Semimetal

Como con los metales y los no metales, los semimetales (también conocidos como metaloides) comprenden una de las tres categorías de elementos químicos siguiendo una clasificación de acuerdo con las propiedades de enlace e ionización.[1] Se caracterizan por presentar un comportamiento intermedio entre los metales y los no metales, compartiendo características de ambos. Por norma general y en la mayoría de los casos, tienden a reaccionar químicamente con no metales, aunque hay ciertos compuestos formados por metal y semimetal como por ejemplo el boruro de magnesio. Pueden ser tanto brillantes como opacos, y su forma puede cambiar fácilmente. Generalmente, los metaloides son mejores conductores de calor y de electricidad que los no metales, pero no tanto como los metales. No hay una forma unívoca de distinguir los metaloides de los metales verdaderos, pero generalmente se diferencian en que los metaloides son semiconductores antes que conductores. A diferencia de los metales, los cuales al aumentar la temperatura disminuye su conductividad eléctrica, en los semimetales aumentar la temperatura supone lo contrario, aumenta su conductividad eléctrica. Los no metales son opacos y de varios colores. Suelen ser utilizados en ocasiones para formar aleaciones. Pueden ser anfóteros o levemente ácidos.

13 14 15 16 17
2 B
Boro		 C
Carbono		 N
Nitrógeno		 O
Oxígeno		 F
Flúor
3 Al
Aluminio		 Si
Silicio		 P
Fósforo		 S
Azufre		 Cl
Cloro
4 Ga
Galio		 Ge
Germanio		 As
Arsénico		 Se
Selenio		 Br
Bromo
5 In
Indio		 Sn
Estaño		 Sb
Antimonio		 Te
Telurio		 I
Iodo
6 Tl
Talio		 Pb
Plomo		 Bi
Bismuto		 Po
Polonio		 At
Astato

Son considerados metaloides los siguientes elementos:

Dentro de la tabla periódica los metaloides se encuentran en línea diagonal desde el boro al ástato (este último no está incluido). Los elementos que se encuentran encima a la derecha son no metales, y los que se encuentran debajo a la izquierda son metales.

Todos estos elementos poseen tres electrones de valencia o más en su última órbita (B 3, Si 4, Ge 4, As 5, Sb 5, Te 6, Po 6). El silicio, por ejemplo, es un metaloide ampliamente utilizado en la fabricación de elementos semiconductores para la industria electrónica, como rectificadores, diodos, transistores, circuitos integrados y microprocesadores.

Definiciones

Basado en el juicio

Un metaloide es un elemento que posee una preponderancia de propiedades intermedias, o que son una mezcla de las de los metales y los no metales, y que, por tanto, es difícil de clasificar como metal o como no metal. Se trata de una definición genérica que se basa en los atributos de los metaloides que se citan sistemáticamente en la literatura

Siguen las definiciones y los extractos de diferentes autores, que ilustran aspectos de la definición genérica:

  • "En química un metaloide es un elemento con propiedades intermedias entre las de los metales y las de los no metales"[2]
  • "Entre los metales y los no metales de la tabla periódica encontramos elementos ... [que] comparten algunas de las propiedades características tanto de los metales como de los no metales, lo que hace difícil situarlos en cualquiera de estas dos categorías principales"[3]
  • "Los químicos a veces utilizan el nombre de metaloide ... para estos elementos que son difíciles de clasificar de una manera u otra"[4]
  • "Dado que los rasgos que distinguen a los metales de los no metales son de naturaleza cualitativa, algunos elementos no caen inequívocamente en ninguna de las dos categorías. Estos elementos ... se llaman metaloides ..."[5]

Más ampliamente, los metaloides han sido denominados como:

  • "elementos que ... son una especie de cruce entre metales y no metales";[6] o
  • "elementos extraños intermedios".[7]

La dificultad de categorización es un atributo clave. La mayoría de los elementos tienen una mezcla de propiedades metálicas y no metálicas,[8] y pueden clasificarse en función de qué conjunto de propiedades sea más pronunciado.[9]

El oro, por ejemplo, tiene propiedades mixtas pero sigue siendo reconocido como el "rey de los metales". Además del comportamiento metálico (como la alta conductividad eléctrica, y la formación de cationes), el oro muestra un comportamiento no metálico:

Sobre su naturaleza de halógeno ver Belpassi et al.,[11] quién indica que en ellos áuridos MAu (M = Li–Cs) el oro "se comporta como un halógeno, intermedio entre el Br y el I"; sobre aurofilicidad ver Schmidbaur and Schier.[12]

Solo los elementos en o cerca de los márgenes, que carecen de una preponderancia suficientemente clara de propiedades metálicas o no metálicas, se clasifican como metaloides..[13]

El boro, silicio, germanio, arsénico, antimonio y teluro normalmente son identificados como metaloides.[14][n 1] Dependiendo del autor, a veces se añaden a la lista uno o más de selenio, polonio o astatina.[16] A veces se excluye el boro, solo o con silicio.[17] A veces el telurio no se considera un metaloide.[18] Se ha cuestionado la inclusión del antimonio, el polonio y la astatina como metaloides.[19].

