The exchange processes in o-vanillin salicyloylhydrazone as studied by two-dimensional NMR

Multidimensional NMR studies of o-vanillin salicyloylhydrazone at various temperatures have been undertaken in deuterated dimethyl sulfoxide and its cryoprotective mixture in H2O and D2O, acetone and acetonitrile. The molecule is found to exist in two conformers in dimethyl sulfoxide and the cryoprotective mixture. The exchange between the two conformers has been detected from the two-dimensional experiments - information which is not easily obtainable from the normal one-dimensional spectra. Results in the different solvents are interpreted in terms of solvent-solute interactions.

Theory of electron transfer processes via chemisorbed intermediates: Part II. Current-potential characteristics

Current-potential characteristics are obtained numerically for a lone-adsorbate-mediated anodic charge transfer at the electrode-solution interface. An increase in the overpotential leads to the appearance of maxima in the anodic current-potential plots instead of the extended activationless region (i.e. a saturation current at large positive overpotentials) predicted by the direct heterogeneous outer-sphere anodic charge transfer process. A detailed analysis of the dependence of current-potential profiles and other kinetic parameters on various system parameters is also presented.

Thermodynamics of flow and vaporization processes in long-chain liquids

The flow and vaporization behaviors of long-chain esters of varying molecular weights (300-900) ana branching (linear, Y-shaped, and +-shaped molecules) have been studied. The flow behavior is found to depend on the structure as well as the molecular weight. Below a molecular weight of 600, the molecules flow wholly but above this, segmental motion occurs, and the flow becomes independent of the molecular weight which is explained from the blob model. The blob concept demonstrates that the hole of a size of about 11 angstrom is needed for the flow to occur and it is much less than the size of the molecule. The blob size is observed to slightly decrease along the series linear and Y- and +-branched esters. The heat of vaporization is found to be independent of the molecular structure since the molecules acquire a coiled spherical shape during vaporization and hence depends only on the molecular weight. A significant structural effect is observed for the esters on their glass transition temperature (T(g)). The T(g) vs molecular weight plot displays contrasting trend for linear and +-branched esters, with Y esters showing an intermediate behavior. It is explained from their molecular packing and entanglement as visualized by the blob model.

Low electric field, easily reversible electrical set and reset processes in a Ge15Te83Si2 glass for phase change memory applications

We report here an easily reversible set-reset process in a new Ge15Te83Si2 glass that could be a promising candidate for phase change random access memory applications. The I-V characteristics of the studied sample show a comparatively low threshold electric field (E-th) of 7.3 kV/cm. Distinct differences in the type of switching behavior are achieved by means of controlling the on state current. It enables the observation of a threshold type for less than 0.7 mA beyond memory type (set) switching. The set and reset processes have been achieved with a similar magnitude of 1 mA, and with a triangular current pulse for the set process and a short duration rectangular pulse of 10 msec width for the reset operation. Further, a self-resetting effect is seen in this material upon excitation with a saw-tooth/square pulse, and their response of leading and trailing edges are discussed. About 6.5 x 10(4) set-reset cycles have been undertaken without any damage to the device. (C) 2011 American Institute of Physics. doi: 10.1063/1.3574659]

Some Basic Aspects of Reaction Engineering of Precipitation Processes

Analysis of precipitation reactions is extremely important in the technology of production of fine particles from the liquid phase. The control of composition and particle size in precipitation processes requires careful analysis of the several reactions that comprise the precipitation system. Since precipitation systems involve several, rapid ionic dissociation reactions among other slower ones, the faster reactions may be assumed to be nearly at equilibrium. However, the elimination of species, and the consequent reduction of the system of equations, is an aspect of analysis fraught with the possibility of subtle errors related to the violation of conservation principles. This paper shows how such errors may be avoided systematically by relying on the methods of linear algebra. Applications are demonstrated by analyzing the reactions leading to the precipitation of calcium carbonate in a stirred tank reactor as well as in a single emulsion drop. Sample calculations show that supersaturation dynamics can assume forms that can lead to subsequent dissolution of particles that have once been precipitated.

