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Elemental Sulfur


Chemistry Department, University of Washington, Seattle, Washington 98 195, and lnorganic Materials Research Division, Lawrence Berkeley
Laboratory, University of California Berkeley, California 94 720

Received March 4, 1975 (Revised Manuscript Received April 22, 1975)

Contents mining to chemical production, recent interest in environ-

I. Introduction 367
mental quality attracted many to study sulfur chemistry and
A. General Background 367
the recovery of sulfur from sulfur dioxide in combustion
B. Nomenclature 369 gases. However, despite 10 years of intensive efforts, the
II. The Sulfur Bond 369
best known processes are still inefficient and uneconomical
A. Electronic Structure 369
applications of limestone. The basic chemistry of the dry
B. Bond Geometry 369
limestone process was patented by Clegg4 in 1815 with the
C. Molecular Variety 370 goal of reducing boiler corrosion. The chemistry of the wet
D. Bond Energy and Spectra 372
limestone process, used to recover SO2 from producers and
111. Solid Sulfur 373
water gas, was described in a patent by Philips4 in 1814. Ob-
A. General 373 viously, much opportunity exists to apply progress in sulfur
B. Allotropes of Cyclic Molecules 373
chemistry to develop new production methods, and much SUI-
C. Allotropes of Polymeric Sulfur 378 fur research remains to be undertaken to improve chemical
D. High-pressure Allotropes 378 production and use of this element, of which 40 million tons
E. Low-Temperature Solids 379 was consumed last year, and a comparable amount was re-
IV. Liquid Sulfur 379 leased into the atmosphere.
A. The Melt below 150 O C 379 This review is primarily concerned with progress during
B. Polymerization at Tx = 159.4 O C 380 the last 10 years. The most reliable and extensive summary
C. Liquid Sulfur above 250 O C 38 1 of old research can be found in Gmelin. Since then, several
V. Sulfur Vapor 382 summaries of specialized areas have appeared. The proper-
A. General 382 ties of solid allotropes have been reviewed in this journal.6
B. Individual Species 383 Donohue7 has described the discovery of the structure of the
VI. Solutions 384 solid allotropes: Schmidt8 reviewed general properties of SUI-
VII. Conclusion 386 fur, as well as the eight new metastable allotropes which his
V111. References 386 group synthesized, and the late Tobolskyio summarized his
contribution to the present understanding of the polymer.
1. Introduction Harris discussed the composition of the melt, BerkowitziZ
~ of so-
that of the vapor, and ScottI3 and W i e w i o r ~ w s k ithat
A. General Background
lutions. Many chemical and physical proper tie^'^ of solid, liq-
During the last 10 years 12 new elemental sulfur rings uid, and gaseous sulfur have been reviewed. The properties
have been synthesized, the structure of the third solid cy- and reactions of sulfur compounds are treated in volumes
clooctasulfur allotrope has been determined, and much has edited by Nickless, Senning, Tobolsky,8 and Kar-
been learned about the molecular composition of solid, liq- chmer. l Further reviews have been published by Schmidt,z0
uid, and gaseous sulfur. Many bulk properties are more accu- and others.2 The structure of polysulfides has been dis-
rately known, and the color of liquid and gaseous sulfur can cussed by Rahman, and organic reactions of elemental SUI-
now be explained. The purpose of the present review is to fur are included in the classical series by Reid23 and Khar-
discuss these recent discoveries, and to present an up-to- a s ~ h The. ~ reaction
~ mechanisms have been discussed by
date picture of our present knowledge of elemental sulfur. Pry~r.~
Elemental sulfur has been known and used for several Since the last review, high-purity elemental sulfur has be-
thousand years. Until 1880, the most important source of in- come commercially available and is now almost universally
dustrial sulfur was the volcanic soil of Sicily. Since 1891, the used. Research on ultrapure sulfur has been quite success-
patents of Fraschl permitted mining of ever-increasing vol- fu1,26 and analytical methods2 for impurities in sulfur, and
umes of very pure elemental sulfur from salt domes in North traces of sulfur, are established. Furthermore, highly en-
America. In 1971 almost 10 million tons of Frasch sulfur was riched sulfur isotopes have become available. 34S is now
produced in the U.S. In contrast, and despite the excellent being separated both by thermodiffusion in liquid CS2, and by
process of Claus,2 1882, chemical recovery of sulfur from exchange between SO2 and HS03-. It has been estimatedz8
smelting and refining operations remained comparatively in- that 90% enriched 34S will be available for about $lOO/g,
significant, until the recent demand for energy forced the re- i.e., about a 1000 times cheaper than up to now.
covery of by-product sulfur from natural gas. In 1971, for the Most chemists are now aware of the unusual molecular
first time, chemical production of Claus sulfur exceeded min- complexity of elemental sulfur, and the fact that the physical
ing of Frasch ~ u l f u rParallel
.~ to this historic transition from and chemical properties of solid sulfur are dependent on its
* Address correspondence to author at the University of Washington ad- temperature history. However, the nomenclature of sulfur
dress. species is still unsati~factory~~
and confusing.
368 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

TABLE I. Guide to Nomenclature

Molecular Designation used Section
Name Synonyms species in this review or ref

CY (alpha) Rhombic, Cycloocta-S Or thorh om bic-(Y 1II.B

Muthmanns I
Monoclinic i, Cycl oocta-S Monoclinic-fl 1II.B
Muthmanns I I,
Monoclinic II, Cycl oocta-S Monocl i nic-y 1II.B
Muthmanns I I I,
nacreus, mother-of-
pearl, Gernez
6 (delta) Monoclinic I l l , Cycloocta-S Allotropes of S, 6, 7
Muthmanns IV,
E (epsilon) Engel, Aten, rhombo- Cyclohexa-S Rhom bohedral 6, 7
hedral, monoclinic
5th monoclinic, Cycl oocta-S Allotrope of S , 6, 7
4th monoclinic, Cycl oocta-S Allotrope of S, 6, 7
Tetragonal, Korinth Cycloocta-S Allotrope of S, 6, 7
Erametsa Cycloocta-S Allotrope of S, 6
Erametsa Cycl oocta-S Allotrope of S , 6
Cycloocta-S Cycloocta-S, 6
( a ) Insoluble Catenapoly-S Solid or liquid 1II.C
(b) Polymeric Polymeric-S 1V.B
P Mixture Solid polymeric 1II.C
Triclinic, Korinth Cycloocta-S Allotrope of S , 6, 7
Erametsa Cycloocta-S Allotrope of S, 6, 7
(a) Aten, Erametsa Ring mixture Frozen liquid 1V.A
(b) Catenaocta-S 6
Aten, Engel Cyclohexa-S Cyclohexa-S 1II.B
Erametsa Cycloocta-S Allotrope of S,
Fibrous Mixture Fibrous III.C, D
Fibrous, plastic Polycatena-S Fibrous I I I.C, D
Plastic Mixture PoI y mer ic 1II.C
Fibrous Mixture Fibrous III.C, D
Insoluble, white, Das Mixture Polymeric I1I.C
supersubl imation
m Triclinic Cycloocta-S Allotrope of S , 6
n I.1 Solid 1II.C
Aten See E , p Cyclohexa-S Rhombohedral 1II.B
Braun See p Mixture Solid, Polymeric 6
Engel See E , p Cyclohexa-S Rhombohedral 1II.B
Korinth See 8, n, 8 , t Cycloocta-S 6
Muthmann See CY,P, Y,6 Cycloocta-S 6
Schmidt See orthorhombic-S,, Cyclododeca-S 111.8
Amorphous P Mixture Solid, polymeric 1II.C
Cubic High pressure cubic High pressure forms 111.0
Fibrous $, Q, phase I I Catenapoly-S Fibrous III.C, D
Insoluble Crystex, super- Mixture Insoluble 1II.C
Laminar Phase I, white, w , p,x Catenapoly-S L a mi nar III.C, D
MetaI 1 ic High pressure metallic ? High pressure 1II.D
Photosulfur Insoluble ? Photosulf ur VI
Black (a) Skjerven ? Quenched liquid 1II.E
(b) Rice, Schenk Mixture Trapped vapor
Brown Maltsev Mix tu re Trapped vapor 1II.E
Green Rice Mixture Trapped vapor 1II.E
Orange Erametsa 6
Purple Rice Mixture Trapped vapor 1II.E
Red (a) Rice Mixture Trapped vapor 1II.E
(b) Erametsa Mix tu re Trapped vapor 1II.E
Rice Mixture Trapped vapor 1II.E
Erametsas red Mixture Allotrope of S, 6
Orange 6
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 369

TABLE I I. Orbital Ionization Potential ( I " ) , Electron

Affinity (E,,), and Mulliken's Electronegativity
+::- e band

(x) of Atomic Sulfur8

Configuration Orbital I,, E" X

S ~ D. ~. D D P 12.4 2.4 7.4
(sp3)2 (5 p 3 ) 2 5 p3sp3 5P3 15.5 4.8 10.1
(sp2)2(sp2)*5p277 SP2 16.3 5.4 10.9
71 12.7 2.8 7.7
a Reference 32.
Figure 1. Electronic structure of Sa,and a-sulfur, derived from the
energy levels of the free atom^.^' Both the narrow electron band
This review starts with a short guide to names and syn- and the hole band contribute to the electric conductivity (after Gib-
onyms. In section 11, properties of the S-S bond are dis- bon~~~\.
cussed, and the present experimental knowledge of molecu-
lar variety is summarized. Sections 111, IV, and V deal with the
composition of the solid, liquid, and gas phase, while section
VI discusses phenomena in solutions of nonpolar and ionic
solvents. The latter includes a short discussion of positive
and negative elemental ions. The thermal and spectral data
and the sparse kinetic data will be integrated into the discus-
sion of individual allotropes.

6. Nomenclature
There are many reasons for the confusing multitude of
names and nomenclatures which are in use. Several allo- Figure 2. S-S-S-S bond structure. The unrestrained bond angle'46
tropes were discovered at a time when the molecular struc- is 106', and the torsion angle is 85.3'. Data for various allotropes
are listed in Table XI.
ture and the nature of chemical bonding were not yet under-
stood. As a matter of fact, the preparation and many proper- low-lying unoccupied 3d orbital^,^' and it is widely believed
ties of polymeric sulfur, a-, p-, and y-sulfur, were known be- that the 4s and 3d orbitals of sulfur participate in bonding in a
fore it was proven that sulfur is an element. Periodic attempts manner similar to the participation of 2s and 2p orbitals in
by various authors to systematize the nomenclature have carbon.
failed, as they often lead to further confusion. The third modi- A discussion of the wave-mechanical calculations of vari-
fication of Muthmann, for example, is the second monoclinic ous configurations and the ionization states of the sulfur atom
modification of Korinth, and is also widely called y-sulfur. is given by Cr~ickshank.~' The ionization potentials, electron
There are so many types of sulfur allotropes that a system- affinities, and Mulliken's electronegativity for various orbitals
atic nomenclature yields long and complicated names. Thus, of atomic sulfur are given in Table II. Considerations regard-
the choice is between clumsy or ambiguous names, and trivi- ing the atomic wave functions,33 radial functions from self-
al names will likely remain in use. Table I indicates the consistent field calculations, and orbital energies (the d-orbit-
names chosen for this review and lists some of the most al energies are only about 10% of the p-orbital energies32)
common synonyms encountered in the references. In case of do not justify the belief in strong d-orbital p a r t i ~ i p a t i o nin~ ~
doubt, the least ambiguous of the most widely accepted S-S bonds. An ab initio calculation of S8 arrives at the same
name is used. conclusion.35Recent calculations by Miller and C u ~ a c h on s~~
Greek letters will be used as sparingly as possible. How- cyclo-S8, cyCbs6, cyclo-S4, and catena-S6 ions confirmed
ever, a , @, and y remain the best accepted designations for that the contribution of d orbitals to the ground-state energies
the three fully identified solid allotropes of cyclooctasulfur. In of divalent sulfur compounds37 is negligible, but they ob-
contrast, p and E for identifying cyclohexasulfur are unneces- served that in computations of energy levels of excited states
sary, as only one allotrope exists. The letters x and prefer to the inclusion of d orbitals yields different energies, and that
a different class of compounds. These letters are used as values calculated with d orbitals fit the observed spectra bet-
comprehensive terms for identifying well-known, but poorly ter than those without d orbitals. The same observation was
characterized mixtures: ir refers to all components, other
made by Spitzer and M e ~ e for r ~ an
~ entire series of sulfur
than cyclooctasulfur, in the sulfur melt; cpsulfur is a fibrous rings and chains, and ions. The importance of d orbitals in-
solid allotrope, obtained by quenching liquid polymeric sulfur. creases drastically in the presence of a ligand field, as was
shown by Craig and Zauli3' for SF6. A bond model for S8 in
11. The Sulfur Bond the gas phase and the solid deduced from atomic orbitals has
A. Electronic Structure been given by Gibbons40 and is shown in Figure 1. Clark4'
has described bonding in sulfur chains by a one-electron
The sulfur atom has the same number of valence electrons model and obtained energy levels compatible with those of
as oxygen. Thus, sulfur atoms S2 and S3 have physical and Palma.42 Muller and Heegn43 developed a three-dimensional
chemical properties analogous to those of oxygen and ozone. electron gas model which yields good relative bond energies
Sp has a ground state of 38,-. Its excited electronic energy for sulfur rings of various sizes. The charge distribution in
levelsz9 correspond to those of Oz. S3 has a well-known uv some 100 elemental sulfur molecules and ions has been cal-
spectrum, and probably has a bent structure, analogous to its culated with a Huckel model by Meyer, Peter, and S p i t ~ e r . ~ '
isovalent molecules30 03, SO2, and S20. Accordingly, S3,
thiozone, most likely has ground state '8.However, S8 and
6. Bond Geometry
not Sp is the stable STP form of sulfur. Thus, the chemistry of
the two elements differs because sulfur has a pronounced The observed geometry of the divalent S-S-S bond is
tendency for catenation. The most frequently quoted explana- shown in Figure 2. The sulfur helix of S, yields probably the
tion is based on the electron structure of the atom. Sulfur has best values for an undisturbed bond geometry. This "free"
370 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

