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Properties of Fluids
ChE. PSU.
1
Purpose of this Chapter
2
Property Relations for Homogeneous Phases
Fundamental Properties
H = Enthalpy H U PV …(2.11)
4
Based on one mole (or to a unit mass) of a
homogeneous fluid of constant composition,
they simplified to
dU TdS PdV
dH TdS VdP
dA PdV SdT
dG VdP SdT
5
Maxwell’s equaitons
T P
V S S V
T V
P S S P
P S
T V V T
V S
T P P T
6
Enthalpy and Entropy as Functions of T and P
Temperature derivatives:
H
CP
T P
S CP
T P T
Pressure derivatives:
S V
P T T P
H V
V T
P T T P
7
The most useful property relations for the enthalpy
and entropy of a homogeneous phase result when
these properties are expressed as functions of T
and P (how H and S vary with T and P).
V
dH C p dT V T dP
T P …(6.20)
dT V
dS C P dP …(6.21)
T T P
8
Property Relations for Homogeneous Phases
Internal Energy as Function of P
U V V
T P
P T T P P T
dU Tds PdV
9
Property Relations for Homogeneous Phases
The Ideal Gas State
V ig
R
PV RT
ig
T P P
dH ig C Pig dT (6.23)
dT dP
dS C P
ig ig
R (6.24)
T P
10
Property Relations for Homogeneous Phases
Alternative Forms for Liquids
S
V
P T
H
1 T V
P T
U
P T V
P T
11
Property Relations for Homogeneous Phases
Alternative Forms for Liquids
13
14
H C p T2 T1 1 T2 V P2 P1
T2
S C p ln V P2 P1
T1
For P 1 bar ,
75.305 75.314
Cp 75.310 Jmol 1 K 1
2
18.234 18.174
V 18.204 cm3 mol 1
2
458 568
10 6 513 10 6 K 1
2
15
H C p T2 T1 1 T2 V P2 P1
T2
S C p ln V P2 P1
T1
10
1,883 1,517 3,400 Jmol 1
Note that the effect of P of almost 1,000 bar on H and S of liquid water
is less than that of T of only 25C.
16
Property Relations for Homogeneous Phases
Internal Energy and Entropy as Function of T and V
S CV
T V T
U P
T P
V T T V
P
T V
17
The Partial derivatives dU and dS of homogeneous fluids
of constant composition to temperature and volume are
P
dU CV dT T P dV
T V
dT P
dS CV dV
T T V
M M M
R ig
20
Residual gibbs energy:
G G G
R ig
Residual volume:
RT
V V V
R ig
V
P
RT
V R
Z 1
P
21
Fundamental property relation for residual properties
G V HR
R R
d dP dT ( 6.42 )
RT RT RT 2
V R G R / RT
( 6.43 )
RT P T
HR G / RT
R
T ( 6.44 )
RT T P
22
GR V R
From Eq.(6.43), d dP (const T )
RT RT
GR GR PV
R
P dP GR
dP ( Z 1) (6.45) for ideal gas 0
RT RT P 0 0 RT 0 P RT P 0
HR P Z dP
Eq.(6.45 6.44); T (6.46)
RT 0
T P P
S R H R GR
From
RT RT RT
SR P Z dP P dP
So, T 0 ( Z 1) (const T ) (6.48)
R 0 T
P P P
23
Enthalpy and Entropy from Residual Properties
Applied to H and S ; H H ig H R S S ig S R
Integration of Eq .( 6.23 )and ( 6.24 );
T T
P
H H 0 C P dT
ig ig ig
S S 0 C P dT R ln
ig ig ig
T0 T 0 P0
T
Substituti on ; H H 0 C Pig dT H R
ig
( 6.50 )
T0
T
P
S S 0 C P dT R ln S R ( 6.51 )
ig ig
T 0 P0
24
H ig H 0ig C P H
( T T0
) H R
( 6.52 )
T P
S S 0 C P S ln R ln S R ( 6.53 )
ig ig
T0 P0
T2
P dT
C ig
CP C D
CP T1
H
A BTam ( 4Tam T1T2 )
2
H
T2 T1 R 3 T1T2
T2
dT
T C P T
ig
CP D
CP 1
S
A BTlm TamTlm C 2
S
ln( T2 / T1 ) R T1T2
The true worth of the Eq. for ideal gases is now evident.
