yellow-orange emission under UV light excitation, which is convenient not only for their detection, but also for studying the interactions between the Cm3+ ion and the ligands via changes in the half-life (of the order ~0.1 ms) and spectrum of the fluorescence.[25][72][73][74][75]
Curium has no biological significance.[76] There are a few reports on biosorption of Cm3+ by bacteria and archaea, however no evidence for incorporation of curium into them.[77][78]
Applications
Radionuclides
Curium is one of the most radioactive isolable elements. Its two most common isotopes 242Cm and 244Cm are strong alpha emitters (energy 6 MeV); they have relatively short half-lives of 162.8 days and 18.1 years, and produce as much as 120 W/g and 3 W/g of thermal energy, respectively.[12][79][80] Therefore, curium can be used in its common oxide form in radioisotope thermoelectric generators like those in spacecraft. This application has been studied for the 244Cm isotope, while 242Cm was abandoned due to its prohibitive price of around 2000 USD/g. Curium-243 with a ~30 year half-life and good energy yield of ~1.6 W/g could make for a suitable fuel, but it produces significant amounts of harmful gamma and beta radiation from radioactive decay products. Though as an α-emitter, 244Cm requires a much thinner radiation protection shielding, it has a high spontaneous fission rate, and thus the neutron and gamma radiation rate are relatively strong. As compared to a competing thermoelectric generator isotope such as 238Pu, 244Cm emits a 500 time greater fluence of neutrons, and its higher gamma emission requires a shield that is 20 times thicker — about 2 inches of lead for a 1 kW source, as compared to 0.1 in for 238Pu. Therefore this application of curium is currently considered impractical.[48]
A more promising application of 242Cm is to produce 238Pu, a more suitable radioisotope for thermoelectric generators such as in cardiac pacemakers. The alternative routes to 238Pu use the (n,γ) reaction of 237Np, or the deuteron bombardment of uranium, which both always produce 236Pu as an undesired by-product — since the latter decays to 208Tl with strong gamma emission.[81]
Curium is also a common starting material for the production of higher transuranic elements and transactinides. Thus, bombardment of 248Cm with oxygen (18O) or magnesium (26Mg) yielded certain isotopes of seaborgium (265Sg) and hassium (269Hs and 270Hs).[82] Californium was discovered when a microgram-sized target of curium-242 was irradiated with 35 MeV alpha particles using the 60-英寸(150-厘米) cyclotron at Berkeley:
- 242
96Cm
+ 4
2He
→ 245
98Cf
+ 1
0
n
Only about 5,000 atoms of californium were produced in this experiment.[83]
X-ray spectrometer
The most practical application of 244Cm — though rather limited in total volume — is as α-particle source in the alpha particle X-ray spectrometers (APXS). These instruments were installed on the Sojourner, Mars, Mars 96, Spirit, Athena and Opportunity rovers, as well as the Mars Science Laboratory to analyze the composition and structure of the rocks on the surface of planet Mars.[84] APXS was also used in the Surveyor 5–7 moon probes but with a 242Cm source.[46][85][86]
An elaborated APXS setup is equipped with a sensor head containing six curium sources having the total radioactive decay rate of several tens of millicuries (roughly a gigabecquerel). The sources are collimated on the sample, and the energy spectra of the alpha particles and protons scattered from the sample are analyzed (the proton analysis is implemented only in some spectrometers). These spectra contain quantitative information on all major elements in the samples except for hydrogen, helium and lithium.[87] An APXS will also be used by the Philae lander of the Rosetta spacecraft to probe the surface of the 67P/Churyumov-Gerasimenko comet.[88]
Safety
Owing to its high radioactivity, curium and its compounds must be handled in appropriate laboratories under special arrangements. Whereas curium itself mostly emits α-particles which are absorbed by thin layers of common materials, some of its decay products emit significant fractions of beta and gamma radiation, which require a more elaborate protection.[44] If consumed, curium is excreted within a few days and only 0.05% is absorbed in the blood. From there, about 45% goes to the liver, 45% to the bones, and the remaining 10% is excreted. In the bone, curium accumulates on the inside of the interfaces to the bone marrow and does not significantly redistribute with time; its radiation destroys bone marrow and thus stops red blood cell creation. The biological half-life of curium is about 20 years in the liver and 50 years in the bones.[44][46] Curium is absorbed in the body much more strongly via inhalation, and the allowed total dose of 244Cm in soluble form is 0.3 μC.[12] Intravenous injection of 242Cm and 244Cm containing solutions to rats increased the incidence of bone tumor, and inhalation promoted pulmonary and liver cancer.[44]
Curium isotopes are inevitably present in spent nuclear fuel with a concentration of about 20 g/tonne.[89] Among them, the 245Cm–248Cm isotopes have decay times of thousands of years and need to be removed to neutralize the fuel for disposal.[90] The associated procedure involves several steps, where curium is first separated and then converted by neutron bombardment in special reactors to short-lived nuclides. This procedure, nuclear transmutation, while well documented for other elements, is still being developed for curium.[24]
參考資料
- ^ 1.0 1.1 1.2 Schenkel, R. The electrical resistivity of 244Cm metal. Solid State Communications. 1977, 23 (6): 389. Bibcode:1977SSCom..23..389S. doi:10.1016/0038-1098(77)90239-3.
