2-Fundamental Thermodynamics Property Relations-continued chap 4

Discussion:
(I) Internal energy (U) is an essential thermodynamic function and all
energies are derived from it. H, A, G are additional primary
thermodynamic properties. After Legendre's transformation of U
and all are expressed in canonical variables (V, T, S, P, ni).

n
dU = TdS − PdV + ∑ μ i dni --- EQ(1)
i =1

dH = TdS + VdP + ∑ μi dni

dA = −SdT − PdV + ∑ μi dni
dG = − SdT + VdP + ∑ μ i dni

Recalled from the 2nd thermodynamic law:

dU = Q + W = +TdS − PdV
(+: system absorbed heat; -: system gave work to environment)

From EQ(1) dU − TdS + PdV − ∑ μ i dni = 0

Legendre’s transformation gives:

H = U + PV , A = U − TS , G = U + PV − TS
Referred to p15 (Table 2-1).

31
Note:
These thermo properties (S,V) still be used as canonical variables.
For a homogenous system, all thermodynamic properties are functions of T
and P.

vapor(T,P)

Liquid(T,P)

But for heterogeneous or reaction system, U = f (T, P, surface area, or

magnetic field) = f (T, S, V, P). Such as Kevin effect of small droplets
evaporated fast than big droplets. Please refer to Modell and Reid,
Thermodynamics and its application.

(II) Using G - H equation

α β
If H = ∫ TT C p dT
2
and C p = f (T ) p , x = + + ......
1
T T2

Cp can be obtained from (1) PVT data or from (2) EOS

⎛ ∂ 2V ⎞
Cp −Cp = − T ⎜ 2 ⎟ dP
ideal p
∫0
⎝ ∂T ⎠ p , x
⎛ G ⎞ H
⎜ ⎟ = ∫T −
T
Then 2
dT , which can be obtained by integrating
⎝ RT ⎠ RT 21

⎛ G ⎞.
WRT temperature and never separate ⎜ ⎟
⎝ RT ⎠
32
(II) Cv or Cp can be but can’t be accurately obtained from PVT data by
using the EOS alone, because that Cp, Cv is determined by internal
molecular vibration, and any EOS is sensitive to internal modular
vibration.

⎛ ∂ 2V ⎞
C p = − ∫ T ⎜ 2 ⎟ dP
⎝ ∂T ⎠ P , x
⎛ ∂2P ⎞
Cv = ∫ T ⎜ 2 ⎟ dV
⎝ ∂T ⎠ v, x

⎛ ∂V ⎞ ⎛ ∂P ⎞
And C p − Cv = T ⎜ ⎟ ⎜ ⎟
⎝ ∂T ⎠ p , x ⎝ ∂T ⎠ v , x

⎛ ∂V ⎞ ⎛ ∂P ⎞
These ⎜ ⎟ and ⎜ ⎟ could be obtained from PVT data (or EOS).
⎝ ∂T ⎠ ⎝ ∂T ⎠
Any EOS can correlate the PVT data to get the Cp - Cv.

∂V ⎞ ⎛ ∂P ⎞
But it is not possible to get γ ≡ ⎛⎜ ⎟ ⎜ ⎟
⎝ ∂P ⎠T , x ⎝ ∂V ⎠ S ,x
⎛ ∂V ⎞ ⎛ ∂P ⎞
In which the solution of ⎜ ⎟ ⎜ ⎟ is impossible.
⎝ ∂P ⎠T , x ⎝ ∂V ⎠ S ,x

33
Ideal gas relations

It is necessary to mention this gas before the introductions of real gas

calculations using residual functions and of real mixture in liquid, gas or
solid phase calculations using fugacity (f) and fugacity coefficient (　).

Definitions of an ideal gas:

(i) no molecular volume
(ii) no molecular forces
(iii) obey the equation of state PV = RT.

