GRAVIMETRIC ANALYSIS

One of the oldest analytical methods to determine quantitatively macro amounts of analyte. Obtained by weighing solid product in a pure form.
Analyte + Reagent Precipitating agent Precipitate Pure, can be filtered, well separated

Steps in G.A.
Preparation of solution Precipitation Digestion Filtration Washing Drying or igniting Weighing Calculation
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Steps .
Dissolution
Sample is dried, weighed, dissolved in acid, etc.

Precipitation
Precipitates
Low S Comprises big crystals (easier to filter) Can be dried/ignited to reach stable composition.
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Steps
Precipitation reagent is selective for the analyte During precipitation process, supersaturation occurs, followed by nucleation and precipitation AgNO3 + Cl-

supersaturation [Ag+][Cl-] > Ksp

Ions in Solution (10-7 cm) colloid (10-7 -10-4 cm) Precipitate (10-4 cm)
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Precipitation .
First supersaturation (soln. contains more of the dissolved salt than at equilibrium) occurs. Nucleation particles come together to produce microscopic nuclei. The higher the degree of supersaturation, the greater the rate of nucleation. Nucleation can be induced by scratching vessel surface, dusts, etc.

Steps
Nucleation
Formation of nucleus or primary particles from ion, atoms or molecules, which aggregates to form a stable second phase. Growth of particles
Precipitation on top of formed nucleus.

The higher the degree of supersaturation, the higher the rate of nucleation. If rate of nucleation < rate growth of particles , big particles (crystals ) are formed (easy to filter, less impurities)
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Steps
Q-S S Q degree of supersaturation (Conc. of mixed reagents before ppt.) S solubility of ppts at equilibrium If Q-S high many small crystals (high surface area) S If (Q-S)/S low fewer, larger crystals, (low surface area) Therefore, we want to keep Q low and S high during pptn. 7 von Wiemarn ratio Relative supersaturation =

Favourable conditions for pptn.

Keep Q low by: Precipitate from dilute solution Add dilute ppt reagents slowly, with stirring. Keep S high by: Precipitate from hot solution. Precipitate at as low a pH as possible.

Steps
Digestion
Solution containing ppts are heated before filtering. Done for crystalline ppts (e.g., BaSO4) diameter >10-4 cm. Small particles will dissolve and ppt on top of larger particles. Trapped impurities will be dissolved. Objective: to obtain bigger and purer particles.
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Coprecipitation
Constituents that are normally soluble are precipitated together with the precipitate of interest.

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Coprecipitation
Sources
Adsorption on the surface of ppt. Especially colloidal ppts with high surface area. Eg,: in determination of Cl-, AgCl ppt is contaminated with Ag+ (primary layer) and NO3- (counter-ion layer).
The effect: AgNO3 is coppt with AgCl. Reduce by ==> digestion, wash with volatile electrolytes, ppt again after filtration.
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Coprecipitation
Formation of mixed crystals.
E.g., BaSO4 ppt is contaminated with PbSO4 Minimise by separating the interfering ions.

Occlusion
While crystals are growing, counter-ions are trapped on the surface of the crystal. Minimise by using slow rate formation of ppt, i.e., at low supersaturation conditions.

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Cl- -adsorbs on the particles when in excess (primary layer). Cl adsorbs on the particles when in excess (primary layer). A counter layer of cations forms. A counter layer of cations forms. The neutral double layer causes the colloidal particles to coagulate. The neutral double layer causes the colloidal particles to coagulate. Washing with water will dilute the counter layer and the primary layer charge causes the Washing with water will dilute the counter layer and the primary layer charge causes the particles to revert to the colloidal state (peptization). particles to revert to the colloidal state (peptization). So we wash with an electrolyte that can be volatilized on heating (HNO3).). So we wash with an electrolyte that can be volatilized on heating (HNO
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Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Representation of silver chloride colloidal particle and adsorptive layers when Cl- is in excess.

