J. Chem.

Thermodynamics 1973, 5, 833-844

Thermodynamics of sulphur vapour

HANS RAU, T. R. N. KUTTY, a and
J. R. F. GUEDES DE CARVALHO b

Philips Forschungslaboratorium Aachen GmbH, Aachen, Germany

(Received 1 January 1973; in revised form 26 February 1973)
Density measurements of sulphur vapour up to saturation in the temperature range
between 823 and 1273 K were performed. From the results, together with literature data,
a set of equations was derived which allows the partial pressures of the different molecular
species to be calculated as a function of total pressure and temperature. Real gas corrections
are included, so that these equations can be used up to 1273 K and the saturation pressure
of 144 arm. A FORTRAN program for calculation of the vapour density and the partial
pressures of $2, S~. . . . , Se from the total pressure and the temperature is available from
the first author.
The standard enthalpy of formation of S2(g) was found to be
AH(S2, g, 298.15 K) = (31200 4- 50) calth mo1-1.

1. Introduction
Sulphur vapours are very complex in composition; molecules from $1 to S s are known
to exist in equilibrium. Since the stability of $2 is high, $I molecules become important
only at very high temperatures and low pressures. Therefore, either the equilibrium
between $I and $2 or that between $2 and all the other species from S s to $8 is
dominant. The first of these equilibria is well known c~) and will not be dealt with in
this study.
F o r evaluation of the complex equilibria between $2 and Ss to $8 two different
experimental methods were used: (i) determinations of the mean molar mass as a
function of total pressure and temperature and (ii) mass spectrometry. The first type
of experiment was performed recently by Braune, Peter, and Neveling, ~2) who
measured vapour densities up to 1273 K and about 1 atm.~ Mass spectrometry was
done by Berkowitz et aL (4-6~ and, with a special technique, the electrochemical
Knudsen cell, by Detry et aL c7~ The study of Berkowitz et aL is more qualitative in
character, because distinguishing between parent ions and ions generated by fragmentation in the mass spectrometer was difficult, and also because the sensitivity of the
mass spectrometer for the different species could only be estimated.
The electrochemical Knudsen cell of Detry et al. (7~ allows parent ions and fragments
to be more or less distinguished in the spectrometer. Here an electrochemical cell
a Present address: Indian Institute of Science, Bangalore, India.
Present address: University of Porto, Faculty of Engineering, Porto, Portugal.
t Throughout this paper arm = 101.325 kPa; calth = 4.184 J.

834

H. RAU, T. R. N. KUTTY, AND J. R. F. GUEDES DE CARVALHO

(Ag[AgIIAg2SIPt) is mounted in a Knudsen cell. With the help of the potential

applied to the cell the chemical potential of the sulphur in the Knudsen cell can be
changed within wide limits up to saturation. On the other hand, the current flowing
through the cell is a direct measure of the amount of sulphur penetrating through the
hole of the Knudsen cell.
When the logarithm of the ion intensity in the mass spectrometer is plotted against
the potential, the different species should have different slopes. When the slope
observed for a certain species is in agreement with its theoretical value, this is thought
to be the parent ion intensity, because fragment ions should show more or less the
slope of the ions from which they were generated.
The current through the cell allows the mass spectrometer sensitivity to be calibrated,
because the total current must be the sum of the currents due to the different ions,
parent and fragmentary. Some difficulties arise for the big molecules. Here the slope
of the curve of the logarithm of the ion intensity against potential will always show the
theoretical value, because the intensity of these ions cannot be increased by fragmentary ions (fragmentary ions will always be smaller). On the other hand, part of
these big molecules will become broken up by the electron beam in the mass spectrometer, and determination of this part is not easy.
Mass spectrometric studies connected with a Knudsen cell are restricted to pressures
below about 10- 3 atm. This type of experiment was therefore done at low temperatures
only (for vapour not far from saturation) or on diluted vapours (e.g. vapours above
CdS and ZnS), where only Sa and some $4, besides $2 as the main constituent, are
present.
Nothing is known of dense vapours not far from saturation at high temperatures,
where pressures become high. Mass spectrometric studies are excluded here and it is
only from p, V, T measurements that the equilibria in the vapour phase be derived.
One of us (H. R.)recently designed an all-silica Bourdon gauge(s) which allows
such density measurements to be made with the necessary accuracy. Such measurements, up to 1273 K for diluted and dense vapours (up to their saturation point), are
presented in this paper. From the results and some data from the literature a set of
equations has been derived which allows the partial pressures of all the species from
S2 to $8 to be calculated from the total pressure and the temperature. Real gas
corrections are included in these equations, which can therefore be used between
473 and 1273 K and up to the respective saturation pressures.

