Chapter 2
Chemical and Physical Properties
of Sulphur Dioxide and Sulphur Trioxide
2.1
Introduction
In order to appreciate the impact of the properties of liquid sulphur dioxide and
liquid sulphur trioxide on future technology, it is important that an in-depth analysis
of their properties be understood.
Though the data given in this chapter are available in literature, the practical application of the remarkable physical as well as chemical properties of sulphur dioxide and
sulphur trioxide has been experienced and applied on large scale only recently.
The three main features of these two important chemicals are:
(a) High solubility of sulphur trioxide in liquid sulphur dioxide
(b) Reaction of liquid sulphur trioxide with liquid sulphur in stoichiometric proportions instantaneously to produce sulphur dioxide:
S 2SO3 3 SO2
(c) Liquefaction of pure sulphur dioxide at room temperatures under moderate
pressures of 56 kg/cm2 (Please see Fig. 2.1).
The present sulphonation techniques involves sulphonating agents such as sulphuric acid, 25 % oleum, 65 % oleum and sulphur trioxide. The technique involves
high temperature reactions due to exothermic nature of sulphonation. The current
techniques of sulphonation require elaborate chilling and cooling systems.
Sulphonating processes currently used are generally batch operations and hence
requires a battery of reactors having varying time cycles.
The Author(s) 2016
N.G. Ashar, Advances in Sulphonation Techniques,
SpringerBriefs in Applied Sciences and Technology,
DOI 10.1007/978-3-319-22641-5_2
10
Fig. 2.1 Vaporization curves
for sulphur dioxide
Chemical and Physical Properties
8
10 0
0
60
40
(V
ol.
-
%)
20
4
6
10 8
10
en
t ra
tio
n
SO
PRESSURE OF SO2 . BAR
Co
nc
1
0.7
0.5
0.3
0.2
Curve for 100% SO2 shows relationship of
boiling point to equilibrium vapour pressure
Curve for impure SO2 mixture shows
dependence of dewpoint on SO2 partial pressure
0.1
0.07
0.05
0.03
60
40
20
20
40
DEWPOINT BOILING POINT C
2.2
Sulphur Dioxide Physical Properties
Sulphur dioxide SO2 is a colourless, non-inflammable, toxic gas with a characteristic pungent smell and acidic taste. Table 2.1.
2.3
Vaporisation of SO2
It is important to analyse the physical property of condensation points at various
pressures and concentrations of SO2.
11
2.3 Vaporisation of SO2
Table 2.1 Physical
properties of sulphur dioxide
Property
Value
Molecular weight
Melting point (1013 mb)
Latent heat of fusion (at m.p)
Dynamic viscosity at 0 C
Density at 10 C
Critical density
Critical pressure
Critical temperature
Boiling point (1013 mb)
Latent heat of vaporization
(at b.p.)
Standard density at 0 C
(1012mb)
Density relative to air
(0 C, 1013mb)
Molar volume (0 C, 1013 mb)
Standard enthalpy of formation
64.06
75.5 C
115.6 J/g
368 Pa/s
1.46 g/cm3
0.525 g/cm3
78.8 bar
157.5 C
10 C
Specic heat, Cp (1013 mb)
0 C
100 CC
300 C
500 C
Cp/Cv (15 C, 1013 mb)
402 J/g
2.93 kg/m3
2.263
21.9 l/mol
70.94 kcal/mol
4636 J/g
586 K/(kg K)
662 J/(kg K)
754 J/(kg K)
816 K/(kg K)
1.29
It can be observed from the attached Fig. 1.2 that for 100 % liquid SO2 moderate
pressures are required to liquefy SO2 at ambient temperatures between 30 and
40 deg C.
2.4
The Solubility of SO2 in Sulphuric Acid
The solubility of sulphur dioxide in Sulphuric acid (see Fig. 1.3) rises in proportion
to the SO2 partial pressure in good conformity with Henrys law and is increased by
lowering the temperature, as represented graphically in Fig. 1.2. In the solution,
sulphur dioxide is present mainly as SO2 molecules, but Raman spectroscopy
conrms the presence in minor proportions of the species HSO3, S2O5 and H2SO3.
The last of these, sulphurous acid (the anhydride of which is sulphur dioxide),
exists only in aqueous solution. Aqueous solution of alkaline compounds will
absorb much more sulphur dioxide than pure water (Please see Fig. 2.2) because of
the formation of hydrogen sulphite (bisulphite) and sulphite ions.
12
Chemical and Physical Properties
Fig. 2.2 Solubility of sulphur
dioxide in water
2.5
Solubility of Sulphur Dioxide in Water
It can be observed from Fig. 2.2 that the solubility of sulphur dioxide in g/kg H2O
increases with pressure and reduces with temperature.
This property is of importance in industrial applications in scrubbling of sulphur
dioxide in tail gases.
2.6
Chemical Properties of Sulphur Dioxide
Sulphur dioxide is very stable; thermal dissociation becomes signicant only above
2,000 C. It can be decomposed by shock waves, irradiation with ultraviolet or
X-rays, or by electric discharges
The reaction of sulphur dioxide with oxygen to form sulphur trioxide is
industrially the most signicant of all its reactions because of its importance in
sulphuric acid production. In the gas phase, it will only take place at elevated
temperatures and, for a satisfactory yield of sulphur trioxide; it requires the presence
of a catalyst. In aqueous solution, sulphur dioxide is oxidized to sulphuric acid at
low temperatures by air in the presence of activated coke or nitrous gases or by
oxidizing agents like hydrogen peroxide.
