Kinetics of hydantoin formation

The reaction of lignite in a slagging gasifier produces reactants which in turn form 5,5-dimethylhydantoin (DMH) as a major constituent in the condensate water. Variations in plant operating conditions made it impossible to accurately study the kinetics of formation of DMH in the actual gasifier water, and thus a model system was chosen. The reaction of acetone cyanohydrin in the presence of excess ammonium carbonate at concentrations approaching those obtained in the condensate water were studied at 50,70, and 90 °C. Secondorder kinetics were obeyed, and the pseudo second-order rate constants at the respective temperatures were 1.86, 3.6, and 4.62 dm³ mol^{? 1} h^{? 1}. Independent variation of the concentration of either acetone, cyanide, ammonia or carbonate gave results consistent with the interpretation that the formation of DMH is first order in all reactants: rate of formation of DMH = k[acetone][HCN][NH₃][CO₂]. The pseudo second-order rate constant is a complex rate constant including several rapid equilibria. A mechanism consistent with the kinetic data is presented.     

Effect of catalysts on the reaction between a cycloaliphatic diisocyanate (H-MDI) and n-butanol

Kinetics of the reaction between bis(4-isocyanatocyclohexyl)methane, H-MDI, and n-butanol was studied in toluene at 100°C. Effects of various catalysts, such as Hg(CH₃COO)₂, Zn(CH₃COO)₂ · 2H₂O, SnCl₄ · 5H₂O, and dibutyltindilaurate on the reaction rate and kinetics were also investigated. Reactions were followed by determining the unreacted isocyanate as a function of reaction time, using the standard dibutylamine back titration method. All catalysts seem to be very effective in increasing of the rate of the reaction compared to the uncatalyzed system. Depending on the initial stoichiometric ratio of (NCO) and (OH) and the concentration of the catalyst used, it seems possible to have preferential catalysis of the primary reaction between (NCO) and (OH) over the side reactions.     

Clinical psychologists reflect on the usefulness of various components of graduate training.

Graduates of clinical training programs were surveyed to determine the degree to which they have found various graduate school experiences useful in their professional work. Samples of academic clinical psychologists and practicing clinical psychologists reported time allocation and preference for various professional activities, perceived usefulness of various theoretical orientations, and the influence on their current professional work of 19 different graduate training topics. Results suggest that where differences exist, academic clinical psychologists are generally more satisfied with Boulder-model-inspired scientific training than are clinical practitioners. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Further results on local stability of REM algorithm with time-varying delays

This letter presents some further results on the local stability in equilibrium for Internet congestion control algorithm proposed by Low et al., (IEEE/ACM Transactions on Networking, 1999). The propagation delay d(t) is assumed to be time-varying and have maximum and minimum delay bounds (i.e., d/sub m//spl les/d(t)/spl les/d/sub M/), which is more general than the assumption (0相似文献   

The social consequences of expressive suppression.

At times, people keep their emotions from showing during social interactions. The authors' analysis suggests that such expressive suppression should disrupt communication and increase stress levels. To test this hypothesis, the authors conducted 2 studies in which unacquainted pairs of women discussed an upsetting topic. In Study 1, one member of each pair was randomly assigned to (a) suppress her emotional behavior, (b) respond naturally, or (c) cognitively reappraise in a way that reduced emotional responding. Suppression alone disrupted communication and magnified blood pressure responses in the suppressors' partners. In Study 2, suppression had a negative impact on the regulators' emotional experience and increased blood pressure in both regulators and their partners. Suppression also reduced rapport and inhibited relationship formation. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The relationship between bioelectrical impedance phase angle and subjective global assessment in advanced colorectal cancer

Background  

Bioelectrical Impedance (BIA) derived phase angle is increasingly being used as an objective indicator of nutritional status in advanced cancer. Subjective Global Assessment (SGA) is a subjective method of nutritional status. The objective of this study was to investigate the association between BIA derived phase angle and SGA in advanced colorectal cancer.