Defination of Phase and

Gibbs Phase Rule

Dr. Tarun Kumar Naiya

Associate Professor, Department of Petroleum Engineering
IIT (ISM) Dhanbad
Email : trn2711@yahoo.com
• Reservoir fluids typically reservoir fluid depends on
Petroleum Fluids contains hundreds or composition, temperature and
thousands of hydrocarbon pressure.
compounds and a few non-
organic compounds. • Natural gas is composed of
mainly low molecular weight
• The physical properties of a
 2 Alkenes Alkynes Cyclo-Alkanes (Naphthenes)
alkanes (paraffins), CO2, H2S Alkanes (Paraffins)
and N2.
• Most crude oils are composed
of higher molecular weight Hydrocarbons
hydro-carbon compounds
(Aromatic and Naphthenes).
CnH2n+h
Hydrocarbons

Non-aromatic Aromatic
 Phase

Behavior: PT Diagram — Hydrocarbon Systems

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Schematic p-T Diagram: Names represent conventional

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Hydrocarbon Reservoir Fluids ■

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■ Locations of names represent relative locations of these fluidtypes.

Petroleum Fluids – Example Compositions

 4

Structure Formula H
Alkanes CnH2n+2 H
(Paraffins) H
H HC HC HC H HCH C C H
HC H
H H H H HCHH

n-C4H10 : normal-butane i-C4H10 : iso-butane

Alkenes (Olefins) Structure Formula CnH2n

H
HCH C H H
C H

C3H6 : propene

Alkenes are seldom found in reservoir fluids due to their unstable nature
 Course in Advanced Fluid Phase Behavior.

© Pera A/S 6

Alkynes CH3

Structure Formula CnH2n-2

HC C CH3 CH3
C

C6H10 : Heksyne

Alkynes are seldom found in reservoir fluids due to their unstable nature

Cyclo-alkanes (Naphthenes)
Structure Formula
 CnH2n

CH2

CH2 CH2

C3H6 : cyclo-butane

Aromatics CH CH3C

CH CH Benzene
CH CH
CH CH CH
 CH CH CH Tuolene

Fluid Phase Behavior

All substances can occur in three states
(phases): 1. Vapor
2. Liquid
3. Solid
“Thermodynamic Equilibrium”:
▪ No net mass transfer between the phases.

▪ Temperature and pressure of the co-existing phases are the same.

▪ The chemical potential of each component in each phase are

equal. ▪ The system attains it minimum energy level.

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Definition of Phase

Phase is a part of a system that is physically distinct from the

other parts of the system by a surface.
Generally, we think of the three phases of matter that we are familiar with — solid, liquid, and
gas. Each of these are distinct and easily discernible.
In solids and some liquids, there can be internal phases that are not as easy to recognize, but they are
still important.

A good example of one of these materials is the liquid crystalline material that is found in displays.

There is an ordered phase and a disordered phase that pass light very differently.

Phase: A phase is defined as “an homogeneous, physically distinct and mechanically separable portion of
system, which is separated from other such parts of the system by definite boundary surface”.
 A phase diagram is a graph representing the relationship of
all the states of matter of a specific substance. The most
common type of phase diagram relates the state to
temperature and pressure. The temperature is the
horizontal axis and the pressure is the vertical axis.

Different substances have different ranges of

temperature and pressure.
The lines may be longer or shorter and the angles may
vary, but the solid (S), liquid (L) and the gas (G) regions
always have the same basic relationship to each other.

The phase diagram allows to predict which state of

matter exists at a certain temperature and pressure
Phase diagram of pure compound combination.
A critical point (or critical state) is the end point of a phase equilibrium . Triple point of a substance is the temperature
and pressure at which the three phases (gas, liquid, and solid) of that substance coexist in thermodnamic euilibrium .

