CHAPTER II

HOMOGENEOUS CLOSED SYSTEM

A closed system is one that does not exchange matter with
its surroundings, although it may exchange energy.

W nout = 0 dni = 0 (2.1)

System i = 1, 2, 3, . . .

 • No internal energy transported

Q accross boundary.
nin = 0

• All energy exchange between a closed system and its

surroundings appears as heat and work.
• The total energy change of the surroundings equals the net
energy transferred to or from it as heat and work.
First and second laws of Thermodynamcs:

dU  T dS – P dV (2.2)
For reversible process:
dU = T dS – P dV (2.3)

With T dS = dQrev : heat absorbed by the system

P dV = dWrev : work done by the system

If the interaction occurs irreversibly:

dU < T dS – P dV (2.4)
The internal energy change can be calculated by integrating
eq. (2.2):
S2 V2
U  U2  U1   T dS   P dV (2.5)
S1 V1

For process occuring at constant S and V:

dUS,V  0 (2.6)

• At constant S and V, U tends toward a minimum in an

actual or irreversible process in a closed system, and
remains constant in a reversible process.
• Eq. (2.6) provides a criterion for equilibrium in a closed
system.
Definition:
H  U + PV (2.7)
Differentiating eq. (2.7) yields:
dH = dU + V dP + P dV

Combining the above equation with eq. (2.3) leads to:

dH = (T dS – P dV) + V dP + P dV

dH = T dS + V dP (2.8)
For a closed system at constant S and P :
dHP,S  0 (2.9)
 the Helmholtz free energy (A) is a thermodynamic potential
that measures the “useful” work obtainable from a closed
system at a constant temperature and volume.

– A = the maximum amount of work extractable from a

thermodynamic process in which temperature and volume
are held constant..

Under these conditions, it is minimized at equilibrium.

Definition:

A = U – TS
(2.10)
Differentiating eq. (2.10) yields:

dA = dU – d(TS) = dQ + dW – T dS – S dT

= T dS – P dV – T dS – S dT

dA = – S dT – P dV (2.11)

For a closed system at constant T dan V:

dAT,V  0 (2.12)
 Definition:

G  A + PV (2.13)

Gibbs free energy (G) is a thermodynamic potential that

measures the "useful" or process-initiating work obtainable
from a thermodynamic system at a constant temperature and
pressure (isothermal, isobaric).
The Gibbs free energy is the maximum amount of non-
expansion work that can be extracted from a closed system;
this maximum can be attained only in a completely reversible
process.
Differentiating eq. (2.13) yields:

dG = dA + d(PV)

= – S dT – P dV + P dV + V dP

dG = – S dT + V dP (2.14)

For a closed system at constant T and P:

dGT,P  0 (2.15)
If F = F(x,y), the total differential of F is:

 F   F 
dF    dx    dy
 x  y  y  x

F  M dx  N dy (2.16)

 F 
with M  
 x  y

 F 
N  
 y  x
Further differentiation yields
 M   2F
  
 y  x  x y  M   N 
    (2.17)

  
N  2
F  y  x  x  y
 
 x  y  x y
Hence from equation:
F  M dx  N dy (2.16)

we obtain:
 M   N 
    (2.17)
 y  x  x  y
Resume:
dU = T dS – P dV (2.3)

dH = T dS + V dP (2.8)
dA = – S dT – P dV (2.11)

dG = – S dT + V dP (2.14)

According to eq. (2.17):

 T     P    S    P 
    (2.18)     (2.20)
 V  S  S  V  V  T  T  V

 T     V   S     V 
    (2.19)     (2.21)
  P  S  S  P  P  T  T P
ENTHALPY
As a function of P and T, we can express:
H  H T , P  (2.22)
Total differential of eq. (2.22):

 H   H  (2.23)
dH    dT    dP
 T P  P  T
(H/T)P is obtained from the definition of CP:
 H   C
  (2.24)
 T  P
P
(H/P)T is derived from fundamental equation:
dH = T dS + V dP (2.8)
Differentiation with respect of P at constant T yields:
 H   T  S   V
    (2.25)
 P  T  P  T
Combining eq. (2.25) with Maxwell equation (2.21):
 H   V  T  V 
    (2.26)
 P  T  T P
Introducing eqs. (2.24) and (2.26) into eq. (2.23) results in :
  V  
dH  CP dT   V  T    dP (2.27)
  T P 
ENTROPY
Entropy as a function of P and T:
S  S T , P  (2.28)
Total differential of eq. (2.28):

