PRECIPITATION

TITRATION

Dr. B. R. Thorat
Govt. of Maharashtra

Ismail Yusuf Arts, Science and

Commerce College, Mumbai
Sunday, December 4, 2016

B.R.THORAT

Introduction

A special type of titrimetric procedures involves the formation of precipitates during the
course of a titration. The titrant react with the analyte forming an insoluble material and
the titration continues till the very last amount of analyte is consumed. The first drop of
titrant in excess will react with an indicator resulting in a color change and announcing the
termination of the titration.

Argentometric titrations
In precipitation titrations, the widely used and important precipitating reagent, silver
nitrate, (Barium chloride, hydrogen sulphide, etc) which is used for the determination of
the halogens, the halogen like anions, mercaptans, fatty acids, and several divalent
inorganic anions. Titrations with silver nitrate are sometimes called argentometric
titrations.

Precipitation titration curve

Titration curves for precipitation reactions are
calculated in a completely similar way for
titrations involving strong acids and strong bases.
The only difference is that the solubility product
of the precipitate is substituted for the ion-product
constant for water.
Most indicators for argentometric titrations
respond to changes in the concentrations of silver
ions. Because of this response, titration curves for
precipitation reactions usually consist of a plot of
pAg versus volume of the silver reagent
(usually AgNO3).
The titration curve divided into pre-equivalencepoint region (before equivalence point), the postequivalence point region (after equivalence point),
the equivalence point for a typical precipitation
titration.

Example
The silver ion concentration in terms of pAg during the titration of 50.00 ml of 0.05000 M
NaCl with 0.1000 M AgNO3 after the addition of the following volumes of reagent is
calculated:
(a) in the pre-equivalence point region at 10.00 ml,
(b) at the equivalence point (25.00 ml),
(c) after the equivalence point at 26.00 ml. For AgCl, Ksp = 1.82 x 10-10.
(a) Pre-equivalence-Point: At 10.00 ml, [Ag+] is very small and cannot be computed from
stoichiometric considerations, but the molar concentration of chloride, cNaCl can be obtained
readily. The equilibrium concentration of chloride is essentially equal to cNaCl.

AgCl(s)

Ag+(aq) +

Cl-(aq)

Ksp = [Ag+][Cl-]

(b) Equivalence Point Data

(c) Postequivalence-Point

With 0.1000 M AgNO3 (Curve A), the

change in pAg in the equivalence-point
region is large, about 2 pAg units. With the
0.01000 M reagent (Curve B), the change is
about 1 pAg unit, but still pronounced.
An indicator that produces a signal in the 4.0
to 6.0 pAg region should give a minimal
error for the stronger solution.

For the more dilute chloride solution (Curve B), the change in pAg in the equivalencepoint region would be drawn out over a fairly large volume of reagent (~ 3 ml as shown by
the dashed lines in the figure) so that to determine the end point accurately would be
impossible.

Titrations with silver nitrate

Chemical, potentiometric, and amperometric end points are used in titrations with
silver nitrate.
In potentiometric titrations, the potential difference between a silver electrode and
a reference electrode is measured as a function of titrant volume. The titration curve
is emf against volume of silver nitrate added.
In amperometric titrations, the current generated between a pair of silver
electrodes is measured and plotted as a function of titrant volume.
Chemical indicators produce a color change or occasionally the appearance or
disappearance of turbidity in the solution being titrated.
The requirements for an indicator for a precipitation titration are that
(1) the color change should occur over a limited range in p-function of the titrant
or the analyte;
(2) the color change should take place within the steep portion of the titration
curve for the analyte. E.g. For the titration of NaCl against silver nitrate, iodide
is used as indicator. It shows color change at pAg range of about 4.0 to 6.0.

Types Argentometric titrations

For argentometric titrations, three classical methods based on color indicators can
be used for end point detection:
Mohr titration formation of colored precipitate at the end point.
Volhard titration formation of a soluble, colored complex at the end point.
Fajans titration adsorption of a colored indicator on the precipitate at the end
point.

Volhards method
In this method, silver ions are titrated with a standard solution of thiocyanate ion:
Iron(III) serves as the indicator. The solution turns red with the first slight excess of
thiocyanate ion due to the formation of

Fe3+ + SCN- = Fe(SCN)2+

The important application of the Volhard method is the indirect determination of halide ions.
A measured excess of standard silver nitrate solution is added to the sample, and the
excess silver is determined by back-titration with a standard thiocyanate solution.
The strongly acidic environment of the Volhard titration is a distinct advantage over other
titrations of halide ions because such ions as carbonate, oxalate, and arsenate do not interfere.

