MAGNETIC-PROPERTIES OF LANTHANUM MANGANITE AND VALENCE EQUILIBRIA OF MANGANESE

The paramagnetic susceptibility of lanthanum manganite has been measured over a wide temperature range (100-1073 K). On the basis of the thermodynamic equilibria between the various manganese ions with different valence and spin states and the magnetic interactions between the various manganese ions, a semiempirical formula has been proposed to calculate the paramagnetic susceptibilities of lanthanum manganite at different temperatures. The results indicate that most of the discrepancies between the calculated and experimental reciprocal susceptibilities of lanthanum manganite are less than 10% and that the relative contents of the various manganese ions in lanthanum manganite vary with temperature. The relative content of the trivalent manganese ion with a high spin state is dominant over the whole temperature range, while be relative content of the tetravalent manganese ion with a high spin state decreases monotonously with increasing temperature. At 300 K the calculated relative content of the tetravalent manganese ion in lanthanum manganite is about 34%, which is in good agreement with the experimental result (30%). There are some divalent manganese ions present in lanthanum manganite from low temperature to high temperature. The ratio of the relative contents of the tetravalent and divalent manganese ions in the compound varies with temperature. Above 750 K the relative content of the tetravalent manganese ion is less than that of the divalent manganese ion. The variation in the electrical resistivity of lanthanum manganite with temperature has also been interpreted reasonably.

Equilibria and Dynamics of a Neural Network Model for Opponent Muscle Control

One of the advantages of biological skeleto-motor systems is the opponent muscle design, which in principle makes it possible to achieve facile independent control of joint angle and joint stiffness. Prior analysis of equilibrium states of a biologically-based neural network for opponent muscle control, the FLETE model, revealed that such independent control requires specialized interneuronal circuitry to efficiently coordinate the opponent force generators. In this chapter, we refine the FLETE circuit variables specification and update the equilibrium analysis. We also incorporate additional neuronal circuitry that ensures efficient opponent force generation and velocity regulation during movement.

Acid-base and electrochemical properties of manganese meso(ortho- and meta-N-ethylpyridyl)porphyrins: potentiometric, spectrophotometric and spectroelectrochemical study of protolytic and redox equilibria.

The difference in electrostatics and reduction potentials between manganese ortho-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP) and manganese meta-tetrakis(N-ethylpyridinium-3-yl)porphyrin (MnTE-3-PyP) is a challenging topic, particularly because of the high likelihood for their clinical development. Hence, a detailed study of the protolytic and electrochemical speciation of Mn(II-IV)TE-2-PyP and Mn(II-IV)TE-3-PyP in a broad pH range has been performed using the combined spectrophotometric and potentiometric methods. The results reveal that in aqueous solutions within the pH range ∼2-13 the following species exist: (H(2)O)Mn(II)TE-m-PyP(4+), (HO)Mn(II)TE-m-PyP(3+), (H(2)O)(2)Mn(III)TE-m-PyP(5+), (HO)(H(2)O)Mn(III)TE-m-PyP(4+), (O)(H(2)O)Mn(III)TE-m-PyP(3+), (O)(H(2)O)Mn(IV)TE-m-PyP(4+) and (O)(HO)Mn(IV)TE-m-PyP(3+) (m = 2, 3). All the protolytic equilibrium constants that include the accessible species as well as the thermodynamic parameters for each particular protolytic equilibrium have been determined. The corresponding formal reduction potentials related to the reduction of the above species and the thermodynamic parameters describing the accessible reduction couples were calculated as well.

Solvation effects on equilibria: Triazoles and N-methyl piperidinol

We have performed calculations of the solvation effects on a number of equilibrium constants in water using a recently proposed hybrid quantum classical scheme in which the liquid environment is modelled using classical solvent molecules and the solute electronic structure is computed using modern quantum chemical methods. The liquid phase space is sampled from a fully classical simulation. We find that solvation effects on both triazole tautomeric equilibrium constants and piperidinol conformational equilibrium constants can be interpreted in terms of subtle differences in the local environment which can be seen in probability densities and radial distribution functions. Lower level calculations were performed for comparison and we conclude that the solvation thermodynamics can be predicted from a good classical model of solvent and solute molecules, but the implicit models that we tried are less successful.

