GIBB) S-HELMHOLTZ EQUATION (oR) REVATION BETWEEN AG and AH Consider the following relations, G =H -TS (Gibbs free energy) Al) H= E+ PV (enthalpy) (2) Substituting equation (2) in (1) it becomes . GaE+PV-TS QB) For infinitesimal change, dG=dE+PdV+VdP-TdS-SdT = ~ @ namics. But according to first and second law of thermody! dE = dq -P dV (first law) dgq=T dS (second law) . dE=TdS- Pav . (5) Substituting equation (5) in (4) we get, dG =TdS ~PdV+Pdv+VdP-Tas-Satwueueeeevee Gg eee Eee TICK HKYIVS 246 Engineering Chemistry - | dG=VdP-SdT ~ ©) AU constant pressure dP = , equation (6) becomes aG=- sar o ac) | = 8) (=) lp Substituting equation (8) in equation (1), we get 9) This is one form of the Gibb’s - Helmholtz, equation, For any two states of the system the equation (7) may be written as dG, =~S,aT (initial state) dG) =~ S;aT (final state) To get the change dG, - dG, =~ Sa - (- 5,47) Gy ~ Gy) =~ (Sp- Sy) aT (SG) =- as dT + 10) ‘At constant pressure the equation (10) becomes [se ]- ac ~» (1) ar But, according to definition of free energyChemical Thermodynamics 2.47 AG = AH - TAS. 12) ol 2) Substituyirig equation (12) in (11), we get AG~ AH _ [232 a (or) .. 3) Similarly aanaer7( 2S] may be derived. This is another form of Gibbs - Helmholtz equation. f—— =-166 kcals. 5. Compute free energy change when 5 moles of an ideal gas expands reversibly and isothermally at 300 K from an initial volume of 50 L. to 1000 L. (AU. Jan 2014) ‘We know that AG = AH -' TAS qa) Since the process takes place isothermally, AH = 0. Hence Equation (1) becomes Since AS = 2.303 nk log 4 Q) ; AG = -nRT log vy AG = -5 x 1,987 x 300 x og, O° X = -5 x 1,987 x 300 x log 20 Rp =—5 x 1.987 x 300 x 1.3010 Ga Sern a = 3.878 kcals