Persistent confusion of total entropy and chemical system entropy in chemical thermodynamics.
The change in free energy with temperature at constant pressure of a chemical reaction is determined by the sum (dS) of changes in entropy of the system of reagents, dS(i), and the additional entropy change of the surroundings, dS(H), that results from the enthalpy change, W. A faulty identification of the total entropy change on reaction with dS(i) has been responsible for the attribution of general validity to the expressions (d deltaG/dT)p = -deltaS(i) and d(deltaG/T)/d(1/T)= deltaH, which are found in most textbooks and in innumerable papers.
Weber
G
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University of Illinois School of Chemical Sciences, Urbana 61801, USA.
D007700:Kinetics; D008956:Models, Chemical; D013696:Temperature; D013816:Thermodynamics