Co‐oxidation of ammonia and ethanol in supercritical water,part 2: Modeling demonstrates the importance of H2NNOx

A co‐oxidation model was constructed from available submechanisms for ammonia and ethanol oxidation. The ammonia submechanism validated for combustion at atmospheric pressure conditions was modified for the higher densities and lower temperatures (655–700°C) of supercritical water. The ethanol submechanism had previously been tested and validated at supercritical water conditions. The initial model poorly reproduced experimental ammonia conversion data and was not able to consistently match nitrous oxide production as a function of temperature over a range from 655–700°C at 246 bar. To improve model predictions, the low‐pressure NH₂ + NO_x submechanism was replaced with a submechanism that included the H₂NNO_x adduct species that are expected to be stabilized in the high‐pressure supercritical water environment. Thermochemical and kinetic parameters for the adduct species were estimated with quantum chemical calculations using Gaussian 98 with the CBS‐Q method. The explicit treatment of the H₂NNO_x adducts resulted in nitrous oxide yield predictions that correctly reproduced experimental trends. This work represents a vital first step in improving the understanding of ammonia oxidation in supercritical water. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 653–662, 2008     

Some Isoperimetric Inequalities in Electrochemistry and Hele Shaw Flows

Isoperimetric inequalities are applied to a moving-boundaryproblem for doubly-connected domains. This problem occurs forexample in electrochemistry, in which case the domains in questionare the electrolyte of an electrolytic cell. The two electrodessurrounding the electrolyte are assumed to grow or dissolve,at different rates in general, by electrochemical reaction.We obtain optimal estimates showing, for example, that the leastchange in volume of each electrode always occurs in sphericalsymmetry.     

New scaling laws for hot and cold jet mixing noise based on a geometric acoustics model

New scaling laws are presented for hot turbulent jet mixing noise outside the cone of silence. These account for mean flow field effects on sound radiation via an analytical high frequency approximate solution to Lilley's equation. Numerical calculations for sound radiation from sources in a cylindrical shear flow are used to test the validity of the approximation. The proposed scaling laws yield an excellent collapse of jet noise measurements over a wide range of conditions. The resulting information has been incorporated into a jet mixing noise prediction scheme which, with appropriate modifications to the analytical high frequency approximation, can be applied both inside and outside the cone of silence. The prediction scheme for angles inside the cone of silence will be described in a subsequent paper.     

Density-and-temperature-dependent volume translation for the SRK EOS: 1. Pure fluids

A mathematical framework for applying a density-and-temperature-dependent volume translation in a thermodynamically consistent manner was developed. Volumetric equations of state (EOS)s that incorporate this translation procedure can be used to generate derived properties, such as fugacity and enthalpy departure, that are based on isothermal departure or residuals from ideal gas state conditions. This kind of translation serves to improve the original EOS and not simply act as a correlation for molar volumes. A density-and-temperature-modified translation of this type was applied to the Soave–Redlich–Kwong EOS and was shown to possess accuracy for saturation pressure predictions equivalent to the untranslated EOS, as well as greatly improved density predictions compared to what is available when using only constant valued translation. The EOS translated in this manner retains many of the important features of the untranslated EOS, such as explicit calculation of volume roots, while having the representation capabilities of substantially more complicated models, such as the extended virial equation of Benedict, Webb, Rubin, and Starling.