Volumetric Properties

of Pure Substances

Engr. Ralph John Erwin R. Ornales

Department of Chemical Engineering
 Learning Objectives

◉ Apply phase rule in determining the number of

variables needed to complete the thermodynamic
state of a system.
◉ Recognize PVT relationships based on ideal and real
behavior.
◉ Solve problems involving thermodynamic properties
of pure substances.

2
 Topics

◉ Phase Rule
◉ PVT Behavior of Pure Substances
◉ Ideal and Real Gases
◉ Virial Equations of State
◉ Cubic Equations of State
◉ Generalized Correlation for Gases and Liquids
◉ Thermodynamic Tables
3
1. Phase Rule

4
 Phase Rule

◉ A phase is a homogeneous region of matter (e.g. gas

or a mixture of gases, liquid or a liquid solution, and a
crystalline solid)
◉ The intensive state of a system at equilibrium is
established when its temperature, pressure, and the
compositions of all phases are fixed.

5
 Phase Rule

For a multiphase system at equilibrium, the number of

independent variables that must be arbitrarily fixed to establish
its intensive state is called the number of degrees of freedom
of the system. This is given by the phase rule of J. Willard
Gibbs.
𝑭=𝟐−𝝅+𝑵
Where F is the number of degrees of freedom, 𝝅 is the number
of phases, and N is the number of chemical species present in
the system.
6
 Phase Rule

As an example, the phase rule may be applied to an

aqueous solution of ethanol in equilibrium with its vapor. Here,
𝑁 = 2 and 𝜋 = 2
𝐹 =2−𝜋+𝑁
𝐹 =2−2+2=𝟐
This is a system in vapor/liquid equilibrium, and it has two
degrees of freedom. If the system exists at specified T and P
(assuming this is possible), its liquid-phase and vapor-phase
compositions are fixed by these conditions.

7
 Sample Problem

1. How many phase-rule variables must be specified to fix

the thermodynamic state of each of the following systems?
a) Liquid water in equilibrium with its vapor
b) Liquid water in equilibrium with a mixture of water vapor
and nitrogen
c) A three-phase system of a saturated aqueous salt
solution at its boiling point with excess salt crystals present.

8
 Sample Problems

a) Liquid water in equilibrium with its vapor

𝐹 =2−𝜋+𝑁 =2−2+1
𝑭=𝟏
b) Liquid water in equilibrium with a mixture of water vapor and
nitrogen
𝐹 =2−𝜋+𝑁 =2−2+2
𝑭=𝟐
c) A three-phase system of a saturated aqueous salt solution at its
boiling point with excess salt crystals present.
𝐹 =2−𝜋+𝑁 =2−3+2
𝑭=𝟏 9
2. PVT Behavior of Pure Substances

10
 Phase Diagram

◉ A graphical representation which

details the form(s) the material
takes under specific conditions.
◉ Phase diagrams illustrate the
variations between the states of
matter of elements or compounds
as they relate to pressure and
temperatures.

11
 Phase Diagram

◉ Triple Point – the point on a phase

diagram at which the three states
coexist
◉ Critical Point – the point on a phase
diagram at which the substance is
indistinguishable between liquid
and gaseous states

12
 Phase Diagram

◉ Fusion curve – the curve on a phase

diagram which represents the
transition between liquid and solid
states
◉ Vaporization curve – the curve on a
phase diagram which represents the
transition between gaseous and liquid
states
◉ Sublimation curve – the curve on a
phase diagram which represents the
transition between gaseous and solid
states 13
Phase Diagram

𝑷𝑪 and 𝑻𝑪 : highest pressure and

highest temperature at which a pure
chemical species is observed to exist I
vapor/liquid equilibrium.

According to phase rule:

𝑭 = 𝟎 : the triple point (invariant)
𝑭 = 𝟏 : if the system exists along any of
the two-phase lines (univariant)
𝑭 = 𝟐 : single-phase regions (divariant)
14
Phase Diagram

15
Phase Diagram

◉ Subcooled liquid – exists at

temperatures below the
boiling point for a given
pressure.
◉ Superheated vapor – exists
at temperatures above the
boiling point for a given
pressure.

16
Phase Diagram

Example: Gas in a piston at an initial

pressure of 1 𝑀𝑃𝑎 is compressed
until it reaches a specific volume of
0.1 𝑚3 /𝑘𝑔 . It is then cooled at
constant volume until it reaches a
pressure of 100 𝑘𝑃𝑎. What are its
final temperature and phase?

Temperature: 100℃
Phase: Liquid/Vapor region

17
 PVT Surfaces

(a) Substance that contracts upon freezing. (b) Substance that expands upon freezing
18
 PVT Surfaces

PVT Surface Projection of a substance that expands on freezing

19
 Single-Phase Regions

◉ PVT Equation of State – relates pressure, molar or

specific volume, and temperature for a pure
homogeneous fluid at equilibrium, expressed
analytically as 𝑓 𝑃, 𝑉, 𝑇 = 0

𝝏𝑽 𝝏𝑽
𝒅𝑽 = 𝒅𝑻 + 𝒅𝑷
𝝏𝑻 𝑷 𝝏𝑷 𝑻

20
 Single-Phase Regions
1 𝜕𝑉
Volume expansivity: 𝛽=
𝑉 𝜕𝑇 𝑃

1 𝜕𝑉
Isothermal compressibility: 𝜅= −
𝑉 𝜕𝑃 𝑇

Combining to the previous equation:

𝒅𝑽
= 𝜷𝒅𝑻 − 𝜿𝒅𝑷
𝑽

*For incompressible fluid, the value of 𝛽 and 𝜅 are zero. No significant

change in volume will transpire even temperature and pressure change.
21
 Sample Problem

