Module-3
Unit-p-Block elements
Chapter : 17-Group elements.
17-Group elements
Group 17 elements :
General introduction,
electronic configuration,
oxidation states,
occurrence,
trends in physical and chemical properties;
preparation, properties and uses of chlorine and
hydrochloric acid.
Compounds of halogens
interhalogen compounds,
oxoacids of halogens (structures only).
This group contains five elements i.e.,
fluorine, chlorine, bromine, iodine and
astatine . They are non-metals and are
collectively named as halogens. The name
halogens meaning sea salt formers.
Fluorine Chlorine
Bromine
17-Gtoup
Iodine
General electronic configuration : ns2np5
OR
ns2 npx2 npy 2 npz 1
This is the elecronic configuration of valency cell. It
indicates this is one electron less than
nearest noble gas configuration.
Fluorine usually shows a negative oxidation
state of -1 except in HOF where it shows an
oxidation state of +1.
The other halogens, in addition to a negative
oxidation state of -1 also show positive
oxidation states +1, +3, +5, +7 .
Halogens are highly reactive elements and hence
do not occur in the free or native state. They
mainly occur in the combined state in form of
their halide salts.
Fluorine is present mainly as insoluble fluorides
and small quantities are present in soil, river
water plants and bones and teeth of animals.
Sea water contains chlorides, bromides and
iodides of sodium, potassium, magnesium and
calcium, but is mainly sodium chloride solution.
Chlorine is the most abundant of all the halogens
and occurs as chlorides. The chief source of
chlorine is sea water, salt wells and salt beds.
(1) Ionisation enthalpy : They have little
tendency to lose electron. Thus they have
very high ionisation enthalpy. Due to increase
in atomic size, ionisation enthalpy decreases
down the group.
F
enthalpy decreases
Ionisation Cl
Br
I
(2) ) Electron gain enthalpy : Halogens have
large negative electron gain enthalpies,
because they have one electron less than the
nearest noble gas configuration.
The negative value decreases down the
group.
The electron gain enthalpy of fluorine is less
negative than the chlorine due to its smaller
size.
(3) Electronegativity : Halogens are highly
electronegative, due to their small size and
high nuclear charge. Fluorine is the most
electronegative element in periodic table with
E.N. value 4.
The electronegativity decreases down the
group.
(4) M.P. and B.P. : All halogens exist as diatomic
molecules in the elemental state, these molecules
are held together by weak van der Waals forces of
attraction. The strength of these forces increases
as the size of the halogen increases from fluorine
to iodine. As a result, F2 and Cl2 are gases at
room temperature, Br2 is a liquid whereas I2 is
solid.
The M.P and B.P. increases down the group
because the forces of attraction increases as the
size of halogen increases.
(5) Enthalpy of dissociation : On moving down in
the group EOD decreases because on moving
down the group size of halogen increases, bond
length of X-X bond increases, bond strength
decreases.
The bond dissociation enthalpy of fluorine is
lower than that of Cl2 and Br2 due to its smaller
size and hence high electronic repulsion.
Thus the bond dissociation enthalpy follows the
sequence :
Cl2 > Br2 > F2 > I2 .
(6) Colour : All the halogens are coloured. The
colour is due to the fact that their molecules
absorb light in the visible region as a result of
which their electrons are excited to higher energy
levels while the remaining light is transmitted.
The colour of halogens is actually the colour of
this transmitted light.
Colour
Pale yellow (F)
Greenish yellow (Cl)
Reddish brown(Br)
Deep violet(I)
(1) Reactivity : All the halogens are highly
reactive.
They react with metals and non-metals to
form halides.
The reactivity of the halogens decreases
down the group.
(2) Oxidising power : Since all the halogens have
a strong tendency to accept an electron, they act
as strong oxidizing agents. This power decreases
down the group. Since F2 is the strongest
oxidizing agent amongst halogens, it will oxidize
all the other halide ions to the corresponding
halogen in solution or in the dry state.
