Property diagrams for phase change processes

 The variations of properties during phase change are best studied and
understood with the help of property diagrams.

 Figure shows a P-T diagram of pure substance.

 This diagram is often called as phase diagram since all three phases are
separated from each other by three lines.
 Phase Diagram
PT diagram of a pure
substance
 The sublimation line
separates the solid and
vapor regions.
 The vaporization point
separates the liquid and
vapor region.
 The melting or fusion line
separates the solid and
liquid regions.
Fusion Curve

Vaporization Curve

Sublimation Curve
PV Diagram
Critical Point

 The critical point is the highest temperature and pressure for vapour liquid equilibrium.
That is at the critical point and at high pressures, liquid and vapour cannot co-exist.
 The vapour phase of a substance is known as gas when it is above the critical
temperature, whereas vapour usually implies a gas that is not far from sate of
condensation.
 The point after which vapours can not be condensed whatever is the pressure and
temperature.
Substance Tc (OC) Pc (atm)
H2O 374.4 219.5
NH3 132.4 111.5
C2H5 31.85 48.08
Critical Point
PVT Surfaces
 PVT Surface of
carbon dioxide
(with isotherms shown in
black and the vapor/liquid
equilibrium curve in
white)
 PVT Equation of States

 An equation that relates pressure, molar or specific volume and temperature

for a pure homogeneous fluid in equilibrium is known as equation of state.

 An equation of state may be solved for any one of the three quantities P,V,
or T as a function of the other two.
Single Phase Region

 At single phase regions in PV diagram, there is a relation connecting P , V and T.

 This relation known as PVT equation of state; f(P,V,T) =0
 If V is considered as a function of T and P, then V = V(T,P)

Volume Isothermal
Expansivity Compressibility
Single Phase Region

 Combining the above equations

 For liquids,  β is almost always positive (liquid water between 0°C and 4°C is an exception), and κ is
necessarily positive.

This is a less restrictive approximation than the assumption of an incompressible fluid.

Practice (Example 3.1)
Solution
Solution