ME 131

Thermodynamics-I
Chapter 3
Pure Substance

Engr. Faraz Ahmad

Pure Substances
• A substance that has a fixed (homogeneous and
invariable) chemical composition throughout is called
a pure substance.

• It may exist in more than one phase, but the chemical

composition is the same in all phases.

• Pure means “…of uniform and invariable chemical

composition (but more than one molecular type is
allowed).” This allows air to be a pure substance.
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 Examples of Pure Substance

• Water (solid, liquid and

vapor phases)
• Mixture of liquid water and
Single Phase Pure Substances
water vapor
• Carbon Dioxide
• Nitrogen
• Homogeneous mixture of
gases, such as air, as long as Multi-phase Multi-phase impure
Pure Substances Substance
there is no change of phases. 3
 Phases of Matter
• Solid phase -- molecules are arranged in a 3D pattern (lattice).
• Liquid phase -- chunks of molecules float about each other, but
maintain an orderly structure and relative positions within each
chunk.
• Gas phase -- random motion, high energy level.

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 Phase Change Processes

LIQUID LIQUID

Compressed or sub cooled Liquid Saturated Liquid

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 Phase Change Processes (2)

Liquid/Vapor vapor

vapor

Saturated Liquid-Vapor Mixture Saturated Vapor

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Phase Change Processes (3)
vapor
Sub cooled liquid -- not about to evaporate
Saturated liquid -- about to evaporate
Saturated liquid-vapor mixture --two phase
Saturated Vapor -- about to condense
Superheated Vapor -- not about to condense

Superheated Vapor

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Phase Change Processes (4)
Isobaric process P = 1 atm

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Saturation Temperature and Pressure

At a given pressure, the temperature at which a pure substance

changes phase is called the saturation temperature, Tsat.

At a pressure of 101.325 kPa, Tsat is 99.97°C.

At a given temperature, the pressure at which a pure substance

changes phase is called the saturation pressure, Psat.

At a temperature of 99.97°C, Psat is 101.325 kPa.

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 Property diagrams for phase change process
T-v diagram for water
An increase in constant pressure above 1
atm shows:

1. Water starts boiling at a much

higher temperature

2. The specific volume of saturated

liquid is larger and the specific
volume of saturated vapor is
smaller than the corresponding
values at 1 atm pressure.

3. The horizontal line connecting

the saturated liquid and
saturated vapor states is much
shorter.
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 Critical Point
On further increase in pressure, the saturation line continues to
shrink, and it becomes a point when the pressure reaches 22.06 MPa
(for water). This point is called the critical point.
The point at which the saturated liquid and saturated vapor
states are identical.

• At supercritical pressures (P>Pcr),

there is no distinct phase-change
process.

• Eventually, it resembles a vapor,

but we can never tell when the
change has occurred.
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T-v diagram of a pure substance

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P-v diagram of a pure substance
Isothermal process

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Evaluating Thermodynamic Properties
• The relationships among thermodynamic properties are too
complex to be expressed by simple equations.

• Therefore, properties are frequently presented in the form of

tables.

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Property Tables for Two Phase fluid (liquid-vapor mix)

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Property Tables for Saturated Liquid (Liquid-Vapor)

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Example 3.1 (Pressure of Saturated Liquid in a Tank)
A rigid tank contains 50 kg of saturated liquid water at
90oC. Determine the pressure in the tank and the volume
of the tank.
EXAMPLE 3.2 (Temperature of Saturated Vapor in a Cylinder)
A piston–cylinder device contains 0.06 m3 of saturated
water vapor at 350 kPa pressure. Determine the
temperature and the mass of the vapor inside the
cylinder?

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 Example (Using Interpolation)
Determine the specific volume of water vapor at a state where p= 10
bar and T=215°C.

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Quality of Steam (Liquid Vapor Mixture)

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Enthalpy—A Combination Property
• Enthalpy is a measurement of energy in
a thermodynamic system.
• It is the thermodynamic quantity equivalent to the total
heat content of a system.
• It is equal to the internal energy of the system plus the
product of pressure and volume.
• Total energy content of a system.

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 Example 3-4
A rigid tank contains 10 kg of water at 90oC. 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.
Example 3-5

An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of

160 kPa. Determine (a) the temperature, (b) the quality, (c) the
enthalpy of the refrigerant, and (d) the volume occupied by the
vapor phase.

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Example 3-6 (Internal Energy of Superheated Vapor)
Determine the internal energy of water at 200kPa and 300oC?

Example 3-7 (Temperature of Superheated Vapor)

Determine the temperature of water at a state of P=0.5 MPa and
h=2890kJ/kg.

