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Thermodynamic Propeties of

Fluids
Chemical Engineering
Thermodynamics II

In this lecture we will talk about


Finding property relations for homogenous
phases in terms of easily measurable variables
Define residual properties and derive residual
relationships
Use of thermodynamic diagrams and tables

Property relations for homogenous


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.

Property relations for homogenous


phases
d (nU ) Td (nS ) Pd (nV )

The primary thermodynamic properties:

P, V , T , U , and S

H U PV

Enthalpy:
For n number of
moles, sub d(nU)

d (nH ) d (nU ) Pd (nV ) (nV )dP


d (nH ) Td (nS ) (nV )dP

Helmholtz energy:

A U TS

d (nA) Pd (nV ) (nS )dT

Gibbs energy:

G H TS

d (nG ) (nV )dP (nS )dT

For one mol of homogeneous fluid of constant composition:


dU TdS PdV

dA PdV SdT

dH TdS VdP

dG VdP SdT

Property relations for homogenous


phases
Remember that for Exact differential equations
= +

=
=

dU TdS PdV

T
P

S
S V

dH TdS VdP

T V

P S S P

dA PdV SdT

P
S

V
T

dG VdP SdT

V
S


T P
P T

Maxwells equations

Enthalpy and Entropy as function of T


and P
H
H
dH
dT
dP
T P
P T
H

CP

dH TdS VdP
H
S

T V
P T
P T
Maxwells
V
S


T P
P T equations
H
V

V T

dH CP dT V T
dP
T P

Enthalpy and Entropy as function of T


and P
S
S
dS
dT dP
T P
P T
dH TdS VdP
H
S

T P
T P

CP
S

T P T

Maxwells equation
V
S


T P
P T

dT V
dS CP

dP
T T P

Example 1
Determine the enthalpy and entropy changes of liquid water for a
change of state from 1 bar and 25C to 1000 bar and 50C. The data
for water are given. (see data on example 6.1, p204)

V
dH CP dT V T
dP

volume expansivity:

H CP (T2 T1 ) 1 T2 V ( P2 P1 )

dH CP dT 1 T VdP

1 (51310
H 75.310(323.15 298.15)
dS CP

V
T P

dT V

dP
T T P

S CP ln

)(323.15) (18.204)(1000 1)
3400 J / mol
10
T2
V ( P2 P1 )
T1

323.15 513 106 (18.204)(1000 1)


S 75.310 ln

5.13J / mol
298.15
10

Example 2
Estimate the change in enthalpy and entropy when liquid ammonia at 270K is
compressed from its saturation pressure of 381 kPa to 1,200 kPa. For saturated
liquid ammonia at 270K, Vl=1.551x10-3 m3kg-1 and =2.095x10-3 K-1
dH C P dT 1 T VdP

Constant T:

dH 1 T VdP

dT
VdP
T
dS VdP

dS C P

H 1 T V ( P2 P1 )
H [1 (2.095 10 3 K 1 )(270 K )](1.55 10 1 m 3 kg 1 )(1200kPa 381kPa)

H 551.7

J
kg

Ans.

S V ( P2 P1 )
S (2.095 10 3 K 1 )(1.55 10 1 m 3 kg 1 )(1200kPa 381kPa)

J
S 2.661
kg K

Ans.

Internal energy and Entropy as


functions of T and V
U
U
dU
dT
dV
T V
V T
U

CV
T V

dU TdS PdV

dU TdS PdV

U
S

T
P
V T
V T

U
S

T V
T V

dU CV dT T
P dV
V T

Maxwells
equations:

S
S
dS
dT

dV
T V
V T

S
P

dU CV dT T
P dV
T V

S
P

CV
S

V T

dT P
dS CV

dV
T T V
Temperature and volume may serve as more
convenieny variables than do temperature
and pressure.

