Constant T “i is) ox) Goole fraction) Figure 1.7; A binary system that exhibits negative deviations from Raoult’s law. 1.15 Example Problem: Chlorine is to be used for the oxidation of cyanide in a 36 °C plating waste according to the reaction: CN’ + HOCI+ HyO = CNO™ + CT +H,07 1, Calculate AG in keal/mole if: [Hoc] [CI] = 3, 540mg/L 2. The pH is changed to 11. Does the alkaline environment makes the energetics for the oxidation of the cyanide more or less favor- able? Solution115. EXAMPLE faa First we need to find the standard Gibbs free energy change for the reaction at 96 °C. This requires knowledge of the equilibrium constant at 25 °C and subsequent application of Van’t Hoff's equation. CN + HOCl + HO «+ CNO + cr + HOt AG} 39.6 -19.1 56.69 23.6 © 3137 -56.69 AH} 31.6 — -28.18 ——-68.32 “33.5 40.00 -68.32 ‘The Gibbs free energy change for the reaction at 25 °C is: AC? = (-111.66) — (-36.19) = -75.47kcal/mole Now AG? = RTInK R= 1.987 kcal/(mole-K) and T = 298K. Solving for Kas (equilibrium constant at 25 °C we get: Kos = 2.00 - 10 Next we need to calculate Kap. wks A & = 3) ‘The standard enthalpy change is: AHigg = (~141.84) — (—64.89) = —76.95kcal/mole Substituting into Van’t Hoff’s equation we get: 1m 2.002108 _ -76.950 (1 1 ‘Ks «21.987 (a i)% CHAPTER 1. ENERGETICS and solving for Kg yields: Kop = 1.95 - 10 ‘The standerd Gibbs free energy change at 36 °C AG can now be found. AG = (-1.987)(309)1n(1.95 - 10) ~75.338kcal/mole ‘Next convert the concentration to moles/L and compute Q. (10~4)(1.95 - 10°4)(1.0001) (0.001)(9.98- 10-4) Q= 9-10 and @ _ 99.104 Kg 195-108 Therefore the reaction proceeds as written. When the pH is raised to 11 Q = 9.9- 107M and -Q@ _ 99-1078 Keg ~ 195-108 Alkaline conditions favor the oxidation process since <1 <1 2 Qpn=s Goma . Opts wre < He <1