The basic relation connecting the Gibbs energy to the temperature

and pressure in any closed system:

(nG) (nG) dT (nV)dP (nS)dT

d(nG) dP
P T,n T P,n

applied to a single-phase fluid in a closed system wherein no

chemical
h i l reactions
ti occur. Chemical potential

Consider a single-phase, open system:

(nG) (nG) (nG)

d(nG)
P T,n

dP
T P,n
dT i
n
i P,T,n j
dn i
Define the chemical potential:

(nG)
i
n i P,T,n j

The fundamental property relation for single-phase fluid systems of constant or

variable composition:

d(nG) (nV)dP (nS)dT i dn i

i

When n = 1, G
V
P T,x
dG VdP SdT i dx
d i
i

G
S
T P,x

Consider
C id a closed
l d systemt consisting
i ti
of two phases in equilibrium:

d(nG) (nV) dP (nS) dT dn

i

i
i

d(nG) (nV) dP (nS) dT i dn i

i

nM (nM) (nM)

d(nG) (nV)dP (nS)dT i dn i i dn i

i i
d(nG) (nV)dP (nS)dT i dn i i dn i
i i

The two phase system is closed thus:
d(nG) (nV)dP (nS)dT

i dn i i dn i 0
i i

dn i dn i

(i i ) dn i 0 i i
i

Multiple
M lti l phases
h att the
th same T andd P are ini equilibrium
ilib i when
h
chemical potential of each species is the same in all phases.
Define the partial molar property of species i:
(nM)
Mi
n i P,T,n j
The chemical potential and the particle molar Gibbs energy are
identical:
i G i

For thermodynamic property M:

nM M(P, T, n1 , n 2 ,..., n i ,...)

M M
d(nM) n dP n dT M i dn i
P T,n T P,n i
 M M dT M dn
d(nM ) n dP n i i
P T ,n T P ,n i

d nM n dM M dn d n i x i dn n dx i

M M dT M (x dn ndx )
ndM M dn n dP n i i i
P T ,n T P ,n i

M dP M dT M dx n M x M dn 0
dM
P



T


i i i i
Tn
T,n P,n
Pn i i

M M
dM dP dT M i dxi 0
P T , n T P ,n i

Summability
y nM ni M i 0 M xi M i 0
relations i i

Calculation of mixture properties from partial properties

 M M dT M dx 0
dM dP i i
P T,n
T T P,n
P i

dM x i dM i M i dx i
i i

M dP M dT x dM 0 The Gibbs/Duhem equation

P T,n

T P,n
i i
i

This equation must be satisfied for all changes in P, T and the M i caused by
changes of state in a homogeneous phase.
phase

For the important special case of changes at constant T

and P
P:
x i dMi 0
i
 For binaryy systems
y M x1M 1 x2 M 2
Const. P and T, using Gibbs/Duhem equation

dM x1dM 1 M 1dx1 x2 dM 2 M 2 dx2

dM M 1dx
d 1 M 2 dx
d 2 dM
M1 M 2
dx1
x1 x2 1

M x1M1 dM
M2 M 1 M x2
dM
(A) M 2 M x1 (B)
x2 d1
dx dx1
The three kinds of properties used in solution
thermodynamics
Solution pproperties
p M, for example
p G,S,
, , H,, U

Partial properties, M i , for example G i , Si , Hi , Ui

Pure-species properties Mi, for example G i ,,Si , Hi , Ui

EXAMPLE
Describe a graphical interpretation of equations (A) and (B)

dM M I2

d x1 x1

dM I1 I2
I1 I2
d x1 1 0
dM
I2 M x1
d x1

dM

I1 M 1 x1 dx 1

I1 M1 I2 M 2
The need arises in a laboratory for 2000 cm3 of an antifreeze solution consisting of 30
mol-% methanol in water. What volumes of pure methanol and of pure water at 25C
must be mixed to form the 2000 cm3 of antifreeze at 25
25C?
C? The partial and pure molar
volumes are given.

