Unit

Objectives The p -Block

7
After studying this Unit, you will be
able to Elements
• appreciate general trends in the
chemistry of elements of groups
15,16,17 and 18;
Diversity in chemistry is the hallmark of p–block elements manifested
• learn the preparation, properties in their ability to react with the elements of s–, d– and f–blocks as
and uses of dinitrogen and well as with their own.
phosphorus and some of their
important compounds;
• describe the preparation, In Class XI, you have learnt that the p-block elements
properties and uses of dioxygen are placed in groups 13 to 18 of the periodic table.
and ozone and chemistry of some Their valence shell electronic configuration is ns2np1–6
simple oxides; 2
(except He which has 1s configuration). The properties
• know allotropic forms of sulphur, of p-block elements like that of others are greatly
chemistry of its important influenced by atomic sizes, ionisation enthalpy, electron
compounds and the structures of gain enthalpy and electronegativity. The absence of d-
its oxoacids;
orbitals in second period and presence of d or d and f
• describe the preparation,
orbitals in heavier elements (starting from third period
properties and uses of chlorine
onwards) have significant effects on the properties of
and hydrochloric acid;
elements. In addition, the presence of all the three types
• know the chemistry of
interhalogens and structures of
of elements; metals, metalloids and non-metals bring
oxoacids of halogens; diversification in chemistry of these elements.
• enumerate the uses of noble Having learnt the chemistry of elements of Groups
gases; 13 and 14 of the p-block of periodic table in Class XI,
• appreciate the importance of you will learn the chemistry of the elements of
these elements and their subsequent groups in this Unit.
compounds in our day to day life.

7.1 Group 15 Group 15 includes nitrogen, phosphorus, arsenic, antimony, bismuth

Elements and moscovium. As we go down the group, there is a shift from non-
metallic to metallic through metalloidic character. Nitrogen and
phosphorus are non-metals, arsenic and antimony metalloids, bismuth
and moscovium are typical metals.

7.1.1 Occurrence Molecular nitrogen comprises 78% by volume of the atmosphere.

In the earth’s crust, it occurs as sodium nitrate, NaNO3 (called Chile
saltpetre) and potassium nitrate (Indian saltpetre). It is found in the
form of proteins in plants and animals. Phosphorus occurs in minerals

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 of the apatite family, Ca9(PO4)6. CaX2 (X = F, Cl or OH) (e.g., fluorapatite
Ca9 (PO4)6. CaF2) which are the main components of phosphate rocks.
Phosphorus is an essential constituent of animal and plant matter. It
is present in bones as well as in living cells. Phosphoproteins are present
in milk and eggs. Arsenic, antimony and bismuth are found mainly as
sulphide minerals. Moscovium is a synthetic radioactive element. Its
symbol is Mc, atomic number 115, atomic mass 289 and electronic
14 10 2 3
configuration [Rn] 5f 6d 7s 7p . Due to very short half life and
availability in very little amount, its chemistry is yet to be established.
Here, except for moscovium, important atomic and physical
properties of other elements of this group along with their electronic
configurations are given in Table 7.1.

Table 7.1: Atomic and Physical Properties of Group 15 Elements

Property N P As Sb Bi
Atomic number 7 15 33 51 83
–1
Atomic mass/g mol 14.01 30.97 74.92 121.75 208.98
2 3 2 3 10 2 3 10 2 3 14 10 2 3
Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
Ionisation enthalpy I 1402 1012 947 834 703
–1
(∆iH/(kJ mol ) II 2856 1903 1798 1595 1610
III 4577 2910 2736 2443 2466
Electronegativity 3.0 2.1 2.0 1.9 1.9
a
Covalent radius/pm 70 110 121 141 148
b b b c c
Ionic radius/pm 171 212 222 76 103
d e
Melting point/K 63* 317 1089 904 544
d f
Boiling point/K 77.2* 554 888 1860 1837
–3 g h
Density/[g cm (298 K)] 0.879 1.823 5.778 6.697 9.808
a
EIII single bond (E = element); b E 3–; c E 3+; d
White phosphorus; e
Grey α-form at 38.6 atm; f Sublimation temperature;
g
At 63 K; hGrey α-form; * Molecular N2.

Trends of some of the atomic, physical and chemical properties of the

group are discussed below.
2 3
7.1.2 Electronic The valence shell electronic configuration of these elements is ns np .
Configuration The s orbital in these elements is completely filled and p orbitals are
half-filled, making their electronic configuration extra stable.

