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Gravimetric Analysis

Gravimetric Analysis
A Gravimetric analysis is
based upon the measurement
of the weight of a substance
that
has
a
KNOWN
composition
AND
IS
chemically related to the
analyte.

Gravimetric Analysis
Accurate and precise.
Possible sources of errors can

be checked.
It is an ABSOLUTE method.
Relatively inexpensive

Gravimetric Analysis
Precipitation methods.
Volatilisation methods.
Electrogravimetry.
Thermogravimetry.

Precipitation:
Dissolve sample
Add ppting
reagent
Filter
Dry
Weigh

dissolved
components
sample

precipitating agent

Gravimetric Analysis
In precipitation methods, the
species
to
be
determined
is
precipitated by a reagent that yields
a sparingly soluble product that has
a known composition or can be
converted to such a substance.

Gravimetric Analysis
Precipitation methods.
Analyte (or chemically related species)

isolated as a sparingly soluble precipitate


of known composition.
Analyte (or chemically related species)

isolated as a sparingly soluble precipitate


that can be converted by heat to species
of known composition.

Gravimetric Analysis
Determination

of silver.
A solution of Ag+ is treated with an
excess of NaCl or KCl solution, the
precipitate is filtered off, washed well
with water to remove soluble salts,
dried at 130 - 150C and weighed as
AgCl.

Gravimetric Analysis
Frequently the constituent being
estimated is weighed in a form other
than that it was precipitated in.

Mg2+: precipitated as Mg(NH4)PO4.6H20

but
is
weighed
as
magnesium
pyrophosphate Mg2P2O7 after ignition.

Gravimetric Analysis
Conditions:

1.
Must
be
a
stoichiometric
reaction.
2. A stable product; no oxidation,
dehydration
or
gelatinous
precipitates.
3. Must avoid side reactions which
result in coprecipitates.

Gravimetric Analysis
Accuracy

Solubility Products.
Solubility.
Particle size.
Coprecipitates.
Drying and ignition.

Gravimetric Analysis
Solubility

Products
Even the most insoluble products
have at least a certain solubility. It is
therefore more correct to call these
compounds
sparingly
soluble
substances, eg: AgCl

Gravimetric Analysis
Equilibrium between AgCl

precipitate and the saturated


solution.

AgCl(s)

Ag+(aq) + Cl-(aq)

Gravimetric Analysis

The corresponding thermodynamic


equilibrium constant KT is given by:

+
[Ag
][Cl
]
KT =
[AgCl]

Gravimetric Analysis

AgCl is in a solid phase


therefore
[AgCl] = 1

KTSP = [Ag+][Cl-]

Gravimetric Analysis
Solubility.

Common ion effect


Ionic strength
Fractional precipitation
Complex ions
Temperature
Solvent

Gravimetric Analysis
Particle size.
Colloidal suspension (10 -6 - 10-4 mm

diameter) to crystalline precipitate.


Depends on nucleation and particle

growth.

Gravimetric Analysis
Coprecipitates.

Removal during precipitation of

compounds which are otherwise


soluble.
Sources:
Surface adsorption
Mixed crystal formation
Occlusion
Mechanical entrapment

Gravimetric Analysis
Drying and ignition.
Removes solvents and volatiles
Decomposition to known form

Gravimetric Analysis
Inorganic:
H2S, AgNO3, HCl, BaCl2

Organic
2,4-DNP

Gravimetric Analysis
8-Hydroxyquinoline

O
Mg2+ + 2

Mg

N
OH

Selectivity

through pH control

+ 2H+

Gravimetric Analysis
8-Hydroxyquinoline Examples
Metal

pH

pH

Initial Ppt.

Complete

Metal

pH

pH

Initial Ppt.

Complete

Ppt

Ppt

Aluminium

2.9

4.7 9.8

Manganese

4.3

5.9 9.5

Bismuth

3.7

5.2 9.4

Molybdenum

2.0

3.6 7.3

Cadmium

4.5

5.5 13.2

Nickel

3.5

4.6 10.0

Calcium

6.8

9.2 12.7

Thorium

3.9

4.4 8.8

Cobalt

3.6

4.9 11.6

Titanium

3.6

4.8 8.6

Copper

3.0

>3.3

Tungsten

3.5

5.0 5.7

Iron(III)

2.5

4.1 11.2

Uranium

3.7

4.9 9.3

Lead

4.8

8.4 12.3

Vanadium

1.4

2.7 6.1

Magnesium

7.0

>8.7

Zinc

3.3

>4.4

Gravimetric Analysis
Dimethylglyoxine

CH3
Ni2+ + 2 CH3

CH3

N N
HO

OH

O N N O
H
H + 2H+
Ni
O N N O
CH3

Weakly alkaline conditions

CH3

Nickel salt bright red

CH3

Summary
Principles
Solution reaction between analytes and

reagents to give sparingly soluble products.


Drying or ignition of precipitates.
Weighing
Apparatus
Flasks, beakers, pipettes, crucibles and

filter papers.
Oven or furnace and a dessicator.
Analytical quality balance.

Summary
Applications
Extensive numbers of inorganic ions

are determined with excellent


precision and accuracy.
Routine assays of metallurgical
samples.
Relative precision 0.1 to 1%.
Good accuracy

Summary
Disadvantages
Careful and time

consuming.
Scrupulously clean
glassware.
Very accurate weighing.
Coprecipitation.