A treatise on heat: Including kinetic theory of gasses by Meghnad Saha

By Meghnad Saha

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If T > 373 K, LG < 0, and the changein stateis spontaneous,whereasif T < 373 K, AG > 0, and the reverseprocess,condensation,occurs spontaneously. Calculation of the free energy for a change in state is not always straightforward. The free energy change,of course,is the sameregardlessof how the changein stateis accomplishedsincethe free energy is a statefunction. 2-11. This is not a reversibleprocesssince the two statesare not in equilibrium. This also is not a spontaneouschangein stateso that AG > 0.

For phasechangesof pure substances,this means that at equilibrium the free energiesof the phasesare equal. If we assumetwo phases, A and B, Eq. 2-26 gives dGo- V^dP - S^dT - dGt= VBdP - SBdT gives Rearrangement ii , irt: ,i i. ,,r dP _ASBA dT AVuo i 1i i- (2-46) where ASuo- SB So and AVuo = Vn- yA. ) This equation is often referred to as the Clapeyron equation. As an example, the phasediagram of water is given in Figure 2-3. The lines in Figure 2-3 indicate when two phasesare in equilibrium and coexist.

For example, membranes contain phospholipids. If phospholipids are mixed with water, they spontaneouslyform bilayer vesicles with the head groups pointing outward toward the solvent so that the interior of the bilayer is the hydrocarbon chains of the phospholipids. A schematic representation of the bilayer is given in Figure 2-4. The hydrocarbon chain can be either disordered, at high temperatures,or ordered, at low temperatures,as indicated schematically in the figure. The transformation from one form to the other behavesas a phasetransition so that phase diagrams can be constructed for phospholipids.

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