Abstract

Investigation of the regularities of chemical processes, not only near but also far from the stationary state, gives additional information on their mechanisms. In this paper, we present a new method for estimating rate constants of adsorption-desorption processes from the experimentally measured values of the nonstationary concentrations of an adsorbed substance, based on calculating the instantaneous rates of the adsorption (or desorption) process. This method allows to connect unknown kinetic parameters of adsorption (desorption) of a substance on the catalyst surface for various most probable assumed mechanisms with the calculated values of the instantaneous rates of adsorption-desorption processes. As a consequence, the method makes it possible to solve two types of inverse problems of chemical kinetics: calculate point and interval values of rates constants of adsorption and desorption; determine the most likely mechanism from several proposed mechanisms of implementation of these processes. Using this method, point and interval values of the rates constants of adsorption and desorption of carbon dioxide were determined on the base of nonstationary experimental data on adsorption on the assumption of carbon dioxide adsorption on a chromoxide catalyst to three proposed mechanisms: linear, bimolecular and dissociative. Based on the results of calculations, the corresponding non-stationary dependences of carbon dioxide adsorption were restored, which were compared with the experimental data. The obtained results confirm that the previously established dissociative mechanism of adsorption of carbon dioxide on the chromoside catalyst is the most probable. The developed simple method does not require the use of complex optimization calculations and can be used to solve the inverse problem of chemical kinetics associated with the determination of mechanisms and the estimation of the rates constants of adsorption and desorption of substances on various catalysts.Forcitation:Kol’tsov N.I., Fedotov V.Kh. Study of carbon dioxide adsorption on chromoxide catalyst on non-stationary concentrations. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 7. P. 37-42

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