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An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
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Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
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Xin Yang R. G. Downing Guan-bo Wang Da-zhi Qian Han-gang Liu Kan Wang 《Journal of Radioanalytical and Nuclear Chemistry》2014,301(1):213-220
This paper presents a Monte Carlo code to get response spectrum of ions for the Neutron Depth Profiling (NDP) technique called Monte Carlo NDP (MC-NDP) that simulates the behavior of ions transmitted through a sample matrix and generates the energy spectrum for a specified detector. The MC-NDP model is based on the Ziegler–Biersack–Littmark Model, but incorporates the advantages of TRIM and CORTEO. The Impulse Approximation method is used to determine the flight length with the indexical interpolation method rather than the Magic algorithm for the scattering angle between ions and nucleus. This makes MC-NDP more efficient and convenient to simulate entire ion histories by a Monte Carlo approach. MC-NDP’s results agree well with both TRIM results and the experimental data. 相似文献
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Pfeifer P Aston L Banks M Barker S Burress J Carter S Coleman J Crockett S Faulhaber C Flavin J Gordon M Hardcastle L Kallenborn Z Kemiki M Lapilli C Pobst J Schott R Shah P Spellerberg S Suppes G Taylor D Tekeei A Wexler C Wood M Buckley P Breier T Downing J Eastman S Freeze P Graham S Grinter S Howard A Martinez J Radke D Vassalli T Ilavsky J 《Chaos (Woodbury, N.Y.)》2007,17(4):041108
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Harry D. Downing Robert H. Hunt 《Journal of Quantitative Spectroscopy & Radiative Transfer》1973,13(4):311-321
The line intensities of the three δ-δ bands of CO2 and their associated Π-Π hot bands in the 2.0 υ region have been measured using a combination of long optical paths and low sample pressures with high resolution (0.035 cm-1). These intensities yield total band strengths of 0.200, 0.969, 0.288, 0.0017, 0.062 and 0.028 cm-2 atm-1 at 296 K for the 0401-0000, 1201-0000, 2001-000, 0511-0110, 1311-0110 and 2111-01 10 bands, respectively. The rotationless dipole moment matrix element and the German-Wallis coefficients are also determined for each band. 相似文献
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