Professional Documents
Culture Documents
Meyer-76 (Sulf) PDF
Meyer-76 (Sulf) PDF
BEAT MEYER
Chemistry Department, University of Washington, Seattle, Washington 98 195, and lnorganic Materials Research Division, Lawrence Berkeley
Laboratory, University of California Berkeley, California 94 720
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
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
8
2.04 105
&-Cystine 2.05 h
t hydrochloride
si * 2.053 137
H2S2 2.055 1
r.095
56 2.057 7
LJ- -LJ s*
S,
2.060
2.066 145
7
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
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
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 +-+--++-
11
3.70
3.72
3.75
2.01
2.23
2.27
+-++--+-
++-+--++
+++-+-+-
++-+-+--+
i-++---+-+
++-i--++-
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
-
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
Atoms Ionb
S per
molecule Ringa Chaina +2 -1 -2
1
2
3
4
5
6
7
8
9
200 400 800 10
6oo nm
11
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
8
CIS non sym
-0.14
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.
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-
s
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
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)
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 ' ~
values
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 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 .
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.
Allo-
trope M ~ , ~ c Remarks Ref
a T h e r m o d y n a m i c melting point.
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 +
+
(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,
Cyclodecasulfur
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-
tion
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
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 ~ 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-
l~~
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
2-
8
I _ 8
1 I I I I I I
100 200 300 400 T Figure 11. Density of liquid sulfur at 159 O C (after Pate11e2).
Temperature
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
E T OC
F
monoclinic &sulfur to pure liquid cyclooctasulfur is not yet m
U
established. The fact that the p, T history reproducibly influ- b 220-
Y
180
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-
1
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
10.
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
charge-
cyclo-S8 r; catena48
catena-S8 + cyclo-S8
This theory has been extensively discussed and thoroughly
-
(1)
catena-S8x2 (11)
I \ I I I I a 1,
I I
' b
-12 I IJ I I I I
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
dC 0.563 g/cm3 -4
VC 2.8 at o ms/m olecu le
-6
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
01
casts light on a formerly unknown phase, which surely must
display interesting chemical properties.
V. Sulfur Vapor
A. General
001
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 ~ ' ~ . ~
showed
' * ~ ~ 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
of~about
~~~~ 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
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.
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-
solutions.
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, ~
occurs
'~ 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
ported.249t250
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
Reagents Allotrope
_ _ ~ . _ _ _ _ _
cyclo-s, K! , O , T ,
Solution, containing sulfur 6,u, w, nl-n2, red (E, F,
compounds G ) , orange (I, K, L, M )
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,
1968.
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-
been investigated by Langer and Above 180 O C liq- tronic Spectra and Electronic Structure of Polyatomic Molecules",
Van Nostrand. Princeton, N.J.. 1966.
uid sulfur reacts with aromatic and other hydrocarbons, and (31) C. E. Moore, "Atomic Energy Levels as Derived from Analysis of Opti-
their halogen derivatives5 This reaction is due to the small cal Spectra", .Val. I., U.S. Government Printing Office, Washington,
D.C., 1949-1958.
sulfur speciess3 formed at this temperature. These reactions (32) (a) D. W. J. Cruickshank and B. C. Webster in "Inorganic Sulfur Chem-
explain the irreversible darkening of all but the purest molten istry", G. Nickless, Ed.. Elsevier. Amsterdam, 1968, p 7; (b) D. W. J.
sulfur. The reaction of high temperature species has only Cruickshank, B. C. Webster. and D. F. Mayers, J. Chem. Phys., 40,
3733 (1964).
been superficially explored.260 However, the reaction of (33) M. Keeton and D. P. Santry, Chem. Phys. Lett., 7 , 105 (1970).
atoms is now well established, due to the work of Gunning (34) (a) W. W. Fogleman, D. J. Miller, H. B. Johassen, and L. C. Cusachs.
lnorg. Chem., 8, 1209 (1969); (b) K. A. Levison and P. G. Perkins,
and Strausz.208 Theor. Chim. Acta. 14, 206 (1969).
Table XXll presents, in conclusion, a summary of those (35) G. L. Carlson and L. G. Pedersen, J: Chem. Phys., 62,4567 (1975).
sulfur allotropes which have been most widely described. A (36) (a) L. C. Cusachs and D. J. Miller, Adv. Chem. Ser., No. 110, 1 (1972);
(b) D. J. Miller, Ph.D. Thesis, Tulane University, New Orleans, La.,
study of the pure allotropes which would yield better bond 1970; (c) D. J. hiller and L. C. Cusachs, "The Jerusalem Symposia on
data and better models for the formation and reaction of S-S Quantum Chemistry and Biochemistry. II. Quantum Aspects of Hetero-
cyclic Compounds in Chemistry and Biochemistry". The Israel Acade-
bonds would be most valuable. my of Sciences and Humanities. Jerusalem, 1970; (d) D. J. Miller and
Acknowledgment. This work was supported, in part, by the L. C. Cusachs, Chem. Phys. Lett., 3, 501 (1969).
