Grindstone Chemistry--a greatly evolved version of Toda’s method of grinding solids together for solvent-free chemical reactions--has been described and its usefulness illustrated by the successful application of this technique to a simplified process for conducting the multi-component Biginelli reaction for the synthesis of physiologically active tetrahydropyrimidinones. 相似文献
A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.
127I NMR studies, as well as quadrupole splitting experiments performed by 2H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.
The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles. 相似文献
The dependence of dissolution rates on the difference of Gibbs free energy is of critical importance for our understanding of crystal dissolution, reactive flow models and their applications to a variety of environmentally related problems. Here, we review experimental data generated with mineral powders and single crystals to develop a better understanding of apparent inconsistencies between otherwise internally consistent data sets. Additional information from direct surface observations and measurements with vertical scanning interferometry (VSI) and atomic force microscopy (AFM) of albite dissolution at 25, 150 and 185 °C may shed new light on this old but unsolved question. Our discussion is based on the importance of etch pit development, its ΔG dependence, and the pits’ role as a source for steps and step movement in the dissolution process. Results indicate that reaction history may be of critical importance in determining the overall reaction mechanism and its rate. Different rates are observed for systems having otherwise identical ΔGr acquired from increasing versus decreasing disequilibrium positions.
In this context, we finally discuss the validity of the common application of transition state theory (TST) to elementary and overall reactions governing the dissolution process. In this discussion of crystal dissolution, we contrast TST applications with a stochastic, many-body treatment that has led to the development of a stepwave model. This discussion also focuses on the controversy caused by the rivalry between surface adsorption models and a probabilistic model that seeks to incorporate the full three-dimensional crystal structure. 相似文献
This paper derives the convection–diffusion-reaction equation governing the reaction between the dissolved oxygen in sea-water and the steel walls of a pulsating crack. By the neglect of the diffusion term it is shown that an exact solution of the convection-reaction equation can be obtained. A numerical method for the solution of the complete convection–diffusion-reaction equation is derived by the use of finite differences. The numerical computation of the initial transient and the final periodic steady-state values is also discussed. 相似文献
Why have molecules only been seen but not heard? For over a century chemists have probed reactions with various spectroscopic methods to learn about structures, dynamics, and reactivities of their molecules. What they have not done is to listen to their molecules react. Although the photoacoustic phenomenon has been known since 1880, it is only in the last twenty years that technology has developed to the point where sound waves produced by reacting molecules can be time resolved and the information contained within the waves deciphered. The information content within the photoacoustic wave is indeed rich, for one can learn about the dynamics and the magnitude of enthalpy changes associated with the reaction as well as the changes in molecular volume. This review article chronicles the development of time-resolved photoacoustic calorimetry and its application to a variety of reactions encountered in organic and organometallic chemistry and biochemistry. 相似文献
The electrocatalytic oxidation of 2-propanol was investigated using on line differential electrochemical mass spectrometry (DEMS) on electrodeposited Pt and an arrange of bimetallics: Pt0.84Rh0.16, Pt0.70Rh0.30, Pt0.55Rh0.45. It has been observed that the Pt0.84Rh0.16 bimetallic electrode presented the best catalytic activity for 2-propanol electrochemical oxidation. Since 2-propanol is a secondary alcohol, only acetone and CO2 are produced. The total yield of CO2 and acetone has been determined from the DEMS measurements. It is found that acetone is the major product, as reported before for other electrodes. The acetone and CO2 yield depends on the electrode composition. High amount of rhodium in the electrode composition strongly diminish the reaction rate as indicated by the decrease of both the acetone and CO2 yield. However, acetone inhibition is much more intense. The only bimetallic electrode that presents considerable mass spectroscopy signals intensity for CO2 and acetone is the Pt0.84Rh0.16 electrode. This electrode shows a slight increase in CO2 selectivity, compared to the other electrodes studied in this work. Only very low coverages of stable adsorbates were present during the reaction. Two and one carbon adsorbate were observed for all the electrodes. Three carbon adsorbates were detected only for the Pt0.84Rh0.16 electrode. Therefore, acetone production does not require a stable adsorbate. 相似文献