ERT 206/4

Thermodynamics
CHAPTER 3
Volumetric Properties of Pure Fluids

Miss. Rahimah Bt. Othman

Email: rahimah@unimap.edu.my
 COURSE OUTCOME 1 CO1)
1. Chapter 1: Introduction to Thermodynamics
2. Chapter 2: The First Law and Other Basic Concepts

2. Chapter 3: Volumetric properties of pure fluids

DESCRIBE and EXPLAIN PVT behavior of pure substances,
Virial Equation of State, Ideal Gas, Virial Equation-
APPLICATION, Cubic Equation of State, Generalized
Correlations for gases and liquids.

4. Chapter 4: Heat effects

5. Chapter 5: Second law of thermodynamics
6. Chapter 6: Thermodynamics properties of fluids
 4. Property Diagrams 5. Property Tables
for Phase-Change
Processes
6. The Ideal-Gas
Equation of State

3. Phase-
Change of PURE 7. Compressibility
Pure SUBSTANCE Factor- A
Substances Measure of
Deviation from
Ideal-Gas
2. Phases of a Behavior
Pure Substance
1. Pure 8. Other Equations
Substance of State
 1. Pure Substance
 A substance that has a fixed
chemical composition throughout is
called a Pure Substance.
 Pure Substance:
- N2, O2, gaseous Air
-A mixture of liquid and gaseous
water is a pure substance, but a
mixture of liquid and gaseous air is
not.
 2. Phases of a Pure Substance

The molecules
in a SOLID are
kept at their
positions by
the large
spring like
inter-molecular
forces. In a solid, the
attractive and
repulsive forces
between the
molecules tend to
maintain them at
relatively constant
distances from each
other.

The arrangement of atoms in different phases: (a) molecules are at relatively

fixed positions in a solid, (b) groups of molecules move about each other in the
LIQUID phase, and (c) molecules move about at random in the GAS phase.
 3. Phase-Change Processes of
Pure Substance
 Compressed liquid or a subcooled liquid:
A liquid that is not about to vaporize.
 Saturated liquid: A liquid that is about
to vaporize.
 Saturated vapor: A vapor that is about
to condense.
 Saturated liquid-vapor mixture: the
liquid and vapor phases coexist in
equilibrium.
 Superheated vapor: A vapor that is not
about to condense
 3. Phase-Change Processes of Pure
Substance
 Saturated temperature, Tsat: At a given
pressure, the temperature at which a pure
substance changes phase.
 Saturated pressure, Psat: At a given
temperature, the pressure at which a pure
substance changes phase.
 Latent heat: the amount of energy absorbed or
released during a phase-change process.
 Latent heat of fusion: the amount of energy
absorbed during melting.
 Latent heat of vaporization: the amount of
energy absorbed during vaporization.
 T-v diagram for the heating process of water at
constant pressure.
2-1
3. Property Diagrams for Phase-Change Processes

Critical point – highest

combination of pressure
PVT BEHAVIOR OF PURE and temperature
SUBSTANCES/ FLUIDSwhere the
fluid exist in liq-vap
equilibrium

The 2-C line, also known as

vaporization curve is where
liquid-vapor is in equilibrium

Triple point, three

phases exist in
The 1-2 line, also The 2-3 line, also known as
equilibrium (F=0)
known as sublimation fusion curve is where solid-
curve is where solid- liquid is in equilibrium
vapor is in
equilibrium
3. Property Diagrams for Phase-Change Processes
 4. Property Tables

 For most substances, the relationships among thermodynamics

properties are too complex to expressed by simple equations.
Therefore properties are presented in the form of tables (Property
Tables).[ Smith et al. (2005); Cengel & Boles (2002)]
 Property tables are given in the Appendix in both SI and English
units.
 The tables in English units carry the same number as the
corresponding tables in SI, followed by an identifier E.
 For example: Tables A-6 and A6-E list properties of superheated
water vapor.[Tables F-2 in Smith et al.]
 Table A-4 until A-8: show internal energy (u), enthalpy (h) and
entropy (s).
 4(a). Saturated Liquid and Saturated Vapor States
 The properties of saturated liquid and saturated vapor for water
are listed in Tables A-4 and A-5.
 Table A-4 properties is listed under temperature, and Table A-5
under pressure.
 Subscript:
f = properties of saturated liquid
g = properties of saturated vapor
fg = difference between properties of saturated vapor and liquid
 For example:
vf = specific volume of saturated liquid
vg = specific volume of saturated vapor
vfg = vg - vf
 Saturated pressure (Psat):
- The pressure when liquid and vapor phases are in equilibrium at a given
temperature value.
 Saturated temperature (Tsat):
- The temperature when liquid and vapor phases are in equilibrium at a given
pressure value.
 Example 3.1 (Pressure of saturated liquid)

