Conductance of Dilute Hydrochloric Acid Solutions to 458 K and 1.4 MPa

Zimmerman, G. H.; Scott, Philip W.; Greynolds, Wendy; Mayorov, D.

doi:10.1007/s10953-009-9381-8

Cited by 6 publications

(13 citation statements)

References 25 publications

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“…More recently, Zimmerman et al 36,37 reported that Λ°could be accurately represented by simple empirical functions of the solvent viscosity. This method was found to be superior up to 250 °C for NaCl 36 and 300 °C for HCl 37 to the reduced density method of Marshall and the Arrhenius method of Oelkers and Helgeson for fitting experimental data. The Journal of Physical Chemistry B…”

Section: Discussionmentioning

confidence: 99%

“…38 Oelkers and Helgeson 35a noted that modeling the pressure and temperature dependence of the Walden product for aqueous ions under hydrothermal conditions requires the use of an empirical "effective" Stokes radius, which they correlated with ionic hydration numbers. Marshall's 34 reduced state relationship between λ°and solvent density, which reproduces ionic conductivities over a very wide rage of temperature and pressure, is also not consistent with Walden's rule, nor is the more recent empirical model by Zimmerman et al 36,37 Nakahara and Ibuki 39 have strongly advocated abandoning Walden's rule and using the Hubbard-Onsager theory, 40 which includes the effects of dielectric friction.…”

Section: Comparison Of Limiting Molarmentioning

confidence: 98%

“…We chose to fit our experimental values for Λ°using an empirical equation of the type reported by Zimmerman et al, 36,37 which takes the form…”

Section: Articlementioning

confidence: 99%

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Deuterium Isotope Effects on the Ionization Constant of Acetic Acid in H₂O and D₂O by AC Conductance from 368 to 548 K at 20 MPa

et al. 2011

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Values of the ionization constant of acetic acid in H(2)O and D(2)O (K(HAc) and K(DAc)) and the deuterium isotope effect, ΔpK = pK(DAc) - pK(HAc), have been determined from T = 368 K to T = 548 K at p = 20 MPa, using a flow-through ac conductance cell built at the University of Delaware. Measurements were made on dilute (ionic strength ∼ 10(-4) mol·kg(-1)) solutions of acetic acid, sodium acetate, hydrochloric acid, and sodium chloride in H(2)O and D(2)O, injected in sequence at each temperature and pressure, so that systematic errors in the measured conductance of each solution would cancel. Experimental values for the molar conductivity, Λ, of the strong electrolytes were used to calculate the molar conductivity at infinite dilution, Λ°, using the Fuoss-Hsia-Fernández-Prini (FHFP) equation. These were used to calculate the molar conductivity at infinite dilution for acetic acid which was in turn used to calculate the degree of dissociation and finally the ionization constants of acetic acid. This same procedure was done for the pertinent deuterated solutes in D(2)O. Measured values of log K(HAc), log K(DAc), and ΔpK were obtained to a precision of ±0.008. The present results are in agreement with the only other accurate study at high temperatures and pressures (Mesmer, R. E.; Herting, D. L. J. Solution Chem.1978, 7, 901-913). The deuterium isotope effects, ΔpK, become independent of temperature above ∼420 K, at a value approximately 0.1 unit lower than that at 298 K. These values are ΔpK = 0.43 ± 0.01 and ΔpK = 0.51 ± 0.01, respectively. The temperature dependence of the Walden product ratio, (λ°η)(D(2)O)/(λ°η)(H(2)O), indicates a change in the relative hydration behavior of ions, whereby the effective Stokes radii of the sodium, chloride, and acetate ions in D(2)O relative to H(2)O reverse above ∼423 K. The results also suggest that the greater efficiency of the well-established proton-hopping transport mechanisms for OH(-) and H(3)O(+) at 298 K, relative to OD(-) and D(3)O(+), is significantly reduced as the temperature increases toward 548 K.

