6 Introduction to Solution Thermodynamics

The purpose in this chapter is to lay the theoretical foundation for applications of
thermodynamics to gas mixtures and liquid solutions. Multicomponent mixtures adds
substantially to the complexity of tabulating and correlating thermodynamic properties, and
leads to the introduction of new variables and relationships among them.

6.1 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:

𝑚𝑖 𝑚̇𝑖
𝑥𝑖 = =
𝑚 𝑚̇

𝑛𝑖 𝑛̇ 𝑖
𝑥𝑖 = =
𝑛 𝑛̇

Molar concentration is defined as the ratio of the mole fraction of a particular chemical species
in a mixture or solution to the molar volume of the mixture or solution:

𝑛𝑖 𝑛𝑖 ⁄𝑛 𝑥𝑖
𝐶𝑖 = = =
𝑉 𝑡 𝑉 𝑡 ⁄𝑛 𝑉

This quantity has units of moles of i per unit volume. For flow processes, convenience suggests
its expression as a ratio of rates. Multiplying and dividing by molar flow rate 𝑛̇ gives:

𝑛̇ 𝑥𝑖 𝑛̇ 𝑖
𝐶𝑖 = =
𝑛̇ 𝑉 𝑉̇

where 𝑛̇ 𝑖 is molar flow rate of species i, and 𝑉̇ is volumetric flow rate.

The molar mass of a mixture or solution is, by definition, the mole-fraction-weighted sum of
the molar masses of all species present:

𝑀 = ∑ 𝑥𝑖 𝑀𝑖
𝑖

For reacting systems, we may take 𝑥𝑖 to represent either a mole fraction or mass fraction. In
reacting systems, it is nearly always best to work in terms of mole fractions.

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6.2 Fundamental property relation
Previously, the total Gibbs energy of any closed system was related to its canonical variables,
temperature and pressure as:

𝑑(𝑛𝐺) = (𝑛𝑉)𝑑𝑃 − (𝑛𝑆)𝑑𝑇 (6. 1)

where n is the total number of moles of the system. It applies 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)
[ ] = 𝑛𝑉 and [ ] = −𝑛𝑆
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛

The subscript n indicates that the numbers of moles of all chemical species are held constant.

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,
T and P:

𝑛𝐺 = 𝑔(𝑃, 𝑇, 𝑛1 , 𝑛2 , … , 𝑛𝑖 )

where 𝑛𝑖 is the number of moles of species i. The total differential of nG is then:

𝜕(𝑛𝐺) 𝜕(𝑛𝐺) 𝜕(𝑛𝐺)

𝑑(𝑛𝐺) = [ ] 𝑑𝑃 + [ ] 𝑑𝑇 + ∑ [ ] 𝑑𝑛𝑖
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑖 𝑗

The summation is over all species present, and subscript 𝑛𝑗 indicates that all mole numbers
except the ith are held constant. The derivative in the final term is given its own symbol and
name as the chemical potential of species i in the mixture:

𝜕(𝑛𝐺)
𝜇𝑖 = [ ] (6. 2)
𝜕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 + ∑ 𝜇𝑖 𝑑𝑛𝑖 (6. 3)

𝑖

Equation (1.2) is the fundamental property relation for single-phase fluid systems of variable
mass and composition. For the special case of one mole of solution, n = 1 and 𝑛𝑖 = 𝑥𝑖 :

69
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 + ∑ 𝜇𝑖 𝑑𝑥𝑖 (6. 4)
𝑖

Implicit in this equation is the functional relationship of the molar Gibbs energy to its canonical
variables, here: T, P, and {𝑥𝑖 }:

𝐺 = 𝐺(𝑃, 𝑇, 𝑥1 , 𝑥2 , … , 𝑥𝑖 )

6.3 The chemical potential and equilibrium

For a closed, single-phase PVT system containing chemically reactive species, equations (1.1)
and (1.3) must both be valid, the former simply because the system is closed and the second
because of its generality. In addition, for a closed system, all differentials 𝑑𝑛𝑖 in Eq. (1.3) must
result from chemical reaction. Comparison of these two equations shows that they can both be
valid only if:

∑ 𝜇𝑖 𝑑𝑛𝑖 = 0
𝑖

This equation therefore represents a general criterion for chemical-reaction equilibrium in a

single-phase closed PVT system, and is the basis for the development of working equations for
the solution of reaction-equilibrium problems.

