LECTURE NOTE - 2025 CHEMISTRY [SECOND YEAR]

CHAPTER - 04
THE p-BLOCK ELEMENTS - II

1.0 INTRODUCTION
The elements of groups 13 to 18 constitute the p-block of the periodic table. Except helium which has 1s2
configuration, their valence shell electronic configuration is ns2 np1–6 where n = 2-6. Like other elements, the
properties of p-block elements are also influenced by variation in atomic size, ionisation enthalpy, electron gain
enthalpy and electronegativity. The absence of d-orbitals in elements of the second period and presence of d-
and/or f-orbitals in the heavier elements have significant effect on the properties of these elements. The p-block
elements can be metals, metalloids or non-metals. This leads to diversification in the chemistry of these elements.
s - block d - block p - block
1 18
2 13 14 15 16 17 2He

5B 6C 7N 8O 9F 10Ne
3 4 5 6 7 8 9 10 11 12 13Al 14Si 15P 16S 17Cl 18Ar
31Ga 32Ge 33As 34Se 35 Br 36Kr

49In 50Sn 51Sb 52Te 53I 54Xe

81Tl 82Pb 83Bi 84Po 85At 86Rn

113Nh 114Fl 115Mc 116Lv 117Ts 118Og

GROUP - 15 ELEMENTS : THE NITROGEN FAMILY

2.0 Introduction
The elements of the nitrogen family (group 15 of the periodic table) are nitrogen (N), phoshorus (P), arsenic
(As), antimony (Sb), and bismuth (Bi). These elements are called pnicogens and their compounds as pniconides,
the names derived from the Greek word pnicomigs meaning suffocation.
The sixth member of this group, moscovium (Mc) is a synthetic, extremely radioactive, transactinide
element of very short half-life (only 0.8 seconds).
2.1.1Occurrence
i. Nitrogen. The first member of this group, nitrogen occurs as a diatomic gas, N2. It constitutes about 78% by
volume of the atmosphere. Despite this, nitrogen is not very abundant on the earth’s crust. It is only the thirty-
third most abundant element by mass in the earth’s crust ( 9 ppm).
Nitrogen mainly occurs as nitrates, e.g., NaNO3 (Chile saltpetre) and KNO3 (Indian saltpetre).
It is an essential constituent of proteins, amino acids and nucleic acids which regulate the growth and control
the hereditary characteristics in living beings.

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ii. Phosphorus. It is a very reactive element and hence it does not occur free in nature. It is the eleventh most
abundant ( 1120 ppm) element by mass in the earth’s crust.
Phosphorus occurs in apatite minerals, Ca9(PO4)6.CaX2 (X = F, Cl or OH), e.g., Fluoroapatite, 3Ca3(PO4)2.
CaF2, Chloroapatite, 3Ca3 (PO4)2.CaCl2, and Hydroxyapatite, 3Ca3(PO4)2.Ca(OH)2. These minerals are the
major components of phosphate rocks.
iii. Arsenic, antimony and bismuth. The elements As, Sb and Bi are not very abundant. They mainly occur
as sulphide minerals such as mispickel (arsenopyrites), FeAsS and stibnite, Sb2S3. Realgar, (As4S4), Orpiment,
(As2S3), bismuth glance or bismuthinite (Bi2S3), and bismite (Bi2O3) are present in traces in other ores.
2.1.2Electronic Configuration. The general valence shell electronic configuration of the elements of group 15 is
ns2 np3, where n = 2 to 6.
Table - 01 Atomic and physical properties of Group 15 elements
Property Nitrogen Phosphorus Arsenic Antimony Bismuth
Atomic number 7 15 33 51 83
2 3 2 3 10 2 3 10 2 3 1 10 2 3
Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
–1)
Atomic mass (g mol 14.01 30.97 74.92 121.76 208.98
Ionisation enthalpy ∆i H1 1402 1012 947 834 703
-1
(kJ mol ) ∆i H2 2856 1903 1798 1595 1610
∆i H3 4577 2910 2736 2443 2466
Electronegativity 3 2.1 2 1.9 1.9
Covalent radius (pm) 70 110 121 141 148
3- 3- 3- 3+ 3+
Ionic radius (pm) 171(N ) 212(P ) 222(As ) 76(Sb ) 103(Bi )
Melting point (K) 63 317.1 1089 904 544
(grey a -form at
(white P)
38.6 atm)
Boiling point (K) 77.2 554 888 1860 1837
(sublimation
(white P)
temperature)
–3
Density (g cm at 298 K) 0.879 1.823 5.778 6.697 9.808
at 63K (grey a -form)

2.1.3 Atomic and ionic radii. a) The atomic (covalent) and ionic radii (of a particular oxidation state) of the
elements of group 15 are lower than the corresponding elements of group 14.
Down the group, the covalent radii increase due to addition of a new shell in each succeeding element. The
considerable increase in covalent radius from N to P is not only due to the addition of a new energy shell but
also due to the strong shielding effect of the s-and p-electrons present in the inner shells. The small increase in
covalent radii from As to Bi is due to the poor shielding of the valence electrons by the d-and/or f-electrons in
the inner shells. As a result, the effective nuclear charge increases which reduces the effect of addition of a new
energy shell to some extent. The same is true of ionic radii.
2.1.4Ionization enthalpy. The ionization enthalpies of group 15 elements are much higher than those of the
corresponding elements of group 14. Down the group, the ionization enthalpies decrease regularly.
The decrease in ionization energies down the group is due to gradual increase in atomic size which reduces the
force of attraction on the electrons by the nucleus.
The successive ionization enthalpies of the elements increase in the order:
 i H1   i H 2   i H 3

