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Gravimetry

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Gravimetric Method of Analysis

Quantitative method in which he mass of a pure compound (product) is used to determine the quantity of the analyte from the original sample.

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Types of Gravimetric Methods

Precipitation Gravimetry
The analyte is separated from a solution of the sample as a precipitate and is converted to a compound of known composition that can be weighed

Example: Analysis precipitation to AgCl

of

KCl

sample

by

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Types of Gravimetric Methods

Volatilization Gravimetry
The analyte is separated from other constituents of a sample by conversion to a gas of known composition. The weight of the gas serves as a measure of analyte concentration.

Example: Determination of NaHCO3 by decomposing the sample with strong acid to convert the analyte into CO2(g) and water. The gas is then weighed.
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Types of Gravimetric Methods

Electrogravimetry
The analyte is separated by deposition on an electrode by an electrical current. The mass of the product then provides a measure of the analyte concentration.

Example: Analysis of Cu by electrodeposition method

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PRECIPITATION METHODS

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Precipitation Gravimetry
Analyte is converted to a sparingly soluble precipitate by addition of a precipitating agent. The precipitate is then filtered, washed free from impurities, converted to a product of known composition by suitable heat treatment, and weighed.

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Analyte

Ppt

Isolated

Weighed

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Properties of Precipitates and Precipitating Agents

Precipitating agent should react specifically or at least selectively with the analyte The precipitate formed should be:
Easily filtered and washed free from contaminants Of sufficiently low solubility that no significant loss of the analyte occurs during filtration and washing Unreactive with constituents of the atmosphere Of known composition after it is dried or, if necessary, ignited.
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Particle Size and Filterability of Precipitates

Large particles as precipitates
Generally deisirable Easy to filter and wash free of impurities Purer than particles of finer size

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Particle Size and Filterability of Precipitates

Crystalline suspension
Particles with sizes of at least 10-4 cm Tends to settle spontaneously and are easily filtered

Colloidal suspension
Less than 10-4 cm particle size (10-4 to 10-7 cm) No tendency to settle Due to electric double-layer effect
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Factors that affect particle size

Precipitate solubility Temperature Reactant concentrations Rate of mixing Reaction pH
R.S. colloidal R.S. crystalline

Von Weimarn Equation

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Experimental Control of Particle Size

Aims to lower the relative supersaturation
Elevated temperature (increases S) Precipitation from dilute solutions (minimize Q) Slow addition of precipitating agent with good stirring (minimizes Q at any given instant) Control of pH

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Mechanism of Precipitate Formation

Nucleation
A process in which a minimum number of atoms, ions, or molecules join together to give a stable solid

Particle Growth Competition between nucleation and particle growth

If nucleation predominates large number of fine particles If particle growth predominates smaller number of larger particles predominate
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Colloidal Precipitates
Too small to be retained by ordinary filters Brownian motion prevents from settling down Can be coagulated or agglomerated to give a filterable mass Can be coagulated by heating, stirring, and adding an excess electrolyte

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Colloidal Precipitates
Peptization
Is a process by which a coagulated colloid returns to its dispersed state

Digestion
Is a process in which a precipitate is heated for an hour or more in the solution from which it was formed mother liquor Results in the removal of weakly bound water molecules from the precipitate; improves filterability
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Colloidal Precipitates
Aging
Allow impurities to be removed (equilibrium process) Allow precipitate to come into contact with supernatant liquid for some time

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Sources of Contamination
Coprecipitation is a process in which normally soluble compounds are carried out of a solution by a precipitate
Surface Adsorption Mixed crystal formation Occlusion Mechanical Entrapment

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Precipitation from Homogeneous Solution

A process in which a precipitate is formed by slow generation of precipitating agent homogeneously throughout the solution Decreases Q

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Drying and Ignition of Precipitates

Drying
Removes solvent and any volatile species carried down by the precipitate

Ignition
Decomposition of the precipitate by high temperature treatment that causes conversion to a more stable weighable form

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Applications of Gravimetric Analysis

Sensitivity
Samples having analyte concentration greater than about 1%

Accuracy
Relative error as low as 0.1 %

Selectivity Ease of Operation

Time consuming

Time
3 to 6 h

Cost
Small reagent and equipment cost High personnel cost
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CALCULATIONS INVOLVING GRAVIMETRIC DATA

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Gravimetric Calculations

Mass A
Divide by MW A

Moles A

Moles B
Divide by MW B

Mass B

Multiply by Stoichiometric ratio

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Worked Problems
What mass of AgNO3 (169.99 g/mol) is needed to convert 2.33 g of Na2CO3 (106.0 g/mol) to Ag2CO3? What mass of Ag2CO3 will be formed?
7.47 g AgNO3 6.06 g Ag2CO3

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Worked Problems
The calcium sample of a natural water was determined by precipitating the cation as CaC2O4. The precipitate was filtered, washed, and ignited in a crucible with an empty mass of 26.6002 g. The mass f the crucible plus CaO (56.077 g/mol) was 26.7134 g. Calculate the concentration of Ca (40.078 g.mol) in water in units of g per 100 mL of the water sample
0.04045 g/100 mL
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Worked Problems
An iron ore was analyzed by dissolving a 1.1324-g sample in concentrated HCl. The resulting solution was diluted with water, and the iron (III) was precipitated as the hydrous oxide Fe2O3 xH2O by the addition of ammonia. After filtration and washing, the residue was ignited at high temperature to give 0.5394 g of pure Fe2O3 (159.69 g.mol). Calculate (a) %Fe (55.547 g/mol) and (b) %%Fe3O4 (231.54 g/mol) in the sample 33.32% Fe 46.04% Fe3O4

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Worked Problems
A 0.2356 g sample containing ONLY NaCl (58.44 g/mol) and BaCl2 (208.23 g/mol) yielded 0.4637 g of dried AgCl (143.32 g/mol). Calculate the % of each halogen compound in the sample
55.01 %NaCl 44.99 %BaCl2

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Worked Problems
A sample containing NaCl, NaBr, & inert material weighs 1.000 g and with excess AgNO3 gives a white precipitate consisting of AgCl and AgBr which weighs 0.5260 g. By heating the precipitate in a current of Cl2 gas, the AgBr (187.78 g/mol) is converted to AgCl (143.32 g/mol) and the precipitate weighs 0.4260 g. Find the %NaCl (58.44 g.mol) and % NaBr (102.909 g/mol) in the sample.
4.219 %NaCl; 23.15 %NaBr
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END
More Problem Sets to Come

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