Module 3 – Gravimetric Methods of Analysis
Gravimetric methods of analysis are based on the conversion of
ion(s)/ element(s)/ radical(s) into a pure and stable compound
which can be directly weighed and quantified.
Types of gravimetric methods:
In electrogravimetry, ions of a substance usually a metal are
electrolyzed. Electrochemical reduction causes the analyte to be
deposited on the cathode. The mass of the cathode is
determined before and after the experiment, and the difference
is used to calculate the mass of analyte in the original solution.
Sample containing ion/element/radical of interest (the analyte)
↓ electrolysis
Deposits (analyte) on the cathode
In particulate gravimetry, the analyte is already present in a
particulate form which can be readily separated from its liquid,
gas, or solid matrix. This method does not rely on a chemical
reaction. Most common methods are filtration, in which solid
particulates from their gas, liquid, or solid matrix; and extraction
which is useful for gas particles, solutes, and solids.
Particulate containing the analyte
↓ filtration/extraction
Separated analyte
In precipitation methods, the analyte is converted to a sparingly
soluble precipitate. This 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.
Sample containing the analyte
↓ add precipitating agent
Precipitate with ion/element/radical of interest
In volatilization methods, the analyte or its decomposition
products are volatilized at a suitable temperature. The volatile
product is then collected and weighed, or, alternatively, the mass
of the product is determined indirectly from the loss in mass of
the sample.
Sample containing the analyte
↓ heating
Collected volatiles or weight loss of the sample
Precipitating the Analyte from the Sample
– gravimetric precipitating agent should react specifically,
or if not, then selectively with the analyte.
– The precipitate (the product of the precipitating agent
with the analyte) should be:
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 of the atmosphere;
4. of known composition after it is dried or, if necessary,
ignited.
Precipitates made up of large particles are generally desirable in
gravimetric work because large particles are easy to filter and
wash free of impurities.
The particle size is related to relative supersaturation:
where Q = concentration (M) of the solute at any instant; S =
equilibrium solubility of the solute
if Q < S: the solution is unsaturated
if Q = S: the solution is saturated
id Q > S: the solution is supersaturated
– for best possible results: Q should be as low as possible
and S should be relatively large.
– when relative supersaturation is large (Q↑, S↓), the
particle size tends to be fine (colloidal);
– when relative supersaturation is small (Q↓, S↑), large
particles (crystalline) are more likely to be generated.
Colloidal vs Crystalline Particle
– Colloidal particles are solid made up of particles having
diameters that are less than 10-4 m.
– Colloidal suspension shows no tendency to settle from
solution, nor are they easily filtered.
– Crystalline particles have dimensions on the order of
tenths of a millimeter or greater and are temporarily
dispersed in the liquid phase is called a crystalline
suspension.
– Crystalline suspension tends to settle spontaneously
and are readily filtered.
Controlling Particle Size
– experimental variables that lead to crystalline precipitates
include:
1. hot solutions (both sample and precipitating agent) -
increase the S;
2. dilute solutions (both sample and precipitating agent) –
decrease Q;
3. slow addition of the precipitating agent with good stirring
– keep Q low and prevent formation of electric bilayer;
4. pH control - increase S.
How do Precipitates form?
– two ways:
1. Nucleation – the process in which a minimum number
of atoms, ions, or molecules join together to produce a
stable solid.
2. Particle growth – growth on existing nuclei
The rate of nucleation is believed to increase enormously with Coagulating Colloids
increasing relative supersaturation. The rate of particle growth
– 2d1 is a distance that is too
is only moderately enhanced by high relative supersaturation.
If nucleation predominates, a large number of small particles great for coagulation to
result. If particle growth predominates, a smaller number of large occur.
particles result. – Three factors:
1. Concentration of the
Why do colloids remain suspended in the solution?
– Colloidal suspensions are stable because all the particles precipitating reagent Copyright 2013 Cengage Learning. Skoog, West,
Holler ansd Crouch. (2012) Fundamentals of
present are either positively or negatively charged. 2. Heating and stirring Analytical Chemistry, 9th ed., Cengage Asia.

