Thermochemistry

Note 1

Thermodynamic Properties of Fluids

 Quiz 1

1. Desarrolle una ecuación global para la primera ley de la

termodinámica, a partir de un balance de energía.

2. Por que el termino de la entropía generada en un proceso

irreversible es una propiedad de trayectoria y no de
punto, demuéstrelo matemáticamente.
 Property relations for homogeneous phases

First law for a closed system d (nU ) = dQ + dW

a special reversible process
d (nU ) = dQrev + dWrev
dWrev = − Pd (nV ) dQrev = Td (nS )
d (nU ) = Td (nS ) − Pd (nV )

Only properties of system are involved:

It can be applied to any process in a closed system (not necessarily
reversible processes).
The change occurs between equilibrium states.
 d ( nU ) = Td (nS ) − Pd (nV )
The primary thermodynamic properties: P, V , T , U , and S
The enthalpy: H ≡ U + PV
The Helmholtz energy: A ≡ U − TS
The Gibbs energy: G ≡ H − TS

For one mol of homogeneous fluid of constant composition:

 ∂T   ∂P 
dU = TdS − PdV   = − 
 ∂V  S  ∂S V
 ∂T   ∂V 
dH = TdS + VdP   = 
 ∂P S  ∂S P
 ∂P   ∂S 
dA = − PdV − SdT   = 
 ∂T V  ∂V T
 ∂V   ∂S  Maxwell’s equations
dG = VdP − SdT   = −  
 ∂T P  ∂P T
Enthalpy, entropy and internal energy change calculations f (P,T)

 ∂H   ∂H   ∂S   ∂S 
dH =   dT +   dP dS =   dT +   dP
 ∂T  P  ∂P T  ∂T  P  ∂P T
 ∂H  dH = TdS + VdP  ∂S  C  ∂V   ∂S 
  = CP   = P   = − 
 ∂T P  ∂T  P T  ∂T  P  ∂P T
 ∂H   ∂S 
  = T  +V
 ∂P T  ∂P T dT  ∂V 
dS = C P −  dP
 ∂H   ∂S  T  ∂T  P
  = T 
 ∂T  P  ∂T  P

  ∂S  
dH = C P dT +  T   + V dP H ≡ U + PV
  ∂P T 

 ∂V   ∂S 
 ∂H   ∂U   ∂V 
  = −     =  + P  +V
 ∂T  P  ∂P T  ∂P T  ∂P T  ∂P T

  ∂V    ∂U   ∂V   ∂V 
dH = C P dT + V − T   dP   = −T   − P  
  ∂T  P   ∂P T  ∂P T  ∂P T
Internal energy and entropy change calculations f (V,T)

 ∂U   ∂U   ∂S   ∂S 
dU =   dT +   dV dS =   dT +   dV
 ∂T V  ∂V T  ∂T V  ∂V T
 ∂U   ∂U   ∂S   ∂U   ∂S   ∂S   ∂P 
  = CV   = T  −P   = T    = − 
 ∂T V  ∂V T  ∂V T  ∂T V  ∂T V  ∂V T  ∂T V

  ∂S    ∂S  CV
dU = CV dT +  T   − P dV   =
  ∂V T   ∂T V T

 ∂S   ∂P  dT  ∂P 
  = −   dS = CV +  dV
 ∂V T  ∂T V T  ∂T V

  ∂P  

dU = CV dT +  T   − P dV
  ∂T V 
 Quiz 2
Calcular  ∂U 
 
 ∂V T

Para el N2 en estado gaseoso a 25oC y 1 atm usando la

siguiente ecuación:
nRT an 2
P= − 2
V − nb V
Información adicional:

a = 1,35 x 106 atm.cm6/mol2

b = 38,6 cm3/mol
V/n = 24,5 x 103 cm3/mol
 Quiz 3

Demuestre que Cp = Cv = C para fluidos incompresibles.

En el caso de este tipo de fluidos β = κ = 0. Este tipo de
modelos son comúnmente usados en mecánica de fluidos.