Thermochemistry of Ionic Liquid-Catalyzed Reactions. Experimental and Theoretical Study of Chemical Equilibria of Isomerization and Transalkylation of tert-Butylbenzenes

The chemical equilibrium of mutual interconversions of tert-butylbenzenes was studied in the temperature range 286 to 423 K using chloroaluminate ionic liquids as a catalyst. Enthalpies of five reactions of isomerization and transalkylation of tert-butylbenzenes were obtained from temperature dependences of the corresponding equilibrium constants in the liquid phase. Molar enthalpies of vaporization of methyl-tert-butylbenzenes and 1,4-ditert-butylbenzene were obtained by the transpiration method and were used for a recalculation of enthalpies of reactions and equilibrium constants into the gaseous phase. Using these experimental results, ab initio methods (B3LYP and G3MP2) have been tested for prediction thermodynamic functions of the five reactions under study successfully. Thermochemical investigations of tert-butyl benzenes available in the literature combined with experimental results have helped to resolve contradictions in the available thermochemical data for tert-butylbenzene and to recommend consistent and reliable enthalpies of formation for this compound in the liquid and the gaseous state.

Partial Cooperative Equilibria: Existence and Characterization

We study the solution concepts of partial cooperative Cournot-Nash equilibria and partial cooperative Stackelberg equilibria. The partial cooperative Cournot-Nash equilibrium is axiomatically characterized by using notions of rationality, consistency and converse consistency with regard to reduced games. We also establish sufficient conditions for which partial cooperative Cournot-Nash equilibria and partial cooperative Stackelberg equilibria exist in supermodular games. Finally, we provide an application to strategic network formation where such solution concepts may be useful.

Structure of Adenine on Metal Nanoparticles: pH Equilibria and Formation of Ag+ Complexes Detected by Surface-Enhanced Raman Spectroscopy

The SERS spectra of adenine recorded under a broad range of pH values and concentrations using both silver and gold colloids provided evidence for the existence of several distinct species. At high concentration (0.5-10 ppm), the spectra recorded between pH 1 and 11 showed only two distinct spectra, rather than the three forms that would be expected for a compound with two pK(a) values of 4.2 and 9.8. The spectra at neutral and alkaline pH were identical and assigned to the deprotonated form of adenine on the basis of DFT calculations, isotope shifts, and comparison with the normal Raman spectra of neutral and deprotonated adenine. The spectra at acidic pH were different, consistent with adenine protonation. Neutral adenine was not detected at any pH studied. At low adenine concentration (

RESONANCE RAMAN INVESTIGATION OF PH-DEPENDENT EQUILIBRIA OF WATER-SOLUBLE IRON PORPHYRINS

Resonance Raman spectroscopy has been used to probe the structures of; tetrakis(1-methylpyridinium-4-yl)-porphinatoiron(III), FeIII (T4MPyP); tetrakis(1-methylpyridium-2-yl)porphinatoiron(III), FeIII (T2MPyP); tetrakis(4-sulphonatophkenyl)porphinatoir(III), FeIII(TSPP); and tetrakis(4-carboxylatophenyl)porphinatoiron(III), FeIII(TCPP), over a wide pH range. The anionic complexes FeIII (TSPP) and FeIII (TCPP) contain high-spin iron(III) at all pHs. Both these complexes exhibit marked spectral changes at ca. pH 6 which correspond to conversion from the diaquo species, in acid solution, to hydroxy- or mu-oxo dimer complexes. Both cationic complexes show similar diaquo to high-spin hydroxy, or mu-oxo dimer, transitions at ca. pH 6. However, at pH > 11.5 for FeIII (T4MPyP) and pH > 9 for FeIII (T2MPyP) a second equilibrium process is observed, leading to two new species. One of these is readily assigned as the low-spin iron(III) dihydroxy complex by analogy with spectra of the dicyano complex. The second species is assigned to the hydroxy iron(II) complex by comparison with photo-chemically generated FeII (T4MPyP) (OH). The formation of iron(II) species in alkaline solutions of FeIII (T4MPyP) and FeIII (T2MPyP) is entirely unexpected and the significance of the observation to previous investigations of the pH-dependent behaviour of these complexes is discussed.

