MODULE - 6 General Characteristics of the p-block Elements

Chemistry of Elements

18
Notes
GENERAL CHARACTERISTICS
OF THE P-BLOCK ELEMENTS

The p-block of the periodic table consists of the elements of groups 13,14, 15,
16, 17 and 18. These elements are characterised by the filling up of electrons in
the outermost p-orbitals of their atoms. Some of these elements and their
compounds play an important role in our daily life. For example:

z Nitrogen is used in the manufacture of ammonia, nitric acid and fertilizers.

Trinitrotoluene (TNT), nitroglycrine, etc., are compounds of nitrogen, which
are used as explosives.

z Oxygen present in air is essential for life and combustion processes.

z Carbohydrates, proteins, vitamins, enzymes, etc., which contain chain of carbon

atoms, are responsible for the growth and development of living organism.

The usual trends (vertical as well as horizontal) in various properties observed in

the s-block are observed in this block, too. As we move from top to bottom
through a vertical column (group) some similarities are observed in the properties.
However, this vertical similarity is less marked in the p-block than that observed
in the s-block, especially in groups 13 and 15; vertical similarity is increasingly
shown by the later groups. As far as the horizontal trend is concerned, the properties
vary in a regular fashion as we move from left to right across a row (period).

In this lesson we shall study some important physical properties w.r.t. the of
electronic configuration of the atom. Finally, we shall relate the periodicity in
atomic properties to the observed chemical behaviour of their compounds, with
special reference to their oxides, hydrides and halides.

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OBJECTIVES
After reading this lesson you will be able to:
z describe the general mode of occurrence of these elements in nature;
z recall the electronic configurations of the p-block elements;
z explain the variations in atomic and physical properties such as Notes
(i) atomic and ionic sizes;
(ii) ionization enhalpy;
(iii) electronegativity;
(iv) electron-gain enthalpy;
(v) metallic and non-metallic behaviours along the period and in a group
of the periodic table;
z correlate the properties of the elements and their compounds with their
positions in the periodic table;
z explain the anomalous properties of the first element in each group of this
block and
z explain inert pair effect.

18.1 OCCURRENCE OF THE P-BLOCK ELEMENTS IN

NATURE
The p-block elements do not follow any set pattern of mode of occurrence in
nature. Some of them occur free as well as in the combined state in nature. For
example, elements such as oxygen, nitrogen, carbon, sulphur occur in both the
forms. Noble gases occur in free state only. All other elements usually occur in
the combined state. The distribution of these elements in nature is also far from
any uniform pattern. Some of them are quite abundant, e.g., oxygen, silicon,
aluminium, nitrogen etc. On the other hand the heavier members in each group of
the block are generally much less abundant. The important minerals associated
with elements will be considered whenever it is necessary at the appropriate places
in the text.

18.2 ELECTRONIC CONFIGURATION

Among the elements of p-block, the p-orbitals are successively filled in a systematic
manner in each row. Corresponding to the filling up of 2p, 3p, 4p, 5p and 6p
orbitals five rows of p-block elements are there. The outer electronic configuration
of the atoms of these elements is ns2np 1–6.

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18.3 ATOMIC SIZE
The atomic radius of the of p-block elements generally decreases on moving
across a period from left to right in the periodic table. It is because the addition of
electrons takes place in the same valence shell and are subjected to an increased
pull of the nuclear charge at each step. The variation in atomic size along a period
is shown in Table 18.1.
Notes
Table 18.1 : Variation in Atomic Size in a row from boron to fluorine
Element Boron Carbon Nitrogen Oxygen Fluorine
Outer electronic
configuration 2s2 2p1 2s2 2p2 2s2 2p3 2s2 2p4 2s2 2p5
Nuclear charge +5 +6 +7 +8 +9
Effective
nuclear charge + 2.60 + 3.25 + 3.90 + 4.55 + 5.20
Atomic size (pm) 88 77 70 66 64