A rigid tank contains 50 kg of saturated liquid water at 90 oC. Determine the

pressure in the tank and the volume of the tank.
Solution

The state of the saturated liquid water is shown on a T-v diagram. Since
saturation conditions exist in the tank, the pressure must be the saturation
pressure at 90 oC.
P = Psat@90oC = 70.14 kPa (Table A-4)
The specific volume of the saturated liquid at 90 oC is
v = vf@90oC = 0.001036 m3/kg (Table A-4)
Then the total volume of the tank is
V = mv = (50 kg)(0.001036 m3/kg) = 0.0518 m3
 Example 3.2 (Temperature of saturated vapor)
A piston-cylinder device contains 2 ft3 of saturated water vapor at 50-psia
pressure. Determine the temperature and the mass of the vapor inside the
cylinder.

Solution

The state of the saturated water vapor is shown on a P-v diagram. Since the
cylinder contains saturated vapor at 50 psia, the temperature inside must be
the saturation temperature at this pressure.
T = Tsat@90oC = 281.03 oF (Table A-5E)
The specific volume of the saturated vapor at 50 psia is;
v = vf@50 psia = 8.518 ft3/lbm (Table A-5E)
Then the mass of water vapor inside the cylinder becomes;
V 2 ft 3
m  3
 0.235 lbm
v 8.518 ft /lbm
 Example 3.3 (Volume and Energy Change during Evaporation)

A mass of 200 g of saturated liquid water is completely vaporized at a

constant pressure of 100 kPa. Determine (a) the volume change and (b) the
amount of energy added to the water.
Solution
(a) The process described is illustrated in a P-v diagram. The volume
change per unit mass during a vaporization process is vfg, which is the
difference between vg and vf.
Reading these values from Table A-5 at 100 kPa and substituting yield
vfg = vg - vf = 1.6940 – 0.001043 = 1.6930 m3/kg
Thus,
∆V = mvfg = (0.2 kg) (1.6930 m3/kg) = 0.3386 m3
(b) The amount of energy needed to vaporize a unit mass of a substance at a
given pressure is the enthalpy of vaporization at that pressure, which is;
hfg = 2258.0 kJ/kg for water at 100 kPa.
mhfg = (0.2 kg)(2258 kJ/kg) = 451.6 kJ.
 4(b). Saturated Liquid-Vapor Mixture
 During the vaporization process, a substance exists as part liquid
and part vapor.
 To analyze this mixture, we need to know the proportions of the
liquid and vapor phases in the mixture.
 This to be done by defining a new property called the quality, x
as the ratio of the mass of vapor to the total mass of the mixture:
mvapor mvapor mg
x   ; 0  x  1
mtotal mliquid  mvapor m f  mg

 Consider a tank that contains a saturated liquid-vapor mixture.

The volume occupied by saturated liquid is Vf, and the volume
occupied by saturated vapor is Vg. The total volume V is the sum
of the two; V  V V f g

m  m f  mg
V  mv, V f  m f v f , Vg  mg v g
 4(b). Saturated Liquid-Vapor Mixture-cont’

 Therefore,
mv  m f v f  mg v g
mf vf mg v g
v 
m m
mg mg
since x 
m m f  mg
mf m  mg
   1 x
m m
 v  (1  x )v f  xvg
or v  v f  x (v g  v f )
with v fg  v g  v f
v  vf
x
v fg
This analysis can be repeated for internal energy and enthalpy;
u  u f  xu fg
h  h f  xhfg
 Example 3.4 (Pressure and Volume of a Saturated Mixture)
A rigid tank contains 10 kg of water at 90 oC. If 8 kg of the water is in the
liquid form and the rest is in the vapor form, determine (a) the pressure in the
tank and (b) the volume of the tank.
Solution
(a) Since the two phases coexist in equilibrium, we have a saturated mixture
and the pressure must be the saturation pressure at the given temperature;

