Halvmetall
Sammen med metaller og ikke- metaller utgjør halvmetaller (også kjent som metalloider ) en av tre kategorier av kjemiske elementer etter en klassifisering i henhold til bindings- og ioniseringsegenskaper . [ 1 ] De er karakterisert ved å presentere en mellomoppførsel mellom metaller og ikke-metaller, og deler egenskapene til begge. Som en generell regel og i de fleste tilfeller har de en tendens til å reagere kjemisk med ikke-metaller , selv om det er visse forbindelser dannet av metall og halvmetall, for eksempel magnesiumborid . De kan være både blanke og matte, og formen kan lett endre seg. Metalloider er generelt bedre ledere av varme og elektrisitet enn ikke-metaller, men ikke like gode som metaller. Det er ingen entydig måte å skille metalloider fra ekte metaller , men de er generelt forskjellige ved at metalloider er halvledere i stedet for ledere . I motsetning til metaller, som øker temperaturen reduserer dens elektriske ledningsevne, i halvmetaller øker temperaturen det motsatte, øker den dens elektriske ledningsevne. Ikke-metaller er ugjennomsiktige og i forskjellige farger. De brukes noen ganger til å danne legeringer . De kan være amfotere eller svakt sure .
Følgende elementer regnes som metalloider:
Innenfor det periodiske systemet finnes metalloidene i en diagonal linje fra bor til astatin (sistnevnte er ikke inkludert). Elementene øverst til høyre er ikke-metaller, og de nederst til venstre er metaller.
Alle disse elementene har tre eller flere valenselektroner i sin siste bane (B3, Si4, Ge4, As5, Sb5, Te6, Po6). Silisium er for eksempel en metalloid som er mye brukt i produksjonen av halvlederelementer for elektronikkindustrien , som likerettere , dioder , transistorer , integrerte kretser og mikroprosessorer .
Definisjoner
Basert på prøven
Et metalloid er et grunnstoff som har en overvekt av mellomegenskaper, eller som er en blanding av metaller og ikke-metaller, og er derfor vanskelig å klassifisere som et metall eller et ikke-metall. Dette er en generisk definisjon som er basert på egenskapene til metalloider som er systematisk sitert i litteraturen.
Definisjoner og utdrag fra forskjellige forfattere følger, og illustrerer aspekter ved den generiske definisjonen:
- "I kjemi er et metalloid et grunnstoff med egenskaper som ligger mellom egenskapene til metaller og ikke-metaller" [ 2 ]
- "Blant metallene og ikke-metallene i det periodiske systemet finner vi elementer ... [som] deler noen av de karakteristiske egenskapene til både metaller og ikke-metaller, noe som gjør det vanskelig å plassere dem i noen av disse to hovedkategoriene" [ 3 ]
- "Kjemikere bruker noen ganger navnet metalloid ... for disse elementene som er vanskelige å klassifisere på en eller annen måte" [ 4 ]
- "Siden egenskapene som skiller metaller fra ikke-metaller er kvalitative i naturen, faller noen elementer ikke entydig inn i noen av kategoriene. Disse elementene ... kalles metalloider ..." [ 5 ]
Mer generelt har metalloidene blitt referert til som:
- "elementer som ... er en slags krysning mellom metaller og ikke-metaller"; [ 6 ] eller
- "mellomfremmede elementer". [ 7 ]
Kategoriseringsvansker er en nøkkelegenskap. De fleste grunnstoffene har en blanding av metalliske og ikke-metalliske egenskaper, [ 8 ] og kan klassifiseres basert på hvilket sett med egenskaper som er mer uttalt. [ 9 ]
Gull , for eksempel, har blandede egenskaper, men er fortsatt anerkjent som "kongen av metaller". I tillegg til metallisk oppførsel (som høy elektrisk ledningsevne og kationdannelse ), viser gull ikke-metallisk oppførsel:
- Den har det høyeste elektrodepotensialet ]
- Den har den tredje høyeste ioniseringsenergien blant metaller (etter sink og kvikksølv )
- Den har den høyeste elektronaffiniteten
- Elektronegativiteten på 2,54 er den høyeste blant metaller og overgår den for noen halvmetaller ( hydrogen 2,2; fosfor 2,19; og radon 2,2) .
