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Contents
■ Group 15 elements
■ Dinitrogen
■ Ammonia ■ Group 17 elements
■ Oxoacids of hydrogen – Nitric Acid
■ Phosphorous ■ Hydrogen Chloride
■ Phosphine
■ Phosphorous Halides
■ Oxoacids of Halogens
■ Group 16 elements ■ Inter Halogen
■ Dioxygen
■ Oxides Compounds
Ozone
■
■ Sulphur
■ Group 18
■ Sulphur Dioxide ■ Xenon discussed in
■ Sulphuric Acid
detail
 p - BLOCK
P –BLOCK
Group - 15

>The Group 15 elements are: Nitrogen

(Elements with atomic number)

Nitrogen (N) 🡪7
Phosphorus (P) 🡪15 Phosphoro
Arsenic
Arsenic (As) 🡪33 us
Antimony (Sb) 🡪51
Bismuth (Bi) 🡪83 Group 15

>Configuration:
N 🡪1s2 2s2 2p3
(ns2 np3)
The s-orbital in these elements is Antimony Bismuth
completely filled and p-orbital
is half filled making their
electronic configuration extra
stable.
 p - BLOCK
■ Size:
As we move from top to bottom, there’s an increase in the
size because of the increase in the number of shells. From N
to P, there’s an increase in the size but from As to Bi, only a
small increase in the size because of the presence of
completely filled d- and/or f-orbital in higher members.

■ Ionization Enthalpy:
It is defined as the amount of the energy required to
remove the outermost electron. Since the size increases
down the group, therefore ionization enthalpy decreases
down the group.

■ Electronegativity:
It is the property to attract the shared pair of electron
towards itself. Down the group, since the size increases,
tendency to attract the shared pair of electron will decrease
and hence electronegativity will decrease.
Physical Properties: p - BLOCK

■ All the elements of this group are polyatomic.

■ Dinitrogen (N2) is a diatomic gas while all others are solid.
■ Nitrogen and Phosphorus are non-metals, Arsenic and
Antimony are metalloids and Bismuth is a metal.
■ Except Nitrogen, all other elements show allotropic nature.

Chemical properties:

Oxidation states:
■ They show oxidation state of -3, +3 and +5.
■ Tendency to exist -3 oxidation state decreases down the
group due to increase in size and metallic character.
■ Bismuth hardly shows -3 oxidation state.
■ The stability of +5 oxidation state decreases down the group
and that of +3 oxidation state increases. This is because of
inert pair effect.
■ The only well established +5 oxidation state in Bismuth is in
BiF5.
Q. What do you understand by inert pair effect? What
happens due to it?
Ans. The non-participation of inner line two s- electrons in the
bond formation is known as inert pair effect. The inner lying
s- electron pair does not participate in bonding and acts as
an inert pair. Because of this effect, tendency to lower
oxidation state increases down the group.

Q. Nitrogen is restricted to a maximum covalency of 4,

why?
Ans. Because only four 2s and 3p orbitals are available for
bonding.

Q. Why the covalency of other elements of group 15

can be increased beyond 4?
Ans. Because they have vacant d-orbitals in their outermost
shell.
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 p - BLOCK

Q. Why and how does Nitrogen show anomalous

behavior?
Ans. This is because of its:
■ small size
■ high electronegativity
■ high ionization enthalpy
■ non-availability of d-orbitals

This is shown as follows:

It has a unique ability to form p∏-p∏ multiple bonds with itself
and with other elements having small size and high
electronegativity.
Catenation tendency is weaker in Nitrogen as compared to
other elements of this group.
 p - BLOCK

Q. Why the heavier elements of group 15 do not

form p∏-p∏ bonds?
Ans. Because their atomic orbitals are so large and diffuse
that they cannot have effective overlapping.

Q. Why is the single bond in N-N much weaker

than single bond in P-P?
Ans. Because of high inter-electronic repulsion of the
non-bonding electrons owing to the small bond lengths.
Because of the above reason, Catenation tendency in
Nitrogen is much weaker as compared to other elements
of this group.
 p - BLOCK

Reactivity towards Hydrogen

■ Group 15 elements form hydrides of the formula EH3
where E is the element of group 15.
■ Hydrides show regular gradation in their properties i.e.
stability decreases from NH3 to BiH3 because of decrease
in bond dissociation enthalpy.
■ Reducing character of hydrides increases i.e. NH3
(ammonia) is the strongest reducing agent while BiH3 is
the weakest.
■ PH3 has lower boiling point than NH3. PH3 molecules are
not associated through hydrogen bonding in liquid state.
 p - BLOCK

Reactivity towards Oxygen

■ They form two types of oxides E2O3 and E2O5.
■ The oxide in higher oxidation state (E2O5) is more acidic.
■ Acidic character decreases down the group.
■ Oxides of the type E2O3 of Nitrogen and Phosphorus are
purely acidic, of Arsenic and Antimony are amphoteric
and of Bismuth are Basic.
 p - BLOCK

Reactivity towards Halogen

■ They form halides of the formula EX3 and EX5.
■ Nitrogen does not form penta halide due to
non-availability of the d-orbitals in the valence shell.
■ Penta halides are more covalent than tri halides.
■ All the tri halides except Nitrogen are stable. NF3 is the
most stable tri halide of Nitrogen.
■ Tri halides except BiF3 are covalent in nature.
 p - BLOCK

Reactivity towards Metals

■ These elements react with metals to form their binary
compounds exhibiting –3 oxidation state.
Examples:
Ca3N2 (Calcium Nitride)
Ca3P2 (Calcium Phosphide)
Na3As2 (Sodium Arsenide)
 p - BLOCK

DINITROGEN
Preparation:

a) Lab preparation

NH4Cl(aq) + NaNO2(aq) → N2(g) + 2H2O(l) + NaCl (aq)

b) General

(NH4)2Cr2O7 → N2 + 4H2O + Cr2O3

c) For obtaining by Thermal Decomposition of Na or Ba azide

Ba(N3)2 → Ba + 3N2
 p - BLOCK
Properties

■ It has two stable isotopes: 14N and 15N.

