1

Fundamental equations for homogeneous

closed system consisting of 1 mole:

dU TdS PdV (4.1)

dH TdS VdP (4.2)

dA SdT PdV (4.3)

dG VdP SdT (4.4)

Fundamental equations for homogeneous
closed system consisting of n moles:

d nU T d nS P d nV (4.5)

d nH T d nS nV dP (4.6)

d nA nS dT P d nV (4.7)

d nG nS dT nV dP (4.8)
For a single-phase fluid in a closed system
wherein no chemical reactions occur, the
composition is necessarily constant, and
therefore:

nG
P nV (4.9)
T ,n

nG
T nS (4.10)
P ,n
For a closed homogeneous system, G is a
function only of T and P:

G = g(T, P) (4.11)

In an open system:

nG = g(P, T, n1, n2, ....., nm) (4.12)

where m is the number of components.

The total differential of eq. (4.12) is

nG nG
d nG dP dT
P T ,n T
P ,n

nG
dni (4.13)
i ni P ,T ,n
j i

Chemical potential is defined as:

nG
i
ni P ,T ,n j i
(4.14)
For a three-component system:
nG nG
d nG dn1 dn2
n1 P ,T ,n2 ,n3 n2 P ,T ,n1 ,n3
nG
dn3
n3 P ,T ,n1 ,n2

nG
d nG dni
i ni
P ,T ,n j i

d nG 1 dn1 2dn2 3 dn3

d nG i dni
i
We may rewrite eq. (4.13) as

d nG nV dP nS dT i dni (4.15)
i

For a system comprising of 1 mole:

dG V dP S dT i dxi (4.16)
i

Eqs. (4.15) and (4.16) are the fundamen-

tal equations for an open system corres-
ponding to eq. (4.4) for a closed system.
According to eq. (4.16)

G = g(T, P, x1, x2, ....., xm-1)

and

G
S (4.17)
T P , x

G
V (4.18)
P T , x
Using similar derivations, we can get the
following relations:

d nU T d nS P d nV i dni (4.19)
i

d nH T d nS nV dP i dni (4.20)
i

d nA nS dT P d nV i dni (4.21)
i
It follows that:

nU nH
i
ni S ,V ,n
j
ni S ,P ,n j

(4.22)
nA nG

ni T ,V ,n
j
ni T ,P ,n j
 Gas
1 (open system)
closed
system
2 Liquid
(open system)
For a closed system undergoing a rever-
sible process, the criterion for equilibrium
is defined in:

d nU T d nS P d nV 0 (4.23)

Within this closed system, each phase is an

open system which is free to transfer mass
to each other.
Eq. (4.23) may be written for each phase:

1 1 1
d nU T 1
d nS P 1
d nV i1dni1
i

(4.24)

2 2 2
d nU T 2
d nS P 2
d nV i2 dni2
i

(4.25)
Total change of internal energy is :
1 2
d nU d nU d nU 0

1 1
T 1
d nS P 1
d nV i dni 1 1
i
2 2
T 2
d nS P 2
d nV i dni 2 2
0
i

d nU T
d nS P
d nV


i dni 0 (4.26)
i
The individual variation d(nS)(1), d(nS)(2),
etc. are subject to the constraints of
constant total entropy, constant total
volume, and constant total moles of each
species:
1 2
d nS d nS d nS 0 (4.27)

1 2
d nV d nV d nV 0 (4.28)

1 2 (4.29)
i
dn dni dni 0

Equations (4.27 4.29) can be written as

1 2 (4.30)
d nS d nS

1 2
d nV d nV (4.31)

1 2
dni dni (4.32)

dn11 dn12

dn21 dn22

dn31 dn32
Eq. (4.26) for a two-phase 3-component
system gives:

1 2
d nU T 1
d nS T 2
d nS (4.33)

1 2
P 1
d nV P 2
d nV

11dn11 21dn21 31dn31

2 2 2 2 2 2
1 dn1 2 dn2 3 dn3
Substituting eqs. (4.30 4.32) into eq.
(4.33)

2 2
d nU T 1
d nS T 2
d nS

2 2
P 1
d nV P 2
d nV

11dn12 21dn22 31dn32

12 dn12 22 dn22 32 dn32 0


d nU T 2
T 1
dnS 2
P 2
P 1
dnV
2

12 11 dn12 22 21 dn22

32 31 dn32 0 (4.34)
 All variations d(nS)(2), d(nV)(2), dn1(2),
dn2(2), etc., are truly independent.

