Inorganic chemistry II

Second stage / Second semester

Seventh lecture 2021/2022 Pro. Dr. Mohammed Hamid
Elements of Group VIA or 16
(The Oxygen Family, ns2np4)
POSITION IN PERIODIC TABLE
Group 16 or VIA of the extended form of periodic table consists of six elements oxygen
(O), sulphur (S). selenium (Se), tellurium (Te), polonium (Po) and ununhexium (Uuh)".
This family is known as oxygen family. These (except polonium and ununhexium) are the
ore forming elements and thus called chalcogens. These are p-block elements as the last
differentiating electron is accommodated on np shell. These elements have six electrons in
their valency shell and thus placed in the VIth group.
The elements oxygen and sulphur are common while selenium, tellurium and polonium
are comparatively rare. Oxygen is the most abundant element and is found both in free as
well as in combined state. Oxygen makes up 20.9% by volume and 23% by mass of
atmosphere. Most of the oxygen present in the atmosphere is produced by photosynthesis
in plants. It also occurs in the form of ozone in the upper atmosphere which protects us
from the harmful radiations of the sun. Oxygen makes up 46.6% by mass of the earth's
crust. Sulphur is the sixteenth most abundant element and constitutes 0.034% by mass of
the earth's crust. It occurs mainly in combined form. The member, polonium is radioactive
in nature. The inclusion of these elements in the same subgroup is justified on the basis of
same electronic configuration and similarities as well as gradation in their physical and
chemical properties.
Like other groups, the first element oxygen differs from other elements of the group in
several respects.
1. Electronic Configuration
The distribution of electrons in various energy shells of the atoms of these elements is
given as below:
Element At.NO. Electronic configuration Inert gas core
2 2 4
O 8 1s 2s 2P [He]2s22P4
S 16 1s22s22P63s23P4 [Ne]3s23P4
Se 34 1s22s22P63s23P63d104s24P4 [Ar]3d104s24P4
Te 52 1s22s22P63s23P63d104s24P64d105s25P4 [Kr]4d105s25P4
Po 84 1s22s22P63s23P63d104s24P64d10 4f14 5s2 5P6 [Xe]4f145d106s2 6P4
5d10 6s2 6P4
Uuh 116 1s22s22P63s23P63d104s24P64d10 4f14 5s2 5P6 [Rn]5f146d107s2 7P4
5f14 5d10 6s2 6P66d107s2 7P4
All have six electrons in their outermost shell, i.e., they have electronic structure s2p4. The
penultimate shell contains 2 electrons in oxygen, 8 electrons in sulphur and 18 electrons in
Se, Te, Po and Uuh. This explains why oxygen differs from sulphur and these two from
the remaining elements.
2. Physical Characteristics
(a) Physical state: Oxygen is a gas while others are solids. Oxygen molecule is diatomic
while the molecules of other elements are more complex. Sulphur, selenium and tellurium
exist as staggered 8-atom rings. However, the tendency to exist in 8-atom rings is
maximum with sulphur and decreases as we go down the group. In Sg molecule, every
sulphur atom is in sp³ hybridized state involving both bonding and non bonding pairs of
electrons.

Staggered ring structure of sulphur molecule, S8

[Oxygen atom has the tendency to form multiple bonds (pπ-pπ interaction) with other
oxygen atom on account of small size while this tendency is missing in sulphur atom. The
bond energy of oxygen-oxygen double bond (O=O) is quite large (about three times that
of oxygen-oxygen single bond, O-O = 34.9 kcal mol) while sulphur-sulphur double bond
(S=S) is not so large (less than double of sulphur-sulphur single bond, S-S = 63.8 kcal
mol). As a result, -O-O-O- chains are less stable as compared to O=O molecule while -S-
S-S- chains are more stable than S=S molecule. Therefore, at room temperature, while
oxygen exists as a diatomic gas molecule, sulphur exists as S8 solid.]
The plastic sulphur which is formed by pouring liquid sulphur into water contains zig-zag
long chains of sulphur atoms.