Methanol : V1 38.632 cm3 mol-1 V1 40.727 cm3 mol-1

Water : V2 17.765 cm3 mol-1 V2 18.068 cm3 mol-1

V x1V1 x2V2 V (0.3)(38.632) (0.7)(17.765) 24.025 cm 3 / mol

n1 (0.3)(83.246) 24.974 mol

Vt
2000
n 83.246 mol
V 24.025 n2 (0.7)(83.246) 58.272 mol

V1t n1V1 (24.974)(40.727 ) 1017 cm 3

V2t n2V2 (58.272)(18.068) 1053 cm 3

The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is:
H 400 x1 600 x2 x1 x2 ( 40 x1 20 x2 )
Determine expressions for H1 and H 2 as functions of x1, numerical values for the
pure-species enthalpies H1 and H2, and numerical values for the partial enthalpies at
infinite dilution H1 and H 2

H 400 x1 600 x2 x1 x2 ( 40 x1 20 x2 )
x 2 1 x1

H 600 180 x1 20 x13 H 1 420 60 x12 40 x13 H 2 600 40 x13

dH
H 1 H x2
dx1

x1 0 x1 1

J J
H 1 420 H 2 640
mol mol
 d ( nG ) ( nV ) dP ( nS ) dT Gi dni
i

G i
T P ,n

(nS)
n i
P,T,n

G i
P T ,n

(nV)
n i P,T,n
j
j

Gi

T
S i
P ,x

G i
P T ,x
Vi

dGi Vi dP S i dT
 H U PV

nH n U P (nV)

(nH) (n U) (n V)
P
n ni P,, T,, n ni P,, T,, n
i P,, T,, n
j j j

Hi Ui P Vi

For every equation providing a linear relation among the

thermodynamic


properties

of a constant
constant-composition



composition




solution there exists a corresponding
. equation
connecting
the corresponding
p g ppartial pproperties
p of each species
p in the
solution.
 nRT pi ni
P yi
Vt P n

n i RT
pi pi yi P i 1, 2,... , N
Vt
 Gibbss theorem
A partial molar property (other than volume) of a constituent
) (
species
in
an ideal-gas mixture
is
equal
to
the corresponding

molar property of
. the species as
a pure ideal
gas at
the mixture
temperature but at a pressure equal to its partial pressure in the
mixture.
M (T , P ) M (T , pi )
i
ig
i
ig
M i
ig
Vi ig

ig (nRT P) RT n
ig (nV ) RT
V
i ni
ni
P ni
n P
T, P, n T, P, n j j
j
ig ig
V V
i i
Since the enthalpy of an ideal gas is independent of pressure:

(T P) H igi (T
H igi (T, (T, p i ) H igi (T
(T, P) H ig yi H iig
i

M y M i i

H ig H ig yi H igi 0
i

i
M M y i M i
i
Enthalpy change of mixing
Property change of mixing

Similarly U igg y i U igig

i

U ig U ig y i U iig 0
i
Internal energy change of mixing
 The entropy of an ideal gas does depend on pressure
dT dP dSigi Rd ln P (T const.)
dS C
ig
R ig
P
T P

P P
S (T, P) S (T, pi ) R ln R ln
ig
i
ig
i R ln y i
pi yi P

M igi (T, P) M iig (T, pi )

Siig (T, P) Siig (T, P) R ln yi

Sig y iSigi R y i ln yi
i i

Sig Sig y iSiig R y i ln yi

i i
G igi H igi TSiig

H (T, P) H (T, P)
ig
i
ig
i
G igi H igi TSiig RT ln y i

(T P) Siig (T,
Siig (T, (T P) R ln yi

igi G iig G iig RT ln y i

ig ig RT
dG V dP dP RT d ln P (const. T)
i i P

G igi i (T) RT ln P igi i (T) RT ln y i P

G ig y i i (T) RT y i ln y i P
i i
Chemical potential:

provides
id fundamental
f d t l criterion
it i forf phase
h equilibria
ilib i

however
however, the Gibbs energy,
energy hence i, is defined in relation to
the internal energy and entropy - (absolute values are
unknown).
 G i ((T)) RT ln P
ig
i

Fugacity: a quantity that takes the place of i

G i i (T) RT ln
l fi

With units of pressure

G i i (T) RT ln f i
fi
G i G RT ln
ig
i
P
G igi i (T) RT ln P
fi
i
P
Fugacity coefficient
G iR RT ln i
G iR
ln i
RT
ig
For ideal gases G iR 0 i 1

