Allotropes of sulfur

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The allotrope of the element, sulfur, most prevalent in nature, cyclo-octasulfur (cyclo-S8).

The allotropes of sulfur refers to the many allotropes of the element sulfur. In terms of large number of allotropes, sulfur is second only to carbon.[1] In addition to the allotropes, each allotrope often exists in polymorphs, delineated by Greek prefixes (α, β, etc.).[2][page needed]

Furthermore, because elemental sulfur has been an item of commerce for centuries, its various forms are given traditional names.[3] Early workers identified some forms that have later proved to be single or mixtures of allotropes.[3][page needed] Some forms have been named for their appearance, e.g. "mother of pearl sulfur", or alternatively named for a chemist who was pre-eminent in identifying them, e.g. "Muthmann's sulfur I" or "Engel's sulfur".[2][page needed][3]

The most commonly encountered form of sulfur is the orthorhombic polymorph of S
8
, which adopts a puckered ring - or "crown" - structure. Two other polymorphs are known, also with nearly identical molecular structures.[1] In addition to S8, sulfur rings of 6, 7, 9–15, 18 and 20 atoms are known.[1] At least five allotropes are uniquely formed at high pressures, two of which are metallic.[3][page needed]

The number of sulfur allotropes reflects the relatively strong S−S bond of 265 kJ/mol.[1] Furthermore, unlike most elements, the allotropes of sulfur can be manipulated in solutions of organic solvents and is amenable to analysis by HPLC.[4]

Phase diagram for sulfur[edit]

An historic phase diagram of sulfur. A phase diagram from 1975, presenting data through 1970. The ordinate is pressure in kilobars (kbar). and the abscissa is temperature in Kelvin (K). (The temperatures 200K, 400K, 600K, and 800K correspond to the approximate temperatures of -73, 127, 327, and 527°C, respectively.) The Roman numerals I-XII refer to known solid phases identified by "volumetric, optical, and electrical resistance techniques," and letters A-E to putative distinct liquid "phases" identified by differential thermal analysis. Phase information is based on the work of G. C. Vezzoli, et. al, as reviewed by David Young; as Young notes, "The literature on the allotropy of sulfur presents the most complex and confused situation of all the elements."[5][6] Phase information, while complete to this date, are incomplete as of 2015, since limited to ≤50 kbar and thus. e.g., omitting metallic phases.[7][non-primary source needed]

The pressure-temperature (P-T) phase diagram for sulfur is complex (see Image). The region labeled I (a solid region), is α-sulfur.[8] See the legend for further identifications and information, and see the section on high pressure forms for information on these phases.

High pressure solid allotropes[edit]

In a high-pressure study at ambient temperatures, four new solid forms, termed II, III, IV, V have been characterized, where α-sulfur is form I.[8] Solid forms II and III are polymeric forms, solid forms IV and V are metallic (and are superconductive below 10 K and 17 K, respectively).[9] Laser irradiation of solid samples produces 3 photo-inducible forms below 200-300 kbar (20–30 GPa).[clarification needed][3][page needed]

Solid cyclo allotrope preparation[edit]

Two methods exist for the preparation of the cyclo-sulfur allotropes. One of the methods, which is most famous for preparing hexasulfur, is to react hydrogen polysulfides with polysulfur dichloride:

H2Sx + SyCl2cyclo-Sx+y + 2 HCl

A second strategy uses titanocene pentasulfide as a source of the S52− unit. This complex is easily made from polysulfide solutions:[10]

[NH4]2[S5] + (C5H5)2TiCl2 → (C5H5)2TiS5 + 2 NH4Cl

Then the resulting pentasulfur-titanocene complex is allowed to react with polysulfur dichloride to give the desired cyclo-sulfur in the series:[11]

(C5H5)2TiS5 + SyCl2cyclo-Sy+5 + (C5H5)2TiCl2

Solid cyclo-sulfur allotropes[edit]

Cyclo-Pentasulfur, cyclo-S5[edit]

This has not been isolated, but has been detected in the vapour phase.[3][page needed]

Cyclo-hexasulfur, cyclo-S6[edit]

