Principles and Applications

of Chemical Equilibria
Gravimetric Methods of Analysis
Titrimetric Methods of Analysis
GRAVIMETRIC METHODS OF
ANALYSIS
Properties of Precipitates and Precipitating Reagents
Drying and Ignition of Precipitates
Calculating Results from Gravimetric Data
Applications of Gravimetric Methods
Gravimetric Methods of Analysis
• Gravimetric methods of analysis are based on the measurement of
mass.
• There are two major types of gravimetric methods:
• Precipitation Methods
• Volatilization methods
PRECIPITATION METHODS
• Analyte is converted to a sparingly soluble precipitate.
• This precipitate is then filtered, washed free of impurities, and
converted to a product of known composition by suitable heat
treatment, and the product is weighed.
• Ex: Determination of Calcium in Natural Waters
VOLATILIZATION METHODS
• Analyte or its decomposition products
are volatilized at a suitable
temperature.
• The volatile product is then collected
and weighed, or, alternatively, the
mass of the product is determined
indirectly from the loss in mass of the
sample.
• Ex: Determination of Sodium
Hydrogen Carbonate content of
antacid tablets.
Properties Of Precipitates And Precipitating
Reagents
• The ideal precipitating reagent would react
with the analyte to give a product that is
• 1. Readily filtered and washed free of
contaminants
• 2. Of sufficiently low solubility so that no
significant loss of the solid occurs during
filtration and washing
• 3. Unreactive with constituents of the
atmosphere
• 4. Of known composition after it is dried or, if
necessary, ignited.
Particle Size and Filterability of Precipitates
Precipitates made up of large
particles are generally desirable in
gravimetric work because large
particles are easy to filter and
wash free of impurities.
COLLOIDA Colloidal particles show no
L tendency to settle from solution,
SUSPENSI nor are they easily filtered.
ON
A colloid is a solid made up of
particles having diameters that are
less than 10-4 cm.

CRYSTALLI The particles of a crystalline

NE suspension tend to settle
SUSPENSI spontaneously and are readily
Factors that Affects Particle Size
• Precipitate solubility The particle size is related to
• Temperature
• Reactant concentrations relative supersaturation, where
• Rate at which reactants are mixed

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.
Formation of Precipitates
• NUCLEATION
• is a process in which a minimum
number of atoms, ions, or molecules
join together to produce a stable solid.
• The rate of nucleation is believed to
increase enormously with increasing
relative supersaturation.
• PARTICLE GROWTH
• Further precipitation then involves a
competition between additional
nucleation and growth on existing
nuclei
• In contrast, the rate of particle
growth is only moderately enhanced
by high relative supersaturations.
Controlling Particle Size
CRYSTALLINE PRECIPITATES
• Elevate the temperature to
increase the solubility of the
precipitate, dilute solutions,
and slow addition of the
precipitating agent with good
stirring.
• Larger particles can also be
obtained by pH control,
provided the solubility of the
precipitate depends on pH.
• The particle size of crystalline
solids can often be improved
significantly by minimizing Q,
maximizing S, or both.
• Digestion of crystalline
precipitates (without stirring)
for some time after formation
frequently yields a purer,
more filterable product.
Controlling Particle Size
COLLOIDAL PRECIPITATES •Peptization is a process by which
• Coagulate, or agglomerate, the individual a coagulated colloid returns to its
particles of most colloids to give a
filterable, amorphous mass that will
dispersed state.
settle out of solution.
• Adsorption is a process in which a
substance (gas, liquid, or solid) is held on
the surface of a solid.
• Coagulation of a colloidal suspension can
often be brought about by a short period
of heating, particularly if accompanied by
stirring. An even more effective way to
coagulate a colloid is to increase the
electrolyte concentration of the solution.
COPRECIPITATION
• Coprecipitation is a process in
which normally soluble
compounds are carried out of
solution by a precipitate.
A. SURFACE ADSORPTION
B. MIXED-CRYSTAL FORMATION
C. OCCLUSION
D. MECHANICAL ENTRAPMENT
SURFACE ADSORPTION
• Adsorption is a common source The net effect of surface
of coprecipitation that is likely to adsorption is therefore the
cause significant contamination carrying down of an otherwise
of precipitates with large specific soluble compound as a surface
surface areas, coagulated contaminant.
colloids.
• Coagulation of a colloid does not
significantly decrease the
amount of adsorption.
SURFACE ADSORPTION
• Minimizing Adsorbed Impurities on Colloids
• DIGESTION
• A process in which a precipitate
is heated without stirring for an
hour more.

• Reprecipitation.
• A drastic but effective way to minimize the
effects of adsorption is reprecipitation,
or double precipitation.
Mixed-Crystal Formation
• In mixed-crystal formation, one of the
ions in the crystal lattice of a solid is
replaced by an ion of another element.
• The extent of mixed-crystal
contamination is governed by the law
of mass action and increases as the
ratio of contaminant to analyte
concentration increases.
Occlusion and Mechanical Entrapment
• Occlusion is a type of • Mechanical entrapment occurs
coprecipitation in which a when crystals lie close together
compound is trapped within a during growth.
pocket formed during rapid
crystal growth.
COPRECIPITATION
•Mixed-crystal formation may
occur in both colloidal and
crystalline precipitates, whereas
occlusion and mechanical
entrapment are confined to
crystalline precipitates.
• Both occlusion and mechanical
entrapment are at a minimum
when the rate of precipitate
formation is low, that is, under
conditions of low supersaturation.
• In addition, digestion is often
remarkably helpful in reducing
these types of coprecipitation.

