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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?
d nU T .d nS P.d nV
(6.1)
Definitions
H = Enthalpy
H U PV
(2.11)
A = Helmholtz energy
A U TS
(6.2)
G = Gibbs energy
G H TS
(6.3)
Change
Maxwells equations
G ( P, T )
dG ...V ......dP ...S ......dT
G
G
dG
dP
dT
P T
T P
V
S
T P
P T
S V
V
S P
V T
V
V
S
T P
P T
T
S
CP
P
CP
Pressure derivatives:
P
H
V
V T
V
dH C p dT V T
dP
T P
dT V
dS C P
dP (6.21)
T T P
(6.20)
dependence of the
V S
S V
internal energy is
T
V
shown as
P S S P
U
V
T
V
P
P
P
dU Tds PdV
T
T
V T
V
V
S
T P
P T
V
dH C p dT V T
expressions of dH
T
and dS (eq.6.20-6.21)
dT V
dS
dP
as functions of T and
P
T T P
P can be simplified as
follows using ideal
gas law:
PV
ig
V ig
RT
T
dH ig C Pig dT
dS ig C Pig
dT
dP
R
T
P
R
P
(6.23)
(6.24)
dP
1 V
V T
dV
V
dP
dT
P
P
V
P T
Relations of liquids
V
S dV
V
can be expressed in V S
dT dP
terms of and as T
V V V
dH
V T
dP
C p dT
follows:
P S S P T P
S
dT SV
dS CP dP
T
T
T
T V V T P
H
1 T V
V
S
P T
T P
P T
U
U
V
V
T
V
T
P
T
P T
T P
P T
dU Tds PdV
Practice 1
Determine the enthalpy and entropy changes of liquid water for
a change of stage from 1 bar 25C to 1,000 bar 50C.
T
( C)
P
(bar)
25
Cp
(Jmol-1K-1
V
(cm3mol-1)
(K-1)
75.305
18.071
256x10-6
25
1000
18.012
366x10-6
50
75.314
18.234
458x10-6
50
1,000
18.174
568x10-6
Constant P
Constant T
H C p T2 T1 1 T2 V P2 P1
T2
S C p ln V P2 P1
T1
Integrated forms of
equations for change in
Enthalpy and Entropy
For P 1 bar ,
75.305 75.314
Cp
75.310 Jmol 1 K 1
2
Average value at T1
and T2 at 1 bar
10 6 513 10 6 K 1
2
Average value at P1
and P2 at 50 oC
H C p T2 T1 1 T2 V P2 P1
T2
S C p ln V P2 P1
T1
10
On substitution of values
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.
T
U
V
P
CV
T
P
T
P
V
P
dU CV dT T
P dV
T V
dT P
dS CV
dV
T T V
Alternative forms of the above equations are
dU CV dT T P dV
dT
dS CV
dV
T
T
1 V
V T
dV
V
dP
P T
dT
P
P
V
P T
dV
dT dP
V
dP
dT
2
RT
RT
RT
V
G RT
RT
P T
H
G RT
T
RT
T
Residual Properties
The definition for the generic residual property is:
M M M
R
M = the Residual
Molar gas
properties which
are at the same
temperature and
pressure.
ig
M is the actual
molar value of
any extensive
thermodynami
cs property: V,
U, H, S, G.
G G G
R
ig
Residual volume:
V V V
R
ig
RT
V
P
RT
Z 1
V
P
R
PV=ZRT
V R G R / RT
( 6.43 )
RT
P
T
R
HR
G / RT
T
( 6.44 )
RT
T
GR V R
d
dP
RT
RT
From Eq.(6.43),
GR GR
RT RT
P 0
Eq.(6.45 6.44);
From
So,
P
0
(const T )
P
VR
dP
dP ( Z 1) (6.45)
0
RT
P
P Z
HR
T
0
RT
T
GR
dP
(6.46)
P
S R H R GR
RT RT RT
P Z
SR
T
0 T
R
dP P
dP
( Z 1)
0
P
P
(const T )
(6.48)
0
P 0
Applied to H and S ; H H ig H R
S S ig S R
P
S S 0 C P dT R ln
T
P0
H H 0 C P dT
ig
ig
ig
ig
T0
ig
ig
Substituti on ; H H 0 C Pig dT H R
ig
( 6.50 )
T0
P
S S 0 C P dT R ln S R ( 6.51 )
T
P0
ig
ig
H ig H 0ig C P
R
(
T
T
)
H
0
H
( 6.52 )
T
P
S S 0 C P S ln R ln S R ( 6.53 )
T0
P0
ig
ig
T2
CP
ig
C
P dT
CP
T2 T1
R
T1
dT
T C P T
CP
ln( T2 / T1 )
R
T2
CP
C
D
2
A BTam ( 4Tam T1T2 )
3
T1T2
ig
D
A BTlm TamTlm C
2
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
Calculate H and S of saturated isobutane vapor
at 630 K from the following information:
1. Table 6.1 gives compressibility-factor data
2. The vapor pressure of isobutane at 630 K
15.46 bar
3. Set H0ig = 18,115 Jmol-1 and S0ig = 295.976
Jmol-1K-1 for the ideal-gas reference state at
300 K 1 bar
4. Cpig/R = 1.7765+33.037x10-3T
(T/K)
Solution 6.3
Eqs. (6.46) and (6.48) are used to calculate HR and SR.