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2.1.5Electronegativity. Group 15 elements are more electronegative than group 14 elements. Electronegativity of
group 15 elements shows a gradual decrease on moving down the group from N to Bi.
2.2 Physical Properties
i) Metallic character. Elements of group 15 are less metallic than the corresponding elements of group
14. However, down the group, metallic character increases.
Due to increased nuclear charge and higher electronegativity, elements of group 15 are less metallic than the
corresponding elements of group 14. Down the group, electronegativity decreases. As a result, valence electrons
are lost more readily and hence the metallic character increases. Thus, N and P are non-metals, As and Sb are
metalloids, and Bi is a typical metal.
ii) Melting and boiling points.
The melting points increase down the group from N to As due to increase in atomic size. The melting points of
Sb and Bi decrease because of their tendency to form three covalent bonds instead of five due to inert pair
effect. This results in weakening of attraction among atoms, thereby lowering their melting points. Because of
larger size, bismuth has weaker interatomic forces than antimony and thus lower melting point.
The boiling points increase down the group from N to Sb due to increase in atomic size.
iii) Density. The density of group 15 elements increases regularly from top to bottom.
iv) Allotropy. Except N and Bi, all the elements of this group exhibit allotropy. Phosphours exists in three
allotropic forms (white, red and black phosphorus), As and Sb exist in two allotropic forms (yellow and grey).
v) Oxidation States. (a) Negative oxidation states. Elements of group 15 have five electrons in the valence
shell (ns2 np3) and thus require three more electrons to attain noble gas configuration. Nitrogen forms N3–
(nitride) ion in nitrides of highly electropositive metals (Mg3N2, Ca3N2, etc.). Other elements form covalent
compounds even with metals and exhibit a formal oxidation state of -3, e.g., calcium phosphide (Ca3P2),
sodium arsenide (Na3As), zinc stibide (Zn3Sb2) and magnesium bismuthide (Mg3Bi2). However, the tendency
to show -3 oxidation state decreases down the group due to gradual decrease in electronegativity and ionisation
enthalpy.
Besides -3, N and P also exhibit -2 oxidation state in hydrazine (NH2NH2) and diphosphine (P2H4). Nitrogen
also shows an oxidation state of -1 in hydroxylamine (NH2OH) but phosphorus does not.
Positive oxidation states. All the elements of group 15 show positive oxidation states of +3 and +5. However,
on moving down the group, the stability of +5 oxidation state decreases while that of +3 oxidation state
increases due to inert pair effect. Thus, +5 state of Bi is less stable than +5 state of Sb. The only stable
compound of bismuth having+5 state is BiF5.
Due to large amount of energy needed to lose all five valence electrons, M+5 ions are not formed. Thus,
compounds of group 15 elements having +5 oxidation state such as PF5, PCl5, SbF5, and BiF5 are covalent.
However, these elements form both ionic (BiF3, SbF3) and covalent compounds (NCl3, PCl3, AsCl3, SbCl3) in
+3 oxidation state. Thus, covalent character decreases in the order:
N > P > As > Sb > Bi
Nitrogen, because of small size, high electronegativity and strong tendency to form p  p multiple bonds,
shows oxidation states from -3 to +5.

Compound : NH3 NH2NH2 NH2OH N2 N 2O NO N 2O 3 NO2 or N2O4 N 2O 5

Oxidation state : –3 –2 –1 0 +1 +2 +3 +4 +5

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vi) Maximum covalency. Since nitrogen does not possess d-orbitals, it can show a maximum covalency of
4 when it donates its lone pair of electrons (NH4+, R4N+), i.e., nitrogen cannot extend its covalency beyond 4.
vii) Disproportionation. All the oxidation states of N from +1 to +4 exhibit disproportionation in acidic
medium.
3 5 2
3HNO 2 
 HNO3  2NO  H 2O
Nitrous acid Nitric acid Nitricoxide

Phosphorus, in all oxidation states from –3 to +5 shows disproportionation both in acidic and basic media.
3 5 3
4H 3 PO3 

 3H 3PO4  PH3
Phosphorus acid Phosphoric acid Phosphine

However, due to inert pair effect, the stability of +3 oxidation state increases from As to Bi and their tendency
to undergo disproportionation decreases.
2.3 Chemical Properties
2.3.1Reactivity towards hydrogen (Formation of hydrides)
All elements of group 15 form volatile trihydrides of the formula EH3; Ammonia (NH3), Phosphine (PH3),
Arsine (AsH3), Stibine (SbH3), and Bismuthine (BiH3).
Hydrides of group 15 elments have pyramidal structures and their bond angles decrease in the following order:
NH3 (107.8o) > PH3 (93.6o)>AsH3 (91.8o) >SbH3 (91.3o)>BiH3 (90o)
Down the group, the size of the central atom increases and its electronegativity decreases. As a result, the bond
pairs tend to lie away from the central atom and therefore, repulsion between adjacent bond pairs is maximum
in NH3 and minimum in BiH3.
Table - 02 Properties of hydrides of Group 15 elements
Proprty NH3 PH3 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
∆fH° (kJ/mol) -46.1 13.4 66.4 145.1 278
-1
∆dissH° (E-H)/kJ mol 389 322 297 255

a. Properties of hydrides
(i) Melting points. Due to intermolecular H- bonding, NH3 has the highest melting point. However, from PH3
to SbH3, molecular size increases and hence melting points increase regularly due to increase in van der Waals
forces.
PH3 (139.5) < AsH3 (156.7 K) < SbH3 (185 K) < NH3 (195.2 K)
(ii) Boiling points. The boiling points increase regularly as we move from PH3 to BiH3. However, the boiling
point of NH3 is higher than those of PH3 and AsH3.
NH3(238.5 K) > PH3(185.5 K) < AsH3(210.6 K) < SbH3(254.6) < BiH3(290 K)

