1

Gravimetry
GRAVIMETRY 2
 This is the process of isolating and weighing an element or a
definite compound of the element (analyte) in as pure of
form as possible.

 The element or compound is separated from a weighted

portion of the substances being examined.

 The weight of the element (or analyte) can then be

calculated from knowledge of the formula of the
compound and the atomic mass of the constituent
elements.
A + rR  A Rr
 Gravimetry cont’d
 = molecules of the analyte, A, that react with r 3
molecules of the reagent, R.

 AaRr is usually a slightly soluble substance that can be

weighed after drying.

 Calcium can be determined gravimetrically by

precipitation of calcium oxalate and ignition of the
oxalate to calcium oxide.

Ca2+ + C2 O42-  Ca C2 O4 (s)

Ca C2 O4 (s)  Ca O (s) + CO2 (g) + CO (g)

An excess of reagent R is normally added to decrease the

solubility of the precipitate.
Gravimetry cont’d 4
 Gravimetry is generally time consuming (classical) but offers
several advantages:

a) It is accurate and precise when using modern analytical

balances.

b) Possible sources of error are readily checked, since filtrate

can
be tested for completeness of precipitation and
precipitates
may be examined for the presence of impurities.

c) Doesn’t require any calibration as it is an absolute

method and direct measurements are done.

d) Determinations can be carried out with relatively

inexpensive
apparatus, only furnace for drying and platinum crucibles
are a
bit costly.
 Gravimetry cont’d 5
For a gravimetric method to be successful certain requirements
should be met.

1. The separation process should be sufficiently complete so that

the quantity of analyte left unprecipitated is 0.1mg or less in
determining a major constituent of a macrosample.

2.The substance weighed should have a definite composition

and should be pure, or almost pure.

%A = mass of analyte x 100

mass of sample
FORMATION AND PROPERTIES OF6
PRECIPITATES
 The aim in gravimetry is to form a pure and filterable
precipitate.

 This is not done easily and has associated problems. We,

therefore, have to look at how the particles are built up
into solid aggregates, sufficiently large to settle as a
precipitate.

 Ideally, precipitates should consist of large particles as they

are easily filtered and washed free of impure substances.

 Usually, these precipitates are relatively pure.

NaC1 (aq) + xs AgNO3 (aq) — AgC1 (s)
FORMATION AND PROPERTIES 7
OF PRECIPITATES Cont’d
 In the precipitation of AgC1, for example starting with Cl
ions in solution, the ions are very small in diameter (10-8cm).
When the Ksp is surpassed, Ag+ and C1- ions begin to fuse
forming particles called nuclei.

 These then grow sufficiently large to settle in a solution.

 For it to settle, particle should have diameter of ~10-4cm.

 Particles with diameters of about 10-7 – 10-4 cm are called

colloids and they do not usually settle from solution and
are not easily filtered.
FORMATION AND PROPERTIES OF PRECIPITATES Cont’d


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Colloidal particles are charged as ions adsorb to their surface. When the AgCl
particles are of colloidal size, there are a large number of Ag+ and Cl- ions on
the surface.

 The ion in solution that is most strongly adsorbed to the AgC1 surface,
however, is Ag as it is in excess. Ag thus form a primary adsorption layer, they
in turn attract principally NO3- ions forming a secondary layer.

 The secondary or counter- ion layer is held more loosely than the primary
layer.

 The force of attraction is merely electrostatic and the ions here are much
more mobile than the ions in the primary layer.

 These two charged layers constitute an electrical double layer. This imparts a
degree of stability to the colloidal dispersion. (see diagram below)
FORMATION AND PROPERTIES OF9
PRECIPITATES Cont’d
 These layers, however, cause colloids to repel one
another and resist the formation of larger particles
that would have settled.
THE MECHANISM OF 10
PRECIPITATION
 The precipitation of an ionic compound from
homogeneous solution says AgC1(s) from AgNO3
+ NaC1.

