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Enthalpies of reaction can also be calculated from individual enthalpies of formation (or heats of formation), Hf , for the reactants and products Because the temperature, pressure, and state of the substance will cause these enthalpies to vary, it is common to use a standard state convention For gases, the standard state is 1 atm pressure For a substance in an aqueous solution, the standard state is 1 molar concentration And for a pure substance (compound or element), the standard state is the most stable form at 1 atm pressure and 25 C A degree symbol to the right of the H indicates a standard state, H The standard enthalpy of formation of a substance ( Hf ) is the change in enthalpy when 1 mol of the substance is formed from its elements when all substances are in their standard states These values are then tabulated and can be used in determining H rxn Hf of an element in its standard state is zero Hf rxn can be determined from the tabulated Hf of the individual reactants and products It is the sum of the Hf of the products minus the sum of the Hf of the reactants: H rxn = Hf products Hf reactants

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Correlations of the excess enthalpy for the temperature range from 32315 to 38315 K (50 to 110 C) lead to infinite-dilution values of C ~ / x 1 x 2 R , which are nearly constant and equal to

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In using this equation be sure to consider the number of moles of each, because Hf for the individual compounds refer to the formation of 1 mol For example, let s use standard enthalpies of formation to calculate Hrxn for: 6 H2O(g) + 4 NO(g) 5 O2(g) + 4 NH3(g) Answer: H rxn = {5[ H f O2 ( g )]+ 4[ H f NH3 ( g )]} {[6 H f H 2O(g)]+ 4[ H f NO(g)]} Using tabulated standard enthalpies of formation gives: Hrxn = [5(000 kJ) + 4( 4619 kJ)] [6( 24185 kJ) + 4(9037)] = 90468 kJ People commonly forget to subtract all the reactants from the products The values of Hf will be given to you on the AP exam, or you will be asked to stop before putting the numbers into the problem An alternative means of estimating the heat of reaction is to take the sum of the average bond energies of the reactant molecules and subtract the sum of the average bond energies of the product molecules

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Equation (1460) may be directly applied with these data to estimate In yIm and In y," for temperatures greater than 36315 K (90 C) The van Laar equations [Eqs (1217)] are well suited to this system, and the parameters for this equation are given as

These data allow prediction of VLE by an equation of state at 36315 K (90 C) and at two higher temperatures, 42315 and 47315 K (150 and 200 C), for which measured VLE l ~ data are given by Barr-David and ~ 0 d ~ ePemberton and Mash report pure-species vapor

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C Pemberton and C J Mash, Znt DATA Series, Sel: B, vol 1, p 66, 1978 reported in Heats ofMizing Data Collection, Chemistry Data Series, vol 111, part 1, pp 457-459, DECHEMA, Frankfumain, 1984 1 2 ~ Ban-David and B F Dodge, J Chem Eng Data, vol 4, pp 107-121, 1959 H

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