At temperatures above the boiling points, sulphur forms a red vapour, which turns to
yellow as temperature is increased. In vapour there exist S8. S6 and S₂ molecules. Above
1000°C, there exist only S₂ molecule, which has structure like O₂.
(b) Metallic and non-metallic character: Metallic character increases with the increase of
atomic number. Oxygen and sulphur are distinctly non-metallic. Selenium and tellurium
show both non-metallic and metallic characters but polonium is definitely a metal.
(c) There is a gradual gradation in physical properties :
(i) Atomic and ionic radii: The atomic radii of the elements of group 16 are smaller than
those of the corresponding elements of group 15. The atomic radii of the elements of this
group increase gradually on moving down the group.
Element O S Se Te Po
Atomic radii (pm) 66 104 117 137 146
[covalent radii (single bond)]

The smaller atomic radii of group 16 elements as compared with corresponding elements
of groups 15 are due to the increased effective nuclear charge with increase in greater
attraction towards nucleus. The attraction brings contraction in size. The gradual increase
on moving down the group is due to the increase in the number of electron shells from
member to member.
In the formation of anions, two electrons are being added to an atom. Therefore, the
effective nuclear charge is reduced and hence, the electron closed expands. Thus, the
negative ions (M²) are bigger in size than the corresponding atoms. Like atomic radii,
ionic radii also increase gradually on moving down the group.
Element O S Se Te
Ionic radii (pm) 140 184 198 221
(ii) Ionisation energy: The ionisation enthalpies are high and thus the elements do not lose
the electrons to form positive ions easily. The values decrease as the atomic number
increases from O to Po and thus the tendency to form positive ion increases gradually, i.e.,
metallic nature incrases.

The ionisation energies of first three elements of group 16 are less than corresponding
elements of group 15 inspite of the fact that nuclear charge increases. The abnormal
behaviour is due to symmetrical and more stable electronic configuration of N. P and As
as compared to O. S and Se respectively. However, the second ionisation values of group
16 elements are higher than those of group 15.
(iii) Electronegativity: Electronegativity decreases gradually. Oxygen is second most
electronegative element after fluorine.
O S Se Te Po
Electronegativity 3.5 2.44 2.48 2.01 1.76
Decreases gradually
This decrease indicates a change from non-metallic to metallic character.
(iv) Melting and boiling points: The melting and boiling points increase gradually with
increase in atomic number.
O S Se Te
Melting point (°C) -219 119 217 450
(Monoclinic)

