SULFUR

I. Sulfur :

I-1 Introduction
Sulphur is the chemical element with atomic number 16, symbol S. It is a member of the
group of chalcogens. It is an abundant, water-insoluble, multivalent non-metal.
Sulphur is mostly known as yellow crystals and is found mostly in volcanic terrains and as
sulfides and sulfates in most minerals such as FeS2 (pyrites), ZnS (blende), PbS (galena) and
CaSO4 (gypsum) and in hydrocarbons. It is an essential element for all living beings, it is
involved in the formula of two natural amino acids, cysteine and methionine and therefore, in
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many proteins. The most stable isotopes are : S (95.02 %), S (0.75 %), S (4.21 %) and
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S (0.02 %).

I-2/ Physical properties :

Sulphur (S), is a chemical element of the family of chalcogens constituting the VIA subgroup
(or the 16th column) of the periodic table. Its external electronic structure is : 3s2 3p4. In STP,
sulphur is a solid, odourless, tasteless and insoluble in water but soluble in ammonia and
carbon disulphide CS2.
By analogy with dioxygen, one could imagine a diatomic molecule S2 with a fairly similar
molecular orbital diagram. This species does indeed exist in the gaseous state, but the ordinary
forms of solid sulphur at room temperature are based on different crystal arrangements of
cyclo-8S forming a crown cycle.

Sulphur has a large amount of allotropes, i.e. different crystalline forms. It is a poor conductor
of heat and electricity (insulator).
At 119 °C, sulphur is a light yellow liquid, if the temperature exceeds 160 °C, the liquid
becomes more and more viscous and blackens, there is a break in theS8 cycles under the effect
of thermal stirring, at 400 °C, the brown liquid consists essentially of paramagnetic S2
molecules, and S8, S6 and S4 molecules. At 1700 °C, only S2 molecules remain in the gas.

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 The following table represents the characteristics of the sulfur atom :
Atomic Number 16
Atomic mass 32,065
Oxidation states - 2, 0, + 2, + 4, + 6
Electronegativity (Pauling) 2.6
Ionization energy (Kj/mol) 999.6
Atomic Radius (Å) 1.27
Melting temperature (°C) 115.21
Boiling temperature (°C) 444.61

I-3/Chemical compounds :
Sulphur has several degrees of oxidation. With oxidation degree - II, sulfur can combine with
hydrogen, metals and some non-metals to give sulfides, and with positive oxidation degrees, it
combines with oxygen and halogens (fluorine and chlorine) to give oxides and halogens
respectively.
 - Sulphides :
Sulphur can replace oxygen in a large number of compounds. In particular, it forms
polymeric or ionic sulphides with metals.
- Ionic sulphides, analogous to oxides of the same type (i.e. containing S2- ion), are
predominant, but there are also polysulphides (containing S44-, S52-, S62-...) whereas
in the chemistry of oxides only the species O2- and O2-.
- Hydrogen sulfide, H2S is the analogue of water. However, the electronegativity
difference between H and S is smaller than between H and O; the bond is therefore
less polar, therefore H2S is a less good donor of hydrogen bonds. The melting point
of H2S is only - 85.6 °C, its boiling point - 60.3 °C
 Combination with halogens :
Together with fluorine and chlorine, sulfur gives covalent molecules such as SF4
(sulfur tetrafluoride), SF6 (sulfur hexafluoride), S2Cl2 (disulfur dichloride), SCl2
(sulfur dichloride), SO2Cl2 (sulfuryl chloride), SOCl2 (thionyl chloride).
 Combination with oxygen (sulphur oxides) :
Theoretically, one would expect a series of compounds with oxidation degrees varying
from + I to + VI. In fact, not everyone is represented.
S2O and SO exist but are unstable. The most significant sulfur oxides are SO2 (sulfur
dioxide or sulfur dioxide) and SO3 (sulfur trioxide or sulfuric dioxide).

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 Sulfur combustion normally stops at SO2 ; in the presence of a catalyst, it is possible to
oxidize SO2 to SO3 by dioxygen. The reaction of the latter compound with water then
provides sulfuric acid.
In STP, SO2 is a dense, colourless and toxic gas, its inhalation is highly irritating.
SO3 is a colorless crystallized solid that melts at a temperature of 16.9 °C giving a
hygroscopic colorless liquid (it absorbs moisture from the air). At high temperature
(>450 °C), SO3 decomposes into sulfur dioxide (SO2) and oxygen (O2).
The following table lists some characteristics of sulphur oxides :

Sulfur oxide SO2 SO3

Melting temperature (°C) - 73 16.8
Boiling temperature (°C) -10 44.7
S-O bond length (Å) 1.43 1.43
Binding angle O—S--O 119.5° 120°

