RWANDA POLYTECHNIC – INTEGRATED

POLYTECHNIC REGIONAL COLLEGE/KIGALI

CAMPUS
“Skills for a better destiny”

MECHANICAL ENGINEERING DEPARTMENT

Subject: ENGINEERING THERMODYNAMICS

Course code: MEE105

Prepped and delivered by

Alexis MUHIRWA, PhD.

This course introduces you to thermodynamics which is a basic science that underlines the principles
of all energy conversion devices and in particular, the transformation of Thermal Energy into
Mechanical Work and vice versa in materials and machines. Thermodynamics has innumerable
applications not only in physics but also in chemistry, biology and engineering and as such, it is an
important course in nigh all fields.

Aims of the course: At the end, you should be able to explain and apply the laws of
thermodynamics to solve problems related to energy conversion processes in mechanical systems

Prerequisites
To follow this course unit, you will require knowledge of partial differential equations and Structure
and Properties of Matter.

Mode of delivery and Study Skills required

This course is conducted as a mix of several teaching methods; Distance and e-learning with
limited face-to-face.
You are advised to set aside at least 4 hours for each lecture. At the end of every the lecture,
you should attempt all the problem sets. You will be called upon to submit solutions to
selected questions from the problem sets for assessment.
Mode of Assessment
Test and/or Assignments - 50%; Written Examinations - 50%
Reference materials
1. T.D Eastop, A. McConckey, (2009) Applied Thermodynamics for Engineering Technologists, 5th
Edition, Dorling Kindersley Pvt, India
2. Manuscript of Thermodynamics lecture (1st year), Academic year 2019 by Emmanuel Kabarinda,
RP-IPRC/Kigali, Mech. Engineering dpt.
2. Brij L., Subrahmanyam N., Hemne P. S., (2008), Heat Thermodynamics and Statistical Physics., S.
Chand & Company Ltd, New Delhi.
3. F.O. Akuffo, A. Brew-Hammond, F. Makau Luti and J.G.M. Massaquoi. ANST, UNESCO (1997),
Nairobi, Kenya.
3. Resnick R., Halliday D., Krane K. S., PHYSICS Vol 1. John Wiley and Sons, Inc., NY.,
4. Aduda B. O., (2004). Structure and Properties of Matter, Distance Learning study module,
University of Nairobi, 2004.
5. D. Halliday, R. Resnick, J. Walker (2015) Fundamentals of Physics, John Wiley & Sons, Ltd, London.
6. Y. A. Cengel, M. A. Boles (2015) Thermodynamics – An Engineering Approach, McGraw Hill, New
York.
7. Sanjeev Chandra (2016) Energy, Entropy and Engines - an introduction to Thermodynamics, John
Wiley & Sons, Ltd
8. Tarik Al-Shemmeri (2010), Engineering thermodynamics, Ventus Publishing ApS
9. M. J. Moran, H. N. Shapiro, D. D. Boettner, M. B. Bailey (2014) Fundamentals of Engineering
Thermodynamics, John Wiley & Sons, Ltd, London.
10. C. Borgnakke, R. E. Sonntag (2012) Fundamentals of Thermodynamics, John Wiley & Sons, Ltd,
London.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 2

 Chapter 1: INTRODUCTION TO ENGINEERING THERMODYNAMICS
1.1 Basics and Significance
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. Birth: Industrial revolution
(late 18th, early 19th century). William Thomson, in 1749, coined the term thermodynamics. The
word “Thermodynamics” is derived from two Greek words “thermes” and “dynamikos” which means
heat/ thermal energy and powerful (motion or mechanical work) respectively.

The branch of physical science that deals with the relations/interconversion between heat/thermal
energy and other forms of energy (such as mechanical, electrical, or chemical energy), and by
extension, energy forms’ interrelations
More pragmatically; 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.

To be more specific, it explains how thermal energy is converted to or from other forms of energy
and how matter is affected by this process. Thermal energy is the energy that comes from heat. This
heat is generated by the movement of tiny particles within an object. The faster these particles
move, the more heat is generated.

The heat from the motion of these particles can transfer into nearby particles, and therefore into
other parts of the material or other materials, through a variety of means:
1. Thermal Contact is when two substances can affect each other's temperature.
2. Thermal Equilibrium is when two substances in thermal contact no longer transfer heat.
3. Thermal Expansion takes place when a substance expands in volume as it gains heat. Thermal
contraction also exists. For solids, the volumetric (or cubical) expansion has linear, area (or
superficial) expansion components:
∆𝑙⁄𝑙0 = 𝛼∆𝑇
{∆𝐴⁄𝐴0 = 2𝛼∆𝑇
∆𝑉⁄𝑉0 = 3𝛼∆𝑇
For liquids, volumetric (or cubical) expansion:
∆𝑉⁄𝑉0 = 𝛽∆𝑇
Where the coefficient of thermal expansion [°C−1 or K−1] defined as the ratio of the fractional change
in size of a material to its change in temperature, is represented by the symbol α (alpha) for solids
and β (beta) for liquids. The molecules of liquids are free to move in all directions within the liquid.
On heating a liquid, the average amplitude of vibration of its molecules increases. The molecules
push each other and need more space to occupy. This accounts for the expansion of the liquid when
heated. The thermal expansion in liquids is greater than solids due to the weak forces between their
molecules. Therefore, the coefficient of volume expansion of liquids is greater than the solids.
Liquids have no definite shape of their own. A liquid always attains the shape of its container in
which it is poured. Therefore, when a liquid is heated, both liquid and the container undergo a
change in their volume. Thus, there are two types of thermal volume expansion for liquid: Apparent
volume expansion and Real volume expansion

Water on cooling below 4C° begins to expand until it reaches 0°C. On further cooling, its volume
increases suddenly as it changes into ice at 0°C. When ice is cooled below 0°C, it contracts i.e., its

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volume decreases like solids. This unusual expansion of water is called the anomalous expansion of
water.
For gases, ideal gas law applies: 𝑃𝑉 = 𝑛𝑅𝑇
4. Conduction (heat exchange by contact) is when heat flows through a heated material.

Fig. Conduction of heat through a solid

The temperature of the lower plate is suddenly increased from the gas-plate equilibrium T1 to T2.
Molecules of the gas in contact with this plate will be raised to the higher temperature and will begin
to move with a greater velocity. These faster moving molecules will collide with those next to them
and, after an exchange of momentum; the previously slower molecules will begin to move faster. The
increase in internal energy will gradually propagate through the gas, until the average velocity
everywhere is higher and the temperature of the gas reaches a new equilibrium value (T2).
If we are making macroscopic measurements of gas properties, we will observe a progressive
increase in gas temperature, starting at the lower surface and gradually propagating upwards. This is
known as heat conduction. Heat transfer occurs at the microscopic level, with no macroscopic
displacement. Heat conduction occurs in all materials, not just gases. In solids, where molecules are
not free to move, raising the temperature increases the amplitude of vibration of molecules about
their equilibrium position. This vibration is passed on to neighbouring molecules and therefore
energy is propagated through the entire solid

Fig. Conduction comparison between a gas and a solid

Fourier's Law for heat conduction, or the thermal conduction equation. For a material of cross-
section area A and length L; spanning a temperature difference ∆𝑇 = 𝑇𝐻 − 𝑇𝐶 as shown in Fig.
𝑄 𝐴
= 𝑘 ∆𝑇 ⟺ 𝑞⃗ = −𝑘∇T
𝑡 𝐿
Where Q represents the transfer of heat in time t, A the area through which the heat is flowing, 𝑞⃗ is
the vector of local heat flux density [W.m-2], ∇T is the temperature gradient [K.m-1], k is the
coefficient of thermal conductivity [W.m-1k-1], which characterizes whether the material is a good
conductor of heat or a poor conductor. Typical ks [W/mK]: Diamond 2000 W/mK, Silver 430, Copper
400, Alluminium 240, Iron 80, Stainless steel 14, Ice 1.7, Concrete 0.8, Glass 0.8, Styrofoam 0.035,
air (200C, 1atm) 0.023W/mK

5. Radiation is when heat is transferred through electromagnetic waves, such as from the sun.
Electromagnetic radiation carries energy. When this radiation meets matter, it may, depending on its
wavelength, be absorbed, be reflected or pass through. The substance that absorbs electromagnetic

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radiation obviously gains the corresponding energy. For each substance, a radiation absorption rate
is defined as a function of its wavelength. A body that looks blue absorbs all wavelengths of the
visible spectrum except those corresponding to blue. A body that looks black absorbs all the
wavelengths of the visible spectrum.

