Chapter 4
Gravimetric Analysis
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Gravimetry
1. Directly: Determining its mass, or the mass of a compound
containing the analyte.
2. Indirectly: Measuring a change in mass due to its loss, or
the mass of a compound formed from the analyte.
Advantages:
3. Accurate & precise when using modern analytical balances.
4. Absolute method.
5. Carried out with relatively inexpensive apparatus.
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Its applications:
1. Analysis of standards w/c are to be used for testing and/or
calibration of instrumental techniques.
2. Analyses requiring high accuracy, although time-consuming.
Conservation of Mass:
Mass of analyte present in a sample be proportional to the
mass or change in mass serving as the analytical signal.
E.g, For the determination of the moisture content we have:
Sample’s initial mass – sample’s final mass = g H2O
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TERMINOLOGY:
Adsorbate: a coprecipitated impurity that adsorbs to the surface
of a precipitate.
Inclusion: a coprecipitated impurity in which the interfering ion
occupies a lattice site in the precipitate.
Occlusion: a coprecipitated impurity trapped within a precipitate.
Digestion: the process by which a precipitate is given time to
form larger, purer particles.
Precipitant: A reagent that causing precipitate of soluble species.
Nucleation: Initial union of small No of ions, atoms & molecules.
Particle Growth: 3-D growth of a particle into a larger crystal.
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Controlling Particle Size:
Precipitate’s particles determines the ease & success of filtration.
Smaller, colloidal particles (10-6 - 10-4 mm) are difficult to filter
because may not readily settle & readily pass through the
pores.
Large, crystalline particles (10-1 - 10 mm), however, settle
spontaneously and are easily filtered.
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Relative supersaturation (RSS):
A measure of extent to w/c a soln, or a localized region of soln,
contains more dissolved solute than that expected at equilibrium.
Can be expressed as: RSS = (Q-S)/S, where
Q = solute’s actual conc.
S = solute’s expected conc. at equilibrium
Q - S = measure of solute’s SS when precipitation begins.
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If RSS is large, nucleation is favored and colloidal suspensions
tend to be formed.
If RSS is small, particle growth will predominate resulting in
crystalline precipitates.
RSS can be minimized by:
Increasing S (elevate temp., PH control)
Decreasing Q (use dilute soln, slowly add reagents, stir the soln).
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Types of Gravimetry:
1. Precipitation gravimetry: Signal is the mass of a precipitate.
2. Volatilization gravimetry: Loss of a volatile species gives
rise to the signal.
3. Particulate gravimetry: Mass of a particulate analyte is
determined following its separation from its matrix.
4. Electrogravimetry: Signal is the mass of an electrodeposit
on the cathode or anode in an electrochemical cell.
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1. Precipitation Gravimetry:
Determination of Mg2+ in Water & Wastewater
Mg2+ is precipitated as MgNH4PO4 .6H2O using (NH4)2HPO4.
(NH4)2HPO4 is not very selective, so a preliminary separation of
Mg2+ from potential interferant (Ca2+) is necessary.
Ca2+ is usually removed by its prior precipitation as oxalate = (C2O4)2-.
Presence of excess NH4 -salts from the precipitant or addition of
too much NH3 can lead to the formation of Mg(NH4)4(PO4)2, w/c is
subsequently isolated as Mg(PO3)2 after drying.
Precipitate is isolated by filtration using rinse soln of dilute NH 3.
9 It is then converted to Mg2P2O7 and weighed.
Quantitative Applications:
Inorganic Analysis
The most important precipitants for inorganic cations are:
chromate, halides, OH-, oxalate, SO42- , S2- & phosphate.
Analy Precipita Precipitate Precipitate Weighed
te nt Formed
Ba2+ (NH4)2CrO4 BaCrO4 BaCrO4
Pb2+ K2CrO4 PbCrO4 PbCrO4
Al3+ NH3 Al(OH)3 Al2O3
Be2+ NH3 Be(OH)2 BeO
Fe3+ NH3 Fe(OH)3 Fe2O3
Ca2+ (NH4)2C2O4 CaC2O4 CaCO3 or CaO
Sb3+ H2S Sb2S3 Sb2S3
Hg2+ H2S HgS HgS
10 Ba2+ H2SO4 BaSO4 BaSO4
Analyte Precipitant Precipitate formed Precipitate weighed
CN- AgNO3 AgCN AgCN
Br- AgNO3 AgBr AgBr
ClO3- FeSO4/AgNO3 AgCl AgCl
SCN- SO2/CuSO4 CuSCN CuSCN
SO42- BaCl2 BaSO4 BaSO4
The majority of inorganic precipitants show poor selectivity.
Most organic precipitants, however, are selective.
E.g., Ni2+ is precipitated by dimethylglyoxime, whereas Co2+ is
precipitated by 1-nitroso -2-naphthol
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Organic Analysis
Several organic functional groups or heteroatoms can be
determined using gravimetric precipitation methods;
E.g., Organic halides are oxidized by HNO3 and precipitated by
AgNO3. Organic sulfur is oxidized by HNO3 and precipitated by
BaCl2.
Quantitative Calculations:
Gravimetric Factor (GF) = g of analyte/g of precipitate.
GF = (fwt of analyte/fwt of ppt)x(n of analyte/n of ppt)
GF = wt of analyte/wt of ppt.
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2. Volatilization Gravimetry:
i. Volatile products may be trapped & weighed.
ii. Residue remaining may be weighed.
Determination of Si in Ores and Alloys:
Dissolving the sample in acid & dehydration of the soln
precipitates silicon as SiO2.
Treating the solid residue with HF results in volatile SiF4.
The decrease in mass following the loss of SiF4 provides an
indirect measure of the amount of silicon in the original sample.
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3. Particulate Gravimetry:
Applicable if the analyte is already present in a form that may
be readily separated from its liquid, gas, or solid matrix.
2 approaches to separate the analyte from its matrix:
Filtration.
Liquid-phase or solid-phase extraction.
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4. Electrogravimetry:
If the analyte’s oxidation/reduction leads to its deposition on
working electrode, it may be possible to determine the
analyte’s mass.
The working electrode is weighed before beginning the
electrolysis and reweighed when electrolysis is complete.
The difference gives the analyte’s mass.
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Thanks!!!
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