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The abnormally high b.p. of NH3 is due to intermolecular H-bonding. van der Waals forces of attraction
increases with molecular mass, therefore, boiling points increase regularly from PH3 to BiH3.
PH3 < AsH3 < NH3 < SbH3 < BiH3.
(iii) Thermal stability. As the size of the atom increases, M–H bond strength decreases, therefore, thermal
stability decreases from NH3 to BiH3.
NH3 > PH3 > AsH3 > SbH3> BiH3.
(iv) Reducing character. The reducing character of group 15 hydrides increases in the order:
NH3 < PH3 < AsH3 < SbH3< BiH3
(v) Basic nature. Hydrides of group 15 elements have a lone pair of electrons on the central atom, therefore,
they are Lewis bases. The basic character decreases down the group from NH3 to BiH3. As the size of the
atom increases, the lone pair of electrons occupies a larger volume. The electron density on the central
atom decreases and consequently its tendency to donate a pair of electrons decreases.
2.3.2Reactivity towards oxygen (Formation of oxides)
All these elements form two types of oxides; E2O3 and E2O5.
In general, oxides of non-metals are acidic, those of metalloids are amphoteric and those of metals are basic.
Greater the electronegativity of the element, greater is the acidic character of the oxide. Among the oxides of
the same element, higher the oxidation state of the element, greater is its acidic strength.
i) Acidic strength of oxides of nitrogen increases in the order : N2O < NO < N2O3 < N2O4 < N2O5.
However, N2O and NO are neutral.
ii) In the group, acidic strength of trioxides follows the order : N2O3 > P4O6 > As4O6 > Sb4O6.
As4O6 and Sb4O6 are amphoteric while Bi2O3 is basic.
iii) Within the group, acidic strength of pentoxides follows the order : N2O5 > P4O10 > As4O10 > Sb4O10
2.3.3Reactivity towards Halogens
The elements of group 15 form two types of halides, viz., trihalides and pentahalides. N does not form
pentahalides due to the absence of d-orbitals in its valence shell.
Pentahalides are thermally less stable than trihalides due to the following reasons:
i) Down the group, the stability of +3 oxidation state increases while that of +5 oxidation state decreases due
to inert pair effect.
ii) As the size of the halogen increases from F to I, the strength of the phosphorus-halogen bond decreases due
to steric hindrance.
2.3.4Reactivity towards Metals (Formation of Binary Compounds)
All elements of group 15 form binary compounds with metals in the +3 oxidation state,e.g., Ca3N2 (calcium
nitride), Ca3P2 (calcium phosphide), Na3As2 (sodium arsenide), Zn3Sb2 (zinc stibide) and Mg3Bi2 (magnesium
bismuthide).
2.3.5Anomalous Properties of Nitrogen
Nitrogen differs from the rest of the elements in group 15 due to: a) exceptionally small atomic size, b) high
electronegativity, c) high ionisation enthalpy, and d) absence of d-orbitals in its valence shell.

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i. pπ - pπ multiple bonds. Because of its small size and high electronegativity, nitrogen forms p  p multiple
bonds with itself and with other elements having small size and high electronegativity (e.g., C, O). Thus,
nitrogen exists as a diatomic molecule with a triple bond (one  bond and two  bonds). The N2 molecules are
held together by weak van der Waals forces of attraction. Therefore, N2 is a gas at room temperature.
The other elements of this group do not form p  p multiple bonds because their atomic orbitals are very
large and diffused so that they cannot have effective overlapping.
ii. Catenation.
Among group 15 elements, phosphorus has the maximum tendency for catenation, forming cyclic as well open
chain compounds. Nitrogen has little tendency for catenation since N–N single bond is very weak due to
repulsion between lone pairs (N–N bond having small bond length).
iii. Reactivity. N2 is inert and unreactive in elemental state due to the presence of a triple bond between
nitrogen atoms. The bond length is very small (109 pm) and hence the bond dissociation energy is very large
(941.4 kJ mol–1). Since P–P single bond is much weaker (213 kJ mol–1) than N  N triple bond,
iv. Maximum covalency. Nitrogen has no d-orbitals in its valence shell, therefore, it does not form pentahalides
(NF5, NCl5, etc.).
v. dπ - pπ multiple bonds. Due to absence of d-orbitals nitrogen cannot form dπ - pπ multiple bonds. Thus,
nitrogen does not form compounds of the type, R3N=O. Heavier elements of group 15 readily form
dπ - pπ multiple bonds.
vi. Nature of trihalides. Except NF3, the trihalides of nitrogen (NCl3, NBr3, NI3) are unstable and explosive.
The trihalides of other elements are stable.
Allotrops of Phosphorus

It shows allotropism - white, red, black (a and )

Phosphorus can’t form P P (P2) as p - p bonds can’t be formed due to large size of phosphorus

White Phosphorus

It contains discreat units of P4

In P4 each P atom is sp3 hybridised with one lone pair on each P atom, with tetrahedral shape

with 6 P-P bonds. bond angle 60o. So there is considerable angle strain.

This makes white phosphorus very reactive

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Red Phosphorous
It is a linear chain of P4 units

573K
 

White P Red P

White Red

discreet units of P4 linear chain of P4

more reactive less reactive

volatile less volatile

dissolves in CS2 Insoluble in CS2

on contact with air it reacts with O2 to givedoesn't give chemiluminescence

(chemiluminescence)

Black Phosphorus

573k
  Red P

803k
This method
White P gives a black

473k
high pressure

This method
gives  black
black P

Most thermodynamically
stable allotrope

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GROUP 16 ELEMENTS : THE OXYGEN FAMILY

3.0 Introduction

Group 16 of the periodic table consists of five elements viz., Oxygen (O), Sulphur (S), Selenium (Se), Tellurium
(Te) and Polonium (Po). The sixth element, Livermorium (Lv) is synthetic, extremely radioactive and
has not been observed in nature. These elements are commonly known as the oxygen family. These are also
called chalcogens (meaning ore forming) because many metals occur as oxides and sulphides.