1) Volumetric Derivatives P,V = f (temperature)

⎛ ∂P ⎞ R⎛ P⎞ ⎛ ∂2P ⎞ ∂ ⎛R⎞
⎜ ⎟ = ⎜≡ ⎟ ⎜ 2 ⎟ = ⎜ ⎟ =0
∂
⎝ ⎠v,x
T V ⎝ T⎠ ⎝ ∂ T ⎠ v , x ∂T ⎝ V ⎠ v , x
⎛ ∂V ⎞ R⎛ V ⎞ ⎛ ∂ 2V ⎞ ∂ ⎛R⎞
⎜ ⎟ = ⎜= ⎟ ⎜ 2 ⎟ = ⎜ ⎟ =0
⎝ ∂T ⎠ p,x P ⎝ T ⎠ ⎝ ∂ T ⎠ p ,x ∂T ⎝ P ⎠ p ,x
⎛ ∂P ⎞ P
⎜ ⎟ =−
⎝ ∂V ⎠T , x V

34
2) Enthalpy (H)

⎡ ⎛ ∂V ⎞ ⎤
( dH ) x = C p dT + ⎢V − T ⎜ ⎟ ⎥ dP = C p dT + [V − V ]dP = C p dT
⎣ ⎝ ∂T ⎠ p, x ⎦

Hint: Enthalpy in ideal gas = f (Temperature only)

⎛ ∂H ⎞ ⎛ ∂H ⎞ ⎛ ∂P ⎞ ⎛ ∂H ⎞
⎜ ⎟ =⎜ ⎟ ⎜ ⎟ = 0, since ⎜ ⎟ =0
⎝ ∂V ⎠T , x ⎝ ∂P ⎠T , x ⎝ ∂V ⎠T , x ⎝ ∂P ⎠T , x

3) Internal energy (U)

⎡ ⎛ ∂P ⎞ ⎤
(dU ) x = Cv dT + ⎢T ⎜ ⎟ − P ⎥ dV = Cv dT
⎣ ⎝ ∂T ⎠ v , x ⎦

Hint: Internal energy = f (temperature)

⎛ ∂U ⎞ ⎛ ∂U ⎞ ⎛ ∂V ⎞
⎜ ⎟ =⎜ ⎟ ⎜ ⎟ =0
⎝ ∂P ⎠T , x ⎝ ∂V ⎠T , x ⎝ ∂P ⎠T , x

35
(4) Entropy (S)
S = f (T , P) or S = f ( P, V ) or S = f (T ,V )

Recalled:
H = f (T , P ) = f ( P,V )
ΔH ⎞
Enthalpy (H) is tightly related with entropy (S). ΔS = ⎛⎜ ⎟.
⎝ T ⎠

But U = f (T , V ) and U ≠ f (P,V).

．Recalled: From statistical Mechanism, every atom have kinetic energy of

3 ⎛3 ⎞
E# = kT ⇒ U ≈ N ⎜ kT ⎟
2 ⎝2 ⎠
T is the only dominate independent variable.

It is possible for S = f (P,V). Just thinking about rats in big box (P =

constant = # of rats, when V increase ⇒ S↓ means that few chance to let
them collide each other than that in a small box (P = C, when V↓ ⇒ S
increase).

Therefore, it is good to use

S = f ( P , V ), like H = f ( P , V ) .

36
For ideal gas:
From most useful Maxwell equations
⎛ ∂S ⎞ ⎛ ∂P ⎞ R
⎜ ⎟ = + ⎜ ⎟ =
⎝ ∂V ⎠T , x ⎝ ∂T ⎠ v , x V
⎛ ∂S ⎞ ⎛ ∂V ⎞ R
⎜ ⎟ = −⎜ ⎟ = −
⎝ ∂P ⎠T , x ⎝ ∂T ⎠ p , x P

