DEPARTMENT OF CHEMICAL ENGINEERING,

FACULTY OF TECHNOLOGY

OBAFEMI AWOLOWO UNIVERSITY, ILE IFE

CHE 201: ENGINEERING THERMODYNAMICS

MODULE 3: FIRST LAW OF THERMODYNAMICS 1:

PROPERTIES OF PURE SUBSTANCES

2023/2024 SESSION

Lecturer: SANDA, O. Ph.D. Chem. Eng.(Ife). Reg. Engr.

(COREN),
PURE SUBSTANCE IN THERMODYNAMICS
In the context of thermodynamics, a pure substance is defined as a system that meets the
following criteria:
1. Homogeneous in Composition: The composition of every part of the system is uniform
and consistent throughout. Composition refers to the relative proportions of the chemical
elements that make up the substance, as determined through chemical analysis.
Importantly, the way these elements are combined (e.g., molecular structure or bonding)
does not affect the classification of the substance as pure.
2. Homogeneous in Chemical Aggregation: The chemical structure and bonding of the
substance remain consistent across the system.
3. Invariable in Chemical Aggregation: The chemical makeup does not change during
analysis or observation within the defined system.
Examples of Pure Substances
 Single chemical compounds (e.g., water, CO₂) where all molecules have identical
chemical compositions and properties.
 Single-phase systems of elements (e.g., liquid mercury or gaseous oxygen).

Phase Change of a Pure Substance

To understand the phase change of a pure substance, let us examine the behavior of 1 kg of
liquid water subjected to constant pressure in a piston-cylinder setup shown in the Figure below:

a. Initial State (Liquid Heating): The water begins at 20°C under a constant pressure of 1
1(a) 1(b) 1(c)
atmosphere (1.0132 bar), as depicted in Figure 1(a). As heat is gradually added, the
temperature of the water rises, reaching 100°C (the boiling point at 1 atmosphere). During
Figure 1 phase change in water heated at constant pressure
this heating phase, the volume of the liquid expands slightly, causing the piston to move
 upwards. This process is shown on the temperature-specific volume (T-v) diagram in
Figure 2.
b. Phase Change (Boiling Begins): Upon reaching 100°C, the water begins to undergo a
phase change from liquid to vapour, as shown in Figure 1(b). During this phase-change
process, the following are observed:
 Heat continues to be added, but the temperature remains constant at 100°C.
 The heat supplied during this phase is known as the heat of vapourization.
 The pressure remains constant at 1 atmosphere, making 100°C the saturation
temperature at this pressure.
c. Completion of Vapourization: As the liquid water is fully converted into vapour, the
volume increases significantly, causing the piston to rise further, as illustrated in Figure
1(c). This significant volume expansion is characteristic of the liquid-to-vapour phase
transition.

UNDERSTANDING PHASE-CHANGE PROCESSES USING PROPERTY DIAGRAMS

Phase-change processes of pure substances are best analyzed through property diagrams. Here,
we explore the T-v, P-v, and P-T diagrams, which provide insights into the behavior of
substances during phase transitions.
1. T-v Diagram (Temperature-Specific Volume Diagram)
The T-v diagram illustrates the relationship between temperature (T) and specific volume (v)
during phase changes.

Phase-Change Process at Different Pressures

At 1 atm pressure, the phase-change process follows a path where water boils at 100°C. The
saturated liquid and vapour states are connected by a horizontal line. If the pressure increases
(e.g., to 1 MPa), the boiling temperature rises (to 179.9°C), and:
o The saturated liquid specific volume becomes slightly larger.
o The saturated vapour specific volume becomes significantly smaller.
Critical Point
As pressure increases further, the saturation line (horizontal line) becomes shorter and eventually
shrinks to a single point, the critical point. At the critical point, the saturated liquid and vapour
states are indistinguishable.

Figure 2: variation of phase change characteristics with increasing pressure

For water, the critical properties are:

o Pcr=22.09 MPa
o Tcr=374.14 °C
o vcr=0.003155 m3/kg
Behaviour Above the Critical Pressure
Above the critical pressure, there is no distinct phase-change process. The substance transitions
smoothly from a liquid-like state to a vapour-like state without a clear boundary.

Regions on the T-v Diagram

 Saturated Liquid Line: Connects all saturated liquid states.
 Saturated Vapour Line: Connects all saturated vapour states.
 Dome (Wet Region): Enclosed by the saturated liquid and vapour lines, representing
states where liquid and vapour coexist.
 Compressed Liquid Region: To the left of the saturated liquid line, where the substance
is entirely liquid.
 Superheated Vapour Region: To the right of the saturated vapour line, where the
substance is entirely vapour.

Figure 3: T – v diagram
P-v Diagram (Pressure-Specific Volume Diagram)
The P-v diagram shows the relationship between pressure (P) and specific volume (v) for a pure
substance.