■ It has a very low solubility in water.
■ It is quite inert at room temperature because of high bond
enthalpy of N≡N bond.
■ As temperature increases, reactivity increases
■ It shows the following reactions:
6Li + N2→ 2Li3N
3Mg + N2→ Mg3N2
N2 (g) + 3H2 (g) → 2NH3 (g) [Haber’s process]
 p - BLOCK

AMMONIA
Preparation

■ Urea

NH2CONH2🡪 + 2H2O → (NH4)2CO3 → 2NH3 + H2O + CO2

■ On small scale

2NH4Cl + Ca(OH)2 →2NH3 + 2H2O + CaCl2

(NH4)2SO4 + 2NaOH → 🡪2NH3 + 2H2O + Na2SO4

■ On large scale

N2(g) + 3H2(g) → 2NH3(g)

Q. What are the conditions in accordance to Le Chatelier’s
principle for the formation of Ammonia ?
Ans. ~Pressure of about 200 atm.
~Temperature of about 700 K.
~Catalyst- Iron oxide with small amounts of K2O
and Al2O3
Q. Draw a flow chart for the production of NH3 by Haber’s
process.
Ans.
 p - BLOCK

Properties
1. Structure of Ammonia:
It has pyramidal structure with one lone pair of electrons.
Hybridization present is sp3 but the tetrahedral angle gets
reduced to 107.8° because of repulsion of lone pair of
electrons.

2. Ammonia gas is highly soluble in water and its aqueous

solution is weakly basic due to the formation of OH– ions.
NH3 (g) + H2O (l) → NH4+ (aq) + OH– (aq)

3. In water, Ammonia forms hydroxide which is knows as

Ammonium Hydroxide.
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Q. What happens when Ammonia Hydroxide is made to react with Zinc Sulphate and
Ferric Chloride respectively?
Ans. ZnSO4 (aq)+ 2NH4OH (aq) → Zn(OH)2 (s) + (NH4)2SO4 (aq)
(White ppt)

2FeCl3 (aq) + NH4OH (aq) → Fe2O3.xH2O + NH4Cl (aq)

(Brown ppt)

Q. How are the metal ions like Cu2+ and Ag+ detected using Ammonia?
Ans. a) Cu2+ (aq) + 4NH3 (aq) → [Cu (NH3)4]2+(aq)
(Blue) (Deep blue)
b) Ag+ (🡪aq)🡪🡪🡪🡪 + Cl- (🡪aq) 🡪🡪→ AgCl 🡪(s)🡪
(Colourless) (White ppt)
AgCl (s) + 🡪2NH3 → [Ag (NH3)2] Cl
(White ppt) (Colourless)

Q. From the reaction, what typical characteristic of NH3 can we gather?

Ans. The presence of lone pair of electrons on the Nitrogen atom of the Ammonium
molecule makes it a Lewis base. It donates the electron pair and forms linkage with
metal ions and this finds an application in detection of metal ions.
Q. Draw a table of the various oxides of Nitrogen. p - BLOCK
Ans.
 p - BLOCK
Q. Draw a table which gives the structure of oxides of Nitrogen.
Ans.
 p - BLOCK
Q. Why does NO2 dimerise?
Ans. The structure of NO2 is

The structure of NO2 as depicted above contains odd number of

valence electrons. It behaves as a typical odd molecule. On
dimerisation, it is converted to stable N2O4 molecule having even
number of molecules.
 p - BLOCK

OXOACIDS of Nitrogen

There are
three oxoacids

Hyponitrous acids Nitrous acids Nitric acid

H2 N 2 O 2 HNO2 HNO3
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NITRIC ACID
Preparation of Nitric Acid

1. In the laboratory, nitric acid is prepared by heating KNO3 or NaNO3 and

concentrated H2SO4 in a
glass retort.
NaNO3 + H2SO4 → NaHSO4 + HNO3
2. On a large scale it is prepared mainly by Ostwald’s process.
4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g)
3NO2 (g) + H2O (l) → 2HNO3 (aq) + NO (g)

Structure of Nitric acid:

 p - BLOCK

Properties
1. In the gaseous state, it exists as a planar molecule.
2. It behaves as a strong acid giving hydronium and nitrate iona.
HNO3(aq) + H2O(l) →🡪H3O+(aq) + NO3–(aq)

3. Concentrated nitric acid is a strong oxidising agent and attacks most metals except
noble metals such as gold and platinum.
3Cu + 8 HNO3(dilute) → 3Cu(NO3)2 + 2NO + 4H2O
Cu + 4HNO3(conc.) → Cu(NO3)2 + 2NO2 + 2H2O
4Zn + 10HNO3(dilute) → 4 Zn (NO3)2 + 5H2O + N2O
Zn + 4HNO3(conc.) →🡪Zn (NO3)2 + 2H2O + 2NO2

4. Some metals (e.g., Cr, Al) do not dissolve in concentrated nitric acid because of the
formation of a film of oxide on the surface.

5. Concentrated nitric acid also oxidizes non-metals

I2 + 10HNO3 →🡪2HIO3 + 10 NO2 + 4H2O
C + 4HNO3 →🡪CO2 + 2H2O + 4NO2
S8 + 48HNO3(conc.) →🡪8H2SO4 + 48NO2 + 16H2O
P4 + 20HNO3(conc.) →🡪4H3PO4 + 20 NO2 + 4H2O
 p - BLOCK

Brown ring test of Nitrates

When to a Nitrate solution, freshly prepared Ferrous

Sulphate solution is added and then conc. H2SO4 acid
along the side of the test tube is added, then a brown
ring at the interphase is formed.

