metalloids

A metalloid is a type of chemical element which has a preponderance of properties in between, or that are a mixture of, those of metals and nonmetals. There is no standard definition of a metalloid and no complete agreement on which elements are metalloids. Despite the lack of specificity, the term remains in use in the literature of chemistry.

The six commonly recognised metalloids are boron, silicon, germanium, arsenic, antimony, and tellurium. Five elements are less frequently so classified: carbon, aluminium, selenium, polonium, and astatine. On a standard periodic table, all eleven elements are in a diagonal region of the p-block extending from boron at the upper left to astatine at lower right. Some periodic tables include a dividing line between metals and nonmetals, and the metalloids may be found close to this line.

Typical metalloids have a metallic appearance, but they are brittle and only fair conductors of electricity. Chemically, they behave mostly as nonmetals. They can form alloys with metals. Most of their other physical properties and chemical properties are intermediate in nature. Metalloids are usually too brittle to have any structural uses. They and their compounds are used in alloys, biological agents, catalysts, flame retardants, glasses, optical storage and optoelectronics, pyrotechnics, semiconductors, and electronics.

The electrical properties of silicon and germanium enabled the establishment of the semiconductor industry in the 1950s and the development of solid-state electronics from the early 1960s.

The term ''metalloid'' originally referred to nonmetals. Its more recent meaning, as a category of elements with intermediate or hybrid properties, became widespread in 1940–1960. Metalloids are sometimes called semimetals, a practice that has been discouraged, as the term ''semimetal'' has a different meaning in physics than in chemistry. In physics, it refers to a specific kind of electronic band structure of a substance. In this context, only arsenic and antimony are semimetals, and commonly recognised as metalloids.

Definitions

Judgment-based

A metalloid is an element that possesses a preponderance of properties in between, or that are a mixture of, those of metals and nonmetals, and which is therefore hard to classify as either a metal or a nonmetal. This is a generic definition that draws on metalloid attributes consistently cited in the literature. Difficulty of categorisation is a key attribute. Most elements have a mixture of metallic and nonmetallic properties, Hopkins & Bailar 1956, p. 458 and can be classified according to which set of properties is more pronounced. Only the elements at or near the margins, lacking a sufficiently clear preponderance of either metallic or nonmetallic properties, are classified as metalloids.

Boron, silicon, germanium, arsenic, antimony, and tellurium are commonly recognised as metalloids. Depending on the author, one or more from selenium, polonium, or astatine are sometimes added to the list. Boron sometimes is excluded, by itself, or with silicon. Sometimes tellurium is not regarded as a metalloid. Swift & Schaefer 1962, p. 100 The inclusion of antimony, polonium, and astatine as metalloids has been questioned.

Other elements are occasionally classified as metalloids. These elements include hydrogen, beryllium, nitrogen, Rausch 1960 phosphorus, sulfur, zinc, gallium, tin, iodine, lead, bismuth, and radon. The term metalloid has also been used for elements that exhibit metallic lustre and electrical conductivity, and that are amphoteric, such as arsenic, antimony, vanadium, chromium, molybdenum, tungsten, tin, lead, and aluminium. The p-block metals, and nonmetals (such as carbon or nitrogen) that can form alloys with metals or modify their properties have also occasionally been considered as metalloids.

Criteria-based

No widely accepted definition of a metalloid exists, nor any division of the periodic table into metals, metalloids, and nonmetals; Hawkes Hawkes 2001, p. 1687 questioned the feasibility of establishing a specific definition, noting that anomalies can be found in several attempted constructs. Classifying an element as a metalloid has been described by Sharp Sharp 1981, p. 299 as "arbitrary".

The number and identities of metalloids depend on what classification criteria are used. Emsley recognised four metalloids (germanium, arsenic, antimony, and tellurium); James et al. listed twelve (Emsley's plus boron, carbon, silicon, selenium, bismuth, polonium, moscovium, and livermorium). On average, seven elements are included in such lists; individual classification arrangements tend to share common ground and vary in the ill-defined margins.

A single quantitative criterion such as electronegativity is commonly used, metalloids having electronegativity values from 1.8 or 1.9 to 2.2. Further examples include packing efficiency (the fraction of volume in a crystal structure occupied by atoms) and the Goldhammer-Herzfeld criterion ratio. The commonly recognised metalloids have packing efficiencies of between 34% and 41%. The Goldhammer-Herzfeld ratio, roughly equal to the cube of the atomic radius divided by the molar volume, is a simple measure of how metallic an element is, the recognised metalloids having ratios from around 0.85 to 1.1 and averaging 1.0.
Other authors have relied on, for example, atomic conductance or bulk coordination number.

