BITS F111

Thermodynamics
Module 2:
Properties of Pure Substances
BITS Pilani By: -
Dubai Campus
Dr. Shashank Khurana
 Objectives

➢ Introduce the concept of a pure substance

➢ Discuss the physics of phase-change processes
➢ Illustrate the P-v, and T-v property diagrams and P-v-T surfaces of pure substances
➢ Demonstrate the procedures for determining thermodynamic properties of pure
substances from tables of property data
➢ Describe the hypothetical substance “ideal gas” and the ideal-gas equation of
state
➢ Apply the ideal-gas equation of state in the solution of typical problems.

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 Pure Substance
• A substance that has a fixed chemical composition throughout
For example: - Water, nitrogen, helium, and carbon dioxide

A mixture of two or more phases of a pure substance is still a pure substance as long
as the chemical composition of all phases is the same
→True for Liquid and Gaseous Water Mixture, but not for Liquid and Gaseous Air Mixture
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Pure Substance

Question.
Is Icy-Water a Pure Substance ??

→ A mixture of ice and liquid water is

a pure substance
→ Both solid (ice) and liquid (water)
phases have the same chemical
composition.
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Pure Substance
• A mixture of various chemical elements or
compounds also qualifies as a pure
substance as long as the mixture is
homogeneous

Question.
Is Air a Pure Substance ??
→ Although a (homogeneous) mixture of
several gases, is considered to be a pure
substance because it has a uniform
chemical composition
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Pure Substance

Question.
Is Oil and Water Mixture a Pure
Substance??

→ A mixture of oil and water is not a

pure substance.
→ Oil and water being immiscible
(insoluble), form separate layers which
are two chemically dissimilar regions.
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Phases of Pure Substance
Relatively fixed positions Move about each other Move about at random

Solids Liquids Gases

• Molecules in the gas phase are at a considerably higher energy level than they are in the liquid or solid
phases
• Gas must release a large amount of its energy before it can condense or freeze.
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Phase Change Process (of Pure Substance)

❑Water is used to demonstrate the basic principles involved for phase change, though, all
pure substances exhibit the same general behavior

❑Applicability: -
❑ Water exists as a mixture of liquid and vapor in the boiler and the condenser of a
steam power plant
❑ Studying and analyzing the phase-change process for a pure substance is vital

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➢ Constant Pressure Heating, P=1 atm
➢ Process 1-2:
➢ Compressed/Subcooled Liquid
➢ Sensible Heating T↑, v↑
➢ Point 2:
➢ Saturated Liquid (Will vaporize on gaining heat)
➢ Process 2-3:
➢ Latent Heating T=const., v↑↑
➢ Boiling starts
➢ Point 3:
➢ Saturated Liquid-Vapor Mixture
➢ Point 4:
➢ Saturated Vapor (Will condense on losing heat)
➢ Process 4-5:
➢ Superheated vapor T↑, v↑
➢ All Vapor, heated above saturation point
➢ Constant Pressure Heating, P=1 atm Saturated Vapor
➢ Process 1-2:
➢ Compressed/Subcooled Liquid
➢ Sensible Heating T↑, v↑
➢ Point 2:
➢ Saturated Liquid (Will vaporize on gaining heat)
➢ Process 2-3:
➢ Latent Heating T=const., v↑↑
➢ Boiling starts
➢ Point 3: Saturated Liquid
➢ Saturated Liquid-Vapor Mixture
➢ Point 4:
➢ Saturated Vapor (Will condense on losing heat)
➢ Process 4-5:
➢ Superheated vapor T↑, v↑
➢ All Vapor, heated above saturation point
Saturation Temperature and Saturation Pressure
❖ Saturation temperature (Tsat): At a given pressure, the temperature at which a pure substance
changes phase

❖ Saturation pressure (Psat): At a given temperature, the pressure at which a pure substance
changes phase.

