Mehran UET SZAB Campus Khair pur Mir

Mehran University of e

Gibbs Phase Rule and Degree of

freedom
Presented by:
Mazhar Ali Soomro

(K13PG43)

Contents

Phase Rule
Degree of freedom
Thermodynamic of solutions
Phase diagram
Types of phase diagram
Thermodynamic properties

Phase Rule

The Phase Rule describes the possible number of

degrees of freedom in a (closed) system at equilibrium,
in terms of the number of separate phases and the
number of chemical constituents in the system. It was
deduced from thermodynamic principles by J. W. Gibbs
in the 1870s.
The Gibbs phase rule describes the degrees of
freedom available to describe a particular system
with various phases and substances.

f p c 1 2 c p 1 pc p 2 pc c c p 2

Degree of freedom
TheDegrees of Freedom[F] is the number of
independent intensive variables (i.e. those that are
independent of the quantity of material present) that need
to be specified in value to fully determine the state of the
system. Typical such variables might be temperature,
pressure, or concentration.
The rule is:
F = C - P + 2.

single phase (pi=1)

two phases (pi=2)
three phase (pi=3)

F=1-1+2=2
F=2+1-2=1
F=2+1-3=0

3 Phases (solid, liquid-vapor and solid-liquid-gas)

For example:
A system with one component and one phase (a balloon full of
carbon dioxide, perhaps) has two degrees of freedom: temperature
and pressure, s
ay, can be varied independently.
If you have two phases -- liquid and vapor for instance -- you lose a
degree of freedom, and there is only one possible pressure for each
temperature.
Add yet one more phase -- ice, water and water vapor in a sealed
flask -- and you have a "triple point" with fixed temperature and
pressure

Thermodynamics of Solutions

Phases: Part of a system that is chemically and physically

homogeneous, bounded by a distinct interface with other phases
and physically separable from other phases.
Components: Smallest number of chemical entities necessary
to describe the composition of every
phase in the system.
The number of components are determined by the formula
C=N-X-R
Where N= total no: of chemical constituents, X=chemical
reaction
And R= total number of chemical constraints(neutrally charged) on
complete system

Ex: For the reduction of nickel oxide, NiO,

NiO(s) + CO(g) = Ni(s) + CO (g)
2

Solutions: Homogeneous mixture of

two or more
chemical components in which their
concentrations may be freely varied
certain
Canwithin
four phases
existlimits.
together (as in two solid

phases, a liquid phase and the gaseous

phase?

Phase diagram

A figure which summarizes the effect of temperature and

pressure on a substance in a closed container. Every point in
this diagram represents a possible combination of
temperature and pressure for the system. The diagram is
divided into three areas, which represent the solid, liquid,
and gaseous states of the substance.

The best way to remember which area corresponds to each

of these states is to remember the conditions of temperature
and pressure that are most likely to be associated with a
solid, a liquid, and a gas. Low temperatures and high
pressures favor the formation of a solid. Gases, on the other
hand, are most likely to be found at high temperatures and
low pressures. Liquids lie between these extremes.

Phase Diagram

Applications of PD

Phase diagrams are useful tools to

determine:
--the number and types of phases,
--the wt% of each phase, and the
composition of each phase for a given T
and composition of the system.

Phase diagram cont.

11

Triple points: Points where equilibrium boundary lines

meet.
All phases in the adjacent stability fields must coexist.
Critical point the point on a phase diagram at which the
substance is indistinguishable between liquid and gaseous
states.
Fusion(melting) (or freezing) curve the curve on a phase
diagram which represents the transition between liquid and
solid states.
Vaporization (or condensation) curve the curve on a
phase diagram which represents the transition between gaseous
and liquid states.
Sublimation (or deposition) curve the curve on a phase

2D Phase Diagram

12

The simplest phase diagrams are

pressure-temperature diagrams of a
single simple substance, such aswater.
Theaxescorrespond to thepressureand
temperature. The phase diagram shows,
in pressure-temperature space, the lines
of equilibrium or phase boundaries
between the three phases ofsolid,liquid,
andgas.

2D Phase Diagram

Pressure vs.
Temperature

3D phase diagrams

13

It is possible to envision three-dimensional (3D) graphs

showing three

thermodynamic quantities.

For example for a single component, a 3D Cartesian

coordinate type graph can show temperature (T) on one
axis, pressure (P) on a second axis, and specific volume (v)
on a third. Such a 3D graph is sometimes called a P-v-T
diagram.

The equilibrium conditions would be shown as a 3D curved

surface with areas for solid, liquid, and vapor phases and
areas where solid and liquid, solid and vapor, or liquid and
vapor coexist in equilibrium.

A line on the surface called a triple line is where solid,

liquid and vapor can all coexist in equilibrium. The critical
point remains a point on the surface even on a 3D phase
diagram.

3D Phase Diagram cont.

14

An orthographic projection of the 3D P-v-T

graph showing pressure and temperature
as the vertical an horizontal axes
effectively collapses the 3D plot into a 2D
pressure-temperature diagram. When this
happens, the solid-vapor, solid-liquid, and
liquid-vapor surfaces collapse into three
corresponding curved lines meeting at the
triple point, which is the collapsed
orthographic projection of the triple line.

3D phase diagram

15

Types of Liquids

16

Saturated Liquid:
aliquidwhosetemperatureandpressurearesuch
thatanydecreasein
pressurewithoutchangeintemperaturecausesitto
boil.
Unsaturated Liquid:
A Liquid which is not about to vaporize.
Saturated Vapor:
A vapor that is about to condense.
Super heated Vapor:
A vapor that is not about to condense.

Super critical Fluid

17

Asupercritical fluidis any substance at a

temperatureandpressureabove itscritical point
, where distinct liquid and gas phases do not
exist. It caneffusethrough solids like a gas, and
dissolvematerials like a liquid. In addition, close
to the critical point, small changes in pressure or
temperature result in large changes in density,
allowing many properties of a supercritical fluid
to be "fine-tuned". Supercritical fluids are
suitable as a substitute fororganicsolventsin a
range of industrial and laboratory processes.

Thermodynamic properties

18

The properties define the thermodynamic state of a system.

a. Intensive property: does not depend on the mass (m)

or does not change with subdivision of the system,
denoted by lowercase letters, e.g., z.

b. Extensive property: does depend on the mass (m) or

does change with subdivision of the system, denoted by
uppercase letters, e.g., Z.

19

* An intensive property is also called a specific

property if

Z
z
m

For example, volume V is an extensive property, so

v=V/m
(i.e., volume per unit mass) is a specific property
and an
intensive property.