Lecture #8 1

Lecture 8

Objectives
1. Be able to derive a pressure explicit form for the residual function of any thermodynamic
variable.

Pressure Explicit Residual Functions

Most equations of state are pressure explicit, i.e., they are in the form P = f (T, V ), so it turns out
that integrating the functions with respect to pressure is almost always very difficult or impossible.
It would be better to have pressure explicit expressions for ∆J ′ . We have to transform the pressure
dependence to volume dependence. First, we note that J(T, P ) = J(T, V ). Reason: for a pure
fluid, or for a mixture at constant composition, only two variables are independent, so we can
specify any two and the system is in the same state.

∆J ′ (T, P ) = J ′ (T, P ) − J(T, P ) = J ′ (T, P ) − J(T, V )

= J ′ (T, P ) − J ′ (T, V ) + J ′ (T, V ) − J(T, V )
= ∆J ′ (T, V ) + J ′ (T, P ) − J ′ (T, V )

The first term on the R.H.S. is

Z V 
∂J ′
 
∂J
 
′
∆J (T, V ) = − dV
∞ ∂V T ∂V T

To evaluate the second two terms, note that P and V are the pressure and volume of the real fluid,
not the ideal gas. Let V ∗ be the volume occupied by the ideal gas at P, T, n, i.e., V ∗ = nRT /P .
Therefore, J ′ (T, P ) = J ′ (T, nRT /P ) 6= J ′ (T, V )
Z nRT /P 
∂J ′

J ′ (T, P ) − J ′ (T, V ) = J ′ (T, nRT /P ) − J ′ (T, V ) = dV
V ∂V T

Therefore, the fundamental equation for pressure explicit residual functions is

Z V 
∂J ′
 
∂J
  Z nRT /P 
∂J ′

∆J ′ (T, P ) = − dV + dV (1)
∞ ∂V T ∂V T V ∂V T

Now derive pressure explicit expressions for ∆J ′ (T, P ), J ∈ (H, S)

Z V 
∂H ′
 
∂H
  Z nRT /P 
∂H ′

∆H ′ (T, P ) = − dV + dV
∞ ∂V T ∂V T V ∂V T

∂H ∂S ∂P
     
=T +V
∂V T ∂V T ∂V T

But,
∂S ∂ ∂A ∂ ∂A ∂P
           
=− =− =
∂V T ∂V ∂T V T ∂T ∂V T V ∂T V

Hence,
∂H ∂P ∂P
     
=T +V
∂V T ∂T V ∂V T
Lecture #8 2

∂H ′ nR −nRT
 
=T +V =0
∂V T V V2
Therefore,
Z V  
∂P
 
∂P
 
∆H ′ = − V +T dV
∞ ∂V T ∂T V

Now find ∆S ′
Z V 
∂S ′
 
∂S
  Z nRT /P 
∂S ′

′
∆S = − dV + dV
∞ ∂V T ∂V T V ∂V T

∂S ∂P
   
=
∂V T ∂T V

∂S ′ nR
=
∂V T V
Note that
Z nRT /P 
nR

nRT
   
nRT
 
dV = nR ln − ln V = nR ln = −nR ln z
V V P PV
Therefore,
Z V 
nR

∂P
 
′
∆S = − dV − nR ln z
∞ V ∂T V

where z is the compressibility factor.

Note:
nRT
∆V ′ = −V
P
∆U ′ = ∆H ′ − P ∆V ′
∆G′ = ∆H ′ − T ∆S ′
∆A′ = ∆H ′ − T ∆S ′ − P ∆V ′
Alternatively, expressions for ∆U ′ , etc. can be derived from Equation (1).

Example: Pressure Explicit Residual

Find ∆H̃ ′ for the Lorentz EOS. This is the equation for which we obtained a very complex expression
when attempting to define ∆H̃ ′ from the volume explicit formuation for the residual functions. Let’s
see if it is any easier when we use the pressure explicit formulation. We start with
1 b a
 
P = RT + −
Ṽ Ṽ 2 Ṽ 2
   
∂P ∂P
and we need the deravitives Ṽ ∂ Ṽ
and T ∂T .
T Ṽ

∂P RT (RbT − a)
 
V =− −2
∂ Ṽ T Ṽ Ṽ 2
∂P RT RbT
 
T = +
∂T Ṽ Ṽ Ṽ 2
Lecture #8 3

Therefore,
Z Ṽ 
RT (RbT − a) RT RbT
 Z Ṽ RT b − 2a 2a − RT b
′
∆H̃ = − − −2 + + dṼ = dṼ =
∞ Ṽ Ṽ 2 Ṽ Ṽ 2 ∞ Ṽ 2 Ṽ
Consider now how you would compute the temperature of an isenthalpic process, T1 = 500 K,
P1 = 200 bar, P2 = 1 bar, T2 =? Since we know that ∆H = 0 we can write:
! !
Z T2 ∂ H̃ ′
Z P2 ∂ H̃ ′
′ ′
∆H̃ = 0 = ∆H̃ (T1 , P1 ) − ∆H̃ (T2 , P2 ) + dT + dP
T1 ∂T P P1 ∂P T
Z T2
= ∆H̃ ′ (T1 , P1 ) − ∆H̃ ′ (T2 , P2 ) + C̃P′ dT
T1
2a − RT1 b 2a − RT2 b
Z T2
0 = − + C̃P′ dT
Ṽ1 Ṽ2 T1

How do you solve this? You need to be able to find Ṽ = f (T, P ) and then to numerically (iteratively)
solve for T2 until the equation is close to zero.