Calculation of the Properties of Pure Fluids

BT2061: Biochemical Thermodynamics

M. Hamsa Priya

M. Hamsa Priya BT2061:Fluid Properties 1 / 20

Outline

1 Principle of Corresponding States

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 Principle of Corresponding States

Pressure-Volume behaviour of the van der Waals Equation

of State

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 Principle of Corresponding States

Critical Point

Critical Point is the point beyond which there is no vapour-liquid

coexistence or beyond which liquid phase doesn’t exist

M. Hamsa Priya BT2061:Fluid Properties 4 / 20

 Principle of Corresponding States

Critical Point

Critical Point is the point beyond which there is no vapour-liquid

coexistence or beyond which liquid phase doesn’t exist
Gaseous phase below critical temperature is called vapour

M. Hamsa Priya BT2061:Fluid Properties 4 / 20

 Principle of Corresponding States

Critical Point

Critical Point is the point beyond which there is no vapour-liquid

coexistence or beyond which liquid phase doesn’t exist
Gaseous phase below critical temperature is called vapour
Gaseous phase above critical temperature is called gas

M. Hamsa Priya BT2061:Fluid Properties 4 / 20

 Principle of Corresponding States

Critical Point

Critical Point is the point beyond which there is no vapour-liquid

coexistence or beyond which liquid phase doesn’t exist
Gaseous phase below critical temperature is called vapour
Gaseous phase above critical temperature is called gas
Critical point is an inflection point on isotherm in the P − V plane i.e.,
 
∂P
= 0;
∂V Tc
 2 
∂ P
=0
∂V2 Tc

at Pc and Vc

M. Hamsa Priya BT2061:Fluid Properties 4 / 20

 Principle of Corresponding States

Critical Point
Identify whether the following compounds can be classified as vapour
or gas at room temperature.
1. Argon; 2. Benzene; 3. Carbon dioxide; 4. Helium

M. Hamsa Priya BT2061:Fluid Properties 5 / 20

 Principle of Corresponding States

Evaluation of van der Waals Parameters

van der Waals equation of state:

RT a
P= − 2
V−b V

M. Hamsa Priya BT2061:Fluid Properties 6 / 20

 Principle of Corresponding States

Evaluation of van der Waals Parameters

van der Waals equation of state:

RT a
P= − 2
V−b V

van der Waals equation at critical point:

RTc a
Pc = − 2
Vc − b Vc

Using the mathematical condition at the critical point, derive the

expression for the parameters a and b in terms of Tc and Pc

M. Hamsa Priya BT2061:Fluid Properties 6 / 20

 Principle of Corresponding States

Evaluation of van der Waals Parameters

van der Waals equation of state:

RT a
P= − 2
V−b V

van der Waals equation at critical point:

RTc a
Pc = − 2
Vc − b Vc

Using the mathematical condition at the critical point, derive the

expression for the parameters a and b in terms of Tc and Pc

27R2 T2c RTc

a= ;b =
64Pc 8Pc

M. Hamsa Priya BT2061:Fluid Properties 6 / 20

 Principle of Corresponding States

Reduced Properties

Let’s define the property scaled to the property at critical point as

reduced property
T
Reduced Temperature, Tr =
Tc
P
Reduced Pressure, Pr =
Pc
V
Reduced Volume, Vr =
Vc
Using the values of parameters a and b in terms of critical properties,
can you derive an expression for Pr for a van der Waals gas

27R2 T2c 9Vc RTc

a= = = 3Pc V2c
64Pc 8
RTc V
b= = c
8Pc 3

M. Hamsa Priya BT2061:Fluid Properties 7 / 20

 Principle of Corresponding States

Reduced Properties

van der Waals equation of state in terms of reduced properties

8Tr 3
Pr = − 2
3Vr − 1 Vr

M. Hamsa Priya BT2061:Fluid Properties 8 / 20

 Principle of Corresponding States

Reduced Properties

van der Waals equation of state in terms of reduced properties

8Tr 3
Pr = − 2
3Vr − 1 Vr

What do you observe and infer from this expression?

M. Hamsa Priya BT2061:Fluid Properties 8 / 20

 Principle of Corresponding States

Reduced Properties

van der Waals equation of state in terms of reduced properties

8Tr 3
Pr = − 2
3Vr − 1 Vr

What do you observe and infer from this expression?

The expression is independent of any parameters

M. Hamsa Priya BT2061:Fluid Properties 8 / 20

 Principle of Corresponding States

Reduced Properties

van der Waals equation of state in terms of reduced properties

8Tr 3
Pr = − 2
3Vr − 1 Vr

What do you observe and infer from this expression?

The expression is independent of any parameters
This expression is referred as “Generalized vdW EOS” (equation of
state)

M. Hamsa Priya BT2061:Fluid Properties 8 / 20

 Principle of Corresponding States

Reduced Properties

van der Waals equation of state in terms of reduced properties

8Tr 3
Pr = − 2
3Vr − 1 Vr

What do you observe and infer from this expression?

