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7. P- BLOCK ELEMENTS
Introduction

The p-block elements are placed in groups 13 to 18 of the periodic table. Their valence shell electronic configuration is
ns 2 np1 6 (except He which has 1 s 2 configuration). The properties of p -block elements like that of others are greatly
influenced by atomic sizes, ionization enthalpy, electron gain enthalpy and electro negativity. In addition, the presence of
all the three types of elements; metals, metalloids and non-metals brings diversification in chemistry of these elements.

As we have learnt the chemistry of elements of Groups 13 and 14 of the p -block of periodic table in class XI,
you will learn the chemistry of the elements of subsequent groups in this Unit.

GROUP 15 ELEMENTS
Group 15 includes nitrogen, phosphorus, arsenic, antimony and bismuth. Nitrogen and phosphorus are non-
metals, arsenic and antimony metalloids and bismuth is a typical metal.

Occurrence : Molecular nitrogen comprises 78% by volume of the atmosphere. In the earth’s crust, it occurs as sodium
nitrate, NaNO 3 (called Chile saltpetre) and potassium nitrate (Indian saltpetre). It is found in the form of proteins in plants
and animals. Phosphorus occurs in minerals of the apatite family Ca 9  Po 4 6 CaX 2  X 2  F, Cl or OH  , Fluraptile fam
ily Ca 9  Po 4 6 CaF2 . Phosphorus is an essential constituent of animal and plant matter. It is present in bones as well as in
living cells. Phosphoproteins are present in milk and eggs. Arsenic, antimony and bismuth are found mainly as sulphide
minerals.

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

Atomic and Ionic Radii – Covalent and ionic (in a particular state) radii increase down the group.But there is
considerable increase in covalent radius from N to P and from As to Bi only a small increase in covalent radius is
observed.

Ionization Enthalpy – Ionization enthalpy decreases down the group due to gradual increase in atomic size. The
ionization enthalpy of the group 15 elements is much greater than that of group 14 elements in the corresponding periods.

Electro negativity – The electro negativity value, in general, decreases down the group with increasing atomic size.

Physical Properties – All the elements of this group are polyatomic. Dinitrogen is a diatomic gas while all others are
solids. Metallic character increases down the group. Nitrogen and phosphorus are non-metals, arsenic and antimony are
metalloids and bismuth is a metal. The boiling points, in general, increase from top to bottom in the group but the melting
point increases upto arsenic and then decreases upto bismuth. Except nitrogen, all the elements show allotropy

Oxidation states.The common oxidation states of these elements are -3, +3 and +5. Bismuth hardly forms any compound
in -3 oxidation state. In the case of nitrogen, all oxidation states from +1 to +4 tend to disproportionate in acid solution.
For example, 3HNO 2  HNO 3 + H 2 O + 2NO

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Similarly, in case of phosphorus nearly all intermediate oxidation states disproportionate into +5 and -3 both in
alkali and acid. However +3 oxidation state in case of arsenic, antimony and bismuth becomes increasingly stable with
respect to disproportionate.

Anomalous properties of nitrogen

Nitrogen differs from the rest of the members of this group due to its small size, high electronegativity, high ionization
enthalpy and non-availability of d orbitals. Nitrogen has unique ability to form multiple bonds with itself and with other
elements having small size and high electronegativity. Heavier elements of this group do not form p  p bonds as
their atomic orbitals are so large and diffuse that they cannot have effective overlapping. Thus, nitrogen exists as a
diatomic molecule with a triple bond (one s and two p ) between the two atoms. Its bond enthalpy (941.4 kJ mol 1 ) is
very high. Phosphorus, arsenic and antimony form single bonds as P-P. As-As and Sb-Sb while bismuth forms metallic
bonds in elemental state. However, the single N-N bond is weaker than the single P-P bond because of high interelectronic
repulsion of the non-bonding electrons.

Chemical properties

(i) Reactivity towards hydrogen: All the elements of Group 15 form hydrides of the type EH 3 where E = N. P. As. Sb
or Bi. Some of the properties of these hydrides are shown in Table. The hydrides show regular gradation in their
properties. The stability of hydrides decreases from NH 3 to BiH 3 which can be observed from their bond dissociation
enthalpy hence reducing character increases.Ammonia is only a mild reducing agent while BiH 3 is the strongest reducing
agent amongst all the hydrides. Basicity also decreases in the order NH 3 > PH 3 > AsH 3 > SbH 3  BiH 3 .

Properties of Hydrides of Group 15 Elements

Property NH 3 PH 3 AsH 3 SbH 3 BiH 3

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 ( o ) 107.8 93.6 91.8 91.3 -

-46.1 13.4 66.4 145.1 278

 f H  f / kJmol 1

 diss ( E  H ) / kJ mol 1
389 322 297 255 -

(ii) Reactivity towards oxygen : All these elements form two types of oxides : E2O3 and E2 O5 . The oxide in the higher
oxidation state of the element is more acidic than that of lower oxidation state. The oxides of the type E2 O3 of nitrogen
and phosphorus are purely acidic, that of arsenic and antimony amphoteric and those of bismuth predominantly basic.

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(iii) Reactivity towards halogens: These elements react to form two series of halides: EX 3 and EX 5 . Nitrogen does not
form pentahalide due to non-availability of the d orbitals in its valence shell. In case of nitrogen, only NF 3 is known to
be stable.

(iv) Reactivity towards metals: All these elements react with metals to form their binary compounds exhibiting -3
oxidation state, such as, Ca3 N 2 (calcium nitride) Ca3 P2 (calcium phosphide), Na3 As2 (sodium arsenide), Zn3 Sb2 (zinc
antimonide) and Mg 3 Bi2 (magnesium bismuthide)

e.g. - 6Li + N2 → 2 Li3N

6Ca + P4 → 2 Ca3P2

v) Action of oxidizing acid: Hot Conc. HNO3 has no action on nitrogen but reacts with phosphrous and arsenic to form
oxyacids. Antimny form its oxide.

e.g. P4 + 20HNO3 → 4H3PO4 + 20 NO2 + 4H2O

As4 + 20 HNO3 → 4H3AsO4 +20 NO2 + 4 H2O

Dinitrogen: - Preparation

i) Commercial Method:-Dinitrogen is produced commercially by the liquefaction and fractional distillation of air. Liquid
dinitrogen (B.P. 77.2 K) distils out first leaving behind liquid oxygen (b.p. 90 K).

ii) Laboratory Method:-In the laboratory, dinitrogen is prepared by treating an aqueous solution of ammonium chloride
with sodium nitrite.

NH 4 Cl ( aq )  NaNO2 ( aq )  N 2 ( g )  2 H 2 O (1)  NaCl ( aq )

Small amounts of NO and HNO 3 formed in this reaction are impurities and can be removed by passing the gas through
aqueous sulphuric acid containing potassium dischromate.

iii) From Ammonium dichromate:-It can also be obtained by the thermal decomposition of ammonium dichromate.

( N H 4 ) 2 C r2 O 7  H
ea t
 N 2  4 H 2 O  C r2 O 3

iv) From Bleaching poweder

3CaOCl 2  NH 3 
 3CaCl 2  3H 2 O  N 2

Properties

i) Dinitrogen is a colourless, odourless, tasteless, chemical inert and non-toxic gas.

ii) Nitrogen atom has two stable isotopes: 7 14 N and 7 15 N .

iii) It has a very low solubility in water (23.2 cm 3 per litre of water at 273 K and l bar pressure) and low freezing and
boiling points.

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IV) Dinitrogen is chemically inert at room temperature because of the high bond enthalpy of N  N bond. Reactivity,
however, increases rapidly with rise in temperature.

v) At higher temperature, it directly combines with some metals like Li, Mg etc. to form predominantly ionic nitrides and
with non-metals, covalent nitrides. A few typical reactions are:

6Li  N 2  He a t
 2 L i3 N
3M g  N 2  He a t
 M g 3 N 2

 2NO

N 2  O 2 

vi) It combines with hydrogen at about 773 K in the presence of a catalyst (Haber’s Process) to form ammonia:

N 2 (g )  3H 2

(g )  
773 K

 2NH 3 (g ),H f   4 6 .1 k J m o l 1

Uses:

i) The main use of dinitrogen is in the manufacture of ammonia and other industrial chemicals containing nitrogen.

ii) Liquid dinitrogen is used as a refrigerant to preserve biological materials, food items and in cryosurgery.

iii) Dinitrogen dilutes the action of dioxygen in air and thus makes combustion much less rapid.

Compounds of Nitrogen:-Nitrogen forms important compounds like ammonia.nitric acid and oxides of nitrogen

AMMONIA
Preparation

Ammonia is present in small quantities in air and soil where it is formed by the decay of nitrogenous organic
matter e.g., urea.

 2 NH 3  H 2 O  CO2
NH 2 CONH 2  2 H 2 O  ( NH 4 )2 CO3 

i) Laboratory method: Ammonia is obtained from ammonium salts which decompose when treated with caustic
soda or lime.

2 NH 4 Cl  Ca (OH ) 2  2 NH 3  2 H 2 O  CaCl2

( NH 4 ) 2 SO4 2 NaOH  2 NH 3  2 H 2 O  Na2 SO4

ii) Manufacturing Method: Ammonia is manufactured by Haber’s process.


N 2 ( g )  3H 2 ( g )  2 NH 3 ( g )  f H   46.1 kJ mol 1

In accordance with Le Chatelier’s principle, high pressure would favour the formation of ammonia.

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Properties: Ammonia is a colourless gas with a pungent odour. Its freezing and boiling points are 198.4 and 239.7 K
respectively. It is soluble in water and basic in nature. Ammonia gas is highly soluble in water. Its aqueous solution is
weakly basic due to the formation of OH  ions.

Stracture: The ammonia molecule is trigonal pyramidal with the nitrogen atom at the apex. It has three bond pairs and
one lone pair of electrons as shown in the structure.

Reactions:

 NH 4  (aq )  OH  (aq )

NH 3 ( g )  H 2O  L  

It forms ammonium salts with acids, e.g., NH 4 Cl , ( NH 4 ) 2 SO4 , etc. As a weak base, it precipitates the
hydroxides of many metals from theirs salt solutions. For example,

ZnSO4 (aq )  2 NH 4OH ( aq )  Zn(OH ) 2 ( s )  ( NH 4 ) 2 SO4 (aq )

 white ppt 

FeCl3 (aq )  NH 4OH (aq )  Fe2O3 x H 2O ( s )  NH 4Cl (aq )

 brown ppt 

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Oxides of Nitrogen

Nitrogen forms a number of oxides in different oxidation states. The names, formulas, preparation and physical
appearance of these oxides are given in Table

Name Formula Oxidation Common method Physical appearance

state of Of preparation and chemical nature
Nitrogen
Nitrous oxide or N2O +1 Heat
NH 4 NO3   N 2O  2 H 2 O Colourless gas, neutral
Dinitrogen oxide
[Nitrogen (I) oxide]
Laughing Gas
Nitrogen monoxide or NO +2 2 NaNO2  2FeSO4  3H 2 SO4  Colourless gas,
Nitric Oxide neutral, reactive
[Nitrogen (II) oxide] Fe2 (SO4 )3  2 NaHSO4  2H 2 O  2 NO

Dinitrogen trioxide N 2 O3 +3 250 K

2 NO  N 2 O4   2 N 2 O3 Blue, solid, acidic
[Nitrogen (III) oxide]
Nitrogen dioxide NO2 +4 673 K
2 Pb( NO3 ) 2   4 NO2  2 PbO  O2 Brown gas, acidic,
[Nitrogen (IV) oxide reactive

Dinitrogen tetraoxide N 2 O4 +4 Cool

  N 2 O4 Colourless solid /
2 NO2  
[Nitrogen (IV) oxide] Heat liquid, acidic

Dinitrogen pentoxide N 2 O5 +5 4 HNO3  P4 O10  4 HPO3  2 N 2 O5 Colourless ionic soild,

[Nitrogen (V) oxide] unstable acidic

Structure of Oxides of Nitrogen

N O
dimeric structure
O N of NO

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NITRIC ACID

Nitrogen forms oxoacids such as H 2 N 2 O2 (hyponitrous acid), HNO2 (nitrous acid) and HNO3 (nitric acid). Amongst
them HNO3 is the most important.