2. Experimental
MATERIALS
The sulphur used was high purity sulphur from Johnson, Matthey and Co., London
and sulphur "puriss" (i> 99.999 mass per cent) from Fluka AG, Switzerland. The first
sample was used either as delivered or after it had been twice distilled in vacuum to
remove some volatile impurities present (mainly H2S). No significant differences
between the results obtained with the different samples could be detected.

THERMODYNAMICS OF SULPHUR VAPOUR

835

APPARATUS AND MEASUREMENTS

The apparatus consisted of an all-silica Bourdon gauge of known internal volume,
which was mounted inside a furnace in an autoclave. The pointer of the gauge extended
from the furnace and could be observed visually through optical windows in the
autoclave. The gauge was used as a null instrument: the internal pressure (sulphur
vapour) which forces the pointer out of the null position is exactly compensated by
external argon pressure. This argon pressure, maintained in the autoclave, is then
measured with a precise gauge (__+0.1 per cent) connected to the pressure line. Details
of the apparatus and its working principle are given elsewhere, t3, s) where the sensitivity, accuracy, and thermal aspects are also discussed.
For a typical experiment a known quantity of sulphur was poured into the silica
Bourdon gauge, the volume of which was exactly known. After evacuation the gauge
was sealed off and mounted in the autoclave. The pressure exerted by the vapour
was measured for a number of temperatures. When the pressure was less than the
saturation pressure at that temperature, t3) the density of the vapour could be easily
calculated from the mass of the sulphur taken and the volume of the gauge.

3. Previous work
In the vapour there exists a complicated equilibrium between the different molecular
species from $2 to S8. A set of equilibrium constants is necessary in order to describe
this equilibrium state. Some thermodynamic values were already known and were
used for the calculations described below.
HEAT CAPACITIES
Values of Cp are known for $2, ~9) $6, ~1) and Sa,cx~) from spectroscopic studies. For
the other species the values of Cp had to be estimated. For that purpose the vibrational
heat capacity per degree of freedom of $2, $6, and Sa was drawn as a function of the
number of atoms in the molecule with the temperature as a parameter (figure 1). It
was assumed that the vibrational heat capacities of all the molecules lie on the same
curves. Thus the heat capacities of $3, $4, $5, and $7 were estimated to be the sum of
the vibrational heat capacities taken from figure 1 and the rotational and transitional
increments. The heat capacities used for the calculations are shown in table 1.
ENTROPIES
Entropies for the gaseous molecules are given in the literature for $2, c9) $6, ta~ and
Ss .c11'~2) These quantities are calculated from spectral data. Luft~12) and Guthrie
et aL ~ ) used different assignments of the known frequencies of $8, resulting in two
widely differing values for its standard entropy. Luft's value does not agree with the
equilibrium data of Detry et aL(7) and is expected to be incorrect. We therefore took
the value of Guthrie et aL c11)
The entropies of the other molecular species are not known exactly. Values are
given by Detry et aL,(7) calculated from estimated vibrational frequencies. Better
values of these entropies had to be calculated from an adjustment of the equilibrium
constants to the measured vapour densities (see below).

836

H. RAU, T. R. N. KUTTY, AND J. R. F. GUEDES DE CARVALHO

[

|
/

L-

1000 K -4

,, 2.0~i

"

r
3

1
4

.xx3X
~ '7~0K0 K 1

"~ 1.5
I

0.5
2

I
I
[
5
6
7
8
i
FIGURE 1. Vibrational heat capacities C~(vib.)per degree of freedom of gaseous sulphur molecules S~. Experimental points are from spectroscopic investigation.(9-11)
TABLE 1. Heat capacities Cp of gaseous sulphur molecules. C~ is given by
Cdcalth K -1 mo1-1 = A + IO-aB(T/K) + 105C(T/K) 2
(calth = 4.184 J)