(37) S. D. Thompson, D. G. Carroll, F. Watson, M. O'Donnell. and S. P.
U S . Energy Research and DevelQpment Administration McGlynn, J. Chem. Phys., 45, 1367 (1966).
through the Molecular and Materials Research Division, Law- (38) (a) B. Meyer and K. Spitzer. J. Phys. Chem., 76, 2274 (1972); (b) K.
Spitzer, Ph.D. Thesis, University of Washington 1973; (c) B. Meyer. K.
rence Berkeley Laboratory, University of California Berkeley, Spitzer, and L. Peter, unpublished work.
Berkeley, Calif. 94720. The author wishes to thank Professor (39) D. P. Craig and C. Zauli. J. Chem. Phys., 37, 601 (1962).
J. Donohue for helpful suggestions and permission to use (40) D. J. Gibbons, Mol. Cryst. Liq. Cryst., 10, 137 (1970).
(41) L. B. Clark, Ph.D. Thesis, University of Washington, 1963.
Figure 8 , and Professor L. Brewer for making available his (42) (a) A. Palma and N. V. Cohan. Rev. Mex. Fis., 19, 15 (1970); (b) Rev.
reference collection and facilities. lnst. Mex. Pet., 2, 100 (1970).
(43) H. Muller and H. Heegn, Acta Chim. Acad. Sci. Hung.. 53, 67 (1967).
(44) G. Bergson, Ark. Kemi, 18, 409 (1961).
Vlll. References (45) 0. Foss, Adv. lnorg. Chem. Radiochem., 2, 237 (1960).
(46) L. Pauling, Proc. Natl. Acad. Sci. U.S.A.,35, 495 (1949).
(1) H. Frasch. U S Patent 461 429/31 (1891) (47) R. Steudei, Angew. Chem., 87, 683 (1975).
(2) C. F. Claus. British Patent 3608 (1882). (48) I. Lindquist, J. lnorg. Nucl. Chem., 6 , 159 (1958).
(3) K. H. Schmidt, Chem. lnd. (Duesseldorf), 26, 737 (1974). (49) (a) J. A. Semlyen. Trans. Faraday Soc., 83, 743, 2341 (1967); (b) ibid.,
Elemental Sulfur Chemical Reviews, 1976,Vol. 76,No. 3 387
84, 1396 (1968). (105)(a) C. G. Davies, R. J. Gillespie. J. J. Park, and J. Passmore, lnorg.
(50)(a) J. Berkowitz and W. A. Chupka, J. Chem. Phys.. 50, 4245 (1969); Chem., I O , 2781 (1971):(b) A. Bali and K. C . Malhotra, Aust. J.
(b) J. Berkowitz and C. Lifshitz, ibid., 48, 4346 (1968);
(c) J. Berkowitz, Chem., 28, 983 (1975).
ibid., 82, 4074 (1975). (106)(a) G. W. Frank and P. J. Degen, Acta Crystallogr., Sect. 8,29, 1815
(51)D. Detry, J. Drowart, P. Goldfinger. H. Keller, and H. Rickert, 2. Phys. (1973);(b) R. Steudel, P. Luger, H. Bradaczek, and M. Rebsch. Angew.
Chem. (FrankfurtamMain), 55, 314 (1967). Chem., 85, 452 (1973):(c) R. Cooper and J. V. Culka. J. lnorg. Nucl.
(52)M. Schmidt, Chem. 2..7, 1 1 (1973). Chem., 29, 1217 (1967);32, 1857 (1970);(d) J. Weiss and M. Pupp,
(53)D. A. Johnson in "Sulfur in Organic and Inorganic Chemistry", Voi. 2, Angew. Chem., 82,447(1970).
A. Senning. Ed., Marcel Dekker, New York, N.Y., 1972,p 37. (107)H. L. Strauss and J. A. Greenhouse, ref lob. p 241.
(54) M. Schmidt and H. D. Block, Angew. Chem., 79, 944 (1967). (108)A. T. Ward, J. Phys. Chem.. 72, 744 (1968).
(55)A. Wigand, Ann. Phys., 29, l(l911). (109)G. A. Ozin. J. Chem. Soc. A, 116 (1969).
(56)(a) M. Schmidt, ref l o b , p 301;(b) M. Schmidt, Chem. Z., 84, 236 (110)A. Anderson and Y. T. Loh, Can. J. Chem., 47, 879 (1969).
(1963). (111)G. Gautier and M. Debeau, Spectrochim.. Acta, Part A, 30, 1193
(57)(a) J. Buttet, Chem. Phys. Left.. 1, 297 (1967);(b) A. Chatelain and J. (1974).