Preparation

Laboratory Method: - In the laboratory nitric acid is prepared by distillation of KNO3 or NaNO3 and concentrated
H 2 SO4 .

NaNO3  H 2 SO4  NaHSO 4  HNO3

sodioum hydrogen sulphate

Large scale preparation: - It is prepared by Ostwald’s process. This method is based upon catalytic oxidation of NH 3
by atmospheric oxygen.

Pt / Rh gauge catalyst
4 NH 3 ( g )  5O2 ( g ) 
500 K , 9 bar
4 NO( g )  6H 2 O ( g )
( from air )

Nitric oxide thus formed combines with oxygen giving NO2 .

 2 NO2 ( g )
2 NO( g )  O2 ( g ) 

Nitrogen dioxide so formed, dissolves in water to give HNO3 .

3 NO2 ( g )  H 2 O ( I )  2 HNO3 (aq )  NO ( g )

NO thus formed is recycled for obtaining NO2- and the aqueous HNO3 can be concentrated by distillation by
forming 68 % by mass and futher concentration to 98% by dehydration with concentrated H 2 SO4 .

Properties

i) It is a colourless liquid (f. p. 231.4 K and b. p. 355.6 K). Laboratory grade nitric acid contains  68% of the HNO3 by
mass and has a specific gravity of 1.504.

ii) In the gaseous state, HNO3 exists as a planar molecule with the structure as shown.

iii) In aqueous solution, nitric acid behaves as a strong acid giving hydronium and nitrate ions.

HNO3 (aq)  H 2O (l )  H 3O  (aq )  NO3 (aq )

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iv) Concentrated nitric acid is a strong oxidising agent and attacks most metals except noble metals such as gold and
platinum. The nature of products of oxidation depend upon the concentration of the acid, temperature and the nature of
the material undergoing oxidation.

3Cu  8 HNO3 (dilute)  3Cu ( NO3 ) 2  2 NO  4 H 2 O

Cu  4 HNO3 (conc.)  Cu ( NO3 ) 2  2 NO2  2 H 2 O

S8 + 48HNO 3 → 8H2SO4 + 48 NO2 + 16 H2O

v) Concentrated nitric acid also oxidises non-metals and their compounds. Iodine is oxidized to iodic acid, carbon
dioxide, sulphur to H 2 SO4 , and phosphorus to phosphoric acid.

I 2  10 HNO3 ( dil )  2 HIO3  10 NO2  4 H 2 O

C  4 HNO3( conc )  CO2  2 H 2 O  4 NO2

vi) Brown Ring Test: The famililar brown ring test for nitrates depends on the ability of Fe2 to reduce nitrates to nitric
oxide, which reacts with Fe2 to form a brown coloured complex. The test is usually carried out by adding dilute ferrous
sulphate solution to an aqueous solution containing nitrate ion, and then carefully adding concertrated sulphuric acid along
the sides of the test tube. A brown ring at the interface between the solution and sulphuric acid layers indicates the
presence of nitrate ion in solution.

NO3  3Fe2   4 H   NO  3Fe3  2 H 2 O

[ Fe( H 2 O )6 ]2  NO  [ Fe ( H 2 O)5 ( NO )]2   H 2 O
(brown)

Uses: - The major use of nitric acid is in the manufacture of ammonium nitrate for fertilizers and other nitrates for use in
explosives and pyrotechnics. It is also used for the preparation of nitroglycerin, trinitrotoluene and other organic nitro
compounds. Other major uses are in the pickling of stainless steel, etching of metals and as an oxidizer in rocket fuels and
organic dyes.

Phosphorus

Allotropic forms: Phosphorus is found in many allotropic forms, the important ones being white, red and black.

White phosphorus: i) It is a translucent white waxy solid.

(ii)It is poisonous, insoluble in water but soluble in carbon disulphide.

(iii)It dissolves in boiling NaOH solution in an inert atmosphere giving PH 3 .

P4  3NaOH  3H 2O  PH 3  3NaH 2 PO2

(sodium hypophosphite)

iv) It catches fire in air due to oxidation of phosphours vapour and gives faint green glow and white fumes of P4O10.This is
called as chemi luminescence effect.

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White phosphorus is less stable and therefore, more reactive than the other solid phases under normal conditions because
of angular strain in the P4 molecule where the angles are only 60 o .

Red phosphorus: i) is obtained by heating white phosphorus at 573K in an inert atmosphere for several days. Red
phosphorus possesses iron grey luster.
(ii)It is odourless, non-poisonous and insoluble in water as well as in carbon disulphide.
(iii)Chemically, red phosphorus is much less reactive than white phosphorus. It does not glow in the dark.
(iv)It is polymer in which P4 tetra hedral units are held by covalent bonding.Hence,It has high melting point than white
phosphours

Black phosphorus: (i) It exist two forms   black phosphorus and   black phosphorus.
(ii)   Black phosphorus is formed when red phosphorus is heated in a sealed tube at 803K.While   black phosphours
is formed on heating at 453 K
PHOSPHINE (PH3)

Preparation

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

Ca3 P2  6 H 2O  3Ca (OH ) 2  2 PH 3 

Ca3 P2  6 HCl  3CaCl2  2 PH 3 

In the laboratory, it is prepared by heating white phosphorus with concentrated NaOH solution in an inert
atmosphere of CO2

When pure, it is non inflammable but becomes inflammable owing to the presence of P2 H 4 or P4 vapours.

Properties
i) It is a colourless gas with rotten fish smell and is highly poisonous.
ii) It explodes in contact with traces of oxidising agents like HNO3 , Cl2 and Br2 vapours.

PH3 + 4Cl2 → PCl5 + 3HCl

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iii) It is slightly soluble in water. The solution of PH 3 in water decomposes in presence of light giving red phosphorus
and H 2 .
iv) When reacted copper sulphate or mercuric chloride solution, the corresponding phosphides are obtained.

3CuSO4  2 PH 3  Cu3 P2  3H 2 SO4

3HgCl2  2 PH 3  Hg3 P2  6HCl

v) With acids, it forms phosphonium salts.

PH3 + HBr → PH4Br
vi) It dosent exhibit hydrogen bonding like NH3.

Phosphorus Halides

Phosphorus forms two types of halides, PX 3 ( X  F , Cl , Br , I ) and PX 5 ( X  F , Cl , Br ).

Phosphorus Trichloride

Preparation

i) It is obtained by passing dry chlorine over heated white phosphorus.

P4  6Cl2  4 PCl3

ii) It is also obtained by the action of thionyl chloride with white phosphorus.

P4  8SOCl2  4 PCl3  4 SO2  2 S 2 Cl2

Properties

i) It is a colourless oily liquid and hydrolyses in the presence of moisture.

PCl3  3H 2 O  H 3 PO3  3HCl

ii) It reacts with organic compounds containing –OH group such as CH 3 COOH , C 2 H 5 OH .

3CH 3COOH  PCl3  3CH 3COCl  H 3 PO3

3C2 H 5OH  PCl3  3C2 H 5Cl  H 3 PO3

iii) It has a pyramidal shape as shown, in which phosphorus is sp3 hydridised.

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Phosphorus Pentachloride

Preparation

i) Phosphorus pentachloride is prepared by the reaction of white phosphorus with excess of dry chlorine.

P4  10Cl2  4 PCl5

ii) It can also be prepared by the action of SO 2 Cl2 on phosphorus.

P4  10SO 2 Cl 2  4PCl5  10SO 2

Properties

PCl5 Is a yellowish white powder and in moist air, it hydrolyses to POCl3 and finally gets converted to phosphoric
acid.

PCl5  H 2 O  POCl3  2HCl

POCl3  3H 2 O  H 3 PO4  3HCl

When heated, it sublimes but decomposes on stronger heating.

Heat
PCl5   PCl3  Cl2

Finely divided metals on heating with PCl5 give corresponding chlorides.

2 Ag  PCl5  2 AgCl  PCl3

Sn  2 PCl5  SnCl4  2PCl3

Cl
Cl
240 pm

202 pm
P Cl

Cl
Cl

Bipyramidal structure of PCl5

It is used in the synthesis of some organic compounds, e.g., C 2 H 5 Cl , CH 3COCl.

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Oxyacids of Phosphorus

Phosphorus forms a number of oxoacids. The important oxoacids of phosphorus with their formulas, methods of
preparation and the presence of some characteristic bonds in their structures are given in Table.

Name Formula Oxidation state of Characteristic bonds Preparation

phosphorus and their number

Hypophosphorous H 3 PO2 +1 One P- OH White P4 + alkali

(Phosphinic) Two P-H
One P= O

Orthophosphorous H 3 PO3 +3 Two P- OH P2 O3  H 2 O

(Phosphonic) One P- H
One P=O

Pyrophosphorous H 4 P2 O5 +3 Two P- OH PCl3  H 3 PO3

Two P- H
Two P= O

Hypophosphoric H 4 P2 O6 +4 Four P- OH Red P4 + alkali

Two P= O
One P- P

Orthophosphoric H 3 PO4 +5 Three P- OH P4 O10  H 2 O

One P= O

Pyrophosphoric H 4 P2 O7 +5 Four P- OH Heat phosphoric acid

Two P= O
One P- O- P

Metaphosphoric ( HPO3 )n +5 Three P- OH Phosphorus acid +

Three P = O Br2 . Heat in a sealed
Three P- O- P tube

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Structure of some important oxoacids of Phosphorus

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In oxoacids phosphorus is tetrahedrally surrounded by other atoms. All these acids contain at least one P=O and one P-OH
bond. The oxoacids in which phosphorus has lower oxidation state (less than +5) contain, in addition to P=O and P-OH
bonds, either P-P (e.g., in H 2 P2 O6 ) or P-H (e.g., in H 3 PO2 ) bonds but not both.

The acids which contain P-H bond have strong reducing properties. Thus, hypophosphorous acid is a good reducing agent
as it contains two P-H bonds and reduces, for example, AgNO3 to metallic silver.