The A-B line is the solid-vapor line. Sublimination

occurs as the the temperature progresses from the
left to the right side of the A—B line.
The A—D line is the solid-liquid line. Melting
occurs as the line is crossed from left to right.
Line A—C is the liquid-vapor equilibrium line. Boiling
occurs when moving from left to right across this line.
Starting at I and moving to J progresses from a
solid to a liquid and then to a vapor.
Point A is called the tripple point because at this
point the solid, liquid, and vapor phases exist at
equilibrium.
All pure hydrocarbons have similar PT diagrams.
Terms Related
to Phase Diagram

Phase
A phase is defined as a part of a system which is homogeneous throughout and is separated from other
homogeneous parts of the system by means of a definite boundary. A phase is physically distinct and
mechanically separable part of the system.
 Component
The composition of a system can be described in terms of species present in the system. The number of
components of the system is the minimum number of constituents necessary to define the composition of the
system.

Degrees of Freedom
The degrees of freedom or the variance of a system is defined as the smallest number of independent variables
such as pressure, temperature and concentration that must be specified in order to describe completely the
state of the system.
The smallest number of independently variable factors such as temperature, pressure and concentration which
must be required in order to define the system completely are called the degree of freedom. Degree of freedom
of a system is also known as variance.
When a system having no degree of freedom
F = 0 it is called non-variant system or invariant system.
The term degree of freedom can be understood with the help of following examples:
A) The system ice = water = vapour has no degree of freedom (i.e., F = 0). The three phases of water i.e.
ice, liquid water and vapour can exist together in equilibrium only at a particular-temperature and
pressure (corresponding to the freezing point) and no factor is necessary to be specified to define the
system. Hence, a system consisting of ice, water and vapour in equilibrium has no degree of freedom i.e.
it is a non variant system.

B) For a mixture of gases, the number of degrees of freedom is three (i.e., F = 3). Such a system can be completely
defined when the temperature, pressure and composition are fixed. In this case, the remaining factor i.e., volume
 gets automatically fixed. For example, a gaseous mixture
consisting of 70% N2 and 30% O2 at 22°C and 1 atm pressure is completely defined and does not require any
other information for its description. Hence, a system consisting of a mixture of gases has three degrees of
freedom i.e. it is a trivariant system.

C) For a saturated LiCl solution, the number of degrees of freedom is one (i.e., F = 1). This is because the system
can be completely defined by specifying the temperature only. The other two factors i.e. composition and vapour
pressure get automatically fixed when the temperature is fixed. Hence, a system consisting of a saturated LiCl
solution is a univariant system.
Thermodynamic Phase Diagram

Unary System Phase Diagram

In a one-component system or unary system only one chemical component is required to describe the phase
). There are many one
relationship, for example, iron (Fe), water (H2O) or methane (CH4 component systems, including
all of the pure elements and compounds. The phase that can exist in a one-component system are limited to vapor,
liquid and solid. Phase diagrams for one-component system are specified in terms of two variables, temperature,
normally specified in degrees centigrade, and pressure specified in atmospheres.
Binary System Phase Diagram
Binary systems contain two components, for example, Fe + C, NaNbO3 + LiNbO3, Pb + Sn. The added component
means that three variables are needed to display a phase diagram. The variables are usually chosen as temperature,
pressure and composition.

A binary phase diagram thus needs to be plotted as a three-axis diagram. A single phase will be represented by a
volume in the diagram.
Ternary System Phase Diagram

For a three component system a complete phase diagram would require four dimensions representing T, P and
two mole fractions.

If the pressure is held fixed, a temperature composition phase diagram is obtained that requires three
dimensions. However, if the pressure and temperature is kept constant then the degree of freedom reduces to
two and the system can be represented on a two-dimensional plane.
 Several schemes have been in use for representing the equilibria in three component system, but the equilateral
triangle method suggested by Gibbs and Roozeboom is extensively used.

The concentrations of three components are plotted on an equilateral

triangle.
Phase Rule :

The phase rule is a generalization given by Willard Gibbs (1874), which

seeks to explain the equilibria existing in heterogeneous system.

It may be stated as: “provided the equilibrium between any number of

phases is not influenced by gravity, or electrical, or magnetic forces or
by surface action and only by temperature, pressure and concentration,
then the number of degrees of freedom (F) of the system is related to
number of components (C) and of phases (P) by the phase rule equation for any system at equilibrium at a
definite temperature and pressure.

Gibbs Phase Rule F=c–p+2

• F = Degrees of freedom (number of independent variables).
• Π = Number of components.
• P = Number of phases.
▪ Intensive thermodynamic variables such as temperature, pressure, composition, and
density, do not depend upon the extent of the system.

