Group 7

k) recall the appearance and physical state of the halogens at room temperature

l) recall the appearance of solutions of the group 7 elements in water and in

hydrocarbon solvents

s) make predictions about fluorine, astatine and their compounds based on the
trends in physical and chemical properties of the halogens.

Haloge Physical State Appearance at room Appearance in Appearance in

n at room temperature aqueous hydrocarbon
temperature solution solution
Chlorin Gas Yellowy-Green gas Slightly yellow Yellow/Green*
e
Bromin (Fuming) Dark red liquid fuming Orange Orange*
e Liquid with orange vapour
Iodine Solid Lustrous grey-black Insoluble Violet*
solid (yellow/brown
in potassium
iodide solution,
KI3)
* Same as vapour colour of halogen in gaseous state

Descending Group 7, all (fluorine -> astatine) of the Halogens.....

Become less reactive as neutral element (X2 becomes weaker oxidising

agent)
Become more reactive as negative halide ions (X- becomes stronger
reducing agent )
Have higher melting and boiling points as neutral element (more
electrons, stronger London Forces)
Become more polarisable as negative halide ions (more electrons, greater
ionic radius)
Become more strongly coloured (tending towards black)
Become less soluble in water

m) describe the following reactions giving the names, appearance and formulae
of the reactants and the products, the equations for the reactions and the
conditions needed for the reactions to take place:-

n) redox reactions of halogens with metals, non-metals and ions such as Fe 2+

Reaction with Fe2+(aq) - Halogens become less reactive down group 7 when
neutral elements (X2 becomes weaker oxidising agent)

2 Fe2+(aq)+ Cl2 (aq) 2 Fe3+ (aq) + 2 Cl-(aq)

(Iron (II) ions are oxidised by Chlorine)

2 Fe2+(aq)+ Br2 (aq) 2 Fe3+ (aq) + 2 Br-(aq)

 (Iron (II) ions are oxidised by Bromine)

Iodine is too weak an oxidising agent to oxidise Iron (II) ions, so no reaction is
observed

Reaction with Metals Chlorine and Bromine react as expected with metals
to form simple colourless ionic compounds:-

Mg(s)+ Cl2 (g) MgCl2 (s)

(Very exothermic as large lattice enthalpy)

2 Na(s)+ Br2 (g) 2 NaBr (s)

Transition metals will form salts with the metals in higher oxidation states (eg
Iron(III)Chloride not Iron (II) Chloride due to relatively strong oxidising strength of
these 2 elements.

2 Fe(s)+3 Cl2 (g) 2 FeCl3 (s)

(Iron metal is oxidised by Chlorine to Fe3+; very exothermic)

2 Fe(s)+3 Br2 (g) 2 FeCl3 (s)

(Iron metal is oxidised by Bromine to Fe 3+; less exothermic as is weaker oxidising

agent)

IODINE is so weakly oxidising, it can only oxidise Iron metal to Iron (II) Iodide.

Fe(s)+ I2 (g) FeI2 (s)

If iodine reacts with Lithium or Aluminium, the compounds formed are not simple
ionic substances as high polarising power of Al 3+ or Li+ coupled with high
polarisability of I- produces very polar-covalent bonds. Aluminium and Lithium
Iodide therefore have different properties compared to other metal halides.

Reaction with Non-Metals

Hydrogen Gaseous halogens react with hydrogen gas to form a colourless

hydrogen halide gas.

H2(g)+ Cl2 (g) 2 HCl (g)

{violent explosion}

H2(g)+ Br2 (g) 2 HBr (g)

{pale blue flame, smooth reaction}

H2(g)+ I2 (g) 2 HI(g)

{reversible reaction}
 As descend group 2, halogen reactivity decreases; this explains the
change in observations for these reactions

Phosphorus and Sulphur Halogens react when heated to make molecular

halides of larger non-metal elements (not period 2 elements).

