41 The Halogens

41.1 Characteristic Properties of the Halogens

41.2 Variation in Properties of the Halogens
41.3 Comparative Study of the Reactions of
Halide Ions
41.4 Acidic Properties of Hydrogen Halides and
the Anomalous Behaviour of Hydrogen
Fluoride
41.1
Characteristic
Properties of the
Halogens
41.1 Characteristic Properties of the Halogens (SB p.78)

Introduction
• Group VIIA elements include
 fluorine
 chlorine
 bromine
 iodine
 astatine
41.1 Characteristic Properties of the Halogens (SB p.78)

Introduction
• Astatine
 not much is known
 radioactive
41.1 Characteristic Properties of the Halogens (SB p.78)

Introduction
• Group VIIA elements
 also called halogens
41.1 Characteristic Properties of the Halogens (SB p.78)

The halogens
41.1 Characteristic Properties of the Halogens (SB p.79)

Introduction
• All halogens
 outermost shell electronic
configuration of ns2np5
 one electron short of the octet
electronic configuration
41.1 Characteristic Properties of the Halogens (SB p.79)

Introduction
• In the free elemental state
 form diatomic molecules
 complete their octets by sharing their
single unpaired p electrons
41.1 Characteristic Properties of the Halogens (SB p.79)

Introduction
• When halogens react with other elements
 complete their octets
 depending on the electronegativity of
the element
41.1 Characteristic Properties of the Halogens (SB p.79)

Introduction
• Either
 gaining an additional electron to form
halide ions
 or sharing their single unpaired p
electrons to form single covalent
bonds
41.1 Characteristic Properties of the Halogens (SB p.79)

chlorine

Appearances of halogens at room

temperature and pressure: chlorine
41.1 Characteristic Properties of the Halogens (SB p.79)

bromine

Appearances of halogens at room

temperature and pressure: bromine
41.1 Characteristic Properties of the Halogens (SB p.79)

iodine

Appearances of halogens at room

temperature and pressure: iodine
41.1 Characteristic Properties of the Halogens (SB p.79)

High Electronegativity

Electronegativity is the relative tendency

of an atom to attract bonding electrons
towards itself in a covalent bond.
41.1 Characteristic Properties of the Halogens (SB p.79)

High Electronegativity
• All halogens
 high electronegativity values
 high tendency to attract an additional
electron to achieve the stable octet
electronic configuration
 highest among the elements in the
same period
41.1 Characteristic Properties of the Halogens (SB p.79)

Electronegativity values of halogens

Halogen Electronegativity value
F 4.0
Cl 3.0
Br 2.8
I 2.5
At 2.2
41.1 Characteristic Properties of the Halogens (SB p.79)

High Electron Affinity

Electron affinity is the enthalpy change

when one mole of electrons is added to
one mole of atoms or ions in the gaseous
state.
41.1 Characteristic Properties of the Halogens (SB p.79)

High Electron Affinity

• Its value
 indicates the ease of formation of
anions
41.1 Characteristic Properties of the Halogens (SB p.79)

High Electron Affinity

• All halogens
 negative values of electron affinity
 high tendency to attract an additional
electron to form the respective halide
ions
41.1 Characteristic Properties of the Halogens (SB p.79)

Electron affinities of halogens

Halogen Electron affinity (kJ mol–1)

F –348
Cl –364
Br –342
I –314
At –285
41.1 Characteristic Properties of the Halogens (SB p.80)

Bonding and Oxidation State

• Halogens
 gain an additional electron to form
the halide ions
 combine with metals to form metal
halides
 held together by ionic bonding
41.1 Characteristic Properties of the Halogens (SB p.80)

Bonding and Oxidation State

• The oxidation states of the halogens = –1
41.1 Characteristic Properties of the Halogens (SB p.80)

Bonding and Oxidation State

• The halogen atoms
 share their unpaired p electrons with
a non-metallic atom
 form a covalent bond
41.1 Characteristic Properties of the Halogens (SB p.80)

Bonding and Oxidation State

• Halogens (except fluorine)
 exhibit an oxidation state of –1 or +1
in the covalent molecules formed
 depend on the electronegativity of the
elements that are covalently bonded
with the halogens
41.1 Characteristic Properties of the Halogens (SB p.80)

Bonding and Oxidation State

• All halogens (except fluorine)
 can expand their octets of electrons
by utilizing the vacant, low-lying d
orbitals
41.1 Characteristic Properties of the Halogens (SB p.80)

Bonding and Oxidation State

• Each of these halogen atoms
 have variable numbers of unpaired
electrons to pair up with electrons
from other atoms
 able to form compounds of different
oxidation states
41.1 Characteristic Properties of the Halogens (SB p.80)

“Electrons-in-boxes” diagrams of the

electronic configuration of a halogen atom of
the ground state and various excited states
41.1 Characteristic Properties of the Halogens (SB p.81)

Various oxidation states of halogens in their ions or compounds

Oxidation state
Ion / Compound
of halogen
F– Cl– Br– I–
–1 HF HCl HBr HI
OF2
0 F2 Cl2 Br2 I2

Cl2O Br2O
+1 HOCl HOBr
OCl– OBr–
HClO2
+3
ClO2–
41.1 Characteristic Properties of the Halogens (SB p.81)

Various oxidation states of halogens in their ions or compounds

Oxidation state
Ion / Compound
of halogen
+4 ClO2 BrO2

HClO3 HBrO3 I2O5

+5
ClO3– BrO3– HIO3
IO3–
+6 Cl2O6 BrO3

Cl2O7 H5IO6
+7 HClO4 HIO4
ClO4– IO4–
41.1 Characteristic Properties of the Halogens (SB p.81)

Bonding and Oxidation State

• Fluorine
 cannot expand its octet
 no low-lying empty d orbitals
available
 the energy required to promote
electrons into the third quantum shell
is very high
41.1 Characteristic Properties of the Halogens (SB p.81)

Bonding and Oxidation State

• Fluorine
 the most electronegative element
 only one unpaired p electron
available for bonding
 oxidation state is limited to –1
41.1 Characteristic Properties of the Halogens (SB p.82)

Colour
• All halogens
 coloured
 the absorption of radiation in the
visible light region of the
electromagnetic spectrum
41.1 Characteristic Properties of the Halogens (SB p.82)

Colour
• The absorbed radiation
 the excitation of electrons to higher
energy levels
41.1 Characteristic Properties of the Halogens (SB p.82)

Colour
• Fluorine atom
 smaller size
 absorb the radiation of relatively high
frequency (i.e. blue light)
 appears yellow
41.1 Characteristic Properties of the Halogens (SB p.82)