Gibbs energy as a Generating Function


dG VdP SdT

Thermodynamic property of great potential utility

G
G 1
d
dG
dT

2
RT
RT RT
G H TS

G
d
RT

Total differential equation as a function of P, T

dG VdP SdT

H
V

dP

dT

2
RT
RT

V
(G / RT )

RT
P
T
H
(G / RT )
T

RT

G
G

( P, T )
RT RT

G
d
RT

S
H
G

R RT RT
U
H
PV

RT RT RT

(G / RT )
(G / RT )

dP

dT
P
T

T

G(P,T) 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
d
RT

VR
HR

dP
dT
2
RT
RT

Residual properties
GR
d
RT

VR
HR

dP
dT
2
RT
RT

GR
d
RT

VR

dP
RT

V R V V ig

R
PV
GR

dP
0
RT
RT
P
GR
dP
( Z 1)
0
RT
P

H
(G / RT )
T

RT

P
P Z dP
HR
T

0
RT
T P P

ZRT RT

P
P

S R H R GR

R
RT RT
P Z dP
P
SR
dP
T
( Z 1)

0
0
R
P
T P P

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.

Residual properties by equation of


state
two-term virial equation: Z 1 BP
RT

P
GR
dP
( Z 1)
0
RT
P
P Z dP
HR
T

0
RT
T P P

G R BP

RT RT
P
HR
BP dP
T
(1
)
0
RT
RT P P
T

P P 1 dB
HR
B dP
T
2
0
RT
R T dT T P P

H R P B dB

RT R T dT

SR
P dB

RT
R dT

Residual properties by equation of


state
three-term virial equation:
P
GR
dP
( Z 1)
0
RT
P
P Z dP
HR
T

0
RT
T P P

Z 1 B C 2

P ZRT

GR
3
2 B C 2 ln Z
RT
2
Z d
HR
T
Z 1

0
RT
T

B dB
HR
C 1 dC 2
T


RT
T 2 dT
T dT
S R H R GR

R
RT RT

B dB
HR
1 C dC 2
ln Z T



RT
2 T dT
T dT

Residual properties of the cubic


equation of state
P

RT
a(T )

V b (V b)(V b)

P
RT
(T )

RT RT (V b) (V b)(V b)

1
b
Z
q
1 b
(1 b)(1 b)

( Z 1)

dq
Z d

dT
T

d ( b)
(1 b)(1 b)

bP
RT

ln(1 b) qI

Case I:

const T

Case II: ;

Z
1
ln
Z


b

1 b Z

Residual properties of the cubic


equation of state
Van der Waals equation of state

( Z 1)

Case II:


b

1 b Z

ln(1 b) qI

dq
Z d

dT
T

Virial equation of state;

G
Z 1 ln( Z ) qI
RT

d ln (Tr )
HR
Z 1
1 qI
RT
d ln Tr

d ln (Tr )
SR
ln Z
1 qI
R
d ln Tr

Example 3
Find values for the residual enthalpy HR and the residual entropy SR
for n-butane gas at 500 K and 50 bar as given by Redlich/Kwong
equation.
0
Z
Z 1 q
1
( Z )( Z )
500
50
1.317
Tr
1.176 Pr
37.96
425.1

Z 1 0.09703 (3.8689)(0.09703)

Z 0.0973
( Z )( Z 0.0973)

Z 0.685

Case II:

Z
1
ln
Z

Pr
0.09703
Tr

0.13247

(Tr )
3.8689
Tr

Example 3
Find values for the residual enthalpy HR and the residual entropy SR
for n-butane gas at 500 K and 50 bar as given by Redlich/Kwong
equation.
Z 0.685

Case II:
(T ) Tr1 / 2

Z
1
0.13247
ln
Z
1
ln (T ) ln Tr d ln (T ) / d ln Tr 1 / 2
2
I

d ln (Tr )
HR
Z 1
1 qI
RT
d ln Tr

d ln (Tr )
SR
ln Z
1 qI
R
d ln Tr

J
H 4505
mol
R

S R 6.546

J
mol K

Ans.

Ans.