- ^ Hall, Nina. The New Chemistry: A Showcase for Modern Chemistry and Its Applications. Cambridge University Press. 2000: 8–9. ISBN 978-0-521-45224-3.
- ^ 3.0 3.1 Seaborg, G. T.; James, R. A. and Ghiorso, A.: "The New Element Curium (Atomic Number 96)", NNES PPR (National Nuclear Energy Series, Plutonium Project Record), Vol. 14 B, The Transuranium Elements: Research Papers, Paper No. 22.2, McGraw-Hill Book Co., Inc., New York, 1949; Abstract; Full text (January 1948).
- ^ 4.0 4.1 4.2 4.3 4.4 Morss, L. R.; Edelstein, N. M. and Fugere, J. (eds): The Chemistry of the Actinide Elements and transactinides, volume 3, Springer-Verlag, Dordrecht 2006, ISBN 1-4020-3555-1.
- ^ 5.0 5.1 Pepling, Rachel Sheremeta. Chemical & Engineering News: It's Elemental: The Periodic Table – Americium. 2003 [07-12-2008].
- ^ Krebs, Robert E. The history and use of our earth's chemical elements: a reference guide, Greenwood Publishing Group, 2006, ISBN 0-313-33438-2 p. 322
- ^ Harper, Douglas. pandemonium. Online Etymology Dictionary.
- ^ Harper, Douglas. delirium. Online Etymology Dictionary.
- ^ 9.0 9.1 9.2 Audi, G. The N? evaluation of nuclear and decay properties (PDF). Nuclear Physics A. 1997, 624 (1): 1. Bibcode:1997NuPhA.624....1A. doi:10.1016/S0375-9474(97)00482-X.
- ^ Seaborg, G. T. 美國專利第3,161,462号 "Element", Filing date: 7 February 1949, Issue date: December 1964
- ^ Greenwood, p. 1252
- ^ 12.0 12.1 12.2 12.3 12.4 Hammond C. R. "The elements" in Lide, D. R. (编), CRC Handbook of Chemistry and Physics 86th, Boca Raton (FL): CRC Press, 2005, ISBN 0-8493-0486-5
- ^ L. B. Werner, I. Perlman: "Isolation of Curium", NNES PPR (National Nuclear Energy Series, Plutonium Project Record), Vol. 14 B, The Transuranium Elements: Research Papers, Paper No. 22.5, McGraw-Hill Book Co., Inc., New York, 1949.
- ^ National Academy of Sciences. Isadore Perlman 1915–1991. Nap.edu. [2011-03-25].
- ^ 15.0 15.1 Wallmann, J. C.; Crane, W. W. T.; Cunningham, B. B. The Preparation and Some Properties of Curium Metal. Journal of the American Chemical Society. 1951, 73 (1): 493–494. doi:10.1021/ja01145a537.