Colour
• Atoms of other halogens
 larger sizes
 absorb radiation of lower frequency
41.1 Characteristic Properties of the Halogens (SB p.82)

Colour
• Iodine
 absorbs the radiation of relatively low
frequency (i.e. yellow light)
 appears violet
41.1 Characteristic Properties of the Halogens (SB p.82)

Colour
• Halogens
 different colours when dissolved in
different solvents
41.1 Characteristic Properties of the Halogens (SB p.82)

Colour
• Halogens
 non-polar molecules
 not very soluble in polar solvents
(such as water)
 but very soluble in organic solvents
(such as 1,1,1-trichloroethane)
41.1 Characteristic Properties of the Halogens (SB p.82)

Colours of halogens in pure form and in solutions

Colour
Halogen
in pure form in water in 1,1,1-trichloroethane

F2 Pale yellow Pale yellow Pale yellow

Cl2 Greenish yellow Pale yellow Yellow

Br2 Reddish brown Yellow Orange

Yellow (only
I2 Violet black Violet
slightly soluble)
41.1 Characteristic Properties of the Halogens (SB p.82)

(a) (b) (c)

Colours of halogens in water:

(a) chlorine; (b) bromine; (c) iodine
41.1 Characteristic Properties of the Halogens (SB p.83)

(a) (b) (c)

Colours of halogens in 1,1,1-trichloroethane:

(a) chlorine; (b) bromine; (c) iodine
41.1 Characteristic Properties of the Halogens (SB p.83)

Check Point 41-1

41.2 Variation in Properties of the Halogens (SB p.83)

Introduction
• All halogens
 exist as diatomic molecules
41.2 Variation in Properties of the Halogens (SB p.83)

Introduction
• In the diatomic molecules
 the halogen atoms are held together
by strong covalent bonds
41.2 Variation in Properties of the Halogens (SB p.83)

Introduction
• The molecules
 only held together by weak van der
Waals’ forces (i.e. instantaneous
dipole-induced dipole interaction)
41.2 Variation in Properties of the Halogens (SB p.83)

Introduction
• The physical properties of halogens
 strongly affected by the way that the
atoms are joined together
 the interactions that hold the
molecules together
41.2 Variation in Properties of the Halogens (SB p.83)

Some physical properties of the halogens

Colour and state at room Atomic radius Ionic radius
Halogen
temperature and pressure (nm) (nm)

Fluorine Pale yellow gas 0.072 0.133

Chlorine Greenish yellow gas 0.099 0.181
Bromine Reddish brown liquid 0.114 0.195
Iodine Violet black solid 0.133 0.216
Astatine – – –
41.2 Variation in Properties of the Halogens (SB p.83)

Some physical properties of the halogens

Density at 20 C
Halogen Melting point (C) Boiling point (C)
(g cm–3)

Fluorine –220 –188 1.11

Chlorine –101 –34.7 1.56
Bromine –7.2 58.8 3.12
Iodine 114 184 4.93
Astatine 302 380 –
41.2 Variation in Properties of the Halogens (SB p.84)

Variation in Physical Properties

1. Melting Point and Boiling Point

• Halogens
 exist as non-polar diatomic molecules
41.2 Variation in Properties of the Halogens (SB p.84)

1. Melting Point and Boiling Point

• Going down the group

 the melting points and boiling points
of halogens increase
41.2 Variation in Properties of the Halogens (SB p.84)

1. Melting Point and Boiling Point

• These physical properties depend on

 the strength of van der Waals’ forces
holding the halogen molecules
together
41.2 Variation in Properties of the Halogens (SB p.84)

1. Melting Point and Boiling Point

• Going down the group

 the molecular size increases
 the electron clouds of the molecules
become larger
 more polarizable
41.2 Variation in Properties of the Halogens (SB p.84)

1. Melting Point and Boiling Point

• Instantaneous dipoles
 more readily formed
 the instantaneous dipole-induced
dipole interaction between the
molecules is stronger
41.2 Variation in Properties of the Halogens (SB p.84)

1. Melting Point and Boiling Point

• A greater amount of energy is required

 separate the molecules in the
processes of melting and boiling
 the melting points and boiling points
increase progressively from fluorine
to astatine
41.2 Variation in Properties of the Halogens (SB p.84)

Variations in melting point and

boiling point of the halogens
41.2 Variation in Properties of the Halogens (SB p.84)

2. Electronegativity

Electronegativity is the relative tendency

of the nucleus of an atom to attract
bonding electrons towards itself in a
covalent bond.
41.2 Variation in Properties of the Halogens (SB p.84)

2. Electronegativity

• Going down the group

 the electronegativity values of
halogens decrease
41.2 Variation in Properties of the Halogens (SB p.84)

2. Electronegativity

• Going down the group

 the atomic size increases
 the number of electron shells
increases
 creates a greater screening effect
41.2 Variation in Properties of the Halogens (SB p.84)

2. Electronegativity

• The atomic size increases

 The tendency of the nucleus of the
halogen atom attract bonding
electrons towards itself in a covalent
bond decreases
41.2 Variation in Properties of the Halogens (SB p.85)

Variations in electronegativity
value of the halogens
41.2 Variation in Properties of the Halogens (SB p.85)

3. Electron Affinity

Electron affinity of halogens is the

enthalpy change when one mole of
electrons is added to one mole of halogen
atoms or ions in the gaseous state.
41.2 Variation in Properties of the Halogens (SB p.85)

3. Electron Affinity

• The electron affinity

 increases from fluorine to chlorine
 decreases from chlorine to astatine
41.2 Variation in Properties of the Halogens (SB p.85)

3. Electron Affinity

• The general decrease in electron affinity

 the atomic size increases
 the number of electrons shells down
the group increases
 the effective nuclear charge decreases
 tendency of the nuclei of halogen atoms
to attract additional electrons decreases
41.2 Variation in Properties of the Halogens (SB p.85)

3. Electron Affinity

• Fluorine
 abnormally low electron affinity
41.2 Variation in Properties of the Halogens (SB p.85)

3. Electron Affinity

• Fluorine atom
 very small atomic size
 energy is required to overcome the
repulsion between the additional
electron and the electrons present in
the electron shell
41.2 Variation in Properties of the Halogens (SB p.85)

Variations in electron affinity

of the halogens
41.2 Variation in Properties of the Halogens (SB p.86)

Check Point 41-2A

41.2 Variation in Properties of the Halogens (SB p.86)

Variation in Chemical Properties

• Halogens
 the most reactive group of non-
metallic elements
 all halogens have one electron short
of the octet electronic configuration
 tend to attract an additional electron
to attain the octet electronic
configuration
41.2 Variation in Properties of the Halogens (SB p.86)