$2
$3
$4
$5
$6
$7
Sa

8.54
12.854
19.092
25.558
31.580
37.038
42.670

0.28
1.04
0.783
0.253
0.120
0.613
0.860

-- 0.79
-- 1.554
-- 2.820
-- 3.771
-- 4.400
-- 4.723
-- 5.110

ENTHALPIES OF FORMATION
Enthalpies of formation can be found in the literature for $2, ) and Ss. (11) The value
for $2 given by Kubaschewski e t al., (9) (31.0+ 1.0)kcalth mo1-1, has far too wide
limits of error to be used in this study. From the partial pressures of S2 in the saturated
vapour given by Detry e t al. (7) a value of 30.83 kcalth mo1-1 can be calculated.
The enthalpy of formation of $8 was calculated by Guthrie e t al. (H) to be 25.23
kcalth mol-1, using their own entropy value and vapour pressures of rhombic sulphur
near room temperature taken from the literature. Here Ss is the only species in the
vapour phase. Unfortunately, Guthde e t aL apparently made a mistake in their
calculations. Taking the pressures cited by them and the heat capacities of $2 and
rhombic sulphur, the correct value of the enthalpy of formation of $8 is found to be
24.32 kcalth m o l - 2.
Approximate values for the enthalpies of formation can be derived from the
composition of the saturated vapours between 473 and 673 K given by Detry e t aL (7)

THERMODYNAMICS OF SULPHUR VAPOUR

837

4. Calculations
REAL GAS CORRECTIONS
From the preceding section it follows that the thermodynamic properties of S 3, S,, Ss,
$6, and $7 are only approximately known and that these quantifies have to be fitted
to the densities measured here. Fugacity coefficients have to be included to correct the
equilibrium constants, which describe the equilibria between $2 and all the other
species for real gas behaviour when pressures are high.
The critical properties of sulphur were recently determined by the authors. O) There
it was also mentioned that sulphur vapours can be assumed to behave like ideal
mixtures of the different molecular species. In other words, the partial molar volumes
of the species are equal to the volumes the pure species would have under the pressure
of the mixture. Hence the fugacity coefficients Ss are equal for all the different species
and depend on only the total pressure and the temperature: (13)
(S2) --- qS(S3) . . . . .
q~(Ss) = qS(Ptota,).
A similar equation holds for the partial molar compression factors Zs, where
p V = ZRT,

(1)
(2)

which are equal for all the species too:

Z ( S 2 ) ---~Z ( S 3 ) . . . . .

Z ( S s ) = Z(Ptotal).

(3)

Values of ~b and Z were taken from the "tables of the generalized properties of
pure gases and liquids", (14) using as parameters the critical properties of sulphur. O)
The total pressure p is a sum of the partial pressures of the species:
8

p = E p(S,).
S=2

(4)

The equilibria:

Ss =

iS2,

are given by the equilibrium constants Ks:

Kf = p(S2)~/2qbf/2/p(S~)c~,
From equation (6):
p(S~) = p($2)~/2~ ('/2- a)/Ks,

(5)

(6)
(7)

hence
S

p = F. p(S2)f/24~(f/2-1)/K~,

(8)

f=2

where K 2 = 1.
The contribution Ps of the i-th species to the density is
Ps = P(S3MdZRT,
where the molar mass Ms is given by
Ms = 32.064i g mol- 1.

(9)
(10)

The density p of the vapour is therefore given by the sum of the contributions Ps:
8

