THE p-BLOCK ELEMENTS 315

UNIT 11

THE p -BLOCK ELEMENTS

The variation in properties of the p-block elements due to the

influence of d and f electrons in the inner core of the heavier
elements makes their chemistry interesting

After studying this unit, you will be

able to
• appreciate the general trends in the In p-block elements the last electron enters the outermost
chemistry of p-block elements; p orbital. As we know that the number of p orbitals is three
• describe the trends in physical and and, therefore, the maximum number of electrons that can
chemical properties of group 13 and be accommodated in a set of p orbitals is six. Consequently
14 elements; there are six groups of p–block elements in the periodic
• explain anomalous behaviour of table numbering from 13 to 18. Boron, carbon, nitrogen,
boron and carbon; oxygen, fluorine and helium head the groups. Their valence
2 1-6
shell electronic configuration is ns np (except for He).
• describe allotropic forms of carbon;
The inner core of the electronic configuration may,
• know the chemistry of some however, differ. The difference in inner core of elements
important compounds of boron, greatly influences their physical properties (such as atomic
carbon and silicon; and ionic radii, ionisation enthalpy, etc.) as well as chemical
• list the important uses of group 13 properties. Consequently, a lot of variation in properties of
and 14 elements and their elements in a group of p-block is observed. The maximum
compounds. oxidation state shown by a p-block element is equal to the
total number of valence electrons (i.e., the sum of the s-
and p-electrons). Clearly, the number of possible oxidation
states increases towards the right of the periodic table. In
addition to this so called group oxidation state, p-block
elements may show other oxidation states which normally,
but not necessarily, differ from the total number of valence
electrons by unit of two. The important oxidation states
exhibited by p-block elements are shown in Table 11.1. In
boron, carbon and nitrogen families the group oxidation
state is the most stable state for the lighter elements in the
group. However, the oxidation state two unit less than the
group oxidation state becomes progressively more stable
for the heavier elements in each group. The occurrence of
oxidation states two unit less than the group oxidation
states are sometime attributed to the ‘inert pair effect’.

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Table 11.1 General Electronic Configuration and Oxidation States of p-Block Elements

Group 13 14 15 16 17 18
General
electronic ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 ns2np6
configuration (1s2 for He)

First member
of the B C N O F He
group

Group
oxidation +3 +4 +5 +6 +7 +8
state
Other
oxidation +1 +2, – 4 +3, – 3 +4, +2, –2 +5, + 3, +1, –1 +6, +4, +2
states

The relative stabilities of these two oxidation The first member of p-block differs from the
states – group oxidation state and two unit less remaining members of their corresponding
than the group oxidation state – may vary from group in two major respects. First is the size
group to group and will be discussed at and all other properties which depend on size.
appropriate places. Thus, the lightest p-block elements show the
It is interesting to note that the non-metals same kind of differences as the lightest s-block
and metalloids exist only in the p-block of the elements, lithium and beryllium. The second
periodic table. The non-metallic character of important difference, which applies only to the
p-block elements, arises from the effect of d-
elements decreases down the group. In fact the
orbitals in the valence shell of heavier elements
heaviest element in each p-block group is the
(starting from the third period onwards) and
most metallic in nature. This change from non-
their lack in second period elements. The
metallic to metallic character brings diversity
second period elements of p-groups starting
in the chemistry of these elements depending
from boron are restricted to a maximum
on the group to which they belong.
covalence of four (using 2s and three 2p
In general, non-metals have higher ionisation orbitals). In contrast, the third period elements
enthalpies and higher electronegativities than of p-groups with the electronic configuration
the metals. Hence, in contrast to metals which n
3s 2 3p have the vacant 3d orbitals lying
readily form cations, non-metals readily form between the 3p and the 4s levels of energy.
anions. The compounds formed by highly Using these d-orbitals the third period
reactive non-metals with highly reactive metals elements can expand their covalence above
are generally ionic because of large differences four. For example, while boron forms only
– 3–
in their electronegativities. On the other hand, [BF 4 ] , aluminium gives [AlF 6 ] ion. The
compounds formed between non-metals presence of these d-orbitals influences the
themselves are largely covalent in character chemistry of the heavier elements in a number
because of small differences in their of other ways. The combined effect of size and
electronegativities. The change of non-metallic availability of d orbitals considerably
to metallic character can be best illustrated by influences the ability of these elements to form
the nature of oxides they form. The non-metal π bonds. The first member of a group differs
oxides are acidic or neutral whereas metal from the heavier members in its ability to form
oxides are basic in nature. pπ - pπ multiple bonds to itself ( e.g., C=C, C≡C,