19 y 26 de septiembre Nicolas. Excel

nmirandah@unal.edu.co
E-mail horario de atención.
Gibbs energy G = G (P,T)

dG = VdP − SdT Thermodynamic property of great potential utility

 G  1 G
d ≡ dG − 2
dT
 RT  RT RT
G ≡ H − TS dG = VdP − SdT

 G  V H  G   ∂ (G / RT )   ∂ (G / RT ) 
d  ≡ dP − dT d =  dP +   dT
 RT  RT RT 2
 RT   ∂P T  ∂T P

V  ∂ (G / RT ) 
= 
RT  ∂P T
H  ∂ (G / RT ) 
= −T  
RT  ∂T P G/RT = g (P,T)

The Gibbs energy serves as a generating function

for the other thermodynamic properties.
 Residual properties

• The definition for the generic residual property:

M R ≡ M − M ig
– M and Mig are the actual and ideal-gas properties,
respectively.
– M is the molar value of any extensive thermodynamic
properties, e.g., V, U, H, S, or G.
• The residual Gibbs energy serves as a generating
function for the other residual properties:
 GR  V R HR
d   = dP − 2
dT
 RT  RT RT
  GR  V R HR const T  GR  VR
d   = dP − 2
dT d   = dP
 RT  RT RT  RT  RT

GR PV
R
=∫ dP
RT 0 RT
R ig ZRT RT
V = V −V = −
H  ∂ (G / RT )  P P
= −T  
HR P  ∂Z  dP RT  ∂T P GR P dP
= −T ∫   = ∫ ( Z − 1)
RT 0
 ∂T  P P RT 0 P const T

S R H R GR SR P  ∂Z  dP P dP
= − = −T ∫   − ∫ ( Z − 1)
R RT RT R 0
 ∂T  P P 0 P

const T
Z = PV/RT: experimental measurement .Given PVT data or an appropriate equation
of state, we can evaluate HR and SR and hence all other residual properties.
 ig R
{
H = H + H = H + ∫ C dT + − RT ∫ 
ig
0
T0
T 

ig
P }
2
0
P  ∂Z  dP 

 ∂T

P P


 P  ∂Z  dP 
{ ig
}
= H 0 + R × ICPH (T0 , T ; A, B, C , D) + − RT ∫ 
2
 
 0
 ∂ T P P 
 P  ∂Z  dP 
{ ig
= H + C
0
ig
P H }
(T − T0 ) + − RT ∫0  
2

 ∂T P P

 
 P  ∂Z  dP 
{ }
= H 0ig + R × MCPH (T0 , T ; A, B, C , D )(T − T0 ) + − RT 2 ∫   
 0
 ∂T P P 
 T dT P  P  ∂Z  dP P dP 
S = S ig + S R = S 0ig + ∫ C Pig − R ln  + R − T ∫   − ∫ ( Z − 1) 
 T0 T P0  0
 ∂ T P P 0 P 
 ig P  P  ∂Z  dP P dP 
= S 0 + R × ICPS (T0 , T ; A, B, C , D) − R ln  + R − T ∫   − ∫ ( Z − 1) 
 P0   0
 ∂T  P P 0 P
 ig T P  P  ∂Z  dP P dP 
= S 0 + C P ln − R ln  + R − T ∫ 
ig
 − ∫ ( Z − 1) 

S T 0 P0  0
 ∂T P P 0 P
 T P  P  ∂Z  dP P dP 
= S 0ig + R × MCPS (T0 , T ; A, B, C , D) ln − R ln  + R − T ∫   − ∫ ( Z − 1) 
 T0 P0  0
 ∂T P P 0 P 
 Calculate the enthalpy and entropy of saturated isobutane vapor at 360
K from the following information: (1) compressibility-factor for
isobutane vapor; (2) the vapor pressure of isobutane at 360 K is 15.41
bar; (3) at 300K and 1 bar, H 0ig = 18115 J / mol S 0ig = 295.976 J / mol ⋅ K (4) the
ideal-gas heat capacity of isobutane vapor: CPig / R = 1.7765 + 33.037 ×10−3 T

HR P  ∂Z  dP SR P  ∂Z  dP P dP
= −T ∫   = −T ∫   − ∫0 ( Z − 1)
RT 0
 ∂T P P R 0
 ∂T P P P
 ∂Z 
Graphical integration requires plots of   / P and (Z-1)/P vs. P.
 ∂T  P