Figure 4: P – v diagram

Phase-Change Process at Constant Temperature

Consider a piston-cylinder device containing water at 1 MPa and 150°C (compressed liquid).
As pressure decreases at constant temperature, the specific volume increases slightly. When the
pressure reaches the saturation pressure (Psat) for the given temperature (T=150°C), water begins
to boil. During boiling, both pressure and temperature remain constant, but specific volume
increases significantly.
Repeating this process for other temperatures produces similar curves. Connecting the saturated
liquid and vapour states for various temperatures forms the P-v diagram.
P-T Diagram (Pressure-Temperature Diagram)
The P-T diagram describes the phase-change boundaries of a pure substance:
 Sublimation Line: Separates the solid and vapour phases.
 Fusion Line: Separates the solid and liquid phases.
 Vapourization Line: Separates the liquid and vapour phases.

Figure 5: A typical P – T diagram showing the triple point

At the intersection of these lines is the triple point, where all three phases coexist in equilibrium.
The P-v-T Surface: Understanding the Thermodynamic State
In thermodynamics, the state of a simple compressible substance is completely defined by any
two independent intensive properties. Once these two properties are known, all other
properties become dependent. This concept allows us to represent the relationship between
pressure (P), specific volume (v), and temperature (T) as a three-dimensional surface, known as
the P-v-T surface.

Figure 6: A typical P – v – T surface

Representation of the P-v-T Surface
1. Three-Dimensional Surface: The P-v-T surface represents equilibrium states of a substance
in a 3D space where Temperature (T) and specific volume (v) serve as independent
variables (the base), and Pressure (P) is the dependent variable (the height).
2. Quasi-Equilibrium Processes: All points on the P-v-T surface correspond to equilibrium
states.
3. Single-Phase and Two-Phase Regions: The single-phase regions (solid, liquid, or vapour)
appear as smooth, curved surfaces.
 The two-phase regions (e.g., saturated liquid-vapour mixtures) appear as surfaces
perpendicular to the P-T plane, while the intersection of two-phase regions with the P-T
plane forms phase boundary lines.

The P-v-T surface combines a vast amount of thermodynamic information in a single

representation. However, its complexity often makes it impractical for routine calculations or
visual analysis.
THERMODYNAMIC PROPERTY TABLES
Thermodynamic property tables provide a systematic way to determine the properties of
substances (like water, refrigerants, and air) in different phases. They are essential tools in
engineering thermodynamics, used to solve problems involving heat, work, and energy transfer.
Property tables are vital for:
 Evaluating the thermodynamic state of a system.
 Determining specific properties like pressure, temperature, specific volume, enthalpy,
internal energy, and entropy.
 Simplifying the analysis of thermodynamic processes.

Types of Thermodynamic Property Tables

Property tables are typically organized based on the phases of matter:
1. Saturated Tables:
o Saturated Liquid: Contains properties of a substance as a liquid at the saturation
temperature.
o Saturated Vapour: Contains properties of a substance as a vapor at the saturation
temperature.
o Saturated Mixture: Includes data for two-phase systems (mixtures of liquid and
vapor).
2. Superheated Vapour Tables: Provide data for substances in the vapor phase above the
saturation temperature (T > Tsat)
3. Compressed Liquid Tables: Contain properties of a liquid below the saturation
temperature and pressure.
4. Ideal Gas Tables: Include properties of gases assuming ideal behavior.

Key Properties in the Tables

The main properties listed in thermodynamic tables include:
1. Pressure (P): Force per unit area exerted by a fluid.
2. Temperature (T): A measure of thermal energy.
3. Specific Volume (v): Volume occupied per unit mass (m3/kg);
 4. Enthalpy (h): Total energy content per unit mass, combining internal energy and flow
work (kJ/kg);
5. Internal Energy (u): Energy stored in the molecular structure of the substance (kJ/kg);
6. Entropy (s): Measure of randomness or disorder (kJ/kg⋅K)

Table 1: Saturated water tables

Table 2: some superheated steam tables
Saturation Properties
 Saturation Temperature (Tsat): The temperature at which a substance undergoes a phase
change at a given pressure.
 Saturation Pressure (Psat): The pressure at which a substance undergoes a phase change at
a given temperature.
 Properties in the Saturated Table are split into:
o Saturated liquid properties (subscript f).
o Saturated vapor properties (subscript g).
o Two-phase region values, using the quality x, where:
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑉𝑎𝑝𝑜𝑟
𝑥= , 0≤𝑥≤1
𝑇𝑜𝑡𝑎𝑙 𝑀𝑎𝑠𝑠
For mixtures, we have:
𝑣 = 𝑣𝑓 + 𝑥(𝑣𝑔 − 𝑣𝑓 ),
ℎ = ℎ𝑓 + 𝑥(ℎ𝑔 − ℎ𝑓 ),
𝑢 = 𝑢𝑓 + 𝑥(𝑢𝑔 − 𝑢𝑓 ),
𝑠 = 𝑠𝑓 + 𝑥(𝑠𝑔 − 𝑠𝑓 )
For the enthalpy column, we have an entry designated “hfg”. This is the latent heat of
vapourization for the given conditions of temperature and pressure, and it is the same as:
𝒉𝒇𝒈 = 𝒉𝒈 − 𝒉𝒇
So that:
𝒉 = 𝒉𝒇 + 𝒙𝒉𝒇𝒈

Using the Tables…

1. Identify the given properties (e.g., P, T, x).
2. Locate the appropriate table (saturated, superheated, or compressed liquid).
3. Interpolate if the given value is between tabulated values.