Then
Cp ⎛ ∂V ⎞ Cp R
(dS ) x = dT − ⎜ ⎟ dP = dT − dP ---EQ(1)
T ⎝ ∂T ⎠ p , x T P

Cv ⎛ ∂P ⎞ C R
( dS ) x = dT − ⎜ ⎟ dV = v dT + dV ---EQ(2)
T ⎝ ∂T ⎠ v , x T V

Cv ⎛ ∂T ⎞ C p ⎛ ∂T ⎞ Cv Cp
(dS ) x = ⎜ ⎟ dP + ⎜ ⎟ dV = dP + dV
T ⎝ ∂P ⎠ v , x T ⎝ ∂V ⎠ p , x P V

Hence:
R ⎛−R⎞
S = ∫ dS = ∫ TT,,vv ,,xx
2
dV = ∫ TT,,pp ,,xx ⎜
2
⎟dP
1
V 1
⎝ P ⎠

S = RLnV V = − RLn P P
V2 P2
1 1

37
(5) Heat capacities

⎛ ∂C p ⎞ ⎛ ∂ ⎛ ∂H ⎞ ⎞ ∂ ⎛ ∂H ⎞
⎜⎜ ⎟⎟ = −⎜⎜ ⎜ ⎟ ⎟⎟ = ⎜ ⎟ =0
⎝ ∂P ⎠T , x ∂
⎝ ⎝
P ∂T ⎠ P , x ⎠T , x ∂T ⎝ ∂P ⎠T , x

⎛ ∂CV ⎞ ⎛ ∂ ⎛ ∂U ⎞ ⎞ ∂ ⎛ ∂U ⎞
⎜ ⎟ = −⎜⎜ ⎜ ⎟ ⎟⎟ = ⎜ ⎟ =0
⎝ ∂V ⎠T , x ∂
⎝ ⎝
V ∂T ⎠v ,x ⎠T , x ∂T ⎝ ∂V ⎠T ,x

C p − Cv = R

⎛ ∂P ⎞
−⎜ ⎟
⎛ ∂V ⎞ ⎛ ∂P ⎞ ⎛ V ⎞⎛ ∂P ⎞ ∂l P
= ⎝ ⎠ =− n
Cp P
r≡ =⎜ ⎟ ⎜ ⎟ = −⎜ ⎟⎜ ⎟
Cv ⎝ ∂P ⎠T , x ⎝ ∂V ⎠ S , x ⎝ ⎠⎝
P ∂V ⎠S,x ⎛ ∂V ⎞ ∂l nV s , x
⎜ ⎟
⎝ V ⎠ s, x

(6) Joule-Thompson Coefficient

⎛ ∂V ⎞
⎟ − V T ⎛⎜ ⎞⎟ − V
T⎜ V
∂T ⎞ ⎝ ∂T ⎠ p , x
μ = ⎛⎜ = ⎝ ⎠
T
⎟ = =0
∂
⎝ ⎠ H ,x
P Cp Cp

38
Some Iso-process:
．Isenthalpical expansion process

When P decrease ⇒
(T H → T L ) mean 　 is positive for most fluids.
(T L → T H ) mean 　 is negative for Helium.

．Isothermal process mean ΔT = 0.

．Isentropical process ΔS = 0 mean Isenthalpical and reversible process.

．Isobaric process mean ΔP = 0.

．Naturally favorable process mean ΔS ≥ 0

For example:
A hydrophobic solid try to be soluble in a hydrophilic liquid at constant T
and 　 H. Supposed that the solubility is 10-4 mole fraction and the 　
enthaply change 　　　 H) is usually positive.

The macroscopic change of Gibbs energy (ΔG) in this process must be

positive and follows
ΔG = ΔH − TΔS and ΔG = −RTln(Xs).
Then the ΔS value must be negative means that the process doesn’t want to
be happen naturally.