TABLE Ill. Representative S-S Bond Distances

S-S bond
Molecule l e n g t h . .4 Re

52 1.887 29
S2F2 1.89 a
s20,2- 2.00 b
Diphenyl disulfide 2.03 C
&-Cystine 2.03 d
Me252 2.038 e
s, (C FA2 2.065 f
S,(Me)2 2.04 g
2.04-2.20 106b
s5 87 -02
2.04 105
&-Cystine 2.05 h
t hydrochloride
si * 2.053 137
H2S2 2.055 1
56 2.057 7
LJ- -LJ s*
2.066 145

Figure 3. Structure of the sulfur helix. The molecular unit contains sn0,2- n =3 2.15 j
three atoms in three turns. The helix radius is 0.95 21, the molecular n = 4 2.02 k
unit axis, c = 13.8 A. In the solid, left- and right-handed helices
combine in various ways to form the different structures of polymer- n=5 2.04; 2.12 1
ic sulfur. Figure 2 (top) is a view along the c axis. n=6 2.04; 2.10 m
s20,2- 2.15 n
bond is characterized by a torsion angle of 85.3', a bond s20,2- 2.209 0

angle of 106', and a bond distance of 2.066 A. In Figure 2, s,o,z- 2.389 P

sp3 hybrid orbitals40 are indicated at the terminal atoms, to S4N4 2.58 4
suggest the direction of further bonds. B e r g ~ o and n ~ ~others 0 R. L. K u c z k o w s k i , J . Am. C h e m . S O C . , 8 6 , 3 6 1 7 ( 1 9 6 4 ) . b L.
have proposed that the S-S dihedral angle is determined by Csordas, A c t a C h i m . ( B u d a p e s t ) , 6 2 , 3 7 1 ( 1 9 6 9 ) . CJ. D. L e e a n d
M . W. R. B r y a n t , A c t a Crystallogr., S e c t . B , 2 5 , 2 0 9 4 ( 1 9 6 9 ) .
repulsion between lone electron pairs on adjacent atoms. dB. M. O u g h t o n a n d P. M. H a r r i s o n , A c t a Crystallogr., 1 2 , 3 9 6
The significance of different bond distances has been dis- (1959). e D . Sutter, Dreizler, a n d H. D. R u d o l p h , Z . N a t u r f o r s c h .
A , 20, 1 6 7 6 (1965).?H. J. M. B o w e n , Trans. Faraday S O C . ,5 0 , 1
cussed by F o s s . A ~ ~list of S-S bond distances is given in ( 1 9 5 4 ) . gJ. D o n o h u e a n d V. S c h o m a k e r , J . C h e m . Phys., 1 6 , 9 2
Table Ill. The short S-S bondz9 in Sz is probably due to x ( 1 9 4 8 ) . L. K. S t e i n r a u f , J . Peterson, a n d L. H. Jensen, J . A m .
C h e m . S o c . , 8 0 , 3 8 3 5 ( 1 9 5 8 ) . ' c 4 . Winnewisser a n d J. Haase, Z .
bonding. Partial x bonding accounts for all bonds shorter than :Vaturforsch. A . 23, 5 6 ( 1 9 6 8 ) . I W . H. Zachariasen, Z . Kristallogr.,
2.06 A. P a ~ l i n g assumed
~~ a single bond value of 2.08 A, 8 9 , 5 2 9 ( 1 9 3 4 ) . k O . Foss, S. F u r b e r g , a n d H. Zacharisen, A c t a
C h e m . S c a n d . , 8 , 4 5 9 ( 1 9 5 4 ) . IO.Foss a n d 0. T j o m s l a n d , i b i d . ,
using the s8 ring as the basis for determining free bonds. His 10, 2 8 8 ( 1 9 5 6 ) . m O . Foss a n d K. J o h n s o n , ibid., 1 9 , 2 2 0 7 ( 1 9 6 5 ) .
choice proved to be restrictive, as will be discussed below. E. S t a n l e y , A c t a Crystallogr., 9 , 8 9 7 ( 1 9 5 6 ) . I. L i n d q v i s t a n d
M. M o r t s e l l , i b i d . , 1 0 , 4 0 6 ( 1 9 5 7 ) . P J . D. D u n i t z , i b i d . , 9 , 5 7 9
The unstrained bond d i s t a n ~ e is ~ . ~ ~ about 2.06 A.
~ probably ( 1 9 5 6 ) . 9 6 . D. Sharma a n d J . D o n o h u e , i b i d . , 1 6 , 8 9 1 ( 1 9 6 3 ) .
L i n d q ~ i s correlated
t~~ the S-S bond distance to the ratio of
s/p hybridization. Torsion around the bond is restricted. Sem- TABLE I V . Conformations of Catena Sulfur Compounds
lyen4' estimated an activation energy of A = 6 kcal/mol for
the transition from cis (+-) to trans (+-I-) conformations. Conformation0 Compound

Figure 3 shows the left- and right-handed helices of fibrous ++ Di-2-iodoethyl trisulfide
sulfur, which result from continued +- configurations. A Dibenzenesulfonyl trisulfide
view along the c axis shows the staggering of atoms. Table Di-p-to I u enesu If on y I t r isu If ide
IV indicates the conformations observed for some other sul- Dimethanesulfonyl trisulfide
fur compounds. Some species can exist in two different con- Ammonium telluropentathionate
formations, depending on the nature of the terminal group or +- Cyanogen trisulfide
the cation with which the sulfur chain shares the solid phase. Triclinic barium pentathionate dihydrate
The observed bond data are listed in Table VI. Barium pentathionate hydrate acetonate
Orthorhombic barium pentathionate
C. Molecular Variety dihydrate
+++ Cesium hexasulf ide
There has been much controversy whether sulfur mole- trans-Dichlorodienylcobalt ( I I I ) hexa-
cules in the various phases exist as rings, chains, or both. thionate monohydrate
Rings can only form if the chain ends can come within bond- +-+ Potassium barium hexathionate
ing distance.49 The necessary configurations are known to
@ T h eslgn c o r r e s p o n d s t o t h e sign o f t h e i n t e r n a l r o t a t i o n a l angle:
exist4' for molecules with six or more atoms. In S4 and S5 + + and --corresponds t o trans: + - t o cis. See ref 2 2 a n d 49.
considerable distortion of the normal divalent sulfur bond
must occur before a ring can be formed. Table V lists some molecules, S, 6 < n < 12, including S7, Sg, and Sl0, which
chain configurations, and the distance between terminal suffer from unfavorable distances and contain inequivalent
atoms for some short chains. The values are based on a atoms, exist as rings in all phases.
model by Seml~en,~' and are based on P a ~ l i n g ' bond
s ~ ~ as- Obviously, the larger the chain, the greater is the probabili-
sumptions of a bond angle supplement of 74', an internal ro- ty that some of the configurations allow strain-free ring clo-
tational angle of 90, and a bond distance of 2.06 A. The sure. However, neither thermodynamic nor kinetic stability of
values are good enough for a qualitative comparison. Experi- the rings increases with size. Experiments show that Sa, SI*,
mental ionization patterns5' and thermodynamic consider- and Sg are the most stable molecules, in that order,5zproba-
~ ' well as theoretical calculation^^^ indicate that all
a t i o n ~ as bly because of symmetry considerations and because of non-
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 371

TABLE V . Chain Conformations Favoring Ring Formationa

N o . of between
atoms terminal
in atoms,
chain A Chain c o n f o r m a t i o n s

5 3.59 +-+
6 2.06 +-+-
7 1.01 +-+-+
3.68 ++-+-
8 1.56 +-+---
2.94 ++-+-+
9 2.43 +i-+-+-

3.26 +-+-+-+
3.71 +++-+-+
10 1.07 ++-i-+--

3.24 +-+-+--+
3.42 +-+--++-

0 2.060a

2.54 +++-i-+--
2.59 ++--+-++-
2.63 ++--++---+
12 0.20 +-I-----++-+-
0.53 -++-+--++-+ Figure 4. The structures of S8 and SI*,
0.66 +I---+-++--
0.91 ++--++--+i
1.57 +--f----+-+
20 + + t--+ +t
+ i---+ i + t

a See ref 49.

neighbor interactiod3 and atoms across the ring. The struc-

a b
ture of s8 and S12is shown in Figure 4. Experimental bond
data of these molecules are well established, and listed in
Table XI. se has a chair structure, as is seen in Figure 5. The
crown-shaped s 8 is the thermodynamic stable form of sulfur
at STP, and was used by Pauling and his predecessors as the
basis for determining "free" S-S-S dimensions. This proce-
dure constituted the best possible approach at that time and
was very successful, even though bonding in s8 differs from
that in other rings, as the crown structure allows for consid- S 18 s20
erable cross-ring i n t e r a ~ t i o nbetween
~~ nonbonded atoms. C d
The existence of the amazingly stable S12 ring54 confirms
that Pauling's assumptions about the S-S bond were correct, Figure 5. Views of (a) Ss, (b) S, (c) S18, and (d) S 2 0 . Molecular data
are summarized in Table XI, the structures of the solids in Table XIII.
even though his unnecessarily restrictive assumptions about
S-S-S bond conformations led him to forbid its existence. All known rings exhibit yellow hues.58The spectra, as far as
Large rings are unstable because they lack higher order known, all show an absorption band in the 250-300-nm re-
bond contributions, are awkward, and have unshielded atoms. gion. The transition energies38are shown in Figure 6. The uv
Furthermore, the S-S bonds have low-lying triplet states38b absorption of the corresponding yellow H-S,-H chains is
which make them p h o t o ~ e n s i t i v e ,and
~ ~ the resulting chains well e ~ t a b l i s h e d It
. ~lies
~ in the 280-nm region. With increas-

undergo quick d e g r a d a t i ~ n : ~ . ~ ~ ing chain length, the absorption shifts to the red and conver-
ges toward 330 nm. It fits the sequence of electronic transi-
-s,- s8 f -sx-8-
tion energies calculated60with a one-electron model, as well
The synthesis of large rings is interrupted by formation of as those obtained with an extended Huckel c a l ~ u l a t i o nThe.~~
s8 rings, whenever the chains are long enough. However, elemental free-radical chains absorb in the visible. The ob-
Schmidtg showed that large rings can be made, that they served absorption of short chain members and the calculated
occur in the melt54 and that such rings, once they are transitions are also shown in Figure 6.
formed, are far more stable than had been anticipated. The calculation^^^^^^ predict that with increasing chain
Rings and chains having a given number of atoms have length the transition energy converges toward 850 nm, i.e.,
very different electron structure. Sulfur chains, except S3, the near-infrared. The convergence of transition energies is
are expected to be d i r a d i ~ a l s , ~ 'while
, ~ ~ rings have fully an intrinsic property of all homologue series. It has been
paired electrons. Thus, rings correspond to chains with termi- thoroughly discussed for the alkane series.61 In the case of
nal groups, such as, for example, sulfanes H-S,-H. The dif- free-radical chains of sulfur, it indicates that interaction be-
ference between the ring and chain shows in chemical reac- tween terminal atoms, via the chain, becomes negligible. The
tivity, as well as in physical properties, for example, color. shift of proton NMR spectra of the sulfanes6* H-S,-H, of the
372 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

T A B L E V I . Summary of Observed Sulfur Species


Atoms Ionb
S per
molecule Ringa Chaina +2 -1 -2

200 400 800 10
6oo nm
Figure 6. First allowed transition for (a) sulfur chains, (b) sulfur rings, 12
and (c) sulfanes as a function of chain length: (0)observed points,
(X) calculated value. 18 r

CIS non sym

P aparentheses i n d i c a t e t h a t t h e s t r u c t u r e is u n c e r t a i n : s, I, and g
i n d i c a t e s o l i d , l i q u i d , a n d gas phase. b All i o n s o c c u r i n s o l u t i o n : C
indicates chain, r indicates rings.

question whether sulfur forms branched molecules has been

raised periodically, but has always been rejected, largely by
analogy with experimental evidence regarding larger mole-
cules. However, the idea of a branched S4 structure is not as
far fetched as it might seem for longer chains, because S4 is
isovalent with SO3. The calculated electronic charge, indicat-
ed on the terminal atoms in all molecules in Figure 7, ap-
pears also reasonable. It should be noted that the S42+ ion,
observed by G i l l e ~ p i e has
, ~ ~quite a different electron config-
branched tetrahedron uration from that of S4. It probably has a planar ring struc-
D3h Td t ~ r eanalogous
, ~ ~ to that observed for Se42+.
S5 occurs in the gas phase, and in the liquid. Table V
shows that a nonsymmetric ring would be highly stressed. A
planar ring would require a quite unnatural bond angle of 75.
Thermodynamic reasoning seems to favor Ss as a ring5* in
the solid, as a diradical chain in the liquid, and as a ring in
the vapor. Maybe a structural elucidation of S4N-, which is
Figure 7. Six isomers of S4. The numbers on the terminal atoms in- isoelectronic with S5, will bring further information.
dicate the electronic charge. Table VI lists all species which have been observed. If one
considers the polymeric chains, with an average number of
corresponding Raman spectra,59and the calculation^^^^^^ for
atoms of up to lo6, several million different sulfur molecules
these compounds, and elemental sulfur chains indicate that exist. According to their properties they can be assigned to
approximately eight atoms are sufficient to interrupt intra-
one of four groups. All observed rings containing up to 20
chain communication between terminal groups. Thus, termi- atoms can now be isolated as pure solids. Small molecules
nal groups in long chains act as independent functions, and
occur as part of the vapor. Large, polymeric molecules occur
intermediate chain members behave increasingly like mem- both in the solid and liquid phase, while ions are formed only
bers of a large ring. Sulfur chains,63absorbing in the visible,
in ionic solution. Each group will be discussed in connection
are deeply colored, and according to these considerations, with the phase in which it normally exists.
-S-- must be black. However, polymeric sulfur is yellow and
absorbs in the uv, as is seen in Figure 14b. The puzzling
color of polymeric sulfur,58and its significance for the eluci-
D. Bond Energy and Spectra
dation of the structure, will be discussed later. The thermochemical bond strength and the bond dissocia-
Another interesting, unsolved structural problem regards tion energy have been measured for many sulfur com-
the structure of S4 and S5. As mentimed, normal bond geom- p o u n d ~ . ~However,
~ . ~ ~ * until
~ ~ recently, little was known
etry prevents formation of an unstrained S4 ring. However, about the data for various allotropes.
for this molecule, several other structures are feasible. Fig- The average bond of the S-S bond is about 63
ure 7 shows six possible isomers of S4. Extended Huckel cal- kcal/mol. The dissociation energy8i69.70is about 33 kcal/
c u l a t i o n ~ ,based
~~ on spectroscopic atomic parameter^,^' mol. It depends on the position of the S-S bond in the mole-
suggest that the ++ conformation and the branched D3,, cules chain. The bond energies of the gaseous sulfur mole-
form have comparable stability. All others, including the pla- cules, believed to be rings, were calculated by Berkowitzi2
nar ring, are calculated to be significantly less stable. It will from experimental data. Muller43 used a three-dimensional
be shown later that experimental evidence is insufficient to free electron model to compute bond energies in the corre-
determine the structure of S4, even though thermodynamic5 sponding rings and chains. Such calculations do not yet yield
and p h o t o i o n i ~ a t i o nevidence
~~ seems to favor the ring. The reliable absolute values, but their trends are quite reliable
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 373

