Part 1

 Fundamental Property Relation

 The Chemical Potential and Phase Equilibria
 Partial Properties
1
 Course Learning Outcomes
The student should be able to:
• Define and describe the important of the
thermodynamic terms such as partial and
residual properties, fugacity and fugacity
coefficient in chemical engineering.
• Differentiate the difference between pure,
partial, and solution properties.
• Estimate the fugacity and fugacity coefficient for
given pure (ideal or real), and mixture species at
specified conditions and approaches
2
 Fundamental Property Relation
d (nG)  (nV )dP  (nS )dT Eq. (6.6)
• Equation (6.6) relates the total Gibbs energy of any closed
system to its canonical variables, temperature and pressure
where n is the total number of moles of the system.
• An appropriate application is to a single phase fluid in a closed
system wherein no chemical reactions occur.

• For such a system the composition is necessarily constant, and

therefore
 (nG)   (nG) 
 P   nV and  T    nS
  T ,n   P ,n
The subscript n indicates that the numbers of moles of all
chemical species are held constant.
3
• For a single phase; open system, material may pass into and
out of the system, and nG becomes a function of the numbers
of moles of the chemical species present, and still a function
of T and P.
nG  g  P,T , n1, n2 ,..., ni ,... where ni is the number of
moles of species i.
• Total differential of nG is

  (nG)    (nG)    (nG) 

d (nG)    dP    dT     dni
 P  T ,n  T  P ,n i  ni  P ,T ,n j

• The summation is over all species present, and subscript nj

indicates that all mole numbers except the ith are held
constant.

4
• The derivative in the final term is called the chemical
potential. It is define as
  (nG) 
i    Eq. (11.1)
 ni  P ,T ,n j
• With this definition and with the first two partial derivatives
replaced by (nV) and –(nS), the preceding equation becomes
d (nG)  (nV )dP  (nS)dT   i dni Eq. (11.2)
i

• Equation (11.2) is the fundamental property relation for single

phase fluid systems of variable mass and composition.
• For special case of one mole of solution, n = 1 and ni = xi:
dG  VdP  SdT   i dxi
i
Eq. (11.3)

5
• Equation (6.10) for a constant composition solution is a
special case of Equation (11.3).
dG  VdP  SdT Eq. (6.10)
• Although the mole numbers ni of Eq. (11.2) are independent
variables, the mole fractions xi in Eq. (11.3) are not, because
i xi = 1.
• Eq. (11.3) does imply
 G   G 
V   Eq. (11.4) S    Eq. (11.5)
 P T , x  T  P , x
• Other solution properties come from definitions; e.g., the
enthalpy, from H = G + TS.
• Thus, by Eq. (11.5),
 G 
H  G T 
 T  P , x
6
When the Gibbs energy is expressed as a function of its
canonical variables, it plays the role of a generating
function, providing the means for calculation of all other
thermodynamic properties by simple mathematical
operations (differentiation and elementary algebra), and
implicitly represents complete property information.

7
 The Chemical Potential
and Phase Equilibria
• For a closed system consisting of two phases in equilibrium,
each individual phase is open to the other, and mass transfer
between phases may occur.

• Equation (11.2) applies separately to each phase:

d (nG)  (nV ) dP  (nS) dT   i dni
 

d (nG)   (nV )  dP  (nS) dT   i dni

 

where superscripts  and  identify the phases.

• The presumption here is that equilibrium implies uniformity
of T and P throughout the entire system.

8
• The change in the total Gibbs energy of the two phase system
is the sum of these equations.
• When each total system property is expressed by an equation
of the form,
nM  (nM)α  (nM)β
the sum is
d (nG)  (nV )dP  (nS)dT   i dni   i dni
   

i i

• Because the two phase system is closed, Eq. (6.6) is also valid.
d (nG)  (nV )dP  (nS )dT
• Comparison of the two equations shows that at equilibrium,
 i i  i i 0
   
 dn   dn
i i

9
• The changes dni and dni result from mass transfer between
the phases; mass conservation therefore requires
 (i  i )dni  0
    
dni  dni and
i

• Quantities dni are independent and arbitrary; therefore the

only way the left side of the second equation can in general
be zero is for each term in parentheses separately to be zero.
• Hence,
where N is the number of
i   i  (i  1,2,...,N)
species present in the
system.

