K.

Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Group 17 elements
General introduction
Trends in physical and Chemical properties
Chlorine & Hydrogen chloride preparation, properties & uses
Oxoacids of halogens
Interhalogen compounds

Prepared by
K.Rajeswara Reddy, M.Sc,B.Ed.
Qualified in NET, GATE, APSET.
Faculty in IIIT Srikakulam, RGUKT AP.
Mobile : 9502525616

E-Mail : rajeswarareddy616@gmail.com

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Group 17 elements (Halogen family)

Introduction to the Halogen family:
 Group 17 of the periodic table contains the elements fluorine, chlorine, bromine, iodine
and astatine. These elements are collectively known as HALOGENS. This name is
derived from two Greek words Halo and genes meaning ‘salt producing’.
 Halogens are most reactive non metals.
 Astatine is radioactive element and is, therefore, studied separately.
 Halogens have very strong tendency to acquire stable inert gas configuration by
accepting one electron.

Electron configuration:
The atoms of group 17 have seven electrons in the outermost shell, and have the general
electronic configuration ns2np5.

Occurrence:
 Astatine is radioactive element with very short life.
 All other halogens are abundant in nature in the combined state.
 The very high electro negativities of halogens make them very reactive and hence, they
are not found in free state.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

 In the combined state,

I. Fluorine occurs as –
Cryolite (Na3AlF6), Fluorspar (CaF2), Fluorapatite (3Ca3(PO4)2CaF2)
II. Chorine occurs as –
Sodium chloride (NaCl) (rock-salt) or in sea water.
III. Bromine occurs as –
Bromides of alkali metals or alkaline earth metals in sea water.
IV. Iodine occurs as –
Iodides of alkali metals in sea water, Sodium iodate NaIO3 in chile salt peter.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Oxidation States:
 Halogens have only one electron less than the next noble gas. Therefore, they can get
the noble gas configuration either by gaining one electron to form uninegative ion, X -, or
by sharing electrons with other atoms. Thus they show an oxidation state of -1.

Since fluorine is the most electronegative element, it always shows an oxidation state of
-1. It does not show any positive oxidation state.
 The other elements also show positive oxidation state of +1, +3, +5, +7. The higher
oxidation states of chlorine, bromine and iodine are due to the presence of vacant d-
orbitals in their valence shells. As a result the outer s-or p-electrons can easily be
promoted to the vcacant d-orbitals as shown below.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Physical characteristics of Group 17 elements:

1. Atomic and Ionic radii:

 Among the halogens, the atomic and ionic radii increase with an increase in atomic
number. This is due to increase in the number of electron shells.

2. Ionization energies:
 In group 17 elements i.e, halogens, on going down the group from fluorine to astatine,
the ionization energy decreases. This is due to gradual increase in atomic size, which is
maximum for iodine.

3. Melting and boiling points:

 The melting and boiling points of halogens increases with increase in atomic number
down the group.
 At room temperature, fluorine and chlorine are gases, bromine is a liquid while iodine
and astatine are solids.

4. Electron affinities:
 Electron affinity order of halogens is Cl > F > Br > I.
 Chlorine has the highest electron affinity for an element in the periodic table.

5. Electro negativity:
 The electro negativity values of halogens decrease down the group from fluorine to
iodine because the atomic size increases.
 Fluorine is the most electronegative element in the periodic table.

6. Metallic or non- metallic character:

 All halogens are having non- metallic character. However, in halogens the non metallic
character decreases as we go down the group. Therefore, the last element, iodine is a
solid with a metallic luster.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Chemical Properties:

1. Reactivity with Hydrogen:

 All halogens react with hydrogen to form hydrides, HX, Known as halogen hydrides.

 In Halogen hydrides HF is a low boiling liquid (boiling point 292 K) while HCl, HBr and HI
are gases. The anomalous property of HF is due to hydrogen bonding between the
molecules. HF exists as an associated molecule (HF)n.

 The acidic strength order of halogen hydrides is HF < HCl < HBr < HI.
 The stability of these halides decreases down the group due to decrease in the bond
(H-X) dissociation enthalpy in the order.
H-F > H-Cl > H-Br > H-I

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

2. Reactivity with oxygen:

 Halogens form many oxides with oxygen but most of them are unstable.

