CHAPTER

5 The Halogens And The Noble

Gases

Animation 5.1: Halogens

Source & Credit: Media
5. The Halogens and the Noble Gases eLearn.Punjab

IN THIS CHAPTER YOU WILL LEARN:

1. The electronic configurations and the occurrence of halogens, the peculiar
behaviour of fluorine.
2. The volatility of halides and its explanation in terms of van der Waals forces.
3. The relative reactivities of halogens as oxidizing agents.
4. The properties of hydrogen halides, oxides and oxyacids of halogens.
5. The comparison of thermal stability of hydrides in terms of bond energies.
6. Reaction of chlorine with sodium hydroxide (hot/cold).
7. The preparation and reaction of bleaching powder.
8. The commercial uses of halogens and their compounds as bleaches,
refrigerants and aerosols.
9. The electronic configurations, physical properties, inertness and isolation of
noble gases from air.
10. The properties of oxides, fluorides and oxyfluorides of xenon.

5.1 Introduction

The elements fluorine (F), chlorine(Cl), bromine(Br), iodine(I) and astatine(At)

are called halogens.These elements are called the halogens from Greek
hals, “salt” and gennan, “to form or generate”, because they are literally
the salt formers.The halogen elements form a group of very reactive non-
metals and are quite similar to each other in their chemical properties.
First four elements are the common elements of the halogen family but
astatine is a rare halogen. It is radioactive and its most stable isotope has a
half life of 8.3 hrs.
Halogens exist as discrete diatomic molecules in all phases (gas, liquid or
solid ).Fluorine and chlorine are gases of pale yellow and greenish yellow
colours respectively at room temperature and pressure. Bromine is a liquid
of red-brown colour and iodine is a metallic-appearing shiny greyish black
solid. The halogens have irritating odours, and they attack the skin. Bromine
in particular causes burns that heal slowly.The outer shell of halogens have
the configuration ns2 np5 (one electron short of the stable octet of the noble
gases). The electronic configurations and the important physical properties of
the halogens are given in the Table 5.1

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The ionization energy data of the halogens show that the

fluorine atom holds its electrons tightly whereas the electrons
are least tightly bound in iodine. The trend can be correlated
with the sizes of the halogen atoms as shown in the Table 5.1.
The electron affinity values of halogens are large and negative, that is
why halogens gain electrons readily. They have large, positive standard
electrode potentials and their electronegatvities are also fairly high.

Animation 5.2: Halogens

Source & Credit: tumblr

The intermolecular attraction is greater in the larger molecules having

greater masses. Due to their large size the van der Waal’s forces in iodine
molecules are stronger than in the smaller molecules of the other halogens.

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5. The Halogens and the Noble Gases eLearn.Punjab

Table 5.1 The Electronic Configurations and the Important Physical

Properties of the Halogens.
Properties Fluorine Chlorine Bromine Iodine

Atomic number 9 17 35 53
Electronic [Ne]3s2,3p5
[Kr]4d10,5s2,5p5
configuration [He]2s 2p
2 5
[Ar]3d ,4s \4p
10 2 5

Physical Pale Yellow Greenish Shiny greyish

appearance Red-brown liquid
gas yellow gas black solid
Ionization energy
1681 1251 1140 1008
(kJmole-1)
Electron affinity,
(kjmole-1) -322 -349 -325 -295

Electronegativity 4.00 3.00 2.8 2.5

Ionic radius (pm) 136 181 196 216
Covalent radius
72 99 114 133
(pm)
Melting point (°C) -220 -101 -7.2 114
Boiling point (°C) -188 -34.6 58.8 184.4
Density (g/cm3) 0.00181 0.00321 3.12 4.93
Oxidation states - l,+ l,+ 3 ,
-1 -1,1 ,+ 3 ,+ 5 ,+ 7 -1 ,1 ,+ 3 ,+ 5 ,+ 7
+ 5 ,+ 7
Bond energy
154.80 242.67 192.46 150.6
(kJmoie-l)(X-X)

5.2 OCCURRENCE

Elements with the higher values of electronegativity usually exist as

negative ions, and those with the lower values of electronegativity exist
as positive ions. Elements with intermediate values of electronegativity
are often found as ions or molecules or in free (elemental)form.

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None of the halogens is found in free form in nature. The halogens exist
in nature primarily in the form of compounds. Their most common state
is the halide ions F-, Cl-, Br- and I- . These halides are soluble in water
and are found in sea, in salt lakes and as underground beds of salt.
Fluorine Chlorine

Fluorospar CaF2 Halite NaCl

Cryolite Na3AIF6 (Salt beds, brine wells, sea water)
Fluoroapatite Ca5(PO4)3F Carnallite KCl. MgCl2.6H2O
Bromine Iodine

Brine wells, sea water, NaBr, KBr, MgBr2 NaIO3, NaIO4, deposits in Chile
brine wells.

