KMM3531 Chemical Engineering Thermodynamics II

Solution Thermodynamics

Prof. Dr. Hasan SADIKOĞLU

Yıldız Technical University
Department of Chemical Engineering
• Develop a fundamental property relation that is applicable to open phases of
variable composition.
• Define the chemical potential, a fundamental new property that facilitates
treatment of phase and chemical-reaction equilibria.
• Introduce partial properties, a class of thermodynamic properties defined
mathematically to distribute total mixture properties among individual species
as they exist in a mixture. These are composition-dependent and distinct from
the molar properties of pure species.
• Develop property relations for the ideal-gas-state mixture, which provide the
basis for treatment of real-gas mixtures.
• Define yet another useful property, the fugacity. Related to the chemical
potential, it lends itself to mathematical formulation of both phase- and
chemical-reaction-equilibrium problems.
• Introduce a useful class of solution properties, known as excess properties, in
conjunction with an idealization of solution behavior called the ideal-solution
model, which serves as a reference for real-solution behavior.
❑ Solution Thermodynamics Theory

❑ Fundamental Property Relation

❑ Partial properties

❑ Gibbs-Duhem Equation

❑ Ideal Gas Mixtures

❑ Fugacity and Fugacity coefficient of pure species and

species in solution

❑ Ideal solution, Lewis Randall rule

• Most of the materials of the real world are not pure substances with all
atoms or molecules identical but rather are mixtures of one type or
another.

• The pure substances from which a solution may be prepared are called
components, or constituents, of the solution.

• Solutions are not limited to liquids: for example air, a mixture of

predominantly N2 and O2, forms a vapor solution. Solid solutions such
as the solid phase in the Si-Ge system are also common
 Multicomponent Systems – Basic Relations

• Single component system:

– Intensive properties: depends on Pressure, Temperature
– Extensive properties: depends on Pressure, Temperature, and amount

• Multicomponent system:
– Intensive properties: depends on Pressure, Temperature, and composition
– Extensive properties: depends on Pressure, Temperature, amount of each
component
Measures of Composition

The three most common measures of composition in thermodynamics are

mass fraction, mole fraction, and molar concentration. Mass or mole
fraction is defined as the ratio of the mass or number of moles of a
particular chemical species in a mixture to the total mass or number of
moles of mixture:

For binary system (solution):

In dealing with dilute solutions it is convenient to speak of the component present in

the largest amount as the solvent, while the diluted component is called the solute.
Other Measures of Composition

• Mass fraction – preferable where the definition of molecular weight

is ambiguous (eg. Polymer molecules)

• Molarity – moles per liter of solution

• Molality – moles per kilogram of solvent. The molality is usually

preferred, since it does not depend on temperature or pressure,
whereas any concentration unit is so dependent.

• Volume fraction

• Mole ratio or volume ratio (for binary systems)

Properties of Solutions
• The properties of solutions are, in general, not additive properties of
the pure components.

• The actual contribution to any extensive property is designated as

its partial property. The term partial property is used to designate
the property of a component when it is in admixture with one or
more other components

• Because most chemical, biological, and geological processes occur at

constant temperature and pressure, it is convenient to provide a
special name for the partial derivatives of all thermodynamic
properties with respect to mole number at constant pressure and
temperature. They are called partial molar properties
Ethanol-Water System at 20oC

Molar volumes: Partial molar volumes

Water: 18 mL/mol (at 50 mole% of
Ethanol: 58 mL/mol Ethanol):

Water: 16.9 mL/mol

Ethanol: 57.4 mL/mol

Volume before mixing = (1 mole) (18.0 mL/mole) + (1 mole) (58.0 mL/mole) = 76 mL

Volume after mixing = (1 mole) (16.9 mL/mole) + (1 mole) (57.4 mL/mole) = 74.3 mL
Fundamental Property Relation
• Total Gibbs energy change of any CLOSED system:

*applied to a single phase fluid in a closed system wherein no chemical

reactions occurs & the composition is constant.

