Generalized Correlations for the Fugacity Coefficient

r dP dP ln( ) = ( Z 0 1) r + Z 1 r Pr Pr 0 0

Extension to Mixtures

Pr

i , j =
B 0 = 0.083 0.422 Tr1.6 B1 = 0.139 0.172 Tr 4.2

i + j
2
2

ln( ) = ln( 0 ) + ln( 1 )

Tci ,cj = (TciTcj ) (1 kij ) kij usually equals 0

1 2

Z cij RTcij Pcij = Vcij

Z + Z cj Zcij = ci 2
ln(1 ) =

Vcij

3 3 V 1 +V 1 cj = ci 2

= ( 0 ) ln( 1 )

= exp

Pr 0 ( B + B1 ) Tr
id

V sat = Vc Z c (1Tr )7 f = P
Lewis Randall Rule

Bij = B 0 + ij B1

BP Bij ij cij RTcij

12 = 2 B12 B11 B22

P ( B11 + y2212 ) RT

ln(2 ) =

P ( B22 + y1212 ) RT

Ideal Solution Model

G = xi Gi + RT xi ln( xi )
id i i

S = xi Si R xi ln( xi )
i i

id

= xiVi
i

H = xi H i
id i

i i (T ) + RT ln( fi )

G i i (T ) + RT ln( f i )

i i (T ) + RT ln

fi fi

i id Gi id = Gi (T ) + RT ln
GE = xi ln ( i ) RT i

f i id fi

f i id = xi f i i id = i

Excess Properties M M M
E id

G G G
E

id

H H H
E

id

S SS
E

id

G H T S
E E

M E = M R xi M R
i

M iE = M i M i id

The Excess Gibbs Energy and the Activity Coefficient f f i i Gi Gi id = RT ln i Gi E = RT ln ( i ) Gi = Gi + RT ln ( i xi ) x f xi f i i i i ig = G ig i + RT ln ( yi ) i id = Gi + RT ln ( xi ) i = Gi + RT ln ( i xi ) Excess Gibbs Energy

x d ln ( ) = 0 Gibbs / Duhem
i i i

Liquid-Phase Properties From VLE Data

f iv = yii v P

f li = yii l P

f v = f l = yi P lim
xi 0

f1 = y1 P f 2 = y2 P fi dfi = Hi dx xi i x =0 i

fi id = xi fi fi = xi H i

f fi i i = id xi fi fi

GE = x1 ln ( 1 ) + x2 ln ( 2 ) RT

x1

d ln 1 d ln 2 + x2 = 0 ( Const. T,P ) dx1 dx1

dx1

( ) = ln
GE RT

d GE RT lim x1 0 dx 1

( ) = lim ln

x1 0

= ln 1

i =

yi P yP = i ( i = 1, 2,..., N ) xi fi xi Pi sat

Margules Equation ln( 1 ) = A12 ( x1 = 0)

sat sat sat

ln( 2 ) = A21 ( x2 = 0)
sat

y1 P = x1 1 P sat 1

y2 P = x2 2
2

x1 1 P 1 P2 P = x1 1 P + x2 2 P2 y1 = 1 x1 1 P sat + x2 2 P2 sat 1 Property Changes of Mixing G E = G xi Gi RT xi ln( x1 ) SE = S xi Si + RT xi ln( x1 )

GE GE lim lim = ln 1 = ln 2 x1 0 x x RT x1 1 x x RT 1 2 1 2 Models for The Excess Gibbs Energy GE Two Suffix Margules: = Ax1 x2 ln( 1 ) = Ax2 2 ln( 2 ) = Ax12 RT Three Suffix Margules: ln( 1 ) = x2 2 A12 + 2 x1 ( A21 A12 ) ln( 2 ) = x12 A21 + 2 x2 ( A12 A21 )
Partial Molar Properties

V E = V xiVi
i

H E = H xi H i
i

M 1 = M + x2

dM dx1

M 2 = M x1

dM dx1

Heat Effects of Mixing Processes

Equilibrium and Stability

H = H x1 H i
i

H = x1 H1 + x2 H 2 + H x1 = 1 % 1+ n

% n=

x2 ( n1 + n2 ) 1 x1 = x1 ( n1 + n2 ) x1

% H Heats of Solution H = x1
i

S MIX = R yi ln( yi )

SUNMIX = R yi ln( yi )
i

( dG t )

T ,P

=0

S = S MIX + SUNMIX

& Q & & SG = mS T f i = f i = f i xi i = xi i ln 2 2

d 2 GE 1 RT > 2 dx1 x1 x2 T ,P

( )

d ln ( 1 ) df d i 1 > i > 0 & > 0 (Const T & P) x1 T ,P dx1 dx1 dx1

Liquid/Liquid Equilibrium f = f i xi i fi = xi i f i i

i = i ( x1 , T )
2

i = i ( x1 , T )
2

x ln 1 = ln 1 1 x1 A ( x1 ) ( x1 )
2 2

A (1 x1 ) (1 x1 )

= ln x1 x1

1 x1 ) = ln ( (1 x1 )

(1 x ) = (1 x ) (1 x ) = ln (1 x )

1 2 1

Vapor/Liquid/Liquid Equilibrium (VLLE)

x1 1 P sat = y1 P 1 y =

x1 1 P sat = y1 P 1

x2 2 P2 sat = y2 P

x2 2 P2 sat = y2 P

P = x1 1 P sat + x2 2 P2 sat 1

x1 = 1 x1

x1 1 P sat 1 Metastable: Of, relating to, or being an unstable and transient but relatively long-lived state of a P chemical or physical system, as of a supersaturated solution or an excited atom.

1 x1 a A (1 2 x1 ) = ln A = + b c ln(T ) T x1 Colligative Properties RT 2 RT 2 (T TBoil ) = Boil x (T TMelt ) = Melt x H Evap H Fusion

J H Fusion, Evap = & x= [ mole fraction ] mol

J R= mol K

& T = [K ]

This equation is known as the Lewis/Randall Rule, applies to each species in an ideal solution at all conditions of temperature, pressure, and composition. It shows that the fugacity of each species in an ideal solution is proportional to its mole fraction; the proportionality constant is the fugacity of pure species I in the same physical state as the solution and at the same T & P. 2 E Where A12 & A21 are the values of the intercepts at x1=0 and x1=1 of the straight line drawn to represent the G /x1x2RT data points.