2.6 Chemical Properties of Sulphur Dioxide
13
The reduction of sulphur dioxide with hydrogen, carbon or carbon compounds
such as methane or carbon monoxide is also of industrial interest. These reactions
require high temperatures or catalysts or both. They result in mixtures of elemental
sulphur with hydrogen sulphide. If carbon or a carbon compound has been used as
the reducing agent, carbon-containing species such as carbon dioxide, carbonyl
sulphide and carbon disulphide will be formed as well.
Sulphur dioxide will normally oxidize metals at elevated temperatures,
simultaneously forming metal sulphides and oxides. Liquid sulphur dioxide is a
relatively efcient solvent with some water-like properties. Polar inorganic
compounds are usually insoluble or only sparingly soluble in liquid sulphur
dioxide, whereas covalent inorganic and organic compounds are often dissolved,
mostly forming stable solutions. The fact that aromatic hydrocarbons will dissolve more readily than aliphatics in sulphur dioxide is exploited on an
industrial scale for the extraction of aromatics from crude oil according to the
Edeleanu process.
2.7
Physical Properties of Sulphur Trioxide
Sulphur trioxide is produced by catalytic oxidation of sulphur dioxide in concentrations of 1215 % in gaseous form. To produce pure sulphur trioxide the plant
gases are passed through oleum towers to produce 2530 % free SO3 oleums.
These oleums are boiled in steam heated or gas heated heat exchangers to
produce pure sulphur trioxide.
This is then sent to condensers to produce liquid sulphur trioxide.
2.8
General Properties of Liquid Sulphur Trioxide
Empirical formula
SO3
Molecular wt. of monomer
Boiling point
Density (20 C)
Specic heat (cal/g at 2535 C)
Heat of dilution (cal/g)
Critical temperature
Critical pressure
Critical density
van der Waals constants
80.06
44.8 C (112.6 F)
1.9224
0.77
504
218.3 C (424.9 F)
83.8 atm
0.633 g/ml
a = 2105
b = 0.964
14
2.9
Chemical and Physical Properties
Properties of Liquid Sulphur Trioxide
See Fig. 2.3.
Fig. 2.3 Properties of different molecular forms of liquid sulphur trioxide
2.10
Viscosity of Liquid Sulphur Trioxide
Fig. 2.4 Viscosity of liquid sulphur trioxide
2.10
Viscosity of Liquid Sulphur Trioxide
See Fig. 2.4.
2.11
Specic Gravity of Sulphur Trioxide
See Fig. 2.5.
2.12
Vapour Pressure of Liquid Sulphur Trioxide
See Fig. 2.6.
15
16
Chemical and Physical Properties
Fig. 2.5 Properties of sulphur trioxide
2.13
Molar Heat Capacity of Liquid Sulphur Trioxide
See Fig. 2.7.
2.14
Vaporisation Curves for Sulphur Dioxide
See Fig. 2.1.
2.15
Enthalpy of Sulphur Trioxide Gas
See Fig. 2.8.
2.16
Chemical Properties of Sulphur Trioxide
17
Fig. 2.6 Properties of sulphur trioxide
2.16
Chemical Properties of Sulphur Trioxide
2.16.1 Commercially Sulphur Trioxide Is Produced
by Converting 1012 % SO2 by Catalytic Conversion
at Temperatures Between 360600 C in Multipass
Converter of Sulphuric Acid Plant
This is then further reacted with water to form Sulphuric acid by the equation
H2 S2 O7 H2 O ! 2H2 SO4
It is important to note that reaction of sulphur trioxide gas with water would
form micron size droplet and cannot be absorbed to form H2SO4.
18
Chemical and Physical Properties
Fig. 2.7 Properties of sulphur trioxide
Formation of Sulphuric acid from SO3 gas is exothermic and the absorbing
H2SO4 in the absorption towers need to be cooled to maintain efciency of
absorption.
2.17
One of the Special Chemical Properties of SO3 Which
Has Been Safer but not Explored till date
S 2SO3liq ! 3SO2gas
DH 74:3 kcal=g mole
DF 36:71 kcal=g mole
Since the free energy change is large and negative, the reaction is almost
instantenous. In addition, the reaction generates one additional mole in gaseous
form, so there is a pressure increase.
2.18
Sulphur Trioxide Is a Strong Sulphonating Agent
19
Fig. 2.8 Properties of sulphur trioxide
2.18
Sulphur Trioxide Is a Strong Sulphonating Agent
for Difcult, Organic and Inorganic Chemicals
2.18.1 Treatment of Sulphuric Acid Plant Tail Gas
from Final Absorption Tower
The tail gases of sulphuric acid contact plants consist chiefly of nitrogen and
residual oxygen. They also contain sulphur dioxide in low concentrations which
depend on the conversion efciency attained in the conversion stages. The content
of gaseous sulphur trioxide and sulphuric acid is essentially a function of the
temperature and concentration of the irrigation acid in the nal absorber. Under
unfavourable operating conditions, as, for example, when the sulphur
dioxide-containing converter feed gases are inadequately dried or contain hydrocarbons, sulphuric acid mists can be formed which are not removed in the
absorption system, even when the concentration and temperature of the absorber
acid are at their optimum values. The safest way of removing these acid mists is
using a candle type demister. However, this is not very effective in removing
excessive sulphur trioxide concentrations, which may result from poor acid distribution in the absorber.
http://www.springer.com/978-3-319-22640-8