Like elements of groups 14 and 15, elements of this group also exhibit an increase in metallic character down
the group. Thus, oxygen and sulphur are non-metals, selenium and tellurium, are metalloids, and polonium is
metallic. Polonium is radioactive with very short half-life.

3.1.1 Occurrence

Oxygen is the most abundant element.

Oxygen makes up 46.6% by weight of the earth’s crust where it mainly occurs as silicate minerals.

It also makes up 89% by weight of water in oceans.

Sulphur is the sixteenth most abundant element and constitutes 0.03 to 0.1% by mass of the earth’s crust. In
the combined state, it occurs as sulphates such as gypsm, CaSO4.2H2O; epsom salt, MgSO4.7H2O; baryte,
BaSO4 and as sulphides such as galena, PbS; zinc blende, ZnS and copper pyrites, CuFeS2.

Another source of sulphur is H2S present in natural gas and crude oil. Sulphur also exists in the combined state
in living matter and is a constituent of many organic materials.

Selenium and tellurium are less abundant (0.05 ppm and 0.002 ppm respectively in earth’s crust) and occur as
selenides and tellurides in sulphide ores. The principal source of Se and Te is the anode mud deposited during
electrolytic refining of Cu.

Polonium is even less abundant (0.001 ppm). It occurs as decay product of thorium and uranium minerals.

3.1.2 Electronic Configuration. The general outer electronic configuration of group 16 elements is ns2np4.

3.1.3 Atomic and ionic radii. The atomic radii of group 16 elements are smaller than those of the corresponding
elements of group 15.

The atomic radii of group 16 elements increase down the group.

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Table - 07 Atomic and physical properties of Group 16 elements.

Property Oxygen Sulphur Sele nium Tellurium Polonium
Atomic number 8 16 34 52 84
2 4 2 4 10 2 4 10 2 4 1 10 2 4
Electronic configuration [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p [Kr]4d 5s 5p [Xe]4f 5d 6s 6p
Atomic mass (g mol )
-1 16 32.06 78.96 127.6 210
Covalent radius (pm) 66 104 117 137 146
2-
Ionic radius (E )/ (pm) 140 184 198 221 230
Ionisation enthalpy (∆i H1) 1314 1000 941 869 813
-1
(kJ mol ) (∆i H2) 3388 2251 2045 1790 _
Electronegativity 3.5 2.44 2.48 2.01 1.76
Electron gain enthalpy
(egH)/kJ mol
-1 -141 -200 -195 -190 -174
-3
Density/g cm at 293K 1.32 (at m.p) 2.06 (a -S) 4.19 (grey) 6.25 9.4
Melting point/K 55 393 490 725 520
(monoclinic
form, 673K)
Boiling point/K 90 718 958 1260 1235
Oxidation state -2,-1,+1,+2 -2,+2,+4,+6 -2,+2,+4,+6 -2,+2,+4,+6 +2, +4

3.1.4 Ionization enthalpy. The first ionization enthalpies () of group 16 elements are low while their
second ionization enthalpies () are higher than those of the corresponding elements of group 15.
This is due to the relatively symmetrical and more stable electronic configuration of group 15 elements as
compared to those of group 16.
The first and second ionization enthalpies of the elements of group 16 decrease down the group due to
increasing atomic size and increasing shielding effect of the inner electrons.
3.1.5 Electron gain enthalpy. The electron gain enthalpy of oxygen is the least negative. This is because its small
size due to which, electron-electron repulsions in the relatively small 2p-subshell are comparatively high and
hence the incoming electrons are not accepted with the same ease as in case of other members.
3.1.6 Electronegativity. Elements of group 16 have higher electronegativities than the corresponding elements of
group 15. Oxygen is the second most electronegative element (EN = 3.5).
The electronegativity decreases slowly but regularly from selenium to polonium as the atomic size of atom
increases.
3.2 Physical Properties
i. Metallic character. Because of high ionization enthalpy, elements of group 16 are less metallic. However,
down the group, metallic character increases due to decrease in ionisation enthalpy.

Thus, oxygen is the most non-metallic element of group 16. Sulphur is also a typical non-metal and is an
insulator. Se and Te are metalloids and hence semiconductors. Polonium is a radioactive metal with a short half
life (13.8 days).

ii. Melting and boiling points. The melting and boiling points increase regularly as we go down the
group upto tellurium. However, melting and boiling points of polonium are lower than those of tellurium.

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On descending the group, the atomic size increases. As a result, van der Waals forces of attraction also
increase and hence melting and boiling points increase regularly from O to Te. However, due to intervening d-
and f- electrons, inert pair effect is maximum in polonium. As a result, van der Waals forces of attraction are
weaker in Po than in Te, and therefore, m.p. and b.p. of Po are lower than that of Te.

iii. Density. Densities increase regularly as we go down the group due to increase in van der Waals forces of
attraction between atoms.

iv. Elemental state. Oxygen exists as a diatomic gas at room temperature while other elements
(S, Se and Te) exist as octaatomic solids.

v. Catenation. Because of stronger S–S bonds as compared to O–O bonds, sulphur has greater tendency
for catenation than oxygen.

vi. Allotropy. All the elements of this group show allotropy. Oxygen exists in two forms, viz., dioxygen (O2)
and ozone or trioxygen (O3). Sulphur has several allotropic forms.

Since conduction increases with intensity of light, selenium is used for measuring the intensity of light.

3.3 Chemical Properties

1. Oxidation States. As group 16 elements have ns2np4 configuration in their valence shell, they can attain
noble gas configuration either by gaining or by sharing of electrons.-----------------------add matter

3.3.2 Formation of Hydrides (Reactivity towards Hydrogen). All the elements of group 16 form hydrides of the
general formula, H2E , i.e., H2O, H2S, H2Se, H2Te and H2Po.

b. Structure of Hydrides. These hydrides have angular shape involving sp3-hybridization of the central atom.
The bond angles, however, decrease from H2O to H2Te:

H2 O H2S H2Se H2Te

104.5o 92.1o 91o 90o

Oxygen forms another hydride, H2O2.

