Chapter 3:

Solution Thermodynamics:
Theory
3.0 The Notations for Solution
Thermodynamics
M = the properties of the solution
(h, s, v)
Mi = partial properties (e.g., hi , si )

of species i in the solution

Mi = pure-species properties

(e.g., gi , si )

188

3.1 Fundamental Property Relations

We can re-write the following
relationship (Eq. 2.13)
dg = vdP sdT

(2.13)

for a system with a total number of

moles of n, as follows
d ( ng ) = ( nv ) dP ( ns ) dT

(3.1)

Since ng is f(P, T) (do you know

WHY?), we obtain the following
mathematical implication
( ng )
( ng )
d ( ng ) =
dP +
dT

P T ,n
T P ,n

189

(3.2)

By comparing Eq. 3.1 with Eq. 3.2,

we obtain the following relationships

and

( ng )
P = nv

T ,n

(3.3)

( ng )
T = ns

P ,n

(3.4)

where
n = total # of moles or # of moles
of all chemical species in the
solution
= n1 + n2 + n3 + ... + nn
(for n species)

Accordingly,
ng = f ( T , P, n1, n2 , n3 , .... )
190

Thus, we can re-write Eq. 3.2 as

follows
( ng )
( ng )
d ( ng ) =
dP +
dT

P T ,n
T P ,n
( ng )
dni
+

ni P ,T ,n
i =1
j
n

(3.5)

where nj is all species EXCEPT species i

( ng )
The term
is defined as

ni P,T ,nj

CHEMICAL POTENTIAL, i
( ng )
i =

P , T , nj
i

191

(3.6)

Combining Eqs. 3.2-3.6 together yields

n

d ( ng ) = ( nv ) dP ( ns ) dT + i dni (3.7)
i =1

In the case that n = 1 ni = xi , Eq. 3.7

can be re-written as follows
n

dg = vdP sdT + i dxi

(3.8)

i =1

From Eq. 3.8, it implies that

g = f ( T , P, x1, x2 , x3 , .... )

Accordingly, it can be implied

mathematically that

and

g
=v
P T ,x

(3.9)

g
= s
T P,x

(3.10)

192

This confirms that Gibbs free

energy still serves as a generating
function for other thermodynamic
properties, even in the system where
compositions of all species vary with
time

193

3.2 The Chemical Potential & Phase

Equilibria
Consider a closed system where
2 phases co-exist and are in equilibrium
with each other
We can write Eq. 3.7 for each phase
(phases & ), as follows
n

d ( ng ) = ( nv ) dP ( ns ) dT + i dni

(3.11)

i =1
n

d ( ng ) = ( nv ) dP ( ns ) dT + i dni

i =1

194

(3.12)

A total property of the system are

obtained when the property of each
phase is combined together, as
shown in the following equation
nM = ( nM) + ( nM)

(3.13)

where M = any system property

Hence, by combining Eq. 3.11 with
Eq. 3.12, we obtain
n

d ( ng ) = ( nv ) dP ( ns ) dT + i dni + i dni

i =1

i =1

(3.14)
From Eq. 3.1, we knew that
d ( ng ) = ( nv ) dP ( ns ) dT
195

(3.1)

Thus, Eq. 3.14 becomes

n

d ( ng ) = d ( ng ) + i dni + i dni

i =1

i =1

i =1

i =1

dn
+

dn
i i i i =0

(3.15)

Since this is a closed system, a

decrease in the number of moles of
Phase will result in an increase in
the same number of moles of Phase
, or vice versa, or it means that
dni = dni

(3.16)

Combining Eq. 3.15 with Eq. 3.16

yields
196

dn
+

dn
i i i ( i )=0

i =1

i =1

(
i =1

i )dni = 0

and, eventually
i = i

(3.17)

This principle can also be

extended to any phases, as follows
i = i = i = .... = i

Multiple phases at the same T &

P are in equilibrium with one
another when the chemical
potential of each species is the
same for all phases

197

3.3 Partial Properties

We can extend the principle of
chemical potential (Eq. 3.6) to any other
thermodynamic properties, as follows
( nM)
Mi =

P , T , nj
i

where

(3.18)

M = any system property

(e.g., h, s)

This is called PARTIAL PROPERTY or

RESPONSE FUNCTION, which represents
the change in the total property, nM, due
to the addition of a small (differential)
amount of (moles of) species i, at constant
T & P, to the solution
198

Combining Eqs. 3.6 & 3.18 together

results in
( ng )
i = gi =

P ,T ,n j
i

(3.19)

This implies that the chemical

potential is, in fact, partial Gibbs
free energy

199

3.3.1 Properties & Partial Properties

We can extend Eq. 3.5 to any other
thermodynamic properties (M) as
follows
( nM)
( nM)
d ( nM) =
dP
dT
+

P T ,n
T P ,n
( nM)
dni
+

ni P,T ,n
i =1
j

(3.20)

and when combining Eq. 3.20 with Eq.

