Double

Single 𝑋 −𝑋 𝑋−𝑋 𝑋 𝑋 𝑋
𝑀= 𝑀 + 𝑀 Interpolation
Interpolation 𝑋 −𝑋 𝑋 −𝑋
𝑌 𝑀 , 𝑀 ,
𝑌 𝑀 ,
𝑋 −𝑋 𝑋−𝑋 𝑦 −𝑦
𝑀= 𝑀 , + 𝑀, 𝑌 𝑀 , 𝑀 ,
Double 𝑋 −𝑋 𝑋 −𝑋 𝑦 −𝑦
Interpolation 𝑋 −𝑋 𝑋−𝑋 𝑦−𝑦
+ 𝑀 , + 𝑀, SRK EOS:
𝑋 −𝑋 𝑋 −𝑋 𝑦 −𝑦
𝑅𝑇 𝑎
SRK EOS 𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
Ideal Gas 𝑃𝑉 = 𝑅𝑇

Compressibility factor: 𝑍= . Z form 𝑍 − 𝑍 + (𝐴 − 𝐵 − 𝐵 )𝑍 − 𝐴𝐵 = 0

( ) / 0.42748𝛼𝑅 𝑇 0.08664𝑅𝑇
Volume of saturation for liquids: 𝑉 = 𝑉𝑍 𝑎= 𝑏=
𝑃 𝑃

𝜔 = −1 − 𝑙𝑜𝑔 (𝑃 ) .
𝛼 = 1 + 𝜅 1 − √𝑇𝑟 𝜅 = 0.48 + 1.574𝜔 − 0.176𝜔

Virial EOS (only Gasses):-

𝑅𝑇
Pressure explicit 𝑅𝑇 𝐵 𝐶 𝐷 𝑉 =
Vapor like 𝑃
𝑃= 1+ + + +⋯
form 𝑉 𝑉 𝑉 𝑉
phase 𝑅𝑇 𝑎(𝑉 − 𝑏)
One term quadratic 𝑅𝑇 𝐵𝑅𝑇 𝑉 = +𝑏−
𝑉 − 𝑉− =0 𝑃 𝑃𝑉 (𝑉 + 𝑏)
form 𝑃 𝑃
𝑅𝑇 𝐵𝑅𝑇 𝐶𝑅𝑇 𝑉 =𝑏
Two term cubic form 𝑉 − 𝑉 − 𝑉− =0 Liquid like
𝑃 𝑃 𝑃 𝑅𝑇 + 𝑏𝑃 − 𝑉 𝑃
phase 𝑉 = 𝑏 + 𝑉 (𝑉 + 𝑏)
Volume explicit form 𝑅𝑇 𝑎
𝑉= (1 + 𝐵 𝑃 + 𝐶 𝑃 + 𝐷 𝑃 + ⋯ )
𝑃
PR EOS:
𝐵 𝐶−𝐵 𝐷 − 3𝐵𝐶 + 2𝐵
𝐵 = 𝐶 = 𝐷 =
𝑅𝑇 (𝑅𝑇) (𝑅𝑇)
𝑅𝑇 𝑎
PR EOS 𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏) + 𝑏(𝑉 − 𝑏)
All VND, RK, SRK, PR:-
𝑎𝑃 𝑏𝑃 𝑍 + (𝐵 − 1)𝑍 + (𝐴 − 2𝐵 − 3𝐵 )𝑍 − 𝐴𝐵 + 𝐵 + 𝐵
𝐴= 𝐵= Z form
(𝑅𝑇) 𝑅𝑇 =0
𝑇 𝑃 0.45724𝛼𝑅 𝑇 0.07780𝑅𝑇
𝑇 = 𝑃 = 𝑎= 𝑏=
𝑇 𝑃 𝑃 𝑃