Buttet, ref lob. p 209; (c) A. Chatelain, Helv. Phys. Acta, 42, 117 (112)R. Zallen. Phys. Rev. 8,(9),4485 (1974).
(1969). (113)D. W. Scott, J. P. McCullough. and F. H. Krause, J. Mol. Spectrosc.,
(58) B. Meyer, M. Gouterman, D. Jensen. T. Oommen, and T. Stroyer-Han- 13, 313 (1964).
sen, Adv. Chem. Ser., No. 110, 53 (1972). (114) B. Meyer and E. von Deuster, unpublished results.
(59)F. Feher and G. Winkhaus, Z.Anorg. Allg. Chem., 292, 210 (1957). (115)(a) S. J. Cyvin, Acta Chem. Scand., 24, 3259 (1970);(b) K. Venka-
(60)F. Feher and H. Munzer, Chem. Ber., 98, 1131 (1963). teswarlu and K. Babu Joseph, Bull. SOC.R. Sci. Liege, 38, 173 (1967).
(61)J. W. Raimonda and W. T. Simpson. J. Chem. Phys., 47, 430 (1967). (116)S.C. Abraham, Acta Crystallogr.. 8, 661 (1955).
(62)H. Schmidbaur, M. Schmidt, and W. Siebert, Chem. 8er.. 97, 33L4 (117)(a) A. Caron and J. Donohue, Acta Crystallogr., 18, 562 (1965):(b) J.
(1964). Donohue, A. Caron, and E. Goldish, J. Am. Chern. SOC., 83, 3748
(63) (a) T. V. Oommen, Ph.D. Thesis, University of Washington, 1971;Diss. (1961).
Abstr. lnt. 8, 31, 3904 (1971):(b) B. Meyer, T. V. Oommen. and D. (118)G. S. Pawley and R. P. Rinaldi, Acta Crystallogr., Sect. B, 28, 3605
Jensen, J. Phys. Chem., 75, 912 (1971);(c) B. Meyer, T. Stroyer-Han- (1972).
sen, D. Jensen, and T. V. Oommen, J. Am. Chem. Soc., 93, 1034 (119)(a) M. Thackray. J. Chem. Eng. Data, 15, 495 (1970);(b) M. Thackray,
(1971). ref lob, p 45.
(64)(a) R. J. Gillespie and J. Passmore, Acc. Res., 4, 413 (1971):(b) MTP (120)(a) E. M. Hampton, B. S. Shaw, and J. N. Sherwood. J. Cryst. Growth.
inf. Rev. lnorg. Chem., Ser. Two, 3, 121 (1975). 22, 22 (1974); (b) E. M. Hampton and J. N. Sherwood, Phil. Mag., 29,
(65)P. J. Stephens, J. Chem. SOC.D, 1496 (1969). 763 (1973).
(66)M. J. Cardone, ref 19,Vol. 2, 1972,p 89. (121)I. Srb and A. Vasco, J. Chem. Phys., 37, 1892 (1962).
(67)H. Mackle and R. G. Mayrich, Trans. Faraday SOC.,58, 238 (1962). (122)B. R. Curreil and A. J. Williams, Thermochim. Acta, 9, 255 (1974).
(68)T. L. Allen, J. Chem. Phys., 31, 1039 (1959). (123)(a) W. E. Spear and A. R. Adams, ref lob. p 185;(b) F. Fittipaldi and L.
(69)(a) S. Sunner. CODATA Bull., No. 8 (1971):Chem. Absfr., 75, 41202 Pauciulo, J. Appl. Phys., 37, 4292 (1966).
(1971);(b) E. F. Muller and J. B. Hyne, J. Am. Chem. SOC..91, 1907 (124)(a) Y. Kuramoto, Y. Watanabe, and Y. Inuishi, Techno/. Rep. Osaka
(1969). Univ., 19, 571 (1969):(b) Y. Watanabe, N. Saito, and Y. Inuishi. J.
(70)J. Kende, T. L. Pickering. and A. V. Tobolski, J. Am. Chem. Soc., 87, Phys. SOC.Jpn., 25, 1081 (1968).
5582 (1965). (125)J. J. Trillat and J. Forestier, C. R. Acad. Sci., Paris, 192, 559 (1931).
(71)(a) A. V. Tobolsky and A. Eisenberg, J. Am. Chem. Soc., 82, 289 (126)J. T. Burwell, Z.Kristallogr., 97, 123 (1937).
(1960);(b) ibid., 81, 780 (1959);(c) A. V. Tobolsky, W. J. MacKnight, (127)(a) D. E. Sands, J. Am. Chem. Soc.. 87, 1395 (1965);(b) D. E. Sands,
R. B. Beevers. and V. D. Gupta, Polymer, 4, 423 (1963); (d) A. V. To- private communication (see ref 7).
bolsky and M. Takahashi, J. Poiym. Sci., Part A2, 1987 (1964). (128)G. W. Miller, J. Appl. Polym. Sci., 15, 1985(1971).