Main article: Hexasulfur
cyclo-hexasulfur, cyclo-S6

This was first prepared by R.C. Engel in 1891 by reacting HCl with thiosulfate, HS2O3.[1] Cyclo-S6 is orange-red and forms a rhombohedral crystal.[1] It is called ρ-sulfur, ε-sulfur, Engel's sulfur and Aten's sulfur.[2][page needed] Another method of preparation involves reacting a polysulfane with sulfur monochloride:[1]

H2S4 + S2Cl2 → cyclo-S6 + 2 HCl (dilute solution in diethyl ether)

The sulfur ring in cyclo-S6 has a "chair" conformation, reminiscent of the chair form of cyclohexane.[1] All of the sulfur atoms are equivalent.[1]

Cyclo-heptasulfur, cyclo-S7[edit]

It is a bright yellow solid.[3][page needed] Four (α-, β-, γ-, δ-) forms of cyclo-heptasulfur are known.[1] Two forms (γ-, δ-)have been characterized.[3][page needed] The cyclo-S7 ring has an unusual range of bond lengths of 199.3–218.1 pm.[3][page needed] It is said to be the least stable of all of the sulfur allotropes.[3][page needed]

Cyclo-octasulfur, cyclo-S8[edit]

Main article: Octasulfur

α-Sulfur[edit]

α-Sulfur, see image, is the form most commonly found in nature.[1] When pure it has a greenish-yellow colour (traces of cyclo-S7 in commercially available samples make it appear yellower).[3][page needed] It is practically insoluble in water and is a good electrical insulator with poor thermal conductivity.[1] It is quite soluble in carbon disulfide: 35.5 g/100 g solvent at 25 °C.[1] It has a rhombohedral crystal structure.[1] This is the predominant form found in "flowers of sulfur", "roll sulfur" and "milk of sulfur".[3][page needed] It contains S8 puckered rings, alternatively called a crown shape.[1] The S-S bond lengths are all 206 pm and the S-S-S angles are 108° with a dihedral angle of 98°.[1] At 95.3 °C, α-sulfur converts to β-sulfur.[1]

β-Sulfur[edit]

This is a yellow solid with a monoclinic crystal form and is less dense than α-sulfur.[1] Like the α- form it contains puckered S8 rings and only differs from it in the way the rings are packed in the crystal.[1] It is unusual because it is only stable above 95.3 °C, below this it converts to α-sulfur.[1] It can be prepared by crystallising at 100 °C and cooling rapidly to slow down formation of α-sulfur.[1] It has a melting point variously quoted as 119.6 °C[12] and 119.8 °C but as it decomposes to other forms at around this temperature the observed melting point can vary from this. The 119 °C melting point has been termed the "ideal melting point" and the typical lower value (114.5 °C) when decomposition occurs, the "natural melting point".[12]

γ-Sulfur[edit]

This form, first prepared by F.W Muthmann in 1890, is sometimes called "nacreous sulfur" or "mother of pearl sulfur" because of its appearance. It crystallises in pale yellow monoclinic needles.[1] It contains puckered S8 rings like α-sulfur and β-sulfur and only differs from them in the way that these rings are packed.[1] It is the densest form of the three.[1] It can be prepared by slowly cooling molten sulfur that has been heated above 150 °C or by chilling solutions of sulfur in carbon disulfide, ethyl alcohol or hydrocarbons.[1] It is found in nature as the mineral rosickyite.[3][page needed]

Cyclo-Sn (n = 9-15, 18, 20)[edit]

cyclo-dodecasulfur, cyclo-S12

These allotropes have been synthesised by various methods for example, reacting titanocene pentasulfide and a dichlorosulfane of suitable sulfur chain length, Sn−5Cl2:[1]

(η5-C5H5)2TiS5 + Sn−5Cl2 → cyclo-Sn

or alternatively reacting a dichlorosulfane, SnmCl2 and a polysulfane, H2Sm:[1]

SnmCl2 + H2Sm → cyclo-Sn

S12, S18 and S20 can also be prepared from S8.[12] With the exception of cyclo-S12, the rings contain S-S bond lengths and S-S-S bond angle that differ one from another.[1]

Cyclo-S12 is the second most stable cyclo- allotrope after cyclo-S8.[1] Its structure can be visualised as having sulfur atoms in three parallel planes, 3 in the top, 6 in the middle and three in the bottom.[1]

Two forms (α-, β-) of cyclo-S9 are known, one of which has been characterized.[3][page needed]