 Precipitate formation is a dynamic process - a

reaction that is proceeding from an unstable
solution toward an equilibrium between solution
and solid.
Ag NO3 (aq) + Na C1(s)  Ag Cl(s) + NaNO3
(aq)

 Generally speaking, there are three important

stages of precipitate formation: nucleation, crystal
growth, and aging.
 Nucleation:
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 (a) - first supersaturation is achieved by adding precipitant to the
solution. Supersaturation occurs when the solution phase contains
more of the dissolved precipitate than can be present at equilibrium.

 (b) Then the smallest particles of precipitate (nuclei) that can grow
spontaneously from the super saturated solution.

Crystal Growth
 Crystal (particle) growth follows. This process consists of deposition of
ions or atoms from the solution onto the surface of the solid
particles present. The precipitation nuclei grow to form crystal colloids
(having regular, geometric pattern l nm- 100nm in diameter).
Aggregate (Particle) Growth
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 Aggregation of the solid particles may begin next.
Particles aggregate by colloiding and sticking
together.

 It is a process that competes with crystal growth to

form larger particles from the solution.

 Aggregation and crystal growth compete.

Depending on the conditions, the final precipitate
may be composed of coarse crystals, aggregates
of fine crystals, and/or aggregates of colloids.
FACTORS THAT DETERMINE THE 13
PARTICLE SIZE OF PRECIPITATES
 The aim of a gravimetric procedure is to produce a
precipitate that is pure and that is easily filtered. The
ease with which a precipitate is isolated, and its purity,
depends on the size of the particles making up the
precipitate.

 The particle size of precipitates varies greatly. From

colloids (<10-4 cm in diameter to particles with dia > 10-4
cm).

 The particle size of a precipitate is influenced by

variables such as precipitate solubility, temperature,
reactant concentration, and rate of which reactants are
mixed.
 14
 These variables can be accounted for
qualitatively if we assume that the particle size is
related to a single property called relative super
saturation or supersaturation ratio.
RSS = Q –S
S

von-Weimarn Equation:
Q = concentration of solute at any instant
S = its equilibrium solubility (force causing
precipitate to redissolve)
Q - S = degree of supersaturation at the
moment precipitation begins.
 15
 Experimental evidence show that the particle size of a
precipitate varies inversely with average RSS during the time
the reagent is being added.

 When RSS is large, particles have small diameter, hence

colloidal.

 However, when RSS is small or Q-S is small a crystalline solid is

more likely.
Selecting Optimal Experimental 16
 Experimental variables that minimize
Conditions
supersaturation and thus leads to crystalline
precipitates include:

 elevated temperatures to increase the

solubility of the precipitate (S)

 dilute solutions (to minimize Q) and slow

addition of the precipitating agent with good
stirring.

 good stirring avoids locally high concentrations

of precipitating reagent.
 17
 Larger particles can also be obtained by
control of acidity provided (if) the solubility
of the precipitate depends upon pH.

 For example, salts of weak acids, such as

CaC2O4 and ZnS are better precipitated in
weakly acidic rather than alkaline ones.
 COLLOIDS: Coagulating Colloids 18
 They can be made to coagulate so as to effect filtration in
several ways.

 These can be made to coagulate by adding some NaCl to the

solution.

 The additional NaCl decreases the Ag+ ion concentration in

the primary layer.

 The Cl- ion will be more strongly attached to the primary layer
of Ag+ than the NO3-, and they replace the NO3- ion in the
secondary layer and then ‘neutralize” the positive charge
contributed by the primary layer.
 19
 The surface charge of the colloid is now at as minimum.
When this happens the repulsion between colloids break
down and coagulation takes over.

 Another effective way to generate a colloid is to

increase the ionic strength by adding a soluble
electrolyte.

 This has the effect of increasing the concentration of

excess ion in the counter-ion layer.

 The volume of solution that contains sufficient counter

ions to balance the charge that is on the primary layer is
less.

 Thus addition of an electrolyte causes a reduction in the

size of the counter ion layer and the particles can
approach one another more closely.
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 Coagulation can also be achieved by
heating for a short period especially with
simultaneous stirring.

 Heating reduces the number of adsorbed

ions and the thickness of the double layer.