Therefore;

No of moles of all chemical species are held constant.

Fundamental Property Relation
For the more general case of 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. It
remains a function of T and P, and we can therefore write the functional relation:

The total differential of nG is then

where ni is the no of moles of species i.

* nj indicates that all mole no except the ith are held constant.
ential, μ i
ical pot
d as chem
Define
Fundamental Property Relation

Since

total change of Gibbs energy for OPEN system becomes:

This equation is a fundamental property relation for

SINGLE-PHASE FLUID SYSTEM of variable mass & composition
Fundamental Property Relation

• For special case of one mol of solution, n=1 & ni = xi ,

becomes

G as a function of T, P
and xi

At constant T & x: At constant P & x: At constant P & x:

from
When the Gibbs energy is expressed as a
function of its canonical variables, it serves as
a generating function, providing the means for
the calculation of all other thermodynamic
properties by simple mathematical operations
(differentiation and elementary algebra), and
it implicitly represents complete property
information.
2. The Chemical Potential & Equilibrium

• For a CLOSED system consisting of TWO phases in equilibrium, each

individual phase is OPEN to other (mass transfer between phases may
occur).

phase

Presumption: At equilibrium, T & P are

the same in all phases.
2. The Chemical Potential & Equilibrium

• The change in total Gibbs energy of the two-phase system is the

sum of these equations:

Reduced to this form:

2. The Chemical Potential & Equilibrium

• At equilibrium,
The changes of &
result from mass transfer
between the phases.

Therefore,
2. The Chemical Potential & Equilibrium

• Since Thus, multiple phases at the same

T and P are in equilibrium when
the chemical potential of each
species is the same in all phases.
Therefore, or

Multiple phases at the same T & P

are in equilibrium when the chemical
potential of each species is the SAME
in all phases.
10.3 PARTIAL PROPERTIES

Partial molar property, of species i in solution,

Sometimes called a response function, it is a measure of the response of

total property nM to the addition of an infinitesimal amount of species
i to a finite amount of solution, at constant T and P.
10.3 PARTIAL PROPERTIES

Properties example
Solution properties

Partial properties

Pure-species properties
10.3 PARTIAL PROPERTIES

Since

Therefore,

or
Because:
10.3.1. Equations Relating Molar and Partial Molar Properties

The total thermodynamic properties of a homogeneous phase are functions of T, P, and

the no of moles of individual species.

The total differential of nM is:

At constant n,

*x denotes differentiation at constant composition

10.3.1. Equations Relating Molar and Partial Molar Properties

Because

According to product rule,

10.3.1. Equations Relating Molar and Partial Molar Properties

Factorizing n and dn terms,

Mathematically,

x n
10.3.1. Equations Relating Molar and Partial Molar Properties

summability
equation

Co
mp
ari
ng

Gibbs/Duhem
equation
(at constant T & P)
Example 10.1
The partial molar volume is defined as:

What physical interpretation can be given to this equation?

Solution 10.1
Suppose an open beaker containing an equimolar mixture of ethanol and water
occupies a total volume nV at room temperature T and atmospheric pressure P.
Add to this solution a drop of pure water, also at T and P, containing Δnw moles,
and mix it thoroughly into the solution, allowing sufficient time for heat Exchange
to return the contents of the beaker to the initial temperature. One might expect
that the volume of solution increases by an amount equal to the volume of the
water added, i.e., by VwΔnw, where Vw is the molar volume of pure water at T and
P. If this were true, the total volume change would be:
However, experimental observations show that the actual volume change is somewhat less.
Evidently, the effective molar volume of water in the final solution is less than the molar
volume of pure water at the same T and P. We may therefore write:

where represents the effective molar volume of water in the final solution. Its experimental
value is given by:

In the process described, a drop of water is mixed with a substantial amount of solution,
and the result is a small but measurable change in composition of the solution.