The expression is independent of any parameters
This expression is referred as “Generalized vdW EOS” (equation of
state)
The Pr − Vr at a given Tr is the same for all van der Waals gases,
irrespective of the difference in their chemical identity

M. Hamsa Priya BT2061:Fluid Properties 8 / 20

 Principle of Corresponding States

Reduced Properties

van der Waals equation of state in terms of reduced properties

8Tr 3
Pr = − 2
3Vr − 1 Vr

What do you observe and infer from this expression?

The expression is independent of any parameters
This expression is referred as “Generalized vdW EOS” (equation of
state)
The Pr − Vr at a given Tr is the same for all van der Waals gases,
irrespective of the difference in their chemical identity
Given Pr and Tr , any fluid will have the same Vr , the two fluids are
said to be in corresponding states

M. Hamsa Priya BT2061:Fluid Properties 8 / 20

 Principle of Corresponding States

Compressibility
PV
Let’s define compressibility as Z =
RT
The compressibility of a van der Waals gas at critical point

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 Principle of Corresponding States

Compressibility
PV
Let’s define compressibility as Z =
RT
The compressibility of a van der Waals gas at critical point
Pc V c 3
Zc = = = 0.375
RTc 8

M. Hamsa Priya BT2061:Fluid Properties 9 / 20

 Principle of Corresponding States

Compressibility
PV
Let’s define compressibility as Z =
RT
The compressibility of a van der Waals gas at critical point
Pc V c 3
Zc = = = 0.375
RTc 8

For most fluids, experimentally determined, the critical compressibility

Zc is in the range of 0.23 – 31

M. Hamsa Priya BT2061:Fluid Properties 9 / 20

 Principle of Corresponding States

Compressibility
PV
Let’s define compressibility as Z =
RT
The compressibility of a van der Waals gas at critical point
Pc V c 3
Zc = = = 0.375
RTc 8

For most fluids, experimentally determined, the critical compressibility

Zc is in the range of 0.23 – 31
van der Waals equation fails to predict accurate critical-point behavior

M. Hamsa Priya BT2061:Fluid Properties 9 / 20

 Principle of Corresponding States

Compressibility
PV
Let’s define compressibility as Z =
RT
The compressibility of a van der Waals gas at critical point
Pc V c 3
Zc = = = 0.375
RTc 8

For most fluids, experimentally determined, the critical compressibility

Zc is in the range of 0.23 – 31
van der Waals equation fails to predict accurate critical-point behavior
It is, however, a great improvement over the ideal gas equation of
state, which predicts Z = 1 for all conditions

M. Hamsa Priya BT2061:Fluid Properties 9 / 20

 Principle of Corresponding States

Compressibility
PV
Let’s define compressibility as Z =
RT
The compressibility of a van der Waals gas at critical point
Pc V c 3
Zc = = = 0.375
RTc 8

For most fluids, experimentally determined, the critical compressibility

Zc is in the range of 0.23 – 31
van der Waals equation fails to predict accurate critical-point behavior
It is, however, a great improvement over the ideal gas equation of
state, which predicts Z = 1 for all conditions
Although vdW EOS is not accurate, the idea of a corresponding
states derived from it is both appealing and useful

M. Hamsa Priya BT2061:Fluid Properties 9 / 20

 Principle of Corresponding States

Two-parameter Corresponding States

Compressibility depends on two parameters
PV
Z= = Z(Pr , Tr )
RT
6.6 The Principle of Corresponding States 243

1.1 I
I I- I I I

Reduced pressure, P,

Figure 6.6-1 Compressibility factors for different fluids as a function of the reduced teillpeKltL1~eand PriSSUrF.
[Reprinted with perinission from G.-J. Su, bid Etg. Clienr. 38. 803 (1946). Copyright American Chenlic~l
M. Hamsa Priya Society.] BT2061:Fluid Properties 10 / 20
 Principle of Corresponding States

Three-parameter Corresponding States

The systematic deviation like compressibility of inorganic fluids are
almost always below those for the hydrocarbons
van der Waals Zc = 0.375, while the real fluids have Zc ranging from
0.23-0.31

M. Hamsa Priya BT2061:Fluid Properties 11 / 20

 Principle of Corresponding States

Three-parameter Corresponding States

The systematic deviation like compressibility of inorganic fluids are
almost always below those for the hydrocarbons
van der Waals Zc = 0.375, while the real fluids have Zc ranging from
0.23-0.31
These short-comings led to 3-parameter corresponding state model
Z = Z(Pr , Tr , Zc )
Pitzer suggested that for non-spherical molecules the acentric factor
ω be used as the third correlative parameter
Z = Z(Pr , Tr , ω)
ω = −1.0 − log10 [Pvap (Tr = 0.7)/Pc ] ,
Pvap (Tr = 0.7) is the vapor pressure of the fluid at Tr = 0.7, a
temperature near normal boiling point
Still the model is not applicable for fluids with permanent dipole and
quadropoles
M. Hamsa Priya BT2061:Fluid Properties 11 / 20
 Principle of Corresponding States