Variation in Chemical Properties

• Halogens
 highly electronegative
 highly negative electron affinity
values
 strong oxidizing agents
41.2 Variation in Properties of the Halogens (SB p.86)

Variation in Chemical Properties

• Fluorine
 very strong oxidizing agent
41.2 Variation in Properties of the Halogens (SB p.86)

Variation in Chemical Properties

• Other elements that combine with fluorine
 have their highest possible oxidation
numbers
41.2 Variation in Properties of the Halogens (SB p.86)

1. Relative Oxidizing Power of Halogens

Reactions with Sodium

• All halogens
 combine directly with sodium to form
sodium halides
 the reactivity decreases down the
group from fluorine to iodine
41.2 Variation in Properties of the Halogens (SB p.86)

Reactions with Sodium

• Fluorine
 react explosively to form sodium
fluoride
2Na(s) + F2(g)  2NaF(s)
41.2 Variation in Properties of the Halogens (SB p.86)

Reactions with Sodium

• Chlorine
 react violently to form sodium
chloride
2Na(s) + Cl2(g)  2NaCl(s)
41.2 Variation in Properties of the Halogens (SB p.86)

Reactions with Sodium

• Bromine
 burns steadily in bromine vapours to
form sodium bromide
2Na(s) + Br2(g)  2NaBr(s)
41.2 Variation in Properties of the Halogens (SB p.86)

Reactions with Sodium

• Iodine
 burns steadily in iodine vapours to
form sodium iodide
2Na(s) + I2(g)  2NaI(s)
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Iron(II) Ions

• Aqueous chlorine
 oxidizes green iron(II) ions to
yellowish brown iron(III) ions
2Fe2+(aq) + Cl2(aq)
 2Fe3+(aq) + 2Cl–(aq)
= +0.59 V
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Iron(II) Ions

• Aqueous bromine
 oxidizes green iron(II) ions to
yellowish brown iron(III)
2Fe2+(aq) + Br2(aq)
 2Fe3+(aq) + 2Br–(aq)
= +0.30 V
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Iron(II) Ions

• Iodine
 a mild oxidizing agent
 not strong enough to oxidize iron(II)
ions.
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Iron(II) Ions

• The spontaneity of a reaction can be

worked out
 adding the standard electrode
potentials of the two half reactions
concerned
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Iron(II) Ions

• If the overall standard electrode potential

(i.e. the standard cell electromotive force,
) is a positive value
 the reaction is predicted to be
spontaneous
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Iron(II) Ions

• Aqueous chlorine and bromine

 the for both reactions are

positive
 the oxidation reactions of aqueous
iron(II) ions are spontaneous
41.2 Variation in Properties of the Halogens (SB p.87)

Standard electrode potentials of some related half reactions

Half reaction Standard electrode potential (V)
Cl2(aq) + 2e–  2Cl–(aq) +1.36
Br2(aq) + 2e –  2Br–(aq) +1.07
I2(aq) + 2e–  2I–(aq) +0.54

Fe3+(aq) + e–  Fe2+(aq) +0.77

41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Iron(II) Ions

• Aqueous iodine

 the = –0.23 V
 this reaction is not spontaneous
2Fe2+(aq) + I2(aq)
 2Fe3+(aq) + 2I–
(aq)
= –0.23 V
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Thiosulphate Ions

• Thiosulphate ions
 a reducing agent
 reacts differently with halogens of
different oxidizing power
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Thiosulphate Ions

• Iodine
 reacts with sodium thiosulphate to
form sodium tetrathionate and
sodium iodide
41.2 Variation in Properties of the Halogens (SB p.87)

Reactions with Thiosulphate Ions

• This is a typical reaction

 determine the concentration of iodine
in a solution
 by titration with standard thiosulphate
solution (iodometric titration)
I2(aq) + 2S2O32–(aq)
 2I–(aq) + S4O62–(aq)
41.2 Variation in Properties of the Halogens (SB p.88)

Reactions with Thiosulphate Ions

• Chlorine and bromine

 more powerful oxidizing agents
 oxidize thiosulphate ions to
sulphate(VI) ions
41.2 Variation in Properties of the Halogens (SB p.88)

Reactions with Thiosulphate Ions

• Chlorine
4Cl2(aq) + S2O32–(aq) + 5H2O(l)
 8Cl–(aq) + 2SO42–(aq) + 10H+(aq)
41.2 Variation in Properties of the Halogens (SB p.88)

Reactions with Thiosulphate Ions

• Bromine
4Br2(aq) + S2O32–(aq) + 5H2O(l)
 8Br–(aq) + 2SO42–(aq) + 10H+(aq)
41.2 Variation in Properties of the Halogens (SB p.88)

Reactions of halogens with sodium

Halogens
Chlorine Bromine Iodine
Reactant
Sodium They react Sodium burns in Sodium burns in
violently to form bromine vapour iodine vapour to
sodium chloride to form sodium form sodium
bromide iodide
41.2 Variation in Properties of the Halogens (SB p.88)

Reactions of halogens with iron(II) ions

Halogens
Chlorine Bromine Iodine
Reactant
Iron(II) ions The green iron(II) The green iron(II) The solution
ions are oxidized ions are oxidized remains green
to yellowish to yellowish since iron(II) ions
brown iron(III) brown iron(III) are not oxidized
ions ions by iodine
41.2 Variation in Properties of the Halogens (SB p.88)

Reactions of halogens with thiosulphate ions

Halogens
Chlorine Bromine Iodine
Reactant
Thiosulphate The thiosulphate The thiosulphate The thiosulphate
ions ions are oxidized ions are oxidized ions are oxidized
to sulphate(VI) to sulphate(VI) to tetrathionate
ions ions and iodide ions
41.2 Variation in Properties of the Halogens (SB p.88)

Reactions with Thiosulphate Ions

• The relative oxidizing power of the

halogens decreases in the order:
F2 > Cl2 > Br2 > I2
41.2 Variation in Properties of the Halogens (SB p.89)

2. Disproportionation of the Halogens in

Water and Alkalis

Reactions with Water

• Fluorine
 reacts vigorously with water to form
hydrogen fluoride and oxygen
2F2(g) + 2H2O(l)  4HF(aq) + O2(g)
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• Chlorine
 less reactive than fluorine
 reacts with water to form hydrochloric
acid and chloric(I) acid (also known
as hypochlorous acid
41.2 Variation in Properties of the Halogens (SB p.89)
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• The oxidation number of chlorine

 decreases from 0 in Cl2(g) to –1 in
HCl(aq)
 increases from 0 in Cl2(g) to +1 in
HOCl(aq)
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• Cl2(g)
 simultaneously oxidized and reduced
 an example of disproportionation
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

