Introduction to Thermodynamics II.

PVT Behavior of Pure Substances

ღ PVT Surfaces
Topics:
I. Phase Rule
II. PVT Behavior of Pure Substances
a. PVT Surfaces
b. PT Diagram (Phase Diagram)
c. PV Diagram
d. TV Diagram
e. Critical Behavior
f. Single Phase Region
III. Viral Equation of State
a. Ideal-Gas Temperature, Universal Constant
b. Virial Equation of State
c. Virial Expansion
d. Truncated Virial Equation
IV. Cubic Equation of State
a. Van der Waals Equation
b. Redlich- Kwong Equation
c. Berthelot Equation
d. Dieterici Equation
e. Principle of Corresponding States contracts on freezing
V. Generalized Correlation for Gases
a. Lee Kessler Correlation
b. Pitzer Correlation for Second Virial Coefficient
c. Pitzer Correlation for Third Virial Coefficient
VI. Generalized Correlation for Liquids
VII. Thermodynamic Tables

I. Phase Rule
 Phase – homogeneous region of matter
 intensive state of a system at equilibrium:
temperature, pressure, and the
compositions are fixed
 number of degrees of freedom – number of
independent variables that must be
arbitrarily fixed to establish its intensive
state
expands on freezing (like water)
F=2– π +N
 For non-reactive system: F = C – P + 2
ღ PT/Phase Diagram
Example 3.1
How many phase-rule variables must be specified
to fix the thermodynamic state of each of the
following systems?
(a) Liquid water in equilibrium with its vapor.
F = C – P + 2 = 1 – 2 +2 = 1
(b) Liquid water in equilibrium with a mixture of
water vapor and nitrogen.
F = C – P + 2 = 2 – 2 +2 = 2
(c) A three-phase system of a saturated aqueous
salt solution at its boiling point with excess salt
crystals present.
F=C–P+2=2–3+2=1  Pc and Tc – highest pressure and highest
temperature at which a pure chemical
species is observed to exist in vapor/liquid
equilibrium
 Vaporization Curve – separates the liquid Example
and gas regions Gas in a piston at an initial pressure of 1MPa is
 Fusion Curve – separates the solid and compressed at constant pressure until it reaches
liquid regions a specific volume of 0.1 m3/kg. It is then cooled
 Sublimation Curve – separates the solid and at constant volume until it reaches a pressure of
gas regions 100 kPa. What are its final temperature and phase?
 Accdg to phase rule,
o F = 0, triple point (invariant) Final temp = 100°C
o F = 1, along two-phase lines Final Phase = liquid/vapor
(univariant)
o F = 2, single-phase regions ღ Critical Behavior
Critical Point – condition at which the start
ღ PV Diagram of fluid behavior where the liquid and gas
can no longer be distinguished

ღ Single Phase Region

 PVT Equation of State – relates pressure,
molar/specific volume, and temperature

 Liquids and vapors (BCD) are said to be

saturated.
 two-phase liquid/vapor region lies under
dome BCD
 subcooled-liquid region: left of the
saturated-liquid curve BC Final Equation:
 superheated-vapor region: right of the
saturated-vapor curve CD

 Subcooled-liquid: exists at temperatures

below the boiling point for the given Example 3.2
pressure For liquid acetone at 20°C and 1 bar,
 Superheated-vapor: exists at temperatures β = 1.487 × 10−3°C−1
above the boiling point for the given κ = 62 × 10−6 bar−1
pressure V = 1.287 cm3⋅g−1

ღ TV Diagram For acetone, find:

(a) The value of (∂ P / ∂ T) V at 20°C and 1 bar.
dP β 1.48 ×10−3 ℃−1
= =
dT κ 62×10−6 ¿¯−1=23.98 ¯¿ ¿ ¿
℃

(b) The pressure after heating at constant V from

20°C and 1 bar to 30°C.
T1 = 20°C ; T2 = 30°C
P1 = 1 bar ; P2

V2
ln V =β ( T 2−T 1 )−κ ( P2−P1 ) ¿
1
¿
 β
P2=P1 + ( T 2 −T 1 )
κ
¯
+1.487 × 10
−3
P2=1 −6
(30 ℃−20 ℃)  3 terms- above applicability of two terms
62×10
P2 = 240.84 bar but below critical pressure

(c) The volume change when T and P go from 20°C

and 1 bar to 0°C and 10 bar. Example 3.8
T1 = 20°C , T2 = 0°C Reported values for the virial coefficients of
P1 = 1 bar, P2 = 10 bar isopropanol vapor at 200°C are:
B = − 388 cm3· mol−1 ; C = − 26,000 cm6· mol−2
V2 Calculate V and Z for isopropanol vapor at 200°C
ln V =β ( T 2−T 1 )−κ ( P2−P1 ) ¿ and 10 bar:
1
¿ (a) For the ideal-gas state;
V2 −3 −6 (b) By Virial Equation truncated to two terms;
ln V =1.487× 10 ( 0 ℃−20℃ )−62 ×10 ¿ ¿ (c) By Virial Equation truncated to three terms
1
¿
V2
=0.9702
V1