- ^ Werner, L. B.; Perlman, I. First Isolation of Curium. Journal of the American Chemical Society. 1951, 73 (1): 5215–5217. doi:10.1021/ja01155a063.
- ^ 17.0 17.1 Milman, V. Crystal structures of curium compounds: an ab initio study. Journal of Nuclear Materials. 2003, 322 (2–3): 165. Bibcode:2003JNuM..322..165M. doi:10.1016/S0022-3115(03)00321-0.
- ^ Young, D. A. Phase diagrams of the elements, University of California Press, 1991, ISBN 0-520-07483-1p. 227
- ^ Haire, R; Peterson, J; Benedict, U; Dufour, C; Itie, J. X-ray diffraction of curium-248 metal under pressures of up to 52 GPa. Journal of the Less Common Metals. 1985, 109 (1): 71. doi:10.1016/0022-5088(85)90108-0.
- ^ Kanellakopulos, B. The magnetic susceptibility of Americium and curium metal. Solid State Communications. 1975, 17 (6): 713. Bibcode:1975SSCom..17..713K. doi:10.1016/0038-1098(75)90392-0.
- ^ Fournier, J. Curium: A new magnetic element. Physica B+C. 1977, 86–88: 30. Bibcode:1977PhyBC..86...30F. doi:10.1016/0378-4363(77)90214-5.
- ^ Nave, S. E.; Huray, P. G.; Peterson, J. R. and Damien, D. A. Magnetic susceptibility of curium pnictides, Oak Ridge National Laboratory
- ^ Schenkel, R. The electrical resistivity of 244Cm metal. Solid State Communications. 1977, 23 (6): 389. Bibcode:1977SSCom..23..389S. doi:10.1016/0038-1098(77)90239-3.
- ^ 24.0 24.1 24.2 Denecke, Melissa A.; Rossberg, André; Panak, Petra J.; Weigl, Michael; Schimmelpfennig, Bernd; Geist, Andreas. Characterization and Comparison of Cm(III) and Eu(III) Complexed with 2,6-Di(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine Using EXAFS, TRFLS, and Quantum-Chemical Methods. Inorganic Chemistry. 2005, 44 (23): 8418. PMID 16270980. doi:10.1021/ic0511726.
- ^ 25.0 25.1 Bünzli, J.-C. G. and Choppin, G. R. Lanthanide probes in life, chemical, and earth sciences: theory and practice, Elsevier, Amsterdam, 1989 ISBN 0-444-88199-9
- ^ Penneman, p. 24
- ^ Keenan, Thomas K. Journal of the American Chemical Society. 1961, 83 (17): 3719. doi:10.1021/ja01478a039. 缺少或
|title=
为空 (帮助) - ^ 28.0 28.1 28.2 Asprey, L. B.; Ellinger, F. H.; Fried, S.; Zachariasen, W. H. Journal of the American Chemical Society. 1955, 77 (6): 1707. doi:10.1021/ja01611a108. 缺少或
|title=
为空 (帮助) - ^ Greenwood, p. 1265
- ^ Holleman, p. 1956
- ^ Penneman, pp. 25–26
- ^ Jensen, Mark P.; Bond, Andrew H. Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations. Journal of the American Chemical Society. 2002, 124 (33): 9870. PMID 12175247. doi:10.1021/ja0178620.
- ^ Seaborg, G. T. Overview of the Actinide and Lanthanide (the f) Elements. Radiochimica Acta. 1993, 61: 115–122.
- ^ Greenwood, p. 1267
- ^ Pfennig, G.; Klewe-Nebenius, H. and Seelmann Eggebert, W. (Eds.): Karlsruhe nuclide, 6th Ed. 1998
- ^ Kang, Jungmin; Von Hippel, Frank. Limited Proliferation-Resistance Benefits from Recycling Unseparated Transuranics and Lanthanides from Light-Water Reactor Spent Fuel (PDF). Science and Global Security. 2005, 13 (3): 169. doi:10.1080/08929880500357682.
- ^ Osaka, M.; et al. Analysis of Curium Isotopes in Mixed Oxide Fuel Irradiated in Fast Reactor (PDF). Journal of Nuclear Science and Technology. 2001, 38 (10): 912–914. doi:10.3327/jnst.38.912.
