Partial covalent character of lithium halides

The salts of the alkali metals are the most ionic salts known.
Although lithium is an alkali metal, yet its compounds, particularly
halides, are slightly covalent in nature. This is because the Li+ ion has
small size and maximum tendency to withdraw the electrons
towards itself from the negative ion.

In other words, it distorts the electron cloud of the anion towards

itself. This distortion of the electron cloud of the negative ion by the
positive ion is known as polarization. As a result, the charges on the
ions become less because some of its charges get neutralized.

This leads to covalent character.

So if polarization is more, then covalent character will also be large.

The polarization depends on:

i) Size of the cation: smaller the size larger will be the

polarizing character.
 ii) Size of anion: Larger the size of the anion, larger will be the
polarizing character.

This is because anion gets polarized. If the anion is large, its

electron cloud will be weakly held by the nucleus and can be
easily deformed towards the cation.

iii) The polarization increases with the increase in charge of the

ion (cation or anion)

Thus, lithium ion (Li+) being small in size polarizes the anion and
results in decrease of the positive charge on Li+ ion. Therefore
lithium halides are covalent in nature.

Caesium iodide also has low solubility in water because of smaller

hydration energy of its large sized ions.

LiCl, LiBr, LiI are soluble in organic solvents due to predominant

covalent character of these halides.

LiI has maximum covalent character due to large Polarizability of

iodized ion.

Solubility in liquid ammonia:

All alkali metals when dissolved in liquid ammonia give deep blue
solutions which are conducting in nature. These solutions contain
ammoniated cations and ammoniated electrons.
The deep blue color of the solution is due to the ammoniated
electrons. These electrons are which absorb energy corresponding to
red region of visible lights to get excited for jumping to the higher
energy level. The transmitted light imparts blue color to the solution.

The electrical conductivity of the solution is because of the presence

of ammoniated cations and ammoniated electrons.

Reaction with Sulphur and Phosphorus:

Alkali metals when treated with sulphur and phosphorus, they form
sulphides and phosphides respectively on heating.

Reaction with Mercury :

Alkali metals when combined with mercury form amalgam.

Complex compounds:

Alkali metal ions form fewer complex compounds than any other
group of metal ions. The complex forming ability decreases from Li
to Cs.

Anomalous properties of Lithium and its diagonal relationship with

magnesium:

Lithium has different properties from other alkali metals but it shows
greater resemblance with magnesium, which is diagonally opposite
element of group II. The anomalous behavior of Lithium as compared
to other alkali metals is due to the following reasons.

1) The extremely small size of Lithium atom and its sign

2) Greater polarizing power of Lithium ion due to its small size,

which results in covalent character in its compound.

3) High ionization enthalpy and least Electropositive character

than other alkali metals.

Lithium resembles magnesium because these two elements have

almost same atomic radii (Li = 152 pm and Mg = 160 pm) and ionic
radii (Li+ = 76 pm, Mg2+ = 72 pm).
1) Lithium is much harder than other alkali metals. Magnesium is
also hard metal.

2) Melting and boiling point of Lithium are comparatively high as

compared to other alkali metals.

3) Lithium forms normal oxide with oxygen while other alkali

metals form peroxide and super oxides. Magnesium also forms
normal oxides.

4) Lithium and Magnesium hydroxides (LiOH, Mg(OH)2) are

weak bases. Hydroxides of other alkali metals are strong bases

5) The halides and alkalis of Lithium and Magnesium are soluble

in organic solvents because of their covalent nature.

6) Unlike elements of group I, Magnesium and Lithium form

nitrides with nitrogen.

7) Lithium chloride is deliquescent and crystallizes as hydrate;

LiCl.2H2O.Other alkali metals don’t form hydrates but
magnesium chloride forms hydrate as MgCl2.8H2O.
8) Lithium and magnesium react directly with carbon and form
ionic carbides while other alkali metals don’t react.

9) The carbonates, hydroxides and nitrates of lithium as well as

magnesium decompose on heating

10) Lithium nitrate on decomposition gives lithium oxide, LiO2

where as other alkali metal nitrates decompose to give the
corresponding nitrite.
11) Li2CO3 ,LiOH ,LiF and LiPO4 are the only alkali metal salts
which are insoluble in water. The corresponding magnesium
compounds are also insoluble in water.

12) Hydrogen carbonates of lithium and magnesium can’t be

isolated in solid state. While hydrogen carbonates of other alkali
metals can be isolated in solid state.

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