Extending The Diagrams To Include The Solid Phase

Extending the Diagrams to Include the Solid Phase:
The two equilibrium diagrams developed so far represent the equilibrium states involving the liquid and the vapor phases only. However, these diagrams can easily be extended to include the solid phase as well as the solidliquid and the solidvapor saturation regions. The basic principles discussed in conjunction with the liquidvapor phase-change process apply equally to the solidliquid and solidvapor phase-change processes. Most substances contract during a solidification (i.e., freezing) process. Others, like water, expand as they freeze. The P-v diagrams for both groups of substances are given in Figs. and . These two diagrams differ only in the solidliquid saturation region. The fact that water expands upon freezing has vital consequences in nature. If water contracted on freezing as most other substances do, the ice formed would be heavier than the liquid water, and it would settle to the bottom of rivers, lakes, and oceans instead of floating at the top. The suns rays would never reach these ice layers, and the bottoms of many rivers, lakes, and oceans would be covered with ice at times, seriously disrupting marine life.
Figure - P-v diagram of a substance that contracts on freezing.
Figure - P-v diagram of a substance that expands on freezing. We are all familiar with two phases being in equilibrium, but under some conditions all three phases of a pure substance coexist in equilibrium (Fig. ). On P-v or T-v diagrams, these triple-phase states form a line called the triple line. The states on the triple line of a substance have the same pressure and temperature but different specific volumes. The triple line appears as a point on the P-T diagrams and, therefore, is often called the triple point.
The triple-point temperatures and pressures of various substances are given in Table .
However, substances at high pressures can exist in the liquid phase at temperatures below the triple-point temperature. For example, water cannot exist in liquid form in equilibrium at atmospheric pressure at temperatures below C, but it can exist as a liquid at -C at MPa pressure. There are two ways a substance can pass from the solid to vapor phase: either it melts first into a liquid and subsequently evaporates, or it evaporates directly without melting first. The latter occurs at pressures below the triple point value, since a pure substance cannot exist in the liquid phase at those pressures. Passing from the solid phase directly into the vapor phase is called sublimation. The P-T Diagram: Figure shows the P-T diagram of a pure substance. This diagram is often called the phase diagram since all three phases are separated from each other by three lines. The sublimation line separates the solid and vapor regions, the vaporization line separates the liquid and vapor regions, and the melting (or fusion) line separates the solid and liquid regions. These three lines meet at the triple point, where all three phases coexist in equilibrium. The vaporization line ends at the critical point because no distinction can be made between liquid and vapor phases above the critical point.
figure - P-T diagram of pure substances.
PROPERTY TABLES:
For most substances, the relationships among thermodynamic properties are too complex to be expressed by simple equations. Therefore, properties are frequently presented in the form of tables. Some thermodynamic properties can be measured easily, but others cannot and are calculated by using the relations between them
and measurable properties. The results of these measurements and calculations are presented in tables in a convenient format. In the following discussion, the steam tables are used to demonstrate the use of thermodynamic property tables. Property tables of other substances are used in the same manner. separate table is prepared for each region of interest such as the superheated vapor, compressed liquid, and saturated (mixture) regions. Before we get into the discussion of property tables, we define a new property called enthalpy.
EnthalpyA Combination Property:

A person looking at the tables will notice two new properties: enthalpy h and entropy s. we frequently encounter the combination of properties u + Pv. For the sake of simplicity and convenience, this combination is defined as a new property, enthalpy, and given the symbol h:
h = u + Pv kJ/kg kJ
or
H = U +PV
Figure -The product pressure x volume has energy units.
Saturated Liquid and Saturated Vapor States:

The properties of saturated liquid and saturated vapor for water are listed in Tables A and A. Both tables give the same information. The only difference is that in Table A properties are listed under temperature and in Table A under pressure. Therefore, it is more convenient to use Table A when temperature is given and Table A when pressure is given. The use of Table A is illustrated in Fig. .
Figure - A partial list of Table A.
The subscript f is used to denote properties of a saturated liquid, and the subscript g to denote the properties of saturated vapor. These symbols are commonly used in thermodynamics and originated from German. Another subscript commonly used is fg, which denotes the difference between the saturated vapor and saturated liquid values of the same property. For example, =specific volume of saturated liquid. vg = specific volume of saturated vapor. vfg = difference between vg and vf (that is, vfg = vg _ vf ). The quantity hfg is called the enthalpy of vaporization (or latent heat of vaporization). It represents the amount of energy needed to vaporize a unit mass of saturated liquid at a given temperature or pressure. It decreases as the temperature or pressure increases and becomes zero at the critical point.

Extending The Diagrams To Include The Solid Phase

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Extending The Diagrams To Include The Solid Phase

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Extending the Diagrams to Include the Solid Phase:

Figure - P-v diagram of a substance that contracts on freezing.

figure - P-T diagram of pure substances.

EnthalpyA Combination Property:

Figure -The product pressure x volume has energy units.

Saturated Liquid and Saturated Vapor States:

Figure - A partial list of Table A.

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