GROUP VIA

Oxygen, Sulfur, Selenium, Tellurium, Polonium

OXYGEN 1s2 2s22p4

Oxygen occurs in three isotopic species
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O (99.759%); 17
O (0.0374%); 18
O (0.2039%)
Has two allotropes: O2 and O3.

Completion of Octet
(i) Electron gain to form O2-
(ii) Formation of two single covalent bonds – O –, or a double
bond = O as in O=C=O, (CH3)2C=O.
(iii) Formation of one single bond and electron gain as in OH -.
(iv) Formation of three- or four- covalent bonds as in H 3O+ or R3O+.
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Note:
 O2 compounds of all the elements except He, Ne,
and Ar are known.
 O2 combines directly with all the elements except the
halogens, a few metals & noble gases.

OXIDES:
The formation of the oxide ion from molecular oxygen
requires a lot of energy:
½ O2(g) = O (g) H = 248 kJ/mol
O(g) + 2e- = O2-(g) H = 752 kJ/mol
TOTAL H = 1000 kJ/mol

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QN: Why are there so many oxides?
 The existence of the many ionic oxides [e.g. CaO] is
a result of the high lattice energies of oxides that
contain the small charged ion (O2-).

 When the lattice energy is insufficient to provide the

necessary energy for complete ionization, oxides with
substantial covalent character are formed . E.g. BeO,
SiO2, B2O3.

 Essentially covalent molecular oxides such as CO2,

SO2, SO3 also exist. (These are non metallic).

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Basic oxides

Oxide ions, O2- cannot exist in any appreciable concentration

in aqueous solution due to the hydrolytic reaction:
O2-(s) + H2O = 2OH-(aq) K > 1022.

ie. They function as Basic anhydrides.

When the oxides are insoluble in water e.g. MgO, they
usually dissolve in dilute acids.
MgO(s) + 2H+(aq)  Mg2+(aq) + H2O.

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Acidic oxides
• Covalent oxides of the non-metals are usually acidic.
They dissolve in water producing solutions of acids.
They are also known as Acid anhydrides. E.g
N2O5(s) + H2O  2H+(aq) + 2NO-3 (aq).

Amphoteric oxides
These oxides behave acidically towards strong bases
and as bases towards strong acids.
ZnO + 2H+(aq)  Zn2+ + H2O
ZnO + 2OH- + H2O  Zn(OH)42-

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NOTE:
 Some oxides are relatively inert dissolving in neither acids
nor bases, eg. CO, MnO2.

 For an element which forms several oxides, the oxide of

the element in the highest oxidation state is the most
acidic.
eg. CrO = Basic Cr has Oxidation state +2
Cr2O3 = Amphoteric Cr has Oxidation state +3
CrO3 = Acidic. Cr has Oxidation state +6

CATENATION:
 Occurs only to a very limited extent e.g. O3 & O3- These are
well established chains of Three Oxygen atoms.

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TWO CO-ORDINATE OXYGEN:

The majority of O2 compounds have two unshared pairs

of electrons and two single bonds. (sp3 hybridization).
In cases where the O-bonds are not supplemented by
–bonds the M-O-M group is always bent.

e.g. H2O has the HÔH = 104.5o,

(CH3)2O has the CÔC = 111o

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NOTE:
If the M atom has orbitals (usually d-orbitals) capable of
interacting with the lone pair orbitals of the oxygen,
the M-O bond acquires some  character due to d –
p interaction.

Such interaction causes shortening of the length of the M-O

bonds and generally widens the MÔM angle.
e.g. (C6H5)2O ; Angle = 124o
Si-Ô-Si in quartz = 142o
H3Si-Ô-SiH3 > 150o.

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OZONE:
 Ozone gas is perceptibly blue in colour &
diamagnetic
 The pure liquid is deep blue (bp -112oC) and
EXPLOSIVE.
 Very endothermic:
O3 = 3/2 O2 H = -142 kJ/mol.
 An important natural constituent of the Atmosphere:
(up to appr. 27% by weight between altitudes of 15-
25 km).

NOTE:
Bond length O-O = 1.28 Å, cf. O=O in O2 = 1.21 Å,
HO-OH = 1.49 Å
Therefore, the O-O bond in O3 has considerable double bond
character.
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NOTE: The Action of Solar ultraviolet radiation on O2
produces O3 in the Upper Atmosphere.
O2  2O (ultraviolet radiation, 240-300 nm)
O + O2 O3 (reversible between 200-360 nm)
resulting in a steady state concentration.

Destruction of the Ozone layer

By the action of NO from aircrafts

NO + O3  NO2 + O2
NO2 + O  NO + O2
By the action of chlorofluorocarbons (CFC)
Cl + O3  ClO + O2
ClO + O  Cl + O2
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OXYGEN COMPOUNDS
1. Oxygen Fluorides:
Intensively studied as potential rocket fuel oxidizers.
OF2 – Oxygen difluoride:
 Pale yellow poisonous gas
 Relatively not reactive and can be mixed with H2,
CH4 or CO without reaction, although sparking
causes violent explosion.
 Mixtures of OF2 with Cl2, Br2 or I2 explode at RT.

Readily hydrolyzed by base

OF2 + 2OH-  O2 + 2F- + H2O
Reacts more slowly with water but explodes with steam:
OF2 +H2O  O2 + 2HF
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2. Hydrogen peroxide

 Pure H2O2 is a colourless liquid (bp 150.2oC)

 Resembles H2O in many of its physical properties.

