GRAVIMETRIC

ANALYSIS
Definition-Gravimetry
Any method in which the signal is a mass or change
in mass.
Types of gravimetric methods
• Precipitation gravimetry
• Electrogravimetry
• Volatiization gravimetry
• Particulate gravimetry
Precipitation gravimetry
- A gravimetric method in which the signal is the mass of a
precipitate.

Electrogravimetry
- A gravimetric method in which the signal is the mass of an
electrodeposit on the cathode or anode in an electrochemical cell
Volatilization gravimetry
- A gravimetric method in which the loss of a volatile
species gives rise to the signal.

Particulate gravimetry
-A gravimetric method in which the mass of a particulate
analyte is determined following its separation from its matrix
Consideration for a successful gravimetric
analysis
• Separation of the constituent sought should be complete or
nearly so.
• The isolated constituent should be obtained in pure condition.
• The products weighed should be of definite chemical
composition

Most common isolation method is precipitation.

Selected Gravimetric Method for Inorganic Cations Based on Precipitation
Selected Gravimetric Methods for
Inorganic Anions Based on Precipitation
Steps in the analysis
1. Weighing the sample
2. Dissolving the sample
3. Precipitation- A 10% excess reagent is desirable. Too great an excess
of precipitant increase adsorption and coprecipitation effects and
causes secondary reaction to occur
4. Digestion of the ppt
5. Filtration and washing of the ppt
6. Drying and ignition of the precipitate
7. Weighing of the ignited precipitate
Digestion
The process by which a precipitate is given time to form larger, purer
particles.

• Heating of the precipitate in contact with the mother liquor near

the boiling point of the solution
• Small crystals dissolved and redeposited of larger crystals
(Ostwald ripening)
Filtration
Washing
• Immediately after filtration all precipitates must
be washed free of soluble impurities.
Drying and ignition
1. Bring the crucible to constant weight.
2. Transfer the precipitate to crucible.
3. Dry the precipitate and the filter.
4. Char the paper.
5. Oxidize the carbon by increasing the size of the flame until the
bottom of the crucible is heated to redness.
6. Ignite at the prescribe temperature.
Mechanism of precipitate formation
1. Nucleation
2. Particle growth

• Nucleation dominates, a large number of very fine precipitate results.

• Particle growth predominates a smaller number of large particles is
formed.
 Controlling particle size
Von Weimarn ratio

Relative supersaturation
Q-instantenous concentration of the substance that precipitates
S-equilibrium solubility of the substance the precipitates
Relative supersaturation
If 25,000-curdy precipitate
1,300-fine feathery crystals
125-compact crystals
25-large crystals
Particle Size and Filterability of Precipitates

• Precipitates made up of large particles are generally

desirable in gravimetric analysis because large particles
are easier to filter and wash free of impurities.
• Large particles are usually pure than precipiates made
up of finer particles.
Factors affecting particle size
1. Precipitate solubility
2. Temperature
3. Reactant concentration
4. The rate at which reactants are mixed
Increase particle size
1. In a dilute solution of the analyte-Q
should be maintained just slightly
above S.
2. At a temperature close to the boiling
point of water-increase T increases S.
3. With constant stirring- decreases the relative
supersaturation at the portion where the solution first mixes.

4. By homogeneous precipitation- the precipitating ion is

produced in the solution by a solution reaction.

5. At low pH-applicable in cases where the precipitate is a salt

of a weak acid
Schematic model of the solid–
solution interface at a particle of AgCl
in a solution containing excess
AgNO3.
Avoiding Impurities
Inclusion- A coprecipitated impurity in which the interfering ion
occupies a lattice site in the precipitate.

schematic of a chemically
adsorbed inclusion or a
physically adsorbed
occlusion in a crystal
lattice
Avoiding Impurities
Occlusion-A coprecipitated impurity trapped within a precipitate
as it forms.

schematic of an occlusion by
entrapment of supernatant solution
Avoiding Impurities
Adsorbate- A coprecipitated impurity that adsorbs to the surface
of a precipitate.

Surface adsorption of excess C

Calculating Results from Gravimetric Data
•Mass of the sample
•Mass of a product of known composition