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XII : P-BLOCK ELEMENTS [TOTAL MARKS = 6 ]Revised 23

Group 17 elements F, Cl, Br, I, At . ( Halogen Family ) SRL-1 By Nitul Sir

General discussion:
1. Elements present : Fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and astatine
(At) are the members of Group 17. They (except At) are collectively known as the
halogens (means salt producers).At is radioactive .
2. Physical state : F2 : Gas , Cl2 : Greenish yellow gas , Br2 : Reddish brown liquid , I2 :
Violet solid
3. Electronic configuration

General electronic configuration:ns2np5 , where n = 2,3,4,5 : for the group n= 2 to 6

Fluorine does not have any vacant orbitals in it’s outermost shell .
4. Oxidation states
F : -1
Cl : -1 , + 1 , + 3 , + 5 , +7
Br : -1 , + 1 , + 3 , + 5 , +7
I : -1 , + 1 , + 3 , + 5 , +7
All the halogens exhibit –1 oxidation state. Chlorine, bromine and iodine also show + 1,
+ 3, + 5 and + 7 oxidation states in their oxides, oxy acids and in inter halogen
compounds.
Due to the absence of vacant d orbitals and the maximum electronegativity,
fluorine exhibits only –1 oxidation state.
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5. Atomic and ionic radii: Halogens have the smallest atomic radii in their respective periods
because of maximum effective nuclear charge.
6. Ionisation enthalpy: They have very high ionization enthalpy because of small size as
compared to other groups.

7. 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 these elements
decreases down the group. However, the negative electron gain enthalpy of fluorine is less than
that of chlorine. It is because, in fluorine the incoming electron goes to the 2p subshell, but in
Cl it enters in to the 3p subshell. Due to the compactness of 2p subshell compared to 3p
subshell, the electron – electron repulsion is greater in fluorine than in chlorine. So F does not
easily gains electron

8. Eelctronegativity: These elements are highly electronegative and electronegativity

decreases down the group. They have high effective nuclear charge. Fluorine is the most
electronegative element in the periodic table.

9. Bond dissociation enthalpy: Bond dissociation enthalpy follows the order Cl2 > Br2 > F2 > I2
Bond dissociation enthalpy of F2is less than Cl2 and Br2 because of large electron –electron [2P-2P]
repulsion among the non-bonding p-electrons in Fluorine , it being small in size .

10. Colour : All halogens are coloured because of absorption of radiations in visible region
which results in the excitation of outer electrons to higher energy levels.
11. Oxidising power: All halogens are strong oxidisinga gents because they have a strong
tendency to accept electrons. Order of oxidizing power is F 2 > Cl2 > Br2 > I2

12. Hydrides of halogens

a/ Stability: HF > HCl > HBr > HI This is because of decrease in bond dissociation
enthalpy.
b/ Boiling point: HCl < HBr < HI < HF HF has strong intermolecular H bonding As
the size increases van der Waals forces increases and hence boiling point
increases.
c/ % Ionic character: HF > HCl > HBr > HI
d/ Dipole moment: HF > HCl > HBr > HI
e/ The acidic strength and reducing power: HF < HCl < HBr < HI
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13. Anomalous behavior of fluorine

Due to the small size, highest electronegativity, low F-F bond dissociation
enthalpy, and non availability of d orbitals in valence shell, fluorine shows
properties different from other halogens.Some of the anomalous properties of
fluorine are:
1. Ionisation enthalpy, electronegativity, enthalpy of bond dissociation and
electrode potentials arehigher for fluorine than expected.
2. Ionic and covalent radii, m.p. and b.p. and electron gain enthalpy are quite
lower than expected.
3. Most of the reactions of fluorine are exothermic (due to the small and strong
bond formed by it withother elements).
4. F forms only one oxoacid while other halogens form a number of oxoacids.
5. Hydrogen fluoride is a liquid due to strong hydrogen bonding. While the
hydrogen halides of otherelements are gases.
CHLORINE (Cl2)
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
Conc. HCl can be replaced by a mixture of common salt and concentrated H 2SO4
4NaCl + MnO2 + 4H2SO4 → MnCl2+ 4NaHSO4 + 2H2O + Cl2

(ii) By the action of HCl on potassium permanganate.

