James E. Hardy

Oxidation kinetics of wet CO in trace concentrations

Abstract The title reaction is observed at temperatures from 1123°K to 1298°K for pressures of 1.22 to 2.44 atm for initial concentrations of CO as small as 3.1 ppm. Sensitivity analysis demonstrates that at these low CO concentrations the kinetics of the overall reaction are effectively sensitive to only one elementary reaction, CO + OH → CO 2 + H. Thus the good agreement between the observed reaction kinetics and the kinetics predicted by computer modeling confirms the literature value for k CO+OH .

Technique for Measuring the Total Concentration of Gaseous Fixed Nitrogen Species

An improved analytical procedure has been described for the measurement of total fixed-nitrogen species in combustion gases. The procedure consists of using a platinum catalyst at low pressure in a quartz vessel, in conjunction with a chemiluminescent NO analyzer. The procedure has been shown to be as accurate for NH/sub 3/ and HCN as the conventional chemiluminescent analyzer method is for NO and NO/sub 2/.

Influence of inert gas pressure on the kinetics of wet CO oxidation

The kinetics of wet CO oxidation have been experimentally studied in considerable detail (see Ref. [1] and references therein) and have been very successfully reproduced by computer modeling I-2]. As a result the process is generally regarded as well understood. In a previous paper [3], however, the authors showed that, contrary to the global rate law determined by Dryer and Glassman [1], the rate of CO oxidation departs from first order in CO at low CO concentration and may essentially stop. This paper reports another complication, the effect of inert gas pressure upon the CO oxidation rate. While this effect may appear surprising and it is certainly not explicitly recognized in the previous literature, one may deduce its existence from elementary considerations via the following argument: Dryers empirical rate law is based on experiments in which CO was oxidized in the presence of large amounts of nonreactive gases, N 2 and CO 2, in an apparatus restricted t o operation at one atmosphere total pressure [1]. The observed rate was first-order in CO, half-order in H20, and quarter-order in 0 2 . It is generally accepted that wet CO oxidation occurs chiefly by the reaction CO + OH--*CO 2 + H. By comparing the known rate constant for this elementary reaction with the rate of the overall oxidation, one may deduce that the OH concentration has a steady state value 100 times its equilibrium value for the conditions of the Dryer experiment. Steady state implies a balance between chain carrier production via the chainbranching reaction cycle and chain carrier removal via three-body processes. The latter may occur by

The Domino Theory of steam gasification of spent shale

Abstract This Paper reports a study of the chemistry which occurs during the steam gasification of spent (i.e. retorted) Green River oil shale. The results suggest that in the presence of steam there is an unusual and strong coupling between the decomposition of the inorganic carbonates, the gasification of organic carbon by steam, and the removal of nitrogen from the shale.