4 AgNO3  2 H 2 O  H 3 PO2  4 Ag  4 HNO3  H 3 PO4

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QUESTIONS (including Board questions)

1. What is the basicity of H 3 PO4 ?

2. What happens when H 3 PO3 is heated

3. What happens when PCl5 is heated?

4. Write a balanced equation for the hydrolytic reaction of PCl5 in heavy water.

5. What is the covalence of nitrogen in N 2 O5 ?

6. Bond angle in PH 4 is higher than that in PH 3 . Why?

7. What happens when white phosphorus is heated with concentrated NaOH solution in an inert
atmosphere of CO2 ?
8. Explain the structure of ammonia.
9. How is ammonia prepared in the laboratory?
10. How is ammonia manufactured?
11. Why does NH 3 act as a Lewis base?
12. Why pentahalides more covalent than trihalides?
13. Why is BiH 3 the strongest reducing agent amongst all the hydrides of Group 15 elements?
14. Distinguish between white phosphorus and red phosphorus.
15. Draw structure and write geometry of PCl3 and PCl5 (March 2013)
16. What is the action of following reagents on ammonia (March 2013)
(a) excess of air (b) excess of chlorine (c) Na metal
17. NF3 is possible but not NF5. Why ? (Oct 2013)
18. Draw the structure of H4P2O6 ( Oct 2013)
19. What is the action of following reagents on ammonia (March 2014)
(a) Nessler’s reagent (b) sodium metal
20. Explain Brown ring test with the help of chemical equation . ( March 2015)
21. Describe the laboratory method for the preparation of ammonia. (Oct 2015)
22. What is the action of hot and conc HNO3 on
(a) Arsenic (b) Antimony ( Oct 2014)
23. Draw the structure of (a) orthophosphoric acid (b) Pyrophosphoric acid (Oct 2014)
24. Explain how does nitrogen exhibit anomalous behaviour among group 15 elements? (March 2015)
25. Write four points of differences between properties of nitrogen and other elements of group 15 (March
2016)

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GROUP 16
Elements
Oxygen sulphur, selenium, tellurium and polonium constitute Group 16 of the periodic table. This is sometimes known as
group of chalcogens.

Occurrence – Oxygen is the most abundant of all the elements on earth. Oxygen forms about 46.6% by mass of earth’s
crust. Dry air contains 20.946% oxygen by volume.

However, the abundance of sulphur in the earth’s crust is only 0.03-0.1%. Combined sulphur exists primarily as
sulphates such as gypsum CaSO4 .2 H 2 O, Epsom salt MgSO4 .7 H 2 O, barite BaSO4 and sulphides such as galena PbS ,
zinc blende ZnS , copper pyrites CuFeS 2 . Trance of sulphur occur as hydrogen sulphide in volcanoes. Organic materials
such as eggs, proteins, garlic, onion, mustard, hair and wool contain sulphur.

Selenium and tellurium are also found as metal selenides and tellurides in sulphide ores.

Electronic Configuration : The elements of Group 16 have six electrons in the outermost shell and have ns 2 np 4 general
electronic configuration.

TRENDS IN PHYSICAL PROPERTIES: -

Atomic and Ionic Radii: Due to increase in the number of shells, atomic and ionic radii increase from top to bottom in
the group. The size of oxygen atom is, however, exceptionally small.

Ionisation 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 compound to those of Group 15 in the corresponding periods. This is
due to the fact that Group 15 elements have extra stable half-filled p orbitals electronic configurations.

Electron Gain Enthalpy: Group 16 elements have high values of electron gain enthalpy, it has less negative electron gain
enthalpy than sulphur. However, from sulphur onwards the value decreases upto polonium. On moving down the group,
electron gain enthalpydecreas from S to Po. Oxygen has less negative electron gain enthalpy due to high electron
negativity, small size and high electron density, so that incoming electron is repelled.

Electronegativity: Next to fluorine, oxygen has the highest electronegativity value amongst the elements. Within the
group, electronegativity decreases with an increase in atomic number. This implies that the metallic character increases
from oxygen to polonium.

Metallic character: Oxygen and sulphur are non-metals, selenium and tellurium metalloids, whereas polonium is a
metal. Polonium is radioactive and is short lived (Half-life 13.8 days).

Allotropy: All these elements exhibit allotropy. Oxygen exists as O2 and ozone as O3. Sulpher as α, β and γ. Se in
crystalline and amorphous form.

Melting and boiling point: The melting Oxygen exists as O 2 and ozone as O3. Sulpher as α, β and γ. Se in crystalline
and amorphous form.and boiling points increase with an increase in atomic number down the group. The large
difference between the melting and boiling points of oxygen and sulphur may be explained on the basis of their atomicity;
oxygen exists as diatomic molecule (O2 ) whereas sulphur exists as polyatomic molecule ( S8 ) .Oxygen exists as O 2 and
ozone as O 3. Sulpher as α, β and γ. Se in crystalline and amorphous form.

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Catenation: Group 16 element has less tendancy for catenation and it decrease for oxygen to polonium.
Oxidation States:

The elements of Group 16 exhibit a number of oxidation states. The stability of – 2 oxidation state decreases down the
group. Polonium hardly shown – 2 oxidation state. Since electronegativity of oxygen is very high. It shows only negative
oxidation state as – 2 except in the case of OF2 where its oxidation state is + 2. Other elements of the group exhibit + 2, +
4, + 6 oxidation states but + 4 and + 6 are more common. Sulphur, selenium and tellurium usually show + 4 oxidation
state in their compounds with oxygen and + 6 with fluorine.

Some Physical Properties of Group 16 Elements

Property O S Se Te Po

Atomic number 8 16 34 52 84

Atomic mass/g mol 1 16.00 32.06 78.96 127.60 210.00

Electronic configuration ( He )2 s 2 2 p 4 ( Ne)3s 2 3 p 4 ( Ar )3d 10 4 s 2 4 p 4 ( Kr )4d 10 5s 2 5 p 4 ( Xe)4 f 14 5d 10 6 s 2 6 p 4

Covalent radius/ ( pm) a 66 104 117 137 146

Ionic radius, E 2  /pm 140 184 198 221 230 b

Electron gain enthalpy, / -141 -200 -195 -190 -183

1
eg H kJ mol

Ionisation enthalpy (1 H1 ) / 1314 1000 941 870 812

kJ mol 1

Electronegativity 3.50 2.44 2.48 2.01 1.76

Density / g cm3 (298 K) 1.32 c 2.06 d 4.19 e 6.25 

Melting points / K 55 393 490 725 520

Boiling points / K 90 718 958 1260 1235

Oxidation states* -2,-1,1,2 -2,2,4,6 -2,2,4,6 -2,2,4,6 2,4

d e
“Single bond : “Approximate value : ‘At the melting point : Rhombic sulphur Hexagonal grey : Monocinic form, 673 K.
*Oxygen shows oxidation states of +2 and +1 in oxiygen fluorides OF2 and O2 F2 respectively.

CHEMICAL PROPERTIES:
A) All the elements are reacting but reactivity decreases down the group.
1) Action of alkallies - 3S + 6NaOH ⟶ Na2SO3 + 2Na2S + 3H2O
2) Action of air – S + O2 ⟶ SO2 Se + O2 ⟶ SeO2
3) Action of acids - S + 6NHO3 ⟶ H2SO 4 + 6NO 2 + 2H2O

Se + 4HNO 3 ⟶ H2SeO3 + 4NO2 + H2O

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4) Action of non-metals - 2S + C ⟶ CS2 S + H2 ⟶ H2S

Se + 2Cl2 ⟶ SeCl4 S + 3F2 ⟶ SF6
5) Action of metals - Cu + S ⟶ CuS Cd + Se ⟶ CdSe

B) Hydrides, halides and oxides.

1) Reactivity with hydrogen –

(i) All the elements of group 16 react with hydrogen and form hydrides of the type H2M where M=O,S,Se,Te and Po.
(ii) The hydrides of these elements show regular trends in their physical and chemical properties.
2) Volatility – Volatility of hydrides increase from H2O to H2S and then decreases. H2O  H2S  H2Se  H2Te
At ordinary temperature H2O is a liquid while all other hydrides are gases.
3) Thermal stability –
(i) The thermal stability of hydrides decreases in the order of H2O  H2S  H2Se  H2Te.
(ii) Since atomic size increases from O to Te, the tendency to form hydride bond, M-H decreases. Hence M-H bond in
O-H is the strongest and in Te-H the weakest. Therefore thermal stability decreases from H2O to HeTe. For example, H2O
dissociates at 2073-2273 K and H2S dissociates at 873 K.
4) Acidic character –
(i) the hydrides of group 16 elements are weakly acidic and acidic strength increases from H2O to H2Te.
(ii) These hydrides behave diprotic weak acids in aqueous solutions. M-H bond in hydrides is polar; hence they
dissociate forming H3O+ ions.
H2S (aq) + H2O (1) ⇌ H3O+ (aq) + HS – (aq);
HS- (aq) + H2O (1) ⇌ H3O+ (aq) + S2- (aq)
(iii) On reaction with base, these hydrides from salts.
H2S + NaOH ⟶ NaHS + H2O
Sodium hydrosulphide
NaHS + NaOH ⟶ Na2S + H2O
Sodium sulphide
(iv) Since M-H bond strength decreases, bond enthalpy decreases, acidic character increases.
5) Reducing power –
(i) Except H2O, all hydrides of group 16elements are reducing agents.
(ii) Reducing power increases from H2S to H2Te.
(iii) Reducing power of the hydrides is due to their less stability and tendency to dissociate, which increases
from H2S to H2Te.

C) Reactivity towards halogens –

(i) The group 16 elements with halogens from a large number of halides of the type EX2, EX4 and EX6 where E
is an element of the group and X is a halogen.
(ii) Oxygen forms mono, di,tera and hexa halides and their stability decreases in the order of F->Cl- >Br-> I-
(iii) In hexahalides, hexafluorides are only stable halides. SF6 is exceptionally stable, which has sp3d2
hybridisation. (iv) Tetrahalides have sp3d hybridization and trigonal bipyramidal structure and seesaw
geometry. SF4 is gaseous. SeF4 is a liquid while TeF4 is a solid.
(v) All elements from dihalides having tetrahedral structure due to sp3 hybridisation. These dihalides have a
tendency to undergo disproportionation.

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Anomalous behavior of oxygen

Oxygen the first member of the group 16 differs considerably from other elements in several properties. The
anomalous nature of oxygen is due to (i) its small size (ii) its high electronegativity (iii) the absence of vacant d-orbitals
in its valence shell.

Some important points of difference between oxygen and other elements of group 16 are as follows.

i) Physical state: Oxygen is a gas at ordinary temperature while other members are solids.

ii) Atomicity: Oxygen molecule is diatomic (O2 ) . While molecules of other elements of group 16 are polyatomic, for
example, sulphur and selenium form octatomic molecules ( S8 and Se8 ) and have puckered ring structure.

iii) Magnetic behavior: Molecular oxygen (O2 ) is paramagnetic in nature. While other elements are diamagnetic. The
paramagnetic nature of O2 is explained on the basis of molecular orbital theory.

iv) Oxidation states: oxygen shown an oxidation state of -2 in most of its compounds. Due to absence of vacant d
orbitals it cannot exhibit higher oxidation state. The other elements of the group exhibit +2, +4 and +6 oxidation states in
addition to -2 oxidation states.

v) Hydrogen bonding: Due to higher value of electronegativity, oxygen is capable of forming hydrogen bonding in its
compounds like water, alcohols, carboxylic acids etc. Other elements of the group being much less electronegative do not
form hydrogen bonds.
vi) Nature of compounds: The compounds of oxygen are more ionic than those of the other elements of the group. Thus
O 2  is very common but S 2 , Se 2 and Te 2 are less common.
vii) Multiple bonds: Oxygen is capable of forming p  p multiple bonds with elements of comparable size like
carbon, nitrogen etc. The other elements of the group do not show much tendency to form such multiple bonds.
viii) Hydrides: The hydrides of oxygen, i.e. H 2 O is a liquid at room temperature while the hydrides of all other
elements are gases.