Modelling transport processes during microwave heating: A review

The review is concerned with models that analyze transport:processes that occur during microwave heating. Early models on microwave. heating used Lambert's law to describe the microwave power absorption. Over the last decade, models for transport processes have been developed with the microwave power derived from Maxwell's equations. Those models, primarily based on plane waves, have been used for analyzing microwave heating of solids, liquids, emulsions, microwave thawing and drying. The models illustrate phenomena such a resonances, hot spots, edge and runaway heating. The literature on microwave sintering, susceptor heating and microwave assisted synthesis is largely experimental in nature and only key issues are highlighted. To fully appreciate the models for microwave heating, a section on the theory of electromagnetic wave propagation is included, where expressions for the electric field in dielectric slabs and cylinders are presented.

Residence time distribution for a class of Gaussian Markov processes

We study the distribution of residence time or equivalently that of "mean magnetization" for a family of Gaussian Markov processes indexed by a positive parameter alpha. The persistence exponent for these processes is simply given by theta=alpha but the residence time distribution is nontrivial. The shape of this distribution undergoes a qualitative change as theta increases, indicating a sharp change in the ergodic properties of the process. We develop two alternate methods to calculate exactly but recursively the moments of the distribution for arbitrary alpha. For some special values of alpha, we obtain closed form expressions of the distribution function. [S1063-651X(99)03306-1].

Jointly Optimal MMSE design for non-redundant FIR precoding and equalization

We provide a filterbank precoding framework (FBP) for frequency selective channels using the minimum mean squared error (MMSE) criterion. The design obviates the need for introducing a guard interval between successive blocks, and hence can achieve the maximum possible bandwidth efficiency. This is especially useful in cases where the channel is of a high order. We treat both the presence and the absence of channel knowledge at the transmitter. In the former case, we obtain the jointly optimal precoder-equalizer pair of the specified order. In the latter case, we use a zero padding precoder, and obtain the MMSE equalizer. No restriction on the dimension or nature of the channel matrix is imposed. Simulation results indicate that the filterbank approach outperforms block based methods like OFDM and eigenmode precoding.

Damped Belief Propagation Based Near-Optimal Equalization of Severely Delay-Spread UWB MIMO-ISI Channels

In this paper, we present a belief propagation (BP) based equalizer for ultrawideband (UWB) multiple-input multiple-output (MIMO) inter-symbol interference (ISI) channels characterized by severe delay spreads. We employ a Markov random field (MRF) graphical model of the system on which we carry out message passing. The proposed BP equalizer is shown to perform increasingly closer to optimal performance for increasing number of multipath components (MPC) at a much lesser complexity than that of the optimum equalizer. The proposed equalizer performs close to within 0.25 dB of SISO AWGN performance at 10-3 bit error rate on a severely delay-spread MIMO-ISI channel with 20 equal-energy MPCs. We point out that, although MIMO/UWB systems are characterized by fully/densely connected graphical models, the following two proposed features are instrumental in achieving near-optimal performance for large number of MPCs at low complexities: i) use of pairwise compatibility functions in densely connected MRFs, and ii) use of damping of messages.

Geochemistry of water and ground water in the Nhecolandia, Pantanal of Mato Grosso, Brazil: Variability and associated processes

