MAE 204 Thermodynamics Chapter 3

Chapter 3 (Properties of Pure Substances)

Pure Substance: Any substance with a fixed and uniform chemical composition, e.g.
A substance with a single element or compound.
A substance with a uniform, well mixed (homogeneous) materials, e.g. air, water.
A mixture of water and oil at equilibrium is not a pure substance, but individually they are pure
substances.

Oil

Water

1. Solid (Crystalline): The molecules are in a well-defined 3-D pattern called lattice. The
bonds between molecules are strong, but not rigid. Molecules oscillate and the amount of
oscillation depends on temperature.
2. Liquid: Molecules are still together, with the intra molecular distances are about the same
as solid. But intra molecular bonds are weaker. Molecules rotate, slide, shear etc.
3. Gas (Vapor): Intermolecular distance is huge and bonds are significantly week. They
expand to fill the container.

Gas

Liquid

Solid

Phase Change of Pure Substance: A system of a pure substance will undergo a phase change like
figure.
Solidification Vaporization/Boiling
Solid Liquid Gas
Melting Liquefaction

Sublimation

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MAE 204 Thermodynamics Chapter 3

During phase change huge energy is added or reduced to or from the system. Look at the heating
of liquid water in a piston-cylinder that maintains pressure at 1 atm.

State 1 – Compressed liquid (or sub cooled liquid): For a compressed liquid (Figure 1)
Energy added to the liquid will not result in any vapor formation.
The temperature will increase.
The fluid will expand.
It continues up to boiling point (100°C).

P = 1 atm
T = 20°C

Qin
Figure 1: Sub cool liquid to saturated liquid

State 2 – Saturated liquid: P = 1 atm and T = 100°C

It is still al liquid.
Any energy added to the system, a portion of liquid will boil (phase change).
Any energy removed from the system, will not change the phase.
The stage is called saturated liquid.

State 3 – Two phase (liquid + vapor): P = 1 atm and T = 100°C (Figure 2)

A part is saturated liquid and rest is saturated vapor (a gas at 1atm and 100°C).
Any energy loss results in fewer vapors and more liquid.
Any energy gain results in more vapors and less liquid.
The temperature and pressure remain constant in this state.

Vapor

Liquid

Qin

Figure 2: Saturated mixture

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MAE 204 Thermodynamics Chapter 3

State 4 – Saturated vapor: P = 1 atm and T = 100°C

The substance is all vapor.
Any energy loss results in a phase change of liquefaction.

State 5 – Superheated vapor:

A vapor that is not about to condense.
Any energy change will result in a temperature change.
It starts from boiling point (100°C).

The sequence is represented in T-v diagram.

Superheated
Saturated Vapor
Liquid 5

2 3 4
Compressed
Saturated
Liquid
Vapor

1
v

Figure 3: From state 1 to state 5

For a given material, the temperature and pressure at which a saturated mixture occurs called the
saturation temperature (Tsat) and saturation pressure (Psat)

Tsat: For a given pressure, Tsat is the temperature at which a pure substance changes phase
between a vapor and liquid.

Psat: For a given temperature, Psat is the pressure at which a pure substance changes phase
between a vapor and liquid.

Latent heat: The total amount of energy needed to convert a saturated liquid to a saturated vapor
is called the latent heat of vaporization. This depends on material, temperature and pressure. The
same for solid to liquid is called the latent heat of fusion.

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MAE 204 Thermodynamics Chapter 3

Property diagram: It is a diagram that relates state variables (e.g. T, v, P, h etc.) to the phase of
the system, e.g. T-v (Temperature vs Specific volume), P-v (Pressure vs Specific volume), P-T
(Pressure vs Temperature) etc.

P3 > P2
Superheated
Compressed Vapor
P2 > P1
Liquid

Saturated
Liquid P1 = Constant

Saturated
Vapor

Saturation Curve

v
Figure 4: T-v diagram

As the pressure increases, the saturated liquid and saturated vapor points get closer. At some
pressure these two points coincide, and this is called the critical point. The corresponding
pressure, temperature and specific volume at this point are called critical pressure, temperature
and specific volume respectively.

