SYSTEMS OF VARIABLE COMPOSITION PARTIAL MOLAR QUANTITIES Dependence of thermodynamic parameters on composition. The study of thermodynamic concept so far remains confined to the study of change in thermodynamic properties with the variation of sate variables. The possibility of change with the transport of mass from or to the system have teen excluded. The system is said to be an open system in which the transfer of mass takes place while the one in which no transfer of mass occurs is called closed system. We know that, U, H, S, A and G are extensive properties. With the transfer of mass, the extensive functions suffer a proportionate change in their values. GN. Lewis introduced the concept of partial molar properties for thermodynamic study of heterogeneous systems containing two or more phases (Solutions of two or ‘ore components). In these cases, both mass and composition vary. The values of the extensive properties such as U, H, S, A and G are completely determined if the state variables P, T and composition are fixed. An extensive thermodynamic property X may be tepesented as : X= fT, my, ny wn nj) (i) Here ny, ny, nny nj ate the number of moles of various components of the system. eg t® Stange in the property X may be represented by equation (i) when the variables slightly tr from their fixed values dx -(3) ars) an) Pin LOT 8M HN mys nge nm ax ax +/- dn; + | 5 oii) M2 Ter, mys .ceeot 3 JP, T, my mM = “i dn,sac mmmmmmmmmmmimnicouscncinncre cy, 266 ey, . ax ‘The form | > ~ AM; Jp Tmyamgyeee _ ae called the partial molar property of the constituent and is the partial derivative of the e + 1 - all other derivatives except "i remain constant. It is written as X; Thus, we e fe ax < ( ax } : s = is (=) ™ any PT, mys M352 4M Jp T, nyy gy ee bn “a ii 4; Jp. 7,m,m.- ‘Thus, equation (ji) may be written as ; ; ap w+(| aU 4X1 dry + X2 dry +... 4X; dn, & lap Jey Tp If T and P are kept constant, then (Xp, p= Xy dry + X2 dry +... + Xi dry For a sytem of definite composition represented by mole numbers m,n, found by integration of equation (). Thus, (Xp p = Kim + Xp my be. Xi 9 A general differentiation of equation (vi) gives (Xp, p = Xidn, +n, AX + Xo diy + mydXy +... Xi day + mdXi i From (v) and (vii), we get mdXy + nydXo +0... + mdXi sD njdXi = 0 li) i Thus, relation (viii) is applicable to a system of definite composition at constant T and P. Significance. Partial molar quantities have the following significance : 1. The sum total property (X) for the mixture can be expressed in terms of the numberof nok and the partial molar properties of the various constituents as given by the expression given belo: (Xp, p= Xiny + Xan +o... + Xin; 2. It defines the increase of property X by the addition of 1 mole of the constituent ina mu at constant T and P to such large quantity of the mixture that the composition almost remains consatt change BS hecomositonX changes wit he change in composition, the patil mola quan ige with change in composition. Clearly, the partial molar quantities are not the same * ad _ te various constituents in the pure state X; .; is generally called the pera of the constituent i and it is the rat mixture concentation of the component, fon nanB® OF te foal property X al 4.X; is intensi ive property. ,ws OF VARIABLE COMPOSITION nical Potential (Partial Molar Free Energy) know that the thermodynamic properties, vi yD » viz., U, ecg of sate of the system which involves these prontiis/s ott G ae extensive properties. j ture and pressure only. Moreover, in the deri ‘operties is considered to be due to change ie that a system under consideration is a closed system. It may be ions A em containing two or More components, there can be ct lay be noted that in case of an open astoens as well. Clearly, an extensive property such as Gi 7 a pressure but of the number of moles of various Saupe th ea Consider a system at temperature, T and pressure, P. Let m,n ie e a > Np, \e Tespective ‘of moles of its components 1, 2, 3..... j..Cleat junction of temperature, pressure and the number of mole aie ear a Paar G= f(T Pym, mp, 13... n) Hae nytnptt + 15 = Total number of moles = N (say) For a small change in temperature, pressure and the change in fee energy, dG, will be given by the te of moles of the components, the aG aG « = {8} ars {h 41S aT aT * an PLN T.N 8 ng aj aG aG +{2\ dny + {=| dn; TP, m,n... nj