NO3 + 3Fe2+ + 4H+ →🡪NO + 3Fe3+ + 2H2O

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

(Brown)
 p - BLOCK

PHOSPHOROUS

White

It exists in
three
allotropic
forms

Red Black
White Phosphorus p - BLOCK

■ It is a white waxy solid.

■ It is poisonous.
■ Insoluble in water but soluble in Carbon disulphide (CS2).
■ It glows in dark (chemiluminescence).

■ It dissolves in boiling NaOH solution in an inert atmosphere

giving Phosphine and Sodium hypophosphite.
P+ 3NaOH + 3H2O →PH3 + 3NaH2PO2

■ It is less stable and therefore, more reactive than the other

solid phases because of angular strain in the P4 molecule.
■ It readily catches fire in air to give dense white fumes of P4O10.
■ It exists as discrete tetrahedral P4 molecule.
 p - BLOCK
Red Phosphorus

■ It is obtained by heating white phosphorus at 573K in an

inert atmosphere for several days.
■ It has iron grey lustre.
■ It is odourless, nonpoisonous.
■ Insoluble in water as well as in carbon disulphide.
■ It does not glow in the dark.
■ Chemically, red phosphorus is much less reactive than
white phosphorus because it is a polymeric in nature
consisting of a number of P4 tetrahedral units joined
together.
 p - BLOCK
Black phosphorus:

■ It has two forms α-black phosphorus and β-black phosphorus.

α-black phosphorus

~α is formed when Red phosphorus is heated in a sealed tube at

803K.
~It can be sublimed in air.
~It has opaque, monoclinic or rhombohedral crystals.
~It does not oxidize in air.

β-black phosphorus

~β is prepared by heating white phosphorus at 473 K under high

pressure.
~It does not burn in air upto 673K.
 p - BLOCK

PHOSPHINE ( PH3 )
Preparation:

Ca3P2 + 6H2O →🡪3Ca(OH)2 + 2PH3

Ca3P2 + 6HCl →🡪3CaCl2 + 2PH3
Laboratory preparation:
P4 + 3NaOH (conc.) + 3H2O → PH3 + 3Na H2PO2
(Sodium hypophosphite)
When pure, it is non inflammable but becomes inflammable
owing to the presence of P2H4 or P4 vapours. To purify it from the impurities,
it is absorbed in HI to form phosphonium iodide which on treating with KOH
gives off phosphine.

PH4I🡪 + KOH🡪 → KI + 🡪H2O🡪 + PH3

 p - BLOCK
Properties
■ In the pure state, it is non-inflammable but becomes flammable owing to the
presence of P2H4 or P4 vapour.

■ It is a colourless gas with rotten fish smell

■ Highly poisonous.

■ It explodes in contact with traces of oxidizing agents like HNO 3, Cl2 and Br2 vapours.

■ It is slightly soluble in water.

■ It decomposes in water in presence of light giving red phosphorus and H 2.

■ It is weakly basic like Ammonia and gives Phosphonium compounds like acids.
PH3 + HBr → PH4Br

■ It interacts with Phosphonic acid and mercuric chloride

3CuSO4 +2PH3 →Cu3P2 + 3H2SO4
3HgCl2 + 2PH3 → Hg3P2 + 6HCl
 p - BLOCK

PHOSPHOROUS HALIDES
It forms two types of halides, PX3 and PX5.
In PX3 (X = F, Cl, Br, I)
PX5 (X = F, Cl, Br)

It is obtained by reacting white phosphorus with

thionyl chloride.
P4 + 8SOCl2 → 4PCl3 + 4SO2 + 2S2Cl2

It is obtained by dry chlorine with white

phosphorous on heating.
P4 + 6Cl2 → 4PCl3
 p - BLOCK

Structure:
Phosphorus trichloride

(shape – pyramidal)
 p - BLOCK

Properties
■ It is a colourless oily liquid.
■ Hydrolyses in the presence of moisture.
PCl3 + 3H2O → H3PO2 + 3HCl
■ It reacts with organic compounds containing –OH group
such as CH3COOH, C2H5OH.
3CH3COOH + PCl3 → 3CH3COCl + H3PO3
3C2H5OH + PCl3 → 3C2H5Cl + H3PO3
 p - BLOCK

PHOSPHOROUS PENTACHLORIDE

Preparation

■ Phosphorus pentachloride is prepared by the reaction of

white phosphorus with excess of dry chlorine.
P4 + 10Cl2 → 4PCl5

■ It can also be prepared by the action of SO2Cl2 on

phosphorus.
P4 + 10SO2Cl2 → 4PCl5 + 10SO2
 p - BLOCK

Properties
■ It is a yellowish white powder
■ It hydrolysis in moist air to POCl3 and finally gets converted to
phosphoric acid.
PCl5 + H2O → POCl3 + 2HCl
POCl3 + 3H2O → H3PO4 + 3HCl
■ When heated, it sublimes but decomposes on stronger heating.
PCl5 → PCl3 + Cl2
■ It reacts with organic compounds containing –OH group converting
them to chloro derivatives.
C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl
CH3COOH + PCl5 → CH3COCl + POCl3 + HCl
■ Finely divided metals on heating with PCl5 give corresponding
chlorides.
2Ag + PCl5 → 2AgCl + PCl3
Sn + 2PCl5 → SnCl2 + 2PCl3
 Structure of PCl5 with bond formation (in gaseous
and liquid state)

■ There are two types of bonds: 2 are axial and other three are equatorial.
■ → Axial PCl is longer than equatorial PCl bond length because of the
repulsion.
■ → In the solid state, it exists as ionic solid PCl4, PCl6 with cationic part as
tetrahedral and anionic part is octahedral.