3. Electrolyte concentration

In dilute precipitating reagent, the two

particles can approach within 2d2 of one
another. The distance between particles
becomes small enough for the forces of
agglomeration to take effect and a
coagulated precipitate to appear.
Notes about the graph: The effective charge (can be +/-) is larger at the surface
(d = 0) of the particle where number of counterions is greater than the number
of primarily adsorbed ions. Effective charge approaches zero (d = d2), as the
number of counterions decreases until it is approximately equal to the number
of primarily adsorbed ions.

Copyright 2013 Cengage Learning. Skoog, West, Holler and Crouch. (2012) Fundamentals of Analytical Chemistry, 9 th ed., Cengage
Asia.
Coagulation of a colloidal suspension can often be brought about
by a short period of heating, particularly if accompanied by
– The charge on a colloidal particle results from cations stirring. Heating decreases the number of adsorbed ions and thus
and anions that are bound to the surface of the particles the thickness, di, of the double layer. The particles may also gain
(adsorption). enough kinetic energy at the higher temperature to overcome
– When the precipitation is complete, the charge on a the barrier to close approach posed by the double layer.
colloidal particle formed in a gravimetric analysis is
An even more effective way to coagulate a colloid is to increase
determined by the charge of the lattice ion that is in the electrolyte concentration of the solution.
excess.
– Attached directly to the solid surface is a charged – The net effect of adding a
primary adsorption layer. Surrounding the charged suitable electrolyte to a colloidal
particle is the counter-ion layer (has an opposite charge suspension is a shrinkage of the
with the primary layer). The primary adsorbed silver counter-ion layer because the
ions and the counter-ion layer constitute an electrical solution now contains sufficient
double layer that imparts stability to the colloidal counter-ions to balance the
suspension. charge of the primary
Copyright 2013 Cengage Learning. Skoog, West,
Holler ansd Crouch. (2012) Fundamentals of
Analytical Chemistry, 9th ed., Cengage Asia.
adsorption layer.

Copyright 2013 Cengage Learning. Skoog, West, Holler

and Crouch. (2012) Fundamentals of Analytical
Chemistry, 9th ed., Cengage Asia.

