Gibbs Phase Rule

IN 1875, Josiah williard gibbs published a general principle governing systems in
thermodynamics equilibrium called the phase rule in a paper titled On the Equilibrium of
Heterogeneous substances. He was an American scientist who made significant theoretical
contributions to physics, chemistry, and mathematics.
So before that, let’s get familiar with some basic terms that being used for this study. The
first one is phase. Basically, the state of matters are solid, liquid and gas. The second one is
System. It may be separated from environments by boundaries which some types of system
are closed system, adiabatic system and isolated system. The last one is component which
also indicates the minimum number of species, part or element in a system.
All of this basic terms can be easily understand through a simple example. A plain water in a
glass. The system is the water itself. The component is H2O while the phase is liquid. The
other example is salt in water. The system is water. The components are H2O and salt or
calcium chloride. The phases are solid and liquid.
The phase rule allows one to determine the number of degrees of freedom which is F or
variance of a chemical system. It has been mathematically represented as the following
formulation.
F in the formulation stand for number of degrees of freedom. It is the number of intensive
variables that are independent of each other. So what are intensive variables? Intensive and
extensive are not similar. An extensive variable is one which depends on system size (the
example are mass or volume) An intensive variable is one which does not depend on
system size (like temperature, pressure, or density). Just like in this rule, the variable that
being studied are pressure, temperature and concentration. C stands for the number of
components in an equilibrium and P is the number of phases in a system. The number two is
specified because this formulation assumes that T and P can be varied.
Thus, this rule is being applied under some conditions such as dynamic and reversible
processes, system is heterogeneous and is in equilibrium. The variable under study are
pressure, temperature and concentration.
This rule being applied for two different system which are one component system and two
component system (which also called as binary system). It is different on the maximum
number of variables. For one component system, the max number of variables to be
considered is two which are temperature and pressure. For binary system, the max num of
variables are three which are Temperature, pressure and concentration.
This diagram shows some of familiar phase change. Sublimation is the transition from solid
to gas phase. It is an endothermic process. solid changes to liquid phase in melting make it
an endothermic process. vaporization which also called as evaporation involved phase
change from liquid to gas and also an endothermic process. condensation and freezing are
both exothermic process. the last one is deposition. It involved phase change from vapour to
solid phase. Heat energy released to the environment and make it an exothermic process.
Phase changes related with energy changes. As we know, if heat energy being absorbed or
taken from the environment, the process is an endothermic. While if the heat energy being
released to the environment, the process is an exothermic. A negative enthalpy represents
an exothermic reaction, releasing heat. A reaction that absorbs heat is endothermic
Phase diagram is also known as equilibrium phase diagram or equilibrium diagram. It

summaries the conditions of substance that exists either in solid, liquid or gas. Phase
diagram different for one component system and two component system. One component
system is a system that consists of one independent species but with different phase.
The following is an example of phase diagram. Pressure is on y axis and temperature is on x
axis. Triple point is where temperature and pressure at which all three phases are in
equilibrium. In a phase diagram, The critical point or critical state is the point at which
two phases of a substance initially become indistinguishable from one another.
The water system consists of three phases which are ice, water and water vapour. Since
H2O is the only chemical compound involved, it is a single or one component system.
Therefore, from the phase rule, C equal to 1. At the curve, two phases can co-exist at
equilibrium. Thus, P is equal to two and F obtained is 1. In the areas which the field where
solid, liquid and vapour exist respectively. Thus, P is equal to 1 since it is single phase area.
C is 1 because the component exist is only H2O and F is equal to 2. Last but not least, at
triple point where solid, liquid and vapour are simultaneously at equilibrium. Thus P equal to
3 and F equal to 0 (zero)
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IN 1875, Josiah williard gibbs published a general principle governing systems in

Phase diagram is also known as equilibrium phase diagram or equilibrium diagram. It

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