Sulfur

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Sulfur is located under oxygen in the periodic table. Thus like oxygen sulfur too tends to form directed covalent bonds (usually two – see: limits of the construction kit analogy), Having two strong directed covalent bonds makes it especially useful for gemstone metamaterial technology (advanced APM). Right after carbon, hydrogen, oxygen, and nitrogen sulfur is probably the next most important element for gemstone metamaterial technology.

On sulfurs abundance: Sulfur is not one of the extremely abundant elements, but
it often occurs in concentrated deposits making it decently accessible.

Weak sulfur bonds (compared to oxygen):
The covalent bonds that sulfur forms are not quite as strong as the bonds that oxygen forms.
This is probably mostly due to sulfurs notably bigger atomic radius. This is not a problem though for ...

Soft sulfur compounds:
Also the minerals sulfur compounds tend to form tend to be weak in terms of Mohs hardness. In nature sulfur tends to form minerals with heavy/toxic/rare elements leaning to the right side of the periodic table. In contrast to oxides many sulfide compounds are rather soft.

Sulfur in macroscale style machinery at the nanoscale

Sulfur passivation in diamondoid bearings and gears

Due to sulfurs:

  • larger size than oxygen
  • still quite covalent behaviour and
  • typical bond order of two

Sulfur seems especially useful for:

See: Examples of diamondoid molecular machine elements
Lot's of sulfur there. Indicated by yellow color.

Passivating bearing surfaces with atoms with two bonds to the underlying surface can prevent atomic scale snapback for higher internal bearing pressures.

It is convenient that sulfur is a decently common element.
Also it's mostly needed on surfaces. Which make a small fraction of the volume.

Sulfur for other surface passivation (beside diamond and allotropes)

Unlike silicon dioxide (SiO2) silicon disulfide (SiS2) forms polymer chains.
This might point to sulfur being a good candidate for passivating silicon rich surfaces that shall contact each other and slide on each other.

Sulfur with lots of oxygen as directly adjacent neighbours (highly oxidized sulfur)

Oxygen likes to (double)bond to sulfur:
(may be more useful as a reactive functional group than a passive surface capping – depends on how well controlled the environment is)

Sulfur based gemstone like compounds

Sulfur as drop in replacement for oxygen

Since it's directly above in the periodic table and thus chemically similar.

  • TiO2 (rutile sructure) => TiS2 [1] (insoluble in water) thermodynamic production leads to but a layered structure very different to the rutile structure. (TODO: investigate mechanosynthesizability and degree of metastability stability of rutile structure TiS2) (infos about mechanical properties overshadowed by electronic properties)
  • Al2O3 (sapphire) or other other phases, including the cubic γ and η phases, the monoclinic θ phase, the hexagonal χ phase, the orthorhombic κ phase and the δ phase that can be tetragonal or orthorhombic.
  • Al2S3 (sapphire structure) still hard but reacts with water -- more than six other crystalline forms are known to be thermodynamically accessible (TODO: How can Al2S3 feature wurtzite structure when stoichiometry is not 1:1)

Common natural sulfides (occurring as minerals)

  • Iron sulfides [2] – pyrite marcasite (both FeS2), troilite (FeS) and many more
  • Zinc sulfide [3] – Minearls sphalerite [4] (ZnS)
  • Copper sulfides [5] – Many minerals including very soft Covellite (CuS) and soft Chalcocite (Cu2) (analog to mid hard transparent cuprite?)
  • Lead sulfides: [6] galena (PbS)

Rare but notable:

  • Typical sulfides: Cinnabar HgS; Arsenic sulfide minerals [7]
  • Despite titaniums abundance titanium sulfide minerals are very rare. – Wassonite (TiS) & [8] (TiS2)
  • Millerite NiS – (nickel is rare on earth but common in metallic asteroids)

Rare exotic synthetic sulfur compounds

Continuously going right in the periodic table pairing more and more electronegative elements with the already electronegative element sulfur can lead to uncommon oxidation numbers and more and more reactive species less and less suitable as structural material.