Animation 5.3: Periodic Table

Source & Credit: excelhero

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5. The Halogens and the Noble Gases eLearn.Punjab

5.3 PECULIAR BEHAVIOUR OF FLUORINE

The halogens form a homologous series but fluorine differs from the other
halogens in many respects which is due to:
1. Small size of F atom and of F- ion.
2. High first ionization energy and electronegativity.
3. Low dissociation energy of F2 molecule as compared to Cl2 and Br2.
4. Restriction of the valence shell to an octet.
5. Direct combination with inert gases.
Due to the small size of the F atom (or F- ion), there will be a better overlap
of orbitals and consequently leads to shorter and stronger bonds with
elements other than O, N and itself. Ionic fluorides have higher lattice
energies than the other halides and these values are responsible for the
insolubility of the fluorides of Ca, Mg, Ba,Sr and lanthanides in water. Due
to the low dissociation energy of fluorine molecule, it is highly reactive.
The other halogens react slowly under similar conditions. The fluorides
are, however, more stable with respect to dissociation into elements.
Due to the restriction of valence shell to an octet, many fluoro
compounds show inertness, e.g. CF4 and SF6. Also due to this
restriction, fluorine remains restricted to -1 oxidation state.
Fluorine is the only element that combines directly with
noble gases like Kr, Xe, and Rn forming their fluorides.

5.4 OXIDIZING PROPERTIES

Relative Reactivities of the Halogens as Oxidizing Agents

All the free halogens act as oxidizing agents when they react with metals
or nonmetals. The reactant elements acquire positive oxidation state
in the compounds formed. On forming ionic compounds with metals,
the halogens gain electrons and are converted to negative halide ions.

2Na + Cl2 → 2Na + Cl-


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The oxidizing power of halogens decreases with increase in atomic

number. Fluorine has the highest oxidizing power and iodine the least.
The order of decreasing power as an oxidizing agent is F2 > Cl2 > Br2 > I2

The oxidizing power of halogens depends upon the following factors:

1. Energy of dissociation
2. Electron affinity of atoms
3. Hydration energies of ions
4. Heats of vapourization (for Br2 and I2)

If a halogen has a low energy of dissociation, a high electron affinity and

a higher hydration energy of its ions, it will have a high oxidizing power.
Oxidizing power of F2 is higher, because it has low energy of
dissociation and higher hydration energy of its ions. Due to the
relative strength as oxidizing agents, it is possible for each free
halogen to oxidize the ions of other halogens next to it in the
family. Standard electrode potential measures oxidizing power.

F2 CI2 Br2 I2
Standard reduction potential. E (V)
o

X + 2e- →2X
X22+2e -
2X +2.87 +1.36 +1.07 +0.54

Fluorine can oxidize all the halide ions to molecular halogens.

(A reaction will occur if the value of E°is positive) Iodine being
a weak oxidizing agent cannot oxidize chloride or bromide ion.

F2 + 2e- 
→ 2F- E o =2.87V
-
2Cl  → Cl2 +2e -
E o = -1.36V
F2 +2Cl- 
→ Cl2 +2F- E o =+1.51V

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In the similar way, chlorine will oxidize both bromide and io-
dide ions, while bromine can oxidize only iodide ion.

Cl2 +2Br - 
→ Br2 +2Cl-
Br2 +2l- 
→ I 2 +2Br -
Fluorine and chlorine can oxidize various coloured
dyes to colourless substances, e.g. litmus and univer-
sal indicator can be decolourized when exposed to fluorine or
chlorine. When used for bleaching, chlorine acts as an oxidizing agent.

5.5 COMPOUNDS OF HALOGENS

5.5.1 Hydrides (hydrogen halides, HX)

All halogens react with hydrogen forming hydrides. The reaction of

molecular hydrogen and fluorine is very fast and explosive. With chlorine,
molecular hydrogen reacts in the presence of sunlight. Bromine and iodine
react with molecular hydrogen at a higher temperature. The reaction
with iodine is very slow and reversible. Direct combination is used as a
preparative method only for HCl and HBr. Hydrogen fluoride and hydrogen
chloride can also be obtained by the action of concentrated sulphuric acid
on fluorides and chlorides, but analogous reactions with bromides and
iodides result in partial oxidation of the hydrogen halide to the free halogen.

2NaCl(s)+H 2SO 4 (conc.) 

→ Na 2SO 4 (aq)+2HCl(g)
2NaBr(s)+2H 2SO 4 (conc.) 
→ Na 2SO 4 (aq)+Br2 (l)+SO 2 (g)+2H 2O
Properties of Hydrogen Halides

HF is a colourless volatile liquid whereas other hydrogen

halides (HCI, HBr, HI) are colourless gases at room temperature.
They give fumes in moist air. They are strong irritants.

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Hydrogen fluoride attacks glass and has found applications as a non-

aqueous solvent. It can be handled in teflon ( polytetrafluoroethylene)
containers or if absolutely dry, in copper or stainless- steel vessels
kept under vacuum. Pure liquid HF is strongly hydrogen bonded and
is a viscous liquid. Its viscosity is less than that of water due to the
absence of a three dimensional network of H-bonds which occur in H2O.
Hydrogen bonding is also responsible for the association of HF molecules
in the vapour phase. Various test results indicate that gaseous HF consists
of an equilibrium mixture of monomers and cyclic hexamers, Fig.5.2.

6HF �� ��
� � (HF)6
Chain polymers may also exist under certain conditions. Chains and rings of
HF are of various sizes, some of these persist in the vapour phase as well.
Some of the physical properties of hydrogen halides are given in Table 5.2.