 S   S  (2.29)
dS    dT    dP
 T P  P  T

(S/P)T is obtained from Maxwell eq. (2.21):

 S     V 
    (2.21)
 P  T  T P
(S/T)P is derived from fundamental equation:
dH = T dS + V dP (2.8)
Differentiation with respect of T at constant P yields:
 H   T  S 
    (2.30)
 T  P  T  P
Combining eqs. (2.30) with (2.24):
 S   C P
  (2.31)
 T  P T
Introducing eqs. (2.21) and (2.31) into eq. (2.29) results in :
dT  V 
dS  CP    dP (2.32)
T  T P
INTERNAL ENERGY
As a function of T and V, we can express:
U  U T , V  (2.33)
Total differential of eq. (2.33):

 U   U  (2.34)
dU    dT    dV
 T  V  V  T
(U/T)V is obtained from the definition of CV:
 U   C
  (2.35)
 T  V
V
(U/T)V is derived from fundamental equation:
dU = T dS – P dV (2.3)
Differentiation with respect of V at constant T yields:

 U   T  S   P (2.36)
   
 V  T  V  T
Combining eqs. (2.36) and Maxwell equation (2.20):
 U   T  P   P
    (2.37)
 V  T  T  V
Introducing eqs. (2.35) and (2.37) into eq. (2.34) results in :
  P  
dU  C V dT   T    P dV (2.38)
  T  V 
ENTROPY
Entropy as a function of P and V:
S  S T , V  (2.39)
Total differential of eq. (2.39):

 S   S  (2.40)
dS    dT    dV
 T  V  V  T

(S/V)T is obtained from Maxwell eq. (2.20):

  S    P 
    (2.20)
 V  T  T  V
(S/T)V is derived from fundamental equation:
dU = T dS – P dV (2.3)
Differentiation with respect of T at constant V yields:

 U   T  S  (2.41)
   
 T  V  T  V
Combining eqs. (2.41) and (2.35):
 S   C V
  (2.42)
 T  V T
Introducing eqs. (2.20) and (2.42) into eq. (2.40) results in :
dT  P 
dS  C V    dV (2.43)
T  T  V
Fundamental equation:
dG = – S dT + V dP (2.14)

expressed as functional relation

G = G(T, P) (2.44)

Thus the special, or canonical, variables for the Gibbs energy

are temperature and pressure. Since these variables can be
directly measured and controlled, the Gibbs energy is a
thermodynamic property of great potential utility
An alternative form of Eq. (2.14), a fundamental property
relation, follows from the mathematical identity:

 G 1 G
d   dG  2 dT (2.45)
 RT  RT RT

Substitution for dG by Eq. (2.14) and for G by Eq. (2.13) gives,

after algebraic reduction
 G V H
d   dP  2 dT (2.46)
 RT  RT RT
The advantage of this equation is that all terms are dimension-
less; moreover, in contrast to eq. (2.14), the enthalpy rather
than the entropy appears on the right side.
 From eq. (2.46):

V   G RT  (2.47)

RT  P  T

H   G RT  (2.48)
 T
RT  T  P

When G/RT is known as a function of T and P, V/RT and

H/RT follow by simple differentiation.
The remaining properties are given by defining equations. In
particular,
S H G U H PV
  and  
R RT RT RT RT RT
No experimental method for the direct measurement of
numerical values of G or GIRT is known, and the equations
which follow directly from the Gibbs energy are ofblittle
practical use.

by definition the residual Gibbs energy is:

GR = G – Gig (2.49)

where G and Gig are the actual and the ideal-gas values of the
Gibbs energy at the same temperature and pressure.
Other residual properties are defined in an analogous way.
The residual volume, for example, is:

RT
V  VV  V
R ig
(2.50)
P

Since V = ZRT/P, the residual volume and the compressibility

factor are related:

RT
V   Z  1
R
(2.51)
P
The definition for the generic residual property is:

MR = M – Mig (2.52)

where M is the molar value of any extensive thermodynamic

property, e.g., V, U, H , S, or G. Note that M and Mig, the
actual and ideal-gas properties, are at the same temperature
and pressure.
Equation (2.46), written for the special case of an ideal gas,
becomes
 Gig  V ig Hig (2.53)
d   dP  2 dT
 RT  RT RT
 Residual Property:

 GR  VR HR
d   dP  2 dT (2.54)
 RT  RT RT

This fundamental property relation for residual properties

applies to fluids of constant composition.
Useful restricted forms are:
VR   GR RT 

RT  P  T
(2.55)

HR   GR RT 
 T   (2.56)
RT   T P
Residual Gibbs energy:

GR = HR – T SR (2.57)

The residual entropy is therefore

R R R
S H G
  (2.58)
R RT RT

For constant T, eq. (2.54) becomes:

 GR  V R
d  dP (contant T) (2.59)
 RT  RT
Integration from zero pressure to arbitrary pressure P yields:

GR P V R
 dP (constant T) (2.60)
RT 0 RT
where at the lower limit GR/RT is equal to zero because the
zero-pressure state is an ideal-gas state. In view of eq. (2.51):

GR P dP
  Z  1 (constant T) (2.61)
RT 0 P
Differentiation of eq. (2.61) with respect to temperature gives

 GR RT   Z  (2.62)
 T    T 
 P P
Combining eqs. (2.62) and (2.54) gives

HR P Z

 T     dP
(constant T) (2.63)
RT 0  T  P P

The residual entropy is found by combination of eqs.

(2.58), (2.61), and (2.63):

SR P Z

 T     dP P
   Z  1
dP
(constant T) (2.64)
R 0  T P P 0 p
RESIDUAL PROPERTY FROM VIRIAL EOS

For two-term virial equation

BP
Z 1
RT
From eq. (2.61):

GR P dP
  Z  1 (T konstan) (2.61)
RT 0 P

GR BP
We can get:  (2.65)
RT RT
Differentiation of eq. (2.56) with respect to T at constant P gives
  GR RT  BP P  dB 
 T    RT 2  RT  dT 
(2.66)
 P
Introducing eq. (2.62) into eq. (2.56):
R
H  P   1 dB B 
 T     2
RT  R   T dT T 
HR P  B dB 
    (2.67)
RT R  T dT 
Introducing eqs. (2.65) and (2.67) into eq. (2.58)
SR P dB
 (2.68)
R R dT
RESIDUAL PROPERTY FROM CUBIC EOS
Equations (2.61), (2.62), and (2.64) are incompatible with
pressure-explicit equations of state, and must be transformed
to make V the variable of integration.
ZRT
P (2.69)
V
RT ZRT (constant T)
dP  dZ  2 dV
V V
dP RT ZRT
 dZ  2 dV (constant T)
P PV PV
dP dZ dV
  (constant T) (2.70)
P Z V
Introducing eq. (2.70) into eq. (2.61):
R
G P
 dZ dV 
   Z  1   (constant T)
 (2.71)
RT 0  Z V 
The lower limit of the integration is P = 0 is the condition of
ideal gas:
P = 0  V =  and Z = 1

Hence, eq. (2.71) becomes:

R
G Z
 dZ  V 
   Z  1      Z  1 
dV 
 (constant T)
RT 1  Z    V 
 R
G Z
 1 V

   1   dZ   Z  1 
dV 
 (constant T)
RT 1  Z   V 

GR V
 dV 
 Z  1  ln Z   Z  1   (constant T)
RT   V 

GR 
V Z 1
 Z  1  ln Z      dV (constant T) (2.72)
RT  V V
Generalized form of cubic eos:
RT a
P 
V  b  V  b  V  b 

Z P 1 a
  
V RT V  b RT V  b  V  b 

Substituting the above equation into eq. (2.72) yields:

GR V 1 a 1
 Z  1  ln Z      dV
RT  V  b RT V  b  V  b  V 

(constant T) (2.73)
Consider the terms in the bracket of right hand side:
1 a 1
 
V  b RT V  b  V  b  V
1 a  1 1  1
     
V  b    bRT   V  b   V  b   V

Integration of the equation:

V
 1 a  1 1  1
      dV
V  b    bRT   V  b   V  b   V 
V
a  V  b 
 ln V  b   ln   ln V
   bRT  V  b  
 V
 V b a  V  b 
 ln  ln 
 V     bRT  V  b  

 V b a  V  b 
 ln  ln 
 V     bRT  V  b 

Introducing the last equation into eq. (2.73):

