2024/07/05 by Yu Qiao, Meng Wang, Qiao, Yu +1
Chemistry · Engineering · Physics and Astronomy · #Chemical Physics (physics.chem-ph) #Electrostatics and Colloid Interactions #FOS: Physical sciences #Ion-surface interactions and analysis #Nanopore and Nanochannel Transport Studies #Soft Condensed Matter (cond-mat.soft) #Statistical Mechanics (cond-mat.stat-mech) #cond-mat.soft #cond-mat.stat-mech #physics.chem-ph
paper · pdf · doi:10.48550/arxiv.2407.04599
43 pages, 9 figures
openalex publication_date 2024/07/05 · openalex created_date 2024/07/09 · arxiv created 2026/07/30 · arxiv updated 2026/07/31 · openalex updated_date 2026/08/02
Recent theoretical research on the fundamentals of statistical mechanics has led to a counterintuitive discovery [2-4]: with a locally nonchaotic energy barrier, a macroscopic system may reach an intrinsic-nonequilibrium steady date without any external driving force, which breaks the boundaries of the second law of thermodynamics. In the current investigation, we experimentally validate the concept of intrinsic nonequilibrium, with the weak gravitational force in the "toy model" being changed to the strong Coulomb force. The tests are performed on a set of nanoporous carbon electrodes immersed in aqueous cesium pivalate solutions. The key characteristic is that the effective nanopore size is only slightly larger than the effective ion size, less than twice the ion size. At first glance, the supercapacitive cells exhibit "normal" charge curves. However, the steady-state distribution of the large ions in the charged small nanopores intrinsically differs from thermodynamic equilibrium. Such a phenomenon is consistent with molecular dynamics simulations reported in the open literature.