Chapter 12:

Gravimetric Methods of Analysis

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 Gravimetric methods: The quantitative methods that are
based on determining the mass of a pure compound to
which the analyte is chemically related.
• Precipitation gravimetry: The analyte is separated from a
solution of the sample as a precipitate and is converted
to a compound of known composition that can be
weighed.
• Volatilization gravimetry: The analyte is separated from
other constituents of a sample by converting it to a gas of
known chemical composition that can be weighed.
• Electrogravimetry: The analyte is separated by deposition
on an electrode by an electrical current.

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12A Precipitation gravimetry
The analyte is converted to a sparingly soluble precipitate
that is then filtered, washed free of impurities and converted to
a product of known composition by suitable heat treatment
and weighed.
Ex., for determining the [Ca2+] in water:
2NH 3(aq) + H 2C 2 O 4(aq)  2NH +4(aq) + C 2O 2-4(aq)
Ca 2 + C 2O 2-4(aq)  CaC 2O 4(s)
filtered, dried, ignited

CaC2 O 4(s)   CaO (s) + CO (g) + CO 2(g)

After cooling, the precipitate is weighed and the mass is

determined.

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12A-1 Properties of Precipitates and Precipitating Reagents
A gravimetric precipitating agent should react specifically or
at least selectively with the analyte and give precipitates that
is:
1.Enough particle size for retaining on filter paper
2.High purity (free of contaminants)
3.Low solubility that no significant loss of the analyte occurs
during filtration and washing
4.Unreactive with air (stable)
5.Known stoichimetric composition

* Specific reagents: react only with a single chemical

species.
Selective reagents: react with a limited number of
species.
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12A-2 Particle Size and Filterability of Precipitates
Characteristics of Ion, colloid and particle
Name Diameter Characteristics
Ion ~10-8 cm Dissolved
Colloid 10-7~10-4 cm Suspended
Crystalline >10-4cm Settled from solution (filterable)

 Nucleation and Particle growth

• Nucleation: The initial formation process in which a
minimum number of atoms, ions, or molecules join
together to give a stable solid.
• Particle growth: The subsequent growth after
nucleation.

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 Relative supersaturation (RSS) (von Weimann's theory):
Q -S
RSS 
S
Q: the concentration of the solute at any instant
S: the expected concentration solute at equilibrium
RSS Process Result
Large Nucleation dominate Smaller particles
Small Particle growth Larger Particle
dominate

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 Experimental Control of Particle Size
(the lower RSS value the larger particles)
 Increase S:
 Heating
 pH adjustment (If the solubility of the precipitate
depends on pH)
 Adding complexing agent
 Decrease Q:
 Using dilute precipitating solution
 Adding precipitating agent slowly and stirring
 Using homogeneous precipitation technique

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12A-2 Colloidal Precipitates
Colloidal Precipitates: The amorphous precipitates which is
formed by decreasing the repulsion force between alike
charged colloids and leading those colloids to be coagulated to
give a filterable particles.

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 A colloidal silver chloride (AgCl) suspended in a solution of
excess AgNO3 for example – a electric double layer:

Primary adsorption layer

on colloidal particle
(+ charged)

Neutral aqueous
solution

Counter-ion layer
(- charged)

* Adsorption: A process in which a substance (gas, liquid, or solid) is

held on the surface of a solid.
Absorption: A process in which a substance within the pores of a
solid.
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 Effect of AgNO3 and electrolyte concentration on the thickness of double
layer surrounding a colloidal AgCl particle in a solution containing excess
AgNO3.

* The effective charge can be thought as a measure of the repulsive

force that the particle exerts on like particles in the solution.
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 Coagulation of Colloids
Coagulation can be hastened by heating, by stirring, and
by adding an electrolyte to the medium because of
decreasing the volume of the counter-ion layer.

A coagulated
colloid

* Digestion (standard for some time) result in a denser

mass precipitate.

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 Peptization of Colloids
 Peptization: The process by which a coagulated colloid
reverts to its original dispersed colloidal suspensions.
(When a coagulated colloid is washed, some of the
electrolyte responsible for its coagulation is removed,
therefore, the repulsive forces as well as the original colloidal
state are reestablished.)
 Volatile electrolyte is used as washing solution, e.g., HNO3,
NH4NO3, to avoid peptization.
• Electrolyte prevent the losses of precipitate from
peptization.
• Volatile electrolyte out to atomosphere once heating.