■ Q. What indicates the basicity of the oxoacids of Phosphorus?

■ Ans. The presence of Hydrogen atoms which are directly attached to PO
indicate the basicity.
Oxoacids of phosphorus
Structures of Oxoacids
The acids which contain P-H bond have strong reducing
properties
Hypophosphorous acid is a good reducing agent as it contains
two P-H bonds and reduces silver nitrate to silver
The P-H bonds are not ionisable to give H+ and do not play any
role in basicity
Only those hydrogen atoms which are attached with oxygen in
P-OH form are ionisable and cause basicity
H3PO3 and H3 PO4 are dibasic and tribasic respectively as the
structure have two P-OH bonds and three P-OH bonds
respectively
 p - BLOCK

GROUP 16
includes:
1. Oxygen (O)
2. Sulphur (S)
3. Selenium (Se)
4. Tellurium (Te)
5. Polonium (Po)
 p - BLOCK
Anomalous behavior of Oxygen

This is due to
The following
reasons:

High Absence of
Small size
eletronegativity d-orbitals
 IONIZATION ENTHALPY
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.
Q. Why water is a liquid and H2S is a gas though oxygen
and sulphur belong to the same group?
Ans. Oxygen atom has a small size and high electronegativity,
therefore, it is capable of forming hydrogen bonds which is not
possible in H2S. Due to the presence of hydrogen bonding it has
a compact structure and is present in liquid state.

Q. Why does the stability of +4 oxidation state increase

down the group while that of +6 decrease ?
Ans. The general outer electronic configuration of 16 group
elements is ns2np4 . Therefore, the common oxidation state
would be +4 and +6 . Stability of +4 will increase due to the
inert pair effect.

Q. Why does oxygen limit its covalency to 4 ? OR Why

cannot oxygen expand its covalency beyond 4 while
the other elements can do so?
Ans. This is due to the absence of the d-orbitals in the oxygen
atom.
Reactivity towards Hydrogen
 p - BLOCK

Reactivity towards Hydrogen

■ All the elements combine with hydrogen to form
hydrides of the type H2E
■ Acidic character increases from top to bottom because of
decrease in bond dissociation enthalpy down the group
■ Thermal stability decreases down the group because of
the increase in the bond length
■ Except water all hydrides have reducing property and
this increases down the group.
 Reasoning Questions
Q: H2S is less acidic than H2Te. Why?
A: Due to the decrease in bond (E–H)
dissociation enthalpy down the group, acidic
character increases.
Q: H2Te is the strongest reducing agent
amongst the group 16 hydrides. Why?
A: Down the group bond enthalpy decreases
making the loss of H easier, hence reducing
property increases. Te is the last member,
hence the strongest reducing agent.
Physical properties of hydrides
 p - BLOCK

Reactivity towards Oxygen

■ All the elements form oxides of the formula EO2 and EO3
■ Reducing properties of dioxides decreases down the
group
■ All oxides are acidic in nature .
 Reasoning Questions

Q: Reducing property of dioxide decreases

from SO2 to TeO2 . Why?

Q: SO2 is reducing while TeO2 is an oxidising

agent. Why?
 p - BLOCK

Reactivity towards Halogens

■ They form a large number of halides of the formula EX6,
EX4, EX2
■ The stability of the halides decreases down the group, in
the order F > Cl > Br > I ( Stability decreasing )
■ Among Hexahalides, Hexa fluorides are the only stable
halides. They are gaseous in nature and have octahedral
structure.
■ Sulphur hexafluoride, SF6 is exceptionally stable for steric
reasons.
 p - BLOCK

DIOXYGEN ( o2 )
Preparation of Dioxygen
1. From KClO3

2. From Oxides (Thermal decomposition of oxides of

metals)

3. From decomposition of hydrogen peroxide

4. On a large scale it is prepared by electrolysis of

water
 p - BLOCK

Properties of O2

■ Dioxygen is odourless and colourless

■ It is paramagnetic inspite of having ‘even’
number of electrons
■ It reacts with nearly all metals and
non-metals except gold, platinum and
some noble gases.
 p - BLOCK

Some of the common reactions of Dioxygen

are
 p - BLOCK

OXIDES
■ Oxides are a binary compound of oxygen with
another element is called oxide
■ Oxides can be simple (MgO, Al O ) or mixed
2 3
(Pb3O4, Fe3O4)
■ Another way of classification of simple oxides is-
a) Acidic
b) Basic
c) Amphoteric and
d) Neutral
ACIDIC OXIDE p - BLOCK
~An oxide which combines with water to give an acid is called an Acidic Oxide
E.g.. : SO2, CO2, N2O5
~Generally non-metallic oxides are acidic

BASIC OXIDE
~The oxides which give a base on reaction with water are called Basic Oxides
E.g.. : Na2O, CaO, BaO
~Generally, metallic oxides are basic in nature

AMPHOTERIC OXIDE
~These are oxides which exhibit a dual behavior i.e. they show properties of both acidic and basic
oxides
E.g.. : Al2O3

NEUTRAL OXIDE
~Oxides which are neither acidic nor basic
E.g.. : CO, NO, N2O
 p - BLOCK

OZONE
■ Ozone is an allotropic forms of oxygen
■ It is formed from atmospheric oxygen in the presence of
sunlight
■ Ozone protects the earth’s surface from excessive
concentration of ultraviolet (UV) radiations
■ It is a pale blue gas, dark blue liquid or violet-black solid
■ Ozone is thermodynamically unstable and gives dioxygen
and nascent oxygen on decomposition and because of this
nascent oxygen, it is a powerful oxidising agent
■ Two chemical reactions to show the oxidising nature of
ozone are
 Reasoning Question
Q: Ozone is thermodynamically unstable
with respect to oxygen . Why?
A: Decomposition of ozone into oxygen
results in :
■the liberation of heat (ΔH is negative) and

■ an increase in entropy (ΔS is positive).