p = Z ps.
f=2

838

H. RAU, T. R. N. KUTTY, AND J. R. F. GUEDES DE CARVALHO

A computer program was written which (1) interpolates the fugacity and the
compression factors from the "tables of the generalized properties of pure gases and
liquids ''(14) by parabolic functions, (2) calculates the equilibrium constants K~ from
a given set of enthalpies of formation, standard entropies, and heat capacities of all
the species, (3) calculates the partial pressures p(Si) in such a way that the sum of
these is equal to the measured total pressure p according to equations (7) and (8), and
(4) computes the density p from these partial pressures according to equation (I 1).
As already mentioned, exact thermodynamic properties were not known for $3, $4,
$5, $6, and S7. We therefore started with the approximate values derived from the
work of Detry et aL(7) The final set of thermodynamic properties should fulfil the
following conditions: in the temperature range of the investigations of Detry et a/.(7)
the measured partial pressures of the different species should be represented by the
calculated pressures within the limits of error; and the calculated densities of the
vapours should be in agreement with the experiments over the whole range of temperature and pressure.
Detry et aL(v) accurately measured the equilibria of Ss with S7 and of $8 with $6,
respectively. Error limits were small in these cases. Since the thermodynamic properties
of $8 are exactly known, the results of Detry et al. allow the thermodynamic properties
of $6 (enthalpy of formation) and of $7 (enthalpy of formation and standard entropy)
to be calculated. At not too high temperatures $6, $7, and $8 are the main constituents
in the vapour phase when the total pressure approaches the saturation point. Therefore, even if the partial pressures of $2 to S5 were known only approximately from
the data of Detry et aL, the densities calculated on the basis of their data should be in
reasonable agreement with the experiments. A first check in that direction showed
this not to be the case. Even variations of the equilibrium constants for the formation
of Sa, $4, and $5 f ~ m S2 could not bring experimental and calculated values into
agreement.
Two possible reasons for this behaviour were considered: either tautomers of the
bigger molecules are present at higher temperatures, or the enthalpy of formation of
$2 derived from the data of Detry et al. (7) is not completely correct.
The possible presence of tautomers of $8 in high temperature vapours was discussed
by Guthrie et al. (a a) on the basis of machined models of the $8 molecule. They found
that besides the normal molecule of D4d symmetry ("crown" modification) two other
molecules of D2a and of Ca symmetry should be taken into account. Estimates of the
difference in internal energy of these molecules compared with the crown modification
were made by Guthrie et aL (al) from the energy of bond rotations of molecules like
S2C12, and by Pauling(aS) from the difference in the enthalpies of formation of $6
and Ss, with quite different results. These lie in the range between 4.9 kcalth tool -a
(Pauling) and 9 to 15 kcalta tool -a (Guthrie et aL).
The symmetry numbers of the tautomeric molecules are 2 (D2a) and 8 (C0, (ta)
where the second number must be doubled because of d- and 1-isomers. For the
simplest case, where only the symmetry number of the molecules contributes to the
entropy, one has for Ks, the equilibrium constant of the reaction:
S8 -- 4S2,

(12)

THERMODYNAMICS OF SULPHUR VAPOUR

839

K~ = Ks/{1 + 18 e x p ( - E / k T ) } ,

(13)

the expression:
where/(8 is the constant of reaction (12) formulated for the crown modification only
and E is the difference in internal energy between the crown form and the 18 tautomeric molecules. Differences in moments of inertia and vibrational frequencies from
those of the crown modification will alter the entropy contribution somewhat from
Rln 18.
Similar tautomeric molecules could be thought of for the other molecules, and a
set of equations similar to equations (13) can be expected in this case. When the energy
differences lie below about 8 kcalth mo1-1, as estimated by Pauling,(15) these tautomeric molecules will contribute appreciably to the vapour composition.
We have attempted to fit the experimental results to equilibrium constants based on
the thermodynamic properties given by Detry et aL, (7) especially the enthalpy of
formation of $2 derived from their results, taking into account the possible presence
of tautomeric molecules in the way discussed here. The result was negative: (i) systematic deviations of the calculated densities from the measured ones at medium
temperatures were found, and (ii) the partial pressures of $6, S7, and Ss showed, at
lower temperatures, a completely different variation with temperature to that found
experimentally by Detry et al. (7) Consequently, the presence of significant amounts of
tantomeric molecules even at the highest temperatures under consideration was ruled
out. This means that the energy difference between the tautomeric and the normal
molecules is higher than about 10 kcalth tool-1.
The second possibility, that the enthalpy of formation of Sz(g) is incorrect, implies
that the partial pressures of Sz in the saturated vapours given by Detry et aL (7) are
not correct. This is not easy to understand from the type of measurements (electrochemical Knudsen cell) performed. The calibration of the Knudsen cell is then easy,
because $2 is the main or even only constituent in diluted vapours, and the extrapolation to the saturation point was done with the theoretical slope of the curve:
logarithm of the current connected with the Sz molecule against the potential of the
cell. This seems to be a sound procedure. On the other hand, it will now be shown that
the enthalpy of formation of $2 is higher by some 100 calth mo1-1 than that derived
from the data of Detry et a/. (7) Perhaps there was an overpotential or an electrical
leakage in the cell used by these authors.
When the enthalpy of formation of S2 is varied, then, the bigger the molecules
involved, the greater is the variation of the equilibrium constants of the reactions
S~ = iS2.

