Unsteady motion in single-line flow-injection systems

Unsteady motion in single-line flow-injection systems consisting of n tubular elements with valve or hydrodynamic injection is studied theoretically. A formula for the duration of the initial period of unsteady flow is derived. This initial period is much shorter than the mean residence time of the analyte in practical systems. It can therefore be neglected in mathematical modelling of such systems. Experimental data obtained with single-line systems with valve and hydrodynamic injection confirmed the validity of the theoretical equations.     

Weak distributive laws and their role in lattices of congruences and equational theories

By a result of Pigozzi and Kogalovskii, every algebraic latticeL having a completely join —irreducible top element can be represented as the lattice L() of equational theories extending some fixed theory . Conversely, strengthening a recent result due to Lampe, we show that such a representationL=L() forcesL to satisfy the following condition: if the top element ofL is the join of a nonempty subsetB ofL then there are elementsb..., B such thata=(... (((b₁ a) b₂) a) ... b_n) a for alla L. In presence of modularity, this equation reduces to the identitya=(a b₁) ... (a b_n). Motivated by these facts, we study several weak forms of distributive laws in arbitrary lattices and related types of prime elements. The main tool for applications to universal algebra is a generalized version of Lampe's Zipper Lemma.Presented by Ralph Freese.     

Tensor products of contexts and complete lattices

Although the categoryCLC of complete lattices and complete homomorphisms does not possess arbitrary coproducts, we show that the tensor product introduced by Wille has the universal property of coproducts for so-called distributing families of morphisms (and only for these). As every family of morphisms into a completely distributive lattice is distributing, this includes the known fact that in the category of completely distributive lattices, arbitrary coproducts exist and coincide with the tensor products. Since the definition of tensor products is based on the notion of contexts and their concept lattices, many results on tensor products extend from complete lattices to contexts. Thus we introduce two kinds of tensor products for arbitrary families of contexts, a partial and a complete one, and establish universal properties of these tensor products.Presented by B. Jonsson.     

Posets isomorphic to their extensions

A standard extension for a poset P is a system Q of lower ends (descending subsets) of P containing all principal ideals of P. An isomorphism between P and Q is called recycling if [Y]Q for all YQ. The existence of such an isomorphism has rather restrictive consequences for the system Q in question. For example, if Q contains all lower ends generated by chains then a recycling isomorphism between P and Q forces Q to be precisely the system of all principal ideals. For certain standard extensions Q, it turns out that every isomorphism between P and Q (if there is any) must be recycling. Our results include the well-known fact that a poset cannot be isomorphic to the system of all lower ends, as well as the fact that a poset is isomorphic to the system of all ideals (i.e., directed lower ends) only if every ideal is principal.     

Numerical solution of hydraulic models based on the axially-dispersed plug flow model by Laplace transforms

The problem of solving hydraulic models based on the axially-dispersed plug flow model which are applicable for the mathematical modelling of different flow-through systems both in chemical analysis (e.g., chromatography, flow injection analysis) and chemical industry (e.g., different tubular reactors) is discussed. Methods for numerical inversion of the model solution in the Laplace domain by expanding it into series of orthogonal functions are compared. Best results with respect to precision and consumption of computation time are given by the methods employing Chebyshov polynomials of the first kind and Fourier sine series. These methods were found to be better in these respects than some other frequently used numerical inversion methods.     

Influence of structural changes on the ion selectivities of magnesium ionophores based on malonic acid diamides

In an investigation of octamethylene bis(malonic acid diamides) and their selectivities for magnesium, it was found that presence of secondary amides within the particular ionophore played a considerable role in the enhancement of magnesium selectivity. Similar effects in other ionophores, i.e. tris(malonic acid diamides), were thus systematically looked at with the help of selectivity measurements with the hope of optimizing the number of secondary and tertiary amides so as to improve the magnesium selectivity. The syntheses of several investigated tris(malonic acid diamide) isologues are equally reported.Deceased in November 1992     

Solution dynamics and stability of lanthanide(III) (S)-2-(p-nitrobenzyl)DOTA complexes

Addition of a benzyl substituent to the macrocyclic ring of DOTA has a substantial impact on the conformational ring flipping motion of the macrocycle in the resulting LnDOTA complexes. The p-NO2-benzyl substituent in the Ln(p-NO2-Bn-DOTA)- complexes lies in an equatorial position and effectively "locks" the conformation of the ring into the deltadeltadeltadelta configuration. The presence of the p-NO2-benzyl group also increases the population of the square antiprismatic (SAP) coordination isomer for all Ln(p-NO2-Bn-DOTA)- complexes relative to that seen for the respective LnDOTA- complexes. Despite this increase in SAP isomer population, the rate of water exchange in these complexes remains comparatively fast. The kinetic and thermodynamic stabilities of the Ln(p-NO2-Bn-DOTA)- complexes are also slightly lower than the corresponding LnDOTA- complexes but appear to be sufficiently high for in vivo use.     