P dP
l i 0 (Zi 1)
ln (const.
( t T)
P
When the compressibility factor is given by two terms virial equation
Bii P
Zi 1
RT P

Bii
ln i dP
0
RT
P dP
ln i 0 (Zi 1) (const. T)
P

Bii P
ln i
RT
 v v
Saturated vapor: G i i (T) RT ln fi

Saturated liquid: G il i (T) RT ln fil

fiv
G iv G il G iv G il RT ln
fil

fiv
RT ln 0
fil
fiv fil fisat
iv =il =sat
i

For a p
pure species
p coexistingg liquid
q and vapor
p phases
p are in equilibrium
q
when they have the same temperature, pressure, fugacity and fugacity
coefficient.
The fugacity of pure species i as a compressed liquid:
G i i (T) RT ln fi
fi
Gi G sat
i RT ln sat
fi
G sat
i i (T) RT ln fi
sat

P
dG = V dP S dT Gi G sat
Vi dP (const. T)
Psat
i
i

Since Vi is a weak function of P P

f 1
ln sati Vi dP
fi RT Psat
i

f i Vil (P-Pisat ) f isat =sat P sat

l sat
ln sat =
i i
V (P
(P-P
Pi )
fi RT f i =sat
i Pi
sat
exp i

RT
For H2O at a temperature of 300C and for pressures up to 10,000 kPa (100 bar)
calculate values of fi and i from data in the steam tables and plot them vs. P.

For a state at P: Gi i (T ) RT ln f i
For a low pressure reference state: Gi* i (T ) RT ln f i *

Gi H i TS i
fi 1 H i H i* * fi 1
ln * ( Si Si ) ln *
(Gi Gi
*
)
fi R T fi RT
f i * P * 1 kPa

The low pressure (say 1 kPa) at 300C: H i* 3076.8 J

g
S i* 10.3450 J
gK

fi18.015 H i 3076.8
ln (Si 10.345)
10 345)
1 8.314 573.15
For different values of P up to the saturated pressure at 300C, one obtains the
values of fi ,and hence i . Note, values of fi and i at 8592.7 kPa are obtained

P = 4000 kPa Hi = 2962 J/g

T = 300 C
C Si = 6.3642
6 3642 J/gK

fi 18.015 2962 3076.8

ln (6.3642 10.345)
1 8.314 573.15

f i 3611 kPa

i 3611/ 4000 0.9028

T = 300 C Psat = 8592.7 kPa

Hi = 2751 J/g
Si = 5.7081 J/gK
Vi = 1.403 cm3/g

fisat 18 015 2751 3076

18.015 3076.88
ln (5.7081 10.345)
1 8.314 573.15

fisat 6738.9
6738 9 kPa

sat
i
6738.9 / 8592.7 0.7843
Values of fi and i at higher pressure

Vil (P Pisat )
fi sat
i
Pi
sat
exp
RT

Vil (1.403)(18.015) 25.28 cm3 / mol

25.28(P 8592.7)
f i 6738.9 exp
8314 573.15

P = 10000 kPa

25.28(10000 8592.7)
f i 6738.9exp 6789.4 kPa
8314 573.15

i 6789.4 / 10000 0.6789

Fugacity and fugacity coefficient: species in
solution
For species i in an ideal gas mixture:

ig
i
i (T) RT ln yi P

For species i in a mixture of real gases or in a solution of liquids:

i i (T) RT ln fi

Fugacity of species i in
solution (replacing the partial
pressure)
Multiple phases at the same T and P are in equilibrium when the fugacity of each
constituent species is the same in all phases:

fi fi ... fi
The residual property: M R M M ig

The partial residual property: M iR M i M ig

i

G iR G i G ig
i

i G i i (T) RT ln fi
fi
G i G ig
i
RT ln
ig G ig
i ((T)) RT ln yi P yi P
i i
f
i i
yi P
The fugacity coefficient of
species i in solution

G iR RT ln i
For ideal gas G iR 0
fiig
iig 1
yi P
G iR RT ln i

fiig yi P
 Fundamental residual-property
relation
nG 1 nG
d d(nG) 2
dT
RT RT RT

G H TS d(nG) (nV)dP (nS)dT dn

i
i i

nG nV nH Gi
d
RT RT
dP
RT 2
dT
i RT
dni nG
RT
f ( P, T , ni )