my TP, mM. a ‘The quantity {22} ITP, my... nj iscalled partial molal free energy, Gj. It is also called chemical potential (u,) of the component i. Clearly; = u; = {st 9M}, P mm... nj Physical Significance of Chemical Potential. The chemical potential of a given substance is the change in free energy of the system that results on the addition of 1 mole of that particular substance to such a large quantity of the system (at constant temperature and pressure) that there is no appreciable change in the overall composition of the system. Thus, the equation for the change in free energy of the system is written as dG = {| aT+ {2 AP + peydny + Madny +... -fejNj. A) Ter Pion Nee 1, Hy sun and yt; are the chemical potentials of the components 1, 2 su. and j respectively. If temperature and pressure remain constant, then the expression becomes (dG)p, p= My day + My dy + oom + Mi ty the sytem has definite composition having my My =~ 1 oles ofthe components 1 2, Bex "ectively, then on integrating the above expression, we get Gr, p= my Hat Ma Hat M3 Ms tom GM / From this relation, we say that chemical potential is the contribution of each particular component of Ttixue to the total free energy of the system under conditions of constant temPeralire ‘and pressure. te— i MODERN COLLEGE CHEMIstTRy (c, . F 268 naan BCs. GIBB'S DUHEM EQUAT: My ing an, extensive thermodynamic property, can be o ‘The free energy G being ar, ex a OMplete 5 : ables T, P and composition. Thus the free energy G yon tely gy by fixing the state variables T, po 8G may tere — Ga fT Ph omy ng ws 4 are the number of moles of the various Constituents of the eae ne ray G may be represented by equation (ii) when the variables sligl in values, 6 a wG = %) ar) w{%) dn, FT en C0, a (2) an +(2) , 912 Jp, myn th nj PTnimy, ti Using equation (i), equation (iii) may be rewritten as Pe -(2) a+(Z) AP + py dy + feydng + 2... My dy PLN. 'T, N system, a” ly cites wate ; oT oP For an infinitesimal change in a closed system, equation (iv) reduces to aG (2) =|— aT +|— aP a a ie oP) 0) But dG is also given as dG =-$ dT + VdP rm) [- G=H-TS =U+PV-1y dG = dU + PdV + VdP - TdS - SdT But 64, = dU+ dw, (First Law) Aa) and Ste st Grey = TdS and OW,., = PdV o TdS = dU + Pdv | Putting this in equation (a) we get dG = dU + PdV + VdP- dU - PdV -~SdT a dG = -SdT + VaP From equations (v) and (vi), it is clear that (2) =-Sand (2 =V lvl) oT Je, a) i Putting these values in equation (iv), we get dG =~ SdT + VAP + py drys iy dy +. + 4; dn; At constant temperature and Pressure equation (viii) becomes (a) Gp, p= ey dey + pe dy oe 4 My; dn, Al vi)oe J grants OF VARIABLE COMPOSITIEH | k For a system of definite compositio, " ; Nn rey s ‘A 0 f . Present heeled [poe inezation of equation (in, SA by mole numbers n aot Or, P= MM tomy egy Wm is G is obtained | A general differentiation of equation (x) ate Gr, P= 1 d+ das ns a aa. : Bt | 2 diy + n, ‘A comparison of equations (éx) and (xi) yields ite : is Foe Mj dy + ny dp, (ei followin often exe. il md ty t+ yd ty tng my diy = ig oe at constant T and P, uation (tii) is called Gibb’ Se PRL i cane and b's Duhem equation and is applic aD temperature and pressure, applicable to a system at constant For a binary solution, ie., for a system of two components, it red it reduces to md uyt+ mad uy=0or du =-2 gy m2 Axi) It is obvious from equation (xiii) that the chemical i “ tential ofthe other component. With the increase of chemical ota of oe Smipooet aft the value cpemical potential of the other component, i.e., > decreases, Pee ae VARIATION OF CHEMICAL POTENTIAL WITH TEMPERATURE AND PRESSURE In case of closed systems in which there is no change in the number of moles of different constituents, ie., no change in composition ie. dn; =0, diz = 0 and so on. a dG = (2) aT + (3) AP + pydny + Mydny +... +m dy A) oT pn PN aG reduces to dG = (2) a+(%) dP (2) oT /pN oP /rn i Also for a closed system, dG = VdP - Sal 7 Thus, equating the coefficients of dT and dP in equation (2) and ( ) s ==(5) le ev (=) pie a0) ah Een i be written as : % ition (1) can In view of the relations (4) and (5), i general, equatio in D Hid dG =-SdT + VaP+ © ed to derive the : be uss described below = th temperature af ical expressions for the variation of chemi Equations (4) and (5) can Potential with temperature and pressure Vatiation of chemical potential wit