Table - 08 Properties of hydrides of Group 16 elements.

Prope rty H 2O H 2S H 2Se H2Te

Melting point (K) 273 188 208 222
Boiling point (K) 373 213 232 269
H-E distance (pm) 96 134 146 169
HEH angle (°) 104.5 92.1 91 90
-1
∆fH° (kJ mol ) -286 -20 73 100
-1
∆dissH (H-E)/kJ mol 463 347 276 238
Dissociation constant in 1.8×10
-16
1.3×10
-7
1.3×10
-4
2.3×10
-3

(aqueous solution at 298 K)

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c. Physical properties of hydrides

H2O H2S H2Se H 2Te

373K 213K 232K 269K

Figure - 11 (a) Structure of H2O molecule.

The high boiling point of H2O is due to strong intermolecular H-bonding. Other elements of the group have
much lower electronegativity, therefore, they do not form H-bonds. As the size of the atom increases, van der
Waals forces of attraction increases and therefore, the boiling point increases gradually from H2S to H2Se.
Thus, volatility decreases in the order : H 2S  H 2Se  H 2Te  H 2O.

i) Acidic character. The hydrides of group 16 elements act as weak, diprotic or dibasic acids. Acid strength,
increases down the group, from H2O to H2Te :H2O < H2S < H2Se < H2Te.

The increase in acid strength is due to decrease in bond dissociation energy.

ii) Thermal stability. Thermal stability of hydrides decreases from H2O to H2Te.

As the size of the atom E in H2E increases, the H–E bond becomes weaker and thus breaks easily on heating.

iii) Reducing character. Hydrides of group 16 elements except oxygen (water) are reducing agents. Their
reducing character increases from H2S to H2 Te.

This is due to the decrease in thermal stability. As thermal stability decreases, reducing character increases.
3.3.3 Reactivity towards oxygen (formation of oxides)
All the elements of this group form two types of oxides, i.e., EO2 and EO3.
a. Dioxides. S, Se and Te, when burnt in air form dioxides of the formula EO2.

S8 ( s   8O 2 ( g  
 8SO 2 ( g 

Ozone(O3) and SO2 are gases at room temperature.SeO2, TeO2 and PoO2 are crystalline ionic solids.
i) Reducing-oxidising properties of oxides. Since +6 oxidation state of S is more stable than +4, SO2 acts
as a reducing agent. The stability of +6 state decreases from S to Te, and therefore, the reducing character of
dioxides decreases while their oxidising character increases. Thus, TeO2 acts as an oxidising agent.
b. Trioxides. Elements of 16 group form trioxides of the formula EO3. O3 and SO3 are gases. All trioxides are
acidic in nature.

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3.3.4 Formation of Halides (Reactivity towards Halogens)

The stability of the halides in any particular oxidation state decreases in the order : F > Cl > Br > I. The highest
oxidation state is realised only in the case of fluorides, e.g., SF6.
a. Type of halides
i) Monohalides. Most monohalides are dimeric in nature, e.g., S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These
dimeric halides undergo disproportionation.
1 4 0
2Se2 Cl2 
 SeCl4  3Se
ii) Dihalides. All group 16 elements except selenium form dihalides. The dihalides have sp3-hybridisation.
iii) Tetrahalides. Among tetrahalides, tetrafluorides are the most stable. SF4 is a gas, SeF4 is a liquid and
TeF4 is a solid. These fluorides have sp3d hybridisation and thus, have trigonal bipyramidal structures in which
one of the equatorial positions is occupied by a lone pair of electrons. Thus, these molecule have see-saw
geometry.
iv) Hexahalides. Only fluorine forms hexa halide. All hexafluorides are gases. .
SeF6 is thermally stable and chemically inert.
3.3.5 Anomalous Behaviour of Oxygen
Oxygen, differs considerably from the rest of the Group 16 elements due to small size, higher electronegativity
and non-availability of d-orbitals.
i) Physical state. At room temperature, oxygen is a gas while all other members of group 16 are solids.
ii) Atomicity. Oxygen molecule is diatomic (O2) while sulphur and selenium have octaatomic molecules
(S8 and Se8) with puckered ring structures.
iii) Non-metallic/metallic character. Being highly electronegative (3.5), oxygen is a typical non-metal. Sulphur
(EN = 2.5) is also non-metallic while other members exhibit metallic character.
iv) Oxidation states. Being the most electronegative element of the group, oxygen usually shows an oxidation
state of –2 in most of its compounds (except in peroxides, O2F2 and OF2).
Due to the absence of d-orbitals, oxygen cannot expand its octet and hence cannot show positive oxidation
states.
v) Hydrides. Due to high electronegativity, oxygen forms H- bonds in H2O while hydrides of other elements
(H2S, H2Se, etc.) do not. Thus, H2O is a liquid while hydrides of other elements are gases at room temperature.
Allotropes of Sulphur
Main allotropes : a rhombic sulphur

 monoclinic sulphur

 plastic sulphur

 colloidal sulphur
In addition to this sulphur can exists as long chains known as catena - Sn or rings known as Sn
because it shows higher degree of catination.

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a rhombic and  monoclinic  crystalline

 plastic and  colloidal  amorphous

a and  are the crystalline allotropes having formula S8 with a crown shape structure.

S S S
S S

S a and  differ only in arrangement of S rings.

S S

369K
a   (369K  transition temperature)

a is the thermodynamically stable allotrope.

S
S S
S6  S S chair like structure.

