CHAPTER 2: PURE SUBSTANCE

2.1 Phase

A phase is any homogeneous part of a system which is physically distinct and is separated from other parts of the system
by distinct bounding surfaces. The three different phases of pure substance are solid, liquid, and vapor or gas. Ice, liquid
water, and water vapor constitute three different phases or water, since each form is homogeneous and physically
different from the others and is clearly defined by distinct boundaries existing between them. A liquid solution constitutes
a single phase no matter if it is homogeneous. For example, a solution of sugar in water is consists of one phase; sugar
and water (assuming that sugar is dissolved in water). If additional amounts of sugar are added until sugar no longer
dissolves in water; then this constitutes to different phases sugar solution and solid sugar. The same thing goes for solid
or vapor solution. Even if solid or liquid is composed of several substances as long as solution is homogeneous then the
substance is solid is said to be a single phase.

2.2 Definition of Pure Substance

A pure substance is one that is chemically homogeneous and invariable in chemical composition. It may exist in
more than one phase, as long as the chemical composition is the same then it is said to be a pure substance. For example,
a mixture of liquid water and water vapor (steam) or, a mixture of ice and liquid water are both pure substances since
every phase has the same chemical composition. Air which is a mixture of (mainly) oxygen, and nitrogen is considered a
pure substance provided there is no change of phase. It is so because the chemical composition of liquid air is different
from that of gaseous air and therefore the mixture of liquid and gaseous air is no longer a pure substance (liquid air has
higher fraction of nitrogen than gaseous air).

2.3 Phase Diagrams

Two phases of pure substance can coexist in equilibrium at a given temperature only if the pressure is a particular
value which corresponds to that pressure. These corresponding values of pressure and temperature are called saturation
pressures and saturation temperatures. Remember that there is only one saturation temperature for a given saturation
pressure and vice versa. The condition under which two or more phases of a pure substance can exist together in
equilibrium is called saturation conditions. A phase diagram is a pressure-temperature diagram showing more than one
of the saturation lines (liquid-vapor, liquid-solid, solid-vapor of a pure substance. A phase diagram for water (a substance
which expands on freezing) is shown in Fig. 2.1. Any point on a saturation line of the phase diagram represents conditions
of pressure and temperature under which two phases exist in equilibrium.

The three lines are called saturation lines namely solid-liquid, solid-vapor, and liquid-vapor lines. All points not on a
saturation line represent conditions under which only one phase of the pure substance can exist. Points between the solid-
liquid and liquid-vapor lines represent liquid states, and this region is called liquid region. Points to the left of the solid-
vapor and solid-liquid lines represent solid states, and this region is called solid region. Points to the right of the solid-
vapor and liquid-vapor lines represent vapor states, and the region is now called vapor region. Liquid whose temperature
is lower than its saturation temperature at the same pressure is called subcooled liquid. The other term for subcooled
liquid is compressed liquid since the actual pressure of liquid is higher that its saturation pressure at the same actual
temperature.

Therefore all points in the liquid region and not on the liquid-vapor saturation line represent states of subcooled liquids.
Vapor at a temperature higher than its saturation temperature at the same pressure is called super heated vapor. The
intersection of the vaporization line (line bd), fusion line (line bc), and sublimation line (line ab) on a pT diagram represents
the conditions under which three phases can coexist in equilibrium is called the triple point (point b), to the end of the
liquid-vapor line is point d known as the critical point. At pressures or temperatures higher than the critical point, there
is no distinction whether the substance is liquid nor vapor and the specific volume of liquid and vapor are equal.
Let us look at the pressure-volume diagram for water and examine the important states and different phases of the
substance. Line ab as in the previous figure is called saturated solid line which is a series of saturation points at different
temperatures. A point to the left of this line is at a higher pressure than the saturation pressure at the same temperature.
Line bc is called solid-liquid line or fusion line. This is when solid is slowly turning into liquid.

For example, ice when exposed to the sun melts while at constant temperature of 0oC the heat involved after the complete
changed from solid to liquid is called heat of fusion. All the points to the right of line ab and to the left of line gh are called
mixture of solid and vapor. This happens during the process of sublimation where solid is directly changed into vapor
without passing the liquid phase. This happens at a relatively low pressure such as for carbon dioxide (dry ice).

Line ce is called saturated liquid which is a series of saturation points at different temperatures. To the left of this line and
to the right of the solid-liquid line is called subcooled liquid. Line df is called liquid-vapor line. This is when liquid turned
into vapor at unchanging temperature. For example, liquid water when heated at constant pressure will vaporize at 100 oC.
The heat involved during the process is called heat of vaporization and the process is called vaporization process. The
area enclosed by line def is called liquid-vapor region. Point e is the critical point mentioned previously. Line eh is called
saturated vapor line which is a series of saturation points at different temperatures. To the right of this line is called
superheated vapor region where the temperature of vapor is higher than its saturation temperature at the same pressure.

Ice at a temperature lower than 0oC when heated will increase its temperature to its melting temperature, 0 oC. Further
addition of heat will result to melting of ice at while the temperature remains constant. Water at 0 oC when heated will
increase its temperature to 100 oC and it’s only at this point when liquid will change into vapor until it becomes saturated
vapor.

2.4 Quality of Mixture

Quality, denoted by the symbol x, is defined as the fraction by mass of vapor in a mixture of liquid and vapor. The
term quality is not used for subcooled liquid and superheated vapor. The limiting values of quality are 1.0 for saturated
vapor (meaning pure vapor) and 0 for saturated liquid (meaning pure liquid) or 100 percent for saturated vapor and 0
percent for saturated liquid. Saturated vapor is often called “dry saturated vapor or dry steam” and a mixture of vapor
and liquid as “wet vapor”.
 Looking at Figure 2.4, which is a detailed picture of the p-v diagram for liquid and vapor alone shows vf and vg.
These two symbols are for the specific volumes of saturated liquid and saturated vapor respectively. Point c is a mixture
of liquid and vapor whose specific volume is known as vfg which is the difference between the specific volumes of saturated
vapor and saturated liquid (vfg = vg - vf ).

The specific volume of mixture, Vx as seen from the Figure 2.4 depends on the amount of vapor present in the mixture of
liquid and vapor. An equation can be derived using the definition of quality and showing that vx is a function of the quality
and the difference of specific volumes of saturated vapor and saturated liquid, Vfg.

Let mf be the mass of liquid and mg be the mass of vapor. Vf and Vg stands for the total volumes of the liquid and
vapor present in the mixture respectively.

Using the definition of quality

V Vf + Vg mfvf + mgvg
Vx = ------ = ------------- = ---------------------
M m f + mg mf + m g
Separating the two terms

mf mg
Vx = ----------------- vf + -------------- vg
mf + m g mf + m g
from the definition of quality the equation can be written as

Vx = xvf + (1 - x)vg or xvf + yvg, where y = (1 -x)

Simplify the terms leads to

Vx = vg + x(vf - vg) or vf + x(vg - vf)

Vx = vf + xvfg Ux = Uf + xUfg hx = hf + Ufg

This shows that, when x = 50%, the point represents the states of the mixture midway between b and d.