This results in large negative Gibbs energy

change
Q: Why does O3 act as a powerful oxidising
agent?

Q: How is O3 estimated quantitatively?

A: 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.
■ The structure of ozone is as follows p - BLOCK

■ Q: All the O-O bonds in ozone are equivalent. Explain why?

■ Ozone saves us from the UV radiations but there is a depletion

in the ozone concentration in the upper layer of the
atmosphere due to supersonic jet airoplanes and use of freons
which are used in the aerosol sprays and as refrigerants .
 p - BLOCK
SULPHUR
■ Sulphur exists in numerous allotropes of which two are the most
important which are – yellow rhombic (∞) and monoclinic (🡪)

■ At room temperature, Rhombic is stabler and it transforms to Yellow

monoclinic sulphur when heated above 369 K
Rhomb
■ Rhombic Sulphur is ic
~yellow in colour
~melting point - 385.8 K
~specific gravity – 2.06
~formed on evaporating the solution of Roll Sulphur in
carbon disulphide Sulphu
r
~insoluble in water and readily soluble in carbon disulphide
■ Monoclinic sulphur
~melting point – 393 K
~specific gravity – 1.98
~soluble in carbon disulphide
α
~prepared by melting rhombic sulphur in a dish and cooling Sulphu
r
 p - BLOCK
■ α sulphur is stable below 369 K and transforms into β
sulphur above this temperature. At 369 K both the forms
are stable, hence this temperature is called –
Transition Temperature
■ Both Rhombic and Monoclinic Sulphur have S8
molecules. They both have puckered or typical forms.
Several other modifications of sulphur containing 6 – 20
atoms per ring have been prepared.
 QUESTION

■ Which form of sulphur shows

paramagnetic behaviour ?
■ In vapour state sulphur partly exists as S2
molecule which has two unpaired
electrons in the antibonding π * orbitals
like O2 and, hence, exhibits
paramagnetism.
 p - BLOCK

SULPHUR DIOXIDE
Methods of Preparation:
■ General Method
S (s) + O2 🡪 SO2 (g)
■ Lab Method
SO32- (aq) + 2H+ 🡪 H20 (l) + SO2 (g)
■ Industrial Method
4FeS2 (g) + 11O2 (g) 🡪 2Fe2O3 (s) + 8SO2 (g)

Properties:
■ Colourless gas
■ Pungent smell
■ Highly soluble in water
■ When passed through water forms sulphurous acid (H2SO3)
■ When passed through NaOH
2NaOH + SO2 🡪 Na2SO3 + H2O
Na2SO3 + H2O + SO2 🡪 2NaHSO3
 p - BLOCK

Properties continued….

■ When made to react with chlorine it gives sulphuryl chloride

SO2 (g) + Cl2 (g) 🡪 SO2Cl2 (l)
■ When reacted with oxygen in presence of vanadium (V)
pentoxide forms sulphur dioxide
V2O5
2SO2 (g) + O2 (g) ----🡪 2SO3 (g)
■ It behaves as Reducing agents
■ Converts Fe3+ 🡪 Fe2+
2Fe3+ + SO2 + 2H2O 🡪 2Fe2+ + SO42- + 4H+
■ Decolourises acidified KMnO4 solution
5SO2 + 2MnO4- + 2H2O 🡪 5SO42- + 4H+ + 2Mn2+
■ It is a detection of SO2
■ Its angular in shape
Resonating structures:
 QUESTIONS
■ Show with the help of reactions, that the
behaviour of sulphur dioxide is very similar
to that of carbon dioxide.
■ What happens when sulphur dioxide is
passed through an aqueous solution of
Fe(III) salt?
■ How is the presence of SO2 detected ?
■ Comment on the nature of two S–O bonds
formed in SO2 molecule. Are the two S–O
bonds in this molecule equal ?
OXOACIDS OF SULPHUR
 p - BLOCK

SULPHURIC ACID
Preparation of Sulphuric acid –CONTACT PROCESS

1. Burning of sulphur or sulphide ore in air to generate SO2.

S + O2 -----🡪 SO2

2. Conversion of SO2 to SO3 by the reaction with oxygen in the

presence of a catalyst V2O5.
V 2 O5
2SO2 (g) + O2 (g) ----🡪 2SO3 (g) + H

3. Absorption of SO3 in H2SO4 to give Oleum (H2S2O7)

SO3 + H2SO4 🡪 H2S2O7 (oleum)

H2S2O7 + H2O 🡪 H2SO4
 p - BLOCK

Q. Give a flow chart for the formation/manufacture of

H2SO4.
Ans. The flow diagram is as follows
 p - BLOCK

Properties
a) Colourless, dense, oily liquid
b) Dissolves in water with large quantity of heat evolved. This is the
reason why concentrated acid must be added slowly into water with
constant stirring.
c) Chemical activities/chemical reaction/chemical properties of sulphuric
acid are a result of following characteristics
■ low volatility
■ strong acidic character
■ strong affinity for water
■ ability to act as an oxidizing agent

