GRAVIMETRIC ANALYSIS
Kim Anh NGUYEN, BPharm, PhD
[email protected] April 2025
LEARNING OBJECTIVES
• Describe gravimetric methods
• Explain a gravimetric analysis procedure
• Know how to calculate results from gravimetric data
• Explain factors to be considered in order to obtain
quantitative results in precipitation gravimetry
2
OUTLINE
• Gravimetric analysis
• Volatilization gravimetry
• Precipitation gravimetry
• Exercises
3
GRAVIMETRIC ANALYSIS (GRAVIMETRY)
Quantitative method based on mass measurements
The oldest quantitative analytical technique
Theodore W. Richards Marie Curie
Nobel Prize in Chemistry 1914 Nobel Prize in Chemistry 1911
accurate determinations of the discovery of radium and polonium,
atomic weight of 25 elements isolation and study of the nature
and compounds of radium 4
GRAVIMETRIC ANALYSIS (GRAVIMETRY)
Separation Weight Concentration
(mass)
• Precipitation Gravimetry The analyte is separated from a sample as
a precipitate
• Volatilization Gravimetry The analyte is separated from a sample by
converting it to a gas
• Electrogravimetry The analyte is separated by an electrical
current.
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VOLATILIZATION GRAVIMETRY
Thermogravimetric method Moisture Content Analysis
The loss of mass observed when the sample is heated
This method does not distinguish weight loss of water from loss of
volatile components or sample decomposition
Moisture analyzer
(Moisture balance)
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VOLATILIZATION GRAVIMETRY
Thermogravimetric method
mg
mg
mg
Thermogram for CaC2O4•H2O obtained by heating a sample from
room temperature to 1000 oC at a rate of 20 oC/min. 7
VOLATILIZATION GRAVIMETRY
Thermogravimetric method
For each step in the thermogram, identify the volatilization product and
the solid residue that remains
• From 100–200 oC:
The sample loses 2.17 mg 12.3% of the original
mass a decrease in the molar mass of 18 g/mol
loss of H2O
• From 400–550 oC:
The sample loses 3.38 mg 19.2% of the original
mass a decrease in the molar mass of 28 g/mol
loss of CO
• From 600–800 oC:
The sample loses 5.30 mg 30.1% of the original
mass a decrease in the molar mass of 44 g/mol
loss of CO2 8
VOLATILIZATION GRAVIMETRY
Volatilization of carbon dioxide
Example: determination of the sodium hydrogen carbonate content of
antacid tablets
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
1. Preparation of the solution
2. Precipitation
3. Digestion
4. Filtration
5. Washing
6. Drying or igniting
7. Weighing
8. Calculation
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
1. Preparation of the solution
Factors that must be considered:
- Volume of the solution
- Concentration of the test substance
- The presence and concentrations of other constituents
- Temperature
- pH
- …
solubility
interfering materials
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
2. Precipitation (addition of a precipitating agent/precipitant)
Properties of precipitants: specific or selective
- Specific agents: react only with a single chemical species
- Selective agents: react with a limited number of species
AgNO3: precipitates Cl-, Br-, I-, and SCN- (acidic conditions)
Interfering ions
Dimethylglyoxime: precipitates only Ni2+ (alkaline conditions)
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Inorganic precipitants
(for analyzing inorganic cations / anions)
Analyte Precipitant Precipitate formed Weighing form
Ag+ HCl AgCl AgCl
Cl- AgNO3 AgCl AgCl
Br- AgNO3 AgBr AgBr
I- AgNO3 AgI AgI
SO42- BaCl2 BaSO4 BaSO4
Ba2+ H2SO4 BaSO4 BaSO4
Pb2+ H2SO4 PbSO4 PbSO4
Ca2+ H2C2O4 CaC2O4 CaO
Mg2+ (NH4)2HPO4 NH4MgPO4 Mg2P2O7
PO43- MgCl2, NH4Cl NH4MgPO4 Mg2P2O7
Al3+ NH4OH Al(OH)3 Al2O3
Fe3+ NH4OH Fe(OH)3 Fe2O3
Organic precipitants
(for analyzing inorganic cations)
Analyte Precipitant
Mg2+ 8-Hydroxyquinoline
Ni2+ Dimethylglyoxime
K+ or NH4+ Sodium
tetraphenylborate
PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
2. Precipitation Check for completeness of precipitation
Add a slight excess (~10%) of precipitating reagent to decrease the
solubility (common ion effect) and to assure complete precipitation.
Avoid a large excess of precipitating agent (adsorption on the surface
of the precipitate/dissolution).
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
2. Precipitation
Properties of precipitates:
- low solubility (minimize loss during filtration and washing)
- unreactive with constituents of the atmosphere
- known chemical composition
- large crystals (easily filtered and minimize contamination
and redissolution)
Crystalline precipitate Colloidal precipitate 16
PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
2. Precipitation
Supersaturated solution: contains a higher solute concentration
than a saturated solution.
High relative supersaturation → many small crystals
Low relative supersaturation → fewer, larger crystals
𝑄−𝑆 Q: concentration of the solute
S: solubility
𝑆
• Larger surface area → more impurities adsorbed
• Competition between additional nucleation and particle growth
• Increased growth rate → more imperfections in the crystal → more
trapped impurities 17
PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
2. Precipitation
How to minimize supersaturation?