A distinctive feature of the Nhecolandia, a sub-region of the Pantanal wetland in Brazil, is the presence of both saline and freshwater lakes. Saline lakes used to be attributed to a past and phase during the Pleistocene. However, recent studies have shown that saline and fresh water lakes are linked by a continuous water table, indicating that saline water could come from a contemporary concentration process. This concentration process could also be responsible for the large chemical variability of the waters observed in the area. A regional water sampling has been conducted in surface and sub-surface water and the water table, and the results of the geochemical and statistical analysis are presented. Based on sodium contents, the concentration shows a 1: 4443 ratio. All the samples belong to the same chemical family and evolve in a sodic alkaline manner. Calcite or magnesian calcite precipitates very early in the process of concentration, probably followed by the precipitation of magnesian silicates. The most concentrated solutions remain under-saturated with respect to the sodium carbonate salt, even if this equilibrium is likely reached around the saline lakes. Apparently, significant amounts of sulfate and chloride are lost simultaneously from the solutions, and this cannot be explained solely by evaporative concentration. This could be attributed to the sorption on reduced minerals in a green sub-surface horizon in the "cordilhieira" areas. In the saline lakes, low potassium, phosphate, magnesium, and sulfate are attributed to algal blooms. Under the influence of evaporation, the concentration of solutions and associated chemical precipitations are identified as the main factors responsible for the geochemical variability in this environment (about 92 % of the variance). Therefore, the saline lakes of Nhecolandia have to be managed as landscape units in equilibrium with the present water flows and not inherited from a past and phase. In order to elaborate hydrochemical tracers for a quantitative estimation of water flows, three points have to be investigated more precisely: (1) the quantification of magnesium involved in the Mg-calcite precipitation; (2) the identification of the precise stoichiometry of the Mg-silicate; and (3) the verification of the loss of chloride and sulfate by sorption onto labile iron minerals.

Reversible and irreversible switching processes in pure and lanthanum modified lead zirconate thin films

The mechanism of field induced phase switching in antiferroelectric lead zirconate and La-modified lead zirconate thin films has been analysed in terms of reversible and irreversible switching process under weak fields as a function of donor concentration. Extension of Rayleigh law of ferromagnetic materials to the present antiferroelectric and modified antiferroelectric compositions have clearly showed that origin of small signal dielectric permittivity is due to reversible domain wall motion. Rayleigh's constant, a measure of irreversible switching process, exhibited a slight increase with lower La3+ concentrations and followed by a gradual fall for higher concentration. This clearly illustrates that donor addition to antiferroelectric thin films controls the domain switching even under weak fields. (C) 2002 Elsevier Science B.V. All rights reserved.

Risk-sensitive optimal control for Markov decision processes with monotone cost

The existence of an optimal feedback law is established for the risk-sensitive optimal control problem with denumerable state space. The main assumptions imposed are irreducibility and a near monotonicity condition on the one-step cost function. A solution can be found constructively using either value iteration or policy iteration under suitable conditions on initial feedback law.

Thermal degradation processes in polysulfide copolymers investigated by direct pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/mass spectrometry

This is the first report on the analysis of random block polysulfide copolymers containing different amounts of repeating units in the copolymer backbone, which has been studied by direct pyrolysis mass spectrometry (DPMS) and by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The homopolymers such as poly(ethylene sulfide) (PES), poly(styrene sulfide) (PSS), and two random copolymers, viz., poly(ethylene sulfide(x)-co-styrene sulfide(y)) [copolymer I (x = y = 0.5) and copolymer II (x = 0.74, y = 0.26)] were investigated by both DPMS and Py-GC/MS (except copolymer II) techniques. In the case of copolymer I, the thermal degradation products of SE1, SE2, S-2, and S2E (S = styrene sulfide, E = ethylene sulfide) were detected in DPMS, whereas the formation of SE1 and SE2 were observed by Py-GC/MS technique. However, for copolymer II, SE3 was also found along with SE1, SE2, S-2, and S2E in DPMS. The formation of additional product (SE3) observed in copolymer II could be due to an increase in the block length formed during copolymerization. Further, a comparative study on thermal degradation of PES, poly(ethylene disulfide) (PEDS), and poly(ethylene tetrasulfide) (PETS) were investigated by Py-GC/MS. The pyrolysis products detected by both DPMS and Py-GC/MS indicates that the thermal decomposition of these polymers yield cyclic sulfides through an intramolecular exchange or by backbiting processes. The linear products with thiol and vinyl groups were also observed by Py-GC/MS along with the cyclic products via carbon hydrogen transfer reaction.