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GRAVIMETRIC
ANALYSIS
By Dr Mark Selby
(from lecture slides developed by
D. Sharma, Department of Chemistry, Simon Fraser
University, British Columbia, Canada)
GRAVIMETRIC
ANALYSIS
Chapter 10 in Christian (7th Ed.) pages 342f.
CVB212 Industrial Analytical Chemistry 3
Gravimetric Analysis
Gravimetric analysis is the quantitative determination of
analyte concentration through a process of precipitation
of the analyte, isolation of the precipitate, and weighing
the isolated product.
Gravimetric Analysis
1. A weighed sample is dissolved
2. An excess of a precipitating agent is added to
this solution
3. The resulting precipitate is filtered, dried (or
ignited) and weighed
4. From the mass and known composition of the
precipitate, the amount of the original ion can
be determined
5. Stoichiometry is important (write down the
chemical equation!)
CVB212 Industrial Analytical Chemistry 5
Ag Cl AgCl (s )
Practical 1:
Determination of
Nickel in Steel
CVB212 Industrial Analytical Chemistry 9
Example: Ni in Steel
• To measure Ni in steel, the alloy is dissolved in 12 M HCl and
neutralised in the presence of citrate ion, which maintains iron in
solution.
• The slightly basic solution is warmed and dimethylglyoxime (DMG)
is added to precipitate the red DMG-nickel complex quantitatively.
• The product is filtered, washed with cold water, and dried at 110 °C.
Mechanism of Precipitation
• Induction period
• The time before nucleation occurs after the addition
of the precipitating agent to the solution
• May range from milliseconds to several minutes
• Nucleation
• Formation of small, stable aggregates or nuclei of
precipitate
• Nuclei have sizes down to ~1 nm, composed of a
few atoms, and there may be up to 1010 nuclei per
mole of analyte
• Excess ions from solution collect around the nuclei
CVB212 Industrial Analytical Chemistry 11
Mechanism of Precipitation
Silver nitrate is added very slowly to an acidic solution containing chloride. Silver
chloride nuclei form with a surface layer of ions. The “charged” AgCl particles
(or colloidal particles) repel each other.
Illustration of an Electrical
Loosely Double Layer
associated
counter ion
Nucleus of
AgCl(s) colloid
Homogeneous
solution (charges
balanced)
Mechanism of Precipitation
• In addition to the primary adsorbed silver ions, some nitrate
ions form an electrostatic layer around the nucleus.
• These counter ions 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.
• Counter ions are less tightly held than the primary adsorbed
ions and the counter ion layer is somewhat diffuse and
contains ions other than those of the counter ions.
• These layers of charged ions associated with the surface of
the nuclei are known as the electric double layer.
CVB212 Industrial Analytical Chemistry 13
More Terminology
• Adsorption is a process in which a substance
(gas, liquid, or solid) condenses onto the surface
of a solid
• The electric double layer of a colloid consists of
a layer of charge associated with the surface of
the particles and a layer with a net opposite
charge in the solution surrounding the particles
• A colloid is a finely divided particle (typically with
diameters from 10 nm to 1 m) that forms a stable
dispersion within a medium (air or liquid)
CVB212 Industrial Analytical Chemistry 14
Mechanism of Precipitation
Digestion
• Heating the precipitate within the mother liquor (or
solution from which it precipitated) for a certain period
of time to encourage densification of nuclei.
• During digestion, small particles dissolve and larger
ones grow (Ostwald ripening). This process helps
produce larger crystals that are more easily filtered
from solution
T
CVB212 Industrial Analytical Chemistry 15
Impurities in Precipitates
• Coprecipitation…
…is the precipitation of an unwanted species along
with your analyte of interest;
… occurs to some degree in every gravimetric
analysis;
• A major factor for precipitations of barium sulfate and those
involving hydrous oxides
Impurities in Precipitates
• Surface adsorption
• Unwanted material is
adsorbed onto the surface Scaling per Particle
of the precipitate 3
Particle Volume = 4/3(r )
• Digestion of a precipitate
2
Particle Surface Area = 4(r )
Impurities in Precipitates
• Occlusion
• A type of coprecipitation
in which impurities are
trapped within the growing
crystal
• Post-precipitation
– Sometimes a precipitate in contact with the mother liquor is
contaminated by the precipitation of an impurity
CVB212 Industrial Analytical Chemistry 22
Impurities in Precipitates
• Inclusion
• A type of coprecipitation in which
the impurities occupy the crystal
lattice sites
• Peptidization
• A procedure where the precipitate is
washed and filtered, but part of the AgCl (s) → AgCl (colloid)
precipitate reverts to the colloidal
form because supporting electrolyte
is gone.
• Cooling the system with an ice-
water bath minimizes loss of
precipitate due to dissolution
CVB212 Industrial Analytical Chemistry 23
Increasing Purity
• Re-precipitation
• a procedure including washing away the mother
liquor, redissolving the precipitate, and precipitating
the product again
• Drying the solid
• Generally the solids are dried at
~120 oC, but conditions for
drying can vary considerably.
CVB212 Industrial Analytical Chemistry 24
Increasing Purity
• Precipitation in the presence of electrolyte
• Coulombic repulsion is diminished in the presence of
electrolyte because of a compression of the volume
of the ionic atmosphere
• Digestion
• Raising the temperature will increase the collision
energy for colloidal particles and overcome
Coulombic repulsion, leading to formation of larger
particles (coalescence)
CVB212 Industrial Analytical Chemistry 25
Gravimetric Analysis
0.4368g
3.048 10 - 3 mol
143.321g/m ol
3
3.048 10 mol
Concentration of Cl
- 0.3048 M
0.01000 L
CVB212 Industrial Analytical Chemistry 27
Other Analytes
Christian 7th Ed., Table 10.1, page 353
Gravimetric Factor
In general the precipitate we weigh is usually in a different form
than the analyte whose weight we wish to report.
FW analyte (g/mol) a
GF (mol analyte/mol precipitate)
FW precipitate (g/mol) b
2/20/2015 Footer Text 29
Answer:
FW Bi 2S3 (g/mol) 1
g Bi 2S3 /g BaSO 4 = (mol Bi 2S3 / mol BaSO 4 )
FW BaSO 4 (g/mol) 3
514.15(g Bi 2S3 /mol) 1
GF = 0.73429 g Bi 2S3 /g BaSO 4
233.40(g BaSO 4 /mol) 3
CVB212 Industrial Analytical Chemistry 30
Sample Calculation
A certain barium halide exists as the hydrated salt BaX2.2H2O, where X is
the halogen.
Sample Calculation
The precipitate is barium sulfate. The first stage is to determine the
number of moles of barium sulfate produced, this will, in turn give us
the number of moles of barium in the original sample.
Sample Calculation
This is the number of moles of barium present in the precipitate and,
therefore, the number of moles of barium in the original sample. Given the
formula of the halide, (i.e., it contains one barium per formula unit), this
must also be the number of moles of the halide. From this information we
can deduce the relative molecular mass of the original halide salt:
Mr = mass / number of moles = 0.2650 (g) / 1.09 x 10-3 (mol)
= 244.18 (g/mol)
PQB313 Analytical Chemistry for Industry 33
Sample Calculation
The atomic mass (Ar) of 2 X will be given by the Ar of the whole salt – that of the
remaining components:
The Ar of chlorine is 35.45 (g/mol), which is in good agreement with the result
obtained and hence the halide salt is hydrated barium chloride and
X = Chlorine
Compare this example with the worked solution for RaCl2, in Harris 8th Ed., 674.