Z
0 T
P
dP
P
dP
0 (Z 1) P
P
0
T
dP
dP
P
4
1
26.37 10 K
0 ( Z 1 ) 0.2596
P
P P
R
H
By Eq . ( 6.46 ),
( 360 )( 26.37 10 4 ) 0.9493
RT
R
S
By Eq . ( 6.48 ),
0.9493 0.2596 0.6897
R
For R 8.314 Jmol 1 K 1
P
C Pig
R
C Pig
T0 T1 300 360
330 K
2
2
T1 T0
360 300
Tlm
329.09 K
ln( T1 / T0 ) ln( 360 / 300 )
Tam
C Pig
C Pig
So,
G R BP
RT RT
(6.54)
G R / RT
HR
By Eq.(6.44),
T
RT
P B dB
(6.55)
R T dT
SR
P dB
Substitution int o Eq.(6.47),
R
R dT
(6.56)
P ZRT ( 6.57 ), dP RT ( Zd dZ )
Substitue int o Eq .( 6.49 );
GR
d
( Z 1 ) Z 1 ln Z ( 6.58 )
RT 0
H R Z 1 P
From Eq .( 6.40 ) and ( 6.42 ),
2
RT
P T
R
( G / RT )
HR
Z d
Differentition of Eq .( 6.57 ) and ( 6.58 );
T
Z 1 ( 6.59 )
0 T
RT
SR
d
Z d
From Eq .( 6.47 ),
ln Z T
(
Z
1
)
( 6.60 )
0 T
0
R
GR
3
2 B C 2 ln Z
(6.61)
RT
2
B dB
HR
C 1 dC 2
T
(6.62)
RT
T 2 dT
T dT
B dB
SR
1 C dC 2
ln Z T
(6.63)
R
2 T dT
T dT
1
b
q
1 b
(1 b)(1 b)
b
b
Z 1
q
(6.64)
1 b
(1 b)(1 b)
Z
b
dq
dT
(1 b)(1 b)
d
b d ( b)
d ( b)
(Z
1)
q
0
0 (1 b)(1 b)
0 1 b b
Z
0 T
d
dq
d ( b)
dT 0 (1 b)(1 b)
d
To simplify ; (Z - 1)
ln(1 b) qI ,
Z
0 T
d
dq
dT
1 b
1
Case I : I
ln
1 b
When is eliminated in favor of Z.
bP
RT
Case II :
P
Z
RT
(6.65a)
whence
b
Z
Z
1
I
ln
Z
b
1 b Z
(6.65b)
G
Z 1 ln(1 b) Z qI (6.66a )
RT
GR
Z 1 ln(Z ) Z qI (6.66b)
RT
R
d ln (Tr )
H
Z 1
1 qI (6.67)
RT
d ln Tr
S
d ln (Tr )
ln(Z )
qI (6.68)
R
d ln Tr
R
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
Pr
1.317
Eq.(3.53); 0.08664
0.09703
Tr
1.176
Tr
0.42748
Eq.(3.54); q
3.8689
3/ 2
Tr
0.086641.176
Eq.(3.52) : Z 1 q
Z
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,
TWO-PHASE SYSTEMS
G G , dG dG V dP sat S dT V dP sat S dT
dP sat S S S
Re arrangemen t ,
dT V V
V
Integration of Eq .( 6.8 ); H TS ( The latent heat of phase transition )
dP sat
H
Thus , S H / T
dT
TV
dP sat
H l
Phase transition from liquid to vapor ;
( 6.72 )
l
dT
TV
RT
d ln P sat
H l
l
l
But V sat Z
( 6.73 )
2
l
P
dT
RT Z
The Clapeyron eq.