- Det danner auridiumanion Au − , hvor det i dette tilfellet fungerer som et halogen
- Noen ganger viser den en tendens, kalt " aurofilisitet ", til å binde seg til seg selv. [ 10 ]
Om sin halogennatur, se Belpassi et al., [ 11 ] som indikerer at i dem MAu aurider (M = Li–Cs ) "oppfører seg som et halogen, mellom Br og I "; om aurofilisitet se Schmidbaur og Schier. [ 12 ]
Bare elementer ved eller nær marginene, som mangler en tilstrekkelig klar overvekt av metalliske eller ikke-metalliske egenskaper, er klassifisert som metalloider. [ 13 ]
Bor, silisium, germanium, arsen, antimon og tellur er ofte identifisert som metalloider. [ 14 ] [ n 1 ] Avhengig av forfatteren, blir ett eller flere selen , polonium eller astatin noen ganger lagt til listen . [ 16 ] Noen ganger er bor utelukket, alene eller med silisium. [ 17 ] Noen ganger regnes ikke tellur som en metalloid. [ 18 ] Inkluderingen av antimon , polonium og astatin som metalloider har vært omstridt. [ 19 ] .
Andre grunnstoffer blir tidvis klassifisert som metalloider. Disse elementene inkluderer [ 20 ] hydrogen, [ 21 ] beryllium , [ 22 ] nitrogen , [ 23 ] fosfor , [ 24 ] svovel , [ 25 ] sink , [ 26 ] gallium , [ 27 ] tinn , jod ] , bly , [ 2 , [ 29 ] vismut , [ 18 ] og radon. [ 30 ] Begrepet metalloid har også blitt brukt om elementer som har en metallisk glans og elektrisk ledningsevne, og som er amfotere , som arsen, antimon, vanadium , krom , molybden , wolfram , tinn, bly og aluminium. [ 31 ] P-blokkmetallene , [ 32 ] og ikke-metaller (som karbon eller nitrogen) som kan danne legeringer med metallene [ 33 ] eller endre deres egenskaper [ 34 ] har også noen ganger blitt betraktet som metalloider.
Basert på kriterier
Element
|
EI (kcal/mol)
|
EI (kJ/mol)
|
I
|
elektronisk båndstruktur
|
Bor
|
191
|
801
|
2.04
|
halvleder
|
Silisium
|
188
|
787
|
1,90
|
halvleder
|
Germanium
|
182
|
762
|
2.01
|
halvleder
|
Arsenikk
|
226
|
944
|
2.18
|
halvmetall
|
Antimon
|
199
|
831
|
2.05
|
halvmetall
|
Tellur
|
208
|
869
|
2.10
|
halvleder
|
gjennomsnitt
|
199
|
832
|
2.05
|
|
Elementene som vanligvis er anerkjent som metalloider, og deres ioniseringsenergier (IE); [ 35 ] elektronegativiteter (EN, revidert Pauling-skala); og elektroniske båndstrukturer [ 36 ] (mer termodynamisk stabile former under omgivelsesforhold).
|
Det er ingen allment akseptert definisjon av en metalloid, og heller ingen inndeling av det periodiske systemet i metaller, metalloider og ikke-metaller; [ 37 ] Hawkes [ 38 ] stilte spørsmål ved gjennomførbarheten av å etablere en spesifikk definisjon, og la merke til at anomalier kan finnes i forskjellige forsøk på konstruksjoner. Klassifiseringen av et grunnstoff som et metalloid har blitt beskrevet av Sharp [ 39 ] som "vilkårlig".
