p- Block Elements

GENERAL TRENDS IN THE CHEMISTRY OF p-BLOCK ELEMENTS

1. Electronic configuration: Except for helium, the valence shell electronic configuration of
2 1−6
p-block elements is ns np
2. Oxidation state : The maximum oxidation state exhibited by a p-block element is equal
to the sum of the ns and np electrons

2
3. Inert pair effect : The inert pair effect involves the reluctance of ns electron pair to get
excited and to take part in bond formation. As one moves down a group resulting in a
decrease in the stability of the group oxidation state.

Question: Give reason: In group 15, the stability of the group oxidation state, i.e., +5 state
decreases while that of +3 oxidation state increases on moving down the group.

Ans: Due to Inert pair effect.

4. General chemical behaviour : Non-metals and metalloids exist only in the p-block in the
periodic table. The non-metallic character of elements decreases on moving down a
group in the p-block and the heaviest element in each group is most metallic in nature.
5. Anomalous behaviour of the first element :

Question: Give reason: The first element of each group in p-block shows an anomalous
behaviour and differs from the other elements of the group in several properties.

Answer: (a) The smallest size of the first element in the group.

(b) High ionisation enthalpy of the first element.

(c)High electronegativity of the first element.

(d) Absence of vacant d-orbitals in the valence shell of the first element.

Question: Why the first member of each group is able to form pπ-pπ multiple bonds ?
Due to the combined effect of size and availability of d-orbitals . The first member of a group
can form pπ-pπ multiple bonds to itself (e.g., C == C, C ≡≡ C, N ≡≡ N) and to the other second
row elements (e.g., C == O, C ≡≡ N, N == O).

NOTE: The heavier elements prefer to form π-bond by involving d-orbitals, e.g., they usually form dπ- pπ and dπ-dπ
bonds. As the d orbitals are of higher energy than the p orbitals, they contribute less to the overall stability
of molecules than does pπ - pπ bonding of the second row elements.

GROUP 13 ELEMENTS : THE BORON FAMILY

The group 13 of the periodic table consists of five elements. These are boron (B), aluminium (Al), gallium (Ga),
indium (In) and thallium (Tl).

E 2 1
lectronic configuration of the type ns np

1. Atomic and ionic radii :

(a) The atomic and ionic radii of group 13 elements are smaller than those of the corresponding elements of group
2. Explanation : When one moves from group 2 to group 13 in a particular period in the periodic table, the nuclear
charge increases but number of shells remains the same because the differentitating electron is added in the same
shell. The effective nuclear charge increases and electrons experience a greater nuclear pull. This decreases the size
of atom or ion.

(b) In general, the atomic and ionic radii of group 13 elements increase on moving down the group.

Explanation : This is due to the introduction of a new electron shell at each succeeding element on moving down
the group. The increase in the nuclear charge is compensated by the screening effect of the inner electrons.

(c) The atomic radius of Ga (135 pm) is slightly lower than that of Al (143 pm).

Explanation : As expected, the atomic radius of gallium should be more than that of aluminium due to introduction
of a new electron shell. But the observed atomic radius of Ga (135 pm) is slightly less than that of aluminium (143
pm). The anomaly can be explained as follows .

In between Al (Z = 13) and Ga (Z = 31), there are ten elements of the first transition series of d-block (Z = 21 - 30)
in which the differentiating electrons enter into the inner d-orbitals. The screening effect of the d-orbitals is
imperfect due to their peculiar shapes and poor penetration power. Thus, the d-orbitals present in gallium are unable
to screen the nucleus effectively. As a result, the effective nuclear charge in Ga becomes more than that in Al.
Consequently, the electrons present in gallium experience a greater nuclear pull and are pulled more towards the
nucleus. This reduces the size of gallium atom.

2. Ionisation enthalpy: The ionisation enthalpy values of group 13 elements exhibit the following trends.

(a) The first ionisation enthalpy of group 13 elements are lower than those of the corresponding elements of group
2.