3.18, we obtain
( nM)
( nM)
d ( nM) =
dP +
dT

P T ,n
T P ,n
n

+ Mdn
i
i
i =1

200

(3.21)

Since n = total # of moles of all species

in the solution, it must be constant; thus,
M
M
d ( nM) = n
dP
+
n

dT
P T ,n
T P ,n

(3.22)

+ Mdn
i
i
i =1

For a special case, when n = 1, we

obtain the following relationships
M
M
=

P
P

T ,n
T ,x
M
M

T
T

P ,n
P ,x

and

Thus, Eq. 3.22 can be re-written as

follows
M
M
d ( nM) = n
dP
+
n

dT
P T ,x
T P,x
n

+ Mdn
i
i
i =1

201

(3.23)

Mdn

Consider the term

i =1

in Eq. 3.23

ni
Since xi = ni = xi n
n

Thus,
dni = d ( xi n) = xi dn + ndxi

Accordingly,
n

Mdn = M ( x dn + ndx )
i =1

i =1

(3.24)

Consider the term d ( nM) in Eq. 3.23

d ( nM) = ndM + Mdn

(3.25)

Combining Eqs. 3.23-3.25 together

yields

202

 M
M
ndM + Mdn = n
dP + n
dT
P T ,x
T P ,x
n

+ Mi ( xi dn + ndxi )
i =1

Rearranging the above equation

yields

M
M
i
in
dM P dP T dT Mdx

T ,x

P ,x

+ M xi Mi dn = 0

(3.26)
Eq. 3.26 will be true only if

M
M
i
i = 0
dM P dP T dT Mdx

T ,x

P ,x

and
M xi Mi = 0
203

Hence,
M
M
dM =
dP
+

dT + Mdx
i
i

P
T

T ,x

P ,x

M = xi Mi

(3.27)
(3.28)

Note that Eq. 3.27 is a special case of

Eq. 3.23 when n = 1 and, thus, ni = xi
Multiplying Eq. 3.28 with n yields
nM = ( xi n) Mi
nM = ni Mi

(3.29)

Eq. 3.29 is called summability relations

Differentiating Eq. 3.28 gives

dM = xi dMi + Mdx
i
i
204

(3.30)

Combining Eq. 3.27 with Eq. 3.30 yields

x dM + Mdx
i

M
M
dP
+

dT + Mdx
i
i

T ,x

P ,x

Rearranging the above equation gives

M
M

dP +
dT xi dMi = 0
P T ,x
T P,x

(3.31)
Note that Eq. 3.31 is called a Gibbs/
Duhem equation
In the case where T & P are constant, a
Gibbs/Duhem equation (Eq. 3.31) becomes

x dM = 0
i

205

(3.32)

3.3.2 Partial Properties in Binary

Solutions
Consider a solution with 2 components
(in other words, a binary solution)

Writing Eq. 3.28,

M = xi Mi

(3.28)

for a binary solution yields

M = x1M1 + x2 M2

(3.33)

Differentiating Eq. 3.33 results in

dM = x1dM1 + Mdx
1
1 + x2 dM2 + M2 dx2

(3.34)

206

Writing the Gibbs/Duhem equation

for a system where T & P are constant
results in

x dM = 0
i

(3.32)

Eq. 3.32 can be written for a binary

solution, as follows
x1dM1 + x2 dM2 = 0

(3.35)

Combining Eq. 3.34 with Eq. 3.35

yields
dM = Mdx
1
1 + M2 dx2 + ( x1dM1 + x2 dM2 )
dM = Mdx
1
1 + M2 dx2

207

(3.36)

Since, for a binary solution, x1 + x2 = 1

x1 = 1 x2 ; hence, dx1 = dx2 or dx2 = dx1

Eq. 3.36 can then be re-written as

follows:
dM = Mdx
1
1 + M2 ( dx1 )
= Mdx
1
1 M2 dx1
= ( M1 M2 ) dx1
dM
= M1 M2
dx1

Rearranging the above equation

results in
dM
M1 = M2 +
dx1

208

(3.37)

Rearranging Eq. 3.33 gives

x2 M2 = M x1M1
M x1
M2 = M1
x2 x2

(3.38)

Substituting Eq. 3.38 into Eq. 3.37 and

rearranging the resulting equation yield
M x1 dM
M1 = M1 +
x2 x2 dx1
x
M dM
M1 + 1 M1 = +
x2
x2 dx1
x2 M1 + x1M1 M dM
= +
x2
x2 dx1

209

(3.39)

Multiplying Eq. 3.39 with x2 yields

dM
x2 M1 + x1M1 = M + x2
dx1

( x2 + x1 ) M1 = M + x2

dM
dx1

(3.40)

Since x1 + x2 = 1 (for a binary system),

Eq. 3.40 can be written as follows:
dM
M1 = M + x2
dx1

(3.41)

