* GRAVIMETRIC ANALYSIS : e Usually based on a chemical reaction aA + rR > AaRr where A = analyte R = reagent AaRr = product, slightly soluble substance a R is generally added in excess to repress the solubility of the precipitate “REQUIREMENTS OF GRAVIMETRIC METHODS 1. sufficiently complete separation process e < 0.1 mg analyte left unprecipitated in determining the major constituent of a macro sample 2. weighed substance has a definite composition, pure (or very nearly so) TYPES OF GRAVIMETRIC METHODS 1. Precipitation e Analyte converted to sparingly soluble precipitate e Precipitate is filtered, washed, converted to product of known composition e Product is weighed 2. Volatilization e Analyte/decomposition product volatilized e Product collected, weighed OR mass indirectly determined from loss in sample massaren STEPS IN GRAVIMETRIC ANALYSIS A. Precipitation e Conversion of a constituent to an insoluble ~ substance (precipitate) Filtration e Separation of a precipitate from its mother liquor e Precipitate is retained and concentrated on-the filter, while mother liquor passes through e Washing required to separate last traces of mother liquor from precipitate v Important to test for completeness of precipitation prior to filtration Drying and Ignition e Conversion of separated (precipitated) substance into a from suitable for weighing e Removal of water, electrolytes added to the wash solution/water e Depends on the chemical properties of the precipitate and the tenacity with which water is held by the solid Methods of Filtration i Zs a. Filter paper and funnel Filter crucibles sintered glass crucible ¢ all glass, porous, sintered glass mat for bottom e max temp 500° Cb. Gooch crucible e Porcelain, perforated bottom e Filter mat of asbestos fibers 3. Glass-fiber filters Methods of Drying and Ignition 1. Air drying (ambient: temperature) e Wash precipitate with volatile solvent, i.e., ether e Dry at ambient temperature e Water may not be removed completely 2. Air drying (low temperature) e Dry at 100° to 130°C 3. Ignition of precipitate e Complete removal of occluded or adsorbed water e Complete conversion of some precipitate to desired compound ¢ Gelatinous precipitates such as hydrous oxides to remove strongly adsorbed water . TYPES OF PRECIPITATES en yt : 1. COLLOIDAL Pca YL ,~fy * Particles do not tend to settle from solution ‘ a e Difficult to filter, not useful for gravimetric analysis 2. CRYSTALLINE e Particles settle spontaneously 2 tem e Readily filtered celleds + . = or jos lo em > pott te” om 7 > h0- tee Size of individual particles and.filterability can be controlled to a certain degree STAGES OF PRECIPITATE FORMATION 1. ‘Nucleation e Formation, in a supersaturated solution, of the smallest aggregate of molecules capable of growing into a large precipitate particle 2. Crystal growth e Growth of nucleation aggregate as ions or molecules from solution deposit on the aggregates’ surface in a regular, geometric pattern’ HANDLING COLLOIDAL PRECIPITATES COAGULATION/AGGLOMERATION ¢ Conversion of colloidal suspension into filterable solid e Breaking the stability of colloidal suspension by: 1. Heating a Decreases number of adsorbed ions a Decreases thickness of double layer a Increases kinetic energy of particles 2. Stirring a Increased chances for particles to come in contact with each other 3. Increasing electrolyte concentration a Increased concentration of counter-ion, shrinking the counter-ion layer (vane decrees)VON WEIMARN EQUATION Nucleation Rate of nucleation and crystal growth Q-S Ss Relative supersaturation = Q-S Ss Where Q*= concentration of species at any time S = equilibrium solubility Relative supersaturation or supersaturation ratio: e Q-S = measure of degree of supersaturation e Rate of nucleation increases exponentially with relative supersaturation e Rate of growth increases linearly with relative supersaturation e Most favorable relationship between growth and nucleation: (Q-S)/S is smallest HOW? Keep Q small by: a. using dilute solutionsb. slow addition of precipitating ‘agent c. rapid mixing e keep S large (to keep the ratio small) by increasing T, to increase solubility S e (Q-S)/S js large, colloidal precipitate e (Q-S)/S is small, crystalline precipitate COPRECIPITATION ¢ normally soluble compounds are removed from solution by a precipitate TYPES OF COPRECIPITATION 1. Surface adsorption 2. Mixed crystal formation 3. Occlusion 4. Mechanical entrapment SURFACE ADSORPTION e Common in coagulated colloids due to large surface area (internal surfaces still intact) e Lattice ions originally adsorbed on surface before coagulation and counter ion in solution adjacent to particle e An otherwise soluble compound carried down as surface contaminantCacn MIXED CRYSTAL FORMATION / /CLUS(EN Bs ¢ One of ions in crystal lattice of solid replaced by an ion of another element e Réplacement ion of the same charge, up to 5% or size, same crystal class e Increases as contaminant to analyte concentration ratio increases e Occurs in both colloidal and crystalline precipitate OCCLUSION e A compound is trapped within a pocket formed during rapid crystal growth ¢ Greatest amount occluded in portion of crystal initially formed (growth rate initially fastest, supersaturation highest, precipitation highest) e Occurs in crystalline precipitates MECHANICAL ENTRAPMENT Crystals close together trap portion of solution in tiny pocket e Occurs in crystalline precipitates MINIMIZING COPRECIPITATION PROBLEMS 1. Surface adsorption e Digestion Water is removed from solid Density increases, surface area decreasese Washing with volatile electrolyte ° ¢ Reprecipitation — filtered solid is redissolved and reprecipitated (lower contaminant concentration than the original for the second solution) 2. ‘Mixed crystal formation e Separate interfering ion prior to precipitation e Use a “specific” precipitating agent: Dimethylglyoxime is specific for Ni(II) AgNO; is selective for chloride, bromide and iodide 3. Occlusion and mechanical entrapment e Low supersaturation or low precipitation e Digestion (increased T releases impurities entrapped in pockets)