By Dana Bell
Air strength colours Vol.I: 1926-1942
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Extra info for Air Force Colors, Vol.I. 1926-1942
77) Thus heat may flow from the environment into the reaction mixture or vice versa, and entropy may be exchanged between them, but a necessary and sufficient condition for equilibrium within the reaction mixture is that no process can lead to a freeenergy change. The derivation assumes that temperature and pressure remain constant during any possible change. Actually it is only necessary that the temperature and pressure be the same at the end of a change as at the beginning, for dG and Ll G depend only on the initial and final states of a system.
0 fA LJ G ' IS a mea sure Free Energy and the Equilibrium Constant. For a chan e of free ener . at constant temperature (dT = 0), Eqs. (71) and (72) gi~e gy wIth pressure OP T =V dLlG dP =LI V. and 1 LlG= JLlVdP= J(RT/P)dP=RT Jd In P. (83) (84) If LI G1 for P 1 -1 atm isdefin ed as a standard free-energy change LI GO th . b ecomes , e equatIOn ' (85) At some one value of P defi d h liquid and vapor are in ~q' uilib:~u~sa:; :aGPo~POreHssure at a given temperature, LJ 2-' -LlGO=RT In P ence d In f = d GIRT (at constant temperature) (88) where f and G are the fugacity and molal free energy of the gas.
13). Now for a chemical reaction (91) bB+dD~yY+zZ Eq. f the s~cond equation is applied to the vaporization of a ure l i ' . IS practIcally equal to the volume of vapor. If the vapor hqu1d ~r sohd, LI V LI V for I f 0 eys t e perLect-gas law and Eq • (82) l'S rea dil' one mo e 0 gas may be set equal to RTiP I , y tntegrable:' Hence a substance would exert if its vapor behaved as a perfect gas. One way of expressing this definition offugacity is by writing Eq. (86) in differential form for a single substance: (90) The correspondin~ criterion for a spontaneous reaction at constant volume an constant temperature IS the statement that LlA b '.
Air Force Colors, Vol.I. 1926-1942 by Dana Bell