AC06 - Precipitation and Volatilization Gravimetry

PRECIPITATION AND VOLATILIZATION
GRAVIMETRY
Lecture Notes 06
Analytical Chemistry 01
CHEM 20105
OUTLINE
1. Introduction
2. Precipitation Gravimetry
3. Volatilization Gravimetry
4. Applications of Gravimetric Methods
5. Calculation of Results from Gravimetric Data
6. Additional Problems
7. References
Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
INTRODUCTION
Gravimetric methods are quantitative methods that are based on determining the mass of a
pure compound to which the analyte is chemically related.
• 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.
• Volatilization gravimetry: the analyte is separated from other constituents of a sample by

converting it to a gas of known chemical composition. The mass of the gas serves as a
measure of the analyte concentration.
• Electrogravimetry: the analyte is separated by deposition on an electrode by an electrical

current. The mass of this product provides a measure of the analyte concentration.
• Gravimetric titrimetry: the mass of a reagent of known concentration required to react

completely with the analyte provides the information needed to determine the analyte
concentration.
• Atomic mass spectrometry: uses a mass spectrometer to separate the gaseous ions
formed from the elements making up a sample of matter. The concentration of the
resulting ions is then determined by measuring the electrical current produced when
they fall on the surface of an ion detector.
PRECIPITATION GRAVIMETRY
GENERAL STEPS IN PRECIPITATION GRAVIMETRY
1. Conversion of analyte to soluble precipitate.

2. Filtration of precipitate.
3. Washing of precipitate to free it from impurities.
4. Conversion of precipitate to a product of known
composition by suitable heat treatment.
5. Weighing of precipitate.
6. Computation of the amount of analyte.
EXAMPLE OF PRECIPITATION GRAVIMETRY:
Determination of Calcium in Water by the Association of Official Analytical Chemists
1. An excess of oxalic acid, H2C2O4, is added to an aqueous solution of the

sample. Ammonia is then added, which neutralizes the acid and causes
essentially all of the calcium in the sample to precipitate as calcium oxalate.
2. The precipitate is filtered using a weighed filtering crucible.

3. The precipitate is washed.
4. The precipitate is dried and ignited.
5. After cooling, the crucible and precipitate are weighed.

6. The mass of calcium oxide is determined by subtracting the known mass of the
crucible. The calcium content of the sample is computed.
PROPERTIES OF PRECIPITATING REAGENTS AND PRECIPITATES
1. It should react specifically or at least selectively with the

analyte.
2. It should react with the analyte that would give a product
that is:
a. easily filtered and washed free of contaminants;

b. of sufficiently low solubility that no significant loss of the
analyte occurs during filtration and washing;
c. unreactive with constituents of the atmosphere;
d. of known chemical composition after it is dried or if
necessary, ignited
PARTICLE SIZE AND FILTERABILITY OF PRECIPITATES
• Precipitates consisting of large particles are generally
desirable for gravimetric work because these particles are
easy to filter and wash free of impurities and are usually
purer than are precipitates made up of fine particles.
Types of precipitates
• Colloidal suspensions: solid particles with diameters that
are less than 10-4 cm; show no tendency to settle from
solution and are difficult to filter
• Crystalline suspensions: are particles with dimensions on
the order of tenths of a millimeter or greater; tend to
settle spontaneously and are easily filtered.
Factors that determine the particle size of precipitates
1. Precipitate solubility
2. Temperature
3. Reactant concentrations
4. Rate ate which reactants are mixed.
Mechanism of precipitate formation

• Nucleation: a process in which a minimum number of atoms,
ions, or molecules join together to give a stable solid.
• Particle Growth: growth of existing nuclei
NOTE: If nucleation predominates, a precipitate containing a

large number of small particles results, and if growth
predominates, a smaller number of larger particles is produced.
• At high relative supersaturation, nucleation is the major
precipitation mechanism, and a large number of small
particles is formed.
• At low relative supersaturations, the rate of particle
growth tends to predominate, and deposition of solid on
existing particles occurs rather than further nucleation.
Low relative supersaturation produces crystalline
suspensions.
where Q = is the concentration of solute at any instant

