CHEMICAL ENGINEERING

THERMODYNAMICS
BKF2413

VOLUMETRIC PROPERTIES OF PURE

FLUIDS
Chapter 3
 Outline
• PVT Behavior of Pure Substances (W1)
– PT diagram for pure substance
– PV diagram and critical behavior
– Single phase region
• Virial Equations of State and Its Applications (W1)
– Universal gas constant
– Forms of virial equation
– Application
• Cubic Equations of State (W2)
• Generalized Correlations for Gases and Liquids (W2)
 Expected outcome
• Explain the PVT behavior of pure
substance
• Estimate volumetric properties of
pure substance using Virial EOS,
cubic equations of state and
generalized correlations for gases
and liquids.
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
P
• Triple point: a point, where all
the 3 phases are in equilibrium
• Critical point: the coordinates
are Pc & Tc
• Changes of state
Fig 3.1:PT diagram of a pure substance – 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
• Isotherm in the subcooled-
liq region are very steep
• The triple point of Fig.3.1
becomes horizontal line,
where the 3 phases coexist
at a single temperature
Fig 3.2: (a) PV diagram of pure substance and pressure.
(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 (b) shows
liquid, Liquid/vapor
regions with 4
isotherms

• BC: saturated liquid

• CD: saturated vapor

SL

• Isotherm in subcooled
region are very steep,
SH-V since liquid volumes
Two phase change little with large
region changes in pressure.

Fig 3.3 (b) : PV diagram for the liquid, liquid/vapour, and vapour
regions of a pure fluid with isotherms
 Critical Behavior
Cons. vol path
• Heating from J,K to Q
departs form the vapor-
pressure curve along the
line of cons molar volume
𝑉2𝑙
• Heating from J,K to N
Subcooled-
liq
departs form the vapor-
Superheat pressure curve along the
ed line of cons molar volume
𝑉2𝑣
Vap curve
• Heating from J,K to C
departs form the vapor-
pressure curve along the
line of cons molar volume
𝑉𝑐 (single phase region)
 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)
• 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 20 C and 1 bar, β=1.487x10-3 C-1,
κ=62x10-6 bar-1, V=1.287 cm3g-1. Find:
𝜕𝑃
a) The value of at 20oC and 1 bar
𝜕𝑇
b) The pressure generated when acetone is heated at
constant volume from 20 C and 1 bar to 40 C.
c) The volume change when acetone is changed from 20 C
and 1 bar to 0 C and 8 bar.
 Example 1 (page 69)
• For liquid acetone at 20 C and 1 bar, β=1.487x10-3 C-1,
κ=62x10-6 bar-1, V=1.287 cm3g-1. Find:
𝜕𝑃
a) The value of at 20 C and 1 bar
𝜕𝑇
𝛽𝑑𝑇 − κ𝑑𝑃 = 0 (constant V)
𝜕𝑃 𝛽
( )v = = 23.98 bar C-1
𝜕𝑇 κ

b) The pressure generated when acetone is heated at

constant volume from 20 C and 1 bar to 40 C.

c) The volume change when acetone is changed from 20 C

and 1 bar to 0 C and 8 bar.
 Example 1 (page 69)
• For liquid acetone at 20 C and 1 bar, β=1.487x10-3 C-1,
κ=62x10-6bar-1, V=1.287cm3g-1. Find:
𝜕𝑃
a) The value of at 20 C and 1 bar
𝜕𝑇
b) The pressure generated when acetone is heated at
constant volume from 20 C and 1 bar to 40 C.
𝛽 and κ are assumed to be constant, and T = 20 C, thus:
𝛽
P = T = 479.6 bar
κ
P2 = P1 + P = 480.6 bar
c) The volume change when acetone is changed from 20 C
and 1 bar to 0 C and 8 bar.
 Example 1 (page 69)
• For liquid acetone at 20 C and 1 bar, β=1.487x10-3 C-1,
κ=62x10-6bar-1, V=1.287cm3g-1. Find:
𝜕𝑃
a) The value of at 20 C and 1 bar
𝜕𝑇
b) The pressure generated when acetone is heated at
constant volume from 20 C and 1 bar to 40 C.
c) The volume change when acetone is changed from 20 C
and 1 bar to 0 C and 8 bar.
𝑉2
ln = 𝛽 𝑇2 − 𝑇1 − κ 𝑃2 − 𝑃1 solve the equation for V
𝑉1
 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+…
• If b ≡ aB’, c ≡ aC’ etc
PV=a (1+ B’P+ C’P2+D’P3+ …) (3.6)
where a, B’, C’ etc are constants for a given T and P
• Makes (PV)* directly proportional to T, with R as the
proportionality constant: (PV)*= a ≡ RT
 Virial EOS
• A useful property – compressibility factor defined by
𝑃𝑉
Z≡
𝑅𝑇
• With a=RT;
Z = 1+ B’P+ C’P2+D’P3+ … (3.11)

• Alternative form of Z is as follows;

𝐵 𝐶 𝐷
Z=1+ + + +⋯ (3.12)
𝑉 𝑉2 𝑉3
 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;
𝐵 𝐶 − 𝐵 2 𝐷 − 3𝐵𝐶 + 2𝐵 3
𝐵′ = , 𝐶′ = , 𝐷 ′
=
𝑅𝑇 𝑅𝑇 2 𝑅𝑇 3

• 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+ B’P
𝑃𝑉 𝐵𝑃
𝑍= =1+ (3.38)
𝑅𝑇 𝑅𝑇

– 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;
𝑃𝑉 𝐵
𝑍= =1+ (3.39)
𝑅𝑇 𝑉

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

𝑃𝑉 𝐵 𝐶
𝑍= =1+ + (3.40)
𝑅𝑇 𝑉 𝑉2
 Application of the Virial EOS
• Extended virial equations is illustrated by the
Benedict/Webb/Rubin equation;
𝐵0 𝑅𝑇 − 𝐴0 − 𝐶0
𝑅𝑇 𝑇 2 𝑏𝑅𝑇 − 𝑎
𝑃= + 2
+
𝑉 𝑉 𝑉3
𝑎𝛼 𝑐 𝛾 −𝛾
+ 6 + 3 2 1 + 2 𝑒 𝑉2
𝑉 𝑉 𝑇 𝑉
A0, B0, C0, a, b, c, α, γ: 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
 TUTORIAL QUESTIONS
Smith et al., 2005, 7th ed. (3.30 and 3.35)

Data for methyl chloride at 100°C for the second and third virial coefficients
are: B= - 242.5 cm3mol-1 C=25200 cm6mol-2. Calculate the work of
mechanically reversible, isothermal compression of 1 mol of methyl chloride
from 1 bar to 55 bar at 100°C. Based the calculation on the following forms
𝑃𝑉 𝐵 𝐶
of the virial equation: 𝑍 = =1+ + 2
𝑅𝑇 𝑉 𝑉
Ans: W=12.62 kJ/mol

Determine Z and V for steam at 250 deg C and 1800 kPa with the following
experimental values of virial coefficients: B=-152.5 cm3mol-1 and C=-5800
cm6mol-2. Based the calculation on the following forms of the virial
𝑃𝑉 𝐵 𝐶
equation: 𝑍 = 𝑅𝑇 = 1 + 𝑉 + 𝑉 2

Ans: V=2250 cm3/mol, Z=0.931

Phase determination
THE END

Questions?