TEEE 3103 THERMODYNAMICS LECTURE NOTES BY Eng.
UTHUMAN KOIRE
Email:[email protected] Tel:0784988474/0740019197
LECTURE 1
THERMODYNAMIC CONCEPTS AND ZEROTH LAW OF THERMODYNAMICS
Lecture 1 Outline
1.1 Introduction
1.2 Lecture Objectives
1.3 Introduction to Thermodynamic
1.4 Thermodynamic Concepts
1.5 Behaviour of Gases
1.6 The Zeroth Law of Thermodynamics
1.7 Temperature and Temperature Scales
1.1 Introduction
This lecture introduces you to the study of thermodynamics and what it
entails. We shall start by familiarizing ourselves with terminologies that
are often used when dealing with the subject of thermodynamics and it is
therefore very important that these terminologies become part and parcel
of your vocabulary.
We shall also introduce the ideal gas laws and the equation of state.
Thereafter, the Zeroth law of Thermodynamics is discussed which
introduces the concept of temperature and thermometric properties.
1.2 Objectives
At the end of this lecture, you should be able to:
1. Explain what thermodynamics entails
2. Define the basic concepts relating to a thermodynamic system.
3. Define thermodynamic equilibrium and distinguish between the
various types of equilibrium
4. Explain an Ideal gas and the ideal gas Laws
5. Explain the Zeroth Law of Thermodynamics and its importance in
temperature measurements
6. Explain the concept of temperature and the various temperature
scales
1.3 Introduction to Thermodynamics
Every time you drive a car, turn on an air conditioner, use a refrigerator or any electric appliance, you
reap the practical benefits of thermodynamics. The term Thermodynamics is a combination of two
words:
Thermo ≡ associated with thermal/heat energy
Dynamics ≡ motion or mechanical work
Literally, Thermodynamics is a science which is based upon the general laws of nature which govern
the conversion of heat into mechanical work and vice-versa.
In terms of classification, Thermodynamics is classified as part of classical mechanics, which is a
branch of physics where we study the behaviour of a system by considering only the large scale
response (macroscopic properties) or the bulk properties (such as density, volume, pressure etc.) of
the system that we can observe and measure in experiments. This is unlike modern physics which
attempts to explain the behaviour of matter from a microscopic or atomic viewpoint (using quantum
and statistical mechanics) by taking into account the atomic constitution of matter i.e., structure etc.
The study of thermodynamics was inaugurated by 19th -century engineers, who wanted to know the
ultimate limitations the laws of physics impose on the operation of steam engines and other machines
that generate mechanical energy
or heat energy. Today the scope of thermodynamics has immensely increased with innumerable
applications in chemistry and engineering.
Definition
Thermodynamics is the study of relationships involving heat, mechanical work and other aspects of
energy transfer that takes place in thermodynamic systems such as refrigerators, heat pumps,
internal combustion engines etc.
These relationships are governed by the laws of thermodynamics which have become some of the
most important fundamental laws not only in physics and other sciences but also nature in general.
The four principles (referred to as "Laws of thermodynamics") are:
Zeroth Law of Thermodynamics, which introduces the concept of temperature and thermodynamic
equilibrium where two objects attain the same temperature when brought in thermal contact.
First Law of Thermodynamics, which mandates conservation of energy, and represents the
relationship between heat and mechanical work.
Second Law of Thermodynamics, which depicts the manner in which energy changes take place
by stating natural processes take place in a direction such as to increase the disorder (Entropy) of
the system OR equivalently, the Entropy of an isolated macroscopic system never decreases.
Third Law of Thermodynamics, which explains the nature of bodies in the neighbourhood of
absolute zero temperature. The entropy of a perfect crystal tends to zero at absolute zero
temperature, implying that it is impossible to cool a system all the way to absolute zero.
1.4 Thermodynamic Concepts
To define terminologies related to thermodynamics, we shall consider a
thermodynamic device such as a refrigerator or a gasoline engine where energy
transfer takes place in the form of heat or mechanical work into or out of the device.
