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Brown's Chemistry Clinic
GCSE-IGCSE-KS4 Science Revision-Chemistry Information Notes on
Group
7 The Halogens
GCSE Quiz Foundation
or Higher
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KEYWORDS: astatine
*
bleach * bromine * chemical characteristics
*
chlorine * data on the elements
* displacement
reaction * electrolysis
of NaCl * explaining reactivity
trend * fluorine * hydrochloric acid
*
hydrogen halides * iodine
* naming halogen compounds * physical characteristics
* PVC
* reaction of sodium hydroxide and chlorine * reaction with metals
* reaction
with hydrogen * silver halide photography *
uses of chlorine
* uses of fluorine, bromine and iodine * uses of hydrogen
* uses of sodium chloride * uses
of sodium hydroxide *
and on separate web pages: GCSE-KS4-IGCSE Group 7 Halogens
task/worksheet * Halogen Quizzes *
Extra electrochemistry with
more on electrolysis

Note:
Using 0
to denote the Group number of Noble Gases is very historic now since
compounds of xenon known exhibiting a valency of 8.
Because of the
horizontal series of elements e.g. like the Sc to Zn block (10 elements),
Groups 3 to 8 can also be numbered as Groups 13 to 18 to fit in with the
actual number of vertical columns of elements. This can make things confusing, but there
it is, classification is still in progress!

Introduction
to the Halogens
(see also halogens data table
below)
The Halogens are typical non-metals
and
form the 7th Group
in the Periodic Table (the vertical pink column above). 'Halogens'
means 'salt formers' and the most common compound is sodium
chloride which is found from natural evaporation as huge deposits of 'rock salt' or
the even more abundant 'sea salt' in the seas and oceans.
Physical features
and important
trends down the Group with
increasing atomic number (see
halogens data table
below
too) ...
-
typical non-metals with relatively
low melting points and boiling points.
-
The melting points and
boiling increase steadily down the group (so the change in state at room temperature
from gas ==> liquid ==> solid), this is because the weak
electrical intermolecular
attractive forces increase with increasing size of atom or molecule.
-
They are all coloured
non-metallic elements and the colour gets darker down the group.
-
They are all poor
conductors of heat and electricity - typical of non-metals.
-
When solid they
are brittle and crumbly e.g. iodine.
-
The size of the atom gets
bigger as more inner electron shells are filled going down from
one period to another.
Chemical features, similarities, and physical property
and reactivity trends
-
The atoms all have 7 outer electrons,
this outer electron similarity, as with any Group in the Periodic Table,
makes them have very similar chemical properties e.g.
-
they form singly
charged negative ions e.g. chloride Cl-
because they
are one electron short of a noble gas electron structure. They
gain one negative electron (reduction) to be stable and this gives a surplus
electric charge of -1. These ions are
called the halide ions, two others you will encounter are
called the bromide Br- and iodide I-
ions.
-
they form ionic
compounds with metals e.g. sodium chloride Na+Cl-.
(ionic bonding revision notes page)
-
they form covalent
compounds with non-metals and with themselves (see below). The
bonding in the molecule involves single covalent bonds e.g. hydrogen
chloride HCl or H-Cl. (covalent
bonding revision notes page)
-
Note on
naming
halogen compounds:
-
When combined with
other elements in simple compounds the name of the halogen element changes
slightly from ...ine to ...ide.
-
Fluorine forms a
fluoride (ion F-), chlorine forms a chloride
(ion Cl-), bromine a bromide (ion Br-) and
iodine an iodide (ion I-).
-
The other element at
the start of the compound name e.g. hydrogen, sodium, potassium,
magnesium, calcium, etc. remains unchanged.
-
So typical
halogen compound names are, potassium fluoride, hydrogen
chloride, sodium chloride, calcium bromide, magnesium iodide etc.
-
The elements all exist as X2
or X-X, diatomic molecules
where X represents the halogen atom.
-
A more reactive
halogen can displace a less reactive halogen from its salts (halogen
displacement description).
-
The reactivity
decreases down the group (explanation of halogen
reactivity trendn.
-
they are all TOXIC
elements (for more detail see
uses of Halogens).
-
Astatine
is very radioactive, so difficult to study BUT its properties can
be predicted using the principles of the Periodic Table and the
Halogen Group trends!
-
Details of how to
identify halogens and their compounds are on the Chemical
Tests page (use the alphabetical list at the
top of this other page).
|
DATA
Selected Properties
of the Group 7 Halogens (more
Group 7 halogens AS-A2 data)
|
|
Symbol and Name
|
Atomic
Number |
Electron
arrangement |
State
and colour at room temperature, colour of vapour when heated |
Melting
point |
Boiling
point |
atom
radius pm |
|
F
Fluorine
|
9 |
2.7 |
pale
yellow gas |
-219oC,
54K |
-188oC
85K |
64 |
|
Cl
Chlorine
|
17 |
2.8.7 |
green
gas |
-101oC,
172K |
-34oC,
239K |
99 |
| Br
Bromine
|
35 |
2.8.18.7 |
dark
red liquid, brown vapour |
-7oC,
266K |
59oC,
332K |
114 |
|
I
Iodine
|
53 |
2.8.18.18.7 |
dark crumbly solid, purple vapour |
114oC,
387K |
184oC,
457K |
133 |
| At
Astatine |
85 |
2.8.18.32.18.7
|
 black
solid, dark vapour |
302oC
575K |
380oC
653K |
140 |