2KMnO4 + 16HCl → 2KCl + 2MnCl2 + 8H2O + 5Cl2

Manufacture of chlorine
(i) Deacon’s process: By oxidation of hydrogen chloride gas by atmospheric oxygen in
the presence of CuCl2 (catalyst) at 723 K.
4HCl+O2 →2Cl2 +2H2O
Properties: It is a greenish yellow gas with pungent and suffocating odour. It is soluble
in water. It can be liquefied easily into greenish yellow liquid which boils at 239 K

Chemical properties :

1. It 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 ;
2. It has a great affinity for H2 . It reacts with H2 and compounds containing
hydrogen to form HCl
H2 + Cl2 →2HCl
H2S + Cl2 →2HCl + S

3. Reaction with NH3 : Cl2 reacts with NH3 in two ways as follows :
a) When NH3 is in excess , nitrogen and ammonium chloride are formed nitrogen
8NH3 + 3Cl2 → 6NH4Cl + N2;
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(excess)
b) When Cl2 is in excess, NCl3 ( explosive ) and HCl are formed
NH3 + 3Cl2 → NCl3 + 3HCl
(excess)
4. Reaction with Alkali : Cl2 reacts with alkali indifferent ways as follows :
a) With cold and dilute alkalis chlorine produces a mixture of chloride (Cl -) and
hypochlorite(ClO-)
2NaOH + Cl2 → NaCl + NaOCl + H2O
(cold and dilute)
2KOH + Cl2 → KCl + KOCl + H2O
(cold and dilute)

b) With hot and concentrated alkalis , chlorine produces a mixture of chloride

(Cl-) and chlorate (ClO3-)
6 NaOH + 3Cl2 → 5NaCl + NaClO3 + 3H2O
(hot and conc.)
6 KOH + 3Cl2 → 5KCl + KClO3 + 3H2O
(hot and conc.)
c) With dry slaked lime it gives bleaching powder.
2Ca(OH)2 + 2Cl2 → Ca(OCl)2 + CaCl2 + 2H2O

5. Chlorine dissolves in water giving Chlorine water. Chlorine water on standing

loses its yellow colour due to the formation of HCl and HOCl. Hypochlorous acid
(HOCl) so formed is unstable and dissociates to give nascent oxygen which is
responsible for oxidising and bleaching properties of chlorine.
HOCl → HCl + [O]
(i) It oxidises ferrous to ferric, sulphite to sulphate, sulphur dioxide to sulphuric
acid and iodine to iodic acid.
2FeSO4 + H2SO4 + Cl2 → Fe2(SO4)3 + 2HCl
Na2SO3 + Cl2 + H2O → Na2SO4 + 2HCl
SO2 + 2H2O + Cl2 → H2SO4 + 2HCl
I2 + 6H2O + 5Cl2 → 2HIO3 + 10HCl
It will be better for you to use the Partial equation method for the above
reactions

(ii) It is a powerful bleaching agent; bleaching action is due to oxidation.

Cl2 + H2O → 2HCl + [O]
Coloured substance + [O] → Colourless substance
It bleaches vegetable or organic matter in the presence of moisture. Its bleaching
action is permanent.
Uses: It is used
(i) For bleaching wood pulp, bleaching cotton and textiles,
(ii) In the extraction of gold and platinum
(iii) In the manufacture of dyes, drugs and organic compounds such as CCl 4,
CHCl3, DDT, refrigerants, etc.
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(iv) In sterilising drinking water and

