3.7.3 Periodic Trends and Chemical Reactivity

 We have observed the periodic trends in certain fundamental properties such as atomic and ionic radii, ionization enthalpy, electron gain enthalpy and valence. We know by now that the periodicity is related to electronic configuration. That is, all chemical and physical properties are a manifestation of the electronic configuration of elements. We shall now try to explore relationships between these fundamental properties of elements with their chemical reactivity.

The atomic and ionic radii, as we know, generally decrease in a period from left to right. As a consequence, the ionization enthalpies generally increase (with some exceptions as outlined in section 3.7.1(a)) and electron gain enthalpies become more negative across a period. In other words, the ionization enthalpy of the extreme left element in a period is the least and the electron gain enthalpy of the element on the extreme right is the highest negative (note : noble gases having completely filled shells have rather positive electron gain enthalpy values). This results into high chemical reactivity at the two extremes and the lowest in the centre. Thus, the maximum chemical reactivity at the extreme left (among alkali metals) is exhibited by the loss of an electron leading to the formation of a cation and at the extreme right (among halogens) shown by the gain of an electron forming an anion. This property can be related with the reducing and oxidizing behaviour of the elements which you will learn later. However, here it can be directly related to the metallic and non-metallic character of elements. Thus, the metallic character of an element, which is highest at the extremely left decreases and the non-metallic character increases while moving from left to right across the period. The chemical reactivity of an element can be best shown by its reactions with oxygen and halogens. Here, we shall consider the reaction of the elements with oxygen only. Elements on two extremes of a period easily combine with oxygen to form oxides. The normal oxide formed by the element on extreme left is the most basic (e.g., Na2O), whereas that formed by the element on extreme right is the most acidic (e.g., Cl2O7). Oxides of elements in the centre are amphoteric (e.g., Al2O3, As2O3) or neutral (e.g., CO, NO, N2O). Amphoteric oxides behave as acidic with bases and as basic with acids, whereas neutral oxides have no acidic or basic properties.

 Among transition metals (3d series), the change in atomic radii is much smaller as compared to those of representative elements across the period. The change in atomic radii is still smaller among inner-transition metals
(4f series). The ionization enthalpies are intermediate between those of s- and p-blocks. As a consequence, they are less electropositive than group 1 and 2 metals.

 In a group, the increase in atomic and ionic radii with increase in atomic number generally results in a gradual decrease in ionization enthalpies and a regular decrease (with exception in some third period elements as shown in section 3.7.1(d)) in electron gain enthalpies in the case of main group elements. Thus, the metallic character increases down the group and non-metallic character decreases. This trend can be related with their reducing and oxidizing property which you will learn later. In the case of transition elements, however, a reverse trend is observed. This can be explained in terms of atomic size and ionization enthalpy.