Disproportionation is a chemical change in

which oxidation and reduction of the same
species (which may be a molecule, atom
or ion) take place at the same time.
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• Chlorine water
 a mixture of hydrochloric acid and
chloric(I) acid
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• Chlorate(I) ion (also known as

hypochlorite ion)
 an unstable ion
 decomposes when exposed to
sunlight or high temperatures to give
chloride ions and oxygen
2OCl–(aq)  2Cl–(aq) + O2(g)
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• Chlorate(I) ion
 able to oxidize dyes to form
colourless compounds
 bleaching power
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• Chlorate(I) ion
Cl2(aq) + H2O(l)
2H+(aq) + Cl–(aq) + OCl–(aq)
OCl–(aq) + dye  Cl–(aq) + (dye + O)
coloured colourless
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• Bromine
 only slightly soluble in water
 mainly exists as molecules in
saturated bromine water
41.2 Variation in Properties of the Halogens (SB p.89)

Reactions with Water

• When the solution is diluted

 hydrolysis takes place
 hydrobromic acid and bromic(I) acid
(also called hydrobromous acid) are
formed
Br2(l) + H2O(l)
HBr(aq) + HOBr(aq)
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Water

• Bromate(I) ion
 also unstable
 forms colourless compounds when
reacting with dyes
OBr–(aq) + dye
coloured
 Br–(aq) + (dye + O)
colourless
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Water

• Iodine
 does not react with water
 only slightly soluble in water
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Water

• Iodine
 soluble in potassium iodide solution
 exists as triiodide ions in thesolution
 often called iodine solution
I2(s) + KI(aq)  KI3(aq)
iodine solution
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• All halogens
 react with aqueous alkalis
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• The reactions between halogens and

aqueous alkalis
 disproportionation (except fluorine)
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• Halogens
 react differently under cold / hot and
dilute / concentrated conditions
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• In general
 their reactivities decrease down the
group
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• Fluorine is passed through a cold and

very dilute (2%) sodium hydroxide
solution
 oxygen difluoride (OF2) is formed
2F2(g) + 2NaOH(aq)
0 cold, very dilute

 2NaF(aq) + OF2(g) + H2O(l)

–1 –1
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• When fluorine is passed through a hot

and concentrated sodium hydroxide
solution
 oxygen is formed instead
2F2(g) + 4NaOH(aq)
0 –2
hot, concentrated

 4NaF(aq) + O2(g) + 2H2O(l)

–1 0
41.2 Variation in Properties of the Halogens (SB p.90)
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• Chlorine
 reacts with cold and dilute sodium
hydroxide solution to form sodium
chloride and sodium chlorate(I) (also
called sodium hypochlorite)
Cl2(aq) + 2NaOH(aq)
0 cold, dilute
 NaCl(aq) + NaOCl(aq) + H2O(l)
–1 +1
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• Chlorine
 reacts with hot and concentrated
sodium hydroxide solution to form
sodium chloride and sodium
chlorate(V)
3Cl2(aq) + 6NaOH(aq)
0 hot, concentrated
 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
–1 +5
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• Bromine
 undergoes similar reactions with
alkalis as chlorine
 sodium bromate(I) formed is unstable
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• Sodium bromate(I) formed

 disproportionates to form sodium
bromide and sodium bromate(V)
readily at room temperature and
pressure
 reversible
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

Br2(aq) + 2NaOH(aq)
cold, dilute
 NaBr(aq) + NaOBr(aq) + H2O(l)

3NaOBr(aq)
2NaBr(aq) + NaBrO3(aq)
41.2 Variation in Properties of the Halogens (SB p.90)

Reactions with Alkalis

• The chemical equation for the overall

reaction:
3Br2(aq) + 6NaOH(aq)
0 cold, dilute
 5NaBr(aq) + NaBrO3(aq) + 3H2O(l)
–1 +5
41.2 Variation in Properties of the Halogens (SB p.91)

Reactions with Alkalis

• Iodine
 behaves similarly as bromine
41.2 Variation in Properties of the Halogens (SB p.91)

Reactions with Alkalis

• Except that the reaction with a cold and

dilute alkali
 reversible
3I2(aq) + 6NaOH(aq)
0 cold, dilute
5NaI(aq) + NaIO3(aq) + 3H2O(l)
–1 +5
41.2 Variation in Properties of the Halogens (SB p.91)

Reactions with Alkalis

• The backward reaction

 often used to prepare standard iodine
solution for iodometric titrations
41.2 Variation in Properties of the Halogens (SB p.91)

Reactions with Alkalis

• Dissolving a known quantity of potassium

iodate(V) in excess potassium iodide
solution and dilute sulphuric(VI) acid
 generated a known amount of iodine
solution
KIO3(aq) + 5KI(aq) + 6H+(aq)
 3I2(aq) + 3H2O(l) + 6K+(aq)
41.2 Variation in Properties of the Halogens (SB p.91)

Reactions with Alkalis

• The iodine generated

 used to oxidize reducing agents
 such as sulphate(IV) ions and
ascorbic acid (vitamin C)
41.2 Variation in Properties of the Halogens (SB p.91)

Reactions with Alkalis

• Excess iodine
 can be determined by back titration
with sodium thiosulphate solution
I2(aq) + 2S2O32–(aq)
 2I–(aq) + S4O62–(aq)
41.2 Variation in Properties of the Halogens (SB p.91)

Check Point 41-2B

41.3 Comparative Study of the Reactions of Halide Ions (SB p.91)

Introduction
• All metal halides
 basically ionic compounds
 the ionic character of metal halides
decreases on going down from
fluorides to iodides
41.3 Comparative Study of the Reactions of Halide Ions (SB p.91)

Introduction
• Lithium fluoride
 ionic
41.3 Comparative Study of the Reactions of Halide Ions (SB p.91)

Introduction
• Lithium iodide
 considerable covalent character
41.3 Comparative Study of the Reactions of Halide Ions (SB p.91)

Introduction
• Chlorides, bromides and iodides
 similar solubilities in water
41.3 Comparative Study of the Reactions of Halide Ions (SB p.91)

Introduction
• Fluorides
 anomalous properties
41.3 Comparative Study of the Reactions of Halide Ions (SB p.91)

Introduction
• Silver chloride, silver bromide and silver
iodide
 insoluble in water
41.3 Comparative Study of the Reactions of Halide Ions (SB p.91)

