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91.
Cyclopentane and methylcyclopentane oxidation was investigated in a jet-stirred reactor at atmospheric pressure, over temperatures ranging from 900 to 1250 K, for fuel-lean, stoichiometric, and fuel-rich mixtures at a constant residence time of 70 ms. The initial mole fraction of both fuels was kept constant at 1000 ppm. The reactants were highly diluted by a flow of nitrogen to ensure thermal homogeneity. Samples of the reacting mixture were analyzed online and off-line by Fourier transform infrared spectroscopy and gas chromatography. A detailed kinetic mechanism consisting of 590 species involved in 3469 reactions was developed, and simulation results were compared to these new experimental data and previously reported ignition delays. Reaction pathways analysis as well as sensitivity analyses were performed to get insights into the differences observed during the oxidation process of cyclopentane and methylcyclopentane. 相似文献
92.
Nikolaos V. Tzouras Dr. Fady Nahra Dr. Laura Falivene Prof. Dr. Luigi Cavallo Marina Saab Prof. Dr. Kristof Van Hecke Dr. Alba Collado Dr. Christopher J. Collett Prof. Dr. Andrew D. Smith Prof. Dr. Catherine S. J. Cazin Prof. Dr. Steven P. Nolan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(20):4515-4519
We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal–N-heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base-assisted concerted process that does not require free NHC formation. The synthetic protocol was found applicable to a number of transition-metal- and main-group-centered NHC compounds and could become the synthetic route of choice to form M–NHC bonds. 相似文献
93.
Dr. Yashapal Singh Prof. Dr. Alexei V. Demchenko 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(5):1042-1051
Following the recent discovery that traditional silver(I) oxide-promoted glycosidations of glycosyl bromides (Koenigs–Knorr reaction) can be greatly accelerated in the presence of catalytic TMSOTf, reported herein is a dedicated study of all major aspects of this reaction. A thorough investigation of numerous silver salts and careful refinement of the reaction conditions led to an improved mechanistic understanding. This, in turn, led to a significant reduction in the amount of silver salt required for these glycosylations. The progress of this reaction can be monitored by naked eye, and the completion of the reaction can be judged by the disappearance of characteristic dark color of Ag2O. Further evidence on higher reactivity of benzoylated α-bromides in comparison to that of their benzylated counterparts has been acquired. 相似文献
94.
《Electroanalysis》2018,30(8):1653-1658
A gold electrode surface was functionalized by means of an electropolymerized conductive poly(3,4‐ethylenedioxythiophene) (PEDOT) organic layer. This modified electrode was used for the electrochemical detection of ascorbic (AA) and uric (UA) acids in an aqueous mixture with a selectivity around 340 mV. The electrochemical reactions kinetics were limited by AA diffusion and UA adsorption at the electrode surface, respectively. Following a previous study ([Electrochem Comm. 2011 , 13, 423–425]) cyclic voltammetry was used to provide a better understanding of the EC’ mechanism of regeneration of UA by AA. Experiments particularly showed that allantoin (i. e. the final product of UA oxidation) is not actually involved in the synergic mechanism but rather the oxidized UA product diimine which is adsorbed at the electrode surface. 相似文献
95.
A significant amount of work has been previously dedicated to the understanding of methylene selectivity parameter. The conventional theory applied for this understanding was mostly based on the assumption that the difference in the Gibbs free energy of transfer from the mobile phase to the stationary phase is a constant for any two compounds in a homologous series that differ by a CH2 group. In the present study, it is shown based on solvophobic theory that this assumption is indeed correct, but it provides a theoretical justification for it. Exemplification of the results of theory was obtained using the values for methylene selectivity (α(CH2)) measured experimentally for seven different C18 chromatographic columns including two core–shell columns and using water and either methanol or acetonitrile as an organic component. Four different homologous series of compounds were used for evaluation. The study proved the theoretical prediction that the values for α(CH2) obtained using different homologous series of compounds are only slightly different from those obtained using the toluene–butylbenzene series. Even using different homologous series, the same type of information regarding the columns comparison, and the changes in log α(CH2) with the solvent composition was obtained. 相似文献
96.