For liquid acetone at 20℃ and 1 𝑏𝑎𝑟,

𝛽 = 1.487 × 10−3 /℃
𝜅 = 62 × 10−6 /𝑏𝑎𝑟
𝑉 = 1.287 𝑐𝑚3 /𝑔
For acetone, find:
𝜕𝑃
a) The value of at 20℃ and 1 𝑏𝑎𝑟.
𝜕𝑇 𝑉
b) The pressure after heating at constant V from 20℃ and 1 𝑏𝑎𝑟 to 30℃.
c) The volume change when T and P go from 20℃ and 1 𝑏𝑎𝑟 to 0℃ and
10 𝑏𝑎𝑟
22
 Sample Problem
𝜕𝑃
a) The value of 𝜕𝑇 𝑉
at 20℃ and 1 𝑏𝑎𝑟.

Solution:
𝛽𝑑𝑇 − 𝜅𝑑𝑃 = 0 (constant V)
𝜕𝑃 𝛽 1.487 × 10−3 /℃
= = = 𝟐𝟑. 𝟗𝟖 𝒃𝒂𝒓/℃
𝜕𝑇 𝑉 𝜅 62 × 10−6 /𝑏𝑎𝑟

b) The pressure after heating at constant V from 20℃ and 1 𝑏𝑎𝑟 to 30℃.
Solution:
𝑑𝑉 𝑉
𝑉
= 𝛽𝑑𝑇 − 𝜅𝑑𝑃 ⇒ 𝑙𝑛 𝑉2 = 𝛽(𝑇2 − 𝑇1 ) − 𝜅(𝑃2 − 𝑃1 )
1

At constant V, 𝛽 𝑇2 − 𝑇1 = 𝜅(𝑃2 − 𝑃1 )
10−3 10−6
1.487 × 30℃ − 20℃ = 62 × 𝑃2 − 1 𝑏𝑎𝑟 ⇒ 𝑷𝟐 = 𝟐𝟒𝟎. 𝟖𝟒 𝒃𝒂𝒓
℃ 𝑏𝑎𝑟
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 Sample Problem

c) The volume change when T and P go from 20℃ and 1 𝑏𝑎𝑟 to 0℃ and
10 𝑏𝑎𝑟.
Solution:
𝑑𝑉 𝑉2
= 𝛽𝑑𝑇 − 𝜅𝑑𝑃 ⇒ 𝑙𝑛 = 𝛽(𝑇2 − 𝑇1 ) − 𝜅(𝑃2 − 𝑃1 )
𝑉 𝑉1
𝑉 10−3 10−6
𝑙𝑛 2 = 1.487 × 0℃ − 20℃ − 62 × 10 𝑏𝑎𝑟 − 1 𝑏𝑎𝑟
𝑉1 ℃ 𝑏𝑎𝑟
𝑉2 𝑐𝑚3
= 0.9701 ⇒ 𝑉2 = 0.9701𝑉1 = 0.9701 1.287 = 1.2485 𝑐𝑚3 /𝑔
𝑉1 𝑔
∆𝑉 = 𝑉2 − 𝑉1 = 1.2485 − 1.287 = −𝟎. 𝟎𝟑𝟖𝟓 𝒄𝒎𝟑 /𝒈

24
3. Ideal and Real Gases

25
 Ideal Gas

◉ A hypothetical gas whose molecules occupy negligible

space and have no interactions, and which consequently
obeys the gas laws exactly.
◉ In ideal gases, the volume occupied by the molecules
themselves is negligible compared with the total volume
at all pressures and temperatures and the intermolecular
attraction is extremely small under all conditions.
◉ Also called perfect gas

26
 Ideal Gas Law

◉ The equation of state of a hypothetical ideal gas.

◉ States the relationship between the pressure applied by a
gas, the amount of gaseous substance, the absolute
temperature of the gas, and the volume occupied by the
gas.
𝑷𝑽 = 𝒏𝑹𝑻
𝑳∙𝒂𝒕𝒎
Where R is the gas constant with values 𝟎. 𝟎𝟖𝟐𝟎𝟔 ,
𝒎𝒐𝒍∙𝑲
𝑷𝒂∙𝒎𝟑 𝒃𝒂𝒓∙𝒄𝒎𝟑
𝟖. 𝟑𝟏𝟒 and 𝟖𝟑. 𝟏𝟒
𝒎𝒐𝒍∙𝑲 𝒎𝒐𝒍∙𝑲
27
 Universal Gas Constant

Appendix A, Intro to ChE Thermo by Van Ness, Smith, 8th ed.

28 Table 1-13, Perry’s Handbook, 9th ed.

 Real Gas
◉ A gas that does not behave according to the assumptions of
kinetic molecular theory
◉ For non-ideal or real gases, the volume occupied and the
intermolecular interaction are appreciable, the magnitude of
each depending on the nature, temperature, and pressure of
the gas.
◉ Deviates most from an ideal gas at low temperatures and
high pressures.
◉ At room temperature and pressure, real gases tend to
behave very much like ideal gases.
29
 Compressibility Factor

◉ In thermodynamics, the compressibility factor, also known

as the compression factor or gas deviation factor, describes
the deviation of a real gas from ideal gas behavior.
◉ It is simply defined as the ratio of the molar volume of a gas
to the molar volume of an ideal gas at the same
temperature and pressure.
◉ For ideal gases, 𝒁 = 𝟏
𝑷𝑽 𝑽
𝒁= =
𝑹𝑻 𝑽𝒊𝒈
30
 Sample Problems

1. An ideal gas is contained in a closed assembly with an initial

pressure and temperature of 220 𝑘𝑃𝑎 and 70℃ respectively. if
the volume of the system is increased 1.5 𝑡𝑖𝑚𝑒𝑠 and the
temperature drops to 15℃, determine the final pressure of the
gas.

