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CHEMICAL ENGINEERING THERMODYNAMICS

VOLUMETRIC PROPERTIES OF PURE FLUIDS


LECTURE 1 (1.1 1.2)

PVT Behavior of Pure Substances

Fig 3.1:PT diagram of a pure substances

Fig 3.1 showed the phase boundaries on PT diagram 1-2: sublimation curve 2-3: fusion curve 2-C: vaporization curve Triple point: a point, where all the 3 phases are in equilibrium Critical point: the coordinates are Pc & Tc Changes of state Isothermal vertical line Isobaric horizontal line

PVT Behavior of Pure Substances

Fig 3.2: The PV diagram shows 2 phases coexisting in equilibrium at given temperature & pressure; Solid/Liquid Solid/Vapor Liquid/vapor The triple point of Fig.3.1 becomes horizontal line, where the 3 phases coexist at a single temperature and pressure.

Fig 3.2: PV diagram of pure substance (showing solid, liquid and gas region)

PVT Behavior of Pure Substances


Saturated Liquid: about to vaporize Saturated Vapor: about to condense For a fluid to be in a saturated state: = = =

At lower T or higher P: Subcooled liquid At higher T or lower P: Superheated vapour

PVT Behavior of Pure Substances

Fig. 3.3 shows liquid, Liquid/vapor regions with 4 isotherms BC: saturated liquid CD: saturated vapor Isotherm in subcooled region are very steep, since liquid volumes change little with large changes in pressure.
Subcooled Liquid

Two phase region

Superheated Vapor

Fig 3.3: PV diagram for the liquid, liquid/vapour, and vapour regions of a pure fluid with isotherms

Critical Behavior

Single Phase Region

For the regions of diagrams where a single phase exists, implies a relation connecting P, V & T f (P, V, T) = 0 (PVT EOS)

Ideal gas EOS : PV = RT

(for low P gas region)

To solve the equation : V = f (P, T)

Single Phase Region

The partial derivative of the equation is

Single Phase Region

Volume expansivity,

Isothermal compressibility,
Combine it to become;

Single Phase Region

Integrate to get the following equation

2 ln = 2 1 2 1 1

For L phase (incompressible), and are very small until almost zero.

Example 1 (page 69)

For liquid acetone at 20oC and 1 bar, =1.487x10-3oC-1, =62x10-6bar-1, V=1.287cm3g-1. Find:
a) The value of

b) The pressure generated when acetone is heated at constant volume from 20oC and 1 bar to 40oC. c) The volume change when acetone is changed from 20oC and 1bar to 0oC and 8 bar.

Virial EOS

Virial EOS: used to describe the PVT behavior of pure substance Virial denotes the use of a power series on one sides of the equation

PV for an isotherm by a power series in P; PV=a+bP+cP2+

Virial EOS

If b aB, c aC etc PV=a(1+ BP+ CP2+DP3+ )

(3.6)

Where a, B, C etc are constants for a given T and P

Virial EOS

A useful property compressibility factor defined by Z With a=RT; Z = 1+ BP+ CP2+DP3+ Alternative form of Z is as follows;

Z=1+ + 2+ 3

Virial EOS

Both form of Z are called the virial expansion Parameters B, C, D, etc and B, C, D are the virial coefficients and depends on T They are related as follows;

2 3 3 + 2 = , = , = 2 3

Virial EOS

Equation 2nd term: interaction between pairs of molecules. Equation 3rd term: three-body interactions. Because 2-body interactions 3-body, 3-body interactions 4-body, higher-ordered terms have less effect on Z.

Ideal Gas

Virial expansion arise on account of interaction between molecules. For ideal gas, there are no molecular interactions. Hence; Z=1 PV=RT

Application of the Virial EOS

A common form of Z is ; Z = 1+ BP

=1+

(3.37)

It is applicable for vapors at subcritical T up to their saturation P. It can be the approximation for gases at higher T up to P of 5 bar.

Application of the Virial EOS

For application at low P, the equation may be truncated to 2 terms;

=1+

(3.38)

Application of the Virial EOS

For application at high P, but below critical pressure, the equation may be truncated to 3 terms;

=1+ +

(3.39)

Application of the Virial EOS

Extended virial equations is illustrated by the Benedict/Webb/Rubin equation; 0 0 0 2 = + + 2 3 + 6 + 3 2 1 + 2 2

A0, B0, C0, a, b, c, , : constant for a given fluid

Equation used for petroleum and natural gas industries

Example 2 (page 89)

Reported value for virial coefficients of X vapor at 200 oC are: B=-388cm3mol-1, C=26000cm6mol-2. calculate V and Z for X vapor at 200oC and 8 bar by:

A) the ideal gas equation B) equation 3.38 C) equation 3.40

THE END

Questions?