Group VII A Elements (Halogen Family)

The word halogen means salt former. Halogens belong to group VII-A or group 7 or group 17 of the periodic table.

This group consists of the elements which are given in the following.

Electronic Configuration of Group VII-A (Halogens)

Fluorine (F) (1s², 2s², 2p⁵ )

Chlorine (Cl) (1s², 2s², 2p⁶, 3s², 3p⁵)

Bromine (Br) (1s², 2s², 2p⁶, 3s², 3p⁶, 4s², 3d¹⁰, 4p⁵ )

Iodine (I) (1s², 2s², 2p⁶, 3s², 3p⁶, 4s², 3d¹⁰, 4p⁶, 5s², 4d¹⁰, 5p⁵)

Astatine (At) (1s², 2s², 2p⁶, 3s², 3p⁶, 4s², 3d¹⁰, 4p⁶, 5s², 4d¹⁰, 5p⁶, 6s², 4f¹⁴, 5d¹⁰, 6p⁵)

General Properties of group 7A (VII A)

Group VII A general valence shell configuration

Their general valence shell configuration of group 7 (Halogens) is ns2, np5.

Non-metals

All halogens are non-metals.

Diatomic molecules

They exist as discrete diatomic molecules F2, Cl2, Br2, I2, At2.

Group VII A atomic radii

Their atomic radii increase down the group.

Group VII A electronegativity

Their electronegativities are high and decrease down the group. Fluorine has the highest electronegativity which is four.

Halogens Group VII A Electron affinity

Electron affinity is the energy released or absorbed when an electron is added to a gaseous atom or ion. It is the measure of attraction between incoming electrons and the nucleus. Higher is the attraction higher will be the electron affinity.

what is electron affinity in simple words — what is electron affinity

Electron affinity Trend

F < Cl > B r > I > At

At < I < Br < F < Cl

Element: F Cl Br I At

Electron Affinity (kJ/mol)

328 349 325 295 270

The trend is not regular. Fluorine is showing an exceptionally low value than chlorine. Due to its very smaller atomic size valence shell is smaller so electrons present in it repel the incoming electron. This difference between the energy released due to attraction by the nucleus and energy absorbed during repulsion by the electrons is less and therefore, the electron affinity of fluorine is less than chlorine.

Melting and Boiling points of Halogens

Their melting and boiling points of halogens increase down the group. Thus from top to bottom, they change from gas to solid. Astatine is radioactive and its half-life is 8.3hrs.

Element State M.P B.P

Fluorine gas -219.6^oC -188.2^oC pale yellow

Chlorine gas -101.0^oC -34.7^oC yellowish green

Bromine liquid -7.2^oC 59^oC dark red (vapors reddish brown)

Iodine solid 113.7^oC 184^oC dark crumbly (vapors violet)

Astatine solid 300^oC 380^oC black (vapors dark)

Halogens Bond Enthalpy

Bond Enthalpy is the energy required to break one mole of chemical bonds in gaseous molecules to form gaseous atoms.

Cl2(g) → 2Cl(g) ∆H = 242 kJ/mol

F2 has an abnormally low bond enthalpy than chlorine due to its smaller atomic size. Due to the smaller size distance between nuclei of two atoms will be less and hence repulsion between nuclei will be more. As a result, bond will be weaker.

Halogens are good oxidizing agents

Halogens are good oxidizing agents; however, their oxidizing power decreases down the group.

Their oxidizing power depends upon

Dissociation energy more is dissociation energy less is oxidizing power.
Electron affinity: more is electron affinity more is oxidizing power.
Reduction potential: more is reduction potential more is oxidizing power.

The dominating factor is reduction potential.

Order of oxidizing power is F2 > Cl2 > Br2 > I2

Standard reduction potential (V) 2.87 1.36 1.06 0.54

Halogens take electrons from other elements and thus oxidize them.

2Na + Cl2 → 2Na+ Cl–

e.g. (i) Fluorine and chlorine can oxidize coloured dyes to colourless. Thus they are used as bleaching agents.

e.g. (ii) Chlorine water oxidizes KI to iodine and the solution turns brown due to the formation of iodine.

Cl2(g) + KI(aq) → KCl(aq) + I2(s)

In this reaction, Cl2 has oxidized I– to I2. Similarly, Cl2 can oxidize Br– to Br2.

Reducing power of halide ions depends upon their sizes.

The larger the size of the halide ion more is its reducing power. Larger ions can easily donate an electron and thus can easily reduce other substances.

The order of reducing power is :

I– > Br – > Cl– > F–

Ionic radius (nm)

0.216 0.195 0.181 0.136

e.g. (i) Br – ion reduces sulphate ion of sulphuric acid to SO2.

H2SO4 + 2H+ + 2Br – → Br2 + SO2 + 2H2O

e.g. (ii) I – ion is larger than Br – ion so it is a stronger reducing agent than Br – ion. It reduces the sulphate ion of sulphuric acid to S-2 ion.

H2SO4 + 8H+ + 8I – → 4I2 + H2S + 2H2O

Halogens have irritating odours and they attack the skin.

Bromine causes burns that heal slowly.

Halogens have high ionization energies, electron affinities and electronegativities.

Group 7A Halogens Common oxidation state

Common oxidation state for halogens is -1, but they also show +1, +3, +5, and +7 oxidation states in their compounds. However, fluorine does not show a positive oxidation state as it has the highest electronegativity.

Ionic Compounds Formation

They form ionic compounds with group I-A and group II-A elements.

(xv) Halogens directly react with hydrogen under different conditions to produce their hydrides (Hydrogen halides).

H2 + F2 → 2HF vigorous reaction

H2 + Cl2 → 2HCl in presence of sunlight

H2 + Br2 → 2HBr in presence of sunlight

H2 + I2 ⇋ 2HI in presence of sunlight

The order of reactivity of halogens towards this reaction is

F2 > Cl2 > Br2 > I2

As the size of halogen increases, the H – X bond energy decreases, and thus, the stability of halide decreases and the bond’s polarity decreases.

The order of stability and polarity is HF > HCl > HBr > HI
While the order of reactivity of halogen acids is HI > HBr >HCl > HF
The acidic strength of hydrogen halides increases down the group. As the stability of halogen acids decreases down the group accordingly their acidic strength increases down group.