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General Relation Valid for Electrolytic Systems

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Journal of Analytical Sciences, Methods and Instrumentation 2015年第4期5卷 74-85页

作者： Anna Maria Michalowska-Kaczmarczyk tadeusz michalowski Department of Oncology The University Hospital in CracowCracowPoland Department of Analytical Chemistry Technical University of CracowCracowPoland

A simple general relation P = Q + R + 1 between the number P of kinds of species, the number Q of charge and elemental/core balances and the number R of independent equilibrium constants is deduced, and its validity i... 详细信息

关键词： Electrolytic Systems Species Balances Equilibrium Constants

Compact Formulation of Redox Systems According to GATES/GEB Principles

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Journal of Analytical Sciences, Methods and Instrumentation 2014年第2期4卷 39-45页

The Generalized Electron Balance (GEB), together with charge balance and concentration balances, completes the set of equations needed for resolution of electrolytic redox systems. The general formulae for GEB were obtained according to Approach II to GEB, i.e., on the basis of the equation 2?f(O) ? f(H) obtained from elemental balances: f(H) for H, and f(O) for O. Equivalency of the Approach II and the Approach I to GEB was proved for an aqueous solution and a binary-solvent system. On this basis, a compact form of GEB was derived.

关键词： Electrolytic Redox Systems Generalized Electron Balance

Simplex Optimization and Its Applicability for Solving Analytical Problems

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Journal of Applied Mathematics and Physics 2014年第7期2卷 723-736页

Formulation of the simplex matrix referred to n-D space, is presented in terms of the scalar product of vectors, known from elementary algebra. The principles of a simplex optimization procedure are presented on a simple example, with use of a target function taken as a criterion of optimization, where accuracy and precision are treated equally in searching optimal conditions of a gravimetric analysis.

关键词： Simplex Simplex Optimization Procedure

Evaluation of Transition Points between Different Solid Phases in Aqueous Media

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Journal of Analytical Sciences, Methods and Instrumentation 2014年第3期4卷 87-94页

作者： Anna M.Michalowska-Kaczmarczyk tadeusz michalowski Department of Oncology The University Hospital in CracowCracowPoland Faculty of Engineering and Chemical Technology Technical University of CracowCracowPoland

A uniform procedure is suggested for calculation of the pHt value(s) separating equilibrium solid phases in pH scale, at an excess of the precipitating agent. The pHt value, related to pairs of precipitates formed from the species ??and ?, fulfils the relation , where F is a constant value involving pKso’s for solubility products (Kso’s) of these precipitates, and the equilibrium data, related to the species composing these precipitates.

关键词： Electrolytic Systems Precipitates pH-Intervals

Formulation of the System of Isohydric Solutions

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Journal of Analytical Sciences, Methods and Instrumentation 2012年第1期2卷 1-4页

作者： tadeusz michalowski Agustin G.Asuero Faculty of Engineering and Chemical Technology Technical University of CracowKrakówPoland Department of Analytical Chemistry The University of SevilleSevilleSpain

The isohydricity (pH constancy) as the property referred to mixtures of acids or bases, is illustrated on a simple example of the solutions: HL (C0, mol/L) and HL (C mol/L) mixed according to titrimetric mode (pH titration). A new derivation of the michalowski formula C0=C+C2·10PK1 expressing this property is presented, and its applicability for determination of pK1 = – logK1 value is indicated. The principle of the isohydric method of pK1 determination is also outlined.

关键词： Isohydric Solutions pH Titration

Calculation of Solubility of Oxyquinolinates

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Journal of Analytical Sciences, Methods and Instrumentation 2014年第3期4卷 71-79页

The solubilities (s, mol/L) of different oxyquinolinates (oxinates, MeL2) are calculated using the formulae obtained according to elementary algebra, with the use of Excel spreadsheets. The calculations are involved with solution of algebraic equation of the third degree, obtained on the basis of concentration balances. The root of this equation, , is then inserted into the charge balance, and resolved according to zeroing procedure. In principle, the calculations are related to aqueous media. Nonetheless, the extension on liquid-liquid extraction systems is also proposed.

关键词： Solubility Oxyquinolinates

Disproportionation Reactions of HIO and NaIO in Static and Dynamic Systems

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American Journal of Analytical Chemistry 2014年第15期5卷 1046-1056页

作者： Marcin Toporek Anna Maria Michalowska-Kaczmarczyk tadeusz michalowski Faculty of Engineering and Chemical Technology Technical University of CracowCracowPoland Department of Oncology The University Hospital in CracowCracowPoland

The paper refers to disproportionation of HIO and NaIO in aqueous media, in static and dynamic systems. The results of calculations, realized according to GATES/GEB principles, with use of an iterative computer program, are presented graphically. An example of the computer program with all physicochemical knowledge involved in the related algorithm is attached herewith.

关键词： Disproportionation Generalized Approach to Electrolytic Systems Generalized Electron Balance HIO NaIO

Linear Dependence of Balances for Non-Redox Electrolytic Systems

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American Journal of Analytical Chemistry 2014年第17期5卷 1285-1289页

作者： Anna M. Michalowska-Kaczmarczyk tadeusz michalowski Department of Oncology The University Hospital in CracowCracowPoland Faculty of Engineering and Chemical Technology Technical University of CracowCracowPoland

Two complex dynamic non-redox systems are considered as examples, providing interdependent linear equations. A simple and efficient linear combination method that leads the system of equations to the identity, 0 = 0, is used for this purpose. These examples are clear confirmations of the general property differentiating non-redox and redox electrolytic systems. This property is involved with linear dependence or independence of 2·f(O)-f(H) on charge and elemental/core balances for elements/cores ≠H, O, where f(H) and?f(O) are elemental balances for H and O, respectively.

关键词： Titration Liebig-Denigès Method Complexonometric Detemination of Zinc

Solubility and Dissolution in Terms of Generalized Approach to Electrolytic Systems Principles

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Journal of Analytical Sciences, Methods and Instrumentation 2015年第4期5卷 47-58页

作者： Anna Maria Michalowska-Kaczmarczyk tadeusz michalowski Marcin Toporek Andrzej Pietrzyk Department of Oncology The University Hospital in CracowCracowPoland Department of Analytical Chemistry Technical University of CracowCracowPoland

The correct approach, based on the rules of conservation and detailed physicochemical/thermodynamic knowledge on the system considered is opposed to conventional approach to solubility and dissolution, based on stoichiometry of a reaction notation and on the solubility product (Ksp) of a precipitate. The correct approach is realized according to Generalized Approach to Electrolytic Systems (GATES) principles, with use of iterative programs applied for computational purposes. All the qualitative and quantitative knowledge is involved in the balances and independent expressions for the equilibrium constants. Three two-phase electrolytic systems with diversified chemical properties were selected carefully, from the viewpoint of their diversity. The results of calculations are presented graphically and discussed. The advantages of the GATES in resolution of two-phase (static) non-redox systems and one complex (dynamic) redox system are proved.

关键词： Solubility Dissolution GATES