Kambale Mondo Senda Agrebi Fathi Hamdi Fatma Lakhal Amsini Sadiki Mouldi Chrigui 《Entropy (Basel, Switzerland)》2022,24(5)
Even though there is a pressing interest in clean energy sources, compression ignition (CI) engines, also called diesel engines, will remain of great importance for transportation sectors as well as for power generation in stationary applications in the foreseeable future. In order to promote applications dealing with complex diesel alternative fuels by facilitating their integration in numerical simulation, this paper targets three objectives. First, generate novel diesel fuel surrogates with more than one component. Here, five surrogates are generated using an advanced chemistry solver and are compared against three mechanisms from the literature. Second, validate the suggested reaction mechanisms (RMs) with experimental data. For this purpose, an engine configuration, which features a reacting spray flow evolving in a direct-injection (DI), single-cylinder, and four-stroke motor, is used. The RNG k-Epsilon coupled to power-law combustion models is applied to describe the complex in-cylinder turbulent reacting flow, while the hybrid Eulerian-Lagrangian Kelvin Helmholtz-Rayleigh Taylor (KH-RT) spray model is employed to capture the spray breakup. Third, highlight the impact of these surrogate fuels on the combustion properties along with the exergy of the engine. The results include distribution of temperature, pressure, heat release rate (HRR), vapor penetration length, and exergy efficiency. The effect of the surrogates on pollutant formation (, , ) is also highlighted. The fifth surrogate showed 47% exergy efficiency. The fourth surrogate agreed well with the maximum experimental pressure, which equaled 85 Mpa. The first, second, and third surrogates registered 400, 316, and 276 g/kg fuel, respectively, of the total CO mass fraction at the outlet. These quantities were relatively higher compared to the fourth and fifth RMs. 相似文献
97.
To address the problem of a poor security image encryption algorithm based on a single chaotic map, this paper proposes a cascade modulation chaotic system (CMCS) that can generate multiple chaotic maps. On this basis, a multi-image encryption algorithm with block-scrambling-diffusion is proposed using CMCS. The algorithm makes full use of the features of CMCS to achieve the effect of one encryption at a time for images. Firstly, the key-value associated with the plaintexts is generated using a secure hash algorithm-512 (SHA-512) operation and random sequence, and the three images are fully confused by the double scrambling mechanism. Secondly, the scrambled image is converted into a bit-level matrix, and the pixel values are evenly distributed using the bit-group diffusion. Finally, the non-sequence diffusion of hexadecimal addition and subtraction rules is used to improve the security of the encryption algorithm. Experimental results demonstrate that the encryption algorithm proposed in this paper has a good encryption effect and can resist various attacks. 相似文献
98.
99.
基于聚类分割和形态学的可见光与SAR图像配准 总被引:1,自引:0,他引:1
针对可见光与SAR图像灰度差异大,共有特征提取难的问题,提出了一种基于k-均值聚类分割和形态学处理的轮廓特征配准方法。利用k-均值聚类算法对两类图像进行分割,得到图像分割区域;通过形态学处理,有效减少SAR图像斑点噪声影响,准确提取两类图像的封闭轮廓;采用轮廓不变矩理论,引入矩变量距离均值、方差约束机制和一致性检查的匹配策略,获取最佳匹配对,实现了两类图像的配准。通过实验,三组图像的配准精度分别达到0.3450、0.2163和0.1810,结果表明该法可行且能达到亚像素的配准精度。 相似文献
100.
Feng Liu Jing Liu Yingju Yang Zhen Wang Chuguang Zheng 《Proceedings of the Combustion Institute》2019,37(4):4399-4408
Spinel CuFe2O4 is a promising oxygen carrier due to its synergistic enhanced performance. A fundamental understanding of the reaction mechanism between oxygen carrier and fuels is important for a rational design of highly efficient oxygen carrier. The reaction mechanism of spinel CuFe2O4 with CO during chemical-looping combustion (CLC) was studied based on thermogravimetric analyses (TGA) and density functional theory (DFT) calculations. Two distinct reaction stages were clearly observed. CuFe2O4 was mainly transformed into Cu and Fe3O4 with a rapid reaction rate in the initial stage, and then product Fe3O4 was slowly reduced to FeO or even to Fe. The reactivity of CuFe2O4 is much higher than that of Fe2O3, which is ascribed to the existence of Cu. The enhanced oxygen evolution activity of CuFe2O4 at low temperature is validated by both the experimental and theoretical methods. Three types of surface oxygen coordinated with different metal atoms show different reactivity. Two kinds of reaction pathways are involved in CO oxidation over CuFe2O4. In the one-step reaction pathway, CO directly reacts with the oxygen bonding to two octahedral Cu and one octahedral Fe atoms to form a CO2 molecule without an energy barrier, which corresponds to the surface oxygen consumption observed in TGA experiments. In the possible two-step reaction pathway, CO first adsorbs on the surface, and then reacts with the oxygen bound to one octahedral Cu and two octahedral Fe atoms to generate CO2 by surmounting an energy barrier of 10.84 kJ/mol, which is the most kinetically and thermodynamically favorable pathway. 相似文献