Group 17 elements

Group 17 elements are fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and
astatine (At) are collectively known as halogens and are having the general
electronic configuration of ns2, np5.
Atomic and ionic radii
The halogens have the smallest atomic radii in their respective periods due to
maximum effective nuclear charge. Atomic and ionic radii increases down the
group due to the addition of a new shell at each step.
Ionisation enthalpy
Due to their small size halogens have little tendency to lose electron. Thus they
have very high ionisation enthalpy. Ionisation enthalpy decreases down the
group due to the increase in atomic size.
Electron gain enthalpy
Electron gain enthalpy of halogens is very high as they are short of only one
electron to attain noble gas configuration. Electron gain enthalpy becomes less
negative as we move down the group. However F has less electron gain
enthalpy than Cl due to its small size and high electron density.

Electronegativity
Electronegativity decreases down the group. F is the most electronegative
element in the periodic table.

Melting and boiling point

The melting and boiling points increases down the group.

Bond dissociation enthalpy

Bond dissociation enthalpy decreases as we move down the group. F2 has less
ΔHdiss. Then Cl2 due to small size and strong lone pair-lone pair repulsion.
Colour
All halogens exhibit colour due to the absorption of radiations in visible region
of light due to which the electrons get excited to higher energy levels.

For example, F2 has yellow, Cl2 has greenish yellow, Br2 has red and I2 has
violet colour.

Oxidation state
The most common oxidation state of halogens is −1. Cl, Br, I also shows positive
oxidation states of +1, +3, + 5, + 7. F does not show positive oxidation states due
to non-availability of d-orbistate

Reactivity
All halogens are highly reactive and the reactivity decreases down the group.

Anomalous behaviour of fluorine

Fluorine is anomalous in many properties like, ionisation enthalpy,

electronegativity, enthalpy of bond dissociation that are higher than expected
from the regular trends among the halogens. Its ionic and covalent radii,
melting and boiling points, and electron gain enthalpy quite lower than
expected.
Reasons for the anomalous behaviour of fluorine are:

• Small size and highest electronegativity

• Low F-F bond dissociation enthalpy

• Absence of d-orbitals

Reactivity towards hydrogen

All halogens reacts with H2 to form hydrogen halides (HX) and the reactivity
towards H2 decreases down the group

Acidic strength

As the size of X increases and the strength of H─X bond decreases down the
group, acidic strength dectreses down the group

HF < HCl < HBr < HI

Stability

As the bond dissociation enthalpy decreases down the group so the stability of
hydrogen halides also decreases from HF to HI.

HF > HCl > HBr > HI

Boiling point
Due to the increase in size of halogens the van der Waals forces increases down
the group resulting in the increase in boiling point from HCl to HI. HF has the
highest boiling point due to the presence of strong intermolecular H bonding

HCl < HBr < HI < HF.

Ionic character

Due to the decrease in electronegativity down the group the ionic character of
hydrogen halides also decreases down the group.

HF > HCl > HBr > HI

Dipole moment

Due to the decrease in electronegativity down the group the ionic character of
hydrogen halides also decreases down the group.

HF > HCl > HBr > HI

Reducing power

As the bond dissociation enthalpy decreases, so it becomes easier to give out

the hydrogen atom causing the reducing power to increase from HF to HI.

HF < HCl < HBr < HI

Reactivity towards metals:

Halogens react with metals to form metal halides of the form MX, where M is a
monovalent metal.

Ionic character

Due to the decrease in electronegativity down the group the ionic character of
metal halides also decreases down the group

MF > MCl > MBr > MI