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Introduction to

Analytical Chemistry
Chapter 4
Gravimetric Methods of Analysis

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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 and
volatilization methods.
• In precipitation methods, the analyte is
converted to a sparingly soluble precipitate.

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Gravimetric Methods of Analysis
• 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.

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Gravimetric Methods of Analysis
• In volatilization methods, the 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.

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Figure 4-1

Figure 4-1 Apparatus for determining the sodium hydrogen carbonate content of
antacid tablets by a gravimetric volatilization procedure.

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4A Properties Of Precipitates
And Precipitating Reagents
• Ideally, a gravimetric precipitating agent
should react specifically, or if not, then
selectively with the analyte.

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4A 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
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4A-1 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.
• A colloid is a solid made up of particles having
diameters that are less than 10-4 cm.

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4A-1 Particle Size and Filterability of
Precipitates
• What Factors Determine Particle Size?
– Colloidal particles show no tendency to settle
from solution, nor are they easily filtered.
– The particles, with dimensions on the order of
tenths of a millimeter or greater, temporary
dispersed in the liquid phase is called a crystalline
suspension.
– The particles of a crystalline suspension tend to
settle spontaneously and are readily filtered.

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4A-1 Particle Size and Filterability of
Precipitates
• What Factors Determine Particle Size?
– The particle size of a precipitate is influenced by
such experimental variables as precipitate
solubility, temperature, reactant concentrations,
and the rate at which reactants are mixed.

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4A-1 Particle Size and Filterability of
Precipitates
• What Factors Determine Particle Size?
– The particle size is related to relative
supersaturation, where

(4-1)

– Q is the concentration of the solute at any instant


and S is its equilibrium solubility.

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4A-1 Particle Size and Filterability of
Precipitates
• What Factors Determine Particle Size?
– When (Q - S)/S is large, the precipitate tends to be
colloidal; when (Q - S)/S is small, a crystalline solid
is more likely.

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4A-1 Particle Size and Filterability of
Precipitates
• How Do Precipitates Form?
– Assume that precipitates form in two ways,
namely by nucleation and by particle growth.
– The particle size of a freshly formed precipitate is
determined by which way is faster.

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4A-1 Particle Size and Filterability of
Precipitates
• How Do Precipitates Form?
– Nucleation is a process in which a minimum
number of atoms, ions, or molecules join together
to produce a stable solid.
– Further precipitation then involves a competition
between additional nucleation and growth on
existing nuclei (particle growth).

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4A-1 Particle Size and Filterability of
Precipitates
• How Do Precipitates Form?
– The rate of nucleation is believed to increase
enormously with increasing relative
supersaturation.
– In contrast, the rate of particle growth is only
moderately enhanced by high relative
supersaturations.

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4A-1 Particle Size and Filterability of
Precipitates
• Controlling Particle Size
– Experimental variables lead to crystalline
precipitates include elevated temperatures 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.

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4A-2 Colloidal Precipitates
• Coagulate, or agglomerate, the individual
particles of most colloids to give a filterable,
amorphous mass that will settle out of
solution.

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4A-2 Colloidal Precipitates
• Coagulation of Colloids
– Coagulation can be hastened by heating, stirring,
and adding an electrolyte to the medium.
– The charge on a colloidal particle formed in a
gravimetric analysis is determined by the charge
of the lattice ion that is in excess when the
precipitation is complete.

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4A-2 Colloidal Precipitates
• Coagulation of Colloids
– Adsorption is a process in which a substance (gas,
liquid, or solid) is held on the surface of a solid. In
contrast, absorption involves retention of a
substance within the pores of a solid.
– The charge on a colloidal particle formed in a
gravimetric analysis is determined by the charge
of the lattice ion that is in excess when the
precipitation is complete.

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Figure 4-2
Figure 4-2 A
colloidal silver
chloride particle
suspended in a
solution of silver
nitrate.

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Figure 4-3
Figure 4-3 Effect
of AgNO3 and
electrolyte
concentration on
the thickness of
the double layer
surrounding a
colloidal AgCl
particle in a
solution
containing excess
of AgNO3 .

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Figure 4-4
Figure 4-4 The electric double layer
of a colloid consists of a layer of
charge adsorbed on the surface of
the particle (the primary
adsorption layer) and a layer of
opposite charge (the counter-ion
layer) in the solution surrounding
the particle. Increasing the
electrolyte concentration has the
effect of decreasing the volume of
the counter-ion layer, thereby
increasing the chances for
coagulation.
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4A-2 Colloidal Precipitates
• Coagulation of Colloids
– 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.