GROUP 17 ELEMENTS : THE HALOGEN FAMILY

4.0 Introduction
Group 17 of the periodic table consists of fluorine, chlorine, bromine, iodine, astatine and tennessine. These
are collectively named as halogens. The name halogen (Greek, halo = sea salts, genes = producing), meaning
sea salt formers, was given to them by Schweigger in 1811 because chlorides, bromides and iodides occur in
sea water. Among the halogens, fluorine is the most reactive and hence is also called super halogen. Astatine,
is radioactive and hence occurs only in traces. Tennessine (Ts) is synthetic and highly radioactive with a
half-life of about 80 milliseconds.
4.1.1 Occurrence
a) Fluorine The chief minerals are: i) Fluorspar, CaF2, ii) Cryolite, Na3AlF6 and iii) Fluoroapatite,
CaF2.3Ca3(PO4)2.
b) Chlorine is the most abundant halogen . The chief sources of chlorine are sea water (2.5% by mass), salt
wells and salt beds. In salt beds, it mainly occurs as : i) Sodium chloride (Rock salt), NaCl, ii) Carnallite KCl.
MgCl2.6H2O, and iii) Calcium chloride, CaCl2.
c) Bromine mainly occurs in sea water and salt lakes as bromides of alkali and alkaline earth metals, i.e.,
NaBr, KBr and MgBr2.
d) Iodine. It mainly occurs in (i) sea weeds (0.5% by mass) as alkali metal iodides. ii) Caliche (crude chile
saltpetre) which is mainly sodium nitrate containing 0.2% by mass of iodine as sodium iodate (NaIO3).
4.1.2 Electronic Configuration. The elements of group 17 have seven electrons in the valence shell. Their general
outer electronic configuration (ns2np5) is one electron short of the nearest inert gas.

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4.1.3 Atomic and ionic radii.

The atomic and ionic radii increase from fluorine to astatine due to increase in the number of shells.
4.1.4 Ionization enthalpy. Halogens have very little tendency to lose electrons. Therefore, ionization enthalpies of
halogens are very high (next only to the inert gas in each period).
However, on moving down the group, F to I, ionization enthalpies decrease with increase in size.
4.1.5 Electron gain enthalpy.
In the group, the electron gain enthalpies become less negative as the size of the halogen increases.
Due to small size, strong electron-electron respulsions are present in the relatively compact 2p-orbitals of
fluorine. Therefore, electron gain enthalpy of fluorine is less negative than chlorine. The order of
negative values of electron gain enthalpies are : Cl > F> Br > I
4.1.6 Electronegativity. Halogens are highly electronegative. Due to small size and high nuclear charge, halogen
has the highest electronegativity in its period. Fluorine has the highest electronegativity value of 4.0. Down the
group, electronegativity decreases due to increase in the size of the atom.
Table - 12 Atomic and physical properties of Group 17 elements.

Property/Element Fluorine Chlorine Bromine Iodine Astatine

Atomic number 9 17 35 53 85
Electronic configuration 2
[He]2s 2p
5 2
[Ne]3s 3p
5 10
[Ar]3d 4s 4p
2 5
[Kr]4d
10
[Xe]4f 5d
1 10

2 5 2 5
5s 5p 6s 6p
-1
Atomic mass/g mol 19.00 35.45 79.90 126.90 210
Covalent radius/pm 64 99 114 133 150
-
Ionic radius (X )/pm 133 184 196 220 202
-1
Ionisation enthalpy/kJ mol 1680 1256 1142 1008 899
Electronegativity 4.0 3.2 3.0 2.7 2.2
Electron gain enthalpy
-1
(kJ mol ) -333 -349 -325 -296 -
- -1
 Hyd.H(X )/kJ mol 515 381 347 305 -
Oxidation states -1 -1,+1,+3,+5,+7 -1,+1,+3,+5,+7 -1,+1,+3,+5,+7
F2 Cl2 Br2 I2 At
Melting point/K 54.4 172 265.8 386.6 575
Boiling point/K 84.9 239 332.5 458.2 610
-3
Density/g cm (liquid) 1.51 (85K) 1.66 (203K) 3.19 (293K) 4.94 (273K) 6.35
Distance X-X/pm 143 199 228 266 -
-1
X2(g)  2X (g)/kg mol 158.8 242.6 192.8 151.1 -
o
E /V 2.87 1.36 1.09 0.54 -
4.2 Physical Properties
i. Atomicity. All halogens exist as diatomic molecules.
ii. Melting and boiling points.
Due to increase in van der Waals forces of attraction, the melting and boiling points increases down the group.

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iii. Non-metallic character. Due to high ionization enthalpies and electronegativities, halogens are non-metallic
in nature. Non-metallic character decreases from fluorine to iodine.
iv. Enthalpy of dissociation. The bond dissociation enthalpy follows the sequence : Cl2  Br2  F2  I 2 .
The F–F bond dissociation enthalpy is smaller than that of Cl–Cl and Br–Br. This is because F atom is very
small and hence electron-electron repulsion between the lone pairs is very large.
v. Colour. Halogens are coloured due to absorbtion of light in the visible region for excitation of electrons to
higher energy levels. The colour of halogens is the colour of the trasmitted light (complementary colour).
Halogen Fluorine Chlorine Bromine Iodine
Colour Pale yellow Greenish yellow Reddish brown Deep violet
vi. Solubility. F2 and Cl2 react with water. Br2 and I2 are sparingly soluble in water, but soluble in organic
solvents such as CHCl3, CCl4, CS2, and hydrocarbons such as hexane, benzene, etc., to give coloured solutions.
4.3 Chemical Properties
4.3.1 Oxidation States. All halogens exhibit -1 oxidation state. Chlorine, bromine and iodine exhibit +1, +3, +5,
and +7 oxidation states.
4.3.2 Trends in Chemical Reactivity. Halogens have a very strong tendency to gain one electron. They are highly
reactive due to (i) low bond dissociation energy and (ii) high negative electron gain enthalpy. In the group,
reactivity decreases in the order: F2>Cl2>Br2>I2.
4.3.3 Oxidising Power. Halogens have strong tendency to accept an electron, therefore, they act as strong oxidising
agents. Oxidising power decreases from F2 to I2. F2 is the strongest oxidising agent amongst halogens. It
oxidises all other halide ions to the corresponding halogen.

