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Mutual Diffusion Coefficients and Refractive Index Increments of K2SO4(aq) at 298.15 K from Rayleigh Interferometry

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Donald G. Miller: Deceased.

Abstract

Isothermal mutual diffusion coefficients (interdiffusion coefficients) were measured for K2SO4(aq) at 298.15 ± 0.005 K, at numerous concentrations ranging from dilute solutions to near saturation (0.59648 mol·dm–3; 0.61349 mol·kg–1) under free diffusion boundary conditions, using high precision Rayleigh interferometry. Under the experimental conditions these diffusion coefficients are on the volume-fixed reference frame Dv. Two series of experiments were performed, the first using the traditional experimental approach with a mercury lamp source and with the interference patterns being recorded on glass photographic plates, and the second with a He–Ne laser light source and computerized data acquisition using a photodiode array. The results from both series of experiments are in excellent agreement, and generally yield diffusion coefficients precise to at least 0.002 × 10–9 m2·s–1 (0.15% to 0.19%) and in most cases to 0.001 × 10–9 m2·s–1 (0.07% to 0.1%). These experiments also yield accurate values of the refractive index differences for the solution pairs used in the diffusion experiments. The new diffusion coefficients are compared to two sets of published values of diffusion coefficients for K2SO4(aq) which are somewhat discrepant from each other. This study extends and complements our earlier work on the diffusion coefficients of the most common brine salts: NaCl(aq), KCl(aq), MgCl2(aq), CaCl2(aq), Na2SO4(aq),]MgSO4(aq), NaHCO3(aq), and KHCO3(aq) at 298.15 K.

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Acknowledgements

This work was performed under the auspices of the U.S. Department of Energy (DOE) by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Support from the Chemistry and Biochemistry Department of Texas Christian University for J.G.A. and O.A. is gratefully acknowledged. The work of J.A.R. and D.G.M. was performed in part under the auspices of the Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences of the U. S. Department of Energy by University of California, Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48. Lawrence Livermore National Laboratory is now managed by Lawrence Livermore National Security LLC rather than the University of California. We thank Dr. Donald A. Palmer for supplying us with the Aldrich “Gold Label” K2SO4(s)

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  1. Joseph A. Rard

    Present address: Lawrence Livermore National Laboratory, Livermore, CA, USA

  2. Manfred E. Zeidler

    Present address: , Munich, Germany

Authors and Affiliations

  1. Lawrence Livermore National Laboratory, Livermore, CA, USA

    Donald G. Miller

  2. Department of Chemistry and Biochemistry, Texas Christian University, Fort Worth, TX, 76129, USA

    John G. Albright & Onofrio Annunziata

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Rard, J.A., Miller, D.G., Albright, J.G. et al. Mutual Diffusion Coefficients and Refractive Index Increments of K2SO4(aq) at 298.15 K from Rayleigh Interferometry. J Solution Chem 50, 1315–1334 (2021). https://doi.org/10.1007/s10953-021-01118-y

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