Chapter 2:

Properties of Pure Substances

Pure Substance
A pure substance has a homogeneous and invariable chemical
composition and may exist in more than one phase.
Examples:
1. Water (solid, liquid, and vapor phases)
2. Mixture of liquid water and water vapor
3. Carbon dioxide, CO2
4. Nitrogen, N2
5. Mixtures of gases, such as air, as long as there is no change of
phase.
The P-V-T Surface for a Real Substance
Real substances that readily change phase from solid to liquid to
gas such as water, refrigerant-134a, and ammonia cannot be treated
as ideal gases in general.
The pressure, volume, temperature relation, or equation of state for these
substances is generally very complicated, and the thermodynamic
properties are given in table form.
The properties of these substances may be illustrated by the functional
2
relation F(P,v,T)=0, called an equation of state.
Molecules in the solid phase (a), in the liquid phase (b), and in the gas phase

3
Let's consider the results of heating liquid water from 20C, 1 atm
while keeping the pressure constant. We will follow the constant
pressure process shown in the next figures. First place liquid water
In a piston-cylinder device where a fixed weight is placed on the
piston to keep the pressure of the water constant at all times. As
liquid water is heated while the pressure is held constant, the following
events occur.
Process 1-2:
The temperature and specific volume will increase from the compressed
liquid, or subcooled liquid, state 1, to the saturated liquid state 2. In
the compressed liquid region, the properties of the liquid are
approximately equal to the properties of the saturated liquid state at the
temperature.

4
Process 2-3:
At state 2 the liquid has reached the temperature at which it begins
to boil, called the saturation temperature, and is said to exist as a
saturated liquid. Properties at the saturated liquid state are noted
by the subscript f and v2 = vf. During the phase change both the
temperature and pressure remain constant (according to the
ITS-90, water boils at 99.975C  100C when the pressure is 1 atm). At
state 3 the liquid and vapor phase are in equilibrium and any point on the
line between states 2 and 3 has the same temperature and pressure.

5
Process 3-4:
At state 4 a saturated vapor exists and vaporization is complete.
The subscript g will always denote a saturated vapor state.
Note v4 = vg.

Thermodynamic properties at the saturated liquid state and saturated vapor

state are given in Table A-4 as the saturated temperature table and Table
A-5 as the saturated pressure table. In Table A-4 the saturation temperature
is the independent property, and in Table A-5 the saturation pressure is the
independent property. The saturation pressure is the pressure at which
phase change will occur for a given temperature. In the saturation region the
temperature and pressure are dependent properties; if one is known, then
the other is automatically known. 6
Process 4-5:
If the constant pressure heating is continued, the temperature will
begin to increase above the saturation temperature, 100 C in this
example, and the volume also increases. State 5 is called a
superheated state because T5 is greater than the saturation
temperature for the pressure and the vapor is not about to condense.
Thermodynamic properties for water in the superheated region are found in
the superheated steam tables, Table A-6.
This constant pressure heating process
is illustrated in the following figure.

99.975 

7
Consider repeating this process for other constant pressure lines
as shown below.

8
If all of the saturated liquid states are connected, the saturated
liquid line is established. If all of the saturated vapor states are
connected, the saturated vapor line is established. These two
lines intersect at the critical point and form what is often called
the “steam dome.”

The region between the saturated liquid line and the saturated vapor line is
called by these terms: saturated liquid-vapor mixture region, wet region
(i.e., a mixture of saturated liquid and saturated vapor), two-phase region,
and just the saturation region.

Notice that the trend of the temperature following a constant pressure line is
to increase with increasing volume and the trend of the pressure following a
constant temperature line is to decrease with increasing volume.

9
10
The region to the left of the saturated liquid line and below the
critical temperature is called the compressed liquid region. The
region to the right of the saturated vapor line and above the critical
temperature is called the superheated region. See Table A-1 for the
critical point data for selected substances.

At temperatures and pressures above the critical point, the phase transition
from liquid to vapor is no longer discrete.

