Gravimetric Methods of

Analysis.
Gravimetric analysis:
•Often the last choice
•Tedious
•Time consuming.
•But when applicable, one of the most
accurate methods of analysis.
Why?
– Analysis is based on the measurement of
mass.
 Two Types of Gravimetric Analyses

(1) Precipitation methods

– The analyte is converted to a sparingly soluble
precipitate.

– The precipitate is filtered and washed.

– A third step may be employed, which converts the

precipitate to a product of known composition using
heat. (stoichiometrically)

– The mass of the product is then determined.

.
(2) Volatilisation methods
– The analyte or its decomposition products are
volatilised at a suitable temperature.

– The volatile product is collected and weighed.

– Alternatively, the loss of mass of the sample is

measured and indirectly the mass of the volatile
component is determined.
 Stoichiometry
• Defined as the mass relationship among
reacting chemical species.

• A balanced chemical reaction is a statement of

the combining ratios, or stoichiometry (in units of
moles) between each reacting substance and
their products.

• We must understand stoichiometry to solve

gravimetric problems.
 The basis of All Gravimetric Analyses

Mass of Moles of Moles of Mass of

Known Known Unknown Unknown

Balanced Chemical Equation

In the analysis of Pb by gravimetric methods

•2NaI(aq) + Pb(NO3)2(aq)  PbI2(s) + 2NaNO3(aq)

•The stoichiometric relationship is:

– 2 mole of aqueous sodium iodide combines with 1 mole
of aqueous lead nitrate to produce a precipitate of 1
mole of lead iodide and 2 mole of aqueous sodium
nitrate.

•Understanding the stoichiometry enables the

calculation of the quantities of each species, given
we know the quantity of one.
For example.

(a) What mass of AgNO3 (169.9 g/mol) is

needed to convert 2.33g of Na2CO3 (106.0
g/mol) to Ag2CO3?

(b) What mass of Ag2CO3 (275.7 g/mol) will

be formed?
First write a balanced equation.

Na2CO3 + 2AgNO3  Ag2CO3 + 2NaNO3

 Calculations
Step 1.
• Transform the known mass of substance to
moles.
• 2.33 g of Na2CO3

Moles = mass/Mw
= 2.33 g/106.0 g/mol
= 0.02198 mol Na2CO3
Step 2.
• Note the stoichiometric factors.

1 mol of Na2CO3 : 2 mol AgNO3

0.02198 mol of Na2CO3 : x mol AgNO3.
x 0.02198

2 1

x = 0.04396 mol of AgNO3.

Step 3.
• Reconvert the number of moles back to
the metric units called for in the question.

Since
• n(moles) = mass/Mw
• 0.04396 (mol of AgNO3) = mass (g) /169.9
g/mol
• Mass (AgNO3) = 7.47 g.
Repeat same procedure for question (b).

Ans (b) = 6.06 g of Ag2CO3.

 Properties of Precipitates and
Precipitating Agents.
• Ideally a precipitating agent should react
specifically or at least selectively with
the analyte.

– Specifically – reacts only with that analyte

(not very common).
– Selectively – reacts with a single chemical
species.
• (example – silver nitrate reacts with halides)
• In addition the ideal precipitating agent should
yield a product that is:

– Readily filtered and washed free from contaminants.

– Of low solubility so that no significant loss is incurred

during filtration and washing.

– Unreactive with constituents in the atmosphere.

– Of known composition after it is dried, or ignited.

 Particle size and filterability of
precipitates
• Precipitates vary in size from colloidal
particles/suspensions (almost invisible – nm
size) to crystalline particles that might be a
millimetre in diameter.
 Particle size and filterability of
precipitates

•Factors that influence the size are complicated –

they include:
– Precipitate solubility
– Temperature
– Reactant concentrations
– Rate of mixing.
 Relative Supersaturation.
The net affect can be qualitatively accounted for by
relating the particle size to a single property of the
system called its Relative Supersaturation.

Q S
Relative supersaturation 
S

In this equation Q is the concentration of a species

at any time and S is its equilibrium solubility
Experimentally, particle
size varies inversely
with the average relative
supersaturation.

Therefore to increase
particle size you need to
decrease the relative
supersaturation
 Precipitate Formation
Precipitates form by two mechanisms.
Nucleation - a stable solid is formed by the coming together of several ions,
molecules or atoms. (This often occurs on the surface of suspended solid
contaminants). Further precipitation then depends on the competition between
more nucleations or particle growth of existing nuclei.

Visualisation of nucleation: finger

immersed in a carbonated drink. CO2
bubbles form on the surface of the skin.

If nucleation predominates a colloidal suspension occurs containing a large

number of small particles. If particle growth predominates a small number of
large particles are produced.
• The rate of nucleation is believed to be
enormously increased with increasing relative
supersaturation, while particle growth is only
moderately affected.

