Chemical kinetics at high pressure

Abstract

Numerous studies have demonstrated the importance to include pressure as a kinetic parameter in the elucidation of inorganic reaction mechanisms. These studies have specially led to a better understanding and a systematic classification of solvent exchange and ligand substitution reactions of octahedral complexes of transition metal elements. The mechanistic picture for substution reactions on square planar complexes is well established and involves a concurrent bimolecular attack by solvent and the nucleophile on the substrate with a considerable discrimination among different entering groups. The search for factor promoting the conversion of the normal associative mode of activation into a dissociative process has then attracted much attention. Two attempts to induce dissociation, as studied by high-pressure NMR, are presented: one is to prevent the formation by means of sterically hindered ligands, the other one is to promote bond weakening at the leaving group.     

Application of diffusion‐edited NMR spectroscopy for selective suppression of water signal in the determination of monomer composition in alginates

Alginate is a linear copolymer of 1‐4 linked β‐D ‐mannuronic acid (M) and 1‐4 linked α‐L ‐guluronic acid (G). The physical properties of these polysaccharides such as gel properties and viscosity are largely correlated to the monomer composition (M/G ratio), the sequence of the polymer and the molecular weight. Determination of the M/G ratio is therefore important and NMR spectroscopy is among the most common methods used to accurately obtain this ratio. Instead of using time consuming, possibly sample altering, acid hydrolysis to reduce the viscosity of the alginate sample prior to analysis, samples of low concentrations can be used. However, this results in a water peak in the NMR spectrum that is several orders of magnitude larger than the alginate signals and water suppression is required. In this article, a diffusion‐edited NMR experiment that suppresses the water peak while retaining the signals of interest has been used to enable correct M/G ratio determination. This approach exploits the difference in translational diffusion between the larger alginate molecules and the smaller water molecules. Using this method, the monomer composition of 20 different alginate powders was determined. The diffusion parameters were optimized to allow measurement for samples covering a large range of M/G ratios and viscosities. Thus, such method should be useful for analyzing large numbers of unknown alginate samples using, for example, automation procedures. Copyright © 2011 John Wiley & Sons, Ltd.     

Low temperature synthesis of ITO nanoparticles using polyol process

A low temperature synthesis technique to prepare indium tin oxide (ITO) nanoparticles by the polyol process is proposed. On examining the phase formation of ITO nanoparticles in polyols and alcohols such as ethylene glycol, trimethylene glycol, and 1-heptanol, it was found that ITO nanoparticles could be synthesized directly without any post--annealing treatments at 175 °C in 1-heptanol. The morphology of the particles is influenced by the type of polyol. The composition of Sn in the ITO system could be easily controlled by simply varying the In/Sn precursor ratio in 1-heptanol. The low temperature synthesis method has enabled the formation of highly crystalline ITO nanoparticles with diameters less than 25 nm even at annealing temperatures as high as 700 °C.     

CdS films deposited by chemical bath under rotation

Cadmium sulfide (CdS) films were deposited on rotating substrates by the chemical bath technique. The effects of the rotation speed on the morphological, optical, and structural properties of the films were discussed. A rotating substrate-holder was fabricated such that substrates can be taken out from the bath during the deposition. CdS films were deposited at different deposition times (10, 20, 30, 40 and 50 min) onto Corning glass substrates at different rotation velocities (150, 300, 450, and 600 rpm) during chemical deposition. The chemical bath was composed by CdCl₂, KOH, NH₄NO₃ and CS(NH₂)₂ as chemical reagents and heated at 75 °C. The results show no critical effects on the band gap energy and the surface roughness of the CdS films when the rotation speed changes. However, a linear increase on the deposition rate with the rotation energy was observed, meanwhile the stoichiometry was strongly affected by the rotation speed, resulting a better 1:1 Cd/S ratio as speed increases. Rotation effects may be of interest in industrial production of CdTe/CdS solar cells.     