• Precipitate from dilute solution
• Add dilute precipitating reagents slowly, with stirring
• Precipitate from hot solution (increase solubility), then the solution
may be cooled to make the precipitation quantitative
• Control the pH (increase solubility and slow the rate of precipitation)
Precipitates that have very low solubilities
(Q>>S) generally form as colloids 18
PRECIPITATION GRAVIMETRY
Adsorption
Colloidal particles are very small (1 to 100 nm) and have a very
large surface area, which promotes surface adsorption
electric double layer
The surface tends to adsorb the
ion of the precipitate particle
that is in excess in the solution
Colloidal particles are charged and thus repel one another
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PRECIPITATION GRAVIMETRY
Coprecipitation: otherwise soluble compounds are removed from
solution during precipitation impurities in the precipitate
• Surface Adsorption
How to remove? Errors
Washing / Digestion
• Occlusion and Inclusion
Ions (similar size and charge) are trapped within the crystal lattice
Material that is not part of the crystal structure is trapped within a crystal
How to remove?
Washing: ineffective
Digestion: not completely effective
Reprecipitation
Removal of interfering ion before precipitation
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
3. Digestion (Ostwald ripening)
A process in which a precipitate is heated without stirring in the
solution from which it was formed (the mother liquor) and allowed
to stand in contact with the solution.
dissolution recrystallization
• Small particles dissolve and recrystallize on the surface of large particles
• Bridging between adjacent particles
• Release of trapped impurities and weakly bound water
Improves the purity and filterability of the precipitate
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
4. Filtration
If the particles collect together to form larger ones
Coagulation filterable, amorphous mass
How to coagulate colloidal particles:
• Heating
• Stirring
• Increasing the electrolyte concentration
decrease the volume of the counter-ion layer
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
5. Washing Test for completeness of washing
Washing the particles with water
Loss of the secondary layer
The particles revert to the colloidal state (peptization)
How to avoid peptization:
• Wash the precipitate with a solution containing an electrolyte
that can be removed during the drying step.
Example: silver chloride is usually washed with a dilute solution of
nitric acid (volatilized when dried at 110 oC)
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
6. Drying or igniting
• Drying: removal of the volatiles (solvent and electrolyte) until
its mass becomes constant Usually 110 to 120 oC for 1 - 2 h
• Ignition: conversion of the precipitate to a more suitable form
for weighing at a much higher temperature
MgNH4PO4 is decomposed to the pyrophosphate, Mg2P2O7, by heating at 900 oC
Mass
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
7. Weighing
8. Calculation
Mass of the weighing form Mass of the analyte
(concentration)
Stoichiometry: Mole-Mass Relationships in Chemical Reactions
Example: The calcium in a 200.0-mL sample of a natural water was
determined by precipitating the cation as CaC2O4. The precipitate was
filtered, washed, and ignited. The mass of CaO (56.077 g/mol) was 0.1132 g.
Calculate the concentration (% or grams per 100 mL) of Ca (40.078 g/mol) in
the water sample.
The number of moles of Ca2+ in the sample = the number of moles of CaO
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PRECIPITATION GRAVIMETRY
Procedure for gravimetric analysis
7. Weighing
8. Calculation
Gravimetric factor (GF) the weight of analyte per unit weight of weighing form
𝑚𝑎𝑛𝑎𝑙𝑦𝑡𝑒 = 𝑚𝑤𝑒𝑖𝑔ℎ𝑖𝑛𝑔 𝑓𝑜𝑟𝑚 × GF
molar massanalyte 𝑚𝑜𝑙𝑎𝑛𝑎𝑙𝑦𝑡𝑒
GF = ×
molar massweighing form 𝑚𝑜𝑙𝑤𝑒𝑖𝑔ℎ𝑖𝑛𝑔 𝑓𝑜𝑟𝑚
Example: calculate the GF for the conversion of Bi2S3 to BaSO4
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GRAVIMETRIC ANALYSIS
Advantages
• Precise analysis
• Standards for calculation are not necessary
• Simple equipment
Disadvantages
• Tedious (requires careful manipulation) and time consuming
• Interfering species, impurities
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EXERCISES
Precipitation gravimetry
In her PhD research, Marie Curie measured the atomic mass of the
element radium. When 0.09192 g of the pure RaCl2 was dissolved and
treated with excess AgNO3, 0.08890 g of AgCl precipitated. Find the
atomic mass of radium.
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Precipitation gravimetry
The aluminum content of an alloy is determined gravimetrically by
precipitating it with 8-hydroxyquinoline to give Al(C9H6ON)3. If a
1.021 g sample yielded 0.1862 g of precipitate. What is the percent
aluminum in the alloy?
Precipitation gravimetry
The aluminum in a 1.200 g sample of impure ammonium aluminum
sulfate was precipitated with aqueous ammonia as the hydrous
Al2O3 · xH2O. The precipitate was filtered and ignited at 1000°C to
give anhydrous Al2O3, which weighed 0.2001 g. Express the result of
this analysis in terms of % NH4Al(SO4)2.
Precipitate mixtures
A mixture containing only BaO and CaO weighs 2.00 g. The oxides
are converted to the corresponding mixed sulfates, which weigh
4.00 g. Calculate the percent Ba and Ca in the original mixture.
Volatilization gravimetry
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.
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