2 P(s)+3 Cl2 (g) 2 PCl3 (l)

Si (s) + 2 Cl2 (g) SiCl4 (l)

Carbon, Nitrogen and Oxygen period 2 non-metal halides (eg NCl3, CBr4) do
exist, but halogens do not react directly with these elements. Free radical
substitution of methane produces CBr4, for example.

o) disproportionation reactions of halogens with cold and hot alkali

Disproportionation is the simultaneous reduction and oxidation of the

same element in a reaction
Reaction of a halogen with cold metal hydroxide produces a mixture of the
metal Halate and metal halide salts in a reversible reaction:

Cl2(aq) + 2 NaOH (aq) NaOCl (aq) + NaCl (aq) + H2O (l)

0 +1 -1
Chlorine, oxidation state 0 is both oxidised and reduced to +1 in NaOCl
(sodium hypochlorite) and -1 in NaCl (sodium chloride)
NaOCl (sodium hypochlorite) is common bleach this reaction smells of
bleach therefore!
Hypochlorite, ClO- is thermally unstable and will disproportionate if heated:

3 NaOCl (aq) 2 NaCl (aq) + NaClO3 (l)

+1 -1 +5

If Chlorine is therefore mixed with a hot alkalis, it will ultimately form a

solution containing a mixture of chloride and chlorate (V) ions
Bromine and Iodine react with cold and hot alkalis in the same way as
Chlorine, except thermal stability decreases as halogen gets bigger, so
disproportionation occurs at lower temperatures

p) reactions of potassium halides with halogens and with silver nitrate solution

r) describe the behaviour of silver halides in sunlight and their solubilities in

aqueous ammonia solution

Potassium halide salts are water soluble white crystalline solids that form
colourless solutions. The potassium ion is unreactive, however the halide ion is
able to undergo limited chemistry:
Reaction with Halogens

Larger halide ions can reduce smaller halogen molecules

2 I- (aq) + Cl2 (aq) 2 Cl- (aq) + I2 (aq)

Redox occurs as chlorine has a greater affinity for electrons than Iodide
ions (less shielding, outer energy level electrons closer to the nucleus,
stronger electrostatic attraction between nucleus and outer electrons
Conversely, smaller halide ions cannot reduce larger halogen
molecules
When a halide displaces a different halogen (ie react together), there is an
observable change in the aqueous solution as one halogen is consumed
and another is produced
Halogens are not very soluble in water, so an organic solvent (hexane or
cyclohexane) is often added to the test tube and shaken; this causes the
halogen to migrate from the water into the hydrocarbon layer, where its
distinctive colour is observed.
Look at this :
http://www.jce.divched.org/JCESoft/CCA/CCA3/MAIN/HALOGEN/PAGE1.HTM
You need to be able to describe the physical changes observed during
such a reaction
Summary table : -

Reaction with Silver Nitrate Solution

 Silver Nitrate solution undergoes a precipitation reaction with halide
ions to form colourless insoluble silver halide salts

Ag+(aq) + Cl- (aq) AgCl (s)

Silver Halide salts have different colours, solubilities in ammonia

solution and photochemical reactions with sunlight; considering these 3
factors allows you to distinguish them apart {This is the test for Halide
ions}:
o AgCl (s) White, darkens in sunlight, soluble in dilute and conc.
Ammonia
o AgBr (s) Cream, turns green-yellow in sunlight, only soluble in
conc. Ammonia
o AgI (s) Yellow, unaffected by sunlight, insoluble in dilute and
conc. Ammonia.
Silver halide test can be used to prove that an organic molecule was a
halogenoalkane:

Step 1 Destroy the halogenoalkane by hydrolysing the carbon-halogen bond

with hydroxide ions

C4H9Br (l) + KOH(aq) C4H9OH (l) + KBr(aq)

Step 2 Perform Silver Nitrate test on a sample of reaction mixture to detect

presence of halide ion:

AgNO3(aq) + KBr (aq) KNO3(aq) + KBr(s)

A positive result proves that, originally, the organic molecule contained a

halogenoalkane functional group (NOT A HALIDE ION!)

q) reactions of hydrogen halides with ammonia and with water to produce acid

Hydrogen Halides

Hydrogen Halides (HX)are colourless gases at room temperature which

fume in moist air
Very soluble in water, ionising fully when they dissolve into H + and X- ions

HCl (g) + H2O (l) H3O+(aq) + Cl-(aq)

Aqueous Hydrogen Halide solutions are very strongly acidic as a result

(low pH)
Hydrogen Halide gases react with ammonia gas produces a white smoke
(not fumes!) of an ammonium halide salt:

HCl (g) + NH3 (g) NH4 Cl(s)

Sulphuric Acid
 Sulphuric Acid is a compound containing sulphur in a very high oxidation
state (+6)
Halide ions have different reducing strengths and may reduce
concentrated sulphuric acid to lower oxidation states, depending on the
halide involved
Any reaction that could possibly cause halide ions and concentrated
sulphuric acid to come into contact must be thought about carefully, as
TOXIC by-products could be formed!