(72)H. C. Whitehead and G. Andermann. J. Phys. Chem., 77,721 (1973). (129)0.Erametsa and L. Niinisto, Suom. Kemistil. 8,42, 471 (1969).
(73)K. I. Narkuts. lzv. Akad. Nauk SSSR,Ser. Fiz., 38, 548 (1974). (130)W. Muthmann, 2. Kristallogr., 17, 336 (1890).
(74)D. Jensen in "Selected Values of Thermodynamic Properties of the El- (131)Y. Watanabe, Acta Crystallogr.. Sect. 8. 30, 1396 (1974).
ements", D. T. Hawkins, M. Gleiser, and K. K. Kelly, Ed., American (132) Y. M. de Haan. Physica, 24, 855 (1958).
Society of Metals, New York, N.Y., 1973. (133)M. Schmidt and E. Wilhelm. J. Chem. SOC.D,17 (1970).
(75)(a) R. L. Montgomery, Science, 184, 562 (1974);(b) PhD. Thesis, Uni- (134)M. Schmidt and E. Wiihelm, unpublished results.
versity of Oklahoma, 1975. (135)M. Schmidt and E. Wilhelm, Angew. Chem., 78, 1020 (1966).
(76) (a) L. J. Ericks and R. L. Powell, "Thermal Conductivity of Solids at (136)M. Schmidt, G. Knippschild. and E. Wilhelm, Chem. Ber., 101, 381
Low Temperatures", Natl. Bur. Stand. (U.S.), Monogr. (1971); (b) R. W. (1968).
Powell, C. Y. Ho, and P. E. Liley, Nafl. Stand. Ref. Data Ser., Nat. Bur. (137)A. Kutoglu and E. Hellner. Angew. Chem., 78, 1021 (1966).
Stand., No. 8, part 1 (1966). (138)M. Schmidt and H. D. Block, 2. Anorg. Allg. Chem., 385, 119 (1971).
(77)B. M. Mogilevskii and A. F. Chudnovskii, Proc. lnt. Conf. Phys. Semi- (139)J. Buchler, Angew. Chem., 78, 1021 (1966).
cond., 2,1241 (1968). (140)(a) R . Steudel and M. Rebsch, J. Mol. Spectrosc.. 51, 189 (1974);(b) J.
(78)J. M. Dale and A. C. Ludwig, ref l o b , p 161. Weiss and W. Bachtler, Z.Nafurforsch. 8. 28, 523 (1973):(c) R. Steu-
(79)E. Wilhelm, Ph.D. Thesis, Marburg, Germany, 1966. del and M. Rebsch, 2. Anorg. Allg. Chem., 413, 252 (1975);(d) R.
(80)M. Schmidt, B. Block, H. D. Block, H. Kopf, and E. Wilhelm, Angew. Steudel and D. F. Eggers, Spectrochim. Acta, Part A, 31, 871, 875
Chem., 80, 660 (1968):Angew. Chem., lnt. Ed. Engl., 7, 632 (1968). (1975).
(81)(a) F. Feher and G. Winkhaus, 2. Anorg. Ailg. Chem., 288, 123 (1956); 141) M. Schmidt, E. Wilhelm, T. Debaerdemaeker, E. Hellner. and A. Kuto-
(b) F. Feher and W. Kruse, ibid., 293, 302 (1957):(c) F. Feher, K. glu, 2. Anorg. Allg. Chem., 405, 153 (1974).
Naused, and H. Weber, ;bid., 290, 303 (1957). 142) (a) T. Debaerdemaeker and A. Kutoglu, Naturwissenschaften. 60, 49
(82)H. Kopf. B. Block, and M. Schmidt, Chem. Ber., 101, 272 (1968). (1973):(b) Cryst. Sfruct. Comm., 3, 611 (1974).
(83)K. A. Hofmann and F. Hochtlen, Chem. Ber., 38, 3090 (1903). 143) M. Schmidt, Unpublished results.
(84)H. Kopf. Angew. Chem., lnt. Ed. Engl., 8, 962 (1969). 144) (a) J. A. Prins, J. Schenk, and L. H. J. Wachters, Physica, 23, 746
(85)H. Kopf. Angew. Chem., 81, 332 (1969);Angew. Chem., lnt. Ed. Engl., (1957);(b) J. A. Prins and F. Tuinstra. ibid., 29, 328,884 (1963);(c) J.
8, 375 (1969). A. Prins, private communication.
(86)M. R. Engel. C.R. Acad. Sci., Paris, 112, 866 (189 1). 145) (a) F. Tuinstra, Physica, 34, 113 (1967);(b) Acta Crystallogr.. 20, 341
(87)A. H. W. Aten, Z.Phys. Chem., 88, 321 (1914). (1966);(c) "Structural Aspects of the Allotropes of Sulfur and other
(88)(a) A. M. Kelias. J. Chem. Soc., 113, 903 (1918):(b) E. Eotvos, Ann. Divalent Elements", Waltman. Delft, 1967.