Two forms of cyclo-S18 are known where the conformation of the ring is different. To differentiate these structures, rather than using the normal crystallographic convention of α-, β-, etc., which in other cyclo-Sn compounds refer to different packings of essentially the same conformer, these two conformers have been termed endo- and exo-.[3][page needed]

Cyclo-S6.cyclo-S10 adduct[edit]

This is produced from a solution of cyclo-S6 and cyclo-S10 in CS2.[3][page needed] It has a density midway between cyclo-S6 and cyclo-S10.[3][page needed] The crystal consists of alternate layers of cyclo-S6 and cyclo-S10.[3][page needed] For all the elements this may be the only allotrope which contains molecules of different sizes.[3][page needed]

Solid catena allotropes[edit]

The production of pure forms of catena-sulfur has proved to be extremely difficult. Complicating factors include the purity of the starting material and the thermal history of the sample.

ψ-Sulfur[edit]

This form, also called fibrous sulfur or ω1-sulfur,[2][page needed] has been well characterized. It has a density of 2.01 g·cm−3 (α-sulfur 2.069 g·cm−3) and decomposes around its melting point of 104 °C. It consists of parallel helical sulfur chains.[1] These chains have both left and right-handed "twists" and a radius of 95 pm.[1] The S-S bond length is 206.6 pm, the S-S-S bond angle is 106° and the dihedral angle is 85.3°, (comparable figures for α-sulfur are 203.7 pm, 107.8° and 98.3°).[1]

Lamina sulfur[edit]

This has not been well characterized but is believed to consist of criss-crossed helices.[3][page needed] It is also called χ-sulfur or ω2-sulfur.[2][page needed]

Catena sulfur forms[edit]

The naming of the different forms is very confusing and care has to be taken to determine what is being described as the same names are used interchangeably.[2][page needed]

Amorphous sulfur[edit]

This is the quenched product of sulfur melts above 160 °C (at this point the properties of the liquid melt change remarkably, e.g. large increase in viscosity[1]). Its form changes from an initial plastic form gradually to a glassy form, hence its other names of plastic, glassy or vitreous sulfur.[3][page needed] It is also called χ-sulfur.[2][page needed] It contains a complex mixture of catena-sulfur forms mixed with cyclo-forms.[3][page needed]

Insoluble sulfur[edit]

This is obtained by washing quenched liquid sulfur with CS2.[3][page needed] It is sometimes called polymeric sulfur, μ-S or ω-S.[2][page needed]

Fibrous (φ-) sulfur[edit]

This is a mixture of the allotropic ψ- form and γ-cycloS8.[3][page needed]

ω-Sulfur[edit]

This is a commercially available product prepared from amorphous sulfur that has NOT been stretched prior to extraction of soluble forms with CS2. It sometimes called "white sulfur of Das" or supersublimated sulfur. It is a mixture of ψ-sulfur and lamina sulfur. The composition depends on the exact method of production and the samples history. One well known commercial form is "Crystex". ω-sulfur is used in the vulcanization of rubber.[3][page needed]

λ-Sulfur[edit]

This name is given to the molten sulfur immediately after melting, cooling this gives predominantly β-sulfur.[3][page needed]

μ-Sulfur[edit]

This name is applied to solid insoluble sulfur and the melt prior to quenching.[3][page needed]

π-Sulfur[edit]

Dark-coloured liquid formed when λ-sulfur is left to stay molten. Contains mixture of Sn rings.[12]

Biradical catena (S) chains[edit]

This term is applied to biradical catena- chains in sulfur melts or the chains in the solid.[1]

List of allotropes and forms[edit]

Allotropes are in Bold.

