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71.
LEED, RHEED and Auger spectroscopy have been used to study the adsorption of oxygen on to a clean and carbon contaminated (112) face of tungsten. At room temperature all the features reported previously were observed together with a p(1 × 4) surface structure which appeared at an exposure of about 1. 4L just before the formation of the p(1 × 2). Previously a p(1 × 4) structure has been reported only after heating to 2000K. RHEED showed this p(1 × 4) structure clearly; using LEED, the structure was difficult to distinguish. This appears to confirm suspicions that in some situations involving gas adsorption, RHEED has a greater sensitivity than LEED. Possibly most of these situations involve, as does the present p(1 × 4) structure, monolayer islands where the differing coherence widths of the RHEED and LEED beams account for the differing sensitivities. Carbon on the (112) surface also appears to exist as thin islands, either of the previously reported c(6 × 4) structure, or in smaller amounts, on a surface showing (1 × 1) symmetry. Removal of all carbon by heat treatment alone was found to be impossible in a reasonable time and heating in oxygen was necessary. Oxygen adsorption on a carbon contaminated surface did not give rise to any new structures but rather a reduction in the visibility/formation of the clean surface/oxygen structures. 相似文献
72.
Louis Watts Clark 《国际化学动力学杂志》1974,6(5):713-724
Rate constants and activation parameters are reported for the decarboxylation of malonic acid in seven normal alkanols (butanol-l to decanol-l inclusive). It is found that the enthalpy of activation of the reaction is a linear function of the number of carbon atoms in the hydrocarbon chain of tthe solvent, expressed by the equation: ΔH≠ = –600n + 30,000, where n is thenumber of carbon atoms in the chain. Also an equation is developed relatingthe rate constant for the decarboxylation of malonic acid in normal alkanols to n (the number of carbon atoms in the chain): log K = 10.854283 – 0.3212674n + (131.136876n – 6556.5438)/T + log T. With the aid of this equation rate constants may be calulated for the decarboxylationof malonic acid in any alcohol at any temperature which agree with experimental values to within the limit of error of the experiments. A comparison of the data obtained in the present research for the decarboxylation of malonic acid in normal alkanols with previously reported data for the reaction in amines indicates that for reaction taking place in alcohols the transition state probably contains two molecules of solvent but only one for the reaction in amines. 相似文献
73.
High-resolution infrared predissociation spectra have been measured for dilute mixtures of CO2 and N2O in helium. Rotational fine structure is clearly resolved for both (CO2)2 and (N2O)2, the linewidths being instrument-limited. This establishes that predissociation lifetimes are longer than approximately 50 ns. 相似文献
74.
75.
Surface enhanced Raman scattering has been observed for O2 molecules adsorbed on polydiacetylene single crystals. The spectral dependence of the Raman cross section suggests that the enhancement is due to a well-defined electronic transition of energy 2.39 eV which involves a significant degree of charge transfer from the conjugated polydiacetylene backbone to the O2 molecule. 相似文献
76.
Ohne Zusammenfassung 相似文献
77.
The anion of the isoquinoline Reissert compound has been found to react with 4-piperidones to give esters of tertiary alcohols. 相似文献
78.
Louis Watts Clark 《国际化学动力学杂志》1975,7(6):807-816
Rate constants and activation parameters are reported for the decarboxylation of n-butylmalonic acid in four normal alkanols (hexanol? 1, octanol? 1, decanol? 1, and dodecanol? 1) and in five amines (aniline, N-methylaniline, N-ethylaniline, N-n-propylaniline, and N-n-butylaniline). Both ΔH? and ΔS? of the reaction in both homologous series decrease regularly with increasing length of the hydrocarbon chain of solvent. If we compare data for the reaction in alkanol–amine pairs containing the same total number of carbon atoms in the molecule, we find that the ΔH? values are identical, but that the value of ΔS? is 0.8 eu/mole higher for the reaction in the amines as compared with the alcohol. The rate constant, at all temperatures, is 1.5 times as large in the amine as it is in the corresponding alcohol. Empirical equations are deduced relating the parameters ΔH? ΔS? ΔG? and k of the reaction to the parameters n and T, where n is the total number of carbon atoms in the solvent molecule and T is the absolute temperature. The results reported herein are compared with previously reported data for malonic acid. 相似文献
79.
80.
Cammidge AN Goddard VH Gopee H Harrison NL Hughes DL Schubert CJ Sutton BM Watts GL Whitehead AJ 《Organic letters》2006,8(18):4071-4074
A conceptually and practically simple alternative approach to the use of arylboron species as the organometallic component in cross-coupling processes is described whereby trihydroxyborate salts are isolated and directly employed. The protocol derives practical benefit from the ease and convenience of the isolation and subsequent use of the discrete borate salts, eliminates the need for additional base, and aids the use of correct reaction stoichiometry. 相似文献