Chloride ions and Sulphuric acid

Cl- ions are the weakest-reducing halide ions you will encounter, they
cannot reduce sulphuric acid
Instead, a simple reversible displacement reaction occurs:

NaCl (s) + H2SO4(aq) NaHSO 4 (aq) + HCl (g)

This reaction is often used in organic chemistry to safely make HCl gas in-
situ safely for making chloroalkanes from alkenes

Bromide ions and Sulphuric acid

Bromide ions are stronger reducing agents than chloride ions and will
reduce sulphuric acid that is more than 50% concentrated

Initial (Displacement) reaction : NaBr(s) + H 2SO4(aq) NaHSO4 (aq)

+ HBr (g)

Secondary (Redox) reaction : H 2SO4 (aq) + 2 HBr (g) Br2 (g) + 2

H2O (l) + SO2 (g)

Exothermic reaction, steaming fumes (HBr gas reacting with air moisture)
and orange Br2 vapours are observed
If HBr(g) is prepared in this way in-situ to make a bromoalkane, the
sulphuric acid must be at least 50% dilute, else toxic Br2 and SO2 gases
will be produced!

Iodide ions and Sulphuric acid

Iodide ions are strong reducing agents than chloride ions and will reduce
sulphuric acid to very low oxidation states:

Initial (Displacement) reaction : NaI(s) + H 2SO4(aq)

NaHSO4 (aq) + HI (g)

Secondary (Redox) reaction : H 2SO4 (aq) + 2 HI (g) I2

(g) + 2 H2O (l) + SO2 (g)
 Tertiary (Redox) Reaction: SO 2 (g) + 4 HI (g)
S (s) + 2 I2 (g) + 2 H2O (l)

Quaternary (Redox) Reaction: S (s) + 2 HI (g)

I2 (g) + H2S (g)

Very exothermic reaction, steaming fumes (HI gas reacting with air
moisture), purple vapour (Iodine gas) sometimes observed, usually grey
solid Iodine seen instead, yellow precipitate (sulphur) and rotten egg smell
(H2S gas) are observed
Iodide is so strongly reducing, it cannot be used to produce just HI(g) /
some reduction of the acid always occurs, and so is never used to make
iodoalkanes

s) carry out an iodine/thiosulfate titration, including calculationof the results and

evaluation of the procedures involved, egdetermination of the purity of potassium
iodate(V) by liberation of iodine and titration with standard sodium thiosulfate
solution

Measuring the purity of a sample of potassium iodate( V)

Example of a procedure you should understand and be able to suggest:

Procedure

A Weigh accurately a specimen of potassium iodate( V) in a sample tube

(about 0.10g).

B Dissolve the sample in distilled water. Transfer all the solution to a 100cm3
graduated volumetric flask and dilute with distilled water up to the mark on
the flask, mixing well.

C Use a pipette to measure 10.0cm3 of a potassium iodate(V) solution into a

titration flask. Add about 10cm3 of 0.1moldm3 potassium iodide solution
and 10cm3 of 1moldm3 sulfuric acid.

D Titrate the iodine produced with 0.010moldm3 sodium thiosulfate solution

from a burette. Add starch indicator near the end-point when the solution is
pale yellow. Repeat the titration until you have at least two accurate results
within 0.1cm3 of each other.

E Record your results in a table.

Example of analysis of titration results you should be able to follow and

complete:

1 Write down the equations for the two reactions involved: the reaction of
iodate(V) ions with iodide ions in acid, and the reaction of thiosulfate ions with
 iodine. Hence work out the amount in moles of thiosulfate ions needed to react
with the iodine produced by 1mol of iodate(V) ions.

2 The volume of sodium thiosulfate solution used in an average titration and its
concentration are known from the results. Use this to work out the amount in
moles of thiosulfate ions added in an average titration.

3 From your answers to questions 1 and 2 work out the amount in moles of
iodate(V) ions in a 10cm3 sample of the solution measured out with the
pipette. This is the amount of iodate( V) ions in one-tenth of the sample you
weighed out. What was the amount in moles of iodate( V) ions in the whole
sample?

4 Find the molar mass of potassium iodate(V) and hence calculate the mass of
pure salt in the sample that was weighed out.

5 Calculate the percentage purity of the original sample of potassium iodate( V).