Therefore, at equilibrium in the closed

system where d(nU) = 0, it follows that

nU
2 0 T 2 T 1
nS

nU
2 0 P 2 P 1
nV
 nU 12 11
2 0
n1

nU
2 0
22 21
n2

nU
2 0
32 31
n3
Thus, at equilibrium
1 2
T T T (4.35)
1 2
P P P (4.36)

1 2
i i i (i = 1, 2, ., N)
(4.37)
11 12 1 (4.38)

1 2
N N N (4.39)
Partial molar property is defined as

nM
Mi (4.40)
ni T ,P ,n j

Ui , Hi , Si , Gi , Ai , Vi ,

Partial molar property is a response

function.
Thus for thermodynamic property M:
nM f T , P, n1, n2 , , ni , (4.41)

The total differential of nM is

nM nM
d nM dP dT
P T ,n T
P ,n

nM (4.42)
dni
i ni P ,T ,n
j i
Because the first two partial derivatives on
the right are evaluated at constant n and
because the partial derivative of the last
term is given by Eq. (4.40), this equation
has the simpler form:

M M
d nM n dP n dT Mi dni
P T , x T P , x i

(4.43)
 ni = xi n dni xi dn n dxi

d nM n dM M dn

Equation (4.43) becomes:

M M
n dM M dn n dP n dT
P T , x T P , x
Mi xi dn n dxi
i
The terms containing n are collected and
separated from those containing dn to
yield:

M M
dM P dP T dT Mi dxi n
T , x P ,x i
M xi Mi dn 0
i
(4.44)
In application, one is free to choose a
system of any size (n), and to choose any
variation in its size (dn).

Thus n and dn are independent and

arbitrary.

The only way that the left side of this

equation can be zero is for each term in
brackets to be zero.
Therefore:

M M
dM dP dT Mi dxi 0
P T , x T P , x i

(4.45)

M xi Mi
i (4.46)

Eq. (4.46) is an important relations

(summability relation) for partial molar
properties.
Since Eq. (4.46) is a general expression for
M, differentiation yields a general
expression for dM:

dM d xi Mi xi dMi Mi dxi
i i i

(4.47)
Combining eqs. (4.45) and (4.47) yields
Gibbs-Duhem equation :

M M (4.48)
dP dT xi dMi 0
P T , x T P , x i

For the important special case of changes

at constant T and P, it simplifies to:

xi dMi 0 (4.49)
i
Eq. (4.46) for a binary solution:

M x1M1 x2M2 (A)

whence

dM x1dM1 M1dx1 x2dM2 M2dx2 (B)

When M is known as a function of x1 at
constant T and P, the appropriate form of
the Gibbs-Duhem equation is Eq. (4.49),
expressed here as:

x dM 0
i i
i

x1 dM1 x2 dM2 0 (C)

Since x1+ x2 = 1 dx2 = dx1.

Eq. (B) becomes:

dM x1dM1 M1dx1 x2dM2 M2dx1

dM x1dM1 x2dM2 M1dx1 M2dx1

dM M1dx1 M2dx1 M1 M2 dx1

dM
M1 M2
dx1

dM (D)
M2 M1
dx1
Substituting Eq. (D) to Eq. (A):

