Abstract
Abstract. The partitioning of nitrogen oxides between ice and air is of importance to the ozone budget in the upper troposphere. In the present study, adsorption of nitrogen oxides on ice was investigated at atmospheric pressure using a chromatographic technique with radioactively labelled nitrogen oxides at low concentrations. The measured retentions solely depended on molecular adsorption and were not influenced by dimerisation, formation of encapsulated hydrates on the ice surface, dissociation of the acids, nor by migration into a quasi-liquid layer or grain boundaries. Based on the chromatographic retention and the model of thermo-chromatography, the standard adsorption enthalpy of -20 kJ mol-1 for NO, -22kJ mol-1 for NO2, -30kJ mol-1 for peroxyacetyl nitrate, -32kJ mol-1 for HON} and -44 kJ mol-1 for HNO3 was calculated. To perform those calculations within the model of thermo-chromatography, the standard adsorption entropy was calculated based on statistical thermodynamics. In this work, two different choices of standard states were applied, and consequently different values of the standard adsorption entropy, of either between -39 kJ mol-1 and -45kJ mol-1, or -164 kJ mol-1 and -169 kJ mol-1 for each nitrogen oxide were derived. The standard adsorption enthalpy was identical for both standard adsorption entropies and thus shown to be independent of the choice of standard state. A brief outlook on environmental implications of our findings indicates that adsorption on ice might be an important removal process of HNO3. In addition, it might be of some importance for HONO and peroxyacetyl nitrate and irrelevant for NO and NO2.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.