On moving down a group, the atomic radius of the elements increases as the
atomic number increases. This is due to the increase in the number of shells as we
move from one element to the next down the group. The increase in nuclear
charge is more than compensated by the additional shell. The variation in atomic
size on moving down a group is shown in Table 18.2.
Table 18.2 : Variation in atomic size down a group
Elements of Outer electron Nuclear Effective nuclear Atomic size
Group 13 configuration charge charge (pm)
Boron 2s2 2p1 +5 + 2.60 88
Aluminium 3s2 3p1 + 13 + 11.60 118
2 1
Gallium 4s 4p + 31 + 29.60 124
2 1
Indium 5s 5p + 49 + 47.60 152
2 1
Thallium 6s 6p + 81 + 79.60 178

18.4 IONIZATION ENTHALPY

It is the amount of energy required to remove the most loosely bound electron
from the outermost shell of a neutral gaseous atom. It is measured in kJ mol–1 and
is known as first ionization enthalpy.
The first ionization enthalpy of the p-block elements generally increases on moving
from left to right along a period. It is because as we move from left to right along
a period, the atomic size decreases. In a small atom, the electrons are held tightly.
The larger the atom, the less strongly the electrons are held by the nucleus. The
ionization enthalpy, therefore, increases with decrease in atomic size. However,
there are certain exceptions, e.g., the first ionization enthalpy of a group 16 element

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is lower than that of a group 15 element. It is because in case of a group 15 element,
the electron is to be removed from the half-filled p-orbitals. A comparison of first
ionization energies of some elements is given in Table 18.3.
Table 18.3 : Comparison of first ionization enthalpies (kJ mol–1)
B C N O F Ne
801 1086 1403 1310 1681 2080
AI Si P S CI Ar
Notes
577 796 1062 999 1255 1521

In general the first ionization enthalpy decreases in a regular way on descending

a group. It is because on descending a group, the atomic size increases. As a
result the electrons are less tightly held by the nucleus and therefore, first ionization
enthalpy decreases.

INTEXT QUESTIONS 18.1

1. Which of the following atoms is expected to have smaller size?
(i) 9F and 17CI (ii) 6C and 14Si (iii) 5B and 6C (iv) 6C and 7N
2. Which atom in the following pairs of atoms is expected to have higher
ionization enthalpy?
(i) 4Be and 5B (ii) 16S and 17CI (iii) 2He and 10Ne (iv) 8O and 16S
3. Arrange the following atoms in order of increasing ionization enthalpy: 2He,
4
Be, 7N, 11Na.
4. How does the ionization enthalpy vary in general in a group and in a period
of the p-block elemetns?

18.5 ELECTRON GAIN ENTHALPY

When an electron is added to a neutral gaseous atom, heat enegy is either released
or absorbed. The amount of heat energy released or absorbed when an extra
electron is added to a neutral gaseous atom is termed as electron gain enthalpy,
i.e., energy change for the process :
X (g) + e– X − (g)
Generally for most of the atoms, the electron gain enthalpy is negative, i.e., energy
is released when an electron is added to a neutral gaseous atom. But for some
atoms, the electron gain enthalpy is a positive quantity, i.e., energy is absorbed
during the addition of an electron.
Electron affinity generally becomes more negative on moving from left to right
along a period. It is because on moving across a period, the atomic size decreases.
As a result the force of attraction exerted by the nucleus on the electron increases.

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Consequently the atom has a greater tendency to gain an electron. Hence, electron
gain enthalpy becomes more negative.
On moving down a group, the electron gain enthalpy becomes less negative. This
is due to the increase in atomic size and thus, less attraction for the electrons; the
atom will have less tendency to gain an electron. Hence, electron gain enthalpy
becomes less negative. But in the halogen group, the electron gain enthalpy of
Notes chlorine is more negative than that of fluorine. It is because the size of the F atom
is very small which makes the addition of electron less favourable due to inter
electronic repulsion. Similar situation exists for the first element of each group.
Table 18.4 : Electron gain enthalpies of some p-block elements in kJ mol–1
B C N O F
– 0.30 – 1.25 + 0.20 – 1.48 – 3.6
AI Si P S CI

– 0.52 – 1.90 – 0.80 – 2.0 – 3.8

18.6 ELECTRONEGATIVITY
Electronegativity is defined as a measure of the ability of an atom to attract the
shared electron pair in a covalent bond to itself.
Electronegativity increases along the period and decreases down the group.
Fluorine is the most electronegative of all the elements. The second most
electronegative element is oxygen followed by nitrogen in the third position.

