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Thermodynamics and Phase Behavior

Phase behavior describes the complex interaction between physically distinct,
separable portions of matter called phases that are in contact with each other.
Typical phases are solids, liquids, and vapors. Phase behavior plays a vital role in
many petroleum applications, such as enhanced oil recovery, compositional
simulation, geochemical behavior, wellbore stability, geothermal energy,
environmental cleanup, multiphase flow in wellbores and pipes, and surface
facilities.
Thermodynamics, which is central to understanding phase behavior, is the study of
energy and its transformations. Using thermodynamics, we can follow the energy
changes that occur during phase changes and predict the outcome of a process.
Thermodynamics began as the study of heat applied to steam power but was
substantially broadened by Gibbs in the middle to late 1800s. Gibbs most
significant contribution was the development of phase-equilibrium thermodynamics
applied to multicomponent mixtures, particularly the concept of chemical potential.
[1] The concept of chemical potential leads to the result that, at equilibrium, the
chemical potential of each component must be the same in all phases (iL = iV).
Phase-equilibrium thermodynamics seeks to determine properties such as
temperature, pressure, and phase compositions that establish themselves once all
tendencies for further change have disappeared. This chapter reviews the
fundamentals of phase-equilibrium thermodynamics used in petroleum applications,
especially those that require liquid-vapor phase behavior.

Fig. 7.1 is a schematic showing a closed container of liquid and vapor. Given constant and known temperature,
pressure, and overall compositions (zi where i = 1, , nc) at equilibrium, the fundamental task is to quantify the molar
fractions of the phases (L, V) and compositions of the vapor (yi where i = 1, , nc) and liquid phases (xi where i = 1,
, nc) that form at equilibrium. The phases are assumed to be homogeneous, in which intensive parameters such as
pressure, temperature, density, viscosity, and phase compositions are uniform throughout the phase. (Thus, gravity
effects are not typically considered.) Intensive properties are those that are independent of the amount of the phases
(e.g., phase density, pressure, and temperature). Alternatively, extensive properties depend on the amount of the

phases (e.g., total volume and moles of liquid). Intensive properties can be determined as the ratio of two extensive
properties; for example, molar density is the number of moles divided by the total volume.
he overall compositions and phase compositions in Fig. 7.1 are written as mole fractions, which are defined by

and

where
amounts

of

for the container,

the
phases

are

for liquid, and

defined
by
the

phase

for vapor. The relative

mole
fractions,

and

where L + V = 1. The phase molar fractions are not saturations, although they could be converted to saturations from
the phase densities. The molar fractions of the phases are related to the overall and phase compositions by

....................(7.1)
Thus, once the overall compositions and phase compositions are known, the phase molar fractions, L and V, are also
known.

Gibbs Phase Rule and Duhems Theorem

The Gibbs phase rule and Duhems theorem assure us that the problem illustrated in Fig. 7.1 can be solved. Ideas
and theories from thermodynamics are based on observations. Gibbs, for example, observed that the equilibrium
intensive state of the system is fully known once the pressure, temperature, and phase compositions are specified.
The number of intensive properties that we would like to know is, therefore, 2 + ncnp, where np is the number of
phases (for vapor/liquid equilibrium, np is two). These intensive properties can only be determined if a sufficient
number of equations are available or if some of them are explicitly specified. An inventory of equations shows that
there are np summation equations (i.e., the phase mole fractions for each phase sum to 1.0) and nc(np - 1) equilibrium
relations, for a total of np + nc(np - 1) equations. The equilibrium relations could be given as K-values
which relate the component liquid and vapor mole fractions or, as described later, chemical potential criteria for
equilibrium (i.e., iL = iV).

The Gibbs phase rule says that the degrees of freedom are 2 + nc - np, which is the difference between the number of
required intensive properties (unknowns) and the number of relations (equations). The Gibbs phase rule is only
practically useful for a small number of components but does offer significant insight into the maximum number of
phases that can form as well as how many intensive properties can be independently specified.
For example, suppose that only one phase (np = 1) is present at equilibrium in a system containing a pure fluid (nc =
1). The Gibbs phase rule says that only two intensive properties can be specified (degrees of freedom are two). We
cannot specify three or more intensive properties for this case, but we are free to choose which intensive properties
are set. Typically, we would choose temperature and pressure. The choice of intensive properties is not completely
arbitrary, for only properties related to an individual phase can be selected. Thus, properties such as the overall
density of the two-phase system or the phase molar fractions, L and V, cannot be used to reduce the degrees of
freedom.
Suppose next that three equilibrium phases exist in the pure fluid (i.e., the triple point). For this case, the degrees of
freedom are zero, and no intensive properties can be specified. That is, the intensive properties, such as temperature
and pressure, are determined and are not arbitrary at the triple point. Four phases in equilibrium with each other are
not allowed by the Gibbs phase rule (neither are they observed experimentally).
Duhems theorem is another rule, similar to the phase rule, but it specifies when both the extensive and intensive
states of the system are determined. The theorem states that for any closed system containing specified moles
of nc components (from which the overall compositions can be calculated), the equilibrium state is completely
determined when any two independent properties are fixed. The two independent properties may be either intensive
or extensive; however, the maximum number of independent intensive properties that can be specified is given by the
Gibbs phase rule. For example, when the degrees of freedom are one, at least one of the two variables must be
extensive. When the degrees of freedom are zero, both must be extensive. Thus, the combination of the Gibbs phase
rule and Duhems theorem shows that the extensive and intensive state of the two-phase problem in Fig. 7.1 can be
determined when the temperature, pressure, and moles of all the components are specified. For a pure component
system, the intensive and extensive state of the system is determined when the temperature, pressure, and the total
number of moles are given.