Phys. Chem., 27, 452 (1886). (146)(a) M. D. Lind and S. Geller, J. Chern. Phys., 51, 348 (1969);(b) S.Gel-
(89)C. Frondel and R. E. Whitfield. Acta Crystallogr., 3, 242 (1950). ler and M. D. Lind, Acta Crystallogr., Sect. 8,25, 2166 (1969).
(90)A . Caron and J. Donohue, J. Phys. Chem., 64, 1767 (1960). (147)(a) J. J. Trillat and J. Forestier, C. R. Acad. Sci., Paris, 192, 559
(91)(a) J. Berkowitz, W. A. Chupka, E. Bromels, and R. L. Belford, J. (1931):(b) K. H. Meyerand Y. Go, Helv. Chim. Acta, 17, 1081 (1934).
Chem. Phys., 47, 4320 (1967); (b) E. Bromels, Ph.D. Thesis, University (148)J. Donohue, S. H. Goodman, and M. Crisp, Acta Crystallogr., Sect. 8,
of Illinois, Urbana, Ill., 1968. 25, 2168 (1969).
(92)(a) L. A. Nimon, V. D. Neff, R. E. Cantley, and R. 0. Buttlar, J. Mol. (149)R. B. Roof, Aust. J. Phys., 25, 335 (1972).
Spectrosc., 22, 105 (1967);(b) L. A. Nimon, Ph.D. Thesis, Kent State (150)C. M. Loomar and F. Tuinstra. Physica, 42, 291 (1969).
University, Kent, Ohio, 1967. (151)J. A. Prins, J. Schenk. and P. A. M. Hospel. Physica, 22, 770 (1956).
(93)S.J. Cyvin, 2. Anorg. Allg, Chem., 378, 117 (1970). (152)S.R. Das. lnd. J. Phys., 12, 163 (1938).
(94) P. D. Bartlett, G. Lohause, and C. D. Weis. J. Am. Chem. SOC., 80, (153)B. C. DeatonandF. A. Blum. Phys. Rev. A, 137, 1131 (1965).
5064 (1958). (154)(a) G. C. Vezzoli, F. Dachille. and R. Roy, Science, 188, 218 (1969);
(95)(a) H. Krebs and H. Beine, 2. Anorg. Ailg. Chem., 355, 113 (1967); (b) (b) lnorg. Chem., 8, 2658 (1969);(c) G. C. Vezzoli and F. Dachille,
H. Krebs and E. F. Weber, 2. Anorg. Allg. Chem., 272, 288 (1953). ibid., 9, 1973 (1970):(d) G. C. Vezzoli and R. J. Zeto, ibid., 9, 2478
(96)H. Rau, T. R. N. Kutty. and J. R. F. Guedes de Carvalho, J. Chem. Ther- (1970);(e) Adv. Chem. Ser., No. 110, 103 (1972);(f) G. C. Vezzoli. J.
modyn., 5, 833 (1973). Polvm. Sci.. 8. 1587 (1970):(a) G.C. Vezzoli. F. Dachille. and R. ROY,
(97)Reference 52,footnote 6. J. klym. SC;.,'~,1557 (1969):
(98)R. E. Davis and H. F. Nakshbendi, J. Am. Chem. Soc., 84, 2085 (155)(a) c. Susse, R. Epain, and B. Vodar, C. R. Acad. Fr., 258, 4513
(1962). (1964);(b) C. Susse and R. Epain, C. R. Acad. Sci.. Paris, Ser. C, 283,
(99)M. Schmidt and E. Wilhelm, lnorg. Nucl. Chem. Leff., I , 39 (1965). 613 11966).
(100)M. Schmidt and H. D. Block, 2.Anorg. Allg. Chem., 385, 119 (1971). (156)C. B: Sklar. L. C. Carrison, W. B. Gager, and 0. M. Stewart, J. Phys.
(101)U. I. Zahorszky, Angew. Chem., 80, 661 (1968). Chern. Solids, 27, 1339 (1966).
(102)I. Kawada and E. Hellner. Angew. Chem., 82, 390 (1970). (157)K. B. Ward, Jr., and B. C. Deaton. Phys. Rev., 153, 947 (1967).
(103)M. Gardner and A. Rogstad, J. Chem. Soc., Dalton Trans., 599 (1973). (158)I. E. P. Paukov, E. Y. Tonkov, and D. S. Mirinski, Dokl. Acad. Nauk.
(104)E. M. Baur and D. A. Horsma, J. Phys. Chem., 78, 1670 (1974). SSSR, 164, 588 (1965).
