Group 16 Elements .

Atomic radius(pm)

O 74

Large increase in atomic radius due to strong

shielding effect of s & p electrons

S 104

Se 117

Small increase in atomic radius due to poor

shielding effect of d / f electrons.
Te 137
The smaller atomic radius of group 16
elements as compared with corresponding
elements of group 15 due to increase in
Po 140 effective nuclear charge
Group 16 Elements Ionisation enthalpy

(k J / mol)

O 1310
Large decrease in ionisation enthalpy due to large increase in atomic size and strong
shielding effect of s & p electrons

The ionisation energies of first three elements

S 1000 of group 16 are less than the corresponding
elements of group 15 inspite of the fact that
effective nuclear charge increases.This is due to
symmetrical and thus more stable electronic
configuration of N,Pand As as compared to O,S
Se 941
and Se respectively
Small increase in atomic size and poor
shielding effect of d / f electrons
Te 870

Po 812
Group 15 Elements Ionisation enthalpy

(k J / mol)

N 1402
Large decrease in ionisation enthalpy due to large increase in atomic size and strong
shielding effect of s & p electrons in P

P 1012

As 947

Small increase in atomic size and poor

shielding effect of d / f electrons
Sb 834

Bi 703
Group 16 Elements Electronegativity
Oxygen is the second most
electronegative element
after fluorine

O 3.5

S 2.5

Electronegativity decreases
Se 2.48 down the group due to
increase in atomic size

Te 2.1

Po 2.0
 Metallic character &
Group 16 Elements non metallic character

S Non metals On moving down the group,

the atomic size increases, the
screening effect increases,
electronegativity decreases.
Se
Therefore tendency to lose
Metalloids electron increases i.e metallic
Te character increases

Po Metal
Group 16 Elements

Melting point(K) Boiling point(K)

On moving down
O 55 90
the group, the
molecular size
386 (for increases. As a
S monoclinic form) result, the van 718
der waals forces
increase and
490 therefore the 958
Se
melting and
boiling points
increase
Te 723 gradually. 1263

Po 527 1233
Group 16 Elements
Density(g/ml)

Density increases down the group. This is due to

O 1.32 less increase of size with reference to atomic mass.
On moving down the group increases the
magnitude of van der Waals forces of attraction
acting between the molecules and consequently
S 2.06 the lattice become more compact.

Se 4.19

Te 6.25

Po 9.4
PHYSICAL STATE
Oxygen is gas while others are solids.

The oxygen atom has tendency to form multiple bonds(p∏ - p∏ interaction)

with other oxygen atom on account of small size and high electronegativity. The
molecules are held together by weak van der waals forces of attraction. Hence
oxygen exist as gas at room temperature.

The rest of the elements do not form p∏ - p∏ multiple bond due to their large
size and thus do not exist as diatomic molecules. They prefer to form single bond
and possess complex structure, i.e. octaatomic molecules having puckered 8
membered crown shaped rings.

The tendency to exist in 8 atoms ring is maximum with S and decreases as we

go down the group
S S

204 pm
S

1070

S S

S S

CROWN SHAPED PUCKERED RING OF S8

 OXIDATON STATE
As the configuration of outermost shell is ns2 np4 , they show -2 , +2,+4 & +6 oxidation state

OXYGEN (O)
Oxygen being highly electronegative shows generally -2 oxidation state .
Most of the metal oxides are ionic and contain oxygen as dinegative anion.
In F2O, the oxidation state of oxygen is +2 (because F is more electronegative than O)
In peroxide H2O2, the oxidation state of oxygen is -1.
O has no d-orbitals therefore O can not show +4 and +6 oxidation state

As we go down the group 16 , tendency to show -2 oxidation state decreases due to

decrease in electronegativity

SULPHUR(S), SELENIUM(Se), TELLURIUM(Te) & POLONIUM(Po)

S, Se, Te & Po shows positive oxidation state +2, +4 & +6. The show +4 & +6 oxidation
state due to availability of d-orbitals.