TABLE V I I . v , of Ten Sulfur Allotropes ized. Other well-established solid allotropes containing cyclo-
hexa-S, cyclododeca-S, and other sulfur rings have been pre-
Species v , , crn-' T, K Ref
pared by reaction of sulfur compounds. Another class of allo-
5 2 718 (9) 880 206 tropes, made by decomposition of sulfur compounds in aque-
3 590 (m) 650 199 ous solution or by quenching hot liquid or gaseous sulfur,
5.4 668 (m) 20 199,200 comprises insoluble and other types of sulfurs. All contain
S,Z+ 584 300 64, 65 long helices of polymeric sulfur, which is easily prepared,
sx 559 (9) 880 206 much used commercially, and has well-known bulk proper-
'6 471 (s) 300 91 ties. However, its structure is still incompletely character-
s, 481 (s) 300 103 ized, as it contains helices mixed with other molecular
s, 475 (s) 30 111, 114 species. The best identified form of polymeric sulfur is fi-
S I2 459 (s) 200 140 brous sulfur, which is identical with one of the many high-
SCO 456 (I) 400 109 pressure allotropes which have been reported.
(5) 3 00 192

TABLE V I I I . Thermal Data for Phase Transitions

AH, AS, c a l /
Transition Process or r e a c t i o n T, K kcal/g-atorna deg,g-atom Ref

P a-S,(s) P-S,(S)
368.46 i 0.1 0.096 0.261 119, 128
Sublimation 01 a-S,(s) cyclo-S,(g)
+ 368.5 2.979 8.191
P P-S,(S) -* cYClo-S,(g) 368.5 2.883 7.93 172

-- -
E E-S,(S) -cyclo-S,(g)
300 4.02 8.38 6
Fusion (Y cU-S,(s) cycio-S,(I) + ? b 383C 0.507 52, 119, 122, 172
P P-S,(S) cyclo-S,(I) + ? b 392.9c 0.3842 0.75 173, 174
h, cyclo-S,(I) catena-S,(I) 43 2 4.1 2.88 71, 193
Polymerization catena-S,(I) + cyclo-S,(I) 442.8 0.396d 0.58 10
--* catena-S,(I)

Vaporization Si(l1 * Si(S) 717.824e 2.5 3.5 6

= 444.674 " C

a 1 9 - a t o m o f Sulfur = 32.066 9. b T h e c o m p o s i t i o n o f t h e m e l t i s n o t known. CSee also T a b l e X I V . dSee r e f 10. e S u l f u r i s a secondary

t e m p e r a t u r e r e f e r e n c e p o i n t on t h e I n t e r n a t i o n a l P r a c t i c a l T e m p e r a t u r e Scale, r e f 201.

and indicate that, except for S3, rings are indeed more stable All these allotropes will be discussed in the following sec-
than the chains. tions which are organized according to the molecular species
The trend in bond energies and dissociation energies for of which the solid is composed. Thermal data74for the con-
polysulfides with different terminal groups has been re-
~ i e w e d . ~ The
' , ~ ~activation energies for various reactions of
the S-S bond are deduced from thermal e q ~ i l i b r i a . This
~ ' can
version of various forms are given in Table VIII. The transition
a ( s ) P(s) is well established by experiment. The heat of
sublimation of cycloocta-S allotropes and of cyclohexa-S has
be dangerous in the case of sulfur, as traces of impurities been calculated and seems reliable. The fusion and freezing
can totally alter processes56such as bond dissociation, by in- of sulfur are far more controversial and are separately re-
ducing ionic reactions which proceed far quicker and by a viewed in Table Vlll and discussed in the section on liquid
different mechanism than the homolytic scission. Another sulfur, as is ring scission and polymerization.
problem is caused by the p h o t o ~ e n s i t i v i t yof
~ ~the sulfur The specific heat of elemental sulfur has been recently re-
bond, which is not yet satisfactorily explained. Since reliable viewed by J e n ~ e nSome. ~ ~ selected values are listed in Table
methods for the preparation of pure sulfur allotropes have IX. Most are close to those observed by West,74 except for
become available, accurate thermochemical data can be ex- 0-sulfur, for which new data have recently become avail-
pected within the next few years. able.75
The strength of S-S bonding is reflected in the bond dis- The thermal conductivity of decreases from 11
tance, shown in Table Ill. The Raman and ir frequencies also Wlm-deg at 4.2 K to 0.29 Wlm-deg at 0 OC. At 100 OC it is
provide valuable information. Table VI1 lists the stretching 0.15 Wlm-deg. Sulfur ranks with mica and wood among the
frequency, v 1 , for nine elemental sulfur molecules for which best thermal insulators. Recent data have been reviewed by
an assignment seems reliable. Except for S4, for which the M~gilevskii.'~ Mechanical properties of solid allotropes have
assignment is not reliable, and for which a branched struc- been reviewed by Dale.78
ture is possible, the trend follows that expected for a homolo- Standard reference sources list different values for the
gue series. The high value of S7 is clearly due to the bond vapor pressure of sulfur. Some critically ~ e l e c t e d ' ~
strain, discussed above. These spectra will be discussed in are listed in Table X. The high-temperature and high-pressure
connection with the individual allotropes. Evaluation of x-ray data will be discussed in the section on sulfur vapor.
spectra in terms of S-S bonds has been performed by White-
head7* and N a r k ~ t s . ~ ~ B. Allotropes of Cyclic Molecules
Rings of the formula S, 6 n < <
24, are expected to
Ill. Solid Sulfur occur in equilibrium with chains in liquid sulfur near the melt-
ing point, as part of the fraction called *-sulfur. The smaller
A. General
rings have been found in a mass spectrometer in the vapor.'*
The stable STP form of sulfur is orthorhombic a-sulfur These pure solid allotropes are not very stable, as some con-
consisting of cycloocta-S molecules. At 95.3 OC a-sulfur tain very strained bonds.
converts into monoclinic 0-sulfur, which melts at 119.6 OC. During the last 10 years, Schmidtg and his group obtained
Other allotropes of cyclooctasulfur can be obtained from so- seven new metastable allotropes by coupling two compounds
lutions. Of these, only monoclinic y-sulfur is well character- with the correct combined number of sulfur atoms and the
374 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

TABLE I X . Specific Heat of Elemental TABLE X I . Structural Parameters of Sulfur Molecules

su If ur (cal/g-atom ) a
Sulfur species Bond Bond angle, angle,
Molecule length, A deg deg Ref
T, K @-s(s) ~-S(S)~ Liquid Vapor
52 1.889 29
10 0.103 0.163 5 6 2.057 102 74.5 7, 102
15 0.348 0.412
5 8 2.060 108.0 i 0.7 98.3 7
20 0.608 0.666
SI 2 2.053 106.5 r 1.4 86.1 137
25 0.868 0.906
51 8
2.059 106.3 84.4 141
40 1.465 1.490 2.047 106.5 83.0 142
50 1.795 1.808 2.066 106.0 85.3 146
60 2.089 2.101 Saz+ion 2.04 102 (93) 105
100 3.090 3.077 580 2.04; 2.20 106 106
150 3.990 4.072
200 4.650 4.81 7
298.15 5.430 5.551 5.659 The strain in cyclopenta-S becomes evident from the separa-
368.54 5.778 5.913 7.579c tion of 3.59 A between the terminal atoms47 in the curled
388.36 6.053 7.579 5.569 chain (Table V). Semiempirical calculation^^^ indicate that
400 7.712 the chain isomer would be thermodynamically most stable.
420 8.190 The photoionization energy50of S5 is 8.60 eV.
433 11.930
440 10.800
460 9.925 2. S6,Cyclohexasulfur
717.75 7.694 5.252 Cyclohexasulfur was first prepared by EngeIa6by the reac-
1000 5.137 tion of concentrated hydrochloric acid with a saturated solu-
a Reference 74. b Reference 75. Reference 1 7 6 gives 7.423. tion of thiosulfate at 0 C . Atena7 identified the rhombohedral
crystals and proposed their presence in liquid sulfur. Kellasaa
TABLE X. Vapor Pressure of Elemental Sulfur believed that sg formed the liquid constituent responsible for
polymerization. However, most chemists ignored the exis-
p, T, a p, T,
tence of cyclohexa-S, until Frondel and WhitfieIda deter-
Torr C atm O C
mined the unit cell, Donnay7 established that the lattice is
10-5 39.0 1 444.61 rhombohedral, and D o n o h ~ 17b e ~proved
~ ~ ~ the structure. The
10- 58.8 2 495 molecule has the chair form, shown in Figure 5a. The bond
10-3 81.1 5 5 74 length and bond angle are comparable to those of Sa, but the
10-2 106.9 10 644 torsion angle is smaller than that of any other known allo-
lo- 141 20 721 trope, Table XI:
1 186 40 800
10 244.9 50 8 33 S-S bond length (4= 2.057 f 0.018 A
100 328 100 936
S-S-S bond angle = 102.2 f 1.6
760 444.61 200 1035
West a n d M e n ~ i e s . ~R o u n d e d average values; see B a k e r z o 2
S-S-S-S torsion angle = 74.5 f 2.5
and R a u . 9 6 2 0 3
The ir and Raman spectrum of Sg has been recorded by
appropriate, reactive terminal group. S12, for example,a0 is Berkowitz, Chupka, and Bromelsgl and N i m 0 t - 1 .The ~ ~ fre-
best prepared from reaction of a sulfanee with n sulfur quency and their assignment are listed in Table XII. Cyving3
- reported mean amplitudes at 0 and 300 K, and a normal
atoms, and a chlorosulfane with 12 n atoms:79
H2S, +
S(j2-n)C12 Si2 -
2HCI +
With this reaction, s6, SIO, SIP, Sle, and 5 2 0 can be pre-
coordinate analysis. The uv spectrum has been published by
Bartlettg4and 0 0 m m e n . ~ ~
s g occurs in the equilibrium liquid,95 and in equilibrium
vapor,12 where it is believed to occur as a ring. The thermo-
pared. The molecules S7, Sg,Sl0, and SI1are best prepared
dynamic propertiesg6 have been calculated with a semiem-
by pirical theory by Miller and C u ~ a c h sand
, ~ ~by S p i t ~ e r who
also calculated transition energies and charge distribution for
the catenahexa-S. s 6 reacts l o 4 times faster with nucleophil-
The titanium dicyclopentadienyl pentasulfide was synthe-
ic agents than sa. In sunlight sg decomposesg7forming sa,
sized by Kopf,82 using procedures analogous to those em-
and some SI2.
ployed by H ~ f f m a n n , who
~ in 1903 prepared (NH4)2PtS15r
The best method to prepare sg was discovered by Wil-
which is now known to contain three S5 chains forming six-
helm.79~99 Dilute solutions of dichlorodisulfane and tetrasul-
membered rings with the central platinum A similar
fane in ether are combined to form cyclohexa-S in 87%
compound of molybdenuma5contains four sulfur atoms in a
five-membered ring: (C5H5)2MoS4.
H2S4 sic12 sg 2HCI + + +
1. Sg,Cyclopentasulfur
The orange-red solid can be purified by recrystallization
Pure S5 has not yet been synthesized, but Schmidt52 pro- from toluene or CS2. The solubility00 has been measured in
posed the following synthesis of cyclopenta-S: CS2 and benzene. The rhombohedral crystals have a density
(C&i5)2M0S4 + SC12 + S5 +(C~H~)~MOCI~ of 2.209 g/cm3. This is the highest density of any sulfur form.
Obviously, the 18 molecules of s6 are very effsiently
Schmidt reports that this allotrope is liquid and polymerizes packed7 in the unit cell, which has the space group R3-C3?.
in daylight. It has been explained above that S5 is expected to The lattice constants are a = 10.818 A, c = 4.280 A, and
be very unstable, because of its unfavorable bond geometry. c/a = 0.3956.
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 375

TABLE X I I . Observed Infrared and Raman Frequencies of Four Sulfur Allotropes (cm-I)

sa (30 K)
S,2+ s.5 SI Designa s12
(planar) (8 fundamentals) (15 f u n d a m e n t a l s ) (1 1 f u n d a m e n t a l s ) tiona (20 f u n d a m e n t a l s )

A,, V, = 548 A,, V, = 471 v, = 262 v, = 481 v, = 236 v , = 475 v, = 218 a, R v , = 459
A,, v,=390 v, = 397 V, = 411 bl I
A, v, = 313 v, = 274 V, = 243 b, Ir
V? = 530 E, v, = 463 V , = 180 v, = 516 v, = 180 v, = 471 v, 191 e, lr
= v, = 465
E, v,=460 E, v , = 4 4 8 v 8 = 202 v8 = 145 v, = 475 v8 = 152 e, R v, = 425 v, = 266
B, V , = 330 v, = 86 v , = 62
v , , = 356 v,, = 274 v,, = 437 v , , = 248 e 3 R
Ref 64, 65 Ref 9 1-93 Ref 103 Ref 107-115, 121 Ref 140
a R = R a m a n active, I = i n a c t i v e , a n d Ir = i n f r a r e d a c t i v e .