G/RT as a function of its canonical variables allows evaluation of all other

thermodynamic properties, and implicitly contains complete property information.
GiR
RT dn
Gi
RT dn
nG nV nH nG R nV R nH R
d dP 2
dT i d dP dT
RT RT RT RT RT RT 2 i
i i

G ig
G ig nV
Vig Hig
RT
nG nH
ln dn
d dP dT i
dn i nG R nV R nH R
RT RT RT 2
or d dP 2
dT i i
i RT RT RT i
 ln dn
nG R nV R nH R
d dP 2
dT i i
RT RT RT i

V R (G R / RT)

RT P T,x
Tx

HR (G R / RT)
T
RT T P,x

(nG R / RT)
ln i
n i P,T,n j
 Develop a general equation for calculation of ln i values form compressibility-
factor data.

(nG R
RT)
ln i
n i P,T,n j P
((nZ n))

ddP
l i
ln
nG R P dP 0 n i P,T,n P
( nZ n) j
RT 0 P (nZ)
Zi
n i
n
1
n i

P d Integration at constant
dP
ln i ( Z i 1)
0 P temperature and composition
Generalized correlations for the fugacity coefficient
Pr dPr
l i ( Z i 1)
ln (const . Tr )
0 Pr
Z Z 0
Z 1

Pr dPr Pr
1 dPr
l
ln ( Z 1)
0
Z (const . Tr )
0 Pr 0 Pr
Pr dPr
ln ( Z 1)
0 0
0 Pr
1 dPr
Pr
ln Z
1
0 Pr
ln ln ln
0 1
For p
pure ggas
1
( )
0
Table E13-E16
Estimate a value for the fugacity of 1-butene vapor at 200C and 70 bar.

Tr 1.127 Table E15 and E16 0.627

0

Pr 1.731 1 1.096
0.191

1
( )
0

0.638

f P (0.638)(70) 44.7 bar

Generalized correlations for the fugacity coefficient
Pr BPc
Z 1
Tr RTc Pr 0
Z 1 (B( B1 )
Tr
BPc
B0 B1
RTc Pr dPr
ln i (Z 1) (const. Tr )
0 Pr
0.422
Pr 0 B 0.083 1.6
0

ln= (B +B )
1 Tr
Tr 0.172
B1 0.139
Tr4.2
For pure gas
Fugacity coefficient from the virial E.O.S
The virial equation
BP
Z 1
RT

The mixture second virial coefficient B

B yi y j Bij
i j

For a binary mixture

B y1 y1 B11 y1 y 2 B12 y 2 y1 B21 y 2 y 2 B22

Fugacity coefficient from the virial E.O.S

nBP
Z n
nZ
RT

( nZ ) P ( nB )
Z1 1
n1 P ,T , n2 RT n1 T , n2

1 P ( nB ) P ( nB )
l 1
ln
RT 0
n
dP
1 T , n2
d
RT

n

1 T , n2
 B y1 y1B11 y1 y 2 B12 y 2 y1B21 y 2 y 2 B22

B y1 (1 y 2 )B11 y1 y 2 B12 y 2 y1B21 y 2 (1 y1 )B22

B y1B11 y 2 B22 y1 y 2 (2B12 B11 B22 )

12 2B12 B11 B22

B y1B11 y 2 B22 y1 y 2 12
n1 n2 n1 n 2
B B11 B22 12
yi ni / n n n n n

n 1n 2
nB n1B11 n 2 B22 12
n

((nB)) n 2 n n 1n 2
B11 12
n1 T,n 2
2
n
 (nB) n 2 n n 1n 2
B11 ( 2 2 )12
n1 T,n, 2 n n

(nB) n 2 n1 n 2
B11 ( )12
n1 T,n 2 n n n
(nB) (nB)
B11 (y 2 y1 y 2 )12 B11 y 2 (1 y1 )12
n1 T,n 2 n1 T,n 2

