Types of Gravimetric Methods of Analysis
Gravimetric Methods of Analysis are of following types
Particulate gravimetry
Precipitation gravimetry
Volatilization gravimetry
Electrogravimetry
In particulate gravimetry the analyte
is determined following its removal from the sample Particulate gravimetry:
matrix by filtration or extraction. The determination A gravimetric method in which
of suspended solids from water released from a the mass of a particulate analyte
sewage-treatment facility is one example of
is determined following its
particulate gravimetry.
separation from its matrix.
When the signal is the mass of a precipitate,
we call the method precipitation gravimetry. The
indirect determination of PO33– by precipitating Precipitation gravimetry:
Hg2Cl2 is a representative example as phosphite, A gravimetric method in which
PO33–, reduces Hg2+ to Hg22+, so in the presence of the signal is the mass of a
Cl– a solid precipitate of Hg2Cl2 forms. The direct precipitate.
determination of Cl– by precipitating AgCl is the
example of direct determination of precipitate.
When thermal or chemical energy is used to Volatilization gravimetry:
remove a volatile species, we call the method A gravimetric method in which
volatilization gravimetry. In determining the moisture the loss of a volatile species
content of food, thermal energy vaporizes the H2O. gives rise to the signal.
The amount of carbon in an organic compound may
be determined by using the chemical energy of
combustion to convert C to CO2. Electrogravimetry:
Finally, in electrogravimetry the analyte is A gravimetric method in which
deposited as a solid film on one electrode in an the signal is the mass of an
electrochemical cell. The oxidation of Pb2+ and its electrodeposit on the cathode or
deposition as PbO2 on a Pt anode is one example of anode in an electrochemical
electrogravimetry. Reduction also may be used in cell.
electrogravimetry. The electrodeposition of Cu on a
Pt cathode, for example, provides a direct analysis for Cu2+.
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Precipitation Gravimetry
In the majority of cases; gravimetric methods rely on the use of precipitation reactions.
The quantitative determination of a substance by the precipitation method of gravimetric
analysis involves isolation of an ion in solution by a precipitation reaction (which causes
the formation of insoluble compound following the addition of precipitating reagent
called “precipitant”). Once the precipitates are formed; these are filtered, washed to make
them free from contaminants, converted to a product of known composition and finally
weighed to determine its mass by difference. From the mass and known composition of
the precipitate, the amount of the original ion can be determined.
Many metallic elements in their ionic forms react with negative counter ions to
produce stable precipitates. Silver ions form stable and highly insoluble salts with
chloride, bromide or iodide.
Determination of Calcium form natural water involves the formation of precipitates with
oxalate ion
Barium precipitates quantitatively as the sulfate. The reactions often follow the same
patterns i.e. positive and negative ions in an aqueous solution produce highly insoluble
precipitates with certain added reagents.
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.
Procedure to carry out precipitation
1. Weigh the sample to be analysed.
2. Dissolve the sample in a suitable solvent, eg, water.
3. Add an excess of the precipiating agent to the solution to precipitate the analyte.
4. Heat the solution on a hot plate to increase the particle size for easier filtering (optional).
This is usually referred to as digestion.
5. Filter the mixture to separate the precipitate from the solution. It is important that the
precipitate is quantitatively transferred to the filter. If any remains in the beaker, the mass
obtained will be inaccurate.
6. Wash the precipitate to remove any impurities and dry by heating to remove water.
7. Cool the precipitate in a dessicator to prevent the precipitate absorbing moisture from the
air.
8. Weigh the cooled precipitate.
9. Repeat the drying and weighing process until a constant mass for the precipitate is
achieved.
10. Calculate the percent by mass of analyte in the sample.
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Properties of Precipitates and Precipitants
Precipitates
1. Must be in the state so that readily filtered and washed free of contaminants.
2. Of sufficiently low solubility so that no significant loss of the analyte occurs
during filtration and washing.
3. Unreactive with constituents of the atmosphere.
4. Of known composition after it is dried or, if necessary, ignited.
Precipitants
Specific (rare): react only with a single chemical species.
As Dimethylglyoxime (DMG) is used for Ni2+
2 DMG + Ni2+ Ni(DMG)2(s) + 2 H+
Selective (common): react with a limited number of species.
