BFF2233 THERMO Chap 3 PDF

BFF 2233
Thermodynamics
Prepared by : Ahmad Redza bin Ahmad Mokhtar

E-mail: ahmadredza@ump.edu.my
BFF 2233 THERMODYNAMICS
Topic 3. Properties of Pure Substances
OBJECTIVES
1. Introduce the concept of a pure substance.
2. Discuss the physics of phase-change processes.
3. Illustrate the P-v, T-v, and P-T property diagrams and P-v-T surfaces
of pure substances.
4. Demonstrate the procedures for determining thermodynamic
properties of pure substances from tables of property data.
5. Describe the hypothetical substance “ideal gas” and the ideal-gas
equation of state.
6. Apply the ideal-gas equation of state in the solution of typical
problems.
7. Introduce the compressibility factor, which accounts for the
deviation of real gases from ideal-gas behavior.
8. Present some of the best-known equations of state.
3.1 Pure Substances
A substance that has a fixed chemical composition throughout.

 Air is a mixture of several gases, but it is considered to be a pure
substance.
Nitrogen and gaseous air are (a) Mixture of liquid and gaseous water is pure
pure substances substance
(b) Mixture of liquid and gaseous air is not pure
substance due to different composition
3.2 Phases of Pure Substances
 In a solid, the attractive and repulsive forces between the

molecules tend to maintain them at relatively constant
distances from each other.
 The molecules in a solid are kept at their positions by the
large spring-like inter-molecular forces.
4
3.3 Phase-change Processes of Pure Substances
Compressed and Saturated Liquid
• Compressed liquid (sub-cooled liquid): A substance not about to vaporize.

• Saturated liquid: A liquid that is about to vaporize.
At 1 atm and At 1 atm pressure

20°C, water and 100°C, water
exists in the exists as a liquid
liquid phase that is ready to
(compressed vaporize
liquid). (saturated liquid).
Saturated and Superheated Vapor
• Saturated vapor: A vapor that is about to condense.
• Saturated liquid–vapor mixture: Liquid and vapor phases coexist in equilibrium.
• Superheated vapor: A vapor that is not about to condense; not a saturated vapor.
As more heat is transferred, Temperature remains As more heat is transferred,

part of the saturated liquid constant at 100°C until the temperature of the
vaporizes (saturated liquid– vaporized (saturated vapor starts to rise
6
vapor mixture). vapor). (superheated vapor).
G 5
3
4
L L G
+
T-v diagram for the heating process of water at constant pressure.

Saturated liquid: Superheated vapor :
water exists as a liquid A vapor that is not
that is ready to about to condense
vaporize.
G 5
3
4
L L G
+ Saturated vapor :
-The last drop of
liquid is vaporized at
100°C.
- A vapor that is
about to condense

Process 1 and 5 can be reversed

by cooling the water while
maintaining the pressure.
The water will go back to state 1
with the same path, and released 5
exactly same amount of heat
added during the heating
process.
3
4

• Boiling point depends on the pressure and temperature. Solid-Liquid
Liquid-Gas
• Water boils at 100C at 1 atm pressure.
• Saturation temperature Tsat: The temperature at which a pure substance
begins or ends phase change at a given pressure.
• Saturation pressure Psat: The pressure at which a pure substance begins or
ends changes phase at a given temperature.
The liquid–vapor saturation (Boiling) curve of a pure substance (water).

• 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.
Latent heat
Of Vaporization
L 3
At 1 atm pressure, the latent heat of fusion of

water is 333.7 kJ/kg and the latent heat of
vaporization is 2256.5 kJ/kg.
• Property diagrams such as the T-v, P-v, and P-T diagrams can help in
understanding the variations of properties during phase-change processes.
Superheated
Vapour
Liquid
Saturated liquid-vapour
T-v diagram of phase-change processes of a pure substance at constant-pressure (numerical

values are for water).
• Property diagrams such as the T-v, P-v, and P-T diagrams can help in
understanding the variations of properties during phase-change processes.
Superheated
Vapour
Liquid
Saturated liquid-vapour
T-v diagram of phase-change processes of a pure substance at constant-pressure (numerical

values are for water).
Supercritical State
Critical Point
Compressed Superheated
Liquid Region Vapor Region
Or
G
Subcooled
Liquid State
L G
L +
Saturated Liquid-Vapor Region
T-v diagram of a pure substance.

