Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions at alkane by the C2H5 radical on-the-fly. The linear energy relationship (LER), developed for acyclic alkanes, was also proven to hold for cyclic alkanes. We have derived all RCTST parameters from rate constants of 19 representative reactions, coupling with LER and the barrier height grouping (BHG) approach. Both the RC-TST/LER, where only reaction energy is needed, and the RC-TST/BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy for combustion modeling. Our analysis indicates that less than 50% systematic errors on the average exist in the predicted rate constants using either the RC-TST/LER or RC-TST/BHG method, while in comparison with explicit rate calculations, the differences are within a factor of 2 on the average. The results also show that the RC-TST method is not sensitive to the choice of density functional theory used

Kinetics of 1,6-hydrogen migration in alkyl radical reaction class

The kinetics of the 1,6-intramolecular hydrogen migration in the alkyl radical reaction class has been studied using the reaction class transition state theory (RC-TST) combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approach. The RC-TST/LER, where only reaction energy is needed, and RC-TST/BHG, where no other information is needed, are found to be promising methods for predicting rate constants for any reaction in the 1,6-intramolecular H migration in alkyl radicals reaction class. Direct comparison with available experimental data indicates that the RC-TST/LER, where only reaction energy is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy

Catalysis engineering: From the catalytic material to the catalytic reactor

This chapter deals with the application of chemical reaction engineering and computational fluid dynamics (CFD) for the analysis and assessment of the interactions between mass and heat transport and chemical reactions. In the first part of the Chapter, we review fundamental concepts of chemical reaction engineering, by showing the potential impact of transport phenomena at the macroscale on the observed functionality of the catalytic material. This includes both the effect of the distribution of the residence times in the reactor and the impact of internal and external transport phenomena. In the second part, we illustrate modern approaches to catalytic reaction engineering based on CFD simulations. In particular, we present the algorithms to couple microkinetic models and kinetic Monte Carlo (kMC) simulations with CFD. The potentialities of the method are assessed by means of a showcase of the CFD-based analysis of a spectroscopic cell for operando experiments. This example clearly shows that transport artifacts in standard equipment may lead to an erroneous interpretation of the experiments if not properly accounted for

Late Quaternary climatic changes in southern Chile, as recorded in a diatom sequence of Lago Puyehue (40 degrees 40 ' S)

A late Quaternary diatom stratigraphy of Lago Puyehue (40 degrees 40'S, 72 degrees 28'W) was examined in order to infer past limnological and climatic changes in the South-Chilean Lake District. The diatom assemblages were well preserved in a 1,122 cm long, C-14-dated sediment core spanning the last 17,900 years, and were in support of an early deglaciation of Lago Puyehue. The presence of a short cold spell in South Chile, equivalent to the Younger Dryas event in the Northern Hemisphere, the Antarctic Cold Reversal in Antarctica, or the Huelmo-Mascardi event in southern South America, was not clearly evidenced in the diatom data, although some climate instability may have occurred between 13,400 and 11,700 cal. yr. BP, and a relatively long period (between 16,850 and 12,810 cal. yr. BP) with low absolute abundances and biovolumes could be tentatively interpreted as a period of low rainfall and/or temperatures. An increase in the moisture supply to the lake was tentatively inferred at 12,810 cal. yr. BP. After 9,550 cal. yr. BP, inferred stronger and longer persisting summer stratification, may have been the result of the higher temperatures associated with an early-Holocene thermal optimum. The mid-Holocene appeared to be characterized by a decrease in precipitation, culminating around 5,000 cal. yr. BP, and rising again after 3,000 cal. yr. BP, likely associated with a previously documented lowered frequency and amplitude of El Nino events. An increase in precipitation during the late Holocene (3,000 cal. yr. BP-present) might have marked subsequent increased frequency of El Nino occurrences, leading to drier summers and slightly moister winters in the area