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Chapter 3: Volumetric

Properties of Pure Fluids


CBE 210
Friday, 3 February 2017
Review - Ideal gas thermodynamics
• For an adiabatic process

P2V2  P1V1
W PV   const.
 1

• PVT relationship for real gases


HW problem #5

P1 ,T1 P2 , V2 , T2

Pf , V f , T f
Equation of state for real gases

1) Virial expansion – valid for gases only

2) Cubic equation of state – valid for gases and liquids


Compressibility factor (Z)
PV
Z Z for methane
RT
Ideal gas: Z = 1

Intermediate pressure: Z < 1


Due to dominance attractive
forces compression is favored

High pressure: Z > 1


Due to repulsive forces
expansion is favored
Virial equation of state
The virial equation of state are power series expansions for
compressibility factor in either pressure

PV
Z  1  BP  C P 2    
RT
or specific volume

PV B C
Z  1  2  
RT V V

B and B’ are related, as are C and C’


Example - Using virial equation of state
Q: Calculate Z and V for ethylene at 25 °C and 12 bar
using the truncated virial equation

Iterative method to solve for V


B = -140.5 cm3/mol
RT
C = 7,200 cm6/mol2 Start with V0  and solve for V1
P
 B C 
Truncated virial equation
RT
PV B C V1  1   2 
Z  1  2 P  V V 
RT V V  0 0 

Keep iterating until difference between


Rewrite the above equation as Vn and Vn+1 is small

RT  B C  RT  B C 
V 1   2  Vn 1  1   2 
P  V V  P  V V 
 n n 
Cubic equation of state
Cubic equations were developed to explain behavior of both
liquid and vapors
RT a
P  2 (van der Waal’s equation)
V b V

Isotherms in van
der Waals equation
Other cubic equations of state
1) Redlich-Kwong (1949)
2) Soave-Redlich-Kwong (1972)
3) Peng-Robinson (1976)

All the above equation of states can be written in the generic


form

RT a (T )
P 
V  b (V  b)(V  b)
Example – using cubic equation of state
Q: Find the molar volume of n-pentane at T = 100oC and P = 1bar.
The Peng-Robinson parameters for n-pentane at this temperature
are a = 2.417 *107 bar cm6/mol2 and b = 90.18 cm3/mol

RT a
Peng-Robinson EOS P 
V  b V (V  b)  b(V  b)

Ans : V  30324 cm3 / mol


P-T phase diagram for pure substances
look similar
Carbon dioxide Water

What if we change the axis to


Pr = P/Pc and Tr = T/Tc ?
Theory of corresponding states

P
Pc

V / VC

Using the reduced temperature Tr and reduced pressure Pr


makes the PVT behavior of different gases “correspond”
Theory of corresponding states

All fluids when compared at the same reduced temperature


and reduced pressure have the same compressibility factor
Theory of corresponding states
• If solving for V for any gas at known P and T,
 Look up PC and TC
 Use the graph or tabulated values to find Z
 Calculate V

Example: using compressibility chart, what is the density of


propane at T = 406.8 K and P = 8.5 MPa?

Propane Tc = 369.8K and Pc = 4.25MPa

Tr = 406.8/369.8 = 1.1 and Pr = 8.5/4.25 = 2


Example cont.

Tr = 1.1
Pr = 2

PV
Z  0.4
RT

V  1.6 10 4 m 3

See also example 3.9 in book

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