F2 + 2 X- ----> 2F- + X2 ; (X- = Cl- , Br- , I- )
In general, a halogen of lower atomic number
oxidizes halide ions of higher atomic number.
(3) Reactivity towards hydrogen: All the halogens
combine with hydrogen to form hydrogen halides
(HX).
H2 + X2 ----------> 2HX
The reactivity decreases down the group, fluorine
combines with hydrogen violently even in dark,
chlorine reacts in diffused sunlight, bromine reacts
with hydrogen only on heating while iodine reacts
with hydrogen in presence of Pt as catalyst. Hydrogen
halides dissolve in water to form hydrohalic acids.
The acidic strength of these acids varies 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.
Indroduction :
Chlorine was discovered in 1774 by Scheele
by the action of HCl on MnO2.
In 1810 Davy established its elementary
nature and suggested the name chlorine on
account of its colour (Greek, chloros =
greenish yellow).
Preparation :
It can be prepared by any one of the following
methods:
(i) By heating manganese dioxide with
concentrated hydrochloric acid.
MnO2 + 4HCl --> MnCl2 + Cl2 + 2H2O
However, a mixture of common salt and
concentrated H2SO4 is used in place of HCl.
MnO2 + 4NaCl + 4H2SO4 ---> MnCl2 + 4NaHSO4 + 2H2O + Cl2
(ii) By the action of HCl on potassium
permanganate.
2KMnO4 + 16HCl -->2KCl +2MnCl2 +8H2O+ 5Cl2
Preparation :
It can be prepared by any one of the following
methods:
(i) By heating manganese dioxide with
concentrated hydrochloric acid.
MnO2 + 4HCl --> MnCl2 + Cl2 + 2H2O
However, a mixture of common salt and
concentrated H2SO4 is used in place of HCl.
MnO2 + 4NaCl + 4H2SO4 ---> MnCl2 + 4NaHSO4 + 2H2O + Cl2
(ii) By the action of HCl on potassium
permanganate.
2KMnO4 + 16HCl -->2KCl +2MnCl2 +8H2O+ 5Cl2
Properties :
(1) It is a greenish yellow gas with pungent and suffocating odour.
It is about 2-5 times heavier than air. It can be liquefied easily
into greenish yellow liquid which boils at 239 K.
It is soluble in water.
(2) Chlorine reacts with a number of metals and non-metals to form
chlorides.
2Al + 3Cl2 --> 2AlCl3 ; P4 + 6Cl2 ---> 4PCl3
2Na + Cl2 ---> 2NaCl; S8 + 4Cl2 ---->4S2Cl2
2Fe + 3Cl2 --> 2FeCl3
(3) It has great affinity for hydrogen. It reacts with compounds
containing hydrogen to form HCl.
H2S + Cl2 -----> 2HCl + S
C10H16 + Cl2 -------> 16 HCl + 10C
(4) ) With excess ammonia, chlorine gives nitrogen and ammonium
chloride whereas with excess chlorine, nitrogen trichloride
(explosive) is formed.
8NH3 + 3Cl2 --> 6NH4Cl + N2;
NH3 + 3Cl2 --->NCl3 + 3HCl
Properties :
(5) With cold and dilute alkalies chlorine produces
a mixture of chloride and hypochlorite but with
hot and concentrated alkalies it gives chloride
and chlorate.
2NaOH + Cl2 ----> NaCl + NaOCl + H2O
(cold and dilute)
6 NaOH + 3Cl2 ---> 5NaCl + NaClO3 + 3H2O
(hot and conc.)
(6) With dry slaked lime it gives bleaching powder.
2Ca(OH)2 + 2Cl2 ----> Ca(OCl)2 + CaCl2 + 2H2O
(bleaching powder)
Properties :
(7) It is a powerful bleaching agent; bleaching
action is due to oxidation.
Cl2 + H2O ---> 2HCl + O
(nascent oxygen)
Coloured substance + O --> Colourless substance
Uses :
It is used (i) for bleaching wood pulp (required for
the manufacture of paper and rayon), bleaching
cotton and textiles,
(ii) in the extraction of gold and platinum
(iii) in the manufacture of dyes, drugs and organic
compounds such as CCl4, CHCl3, DDT,
refrigerants, etc.