Table 5.2 Some Physical Properties of Hydrogen Halides

Property HF HCI HBr HI
Melting points(°C) -83.8 -114.2 -86.9 -50.8
Boiling points (°C) 19.5 -85.0 -66.7 -35.3
Heat of fusion at M.P. (kJ/mol) 4.58 1.99 2.41 2.87
Heat of vaporization at B.P. (kJ/mol) 30.3 16.2 17.6 19.7
Heat of formation /kJ mol-1(rHf) -270.0 -92.0 -36.0 +26.0
Bond energy (kJ /mol-1) 566 431 366 299
H-X Bond length (pm) 92 128 141 160
Dissociation into elements at 1000°C (%) 0 0.014 0.5 33
Dipole moment (Debye) 1.8 1.1 0.8 0.4

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Melting points, boiling points, heats of fusion and heats of vapourization

generally increase regularly from HCl to HI. The HF has much higher values
for these properties due to hydrogen bonding. A very high boiling point of
hydrogen fluoride is a major evidence of the presence of hydrogen bonding
among its molecules.The relative volatility of HCl, HBr and HI reflects the
strengthening of the van der Waal’s forces due to increasing size of halogens.
Since the dipole moment of molecules decreases from HCI to
HI, probably dipole-induced dipole forces play an important
role in the intermolecular binding of the heavier HX molecules.
The strength of the hydrogen halogen bond is very high in HF. It decreases
with increasing size of the halogen atom. The bond strength is reflected
in the case of dissociation of hydrogen halides at elevated temperatures.

HF, HCl, HBr and HI act as reducing agents in the following order:

HF<HCl<HBr<HI
Hydrogen iodide is a strong reducing agent. In redox reactions
the hydrogen halides are oxidized to elemental halogens, e.g.

2HI+S �� ��
� � I 2 +H 2 S
In water, hydrogen halides give hydrofluoric, hydrochloric, hydrobromic
and hydroiodic acids. Hydrofluoric acid is a weak acid due to limited ionization.
The other three acids are very strong acids. The acidic strength increases
in the order.
HF<HCl<HBr<HI
5.5.2 Oxides of Halogens

The halogens do not react directly with oxygen. With the help of some
indirect methods, following oxides of group VIIA elements have been made.

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Table 5.3 Oxides of Halogens

FLUORINE CHLORINE BROMINE IODINE

Oxygen difluoride, OF2 Dichlorine monoxide, CI2O Brominemonoxide,Br2O Iodine tetraoxide, I2O4

Dioxygen difluoride,O2F2 Chlorine dioxide, CIO2 Bromine dioxide,BrO2 Iodine iodate, I4O9
Trioxygen difluoride Chorine hexaoxide, CI2O6 Bromine trioxide, Iodine pentoxide,I2O5
Chlorine heptaoxide.Cl2O7 BrO3,(Br3O8)

Oxides of Fluorine

Trioxygen Difluoride, O3F2

This oxide can be prepared
when a mixture of fluorine
and oxygen is subjected
to electric discharge. At 363 °C,
it is a dark red viscous liquid but
turns to reddish brown solid
at 350 °C. On decomposition it
gives oxygen and other oxide of
fluorine.

2O3F2 
→ 2O 2 F2 +O 2
O3F2 reacts with F2 in the presence of electric discharge to produce O2F2

2O3F2 +F2 
→ 3O 2 F2
OXIDES OF CHLORINE

The oxides of chlorine are generally unstable. It is not possible

to synthesize them by direct combination of the elements
Cl2 and O2. They have extensive industrial use as commercial
bleaching agents for wood, paper- pulp and for water treatment.

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1. Chlorine dioxide, CIO2

It is a pale yellow gas. It is prepared by reducing NaCIO3, with NaCl or SO2 or
CH3OH in strongly acidic solution.

2CIO - 3 +2CI- +4H + 

→ 2CIO 2 +CI 2 +2H 2O
CIO2 can also be prepared by the action of concentrated H2SO4 on KCIO3,.
This reaction is violent. To control the reaction oxalic acid should be
added.

2KCIO3 +H 2C2O 4 +H 2SO 4 

→ K 2SO 4 +2H 2O+2CO 2 +2CIO 2
CIO2 explodes into Cl2 and O2 on warming. It is soluble in water and is stable
in dark. It decomposes slowly in H2O to HCI and HCIO3. It is a paramagnetic
substance. It is used as an antiseptic, for purification of water and to
bleach cellulose material.
2. Chlorine Heptaoxide, CI2O7
CI2O7 is an anhydride of perchloric acid (HCIO4). It can be obtained at -10oC by
dehydration of HCIO4 with P2O5.

-10o C
2HCIO 4 +P2O5 
→ Cl2O7 +2HPO3
OXIDES OF BROMINE
Oxides of bromine are dark volatile liquids with low thermal stability.
Bromine Monoxide Br2O
It can be prepared by the reaction of bromine vapours with mercuric
oxide. o
50 C
HgO+2Br2  → HgBr2 +Br2O
Br2O can also be prepared by treating the suspension of mercuric oxide in
CCI4 with bromine.It is stable in dark in CCI4 at -20°C. It has oxidizing
properties.
OXIDES OF IODINE
Out of all the oxides of iodine only iodine pentaoxide (I2O5) is important.
The other compounds, I2O4 and I2O9 are salt like and are considered
as iodine-iodates.
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Iodine Pentoxide I2O5

It can be prepared by heating iodic acid at 240°C.
240o C
2HIO3 
→ I 2O5 +H 2O
It is a white crystalline solid, stable up to 300°C. It has a polymeric
structure. It is insoluble in organic solvents. It forms iodic acid with water.