With respect to phase equilibrium, we note that for a closed nonreacting system consisting of
two phases in equilibrium, each individual phase is open to the other, and mass transfer between
phases may occur. Equation (1.3) applies separately to each phase:

𝑑(𝑛𝐺)𝛼 = (𝑛𝑉)𝛼 𝑑𝑃 − (𝑛𝑆)𝛼 𝑑𝑇 + ∑ 𝜇𝑖 𝛼 𝑑𝑛𝑖 𝛼

𝑖

𝑑(𝑛𝐺)𝛽 = (𝑛𝑉)𝛽 𝑑𝑃 − (𝑛𝑆)𝛽 𝑑𝑇 + ∑ 𝜇𝑖 𝛽 𝑑𝑛𝑖 𝛽

𝑖

where superscripts α and β identify the phases. For the system to be in thermal and mechanical
equilibrium, T and P must be uniform.

The change in the total Gibbs energy of the two-phase system is the sum of the equations for
the separate phases:

𝑑(𝑛𝐺) = (𝑛𝑉)𝑑𝑃 − (𝑛𝑆)𝑑𝑇 + ∑ 𝜇𝑖 𝛼 𝑑𝑛𝑖 𝛼 + ∑ 𝜇𝑖 𝛽 𝑑𝑛𝑖 𝛽

𝑖 𝑖

where each total-system property is expressed by an equation of the form:

70
 𝑛𝑋 = (𝑛𝑋)𝛼 + (𝑛𝑋)𝛽

Because the two-phase system is closed, Eq. (1.1) is also valid. Comparison of the two
equations shows that at equilibrium:

∑ 𝜇𝑖 𝛼 𝑑𝑛𝑖 𝛼 + ∑ 𝜇𝑖 𝛽 𝑑𝑛𝑖 𝛽 = 0
𝑖 𝑖

The changes 𝑑𝑛𝑖 𝛼 and 𝑑𝑛𝑖 𝛽 result from mass transfer between the phases; mass conservation
therefore requires:

𝑑𝑛𝑖 𝛼 = −𝑑𝑛𝑖 𝛽

∑ 𝜇𝑖 𝛼 𝑑𝑛𝑖 𝛼 − ∑ 𝜇𝑖 𝛽 𝑑𝑛𝑖 𝛼 = 0
𝑖 𝑖

∑(𝜇𝑖 𝛼 − 𝜇𝑖 𝛽 )𝑑𝑛𝑖 𝛼 = 0
𝑖

Quantities 𝑑𝑛𝑖 𝛼 are independent and arbitrary, and 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,

𝜇𝑖 𝛼 = 𝜇𝑖 𝛽

Successive application of this result to pairs of phases permits its generalization to multiple
phases; for π phases:

𝜇𝑖 𝛼 = 𝜇𝑖 𝛽 = ⋯ = 𝜇𝑖 𝜋 (6. 5)

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.

6.4 Partial properties

The definition of the chemical potential by Eq. (1.2) as the mole-number derivative of nG
suggests that other derivatives of this kind may prove useful in solution thermodynamics. Thus,
̅𝑖 of species i in solution as:
we define the partial molar property 𝑀

𝜕(𝑛𝑀)
̅𝑖 = [
𝑀 ] (6. 6)
𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗

71
The partial property 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. Equation
(1.6) yields partial properties from total properties.