As AgNO3 can be used for Cl-, Br-, I- & SCN-
Ag+ + X- → AgX, (X= Cl, Br, I, F)
The determinations involving the use of AgNO3 solution are referred as
“Argentometry” or “Argentrimetry”.
Calculation steps to solve the Problems related to find out percentage of Analyte
1) Write the balanced chemical equation for the precipitation reaction.
2) Calculate the moles of precipitate- (moles = mass ÷ molecular mass).
3) Calculate moles of analyte from the balanced chemical equation using the
mole ratio of analyte : precipitate
4) Calculate mass of analyte- (mass = moles x molecular mass)
5) Calculate percent by mass of analyte in sample (mass analyte ÷ mass sample)
x 100
Sources of Error
1) Incomplete precipitation results in a value for the percentage of analyte in the
sample that is too low.
2) Incomplete drying of the sample results in a value for the percentage of analyte in
the sample that is too high.
3) Other ions in the sample may also be precipitated resulting in a value for the
percentage of analyte in the sample that is too high.
Example (Problem)
2.00g sample of limestone was dissolved in hydrochloric acid and all the calcium
present in the sample was converted to Ca2+(aq). Excess ammonium oxalate solution,
(NH4)2C2O4(aq) was added to the solution to precipitate the calcium ions as calcium
oxalate, CaC2O4(s). The precipitate was filtered, dried and weighed to a constant mass of
2.43g. Determine the percentage by mass of calcium in the limestone sample.
(Molecular weight of CaC2O4 = 128.04)
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Data : Mass of Sample = 2.0 g
Mass of precipitate = 2.43 g
Percent mass of analyte =?
Solution
1. Write the balanced chemical equation for the precipitation reaction:
Ca2+(aq) + C2O42-(aq) → CaC2O4(s)
2. Calculate the moles (n) of calcium oxalate precipitated.
n (CaC2O4(s)) = given mass ÷ molecular mass
n(CaC2O4(s)) = 2.43 ÷ 128.04
n (CaC2O4(s)) = 0.019 moles
3. Find the moles of Ca2+(aq).
From the balanced chemical equation, the mole ratio of Ca2+ : CaC2O4(s) is 1 : 1
So, n(Ca2+(aq)) = n(CaC2O4(s)) = 0.019 moles
4. Calculate the mass of calcium in grams
mass (Ca) = n x molecular weight
mass (Ca) = 0.019 x 40.08 = 0.76g
5. Calculate the percentage by mass of calcium in the original sample:
% Ca = (mass of analyte ÷ mass sample) x 100
% Ca = (0.76 ÷ 2.00) x 100 = 38%
Example: Analysis of chloride
When mass of sample of unknown chloride after drying is 0.0984 g and mass of
AgCl precipitate is 0.2290 g, so percentage by mass of Cl- in the given solution of
becomes 57.57%.
If Pb2+ had been used to precipitate the chloride, the calculation would need to be
modified to account for the fact that each mole of PbCl2 contains two moles of chloride.
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Marie Curie's Measurement of the Atomic Mass of Radium
As part of her Ph.D. research (Radioactive Substances, 1903), Marie Curie measured the atomic
mass of radium, a new, radioactive element that she discovered. She knew that radium is in the
same family as barium, so the formula of radium chloride is RaCl2. In one experiment, 0.091 92 g
of pure RaCl2 was dissolved and treated with excess AgN03 to precipitate 0.088 90 g of AgCl.
How many moles of CI were in the RaCI2? From this measurement, find the atomic mass of Ra.
Marie Curie, Pierre Curie and Henri Becquerel shared the Nobel Prize in physics in 1903
for pioneering investigations of radioactivity. The Curies needed 4 years to isolate 100 mg
of RaCl2 from several tons of ore. Marie received the Nobel Prize in chemistry in 1911 for
her isolation of metallic radium. Linus Pauling, John Bardeen, and Frederick Sanger are
the only others who received two Nobel Prizes.
Exercise:
1. When a sample of impure KCl (0.415g) was dissolved in water and treated
with an excess of AgNo3, 0.8402 g of AgCl was precipitated. Calculate the
percentage of KCl in original sample.
Suggested Books
1. Modern Analytical Chemistry by David Harvey
2. Quantitative Chemical Analysis by Daniel C. Harris (7th Edition)
3. Analytical Chemistry by G.D. Christian
