CHEMICAL

ENGINEERING
THERMODYNAMICS
VOLUMETRIC PROPERTIES
OF PURE FLUIDS
Chapter 3
 PVT Behavior of 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

Fig 3.1:PT diagram of a pure substance  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:

𝑃𝑙𝑖𝑞 = 𝑃𝑣𝑎𝑝
𝑇𝑙𝑖𝑞 = 𝑇𝑣𝑎𝑝
𝐺𝑙𝑖𝑞 = 𝐺𝑣𝑎𝑝
 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

Subcooled Liquid
 BC: saturated liquid
Super-
Two
heated
 CD: saturated vapor phase
Vapor
region

 Isotherm in subcooled region

are very steep, since liquid
volumes change little with
large changes in pressure.
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

𝛿𝑉 𝛿𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃
𝛿𝑇 𝑃
𝛿𝑃 𝑇
 Single Phase Region
1 𝛿𝑉
 Volume expansivity, 𝛽 ≡
𝑉 𝛿𝑇 𝑃

1 𝛿𝑉
 Isothermal compressibility, κ ≡ −
𝑉 𝛿𝑃 𝑇

ⅆ𝑉
 Combine it to become; ≡ 𝛽𝑑𝑇 − κ𝑑𝑃
𝑉
 Single Phase Region
 Integrate to get the following equation
𝑉2
ln = 𝛽 𝑇2 − 𝑇1 − κ 𝑃2 − 𝑃1
𝑉1

 For L phase (incompressible), β and κ are very small

until almost zero.
 Example 1 (page 69)
 For liquid acetone at 20oC and 1 bar,
β=1.487x10-3oC-1, κ=62x10-6bar-1,
V=1.287cm3g-1. Find:
𝜕𝑃
a) The value of
𝜕𝑇
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.