CHM 201: INORGANIC CHEMISTRY I

Dr. Segun A. Ogundare

Lecture content

1. Fajan’s rule and the consequences of the rule.

2. Stereochemistry of simple molecules
3. molecular orbital theory of simple molecules including homo and heteroatoms.
4. Comparative chemistry of group V, VI and VII, physical and chemical properties of
some important chemicals in Chemistry, Agriculture, Medicine and industry.

1. Fajan’s rules (covalent character in ionic compounds)

Fajan’s rules are a set of four basic rules used to describe the degree of covalency (or covalent
nature) of ionic compounds. Generally, ionic compounds are expected to have bond based on
electrostatic attraction between two charges of opposite signs. However, it was observed that
some ionic compounds show covalent character.

It is well known that ionic compounds have; High melting points, high solubility in polar
solvents, high thermal stability. On the other hand, covalent compounds have low melting point,
poor solubility in polar solvents and poor thermal stability.

When ionic compounds show decrease in ionic characters, a degree of covalency may be
involved.

Factors contributing to covalency in ionic compounds are described by Fajan's rules. When a
cation (M+) approaches an anion, the electron cloud of the anion is attracted towards the cation
nucleus and the anion electron cloud will get distorted (deformed). This effect is called
polarization of the anion. The cation is said to possess polarizing power while the anion is said to
be polarized

The polarizability of an anion determines the degree of covalency in an ionic compound. The
greater the polarizability, the lower the ionic character and the greater the degree of covalency.

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The power of a cation to polarize an anion is called polarizing power. It is determined by ionic
potential which is the ratio of charge to ionic radius of the cation.

The ionic potential φ = charge of cation / ionic radius of cation

The tendency of an anion to be polarized is called polarizability. The polarizing power of cation
and the polarizability of anion is governed by Fajan's rules.

Fajan's rules state that:

1. The smaller the cation the greater the polarizing power. In group IA of the periodic table,
lithium chloride has the highest covalent character and caesium chloride has the highest ionic
character.

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2. The larger the anion, the greater the polarizability, the higher the covalency

3. As the charges on the cation or anion increase the degree of covalency increases. Remember,
the ionic radius of a given cation decreases with increase in charge and the ionic potential also

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increases correspondingly. Similarly, as the charges on the anions increase, the size of the anions
increases and the tendency for polarizability also increases.

4. The electronic configuration of pseudo-noble-gas ions such as Cu2+ will lead to reduction in
effective nuclear charge and increase in ionic potential due to the poor shielding effect of the d-
orbital electrons. With respect to covalent character, CuCl > NaCl an KCl > AgCl

Assignment

1. Compare the thermal stability of sodium carbonate (Na2CO3) and calcium carbonate (CaCO3).
Identify the compound that is more stable

2. With reason, arrange the following in order of increasing covalency; MnO3, MnO, MnO2,
Mn2O3, Mn2O5, Mn2O7

3. Arrange the following in decreasing order of ionic character; FeCl2, FeCl3, FeF2, FeF3, FeBr2,
FeBr3, FeI2, FeI3

4. Which of the following will likely have the highest melting point: AlCl3, AlI3, AlF3, AlBr3

5. Which of the following will have highest degree of covalency; K2O, K2O2, KO2

2. Stereochemistry of simple molecules based on valence Shell Electron Pair Repulsion

Theory

Valence shell electron pair repulsion theory (VSEPRT) was proposed by Gillespe and Nyholm to
predict and explain molecular shapes, bond angle and bond length. VSEPRT states that the shape
(stereochemistry) of a molecule is determined by repulsion between all the groups of electrons
surrounding the central atom in the molecule. The groups of electrons will stay as far apart as
possible to minimize the repulsion between them, as like charges repels. By definition a group of

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electron could be a lone pair, bond pair (single, double or triple bond), or an unpaired electron
(single electron). The lone pair possesses greater repulsion and can freely rotate because it is
only attached to the central atom unlike bond pair attached to two atoms.

The order of repulsion between the various groups of electrons is:

Lone pair-lone pair ˃ lone pair-bond pair ˃ bond pair-bond pair. Also among the bond pairs, the
trend is as follow: triple bond- single pair ˃ double bond-single bond ˃ single bond-single bond.
According to VSEPRT, a molecule will adopt a shape that will minimize the repulsion between
the groups of electrons surrounding the central atom. Below are examples of shapes adopted by
simple inorganic compounds. The shapes depend on the number of groups of electrons and the
types of the groups of electrons. The presence of one or more lone pair leads to deviation from a
regular shape. Regular shapes include; linear shape (sp), trigonal planar (sp2) tetrahedral (sp3 or
sd3) or square planar (sp2d or dsp2), trigonal bipyramidal (sp3d) and octahedral (sp3d2). The
irregular shapes include bent, trigonal pyramidal, see-saw and distorted octahedral.

Hybridization of orbitals

Hybridization is the mixing of orbitals of different energy levels to form a set of orbitals with the
same energy. The set of orbitals are called hybridized orbitals. The number of orbitals combined
during hybridization is equal to the number of hybridized orbitals formed. The nomenclature of
the hybridized orbitals is derived by considering the letters of the orbitals combined during
hybridization. A combination of s and p will give sp hybridized orbitals.

Table 1: Combination of orbitals and hybridized orbitals formed with bond angles and shapes
with suitable examples

Combining Orbitals Hybridized orbital Angle(o) shape Example

formed
s, p Sp 180 Linear BeCl2
2
s, p, p sp 120 Trigonal BF3
planar
s, p, p, p sp3 109 tetrahedral CH4
s, p, p, p, d sp2d 90, 120 Pentagonal PCl5
bipyramidal
s, p, p, p, d, d sp3d2 90 Octahedral SF6

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 VSEPR notation gives a representative notation for classifying simple chemical compounds
based on the number and types of electron pairs around their central atom. Examples: BeH2, CO2
(AB2) and SO2 (AB2E). Conventionally, A is used to represent the central atom, B or X is used to
represent the number of atoms bonded to the central atom and E represents the number of lone
pairs on the central atom (ignore lone pairs on bonded)

Table 2: Groups of electrons, hybridization, bond angle and possible stereochemistry with
examples of simple molecules.

No of Bond Lone Hybridization Shape Bond Examples

group of pair pair Angle
electrons
2 (AB2) 2 - Sp Linear 180o CO2, BeCl2, HCN
3 (AB3) 3 - sp2 Trigonal planar 120o BF3, BCl3, SO3, NO3-
3 (AB2E) 2 1 sp2 Bent or angular ＜120o SO2, SnCl2, NO2
4 (AB4) 4 - sp3 Tetrahedral 109o CH4, NH4+, CF4
4 (AB4) 4 - sd3 Tetrahedral 109o MnO4-, CrO42-
4 (AB3E) 3 1 sp3 Trigonal 107o NH3, H3O+, SOCl2
pyramid
4 (AB2E2) 2 2 sp3 Bent or angular ~105o H2O, H2S, Cl2O, NH2-
5 (AB5) 5 - sp3d Trigonal 90o, 120o, PCl5, PF5
bipyramid 180o
5 (AB4E) 4 1 sp3d See-saw, ＜90o SCl4, SF4, SbF4-
sawhorse,
Distorted ＜120o
tetrahedral
5 (AB3E2) 3 2 sp3d T-shape ~90o BrF3, ClF3, ICl3

~180o
5 (AB2E3) 2 3 sp3d Linear 180o XeF2, ICl2-
6 (AB6) 6 - sp3d2 Octahedral 90o SF6, PF6-
6 (AB5E) 5 1 sp3d2 Distorted ~90o ClF5, IF5, BrF5
octahedral,
square pyramid

6 (AB4E2) 4 2 sp3d2 Square planar 90o XeF4

7 (AB7) 7 - sp3d3 Pentagonal 72o, 90o IF7
bipyramid
7 (AB6E) 6 1 sp3d3 Distorted XeF6
octahedral
8 (AB8) 8 - sp3d4 Square antiprism 90o IF8-

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Table 3: Spatial representation of simple molecules

Molecular orbital theory of simple molecules including examples on homo and

heteroatoms.

