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Validity of the Local Equilibrium Assumption for Modeling Sorbing Solute Transport Through Homogeneous Soils
Author(s) -
Valocchi Albert J.
Publication year - 1985
Publication title -
water resources research
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.863
H-Index - 217
eISSN - 1944-7973
pISSN - 0043-1397
DOI - 10.1029/wr021i006p00808
Subject(s) - non equilibrium thermodynamics , sorption , thermodynamics , porous medium , equilibrium thermodynamics , chemical equilibrium , flow (mathematics) , moment (physics) , statistical physics , mechanics , chemistry , physics , geotechnical engineering , porosity , geology , classical mechanics , adsorption
Sorption processes that occur during reactive solute movement through porous media can be modeled using either an equilibrium or kinetic approach. Because of the resulting conceptual and mathematical simplification, many transport models assume local chemical equilibrium is valid for describing sorption reactions. This paper presents quantitative criteria to assess the validity of the local equilibrium assumption for one‐dimensional, steady flow through homogeneous soils. A method is described whereby formulas for solute breakthrough curve time moments can be determined without knowledge of the nalytical solution to the mass transport model. This method is applied to several commonly used nonequilibrium formulations as well as the standard linear equilibrium model. The formulations considered include both the physical nonequilibrium models where the sorption rate is controlled by diffusive solute transfer between mobile and stagnant fluid zones and the chemical nonequilibrium models where the overall sorption rate is governed by the rate of reaction at the soil‐solution interfaces. Criteria for local equilibrium to be valid are derived by comparing the time moment formulas for the nonequilibrium and equilibrium models. These criteria explicitly show that basic system parameters (e.g., seepage velocity, dispersion coefficient, distribution coefficient, sorption rate, boundary conditions) have a significant influence on the attainment of local equilibrium.