Henry Su December 12, 2001

Chapter Notes Chemistry 221

Chapter 8 Dr. Rahni

Gravimetric Methods of Analysis

-Gravimetric methods of analysis are based on the measurement of mass
-Two major types of gravimetric methods
-Precipitation Methods
-Analyte is converted into sparingly soluble precipitate
-Precipitate is then filtered, washed free of impurities, and converted to a
product of known composition by suitable heat treatment, and the product
is weighed
-Volatilization Methods
-The analyte or its decomposition products are volatilized at a suitable
temperature
-The volatile product is then collected and weighed
8A—Properties of precipitates and Precipitating Agents
-Ideally, a gravimetric precipitating agent should react specifically or at least selectively
with the analyte
-Specific reagents(rare) react only with a single chemical species
-Selective reagents(more common) react with only a limited number of species
-Characteristics of Ideal Precipitating Reagents
1-Readily filtered and washed free of contaminants
2-Of sufficiently low solubility so that no significant loss of the solid occurs
during filtration and washing
3-Unreactive with constituents in the atmosphere
4-Of known composition after it is dried or ignited
-8A-1 Particle Size and Filterability of Precipitates
-Precipitates made up of large particles are generally desirable in gravimetric
analysis because large particles are easier to filter and wash free of impurities.
Also, they are usually purer than precipitates made up of finer particles
-What Factors Determine Particle Size?
-Colloidal suspensions 1e-7 to 1e-4 cm in diameter
-No tendency to settle from solution, not easily filtered
-Crystalline suspension > 1/10 mm in diameter
-Settle spontaneously and readily filtered
-Particle size is influenced by precipitate solubility, temperature, reactant
concentrations, and the rate at which reactants are mixed

Relative supersaturation = Q – S large---colloidal

S small---crystalline
Q-conc. Of the solute at any instant
S-solubility at equilibrium
 -How Do Precipitates Form?
-Nucleation is a process in which a minimum number of atoms, ions, or
molecules join together to form a stable solid
-Precipitates form by nucleation and particle growth
-If nucleation predominates, a large number of small particles result
-If particle growth predominates, a smaller number of large particles result
-Controlling Particle Size
-Temperature elevation can increase solubility of the precipitate
-Larger particles can be obtained by pH control
-8A-2 Colloidal Precipitates
-Individual colloidal particles are so small that they are not retained by ordinary
filters and Brownian motion prevents settling
-Coagulation of Colloids
-Coagulation can be hastened by heating, stirring, and adding an
electrolyte to the medium.
-Colloidal suspensions are stable because all the particles present are
either positively or negatively charged
-Adsorption is a process in which a substance is held on the surface of a
solid
-Absorption involves retention of a substance within the pores of a solid
-The charge on a colloidal particle formed in a gravimetric analysis is
determined by the charge of the lattice ion that is in excess when the
precipitation is complete
-Peptization of Colloids
-Peptization is a process by which a coagulated colloid returns to its
dispersed state
-Occurs when a coagulated colloid is washed
-Treatment of Colloidal Precipitates
-Colloids are best precipitated from hot, stirred solutions containing
sufficient electrolyte to ensure coagulation
-Digestion is a process in which a precipitate is heated for an hour or more
in the solution from which it is formed
-8A-3 Crystalline Precipitates
-Crystalline precipitates are generally more easily filtered and purified than
coagulated colloids
-Improving Particle Size and Filterability
-The particle size and filterability of crystalline solids can be improved by
minimizing Q and/or maximizing S
-Digestion improves the purity and filterability of crystalline solids
-8A-4 Coprecipitation
-Coprecipitation is a process in which normally soluble compounds are carried
out of solution by a precipitate
1-Surface Adsorption
-Major source of contamination in coagulated colloids, but is of no
significance in crystalline precipitates
2-Mixed-Crystal Contamination
-Type of coprecipitation in which a contaminant ion replaces an ion in the
lattice of a crystal
3-Occlusion and Mechanical Entrapment
-Compound is trapped within a pocket formed during rapid crystal growth
4-Coprecipitation Errors
-Coprecipitation can cause either positive or negative errors
-8A-5 Precipitation from Homogeneous Solution
-Homogeneous precipitation is a process in which a precipitate is formed by slow
generation of a precipitating reagent homogeneously throughout a solution
-Solids formed by homogeneous precipitation are generally purer and more easily
filtered than precipitates generated by direct addition of a reagent to the analyte
solution
8B—Drying and Ignition of Precipitates
-After filtration, a gravimetric precipitate is heated until its mass is constant(weighing
form)
-The temperature required to dehydrate a precipitate may be as low as 100°C or as high
as 1000°C
-Recording thermal decomposition curves is often called thermogravimetry or thermal
gravimetric analysis, and the mass vs. temp. curves generated are called thermograms

8C—Calculating Results from Gravimetric Data

-The results of a gravimetric analysis are generally computed from two experimental
measurements
1-The mass of the sample
2-The mass of a product of known composition
Example: The calcium in a 200 mL sample of a natural water was determined by precipitating the cation as
CaC2O4. The precipitate was filtered, washed, and ignited in a crucible with empty mass of 26.6002 g. The
mass of the crucible and CaO(56.099 g/mol) was 26.7134 g. Calculate the concentration of Ca(40.078
g/mol) in the water in units of grams per 100 mL.
The mass of CaO is
26.7134 g –26.6002 g = 0.1132 g
The number of moles Ca in the sample is equal to the number of moles CaO

Amount Ca = 0.1132 g CaO x 1mol CaO x 1 mol Ca = 2.0168e-3 mol Ca

56.077 g mol CaO

Mass Ca/100mL = 2.0186e-3 x 40.078 g Ca/mol Ca x 100 mL = 0.04045 g/ 100ml

200 ml sample
8D—Applications of Gravimetric Methods
1-Inorganic Precipitating Agents
2-Reducing Agents
3-Organic Precipitating Agents
4-Organic Functional Group Analysis
5-Volatilization Methods