Group VII Second Year Advanced Dr Colette Pace

6HI(g) + H2SO4(l) 3I2(s) + 4H2O(l) + S(g)

8HI(g) + H2SO4(l) 4I2(s) + 4H2O(l) + H2S(g)

These reactions show the strength of the hydrogen halides as reducing agents. HI is the
strongest reducing agent – reason: outer shell electrons are further away from the nucleus,
easier to lose. HI>HBr>HCl

In fact, the bond strength order is H-I<H-Br<H-Cl, meaning that the H-I bond is the most easily
broken forming the free halogen, then forming I2.

11.12 Boiling point of HX molecules

All HX molecules are polar with a delta + in the H and a delta – on the X, since the halogens
are more electronegative than the hydrogen. The boiling point of HF is much higher than
expected. This is also observed in H2O and NH3 compared to other group 6 and group 5
hydrides. The reason for the high boiling point of HF is due to the strong intermolecular forces
between the HF molecules. Fluorine is the most electronegative element in the periodic table,
therefore the delta + and delta – generated are very strong. The intermolecular forces in HF are
H-bonds, while in the other hydrogen halides PDDs are present. H-bonds are much stronger,
making them more difficult to break and therefore higher boiling point than expected.

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Group VII Second Year Advanced Dr Colette Pace

11.13 Acidity of HX
All the HX molecules are strong acids, except for HF. HF is a weak acid.

Reason: The stronger the covalent bond between the halogen and hydrogen, the more difficult
it is to break. F is the smallest of the halogens resulting in more attraction to the shared pair of
electrons, therefore a stronger covalent bond.

The larger the halogen, the larger the distance between the nucleus and the shared pair of
electrons and the weaker the bond. This means that the H is more easily lost as an H+ ion, with
the halogen taking both electrons, forming an X- ion.

Ka values for HX

Acid pKa value

HF 3.14
HCl -8
HBr -9
HI -10

The smaller the Ka value, the stronger the acid.

11.14 Reactions of Halogens with H2O and NaOH

Reaction with water

Cl2 + H2O  HCl + HOCl

Br2 + H2O ↔ HBr + HOBr

I2 + H2O ↔ HI + HOI

Iodine is the least reactive, with most of the iodine added to the water remaining undissolved.
Chlorine reacts with water very well in the presence of UV radiation.

Reaction with NaOH at RT

Cl2 + 2NaOH  NaCl + NaOCl + H2O

3Br2 + 6NaOH  5NaBr + NaBrO3 + 3H2O

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Group VII Second Year Advanced Dr Colette Pace

3I2 + 6NaOH  5NaI + NaIO3 + 3H2O

Reaction with NaOH at 70oC

3Cl2 + 6NaOH  5NaCl + NaClO3 + H2O

3Br2 + 6NaOH  5NaBr + NaBrO3 + 3H2O

3I2 + 6NaOH  5NaI + NaIO3 + 3H2O

In base HF forms F- and HF2-. Draw the shape for HF2-

Since hydrogen cannot form more than one covalent bond, it forms a covalent bond with the F
atom and the fluoride ion forms a hydrogen bond with the H, forming HF2-. This hydrogen
bond is the strongest hydrogen bond which exists.

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Group VII Second Year Advanced Dr Colette Pace

11.15 Oxidation states

All of the halogens exist in the -1 oxidation state, however chlorine, bromine and iodine also
show +1, +3, +5 and +7 states. The higher oxidation states are found when these halogens are
combined to small and highly electronegative atoms of fluorine and oxygen. The oxides and
oxoacids of chlorine and bromine have +4 and +5 oxidation states. Some of the halogens can
carry more than 8 electrons in their outer shell, however F has no valence d orbitals, therefore
it cannot expand its octet. Fluorine is also the most electronegative element in the periodic
table, therefore it exhibits only the -1 oxidation state.

Oxidation State Examples

-1 CaF2, HCl, NaBr, AgI
0 F2, Cl2, Br2 and I2
+1 HClO, ClF
+3 HClO2, ClF3
+5 HClO3, BrF5, BrF6-, IF5
+7 HClO4, BrF6+, IF7

Interhalogen compounds – These are made up of different halogens, such as BrCl, ClF3 and
IF7 formed by the reactions with different halogens.

Neutral oxides – such as Cl2O, Cl2O3, ClO2, Cl2O4, Cl2O6 and Cl2O7. These are very unstable
and are formed from the dehydration of perchloric acid. These oxides may explode is subject
to thermal (above -40oC) and physical shock.