((nB))
B11 y 2 12
2

n1 T,n 2 P
P (nB)

ln1 =
RT
B11 +y 2 12
2

ln 1
RT n1 T,n
2

P
Similarly:

ln 2
RT
B22 y1 12
2
For multi-component systems

P 1

ln k Bkk yi y j (2ik ij )
RT 2 i j

Where: ik 2Bik Bii Bkk

 RTcij 0 1 i + j
B ij = (B +
ij B ) ij =
Pcij 2

Tcij = (Tci Tcj )(1-k ij )

E i i l interaction
Empirical i t ti parameter
t
ZcijRTcij Zcci +Zcj
Pcij = Zcij =
Vcij 2

3
V +V
1/3
ci
1/3
cj

Vcij =
2

Determine the fugacity coefficients for nitrogen and methane in N2(1)/CH4(2) mixture
at 200K and 30 bar if the mixture contains 40 mol-% N2.

3
12 2 B12 B11 B22 2( 59.8) 35.2 105.0 20.6 cm mol

ln 1
P
RT

B11 y2212
30
(83.14)( 200)

35.2 (0.6) 2 ( 20.6) 0.0501

1 0.9511

l 2
ln
P
RT

B22 y1 12
2
30
(83.14)( 200)

105.0 (0.4) 2 (20.6) 0.1835

2 0.8324
Estimate 1 and 2 for an equimolar mixture of methyl ethyl ketone (1) /
toluene (2) at 50C and 25 kPa. Set all kij = 0.

i j Z ci Z cj Z cij RTcij V V
1/ 3 1/ 3 3
ij Z cij Pcij Vcij
ci cj

2 2 Vcij 2

RTcij Tcij (TciTcj ) (1 kij ) 12 2 B12 B11 B22
Bij ( B 0 ij B1 )
Pcij

ln 1
P
RT

B11 y2212 0.0128 1 0.987

ln 2
P
RT

B22 y1212 0.0172 2 0.983
 The ideal solution
Serves as a standard to be compared:
M id xi M iid
Gi Gi RT ln xi
id
i
G id xi Gi RT xi ln xi
i i

cf Gi Gi RT ln yi
ig ig
cf.
Gi id G id
xi S i R xi ln xi
S id
i R ln xi S id
S i R ln xi S
T T
i i
P,
P x P i i

Gi id G xiVi
i
id
Vi id
Vi id
Vi V
P T , x P T i

H id
Gi TS
id id
Gi RT ln xi TS i RT ln xi H id
Hi H id
xi H i
i i i
i
 The Lewis/Randall Rule
For a special case of species i in an ideal solution:
i i (T ) RT ln fi iid Gi id i (T ) RT ln fi id

Gi id Gi RT ln xi
Gi i (T ) RT ln f i

The Lewis/Randall rule fi id xi f i

iid i
The fugacity coefficient of species i in an ideal solution is
equal to the fugacity coefficient of pure species i in the same
physical state as the solution and at the same T and P.
 Excess properties
The mathematical formalism of excess properties
is analogous to that of the residual properties:
M E M M id
where M represents the molar (or unit-mass) value of
any extensive
i thermodynamic
h d i property (e.g.,
( V, U, H, S,
G, etc.)
Similarly,
Similarly we have:
nG E nV E nH E Gi
E
d dP 2
dT dni
RT RT RT i RT

The fundamental excess-property relation

The excess Gibbs energy and the
activity coefficient
The excess Gibbs energy is of particular interest:
G E G G id
Gi i (T ) RT ln fi
Gi id i (T ) RT ln xi f i

fi
Gi RT ln
E

xi f i
fi The activity coefficient of species i in solution.
i A factor introduced into Raoults law to
xi f i
account for liquid-phase
q p non-idealities.
Gi E RT ln i For ideal solution, G E 0, 1
i i

c.f. Gi R RT ln i
 nG E nV E nH E Gi
E
d dP 2
dT dni
RT RT RT i RT

nG E nV E nH E
d dP 2
dT ln i dni
RT RT RT i

V E (G E / RT )

RT P T , x
Experimental accessible values:
H E
(G / RT )
E
T activity coefficients from VLE data,
RT T P,
P x VE and HE values come from mixing experiments
experiments.
( nG E / RT )
ln i
ni P ,T ,n j

GE
xi ln i
RT i Important application in phase-equilibrium
x d ln
i
i i 0 (const . T , P ) thermod namics
thermodynamics.