11
The P-V-T Surface for a Real Substance
Real substances that readily change phase from solid to liquid to
gas such as water, refrigerant-134a, and ammonia cannot be
Treated as ideal gases in general. The pressure, volume,
temperature relation, or equation of state for these substances is generally
very complicated, and the thermodynamic properties are given in table
form. The properties of these substances may be illustrated by the
functional relation F(P,v,T)=0, called an equation of state.

12
P-V-T Surface for a Substance
that contracts upon freezing

P-V-T Surface for a Substance

that expands upon freezing

13
The above two figures illustrate the function for a substance that
contracts on freezing and a substance that expands on freezing.
These figures show three regions where a substance like water may exist
as a solid, liquid or gas (or vapor). Also these figures show that a
substance may exist as a mixture of two phases during phase change,
solid-vapor, solid-liquid, and liquid-vapor.
Water may exist in the compressed liquid region, a region where
saturated liquid water and saturated water vapor are in equilibrium (called
the saturation region), and the superheated vapor region (the solid or ice
region is not shown).

14
Next figure shows the P-T diagram, often called the phase diagram,
for pure substances that contract and expand upon freezing.

The triple point of water is 0.01oC, 0.6117 kPa.

The critical point of water is 373.95oC, 22.064 MPa (Table A-1).

15
TABLE A-4 Saturated Water Temperature-Tables
Temp., T Sat. Specific volume, Internal energy, Enthalpy, Entropy,
C Press., Psat m3/kg kJ/kg kJ/kg kJ/kgK
kPa
Sat. liquid, Sat. Sat. liquid, Evap., Sat. Sat. Evap., hfg Sat. Sat. Evap., sfg Sat.
vf vapor, uf ufg vapor, ug liquid, vapor, hg liquid, sf vapor,
vg hf sg

0.01 0.6117 0.001000 206.00 0.00 2374.9 2374.9 0.00 2500.9 2500.9 0.0000 9.1556 9.1556

5 0.8725 0.001000 147.03 21.02 2360.8 2381.8 21.02 2489.1 2510.1 0.0763 8.9487 9.0249

10 1.228 0.001000 106.32 42.02 2346.6 2388.7 42.02 2477.2 2519.2 0.1511 8.7488 8.8999

15 1.706 0.001001 77.885 62.98 2332.5 2395.5 62.98 2465.4 2528.3 0.2245 8.5559 8.7803

20 2.339 0.001002 57.762 83.91 2318.4 2402.3 83.91 2453.5 2537.4 0.2965 8.3696 8.6661

25 3.170 0.001003 43.340 104.83 2304.3 2409.1 104.83 2441.7 2546.5 0.3672 8.1895 8.5567

30 4.247 0.001004 32.879 125.73 2290.2 2415.9 125.74 2429.8 2555.6 0.4368 8.0152 8.4520

35 5.629 0.001006 25.205 146.63 2276.0 2422.7 146.64 2417.9 2564.6 0.5051 7.8466 8.3517

40 7.385 0.001008 19.515 167.53 2261.9 2429.4 167.53 2406.0 2573.5 0.5724 7.6832 8.2556

45 9.595 0.001010 15.251 188.43 2247.7 2436.1 188.44 2394.0 2582.4 0.6386 7.5247 8.1633

50 12.35 0.001012 12.026 209.33 2233.4 2442.7 209.34 2382.0 2591.3 0.7038 7.3710 8.0748

55 15.76 0.001015 9.5639 230.24 2219.1 2449.3 230.26 2369.8 2600.1 0.7680 7.2218 7.9898

60 19.95 0.001017 7.6670 251.16 2204.7 2455.9 251.18 2357.7 2608.8 0.8313 7.0769 7.9082

65 25.04 0.001020 6.1935 272.09 2190.3 2462.4 272.12 2345.4 2617.5 0.8937 6.9360 7.8296

70 31.20 0.001023 5.0396 293.04 2175.8 2468.9 293.07 2333.0 2626.1 0.9551 6.7989 7.7540