The chemical potential and the partial molar Gibbs energy are identical; i.e.,

𝜇𝑖 = 𝐺̅𝑖
Equations Relating Molar and Partial Molar Properties

The partial molar property can be calculated from solution-property data. Similarly, solution
properties can be determined from partial properties. The total thermodynamic properties of a
homogeneous phase are functions of T, P, and the numbers of moles of the individual species
that comprise the phase. Thus for property M, we can write nM as a function:

𝑛𝑀 = 𝕄(𝑃, 𝑇, 𝑛1 , 𝑛2 , … , 𝑛𝑖 )

The total differential of nM is:

𝜕(𝑛𝑀) 𝜕(𝑛𝑀) 𝜕(𝑛𝑀)

𝑑(𝑛𝑀) = [ ] 𝑑𝑃 + [ ] 𝑑𝑇 + ∑ [ ] 𝑑𝑛𝑖
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑖 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. (1.6), this equation has the simpler form:

𝜕𝑀 𝜕𝑀 ̅ 𝑖 𝑑𝑛𝑖
𝑑(𝑛𝑀) = 𝑛 ( ) 𝑑𝑃 + 𝑛 ( ) 𝑑𝑇 + ∑ 𝑀 (6. 7)
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
𝑖

where subscript x denotes differentiation at constant composition. Because 𝑛𝑖 = 𝑥𝑖 𝑛,

𝑑𝑛𝑖 = 𝑑(𝑥𝑖 𝑛) = 𝑥𝑖 𝑑𝑛 + 𝑛 𝑑𝑥𝑖

Moreover,

𝑑(𝑛𝑀) = 𝑛 𝑑𝑀 + 𝑀 𝑑𝑛

Equation (1.7) becomes:

𝜕𝑀 𝜕𝑀 ̅ 𝑖 (𝑥𝑖 𝑑𝑛 + 𝑛 𝑑𝑥𝑖 )
𝑛 𝑑𝑀 + 𝑀 𝑑𝑛 = 𝑛 ( ) 𝑑𝑃 + 𝑛 ( ) 𝑑𝑇 + ∑ 𝑀
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
𝑖

The terms containing n are collected and separated from those containing dn to yield:

72
 𝜕𝑀 𝜕𝑀 ̅ 𝑖 𝑑𝑥𝑖 ] 𝑛 + [𝑀 − ∑ 𝑥𝑖 𝑀
̅ 𝑖 ] 𝑑𝑛 = 0
[𝑑𝑀 − ( ) 𝑑𝑃 − ( ) 𝑑𝑇 − ∑ 𝑀
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
𝑖 𝑖

In application, the system can be any size, as represented by n, and vary by any size, as
represented by dn. Thus, n and dn are independent and arbitrary. The only way that the left side
of this equation can then, in general, be zero is for each term in the square brackets to be zero.
Therefore,

𝜕𝑀 𝜕𝑀 ̅ 𝑖 𝑑𝑥𝑖
𝑑𝑀 = ( ) 𝑑𝑃 + ( ) 𝑑𝑇 + ∑ 𝑀 (6. 8)
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
𝑖

̅𝑖
𝑀 = ∑ 𝑥𝑖 𝑀 (6. 9)
𝑖

This equation yields total properties from partial properties. It shows that the mole-fraction-
weighted sum of the partial molar properties must yield the overall solution property.
Multiplication by n yields the alternative expression:

̅ 𝑖 = ∑ 𝑛𝑖 𝑀
𝑛𝑀 = ∑ 𝑥𝑖 𝑛𝑀 ̅𝑖 (6. 10)
𝑖 𝑖

Equations (1.9) and (1.10) are known as summability relations. They allow the calculation of
mixture properties from partial properties.