Molecular orbital theory (MOT) deals with Linear Combination of Atomic Orbitals (LCAO).
This linear combination leads to molecular orbitals. Under the MOT, electrons are considered as
waves which can be described with wave function (φ). For a bond to be formed, there must be
combination of wave functions of atomic orbitals where electrons reside. The combination of
atomic orbitals is similar to superimposition of wave fonts; such combination can lead to
constructive or destructive interference. If the two atomic orbitals combine or overlap such that

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the amplitude (displacement along the vertical axis) of the resulting wave font is greater than
those of the atomic orbitals combined, a constructive interference is developed.

For example, 1s atomic orbital will combine with another 1s atomic orbital to give a constructive
interference called bonding molecular orbital. Similarly, the two atomic orbitals can combine to
give destructive interference if they move with opposing orientation in space.

φ1s + φ1s = ψ1s, note that φ1s = atomic orbital and ψ1s = bonding molecular orbital

φ1s - φ1s = ψ*1s, ψ*1s = antibonding molecular orbital.

In this description, the + and – signs indicate orientation in space and (*) is used to indicate
antibonding. With similar orientation, bonding molecular orbital is formed but with opposing
orientation antibonding molecular orbital is formed.

bonding molecular orbitals are of lower energy and most likely contain electrons while
antibonding molecular orbitals are of high energy, which will not accommodate electrons until
bonding molecular orbitals are fully occupied. Orbitals that do not take part in bonding are called
non-bonding molecular orbitals. These orbitals are found in molecules with atoms possessing
lone pairs.

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Molecular orbital diagrams

These are diagrams that show the atomic orbitals that combined to form molecular orbitals. In
the diagrams the molecular orbitals are arranged in order of increasing energy. The total number
of the combined atomic orbitals also represents the total number of molecular orbitals formed.
From the diagram, bond order can be calculated and electronic configurations can be written for
the molecules.

Bond order (B. O.) is the number of electrons in the bonding orbital (B. E.) minus the number of
electrons in the antibonding orbitals (AB. E.) divided by 2.

𝐵.𝐸.− 𝐴𝐵.𝐸.
B. O. = 2

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4. Comparative chemistry of group V, VI and VII, physical and chemical properties of
some important chemicals in Chemistry, Agriculture, Medicine and industry.

Group VA elements

The elements in this group include; nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb)
and bismuth (Bi). The valence shell of the elements has ns2 np3 electronic configuration, hence
their group number. They are p-block elements with their last valence electron in p orbital. The
elements mostly interact with other elements to form covalent compounds, with oxidation
number varying from +5 to -3 especially for nitrogen compounds. some elements in the group
like bismuth form ionic compounds.

[NO3]- (+5), N2O4 (+4), [NO2]- (+3), NO (+2), N2O (+1), N2 (0), NH2OH (-1), N2H4 (-2), NH3 (-3).

Nitrogen

Nitrogen occurs as a very stable diatomic molecule. Only two naturally occurring isotopes are
found, 14N (99.635%) and 15N (0.365%). Nitrogen molecule (N2) is small, having a bond length
of only 110 pm (1.10Å) due to the strong triple bond holding the atoms together (945kJ/mol).
This very strong and stable bond is partially responsible for the explosive nature of some
nitrogen compounds. The shape of N2 revealed that the bond order is 3.

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Nitrogen is important to life, it is an essential constituent amino acids, which are
involved in almost every biochemical process that occurs in living organisms. Most
of the available nitrogen on earth, however, is present as nitrogen gas (dinitrogen) in the air.
Dinitrogen (N2) makes up major constituent of air (78.1%). Nitrogen is obtained from the
atmosphere by liquefaction and fractional distillation. Its normal boiling point (77 K or -196°C)
and its abundance makes it a useful coolant. It reacts directly with rather few elements and is
often used as an inert filling or ‘blanket’ for metallurgical processes. The majority of industrial
nitrogen, however, is used to make ammonia and other compounds.

Preparation

Nitrogen is obtained industrially by fractional distillation of liquid air, and the product usually
contains argon and traces of O2. Oxygen can be removed by addition of a small amount of H2
and passage over a Pt catalyst, or by bubbling the gas through an aqueous solution of CrCl2.
Small amounts of N2 can be prepared by thermal decomposition of sodium azide (NaN3) or by
decomposition of ammonium nitrite (NH4NO2) and ammonium nitrate (NH4NO3). The latter
should be carried out cautiously because of the risk of explosion; ammonium nitrite is potentially
explosive, as well as ammonium nitrate which is a powerful oxidant and a component of
dynamite. In car airbags, the decomposition of NaN3 is initiated by an electrical impulse.

2NaN3 → 2Na + 3N2 NH4NO2 → N2 + 2H2O 2NH4NO3 → 2N2 + 4H2O + O2

Properties and Uses of Nitrogen

Daniel Rutherford discovered nitrogen, N2, in air in 1772. In his experiments, he removed the
oxygen from air by burning a substance in it. When burning carbon-containing substances, he
removed the carbon dioxide that formed by reacting it with aqueous potassium hydroxide. He
then showed that the residual gas would no longer support either combustion or living
organisms. Although this residual gas is mostly N2, it does contain
small amounts of noble gases. Nitrogen, N2, is a relatively unreactive element because of the
stability of the nitrogen–nitrogen triple bond. When substances burn in air, they generally
react with oxygen, leaving the nitrogen unreacted. However, some very reactive metals do react
directly with nitrogen. For example, when magnesium metal burns in air, it forms the nitride, as
well as the oxide. The magnesium nitride dissolves in water to give ammonia

3Mg + N2 → Mg3N2 Mg3N2 + 6H2O → 3Mg(OH)2 + 2NH3

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Liquid nitrogen is used as a refrigerant to freeze foods, to freeze soft or rubbery materials prior to
grinding them, and to freeze biological materials. Large quantities of nitrogen are also used as a
blanketing gas, whose purpose is to protect a material from oxygen during processing or storage.
Thus, electronic components are often made under a nitrogen atmosphere. The other principal
use of nitrogen is to prepare nitrogen compounds.

Hydrogen compounds of nitrogen

Ammonia

Ammonia (NH3) is manufactured industrially in larger molar quantities than any other substance.
The manufacturing process of ammonia is called Haber process, which involves direct synthesis
from the elements (N2 and H2) at around 723 K under high pressure (300 atm.). The reaction will
take place in the presence of a potassium promoted iron catalyst. Small amounts can be prepared
in the laboratory by heating a solution of an ammonium salt with a strong base, such as NaOH or
Ca(OH)2. NaOH + NH4Cl → NH3 + NaCl + H2O

Ammonia is used to make nitric acid and other chemicals including many plastics and
pharmaceuticals. It is a colorless gas with a characteristic irritating or pungent odor. Ammonia is
easily liquefied, and the liquid is used as a nitrogen fertilizer. Ammonium salts, such as the
sulphate and nitrate, are also sold as fertilizers. Large quantities of ammonia are converted to
urea, NH2CONH2, which is used as a fertilizer, as a livestock feed supplement, and in the
manufacture of urea–formaldehyde plastics. Ammonia is also the starting compound for the
preparation of most other nitrogen compounds.

