高温水溶液pH值原位测量系统与机理

doi:10.11944/j.issn.1000-0518.2016.11.160082

摘要/Abstract

摘要：

研制了以氧化钇稳定氧化锆(YSZ)陶瓷薄膜电极为pH电极、外置压力平衡式Ag/AgCl电极为参比电极的高温高压水溶液pH值原位测量系统,测量了H₃BO₃\LiOH水溶液在473.15~573.15 K范围内的pH值,并与热力学计算得到的pH值比较。结果表明,当温度高于548.15 K时,测量系统可以实现pH值的准确测量;而低于此温度时,由于YSZ陶瓷膜内阻过大,测得的pH值与理论计算值存在偏差,且随温度的降低,测量偏差增大。讨论了该系统的pH值测量机理。

关键词: 高温高压水, pH值, 陶瓷薄膜电极, YSZ电极, 原位测量, 热力学计算

Abstract:

A system based on yttria-stabilized zirconia(YSZ) membrane electrode and external pressure balanced Ag/AgCl electrode has been developed for in-situ pH measurement in high temperature aqueous solutions. The pH values of H₃BO₃\LiOH solutions at 473.15 K to 573.15 K were measured by this system and compared with thermodynamically calculated pH values. The precise pH measurement is achieved when temperature is higher than 548.15 K. While below 548.15 K, deviation exists due to the large resistance of YSZ ceramic membrane and it increases with decreasing temperature. The mechanism of pH measurement in high temperature aqueous solutions is also discussed.

Key words: high temperature aqueous environment, pH measurement, membrane electrode, yttria-stabilized zirconia electrode, in-situ measurement, thermodynamical calculation

郭琦, 吴欣强, 韩恩厚, 柯伟. 高温水溶液pH值原位测量系统与机理[J]. 应用化学, 2016, 33(11): 1329-1336.

GUO Qi, WU Xinqiang, HAN Enhou, KE Wei. In-situ pH Measurement System and Mechanism for High Temperature Aqueous Solutions[J]. Chinese Journal of Applied Chemistry, 2016, 33(11): 1329-1336.

