A Test of the Onsager Reciprocal Relations and a Discussion of the Ionic Isothermal Vector Transport Coefficients I(Ij) for Aqueous AgNO(3) at 25 degrees C

Values of I(ij) calculated from experimental data are given for AgNO(3) at 25 degrees C Experimental values of the ratio I(12)/I(21) are calculated to provide a sensitive direct test of the Onsager reciprocal relations, I(12) = I(21). This ratio is found to be unity within experimental error(ca. 2%). The general physical interpretation of I(ij)/N as mobilities is discussed. An approximate way of estimating I(ij) for dissociated salts is considered. A comparison is made between AgNO(3) I(ij) data and corresponding data for NaCl and KCl. It is concluded that ion-pair formation (1) sharply increases the magnitude of the interaction mobility, I(12)/N; and (2) increases the "intrinsic mobility" of Ag(+), I(11)/N, and decreases the intrinsic mobility of NO(3)(-), I(22)/N.