Organic light‐emitting device dark spot growth behavior analysis by diffusion reaction theory

Dark spot growth rate tracing experiments performed on an organic light‐emitting device show that moisture entering into the device is relatively properly fitted by Fick's diffusion equation in the substrate/indium tin oxide (ITO)/hole transport layer (HTL)/silver (Ag) structure. It is believed that the moisture is dissolved into the polymer layer, which results in a decrease in the diffusion coefficient in the device with the substrate/ITO/HTL/electroluminescent (EL) polymer/Ag structure. The diffusion and chemical reaction occurring in the cathode layer further decreases the diffusion coefficient in the device with the substrate/ITO/HTL/EL polymer/calcium/Ag structure. Useful parameters, such as diffusion and solubility constants, describing possible mechanisms happening during dark spot growth on organic light‐emitting diode devices are extracted. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1697–1703, 2001     

Improvement of pour point and oxidative stability of synthetic ester basestocks for biolubricant applications

For environmental reasons, as well as the dwindling source of petroleum, a new class of environmentally acceptable and renewable biolubricants based on plant oils is available. Even though plant oils possess excellent lubricant-related properties, there are some concerns about using it as biolubricant base oil. In this study we present a series of structures derived from oleic acid to be used as synthetic biolubricant basestocks. Measuring of pour point (PP), flash point, viscosity index (VI), oxidation onset temperature (OT) and signal maximum temperature (SMT) was carried out for each compound. Furthermore, the friction and wear properties were measured using a high-frequency reciprocating rig (HFRR). The resulting product structures were confirmed by NMR and FTIR spectroscopic analysis. The results showed that ethylhexyl 9-(octanoyloxy)-10-(behenoxy)octadecanoate with behenyl mid-chain ester exhibited the most favorable low temperature performance (PP ?48 °C) and ethylhexyl 9-(octanoyloxy)-10-(octyloxy)octadecanoate octyl mid-chain ester exhibited higher oxidation stability (OT 142 °C) than the other synthetic ester oils. On the other hand, the highest ball wear scan diameter was obtained for ethylhexyl 9-(octanoyloxy)-10-(behenoxy)octadecanoate while the lowest value was obtained for 9-hydroxy-10-octyloxyoctadecanoic acid. Overall, it was concluded that these synthetic ester oils have potential in formulation of industrial fluids for different temperature applications.     

Finite-time lag synchronization of coupled reaction–diffusion systems with time-varying delay via periodically intermittent control

In this paper, the issue of finite-time lag synchronization of coupled reaction–diffusion systems with time-varying delay (CRDSTD) is considered. A periodically intermittent controller is designed such that drive system and corresponding response system can achieve finite-time lag synchronization. By using graph theory and Lyapunov method, two sufficient criteria are presented to guarantee the finite-time lag synchronization of CRDSTD. Moreover, the time of achieving lag synchronization of CRDSTD is estimated. Finally, a numerical example is given to show the effectiveness of the proposed results.     

Prevention of blow-up by fast diffusion in chemotaxis

In this paper, we study a strongly coupled parabolic system with cross diffusion term which models chemotaxis. The diffusion coefficient goes to infinity when cell density tends to an allowable maximum value. Such ‘fast diffusion’ leads to global existence of solutions in bounded domains for any given initial data irrespective of the spatial dimension, which is usually the goal of many modifications to the classical Keller–Segel model. The key estimates that make this possible have been obtained by a technique that uses ideas from Moser's iterations.     

The Effect of Platinum on Diffusion Kinetics in β‐NiAl: Implications for Thermal Barrier Coating Lifetimes

Platinum is added to thermal barrier coatings (TBCs) as it is observed empirically to extend their lifetime, but the mechanism by which Pt acts is unknown. Since Pt has been proposed to alter diffusivities in NiAl, a key component of TBCs, we use first‐principles quantum mechanics calculations to investigate atomic level diffusion mechanisms. Here, we examine the effect of Pt on five previously proposed mechanisms for Ni diffusion in NiAl: next‐nearest‐neighbor jumps, the triple defect mechanism, and three variants of the six jump cycle. We predict that Pt increases the rate of Ni diffusion by stabilizing point defects and defect clusters that are diffusion intermediates. Previously, we predicted the triple defect mechanism to be a dominant Ni diffusion mechanism; it simultaneously results in long‐range Al diffusion in the opposite direction. Since Pt increases the rate of Ni diffusion, it also increases Al diffusion in NiAl, which may be key to extending the coating lifetime.