Discuss the anamolous behaviour of fluorine among the halogens. G

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611. Discuss the anamolous behaviour of fluorine among the halogens. Give reason also.


(A) Fluorine shows abnormal behaviour because of the following facts:
(i)    Smaller atomic size.
(ii)    Higher electronegativity.
(iii)    Non-availability of empty d-orbitals in its valency shell.
The main points of difference are:

(i)    Fluorine exhibits on oxidation state-1 only whereas remaining halogens may exhibit oxidation states –1, + 1, + 3, – 5 and + 7. The higher oxidation states arise due to the presence of vacant d-orbitals in their valency shells.

(ii)    On account of high. electronegativity fluorine enters into hydrogen bond formation in its compounds with hydrogen. Thus hydrogen fluoride is an associated molecule due to hydrogen bonding.

 

The phenomenon of hydrogen bonding is not shown by other hydracids.

(iii) Reactivity: Fluorine is most reactive among the halogens. This is due to high electronegativity, small size of its atom, extremely high oxidizing power and its low F—F bond energy (38.5 k cal/ mole). This is indicated by the following properties

(a)    Combination with hydrogen: Fluorine reacts with hydrogen in dark at a low temperature. The other halogens do not react with hydrogen in dark.

(b)    Action with metals : Fluorine reacts with metals like gold and platinum. The other halogens do not react with these metals.

(c) Action with non-metals: Fluorine combines directly with the non-metals like carbon, silicon, nitrogen etc. to give their fluorides.
C+2F2   CF4N2+3F2  2NF3
The other halogens do not combine directly with these elements.

(iv) Action with water : Fluorine reacts with water forming HF, O2, and O3.
2F2+2H2O   4HF+O2 
3F2+3H2O  6HF+O3

The other halogens do not give ozone with water.

(v) Action with alkalies: Fluorine reacts with caustic alkalies to form oxygen difluoride
2NaOH+2F2   2NaF+H2O+OF2
The other halogens react with cold and dilute alkalies to form hypohalites and with hot and conc. alkalies to form higher oxy salts, halates, with cold and dilute alkali:
2NaOH+Cl2    NaCl + NaClOSodium hpochlorite+H2O
with hot and conc. alkali 
6NaOH+3Cl2    5NaClSodium Chlorate + NaClO3+3H2O

vi)    Formation of oxy acids: Fluorine does not form any oxyacid because it is the strongest oxidising agent while the remaining halogens form four types of oxyacids.
HXO — Hypohalous acid
HXO2 — halous acid
HXO3 — Halic acid
HXO4, — Per-halic acid.

(vii)    Behaviour of hydracids:

(a) HF is a liquid whereas other hydracids HCI, HBr HI are gases at ordinary temperature.

(b)    HF is a weak acid, while the other hydr– acids are strong acids.

(c)    HF is most stable of all the hydracids of remaining halogens.

(d)    HF forms acid salts such as NaHF2 while the other halogens acids do not form such salts.

(e)    HF can form complex acids such as HBF4, H2SiF6, while the other halogen acids do not form such acids.

(f) HF is the only acid which reacts with silica, silicates and hence attacks glass.

SiO2Silica + 4HF   SiF4 + 2H2ONa2SiO3Sodium silicate+ 6HF   Na2SiF6Sodium fluosilicate+3H2OCaSiO3Calcium silicate+6HF   CaSiF6Calcium fluosilicate + 3H2O


(viii) Behaviour of salts:
(a) AgF is soluble in water, whereas other silver halides (AgCl, AgBr, Agl) are insoluble.

(b) The fluorides of calcium, strontium and barium are insoluble in water, whereas corresponding salts of other halogens are soluble.

(B) (i) Electron affinity: Cl > F > Br > I.
(ii) Oxidizing power: F2 > Cl2, > Br2 > I2.



 

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