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N≡N) and to other second row elements (e.g., isotope is 20 seconds. Due to these reasons its
C=O, C=N, C≡N, N=O). This type of π - bonding chemistry has not been established.
is not particularly strong for the heavier Nihonium is a synthetically prepared
p-block elements. The heavier elements do form radioactive element. Here atomic, physical and
π bonds but this involves d orbitals (dπ – pπ chemical properties of elements of this group
or dπ –dπ ). As the d orbitals are of higher leaving nihonium are discussed below.
energy than the p orbitals, they contribute less
to the overall stability of molecules than does 11.1.1 Electronic Configuration
pπ - pπ bonding of the second row elements. The outer electronic configuration of these
2 1
However, the coordination number in species elements is ns np . A close look at the
of heavier elements may be higher than for electronic configuration suggests that while
the first element in the same oxidation state. boron and aluminium have noble gas
For example, in +5 oxidation state both N and core, gallium and indium have noble gas plus
– 10 d-electrons, and thallium has noble gas
P form oxoanions : NO3 (three-coordination
with π – bond involving one nitrogen p-orbital) plus 14 f- electrons plus 10 d-electron cores.
and PO34− (four-coordination involving s, p and Thus, the electronic structures of these
d orbitals contributing to the π – bond). In elements are more complex than for the first
this unit we will study the chemistry of group two groups of elements discussed in unit 10.
13 and 14 elements of the periodic table. This difference in electronic structures affects
the other properties and consequently the
11.1 GROUP 13 ELEMENTS: THE BORON chemistry of all the elements of this group.
FAMILY
11.1.2 Atomic Radii
This group elements show a wide variation in
On moving down the group, for each successive
properties. Boron is a typical non-metal, member one extra shell of electrons is added
aluminium is a metal but shows many and, therefore, atomic radius is expected to
chemical similarities to boron, and gallium, increase. However, a deviation can be seen.
indium, thallium and nihonium are almost Atomic radius of Ga is less than that of Al. This
exclusively metallic in character. can be understood from the variation in the
Boron is a fairly rare element, mainly inner core of the electronic configuration. The
occurs as orthoboric acid, (H3BO3), borax, presence of additional 10 d-electrons offer
Na2B4O7·10H2O, and kernite, Na2B4O7·4H2O. only poor screening effect (Unit 2) for the outer
In India borax occurs in Puga Valley (Ladakh) electrons from the increased nuclear charge in
and Sambhar Lake (Rajasthan). The gallium. Consequently, the atomic radius of
abundance of boron in earth crust is less than gallium (135 pm) is less than that of
0.0001% by mass. There are two isotopic aluminium (143 pm).
10 11
forms of boron B (19%) and B (81%).
11.1.3 Ionization Enthalpy
Aluminium is the most abundant metal and
the third most abundant element in the earth’s The ionisation enthalpy values as expected
crust (8.3% by mass) after oxygen (45.5%) and from the general trends do not decrease
Si (27.7%). Bauxite, Al2O3. 2H2O and cryolite, smoothly down the group. The decrease from
Na 3 AlF 6 are the important minerals of B to Al is associated with increase in size. The
aluminium. In India it is found as mica in observed discontinuity in the ionisation
Madhya Pradesh, Karnataka, Orissa and enthalpy values between Al and Ga, and
Jammu. Gallium, indium and thallium are less between In and Tl are due to inability of d- and
abundant elements in nature. Nihonium has f-electrons ,which have low screening effect, to
symbol Nh, atomic number 113, atomic mass compensate the increase in nuclear charge.
-1
286 g mol and electronic configuration [Rn] The order of ionisation enthalpies, as
14 10 2 2
5f 6d 7s 7p . So far it has been prepared expected, is ∆i H1<∆i H2<∆i H3. The sum of the
in small amount and half life of its most stable first three ionisation enthalpies for each of the

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elements is very high. Effect of this will be 11.1.6 Chemical Properties

apparent when you study their chemical Oxidation state and trends in chemical
properties. reactivity
11.1.4 Electronegativity Due to small size of boron, the sum of its first
Down the group, electronegativity first three ionization enthalpies is very high. This
decreases from B to Al and then increases prevents it to form +3 ions and forces it to form
marginally (Table 11.2). This is because of the only covalent compounds. But as we move from
discrepancies in atomic size of the elements. B to Al, the sum of the first three ionisation
enthalpies of Al considerably decreases, and
11.1.5 Physical Properties 3+
is therefore able to form Al ions. In fact,
Boron is non-metallic in nature. It is extremely aluminium is a highly electropositive metal.
hard and black coloured solid. It exists in many However, down the group, due to poor
allotropic forms. Due to very strong crystalline shielding effect of intervening d and f orbitals,
lattice, boron has unusually high melting point. the increased effective nuclear charge holds ns
Rest of the members are soft metals with low electrons tightly (responsible for inert pair
melting point and high electrical conductivity. effect) and thereby, restricting their
It is worthwhile to note that gallium with participation in bonding. As a result of this,
unusually low melting point (303 K), could only p-orbital electron may be involved in
exist in liquid state during summer. Its high bonding. In fact in Ga, In and Tl, both +1 and
boiling point (2676 K) makes it a useful +3 oxidation states are observed. The relative
material for measuring high temperatures. stability of +1 oxidation state progressively
Density of the elements increases down the increases for heavier elements: Al<Ga<In<Tl. In
group from boron to thallium. thallium +1 oxidation state is predominant
Table 11.2 Atomic and Physical Properties of Group 13 Elements
Element
Property Boron Aluminium Gallium Indium Thallium
B Al Ga In Tl
Atomic number 5 13 31 49 81
–1
Atomic mass(g mol ) 10.81 26.98 69.72 114.82 204.38
2 1 2 1 10 2 1 10 2 1
Electronic [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f145d106s26p1
Configuration
Atomic radius/pma (88) 143 135 167 170
Ionic radius (27) 53.5 62.0 80.0 88.5
M3+/pmb
Ionic radius - - 120 140 150
M+/pm
Ionization ∆iH1 801 577 579 558 589
enthalpy ∆iH2 2427 1816 1979 1820 1971
(kJ mol–1) ∆iH3 3659 2744 2962 2704 2877
Electronegativityc 2.0 1.5 1.6 1.7 1.8
–3
Density /g cm 2.35 2.70 5.90 7.31 11.85
at 298 K
Melting point / K 2453 933 303 430 576
Boiling point / K 3923 2740 2676 2353 1730
 3+
E / V for (M /M) - –1.66 –0.56 –0.34 +1.26
 +
E / V for (M /M) - +0.55 -0.79(acid) –0.18 –0.34
–1.39(alkali)
a b c
Metallic radius, 6-coordination, Pauling scale,

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THE p-BLOCK ELEMENTS 319

whereas the +3 oxidation state is highly Solution

oxidising in character. The compounds in
Standard electrode potential values for two
+1 oxidation state, as expected from energy
half cell reactions suggest that aluminium
considerations, are more ionic than those in 3+
has high tendency to make Al (aq) ions,
+3 oxidation state. 3+
whereas Tl is not only unstable in
In trivalent state, the number of electrons solution but is a powerful oxidising agent
around the central atom in a molecule +
also. Thus Tl is more stable in solution
of the compounds of these elements 3+
than Tl . Aluminium being able to form
(e.g., boron in BF3) will be only six. Such
+3 ions easily, is more electropositive than
electron deficient molecules have tendency
thallium.
to accept a pair of electrons to achieve stable
electronic configuration and thus, behave as (i) Reactivity towards air
Lewis acids. The tendency to behave as Lewis Boron is unreactive in crystalline form.
acid decreases with the increase in the size Aluminium forms a very thin oxide layer on
down the group. BCl3 easily accepts a lone pair the surface which protects the metal from
of electrons from ammonia to form BCl3⋅NH3. further attack. Amorphous boron and
aluminium metal on heating in air form B2O3
and Al2O3 respectively. With dinitrogen at high
temperature they form nitrides.