P = Psat@90oC = 70.14 kPa (Table A-4)

(b) At 90 oC, we have vf = 0.001036 m3/kg and vg = 2.361 m3/kg (Table A-4)
One way of finding the volume tank is to determine the volume occupied by
each phase and then add them:
V  V f  Vg  m f v f  m g v g
 (8 kg)(0.0010 36 m 3 /kg)  (2kg)(2.36 1m 3 /kg)
 4.73m 3
 Example 3.4 (Pressure and Volume of a Saturated Mixture) cont’

(b) Another way is to first determine the quality x, then the average specific
volume v, and finally the total volume:
mg 2 kg
x   0.2
mf 10 kg
v  v f  xv fg
 0.001036 m 3 /kg  [( 2.361  0.001036)m 3 /kg]
 0.473 m 3 /kg
and
V  mv  (10 kg)(0.473 m 3 /kg)  4.73 m 3
 Example 3.5 (Properties of Saturated Liquid-Vapor Mixture)
A 80-L vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.
Determine (a) the temperature of the refrigerant, (b) the quality, the enthalpy
of the refrigerant, and (d) the volume occupied by the vapor phase.
Solution
(a) Basically, we do not know whether the refrigerant is in the compressed
liquid, superheated vapor, or saturated mixture region.
This can be determined by comparing a suitable property to the saturated
liquid and saturated vapor values. From the given information, we can
determine the specific volume;

V 0.080 m3
v   0.02 m3 /kg
m 4 kg
At 160 kPa, we read

v f  0.0007435 m3 /kg
vg  0.1229 m3 /kg Table A -12
 Example 3.5 (Properties of Saturated Liquid-Vapor Mixture)-cont’

Obviously, vf ˂ v ˃ vg, and, the refrigerant is in the saturated mixture region.

Thus, the temperature must be the saturation temperature at the specified
pressure:
T = Tsat@ 160 kPa = -15.62 oC (Table A-12)

(b) Quality can be determined from;

v  vf 0.02 - 0.007435
x   0.158
v fg 0.1229 - 0.0007435

(c) At 160 kPa, we also read from Table A-12 that hf = 29.78 kJ/kg and
hfg = 208.18 kJ/kg. Then;

h  h f  xhfg
 29.78 kJ/kg  (0.158)(20 8.18 kJ/kg)
 62.7 kJ/kg
 Example 3.5 (Properties of Saturated Liquid-Vapor Mixture)-cont’

(d) The mass of the vapor is;

mg  xmt  (0.158)(4 kg)  0.632 kg

and the volume occupied by the vapor phase is;

Vg  mg vg  (0.632 kg)(0.1229 m3/kg)  0.0777 m3 (or 77.7 L)

The rest of the volume (2.3 L) is occupied by the liquid.

 4(c). Superheated Vapor

 In the region to the right of the saturated vapor line and at

temperatures above the critical point temperature, a substance
exists as superheated vapor.
 Superheated vapor is characterized by;

Lower pressures (P < Psat at a given T)

Higher temperatures (T > Tsat at a given P)
Higher specific volumes (v > vg at a given P or T)
Higher internal energies (u > ug at a given P or T)
Higher enthalpies (h > hg at a given P or T)
 Example 3.6 (Temperature of Superheated Vapor)

Determine the temperature of water at a state of P = 0.5 MPa and

h = 2890 kJ/kg.
Solution
At 0.5 Mpa, the enthalpy of saturated water vapor is hg = 2748.7 kJ/kg. Since
h > hg, now we have superheated vapor.
Under 0.5 MPa. In Table A-6 we read;
T, oC h, kJ/kg
200 2855.4
250 2960.7

Obviously, the temperature is between 200 and 250 oC. By linear interpolation
it is determined to be:
T = 216.4 oC.
 4(d). Compressed Liquid

 In general, a compressed liquid is characterized by;

Higher pressures (P > Psat at a given T)