The black body is defined as an ideal substance that perfectly absorbs radiation at all wavelengths
(not just the visible ones!). It is demonstrated that each surface element dS of a black body X of
temperature TX emits spontaneously an electromagnetic radiation of power

𝑑𝑃 = 𝜎𝑇𝑥4 𝑑𝑆
The wavelength distribution of the emitted radiation, and thus the perceived colour, depends on the
temperature of the black body. It is this phenomenon which explains that the stars have different
colours according to their temperatures.

If we have a body X (convex, to simplify) of surface S at temperature TX

in an environment at temperature TY (for example by putting it in an
enclosure), two phenomena occur:
• The body X loses energy by black body radiation with a power 𝜎𝑆𝑇𝑥4
• The body X absorbs the energy emitted by the environment.
It is shown that the power received is simply 𝜎𝑆𝑇𝑥4 . By combining these
two effects, the heat δQ gained by X during dt by radiation is written
𝛿𝑄 = 𝜎𝑆(𝑇𝑌4 − 𝑇𝑥4 )𝑑𝑡

All objects emit energy in the form of radiation, electromagnetic waves generated by oscillating
electric charges in the atoms that form the object. If heat energy Q is radiated in a time interval ∆t
by an object with surface area A and absolute temperature T, the rate of heat transfer is found to be
𝑄
= 𝑒𝜎𝐴𝑇 4
∆𝑡
The parameter e is the emissivity of the surface, a measure of how effectively it radiates. The value
of e ranges from 0 to 1. σ is a constant, known as the Stefan-Boltzmann constant, with the value σ =
5.67 × 10–8 W/m2K4.

6. Convection (Heat exchange via a fluid, i.e. macroscopic motion (a current)): e.g. cooking something
in boiling water.
Air is a poor conductor of heat, but thermal energy is easily transferred through
air, water, and other fluids because the air and water can flow.

Forced convection, when the fluid is set in motion externally; For example,
blowing (e.g. to cool down soup) with a fan, etc.

Free convection, when the fluid motion starts spontaneously because the
temperature is not uniform. For example, in a pot of water placed on fire,
convection cells are created: hot water from the bottom of the pot rises to the
surface, cools in contact with the atmosphere and goes down to warm up at the
bottom of the pot.
Fig. Warm water (coloured) moves by convection
A pan of water on the stove is heated at the bottom. This heated water expands, becomes less
dense than the water above. It, and thus rises to the surface, while cooler, denser water sinks to
take its place. The same thing happens to air.

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7. Insulation is when a low-conducting material is used to prevent heat transfer.
Thermodynamics is not concerned about how and at what rate these energy transformations are
carried out but is based on initial and final states of a system undergoing the change. It should also
be noted that Thermodynamics is a science of macroscopic system i.e. of systems composed of N
particles (atoms, molecules, ions, etc.), N being very large (N≫1). This means that it deals with the
bulk system and does not deal with the molecular constitution of matter.

Orders of magnitude: Under normal conditions, the typical distance between particles is
approximately: 3Å = 0.3nm = 3.10-10m for solids or liquids and 3nm for gases. In 1cm3 of matter,
there are typically between: 1022 to 1023 particles for solids or liquids and 1019 to 1020 particles for
gases.
Recall that a mole is defined as the amount of substance in 12g of carbon 12 and the Avogadro
constant NA gives the number of particles per mole: NA = 6:022 1023 mol-1

Example

A mass of m = 1 kg is initially at rest and is dropped from a height of y = yo = 10 m above the ground,
where gravitational acceleration g = 9.81 m/s2. Neglect drag forces. Find the time to reach the
ground, the kinetic energy as a function of time, and the potential energy as a function of time. Plot
key results

Fig.: Sketch of problem for particle motion in a gravitational field

Soln.:
The principle governing the motion of the body is Newton’s second law, embodied in a second order
differential equation. The only force is the gravitational force acting in the negative y direction. This
gives the equation
𝑑2 𝑦 𝑑2 𝑦
𝑚 2 = −𝑚𝑔 ⟺ 2 = −𝑔
𝑑𝑡 𝑑𝑡
Integrate once and second time and using two initial conditions (t=0), we get
𝑑𝑦 1
= −𝑔𝑡 + 𝐶1 ⟹ 𝑦(𝑡) = − 𝑔𝑡 2 + 𝐶1 𝑡 + 𝐶2
𝑑𝑡 2
𝑑𝑦 1 1
𝑦(0) = 𝑦0 , ∴ (0) = 0 ⟺ 𝑦0 = − 𝑔(0)2 + 𝐶1 (0) + 𝐶2 = 𝐶2 ⟹ 𝑦(𝑡) = − 𝑔𝑡 2 + 𝐶1 𝑡 + 𝑦0
𝑑𝑡 2 2
Apply the second initial condition to get
𝟏
0 = −𝑔(0) + 𝐶1 = 𝐶1 ⇔ 𝒚(𝒕) = − 𝒈𝒕𝟐 + 𝒚𝟎
𝟐
For the velocity, we get
𝒅𝒚
= −𝒈𝒕
𝒅𝒕
When the mass reaches the ground, y = 0. Solving for the time when y = 0, we get
1 2𝑦0 2(10𝑚)
0 = − 𝑔𝑡 2 + 𝑦0 ⟹ 𝑡 = ±√ =√ = 1.43𝑠
2 𝑔 9.81 𝑚⁄𝑠 2

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 1 𝑑𝑦 2 1
𝐾𝐸 = 𝑚 ( ) = 𝑚𝑔2 𝑡 2
2 𝑑𝑡 2 ⇔ 𝑲𝑬 + 𝑷𝑬 = 𝒎𝒈𝒚𝟎 = 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕
1 2 2
{𝑃𝐸 = 𝑚𝑔𝑦 = 𝑚𝑔𝑦0 − 2 𝑚𝑔 𝑡
Thus, mechanical energy is conserved here! By conserved, we mean it does not change.
Numerically, we have for y(t), KE(t), and PE(t),
1
𝑦(𝑡) = − (9.81)𝑡 2 + 10 = −4.904𝑡 2 + 10
2
1
𝐾𝐸 = (1)(−9.81)2 𝑡 2 = 48.12𝑡 2
{ 2
1
𝑃𝐸 = (1)(9.81)(10) − (1)(9.81)2 𝑡 2 = 9.81 − 48.12𝑡 2
2
The position as a function of time, the kinetic, potential, and total mechanical energies as functions
of time are plotted in Fig.