By performing the same derivation

for M2 , we obtain the following equation
dM
M2 = M x1
dx1

210

(3.42)

Eqs. 3.41 & 3.42 illustrate that any

partial property ( Mi ) can be calculated
from the property of the solution (M),
when the composition of each species
is known, which can be illustrated
graphically as follows

Lets consider a plot between M

(M can be either h, s, or v, or etc.
any system property) and x1 (Figure
3.1)

211

I1

M
I2

x1

Figure 3.1: A Plot between M (any

thermodynamic property) and x1

The slope of the line I1I2 can be

calculated as follows

and

dM M I2 M I2
=
=
dx1 x1 0
x1

(3.43)

dM I1 I2
=
= I1 I2
dx1 1 0

(3.44)

212

Rearranging Eq. 3.43 gives

dM
I2 = M x1
dx1

(3.45)

and rearranging Eq. 3.44 yields

dM
I1 =
+ I2
dx1

(3.46)

Combining Eq. 3.46 with Eq. 3.45

and rearranging result in
dM
dM
+ M x1
I1 =
dx1
dx1
dM
= (1 x1 )
+M
dx1

but x1 + x2 = 1 x2 = 1 x1

213

Hence,
dM
I1 = M + x2
dx1

(3.47)

Comparing Eq. 3.47 with Eq. 3.41

and Eq. 3.45 with Eq. 3.42 yields
I1 = M1 and I2 = M2

214

dM
Lets consider the value of
when
dx1

x1 0 (or it is called infinite dilution of

species 1) from Figure 3.2
M1
M

M1

M2

x1

Figure 3.2: A Plot between M (any

thermodynamic property) and x1
when x1 0

215

Comparing Figure 3.2 with Figure

3.1 gives
I1 = M1 = M1 and I2 = M2 = M2

This indicates that when x1 0 (i.e.

pure x2), M2 = M2
dM
Lets consider the value of
when
dx1

x1 1 or x2 0 (i.e. infinite dilution of

species 2), in Figure 3.3

216

M1

M2
M2

x1

Figure 3.3: A Plot between M (any

thermodynamic property) and x1
when x1 1 (or x2 0)

Comparing Figure 3.3 with Figure 3.1

yields
I1 = M1 = M1 and I2 = M2 = M2

meaning that when x1 1 (i.e. pure

species 1): M1 = M1
217

Example The enthalpy of a binary

liquid system of species 1 & 2 at
constant T & P is presented by the
following equation
h = 400 x1 + 600 x2 + x1x2 ( 40 x1 + 20 x2 )

(3.48)
Determine the values of h1, h2 , h1 , &
h2

218

Rearranging Eq. 3.48 to be a

function of x1 only (note that, for a
binary system, x2 = 1 x1) gives
h = 600 180 x1 20 x13

(3.49)

Differentiating Eq. 3.49 with respect

to x1 yields
dh
= 180 60 x12
dx1

(3.50)

Writing Eqs. 3.41 & 3.42

dM
M1 = M + x2
dx1

(3.41)

dM
dx1

(3.42)

M2 = M x1

for this case yields

219

dh
h1 = h + (1 x1 )
dx1

(3.51)

dh
h2 = h x1
dx1

(3.52)

Combining Eqs. 3.49 & 3.50 with

Eqs. 3.51 & 3.52 and rearranging give
h1 = 600 180 x1 20 x13

+ (1 x1 ) ( 180 60 x12 )

h1 = 420 60 x12 + 40 x13

(3.53)

h2 = 600 + 40 x13

(3.54)

220

From Figures 3.2 & 3.3, we knew

that, when x1 0:
M2 = M2 and M1 = M1

and when x1 1:
M1 = M1 and M2 = M2

Hence, by substituting corresponding

numerical values into Eqs. 3.53 & 3.54, we
obtain:
h1 = h1 ( x1 = 1) = 420 60 (1) + 40 (1) = 400
2

h2 = h2 ( x1 = 0 ) = 600 + 40 ( 0 ) = 600
3

h1 = h1 ( x1 = 0 ) = 420 60 ( 0 ) + 40 ( 0 ) = 420
2

h = h2(x1 = 1) = 600 + 40 (1) = 640

3

221

The values of h1, h2 , h1 , and h2 can

be shown graphically as follows

700

h2

600

h1

h2

500
400

h1
300
200
100
0
0

0.2

0.4

0.6

x1

222

0.8

3.3.3 Relations among Partial

Properties
Combining Eq. 3.7
d ( ng ) = ( nv ) dP ( ns ) dT + i dni (3.7)

with Eq. 3.19

( ng )
i = gi =

P ,T ,n j
i

(3.19)

results in
d ( ng ) = ( nv ) dP ( ns ) dT + gi dni (3.55)

From an exact differential expression,

we obtain the following relationships

223

 ( nv )
( ns )
T = P

P ,n

T ,n

and

v
s
=
T P,n
P T ,n

(3.56)