Stability of +6 oxidation state decreases down the group due to inert pair effect.
+6 oxidation state is most stable in S in SF6
CATENATION (Tendency of an atom to form bonds with identical atoms)

OXYGEN & SULPHUR SHOW THE PROPERTY OF CATENATION

Catenation property is greater in Sulphur than

Oxygen.
This is because S-S bond is stronger (213kJ/mol)
than O-O bond (138kJ/mol).
Because of small size of oxygen atom, the repulsion
between the lone pair of electrons on oxygen atom
and bond pair of electrons of O-O bond is greater
than repulsion between lone pair electrons on
sulphur atom and bond pair of electrons of S-S bond.
Examples of catenation are

H2O2 H-O-O-H
H2S2 H-S-S-H
H2S3 H-S-S-S-H
H2S4 H-S-S-S-S-H
 ALLOTROPY IN GROUP 16 ELEMENTS
ELEMENT ALLOTROPIC FORMS

O Dioxygen(O2) & Ozone(O3 )

S Rhombic , monoclinic , plastic & amorphous

Se Red form(non metallic), grey form (metallic), amorphous black

form

Te Crystalline form and amorphous form

Po α- and β- form
ALLOTROPES OF OXYGEN
DIOXYGEN (O2)
Dioxygen molecule is highly stable. The bonds are very strong as the bond
dissociation energy is high(493.4kJ/mol). The two atoms are held together by
covalent double bond (one sigma and one ∏ bond). The bond length is 121pm.

OZONE (O3)
Ozone molecule is angular with O-O-O bond angle as 1170 since the central
atom in ozone molecule is sp2 hybridised.Both the O-O bonds are identical
having bond length 128 pm which is intermediate between single bond(148
pm ) and double bond (121pm). The ozone molecule is therefore considered
to be resonance hybrid.
RESONATING STRUCTURE OF OZONE

128 pm
1170

Resonance hybrid
 ALLOTROPES OF SULPHUR
PROPERTY RHOMBIC SULPHUR MONOCLINIC PLASTIC SULPHUR
(α – Sulphur) SULPHUR (β – (γ – Sulphur)
Sulphur)
PREPARATION By slowly By melting rhombic By pouring molten
evaporating the sulphur in a dish and sulphur into cold
solution of sulphur cooling till crust is water
in CS2 in a dish. formed.

STRUCTURE Octahedral crystals Needle shaped Amorphous form . It

Consists of S8 ring crystals. Consists of consists of an open
forming crown S8 ring forming chain structure
shape structure crown shape
structure
APPEARANCE Bright yellow colour Dull yellow colour Soft rubber like

SPECIFIC GRAVITY 2.07 g / cm3 1.98 g / cm3 1.95 g / cm3

SOLUBILITY Insoluble in water Insoluble in water Insoluble in water &

but dissolves readily but dissolves readily CS2
soluble in CS2 soluble in CS2
PROPERTY RHOMBIC SULPHUR MONOCLINIC PLASTIC SULPHUR
(α – Sulphur) SULPHUR (β – (γ – Sulphur)
Sulphur)

MELTING POINT 385.8 K 393 K No sharp melting

point
TRANSITION
TEMPERATURE
above 369 K
Rhombic sulphur Monoclinic sulphur
below 369 K

At 369 K both the form exist. This temperature is

called transition temperature.
RHOMBIC SULPHUR & MONOCLINIC SULPHUR

S S

204 pm
S

1070

S S

S S

CROWN SHAPED PUCKERED RING OF S8

 RHOMBIC SULPHUR & MONOCLINIC SULPHUR
ARRANGEMENT OF S8 MOLECULES

Rhombic sulphur Monoclinic sulphur

S8 rings fit comfortably S8 rings are sacked on the
into each other top of each other
 PLASTIC SULPHUR

S S S

S S S S

Sulphur atoms are linked together to form open chain

molecules
 PROPERTIES OF HYDRIDES OF GROUP 16 ELEMENTS
Property H2O H2S H2Se H2Te REMARKS

Due to decrease in
repulsion between
electron pair which is
H-E-H Angle 104.5 92.1 91 90 due to increase in
atomic size of central
DECREASES BOND ANGLE atom

