Tadeusz Michalowski

By Tadeusz Michałowski

Part of the book: Applications of MATLAB in Science and Engineering

By Anna Maria Michałowska-Kaczmarczyk, Aneta Spórna-Kucab and Tadeusz Michałowski

The chapter refers to a general concept of solubility product Ksp of sparingly soluble hydroxides and different salts and calculation of solubility of some hydroxides, oxides, and different salts in aqueous media. A (criticized) conventional approach, based on stoichiometry of a reaction notation and the solubility product of a precipitate, is compared with the unconventional/correct approach based on charge and concentration balances and a detailed physicochemical knowledge on the system considered, and calculations realized according to generalized approach to electrolytic systems (GATES) principles. An indisputable advantage of the latter approach is proved in simulation of static or dynamic, two-phase nonredox or redox systems.

Part of the book: Descriptive Inorganic Chemistry Researches of Metal Compounds

By Anna Maria Michałowska-Kaczmarczyk, Aneta Spórna-Kucab and Tadeusz Michałowski

The balance 2∙f(O)−f(H) provides a general criterion distinguishing between electrolytic redox and non-redox systems of any degree of complexity, in aqueous, non-aqueous and mixed-solvent media. When referred to redox systems, it is an equation linearly independent on charge (ChB) and elemental/core balances f(Yg) for elements/cores Yg ≠ H and O, whereas for non-redox systems, 2∙f(O)−f(H) is linearly dependent on these balances. The balance 2∙f(O)−f(H) formulated for redox systems is the primary form (pr-GEB) of the generalized electron balance (GEB) as the fundamental equation needed for resolution of these systems. Formulation of GEB for redox systems needs no prior knowledge of oxidation numbers for all elements of the system. Any prior knowledge of oxidation numbers for all elements in components forming a redox system and in the species of the system thus formed is not necessary within the Approach II to GEB. Oxidants and reductants are not indicated. Stoichiometry and equivalent mass are redundant concepts only. The GEB, together with charge balance and concentration balances for elements ≠ H and O, and the complete set of independent equations for equilibrium constants form an algorithm, resolvable with use of an iterative computer program. All attainable physicochemical knowledge can be included in the algorithm. Some variations involved with tests of possible reaction paths for metastable systems can also be made. The effects of incomplete physicochemical knowledge on the system can be also tested. One of the main purposes of this chapter is to provide the GEB formulation needed for resolution of redox systems and familiarize it to a wider community of chemists.

Part of the book: Advances in Titration Techniques

By Anna Maria Michałowska‐Kaczmarczyk, Aneta Spórna‐Kucab and Tadeusz Michałowski

The generalized equivalent mass (GEM) concept, based on firm algebraic foundations of the generalized approach to electrolytic systems (GATES) is considered, and put against the equivalent “weight” concept, based on a “fragile” stoichiometric reaction notation, still advocated by IUPAC. The GEM is formulated a priori, with no relevance to a stoichiometry. GEM is formulated in unified manner, and referred to systems of any degree of complexity, with special emphasis put on redox systems, where generalized electron balance (GEB) is involved. GEM is formulated on the basis of all attainable (and preselected) physicochemical knowledge on the system in question, and resolved with use of iterative computer programs. It is possible to calculate coordinates of the end points, taken from the vicinity of equivalence point. This way, one can choose (among others) a proper indicator and the most appropriate (from analytical viewpoint) color change of the indicator. Some interpolative and extrapolative methods of equivalence volume Veq determination are recalled and discussed. The GATES realized for GEM purposes provides the basis for optimization of analytical procedures a priori. The GATES procedure realized for GEM purposes enables to foresee and optimize new analytical methods, or modify, improve, and optimize old analytical methods.

Part of the book: Advances in Titration Techniques

By Anna Maria Michałowska-Kaczmarczyk, Aneta Spórna-Kucab and Tadeusz Michałowski

This chapter refers to fundamental/general/obligatory regularities of electrolytic systems. The linear combination 2·f(O) − f(H) of elemental balances, f(H) for H and f(O) for O, provides a rigorous criterion distinguishing between redox and non-redox systems is presented as the general relation distinguishing between electrolytic redox and non-redox systems in aqueous media. As the linearly independent equation for a redox system, 2·f(O) − f(H) is considered as the primary form of the generalized electron balance (GEB), perceived as a law of nature, as the hidden connection of physicochemical laws and the breakthrough in thermodynamic theory of electrolytic redox systems. GEB completes the set of 2+K equations necessary for thermodynamic resolution of redox systems according to generalized approach to electrolytic systems (GATES) applying all relevant, physicochemical knowledge available. GATES/GEB, perceived as an example of excellent paradigm, provides the best thermodynamic approach to electrolytic redox systems of any degree of complexity, in aqueous, non-aqueous, and mixed-solvent media. The formulation of GEB does not need prior knowledge of oxidation numbers for all elements in components forming any electrolytic system, within GATES/GEB, the stoichiometry, oxidation number, oxidant, reductant and equivalent mass are as derivative concepts.

Part of the book: Redox