CHE 115

Gravimetric Analysis

VIII. Gravimetric Analysis

Gravimetric analysis is the quantitative isolation of a substance by precipitation and the weighing of the precipitate. Procedure: (Example: Analysis of Ca2+)
C

Dissolve a weighed sample in water.

Precipitate the sought substance (Ca2+) with the addition of a precipitating reagent (C2O42-). Ca 2% (aq)

% C2O42& (aq)

CaC2O4 @ H2O (s)

Filter, dry, and weigh the precipitate. Calculate moles of precipitate, moles of sought substance, and percentage of sought substance in the sample.

In a successful gravimetric analysis

C

The sought substance must be completely isolated from the remainder of the sample, To achieve this goal B Precipitates with very low solubilities (Ksp is very small) are selected and
CaC2O4 @ H2O (s)
B

Ca 2% (aq) % C2O42& (aq)

Ksp ' 2.1 @ 10& 9

An excess of the precipitating reagent is added.

The weighed precipitate must be a pure substance of known chemical composition, And the precipitate must be easily filtered.

A) Mechanism for Precipitation

C

Nucleation: Several ions of the precipitate come together to form a microsize particle called the nucleus. Growth: The particle grows with the addition of ions of the precipitate until the system comes to equilibrium.

CHE 115

Gravimetric Analysis

NH4+ Na+ NH4+ C2O42-

NH4+ C2O42Ca2+
C2O42-

NH4+
Ca2+

C2O42Ca2+

Solution
NH4+ NH4+ Na+

C2O42Ca2+ C2O42Ca2+

C2O42-

C2O42C2O42Ca2+ C2O42-

2Ca2+ C2O4

Primary Adsorbed Ions

C2O42Ca2+ C2O42-

Ca2+ Ca2+ C2O42C2O42- Ca2+ Ca2+

NH4+

Counter Ions

C2O42Na+ NH4+

Ca2+ C2O42-

Ca2+ C2O42-

Nucleus
Ca2+ C2O42-

C2O42Ca2+ C2O42-

Counter Ions

NH4

Ca2+ C2O42Ca2+ C2O42C2O42+

NH4+

NH4+

Na+

NH4+

Surface of Macrosize Particle

Solution

Primary adsorbed ions are ions of the precipitate that are adsorbed on the surface of the macrosize particle. As a result of the adsorption of these ions, the surface of the macrosize particle is charged. Ions of opposite charge are attracted to the region of the solution surrounding the particle. These ions are called counter ions.

B) Factors Affecting Particle Size As the particle size of the precipitate increases, the impurities decrease and the ease of filtration increases. The particle size of the precipitate is inversely proportional to the relative supersaturation. Relative Supersaturation

' Q&S
S

where Q is the concentration of the solute in solution at the instant the reagents are mixed, S is the concentration of the solute in a saturated solution (a saturated solution is a solution in which the solute in solution is in equilibrium with the solid solute), and Q - S , called supersaturation, is the concentration of the solute in excess of that found in a saturated solution.
Q

&S

When S is large, then the rate of nucleation is much greater than the rate of growth and the particle size of the precipitate is very small. 2

CHE 115

Gravimetric Analysis

&S
S

Techniques to minimize
C

Precipitation from a very dilute solution (Q is kept small) Slow addition of the precipitating reagent (Q is kept small) In Experiment #8 the precipitating reagent is slowly generated in situ
(H2N)2CO (aq) % 2 H2O urea H2C2O4 (aq) % 2 NH3 (aq) Oxalic acid
heat

NH3 (aq) % HCO3& (aq) % NH4% (aq)

2 NH4% (aq) % C2O42% (aq) oxalate ion (precipitating

reagent)

Precipitation from a hot solution ( Initially, S is kept large. When Q is very small at the end of the precipitation, S is reduced by cooling the solution.) Precipitation from an acidic solution ( Initially, S is kept large. When Q is very small at the end of the precipitation, S is reduced by neutralizing the solution.)

C) Calculations (Just Stoichiometry)

C

Find moles of precipitate. moles of precipitate

' wt of precipitate
FWprecipitate

Find moles of sought substance. moles of sought substance

'

wt of precipitate (mole ratio) FWprecipitate

Find weight of sought substance.

Calculate the percentage of the sample that is the sought substance.

CHE 115

Gravimetric Analysis

% sought substance

'

wt of sought substance 100 wt of sample

Example: A 0.4960 g sample of a CaCO3 is dissolved in an acidic solution. The calcium is precipitated as CaC2O4@H2O and the dry precipitate is found to weigh 0.6186 g. What is the percentage of CaO in the sample?
Unknown: % CaO in the 0.4960 g sample of CaCO3 Knowns: wt of CaCO3 sample = 0.4960 g, wt of CaC2O4@H2O = 0.6186 g Concepts: gravimetric factor, moles, mole ratio, FW wt of CaO ' (wt of CaC2O4@H2) 1 mole CaO 1 mole Ca 1 mole Ca 1 mole CaC2O4@H2O FWCaO

FWprecipitate

1 mole CaO wt of CaO ' (0.6186 g) 1 mole CaC O @H O 2 4 2 wt of CaO ' 0.2374 g

56.08

g mole g mole

146.12

% CaO '

wt of CaO 100 ' wt of sample

0.2374 g 100 ' 47.87 % 0.4960 g