Given: 𝑃1 = 220 𝑘𝑃𝑎 Required: 𝑃2

𝑇1 = 70℃ ≈ 343.15 𝐾 Formula: 𝑃𝑉 = 𝑛𝑅𝑇
𝑉2 = 1.5𝑉1
𝑇2 = 15℃ ≈ 288.15 𝐾
31
 Sample Problems

𝑃𝑉
Solution: 𝑃𝑉 = 𝑛𝑅𝑇 ; 𝑛 =
𝑅𝑇
𝑃 𝑉 𝑃 𝑉
For two states: 𝑛1 = 𝑛2 ; 1 1 = 2 2
𝑅𝑇1 𝑅𝑇2
𝑃 𝑉 𝑅𝑇 220 𝑘𝑃𝑎 𝑉1 (288.15 𝐾)
𝑃2 = 1 1 2 =
𝑅𝑇1 𝑉2 (343.15 𝐾)(1.5𝑉1 )
𝑷𝟐 = 𝟏𝟐𝟑. 𝟏𝟔 𝒌𝑷𝒂

32
 Sample Problems

2. An automobile tire with a volume of 0.6 𝑚3 is inflated to a

gauge pressure of 200 𝑘𝑃𝑎. Calculate the mass of air in the tire
if the temperature is 20℃.

Given: 𝑉 = 0.6 𝑚3
𝑃𝑔𝑎𝑢𝑔𝑒 = 200 𝑘𝑃𝑎
𝑇 = 20℃ ≈ 293.15 𝐾
Required: mass of air
Formula: 𝑃𝑉 = 𝑛𝑅𝑇
33
 Sample Problems

𝑚
Solution: 𝑃𝑉 = 𝑛𝑅𝑇 ; 𝑛 = 𝑤ℎ𝑒𝑟𝑒 𝑀 𝑖𝑠 𝑡ℎ𝑒 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
𝑀
For air: 𝑀 = 29 𝑔/𝑚𝑜𝑙
𝑚 𝑃𝑉𝑀
𝑃𝑉 = 𝑅𝑇 ; 𝑚=
𝑀 𝑅𝑇
𝑃 = 𝑃𝑔𝑎𝑢𝑔𝑒 + 𝑃𝑎𝑡𝑚 = 200 𝑘𝑃𝑎 + 101.325 𝑘𝑃𝑎 = 301.325 𝑘𝑃𝑎
𝑔
301.325×103 𝑃𝑎 0.6 𝑚3 29𝑚𝑜𝑙
𝑚= 𝑃𝑎∙𝑚3
8.314 𝑚𝑜𝑙∙𝐾 (293.15 𝐾)

𝒎 = 𝟐𝟏𝟓𝟏. 𝟐𝟐 𝒈

34
4. Virial Equations of State

35
 Virial Equations of State

Applicable to gases based on the isotherms for gases and

vapors lying at the right of the saturated vapor curve in a
phase diagram, where PV for a given T varies more slowly
giving the equation as a function of P.
𝑷𝑽 = 𝒂 + 𝒃𝑷 + 𝒄𝑷𝟐 + ⋯
If 𝑏 = 𝑎𝐵′, 𝑐 = 𝑎𝐶′, etc. Then,
𝑷𝑽 = 𝒂 (𝟏 + 𝑩′ 𝑷 + 𝑪′ 𝑷𝟐 + 𝑫′ 𝑷𝟑 + ⋯ )
Where 𝐵′ , 𝐶′ , and others are constants for a given
temperature and a given substance.
36
 Virial Equations of State
𝑃𝑉
With 𝒁 defined as and with 𝑎 = 𝑅𝑇,
𝑅𝑇
𝒁 = 𝟏 + 𝑩′ 𝑷 + 𝑪′ 𝑷𝟐 + 𝑫′ 𝑷𝟑 + ⋯
An alternative expression for 𝒁 that is also commonly used is:
𝑩 𝑪 𝑫
𝒁=𝟏+ + + +⋯
𝑽 𝑽𝟐 𝑽𝟑
These equations are known as virial expansion, and the parameters
𝑩′ , 𝑪′ , 𝑫′ , etc. and B, C, D, etc. are called virial coefficients. The
parameters 𝑩′ and B is second virial coefficient; 𝑪′ and C is third virial
coefficient, and so on. For a given gas, the virial coefficients are
functions of temperature only.
37
 Virial Equations of State

Truncated Virial Equation (Two Terms) – for application at

low pressures:
𝑷𝑽 𝑩𝑷 𝑩
𝒁= =𝟏+ =𝟏+
𝑹𝑻 𝑹𝑻 𝑽
Truncated Virial Equation (Three Terms) – for pressures
above the range of applicability of two terms but below the
critical pressure:
𝑷𝑽 𝑩 𝑪
𝒁= =𝟏+ + 𝟐
𝑹𝑻 𝑽 𝑽
38
 Sample Problem