Oxoacids of Halogens
Due to high electronegativity and small size, fluorine forms only one oxoacid, HOF
known as fluoric (I) acid or hypofluorous acid. The other halogens form several
oxoacids like Hypohalous acid (HOX), halous acid (HOXO) , halic acid(HOXO 2) and
perhalic acid (HOXO3). They are stable only in aqueous solutions or in the form of their
salts.Chlorine forms 4 types of oxoacids – hypochlorous acid (HOCl), Chlorous acid
(HOClO or HClO2), Choric acid (HOClO2 or HClO3) and perchloric acid (HOClO3 or HClO4).
The structures of them are:

Interhalogen Compounds
When two different halogens react with each other, interhalogen compounds are
formed. They can be assigned general compositions as AX, AX3, AX5 and AX7, where
both A and X are halogens. A is larger and more electropositive than X. As the size of the
central atom (A) increases, the stability of the compound also increases.
Preparation
The interhalogen compounds can be prepared by the direct combination or by the
action of halogen on lower interhalogen compounds.
Cl2 + F2 →2ClF(437K) I2 + 3Cl2 → 2ICl3
(equal volume) (excess)
Cl2 + 3F2 →2ClF3 (573K) Br2 + 3F2 →2BrF3
(excess) (diluted with water)
I2 + Cl2 →2ICl Br2 + 5F2 →2BrF5
(equimolar) (excess)
Properties:
These are all covalent molecules and are diamagnetic in nature. They are volatile solids
or liquids except CIF which is a gas at 298 K. Their physical properties are
intermediate between those of constituent halogens. The interhalogen compounds are
more reactive than halogens (except fluorine). This is because A–X bond in
interhalogens is weaker than X–X bond in halogens except F–F bond.
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Type Examples Structure

AX ClF, BrF, IF, BrCl, BrI Linear
AX3 ClF3, BrF3, IF3, ICl3, IBr3 Bent T-shaped
etc.
AX5 ClF5, BrF5, IF5 Square pyramidal
AX7 IF7 Pentagonal
bipyramidal

Uses: These compounds can be used as non aqueous solvents. Interhalogen compounds
are very useful fluorinating agents.

CONCEPTIONAL Q/A
1. Halogens have maximum negative electron gain enthalpy in the respective
periods of the periodic table. Why?
Ans: Halogens have the smallest size in their respective periods and therefore
high effective nuclear charge. As a consequence, they readily accept one
electron to acquire noble gas electronic configuration.

2. Although electron gain enthalpy of fluorine is less negative as compared

to chlorine, fluorine is a stronger oxidizing agent than chlorine. Why?
Ans: It is due to (i) low enthalpy of dissociation of F-F bond
(ii) high hydration enthalpy of F–

3. The electron gain enthalpy of Fluorine is less negative than Chlorine Why?
Answer. Due to small size of Fluorine , there is strong inter electronic repulsion in the small
2p orbital is high.

4. All halogens are coloured .Why?

Answer. Due to absorption of radiation in the visible region which results in the excitation of
outer electrons to higher energy levels .
5. The bond dissociation enthalpy of F2 is smaller than that of Chlorine .Why?
Answer. Due to large electron –electron repulsion among the lone pairs of electrons in
Fluorine

6. Fluorine is a strong oxidizing agent than Chlorine .Why?

Answer. This is due to a). Low bond enthalpy of F2. b). high hydration enthalpy of F-

7. Fluorine doesn’t show positive oxidation state.Why?

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Answer. Due to it’s highest electronegativity and absence of vacant d- orbitals in it’s
outermost shell.

8. Fluorine can’t expand its covalency beyond one .Why?

Answer. Due to absence of vacant ‘d’ orbital.