Introduction
• Silver fluoride
 soluble in water
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• The reactions of halogens with halide
ions follow the order of relative oxidizing
power:
F2 > Cl2 > Br2 > I2
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Fluorine
 displace all other halogens from the
corresponding halide ions
F2(g) + 2Cl–(aq)  2F–(aq) + Cl2(aq)
F2(g) + 2Br–(aq)  2F–(aq) + Br2(aq)
F2(g) + 2I–(aq)  2F–(aq) + I2(aq)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Chlorine
 displace bromine and iodine from
bromide and iodide ions respectively
Cl2(aq) + 2Br–(aq)  Br2(aq) + 2Cl–(aq)
Cl2(aq) + 2I–(aq)  I2(aq) + 2Cl–(aq)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

(a) (b)

The mixture of chlorine water with (a) potassium

bromide solution; (b) potassium iodide solution
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Bromine
 displace iodine from iodide ions only
Br2(aq) + 2I–(aq)  I2(aq) + 2Br–(aq)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Iodine
 cannot displace the other halogens
from the corresponding halide ions
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• The feasibility of redox reactions at
standard states in aqueous solutions
 predicted by using the values of
standard electrode potentials
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Adding up the standard cell electrode
potentials of the two corresponding half
reactions
 obtain the of the overall
cell reaction
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• If the is a positive value

 spontaneous
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Consider whether the following redox
reaction will take place at standard
states:
Br2(aq) + 2I–(aq)  I2(aq) + 2Br–(aq)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Considered as the combination of the
following two equilibria competing with
one another:
Br2(aq) + 2e–
2Br–(aq) = +1.07 V
I2(aq) + 2e–
2I–(aq) = +0.54 V
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• The half reaction Br2(aq) + 2e–
2Br–(aq)
 more positive standard electrode
potential
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Bromine
 higher tendency to gain electrons (i.e.
stronger oxidizing power)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• Therefore
Br2(aq) + 2e–
2Br–(aq) = +1.07 V
I2(aq) + 2e–
–) 2I–(aq) = +0.54 V
Br2(aq) + I2(aq)
2Br–(aq) + 2I–(aq) = +0.53 V
41.3 Comparative Study of the Reactions of Halide Ions (SB p.92)

Reactions of Halogens
• The of the overall reaction

 a positive value
 proceed spontaneously
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of halide ions with halogens

Halogen added
Aqueous
solution F2 Cl2 Br2 I2

F– No reaction No reaction No reaction No reaction

A pale yellow No reaction No reaction No reaction
solution is
Cl–
formed (Cl2 is
formed)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of halide ions with halogens

Halogen added
Aqueous
solution F2 Cl2 Br2 I2

A yellow A yellow No reaction No reaction

solution solution
Br–
is formed (Br2 is is formed (Br2 is
formed) formed)
A yellowish A yellowish A yellowish No reaction
brown brown brown
I– solution is solution is solution is
formed formed formed (I2 is
(I2 is formed) (I2 is formed) formed)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of Halogens
• The most convenient way to carry out
displacement reactions:
 mix aqueous solutions of the
halogens with aqueous solutions of
potassium iodide, potassium bromide
and potassium chloride
 shake them well
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of Halogens
• Iodine
 almost insoluble in water
 dissolves readily in a solution
containing iodide ions
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of Halogens
• The soluble triiodide ion, I3–, is formed in
this way:
I2(s) + I–(aq) I3–(aq)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of Halogens
• Observing the colour changes
 difficult to determine whether certain
reactions have taken place or not by
only
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of Halogens
• To determine whether the reaction
mixture contains bromine or iodine
 add a small amount of 1,1,1-
trichloroethane to the reaction
mixture
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of Halogens
• Any bromine or iodine present
 dissolve more readily in the organic
solvent than in water
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of Halogens
• If the reaction mixture contains bromine
 the bromine will dissolve in the
bottom organic layer
 give a deep orange colour
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Reactions of Halogens
• If the reaction mixture contains iodine
 the iodine will dissolve in the bottom
organic layer
 give a violet colour
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

(a) (b)

(a) If the reaction mixture contains bromine, the

bottom organic layer will appear deep orange; (b) If
the reaction mixture contains iodine, the bottom
organic layer will appear violet.
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

Check Point 41-3A

41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

• Aqueous solutions of chlorides, bromides
and iodides
 give precipitates when reacting
with silver nitrate(V) solution
 a characteristic test to show the
presence of halide ions (except
fluoride ions)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

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
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

• All silver halides
 insoluble in acids
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

• Dilute nitric(V) acid should be added
before silver nitrate(V) solution
 remove interfering ions
 like sulphate (IV) ions or carbonate
ions
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

• The formation of the white precipitate of
silver sulphate(IV) or silver carbonate
 may be mistaken as silver halides,
can be prevented
2H+(aq) + SO32–(aq)
 SO2(g) + H2O(l)
2H+(aq) + CO32–(aq)
 CO2(g) + H2O(l)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

AgCl(s)

Formation of silver halides:

silver chloride
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

AgBr(s)

Formation of silver halides:

silver bromide
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

AgI(s)

Formation of silver halides:

silver iodide
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

• The formation of silver chloride, silver
bromide and silver iodide
 identified by their colours
 or by their reactions with aqueous
ammonia
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

• Silver chloride
 dissolves readily in aqueous
ammonia
 the formation of the complex
diamminesilver(I) ion ([Ag(NH3)2]+
(aq))
 soluble in water
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

AgCl(s) + 2NH3(aq)
 [Ag(NH3)2]+(aq) + Cl–(aq)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

• Silver bromide
 slightly soluble in aqueous ammonia
41.3 Comparative Study of the Reactions of Halide Ions (SB p.94)

Reactions with Silver Ions

• Silver iodide
 insoluble in aqueous ammonia
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

Reactions with Silver Ions

• When exposed to sunlight
 silver chloride turns grey
 silver bromide turns yellowish grey
 silver iodide remains yellow
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

Reactions with Silver Ions

• The colour changes of silver chloride and
silver bromide
 photochemical decomposition of the
silver halides into their constituent
elements (i.e. silver and halogens)
light
2AgCl(s)  2Ag(s) + Cl2(g)
light
2AgBr(s)  2Ag(s) + Br2(g)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

Action of acidified silver nitrate(V) solution on halides

Confirmatory test of the product
Action of acidified
Ion silver nitrate(V) Effect of exposure Effect of adding
solution on halides to sunlight aqueous ammonia

A white precipitate The solution turns The white

Cl– is formed (AgCl is grey precipitate dissolves
formed)
A pale yellow The solution turns The pale yellow
Br– precipitate is formed yellowish grey precipitate slightly
(AgBr is formed) dissolves
A yellow precipitate The solution remains The yellow
I– is formed (AgI is yellow precipitate does not
formed) dissolve
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

