The Halogens

Chapter 40
Position in Periodic Table
Gp VII

Cl

Br

At
 General information
Halogen Atomic Ionic Melting Boiling Density (g Abundance
radius (nm) radius (nm) Point (oC) Point (oC) cm-3) on Earth
(%)
Fluorine 0.072 0.133 -220 -188 1.11 0.062

Chlorine 0.099 0.181 -101 -34.7 1.56 0.013

Bromine 0.114 0.195 -7.2 58.8 3.12 0.0003

Iodine 0.133 0.216 114 184 4.93 0.00005

Astatine - - 302 380 - Trace

 Characteristic properties
• Very reactive non-metals
– High electronegativity
– High electron affinity
• Bonding and Oxidation states
• Colour
 Electronegativity

A measure of the attracting Element EN value

ability of bonding
electrons.
F 4.0
Cl 3.0
Due to their large effective
nuclear charge, Br 2.8
halogens are the most
electronegative element I 2.5
in the periodic table.
 Electron Affinity

Element EA
Generally high electron
affinity. All are exothermic.
kJ/mol
F -348
X(g) + e- → X-(aq)
Cl -364
Br -342
I -285
 Bonding and Oxidation State
• ns2np5
• Ionic or covalent bond with oxidation state
–1 or +1 (F shows –1 only)
• Except F, all other halogens can expand
their octet by using the low-lying, vacant d-
orbitals to form bonding. Their oxidation
states range from –1 to +7.
 Bonding and Oxidation State

↑ nd

nd ↑↓ ↑ ↑ np

↑↓ ↑↓ ↑ np ↑↓ ns

↑↓ ns (+3 states)

(0, +1, -1 states) HClO2, ClO2-

Cl2, Cl-, OCl2
 Bonding and Oxidation State

↑ ↑ ↑ nd
↑ ↑ nd ↑ ↑ ↑ np

↑ ↑ ↑ np ↑ ns
↑↓ ns (+7 state)

(+5 state) Cl2O7, HIO4

HClO3, HBrO3, I2O5
 Colour
Element Colour

In Standard State In Water In 1,1,1-

trichloroethane
F Pale yellow Pale yellow Pale yellow

Cl Greenish yellow Pale yellow Yellow

Br Reddish brown Yellow Orange

I Violet black Brown Violet

 Colour

White light

Iodine
 Check point 40-1

∆E2

∆E1

Iodine Fluorine
 Variation in properties of
Halogens

400
b.p.

(Temp. oC) m.p.

m.p./b.p. increase as Mr increase

0because Van der Waals’ Force increase
with Mr F Cl Br I At

-300
 Electronegativity

4 4.0
F form ionic compound
3.0 with –1 oxidation state.
3 2.8
2.5
I shows highly positive
2 oxidation states with
more electronegative
1 element.
e.g. KIO4

F Cl Br I
 Electron affinity
EA decrease from
Cl to I due to increasing
atomic size which lowers
340
the nuclear attraction to
the added electron.
320
F has exceptional lower
EA because its 2nd shell
is already crowded with
280
7 e-, the additional e-
will experienced a greater
F Cl Br I e-e repulsion than other
halogens.
Variation in Chemical Properties
of elements
All are good oxidizing agents. (F2>Cl2>Br2>I2)
∆H
½ X2(std.state)  X-(aq)

∆Hatom
∆Hhyd
X(g)

∆HEA

X-(g)
∆H = ∆Hatom + ∆HEA + ∆Hhyd
 Oxidizing power
Element
∆Hatom ∆HEA ∆Hhyd ∆H
F 79.1 -348 -506 -774.9

Cl 121 -364 -364 -607

Br 112 -342 -335 -565

I 107 -314 -293 -500 Oxidizing

strength
 Oxidizing properties
Standard electrode
1. Oxidation of metals potential (V)
a. F2 oxidizes all metals Cl2+e- 1.36
including Au and Ag. →Cl-
b. Cl2 oxidizes common Br2+e- 1.07
metals such as Na and Cu. →Br-
I2+e-→ 0.54
• Reactions with Fe (aq)
2+
I-
2Fe2+ + Cl2→2Fe3+ + 2Cl-
Fe3++e- 0.77
2Fe2+ + Br2→2Fe3+ + 2Br- →Fe2+
2Fe3+ + 2I-→2Fe2+ + I2
 Oxidizing properties
3. Reaction with phosphorus
2P + 3X2 → 2PX3
2P + 5X2 → 2PX5

F2 and Cl2 form PX5 as they have high oxidizing

Strength. They combine with P to exhibit its maximum
oxidation state.

Br2 and I2 form PX3 only.

 Reaction with water
Fluorine oxidizes water to form HF and O2

2F2 + 2H2O → 2HF + O2

Chlorine undergoes disproportionation(self oxidation

and reduction) to form HCl and HOCl.

Cl2 + H2O → HCl + HOCl

 Reaction with water
A mixture of Cl2(aq), HCl(aq) and HOCl(aq)
is called chlorine water.

OCl- , chloric(I) ion

3. Strong oxidizing agent with bleaching property

OCl- + dye (coloured) → Cl- + dye (colourless)
5. Unstable to heat and light
2OCl- → O2 + 2Cl-
 Reaction with water

Br2 is only slightly soluble in water.

