PHASE RULE
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Ashraf J KilandePHASE RULE
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Ashraf J KilandePHASE RULE: Is a rule relating possible numbers of phases, constituents and degree of
freedom in chemical system
Gibb`s phase rule was prepared by Josiah Willard Gibbs in his landmark paper titled on
the equilibrium of heterogeneous substances (1875-1878)
The rule applies to non-reactive multi component heterogeneous system in
thermodynamic equilibrium and it given by;
(P+F=C+2) or (F=C-P+2)
Where;
P is the number of phases in the system
A phase is any physically separable material in the system. Every unique mineral is a
phase (including polymorphs); igneous melts, liquids (aqueous solutions), and vapor are
also considered unique phases. It is possible to have two or more phases in the same state
of matter (e.g. solid mineral assemblages, immiscible silicate and sulfide melts,
immiscible liquids such as water and hydrocarbons, etc.) Phases may either be pure
compounds or mixtures such as solid or aqueous solutions–but they must "behave" as a
coherent substance with fixed chemical and physical properties.
C is the minimum number of chemical components required to constitute all the
phases in the system
For historical reasons, geologists normally define components in terms of the simple
oxides (e.g. SiO2, Al2O3, CaO, etc.). If two possible components always occur in the same
proportions in multiple phases in a system, these can be combined into a single
component (remember, we are always trying to define the minimum number of
components required to make all the phases in the system). Consider the reaction:
CaMg(CO3)2 + 2 SiO2 = CaMgSi2O6 + 2 CO2
Dolomite + 2 Quartz = Diopside + 2 Carbon Dioxide
Normally we would pick the 4 components: CaO, MgO, SiO2, and CO2 based on the
simple oxides. However, because Ca and Mg are in a 1:1 ratio in both dolomite and
diopside (and not present in quartz or carbon dioxide), we can consider this a ternary
system with components: CaMgO2, SiO2, and CO2
In some geologic systems it is convenient to define the components in terms of end-
member compositions (e.g. binary systems such as carbonates, CaCO3 - MgCO3; alkali
feldspars, NaAlSi3O8 - KAlSi3O8, etc.).
In some cases, a given mineral assemblage may be represented by a sub-set of the whole
system if fewer components are needed to define the compositions of the observed
mineral assemblage–this is known as a degenerate system. A good example of this can be
seen on a ternary (3 component) chemographic projection if the phases of interest plot in
a co-linear fashion (i.e. requiring only two components to define the phase compositions
in what is otherwise a three component system).
A more complete discussion of components can be found in the section on Plotting
Mineral Compositions and Chemographic Projections.
F is the number of degrees of freedom in the system (also referred to as the variance
of the system).
For geologic applications, this generally refers to the number of variables (e.g. pressure
and temperature) that can be independently changed without altering the state of the
system (i.e. the number of phases and their compositions are constant). Three common
types of equilibria are possible:
Invariant equilibria, in which neither P or T can be changed; on a phase diagram,
this is represented as a singular invariant point
Univariant equilibria, in which either P or T can be changed independently, but to
maintain the state of the system, there must be a corresponding change in the
other variable; on a phase diagram this is referred to as a univariant curve
and
Divariant equilibria, in which both P and T are free to change independently
without changing the state of the system (but bounded by the conditions defined
by the univariant equilibria).
The integer in the Gibbs Phase Rule
is related to the number of intensive parameters (i.e. those that are independent of mass;
such as pressure and temperature) that are being considered. Note that many phase
diagrams consider only one intensive parameter (e.g. T-Xfluid, where T is intensive, and
the mole fraction of fluid is related to the amount of mass of the fluid components); in
this case, the Gibbs Phase Rule would be: P + F = C + 1.
It is generally the case that as the number of components increase, the variance of the
system must also increase. Conversely, as the number of phases increase in the system,
the variance of the system must correspondingly decrease.
Consider a glass of water. This is a pure substance (H2O) in a single phase. It can be
described with a number of thermodynamic properties including temperature, pressure,
volume, entropy, enthalpy and Gibbs energy. However not all of these properties are
independent. In fact, for the glass of water, only two intensive thermodynamic properties
are independent. Thus, if we specify temperature and pressure, all the other properties, in
their intensive (i.e. their value per mole of substance) form, can be determined.
Temperature and pressure are often taken as independent intensive variables.(see P-T
diagram) This is because it is usually easy to experimentally vary and measure these two
properties directly. However, any intensive property can be choosen to be one of the
independent variables. If the intensive enthalpy (J/mol) and intensive entropy (J/mol K) of
the water in the glass were specified, its temperature and pressure could then be found using
the steam tables or a Mollier diagram.
The Gibbs phase rule tells how many independent intensive properties, F, can be chosen.
This will depend on the number of chemical species, N, and number of phases, pi,
present. In the absence of chemical reaction, the Gibbs phase rule is simply:
F=2+N-pi
For a pure substance (N=1), the Gibbs phase rule can be applied as follows:
single phase (pi=1) F=2+1-1=2
two phases (pi=2) F=2+1-2=1
three phase (pi=3) F=2+1-3=0
An example showing that for a single phase of a pure substance, F=2:
For a glass of liquid water, specify one of the independent intensive variables to be
pressure. Choose this pressure to be 1 atm. If liquid is in the glass, the temperature can
take any value between 0 'C and 100 'C. Within this range, the temperature can be chosen
independently of the pressure. Thus, both T and P are independent. After choosing a (T,
P) pair, any other property, such as volume or entropy, can be found using the steam
tables or a Moliere diagram. Therefore the remaining properties can not be independently
chosen after T and P are specified.
Example showing that for two coexistent phases of a pure substance, F=1.
For a glass of boiling water (also call saturated liquid water) in equilibrium with saturated
steam, specify the one of the independent intensive variables to be pressure. Choose this
pressure to be 1 atm. In order for the water to boil (or be saturated) at this pressure, the
temperature must be 100 'C. Thus, the temperature can not be choosen independently of
the pressure when both liquid and vapor water are present. Thus, only the P is
independent. The temperature required at other pressures, as well as the values of all
remaining thermodynamic properties, can be found in the tables for saturated steam or on
a Mollier diagram.
Example showing that for three coexistant phases of a pure substance, F=0.
At the triple point; vapor, liquid and solid all coexist. For any given substance, the triple
point occurs only at one a specific pair of temperature and pressure. Once it is stated the
substance at the triple point, the values of this temperature and pressure pair as well as
the values of all other thermodynamic properties can be found in a table or graph. Thus,
no thermodynamic property can be choosen independently.
The Gibbs Phase rule can be applied to a P-T thermodynamic diagrams for pure
substances. On any such of diagram, each point represents a state of the material. Once
the point has been located, all other thermodynamic properties can be read off.
For a single phase, the required point can fall anywhere on the region of the plane
representing this phase. Thus, two coordinates are needed to specify a point within that
part of the plane. For example the horizontal and vertical axis values, T and P, can be
given. (F=2)
A two phase region on a P-T is represented by a curved line. Thus, to specify a point on
this curve only one additional coordinate, either T or P is needed. (F=1)
The triple point is represented by a single point. No additional information, neither T nor
P is needed. (F=0)
REFERENCES;
Atkins, P.W.; de Paula J. (2006). Physical chemistry (8th edition). Oxford university press.
ISBN 0-19-870072-5. Chapter 6
Gibbs, J.W Scientific papers (Dover New York, 1961).