Nash equilibria of network formation games under consent

We investigate the Nash equilibria of game theoretic models of network formation based on explicit consent in link formation. These so-called “consent models” explicitly take account of link formation costs. We provide characterizations of Nash equilibria of such consent models under both one-sided and two-sided costs of link formation. We relate these equilibrium concepts to link-based stability concepts, in particular strong link deletion proofness.

Phase Equilibria of Binary and Ternary Systems Containing ILs, Dodecane, and Cyclohexanecarboxylic Acid

This paper reports both the binary and ternary phase behavior of ionic liquids for extracting cyclohexanecarboxylic acid (CCA) from dodecane. This system is a model for the extraction of acids representative of naphthenic acids found in crude oils. In order to develop an effective ternary liquid-liquid extraction system the preliminary selection of ionic liquids was based on CCA miscibility and the dodecane immiscibility with selected ILs. A wide range of ILs based on different cations, anions, cation alkyl-chain length, as well as the effect of temperature on the overall fluid phase behavior is reported. Factors such as variation of cation group, anion effect, alkyl-chain length, and temperature all impact the extraction to various degrees. The largest effects were found to be the lipophilicity of the IL cation and the co-ordination ability of the anion. While CCA capacity increased with lipophilicity of the cation, as did the dodecane. Highly coordinating anions such as trifluoroacetate and triflate demonstrated that highly efficient extraction could be obtained producing favorable tie-lines in the ternary phase diagram. Overall, this study demonstrates that ILs can selectively extract acids from hydrocarbon streams and offers possible treatment solutions for problems associated with the processing of high acid crude oils.

Solid–liquid equilibria in systems [Cxmim][Tf2N] with diethylamine

In the present work, the solid–liquid–liquid equilibrium in the binary system of diethylamine (1) and ionic liquid (2) 1-methyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide and solid–liquid equilibrium in system 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide was studied. Phase equilibrium was determined experimentally by means of a polythermic method. These data were then used to determine the activity coefficients for both ionic liquids. For the pure diethylamine the enthalpy of fusion was determined by differential scanning calorimetry, because to the best of our knowledge, this data is not yet reported in the open literature, a contrario of pure ionic liquids tested during this work.

Evaluation of the ionic liquids 1-alkyl-3-methylimidazolium hexafluorophosphate as a solvent for the extraction of benzene from cyclohexane : ( Liquid + liquid ) equilibria

In the catalytic hydrogenation of benzene to cyclohexane, the separation of unreacted benzene from the product stream is inevitable and essential for an economically viable process. In order to evaluate the separation efficiency of ionic liquids (ILs) as a solvent in this extraction processes, the ternary (liquid + liquid) equilibrium of 1-alkyl-3-methylimidazolium hexafluorophosphate, [Cnmim][PF6] (n = 4, 5, 6), with benzene and cyclohexane was studied at T = 298.15 K and atmospheric pressure. The reliability of the experimentally determined tie-line data was confirmed by applying the Othmer–Tobias equation. The solute distribution coefficient and solvent selectivity for the systems studied were calculated and compared with literature data for other ILs and sulfolane. It turns out that the benzene distribution coefficient increases and solvent selectivity decreases as the length of the cation alkyl chain grows, and the ionic liquids [Cnmim][PF6] proved to be promising solvents for benzene–cyclohexane extractive separation. Finally, an NRTL model was applied to correlate and fit the experimental LLE data for the ternary systems studied.