2E ( s ) + 3O 2 ( g ) →
∆
2E 2 O 3 ( s )
2E ( s ) + N 2 ( g ) →
∆
2EN ( s )
AlCl3 achieves stability by forming a dimer (E = element)
The nature of these oxides varies down the
group. Boron trioxide is acidic and reacts with
basic (metallic) oxides forming metal borates.
Aluminium and gallium oxides are amphoteric
and those of indium and thallium are basic in
their properties.
(ii) Reactivity towards acids and alkalies
In trivalent state most of the compounds Boron does not react with acids and alkalies
being covalent are hydrolysed in water. For even at moderate temperature; but aluminium
example, the trichlorides on hyrolysis in water dissolves in mineral acids and aqueous alkalies
− and thus shows amphoteric character.
form tetrahedral  M ( OH )4  species; the
3 Aluminium dissolves in dilute HCl and
hybridisation state of element M is sp .
liberates dihydrogen.
Aluminium chloride in acidified aqueous 3+ –
3+ 2Al(s) + 6HCl (aq) → 2Al (aq) + 6Cl (aq)
solution forms octahedral  Al ( H2 O )6  ion.
+ 3H2 (g)
In this complex ion, the 3d orbitals of Al are However, concentrated nitric acid renders
involved and the hybridisation state of Al is aluminium passive by forming a protective
sp3d2. oxide layer on the surface.
Problem 11.1 Aluminium also reacts with aqueous alkali

Standard electrode potential values, E and liberates dihydrogen.
3+ 3+
for Al /Al is –1.66 V and that of Tl /Tl 2Al (s) + 2NaOH(aq) + 6H2O(l)
is +1.26 V. Predict about the formation of ↓
3+ + –
M ion in solution and compare the 2 Na [Al(OH)4] (aq) + 3H2(g)
electropositive character of the two Sodium
metals. tetrahydroxoaluminate(III)

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(iii) Reactivity towards halogens the maximum covalence of boron cannot

These elements react with halogens to form exceed 4.
trihalides (except Tl I3).
2E(s) + 3 X2 (g) → 2EX3 (s) (X = F, Cl, Br, I) 11.3 SOME IMPORTANT COMPOUNDS OF
BORON
Problem 11.2 Some useful compounds of boron are borax,
White fumes appear around the bottle of orthoboric acid and diborane. We will briefly
anhydrous aluminium chloride. Give study their chemistry.
reason.
11.3.1 Borax
Solution
It is the most important compound of boron.
Anhydrous aluminium chloride is It is a white crystalline solid of formula
partially hydrolysed with atmospheric Na 2 B 4 O 7⋅ 10H 2 O. In fact it contains the
moisture to liberate HCl gas. Moist HCl 2−
appears white in colour. tetranuclear units  B4 O5 ( OH )4  and correct
formula; therefore, is Na2[B4O5 (OH)4].8H2O.
11.2 IMPORTANT TRENDS AND Borax dissolves in water to give an alkaline
ANOMALOUS PROPERTIES OF solution.
BORON
Na2B4O7 + 7H2O → 2NaOH + 4H3BO3
Certain important trends can be observed
in the chemical behaviour of group Orthoboric acid
13 elements. The tri-chlorides, bromides On heating, borax first loses water
and iodides of all these elements being molecules and swells up. On further heating it
covalent in nature are hydrolysed in water. turns into a transparent liquid, which solidifies
–
Species like tetrahedral [M(OH) 4] and into glass like material known as borax
3+
octahedral [M(H2O)6] , except in boron, exist bead.
in aqueous medium.
∆
Na2B4O7.10H2O → ∆
Na2B4O7 → 2NaBO2
The monomeric trihalides, being electron
deficient, are strong Lewis acids. Boron Sodium + B2O3
trifluoride easily reacts with Lewis bases such metaborate Boric
as NH3 to complete octet around boron. anhydride
The metaborates of many transition metals
F3 B + :NH 3 → F3 B ← NH3
have characteristic colours and, therefore,
It is due to the absence of d orbitals that borax bead test can be used to identify them
the maximum covalence of B is 4. Since the in the laboratory. For example, when borax is
d orbitals are available with Al and other heated in a Bunsen burner flame with CoO on
elements, the maximum covalence can be a loop of platinum wire, a blue coloured
expected beyond 4. Most of the other metal Co(BO2)2 bead is formed.
halides (e.g., AlCl3) are dimerised through
halogen bridging (e.g., Al2Cl6). The metal 11.3.2 Orthoboric acid
species completes its octet by accepting Orthoboric acid, H3BO3 is a white crystalline
electrons from halogen in these halogen solid, with soapy touch. It is sparingly soluble
bridged molecules. in water but highly soluble in hot water. It can
be prepared by acidifying an aqueous solution
Problem 11.3
3–
of borax.
Boron is unable to form BF6 ion. Explain.
Na2B4O7 + 2HCl + 5H2O → 2NaCl + 4B(OH)3
Solution
It is also formed by the hydrolysis (reaction
Due to non-availability of d orbitals, boron
with water or dilute acid) of most boron
is unable to expand its octet. Therefore,
compounds (halides, hydrides, etc.). It has a