2 1
Explanation : The valence shell electronic configurations of group 13 elements are of the type ns np , while those
2
of group 2 elements are of the type ns . Obviously, the first ionisation enthalpy value of a group 13 element will be
1
the energy involved in the removal of np electron while that of a group 2 element will be the energy involved in the
2
removal of one of the ns electrons. Since an s-orbital is more penetrating than a p-orbital, the energy required for
the removal of an s-electron is higher than that needed for the removal of a p-electron.

(b) The second and third ionisation enthalpies of group 13 elements are much higher as compared to their first
ionisation enthalpies.

Explanation : After the removal of first electron (np electron), the effective nuclear charge increases. As a result,
1
the remaining electrons experience a greater nuclear pull and it becomes more difficult to remove second and third
2
electrons. Moreover, the second and the third electrons to be removed (ns electrons) belong to the s-orbital. The s-
orbitals are more penetrating and the electrons present in them are more tightly held by the nucleus. Therefore, it
requires large amounts of energy to remove second and third electrons from an atom of group 13 elements.

(c) On moving down the group, the first ionisation enthalpy of group 13 elements decreases sharply from B to Al.
Therefore, gallium and thallium exhibit a slight increase in the first ionisation enthalpy.

Explanation : The sharp decrease in the first ionisation enthalpy in going from B to Al is due to an increase in the
size of atom on account of the addition of a new shell. The next element gallium possesses d-electrons in its
penultimate shell. Since, d-electrons shield the nuclear charge less effectively, the ionisation enthalpy of gallium
becomes slightly more than that of aluminium inspite of the increase in atomic size. Thallium possesses f-electrons
in addition to d-electrons in its anti-penultimate shell. The f-electrons shield the nuclear charge still less effectively.
This is why the valence electrons in thallium experience a greater nuclear pull. Consequently, thallium has a higher
ionisation enthalpy than indium (which does not contain inner f-electrons)

3. Electronegativity: The elements of group 13 are more electronegative than those of groups 1 and 2. The
electronegativity first decreases from B to Al and then increases on moving down the group.

Explanation : The higher electronegativities of group 13 elements as compared to those of groups 1 and 2 may be
attributed to their comparatively smaller atomic sizes. The increase in electronegativity is due to the discrepencies in
atomic size of elements.

4. Melting and boiling points : The melting and boiling points of group 13 elements are much higher than those of
group 2 elements. This is due to stronger interatomic attractions existing between their atoms both in the solid as
well as in the liquid states.
The melting and boiling points of boron are much higher as compared to the other elements of the group. This is
due to the three dimensional structure of boron in which boron atoms are strongly held together by covalent bonds.

Gallium with unusually low melting point (303 K), could exist in liquid state during summer. Its high
boiling point (2676K) makes it a useful material for measuring high temperatures.

5.Density : Densities of group 13 elements are higher than those of group 2 elements. The densities increase on
moving down the group.

Explanation : As the atomic and ionic radii of group 13 elements are smaller as compared to those of group 2
elements, they pack more efficiently in the lattice. This is why group 13 elements possess higher densities than those
of group 2 elements.

Chemical Properties

Oxidation state and trends in chemical reactivity:

Boron, the first member of group 13, forms covalent compounds. Infact, boron is unable to form ionic compounds
3+
containing B ions. This is because the first three ionisation energies of boron are much higher than the
3+
corresponding values for the remaining elements of the group. The total energy required to produce a B ion (IE1 +
IE2 + IE3) is too large to be compensated by lattice energies (in case of solids) or by hydration energies (in aqueous
solutions). This is why boron prefers to form covalent compounds by sharing its valence electrons .

On moving down the group, the tendency of formation of covalent compounds decreases while that of the formation
of ionic compounds increases. This is due to a progressive increase in the atomic size and decrease in the ionisation
energies. The compounds of aluminium are also predominantly covalent due to the small size and high charge of
3+
Al ion. The other elements of the group form ionic compounds.

2. Reactivity towards halogens

These elements react with halogens to form trihalides (except Tl I 3).