For the effective molar volume of the water to be considered a property of the original
equimolar solution, the process must be taken to the limit of an infinitesimal drop. Whence,
Δnw → 0, and Eq. (C) becomes:
Because T, P, and na (the number of moles of alcohol) are constant, this equation is more
appropriately written:

Comparison with Eq. (A) shows that in this limit is the partial molar volume of the
water in the equimolar solution, i.e., the rate of change of the total solution volume with
nw at constant T, P, and na for a specific composition. Written for the addition of dnw
moles of water to the solution, Eq. (B) is then:

When is considered the molar property of water as it exists in solution, the

total volume change d(nV) is merely this molar property multiplied by the number
of moles dnw of water added.
If dnw moles of water is added to a volume of pure water, then we have every
reason to expect the volume change of the system to be:

where Vw is the molar volume of pure water at T and P. Comparison of Eqs.

(D)
and (E) indicates that when the “solution” is pure water.
A Rationale for Partial Properties
Partial properties, like solution properties, are functions of composition. In the
limit as a solution becomes pure in species i, both M and approach the
pure-species property Mi. Mathematically,

For a partial property of a species that approaches its infinite-dilution limit, i.e., a
partial property value of a species as its mole fraction approaches zero, we can
make no general statements. Values come from experiment or from models of
solution behavior. Because it is an important quantity, we do give it a symbol, and
by definition we write:
A Rationale for Partial Properties

The essential equations of this section are thus summarized as follows:

which shows that the partial properties of species making up a solution are not
independent of one another.
 10.3.2 Partial Properties in Binary Solutions

For binary solution, the summability relation, becomes:

(A)

(B)

At constant T & P, Gibbs/Duhem eq,

becomes

Thus, for binary solution, Gibbs/Duhem eq. can be written as,

(C)
10.3.2 Partial Properties in Binary Solutions

Substituting into differential of summability

relation:
(B)

Because x1+x2=1, x1=1-x2 and dx1=-dx2,

(D)
10.3.2 Partial Properties in Binary Solutions

The summability relation, can also be written

as:
 10.3.2 Partial Properties in Binary Solutions

Gibbs/Duhem equations, may be written in derivative forms:

 Example 10.2
Describe a graphical interpretation of following Equations:

Graphical construction of Example 10.2. Infinite-dilution values of partial properties

Figure 10.1(a) shows a representative plot of M vs. x1 for a binary system. The
tangent line shown extends across the figure, intersecting the edges (at x1 = 1 and
x1 = 0) at points labeled I1 and I2. As is evident from the figure, two equivalent
expressions can be written for the slope of this tangent line:

The first equation is solved for I2; it combines with the second to give I1:

Comparisons of these expressions with equations show that:

Thus, the tangent intercepts give directly the values of the two partial
properties. These intercepts of course shift as the point of tangency moves along
the curve, and the limiting values are indicated by the constructions shown in
Fig. 10.1(b). For the tangent line drawn at x1 = 0 (pure species 2) and
at the opposite intercept .Similar comments apply to the tangent drawn
at x1 = 1 (pure species 1). In this case
Example 10.3
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
25°C must be mixed to form the 2000 cm3 of antifreeze, also at 25°C? Partial molar
volumes for methanol and water in a 30 mol-% methanol solution and their
pure-species molar volumes, both at 25°C, are:
The summability relation, , is written for the molar volume of the

binary antifreeze solution, and known values are substituted for the mole fractions
and partial molar volumes:

Because the required total volume of solution is Vt = 2000 cm3, the total number
of moles required is:

Of this, 30% is methanol, and 70% is water:

The volume of each pure species is ; thus,

Example 10.4
The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is
represented by the equation:
where H is in J·mol–1.