Peptization is a process by which a coagulated colloid return to

its dispersed state because the supporting electrolyte is washed
off from the precipitate environment (Expounded below). This
– As colloidal particles approach one another, this double process decreases the particle size and filterability of the
layer exerts an electrostatic repulsive force that precipitate.
prevents particles from colliding and adhering.
– This problem is commonly solved by washing the
– individual particles of most colloids can be coagulated
precipitate with a solution containing an electrolyte
or agglomerated to give a filterable, amorphous mass
solution that volatilizes when precipitate is dried or
that will settle out of solution.
ignited.
Digestion (Ostwald ripening) is the process in which the
coagulated colloid is allowed to stand for an hour or more in
contact with the hot solution from which is was formed (mother
liquor). It promotes slow recrystallization, increase particle size
and expelling of impurities.
Purity of Precipitation
Coprecipitation is a process in which normally soluble
compounds are carried out of solution by a precipitate which
causes impurities in the precipitate. Four types of
coprecipitation:
1. Surface Adsorption
Coagulation of a colloid does not significantly decrease the
amount of adsorption.
– The net effect of surface adsorption is therefore the
carrying down of an otherwise soluble compound as a
surface contaminant.
– The purity of many coagulated colloids is improved by
digestion.
– A drastic but effective way to minimize the effects of
adsorption is reprecipitation, or double precipitation or
recrystallization.
2. Mixed-Crystal Formation/Inclusion
– a process in which one of the ions in the crystal lattice of
a solid is replaced by an ion of another similar ions.
– The extent of mixed-crystal contamination is governed by
the law of mass action and increases as the ratio of
contaminant to analyte concentration increases.
3. Occlusion and Mechanical Entrapment
– Occlusion is a type of coprecipitation in which a
compound is trapped within a pocket formed during
rapid crystal growth.
– Mechanical entrapment occurs when crystals lie close
together during growth.
– Both occlusion and mechanical entrapment are at a
minimum when the rate of precipitate formation is low,
that is, under conditions of low supersaturation.
– In addition, digestion is often remarkably helpful in
reducing these types of coprecipitation.
Mixed-crystal formation may occur in both colloidal and
crystalline precipitates, whereas occlusion and mechanical
entrapment are confined to crystalline precipitates.
Coprecipitated impurities may cause either negative or positive
systematic errors in an analyte.
– If the contaminant is not a compound of the ion being
determined, a positive error will always result. Thus, a
positive error is observed whenever colloidal silver adsorbs
silver nitrate during a chloride analysis.
– When the contaminant does contain the ion being
determined, either positive or negative errors may be
observed. For example, in the determination of barium by
precipitation as barium sulfate, occlusion of other barium
salts occurs. If the occluded contaminant is barium nitrate,
a positive error is observed because this compound has a
larger molar mass than the barium sulfate that would have
formed had no coprecipitation occurred. If the barium
chloride is the contaminant, the error is negative because
its molar mass is less than that of the barium salt.
– To minimize co-precipitation: careful precipitation with
vigorous stirring upon addition of precipitating agent,
complete digestion process, and thorough washing of the
precipitate is required.
Drying and Ignition of Precipitates
• After separating the precipitate through filtration, the
gravimetric precipitate is heated until its mass becomes
constant.
• Some precipitates are also ignited to decompose the solid
and form a compound of known composition. This new
compound is often called the weighing form.
Summary:
To achieve ideal precipitate, it should have
1. low solubility – achieved through careful choice of
precipitating agent
2. large particles – achieved through careful control of
conditions of low unsaturation.
3. high purity – minimized through recrystallization,
digestion, use of electrolyte solution and ignition of
precipitate
Calculating Results from Gravimetric Data
The results of a gravimetric analysis are generally computed
from the mass of sample and the mass of a product of known
composition.
g product (precipitate)
↓ use molar mass of precipitate
moles of precipitate
↓ use mole ratio of precipitate and compound containing
the analyte
moles of compound containing the analyte
↓ use mole ratio of the compound and the analyte
moles of ion/element/radical of interest
↓ use molar mass of the analyte
g analyte
↓ divided by g sample then multiply with 100%
Percent of analyte in a given sample.
Example:
An iron ore was analyzed by dissolving a 1.1324-g sample in
concentrated HCl. The resulting solution was diluted with water,
and the iron(III) was precipitated as the hydrous oxide Fe2O3･
xH2O by the addition of NH3. After filtration and washing, the
residue was ignited at a high temperature to give 0.5394 g of
pure Fe2O3 (159.69 g/mol). Calculate: (a) the % Fe (55.847 g/mol)
and (b) the % Fe3O4 (231.54 g/mol) in the sample.
For both parts of this problem, we need to calculate the number
of moles of Fe2O3. Thus,
Definition of Terms
effective charge - can be thought of as a measure of the repulsive
force the particle exerts on like particles in the solution.
signal - (in the context of chemical analysis) a detectable physical
quantity or impulse by which information can be derived
analyte – a chemical substance that is the subject of chemical
analysis
REFERENCES
Skoog, West, Holler and Crouch. (2012) Fundamentals of
Analytical Chemistry, 9th ed., Cengage Asia
Harvey, David. (2008) Modern Analytical Chemistry, McGraw-Hill
Companies. ISBN 0–07–237547–7

LINKS for Lecture videos:

(a) The number of moles of Fe is twice the number of moles of
Fe2O3, and Concept (Part 1)

https://www.youtube.com/watch?v=hDvphHmf66A&t=619s

Calculation (Part 2)

https://www.youtube.com/watch?v=fglF96kvmBQ

MORE PRACTICE CALCULATION

(b) As shown by the following balanced equation, 3 mol of Fe 2O3 https://www.youtube.com/watch?v=5kf7EIURWZA&t=98s
are chemically equivalent to 2 mol of Fe3O4. That is,
Link for Problem set:

https://forms.gle/h8sBfDDf5GVNxVU68

Problem exercises:

1. When an impure sample of potassium chloride (0.4500g)

was dissolved in water and treated with an excess of silver
nitrate, 0.8402 g of silver chloride was precipitated.
Calculate the percentage KCl in the original sample.
2. An ore is analyzed for the manganese content by converting
the manganese to Mn3O4 and weighing it. If a 1.52g sample
yields Mn3O4 weighing 0.126 g, what would be the percent
Mn3O3 in the sample? The percent of Mn?
3. Five hundred mL of a river water are subjected to sulfate
determination by the barium gravimetric method. The final
weight of the precipitate was 73.5 mg. What was the sulfate
concentration in mg/L?