( ns )
gi
T = n

P ,n

i P ,T ,n j

(3.57)

( nv )
gi
P = n

T ,n
P ,T ,n j
i

(3.58)

By employing Eq. 3.18

( nM)
Mi =

P , T , nj
i

(3.18)

we can re-write Eqs. 3.57 & 3.58 as follows

gi
T = si

P ,n

(3.59)

gi
P = vi

T ,n

(3.60)

224

When comparing with Eqs. 3.10 & 3.9

g
= s
T P,n

(3.10)

g
=v
P T ,n

(3.9)

we can conclude that

Every equation that provides a linear
relation among thermodynamic
properties of a constant-composition
solution has its counterpart as an
equation connecting the corresponding
partial properties of each species in the
solution

225

Example In the case of a constantcomposition solution ( i.e. dni = 0 ) , we

know that
gi = f ( T , P )

Hence,
gi
gi
dgi =
dT +
dP

T P,n
P T ,n

Combining the above equation

with Eqs. 3.59 & 3.60 results in
dgi = si dT + vi dP

(3.61)

which is in accord with Eq. 2.13

dg = sdT + vdP

226

(2.13)

3.4 Ideal-Gas Mixtures

If n moles of a mixture of ideal
gases contain in a container with a
volume of V t at the temperature of T,
the total pressure of the container
can be calculated using the
following equation:
nRT
P= t
V

227

(3.62)

and if ni moles of species i contain in the

same container, the partial pressure of
species i ( Pi ) at the same temperature,
T, is as follows:
ni RT
Pi = t
V

(3.63)/(3.62) gives
ni RT
t
Pi
ni
V
=
= = xi
P nRT n
Vt

or

Pi = xi P

228

(3.63)

Partial volume of species i (ideal gas)

can be written in the form of equation
as follows:
vi

ig

nv ig
=

i T ,P ,nj
RT
n P
=

ni

T ,P,nj
=

RT n
P ni T ,P,n

Since n = ni + nj , but nj is constant,

we obtain
( ni + nj )
n
=

ni
i T ,P,nj
T ,P,nj

( nj )
ni
=
+
=1

ni T ,P,nj ni T ,P,nj
229

Thus,
vi

ig

RT
=
= viig
P

which illustrates that, in the case of an

ideal-gas mixture
vi ig = vi ig

(3.64)

The above relation can also be

extended to other thermodynamic
properties:
A partial molar property 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 same
temperature, but at a pressure equal to its
partial pressure in the mixture

230

which can be written in the form of

equation as follows:
Mi ig ( T , P ) = Mi ig ( T , Pi )

(3.65)

3.4.1 For Enthalpy:

hi ig ( T , P ) = hi ig ( T , Pi )

However, we have known (from

Chapter 2) that an enthalpy of an ideal
gas is independent of P
Hence,
hi ig ( T , P ) = hi ig ( T , Pi ) = hi ig ( T , P )

meaning that
hi ig = hi ig

231

(3.66)

Applying Eq. 3.28

M = xi Mi

(3.28)

to enthalpy, yields
hig = xi hiig = xi hiig

(3.67)

This indicates that, for an ideal-gas

solution, the summation of an enthalpy
of each pure species is equal to the
enthalpy of the solution

232

3.4.2 For Entropy:

Since an entropy of an ideal gas
depends on both T & P (see Chapter 2),
by considering Eq. 2.31 when T is
constant, we obtain
0

dsi ig = cp

dT
dP
R
T
P

dP
P
= Rd ln P

dsi ig = R

Integrating the above equation

from P = Pi to P = P yields

233

Pi

Pi

ig
ds
i = Rd ln P
P

= R d ln P
Pi

si ig ( T , P ) si ig ( T , Pi ) = R [ln P ln Pi ]

P
si ( T , P ) si ( T , Pi ) = R ln
Pi
ig

ig

Pi
but xi = Pi = xi P
P

Accordingly,
P
1
= R ln
si ( T , P ) si ( T , Pi ) = R ln
xi P
xi
ig

ig

si ig ( T , P ) si ig ( T , Pi ) = R ln xi

234

(3.68)

Applying Eq. 3.65 to entropy yields

si ig ( T , P ) = si ig ( T , Pi )

(3.69)

Combining Eq. 3.68 with Eq. 3.69 results in

si ig ( T , P ) si ig ( T , P ) = R ln xi

(3.70)

Rearranging Eq. 3.70 gives

si ig ( T , P ) = si ig ( T , P ) R ln xi

(3.71)

Multiplying Eq. 3.71 with xi gives

xi si ig ( T , P ) = xi si ig ( T , P ) Rxi ln xi

(3.72)

Applying Eq. 3.28 ( M = xi Mi ) to Eq. 3.72

yields
ig
ig
x
s
T
,
P
=
x
s
(
)
ii
i i ( T , P ) R xi ln xi

sig = xi si ig ( T , P ) R xi ln xi

235

(3.73)

Rearranging Eq. 3.73 gives

1
s xi si ( T , P ) = R xi ln
xi
ig

ig

(3.74)

Note that sig xi si ig ( T , P ) = entropy

change of mixing for ideal gas
Since 1 xi > 1, sig xi si ig ( T , P ) > 0
(positive, +, sign) in agreement
with the 2nd law of thermodynamics
(what does the 2nd law say?)

