Year: 2026
Type: article
Abstract: ABSTRACT Supercooled liquids with negative Clapeyron slopes are more stable at constant volume than at constant pressure. We compare the isochoric and isobaric driving forces for incipient solidification via a first‐order perturbation expansion of the thermodynamic potentials in the solid mass fraction. The analysis yields a geometry‐independent inequality: the isochoric Helmholtz driving force is strictly smaller than the isobaric Gibbs driving force. It also introduces a dimensionless stability number Π 0 = , where and are the solid and liquid specific volumes, is the latent heat of fusion, and κ l is the liquid isothermal compressibility. ranks materials and guides supercooling design for negative‐Clapeyron‐slope substances. For water, ≈ 0.048. Cryoprotectants increase it several‐fold, suppressing nucleation beyond colligative freezing‐point depression.
DOI: 10.1111/nyas.70417
Author: Boris Rubinsky
Institution: University of California, Berkeley
Language: English
Subfield: Atmospheric Science
Field: Earth and Planetary Sciences
Domain: Physical Sciences
Open Access status: green
Funder: National Science Foundation
OpenAlex ID: W7158883890