TABLE X I I I . Structure of Solid Allotropes

Mole- Unit Density, Mp or

cule Space g r o u p cella a b C P , de, Color gm/cm3 d e c , OC Ref

R3-CSi2 3-18 10.818 cla = 0.3956 4.280 Orange-red 2.209 50-60 90

? 16-112 21.77 20.97 6.09 Yellow 2.090 39 102
Fddd-D,, 16-128 10.4646 12.8660 24.4860 Yellow 2.069 94 (112) 116-1 1 8
P2 ,fa-c,), 6-48 10.778 10.844 10.924 95.80 Yellow 1.94 133 126
P ~ / c - C , , , ~ 4-32 8.442 13.025 9.356 124 98 Light yellow 2.19 20 - 131, 132
Pnnm-D,h l 2-24 4.730 9.104 14.574 Pale yellow 2.036 148 137
P 2 , 2 , 2 , - D 2 4 4-72 21.152 11.441 7.581 Lemon yellow 2.090 128 141
Pbcn-DZh14 4-80 18.580 13.181 8.600 Pale yellow 2.016 124-125 142
C ~ r n 2 , - C , , ,16Ob
~~ 13.8 4 X 8.10 9.25 Yellow 2.0 1 104 146, 149
F i r s t n u m b e r is t h e n u m b e r o f m o l e c u l e s i n t h e unit c e l l ; second n u m b e r i s t h e n u m b e r o f a t o m s . b T e n a t o m s f o r t h r e e t u r n s .

The structure of all solid allotropes is summarized in Table that a chair configuration might exist in liquid sulfur. s82+has
XIII. The crystals d e c o m p o ~ eat~ , 50
~ ~ OC, but under high such a chair c o n f i g u r a t i ~ n . In
~ ~S4N4 diagonal sulfur atoms
vacuum, for example, in a mass spectrometer,12 cyclohexa- lie in planes above and below the nitrogen atoms,8 while
S molecules vaporize without dissociation. The photoioniza- S4(CH2)4 has the s8 crown structure. A similar structurelo6
tion energy5 of s6 is 10.2 eV. has been found by Steudel for S8O, by Cooper for mixed
SnSee-, rings, and by Weiss for S7TeCI2.
3. S7, Cycloheptasulfur Above 150 OC substantial ring scission is observed. The
bond dissociation en erg^^^-^' is estimated to be about 33
This allotrope is formed by the reaction
(C5H&TiS5 + S2C12 -
The S7 molecule has the structure shown in Figure 5b. The
S7 + (C5H5)2TiC12
kcal/mol. The molecule is sensitive to visible light.55 The
photoionization energy5 is 9.04 eV. It is not certain whether
this is due to the absorption edge63at 280 nm, or whether
has a weak triplet absorption in the green. The electronic en-
identity was confirmed by Zahorszky.l Not all sulfur atoms ergy levels have been computed and discussed by Palma,42
are equivalent. The x-ray structure02 and the ir spe~trurn~ Clark,41 Miller,36 and S p i t ~ e r . ~Gibbons4
discussed the en-
confirm this fact. The frequencies of the ir spectrum in soh- ergy levels of s8 in the solid phase. The other properties of
tion, and the Raman spectrum of the solid in solutions, are s8 are well r e ~ i e w e d except
,~ for recent Raman work. Since
listed in Table XII. Fifteen fundamentals are expected. the review of Strauss,lo7 Ward,08 O ~ i n , ~Anderson,
The light yellow needles have a density of d = 2.090 g/ Gautier, and Zallen12 have studied s8 in solution and in
cm3. The lattice constants are102 a = 21.77 A, b = 20.97 A, single crystals. They confirmed the assignment of the 11
and c = 6.09 A. modes by Scott.I3 The Raman spectrum of 34S8 has been
The space group of this allotrope, which decomposesg at measured by von Deuster. l 4 A normal coordinate l 5 analy-
39 OC, is not yet known. Sixteen molecules, i.e., 122 atoms, sis has been performed by Cyvin, and mean square ampli-
occupy the unit cell. tudes l 5 have been recalculated by Venkateswarlu. Raman
Semiempirical Huckel calculation^^^ for S7 chains, but not and ir spectral data are summarized in Table XII.
for rings, are available. The photoionization energy5 is 8.67 Cycloocta-S can crystallize in several different lattices;
eV . the structure of three solid allotropes is now well established.

4. Allotropes of Cyclooctasulfur a. Orthorhombic a-Sulfur

Cycloocta-S has the crown shape shown in Figure 4a. The a-Sulfur is the STP form of cycloocta-S. Abrahamsl6 has
symmetry is D4dor D4,,. The structure is well established: reported very accurate structure parameters7 Caron and Do-
S-S bond length (d)= 2.060 f 0.003 A nohue l 7 established the stacking of molecules, and Pawley
and Rinaldi118confirmed the structure, and measured the in-
S-S-S bond angle = 108.0 f 0.7 termolecular distances. The molecular packing is com-
plex.17 Figure 8a shows a projection perpendicular to the
S-S-S-S torsion angle = 98.3 f 2.1
mean plane of half of the molecules. This figure shows the
The molecule occurs in the solid, liquid, and gas phase. crankshaft structure l7 of this allotrope, which is still erro-
The is the most stable configuration at STP. The stability neously assumed by many to contain coaxially stacked rings.
is probably due to cross-ring resonance. Baurlo4suggested The lattice constants are a = 10.4646 A, b = 12.8660 A,
376 Chemical Reviews, 1976,Vol. 76,No. 3 Beat Meyer

TABLE X I V . Melting Point of Allotropes

trope M ~ , ~ c Remarks Ref

a-S 112.8 Single crystal 122

115.11 Microcrystal 119
&S 114.6 Natural 172
119.60 ldeai and obsd 122, 174
120.4 Microcrystal 119
133 Ideal calcd 52
yS 106.8 Classic 5, 6
108 Optical, DTA 128
108.6 MicrocrystaI 119
6-S 106.0 Microcrystal 119
WS 77;90; 160 Optical, TDA, DTA 128
104 122
s, 75 Optical 128
104 Classic 5
s, (50- 1 Decornposition 52.86
s, (39-1 Decomposition 52,82
S,, 148 Decomposition 52, 135-137
S,, 128 Decornposit ion 141
S, 124 Decomposit ion 141

a T h e r m o d y n a m i c melting point.

of lattice frequencies which are well resolved at the low tem-

perature. Ward published crystal splitting effects. The
electronic spectrum of solid sa has been discussed by Spit-
zer38 and Gibbons.40 The latter concludes that electric con-
ductivity of a-S is due to two contributions: (a) to hole mobili-
ty, which has a value of about 10 cm2/V.s, and exhibits a
negative temperature coefficient, and (b) to electron trans-
port in the electronic band (Figure l),which is narrow enough
C for strong vibrational interaction. This contributes approxi-
mately cm2/V.s to the conductivity. Gibbons gives a
site jump probability of 109/s, which would indicate that elec-
trons are located on an individual molecule for several vibra-
tions, i.e., that ions can be formed. The self-diffusion rate in
a crystals was measured by Hampton and Sherwood.20 The
electric conductivity was measured by Spear and Ad-
a m ~ F i,t t i ~~ a l~d i ,~and
~ ~~~Kuramoto and Watanabe.lZ4The
thermal c o n d ~ c t i v i t yof~ ~a-sulfur is 1 1 W/m-deg at 4.2 K,
0.29 Wlm-deg at 0 OC, and 0.15at 95 O C . The specific heat
of a-sulfur is summarized in Table IX; the heat of transition in
Table VIII.

b. Monoclinic &Sulfur
The structure of @-sulfurwas determined by Trillat and Fo-
Flgure 8. The structure of the solid allotropes of cyclooctasulfur:(a) restier,lZ5 Burwell,lZ6 and Sands. The space group is
the crankshaft structure of orthorhombic a-sulfur, (b) monoclinic ~ . sa molecules, i.e., 48 atoms, occupy the
~ ? , / a - C 2 ~Six
@-sulfur,and (c) the sheared penny roll structure of monoclinic unit cell. A view of the lattice along the b axis is shown in
y-sulfur. All views are perpendicular to the c axis (after Donohue,
Figure 8b. The lattice constants are a = 10.778 A, b =
ref 15).
10.844A, c = 10.924A, and p = 95.8.
@-Sulfur forms at 94.4 OC from a - s ~ l f u r . It~ melts
~ at
and c = 24.4860A. The space group is Fddd-DZhz4,the unit 119.6 OC. A thermal analysis has been conducted by Mil-
cell contains 16 molecules, i.e., 128 atoms, and the density
lerIz8 and by Curre11.122E r a m e t ~ a described
~~ formation
is 2.069g/cm3.
from the melt; Thackrayllg the melting of the solid. Thermal
The crystal growth of a-sulfur has been carefully studied
data for transitions are in Table VIII. The density is 1.94 g/
by Thackray l9 and Hampton.lZ0Almost perfect single crys-
cm3, Le., about 12% smaller than that of a-sulfur.
tals with only very few dislocations can be grown from CS2;
There has been some controversy about a phase transition
however, such crystals contain traces of CSp, which has an ir at 101 OC, but this effect was caused by evaporation of water
frequency at 658 cm- which has long been mistaken for a
traces. Recently new C, values have been reported by Mont-
fundamentallZ1of sa. Single crystals of a-sulfur do not easily
g ~ m e r ywho , ~ ~reports an anomaly at 186 K. The ir spectrum
convert to monoclinic sulfur. Instead, they melt122at 112 OC of @-monoclinicsulfur has been described by Strauss.
(Table XIV). lr and Raman spectra of a-sulfur have recently
been recorded by Ward,Io8 Ozin,Io9 Anderson, l o and von
c. y-Monoclinic Sulfur
Deuster.ll4 These data are summarized in Table XII. Gau-

tier l l observed crystals at 30 K, and reports a large number The structure of y-sulfur, first described by Muthmann13
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 377

in 1890, has been determined by Watanabe,13 1974, who TABLE X V . Preparation Methods f o r
confirmed the sheared penny roll stacking, proposed by de Metastable Allotropes
Haan132(Figure 8c). This allotrope can be obtained from so-
Species Reagents Kef
lutions of cycloocta-S, and from its melt, but the best way to
prepare the light yellow y needles, which slowly decompose (C,H,),MoS, + SCI, 82
at room temperature, is to treat cuprous ethyl xanthate with (a j HS,O,- + HCI 86
pyridine.I3 y-Sulfur crystallizes from the brown decomposi- (b) S,CI, + H,S, 7 4 , 99
tion product in large needles. The lattice constants are a = (C,H,),TiS, + S,CI, 82, 8 5
8.442 A, b = 13.025 A, c = 9.356 A, and p = 124 98. CuSSCOC,H, + pyridine 131
The space group is R / c . Some confusion about the struc- (C,H,),TiS, + S,CI, 133, 1 3 4
ture has been caused by different choices of axes. The con- (a) H,S, + S,CI, 79
version of coordinates has been reviewed by D ~ n o h u eFour
.~ (b) (C,H,),TiS, + SO,CI, 138
S8 molecules occupy one unit cell. The density of this allo- (C,H,),TiS, + S6CI, 138
trope is 2.19 g/cm3, i.e., higher than a- or 6-sulfur. H,S, + S,CI, 135, 1 3 6
H,S8 + SIOCI2 141
H,S,O S,OCI, 141
d. Other Allotropes of Cyclooctasulfur +

During the last 100 years about 24 allotropes containing

The first reaction135yields 3 % S12;the second,136discov-
cyclo-S8 have been described.6 Some of these are listed in ered later, has a yield of 18%. The reaction is conducted in a
Table I. It is doubtful whether any structures other than a-, b-, dilute solution of ether, and the reagents are slowly and si-
and y-sulfur are reasonably stable. Instead, most of the other multaneously added. In this way, the reagents have time to
Greek letter allotropes are probably mixtures of a-sulfur, 6- react, by forming an intermediate chain
sulfur, or y-sulfur, or constitute merely unusual crystal forms.
As little progress has been made7 in developing reliable H-S- - -Sx-S-CI
preparation methods, no new information has become avail-
and can complete ring closure before reaction with further
able since the last review.6 Thus, we can omit discussion of
reagents occurs. The principle of this synthesis is as beauti-
the confusing list of species, and refer for details to earlier
ful as it is simple. Schmidt and Wilhelm have since prepared
eight other new ringsg with similar methods. A summary of
their preparation methods is given in Table X V .
5. S9,Cycloenneasulfur The S I 2molecule has the structure137shown in Figure 4b
Schmidt and Wilhelm133prepared deep yellow needles of in D3d,but in the solid it is slightly distorted to C2h.The bond
cyclo-Sg by the reaction properties are:

(C5H5)2TiS5 S4C12 -+ (C5H&TiC12 f Sg S-S bond length (d)= 2.053 f 0.007 A
The structure of this compound has not yet been published. S-S-S bond angle = 106.5 f 1.4
Thermodynamic consideration^^^^^^ indicate that this ring
S-S-S-S torsion angle = 86.1 f 5.5
molecule also occurs in the vapor. The photoionization ener-
gy50 of S g is not published. These values are very similar to those for S8 and fibrous
S, i.e., the unperturbed bond value. As discussed above,
this fits P a ~ l i n g sprediction
~~ for the bond value of sulfur
6. Slo,
species, even though he did not properly analyze all possible
Schmidt and Wilhelmg9 prepared yellow-green solids con- conformations of S12,and rejected this molecule from the list
taining Slo rings by the reaction of chlorosulfane with sul- of metastable allotropes. However, experiments show that
fanes. Slo is separated from s6 by recrystallization, as their S I Pis more stable than s g . It is formed in liquid ~ u l f u r , ~and

solubilities differ substantially.100A far better yield of 35% forms as a decomposition product of s6 in toluene upon irra-
can be obtained if the following reaction8 is conducted at diation with light.g The solubility of S12in CS2 and benzene
-78 C: has been discussed by Schmidt.138The mass spectrum was
(C5H5)2TiS54- 2SO2C12 + Slo + 2S02 + (C5H5)2TiC12 ~ ~ S I 2melts at 148 C. The lattice
studied by B ~ c h l e r . Solid
constants were determined by Hellner and K u t o g l ~ : ~a =
The structure has not yet been published, and the mass spec- 4.730 A, b = 9.104 A, and c = 14.7574 A.
truml0Ia indicated limited stability. The solid must be stored The space group is Pnmm-D2h2. The unit cell contains
at -40 C. two molecules, i.e., 24 atoms. This allotrope has a density of
2.036 g/cm3. Mixed crystals of SnSe12-n have a very similar
7. SI1, Cycloundecasulfur structure. The Raman and ir spectrum was studied by Steu-
who tentatively assigned 6 of the 20 fundamentals.
Schmidt and Wilhelm134 prepared cyclo-S1l by the reac-
9. Sl8, Cyclooctadecasulfur
(C5H5)2TiS5 + s6c12 + SI1 + (C5H&TiCl2 S18 has been prepared from sulfane and chlorosulfane
Details of the properties and structure have not yet been pub- mixtures141of the average formula
lished. H2S8 + S1oC12 Si8 2HCI
The starting materials cannot be made in pure form, but are
8. SI2, Cyclododecasulfur synthesized from shorter sulfanes to prevent formation of the
In 1966 Schmidt and Wilhelm52i33prepared S I 2by the re- more stable SI>,and other allotropes. Figure 5 shows a pro-
action of sulfanes and chlorosulfane of proper chain length: jection of the cycIo-SI8 molecule. This lemon colored allo-
2HzS4 + 2S2C12 + Si2+ 4 HCI trope forms in a mixture with C ~ C I O - S and
~ ~must
, be sepa-
rated by recrystallization. The solubility of SI*in CS2 is 240
H2S8 S4C12 + SI2 + 2HCI mg/100 ml at 20 C. This unexpectedly stable allotrope
378 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

melts at 128 C, and can be stored in the dark for several

days, without a noticeable change in the x-ray diffraction pat-
tern. The bond parameter^'^^^'^^ are:
S-S bond length (d)= 2.059 8,
S-S-S bond angle = 106.3
6oo t liquid

S-S-S-S torsion angle = 84.4

The bond properties are intermediate to those of sg and
Sg, and similar to those of fibrous sulfur helices, given in
Table XI. The lattice constants42 are a = 21.152 A, b =
11.441 A, and c = 7.581 8,.
Four molecules, i.e., 72 atoms, form a unit cell. The space
group is P 2 1 2 ~ and
2 ~ the density is 2.090 g/cm3.

70. S ~ OCycloicosasulfur
~ - ~ ~ S20 by combination of carefully
S ~ h m i d t ~prepared
prepared intermediates 0 20 40 60
H2S10 + S1oC12 + S20 + 2HCI pressure (kbar)

S20 melts at 124 C, but already decomposes in solution at Flgure 9. Melting curve of sulfur, and structure of allotropes ob-
35 C. The pale yellow crystals have a density of d = 2.016 tained b quenching: (1) D e a t ~ nand
~ ~V e ~ z o l i , (2)
~ ~S u s ~ eand
Sklar,151(3) Ward and Deaton15 and P a n k o ~ , and ~ ~ (4) Baak.15
g/cm3. The structure of the molecule, Figure 5, provides for The zone from which laminar,48 fibrous,14 and plastic156allo-
four atoms each in a plane. The bond values42 are: tropes have been quenched is also indicated.
S-S bond length (d)= 2.047 A
1. Fibrous Sulfur
S-S-S bond angle = 106.5
The x-ray diffraction of freshly drawn fibrous was
S-S-S-S torsion angle = 83 first analyzed by Trillat and Forestier in 1931, and by Meyer
and Go in 1934. The data by D ~ n o h u e , T ~~~i n s t r a , and
similar to those of SIP, S18. and fibrous sulfur. The lattice pa-
Geller46 indicate that the unit cell contains 160 atoms. The
rameters are a = 18.580 A, b = 13.181 A, and c = 8.600 8,.
Four molecules, with 80 atoms, form a unit cell. space group is C~rn21-C2,~. The structural parameter^'^^
are a = 13.8 A, b = 4 X 8.10 A, c = 9.25 A, and 6 = 85.3.
Gellers analysis was conducted on diffraction patterns ob-
C. Allotropes of Polymeric Sulfur tained with samples prepared at 27 kbars. The density of fi-
All of the allotropes described below contain polycatena- brous sulfur is d = 2.01 g/cm3. Lind and Geller46 believe
sulfur. The polycatena molecule forms long he lice^.^*'^^*'^^ that their preparation of phase II yields single crystals of
Figure 3 shows a section of a left- and a right-handed helix. psulfur. The phase II structure has been indexed by Roof.149
Three turns of the helix contain 10 atoms. The bond charac- The thermal expansion c ~ e f f i c i e n t of
~ ~psulfur is 19 X
t e r i s t i c ~are:
~,~~~ cm/deg along the pitch, 94 X cm/deg along the a
axis, and 72 X cm/deg along the b axis. Thermal tran-
S-S bond length (d)= 2.066 A sition, polarization, dilatometry, and other properties have
S-S-S bond angle = 106 been reported by Miller.28

S-S-S-S torsion angle = 85.3

2. Lakinar Sulfur
These values are very close to those in S20 and S12, and lie Laminar sulfur first described by D ~ s ,seems ~ ~ to be iden-
between those of S8 and s g . It is believed that they represent tical with Gellers phase I, obtained at 250-300 C and 20
the unperturbed values of the S-S bond. kbars (Figure 9). Its structure has been discussed by Dono-
Solid polycatenasulfur comes in many forms.6~7,10~145 It is hue.7 The characterization seems still incomplete; it is very
present in rubbery sulfur, plasic (x) sulfur, laminar sulfur, fi- similar to, or possibly identical with, insoluble w-sulfur and
brous (4, v,
qh), p , and insoluble o,supersublimation, white, the second fibrous sulfur of T u i n ~ t r a . ~ ~
All~ of
and c r y ~ t e x . ~ ~ *these
~ forms are metastable mixtures
of allotropes containing more or less well-defined concentra- D. High-pressure Allotropes
tions of helices, cyclo-S8, and other forms, depending on
how they are made. Their composition changes with time. Various sulfur allotropes can be obtained by heating sulfur
Unless impurities are present, formation of S8 sets in and under pressure. Figure 9 shows some of the high pressure
conversion to a-S will occur within less than 1 month. They effects observed. D e a t ~ nobtained
~~ a melting curve which
are prepared by precipitation of sulfur in solution, or by is similar to that of V e ~ z o l i . S
~u~~ s e obtained
~~ a curve
quenching of hot liquid sulfur. In some allotropes, the helices similar to that of Sklar.56 Ward and D e a t ~ n published
~~ an-
can be purified by extraction of the nonpolymeric fraction other melting curve which matches that of P a ~ k 0 v . l ~ ~
with CS2 or other solvents. B a a k ~ melting
~~ curve is also shown in Figure 9, but his
Donohue7 summarized the structural information on the cubic phase is not indicated, as it has not yet been con-
various forms in which the helices are stacked or curled. The firmed. However, Figure 9 shows the p, T zones from which
best defined forms are fibrous sulfur, in which helices are laminar and fibrous sulfur49 have been quenched.
mainly parallel because of stretching during their solidifica- The plastic sulfur zone of Sklar56 agrees well with Gellerls
tion, and laminar sulfur in which helices are at least partly observations, Tonkov161measured the molar volume of liquid
criss-crossed in a cross-grained or a plywood like struc- sulfur under pressure, Brollos and Schneider162 report the
ture. optical properties of sulfur under pressure, and Kuballa and
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 379

S ~ h n e i d e r 'report
~~ a differential thermal analysis of sulfur T A B L E X V I . Freezing Point Depression
under pressure. Block and Piermarini's experiment^'^^ ex-
plain the divergent observations reported for pressures above TA - Tf,"C Av no.
Equilibrated of
24 kbars and temperatures above 250 OC. They waited at at T, "C Calcd Obsd atorns/ring
this point for 3 days without observing equilibrium, and ex-
plain this effect by slow kinetics and the poor thermal con- 120 4.6 13.8
d u ~ t i v i t y No
. ~ ~wonder that authors using different equipment 130 5.7 4.9 14.6
and different p , T cycling techniques observe dozens of dif- 140 7.1 5.9 15.7
ferent phases! The best established high-pressure forms are 150 9.1 7.6 17.6
phase I and phase I1 of Geller.i46 In contrast, metallic sulfur ref 11. 174, 179, 180,and 187.
has not been reproduced.i60 It is likely that some of the 12
phases of V e ~ z o l icontain
l ~ ~ interesting new structures. the melting point of pure P-sulfur is 119.6 OC, but Thack-
ray119observed melting of microcrystals at 120.4 OC, while
E. Low-Temperature Solids S ~ h m i d t indicates
~ , ~ ~ that the ideal melting point might be as
high as 133 OC. The freezing point of an equilibrated melt is
Cyclo-S7, -Sg, and -Sio must be stored below room tem-
114.6 OC. This point has been called "natural" melting
p e r a t ~ r e .At
~ . -78
~ ~ OC and below quickly quenched hot liq-
point.172The best value of the heat of melting seems to be
uid sulfur or hot sulfur vapor contains a variety of colored
the one observed by P a ~ o rand l ~ Feher,174
~ AH,.,, = 384.2 f
metastable solids.63-165Ir and uv spectra have shown that
1.9 cal/g-atom at 119.6 OC, while the higher values of up to
these solids contain S3, S4, and other allotropes. In the next
414.8 f 2.4 cal/g-atom are valid at 114 OC in an impure mix-
section it will be shown that these quenched phases have
ture. The specific heat174of the liquid at 120 OC is 7.02 cal/
been repeatedly used to determine the composition of hot
g-atom-deg. Feher also measured the expansion coeffi-
sulfur, and the T fraction. However, great experimental care
cient, 175 the electric conductivity,176and the viscosity of the
must be taken if a significant fraction of the high temperature
melt, as did Bacon and Fanellii68 and Doi.177
species is to be trapped, because these particles recombine
G e r n e ~ reported
'~~ in 1876 that the melting point and the
quickly and because sulfur is such a poor thermal conduc-
freezing point of sulfur differed. He recognized that this effect
tor76 that heat exchange is slow. Most molecules formed in
was not fully due to supercooling, or to impurities, but to a
trapped or quenched solids are intermediates,166i.e., recom-
chemical effect which could be influenced by annealing the
bination products. The properties of these are discussed in
liquid at various temperatures. Aten178proposed in 1913 that
the next two sections together with those of the starting ma-
the freezing temperature was caused by autodissociation of
terial. The absorption spectra of various molecules in frozen
sulfur, forming a new species, nsulfur, the concentration of
low-temperature solution or rare gas matrices are indicated which determined the freezing point depression. Krebsg5ar-
in Figure 14. Sp can be produced in rare gas matrices from gued in 1953 in favor of the existence of small rings in liquid
elemental sulfur vapor trapped at 20 K, or by photolysisi67 of sulfur, and determined the concentration of x-sulfur in liquid
S2C12 in matrices. S3 is best prepared from the vapor, by
sulfur by quickly quenching it, extracting the solid with CS2,
combination of atoms with S2, or by gentle photolysis of
and isolating r-sulfur, which precipitates from the extract
S3CI2 in frozen solution. S4 can be prepared from S4C12, or
upon cooling to -78 OC. The problem with this fraction is
by recombination of S2 in matrices. S5 has been deposited in
that it changes its composition for several days. Furthermore,
mixtures from vapor, and s6 and s8can be studied in frozen
it is questionable whether quenching of an insulator such as
solution. Polymeric sulfur can be quenched as a thin film.
sulfur and extraction of the solid preserve the composition of
Slowly quenched polymeric sulfur is yellow. Polymer quickly
the liquid. Most physical chemists familiar with P a ~ l i n g ' s ~ ~
quenched to 76 K is red, because it contains small molecules
paper tended to distrust explanations based on rings other
which recombine at -100 0C.165The properties and reaction
than or s6, until S ~ h m i d tproved
~ , ~ ~ that at least seven of
of the species will be discussed in the section on liquid sulfur
these can be prepared, are metastable, and that, for exam-
and sulfur vapor, i.e., in the phase in which they are stable.
ple, S12can be found in all solidified melts. In 1967 Krebs
published another very careful studyg5 on r-sulfur which he
IV. Liquid Sulfur extracted with a mixture of CS2-methanol. In these solvents,
s6 has a distribution coefficient of 0.13, while the coefficient
The appearance and the molecular composition of liquid
sulfur differ in three distinct temperature ranges. These re- for S8 is 0.11. After 700 distribution steps, r-sulfur could be
gions and the effect of high pressure on liquid sulfur will be separated into three fractions, one having a molecular weight
discussed separately. of about s6, a middle fraction containing Sa, and an average
composition of about S9.2, and a heavy fraction in which he
A. The Melt below 150 O C
suspected S, rings, with 20 < <n 33. W i e w i o r o ~ s k iana-
lyzed the freezing point depression and computed the con-
At least 19 different melting points of sulfur have been centration of cycloocta-s, and determined for this molecule a
published. Table XIV gives a selection of values for the melt- bond dissociation energy of 32 kcal/mol. This value agrees
ing points of @-sulfur,which constitutes the stable solid at the well with that of 32.8 kcal/mol obtained by Tobolskylo by
melting point, and for other allotropes. The freezing point of analysis of the polymerization at higher temperature. Table
sulfur is influenced by the p , T history of the melt, and by im- XVI shows the freezing point depression observed, and the
purities. As high-purity sulfur was not readily availablei68 average number of atoms per ring calculated by Semlyenis0
until 1942, most old data are unreliable; i.e., the freezing with the help of a polymer model.
points are too low. Obviously, the equilibrium composition of the sulfur melt is
Small droplets of sulfur can be supercooled. LaMer16' kept not yet established, The "natural" thermodynamic melting
particles with a diameter of 0.2 p liquid at 25 OC for up to 20 point is difficult to determine because of slow kinetics. It is
days. Hamada17' observed nucleation of droplets at -70 to now assumed to be 119.6 OC. At this point, solid monoclinic
-120 OC under a microscope, and determined a crystalliza- @-sulfur is in equilibrium with a liquid mixture of unknown
' -50 OC. bolo to^'^^ and others
tion rate of 1.16 c ~ - ~ . s - at composition. Higher "ideal" melting points can be observed
have observed formation of various types of spherulites dur- because of the slow kinetics of the cyclooctasulfur ring dis-
ing crystallization of molten sulfur. The best present value for sociation. The "ideal" melting point for the transition of solid
380 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