Flow-injection approach for the determination of the dynamic response characteristics of ion-selective electrodes. Part 1. Theoretical considerations

A single-line flow-injection system with a straight tube reactor is proposed for investigating the dynamic response behaviour of ion-selective electrodes. The principle of the method is based on the fact that the concentration—time curve at the electrode surface can be described theoretically in the flow-injection system under certain practically realizable conditions. The response of the ion-selective electrode to that input signal can be measured experimentally. Thus, knowing the input and the output signal of an ion-selective electrode, an appropriate model describing its dynamic behaviour can be selected among the relevant models existing in the literature. Theoretical expressions for predicting the transient response of ion-selective electrodes in the flow system when the rate-determining step is an ion-transport process through a diffusion layer or a kinetic process were elaborated.     

Mössbauer study of new vanadate glass with large charge-discharge capacity

Charge-discharge capacity and cyclicity of lithium ion battery (LIB) was evaluated in which 15Li₂O·10Fe₂O₃·xSnO₂·5P₂O₅·(70–x)V₂O₅ glass (x?=?0 and 20 in mol%, abbreviated as xLFSPV) was used as a cathode. A local structure of xLFSPV glass before and after charging was investigated by ⁵⁷Fe- and ¹¹⁹Sn-Mössbauer spectroscopies. ⁵⁷Fe-Mössbauer spectrum of xLFSPV glass with ‘x’ of 20 was composed of a doublet with isomer shift (δ) of 0.35_±0.02 mm s^???1 and quadrupole splitting (Δ) of 0.88_±0.03 mm s^???1 due to distorted Fe^IIIO₄ tetrahedra. ¹¹⁹Sn-Mössbauer spectrum of this glass consisted of a doublet with δ of 0.08_±0.01 and Δ of 0.52_±0.01 mms^???1 due to distorted Sn^VIO₆ octahedra. After discharging the battery from 4.5 to 1.0 V, larger δ of 0.40_±0.03 mm s^???1 and Δ of 0.94_±0.04 mm s^???1 were obtained, indicating that both iconicity of Fe-O bonds and local distortion of Fe^IIIO₄ tetrahedra were increased. On the contrary, identical δ of 0.09_±0.01 mm s^???1 and Δ of 0.50_±0.01 mm s^???1 were observed in the ¹¹⁹Sn-Mössbauer spectrum of 20LFSPV glass after the discharge, indicating that chemical environment of Sn^IVO₆ octahedra was not affected after the discharge. Charge-discharge curve of LIB containing 20LFSPV glass as a cathode active material recorded under the current density of 8.3 mA g^???1 (0.011 mA cm^???2) between 1.0 and 4.5 V showed a large initial charge capacity of 431.1 mAh g^???1 and discharge capacity of 382.3 mAh g^???1, respectively. These results indicate that 20LFSPV glass could be a new cathode active material for LIB.     

Redox interactions between structurally different alkylresorcinols and iron(III) in aqueous media: frozen-solution 57Fe Mössbauer spectroscopic studies,redox kinetics and quantum chemical evaluation of the alkylresorcinol reactivities

Iron(III)-containing aqueous solutions of 5-methylresorcinol (5-MR), 5-n-propylresorcinol (5-n-PR) and 4-n-hexylresorcinol (4-n-HR) at pH ~ 3 were studied by means of ⁵⁷Fe transmission Mössbauer spectroscopy. Kinetic considerations were applied to the redox reactions. Density Functional Theory (DFT) calculations were performed for the alkylresorcinol (AR) molecules and their non-alkylated analogue (resorcinol). Mössbauer spectra consisted of quadrupole doublets assigned to high-spin Fe(III) and Fe(II) species. From changes in their relative spectral areas, a gradual reduction of Fe(III) by all the ARs studied was observed. However, significant differences were found for the reduction rates among the ARs. The following series of the reduction rates was established by means of Mössbauer spectroscopy: 4-n-HR ? 5-MR > 5-n-PR, supplemented by rate constants calculated using a kinetic model. DFT calculations resulted in the following series: 4-n-HR ? 5-n-PR > 5-MR ? resorcinol (the latter is not oxidised under the conditions applied). The reversed order of the experimentally observed 5-MR and 5-n-PR oxidation rates may be explained in terms of their different kinetic parameters related to their structure.