Boiling point (°C) -183 445 688 990

(v) Electron affinity: Group 16 elements have high electron affinities. On moving from
oxygen to sulphur, the EA₁ value increases and then decreases from S to Po.
Element O S Se Te Po
EA, (kJ mol¹) -141 -200 -195 -190 -183
The electron density in 2p energy shell in oxygen is high due to small size of oxygen atom
and thus, there is some resistance to the incoming electron and thereby the EA of oxygen
is comparatively low. Sulphur has maximum value and on moving from S to Po, the EA1
values decrease due to increased size. the elements show allotropy:
(d) Allotropy: All the Element show Allotropic
Element Allotropic forms
Oxygen Ordinary oxygen and ozone
Sulphur Rhombic, monoclinic, plastic, amorphous
Selenium Red form (non-metallic),grey form (metallic form)
Tellurium Crystalline and amorphous
Polonium α and β forms (Both are metallic forms)
(e) Catenation : Oxygen and sulphur show the property of catenation. The property is
more pronounced in sulphur. H-O-O-H, H-S-S-H, H-S-S-S-H, H-S-S S-S-H, the peroxides
and polysulphides are fairly stable.
(f) Oxidation states: As the configuration of outer most shell is ns² np4, these elements try
to gain or share two electrons in order to attain inert gas configuration. Oxygen being
highly electronegative shows-2 oxidation state in its compounds except in oxygen
fluorides and most of the metal oxides are ionic and contain oxygen as dinegative anion.
O²- Since the electronegativity decreases, the tendency to exhibit -2 oxidation state
decreases as we go down in the group. However, positive oxidation states are exhibited by
S, Se, Te and Po. In addition to +2 oxidation state, +4 and +6 oxidation states are
observed. This is due to the availability of d-orbitals in these elements. Oxygen has no d-
orbitals and hence cannot show +4 and +6 oxidation states while sulphur can have 2, 4 or
6 unpaired orbitals forming 2, 4 or 6 covalent bonds.
Thus, oxygen is never more than divalent while other members may be divalent,
tetravalent and hexavalent. The compounds having +4 oxidation state show both oxidising
and reducing properties while compounds having +6 oxidation states are only oxidising.
(g) Multiple bonding: Oxygen atom has the tendency to form multiple bonds (pπ-pπ
interaction) with the other oxygen atom on account of small size and high
electronegativity. However, the rest of the elements do not form pπ-pπ multiple bonds due
to their large size. Sulphur and higher members of group 16 possess vacant d-orbitals in
their valence shell. They use these orbitals to form dπ-pπ bonds. However, this tendency is
maximum and stronger in sulphur and decreases from sulphur onwards.
3. Trends in Chemical Reactivity
Oxygen is the most reactive element of the group despite it has high bond dissociation
energy of oxygen molecule (493.4 kJ mol-¹) as nearly all its reactions are exothermic.
Once initiated, these reactions continue spontaneously. Oxygen directly combines with
almost all the metals except noble metals, all the non-metals except noble gases and
halogens and many compounds under suitable conditions. The oxides are generally stable
compounds. The elements such as W, Pt, Au, halogens and noble gases which do not
directly combine with oxygen, form compounds with oxygen indirectly.
After oxygen, sulphur is quite reactive element especially at high temperatures which help
in breaking of S-S bonds. Sulphur burns in air and reacts directly with carbon,
phosphorus, arsenic and many metals. Oxidising acids oxidise it into SO2 and alkalies
dissolve it to give sulphides and thiosulphates. It reacts with H₂ and halogens. The
sulphides are stable compounds and many metals are found in nature in the form of
sulphides.
However, the reactivity of group 16 elements decreases from oxygen to polonium..
O > S > Se> Te > Po
Selenium and tellurium combine with highly electropositive elements such as alkali and
alkaline earth metals. Se and Te combine with oxygen, fluorine and chlorine. In general,
the compounds of selenium and tellurium are less stable than oxygen and sulphur.
Some important trends in chemical reactivity of elements of group 16 are discussed
here.
(a) Hydrides
All the elements of this group form the hydrides of type H₂M where, M = O, S, Se, Te and
Po, i.e.,
H₂O, H₂S, H₂Se, H₂Te and H₂Po
H₂O is obtained by burning hydrogen in the atmosphere of oxygen while H₂S, H₂Se and
H₂Te are obtained by the action of acids on sulphides, selenides and tellurides.
FeS + H₂SO4 → FeSO4 + H₂S.
Na₂Se + H₂SO4 → Na₂SO4 + H₂Se
(i) Physical state: Water is colourless, odourless liquid while other hydrides are colourless,
poisonous gases with bad odours.
(ii) Volatility: Water has low volatility (high boiling point) as hydrogen bonding brings
association. H₂S has high volatility as no hydrogen bonding is present. Volatility
decreases from H₂S to H₂Te due to increase in molecular masses of the hydrides.
(iii) Covalent character: As the electronegativity difference between M and H decreases,
the covalent character of these hydrides increases from H₂O to H₂Te. Water molecule is
highly polar. It has high dielectric constant and hence acts as an excellent solvent for
inorganic compounds.
(iv) Thermal stability: The thermal stability decreases as the atomic mass increases. Water
dissociates at 2000°C while tellurium hydride, H₂Te, decomposes at room tem perature.
This is due to an increase in M-H bond length.
(v) Acidic nature:The hydrides are all weak acids and dissociate to varying degrees to give
H+ ions. The acidic strength increases from H₂O to H₂Te as it is evident from the values
of dissociation constants.

H₂O H₂S H₂Se H₂Te

Dissociation 1.0 x 10-14 1.0 x 10-7 1.7 x 10-4 2.3 x 10-3
constant (25°C)

