The law of chemical equivalence has specific limitations in complex reactions

How Many Kelvins are Equivalent to One Electron Volt: An Investigation of Unit Conversion in Catalysis. 2025. https://doi.org/10.26434/chemrxiv-2025-d5ssm

The classical thermodynamic framework gives an energy-temperature equivalence (1 eV ~ 11606 K) which defies experimental evidence, as chemical reactions with activation barriers of electron volts routinely proceed at ambient temperatures (~300 K). This paradox exposes fundamental limitations in Boltzmann-derived thermal scaling when applied to quantum-governed processes. Chemical reactions occurring at local active sites and governed by energy transfer in discrete k space break the global and continuum assumption for the zeroth law of thermodynamics. These effects decouple reactivity from classical thermal constraints, enabling pathway-specific control even at modest temperatures. By reconciling discrepancies between continuum thermodynamics and microscopic quantum processes, our work challenges the classical paradigm, proposing instead a context-dependent unit conversion governed by localized energy transduction mechanisms with energy balance between k and real space kinetic energy. This framework advances strategies for catalyst design—such as engineering interfacial phonons or resonant fields—to exploit discrete quantum interactions, bridging energy equivalence with macroscopic kinetics and redefining temperature-energy scaling for molecular-scale systems.