I 2O5 +H 2O 
→ 2HIO3
It reacts with H2S, HCI and CO as an oxidizing agent.
It is used for the quantitative analysis of CO.

5CO+I 2O5 
→ I 2+5CO 2
5.5.3 Reactions of Chlorine with Cold and Hot NaOH

The reactions of chlorine with cold and hot NaOH are examples of
“Disproportionation reactions”.
A reaction in which a species (molecule, atom or ion)is simultaneously
oxidized and reduced, is called a “disproportionation reaction”.
In cold (15°C) state chlorine will react with NaOH (aq) to form hypochlorite
and a halide.

15o C
2NaOH(aq)+Cl2 (g) 
→ NaCl(aq)+NaClO(aq)+H 2O(aq) (a)
Sod.hypochlorite
The reaction is a disproportionation reaction, because the zero oxidation
state of chlorine atom in Cl2, is converted to -1 in chloride and +1 in
hypochlorite.

Sodium hypochlorite which is produced in cold state in the above reaction,

decomposes forming sodium chloride and sodium chlorate at 70°C.

70o C
3NaClO(aq) 
→ 2NaCl(aq)+NaClO3 (aq) )b(

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The reaction (b) involves the disproportionation of hypochlorite ion.

To balance overall reaction in hot state, multiply equation (a) with 3 and then
add (a) and (b).
6NaOH+3Cl2 
→ 3NaCl+3NaClO+3H 2O
3NaClO → 2NaCl+NaClO3
6NaOH(aq)+3Cl2 (g) 
→ 5NaCl(aq)+NaClO3 (aq)+3H 2 O
The above two reactions (a) and (b) show that chlorine atoms are both
reduced and oxidized.

5.5.4 Oxyacids

An important class of the compounds of the halogens is the oxygen containing

acids and their salts.
No oxygen containing stable acid of fluorine is known (HOF is
prepared recently, but it is highly unstable). Other halogens form
oxyacids though most of them cannot be isolated in pure form
and are stable only in aqueous solutions in the form of their salts.
A system of nomenclature for these acids and their salts is based on the
oxidation state of the halogen atom. According to this system, characteristic
prefixes and suffixes are attached to a stem that is derived from the
name of the central nonmetal (halogen) atom. The system is as follows:-

1. Some common acid is orbitrarily called the _____ ic acid (e.g. HCIO3 is
designated as chloric acid). The name of a salt of this acid ends in _____
ate.
2. An acid whose parent atom has an oxidation state next lower than the
_____ ic acid (one less oxygen atom) is called ous acid and the name of the
salt of this acid ends in _____ ite. For example, chlorous acid (HCIO2).
3. The acid in which the oxidation state of the parent atom is higher than it
is in the _____ ic acid (one more oxygen atom) is called per_____ ic acid. A
salt of this acid is a per _____ ate salt. For example, perchloric acid (HCIO4).

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4. An acid in which the oxidation state of the parent atom is lower than it is
in the___ ous acid is called hypo _____ ous acid and a salt of this acid is a hypo
_____ ite salt. For example, hypochlorous acid (HCIO).
5. The root of the name of the acid or the salt indicates the parent atom.

Table 5.4 shows the oxyacids of halogens (other than fluorine)

Table 5.4 Oxyacids of Halogens
Oxidation Formula of the oxyacids of
General names of
state halogens
of halogen Chlorine Bromine Iodine Oxyacids Salts of
oxyacids
+1 HCIO HBrO HIO Hypohalous acid Hypo__ite
+3 HCIO2 ------ ------ Halous acid ____ite
+5 HCIO3 HBrO3 HIO3 Halic acid ____ ate
+7 HCIO4 HIO4, H5IO6 Perhalic acid Per____
ate
It is evident from the above given formulas of the oxy acids that
the halogen serves as a central atom to which one or more oxygen
atoms are covlently bonded. These bonds are polar in character due
to the electronegativity difference between halogen and oxygen.

The increase in the oxidation state of the halogen from +1 to + 7 is

accompanied by :
(a) an increase in the thermal stability of the acid
(b) the decrease in oxidizing power of the acid
(c) the increase in acidic strength of the acid

The more the number of oxygen atoms in the series of oxyacids of a halogen,
the greater is the thermal stability.
The acid strength increases with the increase in the number of oxygen
atoms. As the oxidation state of the halogen increases, the bonding electrons
are shifted away from the Hatom and the tendency of the molecule to lose
a proton increases. This accounts for the change of strength of oxyacids.
The oxyacids of halogens show their strength in the order given below:

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HXO 4 >HXO3 >HXO 2 >HXO

An oxyacid molecule contains hydrogen linked to the halogen through an
oxygen atom.
The oxyacids of chlorine are stronger than the corresponding oxyacids of
bromine which are, in turn, stronger than the corresponding oxyacids of
iodine. It is due to decrease in the electronegativity and increase in the size of
the halogen.
We will discuss perchloric acid (HClO4) only at this stage.