Van Der Waals EOS:- 𝛼 = 1 + 𝜅 1 − √𝑇𝑟 𝜅 = 0.37464 + 1.54226𝜔 − 0.26992𝜔

Van Der Waals 𝑅𝑇 𝑎
𝑃= − 𝑅𝑇
EOS 𝑉−𝑏 𝑉 𝑉 =
𝑃
Cubic form 𝑃𝑉 − (𝑃𝑏 + 𝑅𝑇)𝑉 + 𝑎𝑉 − 𝑎𝑏 = 0 Vapor like
Z form 𝑍 − (1 + 𝐵)𝑍 + 𝐴𝑍 − 𝐴𝐵 = 0 phase 𝑅𝑇 𝑎 (𝑉 − 𝑏)
𝑉 = +𝑏−
27𝑅 𝑇 𝑅𝑇 𝑃 𝑃 (𝑉 + 1 − √2 𝑏)(𝑉 + 1 + √2 𝑏)
𝑎= 𝑏=
64𝑃 8𝑃
8𝑎 𝑎 𝑉 =𝑏
𝑉 = 3𝑏 𝑇 = 𝑃 = Liquid like
27𝑏𝑅 27𝑏
phase 𝑅𝑇 + 𝑏𝑃 − 𝑉 𝑃
𝑅𝑇 𝑉 = 𝑏 + (𝑉 + 1 − √2 𝑏)(𝑉 + 1 + √2 𝑏)
𝑉 = 𝑎
𝑃
Vapor like phase
𝑅𝑇 𝑎(𝑉 − 𝑏)
𝑉 = +𝑏− Pitzer correlation (Lee & Kesler method)
𝑃 𝑃𝑉
𝑉 =𝑏 Pitzer correlation 𝑍 = 𝑍 + 𝜔𝑍
Liquid like phase 𝑅𝑇 + 𝑏𝑃 − 𝑉 𝑃
𝑉 =𝑏+𝑉 𝑃
𝑎 𝑍 = 1+𝐵
𝑇
𝐵 = 𝐵 + 𝜔𝐵
RK EOS:
Pitzer correlation for one 0.422
𝑅𝑇 𝑎 𝐵 = 0.083 −
term virial coefficient 𝑇 .
RK EOS 𝑃= −
𝑉 − 𝑏 𝑉(𝑉 + 𝑏)
0.172
Z form 𝑍 − 𝑍 + (𝐴 − 𝐵 − 𝐵 )𝑍 − 𝐴𝐵 = 0 𝐵 = 0.139 −
𝑇 .
.
0.42748𝑅 𝑇 0.08664𝑅𝑇
𝑎= 𝑏= 𝑃 𝑃
𝑃 √𝑇 𝑃 𝑍 =1+𝐵 +𝐶
𝑇𝑍 𝑇𝑍
𝑅𝑇 𝐶 = 𝐶 + 𝜔𝐶
𝑉 = Pitzer correlation for two
𝑃 0.00313 0.02432
Vapor like phase term virial coefficients 𝐶 = 0.01407 − +
𝑅𝑇 𝑎(𝑉 − 𝑏) 𝑇 . 𝑇
𝑉 = +𝑏−
𝑃 𝑃𝑉 (𝑉 + 𝑏) 0.05539 0.00242
𝐶 = −0.02676 + −
𝑉 =𝑏 𝑇 . 𝑇 .
Liquid like phase 𝑅𝑇 + 𝑏𝑃 − 𝑉 𝑃 𝐵 𝑅𝑇 𝐶𝑅 𝑇
𝑉 = 𝑏 + 𝑉 (𝑉 + 𝑏) 𝐵= 𝐶=
𝑎 𝑃 𝑃
 The ideal gas Process calculations for ideal gases
• Assumptions: • Consider a closed system process:
• Molecules have a negligible volume
• 1st law of thermodynamics: dQ = dU − dW
• Molecules exert no forces on one another (when p → 0, Z → 1)
• Molecules collide elastically with the walls of their container • If the process is mechanically reversible: dW = − pdV
• If it involves an ideal gas: dU = CV dT
• The pVT behavior of an ideal gas is described by the ideal
gas law: dQ = CV dT + pdV
pV = RT
• One property (p, V or T) can be removed from this equation
• For any change in state of an ideal gas: using the ideal gas EoS:
T2
dU = CV dT RT pV RT
U =  CV dT p= T= V=
T1 Independent of type of process V R p
(isobaric/isothermal/isochoric/
T2 adiabatic)
dH = C P dT H =  C P dT
75 76
T1