S = equilibrium solubility
Experimental control of particle size
1. elevated temperatures to increase the solubility of the
precipitate
2. dilute solutions (to minimize Q)
3. slow addition of the precipitating agent with good
stirring (to minimize the concentration of the solute (Q)
at any given instant.
4. if the solubility of the precipitate depends on pH, larger
particles can also be produced by controlling pH.
COLLOIDAL PRECIPITATES
We can coagulate, or
agglomerate, the
individual particles of
most colloids to give a
filterable, amorphous
mass that will settle out of
solution.
Colloidal suspensions can

often be coagulated by
heating, stirring, and
adding anelectrolyte.
Peptization of colloids
• Peptization is the process by which a coagulated colloid
reverts to its original dispersed state.
• Petization occurs during the washing of precipitates to
remove contaminants. To avoid peptization to occur, the
precipitate should be washed with a solution containing
an electrolyte that volatilizes when the precipitate is
dried or ignited.
Practical treatment of colloidal precipitates

• Digestion is a process in which a precipitate is heated in
the solution from which it was formed (the mother
liquor) and allowed to stand in contact with the solution.
CRYSTALLINE PRECIPITATES
Methods of improving particle size and filterability
1. Use of dilute solutions (to minimize Q)

2. Adding the precipitating agent slowly with good mixing (
to minimize Q)
3. Precipitating from hot solution (to increase S)
4. Adjusting the pH of the precipitating medium (to
increase S)
5. Digestion without stirring
COPRECIPITATION
• Coprecipitation is a process in which normally soluble
compounds are carried out of solution by a precipitate.
Types of coprecipitation
• Surface 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.
- Reprecipitation: the filtered solid is redissolved and
reprecipitated. A drastic but effective way to minimize
the effects of adsorption.
Types of coprecipitation (continuation)
• Mixed-crystal formation: is a type of coprecipitation in which a

contaminant ion replaces an ion in the lattice of a crystal. For this
exchange to occur, it is necessary that the two ions have the same charge
and that their sizes differ by no more than about 5%. Furthermore, the
two salts must belong to the same crystal class. Alternatively, a different
precipitating reagent that does not give mixed crystals with the ions in
question may be used.
• Occlusion: is a type of coprecipitation in which a compound is trapped

within a pocket formed during rapid crystal growth. Digestion often
reduces the effects of this of coprecipitation.
• Mechanical entrapment: occurs when crystals lie close together during

growth. Several crystals grow together and in so doing trap a portion of
the solution in a tiny pocket. Digestion often reduces the effects of this of
coprecipitation.
Coprecipitation errors
• If the contaminant is not a compound of the ion being

determined, a positive error will always result.
• When the contaminant does contain the ion being
determined, either positive or negative errors may occur.
PRECIPITATION FROM HOMOGENOUS 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.
DRYING AND IGNITION OF PRECIPITATES
• After filtration, a gravimetric precipitate is heated until its
mass becomes constant.
• Heating removes the solvent and any volatile species
carried down with the precipitate.
• 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.
VOLATILIZATION GRAVIMETRY
APPLICATIONS OF GRAVIMETRIC METHODS
• Inorganic precipitating agents
• Inorganic precipitating agents
• Reducing agents
• Organic functional groups analysis
CALCULATION OF RESULTS FROM GRAVIMETRIC DATA
ADDITIONAL PROBLEM (1)
Write an equation showing how the mass of the substance
sought can be converted to the mass of the weighed
substance on the right.
Treatment of a 0.2500-g sample of impure potassium
chloride with an excess of AgNO3 resulted in the formation
of 0.2912 g of AgCl. Calculate the percentage of KCl in the
sample.
• What mass of Cu(IO3)2 can be formed from 0.650 g of
CuSO4 · 5H2O?
What mass of AgI can be produced from a 0.512-g
sample that assays 20.1% AlI3?
A 0.2121-g sample of an organic compound was
burned in a stream of oxygen, and the CO2
produced was collected in a solution of barium
hydroxide. Calculate the percentage of carbon in the
sample if 0.6006 g of BaCO3 was formed.
The mercury in a 1.0451-g sample was precipitated
with an excess of paraperiodic acid, H5IO6:
The precipitate was filtered, washed free of

precipitating agent, dried, and weighed, and 0.5718
g was recovered. Calculate the percentage of Hg2Cl2
in the sample.
Ammoniacal nitrogen can be determined by treatment
of the sample with chloroplatinic acid; the product is
slightly soluble ammonium chloroplatinate:
The precipitate decomposes on ignition, yielding

metallic platinum and gaseous products:
Calculate the percentage of ammonia in a sample if