Two-phase systems
Whenever a phase transition at constant
temperature and pressure occurs,
The molar or specific V, U, H, and S 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 and of a pure species coexisting at
equilibrium:

G G
where G and G are the molar or specific Gibbs energies of the
individual phases

Two-phase systems
dG dG

dG VdP SdT

V dP sat S dT V dP sat S dT
dP sat S S
S

dT
V V
V

At constant T, P

H TS

dH TdS VdP

The latent heat of phase transition

dP sat H

dT
TV
RT
P sat
Ideal gas, and Vl << Vg
V V v

The Clapeyron equation

sat
d
ln
P
H lv R
d (1 / T )

The Clausius/Clapeyron
equation

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 )M x M
v

Where M represents V, U, H, S, etc.


e.g for volume:

V (1 x v )V v x vV v

Thermodynamic diagrams and tables


A thermodynamic diagram represents the temperature,
pressure, volume, enthalpy, and entropy of a substance on a
single plot. Common diagrams are:
TS diagram
PH diagram (ln P vs. H)
HS diagram (Mollier diagram)

In many instances, thermodynamic properties are reported in


tables. The steam tables are the most thorough compilation of
properties for a single material.

Example diagrams

PH Diagram

TS Diagram

Example diagrams
Liquid water below its boiling point is
superheated to steam:

Line 1 2 : Heated at constant P to


saturated temperature
Line 2 3 : Vaporized at constant T, P

Line 3 4 : Superheated at constant P

PH Diagram

Exampl 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 = 250C, and P2 = 200 kPa.
(b) P1 = 150 psia, T1 = 500F, 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 = 250C:
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

Exampl 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 = 250C, and P2 = 200 kPa.

S2 (1 x2v )S2l x2v S2v

6.9252 1.5301(1 x2v ) 7.1268x2v


x2v 0.9640

H 2 (1 x2v ) H 2l x2v H 2v
H 2 (1 0.964)(504.7) (0.964)(2706.3) 2627.0
H H 2 H1 315.9

kJ
kg

Ans.

Exampl 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:
(b) P1 = 150 psia, T1 = 500F, and P2 = 50 psia.

From the steam stable and the use of interpolation,


At P1 = 150 psia, T1 = 500F:
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 283.28 F

H 2 1175.3 Btu / lbm

H H 2 H1 99.0

Btu
lbm

Ans.

Example 5
A 1.5 m3 tank contains 500 kg of liquid water in equilibrium with pure water
vapor, which fills the remainder of the tank. The temperature and pressure
are 100C, and 101.33 kPa. From a water line at a constant temperature of
70C and a constant pressure somewhat above 101.33 kPa, 750 kg of liquid is
bled into the tank. If the temperature and pressure in the tank are not to
change as a result of the process, how much energy as heat must be
transferred to the tank?
Energy balance: d (mU ) cv Q H m
dt

d (mU ) cv
dm
Q H cv
dt
dt

Q (mU )cv H mcv


H U PV

Q (mH )cv ( PmV )cv H mcv


Q (m2 H 2 )cv (m1H1 )cv H mcv

Example 5
A 1.5 m3 tank contains 500 kg of liquid water in equilibrium with pure water
vapor, which fills the remainder of the tank. The temperature and pressure
are 100C, and 101.33 kPa. From a water line at a constant temperature of
70C and a constant pressure somewhat above 101.33 kPa, 750 kg of liquid is
bled into the tank. If the temperature and pressure in the tank are not to
change as a result of the process, how much energy as heat must be
transferred to the tank?

At the end of the process, the tank still contains saturated liquid and
saturated vapor in equilibrium at 100C and 101.33 kPa.
H 293.0

kJ
kg

saturated liquid @ 70 C

H cvl 419.1

kJ
kg

H cvv 2676.0

kJ
kg

saturated liquid @100 C


saturated vapor @100 C

From the steam table, the specific volumes of saturated liquid


and saturated vapor at 100C are 0.001044 and 1.673 m3/kg ,
respectively.