dM
M x1M1 x2 M1
dx1 dM
M2 M1
dx1
dM
M x1 x2 M1 x2
dx1
dM
M M1 x2
dx1

dM
M1 M x2 (4.50)
dx1
 dM
dM M1 M 1 x1
M1 M x2 dx1
dx1
M f x1 a0 a1 x1 a2 x12

Hitung M1 pada x1 = 0,3

Mx1 0,3 a0 a1 0,3 a2 0,3

2

dM
a1 2a2 x1
dx1

dM
a1 2a2 0,3
dx1 x 0,3
1
 dM k
M1 M 1 x1 M x2 Mk
dx1 x2

M k
h
M0,3

dM h
h
dx1 x 0,3 1
1

0,0 0,3 1,0 dM k

x1
dx1 x 0,3 x2
1
 dM
M x1M1 x2 M1
dx1

M x1M1 x2M2 (A)

dM (D)
M2 M1
dx1
Elimination of M1 Eq. (A) yields:
Pers. (4.50)
M x1M1 x2M2
dM
M x1 M2 x2M2
dx1

dM
M x1 x2 M2 x1
dx1
dM
M M2 x1
dx1
dM
M2 M x1 (4.51)
dx1
 dM
M2 M x1
dx1
M f x1 a0 a1 x1 a2 x12

Hitung M2 pada x1 = 0,3

Mx1 0,3 a0 a1 0,3 a2 0,3

2

dM
a1 2a2 x1
dx1

dM
a1 2a2 0,3
dx1 x 0,3
1
 dM m
M2 M x1 M x1 Mm
dx1 x1

M0,3
m
dM m

dx1 x 0,3 x1
1

0,0 0,3 1,0

x1
 M1 x 0,3
1

M0,3
m
M2 x 0,3
1

0,0 0,3 1,0

x1
 M1 x 0 1

x1 0 M1

M
M1

M2

0,0 0,3 1,0

x1
M f x1 a0 a1 x1 a2 x12 Mx 0 a0
1

dM dM
a1 2a2 x1 a1
dx1 dx1 x 0
1

dM
M1 M 1 x1
dx1

M 1

M1 x 0 a0 a1
1
 x2 0

M2 x 0
2

M1
M 2

M2

0,0 0,3 1,0

x1
Example 4.1

Describe a graphical interpretation of

eqs. (4.50) and(4.51).
Solution

I1 I2

1
Tangent line at x1:
at x1 = 1 intercept = I1
at x1 = 0 intercept = I2

From the figure :

dM M I2 dM
I2 M x1
dx1 x1 dx1

dM dM
I1 I2 I1 M 1 x1
dx1 dx1
dM
I1 M x2
dx1
 dM
M1 M x2
dx1
(4.50)
I1 M1
dM
I1 M x2
dx1

dM
M2 M x1
dx1
(4.51) I2 M2
dM
I2 M x1
dx1
The tangent intercepts give directly the
values of two partial properties.

at x1 = 0

M2 M2 M1 M1

at x1 = 1 and

M1 M1 M2 M2
4.2
SOLUTION 4.2

Molar volume of the solution is

V x1V1 x2V2 M xi Mi
i

0.338.632 0.717.765 (4.46)

= 24.025 cm3 mol-1

Since the required volume is Vt = 2000 cm3,

the total number of moles required is:
t 3
V 2000 cm
n 3 1
83.246 mol
V 24.025 cm mol
Of this, 30% is methanol and 70% is
water,
n1 = 24.794 mol
n2 = 58.272 mol

The volume of each species is:

V1t n1V1 1017 cm3

V2t n2V2 1053 cm3

LATIHAN

Density molar dari campuran biner

dapat dinyatakan dengan persamaan:

a0 a1 x1 a2 x12

Turunkan persamaan untuk V1 dan V2

V1 V2

PENYELESAIAN

a0 a1 x1 a2 x2
1

V a0 a1 x1 a2 x
2 1
1

dV
a0 a1 x1 a2 x1 a1 2a2 x1
2 2

dx1

dV
V 2 a1 2a2 x1
dx1
 dM dV
M1 M x2 V1 V x2
dx1 dx1

V1 V x2V a1 2a2 x1
2

V 1

V1 x 0 V V a1
1
2

dM dV
M2 M x1 V2 V x1
dx1 dx1
V2 V x1V a1 2a2 x1
2

V 2

V2 x 2 0
V V a1 2a2
2
 Every equation that provides a linear
relation among thermodynamic properties
of a constant-composition solution has as
its counterpart an equation connecting
the corresponding partial properties of
each species in the solution
Consider the equation for enthalpy:

H U PV

For n moles

nH nU P nV

Differentiation with respect to ni at constant

T, P, and nj yields:

nH nU nV
n P
i P ,T ,n j ni P ,T ,n j ni P ,T ,n j
 nH nU nV
n P
i P ,T ,n j ni P ,T ,n j ni P ,T ,n j

Hi Ui PVi H U PV (4.52)

For other properties:

Ai Ui TSi (4.53)

Gi Hi TSi (4.54)
(Kelas B, 20-9-2016)
Eq. (4.15) may be written:

d nG nV dP nS dT Gi dni (4.55)
i

nG
T nS
P ,n

nG nS
T n

in P ,n T ,P ,n i T ,P ,n j
j
 nG nS
T n

in P ,n T ,P ,n i T ,P ,n j
j

nG
Si
T ni T ,P ,n j P ,n

Gi Gi (4.56)
Si
T P ,n T P , x
d nG nV dP nS dT Gi dni
i

nG
P nV
T ,n

nG nV
P n
ni T ,n T ,P ,n
j
i T ,P ,n j

nG
Vi
P ni T ,P ,n j T ,n

Gi Gi
Vi (4.57)
P T ,n P T , x
In a constant-composition solution, G is a
i
function of P and T, and therefore:

Gi Gi
dGi dP dT
P T , x T P , x

and:

dGi Vi dP Si dT (4.58)

dG S dT V dP
We can therefore write simply by analogy
many equations that relate partial
properties.

dUi TdSi PdVi (4.59)

dHi TdSi Vi dP (4.60)

dAi Si dT PdVi (4.61)

 nRT ni RT
P t pi
V Vt

pi ni RT V t ni
t
yi
P nRT V n

pi y i P

(i = 1, 2, . . . , n)
Partial molar volume of ideal gas:

ig nV ig nRT P
Vi
ni T ,P ,n j ni T ,P ,n j

RT ni RT

P n n
j
P

ig ig
Vi V (4.62)
 GIBBS THEOREM

A partial molar property (other than

volume) of 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

Mi T , P M T , pi
ig ig
ig
i
ig
for Mi Vi

(4.63)
ENTHALPY

Enthalpy of an ideal gas is independent of P

Hi T , P H T , pi H T , P
ig
i
ig
i
ig

Hiig Hiig (4.64)

Application of summability relation:

H ig y i Hiig (4.65)
i
ENTROPY
Equation for entropy:

dT V
dS CP dP
T T P
For ideal gas:
ig
ig dT Vi
dSiig CPi dP
T T P

ig dT
ig dP
dS i C PiR (4.66)
T P
 For a constant T process

ig dP
dS i R (constant T)
P
Siig T ,P
ig
P
dP (constant T)
dS i R
Siig T , pi pi P

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

Siig T , pi Siig T , P R ln y i (4.67)

According to eq. (3.60):

Siig T , P Siig T , pi

Eq. (4.67)

Siig T , P Siig T , P R ln y i

Siig Siig R ln y i (4.68)

By the summability relation, eq. (4.46):

S ig y i Siig y i Siig R ln y i
i i

or: S ig y i Siig R y i ln y i
i i

This equation is rearranged as

S ig y i Siig R y i ln y i
i i

ig ig 1 (4.69)
S yi S i R y i ln
i i yi
 ig ig 1
S yi S i R y i ln
i i yi

the left side is the entropy change of mixing

for ideal gases.
Since 1/yi >1, this quantity is always
positive, in agreement with the second law.
The mixing process is inherently irrever-
sible, and for ideal gases mixing at constant
T and P is not accompanied by heat
transfer.
GIBBS ENERGY