75 38.60 0.001026 4.1291 313.99 2161.3 2475.3 314.03 2320.6 2634.6 1.0158 6.6655 7.6812

80 47.42 0.001029 3.4053 334.97 2146.6 2481.6 335.02 2308.0 2643.0 1.0756 6.5355 7.6111

85 57.87 0.001032 2.8261 355.96 2131.9 2487.8 356.02 2295.3 2651.4 1.1346 6.4089 7.5435

90 70.18 0.001036 2.3593 376.97 2117.0 2494.0 377.04 2282.5 2659.6 1.1929 6.2853 7.4782

95 84.61 0.001040 1.9808 398.00 2102.0 2500.1 398.09 2269.6 2667.6 1.2504 6.1647 7.4151

100 101.42 0.001043 1.6720 419.06 2087.0 2506.0 419.17 2256.4 2675.6 1.3072 6.0470 7.3542

۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰

۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰

360 18666 0.001895 0.006950 1726.16 625.7 2351.9 1761.53 720.1 2481.6 3.9165 1.1373 5.0537

365 19822 0.002015 0.006009 1777.22 526.4 2303.6 1817.16 605.5 2422.7 4.0004 0.9489 4.9493
16
370 21044 0.002217 0.004953 1844.53 385.6 2230.1 1891.19 443.1 2334.3 4.1119 0.6890 4.8009

373.95 22064 0.003106 0.003106 2015.8 0 2015.8 2084.3 0 2084.3 4.4070 0 4.4070
TABLE A-5 Saturated water-Pressure table
Press. Sat. Temp., Specific volume, Internal energy, Enthalpy, Entropy,
P kPa Tsat C m3/kg kJ/kg kJ/kg kJ/kgK

Sat. Sat. Sat. Evap., Sat. Sat. Evap., Sat. Sat. Evap., Sat.
liquid, vapor, liquid, ufg vapor, liquid, hfg vapor, liquid, sfg vapor,
vf vg uf ug hf hg sf sg

0.6117 0.01 0.001000 206.00 0.00 2374.9 2374.9 0.00 2500.9 2500.9 0.0000 9.1556 9.1556

1.0 6.97 0.001000 129.19 29.30 2355.2 2384.5 29.30 2484.4 2513.7 0.1059 8.8690 8.9749

1.5 13.02 0.001001 87.964 54.69 2338.1 2392.8 54.69 2470.1 2524.7 0.1956 8.6314 8.8270

2.0 17.50 0.001001 66.990 73.43 2325.5 2398.9 73.43 2459.5 2532.9 0.2606 8.4621 8.7227

2.5 21.08 0.001002 54.242 88.42 2315.4 2403.8 88.42 2451.0 2539.4 0.3118 8.3302 8.6421

3.0 24.08 0.001003 45.654 100.98 2306.9 2407.9 100.98 2443.9 2544.8 0.3543 8.2222 8.5765

4.0 28.96 0.001004 34.791 121.39 2293.1 2414.5 121.39 2432.3 2553.7 0.4224 8.0510 8.4734

5.0 32.87 0.001005 28.185 137.75 2282.1 2419.8 137.75 2423.0 2560.7 0.4762 7.9176 8.3938

7.5 40.29 0.001008 19.233 168.74 2261.1 2429.8 168.75 2405.3 2574.0 0.5763 7.6738 8.2501

10 45.81 0.001010 14.670 191.79 2245.4 2437.2 191.81 2392.1 2583.9 0.6492 7.4996 8.1488

15 53.97 0.001014 10.020 225.93 2222.1 2448.0 225.94 2372.3 2598.3 0.7549 7.2522 8.0071

20 60.06 0.001017 7.6481 251.40 2204.6 2456.0 251.42 2357.5 2608.9 0.8320 7.0752 7.9073

25 64.96 0.001020 6.2034 271.93 2190.4 2462.4 271.96 2345.5 2617.5 0.8932 6.9370 7.8302

