PRECIPITATION TITRATIONS

ALIYA NUR HASANAH/IDA MUSFIROH

ANALYTICAL CHEMISTRY LABORATORY
2015
 DEFINITIONS

TITRATION BASED ON A REACTION IN

WHICH THE ANALYTE AND TITRANT
FORM AN INSOLUBLE PRECIPITATE
 HISTORY
Developed at the end of the eighteen century, was for the
analysis of K2CO3 and K2SO4 in potash.
Calcium nitrate was used as a titrant, forming a precipitate of
CaCO3 and CaSO4. the end point was signaled by nothing
when the addition of titrant eased to generate additional
precipitate.
Now, titration use to determine halide groups (especially)
and others.
FIELDS OF APPLICATION

Environment : determination of chloride in water

Food and beverage :
- Determination of chloride in many finished products (cooked meats,
preserves)
- Determination of chloride in dairy product
Pharmaceuticals : Titrations of halides
ARGENTOMETRY
DETERMINATION OF END POINT

 Formation of colour precipitate (Mohr Method)

 Formation of a soluble colour compound (Volhard
Method)
 Use of adsorption indicator (Fajans Method)
MOHR METHOD

 Silver nitrate use as a titrant

 For determination of chloride and bromide

 Potassium chromate solution use as indicator

 End point : chromate ion combine with silver ion to form the sparingly
soluble, red, silver chromate

 Titration of iodide and thiocyanate is not succesfull because silver iodide

and silver thiocyanate adsorb chromate ions so strongly that a false and
somewhat indistinct end point is obtained
Awal titrasi Akhir titrasi
VOLHARD METHOD
• Titration of silver in the presence of free nitric acid with standard potassium
thiocyanate or ammonium thiocyanate solution
• The indicator is a solution of iron (III) nitrate or of iron (III) ammonium
sulphate
• the addition of thiocyanate solution produces first a precipitate of silver
thiocyanate

• When this reaction is complete, the slightest excess of thiocyanate produces

a reddish brown coloration, due to the formation of a complex ion :
• can be used to determined chloride, bromide, iodide in acid solution
• excess of standard silver nitrate solution is added, and the excess is
back titrated with standard thiocyanate solution
• For the chloride estimation, we have the following two equilibria
during the titration of excess of silver ions :

• the excess of thiocyanate reacts with Fe(III) solution to form soluble

compound Fe-thiocyanate
• must be added masking agent for determination of chloride ions
Why added masking agent ?

When the excess of silver has reacted, the thiocyanate may react with
the silver chloride, since silver thiocyanate is the less soluble salt. The
reaction are :

This will take place before reaction occurs with the iron (III) ions in the
solution, and there will be consequently be a considerable titration error.
It is therefore absolutely necessary to prevent the reation between the
thiocyante and the silver chloride
HOW TO PREVENT THE REACTION ?

1. The silver chloride is filtered off before back. titrating the suspension
should be boiled for a few minutes to coagulate the silver chloride and
thus remove most of the adsorbed silver ions from its surface before
filtration. The cold filtrate is titrated
2. After the addition of silver nitrate, potassium nitrate is added as
coagulant, the suspension is boiled for about 3 minutes, cooled and
then titrated immediately
3. An immiscible liquid is added to “coat” the silver chloride particles and
thereby protect them from interaction with the thiocyanate. The most
succesfull liquid is nitrobenzene (1 mL for each 50 mg of chloride); the
suspension is well shaken to coagulate the precipitate before back
titration
 FAJANS METHOD
• Adsorption indicator :
At the equivalence point the indicator is adsorbed by the precipitate, and during the
process of adsorption a change occurs in the indicator which leads to a substance
of different colour.
• the substances are acid dyes, such as those of the fluorescein series (fluorescein
and eosin as the sodium salts), or basic dyes (rhodamine series as the halogen
salts)
EXAMPLE

The % w/w I- in a 0,6712 g sample was determined by a Volhard

titration. After adding 50 mL of 0,05619 M AgNO3 and allowing the
precipitate to form, the remaining silver was back titrated with
0,05322 M KSCN, requiring 35,14 mL to reach the end point. Report
the % w/w I- in the sample
SOLUTION

Conservation of charge for this back titration requires that :

Moles Ag+ = Moles I- + moles SCN-
Making appropriate substitutions for moles of Ag+, I-, and SCN- leaves us
with :
MAg VAg = g I- /MW I- + MSCN VSCN
Solving for the grams of I-, we find :
Mass of I- = (MW I-) (MAgVAg-MSCN VSCN)
= (126,9) [(0,05619)(0,05L)-(0,05322)(0,03514)
= 0,1192 g
That there is 0,1192 g of iodide. The weight percent iodide, therefore is
0,1192/0,6712 x 100% = 17,76%
 Example
Sketch a titration curve for the titration Of 40 mL 0,05 M
Cl- With 0,1 M Ag+. 5 mL Ag+, 20 mL Ag+, 35mL Ag+.
Plot pAg versus volume Ag+. Ksp = 1,8 x 10 -10