Properties of ammonia

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Ammonia is a colorless gas with melting and boiling points of -77.8°C and -33.35°C). It has a
characteristic odor due to the polar nature of the N–H bonds, there is formation of strong
hydrogen bonds between the molecules in the liquid and solid states. It is very soluble in water
with partial ionization forming ammonium ion.

NH3 + H2O ⇌ NH4+ + OH-

Just like water, ammonia can also function as solvent in reaction as it can dissolve many ionic
and polar compounds. Ammonia reacts with metals to give metal amide though the reaction is
less vigorous compare to metals reacting with water.

2NH3 + 2K → 2KNH2 + H2

Hydrazine (N2H4)

Hydrazine is used as rocket fuel because it burns to give huge amount of heat energy and
nitrogen as by-product and it is sometimes used as reducing agent for silver ion during the
production of mirrors. It is produced by Rauschig synthesis:

2NH3 + NaOCl → N2H4 + NaCl + H2O

N2H4 + O2 → N2 + 2H2O (-620KJ/mol) N2H4 + 4Ag+ + 4OH-→ N2 + 4H2O + 4Ag

Diimine (N2H2)

Another compound of nitrogen and hydrogen is diimine, N2H2, which has the structure HN=NH.
The compound is very unstable and decomposes to give N2 and H2. It is formed by the reaction
between ammonia and sodium hypochlorite

NH3 + NaOCl → NH2Cl + NaOH

NH2Cl + NaOH → NaNHCl + H2O

NH2Cl + NaNHCl → N2H2 + HCl + NaCl

Compounds of metals and nitrogen

Nitrogen reacts directly with some electropositive metals to form nitrides such as Li3N and
Ca3N2. Similarly, nitrides are generated from decomposition of metal amides. Although these
can be formulated with nitride ion N3- the bonding may be partially covalent. Other compounds
with metals are amides and imides (containing NH2- and NH2-, respectively) and azides (N3-).
Metal azides are thermodynamically unstable and often explosive.

3Mg + N2 → Mg3N2 3Ca + N2 → Ca3N2 6Li + N2 → 3Li3N

3Ba(NH2)2 → Ba3N2 + 4NH3

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Although nitrogen combines with other elements that are nonmetals (O and F), the compounds
(NO, NO2, NF3) formed are not considered as nitrides because the term is reserved for
compounds containing nitrogen and more electropositive elements usually metals.

Oxides of nitrogen

Dinitrogen monoxide (N2O)

Dinitrogen monoxide, commonly known as nitrous oxide, N2O, is a colorless gas with a sweet
odor. It can be prepared by careful heating of molten ammonium nitrate. (If heated strongly, it
explodes.) Nitrous oxide, or laughing gas, is used as a dental anesthetic.

NH4NO3 → N2O + 2H2O

It reacts with hydrogen as a oxidizing agent and with metals liberating nitrogen gas. It is mixed
with acetylene to generate heat used in welding.

N2O + H2 → N2 + H2O N2O + Mg → N2 + MgO 5N2O + C2H2 → 5N2 + 2CO2 + H2O

Nitrogen monoxide (NO)

Nitrogen monoxide, commonly known as nitric oxide, NO, is a colorless gas that is of great
industrial and biological importance. Although it can be prepared by the direct combination of
the elements at elevated temperatures, large amounts are prepared from ammonia as the first step
in the commercial preparation of nitric acid. The ammonia is oxidized in the presence of a
platinum catalyst. It is an important oxide in production of nitric acid.

4NH3 + 5O2 → 4NO + 6H2O

Nitrogen dioxide (NO2)

Nitrogen dioxide is a toxic gas that can be prepared by the oxidation of NO or by thermal
decomposition of nitrates of heavy metals. It can exist as a dimer (N2O4). Liquid N2O4 is used as
non-aqueous solvent in reaction. NO2 dissolves in water to form nitric acid while N2O4 liquid
reacts with metals to form nitrate.
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2NO + O2 → 2NO2 2Pb(NO3)2 → 2PbO + 4NO2 + O2

3NO2 + H2O → 2HNO3 + NO N2O4 + Mg → MgNO3 + NO

Oxidation of NO2 in the presence of ozone (O3) results in dinitrogen pentoxide (N2O5) which can
be considered as anhydride of HNO3. It is also generated from the reaction of nitric acid and
P4O10. It is a solid that sublimes as 32°C.

O3 + 2NO2 → N2O5 + O2 P4O10 + 4HNO3 → 2N2O5 + 4HPO32-

Nitric acid (HNO3)

Nitric acid, HNO3, is an important industrial acid. It is used to prepare explosives, nylon, and
polyurethane plastics. Nitric acid is produced commercially by the Ostwald process, which is an
industrial preparation of nitric acid starting from the catalytic oxidation of ammonia to nitrogen
monoxide. In this process, ammonia is burned in the presence of a platinum catalyst to give NO,
which is then reacted with oxygen to form NO2. The NO2 is dissolved in water, where it reacts to
form nitric acid and nitrogen monoxide. The nitrogen monoxide produced in the last step is
recycled for use in the second step.

4NH3 + 5O2 → 4NO + 6H2O

2NO + O2 → 2NO2

3NO2 + H2O → 2HNO3 + NO

Nitrous acid (HNO2)

Nitrous acid is an unstable acid which can be prepared by reaction of nitrite with strong acid
H2SO4. This acid decomposes to nitric acid and nitrous oxide at low temperature and at high
temperature, the acid decomposes to give NO and NO2

Ba(NO2)2 + H2SO4 → BaSO4 + 2HNO2

3HNO2 → HNO3 + H2O + 2NO (low temperature)

2HNO2 → NO2 + H2O + NO (high temperature)

Phosphorus

Phosphorus is the most abundant of the Group VA elements. Its compounds occur widely in
nature as phosphates in rocks and minerals, bones, teeth, DNA and ATP. Phosphate minerals
include calcium phosphate (Ca3(PO4)2), apatite (Ca5(PO4)3OH), fluoroapatite, (Ca5(PO4)3F) and
chloroapatite (Ca5(PO4)3Cl). Unlike nitrogen, which exists in important compounds with
oxidation states between -3 and +5, the most important oxidation states of phosphorus are +3 and
+5.

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Allotropes of Phosphorus

Phosphorus has two common allotropes: white phosphorus and red phosphorus. White
phosphorus is a white waxy solid, which is very poisonous and highly reactive. On exposure to
air, white phosphorus will burst instantly into flame. Because of its reactivity with oxygen, white
phosphorus is stored under water, in which it is insoluble. White phosphorus has formula P4 with
low melting point (44OC). the atoms in the P4 molecule are arranged at the corners of a regular
tetrahedron such that each atom is single-bonded to the other three. White phosphorus is a major
industrial chemical and is prepared by heating phosphate rock with coke (C) and quartz sand
(SiO2) in an electric furnace at 1500OC. The gases from the furnace are cooled by water to
condense the phosphorus vapor to the liquid; the carbon monoxide gas is used as a fuel. The
other product, calcium silicate glass (called slag), is drained periodically from the bottom of the
furnace. Most of the white phosphorus produced is used to manufacture phosphoric acid,
H3PO4. Some white phosphorus is converted to red phosphorus, which has a chain
structure. Red phosphorus is much less reactive than white phosphorus and can be stored in the
presence of air. This phosphorus allotrope is relatively non-toxic and is used in the striking
surface for safety matches. Red phosphorus is made by heating white phosphorus at about 400OC
for several hours.