HR P  ∂Z  dP
= −T ∫   = −(360)(26.37 × 10 − 4 ) = −0.9493 H R = −2841.3 J / mol
RT 0
 ∂T  P P
SR P  ∂Z  dP P dP
= −T ∫   − ∫ ( Z − 1) = −0.9493 − (−0.02596) = −0.6897 S R = −5.734 J / mol ⋅ K
R 0
 ∂T P P 0 P
J
{ }
H = H 0ig + R × ICPH (300,360;1.7765,33.037 E − 3,0.0,0.0) + H R = 21598.5
mol
15.41 J
{ }
S = S 0ig + R × ICPS (300,360;1.7765,33.037 E − 3,0.0,0.0) − R ln
1
+ S R = 286.676
mol ⋅ K
 Residual properties by equation
of state
• If Z = f (P,T):
HR P  ∂Z  dP SR P  ∂Z  dP P dP
= −T ∫   = −T ∫   − ∫ ( Z − 1)
RT 0
 ∂T  P P R 0
 ∂T  P P 0 P

• The calculation of residual properties for gases

and vapors through use of the virial equations and
cubic equation of state.
 Use of the virial equation of state
BP
Z −1 =
GR P dP two-term virial equation RT G R BP
= ∫ ( Z − 1) =
RT 0 P RT RT
BP
Z −1 =
HR P  ∂Z  dP RT HR P ∂ BP  dP
= −T ∫   = −T ∫  (1 + )
RT 0
 ∂T  P P RT 0
 ∂T RT  P P

HR P   P  1 dB B   dP
= −T ∫    − 2  
RT 0
  R  T dT T   P P

H R P  B dB 
=  − 
RT R  T dT 
S R H R GR SR P dB
= − =−
RT RT RT RT R dT
Three-term virial equation Z − 1 = Bρ + Cρ 2 P = ZρRT

GR P dP GR 3
= ∫ ( Z − 1) = 2 Bρ + Cρ 2 − ln Z
RT 0 P RT 2

HR P  ∂Z  dP HR  B dB   C 1 dC  2 
= −T ∫   = T  − ρ +  − ρ 
RT 0
 ∂T  P P RT  T dT   T 2 dT  

S R H R GR
= − Application up to moderate pressure
R RT RT

Homework
Diagrama P – T para el agua.
 Two-phase systems
• Whenever a phase transition at constant
temperature and pressure occurs,
– The molar or specific volume, internal energy, enthalpy,
and entropy changes abruptly. The exception is the
molar or specific Gibbs energy, which for a pure
species does not change during a phase transition.
– For two phases α and β of a pure species coexisting at
equilibrium:
Gα = G β
where Gα and Gβ are the molar or specific Gibbs energies of the individual phases
Gα = G β dG α = dG β
dG = VdP − SdT
α sat α β sat β dP sat S α − S β ∆S αβ
V dP − S dT = V dP − S dT = α β
=
dT V −V ∆V αβ

dH = TdS + VdP ∆H αβ = T∆S αβ

The latent heat of phase transition
dP sat ∆H αβ
=
The Clapeyron equation dT T∆V αβ

RT
∆V αβ = V v =
P sat
Ideal gas, and Vl << Vg

lv d ln P sat
∆H = − R
d (1 / T )
The Clausius/Clapeyron equation
dP sat ∆H αβ
=
dT T∆V αβ
The Clapeyron equation: a vital connection between the properties of different phases.

P = f (T )

B For the entire temperature range from the triple point

ln P sat = A −
T to the critical point

B
ln P sat = A − The Antoine equation, for a specific temperature range
T +C

Aτ + Bτ 1.5 + Cτ 3 + Dτ 6 The Wagner equation, over a wide

ln Prsat =
1 −τ temperature range.
τ = 1 − Tr
 Two-phase liquid/vapor systems
• When a system consists of saturated-liquid and
saturated-vapor phases coexisting in equilibrium,
the total value of any extensive property of the
two-phase system is the sum of the total properties
of the phases: M = (1 − x v ) M l + x v M v
– M represents V, U, H, S, etc.
v l v v
– e.g., V = (1 − x )V + x V
 QUIZ 4