18.7 METALLIC AND NON-METALLIC BEHAVIOUR

The elements can be broadly classified into metals and non-metals. Metals are
electropositive in character i.e., they readily form positive ions by the loss of
electrons, whereas non-metals are electronegative in character i.e., they readily
form negative ions by the gain of electrons. The metallic and non-metallic character
of p-block elements varies as follows:
Along the period the metallic character decreases, whereas non-metallic character
increases. It is because on moving across the period, the atomic size decreases
due to the increased nuclear charge and hence, ionization energy increases.
On moving down the group the metallic character increases, whereas non-metallic
character, decreases. It is because on moving down a group, the atomic size
increases. As a result the ionization energy decreases and tendency to lose electrons
increases. Therefore, metallic character increases and non-metallic character
decreases.

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18.8 ANOMALOUS BEHAVIOUR OF THE FIRST
ELEMENT IN EACH GROUP OF THE p-BLOCK
The elements comprising s-block and p-block are called main groups or
representative elements.
Since the atomic radii decrease across a period, the p-block atoms are smaller
than their nearest s or d block atoms; thus F atom has the smallest radius. Notes
Associated with small atom the 2p orbitals are very compact and influence the
bonds formed. Interelectronic repulsions are thus more significant in 2p than in
np orbitals (where n > 2). This results in the N–N, O–O and F–F bonds being
comparatively weaker than the P–P, S–S and CI–CI bonds, respectively.
The small size of the atoms of N, O and F results in their high electonegativity
values. This is reflected in the formation of relatively strong hydrogen bonds in X
– H....Y, where X and Y may be N, O or F.
Carbon, nitrogen and oxygen differ from other elements of their respective groups
due to their unique ability to form pπ–pπ multiple bonds. For example C=C,
C≡C, N=N, O=O, etc. The later members such as Si, P, S, etc., do not form pπ–
pπ bonds because the atomic orbitals (3p) are too large to achieve effective
overlapping.
The valence shell capacity of the p-block elements in the second period limits the
coordination number to a maximum of 4. However, in compounds of the heavier
members the higher coordination numbers are attainable. Thus BH 4– and BF4–
contrast with [AlF6]3–; CF4 contrasts with [Si F6]2– and NH +4 contrasts with [PCl6 ]− .
In the heavier members of each group d-orbitals are available for bonding and
their participation may be envisaged in the attainment of the higher coordination
number.

18.9 INERT PAIR EFFECT

Among the elements of p-block, in groups 13,14 and 15, there is a general trend
that the higher oxidation states become less stable in going down the group. Thus
although boron and aluminium are universally trivalent, gallium, indium and
thallium exhibit +1 state as well. In fact +1 state of thallium is very stable. Similar
situations are noticed in groups 14 and 15. Though carbon is universally tetravalent,
it is possible to prepare divalent germanium, tin and lead compounds. The stable
state of +3 in antimony and bismuth in group 15 is another example.
Outer electron configurations of group 13, 14 and 15 elements are ns2np1, ns2np2
and ns2np3, respectively. They are thus expected to show the higher oxidation
state of +3, +4 and +5 respectively. But the preference of heavier elements of these

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groups to show +1, +2 and +3 states, respectively indicate that two electrons do
not participate in bonding. The reluctance of s-electrons to take part in chemical
bonding is known as inert pair effect.
The so called “inert pair effect” is therefore, ascribed to two factors.
1. The increase in the promotion energy from the ground state (ns2 np1) to the
valence state (ns1 np2)
Notes
2. Poorer overlap of the orbitals of the large atoms and hence poorer bond
energy.
The net result is the lesser stability of higher oxidation state with the increasing
atomic number in these groups. Once the involved energies are taken into
consideration, the so called “inert pair effect” term loses its significance.