2Ca3(PO4)2 + 6SiO2 + 10C → 6CaSiO3 + 10CO + P4

Hydrogen compounds of phosphorus

The most elements in group VA form binary compounds with hydrogen, some of which are
similar to the hydrogen compounds (NH3, N2H4, and N2H2) of nitrogen. PH3 is less stable
compare to NH3. It is also less basic as a Lewis base. In the nitrogen compounds, the lone pair of
electrons function as a hard base, and they are good proton acceptors. In PH3, PR3, the lone pair
of electrons resides in a larger orbital, so they are soft bases that have lower basicity toward
proton donors. PH3 is a much weaker Brønsted base than is NH3. Formation of stable
phosphonium salts (PH4+) requires that the acid be strong and the anion be large so there is a
close match in the size of anion and cation. Being a soft base, PH3 forms more stable complexes
with soft acids such as Pt2+ and Ag+. PH3 + HI → PH4I

Phosphine is prepared by hydrolysis of metal phosphide.

6Ca + P4 → 2Ca3P2 Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3

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Phosphorus Oxides

Phosphorus has two common oxides, tetraphosphorus hexaoxide, P4O6, and tetraphosphorus
decaoxide, P4O10. Their common names are phosphorus trioxide and phosphorus pentoxide,
respectively. The names are from their empirical formulas, which are P2O3 and P2O5
respectively. Tetraphosphorus hexaoxide is a low-melting solid (m. p. 23°C) and it dissolves in
water to give phosphorous acid, H3PO3, which does not have the structure P(OH)3 that its
formula suggests, but is tetrahedral with a P–H bond: HPO(OH)2. It is thus diprotic.
Tetraphosphorus decaoxide is an important oxide; it is a white solid, which sublimes at 360°C.
This oxide will dissolve in water to give phosphoric acid, H3PO4 (PO(OH)3). The reaction with
water is quite vigorous, making tetraphosphorus decaoxide useful in the laboratory as a drying
agent. It is prepared by burning white phosphorus in air. Organic phosphates are prepared by the
reactions of P4O10 with alcohols.

P4 + 5O2 → P4O10 P4O10 + 6H2O → 4H3PO4 P4O6 + 6H2O → 4H3PO3

P4O6 + 12ROH → 4PO(OR)3 + 6H2O

Oxoacids of Phosphorus

Phosphorus has many oxygen containing acids. These acids are can be considered as derivatives
of phosphoric acid. Phosphoric acid is a colorless solid, which melts at 42°C. Phosphoric acid is
a triprotic acid (with three replaceable acidic H atoms per molecule). Possible sodium salts are;
sodium dihydrogen phosphate (NaH2PO4), disodium hydrogen phosphate (Na2HPO4), and
trisodium phosphate (Na3PO4).

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Phosphoric acid is manufactured in large quantity by either directly from phosphate rock or from
tetraphosphorus decaoxide, which can be obtained by burning white phosphorus. In the direct
process, phosphate rock is treated with sulphuric acid, from which a solution of phosphoric acid
is obtained by filtering off the calcium sulphate and other solid materials. The product is an
impure phosphoric acid, which is used in the manufacture of phosphate fertilizers. Phosphoric
acid of higher purity is obtained by reacting tetraphosphorus decaoxide with water. It is used in
soft drinks for tartness (sourness or bitterness) and also in making phosphates for detergent
formulations. Phosphoric acid will undergo condensation reactions to form other phosphoric
acids. Example, two phosphoric acid molecules condense to form diphosphoric acid (also called
pyrophosphoric acid).

Two series of these phosphoric acids exist (all having phosphorus in the +5 oxidation state). One
series consists of the linear polyphosphoric acids, which are acids with the general formula Hn +
2PnO3n + 1 formed from linear chains of P–O bonds.

The other series is called metaphosphoric acids, which are acids with the general formula
(HPO3)n. They have cyclic or ring structures. When a linear polyphosphoric acid chain is very
long, the formula becomes (HPO3)n. The polyphosphates and metaphosphates are used in
detergents, where they act as water softeners by complexing with metal ions in the water.
Sodium triphosphate, Na5P3O10, one of the most commonly used polyphosphates, is
manufactured by adding sufficient sodium carbonate to phosphoric acid to give a solution of the
salts NaH2PO4 and Na2HPO4. When this solution is sprayed into a hot kiln (furnace), the
orthophosphate ions condense to give sodium triphosphate.

The use of phosphates in detergents has been criticized for contributing to the over-fertilization
of plants and algae in lakes (a process referred to as eutrophication). Such lakes become
oxygen-deficient from decomposing plants and algae, and the fish die. The use of phosphates in
laundry detergents has been banned in some part of the world.

Phosphates are also used as fertilizers, example calcium dihydrogen phosphate and calcium
sulphate (gypsum) known as superphosphate of lime. Another type of fertilizer is obtained by

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utilizing phosphoric acid instead of sulphuric acid, the product formed is richer in calcium
dihydrogen phosphate and it is called triple superphosphate. With nitric acid a fertilizer rich in
phosphate and nitrate is formed.

Ca3(PO4)2 + 2H2SO4 + 4H2O → Ca(H2PO4)2 + 2Ca(SO4).2H2O

Ca3(PO4)2 + 4H3PO4 → 3Ca(H2PO4)2 Ca3(PO4)2 + 4HNO3 → Ca(H2PO4)2 + 2Ca(NO3)2

Group VIA elements

Group VIA shows the trend from nonmetallic to metallic from top to bottom of the column of
elements. Oxygen and sulphur are strictly nonmetallic. Although the chemical properties of
selenium and tellurium are predominantly those of nonmetals, they do have semiconducting
allotropes as expected of metalloids. Polonium is a radioactive metal.

Oxygen

Oxygen is the most abundant element on Earth, making around 46% of the Earth’s crust by mass.
The commonest minerals are complex oxides such as silicates and carbonates. Oxygen is also a
constituent of water, and of nearly all biological molecules. Atmospheric O2 comes almost
entirely from photosynthesis by green plants. Reactions involving oxygen, both in
photosynthesis and in respiration by air-breathing animals, are important in nature. Oxygen can
be extracted from the atmosphere by liquefaction and fractional distillation. The liquid boils at -
183°C (90 K) and is dangerous when mixed with combustible materials. The compressed gas is
used in metallurgy (e.g. steelmaking) and the liquid as an oxidizer for rocket propulsion.

Oxygen, a second-period element, has rather different properties from those of the other
members of Group VIA. It is very electronegative, and bonding involves only s and p orbitals.
For the other members of Group VIA, d orbitals become a factor in bonding. Oxygen exists in
compounds mainly in the -2 oxidation state other states; -1 and -1/2 also do exist. The other Group
VIA elements exist in compounds in this state also, but the 4 and 6 states are common. Sulphur,
although not as abundant as oxygen, is a common element. Both oxygen and sulphur are
important to living organisms.

Allotropes of oxygen

Oxygen has two allotropes, the normal dioxygen O2 form and ozone O3 formed by subjecting O2
to an electric discharge. Ozone is a trace constituent of the atmosphere, where it plays an
important role as an absorber of UV radiation.

Oxygen can be prepared in small quantities by decomposing certain oxygen containing

compounds. Both the Swedish chemist Karl Wilhelm Scheele and the British chemist Joseph
Priestley are credited with the discovery of oxygen. Priestley obtained the gas in 1774 by heating

23
mercury(II) oxide. In one laboratory preparation, potassium chlorate, KClO3, is heated with pure
manganese(IV) oxide, MnO2, as a catalyst.