(iv) in sterilising drinking water and
(v) preparation of poisonous gases such as
phosgene (COCl2), tear gas
(CCl3NO2), mustard gas (ClCH2CH2SCH2CH2Cl).
Preparation :
Laboratory method :
It is prepared by heating sodium chloride withConc.
sulphuric acid.
NaCl + H2SO4 -->NaHSO4 + HCl
NaHSO4 + NaCl --> Na2SO4 + HCl
HCl gas can be dried by passing through
concentrated sulphuric acid.
Properties :
(1) It is a colourless and pungent smelling gas.
It is easily liquefied to a colourless liquid
(b.p.189 K) and freezes to a white crystalline
solid (f.p. 159 K).
(2) It is extremely soluble in water and ionises
as follows:
HCl (g) + H2O (l) -----> H3O+ (aq) + Cl-(aq)
Properties :
(3) It reacts with NH3 and gives white fumes of
NH4Cl.
NH3 + HCl ---------> NH4Cl
(4) Hydrochloric acid decomposes salts of weaker
acids, e.g., carbonates, hydrogencarbonates,
sulphites, etc.
Na2CO3 + 2HCl ---->2NaCl + H2O + CO2
NaHCO3 + HCl ----> NaCl + H2O + CO2
Na2SO3 + 2HCl ----> 2NaCl + H2O + SO2
Uses :
It is used
(i) in the manufacture of chlorine, NH4Cl and
glucose (from corn starch),
(ii) for extracting glue from bones and
purifying bone black,
(iii) in medicine and as a laboratory reagent.
When two different halogens react with each other,
interhalogen compounds are formed.
They can be assigned general compositions as XY , XY3
, XY5 and XY7 where X is halogen of larger size and Y
of smaller size and X is more electropositive than Y.
As the ratio between radii of X and Y increases, the
number of atoms per molecule also increases. Thus,
iodine (VII) fluoride should have maximum number of
atoms as the ratio of radii between I and F should be
maximum. That is why its formula is IF7 (having
maximum number of atoms).
Peparation :
All interhalogen compounds are prepared by
direct combination between the halogens.
At different temperature and at different
conditions different interhalogen compounds are
formed.
Cl2 + F2 ----> 2ClF ( at 437 K)
Cl2 + 3F2 --> 2 ClF3 ( at 573 K)
Br2(l) + 5 F2 --> 2BrF5(l) (F2 in excess)
I2(g) + 7 F2(g) ------> 2IF7(g) ( 523- 573 K)
Properties :
(1) These are all covalent molecules and are
diamagnetic in nature. They are volatile solids
or liquids at 298 K except ClF which is a gas.
Their physical properties are intermediate
between those of constituent halogens except
that their m.p. and b.p. are a little higher than
expected.
(2) Their chemical reactions can be compared with
the individual halogens. In general,
interhalogen compounds are more reactive than
halogens (except fluorine). This is because X–Y
bond in interhalogens is weaker than X–X bond
in halogens except F–F bond.
Properties :
(3) All these undergo hydrolysis giving halide ion
derived from the smaller halogen and a
hypohalite ( when XY), halite ( when XY3), halate
(when XY5) and perhalate (when XY7) anion
derived from the larger halogen.
XY + H2 O --> HY + HOX
(4) Their molecular structures are very interesting
which can be explained on the basis of VSEPR
theory ( The XY3 compounds have the bent ‘T’
shape, XY5 compounds square pyramidal and IF7
has pentagonal bipyramidal structures.
Uses :
These compounds can be used as non
aqueous solvents.
Interhalogen compounds are very useful
fluorinating agents.
ClF3 and BrF3 are used for the production of
UF6 in the enrichment of 235U.
U(s) + 3ClF3(l) ----->UF6(g) + 3ClF(g)
*
THE END
