GRAVIMETRIC ANALYSIS

1
GRAVIMETRIC ANALYSIS
Gravimetric analysis is the quantitative determination of analyte
concentration through a process of precipitation of the analyte,
isolation of the precipitate, and weighing the isolated product.

Uses of gravimetric analysis…

– Chemical analysis of ores and
industrial materials
– Calibration of instrumentation
– Elemental analysis of
inorganic compounds
2
GRAVIMETRIC ANALYSIS
1. A weighed sample is dissolved
2. An excess of a precipitating agent is added to this
solution
3. The resulting precipitate is filtered, dried (or
ignited) and weighed
4. From the mass and known composition of the
precipitate, the amount of the original ion can be
determined
3
CRITERIA FOR GRAVIMETRIC ANALYSIS
1. The desired substance must completely precipitate from
solution
• In most determinations the precipitate is of such low
solubility that dissolution of the analyte is negligible
• An additional factor is the "common ion" effect, further
reducing the solubility of the precipitate

4
CRITERIA FOR GRAVIMETRIC ANALYSIS

When Ag+ is precipitated from solution through the addition

of Cl-
Ag   Cl   AgCl (s )

the (low) solubility of AgCl is further reduced by the excess

of Cl- that is added, pushing the equilibrium to the right
(Le Chatelier’s Principle).
5
CRITERIA FOR GRAVIMETRIC ANALYSIS

2. The weighed form of the product should be of

known composition.
3. The product should be "pure" and easily filtered.
• It is usually difficult to obtain a product that is "pure“ (i.e.,
one that is free from impurities)
• Careful precipitation and sufficient washing may reduce
the level of impurities
6
MECHANISM OF PRECIPITATION
 Induction period
 The time before nucleation occurs after the addition of the
precipitating agent to the solution
 May range from milliseconds to several minutes
 Nucleation
 Formation of small, stable aggregates or nuclei of precipitate
 Nuclei have sizes down to ~1 nm, composed of a few atoms, and
there may be up to 1010 nuclei per mole of analyte
 Excess ions from solution collect around the nuclei

7
MECHANISM OF PRECIPITATION
Silver nitrate is added very slowly
to an acidic solution containing
chloride. Silver chloride nuclei
form with a surface layer of
ions. The “charged” AgCl
particles (or colloidal particles)
repel each other.

8
MECHANISM OF PRECIPITATION
 In addition to the primary adsorbed silver ions, some nitrate ions form an
electrostatic layer around the nucleus.
 These counter ions tend to aggregate around the [AgCl:Ag]+ center
because these centers have a net positive charge (excess Ag +) and
additional negative charge is required to maintain electrical neutrality.
 Counter ions are less tightly held than the primary adsorbed ions and the
counter ion layer is somewhat diffuse and contains ions other than those of
the counter ions.
 These layers of charged ions associated with the surface of the nuclei are
known as the electric double layer.

9
MECHANISM OF PRECIPITATION

10
MORE TERMINOLOGY
 Adsorption is a process in which a substance (gas, liquid,
or solid) condenses onto the surface of a solid
 The electric double layer of a colloid consists of a layer of
charge associated with the surface of the particles and a
layer with a net opposite charge in the solution surrounding
the particles
 A colloid is a finely divided particle (typically with
diameters from 10 nm to 1 m) that forms a stable
dispersion within a medium (air or liquid) 11
CONDITIONS FOR ANALYTICAL
PRECIPITATION
 Von Weimarn showed that particle size of precipitates is
inversely proportional to the relative supersaturation of the
solution during precipitation
 Relative supersaturation = (Q-S)/S
 Where Q is the molar concentration of the mixed reagents before any
precipitation occurs and S is the molar solubility of the product
(precipitate) when the system has reached equilibrium.
 For the best possible results, conditions need to be adjusted such that Q
will be as low as possible and S will be relatively large.

12
CONDITIONS FOR ANALYTICAL
PRECIPITATION
 Precipitation from hot solution
 The molar solubility (S) of precipitates increases with an
increase in temperature
 An increase in S decreases the supersaturation and increases
the size of the particle.
 Precipitation from dilute solution
 This keeps the molar concentration of the mixed reagents low.
Slow addition of precipitating reagent and thorough stirring
keeps Q low. (Uniform stirring prevents high local
concentrations of the precipitating agent.)
13
CONDITIONS FOR ANALYTICAL
PRECIPITATION
 Precipitationat a pH near the acidic end of the pH
range in which the precipitate is quantitative.
 Many precipitates are more soluble at the lower (more acidic)
pH values and so the rate of precipitation is slower.
 Digestion of the precipitate.
 The digestion period can lead to improvements in the
organization of atoms within the crystalline nuclei, such as
expulsion of foreign atoms (or other impurities).

14
Heating the precipitate within the mother liquor (or solution
from which it precipitated) for a certain period of time to
encourage densification of nuclei.
 During digestion, small particles dissolve and larger
ones grow. This process helps produce larger crystals
that are more easily filtered from solution

T

15
Homogeneous Precipitation
What?
Precipitating agent generated slowly by chemical reaction in
analyte solution
Why?
Precipitant appears gradually throughout
Keeps relative supersaturation low
Larger, less-contaminated particles
How?
(OH-) by urea decomposition
(NH2)2CO  2 OH- + CO2 + 2 NH4+

i.e Precipitation of Barium chromate

IMPURITIES IN PRECIPITATES
 Coprecipitation…

…is the precipitation of an unwanted species along with your

analyte of interest;
… occurs to some degree in every gravimetric analysis;
 A major factor for precipitations of barium sulfate and those
involving hydrous oxides
… and cannot be avoided, but can be minimized by careful
precipitation and a thorough washing of the precipitate.

17
IMPURITIES IN PRECIPITATES
 Surface adsorption
 Unwanted material is adsorbed onto the
surface of the precipitate
 Digestion of a precipitate reduces the
relative surface area and, therefore, the
area available for adsorption of
impurities
 Washing can remove impurities bound to
the surface 18
IMPURITIES IN PRECIPITATES
 Occlusion
 A type of coprecipitation in which impurities are
trapped within the growing crystal

• Post-precipitation
– Sometimes a precipitate in contact with the mother
liquor is contaminated by the precipitation of an
impurity
19
 Inclusion
 A type of coprecipitation in which the
impurities occupy the crystal lattice sites

Isomorphous Inclusion

Compounds with the same type of

formula crystallizing in similar
geometric forms
20
 Gathering
Precipitation of low concentration substances (i.e trace
metals) by co-precipitation onto a macro quantity of another
precipitate.
• Peptidization
– A procedure where the precipitate is AgCl (s)  →  AgCl (colloid)
washed and filtered, but part of the
precipitate reverts to the colloidal
form because supporting electrolyte
is gone.
21