2HgO → 2Hg + O2 2KClO3 → 2KCl + 3O2

Oxides

Oxygen forms binary compounds with nearly all elements. Most may be obtained by direct
reaction, although other methods (such as the thermal decomposition of carbonates or
hydroxides) are sometimes more convenient. Oxides may be broadly classified as molecular
(CO2, H2O, SO2), polymeric (SiO2) or ionic (Na2O). Covalent oxides are formed with non-
metals.

Most metals react readily with oxygen to form oxides, especially if the metal is in a form that
exposes sufficient surface area. For example, magnesium wire and iron wool burn brightly in air
to yield the oxides.

2Mg + O2 → 2MgO 3Fe + 2O2 → Fe3O4

The alkali metals form an interesting series of binary compounds with oxygen. When an alkali
metal burns in air, the principal product with oxygen depends on the metal. With lithium, the
product is the basic oxide, Li2O. With the other alkali metals, the product is predominantly the
peroxide and superoxide. A peroxide is a compound with oxygen in the -1 oxidation state.
(Peroxides contain either the O22- ion) A superoxide is a binary compound
with oxygen in the -1/2 oxidation state; superoxides contain the superoxide ion, O2-.
Sodium metal burns in air to give mainly the peroxide.

4Na + O2 → 2Na2O K + O2 → KO2

Nonmetals react with oxygen to form covalent oxides, most of which are acidic. For example,
carbon burns in an excess of oxygen to give carbon dioxide, which is the acid anhydride of
carbonic acid (H2CO3). Sulphur burns in oxygen to give sulphur dioxide, SO2, the acid anhydride
of sulphurous acid (H2SO3). Sulphur forms another oxide, sulphur trioxide, SO3, but only small
amounts are obtained during the burning of sulphur in air. Sulphur trioxide is the acid anhydride
of sulphuric acid (H2SO4). Compounds of hydrocarbon such as methane, CH4, burns to give
carbon dioxide and water.

C + O2 → CO2 H2O + CO2 → H2CO3

S + O2 → SO2 H2O + SO2 → H2SO3
2S + 3O2 → 2SO3 H2O + SO3 → H2SO4
CH4 + 2O2 → CO2 + 2H2O

24
Water (H2O)
Water is the most abundant molecular substance on Earth. It is highly polar, with physical
properties dominated by hydrogen bonding, and an excellent solvent for ionic substances and
reactions. Autoprotolysis (self-dissociation) gives the ions H3O+ and OH-.

Peroxide (H2O2)

The alkali metals do not react with oxygen to produce normal oxides when there is an excess of
oxygen available. In some cases, a peroxide is obtained, which will react with water to produce
hydrogen peroxide.

Na2O2 + H2O → 2NaOH + H2O2

The most common form of H2O2 available in retail stores is a 3% solution, but this solution is an
effective disinfectant. It is possible to concentrate hydrogen peroxide by distillation up to a
concentration of approximately 30%. When that concentration is reached, the rate of
decomposition is high enough that no further concentration occurs. Decomposition of hydrogen
peroxide is catalyzed by minute traces of transition metal ions, which is easily seen when a drop
of 3% H2O2 is placed on a cut where blood is exposed. When handling concentrated H2O2, the
containers must be clean and free of metal compounds. Solutions that contain about 90% H2O2
are very strong oxidizing agents that have been used as the oxidizing agent in rockets. Hydrogen
peroxide has many uses that vary from bleaching paper pulp to production of polymers. The
decomposition of hydrogen peroxide can be shown as:

2H2O2 → 2H2O + O2

Positive oxidation states

Reaction with strong oxidizing agents gives the ion, which has a stronger and shorter bond than
O2.

25
2O2 + F2 + 2BF3 → 2[O2]+ [BF4]- (+1/2) 2F2 + O2 → 2F2O (+1) F2 + O2 → F2O2 (+1/2)

Ozone
Ozone is formed when electric spark is passed through oxygen an unusual odor results. That odor
is caused by ozone, O3, which has a characteristic pungent smell. In fact, ozone can be detected
at very low levels by its intense odor, and the Greek word ozein meaning to smell is origin of
the name ozone. Ozone (m.p. -193°C and b.p. -112°C) has a heat of formation of 143kJ/mol, so
it is unstable with respect to O2. Mixtures of ozone and oxygen are explosive. The O3 molecule is
isoelectronic with SO2, NO2-, and other triatomic species containing 18 valence shell electrons.
As a result, the structure can be represented by the resonance structures.

Ozone is unstable when compared to oxygen, and it can decompose explosively in the presence
of catalysts or ultraviolet radiation. Several substances catalyze the decomposition, including
Na2O, K2O, MgO, Al2O3, and Cl2. The real value of ozone lies in the fact that in the
upper atmosphere it absorbs ultraviolet radiation. The maximum in the absorption band is at
255nm. It is believed that chlorofluorocarbons used as a refrigerating gas and as a propellant for
aerosols are contributing to a reduction in the ozone layer. This has been the subject of much
research and discussion and has led to discontinuing the widespread use of chlorofluorocarbons.

For laboratory use, ozone is normally produced at the time and location of use by means of an
ozonizer. This device bombards oxygen with low frequency electrical oscillation (so-called silent
electric discharge) in a flow system. The effluent gas contains several percent O3, which is
usually passed directly into the reaction vessel. The reaction can be shown as

3O2 → 2O3

The ozone molecule can accept an electron to produce an ozonide, O3-. One of the most common
stable ozonides is KO3, which is a powerful and useful oxidizing agent. It is stable at
temperatures below 60°C, but it reacts with water,

K + O3 → KO3 4KO3 + 2H2O → 4KOH + 5O2

Uses of Ozone

Ozone itself is a useful and strong oxidizing agent that is comparable in strength to fluorine and
atomic oxygen. It is particularly useful in situations where a “clean” oxidizing agent is needed

26
because the reduction product is only oxygen. Water purification is such a situation, and ozone is
an effective germicide.

Ozone is a useful oxidizing agent in organic reactions, especially when double bonds are
involved. The product of such a reaction is known as an ozonide, and the general reaction can be
shown as

Sulphur

Sulphur occurs in sulphate minerals, such as gypsum (CaSO4.2H2O), and in sulphide (S2-);
galena (PbS), zinc blende (ZnS), cinnabar (HgS), and disulphide (S22-) minerals, many of which
are important metal ores. Pyrite is iron(II) disulphide, FeS2; while chalcopyrite, CuS2. These
compound consist of M2+ and S22- ions. Sulphur is also present in coal and petroleum as organic
sulphur compounds and in natural gas as hydrogen sulphide, H2S. Free sulphur occurs in some
volcanic areas, perhaps formed by the reaction of hydrogen sulphide and sulphur dioxide, which
are present in volcanic gases. Commercial deposits of free sulphur also occur in the rock at the
top of salt domes, which are massive columns of salt embedded in rock a hundred meters or
more below the earth’s surface. These deposits are believed to have formed by bacterial action
involving calcium sulphate minerals. Sulphur also occurs in several amino acids, which are the
building blocks of the proteins in living organisms. Plants are able to use sulphate ion as a source
of sulphur for the synthesis of amino acids. Animals and decay bacteria derive most of their
nutritional sulphur from organic sources.