Dioxygen
Preparation- General Method
Dioxygen can be obtained in the laboratory by the following ways:
(i) By heating oxygen containing salts such as chlorates, nitrates and permanganates.
H eat
2 K C lO 3  MnO2
 2 K C l  3 O 2
(ii) By the thermal decomposition of the oxides of metals low in the electrochemical series and higher oxides of some
metals.
2 Ag 2O(s)  4 Ag ( s)  O2 ( g ) ; 2 Pb3O4 ( s)  6 PbO( s)  O2 ( g )
2 HgO( s)  2 Hg ( I )  O2 ( g ) ; 2 PbO2 ( s)  2 PbO( s)  O2 ( g )
(iii) Hydrogen peroxide is readily decomposed into water and dioxygen by catalysts such as finely divided metals and
manganese dioxide.

2 H 2 O2 ( aq )  2 H 2 O (1)  O2 ( g )
On large scale it can be prepared from water or air. Industrially, dioxygen is obtained from air by first removing
carbon dioxide and water vapour and then, remaining gases are liquefied and fractionally distilled to give dinitrogen and
dioxygen.

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Properties of Dioxygen
i) Dioxygen is a colourless and odourless gas and testless gas.
ii) Its solubility in water is to the extent of 3.08 cm 3 water at 293 K which is just sufficient for the vital support of marine
and aquatic life. It liquefies at 90 K and freezes at 55 K.
16
iii)Oxygen atom has three stable isotopes O,17 O,18 O
iv)Dioxygen directly reacts with nearly all metals and non-metals except some metals (e.g. Au, Pt) and some noble gases.
v) It is heavier than air.
vi) It is paramagnetic in nature

Chemical Properties
Due to high bond dissociation energy (493.4 kJmol 1 ) dixoygen is quite stable at ordinary temperature and does
not show much chemical reactivity. Hence, the reactions of oxygen require initiations by external heating. At higher
temperature, the dissociation of the molecule takes place and it combines with large number of elements and shows a
variety of oxidation reactions.

1. Support of combustion: Dioxygen is not combustible but supports combustion.

2. Reaction with metals: Different types of metals combine with dioxygen under different conditions to form their
oxides.
(a) Active metals like Na, K, and Ca etc react with dioxygen event at ordinary temperature and form their
oxides.
i) 2Ca  O2 
 2CaO ii) 4 Na  O2 
 2 Na2 O (Sodium oxide)
(b) Magnesium burns in dioxygen to form magnesium oxide.
2 Mg  O2 
 2 MgO
(c) Metals like Al, Fe etc combine with dioxygen on heating to form their oxides.
i) 4 Fe  3O2 
 2 Fe2 O3 ii) 4 Al  3O2 
 2 Al2 O3

3. Reaction with non-metals: Several non metals burn brightly in dioxygen and from their respective oxides. For
example,
i) S  O2 
 SO2 ii) P4  5O2 
 P4 O10
iii) 2C  O2 
 2CO Iv) C  O2 
 CO2
(Limited) (Excess)

v) 2 H 2  O2 
 2H 2O Vi) N 2  O2 
 2 NO
Nitric Oxide
4. Reaction with compounds: Dioxygen can oxidize a large number of compounds under suitable sets of
conditions.

i) Reactions with ammonia: It oxidizes ammonia into nitric oxide in presence of red hot platinum guaze
which acts as a catalyst.
1073K
4 NH3  5O2 Pt
 4NO  6H 2 O
ii) Reaction with hydrogen chloride: It oxidizes hydrogen chloride gas into chlorine gas at 700K in
presence of cupric chloride as a catalyst

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700 K
4HCl( g )  O2 ( g ) 
CuCl2
 2H2O( g )  2Cl2( g )
iii) Reaction with sulphur dioxide: Dioxygen oxidizes sulphur dioxide into sulphur trioxide ( SO3 ) at
725 K in presence of finely divided platinum.
725 K
2SO2( g )  O2 ( g ) 
Pt
 2SO3 ( g )
iv) Reaction with carbon disulphide: Carbon disulphide burns in dioxygen to form carbon dioxide and
sulphur dioxide.
CS2  3O2 
 CO2  2 SO2

Classification of oxides:
Oxygen combines with a large number of metals and non-metals to form binary compounds. These binary
compounds are called oxides. Several elements form more than one type of oxides. For example carbon forms monoxide
as CO and dioxide as CO2 . These oxides widely differ in their properties. The oxides of elements may differ in their
bonding also. Oxides are classified as acidic oxides, basic oxides and amphoteric oxides.

1. Acidic oxides: The oxide which combines with water to give an acid is referred as acidic oxide. The acidic oxide is
formed by the combination of oxygen with non-metals. (It is binary compound of non-metal with oxygen) e. g.
CO2 , B2 O3 (boron trioxide), N 2 O5 (Nitrogen pentoxide), SO2 (Sulphur dioxide), SO3 (Sulphur trioxide), Cl2 O7
(chlorine heptoxide). These oxides when tested with water, they form acids.

i) CO2 ( g )  H2O (1) 

 H2CO3 ( aq ) ii) N2O5 ( g )  H2 O (1) 
 2HNO3 (aq)
Carbonic acid Nitric acid
iii) P4 O10 ( s )  6H2 O (1) 
 4H3 PO4 ( aq ) iv) Cl2 O7 ( g )  H2 O (1) 
 2HClO4 ( aq)
Phosphoric acid Perchloric acid
v) SO3  H 2 O 
 H 2 SO4
Sulphuric acid

2. Basic oxides: The oxide which combines with water to form a base is termed as basic oxide. The basic oxides are
formed by the combination of highly electro positive metals with oxygen and generally ionic in nature, e.g. CaO
(calcium oxide), Na2 O (sodium oxide), K 2 O (potassium oxide), MgO (Magnesium oxide).
i) CaO (S)  H2O (1) 
 Ca(OH )2 (aq) ii) Na2O ( s )  H2O (1) 
 2NaOH ( aq )
iii) BaO ( s)  H 2O (1) 
 Ba(OH )2 ( aq)

These oxides dissolve in water to give basic solution.

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3. Amphoteric oxides: The oxide which show both acidic and basic characteristics are called amphoteric oxides. The
oxides react with acids as well as bases to form salts. Amphoteric oxides are formed by the elements which lie on the
border line between metals and non-metals, e.g. Al2 O3 , SiO2 , ZnO , PbO, SnO etc.

Al2 O3 ( s )  6 HCl ( aq ) 
 2 AlCl3 ( aq )  3H 2 O (1)
Al2 O3 ( s )  6 NaOH ( aq )  3H 2 O 
 2 Na3 [ Al (OH ) 6 ] ( aq )
ZnO ( s )  2HCl ( aq ) 
 ZnCl2 ( aq )  H 2 O (1)
ZnO ( aq )  2 NaOH 
 Na2 ZnO2 ( aq )  H 2 O (1)
(Excess)

On moving from left to right in a period the nature of oxide changes from strongly basic to amphoteric and then to
strongly acidic. For example the oxides of the elements of third period exhibits the following gradation in their nature.
Acidic character increases, basic character decreases in a period.
Na2O MgO Al2O3 SiO2 P4O10 SO2 , Cl2 O
strongly basic basic amphotric weakly acidic acidic strongly acidic
There are some oxides which are neither acidic nor basic. Such oxides are known as neutral oxides. Examples of neutral
oxides are NO , N 2 O and CO.

Ozone (O3 )
Ozone is allotropic form of oxygen. It is too reactive to remain for long in the atmosphere at sea level. At a height
of about 20 kilometres, it is formed from atmosphere oxygen in the presence of sunlight. This ozone layer protects the
earth’s surface from an excessive concentration of ultraviolet (UV) radiations.

Preparation: Laboratory
When a slow dry stream of oxygen is passed through a silent electrical discharge, conversion of oxygen to ozone
(10%) occurs. The product is known as ozonised oxygen.
3O2  2O3 H (298 K )   142 kJ mol 1
Properties
1. Pure ozone is a pale blue gas, dark blue liquid and violet-black solid.
2. Ozone has a characteristic smell and in small concentrations it is harmless.
3. However, if the concentration rises above about 100 parts per million, breathing becomes uncomfortable resulting
in headache and nausea.

4. Ozone is thermodynamically unstable with respect to oxygen since its decomposition into oxygen results in the
liberation of heat (H is negative) and an increase in entropy (S is positive).
5. It acts as a powerful oxidising agent. For example, it oxidises lead sulphide to lead sulphate and iodide ions to
iodine.
i) PbS ( s )  4O3 ( g )  PbSO4 ( s )  4O2 ( g )

ii) 2KI( aq )  H 2 O  O3 (g) 

 2KOH( aq )  I 2 ( s)  O2 ( g )

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Sulphur
Allotropic Forms
Sulphur forms numerous allotropes of which the yellow rhombic (  sulphur) and monoclinic (  sulphur)
forms are the most important. The stable form at room temperature is rhombic sulphur, which transforms to monoclinic
sulphur when heated above 369 K.

1) Rhombic sulphur (  sulphur) :

This is a most common and most stable form of sulphur. This allotrope is yellow in colour, m.p. 385.8 K and
specific gravity 2.06. Rhombic sulphur crystals are formed on evaporating the solution of roll sulphur in CS 2 . It is
insoluble in water but dissolves to some extent in benzene, alcohol and ether. It is readily soluble in CS 2 .

2) Monoclinic sulphur (   sulphur):

Its m.p. is 393 K and specific gravity 1.98. It is soluable in CS 2 . This form of sulphur is prepared by melting
rhombic sulphur in a dish and cooling, till crust is formed. Two holes are made in the crust and the remaining liquid
poured out. On removing the crust, colourless needle shaped crystals of   sulphur are formed. It is stable above 369 K
and transforms into   sulphur below it. Conversely,   sulphur is stable below 369 K and transforms into   sulphur
above this. At 369 K both the forms are stable. This temperature is called transition temperature.

3) Plastic sulphur ( S  ) :
It is also called   sulphur. It is prepared by pouring boiling sulphur in cold water when plastic sulphur is
obtained. It is a soft rubber like amorphous mass. Its specific gravity is 1.95. It possesses no sharp melting point. It is
soluble neither in water nor in carbon disulphide. It is unstable and changes into rhombic form on standing. Plastic sulphur
consists consists of an open chain structure. The sulphur atoms are linked together to form open chain molecules. In such
a way that each sulphur atom is linked to two other sulphur atoms by covalent bonds.

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4) Milk of sulphur:
When flowers of sulphur are boiled with milk of lime, a mixture of calcium pentasulphide (CaS 5 ) and calcium
thiosulphate (CuS 2 O3 ) is formed. This mixture on being treated with hydrochloric acid gives a white amorphous
precipitate known as milk of sulphur.
3Ca (OH ) 2  12 S 
 2CaS5  CaS 2 O3  3H 2 O
(calcium pentasulphide ) (Calicum thi sup hate)
2CaS 2  CaS 2 O3  6 HCl 
 3CaCl2  3H 2 O  12 S
Milk ofsulphur
Milk of sulphur is soluble in CS 2 . It tends to revert to the rhombic variety on standing for long time. It is used in
medicine.

5) Colloidal sulphur:
Colloidal form of sulphur may be obtained by passing hydrogen sulphide through nitric acid or by treating sodium
thiosulphate solution with concentrated hydrochloric acid.
H 2 S  2 HNO3 
 2H 2O  2 NO2  S
Colloidal sulphur
Na2 S2O3  2 HCl 
 2 NaCl  SO2  H 2 O  S
(conc.) Colloidal sulphur
It may be obtained by treating hydrogen sulphide with sulphur dioxide.
2 H 2 S  SO2 
 2 H 2 O  3S
Colloidal sulphur
Colloidal sulphur changes into ordinary sulphur on heating or on keeping for long time. Variety of colours of colloidal
sulphur are obtained, depending upon size of the sulphur particles.

