ANALISIS GRAVIMETRI

Djadjat Tisnadjaja

Theodore W. Richards (1868 - 1928) and his

graduate students at Harvard developed or refined
many of the techniques of gravimetric analysis of
silver and chlorin
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 Introduction
• Gravimetric analysis describes a set of methods in analytical chemistry for
the quantitative determination of an analyte based on the mass of a solid. A
simple example is the measurement of solids suspended in a water sample:
A known volume of water is filtered, and the collected solids are weighed.
• In most cases, the analyte must first be converted to a solid by
precipitation with an appropriate reagent. The precipitate can then be
collected by filtration, washed, dried to remove traces of moisture from the
solution, and weighed. The amount of analyte in the original sample can
then be calculated from the mass of the precipitate and its chemical
composition.
• In other cases, it may be easier to remove the analyte by vaporization. The
analyte might be collected -- perhaps in a cryogenic trap or on some
absorbent material such as activated carbon -- and measured directly. Or,
the sample can be weighed before and after it is dried; the difference
between the two masses gives the mass of analyte lost. This is especially
useful in determining the water content of complex materials such as
foodstuffs.
• Gravimetric analysis, which by definition is based upon the measurement of
mass, can be generalized into two types; precipitation and volatilization.

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 Introduction, continue
• The quantitative determination of a substance by the precipitation method of
gravimetric analysis involves isolation of an ion in solution by a precipitation
reaction, filtering, washing the precipitate free of contaminants, conversion
of the precipitate to a product of known composition, and finally weighing
the precipitate and determining its mass by difference. From the mass and
known composition of the precipitate, the amount of the original ion can be
determined.
• For successful determinations the desired substance must be completely
precipitated.
• In example, when Cl- is precipitated out by addition of Ag+
Ag+ + Cl- AgCl(s)
• The (low) solubility of AgCl is reduced still further by the excess of Ag+
which is added, pushing the equilibrium to the right. We can further
decrease the solubility by decreasing the temperature of the solution by
using an ice bath. The weighed form of the product should be of known
composition. The product should be "pure" and easily filtered.
• It is usually difficult to obtain a product which is "pure" , but careful
precipitation and sufficient washing helps reduce the level of impurity.

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 Mechanism of Precipitation
• After the addition of the precipitating agent to the solution of the ion under
analysis there is an initial induction period before nucleation occurs. This
induction period may range from a very short time period to one which is
relatively long, ranging from almost instantaneous to several minutes.
• After induction, nucleation occurs, here small aggregates or nuclei of
atoms form and it is from these "clumps" of atoms that the crystals started
to grow. As these nuclei form ions from the solution (which at this point are
in excess) congregate around them .
• For example if hydrochloric acid were added very slowly to a solution of
silver nitrate, silver chloride nuclei would form and silver ions (which would
be in excess relative to Cl- ions) would congregate around them.
• In addition to the primary adsorbed silver ion, there are some nitrate ions
aggregating further from the AgCl nucleus. These are counter ions and
tend to aggregate around the [AgCl:Ag]+ center because these centers have
a net positive charge (excess Ag+) and additional negative charge is
required to maintain electrical neutrality.

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Growth of larger nuclei or crystallites can be encouraged by digestion,
a process which involves heating the solid and mother liquor for a
certain period of time. During digestion, small particles dissolve and
larger ones grow. Digestion of the product is an important practical
process and you will find that most if not all gravimetric analysis involve
a digestion period.

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 Conditions for analytical precipitation
• In an ideal world, an analytical precipitate for gravimetric
analysis should consist of perfect crystals large enough
to be easily washed and filtered. The perfect crystal
would be free from impurities and be large enough so
that it presented a minimum surface area onto which
foreign ions could be adsorbed. The precipitate should
also be "insoluble" (i.e. be of such slight solubility that
loses from dissolution would be minimal).
• Without going into detail, it has been shown (Von
Weimarn) that the particle size of precipitates is inversely
proportional to the relative supersaturation of the solution
during precipitation;
• relative supersaturation = (Q-S)/S
• For the best possible results, conditions need to be
adjusted such that Q will be as low as possible and S will
be relatively large.
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 Coprecipitation
• This is anything unwanted which precipitates with the thing
you do want. Coprecipitation occurs to some degree in every
gravimetric analysis (especially barium sulfate and those
involving hydrous oxides). You cannot avoid it - all you can do
is minimize it by careful precipitation and thorough washing.

Surface adsorption
• Here unwanted material is adsorbed onto the surface of the
precipitate. Digestion of a precipitate reduces the amount of
surface area and hence the area available for surface
adsorption. Washing can also remove surface material.

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 PROCEDURE
• The sample is dissolved, if it is not already insoluble.
• The solution may be treated to adjust the pH (so that the proper
precipitate is formed, or to suppress the formation of other
precipitates). If it is known that species are present which interfere
(by also forming precipitates under the same conditions as the
analyte), the sample might require treatment with a different
reagent to remove these interference.
• The precipitating reagent is added at a concentration that favors
the formation of a "good" precipitate. This may require low
concentration, extensive heating, or careful control of the pH.
• After the precipitate has formed, the solution is carefully filtered.
The filter is chosen to trap the precipitate; smaller particles are
more difficult to filter.
• After the solution has been filtered, it should be tested to make
sure that the analyte has been completely precipitated. This is
easily done by adding a few drops of the precipitating reagent; if a
precipitate is observed, the precipitation is incomplete.

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 Procedure, continue

• After filtration, the precipitate – including the filter paper or

crucible – is heated. Here, the remaining moisture is removed
(drying), and the precipitate is converted to a more stable form. To
avoid in-accuracy caused by filter paper, normally an ashless filter
paper is used.
• After the precipitate is allowed to cool (preferably in a desiccator
to keep it from absorbing moisture), it is weighed (in the crucible).
• Since the composition of the precipitate is known, it is simple to
calculate the mass of analyte in the original sample.

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 Advantages
• Gravimetric analysis, if methods are followed carefully,
provides for exceedingly precise analysis. In fact,
gravimetric analysis was used to determine the atomic
masses of many elements to six figure accuracy.
Gravimetry provides very little room for instrumental
error and does not require a series of standards for
calculation of an unknown. Also, methods often do not
require expensive equipment. Gravimetric analysis, due
to its high degree of accuracy, when performed correctly,
can also be used to calibrate other instruments in lieu of
reference standards.

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 Disadvantages
• Gravimetric analysis usually only provides for the
analysis of a single element, or a limited group of
elements, at a time. Comparing modern dynamic flash
combustion coupled with gas chromatography with
traditional combustion analysis will show that the former
is both faster and allows for simultaneous determination
of multiple elements while traditional determination
allowed only for the determination of carbon and
hydrogen. Methods are often convoluted and a slight
mis-step in a procedure can often mean disaster for the
analysis (colloid formation in precipitation gravimetry, for
example). Compare this with hardy methods such as
spectrophotometry and one will find that analysis by
these methods is much more efficient.

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 Worked Example
• A certain barium halide exists as the hydrated salt
BaX2.2H2O, where X is the halogen. The barium content
of the salt can be determined by gravimetric methods. A
sample of the halide (0.2650 g) was dissolved in water
(200 cm3) and excess sulfuric acid added. The mixture
was then heated and held at boiling for 45 minutes. The
precipitate (barium sulfate) was filtered off, washed and
dried. Mass of precipitate obtained = 0.2533 g.
Determine the identity of X.

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