Chapter 3 Volumetric Properties of Pure Fluids

(PVT Behaviour of Pure Fluids)

Equilibrium: the absence of change; all forces are in exact balance; the absence of driving force
The equilibrium state of a system is completely described by a fixed number of independent
variables (degrees of freedom). The other independent variables are specified using equations of state.

The Phase Rule (Josiah Willard Gibbs)

for non-reacting system: F=2–π+N
Where:
π = number of phases
N = number of chemical species
F = degrees of freedom of the system
• the intensive state of the system at equilibrium is fixed when its T, P, and composition of all phases
are fixed
• composition may be mass or mole fractions

Example 2.5/p30
How many degrees of freedom have 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 liquid solution of alcohol in water in equilibrium with its vapor
Answer:
(a) F = 2 – π+ N = 2 – 2 + 1 = 1
(b) F = 2 – π + N = 2 – 2 + 2 = 2
(c) F = 2 – π + N = 2 – 2 + 2 = 2

PT Diagram for a Pure Substance

• the sublimation curve (line 1-2) separates the solid and gas regions (F=1)
• the fusion curve (line 2-3) separates the solid and liquid regions (F=1)
• the vaporization curve (line 2-C) separates the liquid and gas regions (F=1)
• the triple point (point 2) where the three lines meet and the three phases solid, liquid, and gas coexist in
equilibrium, there is a unique temperature and pressure at this point (F=0)
• the critical point (point C), its coordinates PC and TC are the highest pressure and highest temperature at
which a pure chemical species is observed to exist in vapor/liquid equilibrium
• the material that is above the PC and TC is called a supercritical fluid.

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PV Diagram for a Pure Substance

• The isotherms
– the subcooled-liquid and the superheated-vapor regions
– isotherms in the subcooled-liquid regions are steep because liquid volumes change little
with large change in pressure
• The two-phase coexist regions
• The triple point is the horizontal line
• The critical point
Equations of State (EOS)
- An EOS relates pressure, molar or specific volume, and temperature for any pure homogeneous
fluid.
- empirical relationships that mathematically model the PVT behaviour of fluids
PVT equation of state is expressed analytically as: f(P,V,T) = 0
- equation may be solved for any one of the three quantities P, V, or T as a function of the other
two
for example: V = V(T,P) P = P(V,T) T = T(V,P)

Liquids
V  V (T , P )
 V   V 
dV  
T 
 dT  
 P dP
 P  T

The partial derivatives in the equation have definite physical meanings and are related to two
properties, volume expansivity (β) and isothermal compressibility (κ)

1 V 
   
V  T P

1  V 
    
V   P T

β and κ can be assumed constant for liquids, at conditions not close to the critical point.

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 The equation of state for liquids can then be written as:

dV
  dT   dP
V Values of  and  are found in many handbooks.
V
ln 2    T2  T1     P2  P1 
V1

Example 3.1/p69
For liquid acetone at 20oC and 1 bar,
β = 1.487 x 10-3 oC-1 κ = 62 x 10-6 bar-1 V = 1.287 cm g-1
For acetone, find the
(a) value of ( ) at 20oC and 1 bar
(b) pressure generated by heating at constant V from 20oC and 1 bar to 30oC
(c) change in volume for a change from 20oC and 1 bar to 0oC and 10 bar.

Solution:
(a)
P  P (V , T )
0 at constant volume
 P  P
dP  
T 
 dT  
 V 
 dV
 V  T
dP  P  = (from EoS for liquids)

 T 

dT  V

Assignment: Problems 3.4, 3.5 and 3.6/pp 111-112

Virial Equations of State

PV  a  bP  cP 2
If b aB’, c aC’, etc., then

PV  a(1  BP  C P 2  DP 3  ...)

the parameters B’, C’, D’, etc. are virial coefficients, accounting of interactions between
molecules

PV T PV=RT Z = compressibility factor

a=f(T) Z  (1  BP  C P 2  DP 3  ...)