2E(s)+3X2 (g)→2EX3 (s) (X=F,Cl,Br,I)

(i ) All the trihalides of boron are covalent in nature and exist as monomeric species
(ii) Boron trihalides act as Lewis acids. The boron atom in BX3 does not possess an octet. It has only six electrons
in its valence shell (three electrons already present in the valence shell and three gained by covalent bond
formation). Due to an incomplete octet of boron in a boron trihalide, it has a strong tendency to accept a pair of
electrons to acquire the nearest noble gas configuration. The electron pair thus taken can be accommodated in the
vacant unhybridised 2p-orbital (Fig. 11.2). This is why boron trihalides act as strong Lewis acids. They readily
combine with electron donors (Lewis bases) such as NH3, amines, ethers, sulphides, phosphines, etc., to form
addition compounds. For example,

(i) Boron is a non-metal, while the other members of the group are metals.
(ii) The melting and boiling points of boron are much higher than those of aluminium and the other members
of the group.
(iii) Boron is a bad conductor of electricity while the other elements of the group are good conductors.
(iv) Boron forms only covalent compounds, while the next member aluminium forms both covalent as well as
ionic compounds. The other members of the group form mainly ionic compounds.
(v)
(vi) The tri-chlorides, bromides and iodides of group 13 elements being covalent in nature are
– 3+
hydrolysed in water. Species like tetrahedral [M(OH)4] and octahedral [M(H2O)6] , except in
boron, exist in aqueous medium.
(vii) The monomeric trihalides, being electron deficient, are strong Lewis acids. Boron
trifluoride easily reacts with Lewis bases such as NH3 to complete octet around boron.

(viii) It is due to the absence of d orbitals that the maximum covalence of B is 4. Since the d
orbitals are available with aluminium and other elemenets the maximum covalence can be
expected beyond 4.
(ix) The trihalides of boron exist as discrete monomeric molecules while those of the other elements of the
group exist as dimers having halogen-bridged structures.
 (x) The oxide and hydroxide of boron are weakly acidic, while those of aluminium and the other members of
the group are either amphoteric or basic in nature.

Electronic Configuration
In these elements, the differentiating electron enters

into np subshell. They have four electrons in their outermost shell and possess electronic configuration of the type
2 2
ns np

Atomic and ionic radii : The atomic and ionic radii of group 14 elements are smaller than those of the
corresponding elements of group 13. The atomic and ionic radii increase on moving down the group.

Explanation : On moving from group 13 to group 14 in the same period, the effective nuclear charge increases.
Therefore, the atomic and ionic radii decrease due to the stronger forces of attraction experienced by the electrons.

When one moves down the group, the atomic and ionic radii increase due to addition of a new shell at each
succeeding element. The increase in atomic radii from Si onwards is small due to the ineffective shielding of d- and
f- orbitals present in the higher elements.

Ionisation enthalpy : The ionisation enthalpy values of these elements follow the following trends.

(a) The first ionisation enthalpy of group 14 elements are higher than those of the corresponding elements of group
13.

Explanation : This is due to the higher nuclear charge and smaller size of the atoms of group 14 elements as
compared to those of group 13 elements.

(b) The ionisation enthalpies decrease on moving down the group.

Explanation : On moving down the group, the atomic size as well as the screening effect of the inner electrons
increase. This decreases the effective nuclear charge experienced by the valence electrons. Consequently, the
ionisation enthalpies decrease on moving down the group.

(c) The decrease in the first ionisation enthalpy values is very sharp from C to Si followed by a slower decrease upto
Sn. The ionisation enthalpy of Pb is slightly higher than that of Sn.

Explanation : The observed slower decrease in the ionisation enthalpy from silicon to tin and the slight increase in
the ionisation enthalpy from Sn to Pb is due to the combined effect of the following factors :

(i) Poor shielding effect of d-electrons in Ge and Sn and of d- and f-electrons in Pb.
(ii) The increase in the size of atoms on moving down the group.