Some comments on multicomponent diffusion: negative main term diffusion coefficients, second law constraints, solvent choices, and reference frame transformations

Journal Article · Thu Apr 10 04:00:00 EST 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100399a010· OSTI ID:5905414

Miller, D G; Vitagliano, V; Sartorio, R

Some interesting aspects of multicomponent diffusion in liquids are discussed. These include the existence of a negative main term diffusion coefficient; the utility of taking different components as the solvent; the change-of-solvent transformation for Fick's law coefficients and Onsager coefficients; the validity of the Onsager reciprocal relations on changing solvents; and the calculation of partial molar volumes from diffusion data. Previous work is surveyed on the irreversible thermodynamic basis for macroscopic diffusion; the importance of reference frames and transformations among them; and second law conditions on the volume-fixed diffusion coefficient matrix. Certain diffusion descriptions in other reference frames do not preserve these second law conditions. 78 references, 5 tables.

• Research Organization: Lawrence Livermore National Lab., CA
• DOE Contract Number: W-7405-ENG-48
• OSTI ID: 5905414
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:8; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
DIFFUSION
DOCUMENT TYPES
FICK LAWS
IRREVERSIBLE PROCESSES
MATHEMATICAL MODELS
ONSAGER RELATIONS
REVIEWS
SOLVENT PROPERTIES
SOLVENTS
THERMODYNAMICS