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THE p-BLOCK ELEMENTS 321

layer structure in which planar BO3 units are 2NaBH4 + I2 → B2H6 + 2NaI + H2
joined by hydrogen bonds as shown in Diborane is produced on an industrial scale
Fig. 11.1. by the reaction of BF3 with sodium hydride.
Boric acid is a weak monobasic acid. It is 450K
2BF3 + 6NaH  →B2H6 + 6NaF
not a protonic acid but acts as a Lewis acid
by accepting electrons from a hydroxyl ion: Diborane is a colourless, highly toxic gas
–
B(OH)3 + 2HOH → [B(OH)4] + H3O
+ with a b.p. of 180 K. Diborane catches fire
spontaneously upon exposure to air. It burns
On heating, orthoboric acid above 370K
in oxygen releasing an enormous amount of
forms metaboric acid, HBO2 which on further energy.
heating yields boric oxide, B2O3.
B2 H6 +3O2 → B2 O3 + 3H2 O;
H3BO3 ∆→ HBO2 ∆→ B2O3 
∆c H = −1976 kJ mol−1
Most of the higher boranes are also
spontaneously flammable in air. Boranes are
readily hydrolysed by water to give boric acid.
B2H6(g) + 6H2O(l) → 2B(OH)3(aq) + 6H2(g)
Diborane undergoes cleavage reactions
with Lewis bases(L) to give borane adducts,
BH3⋅L
B2H6 + 2 NMe3 → 2BH3⋅NMe3
B2H6 + 2 CO → 2BH3⋅CO
Reaction of ammonia with diborane gives
initially B2H6.2NH3 which is formulated as
+ –
[BH2(NH3)2] [BH4] ; further heating gives
borazine, B 3 N 3 H 6 known as “inorganic
Fig. 11. 1 Structure of boric acid; the dotted lines benzene” in view of its ring structure with
represent hydrogen bonds alternate BH and NH groups.
–
3B2H6 +6NH3 → 3[BH2 (NH3 )2 ]+ [BH4 ]
Problem 11.4 Heat
 →2B3 N3 H6 +12H2
Why is boric acid considered as a weak
acid? The structure of diborane is shown in
Fig.11.2(a). The four terminal hydrogen atoms
Solution
+
and the two boron atoms lie in one plane.
Because it is not able to release H ions Above and below this plane, there are two
–
on its own. It receives OH ions from water bridging hydrogen atoms. The four terminal
molecule to complete its octet and in turn B-H bonds are regular two centre-two electron
+
releases H ions. bonds while the two bridge (B-H-B) bonds are
different and can be described in terms of three
11.3.3 Diborane, B2H6
The simplest boron hydride known, is
diborane. It is prepared by treating boron
trifluoride with LiAlH4 in diethyl ether.
4BF3 + 3 LiAlH4 → 2B2H6 + 3LiF + 3AlF3
A convenient laboratory method for the
preparation of diborane involves the oxidation
of sodium borohydride with iodine. Fig.11.2(a) The structure of diborane, B2H6

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322 CHEMISTRY

centre–two electron bonds shown in orthoboric acid is generally used as a mild

Fig.11.2 (b). antiseptic.
Boron also forms a series of hydridoborates; Aluminium is a bright silvery-white metal,
–
the most important one is the tetrahedral [BH4] with high tensile strength. It has a high
ion. Tetrahydridoborates of several metals are electrical and thermal conductivity. On a
known. Lithium and sodium tetra- weight-to-weight basis, the electrical
hydridoborates, also known as borohydrides, conductivity of aluminium is twice that of
are prepared by the reaction of metal hydrides copper. Aluminium is used extensively in
with B2H6 in diethyl ether. industry and everyday life. It forms alloys with
+ –
2MH + B2H6 → 2 M [BH4] (M = Li or Na) Cu, Mn, Mg, Si and Zn. Aluminium and its
alloys can be given shapes of pipe, tubes,
rods, wires, plates or foils and, therefore, find
uses in packing, utensil making,
construction, aeroplane and transportation
industry. The use of aluminium and its
compounds for domestic purposes is now
reduced considerably because of their toxic
Fig.11.2(b) Bonding in diborane. Each B atom nature.
uses sp3 hybrids for bonding. Out
of the four sp3 hybrids on each B 11.5 GROUP 14 ELEMENTS: THE CARBON
atom, one is without an electron FAMILY
shown in broken lines. The terminal Carbon, silicon, germanium, tin lead and
B-H bonds are normal 2-centre-2- flerovium are the members of group 14. Carbon
electron bonds but the two bridge
is the seventeenth most abundant element by
bonds are 3-centre-2-electron bonds.
The 3-centre-2-electron bridge bonds
mass in the earth’s crust. It is widely
are also referred to as banana bonds. distributed in nature in free as well as in the
combined state. In elemental state it is available
Both LiBH 4 and NaBH 4 are used as as coal, graphite and diamond; however, in
reducing agents in organic synthesis. They are combined state it is present as metal
useful starting materials for preparing other carbonates, hydrocarbons and carbon dioxide
metal borohydrides. gas (0.03%) in air. One can emphatically say
that carbon is the most versatile element in the
11.4 USES OF BORON AND ALUMINIUM
world. Its combination with other elements
AND THEIR COMPOUNDS
Boron being extremely hard refractory solid of such as dihydrogen, dioxygen, chlorine and
high melting point, low density and very low sulphur provides an astonishing array of
electrical conductivity, finds many materials ranging from living tissues to drugs
applications. Boron fibres are used in making and plastics. Organic chemistry is devoted to
bullet-proof vest and light composite material carbon containing compounds. It is an
10
for aircraft. The boron-10 ( B) isotope has high essential constituent of all living organisms.
ability to absorb neutrons and, therefore, Naturally occurring carbon contains two stable
12 13
metal borides are used in nuclear industry as isotopes: C and C. In addition to these, third
14
protective shields and control rods. The main isotope, C is also present. It is a radioactive
industrial application of borax and boric acid isotope with half-life 5770 years and used for
is in the manufacture of heat resistant glasses radiocarbon dating. Silicon is the second
(e.g., Pyrex), glass-wool and fibreglass. Borax (27.7 % by mass) most abundant element on
is also used as a flux for soldering metals, for the earth’s crust and is present in nature in
heat, scratch and stain resistant glazed coating the form of silica and silicates. Silicon is a very
to earthenwares and as constituent of important component of ceramics, glass and
medicinal soaps. An aqueous solution of cement. Germanium exists only in traces. Tin