Gibbs energy for an ideal gas mixture:

G ig H ig TS ig

Partial Gibbs energy :

Gi ig Hiig TSiig
In combination with eqs. (4.64) and (4.68)
this becomes

Gi ig Hiig TSiig RT ln y i Giig RT ln y i

or:

iig Gi ig Giig RT ln y i (4.70)

An alternative expression for the chemical
potential can be derived from fundamental
eq. (4.8) for ideal gas:

ig ig ig
dG i S i dT Vi dP (4.8)

At constant temperature:

dP
dG i
ig
Vi ig
dP RT (constant T)
P
Integration gives:

Gi
ig
i T RT ln P (4.71)

Combining eqs. (4.70) and (4.71) results in:

ig
i i T RT lny i P (4.72)
Gibbs energy for pure ideal gas:
(4.73)
G i
ig
i T RT ln P

Analogous equation for pure real gas defines

the fugacity (fi) of pure species:

Gi i T RT ln fi (4.74)
Chemical potential of a component in ideal
gas mixture:

iig i T RT lny i P (4.72)

The analogous eq. for species i in a mixture

of real gases or in a solution of liquids is:

i Gi i T RT ln fi (4.75)

where fi is the fugacity of species i in

solution, replacing the partial pressure yi P.
This definition of fi does not make it a
partial molar property, and it is therefore
identified by a circumflex rather than by
an overbar.
Eq. (4.32) is the fundamental criterion for
phase equilibrium.

i1 i2 i (i = 1, 2, ., N)

Since all phases in equilibrium are at the

same temperature, an alternative and
equally general criterion follows
immediately from Eq. (4.75):

fi 1 fi 2 fi (i = 1, 2, ., N)

(4.76)
 Thus, multiple phases at the same T and
P are in equilibrium when the fugacity of
each constituent species is the same in all
phases.
The definition of a residual property is:

R ig
M MM

Multiplied by n mol of mixture, it becomes

R ig
nM nM nM
Differentiation with respect to ni at constant
T, P, and nj gives:

nM R nM nM ig
n
i T ,P ,n j ni T ,P ,n j ni T ,P ,n j

M R M M ig (4.77)

For Gibbs energy:

G R G G ig (4.78)
 Gi i i T RT ln fi

Gi ig iig i T RT lny i P
()
fi
Gi Gi ig
i ig
i RT ln

y P
i

Gi RT ln i
R
(4.79)

where: fi
i
yi P (4.80)
For an ideal gas:

Gi R 0 iig 1

ig
fi y i P (4.81)

Thus the fugacity of species i in an ideal -

gas mixture is equal to its partial pressure.
Alternative form of nG is nG/RT which can
be differentiate as

nG 1 nG
d d nG 2
dT
RT RT RT

d(nG) is replaced by Eq. (4.15) and G is

replaced by its definition, H TS:

nG nV nH Gi
d dP 2
dT dni
RT RT RT i RT

(4.82)
For the special case of an ideal gas:

nG ig nV ig nH ig
Gi ig
d dP 2
dT dni
RT RT RT i RT

subtracting this equation from Eq. (4.82):

nG R nV R nH R Gi R
d dP 2
dT dni
RT RT RT i RT

(4.83)
fundamental residual-property relation
An alternative form of Eq. (4.83) follows by
introduction of the fugacity coefficient as
given by Eq. (4.79)

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

(4.84)

Equations (4.83) and (4.84) are so general

that they are useful for practical application
only in their restricted forms.
 V R G R RT (4.85)

RT T P ,x

HR G R RT
T (4.86)
RT P T , x

nG R RT
ln i (4.87)
n i P ,T ,n j i

This equation demonstrates thatln i is a

partial property with respect to GR
Fugacity coefficient from virial eos

The relation of residual Gibbs energy and eos:

GR P dP
Z 1 (const. T) (4.88)
RT 0 P

For a mixture composed of n moles:

nG R P dP
nZ n (const. T) (4.89)
RT 0 P
Differentiation gives:

nG R RT P
nZ n dP

n i T ,P ,n j 0 ni T ,P ,n j P

P nZ n dP
lni
0 ni T ,P ,n n P
j
i T , P , n j

P
dP
ln i Zi 1 (4.90)
0 P

nZ (4.91)
where Zi
ni T ,P ,n j
For 2-term virial eos

BP
Z 1
RT

nBP
nZ n
RT

nZ P nB
Zi 1 n
ni T ,P ,n j RT i T ,P ,n j

(4.92)
Introducing eq. (4.92) into eq. (4.90) yields:
P nB dP
ln i 1 1
0 ni T ,P ,nj P

1 P
nB

ln i n dP
RT 0 i T ,P ,n j

As B is usually a function of T, the above

equation can be integrated as:

P nB
ln i (4.93)
RT ni T ,n j
The second virial coefficient for a mixture
B y i y j Bij
i j

For a binary mixture:

B y12B11 y22B22 2y1y2B12

n1 2 n2
2
n1n2
nB n B11 B22 2 2 B12
n n n
1 2
nB n1 B11 n22B22 2n1n2B12
n
 nB 1 2
n 2 n1 B11 n2 B22 2n1n2B12
2

1 T ,n
2
n
1
2n1B11 2n2B12
n
nB
n y1 B11 y2 B22 2y1y2B12
2 2

1 T ,n
2

2y1B11 2y2B12

nB n

n B 2 y j Bij
i T ,n j j 1 (4.94)
Fugacity coefficient from cubic eos

Eq. (4.71) i Gi i T RT ln fi

Differentiation at constant T gives

dGi RT d ln fi (4.95)

Eq. (4.55) dGi Vi dP Si dT

At constant T

dGi Vi dP (4.96)
Combining eqs. (4.95) and (4.96):

RT d ln fi Vi dP

nV
RT d ln fi dP
ni
dP is eliminated using chain rule:

nV ni P
n P nV 1
i

nV P
n dP n nV
i i
 P
RT d ln fi d nV
ni
Adding RT dln (V/RT) to both sides of the eq.:

V
RT d ln fi RT d ln
RT
P V
d nV RT d ln
ni RT

fiV P V
RT d ln
d nV RT d ln
RT ni RT
 fiV P 1 V
RT d ln
d nV RT d ln
RT ni V RT RT

fiV P
RT d ln
d nV
RT ni
1 1
RT d nV
nV RT RT

fiV P 1
RT d ln
d nV RT d nV
RT ni nV
 fiV P RT
RT d ln
d nV
RT ni nV

fiV fi
Considering that lim ln limln ln y i
V RT P 0 P

We get

fiV V P RT
ln fi
RT d ln
d nV
ln y i RT ni nV
 fiV P RT
RT ln ln y i d nV
RT V ni nV

fiV
P RT
RT ln RT ln yi d nV
RT V ni nV

V
RT ln fi RT ln RT ln y i
RT

P RT
n nV d nV
V i
 RT ln fi RT ln y i

P RT V
n nV d nV RT ln RT
V i
fi
P RT V
RT ln d nV RT ln
y i V ni nV RT

Subtracting RT ln P from both sides:

fi P RT PV
RT ln
d nV RT ln
yi P V ni nV RT

P RT
RT ln i d nV RT ln Z
V ni nV

(4.97)
Fugacity coefficient from van der Waals eos:

2 y j aij
bi V bm
lni ln Z
j

V bm V RTV
(4.98)
Fugacity coefficient from RK and SRK eos:

bi bm
lni Z 1 lnZ 1
bm V

2 y j a ij

a m bi
j
ln1
bm

bmRT bm a m V

(4.99)
 Fugacity coefficient from PR eos:

bi bm
lni Z 1 lnZ 1
bm V

2 y j a ij

a m bi
j V 2,414bm
ln
4,828bmRT bm a m V 0,414bm

(4.100)