General electronic configuration of p block - ns2np1-6.

Reasons of anomalous behaviour of 2nd period elements of p block

i.Small size ii.High electronegativity iii. Absence of d orbitals
Group 15
Includes nitrogen, phosphorus, arsenic, antimony and bismuth.
1. Occurrence
a. Minerals of Nitrogen
i. NaNO3 (Chile saltpetre) ii.KNO3 (Indian saltpetre)
b. Minerals of Phosphophorus
i. Fluorapatite 3Ca3(PO4)2.CaF2
ii. Chlorapatite 3Ca3(PO4)2.CaCl2
iii. Hydroxyapatite 3Ca3(PO4)2.Ca(OH)2
2. Electronic configuration – ns2np3. s orbital in these elements is completely filled and p
orbitals are exactly half-filled, making their electronic configuration extra stable.
3. Atomic and ionic radii – increase down the group due to addition of new shells.
4. Ionization enthalpy is higher than group 16 and group 14 due to extra stable electronic
configuration(exactly half filled p subshell).
5. Anomalous properties of nitrogen
a. Reasons
i. Small size
ii. High electronegativity
iii. Non-availability of d orbitals
b. Anomalous properties
i. Nitrogen has unique ability to form pπ -pπ multiple bonds due to small size and high
electronegativity. 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
between the two atoms. Consequently, its bond enthalpy 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.
ii. Catenation tendency is weaker in nitrogen than phosphorus. Reason – single 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.
iii. Nitrogen cannot extend its covalence beyond 4 (NH4+)
Reason – Absence of d orbitals.
Result – Nitrogen does not form pentachloride, NCl5.
iv. Nitrogen exists as gas while other elements of group 15 are solids
Reason – Nitrogen forms pπ –pπ multiple bonds. Thus its valence shell gets satisfied
in diatomic state. Other group 15 elements do not form pπ –pπ multiple bonds and
 hence exist as tetra-atomic molecules. Boiling point increases with atomicity (no. of
atoms in a molecule).

6. Chemical properties
a. Common oxidation states of group 15 are -3,+3 and +5.
b. Tendency to exhibit –3 oxidation state decreases down the group due to increase in size
and metallic character.
c. Inert pair effect – Reluctance of outermost s-electrons to take part in bond formation.
Inert pair effect explains increasing stability of oxidation states that are 2 less than the
group valency for the heavier elements of groups 13, 14, 15 and 16.
d. Stability of +5 oxidation state decreases and that of +3 state increases (due to inert pair
effect) down the group. Therefore PCl5 exists but BiCl5 does not.
e. Disproportionation – In nitrogen, all oxidation states from +1 to +4 disproportionate in acid
solution. For example,
3HNO2 → HNO3 + H2O + 2NO
Similarly, in case of phosphorus, intermediate oxidation states disproportionate into +5 and
–3 both in alkali and acid.
f. Reaction with hydrogen – All elements of Group 15 form hydrides of type EH 3 where E = N,
P, As, Sb or Bi.
Properties of hydrides
i. Structure – sp3 hybridization with one lone pair, pyramidal structure.
ii. Bond angle decreases down the group.
Reason – Electronegativity decreases, hence bond pair shifts away from central
atom, consequently shifts away from each other, repulsion decreases.
iii. Boiling point increases from PH3 to BiH3 due to decrease in van der Waals forces. But
boiling point of NH3 is higher that PH3 due to Hydrogen bonding.
iv. Solubility – Only ammonia is soluble in water since it makes H-bonds with water.
v. Thermal stability – decreases down the group due to increase in bond length.
vi. Reducing character – Increases down the group.
Reason – Thermal stability decreases down the group. This increases tendency to
liberate hydrogen which increases reducing character(addition of hydrogen is
reduction).
vii. Basic nature – decreases down the group due to increase in size of central atom
which decreases electron density on central atom.
g. Reactivity towards oxygen: All group 15 elements form two types of oxides: E 2O3 and E2O5.
i. Oxide in the higher oxidation state of the element is more acidic than that of lower
oxidation state.
ii. Their acidic character decreases down the group. The oxides of the type E 2O3 of
nitrogen and phosphorus are purely acidic, that of arsenic and antimony amphoteric
and those of bismuth is predominantly basic.
 h. Reactivity towards halogens: These elements react to form two series of halides: EX 3 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 (remember Fajans rules)

7. Dinitrogen
a. Preparation –
i. 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).
ii. In laboratory, by treating an aqueous solution of ammonium chloride with sodium
nitrite.
NH4CI(aq) + NaNO2(aq) → N2(g) + 2H2O(l) + NaCl (aq)
iii. Thermal decomposition of ammonium dichromate

iv. Very pure nitrogen can be obtained by the thermal decomposition

of sodium azide or barium azide.
2NaN3 → 2Na + 3N2
Ba(N3)2 → Ba + 3N2
b. Properties
i. Dinitrogen is inert at room temperature because of high bond enthalpy of N≡N bond.
ii. At higher temperatures, nitrogen combines with metals to form ionic nitrides and
with non-metals to form covalent nitrides.
e.g.

iii. At high temperatures, dinitrogen combines with dioxygen to form nitric oxide, NO.

