Communication

pubs.acs.org/jchemeduc

Which Elements Are Metalloids?

René E. Vernon*
Charles Sturt University, Locked Bag 588, Wagga Wagga, New South Wales 2678, Australia

ABSTRACT: The results of a recent survey of 194 metalloid lists are consistent with a three-criterion description of metalloids
published over 35 years ago. The classifications of selenium, polonium, and astatine, and other metalloid-like elements, are briefly
reviewed in this light.
KEYWORDS: High School/Introductory Chemistry, First-Year Undergraduate/General, Inorganic Chemistry, Physical Chemistry,
Misconceptions/Discrepant Events, Metalloids/Semimetals, Periodicity/Periodic Table

that metalloids are typically semiconductors, “although

P ast issues of this Journal have reviewed the concept of a
metalloid,1 investigated the most easily defensible list of
metalloids,2 and challenged the basis for classifying polonium
antimony and arsenic [being semimetals in the physics-based
sense] have electrical conductivities which approach those of
and astatine as metalloids.3,4 The concept of a metalloidas a metals”.13 The applicable elements and criterion values are
member of a class of elements intermediate between metals and listed in Table 1.
nonmetalsis a relatively old one, straddling the establishment
of the periodic law in 1869.5 Even so, this concept has only Table 1. The Six Elements Commonly Recognized as
been reasonably well accepted since 1940−1960, and has yet to Metalloids12,14−16
be more clearly defined, even if only to establish a common or
core set of metalloids. The related purpose of this IP/ IP/ Electronic
Element (kcal/mol) (kJ/mol) ENa ENb Band Structurec
communication is to draw attention to a recent survey of 194
metalloid lists and to an older (little known) description of β-Boron 193 800 2.0 2.04 semiconductor
metalloids based on three criteria. It transpires that the α-Silicon 189 786 1.8 1.90 semiconductor
elements most commonly recognized as metalloids in the α-Germanium 184 762 1.8 2.01 semiconductor
survey are the same as the elements whose properties were used α-Arsenic 228 944 2.0 2.18 semimetal
to inform the three-criterion description. The classifications of α-Antimony 201 830 1.9 2.05 semimetal
selenium, polonium, and astatine, as well as gray tin and other α-Tellurium 210 869 2.1 2.10 semiconductor
metalloid-like elements, are briefly reviewed in this light. Average 201 832 1.9 2.05 -

■
SURVEY OF ELEMENTS COMMONLY RECOGNIZED
AS METALLOIDS
By way of a literature search, the author compiled a list of 194
metalloid lists, dating from 1947 onward.6 The list includes 26
different elements identified as metalloids, across 67 different
list configurations, with an average of just over seven elements
per list. The percentage appearance frequencies of the elements
most frequently identified as metalloids are boron (86), silicon
(95), germanium (96), arsenic (100), selenium (23), antimony
(88), tellurium (98), polonium (49), and astatine (40). Of the
menagerie of other elements occasionally identified as metal-
loids, carbon (9), aluminum (9), and bismuth (6) are the front
runners.
The survey results are consistent with the assertions made by
other authors that six elements are commonly recognized as
metalloids: boron, silicon, germanium, arsenic, antimony, and
tellurium.1,2,7−11
a
Original Pauling electronegativity value. bRevised Pauling value. cFor
the element in its standard state, as shown in the first column.
Masterton and Slowinski’s description is remarkable for its
use of these three more-or-less clearly defined criteria. In
contrast, metalloids tend to be collectively characterized in
terms of generalities or a few broadly indicative physical or
chemical properties,1 with a single quantitative criterion or
attribute (such as electrical conductivity,17 packing efficiency,18
or the acid−base character of group oxides19) being mentioned
only occasionally.20 Their description can be expressed more
formally, in SI units, to give the following semiquantitative
working definition:
A metalloid is a chemical element that, in its standard state,
has (a) the electronic band structure of a semiconductor or a
semimetal, (b) an intermediate first ionization potential (say,
750−1,000 kJ/mol), and (c) an intermediate electronegativity
(1.9−2.2, revised Pauling).

