Advanced Thermodynamics

Note 2
Volumetric Properties of Pure Fluids
Lecturer:

A pressure-temperature diagram
the sublimation curve
the fusion curve
the vaporization curve
the triple point
the critical point

Fig 3.1

A pressure-volume diagram
The isotherms
the subcooled-liquid and the
superheated-vapor regions
isotherms in the subcooledliquid regions are steep
because liquid volumes change
little with large change in
pressure

The two-phase coexist region

The triple point is the
horizontal line
The critical point

Fig 3.2

 An equation of state exists relating pressure, molar or specific volume, and

temperature for any pure homogeneous fluid in equilibrium states.
An equation of state may be solved for any one of the three quantities P, V, or T as a
function of the other two.
Example:

V
V
dT
dP

dV

Volume

1 V

V P

1 V
For incompressible fluid,
zero.
expansivity:
Isothermal
compressibility:
both and are
For liquids is almostVpositive
(liquid
water
between
0C
and 4C is an exception), and is
T P
necessarily positive.
At conditions not close to dV
the critical point, and can be assumed constant:
V

ln

dT dP

V2
(T2 T1 ) ( P2 P1 )
V1

Virial equations of state

PV along an isotherm:
PV a bP cP 2 a (1 BP C P 2 DP 3 ...)

The limiting value of PV as P 0 for all the gases:

PV
a f (,Twith
) R as the proportionally constant.

*
PV the
value
a RT
Assign
of 273.16 K to the temperature of the triple point of
water:

Ideal gas:

PV *t R 273.16

the pressure ~ 0; the molecules are separated by infinite distance; the

intermolecular forces approaches zero.

PV *t

cm3 bar
R
83.1447
273.16
mol K

The virial equations

The compressibility factor:
the virial expansion:

PV
Z
RT

Z (1 BP C P 2 DP 3 ...)

the parameters B, C, D, etc. are virial coefficients,

accounting of interactions between molecules.
the only equation of state proposed for gases having a firm
basis in theory.
The methods of statistical mechanics allow derivation of the
virial equations and provide physical significance to the virial
coefficients.

Ideal gas
No interactions between molecules.
gases at pressure up to a few bars may often be considered
ideal and simple equations then apply
the internal energy of gas depends on temperature only.
Z = 1; PV = RT
U = U (T)

dU
U
H
CV

C
(T
)
C

V
P
T

dT

U CV dT H C P dT

dH dU

R CV R C P (T )
dT dT

Mechanically reversible closed-system process, for a unit mass or a

mole:
CV
C
dQ dW CV dT
dQ
VdP P PdV
R
R
dW PdV

 For ideal gas with constant heat capacities undergoing a mechanically reversible
adiabatic process:

dQ dW CV dT

T2 P2

T1 P1

CP

dW PdV
for monatomic gases,
R
fordT
diatomic gases,
R dV
T2 V1 CV

for simple polyatomic gases, such as CO2, SO2, NH3 , and CH4,

CV V

T1

V2

PV const.
C
P
CV

The work of an irreversible process is calculated:

First, the work is determined for a mechanically

1.67 reversible process.
Second, the result is multiple or divided
1.4by an efficiency to give the actual work.

1.3

Air is compressed from an initial condition of 1 bar and 25C to a final state of 5
bar and 25 C by three different mechanically reversible processes in a closed
system. (1) heating at constant volume followed by cooling at constant pressure;
(2) isothermal compression; (3) adiabatic compression followed by cooling at
constant volume. Assume air to be an ideal gas with the constant heat capacities,
CV = (5/2)R and CP = (7/2)R. Calculate the work required, heat transferred, and the
changes in internal energy and enthalpy of the air in each process.