Br2 (aq) + H2O (l)  HBr(aq) + HOBr(aq)

OBr-(aq) is unstable and with bleaching property:

• 2OBr- → O2 + 2Br-
2. OBr- + dye(coloured) → Br- + dye(colourless)
 Reaction with water

I2 does not react with water and only very

slightly soluble in water.

I2 is more soluble in ethanol or in KI(aq).

I2(aq) + I-(aq)  I3-(aq)
 Reaction with alkalis

All halogens react with aqueous alkalis and

disproportionate in it. The products depend on
temperature
and
concentration of the alkalis.
 Reaction with alkalis
Cold 2F2 + 2NaOH → 2NaF + OF2 + H2O
dil.NaOH
Cl2 + 2NaOH → NaCl + NaOCl + H2O

Br2 + 2NaOH  NaBr + NaOBr + H2O

3NaOBr  2NaBr + NaBrO3
(3Br2 + 6NaOH  5NaBr + NaBrO3 + 3H2O

I2 + 2NaOH → NaI + NaOI + H2O

3NaOI  2NaI+ NaIO3
(3I2 + 6NaOH  5NaI + NaIO3 + 3H2O
 Reaction with alkalis
More 2F2 + 4NaOH → 4NaF + O2 + 2H2O
concentrated
NaOH
Hot Cl2 + 2NaOH → NaCl + NaCl + H2O
concentrated 3NaOCl → 2NaCl + NaClO3
NaOH (3Cl2 + 6NaOH → 5NaCl + NaClO3 + 3H2O
 Reaction with alkalis
The reverse reaction of I2 and KOH is used
to prepare standard iodine solution for iodometric
titration. Know amount of iodine is generated by
dissolving known quantity of KIO3 in excess KI
and H+.

5KI + KIO3 + 3H+  3I2 + 6K+ + 3H2O

Variation in properties of halides
Halogen Displacement reactions

Oxidizing strength : F2 >Cl2 >Br2 >I2

Cl2 + 2Br- → 2Cl- + Br2

Cl2 + 2I- → 2Cl- + I2

Br2 + 2I- → 2Br- + I2

 Halide + c. H2SO4
NaCl + H2SO4 → NaHSO4 + HCl
2NaCl + H2SO4 → Na2SO4 + HCl (500oC)

2NaBr + 2H2SO4 → 2HBr + Na2SO4

2HI + H2SO4 → SO2 + Br2 + 2H2O

2NaI + 2H2SO4 → 2HI + Na2SO4

8HI + H2SO4 → H2S + 4I2 + 4H2O

Relative reducing power: HCl < HBr < HI

 Halide + c. H3PO4

3NaCl + H3PO4 → Na3PO4 + 3HCl

3NaBr + H3PO4 → Na3PO4 + 3HBr
3NaI + H3PO4 → Na3PO4 + 3HI

H3PO4 is NOT a strong oxidizing agent.

It reacts with halides to form HX.
 Halides + Ag+(aq)
Ag+(aq) + Cl-(aq) → AgCl(s) , white precipitate

Ag+(aq) + Br-(aq) → AgBr(s) , pale yellow precipitate

Ag+(aq) + I-(aq) → AgI(s) , yellow precipitate

 Halides + Ag+(aq)
Ion Action of Effect of Effect of
AgNO3= Standing in adding excess
sunlight aq. NH3
Cl- White ppt. Turns grey White ppt.
dissolves

Br- Pale yellow Turns Pale yellow

ppt. yellowish grey ppt. slightly
dissolves
I- Yellow ppt. Remains Yellow ppt.
yellow does not
dissolve
 Relative acidity of HX
Hydrogen Halide Dissociation constant Degree of dissociation
in 0.1M solution

HF 7x10-4 0.085

HCl 1x107 0.920

HBr 1x109 0.930

HI 1x1011 0.950
 Relative Acidity of HX
∆H
HX(aq) H+(aq) + X-(aq)

∆H5 ∆H6
∆H1
H+(g) + X-(g)

∆H3 ∆H4
∆H2
HX(g) H (g) + X (g)
 Relative Acidity of HX

HX ∆H1 ∆H2 ∆H3 ∆H4 ∆H5 ∆H6 ∆H T∆S ∆G

HF 48 566 1311 -333 -1091 -515 -14 -29 15

HCl 18 431
Explanation of weak acid strength
1311 -348 -1091 -381 -60
of HF:
-13 -47
• HF has the greatest bond dissociation
HBr 21 366 energy-324
1311 and exceptionally
-1091 -347 small -64 -4 -60
electron affinity. It has the least
HI 23 299 1311 -295 ∆H.
exothermic -1091 -305 -58 4 -62
6. Due to formation of strong hydrogen
bond and greatest degree of hydration,
HF has the smallest decrease of T∆S.
Anomalous behaviour of HF

According to La Chatelier’s Principle, the degree

of dissociation of a weak acid increases with dilution.
HA H+ + X-
However, the acidity of conc. HF is greater than
dilute HF. Why?

In conc. HF, HF molecules form dimers H2F2 by

hydrogen bond. The acid strength of H2F2 is
stronger than HF.
H2F2  H+ + HF2-
 Uses of Halogens and Halides
• Teflon
• Na2SiF6 or NaF is used to fluoridate drinking
water.
• Chlorine bleach, sterilization of water, PVC.
• Anti-knocking agent (leaded petrol)
• AgBr coating in film
• Iodine tincture
• AgI in coating film