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LOGO THERMODYNAMICS 1

Volumetric Properties of Pure Fluids

Department of Chemical Engineering, Semarang State University

Dhoni Hartanto S.T., M.T., M.Sc.
 Introduction
Pressure, Volume, and Temperature (PVT) are important properties
such purposes as the metering of fluids
and the sizing of vessel and pipelines.

Quantitive description of real fluids

Equation of State (EoS)

Generalized correlation are used to predict PVT behaviour

of fluid which has no experimental data
 PVT Behaviour of Pure Substances
PT Diagram
C : critical point
(critical pressure Pc and Tc)
 the highest temperature 3 Fluid

and pressure at which a pure A

chemical species can exist in
Solid

P
vapor/liquid equilibrium Liquid C

Pc
In critical condition, fluid is
classified as liquid or gas 2 B
(the two phase become Triple Gas Region
indistinguishable) point Vapor
1
Sublimation curve
Gas in left side of dashed line can
be condensed as vapor Tc
T
Gas in right side of dashed line
(T >TC) is supercritical condition
 PVT Behaviour of Pure Substances

PV Diagram B to C line  single-phase saturated

liquids at their boling temperature

C to D line  single-phase saturated

vapor at their condensation
temperature
P

Fluid

Pc C Under curve BCD :

Subcooled-liquid (T below T boiling)
Solid+Liquid
Liquid
Solid

Superheated-vapor (T above T boil.)

Liquid+Vapor

B Solid+Vapor T<Tc Tc T>Tc

D
VL Vc VV
V
 PVT Behaviour of Pure Substances
Equation of State (EoS) : Functional equation to express
the relation between P, V, and T f ( P,V , T )  0

Partial derivatifve :  V   V 
dV    dT    dP
 T  P  P T
Partial derivatifve related to 2 properties:

Volume expansivity : Isothermal compressibility:

1  V  1  V 
      
V  T  P V  P T

Thus:
dV
 dT  dP
V
 PVT Behaviour of Pure Substances
If  and  are constant (for liquid approximation)
V 
ln  2    T2  T1    P2  P1  Simple EoS
 V1 

 Is almost always positive,  is necessarily positive

The value of  dan  has been commonly tabulated

PVT relation
 PVT Behaviour of Pure Substances
Example :
Acetone at 293.15 K and 1 bar has  =1.487 x 10-3 K-1 ,  = 62 x 10-6 bar-1, and V
= 1.287 x 10-3 m3 kg-1
a) Find the value of (P / T )V
b) The pressure generated when acetone is heated at constant volume from
293.15 K and 1 bar to 303.15 K
c) The volume change when acetone is changed from 293.15 K and 1 bar to
273.15 K and 10 bar

Solution :
a) dV
 dT  dP
V
V is constant  dV = 0,
0  dT  dP

 P   1.487  103 1
     24 bar K
 T V  62  106
 PVT Behaviour of Pure Substances
Solution :
b) The value of  and  can be assumed constant at interval temperature 10 K
The equation in (a) :

P  T  (24) (10)  240 bar

and
P2  P1  P  1  240  241bar

V 
c) ln  2    T2  T1    P2  P1 
 V1 
V 
ln  2   (1.487 10 3 ) 20  (62 10 6 )9  0.0303
 V1 

V2
 0.9702; V2  0.9702 (1.287 10 3 )  1.249 10 3 m3 kg 1
V1
V  V2  V1  (1.249  1.287) (10 3 )  (0.038) (10 3 ) m3 kg 1
 Virial Equation of State

• Equation of State (EoS)

f ( P,V , T )  0
• Gas Ideal (Simplest EoS)
PV  RT
- Volume individual = 0
- No interaction
- Valid in low pressure
• Real Gas
PV
PV  ZRT ; Z 
RT