They are important because they provide a convenient base
for the calculation of real-gas properties.
25
Example 6.3
26
27
Solution 6.3
P Z dP P dP
0 T P P 0 (Z 1) P
Plot (Z/T)P/P and (Z-1)/P vs. P
From the compressibility-factor data at 360 K (Z-1)/P
The slope of a plot of Z vs. T (Z/T)P/P
Data for the required plots are shown in Table 6.2.
28
29
Z dP dP
26.37 10 K 0 ( Z 1 ) 0.2596
P P
0
4 1
T P P P
H R
30
C Pig H
A BTam 1.7765 33.037 10 3 Tam
R
C Pig S
A BTlm 1.7765 33.037 10 3 Tlm
R
T0 T1 300 360
Tam 330 K
2 2
T1 T0 360 300
Tlm 329.09 K
ln( T1 / T0 ) ln( 360 / 300 )
C Pig H
12.679( 8.314 ) 105.41 Jmol 1 K 1
C Pig S
12.649( 8.314 ) 105.16 Jmol 1 K 1
Substitute int o Eq .( 6.50 ) and ( 6.51 )
H 18 ,115 105.41( 360 300 ) 2 ,841.2 21,598.5 Jmol 1
360
S 295.576 105.16 ln( ) 8.314 ln15.41 5.734 286.676 Jmol 1 K 1
300
31
Residual Properties by Equations of State
Residual Properties from the Virial Equation of State
G R BP
So, (6.54)
RT RT
HR
T
G R / RT P B dB
By Eq.(6.44), (6.55)
RT T P R T dT
SR P dB
Substitution int o Eq.(6.47), (6.56)
R R dT
32
In application is a more convenient variable than V,
PV = ZRT is written in the alternative form.
dP d dZ
P ZRT ( 6.57 ), dP RT ( Zd dZ )
P Z
GR d
Substitue int o Eq .( 6.49 ); ( Z 1 ) Z 1 ln Z ( 6.58 )
RT 0
HR Z 1 P ( G R / RT )
From Eq .( 6.40 ) and ( 6.42 ),
RT 2
P T T
HR
Z d
Differenti tion of Eq .( 6.57 ) and ( 6.58 ); T Z 1 ( 6.59 )
RT 0 T
SR
Z d d
From Eq .( 6.47 ), ln Z T ( Z 1 ) ( 6.60 )
R 0 T 0
33
The three-term virial equation.
GR 3
2 B C 2 ln Z (6.61)
RT 2
HR B dB C 1 dC 2
T (6.62)
RT T dT T 2 dT
SR B dB 1 C dC 2
ln Z T (6.63)
R T dT 2 T dT
Z d dq d ( b )
0 0
T dT ( 1 b )( 1 b )
d
Z d dq
To simplify ; (Z - 1) ln( 1 b ) qI , I
0 0 T
dT 35
The generic equation of state presents two cases.
1 1 b
Case I : I ln ( 6.65a )
1 b
When ρ is eliminated in favor of Z.
bP P
Z whence b
RT RT Z
1 Z
I ln ( 6.65b )
Z
b
Case II : I
1 b Z
36
R
G
Z 1 ln(1 b) Z qI (6.66a )
RT
GR
Z 1 ln(Z ) Z qI (6.66b)
RT
H R
d ln (Tr )
Z 1 1 qI (6.67)
RT d ln Tr
SR
d ln (Tr )
ln(Z ) qI (6.68)
R d ln Tr
37
Ex. 6.4
Find values for the HR and SR for n-butane gas at 500 K
50 bar as given by the Redlich/Kwong Eequation.