Antallet og identitetene til metalloidene avhenger av klassifiseringskriteriene som brukes. Emsley [ 40 ] gjenkjente fire metalloider (germanium, arsen, antimon og tellur); James et al. [ 41 ] de listet opp tolv (Emsleys pluss bor, karbon, silisium, selen, vismut, polonium, moscovium og livermorium ). I gjennomsnitt er syv elementer inkludert i metalloidlister; individuelle klassifiseringsordninger har en tendens til å dele felles grunnlag og varierer med dårlig definerte [ 42 ] marginer. [ n 2 ] [ n 3 ]
Et enkelt kvantitativt kriterium som elektronegativitet brukes ofte , [ 45 ] metalloider har elektronegativitetsverdier på 1,8 eller 1,9 til 2,2. [ 46 ] Andre eksempler inkluderer pakkingseffektiviteten (volumfraksjonen i en krystallstruktur okkupert av atomer) og Goldhammer-Herzfeld kriterieforholdet. [ 47 ] Vanlig anerkjente metalloider har pakkingseffektivitet mellom 34 % og 41 %. [ n 4 ]
Andre forfattere har for eksempel basert seg på atomkonduktansen [ n 5 ] [ 51 ] eller globalt koordinasjonsnummer. [ 52 ]
Jones, som skrev om klassifiseringens rolle i vitenskapen, observerte at "[klasser] vanligvis er definert av mer enn to attributter". [ 53 ] Masterton og Slowinski [ 54 ] brukte tre kriterier for å beskrive de seks elementene som vanligvis er anerkjent som metalloider: metalloider har ioniseringsenergier rundt 200 kcal/mol (837 kJ/mol) og elektronegativitetsverdier nær 2, 0. De sa også at metalloider vanligvis er halvledere, selv om antimon og arsen (halvmetaller fra et fysisk perspektiv) har elektrisk ledningsevne som nærmer seg metaller. Selen og polonium mistenkes ikke å være i denne ordningen, mens statusen til astatin er usikker. [ n 6 ]
I denne sammenhengen foreslo Vernon at en metalloid er et kjemisk grunnstoff som i sin standardtilstand har (a) den elektroniske båndstrukturen til en halvleder eller semimetall; og (b) et første mellomliggende ioniseringspotensial "(si 750-1000 kJ/mol)"; og (c) en mellomliggende elektronegativitet (1,9-2,2). [ 57 ]
Referanser
- ↑ Greenwood NN & Earnshaw A 2002, Chemistry of the Elements, 2nd ed., Butterworth-Heinemann, ISBN 0-7506-3365-4
- ↑ Cusack 1987, s. 360
- ↑ Kelter, Mosher & Scott 2009, s. 268
- ^ a b Hill & Holman 2000, s. 41
- ↑ King 1979, s. 1. 3
- ^ Moore 2011, s. 81
- ↑ Grå 2010
- ↑ Hopkins & Dance 1956, s. 458
- ^ Glinka 1965, s. 77
- ^ Wiberg 2001, s. 1279
- ↑ Belpassi et al. 2006, s. 4543–44
- ↑ Schmidbaur & Schier 2008, s. 1931–51
- ↑ Tyler Miller 1987, s. 59
- ↑ Goldsmith 1982, s. 526 ; Kotz, Treichel & Weaver 2009, s. 62 ; Bettelheim et al. 2010, s. 46
- ↑ Siter feil: Ugyldig tag <ref>; innholdet i de kalte referansene er ikke definertMann
- ^ Hawkes 2001, s. 1686 ; Segal 1989, s. 965 ; McMurray & Fay 2009, s. 767
- ↑ Bucat 1983, s. 26 ; Brun c. 2007
- ^ a b Swift & Schaefer 1962, s. 100
- ^ Hawkes 2001, s. 1686 ; Hawkes 2010 ; Holt, Rinehart og Wilsonc. 2007
- ↑ Dunstan 1968, s. 310, 409 . Dunstan lister Be, Al, Ge (kanskje), As, Se (kanskje), Sn, Sb, Te, Pb, Bi og Po som metalloider (s. 310, 323, 409, 419).