39
Physical observables:
P, T, V, Q, W can be measured in the laboratory, but not U, H, A, G, S.

The following are common physical observables:

1 ⎛ ∂V ⎞
(a) Thermal expansion coefficient: β= ⎜ ⎟
V ⎝ ∂T ⎠ p
1 ⎛ ∂V ⎞
(b) Isothermal compressibility: KT = − ⎜ ⎟
V ⎝ ∂P ⎠T
⎛ ∂P ⎞ 1
(c) Bulk Isothermal modulus: BT = −V ⎜ ⎟ =
⎝ ∂V ⎠T KT
1 ⎛ ∂V ⎞
(e) Isentropic compressibility: KS = − ⎜ ⎟
V ⎝ ∂P ⎠ S
⎛ ∂P ⎞ 1
(f) Isentropic (adiabatic) Bulk modulus: Bs = −V ⎜ ⎟ =+
⎝ ∂V ⎠ S Ks
1 ⎛ ∂P ⎞
(g) Thermal pressure coefficient γ= ⎜ ⎟
p ⎝ ∂T ⎠V

The relationship of (a), (b), (g) give:

⎛ ∂P ⎞ ⎛ ∂T ⎞ ⎛ ∂V ⎞ γPkT
⎜ ⎟ ⎜ ⎟ ⎜ ⎟ = −1 ⇒ =1
⎝ ∂T ⎠V ⎝ ∂V ⎠ P ⎝ ∂P ⎠ T β

40
Furthermore the relationship of (a) and (b) give:

⎛ 1 ⎞ ⎛ ∂V ⎞
2 2

TV ⎜ ⎟ ⎜ ⎟
TVβ 2 ⎝ V ⎠ ⎝ ∂T ⎠ P ⎛ ∂V ⎞ ⎡⎛ ∂V ⎞ ⎛ ∂P ⎞ ⎤
C p − Cv = = = −T ⎜ ⎟ ⎜ ⎟ ⎜ ⎟
KT 1 ⎛ ∂V ⎞ ⎝ ∂T ⎠ P ⎢⎣⎝ ∂T ⎠ P ⎝ ∂V ⎠T ⎥⎦
− ⎜ ⎟
V ⎝ ∂P ⎠T

⎛ ∂V ⎞ ⎛ − ∂P ⎞
= −T ⎜ ⎟ ⎜ ⎟
⎝ ∂T ⎠ p ⎝ ∂T ⎠ v

TVβ 2 ⎛ ∂V ⎞ ⎛ ∂P ⎞
C p − Cv = = T⎜ ⎟ ⎜ ⎟
KT ⎝ ∂T ⎠ P ⎝ ∂T ⎠V

Discussion:
∂T ⎞
In the μ = ⎛⎜ ⎟ calculation,
⎝ ∂P ⎠ H , x

⎡ ⎛ ∂V ⎞ ⎤
( dH ) x = C p dT + ⎢V − T ⎜ ⎟ ⎥ dP = 0
⎣ ⎝ ∂T ⎠ p, x ⎦
Mean that Cp can’t be found from any of EOS, therefore, μ can't be found
from any of EOS, but they could be found experimentally.

41
Residual functions for calculating properties of a real gas
1. For a general real gas property (M)
ΔM'(T, P, x) = M'(T, P, x) − M(T, P, x) = residual property of M
ΔM' = difference between an ideal gas (M') and a real gas (M).

2. Calculating real gas property (M) using a chain rule, usually pressure
affects the non-ideality of a real gas.

⎛ ∂M ' ⎞ ⎛ ∂M ⎞
d (ΔM ' )T . x = ⎜ ⎟ dP − ⎜ ⎟ dP
⎝ ∂P ⎠T , x ⎝ ∂P ⎠T , x

⎧ ∂M ' ⎞ ⎛ ∂M ⎞ ⎫
ΔM ' (T , P, x ) = ΔM ' (T ,0, x ) + ∫ TT,,0P, ,xx ⎨⎛⎜ ⎟ −⎜ ⎟ ⎬dP
⎩⎝ ∂P ⎠ T , x ⎝ ∂P ⎠ T , x ⎭
---EQ(1)