30 69.09 0.001022 5.2287 289.24 2178.5 2467.7 289.27 2335.3 2624.6 0.9441 6.8234 7.7675

40 75.86 0.001026 3.9933 317.58 2158.8 2476.3 317.62 2318.4 2636.1 1.0261 6.6430 7.6691

50 81.32 0.001030 3.2403 340.49 2142.7 2483.2 340.54 2304.7 2645.2 1.0912 6.5019 7.5931

75 91.76 0.001037 2.2172 384.36 2111.8 2496.1 384.44 2278.0 2662.4 1.2132 6.2426 7.4558

100 99.61 0.001043 1.6941 417.40 2088.2 2505.6 417.51 2257.5 2675.0 1.3028 6.0562 7.3589

125 105.97 0.001048 1.3750 444.23 2068.8 2513.0 444.36 2240.6 2684.9 1.3741 5.9100 7.2841

۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰

۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰ ۰

20,000 365.75 0.002038 0.005862 1785.84 509.0 2294.8 1826.59 585.5 2412.1 4.0146 0.9164 4.9310

21,000 369.83 0.002207 0.004994 1841.62 391.9 2233.5 1887.97 450.4 2338.4 4.1071 0.7005 4.8076

22,000 373.71 0.002703 0.003644 1951.65 140.8 2092.4 2011.12 161.5 2172.6 4.2942 0.2496 4.5439

22,064 373.95 0.003106 0.003106 2015.8 0 2015.8 2084.3 0 2084.3 4.4070 0 4.4070 17
Property Tables
In addition to the temperature, pressure, and volume data,
Tables A-4 through A-8 contain the data for the specific internal
energy u, the specific enthalpy h, and the specific entropy s. The
enthalpy is a convenient grouping of the internal energy, pressure,
and volume and is given by
H  U  PV
The enthalpy per unit mass is
h  u  Pv
 We will find that the enthalpy h is quite useful in calculating the energy of
mass streams flowing into and out of control volumes.
 The enthalpy is also useful in the energy balance during a constant
pressure process for a substance contained in a closed piston-cylinder
device.
 The enthalpy has units of energy per unit mass, kJ/kg.
 The entropy s is a property defined by the second law of thermodynamics
and is related to the heat transfer to a system divided by the system
temperature; thus, the entropy has units of energy divided by temperature.
The concept of entropy is explained in Chapters 6 and 7. 18
Saturation pressure is the pressure at which the liquid and vapor
phases are in equilibrium at a given temperature.

Saturation temperature is the temperature at which the liquid and

vapor phases are in equilibrium at a given pressure.

The subscript fg used in Tables A-4 and A-5 refers to the difference between
the saturated vapor value and the saturated liquid value region. That is,

u fg  ug  u f
h fg  hg  h f
s fg  sg  s f

The quantity hfg is called the enthalpy of vaporization (or latent heat of
vaporization). It represents the amount of energy needed to vaporize a unit
of mass of saturated liquid at a given temperature or pressure. It decreases
as the temperature or pressure increases, and becomes zero at the critical
point.

19
Quality and Saturated Liquid-Vapor Mixture
Now, let’s review the constant pressure heat addition process for
water shown in Figure 3-11. Since state 3 is a mixture of saturated
liquid and saturated vapor, how do we locate it on the T-v diagram?
To establish the location of state 3 a new parameter called the
quality x is defined as
mass saturatedvapor mg
x 
mass total m f  mg
The quality is zero for the saturated liquid and one for the saturated vapor (0
≤ x ≤ 1). The average specific volume at any state 3 is given in terms of the
quality as follows. Consider a mixture of saturated liquid and saturated
vapor. The liquid has a mass mf and occupies a volume Vf. The vapor has
a mass mg and occupies a volume Vg.