10
• Successive application of this result to pairs of phases permits
its generalization to multiple phases; for  phases:

i  i   ...  i  (i  1,2,...,N)

Eq. (11.6)

• A similar but more comprehensive derivation shows that for

equilibrium T and P must be the same in all phases.
Multiple phases at the same T and P are in
equilibrium when the chemical potential
of each species is the same in all phases.

11
 Partial Properties
• Partial molar property Mi of a species i in a solution is define
as
  (nM ) 
Mi    Eq. (11.7)
 ni  P ,T ,n j
• It is a response function, i.e., a measure of the response of
total property nM to the addition at constant T and P of a
differential amount of species i to a finite amount of solution.

• Three kinds of properties used in solution thermodynamics

are distinguished by the following symbolism:
– Solution properties M, for example: V,U,H,S,G
– Partial properties M i , for example: Vi ,U i , H i , Si , Gi
– Pure species properties Mi, for example: Vi ,Ui ,Hi ,Si ,Gi
12
• Comparison of Eq. (11.1) with Eq. (11.7) written for the Gibbs
energy shows that the chemical potential and the partial
molar Gibbs energy are identical; i.e.,

  (nG)    (nM ) 
i    Eq. (11.1) Mi    Eq. (11.7)
 ni  P ,T ,n j  ni  P ,T ,n j

μi  Gi Eq. (11.8)

• Eq.(11.7) provides the calculation of partial properties from

mixture properties.

13
Equations Relating Molar and Partial Molar Properties
• For property M:
nM  Μ(T , P, n1 , n2 ,..., ni ,...)
• The total differential of nM is
  (nM )    (nM )    (nM ) 
d (nM )    dP    dT     dni
 P  T , n  T  P , n i  ni  P ,T , n
j

where subscript n indicates that all mole numbers are held constant,
and subscript nj that all mole numbers except ni are held constant.
• 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. (11.7), this equation has the
simpler form:
 M   M 
d (nM )  n  dP  n  dT   M i dni Eq. (11.9)
 P T , x  T  P, x i

where subscript x denotes differentiation at constant composition.

14
• Because ni = xin,
dni  xi dn  ndxi
• Moreover,
d (nM )  ndM  Mdn

• When dni and d(nM) are replaced in Eq. (11.9), it becomes

 M   M 
ndM  Mdn  n  dP  n  dT   M i ( xi dn  ndxi )
 P T , x  T  P , x i

• The terms containing n are collected and separated from

those containing dn to yield
  M   M    
 dM   
 P T , x
dP   
 T  P , x
dT   M i dxi  n   M   xi M i  dn  0
 i   i 

15
• The left side of this equation can be zero if each term in
brackets be zero too. Therefore,
 M   M 
dM    dP    dT   M i dxi Eq. (11.10)
 P T , x  T  P, x i
• and;
M   xi M i Eq. (11.11)
i

• Multiplication of Eq.(11.11) by n yields the alternative

expression:
nM   ni M i Eq. (11.12)
i

• Eq.(11.11) and (11.12) are known as summability relations,

they allow calculation of mixture properties from partial
properties.

16
• Differentiate Eq. (11.11) yields:
dM   xi dM i   M i dxi
i i

• Comparison of this equation with Eq. (11.10), yields the

Gibbs/Duhem equation:
 M   M 
  dP    dT   xi dM i  0 Eq. (11.13)
 P T , x  T  P , x 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.

• For the case of changes at constant T and P,

 x dM
i
i i 0 Eq. (11.14)
17
A Rationale for Partial Properties
• Solution property M represent a “whole”; the sum of its parts as
represented by partial properties M i of the constituent species.
M   xi M i Eq. (11.11)
i

• Partial properties M i is given by formula which assigns to each

species i its share of the solution property.
  (nM ) 
Mi    Eq. (11.7)
 ni  P ,T ,n j

• Partial properties like solution properties are functions of

composition. In the limit as a solution becomes pure in species i,
both M and M i approach the pure-species property Mi .
lim M  lim M i  M i
xi 1 xi 1
18
• For a species that approaches its infinite-dilution limits, i.e. the value as its
mole fraction approaches zero, we can make no general statements. The
values come from experiment or from models of solution behavior.
Because it is an important quantity, we do give it a symbol:

lim M i  M i
xi 0

Summary:
  (nM ) 
Definition Mi   
yields partial properties from
 ni  P ,T ,n j total properties