236

Applying the relations among

partial properties to the Gibbs free
energy for an ideal gas
gig = hig Tsig

(3.75)

gi ig = hi ig Tsi ig

(3.76)

gives

Combining Eq. 3.76 with Eqs. 3.66

& 3.71 yields
gi ig = hi ig T ( si ig R ln xi )

(3.77)

Rearranging Eq. 3.77 results in

gi ig = ( hi ig Tsi ig ) + RT ln xi

gi ig = i = giig + RT ln xi
237

(3.78)

For an ideal gas when T is constant,

Eq. 2.13
dg = vdP sdT

(2.13)

becomes
dgiig = vdP
RT
=
dP
P
dP
= RT
P
dgiig = RTd ln P

(3.79)

Integrating Eq. 3.79 yields

giig = RT ln P + i ( T )

where

(3.80)

i ( T ) = integration constant
= f(T)

238

Combining Eq. 3.78 with Eq. 3.80

results in
giig = giig + RT ln xi
= RT ln P + i ( T ) + RT ln xi
= i ( T ) + RT (ln xi + ln P )
giig = i ( T ) + RT ln xi P

(3.81)

Applying Eq. 3.28 to Eq. 3.81 yields

gig = xi giig = xi i ( T ) + RT xi ln xi P

(3.82)

239

3.5 Fugacity and Fugacity

Coefficient: Pure Species
Re-writing Eq. 3.80
giig = RT ln P + i ( T )

(3.80)

for pure & real fluids at constant T

gives
gi = RT ln fi + i ( T )

(3.83)

The property fi in Eq. 3.83 is called

a FUGACITY
Accordingly, fugacity has the
same unit as pressure

240

(3.83) (3.80) yields

gi giig = RT ln fi + i ( T ) RT ln P + i ( T )
= RT ln

fi
P

but gi giig = giR (see Chapter 2); thus,

fi
g = RT ln
P
R
i

Note that

fi
= i = FUGACITY
P

COEFFICIENT
Hence,
giR = RT lni

241

(3.84)

In the case of an ideal gas: fi = P

i =

fi
= 1 giR = RT ln (1) = 0
P

Rearranging Eq. 3.84 gives

giR
lni =
RT

(3.85)

Combining Eq. 3.85 with Eq. 2.67

(see Chapter 2)
P

gR
dP
= ( Z 1)
RT 0
P

(2.67)

yields
P

giR
dP
lni =
= ( Zi 1)
RT 0
P

242

(3.86)

In the case of cubic EoS (e.g.,

Redlich-Kwong, Soave-Redlich-Kwong,
gR
& Peng-Robinson EoS), the property
RT

can be written for species i, as follows

giR
= ln (1 b ) Zi qI + ( Zi 1)
RT

(2.85a)

Combining Eq. 2.85a with Eq. 3.85

giR
lni =
RT

(3.85)

gives
gi R
lni =
= ln (1 b ) Zi qI + ( Zi 1)
RT

243

(3.87)

but, from Eq. 2.95 (See Chapter 2)

B
= b
Z

(2.95)

or, for species i

Bi
= b
Zi

(2.95a)

Eq. 3.87 can, thus, be re-written as

follows:
gi R
lni =
= ln ( Zi Bi ) qI + ( Zi 1)
RT

244

(3.88)

3.6 Vapour/Liquid Equilibrium (VLE)

for Pure Species
When a system consists of liquid (l)
and vapour (v), we can write Eq. 3.83
for each phase, as follows:
giv = RT ln fi v + i ( T )

(3.89)

gil = RT ln fi l + i ( T )

(3.90)

(3.89) (3.90) yields

giv gil = RT ln fi v RT ln fi l
fi v
= RT ln l
fi

245

At equilibrium,
giv = gil

or

giv gil = 0

Thus, this means that

fi v
ln l = 0
fi

or

fi v = fi l = fi sat

(3.92)

For a pure species coexisting

liquid and vapour phases are in
equilibrium when they have the
same T, P, and FUGACITY

246

Dividing Eq. 3.92 with P results in

fi v fi l fi sat
= =
P P
P

iv = il = isat

(3.93)

which implies that, when two phases

are in equilibrium with each other at
constant T & P, in addition to the fact
that the fugacity of each phase is
equal to each other, their fugacity
coefficients are also identical

247

Example

For H2O at a T of 300 oC and for

P up to 10,000 kPa (100 bar), calculate

values of fi and i using data from steam
tables
Writing Eq. 3.83 for a constant-P system
at P = P gives
gi = RT ln fi + i ( T )