8. Ammonia
a. Preparation – ammonia is manufactured by Haber’s process.

Optimum conditions for manufacture of ammonia

i. High pressure around 200 atm (since forward reaction results in decrease in
number of moles, Le Chatelier’s principle)
ii. Temperature around 700 K.
iii. Use of catalyst such as iron oxide.
b. Properties
i. In solid and liquid states, ammonia is associated through hydrogen bonds. This is the
reason for its higher melting and boiling points than expected on basis of its
molecular mass.
ii. Shape of ammonia molecule is trigonal pyramidal with three bond pairs and one lone
pair.
iii. Ammonia gas is highly soluble in water due to hydrogen bonding.
iv. Aqueous solution of ammonia is weakly basic due to formation of OH- ions.

v. As a weak base, it precipitates hydroxides of many metals from their salt solutions.
E.g.

vi. Presence of a lone pair of electrons on nitrogen atom of ammonia makes it a Lewis
base. It donates electron pair and forms linkage with metal ions and formation of
such complex compounds finds applications in detection of metal ions such as Cu 2+,
Ag+
9. Oxides of Nitrogen

Resonance Structures of oxides of nitrogen

10. Nitric acid
a. Preparation – Nitric acid is prepared by Ostwald’s process. This method is based upon
catalytic oxidation of NH3 by atmospheric oxygen.

b. Properties –
i. In aqueous solution, nitric acid behaves as a strong acid giving hydronium and nitrate
ions.
HNO3(aq) + H2O(l) → H3O+(aq) + NO3- (aq)
ii. Concentrated nitric acid is a strong oxidizing agent and attacks most metals except
noble metals such as gold and platinum. The products of oxidation depend upon
concentration of the acid.
 3Cu + 8 HNO3(dilute) → 3Cu(NO3)2 + 2NO + 4H2O
Cu + 4HNO3(conc.) → Cu(NO3)2 + 2NO2 + 2H2O
Zinc reacts with dilute nitric acid to give N2O and with concentrated
acid to give NO2.
4Zn + 10HNO3(dilute) → 4 Zn (NO3)2 + 5H2O + N2O
Zn + 4HNO3(conc.) → Zn (NO3)2 + 2H2O + 2NO2
iii. Some metals (e.g., Cr, Al) do not dissolve in concentrated nitric acid because of
formation of a passive film of oxide on the surface.
iv. Concentrated nitric acid also oxidises non–metals and their compounds. Iodine is
oxidised to iodic acid, carbon to carbon dioxide, sulphur to H 2SO4, and phosphorus to
phosphoric acid.
I2 + 10HNO3 → 2HIO3+ 10 NO2 + 4H2O
C + 4HNO3 → CO2 + 2H2O + 4NO2
S8 + 48HNO3(conc.) → 8H2SO4 + 48NO2 + 16H2O
P4 + 20HNO3(conc.) → 4H3PO4 + 20 NO2 + 4H2O
v. Brown Ring Test: Brown ring test for nitrates depends on ability of Fe 2+ to reduce
nitrates to nitric oxide, which reacts with Fe2+ to form a brown coloured complex.
Brown ring test is carried out by adding dilute ferrous sulphate solution to an aqueous
solution containing nitrate ion, and then adding concentrated sulphuric acid along the
sides of the test tube. A brown ring at the interface between the solution and
sulphuric acid layers indicates presence of nitrate ion in solution.
NO3-+ 3Fe2+ + 4H+ → NO + 3Fe+ + 2H2O

[Fe (H2O)6 ]2+ + NO → [Fe (H2O)5 (NO)]2+ + H2O

(brown)

11. Phosphorus – Is found in three allotropic forms, white, red and black.
a. White phosphorus
i. Reacts with NaOH to give phosphine (PH3)

sodium hypophosphite
ii. White phosphorus is less stable and therefore, more reactive
because of angular strain in the P4 molecule where the angles are only 60° (sp3
hybridization, expected bond angle 109.5°) . It readily
catches fire in air to give dense white fumes of P4O10.

iii. It consists of discrete tetrahedral P4 molecules with bond angle of 60°

 b. Red phosphorus
i. Red phosphorus is much less reactive than white phosphorus. It does not glow in the
dark.
ii. Red phosphorus has polymeric structure, consisting of chains of P 4 tetrahedra linked
together.

