Experiment 5

PRECIPITATION TITRATIONS

Purpose:
To determine the amount of chloride ion in an unknown by using two different methods which
are Mohr Method and Volhard Method.

Theory:
Precipitation titrations yield ionic compounds of limited solubility. It is based on reactions and is
one of the oldest analytical methods. There are a few precipitating agent that can be used in
titration due to slow rate of formation of most precipitates and the most widely used precipitating
agent is silver nitrate.

Mohr Method is used in the determination of Chloride ion by titrating with silver nitrate. At the
end of this titration silver chloride forms. The rection is:

Ag+(aq) + Cl-(aq)  AgCl(s) ( white)

Then dilute potassium chromate solution is added. After all chloride ions are reacted, excess
silver nitrate is added and it reacts with chromate ions and red color occurs. The reaction is:

2Ag+(aq) + CrO42-(aq)  Ag2CrO4(s)

In the Volhard Method, before the titration an amount of a silver nitrate solution is added to the
solution containing chloride ions, forming a precipitate of silver chloride. The reaction is :

Ag+(aq) + Cl-(aq)  AgCl(s)

Then, indicator Fe3+ is then added and silver ions are titared with thiocyanate. The reaction is:

Ag+(aq) + SCN -(aq)  AgSCN(s) (white)

The solution turns red by the first slight excess of thiocyanate ion. The reaction is:

Fe3+(aq) + SCN -(aq)  FeSCN2+(aq)

Discussion :
In Mohr method: chromate ion is the conjugate base of the weak chromic acid, therefore, Mohr
titrations should be carried out at a pH between 7 and 10. In high acidic solutions, chromate ion
concentration is too low to produce precipitate near the equivalence point ( Saturating analyte
solution with sodium hydrogen carbonate, can be approached to a suitable pH.). In solutions
which have pH below 7, chromate ion is protonated. Therefore, it is important to determine the
pH of titration medium. The indicator reaction is:

2Ag+(aq) + CrO42-(aq)  Ag2CrO4(s)

After silver chloride formation, dilute potassium chromate solution is added. After all chloride
ions are reacted, excess silver nitrate is required before precipitation begins. This additional
excess of the reagent should be added to produce enough silver chromate to be seen. The result of
these two factors creates a positive systematic error and for correction of this error can be made
by blank titration. This is another reason of using blank beside to dissipate the error brought
about by impurities.

By titrating a solution of a little of chloride free CaCO3 and indicator K2CrO4 with standard silver
nitrate solution blank can be determined. Calcium carbonate is used to imitate the white silver
chloride precipitate. Therefore, volumes are corrected for blank.

The silver ion concentration at chemical equivalence in the titration of chloride with
silver ions is :

[Ag +] = Ksp = 1.82* 10-10 = 1.35 x 10 M

The chromate ion concentration required to initiate formation of silver chromate:

[CrO42-] = Ksp / [Ag + ]2 = (1.2* 10-12) / (1.35*10-5) 2 = 6.6 ×10 M

In principle, in an amount, chromate should be added to give this concentration, in order to

develop the red precipitate after the equivalence point. However, a chromate ion
concentration of 6.6 x 10-3 M imparts such an intense yellow color to the solution that
formation of the red silver chromate is not readily detected. Therefore, lower concentrations of
chromate ions are generally used.

In Volhard method: Titration should be carried out in acidic solution. Because otherwise,
precipitation of iron(III) as the hydrated oxide forms. Indicator reaction:

Fe3+(aq) + SCN -(aq)  FeSCN2+(aq)

.
In Volhard Method, Iron(III) solution prepared in HNO3 is used. In experiment HCl cannot be
use instead of HNO3 because when it is used extra Cl- ions will come that will affect the result
therefore, HCl cannot be use in Volhard method.

A measured excess of silver nitrate solution is added to the sample and excess silver is
determined by back-titration. This is the indirect determination of halide ions.

KSCN is less soluble than AgCl, therefore, to coat the AgCl particles and prevent them from re-
dissolving, nitrobenzene is added.

When the experimental results and the true value are compared, it is seen that there is no big
errors. For the first part of experiment, relative error is 1.823%, an acceptable value. Because the
both data of first crucible and second crucible are equal (so they are equal to the mean), standard
deviation and %RSD became zero. For the second part of the experiment, relative error is 4.012%
and standard deviation is 0.353 means both results of first and second crucible close to the mean
and 2.394% RSD is an acceptable value. Reasons of these errors in both first and the second part
can be because of wrong determination of end point, in other words, after awhile of color
changing appearance, volume noted. Therefore, a positive error was occurred. Another reason
can be because of impurities in volume that is used in calculations.

Conclusion:
In experiment, I determined the amount of chloride ion in an unkown by using two different
methods which are Mohr Method and Volhard Method. After determination it was seen that there
were errors when the experimental results and the true result was compared with each other.
Despite of the errors, results were not much different.

Referances:
A.Skkog, M.West, R.Crouch, Fundamentals of Analytical Chemistry, Chap.13, pp. 353-365,
Thomson Brooks/Cole, 2004.