Lower temperatures (T < Tsat at a given P)
Lower specific volumes (v < vg at a given P or T)
Lower internal energies (u < ug at a given P or T)
Lower enthalpies (h < hg at a given P or T)

 In the absence of compressed liquid data, a general approximation

is to treat compressed liquid as saturated liquid at the given
temperature.
 This is because the compressed liquid properties depend on
temperature much more strongly than they do on pressure.
 Example 3.7 (Approximation Compressed Liquid as Saturated Liquid)

Determine the internal energy of compressed liquid water at 80 oC and

5 MPa, using (a) data from the compressed liquid table and (b) saturated
liquid data. What is the error involved in the second case?
Solution
At 80 oC, the saturation pressure of water is 47.39 kPa, and since
5 MPa > Psat, we obviously have compressed liquid.
(a) From the compressed liquid table (Table A-7)
P  5 MPa 
 u  333.72 kJ/kg
T  80 C 
o

(b) From the saturation table (Table A-4), we read

u  u f @80 oC  334.86 kJ/kg
The error involved is 334.86  333.72
x 100  0.34 %
333.72
which is less than 1 percent.
 EXERCISE 1
Determine the missing properties and the phase descriptions in the following
table of water:

T, oC P, kPa u, kJ/kg x Phase description

(a) 200 0.6

(b) 125 1600
(c) 1000 2950
(d) 75 500
(e) 850 0.0
 EXERCISE 1
Determine the missing properties and the phase descriptions in the following
table of water:

Answer:

T, oC P, kPa u, kJ/kg x Phase description

(a) 120.23 200 1719.49 0.6 Saturated liquid-vapor mixture

(b) 125 232.1 1600 0.535 Saturated liquid-vapor mixture
(c) 395.6 1000 2950 No meaning Superheated vapor
(d) 75 500 313.90 No meaning Compressed liquid
(e) 172.96 850 731.27 0.0 Saturated liquid
 6. The Ideal-Gas Equation of State

• Equation of state: Any equation that

relates the pressure, temperature, and
specific volume of a substance.
• The simplest and best-known equation of
state for substances in the gas phase is the
ideal-gas equation of state. This equation
predicts the P-v-T behavior of a gas quite
accurately within some properly selected
region.
Ideal gas
equation of
state

R : gas constant
M : molar mass (kg/kmol)
Ru : universal gas constant
Different substances have
U = U(T) (Ideal gas) (3.15) different gas constants.
 7. Compressibility Factor - A Measure of
Deviation from Ideal-Gas Behavior
 The ideal-gas equation is very simple and thus very convenient to
use. But, gases deviate from ideal-gas behavior significantly at
states near the saturation region and the critical point.
 This deviation from ideal-gas behavior at a given temperature and
pressure can accurately accounted by correction factor called as
compressibility factor, Z.
Pv
Z
RT
or
Pv  ZRT
It can also be expressed as;
v actual
Z
v ideal
 7. Compressibility Factor - A Measure of
Deviation from Ideal-Gas Behavior
 Gases behave differently at a given temperature and pressure, but they
behave very much the same at temperatures and pressures normalized with
respect to their critical temperatures and pressures.
 The normalization is done as; P T
PR  and TR 
Pcr Tcr

where PR = reduced pressure, TR = reduced temperature.

 When P and v, or T and v, are given instead of P and T, the generalized
compressibility chart can still be used to determine the third property, but it
would involve tedious trial and error.
 Therefore, it is necessary to define one more reduced property called the
pseudo-reduced specific volume , vR as: v
vR  actual
RTcr / Pcr
 The Generalized Compressibility Chart can be used for all gasses.
[Figure A-30a until A-30c]
 Example 3.8 (The use of Generalized Charts)
Determine the specific volume of refrigerant-134a at 1 MPa and 50 oC,
using (a) the ideal-gas equation of state and (b) the generalized
compressibility chart. Compare the values obtained to the actual value of
0.02171 m3/kg and determine the error involved in each case.
Solution
The gas constant, the critical pressure, and the critical temperature of
refrigerant-134a are determine from Table A-1 to be;

