Thermodynamic Third class

Chapter 6
Thermodynamic Properties of Fluids

Initial purpose in this chapter is to develop from the first and second laws the fundamental
property relations which underlie the mathematical structure of thermodynamics. From these,
we derive equations which allow calculation of enthalpy and entropy values from PVT and
heat-capacity data. We then discuss the diagrams and tables by which property values are
presented for convenient use. Finally, we develop generalized correlations which provide
estimates of property values in the absence of complete experimental information.

6.1 PROPERTY RELATIONS FOR HOMOGENEOUS PHASES

The first law for a closed system of n moles is:

For the special case of a reversible process,

Equations (1.2) and (5.12) are here written:

Together these three equations give:

where U, S, and V are molar values of the internal energy, entropy, and volume.

In Chap. 2 the enthalpy was defined as a matter of convenience by the equation:

Two additional properties, also defined for convenience, are the Helmholtz energy,

and the Gibbs energy,

Each of these defined properties leads directly to an equation like Eq. (6.1). Upon
multiplication by n, Eq. (2.11) becomes:

Differentiation gives:

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When d(nU) is replaced by Eq. (6. 1), this reduces to:

Similarly, from Eq. (6.2),

Eliminating d(nU) by Eq. (6.1) gives:

In analogous fashion, Eqs. (6.3) and (6.4) combine to yield:

Equations (6.4) through (6.6) are subject to the same restrictions as Eq. (6.1). All are written
for the entire mass of any closed system.

Immediate application of these equations is to one mole (or to a unit mass) of a homogeneous
fluid of constant composition. For this case, they simplify to:

These fundamental property relations are general equations for a homogeneous fluid of
constant composition.

The thermodynamic properties U, H, A, and G are known to be functions of the variables on

the right sides of Eqs. (6.7) through (6.10); we may therefore write the relationship expressed
for each of these equations:

These are Maxwell's equations.

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Enthalpy and Entropy as Functions of T and P:

Consider first the temperature derivatives. Equation (2.20) defines the heat capacity at
constant pressure:

Another expression for this quantity is obtained by division of Eq. (6.8) by dT and restriction
of the result to constant P

Combination of this equation with Eq. (2.20) gives:

The pressure derivative of the entropy results directly from Eq. (6.16):

The corresponding derivative for the enthalpy is found by division of Eq. (6.8) by dP and
restriction to constant T:

As a result of Eq. (6.18) this becomes:

The functional relations chosen here for H and S are:

whence

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The partial derivatives in these two equations are given by Eqs. (2.20) and (6.17) through (6.19):

These are general equations relating the properties of homogeneous fluids of constant
composition to temperature and pressure.

The Ideal-Gas State:

The coefficients of dT and dP in Eqs. (6.20) and (6.21) are evaluated from heat-capacity and
PVT data. The ideal-gas state provides an example of PVT behavior:

Substituting these equations into Eqs. (6.20) and (6.21) reduces them to:

where superscript "ig" denotes an ideal-gas value. These are merely restatements of equations for
ideal gases presented in Secs. 3.3 and 5.

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6.2 RESIDUAL PROPERTIES:

Unfortunately, no experimental method for the direct measurement of numerical values of G or G/RT is known, and the
equations which follow directly from the Gibbs energy are of little practical use. Thus, by definition the residual Gibbs
energy is:

where G and Gig are the actual and the ideal-gas values of the Gibbs energy at the same temperature and pressure. Other
residual properties are defined in an analogous way. The residual volume, for example, is:

Since V = ZRT/P, the residual volume and the compressibility factor are related:
The definition for the generic residual property is:

where M is the molar value of any extensive thermodynamic property, e.g., V, U, H, S, or G. Note that M and M ig, the
actual and ideal-gas properties, are at the same temperature and pressure.

Enthalpy and Entropy from residual properties

Applied to the enthalpy and entropy, Eq. (6.41) is written:

Thus, H and S follow from the corresponding ideal-gas and residual properties by simple addition. General expressions
for Hig and Sig are found by integration of Eqs. (6.23) and (6.24) from an ideal-gas state at reference conditions
To and Po to the ideal-gas state at T and P

Substitution into the preceding equations gives:

Equations (6.50) and (6.51) may be expressed alternatively to include the mean heat capacities introduced
in Secs. 4.1 and 5.5:

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6.3 TWO-PHASE SYSTEMS

The exception is the molar or specific Gibbs energy, which for a pure species does not change during a phase transition
such as melting, vaporization, or sublimation. Consider a pure liquid in equilibrium with its vapor in a piston/
cylinder arrangement at temperature T and the corresponding vapor pressure P sat. When a differential amount of
liquid is caused to evaporate at constant temperature and pressure, Eq. (6.6) applied to the process reduces to
d(nG) = 0. Since the number of moles n is constant, dG = 0, and this requires the molar (or specific) Gibbs energy
of the vapor to be identical with that of the liquid. More generally, for two phases , and β of a pure species coexisting
at equilibrium,

where Gα and Gβ are the molar or specific Gibbs energies of the individual phases. If the temperature of a two-phase
system is changed, then the pressure must also change in accord with the relation between vapor pressure and temperature
if the two phases continue to coexist in equilibrium. Since Eq. (6.69) applies throughout this change,

Substituting expressions for dGα and dGβ as given by Eq. (6.10) yields:

which upon rearrangement becomes:

The entropy change ΔSαβ and the volume change ΔVαβ are changes which occur when a unit amount of a pure chemical
species is transferred from phase α to phase β at the equilibrium temperature and pressure. Integration of Eq. (6.8) for this change
yields the latent heat of phase transition:

Thus, ΔSαβ = ΔHαβ / T, and substitution in the preceding equation gives:

which is the Clapeyron equation.

For the particularly important case of phase transition from liquid l to vapor v, Eq. (6.71) is written:

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Where ΔZlv is the compressibility factor change of vaporization, combination of last two equations gives on rearrangement

Equations (6.72) through (6.74) are equivalent, exact forms of the Clapeyron equation for pure species vaporization

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