- ↑ Tilden 1876, s. 172, 198-201 ; Smith 1994, s. 252 ; Bodner & Pardue 1993, s. 354
- ^ Bassett et al. 1966, s. 127
- ↑ Rauch 1960
- ↑ Thayer 1977, s. 604 ; Warren & Geballe 1981 ; Masters & Ella 2008, s. 190
- ↑ Warren & Geballe 1981 ; Chalmers 1959, s. 72 ; US Naval Personnel Bureau 1965, s. 26
- ↑ Siebring 1967, s. 513
- ^ Wiberg 2001, s. 282
- ^ Rausch 1960 ; Venner 1953, s. 68
- ↑ Murray 1928, s. 1295
- ^ Hampel & Hawley 1966, s. 950 ; Stein 1985 ; Stein 1987, s. 240, 247-48
- ↑ Hatcher 1949, s. 223 ; Secret & Powers 1966, s. 459
- ↑ Taylor 1960, s. 614
- ↑ Considine & Considine 1984, s. 568 ; Cegielski 1998, s. 147 ; The American heritage science dictionary 2005 , s. 397
- ↑ Woodward 1948, s. 1
- ^ NIST 2010 . Verdiene vist i tabellen ovenfor er konvertert fra NIST-verdier, som er gitt i eV.
- ^ Berger 1997 ; Lovett 1977, s. 3
- ↑ Goldsmith 1982, s. 526 ; Hawkes 2001, s. 1686
- ^ Hawkes 2001, s. 1687
- ↑ Sharp 1981, s. 299
- ^ Emsley 1971, s. 1
- ↑ James et al. 2000, s. 480
- ↑ Chatt 1951, s. 417 "Grensen mellom metaller og metalloider er ubestemt..."; Burrows et al. 2009, s. 1192 : "Selv om elementene praktisk beskrives som metaller, metalloider og ikke-metaller, er overgangene ikke nøyaktige ..."
- ↑ Jones 2010, s. 170
- ↑ Kneen, Rogers & Simpson 1972, s. 218-20
- ^ Rockow 1966, s. 1, 4-7
- ^ Rochow 1977, s. 76 ; Mann et al. 2000, s. 2783
- ↑ Askeland, Phule & Wright 2011, s. 69
- ↑ Edwards 1999, s. 416
- ↑ Steurer 2007, s. 142 ; Pyykkö 2012, s. 56
- ↑ Edwards & Sienko 1983, s. 695
- ↑ Hill & Holman 2000, s. 160 . De karakteriserer metalloider (delvis) på grunnlag av at de er "dårlige ledere av elektrisitet med atomledningsevne vanligvis mindre enn 10 −3 men større enn 10 −5 ohm −1 cm −4 ".
- ↑ Bond 2005, s. 3 : "Et kriterium for å skille halvmetaller fra ekte metaller under normale forhold er at bulkkoordinasjonstallet til førstnevnte aldri er større enn åtte, mens det for metaller vanligvis er tolv (eller mer, hvis for den kroppssentrerte kubiske strukturen) man regner med de nærmeste naboene også)."
- ↑ Jones 2010, s. 169
- ↑ Masterton & Slowinski 1977, s. 160 liste B, Si, Ge, As, Sb og Te som metalloider, og kommentere at Po og At vanligvis er klassifisert som metalloider, men legg til at dette er vilkårlig siden så lite er kjent om dem.
- ↑ Kraig, Roundy & Cohen 2004, s. 412 ; Alloul 2010, s. 83
- ↑ Vernon 2013, s. 1704
- ↑ Vernon 2013, s. 1703
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