( )
3 3
cm cm
V 2=( 0.9702) 1.287 =1.2486
g g
3 3 3
cm cm cm
∆ V =1.2486 −1.287 =−0.0384
g g g

III. Virial Equation of State

ღ Ideal-Gas State, Universal Constant

ღ Virial Equation of State

 Applicable to gases based on the
isotherms for gases and vapors lying at
the right of the saturated vapor curve in
a phase diagram, where PV for a given T IV. Cubic Equation of State
varies more slowly giving the equation  Cubic Equations - the simplest equations
as a function of P. capable of representing both liquid and
 Equation: vapor behavior
PV V
Z≡ =
RT V ig

ღ Virial Expansion
' ' 2 ' 3
Z=1+B P+C P + D P +…
B C D
Z=1+ + 2 + 3 + …
V V V
 Vapor

ღ Truncated Virial Equations

 2 terms – low pressures
 n-butane:
Tc = 425.12 K
Pc = 3.796 Mpa -> 37.96 bar
T = 350K
P = 9.4573 bar

 Z=1 P 9.4573
Pr = = =0.2491
Pc 37.96
 Liquid T 350
T r= = =0.8233
T c 452.12
−0.5
a ( T r ) =( 0.8233 ) =1.1021

( )
P 0.2491
β=Ω r =( 0.08664 ) =0.0262
Tr 0.8233
−1
 Z=β 2
−1
ψT r( 0.42748 )( 0.8233 ) 2
q= = =6.6048
Ω Tr (0.08664)(0.8233)

 Reduced Temperature and Pressure

T P
T r= Pr =
Tc Pc a. sat’d vapor
Z−β
Z=1+ β−qβ
ღ Van der Waals Equation of State ( z +ϵβ )( Z+ σβ )
- J. D. van der Waals, 1873 Z −0.026214
RT a Z=1+0.0262−(6.6048)(0.026214)
P= − 2 ( Z )( Z +0.026214)
V −b V Z = 0.8305
a/V2 = accounts for the attractive forces between molecules
b = account for the finite size of molecules, which makes the
volume larger than in the ideal-gas state
PV ZRT (0.8305)(83.14)(350) c
Z= →V= = =2555.35
RT P (9.4573) m
ღ Redlich Kwong (RK) Equation of State (1949)
RT a(T )
P= − b. sat’d liq
V −b V (V +b)

ღ Berthelot Equation of State

Z=β+ ( Z +ϵβ )( Z+ σβ ) ( 1+qββ−Z )
P=
RT
−
a
V −b T V 2
Z=0.0262+ ( Z+(0)(0.0262) )( Z +(1)(0.0262))
( (6.6048
1+0.026
)( 0
2 3
RTc Z = 0.0433
27 R T c
a= b=
64 Pc 8 Pc
PV ZRT (0. 0433)(83.14)(350) cm
Z= →V= = =133.23
RT P (9.4573) m
ღ Dieterici Equation of State

P=
RT
V −b
exp
−a
RTV ( ) ღ Corresponding States
 Two-parameter corresponding states
2 2
4 R Tc RTc All fluids, when compared at the same
a= b=
P c exp ( 2 ) P c exp ( 2 ) reduced temperature and reduced
pressure, have approximately the same
Example 3.9 compressibility factor, and all deviate from
Given that the vapor pressure of n-butane at 350 K ideal-gas behavior to about the same
is 9.4573 bar, find the molar volumes of degree.
(a) saturated-vapor and Two Parameters: Tc, Pc
(b) saturated-liquid n-butane at these conditions as Equations of state: vdW, RK
given by the Redlich/Kwong equation.  Three-parameter corresponding states
Given:
 All fluids having the same value of acentric Determine the molar volume in cm3/mol of n-
factor, when compared at the same butane at 510 K and 25 bar based on each of the
reduced temperature and reduced following:
pressure, have about the same Given:
compressibility factor, and all deviate from T = 510 K
ideal gas behavior to about P = 25 bar
the same degree.
Three Parameters: Tc, Pc, ω (acentric (a) The ideal-gas state. (R= 83.14 bar-cm3/ mol –K)
factor) RT ( 83.14)(510) c m3
Equations of state: SRK, PR
V= = =1696.056
P (25) mol
(Peng/Robinson)
(b) The generalized compressibility-factor
correlation.
Tc = 425.12 K ; Pc = 3.796 MPa = 37.96 bar

V. Generalized Correlations for Gases P 25

Pr = = =0. 6586
 Pitzer correlation: Z=Z 0 +ω Z 1 Pc 37.96
T 510
T r= = =1.1997
ღ Lee/Kessler Correlation T c 452.12
- Appendix D, Table D.1 to D.4 ω = 0.2002