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12-4 Crystalline Precipitates
Crystalline precipitates are generally more easily filtered and
purified than are coagulated colloids.
Particle size of crystalline solids can often be improved
significantly by minimizing Q (by using dilute solutions) or
maximizing S (precipitating from hot solution or by adjusting the
pH), or both.
Digestion improves the purity and filterability of both colloidal
and crystalline precipitates.

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12-5 Coprecipitation
Coprecipitation: A process in which normally soluble
compounds are carried out of solution by a precipitate. (It may
resulted in impurities within the desired precipitates.)
 There are four types of coprecipitation: surface
adsorption, mixed-crystal formation, occlusion, and
mechanical entrapment.
 Coprecipitated impurities may cause either negative or
positive errors.

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 Surface Adsorption: The impurity is chemically or physically
adsorbed onto the surface of precipitates.
Cause significant contamination in coagulated colloids but of
no significance in crystalline precipitates.
 Problem solving:
• Washing a coagulated colloid with a solution containing a
volatile electrolyte
• Reprecipitation

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 Mixed-Crystal Formation: A type of coprecipitation in which
a contaminant ion replaces an ion in the lattice of a crystal.
EX. SrSO4 in BaSO4

 Problem solving:
• Change to another more selective precipitating agent
• Reprecipitation
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 Occlusion: A type of coprecipitation in which coprecipitated
physically trap contaminated counter ions within a
precipitate during rapid precipitate formation.

 Problem solving: Digestion

* Digestion: The process which has a waiting time to achieve
desired outcome. (The solubility–precipitation is in a
dynamic equilibrium, digestion ensures the occluded
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material is eventually exposed to the supernatant solution.)
 Mechanical Entrapment: A type of coprecipitation in which
coprecipitated physically trap a pocket of solution within a
precipitate during rapid precipitate formation.

 Problem solving: Digestion

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12A-6 Precipitation from Homogeneous Solution
Homogeneous precipitation: 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 larger size particles.

Example 1: For generating OH– as precipitant

CO(NH2)2(aq) + H2O(l)  CO2(g) + 2NH3(aq)
NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq)
* Generation rate can be controlled by temperature

Example 2: For generating SO42– as precipitant

NH2SO3H(aq) + 2H2O(l)  NH4+(aq) + H3O+(aq) + SO42–(aq)
* Generation rate can be controlled by pH
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12A-7 Drying and Ignition of Precipitates
 A gravimetric precipitatate
is heated until its mass
becomes constant. This
new compound is called the
weighing form.
 Thermogram: A graph show
mass loss as a function of
temperature.

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Figure 12-7 Schematic of a thermobalance: A: beam; B: sample cup and holder; C:
counterweight; D: lamp and photodiodes; E: coil; F: magnet; G: control amplifier; H:
tare calculator; I: amplifier; and J: recorder.

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12B Calculation of results from gravimetric data

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 Gravimetric factor: A gravimetric factor is an algebraic
expression that converts grams of a compound into grams of
a single element. It is the ratio of the formula weight (FW) of
the substance being sought to that of the substance weighed.
Example 1. Fe is sought, Fe2O3 is weighed:

Example 2. Fe3O4 is sought, Fe2O3 is weighed:

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12C Applications of gravimetric methods
12C -1 Inorganic Precipitating Agents

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12C-2 Reducing Agents
(convert an analyte to its element form for weighing)

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12C-3 Organic Precipitating Agents
 Some organic reagents react with metal ions then produce
insoluble coordination compounds.
 Reagents that form coordination compounds of this type
are called chelating agents, and their products are called
chelates.
 Those metal chelates are relatively nonpolar and have low
solubilities in water.

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12C-4 Organic Functional Group Analysis

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12C-5 Volatilization Gravimetry
Figure 12-8 Apparatus for determining the sodium hydrogen carbonate
content of antacid tablets by a gravimetric volatilization procedure.

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 Homework (Due 2013/11/7)
Skoog 9th edition, Chapter 12, Questions and Problems
12-1
12-2
12-4
12-5
12-7

End of Chapter 12

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