Fig 3.7

Choose the system as 1 mol of air, contained in an imaginary frictionless piston

/cylinder arrangement.
For R = 8.314 J/mol.K, CV = 20.785, CP = 29.099 J/mol.K
The initial and final molar volumes are: V1 = 0.02479 m3 and V2 = 0.004958 m3
The initial and final temperatures are identical: U = H = 0
(1) Q = CVT + CPT = -9915 J; W = U - Q = 9915 J
P1
3990 J
(2) Q W RT ln
P2

(3) adiabatic

V1
T

T
compression: 2 1 V
2

567.57 K

W CV T 5600 J
cooling at constant V, W = 0.
overall, W = 5600 J, Q = U - W = -5600 J.

V
P2 P1 1
V2

9.52 bar

An ideal gas undergoes the following sequence of mechanically reversible

processes in a closed system:
(1) From an initial state of 70C and 1 bar, it is compressed adiabatically to 150 C.
(2) It is then cooled from 150 to 70 C at constant pressure.
(3) Finally, it is expanded isothermally to its original state.
Calculate W, Q, U, and H for each of the three processes and for the entire
cycle. Take CV = (3/2)R and CP = (5/2)R. If these processes are carried out
irreversibly but so as to accomplish exactly the same changes of state (i.e. the same
changes in P, T, U, and H), then different values of Q and W result. Calculate Q
and W if each step is carried out with an efficiency of 80%.

Fig 3.8

Choose the system as 1 mol of air, contained in an imaginary frictionless piston

/cylinder arrangement. For R = 8.314 J/mol.K, CV = 12.471, CP = 20.785 J/mol.K
(1) For an ideal gas undergoing adiabatic compression, Q = 0
U = W = CVT = 12.471(150 70) = 998 J
H = CPT = 20.785(150 70) = 1663 J

T
P2 P1 2
T1

( 1)

1.689 bar

(2) For the constant-pressure process:

Q = H = CPT = 20.785(70 150) = -1663 J
U = CVT = 12.471(70 150) = -998 J
W = U Q = 665 J
(3) Isotherm process, U and H are zero:
P3
1495 J
Q W RT ln
P1

(4) Overall: Q = 0 1663 + 1495 = -168 J

W = 998 + 665 1495 = 168 J
U = 0
H = 0

Irreversible processes:
(1) For 80% efficiency:
W(irreversible) = W(reversible) / 0.8 = 1248 J
U(irreversible) = U(reversible) = 998 J
Q(irreversible) = U W = -250 J
(2) For 80% efficiency:
W(irreversible) = W(reversible) / 0.8 = 831 J
U = CVT = 12.471(70 150) = -998 J
Q = U W = -998 831 = -1829 J
(3) Isotherm process, U and H are zero:
W(irreversible) = W(reversible) x 0.8 = -1196 J
Q = U W = 1196 J
(4) Overall: Q = -250 1829 + 1196 = -883 J
W = 1248 + 831 1196 = 883 J
U = 0
H = 0
The total work required when the cycle consists of three irreversible steps is
more than 5 times the total work required when the steps are mechanically
reversible, even though each irreversible step is assumed 80% efficient.

A 400g mass of nitrogen at 27 C is held in a vertical cylinder by a frictionless

piston. The weight of the piston makes the pressure of the nitrogen 0.35 bar higher
than that of the surrounding atmosphere, which is at 1 bar and 27C. Take C V =
(5/2)R and CP = (7/2)R. Consider the following sequence of processes:
(1) Immersed in an ice/water bath and comes to equilibrium
(2) Compressed reversibly at the constant temperature of 0C until the gas volume
reaches one-half the value at the end of step (1) and fixed the piston by latches
(3) Removed from the ice/water bath and comes to equilibrium to thermal
equilibrium with the surrounding atmosphere
(4) Remove the latches and the apparatus return to complete equilibrium with its
surroundings.
Nitrogen may be considered an ideal gas. Calculate W, Q, U, and H for each
step of the cycle.
The steps:
(1) 27 C , 1.35bar

(3)

0 C , 1.35bar
1
0 C , V2 const
T 0 C , V3 V2
2
0 C , V3 const
V 27 C , V4 V3

(4)

