Gravimetric Methods

of Analysis
 Gravimetry

- quantitative method based on determining the mass of a pure

compound to which the analyte is chemically related
Types of Gravimetric Analysis

1. VOLATILIZATION METHOD

- the analyte or its decomposition products are volatilized at

a suitable temperature, subsequently adsorbed and weighed

2. PRECIPITATION METHOD

- the analyte is converted to a sparingly soluble precipitate;

the precipitate is then filtered, washed, dried/ignited, and
weighed
Types of Gravimetric Analysis
1. VOLATILIZATION METHOD
- the analyte or its decomposition products are volatilized at a suitable
temperature, subsequently adsorbed and weighed

NaHCO3 (aq) + H2SO4 (aq) CO2 (g) + H2O (l) + NaHSO4 (aq)
Types of Gravimetric Analysis
2. PRECIPITATION METHOD
Example
Determination of Calcium in Water [AOAC Official Methods of Analysis]

Water sample Precipitation Reactions

+ H2C2O42H2O and HCl
heat to b.pt. 2 NH3 + H2C2O4 2 NH4+ + C2O42-
+ NH3
CaC2O4 ppt C2O42- (aq) + Ca2+ (aq) CaC2O4 (s)
filter, wash (in crucible)
dry Ignition Reaction
ignite at >950C
CaC2O4 (s) CaO (s) + CO (g) + CO2
CaO residue
(g)
weigh
PROPERTIES OF PRECIPITATING REAGENTS

1. react specifically or selectively with the analyte

2. react with the analyte to give a precipitate with ideal properties

SELECTIVITY vs. SPECIFICITY

AgNO3 precipitates Cl-, Br-, I-, and SCN- (in acidic medium) [SELECTIVE]

Dimethylglyoxime precipitates Ni2+ only (in basic medium) [SPECIFIC]

PROPERTIES OF PRECIPITATES

1. readily filtered and washed free of contaminants*

2. of sufficiently low solubility so that no significant loss of the
solid occurs during filtration and washing
3. unreactive with constituents of the atmosphere
4. of known composition after it is dried or, if necessary, ignited
Particle Size and Filterability of Precipitates
easy to filter and wash free of contaminants = large particles

range of precipitate particle sizes:

COLLOIDS CRYSTALS
10-7 to 10-4 cm diameter tenths of a mm (or greater) in diameter
remain suspended in solution settle spontaneously
not easily filtered easily filtered
FACTORS THAT AFFECT PARTICLE SIZE

1. Solubility
2. Temperature
3. Reactant concentrations
4. Rate of mixing
5. Relative supersaturation (qualitative)

Von-Weimarn equation
Q-S
relative supersaturation =
S
where,
Q = concentration of solute at any instant
S = equilibrium solubility

Q-S Q-S
crystalline ppt

colloidal ppt S
S desirable
Precipitate Formation Processes

Nucleation
- a small number of ions, atoms, Particle Growth
or molecules come together to
form a stable solid (nuclei) - growth on existing nuclei
- nuclei formation is initiated on
surface of any solid contaminants - rate increases with decreasing
present (e.g. dust particles) relative supersaturation
- rate increases with increasing
relative supersaturation

predomination of Nucleation
large number of predomination of Particle Growth

very fine particles smaller number of
large particles
 Controlling Particle Size
LOW RELATIVE
SUPERSATURATION
predomination of
Q-S Particle Growth
relative supersaturation =
S smaller number of
large particles
S - increase temperature (CRYSTALLINE PPT)
- control pH

Q - precipitate from dilute solutions

- slow addition of precipitating agent
with good stirring
 ANALYTE
+ PRECIPITATING REAGENT

PPT

YES crystalline? NO, Colloidal Peptization

DIGESTION INDUCE
REPRECIPITATION COAGULATION IF FILTERED,
AND WASHED
Purer, more WITH PURE H2O
filterable PPT Coagulated COLLOID
DIGESTED,
FILTERED, WASHED FILTERED, WASHED
WITH A VOLATILE WITH A VOLATILE
ELECTROLYTE, ELECTROLYTE,
DRIED IN OVEN, OR DRIED IN OVEN, OR
IGNITED IN FURNACE IGNITED IN FURNACE

PPT suitable PPT suitable

for weighing for weighing
ELECTRICAL DOUBLE LAYER = Primary Adsorbed Ion + Counter-Ion Layer
 Inducing Colloid Coagulation

HEATING, STIRRING
ELECTROLYTE
CONCENTRATION COAGULATED
COLLOID
DIGESTION* (heating of the
Precipitate for 1 hour
in the mother liquor)

*DIGESTION also improves the purity DENSER MASS

and filterability of crystalline precipitates
Peptization
- the process by which a coagulated colloid
reverts back to its original dispersed state

- brought about by washing of the coagulated colloid

with pure water

- avoided by washing the precipitate with a solution

containing an electrolyte that volatilizes when the
precipitate is dried or ignited (e.g. HNO3 or HCl)
Coprecipitation
- the process by which normally soluble compounds are
carried out of solution by a precipitate

1. SURFACE ADSORPTION process in which the primary

adsorbed ions and counter ions are carried out of solution on
the surface of a solid

- major source of contamination in coagulated colloids

- can be minimized by washing the coagulated colloid with
a solution containing a volatile electrolyte
Coprecipitation

2. MIXED-CRYSTAL FORMATION/INCLUSION process

in which a contaminant ion REPLACES an ion in the lattice
of the crystal

examples:
PbSO4 in BaSO4
SrSO4 in BaSO4
MnS in CdS
MgKPO4 in MgNH4PO4

requirement for ion replacement:

ions are of the same charge and almost the same size
the two salts form the same crystal structure
Coprecipitation

3. OCCLUSION process in which foreign ions in the counter-

ion layer is trapped within a pocket formed during rapid
crystal growth
4. MECHANICAL ENTRAPMENT process in which
several crystals grow together and trap a portion of the
solution in a tiny pocket

- minimized by keeping relative supersaturation low

- contamination can also be minimized by DIGESTION
(opens up the pockets)