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where This general equation makes use of excess Gibbs-energy data at temperature To,excess enthalpy (heat-of-mixing) data at T I ,and excess heat-capacity data at T2 Evaluation of integral J requires information with respect to the temperature dependence of c; Because of the relative paucity of excess-heat-capacity data, the usual assumption is that this property is constant, independent of T In this event, integral J is zero, and the closer To and TI are to T, the less the influence of this assumption When no information is available with respect to c;, and excess enthalpy data are available at only a single temperature, the excess heat capacity must be assumed zero In this case only the first two terms on the right side of Eq (1459) are retained, and it more rapidly becomes imprecise as T increases Because the parameters of 2-parameter correlations of G E data are directly related to infinite-dilution values of the activity coefficients, our primary interest in Eq (1459) is its application to binary systems at infinite dilution of one of the constituent species For this purpose, we divide Eq (1459) by the product ~ 1 x 2For CF independent of T (and thus with

142 VLEfrom Cubic Equations of State J = O), it then becomes:

That s not what my father was about, and that certainly wasn t his leadership model So what exactly did Vince Lombardi say about winning and results, and what did he mean by it

As shown in Sec 121, The preceding equation applied at infinite dilution of species i may therefore be written:

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If the reaction above for the formation of water were reversed, the sign of H would be reversed That would indicate that it would take 4836 kJ of energy to decompose 2 mol of water This would then become an endothermic process H is dependent upon the state of matter The enthalpy change would be different for the formation of liquid water instead of gaseous water H can also indicate whether a reaction will be spontaneous A negative (exothermic) value of H is associated with a spontaneous reaction However, in many reactions this is not the case There is another factor to consider in predicting a reaction s spontaneity We will cover this other factor a little later in this chapter Enthalpies of reaction can be measured using a calorimeter However, they can also be calculated in other ways Hess s law states that if a reaction occurs in a series of steps, then the enthalpy change for the overall reaction is simply the sum of the enthalpy changes of the individual steps If, in adding the equations of the steps together, it is necessary to reverse one of the given reactions, then the sign of H must also be reversed Also, particular attention must be used if the reaction stoichiometry has to be adjusted The value of an individual H may need to be adjusted It doesn t matter whether the steps used are the actual steps in the mechanism of the reaction because Hreaction ( Hrxn) is a state function, a function that doesn t depend on the pathway, but only on the initial and final states Let s see how Hess s law can be applied, given the following information: C(s) + O2(g) CO2(g) H2(g) + (1/2)O2 (g) H2O(1) C2H2(g) + (5/2)O2(g) 2 CO2(g) + H2O(1) find the enthalpy change for: 2C(s) + H2(g) C2H2(g) Answer: 2[C(s) + O2(g) CO2(g)] H2(g) + (1/2) O2(g) H2O(1) 2 CO2(g) + H2O(1) C2H2(g) + (5/2) O2(g) 2C(s) + H2(g) C2H2(g) 2 ( 3935 kJ) 2858 kJ ( 12998 kJ) 2270 kJ H = 3935 kJ H = 2858 kJ H = 12998 kJ.

Data for the ethanol(l)/water(2) binary system provide a specific illustration At a base temperature To of 36315 K (90 C), the VLE data of Pemberton and ash" yield accurate values for infinite-dilution activity coefficients: (In Y )~,= 17720 and (In ~ 2 0 0 = 09042 )~~

THE WILL TO WIN As I set out to answer this question, I m much indebted to Michael O Brien and David Maraniss, the authors of the two best biographies of my father (Vince and When Pride Still Mattered, respectively) Their having tracked down the colorful origins of the comment gives me more confidence in my analysis of it Red Blaik, the legendary head football coach at West Point, was my father s boss, and, by my father s own accounting, the most important influence on his coaching philosophy Blaik arranged to have hung on the walls of the Army dressing room what he called the Ten Football Axioms (This technique of hanging inspirational signs on the locker room walls was imitated by my father in Green Bay) The purpose of the game is to win, read one of Blaik s axioms To dilute the will to win is to destroy the purpose of the game Blaik s wall hangings certainly had a profound effect on my father s psyche The will to win became a stock phrase in The Speech and other of my father s public utterances

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