Critical Point
Supercritical State
Critical Point
ssed Superheated
Region Vapor Region
ed G
tate
L G
L + - At supercritical
pressures (P > Pcr),
Saturated Liquid-Vapor Region there is no distinct
phase-change (boiling)
process.
- The highest pressure
and temperature at
which distinct liquid
T-v diagram of a pure substance. and gas phases can
coexist
P-v diagram of a pure substance.

Saturation Temperature and Saturation Pressure
• 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. It is equivalent to the
amount of energy released during freezing.
• Latent heat of vaporization: The amount of energy
absorbed during vaporization and it is equivalent to
the energy released during condensation.
• The magnitudes of the latent heats depend on the
temperature or pressure at which the phase change
occurs.
• At 1 atm pressure, the latent heat of fusion of water
is 333.7 kJ/kg and the latent heat of vaporization is
2256.5 kJ/kg.
• The atmospheric pressure, and thus the boiling
temperature of water, decreases with elevation.
3.4 Property Diagrams For Phase-change Processes
Extended P-v Diagrams to Include the Solid Phase
At triple-point pressure and temperature

substance exists in three phases in
equilibrium.
Most substance s contract during
solidification
3.4 Property Diagrams For Phase-change Processes
Extended P-v Diagrams to Include the Solid Phase
At triple-point pressure and temperature

substance exists in three phases in
equilibrium.
Water expand during solidification
Ttp = 0.01°C , Ptp = 0.6117 kPa
3.5 Property Table
• Thermodynamic properties relationships in most substance are complex,
• calculation using the relations and measurable properties,
• frequently presented in the form of tables e.g. steam table
Enthalpy—A Combination Property

The combination u + Pv is frequently encountered in the analysis of control volumes.
Pressure  volume = Energy

3.5 Property Table
Saturated Liquid and Vapor States
• Table A–4: Saturation properties of water under temperature.
• Table A–5: Saturation properties of water under pressure.
Enthalpy of vaporization, hfg

(Latent heat of vaporization)
The amount of energy needed to vaporize a unit
mass of saturated liquid at a given temperature
or pressure.
3.5 Property Table
Examples 3-1: A rigid tank contains 50kg of saturated liquid water at 90℃.
Determine the pressure in the tank and the volume of the tank.
Solution:
3.5 Property Table
Examples 3-1: A rigid tank contains 50kg of saturated liquid water at 90℃.
Determine the pressure in the tank and the volume of the tank.
Solution:
0.001036 m3/kg
3.5 Property Table
Examples 3-2: A piston-cylinder device contains 0.06m3 of saturated water

vapor at 350kPa. Determine the temperature and the mass of the
vapor inside the cylinder.
Solution:
3.5 Property Table
Examples 3-2: A piston-cylinder device contains 0.06m3 of saturated water

vapor at 350kPa. Determine the temperature and the mass of the
vapor inside the cylinder.
Solution:
0.001079 m3/kg
3.5 Property Table
Examples 3-3: A mass of 200g of saturated liquid water is completely vaporized

at a constant pressure of 100kPa. Determine
(a) The volume change
(b) the amount of energy transfered to
the water.
Solution:
3.5 Property Table
Examples 3-3: A mass of 200g of saturated liquid water is completely vaporized

at a constant pressure of 100kPa. Determine
(a) The volume change
(b) the amount of energy transfered to
the water.
Solution:
0.001043 m3/kg 1.6941 m3/kg

3.5 Property Table
Saturated Liquid and Vapor Mixture
Quality x : The ratio of the mass of vapor to the total mass of the mixture.
0: Saturated liquid 1: Saturated vapour
Temperature
and pressure are
dependent
properties for a
mixture.
A two-phase system can be

treated as a homogeneous
mixture for convenience.
3.5 Property Table
Definition
Quality
Similarly
3.5 Property Table
Examples 3-4: A rigid tank contains 10kg of water at 90 ℃. If 8kg of the water is in
liquid form and in the rest is in the vapor form, determine:
(a) The pressure in the tank 10 kg water: determine V, x, v
Water
(b) The volume of the tank
3.5 Property Table
Examples 3-4: A rigid tank contains 10kg of water at 90 ℃. If 8kg of the water is in
liquid form and in the rest is in the vapor form, determine:
(a) The pressure in the tank 10 kg water: determine V, x, v
Water
(b) The volume of the tank
Solution:
(a) Under saturated liquid and vapor mixture,
temperature and pressure are dependence properties.
Thus, from table A-4. At Tsat= 90 ℃, Psat= 70.183kPa.
(b) From equation V=Vf+Vg=mvf+mvg, V= 4.73m3
Or
From x=mg/mt, v=vf +xvg and V=mv, V= 4.73m3
3.5 Property Table
Superheated Vapor
Region to the right of the saturated vapor line, substance is in superheated
vapor where temperature and pressure are independent properties.
P
At specified P,
superheated
vapor exists at
a higher h than
the saturated
vapor.
A partial listing of Table A–6.