Q. How do you prove that it is a dibasic acid ?

Ans. This acid forms two series of salts: Normal sulphates and acid
sulphates (Bisulphates).
It can also be proved by following two reactions :
H2SO4 (aq) + H2O (l) 🡪 H3O+ (aq ) + HSO4- (aq)
HSO4- (aq) + H2O (l) 🡪 H3O+ (aq) + SO42- (aq)
 p - BLOCK
d) Because of its low volatility it is used in manufacture of
more volatile acids from their volatile salts
2MX + H2SO4 🡪 2HX + M2SO4 (X= F, Cl, NO3)

e) Concentrated H2SO4 is a strong dehydrating agent

🡪It is used to dry wet gases provided; they do not react
with it.
🡪It is used toHremove
2
SO4
water from organic compound
like charring of carbohydrates.
C12H22O11 ------🡪 12C + 11H2O

f) Strong oxidizing agent property of hot concentrated

H2SO4 is intermediate between phosphoric and nitric
acid.
Cu + 2H2SO4 (conc.) 🡪 CuSO4 + SO2 + 2H2O
C + 2H2SO4 (conc. ) 🡪 CO2 + 2SO2 + 2H20
3S + 2H2SO4 (conc. ) 🡪 3SO2 + 2H2O
 QUESTIONS

■ Why is Ka2<<Ka1 for H2SO4 in water?

 USES
Sulphuric acid is a very important industrial chemical.
A nation’s industrial strength can be judged by the
quantity of sulphuric acid it produces and consumes.
It is needed for the manufacture of hundreds of other
compounds and also in many industrial processes. The
bulk of sulphuric acid produced is used in the
manufacture of fertilisers (e.g., ammonium sulphate,
superphosphate). Other uses are in:
(a) petroleum refining (b) manufacture of pigments,
paints and dyestuff intermediates (c) detergent
industry (d) metallurgical applications (e.g., cleansing
metals before enameling, electroplating and
galvanising (e) storage batteries (f) in the
manufacture of nitrocellulose products and (g) as a
laboratory reagent.
 p - BLOCK

Group 17
includes:
1. Fluorine ( F )
2. Chlorine ( Cl )
3. Bromine ( Br )
4. Iodine ( I )
5. Astatine ( At ) ( Radioactive )
 PROPERTIES

■ Halogens are coloured - F2, has yellow,

Cl2 , greenish yellow, Br2, red and I2,
violet colour.
■ One curious anomaly is the smaller
enthalpy of dissociation of F2 compared to
that of Cl2
 QUESTIONS
Q: Why does F2 have a low F-F bond
dissociation enthalpy?

Q: Why are halogens 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.
PHYSICAL PROPERTIES
 p - BLOCK
Q. Why do halogens have maximum negative electron
gain enthalpy in their respective periods ?
Ans. Because of the small size and high effective
nuclear charge
They readily accept one electron to change their
configuration from ns2np5 to ns2np6.

Q. Although electron gain enthalpy of fluorine is less

negative as compared to chlorine but F2 is stronger
oxidizing agent than chlorine (Cl2)
Ans. Due to two reasons
🡪 Due to low enthalpy of dissociation of F-F
bond.
🡪 High hydration enthalpy of F-
Q. Why does Fluorine exhibit only one oxidation
state of -1 while others of the family exhibit
besides -1,+1,+3,+5 and +7 oxidation states ?
Ans . Fluorine atom has no d-orbitals in its valence
shell and therefore, cannot expand its octet.
Being the most electronegative it exhibits only -1
oxidation state. While the others do not face this
problem.
 p - BLOCK
GROUP 1 [Aashi Sharma, Abhishree, Akshita, Antara, Dafiya]
Q. What are the causes of anomalous behaviour of fluorine ?

GROUP 2 [Deeksha, Diya , Fiza, Hiba , Keiara ]

Q. Why are halogens coloured?

GROUP 3 [Krithika, Nikitha, ritu , Rushda , Sai Bhavika]

Q. Why does fluorine have low bond dissociation enthalpy?

GROUP 4 [Sanjana, Sanjanaa Sriram, sarah, Saumya, Savannah]

Q. Why is electron gain enthalpy of chlorine more negative than that of
fluorine?

GROUP 5 [Shamita, Shehzeen, Shreya Shree, Syeda Zainab, Tanisha]

Q. Explain why fluorine is the strongest oxidizing agent amongst group
17.
Reactivity of Hydrogen towards Halogens. p - BLOCK

1. They form Hydrogen Halides. H2+X2 🡪 2HX

2. Stability of Halides decreases down the group. HF is most
stable.
3. Acid strength increases down the group. HF is most
reactive.
4. Acid strength 🡪 HF < HCl < HBr < HI

Q. Hydrogen Fluoride is liquid while all other hydrogen halide

are gases.
Ans.
Fluorine being the most electronegative element is capable of
forming hydrogen bonds and hence it is in a more
compact state and i.e. liquid.
PHYSICAL PROPERTIES OF HX
Reactivity of oxygen towards halogens:
1. When oxygen combines with halogens, it forms oxides
except when oxygen and Fluorine combine together
the compound formed called oxygen fluoride..
2. Fluorine and oxygen forms two compounds OF2 and
O2F2. OF2 is thermally stable. 🡪 Both of them are good
fluorinating agents
3. Chlorine forms oxide with the formula Cl2O, ClO2,
Cl2O6, Cl2O7. ClO2 is a very good bleaching agent for
paper pulp and textile and in water treatment.
4. Bromine oxides are the least stable halogen oxides
which exist only at low temp. They are powerful
oxidizing agents. Common formulae for Bromine oxides
are Br2O, BrO2, BrO3.
5. Iodine oxides are insoluble solids and decompose on
heating. Their oxides have the formula I2O4, I2O3 and
I2O7. I2O5 is a strong oxidising agent and is used in the
estimation of carbon monoxide.
 p - BLOCK
Reactivity of Halogens towards metals.