Compounds of sulphur

Sulphur dioxide:
Preparation
1. Sulphur dioxide is formed together with a little (6-8%) sulphur trioxide when sulphur trioxide when sulphur is
burnt in air or oxygen:
S ( s )  O2 ( g )  SO2 ( g )
2. In the laboratory it is readily generated by treating a sulphite with dilute sulphuric acid.
SO32 ( aq )  2 H  ( aq )  H 2 O(1)  SO2 ( g )
3. Industrially, it is produced as a by-product of the roasting of sulphide ores.
4 FeS 2 ( s )  110 2 ( g )  2 Fe2 O3 ( s )  8SO2 ( g )
The gas after drying is liquefied under pressure and stored in steel cylinders.

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Properties

1. Sulphur dioxide is a colourless gas with pungent smell and is highly soluble in water.
2. It liquefies at room temperature under a pressure of two atmospheres and boils at 263 K.
3. Sulphur dioxide, when passed through water, forms a solution of sulphurous acid.

SO2 ( g )  H2 O (1)  H2 SO3 (aq)
4. It reacts readily with sodium hydroxide solution, forming sodium sulphite, which then reacts with more sulphur
dioxide to form sodium hydrogen sulphite.
2 NaOH  SO2  Na2 SO3  H 2 O
Na2 SO3  H 2O  SO2  2 NaHSO3
5. Sulphur dioxide reacts with chlorine in the presence of charcoal (which acts as a catalyst) to give sulphury
chloride, SO2 Cl2 . It is oxidized to sulphur trioxide by oxygen in the presence of vanadium (V) oxide catalyst.

SO 2 ( g )  C l 2 ( g )  SO 2 C l 2 ( l )
2 SO 2 ( g )  O 2 ( g ) V
2 O5
 2 SO 3 ( g )
6. When moist, sulphur dioxide behaves as a reducing agent. For example, it converts iron (III) ions to iron (II) ions
and decolourises acidified potassium permanganate (VII) solution; the latter reaction is a convenient test for the
gas.
2 Fe3  SO2  2 H 2 O  2 Fe 2  SO42   4 H 

Uses:
(i) In refining petroleum and sugar (ii) in bleaching wool and silk and (iii) as an anti-chlor, disinfectant and
preservative. Sulphuric acid, sodium hydrogen sulphite and calcium hydrogen sulphite (industrial chemicals) are
manufactured from sulphur dioxide. Liquid SO2 is used as a solvent to dissolve a number of organic and inorganic

chemicals.

Structure of SO2 molecule

The molecule of SO2 has a bent structure with a O-S-O bond angle of 119 o , sulphur is sp 2 hybridized and the
lone pair of electrons of sulphur reduces the angle from 120 o C to 119 o . In the structure, each oxygen atom is joined to
sulphur by a  and a  bond. The  bonds between S and O are formed by sp 2  p overlap while one of the  bonds
arises from p  p overlap and other from p  d  overlap but even then both of the S-O bonds are identical
(143pm) due to resonance. It has following structure.

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Sulphuric acid

Manufacturing process: Sulphuric acid is important chemical used in many industries. It is also celled oil of vitriol in
ancient days.There are two manufacturing processes.
(a) Contact process (b) lead chamber process

(A) Contact process: This process involves following important steps.

(a) Preparation of SO2 : Sulphur or iron pyrites FeS 2 when burned in excess of air, SO2 is obtained.
S( g )  O2 ( g ) 
 SO2 ( g )
4 FeS2  11O2 
 2 Fe2 O3  8SO2

(b) Oxidation of SO2 to SO3 : In presence of atmospheric oxygen and a catalyst, V2 O5 , the SO2 gets oxidized to SO3 .
The reactions is reversible and exothermic

V2 O5
2 SO2 ( g )  O2 ( g )  
 2 SO3 H   196.6 KJ
The impurities like dust, moisture and arsenious oxide poison the catalyst hence the gases SO2 and O2 must be purified
before combining to form SO3 . The forward reaction involves decrease in volume, hence favoured by increase in
pressure. The optimum pressure used is 2-3 atm. As the forward reaction is exothermic it is favoured at low temperature,
optimum temperature used is around 723K and SO2 and O2 are taken in the ration 2:3

(c) Dissolution of SO3 in H 2 SO4 : Sulphur trioxide gas from catalytic converter is absorbed in 98%. H 2 SO4 to get
H 2 S 2 O7 , oleum (fuming sulphuric acid) SO3  H 2 SO4 
 H 2 S 2 O7 .
(d) Dilution of oleum, H 2 S 2 O7 : To convert oleum into sulphuric acid ( H 2 SO4 ) it is mixed with water to get
sulphuric acid of desired concentration. Sulphuric acid obtained by this process is 96-98% pure. Shows the flow chart for
industrial process of manufacturing H 2 SO4 .
H 2 S 2 O7  H 2 O 
 2 H 2 SO4

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(B) Lead chamber process: In this process a mixture of SO2 , NO and air is treated with steam to obtain H 2 SO4 .
Nitric oxide ( NO ) acts as a catalyst.
NO
2 SO2  O2  2 H 2 O  2 H 2 SO4
The above net reaction can be written as the sum of following reactions taking place in different steps.
 HNO3  3H 
a) 2 H 2 O  NO 
b) S  O2 
 SO2 (oxidation of sulphur )
c) 2 HNO3  2 SO2 
 H 2 O  NO  NO2  2 SO3
Nitric acid or NO2 is used to oxidize SO2 to SO3
or SO2  NO2 
 SO3  NO
d) SO3  H 2 O 
 H 2 SO4
Sulphur trioxide reacts with water to from H 2 SO4.
Properties
(1) It is a colourless, dense, oily liquid. It has specific gravity of 1.84 at 298K.
(2) Freezing point of sulphuric acid is 283K and the boiling point at 611K.
(3) Pure sulphuric acid has strong affinity for water and it dissolves in it with evolution of considerable amount
of heat. Therefore, care must be taken while preparing sulphuric acid solution from concentrated sulphuric acid.
The concentrated acid must always be added slowly into fine stream of water with constant stirring. Water is
never added to concentrated acid as acid spirts, due to formation of steam.
(4) It is a strong acid with powerful affinity for water, less volatile and acts as oxidizing agent.
(5) It is highly viscous due to hydrogen bonding.
(6) It is a dibasic acid.
In aqueous solution sulphuric acid ionizes in two steps.

 H   HSO4
(i) H 2 SO4 
 Ka1  10

 H   SO42 
(ii) HSO4 
 Ka2  1.2  102
(iii) HSO4  H 2 O 
 H 3 O   SO42

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The larger value of Ka1 ( Ka1  10) of H 2 SO4 shows more dissociation into H  and HSO4 . Greater the value of
dissociation constant ( Ka ) the stronger is the acid.
Dehydrating agent
Concentrated H 2 SO4 is a powerful dehydrating agent. Its corrosive action on skin is also due to dehydration of
skin which then burn and develops itching sensation.
Some reactions related to dehydration property of H 2 SO4 are as follows :
H 2 SO4 H 2 SO4
HCOOH   CO  H 2 O (COOH )2   CO  CO2  H 2 O
(a) (b)
Formic acid Oxalic Acid

H 2 SO4
C6 H12 O6   6C  6 H 2 O H 2 SO4
(c) (d) C12 H 22 O11   12C  11H 2 O
Glu cos e
H 2 SO4
2C2 H 5 OH   C2 H 5 OC2 H 2  H 2 O
(e)
Ethyl Alcohol Ether

Oxidizing property
Since concentrated H 2 SO4 , gives oxygen on strong heating, hot concentrated H 2 SO4 acts as oxidizing agent.
 H 2O  SO2   O 
H 2SO4 
 It oxidizes non metal, carbon, sulphur, phosphorous.
i) C  2 H 2 SO4 
 CO2  2 SO2  2 H 2 O ii) S  2 H 2 SO4 
 3SO2  2 H 2 O
iii) P4  10 H 2 SO4 
 P4 O10  10 SO2  10 H 2 O iv) P4 O10  6 H 2 O 
 4 H 3 PO4
 Sulphuric acid oxidizes the metals above hydrogen in electrochemical series. Example, Zn
Zn  2 H 2 SO4 
 ZnSO4  2 H 2 O  SO2
 Oxidation of metals below hydrogen in electrochemical series. For example, Cu
Cu  2 H 2 SO4 
 CuSO4  SO2  2 H 2 O

Oxidation of other compounds: Halogen acids and ferrous sulphate are oxidizes by sulphuric acid.
Heat
2 HX  H 2 SO4   X 2  SO2  2H 2 O
(where X  Br or I )
Heat
2 FeSO 4  2 H 2 SO4   Fe2 ( SO4 ) 3  SO2  2 H 2 O
Heat
2 HI  H 2 SO4   2 H 2 O  SO2  I 2

Action of dilute sulphuric acid on metals: Metals above the hydrogen in the electrochemical series react with dil.
H 2 SO4 with the evolution of hydrogen. E.g. Mg , Zn, Fe
Fe  H2 SO4 
 FeSO4  H2( g )
Metals like Cu , Pb, Hg , Bi and noble metals are not attacked by dilute H 2 SO4 with the evolution of hydrogen. E.g. Mg,
Zn, Fe
Fe  H2 SO4 
 FeSO4  H2 ( g )

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Metals like Cu, Pb, Hg, Bi and noble metals are not attacked by dilute H 2 SO4 .
It acts as a sulphonating agent.
C6 H 6  HOSO2 OH 
 C6 H 5 SO2.OH  H 2 O
Benzene sulphoric acid
Reaction with PCl5
HO.SO2 . OH  PCl5 
 ClSO2OH  POCl3  HCI
(Chorosulphuric acid )
ClSO2OH  PCl5 
 ClSO2Cl  POCl3  HCl
( Sulphury chloride)
Crystals of [ K 4 Fe(CN )6 ] when heated with conc. H 2 SO4 , carbon monoxide is evolved.
[ K 4 Fe(CN )6 ]  6 H 2 SO4  6 H 2 O 
 2 K 2 SO4  FeSO4  3( NH 4 ) 2 SO4  6CO
Action of conc. H 2 SO4 on KClO3 (potassium chlorate)
3KClO3  3H 2 SO4 
 3KHSO4  HClO4  2ClO2  H 2 O
It forms normal salts like Na2 SO4 , CuSO4 and acid sulphates like NaHSO4 .
It forms hydrogen fluoride with CaF2 .
CaF2  H 2 SO4 
 CaSO4  2 HF
Sulphuric acid, because of its low volatility can be used to manufacture more volatile acids from their corresponding salts.
2 MX  H 2 SO4 
 2 HX  M 2 SO4
(Where X = F, Cl, NO 3 and M = metal)

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Uses of H 2 SO4
i) It is regarded as king of chemicals. It is used in the manufacture of dyes, fertilizers (ammonium sulphate, super
phosphate), detergents, explosive (T. N. T. nitroglycerine, green cotton) etc.

ii) Sulphuric acid is used in the preparation of other important chemicals like HNO3 , HCl , H 3 PO4 , Na2 CO3 , sulphates,
alums, ether etc.

iii) In lead storage batteries (containing sulphuric acid) involve the following reaction.
PbO2  Pb  2 H 2 SO4 
 2 PbSO4  2 H 2 O

iv) Sulphuric acid is commonly used as a laboratory reagent.

v) It is dehydrating agent. Many wet gases can be dried by passing them through sulphuric acid provided the gases do not
react with acid.
vi) It works as oxidizing agent.
vii) It is used in refining of petroleum.
viii) Sulphuric acid is used as a pickling is an industrial process for removing layers of basic oxides from metals like Fe
and Cu before electroplating, enameling, galvanizing and soldering.