The Reactivity
Order and Displacement
Reactions
Chlorine water, bromine water
and iodine water are added in turn to aqueous solutions of the salts
potassium chloride (KCl),
potassium bromide (KBr) and potassium iodide (KI). Three
combinations produce a reaction (and 3 don't!).
You
can get the observations from the diagrams! A
darkening effect compared to a water blank confirms a displacement
reaction has happened. Chlorine displaces
bromine from potassium bromide and iodine from potassium iodide.
Bromine only displaces iodine from potassium iodide but iodine displaces non of
the other two.
On the basis that the most reactive element displaces a
least reactive element the reactivity order must be chlorine >
bromine > iodine.
Word and symbol
equations: e.g. (i) chlorine +
potassium bromide
==> potassium chloride + bromine
Cl2(aq) + 2KBr(aq)
==> 2KCl(aq) + Br2(aq)
Higher GCSE level Oxidation-Reduction
Theory
The halogen
molecule is the electron acceptor (the oxidising agent) and is reduced
by electron gain to form a
halide ion
The halide
ion is the electron donor (the reducing agent) and is oxidised
by electron loss to form a halogen molecule
chlorine molecule
+ bromide ion
==> chloride ion + bromine molecule
ionically the
redox equations are written ...
Cl2(aq) +
2Br-(aq)
==> 2Cl-(aq) + Br2(aq)
because the
potassium ion, K+, is a spectator ion, that is, it does not take
part in the reaction. The other two possible reaction equations
involving (ii) chlorine + iodide and (iii) bromine +
iodide, are similar to the example above.

Explaining the Reactivity
Trend of the
Group 7 Halogen
F [2.7] + e-
==> F- [2.8]-
Cl [2.8.7] + e-
==> Cl- [2.8.8]-
Br [2.8.18.7] + e-
==> Br- [2.8.18.8]-
I [2.8.18.18.7] + e-
==> I- [2.8.18.18.8]-
-
When a halogen atom
reacts, it gains an electron to form a singly negative charged ion e.g.
Cl + e- ==> Cl- which has a stable
noble gas electron structure like argon. (2.8.7 ==> 2.8.8)
-
As you go down the group
from one Group 7 halogen element down to the next ..
F => Cl => Br => I ...
-
the atomic radius gets
bigger due to an extra filled
electron shell,
-
the outer electrons are
further and further from the nucleus and are also shielded by the
extra full electron shell of negative electron charge,
-
therefore the outer
electrons are less and less strongly attracted by the positive nucleus
as would be any 'incoming' electrons to form a halide ion (or shared
to form a covalent bond).
-
SO, this combination of
factors means to attract an 8th outer electron is more and more
difficult as you go down the group, so the element is less reactive as you go down the
group, i.e. less 'energetically' able to form the X-
halide ion with increase in atomic
number.