Chemical Reviews, 1976, Vol. 76, No. 3 Beat Meyer
T. Baak. Science, 148. 1220 (1965). (210) D. D. Davis, R . B. Klemm, and M. Pilling, lnt. J. Chem. Kinet., 4, 367
R. E. Harris and G. Jura, ref lob. p 179. (1972).
E. J. Tonkov, Dokl. Akad. Nauk SSSR, 190, 912 (1970). (211) G. Black, R . L. Sharpless, T. G. Sanger. and D. C. Lorends, J. Chem.
K. Brollos and G. M. Schneider, Ber. Bunsenges. Phys. Chem., 78, 296 Phys. 62, 4274 (1975).
(1974). (212) R. W. Fair, A. Van Roodselaar, and 0. P. Strausz, Can. J. Chem., 49,
M. Kuballa and G. M. Schneider, Ber. Bunsenges. Phys. Chem., 75, 6 1659 (1971).
(1971). (213) (a) R. J. Donovan and D. J. Little, Chem. Phys. Lett., 13, 488 (1972);
S. Block and G. J. Piermarhi, High Temp. High Pressure, 5, 567 (b) R. J. Donovan, D. Husain. and P. T. Jackson, Trans. Faraday Soc.,
(1973). 64, 1798 (1968); (c) R. J. Donovan and W. H. Breckenridge, Chem.
(a) H. Staudinger and W. Kreis, Helv. Chim. Acta, 8, 71 (1924); (b) F. Phys. Lett., 11, 520 (1971); (d) D. J. Little, A. Dalgleish, and R. J. Do-
0. Rice and J. Ditter. J. Am. Chem. Soc.. 75, 6066 (1953); (c) F. 0. novan, Faraday Discuss. Chem. SOC.,53, 21 1 (1972).
Rice and C. Sparrow, ibid., 75, 848 (1953); (d) B. Meyer and E. Schu- (214) R. L. Brown, J. Chem. Phys., 44, 2827 (1966).
macher, Nature (London), 188, 801 (1960); (e) Helv. Chim. Acta, 43, (215) "JANEF Thermochemical Tables", 1974 Suppl. Dow Chemical Co.,
1333 (1960). Midland, Mich.; J. Phys. Chem. Ref. Data, 3, 471 (1974).
B. Meyer, "Low Temperature Spectroscopy, Optical Properties of (216) M. Elbanowski. Rocz. Chem., 43, 1883 (1969).
Molecules in Matrices, Mixed Crystals and Glasses", American Else- (217) R . B. Langford and G. A. Oldershaw, J. Chem. Soc., Faraday Trans. 1,
vier, New York, N.Y., 1971. 70, 1389 (1974).
A. Morelle, Ph.D. Thesis, University of Washington, Seattle, Wash., (218) 0. P. Strausz, R . J. Donovan, and M. deSorgo. Ber. Bunsenges. Phys.
1971. Chem., 72, 253 (1968).
(a) R . F. Bacon and R. Fanelli. lnd. Eng. Chem., 34, 1043 (1942); (b) J. (219) F. D. Wayne, P. B. Davies, and B. A. Thrush, Mol. Phys., 28, 989
Am. Chem. Soc., 65,639 (1943). (1974).
G. P. Ford and V. K. LaMer. J. Am. Chem. SOC.,72, 1959 (1950). (220) J. F. Bott and T. A. Jacobs, J. Chem. Phys., 52, 3545 (1970).
S. Hamada, Y. Nakazawa, and T. Shirai, Bull. Chem. SOC. Jpn., 43, (221) J. Drowart and P. Goldfinger, 0.Rev., Chem. SOC.,20, 545 (1966).
3096 (1970). (222) P. Budininkas, R. K. Edwards, and P. G. Wahlbeck, J. Chem. Phys., 48,
I. E. Bolotov. G. N. Kleptsova. and P. S. Mel'nikov, Kristallografiya, 16, 2859 (1968).
400 (1971). (223) V. H. Dlbeler and S. K. Liston, J. Chem. Phys., 49, 482 (1968).
M. D. Gernez, C. R. Acad. Sci. Fr., 82, 115 (1876). (224) J. M. Ricks and R. F. Barrow, Can. J. Phys., 47, 2423 (1969).
P. Pacor, Anal. Chim. Acta, 37, 200 (1967). (225) (a) L. Brewer, G. D. Brabson, and 8. Meyer, J. Chem. Phys., 42, 1385
F. Feher. G. P. Goerler, and H. D. Lutz. Z. Anorg. Allg. Chem., 382, (1965); (b) L. Brewer and G. D. Brabson. ibid., 44, 3274 (1966); (c) B.
135 (1971). Meyer, ibid., 37, 1577 (1962); (d) R . E. Barletta. H. H. Claessen, and R .
F. Feher and E. Helling, Z. Anorg. Allg. Chem., 294, 63 (1958). L. McBeth. ibid., 55, 5409 (1971).
F. Feher and H. D. Lutz, 2. Anorg. Allg. Chem., 333, 216 (1964). (226) H. Erdmann, Justus Liebigs Ann. Chem., 362, 133 (1908).