Example 5
A 1.5 m3 tank contains 500 kg of liquid water in equilibrium with pure water
vapor, which fills the remainder of the tank. The temperature and pressure
are 100C, and 101.33 kPa. From a water line at a constant temperature of
70C and a constant pressure somewhat above 101.33 kPa, 750 kg of liquid is
bled into the tank. If the temperature and pressure in the tank are not to
change as a result of the process, how much energy as heat must be
transferred to the tank?
m1v

1.5 (500)(0.001044)
0.7772kg
1.673

m2 500 0.7772 750 m2l m2v

1.5 1.673m 0.001044m


v
2

l
2

m2l 1250.65kg

m2v 0.116kg

(m2 H 2 )cv m2l H 2l m2v H 2v 524458kJ


Q (m2 H 2 )cv (m1H1 )cv H mcv 524458 211616 (750)(293.0) 93092kJ

Example 5
A 1.5 m3 tank contains 500 kg of liquid water in equilibrium with pure water
vapor, which fills the remainder of the tank. The temperature and pressure
are 100C, and 101.33 kPa. From a water line at a constant temperature of
70C and a constant pressure somewhat above 101.33 kPa, 750 kg of liquid is
bled into the tank. If the temperature and pressure in the tank are not to
change as a result of the process, how much energy as heat must be
transferred to the tank?
(m1H1 ) cv m1l H1l m1v H1v 500(419.1)

1.5 (500)(0.001044)
(2676.0) 211616kJ
1.673

1.5 (500)(0.001044)
750 m2l m2v
1.673
1.5 1.673m2v 0.001044m2l

m2 500

(m2 H 2 )cv m2l H 2l m2v H 2v 524458kJ


Q (m2 H 2 )cv (m1H1 )cv H mcv 524458 211616 (750)(293.0) 93092kJ Ans.

Generalized property correlation for


gasses
P Z dP
HR
T

0
RT

P P

Pr Z
HR
2
Tr
0
RTc
Tr

P Pc Pr

T TcTr

dPr

Pr Pr

P Z dP
P
SR
dP
T
( Z 1)