Boron group:

  • Boron sulfide B2S3 [9] reacts with water (bad combo with boron)
  • Aluminium sulfide Al2S3 [10] reacts with water (bad combo with aluminium) (Isostructural sulfur analog to sapphire Al2O3? If so pseudo polymorphs might be stable)

Carbon group:

  • Carbon disulfide [11] – the "thermodynamic polymorph" is a a highly toxic volatile liquid
  • Silicon disulfide [12] (chains)
  • Germanium disulfide [13] – thermodynamic production gives glassy amorphous 3D polymers indicating strongly covalent behaviour (desirable) – But germanium is a rather rare element not suitable as structural material.
  • Tin disulfide [14] (mineral berndtite) (cadmium iodide structure)
  • Lead disulfide [15] (not to confuse with the as mineral occurring lead monosulfide: galena) (cadmium iodide structure)

Pnictogen group:

  • Sulfur nitrides: [16] especially terasulfur tetranitride [17] (explosive)
  • Phosphorus sulfides: [18] e.g. P4S10 P4S3 (all very unhealthy)

Chalcogenide group (sulfurs own group):

  • Sulfur oxides: [19] – precursor to: sulfuric acid, sulfurous acid, ...

Halogenide group (counting hydrogen to the halogenides):

  • (Di)Hydrogen sulfide [20] – (infamous)
  • Sulfur fluorides: [21] – all but one are toxic (as expectable) with the odd exception of sulfur hexafluoride [22]
  • Sulfur chlorides: [23] – beside SCl2 there are S2Cl2 and SCl4

Earth alkali sulfides:
Calcium sulfide [24] and magnesium sulfide [25] occur as mineral despite hygroscopic it calcium-oldhamite & magnesium-oldhamite

Sulfur in the solar system

Sulfur is a borderline volatile ("atmosphere seeking") element.

  • On Earth the bulk of all the sulfur was drawn from the atmosphere by life (just as the carbon).
  • On Venus a huge amount of sulfur has accumulated in the atmosphere in the form of sulfur trioxide SO3 (alongside the carbon dioxide and nitrogen)
  • On Titan all the sulfur is certainly frozen out due to the cold temperatures (maybe even sunk down to the silicate core - we don't know yet).
  • On Mars the lack of sulfur in the atmosphere is probably because a combination of low temperatures and limited volcanic activity

Extreme amounts of sulfur can be found on Jupiter's giant moon Io.
Io is the nearest giant moon of Jupiter (one of four). So near that the tidal forces heat it up enough to convert it into a giant volcano moon. The heat seem to have evaporated off the lightest volatiles like water. Lacking a wealth of heavy elements too (known from low density) all thats left are mid mass elements like mostly silicon, (oxygen) and a lot of sulfur. Beside lava flows there are gargantuan geyser like vents where material re-sublimes to "sulfuric snow". All this makes Io it very colorful and pretty (poisonous pretty). Since Io has no atmosphere ejected "snow" falls back to the surface in a throwing parabola. (Also since Io has no atmosphere if water comes up it boils even at O°C).

We have no ground based images of Io's surface yet. But there is a place on earth that might look similar (Ethiopia – Danakil Depression – Dallol) "Dallol" means dissolution / colorful area / ? (to check). Very fitting for all the concentrated sulfuric acid puddles there.

All the color images we have of Io likely do not show the colors as our human eyes would perceive them. This is because scientific interest had higher priority thus the color fiters in both visiting spaceprobes ( did not match the RGB of our screens or the "RGB" of our eyes. In contrast newest mars images are excellent in this regard, even taking the dynamic color temperature adaption of the human eyes into account.

Sulfur forming two bonds and the limits to that

In organic chemistry sulfur likes to form two bonds. Just like oxygen above it in the periodic table.
And to lesser degree like the much more rate selenium below in the periodic table.
Thus sulfur van serve as nanoscale passivation element for sliding interfaces that do not bond on contact.
It's bigger size than carbon means that it is more compatible with silicon than with carbon for a low energy stable surface.
On the other hand this can be used for intentional bending.

Sulfur being bigger with weaker bond farther apart valence electrons can also can form numbers of bonds differing from two. And that not only in the form of electron deficiency bonds.

Sulfurs borderline volatility

Sulfur is a kind of borderline volatile element.
On Earth in hot volcanism sulfur gets expelled just like water,
It gets easily oxidizes goes into the atmosphere.
But then it quickly becomes sulfuric and rains down (gets washed out),
reacting with the cold ground where it reacts and gets bound again.

Extraterrestrial sulfur

On Venus the situation is similar to Earth. Just that Venus has very little water.
So a lot of SO<ub>3</sub> stays non-hydrated.

On Io without any oxygen or water gas around the volcanically expelled sulfur vapor
can't even oxidize. It likely re-sublimates to "spaceosols" falling back down in a parabolic arc.
Interactions with radiation give some chemistry.
Depending on the rate of falling sulfur snow this may or may not pose a problem for exploratory spacecraft like rovers.

Related

External links

Wikipedia

(wiki-TODO: maybe add illustrative images -- Dallol, Io (real color trouble), ...?)

  • Disulfur (unlike O2 weak unstable S=S double bond - but also a dirarical)
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