B.P of water is highest

due to presence of H
bonding. B.P increases
Increases from H2S to H2Se due
to increase in van der
Boiling Point(K) 373 213 232 269 Waals force which is
Decreases due to increase in
molecular size.
 PROPERTIES OF HYDRIDES OF GROUP 16 ELEMENTS
Property H2O H2S H2Se H2Te REMARKS

Thermal stability
Decreases decreases due to
∆diss (M-H) KJ /mol decrease in strength
463 K 347 K 276 K 238 K of M – H bond which
(Dissociation enthalpy)
is due to increase in
atomic size of group
16 element down the
group.
Acidic strength is in the Due to decrease in
order dissociation enthalpy
Acidic Nature
H2O < H2S < H2Se < H2Te of bond M-H down
the group.
 PROPERTIES OF HYDRIDES OF GROUP 16 ELEMENTS
Property H2O H2S H2Se H2Te REMARKS
Reducing property Since water is very
Reducing property of stable, it does not act
hydrides is in the order as reducing agent. As
thermal stability
H2S < H2Se < H2Te decreases from H2S to
H2Te, reducing power
increases.
OXIDES OF GROUP 16 ELEMENTS

All the members form dioxides of the type MO2

SO2 is a gas. SeO2 is volatile solid and TeO2 and PoO2 are crystalline solids.
The dioxides are formed when element is burnt in air.

The reducing property of dioxides decreases from SO2 to TeO2.

SO2 is reducing agent while TeO2 is oxidizing agent.

MO3 type of oxides are also formed as SO3, SeO3 and TeO3

Both type of oxides are acidic in nature

HALIDES OF GROUP 16 ELEMENTS
ELEMENT FLUORIDES CHLORIDES BROMIDES IODIDES

OXYGEN OF2, O2F2 Cl2O, ClO2, Br2O I2O5

Cl2O7
SULPHUR S2F2, SF2, S2Cl2, SCl2, S2Br2, SBr2 S2I2
SF4, SF6 SCl4
SELENIUM Se2F2, SeF4, Se2Cl2, SeBr2, SeBr4 _
SeF6 SeCl2, SeCl4
TELLURIUM TeF4, TeF6, TeCl2, TeCl4 TeBr2, TeBr4 TeI4

Polonium _ PoCl2, PoCl4 PoBr2, PoI4

PoBr4
STABILITY OF HALIDES DECREASES IN THE ORDER: F - > Cl - > Br- > I-
HALIDES OF GROUP 16 ELEMENTS
HEXAHALIDES
S, Se and Te form hexahalide .Among hexahalides, hexafluorides
are stable compound (SF6 , SeF6 ,TeF6).
The central atom undergoes sp3d2 hybridisation to form six sp3d2
hybrid orbital.
Thus hexahalide possess octahedral structure.
F
F F
S
F F

F
HALIDES OF GROUP 16 ELEMENTS
TETRAHALIDES
Among tetrahalides, tetrafluorides are most stable (SF4 , SeF4 ,TeF4). SF4
is gas, SeF4 is liquid and TeF4 is solid.
The central atom undergoes sp3d hybridisation to form five sp3d
hybrid orbital. They have trigonal bipyramidal structure in which one
of the equatorial positions is occupied by a lone pair of electrons. The
geometry is regarded as see-saw geometry.
Due to large lone pair – bond pair repulsion than bond pair – bond
pair repulsion, the bond angle decreases from 180o to 173o
X
..

X
S

X
HALIDES OF GROUP 16 ELEMENTS
DIHALIDES
All the elements except selenium form stable dihalide.
Di-iodide is not formed.
SCl2 is well known dihalide of group 16.
The central atom undergoes sp3 hybridisation to form four sp3 hybrid orbital.
The four sp3 hybrid orbital are directed at the corners of tetrahedron out of which two
contain lone pair of electrons.
Thus dihalides are angular in shape. The H-M-H bond angle decreases from 109o 28’
to 103 o due to lone pair- lone pair and lone pair – bond pair repulsion is greater than
bond pair – bond pair repulsion.

..

M
X
..

X
HALIDES OF GROUP 16 ELEMENTS
MONOHALIDES
Monohalides as S2F2, S2Cl2 and S2Br2 are known. Their structures
are similar to H2O2
Cl

199pm
205pm S
S
104o

Cl