Page 254 - Characterization and Properties of Petroleum Fractions - M.R. Riazi

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234 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
α, β
Value of a property for phase α or phase β
∞ Value of a property for i in the liquid solution at IN CHAPTER 5 THE PVT relations and theory of intermolecu-
lar forces were discussed. The PVT relations and equations of
infinite dilution as x i → 0 states are the basis of property calculations as all physical and
◦ Value of a property at standard state, usually the thermodynamic properties can be related to PVT properties.
standard state is chosen at pure component at T In this chapter we review principles and theory of property
and P of the mixture according to the estimation methods and basic thermodynamic relations that
Lewis/Randall rule will be used to calculate physical and thermodynamic prop-
Value of molar property of a component in the erties.
∧
mixture The PVT relations and equations of state are perhaps the
most important thermodynamic relations for pure fluids and
their mixtures. Once the PVT relation is known, various phys-
Subscripts ical and thermodynamic properties needed for design and op-
eration of units in the petroleum and related industries can be
c Value of a property at the critical point
i A component in a mixture calculated. Density can be directly calculated from knowledge
j A component in a mixture of molar volume or compressibility factor through Eq. (5.15).
i, j Effect of binary interaction on a property Various thermodynamic properties such heat capacity, en-
m Value of a property for a mixture thalpy, vapor pressure, phase behavior and vapor liquid equi-
mix Change in value of a property due to mixing at librium (VLE), equilibrium ratios, intermolecular parame-
constant T and P ters, and transport properties all can be calculated through
PR Value of a property determined from PR EOS accurate knowledge of PVT relation for the fluid. Some of
SRK Value of a property determined from SRK EOS these relations are developed in this chapter through funda-
mental thermodynamic relations. Once a property is related
to PVT, using an appropriate EOS, it can be estimated at any
temperature and pressure for pure fluids and fluid mixtures.
Acronyms
Development of such important relations is discussed in this
API-TDB American Petroleum Institute—Technical Data chapter, while their use to estimate thermophysical properties
Book for petroleum mixtures are discussed in the next chapter.
BIP Binary interaction parameter
bbl Barrel, unit of volume of liquid as given in Section
1.7.11 6.1 DEFINITIONS AND FUNDAMENTAL
CS Carnahan–Starling EOS (see Eq. 5.93) THERMODYNAMIC RELATIONS
DIPPR Design Institute for Physical Property Data
EOS Equation of state In this section, thermodynamic properties such as entropy,
GC Generalized correlation Gibbs energy, heat capacity, residual properties, and fugacity
GD Gibbs–Duhem equation (see Eq. 6.81) are defined. Thermodynamic relations that relate these prop-
HS Hard sphere erties to PVT relation of pure fluids are developed.
HSP Hard sphere potential given by Eq. (5.13)
IAPWS International Association for the Properties of 6.1.1 Thermodynamic Properties and
Water and Steam Fundamental Relations
LJ Lennard–Jones potential given by Eq. (5.11)
LJ EOS Lennard–Jones EOS given by Eq. (5.96) Previously two thermodynamic properties, namely internal
LK EOS Lee–Kesler EOS given by Eq. (5.104) energy (U) and enthalpy (H), were defined in Section 5.1.
LLE Liquid–liquid equilibria The enthalpy is defined in terms of U and PV (Eq. 5.5) as
NIST National Institute of Standards and Technology (6.1) H = U + PV
PVT Pressure–volume–temperature
PR Peng–Robinson EOS (see Eq. 5.39) Another thermodynamic property that is used to formulate
RHS Right-hand side of an equation the second law of thermodynamics is called entropy and it is
RK Redlich–Kwong EOS (see Eq. 5.38) defined as
SRK Soave–Redlich–Kwong EOS given by Eq. (5.38) δQ rev
and parameters in Table 5.1 (6.2) dS = T
SAFT Statistical associating fluid theory (see
Eq. 5.98) where S is the entropy and δQ rev is the amount of heat trans-
SLE Solid–liquid equilibrium ferred to the system at temperature T through a reversible
SLVE Solid–liquid–vapor equilibrium process. The symbol δ is used for the differential heat Q to
VLE Vapor–liquid equilibrium indicate that heat is not a thermodynamic property such as
VLS Vapor–liquid–solid equilibrium H or S. The unit of entropy is energy per absolute degrees, e.g.
VS Vapor–solid equilibrium J/K, or on a molar basis it has the unit of J/mol · K in the SI
%AAD Average absolute deviation percentage defined by unit system. The first law of thermodynamics is derived based
--`,```,`,``````,`,````,```,,-`-`,,`,,`,`,,`---
Eq. (2.135) on the law of conservation of energy and for a closed system
%AD Absolute deviation percentage defined by (constant composition and mass) is given as follows [1, 2]:
Eq. (2.134) (6.3) dU = δQ − PdV

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