CHEMISTRY 59-320ANALYTICAL CHEMISTRY Fall - 2010.ppt

CHEMISTRY 59-320ANALYTICAL CHEMISTRY Fall - 2010 Lecture 16 Chapter 12: EDTA Titrations 12-1 Metal-Chelate complexes Metal ions are Lewis acids, accepting electrons pairs from electron-donating ligands that are Lewis bases. Monodentate ligand: binds to a metal ion through only one atom. Multidentate ligand: attaches to a metal ion through more than one ligand atom, also known as chelating ligand. Chelate effect: the ability of multidentate ligands to form more stable metal complexes than those formed by similar monodentate ligands. A titration based on complex formation is called a complexometric titration. Following are structures of analytically useful chelating agents: 12-2 EDTA EDTA is an abbreviation for ethylenediaminetetraacetic acid, a compound that forms strong 1:1 complexes with most metal ions. EDTA is a hexaprotic system, designated H6Y2+. The highlighted, acidic hydrogen atoms are the ones that are lost upon metal-complex formation. The neutral acid of EDTA is tetraprotic, with the formula H4Y. A commonly used reagent is the disodium salt, Na2H2Y · 2H2O We can define α for each species as the fraction of EDTA in that form. For example, is defined above. Fractional composition diagram for EDTA The equilibrium constant for the reaction of a metal with a ligand is called the formation constant, Kf, or the stability constant The number is called the conditional formation constant, or the effective formation constant. It describes the formation of MYn?4 at any particular pH. pH affects the titration of Ca2+ with EDTA. Below pH ≈ 8, the end point is not sharp enough to allow accurate determination. The conditional formation constant for CaY2? is just too small for “complete” reaction at low pH. 12-3 EDTA Titration Curves Since at equivalence point, there is exactly as much EDTA as metal in the solution, we can treat the solution as if it had been made by dissolving pure MYn?4. Some free Mn+ is generated by