MODULE 2

Volumetric Properties of Pure Fluids

Outline
■ PVT Behavior of Pure Liquids
■ The Virial Equation of State
■ Cubic Equations of State
■ Generalized Pitzer Correlations
PVT Behavior of Pure Liquids
■ An equation of state can be derived expressing volume
as a function of temperature and pressure.
■ For simplification purposes, two parameters are
introduced: the isothermal compressibility and the
volumetric expansivity.
1 𝜕𝑉
𝛽=
𝑉 𝜕𝑇 𝑃
1 𝜕𝑉
𝜅=−
𝑉 𝜕𝑃 𝑇
PVT Behavior of Pure Liquids
 Sample Problem 1
The following table shows the molar volume coefficient of thermal
expansion and coefficient of isothermal compressibility at 20˚C of
substances in condensed phases.
a. What is the molar volume change for copper for the large
pressure change of going from 1bar to 1000bar at 20˚C?
b. What is the volume change for sodium chloride?

Solid V (cm3/mol) αx104/K κx106/bar

Copper 7.12 0.492 0.77
Sodium Chloride 27.02 1.21 4.15
 Solid V (cm3/mol) αx104/K κx106/bar
Copper 7.12 0.492 0.77
Sodium Chloride 27.02 1.21 4.15
 Sample Problem 2
For liquid acetone at 20˚C & 1bar,
β=1.487x10-3 ˚C-1, κ=62x10-6bar-1, and
V=1.287cm3/g.
a. What is the value of (∂P/∂T)V?
b. What is the pressure generated by heating at
constant V from 20˚C and 1bar to 30˚C?
c. What is the change in volume for a change
from 20˚C and 1bar to 0˚C and 10bar?
 Sample Problem 3
5kg of CCl4 undergoes a mechanically reversible,
isobaric change of state at 1bar during which the
temperature changes from 0˚C to 20˚C. The
properties for liquid CCl4 at 1bar and 0˚C may be
assumed independent of temperature:
β=1.2x10-3/K, CP=0.84kJ/kg-K, and ρ=1590kg/m3.
a. Determine ΔV
b. Determine W
c. Determine Q.
d. Determine ΔU.
 Sample Problem 4
For liquid water, the isothermal compressibility
is given by:
𝐶
𝜅=
𝑉(𝑃 + 𝑏)
Where C and b are functions of temperature
only. If 1kg of water is compressed isothermally
from 1 to 500bar at 60˚C, how much work is
required? At 60˚C, b=2700bar and
C=0.125cm3/g.
The Virial Equation of State
■ When calculating the properties of a real gas, the
compressibility factor Z is introduced to account its
deviation from ideality.
𝑃𝑉𝑚 𝐵 𝐶
𝑍= =1+ + 2+⋯
𝑅𝑇 𝑉𝑚 𝑉𝑚
 Sample Problem 5
Reported virial coefficients of isopropanol
vapor at 200 ˚C are: B = -388 cm3/mol and C =
26000 cm6/mol2.
a. Calculate V for isopropanol vapor at 200˚C
and 10bar by ideal gas.
b. Calculate V and Z by the virial equation of
state.
Cubic Equations of State
■ Cubic Equation of State (Liquids)
1+𝛽−𝑍
𝑍 = 𝛽 + (𝑍 + 𝜀𝛽)(𝑍 + 𝜎𝛽)
𝑞𝛽
■ Cubic Equation Of State (Vapor)
𝑞𝛽(𝑍 − 𝛽)
𝑍 = 1+𝛽−
(𝑍 + 𝜀𝛽)(𝑍 + 𝜎𝛽)
Where:
Ω𝑃𝑟 Ψ𝛼 𝑇𝑟 𝑃 𝑇
𝛽= ,𝑞 = , 𝑃𝑟 = , 𝑇𝑟 =
𝑇𝑟 Ω𝑇𝑟 𝑃𝑐 𝑇𝑐
Equation α(TR) σ ε Ω Ψ
Van Der Waals 1 0 0 1/8 27/64
Redlich-Kwong TR-1/2 1 0 0.08664 0.42748
Soave-Redlich Kwong αSRK(TR,ω) 1 0 0.08664 0.42748
Peng-Robinson αPR(TR,ω) 1+ 2 1− 2 0.0778 0.45724

2
𝛼𝑆𝑅𝐾 𝑇𝑟 , 𝜔 = 1 + 0.48 + 1.574𝜔 − 0.176𝜔2 1 − 𝑇𝑟
2
𝛼𝑃𝑅 𝑇𝑟 , 𝜔 = 1 + 0.37464 + 1.54226𝜔 − 0.26992𝜔2 1 − 𝑇𝑟
Generalized Pitzer Correlations
■ Generalized compressibility-factor correlation
𝑍 = 𝑍° + 𝜔𝑍′
■ Generalized Correlation for B
′
𝑃𝑟
𝑍 = 1 + (𝐵° + 𝜔𝐵 )
𝑇𝑟
Where:
0.422
𝐵° = 0.083 − 1.6
𝑇𝑟

0.172
𝐵′ = 0.139 − 4.2
𝑇𝑟
Generalized Pitzer Correlations
■ Generalized Correlation for C
2
𝑃𝑟 𝑃𝑟
𝑍 = 1 + 𝐵෠ + 𝐶መ
𝑇𝑟 𝑍 𝑇𝑟 𝑍
Where:
𝐵෠ = 𝐵° + 𝜔𝐵′
𝐶መ = 𝐶° + 𝜔𝐶 ′

0.02432 0.00313
𝐶° = 0.01407 + −
𝑇𝑟 𝑇𝑟10.5

0.05539 0.00242
𝐶′ = −0.02676 + 2.7 −
𝑇𝑟 𝑇𝑟10.5
 Sample Problem 6
It is required to store 1kmol of methane at
320K and 60MPa. Estimate the volume of the
vessel which must be provided.
a. Use the ideal gas equation.
b. Use the Van der Waal’s Equation.
c. Use a generalized compressibility-factor
correlation.
 Sample Problem 7
Given that the vapor pressure of butane at 350K is 9.4573bar, find:
a. The molar volume of saturated vapor using the Redlich Kwong
Equation.
b. The molar volume of saturated liquid using the Redlich Kwong
Equation
c. The molar volume of saturated vapor using the Peng Robinson
Equation.
d. The molar volume of butane at 510K and 25bar using the
generalized compressibility-factor correlation.
e. The molar volume of butane at 510K and 25bar using the
equation with the generalized correlation for B.
 Sample Problem 8
a. Calculate the molar volume for ethylene at 25˚C and 12bar by
the truncated virial equation with the following experimental
values of virial coefficients: B=-140cm3/mol, C=7200cm6/mol2.
b. Calculate the molar volume for ethylene by the Redlich Kwong
Equation.
c. Calculate the molar volume for ethylene by the Peng Robinson
Equation.
d. Calculate the molar volume for ethylene by the truncated virial
equation with the value of B from the generated Pitzer
correlation.
e. Calculate the molar volume for ethylene at 25˚C and 12bar by
the generalized correlation for C.
 Sample Problem 9
In a system where 1lbmol of methane is stored
in a volume of 2ft3 at 122˚F, calculate the
pressure generated based on the following:
a. Ideal gas equation
b. The Redlich Kwong equation
c. A generalized correlation