大连理工大学：《工程热力学》课程教学资源（PPT课件）7 溶液热力学和相平衡基础 Solution Thermodynamics & Phase Equilibrium

According to property featuredz = Mdx + NdydU =TdS- pdVamandH = TdS+Vdpax01dA=-SdT- pdVaTapdG =-SdT +VdpOyasaTOvasapMaxwellrelationsasapaTOvasOvaTop

According to property feature d d d x y s v s p T v T p z M x N y M N y x T p v s T v p s s p v T s v p T = +        =                   = −              =                  =               = −       Maxwell relations d d d d d d d d d d d d U T S p V H T S V p A S T p V G S T V p = − = + = − − = − +

7.2.1 Closed System1 Molehomogenous fluid with constant compositiondUm = TdSm- pdVMolarPropertymdH.. = TdS. +V.dp1.AppliedtoReversibleormmnon-reversibleprocessdAm =-pdVm- SmdT2.No mass exchange betweensystemand surroundingsdGm =V.dp-SmdT

7.2.1 Closed System d d d d d d d d d d d d m m m m m m m m m m m m U T S p V H T S V p A p V S T G V p S T = − = + = − − = − Molar Property 1. Applied to Reversible or non-reversible process; 2. No mass exchange between system and surroundings. 1 Mole homogenous fluid with constant composition

...also could be applied to .i. Constant compositioni.Singleliquidphaseorgasphaseili.No chemical reactioniv.Closed mixture systemdU = TdS- pdV =U =U(S,V)auaudVdUdsasavauaudsd-pasavMolar number of componentis unchanged

.also could be applied to . i. Constant composition ii. Single liquid phase or gas phase iii. No chemical reaction iv. Closed mixture system d d d ( , ) U T S p V U U S V = −  = , , d ( ) d ( ) d V n S n U U U S V S V   = +   , , ( ) d , ( ) d V n S n U U S T V p S V   = = −   Molar number of component is unchanged

Opensystem,singlephaseU =U(S,V,nj,n2auauOUdudVdndss.V,nasavon;n, - Molar number keeps constant except NO. i componentauuOnChemicalPotentialdU = TdS- pdV +μ,dn;

Open system , single phase ( , , , ,., ) U U S V n n n = 1 2 i , , , , d ( ) d ( ) d ( ) d V n S n S V n i j i i U U U U S V n S V n    = + +     j n − Molar number keeps constant except NO. i component , , ( ) j i S V n i U n     Chemical Potential i d d d d i i U T S p V n = − +

aHauunan,S.V,nS,p,naAaGan;anT.p,ndU = TdS - pdV + Zμudn,dH = TdS +Vdp + Zudn,dA = -SdT - pdV+ ZμdnidG = -SdT +Vdp+ Zudn,i

, , , , j j i i i S V n S p n U H n n        = =           j T p nj i V T n ni G n A , , , ,           =           = i i i i d d d d d d d d d d d d d d d d i i i i i i i i U T S p V n H T S V p n A S T p V n G S T V p n     = − + = + + = − − + = − + +    