0.2115 g gave rise to 0.4693 g of platinum.
A series of sulfate samples is to be analyzed by
precipitation as BaSO4. If it is known that the sulfate
content in these samples ranges between 20% and
55%, what minimum sample mass should be taken
to ensure that a precipitate mass no smaller than
0.200 g is produced? What is the maximum
precipitate mass to be expected if this quantity of
sample is taken?
The efficiency of a particular catalyst is highly dependent on its
zirconium content. The starting material for this preparation is
received in batches that assay between 68% and 84% ZrCl4.
Routine analysis based on precipitation of AgCl is feasible, it having
been established that there are no sources of chloride ion other
than the ZrCl4 in the sample.
(a) What sample mass should be taken to ensure an AgCl

precipitate that weighs at least 0.400 g?
(b) If this sample mass is used, what is the maximum mass of AgCl
that can be expected in this analysis?
(c) To simplify calculations, what sample mass should be taken to

have the percentage of ZrCl4 exceed the mass of AgCl produced
by a factor of 100?
A 0.6407-g sample containing chloride and iodide
ions gave a silver halide precipitate weighing 0.4430
g. This precipitate was then strongly heated in a
stream of Cl2 gas to convert the AgI to AgCl; on
completion of this treatment, the precipitate
weighed 0.3181 g. Calculate the percentage of
chloride and iodide in the sample.
What mass in grams of CO2 is evolved in the
complete decomposition of a 2.300-g sample that is
38.0% MgCO3 and 42.0% K2CO3 by mass?
A 50.0-mL portion of a solution containing 0.200 g
of BaCl2.2H2O is mixed with 50.0 mL of a solution
containing 0.300 g of NaIO3. Assume that the
solubility of Ba(IO3)2 in water is negligibly small and
calculate
(a) the mass of the precipitated Ba(IO3)2.
(b) the mass of the unreacted compound that
remains in solution.
ADDITIONAL PROBLEMS (Answers)
REFERENCES/SOURCES:
• Skoog, D.A., West, D.M., Holler, F.J. & Crouch,

S.R. (2013) Fundamentals of Analytical
Chemistry, 9th Edition. Brookes/Cole, Cengage
Learning, Belmont, USA

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PRECIPITATION AND VOLATILIZATION

• Precipitation gravimetry: the analyte is separated from a solution of the sample as a

• Volatilization gravimetry: the analyte is separated from other constituents of a sample by

• Electrogravimetry: the analyte is separated by deposition on an electrode by an electrical

• Gravimetric titrimetry: the mass of a reagent of known concentration required to react

1. Conversion of analyte to soluble precipitate.

1. An excess of oxalic acid, H2C2O4, is added to an aqueous solution of the

2. The precipitate is filtered using a weighed filtering crucible.

5. After cooling, the crucible and precipitate are weighed.

1. It should react specifically or at least selectively with the

a. easily filtered and washed free of contaminants;

Mechanism of precipitate formation

NOTE: If nucleation predominates, a precipitate containing a

where Q = is the concentration of solute at any instant

Colloidal suspensions can

Practical treatment of colloidal precipitates

Methods of improving particle size and filterability

1. Use of dilute solutions (to minimize Q)

• Mixed-crystal formation: is a type of coprecipitation in which a

• Occlusion: is a type of coprecipitation in which a compound is trapped

• Mechanical entrapment: occurs when crystals lie close together during

• If the contaminant is not a compound of the ion being

The precipitate was filtered, washed free of

The precipitate decomposes on ignition, yielding

Calculate the percentage of ammonia in a sample if

(a) What sample mass should be taken to ensure an AgCl

(c) To simplify calculations, what sample mass should be taken to

• Skoog, D.A., West, D.M., Holler, F.J. & Crouch,

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