Fig.: Position versus time and KE(t), PE(t) and total mechanical energy for particle accelerating in a
gravitational field with no drag force.
One can tell by inspection that as potential energy decreases, kinetic energy increases just as much,
rendering the total mechanical energy to be constant. If we include drag forces, the total
mechanical energy is not constant; in fact, it dissipates with time. We will omit the details, but if we
include a simple drag force proportional to the particle velocity, we get the equations

𝑑2 𝑦 𝑑𝑦 𝑑𝑦
𝑚 2
= −𝑐 − 𝑚𝑔, 𝑦(0) = 𝑦0 , (𝑡 = 0) = 0
𝑑𝑡 𝑑𝑡 𝑑𝑡
Skipping the details of calculation, if we take c = 0.1 N s/m, and all other parameters as before, we
find
𝑦(𝑡) = 991 − 981𝑒 −𝑡⁄10 − 98.1𝑡

𝐾𝐸(𝑡) + 𝑃𝐸(𝑡) = 14533.5 + 4811.8𝑒 −𝑡⁄20 − 19247.2𝑒 −𝑡⁄10 − 962.361𝑡

The kinetic, potential, and total mechanical energies as functions of time are plotted in Fig.

Fig.: KE(t), PE(t) and total mechanical energy for a particle accelerating in a gravitational field in the
presence of a drag force.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 7

When drag forces are included, we begin with the same amount of total mechanical energy and
potential energy. At the end of the calculation, we have the same amount of potential energy (zero),
but less kinetic energy and less total mechanical energy. Where did this energy go? In fact, it is
transformed into another form of energy, thermal energy that is not accounted for in Newtonian
mechanics.

1.2 Branches of thermodynamics

Classical Thermodynamics: The behaviour of matter undergoing the process is analysed with a
macroscopic approach (e.g. by means of temperature and pressure).

Statistical Thermodynamics: every molecule is under the spotlight i.e. the properties of each and
every molecule and ways in which they interact are taken into consideration to characterize the
behaviour of a group of molecules.

Chemical Thermodynamics: is the study of how work and heat relate to each other both in chemical
reactions and in changes of states.

Equilibrium Thermodynamics: is the study of transformations of energy and matter as they

approach the state of equilibrium.

1.3 Selected Application areas of Engineering Thermodynamics

Thermodynamics covers a wide Application in (i) Energy change associated to all chemical and
physical processes, (ii) Mutual transformation of different kinds of energy and, (iii) predicting the
direction and extent of chemical reaction.

Almost all process and engineering industries, agriculture, transport, commercial and domestic
activities use thermal engineering. Typical applications involve: (a) Fossil- and nuclear-fuelled power
stations, turbines, compressors and pumps: Central thermal power plants, captive power plants
based on coal, Nuclear power plants and gas turbine power plant, (b) Cooling of electronic
equipment; (c) Combustion systems: Engines for automobile, ships, airways, spacecraft, Propulsion
systems for aircraft and rockets (d) Alternative energy systems: fuel cells, thermoelectric and
thermionic devices; Magnetohydrodynamic (MHD) converters; Solar-activated heating, cooling, and
power generation; Geothermal systems; Ocean thermal, wave, and tidal power generation; Wind
power. (e) Heating, ventilating, and air-conditioning systems: Vapor compression and absorption
refrigeration, Heat pumps, cooling, heating and ventilation plants, (f) Domestic, commercial, and
industrial lighting, (g) Agriculture, transport and industrial machines, h) Biomedical applications: Life-
support systems, Artificial organs; i) Cryogenic systems, gas separation, and liquefaction

Fig.: Turbojet engine

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 Fig. Steam-fueled electrical power plant and biomedical applications

Fig. Internal combustion 4-stroke Otto-cycle automobile engine

Fig.: Refrigerant circuit and a typical single-stage vapour compression refrigeration and International
Space Station

1.4 State of matter

A state of matter is a description of the type of physical structure that a material substance
manifests, with properties that describe how the material holds together (or doesn’t). There are five
states of matter, though only the first three of them are usually included in the way we think about
states of matter: Gas, Liquid, Solid, Plasma, and Superfluid (such as a Bose-Einstein Condensate).

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All matter consists of atoms or molecules that interact with each other by exerting forces known as
interatomic or intermolecular bonds. The magnitude of these forces determines the state of any
material. Pure substances are commonly found in one of three different states: solid, liquid or gas.
Solids have very strong intermolecular forces so the molecules are close together and their positions
relative to each other are fixed (Fig. a). Liquids have weaker intermolecular forces and the
molecules, though still close, are free to move so that liquids, unlike solids, can flow (Fig. b). Gases
have very large spacing between the molecules, which are free to move randomly. Intermolecular
forces in gases are so weak as to be negligible (Fig. c).

Fig. Molecular arrangements for different states of matter: (a) solid, (b) liquid and (c) gas

A phase is a quantity of matter with uniform chemical composition and physical properties. The three
states of matter, solids, liquids and gases, therefore constitute different phases because they have
different physical properties, even though they may have the same chemical structure. We can have
different phases with the same chemical composition and state: snowflakes and icicles are both solid
forms of water, but have quite distinct molecular structures and properties. Similarly, diamond and
graphite are different phases of carbon.

A phase transition occurs when a material is transformed from one phase to another. The
most common phase transitions are those between liquid and solid phases (freezing versus melting)
or liquid and gas phases (evaporation versus condensation) solid to gas (sublimation or vaporization-
liquid or solid to gas), while only a few rare substances are known to be able to enter a superfluid
state. Plasma is a distinct state of matter, such as lightning. Altering the intermolecular forces and
spacing, typically by changing the temperature or pressure of a substance, produces phase
transitions. As a solid is heated the molecules gain energy and begin to vibrate about their mean
position. Eventually they break loose from their fixed positions and begin to move randomly – the
material melts and becomes liquid. Further heating increases the velocity of molecules and the
spacing between them. The substance expands in volume and the spacing between molecules
increases. Intermolecular forces decrease in magnitude until they become negligible and the material
becomes a gas in which molecules interact only when they collide with each other.

1.5 Energy

News headlines regularly announce that the world faces an energy crisis. Modern societies use
vast amounts of energy to heat and light homes, power factories and fuel vehicles. At the same time
we are told that power can be extracted from fossils, plants, sunlight, tides and wind. It seems that
we are surrounded by energy.

Forms of energy
There are three different ways in which energy can be stored in a system. Potential energy and
kinetic energy are macroscopic forms, and altering them requires a change in the position or velocity
of the system. Internal energy includes all microscopic forms of energy storage. Variations in internal
energy are not the result of a displacement of the system, but correspond to changes in its
temperature, pressure, chemical composition, electrical or magnetic state.

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Fig. Lifting a weight using: (a) the kinetic energy of a moving object, (b) the potential energy of a
raised mass, (c) the internal energy in the chemical bonds of a fuel

Thermodynamics is the study of energy (in the form of heat and/or work) interactions between
systems and the effect of these interactions on the system properties. Roughly speaking, the energy
is the ability to do work, found from the product of force and distance [J = Nm]. In thermodynamics,
we deal with change of the total energy only. Thus, the total energy of a system can be assigned a
value of zero at some reference point. Total energy of a system has two groups: macroscopic and
microscopic.

Macroscopic forms of energy: forms of energy that a system possesses as a whole with respect to
some outside reference frame, such as kinetic and potential energy. The macroscopic energy of a
system is related to motion and the influence of some external effects such as gravity, magnetism,
electricity, and surface tension.

Microscopic forms of energy: are those related to molecular structure of a system. They are
independent of outside reference frames. The sum of microscopic energy is called the internal
energy, U.