INTEXT QUESTIONS 18.2

1. Why does fluorine have electron gain enthalpy lower than chlorine?
2. Which atom in the following pair of atoms has greater electron gain enthalpy?
(i) F, Cl (ii) Br, I (iii)I, Xe (iv) O, F (v) O,S
3. Give two reasons for the fact that the first element in each group of p-block
exhibits unique behaviour.
4. Explain why oxygen exists as a gas whereas sulphur exists as a solid.
5. Mention two reasons which are responsible for the so called “inert pair
effect”.
6. What is the consequence of “inert pair effect” on the oxidation states of Tl
and Pb?

18.10 GENERAL TRENDS IN THE CHEMISTRY OF THE

P-BLOCK ELEMENTS
The p-block elements except noble gases react with hydrogen, oxygen and halogens
to form various hydrides, oxides and halides respectively. A more or less regular
trend is observed in the properties of these compounds on moving down any
particular group. The noble gases have almost zero electron afinity and have very
high ionization enthalpies. Therefore, under normal conditions, the atoms of noble
gases have little tendency to gain or lose electrons.

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18.10.1 Hydrides
The hydrides of the p-block elements are listed in table 18.5. They are covalent
molecules and their bond angles are consistent with VSEPR theory. The angles
decrease from 109.50 in CH4 to 1070 in NH3 and 1040 in H2O.
These hydrides are volatile in nature. Generally their acid strength increases from
left to right and from top to bottom.
Notes
Table 18.5 : Hydrides of p-block elements
Group
13 14 15 16 17
B2H6 CH4 NH3 H2O HF
(AIH3)x SiH4 PH3 H2S HCI
Ga2H6 GeH4 AsH3 H2Se HBr
InH3 SnH4 SbH3 H2Te HI
TIH3 PbH4 BiH3 H2Po –

18.10.2 Oxides
p-Block elements form a number of oxides on reacting with oxygen. The oxides
E2On (n = 3, 5 or 7) are the highest oxides formed by the elements in the groups
13, 15 or 17 respectively. The oxides EOn (n = 2, 3 or 4) are formed by the
elements in groups 14, 16 or 18 respectively. Thus, nitrogen forms NO, NO2,
N2O3, and N2O5; phosphorus forms P4O6 and P4O10, xenon forms XeO3 and XeO4.
z In any particular group, the basic nature of the oxides (oxidation state of the
element remaining same) increases with increase in atomic number.
z In a particular period the acidity increases with increase in the oxidation state
of the element.

18.10.3 Halides
A review of the properties of halides of p-block elements reveals that most of
them are covalent halides. In a group the covalent character of halides decreases
down the group. Where an element exhibits more than one oxidation state, the
covalent character of a halide increases with the increase in the oxidation state of
the element forming halides. For example, whereas PbCl2 is an ionic halide, PbCl4
is covalent. Similarly the covalent character of halides of a particular element
increases from fluoride to chloride to bromide.
Covalent halides are generally gases, liquids or solids with low melting points.
These halides usually hydrolyse to give the oxoacid of the element. For example
SiCl4 reacts vigorously with water

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SiCl4 + 4H2O Si(OH)4 + 4HCl

In general the chlorides, bromides and iodides are found to be more stable with
lower oxidation state of the element, whereas fluorides are formed in the higher
oxidation states. The halides are usually formed by the direct union of the element
with the halogen. For example

Notes C(s) + Cl2(g) CCl4(l)

2As(s) + Cl2(g) AsCl3(s)

