CHAPTER 12: CLASSICAL METHODS OF of the gas serves a measure of the

ANALYSIS analyte concentration)

 Electrogravimetry – separated
through “deposition” on an
 Gravimetric Methods of Analysis electrode by electrical current
 Titration in Analytical Chemistry
 Principles of Neutralization
Titrations PROPERTIES OF PRECIPITATES AND
 Applications of Neutralization PRECIPITATING REAGENTS
Titrations
 Complex Acid/Base Systems
 Complexation and Precipitation  Specific Reagent – reacts with one
Reactions and Titrations chemical species
 Selective Reagent – common; reacts
with a limited number of chemical
GRAVIMETRIC METHODS OF ANALYSIS species
Precipitating agents should react
specifically or at least selectively with the
Gravimetric Methods – quantitative
analyte
methods; determining the mass of a pure
compound (related to the analyte); based
on mass measurement
PRODUCTS IN GRAVIMETRIC METHODS
SHOULD BE:
Analytical Balance – instrument, in
gravimetric methods, that yields highly
1. Easily filtered and washed free of
accurate and precise data
contaminants
2. Sufficiently low solubility (no
significant loss of the analyte)
3 KINDS OF GRAVIMETRIC METHODS OF
3. Unreactive with constituents of the
ANALYSIS
atmosphere
4. Of known chemical composition
after it’s dried
 Precipitation Gravimetry – the
analyte is separated from the Large particles are desirable because they
solution as a soluble precipitate and are purer, easy to filter, and easy to wash
converted into a compound, by heat free of impurities
treatment, that can be weighed
 Volatilization Gravimetry – the
analyte is converted into a gas (mass
TWO PARTICLE SIZES OF PRECIPITATES Relative Supersaturation – particle size is
related to a single property of a system
(Q-S)/S
 Colloidal Suspension – a colloid
consists of solid particles from 10-7 - Q = concentration of the solute
10-4 cm in diameter; invisible to the
S = equilibrium solubility
naked eye; no tendency to settle
from a solution (Brownian
movement); difficult to filter;
Supersaturated Solution – unstable
perfectly clear in diffuse light; are
solution; higher solute concentration than a
stable because they appear as
saturated solution
positive and negative ions i.e. repel
each other out As solute precipitates, supersaturation
 Tyndall Effect - the path of decreases to zero
the beam can be seen
through the scattering visible
radiation; the amount of 2 MECHANISM OF PRECIPITATE
scattering depends on the: FORMATION
frequency of the light and
density of the particles
 Nucleation – atoms, and molecules
Coagulate colloidal particles to produce
join together to give a stable solid;
large particles that are easy to filter
nuclei forms in the surface of
 Crystalline Suspension – particles suspended solid contaminants;
with dimensions on the order of
Rate of nucleation is directly proportional to
tenths of a millimeter or greater
the relative supersaturation
(liquid phase); settle spontaneously;
easily filtered
 Particle Growth
if nucleation predominates = several fine
THE PARTICLE SIZE OF A PRECIPITATE IS
particles; if particle growth predominates =
INFLUENCED BY (4):
few large particles

 Precipitate solubility
high relative supersaturation = nucleation;
 Temperature
low relative supersaturation = particle
 Reactant concentration
growth
 The rate at which reactants are
mixed
EXPERIMENTAL CONTROL OF PARTICLE PEPTIZATION OF COLLOIDS
SIZE

Peptization – coagulated colloid reverts to

 Elevated temperature its original dispersed state; electrolytes in
 Increase the solubility (large coagulated colloids are leached from the
particles can be produced by internal liquid, therefore, increase the
controlling pH) volume of the counter-ion layer
 Dilute the solution to minimize Q
 Slow addition with good stirring
PRACTICAL TREATMENT OF COLLOIDAL
Precipitates with low solubility (sulfides and
PRECIPITATE
hydrous oxides) appear as colloids

Colloids are best precipitated in hot, stirred

Colloidal Precipitates – are too small to be
solution containing sufficient electrolyte to
retained by filters; Brownian motion
ensure coagulation
prevents the settling out of the solution

Digestion – precipitate is heated in the

COAGULATION OF COLLOIDS
solution (“Mother Liquor” – a solution from
which a precipitate was formed); improves
purity and filterability of both precipitates
Can be hastened by heating, stirring, and by
adding an electrolyte to the medium
CRYSTALLINE PRECIPITATES
Adsorption – the process in which a
substance is held on the surface of a solid;
are more easily filtered than colloidal
crystal growth
precipitates

Absorption – retention of a substance

within the pores of a solid
 Chelating Agent – organic reagents that
yield sparingly soluble coordination
DRYING AND IGNITION OF PRECIPITATES
compounds typically containing at least two
functional groups (5 or 6 membered rings)

Weighing Form – when a gravimetric

precipitate is heated until the mass
Chelates – the product of chelating agents
becomes constant

VOLATILIZATION GRAVIMETRY
Mass loss as a function of temperature for:
 Silver chloride
 Barium sulfate Determines water (vapor) and carbon
 Aluminum oxide dioxide

The temperature required to dehydrate a Direct Determination – mass is determined

precipitate may be as low as 100oC or as from the mass gain of the desiccant
high as 1000oC

Indirect Method – the amount of water is

Thermogravimetric Analysis – recording of determined by the loss of mass of the
thermal decomposition sample (during heating)
Thermograms – mass vs temperature
curves

Gravimetric methods do not require

calibration

ORGANIC PRECIPITATING AGENTS

2 Types of Organic Reagents:

 Coordination compounds – soluble;
nonionic
 Largely ionic products