Other
Reactions of the
Halogensnote: fluorine forms fluorides,
chlorine forms chlorides and iodine forms iodides
Reaction with hydrogen H2
-
Halogens
readily combine with hydrogen to form the hydrogen halides which are
colourless gaseous covalent molecules. Complete covalent
bonding details revision notes on another page.
-
e.g. hydrogen + chlorine ==>
hydrogen chloride
-
H2(g) + Cl2(g)
==> 2HCl(g)
-
The hydrogen halides
dissolve in water to form very strong acids with solutions of pH1
e.g. hydrogen chloride forms hydrochloric acid in water HCl(aq)
or H+Cl-(aq) because they are fully ionised
in aqueous solution even though the original hydrogen halides were
covalent! An acid is a substance that forms H+ ions in
water.
-
Bromine forms hydrogen
bromide gas HBr(g), which dissolved in water forms hydrobromic
acid HBr(aq). Iodine
forms hydrogen iodide gas HI(g), which dissolved in water forms
hydriodic acid HI(aq). Note the group formula pattern.
Reaction with Group 1 Alkali Metals Li Na K etc.
-
Alkali
metals burn very exothermically and vigorously when heated in chlorine to form colourless crystalline ionic
salts e.g. NaCl or Na+Cl-. This is a very expensive way to
make salt! Its much cheaper to produce
it by evaporating sea water!
-
e.g. sodium +
chlorine ==> sodium chloride
-
2Na(s) + Cl2(g)
==> 2NaCl(s)
-
The sodium chloride is soluble in water to
give a neutral solution pH 7, universal indicator is green. The salt
is a typical ionic compound i.e. a brittle solid with a high melting
point. Similarly potassium and bromine form potassium bromide KBr,
or lithium and iodine form lithium iodide LiI. Again note the
group formula pattern.
-
Complete ionic
bonding details revision notes on another page.
Reaction with other metals
-
If aluminium or iron is
heated strongly in a stream of chlorine (or plunge the hot metal into a
gas jar of chlorine carefully in a fume cupboard) the solid chloride is
formed.
-
aluminium + chlorine ==>
aluminium chloride(white solid)
-
iron + chlorine ==>
iron(III) chloride(brown solid)
-
If the iron is repeated with
bromine the reaction is less vigorous, with iodine there is little
reaction, these also illustrate the halogen reactivity series.
|
The
Industrial Electrolysis of Sodium Chloride Solution
or brine
made from concentrated 'rock salt' solution
(sodium chloride (brine) electrolysis product
uses further on)
|
|

THE ELECTROLYSIS CELL
Summary
of the ions involved and what happens to them at the two electrodes.
|
|
negative electrode
(cathode) product
|
ions
from water |
ions
from salt |
positive
electrode (anode) product
|
|
hydrogen gas formed
H2(g)
<==
|
hydrogen ion H+(aq)
changes to <==
|
chloride ion Cl-(aq)
changes to ==>
|
==> chlorine gas formed Cl2(g)
|
|
ion
left ==>
|
OH- |
Na+ |
<==
ion left in solution
|
| When
electricity is passed through the sodium chloride solution (brine)
there are three products,
(1) hydrogen is
formed at the negative electrode (-ve cathode),
(2) chlorine
at the positive electrode (+ve
anode) and (3) sodium
hydroxide is left in solution (Na+ plus OH-). |
|
Summary equation:
- sodium chloride + water
==> sodium hydroxide + hydrogen + chlorine
- 2NaCl (aq) + 2H2O
(l) + elec. energy ==> 2NaOH (aq) + H2 (g) + Cl2
(g)
|
The
industrial electrodes must be made of an inert material like
titanium which is not attacked by chlorine or alkali.
- However a
simple cell using carbon electrodes can be used to demonstrate the
industrial process in the laboratory.
- The (-) cathode gas gives
a squeaky pop with a lit splint - hydrogen. The (+) anode
gas turns damp blue litmus red and then bleaches it white - chlorine.
|
The
electrode equation theory and details
-
The (-) cathode
attracts the Na+ and H+ ions.
The hydrogen ions are reduced by
electron (e-) gain to form hydrogen molecules:
-
2H+(aq)
+ 2e- ==> H2(g)
-
The (+) anode
attracts the OH- and Cl- ions. The
chloride ions are oxidised by electron loss to give chlorine
molecules:
-
2Cl-(aq)
==> Cl2(g) + 2e-
-
See Electrochemistry
page for more on electrolysis
|

The
Uses of Chlorine, the brine electrolysis products and other halogens
and their compounds
|
Sodium
Chloride NaCl |
|
|

