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Thermodynamics-I
Lecture 4
Prof.Dr.Mahmood Saleem
Institute of Chemical Engineering &
Technology
University of the Punjab, Lahore
Contents
Introduction
Property relations for Homogeneous Phase
Residual Properties
Residual Properties by Equation of State
Property Relations for Two Phase Systems
Thermodynamic Property Diagrams and Tables
Generalized property Correlations for Gases
Extension of Generalized property Correlations for
Gases to Mixtures
Exercises
Introduction
Processing of materials (pure and mixtures) is
key affair in chemical processes
Estimation of many properties (and change)
other than volumetric properties (H,U,s,G etc.)
are required.
How to know complete property set when
volumetric properties are not available
What tools can one use to handle such issues?
Property Relations for Homogeneous Phases
Fundamental Properties
H = Enthalpy H U PV (2.11)
T V
G G P S P
dG dP dT S
P T T P P
S
T V T
V S
V
. V
S
T P P T T P P T
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
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
Property Relations for Homogeneous
Phases
Internal Energy as Function of P (U(P))
The pressure T P
dependence of the V S S V
internal energy is
T V
shown as
P S S P
P S
U V V
T P T V V T
P T T P P T
V S
dU Tds PdV
T P P T
Property Relations for Homogeneous
Phases
The Ideal Gas State
For ideal gas,
V
expressions of dH dH C p dT V T dP
T
and dS (eq.6.20-6.21)
P
dT V
as functions of T and dS C P dP
T T P
P can be simplified as
follows using ideal
gas law:
V ig R
PV ig
RT
T P
P
dH ig C Pig dT (6.23)
dT dP
dS ig C Pig R (6.24)
T P
V V
dV dT dP
Property Relations for Homogeneous T P P T
1 V
Phases
V T
P
Alternative Forms for Liquids V
1
T P
Relations of liquids V
P T
can be expressed in V S S dV V
dT dP
terms of and as T V V V
dH C p dT V T dP
follows: P S S P T P
S
V P
dS CP dP dT SV
P T T T
T V V T P
H
1 T V V S
P T
T P P T
U U V V
P T V
T
P
P T P T T P P T
dU Tds PdV
Property Relations for Homogeneous Phases
Alternative Forms for Liquids
Constant T
H C p T2 T1 1 T2 V P2 P1 Integrated forms of
T2 equations for change in
S C p ln V P2 P1 Enthalpy and Entropy
T1
10
1,883 1,517 3,400 Jmol 1 On substitution of values
S 75.310 ln
323.15 513 10 6 18.204 1,000 1
298.15 10
6.06 0.93 5.13 Jmol 1 K 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.
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
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
V
dV dT
V
dP
dU CV dT T P dV T P T
P
1 V
dT V T P
dS CV dV 1 V
T
V
P T
dV
dT dP
V
Property Relations for Homogeneous Phases
The Gibbs Energy
An alternative form of a fundamental property
relation as defined in dimensionless terms:
G V H
d dP 2
dT
RT RT RT
V G RT
RT P T
H G RT
T
RT T P
M M M
R ig
G G G
R ig
Residual volume:
RT PV=ZRT
V V V
R ig
V
P
RT
V R
Z 1
P
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
GR V R
From Eq.(6.43), d dP (const T )
RT RT
GR GR P VR 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 ( Z 1) (const T ) (6.48)
R 0 T P P
P
0
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
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.
Practice 2
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.
Z
dP dP
26.37 10 K 0 ( Z 1 ) 0.2596
P P
0
4 1
T
P P P
H R
GR P dP
( Z 1)
RT 0 P
G R BP
So, (6.54)
RT RT
By Eq.(6.44),
HR
T
G R / RT P B dB
(6.55)
RT T P
R T dT
SR P dB
Substitution int o Eq.(6.47), (6.56)
R R dT
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
H R Z 1 P ( G / RT )
R
HR
Z d
Differentition 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
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
1 1 b
Case I : I ln (6.65a)
1 b
When 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
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
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 0.086641.176 3/ 2
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
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
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
where
Trn : The reduced normal boiling point
Prnsat : The reduced vapor pressure corresponding to 1 atm
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 P rsat
Solution
(a) 2696.04
ln P sat 13.8193
t 224.317
(b) Eq.(6.78); Tr
341.9
0.6736, Prsat
1.01325
0.03350
From Table B.1, 507.6n
30.25
n
nV n lV l n V n nl nv (moles)
V x lV l x V x : mass fraction
V (1 x v )V l x V xl 1 xv
HR dPr dPr
P P
r
Z 0
r
Z 1
Eq.(6.83) : Tr
2
Tr
2
RTc 0
Tr Pr 0
Tr Pr
Pr Pr
HR
HR
HR
0
1
(6.85)
RTc RTc RTc
SR r dPr dP
P Pr
Z 1 Z 1
Eq.(6.84) : Tr Z 1
0
Tr Z 1
r
R 0
Tr Pr
Pr
0 Tr Pr
Pr
SR
SR
SR
0
1
(6.86)
R R R Table E.5 - E.12
Analytical correlation of the residual properties at low pressure
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
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
0.368
H lv
21,810
S
lv
79.84 Jmol K 1 1
T 273.15
Step (b): Transformation of saturated vapor into an ideal
gas at (T1, P1).
0.422
B 0.083 1.6
0
(3.65)
H R 0
dB d B 1 Tr
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
dT T2
P2 T2 P2
Eq .( 6.96 ) : S S 2 S1 C P
ig ig ig
R ln C Pig
ig
ln R ln
T T 1 P1 S
T1 P1
T P
TPr (6.100) PPr (6.101)
Tpc Ppc
Solution
From Table B.1,
y11 y22 (0.5)(0.224) (0.5)(0.152) 0.188
T pc 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, T pr 1.335 Ppr 2.41
337.0 58.15
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