20
We note
V  V f  Vg
m  m f  mg
V  mv , V f  m f v f , Vg  mg v g

mv  m f v f  mg v g
mf v f mg v g
v 
m m
Recall the definition of quality x
mg mg
x 
m m f  mg
Then
mf m  mg
  1 x
m m
Note, quantity 1- x is often given the name moisture. The specific volume of
the saturated mixture becomes
v  (1  x )v f  xv g
21
The form that we use most often is
v  v f  x (v g  v f )

It is noted that the value of any extensive property per unit mass in
the saturation region is calculated from an equation having a form
similar to that of the above equation. Let Y be any extensive property and let
y be the corresponding intensive property, Y/m, then

Y
y  y f  x( yg  y f )
m
 y f  x y fg
where y fg  y g  y f

The term yfg is the difference between the saturated vapor and the saturated
liquid values of the property y; y may be replaced by any of the variables v,
u, h, or s.

We often use the above equation to determine the quality x of a saturated

liquid-vapor state.
22
The following application is called the Lever Rule:
y  yf
x
y fg

The Lever Rule is illustrated in the following figures.

23
Superheated Water Table
A substance is said to be superheated if the given temperature is
greater than the saturation temperature for the given pressure.
In the superheated water Table A-6, T and P are the independent
properties. The value of temperature to the right of the pressure is
the saturation temperature for the pressure.
The first entry in the table is the saturated vapor state at the pressure.

24
Compressed Liquid Water Table
A substance is said to be a compressed liquid when the pressure
is greater than the saturation pressure for the temperature.
Data for water compressed liquid states are found in the compressed liquid
tables, Table A-7. Table A-7 is arranged like Table A-6, except the
saturation states are the saturated liquid states. Note that the data in Table
A-7 begins at 5 MPa or 50 times atmospheric pressure.

25
At pressures below 5 MPa for water, the data are approximately
equal to the saturated liquid data at the given temperature. We
approximate intensive parameter y, that is v, u, h, and s data as
y  y f @T
For example, the compressed liquid enthalpy may be approximated by
h  h f @T

26
How to Choose the Right Table
The correct table to use to find the thermodynamic properties of a
real substance can always be determined by comparing the known
state properties to the properties in the saturation region. Given
the temperature or pressure and one other property from the group
v, u, h, and s, the following procedure is used. For example if the
pressure and specific volume are specified, three questions are
asked: For the given pressure,
Is v  v f ?  compressed liquid
Is v f  v  vg ?  saturated mixture
Is vg  v ?  superheated steam

Some tables may not always give the internal energy. When it is not listed,
the internal energy is calculated from the definition of the enthalpy as
u  h  pv

27
Equations of State

The relationship among the state variables, temperature, pressure,

and specific volume is called the equation of state. We now consider
the equation of state for the vapor or gaseous phase of simple
compressible substances.

Ideal Gas
Based on our experience in chemistry and physics we recall that the
combination of Boyle’s and Charles’ laws for gases at low pressure result in
the equation of state for the ideal gas as

where R is the constant of proportionality and is called the gas constant and
takes on a different value for each gas. If a gas obeys this relation, it is
called an ideal gas. We often write this equation as

Pv  RT
28
The gas constant for ideal gases is related to the universal gas
constant valid for all substances through the molar mass (or
molecular weight). Let Ru be the universal gas constant. Then,
Ru
R
M
The mass, m, is related to the moles, N, of substance through the molecular
weight or molar mass, M, see Table A-1. The molar mass is the ratio of
mass to moles and has the same value regardless of the system of units.
g kg lbm
M air  28.97  28.97  28.97
gmol kmol lbmol
Since 1 kmol = 1000 gmol or 1000 gram-mole and 1 kg = 1000 g, 1 kmol of
air has a mass of 28.97 kg or 28,970 grams.
mNM