(3.83)

and at P = low P yields

gi* = RT ln fi * + i ( T )

(3.94)

(3.83) (3.94) results in

fi
gi g = RT ln *
fi
*
i

fi gi gi*
ln * =
RT
fi
248

(3.95)

Writing the following equation

(3.96)

gi = hi Tsi

for a low-P system gives

(3.97)

gi* = hi* Tsi*

(3.96) (3.97) results in

gi gi* = ( hi hi* ) T ( si si* )

(3.98)

Dividing Eq. 3.98 with RT yields

*
*
gi gi* ( hi hi ) ( si si )
=

RT
RT
R

Substituting the above Eq. into Eq. 3.95

results in
fi
ln * =
fi

*
h

h
( i i)

RT

249

*
s

s
( i i)

(3.99)

Let low P = 6 kPa, and when T = 300 oC

(note that, at low P (& high T as T = 300 oC),
water vapour (H2O) can be assumed to be
an ideal gas; hence, fi * = P* = 6 kPa )
h = 3,076.8 kJ/kg & s = 9.5162 kJ/kg-K
(by reading from a superheated steam table)

At P = 4,000 kPa (4 MPa) & T = 300 oC

(superheated vapour), we obtain the
following values
h = 2,958.6 kJ/kg & s = 6.3531 kJ/kg-K

Substituting corresponding numerical

values into Eq. 3.99 results in

250

(18.02 [2,958.6 3,076.8])

kJ
kmol

fi
ln * =
kJ
fi

8.314

([ 300 + 273 ] K )
kmol-K

kJ
(18.02 [6.3561 9.5162]) kmol-K

kJ

8.314

kmol-K

= 6.395
(note that we have to multiply the values of h
& s obtained from the steam table with MW of water
(= 18.02) to convert the units of h & s to be kJ/kmol
& kJ/kmol-K, respectively)

Thus,
fi
= exp(6.395) = 598.84
*
fi

fi = 598.84fi * = 598.84 ( 6 kPa) = 3,593 kPa

and
fi 3,593 kPa
i = =
= 0.898
P 4,000 kPa
251

When P = 10,000 kPa & T = 300 oC

(the system (H2O) is now in the form of
compressed liquid), we obtain the
following
h = 1,347.3 kJ/kg & s = 3.2519 kJ/kg-K

Substituting corresponding numerical

values into Eq. 3.99 yields
kJ
kmol

fi (18.02 [1,347.3 3076.8 ])

ln * =
kJ
fi

8.314

([ 300 + 273 ] K )
kmol-K

kJ
18.02
3.2519
9.5162

[
]) kmol-K
(

kJ

8.314

kmol-K

= 7.057

252

Hence,
fi
= exp(7.057) = 1,160.96
*
fi
fi = 1,160.96fi * = 1,160.96 ( 6 kPa) = 6,966 kPa

and
fi 6,966 kPa
i = =
= 0.697
P 10,000 kPa

It can be observed, from this

Example, that when P is getting higher,
the discrepancy between the values of
fi and P is getting larger

Also, when P is getting higher, the

value of i is lower and getting more
and more deviated from unity (i.e. 1)
253

3.7 Fugacity and Fugacity

Coefficient: Species in Solutions
Combining Eq. 3.78
iig = giig = giig + RT ln xi

(3.78)

with Eq. 3.80

gigi = i ( T ) + RT ln P

(3.80)

gives the following equation:

iig = giig = ( i ( T ) + RT ln P ) + RT ln xi

Rearranging the above equation

gives
iig = giig = i ( T ) + RT ln ( xi P )

which is the same as Eq. 3.81

254

(3.100)

If this is a real solution (can be

either gaseous or liquid solution), Eq.
3.100 can be re-written as follows:
i = gi = i ( T ) + RT ln fi

(3.101)

where
fi = fugacity of species i in a solution

We have just learned that, if there

are 2 phases (e.g., phases & ) coexisting in equilibrium at given T & P, it
results in the fact that
fi = fi

255

The above equation can also be

applied to any species in a solution
as follows
fi = fi

Multiple phases at the same

T & P are in equilibrium when
the fugacity of each constituent
species is the same in all phases

256

We have learned, from Chapter 2,

that
MR = M Mig

(2.55)

Hence, (3.101) (3.100) results in

giR = gi giig = i iig
= RT ln fi RT ln ( xi P )

fi
g = RT ln

x
P
i
R
i

Let

(3.102)

fi
fi
i =
=
xi P Pi

Thus,
giR = RT lni

(3.103)

where i = fugacity coefficient of

species i in a solution
257

We do the same as did previously

for i (see Page 242) and, thus,
obtain
P

lni = ( Zi 1)
0

258

dP
P

(3.104)

