Single component phase change: Role of temperature and pressure

In the context of more likely phase change on the hot side of a heat exchanger the discussion is
restricted to a single component system to explain the role of temperature and pressure in the
phase change. The simplest example is of a single component is water – vapor phase change.

This is a pressure-enthalpy [P-H] diagram of water. Y-axis is pressure. X-axis is enthalpy. There are
three distinct regions in the diagram. The left side of the dome is the water region. The dome
represents the two-phase region when water transforms to vapor. The right side is the steam
region. Left- side outer line of the dome represents the saturated water line. The right-side outer
line of the dome represents the saturated steam line. The meeting point of these two lines shown
by small red dot on the top of the dome is the critical point.
Phase change occurs between saturation point of water on the left outer line and the saturation
point of steam on the right outer line of the dome. In the case of water saturated water exists at
100 degc/1 bar pressure with dryness fraction, X = 0 and saturated steam forms at 100 degc/1 bar
pressure with dryness fraction, X = 1. The steam dryness fraction is used to quantify the amount of
water within steam. If steam contains no water, it has a dryness fraction X =1.
Why and when a phase change occurs?
The phase change occurs by external intervention when the phase is saturated with energy and it
has no space to accommodate any more energy. Depending on the type of external intervention
cooling or heating a saturated phase converts into a new phase. When saturated water is further
heated For example, it converts to vapor and saturated steam is cooled it converts into a new water
phase.
Why phase change occurs at constant temperature?
Phase change occurs at constant temperature because water [liquid] beyond saturation point has
no more heat capacity left to increase its temperature. The heat applied beyond saturation point
goes to break intermolecular bonds, generating vapor, expansion of vapor [PdV work] and doing
entropy generation as the vapor expands. This supplied heat remains latent and expressed as
enthalpy of vaporization or latent heat. Entropy is accounted for separately. These entire
phenomena happen inside the dome until two phase of water-vapor combines into a single dry
steam called saturated steam on the right- side outer line of the dome.
What is the role of pressure in a two- phase system [ liquid-vapor]?
A phase change happens at a constant pressure fixed by the temperature. For example, the phase
change of water to vapor happens at 100 degc/1 bar pressure.
Explanation
Gibbs phase rule

The thermodynamic state of a phase is defined by ‘PVT’ [ pressure, temperature and volume] In
thermodynamics.
The phase rule is a general principle governing "PVT" systems in thermodynamic equilibrium.
According to the phase rule, F = C - P +2
F is the number of degrees of freedom, C is the number of components and P is the number of
phases. The degrees of freedom signify the number of intensive independent variables which
define a phase. An independent variable is one which can vary independently without its effect on
the other variables.
Explanation
There are two intensive variables P [pressure] and T [temperature] relevant for a single component
system.
Single phase and single component
Let us refer to the above phase [P-T] diagram of water. Y-axis is pressure. X-axis is temperature.
For a single component and single phase like a pure water [liquid]
C [component] = 1
P [ phase] = 1
Therefore, F = 1 – 1 + 2 = 2
Therefore, F = 2
It means a pure liquid [water] can be defined by two independent intensive variables. Now let’s
look at the water phase diagram. DAE represents water region. You may observe that within this
area there can be any pressure P and any temperature T to define liquid water.
Phase change
At phase change while the system remains to be a single component system, it becomes a two-
phase system.
C=1
P =2
F = C-P+2 = 1 -2 + 2 = 1
Therefore, we can see that the degrees of freedom or number of independent intensive variable is
one when the phase change occurs. Therefore, it means that a phase change has only one
independent variable and the other variable becomes a dependent variable.
Let’s go back to the phase diagram. AD and AE are the two boundary lines of water phase
separating it from solid [ice] and vapor[steam]
You may observe that at every point on these two lines there is only one intensive variable either T
or P represents the phase change, the other gets automatically fixed.
Coming back to water phase change, the temperature gets fixed at 100 degc at phase change
because there is no more heat capacity to raise its sensible heat. Since there is one independent
intensive variable the pressure gets automatically fixed at 1 bar which is the saturated vapor
pressure of water at 1 bar.
Advantage of constant pressure at phase change
The advantage of constant pressure at phase change is consistent supply of heat even though the is
expansion of vapor by maintain constant pressure and thereby supply of maximum energy..