Red phosphorus

c. Phosphine
i. Phosphine is prepared by the reaction of calcium phosphide with water or dilute HCl.

ii. When pure, it is non inflammable but becomes inflammable due to presence of P 2H4 or
P4 vapours.
iii. Purification – To purify it from the impurities, it is absorbed in HI to form phosphonium
iodide (PH4I) which on treating with KOH gives off phosphine.

iv. On reacting with copper sulphate or mercuric chloride solution, phosphine forms
corresponding phosphides.

v. Phosphine is weakly basic and like ammonia, gives phosphonium compounds with
acids e.g.,
Phosphorus forms two types of halides, PX3 (X = F, Cl, Br, I) and
PX5 (X = F, Cl, Br).
d. Phosphorus Trichloride
i. Preparation
It is obtained by passing dry chlorine over heated white phosphorus.

ii. Properties
- Hydrolysis – PCl3 hydrolyses in presence of moisture to form phosphorus acid.

- It reacts with organic compounds containing –OH group such as CH3COOH, C2H5OH.

- Shape of molecule – Pyramidal shape with sp3 hybridisation of phosphorus.

Phosphorus trichloride

e. Phosphorus pentachloride
i. Preparation – Reaction of white phosphorus with excess chlorine.

ii. Properties
- Hydrolysis

- Action of heat – Decomposes to form PCl3 and Cl2

- Reacts with organic compounds containing –OH group converting them to chloro
derivatives.
- Structure – trigonal bipyramidal. Three equatorial P–Cl bonds are equivalent, while two
axial bonds are longer than equatorial bonds. Reason - axial bond pairs suffer more
repulsion as compared to equatorial bond pairs.

f. Oxoacids (acids containing oxygen) of phosphorus

Structures of some important oxoacids of phosphorus
 i. Properties
- Disproportionation – Oxoacids of phosphorus in +3 oxidation state disproportionate
to higher and lower oxidation states. For example, orthophophorous acid (or
phosphorous acid) on heating disproportionates to give orthophosphoric acid (or
phosphoric acid) and phosphine.

- Acids which contain P–H bond have strong reducing properties. E.g.
hypophosphorous acid is a good reducing agent as it contains two P–H bonds and
reduces AgNO3 to metallic silver.

- P–H bonds are not ionisable to give H+ and do not play any role in basicity. Only those
H atoms which are attached with oxygen in P–OH form are ionisable and cause the
basicity. Thus, H3PO3 and H3PO4 are dibasic and tribasic, respectively as the structure
of H3PO3 has two P–OH bonds and H3PO4 three.

Group 16
1. Occurrence - Minerals of sulphur gypsum CaSO4.2H2O, epsom salt MgSO4.7H4O, baryte
BaSO4 and sulphides such as galena PbS, zinc blende ZnS, copper pyrites CuFeS 2.
2. Electronic configuration – ns3np4
3. Ionisation enthalpy decreases down the group. It is due to increase in size. However, the
elements of this group have lower ionisation enthalpy values compared to those of
Group15 in the corresponding periods. This is due to the fact that Group 15 elements have
extra stable half filled p orbitals electronic configurations.
4. Electron Gain Enthalpy - Because of small size of oxygen atom, it has less negative electron
gain enthalpy than sulphur. However, from sulphur onwards the value again becomes less
negative upto polonium.
5. Electronegativity – Oxygen is the second most electronegative element after fluorine. Down
the group, electronegativity decreases, therefore metallic character increases.
 6. Physical properties – oxygen exists as diatomic molecule (O2) whereas sulphur exists as
polyatomic molecule (S8). Reason – Oxygen forms pπ-pπ multiple bonds but sulphur does
not (due to small size of oxygen). Consequence – Oxygen has much lower boiling point than
sulphur(boiling point increases with atomicity).
7. Chemical properties
a. Oxidation state – Possible oxidation states of group 16 are -2,+2,+4,+6.
i. Stabilty of -2 oxidation state decreases down the group due to decrease in
electronegativity.
ii. Since electronegativity of oxygen is very high, it shows only negative oxidation state as –2
except in case of OF2 where its oxidation state is + 2.
iii. Stability of + 6 oxidation state decreases down the group and stability of + 4
oxidation state increase (inert pair effect).
iv. Bonding in +4 and +6 oxidation states are mostly covalent (Fajan’s rules).
b. Anomalous behavior of oxygen – like other members of p-block present in second period is
due to its small size, high electronegativity and absence of d-orbitals.
i. Oxygen is diatomic (O2) while other members are octa-atomic (S8,Se8).
Reason – Small size allows formation of pπ-pπ bonds. Therefore, valency of oxygen gets
satisfied after bonding with one atom. This is also the reason for oxygen being a gas while
other group 16 elements are solids (boiling point increases with atomicity.
ii. Hydrogen bonding – is present in H2O but not in other group 16 hydrides. Therefore water is
liquid but other hydrides are gases.
Reason – High electronegativity.
iii. Oxygen does not show oxidation state +4 or +6 while other group 16 elements do.
Reason – Absence of d-orbitals.
c. Group 16 hydrides – H2O, H2S, H2Se, H2Te
i. Structure – Angular shape with sp3hybridisation of central atom and 2 lone pairs.
ii. Bond angle decreases from H2O to H2Te due to decrease in electronegativity of central atom
which results in bonding electron pair shifting away from central atom.
iii. Boiling point decreases from H2O to H2S (H bonding in H2O), then increases from H2S to H2Te
(increase in van der Waals forces due to increase in size).
iv. Acidic strength - Increases from H2O to H2Te due to decrease in bond strength down the
group. As atomic size increases down the group, distance between central atom and
hydrogen increases and breaking H-X bond (X=O,S, Se, Te) becomes easier.
v. Thermal stability - decreases down the group. Reason – same as iv above.
vi. Reducing character - increases down the group due to increase in tendency to give hydrogen
(addition of hydrogen is reduction). Reason – same as iv above.