- ^ Sasahara, Akihiro; Matsumura, Tetsuo; Nicolaou, Giorgos; Papaioannou, Dimitri. Neutron and Gamma Ray Source Evaluation of LWR High Burn-up UO2 and MOX Spent Fuels. Journal of Nuclear Science and Technology. 2004, 41 (4): 448–456. doi:10.3327/jnst.41.448.
- ^ 39.0 39.1 Institut de Radioprotection et de Sûreté Nucléaire: "Evaluation of nuclear criticality safety. data and limits for actinides in transport", p. 16
- ^ National Research Council (U.S.). Committee on Separations Technology and Transmutation Systems. Nuclear wastes: technologies for separations and transmutation. National Academies Press. 1996: 231– [19 April 2011]. ISBN 978-0-309-05226-9.
- ^ Okundo, H. and Kawasaki, H. Critical and Subcritical Mass Calculations of Curium-243 to −247 Based on JENDL-3.2 for Revision of ANSI/ANS-8.15. Journal of Nuclear Science and Technology. 2002, 39 (10): 1072–1085. doi:10.3327/jnst.39.1072.
- ^ § 2 Begriffsbestimmungen (Atomic Energy Act) (in German)
- ^ Jukka Lehto; Xiaolin Hou. Chemistry and Analysis of Radionuclides: Laboratory Techniques and Methodology. Wiley-VCH. 2 February 2011: 303– [19 April 2011]. ISBN 978-3-527-32658-7.
- ^ 44.0 44.1 44.2 44.3 44.4 Curium (in German)
- ^ Fields, P.; Studier, M.; Diamond, H.; Mech, J.; Inghram, M.; Pyle, G.; Stevens, C.; Fried, S.; Manning, W. Transplutonium Elements in Thermonuclear Test Debris. Physical Review. 1956, 102 (1): 180. Bibcode:1956PhRv..102..180F. doi:10.1103/PhysRev.102.180.
- ^ 46.0 46.1 46.2 Human Health Fact Sheet on Curium, Los Alamos National Laboratory
- ^ Emsley, John. Nature's Building Blocks: An A-Z Guide to the Elements New. New York, NY: Oxford University Press. 2011. ISBN 978-0-19-960563-7.
- ^ 48.0 48.1 Basic elements of static RTGs, G.L. Kulcinski, NEEP 602 Course Notes (Spring 2000), Nuclear Power in Space, University of Wisconsin Fusion Technology Institute (see last page)
- ^ 49.0 49.1 49.2 Haire, Richard G. Curium. Morss; Edelstein, Norman M.; Fuger, Jean (编). The Chemistry of the Actinide and Transactinide Elements (PDF) 3rd. Dordrecht, The Netherlands: Springer Science+Business Media. 2006: 1401. ISBN 1-4020-3555-1.
- ^ Penneman, pp. 34–48
- ^ Magnusson D, Christiansen B, Foreman MRS, Geist A, Glatz JP, Malmbeck R, Modolo G, Serrano-Purroy D and Sorel C. Demonstration of a SANEX Process in Centrifugal Contactors using the CyMe4-BTBP Molecule on a Genuine Fuel Solution. Solvent Extraction and Ion Exchange. 2009, 27 (2): 97. doi:10.1080/07366290802672204.
- ^ Penneman, p. 25
- ^ Cunningham, B.B.; Wallmann, J.C. Crystal structure and melting point of curium metal. Journal of Inorganic and Nuclear Chemistry. 1964, 26 (2): 271. doi:10.1016/0022-1902(64)80069-5.
- ^ Stevenson, J; Peterson, J. Preparation and structural studies of elemental curium-248 and the nitrides of curium-248 and berkelium-249. Journal of the Less Common Metals. 1979, 66 (2): 201. doi:10.1016/0022-5088(79)90229-7.
- ^ Gmelin Handbook of Inorganic Chemistry, System No. 71, Volume 7 a, transuranics, Part B 1, pp. 67–68.
- ^ Eubanks, I. Preparation of curium metal. Inorganic and Nuclear Chemistry Letters. 1969, 5 (3): 187. doi:10.1016/0020-1650(69)80221-7.
