Thermomechanical and Energetic Coupling in DVB-Based Copolymers: A Unified Physicochemical Study of Adsorption Distance, Surface Energy, and Specific Surface Area

Abstract

The adsorption behavior of organic probe molecules on DVB-based copolymers and hyper-crosslinked resins was investigated by inverse gas chromatography using a thermomechanical framework that explicitly couples adsorption energetics with temperature and specific surface area. Retention measurements performed over a broad temperature range enabled the determination of Gibbs free energies of adsorption, which were further decomposed into dispersive contributions governed by London interactions. The intermolecular separation distance between probe molecules and polymer surfaces was shown to obey a universal thermomechanical law, exhibiting a bilinear dependence on temperature and copolymer specific surface area. This behavior reveals that surface morphology acts as a direct control parameter of adsorption dilation rather than a purely geometric descriptor.The London dispersive surface energy of the copolymers displayed a systematic temperature dependence consistent with fundamental dispersion-interaction scaling. Importantly, the surfacearea derivative of the dispersive surface energy followed a strict linear temperature law, demonstrating intrinsic coupling between thermal agitation and accessible surface morphology. Enthalpy-entropy compensation analysis further revealed that the intrinsic compensation temperature and enthalpic reference state are deterministic functions of specific surface area, leading to a generalized morphology-resolved compensation framework. The quadratic specific surface area scaling of compensation parameters provides direct experimental evidence that adsorption thermodynamics on polymeric networks are governed by thermomechanical constraints imposed by cross-linking architecture.These results establish a unified methodology for extracting physically meaningful surface parameters of polymeric solids, offering a molecular-scale interpretation of adsorption distances, dispersive surface energetics, and morphology-dependent thermodynamic invariants.