TESTING FOR HALIDE IONS

This page describes and explains the tests for halide ions
(fluoride, chloride, bromide and iodide) using silver nitrate
solution followed by ammonia solution.

Using silver nitrate solution

Carrying out the test

This test has to be done in solution. If you start from a solid, it

must first be dissolved in pure water.

The solution is acidified by adding dilute nitric acid. (Remember:

silver nitrate + dilute nitric acid.) The nitric acid reacts with, and
removes, other ions that might also give a confusing precipitate
with silver nitrate.

Silver nitrate solution is then added to give:

ion present observation

F- no precipitate

Cl- white precipitate

Br- very pale cream precipitate

I- very pale yellow precipitate

The chloride, bromide and iodide precipitates are shown in the

photograph:

The chloride precipitate is obviously white, but the other two

aren't really very different from each other. You couldn't be sure
which you had unless you compared them side-by-side.

All of the precipitates change colour if they are exposed to light -

taking on grey or purplish tints.

The absence of a precipitate with fluoride ions doesn't prove

anything unless you already know that you must have a halogen
present and are simply trying to find out which one. All the
absence of a precipitate shows is that you haven't got chloride,
bromide or iodide ions present.

The chemistry of the test

The precipitates are the insoluble silver halides - silver chloride,

silver bromide or silver iodide.

Silver fluoride is soluble, and so you don't get a precipitate.

Confirming the precipitate using ammonia solution

Carrying out the confirmation

Ammonia solution is added to the precipitates.

original
observation
precipitate

precipitate dissolves to give a colourless

AgCl
solution

precipitate is almost unchanged using dilute

ammonia solution, but dissolves in
AgBr
concentrated ammonia solution to give a
colourless solution

precipitate is insoluble in ammonia solution of

AgI
any concentration

Explaining what happens

Background

There is no such thing as an absolutely insoluble ionic

compound. A precipitate will only form if the concentrations of
the ions in solution in water exceed a certain value - different for
every different compound.
This value can be quoted as a solubility product. For the silver
halides, the solubility product is given by the expression:

Ksp = [Ag+(aq)][X-(aq)]

The square brackets have their normal meaning, showing

concentrations in mol dm-3.

If the actual concentrations of the ions in solution produce a

value less than the solubility product, you don't get a precipitate.
If the product of the concentrations would exceed this value, you
do get a precipitate.

Essentially, the product of the ionic concentrations can never be

greater than the solubility product value. Enough of the solid is
precipitated so that the ionic product is lowered to the value of
the solubility product.

Note:  If your syllabus says that you need to know about
solubility product calculations, you might be interested in my
chemistry calculations book where they are explained in
detail.

Look at the way the solubility products vary from silver chloride
to silver iodide. (You can't quote a solubility product value for
silver fluoride because it is too soluble. Solubility products only
work with compounds which are very, very sparingly soluble.)

Ksp
 
(mol2dm-6)

AgCl 1.8 x 10-10

AgBr 7.7 x 10-13

AgI 8.3 x 10-17

Note:  These figures come from the Chemistry Data Book by

Stark and Wallace.

You can see that the compounds are all pretty insoluble, but
become even less soluble as you go from the chloride to the
bromide to the iodide.

What is the ammonia doing?

The ammonia combines with silver ions to produce a complex
ion called the diamminesilver(I) ion, [Ag(NH3)2]+. This is a
reversible reaction, but the complex is very stable, and the
position of equilibrium lies well to the right.

A solution in contact with one of the silver halide precipitates

will contain a very small concentration of dissolved silver ions.
The effect of adding the ammonia is to lower this concentration
still further.

What happens if you multiply this new silver ion concentration

by the halide ion concentration? If the answer is less than the
solubility product, the precipitate will dissolve.

That happens with the silver chloride, and with the silver
bromide if concentrated ammonia is used. The more
concentrated ammonia tips the equilibrium even further to the
right, lowering the silver ion concentration even more.

The silver iodide is so insoluble that the ammonia won't lower

the silver ion concentration enough for the precipitate to
dissolve.

An alternative test using concentrated sulphuric acid

If you add concentrated sulphuric acid to a solid sample of one

of the halides you get these results:

ion
observation
present

F- steamy acidic fumes (of HF)

Cl- steamy acidic fumes (of HCl)

steamy acidic fumes (of HBr) contaminated with

Br-
brown bromine vapour

Some steamy fumes (of HI), but lots of purple

I- iodine vapour (plus various red colours in the
tube)
 Note:  The chemistry of this test is explained in detail on
another page.

The only possible confusion is between a fluoride and a chloride

- they would behave identically. You could distinguish between
them by dissolving the original solid in water and then testing
with silver nitrate solution. The chloride gives a white precipitate;
the fluoride doesn't give a precipitate.

Questions to test your understanding

If this is the first set of questions you have done, please read the
introductory page before you start. You will need to use the BACK BUTTON
on your browser to come back here afterwards.

questions on testing for halide ions

answers

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© Jim Clark 2002 (modified June 2015)