R  0.0815 kPa. m 3 /kg. K

Pcr  4.067 MPa
Tcr  374.3 K
(a) The specific volume of refrigerant-134a under the ideal-gas assumption is;

v
RT

 
0.0815 kPa. m3 /kg. K 323 K 
 0.02632m3 /kg
P 1000 kPa
Therefore, treating the R-134a vapor as an ideal gas would result in an error of
(0.02632-0.02171)/0.02171=0.212, or 21.2 percent in this case.
 Example 3.8 (The use of Generalized Charts)-cont’

(b) To determine the correction factor Z from the compressibility chart, we can
first need to calculate the reduced pressure and temperature:

P 1 MPa 
PR    0.246
Pcr 4.067 MPa 
Z  0.84
T 323 K
TR    0.863 
Tcr 374.3 K 
Thus,
v  Zvideal  (0.84)(0.02632 m 3 /kg )

The error in this result is less than 2 percent. Therefore, in the absence of
tabulated data, the generalized compressibility chart can be used with
confidence.
 Example 3.9 (Using Generalized Charts to Determine Pressure)

Determine the pressure of water vapor at 600 oF and 0.514 ft3/lbm, using (a)
the steam tables (b) the ideal equation, and (c) the generalized
compressibility chart.
Solution
The gas constant, the critical pressure, and the critical temperature of
refrigerant-134a are determine from Table A-1E to be;
R  0.05956 psia. ft 3 /lbm. R
Pcr  3204 psia
Tcr  1165.3 R
(a) The pressure at the specified state is determined from Table A-6E to be;
v  0.0514 ft 3 /lbm 
 P  1000 psia
T  600 F
o


This is the experimentally determined value, and thus it is the most accurate.
 Example 3.9 (Using Generalized Charts to Determine Pressure)-cont’

(b) The pressure of steam under the ideal-gas assumption is determined from the
ideal-gas relation to be;

P
RT

 
0.5956 psia. ft 3 /lbm. R 1060 R 
 1228 psia
3
v 0.514 ft /lbm
Therefore, treating the steam as an ideal gas would result in an error of (1228-
1000)/1000 = 0.228, or 22.8 percent in this case.
(c) To determine the correction factor Z from the compressibility chart
(Fig A-30), we first need to calculate the pseudo-reduced specific volume
and the reduced temperature.
vactual (0.514 ft 3 /lbm)(3204 psia) 
vR    2.373

3
RTcr / Pcr (0.5956 psia.ft /lbm. R)(1165.3 R)
 PR  0.33
TR 
T

1060 R
 0.91 
Tcr 1165.3 R 

Thus, P  PR Pcr  (0.33)(3204 psia)  1057 psia .

Using the compressibility chart reduced the error from 22.8 to 5.7 percent.
 8. Other Equations of State
 Van der Waals Equation: RT a
P  2 a , b  constant
V b V
27 R 2Tcr2 RTcr
where a and b 
64 Pcr 8Pcr
 Redlich/Kwong Equation:
RT a
P  1/ 2 a,b  constant
V  b T V (V  b)
 Soave/Redlich/Kwong Equation:
RT a
P  a,b  constant
V  b V (V  b)
 Peng/Robinson Equation:

RT a
P  2 a,b  constant
V  b V  2bV  b
 8. Other Equations of State –cont’
 Viral Equation:
PV
Z (3.10)
RT

Z  a( 1  B'P  C'P 2  D'P 3  ...) (3.11)

B C D
Z  1   2  3  ... (3.12)
V V V

B
B'  (3.13a )
RT

C  B2 D  3BC  2 B 3
C'  (3.13b) D'  (3.13c)
( RT ) 2 ( RT )3
 Equations of State Application

Equation Application
Ideal-gas Pr < 0.05, Tr >1.5
or, P < 2 atm, T > 25 oC
Van der Waals Only for vapor.
Lower pressure.
Viral Equation Only for vapor.
(C = D =…0) Tr > 0.436 Pr +0.6
Redlich/Kwong Only for vapor.
Lower pressure.
Soave/Redlich/Kwong Saturated vapor and saturated liquid.
Higher pressure.
Peng Robingson Saturated vapor and saturated liquid.
Higher pressure.
Standard to hydrocarbon industry.
 Thank you

Prepared by,
MISS RAHIMAH OTHMAN