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4A-2 Colloidal Precipitates
• Peptization of Colloids
– Peptization is a process by which a coagulated
colloid returns to its dispersed state.

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4A-2 Colloidal Precipitates
• Treatment of Colloidal Precipitates
– Colloids are best precipitated from hot, stirred
solutions containing sufficient electrolyte to
ensure coagulation.

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4A-3 Crystalline Precipitates
• Improving Particle Size and Filterability
– 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.

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4A-4 Coprecipitation
• There are four types of coprecipitation:
surface adsorption, mixed-crystal formation,
occlusion, and mechanical entrapment.
• Coprecipitation is a process in which normally
soluble compounds are carried out of solution
by a precipitate.

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4A-4 Coprecipitation
• Surface Adsorption
– Adsorption is a common source of coprecipitation
that is likely to cause significant contamination of
precipitates with large specific surface areas,
coagulated colloids .

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4A-4 Coprecipitation
• Surface Adsorption
– Coagulation of a colloid does not significantly
decrease the amount of adsorption.
– The net effect of surface adsorption is therefore
the carrying down of an otherwise soluble
compound as a surface contaminant.

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4A-4 Coprecipitation
• Surface Adsorption
– Minimizing Adsorbed Impurities on Colloids.
– The purity of many coagulated colloids is
improved by digestion.
– Regardless of the method of treatment, a
coagulated colloid is always contaminated to some
degree, even after extensive washing.

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4A-4 Coprecipitation
• Surface Adsorption
– Reprecipitation.
– A drastic but effective way to minimize the effects
of adsorption is reprecipitation, or double
precipitation.

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4A-4 Coprecipitation
• 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.

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4A-4 Coprecipitation
• Occlusion and Mechanical Entrapment
– When a crystal is growing rapidly during
precipitate formation, foreign ions in the counter-
ion layer may become trapped, or occluded,
within the growing crystal.
– Occlusion is a type of coprecipitation in which a
compound is trapped within a pocket formed
during rapid crystal growth.

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4A-4 Coprecipitation
• Occlusion and Mechanical Entrapment
– Mixed-crystal formation may occur in both
colloidal and crystalline precipitates, whereas
occlusion and mechanical entrapment are
confined to crystalline precipitates.
– Mechanical entrapment occurs when crystals lie
close together during growth.

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4A-4 Coprecipitation
• Occlusion and Mechanical Entrapment
– 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.

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4A-4 Coprecipitation
• Coprecipitation Errors
– Coprecipitation can cause either negative or
positive errors.

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4A-5 Precipitation from Homogeneous
Solution
• 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.

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4B 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.

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4B Drying And Ignition Of Precipitates

• Recording thermal decomposition curves


isoften called thermogravimetry or
thermalgravimetric analysis, and the mass vs.
temperature curves are called thermograms.

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Figure 4-7
Figure 4-7 Effect of
temperature on precipitate
mass.

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4C 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.

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Example 4.2
• 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.
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Example 4.2
• For both parts of this problem, we need to
calculate the number of moles of Fe2O3 . Thus,

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Example 4.2
• (a) The number of moles of Fe is twice the
number of moles of Fe2O3 , and

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Example 4.2
• (b) As shown by the following balanced
equation, 3 mol of Fe2O3 are chemically
equivalent to 2 mol of Fe3O4 . That is,

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4D 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.
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4D-1 Inorganic Precipitating Agents
• These reagents typically form slightly soluble
salts or hydrous oxides with the analyte.
• Most inorganic reagents are not very selective.

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4D-3 Organic Precipitating Agents
• Numerous organic reagents have been
developed for the gravimetric determination
of inorganic species.
• One forms slightly soluble nonionic products
called coordination compounds; the other
forms products in which the bonding between
the inorganic species and the reagent is
largely ionic.

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4D-3 Organic Precipitating Agents
• 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.

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4D-3 Organic Precipitating Agents
• 8-Hydroxyquinoline

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4D-3 Organic Precipitating Agents
• Dimethylglyoxime

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4D-3 Organic Precipitating Agents
• Sodium TetraphenylborateDimethylglyoxime
– Sodium tetraphenylborate, (C6H5) 4B-Na+, is an
important example of an organic precipitating
reagent that forms salt-like precipitates.

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4D-5 Volatilization Methods
• The two most common gravimetric methods
based on volatilization are those for water and
carbon dioxide.
• Carbonates are ordinarily decomposed by
acids to give carbon dioxide, which is readily
evolved from solution by heat.

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THE END

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