Otros elementos se clasifican ocasionalmente como metaloides. Estos elementos incluyen[20] hidrógeno,[21] berilio,[22] nitrógeno,[23] fósforo,[24] azufre,[25] zinc,[26] galio,[27] estaño, yodo,[28] plomo,[29] bismuto,[18] y radón.[30] El término metaloide también se ha utilizado para los elementos que presentan brillo metálico y conductividad eléctrica, y que son anfóteros, como el arsénico, el antimonio, el vanadio, el cromo, el molibdeno, el tungsteno, el estaño, el plomo y el aluminio.[31] El metales de bloque p,[32] y los no metales (como el carbono o el nitrógeno) que pueden formar aleacións con los metales[33] o modificar sus propiedades[34] también han sido considerados ocasionalmente como metaloides.

Basado en criterios
Elemento EI
(kcal/mol)		 EI
(kJ/mol)		 EN Estructura de banda electrónica
Boro 191 801 2.04 semiconductor
Silicio 188 787 1.90 semiconductor
Germanio 182 762 2.01 semiconductor
Arsénico 226 944 2,18 semimetal
Antimonio 199 831 2.05 semimetal
Telurio 208 869 2,10 semiconductor
promedio 199 832 2.05
Los elementos comúnmente reconocidos como metaloides, y sus energías de ionización (IE);[35] electronegatividades (EN, escala de Pauling revisada); y estructuras de banda electrónica[36] (formas más estables termodinámicamente en condiciones ambientales).

No existe ninguna definición ampliamente aceptada de metaloide, ni ninguna división de la tabla periódica en metales, metaloides y no metales;[37] Hawkes[38] cuestionó la viabilidad de establecer una definición específica, señalando que se pueden encontrar anomalías en varias construcciones intentadas. La clasificación de un elemento como metaloide ha sido descrita por Sharp[39] como "arbitraria".

El número y las identidades de los metaloides dependen de los criterios de clasificación que se utilicen. Emsley[40] reconoció cuatro metaloides (germanio, arsénico, antimonio y telurio); James et al.[41] enumeraron doce (los de Emsley más el boro, el carbono, el silicio, el selenio, el bismuto, el polonio, el moscovio y el livermorio). Por término medio, se incluyen siete elementos en las listas de metaloides; los arreglos individuales de clasificación tienden a compartir un terreno común y varían en el mal definido[42] márgenes.[n 2][n 3]

Se suele utilizar un único criterio cuantitativo como la electronegatividad,[45] los metaloides tienen valores de electronegatividad de 1,8 o 1,9 a 2,2.[46] Otros ejemplos incluyen el eficiencia de empaquetamiento (la fracción de volumen en una estructura cristalina ocupada por átomos) y la relación del criterio Goldhammer-Herzfeld.[47] Los metaloides comúnmente reconocidos tienen eficiencias de empaquetamiento de entre el 34% y el 41%.[n 4]

Otros autores se han basado, por ejemplo, en la conductancia atómica[n 5][51] o número de coordinación global.[52]

Jones, al escribir sobre el papel de la clasificación en la ciencia, observó que "[las clases] generalmente se definen por más de dos atributos".[53] Masterton and Slowinski[54] utilizaron tres criterios para describir los seis elementos comúnmente reconocidos como metaloides: los metaloides tienen energías de ionización alrededor de 200 kcal/mol (837 kJ/mol) y valores de electronegatividad cercanos a 2,0. También dijeron que los metaloides son típicamente semiconductores, aunque el antimonio y el arsénico (semimetales desde una perspectiva física) tienen conductividades eléctricas que se acercan a las de los metales. Se sospecha que el selenio y el polonio no están en este esquema, mientras que el estatus de la astatina es incierto.[n 6]

En este contexto, Vernon propuso que un metaloide es un elemento químico que, en su estado estándar, tiene (a) la estructura de banda electrónica de un semiconductor o un semimetal; y (b) un primer potencial de ionización intermedio "(digamos 750-1.000 kJ/mol)"; y (c) una electronegatividad intermedia (1,9-2,2).[57]

Notas
  1. Mann et al.[15] se refieren a estos elementos como "los metaloides reconocidos".
  2. Jones[43] escribe: "Aunque la clasificación es una característica esencial en todas las ramas de la ciencia, siempre hay casos difíciles en los límites. De hecho, el límite de una clase rara vez es nítido."
  3. La falta de una división estándar de los elementos en metales, metaloides y no metales no es necesariamente un problema. Existe, más o menos, una progresión continua de lo metálico a lo no metálico. Un subconjunto específico de este continuo podría servir para su propósito particular tan bien como cualquier otro.[44]
  4. Como la relación se basa en argumentos clásicos[48] no da cabida al hallazgo de que el polonio, que tiene un valor de ~0,95, adopta una estructura metálica (en lugar de covalente) cristalina, por motivos relativista.[49] Even so it offers a first order rationalization for the occurrence of metallic character amongst the elements.[50]
  5. Atomic conductance is the electrical conductivity of one mole of a substance. It is equal to electrical conductivity divided by molar volume.[4]
  6. El selenio tiene una energía de ionización (IE) de 225 kcal/mol (941 kJ/mol) y a veces se describe como un semiconductor. Tiene una electronegatividad (EN) relativamente alta de 2,55. El polonio tiene un IE de 194 kcal/mol (812 kJ/mol) y una EN de 2,0, pero tiene una estructura de banda metálica.[55] La astatina tiene un IE de 215 kJ/mol (899 kJ/mol) y un EN de 2,2.[56] Su estructura de banda electrónica no se conoce con certeza.

