Correspondence. Macroscopic Approach to Irreversible Thermodynamics

Derivation of Higher Order Reciprocal Relations

“…Andrews has recently presented a review article discussing the macroscopic approach to reciprocal relations, in which he concludes that macroscopic derivations are likely to end in failure (Andrews, 1967b). We agree with Andrews and others (Fitts, 1962;Mixon, 1963; Wei and Zahner, 1965) that attempts to derive reciprocal relations from pure macroscopic considerations do not seem promising.…”

“…The above-mentioned derivations are all based on macroscopic considerations without invoking the principle of microscopic reversibility as used by Onsager in his derivation of Equation 3. It is the opinion of several authors that this microscopic approach is essential (Andrews, 1964(Andrews, , 1967aMixon, 1963;Fitts, 1962;Wei and Zahner, 1966). This work presents a derivation of a set of relations among the firstand higher-order coefficients in Equation 1, based on the principle of microscopic reversibility.…”

Communication. Note on the Onsager Reciprocal Principle

“…(11) Masamune, Shinobu, Smith, J. M., A.I.Ch.E. J., to be pub- which, admittedly, are somewhat controversial have been presented in this journal recently (5,6) on the derivation of Onsager reciprocal relationships. This note has been prepared with the hope that a survey of the recent literature on the subject may shed some light on the basic problem underlying the controversy.…”