2.

7 Inorganic chemistry of group 7

(limited to chlorine, bromine and iodine)

Cro2012

Group 7 the halogens

The elements in group 7 of the periodic table, on the right,
are called the halogens.
F

fluorine

Cl

chlorine

Br

bromine

I
At

iodine
astatine

a.

recall the characteristic physical properties of the elements

limited to the appearance of solutions of the elements in water
and hydrocarbon solvents

In water:

In hydrocarbon solvents:

Chlorine solution is pale green

Bromine solution is yellow to
orange
Iodine solution is brown.

Chlorine solution is pale green

Bromine solution is yellow to orange
Iodine solution is pink-purple.

Oxidation Reaction of Halogens

b.

describe and carry out the following chemical reactions of halogens:

i.
oxidation reactions with metal and non-metallic elements and ions such as iron(II) and iron(III) ions
in solution

With Metals:
React strongly with electropositive metals, removing the
outer electrons to become reduced themselves.

Oxidation Reaction of Halogens

b.

describe and carry out the following chemical reactions of halogens:

i.
oxidation reactions with metal and non-metallic elements and ions such as iron(II) and iron(III) ions
in solution

With Non-Metals:
The halogen usually achieves a noble gas configuration
by forming a covalent bond:

Reactivity decreases

Oxidation Reaction of Halogens

b.

describe and carry out the following chemical reactions of halogens:

i.
oxidation reactions with metal and non-metallic elements and ions such as iron(II) and iron(III) ions
in solution

With Iron(II) chloride solution:

Disproportionation
b.

describe and carry out the following chemical reactions of halogens:

ii. disproportionation reactions with cold and hot alkali, eg hot
potassium hydroxide with iodine to produce potassium iodate(V)

Give the oxidation

numbers for the chlorine
containing species.

Disproportionation
b.

describe and carry out the following chemical reactions of halogens:

ii. disproportionation reactions with cold and hot alkali, eg hot
potassium hydroxide with iodine to produce potassium iodate(V)

Iodine/thiosulfate titration
c.

carry out an iodine/thiosulfate titration, including calculation of the results and evaluation of the
procedures involved, eg determination of the purity of potassium iodate(V) by liberation of
iodine and titration with standard sodium thiosulfate solution

Remember that when carrying out this titration the starch is added near the end
point (when the solution is pale yellow).
Addition of starch to a solution that contains iodine or triiodide ion forms a
reversible blue complex. The disappearance of this blue coloured complex is a
much more sensitive method of determining the end point.
However, if the starch is added to a solution which contains a great deal of iodine,
the complex which forms may not be reversible. Therefore, the starch is not
added until shortly before the end point is reached.

Reaction with conc. Sulphuric Acid

d.

describe and carry out the following reactions:

i.
potassium halides with concentrated sulfuric acid, halogens and silver
nitrate solution

White steamy fumes

With sodium bromide/iodide, the hydrogen

halides are oxidised by the acid:

Orange/brown
fumes or colour

Purple fumes
and/or black solid

Displacement (Redox) Reactions

d.

describe and carry out the following reactions:

i. potassium halides with concentrated sulfuric acid, halogens
and silver nitrate solution

Potassium halides react

with other halogens:

What gets reduced and

what gets oxidised?
A more reactive halogen will displace a less
reactive halogen from its halide in solution.
So:
Cl2 displaces Br2 from Br- and I2 from I Br2 displaces I2 from I-

d.

Testing for Halides: Silver

Halides

describe and carry out the following reactions:

i.
potassium halides with concentrated sulfuric acid, halogens and silver
nitrate solution
ii.
silver halides with sunlight and their solubilities in aqueous ammonia
solution

Addition of dilute nitric acid

Then add aqueous silver
Nitrate solution.

Testing for Halides: Silver

Halides
Equations
Partial decomposition turns AgCl into
grayish precipitate in sunlight.

d.

describe and carry out the following reactions:

ii. silver halides with sunlight and their solubilities in aqueous
ammonia solution

The silver halides are unstable in the presence of sunlight. They

decompose forming silver (seen as dark specs) and the halogen,
for example:
2AgI(s) 2Ag(s) + I2(s)

Reaction of Hydrogen Halides

d.

describe and carry out the following reactions:

iii.

hydrogen halides with ammonia and with water (to produce acids)

Hydrogen halides react with

ammonia gas to form
ammonium halides:

Hydrogen chloride dissolves

in water to form
hydrochloric acid.

e.

make predictions about fluorine and astatine and their

compounds based on the trends in the physical and chemical
properties of halogens.

What are the general properties of

the halogens?
All the halogens are:
Diatomic non-metals and so do not conduct electricity
brittle and crumbly when solid
poisonous and smelly.
Very reactive and strong oxidising agents.
They become darker in colour down the group:
is pale yellow
is yellow-green
is red-brown
is grey

What is the electron structure of the

halogens?
All halogens have seven
electrons in their outer
shell. This means that:
They can easily obtain a
full outer shell by gaining
one electron.
They all gain an electron
in reactions to form
negative ions with a -1
charge.
They have similar
chemical properties.

fluorine
2,7

chlorine
2,8,7

bromine
2,8,8,7

The reactivity of alkali metals decreases going down the

group. What is the reason for this?
The atoms of each element get
F
larger going down the group.
This means that the outer shell gets
further away from the nucleus and
is shielded by more electron shells.
Cl
The further the outer shell is from
the positive attraction of the
nucleus, the harder it is to attract
another electron to complete the
outer shell.
Br
This is why the reactivity of the
halogens decreases going down
group 7.

decrease in reactivity

How does electron structure affect

reactivity?

What is the physical state of the

halogens?

The melting and boiling points of the halogens increase

down the group, as the molecules become bigger.
Halogen

Relative
size

Melting
point (C)

Boiling
point (C)

State

-220

-118

gas

-101

-34

gas

-7

59

liquid

114

184

solid

What is the state of each halogen at room temperature?

Halogen Solubility
Solubility in water decreases down group.
Chlorine reacts in water to form chlorine water ( a
mixture of HCl and chloric (I) acid:

Chloric (I) acid is what gives a solution of chlorine

its bleaching properties.
Bromine reacts in a similar way, but to a lesser
extent.