Gravimetry

unit 4
Dr. Deon Bennett
Gravimetry 2016
 GRAVIMETRY
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 contd
= molecules of the analyte, A, that react with r 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 contd
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) Doesnt 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 contd
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 OF
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 OF
PRECIPITATES Contd
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 Contd
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 OF
PRECIPITATES Contd
These layers, however, cause colloids to repel one another
and resist the formation of larger particles that would have
settled.
 THE MECHANISM OF
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:
(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
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
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.
 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.
 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 Conditions
Experimental variables that minimize 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.
 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
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.
 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 flocculate 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.
 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
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
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
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.
The digestion of colloidial particles of silver chloride
in excess silver nitrate may be shown symbolically as
follows:
 COPRECIPITATION AND PURITY OF 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.

eg BaCl2 + H2SO4 BaSO4(s)

Small amt + NO3- Ba (NO3)2

Nitrate is coprecipitated with the sulphate.

By careful precipitation and thorough washing, the effects of
coprecipitation can be minimized but not always eliminated.
 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 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 AgC1Cl-
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.
 Occlusion and Mechanical Entrapment
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.
 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.

 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
 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.