Reactions with Concentrated

Sulphuric(VI) Acid

• Concentrated sulphuric(VI) acid

 an oxidizing acid
 exhibits both oxidizing and acidic
properties
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

Reactions with Concentrated

Sulphuric(VI) Acid

• On treatment with concentrated

sulphuric(VI) acid
 fluorides and chlorides give hydrogen
fluoride and hydrogen chloride
respectively
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

Reactions with Concentrated

Sulphuric(VI) Acid

• Example:
NaF(s) + H2SO4(l)
 NaHSO4(s) + HF(g)
NaCl(s) + H2SO4(l)
 NaHSO4(s) + HCl(g)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

Reactions with Concentrated

Sulphuric(VI) Acid

• Bromides and iodides

 do not give hydrogen bromide and
hydrogen iodide respectively
 sulphur dioxide or hydrogen sulphide
is formed
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

(a) (b)

Action of concentrated sulphuric(VI) acid on:

(a) sodium bromide; (b) sodium iodide
41.3 Comparative Study of the Reactions of Halide Ions (SB p.95)

Reactions with Concentrated

Sulphuric(VI) Acid

• Bromides
NaBr(s) + H2SO4(l)
 NaHSO4(s) + HBr(g)
2HBr(g) + H2SO4(l)
 SO2(g) + Br2(g) + 2H2O(l)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Reactions with Concentrated

Sulphuric(VI) Acid

• The chemical equation for the overall

reaction is
2NaBr(s) + 3H2SO4(l)
 2NaHSO4(s) + SO2(g) +
Br2(g) + 2H2O(l)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Reactions with Concentrated

Sulphuric(VI) Acid

• Iodides
NaI(s) + H2SO4(l)  NaHSO4(s) + HI(g)
8HI(g) + H2SO4(l)
 H2S(g) + 4I2(g) + 4H2O(l)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Reactions with Concentrated

Sulphuric(VI) Acid

• The chemical equation for the overall

reaction is
8NaI(s) + 9H2SO4(l)
 8NaHSO4(s) + H2S(g) +
4I2(g) + 4H2O(l)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Reactions with Concentrated

Sulphuric(VI) Acid

• Bromides and iodides

 do not react in the same way as
fluorides and chlorides
 the hydrogen bromide and hydrogen
iodide produced are oxidized by
concentrated sulphuric(VI) acid to
bromine and iodine respectively
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Reactions with Concentrated

Sulphuric(VI) Acid

• Hydrogen chloride
 is not oxidized by concentrated
sulphuric(VI) acid
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Action of concentrated sulphuric(VI) acid on halides

Halide Action of concentrated Confirmatory test of

Product
ion sulphuric(VI) acid the product

• Steamy fumes are HCl • Dense white fumes are

formed formed with aqueous
Cl– • No green gas is ammonia
evolved even on • It turns blue litmus paper
heating red but not bleached
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Action of concentrated sulphuric(VI) acid on halides

Halide Action of concentrated Confirmatory test of
Product
ion sulphuric(VI) acid the product

• Steamy fumes are HBr • White fumes are formed

formed with aqueous ammonia
• A pungent smell is SO2 • It turns orange
Br– detected dichromate(VI) solution
• A brown gas is green
evolved on warming Br2 • A red colour is observed
when adding hexane
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Action of concentrated sulphuric(VI) acid on halides

Halide Action of concentrated Confirmatory test of
Product
ion sulphuric(VI) acid the product
• Steamy violet fumes HI • White fumes are formed
are formed with aqueous ammonia
• A bad egg smell is H 2S • It turns lead(II) ethanoate
I– detected paper black
I2 • A violet colour is
observed when adding
hexane
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Reactions with Concentrated

Sulphuric(VI) Acid

• The reaction of chlorides with

concentrated sulphuric(VI) acid
 used for the preparation of hydrogen
chloride in the laboratory
41.3 Comparative Study of the Reactions of Halide Ions (SB p.96)

Reactions with Concentrated

Sulphuric(VI) Acid

• Hydrogen bromide and hydrogen iodide

 cannot be prepared in this way
41.3 Comparative Study of the Reactions of Halide Ions (SB p.97)

Reactions with Phosphoric(V) Acid

• Phosphoric(V) acid
 not an oxidizing agent
 reacts with halides to form the
corresponding hydrogen halides
 a general method to prepare
hydrogen halides in the laboratory
41.3 Comparative Study of the Reactions of Halide Ions (SB p.97)

Reactions with Phosphoric(V) Acid

3NaCl(s) + H3PO4(l)
 Na3PO4(s) + 3HCl(g)
3NaBr(s) + H3PO4(l)
 Na3PO4(s) + 3HBr(g)
3NaI(s) + H3PO4(l)
 Na3PO4(s) + 3HI(g)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.97)

Action of concentrated phosphoric(V) acid on halides

Halide Action of concentrated Confirmatory test of
Product
ion phosphoric(V) acid the product

Cl– Steamy fumes are HCl White fumes are formed

Br– formed on warming HBr with aqueous ammonia

I– HI

Check Point 41-3B

41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Introduction
• Hydrogen halides
 prepared by the direct reactions of
hydrogen with halogens
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Introduction
• Hydrogen
 reacts explosively with fluorine
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Introduction
• Hydrogen chloride is formed
 when hydrogen burns in chlorine gas
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Introduction
• Hydrogen
 reacts with bromine or iodine in the
presence of a catalyst at high
temperatures
 form hydrogen bromide and
hydrogen iodide respectively
H2(g) + X2(g)  2HX(g)
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Introduction
• Hydrogen halides
 prepared by adding concentrated
phosphoric(V) acid to the halides
3X–(aq) + H3PO4(l)
 PO43–(aq) + 3HX(g)
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Some physical properties of hydrogen halides

Relative Melting Physical state at
Hydrogen Boiling
molecular point room temperature
halide point (C)
mass (C) and pressure
HF 20.0 –83.1 19 Liquid
HCl 36.5 –115 –85 Gas
HBr 87 80.9 –67 Gas
HI 127.9 –50 –36 Gas
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Acidic Properties of Hydrogen Halides

• Hydrogen halides
 dissociate in water to form acidic
solutions
HX(g) + H2O(l)
H3O+(aq) + X–(aq)
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Acidic Properties of Hydrogen Halides

• The larger the acid dissociation constant
 the stronger its acid strength
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.98)

Acidic Properties of Hydrogen Halides

• The acid strength of hydrogen halides
decreases in the order:
HI > HBr > HCl >> HF
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