d. Group 16 oxides - All these elements form oxides of type EO 2 and EO3 where E = S, Se, Te or
Po. All these oxides are acidic. Acidic character of oxides decreases down the group.
e. Group 16 halides
i. Elements of Group 16 form halides of the type, EX2, EX4 and EX6 where E is an element of the
group and X is a halogen.
ii. Stability of halides decreases in the order F- > Cl- > Br- > I-
iii. Hexafluorides have octahedral structure.
iv. Sulphur hexafluoride, SF6 is exceptionally stable for steric reasons since the six fluorine atoms
shield the central sulfur atom from attack.
v. Tetrafluorides (SF4,SeF4,TeF4) have sp3d hybridisation and thus, have trigonal
bipyramidal structures in which one of the equatorial positions is occupied by a lone pair of
electrons. This geometry is called see-saw geometry.
vi. Dihalides have sp3 hybridization with 2 lone pairs (bent shape).
vii. Monohalides are dimeric in nature. Examples are S2F2, S2Cl2, Se2Cl2 and Se2Br2. These dimeric
halides undergo disproportionation as given below:
2Se2Cl2 → SeCl4 + 3Se
8. Dioxygen
a. Preparation
i. By heating oxygen containing salts such as chlorates, nitrates and permanganates.

ii. By the thermal decomposition of the oxides of metals low in electrochemical series and
higher oxides of some metals.

iii. Hydrogen peroxide is readily decomposed into water and dioxygen by catalysts such as finely
divided metals and manganese dioxide.

iv. On large scale it can be prepared from water or air. Electrolysis of water leads to the release
of hydrogen at cathode and oxygen at anode.
v. Industrially, dioxygen is obtained from air by first removing carbon dioxide and water vapour
and then, the remaining gases are liquefied and fractionally distilled to give dinitrogen and
dioxygen.
b. Properties
i. Molecular oxygen, O2 is unique in being paramagnetic inspite of having even
number of electrons, since it has 2 unpaired electrons in antibonding molecular orbitals.
ii. Combination of oxygen with other elements is strongly exothermic which helps in sustaining
the reaction. However, to initiate the reaction, some external heating is required as bond
dissociation enthalpy of oxgyen-oxygen double bond is high.
iii. Some reactions of dioxygen are given below

Some compounds are catalytically oxidised. e.g.

iv. Oxides
1. Acidic oxides - An oxide that combines with water to give an acid is termed acidic oxide (e.g.,
SO2, Cl2O7, CO2, N2O5 ). For example, SO2 combines with water to give sulphurous acid(H2SO3)

As a general rule, only non-metal oxides are acidic but oxides of some metals in high
oxidation state also have acidic character (e.g. Mn2O7, CrO3, V2O5).
2. Basic oxides - Oxides which give a base with water are known as basic oxides (e.g., Na 2O,
CaO, BaO). For example, CaO combines with water to give Ca(OH) 2, a base.

In general, metallic oxides are basic.

3. Amphoteric oxides - Metallic oxides which show characteristics of both acidic as well as basic
oxides. They react with acids as well as alkalies. E.g. Al2O3, ZnO.

4. Neutral oxides - Oxides which are neither acidic nor basic. E.g. CO, NO, N 2O.

9. Ozone - Ozone is too reactive to remain for long in the atmosphere at sea level.
a. Preparation - When a stream of oxygen is passed through a silent electrical
discharge, it gets converted to ozone.

Since formation of ozone from oxygen is an endothermic process,

it is necessary to use a silent electrical discharge in its preparation to prevent its
decomposition.
b. Ozone is thermodynamically unstable with respect to oxygen since its decomposition into
oxygen results in liberation of heat (ΔH is negative) and an increase in entropy (ΔS is
positive). These two effects reinforce each other, resulting in large negative Gibbs energy
change (ΔG) for its conversion into oxygen. Therefore,high concentrations of ozone can be
dangerously explosive.
c. Due to the ease with which ozone liberates atoms of nascent oxygen
(O3 → O2 + O nascent), it acts as a powerful oxidising agent. E.g. it oxidizes lead sulphide to
lead sulphate and iodide ions to iodine
d. Quantitative estimation of ozone - When ozone reacts with an excess of potassium iodide
solution,iodine is liberated which can be titrated against a standard solution of sodium
thiosulphate. This is a quantitative method for estimating O3 gas.

e. Nitrogen oxides emitted from jet aeroplanes depletes ozone layer in upper atmosphere.

f. Structure - Central oxygen is sp2 hybridized with 1 lone pair. Hence ozone molecule is bent
in shape. The two oxygen-oxygen bond lengths in ozone
molecule are identical due to resonance.