0
0
R
P
T P P

Pr Z
SR
Tr
0
R
Tr

Pr
dPr
dP

( Z 1) r
0
Pr
Pr Pr

Z Z 0 Z 1
1

Pr Z
H R 2 Pr Z 0 dPr
dPr
2

Tr

Tr
0
0
RTc

T
P

T
P

r Pr r
r Pr r

0
1

Pr Z
Pr
Pr Z
Pr
SR
dPr
dPr
dPr
dPr
0
1

Tr

Tr
( Z 1)
( Z 1)
0
0
0
0
R

T
P
P

T
P
P

r
r
r Pr r
r Pr r

Generalized property correlation for


gasses
1

Pr Z
H R 2 Pr Z 0 dPr
dPr
2

Tr

Tr
0
0
RTc

Tr Pr Pr
Tr Pr Pr

( H R )0
RTc

( H R )1
RTc

H R ( H R )0
( H R )1

RTc
RTc
RTc
0
1

Pr Z
Pr
Pr Z
Pr
SR
dPr
dPr
dPr
dPr
0
1

Tr

Tr
( Z 1)
( Z 1)
0
0
0
0
R
Pr
Pr

Tr Pr Pr
Tr Pr Pr

S R (S R )0
( S R )1

RTc
RTc
RTc

Lee/Kesler correlation

Generalized property correlation for


gasses
Generalized second-virial coefficient mixing rule
BPC
dB dB 0
dB1
0
1

B
B B

RTC
dTr dTr
dTr
H R P B dB

RT R T dT

1
0 dB 0
1

HR
dB

Pr B
B Tr
RTc
dTr
dTr

SR
P dB

RT
R dT

dB 0
SR
dB1

Pr

R
dTr
dTr

B 0 0.083

0.422
Tr1.6

B1 0.139

0.172
Tr4.2

Generalized property correlation for


gasses
1
0 dB 0
1

HR
dB


Pr B
B Tr
RTc
dTr
dTr

H H H
ig

dB 0
SR
dB1

Pr

R
dTr
dTr

T2

H C Pig dt H 2R H1R
T1

H C Pig
S S S
ig

(T2 T1 ) H 2R H1R

S C Pig

dT
P
R ln 2 S 2R S1R
T
P1

S C Pig

ln

T2

T1

T2
P
R ln 2 S 2R S1R
T1
P1

Example
Estimate U, H, and S for 1-butene vapor at 200C and 70 bar if H and S are set
equal to zero for saturated liquid at 0C. Assume the only data available are:
0.191
Tc 420.0 K Tn 266.9 K Pc 40.43bar

C Pig
1.967 31.630 10 3 T 9.837 10 6 T 2
R
(a) Vaporization at T1 and P1=Psat
(b) Transition to ideal gas state at
T1 and P1
(c) Change to T2 and P2 in the ideal
gas state
(d) Transition to the actual final
state at T2 and P2

Example 6
Estimate U, H, and S for 1-butene vapor at 200C and 70 bar if H and S are set
equal to zero for saturated liquid at 0C. Assume the only data available are:
0.191
Tc 420.0 K Tn 266.9 K Pc 40.43bar

C Pig
1.967 31.630 10 3 T 9.837 10 6 T 2
R
(a) Vaporization at T1 and P1=Psat

B
T
From normal boiling point and critical point P and T
B
B
ln 1.0133 A
ln 40.43 A
266.9
420
at 0C,
ln P sat A

ln P sat 10.1260

2699.11
273.15

P sat 1.2771bar

A 10.1260
B 2699.11

Example 6
Estimate U, H, and S for 1-butene vapor at 200C and 70 bar if H and S are set
equal to zero for saturated liquid at 0C. Assume the only data available are:
0.191
Tc 420.0 K Tn 266.9 K Pc 40.43bar

C Pig
1.967 31.630 10 3 T 9.837 10 6 T 2
R

H lv
H nlv

1 Tr

1 Tr
n

0.38

H n 1.092(ln Pc 1.013)

RTn
0.930 Trn

H n 1.092(ln Pc 1.013)

RTn
0.930 Trn

H n

1.092(ln 40.43 1.013)


(8.314)(266.9)
0.930 0.636

22,137 J / mol
1 Tr

lv
H n 1 Trn
H lv

0.38

H lv TS lv

H lv 21,810 J / mol
S lv 21,810 J mol 1 / 273.15 K

S lv 78.83 J / mol K

Example 6
Estimate U, H, and S for 1-butene vapor at 200C and 70 bar if H and S are set
equal to zero for saturated liquid at 0C. Assume the only data available are:
0.191
Tc 420.0 K Tn 266.9 K Pc 40.43bar

C Pig
1.967 31.630 10 3 T 9.837 10 6 T 2
R
(d) Transition to the actual final state at T2 and P2
Use Lee/Kesler correlations

H R ( H R )0
( H R )1

RTc
RTc
RTc
S R (S R )0
( S R )1

RTc
RTc
RTc

H 2R (2.294) (0.191)(0.713)(8.314)(266.9)

8,485 J / mol
S 2R (1.566) (0.191)(0.726)(8.314)(266.9)

14.18 J / mol K

Example 6
Estimate U, H, and S for 1-butene vapor at 200C and 70 bar if H and S are set
equal to zero for saturated liquid at 0C. Assume the only data available are:
0.191
Tc 420.0 K Tn 266.9 K Pc 40.43bar

C Pig
1.967 31.630 10 3 T 9.837 10 6 T 2
R
Finally,

H 21,810 (344) 20,564 8,485 34,233J / mol


S 78.84 (0.88) 22.18 14.18 88.72 J / mol K

U H PV
34,233

(70)(287.8)
32,218 J / mol
3
1
10cm bar J