(5)

Thus, with a value of

AH~(S2, g, 298.15 K) = 31.20 kcalth mol- ~,
the measured densities at all temperatures and the partial pressures of S6 to Sa found
by Detry et al. (7) at temperatures between 473 and 673 K are represented well by the
values calculated from the equilibrium constants (see equations (4) to (11)). Some
smaller corrections of the thermodynamic properties of Sa, $4, and Ss were necessary
in order to bring the values calculated as near as possible to those measured. These

840

H. RAU, T. R. N. KUTTY, AND J. R. F. GUEDES DE CARVALHO

corrections are within t h e e r r o r limits given b y D e t r y et aL for their results. The

t h e r m o d y n a m i c p r o p e r t i e s o f the different m o l e c u l a r species fitted to the experimental
results are given in t a b l e 2. T a b l e 3 c o m p a r e s the m e a s u r e d v a p o u r densities (present
values) with the densities calculated f r o m the equations for the equilibrium constants
using the d a t a in tables 1 a n d 2. T a b l e 4 c o m p a r e s the p a r t i a l pressures derived from
these equations with t h o s e f o u n d experimentally b y D e t r y et al. (7) As can be seen,
the densities agree m o s t l y within _+4 per cent with t h o s e calculated; a n d the partial
pressures, except those o f S 2 which are d e a r l y smaller, are in acceptable agreement
with the e x p e r i m e n t a l values.
T h e densities m e a s u r e d b y Braune, Peter, a n d Neveling (2) are also in close agreement
w i t h t h o s e calculated f r o m the d a t a given in tables 1 a n d 2.
F i g u r e 2 is a survey o f the mole fractions o f the different species in the saturated
v a p o u r s b e t w e e n 773 a n d 1273 K . A t low t e m p e r a t u r e s the b i g molecules, S 6 to Ss,
p r e d o m i n a t e , b u t their a m o u n t s decrease with t e m p e r a t u r e , a n d s o o n $2 a n d S a
predominate.

TABLE 2. Thermodynamic data of the gaseous sulphur molecules S~ (i = 2 to 8). The standard state
is the ideal gas at 1 atm pressure and 298.15 K
(caltn = 4.184 J)
i

AHt/kcalt~ tool- 1

2
3
4
5
6
7
8

31.20
33.81
34.84
26.14
24.36
27.17
24.32

S/cal~hK - x mol- 1
54.40 ()
64.39
74.22
73.74
84.60 el)
97.41
102.76 (11)

TABLE 3. Comparison of calculated and measured vapour densities p as a function of pressure p.

The calculations are performed with the thermodynamic data in tables 1 and 2 according to
equations (8) and (11). Experimental results from this work only.
(atm -- 101.325 kPa)
p/atm