27 C , P4 T 4 T1 27 C , 1.35bar

(2)

const P

m
14.286 mol
M

Fig 3.9

(1) W n PdV nPV nRT 3207 J Q nH nC T 11224 J

1
1
P
1

nU1 Q1 W1 11224 3207 8017 J

(2) U 2 H 2 0

Q2 W2 nRT ln

V3
22487 J
V2

(3) W3 0 Q3 nU 3 nCV T 8017 J nH 3 nC P T 11224 J

(4) the oscillation of the piston

U 4 H 4 0 Q4 W4

Air flows at a steady rate through a horizontal insulated pipe which

contains a partly closed valve. The conditions of the air upstream
from the valve are 20C and 6 bar, and the downstream pressure is 3
bar. The line leaving the valve is enough larger than the entrance line
so that the kinetic-energy change as it flows through the valve is
negligible. If air is regarded as an ideal gas, what is the temperature
of the air some distance downstream from the valve?
Flow through a partly closed valve is known as a throttling process.
For steady flow system:

d (mU ) cv
1

H u 2 zg m
dt
2

Ideal gas:

Q W

H 0

fs

H C P dT

The result that H = 0 is general for a throttling process.

T2 T1

If the flow rate of the air is 1 mol/s and if the pipe has an inner diameter of 5 cm,
both upstream and downstream from the valve, what is the kinetic-energy change
of the air and what is its temperature change? For air, C P = (7/2)R and the molar
mass is M = 29 g/mol.
Upstream molar volume:
RT1 83.14 293.15
1
V
6
3 m 2
V1

10 4.062 10
u

n
2.069 m
1
mol
s
P1
6
A
A

Downstream molar volume:

V2 2V1 u 2u 4.138 m
2
1

The rate of the change in kinetic energy:

2
2
1 2
1 2
3 ( 4.138 2.069 )
m u n M u (1 29 10 )
0.186 J
s
2
2
2

d (mU ) cv
1

H u 2 zg m
dt
2

Q W
fs

C
1
m P T u 2
2
M

T 0.0064 K

Application of the virial equations

Differentiation:
Z

B 2C P 3DP 2 ...
T

B
T ; P 0

the virial equation truncated to two terms satisfactorily

represent the PVT behavior up to about 5 bar

Z 1 BP

Z 1

BP
B
1
RT
V

the virial equation truncated to three terms provides good

results for pressure range above 5 bar but below the critical
pressure

Z 1 BP C P

Z 1

B C
2
V V

Reported values for the virial coefficients of isopropanol vapor at 200C are:
B = -388 cm3/mol and C = -26000 cm6/mol2. Calculate V and Z for isopropanol
vapor at 200 C and 10 bar by (1) the ideal gas equation; (2) two-term virial
equation; (3) three-term virial equation.
(1) For an ideal gas, Z = 1:
V

3
RT 83.14 473.15

3934 cm
mol
P
10

(2) two-term virial equation:

V

3
RT
B 3934 388 3546 cm
mol
P

PV
0.9014
RT

(3) three-term virial equation:

Vi 1

RT
P

B C
388 26000
cm 3
st

2 3934 1

3539
1
iteration
2
mol
Vi Vi
3934
(
3934
)

Ideal gas value

...
3

After 5 iterations V4 ~ V5 3488 cm

mol

PV
0.8866
RT

Cubic equations of state

Simple equation capable of representing both liquid and
vapor behavior.
The van del Waals equation of state:
RT
a
P

V b V 2
a and b are positive constants
unrealistic behavior in the two-phase region. In reality, two,
within the two-phase region, saturated liquid and saturated
vapor coexist in varying proportions at the saturation or vapor
pressure.
Three volume roots, of which two may be complex.
Physically meaningful values of V are always real, positive, and
greater than constant b.

Fig 3.12

A generic cubic equation of state

General form:

RT
(V )

V b (V b)(V 2 V )

where b, , , and are parameters depend on temperature and

(mixture) composition.
Reduce to the van der Waals equation when = b, = a, and == 0.
Set = b, = a (T), = (+) b, = b 2, we have:

RT
a (T )

b (Vthe
same
b)(Vfor
allb)substances, whereas
where and are pureVnumbers,
P

a(T) and b are substance dependent.