Acid dissociation constants of hydrogen halides and their

degrees of dissociation in 0.1 M solutions
Acid dissociation Degree of
Hydrogen Acid
constant, dissociation in 0.1 M
halide strength
Ka (mol dm–3) solution (%)
HF 7 × 10–4 8.5 Low
HCl 1 × 107 92 Strong
HBr 1 × 109 93 Strong
HI 1 × 1011 95 Very strong
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

Anomalous Behaviour of Hydrogen

Fluoride

1. Hydrogen fluoride has abnormally high

boiling point and melting point among
the hydrogen halides
• Molecules of all other hydrogen halides
 held together by weak van der Waal’s
forces only
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

Formation of the extensive intermolecular hydrogen

bonds among hydrogen fluoride molecules
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

2. Hydrogen fluoride is soluble in water

• A dilute solution of hydrogen fluoride

 behaves only as a weak acid
HF(l) + H2O(l)
H3O+(aq) + F–(aq) ..…... (1)
Ka = 7 × 10–4 mol dm–3
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

2. Hydrogen fluoride is soluble in water

• A more concentrated solution of

hydrogen fluoride
 another equilibrium is established
 the fluoride ion form the complex ion
[HF2]–
F–(aq) + HF(l)
[HF2]–(aq) .…....
(2)
K = 5.1 dm3 mol–1
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

2. Hydrogen fluoride is soluble in water

• The equilibrium of reaction (2)

 shifts to the right
 the concentration of hydrogen
fluoride increases
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

2. Hydrogen fluoride is soluble in water

• The consumption of fluoride ions in

reaction (2)
 the equilibrium of reaction (1) also
shifts to the right
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

2. Hydrogen fluoride is soluble in water

• The acid strength of hydrogen fluoride

 enhanced
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.99)

2. Hydrogen fluoride is soluble in water

• A concentration of approximately
5 to 15 M of hydrogen fluoride
 effectively a strong acid
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.100)

3. Other fluorides (e.g. potassium fluoride)

also react with hydrogen fluoride to form
acid salts containing the stable [HF2]–ion

KF(s) + HF(l) KHF2(s)

41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.100)

3. Other fluorides (e.g. potassium fluoride)

also react with hydrogen fluoride to form
acid salts containing the stable [HF2]–ion

• Heating the solid potassium hydrogen

difluoride
 reverses the reaction
 a convenient way to obtain
anhydrous hydrogen fluoride
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.100)

4. A special property of hydrofluoric acid is

its ability to react with glass

• Use to etch glass

41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.100)

A glass is etched by
hydrofluoric acid
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.100)

4. A special property of hydrofluoric acid is

its ability to react with glass

• The glass object to be etched

 coated with wax or a similar acid-
proof material
 cutting through the wax layer to
expose the glass
 apply hydrofluoric acid
41.4 Acidic Properties of Hydrogen Halides and the Anomalous Behaviour of
Hydrogen Fluoride (SB p.100)

4. A special property of hydrofluoric acid is

its ability to react with glass

• The principle of etching glass

CaSiO3(s) + 6HF(aq)
 CaF2(aq) + SiF4(aq) + 3H2O(l)

Check Point 41-4

The END
41.1 Characteristic Properties of the Halogens (SB p.82)

What is the predicted colour of astatine?

The colour of astatine is black.

Answer

Back
41.1 Characteristic Properties of the Halogens (SB p.83)

(a) Write the electronic configuration of each of the

halogens. What is in common about these electronic
configurations?
Answer
41.1 Characteristic Properties of the Halogens (SB p.83)

(a)
Halogen Electronic configuration
F 1s22s22p5
Cl 1s22s22p63s23p5
Br 1s22s22p63s23p63d104s24p5
I 1s22s22p63s23p63d104s24p64d105s25p5
At 1s22s22p63s23p63d104s24p64d104f145s25p65d106s66p5

They have the outermost shell electronic configuration of ns2np5.

41.1 Characteristic Properties of the Halogens (SB p.83)

(b) Does a halogen atom gain or lose an electron more

readily when forming a compound?
Answer
(b) A halogen atom tends to gain an electron when forming a
compound.
41.1 Characteristic Properties of the Halogens (SB p.83)

(c) The colour of halogens darkens on going down the

group. Explain why.

(c) Going down the halogen, the sizes of the halogen atoms Answer
increase,
and the radiation of lower frequency is absorbed. For instance, since
fluorine atom has a smaller size, it tends to absorb the radiation of
relatively high frequency (i.e. blue light), hence fluorine appears
yellow. Atoms of other halogens have larger sizes and they absorb
radiation of lower frequency. For example, iodine absorbs the
radiation of relatively low frequency (i.e. yellow light), hence iodine
appears violet.
Back
41.2 Variation in Properties of the Halogens (SB p.86)

(a) Explain the term “electron affinity”. Describe the trend

of variation in electron affinity of the halogens.
Answer
41.2 Variation in Properties of the Halogens (SB p.86)

(a) Electron affinity is the enthalpy change when one mole of

electrons is added to one mole of atoms or ions in the gaseous
state. The electron affinity increases from fluorine to chlorine
and then decreases from chlorine to astatine. The general
decrease in electron affinity is due to the increases in atomic
size and number of electron shells down the group. This leads
to a decrease in effective nuclear charge. Therefore, the
tendency of the nuclei of halogen atoms to attract additional
electrons decreases. On the other hand, fluorine has an
abnormally low electron affinity. It is because fluorine atom has
a very small atomic size. Energy is required to overcome the
repulsion between the additional electron and the electrons
present in the electron shell. The electron affinity of fluorine is
therefore lower than expected.
41.2 Variation in Properties of the Halogens (SB p.86)

(b) For each of the following physical properties of the

halogens, state the trend down the group.
(i) Atomic radius (b) (i) Increase
(ii) Ionic radius (ii) Increase
(iii) Increase
(iii) Melting point (iv) Decrease
(iv) Electronegativity (v) Increase

(v) Colour intensity

Answer
Back
41.2 Variation in Properties of the Halogens (SB p.90)

Why does fluorine always behave differently from

chlorine, bromine and iodine?
Answer
Fluorine cannot expand its octet as there are no low-lying empty
d orbitals available, and the energy required to promote electrons
into the third quantum shell is very high. Since fluorine is the most
electronegative element and there is only one unpaired p electron
available for bonding, its oxidation state is limited to –1 when
bonded with other elements.

Back
41.2 Variation in Properties of the Halogens (SB p.91)

(a) Explain why halogens are strong oxidizing agents.