Allotropes of Sulphur

Sulphur has a number of attractive allotropes, which include two crystal forms, rhombic sulphur
and monoclinic sulphur. Rhombic sulphur is the most stable form of sulphur; natural sulphur is
rhombic sulphur. It is a yellow, crystalline solid with a lattice consisting of
crown-shaped S8 molecules. The relative stability of this molecule results in part from the ability
of sulphur atoms to undergo catenation—that is, to form stable bonds to other sulphur atoms.
Rhombic sulphur melts at 113oC to give an orange colored liquid. When this liquid is cooled, it
crystallizes to give monoclinic sulphur. This allotrope also consists of S8 molecules; it differs
from rhombic sulphur only in the way the molecules are packed to form crystals. Monoclinic
sulphur melts at 119oC. It is unstable below 96oC, and in a few weeks at room temperature it
reverts to rhombic sulphur.

Liquid sulphur at temperature above 160oC begins to darken and at somewhat higher
temperatures changes to a dark reddish brown, viscous liquid. The original melt consists of S8

27
molecules, but these rings of sulphur atoms open up, and the fragments join to give long spiral
chains of sulphur atoms. The spiral chains have unpaired electrons at their ends, and these
unpaired electrons are responsible for the color. The viscosity of the liquid increases as compact
S8 molecules are replaced by long spiral chains that can intertwine. At temperatures greater than
200oC, the chains begin to break apart and the viscosity decreases. When molten sulphur above
160oC (but below 200oC) is poured into water, the liquid changes to a rubbery mass, called
plastic sulphur. Plastic sulphur is an amorphous mixture of sulphur chains. The rubberiness of
this sulphur results from the ability of the spiral chains of sulphur atoms to stretch and then relax
to their original length. Plastic sulphur reverts to rhombic sulphur after a period of time.
Sulphur boils at 445oC, giving a vapor of S8, S6, S4, and S2 molecules.

Production of Sulphur

Free sulphur that occurs in deep underground deposits is mined by the Frasch process, a mining
procedure in which underground deposits of solid sulphur are melted in place with superheated
water, and the molten sulphur is forced upward as a froth using air under pressure. A sulphur
well is similar to an oil well but consists of three concentric pipes. Superheated water flows
down the outer pipe, and compressed air flows down the inner pipe. The superheated water melts
the
sulphur, which is then pushed up the middle pipe by the compressed air. Molten sulphur spews
from the well and solidifies in large storage areas. Sulphur obtained this way is 99.6% pure.

Hydrogen sulfide, H2S, recovered from natural gas and petroleum is also a source
of free sulphur. The sulphur is obtained from the hydrogen sulfide gas by the Claus process,
a method of obtaining free sulphur by the partial burning of hydrogen sulfide. The partial
burning of hydrogen sulfide produces some sulphur, as well as sulphur dioxide. The sulphur
dioxide that produced reacts with the hydrogen sulfide to produce more sulphur. Most of the
sulphur produced (almost 90%) is used to make sulphuric acid. The remainder has a wide variety
of uses, including the vulcanization of rubber (sulphur converts the initially tacky material into
useful rubber), the production of carbon disulfide (to make cellophane), and the preparation of
sulphur dioxide for bleaching.

8H2S + 4O2 → S8 + 8H2O

2H2S + 3O2 → 2SO2 + 2H2O

16H2S + 8SO2 → 3S8 + 16H2O

Reactions of sulphur : Sulphur react with oxygen to give SO2 and with silver to give
silver sulphide. Sulphur also reacts with cyanides to give thiocyanates. Phosphorus and halogen
also combine with sulphur. Sulphur is oxidized to SO2 in hot concentrated nitric acid

S8 + 8O2 → 8SO2 S8 + 16Ag → Ag2S S8 + 8O2 → 8SO2 4P4 + 5S8 → 4P4S10

28
24F2 + S8 → 8SF6 8KCN + S8 → 8KSCN S8 + 32HNO3 → 8SO2 + 32NO2 + 16H2O

The most important binary compounds of sulfur and chlorine are S2Cl2 and SCl2. Both of these
compounds are used in large quantities in many ways, but one of the important uses for S2Cl2 is
in the vulcanization of rubber. This compound is prepared by chlorinating sulfur.

S8 + 4Cl2 → 4S2Cl2

Sulphur oxides and oxoacids

Sulphur dioxide (SO2)

Sulphur dioxide gas is very soluble in water, producing acidic solutions. Although these
solutions are often referred to as solutions of sulphurous acid, they appear to be composed
primarily of hydrated species of SO2; the acid H2SO3 has never been isolated. An aqueous
solution of sulphur dioxide, SO2(aq), does apparently contain small amounts of the ions HSO3-
and SO32-, which would be expected to be produced by the ionization of H2SO3; a diprotic acid.

S8 + 8O2 → 8SO2 H2O + SO2 → H2SO3

29
When a base is added to an aqueous solution of sulphur dioxide, the corresponding hydrogen
sulphite salt or sulphite salt is obtained. Sodium hydrogen sulphite (also called sodium
bisulphite) and sodium sulphite are produced this way commercially using sodium carbonate as
the base.

2H2SO3 + Na2CO3 → 2NaHSO3 + CO2 + H2O

H2SO3 + Na2CO3 → Na2SO3 + CO2 + H2O

Sulphites and hydrogen sulphites decompose when treated with acid to give sulphur dioxide.
This reaction can be used to prepare small amounts of sulphur dioxide in the laboratory.

Na2SO3 + 2HCl → 2NaCl + SO2 + H2O

SO2 react with PCl5 and Cl2 to give thionyl chloride and Sulphuryl chloride respectively. In the
presence of a catalyst, SO2 reacts with O2 to give SO3.

SO2 + PCl5 → SOCl2 + POCl3, SO2 + Cl2 → SO2Cl2, 2SO2 + O2 → 2SO3

Most of the sulphur dioxide is used to manufacture sulphuric acid. Some is used as a bleach
for wood pulp and textiles and as a disinfectant and food preservative (for example, in wine and
dried fruit). Its use as a food preservative depends on the fact that sulphur dioxide is especially
toxic to yeasts, molds, and certain bacteria. Because some people are allergic to sulphur dioxide,
foods containing it must be properly labeled.

Sulphur trioxide (SO3)

Sulphur trioxide is formed in small amounts when sulphur is burned in air, although
the principal product is sulphur dioxide. Thermodynamically, sulphur trioxide is the preferred
product of sulphur and oxygen. Sulphur dioxide does react slowly with oxygen in air to produce
sulphur trioxide, but the reaction is much faster in the presence of a catalyst, such as platinum.
Sulphur trioxide is produced commercially by the oxidation of sulphur dioxide in the presence of
vanadium(V) oxide catalyst. Sulphur trioxide reacts vigorously and exothermically with water to
produce sulphuric acid.

O2 + 2SO2 → 2SO3 H2O + SO3 → H2SO4

30
Sulphuric acid

The contact process is an industrial method for the manufacture of sulphuric acid. It consists of
the reaction of sulphur dioxide with oxygen to form sulphur trioxide using a catalyst of
vanadium(V) oxide, followed by the reaction of sulphur trioxide with water. Because the direct
reaction of sulphur trioxide with water produces mists that are unmanageable, the sulphur
trioxide is actually dissolved in concentrated sulphuric acid, which is then diluted with water.
Sulphuric acid is a component of acid rain and forms in air from sulphur dioxide, following
reactions that are similar to those involved in the contact process. Atmospheric sulphur dioxide
has both natural and human origins. Natural sources include plant and animal decomposition and
volcanic emissions. However, the burning of coal, oil, and natural gas has been identified as a
major source of acid rain pollution. After persisting in the atmosphere for some time, sulphur
dioxide is oxidized to sulphur trioxide, which dissolves in rain to give H2SO4.

More sulphuric acid is made than any other industrial chemical. Most of this acid is used to make
soluble phosphate and ammonium sulphate fertilizers. Sulphuric acid is also used in petroleum
refining and in the manufacture of many chemicals.