10. Sulphur - Two allotropes of sulphur are yellow rhombic (α-sulphur) and monoclinic (β
-sulphur). The stable form at room temperature is rhombic sulphur, which transforms to
monoclinic sulphur when heated above 369 K. At 369 K both forms are stable. This
temperature is called transition temperature. Both rhombic and monoclinic sulphur have S8
molecules.
11. Sulphur dioxide
a. Preparation
i. sulphur is burnt in air or oxygen
S(s) + O2(g) → SO2(g)
ii. In lab,by treating a sulphite with dilute sulphuric acid.
SO32-(aq) + 2H+ (aq) → H2O(l) + SO2 (g)
iii. Industrially as a by-product of roasting of sulphide ores.

b. Properties
i. Structure - Central atom (S) has sp2 hybridization with one lone pair (bent shape).
It is a resonance hybrid of two canonical forms

ii. Sulphur dioxide, passed through water, forms a solution of sulphurous acid.

iii. SO2 reacts with sodium hydroxide solution, forming sodium sulphite, which reacts with more
sulphur dioxide to form sodium hydrogen sulphite.
iv. Sulphur dioxide reacts with chlorine to give sulphuryl chloride, SO 2Cl2. It is oxidised to sulphur
trioxide by oxygen in presence of vanadium(V) oxide catalyst.
SO2(g) + Cl2 (g) → SO2Cl2(l)

v. When moist, sulphur dioxide behaves as a reducing agent. For example, it converts iron(III)
ions to iron(II) ions

vi. Test for SO2 - Since SO2 acts as a reducing agent, it decolourises acidified potassium
permanganate(VII) solution.

This reaction serves as a test for SO2.

12.Oxoacids of sulphur

13. Sulphuric acid

a. Manufacture - Sulphuric acid is manufactured by the Contact Process which involves three
steps:
i. burning of sulphur or sulphide ores in air to generate SO2.
ii. conversion of SO2 to SO3 by reaction with oxygen in presence of a catalyst (V2O5)
iii. absorption of SO3 in H2SO4 to give Oleum (H2S2O7).
The key step in the manufacture of H2SO4 is the catalytic oxidation
of SO2with O2 to give SO3 in the presence of V2O5 (catalyst).

The reaction is exothermic, reversible and forward reaction leads

to a decrease in volume. Therefore, low temperature and high pressure
are favourable conditions for maximum yield. But temperature
should not be very low otherwise rate of reaction will become slow.

b. Properties - chemical reactions of sulphuric acid are as a result of following characteristics:

(a) low volatility (b) strong acidic character (c) strong affinity for water (d) ability to act as an
oxidising agent.
 i. Sulphuric acid, because of its low volatility can be used to manufacture more volatile acids
from their corresponding salts.

ii. Concentrated sulphuric acid is a strong dehydrating agent. Many wet gases can be dried by
passing them through sulphuric acid, provided the gases do not react with the acid. Sulphuric
acid removes water from organic compounds; it is evident by its charring action on
carbohydrates.

iii. Hot concentrated sulphuric acid is a strong oxidizing agent. Both metals and non-metals are
oxidised by concentrated sulphuric acid, which is reduced to SO2.

Group 17 Halogens (Salt producers)

1. Occurrence
a. Minerals of Fluorine
i. Fluorspar - CaF2 ii. Cryolite Na3AlF6 iii. Fluoroapatite 3Ca3(PO4)2.CaF2
b. Mineral of Chlorine
Carnallite KCl.MgCl2.6H2O
2. Electronic configuration – ns2np5. One electron short of the next noble gas.
3. Atomic and Ionic radii - Halogens have smallest atomic radii in their respective periods due to
maximum effective nuclear charge. Atomic and ionic radii increase from fluorine to iodine
due to increasing number of quantum shells.
4. Ionization enthalpy - Very high. Due to increase in atomic size, ionisation enthalpy decreases
down the group.
5. Electron gain enthalpy - Halogens have maximum negative electron gain enthalpy because
they have only one electron less than stable noble gas configurations. Electron gain enthalpy
of halogens becomes less negative down the group.
Electron gain enthalpy of fluorine is less negative than that of chlorine.
Reason - Due to small size of fluorine atom,there are strong interelectronic repulsions in 2p
orbitals of fluorine. Therefore, incoming electron does not experience much attraction.
6. Electronegativity - Very high. Decreases down the group. Fluorine most electronegative
element of periodic table.
7. Physical properties
a. Melting and boiling points increase with increase in atomic number due to increase in van
der Waals forces.
b. Halogens are coloured. F2, has yellow, Cl2 , greenish yellow, Br2, red and I2, violet colour.
Reason - absorption of radiations in visible region which results in excitation of outer
electrons to higher energy level.
c. Bond dissociation enthalpy of fluorine is less than chlorine.
Reason - Small size of fluorine which results in large electron-electron repulsion among
lone pairs in F2 molecule.
8. Chemical properties
a. Oxidation states -
All the halogens exhibit –1 oxidation state. However, chlorine, bromine and iodine exhibit
+ 1, + 3, + 5 and + 7 oxidation states also as explained below:

The higher oxidation states of chlorine, bromine and iodine are realised when the halogens
are in combination with the small and highly electronegative fluorine and oxygen atoms. e.g.,
in interhalogens, oxides and oxoacids.
Fluorine shows oxidation state -1 only since it does not have empty d orbitals and it is most
electronegative.
b. Strong oxidizing nature - oxidising power of halogens decreases in the order F 2 > Cl2 > Br2 > I2
A halogen oxidises halide ions of higher atomic number

Electrode potentials depend on three factors

-bond dissociation enthalpy
-electron gain enthalpy
-enthalpy of hydration
 Relative oxidising power of halogens can be illustrated by their reactions with water. Fluorine
oxidises water to oxygen whereas chlorine and bromine react with water to form
corresponding hydrohalic and hypohalous acids. Reaction of iodine with water is
nonspontaneous. In fact, I- can be oxidised by oxygen in acidic medium;
just the reverse of the reaction observed with fluorine.

c. Anomalous properties of fluorine

i. Ionization enthalpy, electronegativity, enthalpy of bond dissociation and electrode potentials
are all higher for fluorine than expected from the trends set by other halogens.
ii. Ionic and covalent radii, m.p. and b.p. and electron gain enthalpy are quite lower than
expected.
iii. Fluorine forms only one oxoacid (HOF hypofluorous acid) while other halogens form a
number of oxoacids.
iv. Hydrogen fluoride is a liquid due to strong hydrogen bonding. Other hydrogen halides are
gases.
d. Hydrides of group 17 - stability of these halides decreases down the group due to decrease in
bond (H–X) dissociation enthalpy in the order: H–F > H–Cl > H–Br > H–I. As a result, acidic
strength(ease of giving H+ ions) increases down the group.
e. Oxides of group 17
i. Higher oxides of halogens (oxides containing halogens in higher oxidation state) are more
stable than lower oxides (oxides containing halogens in lower oxidation state). E.g. order of
stability of oxides of chlorine is Cl2O< ClO2< Cl2 O6< Cl2 O7.
ii. ClO2 is used as a bleaching agent for paper pulp and textiles and in water treatment.
iii. Bromine oxides, Br2O, BrO2 , BrO3 are the least stable halogen oxides.
iv. I2O5 is used in estimation of carbon monoxide.
f. Reactivity towards metals - Halogens react with metals to form metal halides. For e.g.,
bromine reacts with magnesium to give magnesium bromide.
Mg (s) + Br2 (l) → MgBr2(s)
Fajan’s rules
Ionic character of the halides decreases in the order MF > MCl > MBr > MI where M is a
monovalent metal. If a metal exhibits more than one oxidation state, the halides in higher
oxidation state will be more covalent than the one in lower oxidation state. For e.g., SnCl4,
PbCl4, SbCl5 and UF6 are more covalent than SnCl2, PbCl2, SbCl3 and UF4 respectively.
9. Chlorine
a. Preparation
i. Heat manganese dioxide with concentrated hydrochloric acid

ii. Action of HCl on potassium permanganate

2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 5Cl2
b. Manufacture
i. Deacon’s process: By oxidation of hydrogen chloride gas by atmospheric oxygen in presence
of CuCl2 (catalyst)

ii. Electrolytic process: Chlorine is obtained by the electrolysis of brine (concentrated NaCl
solution). Chlorine is liberated at anode.
c. Chemical properties
i. Chlorine reacts with metals and non-metals to form chlorides.

ii. Chlorine has great affinity for hydrogen. It reacts with compounds containing hydrogen to
form HCl.

iii. With excess ammonia, chlorine gives nitrogen and ammonium chloride whereas with excess
chlorine, nitrogen trichloride (explosive) is formed.

iv. With cold and dilute alkalies chlorine produces a mixture of chloride and hypochlorite but
with hot and concentrated alkalies it gives chloride and chlorate.

v. Chlorine reacts with dry slaked lime to give bleaching powder

The composition of bleaching powder is Ca(OCl)2.CaCl2.Ca(OH)2.2H2O.

vi. Chlorine reacts with hydrocarbons and gives substitution products with saturated
hydrocarbons and addition products with unsaturated hydrocarbons. For example,
vii. Chlorine water on standing loses its yellow colour due to formation of HCl and HOCl.
Hypochlorous acid (HOCl) so formed, gives nascent oxygen which is responsible for oxidising
and bleaching properties of chlorine.
- Chlorine oxidises ferrous to ferric, sulphite to sulphate, sulphur dioxide to sulphuric acid
and iodine to iodic acid.