Referencias
  1. Greenwood NN & Earnshaw A 2002, Chemistry of the Elements, 2nd ed., Butterworth-Heinemann, ISBN 0-7506-3365-4
  2. Cusack 1987, p. 360
  3. Kelter, Mosher & Scott 2009, p. 268
  4. Hill & Holman 2000, p. 41
  5. King 1979, p. 13
  6. Moore 2011, p. 81
  7. Gray 2010
  8. Hopkins & Bailar 1956, p. 458
  9. Glinka 1965, p. 77
  10. Wiberg 2001, p. 1279
  11. Belpassi et al. 2006, pp. 4543–44
  12. Schmidbaur & Schier 2008, pp. 1931–51
  13. Tyler Miller 1987, p. 59
  14. Goldsmith 1982, p. 526; Kotz, Treichel & Weaver 2009, p.  62; Bettelheim et al. 2010, p. 46
  16. Hawkes 2001, p. 1686; Segal 1989, p.  965; McMurray & Fay 2009, p. 767
  17. Bucat 1983, p. 26; Brown c. 2007
  18. Swift & Schaefer 1962, p.  100
  19. Hawkes 2001, p. 1686; Hawkes 2010; Holt, Rinehart & Wilson c. 2007
  20. Dunstan 1968, pp. 310, 409. Dunstan enumera como metaloides a Be, Al, Ge (quizás), As, Se (quizás), Sn, Sb, Te, Pb, Bi y Po (pp. 310, 323, 409, 419).
  21. Tilden 1876, pp. 172, 198-201; Smith 1994, p. 252; Bodner & Pardue 1993, p.  354
  22. Bassett et al. 1966, p. 127
  23. Rausch 1960
  24. Thayer 1977, p.  604; Warren & Geballe 1981; Masters & Ela 2008, p.  190
  25. Warren & Geballe 1981; Chalmers 1959, p. 72; Buró de Personal Naval de EE.UU. 1965, p. 26
  26. Siebring 1967, p.  513
  27. Wiberg 2001, p. 282
  28. Rausch 1960; Friend 1953, p.  68
  29. Murray 1928, p. 1295
  30. Hampel & Hawley 1966, p. 950; Stein 1985; Stein 1987, pp.  240, 247-48
  31. Hatcher 1949, p. 223; Secrist & Powers 1966, p.  459
  32. Taylor 1960, p. 614
  33. Considine & Considine 1984, p.  568; Cegielski 1998, p. 147; The American heritage science dictionary 2005, p. 397
  34. Woodward 1948, p. 1
  35. NIST 2010. Los valores mostrados en la tabla anterior se han convertido a partir de los valores del NIST, que se dan en eV.
  36. Berger 1997; Lovett 1977, p. 3
  37. Goldsmith 1982, p. 526; Hawkes 2001, p.  1686
  38. Hawkes 2001, p. 1687
  39. Sharp 1981, p. 299
  40. Emsley 1971, p. 1
  41. James et al. 2000, p. 480
  42. Chatt 1951, p. 417 "El límite entre metales y metaloides es indefinido ..."; Burrows et al. 2009, p. 1192: "Aunque los elementos se describen convenientemente como metales, metaloides y no metales, las transiciones no son exactas ..."
  43. Jones 2010, p. 170
  44. Kneen, Rogers & Simpson 1972, pp. 218-20
  45. Rochow 1966, pp. 1, 4-7
  46. Rochow 1977, p. 76; Mann et al. 2000, p.  2783
  47. Askeland, Phulé & Wright 2011, p. 69
  48. Edwards 1999, p. 416
  49. Steurer 2007, p. 142; Pyykkö 2012, p. 56
  50. Edwards & Sienko 1983, p. 695
  51. Hill & Holman 2000, p. 160. They characterise metalloids (in part) on the basis that they are "poor conductors of electricity with atomic conductance usually less than 10−3 but greater than 10−5 ohm−1 cm−4".
  52. Bond 2005, p. 3: "One criterion for distinguishing semi-metals from true metals under normal conditions is that the bulk coordination number of the former is never greater than eight, while for metals it is usually twelve (or more, if for the body-centred cubic structure one counts next-nearest neighbours as well)."
  53. Jones 2010, p. 169
  54. Masterton & Slowinski 1977, p.  160 enumeran el B, Si, Ge, As, Sb y Te como metaloides, y comentan que el Po y el At se clasifican ordinariamente como metaloides, pero añaden que esto es arbitrario ya que se conoce muy poco sobre ellos.
  55. Kraig, Roundy & Cohen 2004, p. 412; Alloul 2010, p.  83
  56. Vernon 2013, p. 1704
  57. Vernon 2013, p. 1703

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