Differentiation of Eq. (1.9) yields a general expression for dM:

̅ 𝑖 𝑥𝑖 ) = ∑ 𝑥𝑖 𝑑𝑀
𝑑𝑀 = ∑ 𝑑(𝑀 ̅𝑖 + ∑𝑀
̅ 𝑖 𝑑𝑥𝑖 (6. 11)
𝑖 𝑖 𝑖

Combining this equation with Eq. (1.8) yields:

̅𝑖 + ∑𝑀
̅ 𝑖 𝑑𝑥𝑖 = (
𝜕𝑀 𝜕𝑀 ̅ 𝑖 𝑑𝑥𝑖
𝑑𝑀 = ∑ 𝑥𝑖 𝑑𝑀 ) 𝑑𝑃 + ( ) 𝑑𝑇 + ∑ 𝑀
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
𝑖 𝑖 𝑖

𝜕𝑀 𝜕𝑀
̅𝑖 = ( ) 𝑑𝑃 + ( ) 𝑑𝑇
∑ 𝑥𝑖 𝑑𝑀 (6. 12)
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥
𝑖

Equation (1.12) is known as the Gibbs/Duhem equation. This equation must be satisfied for all
changes occurring in a homogeneous phase. For the important special case of changes in
composition at constant T and P, it simplifies to:

73
 ̅𝑖 = 0
∑ 𝑥𝑖 𝑑𝑀 (const 𝑇, 𝑃) (6. 13)
𝑖

This equation shows that the partial properties of species making up a solution are not
independent of one another and cannot all vary independently. This constraint is analogous to
the constraint on mole fractions, which are not all independent because they must sum to one.

Partial Properties in Binary Solutions

For a binary solution, the summability relation, Eq. (1.9), becomes:

̅1 + 𝑥2 𝑀
𝑀 = 𝑥1 𝑀 ̅2 (𝐴)

Whence,

̅1 + 𝑀
𝑑𝑀 = 𝑥1 𝑑𝑀 ̅1 𝑑𝑥1 + 𝑥2 𝑑𝑀
̅2 + 𝑀
̅2 𝑑𝑥2 (𝐵)

The Gibbs/Duhem equation at constant T and P (eq. 1.13) is then:

̅1 + 𝑥2 𝑑𝑀
𝑥1 𝑑𝑀 ̅2 = 0 (𝐶)

Because 𝑥1 + 𝑥2 = 1, it follows that 𝑑𝑥1 = −𝑑𝑥2 . Eliminating 𝑑𝑥2 from equation (B) yields:

̅1 + 𝑀
𝑑𝑀 = 𝑥1 𝑑𝑀 ̅1 𝑑𝑥1 + 𝑥2 𝑑𝑀
̅2 − 𝑀
̅2 𝑑𝑥1

Using equation (C) to eliminate 𝑥2 yields:

̅1 + 𝑀
𝑑𝑀 = 𝑥1 𝑑𝑀 ̅1 𝑑𝑥1 − 𝑥1 𝑑𝑀
̅1 − 𝑀
̅2 𝑑𝑥1 = 𝑀
̅1 𝑑𝑥1 − 𝑀
̅2 𝑑𝑥1

𝑑𝑀
̅1 − 𝑀
=𝑀 ̅2 (𝐷)
𝑑𝑥1

Eliminating 𝑥1 from equation (A) yields:

̅1 + 𝑥2 𝑀
𝑀 = (1 − 𝑥2 )𝑀 ̅2 = 𝑀
̅1 − 𝑥2 𝑀
̅1 + 𝑥2 𝑀
̅2

̅1 − 𝑥2 (𝑀
𝑀=𝑀 ̅1 − 𝑀
̅2 )

Combining this with equation (D) yields:

𝑑𝑀
̅1 = 𝑀 + 𝑥2
𝑀 (6. 14)
𝑑𝑥1

Eliminating 𝑥2 from equation (A) yields:

̅1 + (1 − 𝑥1 )𝑀
𝑀 = 𝑥1 𝑀 ̅2 = 𝑥1 𝑀
̅1 + 𝑀
̅2 − 𝑥1 𝑀
̅2

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 ̅1 − 𝑀
𝑀 = 𝑥1 (𝑀 ̅2 ) + 𝑀
̅2

Combining this with equation (D) yields:

𝑑𝑀
̅2 = 𝑀 − 𝑥1
𝑀 (6. 15)
𝑑𝑥1

Equation (1.14 and 1.15) shows that, for binary systems, the partial properties can be calculated
directly from the solution property as a function of composition at constant T and P.

