GENERAL PROPERTY

RELATION
Thermodynamics
Universitas Pertamina
2017
OUTLINE
• Maxwell Relation
• Enthalpy General Relation
• Entropy General Relation
OBJECTIVE
• Estimate Enthalpy (h) and Entropy
(s) value of real gas using
generalized chart (Appendix Fig. A
29-30)
• Compare with the ideal gas value
(Appendix Table 17-25)
THE ORIGIN OF THERMODYNAMICS RELATION
Gibbs-Hemholtz Fundamental thermodynamics
Equation equation

Maxwell Relation of its

partial derivative
Equation
Relation of change in
other properties (U,
H,S) relative to change
in P,V,T.
Can be described in
Thermodynamics General generalized chart (for
Relation all substances) by PR &
TR value
GIBBS-HEMHOLTZ & MAXWELL RELATION
Partial derivative relations

Derivative of z(x,y):

Taking the partial derivative of M with respect to y and of N with respect to x yields:
GIBBS-HEMHOLTZ & MAXWELL RELATION
Maxwell Relation

Four Gibbs-Hemholtz Relation

Partial
Derivation

Significance of Maxwell relation:

• Helpful in determining Δs by simply measuring the change in properties PVT
• LIMITED TO SIMPLE COMPRESSIBLE SYSTEMS
ENTHALPY GENERAL RELATION
1. Define ethalphy (h) as a function of P & T → h = h (T,P)
2. By the definition of total differential:

(1)
3. By substitution of Cp:

(2)
4. Doing step 1 & 2 with entropy (S) → s = s(T,P) and substituting the obtained
ds into relation dh = Tds + vdP :
(3)

5. Combine Eq (2) and (3):

(4)
ENTHALPY GENERAL RELATION

(4)

6. Using the fourth Maxwell Relation:

(5)
7. Substitute (5) into (2):

(6)
ENTHALPY GENERAL RELATION : REAL GAS DEVIATION

(7)
• General enthalpy relation :

(6)

• Calculate each value of ∆h from Eq. (6):

(8)

Enthalpy departure: variation of the enthalpy of a gas with pressure at a fixed temperature
Let’s focus on the last equation!
ENTHALPY GENERAL RELATION : FOR REAL GAS

(8)

Substitute v=ZRT/P (remember EOS relation Pv = ZRT for real gas!) and choosing Po = 0

𝑃 𝑃
𝑍𝑅𝑇 𝜕 𝑍𝑅𝑇/𝑃 𝑍𝑅𝑇 𝑅𝑇 𝜕 𝑍𝑇
ℎ∗ − ℎ = −න −𝑇 𝑑𝑃 = − න − 𝑑𝑃
0 𝑃 𝜕𝑇 𝑃 0 𝑃 𝑃 𝜕𝑇 𝑃

𝑃
𝑍𝑅𝑇 𝑅𝑇 𝑇𝜕𝑍 𝑍𝜕𝑇
ℎ∗ − ℎ = −න − + 𝑑𝑃
0 𝑃 𝑃 𝜕𝑇 𝜕𝑇 𝑃

(9)

Substituting T = TcrTR and P = PcrPR we get

(h*-h)T = Enthalpy departure

(10)
Zh = Enthalpy departure factor
ENTHALPY GENERAL RELATION : FOR REAL GAS

(10)

Enthalpy of a real gas at certain state:

ℎത 𝑇 = ℎത 𝑖𝑑𝑒𝑎𝑙 − 𝑍ℎ 𝑅𝑢 𝑇𝑐𝑟 kJ/kmol (11)

Combining eq. (10) with eq. (7), enthalpy change of a real gas from state 1 to state 2:

(7)

• Zh → From generalized enthalpy

kJ/kg
departure chart
(12)
• (ℎത 2 - ℎത1 )ideal → from ideal gas
or kJ/kmol
tables
Zh (Enthalpy Departure Factor)
Value from Appendix Fig A-29

𝑃
𝑃𝑅 =
𝑃𝐶𝑟

𝑇
𝑇𝑅 =
𝑇𝐶𝑟
• Ideal Gas Value:
Appendix Table 17-25
• Real Gas Value
Appendix Fig A-29
ENTROPY GENERAL RELATION
1. Define entropy (s) as a function of P & T → s = s (T,P) & doing total
differential:

2. Substitution of eq. (4) that we had earlier; and the 4th Maxwell relation to
above equation:

(4)

We get:

(13)
ENTROPY GENERAL RELATION
1. We can also define similar relation by deriving internal energy (u) and
entropy (s) as a function of T & v → s = s (T,v) and u = u (T,v) ;
𝜕𝑢
2. Substitution of 𝜕𝑇 with cv and substitution of total differential (ds) of s(T,v)
into du= Tds – Pdv we can get below relation:

3. Combining above relation with third Maxwell relation into the total
differential of s (T,v):

(14)
ENTROPY GENERAL RELATION : REAL GAS
• With similar manner as in enthalpy, we can obtain Entropy Departure Factor for real gas (Zs):

(15)

(s*-s)T,P = Entropy departure Zs = Entropy departure factor

Entropy of a real gas at certain state:

𝑠ҧ𝑇,𝑃 = 𝑠𝑖𝑑𝑒𝑎𝑙
ҧ − 𝑍𝑠 𝑅𝑢 (16)
Entropy change of a real gas from state 1 to state 2:

• Zs → From generalized
kJ/K.kmol
entropy departure chart
(17)
• (𝑠ഥ𝑜2 - 𝑠ഥ𝑜1 )ideal → from ideal
kJ/K.kg
gas tables
Zs (Entropy Departure Factor)
Generalized Chart from
Appendix Fig A-30

𝑇 𝑃
𝑇𝑅 = 𝑃𝑅 =
𝑇𝐶𝑟 𝑃𝐶𝑟
• Ideal Gas Value:
Appendix Table 17-25 + ideal gas entropy equation
• Real Gas Value
Appendix Fig A-29
INTERNAL ENERGY GENERAL RELATION : REAL GAS DEVIATION

Remember: ℎത = 𝑢+
ത P 𝑣ҧ (kJ/kmol)

P 𝑣=
ҧ Z𝑅𝑢 𝑇

Hence, specific internal energy of areal gas: 𝑢ത = ℎത − Z𝑅𝑢 𝑇

Internal energy change (∆u) of a real gas:

kJ/kmol (18)

Z → from EOS (Pv = ZRT)

Generalized compressibility chart (Fig. A-15)
EXERCISE
1. Hitung entalpi nitrogen dalam kJ/kg pada 175 K dan 8 Mpa menggunakan (a)
ideal gas nitrogen table (b) generalized enthalpy departure chart. Bandingkan
dengan nilai aktual = 125.5 kJ/kg.
(a) 181.5 kJ/kg, 44.6% (b) 121.6 kJ/kg, 3.1%

2. 0.55 kg/s gas Metana dikompresi secara adiabatik oleh steady-flow

kompresor dari 2 MPa dan -10oC menjadi 10 MPa dan 110oC. Dengan
menggunakan generalized chart, hitung daya yang dibutuhkan kompresor.
𝑍ℎ,1 = 0.21; 𝑍ℎ,2 = 0.5; ∆ℎ𝑖𝑑𝑒𝑎𝑙 = 277.3 𝑘𝐽/𝑘𝑔; W (real gas)= 136.72 kW

3. Gas CO2 dipanaskan dalam tangki bervolume konstan dari 100oC, 1 MPa
menjadi 1.63 MPa. Hitung perubahan entropi per massa CO2 menggunakan
(a) asumsi gas ideal (b) generalized chart.
𝑘𝐽 𝑘𝐽
(a) 𝑇2 = 608 𝐾; ∆𝑠𝑖𝑑𝑒𝑎𝑙 = 17.4 𝑘𝑚𝑜𝑙.𝐾; (b) 𝑍𝑠,1 = 0.055; 𝑍𝑠,2 = 0.013; ∆𝑠𝑟𝑒𝑎𝑙 = 17.75 𝑘𝑚𝑜𝑙.𝐾
EXERCISE
4. Berapa besarkah kesalahan (error) yang terjadi jika kita menggunakan
asumsi gas ideal untuk menentukan (a) enthalpi dan (b) internal energy CO2
pada 350 K dan 10 MPa?
(a) ℎത 𝑟𝑒𝑎𝑙 = 7557 kJ/kmol ; 50.2%, (b) 𝑢ത 𝑟𝑒𝑎𝑙 = 5694 kJ/kmol ; 48.2%

5. Propana dikompresi secara isotermal menggunakan alat silinder berpiston

dari 100°C dan 1 MPa menjadi 4 MPa. Jika kerja kompresi yang diperlukan
adalah 99.6 kJ/kg, dengan menggunakan generalized charts, tentukan
transfer panas per kg propana

q = -176.1 kJ/kg
References
• Chapter 6 Smith & Van Ness, Chemical Engineering
Thermodynamics 6th Ed
• Chapter 12 Cengel&Boles, Thermodynamics an Engineering
Approach