The total energy of a system consists of the kinetic, potential, and internal energies:
𝐸 = 𝑈 + 𝐾𝐸 + 𝑃𝐸 = 𝑈 + 𝑚𝑣 2⁄2 + 𝑚𝑔𝑧

Where the contributions of magnetic, electric, nuclear energies are neglected; A system is called
simple compressible system in the absence of electrical, magnetic, gravitational, motion, and surface
tension effects (external force fields).

Internal energy is related to the molecular structure and the degree of molecular activity and it
may be viewed as the sum of the kinetic and potential energies of molecules.

 The sum of translational, vibrational, and rotational energies of molecules is the kinetic energy of
molecules, and it is also called the sensible energy. At higher temperatures, system will have higher
sensible energy.
 Internal energy associated with the phase of a system is called latent heat. The intermolecular
forces are strongest in solids and weakest in gases.
 The internal energy associated with the atomic bonds in a molecule is called chemical or bond
energy. The tremendous amount of energy associated with the bonds within the nucleolus of atom
itself is called atomic energy.

Energy is an extensive property and has units of joules (J). We can also define an intensive property,
the specific energy [J/kg]. Other intensive properties are the potential energy per unit mass of the
system, kinetic energy per unit mass and the specific internal energy. The specific energy of a system
is the sum of its specific kinetic, potential and internal energies

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 𝑃𝐸
𝑝𝑒 =
= 𝑔𝑧
𝑚
𝐸 𝐾𝐸 1 2 1
𝑒 = ⇒ 𝑘𝑒 = = 𝑣 ⇔ 𝑒 = 𝑔𝑧 + 𝑣 2 + 𝑢
𝑚 𝑚 2 2
𝑈
{ 𝑢=
𝑚
For a stationary system, which does not move, the potential and kinetic energies are constant and
only the internal energy changes.

Energy as a whole WRT some outside Related to molecular

Energy
reference, and changes with velocity structure and degree of
and elevation to a reference molecular activity

Macroscopic Microscopic

Kinetic Potential Sensible Latent Chemical Atomic

KE = mV2/2 PE = mgz It’s the sum of Inter- Atomic Bonds

translational, molecular bonds within
vibrational, phase nucleus
rotational change of atoms
energies. Higher
at high The summation of all microscopic
temperatures energies is called internal energy, U
E = U + KE + PE [kJ]
Fig. Forms of energy

Internal energy (U): Total kinetic (random chaotic motion) and potential energy (interaction
between atoms and olecules) of system. E.g. Gas in container with (n, P, V, T). Gas molecules
translate, rotate and vibrate so 𝑈 = 𝐸𝑡𝑟𝑎𝑛𝑠 + 𝐸𝑟𝑜𝑡 + 𝐸𝑣𝑖𝑏

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 ∆𝑈 = 𝑈𝑓 − 𝑈𝑖 ⟹ 𝑚𝑒𝑎𝑠𝑢𝑟𝑎𝑏𝑙𝑒

Joule’s law of internal energy states that internal energy of a perfect gas is a function of
temperature only. In other words, internal energy of a gas is dependent on the temperature change
only and is not affected by the change in pressure and volume. We do not know how to find the
absolute quantity of internal energy in any substance. However, what is needed in engineering is the
change of internal energy (ΔU).
Energy interactions with a closed system can occur via heat transfer and work.

1.6 Energy Transfer

Energy can be transferred to or from a system in two ways: as work (W) or heat (Q). Heat transfer is
an exchange of energy that occurs due to a temperature difference between the system and its
surroundings. All other forms of energy transfer are classified as work. Work does not have to be
mechanical: an electrical current entering a system is considered a form of work.

Both heat and work represents energy in transit. Work and heat are the two methods by which
energy is exchanged between system and surroundings. Work is the transfer of mechanical energy.
Both energy types are based on the common feature “Temperature T”, which is a state variable that
quantifies the “hotness” or “coldness” degree of a system. The units of T are degrees Celsius or
Kelvin. Heat is equivalent to work in that both represent ways of transferring energy. This has been
proved by Joules apparatus that converted the potential energy of falling weights into work done on
the water by a rotating paddle.
A mass m which falls from a height H drives the rotation of blades in a volume of thermally insulated
water. Once all macroscopic movements in the water have stopped, a thermometer indicates a
temperature increase. The same result could have been obtained by supplying the system with heat
(in calories) equal to the mass of water (in grams) multiplied by the temperature variation (in
Celsius). Instead a mechanical energy equal to mgH (potential energy of gravity) was supplied. Heat
is therefore a form of energy and calorie can be expressed in joules (1 cal = 4.186 J).

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 13

 Fig.: Joules 's experiment apparatus to establish heat/energy equivalence, Heat ↔Work [W = JQ]:
work expended in the production of heat or obtained from heat

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.

Heat (Q) is energy transferred between the system and the environment as they interact. Thus, it is
defined as the form of energy that is transferred across a boundary by virtue of temperature
difference. The unit of heat is Joules and its rate of transfer is given in KW or W. It is sometimes
confused with the thermal energy Eth which is the energy of the system due to the motion of its
atoms and molecules. Any system has a thermal energy even if it is isolated and not interacting with
its environment. The units of Eth are Joules.
Main characteristics of heat can be stated as:
- The direction of heat transfer is taken from the high temperature to the low temperature system.
- The heat exists only during transfer into or out of the system
- It is not the property of the system because it does not represent an exact differential dQ. It is
therefore represented by δQ. However, the specific heat is a material property and it is defined at
constant pressure (cp) and at constant volume (cv).
- The specific heat capacity is a substance property that indicates the ease with which a substance
heats up. It is the amount of energy required to increase one unity mass/volume of matter (1kg) by
one unity of temperature (10C or 1K). A good thermal conductor would have a low heat capacity,
indicating that a small amount of energy causes a large temperature change. A good thermal
insulator would have a large heat capacity, indicating that much energy transfer is needed for a
temperature change.
Therefore, the heat required to raise the temperature of the body or a system is
𝑄 = 𝑚𝑐(𝑇2 − 𝑇1 )
Where m: mass [kg], T1 and T2 = Temperatures in 0c or K, c = specific heat [kJ/kg K], the product of mc
is the thermal or heat capacity [C or kJ]
- Heat is a path function: the amount of heat transferred when a system changes from state one to
state two depends on the intermediate states through which the system passes (i.e. path). This
makes dQ (1Q2) inexact
2
∫ 𝑑𝑄 = 𝑄1−2
1
When there is a difference in pressure, there will be displacement work. The pressure difference is
cause and work transfer is the effect. Likewise, whenever there is difference in temperature, there

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 14

will be heat flow. The temperature difference is the cause and the heat is the effect. The extensive
property S is yet to be defined. It is called Entropy [J/K]
2 2
𝑊1−2 = ∫ 𝑑𝑊 = ∫ 𝑝𝑑𝑣
1 1
𝑑𝑄 = 𝑇𝑑𝑠 ⟺ 𝑑𝑆 = 𝑑𝑄 ⁄𝑇
This is valid for a quasi-static process, and the work transfer involved is presented by the area under
the path on p-v diagram, as illustrated in Fig.

When work is done by a system, it is arbitrary taken to be positive, and when work is done on a
system, it is taken to be negative. Heat flow into a system is taken to be positive, and heat flow out
of the system is taken to be negative.