Equation (C), the Gibbs/Duhem equation, may be written in derivative forms:

̅1
𝑑𝑀 ̅2
𝑑𝑀
𝑥1 + 𝑥2 =0 (𝐸)
𝑑𝑥1 𝑑𝑥1

̅1
𝑑𝑀 ̅2
𝑥2 𝑑𝑀
=− (𝐹)
𝑑𝑥1 𝑥1 𝑑𝑥1

Example 1.1
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:

Methanol (1): 𝑉̅1 = 38.632 cm3 ⋅ mol−1 𝑉1 = 40.727 cm3 ⋅ mol−1

Water (2): 𝑉̅2 = 17.765 cm3 ⋅ mol−1 𝑉2 = 18.068 cm3 ⋅ mol−1

Solution 1.1
Molar volume of the binary antifreeze solution:

𝑉 = 𝑥1 𝑉̅1 + 𝑥2 𝑉̅2 = (0.3)(38.632) + (0.7)(17.765) = 24.025 cm3 ⋅ mol−1

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

𝑉𝑡 2000
𝑛= = = 83.246 mol
𝑉 24.025

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

𝑛1 = (0.3)(83.246) = 24.974 mol

𝑛2 = (0.7)(83.246) = 58.272 mol

75
The volume of each pure species is 𝑉𝑖𝑡 = 𝑛𝑖 𝑉𝑖 ; thus,

𝑉1𝑡 = (24.974)(40.727) = 1017 cm3

𝑉2𝑡 = (58.272)(18.068) = 1053 cm3

Example 1.2
The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is represented by the
equation:
𝐻 = 400𝑥1 + 600𝑥2 + 𝑥1 𝑥2 (40𝑥1 + 20𝑥2 )
where H is in J·mol–1. Determine expressions for 𝐻
̅1 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
̅1∞ and 𝐻
infinite dilution 𝐻 ̅2∞ .

Solution 1.2

Replacing x2 by 1 – x1 in the given equation for H gives:

𝐻 = 400𝑥1 + 600(1 − 𝑥1 ) + 40𝑥12 (1 − 𝑥1 ) + 20𝑥1 (1 − 𝑥1 )(1 − 𝑥1 )

𝐻 = 400𝑥1 + 600 − 600𝑥1 + 40𝑥12 − 40𝑥13 + 20𝑥1 (1 − 2𝑥1 + 𝑥12 )

𝐻 = 400𝑥1 + 600 − 600𝑥1 + 40𝑥12 − 40𝑥13 + 20𝑥1 − 40𝑥12 + 20𝑥13 )

𝐻 = 600 − 180𝑥1 − 20𝑥13 (𝐴)

and
𝑑𝐻
= −180 − 60𝑥12
𝑑𝑥1

From equation (1.14):

𝑑𝐻
̅1 = 𝐻 + 𝑥2
𝐻
𝑑𝑥1

̅1 = 600 − 180𝑥1 − 20𝑥13 + 𝑥2 (−180 − 60𝑥12 )

𝐻

̅1 = 600 − 180𝑥1 − 20𝑥13 − 180𝑥2 − 60𝑥12 𝑥2

𝐻

̅1 = 600 − 180𝑥1 − 20𝑥13 − 180(1 − 𝑥1 ) − 60𝑥12 (1 − 𝑥1 )

𝐻

̅1 = 600 − 180𝑥1 − 20𝑥13 −180 + 180𝑥1 − 60𝑥12 + 60𝑥13

𝐻

̅1 = 420 − 60𝑥12 + 40𝑥13

𝐻 (𝐵)

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From equation (1.15):