QUESTIONS (including Board questions)

1. List the important sources of sulphur.
2. Write the order of thermal stability of the hydrides of Group 16 elements.
3. Why is H 2 O a liquid and H 2 S a gas?
4. What are the oxidation states of the element in Group 16?
5. How is oxygen prepared by thermal decomposition of certain metallioxides?
6. Different types of oxides? Give example of oxygen.
7. Which of the following does not react with oxygen directly? Zn, Ti, Pt, Fe
8. Complete the following reactions: (i) C2 H 4  O2  (ii) 4 Al  3 O2 
9. Protective umbrella as ozone for uv from sun.
10. Ozone acts as oxidizing and reducing agent explain with example.
11. Why does O3 act as a powerful oxidising agent?

12. How is O3 estimated quantitatively?

13. How does sulphur occur?

14. How is sulphur dioxide manufactured?
15. Explain the structure of SO2 molecule.
16. What are allotropic forms of sulphur.
17. What happens when sulphur dioxide is passed through an aqueous solution of Fe(III) salt?
18. Comment on the nature of two S-O bonds formed in SO2 molecule. Are the two S-O bonds in this molecule
equal?
19. How is the presence of SO2 detected?
20. Why is Ka2 smaller than Ka1 for H 2 SO4 in water?
21. Mention the conditions to maximize the yield of H 2 SO4 by contact process.

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22. Distinguish between white phosphorus and red phosphorus

23. Explain the trends in the following properties with reference to group 16 (March 2013)
(a) Atomic and ionic radii (b) Density (c) ionization enthalpy (d) Electronegativity
24. Write resonating structures of ozone. (March 2014)
25. Describe anomalous behaviour of oxygen as compared to other elements of group 16
With reference to (a) magnetic property (b) Oxidation states (c) hydrides (Oct 2014)
26. Explain the structure of SO2. (March 2015)
27. Write molecular formulae and structures of the following compounds:
(a) dithionic acid (b) peroxy-mono sulphuric acid (c) pyrosulphuric acid (d) dithionous acid (March 2015)
28. What are neutral oxides? Explain the nature of ZnO with the help of reactions. (March 2016)

GROUP 17
Elements
Introduction:
Fluorine, chlorine, bromine, iodine and astatine are members of Group 17. These are collectively known as the halogens
(Greek halo means salt and genes means born i. e. , salt producers). The halogens are highly reactive non-metallic
elements. Like Groups 1 and 2, the elements of Group 17 show great similarity amongst themselves.

Occurrence:
Fluorine is present mainly as insoluble fluorides (fluorspar CaF2 , cryolite Na 3AlF6 and fluoroapatite 3Ca 3 (PO 4 ) 2 .CaF2 )
and small quantities of fluorine are also present as fluorides. Sea water contains chlorides, bromides and iodides of
sodium, potassium, magnesium and calcium, but is mainly sodium chloride solution (2.5% by mass).

Electronic Configuration: All these elements have seven electrons in their outermost shell (ns 2 np 5 ) which is one
electron short of the next noble gas.

Q1. Explain the trendsin in the following properties of groups 17 elements.

(i) physical state
(ii) Atomic and ionic radii
(iii) Ionization enthalpy
(iv) Electron gainenthalpy
(v) Electronegativity
(vi) Melting and boiling point
(vii) Colour

Ans.
(i) Physical State: Halogens display smooth variations in their physical properties. Fluorine and chlorine
are gases, bromine is a liquid and iodine is a solid.
(ii) Atomic and Ionic Radii: The halogens have the smallest atomic radii in their respective periods due to
maximum effective nuclear charge. The atomic radius of fluorine like the other elements of second period
is extremely small. Atomic and ionic radii increase from fluorine to iodine due to increasing number of
quantum shells.
(iii) Ionisation Enthalpy: They have little tendency to lose electron. Thus they have very high ionization
enthalpy. Due to increase in atomic size, ionization enthalpy decreases down the group.

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(iv) Electron Gain Enthalpy: Halogens have maximum negative electron gain enthalpy in the corresponding
periods. This is due to the fact that the atoms of these elements have only one electron less than stable
noble gas configurations. Electron gain enthalpy of the elements of the group becomes less negative down
the group. However, the negative electron gain enthalpy of fluorine is less than that of chlorine. It is due
to small size of fluorine atom.
(v) Electronegativity: They have very high electronegativity. The elctronegativity decreases down the
group. Fluorine is the most electronegative element in the periodic table.
(vi) Melting and boiling point: Their melting and boiling points steadily increase with atomic number.
(vii) Colour: All 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.

Q2. Explain the chemical properties of halogen

Ans.
Halogens are highly reactive elements. In fact, each halogen is the most reactive non-metal of its period. Fluorine
is the most reactive of all the halogens. The reactivity of halogens decreases on moving down the group, i.e., from
F to I. The high reactivity of halogens may be attributed to the following factors.
(i) High negative electron gain enthalpy :Since halogens have high negative electron gain enthalpy, they have
high electron affinity and hence strong tendency to gain an electron.
(ii) Low dissociation energy : The dissociation energy involved in the breaking of X-X bond in halogen (X 2 )
molecules is much lower as compared to other bonds such as H-H, C-C, C-H, C-O, O=O, N  N etc. present in
common molecules. This facilitates the dissociation of their molecules and increases the reactivity.

(1) Oxidizing nature

Being strongly electronegative, halogens have a strong tendency to accept an electron and form anions.
1 x 2  e   x  (x  F, Cl, Br or I)
2
Thus halogens have strong tendency to undergo reduction. It is this tendency which imparts them oxidizing
nature. All halogens acts as strong oxidizing agents. The oxidizing power of halogens decreases from fluorine to
iodine. A halogen can displace all other halogens placed below it in the group.
F2  2X  
 2F  X 2 (X  Cl, Br, I)
eg.
Cl2  2X  
 2Cl   X 2 (X  Br, I)

(2) Reaction with metals and non-metals

All halogens react with metals and many non-metals to form halides. The reactivity decreases as we go down the
group from fluorine to iodine. Halogens react with most of the metals.
eg. Cu  F2 
 CuF2 2Al  3Br2 
 Al 2 Br6
i) Halides of metals having low ionization enthalpy (alkali metals) are ionic in nature and possess higher values
of melting and boiling points.
ii) In case of metal halides, the metal exhibiting more than one oxidation states, the halide in higher oxidation
state of the metal is more covalent than the one in the lower oxidation state.
iii) Most metals exhibit their highest oxidation state in the fluorides e.g. WF6 , OsF6 etc.
iv) With a given non-metal (M), the strength of M – X bond decreases in the following order.
M  F  M  Cl  M  Br  M  I

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(3) Reactivity towards hydrogen

All halogens react with hydrogen to give hydrogen halides but affinity for hydrogen decreases from fluorine to
iodine.

dark diffused
i) H 2  F2   2HF ii) H 2  Cl 2 
sunlight
2HCl
Heat
Heat
iii) H 2  Br2   2HBr 
 2HI
iv) H2  I 2 


The acidic strength of these acids vary in the order.

HF  HCl  HBr  HI
The 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

(4) Reactivity towards oxygen : Halogens react with oxygen to form many oxides. Most of the oxides are unstable.
Fluorine forms two oxides OF2 and O 2 F2 . Only OF2 is thermally stable. Both oxides are strong fluorinating
agents. O 2 F2 is used to oxidise plutonium to PuF6 and the reaction is used for isolating plutonium as PuF6 from
used nuclear fuel.
Chlorine forms oxides like Cl 2 O, ClO 2 , Cl2 O 6 and Cl 2O7 . All these are highly reactive oxidizing agents. ClO 2
is used as bleaching agent
Bromine forms three oxides like Br2 O, BrO 2 , BrO 3 which are unstable and exist only at low temperature.
Iodine forms three oxides like, I 2 O 4 , I 2 O 5 , I 2 O 7 . These solids are insoluble in water and decomposes on heating.
(5) Reaction with metals : Halogens show tendency to react with metals and forms metal halides. Magnesium
readily reacts with chlorine to form magnesium chloride. The ionic character of metal halides decreases in the
order MFn  MCl n  MBrn  MI n where M is metal and n is its valency.

(6) Reaction with water : Halogens react with water, with decreasing vigour from F to I. Fluorine reacts
spontaneously and it oxidizes water to oxygen (or ozone).

e.g. 2F2(g)  2H2O 
 4H (aq)  4F  O2(g)
e.g. X2(g)  H2O(1) 
 HX(aq)  HOX(aq) Where X  Cl or Br

(7) Reaction with hydrocarbons : All the halogens react with hydrocarbons but the reactivity decreases with
increase in atomic number. Fluorine being the most reactive, decomposes hydrocarbons.
e.g. CH 4  2F2 
 C  4HF

(8) Reaction with alkali : Florine reacts spontaneously with alkali giving fluorides, oxygen and water.
4NaOH  2F2 
 4NaF  O 2  2H 2 O
The other halogens react with cold NaOH solution and form halides and hypohalides
2NaOH  Cl2 
 NaCl  NaOCl  H2O
(cold and dilute) (chloride) (Hypochlorite)

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(9) Bleaching action : Fluorine and iodine does not show bleaching action. Moist chlorine is good bleaching agent
where as moist bromine shows slow bleaching action.
Cl2  H 2 O 
 HCl  HOCl
HOCl 
 HCl  [O]

(10) Reactivity of halogens towards other halogens : Halogens when combine amongst themselves form a many
compounds known as interhalogen compounds of the types XX’, XX’ 3 , XX’ 5 , XX’ 7 where X is a larger size
halogen while X’ is halogen while X’ isd halogen having smaller size.

Q3. Why does fluorine exhibit anomolous behaviour and how does it differs from all other halogens.
Or
Explain the anomolous properties of fluorine
Ans. Fluorine exhibits anomalous behaviour, it is due to
(i) it’s small size (ii) highest electronegativity
(iii) low F-F bond dissociation energy (iv) non availability of d-orbitals in valence shell

The main points of difference between fluorine and other elements of the group are as follows
(a) Reactivity : Fluorine is much more reactive than other elements of the group. This is due to a very low value of F-F
bond dissociation energy, which is best explained by its small size and high nuclear charge.
(b) Hydrogen bonding : Due to small atomic size and high electronegativity, fluorine forms hydrogen bonding in its
hydrides. Other elements of the group do not form hydrogen bonding in their hydrides.

(c) Behaviour of HF : Due the presence of hydrogen bonding the behaviour of hydrofluoric acid is different from that
of other halogen acids. For example,
(i) Hydrofluoric acid is a liquid, while other halogen acids are gases under ordinary temperature.
(ii) Hydrofluoric acid is a weak acid, while all other halogen acids are strong acids. This is due to high
dissociation energy of H-F bond.
(d) Oxidation state : Fluorine exhibit only in – 1 oxidation state in all its compounds. Other elements of the group
exhibit +1, +3, +5 and +7 oxidation states in addition to the – 1 oxidation state. The existence of only – 1 oxidation state
of fluorine is due to its highest electronegativity and absence of the vacant d-orbitals in its valence shell.

