High Temperature Aqueous Electrolyte Concentration Cells and the Ionization of Liquid Water to 200 °C

Macdonald, Digby D.; Butler, P. A.; Owen, Dave

doi:10.1139/v73-389

Cited by 25 publications

(8 citation statements)

References 8 publications

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“…The ion product along the liquid–vapour equilibrium has been experimentally determined among others by Bignold et al. (1971), Fischer & Barnes (1972), MacDonald et al. (1973) and Sweeton et al.…”

Section: Properties Of Pure H2o At Elevated P–t Conditionsmentioning

confidence: 99%

“…At elevated P-T conditions, however, K w notably changes. The ion product along the liquid-vapour equilibrium has been experimentally determined among others by Bignold et al (1971), Fischer & Barnes (1972), MacDonald et al (1973 and Sweeton et al (1974). Measurements at elevated pressure and temperature conditions above the critical point of water were performed by Franck (1956) at 350-970 MPa ⁄ 500-1000°C and by Quist (1970) up to 555 MPa and 800°C.…”

Section: Self-dissociationmentioning

confidence: 99%

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Aqueous fluids at elevated pressure and temperature

Liebscher

2010

Geofluids

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The general major component composition of aqueous fluids at elevated pressure and temperature conditions can be represented by H 2 O, different non-polar gases like CO 2 and different dissolved metal halides like NaCl or CaCl 2 . At high pressure, the mutual solubility of H 2 O and silicate melts increases and also silicates may form essential components of aqueous fluids. Given the huge range of P-T-x regimes in crust and mantle, aqueous fluids at elevated pressure and temperature are highly variable in composition and exhibit specific physicochemical properties. This paper reviews principal phase relations in one-and two-component fluid systems, phase relations and properties of binary and ternary fluid systems, properties of pure H 2 O at elevated P-T conditions, and aqueous fluids in H 2 O-silicate systems at high pressure and temperature. At metamorphic conditions, even the physicochemical properties of pure water substantially differ from those at ambient conditions. Under typical mid-to lower-crustal metamorphic conditions, the density of pure H 2 O is q H2O ¼ 0:6À1:0 g cm À3 , the ion product K w = 10 )7.5 to approximately 10 )12.5 , the dielectric constant e = 8-25, and the viscosity g = 0.0001-0.0002 Pa sec compared to q H2O ¼ 1:0 g cm À3 , K w = 10 )14 , e = 78 and g = 0.001 Pa sec at ambient conditions. Adding dissolved metal halides and non-polar gases to H 2 O significantly enlarges the pressure-temperature range, where different aqueous fluids may co-exist and leads to potential two-phase fluid conditions under must mid-to lower-crustal P-T conditions. As a result of the increased mutual solubility between aqueous fluids and silicate melts at high pressure, the differences between fluid and melt vanishes and the distinction between fluid and melt becomes obsolete. Both are completely miscible at pressures above the respective critical curve giving rise to so-called supercritical fluids. These supercritical fluids combine comparably low viscosity with high solute contents and are very effective metasomatising agents within the mantle wedge above subduction zones.

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Section: Properties Of Pure H2o At Elevated P–t Conditionsmentioning

confidence: 99%

Section: Self-dissociationmentioning

confidence: 99%

Aqueous fluids at elevated pressure and temperature

Liebscher

2010

Geofluids

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“…Various versions of the high temperature aqueous hydrogen concentration cell were subsequently developed by Mesmer et al [9][10][11][12][13], Palmer and/or Wesolowski and co-workers [14][15][16][17][18][19][20] and Macdonald et al [21][22][23]. Results using similar cells have also been reported by Shoesmith and Woon [24], Giasson and Tewari [25], Matsushima et al [26], and Bilal and Mueller [27].…”

Section: Hydrogen Electrodesmentioning

confidence: 77%

“…a variety of sensors have been developed to measure the activity of H + in high temperature aqueous solutions, including Pd/H electrodes [61][62][63][64], Pt/ H 2 electrodes [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25], metal/metal oxide electrodes [80,81], glass electrodes [82], and most importantly yttria-stabilized zirconia [Zro 2 (Y 2 o 3 )] electrodes [44,[71][72][73]. The latter [Zro 2 (Y 2 o 3 )] sensors have now been used for monitoring pH in supercritical systems at temperatures to 528°c [73], which is more than 150°c higher than the critical temperature.…”

Section: Ph Sensorsmentioning

confidence: 99%

Electrochemical techniques for monitoring and controlling corrosion in water-cooled nuclear reactor systems

Macdonald

2012

Nuclear Corrosion Science and Engineering

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“…Previous studies involving precise pH measurements in high temperature aqueous systems have employed concentration cells with transport to compare the activity of H + in the solution of interest with that in a standard solution for which the pH can be calculated. This technique has been used extensively by Mesmer et al (1)(2)(3)(4) and by Macdonald and co-workers (5)(6)(7) to study various hydrolysis reactions and transport processes in high temperature solution. Although the technique is very precise, it suffers two restrictive requirements: First, an overpressure of hydrogen is required for the proper operation of the cell.…”

mentioning

confidence: 99%

The Measurement of pH in Aqueous Systems at Elevated Temperatures Using Palladium Hydride Electrodes

Macdonald

Wentrcek

Scott

1980

J. Electrochem. Soc.

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The use of palladium hydride electrodes (Pd black on Pd, Pt, and Au) for the measurement of pH in high temperature aqueous systems (298°–548°K) is described. The electrodes were calibrated against boric acid/lithium hydroxide buffer solutions, whose pHT vs. temperature profiles have been calculated using known dissociation constants for the components. Linear potentialvs. pH correlations are observed for all temperatures studied. However, the gradients of the correlations deviate from the predicted Nernstian values. Furthermore, thermodynamic analyses of the systems demonstrate that above 373°K the observed potential deviates significantly from the equilibrium values calculated on the supposition that the potential‐determining reaction is H++e−⇄Hfalse(normalPd,α+βfalse) . Possible reasons for the observed deviation from ideal behavior are identified.

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High Temperature Aqueous Electrolyte Concentration Cells and the Ionization of Liquid Water to 200 °C

Cited by 25 publications

References 8 publications

Aqueous fluids at elevated pressure and temperature

Aqueous fluids at elevated pressure and temperature

Electrochemical techniques for monitoring and controlling corrosion in water-cooled nuclear reactor systems

The Measurement of pH in Aqueous Systems at Elevated Temperatures Using Palladium Hydride Electrodes

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