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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
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
P ( B11 + y2212 ) RT
ln(2 ) =
P ( B22 + y1212 ) RT
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
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
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
ln( 2 ) = A21 ( x2 = 0)
sat
y1 P = x1 1 P sat 1
y2 P = x2 2
2
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
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
d 2 GE 1 RT > 2 dx1 x1 x2 T ,P
( )
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
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.
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.