Concentrated sulfuric acid contains about 98% of the acid, which is equivalent to an 18 M
solution. There is extensive hydrogen bonding as indicated by the high viscosity and boiling
point of the liquid. The reaction of sulfuric acid with water is exothermic, so dilution should
always be carried out by adding the acid to water while stirring the solution. Because of its
affinity for water, sulfuric acid is a strong dehydrating agent. Several hydrates of sulfuric acid
have been identified, some of which are H2SO4.H2O (m.p. 8.5°C), H2SO4.2H2O (m.p. 39.5°C),
and H2SO4.4H2O (m.p. 28.2°C). Some of the properties of sulfuric acid are as follows.

The fact that the S–O bonds to oxygen atoms that do not have hydrogen atoms attached are
significantly shorter than the others is a manifestation of π bonding. If the structure contained
only single bonds (as just shown) the sulfur would have a +2 formal charge and the two types of
S–O bonds would not differ much in length. In order to reduce the positive formal charge,

31
multiple bonding occurs to two oxygen atoms, which reduces the bond length. That this is
correct is shown by the structure of the HSO4- ion that remains after the H2SO4 molecule
functions as a proton donor. Note that the bond between sulfur and the OH group is not much
different than that in the H2SO4 molecule, but the other three S–O bonds are lengthened
compared to H2SO4 the molecule. This is the result of the π bonding being distributed to three
oxygen atoms rather than just two.

Salts of H2SO4 include both the normal sulfates containing SO42- and acid sulfates or bisulfates
that contain HSO4-. When bisulfates dissolve in water, the solutions are somewhat acidic because
of the dissociation of the HSO4- ion. Bisulfates and sulphates are produced by reactions such as
the following:

NaOH + H2SO4 → NaHSO4 + H2O NaOH + NaHSO4 → Na2SO4 + H2O

NaCl + H2SO4 → NaHSO4 + HCl

CaCl2 + H2SO4 → CaSO4 + 2HCl Ca(OH) + H2SO4 → CaSO4 + 2H2O

Zn + H2SO4 → ZnSO4 + H2

At High temperature, H2SO4 reacts as a powerful oxidizing agent leading to formation of

sulphates and release of SO2

2H2SO4 + Cu → CuSO4 + 2H2O + SO2

32
Disulphorous acid

The acid produced when a molecule of water is removed from two molecules of H2SO3 is
disulphurous (pyrosulphurous) acid, H2S2O5. Even though the acid is not stable, a few salts are
known that contain the S2O52- ion, which has the structure.

When SO2 is added to a solution containing a sulfite (SO32-), the S2O52- ion is produced so the
solution contains a salt of disulfurous acid (pyrosulfurous) acid. In aqueous solutions, these salts
decompose when an acid is added.

Na2SO3 + SO2 → Na2S2O5 Na2S2O5 + HCl → NaHSO3 + SO2 + NaCl

Dithionous acid and Dithionites

One of the unstable oxyacids of sulfur is dithionous acid, H2S2O4, which contains sulfur in the
+3 oxidation state. Reduction of sulfur +4 to produce the dithionite ion is accomplished as shown
in the following equation:

NaHSO3 + SO2 + Zn → S2O42- + ZnSO3 + H2O

The O–S–O bond angle is 108°. The ion is reactive, as indicated by the fact there is isotopic
exchange reaction when labeled SO2 is added to a solution of a dithionite. A typical S–S bond
length is approximately 210 pm, so the bond length of 239 pm indicates a weak, reactive bond,
which is illustrated by the following equation:

2Na2S2O4 + H2O → Na2S2O3 + 2NaHSO3

It is believed that S2O42- establishes an equilibrium that can be represented as

S2O42- ⇋ 2SO2-

Sodium dithionite, Na2S2O4.2H2O, is a widely used reducing agent in several processes.

Dithionic Acid and Dithionates

This is another of the unstable oxyacids of sulfur that appears to contain sulfur 5. The structure
of the dithionate anion is

33
Writing the formula as (HO)S(O)2S(O)2OH shows that it is a strong acid. The S–S bond is
slightly longer than a typical single bond, but the S–O bond length is close to that in sulfuric
acid. Sulfites can be oxidized to give dithionates. When heated, metal dithionates generally
disproportionate to give a sulfate and SO2.

2Na2SO3 + MnO2 + 4HCl → Na2S2O6 + MnCl2 + 2H2O + 2NaCl

Na2S2O6 → Na2SO4 + SO2

The dithionate ion is a good coordinating ion that forms stable chelates. In addition to dithionic
acid, some polythionic acids having the formula H2SnO6 are known in which the sulfur chain
contains more than two sulfur atoms.

Peroxydisulfuric and Peroxymonosulfuric Acids

This acid, H2S2O8, is a solid that melts at 65°C. The acid and its salts are such strong oxidizing
agents that combustible materials can be ignited by them. The usual salts that are widely used as
oxidizing agents are the sodium, potassium, and ammonium salts. Electrolytic oxidation of
bisulfate is the usual method of producing the acid. When H2S2O8 is hydrolyzed, it produces
H2O2 and sulfuric acid. With one molar equivalence of water, a peroxymonosulphuric (Caro’s)
acid is formed, which can also be formed by reaction of chlorosulphonic acid with peroxide.

2HSO4- → H2S2O8 + 2e- H2S2O8 + 2H2O → 2H2SO4 + H2O2

H2S2O8 + H2O → H2SO4 + HOOSO3H HOSO2Cl + H2O2 → HOOSO3H + HCl

Oxohalide of sulphur

The oxyhalides of sulpur constitute a reactive and useful group of compounds. The two most
important types of oxyhalides are the SOX2 and SO2X2.

Thionyl chloride and sulphuryl chloride have structures in which the oxygen and halogen atoms
are attached to the sulfur. The hydrolysis reactions of thionyl chloride takes place readily, and
SOCl2 has such an affinity for water that is used as a dehydrating agent. When dehydrating a
compound such as a metal chloride, the gaseous products of the reaction make it easy to separate
the anhydrous solid.

SO2 + PCl5 → SOCl2 + POCl3, SO2 + Cl2 → SO2Cl2, 2SO3 + SCl2 → SOCl2 + SO2

SOCl2 + H2O → SO2 + 2HCl CoCl2.6H2O + 6SOCl2 → 6SO2 + 12HCl + CoCl3

34
Chlorine is a strong oxidizing agent that converts SO2 into sulphuryl chloride, SO2Cl2. In the
reaction, sulphur is oxidized as chlorine is added.

SO2 + Cl2 → SO2Cl2

The SO2Cl2 molecule can be considered as sulphuric acid in which the OH- groups have been
replaced by Cl- to produce an acid chloride. As expected, it undergoes solvolysis reactions.

SO2Cl2 + 2H2O → H2SO4 + 2HCl SO2Cl2 + 2NH3 → SO(NH2)2 + 2HCl

Sulphuryl fluoride is produced by the reaction of SO2 or SO2Cl2 with fluorine.

SO2Cl2 + F2 → SO2F2 + Cl2 SO2 + F2 → SO2F2

Since sulphuryl chloride and sulphuryl fluoride can be considered as the disubstituted acid
halides of sulfuric acid, the monosubstituted derivatives are also useful compounds that undergo
many reactions a result of the reactive –OH group. The monosubstituted compounds can be
prepared by the following reactions:

SO3 + HCl → HOSO2Cl PCl5 + H2SO4 → POCl3 + HOSO2Cl + HCl

SO3 + HF → HOSO2F HOSO2Cl + KF → HOSO2CF + KCl

HOSO2Cl + H2O → H2SO4 + HCl HOSO2F + H2O → H2SO4 + HF

Fluorosulphonic acid can be used in fluorination reactions, and it functions as a catalyst in

reactions such as alkylation and polymerization. One of the most important uses of FSO2OH and
ClSO2OH is as sulfonating agents to introduce the – SO3H group into various organic materials.