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Section: Discussionmentioning

confidence: 99%

Section: Comparison Of Limiting Molarmentioning

confidence: 98%

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Deuterium Isotope Effects on the Ionization Constant of Acetic Acid in H₂O and D₂O by AC Conductance from 368 to 548 K at 20 MPa

et al. 2011

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“…The values from the two models agreed with the data to within the experimental uncertainty and agreed with one another to within 1 % or better. Recently, Zimmerman et al 15,16 reported that Λ°could be represented accurately by simple empirical functions of the solvent viscosity and density. It was found that the present sodium chloride results and those available in the literature could be fitted, if the viscosity was greater than 0.00055 Poise, using an empirical equation, which takes the form:…”

Section: Ionic Transport Properties Andmentioning

confidence: 99%

Limiting Conductivities and Ion Association Constants of Aqueous NaCl under Hydrothermal Conditions: Experimental Data and Correlations

2012

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Frequency-dependent electrical conductivities of solutions of aqueous sodium chloride have been measured from T = 298 K to T = 623 K at p = 20 MPa, over a very wide range of ionic strength (2·10 −5 to 0.17 mol·kg −1 ) using a unique highprecision flow-through alternating current (AC) electrical conductance instrument. Experimental values for the equivalent conductivity, Λ, were used to calculate molar conductivities at infinite dilution, Λ°, using the Fuoss−Hsia−Fernandez−Prini (FHFP) and Turq−Blum−Bernard−Kunz (TBBK) ionic conductivity models. The resulting values for the limiting conductivity Λ°and the ion association constant of NaCl, from this work and critically evaluated literature data above 277 K, were represented to within the combined experimental uncertainties, as functions of viscosity and solvent density, respectively. New values and new correlations are reported for the limiting equivalent conductivities of the sodium ion, λ°(Na + ), and the chloride ion, λ°(Cl − ) from 277 K and 100 kPa to 1073 K and 500 MPa.

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“…Solute adsorption is increased by the use of platinum black [1,39], and has been standard protocol since the days of Kohlrausch [18] to minimize strong frequency dependency. It may be profitable to remove the platinum black to minimize solute adsorption and deal with the increased frequency dependence through modeling of the impedance spectrum.…”

Section: Improvements To the R H Wood Conductance Instrumentmentioning

confidence: 99%

Extrapolation Methods for AC Impedance Measurements Made with a Concentric Cylinder Cell on Solutions of High Ionic Strength

Zimmerman

Arcis

2014

J Solution Chem

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Different extrapolation methods of AC impedance spectra measured in a conductance cell with concentric cylinder geometry have been evaluated at room temperature. This was undertaken because previous high temperature studies showed that the extrapolation method was one of the largest contributors to the uncertainty for molar conductivities at high concentrations: these high concentrations are needed to determine ion-pairing formation constants under hydrothermal conditions. This was done by measuring the impedance spectrum of sodium chloride solutions with ionic strengths up to 0.49 molÁkg -1 and comparing different extrapolation methods to accurate molar conductivity results reported by other authors using cells designed for concentrated solutions at ambient conditions. The most accurate extrapolation method at high concentrations was found to be the method based on the expression Z Re x ð Þ ¼ R s þ b 0 Á x Àb 1 , where Z Re (x) is the real component of the angular frequency-dependent impedance, and R s , b 0 and b 1 are fitting parameters.

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Conductance of Dilute Hydrochloric Acid Solutions to 458 K and 1.4 MPa

Cited by 6 publications

References 25 publications

Deuterium Isotope Effects on the Ionization Constant of Acetic Acid in H₂O and D₂O by AC Conductance from 368 to 548 K at 20 MPa

Deuterium Isotope Effects on the Ionization Constant of Acetic Acid in H₂O and D₂O by AC Conductance from 368 to 548 K at 20 MPa

Limiting Conductivities and Ion Association Constants of Aqueous NaCl under Hydrothermal Conditions: Experimental Data and Correlations

Extrapolation Methods for AC Impedance Measurements Made with a Concentric Cylinder Cell on Solutions of High Ionic Strength

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Conductance of Dilute Hydrochloric Acid Solutions to 458 K and 1.4 MPa

Cited by 6 publications

References 25 publications

Deuterium Isotope Effects on the Ionization Constant of Acetic Acid in H2O and D2O by AC Conductance from 368 to 548 K at 20 MPa

Deuterium Isotope Effects on the Ionization Constant of Acetic Acid in H2O and D2O by AC Conductance from 368 to 548 K at 20 MPa

Limiting Conductivities and Ion Association Constants of Aqueous NaCl under Hydrothermal Conditions: Experimental Data and Correlations

Extrapolation Methods for AC Impedance Measurements Made with a Concentric Cylinder Cell on Solutions of High Ionic Strength

Contact Info

Product

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Deuterium Isotope Effects on the Ionization Constant of Acetic Acid in H₂O and D₂O by AC Conductance from 368 to 548 K at 20 MPa

Deuterium Isotope Effects on the Ionization Constant of Acetic Acid in H₂O and D₂O by AC Conductance from 368 to 548 K at 20 MPa