I _ 8

1 I I I I I I

-002 0 0.02 004


100 200 300 400 T Figure 11. Density of liquid sulfur at 159 O C (after Pate11e2).
1 I I I l l
Flgure 10. Composition of liquid sulfur I. Estimated mole fraction of 2.3 160
liquid sulfur components of small species, large rings (r), and chains
(n), computed from ref 11. c

monoclinic &sulfur to pure liquid cyclooctasulfur is not yet m
established. The fact that the p, T history reproducibly influ- b 220-
ences the freezing point indicates not only slow kinetics but
also that cooling of the various hot sulfurs proceeds via dif- I-
ferent reaction paths and leads to different metastable mix-
tures of different metastable species, probably mostly rings.
The temperature dependence of the equilibrium composi- 2.10 200
tion of liquid sulfur computed by Harris11,181 from various ob- 20 40 1 00 200 300
served and estimated thermodynamic data is shown in Figure Tme (sed
Figure 12. Temperature dependence of polymerization rate of liquid
Baurio4 observed an unusual molar polarization effect and sulfur, based on 12 observation points (after KlementlQ).
proposed a cyclo-S8 with a chair configuration as a further
component of the liquid. It is now certain that liquid sulfur S ~ h e n kdiscussed
l~~ the viscosity again, as did DO^.'^^ Eyr-
contains rings other than s& Whether, and how much, ca- ingia8 and Tobolsky and Eisenberg7 developed a polymer-
tena-S8 or other catena-S, the melt contains, is not yet es- ization theory which quantitatively explains the viscosity
tablished. However, calculations by Miller,36 and C u ~ a c h s , ~ ~change. It is based on two steps:
and S p i t ~ e show
r ~ ~ that the acid-base character of rings and
chains, first discussed by W i e w i o r o ~ s k i , is
cause formation of cyclo-S,-catena-S,-cyclo-S,
transfer complexes. Such complexes have been invoked to
~ ~sufficient to
cyclo-S8 r; catena48
catena-S8 + cyclo-S8
This theory has been extensively discussed and thoroughly
catena-S8x2 (11)

explain the small concentration of free spins in liquid sulfur at

150 OC. This observation is discussed in detail by Konings- reviewed. Various small modifications adapted to this theory
berger. allow for rings other than Sa, and make possible the explana-
The melting point of sulfur is also pressure depen- tion of other p h e n ~ m e n a . ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
dent.53-i60 Four different melting curves are shown in Figure The thermodynamic properties of the polymerization have
9. The different slopes are probably partly due to different pu- been extensively researched. The values of AH and S (Table
rity of the samples. However, the curves also depend on the VIII) were determined by T o b ~ l s k y . West
~ ~ , ~and
~ Feheri74
p, Thistory because of slow kinetics.164 measured the specific heat (Table IX), and Klement,gl Ku-
balla, and Wardlg2 conducted a differential thermal analy-
sis. Ward1g~i92and Oziniog used laser Raman spectroscopy
B. Polymerization at Tx = 159.4 O C to study the polymerization, which is characterized by inten-
Around 159.4 OC almost all properties of liquid sulfur suf- sity changes of bands at 456, 416, and 273 cm-l. Eisen-
fer a discontinuity. Figure 11 shows, for example, the density berglag discussed the mechanism of the polymerization,
change.182Points close to the transition were observed after comparing a chain-end interchange mechanism with bond in-
12 h of equilibration. The values were interpreted as due to a terchange, and concluded that bond interchange is important
logarithmic singularity, a cooperative phenomenon, which is in viscous sulfur. The kinetics of equilibration have been in-
very rare.182The velocity of sound,IB3 p ~ l a r i z a b i l i t y , com-
~~ vestigated by Klement.lg3 He determined rates at 15 temper-
pressibility,i62 molar p o l a r i ~ a t i o n , the
~ ~ electric conductivi- atures, and found the correlation shown in Figure 12.
ty,176v1833184 the surface tension,65 and many other proper- Wigandlg4 observed as early as 1909 that the polymeriza-
ties have been measured in the same temperature region. tion equilibrium is photosensitive. The influence of impurities
However, the most striking effect of this temperature, which on the degree of polymerization was measured by Feher174
is often called temperature, is the sudden change in vis- for C12, Koningsbergerls1 for 12, Wiewiorowskiig5 for CS2,
cosity. RuberoiS6 for H2S, and Wardig2 for As. Six percent of the lat-
Eotvosse and Kellase8 long ago described the well-known ter causes sulfur to polymerize at the melting point.
sudden gelling of the liquid, as did Schenk. Hammick5 and Schmidt52 showed that 2 % s6 lowers the polymerization
Schenk5 determined the weight percent of polymer. temperature by 10 for over 15 min, while (SCH2)9, added at
Bacon and Fanelli166demonstrated the influence of impuri- 200 O C , reduces the average chain length greatly.
ties on the viscosity, and showed how sulfur can be purified. The effect of pressure on polymerization was reported by
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 381

I \ I I I I a 1,

LI~UK Absorption Edge of Liquid Sulfur

' b

-12 I IJ I I I I

100 200 300 400 500

Tqerature "C
Figure 13. Composition of liquid sulfur II. The weight fraction of the
polymer was computed from data of ref 11 and 186. The average
chain length is from ref 10, and the free spin concentration from ref

Doi.l7' Brollos162used the visible absorption edge of liquid 3CO 400 530 600 nrn
sulfur to study the same effect. Figure 14. Visible absorption edge of liquid sulfur at (a) 120, (b) 250,
The ESR spectrum of liquid sulfur was first observed by and (c) 500 O C . The absorption of individual components was ob-
Gardner and Fraenkel.lg7They found a signal, but it was far tained for Sa at -70 O C in EDTA, for polymeric sulfur at -196 OC,
weaker than anticipated. It was first suggested that this was as a thick film; SB,S4. and Ss in EDTA at -196 OC; and S p at -253
O C , in a rare gas matrix (after ref 58 and 63).
due to line broadening in the hot liquid, but paramagnetic sus-
ceptibility measurements by Poulis and Massenle3gave simi- model of long intertwined rings. However, so far Wiewiorow-
larly small free spin concentrations. Koningsberger'81 com-
ski's charge complex t h e ~ r yexplains ~ ~ ~ 'the
~ ~situation best.
pleted a thorough study of the ESR spectra of pure sulfur, and Sulfur is known to form charge transfer complexes with iodo-
selenium, and of sulfur doped with 12. He obtained the free
form, and possibly with iodine; calculation^^^ indicate that
spin concentrations shown in Figure 13. Koningsberger cor-
S8-SX-S8 should be stable.38
related the spin concentration with the polymer concentra-
tion, which can be computed from the weight f r a ~ t i o n ~of' ~ ' ~ ~
C. Liquid Sulfur above 250 O C
the polymer P and the average chain length, and reported a
similar temperature dependence. Figure 10 shows, however, At high temperature, the viscosity of liquid sulfur de-
that the free spin concentration is also almost identical with creases rapidly, and the color turns first red, then brown, and
the concentration of S5, as computed by Harris" from vari- almost black. Simultaneously, it becomes extremely reac-
ous thermodynamic considerations. It is not clear whether tive. Thus, in all except the most pure sulfur (99.999+%),
the spectrum is due to polymer,'" S5, or charge-transfer the color effect is obscured by irreversible darkening due to
complexes,'95 but this question does not raise doubts regard- reaction of organic impurities. Pure boiling has the
ing the validity of the polymerization theory; it merely raises same color as the equilibrium vapor.63 The absorption edge
the question as to what small species are present in the liq- of Figure 14c corresponds to the spectrum obtained on hot
uid at the polymerization temperature, and in what concen- thin liquid films, quenched in liquid nitrogen. Such films retain
tration. So far, only the uv and visible s p e ~ t r asuggest
~ ~ ? ~an~ the color of the liquid.63 The shoulder in the absorption curve
answer. At the melting point, liquid sulfur is pale yellow. The coincides with the spectra of S3, S4, and S5. The spectra of
corresponding absorption spectrum is shown in Figure 14a. these specie^'^^^^^^ are known from the gas phase, or from
The spectrum of S8 in an organic glass63 at 76 K, indicated in low temperature matrices, in which they can be isolated.
the same figure, explains the absorption edge. At 250 OC, Very little else is known about hot liquid sulfur, except that it
sulfur is still yellow, but the absorption is now due to super- is very reactive toward almost every chemical. This is ex-
position of the spectrum of SE with that of plastic sulfur. plained by the presence of S3, thiozone, and other small mol-
Liquid polymeric sulfur is dark yellow63and has an absorp- ecules.
tion edge at 350 nm. Solid polymeric sulfur, obtained by The boiling point201 of sulfur, believed to be 293 OC by
quenching of a thin film of liquid sulfur at 200 OC in liquid ni- Davy, and 440 OC by Dumas, is 444.64 OC. This transition is
trogen, remains yellow, while cyclo-S8 turns snow white, and no longer a primary, but a secondary temperature reference
has the spectrum indicated in Figure 14b. Thus, polymeric point, according to IUPAC.201The critical point202,203 of sul-
sulfur is not dark red, as is erroneously believed by many fur is at 1040 OC and 200 atm. The critical properties, Table
who know that boiling sulfur is deep red or who have seen XVII, indicate that liquid sulfur, as well as the vapor, consists
impure liquid sulfur turn dark because of organic impurities. essentially of sp, S3, and s4 with very little s5.s6, s7, and
The origin of the red color in the hot liquid will be explained Sa. Figure 15 shows that thermodynamic considerations indi-
in the next section; but the absence of deep dark color in cate that just below the critical point, liquid sulfur has a
solid and liquid polymeric sulfur at 160 and 200 OC remains a smaller average molecular weight than the vapor.96,203It re-
puzzle, because the free-radical chains, according to all mains to be seen whether experiments will confirm this.
known t h e o r i e ~ , should
~ ~ , ~ be
~ deeply colored. Several pos- However, the composition of the vapor12.50,51~96 (Figure 17)
sible explanations have been proposed. One is that mol and of the liquid" (Figure 10) extrapolate smoothly to the
of organic impurity is sufficient to scavenge polymeric chains critical data (Figure 15).
by conversion to ~ u l f a n e sAnother
.~~ explanation revives the The recent discovery of small molecules in hot liquid sulfur
382 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

TABLE X V I I . Critical Data I ' ' I

Quantity Value Ref 2
TC 1313 K = 1040 " C 5
96 0
Pc 179.7 atm
200 atm
20 2 -
VC 158 cm3/mol 0

dC 0.563 g/cm3 -4
VC 2.8 at o ms/m olecu le
8 I I I

Tc 1040% -8
I I I 1 1
0 400 800 1200

nl \
4 J
Temperature T
Figure 16. Equilibriumpressure of sulfur: the total pressure curve 2 ,
was constructed from data in ref 96, 201-203. The partial pressures
of S, 2 < n < 8, were estimated from data of ref 12 and 51.

21 I I I I 1.0 p I I I I I 1

400 800 1200

T "C
Figure 15. Average number of atoms per molecule in vapor and liq-
uid at the critical point (after RauZo3).

casts light on a formerly unknown phase, which surely must
display interesting chemical properties.

