Experimental setup. The line is made of borosilicate glass, equipped with Young viton O-ring stopcocks. Parts of the line in contact with are covered with aluminum foil.
of the produced ozone as a function of pressure and temperature conditions.
Conservation of oxygen isotopes: The isotopic composition of the starting ozone (in terms of ) is compared to the products after reaction (1) [ O, whose isotopic composition is calculated using the isotopic composition of corrected for the isotopic composition of the initial NO using Eq. (4)].
Schematic diagram of the assumed stages in reaction and isotopic redistribution of the ozone component. See Sec. IV B for further explanations.
Relationship between and extracted from the two available models of intramolecular triple isotope distribution in ozone. The red dashed line and blue solid line correspond to the Bhattacharya et al. (Ref. 34) and Liang et al. (Ref. 33) models, respectively.
Plot of as a function of for the Bhattacharya et al. (Ref. 34) and Liang et al. (Ref. 33) models. The function is a metric of the difference between the model and the observation. The minimum of the function gives the value of corresponding to the best agreement between observation and model. Both models give the same value, 0.082, which implies that about 8% of the oxygen atoms in ozone abstracted by NO come from the central position.
Isotope anomaly of the oxygen atom transferred to during the oxidation of NO by ozone. Errors are given at 95% level of confidence .
Evolution of the and the (1)/ reaction rates ratio as a function of time simulated by the IBM chemical kinetic simulator under the conditions of our experimental setup. The simulation demonstrates that under our conditions is the only nitrogen oxide product, generated solely by reaction (1).
Isotopic composition of standard NO and determined using Tesla discharge by different operators at different times. Standard deviations and number of analyses are also given.
Experimental conditions used to study the reaction. Given are the thermodynamical conditions used to form by electrical discharge, the initial and final total pressure in the reaction chamber, and the amounts of reactants introduced and yield of products recovered. Only a qualitative indication is given for the temperature of ozone formation because of the large uncertainty pertaining to the temperature of the discharge zone.
and of the starting ozone, the produced and the O atom transferred to during the reaction of NO with . All data are reported in per mil (‰), with respect to the isotopic composition of the tank used to prepare the ozone.
Non-Arrhenius expressions of the kinetic rate of the reaction, in (in the form , where , being the pre-exponential factor and the activation energy for or 2). The IUPAC recommended value is also given (Ref. 51).
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