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U T = V T dU = PdV + TdS dU dS = P + T dV dV U S P = P + T = P + T VT V T TV dU = CV dT + T P dV = TdS PdV

What is H ? PT

Determination of CP -CV

H C P CV = CV TP ( PV ) U C P CV = + CV TP T P P V T V C P CV = C V + T P + P CV T P T V T P T P P V C P CV = T = T TV T P CP CV = VT

2

Temperature Dependence of the Gibbs Free Energy Gm

A B

dG m = Vm dP Sm dT Gm = Sm T P

solid

liquid Tm

gas Tb T

At point A the solid is in equilibrium with the liquid Gm(S)= Gm(L) At point B the liquid is in equilibrium with the vapor Gm(L)= Gm(V)

Gm Hm Gm = Sm = T T P Gm Gm H m = T T T P Gm H m 1 Gm 2 = 2 T T P T T Gm T H m = T T2 P G T H = 2 T T P

dG m = Vm dP Gm = Vm ( P)dP

Pi Pf

Pf G m = RT ln Pi

At low P, Vm is independent of P

Gm = Vm Pf Pi

G m = Vm ( P )dP

Pi

Pf

Phase Diagram: P = f(V,T) Coexistence Curves Triple Point Critical Point Location of Phase Boundaries:

Gm = Vm P T

if Vm(L) > Vm (S) then Tm increases with Pressure (general) if Vm (L) < Vm (S) then Tm decreases with increasing pressure (water, etc..)

Two phases and are in equilibrium at temperature T and pressure P, if Gm (P,T) = Gm (P,T) Let us change P by dP and find out what is the corresponding dT required to preserve the equilibrium between the two phases. Changes of T by dT and P by dP lead to a change of G by dG d Gm = -Sm dT + Vm dP for the phase and d Gm = -Sm dT + Vm dP for the phase To preserve equilibrium conditions, Gm + d Gm = Gm + d Gm which implies d Gm = -Sm dT + Vm dP = d Gm = -Sm dT + Vm dP (Sm -Sm ) dT = (Vm - Vm ) dP

dP S H = = dT V TV

H fus (T*, P *) T dP H fus (T,P ) = P = P* + ln V fus (T*, P *) T * dT TVfus ( T, P)

if Hfus and Vfus can be assumed independent of T and P Liquid - Vapor Equilibrium

dP H vap ( T, P ) H vap (T, P ) H vap (T, P ) = = TRT dT TVvap (T, P) TVvap (T, P) P dP H vap (T , P) dT = R P T2 1 P H vap 1 ln = P * T T * R

dP H sub (T, P) H sub (T, P) H sub ( T, P) = = TRT dT TVsub ( T, P ) TVsub (T, P) P dP H sub ( T, P) dT = P R T2 P H sub = ln P * R 1 1 T T *

if Hsub can be assumed independent of T and P Close to the triple point Hsub = Hfus + Hvap Because H is a State Function

X XJ = Partial molar value of extensive property X n J n ,P,T is an Intensive property of a component in a mixture I

G = J = n J n ,P,T I

+ RT ln a ( J J

Standard State (P = 1 bar) Ideal Binary A-B Liquid Solution: Raoults Law PA = xA PA* where aA = xA = nA / (nA + nB) mole fraction of A Gmix = (nA+nB)RT(xA ln(xA) + xB ln(xB)) Hmix = 0 Vmix = 0 Smix = - (nA+nB) R (xA ln(xA) + xB ln(xB))

Phase Diagrams

Gibbs Rule of Phase: The number of independent intensive state variables necessary to fully define the state of a system is called the variance of the system(or the # of degrees of freedom) and is given by F = C - P + 2 where C = # of independent constituents (# of species if no reaction) P = # of phases 2 accounts for T and P F = 0 the system is invariant (triple point) F = 1 the system is monovariant (L/S, L/V, S/V coexistence) F = 2 the system is bivariant (single phase & single component) F = 3 the system is trivariant (single phase & 2 components)

Chemical Equilibrium

Consider the reaction 2A + 3B C + 2D If we define the extent of reaction by , when the reaction advances by d , the amount of reactants changes by: dnA = -2 d dnB = -3 d In general, for a reaction written as dnC = d J J = 0, then dnJ = J d dnD = 2 d At constant temperature and pressure: dG = A dnA + B dnB + C dnC + D dnD dG = (- 2A - 3B + C + 2D ) d In general dG = J dnJ = (J J) d

G RG = P,T

G = J = n J n ,P,T I

J

+ RT ln(a J )

where aJ is PJ/P or fJ/P for gases and unity for pure liquid and pure solids. RG = RG +RT lnQ

a1 a 2

D Q= C 2 a 3 aA B

In general, RG = J J

J and Q = a J J

At equilibrium, RG = 0

K = aJJ J eq

a1 a 2 K = C D a3 a2 B A eq

In general,

RT ln K = - RG and K can be calculated at a given temperature from the free energies of formation for each of the reactants and products

R G = J f G ( J )

J

Standard Gibbs Free Energy of Formation of 1 mole of Substance J at temperature T and 1 bar found in thermodynamic tables.

Pressure Dependence: K depends on G(T) and T and NOT on pressure. Temperature Dependence:

G T H = T T2 P G R T R H = T T2 P

R H = J f H ( J)

J

RH ln K = T P RT 2

If the standard reaction enthalpy can be calculated at T* (generally at 298K) and if the molar heat capacity of reactants and products is known as a function of temperature, an expression for the temperature dependence of the reaction enthalpy can be obtained. Then the equilibrium constant can be calculated at any temperature (T1) in terms of the equilibrium constant at T* (the latter being calculated from the standard free energy of formation of products and reactants).

1 T1 R H (T ) dT d ln K = 2 R T* T K (T*) R H (T ) = R H

J K ( T1)

(T *) + R CP (T )dT

T*

R C P (T ) = J Cp,m ( J, T )

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