- ^ Holleman, p. 1972
- ^ Greenwood, p. 1268
- ^ Noe, M. Self-radiation effects on the lattice parameter of 244CmO2. Inorganic and Nuclear Chemistry Letters. 1971, 7 (5): 421. doi:10.1016/0020-1650(71)80177-0.
- ^ Haug, H. Curium sesquioxide Cm2O3. Journal of Inorganic and Nuclear Chemistry. 1967, 29 (11): 2753. doi:10.1016/0022-1902(67)80014-9.
- ^ Fuger, J; Haire, R; Peterson, J. Molar enthalpies of formation of BaCmO3 and BaCfO3. Journal of Alloys and Compounds. 1993, 200 (1–2): 181. doi:10.1016/0925-8388(93)90491-5.
- ^ Keenan, T. Lattice constants of K7Cm6F31 trends in the 1:1 and 7:6 alkali metal-actinide(IV) series. Inorganic and Nuclear Chemistry Letters. 1967, 3 (10): 391. doi:10.1016/0020-1650(67)80092-8.
- ^ Asprey, L. B.; Keenan, T. K.; Kruse, F. H. Inorganic Chemistry. 1965, 4 (7): 985. doi:10.1021/ic50029a013. 缺少或
|title=
为空 (帮助) - ^ Burns, J. Crystallographic studies of some transuranic trihalides: 239PuCl3, 244CmBr3, 249BkBr3 and 249CfBr3. Journal of Inorganic and Nuclear Chemistry. 1975, 37 (3): 743. doi:10.1016/0022-1902(75)80532-X.
- ^ Wallmann, J. Crystal structure and lattice parameters of curium trichloride. Journal of Inorganic and Nuclear Chemistry. 1967, 29 (11): 2745. doi:10.1016/0022-1902(67)80013-7.
- ^ Weigel, F; Wishnevsky, V; Hauske, H. The vapor phase hydrolysis of PuCl3 and CmCl3: heats of formation of PuOC1 and CmOCl. Journal of the Less Common Metals. 1977, 56 (1): 113. doi:10.1016/0022-5088(77)90224-7.
- ^ Troc, R. Actinide Monochalcogenides, Volume 27, Springer, 2009 ISBN 3-540-29177-6, p. 4
- ^ Damien, D. Preparation and lattice parameters of curium sulfides and selenides. Inorganic and Nuclear Chemistry Letters. 1975, 11 (7–8): 451. doi:10.1016/0020-1650(75)80017-1.
- ^ Elschenbroich, Ch. Organometallic Chemistry, 6th edition, Wiesbaden 2008, ISBN 978-3-8351-0167-8, p. 589
- ^ Kerridge, Andrew; Kaltsoyannis, Nikolas. Are the Ground States of the Later Actinocenes Multiconfigurational? All-Electron Spin−Orbit Coupled CASPT2 Calculations on An(η8-C8H8)2(An = Th, U, Pu, Cm). The Journal of Physical Chemistry A. 2009, 113 (30): 8737. PMID 19719318. doi:10.1021/jp903912q.
- ^ Girnt, Denise; Roesky, Peter W.; Geist, Andreas; Ruff, Christian M.; Panak, Petra J.; Denecke, Melissa A. 6-(3,5-Dimethyl-1H-pyrazol-1-yl)-2,2′-bipyridine as Ligand for Actinide(III)/Lanthanide(III) Separation. Inorganic Chemistry. 2010, 49 (20): 9627. PMID 20849125. doi:10.1021/ic101309j.
- ^ 72.0 72.1 Glorius, M.; Moll, H.; Bernhard, G. Complexation of curium(III) with hydroxamic acids investigated by time-resolved laser-induced fluorescence spectroscopy. Polyhedron. 2008, 27 (9–10): 2113. doi:10.1016/j.poly.2008.04.002.