p(expt)
mg cm -a

p(calc)
mg cm -a

p(expt)
mg cm -8

p(calc)
mg em -a

1.864
2.295
3.150
3.559

5.409
7.005
9.695
11.28

5.454
6.863
9.723
11.18

2.783
3.695
4.164
4.008
4.722

7.005
9.695
11.28
10.64
13.09

7.043
9.786
11.23
10.75
12.98

p/atm
T = 823 K

0.689
0.762
1.157
1.757

1.721
1.852
3.059
5.076

1.755
1.974
3.191
5.104

0.905
0.966
1.442
2.109
2.218

1.721
1.852
3.059
5.076
5.409

1.797
1.952
3.215
5.084
5.397

T -- 873 K

841

THERMODYNAMICS OF SULPHUR VAPOUR

p/atm

p(expt)
mg cm -3

TABLE 3--continued
p(calc)
p/atm
mg cm -z

1.204
1.273
1.817
2.651
2.770
3.414
4.471
4.845

1.721
.852
3.059
5.076
5.409
7.005
9.695
10.64

1.802
1.941
3.120
5.094
5.387
7.017
9.808
10.82

1.551
1.620
2.313
3.396
3.518
4.301
5.531
6.022
6.246

1.721
1.852
3.059
5.076
5.409
7.005
9.695
10.64
11.28

1.770
1.874
3.021
5.078
5.326
6.972
9.732
10.88
11.41

1.858
1.980
2.886
4.293
4.430
5.417
6.893
7.778
8.574

1.721
1.852
3.059
5.076
5.409
7.005
9.695
11.28
13.09

1.724
1.861
2.979
5.031
5.248
6.894
9.586
11.31
12.92

2.109
2.266
3.429
5.233
5.437
6.655
8.520
9.316
9.642
10.58
13.20
13.56

1.721
1.852
3.059
5.076
5.409
7.005
9.695
10.64
11.28
13.09
7.46
18.51

1.723
1.865
2.998
5.024
5.274
6.849
9.516
10.74
11.26
12.77
17.35
17.99

12.83
21.94
35.25
46.54

10.64
20.87
40.08
59.45

10.67
21.02
40.22
60.21

15.32
27.92
46.82
62.88
77.30
89.96

10.64
20.87
40.08
59.45
79.82
100.0

10.69
21.17
40.19
59.89
80.79
102.1

p(expt)
nag cm -3

p(cale)
mg cm -3

T = 923 K
5.049
5.661
7.213
7.445
8.316
8.486
9.030

11.28
13.09
7.46
18.51
20.87
21.55
22.95

11.39
13.10
17.58
18.27
20.90
21.42
23.11

6.893
8.764
8.982
10.04
10.76
12.13
13.93
15.45

13.09
17.46
18.51
20.87
22.95
27.31
31.88
37.55

12.98
17.73
18.30
21.11
23.06
26.84
3.96
36.44

10.74
11.04
12.32
13.12
14.72
16.92
18.54
22.35
22.63

17.46
18.51
20.87
22.95
27.31
31.88
37,55
47.52
47.67

17.55
18.21
21.12
22.99
26.82
32.30
36.49
46.84
47.62

15.16
15.25
16.04
17.98
20.65
22.52
23.86
24.29
27.03
27.44
29.97

20.87
20.87
22.95
27.31
31.88
37.55
39.13
40.08
47.52
47.67
55.63

21.02
21.19
22.74
26.64
32.32
36.47
39.52
40.52
47.03
48.04
54.35

55.66
63.21
71.31

79.82
100.0
121.2

78.86
95.90
115.9

120.4
121.2
142.6
168.1
211.7
254.1

122.5
125.8
140.9
168.9
202.1
259.7

T = 973 K

T = 1023 K

T---- 1073 K

T = 1173 K

T----- 1273 K
100.7
102.3
109.4
120.4
130.8
143.6

842

rI. R A U , T. R. N. KUTTY, A N D J. R. F. G U E D E S D E CARVALHO

TABLE 4. Comparison of the partial pressures p, in saturated sulphur vapours given by Detry
et al., cv~ found by measurements with the electrochemical Knudsen cell, with those calculated from
equations (8) and (11) using the thermodynamic data in tables 1 and 2
(atm = 101.325 kPa)
Species

pdatm
Detry et al.

$2
Sa
$4
S~
Se
ST
$8

1.40x
1.70 x
1.65 x
1.56 x
5.50 x
3.28 X
1.89 x

T=473K
10 -6
10 -7
10 -T
10 -5
10 -4
10 -4
10 - 8

$2
Sa
$4
$5
$5
ST
$8

2.68
3.66
3.25
9.64
1.60
1.27
3.64

T=573K
10 -4
x 10 -8
x 10 -5
10 -4
X 10 -2
10 -2
10 -2

Sa
Sa
$4
So

9.40
1.34
1.04
1.43

x
x

Species
This study

8.92
1.47
1.26
1.93
5.63
3.30

x
X

X
X

p,/atm
Detry et aL

10 -7
10 -7
10 -7
10 -n
10 -4
10 -4

1.88 10 - 3

$2
Sa
$4
$5
$6
ST
$8

1.85 x 10 -4
3.93 X 10 -8
3.42 10 -8
8.81X 10 -4
1.56 X 10 -2
1.30 X 10 -2
3.65 10 -2