35
Group VIIA

The halogen group (VIIA) is the most electronegative in the periodic table, and all elements
readily form halide ions X-. Fluorine is limited to an octet of valence electrons. It is the most
electronegative and reactive of all elements. F and Cl are moderately abundant elements,
principal sources being fluorite CaF2 and halide NaCl, from which the very electronegative
elements are obtained by electrolysis. Bromine is mainly obtained by oxidation of Br- found in
salt water; iodine occurs as iodates such as Ca(IO3)2. Astatine is radioactive and only minute
amounts are found in nature. Chlorine is used (as ClO- and ClO2) in bleaches and is an important
industrial chemical, other major uses (as with all the halogens) being in the manufacture of
halogenated organic compounds. The elements form diatomic molecules, F2 and Cl2 being gases
at normal temperature and pressure, Br2 liquid and I2 solid. They react directly with most other
elements and are good oxidizing agents.

All of the halogens form stable compounds in which the element is in the -1 oxidation state. In
fluorine compounds, this is the only oxidation state. Chlorine, bromine, and iodine also have
compounds in which the halogen is in one of the positive oxidation states +1, +3, +5, or +7. The
higher positive oxidation states are due to the involvement of d orbitals in bonding.

Chlorine

Chlorine gas, Cl2, was discovered in 1774 by the Swedish chemist Karl Wilhelm Scheele by
heating hydrochloric acid with manganese dioxide. He immediately noted the suffocating odor of
the gas. Scheele also discovered that chlorine solutions could bleach cotton cloth. Within a few
decades, chlorine-based bleaches became major items of commerce. Currently, chlorine is the
most commercially important halogen.

4HCl + MnO2 → MnCl2 + 2H2O + Cl2

Properties of Chlorine

Chlorine gas has a pale greenish yellow color. It is a very reactive oxidizing agent and supports
the combustion of many substances in a manner similar to oxygen. All of the halogens are
oxidizing agents, though the oxidizing power decreases from fluorine to iodine. Thus, chlorine is
a stronger oxidizing agent than either bromine or iodine. When chlorine gas is bubbled into a
bromide solution, free bromine is obtained. Similarly, chlorine oxidizes iodide ion to iodine.

Cl2 + 2NaBr → 2NaCl + Br2 Cl2 + 2NaI → 2NaCl + I2

These reactions can be used as a test for bromide and iodide ions. Suppose an aqueous solution
of chlorine is added to a test tube containing either bromide or iodide ion. The corresponding
free halogen is formed in the water solution. It is readily identified by adding the organic solvent
methylene chloride, CH2Cl2, which dissolves the halogen, forming a colored layer at the bottom
of the test tube. Bromide ion gives an orange layer; iodide ion gives a violet layer. Of course,

36
neither bromine nor iodine is strong enough to oxidize chloride ion. Chlorine reacts with water
by being both oxidized and reduced.

H2O + Cl2 → HOCl (+1) + HCl (-1)

Preparation and Uses of Chlorine

Chlorine is a major industrial chemical. It is prepared commercially by the electrolysis of

aqueous sodium chloride. Chlorine can be prepared in small amounts for laboratory use by the
reaction of chloride ion with a strong oxidizing agent, such as potassium dichromate or
manganese dioxide. Another but less common industrial reaction is based on the oxidation of
HCl in which oxides of nitrogen function as a catalyst. A procedure used by Scheele in 1774
involves heating a solution of HCl with MnO2.

4HCl + O2 → 2Cl2 + 2H2O 4HCl + MnO2 → MnCl2 + H2O + Cl2

The principal use of chlorine is in the preparation of chlorinated hydrocarbons, such as vinyl
chloride, CH2=CHCl (for polyvinyl chloride plastics), and methyl chloride, CH3Cl (for the
manufacture of silicones, polymers with Si-O bonds and organic groups). Various insecticides
are also chlorinated hydrocarbons; many of these (such as DDT) are now restricted in their use
because of possible environmental damage. Other major uses of chlorine are as a bleaching agent
for textiles and paper pulp and as a disinfectant. Not long after the discovery of chlorine, chlorine
bleaches became available commercially. Chlorine solutions were used as disinfectants early in
the nineteenth century. Today, chlorine gas is commonly used for disinfecting municipal water
supplies.

Hydrogen Chloride

Hydrogen chloride, HCl, is a colorless gas with a sharp, penetrating odor. The gas is very soluble
in water, and the water solution is commonly referred to as hydrochloric acid. The molecular
species HCl ionizes nearly completely in aqueous solution. Hydrogen chloride can be produced
by heating sodium chloride with concentrated sulphuric acid.

Hydrogen bromide and hydrogen iodide can also be produced from their salts by a similar
replacement reaction, but in these cases phosphoric acid is used instead of sulphuric acid, which
tends to oxidize the bromide and iodide ions to the respective elements.

2KCl + H2SO4 → 2HCl + K2SO4 3KI + H3PO4 → 3Hl + K3PO4

Most of the hydrogen chloride available commercially is obtained as a by-product in the

manufacture of chlorinated hydrocarbons. In these reactions, hydrogen bonded to carbon is
replaced by chlorine, forming the chlorinated compound and HCl.

37
Hydrochloric acid is the fourth most important industrial acid (after sulphuric, phosphoric, and
nitric acids). It is used to clean metal surfaces of oxides (a process called pickling) and to extract
certain metal ores, such as those of tungsten.

CH4 + 2Cl2 → CCl4 + 4HCl

Oxoacids of Chlorine

The halogens form a variety of oxoacids. The acidic character of these acids increases with the
number of oxygen atoms bonded to the halogen atom—that is, in the order HClO, HClO2,
HClO3, HClO4. Perchloric acid, HClO4, is the strongest of the common acids. Of the chlorine
oxoacids, only perchloric acid is stable; the other oxoacids have never been isolated and are
known only in aqueous solution. Hypochlorous acid, HClO, is produced when chlorine
disproportionates (is oxidized and reduced) in water.

Solutions of sodium hypochlorite are manufactured by allowing the chlorine gas released by the
electrolysis of aqueous sodium chloride to mix with the cold solution of sodium hydroxide that is
also obtained in the electrolysis. These solutions are sold as a bleach. Hypochlorite ion itself is
unstable, disproportionating into chlorate ion, ClO3-, and chloride ion.

At room temperature the reaction is slow; but in hot solution in the presence of base, the reaction
is fast. Therefore, when chlorine reacts with hot sodium hydroxide solution, sodium chlorate is
the product instead of sodium hypochlorite.

2NaOH + Cl2 → NaOCl + NaCl + H2O 3NaOCl → NaClO3 + 2NaCl

References

1. De, A. Ke. A Textbook of Inorganic Chemistry (9th ed.) New Age International, New
Delhi, 2003.

2. Ebbing, D. D. and Gammon, S. D. General Chemistry (9th ed.) Houghton Mifflin

Company, USA, 2009.

3. Lee, J. D. Concise Inorganic Chemistry (5th ed.) Willey-Blackwell Science, London, 2005

4. Miessler, G. L. and Tarr, D. A. Inorganic Chemistry (3rd ed.) Pearson Education Int,
2010.

5. Wilson, J. G. and Newall, A. B. General and Inorganic Chemistry. Cambridge University

Press, London, 1966.

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