7.1.3 Atomic and Covalent and ionic (in a particular state) radii increase in size
Ionic Radii down the group. There is a considerable increase in covalent radius
from N to P. However, from As to Bi only a small increase in
covalent radius is observed. This is due to the presence of
completely filled d and/or f orbitals in heavier members.

7.1.4 Ionisation Ionisation enthalpy decreases down the group due to gradual increase
Enthalpy in atomic size. Because of the extra stable half-filled p orbitals electronic
configuration and smaller size, the ionisation enthalpy of the group 15
elements is much greater than that of group 14 elements in the
corresponding periods. The order of successive ionisation enthalpies,
as expected is ∆iH1 < ∆iH2 < ∆iH3 (Table 7.1).

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7.1.5 The electronegativity value, in general, decreases down the group with
Electronegativity increasing atomic size. However, amongst the heavier elements, the
difference is not that much pronounced.

7.1.6 Physical All the elements of this group are polyatomic. Dinitrogen is a diatomic gas
Properties while all others are solids. Metallic character increases down the group.
Nitrogen and phosphorus are non-metals, arsenic and antimony metalloids
and bismuth is a metal. This is due to decrease in ionisation enthalpy and
increase in atomic size. The boiling points, in general, increase from top to
bottom in the group but the melting point increases upto arsenic and then
decreases upto bismuth. Except nitrogen, all the elements show allotropy.
7.1.7 Chemical Oxidation states and trends in chemical reactivity
Properties The common oxidation states of these elements are –3, +3 and +5.
The tendency to exhibit –3 oxidation state decreases down the group due
to increase in size and metallic character. In fact last member of the group,
bismuth hardly forms any compound in –3 oxidation state. The stability
of +5 oxidation state decreases down the group. The only well characterised
Bi (V) compound is BiF5. The stability of +5 oxidation state decreases and
that of +3 state increases (due to inert pair effect) down the group. Besides
+5 oxidation state, nitrogen exhibits + 1, + 2, + 4 oxidation states also
when it reacts with oxygen. However, it does not form compounds in
+5 oxidation state with halogens as nitrogen does not have d-orbitals
to accommodate electrons from other elements to form bonds.
Phosphorus also shows +1 and +4 oxidation states in some oxoacids.
In the case of nitrogen, all oxidation states from +1 to +4 tend to
disproportionate in acid solution. For example,
3HNO2 → HNO3 + H2O + 2NO
Similarly, in case of phosphorus nearly all intermediate oxidation
states disproportionate into +5 and –3 both in alkali and acid. However
+3 oxidation state in case of arsenic, antimony and bismuth becomes
increasingly stable with respect to disproportionation.
Nitrogen is restricted to a maximum covalency of 4 since only four
(one s and three p) orbitals are available for bonding. The heavier elements
have vacant d orbitals in the outermost shell which can be used for
–
bonding (covalency) and hence, expand their covalence as in PF6.
Anomalous properties of nitrogen
Nitrogen differs from the rest of the members of this group due to
its small size, high electronegativity, high ionisation enthalpy and
non-availability of d orbitals. Nitrogen has unique ability to form
pπ -p π multiple bonds with itself and with other elements having
small size and high electronegativity (e.g., C, O). Heavier elements of
this group do not form pπ -pπ bonds as their atomic orbitals are so
large and diffuse that they cannot have effective overlapping.
Thus, nitrogen exists as a diatomic molecule with a triple bond (one
s and two p) between the two atoms. Consequently, its bond enthalpy
–1
(941.4 kJ mol ) is very high. On the contrary, phosphorus, arsenic
and antimony form single bonds as P–P, As–As and Sb–Sb while
bismuth forms metallic bonds in elemental state. However, the single