Jones, writing on the role of classification in science, observed that " lassesare usually defined by more than two attributes". Masterton and Slowinski used three criteria to describe the six elements commonly recognised as metalloids: metalloids have ionization energies around 200 kcal/mol (837 kJ/mol) and electronegativity values close to 2.0. They also said that metalloids are typically semiconductors, though antimony and arsenic (semimetals from a physics perspective) have electrical conductivities approaching those of metals. Selenium and polonium are suspected as not in this scheme, while astatine's status is uncertain.

In this context, Vernon proposed that a metalloid is a chemical element that, in its standard state, has (a) the electronic band structure of a semiconductor or a semimetal; and (b) an intermediate first ionization potential "(say 750−1,000 kJ/mol)"; and (c) an intermediate electronegativity (1.9–2.2).

Periodic table territory

Location

Metalloids lie on either side of the dividing line between metals and nonmetals. This can be found, in varying configurations, on some periodic tables. Elements to the lower left of the line generally display increasing metallic behaviour; elements to the upper right display increasing nonmetallic behaviour. When presented as a regular stairstep, elements with the highest critical temperature for their groups (Li, Be, Al, Ge, Sb, Po) lie just below the line.

The diagonal positioning of the metalloids represents an exception to the observation that elements with similar properties tend to occur in vertical groups. Gray 2009, p. 9 A related effect can be seen in other diagonal similarities between some elements and their lower right neighbours, specifically lithium-magnesium, beryllium-aluminium, and boron-silicon. Rayner-Canham Rayner-Canham 2011 has argued that these similarities extend to carbon-phosphorus, nitrogen-sulfur, and into three d-block series.

This exception arises due to competing horizontal and vertical trends in the nuclear charge. Going along a period, the nuclear charge increases with atomic number as do the number of electrons. The additional pull on outer electrons as nuclear charge increases generally outweighs the screening effect of having more electrons. With some irregularities, atoms therefore become smaller, ionization energy increases, and there is a gradual change in character, across a period, from strongly metallic, to weakly metallic, to weakly nonmetallic, to strongly nonmetallic elements. Going down a main group, the effect of increasing nuclear charge is generally outweighed by the effect of additional electrons being further away from the nucleus. Atoms generally become larger, ionization energy falls, and metallic character increases. The net effect is that the location of the metal–nonmetal transition zone shifts to the right in going down a group, and analogous diagonal similarities are seen elsewhere in the periodic table, as noted.

Alternative treatments

Elements bordering the metal–nonmetal dividing line are not always classified as metalloids, noting a binary classification can facilitate the establishment of rules for determining bond types between metals and nonmetals. Roher 2001, pp. 4–6 In such cases, the authors concerned focus on one or more attributes of interest to make their classification decisions, rather than being concerned about the marginal nature of the elements in question. Their considerations may or not be made explicit and may, at times, seem arbitrary. Metalloids may be grouped with metals; or regarded as nonmetals; or treated as a sub-category of nonmetals. Other authors have suggested classifying some elements as metalloids "emphasizes that properties change gradually rather than abruptly as one moves across or down the periodic table". Brown & Holme 2006, p. 57 Some periodic tables distinguish elements that are metalloids and display no formal dividing line between metals and nonmetals. Metalloids are instead shown as occurring in a diagonal band or diffuse region. The key consideration is to explain the context for the taxonomy in use.

Properties

Metalloids usually look like metals but behave largely like nonmetals. Physically, they are shiny, brittle solids with intermediate to relatively good electrical conductivity and the electronic band structure of a semimetal or semiconductor. Chemically, they mostly behave as (weak) nonmetals, have intermediate ionization energies and electronegativity values, and amphoteric or weakly acidic oxides. They can form alloys with metals. Most of their other physical and chemical properties are intermediate in nature.

Compared to metals and nonmetals

Characteristic properties of metals, metalloids, and nonmetals are summarized in the table. Physical properties are listed in order of ease of determination; chemical properties run from general to specific, and then to descriptive.

The above table reflects the hybrid nature of metalloids. The properties of ''form, appearance'', and ''behaviour when mixed with metals'' are more like metals. ''Elasticity'' and ''general chemical behaviour'' are more like nonmetals. ''Electrical conductivity, band structure, ionization energy, electronegativity,'' and ''oxides'' are intermediate between the two.

Common applications

:''The focus of this section is on the recognised metalloids. Elements less often recognised as metalloids are ordinarily classified as either metals or nonmetals; some of these are included here for comparative purposes.''
Metalloids are too brittle to have any structural uses in their pure forms. They and their compounds are used as (or in) alloying components, biological agents (toxicological, nutritional, and medicinal), catalysts, flame retardants, glasses (oxide and metallic), optical storage media and optoelectronics, pyrotechnics, semiconductors, and electronics.