$2
Sa
$4
$8
$8
$7
$5

7.11
1.73
1.47
1.05

This study

T=523K
2.60 X 10 -8
3.38 10 -6
3.04X 10 -8
1.72 10 -4
3.60 X 10 -a
2.63 10 -a
1.02 10 -z
T=623K
1.90 x 10 -a
2.68 10 -4
2.15 10 -a
4.20 10 -a
5.25 10 -z
4.55 10 -2
9.70 10 -z

1.69
3.23
2.81
1.63 x
3.65
2.61X
1.02 x

10 -5
10 -6
10-n
10 -4
10 -3
10 -3
10 -2

1.34
3.08
2.65
3.43
4.96
4.64
9.87

10 -z
10 -4
10 -4
10 -3
10 -2
10 -2
10 -2

1.37 x 10 -1
1.26 x 10 -1
2 . 1 4 x 10 -1

1.28 x 10 -1
1.31 x 10 -1
2.19 x 10 -1

x
X

T=673K
10 -a
10 -a
10 -a
10 -2

10 -a
x 10 -a

$6
$7

x 10 - a

So

x 10 -a

T h e a c c u r a c y o f t h e t h e r m o d y n a m i c p r o p e r t i e s i n t a b l e s 1 a n d 2 c a n h a r d l y be
e s t i m a t e d . T h e e n t h a l p y o f f o r m a t i o n o f $2 m a y b e q u i t e c o r r e c t , p e r h a p s t o w i t h i n
___50 calta m o l - 1 , b e c a u s e a v a r i a t i o n o f this o r d e r o f m a g n i t u d e a l r e a d y results in a
s y s t e m a t i c d e v i a t i o n o f t h e c a l c u l a t e d f r o m t h e m e a s u r e d densities. T h e o t h e r values
m a y b e slightly less a c c u r a t e , b e c a u s e s o m e o f t h e m c a n b e v a r i e d a p p r e c i a b l y
( a l t h o u g h n o t i n d e p e n d e n t l y ) w i t h o u t m u c h effect. T h i s is especially t r u e f o r the
m i n o r c o n s t i t u e n t s , $4 a n d Ss, t h e p r o p e r t i e s o f w h i c h a r e c e r t a i n l y n o t v e r y closely
defined. T h e e n t r o p y o f $6 (lo) is p e r h a p s n o t c o m p l e t e l y c o r r e c t , as c a n b e seen f r o m
t a b l e 4. H e r e t h e p a r t i a l p r e s s u r e o f $6 d e v i a t e s in a s y s t e m a t i c m a n n e r f r o m t h e values
d e t e r m i n e d b y D e t r y e t al.
O n t h e o t h e r h a n d t h e t h e r m o d y n a m i c p r o p e r t i e s in t a b l e s 1 a n d 2 r e p r e s e n t a
s y s t e m w h i c h is o n t h e w h o l e c o n s i s t e n t w i t h t h e e x p e r i m e n t a l results. I f m o r e d e t a i l e d
i n f o r m a t i o n o n t h e p r o p e r t i e s o f o n e o f t h e c o n s t i t u e n t s b e c o m e s a v a i l a b l e , it will
p e r h a p s be n e c e s s a r y t o r e - e v a l u a t e t h e o t h e r v a l u e s t o o .
T h e e q u i l i b r i u m c o n s t a n t K3 f o r t h e r e a c t i o n
$3 = g2S2,

(14)

is in close a g r e e m e n t w i t h t h e v a l u e f o u n d b y B e r k o w i t z a n d M a r q u a r d t (4) f r o m mass

s p e c t r o m e t r i c w o r k o n v a p o u r s a b o v e C d S a n d Z n S . O n t h e o t h e r h a n d , t h e partial
p r e s s u r e s o f $4 at h i g h t e m p e r a t u r e s a r e far less t i t a n e x p e c t e d f r o m t h e e x p e r i m e n t s