𝑑𝐻
̅2 = 𝐻 − 𝑥1
𝐻
𝑑𝑥1

̅2 = 600 − 180𝑥1 − 20𝑥13 − 𝑥1 (−180 − 60𝑥12 )

𝐻

̅2 = 600 − 180𝑥1 − 20𝑥13 + 180𝑥1 + 60𝑥13

𝐻

̅2 = 600 + 40𝑥13
𝐻 (𝐶)

A numerical value for 𝐻1 results by substitution of 𝑥1 = 1 in Eq. (A):

𝐻1 = 600 − 180 − 20 = 400 J · mol–1

Similarly, 𝐻2 is found from Eq. (A) when 𝑥1 = 0:

𝐻2 = 600 J · mol–1

̅1∞ and 𝐻
The infinite-dilution values 𝐻 ̅2∞ are found from Eqs. (B) and (C) when 𝑥1 = 0 in Eq.
(B) and 𝑥1 = 1 in Eq. (C):

̅1∞ = 420 J · mol–1

𝐻

̅2∞ = 600 + 40 = 640 J · mol–1

𝐻

Relations among partial properties

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 solution.

For example, 𝐻 = 𝑈 + 𝑃𝑉 which for n moles becomes 𝑛𝐻 = 𝑛𝑈 + 𝑃(𝑛𝑉)

Differentiation with respect to 𝑛𝑖 at constant P, T and 𝑛𝑗 .

𝜕(𝑛𝐻) 𝜕(𝑛𝑈) 𝜕(𝑛𝑉)

[ ] =[ ] +𝑃[ ]
𝜕𝑛𝑖 𝑃,𝑇,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗 𝑗 𝑗

By the definition of partial properties, this becomes:

̅𝑖 = 𝑈
𝐻 ̅𝑖 + 𝑃𝑉̅𝑖

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This illustrates the parallelism between equations of constant-composition and those for the
partial properties of the species in solution. Many equations that relate partial properties can be
written by analogy.

6.5 The ideal-gas-state mixture model

Molar volumes in the ideal-gas state are 𝑉 𝑖𝑔 = 𝑅𝑇⁄𝑃 regardless of the nature of the gas. Thus,
for the ideal-gas state, whether of pure or mixed gases, the molar volume is the same for given
T and P. The partial molar volume of species i in the ideal-gas-state mixture is:

𝑖𝑔 𝜕(𝑛𝑉 𝑖𝑔 ) 𝜕(𝑛 𝑅𝑇⁄𝑃) 𝑅𝑇 𝜕𝑛 𝑅𝑇 𝜕(𝑛𝑖 + ∑𝑗 𝑛𝑗 ) 𝑅𝑇

̅
𝑉𝑖 = [ ] =[ ] = [ ] = [ ] =
𝜕𝑛𝑖 𝑇,𝑃,𝑛 𝜕𝑛𝑖 𝑇,𝑃,𝑛
𝑃 𝜕𝑛𝑖 𝑛 𝑃 𝜕𝑛𝑖 𝑛
𝑃
𝑗 𝑗 𝑗 𝑗

This result means that for the ideal-gas state at given T and P, the partial molar volume, the
pure-species molar volume, and the mixture molar volume are identical:

𝑖𝑔 𝑖𝑔 𝑅𝑇
𝑉̅𝑖 = 𝑉𝑖 = 𝑉 𝑖𝑔 = (6. 16)
𝑃

We define the partial pressure of species i in the ideal-gas-state mixture (pi) as the
pressure that species i would exert if it alone occupied the molar volume of the mixture. Thus,

𝑦𝑖 𝑅𝑇
𝑝𝑖 = = 𝑦𝑖 𝑃 (𝑖 = 1,2, … 𝑁)
𝑉 𝑖𝑔

where 𝑦𝑖 is the mole fraction of species i. The partial pressures obviously sum to the total
pressure.

