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PROPERTIES

OF PURE SUBSTANCES

91

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PVDiagram

----

CHAPTER 3. Volumetric Properties of Pure Fluids

Figure 3.1 does not provide any information about volume; it merely displays the phase boundaries on a PT diagram. On a P V diagram [Fig. 3.2(a)] these boundaries in turn become regions
where two phases- solidlliquid, solid/vapor, and liquid/vapor- coexist in equilibrium. These
regions are separated by bounding curves that represent single phases, the relative amounts of
which determine the molar (or specific) volumes at intermediate points. The triple point of
Fig. 3.1 here becomes a horizontal line, where the three phases coexist at a single temperature
and pressure.

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liquid, liquid/vapor, and vapor regions with isotherms.
Figure 3.2(b) shows the liquid, liquid/vapor, and vapor regions of the PV diagram, with
four isotherms superimposed. Isotherms on Fig. 3.1 are vertical lines, and at temperatures
greater than Tc do not cross a phase boundary. On Fig. 3.2(b) the isotherm labeled T > Tc is
therefore smooth.
The lines labeled Tl and T2 are for subcritical temperatures, and consist of three segments. The horizontal segment of each isotherm represents all possible mixtures of liquid and
vapor in equilibrium, ranging from 100% liquid at the left end to 100% vapor at the right end.
The locus of these end points is the dome-shaped curve labeled BCD. the left half of which
(from B to C) represents single-phase liquids at their vaporization (boiling) temperatures, and
the right half (from C to D), single-phase vapors at their condensation temperatures. Liquids
and vapors represented by BCD are said to be saturated, and coexisting phases are connected
by the horizontal segment of the isotherm at the saturation pressure specific to the isotherm.
Also called the vapor pressure, it is given by a point on Fig. 3.1 where an isotherm (vertical
line) crosses the vaporization curve.
The two-phase liquid/vapor region lies under dome BC D; the subcooled-liquid region
lies to the left of the saturated-liquid curve BC, and the superheated-vapor region lies to

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