II.

GRAVIMETRIC METHODS
A. Types of Gravimetric Methods
B. Steps in Gravimetric Precipitation
C. Applications
D. The Gravimetric Factor
GRAVIMETRY Any method in which the signal
is mass or change in mass.

Precipitation Gravimetry signal = mass of a precipitate

signal = mass of an electrodeposit

Electrogravimetry
on the cathode or anode in an
electrochemical cell

Volatilization Gravimetry signal = loss of a volatile species

mass of a sample is measured over

Thermogravimetry
time as the temperature changes
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 Volatilization Gravimetry
• thermal or chemical energy is used to remove a volatile species
• the two most common gravimetric methods using volatilization
are those for H2O and CO2 (combustion analysis)

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Steps in Gravimetric Precipitation
1. Weighing of sample

2. Dissolution of sample

4
Steps in Gravimetric Precipitation
3. Precipitation of the analyte
Analyte + Precipitating Agent → Precipitate

should react specifically or

at least selectively

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 Steps in Gravimetric Precipitation
3. Precipitation of the analyte
Analyte + Precipitating Agent → Precipitate

• low solubility
• easily filtered and washed free of contaminants
• unreactive with constituents of the atmosphere
• known chemical composition after it is dried or
ignited
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 Homogeneous precipitation

• A precipitation in which the precipitant is

generated in situ by a chemical reaction.

• Results in marked increased in crystal size

as well as improvements in purity.

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 Steps in Gravimetric Precipitation
3. Precipitation of the analyte
Analyte + Precipitating Agent → Precipitate

LARGE PARTICLES

 easy to filter & wash

 usually free of contaminants

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 Mechanism of precipitate formation

Colloidal particles Crystalline particles

HIGH RS low RS
Nucleation Particle growth

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 Practical treatment of colloidal particles

4. Digestion

Digestion
• precipitate is heated in the
mother liquor and allowed
to stand in contact with the
solution.

Mother liquor
• solution from which a
precipitate was formed.
Awesome timelapse of aspirin crystallization
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https://www.youtube.com/watch?v=OkXenH6SSu0
 Practical treatment of colloidal particles

Peptization Coagulation
Agglomeration
Flocculation
↑ temperature
+ electrolyte

Peptization Coagulation
A coagulated precipitate Smaller particles clumping
reverts to smaller particles. together to form larger particles.
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 Contamination of gravimetric precipitates:
Coprecipitation

SURFACE
INCLUSION OCCLUSION
ADSORPTION

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Harvey (2016). Analytical Chemistry 2.0
 Contamination of gravimetric precipitates:
Coprecipitation

SURFACE
INCLUSION OCCLUSION
ADSORPTION
The impurity occupies a The impurity is trapped The impurity adsorbs to
lattice site in the within a precipitate as it the surface of a
precipitate. forms. precipitate.

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Harvey (2016). Analytical Chemistry 2.0
 Steps in Gravimetric Precipitation
1. Weighing of sample
2. Dissolution of sample
3. Precipitation of the analyte
4. Digestion
5. Filtration and washing
6. Drying and/or ignition
7. Weighing of the residue 14
 Applications of Gravimetric Methods

Gravimetric methods DO NOT require a calibration or

standardization step because the results are calculated
directly from the experimental data and atomic masses.

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 Applications of Gravimetric Methods
When only one or two samples are to be analyzed, a
gravimetric procedure may be the method of choice
because it requires less time and effort than a procedure
that requires preparation of standards and calibration.

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Dimensional Analysis vs. Gravimetric Factor

𝑴𝑴 𝒐𝒇 𝒔𝒖𝒃𝒔𝒕𝒂𝒏𝒄𝒆 𝒔𝒐𝒖𝒈𝒉𝒕
𝑮𝒓𝒂𝒗𝒊𝒎𝒆𝒕𝒓𝒊𝒄 𝒇𝒂𝒄𝒕𝒐𝒓 =
𝑴𝑴 𝒐𝒇 𝒔𝒖𝒃𝒔𝒕𝒂𝒏𝒄𝒆 𝒘𝒆𝒊𝒈𝒉𝒆𝒅 17
 org cpd CO2 BaCO3

𝑀𝑀 𝐶
0.6006 𝑔 𝐵𝑎𝐶𝑂3 𝑀𝑀 𝐵𝑎𝐶𝑂
3
%𝐶 = 𝑥 100 = 17.23
0.2121 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒
 𝟎. 𝟐𝟑𝟓𝟔 𝒈 NaCl, BaCl2 AgCl 𝟎. 𝟒𝟔𝟑𝟕 𝒈

𝒙 𝒚

𝑥 + 𝑦 = 0.2356 𝑔 equation 1
𝑀𝑀 𝐴𝑔𝐶𝑙 2𝑀𝑀 𝐴𝑔𝐶𝑙
𝑥 +𝑦 = 0.4637 𝑔 equation 2
𝑀𝑀 𝑁𝑎𝐶𝑙 𝑀𝑀 𝐵𝑎𝐶𝑙2
𝑀𝑀 𝐴𝑔𝐶𝑙 2𝑀𝑀 𝐴𝑔𝐶𝑙 equation 2
𝑥 + (0.2356 − 𝑥) = 0.4637 𝑔 in terms of 𝑥
𝑀𝑀 𝑁𝑎𝐶𝑙 𝑀𝑀 𝐵𝑎𝐶𝑙2
 𝟎. 𝟐𝟑𝟓𝟔 𝒈 NaCl, BaCl2 AgCl 𝟎. 𝟒𝟔𝟑𝟕 𝒈

𝒙 𝒚

𝑥 = 0.1296 𝑔 𝑁𝑎𝐶𝑙 𝑦 = 0.1060 𝑔 𝐵𝑎𝐶𝑙2

0.1296 𝑔 𝑁𝑎𝐶𝑙 0.1060 𝑔 𝐵𝑎𝐶𝑙2

% 𝑁𝑎𝐶𝑙 = 𝑥 100 % 𝐵𝑎𝐶𝑙2 = 𝑥 100
0.2356 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒 0.2356 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒

% 𝑵𝒂𝑪𝒍 = 𝟓𝟒. 𝟗𝟗 % 𝑩𝒂𝑪𝒍𝟐 = 𝟒𝟓. 𝟎𝟏