V. Sulfur Vapor
A. General
The vapor pressure of sulfur from room temperature to
2300 K was first measured by Bilz and Meyer.15 Some points
of the vapor pressure curve (Figure 16) are listed in Table X. I I I I
400 Boo 1200 %
Recently published high-pressure values202*203 agree well.
The critical temperatures reported by Baker and Rau203are Figure 17. Mole fraction of S, 2 < R < 8, in a saturated vapor, be-
within 1 K, i.e., 0.1%; however, Baker's critical pressure is tween 120 and 1000 OC,estimated from data in ref 12, 51, 63, and
200 atm, i.e., 20% larger than that reported by Rau (Table 201-203.
XVIII). Specific heat and other thermal data for the vapor
have been summarized for JANEF by J e n ~ e and n ~ others.
~ unravel the molecular composition of equilibrium vapor over
Preuner and Schupp204 concluded that equilibrium vapor a large temperature range. At low temperature, S8 accounts
consists of s8,
s g , and S2. Braune and S t e i n b a ~ h estudied
r~~~ for over 90% of the vapor, while s g and S7 make up the rest;
the vapor pressure and the uv spectrum and concluded cor- and the vapor is green due to the uv absorptiong3 of the ter-
rectly that an absorption at 510 nm was due to S4. They also minally excited ground of S8 and of the other mole-
observed the spectrum now known to be due to S 3 , but as- cules. Upon heating, the concentration of S8 in equilibrium
signed it erroneously to another transition of Sd. The 100- vapor steadily decreases, and the vapor consists increasingly
year-old controversy about the vapor composition was finally of the small species. Above 1000 K, S2 is the most abundant
settled when B e r k o w i t ~ ' ~ . ~
' * ~ ~ that vapor contains all species. At the critical the vapor contains mainly
molecules S, 2 < n < 10, including all odd-numbered S p , S3, and S4 (Figure 15). The composition in the intermedi-
species. B u ~ h l e revenl ~ ~ detected S12 in the vapor. The fact ate temperature range is shown in Figure 17. The S5, s g , and
that photoionization yields only one ionization value5' sup- S7 concentration of each goes through a maximum at about
ports earlier thermodynamic reasoning12 that all vapor 1000 K. According to Rau,203 S5 never accounts for more
species occur as rings. than about 3 % of the total vapor pressure, while Baker202
The vapor pressure depends upon the phase with which it estimates a maximum of 18 % at about the same temperature.
is in contact. LaMer produced169airosols with particle diame- The relative concentration of small species increases in
ter of 0.2 1.1 at 25 to 75 OC which are stable for several days unsaturated pressure. Spectral studies206-207 indicate that at
and have five times equilibrium vapor pressure. 800 K and 100 Torr, S2 accounts for over 80% of all vapor
Berkowitz12 has shown by mass spectroscopy that vapor
in equilibrium with rhombohedral cyclohexa-S contains s g .
The preferential vaporization of sulfur species has since
99 YO.This vapor is violet,204due to the B -
species. At 1000 K and 1 Torr, the corresponding value is
X absorption of
S1.The color of this vapor was already studied by G e r n e ~ ' ~ ~
been used by Berkowitz5' and D r ~ w a r t The . ~ ~ latter used in 1876. S3 and S4 in c o n c e n t r a t i ~ n s
~~~~ 10%
~ are
Rickert's electrolytic cell: obtained at about 10 Torr and 800 K. This vapor is cherry
red.63 Sulfur atoms are not present in equilibrium vapor
below the critical point.202They can be prepared as transient
to overcome problems in identifying the molecular ionization species by photolysis.208-212 The thermodynamic properties
pattern in a mass spectrometer. Thus, it became possible to of the various sulfur species are given in Table XIX. The cor-
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 383

TABLE X V I II. Thermodynamic Data of Gaseous Sulfura

B(S-S), kcal/mol
AH f , s,
Molecule Equilibrium kcal/rnol c a l / m o l .deg Obsdb CalcdC

5 2 2S(S) *
S,(g) 31.20 54.40
s3 2S,(g) 2 3S2(9) 33.81 64.39 55.8 48.7
s 4 S,(g) 2 2S,(9) 34.84 74.22 57.8 58.6
s, 2S,(g) 2 5% (4) 26.14 73.74 60.0 58.3
S6 3/4S,(g)2 S,(g) 24.36 84.60 61.8 62.8
s, 1/8s8(g) 2 S,(g) 27.17 97.41 62.2 63.6
S8 S8(g) e 4S2(g) 24.32 102.76 63.0 60.1
a S t a n d a r d state: 1 a t m , 298.15 K; see r e f 12, 96, a n d 51. Reference 12. Reference 43.

TABLE X I X . Heat Capacities C, of Gaseous TABLE X X . Dissociation Energy o f S,

Sulfur Moleculesa
D o 0 ( S , ) ,k c a l / m o l Method Ref Year
C, cal/deg.rnol
100.69 i 0.01 Uv spectroscopya 224 1969
A B C 300 K 1000 K 101.0 f 0.2 Photoionization 12 1969
5101.0 i 0.8 Photoionization 223 1968
8.54 0.28 4.79 0.8 1.8 101.7 i 2.9 Kn u dsen-torsi on 222 1968
12.854 1.04 -1.554 1.3 1.9 effusion
19.092 0.783 -2.820 1.4 1.9 101.0 ? 2.5 Thermochemistry 51, 221 1966
25.558 0.253 -3.771 1.5 1.9 97t 5 Mass spectrometric 221 1964
31.580 0.120 -4.400 1.6 1.9
37.038 0.613 -4.723 1.6 1.9 a 100.69 k c a l j m o l c o r r e s p o n d s t o t h e p r e d i s s o c i a t i o n a t
42.670 0.860 -5.1 10 1.7 1.9 35 5 9 0 c m - .
5.268 6.121 -0.816 5.4
tained in discharges,216or by photolysiss3 of S2C12 and simi-
aSee r e f 203. bSee also T a b l e I X . lar compounds in the gas phase, in organic glass, or in matri-
ces. The formation of S2 via recombination of atoms has
been discussed by O l d e r ~ h a wMany . ~ ~ ~reactions yield a sig-
responding specific heats have been calculated by R ~ U , ~ ~
nificant fraction of S2 in the first electronic excited state
who makes available a computer program which allows com- 1A.218
putation of vapor pressures.
S2 is the most stable of the small sulfur molecules. Its
If hot sulfur vapor is rapidly quenched to 76 K, or below,
ground state29 is 32,-, as is that of 02.However, the triplet
colored solids can be obtained,ls5 which contain a mixture of
levels exhibit a far larger ~ p l i t t i n gthan
~ ~ .0 ~
2 .~Recently,
~ the
various vapor components, together with recombination
products which are formed during condensation. It is possible
ESR s p e ~ t r u m ~of S2 has yielded accurate ground-state
data. The ground-state frequency, observed by Raman spec-
to trap individual vapor species by diluting the vapor with an
inert gas. This matrix method66 has been used to trap Sp, troscopy,206is 718 cm-. The existence of Sp has long been
recognized. Seventeen of its electronic energy levels are
s3, s4, s6, and sa. Photolysis of c h l o r o ~ u l f a n e s
sulfur compounds in glasses and matrices has made possible
selective preparation of solutions containing S atoms, and
chains of S, 2 n < <7. Upon warming, all these systems
~ ~ other
known,29~207 far more than for 0 2 . The violet color is due to
the lowest allowed transition B 3 2 , X 32,- which has a
transition energy of 31 689 cm-. The corresponding B X
- -
yield polymeric sulfur, and eventually sa. emission is observed whenever sulfur compounds are burnt
in a reducing flame. This emission, for which the transition
strength is well determined, is widely used for quantitative
B. Individual Species determination220 of sulfur compounds, separated by gas
Sulfur atoms are not present in equilibrium pressure below chromatography. The properties of electronic energy levels
the critical point.202 Sulfur atoms can be produced as an have been reviewed by B a r r o ~ , who ~ ~ has
, ~ made
~ ~ most of
electric discharge, and by photolysis. Gunning and Strausz208 the original observations.
have perfected gas-phase preparative methods, using COS. There has been an extended controversy about the disso-
The electronic energy levels31 of atomic sulfur are well ciation energy of S2. It can now be considered solved, as
known. Photolysis produces atoms in the 3P ground state, as thermochemical considerations,221Knudsen-torsion effusion
well as in the excited state ID. At short wavelengths the S measurements,222mass s p e c t r o ~ c o p y , ~ and . ~ ~photoion-
level is also obtained in good yield.21 Excited atoms carry 26 ization, listed in Table XX, all agree on the higher of the
kcal/mol excess energy and have a sufficient lifetime to possible values. The p r e d i s s o ~ i a t i o nin~the
~ ~uv ~ ~spectrum
enter chemical reactions. Strausz and Gunning208 have ex- yields the most accurate value; 35 590 cm- = 101.8 f
plored extensively the chemistry of sulfur atoms with organic 0.01 kcal/mol. A recent value for p h o t o i ~ n i z a t i o nis ~ ~9.36
molecules. Some inorganic reactions have been studied by eV, and confirms the earlier value of 9.9f 0.6 eV obtained
Donovan.213With themselves, the atoms form S2, and even- by electron impact. The photoelectron spectrum50 of S2 cor-
tually S8. The ESR spectrum2I4 of two 3P sublevels has been responds, as expected, to that of O2 and Te2.
studied by Brown in a gas stream containing about loi3 Several studies have been conducted on S2 in rare gas
atoms/cm3. Thermodynamic properties215of the atom, such mat rice^.^^^,^^^ S2 is produced by trapping vapor, a dis-
as specific heat, heat of formation, and entropy have been
recently reviewed.
charge, or photolysis. The absorption spectrum shows a sim-
ple progression with vn -
yor, as kT is insufficient at 20 K
S2 constitutes nearly 45% of the equilibrium vapor202,203 to yield vibrationally excited ground state atoms. The emis-
at 1040 OC, the critical point. At 1000 K and 1 Torr, and sion spectrum and a Raman band at 720 cm- have also
lower pressures, S2 is almost 99% pure. S2 can also be ob- been reported. An ir band165at 668 cm- is observed and is
384 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

now assigned200 to S4. Its uv spectrum can be observed chain conformation would leave the terminals 3.5 A apart49
when S2 containing matrices are annealed. (Table V), while for all observed rings, values of about 2 A
The S p - ion will be discussed in the section on ionic solu- are computed. Except for its weak a b s ~ r p t i o n ,its
~ ~vapor
tions. pressure,201s202 which accounts for about 13 % at the critical
S3 was called thiozone by Erdmann,2261908, who as- pressure, and its photoionization energy5' of 8.60 eV, very
sumed that it exists in liquid sulfur. L d'Or published the uv little is known about S5. It is isoelectronic with S4N- which is
spectrum of S3 in 1909, but R ~ s e n assigned
~ ~ it to S2. fairly well known.22aIt should be pointed out that in liquid sul-
8raune2O5 assigned it to S4, and most physical chemists re- fur, S5 might be the most abundant of all small paramagnetic
jected the existence of S3 until 1964, when BerkowitzI2 species." If so, the striking similarity between the S5 con-
found it in the mass spectrometer. It has since been proven centration computed by Harris" (Figure I O ) and the concen-
that S3 occurs in sulfur vapor199and in liquid sulfur.63 At the tration of free species observed by Koningsberger'*' (Figure
critical point, thermodynamic measurement indicates that 13) might not be accidental.
6 % S3 is p r e ~ e n t . ~ ~ ~ , ~ ' ~ so, S7, s6, Sg, Si', and Si2 have all been found in the
The best conditionsE3for observing S 3 in sulfur vapor are v a p ~ r . It' is
~ likely ~ they exist as ring^.'^^^' The same
~ ~ ~that
found at 10 Torr and 440 OC, when it makes up about 10- rings are very likely present in the i~ fraction of liquid SUI-
20% of the vapor, and gives it its characteristic deep, cherry fur,95,178,179 which causes the curious melting phenomena of
red color. The first allowed electronic transitionig9 shows ex- sulfur. However, all these molecules also exist as pure solids
tensive rotational structure. The origin is at 23 465 cm-', as at room temperature, where they can be much more easily
vibrational shifts of 34 bands of 3 2 S 3 show. The bands indi- studied. Thus, they are discussed in section 1118, with solid al-
cate a ground-state stretching frequency of v i = 590 cm-l, lotropes. In the liquid and perhaps also in the vapor, S, 6 <
and VI' = 420 cm-l for the first excited state. The transition n < 12, can also occur as chains, at least as transient equi-
energy is amazingly close to that calculated from a Huckel librium species. These should be easily recognizable by the
using sulfur atom parameters. S3 is not only isoval- deep color which they must exhibit.63
ent with 0 3 , but also with SO2 and S 2 0 , and has accordingly
a bent structure, a ground state of 'E, and carries on the ter- VI. Solutions
minal atom a charge of -0.078. The c a l c ~ l a t i o n sgive ~~ a
In nonpolar liquids, cyclooctasulfur and other rings dis-
bond distance of 1.98 A, and assume a bond angle of 120'.
solve at room temperature without decomposition. Represen-
Uv spectra show that S3 can be prepared in matrices and
tative solubility values of frequently used solvents are indicat-
glasses199by careful photolysis of S3Cl2, and other similar
ed in Table XXI. Distribution factors for s6 and Sa in eight sol-
compounds. Ir frequencies of 585, 490, and 310 cm-' found
vent mixtures can be found in ref 95 and 230. Binary systems
in discharges227of SO2 and Raman227frequencies at 662
including sulfur have been studied and reviewed by Wiewio-
and 583 cm-l of recombination products of S20 have been
rowski.14 Systems including liquid sulfur and aromatic hydro-
recently attributed to S 3 .