Fig. Heat and work transfers between the system and its surroundings
The net heat added to a system in which heat transfer occurs through several streams
labelled Q1, Q2, Q3, …, is given by summing all the heat transfer terms: Similarly the net work done on
the system is found.
𝑄𝑛𝑒𝑡 = ∑ 𝑄𝑖 𝑎𝑛𝑑 𝑊𝑛𝑒𝑡 = ∑ 𝑊𝑖
𝑖 𝑖
A positive value of Qnet means that more heat is added to the system than it loses to the
surroundings. A positive value of Wnet implies that more work is supplied to the system than it does
on the surroundings.
The rate of doing work (𝑊̇ ) is also known as power [J/s] also known as Watt [W] and for mechanical
work done by a constant force F over an infinitesimal distance dx. The rate of heat transfer is
denoted by 𝑄̇ and also has units of watts.
𝛿𝑊 𝐹𝑑𝑥
𝑊̇ = = = 𝐹𝑣
{ 𝑑𝑡 𝑑𝑡
𝛿𝑊
𝑄̇ =
𝑑𝑡
Where V is the velocity of the point of application of the force

It is sometimes useful to talk about the heat transfer per unit mass of the system or the work done
per unit mass of the system. Both q and w have units of J / kg. Remember, though, that heat and
work are not properties of the system, so that q and w are not intensive properties.
𝑄
𝑞=
{ 𝑚
𝑊
𝑤=
𝑚
When a force acts on the boundaries of a system and deforms them, so that the system is either
compressed or expanded, work is done since the point of application of the force moves through a
finite distance. This is known as boundary work. In Fig.; the pressure (P) of the gas resists the
forward movement of the piston, so a force (F) has to be exerted on it. The force must be just

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 15

sufficient to overcome the resistance offered by the gas, so F = PA. No boundary work is done on a
system whose volume remains constant. 𝛿𝑊 = −𝐹𝑑𝑥 = −𝑃𝐴𝑑𝑥 = −𝑃𝑑𝑉

Work done by gas for Volume changes:

Fig. Boundary work done during compression of a gas and Force (PA) exerted by a system during
small expansion
The work done by that force when the piston moves out by a distance dx

𝑑𝑊 = 𝐹𝑑𝑥 = 𝑃𝐴𝑑𝑥 = 𝑃𝑑𝑉 ∴ 𝑉 = 𝐴𝑑𝑥 … (1)

It is possible to have two processes that begin and finish with the same pressure and volume,
but require very different amounts of work.
The work done during process 1–b–2 is greater than that during 1–a–2, as seen by comparing the
areas under the two process curves. It takes more work to compress a hot gas than the same
amount of gas at a lower temperature: that is the reason industrial gas compressors have large
cooling fins to release heat to the atmosphere.

Fig. Work done is the area under the curve on a P‐V diagram and two processes with the same
starting and ending points, but a greater amount of work is done in the second process

In a finite volume change from V1 to V2 and graphically the derived relationship is shown in RHS
figure.

𝑊 = lim 𝑝𝑑𝑉 … (2)

𝑉1⟶𝑉2

Thus eqn (2) can be interpreted graphically as area under the curve between limits V1and V2. If the
pressure remains constant while the volume changes, then work is: 𝑊 = 𝑃(𝑉2 − 𝑉1 ) … (3)

The work done not only depends on initial and final states but also on the intermediate states i.e.,
on the path: Work done in a process is given by area under the process on the PV diagram

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 16

 Fig. pV-diagram for a system undergoing an expansion (work is done by the system against its
surroundings), compression (work is done on the system) with varying pressure and an expansion
with constant pressure

Applications to typical process

Constant pressure: A system in a cylinder with a piston that is free to move (see Fig.) always stays at
constant pressure.

The piston will rise or fall during any process,

maintaining the pressure P1 = P2 = constant
throughout. We can select the pressure that we
want by placing weights on the piston – the
greater the weight the higher the system pressure.
The work done during the process is
𝑉2 𝑉2
𝑊12 = − ∫ 𝑃𝑑𝑉 = 𝑃1 ∫ 𝑃𝑑𝑉 = 𝑃1 (𝑉1 − 𝑉2 )
𝑉1 𝑉1

Fig. Constant pressure process

Solved Examples:
A piston driven by compressed air at 200kPa in a cylinder is required to do 500J of work while
moving through a distance of 0.25m. What should the diameter of the cylinder be?

Soln: Gas pressure is constant at P = 200kPa, work done by system W12 = –500kPa, distance moved
by piston ∆x = –0.25 m. Since the system expands and does work on the surroundings, work and
displacement are negative.
𝑥2 𝑥2
𝑊12 = ∫ 𝑃𝐴𝑑𝑥 = 𝑃𝐴 ∫ 𝑑𝑥 = 𝑃𝐴(𝑥2 − 𝑥1 ) = 𝑃𝐴∆𝑥
𝑥1 𝑥1
where A is the cross‐sectional area of the piston and ∆x is the distance moved by the piston
𝑊12 −500𝐽 4𝐴 4 × 0.01
⟹𝐴= = 3
= 0.01𝑚2 ⟺ 𝐷 = √ = √ = 0.113𝑚
𝑃∆𝑥 200 × 10 𝑃𝑎 × −0.25 𝜋 𝜋

A cylinder with a frictionless piston contains 0.5 kg of air with a volume of 0.3 m 3 at 20°C. The air is
allowed to expand freely while being heated until its temperature reaches 150°C. What is the work
done by the piston on the surroundings?

Soln: Mass of air m=0.5kg, initial volume V1=0.3m3, initial temperature T1=20°C=(273.15+20)K =
293.15K, final temperature T2=150°C=(273.15+150)K=423.15K; Air behaves as an ideal gas, air
pressure remains constant since the piston is free to move P2=P1. The gas constant for air is

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 17

R=0.2870kJ/kgK. We have to find initial pressure, final volume and then, the work done by the
system.

𝑚𝑅𝑇1 0.5 × 0.287 × 103 × 293.15

𝑃1 = =
𝑉1 0.3
= 140.22𝑘𝑃𝑎

𝑚𝑅𝑇2 0.5 × 0.287 × 103 × 423.15

𝑉2 = =
𝑃2 140.22
= 0.43305𝑚3

𝑊12 = 𝑃1 (𝑉1 − 𝑉2 ) = 140.22 × 103 (0.3 − 0.43305)

= −𝟏𝟖. 𝟔𝟓𝟔𝒌𝑱
Fig Constant pressure expansion in a cylinder with a frictionless piston

Constant temperature, ideal gas: If a cylinder filled with gas is immersed in a bath through which
water at a regulated temperature circulates (Figure 4.9), the system stays at constant temperature.
From the equation of state for an ideal gas, P m = RT / V , so the work done is
𝑉2 𝑉2
𝑚𝑅𝑇
𝑊12 = − ∫ 𝑃𝑑𝑉 = − ∫ 𝑑𝑉
𝑉1 𝑉1 𝑉

As m, R and T are all constants for a closed,

isothermal system,
𝑉2
𝑑𝑉 𝑉1
∴ 𝑊12 = −𝑚𝑅𝑇 ∫ = 𝑚𝑅𝑇 𝑙𝑛
𝑉1 𝑉 𝑉2
Fig. Constant temperature process for an ideal gas