3.5 Property Table
Superheated Vapor
Examples 3-7: Determine the temperature of
water at a state of P = 0.5MPa and
h= 2890kJ/kg
3.5 Property Table
Superheated vapor
Examples 3-7: Determine the temperature of
water at a state of P = 0.5MPa and
h= 2890kJ/kg
Solution: At 0.5MPa, hg = 2748.1 kJ/kg.
Thus, we know the water is under
superheated vapor state.
From Table A-6, we know at T = 200℃
degree, h= 2855kJ/kg and at T= 250℃,
h= 2961kJ/kg.
Thus, by linear interpolation, when h of
water is 2890kJ/kg, T= 216℃
3.5 Property Table
Compressed Liquid
•Compressed liquid tables are not commonly available. (Table-A7)
•Because compressed liquid properties depend on temperature more than on pressure.
(dP=100times -> dv or du=1% changes). (v(T,P)=v(T))
•A compressed liquid may be approximated as a saturated liquid at the given temperature.
•However, enthalpy h is sensitive to

variations of pressure.
•A more accurate relation for enthalpy h
3.6 The Ideal-gas Equation of State
• Equation of state: Relates pressure, temperature, and specific volume of substance.
• The simplest and best-known equation of state for substances in the gas phase is the
ideal-gas equation of state.
• It can predict P-v-T with simpler calculation and accurately within some properly
selected region (Real gases behave as an ideal gas at low P, high T)
Ideal gas equation of state

where,
= gas constant
M =molar mass (kg/kmol)
Ru =universal gas constant
Gas constants of different substances

Ideal Gas Law – relates the pressure, volume and temperature in one compact
equation. The properties of an ideal gas at two different states:
𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
=
𝑻𝟏 𝑻𝟐
Examples
1. The gage pressure of an automobile tire is measured to be 210 kPa before a trip and 220
kPa after the trip at a location where the atmospheric pressure is 95 kPa. Assuming the
volume of the tire remains constant and the air temperature before the trip is 25 oC,
determine air temperature in the tire after the trip.
2. A rigid tank whose volume is unknown is divided into two parts by a partition. One side of
the tank contains an ideal gas at 927 oC. The other side is evacuated and has a volume twice
the size of the part containing the gas. The partition is now removed and the gas expands to
fill the entire tank. Heat is now applied to the gas until the pressure equals the initial
pressure. Determine the final temperature of the gas.
Is Water Vapor an Ideal Gas?
 At pressures below 10 kPa, water vapor can

be treated as an ideal gas, regardless of its
temperature, with negligible error (less
than 0.1 percent).
 At higher pressures, however, the ideal gas
assumption yields unacceptable errors,
particularly in the vicinity of the critical
point and the saturated vapor line.
 In air-conditioning applications, the water
vapor in the air can be treated as an ideal
gas. Why? (Pressure is low)
 In steam power plant applications,
however, the pressures involved are usually
very high; therefore, ideal-gas relations
should not be used. (Pressure is very high)
3.7 Compressibility Factor; Deviation From Ideal-gas Behavior
Compressibility factor Z A factor that accounts for the deviation of real gases
from ideal-gas behavior at a given temperature and pressure.
Definition or also
 As the gas deviates from ideal-gas the farther away Z is from unity, behavior.
 Gases behave as an ideal gas at low densities i.e., low pressure, high temperature
Question: What is the criteria for low pressure and high temperature?
Answer: The pressure or temperature of a gas is high or low relative to its critical
temperature or pressure
3.8 Other Equations of State
Several equations to represent the P-v-T behavior of
substances accurately over a larger region with no limitations.
Van der Waals Equation of State