Oxyacids of the halogens

Chlorine reacts with hydroxide ions to form chloride ions and hypochlorite (OCl-) ions.

Cl2(aq) + 2 OH-(aq)  Cl-(aq) + OCl-(aq) + H2O(l)

This is a disproportionation reaction, where chlorine (O.N. of 0) is oxidised to ClO- (O.N. of
+1) and reduced to Cl- (O.N. of -1).

When the reaction is carried out in a hot solution, the products which form are chloride and
chlorate (V) ions.

3 Cl2(aq) + 6 OH-(aq)  5 Cl-(aq) + ClO3-(aq) + 3 H2O(l)

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Group VII Second Year Advanced Dr Colette Pace

Under controlled conditions, hypochlorite ions and chlorate(V) ions react together to form
chlorite (ClO2-).

The names of the oxyacid of the halogens end with ite or ate, to indicate whether halogens have
low or high oxidation states. The prefix hypo or per are used to indicate the very lowest and
very highest oxidation states.

Oxyanion Name Oxyacid Name

ClO- Hypochlorite HClO Hypochlorous acid
ClO2- Chlorite HOClO Chlorous acid
ClO3- Chlorate HOClO2 Chloric acid
ClO4- Perchlorate HOClO3 Perchloric acid
Draw the Shapes for ClO2-, ClO3- and ClO4-.

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Group VII Second Year Advanced Dr Colette Pace

11.16 Effect of heat on KClO3

On heating KClO3 decomposes to KCl and O2. This is a very explosive reaction used for the
fast release of oxygen for explosives and fireworks.

2KClO3  2KCl + 3O2

Oxidation of iodide by chlorate(V);

ClO3- + 6I- + 6H+  3I2 + Cl- + 3H2O

This means that chlorine in chlorate is reduced and iodide are oxidised to iodine

11.17 Reaction of iodine with thiosulfate ion

Iodine is a weak oxidising agent, but it is often used to oxidise the thiosulfate ion S2O32-, to
the tetrathionate, S4O62-:

I2(aq) + 2S2O32-(aq)  2I-(aq) + S4O62-(aq)

Each mole of iodine reacts with 2 moles of thiosulfate.

The colourless thiosulfate solution is placed in the burette. The iodine solution is initially
brown in colour, and as thiosulfate is added it fades to pale yellow. Finally at the end-point
the solution turns colourless. The end-point is rather indistinct and it is usual to add a few
drops of starch solution. The starch forms an intense blue colour with iodine. The end-point is
a sharp change from blue to colourless, when all the iodine is used up.

Group 7 Questions

1. Give the lab preparations for:

Cl2, Br2 and I2

2. What is observed when starch is added to iodine?

3. What are the colours of Br2 and I2 in organic solvent?

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Group VII Second Year Advanced Dr Colette Pace

4. Why do Cl2 and Br2 bleach?

5. Explain why on going from F2 to I2 they change from gas to liquid to solid.
6. What happens to the ionisation energy of the halogens down the group?
7. How does the electron affinity change down the group?
8. All halogens are oxidising agents, however explain which is the strongest oxidising
agent.
9. Write equations for the reaction of the halide ions with silver ions, followed by
ammonia solution.
10. What is expected when Cl-, Br- and I- ions are reacted with concentrated sulfuric acid?
Write all the reactions.
11. When the halide ions are mixed with silver ions, a precipitate forms. Some of the
precipitates dissolve in ammonia or thiosulfate, while others do not. Explain.
12. Sketch a graph showing the boiling points of HX where X is F, Cl, Br and I. Explain
any anomaly.
13. When base is added to the HX acids, HCl forms Cl-, HBr forms Br-, HI forms I- however
HF forms F- and HF2-.
14. Give the equations for the reactions of Cl2, Br2 and I2 with:
a) Water
b) NaOH at rt
c) NaOH at 70oC
15. What is the effect of heat on KClO3?
16. A sample of copper alloy weighing 2.582 g was dissolved in dilute HNO3 to produce a
blue solution. On addition of xs NaOH a blue ppt was formed. The precipitate was
filtered and washed with water. The blue ppt was dissolved in dil H2SO4 and the
solution was made up to 250cm3 with water. 25 cm3 of this solution was treated with
xs KI solution and liberated I2. The I2 required 24.4 cm3 of Na2S2O3 of 0.1 M conc.
Using the above information calculate the mass of Cu present and therefore the % Cu
in the alloy.

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