Gibbs theorem states that a partial molar property (other than volume) of a constituent species
in an ideal-gas-state mixture is equal to the corresponding molar property of the species in the
pure ideal-gas state at the mixture temperature but at a pressure equal to its partial pressure in
the mixture.

̅𝑖𝑖𝑔 ≠ 𝑉̅𝑖 𝑖𝑔
For a generic partial property, 𝑀

̅𝑖𝑖𝑔 (𝑇, 𝑃) = 𝑀𝑖𝑖𝑔 (𝑇, 𝑝𝑖 )

𝑀 (6. 17)

Enthalpy is independent of pressure, therefore:

̅𝑖𝑖𝑔 (𝑇, 𝑃) = 𝐻𝑖𝑖𝑔 (𝑇, 𝑝𝑖 ) = 𝐻𝑖𝑖𝑔 (𝑇, 𝑃)

𝐻

More simply,

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̅ 𝑖𝑔 = 𝐻 𝑖𝑔
𝐻 (6. 18)
𝑖 𝑖

𝑖𝑔
where 𝐻𝑖 is the pure-species value at the mixture T.

Unlike enthalpy, entropy in the ideal-gas state depends on pressure. The relation for entropy of
an ideal gas was derived previously as:

𝑖𝑔 𝑑𝑇 𝑑𝑃
𝑑𝑆 𝑖𝑔 = 𝐶𝑃 −𝑅
𝑇 𝑃

At constant temperature:

𝑑𝑃
𝑑𝑆 𝑖𝑔 = −𝑅 (const T)
𝑃

This provides the basis for computing the entropy difference between a gas at its partial
pressure in the mixture and at the total pressure of the mixture. Integration from 𝑝𝑖 to P gives:

𝑖𝑔
𝑆𝑖 (𝑇,𝑃) 𝑃
𝑖𝑔 𝑑𝑃
∫ 𝑑𝑆𝑖 = −𝑅 ∫
𝑖𝑔
𝑆𝑖 (𝑇,𝑝𝑖 ) 𝑝𝑖 𝑃

𝑖𝑔 𝑖𝑔
𝑆𝑖 (𝑇, 𝑃) − 𝑆𝑖 (𝑇, 𝑝𝑖 ) = −𝑅[ln 𝑃]𝑃𝑝𝑖 = −𝑅[ln 𝑃 − ln 𝑝𝑖 ] = 𝑅[ln 𝑝𝑖 − ln 𝑃]

𝑖𝑔 𝑖𝑔 𝑝𝑖 𝑦𝑖 𝑃
𝑆𝑖 (𝑇, 𝑃) − 𝑆𝑖 (𝑇, 𝑝𝑖 ) = 𝑅 ln = 𝑅 ln = 𝑅 ln 𝑦𝑖
𝑃 𝑃

Whence,

𝑖𝑔 𝑖𝑔
𝑆𝑖 (𝑇, 𝑝𝑖 ) = 𝑆𝑖 (𝑇, 𝑃) − 𝑅 ln 𝑦𝑖

Or,

𝑖𝑔 𝑖𝑔
𝑆𝑖̅ (𝑇, 𝑃) = 𝑆𝑖 (𝑇, 𝑃) − 𝑅 ln 𝑦𝑖

Which can be simplified to:

𝑖𝑔 𝑖𝑔
𝑆𝑖̅ = 𝑆𝑖 − 𝑅 ln 𝑦𝑖 (6. 19)

𝑖𝑔
where 𝑆𝑖 is the pure-species value at the mixture T and P.