- Chlorine is a powerful bleaching agent; bleaching action is due to oxidation and therefore
permanent.
Cl2 + H2O → 2HCl + O
Coloured substance + O → Colourless substance

10. Hydrogen chloride

a. Preparation - In laboratory, hy is prepared by heating sodium chloride with concentrated
sulphuric acid.
NaCl + H2SO4 ⎯→ NaHSO4 + HCl
HCl gas can be dried by passing through concentrated sulphuric acid.
b. Properties
i. Aqueous solution of hydrogen chloride in water is called hydrochloric acid.
-It reacts with NH3 and gives white fumes of NH4Cl.
NH3 + HCl → NH4Cl
- When three parts of concentrated HCl and one part of concentrated HNO 3 are mixed, aqua
regia is formed which is used for dissolving noble metals, e.g., gold, platinum.
Au + H+ + NO3- + Cl-→ AuCl4- + NO H2O
Pt + H+ + NO3- +Cl- → PtCl62- + NO + H2O
- Hydrochloric acid decomposes salts of weaker acids, e.g.,carbonates, hydrogencarbonates,
sulphites.
Na2CO3 + 2HCl → 2NaCl + H2O + CO2
NaHCO3 + HCl → NaCl + H2O + CO2
Na2SO3 + 2HCl → 2NaCl + H2O + SO2

11. Oxoacids of halogens

Fluorine forms only one oxoacid HOF (Fluoric (I) acid or hypofluorous acid) due to high
electronegativity.
Acid strength: HOCl < HClO2 < HClO3 < HClO4 Reason: HClO4 → H+ + ClO4- most stable
Acid strength: HOF > HOCl > HOBr > HOI
Greater the electronegativity of halogen in oxoacids greater is acidic strength of oxoacids.
(F>Cl>Br>I)

Group 17
(i)Halogens have the smallest atomic radii in their respective periods.
Ans:The halogens have the smallest atomic radii in their respective periods
due to maximum effective nuclear charge.

(ii)Halogens have maximum negative electron gain enthalpy in the respective periods of the
periodic table.
Ans:Halogens have the smallest size in their respective periods and therefore high effective
nuclear charge. As a consequence, they readily accept one electron to acquire noble gas
electronic configuration.

(iii) Halogens are coloured.

Ans:Halogens are coloured. This is due to absorption of radiations in visible region which
results in the excitation of outer electrons to higher energy level. By absorbing different
quanta of radiation, they display different colours. For example, F2, has yellow, Cl2 , greenish
yellow, Br2, red and I2, violet colour.

(iv) Bond dissociation energy of F2 is less than Cl2.

Ans:Due to large electron-electron repulsion among the lone pairs in F 2 molecule where they
are much closer to each other than in case of Cl2.

(v)Although electron gain enthalpy of Fluorine is less negative as compared to Chlorine,

Fluorine is stronger oxidizing agent than chlorine.
Ans:It is due to (i) low enthalpy of dissociation of F-F bond (ii) high hydration enthalpy of F-.

(vi) Halogens are strong oxidizing agent.

Ans:Due to strong tendency to accept electrons.

(vii) Fluorine exhibit oxidation state of –1 only whereas other halogens exhibit +1, +3, +5, +7
oxidation states also.
Ans:Fluorine is the most electronegative element and cannot exhibit any positive oxidation
state.Other halogens have d orbitals and therefore, can expand their octets and show + 1, +
3, + 5 and + 7 oxidation states also.

(viii) Fluorine is anomalous in many properties. (I.E, Bond dissociation, etc)

Ans:The anomalous behaviour of fluorine is due to its small size, highest electronegativity,
low F-F bond dissociation enthalpy, and non availability of d orbitals in valence shell.

(ix)Most of the reactions of fluorine are exothermic.

Ans:Due to the small and strong bond formed by it with other elements)

(x)Fluorine forms only one oxoacid, HOF.

Ans:Due to high electronegativity and small size F does not form HOFO,HOFO2&HOFO3 in
which oxdn.no.will be +3,+5 &+7

(xi)The acidic strength of hydrogen halides varies in the order HF<HCl<HBr<HI.

Ans:Because bond (H–X) dissociation enthalpy decrease in the order: H–F > H–Cl >H–Br > H–I.

(xii) HI in aqueous solution is strong acid than HF.

Ans:Due to low bond (H–X) dissociation enthalpy in HI

(xiii) HF is the weakest acid among hydrohalo-acids inspite of the fact that fluorine is most
electronegative.
Ans:Due to highest bond (H–X) dissociation enthalpy in HF

(xiv) Metal fluorides are more ionic than its chlorides.

Ans:Greater the difference in electronegativity, more will be its ionic character, fluorine
being more electronegative than chlorine

(xv) HF has higher boiling point than HCl.