In a refrigerator for example, we do work (to the refrigerator) by extracting heat from
the refrigerator and expelling it to the outside (the room). The refrigerator in this case
is our working system and the room is the surrounding. The fridge will only operate
efficiently if the door is closed i.e., the system has to be isolated from the
surrounding so that we can account for any form of energy input into or out of the
system.
By considering our refrigerator as a thermodynamic system let us now define basic
thermodynamic terminologies/concepts.
Thermodynamic System:– Any portion of the material universe which can be
isolated completely and arbitrarily from the rest for consideration of the changes
which may occur within it under varying conditions. Often a system may be
considered as composed of smaller systems, which together make up the larger
system.
An example of a system is biological organism (Fig. 1-1)
or a mechanical device (Fig. 1-2), or a specialized
material e.g., steam expanding in a turbine. A
thermodynamic system can interact (and exchange heat
or matter) with its surroundings through the boundary wall.
Heat and work are the two means of transferring energy
into or out of a system.
There are three classes of systems namely closed, open
and isolated systems.
Fig. 1-1 Human digestive system is
an open system which exchanges
food (matter) with the surrounding
(body)
Fig. 1-2. A gas in cylinder (closed) system can only
exchange heat with the surrounding
Open systems:- A system where the exchange of both heat and matter can occur through the boundary.
Example is a human digestive system.
Closed systems:- It is a system where only the exchange of heat between it and the surrounding is
possible through the boundary. There is no matter exchange. Example is a refrigerator or a gas enclosed
in a cylinder (Fig. 1.2).
Throughout the course, we will be interested with the exchange of heat energy only, restricting ourselves
to closed systems.
Isolated System:- This is a system which is thermally insulated and has no communication of heat with
the surrounding though work may be done on it. Such changes are called adiabatic changes. Example is a
thermos flask.
Boundary:– This is a “wall” that separates the system from the surrounding. The boundary may allow for
exchange of heat and matter between the system and the surrounding depending on its nature. If the
boundary inhibits the system from changing its volume or shape so that no mechanical work is performed
on it, the wall is said to be rigid.
The surroundings:- Refers to the rest of the universe outside the system.
Diathermal wall:- A wall that allows for exchange of heat between the system and the surrounding. Good
examples are metallic walls. Two systems separated by a diathermal wall are said to be in contact. In other
words, two systems are in thermal contact if heating one of them results in macroscopic changes in the
other.
Adiabatic or Adiathermal wall:- A wall that does not allow for exchange of heat between the system and
the surrounding. A good example is the walls of a vacuum flask. A system enclosed by an adiabatic wall is
called an isolated system.
Thermal equilibrium:- This implies the system is in a steady state condition i.e. the temperature is
uniform throughout the system and remains constant in time such that there is no flow of heat
through the system.
Mechanical equilibrium:- This means that there are no unbalanced forces acting within the system.
Chemical equilibrium:- This means that there are no chemical reactions occurring within the
system.
Thermodynamic (complete) equilibrium:- This represents a condition in which the system
experiences thermal, mechanical and chemical equilibrium. In this case, the bulk physical properties
or thermodynamic variables (Pressure, Volume and Temperature) of the system are uniform and do
not change with time.
State variables:- These are directly measurable variables which are sufficient to describe the bulk
behaviour of the system. In the case of a gas system, these include pressure (P), temperature (T),
volume (V), internal energy (U), Entropy (S) and composition () ). In a magnetic solid, these are the
magnetic field (H), the magnetization (M) and temperature (T). For a homogeneous system,
consisting of a single substance, the composition () ) is fixed.
Usually, we require at least two state variables to specify the state of a system. For example, of
the 3 measurable variables P, V and T, in a gas system, only two are independent and any one
may be expressed in terms of the other two e.g.,
P is a function of V and T or P = P(V, T)
V is a function of P and T or V = V(P, T)
Hence, the state of a gas is equally well specified by quoting (P,V); (P,T) or (V,T). State variables
are also known as thermodynamic variables or coordinates.