Example 3-8 (Approximating compressed liquid as saturated liquid)

Determine the internal energy of compressed liquid water at 80oC
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?
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Related Practice problems
Example 3-9 (The use of steam tables to determine properties)
Determine the missing properties and the phase description in the
following table for water

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 Related Practice problems
All problems from 3.20 to 3.59 excluding 3.21, 3.22, 3.32, 3.37, 3.41,
3.42, 3.43, 3.44, 3.48, 3.49, 3.52)

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Extending the diagrams to include Solid Phase
P-V diagram of a substance that contracts on freezing

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Extending the diagrams to include Solid Phase (2)
P-V diagram of a substance that expands on freezing

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Triple Line and Triple Point
• On P-v or T-v diagrams, under some conditions all three phases of a
pure substance coexist in equilibrium, these triple-phase states
form a line called the triple line.
• The states on the triple line of a substance have the same pressure
and temperature but different specific volumes.
• The triple line appears as a point on the P-T diagrams and,
therefore, is often called the triple point.
• For water, the triple-point temperature and pressure are 0.01°C
and 0.6117 kPa, respectively.

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Importance of Triple Point Pressure and Temperature
• No substance can exist in the liquid phase in stable equilibrium at
pressures below the triple-point pressure.

• Substances at high pressures can exist in the liquid phase at

temperatures below the triple-point temperature.

• For example, water cannot exist in liquid form in equilibrium at

atmospheric pressure at temperatures below 0°C, but it can exist
as a liquid at -20°C at 200 MPa pressure.

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P-T diagram

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P-v-T Surface
P-V-T surface of a substance that contracts on freezing

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P-v-T Surface
P-V-T surface of a substance that expands on freezing

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P-v-T Surface
If you pull off the Pressure-Temperature projection you
create a plot given as phase diagram.

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P-v-T Surface
p-v Diagram from the 3D p-v-T surface model

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P-v-T Surface
T-v Diagram from the 3D p-v-T surface model

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P-v-T Surface

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P-v-T Surface

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Ideal Gas Equation of State
Any equation that relates the pressure, temperature, and specific
volume of a substance is called an equation of state.

Universal Gas Constant Ru = 8.31434 kJ/kmol-K

Molar Mass (Molecular Weight):

The mass of one mole of a substance in grams.
OR
The mass of one kmol of a substance in kilograms.
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Forms of Ideal Gas Law
PV  mRT
Pv  RT
m=MN
PV  NRuT Ru=MR
P v  RuT, v  V/N
P1V1 P2V2

T1 T2
• An ideal gas is an imaginary substance that obeys the relation
Pv=RT
• Ideal-gas relation given closely approximates the P-v-T behavior
of real gases at low densities.
• Dense gases such as water vapor, however, should not be
treated as ideal gases.
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Is Water Vapor an Ideal Gas?

% 𝑬𝒓𝒓𝒐𝒓 =[(𝒗 ¿ ¿ 𝒕𝒂𝒃𝒍𝒆 − 𝒗 𝒊𝒅𝒆𝒂𝒍 )/ 𝒗 𝒕𝒂𝒃𝒍𝒆 ]×𝟏𝟎𝟎 ¿ 39

Measure of Deviation from Ideal Gas Behavior
Good approximation for P-v-T behaviors of real gases at low
densities (low pressure and high temperature).
Air, nitrogen, oxygen, hydrogen, helium, argon, neon, carbon
dioxide, …. ( < 1% error).

Compressibility Factor
The deviation from ideal-gas behavior can be properly accounted
for by using the compressibility factor Z.

Z represents the volume ratio or compressibility.

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Compressibility Factor

or
, where is volume per unit mole.
Z is known as the compressibility factor.
Real gases, Z < 1 or Z > 1.

Compressibility Factor

It accounts mainly for two things

• Molecular structure
• Intermolecular attractive forces

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Principle of Corresponding States
The compressibility factor Z is approximately the same for all gases
at the same reduced temperature and reduced pressure.

Z = Z(PR,TR) for all gases

Reduced Pressure and Temperature

P T
PR  ; TR 
Pcr Tcr

where:
PR and TR are reduced values.
Pcr and Tcr are critical properties. 42
Generalized compressibility Chart

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Pseudo-Reduced Specific Volume
When either P or T is unknown, Z can be determined from the
compressibility chart with the help of the pseudo-reduced
specific volume.
not vcr !

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Generalized compressibility Chart with VR (Fig A-15)

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Generalized compressibility Chart with VR (Fig A-15)

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Problem 3.84
Methane at 10 MPa and 300 K is heated at constant pressure until
its volume has increased by 80 percent. Determine the final
temperature using the ideal gas equation of state and the
compressibility factor. Which of these two results is more
accurate?

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Generalized compressibility Chart for P3.84 (Fig A-15)

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Practice Problems Chapter 3
Examples:
All examples from 3.1 to 3.12

Exercise Problems:
All problems from 3.20 to 3.59 excluding 3.21, 3.22, 3.32, 3.37,
3.41, 3.42, 3.43, 3.44, 3.48, 3.49, 3.52
Ideal Gas/Compressibility Factor
3.63, 3.64, 3.65, 3.67, 3.69, 3.70, 3.71, 3.72, 3.73, 3.76, 3.78, 3.81,
3.83, 3.84, 3.85, 3.86

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