Overview Types of processes

Equations for ideal gas process calculations • Isothermal process: dT = 0

with: p = RT/V V  p 
U = H = 0 and
Q = −W = RT ln 2  = − RT ln 2 
dV dV  V1   p1 
dQ = CV dT + RT dW = − RT
V V • Isobaric process: dp = 0
with: V = RT/p U =  CV dT and Q = H =  C P dT and W = − R(T2 − T1 )
dp dp
dQ = C P dT − RT dW = RT − RdT
p p • Isochoric process: dV = 0 and W = 0

with: T = pV/R Q = U =  CV dT and H =  C P dT and W =0

CP C
dQ = pdV + V Vdp dW = − pdV • Adiabatic process: Q = 0
R R
and and Q=0
77 78
U = W =  CV dT H =  C P dT
 Adiabatic process for ideal gas Adiabatic process for ideal gas

• Adiabatic process: Q = 0 • Adiabatic process: Q = 0

dV dT R dV dp dT R dp
dQ = CV dT + RT =0 =− dQ = C P dT − RT =0 =
V T CV V p T CP p

• Integration (assuming constant CV): • Integration (assuming constant CP):

T  R  V2  using: a.ln(x) = ln(xa)
 T  R  p2  using: a.ln(x) = ln(xa)
ln 2  = − ln  ln 2  = ln 
 T1  CV  V1   T1  C P  p1 

R / CV R / CP
T2  V1  T2  p2 
=  = 
T1  V2  T1  p1 

79 80

Adiabatic process for ideal gas Adiabatic process for ideal gas

R / CV R / CP C P / CV
• Adiabatic process: Q = 0 • Overview: T2  V1  T2  p2  p2  V1 
=  =  = 
C C dp C dV T1  V2  T1  p1  p1  V2 
dQ = P pdV + V Vdp = 0 =− P
R R p CV V
):
• Integration (assuming constant CV and CP):
𝑪𝑷

R C P − CV R C P − CV 1  −1
𝑪𝑽
• Introducing the heat capacity ratio (𝜸 =

p  C V  using: a.ln(x) = ln(xa) = =  −1 = = 1− =

ln 2  = − P ln 2  CV CV CP CP  
 p1  CV  V1 

C P / CV
• Therefore: TV  −1 = constant only for ideal gases with
p2  V1  (Poisson) constant heat capacity
=  Tp (1− ) /  = constant undergoing mechanical
p1  V2  reversible adiabatic
expansion or compression
pV  = constant in a closed system
81 88
 Overview Example 3.3
Equations for ideal gas process calculations
Isothermal process
• Air (ideal gas, CV = 2.5.R, Cp = 3.5.R) can be compressed
V  p  from 1 bar and 25 oC to 5 bar and 25 oC in three different
Q = −W = RT ln  2  = − RT ln  2  at constant T
 V1   p1  (fully reversible) ways:
Isobaric process • Isochoric heating followed by isobaric cooling
• Isothermal compression
Q = H =  C P dT W = − R(T2 − T1 ) at constant p
• Adiabatic compression followed by isochoric cooling
Isochoric process • What are the heat and work requirements and the changes
Q = U =  CV dT W =0 at constant V in internal energy (ΔU) and enthalpy (ΔH) for each process?

Adiabatic process • Solution:

Q=0 W =  CV dT • For each process, the total change in internal energy (ΔU)
(1− ) /   and enthalpy (ΔH) is identical:
TV  −1 = constant; Tp = constant; pV = constant;  = C P / CV
U = H = 0 as Tfinal = Tstart
89 90

Example 3.3 Example 3.3

• Isochoric heating followed by isobaric cooling: • Isothermal compression:

T1 = 298.15 K T3 = 298.15 K T1 = 298.15 K T3 = 298.15 K
1 2
p1 = 1 bar 1 2 3 p3 = 5 bar p1 = 1 bar p3 = 5 bar
RT m3 RT
V1 = 1 V2 = 0.02479 V3 = 3
p1 mol p3
m3 p2 = 5 bar m3 V  p 
= 0.02479 pV = 0.00496 Q = −W = RT ln  2  = − RT ln  2 
mol T2 = 2 2 = 1490.75 K mol
R  V1   p1 
• Step 1→2:
QV = U = CV (T2 − T1 ) = 24788 J/mol and W = 0 J/mol 5
Q = −8.3145  298.15 ln  = −3990 J/mol
1
• Step 2→3:
W = 3990 J/mol
Q p = H = C p (T3 − T2 ) = −34703 J/mol and W = − R(T3 − T2 ) = 9915 J/mol
• Overall:
Q = 24788 − 34703 = −9915 J/mol and W = 9915 J/mol 92
91