Alloys

Writing early in the history of intermetallic compounds, the British metallurgist Cecil Desch observed that "certain non-metallic elements are capable of forming compounds of distinctly metallic character with metals, and these elements may therefore enter into the composition of alloys". He associated silicon, arsenic, and tellurium, in particular, with the alloy-forming elements. Phillips and Williams suggested that compounds of silicon, germanium, arsenic, and antimony with B metals, "are probably best classed as alloys".

Among the lighter metalloids, alloys with transition metals are well-represented. Boron can form intermetallic compounds and alloys with such metals of the composition M_''n''B, if ''n'' > 2. Ferroboron (15% boron) is used to introduce boron into steel; nickel-boron alloys are ingredients in welding alloys and case hardening compositions for the engineering industry. Alloys of silicon with iron and with aluminium are widely used by the steel and automotive industries, respectively. Germanium forms many alloys, most importantly with the coinage metals.

The heavier metalloids continue the theme. Arsenic can form alloys with metals, including platinum and copper; it is also added to copper and its alloys to improve corrosion resistance and appears to confer the same benefit when added to magnesium. Antimony is well known as an alloy-former, including with the coinage metals. Its alloys include pewter (a tin alloy with up to 20% antimony) and type metal (a lead alloy with up to 25% antimony). Tellurium readily alloys with iron, as ferrotellurium (50–58% tellurium), and with copper, in the form of copper tellurium (40–50% tellurium). Ferrotellurium is used as a stabilizer for carbon in steel casting. Of the non-metallic elements less often recognised as metalloids, selenium – in the form of ferroselenium (50–58% selenium) – is used to improve the machinability of stainless steels.

Biological agents

All six of the elements commonly recognised as metalloids have toxic, dietary or medicinal properties. Arsenic and antimony compounds are especially toxic; boron, silicon, and possibly arsenic, are essential trace elements. Boron, silicon, arsenic, and antimony have medical applications, and germanium and tellurium are thought to have potential.

Boron is used in insecticides and herbicides. It is an essential trace element. Science Learning Hub 2009 As boric acid, it has antiseptic, antifungal, and antiviral properties.

Silicon is present in silatrane, a highly toxic rodenticide. Long-term inhalation of silica dust causes silicosis, a fatal disease of the lungs. Silicon is an essential trace element. Silicone gel can be applied to badly burned patients to reduce scarring.

Salts of germanium are potentially harmful to humans and animals if ingested on a prolonged basis. There is interest in the pharmacological actions of germanium compounds but no licensed medicine as yet.

Arsenic is notoriously poisonous and may also be an essential element in ultratrace amounts. Nielsen 1998 During World War I, both sides used "arsenic-based sneezing and vomiting agents…to force enemy soldiers to remove their gas masks before firing mustard or phosgene at them in a second salvo." It has been used as a pharmaceutical agent since antiquity, including for the treatment of syphilis before the development of antibiotics. Jaouen & Gibaud 2010 Arsenic is also a component of melarsoprol, a medicinal drug used in the treatment of human African trypanosomiasis or sleeping sickness. In 2003, arsenic trioxide (under the trade name Trisenox) was re-introduced for the treatment of acute promyelocytic leukaemia, a cancer of the blood and bone marrow. Arsenic in drinking water, which causes lung and bladder cancer, has been associated with a reduction in breast cancer mortality rates.

Metallic antimony is relatively non-toxic, but most antimony compounds are poisonous.
Two antimony compounds, sodium stibogluconate and stibophen, are used as antiparasitical drugs.

Elemental tellurium is not considered particularly toxic; two grams of sodium tellurate, if administered, can be lethal. People exposed to small amounts of airborne tellurium exude a foul and persistent garlic-like odour. Tellurium dioxide has been used to treat seborrhoeic dermatitis; other tellurium compounds were used as antimicrobial agents before the development of antibiotics. In the future, such compounds may need to be substituted for antibiotics that have become ineffective due to bacterial resistance.

Of the elements less often recognised as metalloids, beryllium and lead are noted for their toxicity; lead arsenate has been extensively used as an insecticide. Sulfur is one of the oldest of the fungicides and pesticides. Phosphorus, sulfur, zinc, selenium, and iodine are essential nutrients, and aluminium, tin, and lead may be. Sulfur, gallium, selenium, iodine, and bismuth have medicinal applications. Sulfur is a constituent of sulfonamide drugs, still widely used for conditions such as acne and urinary tract infections. Gallium nitrate is used to treat the side effects of cancer; gallium citrate, a radiopharmaceutical, facilitates imaging of inflamed body areas. Selenium sulfide