▪ Extensive variables such as flow rate, total mass, or liquid volume depends upon the
extent of the system.

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basis of phase rule

• phases are reaction products! therefore, they record the reactions that
occurred, as well as conditions

why is phase rule useful?

• helps to characterize state of the system
• predict equilibrium relations of phases
• helps to construct phase diagrams
 Degree of Freedom
The number of components present in a system determines the maximum number
of phases that can coexist at fixed temperature and pressure.

The phase rule of Gibbs states that the number of independent variables that
must be specified to determine the intensive state of the system is given by �� =
2 + �� − �� − ����
F is the number of degrees of freedom
c is the number of components
�� is the number of phases
Ncis the number of constraints (e.g., chemical reactions).
For a single-component system, the maximum number of phases occurs when there are no
constraints (Nc = 0) and no degrees of freedom (F = 0).
In a binary system, two phases can exist over a range of temperatures and
pressures. The number of degrees of freedom is calculated by �� = 2 −
 ����
therefore, both the temperature and pressure can be chosen, although there is
no guarantee that two phases will occur at a specific choice of T and p.

For multicomponent systems, the phase rule provides little guidance because
the number of phases is always far less than the maximum number that can
occur.

However, for typical applications, the temperature, pressure, and overall

composition of a system are known in advance.
Extensive variables: Extensive variables depend on, and reflect, the size of a
chemical “system.”

The system could be a liquid solution, for example. Extensive variables include the
total volume, the total mass, and the total energy contained in the system, among
 others.

Intensive variables: Variables that do not depend on system size.

Examples are temperature, pressure, chemical potential, density, specific volume,

viscosity, thermal conductivity, mass fractions, mole fractions, among others.

Gibbs Phase Rule applied for systems in which there are no chemical reactions.
DERIVATION OF PIASE RULE EQUATION
The Gibb’s phase rule can be derived on the basis of thermodynamic principle as follows.
Let us consider a heterogeneous system consisting of P(P1, P2, P3 ...P) number of
phases and C(C1, C2, C3 ... C) number of components in equilibrium.

Let us assume that the system is non-reacting i.e. the passage of a componentfrom one phase to another
does not involve any chemical reaction.

When the system is in equilibrium state it can be explained completely by specifying the following
variables: (i) Pressure (ii) Temperature
(iii) Composition of each phase.
Total number of variables required specifying the state of system:
Temperature: same for all phases Pressure: same for all phases Concentration
Independent concentration variables for one phase with respect to the C components = C −
1 [ Conc. of last component is dependent]
Independent concentration variables for P phases with respect to the C components = P(C −
1) Total number of variables = P(C − 1) + 2 ...(1)
(a) The total number of equilibria:
The various phases present in the system can remain in equilibrium only when the
chemical potential (µ) of each component is the same in each phases, i.e.

For each component the no of equilibria for P phases = (P − 1) ………… 1

For C component the no of equilibria for P phases = C(P − 1) ………….. 2
Total no. of equilibria involved (E) = C(P − 1) ...(2) From eq. 1 & 2 we get
F = [P(C − 1) + 2] − [C(P − 1)]
F = [CP − P + 2 − CP + C]
F=C−P+2
In thermodynamics it is discussed that if we have a uniform chemical phase (e.g. a gas, a
solution, a solid) comprised of c chemical species, once you specify c + 1 intensive
variables all other intensive variables are fixed.

For example, if you specify c-1 mole fractions, plus T, plus P, the specification of these c
+ 1 variables is sufficient to determine the values of all other intensive variables.

If the system contains Π phases, each with its own composition, in principle one would
need to specify Π(c+1) intensive variables to completely determine the “intensive” state of
each phase and hence the system.

