Electron energy loss spectroscopy of the decomposition of formic acid on Ru(001)

Electron energy loss spectroscopy has demonstrated the existence of both a monodentate and a symmetric bidentate bridging formate as stable intermediates in the decomposition of formic acid on the Ru(001) surface. The monodentate formate converts upon heating to the bidentate formate which decomposes via two pathways: CH bond cleavage to yield CO₂ and adsorbed hydrogen; and CO bond cleavage to yield adsorbed hydrogen, oxygen and CO. Thermal desorption spectra demonstrate the evolution of H₂,H₂O, CO and CO₂ as gaseous products of the decomposition reaction. The observation of this product distribution from Ru(100), Ni(100) and Ni(110) had prompted the proposal of a formic anhydride intermediate, the existence of which is rendered questionable by the spectroscopic results reported here.     

The electrochemical methoxylation of methoxybenzenes and related compounds : The mechanism of electrochemical methoxylation of 1,4-dimethoxybenzene

Anodic oxidation of benzenoid aromatic ethers in methanolic KOH soln at a platinum electrode constitutes a one step method for the synthesis of the rare class of compounds, herein designated as the quinone diketals. The mechanism of conversion of 1,4-dimethoxybenzene to the diketal of p-benzoquinone, based on the evidence accumulated, is considered to proceed via discharge of the adsorbed aromatic compound, followed by nucleophilic reaction of the solvent system with the electrogenerated cationic species. The quinone diketal products resulting from anisole, 1,4-, 1,2-, and 1,3-dimethoxybenzene, 9,10-dimethoxyanthracene and benzodioxane have been established. In contrast methyl benzoate, anisonitrite, and benzene were found to be unreactive in agreement with a direct discharge scheme which does not involve methoxy radicals.     

An analysis of the structure of the iridium (111) surface by low-energy electron diffraction

Elastic low-energy electron diffraction (LEED) intensity versus voltage (I-V) measurements for the clean Ir(111) surface have been obtained. Seven specular I-V spectra were measured from 15 to 975 eV at incident angles from 7° to 62.5° relative to the surface normal. The outermost atomic layer spacing of the unreconstructed Ir(111) surface was determined both by the convolution-transform method we have presented previously (including certain convenient modifications) and by dynamical calculations. Results from the analysis of the I-V spectra by the convolution-transform method indicate that the outermost Ir(111) layer spacing is either unrelaxed or contracts by 4% of its bulk value depending upon whether the θ=7° data or the θ = 25° data are used. In agreement with this, the dynamical calculations show that the outermost Ir(111) layer spacing contracts by 2.5± 5% and, in addition, that the registry of the first layer of the crystal surface is not shifted, maintaining the fcc structure.     

A method for assessing the coverage dependence of kinetic parameters: Application to carbon monoxide desorption from iridium (110)

A method for analyzing thermal desorption mass spectra has been developed for determining the coverage dependence of the pre-exponential factor and the desorption energy in the Arrhenius equation for a one-step desorption process. The method, which involves variable heating schedules, is applicable to spectra in which several features appear. However, if the desorption process involves multiple steps, or if substantial desorption from multiple sites occurs for any one coverage, this method cannot be used. The method is applied to CO desorption from the (110) surface of Ir. Three features can be resolved in the desorption spectrum. Both the preexponential factor and the desorption energy vary strongly with coverage, and a compensation effect occurs.     

Matroids,generalized networks,and electric network synthesis

Matroid theory has been applied to solve problems in generalized assignment, operations research, control theory, network theory, flow theory, generalized flow theory or linear programming, coding theory, and telecommunication network design. The operations of matroid union, matroid partitioning, matroid intersection, and the theorem on the greedy algorithm, Rado's theorem, and Brualdi's symmetric version of Rado's theorem have been important for some of these applications. In this paper we consider the application of matroids to solve problems in network synthesis. Previously Bruno and Weinberg defined a generalized network, which is a network based on a matroid rather than a graph; for a generalized network the duality principle holds whereas it does not hold for a network based on a graph. We use the concept of the generalized network to formulate a solution to the following problem: What are the necessary and sufficient conditions for a singular matrix of real numbers, of order p and rank s, to be realizable as the open-circuit resistance matrix of a resistance p-port network. A simple algorithm is given for carriyng out the synthesis. We then present a number of unsolved problems, included among which is what could be called the four-color problem of network synthesis, namely, the resistance n-port problem.     

Theorems on matroid connectivity

It is proved that for every k?4 there is a Δ(k) such that for every g there is a graph G with maximal degree at most Δ(k), chromatic number at least k and girth at least g. In fact, for a fixed k, the restriction of the maximal degree to Δ(k) does not seem to slow down the growth of the maximal girth of a k-chromatic graph of order n as n → ∞.