EXPERIMENT 4

SOLUBILITY OF IONIC SALTS IN SEAWATER

Objectives
1. To standardise silver nitrate solution using a known chloride solution.
2. To determine the chloride concentration in seawater.
Introduction
Precipitation Titrations
A titration process that is carried out such that the stoichiometric reaction
between two substances produces a slightly soluble salt that precipitates out in
the solution is called a precipitation titration. A common example of a
precipitation titration is when the chloride ion in a sample is determined by
titrating it with a standard solution of silver nitrate. The equation to show the
precipitation reaction is
Ag+(aq) + Cl-(aq) AgCl(s)
The chloride in the sample reacts with the added silver nitrate which will
then produce a white precipitate of AgCl that settles to the bottom of the flask.
The amount of silver nitrate required to completely react with the chloride can be
calculated frim concentration and volume used to reach the endpoint. According
to the stoichiometric equation, the reaction between the two is one to one;
hence the amount of chloride sample equals that of the silver nitrate added.
Endpoints
In any titration, the completion of a reaction is often physically detected.
This point in the titration is called the endpoint; point which just enough titrant
has been added. The endpoint that signals the completed reaction between the
silver ion and the chloride can be shown by the presence of indicator. In this
experiment, chromate ion, CrO42- is used as the indicator. A solution of chromate
ion is yellow while the precipitate Ag2CrO42- is blood-red. Chromate ion is added
at the beginning of titration. Presence of CrO 42- initially will turn the solution
yellow. Upon addition of standard sliver ion, the silver ion will react with the
chloride in the sample solution. White precipitate of silver chloride will form. This
will continue until there is no more chloride left in the flask. Silver ion still added
after this point will react the chromate ion instead, to produce a precipitate of
Ag2CrO4 which is brick red in colour. This indicated the endpoint for the titration.
What is the minimum concentration of free silver ion that must be present
in the solution before it will react with the chromate ion?
Let us assume that the [CrO42-] in the solution is 0.001 M. then the
solubility product constant, Ksp for silver chromate is
Ksp = 1.12 x 10-12 = [Ag+]2[CrO42-]

Since [CrO42-] = 0.001 M, hence [Ag+]2 = 1.12 x 10-9, and [Ag+] = 3.35 x
10-5.
Thus, only when the concentration of silver ion in the solution exceeds
3.35 x 10-5M, will Ag2CrO4 precipitate form. Below this concentration value, no
silver chromate precipitate will form.
Now let us look at what happens when the concentration of chloride ion in
sample is 0.01 M and we add silver ion on it. The solubility product then is
Ksp = 1.76 x 10-10 = [Ag+][Cl-],
So at the start of the titration,
[Ag+]2 = 1.76 x 10-10 / 1 x 10-2 = 1.76 x 10-8. This is of course very much
less than the minimum concentration of [Ag+] above, that is why no precipitate
of Ag2CrO4 can form at the beginning of the titration.
At the equivalence point, [Ag+] = [Cl-] and
[Ag+]2 = Ksp = 1.76 x 10-1, [Ag+] = 1.33 x 10-5, which is still lower than 3.35
x 10-5.
Thus no precipitate of Ag2CrO4 will form. After this equivalence point when
all chloride is used up, addition of even one drop of silver ion will increase the
concentration of the silver greatly. At this point, the solubility product constant of
silver chromate will be exceeded and you will see the red precipitate due to
Ag2CrO4, signalling the endpoint of the titration is now reached. This method is
known as the Mohr method, a method for determining chloride in a sample
solution using chromate ion as the indicator.
In this experiment, you will carry out the Mohr method to determine the
concentration of the chloride ion in the seawater. Before doing the analysis, you
will first standardise the silver nitrate solution which is to be used in the
determination of chloride ion in the sample.
Procedure
A. Standardisation of the silver nitrate solution
1. About 0.020 g of dry sodium chloride were weighted accurately. Transfer
quantitatively into a 250 mL conical flask. Add approximately 100 mL
distilled water to dissolve the salt.
2. The pH were checked using a pH paper. The pH were adjusted to between
7 and 10 by adding sulphuric acid or sodium hydroxide if necessary.
3. 1.0 mL of 5% potassium chromate indicator were added.
4. A 50 mL burette were cleaned thoroughly with tap water and rinse a few
times with distilled water. Then rinse and fill the burette with the silver
nitrate solution (approximately 0.01 M) you wish to standardise. Titrate the
salt solution earlier with the titrant until a permanent orange pink colour is
obtained.

5. This standardisation process were repeated until you have three values
that agree with each other.
B. Analysis of seawater
1. 10.0 mL portion of seawater were measured accurately. Filter the sample if
it is cloudy. Transfer the sample to 100 mL volumetric flask and dilute to
the mark with distilled water. Use a dropper towards the end to avoid
exceeding the line.
2. 10.0 mL aliquot of the diluted seawater sample were pipetted into a 250
mL conical flask.
3. The pH of the solution is between 7 and 10 were ensured using a pH paper
as above.
4. 1.0 mL of 5% potassium chromate were added and titrate against the
standardised silver nitrate solution.
5. The titration were repeated for another three samples.