The increasing trend can be explained on the basis of dissociation energies. The
dissociation energies decrease as the bond length M-H increases from oxygen to tellurium.
This facilitates the release of proton. The acidic nature can also be explained on the basis
of charge density on M2- anion. The charge density on the M2- ion decreases as the size of
M-atom increases from oxygen to tellurium. The decrease in charge density is responsible
for the decrease in dissociation energies and thereby increasing the tendency to furnish
proton.
(vi) Reducing nature: All hydrides except H₂O act as reducing agents. The reducing
nature increases as the atomic number of the central atom increases. This is due to
weakening of M-H bond as the bond length increases with increase of size of M-atom.
(vii) Burning: H₂S, H₂Se, H₂Te and H₂Po burn in atmosphere of oxygen with blue flame
forming dioxides.
2H₂S + 3O2 → 2H₂O +2SO₂
(viii) Shape: All these hydrides are V-shaped. In these hydrides, the central atom is sp³
hybridized. The bond angles are 104.5°, 92.5°, 91° and 90° in H₂O, H₂S, H₂Se and H₂Te,
respectively.
This can be explained on the basis of decreasing electronegativity of central atom and
decreasing tendency of sp3 hybridization.
Other hydrides
Oxygen and sulphur have a tendency to form polyoxides nd polysulphides which are
comparatively less stable. The wo common examples are H₂O₂ (hydrogen peroxide) and
H2S2 (hydrogen disulphide). They decompose on heating.
2H₂O₂ 2H₂O + O₂
H₂S₂ → H₂S + S
Hydrogen polysulphides (H-Sn -H', n may be 2, 3, 4, 5) are How oily liquids which
possess a more strong odour than H₂S.
(b) Oxides
The most important oxides are of the type MO₂ and MO₂. SO₂ and SeO₂ are acidic oxides
and are soluble in water. TeO2 and PoO₂ are insoluble in water. These are amphoteric
oxides as they dissolve in both acids and bases.
SO₂ + H₂O → H₂SO3 (Sulphurous acid)
SeO₂ + H₂O → H₂SeO3(Selenous acid)
TeO₂ + 2NaOH → Na₂TeO3 + H₂O
Sodium tellurite

2TeO₂ + HNO3 → 2TeO₂ HNO3 or Te₂O3-(OH)NO3

Basic nitrate

SO₂ is a gas, SeO2 is a volatile solid and TeO2 is a white non-volatile solid. All the
dioxides possess different structures. SO₂ is an angular molecule with an O-S-O angle of
119.5⁰. The sulphur undergoes sp² hybridization. Both the bonds have same bond lengths.
This suggests resonance in the molecule. SeO₂ has the same structure as SO₂ in the
gaseous state but the solid has a chain like structure which is not planar.
 TeO₂ and PoO₂ are crystalline ionic solids.
Trioxides: SO3, SeO3 and TeO3 are acidic in nature.
SO3 + H₂O → H₂SO4 (Sulphuric acid)
SeO3 + H₂O → H₂SO4 (Selenic acid)
TeO3 + 3H₂O → HTeO6 (Telluric acid)
The acidic nature decreases on moving down the group. SO3 is a gas and has plane
triangular structure. The structure of SO3 is similar to that of SO₂ except for the fact that
lone pair of electrons of sulphur atom is donated to third oxygen atom. According to
another view, the true structure of SO molecule is considered to be resonance hybrid of
the following structures.

In the solid state ,SO3 exists as a cyclic trimer or a linear chain

Cyclic trimer of SO3 Linear chain of SO3

Solid selenium trioxide is a cyclictetramer [Se4O12]

(c) Oxyacids or oxoacids

Sulphur forms a number of oxyacids but selenium and tellurium form only two series of
oxyacids, the-ous and -ic acids.
H₂SO3 H₂SeO3 H₂TeO3
Sulphurous acid Selenous acid Tellurous acid
Salts Sulphite Selenites Tellurites
H₂SO4 H₂SeO4 H₂TeO4 or HTeO6
Sulphuric acid Selenic acid Telluric acid
Sulphates Selenates Tellurates

Oxyacids with S-S linkages are called thioacids and with O-O linkages are termed peroxy
acids. Thionic acids have two-SO3H groups linked either directly or through a S-chain
(polythionic acids).
With increase oxidation number, the acid strength of oxyacid of an element increases, i.e.,
sulphuric acid is stronger than sulphurous acid. In the oxyacids of group 16 elements in
same oxidation state, the acidic nature decreases from S to Te. The -ous acids act as
reducing agents while -ic acids act as oxidizing agents. These properties decrease from S
to Te. Oxyacids are dibasic in nature.
(d) Halides
S, Se and Te form hexafluorides showing the maximum valency of six. They all involve
sp3d² hybridization.

Thus, hexafluorides possess octahedral structure. These are colourless gases.SF6 is

extremely inert.

SeF6 is slightly reactive while TeF6 is hydrolysed by water.

TeF6 + 6H₂O → 6HF +HTeO6
No other halogen forms the hexahalides due to larger size of Cl, Br and I
Many tetrahalides are known. SF4 is a gas, SeF4 is a liquid while TeF4 is a solid. S, Se, Te
and Po form tetrachlorides and bromides while Te and Po form tetraiodides. All
tetrahalides possess trigonal bipyramid structure with sp3d hybridization.