3. Reactivity towards metals:

 Halogens react with metals to form metal halides.
Ex: bromine reacts with magnesium to give magnesium bromide.

 The ionic character of the metal hydrides decreases in the order MF > MCl > MBr > MI
where M in a monovalent metal.

4. Reactivity of halogens towards other halogens:

 Halogens combine amongst themselves to form a number of compounds known as
interhalogen compounds of the types AB, AB3, AB5, and AB7 where A is larger size
halogen and B is smaller halogen.
Ex: ICl, BrF5, IF5, IF7 ,etc.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Chlorine and Hydrochloric acid:

Chlorine:
 The Swedish chemist Carl Wilhelm Scheele first prepared chlorine in 1770 by treating
hot concentrated hydrochloric acid with manganese dioxide. Unfortunately, he thought
that it was an oxygen containing compound and did not recognized it as an element.
 After more than 30 years, the English chemist Sir Hymphry Davy recognized chlorine as a
separate element and was given the credit for its discovery.
 The word ‘chlorine’ means “greenish yellow” in Greek.

Preparation of Chlorine:

Laboratory Preparation of Chlorine:

 Chlorine can be prepared by removing the hydrogen from hydrochloric acid using an
oxidizing agent such as manganese dioxide, lead dioxide, Potassium permanganate or
potassium dichromate.
 Firstly the oxidizing agents are taken in the round bottomed flask. Concentrated
hydrochloric acid is then added through a thistle funnel. This mixture is then heated. Cl2
gas is liberated.

 Laboratory preparation of Chlorine from HCl

No heating is required in when Potassium permanganate is used as an oxidizing agent in

the above method of preparing chlorine.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Industrial method of Preparation of Chlorine:

Deacon’s process:
 By oxidation of hydrogen chloride gas with atmospheric oxygen in the presence of CuCl2
(catalyst) at 723 K.

 Chlorine is mostly obtained as a by – product during the manufacture of caustic soda, by

the electrolysis of brine solution (molten sodium chloride). During this electrolysis,
chlorine is liberated at the anode.

Physical properties of Chlorine:

 Chlorine has a greenish yellow color.
 Its odor is pungent and suffocating.
 The vapour density of chlorine = 35.5; it is nearly 2.5 times denser than air ( vapour
density of air = 14.4 ).
 Chlorine is only moderately soluble in water. A 100 ml of water can dissolve about 46 ml
of chlorine at 00c. The solution smells of chlorine, and is called ‘Chlorine water’.

Chemical Properties:

1. with Metals:
 The metals like sodium, Copper, etc. when plunged into a jar of chlorine gas catch fire
spontaneously to form their respective chlorides.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

2. with non metals:

 Yellow Phosphorus first melts and then catches fire spontaneously when introduced into
a jar of chlorine gas. It forms thick white fumes of phosphorus (III) Chloride and
Phosphorus (V) chloride.

3. with hydrogen:
 Introduce a jet of burning hydrogen into a jar of chlorine gas. The hydrogen continues to
burn forming hydrogen chloride.

 Hydrogen and chlorine gas also combine directly in presence of sunlight also. A jar of
hydrogen is inverted and placed on a jar containing chlorine in the sun. Hydrogen
chloride is formed.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

4. with hydrocarbons:
 Introduce a burning candle into a jar of chlorine gas. The candle continues to burn with
a reddish flame, producing a lot of soot. The products formed are hydrogen chloride and
fee carbon.

5. Reaction with hydrogen sulphide:

 On passing chlorine and hydrogen sulphide through separate vents in an upright
combustion tube hydrogen sulphide gets oxidized to sulphur. Hydrogen chloride comes
out through the middle tube.

 If chlorine is passed through a solution of hydrogen sulphide in water the solution turns
turbid due to the formation of free sulphur.

6. with ammonia: Depending on which of the two gases is in excess, chlorine reacts with
ammonia in two ways.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

 When ammonia is in excess the final products are ammonium chloride and nitrogen.

 When chlorine is in excess the final product is an oily, explosive liquid called nitrogen
trichloride.

7. with alkalies:
Alkalies, at different temperatures and at different levels of concentration, behave differently
with chlorine.

i. With cold dilute alkalies:

Chlorine reacts with cold dilute alkalies to form their respective chlorides, hypochlorites
and water.

ii. With hot concentrated alkalies:

Chlorine reacts with hot concentrated alkalies to form their respective chlorides,
chlorates and water.