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N–N bond is weaker than the single P–P bond because of high
interelectronic repulsion of the non-bonding electrons, owing to the
small bond length. As a result the catenation tendency is weaker in
nitrogen. Another factor which affects the chemistry of nitrogen is
the absence of d orbitals in its valence shell. Besides restricting its
covalency to four, nitrogen cannot form dπ –pπ bond as the heavier
elements can e.g., R3P = O or R3P = CH2 (R = alkyl group). Phosphorus
and arsenic can form dπ –dπ bond also with transition metals when
their compounds like P(C2H5) 3 and As(C6H5) 3 act as ligands.
(i) Reactivity towards hydrogen: All the elements of Group 15
form hydrides of the type EH3 where E = N, P, As, Sb or Bi.
Some of the properties of these hydrides are shown in Table
7.2. The hydrides show regular gradation in their properties.
The stability of hydrides decreases from NH3 to BiH3 which can
be observed from their bond dissociation enthalpy.
Consequently, the reducing character of the hydrides increases.
Ammonia is only a mild reducing agent while BiH3 is the
strongest reducing agent amongst all the hydrides. Basicity also
decreases in the order NH3 > PH3 > AsH3 > SbH3 > BiH3. Due to
high electronegativity and small size of nitrogen, NH3 exhibits
hydrogen bonding in solid as well as liquid state. Because of this,
it has higher melting and boiling points than that of PH3.

Table 7.2: Properties of Hydrides of Group 15 Elements

Property NH 3 PH 3 AsH3 SbH 3 BiH3

Melting point/K 195.2 139.5 156.7 185 –

Boiling point/K 238.5 185.5 210.6 254.6 290

(E–H) Distance/pm 101.7 141.9 151.9 170.7 –

HEH angle (°) 107.8 93.6 91.8 91.3 –

V –1
∆f H /kJ mol –46.1 13.4 66.4 145.1 278
V –1
∆dissH (E–H)/kJ mol 389 322 297 255 –

(ii) Reactivity towards oxygen: All these elements form two types
of oxides: E2O3 and E2O5. The oxide in the higher oxidation state
of the element is more acidic than that of lower oxidation state.
Their acidic character decreases down the group. The oxides of
the type E2O3 of nitrogen and phosphorus are purely acidic,
that of arsenic and antimony amphoteric and those of bismuth
predominantly basic.
(iii) Reactivity towards halogens: These elements react to form two
series of halides: EX3 and EX5. Nitrogen does not form pentahalide
due to non-availability of the d orbitals in its valence shell.
Pentahalides are more covalent than trihalides. This is due to the
fact that in pentahalides +5 oxidation state exists while in the case
of trihalides +3 oxidation state exists. Since elements in +5 oxidation

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 state will have more polarising power than in +3 oxidation state,
the covalent character of bonds is more in pentahalides. All the
trihalides of these elements except those of nitrogen are stable.
In case of nitrogen, only NF3 is known to be stable. Trihalides
except BiF3 are predominantly covalent in nature.
(iv) Reactivity towards metals: All these elements react with metals
to form their binary compounds exhibiting –3 oxidation state,
such as, Ca3N2 (calcium nitride) Ca3P2 (calcium phosphide),
Na3As (sodium arsenide), Zn3Sb2 (zinc antimonide) and Mg3Bi2
(magnesium bismuthide).

Though nitrogen exhibits +5 oxidation state, it does not form Example 7.1
pentahalide. Give reason.
Nitrogen with n = 2, has s and p orbitals only. It does not have d Solution
orbitals to expand its covalence beyond four. That is why it does not
form pentahalide.

PH3 has lower boiling point than NH3. Why? Example 7.2
Unlike NH3, PH3 molecules are not associated through hydrogen bonding Solution
in liquid state. That is why the boiling point of PH3 is lower than NH3.

Intext Questions
7.1 Why are pentahalides of P, As, Sb and Bi more covalent than their
trihalides?
7.2 Why is BiH3 the strongest reducing agent amongst all the hydrides of
Group 15 elements ?

7.2 Dinitrogen Preparation

Dinitrogen is produced commercially by the liquefaction and fractional
distillation of air. Liquid dinitrogen (b.p. 77.2 K) distils out first leaving
behind liquid oxygen (b.p. 90 K).
In the laboratory, dinitrogen is prepared by treating an aqueous
solution of ammonium chloride with sodium nitrite.
NH4CI(aq) + NaNO2(aq) → N2(g) + 2H2O(l) + NaCl (aq)
Small amounts of NO and HNO3 are also formed in this reaction;
these impurities can be removed by passing the gas through aqueous
sulphuric acid containing potassium dichromate. It can also be obtained
by the thermal decomposition of ammonium dichromate.
(NH4)2Cr2O7 
Heat
→ N2 + 4H2O + Cr2O3

Very pure nitrogen can be obtained by the thermal decomposition

of sodium or barium azide.
Ba(N3)2 → Ba + 3N2

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