参考文献

[1]	Hara N,Macdonald D D.Development of Dissolved Hydrogen Sensors Based on Yttria-Stabilized Zirconia Solid Electrolyte with Noble Metal Electrodes[J]. J Electrochem Soc,1997,144(12):4152-4157.
[2]	Lvov S N,Zhou X Y,Ulmer G C,et al.Progress on Yttria-Stabilized Zirconia Sensors for Hydrothermal pH Measurements[J]. Chem Geol,2003,198(3/4):141-162.
[3]	Mesmer R E,Baes C F Jr. Phosphoric Acid Dissociation Equilibria Aqueous Solutions to 300 Degrees C[J]. J Solution Chem,1974,3(4):307-322.
[4]	Mesmer R E,Baes C F,Sweeton F H.Acidity Measurements at Elevated Temperature.4. Apparent Dissociation Product of Water in 1-M Potassium Chloride up to 292 Degrees[J]. J Phys Chem,1970,74(9):1937-1942.
[5]	Mesmer R E,Baes C F,Sweeton F H.Acidity Measurements at Elevated-Temperatures.6. Boric-Acid Equilibria[J]. Inorg Chem,1972,11(3): 537-543.
[6]	Tsuruta T,Macdonald D D.Measurement of pH and Redox Potential in Boric-Acid Lithium Hydroxide Buffer Solutions at Elevated-Temperatures[J]. J Electrochem Soc,1981,128(6):1199-1203.
[7]	Macdonald D D,Wentrcek P R,Scott A C.The Measurement of pH in Aqueous Systems at Elevated-Temperatures Using Palladium Hydride Electrodes[J]. J Electrochem Soc,1980,127(8):1745-1751.
[8]	Dobson J V,Jasinski R,Chapman B R,et al.Palladium Hydride pH Electrode for Use in Buffered Fluoride Etch Solutions[J]. J Electrochem Soc,1975,122(12):1634-1635.
[9]	Nagy Z,Yonco R M.Palladium Hydrogen Membrane-Electrode for High-Temperature High-Pressure Aqueous-Solutions[J]. J Electrochem Soc,1986,133(11):2232-2235.
[10]	Niedrach L W.Oxygen Ion-Conducting Ceramics-New Application in High-Temperature High-Pressure pH Sensors[J]. Science,1980,207(4436):1200-1202.
[11]	Niedrach L W.A New Membrane-Type pH Sensor for Use in High Temperature-High Pressure Water[J]. J Electrochem Soc,1980,127(10): 2122-2130.
[12]	Hettiarachchi S,Kedzierzawski P,Macdonald D D. pH Measurements of High Temperature Aqueous Environments with Stabilized-Zirconia Membranes[J]. J Electrochem Soc,1985,132(8):1866-1870.
[13]	Tsuruta T,Macdonald D D.Stabilized Ceramic Membrane Electrodes for the Measurement of pH at Elevated-Temperatures[J]. J Electrochem Soc,1982,129(6):1221-1225.
[14]	Hettiarachchi S,Makela K,Song H,et al.The Viability of pH Measurements in Supercritical Aqueous Systems[J]. J Electrochem Soc,1992,139(1): L3-L4.
[15]	Niedrach L W. pH Measurements of High-Temperature Aqueous Environments with Stabilized-Zirconia Membranes[J]. J Electrochem Soc,1986,133(7): 1521-1521.
[16]	Niedrach L W.Use of a High-Temperature pH Sensor as a Pseudo-Reference Electrode in the Monitoring of Corrosion and Redox Potentials at 285-Degrees-C[J]. J Electrochem Soc,1982,129(7):1445-1449.
[17]	Zhang W,Charles E A.A Thermodynamic Approach to Calculate the Yttria-Stabilized Zirconia pH Sensor Potential[J]. J Appl Electrochem,2003,33(11):1025-1033.
[18]	Macdonald D D,Scott A C,Wentrcek P.External Reference Electrodes for Use in High-Temperature Aqueous Systems[J]. J Electrochem Soc,1979,126(6): 908-911.
[19]	Macdonald D D,Hettiarachchi S,Song H,et al.Measurement of pH in Subcritical and Supercritical Aqueous Systems[J]. J Solution Chem,1992,21(8):849-881.
[20]	Kerner Z,Balog J,Nagy G.Testing of High Temperature Reference Electrodes for Light Water Reactor Applications[J]. Corros Sci,2006,48(8):1899-1911.
[21]	Lvov S N,Gao H,Macdonald D D.Advanced Flow-Through External Pressure-Balanced Reference Electrode for Potentiometric and pH Studies in High Temperature Aqueous Solutions[J]. J Electroanal Chem,1998,443(2):186-194.
[22]	GUO Qi,WU Xinqiang,WANG Xiang,et al.A Ceramic Membrane Electrode for Electrochemical Tests in High Temperature High Pressure Water:CN,201510141325.6[P],2015 -03-27(in Chinese). 郭琦,吴欣强,王翔,等. 一种能实现高温高压水电化学测试的陶瓷薄膜电极:中国,201510141325.6[P],2015-03-27.
[23]	Bojinova M,Galtayries A,Kinnunen P,et al.Estimation of the Parameters of Oxide Film Growth on Nickel-Based Alloys in High-Temperature Water Electrolytes[J]. Electrochim Acta,2007,52(26):7475-7483.
[24]	Liu X H,Wu X Q,Han E-H.Influence of Zn Injection on Characteristics of Oxide Film on 304 Stainless Steel in Borated and Lithiated High Temperature Water[J]. Corros Sci,2011,53(10):3337-3345.
[25]	Niedrach L W,Stoddard W H.Zirconia Membrane pH Sensors[J]. Ind Eng Chem Prod Res Dev,1983,22(4):594-599.
[26]	Taylor D F,Caramihas C A.Crevice Corrosion in High-Temperature Aqueous Systems Potential pH Measurements in Alloy-600 Crevices at 288-Degrees-C[J]. J Electrochem Soc,1982,129(11):2458-2464.
[27]	Covington A K,Bates R G,Durst R A.Difinition of pH Scales, Standard Reference Values, Measurement of pH and Related Terminology[J]. Pure Appl Chem,1985,57(3):531-542.
[28]	Covington A K,Ferra M I A,Zou Z Y. Application of Multilinear Regression Analysis to the Evaluation of Standard pH Values for Potassium Hydrogen Phthalate Reference Value Standard Solutions at Temperatures up to 498K[J]. Electrochim Acta,1985,30(6):805-809.
[29]	Wagnera W,Pruβ A.The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use[J]. J Phys Chem Ref Data,2002,31(2):387-535.
[30]	Palmer D A,Bénézeth P,Wesolowski D J.Boric Acid Hydrolysis:A New Look at the Available Data[J]. Power Plant Chem,2000,2(5):261-264.
[31]	Tremaine P R,Von Masscow R,Shierman G R.A Calculation of Gibbs Free Energies for Ferrous Ions and the Solubility of Magnetite in H2O And D2O to 300 C[J]. Thermochim Acta,1977,19(3):287-300.
[32]	IAEA,High Temperature on-Line Monitoring of Water Chemistry and Corrosion Control in Water Cooled Power Reactors[R]. ISBN:92-0-112702- 2,2002.