for pure-species
d ln P sat H l
or
( 6.74 )
l
vaporization
d ( 1 / T ) RZ
B
T
B
The Antoine eq . : ln P A
( 6.76 )
T C
Antoine cons tan ts are given in Table B .2 , App .B
sat
1.5
3
6
A
A function of Tr ; ln Pr sat ( Tr )
( 6.77 )
1
where
1 Tr
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
1.28862 ln Tr 0.169347Tr6 (6.79)
Tr
0
r
15.6875
13.4721 ln Tr 0.43577Tr6 (6.80)
Tr
ln P (Trn )
(6.81)
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
2696.04
(a)
ln P sat 13.8193
t 224.317
341.9
1.01325
(b) Eq.(6.78);
Tr
0.6736, Prsat
0.03350
507.6
30.25
From Table B.1,
From Eq.(6.81) =0.298
n
t/C
0
60
Psat/kPa
Psat/kPa
Psat/kPa
t/C Psat/kPa
(Antoine) (Lee/Kesler
(Antoine) (Lee/Kesler
)
)
6.052
76.46
5.835
76.12
30
90
24.98
189.0
24.49
190.0
n nl nv
V x lV l x V
x : mass fraction
V (1 x v )V l x V
xl 1 xv
(moles)
THERMODYNAMIC DIAGRAMS
GENERALIZED PROPERTY
CORRELATION FOR GASES
P Pc Pr dP Pc dPr ,
T TcTr dT Tc dTr
H
2 Z
Tr
RTc
Tr
0
R
SR
Tr
R
Pr
Z
0 Tr
Pr
P
Pr
dPr
Pr
(6.83)
dPr r
dPr
( Z 1)
(6.84)
Pr 0
Pr
Z
Z Z Z
Tr
0
Pr
Z 0
Tr
0
r
HR
Z
2
Eq.(6.83) :
Tr
RTc
Tr
0
Pr
HR
HR
HR
RTc
RTc
RTc
SR r
Eq.(6.84) :
R 0
Z 1
Tr
Tr
SR
SR
SR
R
R
R
Pr
1
r
dPr
Z
2
Tr
Pr
Tr
Pr
Z 1
Tr
Pr
dPr
Pr
(6.85)
Pr
dPr
0
Z 1
Pr
Pr
Z 1
Tr
Tr
Z
Pr
dP
r
Pr
(6.86)
d B dB 0
dB1
dTr dTr
dTr
R
HR
Pr
RTc
H
d B
S
dB
Pr B Tr
,
Pr
RTc
dTr
R
dTr
0
1
d
B
d
B
(6.87)
B 0 Tr
B1 Tr
dTr
dTr
d B0
SR
d B1
Pr
R
dT
dT
r
r
(6.88)
0.422
B 0.083 1.6
Tr
(3.65)
0.172
B 0.139 4.2
Tr
(3.66)
dB 0 0.675
2.6
dTr
Tr
(6.89)
dB
0.722
5.2
dTr
Tr
(6.90)
H 2 H C dT H
ig
0
ig
P
T1
R
2
H1 H C Pig dT H1R
ig
0
H C Pig dT H 2R H1R
(6.91)
T1
T2
Similarly , S C Pig dT R ln
T1
P2
S 2R S1R
P1
(6.92)
Alternative form
H C Pig
S C Pig
(T2 T1 ) H 2R H1R
ln
(6.93)
T2
P
R ln 2 S 2R S1R
T1
P1
(6.94)
H1ig H1 H1R
S1ig S1 S1R
T2
dT
P2
S S S C
R ln (6.96)
T
P1
T1
ig
ig
2
ig
1
ig
P
Ex. 6.9
Estimate V, U, H and S for 1-butane vapor at 200C, 70 bar
if H and S are set equal to zero for saturated liquid at 0C.
Assume: Tc=420.0 K, Pc=40.43 bar, Tn=266.9 K, =0.191
Cpig/R=1.967+31.630x10-3T-9.837x10-6T2
(T/K)
Solution
200 273.15
70
Tr
1.127
Pr
1.731
420.0
40.43
Eq.(3.57) and Table E.3 and E.4;
Z Z 0 Z 1 0.485 0.191(0.142) 0.512
ZRT 0.512(83.14)(473.15)
V
287.8 cm3mol 1
P
70
B
T
(6.75)
A 10.126
B
266.9
B
420.0
B 2,699.11
9.979
RTn
0.930 Trn
0.930 0.636
H nlv 1 Tr
0.38
lv
From
...( 4.13 )
0.38
0.350
1
H ( 22 ,137 )
21
,
810
Jmol
0.368
lv
H
21,810
lv
1
1
S
79.84 Jmol K
T
273.15
lv
d
B
(6.87)
B1 Tr
dTr
H
dB
Pr B 0 Tr
RTc
dTr
d B0
SR
d B1
Pr
(6.88)
R
dTr
dTr
0.422
B 0.083 1.6
Tr
(3.65)
0.172
B 0.139 4.2
Tr
(3.66)
dB 0 0.675
2.6
dTr
Tr
(6.89)
dB1 0.722
5.2
dTr
Tr
(6.90)
ig
ig
T1
( T2 T1 )
dT
P2
Eq .( 6.96 ) : S S 2 S1 C P
R ln C Pig
T
T
P1
ig
ig
ig
T2
ig
T2
P2
ln R ln
S
T1
P1
Pr = 1.731
(70)(287.8)
32,218 Jmol 1
3
1
10 cm barJ
T
TPr
Tpc
(6.100)
P
PPr
Ppc
(6.101)
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,
140
Ppr
2.41
58.15
196.7 cm3mol 1
P
140
From Table E.7 and E.8; with Eq.(6.85) :
H
RT
pc
1.730
0.169
RT
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