INTEXT QUESTION 18.3

1. Which of the following oxides is the most acidic?

(i) Al2O3 (ii) CO2 (iii) SO2
2. Which of the following hydrides of main group elements is the most acidic?
(i) H2Se (ii) H2O (iii) HCI (iv) HI
3. Arrange the following in the increasing order of covalent character.
SiCl4, CCl4, SnCl4, GeCl4
4. What happens when SiCl4 reacts with water. Write complete chemical
equation for the reaction.
5. How do the bond angles vary among the following hydrides NH3, PH3, AsH3,
SbH3
6. Give equations for the formation of the following from the elements:
(i) Al2O3 (ii) SiCl4 (iii) CCl4
7. Which is more covalent in each of the following pairs?
(i) AlCl3 and BCl3 (ii) PbCl2 and PbCl4

WHAT YOU HAVE LEARNT

z The elements of groups 13, 14, 15, 16, 17 and 18 constitute the p-block of
the periodic table.
z Some of the elements of the p-block are widely and abundantly found in
nature, viz., oxygen, silicon, aluminium, etc.
z Many physical and chemical properties of the p-block main group elements
show periodic variation with atomic number.

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z The ionization enthalpy is the energy required to remove the outermost
electron from a neutral gaseous atom.
z The electron gain enthalpy is the energy change when a neutral atom in a
gaseous state accepts an electron.
zl Electronegativity is the ability of an atom in a molecule to attract the electrons
of a covalent bond to itself.
Notes
z The top element in each group shows a unique behaviour.
z The reluctance of s-electrons to take part in bond formation is known as
“inert pair effect”.
z p-Block elements form a number of oxides on reacting with oxygen.
z Most of the elements of the p-block form covalent halides.
z General characteristies of the p-block hydrides, halides and oxides.

TERMINAL EXERCISE
1. Which groups of the ‘periodic table’ constitute p-block?
2. How does the magnitude of ionization energy of an atom vary along the
group in the periodic table?
3. How does electronegativity change along a row of elements in the periodic
table?
4. Explain ‘Metallic character decreases along a period but increases on moving
down a group’.
5. Discuss the trends in the chemistry of p-block elements with respect to:
(i) acidic and basic nature of the oxides;
(ii) ionic and covalent nature of the hydrides.
6. What is the cause of anomalous behaviour of the top element in each group
of the p-block elements.
7. What is ‘inert pair effect’? Is there any inert pair present or is it a misnomer?
8. Comment on the nature (ionic/covalent) of the hydrides of the p-block
elements
9. How does the covalent character of halides of an element change with
oxidation state of the element?
10. Which is likely to form higher halides with an element exhibiting variable
oxidation state, F2 or Cl2?

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ANSWERS TO INTEXT QUESTIONS

18.1
1. (i) 9F (ii) 6C (iii) 6C (iv) 7N
Notes 2. Be (ii) 17Cl (iii) 2He (iv) 8O
4

3. Na < Be < N < He

4. In a group, it decreases down the group and it usually increases along a
period.

18.2
1. The unexpectedly low value of electron gain enthalpy for F as compared to
that of Cl atom may be attributed to the extremely small size of F atom vis-
a-vis Cl atom. The addition of an electron produces a negative ion which
has a high electron density and leads to increased interelectronic repulsions.
2. (i) Cl (ii) Br (iii) I (iv) F (v) S
3. (i) Small size (ii) absence of d-orbitals
4. Because oxygen can form multiple bonds (O = O).
5. (i) Lower bond energy in the compounds of heavier atoms and (ii) the higher
energy involved in promotion from the ground state (s2p1) to the valence
state (s1p2).
6. Lower oxidation states become more stable.
For Tl, +1 and for Pb, +2.

18.3
1. SO2
2. HI
3. SnCl4 < Ge Cl4 < SiCl4 < CCl4
4. SiCl4 + 4H2O → Si(OH)4 + 4HCl
5. The bond angle decreases from 107º to almost 90º.
6. (i) 4Al(s) + 3O2(g) → 2Al2O3 (s)
(ii) Si(s) + 2Cl2(g) → SiCl4(l)
(iii) C(s) + 2Cl2(g) → CCl4(l)
7. (i) BCl3 (ii) PbCl4

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