*****Coprecipitation can cause either

negative or positive errors.
Homogenous Precipitation
• Homogeneous precipitation is a
process in which a precipitate is
formed by slow generation of a
precipitating reagent homogeneously
throughout a solution.
• In general, homogeneously formed
precipitates, both colloidal and
crystalline, are better suited for
analysis than a solid formed by direct
addition of a precipitating reagent.
Filtration of Precipitates
Drying And Ignition Of Precipitates
• After filtration, a gravimetric precipitate is heated until its mass
becomes constant.
• Some precipitates are also ignited to decompose the solid and form a
compound of known composition. This new compound is often
called the weighing form.
Calculating Results From Gravimetric Data
• The results of a gravimetric analysis are generally computed from the
mass of sample and the mass of a product of known composition.
• EXAMPLE:
The Calcium in a 200 mL sample of a natural water was determined
by precipitating the cation as CaC2O4. The precipitate was filtered,
washed and ignited in a crucible with an empty mass of 26.6002 g.
The mass of the crucible plus CaO (56.077 g/mol) was 26.7134 g.
Calculate the concentration of Ca (40.078 g/mol) in the water in
units of grams per 100 mL.
Calculating Results From Gravimetric Data
• Step 1: Determine the mass of CaO
Solution:
Mass of CaO = Mass of the crucible plus CaO - Mass of the empty
crucible
Mass of Cao = 26.7134 g - 26.6002 g
Mass of Cao = 0.1132 g
• Step 2: Calculate the number of moles of Ca in the sample
Solution:
Calculating Results From Gravimetric Data
• STEP 3: Calculate the concentration of Ca in the water per 100 mL
Solution:
Calculating Results From Gravimetric Data
• LET’S TRY THIS!
An iron ore was analyzed by dissolving a 1.1324-g sample in
concentrated HCl. The resulting solution was diluted with water, and
the iron(III) was precipitated as the hydrous oxide Fe2O3‧xH2O by the
addition of NH3. After filtration and washing, the residue was ignited at
a high temperature to give 0.5394 g of pure Fe2O3 (159.69 g/mol).
Calculate (a) the % Fe (55.847 g/mol) and (b) the % Fe3O4 (231.54
g/mol) in the sample.
Calculating Results From Gravimetric Data
• STEP 1: Calculate the number
of moles of Fe2O3.
• STEP 2: Calculate the number
of moles of Fe present
• STEP 3: Calculate the %Fe
present
Calculating Results From Gravimetric Data
• Step 4: Calculate the % Fe3O4
Applications of Gravimetric Methods
• Gravimetric methods have been developed for most inorganic anions
and cations as well as for such neutral species.
• A variety of organic substances can also be readily determined
gravimetrically.
• Gravimetric methods do not require a calibration or standardization
step because the results are calculated directly from the experimental
data and molar masses.
Applications of Gravimetric Methods
Inorganic Precipitating Agents
• These reagents typically form
slightly soluble salts or hydrous
oxides with the analyte.
• Most inorganic reagents are not
very selective.
Organic Precipitating Agents
• 2 types of organic reagents
• Coordination Compounds- One forms
slightly soluble nonionic products.(2
functional groups)
• The other forms products in which the
bonding between the inorganic species
and the reagent is largely ionic.
Organic Precipitating Agents
Coordination Compounds
• Typically contains atleast 2 functional groups, each group is capable of
bonding with a cation by donating a pair of electrons. This are usually
located in the molecule such that a five-or six-membered ring results
from the reaction.
• Chelates are cyclical metal-organic compounds in which the metal is a
part of one or more five- or six-membered rings.
• 8-Hydroxyquinoline and dimethylglyoxime are two widely used
chelating reagent. Sodium tetraphenyl borate is a near-specific
precipitation agent for potassium and ammonium.
Organic Precipitating Agents
• 8-Hydroxyquinoline
• The solubilities of this metal chelate
vary widely from cation to cation and
are pH-dependent because it is always
deprotonated during chelation
reaction.
• Dimethylglyoxime
• It is an organic precipitating agent of
unparalled specificity.
• It has an exasperating tendency to
creep up the sides of the container as
it is filtered and washed.
Organic Precipitating Agents
• Sodium
TetraphenylborateDimethylglyo
xime
• Sodium tetraphenylborate,
(C6H5) 4B-Na+, is an important
example of an organic
precipitating reagent that
forms salt-like precipitates.
Volatilization Methods
• The two most common gravimetric methods
based on volatilization are those for water
and carbon dioxide.
• Water is quantitatively eliminated from many
inorganic samples by ignition.
• Carbonates are ordinarily decomposed by
acids to give carbon dioxide, which is readily
evolved from solution by heat.
• Sulfides and sulfides can also be determined
by volatilization.
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