The reaction between deuterium and oxygen

Compared with the reaction between hydrogen and oxygen, there have been relatively few studies of the deuterium—oxygen system. Early studies by Hinshelwood et al. [243] dealt with the second explosion limits and the slow reaction in silica vessels while at about the same time Frost and Alyea [14] measured the second limits in a KCl coated Pyrex vessel of 20 mm diameter. More recently Linnett and Selley [244] have determined the relative efficiencies of a number of molecules in reaction (ivD) D + O2 + M = DO2 + M (ivD) 

A more recent study of the Dj + O2 reaction by Baldwin et al. [246] has involved measurements of the second limits, and the induction periods and maximum rates of the slow reaction in an aged boric acid coated vessel of 52 mm diameter. Maximum concentrations of D2 O2 in the slow reaction were also determined. The kinetic parameters of the oxidation process were then determined by a computer optimization treatment similar to that described in Sect. 4.3.3 for the H2 + O2 reaction. Excluding the primary initiation rate 6 which is necessary for the calculation of induction periods, but which needs to be only approximately defined, there are a minimum of seven significant parameters (cf. Table 18). 

In order to make their optimization procedure more realistic in the case of the H2 + O2 reaction, Baldwin et al. [72] used independent measurements of (a) second limits in KCl coated vessels in order to give fe2/fe4 (after correction if necessary for reaction (xi) and for surface termination of H atoms (Sect. 3 and Table 14)), and (b) the homogeneous decomposition of H2 O2 in the presence of hydrogen. The latter measurements give accurate values for 7, and 143/ 14 or fe, j/fe, at high or low hydrogen concentrations respectively, and the combined measurements leave just three adjustable parameters to be determined by the results with the B2O3 coated vessels. 

Unfortunately in the case of the D2 + O2 reaction, similar independent measurements cannot easily be made at 500 °C, firstly because of lack of information about the surface termination of D atoms in KCl coated vessels (such information would involve a detailed study also of the first 

Rate coefficient ratios for H2 and D2 reactions at 500 °C. (1. mole.sec units) [246] 

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