Determine expressions for as functions of x 1, numerical values for the

pure-species enthalpies H1 and H2, and numerical values for the partial
enthalpies at infinite dilution .
 10.3.3 Relations among Partial Properties

The change of Gibbs energy,

Application of the criterion of exactness yields:

Recall:
 10.4. The Ideal-Gas Mixture
Gibbs 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
pressure equal to its partial pressure in the mixture

Thus, for general partial property;

The enthalpy of an ideal gas is independent of pressure;

Also applies to other property that

[1] are independent of pressure
 10.4. The Ideal-Gas Mixture
The entropy of an ideal gas does depend on pressure;

(const T)
 10.4. The Ideal-Gas Mixture

A partial molar property ideal

gas mixture is equal to the
Since molar property of the species as
a pure ideal gas at the mixture
temperature but at pressure
equal to its partial pressure in
the mixture
Thus,

or
[2]
 10.4. The Ideal-Gas Mixture

For Gibbs energy of an ideal-gas mixture,

the partial properties is:
Recall:

Thus,

or
[3]

Recall:
 10.4. The Ideal-Gas Mixture

So far, we have derive:

[1]

[2]

[3]

Substituting [1], [2] & [3] into the summability relation,

[4]

[5]

[6]
 10.4. The Ideal-Gas Mixture
The properties of mixture for enthalpy, entropy and Gibbs energy:
[4]

[5]

[6]

Rearranging [4] & [5] give enthalpy & entropy change of mixing;
For ideal gas, mixing at constant T & P
is not accompanied by heat transfer
 10.4. The Ideal-Gas Mixture

Alternatively, in eq [3] ( ) can be expressed

by giving its T and P dependence:
(const T)

Integration constant
Integration gives; at constant T

[7]

Thus eq [3] becomes:

[8]
 10.4. The Ideal-Gas Mixture
[8]

Substituting Eq. [8] into summability relation,

Thus, Gibbs energy of an ideal-gas mixture, becomes:

10.5. Fugacity & Fugacity Coefficient: Pure Species

Fugacity of pure species i,

• For real fluid; with units of pressure

[8]

• Subtracting Eq. [7] , from eq [8];

Fugacity: pressure of an ideal

gas which has the same
Residual Fugacity chemical potential as the real
Gibbs energy coefficient
gas.
10.5. Fugacity & Fugacity Coefficient: Pure Species

From previous chapter,

Thus,

(const T)
 10.5. Fugacity & Fugacity Coefficient: Pure Species

From previous chapter,

or

Thus, becomes:

(const T)
10.5. Fugacity & Fugacity Coefficient: Pure Species

• For vapor/liquid equilibrium;

For saturated vapor

For saturated liquid

• By difference:

• At equilibrium,

• Thus,
 10.5. Fugacity & Fugacity Coefficient: Pure Species

• Therefore, For a pure species, coexisting liquid and vapor phases are in equilibrium
when they have the same temperature, pressure, and fugacity.

The word fugacity is based on a Latin root meaning to flee or escape, also
the basis for the word fugitive. Thus fugacity has been interpreted to
mean “escaping tendency.” When the escaping tendency is the same for
the two phases, they are in equilibrium. When the escaping tendency of a
species is higher in one phase than another, that species will tend to
transfer to the phase where its fugacity is lower.

For a pure species coexisting liquid & vapor

phases, they are in equilibrium when they
have the same temperature, pressure &
fugacity.
 10.5. Fugacity & Fugacity Coefficient: Pure Species

The fugacity of pure species i as a compressed (subcooled) liquid may be calculated as the product of the
saturation pressure with three ratios that are each relatively easy to evaluate:

A B C
10.5. Fugacity & Fugacity Coefficient: Pure Species

• For pure liquid,

A B C
10.5. Fugacity & Fugacity Coefficient: Pure Species

• For pure liquid,

A B C

From

From
(at constant T)
10.5. Fugacity & Fugacity Coefficient: Pure Species

• Ratio C becomes,

• Substituting A, B, and C terms;

10.6. Fugacity & Fugacity Coefficient: Species in Solution

• For a species i in a mixture of real gas or in a solution of liquids;

Fugacity of species i in solution

• At equilibrium;

