Chemistry Anomalous properties of lithium

### Topics to be covered

=> Anomalous properties of lithium
=> Points of difference between lithium and other alkali metals
=> Points of similarities between Lithium and magnesium

### ANOMALOUS PROPERTIES OF LITHIUM

color{green}(★ \ \ \ "The anomalous behaviour of lithium is due to the : ")

(i) exceptionally small size of its atom and ion.

(ii) high polarising power (i.e., charge/ radius ratio).

color{green}(★) As a result, there is increased covalent character of lithium compounds which is responsible for their solubility in organic solvents.

color{green}(★) Further, lithium shows diagonal relationship to magnesium which has been discussed subsequently.

### Points of Difference between Lithium and other Alkali Metals

(i) Lithium is much harder. Its m.p. and b.p. are higher than the other alkali metals.

(ii) Lithium is least reactive but the strongest reducing agent among all the alkali metals. On combustion in air it forms mainly monoxide, color{red}(Li_2O) and the nitride, color{red}(Li_3N) unlike other alkali metals.

(iii) color{red}(LiCl) is deliquescent and crystallises as a hydrate, color{red}(LiCl.2H_2O) whereas other alkali metal chlorides do not form hydrates.

(iv) Lithium hydrogencarbonate is not obtained in the solid form while all other elements form solid hydrogencarbonates.

(v) Lithium unlike other alkali metals forms no ethynide on reaction with ethyne.

(vi) Lithium nitrate when heated gives lithium oxide, color{red}(Li_2O), whereas other alkali metal nitrates decompose to give the
corresponding nitrite.

color{red}(4LiNO_3 → 2Li_2O + 4NO_2 +O_2)

color{red}(2NaNO_3 → 2NaNO_2 +O_2)

(vii) color{red}(LiF) and color{red}(Li_2O) are comparatively much less soluble in water than the corresponding compounds of other alkali metals.

### Points of Similarities between Lithium and Magnesium

The similarity between lithium and magnesium is particularly striking and arises because of their similar sizes : atomic radii, color{red}("Li = 152") pm, color{red}("Mg = 160") pm; ionic radii : color{red}(Li^+ = 76) pm, color{red}(Mg^(2+)= 72) pm. The main points of similarity are:

(i) Both lithium and magnesium are harder and lighter than other elements in the respective groups.

(ii) Lithium and magnesium react slowly with water. Their oxides and hydroxides are much less soluble and their hydroxides decompose on heating. Both form a nitride, color{red}(Li_3N) and color{red}(Mg_3N_2), by direct combination with nitrogen.

(iii) The oxides, color{red}(Li_2O) and color{red}(MgO) do not combine with excess oxygen to give any superoxide.

(iv) The carbonates of lithium and magnesium decompose easily on heating to form the oxides and color{red}(CO_2). Solid hydrogen carbonates are not formed by lithium and magnesium.

(v) Both color{red}(LiCl) and color{red}(MgCl_2) are soluble in ethanol.

(vi) Both color{red}(LiCl) and color{red}(MgCl_2) are deliquescent and crystallise from aqueous solution as hydrates, color{red}(LiCl·2H_2O) and color{red}(MgCl_2·8H_2O).