- ^ 73.0 73.1 Heller, Anne; Barkleit, Astrid; Bernhard, Gert; Ackermann, Jörg-Uwe. Complexation study of europium(III) and curium(III) with urea in aqueous solution investigated by time-resolved laser-induced fluorescence spectroscopy. Inorganica Chimica Acta. 2009, 362 (4): 1215. doi:10.1016/j.ica.2008.06.016.
- ^ 74.0 74.1 Moll, Henry; Johnsson, Anna; Schäfer, Mathias; Pedersen, Karsten; Budzikiewicz, Herbert; Bernhard, Gert. Curium(III) complexation with pyoverdins secreted by a groundwater strain of Pseudomonas fluorescens. BioMetals. 2007, 21 (2): 219. PMID 17653625. doi:10.1007/s10534-007-9111-x.
- ^ 75.0 75.1 Moll, Henry; Geipel, Gerhard; Bernhard, Gert. Complexation of curium(III) by adenosine 5′-triphosphate (ATP): A time-resolved laser-induced fluorescence spectroscopy (TRLFS) study. Inorganica Chimica Acta. 2005, 358 (7): 2275. doi:10.1016/j.ica.2004.12.055.
- ^ Biochemical Periodic Table – Curium. Umbbd.msi.umn.edu. 2007-06-08 [2011-03-25].
- ^ Moll, H; Stumpf, T; Merroun, M; Rossberg, A; Selenska-Pobell, S; Bernhard, G. Time-resolved laser fluorescence spectroscopy study on the interaction of curium(III) with Desulfovibrio äspöensis DSM 10631T. Environmental Science & Technology. 2004, 38 (5): 1455–9. PMID 15046347. doi:10.1021/es0301166.
- ^ Ozaki, T.; et al. Association of Eu(III) and Cm(III) with Bacillus subtilis and Halobacterium salinarium. Journal of Nuclear Science and Technology. 2002,. Suppl. 3: 950–953.
- ^ Binder, Harry H.: Lexikon der chemischen Elemente, S. Hirzel Verlag, Stuttgart 1999, ISBN 3-7776-0736-3, pp. 174–178.
- ^ Gmelin Handbook of Inorganic Chemistry, System No. 71, Volume 7a, transuranics, Part A2, p. 289
- ^ Kronenberg, Andreas, Plutonium-Batterien (in German)
- ^ Holleman, pp. 1980–1981.
- ^ Seaborg, G. T. Adloff, J. P. , 编. One Hundred Years after the Discovery of Radioactivity. Oldenbourg Wissenschaftsverlag. 1996: 82. ISBN 978-3-486-64252-0.
- ^ Rieder, R.; Wanke, H.; Economou, T. An Alpha Proton X-Ray Spectrometer for Mars-96 and Mars Pathfinder. Bulletin of the American Astronomical Society. 09/1996, 28: 1062. Bibcode:1996DPS....28.0221R.
- ^ Leitenberger, Bernd Die Surveyor Raumsonden (in German)
- ^ Nicks, Oran. Ch. 9. Essentials for Surveyor. SP-480 Far Travelers: The Exploring Machines. NASA. 1985.
- ^ Alpha Particle X-Ray Spectrometer (APXS), Cornell University
- ^ Der Rosetta Lander Philae. Bernd-leitenberger.de. 2003-07-01 [2011-03-25].
- ^ Hoffmann, K. Kann man Gold machen? Gauner, Gaukler und Gelehrte. Aus der Geschichte der chemischen Elemente (Can you make gold? Crooks, clowns and scholars. From the history of the chemical elements), Urania-Verlag, Leipzig, Jena, Berlin 1979, no ISBN, p. 233
- ^ Baetslé, L. H. Application of Partitioning/Transmutation of Radioactive Materials in Radioactive Waste Management, Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001.
書目
- Greenwood, Norman Neill; Earnshaw, Alan. Chemistry of the elements. 2016. ISBN 978-0-7506-3365-9. OCLC 1040112384 (英语).
- Holleman, Arnold F. and Wiberg, Nils Textbook of Inorganic Chemistry, 102 Edition, de Gruyter, Berlin 2007, ISBN 978-3-11-017770-1.
- Penneman, R. A. and Keenan T. K. The radiochemistry of americium and curium, Univsity of California, Los Alamos, California, 1960