However, if the phases are in equilibrium with one another, then the temperatures and
pressures of the phases are equal. Otherwise, there would be a flow of heat to even out the
temperatures, or movement of matter to even out the pressures.
Thus, for phases that are in equilibrium, we only need to specify Π(c+1) – (Π−1)
– (Π−1) intensive variables. Note that equivalency of temperatures and pressures
between phases each provides (Π−1) independent equations. For example, if you
have two phases, equivalence of temperatures yields the single relation T1 = T2.
After enforcing equivalency of temperatures and pressures between phases, we
are left with only Π(c−1) + 2 intensive variables to specify. But we are not done
yet, because equilibrium also implies that the chemical potential of each species
must be the same in all phases.
This requirement yields another (Π−1) independent equations for each component,
for a total of c(Π−1) constraints. Thus, finally, the degrees of freedom (F) available
before the intensive state of a system with Π phases and c components is fully
specified
F = Π(c−1) + 2 − c(Π−1)
F=2+c–Π
Example 1 – A gaseous system having one component. No. of phases in the
system = 1 Every homogeneous phase has an equation of state or phase
equation given by f(P,T,C)=0 where P stands for pressure, T for temperature
and C for concentration.
This phase equation has three variables P,T and C. If the values of 2 variables
are known, the third can be calculated using this equation.

Hence the number of variables that need to be actually specified is equal to

2.

Number of degrees of freedom = Total number of variables – number of

equations connecting the variables F = 3-1=2 The above mentioned system
is a bivariant one.
Derivation of the rule taking that one of the components is present only in P-1 phases.

We consider, as in the earlier case, a system consisting of C components and P phases under equilibrium at constant
temperature and pressure.

One of the components is missing from one phase and hence is present in only P-1 phases.
Let us first find out the total number of intensive variables that are needed to describe the state of the system. As one
component is excluded from one phase, the number of concentration variables will be CP-1.
Merits of phases rule:
1. It is applicable to both physical and chemical equilibria.

2. It require no information regarding molecular/ micro-structure, since it is applicable to macroscopic system.

3. It is a convenient method of classifying equilibrium states in terms of phases, components and degrees of
freedom.

4. It helps us to predict the behaviour of a system, under different sets of variables. 5. It indicates that

different systems with same degree of freedom behave similarly. 6. It does not take into cognizance of

either the nature or quantities of component present in the system.

7. It helps in deciding whether under a given set of condition:

a. various substances would exist together in equilibrium or
b. some of the substances present would be interconverted or
c. some of the substances present would be eliminated .
Limitation of phase rule:
1. It can be applied only for system in equilibrium. Consequently, consequently, it is of little value in case of very
slow equilibrium state attaining system.

2. It applies only to a single equilibrium system: and provided no information regarding any other possible
equilibria in the system.

3. It requires utmost care in deciding the number of phases existing in an equilibrium sate, since it considers only
the number of phases, rather than their amounts. Thus, even if a trace of the phase is present, it accounts
towards the total number of phases.
4. It conditions that all phases of the system must be present simultaneously, under the identical conditions of
temperature and pressure.

5. It conditions that solid and liquid phases must not be in finely – divided state; otherwise deviations occurs.
 Thank you
Single-Component Phase Behavior
F=1–P+2 diagram). ▪ Phase transition (p-V diagram).

• For a single-phase, single-component system F = 2, and the

phase behavior is completely determined by pressure and
temperature (or pressure and volume, at a given temperature).

• For a two-phase, single-component system F = 1, and pressure

or pressure needs to be specified to determine the system.

▪ Vapor curve (p-T • Vapor-Liquid Equilibrium (VLE) occurs only at the Vapor
Pressure, which is a unique function of temperature that
culminates at the Critical Point.
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Single-Component Vapor-Pressure Curve • Along the

vapor-pressure curve, the two-phases are
in thermodynamic equilibrium.
• The vapor-pressure curve ends at the critical point.
• At the critical point the two phases are
indistinguishable.
• Liquid and vapor cannot coexist at temperatures
above the critical temperature, or for pressures
above the critical pressure.

Quiz:
How to go from a liquid to a vapor at nearly the
same conditions, without any abrupt phase
change?

50 e

Single-Component Phase Transfer

r

s
 s

Liquid
 ”Liquid-
like”

”Gas-like”

Critical
point

Gas (Vapor)

Temperature
 51

Single-Component
Pressure-Volume
Curve
• In a single-component system, the transition from
vapor to liquid takes place at a constant pressure.

Quiz:

Vapor Vapor

Liquid Liquid

V < V1 T = T1 P = ?
V = V1 T = T1 P = P1 ρo = ρ1
ρo = ?
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