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During digestion at elevated temperature: During digestion at elevated temperature: Small particles tend to dissolve and reprecipitate on larger ones. Small particles tend to dissolve and reprecipitate on larger ones. Individual particles agglomerate. Individual particles agglomerate. Adsorbed impurities tend to go into solution. Adsorbed impurities tend to go into solution.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Ostwald ripening or digestion.

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Ostwald ripening or digestion. When a ppt. is allowed to stand in the presence of the mother liquor, large crystals grow at the expense of the small ones. The small particles tend to dissolve and reprecipitate on the surfaces of the larger crystals.
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Filtering & washing of ppts

Type of filter will depend on the particle size of ppts.
filter paper Gooch/glass sintered crucible

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Filtration.
Colloidal ppts E.g., AgCl
Mainly small particles. Cannot be filtered using normal filtration as they are not ppt from soln. Particles are charged due to adsorption of ions. Bigger particles are not formed (e.g., AgCl particles adsorb Ag+ and Cl- stronger).

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Colloidal ppts.
Agglomeration of colloidal particles. Is encouraged for formation of matter that can be easily filtered, can be ppt from solutions. Formation of larger particles Achieved if primary layer is not removed. By heating adsorbed ions , repulsion between ionic layers
Increase electrolyte conc in solution (neutralise particle charges)
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Agglomerated colloids
Peptidization
Takes place when washed with distilled water; reformation of small particle colloids. Use dilute HNO3 for washing. HNO3 is volatile when heated.

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Colloidal particles
Treatment
Ppt from hot solutions that is stirred and contain electrolytes, left for 1 hour or more for digestion (aging) Washed with electrolyte solution to avoid peptidization.

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Ppt from homogeneous solutions

Ppt agent is generated in-situ, slowly in analyte solution. Excess localised reagent is avoided (low relative supersaturation) E.g.,Production of OH- from urea (NH2)2CO + 2H20 CO2 + 2NH4+ + 2OHCan be used for the ppt of iron (III) oxide and aluminium Purer and easy to be filtered ppts from this technique.

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Drying/ignition
Ppt. must be in suitable form for weighing. Ppt. must be pure, stable, of certain known composition. Remove water efficiently; electrolytes in washing solvent. Appropriate chemical changes during heating.

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Drying/ignition
E.g.
AgCl drying in over 100 - 130oC to remove physically-bound water. Higher temp. is necessary if water is trapped in crystals / chemically-bound water / or ensure appropriate chemical changes Mg2P2O7 --> MgNH4PO4 900oC CaC2O4 --> CaO 1100oC

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Drying/ignition
Errors that might arise
Reduction of ppts by carbon (from filter paper) E.g., for AgCl use crucible Decomposition

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Calculations
% analyte = Mass analyte Mass sample x 100

Mass analyte = Mass ppt. x Gravimetric Factor (GF)

% analyte = Mass ppt. x GF x 100 Mass sample Gravimetric factor = f wt analyte (g/mol) x a f wt ppt. weighed (g/mol) b
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Weighed as Analyte GF _________________________________ BaSO4 S S____ BaSO4 BaSO4 SO3 SO3___ BaSO4 Fe2O3 FeO 2FeO__ Fe2O3 2MgO Mg2P2O7 Cr2O3 2PbCrO4 2K

Mg2P2O7

MgO

PbCrO4

Cr2O3

K2PtCl6

K2PtCl6 26 No. of atoms of element of interest same for numerator and denominator

Example
1.00 g of Cu3(AsO3)22As2O3Cu(C2H3O3)2 How many grams of CuO produced from above sample? g CuO = 1.00 g x (g/mol CuO) x 4 (g/mol Cu3(AsO3)22As2O3Cu(C2H3O3)2 1

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Example
1.00 g of Cu3(AsO3)22As2O3Cu(C2H3O3)2 How many grams of As2O3 produced from above sample? g As2O3 = 1.00 g x (g/mol As2O3) x (g/mol Cu3(AsO3)22As2O3Cu(C2H3O3)2

3 1

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Organic precipitating agents are chelating agents. Organic precipitating agents are chelating agents. They form insoluble metal chelates. They form insoluble metal chelates.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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Representative gravimetric analysis

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