3. If enthalpy (M = H)

⎛ ∂H ' ⎞
⎜ ⎟ =0
⎝ ∂P ⎠T , x
⎛ ∂H ⎞ ⎛ ∂V ⎞
⎜ ⎟ = V −T⎜ ⎟
⎝ ∂P ⎠T , x ⎝ ∂T ⎠ P, x
and ΔH'(T,0,x) = H'(T,0,x) − H(T,0,x) = H'(T,0,x) − H’(T,0,x) = 0

42
Substituted into EQ(1) ⇒

⎧ ∂V ⎞ ⎫
ΔH ' (T , P, x ) = 0 + ∫ TT,,0P, ,xx ⎨T ⎛⎜ ⎟ − V ⎬ dP
⎩ ⎝ ∂T ⎠ p , x ⎭

⎛ ∂V ⎞
It is required that EOS can be used to get ⎜ ⎟ and V is explicit.
⎝ ∂T ⎠ P , x

4. If entropy (M = S)

⎛ ∂S ' ⎞ R ⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ⎟ =− and ⎜ ⎟ = −⎜ ⎟
⎝ ∂P ⎠ T , x P ⎝ ∂P ⎠ T , x ⎝ ∂T ⎠ p , x

and ΔS'(T,0,x) = S'(T,0,x) − S(T,0,x) = S' − S' = 0 (at ideal condition)

⎧ ∂V R⎫
⇒ ΔS ' (T , P, x) = ∫ TT,,0P, ,xx ⎨⎛⎜ ⎞⎟ − ⎬dP
⎩⎝ ∂T ⎠ P , x P ⎭

⎛ ∂V ⎞
It is required that any EOS to get ⎜ ⎟ and V is explicit.
⎝ ∂T ⎠ P, x

Similarly, using dV (volume dependence) you could get ΔH'(T,V,x) and

43
 ⎛ ∂P ⎞
ΔS'(T,V,x), which it is required that EOS can be used to get ⎜ ⎟
⎝ ∂T ⎠ V , x
and P is explicit.

5. Other functions such as ΔU', ΔG', ΔA', etc.

ΔU' = ΔH' − PΔV'
ΔG' = ΔH' − TΔS'
ΔA' = ΔH' −PΔV' −TΔS'

For an ideal gas ⇒

ΔM'(T,0,x) = ΔU' = ΔH' = ΔG' = ΔA' = ΔS' = 0
But ΔV'(T,0,x) ≠ 0

5. Calculations using residual functions

Consider a change of state of a real gas having the property M2 (T2, P2, x)
from the M1 (T, P, x) is a single phase system.

ΔM = (T2 , P2 , x ) = M 2 (T2 , P2 , x ) − M 1 (T1 , P1 , x )

44
 M 2 (T2 , P2 , x 2 )

M1 (T1 , P1 , x )

M1' (T1 , P1 , x ) M i' (T2 , P1 , x ) M '2 (T2 , P2 , x )

Path independent state functions, such as U, H, G, A, S, etc.

ΔM = M 2 (T2 , P2 , x) − M 1 (T1 , P1 , x)
= ( M 1 '− M 1 ) + ( M i '− M 1 ' ) + ( M 2 '− M i ' ) + ( M 2 − M 2 ' )

= ΔM 1 '+[ M i ' (T2 , P1 , x ) − M 1 ' (T1 , P2 , x )] +

[ M 2 ' (T2 , P2 , x) − M i ' (T2 , P1 , x)] − ΔM 2 '

Where:
⎡ ∂M ' ⎞ ⎛ ∂M ⎞ ⎤
(I) ΔM 1 ' = ΔM 1 ' (T ,0, x ) + ∫ TT ,,0P, x, x ⎢⎛⎜
1 1
⎟ −⎜ ⎟ ⎥ dP
1

⎣⎝ ∂P ⎠ T , x ⎝ ∂P ⎠T , x ⎦
⎛ ∂M ' ⎞
(II) M i '−M 1 ' = ∫ TT ,,PP,,xx ⎜
2 1
⎟ dT
1 1
⎝ ∂T ⎠ p, x