These are material constants and for water, these value are found from Table A-1, which are Tcr
= 373.95°C, Pcr = 22.06 MPa and Vcr = 0.003106 m³/kg.

If we join all saturation points, we get the saturation curve (Figure 4). Left of this curve is the
state of compressed (or sub cooled) liquid, right of this curve is the superheated vapor and
beyond the critical point it is gas.

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MAE 204 Thermodynamics Chapter 3

This can be drawn in P-v diagram,

Critical
Point
Superheated
Compressed Vapor
Liquid

Saturated
Liquid
Saturated
Vapor

Saturation Curve

Figure 5: P-v diagram

Now, we need to include the solid phases for two different kinds of fluids.

(i) Materials that contract on freezing (most)

(ii) Material that expands on freezing (water)

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MAE 204 Thermodynamics Chapter 3

Liquid
Critical
Point
Pressure
Triple
Solid Line
Liquid-
Vapor

Vapor
Solid-
TC
Vapor
Specific Temperature
Volume

(a)

Solid

S L

Pressure Pressure Saturated

Liquid Critical
Critical Vapor line
Point
Solid Saturated Point
PC
Liquid line
L
Liquid-
V Vapor Vapor
Vapor
Triple Line TC
S Triple Point
V Solid- Vapor
Temperature Specific Volume
(b) (c)
Figure: P-v-T surface and projection for a substance that expands on freezing (a) three dimensional
view (b) phase diagram of P-T plane (c) P-v diagram

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MAE 204 Thermodynamics Chapter 3

Solid-
Liquid

Constant
pressure line
Liquid
Critical
Pressure Point
Solid Triple
Line
Liquid-
Vapor

Vapor
Solid-
TC
Vapor
Specific Temperature
Volume

(a)
Solid-
Solid Liquid

S L
Liquid
Pressure Pressure
Critical Critical
Solid Point
PC Point
L Liquid-
V Vapor Vapor
Vapor
Triple Line TC
S Triple Point
V Solid- Vapor
Temperature Specific Volume
(b) (c)
Figure: P-v-T surface and projection for a substance that contracts on freezing (a) three
dimensional view (b) phase diagram of P-T plane (c) P-v diagram

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MAE 204 Thermodynamics Chapter 3

The diagrams are good qualitative measures. They do not give qualitative understandings. For
that, we need property table in the back of the book. The following figures shows the table
number for the properties correspond the area of the fluid.

Pressure

A7

A4 + A5
A6
A8
Solid- Vapor
Specific Volume

Review of Linear Interpolation:

Say that you have a linear function, f(x) = ax + b. Let f(0) = 0 and f(1) = 1.

What is f(½) = ?, here f(½) = ½

f(½)

x
½ 1

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MAE 204 Thermodynamics Chapter 3

Now, say that f(0) = 0 and f(2) = 1, then f(½) = ¼

f

1 (2, 1)

f(½)

x
(0, 0) 1 2

Now, say that f(½) = ¼, f(1½) = -1, f(⅝) = ?

f

x
(0, 0) ½ 1 1½ 2

f(½)

−1

Two ways to get f(⅝),

1. Use a calculator
2. Do manual interpolation. Let's two data points be (x1, f1) and (x3, f3).
We want the value of f2 at x2, where x1 ≤ x2 ≤ x3.

Linear interpolation means,

f 3  f1 f f f f f f
 2 1  3 2 , So, f 2  f1  3 1 x 2  x 1 
x 3  x1 x 2  x1 x 3  x 2 x 3  x1
You may have to do 2D linear interpolation.

