• Develop the study of ionic equilibrium in aqueous solutions.
• Apply the principles of thermodynamic on these equilibriums.
• Acquire new notions in relation with the quantitative methods of analyses.
Reminders & generalities.
1. Introduction: rule of the analytical chemistry; chemical analysis and processes; errors of chemical analysis; models of presentation of results.
2. Solvents & concentrations: structure of liquid water; influence of solvent & ions on solutions; aqueous solutions; activity & concentration.
3. Notion of conductimetry.
Reactions of transfer of 2 particles in homogenous medium.
1. Reactions of transfer of protons & electrons. Redox & acidity: prediction of reactions; quantitative relations of redox potential of solutions; variation of redox properties with pH; prediction of reactions as function of pH; disproportionation under pH effect; potential-pH diagram; construction & applications of some E-pH diagrams.
2. Reactions of transfer of electrons & ions. Redox & complexation: prediction of reactions; dissimulation of ions; successive complexes; dilution of complexes, diagram of repartition; variation of redox properties by formation of complexes; disproportionation, stabilization of the redox degree by formation of complex; diagram of E-pL (some examples, predominance domain, diagram construction).
3. Reactions of transfer of protons & ions. Complexation & acidity: prediction of reactions; dilution of acids & bases; Flood diagram; effect of the pH on the complexation’s equilibriums; complexes comporting a base; complexes with ions in the water; conditional constant of stability (effect of αH & βM & diagram).
Reactions of transfer of 2 particles in heterogenous medium.
1. Precipitation & acidity: precipitation by an excess of reactive; product of solubility; solubility of acids & of bases as function of the pH; case of hydroxides; solubility of salts less soluble (effect of the pKa & pKs); dissolution & precipitation of sulfurs as function of the pH; diagram of solubility as function of the pH; separation by precipitation in controlled pH medium.
2. Precipitation & complexation: selective destruction of complexes by formation of precipitates; effect of the complex stability; selective dissolution of precipitates by formation of complexes; effect of the pKs; precipitation then dissolution by addition of a reactive; separation by precipitation of certain compounds in presence of complexing ions (separations in presence of EDTA).
3. Precipitation & redox: redox properties of elements & dismutation; variation of redox properties by hydroxide precipitations (pH effect); variation of redox properties by precipitation of salts; stability of the oxidation degree by precipitation; dismutation by precipitation; dissolution of salts by redox reactions (sulfur cases); E-pH diagram in a precipitating medium.
4. Varied equilibriums-Transfer of more than 2 species of particles: Attack of metals (Au, Pt) by formation of complexes; redox systems of copper in chloride medium; diagram E-pCl in complexing and precipitating medium.
The ionic equilibriums in aqueous solutions are relatively very developed in the course Chem 101 (in particularly the reactions of transfer of a particle), by consequence, pay attention to not repeat the information & try to use these prerequisites to assume more specific and deep teaching of this course.
• All books of general chemistry or chemistry of solutions for the preparative classes or for the first academic cycle (Hachette, Bréal, Dunod, Masson..).
• G.Charlot, General analytical chemistry, tome I, Aqueous & non aqueous solutions, Masson, 1978.
• M.Guernet & M. Hamon, Abrégé de chimie analytique, tome I, Chimie des solutions, Masson, 1990.
• J.Y.GAL, Analytical study of chemical reactions in w ater. Paris: Tec & Doc-Lavoisier, 1989.
• D.A.Skoog, D.M.West & F.J. Holler, Analytical chemistry, Paris, De Boeck University, 1997.
• R.Gaboriaud, Physical-chemistry of solutions, Masson, 1996.