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THE p-BLOCK ELEMENTS 323

occurs mainly as cassiterite, SnO2 and lead as 11.5.2 Covalent Radius

galena, PbS. Flerovium is synthetically There is a considerable increase in covalent
prepared radioactive element radius from C to Si, thereafter from Si to Pb a
Ultrapure form of germanium and silicon small increase in radius is observed. This is
are used to make transistors and due to the presence of completely filled d and f
semiconductor devices. orbitals in heavier members.
Symbol of Flerovium is Fl. It has atomic 11.5.3 Ionization Enthalpy
-1
number 114, atomic mass 289 gmol and
14 10 2 2 The first ionization enthalpy of group 14
electronic configuration [Rn] 5f 6d 7s 7p . members is higher than the corresponding
It has been prepared only in small amount. members of group 13. The influence of inner
Its half life is short and its chemistry has not core electrons is visible here also. In general the
been established yet. The important atomic ionisation enthalpy decreases down the group.
and physical properties along with their Small decrease in ∆iH from Si to Ge to Sn and
electronic configuration of the elements of slight increase in ∆iH from Sn to Pb is the
group 14 leaving flerovium are given in consequence of poor shielding effect of
Table 11.3. Some of the atomic, physical and intervening d and f orbitals and increase in size
chemical properties are discussed below: of the atom.
11.5.1 Electronic Configuration 11.5.4 Electronegativity
The valence shell electronic configuration of Due to small size, the elements of this group
2 2
these elements is ns np . The inner core of the are slightly more electronegative than group
electronic configuration of elements in this 13 elements. The electronegativity values for
group also differs. elements from Si to Pb are almost the same.

Table 11.3 Atomic and Physical Properties of Group 14 Elements

Element
Property Carbon Silicon Germanium Tin Lead
C Si Ge Sn Pb
Atomic Number 6 14 32 50 82
–1
Atomic mass (g mol ) 12.01 28.09 72.60 118.71 207.2
2 2 2 2 10 2 2 10 2 2 14 10 2 2
Electronic [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
configuration
a
Covalent radius/pm 77 118 122 140 146
4+ b
Ionic radius M /pm – 40 53 69 78
2+ b
Ionic radius M /pm – – 73 118 119
Ionization ∆iH 1 1086 786 761 708 715
enthalpy/ ∆iH 2 2352 1577 1537 1411 1450
kJ mol–1 ∆iH 3 4620 3228 3300 2942 3081
∆iH 4 6220 4354 4409 3929 4082
c
Electronegativity 2.5 1.8 1.8 1.8 1.9
d –3 e f
Density /g cm 3.51 2.34 5.32 7.26 11.34
Melting point/K 4373 1693 1218 505 600
Boiling point/K – 3550 3123 2896 2024
14 16 –5 –5
Electrical resistivity/ 10 –10 50 50 10 2 × 10
ohm cm (293 K)
a IV b c d e
for M oxidation state; 6–coordination; Pauling scale; 293 K; for diamond; for graphite, density is
f
2.22; β-form (stable at room temperature)

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11.5.5 Physical Properties MO2 respectively. SiO only exists at high

All members of group14 are solids. Carbon and temperature. Oxides in higher oxidation states
silicon are non-metals, germanium is a metalloid, of elements are generally more acidic than
whereas tin and lead are soft metals with low those in lower oxidation states. The dioxides
melting points. Melting points and boiling points — CO2, SiO2 and GeO2 are acidic, whereas
of group 14 elements are much higher than those SnO2 and PbO2 are amphoteric in nature.
of corresponding elements of group 13. Among monoxides, CO is neutral, GeO is
distinctly acidic whereas SnO and PbO are
11.5.6 Chemical Properties amphoteric.
Oxidation states and trends in chemical
Problem 11.5
reactivity
The group 14 elements have four electrons in Select the member(s) of group 14 that
outermost shell. The common oxidation states (i) forms the most acidic dioxide, (ii) is
exhibited by these elements are +4 and +2. commonly found in +2 oxidation state,
Carbon also exhibits negative oxidation states. (iii) used as semiconductor.
Since the sum of the first four ionization Solution
enthalpies is very high, compounds in +4
(i) carbon (ii) lead
oxidation state are generally covalent in nature.
(iii) silicon and germanium
In heavier members the tendency to show +2
oxidation state increases in the sequence
Ge<Sn<Pb. It is due to the inability of ns
2 (ii) Reactivity towards water
electrons of valence shell to participate in Carbon, silicon and germanium are not
bonding. The relative stabilities of these two affected by water. Tin decomposes steam to
oxidation states vary down the group. Carbon form dioxide and dihydrogen gas.
and silicon mostly show +4 oxidation state. ∆
Sn + 2H2 O 
→ SnO2 + 2H2
Germanium forms stable compounds in +4
state and only few compounds in +2 state. Tin Lead is unaffected by water, probably
forms compounds in both oxidation states (Sn because of a protective oxide film formation.
in +2 state is a reducing agent). Lead
(iii) Reactivity towards halogen
compounds in +2 state are stable and in +4
state are strong oxidising agents. In tetravalent These elements can form halides of formula
state the number of electrons around the MX2 and MX4 (where X = F, Cl, Br, I). Except
central atom in a molecule (e.g., carbon in CCl4) carbon, all other members react directly with
is eight. Being electron precise molecules, they halogen under suitable condition to make
are normally not expected to act as electron halides. Most of the MX4 are covalent in nature.
acceptor or electron donor species. Although The central metal atom in these halides
3
carbon cannot exceed its covalence more than undergoes sp hybridisation and the molecule
4, other elements of the group can do so. It is is tetrahedral in shape. Exceptions are SnF4
because of the presence of d orbital in them. and PbF4, which are ionic in nature. PbI4 does
Due to this, their halides undergo hydrolysis not exist because Pb—I bond initially formed
and have tendency to form complexes by during the reaction does not release enough
2
accepting electron pairs from donor species. For energy to unpair 6s electrons and excite one
2–
example, the species like, SiF6 , [GeCl6] ,
2– of them to higher orbital to have four unpaired
2–
[Sn(OH)6] exist where the hybridisation of the electrons around lead atom. Heavier members
3 2
central atom is sp d . Ge to Pb are able to make halides of formula
MX2. Stability of dihalides increases down the
(i) Reactivity towards oxygen group. Considering the thermal and chemical
All members when heated in oxygen form stability, GeX4 is more stable than GeX 2,
oxides. There are mainly two types of oxides, whereas PbX2 is more than PbX4. Except CCl4,
i.e., monoxide and dioxide of formula MO and other tetrachlorides are easily hydrolysed

