Preprints
https://doi.org/10.5194/acp-2021-451
https://doi.org/10.5194/acp-2021-451

  08 Jun 2021

08 Jun 2021

Review status: a revised version of this preprint was accepted for the journal ACP and is expected to appear here in due course.

Technical Note: Classical and statistical thermodynamic treatment of adsorption and desorption kinetics and rates

Daniel A. Knopf1 and Markus Ammann2 Daniel A. Knopf and Markus Ammann
  • 1School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, New York, USA
  • 2Laboratory of Environmental Chemistry, Paul Scherrer Institute, Villigen, Switzerland

Abstract. Adsorption and desorption represent the initial processes of the interaction of gas species with the condensed phase. It has important implications for evaluating heterogeneous (gas-to-solid) and multiphase chemical kinetics involved in catalysis, environmental interfaces, and, in particular, aerosol particles. When describing gas uptake, gas-to-particle partitioning, and the chemical transformation of aerosol particles the desorption lifetime is a crucial parameter to assess the underlying chemical kinetics such as surface reaction and surface-to-bulk transfer. The desorption lifetime, in turn, depends on the desorption free energy which is affected by the chosen adsorbate model and standard states. To assess the impact of those conditions on desorption energy and, thus, desorption lifetime, we provide a complete classical and statistical thermodynamic treatment of the adsorption and desorption process considering transition state theory for two typically applied adsorbate models, the 2D ideal gas and the 2D ideal lattice gas, the latter being equivalent to Langmuir adsorption. Both models apply to solid and liquid substrate surfaces. We derive the thermodynamic and microscopic relationships for adsorption and desorption equilibrium constants, adsorption and desorption rates, first-order adsorption and desorption rate coefficients, and the corresponding pre-exponential factors. Although, some of these derivations can be found in the literature, this study aims to bring all derivations into one place to facilitate the interpretation and analysis of desorption energies for their application in multiphase chemical kinetics. This exercise allows for a microscopic interpretation of the underlying processes including the surface accommodation coefficient and highlights the importance of the choice of adsorbate model and standard states when analyzing and interpreting adsorption and desorption processes. We demonstrate how the choice of adsorbate model choice affects equilibrium surface concentrations and coverages, desorption rates, and decay of the adsorbate species with time. In addition, we show how those results differ when applying a concentration- or activity-based description. Our treatment demonstrates that the pre-exponential factor can differ by orders of magnitude depending on the choice of adsorbate model with similar effects on the desorption lifetime, yielding significant uncertainties in the desorption energy. Furthermore, uncertainties in surface coverage and assumptions in standard surface coverage can lead to significant changes in desorption energies derived from measured desorption rates. Providing a comprehensive thermodynamic and microscopic representation aims to guide theoretical and experimental assessments of desorption energies and estimate potential uncertainties in applied desorption energies and corresponding desorption lifetimes important for improving our understanding of multiphase chemical kinetics.

Daniel A. Knopf and Markus Ammann

Status: closed

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2021-451', Anonymous Referee #1, 09 Jul 2021
  • RC2: 'Comment on acp-2021-451', Anonymous Referee #2, 19 Jul 2021

Status: closed

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2021-451', Anonymous Referee #1, 09 Jul 2021
  • RC2: 'Comment on acp-2021-451', Anonymous Referee #2, 19 Jul 2021

Daniel A. Knopf and Markus Ammann

Daniel A. Knopf and Markus Ammann

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Short summary
Adsorption on and desorption of gas molecules from solid or liquid surfaces or interfaces represent the initial interaction of gas-to-condensed phase processes that can define the physicochemical evolution of the condensed phase. We apply a thermodynamic and microscopic treatment of these multiphase processes to evaluate how adsorption and desorption rates and surface accommodation depend on the choice adsorption model and standard states with implications for desorption energy and lifetime.
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