I.

PRECIPITATION GRAVIMETRI
Precipitation gravimetry is based on the formation of an insoluble
compound following the addition of a precipitating reagent, or precipitant,
to a solution of the analyte. In most methods the precipitate is the product
of a simple metathesis reaction between the analyte and precipitant;
however, any reaction generating a precipitate can potentially serve as a
gravimetric method. Most precipitation gravimetric methods were
developed in the nineteenth century as a means for analyzing ores. Many
of these methods continue to serve as standard methods of analysis.
(Harvey,2000:235)
I.1 Teori and Practice
A precipitation gravimetric analysis must have several important
attributes. First, the precipitate must be of low solubility, high purity, and
of known composition if its mass is to accurately reflect the analytes
mass. Second, the precipitate must be in a form that is easy to separate
from the reaction mixture.
(Harvey,2000:235)
Solubility Considerations An accurate precipitation gravimetric
method requires that the precipitates solubility be minimal. Many total
analysis techniques can routinely be performed with an accuracy of better
than 0.1%. To obtain this level of accuracy, the isolated precipitate must
account for at least 99.9% of the analyte. By extending this requirement
to 99.99% we ensure that accuracy is not limited by the precipitates
solubility.
Solubility losses are minimized by carefully controlling the composition
of the solution in which the precipitate forms. This, in turn, requires an
understanding of the relevant equilibrium reactions affecting the
precipitates solubility. For example, Ag + can be determined
gravimetrically by adding Cl as a precipitant, forming a precipitate of
AgCl.
(Harvey,2000:235)
Avoiding Impurities Precipitation gravimetry is based on a known
stoichiometry between the analytes mass and the mass of a precipitate.
It follows, therefore, that the precipitate must be free from impurities.
Since precipitation typically occurs in a solution rich in dissolved solids,
the initial precipitate is often impure. Any impurities present in the
precipitates matrix must be removed before obtaining its weight.
The greatest source of impurities results from chemical and
physical interactions occurring at the precipitates surface. A precipitate is
generally crystalline, even if only on a microscopic scale, with a welldefined lattice structure of cations and anions. Those cations and anions
at the surface of the precipitate carry, respectively, a positive or a
negative charge as a result of their incomplete coordination spheres. In a
precipitate of AgCl, for example, each Ag+ ion in the bulk of the
precipitateis bound to six Cl ions. Silver ions at the surface, however, are

bound to no more than five Cl ions, and carry a partial positive charge
(Figure 8.3).
Precipitate particles grow in size because of the electrostatic
attraction between charged ions on the surface of the precipitate and
oppositely charged ions in solution. Ions common to the precipitate are
chemically adsorbed, extending the crystal lattice. Other ions may be
physically adsorbed and, unless displaced, are incorporated into the
crystal lattice as a coprecipitated impurity. Physically adsorbed ions are
less strongly attracted to the surface and can be displaced by chemically
adsorbed ions.

Figure 8.3 Schematic model of AgCl showing difference between bulk and
surface atoms of silver. Silver and chloride ions are not shown to scale.
One common type of impurity is an inclusion. Potential interfering
ions whose size and charge are similar to a lattice ion may substitute into
the lattice structure by chemical adsorption, provided that the interferent
precipitates with the same crystal structure (Figure 8.4a). The probability
of forming an inclusion is greatest when the interfering ion is present at
substantially higher concentrations than the dissolved lattice ion. The
presence of an inclusion does not decrease the amount of analyte that
precipitates, provided that the precipitant is added in sufficient excess.
Thus, the precipitates mass is always larger than expected.
Inclusions are difficult to remove since the included material is
chemically part of the crystal lattice. The only way to remove included
material is through reprecipitation. After isolating the precipitate from the
supernatant solution, it is dissolved in a small portion of a suitable solvent
at an elevated temperature. The solution is then cooled to re-form the
precipitate. Since the concentration ratio of interferent to analyte is lower
in the new solution than in the original supernatant solution, the mass
percent of included material in the precipitate decreases. This process of

reprecipitation is repeated as needed to completely remove the inclusion.