Example
Air is contained in a 1m3 volume cylinder at a pressure of 100kPa. It is compressed until its volume is
halved while keeping the temperature constant. How much work is required for compression?
Soln.: Initial volume V1 = 1 m3, final volume V2 = 0.5V1, initial pressure P1 = 100kPa, temperature is
constant during compression. Air behaves as an ideal gas.
𝑉1 𝑉1
𝑃1 𝑉1 = 𝑚𝑅𝑇1 ∴ 𝑊12 = 𝑚𝑅𝑇 𝑙𝑛 = 𝑃1 𝑉1 𝑙𝑛
𝑉2 𝑉2
1
𝑊12 = 100 × 103 × 1 × 𝑙𝑛 = 𝟔𝟗. 𝟑𝟏𝟓𝒌𝑱
0.5
Polytropic Process: A variety of common thermodynamic processes can be modeled by a curve of
the form
𝑃𝑉 𝑛 = 𝐶
where C and n are both constants. Any process that follows Equation is known as a polytropic
process, applicable for ideal gases. Specific values of n correspond to different processes. For
example, setting n = 0 give a constant pressure process, n = 1 for an ideal gas undergoing an
isothermal process and n = ∞ a constant volume process. In general,
𝐶 = 𝑃1 𝑉1𝑛 = 𝑃2 𝑉2𝑛
If 𝑛 ≠ 1, the work done during a polytropic process is
𝑉2 𝑉2
𝐶 𝑑𝑉 𝑃2 𝑉2 − 𝑃1 𝑉1
𝑃 = 𝑛 ∴ 𝑊12 = − ∫ 𝑃𝑑𝑉 = −𝐶 ∫ 𝑛
⟺ 𝑊12 = ; 𝑓𝑜𝑟 𝑛 ≠ 1
𝑉 𝑉1 𝑉1 𝑉 𝑛−1
If n = 1, as is the case in an isothermal process,

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 18

 𝑉2 𝑉2
𝑑𝑉 𝑉1
𝑊12 = − ∫ 𝑃𝑑𝑉 = −𝐶 ∫ 𝑛
= 𝐶 𝑙𝑛
𝑉1 𝑉1 𝑉 𝑉2
𝑉1 𝑉1
𝑊12 = 𝑃1 𝑉1 𝑙𝑛 = 𝑃2 𝑉2 𝑙𝑛 ; 𝑓𝑜𝑟 𝑛 = 1
𝑉2 𝑉2
Example
Gas in a cylinder is expanded by a piston in a process for which PVn = C, where C and n are constants.
The initial pressure and volume are 3bar and 0.2m3 respectively and the final volume is 0.6m3.
Determine the work done by the gas if (a) n = 1.4 and (b) n = 1.0.

Soln.: Initial pressure P1 = 3bar, initial volume V1 = 0.2m3, final volume V2 = 0.6m3, gas expands in a
polytropic process where PVn = C. For a polytropic process: ∆𝑃𝐸 = 𝑚𝑔∆𝑧
(a) For n = 1.4, to find the final pressure
1.4 1.4
𝑉1 1.4 0.2 1.4
𝑃1 𝑉1 = 𝑃2 𝑉2 ⟺ 𝑃2 = 𝑃1 ( ) = 3 ( )
𝑉2 0.6
= 0.64439𝑏𝑎𝑟
𝑃2 𝑉2 − 𝑃1 𝑉1
𝑊12 =
𝑛−1
0.64439 × 105 × 0.6 − 3 × 105 × 0.2
= = −𝟓𝟑. 𝟑𝟒𝟐𝒌𝑱
1.4 − 1
Fig. Polytropic expansion of gas in a cylinder
(b) For n = 1
𝑉1 0.2
𝑊12 = 𝑃1 𝑉1 𝑙𝑛 = 3 × 105 × 0.2 × 𝑙𝑛 = −𝟔𝟓. 𝟗𝟏𝟕𝒌𝑱
𝑉2 0.6
1.7 Mass and volume: How do we describe matter? Mass [kg] and volume [m3 or 1l=10-3m3] are the
most obvious properties to describe the quantity of a substance and the amount of space that it
occupies. Molar units are often used to measure mass.

Joseph Gay‐Lussac had observed that hydrogen gas burning in oxygen gives water vapour according
to the reaction below with regular gases volumes: 2l of hydrogen react with 1l of oxygen to produce
2l of steam.
2𝐻2 + 𝑂2 ⟶ 2𝐻2 𝑂2
Amadeo Avogadro’s hypothesis: Equal volumes of gases are made up of an equal number of
molecules. Therefore, 2l of H2 contained twice the number of molecules as 1l of O2 and they would
combine in exactly the required proportion.

Atoms consist of a heavy nucleus surrounded by much lighter electrons. The mass of an atom is
almost entirely that of its nucleus, consisting of positively charged protons, and uncharged neutrons,
which have near equal masses – approximately 1.67 × 10–27 kg. Electrons are much smaller, with a
mass of only 9.11 × 10–31 kg. The atomic mass unit is defined as being one‐twelfth the mass of a
carbon‐12 atom that contains six protons and six neutrons, so that the protons and neutrons both
have masses of almost exactly one atomic mass unit. The masses of atoms are specified in terms of
atomic mass units.

As Many elements do not exist naturally as individual atoms, the mass of a molecule (combination of
alike elements or chemical compound of different specie atoms), specified in atomic mass units, is
known as its molar mass (M).

Careful experimentation has established that 2g of diatomic hydrogen contains 6.022×1023

molecules, which is known as Avogadro’s number (NA). A molecule of diatomic oxygen has a mass 16
times that of a molecule of hydrogen, so 32g of oxygen will also contain NA molecules. The mass of

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 19

any substance that contains NA molecules is known as a gram‐mole (abbreviated gmol) or simply
mole (abbreviated mol). A mole is frequently used as a unit of mass: a mole of any substance is its
molar mass in grams. We can also define a kilogram‐mole (kmol), which is the molar mass in
kilograms. The units of molar mass then become [g/mol or kg/kmol]. We can easily convert between
mass in kg[m] and mass in kmol[N] using the relation

𝑚[𝑘𝑔] = 𝑁[𝑘𝑚𝑜𝑙] × 𝑀[𝑘𝑔⁄𝑘𝑚𝑜𝑙 ]

During the combustion of hydrogen two molecules of hydrogen react with one molecule of oxygen
to produce two molecules of water. To carry out this reaction in the laboratory, a chemist would
burn 2mol of H2 (4g) in 1mol of O2 (32g) to produce 2mol of H2O (36g). These masses will give exactly
the right ratio of oxygen and hydrogen molecules to complete the reaction without having any gas
left over.

Avogadro’s hypothesis can be expressed mathematically by saying that if all other conditions (such
as temperature and pressure) are held constant, the volume of a gas is

𝑉 = 𝐶1 𝑁, 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇 𝑎𝑛𝑑 𝑃
Where C1 is a constant of proportionality and N is the number of moles in the gas. One mole of any
gas has NA = 6.022 × 1023 molecules and therefore occupies the same volume as a mole any other
gas. One mole of gas at 0°C and atmospheric pressure occupies a volume of approximately 22.4l.

Pressure
A gas confined to a closed vessel exerts a force (F) on it due to gas molecules hitting the walls
of the vessel and rebounding. This force, divided by the area (A) on which it is acting, is known as the
gas pressure.

Fig. Force exerted by molecules striking a surface and rebounding and, Pressure within a fluid is
independent of direction
Pressures within fluids can be defined by imagining that an infinitesimally small cube is inserted into
the fluid at the required location. The force exerted by molecules impinging on a wall of this cube,
divided by its area, will give the pressure.

Pressure is the force exerted by a fluid per unit area.

𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝐹𝑜𝑟𝑐𝑒⁄𝐴𝑟𝑒𝑎 [𝑁⁄𝑚2 = 𝑃𝑎, 1𝑏𝑎𝑟 = 105 𝑃𝑎 𝑜𝑟 1𝑎𝑡𝑚 = 1.1325𝑏𝑎𝑟 ≅ 0.1𝑀𝑃𝑎]

In fluids, gases and liquids, we speak of pressure; in solids this is stress. For a fluid at rest, the
pressure at a given point is the same in all directions.
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑚𝑔 𝜌𝐴ℎ𝑔
𝑃= ⇔𝑃= = = 𝜌𝑔ℎ
𝐴𝑟𝑒𝑎 𝐴 𝐴

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 20

Fig.: Pressure of a fluid at rest increases with depth (due to added weight), but constant in horizontal
planes. Absolute, gauge, and vacuum pressures

The actual pressure at a given position is called the absolute pressure, and it is measured relative to
absolute vacuum.
𝑔𝑎𝑢𝑔𝑒 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑎𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 − 𝑎𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑖𝑐 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑝𝑔𝑎𝑢𝑔𝑒 = 𝑝𝑎𝑏𝑠 − 𝑝𝑎𝑡𝑚

∴ 𝑝 > 𝑝𝑎𝑡𝑚

𝑝𝑣𝑎𝑐 = 𝑝𝑎𝑡𝑚 − 𝑝𝑎𝑏𝑠

∴ 𝑝 < 𝑝𝑎𝑡𝑚

In thermodynamics calculations, always use absolute pressure. Most pressure measuring

devices are calibrated to read zero in the atmosphere (they measure Pgauge or Pvac). A device that
measures pressure using a column of liquid is called a Manometer. The cross
sectional area of the tube is not important. The manometer measures the gauge pressure.

𝑝1 = 𝑝𝑎𝑡𝑚 + 𝜌𝑔ℎ [𝑘𝑃𝑎]

Fig.: Basic manometer, Burdon gauge (tub tends to straighten under pressure) and Pressure sensor
with automatic data acquisition

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 21

Bourdon Tube is a device that measures pressure using mechanical deformation. Pressure
Transducers are devices that use piezoelectrics to measure pressure.
Barometer is a device that measures atmospheric pressure. It is a manometer with a near
vacuum on one end.

Note: The usually symbol of pressure is lower case “p” in order to distinguish the pressure from the
power. As the power is rarely mentioned, we sometimes will prefer to use upper case “P” for
pressure, so as to identify it with specific values.

Example:
What is the absolute pressure on the hull of a submarine (a) floating on the surface of the sea and
(b) at a depth of 100 m underwater?

Soln.:

(a) P = Patm = 1.013 25 × 105 Pa = 0.101 33 MPa

(b) P = Patm+ ρgh = 1.01325×105 Pa + 1000 × 9.81 × 100 Pa = 1.0823 MPa

The piston of a cylinder‐piston device has a mass of 60kg and a cross‐sectional area of 0.04m2, as
shown in Fig. The depth of the liquid in the cylinder is 1.8m and has a density of 1558kg/m3. The
local atmospheric pressure is 0.97bar, and the gravitational acceleration is 9.8 m/s2. Determine the
pressure at the bottom of the cylinder.

Soln.: the pressure at the bottom of the cylinder can be found from the summation of the forces due
to atmospheric pressure, piston weight, and the weight of the liquid in the cylinder.

𝑊𝑏𝑜𝑡𝑡𝑜𝑚 = 𝑝𝑎𝑡𝑚 𝐴 + 𝑊𝑙𝑖𝑞𝑢𝑖𝑑 + 𝑊𝑝𝑖𝑠𝑡𝑜𝑛

𝑚𝑔
𝑝𝑏𝑜𝑡𝑡𝑜𝑚 = 𝑝𝑎𝑡𝑚 + + 𝜌𝑔ℎ
𝐴
𝑝𝑏𝑜𝑡𝑡𝑜𝑚 = 0.97𝑏𝑎𝑟
60𝑘𝑔 × 9.8 𝑚⁄𝑠 2
+{ + 1558 𝑘𝑔⁄𝑚3 × 9.8 𝑚⁄𝑠 2
0.04
1 𝑁 ⁄𝑚 2 1𝑏𝑎𝑟
× 1.8𝑚} [( 2 )( 5 )] = 1.2918𝑏𝑎𝑟𝑠
1𝑘𝑔⁄𝑚. 𝑠 10 𝑁⁄𝑚2

1.8 Ideal Gas Equation

When energy is added or removed from a gas its intensive properties such as pressure, temperature
and specific volume may change and change are not all independent. possible to develop equations
that tell us how other properties will change, so that we can write a function of the form

𝑓(𝑃, 𝑣, 𝑇) = 0
Typical equations of state (i.e. giving relations between intensive properties) are:

 Boyle equation stating “the pressure of a fixed mass of gas held at constant temperature
varied inversely with the volume of the container it is confined in”
𝐶2
𝑃 = , (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇)
𝑉
Where C2 is a constant depending on mass and temperature of the gas.

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  Gay‐Lussac’s or Charles’s law “the volume of a fixed mass of gas that is free to expand and
contract at constant pressure is proportional to its temperature”
𝑉 = 𝐶3 𝑇, (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃)
Combining the laws of Avogadro, Boyle and Charles Equations, we obtain the ideal gas equation:
𝑉 = 𝐶1 𝑁, 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇 𝑎𝑛𝑑 𝑃
𝐶
{ 𝑃 = 2 , (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇) ⇔ 𝑷𝑽 = 𝑵𝑹𝒖 𝑻
𝑉
𝑉 = 𝐶3 𝑇, (𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃)
Ru is a constant, known as the universal gas constant, which experiments have shown has the
same value for all gases at sufficiently low density Ru = 8.314kJ/kmolK. Experiments have shown that
the volume of 1mole of any perfect gas at 1bar and 00C is approximately 22.71m3.

𝑝𝑉 1 × 105 × 22.71
𝑅𝑢 = = = 8314.3 𝑁𝑚⁄𝑚𝑜𝑙𝑒 𝐾
𝑛𝑇 1 × 273.15
If we prefer to use kilograms instead of moles as our unit of mass, we can use the relation m = NM to
rewrite the ideal gas equation as
𝑚
𝑃𝑉 = 𝑅𝑢 𝑇
𝑀
Defining a gas constant for each particular gas, R = Ru/M, we have the ideal gas equation in mass
units:
𝑷𝑽 = 𝒎𝑹𝑻
The gas constant R is different for every gas and values for some common substances. All gases
behave as ideal gases when their densities are low, that is, when they are at sufficiently low
pressure and high temperature. Most common gases, such as air, nitrogen, oxygen and carbon
dioxide, behave as ideal gases at atmospheric pressures and temperatures. Steam also behaves as
an ideal gas if it is heated above its boiling point.

In practice, no gas obeys this law rigidly, but many gases tend towards it. An imaginary ideal gas
which obeys this law is called a “perfect gas” and the equation
𝒑𝒗
= 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕 = 𝑹
𝑻
Is called the characteristic equation of a state of a perfect gas. Each perfect gas has a different gas
constant (R [Nm/kgK] or [kJ/kgK]).

For oxygen which has a molecular weight of 32, what is its gas constant
𝑅0 8314
𝑅= = = 259.8 𝑁𝑚⁄𝑘𝑔 𝐾
𝑀 32
What is the pressure of 7 kg of nitrogen gas confined to a volume of 0.4m3 at 20C?

Soln.:
𝑀 7 × 103 𝑔
𝑝𝑉 = 𝑛𝑅𝑇 ∴ 𝑛 = = = 250𝑚𝑜𝑙𝑒𝑠
𝑚 28 𝑔⁄𝑚𝑜𝑙
𝑛𝑅𝑇
𝑝= = 15.2 × 105 𝑁𝑚2
𝑉

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Modelling Ideal Gases
To understand why low‐density gases follow the ideal gas equation, it helps to create a simple model
of gas behaviour. The kinetic theory of gases is based on several simplifying assumptions:
(1) A gas is made of a very large number of elementary particles called molecules that are in
constant, random motion. All molecules have the same mass (me); (2) the total number of molecules
(n) is very large; (3) Molecules collide perfectly elastically with each other and with the walls of the
container. They obey Newton’s laws during collisions; (4) there is no force acting on molecules
except during collisions; (5) the volume of molecules is negligible – they are considered to be point
masses.

