Thermoelectric power of the vitreous electrolyte (AgI)0.79(Ag2O.B2O3)0.21

We have determined the thermoelectric power ? of the high ionic conductivity glass (AgI)_0.79(Ag₂O.B₂O₃)_0.21; ? is negative throughout the investigated T range, 320–500 K. The heat of transport of the mobile Ag⁺, Q_Ag, taken as the slope of the straight line fitting ? versus 1/T, is quite lower than the activation energy obtained from conductivity data, viz. Q_Ag = 2.81 kcal/mole^-1 < E_act = 4.34 kcalmole^-1. To circumvent this discrepancy, the analysis of the experimental data is carried out as follows: (i) it is supposed that Q_Ag = E_act in agreement with the free ion theory for solid electrolytes; (ii) the vibrational part of the silver ion entropy, S(Ag⁺, vib), is assumed to be equal to the entropy of silver, S(Ag); (iii) on the ground of a structural model for this kind of glasses, the ideal configurational entropy of the mobile Ag⁺, S(Ag⁺, conf)_id, is evaluated through a statistical approach. The ideal ionic entropy is defined as S(Ag⁺)_id = {S(Ag⁺, vib) + S(Ag⁺, conf)_id}; (iv) the difference {S(Ag⁺)_exp - S(Ag⁺)_id} is viewed as an excess entropy and is described according to the classical model of the regular solutions.