I-4/Chemical properties :
I-4-1 Acid-base properties :
 Hydrogen sulfide (H2S)
In aqueous solution, H2S behaves like a weak diacid :

H2S + H2O ˂====˃ H3O+ + HS- pka1 = 7

HS- + H2O ˂====˃ H3O+ + S2- pka2 = 15

 Sulphur dioxide (SO2)

SO2 presents the properties of a Lewis base, by its free doublet, the properties of a Lewis acid
by the presence of free d AO and also the properties of a Bronsted acid in solution.
SO2 dissolves in water to give an oxoacid :

SO2 + H2O ====˃ H2SO3

In H2SO3 aqueous solution, sulfurous acid gives the following equilibria

H2SO3 + H2O ˂====˃ H3O+ + HSO3- pka1 = 3.1
HSO3- + H2O ˂====˃ H3O+ + SO32- pka2 = 7.2

H2SO3 acid should be stored away from light. It reacts with oxygen in the air to give sulfuric
acid. The salts corresponding to H2SO3 acid are called sulfites (sodium sulfite: Na2SO3) and
hydrogen sulfites (sodium hydrogen sulfite : NaHSO3).
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  Sulphur trioxide SO3 :
Sulfur trioxide, in the absence of a free doublet on sulfur, behaves only as a Lewis acid. It
dissolves in water to give an oxyacid, sulfuric acid H2SO4.
In aqueous solution, the following reactions are obtained :

SO3 + H2O ====˃ H2SO4

H2SO4 + H2O ˂====˃ H3O+ + HSO4- pka1 = -3
HSO4- + H2O ˂====˃ H3O+ + SO42- pka2 = 1.9

I-4-2 / Redox properties :

 Hydrogen sulphide H2S :
H2S has reducing properties, in the presence of oxygen, it oxidizes to SO2 and in the presence
of SO2 to sulfur:
2 H2S (s) + 3 O2 (g) ====˃ 2 H2O (g) + 2 SO2 (g)
2 H2S (g) + SO2 (g) ====˃ 2 H2O (g) + 3 S

These two equations correspond to the Clauss process, used to recover sulphur from natural gas.
 Sulphur Dioxide
SO2 has reducing properties :
SO2 + ½ O2 ====˃ SO3

With sulfur, SO2 can give the thiosulfate ion :

SO2 + 3 H2O + S ====˃ S2O32- +2 H3O+

In the presence of CO, SO2 undergoes a reduction :

SO2 + 2 CO ====˃ S + 2 CO2

With SO2, oxygen undergoes oxidation in the presence of catalyst :

SO2 + ½ O2 ====˃ SO3
I- 5/ Applications :
Sulphur compounds have multiple applications :
 Sulphur is mainly used in the manufacture of phosphate fertilizers (it ranks
quantitatively just after the three major elements N, P, K, in matches, fireworks,
sulphuric acid production.
 Sulphur dioxide is used as a disinfectant, antiseptic, antibacterial, refrigerant gas,
bleaching agent and preservative for food products (dried fruit). In industry, SO2 is
used mainly for the production of sulphuric acid.
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  Sulphur trioxide allows the direct manufacture of highly concentrated sulphuric acid
by simple hydration.
 Sulphites are used to bleach paper.
 Sodium or ammonium thiosulfate is used as a photographic fixing agent.

I- 6/ Production :
Sulphur can be recovered from natural gas or fromH2Sdepending on the reactions (Clauss
process) :
H2S + 3/2 O2 ====˃ SO2 + H2O
2 H2S + SO2 ====˃ 3 S + 2 H2O

Sulphur dioxide SO2 can be obtained by different methods:

 Sulphur Oxidation :

S8 + 8 O2 ====˃ 8 SO2

 Hydrogen sulfide oxidation :

2 H2S + 3 O2 ====˃ 2 H2O (g) + 2 SO2 (s)

 Oxidation of sulphide minerals :

4 FeS2 (s) + 11 O2 (g) ====˃ 2 Fe2O3 (s) + 8 SO2 (g)
2 ZnS (s) + 3 O2 (g) ====˃ 2 ZnO (s) +2 SO2 (g)

 Oxidation of copper filings by hot sulphuric acid :

Cu + 2 H2SO4 (aq) ====˃ CuSO4 (aq) + SO2 (g) + 2 H2O (l)

II. Sulphuric acid (H2SO4) :

II- 1/ Characteristics :
Pure sulfuric acid is a colorless, odorless, hygroscopic oily liquid that turns brown yellow in
the presence of impurities. It is miscible in water. Dissolution in water or in a water-alcohol
mixture is accompanied by a large release of heat.
In STP, sulfuric acid is not volatile. From 30 °C, it emits vapours. At boiling temperature,
SO3 emerges as white vapors following the decomposition of sulfuric acid according to the
following reaction :
H2SO4 ====˃ H2O + SO3

at 450 °C, SO3 in turn decomposes according to the following reaction :