■ Halogen and metals form Metal Halides. For

example, Magnesium with Bromide form
Magnesium Bromide.
Mg + Br2 🡪 MgBr2
■ Ionic character decreases down the group.
That means MF is more ionic.
MF> MCl > MBr >MI
■ If a metal exhibits more than one oxidation
state than the halide in higher oxidation state
is more covalent i.e. SnCl4, PbCl4, SbCl4 and
HF6 are more covalent than SnCl2, PbCl2, SbCl
and LiF4.
 p - BLOCK

CHLORINE
Methods for the preparation of Chlorine.

■ MnO2 + 4HCl 🡪 MnCl2 + Cl2 + 2H20

■ 4NaCl + MnO2 + 4H2SO4 🡪 MnCl2 + 4NaHSO4 + 2H2O + Cl2
■ 2KMnO4 + 16 HCl 🡪 2KCl + 2MnCl2 + 8H2O + 5Cl2

Q. Give the methods of manufacture of chlorine.

Deacon’s process

■ When HCl gas is treated with atmospheric oxygen in presence of

CuCl2 as catalyst at 723K we get chlorine gas.
■ 4HCl + O2 🡪 2Cl2 + 2H2O

Electrolytic Process

■ It is prepared by electrolysis of Brine i.e. concentrated NaCl

solution. Chlorine is obtained at anode.
 p - BLOCK
Properties of chlorine

■ Greenish yellow gas with pungent and suffocating smell

■ Soluble in water
■ Heavier in air
■ It reacts with metals and non-metals to form chlorides
2Al + 3Cl2 🡪 2AlCl3
2Na + Cl2 🡪 2NaCl
2Fe + 3Cl2 🡪 2FeCl2
P4 + 6Cl2 🡪 4PCl3
S8 + 4Cl2 🡪 4S2Cl2
■ It has high affinity for hydrogen. Therefore, it combines
with compounds containing hydrogen and hydrogen itself
to give HCl.
H2 + Cl2 🡪 2HCl
 p - BLOCK
Q. Give two or three reactions to show that chlorine is very fond of hydrogen.
Ans. H2 + Cl2 🡪 2HCl
H2S + Cl2 🡪 2HCl + S
C10H16 + 8Cl2 🡪 16HCl + 10C

■ Reaction of ammonia with chloride

8NH3 + 3Cl2 🡪 6NH4Cl + N2
(excess)
NH3 + 3Cl2 🡪 NCl3 + 3HCl
(excess)

■ Reaction of ammonia alkalis

2NaOH (cold , dilute) + Cl2 🡪 NaCl + NaOCl + H2O
6NaOH (hot, conc) + 3Cl2 🡪 5NaCl + NaClO3 + 3H2O

■ Reaction with dry slaked lime

2Ca(OH) 2 + 2Cl2 🡪 Ca(OCl) 2 + CaCl2 + 2H2O

Q. Give the formula of Bleaching powder and equation for its equation .
Ca(OCl) 2 . CaCl2. Ca(OH)2. 2H20
Q. What happens to chlorine water on long standing ?
Ans.
■ It looses its yellow colour due to the formation of HCl and HOCl. This HOCl gives
nascent oxygen which is responsible for oxidizing and bleaching properties of
chlorine.
Cl2 + H2O ----🡪 HCl + HOCl
HOCl -----🡪 HCl + (O)
Q. Give equation showing the oxidation properties of chlorine.
Ans. 2FeSO4 + H2SO4 + Cl2 🡪 Fe2 (SO4) 3 + 2HCl
Na2SO3 + Cl2 + H2O 🡪 Na2SO4 + 2HCl
SO2 + 2H2O + Cl2 🡪 H2SO4 + 2HCl

Q. Give the equation to show the bleaching property of chlorine water.

Ans. Cl2 + H2O 🡪 2HCl + O
Coloured substance + O 🡪 colourless substance

Q. Where is chlorine water used for bleaching purposes ? and what type of Bleaching
action it has ?
Ans. It bleaches vegetable or organic matter in presence of moisture. It has permanent
bleaching effect.
 p - BLOCK

HYDROGEN CHLORIDE
Preparation in Lab :
■ NaCl + H2SO4 🡪 NaHSO4 + HCl
■ NaHSO4 + NaCl 🡪 Na2SO4 + HCl

Properties :
1. Colourless gas with pungent smell
2. Extremely soluble in water
HCl (g) + H2O (l) 🡪 H3O+ (aq) + Cl- (aq)
3. In aqueous solution it is called Hydrochloric acid.
4. It reacts with ammonia
NH3 + HCl 🡪 NH4Cl
5. It reacts with ammonia to give ammonium chloride (dense white fumes )
6. When three parts of concentrated HCl are mixed with one part of concentrated
HNO3 we get aqua regia. This is used in dissolving noble metals.
Au + 4H+ + NO3- + 4Cl- 🡪 AuCl4- + NO + 2H2O
3Pt + 16 H+ + 4NO3- + 18Cl- 🡪 3PtCl62- + 4NO + 8H2O
7. Hydrochloric acid decomposes salts of weaker acids
Na2CO3 + 2HCl 🡪 2NaCl + H2O + CO2
NaHCO3 + HCl 🡪 NaCl + H2O + CO2
Na2SO3 + 2HCl 🡪 2NaCl + H2O + SO2
 p - BLOCK

Oxoacids of Halogens
Due to high electronegativity and small size, chlorine forms only one oxoacid
HOF.
STRUCTURE OF OXOACIDS
Interhalogen compounds p - BLOCK
When one Halogen combines with other Halogen atom the compound formed is known as
Interhalogen compounds can have the following formula
XX’, XX’3, XX’5 and XX’7 where X is the larger halogen than X
 p - BLOCK
Interhalogen compounds
■ Most of the portion already covered.
■ Interhalogen compounds are prepared by direct combination of the two halogens.
The product formed depends upon the conditions given:

■ As the ratio between radii of X and X′ increases, the number of atoms per
molecule also increases.
■ Their physical properties are intermediate which means that the of constituent’s
halogens except their melting point and boiling point are little higher than
expected.
■ Interhalogen compounds are more reactive than halogen except Fluorine because
X-X’ bond in interhalogens is weaker than X-X bond in halogens except F-F’ bond.
■ All of them undergo hydrolysis
■ XX’ + H2O → HX’ + HOX
■ Their structure can be explained VSEPR Theory.
■ XX3 has bent ‘T’ shape.
■ XX5 → square pyramidal
■ IX7 → pentagonal bipyramidal
Deduce the molecular shape of BrF3 on the basis of VSEPR theory.