Data point Data point

3 1-D linear
interpolation

Data point Data point

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MAE 204 Thermodynamics Chapter 3

Look at a sample point in Table A-4,

Enthalpy: This is a convenience property. It is defined as,
h = u + Pv (kJ/kg)
H = U + PV (kJ)

Entropy: Deals with 2nd law (later). Many properties cannot be determined directly.
To measure, look at the change from a reference state. The references are;
Water: Saturation liquid at 0.01°C
R134a: Saturation liquid at −40°C
(Thus values may be negative)

How to identify the state / How to read a property table?

1. Saturated liquid or Saturated vapor phase: Simply identify the correct table and read the
data. You many have to do interpolation.
2. Saturation mixture: A mixture is defined as a portion of the substance in a saturated
liquid and the rest is a saturated vapor. The mass ratio of the vapor to the total mass is
called the steam quality of the system.
m vapor m vapor
x 
m total m vapor  m liquid
x = 0 means all saturated liquid
x = 1 means all saturated vapor
0≤x≤1
The quality is a property. It allows you to obtain the average property of the system.
Quantity y: yave = yf + x(yg − yf) = yf + x yfg

Example problems may include:

1. Given x and T, find u.
2. Given P and u, find x.
3. Compressed liquid: Typically compressed liquid table are not available. This is because liquid
properties change little under pressure. They depend much more on temperature.
Thus, if property table is not available, say that, y = yf@T (The property of the saturated liquid at
the same temperature), except enthalpy,
h = hf@T + vf@T (P − Psat@T)
A compressed liquid has,
a. P > Psat at given T.
b. T < Tsat at given P.
c. v < vf at P or T.
d. u < uf at P or T.
e. h < hf at P or T.
4. Superheated vapor: Too much variation with T & P. We must use tables. A superheated vapor
has:
a. P < Psat at given T.
b. T > Tsat at given P.
c. v > vg at P or T.
d. u > ug at P or T.
e. h > hg at P or T.

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MAE 204 Thermodynamics Chapter 3

Equations of State:

An equation of state is an explicit relationship among P, V and T. Most material do not have an
equation of state. But experiment and theoretical evidence show that the relationship (PV=NRuT,
ideal gas law) holds true for some gases. Here, P = Pressure, T = Temperature, V = Volume, N =
# of moles, Ru = Universal gas constant = 8.314 kJ/kmole.K

If we define, R = Ru/M (M = Molecular mass of a gas), then PV = mRT or Pv = RT.

The book has the R values for different gases (Table A-1), e.g. He has the value of 2.0769
kJ/kg.K

Any gas that obeys Pv = RT exactly is an ideal gas. The ideal gases do not exist, but in some
situation it is a close approximation.

Say, that we have a closed system with N moles of a gas. At state 1, we have P1, v1 and T1 and at
state 2, we have P2, v2 and T2. If this is an ideal gas, then

P1v1 Pv Pv Pv
P1v1  RT1   R and similarly 2 2  R , so 1 1  2 2
T1 T2 T1 T2

This relates the states of a closed system with an ideal gas.

Ideal gas approximation holds true when

a. There are very low pressures.
b. If the temperature is very high, but the pressure is not very high.

To classify how close a gas is to ideal gas, use the compressibility factor, Z, which is related as
Pv = ZRT, where Z = 1 for iedal gas.

If we define, videal = RT/P, then Z = vactual/videal

To see how Z changes with P and T, define the reduced pressure PR and reduced temperature TR,
as PR = P/Pcr and TR = T/Tcr

If you plot Z versus PR and TR for various gases, patterns take place. A gas is close to ideal
when,

1. PR << 1
2. TR > 2

Largest deviation from ideal gas is for PR  1 and TR  1.

v actual
Table A-15 has the Z chart. There is also pseudo-reduced specific volume: v R 
RTcr Pcr

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MAE 204 Thermodynamics Chapter 3

Other gas equation of states:

 a  27 R 2 Tcr2 RTcr
(a) Van der Waals:  P  2 v  b  RT , where, a  and b 
 v  64 Pcr 8Pcr

R uT  C  A
(b) Beatie Bridgeman: P  2 
1  2 3 v  B  2 ,
v  vT  v
 a  b
where, A  A 0 1   and B  B0 1  
 v  v

(c) Benedict-Webb-Ruben: Eq. 3-26 in page 143.

