Monte Carlo simulation of hydrogen absorption in palladium and palladium–silver alloys

A modified Monte Carlo (MC) simulation was performed to investigate the hydrogen absorption behavior in Pd and Pd–Ag alloys of the composition Pd_xAg_1−x (x=0.7–0.8) under H₂ pressure (0.1 MPa) at different temperatures. The present method employed can consider the dissociative adsorption of hydrogen molecule and the subsequent absorption of hydrogen atom by formalizing the relationship between the pressure of hydrogen molecule and hydrogen atom. The potential parameters were determined to reproduce the solution enthalpy of hydrogen in pure metals. The results are in good agreement with experimental findings as well as previous theoretical studies. We confirmed that our method is useful to simulate the absorption of hydrogen in metals and alloys.     

Change of characteristics of desulfurization and denitrification by combustion flue gas composition and electrode configuration under pulsed corona discharge

Laboratory-scale and parametric experiments of SO₂ and NO_x removal from the simulated combustion gas by pulsed corona discharge have been performed by changing the combustion gas composition and temperature, the electrode configuration of plasma reactor, and the polarity of high-voltage electrode. The following results are obtained: 1) the higher the concentration of H₂O and O₂, the higher the efficiency of desulfurization and denitrification at the same specific input; 2) the pulsed corona discharge with a voltage pulsewidth as short as 200 ns of negative polarity shows the possibility to attain almost 90 percent deSO_x and deNO_x efficiency at the specific discharge input of 20 J/g, which is almost the same as the specific input in the electron-beam process; 3) the deNO_x characteristics show a little temperature dependence in the range of 70 to 130°C, but the deSO_x efficiency increases rapidly in the temperature region below 100°C suggesting the thermochemical dependence of deSO_x reaction; 4) when desulfurization and denitrification proceed, the white dendritic powder deposits on the plasma reactor whose composition is identified to be 49 mol% (NH₄)₂SO₄ and 47 mol% of 2NH₄NO₃ · (NH₄)₂SO₄, and the ratio of SO₂, NO and NH₃ of the deposit is almost equal to that of supplied gas.     

Composition of mixed octadecadienoates via ozonolysis,chromatography and computer solution of linear equations

An approach to the analysis of 55 possible nonconjugated positional isomers of octadecadienoic acid is described and tested with mixtures of individual synthetic methyl esters. In the first example, by ozonolysis a sevencomponent mixture consisting ofcis,cis 5,12-, 6,10-, 6,11-, 6,12-, 7,12-, 8,12-, and 9,12-octadecadienoates was converted to aldehydes, aldehyde-esters and dialdehydes. These fragments were separated on a 50 m×0.2 mm free fatty acid phase (FFAP) vitreous silica capillary column. Equations for an arbitrarily restricted 12×15 matrix of linear simultaneous equations and a computer solution of the matrix provided the composition of the initial methyl octadecadienoate mixture. The power and significance of this method became apparent with the observation that only two of the seven isomers in the known mixture were resolved as single peaks by state-of-the-art capillary gas chromatography, but all seven were identified and estimated with acceptable error by the ozonolysis-capillary gas chromatography-computer procedure. In a generalized approach to the analysis of the 55 possible nonconjugated isomers, a computer program selects the appropriate matrix of linear simultaneous equations based on the aldehyde data supplied by the analyst. Twenty of 21 combinations of seven isomeric esters taken five at a time have been analyzed to assess the efficiency of the method. To illustrate applicability at this stage of development, the method has been used to analyze the diene products of the hydrazine reduction of γ-linolenic acid and the diene products from the biological desaturation of isomeric monoenes. The possibility of distinguishing geometric and positional isomers of 18∶2 has been opened by the observed separation ofcis-andtrans-unsaturated aldehydes and aldehyde-esters. Presented in part at the 16th World Congress of the International Society for Fat Research, October 4–7, 1983, in Budapest, Hungary, and at the American Oil Chemists' Society Meeting, May 15, 1986, in Honolulu, Hawaii.     

Grigorii Valentinovich Samsonov

Obituaries

Grigorii Valentinovich Samsonov