SO3 ====˃ ½ O2 + SO2

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 The table below shows some characteristics of H2SO4 sulfuric acid :
Physical state Liquid
Molecular weight 98.08
Melting point 3.5 °C (pure acid)
3 to 5 °C (98 % acidic)
38 °C (78 % acidic)
Boiling Point 290 °C (pure acid)
335 °C (98 % acidic)
Density 1,830 (pure acid)
1.836 (98 % acidic)

Acid-base and redox properties :

II-2-1 /Acid properties :
Sulphuric acid is a strong acid :

H2SO4 + H2O ――˃ H3O+ + HSO4- pka1 = - 3

HSO4- + H2O ――˃ H3O+ + SO42- pka2 = 1,9

The dissolution of sulfuric acid in water is highly exothermic. It is dangerous, very violent
and is accompanied by splashing of liquid if water is poured on concentrated acid, a dilution
of acid is always done under cooling, the acid must be poured into the water and not the other
way around, the largest amount of starting water of the dilution is used to dissipate the heat.
Sulfuric acid's affinity for water makes it an excellent dehydrating agent. It is used in the
preparation of many dried fruits.
- H2SO4 reacts with all bases to give the salt (sulfate) and water :

H2SO4 +2 NaOH ====˃ (2 Na+, SO42-) + 2 H2O

H2SO4 +2 NH4OH ====˃ (NH4)2SO4 + 2 H2O

- H2SO4 reacts with acids weaker than it (pka > - 3) by yielding a proton :

H2SO4 + CH3COOH ====˃ CH3COOH2+ + HSO4-

H2SO4 + HNO3 ====˃ HSO4- + NO2+ + H2O

- H2SO4 reacts with acids stronger than itself (pka < - 3) by accepting a proton
H2SO4 + HSbF6 ====˃ H3SO4+ + SbF6-
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- H2SO4 reacts with the salts to give a hydrogen sulfate :
H2SO4 + CH3COONa ====˃ CH3COOH + NaHSO4

- H2SO4 reacts with metal oxides and sulphides to give a sulphate :

H2SO4 + MO ====˃ MSO4 + H2O

H2SO4 + MS ====˃ MSO4 + H2O

II-2-2 Redox properties :

The concentrated and hot sulfuric acid acts as an oxidizing agent and involves the SO42-/SO2
redox couple. It can attack certain metals (M : Cu...).
Diluted sulfuric acid involves the redox couple 2H+/H2, and can attack certain metals (M : Fe,
Zn, Mn...).

3/ Applications :
Sulphuric acid is used in :
 Producing fertilisers
 Textile production
 Processing
 Oil refining
 The storage of electricity in lead-acid batteries.
 pickling of metals
 The synthesis of chemical compounds (dyes, explosives, detergents, etc...)

II- 4/ Production :
The industrial preparation of sulphuric acid is carried out according to two processes : the so-
called "lead chambers" and the one called "of contact" which is the most used :

 Lead chamber process :

The process of lead chambers, in its most modern version (Peterson process), is carried out by
a reaction between sulfur dioxide, water and oxygen, which combine to give sulfuric acid.
This reaction is catalyzed by continuously recycled nitrogen oxides :

SO2 + H2O + NO2 ====˃ HO-SO2-ONO + H2O ====˃ H2SO4 + ½ NO + ½ NO2

Introduced by John Roebuck in 1746, this process provides a less concentrated sulfuric acid
with more impurities, used in the manufacture of superphosphates

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  Contact method :
The contact process is the industrial process currently implemented, called "contact process"
because it requires contact with a catalyst, it is broken down into three stages :
1. Purification of sulphur S and combustion of sulphur in dry air to obtain sulphur
dioxide SO2 in purification of SO2, if not obtained from sulphur.
2. Oxidation of SO2 to sulphur trioxide SO3 using vanadium pentoxide V2O5 (catalyst)
3. Conversion of sulphur trioxide to sulphuric acid H2SO4.

Sulphur trioxide is cooled in a heat exchanger and collected in an absorption tower where it is
dissolved in concentrated sulphuric acid to produce oleum :

H2SO4 (l) + SO3 (g) ====˃ H2S2O7 (l)

which is then hydrated to release sulfuric acid with an average yield of 30 % :

H2S2O7 (l) + H2O (l) ====˃ 2 H2SO4 (l)

Laboratory preparation :
Sulfuric acid can be prepared in small quantities by burning sulfur to produce sulfur dioxide
SO2 and the latter is oxidized by hydrogen peroxide. The reactions involved are as follows :

S + O2 ====˃ SO2
SO2 + H2O2 ====˃ H2SO4