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.

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. (or chemically related species) isolated as a sparingly soluble precipitate that can be converted by heat to species of known composition.

Analyte

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. on nucleation and particle growth.

Depends

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 N OH O N Mg N + 2H+

Selectivity

through pH control

Gravimetric Analysis

8-Hydroxyquinoline Examples
Metal pH Initial Ppt. pH Complete Ppt 4.7 9.8 5.2 9.4 5.5 13.2 9.2 12.7 4.9 11.6 >3.3 4.1 11.2 8.4 12.3 >8.7 Metal pH Initial Ppt. pH Complete Ppt 5.9 9.5 3.6 7.3 4.6 10.0 4.4 8.8 4.8 8.6 5.0 5.7 4.9 9.3 2.7 6.1 >4.4

Aluminium Bismuth Cadmium Calcium Cobalt Copper Iron(III) Lead Magnesium

2.9 3.7 4.5 6.8 3.6 3.0 2.5 4.8 7.0

Manganese Molybdenum Nickel Thorium Titanium Tungsten Uranium Vanadium Zinc

4.3 2.0 3.5 3.9 3.6 3.5 3.7 1.4 3.3

Gravimetric Analysis

Dimethylglyoxine
CH3 C C CH3 O N N O H H + 2H+ Ni O N N O

Ni2+ + 2 CH3 HO

CH3 OH

N N

CH3

CH3

Weakly alkaline conditions

Nickel salt bright red

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. Good accuracy

Summary

Disadvantages
Careful

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