PERCHLORIC ACID (HCIO4)

Perchloric acid (HClO4)is commonly obtained in aqueous solution.

Pure anhydrous compound can by prepared by distilling a mixture of
potassium perchlorate (KCIO4) and conc. H2SO4 under reduced pressure.

Ä
KClO 4 +H 2SO 4 (conc.) 
reduced pressure
→ KHSO 4 (s)+HClO 4 (l)
Perchloric acid is a colourless hygroscopic liquid. At normal
pressure it freezes at -112°C and boils with decomposition at 90° C.

In the cold and dilute state,perchloric acid is a very weak oxidizing agent
but when hot and concentrated its oxidizing power is enhanced. Dissolving
power of perchloric acid is enhanced due to its oxidizing strength.
Perchloric acid is the strongest of all the acids in an aqueous medium.

Pure perchloric acid decomposes explosively when heated.

That is why it is stored and used as 67% solution in water.
Perchloric acid reacts with organic substances violently.

Due to its oxidizing effect, acidic strength and solubility of its salts, it is
considered as a valuable analytical reagent.

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Animation 5.4: Perchloric acid

Source & Credit: bouman

5.5.5 Bleaching Powder, (Ca(OCl)Cl)

Bleaching powder can be manufactured by the action of chlorine

on dry slaked lime using any one of the following methods:

(a) Hasenclever’s method (old method)

(b) Beckmann’s method (modern method)
The reaction in both the cases will be:

Ca(OH) 2 +Cl2 
→ Ca(OCl)Cl+H 2O
Slaked lime Bleaching powder

(1) Hasenclever’s Method

The apparatus used in this method consists of 4 to 8 iron cylinders placed
one above the other horizontally. They are interconnected and provided
with stirrers. The slaked lime is added in through a hopper in the upper
cylinder and is transported from one cylinder to the other with rotating
stirrers. Chlorine introduced into the lowest cylinder rises up and reacts
with slaked lime to form bleaching powder, which is collected through
the outlet in the lowest cylinder.

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(2) Beckmann’s Method

In this method a cast iron tower with eight horizontal shelves is used.
In each shelf there is a rotating rake.Powdered slaked lime is introduced
through hopper at the top with compressed air. A mixture of hot air and
chlorine are introduced from the base of the tower. The slaked lime is pushed
down by the rotating rakes while chlorine rises up. Reaction between slaked
lime and chlorine produces bleaching powder which is collected at the bottom
of the tower, Fig.5.3

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The apparatus works on the countercurrent principle. Thus

maximum reaction of slaked lime and chlorine is brought about
with very little loss of chorine. Bleaching powder should always
be packed in air tight containers to avoid the loss of chlorine.

Bleaching powder is a yellowish white powder with strong smell

of chlorine. Some of its chemical properties are given below.
1. It is an oxidizing agent. This property is due to the generation of
hypochlorite ion (OCl) in water.
H O
CaOCl2 �� �� 2�� �� Ca +2 +Cl- +ClO -
2. With dilute acid it gives hypochlorous acid.

2CaOCl2 +dil.H 2SO 4 

→ CaSO 4 +CaCl2 +2HClO
3. If excess of an acid (weak or strong) is added to bleaching powder,
chlorine is given out.
CaOCl2 +H 2SO 4 
→ CaSO 4 +H 2O+Cl2 ↑
(excess)
The amount of chlorine thus set free is called “available chlorine”. The activity
of bleaching powder is measured in terms of available chlorine. The average
percentage of available chlorine in bleaching powder is 35-40 percent.
The bleaching action of bleaching powder is due to its oxidative character.

4. It oxidizes HC1, HBr and HI giving the corresponding halogens.

CaOCl2 +2HCl 
→ CaCl2 +H 2O+Cl2
5. It oxidizes ammonia to nitrogen

3CaOCl2 +2NH 3 
→ 3CaCl2 +3H 2O+N 2
6. Calcium hypochlorite reacts with carbon dioxide to form calcium
carbonate and release chlorine.

CaOCl2 +CO 2 
→ CaCO3 +Cl2
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Uses

Bleaching powder is used:

1. for the laboratory preparation of chlorine and oxygen. It is also used
in the manufacture of chloroform.
2. as a disinfectant and in the sterilization of water.
3. for making unshrinkable wool.
4. for bleaching cotton, linen and paper pulp. (Delicate fabrics like wool,
silk etc. cannot bebleached with it as these could be damaged by
chlorine).

5.6 COMMERCIAL USES OF HALOGEN AND THEIR

COMPOUNDS

Fluorine is used for the preparation of freons. Freon is the commercial

name of low molecular mass fluorochlorocarbons, CCl2F2, CClF3.
These are being used as refrigerants and aerosol propellants.

Fluorine is used to prepare Teflon (-CF2— CF2-)n. It

is a polymerized tetrafluoro ethylene compound.
It is a valuable plastic which resists the action
of oxidants, acids and alkalies.Corrosion-
proof parts of machinery are made of it.It is
used for coating the electrical wiring.Teflon is
also used as a non-stick coating for cooking
pans.Halothane is used as an anaesthetic.

Fluorides in toothpastes build a protective coating on teeth.