carbons have been reviewed by Scott. l3Recently, fugaci-
The experimental photoionization5' of S3 is 9.68 f 0.03
ties231of similar systems have been measured, however, it
eV. Two ions of S3 are known. The S3- ion, which can be
should be noted that above 130 OC thermal dissociation of
easily recognized by its pale blue color, will be discussed in
the ring by homolytic scission induces free-radical reac-
the section on ions. S32-, the trisulfide ion, forms in aqueous
tions,E usually hydrogen abstraction. Thus, many of the re-
ported systems suffer slow chemical reaction, recognizable
S4 occurs in liquid199-203and gaseous sulfur. Its continu-
by the color change.
ous absorption at 530 nm has been repeatedly re-
W i e w i o r o w ~ k has
i ~ ~demonstrated
~ that liquid sulfur itself
p ~ r t e d . ~ ' ~It, ~
'~ together with S3. Its vapor spectra
makes an excellent solvent, and lends itself to ir studies of
can be best recorded at 450 OC and 20 Torr, where it is as-
reaction. With H2S sulfur forms a reactive system,195$233 as it
sumed to account for about 20% of the vapor.63At the criti-
does with iodine,lEi chlorine,i74 arsenic,lg2 and at higher
cal point, it forms between 24 and 40% of all species.201,202
temperatures with At room temperature, light con-
Bonding considerations suggest that S4 can occur as a ring,50
verts Sa into insoluble photosulfur, which partly redis-
as a chain,38and as a branched m01ecu1e,~~ as shown in Fig-
s o ~ v e s . ~ ~ . ~ ~ ~
ure 7. Semiempirical Huckel c a l c ~ l a t i o n sindicate
~~ that the
In ionic solutions, elemental sulfur suffers nucleophilic or
trans chain and the branched molecule have similar stability,
electrophilic attack and forms deeply colored solutions, first
and that both are far more stable than the pyramid, the planar
described by Geitner,236which contain molecular ions, usual-
ring, or any other form, including the ring. It is quite possible
ly chains.
that the branched S03-type structure, with a charge of -0.12
on the terminal atoms, can exist, at least at low temperature. Molecular Ions. Three classes of molecular ions are
S4 is found in mat rice^^^,^^^ by careful photolysis of tetra- known. The polysulfides are doubly charged negative ions
sulfide, or, much easier, by recombination2'' of Sp. Ir bands that are quite stable in aqueous solutions at high pH, and as
at 688, 483, 320, and 270 cm-' have been assigned to it. solid salts. Singly charged negative ions form in salt melts at
Raman bands in trapped discharges227through SO2 have high temperature, and doubly charged cations are observed
also been assigned to S4. in so-called "super acids".
The photoionization5' of S4 has not been published yet. The polysulfides are formed by chain scission, which is
The electron impact method" yielded a value of 10.4 eV. followed by rapid chain degradation or by polymerization
Three ions of S4 have been reported: S42+ is assumed to yielding chains S, with 1 < n < 20 atoms. The molecular
be planar,65 like Se4*+. S4- supposedly forms in salt melts, bond characteristics of polysulfides are:
while S42-, the stable tetrasulfide ion, occurs in aqueous so- S-S = 2.048 A
lution, at a high pH, as a chain.
S5 has rarely been studied or discussed, even though it oc- S-S-S = 107' 53'
curs in the vapor,I2 the in matrices,63 and possibly s-s-s-s = 900
even as a solid.52 Thermodynamic considerations suggest
that it is a ring.12.50,5'calculation^^^ favor the chain, as do These compounds are pale yellow, and equilibrate rapidly
stereochemical considerations. If the S-S-S-S bond geome- with each other, yielding with well-established
try is to be preserved, even the most favorable unstrained S5 corn position^.^^^^^^*^^^ Feher" prepared the free sulfanes
Elemental Sulfur Chemical Reviews, 1976, Vol. 76, No. 3 385

TABLE X X I . Solubility of Sulfur H2Sn, observed the spectra59of individual, pure sulfanes, and
calculated their uv spectra6' with a one-electron model. A
Solubility semiempirical Huckel c a l ~ u l a t i o ngives ~ ~ very similar transi-
(wt %)
g of SjlOO tion energies. Figure 6 shows that with increasing chain
Solvent g solvent T, "C Ref length the transition energy converges at 320 nm. Recently,
the structure of some alkaline earth di- and trisulfides has
0.14 -60 233 been determined. The S-S bond distancez4' varies between
0.005 0
2.050 A for SrS3 and 2.124 A for BaS2.
1.3 80
The singly charged ions, S2-. S3- and S4-, have been ob-
0.0078 25 234
served when elemental sulfur or certain sulfur compounds
0.039 60
0.46 140 are dissolved in the KCI-LiCI melt,241~z4z in liquid KCNS,243
4 -80 234 and in d i m e t h y l f ~ r m a m i d e . ' ~They
~ . ~ ~also
~ occur in miner-
35.5 25 a l ~The . color
~ ~ of~ various ultramarines is explained by the
55.66 60 presence of such ions, but also by neutral sulfur species.246
CCI, 0.148 -2 4 234 The green S2- ion absorbs24' at 400 nm, and has a
0.86 25 Raman242 active stretching frequency, which lies between
1.94 60 592 cm-' in Nal and 612 cm-' in KBr, depending on the sol-
CHCI, 1.2 60 5, a vents. From this an S-S bond distance of about 2.00 A can
CHBr, 3.64 5.6 be estimated.47
CHI, 42 85 Blue S3- absorbs at 610-620 nm. It has Raman242
H,O-(CH,),SO (1~1) 0.003 60 b frequencies at 523 cm-I and an ir absorption at 580 cm-I.
Ethanol-(CH,),SO (1: 1) 0.37 60 b Its bond distance has been estimated4' to be 1.95 A. The
Acetone-(CH,),SO (1: 1) 0.45 60 b ESR spectrum has been observed.247The molecule has Cpv
NH,-(CH,),SO (1~1) 15 60 b symmetry, and a bond angle smaller than 120'. The omnipre-
"3 38.6 -20 C
sence of this ion,248 i.e., its superior stability in the ionic
21 30
media, is not yet satisfactorily understood. S3- is isoelec-
("412s 37 20 d
tronic with 0 3 - and SO2-, both of which have been re-
S*CI2 7.3 -9 a
17 21
97 110 Gillespie identified cations of sulfur in oleum and in super
Pyridine 10.5 85 27 acids.64 The cations are parts of complex ions: SB2+(AsF6)*.
19.2 100 Sa2+ is known best.Io5 Its structure is well established. The
Aniline 46 130 27 Sa ring is converted into a chair structure, and the bond dis-
Benzene 2.1 25 5, a tances are 2.04 A, i.e., somewhat shorter' than in S8. Like-
17.5 100 wise, nonbonding S-S distances are closer than in Sa. The
Ethanol 0.066 25.3 structure of Sa2+ is intermediateIo6 to that of S4N4. Wilkin-
Ethyl ether 0.283 23 27 studied the ESR spectrum of Ssf.
Acetone 2.7 25 The S42+ ion is quite well e ~ t a b l i s h e d In .~~analogy64 to
Hexane 0.25 20 27 the Se42+ ion, it is expected to be a planar ring. The Raman
2.8 100 frequency252 has been measured and assigned to the fol-
lowing modes:
a D. L. Hannick a n d M. Zvegintzov, J , Chem. Soc., 1 7 8 5 ( 1 9 2 8 ) .
b T. Kawakami, N. K u b o t a , a n d H. Terni. Teclinol. Rep. Iwate Univ.,
7 7 ( 1 9 7 1 ) . C A . K e o u a n t o n , M. Herlem, a n d A. Thiebault, Anal. u1 = 584 cm-' Ai, u3 = 460 cm-' E,
L e f t , , 6 . 1 7 1 ( 1 9 7 3 ) . d ~ Bretsznalder
. a n d J. Ptskorski, Bull. Acad.
Pol. Sci.,C'l. 3, 1 5 , 9 3 ( 1 9 6 7 ) . u2 = 530 cm-l Big u4 = 330 cm-' Bug

TABLE X X I I . Molecular Composition of Sulfur Phases and Reaction Products

Reagents Allotrope
_ _ ~ . _ _ _ _ _

Phase Molecular species Well-established Inconclusive o r mixture

Solid sulfur (a) Stable (STP): Sb (Geller I I ) Laminar, w, orange, me-

Cyclo-S, as a-SS tallic, Vezzoli, Geller,
(b) Metastable: Bask
Solid sulfur Cycl o-s,a
Catena-Si, 16 < i < 10'
Charge transfer complex
c yc I 0- S, -ca t e na-Si-
Liquid sulfur C Y C I O - S ~6, < < 24 ( ? )
Catena-Si, 3 < i < l o s
Sulfur vauor CYCIO-S,, 6 < [I < 12 Crystex, w , red, $, secon-
Catena-Si, 2 < i < 5 dary fibrous, green, blue,
black (Schenk) violet,
green, pgrple
Solution, containing Cycl 0- s, W 1 , 2 ( E ) '$, I*, E? 77, 0 , XI

cyclo-s, K! , O , T ,
Solution, containing sulfur 6,u, w, nl-n2, red (E, F,
compounds G ) , orange (I, K, L, M )

a n = 6 . 7, 8 . 9. 10, 11, 12, 1 8 , 2 0 .

386 Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer

They have also been identified by and circular di- (4) (a) R. C. Clegg. British Patent 3968 (1815); (b) C. R . Philips, British
Patent 4142 (1817).
~hroism.~~ (5) L. Gmelin's "Handbuch der Anorganischen Chemie", Part 9A, 8th ed,
A third species, Gillespie's S1e2+ is also formed in super Verlag Chemie. Weinheim. 1953.
acids, but its identity and properties are still incompletely (6) E. Meyer. Chem. Rev., 64, 429 (1964).
(7) J. Donohue, "The Structures of the Elements", Wiley, New York. N.Y.,
demon~trated.~~ 1974, p 324.
(8) M. Schmidt and W. Sibprt, "Comprehensive Inorganic Chemistry",
Vol. 15, A. F. Trotman-Dickenson, Ed., Pergamon Press, Oxford,
VI/. Conclusion 1973.
. . M. Schmidt. Anaew. Chem.. 85. 474 (1973):
(9) . . Anaew.
- Chem.. lnt. Ed.
In the last 10 years much has been learned about the mo- Engi., 12,334 (7973).
lecular structure of elemental sulfur. lt is now known that 10) (a) A. V. Tobolsky and J. W. MacKnight, "Polymeric Sulfur and Related
Polymers", Interscience, New York, N.Y., 1968; (b) W. J. MacKnight
many different types of rings are sufficiently metastable to and A. V. Tobolsky in "Elemental Sulfur", B. Meyer, Ed., interscience,
exist at room temperature for several days. It is known that at New.~ York. N.Y.. 1965. 95.
11) (a) R . E. Harris,'J. Phj;s:Chem., 74, 3102 (1970); (b) personal commu-
high temperature, the equilibrium composition allows for a nication.
variety of rings and chains to exist in comparable concentra- 12) (a) J. Berkowitz, ref lob, p 125. (b) J. Berkowitz and J. R. Marquart, J.
tion, and it is known that at the boiling point and above, the Chem. Phys.. 39, 275 (1963).
13) (a) R. L. Scott, ref lob, p 337; (b) J. A. Larkin, J. Katz, and R. L. Scott,
vapor as well as the liquid contains small species with three, J. Phys. Chem.. 71, 352 (1967).
four, and five atoms. (14) T. K. Wiewiorowski, MTPlnt. Rev. Sci., lnorg. Chem., Ser. One, 2, 171
Now that many of these species can be isolated in pure (1972).
(15) E. Meyer. Ed., "Elemental Sulfur, Chemistry and Physics", Inter-
form, it should become possible to study the relative reactivi- science, New York, N.Y., 1965.
ty of different allotropes. Such knowledge would make possi- (16) G. Nickless, Ed.. "Inorganic Sulfur Chemistry", Elsevier, Amsterdam,
ble selective reactions, which would open simpler and (17) A. Senning. Ed., "Sulfur in Organic and Inorganic Chemistry", Marcel
cheaper paths to synthesize sulfur compounds, such as poly- Dekker, New York, N.Y., 1971-1972, three volumes.
sulfides, and other industrially important and useful com- (18) A. V. Tobolsky, Ed., "The Chemistry of Sulfides", Interscience, New
York, N.Y., 1969.
pounds. So far, very little is known about the reactivity of dif- (19) J. H. Karchmer, Ed., "Analytical Chemistry of Sulfur and Its Com-
ferent pure allotropes. Bartlettg4 and Davisg8have reported pounds". Wiley-lnterscience, New York, N.Y., 1970.
(20) M. Schmidt, lnorg. Macromol. Rev., 1, 101 (1970).
the kinetics of s6 with triphenylphosphine chloride. Knipps- (21) (a) N. Kharasch, Ed., "International Journal of Sulfur Chemistry, Part
discovered that s6 reacts with many nucleophilics B", 1969; (b) J. Platou, Ed., "Sulphur Institute Journal", The Sulphur
about lo4 times faster ihan does Sa.The quick reaction of s6 Institute, Washington, D.C.. 1964; (c) "Sulphur Research Newsletter",
H. L. Fike, Ed., The Sulphur Institute, Washington, D.C., 1964.
with HI, which reacts only very slowly with Sa, has been re- (22) R. Rahman, S. Safe, and A. Taylor, Q. Rev., Chem. SOC., 24, 208
ported by The mechanism of these reactions is (1970).
(23) E. E. Reid, "Organic Chemistry of Bivalent Sulfur", Chemical Publish-
not yet conclusively established, but the degradation of S-S ing Co., New York, N.Y., 1958-1968.
chains,56as it occurs, for example, in the reaction of sulfur (24) N. Kharasch, Ed., "Chemistry of Organic Sulfur Compounds", Perga-
with the sulfite ion, and the formation of chains,255has been mon Press, New York, N.Y., 1961.
(25) W. A. Pryor. "Mechanism of Sulfur Reactions", McGraw-Hill, New
plausibly explained.25 The work of Norris and his group256 York, N.Y., 1962.
has shown that radioactive marking with 35Scan greatly help (26) (a) V. I. Pavlov and L. N. Kirillov, Tr. Tol'yattinsk. Politekh. lnst., 1, 78
(1969); (b) H. Suzuki, K. Higashi, and Y. Miyake, Bull. Chem. SOC.Jpn.,
with the unraveling of reaction paths and the determination of 47, 759 (1974); (c) H. Suzuki, Y. Osumi, M. Nakane, and Y, Miyake,
the kinetics. ibid., 47, 757 (1974).
The reaction of sulfur with various organic compounds has (27) (a) W. N. Tuller, ref 19, part I: (b) A. Grunert and G. Tolg. Talanta, 18,
881 (1971).
been recently reviewed by J~raszyk.*~' Such reactions are (28) 0. Stachewski, Chem. Tech., 4, 269 (1975).
very sensitive to traces of acids and bases.25 Reactions of (29) "International Tables of Selected Constant", Vol. 17, "Spectroscopic
Data Relative to Diatomic Molecules", B. Rosen, Ed., Pergamon Press,
sulfur with sulfide have been studied by Oae258 and his Oxford, 1970.
group, and many others2' The reactions of liquid sulfur have (30) G. Herzberg, "Molecular Spectra and Molecular Structure. Ill. Elec-
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