⎛ ∂M ' ⎞
(III) M 2 '−M i ' = ∫ TT ,,PP ,,xx ⎜
2 2
⎟ dP
2
⎝1
∂P ⎠T , x

45
 ⎡⎛ ∂M ' ⎞ ⎛ ∂M ⎞ ⎤
(IV) ΔM 2 ' = ΔM 2 ' (T ,0, x ) + ∫ T2 , P2 , x
⎢⎜ ⎟−⎜ ⎟ ⎥ dP
⎣⎝ ∂P ⎠ ⎝ ∂P ⎠ T , x ⎦
T2 , 0 , x

46
Aside from residual property (　M’). What is ΔV':

V V VP
Z ≡ compressib ility factor = = =
V' ⎛ RT ⎞ RT
⎜ ⎟
⎝ P ⎠
⎛ RT V ⎞
or ⎜ = ⎟ for real gas.
⎝ P Z⎠

Definition:
RT V 1 ZRT 1
ΔV ' = V '−V =
− V = − V = V ( −1 + ) = ( −1 + )
P Z Z P Z
RT ZRT RT
= − ⇒ ΔV ' = (1 − Z )
P P P

From above definitions:

⎡ PV ⎤ ⎡ PV ' PΔV ' ⎤

lim( Z )T , x = lim ⎢ = l im −
p → 0 RT ⎥ p → 0 ⎢ RT RT ⎥⎦ T , x
P →0
⎣ ⎦T ,x ⎣
⎡ PΔ V ' ⎤
= lim ⎢1 − =1
p →0
⎣ RT ⎥⎦ T , x

47
If Z = 1 + β' P (Berlin form for Z)

⇒ ΔV ' = − B' RT = cons tan t

IfZ = 1 + B' P + C' P 2

lim( ΔV ' ) = − B' RT
p→0
v→∞

lim( ΔV ' )T ,x ΔV': a very special residual function

p →0

From virial equation definition adopted from the CRC Chemistry

handbook).

PV
Z= = 1 + B' ( T )[ P ] + C' ( T )[ P ] 2 = 1 + B( T )ρ + C ( T )ρ 2
RT
The above are the 2nd order virial equation of Berlin form and Leiden form.

RT ⎡ ρRT ⎤ ⎡ρ 2 RT ⎤
⇒ V= + B( T )⎢ ⎥ + C( T )⎢ ⎥
P ⎣ P ⎦ ⎣ P ⎦
RT ⎡ RT ⎤ ⎡ RT ⎤
= + B( T )⎢ + C ( T )
P ⎣ PV ⎥⎦ ⎢⎣ PV 2 ⎥⎦

For Leiden form:

RT ⎧ RT ⎡ RT ⎤ ⎡ RT ⎤ ⎫
⇒ ΔV ' = V ' −V = −⎨ + B( T )⎢ + C ( T )⎢⎣ PV 2 ⎥⎦ ⎬⎭
P ⎩ P ⎣ PV ⎥⎦

48
　 V’= − B( T )⎡⎢
RT ⎤ ⎡ RT ⎤
− C( T )⎢
⎣ PV ⎥⎦ ⎣ PV ⎥⎦
2

For Berlin form:

RT ⎧ RT ⎡ RT ⎤ ⎫
ΔV ' = V ' −V = −⎨ + B' ( T )( RT ) + C' ( T )[ P 2 ] ⎢ ⎬
P ⎩ P ⎣ P ⎥⎦ ⎭
ΔV ' = V ' −V = {B' ( T ) RT − C' ( T )[ PRT ] }