 2F  X 2 ( X   C  , Br  , I  
F2  2X  

Similarly, Cl2 will oxidise Br– and I– ions while Br2 will oxidise only I– ions from their solutions.

 2Cl  X 2 ( X   Br  , I   ; Br2  2I  
Cl2  2X    2Br   I 2

The relative oxidising power of halogens can be illustrated by their reaction with water. F2 oxidises H2O to
O2 and O3, whereas Cl2 and Br2 react with water to form the corresponding hydrohalic and hypohalous acids.

2F2 ( g   2H 2 O ( l  
 4H  ( aq   4F ( aq   O 2 ( g 

3F2 ( g   3H 2O ( l  
 6H  ( aq   6F ( aq   O 3 ( g 

Cl 2 ( g   H 2 O ( l  
 HCl ( aq   HOCl ( aq 
Hypochlorous acid

Br2 ( g   H 2 O ( l  
 HBr ( aq   HOBr ( aq 
Hypobromous acid

The reaction of I2 with H2O is non-spontaneous. In fact, I– ions can be oxidised by O2 in acidic medium which
is just the reverse of the reaction observed with F2.

4I ( aq   O 2 ( g   4H  ( aq  
 2I 2 ( s   2H 2O ( l 

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4.3.4 Reactivity towards hydrogen

All halogens combine with hydrogen to form hydrogen halides, but reactivity decreases from fluorine to iodine.
b) Properties of Hydrogen Halides
i. Physical state. Whereas HBr, HCl and HI are gases, HF is a low boiling liquid (b.p. 293 K). This is due to
intermolecular hydrogen bonding in HF. Thus, HF exists as associated molecule (HF)n.
ii. Melting points and boiling points. HF has the highest boiling point (293 K) due to extensive intermolecular
hydrogen bonding. As the size of the halogen increases from HCl to HI, boiling points show a regular increase
due to increase in van der Waals’ forces of attraction.
Like boiling point, melting point of HF also is higher than that of HCl due to intermolecular hydrogen bonding.
The melting points of the other halogen acids show a gradual increase from HCl to HI as the size of the halogen
atom increases.
Table -13 Physical properties of hydrogen halides
Property HF HCl HBr HI
Melting point (K) 190 159 185 222
Boiling point (K) 293 189 206 238
Bond length, (H-X)/pm 91.7 127.4 141.4 160.9
o -1
diss H /kJ mol 574 432 363 295
Dipole moment m/D 1.86 1.11 0.79 0.38
Acid dissociation constant/pKa 3.2 -7.0 -9.5 -10.0
iii) Bond length. The bond length increases in the same order as the size of the halogen atom :
HF < HCl < HBr < HI.
iv) Bond strength. Bond strengths or bond dissociation energies are inversely proportional to the bond
lengths. Bond strength increases in the order : HI < HBr < HCl < HF.
v) Thermal stability. Thermal stability is directly proportional to the bond dissociation energy. Thermal
stability increases in the order : HI < HBr < HCl < HF.
vi) Acid strength. The strength of an acid depends on its degree of ionization which, in turn, depends on the
bond strength. pKa values decrease in the order: HF (3.2) > HCl (–7.0) > HBr (–9.5) > HI (–10.0). Acid
strength increases in the order : HF < HCl < HBr < HI.
vii) Reducing power. Reducing power depends on the ease with which HX decomposes to H2 and X2 (bond
dissociation energy). Reducing power increases in the order : HF < HCl < HBr < HI.
4.3.5 Reactivity towards Oxygen
Halogens form binary compounds with oxygen, but most of them are unstable.
1. Oxides of fluorine. Fluorine forms OF2 (oxygen difluoride) and O2F2 (dioxygen difluoride) with oxygen.
OF2is thermally stable at 298 K while O2F2 is highly unstable and decomposes even at 178K. They are called
oxygen fluorides rather than oxides of fluorine since the electronegativity of F is higher than that of O.
2. Oxides of other halogens. The stability of oxides of halogens decreases in the order : I > Cl > Br. The
higher oxides of halogens are more stable than the lower ones.
Chlorine oxides (Cl2O, ClO2, Cl2O6 and Cl2O7 ) are highly reactive oxidising agents and tend to explode. ClO2
is used as a bleaching agent for paper pulp and textiles and in water treatment.