1. Reported values for the virial coefficients of isopropanol

vapor at 200℃ are:
𝐵 = −388 𝑐𝑚3 /𝑚𝑜𝑙
𝐶 = −26,000 𝑐𝑚6 /𝑚𝑜𝑙 2
Calculate Z for isopropanol vapor at 200℃ and 10 𝑏𝑎𝑟:
a) For the ideal gas state
b) Truncated virial equation to two terms
c) Truncated virial equation to three terms
39
 Sample Problems

a) For ideal gas: 𝒁 = 𝟏

𝑏𝑎𝑟∙𝑐𝑚3
𝑅𝑇 83.14 (473.15 𝐾)
𝑚𝑜𝑙∙𝐾
𝑉 𝑖𝑔 = = = 3933.7691 𝑐𝑚3 /𝑚𝑜𝑙
𝑃 10 𝑏𝑎𝑟
b) Truncated virial equation to two terms
𝑃𝑉 𝐵𝑃 𝑅𝑇
𝑍= =1+ ; 𝑉= +𝐵
𝑅𝑇 𝑅𝑇 𝑃
𝑏𝑎𝑟∙𝑐𝑚3
83.14 (473.15 𝐾) 𝑐𝑚3
𝑚𝑜𝑙∙𝐾
𝑉= + −388 = 3545.7691 𝑐𝑚3 /𝑚𝑜𝑙
10 𝑏𝑎𝑟 𝑚𝑜𝑙
𝑉 3545.7691
𝑍= = = 𝟎. 𝟗𝟎𝟏𝟒
𝑉 𝑖𝑔 3933.7691
40
 Sample Problems

c) Truncated virial equation to three terms

𝑃𝑉 𝐵 𝐶
𝑍= =1+ +
𝑅𝑇 𝑉 𝑉2
Using the value of V from truncated virial equation to two
terms:
−388 𝑐𝑚3 /𝑚𝑜𝑙 −26,000 𝑐𝑚6 /𝑚𝑜𝑙 2
𝑍 =1+ +
3545.7691 𝑐𝑚3 /𝑚𝑜𝑙 (3545.7691 𝑐𝑚3 /𝑚𝑜𝑙)2
𝒁 = 𝟎. 𝟖𝟖𝟖𝟓

41
 Sample Problem

2. The virial coefficient B for 𝑁2 (𝑔) at 500 𝐾 is 0.0169 𝐿/𝑚𝑜𝑙.

Calculate the molar volume, 𝑉𝑚 of 𝑁2 (𝑔) at a pressure of
500 𝑏𝑎𝑟 according to
a) the perfect gas law
b) the virial equation

42
 Sample Problems

a) Using perfect gas law:

𝐿∙𝑎𝑡𝑚
𝑅𝑇 0.08206𝑚𝑜𝑙∙𝐾 (500 𝐾)
𝑉𝑚 = = 105 𝑃𝑎 1 𝑎𝑡𝑚
𝑃 500 𝑏𝑎𝑟 1 𝑏𝑎𝑟 101 325 𝑃𝑎
𝑽𝒎 = 𝟎. 𝟎𝟖𝟑𝟏 𝑳/𝒎𝒐𝒍
b) Using the virial equation:
𝑃𝑉 𝐵 𝑅𝑇
𝑍= =1+ ; 𝑉= +𝐵
𝑅𝑇 𝑉 𝑃
𝐿∙𝑎𝑡𝑚
0.08206𝑚𝑜𝑙∙𝐾 (500 𝐾) 𝐿
𝑉𝑚 = 105 𝑃𝑎 1 𝑎𝑡𝑚
+ 0.0169
500 𝑏𝑎𝑟 1 𝑏𝑎𝑟 𝑚𝑜𝑙
101 325 𝑃𝑎
𝑽𝒎 = 𝟎. 𝟏𝟎𝟎𝟎 𝑳/𝒎𝒐𝒍
43
5. Cubic Equations of State

44
 Van der Waals Equation of State

The first practical cubic equation of state was proposed by J.D.

van der Waals in 1873 known as the van der Waals equation:
𝒏𝑹𝑻 𝒂𝒏𝟐 𝑹𝑻 𝒂
𝑷= − or 𝑷 = −
𝑽−𝒏𝒃 𝑽𝟐 𝑽−𝒃 𝑽𝟐

Here, a and b are constants, specific to a particular species;

when they are zero, the equation for ideal gas state is
recovered.

45
 Van der Waals Equation of State

The parameter a is related to intermolecular attractive

force between the molecules and 1/V is the density of the
molecules. The net effect of the intermolecular attractive force
is to reduce the pressure for a given volume and temperature.

The parameter b is related to the size of each molecule.

The volume that the molecules move around is not just the
volume of the container but is reduced to (V-b).

46
Van der Waals Constants

47
 Sample Problem

1. What will be the temperature calculated using the Van

der Waals equation for 1.00 𝑚𝑜𝑙𝑒 of 𝐶𝑙2 (𝑔) in a volume of
1.00 𝐿 at a pressure of 31.0 𝑎𝑡𝑚?
The values of the van der Waals constant for 𝐶𝑙2 (𝑔) are:
𝐿2 ∙𝑎𝑡𝑚
𝑎 = 6.493
𝑚𝑜𝑙 2
𝑏 = 0.5622 𝐿/𝑚𝑜𝑙

48
 Sample Problem

𝑛𝑅𝑇 𝑎𝑛2 𝑎𝑛2 𝑛𝑅𝑇

Solution: 𝑃 = − 2 ; 𝑃+ =
𝑉−𝑛𝑏 𝑉 𝑉2 𝑉−𝑛𝑏
𝑎𝑛2
𝑃+ 2 (𝑉−𝑛𝑏)
𝑉
𝑇=
𝑛𝑅
𝐿2 ∙𝑎𝑡𝑚
6.493 2 1 𝑚𝑜𝑙 2
𝑚𝑜𝑙 𝐿
31 𝑎𝑡𝑚+ 1 𝐿 −(1 𝑚𝑜𝑙)(0.5622𝑚𝑜𝑙)
1𝐿 2
𝑇= 𝐿∙𝑎𝑡𝑚
1 𝑚𝑜𝑙 0.08206
𝑚𝑜𝑙∙𝐾
𝑻 = 𝟐𝟎𝟎. 𝟎𝟐𝟗𝟕 𝑲