8. with Slaked Lime:

 Chlorine reacts with slaked lime to give bleaching powder. A white powder is left
behind. This is bleaching powder.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Uses of Chlorine:
 For bleaching wood pulp (required for the manufacture of paper and rayon), bleaching
cotton and textiles.
 In the extraction of noble metals like gold and platinum.
 In the manufacture of dyes, drugs and organic compounds such as CCl4, CHCl3, DDT,
refrigerants, etc.
 In sterilizing drinking water.
 Preparation of poisonous gases such a phosgene (COCl2), tear gas (CCl3NO2), mustard
gas ( ClCH2CH2SCH2CH2Cl ).

Hydrogen Chloride:
Hydrochloric acid was first discovered around A.D.800 when common salt is mixed with sulfuric
acid.

Preparation of Hydrogen Chloride:

 When concentrated sulphuric acid is heated with metal chlorides, hydrogen chloride gas
is liberated. In the laboratory, the chloride used is sodium chloride (common salt) since
it is the cheapest and the most easily available chloride.

Physical Properties:
 Hydrogen chloride gas is colorless.
 It has a pungent and choking smell.
 It is sour to taste.
 Its vapor density = 18.25 ( vapor density of air = 14.4 ), hence it is nearly 1.25 times
denser than air.
 It is extremely soluble in water.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Chemical Properties:

a) It reacts with reactive metals to form their respective chlorides.

b) It neutralizes with bases to form their respective chlorides and water.

c) It combines with carbonates and hydrogen carbonates to form their respective chlorides and
liberate carbon dioxide.

d) It reacts with silver nitrate and lead nitrate solutions to form their white precipitates.

e) This is a mixture of concentrated hydrochloric acid and concentrated nitric acid in the ratio 3:1
by volume. Aqua-regia also called as “royal water” (aqua=water. Regia=royal). The two acids
react to form nascent chlorine which reacts with the noble metals like gold, platinum etc. to
form their respective chlorides.

Uses of Hydrogen Chloride:

It is used in

 In the manufacture of chlorine, NH4Cl and glucose ( from corn, starch),

 For extracting glue from bones and purifying bone black,
 In medicine and as a laboratory reagent.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Oxoacids of Halogens & Interhalogen compounds:

 Halogens, except fluorine, form a number of oxoacids. The acids may be represented by
the general formulas. HXO; HXO2; HXO3 and HXO4. In these oxoacids the halogen
exhibits +1, +3, +5, +7 oxidation states. Of these oxoacids, the oxoacids of chlorine are
very common.

A. Oxoacids of Halogens:
 Due to high electro negativity and small size, fluorine forms only one oxoacid, HOF
known as fluoric (I) acid or hypoflourous acid. The oxoacids of halogens are given in
below shown table.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

B. Interhalogen compounds:
 Halogens combine amongst themselves to form a number of compounds known as
interhalogen compounds. They are of the types AB, AB3, AB5 and AB7 where A is larger
sized halogen and B is smaller sized halogen. As the ration between radii of A and B
increases, the number of atoms per molecule also increases.

Structures of interhalogen compounds:

It may be noted, then in general, that the central halogen atom assumes.

a) sp3d hybridization in AB3 which has a Bent T-Shaped arrangement.

b) sp3d2 hybridization in AB5, which has square pyramidal arrangement.

c) sp3d3 hybridization in AB7 which has pentagonal bipyramidal arrangement.

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K.Rajeswara Reddy Faculty in IIIT Srikakulam, RGUKT AP Group 17 elements

Some Characteristics of inter halogen compounds are:

 They are all covalent compounds.
 They are more reactive than the constituent halogens.
 They are very good oxidizing agents.
 Their melting and boiling points increase with the increase in the difference of
electronegativity.
 Chlorofluoro hydrocarbons are known as Freons and are used as refrigerants
Ex: Freon-1,1 is CCl3F, Freon-1,2 is CCl2F2, Freon-13 is CClF3 etc.

Uses:
 These compounds can be used as non aqueous solvents.
 Interhalogen compounds are very useful halogenating agents.
 ClF3 and BrF3 are used for the production of UF6 in the enrichment of 235U.

“You are a small particle in this world”

but

“The world is a small particle in your mind”

K.Rajeswara Reddy

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