Critical Review of Transport and Equilibrium Properties of Potassium Chloride in High Temperature Water

Zimmerman, G. H.; Staros, Daniel J.; Arcis, Hugues

doi:10.1021/acs.jced.1c00814

Cited by 3 publications

(1 citation statement)

References 63 publications

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“…Recently, our research group reported several experimental investigations as part of a definitive laboratory study aimed at achieving a better understanding of ionic diffusion under hydrothermal conditions in light − ,, − and heavy waters. − The effects of hydration on ionic diffusion were discussed using deviation plots, showing the difference between the experimental Walden products (λ o η w ) and predictions from the Stokes law false( λ ° η normalw false) exp − false( λ ° η w false) Stokes false( λ ° η normalw false) Stokes = normalΔ λ normalo λ Stokes normalo This comparison provides a convenient, conceptually simple reference point at each temperature, corrected for the effects of viscosity, and is used in the discussion presented below.…”

Section: Discussionmentioning

confidence: 99%

Limiting Conductivities of Strong Acids and Bases in D₂O and H₂O: Deuterium Isotope Effects on Proton Hopping over a Wide Temperature Range

2022

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The molar conductivity (Λ°) of hydrochloric acid, potassium hydroxide, and sodium hydroxide has been measured in both light and heavy waters from 298 to 598 K at p = 20 MPa using a high-precision flow-through alternating current (AC) conductance instrument. The results were used to explore the deuterium isotope effect on ionic transport by proton hopping mechanisms under hydrothermal conditions. Extrapolations of published transport number data to elevated temperature were used to calculate the individual ionic contributions (λ°) for H3O+, D3O+, OH–, and OD–, from which the excess molar conductivities due to proton hopping were calculated. These are the first reported values for the excess conductivities for D3O+ and OD– at temperatures above 318 K. The excess conductivities indicate a strong deuterium isotope effect whereby the transport of D3O+ by proton hopping is reduced by ∼33% relative to H3O+, and OD– is reduced by over 60% relative to OH–, over the entire temperature range. A well-defined maximum in the excess conductivities of D3O+ and H3O+ at ∼420 K suggests that the Eigen cation (H2O)4H+ and the Zundel transition-state cation (H2O)2H+ are destabilized at elevated temperatures as the three-dimensional, tetrahedrally hydrogen-bonded networks in water break down. The less pronounced maximum for OD– and OH– suggested that their Eigen and Zundel anions, (H2O)3OH– and (H2O)OH–, are less destabilized in the two-dimensional networks and chains that dominate the “structure” of liquid water under these conditions.

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Section: Discussionmentioning

confidence: 99%

Limiting Conductivities of Strong Acids and Bases in D₂O and H₂O: Deuterium Isotope Effects on Proton Hopping over a Wide Temperature Range

2022

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Critical Review of Transport Properties of HCl, KOH, and NaOH in High Temperature Water and Correlations for Transport Properties of H3O+ and OH−

Arcis

Lee

Zimmerman

et al. 2023

Journal of Physical and Chemical Reference Data

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High-temperature tracer diffusion coefficients for H3O+ and OH− are important parameters in the modeling of diffusion-controlled reaction kinetics and mass transport processes under hydrothermal conditions, and these tracer diffusion coefficients are directly related to the ionic electrical conductivities in the limit of infinite dilution through the Nernst–Einstein relationship. The limiting conductivity of H3O+ and OH− in water is controlled by two separate mechanisms of ionic movement: (i) the bulk ionic diffusion and (ii) proton hopping, also known as “Grotthuss” mechanism and/or “prototropic transfer.” This work reports a critical assessment of the limiting electrical conductivity data (Λ°) for aqueous HCl, KOH, and NaOH measured above room temperature. The initial assessed dataset included temperatures from 273.15 K up to 873.15 K and water densities from 1000 kg m−3 down to 270 kg m−3 and was reduced down to a final critically evaluated dataset spanning temperatures between 273.15 and 678.15 K and densities between 346 and 1006 kg m−3. The results were used to derive values for the excess conductivity due to prototropic transfer, λE°, of H3O+ and OH− using correlations previously reported for aqueous KCl. Simple empirical correlations of water viscosity and density were derived for Λ°(HCl), Λ°(KOH), Λ°(NaOH), λE°(H3O+), and λE°(OH−). Tests using the λE°(OH−) correlation and a previously reported function for Λ°(NaCl) show that the NaOH data can be accurately reproduced to within the estimated uncertainties. The reported correlations provide a means to model more accurately the tracer diffusion coefficients for H3O+ and OH− to supercritical conditions.

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Revised Parameters for the IAPWS Formulation for the Ionization Constant of Water Over a Wide Range of Temperatures and Densities, Including Near-Critical Conditions

Arcis,

Bachet,

Dickinson

et al. 2024

Journal of Physical and Chemical Reference Data

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The literature database for the ionization constant of water, pKw, has been critically reevaluated to include new accurate flow conductivity data recently reported at near-critical and supercritical conditions. Recently published equations to express the limiting conductivity of fully ionized water were used to correct the conductivity data and yield more accurate pKw values at water densities below 0.6 g cm−3. The ability of the functional forms adopted by the 1980 and 2006 International Association for the Properties of Water and Steam releases to fit the near-critical and supercritical data was tested. Revised parameters for the 2006 “simple” function were derived to improve the accuracy of the model under these conditions. The data fitting procedure made use of estimated standard uncertainties as well as a weighting parameter for each dataset to minimize potential bias due to the very large amount of flow conductivity data now available. Calculations based on the revised formulation were found to be consistent with independent high-temperature data measured using calorimetry and density methods. The revised equation is accurate to within the estimated standard uncertainty limits over the range 0–1000 °C, p = 0–1000 MPa.

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Critical Review of Transport and Equilibrium Properties of Potassium Chloride in High Temperature Water

Cited by 3 publications

References 63 publications

Limiting Conductivities of Strong Acids and Bases in D₂O and H₂O: Deuterium Isotope Effects on Proton Hopping over a Wide Temperature Range

Limiting Conductivities of Strong Acids and Bases in D₂O and H₂O: Deuterium Isotope Effects on Proton Hopping over a Wide Temperature Range

Critical Review of Transport Properties of HCl, KOH, and NaOH in High Temperature Water and Correlations for Transport Properties of H3O+ and OH−

Revised Parameters for the IAPWS Formulation for the Ionization Constant of Water Over a Wide Range of Temperatures and Densities, Including Near-Critical Conditions

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Critical Review of Transport and Equilibrium Properties of Potassium Chloride in High Temperature Water

Cited by 3 publications

References 63 publications

Limiting Conductivities of Strong Acids and Bases in D2O and H2O: Deuterium Isotope Effects on Proton Hopping over a Wide Temperature Range

Limiting Conductivities of Strong Acids and Bases in D2O and H2O: Deuterium Isotope Effects on Proton Hopping over a Wide Temperature Range

Critical Review of Transport Properties of HCl, KOH, and NaOH in High Temperature Water and Correlations for Transport Properties of H3O+ and OH−

Revised Parameters for the IAPWS Formulation for the Ionization Constant of Water Over a Wide Range of Temperatures and Densities, Including Near-Critical Conditions

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Limiting Conductivities of Strong Acids and Bases in D₂O and H₂O: Deuterium Isotope Effects on Proton Hopping over a Wide Temperature Range

Limiting Conductivities of Strong Acids and Bases in D₂O and H₂O: Deuterium Isotope Effects on Proton Hopping over a Wide Temperature Range