49
 Berthelot Equations of State

◉ Named after Daniel Berthelot

◉ One of the real gas equations of state developed to relate
the properties of gases
◉ Modified van der Waals EOS
𝑹𝑻 𝒂
𝑷= − 𝟐
𝑽 − 𝒃 𝑻𝑽
𝟐𝟕𝑹𝟐 𝑻𝒄 𝟑 𝑹𝑻𝒄
Where 𝒂 = and 𝒃 = are the empirical coefficient
𝟔𝟒𝑷𝒄 𝟖𝑷𝒄
and sometimes called van der Waals constant

50
 Dieterici Equations of State

◉ An empirical equation of state for gases

◉ Reduces to the van der Waals model for imperfect fluid at
low energy density
𝑹𝑻 −𝒂
𝑷= 𝒆 𝑹𝑻𝑽
𝑽−𝒃
𝟒𝑹𝟐 𝑻𝒄 𝟐 𝑹𝑻𝒄
Where 𝒂 = and 𝒃 = are the critical constants
𝑷𝒄 𝒆𝟐 𝑷𝒄 𝒆𝟐

51
 Generic Cubic Equation of State

A generic cubic equation of state, written as

𝑹𝑻 𝒂(𝑻)
𝑷= −
𝑽−𝒃 (𝑽+𝝐𝒃)(𝑽+𝝈𝒃)

For a specific form of this equation, 𝝐 and 𝝈 are pure

numbers, the same for all substances, whereas
parameters 𝒂(𝑻) and 𝒃 are substance-dependent.

52
 Roots of the Generic Cubic Equation of State

Equations of state are commonly transformed into expressions

for compressibility factor.
For vapor and vapor-like roots:
𝒁−𝜷
𝒁 = 𝟏 + 𝜷 − 𝒒𝜷
(𝒁+𝜺𝜷)(𝒁+𝝈𝜷)
For liquid and liquid-like roots:
𝟏+𝜷−𝒁
𝒁 = 𝜷 + 𝒁 + 𝜺𝜷 𝒁 + 𝝈𝜷
𝒒𝜷
𝑷𝒓 𝚿𝜶(𝑻𝒓 )
Where 𝜷 = 𝛀 and 𝒒 =
𝑻𝒓 𝛀𝑻𝒓

53
 Cubic Equations of State

◉ Critical Point – the condition at which the start of the fluid

behavior where the liquid and gas can no longer be
distinguished.
◉ Reduced Properties – set of state variables scaled by the
fluid’s state properties at its critical point
𝑷 𝑻
𝑷𝒓 = ; 𝑻𝒓 =
𝑷𝒄 𝑻𝒄

54
 Cubic Equations of State

Reference: Intro to ChE Thermo by Van Ness, Smith, 8th ed.

55
 Redlich-Kwong Equations of State

The Redlich-Kwong Equation of State can be written

simply as
𝑹𝑻 𝒂(𝑻)
𝑷= −
𝑽−𝒃 𝑽(𝑽+𝒃)
Parameters:
𝜶(𝑻𝒓 )𝑹𝟐 𝑻𝒄 𝟐 𝑹𝑻𝒄
𝒂 𝑻 = 𝚿 ; 𝒃= 𝛀
𝑷𝒄 𝑷𝒄

56
 Sample Problem

1. Given that the vapor pressure of n-butane at 350 𝐾 is

9.4573 𝑏𝑎𝑟, find the molar volumes of (a) saturated vapor
and (2) saturated liquid n-butane at these conditions as
given by the Redlich-Kwong equation.

Given: 𝑇 = 350 𝐾
𝑃 = 9.4573 𝑏𝑎𝑟

57
 Cubic Equations of State

Appendix B, Intro to ChE Thermo by Van Ness, Smith, 8th ed.

58
 Sample Problems

Solution:
To solve for the needed parameters:
𝑇 350 𝐾 𝑃 9.4573 𝑏𝑎𝑟
𝑇𝑟 = = = 0.82 ; 𝑃𝑟 = = = 0.25
𝑇𝑐 425.1 𝐾 𝑃𝑐 37.96 𝑏𝑎𝑟
For Redlich-Kwong:
𝛹𝑇𝑟 −1/2 0.42748 (0.82)−1/2
𝑞= = = 6.6447
𝛺𝑇𝑟 0.08664 (0.82)
𝑃𝑟 0.25
𝛽= 𝛺 = 0.08664 = 0.0264
𝑇𝑟 0.82

59
 Sample Problems

𝒁−𝜷
a) For saturated vapor: 𝒁 = 𝟏 + 𝜷 − 𝒒𝜷
(𝒁+𝜺𝜷)(𝒁+𝝈𝜷)
𝑍−𝛽
For Redlich-Kwong: 𝑍 = 1 + 𝛽 − 𝑞𝛽
𝑍(𝑍+𝛽)
𝑍−0.0264
𝑍 = 1 + 0.0264 − (6.6447)(0.0264)
𝑍(𝑍+0.0264)
𝑍 = 0.8275
𝑏𝑎𝑟∙𝑐𝑚3
𝑍𝑅𝑇 0.8275 83.14 𝑚𝑜𝑙∙𝐾 (350𝐾)
𝑉= = = 𝟐𝟓𝟒𝟔. 𝟏𝟐 𝒄𝒎𝟑 /𝒎𝒐𝒍
𝑃 9.4573 𝑏𝑎𝑟

