+ Partial Molar Quantities (Free Energy, Volume, Heat Concept) So far we have discussed the variation of various thermodynamic properties with respect to temperature and pressure while the composition of the system was kept constant (closed system), In 1907. GIN. Lewis started the study of open systems i.e, the variation of various thermodynamic properties with respect to the composition of one or more components. In other words, he studied the behavior of a particular thermodynamic property of the system when a component is removed from or added to the system under sonsideration. Now since a variation like this is observable only for an extensive property, the general definition of partial molar properties can be given as given below. A partial molar property may simply: be defined as a thermodnamic quantity which indicates how ‘an extensive property of @ solution or mixture changes with the variation in the molar composition of the ‘mixture at constant temperature and pressure, Basically, it is the partial derivative of the extensive property with respect to the number of moles of the component under consideration. All extensive properties of a mixture haye corresponding partial molar propertics. In this section, we will discuss some very important partial molar quantities like partial molar free ‘energy (Gj). partial molar volume (¥,) and partial molar enthalpy (Fi). uy> Partial Molar Volume In order to derive the expression for partial molar volume, consider a system that comprises of 7 types of constituents with m, ms, m,n ... moles. So, being an extensive property. volume depends upon not only the temperature and pressure but also on the number of moles of different components. Mathematically, we ean say that F(T Pima nama) (165) Now let us assume a small change in the temperature, pressure and amount of different components this would impart a variation in partial molar volume as given below. (166) The first term on the right-hand side gives the change in the volume with the temperature at constant pressure and compositions; while the second term gives the change in the volume with pressure at constant temperature and compositions. The terms afierward represent the variation in volume with the amount of one component while the temperature, pressure and all other compositions are kept constant. However, if the temperature and pressure of the system are Kept constant i.e. d7°= 0, dl? = 0, the equation (166) takes the form av wv 167 — dny + (— dns. (lee 2 Taman ONS Teme Every term on the right-hand side of the equation (167) is partial molar volume and is symbolized by a “bar” over itie. (168) (mh me (h (169) After putting the values fiom equations like (168 ~ 169) m equation (7), we get (dV) rp dn, + dn, +Vy dus (170) For the th component, we cam say that 5 v 7- (24) am in) Ta nssny ‘The equation (171) gives the general expression for the “partial mola: volume” of the ith species107 > Partial Molar Enthalpy or Partial Molar Heat Content In order to derive the expression for partial molar enthalpy, consider a system that comprises of » types of constituents with m, m, ms, ns... moles. So, being an extensive property. volume depends upon not only the temperature and pressure but also on the number of moles of different components, ¢. H = f(T, P.ny rans.) (172) ‘Now let us assume a small change in the t¢mperature, pressure and amount of different components, this would impart a variation in molar enthalpy as given below (173) The first term on the right-hand side gives the change in the enthalpy with the temperature at constant pressure and compositions; while the second term gives the change in the enthalpy with pressure at constant temperature and compositions. The terms afterward represent the variation in enthalpy with the amount of one component hile the temperature, pressure and all other compositions are kept constant However, ifthe temperature and pressure of the system are kept constant i.e. d7 equation (173) takes the form oH aH (174) Ga) ving + (oy, us amet Oy dns... » MT Pans nz" TPmans, 73 rPana inp Every term on the right-hand side of the equation (174) is partial molar enthalpy and is symbolized by a “bar” over itic ie t \ ‘ "76 pootiom 1 ' yy "After pitting the values from equations like (175 — 176) in earation (174), we get ‘ retin di)pp = amy For the ih component. we can say that it i" ea oH) ‘ (178) i ya oie the AyD action eas 0 NM ap nang iChemical Potential: The partial molar gibbs five energy has been given a specific symbol 1 because of its univerasality in dealing with various aspects of Its signifecance is discussed here, For a multicomponent thermodynamics stud system, free energy is a function of T.P and number of moles (nj) of various specis Thus. And dG = (Dammit + (Frm? * Gale dny + F(T, Py ry, may) aw — _ t( IP +G, dny+Gy dng +... = (1) MyM F, et 1 dry + G2 dng 2) ah Gop) gh dhe MET Py pi= Chemical potential of component i in the system and is defined as the change in the Gibbs free energy with the change in the number of moles of component i when T and P and the moles of othler components are kept constant! 7 It is an intensive property and is a measure of escaping tendency. For a closed system dn, = 0,dny = 0 and equation (1) gives he (26 wg (28 a ? (dG)yo= G),.,,@7 + GPa dl But for a closed system G) dG= -SdT +/VaP ------2!---(4) i Comparing the coefficient in the equation (3) and (4) we get, 5 ‘0G WO ag ie ia)p ue Gep (5) From the equation (1),(2) and (8) we have | AG = -S dT + VP + pj'dn, + jigdny + “S\-SdT + Vdp+ Dj ujdny (6)For constant T and P: dT=0 and dP=0 IG = Fi edn; and = pydrytiydn, +... Equation (7) can be integrated for a constant composition system to give G= amy than, + Da Myr man (8) The total differencial of G is given by AG = pydny+ny duty + node +podny / . ( \ Comparing’ equn. (6) and'(9) we ‘get! -S dT ¥VdP + Di eidn; = wydnytny dy, + ngdigt+pHydny Haut = adn, + pydny + nyduy + ngdito “s are vap t Die ‘dry - t “2 Hr dnp + Lindy; ‘ Terms geting cancel and we get “S dT + VdP =i n ia Or -SdT+VdP- Bini ay = Oeste (10)For an isothermal and isobaric process eqn. (10) reduces to Linjdu; = 0 The Gibbs-Duhem equationVariation of Pr Ssure on chemical potential ; Chemical potential of ith component of a system is defined ac oer Gr TP ny a? as Differenciating equation(1) wrt P at constant T and composition we get (FF) ra, = 35| (Gn) oP 7 Ty OP LON 7 py, eG _ ae aPAn; — aniaP Tani i (2) >a 2) | 1 OP) py, On; [\OP/ 7p, T.Pnj Where ¥, = Partial molar volume of ith component . Fquation (2) can be integrated for suitable limits , Sedu; = Si aP --- Equation (3) can be used fo calculate the chemical potential of th and solids , provide we know the pressure dependence of v (ee) he gases, liquids olume._ Variation of temperature on chemical potenti Oni T Pn; Differenciating equation(1) wrt T at constant P and composition we get ),,- HG). Since G is a state function ne #6 #G aTOn, OnjaT ree anlar) pa eee TP ( a =F Oren) = +) 5, = (SB) Partial molar entropy. On TPH; | From equation (2) it is clear that the cheiital potentialwill decrease with increase temperature as entropy is always a positive quantity. 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