(中國科學(xué)院 上海硅酸鹽研究所， 上海 200050)
摘 要: 應(yīng)用 Na｜Na+βAl2O3｜NaxPb1-x固體電解質(zhì)電池測(cè)定了42個(gè)Na/NaxPb1-x(x =0.043～0.987 8)電池在508～648 K的電動(dòng)勢(shì)。計(jì)算了鈉/高鉛鈉合金(液，x =0.043～0.6)電池電動(dòng)勢(shì)及其溫度系數(shù)， 鈉在合金中的活度系數(shù)、 偏摩爾熵 - S(Na)、 偏摩爾焓-H (Na)和x(Na)的關(guān)系。 熱力學(xué)函數(shù)對(duì)鈉摩爾分?jǐn)?shù)的線性關(guān)系，相應(yīng)于在鈉 鉛相圖中的富鉛相界、共晶體NaPb4, NaPbNaPb3和化合物NaPb組分處產(chǎn)生的偏折，表征液態(tài)鈉鉛合金存在著類似于固相結(jié)構(gòu)的化學(xué)絡(luò)合物。根據(jù)電池電動(dòng)勢(shì)對(duì)組分和溫度的關(guān)系，測(cè)量了合金的熔化溫度及NaPb4, NaPbNaPb3, NaPbNa9Pb4的共晶溫度。
關(guān)鍵字: 鈉β氧化鋁； 固體電解質(zhì)； 鈉鉛合金； 熱力學(xué)函數(shù)
（Shanghai Institute of Ceramics， Chinese Academy of Science， Shanghai 200050， P.R.China）
Abstract:EMFs of fortytwo Na/NaxPb1-x (x=0.043 !33～0.987 8) cells were measured by using a Na｜Na+ βAl2O3｜NaxPb1-x solid electrolyte cell. The EMF and its temperature coefficient of the Na/NaxPb1-x (liquid)， activity coefficient of the sodium in NaxPb1-x， sodium partial molar entropy - S (Na) and partial molar enthalpy -H (Na) were also calculated as a function of x (Na). For the liquid Na/NaxPb1-x cell， the linear relationship between dE/dT，- S (Na)， -H (Na) and x(Na)， respectively， were deflected at x(Na)= 0.083， 0.20， 0.39， 0.48， 0.52 which correspond to the rich lead phase， NaPb4 entectic point， NaPbNaPb3entictic point and NaPb compound analogous to transformation of phase region inthe NaPb system. The results indicate that chemical complex exist in the molten NaxPb1-x near the temperature of liquids line in NaPb phase diagram. The moing temperatures of NaPb alloys and entectic temperatures of NaPb4， NaPbNaPb3and NaPbNa4Pb9 have been determined from the dependence of the cell EMFon component and temperature.
Key words: sodium betaalumina; solid electrolyte; sodiumlead alloy; thermodynamic function
