PRECIPITATION TITRATION

A titrimetric method based on the formation of a slightly soluble precipitate is called a precipitation titration.

PRINCIPLE OF PRECIPITATION TITRATIONS

Involves formation of a precipitate.
Must determine the volume of a standardized titrant needed to just precipitate all of the ion. Need an indicator or electrode to determine when the precipitation is complete.

SOLUBILITY OF PRECIPITATES

It refers to the amount of solute capable to dissolve in a volume of solvent.

Therefore , the chemical substances can be classified depending

upon its solubility to : soluble , or partially soluble , or insoluble .

saturated

solubility

Concentration of ion

SOLUBILITY PRODUCT CONSTANT (K.S.P) :

K.S.P is an important constant which is applied to saturated
solution of slightly soluble but completely ionized such as salts or metal hydroxide.

It is calculated from multiplying of anion and cation

concentrations : AB A+ + B-

K.S.P = [ A+] [ B- ]

SOLUBILITY PRODUCT
Precipitation titrations produce sparingly soluble salts.
Consider a precipitate, AgCl AgCl (AgCl) Ag+ + Cl-

Keq = Ksp = [Ag+][Cl-] = solubility product.

Precipitation will not occur unless the product of [Ag+] and [Cl -] exceeds Ksp.

FACTORS AFFECTING SOLUBILITY OF A PRECIPITATE

1. Temperature 2. Solvent

3. Common Ion Effect

4. Effect of pH 5.Effect of Hydrolysis

6. Effect of Complexation

EFFECT OF HYDRONIUM ION CONCENTRATION (

When anion or cation of precipitate is capable to react with [H3O+] or [OH-] of solvent .

CaF2

Ca+2 + 2F2H3O+ 2HF + 2H2O

CaF2 is a salt of a weak acid (HF). According to Le Chatelier principle,increasing

decreasing in F- concentration.

in [H3O+]

concentration causes an increasing in HF concentration and

Then

solubility of precipitate will be increase.

EFFECT OF TEMPERATURE

Increasing of temperature will causes an increasing

in solubility of precipitate.

It leads to an increase in KSP value for precipitates

which are slightly soluble.

EFFECT OF SOLVENT
Inorganic salts are more soluble in water. A decrease in solubility in organic solvents can be used to separate two compounds. Example : mixture of Ca(NO3)2 and Sr(NO3)2 can be separated in solvent mixture containing alcohol and ether, which yields a soluble Ca(NO3)2 and an insoluble Sr(NO3)2

The different types of precipitation titrations are:

Argentometric method Mercurimetric method Kolthoff titration

ARGENTOMETRIC TITRATION
Argentometry is the useful method of precipitation titration, as it is caused of very low solubility product of halide salts.

There are 3 techniques of end point determination:

Mohrs method (indicator : chromic potassium) Volhard method (indicator : ferric salt) Fajans method (indicator : fluorosceine)

MOHRS METHOD
Developed for the determination of Cl- and Br -. Uses AgNO3 as titrant and Na2CrO4 as indicator Titration reaction: Ag+ + ClAgCl(s) Ksp= 1 x 10-10
Indicator reaction: 2Ag+

CrO 2- --> Ag CrO 4 2 4

(excess) (yellow) (red) Ag CrO is precipitated at the equivalence point 2 4

VOLHARDS METHOD
Volhard titration is an indirect (back titration) technique which is used if reaction is too slow or if there is no appropriate indicator selected for determining the equivalent point.

Titration principle :
Silver solution is added excessively to halide: Br- + Ag+ AgBr (precipitate) excess

After reaction has completed, the precipitate is filtered, then the filtrate is titrated with a standardized thiocyanate solution. Ag+ + SCNAgSCN (solution) Fe(III) indicator reacts with thiocyanate ion to form a

red colour solution :

Fe3+ + SCN[Fe(SCN)]2+

The reaction requires acid condition, as in basic solution the ferric

ions form Fe(OH) precipitate. 3

FAJANS METHOD
Fajans titration use adsorption indicators, i.e. organic compounds which is adsorbed into colloidal precipitate surface during the titration processes. Example : Fluoreseine in form of its fluorescenate (yellowish green)

Anion react with Ag+ to form an intensive red precipitate which

is adsorbed to AgCl precipitate surface caused by ionic pair

interaction Adsorption of colour organic compound on a precipitate surface could induce intermolecular electronic shift then change solution colour.

This phenomenon is usually used for end titration detection of

silver salt precipitation.

Fluorescein is a weak organic acid, forms a fluoresceinate ion

which is not adsorbed by colloidal AgCl precipitate during excess of Cl-.

But in the solution with excess of Ag+ the fluoresceinate anion

will be adsorbed to form a Ag+ shielding layer, followed by change the solution colour to pink.

INDICATOR Dichlorofluorescein Fluorescein Eosin Thorin Methyl violet Bromphenol blue Orthochrome T

ANALYTE ClClBr-, I-, SCNSO42Ag+ Hg22+ Pb2+

TITRANT Ag+ Ag+ Ag+ Ba2+ ClClCrO42-

REACTIONCONDITION pH = 4 pH = 7 8 pH = 2 pH = 1,5 3,5 acid solution solution of 0,1 M neutral 0,02 M soln

MERCURIMETRIC TITRATION
When halide ions is titrated with mercuric nitrate solution,

[Hg2+] is not found at the equivalent point.

It is found in HgCl2 precipitate. After equivalent point, [Hg2+] increases, react with indicator to form a Hg-indicator complex. Hg2+ +2 ClHgCl2

e.g. Nitropruside form white precipitate, acid solution of diphenylcarbazide in forms intensive violet colour solution.

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