Physical Chemistry Chapter 10 Nonideal Solutions
1 Chapter 10 Nonideal Solutions Physical Chemistry
Physical Chemistry Solutions Ideal solutions B at T,Cat T,B-B, C-C △U=0 P P △V=0 mLx △H=0 B+C B-B. C-C △S>0 mux atT. P B-C △G<0 If B-B. C-C and B-C interactions are all different
2 Ideal Solutions Solutions B at T, P C at T, P B + C at T, P B-B, C-C B-B, C-C, B-C Physical Chemistry If B-B, C-C and B-C interactions are all different mixU = 0 mixV = 0 mixH = 0 mixS 0 mixG 0
Physical Chemistry Solutions Nonideal solutions If B-B, C-C and B-C interactions are all different B at T.C at T △U≠0 IB-B C-C △≠0 △mH≠0 The molecules of one B+C B-BC-C, type cluster together atT. p B-C △S≈0 Reorganization of the molecules: orderly mixture Separation is spontaneous △G>0 mIX Liquids become immiscible or partially miscible
3 Nonideal Solutions Solutions B at T, P C at T, P B + C at T, P B-B, C-C B-B, C-C, B-C Physical Chemistry If B-B, C-C and B-C interactions are all different The molecules of one type cluster together Reorganization of the molecules: orderly mixture mixH 0 mixS 0 mixG 0 mixU 0 mixV 0 Separation is spontaneous Liquids become immiscible or partially miscible
Physical Chemistry Nonideal Solutions e The Wide Significance of Chemical Potential The chemicalpotential (u) does more than show how G varies with composition G=U+PV-TS U=-PV+S+G A general infinitesimal change in U for a system of variable composition can be written du=-Pdv-Vdp+ sdT+tds+dG Pdv-VerP+SaT+ TdS +(dP -SaT+u,dn ,+u,dn,+.) =-Pd+7aS+(m1+2dm2+…) At constant v and s thn+2oh2+…=∑
4 The chemical potential () does more than show how G varies with composition. The Wide Significance of Chemical Potential Nonideal Solutions G =U + PV −TS A general infinitesimal change in U for a system of variable composition can be written ( ) ( ) 1 1 2 2 1 1 2 2 = − + + + + + − + + + = − − + + = − − + + + PdV TdS dn dn VdP SdT dn dn PdV VdP SdT TdS dU PdV VdP SdT TdS dG At constant V and S = + + = i dU 1 dn1 2 dn2 i dni U = −PV +TS +G Physical Chemistry
Physical Chemistry Nonideal Solutions e The Wide Significance of Chemical Potential ence U S,V,n1(j≠i) In the same way, it is easy to deduce H aA 1 1 O I/SP ,T,n1(j≠i) H aA 1 S,V,n1(j≠i) S,P,n1(j≠i) V,T,n1(j≠i) G 7,P,n1(j≠)
5 The Wide Significance of Chemical Potential Nonideal Solutions hence S,V ,n ( j i) i i j n U = In the same way, it is easy to deduce , , ( ) , , ( ) , V T n j i i i S P n j i i i j j n A n H = = , , ( ) , , ( ) , , ( ) , , ( ) T P n j i i V T n j i i S P n j i i S V n j i i i j j j j n G n A n H n U = = = = Physical Chemistry