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The bromine oxides, Br2O, BrO2, BrO3 are the least stable halogen oxides (middle row anomally) and exist
only at low temperatures. They are very powerful oxidising agents. Their structures are similar to those of
chlorine oxides having similar molecular formulae.
Iodine forms three oxides, I2O4, I2O5 and I4O9 of which I2O5 is the most stable. It is the only true oxide of
idoine while others are regarded as iodates of tripositive iodine.
I2O5 is a very good oxidising agent and is used in the estimation of carbon monoxide.
6. Reactivity towards Metals. Halogens combine directly with most metals to form the corresponding halides,
e.g., Br2 reacts with magnesium to form magnesium bromide.
Mg ( s   Br2 ( l  
 MgBr2 ( s 
Due to decrease in electronegativity of the halogens, ionic character of the M–X bond, decreases in the
order : M–F > M–Cl > M–Br > M–I
However, when the metal exhibits more than one oxidation state, the halide in the higher oxidation state will be
more covalent, e.g., SnCl4, PbCl4, SbCl5, UF6 are more covalent than SnCl2, PbCl2, SbCl3 and UF4.
4.3.6 Reactivity of Halogens towards other Halogens. Halogens react among themselves to form compounds
called interhalogens of the type XX, XX3 , XX5 and XX7 where X is the halogen with larger size.
4.3.7Anomalous Behaviour of Fluorine
The reasons for the anomalous behaviour of fluorine are : i) small size, ii) high electronegativity, iii) low bond
dissociation enthalpy of F2 molecule, and iv) absence of d-orbitals in the valence shell.
i. Reactivity. Fluorine is the most reactive halogen. This is due to much higher electrode potential of fluorine.
ii. Oxidation state. Being the most electronegative element, it always shows oxidation state of -1, except +1
in HOF. It does not show higher oxidation states due to the absence of d-orbitals in its valence shell. Other
members, however, show oxidation states –1, +1, +3, +5 and +7.
iii. Hydrogen bonding. Due to small atomic size and high electronegativity, certain compounds of fluorine
shows hydrogen bonding.
i) HF is a liquid with a boiling point of 293 K while other hydrogen halides are gases with low boiling points,
under ordinary conditions.
GROUP 18 ELEMENTS : THE NOBLE GASES
5.0 Introduction
The group 18 of the perodic table consists of six monoatomic gaseous elements : helium (He), neon (Ne),
argon (Ar), krypton (Kr), xenon (Xe) and radon (Rn). All these gases except radon are present in the atmosphere
in very small quantities and hence they are known as rare gases. These are also referred to as aerogens
(present in air). These gases do not exhibit chemical reactivity at ordinary temperatures and hence they were
called inert gases. However, a number of compounds of these gases, particularly those of xenon and krypton
have been prepared. This shows that these gases are not completely inert. Therefore, these are called noble
gases in analogy with noble metals like gold and platinum which are also reluctant to react rather than complete
inertness. Oganneson (Og), the seventh member of this group is a highly radioactive and unstable
synthetic chemical element of very short half-life.
5.1.1 Occurrence of Noble Gases
Noble gases occur in elemental state in the atmosphere. Their total percentage in dry air is about 1% by
volume of which argon is the major component. Helium is the second most abundant element in the universe

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(23% as compared to 76% hydrogen) although its terrestial abundance is very low. Helium is also present in
natural gas (2–7%). Helium and sometimes neon are present in small quantities in radioactive minerals such as
clevite, monazite, pitchblende, etc.
Radon is the decay product of radium. It has a halt-life of only 3.82 days.
226 222
88  86 Rn  42 He
Ra 
5.1.3 Electronic Configuration
The general outer electronic configuration of noble gases is ns2np6 except helium, which has 1s2 configuration.
5.1.4 Monoatomic nature. All the noble gases are monoatomic, colourless and odourless. Their monoatomic
nature as well as reluctance to react with other elements is due to stable fully filled outer electronic configuration.
5.1.5 Atomic radii. The atomic radii of noble gases are the largest in their respective periods. This is because they
have only van der Waals radii while others have covalent radii (van der Waals radii are larger than covalent
radii). Down the group, atomic radius increases due to increase in the number of shells.
Table - 17 Atomic and physical properties of Group 18 elements.

5.1.6 Ionisation enthalpy. Due to stable electronic configurations, ionization enthalpies of noble gases are the
highest in their respective periods. Down the group, ionization enthalpies decrease due to increase in atomic
radii and shielding effect of the inner electrons.
5.1.7 Electron gain enthalpy. Noble gases have completely filled subshells, therefore, the additional electron has
to be placed in the next higher shell. Thus, energy has to be supplied to add an electron and hence, electron
gain enthalpy of noble gases is positive. Down the group, size of the atom increases and hence electron gain
enthalpies become less positive, e.g., electron gain enthalpy of Ar is less positive (+96) than that of Ne (+116).
5.2 Physical Properties
i. Melting and boiling points. The melting and boiling points of noble gases are very low. Helium has the
lowest boiling point (4.2 K) of all the known substances. This is because the atoms of these elements are held
together by weak van der Waals forces (dispersion forces) both in the liquid as well as soild states.
ii. Ease of liquefaction. Since the atoms of noble gases are held together by weak van der Waals forces,
these gases cannot be easily liquefied. However, as the atomic size increases, the magnitude of van der Waals

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forces increases and hence ease of liquefaction increases He to Xe.

iii. Diffusion. Helium has an unusual property of diffusing through materials such as glass, rubber and plastics.
5.3 Chemical Properties
The noble gases are chemically inert due to the following reasons.
i) Noble gases have completely filled, ns2 np6, electronic configuration except He(1s2)
ii) They have high ionization enthalpies.
iii) Their electron gain enthalpies are positive.
Thus, noble gases have no tendency to lose or gain electrons and hence do not enter into chemical combination.
However, in 1962, Neil Bartlett observed that platinum hexafluoride (PtF6), a powerful oxidising agent, reacts
with Xe to give a red solid with formula Xe [Pt F6].
278K
Xe  PtF6   Xe  [PtF6 ]
After this discovery, a large number of xenon compounds, mainly highly electronegative elements like fluorine
and oxygen, have been prepared.
Table - 18 Compounds of xenon.
+2 oxidation state +4 oxidation s tate +6 oxidation state +8 oxidation state
XeF2 XeF4 XeF6 XeO4
(Xenon difluoride) (Xenon tetrafluoride) (Xenon hexafluoride) (Xenon tetroxide)
XeOF2 XeOF4 XeO3F2
(Xenon oxydifluoride) (Xenon oxytetrafluoride) (Xenon trioxydifluoride)
XeO2F2
(Xenon dioxydifluoride)
XeO3 (Xenon trioxide)
Compounds of krypton are fewer; only krypton difluoride (KrF2) has been studied in detail. The compounds
of radon (e.g., RnF2) has not been isolated but has only been identified by radiotracer technique. No true
compounds of Ar, Ne or He are known.

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