Summability M   xi M i yields total properties from

i partial properties

 M   M 
Gibbs/Duhem  i
x dM    dP    dT
 P T , x  T  P , x
i
i

which shows that the partial properties of species

making up solution are not independent of one another
19
Partial Properties in Binary Solutions
• For binary solution, the summability relation, Eq.(11.11)
becomes
M  x1M 1  x2 M 2 Eq. (A)

dM  x1dM1  M1dx1  x2 dM 2  M 2 dx2 Eq. (B)

• When M is known as a function of x1 at constant T and P, the

appropriate form of the Gibbs/Duhem equation is expressed
as  xi dM i  0
x1dM 1  x2 dM 2  0
i
Eq. (C)

• Because x1 + x2 = 1, it follows that dx1 = -dx2. Eliminating dx2 in

favor of dx1 in Eq. (B) and combining with Eq. (C) gives
dM
 M1  M 2 Eq. (D)
dx1
20
• Two equivalent forms of Eq.(A) result from elimination
separately of x1 and x2:
M  M1  x2 M1  M 2  and M  x1 M1  M 2   M 2
• In combination with Eq. (D) becomes
dM
M 1  M  x2 Eq. (11.15)
dx1

dM
M 2  M  x1 Eq. (11.16)
dx1

• Partial properties are readily calculated directly from an

expression for the solution property as function of
composition at constant T and P

21
• Eq. (C), the Gibbs/Duhem equation, may be written in
derivative forms:

dM 1 dM 2
x1  x2 0 Eq. (E)
dx1 dx1

dM 1 x dM 2
 2 Eq. (F)
dx1 x1 dx1
• When M1 and M 2 are plotted vs. x1, the slopes must be of
opposite sign.
• Moreover, dM 1 Similarly, dM 2
lim dx  0 lim dx  0
x1 1 1 x2 1 1

• Thus, plot of M1 and M 2 vs. x1 become horizontal as each

species approaches purity.
22
Example 11.2
Describe a graphical interpretation of Eqs. (11.15) and (11.16).

23
 Plot of M vs. x1 for a binary system
 The tangent line shown intersecting
the edges (at x1 = 1 and x1 = 0) at points
labeled I1 and I2.
 Two equivalent expressions for the
slope of this tangent line:
dM1 M  I 2 dM
 and  I1  I 2
dx1 x1 dx1
 The first equation solved for I2:
dM1
I 2  M  x1
dx1
 Then, combined with second equation
to solve for I1:
dM
I1  M  (1  x1 )
dx1
 Compare with Eq. (11.16) and (11.15),
shows that
I1  M 1 and I2  M 2
 Thus, tangent intercepts give directly
the values of two partial properties.
24
 The limiting values are indicated by
construct Fig. 11.1 (b).
 For the tangent line drawn at x1 = 0
(pure species 2),

M2  M2
 and at the opposite intercept,

M1  M1
 For the tangent line drawn at x1 = 1
(pure species 1),
M1  M1
and at the opposite intercept,

M2  M2

25
Example 11.3
The need arises in a laboratory for 2000 cm3 of an antifreeze
solution consisting of 30 mole % methanol in water.
What volumes of pure methanol and of pure water at 25oC
(298.15K) must be mixed to form the 2000 cm3 of antifreeze,
also at 25oC (298.15K)?
Partial molar volumes for methanol and water in a 30 mole %
methanol solution and their pure species molar volumes, both
at 25oC (298.15K), are

Methanol 1 : V1  38.632 cm3 mol-1 V1  40.727 cm3 mol-1

Water  2  : V2  17.765 cm3 mol-1 V2  18.068 cm3 mol-1

26
Solution
 Equation (11.11) written for the molar volume of the binary antifreeze
solution,
V   xiVi
i
 The mole fractions and partial volumes are substituted
V  x1V1  x2V2
V  (0.3)(38.632)  (0.7)(17.765)
V  24.025cm3 mol 1
 Because the required total volume of solution is Vt=2000 cm3, the total
number of moles required is
Vt 2000 cm3
n  3 1
 83.246 mol
V 24.025cm mol
 Of this, 30% is methanol and 70% is water:
n1  (0.3)(83.246)  29.974mol n2  (0.7)(83.246)  58.272mol
 The volume of each pure species is Vit = niVi:
V1  (24.974)(40.727)  1017 cm3 V2  (58.272)(18.068)  1053cm3
t t

27
 Plot of V vs. x1 for a binary solution

 Values of V1 ,V2 and V for the binary

solution methanol(1)/water(2) at 25°C
(298.15K) are plotted as function of x1.

