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Use of Maxwell Relations:

What is the Internal Pressure ?


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

dH = VdP + TdS dS dH =V + T dP dP H S V = V + T = V T PT P T TP H = V (1 T ) P T dH = VdP + TdS = C P dT + V(1 T )dP

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

Properties of the Gibbs Free Energy


Temperature Dependence of the Gibbs Free Energy Gm

A B

Constant Pressure Single Component System


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

solid

liquid Tm

gas Tb T

Sm (S) < Sm (L) << Sm (V)

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)

Gibbs-Helmoltz Equation: Useful in Applications to Chemical Equilibria

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

Pressure Dependence of the Gibbs Free Energy at cst T:


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

ideal gas Vm = RT/P

Pf G m = RT ln Pi

At low P, Vm is independent of P

liquids, solids at low P

liquids, solids at high P At high P, Need E.O.S. Vm =f(P,T)

Gm = Vm Pf Pi

G m = Vm ( P )dP
Pi

Pf

Phase Diagram of Single Component Materials


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

Clapeyron Equation (describes the coexistence curve)

Note at equilibrium, G = H - T S = 0 for the transition

Solid - Liquid Equilibrium


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

if Hvap can be assumed independent of T and P.

Solid - Vapor Equilibrium:


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

Properties of Simple Mixtures


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

Chemical Potential: Partial molar Free Energy: J Activity: aJ


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

Define the Reaction Free Energy as:

G RG = P,T

Define the Chemical Potential of Each Species by:


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

(Q is called the reaction quotient)

For the example above RG = - 2A - 3B + C + 2D and


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.

Response of Chemical Equilibria to Conditions


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

where RH is given by:


R H = J f H ( J)
J

RH ln K = T P RT 2

Note that the enthalpic term will also depend on T !!!

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 )