Superheated steam originally at P1 and T1 expands through a nozzle to an

exhaust pressure P2. Assuming the process is reversible and adiabatic, determine
the downstream state of the steam and ∆H for the following conditions:
(a) P1 = 1000 kPa, T1 = 250°C, and P2 = 200 kPa.
(b) P1 = 150 psia, T1 = 500°F, and P2 = 50 psia.
 Superheated steam originally at P1 and T1 expands through a nozzle to an
exhaust pressure P2. Assuming the process is reversible and adiabatic, determine
the downstream state of the steam and ∆H for the following conditions:
(a) P1 = 1000 kPa, T1 = 250°C, and P2 = 200 kPa.
(b) P1 = 150 psia, T1 = 500°F, and P2 = 50 psia.

Since the process is both reversible and adiabatic, the entropy change
of the steam is zero.
(a) From the steam stable and the use of interpolation,
At P1 = 1000 kPa, T1 = 250°C:
H1 = 2942.9 kJ/kg, S1 = 6.9252 kJ/kg.K
At P2 = 200 kPa,
S2 = S1= 6.9252 kJ/kg.K < Ssaturated vapor,
the final state is in the two-phase liquid-vapor region:
S 2 = (1 − x2v ) S 2l + x2v S 2v 6.9252 = 1.5301(1 − x2v ) + 7.1268 x2v

x2v = 0.9640
kJ
∆H = H 2 − H1 = −315.9 H 2 = (1 − 0.964)(504.7) + (0.964)(2706.3) = 2627.0
kg
(b) From the steam stable and the use of interpolation,
At P1 = 150 psia, T1 = 500°F:
H1 = 1274.3 Btu/lbm, S1 = 1.6602 Btu/lbm.R
At P2 = 50 psia,
S2 = S1= 1.6602 Btu/lbm.K > Ssaturated vapor,
the final state is in the superheat region:
T2 = 283.28o F H 2 = 1175.3 Btu / lbm

Btu
∆H = H 2 − H 1 = −99.0
lbm
 P = Pc Pr T = TcTr Pr  ∂Z
H R
P  ∂Z  dP HR  dPr
= −T ∫   = −Tr2 ∫  
RT 0
 ∂T P P RTc 0
 ∂Tr  Pr Pr
SR P  ∂Z  dP P dP SR Pr  ∂Z  dPr Pr dPr
= −T ∫   − ∫0 ( Z − 1) = −Tr ∫   − ∫ ( Z − 1)
R 0
 ∂T  P P P R 0
 ∂Tr P
 Pr r 0 Pr

Z = Z 0 + ωZ 1

H R  2 Pr  ∂Z 0  dPr   Pr  ∂Z 
1
dPr 
= − Tr ∫    − ω − Tr ∫ 
2
 
RTc  0
 ∂Tr  Pr Pr   0
 ∂Tr  Pr Pr 

SR  Pr  ∂Z 
0
dPr Pr dPr   Pr  ∂Z 
1
dPr Pr dPr 
= − Tr ∫   − ∫ ( Z − 1)
0
 − ω − Tr ∫   − ∫ ( Z − 1)
1

R  0 ∂T
 r  Pr r P 0 Pr   0 ∂T
 r  Pr r P 0 Pr 
  

HR  HR
=
( )
0

+ω
HR 
1
( )
 = HRB (TR, PR, OMEGA)
RTc  RTc RTc 

SR  SR
=
( )
0

+ω
SR ( )  = SRB(TR, PR, OMEGA)
1

Table E5 ~ E12
R  R R 
 T2
H 2 = H + ∫ C Pig dT +H 2R
ig
0 T2
T0
∆H = ∫ C Pig dT +H 2R − H1R
T1 T1
H1 = H + ∫ C dT +H
ig
0
ig
P 1
R
T0