T. Doi, Rev. Phys. Chem. Jpn., 37, 62 (1967). (227) (a) A. G. Hopkins, S.Tang, and C. W. Brown, J. Am. Chem. SOC., 95,
A. H. W. Aten, Z. Phys. Chem.. 83, 442 (1913). 3486 (1973); (b) S. Y. Tang and C. W. Brown, lnorg. Chem., 14, 2856
T. K. Wiewiorowski, A. Parthasarathy. and B. Slaten, J. Phys. Chem., (1975).
72, 1890 (1968). (228) T. Chivers and I. Drummond, lnorg. Chem., 13, 1222 (1974).
J. A. Semlyen, Polymer, 12, 383 (1971). (229) B. Merkenich, Ph.D. Thesis, Bonn, 1960.
(a) D. C. Koningsberger and T. DeNeef. Chem. Phys. Lett., 14, 453 (230) G. Schneider, Z. Phys. Chem., 41, 110 (1964).
(1972); (b) D. C. Koningsberger, Ph.D. Thesis, Eindhoven, 1971. (231) J. W. King and P. R . Quinney, J. Phys. Chem., 78, 2635 (1974).
W. Patel and L. B. Borst, J. Chem. Phys., 54, 822 (1971). (232) R . F. Matson, T. K. Wiewiorowski, D. E. Schoff, Jr.. and R . A. Griffin,
J. A. Poulis and C. H. Massen, ref lob. p 109. unpublished results.
(a) R . K. Steunenberg, C. Trapp, R. M. Yonco, and E. J. Cairns, Adv. (233) D. Jensen, J. Smith, and B. Meyer, J. Chem. Eng. Data, 15, 144
Chem. Ser., No. 110, 190 (1972); (b) 0. Watanabi and S. Tamaki, (1970).
Electrochim. Acta, 13, 11 (1968). (234) J. Austin, D. Jensen, and B. Meyer. J. Chem. Eng. Data, 16, 364
K. Ono and T. Matsushima, J. Sci. Res. (Tohoku Univ.) Ser. A, 9, 309 (1971).
(1957); 10, 58, 375 (1956). (235) M. A. Lallemand, C. R. Acad. Sci., 70, 182 (1870).
J. A. Poulis, C. H. Massen, and P. van der Leeder, Trans. Faraday (236) C. F. Geitner, Pharm. Ann., 129, 350 (1864).
SOC.,58, 52, 474 (1962). (237) A. Teder, Acta Chem. Scand., 25, 1722 (1971).
J. Schenk, Physica, 23, 325 (1957). (238) (a) W. Giggenbach, lnorg. Chem., 13, 1724 (1974); (b) ibid., 11, 1201
H. Eyring and F. W. Cagle, J. Phys. Chem., 57, 942 (1953). (1972).
A. Eisenberg, Macromolecules, 2, 44 (1969). (239) (a) E. F. Muller, Ph.D. Thesis, University of Calgary, Alberta, 1968; (b)
W. J. MacKnight, J. A. Poulis, and C. H. Massen, J. Macromol. Sci. E. F. Muller and J. 6. Hyne, Oil Gas J., 66, 107 (1968); (c) J. 6. Hyne,
(Chem.), A I , 699 (1967). E. F. Muller, and T. K. Wiewiorowski, J. Phys. Chem., 70, 3733 (1966).
W. Klement, J. Chem. Phys., 45, 1421 (1966). (240) H. G. Schnering and N. K. Goh, Naturwissenschaften, 61, 272 (. 1974).
(a) A. T. Ward and M. B. Myers, J. Phys. Chem.. 73, 1374 (1969); (b) (241) (a) M. lkezawa and J. Roife, J. Chem. Phys., 58, 2024 (1973); (b) D. M.
A. T. Ward, ibid., 72, 4133 (1968); (c) Adv. Chem. Ser., No. 110, 163 Gruen. R. L. McBeth, and A. J. Zielen, J. Am. Chem. SOC.,93, 6691
(1972). (1971).
W. Klement. J. Polym. Sci., 12, 815 (1974). (242) (a) W. Holzer, W. F. Murphy, and H. J. Bernstein, Chem. Phys. Lett.. 4,
A. Wigand. Z. Phys. Chem., 85, 442 (1909). 641 (1970); (b) J. Mol. Spectrosc., 32, 13 (1969).
(a) T. K. Wiewiorowski and F. J. Touro. J. Phys. Chem., 70, 234 (243) W. Giggenbach, lnorg. Chem.. I O , 1308 (1971).
(1966); (b) F. J. Touro and T. K. Wiewiorowski, ibid., 70, 239 (1966): (244) (a) W. F. Giggenbach. J. Chem. SOC., Dalton Trans., 729 (1973); (b)
(c) T. K. Wiewiorowski and F. J. Touro, ibid., 70, 3528 (1966); (d) T. K. ibid., 832 (1970); (c) ibid., 852 (1970).