 This is so as the higher kinetic energies of the

ions in the counter ion layer them to
approach the opposite charged ions of the
primary layer more closely.
Peptization of Colloids 21
 A coagulated colloid can revert to its original dispersed
state - peptization. When a coagulated colloid is
washed, some of the electrolyte responsible for its
coagulation is leached.

 This has the effect of increasing the volume of the

counter-ion layer. The forces are then reestablished.

 Peptization can be minimized by washing the

precipitate with a solution containing an electrolyte that
volatilizes during drying or ignition.

 For example, AgCl:Ag+…NO3- can be washed with dilute

HNO3 or NH4NO3 because the nitric acid is volatilized
during the drying step or HCI (dil) and NH4Cl dil to wash
AgCl:Cl-…Na+ Depending on the precipitating agent.
DIGESTION OF PRECIPITATES 22
 In addition to controlling conditions during the actual
precipitation process, the analyst has other recourse
after the precipitate is formed.

 This to digest the precipitate. Here, the precipitate is

allowed to stand in contact with the mother liquor
(solution from which precipitate forms), at elevated
temperature for some time before filtration.

 However, digestion affects crystalline precipitates some

what differently than curdy ones. Curdy - precipitates
are formed from coagulation of colloid eg AgC1.
 Digesting of Crystalline precipitate 23
 During the digestion of crystalline precipitates
the larger crystals grow at the expense of the
smaller ones.

 The small particles dissolve and precipitate

onto the larger more perfectly formed crystals.

 The amount of impurities in crystals usually

decreases with digestion.
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The digestion of colloidial particles of silver

chloride in excess silver nitrate may be
shown symbolically as follows:
COPRECIPITATION AND PURITY OF 25
PRECIPITATES
 One of the most difficult problem in employing
precipitation as a means of separation is
obtaining the precipitate in a high degree of
purity.

 Substances that are normally soluble can be

carried down during precipitation of the desired
substance by process called coprecipitation.
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 There are four main types of coprecipitation.

- Surface adsorption

- Occlusion

- Mixed crystal formation

- Mechanical entrapment
Surface Adsorption
 Adsorption of ions at the surface occurs with all 27
precipitates. Contamination by adsorption causes a
significant error only in cases in which the precipitate has
a very large surface eg coagulated colloids.
eg: AgNO3 + NaCl  AgC1…Cl-
xs Ag + + Ag C1:Cl-  Ag Cl: Ag+ NO3
Ag NO3 which is soluble is carried down with AgCl

 Digestion of precipitate improves purity as mass is denser

and smaller surface area for absorption.

 Washing with suitable electrolyte removes impurities and

replaces then with adsorbed substances that are volatile
on ignition.
28
Occlusion and Mechanical Entrapment 29
 Here, impurities are trapped inside of cavities within the
precipitate.

 If the precipitate is crystalline, the ordered volumes tend

to be along flows and imperfections of the crystal.

 Crystalline occlusion occurs when the impurities are

entrapped during a rapid crystallization.

 However, if the precipitate is an aggregate, the

impurities entrapped in the volumes between the
particles.

 Aggregate occlusion may even trap the mother liquor,

this is called mechanical entrapment.
30
 31
 For occlusion the impurity can only be removed by
reforming the crystal

 While for mechanical entrapment the impurities can

be washed out or reforming the structure.

 Both at a minimum when the rate of precipitate

formation is low.

 Otherwise, digestion reduces these types of

coprecipitation.
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Mixed Crystal Formation or Isomorphism
 The closer the crystal and ionic structures of the
possible impurities match those of the precipitate,
the easier it is for the impurities to coprecipitate.

 When isomorphism is close, the contaminant

becomes evenly distributed in the host crystal.

 When mixed-crystal formation occurs, one of the

ion in a crystal lattice is placed by an ion of another
element
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 Examples if isomorphic precipitates are NaCl, KCl, KBr, KI. Pb2+ will also
replace Ba2+ in BaSO4.

 It is extremely hard to remove such impurities and a different precipitant

that does not give mixed crystals will have to be used.