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

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

Inflection points on some S-shaped curves

This paper refers to inflection point—the fundamental property of S-shaped curves. In this paper, the inflection points are related to pH titration curve pH = pH(V), and to the curve σ = σ(pH) in-volved with surface tension, σ

Generalized Electron Balance (GEB) as the Law of Nature in Electrolytic Redox Systems

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

A Distinguishing Feature of the Balance 2∙f(O)−f(H) in Electrolytic Systems: The Reference to Titrimetric Methods of Analysis

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

Solubility Products and Solubility Concepts

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

Formulation of dynamic buffer capacity for phytic acid

The general formulation of dynamic buffer capacity for polyprotic acids and bases (and polyprotic acid and base salts) has been derived. Polyprotic acids show buffer capacity over a broad range of pH values, according to their successive protonation constants. Polyprotic acids with equidistant pki values behave as universal buffers. The paper covers the dynamic buffer capacity for phytic acid, which posse’s twelve acid groups. Phytic acid, the hexaphosphate ester of myoinositol, has a great biological relevance, and shows antioxidant/anticancer properties

Effect of Entodinium caudatum on starch intake and glycogen formation by Eudiplodinium maggii in the rumen and reticulum.

This study aimed to quantify the engulfed starch and reserve α-glucans (glycogen) in the cells of the ciliates Eudiplodinium maggii, as well the α-glucans in defaunated and selectively faunated sheep. The content of starch inside the cell of ciliates varied from 21 to 183 mg/g protozoal DM relative to the rumen fauna composition whereas, the glycogen fluctuated between 17 and 126 mg/g dry matter (DM) of this ciliate species. Establishment of the population Entodinium caudatum in the rumen of sheep already faunated with E. maggii caused a drop in both types of quantified carbohydrates. The content of α-glucans in the rumen of defaunated sheep varied from 4.4 to 19.9 mg/g DM and increased to 7.4–29.9 or 11.8–33.9 mg/g DM of rumen contents in the presence of only E. maggii or E. maggii and E. caudatum, respectively. The lowest content of the carbohydrates was always found just before feeding and the highest at 4 h thereafter. The α-glucans in the reticulum varied 7.5–40.1, 14.3–76.8 or 21.9–106.1 mg/g DM of reticulum content for defaunated, monofaunated or bifaunated sheep, respectively. The results indicated that both ciliate species engulf starch granules and convert the digestion products to the glycogen, diminishing the pool of starch available for amylolytic bacteria

Influence of Betalain-Rich Extract on Reduction of Discomfort Associated with Osteoarthritis

Summary Introduction. Osteoarthritis (OA) subjects typically experience progressive discomfort related to pain, joint stiffness, and general tiredness. The most common treatment of these conditions includes use of non-steroidal anti-inflammatory drugs (NSAIDS). However, efficacy of NSAID treatment is generally not completely satisfactory. Therefore, further improvements in management of OA-associated discomfort are needed. Aim. The aim was to verify whether a betalain-rich red beet extract at dose range of 35-100 mg twice per day could reduce discomfort associated with osteoarthritis (OA) conditions. Materials and methods. Study participants experiencing OA symptoms were treated with red beet extract (RBE) twice per day for exactly ten days. McGill and Energy Score data were evaluated at days 1, 5 and 10. The serum levels of advanced oxidation protein products (AOPP) were measured using a commercial kit (Cell Biolabs, Inc., #STA318). Sera from volunteers treated with RBE were subjected to a cytokines and chemokines array as offered by Qynsys Inc. Results. Collected data showed that ingestion of RBE for 10 days reduced McGill scores in a time-and dose-dependent manner with maximum 33% reduction as compared to the first day of the treatment. Interestingly, due to the treatment, serum levels of TNF-alpha were reduced in subjects whose serum TNF-alpha was greater than 1 pg/mL prior to initiation of the treatment. It was also found that serum levels of AOPP (proteins oxidized by hypochlorous acid/hypochlorites) were reduced by up to 48% after 10 days of the treatment. Conclusions. This study showed that ingestion of RBE, at dosages greater than 35 mg, had a beneficial effect on pain associated with OA conditions. RBE may act by inhibiting protein oxidation typically induced by hypochlorous acid released from active neutrophils