Compact Formulation of Redox Systems According to GATES/GEB Principles

Abstract

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.

Formulation of Titration Curves for Some Redox Systems

“…In nearly all more complex systems, one can indicate the species (or a group of species) that are in a metastable state, relative to the solvent (e.g., 4 …”

“…It should also be noted that Φ plays a key role in formulation of the Generalized Equivalence Mass (GEM) concept [24] [25]. High buffer capacity of the titrand, resulting from presence of H 2 SO 4 (C 01 ) in it, causes rather small growth in pH value of the system considered ( Figure 4); the pH changes result from acid-base properties of 4 …”

“…To avoid a formulation of contradictory equations, pH = const during the titration was assumed in EA. However, such an assumption is not acceptable, for example, in (1) Br 2 with NaOH; (2) I 2 with NaOH in presence of (2a) KI, (2b) H 2 CO 3 , (2c) CCl 4 (liquid-liquid extraction system), (2d) KI + H 2 CO 3 + CCl 4 ; an interesting case where (3) MgSO 4 is added into I 2 + KI + NaOH was also considered. In all these systems, described in [7], the disproportionation reactions were accompanied by other effects.…”

Disproportionation Reactions of HIO and NaIO in Static and Dynamic Systems

“…The electron balance, termed as the Generalized Electron Balance (GEB) obtained according to Approach II to GEB, stems from linear combination 2•f(O)-f(H) of the elemental balances: f(H) for H, and f(O) for O [1]- [11]. This property was extended on non-aqueous and mixed-solvent media [1] [12] [13], with amphiprotic co-solvents involved. The Approach II is equivalent to the Approach I to GEB, based on the "common pool" of electron-active elements in a system considered.…”

Principles of Titrimetric Analyses According to Generalized Approach to Electrolytic Systems (GATES)

“…The detailed considerations in this chapter are based on principles of the generalized approach to electrolytic systems (GATES), formulated by Michałowski [9] and presented recently in a series of papers, related to redox [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] and nonredox systems [27][28][29][30][31][32] in aqueous and in mixed-solvent media [33][34][35][36][37]. The closed system separated from its environment by diathermal walls secure a heat exchange between the system and its environment, and realize dynamic processes in a quasistatic manner under isothermal conditions.…”