Equilibrium, Stability, and Reversible Thermodynamic Systems

Thermodynamics is a macroscopic viewpoint in that it concerns itself with the properties of a system, such as
temperature and density. Thermodynamics predicts the nature of a new equilibrium statenot the rate at which that
state is reached. One of the characteristics of equilibrium is that the thermodynamic properties are time invariant.
Furthermore, once equilibrium is reached, the process or pathway that led to equilibrium cannot be determined.
The equilibrium state is always time invariant, whether it is dynamic or static. A dynamic equilibrium process is a
steady-state process, in which the properties change spatially but not temporally. A static process, while having the
appearance of reaching a static state on a macroscopic scale (such as that shown in Fig. 7.1), is anything but static
on a microscopic scale. Molecules from the liquid phase continue to move into the vapor phase and vice versa, but
the rates of energy and mass transfer are equal, giving the appearance of equilibrium on a macroscopic scale.
Indeed, this is exactly the definition for equilibrium embodied by the chemical potential criterion iL= iV.
The criterion of time invariance is a necessary, but not sufficient, condition for equilibrium. Some systems can exist in
metastable states that are time invariant. For example, at the Earths surface, diamonds are in a metastable state of
pure carbon, whereas graphite is the equilibrium state. Fig. 7.2 illustrates the concept of equilibrium vs. metastable or
unstable (nonequilibrium) states by considering a ball rolling down a hill into a valley. When the ball is on the side of
the hill, it is unstable and will roll down the slope because of gravitational forces; this is an unstable process. The ball,
however, if initially trapped in a small depression on the side of the hill, will not roll down the hill; this is a metastable

state. Lacking any additional energy, the ball will stay in the metastable position. If the depression is removed, or the
ball is slightly moved, the ball will roll down the hill until it reaches the lowest position, which corresponds to the
lowest gravitational potential energy or equilibrium position.

Fig. 7.2 Potential states of a system illustrated by a ball rolling down a hill.

Later on, we will find that a definition for equilibrium is when the Gibbs free energy of the system is the lowest value
possible, and this is how one can recognize unstable or metastable states from the true equilibrium. Generally,
equilibrium states that arise naturally are stable to small disturbances. On the flip side, metastable equilibrium states,
which are not stable to small disturbances, do not occur often in nature. Our mathematical description of equilibrium,
however, will exhibit these unstable and metastable states, so we must be able to recognize them.
Processes of interest to us are often not time invariant, and it would appear that equilibrium thermodynamics is not
very useful. For example, we typically run transient simulations to estimate the recovery of reservoir oil by injection of
a gas. The concept of local equilibrium and reversibility are used to overcome this apparent limitation of
thermodynamics. Equilibrium at a point in a reservoir, termed local equilibrium, often applies when internal relaxation
processes are rapid with respect to the rate at which changes are imposed on the system. That is, equilibrium
thermodynamics can be applied over small volumes of the reservoir, even though pressure and other gradients
remain in the reservoir. In reservoir simulation, the small volumes are gridblocks, although the size of the gridblocks
must
be
sufficiently
small
so
that
good
accuracy
is
obtained.
The concept of reversibility of a process is also important. A reversible process proceeds in sufficiently small steps so
that it is essentially in equilibrium at any given time (i.e., the process at a point in the reservoir proceeds in a
succession of local equilibrium steps). A process is reversible when its direction can be reversed at any point by an
infinitesimal
change
in
external
conditions.
The concept of reversibility is, in a sense, the temporal equivalent to the spatial concept of local equilibrium. Thus, the
concepts of local equilibrium and reversibility allow the application of equilibrium thermodynamics to real systems,
which are invariably nonequilibrium at large scales. For most cases, very little accuracy is lost in making such
assumptions.