No.

172

New Allotropes of Main Group Elements (3)

Kentaro Sato

Sulfur Fast cooling of the melt in cold water leads to the formation
(1) S8 of amorphous sulfur (or “rubbery” sulfur). It is the product
When it comes to allotropes, sulfur is one of the most of ring-opening polymerization of S8 and very elastic as its
versatile of all elements. High school textbooks list a few of nickname suggests. Upon long storage, it spontaneously
sulfur allotropes, such as orthorhombic sulfur, monoclinic returns to orthorhombic form.
sulfur, and amorphous sulfur. The first two allotropes both
consist of eight-membered ring molecules of sulfur (S 8) The color of rubbery sulfur had been considered either
as a basic unit and differ in the crystal packing pattern. black or dark brown, but in 2009, a seventeen-year-old boy
The yellow crystal we associate with “sulfur” is the experimentally proved it inaccurate and textbooks had to be
orthorhombic sulfur (aka. α-sulfur), which is the only stable rewritten. In the experiment, when he converted a sample
allotrope at room temperature. of orthorhombic sulfur with 99% purity into rubbery sulfur,
he obtained a brown product as expected. However, when
he used 99.5% pure orthorhombic sulfur, he obtained a
surprisingly light yellow product.

It should be noted that the composition of amorphous

sulfur changes depending on how it is prepared and so does
its color. Therefore, the yellow color the boy observed
was probably not the outcome of purity factor alone.
Nevertheless, it was a remarkable finding made thanks to his
careful analysis and critical thinking.

The eight-membered ring sulfur (S8) (Wikipedia) (3) Other cyclic sulfur allotropes
Sulfur can exist in shapes other than eight-membered
ring and many of them have been created by chemical
The molecule of S8 takes a crown-like shape in which synthesis. For example, the six-membered sulfur (S6) was
the sulfur atoms are connected in zigzag-fashion. The bond synthesized by reacting H2S4 and S2C12. On molecular level,
angle is roughly 108° and not so apart from that of carbon S6 takes a chair conformation similar to cyclohexane, and
(109.5°), yet it is interesting that sulfur is most stable as an on macroscopic level, it forms a red-orange rhombohedral
eight-membered ring unlike carbon. crystal.

(2) Amorphous Sulfur The twelve-membered ring sulfur is fairly stable and has
When this orthorhombic sulfur is heated, it melts into a been studied in detail. The molecule of S12 has a three-fold
dark red liquid after passing through monoclinic sulfur state. rotational axis and looks like a compressed cuboctahedron.
scheme 2. Bifunctional catalysts bearing protic chelate amine ligands.

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Interestingly, this structure is unique and different from get more attention if a new unique allotrope is discovered,
other molecules such as cyclododecane and crown ether. but the possibility is uncertain.

Germanium
Germanium is below silicon in the periodic table and
it takes a diamond-like structure like silicon at ambient
temperature and pressure. Having semi-conducting property,
this α-germanium used to be found in transistors.

Germanium has another allotrope called β-germanium.

When a high pressure (higher than 120 kilobar) is applied
The twelve-membered ring sulfur (S12) (Wikipedia)
to α-germanium, it undergoes phase transition to become
β-germanium, which has metallic properties.
In addition, various sulfur allotropes such as 7, 9, 10,
11, 13, 14, 15, 18, and 20-membered rings have been In previous columns, we have covered several examples
synthesized. of flat or almost flat two-dimensional honeycomb-structured
allotropes of boron, silicon, phosphorus, and other elements.
(4) Additional sulfur allotropes Like graphene, these substances exhibit unique physical
The boiling point of sulfur is 445 degrees Celsius. The properties and are attracting attentions.
composition of the vapor is S8 near the boiling point, but
S2 starts to form at around 750 degrees. The purple-colored It is then natural to wonder whether germanium can do
gas of diatomic sulfur is, like oxygen, in the state of triplet the same. The carbon-based graphene and the silicon-based
radical. silicene were synthesized on copper and silver surfaces,
respectively. If copper and silver has been used already,
Other sulfur allotropes include fibrous and sheet sulfurs. why not trying gold next? So, in 2014, when the vapor of
It is said that sulfur has more than 30 allotropes in total. germanium was deposited on a gold surface using a method
Sulfur does not make nanotube- or graphene-equivalent called germanium molecular beam epitaxy, an impressive
structures unlike elements such as phosphorus, but instead single-layered “germanene” was obtained. This is one of the
its allotropes form an impressively diverse chemical space. new promising materials for which further progress can be
It is very well possible that new allotropes of sulfur will be expected.
discovered in future.

Tin
Selenium The element that sits below germanium is tin, which is
Let us touch on selenium, which is positioned below one of the metallic elements we humans have been using for
sulfur in the periodic table. Selenium has many allotropes a long time. There is a famous episode about the allotropes
too, and the most stable one at room temperature and of tin. In 1812, when the Napoleon-led French army went
under normal pressure is called gray selenium or metallic deep into Russia, the soldiers were wearing uniforms
selenium. In gray selenium, the atoms are bonded to form a equipped with buttons made with tin. And the freezing
long helical structure. temperature of the Russian winter caused the tin to undergo
phase transition, from metallic β-tin to nonmetallic α-tin.
On the other hand, selenium also makes an eight- The later has lower density and is weaker, so the buttons
membered ring like sulfur, and the crystalline form of this crumbled and the soldiers couldn’t protect themselves from
is known as α-selenium. Six- and seven-membered ring the cold.
allotropes and amorphous selenium are also known.
However, this story is generally considered to be
Selenium is, however, highly toxic and the compounds doubtful by historians. The actual temperature needed for
often have a strongly bad smell. It was once used in the phase transition of tin is ˗30 degrees Celsius and it takes
rectifiers but is diminishing now after having been replaced a long time too, so it was unlikely that even the Russian
by silicon. Perhaps for these reasons, the research on winter was that harsh. The story was probably made up to
selenium is not as active as other elements. Selenium may explain the nightmarish defeat of the heroic figure.

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In the same way as germanium, α-tin is a non-metal with

diamond-like structure and β-tin is a metal with tetragonal
crystalline structure. However, unlike germanium, the β-tin
is the stable form at ambient temperature and pressure.
Additionally, the allotropes of tin include γ-tin, which exists
at higher than 161 degrees Celsius, and σ-tin, which can
exist only under high pressure conditions.

The tin-equivalent of graphene, silicene, and germenene

as yet another two-dimensional material had been predicted
for some time. In 2015, it was actually synthesized in lab
using molecular beam epitaxy, the same way germanene
was produced.

The newly obtained “stanene” is expected to possess

“perfect conductivity” at room temperature, meaning that
it can transfer electricity without wasting any energy as
heat. Also, stanene is predicted to react quickly with oxides
of nitrogen and sulfur, which could be developed into a
technology for the removal of air pollution substances.

The exciting thing about new materials is that they

open up a new path that expands the possibility of science.
The new allotropes we have just covered will likely trigger
further discoveries and push the scientific research to higher
levels.

Introduction of the author :

Kentaro Sato
[Brief career history] He was born in Ibaraki, Japan, in 1970. 1995 M. Sc. Graduate School of Science and
Engineering, Tokyo Institute of Technology. 1995-2007 Researcher in a pharmaceutical company. 2008-
Present Freelance science writer. 2009-2012 Project assistant professor of the graduate school of Science, the
University of Tokyo. 2014-present Publicist for π-system figuration, scientific research on innovative areas.
[Specialty] Organic chemistry
[Website] The Museum of Organic Chemistry <http://www.org-chem.org/yuuki/MOC.html>

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