Group 7 part 2

Halides
Now we are talking about ions e.g. F- etc.

Reactivity

halide ions are reducing agents

The reactivity is the opposite of the halogens. The halide ions are trying to lose electrons.

as you go down the group the halides become more reactive.

The larger the ion i.e. down the group, the easier it is to lose an outer electron and are therefore the
more reactive it is.

I- is the most powerful. You could say At- is the best reducing agent but Ive never seen a question on it.

In the exam questions, they want to test you on whether you know what the halides do i.e. reduce things,
and also the strength of them. They do this by the reaction with concentrated H2SO4.

Reactions
Reaction with H2SO4

F- and Cl-
Well start at the top of the group with the weakest reducing agents F- and Cl- reacting with sulphuric
acid.

you need to use something like NaCl or NaF, you cant just have F- or Cl- floating about on their own:

NaCl + H2SO4 NaHSO4 + HCl

This is always the first step with any of the halides. H2SO4 is acting as an acid (which might seem obvious)
and donating a proton to form HCl. So this is just an acid-base reaction.

there is no oxidation or reduction taking place yet. Always look at the oxidation states on the S and
the halogen involved. Cl is still -1 and S is 6+.

For HCl and HF, this is as far as the reaction goes.

You can look at this two ways. You could say that H2SO4 is not a strong enough oxidising agent to oxidise
Cl- or you could say that Cl- is not a strong enough reducing agent to reduce H2SO4.

Br-
Going down the group to Br-, a redox reaction does take place. As we said above, the reducing power of
the halides increases down the group.

Step 1
The first step again is the same as above:

NaBr + H2SO4 NaHSO4 + HBr

Step 2
But Br- is a strong enough reducing agent to react with further H2SO4 and a redox reaction now takes
place:

2HBr + H2SO4 Br2 + SO2 + 2H2O

Br- has reduced H2SO4 to SO2 (S6+ to S4+) and the Br- has been oxidised to Br2 (Br- to Br0).

Again you can look at it from the reducing agent point of view or you could alternatively say that the
H2SO4 is a strong enough oxidising agent to oxidise Br-.

I-
Iodide (I-) is the last halide we will look at, which is the strongest reducing agent.

The first two reactions follow those for Br- but the SO2 can be reduced further by HI.

Step 1

NaI + H2SO4 NaHSO4 + HI

Step 2

2HI + H2SO4 I2 + SO2 + 2H2O

Step 3

6HI + SO2 H2S +3I2 + 2H2O

Its just the same arguments as before, I- is strong enough to reduce H2SO4 all the way to H2S.

Again, check the oxidation states of S and I. In the 3rd equation, we have gone from S4+ to S2+ and I- to I0.

Test for halide ions

This part is easy. We are assuming that we have a solution containing Cl-, Br- or I- ions.

1. Add some nitric acid to remove any other ions that might interfere with the test.

2. Add some silver nitrate solution. The silver ions react with the halide a silver halide precipitate (X
just stands for any halide ion):

Ag+ + X- AgX(s)

The colour of the precipitate (see below) tells you which halide ion you have.

However, it is not always easy to tell the colours apart. So, a second test is done to confirm which halide
ion is present.

Aqueous or concentrated ammonia is added to the precipitates to see if it dissolves or not:

Chloride: white precipitate that dissolves in dilute NH3

Bromide: cream precipitate that dissolves in concentrated NH3

Iodide: yellow precipitate that does not dissolve in any NH3 solution

From these two tests you should know conclusively which halide you have.