THERMODYNAMIC

PROPERTIES OF
FLUID
PROPERTY RELATIONS FOR HOMOGENEOUS PHASE

The first law for a closed For the special case of a

system of n moles is: reversible process,

Equations from previous chapters are here written:

Together, these equations give:

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

and volume. This equation, combining the first and second laws, is
derived for the special case of a reversible process.
THERMODYNAMIC
DIAGRAMS AND
TABLES
A thermodynamic diagram is a graph showing for a particular
substance a set of properties. The most common diagrams
are: TS, PH (usually ln P vs. H) and HS (called a Mollier
diagram).

In many instances thermodynamic properties are tabulated.

This has the advantage that data can be represented more
precisely than in diagrams, but the need for interpolation is
introduced. The steam tables are the most thorough
compilation of properties for any single material. However,
tables are available for a number of other substances.
Thermodynamic diagrams usually show
a net of five different lines:
■ Isobars - lines of constant pressure
■ Isotherms – lines of constant temperature
■ Dry adiabats – lines of constant potential temperature representing
the temperature of a rising parcel of dry air
■ Saturated adibats or pseudoadiabats – lines representing the
temperature of a rising parcel saturated with water vapour
■ Mixing ratio – lines representing the dew point of a rising parcel
PITZER CORRELATIONS
FOR SECOND VIRIAL
COEFFICIENT
 ■ Pitzer Correlations for Second Virial
Coefficient
■ The generalized compressibility-factor
correlation gave approximate analysis
expressions for limited range of pressures.
𝐵𝑃 𝑃𝑟
𝑍 = 1+ =1+Ḃ
𝑅𝑇 𝑇𝑟
𝐵𝑃𝑐
Ḃ=
𝑅𝑇𝑐

𝐵𝑃𝑐
= 𝐵° + 𝜔𝐵1
𝑅𝑇𝑐
𝑃𝑟 𝑃𝑟
𝑍 =1+𝐵 °
+ 𝜔𝐵 1 Perry’s HB Eq. 4-73
𝑇𝑟 𝑇𝑟
Since B, B⁰, and B1 are functions of T
only
𝐻𝑅 𝑃 𝑑𝐵
= 𝐵 − 𝑇𝑟
𝑅 𝑅 𝑑𝑇𝑟
𝑆𝑅 𝑃 𝑑𝐵
=
𝑅 𝑅𝑇𝑐 𝑑𝑇𝑟
■ Dependence to Temperature

0.422
𝐵° = 0.083 − 1.6 Perry’s HB Eq. 4-77
𝑇𝑟

1
0.179
𝐵 = 0.139 − Perry’s HB Eq. 4-78
𝑇𝑟 4.2