Ans:Due to presence of intermolecular hydrogen bonding in HF

(xvi) HF is least volatile whereas HCl is most volatile among all halogens.
Ans:HF is associated with intermolecular hydrogen bonding, so it is least volatile whereas HCl
is gas and has least surface area, therefore minimum Vander waals forces of attraction and
minimum boiling point

(xviii)The boiling point of hydrogen halides varies in the order: HF > HI>HBr>HCl.
Ans:The boiling point of HF is highest due to intermolecular hydrogen bonding then
HI>HBr>HCl. ( DecreasingVanderwaals forces

(xix) Interhalogen compounds are more reactive than related elemental halogens.
Ans:In general, interhalogen compounds are more reactive than halogens due to weaker X–
X1 bonding than X–X bond. Thus, ICl is more reactive than I2.

(xx).ICl is more reactive than Cl2.

Ans:Due to weaker I-Cl bonding than Cl-Cl bond. Thus, ICl is more reactive than I2.

(xxi) The acidic strength of oxoacids of halogens varies in the order HOF>HOCl>HOBr>HOI.
Ans:Greater the electronegativity of halogen in oxoacids greater is acidic strength of
oxoacids. (F>Cl>Br>I)

(xxii) The acidic strength of oxoacids of halogens varies in the order:

HClO4> HClO3> HClO2> HClO
Ans:Greater the oxidation state of halogen in oxoacids greater is acidic strength of oxoacids.
(+7>+5>+3>+1)

(xxiii) OF2 should be called oxygen fluoride and not fluorine oxide.
Ans:OF2 should be called oxygen fluoride and not fluorine oxide. Since oxygen is less
electronegative than fluorine, OF2 should be called oxygen diflouride.

(xxiv) ClF3 exists but FCl3 does not.

Ans:Due to unavailability of d-orbitals in fluorine atom it cannot expand its valence shell.
Therefore it is unable to form FCl3 whereas Chlorine has vacant d-orbitals. Hence it can
promote one of the 3 p electrons to the 3-d sub shell and shows +3 oxidation state and forms
ClF3
(xxv)Cl2 bleaches a substance permanently but SO2 does it temporarily.
Ans:Cl2 bleaches a substance permanently because it is due to Oxidation but SO 2 does it
temporarily because it is due to reduction.

(xxvi)When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric
chloride.
Ans:Its reaction with iron produces H2.Fe + 2HCl →FeCl 2 +H2 .Liberation of hydrogen
prevents the formation of ferric chloride.
Group 18
(i)The elements of group 18 are known as noble gases.
The elements present in Group 18 have their valence shell orbitals completely filled and,
therefore, react with a few elements only under certain conditions. Therefore, they are now
known as noble gases.

(ii)Noble gases are mostly chemically inert.

Their inertness to chemical reactivity is attributed to the following reasons:
(i) The noble gases except helium (1s2) have completely filled ns2p6 electronic configuration in
their valence shell. (ii) They have high ionisation enthalpy and more positive electron gain
enthalpy.

(iii)Noble gases have comparatively largest atomic sizes.

In noble gases we can measure only Van der Waals radii which are larger than covalent radii.

(iv)Noble gases exist as monatomic.

Noble gases have stable electronic configuration, therefore, they cannot form covalent
bonds. So they exist as monoatomic

(v)Noble gases exhibit very high ionization enthalpy.

Due to stable electronic configuration these gases exhibit very high ionisation enthalpy.

(vi)Noble gases exhibit large positive values of electron gain enthalpy.

Since noble gases have stable electronic configurations, they have no tendency to accept the
electron and therefore, have large positive values of electron gain enthalpy.

(vii)Noble gases have very low boiling points

Noble gases being monoatomic have no interatomic forces except weak dispersion forces
and therefore, they are liquefied at very low temperatures. Hence, they have low boiling
points.

.(viii) Of the noble gases only Xenon is known to form real chemical compounds.
The ionization energy of xenon is relatively low and therefore, it is possible to excite the
paired electrons from np orbitals to nd subshell
(ix) Noble gases form compounds with fluorine and oxygen only.
Because fluorine and oxygen are strong oxidizing agents(most electronegative elements)

(x) Helium is used for inflating aeroplane tyres & filling balloons for meteorogical
observations.
Helium is a non-inflammable and light gas

(xi)Helium is used in diving apparatus.

Because of its very low solubility in blood.

(xii)It has been difficult to study the chemistry of radon.

Radon is radioactive with very short half-life which makes the study of chemistry of radon
difficult.

(xiii) Xenon readily forms compounds but Krypton does not form compounds easily.
Xenon has lower ionization energy than Krypton, therefore, Xe forms compounds

(xiv) He and Ne does not form compounds with fluorine.

Due to non-availability of vacant d-orbital

(xv) Xe does not forms compounds such as Xe F3 and XeF5.

By the promotion of one, two or three electrons from filled p-orbital to the vacant d-orbital
in the valence shell, 2,4 or 6 half filled orbitals are formed. Thus Xe can combine only with
even number of fluorine and not odd.