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, enthalpy and entropy. We also at this point introduce commonly used shorthand: symbols of the form MR are often used to represent residual properties of the form M-Mig. Usage The change in any intensive property M between two states (1) and (2) can be quantified using residual properties as: ( Or:

( ) (6.1)

)

(

)

(

)

**Integrating with Respect to dP:
**

(6.2)

(

)

∫

[

(

) ]

∫

[

(

) ]

(6.3)

∫

[(

)

]

(6.4)

**Integrating with Respect to dV:
**

(6.5)

∫

* (

)

+

(

)

∫

* (

)

+

(6.6)

( ) ∫ *( ) + (6.7) Summary of Cubic Equations of State The van der Waals equation can be written: or With: and The Soave equation can be written: ( ) or ( )( ) With: [ ( )] The Peng-Robinson equation can be written: ( ) ( ) or ( )[ ( ) ( ) ] With: [ ( )] .

3.167 (Example 6-10). beginning from the van der Waals equation: The partial derivative with respect to T is: ( ) The molar entropy departure function in general is described by equation 6. an expression for the residual enthalpy: ( ) And equation 6. We derived equation 6.156 (Example 6-9 Revisited).1) ( ) ∫ * + .6 we solved problems involving residual functions computed using the van der Walls EOS.Residual Properties from Cubic Equations of State In Section 6. for the residual internal energy: An analogous expression can be found for entropy.144: ( ) ∫ *( ) + Which for the van der Waals equation becomes: (6.

so the ln term is zero (ln 1). including the cubic equations introduced in this chapter. Thus the result is: (6.( √ )( ) * +- ( ) .( √ )( √ √ √ √ ) * √ ) √ ) √ ) √ ) +- (6.7) ( ) .10) .3) [ ( ) ( )]| ( ) * ( )+| (6.( √ )( ) * +- (6.( ) ∫ * + (6.2) Which integrates to: ( ) (6.6) .5) ( ) ( ) Analogous derivations can be performed to obtain residual properties for any equation of state. For the Peng-Robinson equation: √ √ ( ( √ ) √ ) ( ( ( ( (6.9) (6. b is insignificant compared to V.4) At the V = ∞ limit.8) In which: (6.

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