3.8 Generalised Correlations for the

Fugacity Coefficient
Combining Eq. 3.86
P

dP
lni = ( Zi 1)
P
0

(3.86)

with the following equations

P

Pr =
Pc
P = PcPr
dP = d ( PcPr )
= PcdPr

results in

259

(3.105)
(3.106)

Pr

lni = ( Zi 1)
0

PcdPr
PcPr

Pr

dPr
lni = ( Zi 1)
Pr
0

(3.107)

We can write Pitzer et al theorem

of corresponding states
Z = Z ( 0 ) + Z (1)

(1.21)

for species i as follows

Zi = Zi( 0 ) + Zi(1)

260

(3.108)

Subtracting both sides of Eq. 3.108

with 1 results in
(3.109)

Zi 1 = Zi0 1+ Z1i

Combining Eq. 3.107 with Eq. 3.109

gives
Pr

dPr
lni = ( Zi 1)
Pr
0
Pr

dPr
= ( Z 1+ Z )
Pr
0
Pr

0
i

1
i

lni = ( Zi0 1)
0

Pr

dPr
dP
+ Z1i r
Pr
Pr
0

261

Let
Pr

dPr
ln = ( Z 1)
Pr
0
0
i

and

Pr

0
i

dPr
ln = Z
Pr
0
1
i

1
i

Thus,
lni = lni0 + lni1

Rearranging the above equation

yields
lni = ln + ln (
0
i

1
i

0
1

= ln (i )(i )

i = (

0
i

)( )

262

1
i

(3.110)

Note that the values of i0 and i1 in table

format (Tables A.3.1 and A.3.2) are
included at the end of this Chapter (on
Pages 284-285 and 286-287, respectively)

Example

Determine the values of

fugacity coefficient (i ) and fugacity ( fi )

of R-134a at 300 oC, and (a) 80 bar and
(b) 284 bar

For R-134a:
Tc = 374.26 K
Pc = 40.59 bar

= 0.326

263

(a)
Pr =

P
80 bar
=
= 1.97
Pc 40.59 bar

T [ 300 + 273 ] K
= 1.53
Tr = =
374.26 K
Tc

By performing double interpolations

of i( 0 ) and i(1) appeared in Tables A.3.1
and A.3.2, we obtain
i( 0) = 0.8495
i(1) = 1.1828

Hence,
i = ( 0.8495 )(1.1828 )

0.326

= 0.897

and

fi = i P = ( 0.897 )( 80 bar ) = 71.8 bar

264

(b)

P
284 bar
Pr =
=
= 7.0
Pc 40.59 bar

T [ 300 + 273 ] K
= 1.53
Tr = =
374.26 K
Tc

Thus, also by reading from Tables A.3.1

and A.3.2 and performing double
interpolations, we obtain

i( 0) = 0.6866
i(1) = 1.5817

Hence,
i = ( 0.6866 )(1.5817 )

0.326

= 0.797

and
fi = i P = ( 0.797 )( 284 bar )
= 226.3 bar
265

3.9 The Ideal Solution

In the case that we are dealing
with an ideal liquid solution, Eq. 3.78
giig = giig + RT ln xi

(3.78)

can be re-written for an ideal solution

as follows:
giid = gi + RT ln xi

(3.111)

Differentiating Eq. 3.111 with respect

to T, while P and composition are kept
constant, yields
giid
gi
RT ln xi
T = T + T
P ,x
P ,x

P ,x

266

Combining the above equation with Eq.

3.59
gi
T = si

P ,x

(3.59)

results in

g
si id = i + R ln xi
T P,x
and

si

id

gi
=
R ln xi

T P,x

(3.112)

Combining Eq. 3.10

g
= s
T P,x

(3.10)

re-written for species i

gi
T = si

P,x
with Eq. 3.112 gives
267

(3.10a)

si id = ( si ) R ln xi
= si R ln xi

(3.113)

Differentiating Eq. 3.111 with respect

to P, while T and composition are kept
constant, yields
giid
gi
RT ln xi
P = P + P
T ,x
T ,x

T ,x

(3.114)

Combining Eq. 3.114 with Eq. 3.60

gi
P = vi

T ,x

results in
g
viid = i + 0
P T ,x

Note that RT ln xi is a constant

268

(3.60)

By combining the above equation

with Eq. 3.9 re-written for species i
gi
P = vi

T ,x

(3.9a)

viid = vi

(3.115)

we obtain

When we applied the following

equation
g = h Ts

to an ideal solution, we obtain

giid = hiid Tsi id

or
hiid = giid + Tsi id

269

(3.116)

Combining Eq. 3.116 with Eqs. 3.111 &

3.113 gives
hiid = [ gi + RT ln xi ] + T [ si R ln xi ]
= gi + Tsi = hi

which indicates that

(3.117)

hiid = hi

Applying Eq. 3.28

M = xi Mi
i

to an ideal solution gives

Mid = xi Miid
i

270

(3.28)