Potential solubility losses of the analyte, however, cannot be ignored.
Thus, reprecipitation requires a precipitate of low solubility, and a solvent
for which there is a significant difference in the precipitates solubility as a
function of temperature.
(Harvey,2000:238,239)

Figure 8.4 Example of coprecipitation: (a) schematic of a chemically

adsorbed inclusion or a physically adsorbed occlusion in a crystal lattice,
where C and A represent the cationanion pair comprising the analyte and
the precipitant, and is the impurity; (b) schematic of an occlusion by
entrapment of supernatant solution; (c) surface adsorption of excess C.
Occlusions, which are a second type of coprecipitated impurity,
occur when physically adsorbed interfering ions become trapped within
the growing precipitate. Occlusions form in two ways. The most common
mechanism occurs when physically adsorbed ions are surrounded by
additional precipitate before they can be desorbed or displaced (see
Figure 8.4a). In this case the precipitates mass is always greater than
expected. Occlusions also form when rapid precipitation traps a pocket of
solution within the growing precipitate (Figure 8.4b). Since the trapped
solution contains dissolved solids, the precipitates mass normally
increases. The mass of the precipitate may be less than expected,
however, if the occluded material consists primarily of the analyte in a
lower-molecular-weight form from that of the precipitate.
Occlusions are minimized by maintaining the precipitate in equilibrium
with its supernatant solution for an extended time. This process is called
digestion and may be carried out at room temperature or at an elevated
temperature. During digestion,
the dynamic nature of the solubilityprecipitation equilibrium, in which the
precipitate dissolves and re-forms, ensures that occluded material is
eventually exposed to the supernatant solution. Since the rate of
dissolution and reprecipitation
are slow, the chance of forming new occlusions is minimal.
After precipitation is complete the surface continues to attract ions
from solution (Figure 8.4c). These surface adsorbates, which may be
chemically or physically adsorbed, constitute a third type of coprecipitated
impurity. Surface adsorption is minimized by decreasing the precipitates
available surface area. One benefit of digestion is that it also increases
the average size of precipitate particles. This is not surprising since the
probability that a particle will dissolve is inversely proportional to its size.

During digestion larger particles of precipitate increase in size at the

expense of smaller particles. One consequence of forming fewer particles
of larger size is an overall decrease in the precipitates surface area.
Surface adsorbates also may be removed by washing the precipitate.
Potential solubility losses, however, cannot be ignored.
Inclusions,
occlusions,
and
surface
adsorbates
are
called
coprecipitates because they represent soluble species that are brought
into solid form along with the desired precipitate. Another source of
impurities occurs when other species in solution precipitate under the
conditions of the analysis. Solution conditions necessary to minimize the
solubility of a desired precipitate may lead to the formation of an
additional precipitate that interferes in the analysis. For example, the
precipitation of nickel dimethylgloxime requires a pH that is slightly basic.
Under these conditions, however, any Fe3+ that might be present
precipitates as Fe(OH)3. Finally, since most precipitants are not selective
toward a single analyte, there is always a risk that the precipitant will
react, sequentially, with more than one species.
The formation of these additional precipitates can usually be
minimized by carefully controlling solution conditions. Interferents forming
precipitates that are less soluble than the analyte may be precipitated and
removed by filtration, leaving the analyte behind in solution. Alternatively,
either the analyte or the interferent can be masked using a suitable
complexing agent, preventing its precipitation.
(Harvey,2000:239,240)
Controlling Particle Size Following precipitation and digestion, the
precipitate must be separated from the supernatant solution and freed of
any remaining impurities, including residual solvent. These tasks are
accomplished by filtering, rinsing, and drying the precipitate. The size of
the precipitates particles determines the ease and success of filtration.
Smaller, colloidal particles are difficult to filter because they may readily
pass through the pores of the filtering device. Large, crystalline particles,
however, are easily filtered.
By carefully controlling the precipitation reaction we can
significantly increase a precipitates average particle size. Precipitation
consists of two distinct events: nucleation, or the initial formation of
smaller stable particles of precipitate, and the
subsequent growth of these particles. Larger particles form when the rate
of particle
growth exceeds the rate of nucleation.
A solutes relative supersaturation, RSS, can be expressed as