CHLORINE
Cl2
 
|
- All
the Halogens are potentially harmful substances and chlorine in
particular is highly toxic. It is dangerous to ingest
halogens or breathe in any halogen gas or vapour.
- Chlorine
is used to kill bacteria and so sterilise
water for domestic supply or in in swimming pools.
-
The sodium hydroxide
and chlorine can be chemically combined at room temperature to make the bleach,
sodium chlorate(I) NaClO. This is used in some domestic
cleaning agents, it chemically 'scours' and chemically 'kills'
germs!
- Organic phenolic chlorine compounds are used
antiseptics and disinfectants
like 'dettol' or 'TCP'
- Organic chlorine compounds are used
as pesticides, including the now mainly banned DDT.
- Chlorine is used in making CFC
refrigerant gases/liquids but their production and use are being
reduced. They break down in the upper atmosphere and the chlorine
atoms catalyse the destruction of ozone O3 which absorbs
harmful uv radiation.
- PVC: Chlorine
(from electrolysis
of NaCl) and ethene (from
cracking oil fractions) are used to make a chemical called chloro(ethene),
which used to be called vinyl chloride, this is then converted
into the plastic-polymer poly(chloroethene) or PVC,
because it is shorthand for the old name polyvinylchloride!
(equation below)
-

- Poly(chloroethene), old names PVC, from
chloroethene (vinyl chloride) is much tougher than poly(ethene)
and very hard wearing with good heat stability. so it is used
for covering electrical wiring and plugs. It is also replacing
metals for use as gas and water drain pipes and has found a use
as artificial leather and readily dyed to bright colours! (old
names : polyvinyl chloride, shortened to PVC)
- Liquid organic chlorine
compounds are used as dry cleaning or de-greasing solvents.
- PVC
is very tough
hard wearing useful plastic and a good electrical insulator and is used for water piping, window frames, part of
electrical fittings e.g. plug covers etc.
- Chlorine is used in the
manufacture of potassium chlorate weed killer, KClO3.
|


|
-
HCl(g
=> aq)
As described above, some of the hydrogen and chlorine from the
electrolysis of sodium chloride solution are combined to form hydrogen
chloride gas.
- H2(g) + Cl2(g)
==> 2HCl(g)
-
This gas is dissolved in water to manufacture
hydrochloric acid.
- HCl(g) + aq
==> HCl(aq)
or ==> H+(aq) + Cl-(aq)
-
This is a very important acid used in the
chemical industry to make chloride salts.
|
silver
salts Ag+X-
|
-
Silver
chloride (AgCl), silver bromide (AgBr) and silver iodide (AgI) are
all sensitive to light ('photosensitive'), and all three are used
in the production of various types of photographic film used to
detect visible light and beta and gamma radiation from radioactive
materials.
-
Each silver halide salt has a different sensitivity to
light. When radiation hits the film the silver ions in the salt are
reduced by electron gain to silver (Ag+ + e-
==> Ag, the halide ion is oxidised to the halogen molecule
2X- ==> X2 + 2e- ).
-
AgI is the
most sensitive and used in X-ray radiography, AgCl is the most
sensitive and used in 'fast' film for cameras, AgBr is used in most
standard photographic films.
|
| The
other halogens
FLUORINE
F2
BROMINE Br2
IODINE I2
|
-
Fluorine is used as
fluoride salts in toothpaste or added to domestic water supplies to
strengthen teeth enamel helping to minimise tooth decay. (e.g.
potassium fluoride).
-
Fluorine is
used in the manufacture of the tough non-stick plastic PTFE
coating of cooking pans.
-
Fluorine is
used in manufacture of aerosol propellants and refrigerant
gases.
-
Apart from its silver salt use in photography,
bromine is used to manufacture organic pesticides and fungicides
because of their poisonous nature
-
Organic bromine
compounds are used as flame inhibitor
chemicals (flame retardants) for plastic products to reduce their
flammability and as petrol additives to reduce the
buildup of lead in car engines (a use decreasing as 'green'
unleaded fuels are becoming more popular).
-
Bromine and iodine
are both used in 'halogen' car
headlamps.
-
Iodine is
used in hospitals in the mild antiseptic solution 'tincture
of iodine'.
|
| HYDROGEN
H2 |
-
Hydrogen
is used in the manufacture of ammonia (for fertilisers),
margarine (by adding hydrogen to unsaturated fats) and hydrochloric
acid.
-
It isn't a halogen, but it is made from the electrolysis of
salt solution.
|
| SODIUM
HYDROXIDE NaOH |
- Sodium
hydroxide is used in the manufacture of soaps, detergents,
paper, ceramics and to make soluble salts of organic acids with low
solubility in water (e.g. soluble Aspirin).
- It isn't a halogen
compound, but it is made from the electrolysis of salt solution.
-
The sodium hydroxide
and chlorine can be chemically combined at room temperature to make the bleach,
sodium chlorate(I) NaClO. This is used in some domestic
cleaning agents, it chemically 'scours' and chemically 'kills'
germs!
|
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