Solution
Tr = 500/425.1 = 1.176, Pr = 50/37.96 = 1.317
From Table 3.1:
Pr 1.317
Eq.(3.53); 0.08664 0.09703
Tr 1.176
Tr 0.42748
Eq.(3.54); q 3.8689
Tr 0.08664 1.176 3/ 2
38
39
Z
Eq.(3.52) : Z 1 q
Z Z
Z 0.09703
1 0.09703 3.8689 0.09703
Z ( Z 0.09703)
Solution of this Eq. yields Z 0.6850. Then:
Z
I ln 0.13247
Z
1 1
With ln (Tr ) ln Tr , d ln (Tr ) / d ln Tr . Then :
2 2
HR
Eq.(6.67) : 0.6850 1 (0.5 1)(3.8689)(0.13247 ) 1.0838
RT
SR
Eq.(6.68) : ln(0.6850 0.09703) 0.5(3.8689)0.13247 0.78735
R
Thus , H R 8.314 500 1.0838 4,505 Jmol 1
41
TWO-PHASE SYSTEMS
G G , dG dG V dP sat S dT V dP sat S dT
dP sat S S S
Re arrangement ,
dT V V
V
Integration of Eq .( 6.8 ); H TS ( The latent heat of phase transition )
dP sat H
Thus , S H / T
( 6.71 ) : The Clapeyron equation
dT TV
dP sat H l
Phase transition from liquid to vapor ; ( 6.72 )
dT TV l
RT d ln P sat H l
But V sat Z
l l
( 6.73 )
P dT RT Z
2 l
The Clapeyron eq.
d ln P sat H l for pure-species
or ( 6.74 ) vaporization
d ( 1 / T ) RZ l
42
Temperature Dependence of the Vapor
Pressure of Liquids
B
ln P sat
A
T
B
The Antoine eq . : ln P A sat
( 6.76 )
T C
Antoine cons tan ts are given in Table B .2 , App .B
A B 1.5 C 3 D 6
A function of Tr ; ln Pr ( Tr )
sat
( 6.77 )
1
where 1 Tr
43
Corresponding-States Correlations
for Vapor Pressure
Lee / Kesler correlatio n :
ln Prsat (Tr ) ln Pr0 (Tr ) ln Pr1 (Tr ) (6.78)
6.09648
where ln P (Tr ) 5.92714
r
0
1.28862 ln Tr 0.169347Tr6 (6.79)
Tr
15.6875
ln Pr1 (Tr ) 15.2518 13.4721ln Tr 0.43577Tr6 (6.80)
Tr
ln Prnsat ln Pr0 (Trn )
1
(6.81)
ln P (Trn )
r
where
Trn : The reduced normal boiling point
Prnsat : The reduced vapor pressure corresponding to 1 atm
44
Ex. 6.6
Determine the vapor pressure for liquid n-hexane at 0, 30,
60 and 90C: (a) With constants from App. B.2.