Intensive & Extensive Variable
State variables can be extensive or intensive. Extensive variables are macroscopic parameters that
are proportional to the mass or size of the substance present in the system and as such they
correspond to some measure of the system as a whole. Examples include internal energy (U),
entropy (S), mass (m), volume (V), length, heat capacity (C) etc
An intensive variable is discrete (local) in nature i.e., it is independent of mass or size of the
system but it is characteristic of the substance present in the system. Examples of such variables
are pressure, temperature, viscosity, density, magnetic induction etc.
State functions:- These are functions that are dependent only on the value of state variables
P, V, and T at a given equilibrium state and not on the process taking place in the system.
Examples include the internal energy (U), the enthalpy (H), and the entropy (S). On the other
hand, work and heat are dependent on nature of the process (path) and not on the final value
of the state variable and are thus not state functions.
Heat & Work:-
Heat is the transfer of thermal energy between a system and its environment due to the
temperature difference. Work is the transfer of mechanical energy
Heat is equivalent to work in that both represent ways of transferring energy. Neither heat nor
work is an intrinsic property of a system: that is, we cannot say that a system contains a
certain amount of heat or work unlike properties such as pressure, temperature, and the
internal energy. Thus, Heat and work are not properties of the state of the system; they are
not state functions. Instead we say that a certain amount of energy can be transferred, either
into or out of the system, as heat or as work. Both heat and work are thus associated with the
thermodynamic process.
Process:- It is a mechanism of bringing about a change from one
equilibrium state of a system to another. A good example is when pushing a
piston and compressing a gas in a cylinder from one equilibrium state
(𝑃1 , 𝑉1 ) equilibrium state (𝑃2 , 𝑉2 ) . A process may be reversible or
irreversible.
Reversible process:- Reversible implies that in any such change, the
system must be capable of being returned to its original state with the
surrounding unchanged. This requires two conditions
1. The processes must be quasi-static i.e., it should take place very slowly
such that it is always in a succession of equilibrium states at any given time
2. There must be no hysteresis i.e., no dissipative forces such as friction are
present to dissipate energy.
Figure 1-3. Reversible and irreversible processes. Irreversible process
cannot be plotted on an indicator diagram.
Working substance:- This is a gas or fluid enclosed in
the system that either receives energy transfer in the
form of heat or work from the surrounding or transfers
energy in the same form to the surrounding.
Usually, the working substance should remain unchanged at the
end of the process i.e., it should not introduce new parameters
during the process. Because of this, we usually consider a working
substance that is ideal or otherwise called an ideal gas and not a
real gas. In the next section we look at the behaviour of ideal
gases.
1.5 Behaviour of Gases
In a gas, the molecules are well separated and they fly about randomly in the
container. We have no way of ascertaining the initial positions and velocities of
each individual molecule.
In lack of a microscopic description involving the individual positions and velocities
of the molecules of the gas, we must be satisfied with a macroscopic description
involving just a few measurable variables (such as mass of the gas, number of
moles, volume, density, pressure and temperature of the gas) that characterize the
average conditions in the volume of a gas.
We will deal with the study of macroscopic properties of gases and the relationship
between these properties with the average measurable variables of the gas
system.
In order not to introduce other macroscopic variables in our gas system that may
arise due to interactions between the gas molecules, we shall consider an “ideal”
situation or otherwise called an ideal gas.
1.5.1 What is an Ideal gas?
An ideal gas is an abstraction and it is a gas whose properties represent the limiting
behaviour of real gases at sufficiently low densities. In an ideal gas, it is assumed that
(i) There are no intermolecular attractions. This implies that the internal energy of the gas is
entirely kinetic and would be dependent on temperature
(ii) The molecules themselves occupy negligible volume.
The behaviour of an ideal gas is dependent on three factors namely its
temperature, pressure and volume. These parameters obey some simple ideal
gas laws namely:
Boyle’s law
▪ At constant temperature, the volume of a fixed mass of a gas is
inversely proportional to its pressure i.e. P ∝ 1/V. This simply means
applying pressure compresses a gas as shown in Fig 1-2 below. Thus:
PV = constant ………….……………..(1.1) Boyle’s law
Or
𝑃1 𝑉1 = 𝑃2 𝑉2 [For any two states]
Figure 1-5. Boyle’s law on a P-V diagram
Note:
Boyle’s law shows that the PV curve is a hyperbola. The locus of points ( 𝑃1 𝑉1 ) (𝑃2 𝑉2 )
𝑃3 𝑉3 ……. 𝑃𝑛 𝑉𝑛 in thermal equilibrium is called an isotherm.