Example Problem: Given a saturated water-vapor mixture at P=300 kPa with x=0.6, find h.
From the saturated water table at 300 kPa, hf=561.4 kJ/kg and hg=2724.7 kJ/kg. therefore,
h=hf+x(hg−hf)=561.4+0.6(2724.7−561.4)=1859.3 kJ/kg.
Interpolation in Property Tables
When the required value is not directly listed, interpolation is used:
𝑦2 − 𝑦1
𝑦 = 𝑦1 + ( ) (𝑥 − 𝑥1 )
𝑥2 − 𝑥1
Where:
 x1, x2 : Known values around the desired x.
 y1,y2 : Corresponding properties.

Note the following:

1. Ensure proper units when using the tables.
2. Understand the phase behavior of the substance.
3. Use ideal gas approximations when tables are unavailable.

Some Worked Examples with Solutions

Example 1: Using Saturated Water Tables
Determine the specific volume, enthalpy, and entropy of a saturated water-vapor mixture at
P=400 kPa with a quality x=0.25
Solution:
From the Saturated Water Table at Psat=400 kPa,
vf=0.001084 m3/kg,
vg=0.4624 m3/kg.
hf=604.7 kJ/kg,
hg=2737.6 kJ/kg,
sf=1.7764 kJ/kg.K,
sg=6.8943 kJ/kg.K
Using the quality formula:
1. Specific Volume:
v=vf+x(vg−vf)=0.001084+0.25(0.4624−0.001084)=0.1165 m3/kg.
2. Enthalpy:
h=hf+x(hg−hf)=604.7+0.25(2737.6−604.7) =1,137.9 kJ/kg.
3. Entropy:
s=sf+x(sg−sf)=1.7764+0.25(6.8943−1.7764)=3.056 kJ/kg.K

Example 2: Using Superheated Steam Table

Find the enthalpy and entropy of superheated steam at P=1,000 kPa and T=400∘C
Solution:
From the Superheated Steam Table at P=1 MPa and T=400∘C, we have:
h=3,263.9 kJ/kg, s=7.465 kJ/kg.K,
No further calculation is needed since the values are directly available in the table.

Try your hands on these:

1. A closed vessel with a total volume of 0.6 m3 contains 3.0 kg of a saturated water-liquid-vapour
mixture in equilibrium at a pressure of 0.5 MPa. Calculate the following:
a. The mass and volume of the liquid phase.
b. The mass and volume of the vapour phase.

2. A sealed vessel with a total capacity of 0.05 m3 contains a saturated liquid-vapour mixture of
water in equilibrium at a temperature of 245∘C. The mass of the saturated liquid present is 10 kg.
Determine the following:
a. The pressure of the mixture.
b. The total mass of the mixture (liquid and vapour).
c. The specific volume of the mixture.
d. The specific enthalpy of the mixture.
e. The specific entropy of the mixture.
f. The specific internal energy of the mixture.
3. A boiler generates 1000 kg of steam per hour at a pressure of 1.60 MPa with a dryness fraction
of 0.90. The steam then passes through a superheater via the boiler stop valve, where its
temperature is increased to 380∘C. The feed water entering the boiler has a temperature of 30∘C.
Using steam table data and taking the specific heat of superheated steam as 2.2 kJ/kg.K, calculate:
a. The total heat supplied to the feed water per hour to produce wet steam.
b. The total heat absorbed per hour in the superheater.

4. A pressure cooker contains 1.5 kg of saturated steam at a pressure of 5 bar. Heat is rejected from
the system, reducing the quality (dryness fraction) of the steam to 60%. Determine:
a. The quantity of heat that must be rejected to achieve this state.
b. The pressure and temperature of the steam at the new state.

5. A piston-cylinder device contains 50 kg of water at a pressure of 200 kPa and a volume of 0.1 m3.
A mechanical stop inside the cylinder restricts the maximum volume to 0.5 m3. The water is
gradually heated until the piston reaches the stop. Using thermodynamic principles and steam
table data:
a. Determine the state of water (compressed, saturated, or superheated) at the initial condition.
b. Determine the state of water when the piston reaches the stop.
c. Calculate the total heat transfer required to heat the water until the piston reaches the stop.

Hint: to make it easier for you, read Chapter 3 of Engineering Thermodynamics by R. K.

Rajput….