Gravimetric Analysis

gravi metric (weighing - measure)

The Process

Separate - by phases volatilization methods precipitation methods selective ppt'n account for interferences assure completeness (solubility equilibrium)

Precipitation:
Dissolve sample Add ppting reagent Filter Dry Weigh

dissolved components sample

precipitating agent

Calculating Amount of Precipitation Reagent

How many mL of 1% potassium chloride would be needed to precipitate all of the silver in a 0.5 g ore sample that contains 1.5 parts per thousand silver? Allow for a 15% excess of the chloride solution.

Gravimetric Overview

Measure tools for gravimetric analysis filter crucibles, an oven, balance Calculate stoichiometry Report values % composition, ppt, ppm, ppb uncertainty average standard deviation, confidence interval

The Precipitation Process (from solution)

Particle Size / Filterability

produce particles large enough to be 'caught ideally, produce crystals avoid colloidal suspension particle size = 1 - 100 nm

Precipitate Formation

crystallization

nucleation: particles join to produce aggregates crystal growth aggregate grows and 'fall out' of solution We want a few big chunks of precipitate! supersaturation: more solute than should be present in solution relative supersaturation: a measure of supersaturation, (Q-S)/S Q = actual solute concentration S = equilibrium solute concentration

Controlling Precipitation

Increase S

Increase temperature

Decrease Q
Dilute solution Well mixed (stirring)

pH control of precipitation
Ca2+ + C2O42- CaC2O4 (s) H2C2O4 2 H+ + C2O42Feeder Reaction:

Homogeneous Precipitation

Fe3+ + 3 HCO2- Fe(HCO2)3nH2O

(NH2)CO + 3 H2O + heat HCOOH + OH- + CO2 + 2 NH4+ Feeder Reaction:

High Electrolyte Concentration to Aid Precipitation

Excess charge on colloid creates ionic atmosphere around particle

D.C. Harris, Quantitative Chemical Analysis, 6th Ed., p686

Composition by Gravimetric Analysis

Ni2+ (aq) + H2DMG Ni(DMG)2 + 2 H+
A 0.8234 g ore sample produced 0.1397 g of bis(dimethylglyoximate) nickel (II) (FW = 288.91 g/mol). Find the nickel content. Explain how to create a large, filterable precipitate.

Combustion Analysis
Absorbs Absorbs water CO2

Find the empirical formula for a 13.72 mg organic sample that produced 6.97 mg of water and 28.44 mg of carbon dioxide
D.C. Harris, Quantitative Chemical Analysis, 6th Ed., p691

Gravimetric Interferences

Coprecipitated impurities Surface adsorption Contaminants bound to the surface Dry the sample Mixed crystals Replacements in the crystal lattice Reprecipitation Occlusions/mechanical entrapment Impurity pockets Slow digestion/masking agents

Gravimetric Overview

Simple Cheap

Glassware Reagents ovens, etc. Balances

Specific Timely Accurate Precise Sensitive