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THE p-BLOCK ELEMENTS 325

by water because the central atom can Carbon also has unique ability to form
accommodate the lone pair of electrons from pπ– pπ multiple bonds with itself and with other
oxygen atom of water molecule in d orbital. atoms of small size and high electronegativity.
Hydrolysis can be understood by taking Few examples of multiple bonding are: C=C,
the example of SiCl4. It undergoes hydrolysis C ≡ C, C = O, C = S, and C ≡ N. Heavier elements
by initially accepting lone pair of electrons do not form pπ– pπ bonds because their atomic
from water molecule in d orbitals of Si, finally orbitals are too large and diffuse to have
leading to the formation of Si(OH)4 as shown effective overlapping.
below :
Carbon atoms have the tendency to link
with one another through covalent bonds to
form chains and rings. This property is called
catenation. This is because C—C bonds are
very strong. Down the group the size increases
and electronegativity decreases, and, thereby,
tendency to show catenation decreases. This
can be clearly seen from bond enthalpies
values. The order of catenation is C > > Si >
Ge ≈ Sn. Lead does not show catenation.
–1
Bond Bond enthalpy / kJ mol
Problem 11. 6 C—C 348
2– 2–
[SiF6] is known whereas [SiCl6] not. Si —Si 297
Give possible reasons. Ge—Ge 260
Solution Sn—Sn 240
The main reasons are :
Due to property of catenation and pπ– pπ
(i) six large chloride ions cannot be
4+ bond formation, carbon is able to show
accommodated around Si due to
allotropic forms.
limitation of its size.
(ii) interaction between lone pair of 11.7 ALLOTROPES OF CARBON
4+
chloride ion and Si is not very strong. Carbon exhibits many allotropic forms; both
crystalline as well as amorphous. Diamond
11.6 IMPORTANT TRENDS AND and graphite are two well-known crystalline
ANOMALOUS BEHAVIOUR OF forms of carbon. In 1985, third form of carbon
CARBON known as fullerenes was discovered by
Like first member of other groups, carbon H.W.Kroto, E.Smalley and R.F.Curl. For this
also differs from rest of the members of its discovery they were awarded the Nobel Prize
group. It is due to its smaller size, higher in 1996.
electronegativity, higher ionisation enthalpy
and unavailability of d orbitals. 11.7.1 Diamond
In carbon, only s and p orbitals are It has a crystalline lattice. In diamond each
3
available for bonding and, therefore, it can carbon atom undergoes sp hybridisation and
accommodate only four pairs of electrons linked to four other carbon atoms by using
around it. This would limit the maximum hybridised orbitals in tetrahedral fashion. The
covalence to four whereas other members can C–C bond length is 154 pm. The structure
expand their covalence due to the presence of extends in space and produces a rigid three-
d orbitals. dimensional network of carbon atoms. In this

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Fig. 11.3 The structure of diamond Fig 11.4 The structure of graphite

structure (Fig. 11.3) directional covalent bonds therefore, graphite conducts electricity along
are present throughout the lattice. the sheet. Graphite cleaves easily between the
It is very difficult to break extended covalent layers and, therefore, it is very soft and slippery.
bonding and, therefore, diamond is a hardest For this reason graphite is used as a dry
substance on the earth. It is used as an lubricant in machines running at high
abrasive for sharpening hard tools, in making temperature, where oil cannot be used as a
dyes and in the manufacture of tungsten lubricant.
filaments for electric light bulbs. 11.7.3 Fullerenes
Problem 11.7 Fullerenes are made by the heating of graphite
Diamond is covalent, yet it has high in an electric arc in the presence of inert gases
melting point. Why ? such as helium or argon. The sooty material
n
formed by condensation of vapourised C small
Solution molecules consists of mainly C60 with smaller
Diamond has a three-dimensional quantity of C 70 and traces of fullerenes
network involving strong C—C bonds, consisting of even number of carbon atoms up
which are very difficult to break and, in to 350 or above. Fullerenes are the only pure
turn has high melting point. form of carbon because they have smooth
structure without having ‘dangling’ bonds.
11.7.2 Graphite Fullerenes are cage like molecules. C 60
Graphite has layered structure (Fig.11.4). molecule has a shape like soccer ball and
Layers are held by van der Waals forces and called Buckminsterfullerene (Fig. 11.5).
distance between two layers is 340 pm. Each It contains twenty six- membered rings and
layer is composed of planar hexagonal rings twelve five-membered rings. A six membered
of carbon atoms. C—C bond length within the ring is fused with six or five membered rings
layer is 141.5 pm. Each carbon atom in but a five membered ring can only fuse with
2
hexagonal ring undergoes sp hybridisation six membered rings. All the carbon atoms are
2
and makes three sigma bonds with three equal and they undergo sp hybridisation.
neighbouring carbon atoms. Fourth electron Each carbon atom forms three sigma bonds
forms a π bond. The electrons are delocalised with other three carbon atoms. The remaining
over the whole sheet. Electrons are mobile and, electron at each carbon is delocalised in