The central atom Br has seven electrons in the valence shell. Three of
these will form electron-pair bonds with three fluorine atoms leaving
behind four electrons. Thus, there are three bond pairs and two lone
pairs. According to VSEPR theory, these will occupy the corners of a
trigonal bipyramid. The two lone pairs will occupy the equatorial
positions to minimise lone pair-lone pair and the bond pairlone pair
repulsions which are greater than the bond pair-bond pair repulsions.
In addition, the axial fluorine atoms will be bent towards the equatorial
fluorine in order to minimise the lone-pair-lone pair repulsions. The
shape would be that of a slightly bent ‘T’.
 REASONING QUESTIONS

■ Why is ICl more reactive than I2 BUT F2 is

more reactive than ClF ?
 p - BLOCK

GROUP 18

■ Helium (He)
■ Neon (Ne)
■ Argon (Ar)
■ Krypton (Kr)
■ Xenon (Xe)
■ Radon (Rn)
1. All noble gases except radon occur in nature.
2. Radon is obtained as a decay product of Radium

3. The general configuration is ns2np6 and are noble gases

because they generally do not interact with most of the
elements.
4. Due to stable configuration, they have very high ionization
enthalpy.
5. They are monotonic, colorless and sparingly soluble in
water.
6. They have low melting and boiling points because of only
type of inter-atomic interaction in these elements is weak
dispersion forces.
7. Helium has lowest boiling point of 4.2K and has an unusual
property of diffusing through most commonly used gas
materials like rubber, glass or plastics.

p - BLOCK
 10. Neil Bartlett, prepared a red compound which is
formulated as O2+PtF6–. He, then realised that the first
ionisation enthalpy of molecular oxygen (1175 kJmol–1) was
almost identical with that of xenon (1170 kJ mol–1). He
made efforts to prepare same type of compound with Xe and
was successful in preparing another red colour compound
Xe+PtF6– by mixing PtF6 and xenon.
11. Xenon forms three fluorides under three specific conditions

12. Another method of preparation of XeF6 is

p - BLOCK
14. They are powerful fluorinating agents and are readily
hydrolised by water.

There structures are deduced from VSEPR theory

XeF2 - linear
XeF4 – square planar
XeF6 – distorted octahedral

15. Xenon fluorides react with fluorides to form cationic species

and fluoro anions.

p - BLOCK
 p - BLOCK

Hydrolysis of XeF4 and XeF6

1. The hydrolysis is shown as follows

2. Partial hydrolysis of XeF6 gives the following

3. XeO3 is a colorless explosive solid with pyramidal
structure
4. XeF4 is a colorless volatile liquid with square pyramidal
structure

p - BLOCK
■ Uses :
Helium is a non-inflammable and light gas. Hence, it is used in filling
balloons for meteorological observations. It is also used in
gas-cooled nuclear reactors. Liquid helium (b.p. 4.2 K) finds use as
cryogenic agent for carrying out various experiments at low
temperatures. It is used to produce and sustain powerful
superconducting magnets which form an essential part of modern
NMR spectrometers and Magnetic Resonance Imaging (MRI)
systems for clinical diagnosis. It is used as a diluent for oxygen in
modern diving apparatus because of its very low solubility in blood.
Neon is used in discharge tubes and fluorescent bulbs for
advertisement display purposes. Neon bulbs are used in botanical
gardens and in green houses.
Argon is used mainly to provide an inert atmosphere in high
temperature metallurgical processes (arc welding of metals or
alloys) and for filling electric bulbs. It is also used in the laboratory
for handling substances that are air-sensitive.
There are no significant uses of Xenon and Krypton. They are used in
light bulbs designed for special purposes.
 p - BLOCK
Q. Why are noble gases least reactive?
OR
Why are they considered inert?
Ans. 1. Because of their noble gas configuration i.e. ns2np6
2. High ionization enthalpy and more positive electron gain enthalpy.

Q. What made us believe that inert or noble gases can also interact?
Ans. 1. Neil Bartlett observed the reaction of a noble gas.
2. He prepared a red compound with the formula O2+PtF6-
3. This compound made him realize that the first ionization enthalpy of
molecular oxygen (1175 KJ/mol) was almost identical with that of
Xenon (1170 KJ/mol)
4. Therefore, he made compound with Xenon and was successful in
making another red coloured compound.
Xe+PtF6- by mixing PtF6 and Xenon
5. This is how many compounds related to Xenon have been
synthesized.

Q: What inspired N. Bartlett for carrying out reaction between Xe and

PtF6?
Q: Does the hydrolysis of XeF6 lead to a
redox reaction?
A: No, the products of hydrolysis are XeOF4
and XeO2F2 where the oxidation states of all
the elements remain the same as it was in
the reacting state.
Q: Why is helium used in diving apparatus?
Q: How are XeO3 and XeOF4 prepared?
Q: Give the formula and describe the
structure of a noble gas species which is
isostructural with:
(i) ICl4– (ii) IBr2– (iii) BrO3–
Q: Why do noble gases have comparatively
large atomic sizes?

Q: List the uses of neon and argon gases