(b) From the Lee/Kesler correlation for Prsat
Solution
(a) 2696.04
ln P sat 13.8193
t 224.317
nV n lV l n V n nl n v (moles)
V x lV l x V x : mass fraction
V (1 x v )V l x V xl 1 xv
49
GENERALIZED PROPERTY
CORRELATION FOR GASES
Tr (6.83)
RTc 0
Tr Pr Pr
Pr P
SR Z dPr r dPr
R
Tr 0 Tr ( Z 1)
Pr Pr 0 Pr
(6.84)
50
Z Z 0 Z 1
Z Z Z
0 1
Tr Pr Tr Pr Tr Pr
H R 2 r Z 0 dPr Pr Z 1 dP
P
Eq.(6.83) : Tr Tr2 r
RTc 0
Tr P Pr 0 Tr Pr Pr
r
HR
HR
HR
0
1
(6.85)
RTc RTc RTc
SR r Pr dP
P
Z 1 dP Z 1
Eq.(6.84) : Tr Z 0 1 r
Tr Z 1 r
R 0
Tr Pr Pr
0
Tr Pr Pr
SR
SR
0
SR 1
(6.86)
R R R Table E.5 - E.12
51
52
Analytical correlation of the residual properties at low pressure
54
HR and SR with ideal-gas heat capacities
For a change from state 1 to 2:
T2 T1
H 2 H C dT H
ig
0
ig
P
R
2 H1 H C Pig dT H1R
ig
0
0 0
T2 P
S C Pig ln R ln 2 S 2R S1R (6.94)
S T1 P1
55
56
A three-step calculational path
Step 11ig: A hypothetical process that transforms a real
gas into an ideal gas at T1 and P1.
H1ig H1 H1R S1ig S1 S1R
61
The latent heat at 273.15 K Tr 273.15 / 420 0.650
0.38
H lv
1 Tr
From ...( 4.13 )
H nlv 1 Tr
n
0.38
0.350
H ( 22 ,137 )
lv
21,810 Jmol 1
0.368
H lv
21,810
S
lv
79.84 Jmol K1 1
T 273.15
62
Step (b): Transformation of saturated vapor into an ideal
gas at (T1, P1).
0.422
B 0.083 1.6
0
(3.65)
1 Tr
HR d B 0
d B
Pr B 0 Tr B1 Tr (6.87)
RTc dTr dTr 0.172
B 0.139 4.2
1
(3.66)
Tr
dB 0 0.675
SR
d B0 d B1 2.6 (6.89)
Pr (6.88) dTr Tr
R dTr dTr
dB1 0.722
5 .2 (6.90)
dTr Tr
T2
dT P T2 P
Eq .( 6.96 ) : S S 2 S1 C Pig
ig ig ig
R ln 2 C Pig ln R ln 2
T1 T P1 S
T1 P1
64
Step (d): Transformation from the ideal gas to real gas
state at T2 and P2.
Tr = 1.127 Pr = 1.731
At the higher P; Eqs.(6.85) and (6.86) with interpolated
values from Table E.7, E.8, E.11 and E.12.
H 2R
2.294 (0.191)(0.713) 2.430
RTC
S 2R
1.566 (0.191)(0.726) 1.705
R
H 2R (2.430)(8.314)( 420.0) 8,485 Jmol 1
T P
TPr (6.100) PPr (6.101)
Tpc Ppc
66
Ex. 6.10
Estimate V, HR, and SR for an equimolar mixture of
carbon dioxide(1) and propane(2) at 450 K and 140 bar by
the Lee/Kesler correlations.
Solution
From Table B.1,
y11 y22 (0.5)(0.224) (0.5)(0.152) 0.188
Tpc y1Tc1 y2Tc 2 (0.5)(304.2) (0.5)(369.8) 337.0 K
Ppc y1 Pc1 y2 Pc 2 (0.5)(73.83) (0.5)(42.48) 58.15 bar
450 140
Whence, Tpr 1.335 Ppr 2.41
337.0 58.15
67
68
From Table E.3 and E.4;
Z Z 0 Z 1 0.697 (0.188)(0.205) 0.736
ZRT (0.736)(83.14)(450)
V 196.7 cm3mol 1
P 140
From Table E.7 and E.8; with Eq.(6.85) :
0 1
H
R H R
1.730 0.169
RT RT
pc pc
HR
1.730 (0.188)(0.169) 1.762
RTpc
H R (8.314)(337) 1.762 4,937 Jmol 1
From Table E.11 and E.12; with Eq.(6.86) :
SR
0.967 (0.188)(0.330) 1.029
R
S R (8.314)(1.029) 8.56 Jmol 1 K 1 69
70