(a) It is because all halogens have one electron short ofAnswer

the octet
electronic configuration, they tend to attract an additional
electron to complete the octet. They have high electronegativity
values and highly negative electron affinity values. Halogens are
thus strong oxidizing agents.
41.2 Variation in Properties of the Halogens (SB p.91)

(b) What chemical species are present in the following

solutions?
(i) Chlorine water
(ii) Bromine water
(iii) Iodine in potassium iodide solution
Answer
(b) (i) Cl2(aq), Cl–(aq), ClO–(aq), H+(aq), H2O(l )
(ii) Br2(aq), Br–(aq), BrO–(aq), H+(aq), H2O(l )
(iii) I–(aq), K+(aq), I3–(aq), H2O(l) Back
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

(a) Is bromine and iodine more soluble in water or 1,1,1-

trichloroethane? Explain your answer.
Answer
(a) Both bromine and iodine are more soluble in
1,1,1-trichloroethane than in water. It is because
both bromine and iodine are non polar
molecules, and water is a much polar solvent
than 1,1,1-trichloroethane.
41.3 Comparative Study of the Reactions of Halide Ions (SB p.93)

(b) Describe a simple way to increase the solubility of

iodine in water.
Answer
(b) The solubility of iodine in water can be increased
by adding potassium iodide solution. Iodine
exists as triiodide ions in potassium iodide
solution as shown in the following equation:
I2(s) + KI(aq)  KI3(aq)

Back
41.3 Comparative Study of the Reactions of Halide Ions (SB p.97)

(a) State any observable changes when the following

substances are added into sodium iodide solution.
Give appropriate equations, if any.
(i) Iron(II) sulphate(VI) solution
Answer
(a) (i) There is no observable change.
41.3 Comparative Study of the Reactions of Halide Ions (SB p.97)

(a) State any observable changes when the following

substances are added into sodium iodide solution.
Give appropriate equations, if any.
(ii) Chlorine water
Answer
(a) (ii) The solution turns yellowish brown.
Cl2(aq) + 2NaI(aq)  I2(aq) + 2NaCl(aq)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.97)

(a) State any observable changes when the following

substances are added into sodium iodide solution.
Give appropriate equations, if any.
(iii) Sodium iodate(V) solution and dilute
sulphuric(VI) acid
Answer
(a) (iii) The solution turns yellowish brown.
5I–(aq) + IO3–(aq) + 6H+(aq)  3I2(aq) + 3H2O(l)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.97)

(b) If you are given two solutions, sodium fluoride and

sodium chloride, how would you distinguish them
with a simple chemical test? State all observable
changes and write equations where appropriate.

(b) Sodium chloride solution and sodium fluoride solution can Answer
be
distinguished using acidified silver nitrate(V) solution. Sodium
chloride solution reacts with acidified silver nitrate(V) solution to
form a white precipitate, while sodium fluoride solution does not.
Ag+(aq) + Cl–(aq)  AgCl(s)
white precipitate Back
41.3 Comparative Study of the Reactions of Halide Ions (SB p.100)

(a) For each of the following pairs, which is a stronger

acid? Explain your answers.
(i) Dilute hydrochloric acid and dilute hydrofluoric
acid
Answer
41.3 Comparative Study of the Reactions of Halide Ions (SB p.100)

(a) (i) Dilute hydrochloric acid is a stronger acid than dilute

hydrofluoric acid, as hydrochloric acid has a much larger Ka value
than hydrofluoric acid.
HCl(aq) + H2O(l) H3O+(aq) + Cl–(aq)
Ka = 1 × 107 mol dm–3
HF(l) + H2O(l) H3O+(aq) + F–(aq)
Ka = 7 × 10–4 mol dm–3
The small Ka value of hydrofluoric acid indicates that only
a small amount of hydrogen fluoride molecules is ionized. Most of
hydrogen fluoride molecules still exist in the undissociated form.
The large Ka value of hydrochloric acid indicates that
almost all hydrogen chloride molecules are ionized in water. This
can be explained by the presence of extensive intermolecular
hydrogen bonds among hydrogen fluoride molecules.
41.3 Comparative Study of the Reactions of Halide Ions (SB p.100)

(a) For each of the following pairs, which is a stronger

acid? Explain your answers.
(ii) Concentrated hydrochloric acid and concentrated
hydrofluoric acid
Answer
41.3 Comparative Study of the Reactions of Halide Ions (SB p.100)

(a) (ii) Concentrated hydrofluoric acid is a stronger acid than

concentrated hydrochloric acid. Hydrogen fluoride is soluble in
water. In a dilute solution of hydrogen fluoride, it behaves only as a
weak acid.
HF(l) + H2O(l) H3O+(aq) + F–(aq) ...... (1)
Ka = 7 × 10–4 mol dm–3
However, in a more concentrated solution of hydrogen fluoride,
another equilibrium is established with the fluoride ion forming the
complex ion [HF2]–.
F–(aq) + HF(l) [HF2]–(aq) ......…….......(2)
K = 5.1 dm3 mol–1
The equilibrium of reaction (2) shifts to the right as the
concentration of hydrogen fluoride increases. With the consumption
of fluoride ions in reaction (2), the equilibrium of reaction (1) also
shifts to the right. The acid strength of hydrogen fluoride is therefore
enhanced. Hence, concentrated hydrofluoric acid is effectively a
41.3 Comparative Study of the Reactions of Halide Ions (SB p.100)

(b) Explain the following phenomena:

(i) Hydrogen fluoride is a liquid at room
temperature and pressure.
Answer
(b) (i) Hydrogen fluoride exists as a liquid at room
temperature and pressure due to its ability to form extensive
intermolecular hydrogen bonds.
41.3 Comparative Study of the Reactions of Halide Ions (SB p.100)

(b) Explain the following phenomena:

(ii) Hydrogen fluoride forms acid salts – potassium
hydrogen difluoride.
Answer
(b) (ii) Hydrogen fluoride is able to react with other
fluorides (e.g. potassium fluoride) to form acid salts
containing the stable [HF2]– ion (e.g. potassium hydrogen
fluoride).
KF(s) + HF(l) KHF2(s)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.100)

(b) Explain the following phenomena:

(iii) Hydrogen fluoride can be used to etch glass.

(b) (iii) The principle of etching glass by hydrofluoric acid

Answer
can be explained by its reaction with the silicate of glass.
CaSiO3(s) + 6HF(aq)  CaF2(aq) + SiF4(aq) + 3H2O(l)
41.3 Comparative Study of the Reactions of Halide Ions (SB p.100)

(c) Complete and balance the following equations:

(i) F2(g) + H2O(l) 
(ii) F2(g) + KOH(aq) (cold, dilute) 
Answer
(c) (i) 2F2(g) + 2H2O(l )  4HF(aq) + O2(g)
(iii) 2F2(g) + 2KOH(aq)  2KF(aq) + OF2(g) + H2O(l)

Back