(e) Electron gain enthalpy : Inspite of being more electronegative than chlorine, the negative value of electron gain
enthalpy is less than that of chlorine. This is due to very small atomic size of fluorine atom.

(f) Nature of compounds : As fluorine has the highest electronegative, it has strong tendency to form ionic compounds.
Fluorides have the maximum ionic character. For example, AlF3 is ionic, CsF is most ionic. All other halides of
aluminum are covalent in nature.

(g) Polyhalide ions : Fluorine does not form any polyhalide ion, whereas other halogens form polyhalide ions such as
I  3 , Br  3 , and Cl  3 ions. This is due absence of vacant d-orbitals in the valence shell of fluorine.

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Compounds of halogens

(A) Chlorine
Occurrence
Chlorine does not occur in free state due to its high reactivity. It occurs in combined state and widely distributed.
It is the most abundant halogen.
Chlorine occurs to an extent of 0.14% in the earth crust. Some minerals containing chlorine are as follows :
i) rock salt : NaCl , ii) Carnalite : KCl.MgCl2 , 6 H 2 O , iii) Sylvine : KCl , iv) Horn Silver : AgCl
Preparation of chlorine

Q4. How will you prepare chlorine?

Ans. Chlorine can be prepared by any one of the following methods.
(1) By the oxidation of hydrochloric acid
(i) From Manganese dioxide : MnO2 oxidizes HCl to Cl2 as per the following reaction.

MnO2  4 HCl   MnCl2  Cl2  2 H 2 O
(ii) Lead dioxide or red lead : Chlorine can be obtained by treating lead dioxide or red lead with HCl .
PbO2  4 HCl 
 PbCl2  Cl2  2H 2 O
Pb3 O4  8HCl 
 3PbCl2  Cl2  4 H 2 O
Red lead

(2) By the action of mineral acids on bleaching powder :

Chlorine can also be obtained by treating bleaching powder (CaOCl2 ) with minerals acids such as dil.
HCl or dil. H 2 SO4 .
CaOCl2  2 HCl 
 CaCl2  Cl2  H 2 O
(3) By the action of conc. H 2 SO4 on NaCl in the presence of MnO2 .
2 NaCl  MnO2  3H 2 SO4 
 2 NaHSO4  MnSO4  Cl2  2 H 2 O

Q5. How is chlorine manufactured in industry

i) Deacon process : Hydrogen chloride gas is oxidized by atmospheric oxygen in the presence of CuCl2
(catalyst) at 723K.
CuCl2
4 HCl  O2   2Cl2  2 H 2O
ii) Electrolytic process : The process is used for the manufacture of sodium hydroxide when chlorine is
obtained as a byproduct. The process involves the electrolysis of an aqueous solution of brine ( NaCl ). During
electrolysis of brine, hydrogen gas liberates at cathode, whereas chlorine gas librates at anode. Since chlorine
reacts with NaOH and H 2 the cathode must be separated from the anode in such a way that the chlorine
evolved at the anode does not come in contact with NaOH or H 2 produced at the cathode.

Q6. State the physical properties of chlorine

Ans.
i) It is greenish yellow gas with a characteristic pungent and suffocating odour and heavier then air.
ii) It is poisonous gas.
iii) It can be liquefied easily into greenish yellow liquid which boils at 239K.
iv) It is soluble in water and solution is called as Chlorine Water.

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Q7. Explain the chemical properties of chlorine

Ans.
(1) Combustibility: Chlorine is neither combustible nor a supporter of combustion.

(2) Combination with metals: It reacts with a number of metals to form their chlorides. The action of
chlorine on metals increases with increase in the activity of metal. For example, sodium and other alkali
metals, Ca etc. Burn spontaneously in chlorine and form their respective chlorides.
i) 2 Na  Cl2 
 2 NaCl ii) 2 K  Cl2 
 2 KCl
(3) Reaction with water: In the absence of sunlight, chlorine dissolves in water at ordinary temperatures to
from mixture of HCl and HOCl (hydrochloric acid and hypochlorous acids)

Cl2  H2 O  HCl  HOCl
Hypochlorous acid
(4) Combination with non metals: It combines directly with several metalloids and non-metals such as
arsenic antimony, sulphur, phosphorous, boron to form respective chlorides.
i) 2 As  3Cl2 
 2 AsCl3 ii) 2 Sb  3Cl2 
 2 SbCl3
(5) Affinity for hydrogen: Chlorine has a very high affinity for hydrogen. It combines with hydrogen in
the presence of diffused sunlight to form hydrogen chloride.
H 2  Cl2 
 2 HCl
(6) Bleaching Action: Due to its oxidizing nature, chlorine acts as a powerful bleaching agent. In the
presence of moisture, it bleaches the colouring matter of green leaves, flowers, litmus, indigo etc. The
Bleaching action is due to the libration of nascent oxygen which oxidizes the vegetable colouring matter
to a colourless product.
Cl2 + H2O  2HCl + [O]
Therefore chlorine is used to bleach cotton fabrics and wool pulp.
(7) Disinfecting action: Chlorine also acts as a disinfecting agent due to its ablity of killing harmful micro-
organisms. This ability is again due to its oxidizing nature.It is largly used for the sterilization of the municipal
supply water used for drinking purpose.

Q8. Give reasons for the bleaching action of chlorine and explain its bleaching action.
Ans. Due to its oxidizing nature, chlorine acts as a powerful bleaching agent. In the
presence of moisture, it bleaches the colouring matter of green leaves, flowers, litmus, indigo etc. The
bleaching action is due to the liberation of nascent oxygen which oxidizes the vegetable colouring matter
to a colourless product.
Cl2 + H2O  2HCl + [O]
Therefore chlorine is used to bleach cotton fabrics and wool pulp.

Q9. Explain the oxidizing nature of chlorine with the examples.

Ans. i) It oxidizes ferrous salts to ferric salts:
2FeSO4 + H2SO4+Cl2  Fe2 (SO4)3 + 2HC
ii) It oxidizes sulphites to sulphates
Cl2 + Na2SO3 + H2O  Na2SO4 + 2 HCl
iii) It oxidizes H2S to Sulphur
Cl2 + H2S  S + 2HCl
iv) It oxidizes SO2 to H2SO4
Cl2+SO2+2H2O  2HCl + H2SO4

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Q10. Write the uses of chlorine.

Ans. (i) Large quantities of chlorine are used industrially for bleaching wood pulp (required for the manufacture of
paper and rayon), bleaching cotton and textiles.
(ii) It is used in the extraction of gold and platinum.
(iii) It is used for the manufacture of dyes, drugs and organic compounds such as CCl4 ,CHCl3 , refrerants, etc.
(iv) It is used in sterilizing drinking water.

Q11. How is hydrogen chlorine prepared in lab?

Ans. In the laboratory hydrogen chloride is prepared by heating a mixture of sodium chloride and concentrated
sulphuric acid.
420 K
NaCl  H 2 SO4   NaHSO4  HCl
823 K
NaHSO4  NaCl   Na2 SO4  HCl
Q12. State Physical properties of HCl.
Ans. i)It is a colorless gas with pungent odour and heavier than air.
ii) On liquefication HCl gas gives a colourless liquid (B.P. 189K) which on freezing gives white crystalline solid
(m.p. 159K). It is highly soluble in water and ionizes, giving a strongly acidic solution.
 H3O( aq)  Cl 
HCl( g )  H2 O(1)  Ka  107

Q13. Write the reaction of HCl with

i) NaHSO3 ii) Na2CO3
iii) NaHCO3 iv) Mg (OH )2
v) NH 3 vi) Na
Ans.
i) NaHSO3  HCl 
 Nacl  H 2 O  SO2 ii) Na2 CO3  2 HCl 
 2 NaCl  H 2 O  CO2
iii) NaHCO3  HCl 
 NaCl  H 2 O  CO2 iv) Mg (OH ) 2  2 HCl 
 MgCl2  2 H 2 O
v) NH 3  HCl 
 NH 4 Cl ( white fumes )
vi) 2Na + 2 HCl  2NaCl + H2

Q14. What is aquaregia:

Ans. A mixture of three parts of conc. HCl and one part of concentrated HNO3 is known as aquaregia. It is used for
dissolving noble metals, like gold, platinum.
.
Q15. What are the uses of hydrogen chloride (hydrochloric acid)
Ans.
It is used (1) in the manufacture of chlorine and ammonium chloride.
(2) to manufacture dye extensively as laboratory reagent.
(3) to manufacture glucose from corn starch.
(4) for extracting glue from bones and purifying bone black.
(5) in medicine and in galvanizing
Zn  2 HCl 
 ZnCl2  H 2

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Q16. What are Interhalogen compounds give two examples.

Ans.
When two different halogens form compounds among themselves, interhalogen compounds are formed. Such
compounds can be assigned general compositions as XX ', XX '3 , XX '5 and XX '7 . Here X is halogen of large
size and X’ of small size and X is more electropositive than X’. As the ratio between and X and X’ increases, the
number of atoms per molecule also increase. For example Iodine forms IF 7 . The size of iodine is larger than
fluorine, and ratio of radii between I and F is maximum. Hence why iodine forms IF 7 having maximum number
of atoms.
Examples of the types Interhalogen compounds
Type Example
XX ' ClF , BrF , BrCl , ICl
XX '3 ClF3 , BrF3 , IF3 , ICl3 (unstable)
XX '5 IF5 , BrF5 , CIF5
XX '7 IF7

Q16. Explain the methods of preparation of Interhalogen compounds.

Ans.
The interhalogen compounds can be prepared by the direct combination or by the action of halogen on lower
interhalogen compounds.
(i) Formation of ClF (Chlorine monofluoride), it is colourless gas.
437 K
Cl2  F2   2ClF
(equal volume)
(ii) Formation of ClF3 (Chlorine trifluoride) – It is colourless gas.
573 K
Cl2  3F2   2ClF3
(Excess)
(iii) Formation of ICl3 - It is yellow powder.
I 2  3Cl2 
 2 ICl3
(excess)
(iv) Br2 + 5F2  2BrF5

Q17. State the general characteristics of interhalogen compounds

Ans.
(1) Interhalogen compounds are covalent in nature, due to the low electro negativity difference between halogens.
(2) All these compounds are volatile. Most of them are unstable but none is explosive.
(3) They are diamagnetic in nature.
(4) They are more reactive than halogens. This is because X  X ' bonds present in them are weaker than
X ' X or X ' X ' bonds.
(5) Interhalogen compounds undergo hydrolysis when treated with water. For example,

ICl  2 H 2 O   H 3 O   Cl   HOI


2 ICl3  3H 2 O  ICl  HIO3  5 HCl

(6) Interhalogens like ClF3 , BrF3 etc. are very reactive and acts as strong fluorinating agents.

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Q18. Explain the structure of following interhalogen compounds with suitable examples
(i) XX ' (ii) XX '3 (iii) XX '5 4) XX’7

Ans. 1) XX ' Compounds: Interhalogen compounds of type XX ' are very simple and consists of two halogen atoms

linked together through a single covalent bond. Thus their structure can be represented as X  X ' .
2) XX '3 Compounds:

i)Interhalogen of the type XX '3 (X= Cl,Br,I)possess T-shaped or trigonal bipyramidal structure.

