Direct conversion of solid hydrocarbons in a molten carbonate fuel cell

Electrical characteristics of a molten carbonate fuel cell allowing direct electrochemical oxidation of dispersed hydrocarbons have been examined. As the fuel, graphite, anthracite, and cannel coal samples were used. Data illustrating the effect of electrolyte temperature, fuel type and dispersion, and also reactant gas mixture composition on the performance characteristics of the fuel cell, were obtained. Correlation between the specific characteristics of the fuel cell and the hydrogen content of fuel material was established. The maximum current-density values were achieved with hydrogen-rich cannel coal. For dispersed fuel samples, interparticle contact losses were found to have influence on the cell-generated voltage. The maximum cell opencircuit voltage was reached with stoichiometric oxygen-carbon dioxide mixture blown into the cathode. Yet, the largest current-density values were obtained when carbon dioxide lean mixtures were used. Even at zero carbon dioxide concentration the range of cathode polarizations was less than that observed with stoichiometric mixture. The processes proceeding in the cathode and anode packs of the fuel cell are believed to be interrelated processes. In a model fuel cell fueled with dispersed coal, current densities up to 140 mA/cm² and specific powers up to 70 mW/cm² were achieved.     

Determining a 'safe' high-mass limit in matrix-assisted laser desorption/ionisation time-of-flight mass spectra of coal derived materials with reference to instrument noise

Three methods for determining a 'safe' estimate for high-mass limits of MALDI spectra of coal derived liquids were explored, using a sample of coal-tar pitch and its pyridine-insoluble fraction. Co-addition of increasing numbers of single-shot spectra (10, 30, 50 and 100 pulses) showed visually observable reductions in noise levels, consistent with robust and statistically meaningful signals. Three separate types of post-acquisition calculation were used to identify high-mass limits of the spectra. (i) A literature method indicated high-mass limits similar to those observed visually-as a shift from baseline at the highest masses, nearly 350 000 u for the coal tar pitch and about 390 000 u for its pyridine insoluble fraction. (ii) Comparing instrument signal with pre-selected multiples of the standard deviation, upper mass estimates of between 40-60 000 u for the coal-tar pitch and about 95 000 u for its pyridine-insoluble fraction were found. (iii) Calculation of the slope was used to identify 'lift-off' of the spectrum from baseline. The angle between the smoothed spectrum and the baseline was matched to a pre-selected value (e.g. 0.5 degrees and 1 degrees ). However, the arbitrary specification of the key parameter did not establish this last method on a firm basis. The choice of a criterion for estimating high-mass limits of MALDI spectra remains a semi-quantitative procedure; a reasonably conservative high-mass limit may be estimated by comparison of signal with five times the standard deviation. However, evaluation of size exclusion chromatograms of the present samples using polystyrene standards suggests that molecular mass distributions of pitch samples arrived at by MALDI mass spectrometry are, at least partly, determined by the limitations of available instruments. Copyright 1999 John Wiley & Sons, Ltd.     

Syntheses and reactions of some fluorinated dienes,cyclobutenes and furans

There are many reports¹ of the pyrolysis of fluorinated organic compounds, including the defluorination of cyclic fluorocarbons over iron to give aromatic compounds. Extending this technique we have investigated the flow pyrolysis of some readily accessible unsaturated fluorocarbons, such as I, II, and III, and found these to be synthetically

useful routes to fluorinated dienes, cyclobutenes, and furans. Pyrolyses were carried out using a nitrogen flow over platinum, iron or caesium fluoride heated at 430–700°. The various products can all be rationalized in terms of intermediate allylic radicals, and the solid substrate influences which allylic radicals are formed.We are also investigating the chemistry of those now accessible compounds, such as IV, V, and VI, and some of the preliminary results are described.

For example the fluoride ion induced dimerisation of IV gave two major products VII and VIII via a particular interesting mechanism.

     

ChemInform Abstract: The Ground-State Potential Energy Surface of Diazene

has been studied by using a complete active space MCSCF wave function generated by distributing eight electrons among eight orbitals.