 Determination of the parameters:

horizontal inflection at the critical point:
P

2P

2
V

T ;cr
5 parameters (Pc, Vc, TTc,;cra(Tc), b) with
3 equations, one has:

3 RTc
Vc
8 Pc

27 R 2Tc2
a
64 Pc

1 RTc
8 Pc

Unfortunately,
P V it3does not agree with the experiment. Each chemical
Zc c c
species has
RTcits own
8 value of Z c.
Similarly, one obtain a and b at different T.

RT
a (T )
P

V b V (V b)

RT
(Tr ) R 2Tc2
b c
a (T )
Pc
Pc

Two-parameter and three-parameter

theorems of corresponding states
Two-parameter theorem: all fluids, when compared at the same reduced
temperature and reduced pressure, have approximately the same compressibility
factor, and all deviate from ideal-gas behavior to about the same degree.
Define reduced temperature and reduced pressure:

T
P
Tr
Pr
Not really enough to describe the state, a third corresponding-states
Tc parameterPisc
required.

The most popular such parameter is the acentric factor (K.S. Pitzer, 1995):

Three-parameter theorem: all fluids having

sat the same value of , when compared
temperature
1.0 log
Pr Tr pressure,
at the same reduced
and reduced
and all deviate from
0.7
ideal-gas behavior to about the same degree.

 Vapor and vapor-like

V
q

RT
a (T )
V b
b
P
P (V b)(V b)

a (T ) (Tr )

bRT
Tr
Z 1 q

V starts with V(ideal-gas)

and then iteration

bP
P
r
RT
Tr

Z
( Z )( Z )

Liquid and liquid-like

RT bP VP

a (T )

V b (V b)(V b)
q

a (T ) (Tr )

bRT
Tr

V starts with V = b and

then iteration

bP
P
r
RT
Tr

1 Z

Z ( Z )( Z )
q

Equations of state which express Z as a function of Tr and Pr are said to be

generalized, because of their general applicability of all gases and liquids.

2-parameter/3-parameter E.O.S.
Express Z as functions of Tr and Pr only, yield 2parameter corresponding states correlations:
The van der Waals equation
The Redlich/Kwong equation

The acentric factor enters through function (Tr;)

as an additional paramter, yield 3-parameter
corresponding state correlations:
The Soave/Redlich/Kwong (SRK) equation
The Peng/Robinson (PR) equation

Table 3.1

Given that the vapor pressure of n-butane at 350K is 9.4573 bar, find the molar
volumes of (1) saturated-vapor and (2) saturated-liquid n-butane at these
conditions as given by the Redlich/Kwong equation.

350
Tr
0.823
425.1
q

(Tr )
6.6048
Tr

9.4573
Pr
0.2491
37.96

Pr
0.026214
Tr

(1) The saturated vapor

Z 1 q

Z
( Z )( Z )

Z starts at Z = 1 and converges on Z = 0.8305

ZRT
cm3
V
2555
P
mol

(2) The saturated liquid

1 Z

Z ( Z )( Z )
q

ZRT
cm3
V
133.3
P
mol

Z starts at Z = and converges on Z = 0.04331

Generalized correlations for gases

Pitzer correlations for the compressibility factor:
Z Z 0 Z 1

Z0 = F0 (Tr, Pr)
Simple linear relation between Z and for given values
of Tr and Pr.
Of the Pitzer-type correlations available, the Lee/Kesler
correlation provides reliable results for gases which are
nonpolar or only slightly polar (App. E).
Only tabular nature (disadvantage)

Pitzer correlations for the 2nd virial

coefficient
Correlation:

BP
0 Pr
1 Pr
Z 1
1 B
B
RT
Tr
Tr

Z Z 0 Z 1

Z 0 1 B 0

Pr 1
P
Z B1 r
Tr
Tr

Validity at low to moderate pressures

For reduced temperatures greater than Tr ~ 3, there
appears to be no limitation on the pressure. B 0 0.083 0.422
Tr1.6
Simple and recommended.
0.172
Most accurate for nonpolar species.
B1 0.139
Tr4.2

