2020/04/01 by Leonid Rubinovich, Rubinovich, Leonid, Micha Polak +1
Physics and Astronomy · #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #physics.chem-ph
paper · pdf · doi:10.48550/arxiv.2004.00651
arxiv created 2020/07/14 · arxiv updated 2020/07/15
Equilibrium Constant Differential Equations (ECDE) are derived for several nanoconfined elemental bimolecular reactions in the frameworks of statistical mechanics and the ideal gas model. The ECDEs complement the well-known equilibrium-constant ordinary equations that are used for macroscopic systems. Solving the ECDE numerically or analytically furnishes the average reaction extent, as well as its variance and skewness. This original theoretical-computational methodology fills the gap in studies of nanochemical equilibrium providing a consistent and convenient alternative to derivations based on direct employment of the canonical partition-functions. Whereas the latter become more complex and time-consuming with increased number of molecules, the ECDE-based computations are equally efficient for small as well as large numbers of nanoconfined reacting molecules. The ECDE methodology introduced here is confirmed by a complete agreement with partition-function computations. In addition, the new approach is applied to nanoconfined adsorption.