GRAVIMETRIC METHODS OF

ANALYSIS
• Based on the measurement of mass
Properties of Gravimetric Analysis
• Traditional Method
• Cheap, easily available apparatus, simple to carry out
• Slow, especially when accurate results are required
• Wide range of sample concentrations (ng - kg)
• No calibration required (except for the balance)
• Accurate
Classifications of Gravimetric methods
1. Precipitation gravimetry
• the analyte is separated from a solution of the sample as a precipitate and is
converted to a compound of known composition that can be weighed.
2. Volatilization gravimetry
• the analyte is separated from other constituents of a sample by conversion to
a gas of known chemical composition.
• The weight of this gas then serves as a measure of the analyte concentration.
3. Electrogravimetry
• the analyte is separated by deposition on an electrode by an electrical
current. The mass of this product then provides a measure of the analyte
concentration.
• The mass of this product then provides a measure of the analyte
concentration.
 Precipitation
• the analyte is converted to a sparingly soluble
precipitate.

Filter, weigh, dry

• the mass of calcium oxide is determined by subtracting the known mass of

the crucible. The calcium content of the sample is then computed.
Precipitating agents

•Specific reagent - react only with a single

chemical species.
•Selective reagent - react with a limited
number of species.
What is your ideal precipitate:
1. Can be readily filtered and free of contaminants
2. With low solubility to avoid significant loss of the solid during
filtration and washing
3. Unreactive with the constituents of the atmosphere
4. Of known composition after dried or ignited
Easy to filter and usually purer than
Large particle size precipitates with fine particles

Colloidal suspension Very small and does not settle from

(10-7 to 10-4 cm in diameter) solution. Hard to filter.
Formation of precipitate
Particle growth Nucleation

Colloidal suspension/ small

Large particle size particles

Easy to filter and usually

Very small and does not
purer than precipitates with
settle from solution. Hard to
fine particles
filter.
Factors that determine the particle size of
precipitates
Von Weimarn ratio

• Q is the concentration of the solute at any instant and S is its equilibrium

solubility.

• When (Q - S)/S is large, the precipitate tends to be

colloidal
• When (Q - S)/S is small, a crystalline solid is more
likely.
How to decrease the relative supersaturation
(to produce large particle size)
1.Elevated temperatures to increase the solubility of the
precipitate (inc. S)
2.Dilute solutions (dec. Q)
3.Slow addition of the precipitating agent with good stirring
(inc. S)
4. Larger particles can also be obtained by pH control,
provided the solubility of the precipitate depends on pH.
Stability of colloidal suspension
Coagulation of a colloidal suspension
1. Heating
a.↓no. of adsorbed ions and the thickness of the double
layer.
b. gain enough kinetic energy to overcome the barrier to
close approach posed by the double layer.

2. stirring
Coagulation of a colloidal suspension
3. adding an electrolyte:
Results to the increase of the concentration of counter ions in the solution
because of its attraction with the electrolyte

shrinkage of the counter-ion layer in the colloid particle

particle can then approach one another more closely and

agglomerate/ coagulate.
Peptization of coagulated colloid
• a process by which a coagulated colloid returns to its
dispersed state.
• Reverse of coagulation
washing coagulated colloid → removal of electrolyte → volume
of the counter-ion layer increases

Peptization is prevented by washing ppt with a soln of a volatile

electrolyte. ex: AgCl, washed with a diluted HNO3.
Treatment of coagulated colloid
• Digestion - a process in which a ppt is heated for an hour
or more in the soln from which it was formed (the mother
liquor) → high purity and filterability

Methods of Improving Particle Size and

Filterability: Q↓, S↑, digestion
Coprecipitation
• a process in which normally soluble compounds are
carried out of solution by a precipitate.
• Can cause positive or negative errors

Four types of coprecipitation:

1.surface adsorption 1, 2 → equilibrium
2.mixed-crystal formation processes
3, 4 → arise from
3.Occlusion the kinetics of
4.mechanical entrapment crystal growth
Surface Adsorption
• Large surface area results to high surface adsorption
Surface Adsorption
• Adsorption, a normally soluble compound is carried out of solution on
the surface of a coagulated colloid.
• This compound consists of the primarily adsorbed ion and an ion of
opposite charge from the counter-ion layer.

Example:
In chloride analysis:
primary adsorbed ion : Ag+
counter-ion layer : NO3- or other anions
AgNO3 (normally soluble) is coprecipitated with the AgCl.
How to minimize surface adsorption
a. Digestion:
- Results to increase in particle size → decrease specific
surface area → low surface adsorption
b. Washing with volatile electrolyte solution
Example: in Ag+ analysis, primary adsorbed ion: Cl-
washing with an acidic soln → counter-ion layer : H+
→ HCl volatilized when ppt is dried
c. Reprecipitation, double precipitation
- Filtered solid is redissolved and reprecipitated
Mixed-crystal formation
- a contaminant ion replaces an ion in the lattice of a crystal

The contaminant has:

a. the same charge
b. the size differ < 5 %
c. salt : the same crystal class

Example:
(a) PbSO4 in BaSO4; (b) SrSO4 in BaSO4; (c) MnS in CdS
Occlusion
- A compound is trapped within a pocket formed during
rapid crystal growth.
- Caused by rapid crystal growth, decreased by digestion

contaminant
Mechanical entrapment
- Several crystals grow together & in so doing trap a portion
of the solution in a tiny pocket.
- Caused by rapid crystal growth, decreased by digestion

crystal

contaminant
Co-precipitation - positive or negative errors

• Depends on the molecular weight of the contaminant

Example:
In BaSO4 analysis:
If Ba(NO3)2 is the contaminant (larger FW than BaSO4) → (+) error
If BaCl2 (FW: BaCl2 < BaSO4) → (-) error
Homogeneous precipitation
• A precipitate is formed by slow generation of a precipitating
reagent homogeneously throughout a solution.

• Solid formed by homogeneous precipitation are generally

purer and more easily filtered than precipitate generated by
direct addition of a reagent to the analyte solution.
Drying and Ignition of precipitates
• Done to remove the solvent and volatile species carried
down with the precipitate

Weighing form – Compound of known composition formed after

ignition