Formula/name Common name Other names[2][page needed] Notes
S2 disulfur A diatomic gas with a triplet ground state like dioxygen.[1]
S3 trisulfur A cherry red triatomic gas with a bent ozone-like structure.[1]
S4 tetrasulfur Structure not determined but calculations indicate it to be cyclo-S4.[13][non-primary source needed]
cyclo-S5 cyclo-pentasulfur Not yet isolated, only detected in sulfur vapour.[3][page needed]
cyclo-S6 ρ-sulfur cyclo-hexasulfur, "ε-sulfur", "Engel's" sulfur, "Aten's sulfur" The ring adopts a chair form in the solid.[1]
cyclo-S6/cyclo-S10 adduct A mixed crystal with alternating layers of cyclo-S6 and cyclo-S10.[3][page needed]
cyclo-S7 α-, β-, γ-, δ- cycloheptasulfur Four forms known, two(γ-, δ- ) characterized.[3][page needed]
cyclo-S8 α-sulfur "orthorhombic sulfur" "rhombic sulfur", "flowers of sulfur", "roll sulfur" "milk of sulfur", "Muthmann's sulfur I" Yellow solid consisting of S8 puckered rings. The thermodynamically stable form at ordinary temperatures.[1]
cyclo-S8 β-sulfur "monoclinic sulfur" "prismatic sulfur" "Muthmann's sulfur II" Yellow crystalline solid, consisting of S8 puckered rings. Only stable above 95.6 °C, it reverts to α-sulfur at room temperature.[1]
cyclo-S8 γ-sulfur "nacreous sulfur" "mother of pearl sulfur" "Gernez’s sulfur" or "Muthmann's sulfur III". Light yellow solid, crystal monoclinic, consisting of S8 puckered rings.[1] Found in nature as the rare mineral rosickyite.[3][page needed]
cyclo-Sn
n = 9-15, 18, 20
cyclo-(nona; deca; undeca; dodeca; trideca; tetradeca; pentadeca; octadeca; eicosa)sulfur Pure forms all allotropes, cyclo-S9 has four forms, cyclo-S18 has two forms. Generally synthesised rather than obtained by treatment of another form of elemental sulfur.[1]
catena-Sx fibrous (ψ) sulfur Well characterized, contains parallel helical sulfur chains and is difficult to obtain pure.[1]
catena-Sx lamina sulfur Not well characterized, contains helical chains partially crossed.[3][page needed]
amorphous sulfur Quenched molten sulfur plastic sulfur at first crystallises to amorphous or glassy sulfur. Consists of a mixture of catena sulfur and cyclo sulfur.[3][page needed]
insoluble sulfur Quenched liquid sulfur with soluble species extracted with CS2. Sometimes called polymeric sulfur, μ-S or ω-S.
φ-sulfur A mixture of allotropic ψ-sulfur and cyclo forms mainly γ-cyclo-S8.[3][page needed]
ω-sulfur insoluble sulfur A mixture of chains with a minimum of soluble species.[3][page needed]
λ-sulfur Light yellow mobile liquid formed when β-sulfur first melts at 119.6 °C. Consists of S8 rings.[12]
μ-sulfur The dark-coloured viscous liquid formed when π-sulfur is heated and the solid when cooled. Contains a mixture of polymeric chains.[12]
π-sulfur Dark-coloured liquid that develops as λ-sulfur is left molten. Contains mixture of Sn rings.[12]
High-pressure forms of α-sulfur S-II, S-III, S-IV, S-V and others Four high-pressure phases (at ambient temperature) including two that are metallic and become superconducting at low temperature[8][9] and some additional phases photo-induced below 20–30 GPa.

High temperature gaseous allotropes[edit]

Disulfur, S2[edit]

Main article: Disulfur

Disulfur, S2, is the predominant species in sulfur vapour above 720 °C (a temperature above that shown in the phase diagram); at low pressure (1 mmHg) at 530 °C, it comprises 99% of the vapor.[citation needed] It is a triplet diradical (like dioxygen and sulfur monoxide), with an S-S bond length of 188.7 pm.[citation needed] The blue colour of burning sulfur is due to the emission of light by the S2 molecule produced in the flame.[1]

The S2 molecule has been trapped in the compound [S2I4][EF6]2 (E = As, Sb) for crystallographic measurements, produced by reacting elemental sulfur with excess iodine in liquid sulfur dioxide.[citation needed] The [S2I4]2+ cation has an "open-book" structure, in which each [I2]+ ion donates the unpaired electron in the π* molecular orbital to an vacant orbital of the S2 molecule.[citation needed]

Trisulfur, S3[edit]

Main article: Trisulfur

S3 is found in sulfur vapour, comprising 10% of vapour species at 440 °C and 10 mmHg.[1] It is cherry red in colour, with a bent structure, similar to ozone, O3.[1]

Tetrasulfur, S4[edit]

This has been detected in the vapour phase but has not been fully characterized; various forms, (e.g. chains, branched chains and rings) have been proposed.[citation needed] A primary research result based on theoretical calculations suggests that it has a ring structure.[13][non-primary source needed]