Multiple phases at the same T & P are in

equilibrium when the fugacity of each
constituent species is the same in all species
10.6. Fugacity & Fugacity Coefficient: Species in Solution

• For a species i in a mixture of real gas or in a solution of liquids;

Partial residual Gibbs energy

Fugacity coefficient of species i in solution

 The Fundamental Residual-Property Relation

The fundamental property relation given by

(A)

This equation may be written for the special case of the ideal-gas state:

(B)

By substring equation (B) from equation (A)

(C) By Introducing
 (D)

Division of Eqs. (C) and (D), first, by dP with restriction to constant T and composition, and second,
by dT and restriction to constant P and composition leads to:

This equation demonstrates that the logarithm of the fugacity coefficient of a species in
solution is a partial property with respect to GR/RT.
Example 10.6
Develop a general equation to calculate values from compressibility-factor data.
10.6. 1 Fugacity Coefficient from the Virial Equation of State

• Fugacity coefficient;

• Virial equation of state:

• For n mol of gas mixture:

the bimolecular
interaction between
molecule i and j
10.6. 1 Fugacity Coefficient from the Virial Equation of State

Differentiation with respect to n1:

Thus becomes;
10.6. 1 Fugacity Coefficient from the Virial Equation of State

• For binary mixture:

OR can be written as:

OR

with
10.6. 1 Fugacity Coefficient from the Virial Equation of State

Multiplying by n;

Substituting ;

By differentiation;
10.6. 1 Fugacity Coefficient from the Virial Equation of State

Substituting into ;

Similarly;
Example 10.7
Determine the fugacity coefficients as given by Eqs. (10.63) for nitrogen and methane in a
N2 (1)/CH 4 (2) mixture at 200 K and 30 bar if the mixture contains 40 mol-% N 2.
Experimental virial-coefficient data are as follows:
B11 = − 35.2 B22 = − 105.0 B12= − 59.8 cm3 ⋅mol-1
10.6. 1 Fugacity Coefficient from the Virial Equation of State

For multicomponent gas mixtures;

where

and
with
10.7. Generalized Correlation for Fugacity Coefficient

• For pure gases; →

• Hence, at P=Pr , becomes;

At constant Tr

• From Pitzer correlation;

10.7. Generalized Correlation for Fugacity Coefficient

• Substitution of , becomes;

OR

Where;
10.7. Generalized Correlation for Fugacity Coefficient

can also be written as:

Example 10.8
Estimate from a value for the fugacity of 1-butene vapor at 200°C
and 70 bar.
10.7. Generalized Correlation for Fugacity Coefficient

can also be simplified by substituting:

Thus,

OR
10.7. Generalized Correlation for Fugacity Coefficient

• For gas mixtures;

Where;

and
10.7. Generalized Correlation for Fugacity Coefficient

• The calculation for (proposed by Prausnitz et al. );

Interaction parameter
(specific to i-j molecule pair)
10.7. Generalized Correlation for Fugacity Coefficient

EXAMPLE: Estimate & for an equimolar mixture of methyl ethyl

ketone(1)/toluene(2) at 50°C and 25kPa. Set all kij=0
10.7. Generalized Correlation for Fugacity Coefficient

EXAMPLE – Step 1: Calc Tcij, Vcij, Zcij &ωcij for ij=12

ij Tcij /K Pcij/bar Vcij/cm3mol-1 Zcij ωij

11 535.5 41.5 267 0.249 0.323

22 591.8 41.1 316 0.264 0.262

12 563.0 41.3 291 0.256 0.293

10.7. Generalized Correlation for Fugacity Coefficient

EXAMPLE- Step 2: Calc Trij, B0, B1 & Bij for all ij

ij Trij /K B0 B1 Bij/cm3mol-1

11 0.603 -0.865 -1.300 -1,387

22 0.546 -1.028 -2.045 -1,860

12 0.574 -0.943 -1.632 -1,611

10.7. Generalized Correlation for Fugacity Coefficient

EXAMPLE: Step 3:Estimate &