Pressure law
At constant volume, the pressure (P) of a fixed mass of a gas is absolute temperature
(T) as shown in Fig. 1-6. Thus:
𝑃
= Constant ………………………….………..(1.2)
𝑇
NOTE:
Under ideal situations, the pressure goes
to zero at absolute zero of temperature
(0K or −2730 𝐶
Figure 1-6. Pressure law on a P-V diagram
Charles’ Law
▪ At constant pressure, the volume (V) of a fixed mass of a gas (i.e. fixed number of
moles, n) is proportional to its absolute temperature (T) i.e. V T (Fig. 1-7).
𝑉
= Constant ………………………….……………(1.3)
𝑇
NOTE:
Charles law implies that an ideal gas can be
compressed to zero volume at absolute zero
temperature (0K or −2730 𝐶). This cannot
happen with real gases
• Additionally, at low pressures, V Number of moles (n) of the gas i.e.
V n ……………………………………………....(1.4)
Combining equations (1.1) to (1.4) gives
PV = nRT [Equation of state] …….………....(1.5)
Where R is the universal gas constant = 8.314 Jmol−1K−1
A gas that obeys equation (1.15) at all temperatures and pressure is called an ideal
gas. Eqn. (1.15) is usually referred to as the equation of state of an ideal gas.
Worked Examples
1. What is the pressure of 7 kg of nitrogen gas confined to a volume of 0.4 𝑚3 at 200 C ?
Solution
𝑛𝑅𝑇 𝑀 7×103 𝑔
From PV = nRT => P = where n = 𝑚 =28𝑔/𝑚𝑜𝑙 =250moles
𝑉
∴ P = 15.2 × 105 𝑁𝑚−2
Early in the morning, the tires of an automobile are cold (280K) and their air is at a pressure of 3.0
atm. Later in the day, after a long trip, the tires are hot (330K). What is the pressure? Assume
volume of the tires remain constant.
Solution:
𝑃1 𝑃 𝑇2
From = 𝑇2 =>𝑃2 =𝑃1 = 3.5atm
𝑇1 2 𝑇1
1.5.2 Non Ideal gas
A real gas (e.g. oxygen) only approximate the ideal gas behaviour or equation (1.4) at low enough
densities (i.e., at high temperatures and low pressures) but deviates from the law at low temperatures and
high pressures. This is because a real gas is characterized by:
(i) there are intermolecular attractions
(ii) The gas molecules themselves occupy a finite volume and as such, the gas cannot be compressed to
zero volume as stipulated by Charles law. Real gases liquefy at low pressures.
▪ The Equation of state of a real gas that takes into account the above factors is called Van der Waals
gas equation and is given by
Where a & b are constants with a being dependent on
molecular interactions, = V/n is the molecular volume
1.6 The Zeroth law of thermodynamics
It is a common observation that if you place a cup of hot
coffee or glass of ice water on a table at room
temperature, the coffee will get colder and the ice water
will get warmer, the temperature of each approaching
that of the room. In each case, the object will tend Figure 1-9. Bodies in thermal equilibrium
towards thermal equilibrium with its environment i.e., It follows from the Zeroth law, a whole series of
when its temperature does not change over time. systems could be found that would be in thermal
equilibrium with each other, say, A, B, C, D, etc. All
Such approach to thermal equilibrium must involve these systems possess a common property called
energy exchange (in this case heat) between the temperature, which determines the direction of
system and the environment. This is the concept of heat flow.
the Zeroth law of thermodynamics which is stated as
follows: NOTE:
The Zeroth Law introduces the concept of
Zeroth Law: "If body A and body C are each in thermal temperature and provides a means of determining
equilibrium with a third body B, then, A is also in thermal temperature –Through thermal equilibrium.
equilibrium with C." such arrangement is shown in Fig. 1-9.
1.7 Temperature and Temperature scales
The temperature of a system is a property that determines whether or not, that system is in thermal equilibrium
with other systems. We can also define Temperature as a measure of the degree of hotness.
