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Reference systems for assessing viability and accuracy of pH sensors in high temperature subcritical and supercritical aqueous solutions

机译:用于评估pH传感器在高温亚临界和超临界水溶液中的生存力和准确性的参考系统

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摘要

This paper describes an effort in developing reference systems to be used in high temperature subcritical and supercritical aqueous solutions for assessing the viability and accuracy of high-temperature pH sensors. Each of these reference systems consists of a couple of three-component aqueous solutions in which the concentration of NaCl is greater than the concentration of another solute, such as HCl and NaOH. The viability of the reference systems was tested using the recently published experimental data employing a flow-through electrochemical cell at temperatures from 25 degrees C to 400 degrees C and densities from 0.17 to 1 g cm(-3) [S.N. Lvov, X.Y. Zhou, and A.V. Bandura, 1999a, Estimation of Isothermal Potential for HCl/NaCl and NaOH/NaCl Systems in High Temperatures Supercritical Aqueous Solutions, J. Supercrit. fluids, in preparation; S.N. Lvov, X.Y. Zhou, and D.D. Macdonald, 1999, Flow-Through Electrochemical Cell for Accurate pH Measurements at Temperature up to 400 degrees C, J. Electroanal. Chem., 463, 146-156]. The applicability of the method was tested for dilute (0.01 and 0.001 mol kg(-1)) HCl aqueous solutions having background NaCl electrolyte in the amount of 0.1 mol kg-l. The most significant property of the reference systems is that the pH difference, and hence, the cell potential, can easily be estimated with sufficient accuracy using only the analytical concentrations of the electrolytes without considering the speciation calculations, given the fact that the association and dissociation constants at supercritical temperatures have not been accurately determined yet. (C) 2000 Elsevier Science B.V. All rights reserved. [References: 55]
机译:本文描述了开发用于高温亚临界和超临界水溶液的参考系统的工作,以评估高温pH传感器的可行性和准确性。这些参考系统均由一对三组分水溶液组成,其中NaCl的浓度大于另一种溶质(如HCl和NaOH)的浓度。参考系统的可行性使用最近发布的实验数据进行了测试,该实验数据采用流通式电化学电池,温度范围为25摄氏度至400摄氏度,密度为0.17至1 g cm(-3)[S.N. Lvov,X.Y.周和AV班杜拉(Bandura),1999a,高温超临界水溶液中HCl / NaCl和NaOH / NaCl系统的等温势估算,J。Supercrit。准备中的液体;序号Lvov,X.Y.周和D.D. Macdonald,1999,流通式电化学池,用于在高达400摄氏度的温度下进行精确的pH测量,J。Electroanal。化学,463,146-156]。测试了方法的适用性,以稀释的(0.01和0.001 mol kg(-1))HCl水溶液的背景NaCl电解质的量为0.1 mol kg-1。参考系统最重要的特性是,只要考虑到缔合和解离的事实,就可以仅使用电解质的分析浓度而无需考虑形态计算就可以很容易地以足够的准确度估算出pH差以及因此的电池电位。尚未准确确定超临界温度下的常数。 (C)2000 Elsevier Science B.V.保留所有权利。 [参考:55]

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