THERMODYNAMICS OF SULPHUR VAPOUR

1.0

843

$2

0.5
0.2

S3
$4

0.10.05
0.02
0.01 "7 ~
800

F
900

I
1000

I
1100

t
1200

1300

T/K

FIGURE 2. Mole fractions x of the different molecular species in saturated sulphur vapours as
calculated from the data in table 1 and 2 according to equation (8).

of the same authors. All the other constants do not differ much from those expected
from the study of Detry e t aL c7~
The calculations presented here are based on two assumptions: (i) the heat capacities can be interpolated in the way described above and (ii) the fugacity and compression coefficients of all the species in the gas phase are functions of temperature and
total pressure only and can be taken from the table of generalized properties of pure
gases and liquids. (~4)
The interpolation of the heat capacities may be doubtful for S3, S4, and S5 and may
introduce some error in the thermodynamic properties derived from the fitting of the
equilibrium constants so as to reproduce the measured densities as close as possible.
The species S~ and S4 are of importance only at high temperatures (see figure 2). At
low temperatures their mole fractions were assumed to be near those found by Detry
et al. (7) Thus, if the heat capacities of these species were not quite correct, this would
result in a certain, but small, inaccuracy of their enthalpies of formation and entropies,
which were derived from the equilibrium constants by a second-law treatment. Similar
arguments hold for Ss to a higher degree, because S5 is always present at low mole
fractions only. The heat capacity of the big S7 molecule is expected to fit well to the
curves of figure 1.
The assumption concerning the fugacity and compression coefficients has been
discussed in connexion with the estimation of the critical quantities of sulphur. (3) If
this assumption were not completely true, this would have no great influence on the
thermodynamic data presented in table 2. These values are only partially based on the
density measurements at high pressures. In most cases, when pressures are not too
high, the fugacity and compression coefficients are close to unity. On the other hand,
the fact that the treatment applied here describes the experimental results both at
low and at high pressures supports strongly the assumptions made.

844

H. RAU, T. R. N. KUTTY, AND J. R. F: GUEDES DE CARVALHO

5. Computer program
A computer program written in FORTRAN according to the specifications on the
previous page is available from H. R. The data for calculation of the fugacity and
compression coefficients are also provided. This program allows the partial pressures
of $2 to $8 and the density of the vapour to be calculated from the total pressure and
the temperature.

REFERENCES
1. Budininkas, P.; Edwards, R. K.; Wahlbeck, P. G. J. Chem. Phys. 1968, 48, 2859.
2. Braune, H.; Peter, S.; Neveling, V. Z. Naturforsch. 195!, 6a, 32.
3. Ran, H.; Kutty, T. R. N.; Guedes de Carvalho, J. R. F. J. Chem. Thermodynamics, 1973, 5, 291.
4. Berkowitz, J.; Marquardt, J. R.J. Chem. Phys. 1963, 39, 275.
5. Berkowitz, J.; Chupka, W. A. J. Chem. Phys. 1964, 40, 287.
6. Berkowitz, J.; Lifshitz, C. J. Chem. Phys. 1968, 48, 4346.
7. Detry, D.; Drowart, J.; Goldfinger, P.; Keller, H.; Rickert, H. Z. Phys. Chem. N.F. 1967, 55, 314.
8. Ran, H. Rev. Sci. Instrum. 1972, 43, 831.
9. Kubaschewski, O.; Evans, E. L1.; Alcock, C. B. Metallurgical Thermochemistry, 4th edition,
Pergamon Press: Oxford. 1967.
10. Berkowitz, J.; Chnpka, W. A.; Bromels, E.; Belford, R. L. J. Chem. Phys. 1967, 47, 4320.
11. Guthrie Jr., G. B.; Scott, D. W.; Waddington, G. J. Amer. Chem. Soc. 1954, 76, 1488.
12. Luft, N. W. Monatsh. Chem. 1955, 86, 474.
13. Kortiim, G. Einfiihrung in die Chemisehe Thermodynamik, 3rd edition, Verlag Vandenhoeck and
Ruprecht: G6ttingen. 1963, p. 202.
14. Hougan, O. A.; Watson, K. M.; Ragatz, R. A. ChemicalProcess Principles, part II, second edition,
John Wiley Sons, Inc.: New York, London, Sidney. 1966.
15. Pauling, L. Proc. Nat. Acad. ScL U.S. 1949, 35, 495.