∆H = C Pig (T2 − T1 ) + H 2R − H1R

H

T2 dT P
S 2 = S + ∫ C Pig
ig
0 − R ln 2 +S 2R
T0 T P0 T2 dT P
∆S = ∫ C Pig − R ln 2 +S 2R − S1R
dT
T1 P1 T1 T P1
S1 = S + ∫ C
ig
0
ig
− R ln +S1R
P
T0 T P0
P2
∆S = C Pig ln + S 2R − S1R
S P1
Estimate V, U, H, and S for 1-butene vapor at 200°C and 70 bar if H and S are
set equal to zero for saturated liquid at 0°C. Assume that only data available are:
Tc = 420 K Pc = 40.43 bar ω = 0.191 Tn = 266.9 K (nomal boiling pt.)
C Pig / R = 1.967 + 31.630 × 10 −3 T − 9.837 × 10 −6 T 2

Tr = 1.127 Pr = 1.731 Assuming four steps:

(a) Vaporization at T1 and P1 = Psat
Z = Z 0 + ωZ 1
(b) Transition to the ideal-gas state at (T1, P1)
= 0.485 + (0.191)(0.142) (c) Change to (T2, P2) in the ideal-gas state
= 0.512 (d) Transition to the actual final state at (T2, P2)
ZRT cm3
V= = 287.8
P mol

Fig 6.7
Fig 6.7
Step (a) B
ln 1.0133 = A −
B 266.9 For = 273.15K,
ln P sat = A −
T B Psat = 1.2771 bar
ln 40.43 = A −
420
∆H nlv 1.092(ln Pc − 1.013)
The latent heat at normal boiling point: = = 9.979
RTn 0.930 − Trn
0.38
∆H lv  1 − Tr 
The latent heat at 273.15 K: = 
∆H nlv  1 − Tr 
 n 
J ∆H αβ = T∆S αβ J
∆S lv = 79.84 ∆H lv = 21810
mol ⋅ K mol

Step (b) Tr = 0.650 Pr = 0.0316

=
( )
HR  HR
0

+ω
( )
HR 
1

 = HRB (TR, PR, OMEGA) = −0.0985 − H 1R = 344

J
RTc  RTc RTc  mol

=
( )
SR  SR
0

+ω
SR ( )  = SRB(TR, PR, OMEGA) = −0.1063
1
− S1R = 0.88
J
R  R R  mol ⋅ K
Step (c)
J
∆H ig = 8.314 × ICPH (273.15,473.15;1.967,31.630 E − 3,−9.837 E − 6,0.0) = 20564
mol
70
∆S ig = 8.314 × ICPS ( 273.15,473.15;1.967,31.630 E − 3,−9.837 E − 6,0.0) − 8.314 ln
1.2771
J
= 22.18
mol ⋅ K
Step (d) Tr = 1.127 Pr = 1.731
HR  HR
=
( )0

+ω
( )
HR 
1

 = −2.430 H 2R = −8485
J
RTc  RTc RTc  mol

SR  SR
=
( )
0

+ω
SR ( )  = −1.705
1
S 2R = −14.18
J
R  R R  mol ⋅ K

Total J
H = ∆H = 21810 − (−344) + 20564 − 8485 = 34233
mol
J
S = ∆S = 79.84 − (−0.88) + 22.18 − 14.18 = 88.72
mol ⋅ K
J
U = H − PV = 34233 − (70)(287.8) / 10 = 32218
mol
 Gas mixtures
• Simple linear mixing rules
ω ≡ ∑ yiωi TPc ≡ ∑ yiTci PPc ≡ ∑ yi Pci
i i i

Estimate V, HR, and SR for an equimolar mixture of carbon dioxide and propane
at 450K and 140 bar
TPc ≡ ∑ yiTci = (0.5)(304.2) + (0.5)(369.8) = 337 K T pr = 1.335
i Z 0 = 0.697
PPc ≡ ∑ yi Pci = (0.5)(73.83) + (0.5)(42.48) = 58.15bar Ppr = 2.41 Z 1 = 0.205
i

ω ≡ ∑ yiωi = (0.5)(0.224) + (0.5)(0.152) = 0.188

i
Z = Z 0 + ωZ 1 = 0.736

ZRT cm3 H R  (H R )0 (HR) 

1
S R  (S R )
0
(SR) 
1

V= = 196.7 = +ω  = −1.762 = +ω  = −1.029

P mol RT pc  RT pc RT pc  R  R R 
H R = −4937 J / mol S R = −8.56 J / mol ⋅ K