9. The oxidizing tendency of halogens decreases down the group. Why?

Answer. Due to a) decreasing electron gain enthalpy b) decreasing hydration enthalpy of X -

10. What happens when F2 gas is passed through solutions of a) KCl b)KBr c) KI
Fluorine being more reactive oxidizes the halides to the respective halogens .
KCl (aq) + F2 (g) → 2KF (aq) + Cl2(g) :KBr (aq) + F2(g) → 2KF(aq) + Br2(l)
KI(aq) + F2 (g) → 2Kf(aq) + I2(g)

11. How does F2 gas react with water ?

Answer. F2 oxidises water to oxygen gas; F2(g) + 2H2O (l) → 4HF(aq) + O2(g) B’coz, F is more
electro-negativity than O

12. How do Chlorine and Bromine react with water ?

Cl2(g) + H2O(l) → HCl (aq) + HOCl (aq)
Br2(l) + H2O(l) → HBr(aq) + HOBr(aq)

13. What are the reasons for the anomalous behavior of Fluorine ?
Answer. a) small size b) highest electronegativity c) low F-F bond dissociation enthalpy d)
non availability of vacant ‘d ‘ orbitals in the valence shell.

14. Most of the compounds of Fluorine are exothermic. Why?

Answer. Due to small size and strong bond formed by Fluorine with atoms of other elements .

15. Fluorine forms only one oxoacid HOF . Why?

Answer. Due to absence of vacant d - orbitals in its valence shell.

16. HF is a liquid . Why?

Answer. Due to strong intermolecular H-bonding
17. Arrange the hydrides of 17th group elements in the increasing order of the property
mentioned . Acid strength : HF <HCl<HBr<HI Stability : HI<HBr<HCl<HF

18. The stability of the hydrides of 17th group elements decreases down the group.
Why?
Answer : Due to the decreasing bond strength of X-H bond .

Q19 . The bond energy of F2 is less than that of Cl2

Ans. Due to smaller size, the lone pairs of electrons on the F-atoms repel the bond pair of the
F—F bond. In contrast, because of comparatively larger size of CI atoms, the lone pairs of Cl
do not repel the bond pair of CI—Cl bond. As a result, F—F bond energy is lower than that of
Cl—Cl bond energy.
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Q.20. Flourine does not undergo disproportionation reactions but other halogens do.
Explain.
Ans. Disproportionation means simultaneous oxidation-reduction. F being the most
electronegative element undergoes only reduction but not oxidation. As a result, it shows only
—1 oxidation state while other halogens show both negative (—-1) and positive (+1, +3, +5,
+7) oxidation states. Thus, F does not show disproportionation reactions while other halogens
do.

Q21. Write an example of a neutral molecule which is isoelectronic with ClO -.

Ans. CIO- ion has 17 + 8 + 1 = 26 electrons. A neutral molecule with 26 electrons is OF 2 (8+2 ×
9 = 26). Thus OF2 is isoelectronic with CIO-.

Q22. Both NO and C1O2 are odd electron species whereas NO dimerises but C1O 2 does
not. Why?
Ans. In NO, the odd electron on N is attracted by only one O-atom but in C1O2, the odd
electron on Cl is attracted by two O-atoms. As a result, the odd electron on N in NO is localized
while the odd electron on Cl in C1O 2 delocalized. Consequently, NO has a tendency to dimerize
but C1O2 does not.

Q. 23. F-atom is more electronegative than I-atom, yet HF has lower acid strength than
HI. Explain. Or Hydrogen fluoride is a much weaker acid than HCI in aqueous solution.
Ans. F atom being small in size, the bond dissociation energy of H—F is very high as compared
to that of H—I bond because I-atom is very large in size.

Q.24. Why F2 is a stronger oxidizing agent than C12 while electron affinity of fluorine is
less than that of chlorine ?
Ans. F2 is a stronger oxidizing agent than CI 2 because electrode potential of F 2 (+ 2.87 V) is
much higher than that of C1 2 (+ 1.36 V). As a result, F2 is more readily reduced than C12 and
hence F2 is a stronger oxidising agent than Cl2.

Q.25. OF2 should be called oxygen difluoride and not fhiorine oxide. Why ?
Ans. Because F is more electronegative than oxygen.

Q. 26. Iodine is more soluble in KI than in water. Why?

Ans. Iodine combines with KI to form the soluble complex, KI3 (KI + I2 → KI3)