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Ideal Gases
 molecules on average are far apart
 best at large V (low density)
 occurs at low P and high T
 intermolecular forces approach zero
 no interactions between particles

Ideal gas equation of state:

Processes of Non-flow Systems of an Ideal Gas

A non-flow system is a closed system (constant mass) which undergoes processes where no changes
in potential energy and kinetic energy, and no PV work are involved.

General Equations for Non-flow Processes Involving Ideal Gases

1) Ideal Gas Law P1V1 /T1 = P2V2 /T2

2) PV Work

3) First Law of Thermodynamics

4) Internal energy for an ideal gas:

U  U (T )
T2

U   CV dT
T1

5) Enthalpy for an ideal gas:

dH  dU  d ( PV )  dU  RdT  H T 
T2

H   C P dT
T1

6) Heat capacities for ideal gases:

C P  CV  R
5
For monatomic gases: CP  R
2
7
For diatomic gases at high temperatures: CP  R
2

Appen. C, p. 637, gives equations for ideal gas heat capacities as a function of temperature.

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Thermodynamic Processes
Isobaric (Constant-P) Process

Isochoric (Constant-V) Process

Isothermal (Constant-T) Process

Adiabatic Process
 no heat flows in or out of the system
 process occurs when the system is extremely well insulated or when the process
happens very quickly.

Qin  0
then U int  Won,adiabatic  n cV T

C
FoF P V  const ;   C
 P
adiabatic coefficien t
V

T V  1  const
T  P 1  const

Note: Special P-V-T relations are for an adiabatic and reversible process.

Polytropic Process
A polytropic process is a thermodynamic process that obeys the relation:
PVn = C
where P is pressure, V is volume, n is any real number (the polytropic index), and C is a constant.

For certain indices n, the process will be synonymous with other processes:
if n = 0, then PV0=P=const and it is an isobaric process (constant pressure)
if n = 1, then for an ideal gas PV= const and it is an isothermal process (constant temperature)
if n = γ = cp/cV, then for an ideal gas it is an adiabatic process (no heat transferred)
if n = ∞ , then it is an isochoric process (constant volume)

• NOTE: The work of an irreversible process is calculated:

– First, the work is determined for a mechanically reversible process.
– Second, the result is multiplied or divided by an efficiency to give the actual work.

Example 3.2
Air is compressed from an initial condition of 1 bar and 25°C to a final state of 5 bar and 25 °C by
three different mechanically reversible processes in a closed system. (1) heating at constant volume
followed by cooling at constant pressure; (2) isothermal compression; (3) adiabatic compression
followed by cooling at constant volume. Assume air to be an ideal gas with the constant heat capacities,
CV = (5/2)R and CP = (7/2)R. Calculate the work required, heat transferred, and the changes in internal
energy and enthalpy of the air in each process.

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Example 3.3/ Example 3.4
An ideal gas undergoes the following sequence of mechanically reversible processes in a closed
system:
(1) From an initial state of 70°C and 1 bar, it is compressed adiabatically to 150 °C.
(2) It is then cooled from 150 to 70 °C at constant pressure.
(3) Finally, it is expanded isothermally to its original state.
Calculate W, Q, ΔU, and ΔH for each of the three processes and for the entire cycle. Take C V = (3/2)R and
CP = (5/2)R. If these processes are carried out irreversibly but so as to accomplish exactly the same
changes of state (i.e. the same changes in P, T, U, and H), then different values of Q and W result.
Calculate Q and W if each step is carried out with an efficiency of 80%.

Homework
1. An ideal gas initially at 184oC, 3.0 atm with a volume of 25 L undergoes expansion to a final pressure
of 1.4 atm. Determine the work done by the gas if the expansion is
(a) isothermal and reversible Ans. -5792 J
(b) isothermal and against a constant opposing pressure of 1.4 atm Ans. -4053 J

2. One g-mole of an ideal monoatomic gas, Cv = (3/2)R, has an initial pressure of 6 atm and a
temperature of 200oC. It expands to a final pressure of 2 atm. Calculate the work done by the gas on
expansion if the process is
(a) adiabatic and reversible Ans. -2098 J
(b) adiabatic and against a constant opposing pressure of 1.0 atm Ans. -982 J

Non-ideal Gases

Virial Equations of State.