29
The ideal gas equation of state may be written several ways.
pv  RT
pV  mRT
pV  NRuT
pv  RuT
Here P = absolute pressure in MPa, or
kPa
v = molar specific volume in
m3/kmol
T = absolute temperature in K
Ru = 8.314 kJ/(kmolK)
Some values of the universal8.314 kJ/(kmolK)
gas constant are Ru
8.314
kPam3/(kmolK)
1.986
Btu/(lbmolR)
1545
ftlbf/(lbmolR)
30
10.73
psiaft3/(lbmolR)
The ideal gas equation of state can be derived from basic principles
if one assumes
1. Intermolecular forces are small.
2. Volume occupied by the particles is small.
The ideal gas equation of state is used when
(1)When the pressure is small compared to the critical pressure OR
(2)when the temperature is twice the critical temperature and the pressure is
less than 10 times the critical pressure. Critical point data are given in Table
A-1.

Compressibility Factor

To understand the above criteria and to determine how much the ideal gas
equation of state deviates from the actual gas behavior, we introduce the
compressibility factor Z as follows.

Pv  Z Ru T
or
Pv
Z 31

Ru T
For an ideal gas Z = 1, and the deviation of Z from unity measures
the deviation of the actual P-V-T relation from the ideal gas equation
of state. The compressibility factor is expressed as a function of the
reduced pressure and the reduced temperature. The Z factor is
approximately the same for all gases at the same reduced
temperature and reduced pressure, which are defined as

T P
TR  and PR 
Tcr Pcr
where Pcr and Tcr are the critical pressure and temperature, respectively.
The critical constant data for various substances are given in Table A-1.
This is known as the principle of corresponding states. Figure 3-51 gives a
comparison of Z factors for various gases and supports the principle of
corresponding states.

32
When either P or T is unknown, Z can be determined from the compressibility
chart with the help of the pseudo-reduced specific volume, defined as
v
v R  actual
R Tcr
Pcr 33
Figure A-15 presents the generalized compressibility chart based
on data for a large number of gases.
These charts show the conditions for which Z = 1 and the gas
behaves as an ideal gas:

1. PR < 10 and TR > 2 or P < 10Pcr and T > 2Tcr

2. PR << 1 or P << Pcr

Note: When PR is small, we must make sure that the state is not in the
compressed liquid region for the given temperature. A compressed liquid
state is certainly not an ideal gas state.
For instance the critical pressure and temperature for oxygen are 5.08 MPa
and 154.8 K, respectively. For temperatures greater than 300 K and
pressures less than 50 MPa (1 atmosphere pressure is 0.10135 MPa)
oxygen is considered to be an ideal gas.

34
If the system pressure is low enough and the temperature high
enough (P and T are compared to the critical values), gases will
behave as ideal gases. Consider the T-v diagram for water. The
figure below shows the percentage of error for the volume
([|vtable – videal|/vtable]x100) for assuming water (superheated steam)
to be an ideal gas.

35
Other Equations of State

Many attempts have been made to keep the simplicity of the ideal gas
equation of state but yet account for the intermolecular forces and volume
occupied by the particles. Three of these are

van der Waals:

a
(P  2
)(v  b)  R T
v
where
27 R 2 Tcr2 RTcr
a and b
64 Pcr 8 Pcr

36
Beattie-Bridgeman:

where

The constants a, b, c, Ao, Bo for various substances are found in Table 3-4.

Benedict-Webb-Rubin:

The constants for various substances appearing in the Benedict-Webb­-Rubin

equation are given in Table 3-4.

37
The Systematic Thermodynamics Solution Procedure

When we apply a methodical solution procedure, thermodynamics

problems are relatively easy to solve. Each thermodynamics problem is
approached the same way as shown in the following, which is a
modification of the procedure given in the text:

Thermodynamics Solution Method

1. Sketch the system and show energy interactions across the boundaries.

2. Determine the property relation. Is the working substance an ideal gas or a real
substance? Begin to set up and fill in a property table.

3. Determine the process and sketch the process diagram. Continue to fill in the
property table.

4. Apply conservation of mass and conservation of energy principles.

5. Bring in other information from the problem statement, called physical constraints,
such as the volume doubles or the pressure is halved during the process.
38
6. Develop enough equations for the unknowns and solve.