(ii)It is formed by sp 3 d hydribization of the central atom X in its first excited state.
(iii) Two hybrid orbital contains lone pair of electron
For example, the formation of XF3 shown below (a) and (b) in

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3) XX '5 Compounds: i) Interhalogen compounds of the type XX '5 have square pyramidal structure.
ii) They are formed by sp 3 d 2 hybridization of the central X atom in its second excited state.
iii) One hybrid orbital is occupied by lone pair of electron

4) XX’7 Compounds :
i) The only known interhalogen compound of the type XX '7 is IF7 .
ii) It is formed by sp 3 d 3 hybridization of the central I atom in its third excited state.
iii) The molecule has a pentagonal bipyramidal structure as shown below

Q19. Write the uses of interhalogen compounds

Ans.
(i) Interhalogen compounds of the type XX ' (particularly ICl) are used as halogenating agent. ICl is used in the
estimation of iodine number of fats and oils.
(ii) Interhalogen compounds are used for the preparation of polyhalides.
(iii) ClF3 and BrF3 are used as fluorinating agents.
(iv) ClF3 and BrF3 are used as oxidizer in propellants.
(v) Interhalogen compounds can be used as non-aqueous solvents. BrF3 is also used as Lewis acid.

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Q20. Write short note on Oxyacids or oxoacids of halogens

Ans.
Fluorine forms only one oxyacid i.e. HOF hypofluorous acid or fluoric acid. It is due to its high electronegativity
and small size.
The other halogens form many oxoacids. Isolation in pure state is difficult as oxoacids are stable only in aqueous
solutions. Table give some oxyacids of halogens.

Oxyacids of halogens
Oxyacids of halogens Hypohalous acid Halous acid Halic acid Per halic acid
Fluorine HOF   
HypoFluorous acid
Chlorine HOCl HOClO HOClO2 HOClO 3
Hypo chlorus acid Chlorous acid Chloric acid Per chloric acid
Bromine HOBr  HOBrO 2 HOBrO 3
Hypo bromous acid Bromic acid Per bromic acid
Iodine HOI  HOIO 2 HOIO 3
Hypo iodous acid Iodic acid Per iodic acid

Q21. Draw the Structure of oxyacids of chlorine

Ans.

Board Questions
1. What is the action of chlorine on the following (Oct 2013)
(a) cold and dilute caustic soda (b) hot and conc caustic soda (c) KBr solution
2. Describe anomalous behaviour of fluorine with other elements of group 17 with reference to
(a) hydrogen bonding (b) oxidation states (c) polyhalide ions (March 2014)
3. Draw the structure of (a) chlorine trifluoride (b) chlorine penta fluoride (Oct 2015)
4. Write Four uses of hydrochloric acid
5. Write chemical formulae of the following oxo-acids of chlorine:
(a) hypochlorous acid (b) Chlorous acid (c) Chloric acid (d) Perchloric acid (Oct 2015)

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GROUP 18 ELEMENTS (NOBLE GASES)

Q22. Discuss the position of group 18 elements in the periodic table.

Ans.
The group 18 of the periodic table consists of helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe) and
radon (Rn). All these exist in the form of gases only and chemically they are unreactive. They form very few compounds,
hence these elements are also called inert gases or noble gases. Radon is a radioactive in nature. Other gases occur in very
small amounts in atmosphere. Therefore, these gases are also called rare gases.

Q.23. Explain the electronic configuration of group 18 elements.

Ans. The noble gases have very stable electronic configuration. All the available orbitals present in them are
completely filled. The electronic configuration of helium is 1 s 2 , while all other noble gases have general electronic
configuration of the type ns 2 np 6 . Due to completely filled orbitals in the (stable closed shell) electronic configuration,
these elements possess no tendency to lose or gain electrons. Hence they do not take part in chemical reactions and react
with very few elements under certain conditions.

Electronic configuration of noble gases

Element Symbol Atomic Number Electronic configuration
Helium He 2 1s 2
Neon Ne 10 1s 2 2 s 2 2 p 6 Or [ He] 2 s 2 2 p 6
Argon Ar 18 1s 2 2 s 2 2 p 6 3s 2 3 p 6 Or [ Ne] 3s 2 3 p 6
Krypton Kr 36 1s 2 2 s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6
Or [ Ar ] 3d 10 4 s 2 4 p 6
Xenon Xe 54 1s 2 2 s 2 2 p 6 3s 2 3 p 6 3d 10 4 s 2 4 p 6 4d 10 5s 2 5 p 6
Or [ Kr ] 4d 10 5s 2 5 p 6
Radon Rn 86 1s 2 2 s 2 2 p 6 3s 2 3 p 6 3d 10
4 s 2 4 p 6 4d 10 4 f 14 5s 2 5 p 6 5d 10 6 s 2 6 p 6
Or[ Xe]4 f 14 5d 10 6 s 2 6 p 6

Q24. Write the short note on occurrence of group 18 elements.

Ans.
Since noble gases do not react chemically under ordinary sets of conditions they always occur in the free state in
nature. The most important source of noble gases is atmosphere where they are present to an extent of about 1% by
volume of air. Argon is the major constituent.

Q25. Explain the trends of following in the group 18 elements.

(i) Physical state
(ii) Atomic raddi
(iii) Ionization enthalpy
(iv) Electron gain enthalpy
(v) Melting and boiling points
(vi) Liquefication tendency
(vii) Ability to diffuse
(viii) Solubility in water

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Ans.
(1) Physical state : All the elements of group 18 are colourless, odourless and tasteless. All these elements are
monoatomic in nature. Their monoatomic nature is evident from the Cp / Cv values which are close to 1.66. This value
always referes for monoatomic gas. (Here Cp=specific heat at constant pressure. Cv=specific heat at constant volume)

(2) Atomic radius : The atomic radii of elements of group 17 (halogens). The atomic radii increase on moving down
the group i.e. from He to Xe.
In contrast to general trend of variation of atomic radii in a period (the atomic radii decreases on moving left to
right in a period), the atomic radii of noble gases are found to be larger than those of halogens. This is due to increased
electronic repulsions between completely filled valence shell in noble gases.

Some important physical properties of noble gases (group 18 elements)

Property Elements
He Ne Ar Kr Xe Rn
Atomic number 2 10 18 36 54 86
Atomic radii(pm) 99 160 192 197 217 
Ionisation enthalpy kJmol 2372 2080 1520 1350 1170 1037
1

Electron gain enthalpy 48 116 96 96 77 68

1
kJmol
Density at STP (gm/cm 3 1.8 10 4 9.0 10 4 1.8 10 3 3.7 103 5.9 10 3 9.7 103
)
Melting point (K) 3 24.0 84 116.0 161.0 202
Boiling point (K) 4.0 27.0 87.0 121 165.0 211

(3) Ionization enthalpy : Group 18 elements possess very high values of ionization enthalpy. The enthalpy of each
noble gas is the highest in its period. The ionization enthalpy decreases down the group.
The very large ionization enthalpies of noble gases are due to their very stable closed shell electronic configuration as it
requires a very large amount of energy to remove an electron from a completely filled outermost shell.
(4) Electron gain enthalpy : Due to stable electronic configurations, these gases have no tendency to accept electrons.
Hence these elements have large positive values of electron gain enthalpy.
(5) Melting and boiling points : The melting and boiling points of noble gases are much lower as compared to those of
other substances of comparable molecular masses. The melting and boiling points increase regularly on moving down the
group, melting and boiling points of noble gases are very low. This is due to very weak interatomic forces.
(6) Liquefication tendency : Group 18 elements are not easily liquefied. However, the tendency for liquefication
increases on moving down the group.
When the atoms of noble gases are brought closer, the only forces of attraction which can hold their atoms together are
weak van der Waal’s forces. Since, the van der Wall’s forces existing between the atoms of noble gases in the liquid state
are very weak, the noble gases possess very little tendency to get liquefied.
(7) Ability to diffuse : All noble gases are able to diffuse through glass, rubber, plastic material and some metals.
Hence, they are difficult to handle in the laboratory for low temperature research work.
(8) Solubility in water : Noble gases are slightly soluble in water. Helium is least soluble. The solubility of group 18
elements in water increases on moving down the group, i.e. from He to Xe. The solubility of these elements in water is
due to dipole-induced dipole interactions. Due to this, the noble gas atoms get distorted and changes into an induced
dipole.

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Q26. Why are noble gases least reactive.

Ans.
Group 18 elements do not show chemical reactivity under ordinary conditions. The non-reactivity of noble gases
under ordinary sets of conditions is due to the following reasons.
(i) The group 18 elements have completely filled valence shells (1s 2 in case of He, and ns 2 np 6 in case of other
gases). The next available vacant shell is of much higher energy.
(ii) Their electron gain enthalpy values are large and positive.
(iii) Elements possess very high ionization enthalpy.

Q27. Explain Bartlett reaction.

Ans.
Neil Bartlett demonstrated the first chemical reaction of noble gases in 1962. He observed that oxygen gas was
oxidized by PtF6 to form compound O  2 P tF6 . However, the ionization energy of oxygen and Xe are
comparable (about 1170kJmole 1 ). Hence Bartlett conducted reactions between Xe and PtF6 and separated the
first compound of noble gases i.e. Xe  PtF6 . It is an orange yellow crystalline solid.
 Xe PtF6
Xe  PtF6 
[ Xenon hexafluoro  platinate (v)]

Q28. Write the uses of noble gases.

Ans.
Noble gases which are available easily have many uses.
(1) Helium
(i) It is used for filling balloons and air ships as it is light and non combustible.
(ii) It is used in producing inert atmosphere in metallurgical operations and welding of metals.
(iii) Liquid helium is used for the production of low temperature.
(iv) A mixture of helium and oxygen is used for the respiration in deep sea diving instead of air because of
helium is less soluble in the blood than nitrogen under high pressure. It is also for treatment of asthma.
(v) It is used to produce and sustain powerful super-conducting magnets which form an essential part of modern
NMR spectrometers and magnetic Resonance Imaging (MRI) systems for clinical diagnosis.
(vi) It is also used in gas cooled nuclear reactors.

(2) Neon
(i) Neon largely used for production of neon lights. Such units consist of glass tubes filled with neon or mixture
of neon and other gases at low pressure (about 2mm) and glow on the electric discharge.
(ii) Besides being attractive the neon lights have a great penetrating power in mist and fog. (Beacon lights for
pilots). The neon light of various shades may be obtained by varying the composition of the gaseous mixture and
changing the colour of the tube.
(iii) Neon is also used in television sets, spark plug, warning signals etc.
(iv) It is also used in safety devices, electrical instruments like voltage stabilizer and reactifires.
(v) Neon bulbs are used in botanical gardens and in green houses.
(3) Argon
(i) Argon is used to fill incandescent and fluorescent discharge lamps.
(ii) It is used to provide inert atmosphere for welding and several metallurgical processes.
(iii) This gas is used in gas chromatography.
(iv) It is mixed with neon to obtain different colours in neon sign lamps.
(v) It is also used in laboratory for handling substances that are air sensitive.
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(4) Krypton
(i) Krypton is used in filling discharge tubes and electric bulbs.
(ii) It is also used in high efficiency miner’s cap lamps.
(iii) Krypton – 85 is used to measure thickness of sheets of metals and plastics.
(iv) It is used in the signal light on runways of airports because it produces a bright white light during electric
discharge.
(v) It is used for making krypton atomic lamp which is used in cosmic ray instruments.

(5) Xenon
(i) A mixture of Xe and Kr is used in the flash bulbs used in the high speed photography.
(ii) Liquid xenon is used in research laboratories for the detection of mesons and gamma photons.

(6) Radon
(i) It is used in the treatment of cancer by radiotherapy.
(ii) It is used for photographing the interior of opaque materials like steel castings.
(iii) It is also used for research in radioactivity.

Board Questions
1. Write electronic configuration and uses of Neon (October 2013)

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