From Leiden form

⎧ ⎡ RT ⎤ ⎡ RT ⎤ ⎫
⇒ lim ( ΔV ' )T ,x = lim ⎨− B( T )⎢ ⎥⎦ − C ( T )⎢⎣ PV 2 ⎥⎦ ⎬⎭
p →0
V →∞
p →0
V →∞ ⎩ ⎣ PV
⎧ − B( T )⎫
= lim ⎨ ⎬ = − B( T )
V →∞ ⎩ ⎭
p →0 Z
Z =1

From Berlin form

⎧⎪ ⎫⎪
⎨ lim ( ΔV ' )T ,x = lim {− B' ( T )RT − C' ( T )[ PRT ]} = − B' ( T )RT ⎬
⎪⎩V→∞
p →0 p →0
V →∞ ⎪⎭

Discussion:
(I) Both derivations for lim( −ΔV ' )T ,x are suitable.
p →0

CRC used Z = 1 + B' [ P ] + C' [ P ] 2 = 1 + B' P + C' P 2

Statistical Mechanism used Z = 1 + Bρ + Cρ2
B and C is not equal to B’ and C’.

49
 RT
(II) Another derivation using ΔV ' = (1 − Z ) = - B(T)
P
(III) The relationship between B(T) and B’(T)RT is as follows:
B’(T)= B(T)/RT

C
C' = − ( B' )2

(RT )2
(IV) Second virial coefficient B = B'(RT)
If Berlin form
Z = 1 + B'P

( Z −1) BP
lnφ = ∫ 0 dP = = B' P
P

P RT
Hence, viral equation of state ( Z = 1 + B'P ) is only good to estimate Z @
low pressure gas region.

50
51
(V) Physical meaning of fugacity (f) and fugacity coefficient (　) in EOS
Recalled:
Integrated the d ln (f) = d ln (P), give the following:
⇒ f = P (C0)

For ideal gas: C0 = 1

f
For real gas: φ = C0 =
P

−∞

fσ

φσ

52
If both are single phases (or an ideal gas or ideal gas mixture)

μ = RT ln f + C1 (Chemical potential of real gas)

μ* = RTlnP + C1 (Chemical potential of ideal gas)

⎛f⎞
μ Re sidual = μ( P ,T ) − μ* ( P ,T ) = RT ln⎜ ⎟ = RTlnφ ---EQ(1)
⎝ p⎠
⎛ ∂μ R ⎞ RT
⇒⎜ ⎟ = V −V* = ( Z −1)
⎝ ∂P ⎠T p
RT
(Since ΔV ' = ( 1 − Z ) from the above definition of ΔV ' ).
P

⎛ ∂EQ( 1 ) ⎞ ⎛ ∂lnφ ⎞ RT
⎜ ⎟ ⇒ RT ⎜ ⎟= ( Z −1)
⎝ ∂P ⎠T ⎝ ∂P ⎠ P

Integrate the above equation give:

( Z −1)
lnφ = ∫ 0
P
dP
P

The equation is useful in solving for the fugacity coefficient (　) by

knowing any EOS.

53
 (VI) Using L’hospital rule for getting ΔV'

⎧ ⎛ sin x ⎞ ⎛ d sin x ⎞ ⎫
⎨ x →0 ⎜
lim =
⎟ x →0 ⎜
lim ⎟ = lim(cos x ) = 1⎬
⎩ ⎝ x ⎠ ⎝ dx ⎠ x→0 ⎭

⎧ RT ⎫ ⎧1 − Z ⎫ ⎧ d ( 1 − Z )⎫
lim( ΔV ' )T , x = lim ⎨ ( 1 − Z )⎬ = RT lim ⎨ ⎬ = RT lim ⎨ ⎬
p→0 p→0
⎩ P ⎭ p→0
⎩ P ⎭ p→0
⎩ dP ⎭

⎛ dZ ⎞
= − RT lim ⎜ ⎟ = − RT lim
d
{
1 + B' [ P ] + C' [ − P ] 2 }Berlin form
⎝
p → 0 dP
⎠ p → 0 dP

= − RT lim ( B' +2C' P ) = − RT ( B' ) = − B

p →0
v →∞

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