ღ Pitzer Correlations for Second Virial *interpolate for value of Z0 and Z1 in Van Ness Table
Coefficients D.1 to D.4
- Functions of temperature only Z=Z 0 +ω Z 1=0.8646+ ( 0.2002 )( 0.0376 )
- Low to moderate pressures, Z is Z=0.8721
linear in pressure
PV ZRT (0.8721)(83.14)(510) c
Z= →V= = =1479.13
RT P (25) m

(c) Using Pitzer Correlations for the Second Virial

Coefficient, with the generalized correlation for Bˆ.
Tr = 1.1997 ; Pr = 0.6586 ; ω = 0.2002

0.422
B0=0.083− 1.6
Tr
0 0.422
ღ Pitzer Correlations for Third Virial B =0.083− =−0.2324
( 1.1997 )1.6
Coefficients
1 0.17 2
B =0. 13 9− 4.2
Tr
1 0.172
B =0.139− =0.0589
( 1.1997 )4.2

^B=B0 +ω B1
^B=−0.2324+ ( 0.2002 ) ( 0.0589 )=−0.2206

PR 0.6586
^
Z=1+ B =1+ (−0.2206 ) =0.8789
Tr 1.1997

ZRT (0.87 89)(83.14)(510) c m3

V= = =149 0 . 66
Example 3.10 P (25) mol
(d) Using Pitzer Correlations for the Third Virial (b) liquid at 100 bar (V1 for sat’d liquid at 310 K =
Coefficient, with the generalized correlations for Bˆ 29.14 cm3/mol)
and Cˆ. Given:
Tr = 1.1997 ; Pr = 0.6586 ; ω = 0.2002 Tc = 405.65K
B0 = -0.2324 ; B1 = 0.0589 ; ^
B = -0.2206 Pc = 11.28 Mpa = 112.8 bar
Zc = 0.242
0.02432 0.00313 Tr = 0.7642
C 0=0.0 1407+ −
Tr Tr
1 0.5

0.02432 0. 00313 (a) sat’d liq

C 0=0.01407+ − =0.0339 2
1.1997 ( 1.1997 )10.5 7
q=1+ ( 1−0.7642) =1.6618
1 0.0 5539 0.00242 q = 1.0 + (1-Tr)
C =−0.02676+ −

( ) (
2.7 10.5

)
Tr Tr R T c q ( 83.14 )( 405.65 ) 1.6618
0.05539 0.00242 V = Zc = ( 0.242 )
1
C =−0.02676+ − =6.7616 x 10
−3 P c 112.8
( 1.1997 )2.7 ( 1.1997 )10.5 c m3
V =28.2929
mol
^
C=C
0
+ωC
1

^
C=0.0339+ ( 0.2002 ) ( 6.7616 x 10−3 )=0.0353 1 1 1 mol
=V → ρ= = =0.0353

( )
ρ RTc q cm
3
cm
3
Z c 28.2929
Pc mol

( )
2
^ P R +C
Z=1+ B ^ PR (b) liquid at 100 bar
TrZ Tr Z Tc = 405.65K

( )
0.6586 0.6586
2 Pc = 11.28 Mpa = 112.8 bar
Z=1+ (−0.2206 ) + ( 0.0353 ) =0.8756 Zc = 0.242
(1.1997 )( Z ) ( 1.1997 ) ( Z )
Tr = 0.7642
V1 = 29.14 cm3/mol
ZRT (0.87 56)(83.14)(510)
3
cm
V= = =14 85.07
P (25) mol
Pr = 100/112.8 = 0.8865

Based on figure:
ρr1 = 2.34
VI. Generalized Correlation for Liquids ρr2 = 2.38
 Available for estimation of molar volumes
of saturated liquids
 Rackett equation:
ρr 1
( ) ( )
3
2.34 cm
V 2=V 1 =29.14 =28.6503
ρr 2 2.38 mol
1 1 1 mol
=V → ρ= = =0.349
ρ V 28.6503 c m3
 Lydersen, Greenkorn, and Hougen
VII. Thermodynamic Tables
equation:
 Steam Table in Introduction to Chemical
Engineering Thermodynamics (Van Ness et
al., 2018)
 Molar volume: - Appendix E for Saturated and
Superheated Steam Tables on pp.
684-723.
 Thermodynamic Tables in Perry’s Handbook
8th Edition (Perry and Green, 2008)
Example 3.13
- Table 2-184 up to 2-309
For ammonia at 310 K, estimate the density of:
Thermodynamic Properties of All
(a) The saturated liquid;
 Known Substances, pp. 2-207 up to
2-419
- Table 2-304 Saturated Solid/Vapor
Water p. 2-412
- Table 2-305 Thermodynamic
Properties of Water p. 2-413-415
- Table 2-306 Thermodynamic
Properties of Water Substance along
the Melting Line p. 2-416