References[edit]

  1. ^ a b c d e f g h i j k l m n o p q r s t u v w x y z aa ab ac ad ae af ag ah ai aj ak al am an ao ap aq ar as at Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. pp. 645–662. ISBN 0080379419. 
  2. ^ a b c d e f g h i Eilene Theilig, 1982, "A primer on sulfur for the planetary geologist," NASA Contractor Report 3594, Grant NAGW-132, Office of Space Science and Applications, Washington, DC, USA:National Aeronautics and Space Administration, Scientific and Technical Information Branch, 34 pp. plus front and back materials, see [1], accessed 8 July 2015.[page needed]
  3. ^ a b c d e f g h i j k l m n o p q r s t u v w x y z aa ab ac ad ae af ag ah ai R. Steudel, ed. (2004). Elemental sulfur and sulfur-rich compounds I (Topics in current chemistry). Springer. ISBN 3-540-40191-1. [page needed]
  4. ^ Tebbe, F. N.; Wasserman, E.; Peet, W. G.; Vatvars, A.; Hayman, A. C., "Composition of Elemental Sulfur in Solution: Equilibrium of S6, S7, and S8 at Ambient Temperatures", J. Am. Chem. Soc. 1982, vol. 104, pp. 4971. doi:10.1021/ja00382a050
  5. ^ David A. Young, 1975, "Phase Diagrams of the Elements," pp. 14-16, Lawrence Livermore National Laboratory Report UCRL-51902, Contract No. W-7405-Eng-48, U.S. Energy Research & Development Administration, Springfield, VA, USA: U.S. Department of Commerce, National Technical Information Service, 64 pp. plus front materials, see [2], accessed 8 July 2015.
  6. ^ G. C. Vezzoli & R. J. Zeto, 1970, "The ring -> chain high-pressure polymorphic transformation in sulfur and the accompanying change from insulating to modest semiconducting behavior," Inorg. Chem. 9(11), 2478-2484, see [3], accessed 8 July 2015.
  7. ^ Viktor V. Struzhkin, Russell J. Hemley, Ho-kwang Mao & Yuri A. Timofeev, "Superconductivity at 10–17 K in compressed sulphur," Nature 390:382-384 (27 November 1997), DOI 10.1038/37074, see [4], accessed 8 July 2015.[non-primary source needed]
  8. ^ a b c Degtyareva O, Gregoryanz E, Somayazulu M, Ho-Kwang Mao, Hemley R J (2005). "Crystal structure of superconducting phases of S and Se". Phys. Rev. B 71 (21): 214104. arXiv:cond-mat/0501079. Bibcode:2005PhRvB..71u4104D. doi:10.1103/PhysRevB.71.214104. 
  9. ^ a b Gregoryanz E.,Struzhkin V, Hemley, R J, Eremets, M I, Mao Ho-Kwang; Timofeev Y A. (2002). "Superconductivity in the chalcogens up to multimegabar pressures". Physical Review B 65 (6): 064504. arXiv:cond-mat/0108267. Bibcode:2002PhRvB..65f4504G. doi:10.1103/PhysRevB.65.064504. 
  10. ^ Alan Shaver, James M. Mccall, Gabriela Marmolejo, "Cyclometallapolysulfanes (and Selanes) of Bis(η5-Cyclopentadienyl) Titanium(IV), Zirconium(IV), Molybdenum(IV), and Tungsten(IV)" Inorganic Syntheses 1990, Vol. 27, pp. 59–65. doi:10.1002/9780470132586.ch11
  11. ^ Catherine E. Housecroft; Alan G. Sharpe (2008). "Chapter 16: The group 16 elements". Inorganic Chemistry, 3rd Edition. Pearson. p. 498. ISBN 978-0-13-175553-6. 
  12. ^ a b c d e f g Egon Wiberg, Arnold Frederick Holleman (2001). Inorganic Chemistry. Elsevier. ISBN 0-12-352651-5. 
  13. ^ a b Ming Wah Wong, Ralf Steudel (2003). "Structure and spectra of tetrasulfur S4 – an ab initio MO study". Chemical Physics Letters 379 (1–2): 162–169. Bibcode:2003CPL...379..162W. doi:10.1016/j.cplett.2003.08.026. [non-primary source needed]