Silver chloride is more soluble than silver thiocyanate. As a result, in chloride

determinations using the Volhard method, the reaction occurs to a significant extent near the
end of the back-titration.

This reaction causes the end point to fade and results in overconsumption of thiocyanate
ion. The resulting low results for chloride can be overcome by filtering the silver chloride
(wash the residue with distilled water and combine the filtrate) before undertaking the backtitration.
Filtration is not required for other halides because they form silver salts that are less soluble
than silver thiocyanate.

Mohrs method
Potassium chromate can serve as an end point indicator for the argentometric determination
of chloride, bromide and cyanide ions by reacting with silver ions to form a brick-red silver
chromate precipitate in the equivalence point region.
After all the chloride has been precipitated as white silver chloride (white precipitate), the
first excess of titrant results in the formation of a silver chromate precipitate (red
precipitate, by using potassium chromate as indicator), which signals the end point.

Red color formed because of formation of silver chromate disappears initially as the solution
contains high concentration of chloride ions. When the concentration of chloride ions has
decreased, the red color starts disappearing slowly and slowly on shaking and a stage is
reached when all the chloride ions have formed silver chloride. One extra drop of silver
nitrate at this point reacts with potassium chromate and reddish colored silver chromate is
formed.

Limitations of Mohrs method

1. This method can be used to determine the chloride ion concentration of water samples
from many sources such as seawater, stream water, river water and estuary water.
e.g. Seawater. The pH of the sample solutions should be between 6.5 and 10. If the solutions
are acidic, the gravimetric method or Volhards method should be used.
At higher pH silver ions may be removed by precipitation with hydroxide ions, and at low pH
chromate ions may be removed by an acid-base reaction to form hydrogen chromate ions or
dichromate ions, affecting the accuracy of the end point.

2. The Mohr titration is sensitive to the presence of both chloride and bromide ions in
solution and will not be too accurate when there is a significant concentration of bromide
present as well as the chloride.
For this reason, the method can also be used to determine either the total concentration of
chloride and bromide in solution, or the concentration of bromide when the chloride
concentration is known to be negligible and vice versa.
3. The chromate solution needs to be prepared and used with care as chromate is a known
carcinogen. Silver nitrate solution causes staining of skin and fabric (chemical
burns).

Adsorption indicators (Fajans titration)

Adsorption indicators are organic compounds that tend to be adsorbed onto the surface of
the solid precipitate in a precipitation titration.
The indicator result distinct change in color, either on the surface of the precipitate or in
the dye in which it is suspended.

This method of end point indication is sometimes called the Fajan's method after its
originator. A substance which is adsorbed or desorbed with concomitant color change at or
near the equivalence point of a titration.
During the titration, the precipitation of silver chloride from solution chloride and added
silver ions adsorption takes place represented by the following chemical reaction -

Before equivalence point

After equivalence point

Silver chloride forms colloidal particles. Before the equivalence point, the surface of the
precipitant particles will be negatively charged due to the adsorption of excess Cl- to the
surface of the particles. A diffuse positive counter - ion layer will surround the particles. The
primary negative charged adsorption layer repelled the anionic indicator.
When the equivalence point is reached, there is no longer an excess of analyte Cl- and the
surface of the colloidal particles are largely neutral.
After the equivalence point, there will be an excess of titrant Ag+, some of these will adsorb
to the solid AgCl particles, which will now be surrounded by a diffuse negative counter ion
layer. Now, negatively charged fluorescein (indicator) can penetrate the counter ion layer
and adsorb on to the AgCl lattice due to its affinity to Ag+

Fluorescein
A polycyclic compound that ionizes in solution to yield yellow-green fluoresceinate ions.
Fluoresceinate adsorbs to silver ions on the surface of a precipitate when excess silver ion is
present, producing a reddish colored surface. Only the ionized fluoresceinate produces the
red color.

Limitations
1. Adsorption indicators work well when they do not precipitate out silver ion but they
bind to the precipitate only when excess silver ion is present to produce color.
2. The action of the indicator relies on adsorption at the precipitate surface which, in turn,
depends on a large precipitate surface area. The presence of high concentrations of ionic
materials will cause the AgCl particles to coagulate, decrease the surface area and make
the indicator color change almost invisible. We overcome this difficulty by adding
dextrin (starch) to the titration mixture.
3. The indicator is a weakly basic substance and reacts with H+ ions in acid solutions. The
indicator works best above pH 5. However, the pH must be below about 9 to prevent
precipitation of AgOH.
4. The visual endpoint provided by the indicator requires a fairly clear and colorless
solution. The presence of any highly colored substances would completely obscure
the color change reaction.