title: Estimation of uncertainty in pKa values determined by potentiometric titration.
abstract: A procedure is presented for estimation of uncertainty in measurement of the pK(a) of a weak acid by potentiometric titration. The procedure is based on the ISO GUM. The core of the procedure is a mathematical model that involves 40 input parameters. A novel approach is used for taking into account the purity of the acid, the impurities are not treated as inert compounds only, their possible acidic dissociation is also taken into account. Application to an example of practical pK(a) determination is presented. Altogether 67 different sources of uncertainty are identified and quantified within the example. The relative importance of different uncertainty sources is discussed. The most important source of uncertainty (with the experimental set-up of the example) is the uncertainty of pH measurement followed by the accuracy of the burette and the uncertainty of weighing. The procedure gives uncertainty separately for each point of the titration curve. The uncertainty depends on the amount of titrant added, being lowest in the central part of the titration curve. The possibilities of reducing the uncertainty and interpreting the drift of the pK(a) values obtained from the same curve are discussed.
authors.affiliation: Institute of Chemical Physics, Department of Chemistry, University of Tartu, Jakobi 2, 51014 Tartu, Estonia.
authors.forename: Eve
authors.initials: E
authors.lastname: Koort
authors.forename: Koit
authors.initials: K
authors.lastname: Herodes
authors.forename: Viljar
authors.initials: V
authors.lastname: Pihl
authors.forename: Ivo
authors.initials: I
authors.lastname: Leito
mesh_terms: D000143:Acids / Q000032:analysis / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D011199:Potentiometry / Q000379:methods; D012680:Sensitivity and Specificity; D013499:Surface Properties; D017186:Titrimetry
chemical_list: D000143:Acids