For the Gibbs energy in the ideal-gas-state mixture, 𝐺 𝑖𝑔 = 𝐻 𝑖𝑔 + 𝑇𝑆 𝑖𝑔 ; the relation for partial
properties is:

𝑖𝑔 ̅𝑖𝑖𝑔 − 𝑇𝑆𝑖̅ 𝑖𝑔
𝐺𝑖̅ = 𝐻

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This becomes:

𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔
𝐺𝑖̅ = 𝐻𝑖 − 𝑇(𝑆𝑖 − 𝑅 ln 𝑦𝑖 ) = 𝐻𝑖 − 𝑇𝑆𝑖 + 𝑅𝑇 ln 𝑦𝑖

Or,

𝑖𝑔 𝑖𝑔 𝑖𝑔
𝜇𝑖 = 𝐺𝑖̅ = 𝐺𝑖 + 𝑅𝑇 ln 𝑦𝑖 (6. 20)

The summability relation, Eq. (1.9), with Eqs. (1.18), (1.19), and (1.20) yields:

𝑖𝑔
𝐻 𝑖𝑔 = ∑ 𝑦𝑖 𝐻𝑖 (6. 21)
𝑖

𝑖𝑔
𝑆 𝑖𝑔 = ∑ 𝑦𝑖 𝑆𝑖 − 𝑅 ∑ 𝑦𝑖 ln 𝑦𝑖 (6. 22)
𝑖 𝑖

𝑖𝑔
𝐺 𝑖𝑔 = ∑ 𝑦𝑖 𝐺𝑖 + 𝑅𝑇 ∑ 𝑦𝑖 ln 𝑦𝑖 (6. 23)
𝑖 𝑖

Eq. (1.21) can be written as:

𝑖𝑔
𝐻 𝑖𝑔 − ∑ 𝑦𝑖 𝐻𝑖 = 0
𝑖

the difference on the left is the enthalpy change associated with a mixing process at constant T
and P. For the ideal-gas state, this enthalpy change of mixing is zero.

Eq. (1.22) can be rearranged as:

𝑖𝑔 1
𝑆 𝑖𝑔 − ∑ 𝑦𝑖 𝑆𝑖 = 𝑅 ∑ 𝑦𝑖 ln
𝑦𝑖
𝑖 𝑖

the left side is the entropy change of mixing for the ideal-gas state. Because 1⁄𝑦𝑖 > 1, this
quantity is always positive, in agreement with the second law. The mixing process is inherently
irreversible, so the mixing process must increase the total entropy of the system and
surroundings together.

An alternative expression for the chemical potential, can be found as shown next. The
fundamental relation for Gibbs energy was expressed as:

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

At constant T for ideal gas in a mixture:

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 𝑖𝑔 𝑖𝑔 𝑅𝑇 𝑑𝑃
𝑑𝐺𝑖 = 𝑉𝑖 𝑑𝑃 = 𝑑𝑃 = 𝑅𝑇 (const T)
𝑃 𝑃

Integrating:

𝑖𝑔 𝑑𝑃
∫ 𝑑𝐺𝑖 = 𝑅𝑇 ∫
𝑃

𝑖𝑔
𝐺𝑖 = Γ𝑖 (𝑇) + 𝑅𝑇 ln 𝑃 (6. 24)

where Γ𝑖 (𝑇), the integration constant at constant T, is a species-dependent function of

temperature only. Equation (1.20) is now written:

𝑖𝑔 𝑖𝑔
𝜇𝑖 = 𝐺𝑖̅ = Γ𝑖 (𝑇) + 𝑅𝑇 ln 𝑃 + 𝑅𝑇 ln 𝑦𝑖 = Γ𝑖 (𝑇) + 𝑅𝑇(ln 𝑃 + ln 𝑦𝑖 )

𝑖𝑔 𝑖𝑔
𝜇𝑖 = 𝐺𝑖̅ = Γ𝑖 (𝑇) + 𝑅𝑇 ln(𝑦𝑖 𝑃) (6. 25)

Application of the summability relation, Eq. (1.9), produces an expression for the Gibbs energy
for the ideal-gas-state mixture:

𝐺 𝑖𝑔 = ∑ 𝑦𝑖 Γ𝑖 (𝑇) + 𝑅𝑇 ∑ 𝑦𝑖 ln(𝑦𝑖 𝑃) (6. 26)

𝑖 𝑖

These simple equations provide a full description of the ideal-gas-state behaviour.

81