Chlorine is used in the manufacture of bleaching powder.It is used as a
disinfectant in swimming pools and water treatment plants. A number of
antiseptics, insecticides, weedkillers and herbicides are manufactured
from chlorine.It is also used in the manufacture of hydrochloric acid,
which is the cheapest industrial acid.Chlorine is also used in the
manufacture of polyvinyl chloride (PVC) plastics. Chloroform and carbon
tetrachloride are prepared from chlorine which are used as solvents.

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Ethylene dibromide (C2H4Br2) is added to leaded gasoline to save

the engine from lead oxide and lead sulphate deposits. Bromine
is also used as fungicide. Silver bromide is used in photography.
The major applications of iodine are in pharmaceutical
industry.It is used as disinfectant and germicide.Tincture
of iodine and iodex are popular preparations of iodine.
Diet with insufficient iodide ions leads to an enlargement of the thyroid
(Goiter). To ensure the presence of iodide ion in the diet, sodium or
potassium iodide is added to the common salt which is known as iodized
salt.

5.7 NOBLE GASES

5.7.1 Introduction
The elements helium(He), neon (Ne), argon(Ar), krypton (Kr), xenon (Xe) and
radon (Rn) are placed in the zero group or group VIIIA of the periodic table.
All the elements of this group are colourless and odourless monoatomic
gases which can be liquefied and solidified. These are called noble gases
or sometime known as rare gases. The noble gases occur as minor
constituents of the atmosphere (about 1%). The electronic configurations
and some physical properties of noble gases are given in the Table 5.5.
Table 5.5 Electronic Configurations and Physical Properties of Noble Gases

Property He Ne Ar Kr Xe Rn
Atomic number 2 10 18 36 54 86
Electronic Is2 (He)2s2 (Ne)3s2 (Ar)3d10 4s2 (Kr)4d10 (Xe)5d10
configurations 2p6 3p6 4p6 5s2 5p6 6s2 6p6
Ionization energy 2372 2081 1521 1351 1170 1037
(kJmol-1)
Atomic radius (pm) 40 70 94 109 130 140
Melting points (oC) -272 -249 -189 -157 -112 -71
Boiling points (oC) -269 -246 -186 -153 -108 -61
Water solubility (ml/lit) 13.8 14.7 37.9 73.00 110.9 ----
at 20oC
Heat of vapourisation 0.08 1.77 6.5 9.7 13.7 18.0
(kJmol-1)

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5. The Halogens and the Noble Gases eLearn.Punjab

The noble gases are isolated from air, either by fractional distillation or by some
chemical method. The principal commercial source of Ne, Ar, Kr and Xe is air.
Helium is present on earth as a result of radioactive decay. After hydrogen, it
is the second most abundant element in the universe. a-Particles are doubly
ionized helium atoms He2+. It is simple and economical to isolate the helium gas
from certain natural gases by liquefaction method.

Argon is a colourless and odourless gas. It is very inert and not known to form
any true chemical compound. It is obtained as a by-product during the lique
faction of air.
Neon is 1/65000th part of the atmosphere and it is also isolated during
liquefaction of air. In a discharge tube, neon glows reddish (of all the noble
gases, the discharge of neon is the most intense at ordinary voltage and current).
Liquid neon has over 40 times more refrigeration capacity than liquid helium.
Traces of krypton are present in air. It is a colourless, odourless and fairly
expensive gas. It is characterized by its brilliant green and orange spectral lines.
Its compound krypton difluoride (KrF2) can be prepared by various methods.

Xenon is present in the atmosphere to a very small extent (0.08 ppm).

It is obtained as a by-product during the fractional liquefaction of air.
Xenon is available
commercially in cylinders at high pressure. It reacts with fluorine but not
with water. However it is slightly soluble in water to the extent of about
110 ml/lit at 20°C.
Radon is the a-decay product of the radium. Radon is present to a very
small extent in the atmosphere and it could be obtained as a by-product
from the liquefaction of air. However, the small quantities of this gas
which are usually needed can be collected from the radioactive decay of
radium isotopes.
226 222
88 Ra 
→ 86 Rn+ 4X He
The noble gases have valence shells which are closed octets (except He).
Due to closed shells their ionization energy values are very high. They have
low boiling points. The boiling point of helium is the lowest of any known
substance. Their boiling points increase with increasing atomic number
down the group.
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5. The Halogens and the Noble Gases eLearn.Punjab

The very low values of melting and boiling points and low heats of
vapourization show that noble gases have weak forces of attraction
between their atoms. As there are no ordinary electron pair
interaction, these weak forces must be of the van derWaals type.
The solubility of the noble gases in water increases with increasing atomic
number. This is because the bigger atoms are more readily polarized by
water molecules.

5.7.2 Compounds of Xenon

Xenon reacts directly with fluorine only. The known oxidation

state of Xenon in its compounds range from +2 to +8. These
compounds are stable and can be obtained in large quantities.
Some important compounds of Xenon are give in the Table 5.6
Table 5.6 Compounds of Xenon
Oxidation state Compound Physical form Melting Point
of xenon (°C)

+2 XeF2 140
Colourless crystals
+4 Xe F4 Colourless crystals 114
XeOF2 Colourless crystals 90
+6 XeF6 Colourless crystals 48
XeOF4 Colourless liquid -28
+8 XeO3 25 (Explodes)
Colourless crystals
XeO4 -39.9 (Explodes on
Colourless gas
warming)

Animation 5.5: flroride

Source & Credit: waterus

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5. The Halogens and the Noble Gases eLearn.Punjab

5.7.3 Fluorides of Xenon

Three known fluorides of Xenon are XeF2, XeF4 and XeF6.