RSS=

QS
S

(1.2)

where Q is the solutes actual concentration, S is the solutes expected

concentration at equilibrium, and Q S is a measure of the solutes

supersaturation when precipitation begins. A large, positive value of RSS

indicates that a solution is highly supersaturated. Such solutions are
unstable and show high rates of nucleation, producing a precipitate
consisting of numerous small particles. When RSS is small, precipitation is
more likely to occur by particle growth than by nucleation.
Examining equation (1.2) shows that we can minimize RSS by either
decreasing the solutes concentration or increasing the precipitates
solubility. A precipitates solubility usually increases at higher
temperatures, and adjusting pH may affect a precipitates solubility if it
contains an acidic or basic anion. Temperature and pH, therefore, are
useful ways to increase the value of S. Conducting the precipitation in a
dilute solution of analyte, or adding the precipitant slowly and with
vigorous stirring are ways to decrease the value of Q.
There are, however, practical limitations to minimizing RSS.
Precipitates that are extremely insoluble, such as Fe(OH) 3 and PbS, have
such small solubilities that a large RSS cannot be avoided. Such solutes
inevitably form small particles. In addition, conditions that yield a small
RSS may lead to a relatively stable supersaturated solution that requires a
long time to fully precipitate. For example, almost a month is required to
form a visible precipitate of BaSO4 under conditions in which the initial
RSS is 5.
An increase in the time required to form a visible precipitate under
conditions of low RSS is a consequence of both a slow rate of nucleation
and a steady decrease in RSS as the precipitate forms. One solution to the
latter problem is to chemically generate the precipitant in solution as the
product of a slow chemical reaction. This maintains the RSS at an
effectively constant level. The precipitate initially forms under conditions
of low RSS, leading to the nucleation of a limited number of particles. As
additional precipitant is created, nucleation is eventually superseded by
particle growth. This process is called homogeneous precipitation.
Homogeneous precipitation affords the dual advantages of
producing large particles of precipitate that are relatively free from
impurities. These advantages, however, may be offset by increasing the
time needed to produce the precipitate, and a tendency for the precipitate
to deposit as a thin film on the containers walls. The latter problem is
particularly severe for hydroxide precipitates generated using urea.
An additional method for increasing particle size deserves mention.
When a precipitates particles are electrically neutral, they tend to
coagulate into larger particles. Surface adsorption of excess lattice ions,
however, provides the precipitates particles with a net positive or
negative surface charge. Electrostatic repulsion between the particles
prevents them from coagulating into larger particles.

Figure 8.5 Schematic model of the solidsolution interface at a particle of

AgCl in a solution containing excess AgNO 3.
Consider, for instance, the precipitation of AgCl from a solution of
AgNO3, using NaCl as a precipitant. Early in the precipitation, when NaCl
is the limiting reagent, excess Ag + ions chemically adsorb to the AgCl
particles, forming a positively charged primary adsorption layer (Figure
8.5). Anions in solution, in this case NO3 and OH, are attracted toward
the surface, forming a negatively charged secondary adsorption layer that
balances the surfaces positive charge. The solution outside the secondary
adsorption layer remains electrically neutral. Coagulation cannot occur if
the secondary adsorption layer is too thick because the individual
particles of AgCl are unable to approach one another closely enough.
Coagulation can be induced in two ways: by increasing the
concentration of the ions responsible for the secondary adsorption layer or
by heating the solution. One way to induce coagulation is to add an inert
electrolyte, which increases the concentration of ions in the secondary
adsorption layer. With more ions available, the thickness of the secondary
absorption layer decreases. Particles of precipitate may now approach one
another more closely, allowing the precipitate to coagulate. The amount of
electrolyte needed to cause spontaneous coagulation is called the critical
coagulation concentration.
Heating the solution and precipitate provides a second way to
induce coagulation. As the temperature increases, the number of ions in
the primary adsorption layer decreases, lowering the precipitates surface
charge. In addition, increasing the particles kinetic energy may be
sufficient to overcome the electrostatic repulsion preventing coagulation
at lower temperatures.
(Harvey,2000:240-243)
DAFTAR PUSTAKA

Harvey, D. 2000. "Modern Analytical Chemistry". New York: The McGrawHill Companies, Inc.