Two equivalent forms:

Z  1  B' P  C ' P 2  

B C
Z  1    (3.40)
V V2
B C  B2
B'  C'  2 2
RT R T

These two equations are not identical when truncated.

Group activity: Compare the two equations truncated after the 2nd virial coefficient terms for
the problem in Example 3.7, p. 89. Ans.: V=3546 cm3/mol from 1st form, V=3488 from 2nd, a
1.7 % difference.

Cubic Equations of State.

In 1873, Van der Waals developed an equation of state that qualitatively accounts for attractive
forces between molecules and an excluded volume due to the finite size of the molecules:

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 RT a
P  2 (3.41)
V b V

Here, a and b are positive constants; when they are equal to zero, the ideal gas equation is
recovered.
This has been modified to make it better fit real gas behavior by many workers. For example,
Redlich and Kwong proposed the following equation of state in 1949:

RT a (T )
P 
V  b V V  b 
(3.47)

Note that a(T) is a constant, and is given by Eq. (3.45) found on p. 94 in the text.

These two-parameter equations of state are called cubic equations, because they are cubic in V.
Thus, there are three volumes corresponding to a given P and T. For saturated liquid and vapor,
the smallest root will be for the liquid, the largest for the vapor, and a third one will lie in
between (see Fig. 3.11, p. 92).

At the critical point, the P-V curve must obey the following relations:

  P   2 P
    0 (3.43) and (3.44)
 V  T  V 2  T

These allow evaluation of a and b in terms of critical properties for fluids.

See p. 93 for the relations found for the van der Waals equation.
Critical properties are tabulated in Appendix B, pp. 680-681.

The a and b parameters could also be fit to experimental PVT data for the fluid of interest. This
would give a better equation of state within the region of the experimental data, but would not
extrapolate well to other regions.

Other important cubic equations of state are listed below.

Soave-Redlich-Kwong equation of state

RT a
P 
V  b V (V  b)
a  a c (1  k (1  Tr )) 2
0.42748 R 2Tc2
SRK: ac 
Pc
k  0.480  1.574  0.176 2

0.08664 RTc
b
Pc
Peng-Robinson equation of state

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 RT a
P 
V  b V (V  b)  b(V  b)
a  a c (1   (1  Tr )) 2
0.45724 R 2Tc2
PR: ac 
Pc
  0.37464  1.54226  0.26992 2

0.07780 RTc
b
Pc

Generalized Correlations - Gases.

Two-parameter corresponding states:

Z  Z o  Pr , Tr 
* works well for simple fluids (small, nonpolar species like Ar, N 2, CH4, etc.)
* use Tables E.1 and E.3, Append. E, p.695

Three-parameter corresponding states:

Z  Z o  Pr , Tr    Z 1  Pr , Tr 
* good for normal fluids (nonpolar or weakly polar species, independent of size)
* simple fluids, paraffins, other weakly polar organic or inorganic species
* see Appendix B, for table of critical parameters and acentric factors
* use tables in Append. E
* can also be used to find virial coefficients (see Eqns. 3.59-62, p. 102)

BPc
 B o   B1
RTc

Generalized Correlations - Liquids.

Rackett equation for saturated liquid molar volumes:

V sat  Vc Zc 
1Tr 
0 . 2857

(3.72)

Lyderson, Greenkorn, Hougen correlation (Fig. 3.16, p.110):

* a two-parameter corresponding states correlation
* best used to correct Vsat for pressure
 r    sat 
V2  V1  1   V sat  r 
  r2    r2 

* the same correction to Vsat can be made using isothermal compressibilities for specific
fluids

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