Compressibility factor (Z) For ideal gas, Z = 1

 PVT Behaviour of Pure Substances
Virial EoS
B C D
Z  1  2  3  .........
V V V Virial expansions
Z  1  BP  CP 2  DP3  .........
B C
, 2 : 2-body interaction and 3-body interaction between pairs of molecules
V V
B
B' and : Second virial coefficients
V
C
C ' and 2 : Third virial coefficients
V

For a given gas the virial coefficients are functions of temperature only

B C  B2 D  3BC  2 B 3
B'  ; C'  ; D' 
RT ( RT ) 2 ( RT )3
 PVT Behaviour of Pure Substances
Truncated Virial EoS
B
Z  1 Z 1  BP
V

The B value has been tabulated

Z 1  BP for various gases
Z 1

Application :
a) Gas phase only (satisfactory results for vapor at
subcritical T)
b) Significantly molecul interactions
c) For low pressure gas (up to a pressure about 5 bar)
 Application of the Virial Equation
Originate value at Z = 1 for P = 0

The tangent to an isotherm at P = 0

is good approximation

 Z 
  T ; P  B
 P  Z
Tangent line eq. : Z 1  BP

PV BP
Z  1
RT RT

PV B
Z  1
RT V
 Application of the Virial Equation
The pressure above the range eq.
in previous slide but below critical
pressure
 three term virial equation give
excellent result

PV B C
Z  1  2
RT V V

Value of C and B depend on the gas

and on temperature

In figure 3.11, the trends are

similar
 Application of the Virial Equation
Ideal gas Equation of State

Virial EoS
B C D
Z  1   2  3  .........
V V V
If:
P0 or V 

Z 1 or PV  RT

Assumption : no molecule interaction

Good approximation for gas : in very low pressure or high
temperature (big Volume)
 Application of the Virial Equation
 Internal energy for ideal gas

U  U T , P  for real gas

P depend on molecule interaction

In ideal gas, no molecule interaction occured (V= infinite)

U  U T 

 Enthalpy for ideal gas

H  U  PV
H  H( T )
H  U  RT
 Application of the Virial Equation

 Heat capacity for ideal gas

 U 
CV   
 T V
CV  CV ( T )
U  U T 

 H 
CP   
 T P CP  CP ( T )
H  H T 

 The relation between CP and CV for ideal gas

dH  dU  d ( PV )
C p  CV  R
C p dT  CV dT  RdT
 Application of the Virial Equation
Extended virial equation (Benedict/Webb/Rubin Equation)

RT B0 RT  A0  C0 / T 2 bRT  a a c    
P     1   exp
V V2 V3 V6 V3T2  V2  V2

Where : A0 , B0 , C0 , a, b, c,  ,  are all constant for a given fluid

This complex equation are used in the petrolium and natural-gas industries
(light hydrocarbon and a few gas)
 Application of the Virial Equation
Example

The virial coefficients of isopropanol vapor at 200 oC :

B = -388 cm3 mol-1 ; C = -26000 cm6 mol-2
Calculate V and Z for isopropanol vapor at 200 oC and 10 bar by using :
a) The ideal-gas equation
b) Eq.3.37 (Smith Van Ness Handbook 6th ed)
c) Eq.3.39 (Smith Van Ness Handbook 6th ed)

Solution :
The absolute temperature is T = 473.15 K, gas constant (R) = 83.14 cm3 bar mol-1 K-1
a) Ideal gas, Z = 1

RT (83.14)(473.15)
V   3934 cm3 mol-1
P 10
 Application of the Virial Equation
RT
b) Solving eq. 3.37 for V : V  B  3934  (388)  3546 cm3 mol-1
P
PV V 3546
Z    0.9014
RT RT / P 3934

c) Solving eq. 3.39, rearrange equation to facilitate iteration, yield :

 B C 
RT
Vi 1  1   2 
 V V 
 P i i 

 388 26000 
V  3934 1   
 V V 
2

Using goal seek in M. Excel to obtain V , then V = 3488 cm3 mol-1
PV V 3488
Z    0.8866
RT RT / P 3934

The ideal gas value is 13% too high and no (b) is 1.7% too high
compare with this result