sa) Hi = Gi =| an Jp, pamCHEMISTRY (cn “Gs, 270 tential of any constituent i Of a system wi . a y stem with tempeh The variation of chemical pot obtained by differentiating the above equation with respect to temperature and equation, ¢ | iy ke with respect to. nj. Thus, 7, MN a ial --(5] Lan. Gg (iL .8 2 =-3; an; TOT Jpn ONG EL N, my, my. i “0 where S; is known as partial molal entropy cof the component i. Since the entropy of a substance is always positive, hence according to equation chemical potential would decrease with increase temperature. ), ty tial with pressure. Variation of chemical potential ofan Variation of chemical potent 0 m «with pressure can be derived by differentiating the following equations: aG S| 7 a = (B),.7 i DPN... Mj P, with respect to pressure and 1; respectively. Thus, (“) = #6 -(=) =v @ Jp OPO] OM Ip nym. su] where Vj; is known as partial molal volume of the component i. eons CHEMICAL POTENTIAL OF IDEAL MIXTURES Change of Thermodynamic functions on mixing of ideal gases. For a system of id gases let my np -» be the number of moles of each constituent present in a mixture, so tht (m + m+... + mj) = n= total number of moles of gases. According to ideal gas eqation : nT RT PV = nT or V === (my + ma + where P is the total pressure of the gaseous mixture, = Differentiating the above eqution with respect ton; at constant tempera (2) RT 0) 9% Ht Pomsm P Substituting the value of {, from equation (10) to equation (8) we get (#) eee Ald Pn P + nj) ture and presses"res OF VARIABLE COMPOSITION ! Fora constant composition of the gas at constant tem eit] 38 : the above equation can also be du, ,= RT i =p dP =RT d (in Py « ,, be the partial pressure of the constituent j . ‘ fl) aves @8 al ideal gas, therefore ‘Present in the mixture. Since each constituent i pV = nRT (13) \ ni ni; p= RT eM tea RT=7P (14) [ PV =nRT or =P] \ Ri Taking logs, In p; = In| ~~ | + In P Differentiating the above equation din pj =ain(™) same n o din pj=dinP (nj and n are constants and its differential is zero) Substituting in (12), we get du;=RT dn p; (16), On integrating the above eugation (16), Hj = RT In pj + ue? P AD) Where 44;° P is the constant of integration, the value of which depends upon the nature of the gas and also on temperature. (15) Itis clear from equation (17) that the chemical potential of any constituent i in a mixture of ideal , #86 is determined by the partial pressure p; in the mixtre. IF p, is unity, then In pj = O and 4; = wi? (P) Thus, 14;° (P) is the chemical potential of the gaseous constituent i when its partial pressure is unity at constant temperature. n, Also Pi =77 RT (18) 7 pi=c; RT (19) ete c; is the molar concentration, i.e. the number of moles per unit volume of the constituent 7 in j mixture, Substituting the value of p; from equation (19) in equation (17), we get uj = we? (P) + RT In (GRD) = HP @) + RT ln oj + In RT] fj = ue (P) + RT In RT + RT In G Mi (©) = we (+ RT In Gi SE 4° (c) = 4? P + RT In RT. It is a constant depending upon the nat ™perature, If 7 (21) ure of the gas and c; = 1, then y; (c) = Mi? (©) ti n/N. 14° (c) is the chemical potential of the constituen is unity, upon i when its molar concentration in™~ MODERN COLLEGE CHEMISTRy (¢, B. -B.C.s SEY ‘= mole fraction of the constituent iin the mixture, we may write the dy, uation (tg oP Da in equation (21), we get 9 Substituting the value of pi ny sue +RTIn (x P)=H? P+ RT InP +RTInx; Constant up = ay (a) + RT In 3 mical potential of the cons ‘of the gas and the temperature. jal molar volume of methanol in a 1. The density of the solution is 0.91 em. Calculate the partial on at Mola, where 14;° (x) is the che tituent i when its mole fraction is one, j depends upon the nature * Ths Value EXAMPLE 1. The parti %petnanal = 0:39 is 39.2 em? mol” volume of water in the solution. SOLUTION. Here we have 0.39 mol of meth of these substances is one mol. Mol. mass of CH30H = 32 Mol. mass of H20 = 18 Mass of the solution = m= mM, + mM2 = (0.39 mol X 32 g mol!) + (0.61 mol X 18 g mol") = 23.46 g m __ 23468 95.78 Thus, volume 6f the solution, v=—- Pp 091gem~ V) + nV2 or V2 = (Veo — 1Viing anol and 0.61 ml of water so that the total am unt From the expression : Vout = "1 Substituting the values, we have (25.78 cm3) - (0.39 mol) (39.2 cm? mol!V0.6 mol = [25.78 cm? - 15.19 em3/0.6 mol 49 cm°0.6 mol 48 mol! eee a ee ee