THE REDOX REACTIONS BETWEEN HALIDE IONS AND CONCENTRATED SULPHURIC ACID

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The Facts There are two different types of reaction which might go on when concentrated sulphuric acid is added to a solid ionic halide like sodium fluoride, chloride, bromide or iodide. The concentrated sulphuric acid can act both as an acid and as an oxidising agent.

Concentrated sulphuric acid acting as an acid

The concentrated sulphuric acid gives a hydrogen ion to the halide ion to produce a hydrogen halide. Because this is a gas, it immediately escapes from the system. If the hydrogen halide is exposed to moist air, you see it as steamy fumes. As an example, concentrated sulphuric acid reacts with solid sodium chloride in the cold to produce hydrogen chloride and sodium hydrogensulphate.

NaCl + HSO

HCl + NaHSO

All of the halide ions (fluoride, chloride, bromide and iodide) behave similarly.

The reaction Between Sodium Chloride and Anhydrous Phosphoric Acid ( HPO)

The same reaction occurs with Anhydrous Phosphoric Acid:

NaCl + HPO

NaHPO + HCl

Hang On A salt is reacting with an Acid Why???? Please consider the following discussion Next 3 Slides

feel a bit embarrassed asking this question - but I can't work it out.
If I add concentrated sulphuric acid to sodium chloride the text book says NaCl(s) + H2SO4(aq) ----> NaHSO4(s) + HCl(g)

Now no species changes its oxidation state - so I can't use redox / electrode potential to explain why the reaction occurs.
It is not adding acid to a base - as NaCl is a neutral salt - so I can't apply acid-base neutralisation. So how can I explain the reaction? However, I can explain the "second stage" of the sodium bromide and sulphuric acid reaction by redox potentials KBr(s) + H2SO4(aq) ----> KHSO4(s) + HBr(g) displacement << same problem as NaCl to explain 2HBr(g) + H2SO4(aq) ----> Br2(aq) + 2H2O + SO2(g) oxidation of HBr since Br has ox state -1 in HBr and this is oxidized to 0 in Br2 and oxidation state of sulphur changes from +6 to +4 - so I just find the appropriate half-cell / redox equation for that bit. Still can't explain the initial reaction though.

HCl, while very strong acid, is not 100% dissociated, especialy in concentrated solutions of sulfuric acid, where there is abundance of H+ and almost no water. When you have HCl and no water, HCl gets airborne and flies away - and the reaction can proceed. Ahhh ... are you saying all the ions from NaCl and H2SO4are swishing around .. and one potential product is HCl ... Then because of the presence of vast amounts of H+ I need to argue in equilibrium terms ... and (say it quietly) use Le Chatelier to explain why the reaction proceeds from left to right because the HCl is generated as a gas and being constantly lost/driven out rather than staying in solution?

Ta, Clive

Quote from: cliverlong on May 17, 2008, 08:27:20 AM Ahhh ... are you saying all the ions from NaCl and H2SO4are swishing around .. and one potential product is HCl ... Then because of the presence of vast amounts of H+ I need to argue in equilibrium terms ... and (say it quietly) use Le Chatelier to explain why the reaction proceeds from left to right because the HCl is generated as a gas and being constantly lost/driven out rather than staying in solution?
Looks OK to me. And you don't have to wisper Le Chatelier principle - it is very useful in such situations to help predict possible outcome or to help explain what is going on on qualitative level

The hydrogen halides can be formed by direct reaction of the elements. However, the most important means of preparing hydrogen halides is through reaction of a salt of the halide with a strong nonvolatile acid. Hydrogen fluoride and hydrogen chloride are prepared in this manner by reaction of an inexpensive, readily available salt with concentrated sulfuric acid.

Because the hydrogen halide is the only volatile component in the mixture, it can be easily distilled. It is usually absorbed in water to form the corresponding acid.

CaF(s) + HSO(l)

2HF(g) + CaSO(s)

Concentrated sulphuric acid acting as an oxidising agent With fluoride or chloride ions Concentrated sulphuric acid isn't a strong enough oxidising agent to oxidise fluoride or chloride ions. In those cases, all you get produced are the steamy fumes of the hydrogen halide - hydrogen fluoride or hydrogen chloride.

You can look at this another way - from the point of view of the halide ions. The fluoride and chloride ions aren't strong enough reducing agents to reduce the sulphuric acid. Whichever way you look at it, all you get is the hydrogen halide!
That isn't true, though, with bromides and iodides.

With bromide ions The bromide ions are strong enough reducing agents to reduce the concentrated sulphuric acid. In the process the bromide ions are oxidised to bromine. Half Equation:

2Br

Br + 2e

The bromide ions reduce the sulphuric acid to sulphur dioxide gas. This is a decrease of oxidation state of the sulphur from +6 in the sulphuric acid to +4 in the sulphur dioxide. Half Equation: HSO +2H + 2e Combining the Two Half equations you get: HSO + 2Br + 2H Br + SO + 4HO SO + 2HO

With bromide ions

What you see in this reaction are the steamy fumes of hydrogen bromide contaminated with the brown colour of bromine vapour. The sulphur dioxide is a colourless gas, so you couldn't observe its presence directly.

HSO + 2Br + 2H

Br + SO + 4HO

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With iodide ions Iodide ions are stronger reducing agents than bromide ions are. They are oxidised to iodine by the concentrated sulphuric acid.

Half Equation: 2I I + 2e

The reduction of the sulphuric acid is more complicated than before. The iodide ions are powerful enough reducing agents to reduce it first to sulphur dioxide (sulphur oxidation state = +4) then to sulphur itself (oxidation state = 0) and all the way to hydrogen sulphide (sulphur oxidation state = -2). The most important of this mixture of reduction products is probably the hydrogen sulphide. The half-equation for its formation is:

Half Equation: HSO + 8H + 8e HS + 4HO

With iodide ions Combining these last two half-equations gives:

HSO + 8H + 8I

4I + HS + 4HO

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