GR  V b a  V  b 
 Z  1  ln Z  ln  ln 
RT  V     bRT  V  b 

(constant T) (2.74)
The corresponding equation for HR follows from Eq. (2.54),
which in view of Eq. (2.51) may be written:
HR dP  GR 
2
dT  Z  1  d  (2.75)
RT P  RT 
Division by dT and restriction to constant V yields:

HR Z  1  P    GR RT 
    (constant V) (2.76)
RT 2
P  T  V  T  V
Differentiation of eq. (2.69) provides the first derivative on the
right, and differentiation of eq. (2.72) provides the second.
Substitution leads to:
HR V Z
 
 Z  1  T      dV 
 (2.75)
RT   T  V  V 
 Z  is derived from a cubic eos
 
 T  V

PV V aV
Z  
RT V  b RT V  b  V  b 

 Z    aV   1    
 2 
    
 T  V R V  b  V  b   T T  T  V 

 Z    aV  
   T
  
    
 T  V RT  V  b  V  b  
2
 T  V 
 Z    aV  
   T
    1

1 
   
 T  V 2 
   bRT   T  V    V  b   V  b  

The integration part of eq. (2.75):

V
 Z   dV 
T   
  T  V  V 

V a       1 1 
      T    dV
    bRT   T  V    V  b   V  b  

a       V  b 
     T   ln 
   bRT   T  V   V  b 
Introducing the last eq. into eq. (2.75):

HR a       V  b 
 Z  1      T   ln 
RT    bRT   T  V   V  b 

(2.76)
SR is calculated using the equation:
SR HR GR
 
R RT RT
a       V  b 
  Z  1     T   ln 

   bRT   T  V   V  b 
 V b a  V  b 
 Z  1  ln Z  ln  ln 
 V     bRT  V  b 

SR  V b a     V  b 
 ln Z  ln    ln 
R  V     bR  T  V  V  b 

(2.77)
EXAMPLE
Calculate HR and SR for n-butane at 500K and 50 bar using the
RK eos.

SOLUTION
RT a
P 
V  b  V  b  V  b 

For the RK eos: For n-butane:

=1 a = 0,42748 Tc = 425,1 K
=0 b = 0,08664 Pc = 37,96 bar
T 500
Tr    1.1762
Tc 425.1
 R2 Tc2 83,14 2  425,12
a  a  0 ,42748
Pc 37,96
=14066688

R Tc 83,14  425,1
b  b  0 ,08664  80 ,667
Pc 37,96
V is calculated numerically:

RT a  V  b 
V b
P P V V  b

Initial value of V:
RT 83,14 500 
V0    831,4 cm3 / mole
P 50
 RT a Vi1  b 
Vi  b
P P Vi1 Vi1  b 

i Vi-1 Vi error
1 831.40 655.25 2.69E-01
2 655.25 602.97 8.67E-02
3 602.97 583.38 3.36E-02
4 583.38 575.44 1.38E-02
5 575.44 572.12 5.80E-03
6 572.12 570.71 2.46E-03
7 570.71 570.11 1.05E-03
8 570.11 569.86 4.48E-04
9 569.86 569.75 1.91E-04
10 569.75 569.70 8.17E-05
Pada iterasi ke-10 diperoleh hasil V = 569,7 cm3/mol

PV 50 569,7 
Z   0 ,6850
RT 83,14 500 
HR a       V  b 
 Z  1      T   ln 
RT    bRT   T  V   V  b 

  Tr0.5
    0 ,5T 0.5 T 1.5   0.5
 
 T  V
c
Tr0.5 T
HR a  1 0 ,5   V 
 Z  1    0.5  0.5  ln 
RT bRT  Tr Tr   V  b 
HR
 Z  1 
1,5a 
ln
V 

RT bRT Tr0.5
 V b

HR
 0 ,6850  1
RT
1,514066688   569,7 
 ln 
80 ,667 83,14 500 1.1762 0.5
 569,7  80 ,667 

= – 1,0833

HR = (8,314 J mol-1 K-1) (500 K) (– 1,0833)

= – 4.503,3 J mol-1
SR  V b a     V  b 
 ln Z  ln    ln 
R  V     bR  T  V  V  b 

SR  V b 0 ,5a  V 
 ln Z  ln  ln 
R  V  bRT Tr 0.5
 V b

= – 0,78735

SR = (8,314 J mole-1 K-1) (– 1,0833)

= – 6.546 J mole-1 K-1