A New Flow Instrument for Conductance Measurements at Elevated Temperatures and Pressures: Measurements on NaCl(aq) to 458 K and 1.4 MPa

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

doi:10.1007/s10953-007-9144-3

Cited by 16 publications

(21 citation statements)

References 39 publications

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“…At odds with the present results, Zimmerman et al [8] found no differences between Units as in Table 1. In addition, R s ± 95 percent confidence limits, X with leads correction; K exp , K cor , and K lit , SÁcm 2 Ámol -1 ; K cor are K exp are corrected to room pressure using a pressure coefficient calculated from Zimmerman et al [8], K lit have been interpolated from the results reported in Chambers et al [16] and Shedlovsky [17], as taken from Robinson and Stokes [18] at the concentrations of the present results; %dK is the percent difference between K cor and K lit as given by Eq. 27 J Solution Chem methods A and C for a different concentric cylinder high temperature cell.…”

Section: Comparison Of the Extrapolation Methods With Previous Workcontrasting

confidence: 99%

“…They clearly showed that the traditional method of setting the exponent to 0.5 introduced significant error for their new cell and pointed out the work of Ragheb and Geddes [26] that shows that the value of this exponent is dependent upon the type of metal and its surface as well as the solution in the cell. However, since Zimmerman et al [8] found no difference between this method and Methods A and D (see below), this extrapolation was also considered. When applying this method, only frequencies between 1 Simulated impedance spectra using Eq.…”

Section: Methods Cmentioning

confidence: 99%

“…The measurements on NaCl(aq) were done far from the room pressure results with which it was desired to compare. The K exp were therefore corrected to 0.1 MPa and 298.15 K, K cor , by using a pressure coefficient DK°/Dp calculated from Zimmerman et al [8], where DK°is the difference in the molar conductivities at infinite dilution in SÁcm 2 Ámol -1 at each pressure, nominally 19.3 MPa and 0.1 MPa, and assuming that this pressure coefficient is the same for finite concentrations. Examination of the results reported by Fisher and Fox [15] supports this assumption.…”

Section: Application Of the Extrapolation Modelsmentioning

confidence: 99%

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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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Section: Comparison Of the Extrapolation Methods With Previous Workcontrasting

confidence: 99%

Section: Methods Cmentioning

confidence: 99%

Section: Application Of the Extrapolation Modelsmentioning

confidence: 99%

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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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“…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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“…As the first class of solid electrolytes is well studied [5][6][7][8][9][10], the electrical and optical properties of solid electrolytes of the second class are being intensively investigated. Among them are high temperature phases of α-Li 2 SO 4 (586-860 °C), α-Ag 2 SO 4 (412-660 °C) sulfates of one-valent metals (Li + , Na + and Ag + ) and also solids Li 2 SO 4 -Na 2 SO 4 and Li 2 SO 4 -Ag 2 SO 4 , Na 2 SO 4 .…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic Investigation of Composite Polymeric and Monocrystalline Systems with Ionic Conductivity

Radziuk¹,

Möhwald²

2011

Polymers

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Abstract:The conductivity mechanism is studied in the LiCF 3 SO 3 -doped polyethylene oxide by monitoring the vibrations of sulfate groups and mobility of Li + ion along the polymeric chain at different EO/Li molar ratios in the temperature range from 16 to 90 °С. At the high EO/Li ratio (i.e., 30), the intensity of bands increases and a triplet appears at 1,045 cm −1 , indicating the presence of free anions, ionic pairs and aggregates. The existence of free ions in the polymeric electrolyte is also proven by the red shift of bands in Raman spectra and a band shift to the low frequency Infra-red region at 65 < T < 355 °С. Based on quantum mechanical modeling, (method MNDO/d), the energies (minimum and maximum) correspond to the most probable and stable positions of Li + along the polymeric chain. At room temperature, Li + ion overcomes the intermediate state (minimum energy) through non-operating transitions (maximum energy) due to permanent intrapolymeric rotations (rotation of C, H and O atoms around each other). In solid electrolyte (Li 2 SO 4 ) the mobility of Li + ions increases in the temperature range from 20 to 227 °С, yielding higher conductivity. The results of the present work can be practically applied to a wide range of compact electronic devices, which are based on polymeric or solid electrolytes.

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A New Flow Instrument for Conductance Measurements at Elevated Temperatures and Pressures: Measurements on NaCl(aq) to 458 K and 1.4 MPa

Cited by 16 publications

References 39 publications

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

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

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

Spectroscopic Investigation of Composite Polymeric and Monocrystalline Systems with Ionic Conductivity

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