• Hence, larger particles can be obtained using

solutions with a low relative supersaturation.

• Large particles can therefore be obtained using:

– Elevated temperatures (increases solubility, S)
– Dilute solutions (decreases Q)
– Slow addition of the precipitating agent
– Good stirring.
• By stirring the solution and adding the
precipitating agent slowly, high localised
concentrations are avoided.

• In some instances, a colloidal precipitate can not

be avoided. Such as when the solubility of the
product is so low that S becomes negligible with
respect to Q.

• Colloidal suspensions are very stable.

– Their size means that they do not settle under gravity.
– They are too small to be filtered.
– Their surfaces are charged and hence repulsion
between particles prevents particle growth.
 Colloidal Agglomeration
• Coagulation or agglomeration is a process
used to bring the colloids together to produce a
large filterable mass.

• The coagulates are formed by:

– heating the solution. This gives the particles greater
kinetic energy enabling individual particles to
overcome the electrostatic repulsion and approach
each other.
– Addition of an electrolyte.
• Having coagulated a colloidal particle and
collected it by filtration, the precipitate is washed.
– The precipitate must be washed with an electrolytic
solution.
– If not, the colloid will undergo peptization.
– This is the process whereby a coagulated colloid
reverts to its original colloidal form.

• Thus the dilemma exists. A pure compound is

required for the gravimetric analysis, but washing
with pure water will result in peptization.

• Consequently, the drying stage must remove the

contamination resulting from the electrolyte.
 Colloidal Precipitate

Read more on colloidal particles at:

https://chem.libretexts.org/Textbook_Maps/General_Chemistry_Textbook_Maps/
Map%3A_Chem1_(Lower)/07%3A_Solids_and_Liquids/7.10%3A_Colloids_and_th
eir_Uses
 Coprecipitation.
Otherwise soluble compounds are removed from solution along with
the precipitation of the analyte.
The solution is not saturated with the co-precipitant, but
coprecipitation occurs as a result of:

(a)Adsorption
(b)Occlusion
(c)Mechanical entrapment/inclusion
(d)Post precipitation
(e)Mixed crystal formation/inclusion
 Surface adsorption
• Generally the error associated with adsorption is small
and tolerable, except in the case whereby heavy-metal
hydroxides adsorb on the surface of iron or aluminium
hydroxides.

• Reprecipitation may improve the coprecipitation, but it

adds to the analysis time.

• Example, in the analysis of chloride by precipitation with

silver. Silver ions form the primary layer of the
precipitate. Anions, such as, nitrate adsorb to the
surface, contaminating the analysis.
 Occlusion

• Occurs when a crystal grows and traps

another foreign ion within the growing
crystal.

• Occlusion is greatest when the growth

rate is rapid, therefore occurring in the
region of initial crystal formation.
 Mechanical entrapment

• Occurs when crystals lie close to one

another during growth and as a
consequence trap a portion of the
solution in a pocket region.

• Greatest when growth rate is rapid.

 Post precipitation
• A surface impurity formed on the surface of a previously
formed precipitate particle.
• May be due to the primary adsorption of the common ion
which is in excess,
– i.e., the supersaturated solution of the second material is formed
on the surface of the particle and that offers nucleation sites to
break supersaturation and cause the secondary precipitate to
form.
 Mixed crystal formation
• One of the ions in the crystal lattice is replaced by another ion of a
different element.

• The ion must have the same charge as the analyte ion and be of a
similar size.

• Little can be done about removing the contaminant from the lattice.

• The contamination increases as the concentration of the

contaminant increases.

• To minimise this contamination use a precipitating agent that

doesn’t result in the coprecipitation, or remove the coprecipitating
agent prior to the analyte precipitation.
 Homogeneous precipitation
• Instead of a precipitating agent being added to the
solution, a chemical reaction takes place that generates
a precipitating agent.

• Hence localised high concentrations of precipitating

reagents are avoided as the chemical reaction is
homogeneous.

• The precipitating reagent appears slowly and reacts

immediately with the analyte.

• Precipitates are usually more dense and the particle size

is usually larger. This results in a more easily filterable
precipitate. Purity is also usually improved.
• Example. Urea reacts to form the
hydroxide ion, which is useful for
gravimetric analysis where the insoluble
hydroxide salt is formed.

(NH2)2CO + 3H2O  CO2 + 2NH4+ + 2OH-

• The hydroxide then reacts with the analyte

to form the hydroxide salt, eg Fe(OH)3.
Al(OH)3.
• Read more on gravimetric analyses at:
• http://intranet.tdmu.edu.ua/data/kafedra/internal/pharma_2/classes_stud/en/pharm/pr
ov_pharm/ptn/analytical%20chemistry/2%20course/13%20Gravimetric%20analysis.ht
m