RT a T  bT  cT 
(d) Virial: P   2  3  4  ......
v v v v
The a(T), b(T), c(T)’s are found experimentally.

1. A gas with a compressibility factor of Z = 0.80 and Pcr = 4MPa and Tcr = 300K, is at a P
= 14MPa, what is T and v?
Sol. Let R = 0.08 kPA.m³/kg.K
P 14MPa
We know that PR    3.5 , Z = 0.8
Pcr 4MPa
Look at Table A-15, then, vR = 0.35, TR = 1.5
T T
So, TR   1.5   T  450K
Tcr 300K
v actual v actual
Volume, v R   0.35   v actual  0.0021m3 kg
RTcr Pcr 0.08  300 4000
RT 0.08  450
Here, videal    vactual  0.00257m3 kg
P 14000
Note that, videal  Zv actual  0.8  0.00257 m3 kg  0.0021 m3 kg

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MAE 204 Thermodynamics Chapter 3

Phase Problems:
2. Locate the states in P-v and T-v diagrams for the following data.

(a) P = 80 lbf/in² = 80 Psia

P T T = 312.07 °F
80 Psi
Two-phase liquid-vapor
mixture
80 Psi 312.07°F vf = 0.01757 ft³/lb.m,
312.07°F
vg = 5.4733 ft³/lb.m
v = 3 ft³/lb.m
v v then, x = 0.55

(b)
P T 80 Psi
P = 80 lbf/in²
400°F T = 400 °F
80 Psi 312.07°F Superheated
400°F
312.07°F vapor

v v
(c)
P T 360 Psi
247.1 Psi
T = 400 °F
360 Psi P = 360 lbf/in²
247.1 Psi 400°F Subcooled (compressed)
400°F liquid

v v

(d)
P T
89.6 Psi
70 Psi T = 320 °F
P = 70 Psi
89.6 Psi 320°F Superheated
70 Psi
320°F vapor

v v

(e)
P T 14.7 Psi
0..0309 Psi
T = 10 °F
14.7 Psi P = 14.7 lbf/in²
0..0309 Psi 10°F Solid
10°F

v v

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MAE 204 Thermodynamics Chapter 3

Phase Problems:
3. Locate the states in P-v and T-v diagrams for the following data.

(a) P = 5 bar
P T T = 151.9 °C = Tsat
5 bar
Two-phase liquid-
vapor mixture
5 bar 151.9°C uf = 639.54 kJ/kg
151.9°C
ug = 2560.7 kJ/kg
u = 2000 kJ/kg
v v So, x = 0.71

(b) P = 5 bar = 0.5MPa

P T
5 bar T = 200°C
200°C Superheated vapor
Table A-6,
5 bar 151.9°C
200°C v = 0.42503 m³/kg,
151.9°C u = 2643.3 kJ/kg,
h = 2855.8 kJ/kg
v v
(c) P = 2.5MPa = 25 bar
P T 25 bar T = 200 °C
15.54 bar
Subcooled (compressed)
25 bar liquid (Table A-7)
15.54 bar 200°C
200°C

v v
T = 160 °C, P = 0.48 MPa
(d) Superheated vapor (A6)
P T At 0.4MPa (h150°C = 2752.8,
6.178 bar h200°C = 2860.9, So h160°C =
4.8 bar
2774.42 kJ/kg)
6.178 bar 160°C At 0.5MPa (h151.83°C =
4.8 bar 2748.1, h200°C = 2855.8, So
160°C h160°C = 2766.37 kJ/kg)
v v So, at 0.48MPa,
h = 2767.98 kJ/kg
(e)
P T 100 kPa
0.2176 kPa
T = –12 °C
100 kPa P = 1 bar = 100 kPa
0.2176 kPa –12°C Solid
–12°C

v v

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