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THE p-BLOCK ELEMENTS 327

molecular orbitals, which in turn give aromatic filters to remove organic contaminators and in
character to molecule. This ball shaped airconditioning system to control odour.
molecule has 60 vertices and each one is Carbon black is used as black pigment in
occupied by one carbon atom and it also black ink and as filler in automobile tyres. Coke
contains both single and double bonds with is used as a fuel and largely as a reducing
C–C distances of 143.5 pm and 138.3 pm agent in metallurgy. Diamond is a precious
respectively. Spherical fullerenes are also called stone and used in jewellery. It is measured in
bucky balls in short. carats (1 carat = 200 mg).
11.8 SOME IMPORTANT COMPOUNDS OF
CARBON AND SILICON
Oxides of Carbon
Two important oxides of carbon are carbon
monoxide, CO and carbon dioxide, CO2.
11.8.1 Carbon Monoxide
Direct oxidation of C in limited supply of
oxygen or air yields carbon monoxide.
∆
2C(s) + O2 (g)  
→ 2CO(g)
On small scale pure CO is prepared by
dehydration of formic acid with concentrated
H2SO4 at 373 K
373K
Fig.11.5 The structure of C60 , Buckminster- HCOOH 
conc.H SO→ H2 O + CO
2 4
fullerene : Note that molecule has the
shape of a soccer ball (football). On commercial scale it is prepared by the
passage of steam over hot coke. The mixture
It is very important to know that graphite of CO and H2 thus produced is known as water
is thermodynamically most stable allotrope of gas or synthesis gas.

carbon and, therefore, ∆f H of graphite is taken 473−1273K

as zero. ∆f H values of diamond and fullerene, C ( s ) + H2 O ( g )  → CO ( g ) + H2 ( g )
–1
C60 are 1.90 and 38.1 kJ mol , respectively. Water gas
Other forms of elemental carbon like carbon When air is used instead of steam, a mixture
black, coke, and charcoal are all impure forms of CO and N2 is produced, which is called
of graphite or fullerenes. Carbon black is producer gas.
obtained by burning hydrocarbons in a limited 1273K
supply of air. Charcoal and coke are obtained 2C(s) + O2 (g) + 4N 2 (g)  → 2CO(g)
by heating wood or coal respectively at high + 4N 2 (g)
temperatures in the absence of air. Producer gas
11.7.4 Uses of Carbon Water gas and producer gas are very
Graphite fibres embedded in plastic material important industrial fuels. Carbon monoxide
form high strength, lightweight composites. in water gas or producer gas can undergo
The composites are used in products such as further combustion forming carbon dioxide
tennis rackets, fishing rods, aircrafts and with the liberation of heat.
canoes. Being good conductor, graphite is used Carbon monoxide is a colourless,
for electrodes in batteries and industrial odourless and almost water insoluble gas. It
electrolysis. Crucibles made from graphite are is a powerful reducing agent and reduces
inert to dilute acids and alkalies. Being highly almost all metal oxides other than those of the
porous, activated charcoal is used in alkali and alkaline earth metals, aluminium
adsorbing poisonous gases; also used in water and a few transition metals. This property of

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CO is used in the extraction of many metals atmosphere, is removed from it by the process
from their oxides ores. known as photosynthesis. It is the process
∆ by which green plants convert atmospheric
Fe2 O3 ( s ) + 3CO ( g )  → 2Fe ( s ) + 3CO2 ( g )

CO2 into carbohydrates such as glucose. The
∆
ZnO ( s ) + CO ( g )  → Zn ( s ) + CO2 ( g )
 overall chemical change can be expressed as:
In CO molecule, there are one sigma and hν
6CO2 +12H2O → C6 H12O6 + 6O2
two π bonds between carbon and oxygen, Chlorophyll
:C ≡ O: . Because of the presence of a lone pair + 6H2O
on carbon, CO molecule acts as a donor and By this process plants make food for
reacts with certain metals when heated to form themselves as well as for animals and human
metal carbonyls. The highly poisonous beings. Unlike CO, it is not poisonous. But the
nature of CO arises because of its ability to increase in combustion of fossil fuels and
form a complex with haemoglobin, which decomposition of limestone for cement
is about 300 times more stable than the manufacture in recent years seem to increase
oxygen-haemoglobin complex. This prevents the CO2 content of the atmosphere. This may
haemoglobin in the red blood corpuscles from lead to increase in green house effect and
carrying oxygen round the body and ultimately thus, raise the temperature of the atmosphere
resulting in death. which might have serious consequences.
11.8.2 Carbon Dioxide Carbon dioxide can be obtained as a solid
in the form of dry ice by allowing the liquified
It is prepared by complete combustion of
CO2 to expand rapidly. Dry ice is used as a
carbon and carbon containing fuels in excess
refrigerant for ice-cream and frozen food.
of air.
Gaseous CO2 is extensively used to carbonate
∆ soft drinks. Being heavy and non-supporter
C(s) + O2 (g)  
→ CO2 (g)
of combustion it is used as fire extinguisher. A
∆
CH 4 (g) + 2O2 (g) → CO2 (g) + 2H2 O(g) substantial amount of CO 2 is used to
manufacture urea.
In the laboratory it is conveniently
prepared by the action of dilute HCl on calcium In CO2 molecule carbon atom undergoes
carbonate. sp hybridisation. Two sp hybridised orbitals
of carbon atom overlap with two p orbitals of
CaCO3(s) + 2HCl (aq) → CaCl2 (aq) + CO2 (g) +
oxygen atoms to make two sigma bonds while
H2O(l)
other two electrons of carbon atom are involved
On commercial scale it is obtained by in pπ– pπ bonding with oxygen atom. This
heating limestone. results in its linear shape [with both C–O bonds
It is a colourless and odourless gas. Its low of equal length (115 pm)] with no dipole
solubility in water makes it of immense bio- moment. The resonance structures are shown
chemical and geo-chemical importance. With below:
water, it forms carbonic acid, H2CO3 which is
a weak dibasic acid and dissociates in two
steps: Resonance structures of carbon dioxide
– +
H2CO3(aq) + H2O(l) HCO3 (aq) + H3O (aq)
– 2– + 11.8.3 Silicon Dioxide, SiO2
HCO3 (aq) + H2O(l)  CO3 (aq) + H3O (aq)
– 95% of the earth’s crust is made up of silica
H 2 CO 3 /HCO 3 buffer system helps to and silicates. Silicon dioxide, commonly known
maintain pH of blood between 7.26 to 7.42. as silica, occurs in several crystallographic
Being acidic in nature, it combines with alkalies forms. Quartz, cristobalite and tridymite are
to form metal carbonates. some of the crystalline forms of silica, and they
Carbon dioxide, which is normally present are interconvertable at suitable temperature.
to the extent of ~ 0.03 % by volume in the Silicon dioxide is a covalent, three-dimensional