■ THREE-CRITERION DESCRIPTION
The elements commonly recognized as metalloids in the survey
■ SELENIUM, POLONIUM, AND ASTATINE
Neither selenium nor polonium satisfies the working definition
had also been identified and described as such in 1977 by of a metalloid noted above. Selenium has a first ionization
Masterton and Slowinski.12 They wrote that metalloids have potential of 941 kJ mol−1 and is sometimes described as a
first ionization potentials (IP) clustering around 200 kcal/mol
and electronegativity (EN) values close to 2.0. They also said
© XXXX American Chemical Society and
Division of Chemical Education, Inc. A dx.doi.org/10.1021/ed3008457 | J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education
semiconductor. However its electronegativity of 2.55 is too
high. Polonium has an ionization potential of 812.1 kJ mol−1
and an electronegativity of 2.0, but has a metallic band
structure.21,22 Hawkes2,3,23 also concluded that polonium was
better classified as a metal.
Astatine has a first ionization potential24 of 899 kJ·mol−1 and
an electronegativity of 2.2. However, its electronic band
structure is not known with any great degree of certainty.
Batsanov25 gave a calculated band gap energy for diatomic
astatine of 0.7 eV, a figure which could reasonably be associated
with semiconductor status. Evidence for the existence of
diatomic astatine is, however, sparse and inconclusive.26
Edwards and Sienko27 speculate, on the basis of the
Goldhammer−Herzfeld criterion for metallicity, that astatine
is probably a metalloid. Siekierski and Burgess28 contend or
presume that astatine would be a metal if it could form a
condensed phase but do not give a specific basis for their claim.
Hawkes2,3,23 initially concluded that astatine should be
classified as a nonmetal but has subsequently agreed, upon
further reviewing its mixed and intermediate properties (known
and extrapolated),13 that astatine is better classified as a
metalloid.29 This development is consistent with other
references to the character of astatine. Bresler30 commented
that “the properties of the metal and the halogen are curiously
combined in this element”. Rössler31 similarly highlighted “the
chemical ambiguity of astatine between halogen and metal
character”. More recently, Restrepo et al.32 reported that
astatine appeared to share more in common with polonium (a
metal) than it did with the established halogens. They did so on
the basis of detailed comparative studies of the known and
interpolated properties of 72 elements.
■
GRAY TIN AND OTHER METALLOID-LIKE
ELEMENTS
Gray tin is the stable form of tin below around 55 °F (13 °C).
As tin, it has a first ionization potential14 of 708 kJ/mol and an
electronegativity of 1.96 revised Pauling. Unlike ordinary tin,
which has the electronic band structure of a metal, gray tin has
the electronic band structure of a semimetal.33 With its
relatively low first ionization potential, gray tin does not satisfy
the definition of a metalloid suggested here.
Cohen and Chelikowsky34 regard gray tin as a very poor
metal; Pauling35 says it has the properties of a metalloid;
Ebbing and Gammon,36 who distinguish between metals,
metalloids, and nonmetals, treat gray tin as a nonmetal.
Physically, gray tin could be viewed as a metalloid (silvery
metallic appearance; brittle; moderate conductivity, increasing
with temperature; semimetal band structure). Chemically,
however, gray tin falls marginally on the metal side of the
line given tin is ordinarily regarded as chemically weak metal
rather than a chemically weak nonmetal.37,39
Similar to gray tin, there are a number of other elements that
are mentioned in the literature as being “near metalloidal”,
showing metalloid(al) character, or having metalloid-like or
some metallic characteristics. Examples include graphitic
carbon40,41 (a semimetal along its basal plane; a semiconductor
along its edge plane), black phosphorus42−44 (a semi-
conductor), and bismuth45,46 (a semimetal).
An interesting and elegant solution for accommodating these
metalloid-like elements was provided by Adler,47 who suggested
defining a metalloid simply as a semiconductor or a semimetal.
His suggestion can be viewed as a step too far; few other
authors have regarded these additional elements as metalloids.
B dx.doi.org/10.1021/ed3008457 | J. Chem. Educ. XXXX, XXX, XXX−XXX
Communication
As well, the question of which elements would be counted as
insulators rather than semiconductors was not addressed.
There may be some merit in adapting Adler’s suggestion by
distinguishing between the notion of a “metalloid”, and that of a
“near metalloid”. Metalloids are those elements commonly
recognized as such, which fall within the scope of the definition
set out in this article. A near metalloid then becomes any other
chemical element having the electronic band structure of a
semimetal or a semiconductor, with the latter (for this purpose)
being taken as an element having a band gap less than or equal
to the visible spectrum cutoff of 1.8 eV.48 A semiconductor with
such a relatively narrow band gap49 has a metallic or black
appearance,50,51 and metalloids have traditionally been regarded
as looking like metals52 (semiconductors with wider band gaps,
and insulators, appear colored, white, or transparent).53,54 This
definition would include graphitic carbon, black phosphorus,
gray selenium, gray tin, iodine,55 and bismuth. As noted, these
are all elements described in the literature as being metalloid-
like, or words to that effect. Craig,56 for example, refers to the
“near metalloidal” status of selenium; Schroers57 refers to
carbon and phosphorus as near metalloids. Although aluminum
and polonium are also mentioned in the literature as showing
some metalloid character, both elements have the electronic
band structures of metals and, arguably, show at least a
reasonable preponderance of metallic character. They are both
better regarded as poor metals or chemically weak metals.37,38
■ SUMMARY
There are six elements commonly recognized as metalloids.
Thirty-five years ago, Masterton and Slowinksi published a
three-criterion description of metalloids. Their description
provides a useful basis to establish a more formal definition of a
metalloid. In this light, selenium is better classified as a
nonmetal, and polonium as a metal. Astatine may or may not
be a metalloid according to this definition. However, on the
basis of its currently known and extrapolated properties, astatine
is better classified as a metalloid. If it subsequently transpires
that the band structure of astatine is found to be metallic, then
the working definition of a metalloid suggested here may need
to be revisited. Gray tin and other elements with semimetal or
semiconductor band structures, such as graphite and bismuth,
while not falling within the scope of the metalloid definition
suggested in this communication, may be usefully regarded as
near metalloids, in recognition of their metalloid-like character.
■
AUTHOR INFORMATION
Corresponding Author
* E-mail: rene@webone.com.au.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
I gratefully acknowledge the opportunity to put questions about
metalloids to, and discuss related matters with,
Stephen Hawkes, at Oregon State University; William Jensen,
of the Department of Chemistry, University of Cincinnati;
David Johnson, editor of Metals and Chemical Change (2002);58
Peter Nelson, of the Department of Chemistry, University of
Hull; and Alan Russell, lead author of Structure−Property
Relations in Nonferrous Metals (2005).59 The approach taken in
this communication does not necessarily reflect the views of
Journal of Chemical Education
these authors. I thank anonymous reviewers for their helpful
comments and suggestions.
■
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