We have now introduced several thermodynamic parameters that are useful in dealing with energy transfers (U, H, G, etc.). We wish now to see how these quantities are measured and where to find values for them. In later chapters we will see how they are used in detail. However, we have an immediate problem in that we cannot measure the energy parameters U, H, G and A, as discussed in Chapter 4. Because we do not know the absolute values of either the total or molar version of these variables, we are forced to deal only with their changes in processes or reactions of interest to us. But we obviously cannot tabulate these changes for every reaction of potential interest; there are too many. We must tabulate some sort of energy term for each pure substance so that the changes in any reaction between them can be calculated. In the example in §5.7 of water at — 2°C changing to ice at — 2°C, we said that AG was negative. How can we know this without carrying out a research program on the thermodynamic properties of ice and supercooled water? We begin by explaining how this is done. The problem created by not having absolute energy values is handled very conveniently by determining and tabulating, for every pure compound, the difference between the (absolute) G or H of the compound itself and the sum of the (absolute) G or H values of its constituent elements. In other words, AG or AH is determined for the reaction in which the compound is formed from its elements (in their stable states). These differences can be determined experimentally in spite of not knowing the absolute values involved.
Solvent Reorganization Energy and Free Energy Change for Donor/Acceptor Electron Transfer at Micelle Surfaces: Theory and Experiment