Water boils at 100ºC: - Incorrect Statement

Water boils at 100ºC at 1 atm pressure (101.325 kPa): - Correct Statement
→ The temperature at which water starts boiling depends on the pressure; therefore, if the pressure is
fixed, so is the boiling temperature

Representation
➢ At 101.325 kPa pressure, the saturation temperature is 100ºC
➢ At 100ºC temperature, the saturation pressure is 101.325 kPa

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Saturation Temperature and Saturation Pressure
• Saturation Temperature Tsat
increases with Saturation
Pressure Psat

Inference: -
• A substance at higher pressures
boils at higher temperatures

Application: -
• In Kitchen, higher boiling
temperatures (under higher
pressures) mean shorter
cooking times and energy
savings
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Saturation Temperature and Saturation Pressure

Latent Heat
• Amount of energy absorbed or released during a phase-change process

Latent Heat of Vaporization

• Amount of energy absorbed by substance during the vaporization

Latent Heat of Fusion

• Amount of energy absorbed by substance during the fusion

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Saturation Temperature and Saturation Pressure

Latent Heat
• Amount of energy absorbed or released during a phase-change process

Latent Heat of Vaporization

• Amount of energy absorbed by substance during the vaporization

Latent Heat of Fusion

• Amount of energy absorbed by substance during the fusion

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Phase Change Process: T-ν Diagram

With increase in Pressure

•Boiling process starts at higher
temperature
•Latent heat of vaporization decreases
•vsaturated liquid ↑, vsaturated vapor ↓
•(vsaturated liquid − vsaturated vapor) decreases

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Phase Change Process: T-ν Diagram

• Saturated Liquid line

• Saturated Vapor line
• Constant Pressure Lines
• Compressed Liquid region
• Saturated liquid–vapor mixture
region, or the wet region
• Superheated Vapor region
• Critical point

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 Case Study
Case A. Which scenario would start boiling earlier? Why ?
(a) At Sea level (ground)
(b) At Higher Altitudes

Answer→ (b)
As altitude h increases, P decreases.
Boiling temperature decreases, and
hence the process of phase change
(with Pvap.≈Patm) begins by
absorbing lesser amount of heat
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 Case Study
Case B. Which scenario would take longer to cook ? Why ?
(a) At Sea level (ground)
(b) At Higher Altitudes

Answer→ (b)
As altitude h increases, P decreases, in
turn the Boiling temperature
decreases. Latent heat required for
complete phase change, and in turn
cooking increases, which results in
longer cooking times.
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 Case Study
Case C. Pressure cooker reduces the cooking time and saves energy.
True / False ? How?

Answer→ True
•Pressure cooker increases the
Pressure inside
•Boiling temperature increases, and
the necessary amount of heat to be
transferred is available, together with
forcing the liquid into the food, hence
reducing the cooking time and energy
required.
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 Case Study
Case D. A restaurant cooks a same dish in a pan in three different ways,
Namely, (a) uncovered, (b) covered with a light lid, and (c) covered with a
heavy lid. For which case will the cooking time be the shortest? Why?

Answer→ (c)
•One with heavier lid would have the
highest Pressure inside
•Boiling temperature increases, and
the necessary amount of heat to be
transferred is available, together with
forcing the liquid into the food, hence
reducing the cooking time and energy
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Case Study
Case E. 1 kg of saturated liquid water is being vaporized at two different
temperatures: 100ºC and 120ºC. Which case would consume more
energy?

Answer→ 100ºC
Lower temperature renders
higher requirement of latent
heat, hence consuming more
energy for complete
vaporization
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 Case Study
Case F. A perfectly fitting pot and its lid often stick after cooking, and it
becomes very difficult to open the lid when the pot cools down. Explain
why this happens and what you would do to open the lid.