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THE p-BLOCK ELEMENTS 329

network solid in which each silicon atom is substituted chlorosilane of formula MeSiCl3,
covalently bonded in a tetrahedral manner to Me2SiCl2, Me3SiCl with small amount of Me4Si
four oxygen atoms. Each oxygen atom in turn are formed. Hydrolysis of dimethyl-
covalently bonded to another silicon atoms as dichlorosilane, (CH 3 ) 2 SiCl 2 followed by
shown in diagram (Fig 11.6 ). Each corner is condensation polymerisation yields straight
shared with another tetrahedron. The entire chain polymers.
crystal may be considered as giant molecule
in which eight membered rings are formed with
alternate silicon and oxygen atoms.

Fig. 11.6 Three dimensional structure of SiO2

Silica in its normal form is almost non-
reactive because of very high Si — O bond
enthalpy. It resists the attack by halogens,
dihydrogen and most of the acids and metals
even at elevated temperatures. However, it is
attacked by HF and NaOH.
The chain length of the polymer can be
SiO2 + 2NaOH → Na2SiO3 + H2O
controlled by adding (CH3)3SiCl which blocks
SiO2 + 4HF → SiF4 + 2H2O the ends as shown below :
Quartz is extensively used as a piezoelectric
material; it has made possible to develop extremely
accurate clocks, modern radio and television
broadcasting and mobile radio communications.
Silica gel is used as a drying agent and as a support
for chromatographic materials and catalysts.
Kieselghur, an amorphous form of silica is used
in filtration plants.
11.8.4 Silicones
They are a group of organosilicon polymers,
which have (R2SiO) as a repeating unit. The
starting materials for the manufacture of
silicones are alkyl or aryl substituted silicon
chlorides, Rn SiCl (4–n), where R is alkyl or aryl
group. When methyl chloride reacts with
silicon in the presence of copper as a catalyst
at a temperature 573K various types of methyl

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330 CHEMISTRY

Silicones being surrounded by non-polar

alkyl groups are water repelling in nature.
They have in general high thermal stability,
high dielectric strength and resistance to
oxidation and chemicals. They have wide
applications. They are used as sealant, greases,
electrical insulators and for water proofing of
fabrics. Being biocompatible they are also used
in surgical and cosmetic plants.

Problem: 11.8
What are silicones ? (a) (b)
4–
Solution Fig. 11.7 (a) Tetrahedral structure of SiO 4
4–
anion; (b) Representation of SiO4 unit
Simple silicones consist of
neutralised by positively charged metal ions.
chains in which alkyl or phenyl groups If all the four corners are shared with other
occupy the remaining bonding positions tetrahedral units, three-dimensional network
on each silicon. They are hydrophobic is formed.
(water repellant) in nature. Two important man-made silicates are
glass and cement.
11.8.5 Silicates
11.8.6 Zeolites
A large number of silicates minerals exist in
nature. Some of the examples are feldspar, If aluminium atoms replace few silicon atoms
zeolites, mica and asbestos. The basic in three-dimensional network of silicon dioxide,
4– overall structure known as aluminosilicate,
structural unit of silicates is SiO4 (Fig.11.7)
in which silicon atom is bonded to four acquires a negative charge. Cations such as
+ +
oxygen atoms in tetrahedron fashion. In Na , K or Ca2+ balance the negative charge.
silicates either the discrete unit is present or Examples are feldspar and zeolites. Zeolites are
a number of such units are joined together widely used as a catalyst in petrochemical
via corners by sharing 1,2,3 or 4 oxygen industries for cracking of hydrocarbons and
atoms per silicate units. When silicate units isomerisation, e.g., ZSM-5 (A type of zeolite)
are linked together, they form chain, ring, used to convert alcohols directly into gasoline.
sheet or three-dimensional structures. Hydrated zeolites are used as ion exchangers
Negative charge on silicate structure is in softening of “hard” water.

SUMMARY

p-Block of the periodic table is unique in terms of having all types of elements – metals,
non-metals and metalloids. There are six groups of p-block elements in the periodic
2 1–6
table numbering from 13 to 18. Their valence shell electronic configuration is ns np
(except for He). Differences in the inner core of their electronic configuration greatly
influence their physical and chemical properties. As a consequence of this, a lot of
variation in properties among these elements is observed. In addition to the group oxidation
state, these elements show other oxidation states differing from the total number of valence
electrons by unit of two. While the group oxidation state is the most stable for the lighter
elements of the group, lower oxidation states become progressively more stable for the
heavier elements. The combined effect of size and availability of d orbitals considerably

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