Module 3 – Gravimetric Methods of Analysis

Gravimetric methods of analysis are based on the conversion of 4. of known composition after it is dried or, if necessary,
ion(s)/ element(s)/ radical(s) into a pure and stable compound ignited.
which can be directly weighed and quantified.
Precipitates made up of large particles are generally desirable in
Types of gravimetric methods: gravimetric work because large particles are easy to filter and
wash free of impurities.
In electrogravimetry, ions of a substance usually a metal are
electrolyzed. Electrochemical reduction causes the analyte to be The particle size is related to relative supersaturation:
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.
where Q = concentration (M) of the solute at any instant; S =
Sample containing ion/element/radical of interest (the analyte)
equilibrium solubility of the solute
↓ electrolysis
if Q < S: the solution is unsaturated
Deposits (analyte) on the cathode
if Q = S: the solution is saturated
In particulate gravimetry, the analyte is already present in a id Q > S: the solution is supersaturated
particulate form which can be readily separated from its liquid, – for best possible results: Q should be as low as possible
gas, or solid matrix. This method does not rely on a chemical and S should be relatively large.
reaction. Most common methods are filtration, in which solid – when relative supersaturation is large (Q↑, S↓), the
particulates from their gas, liquid, or solid matrix; and extraction particle size tends to be fine (colloidal);
which is useful for gas particles, solutes, and solids. – when relative supersaturation is small (Q↓, S↑), large
Particulate containing the analyte particles (crystalline) are more likely to be generated.
↓ filtration/extraction Colloidal vs Crystalline Particle
Separated analyte – Colloidal particles are solid made up of particles having
diameters that are less than 10-4 m.
In precipitation methods, the analyte is converted to a sparingly
– Colloidal suspension shows no tendency to settle from
soluble precipitate. This precipitate is then filtered, washed free
of impurities, and converted to a product of known composition solution, nor are they easily filtered.
by suitable heat treatment, and the product is weighed. – Crystalline particles have dimensions on the order of
tenths of a millimeter or greater and are temporarily
Sample containing the analyte dispersed in the liquid phase is called a crystalline
↓ add precipitating agent
suspension.
Precipitate with ion/element/radical of interest
– Crystalline suspension tends to settle spontaneously
In volatilization methods, the analyte or its decomposition and are readily filtered.
products are volatilized at a suitable temperature. The volatile
Controlling Particle Size
product is then collected and weighed, or, alternatively, the mass
– experimental variables that lead to crystalline precipitates
of the product is determined indirectly from the loss in mass of
the sample. include:
1. hot solutions (both sample and precipitating agent) -
Sample containing the analyte increase the S;
↓ heating 2. dilute solutions (both sample and precipitating agent) –
Collected volatiles or weight loss of the sample
decrease Q;
Precipitating the Analyte from the Sample 3. slow addition of the precipitating agent with good stirring
– keep Q low and prevent formation of electric bilayer;
– gravimetric precipitating agent should react specifically,
4. pH control - increase S.
or if not, then selectively with the analyte.
– The precipitate (the product of the precipitating agent How do Precipitates form?
with the analyte) should be: – two ways:
1. readily filtered and washed free of contaminants; 1. Nucleation – the process in which a minimum number
2. of sufficiently low solubility so that no significant loss of of atoms, ions, or molecules join together to produce a
the solid occurs during filtration and washing; stable solid.
3. unreactive with constituents of the atmosphere; 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 – If the contaminant is not a compound of the ion being
coagulated colloid is allowed to stand for an hour or more in determined, a positive error will always result. Thus, a
contact with the hot solution from which is was formed (mother positive error is observed whenever colloidal silver adsorbs
liquor). It promotes slow recrystallization, increase particle size silver nitrate during a chloride analysis.
and expelling of impurities.
– When the contaminant does contain the ion being
Purity of Precipitation determined, either positive or negative errors may be
observed. For example, in the determination of barium by
Coprecipitation is a process in which normally soluble
precipitation as barium sulfate, occlusion of other barium
compounds are carried out of solution by a precipitate which
salts occurs. If the occluded contaminant is barium nitrate,
causes impurities in the precipitate. Four types of
coprecipitation: a positive error is observed because this compound has a
larger molar mass than the barium sulfate that would have
1. Surface Adsorption formed had no coprecipitation occurred. If the barium
Coagulation of a colloid does not significantly decrease the chloride is the contaminant, the error is negative because
amount of adsorption. its molar mass is less than that of the barium salt.
– To minimize co-precipitation: careful precipitation with
– The net effect of surface adsorption is therefore the
vigorous stirring upon addition of precipitating agent,
carrying down of an otherwise soluble compound as a
surface contaminant. complete digestion process, and thorough washing of the
precipitate is required.
– The purity of many coagulated colloids is improved by
digestion. Drying and Ignition of Precipitates

– A drastic but effective way to minimize the effects of • After separating the precipitate through filtration, the
adsorption is reprecipitation, or double precipitation or gravimetric precipitate is heated until its mass becomes
recrystallization. constant.
• Some precipitates are also ignited to decompose the solid
2. Mixed-Crystal Formation/Inclusion and form a compound of known composition. This new
compound is often called the weighing form.
– a process in which one of the ions in the crystal lattice of
a solid is replaced by an ion of another similar ions. Summary:
– The extent of mixed-crystal contamination is governed by To achieve ideal precipitate, it should have
the law of mass action and increases as the ratio of 1. low solubility – achieved through careful choice of
contaminant to analyte concentration increases. precipitating agent
2. large particles – achieved through careful control of
3. Occlusion and Mechanical Entrapment
conditions of low unsaturation.
– Occlusion is a type of coprecipitation in which a 3. high purity – minimized through recrystallization,
compound is trapped within a pocket formed during digestion, use of electrolyte solution and ignition of
rapid crystal growth.
precipitate
– Mechanical entrapment occurs when crystals lie close Calculating Results from Gravimetric Data
together during growth.
The results of a gravimetric analysis are generally computed
– Both occlusion and mechanical entrapment are at a from the mass of sample and the mass of a product of known
minimum when the rate of precipitate formation is low, composition.
that is, under conditions of low supersaturation.
g product (precipitate)
– In addition, digestion is often remarkably helpful in ↓ use molar mass of precipitate
reducing these types of coprecipitation. moles of precipitate
↓ use mole ratio of precipitate and compound containing
Mixed-crystal formation may occur in both colloidal and
the analyte
crystalline precipitates, whereas occlusion and mechanical
moles of compound containing the analyte
entrapment are confined to crystalline precipitates.
↓ use mole ratio of the compound and the analyte
Coprecipitated impurities may cause either negative or positive moles of ion/element/radical of interest
systematic errors in an analyte. ↓ use molar mass of the analyte
g analyte Definition of Terms
↓ divided by g sample then multiply with 100%
effective charge - can be thought of as a measure of the repulsive
Percent of analyte in a given sample.
force the particle exerts on like particles in the solution.
Example: signal - (in the context of chemical analysis) a detectable physical
An iron ore was analyzed by dissolving a 1.1324-g sample in quantity or impulse by which information can be derived
concentrated HCl. The resulting solution was diluted with water,
and the iron(III) was precipitated as the hydrous oxide Fe2O3･ analyte – a chemical substance that is the subject of chemical
xH2O by the addition of NH3. After filtration and washing, the analysis
residue was ignited at a high temperature to give 0.5394 g of REFERENCES
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. Skoog, West, Holler and Crouch. (2012) Fundamentals of
Analytical Chemistry, 9th ed., Cengage Asia
For both parts of this problem, we need to calculate the number
of moles of Fe2O3. Thus, 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?