Answer→
•On cooling (losing heat to the
surroundings), the saturation pressure
inside (corresponding to the cooled
temperature) decreases, and becomes
lesser than atmospheric
•Pot can be heated again for a while,
to increase the pressure inside
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 Critical Point For Water

• Point at which the saturated liquid and

saturated vapor states are identical
• For P>Pcr , No distinct phase change
process
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Phase Change Process: P-ν Diagram

Notice the difference between

the Shape of P-v diagram and T-
v diagram for a pure substance

• Saturated Liquid line

• Saturated Vapor line
• Constant Temperature Lines
• Compressed Liquid region
• Saturated liquid–vapor
mixture region, or the wet
region
• Superheated Vapor region
• Critical point
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 Enthalpy – A Combination Property
Specific Enthalpy

Total Enthalpy

• Combination u + Pv is frequently encountered in

the analysis of control volumes.
• For the sake of simplicity and convenience, this
combination is defined as a new property,
enthalpy, and given the symbol h
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 Property Table
Necessity
• For most substances, the relationships among thermodynamic properties are too complex to be
expressed by simple equations.
• Therefore, properties are frequently presented in the form of tables.
• Some thermodynamic properties can be measured easily, but others cannot and are calculated
by using the relations between them and measurable properties.

Organization of Property Table

Depending on the type of pure substance, a separate table is prepared for
one (or more) of the following regions:
• Saturated liquid and vapor mixture (Wet mixture)
• Superheated vapor
• Compressed (subcooled) liquid
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 Property Table:
Saturated Liquid and Saturated Vapor
Subscript Nomenclature: -
f → Saturated liquid
g → Saturated vapor
fg → difference between saturated vapor
and saturated liquid states ~ g−f

hfg = latent heat of vaporization

(amount of energy needed to vaporize a
unit mass of saturated liquid at a given
temperature or pressure)
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 Property Table:
Saturated Liquid and Saturated Vapor
Subscript Nomenclature: -
f → Saturated liquid
g → Saturated vapor
fg → difference between saturated vapor
and saturated liquid states ~ g−f

hfg = latent heat of vaporization

(amount of energy needed to vaporize a
unit mass of saturated liquid at a given
temperature or pressure)
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 Topic: - Saturated Liquid / Saturated Vapor

NUMERICAL
Question 1. A piston cylinder contains 50 kg of saturated liquid water at 90ºC. Determine:
(a) Pressure in the cylinder
(b) Volume of the Cylinder (m3)
(c) Enthalpy (kJ)
(d) Internal Energy (kJ)

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 NUMERICAL
Question 1.
Now the liquid is heated at the constant temperature in order to get the saturated vapor.
Find:
e) Pressure in the cylinder
f) Volume of the cylinder (m3)

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 NUMERICAL
Question 1.
Now the liquid is heated at the constant temperature in order to get the saturated vapor.
Find:
g) Enthalpy (kJ)
h) Internal energy (kJ)
i) The change in Internal energy & Enthalpy transferred to the water (kJ)
j) Draw the process in the T-v and P-v diagram

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 NUMERICAL
Question 1.
j) Draw the process in the T-v and P-v diagram

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 Property Table:
Saturated Liquid-Vapor Mixture

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 Property Table:
Saturated Liquid-Vapor Mixture
Quality or Dryness Fraction, x: -
Ratio of the mass of vapor to the total mass of the mixture

If x=0, saturated liquid

If x=1, saturated vapor

T = Tsat @ given P
P = Psat @ given T
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 Topic: - Saturated Mixture

NUMERICAL
Question 2. A 1.8 m3 rigid tank contains steam at 220ºC. One-third of the
volume is in the liquid phase and the rest is in the vapor form. Determine:
(a) Pressure [kPa]

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 Topic: - Saturated Mixture

NUMERICAL
Question 2.
(b) Mass of liquid [kg]
(c) Mass of vapor [kg]
(d) Quality of the mixture

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 Topic: - Saturated Mixture

NUMERICAL
Question 2.
(e) Specific volume of the mixture [m3/kg]
(f) Specific and total enthalpy of the mixture [kJ/kg, kJ]

Answer →
(a)2317.8 kPa (b) 504.2 kg (c) 13.92 kg (d) 0.0269
(e) 0.0034574 m3/kg (f) 993.6 kJ/kg, 514806 kJ BITS Pilani, Dubai Campus