Four unpaired electrons form bonds with four halogen atoms and one position is occupied
by lone pair.

SF4 is very reactive and is readily hydrolysed by water give SO₂ and HF inspite of the fact
that average bond energy in SF4 is greater than SF6. This is due to the presence of empty
3d-orbitals in sulphur atom in SF4. It is used as fluorinating agent for many inorganic and
organic compounds.
All the elements except selenium form stable dichlorides and dibromides, Di-jodides are
not formed. Dihalides form tetrahedral molecules due to sp3 hybridization.

The bond angle is less than 109°28' due to the presence of lone pairs. The bond angle is
103° in SC1₂, 101.5° in OF, and 98° in TeBr₂.
Dimeric monohalides as S₂F₂. S₂Cl₂ and S₂Br₂ are known.Their structure is similar to
H₂O₂.

[Note: As fluorine is more electronegative than oxygen, the compounds of oxygen and
fluorine are called fluorides. For example, OF₂ is named oxygen difluoride. The
compounds of oxygen and other halogens are called oxides as oxygen is more
electronegative than chlorine, bromine and iodine. For example, ClO₂ is called chlorine
dioxide and I₂O5 is named iodine pentoxide.]
(e) Oxyhalides
Only S and Se form oxyhalides. They are called thionyl and selenyl halides.
SOF₂ SOCl2 SOBr₂
SeOF2 SeOCl₂ SeOBr₂
These react with water readily.
SOCl₂ + H₂O SO₂ + 2HCl
In addition, sulphuryl halides are also known.
SO2X2
These may be regarded as derivatives of H₂SO4 where both the OH groups have been
replaced by two halogens atoms.
ABNORMAL BEHAVIOUR OF OXYGEN
Oxygen differs from rest of the members of VIA group elements. The abnormal behaviour
is attributed due to the following inherent characteristics :
(i) Small size
(ii) High electronegativity
(iii) Non-availability of d-orbitals in the valency shell.
Points of difference
(i) Oxygen is a gas while others are solids.
(ii) It is diatomic molecule, while the rest are complex molecules, e.g., S8. Se8 with
puckered ring structure.
(iii) Oxygen is highly non-metallic due to high value of electronegativity.
(iv) Oxygen is more ionic in its compounds. The dinegative anion O2- is quite common.
The dinegative anions of other members are less common.
(v) Oxygen exhibits an oxidation state of only -2 except in OF2 and peroxides. It does not
show +4 and +6 oxidation states as shown by other members.
(vi) Oxygen molecule is highly stable. The two atoms are held together by multiple bonds.
The bonds are fairly strong and bond energy is quite high (117 kcal per mole). It is only at
a high temperature that these bonds are broken and oxygen atoms react with other
materials. Thus, ordinary oxygen is not active under ordinary conditions.
(vii) Hydrogen bonding is present in water and many other compounds due to high
electronegativity of oxygen. On account of this, water boils at higher temperature.
(viii) Oxygen molecule is paramagnetic in nature in gaseous, liquid and solid states. It is
weakly attracted by a magnet. It has been explained by molecular orbital theory that
oxygen molecule has two unpaired electrons.
(ix) Oxygen is the most abundant element in the earth's crust.
(x) Metals like Cu, Ag, Hg, etc., show lesser affinity with O₂ to form oxide than with
sulphur to form sulphide. It is due to polarizing power of Cu2+, Ag+. Hg2+ ion, owing to
which they form strong bond with S2-
DISSIMILARITIES BETWEEN OXYGEN AND SULPHUR
Property Oxygen Sulphur
1. Electronic configuration 2 electrons in the penul- 8 electrons in the penul-
timate orbit timate orbit
2. Physical state Colourless, odourless gas Pale yellow solid with faint
odour
3. Abundance Most abundant Less abundant

4. Maximum covalency 2 6

5. Action of HNO3 Not affected Oxidised to H₂SO4

6. Nature of hydride H₂O is neutral liquid under H₂S is acidic gas under
ordinary condi tions. ordinary conditions. No
Hydrogen bond ing is hydrogen bonding is
present. present.
7. Molecule Diatomic, O₂ Octatomic, S8
8. Magnetic nature Paramagnetic molecule Diamagnetic molecule