XeF2 can be prepared by direct interaction of the elements.The

compound formed should be removed immediately from the
reaction zone, otherwise further reaction with F2 will give XeF4.
The reaction is completed in about 8 hours. XeF2 is a crystalline
solid. It is stored in nickel vessels. XeF2 is a mild fluorinating agent.

XeF4 can be prepared by heating a mixture of Xe and F2 in 1:5

ratio in a nickel container under 6 atmospheric pressure for
a few hours. It can be stored in nickel vessels. Its properties
are similar to that of XeF2 but it is a strong fluorinating agent.
XeF6 requires more severe conditions. Xe and F2 are taken in 3:20 ratio in
a stainless steel vessel and heated to 300°C at 50 atmospheric pressure.
More than 95% conversion to XeF6 takes place. XeF6 is a crystalline solid.
It is colourless in the solid state but yellow in liquid and gaseous forms.

Xe+F2 
→ XeF2
XeF2 +F2 
→ XeF4
XeF4 +F2 
→ XeF6

Animation 5.6: flroride1

Source & Credit: waterus

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5. The Halogens and the Noble Gases eLearn.Punjab

Chemical Reactions
Fluorides of xenon can be reduced with hydrogen at 400°C, giving xenon and
hydrofluoric acid.
XeF2 +H 2 
→ Xe+2HF
XeF4 +2H 2 
→ Xe+4HF
XeF6 +3H 2 
→ Xe+6HF
Xenon tetra-fluoride is a good fluorinating agent and can be used to prepare metal
fluorides as follows:
XeF4 +2Hg 
→ Xe+2HgF2
Reaction occurs with explosion when XeF4 is brought in contact with liquid
ammonia.
3XeF4 +4NH 3 
→ 3Xe+12HF+2N 2
Hydrolysis of XeF6 with small amount of water gives XeOF4

XeF6 +H 2O 
→ XeOF4 +2HF
5.7.4 Xenon Oxyfluorides

Xenon oxytetrafluoride, XeOF4 is also formed by a rapid reaction of XeF6

with silica (quartz).

2XeF6 +SiO 2 
→ 2XeOF4 +SiF4
XeOF4 is a colourless volatile liquid. It can be kept
in nickel vessel.It reacts with water to give XeO3.

XeOF4 +2H 2O 
→ XeO3 +4HF
Xenon oxydifluoride, XeOF2 is obtained when xenon
reacts with oxygen difluoride in an electric discharge.

Xe+F2O 
→ XeOF2
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5. The Halogens and the Noble Gases eLearn.Punjab

5.7.5 Oxides of Xenon

There are two oxides of xenon

1. Xenon trioxide
2. Xenon tetraoxide

Animation 5.7: Oxidized

Source & Credit: bp.blogspot
1. Xenon Trioxide XeO3
Xenon trioxide can be obtained when XeF6 is hydrolysed slowly.

XeF6 +3H 2O 
→ XeO3 +6HF
It is a crystalline solid. It explodes at very low temperature. It is
weakly acidic and its aqueous solution is almost non-conductor.

2. Xenon Tetraoxide XeO4

It is obtained by the addition of barium or sodium perxenate to conc.H2SO4
Ba 2 XeO6 +2H 2SO 4 
→ XeO 4 +2BaSO 4 +2H 2O
Na 4 XeO6 +2H 2O 4 
→ XeO 4 +2Na 2SO 4 +2H 2O

5.7.6 Applications of the Noble Gases

1. Helium is used in weather balloons, in welding and in traffic signal
light.
2. A mixture of 80% helium and 20% oxygen is used for breathing by the
sea divers.
3. Helium is used as a cooling medium for nuclear reactors.

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5. The Halogens and the Noble Gases eLearn.Punjab

4. Neon is largely used in making neon advertising signs, in high voltage

indicators and TV tubes.
5. Neon and helium arc is used in making glass lasers.
6. Argon is used in electric light bulbs, in fluorescent tubes, in radio tubes,
and in Geiger counters (used to detect radioactivity).
7. Argon is also used for arc welding and cutting.

8. Krypton is used to fill fluorescent tubes and in flash lamps for high speed
photography.
9. Xenon is used in bactericidal lamps.
10. Radon being radioactive is used in radiotherapy for cancer and for
earth quake prediction.

