Thermodynamic derivation of mechanical expressions for interfacial parameters

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发布日期
DOI 10.1039/A906437K
影响因子 3.676
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摘要

We derive mechanical expressions for interfacial parameters from their thermodynamic definition. The ‘classical’ thermodynamics of curved interfaces as first derived by Gibbs and elaborated later by Tolman and contemporaries gives the well-known interfacial tension of an interface, γG. A more recent approach by Boruvka and Neumann gives complementary interfacial parameters: the interfacial tension according to Boruvka and Neumann γBN the bending stress C1, and the torsion stress C2. In the literature both approaches are matched with the classical mechanical expression for the interfacial tension in order to arrive at mechanical expressions for the aforementioned interfacial parameters. We discuss whether this matching can be done unambiguously. Following a thermodynamically consistent formalism, we arrive at mechanical expressions for interfacial parameters which differ significantly from the ones given in the literature which were found with the matching procedure. We prove the consistency of our expressions by showing its accordance with the generalized Laplace equation of capillarity. Moreover, we show by means of a lattice gas model that our expressions give, unlike those in the literature, unambiguous results. The consequences of the new mechanical expressions for the surface of tension and Tolman length are discussed.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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