60
 Sample Problems

𝟏+𝜷−𝒁
b) For saturated liquid: 𝒁 = 𝜷 + 𝒁 + 𝜺𝜷 𝒁 + 𝝈𝜷
𝒒𝜷
1+𝛽−𝑍
For Redlich-Kwong: 𝑍 = 𝛽 + 𝑍 𝑍 + 𝛽
𝑞𝛽
1+0.0264−𝑍
𝑍 = 0.0264 + 𝑍 𝑍 + 0.0264
6.6447 0.0264
𝑍 = 0.0433
𝑏𝑎𝑟∙𝑐𝑚3
𝑍𝑅𝑇 0.0433 83.14 𝑚𝑜𝑙∙𝐾 (350𝐾)
𝑉= = = 𝟏𝟑𝟑. 𝟐𝟑 𝒄𝒎𝟑 /𝒎𝒐𝒍
𝑃 9.4573 𝑏𝑎𝑟

61
 Sample Problem

2. What pressure is generated when 1 𝑘𝑚𝑜𝑙 of methane

is stored in a volume of 0.125 𝑚3 at 323.15 𝐾 using the
Redlich-Kwong equation?

Given: 𝑛 = 1 𝑘𝑚𝑜𝑙
𝑉 = 0.125 𝑚3
𝑇 = 323.15 𝐾
Required: 𝑃 𝑢𝑠𝑖𝑛𝑔 𝑅𝐾 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛
62
 Sample Problems
𝑇 323.15 𝐾
Solution: 𝑇𝑟 = = = 1.70
𝑇𝑐 190.6 𝐾
𝑹𝑻 𝒂(𝑻)
𝑅𝑒𝑑𝑙𝑖𝑐ℎ − 𝐾𝑤𝑜𝑛𝑔 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛: 𝑷 = −
𝑽−𝒃 𝑽(𝑽+𝒃)
𝜶(𝑻𝒓 )𝑹𝟐 𝑻𝒄 𝟐 𝑹𝑻𝒄
𝒂 𝑻 = 𝚿 ; 𝒃=𝛀
𝑷𝒄 𝑷𝒄

For RK: Ψ = 0.42748 ; Ω = 0.08664 ; 𝛼 𝑇𝑟 = 𝑇𝑟 −1/2

1 2
−2 𝑏𝑎𝑟∙𝑚3
1.70 0.08314 (190.6 𝐾)2
𝑘𝑚𝑜𝑙∙𝐾
𝑎 𝑇 = 0.42748
45.99 𝑏𝑎𝑟
𝑎 𝑇 = 1.7902 𝑏𝑎𝑟 ∙ 𝑚6 /𝑘𝑚𝑜𝑙 2
63
 Sample Problems

Solution:
𝑏𝑎𝑟∙𝑚3
0.08314 𝑘𝑚𝑜𝑙∙𝐾 (190.6 𝐾)
𝑏 = 0.08664 = 0.0299 𝑚3 /𝑘𝑚𝑜𝑙
45.99 𝑏𝑎𝑟
𝑹𝑻 𝒂(𝑻)
𝑷= −
𝑽−𝒃 𝑽(𝑽+𝒃)
𝑏𝑎𝑟∙𝑚3
0.08314 𝑘𝑚𝑜𝑙∙𝐾 (323.15 𝐾) 1.7902 𝑏𝑎𝑟∙𝑚6 /𝑘𝑚𝑜𝑙 2
𝑃= 𝑚3 𝑚3
− 𝑚3 𝑚3 𝑚3
0.125 −0.0299 0.125 0.125 +0.0299
𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙

𝑷 = 𝟏𝟗𝟎. 𝟎𝟓𝟐𝟖 𝒃𝒂𝒓

64
 Principle of Corresponding States

Two-Parameter Corresponding States

◉ All fluids, when compared at the same reduced
temperature and reduced pressure, have approximately
the same compressibility factor, and all deviate from
ideal-gas behavior to about the same degree.
Parameters: 𝑃𝐶 and 𝑇𝐶
Equations of State: Van der Waals, Redlich-Kwong

65
 Principle of Corresponding States

Three-Parameter Corresponding States

◉ All fluids having the same value of acentric factor, when
compared at the same reduced temperature and
reduced pressure, have about the same compressibility
factor, and all deviate from ideal-gas behavior to about
the same degree.
Parameters: 𝑃𝐶 , 𝑇𝐶 and 𝜔
Equations of State: Soave-Redlich-Kwong, Peng/Robinson
66
6. Generalized Correlations for Gases

67
 Pitzer Correlations for the Compressibility Factor

A generalized correlation of Z as a function of 𝑇𝑟 and 𝑃𝑟 :

𝑃𝑉
𝑍= = 𝑍(𝑃𝑟 , 𝑇𝑟 )
𝑅𝑇
The correlation for Z is:
𝒁 = 𝒁𝟎 + 𝝎𝒁𝟏
Where 𝑍 0 and 𝑍1 are functions of both 𝑇𝑟 and 𝑃𝑟 and 𝜔 is the
acentric factor.
𝑃𝑣𝑎𝑝 (𝑇𝑟 =0.7)
Acentric factor: 𝜔 = −1.0 − log10
𝑃𝑐
*Values of Acentric Factor are available at Appendix B, Intro to ChE Thermo by Van Ness, Smith, 8th ed.
68
 Pitzer Correlations for the Compressibility Factor

Appendix D, Intro to ChE Thermo by Van Ness, Smith, 8th ed.