Determine the molar volume of n-butane at 510K and 25 bar by, (1) the ideal-gas
equation; (2) the generalized compressibility-factor correlation; (3) the generalized
virial-coefficient correlation.
(1) The ideal-gas equation
RT
cm3
V
1696.1
P
mol

(2) The generalized compressibility-factor correlation

510
25
the acentric factor
0.659
Tr
1.200 Pr
0.200
37.96
425.1
the Lee/Kesler correlation
Z 0.865
0

Z 0.038
1

ZRT
cm3
1480.7
Z Z Z 0.873 V
P
mol
0

(3) The generalized virial-coefficient correlation

0.172
0.422 1
510
0
B

0
.
139

Tr
1.200 B 0.083 1.6
Tr4.2
Tr
425.1

Z 1 B0

3
Pr
P
B1 r 0.879 V ZRT 1489.1 cm
Tr
Tr
P
mol

What pressure is generated when 1 (lb mol) of methane is stored in a volume of 2

(ft)3 at 122F using (1) the ideal-gas equation; (2) the Redlish/Kwong equation; (3)
a generalized correlation .
(1) The ideal-gas equation
P

RT 0.7302(122 459.67)

212.4 atm
V
2

(2) The RK equation

RTc
581.67
(Tr ) R 2Tc2
atm
3
b

0
.
4781
ft
a
(
T
)

453
.
94
Tr
1.695
Pc
Pc
ft 6
343.1
P

RT
a(T )

187.49 atm
V b V (V b)

(3) The generalized compressibility-factor correlation is chosen (high pressure)

P

ZRT Z (0.7302)(122 459.67)

212.4 Z atm
V
2

Pr

581.67
P
Z
Tr
1.695

343.1
45.4 0.2138

P 189.0 atm

Z starts at Z = 1 and
converges on Z = 0.890

A mass of 500 g of gases ammonia is contained in a 30000 cm3 vessel immersed in

a constant-temperature bath at 65C. Calculate the pressure of the gas by (1) the
ideal-gas equation; (2) a generalized correlation .
Vt
cm 3
V
1021.2
n
mol

(1) The ideal-gas equation

P

RT
27.53 bar
V

(2) The generalized virial-coefficient correlation is chosen (low pressure, P r ~ 3 )

0.422
0.172
0
1
338.15
B

0
.
139

0
.
083

Tr
0.834
Tr4.2
Tr1.6
405.7
27.53
Pr ~
0.244 the acentric factor
0.253
112 .8

Z 1 B 0 B 1
P

Pr
P
1 0.541 r
Tr
Tr

ZRT
23.76 bar
V

Generalized correlations for liquids

The generalized cubic equation of state (low accuracy)
The Lee/Kesler correlation includes data for subcooled
liquids
Suitable for nonpolar and slightly polar fluids

Estimation of molar volumes of saturated liquids

Rackett, 1970: V sat V Z (1Tr ) 0.2857
c c
Generalized density correlation for liquid (Lydersen,
Greenkorn, and Hougen, 1955): Vc
r


V2 V1 r1
r 2

Fig 3.17

For ammonia at 310 K, estimate the density of (1) the saturated liquid; (2) the
liquid at 100 bar
(1) Apply the Rackett equation at the reduced temperature
Tr

310
V 72.47 Z c 0.242
0.7641 c
405.7

V sat Vc Z c(1Tr )

0.2857

(2) At 100 bar

100
Pr
0.887
112 .8
Tr

310
0.7641
405.7

cm3
28.33
mol

Fig 3.17

r 2.38

Vc
cm3
V
30.45
r
mol

r1,310 K , saturated liquid

r1
2.34
cm 3
310 K
V2 V1
V
29.14
28.65
r 2
r 2,100bar
2.38
mol