Thus,
gid = xi giid = xi gi + xi RT ln xi
= xi gi + RT xi ln xi

(3.118)

sid = xi si id = xi si R xi ln xi

(3.119)

v id = xi viid = xi vi

(3.120)

hid = xi hiid = xi hi

(3.121)

271

3.10 The Lewis/Randall Rule

When applying Eq. 3.101
i = gi = i ( T ) + RT ln fi

(3.101)

to an ideal solution, we obtain

iid = giid = i ( T ) + RT ln fi id

(3.122)

Combining Eq. 3.83

gi = i ( T ) + RT ln fi

(3.83)

with Eq. 3.111

giid = gi + RT ln xi

yields

272

(3.111)

 i ( T ) + RT ln fi id = i ( T ) + RT ln fi + RT ln xi

Rearranging the above equation

gives
RT ln fi id = RT ln fi + RT ln xi
= RT ln ( xi fi )

fi id = xi fi

(3.123)

Eq. 3.123 = Lewis/Randall Rule

Fugacity of each species in an
ideal solution is proportional to its
mole fraction, where fugacity of
pure species i is a proportionality
constant

273

Dividing Eq. 3.123 with xi P yields

fi id xi fi fi
=
=
xi P xi P P

We have defined (see Page 257) that

fi
i =
xi P

and when applying the above definition to

an ideal solution, we obtain
id

f
f
iid = i = i
xi P P

274

Since
fi
i =
P

(see Page 241)

iid = i

(3.124)

(Note: for IDEAL SOLUTION only)

275

3.11 Excess Properties

As well as a residual property
(2.55)

MR = M Mig

an excess property indicates how far

a real solution deviates from an ideal
solution, which can be written in the
form of equation as follows
(3.125)

ME = M Mid

(3.125) (2.55) results in

ME MR = ( M Mid ) ( M Mig )
= (M M
id

ig

276

(3.126)

Since an ideal-gas mixture is an

ideal-gas solution, when we replace gi
in Eq. 3.118
gid = xi gi + RT xi ln xi

(3.118)

with giig , the resulting equation is as

follows:
gig = xi giig + RT xi ln xi

(3.127)

(by applying Eq. 3.28 to Eq. 3.78)

Eqs. 3.119-3.121 can also be rewritten as a function of Miig in the same

manner as Eq. 3.127 (please try to do it
yourself)

277

Thus, (3.118) (3.127) yields

gid gig = xi gi xi giig = xi giR

When performing the same derivation

for Eqs. 3.119-3.121, we obtain the following
general equation for any property
Mid Mig = xi Mi xi Miig = xi MiR

(3.128)
When combining Eq. 3.128 with
Eq. 3.126, we obtain
ME MR = ( xi MiR )
ME = MR xi MiR

278

(3.129)

Note that Eq. 3.125 can be applied

to any partial property, as follows:
ME = M Mid

279

(3.130)

3.12 The Excess Gibbs Energy and

the Activity Coefficient
We can write Eq. 3.101
i = gi = i ( T ) + RT ln fi

(3.101)

for an ideal solution, as follows

giid = i ( T ) + RT ln fi id

(3.131)

Combining Eq. 3.131 with Eq. 3.123

(Lewis/Radall Rule)
fi id = xi fi

(3.123)

giid = i ( T ) + RT ln xi fi

(3.132)

gives

280

(3.101) (3.132) results in

fi
gi g = g = RT ln
xi fi
id
i

E
i

(3.133)

fi
Let i =
= activity coefficient of
xi fi

species i in a solution
Thus,
giE = RT ln i

(3.134)

giE
= ln i
RT

(3.135)

and

281

When applying Eq. 3.28 to Eq. 3.135,

we obtain
giE
gE
= xi
= xi ln i
RT
RT

(3.136)

The Nature of Excess Properties

(See Figure 3.4)
Strongly depend on T
Weakly depend on P, especially
at moderate T
Depend on composition, but
the dependence varies from
solution to solution
282

Figure 3.4: Examples of the Nature of Excess Properties

(from Introduction to Chemical Engineering Thermodynamics:
7th ed, by Smith, Van Ness, and Abbott, 2005)

283

Table A.3.1: Values of 0 as a function of Tr and Pr

(from Introduction to Chemical Engineering Thermodynamics:

7th ed, by Smith, Van Ness, and Abbott, 2005)

284

Table A.3.1: Values of 0 as a function of Tr and Pr (cont.)

(from Introduction to Chemical Engineering Thermodynamics:
7th ed, by Smith, Van Ness, and Abbott, 2005)

285

Table A.3.2: Values of 1 as a function of Tr and Pr

(from Introduction to Chemical Engineering Thermodynamics:

7th ed, by Smith, Van Ness, and Abbott, 2005)

286

Table A.3.2: Values of 1 as a function of Tr and Pr (cont.)

(from Introduction to Chemical Engineering Thermodynamics:
7th ed, by Smith, Van Ness, and Abbott, 2005)

287