Calculation of diffusion coefficients for aqueous organic species at temperatures from 0 to 350 °C

doi:10.1016/0016-7037(91)90052-7

Geochimica et Cosmochimica Acta

Volume 55, Issue 12, December 1991, Pages 3515-3529

https://doi.org/10.1016/0016-7037(91)90052-7 Get rights and content

Abstract

Evaluation of hydrocarbon transport through the pore spaces of saturated rock in the subsurface as a function of time and distance requires accurate values of diffusion coefficients for aqueous organic species. Analysis of aqueous tracer diffusion coefficients (D⁰) for normal alkanes, alcohols, amides, carboxylic acids, alkylbenzenes, and alkylnaphthalenes reported in the literature indicates that diffusional activation energies decrease with increasing temperature, reaching a constant limiting value of ~3300 cal mol⁻¹ at temperatures a: 1̆00°C. This observation is consistent with the modified Arrhenius expression reported by Oelkers and Helgeson (1988). The Kirkwood-Riseman equation is used to predict D⁰ values as a function of the polymer chain length of hydrocarbons. Regression of experimental D⁰ data with a combined expression of the Kirkwood-Riseman and modified Arrhenius equations yields parameters which permit calculation of tracer diffusion coefficients for over 50 aqueous organic species at temperatures from 0° to 350°C and P_sat. (p_sat refers to pressures corresponding to the liquid-vapor equilibrium curve for H₂O at temperatures greater than 100°C and 1 bar at lower temperatures.) Resulting values of D⁰ permit evaluation of the extent of diffusional mass transfer in both contaminated near-surface environments and in the porewater adjoining oil field reservoirs. The computed tracer diffusion coefficients, which are qualitatively similar to D⁰ values previously calculated for aqueous ions, increase substantially with increasing temperature. For example, the tracer diffusion coefficient of aqueous toluene increases from 0.36 to 27.1 × 10⁻⁵ cm²sec⁻¹ in response to increasing temperature from 0 to 350°C.

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Calculation of diffusion coefficients for aqueous organic species at temperatures from 0 to 350 °C

Abstract

Chem. Eng. Sci.

Geochim. Cosmochim. Acta

Geochim. Cosmochim Acta

Chem. Geol.

Org. Geochem.

Geochim. Cosmochim. Acta

Geochim. Cosmochim. Acta

Org. Geochem.

Chem. Eng. Sci.

Dynamical properties of polymer solutions in good solvent by Rayleigh scattering experiments

Macromolecules

Predicting gas-liquid diffusivities

J. Chem. Eng. Data

Diffusion coefficients of carboxylic acids

Trans. Faraday Soc.

Mutual diffusion in non-ideal binary mixtures

J. Phys. Chem.

Studies in diffusion II. A kinetic theory of diffusion in liquid systems

J. Amer. Chem. Soc.

Primary migration: The importance of water-mineral organic interactions in the source rock

Aqueous molecular diffusivities of carboxylic acids

J. Chem. Eng. Data

Diffusion of aromatic and cycloparaffin hydrocarbons in water from 2 to 60°

J. Phys. Chem.

Diffusion coefficients in some ternary systems

J. Chem. Eng. Data

Liquid diffusivities in the Glycol-water system

J. Phys. Chem.

Pressure and temperature dependence of tracer diffusion coefficients of methanol, ethanol, acetonitrile and formamide in water

J. Phys. Chem.

Kirkwood-Riseman interpretation of the diffusion behavior of short polymer chains in dilute solution

Macromolecules

Liquid diffusion of nonelectrolytes

AIChE J.

Plasticity and diffusion as examples of absolute reaction rates

J. Chem. Phys.

Diffusion coefficients of acetates in aqueous sucrose solutions

J. Chem. Eng. Data

Diffusion of alcohols and amides in water from 4 to 37

J. Phys. Chem.

Liquid diffusion of nonelectrolytes

Part I. AIChE J.

Transport, distribution and fate of volatile organic compounds in groundwater

Prediction of diffusion coefficients for non-electrolytes in dilute aqueous solutions

AIChE J.

Organic/inorganic reactions in metamorphic processes

Diffusion of dissolved gases in liquids

Chem. Rev.

Petroleum Geochemistry and Geology

Diffusion coefficient of ethylene gas in water

J. Chem. Eng. Data

Mobility and effects of linear clays on fluorobenzene tracer and leachate

Groundwater

Coefficients of Diffusion in Liquids, V

Measurement of the diffusion coefficients of sparingly soluble gases in water

J. Geophys. Res.

Diffusion in Solids, Liquids and Gases

Some transport properties of aqueous pentaerthrol solutions at 25°C

J. Phys. Chem.

Binary diffusion coefficients of alcohol water mixtures at higher temperatures by a diaphragm cell method

The general theory of irreversible processes in solutions of macromolecules

J. Polymer Sci.

The intrinsic viscosities and diffusion constants of flexible macromolecules in solution

J. Chem. Phys.

Experimental measurements of diffusion parameters of light hydrocarbons in water-saturated sedimentary rocks—II. Results and geochemical significance.

Org. Geochem.

Experimental measurements of the diffusion parameters of light hydrocarbons in water-saturated sedimentary rocks—I. A new experimental procedure

Org. Geochem.

Interpretation of diffusion and viscosity curves in binary mixtures

Compt. Rend. Seane. Acad. Sci., Paris