Three-parameter Corresponding States

Generalized Peng-Robinson EOS is an example of three parameter

correspondibg state model

RT a(T)
P= −
V − b V(V + b) + b((V − b)

where,
R2 T2c
a(T) = 0.45724 α(T)
Pc
RTc
b = 0.07780
Pc
r !
√ T
α=1+κ 1−
Tc
κ = 0.37464 + 1.54226ω − 0.26992ω 2

M. Hamsa Priya BT2061:Fluid Properties 12 / 20

 Principle of Corresponding States

Corresponding States Principle

Volumetric equation of state behavior of many simple fluids and most
hydrocarbons is6: approximately represented here
244 Ct1:xpter The Thermodynamic Properties of Real Substances

Reduced pressure. P,

Figure 6.6-3 (Reprinted with permissinn from 0. A. Hougen, K. M. Watson, and R. A.

Ragarz. Chemical Process~PrinciplesChctrrs. 2nd ed., John Wiley & Sons, New York,
1960. This figure appears as an Adobe PDF file on the CD-ROM accompanying this book,
Developed from experimental data for molecules with Zc = 0.27
and may be.enlarged and printed for easier reading and for use in solving problems.)

resentation of the equation-of-state behaviorwithin any one class of similar molecules.

Indeed, the volumetric equation-of-state behavior of nmny simple fluids and most hy-
M. Hamsa Priya BT2061:Fluid Properties
drocarbons is approximately represented by the plot in Fig. 6.6-3, which was developed
13 / 20
 Principle of Corresponding States

Corresponding States Principle

216 Chapter 6: The Ther~liodynamicProperties of Real S~tbstancrs

Figure 6.6-4 (Reprinted with pamission from 0. A. Hougen, K. M. Watson, and R. A. Ragatt,
Cl~emicalProcess Principles Clrans, 2nd ed., John Wiley & Sons, New York, 1960. This figure
appears as an Adobe PDF file on the CD-ROM accompanying this book, and may be enlarged
and printed for easier reading and for use in solving problems.)
-
M. Hamsa Priya The form of Eqs. 6.6-9BT2061:Fluid Properties
and 6.6-10 makes good physical sense in that each consists of 14 / 20
 Principle of Corresponding States

Corresponding States Principle

Enthalpy change:
Z T2
H(T2 , P2 ) − H(T1 , P1 ) = C∗P dT
T1
( )
H − HIG

+ Tc
Tc Tr2 ,Pr2
( )
IG 
H−H
− Tc
Tc Tr1 ,Pr1

M. Hamsa Priya BT2061:Fluid Properties 15 / 20

 Principle of Corresponding States

Corresponding States Principle

248 Chapter 6: The Thennodynamic Properties of Real Substances

Figure 6.6-5 (Reprinted with permission from 0. A. Hougen. K. M. Watson, and R. A. Ragatz,
M. Hamsa Priya Chemical Process Principles Charts, 2nd ed., JohnProperties
BT2061:Fluid Wiley & Sons, New York, 1960. This figure 16 / 20
 Principle of Corresponding States

Corresponding States Principle

Entropy change:

C∗P T2
Z P2
Z
dP
S(T2 , P2 ) − S(T1 , P1 ) = dT − R
T T P1 P
 1 IG 
+ S − S Tr ,Pr − S − SIG Tr
 
2 2 1 ,Pr1

M. Hamsa Priya BT2061:Fluid Properties 17 / 20

 Principle of Corresponding States

Third Law of Thermodynamics

Nernst-Simon Statement: The entropy change associated with any

condensed system undergoing a reversible isothermal process
approaches zero as the temperature at which it is performed
approaches 0 K.
Lewis-Randall Statement: If the entropy of each element in some
(perfect) crystalline state be taken as zero at the absolute zero of
temperature, every substance has a finite positive entropy; but at the
absolute zero of temperature the entropy may become zero, and does
so become in the case of perfect crystalline substances.
Another version as stated in Sandler Book: The entropy of all
substances in the perfect crystalline state (for solids) or the perfect
liquid state (for example, for helium) is zero at the absolute zero of
temperature (0 K)

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 Principle of Corresponding States

Third Law of Thermodynamics

The word “perfect” means without any disturbance in the

arrangement of the atoms. That is, the substance must be without
any vacancies, dislocations, or defects in the structure of the solid or
liquid and not contain any impurities
A more correct statement is that all substances in the perfect state
should have the same value of entropy at 0 K
For convenience in the preparation of thermodynamic tables that a
value of entropy of zero at 0 K is chosen

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 Principle of Corresponding States

Implications of Third Law of Thermodynamics

There will be no entropy change on a chemical reaction at 0 K if each

of the reacting substances is in perfect state, to produce one or more
products in perfect state
Infact, the above observation led to the formulation of the third law
It is impossible to obtain a temperature of absolute zero
Nernst statement (1912): ”It is impossible for any procedure to lead
to the isotherm T = 0 in a finite number of steps.”

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