 The line drawn tangent to the V vs. x1

curve at x1=0.3 to obtain values of
V1 and V2

 Conformance with the Gibbs/Duhem

equation (Eq. F), the slopes of the lines
for V1 and V2 are everywhere of opposite
sign.

 The curves for V1 and V2 appear to be

horizontal at both ends.

28
Example 11.4
The enthalpy of a binary liquid system of species 1 and 2 at
fixed T and P is represented by the equation
H  400x1  600 x2  x1x2  40 x1  20 x2 
where H is in Jmol-1.
 
Determine expressions for H1 and H2 as a 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 H2 .


29
Solution
 Replace x2 by 1-x1 for equation H and simplify:
H  400 x1  600 x2  x1 x2 40 x1  20 x2 
H  400 x1  600 (1  x1 )  x1 (1  x1 )40 x1  20(1  x1 ) 

Then, H  600  180 x1  20 x13 Eq. (A)

dH
 180  60 x12
dx1
 By Eq. (11.15), dH
H1  H  x2
Then, dx1
  
H 1  600  180 x1  20 x13  x2  180  60 x12 
H1  600  180 x 1  20 x13   180 x 2  60 x12 x2
 Replace x2 by 1-x1 and simplify:
H1  420  60 x12  40 x13 Eq. (B)
30
 By Eq. (11.16), dH
H 2  H  x1
Then, dx1
  
H 2  600  180 x1  20 x13  x1  180  60 x12 
H 2  600  180 x1  20 x13  180 x1  60 x13
H 2  600  40 x13 Eq. (C)

 Differentiation of the given equation for H by replacing

x2 by 1 – x1 and dx2/dx1 = -1 yields,
 400  600  x1 x2 40  20   40 x1  20 x2  x1  x2 
dH
dx1

 Replacing x2 by 1-x1 reproduces the expression previously

obtained.

31
 Numerical value for H1 results by substitute x1 = 1 in either
Eq. (A) or Eq. (B).
H1  400 Jmol 1
 Numerical value for H2 results by substitute x1 = 0 in either
Eq. (A) or Eq. (C).
1
H 2  600 Jmol

 Infinite-dilution values H1 found from Eq. (B) when x1 = 0.

H1  420 Jmol1


 Infinite-dilution values H 2 found from Eq. (C) when x1 = 1.
 1
H  640 Jmol
2
32
Relations among Partial Properties
• By Eq. (11.8),

i  G i
• and Eq. (11.2) may be written as
d  nG    nV  dP   nS  dT   i dni Eq. (11.2)
i


d  nG    nV  dP   nS  dT   G i dni Eq. (11.17)
i

• Application of the criterion of exactness, Eq. (6.12), yields the

Maxwell relation,
 M   N 
    Eq. (6.12)
 y  x  x y

 V   S 
 T     P  Eq. (6.16)
 P ,n  T ,n 33
 • Plus the two additional equations:
     
  Gi      nV     Gi       nS  
 P  ni  P ,T ,n  T   ni  P ,T ,n j
 T ,n  j  P ,n
where subscript n indicates constancy of all ni, and subscript nj
indicates that all mole numbers except the ith are held
constant.
• In view of Eq. (11.7), the last two equations are most simply
expressed:
     
  Gi   Gi
Partial-property  
analogs of Eq.
 V Eq. (11.18)   S Eq. (11.19)
 P  i
 T  i
(11.4) and (11.5)
 T ,x  P , x

• These equations allow calculation of the effects of P and T on

the partial Gibbs energy (or chemical potential).

34
 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.

• An example is based on the equation that defines 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 ) 
     P 
 ni  P ,T ,n j  ni  P ,T ,n j  ni  P ,T , n j

• By Eq. (11.7) this becomes

Partial-property   
analogs of Eq. (2.11) Hi  Ui  PVi
35
 

• In a constant-composition solution, Gi is a function of P and T,

and therefore:
     
  Gi  dP    Gi
d Gi    dT
 P   T 
 T ,x  P ,x

• By Eqs. (11.18) and (11.19),

Partial-property   

analogs of Eq. (6.10) d Gi  Vi dP  Si dT

• These examples illustrate the parallelism that exists between

equations for a constant-composition solution and the
corresponding equations for partial properties of the species
in solution.

36