 40% denser than water

 Strong oxidizing agent

 In dilute aqueous solution it is more acidic than water:

H2O2 = H+ + HO2- K20o = 1.5 x 10-12.

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 Sulfur, Selenium, Tellurium, Polonium
S - occurs widely in nature as the element, H2S, SO2,
metal sulfides, CaSO4, MgSO4.
Se & Te as Selenides & Telluride impurities in metal
sulphide ores.
Po – occurs in U & Th minerals as a product of
radioactive decay series.

 Elements show essentially Non-metallic covalent

chemistry, except for Po and to a very slight extent
Te.

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Complete the noble gas configuration by forming:
1) Chalconide ions S2-, Se2- and Te2-
2) Two electron pair bonds eg. (CH3)2S, H2S.
3) Ionic species with one bond and one negative
charge eg. HS-, RS-.
4) Three bonds and one positive charge eg.
R3S+.
5) Compds in formal oxidation states IV and VI
eg. SeCl4, TeF6, SeF5- with four, five or six bonds.
Te may give an eight-coordinate ion, TeF8-.

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NOTE:
The Chemistry of O2 is different from that of S with more gradual variations
through Se, Te, Po.

This may be attributable to:

(i) S  Po have lower electronegativities, which means that their
compounds have less ionic character.
(ii) As in other 2nd row and subsequent elements there is multiple d-p
bonding but no p -p bonding, causing shortening of bonds.
eg. SO42- : Expected S-O Bond length = 1.69 Å
Observed S-O Bond length = 1.49 Å
iii) The valence is not confined to two, since d-orbitals can be utilized to
form more than four bonds to other elements. eg. SF6, Te(OH)6.

iv) Sulfur has a strong tendency to catenate and forms compounds with
no O, Se or Te analogs. eg. polysulphide ions, Sn2-. (Energy of S-S
bonds may be as high as 430 kJ/mol).

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Trends
Down the group: Due to increase in size and decrease in
electronegativity; there is:
(i) Decrease in thermal stability of H2X compds.
(ii) Increase in metallic character of the elements eg:
The MO2 oxides of Te & Po are ionic.
(iii) Increasing tendency to form anionic complexes such
as SeBr62-, PoI62-
(iv) Decreasing stability of compounds in high formal
positive oxidation states.
(v) The appearance of some cationic properties for Po
and very marginally Te.

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Elemental S: Main allotropes (crystal forms)
Solid S: All modifications of crystalline sulfur contain, either
a) Sulfur rings which may have from 6-20 sulfur atoms and
are referred to as cyclohexa -, cycloocta- etc. sulfur.
or
b) Chains of sulfur atoms referred to as catenasulfur.

(i) Cyclooctasulfur (S8).

The most common form and has three main
allotropes: S, S and S. S is the most stable
(orthorhombic sulphur).

See the structure of the S8 molecule S.

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COMPOUNDS OF GROUP VIA ELEMENTS

1) HYDRIDES; H2M, M = S, Se, Te.

 Obtained by action of acids on metal sulfides, selenides

or tellurides (chalconides)
H2SO4 + FeSe  H2Se + FeSO4
 Extremely poisonous gases
 Thermal stability and bond strengths decrease from H2S
to H2Te.
 All behave as very weak acids and acidity in water
increases down the series H2S < H2Se < H2Te.

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2) HALIDES
a) Sulfur Fluorides
Direct fluorination of S8 yields mainly SF6 and
Traces of S2F10 and SF4.
S8 + F2  SF6 + S2F10 + SF4

SF4 is extremely reactive and is instantly hydrolyzed

by water to SO2 and HF.
SF4 + 2H2O  SO2 + 4HF

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BUT
SF6 – Very resistant to chemical attack.
This is due to a combination of factors including:
(i) High S-F bond strength.
(ii) Sulfur is both co-ordinatively saturated and
sterically hindered.
(iii) Lack of polarity of the molecule.

b) Sulfur chlorides
Chlorination of molten sulfur yields S2Cl2.

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c) Sulfur Iodides.
No stable compds with S-I bonds are known, except
S7I+

NOTE: SeX4, SeX6, and TeX4, TeX6,

(Where X = F, Cl, Br)
are similar to their S analogues.

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SO2: - Quite soluble in water and its solution in
water has been referred to as sulfurous acid,
H2SO3.

 However H2SO3 is either not present or present

only in infinitesimal quantities.
 The equilibrium in aqueous solns of SO 2 may
be represented as:
SO2 + xH2O  SO2.xH2O (Hydrated SO2)

[SO2.xH2O  H2SO3 K<<<1]

SO2.xH2O = HSO3-(aq) + H3O+ (x-2)H2O

SO2 is used as a NON-AQUEOUS solvent.
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• The other dioxides differ considerably in
structure:
At RT:
SO2 = gas,
SeO2 = A white volatile solid,
TeO2 = A non-volatile white solid.

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• SO3
Prep:
2SO2(g)+ O2(g)  2SO3(g)
Catalyst: V2O5 or NO

• The reaction is slow without catalyst.

Reasons:
1. SO2 is stable due to multiple bonding
2. Difficult in breaking O=O double bond

SO3 reacts violently with water. In industry H2SO4 is

manufactured by the reaction:
• SO3(g) + H2SO4(l)  H2S2O7 (pyrosulfuric
acid)
• H2S2O7(l) + H2O  H2SO4(l)
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