69
 Pitzer Correlations for the Second Virial Coefficient

The simplest form of the virial equation:

𝑩𝑷 𝑩𝑷𝒄 𝑷𝒓 𝑷𝒓
𝒁=𝟏+ =𝟏+ =𝟏+𝑩
𝑹𝑻 𝑹𝑻𝒄 𝑻𝒓 𝑻𝒓
𝐵𝑃𝑐
Where, 𝐵 = = 𝐵0 + 𝜔𝐵1
𝑅𝑇𝑐
For pure chemical species 𝐵0 and 𝐵1 are functions of reduced
temperature only. Substituting,
𝟎 𝟏
𝑷𝒓
𝒁 = 𝟏 + (𝑩 +𝝎𝑩 )
𝑻𝒓
𝟎.𝟒𝟐𝟐 𝟎.𝟏𝟕𝟐
Where 𝑩𝟎 = 𝟎. 𝟎𝟖𝟑 − and 𝑩𝟏 = 𝟎. 𝟏𝟑𝟗 − represented by
𝑻𝒓 𝟏.𝟔 𝑻𝒓 𝟒.𝟐
the Abbott equations.
70
 Pitzer Correlations for the Third Virial Coefficient

A generalized correlation for third virial coefficients can be written as:

𝑷 𝑷𝒓 𝟐
𝒁=𝟏 + 𝑩 𝑻 𝒓𝒁 + 𝑪 𝑻𝒓 𝒁
𝒓
𝐶𝑃𝑐 2
Where, 𝐶 = = 𝐶 0 + 𝜔𝐶 1
𝑅2 𝑇𝑐 2
𝑷𝒓 𝑷𝒓 𝟐
Substituting, 𝒁 𝟎 𝟏 𝟎 𝟏
= 𝟏 + (𝑩 +𝝎𝑩 ) 𝑻 𝒁 + (𝑪 +𝝎𝑪 ) 𝑻 𝒁
𝒓 𝒓

An expression for 𝐶 0 and 𝐶 1 as a function of reduced temperature is given

by Orbey and Vera:
𝟎.𝟎𝟐𝟒𝟑𝟐 𝟎.𝟎𝟎𝟑𝟏𝟑
𝑪𝟎 = 𝟎. 𝟎𝟏𝟒𝟎𝟕 + −
𝑻𝒓 𝑻𝒓 𝟏𝟎.𝟓
𝟎.𝟎𝟓𝟓𝟑𝟗 𝟎.𝟎𝟎𝟐𝟒𝟐
𝑪𝟏 = −𝟎. 𝟎𝟐𝟔𝟕𝟔 + −
𝑻𝒓 𝟐.𝟕 𝑻𝒓 𝟏𝟎.𝟓
71
 Sample Problem

2. Determine the molar volume of n-butane at 510 𝐾 and

25 𝑏𝑎𝑟 by each of the following:
a) The ideal gas state
b) Pitzer correlation for compressibility factor
c) Pitzer correlation for second virial coefficient
d) Pitzer correlation for third virial coefficient

72
 Sample Problems

Solution:
a) Using ideal gas state
𝑏𝑎𝑟∙𝑐𝑚3
𝑅𝑇 83.14 𝑚𝑜𝑙∙𝐾 (510 𝐾)
𝑉𝑚 = =
𝑃 25 𝑏𝑎𝑟
𝑽𝒎 = 𝟏𝟔𝟗𝟔. 𝟎𝟔 𝒄𝒎𝟑 /𝒎𝒐𝒍
b) Using Pitzer correlation for compressibility factor
𝑇 510 𝐾
𝑇𝑟 = = = 1.20
𝑇𝑐 425.1 𝐾
𝑃 25 𝑏𝑎𝑟
𝑃𝑟 = = = 0.66
𝑃𝑐 37.96 𝑏𝑎𝑟
73
 Sample Problems

𝑷𝒓 0.6000 0.66 0.8000 𝑷𝒓 0.6000 0.66 0.8000

𝑻𝒓 𝑻𝒓
1.20 0.8779 0.8644 0.8330 1.20 0.0326 0.0378 0.0499

For these values, 𝑍 0 = 0.8644 𝑎𝑛𝑑 𝑍1 = 0.0378

𝑍 = 𝑍 0 + 𝜔𝑍1 = 0.8644 + 0.200 0.0378
𝑍 = 0.8720
𝑏𝑎𝑟∙𝑐𝑚3
𝑍𝑅𝑇 0.8720 83.14 𝑚𝑜𝑙∙𝐾 (510 𝐾)
𝑉𝑚 = = = 𝟏𝟒𝟕𝟖. 𝟗𝟔 𝒄𝒎𝟑 /𝒎𝒐𝒍
𝑃 25 𝑏𝑎𝑟

