Anomalous Periodic Properties of 2nd Period Element:

All elements are special in their own way even if there are certain trends that have been
observed by scientists over the years. The elements belonging to the second period display
periodic properties that are especially anomalous.

It has been observed that Lithium, Beryllium, Boron, Carbon, Nitrogen, Oxygen, and
Fluorine have slightly different periodic properties than the rest of the elements belonging to
Groups 1, 2, 13-17 respectively. For example, Lithium and Beryllium form covalent compounds,
whereas the rest of the members of Groups 1 and 2 form ionic compounds. Also, the oxide that is
formed by Beryllium when it reacts with Oxygen is amphoteric in nature, unlike other Group 2
elements that form basic oxides. Yet another example is that of Carbon which can form stable
multiple bonds, whereas Si=Si double bonds are not very common.

So, it has clearly been established that the second-period elements are different. In fact,
they display periodic properties that are similar to the second element of the next group (i.e.
Lithium is similar to Magnesium and Beryllium to Aluminum) or in other words, they have a
diagonal relationship.

The reasons for differences in periodic properties and hence in chemical behavior are:

 Small size of these atoms

 High electronegativity

 Large charge/radius ratio

 These elements also have only 4 valence orbitals available (2s and 2p) for bonding as
compared to the 9 available (3s, 3p, and 3d) to the other members of the respective
groups, so their maximum covalency is 4. (This is why Boron can only form
[BF4]– whereas Aluminum can form [AlF6]3-).

These are the reasons for anomalous periodic properties of second-period elements, but there
are several other normal trends in the periodic table as well.
Anomalous Properties of Lithium:
Introduction about Lithium:
Group 1 elements of the periodic table are known as Alkali Metals. Lithium is the
first element of the group 1. The small size of lithium allows it to behave differently from other
alkali elements (Anomalous behavior).
 
Nature of Lithium:
Lithium is highly electropositive in nature which allows it to form covalent bonds. The
polarization behavior of lithium ion is comparable to that of magnesium ion. Thus, lithium shows
a diagonal relationship with magnesium. There are various reasons for diagonal relationship of
lithium with magnesium. These reasons are as follows:

o As one moves from top to bottom in a group, electropositive nature increases. But from left to
right in a period, electropositive nature decreases. Due to this, similar properties are observed
between diagonal elements.

o From top to bottom in a group, size increases; due to this polarizing power decreases but
moving left to right in period polarizing power increases, thus diagonal elements show similar
properties.

o Lithium is a strong element similar to magnesium.

o Lithium and magnesium ion show comparable boiling and melting points.

o Due to small size, the lithium atom has high ionization energy. It reacts with water, liquid
bromine and forms a highly stable hydride unlike other alkali metals. Magnesium exhibits all
these properties.
 Fig. 1. Reasons for Diagonal Relationship

 Lithium and magnesium both forms monoxides.

2Mg + O2→ 2MgO

 Lithium and magnesium both react with nitrogen to form lithium nitride and magnesium
nitride.

(s) + N2(g) → 2Li3N(s)

 Lithium and magnesium both react slowly with water and form oxides and hydroxides which
decompose on heating.

Mg(s) + 2H2O(g) → Mg (OH)2(aq.) + H2(g)

 Oxides of both lithium and magnesium do not form superoxide.

 The carbonates of lithium and magnesium decompose on heating to form the oxides and
carbon-dioxide.
2 Mg(s) + CO2  2 MgO(s) + C(s)
 Lithium chloride (LiCl) and magnesium chloride (MgCl2) both are soluble in ethanol.
 Both LiCl and MgCl2 are deliquescent and form hydrates LiCl·2H2O and MgCl2·8H2O.
 Both magnesium and lithium are less stable towards heat.
 
Difference between Lithium and Other Alkali Metals:
 Lithium is harder than other alkali metals.
 Melting and boiling point is higher than other alkali metals.
 Lithium is least reactive out of all alkali metals.
 It is a strong reducing agent compared to other alkali metal.
It is the only alkali metal that form the monoxide, Li2O.
4Li(s) + O2(g) → 2Li2O(s)
 Unlike other alkali metals, it forms Li3N.
6 Li + N2→ 2 Li3N

 It does not form solid hydrogen carbonates compared to other alkali metals.
 Lithium does not react with ethyne to form ethynide. But all other alkali metals form
ethynide.
 Lithium nitrate on heating form lithium monoxide as compared to other alkali metals which
forms nitrites on decomposition.

4 LiNO3→ 2 Li2O + 4NO2 + O2

 Lithium reacts slowly with bromine as compared to other alkali metals.

 Lithium when heated in NH3 forms amide, Li2 NH while other alkali metals form amides,
MNH2. M can be other alkali metals.