KEY POINTS

1. The halogens are very reactive. Intermolecular forces in halogens increase

down the group, fluorine is a gas but iodine is solid.
2. They form ionic compounds with s-block metals, covalent compounds
with p-block elements and complex ions with d-block metals. Fluorides are
usually ionic.
3. They show oxidation states -1, +1, +3, +5, + 7 but fluorine shows the oxidation
state of -1 only.
4. Oxidizing power of halogens decreases down the group in the following
order:
F2 Cl2 Br2 I2
V

5. Reducing power of halide ions decreases from I- to Br- Chloride and fluoride
ions are not reductants.
6. Chlorine, bromine and iodine form their respective oxides and oxyacids.
7. Halogens and their compounds are used for bleaching, refrigeration and as
aerosols, etc.
8. Noble gases are placed in zero (VIIIA) group of periodic table.
9. They have valence shells which are closed octets (except helium).
10. Very low values of melting and boiling points show that there are
very weak forces of attraction between their atoms.
11. Oxides, fluorides and oxyfluorides of xenon can be prepared.
12. Noble gases have multi-dimensional uses.
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5. The Halogens and the Noble Gases eLearn.Punjab

EXERCISE
Q.l Fill in the blanks.
(i) The halogen with the highest electronegativity is ___________________.
(ii) HI is _________ agent.
(iii) The only halogen acid which is not a strong acid is ________________ .
(iv) Tincture of______________ is a common antiseptic.
(v) The halogen with the lowest melting and boiling points is __________.
(vi) Bleaching powder is prepared from _________ and ____________.
(vii) _____________ is the halogen which causes burns on the skin which
heal slowly.
(viii) _____________is used for making unshrinkable wool.
(ix) A mixture of ___________and ____________ is used for breathing by the
sea divers.
(x) Noble gas used to fill fluorescent tubes is _______________.
Q.2 Indicate True or False.
(i) HF is used for etching glass.
(ii) HI is weaker reducing agent as compared to HF
(iii) Bleaching powder is completely soluble in water.
(iv) The formula of perchloric acid is HCIO2.
(v) On warming, aqueous KOCl disproportionates as follows.
(vi) a-particles emitted by radioactive elements are ions of radon.
(vii) Radon is the only one of the noble gases that is radioactive.
(viii) The molecules of the noble gases are all monoatomic.
(ix) Argon is used to fill electric bulbs.
(x) The noble gas which is present in the largest amount in atmosphere
is krypton.
Q 3. Multiple choice questions. Encircle the correct answer.
(i) Which of the following hydrogen halide is the weakest acid in solution?
(a) HF (b) HBr (c) HI (d) HCI
(ii) Chlorine heptaoxide (Cl2O7) reacts with water to form:
(a) Hypochlorous acid (b) Chloric acid
(c) Perchloric acid (d) Chlorine and oxygen
(iii) Hydrogen bond is the strongest between the molecules of:
(a) HF (b) HCl (c) HBr (d) HI
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5. The Halogens and the Noble Gases eLearn.Punjab

(iv) Which halogen will react spontaneously with Au(s) to produce Au3+?
(a) Br2 (b)F2 (c) I2 (d) Cl2
(v) The anhydride of HCIO4 is :
(a) CIO3 (b) ClO2 (c) Cl2O5 (d) CI2O7
(vi) Bleaching powder may be poduced by passing chlorine over:
(a) calcium carbonate (b) hydrated calcium sulphate
(c) anhydrous calcium sulphate (d) calcium hydroxide
(e) magnesium hydroxide
(vii)Which is the strongest acid?
(a) HCIO (b) HClO2 ( c ) HClO3 (d) HClO4
(viii) Which halogen occurs naturally in a positive oxidation state?
(a) Fluorine (b) Chlorine (c) Bromine (d) Iodine
(ix) An element that has a high ionization energy and tends to be chemically
inactive would most likely to be:
(a) an alkali metal (b) a transition element
(c) a noble gas (d) a halogen
(x) Which of the following represents the correct electronic configuration
of the outermost energy level of an element of zero (VIIIA) group in the
ground state.
(a) s2p2 (b) s2p4 (c) s2p5 (d) s2p6

Q.4 What is bleaching powder? How it is prepared commercially? Give its

uses.

Q.5 (a) Discuss the oxides of chlorine.

(b) What are disproportionation reactions? Explain your answer with an
example.

Q.6 Discuss the system of nomenclature used for oxyacid of halogens.

Support your answer with examples.

Q.7 (a) How the halogen acids are ionized in water?

(b) Why HF is weaker acid than HCl?

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5. The Halogens and the Noble Gases eLearn.Punjab

Q.8 In the following sets, arrange the substances in order of the property
indicated. Give reasons.
(a) Increasing acidic character
HCIO, HCIO2, HClO3, HClO4
(b) Increasing oxidizing power
F2, Cl2, Br2, I2

Q.9 What happens when bleaching powder reacts with the following
reagents dil. H2SO4,excess of conc. H2SO4, NH3, HI and CO2.

Q.10 Discuss the various commercial uses of halogens and their compounds.

Q .11 What are noble gases? Explain their inertness on the basis of their
electronic configuration.

Q.12 Write notes on the followings.

(i) Oxyfluorides of xenon.
(ii) Applications of noble gases.

Q.13 Short questions.

(i) What is “Iodized Salt”?
(ii) What are Freons and Teflon?
(iii) Arrange the following ions in order of increasing size:
F-, CI-, I-, Br-
(iv) Why iodine has metallic luster?
(v) Which halogen sublimes to violet vapours?
(vi) Which halogen is used as an antiseptic?
(vii) Which halogen is used in water treatment to kill becteria ?
(viii) Name the gas, which is used for earthquake prediction.
(ix) Name the gas, which is used in bactericidal lamps.

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