74
 Sample Problems

c) Using Pitzer correlation for second virial coefficient

𝑇 510 𝐾 𝑃 25 𝑏𝑎𝑟
𝑇𝑟 = = = 1.20 ; 𝑃𝑟 = = = 0.66
𝑇𝑐 425.1 𝐾 𝑃𝑐 37.96 𝑏𝑎𝑟
0.422 0.422
𝐵0 = 0.083 − 1.6 = 0.083 − = −0.2322
𝑇𝑟 1.20 1.6
0.172 0.172
𝐵1 = 0.139 − 4.2 = 0.139 − = 0.059
𝑇𝑟 1.20 4.2
𝑃 0.66
𝑍 = 1 + (𝐵0 +𝜔𝐵1 ) 𝑟 = 1 + −0.2322 + 0.200 0.059 = 0.8788
𝑇𝑟 1.20
𝑏𝑎𝑟∙𝑐𝑚3
𝑍𝑅𝑇 0.8788 83.14 𝑚𝑜𝑙∙𝐾 (510 𝐾)
𝑉𝑚 = = = 𝟏𝟒𝟗𝟎. 𝟒𝟗 𝒄𝒎𝟑 /𝒎𝒐𝒍
𝑃 25 𝑏𝑎𝑟
75
 Sample Problems
d) Using Pitzer correlation for third virial coefficient
𝑇 510 𝐾 𝑃 25 𝑏𝑎𝑟
𝑇𝑟 = = = 1.20 ; 𝑃𝑟 = = = 0.66
𝑇𝑐 425.1 𝐾 𝑃𝑐 37.96 𝑏𝑎𝑟
0.02432 0.00313 0.02432 0.00313
𝐶 0 = 0.01407 + − 10.5 = 0.01407 + − = 0.0339
𝑇𝑟 𝑇𝑟 1.20 1.2010.5
0.05539 0.00242 0.05539 0.00242
𝐶 1 = −0.02676 + 2.7 − 10.5 = −0.02676 + − = 0.0067
𝑇𝑟 𝑇𝑟 1.202.7 1.2010.5

0 1 𝑃𝑟 0 1 𝑃𝑟 2
𝑍 = 1 + (𝐵 +𝜔𝐵 ) + (𝐶 +𝜔𝐶 )
𝑇𝑟 𝑍 𝑇𝑟 𝑍
𝑍 = 0.8754
𝑏𝑎𝑟∙𝑐𝑚3
𝑍𝑅𝑇 0.8754 83.14 𝑚𝑜𝑙∙𝐾 (510 𝐾)
𝑉𝑚 = = = 𝟏𝟒𝟖𝟒. 𝟕𝟑 𝒄𝒎𝟑 /𝒎𝒐𝒍
𝑃 25 𝑏𝑎𝑟
7. Generalized Correlation for Liquids

77
 Generalized Correlations for Liquids

Generalized equations are available for the estimation

of molar volumes of saturated liquids. The simplest
equation, proposed by Rackett, is an example:
(𝟏−𝑻𝒓 )𝟐/𝟕
𝑽𝒔𝒂𝒕 = 𝑽𝒄 𝒁𝒄
An alternative form of this equation is sometimes useful:
𝑷𝒓 𝟏+(𝟏−𝑻𝒓 )𝟐/𝟕
𝒁𝒔𝒂𝒕 = 𝒁
𝑻𝒓 𝒄

78
 Generalized Correlations for Liquids

Lyderson, Greenkorn, and Hougen developed a two-parameter

corresponding states correlation for estimation of liquid volumes.
𝝆 𝑽𝒄
𝝆𝒓 = = where 𝜌𝑐 is the density at the critical point
𝝆𝒄 𝑽
To determine the molar volume of a substance using a known
value of molar volume, it can be calculated using:
𝝆𝒓𝟏
𝑽𝟐 = 𝑽𝟏
𝝆𝒓𝟐
Where 𝑽𝟐 is the required volume, 𝑽𝟏 is the known volume, and 𝝆𝒓𝟏
and 𝝆𝒓𝟐 are reduced densities read from Fig. 3.15
79
Generalized Correlations for Liquids

80
 Sample Problem
For ammonia at 310 𝐾, estimate the density and molar volume of
a) The saturated liquid
b) The liquid at 100 𝑏𝑎𝑟

Solution:
a) The saturated liquid applying Rackett equation
𝑇 310 𝐾 𝑃 100 𝑏𝑎𝑟
𝑇𝑟 = 𝑇 = 405.7 𝐾 = 0.76 ; 𝑃𝑟 = 𝑃 = 112.80 𝑏𝑎𝑟 = 0.89
𝑐 𝑐

(1−𝑇𝑟 )2/7 𝑐𝑚3 2/7

𝑉 𝑠𝑎𝑡 = 𝑉𝑐 𝑍𝑐 = 72.5 𝑚𝑜𝑙 (0.242)(1−0.76)
𝒄𝒎𝟑 𝒎𝒐𝒍
𝑽𝒔𝒂𝒕 = 𝟐𝟖. 𝟐𝟐 𝒎𝒐𝒍 ; 𝝆 = 𝟎. 𝟎𝟑𝟓𝟒 𝒄𝒎𝟑
81
 Sample Problems

b) The liquid at 100 𝑏𝑎𝑟

From the figure, 𝜌𝑟 ≈ 2.34
𝑉𝑐 72.5 𝑐𝑚3 /𝑚𝑜𝑙
𝑉= =
𝜌𝑟 2.34
𝑽= 𝟑𝟎. 𝟗𝟖 𝒄𝒎𝟑 /𝒎𝒐𝒍
𝝆 = 𝟎. 𝟎𝟑𝟐𝟑 𝒎𝒐𝒍/𝒄𝒎𝟑
8. Thermodynamic Tables

83
 Thermodynamic Tables
Steam Table in Introduction to ChE Thermodynamics (Van Ness,
et. al., 8th edition)
◉ Appendix E for Saturated and Superheated Steam Tables
Thermodynamic Tables in Perry’s Handbook. 9th edition
◉ Table 2 − 109 up to 2 − 136 for Thermodynamic Properties of all
Known Substances
◉ Table 2 − 134 for Saturated Solid/Water Vapor
◉ Table 2 − 135 for Thermodynamic Properties of Water
◉ Table 2 − 136 for Thermodynamic Properties of Water Substance
along the Melting Line
84
Thanks!
ANY QUESTIONS?

85