Wiewiorowski, Endeavour, 29, 9 (1970). (245) T. Chivers and I. Drummond, J. Chem. SOC., Dalton Trans., 631
P. A. Rubero, J. Chem. Eng. Data, 9, 481 (1964). (1974).
D. M. Gardner and G. K. Fraenkel, J. Am. Chem. SOC., 78, 3279 (246) (a) F. See1 and G. Simon, Z. Naturforsch. B, 27, 1110 (1972); (b) F.
(1956). See1 and H. J. Guttler, Angew. Chem.. lnt. Ed. Engl., 12, 420 (1973).
. . G. C. Havward and P. J. Hendra. Soectrochim. Acta, Pari A, 23,
(a\ (247) S. D. McLaughlan and D. J. Marshall, J. Phys. Chem., 74, 1359 (1970).
1937 (1967); (b) J. Jander and G. Turk, 'Chem. Ber., 97. 25 (1964); (c) (248) T. Chivers. Nature (London), 252, 32 (1974).
T. Bjorvatten. Acta Chim. Scand., 18, 749 (1962). (249) (a) N. G. Vannerberg, Prog. horg. Chem., 4, 125 (1962): (b) L. V. Aza-
(199) B. Meyer. T. Stroyer-Hansen, and T. V. Oommen, J. Mol. Spectrosc., rov and I. Corrin. Proc. Natl. Acad. Sci. U.S.A., 49, 1 (1963); (c) L. An-
42, 335 (1972). drews, personal communication.
(200) 6. Meyer and T. Stroyer-Hansen, J. Phys. Chem., 78, 3968 (1972). (250) (a) E. Hayon, A. Treinin, and J. Wilf, J. Am. Chem. SOC.,94, 47 (1972);
(201) (a) F. D. Rossini, J. Chem. Thermodyn.. 2, 447 (1970); (b) A. Dumas, (b) L. Andrews. personal communication.
Ann. Chim. Phys., 50, 175 (1811); (c) H. Davy, Phil. Trans., 1, 59 (251) (a) M. C. R. Symons, M. Stillings, and J. G. Wilkinson. J. Chem. SOC.,
(1809). Dalton Trans., 372 (1971); (b) M. Stillings. M. C. R . Symons, and J. G.
(202) E. H. Baker, Miner. Process. Extr. Metall.. 60, C93 (1971). Wilkinson, J. Chem. SOC.A, 3201 (1971).
(203) H. Rau, T. R . N. Kutty. and J. R . F. Guedes de Carvalho. J. Chem. Ther- (252) R . A. Beaudet and P. J. Stephens, J. Chem. SOC.D, 1083 (1971).
modyn., 5, 291 (1973). (253) G. Knippschild. Ph.D. Thesis, Wurzburg, 1968.
(204) G. Preuner and W. Schupp. Z. Phys. Chem., 68, 129 (1909). (254) M. Schmidt and D. Eichelsdorfer. Z. Anorg. Allg. Chem.. 330, 122
(205) H. Braune and E. Steinbacher, Z. Naturforsch., A, 7, 486 (1952). ( 1964).
(206) K. K Yee, R. F. Barrow, and A. Rogstad, J. Chem. SOC., Faraday (255) (a) R . E. Davis, J. Am. Chem. SOC., 60, 3565 (1958); (b) Proc. Indiana
Trans. 2, 66, 1808 (1972). Acad. Scl., 70, 100 (1960).
(207) R. F. Barrow and R . P. du Parcq, ref lob, p 251. (256) (a) E. J. Woodhouse and T. H. Norris. J. lnorg. Nucl. Chem., in press;
(208) For references to the work of H. E. Gunning and 0. P. Strausz see: (a) (b) J. R . Mickelsen and T. H. Norris, lnorg. Chem., 5, 917 (1966); (c) D.
H. E. Gunning and 0 . P. Strausz, Adv. Photochem., 4, 143 (1966); (b) E. Burge and T. H. Norris. J. Am. Chem. SOC.,81, 2329 (1959).
0. P. Strausz in "Sulfur in Organic and inorganic Chemistry", Vol. 2, (257) H. Juraszyk, Chem. Z., 98, 127 (1974).
A. Senning, Ed., Marcel Dekker, New York. N.Y.. 1972, p 1; (c) H. E. (258) S. Oae, Bull. Chem. SOC.Jpn., 46, 648 (1973).
Gunning, ref lob, p 265. (259) H. J. Langerand J. B. Hyne, Adv. Chem. Ser., No. 110, 113 (1972).
(209) K. Gollnick and E. Leppin, J. Am. Chem. Soc.. 92, 2217 (1970). (260) 6. Meyer, unpublished results.