This model includes two effects not considered in the ideal-
gas model: the intermolecular attraction forces and the
volume occupied by the molecules themselves. The accuracy
of the van der Waals equation of state is often inadequate.
Critical isotherm
of a pure
substance has an
inflection point
at the critical
state.
Differentiate to
43
eliminate vcr
Beattie-Bridgeman Equation of State
Constants in Table 3–4 for various substances reasonably accurate for ρ → 0.8cr.
Benedict-Webb-Rubin Equation of State
Constants in Table 3–4 for substances ρ → 2.5 cr.
Virial Equation of State
Coefficients a(T), b(T), c(T) etc; functions of temperature called virial coefficients.
Example : Cooling of water at constant pressure
A piston-cylinder device contains water initially at 250 oC and 0.5 MPa.
Determine the amount of heat to be removed from water when it is cooled at
constant pressure to 200 oC. Show the process path on a T-h diagram
Example : Wet mixture in rigid vessel
Determine the temperature and total enthalpy of a 10-kg wet mixture of R-134a
at 300 kPa in a 14-L rigid vessel.
Example Prob 3-29: Refrigerant R-134a in constant pressure process
A piston–cylinder device contains 0.85 kg of refrigerant-134a at -10°C. The piston
that is free to move has a mass of 12 kg and a diameter of 25 cm. The local
atmospheric pressure is 97.6 kPa. Now, heat is transferred to refrigerant-134a
until the temperature is 15°C. Determine the,
(a) final pressure,
(b) change in the volume of the cylinder,
(c) change in the enthalpy of the refrigerant-134a.
T 12 kg
P1
Q
h
Example Prob 3-31: Refrigerant R-134a in rigid vessel
10-kg of R-134a in 1.348 m3 rigid vessel is at an initial temperature of -40 oC. The
container is then heated until the pressure becomes 200 kPa. Determine the
final temperature, and initial pressure.
SUMMARY
1. Pure substance
2. Phases of a pure substance
3. Phase-change processes of pure substances
i. Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor
ii. Saturation temperature and Saturation pressure
4. Property diagrams for phase change processes
i. The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface
5. Property tables
i. Enthalpy
ii. Saturated liquid, saturated vapor, Saturated liquid vapor mixture,
Superheated vapor, compressed liquid
iii. Reference state and reference values
6. The ideal gas equation of state
i. Is water vapor an ideal gas?
7. Compressibility factor
8. Other equations of state
i. van der Waals Equation of State, Beattie-Bridgeman Equation of State
ii. Benedict-Webb-Rubin Equation of State, Virial Equation of State
END
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BFF 2233

Prepared by : Ahmad Redza bin Ahmad Mokhtar

A substance that has a fixed chemical composition throughout.

 In a solid, the attractive and repulsive forces between the

• Compressed liquid (sub-cooled liquid): A substance not about to vaporize.

At 1 atm and At 1 atm pressure

As more heat is transferred, Temperature remains As more heat is transferred,

T-v diagram for the heating process of water at constant pressure.

T-v diagram for the heating process of water at constant pressure.

Process 1 and 5 can be reversed

T-v diagram for the heating process of water at constant pressure.

The liquid–vapor saturation (Boiling) curve of a pure substance (water).

At 1 atm pressure, the latent heat of fusion of

T-v diagram of phase-change processes of a pure substance at constant-pressure (numerical

T-v diagram of phase-change processes of a pure substance at constant-pressure (numerical

Saturated Liquid-Vapor Region

T-v diagram of a pure substance.

P-v diagram of a pure substance.

At triple-point pressure and temperature

At triple-point pressure and temperature

Enthalpy—A Combination Property

Pressure  volume = Energy

Enthalpy of vaporization, hfg

Examples 3-2: A piston-cylinder device contains 0.06m3 of saturated water

Examples 3-2: A piston-cylinder device contains 0.06m3 of saturated water

Examples 3-3: A mass of 200g of saturated liquid water is completely vaporized

Examples 3-3: A mass of 200g of saturated liquid water is completely vaporized

0.001043 m3/kg 1.6941 m3/kg

0: Saturated liquid 1: Saturated vapour

A two-phase system can be

A partial listing of Table A–6.

•However, enthalpy h is sensitive to

Ideal gas equation of state

Gas constants of different substances

 At pressures below 10 kPa, water vapor can

Van der Waals Equation of State

Benedict-Webb-Rubin Equation of State

Constants in Table 3–4 for substances ρ → 2.5 cr.

Virial Equation of State

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