The temperature of a substance is determined by measuring the change in the thermometric property of a
substance that varies linearly with change in temperature. For example, a substance like mercury expands
linearly in proportion to the increase in temperature of the surrounding or substance whose temperature is to be
measured. Most thermometers are based on this principle. Common types of thermometers include:
(i) Liquid thermometers:- Based on principle of change in volume of a liquid with change in temperature e.g.,
mercury thermometer.
(ii) Resistance thermometer:- Based on the principle of the change in the resistance of a conductor is linearly
dependent on temperature e.g., platinum resistance thermometers
(iii) Thermoelectric thermometers or thermocouples:-
(iv) Bimetallic thermometers:-
1.7.1 Scales of Temperature
If X is the thermometric property that varies linearly with change in temperature then, the temperature, TX of a
substance on an X scale can be given by a linear relationship of the form
Where a is a constant whose value is fixed as the reference point.
The customarily chosen reference point is the temperature at which ice, water and vapour coexist
in equilibrium, known as the triple point, TP of water and is assigned a value of 273.16
Which implies a zero of temperature i.e., T x= 0 at X = 0.
We can now apply Eqn (1.7) to several thermometers depending on the thermometric property chosen.
For a liquid-in-glass thermometer, X is the length (L) of the liquid column, so Eqn (1.7) gives
For a gas at constant pressure, X is the volume (V) of the gas, and Eqn (1.7) gives
Likewise, for a platinum resistance thermometer, X is the electrical resistance (R) of the platinum wire such
that Eqn (1.7) gives
The perfect gas scale
The perfect gas scale does not depend on the particular properties of a particular gas but uses pressure and
volume of a gas to indicate temperature.
In this case, quite a wide range of temperature can be covered. In this scale
Where K, the Kelvin, is the unit of temperature on the ideal gas scale.
1.7.2 Commonly used Temperature Scales
There are three commonly used temperature scales namely:
1.7.2 Commonly used Temperature Scales
There are three commonly used temperature scales namely:
(i) The Kelvin scale
The Kelvin, (K) is the unit of temperature on the ideal gas scale. On this scale, the
temperature between ice point and steam point is 100K
(ii) The Celsius Scale
This is a convenient scale whose range is within the range of commonly encountered
temperatures. On this scale, the temperature between ice point and steam point is 100℃
(ii) Fahrenheit scale
This scale has a range of 180 equal parts with the ice point at 32 ℉ and Steam point is 212℉
Relationship between temperature scales
A simple Relationship between the three
temperature scales i.e., Celsius, Fahrenheit
and Kelvin is given by
Worked Examples
1. A platinum resistance thermometer has a resistance R = 90.35 Ω. when its bulb is placed in a triple point
cell. Determine its temperature when the bulb is placed in an environment where its resistance is 96.28Ω.
Solution
2. The temperature of the surface of the sun is about 6500 oC. What is this temperature on the Kelvin scale?
Solution
Assignment one:
1. Explain why a real gas behaves like an ideal gas at low densities but not at high densities
2. Explain the difference between heat and thermal energy
3. Compare and contrast between heat and work
4. Explain why heat and work are not state functions
5. The reading ta and tb of two thermometers A and B agree at Ice point and steam point related by the equation
ta=Ɩ+mtb+ntb2 where Ɩ,m,n are constants. When both immersed in oil thermometer A reads 510C and thermometer
B reads 500C . determine the reading on A when thermometer B reads 250C . Discuss which thermometer is
correct
6. A system of volume V contains a mass m of gas at pressure p and temperature T. The macroscopic properties of the
system obey the following relationship:
𝑎
𝑝 + 𝑉 2 𝑉 − 𝑏 = mRT, where a, b, and R are constants.
Obtain an expression for the displacement work done by the system during a constant-temperature expansion
from volume V1 to volume V2. Calculate the work done by a system which contains 10 kg of this gas expanding
from 1m3 to 10m3 at a temperature of 293 K. Use the values a=15.7x10 Nm4 , b=1.07x10-2m3 and R = 0.278
kJ/kg-K.
To collected on 13/04/2023