A gas is confined in a cubical container with sides of length L. A molecule with

velocity (c) hits the wall normal to the x‐axis and rebounds. After colliding
with the surface the x‐component of the velocity becomes –cx. Since the only
force acting on the molecule is in the x‐direction the other velocity
components (cy, cz) are unchanged.

Fig. A molecule contained in a box of side L hits a wall with x‐velocity component cx and rebounds.
The x‐velocity component becomes –cx.
The change in momentum of the molecule is
∆𝑝 = (−𝑚𝑒 𝑐𝑥 ) − (𝑚𝑒 𝑐𝑥 ) = −2𝑚𝑒 𝑐𝑥
The change in momentum of the container wall is equal in magnitude but opposite in
direction (−∆𝑝 = 2𝑚𝑒 𝑐𝑥 ) , so that total momentum is conserved.
Molecule at the opposing face, rebounds off it and then crosses the length of the box again. The
time taken to cross the length (L) of the box is ∆𝑡 = 𝐿/𝑐𝑥 , so the interval of a molecule to hit twice
the same face again is 2∆𝑡 = 2𝐿/𝑐𝑥 . The force exerted by the molecule on the wall equals the rate
𝑣2 −𝑣1 𝑚𝑣2 −𝑚𝑣1
of momentum transfer to the wall (𝑚. 𝑎 = 𝑚 = )
𝑑𝑡 𝑑𝑡
∆𝑝 𝑐𝑥 𝑚𝑒 𝑐𝑥2
− = (2𝑚𝑒 𝑐𝑥 ) ( ) =
2∆𝑡 2𝐿 𝐿
Summing the force exerted by all the n molecules in the box and dividing by the area of the
surface (L2) gives the total pressure (P) on the wall:
2 2 2 2
𝑚𝑒 𝑐𝑥,1 + 𝑚𝑒 𝑐𝑥,2 + 𝑚𝑒 𝑐𝑥,3 + ⋯ + 𝑚𝑒 𝑐𝑥,𝑛 1
𝑃=( ) ( 2)
𝐿 𝐿
Since the mass of all molecules (me) is the same,
2 2 2 2
𝑚𝑒 2 2 2 2
𝑛𝑚𝑒 𝑐𝑥,1 + 𝑐𝑥,2 + 𝑐𝑥,3 + ⋯ + 𝑐𝑥,𝑛
𝑃 = 3 (𝑐𝑥,1 + 𝑐𝑥,2 + 𝑐𝑥,3 + ⋯ + 𝑐𝑥,𝑛 )= 3 ( )
𝐿 𝐿 𝑛
The total mass of gas in the container is m = nme and the volume of the gas is V = L3. We can define
an average velocity for all the molecules, known as the root mean square (rms) velocity:
2 2 2 2 1⁄2
(𝑐𝑥,1 + 𝑐𝑥,2 + 𝑐𝑥,3 + ⋯ + 𝑐𝑥,𝑛 ) 𝒎
𝑐𝑥,𝑟𝑚𝑠 = [ ] ∴ 𝑷 = 𝒄𝟐𝒙,𝒓𝒎𝒔
𝑛 𝑽
2 2 2 2
The magnitude of the total velocity of a molecule is 𝑐 = 𝑐𝑥 + 𝑐𝑦 + 𝑐𝑧 . Since velocities are random
the average value of their components in all directions should be the same
2 2 2 2 2
𝟏𝒎 𝟐
𝑐𝑥,𝑟𝑚𝑠 = 𝑐𝑦,𝑟𝑚𝑠 = 𝑐𝑧,𝑟𝑚𝑠 ⇔ 𝑐𝑟𝑚𝑠 = 3𝑐𝑥,𝑟𝑚𝑠 ∴𝑷= 𝒄
𝟑 𝑽 𝒓𝒎𝒔
Since m = NM where N is the number of moles of gas and M is its molecular mass,
𝟏
𝑷𝑽 = 𝑵𝑴𝒄𝟐𝒓𝒎𝒔
𝟑

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This equation helps us understand Boyle’s law. If gas temperature is fixed the average molecular
speed does not change and the right hand side of Equation is a constant. Gas pressure will vary
inversely with volume in this case.
Internal energy
If we combine this equation with the ideal gas equation, and dividing by 2 and Avogadro’s number
(NA) on both sides,
1 2 1 1𝑀 2 3 𝑅𝑢
𝑃𝑉 = 𝑁𝑀𝑐𝑟𝑚𝑠 ⇔ 𝑀𝑐𝑟𝑚𝑠 2
= 𝑅𝑢 𝑇 ⇔ 𝑐𝑟𝑚𝑠 = 𝑇
{ 3
𝑃𝑉 = 𝑁𝑅𝑢 𝑇 3 2 𝑁𝐴 2 𝑁𝐴
Since the mass of a single molecule is me = M/NA;
1 2
3
𝑚𝑒 𝑐𝑟𝑚𝑠 = 𝑘𝑇
2 2
Where 𝑘 = 𝑅𝑢 ⁄𝑁𝐴 is known as the Boltzmann constant and has a value of 1.38 × 10–23 J/K
Therefore, the kinetic energy of a single molecule (RHS of equation) is proportional to the
temperature of the gas. This gives us an interpretation for what temperature means at the
molecular level: it is a measure of the energy stored in the motion of molecules. the total
molecular kinetic energy of a gas is obtained by multiplying the number of molecules (n):
1 2
3 3 𝑛 3
𝑚𝑒 𝑛𝑐𝑟𝑚𝑠 = 𝑛𝑘𝑇 = ( ) (𝑁𝐴 𝑘𝑇) = 𝑁𝑅𝑢 𝑇
2 2 2 𝑁𝐴 2
Even though the bulk gas itself is not moving, and has no macroscopic kinetic energy, it can store
energy at a microscopic level in the motion of its molecules. The total microscopic energy of all the
molecules is known as internal energy. The internal energy (U), is an extensive property with units of
joules, given by
3
𝑈 = 𝑁𝑅𝑢 𝑇
2
If we change the temperature of an ideal gas from T1 to T2 its energy changes by LHS equation and
dividing by the mass of the gas (m), the specific internal energy change is found
3 3
𝑈2 − 𝑈1 = 𝑁𝑅𝑢 (𝑇2 − 𝑇1 ) ⇔ 𝑢2 − 𝑢1 = 𝑅(𝑇2 − 𝑇1 )
2 2
Thus, the internal energy of an ideal gas is a function only of its temperature: as the temperature
increases so does the energy. This equation was derived assuming that molecules are point masses,
so that they can only store translational kinetic energy. This is a good assumption for molecules that
have only a single atom, such as helium or argon. It predicts the internal energy of monoatomic
gases very accurately, but does not work well for larger molecules.
More complex gases with more than one atom, such as oxygen, nitrogen, or water vapour can store
energy in other modes such as rotation or vibration. In general, the internal energy of any system
includes all the energy stored at a molecular level, including molecular kinetic energy (due to
translation, vibration or rotation), molecular potential energy (due to electric and magnetic fields)
and the energy stored in chemical bonds.
Molecules in an ideal gas are so far apart that long‐distance forces between them are negligible.
Increasing the pressure and bringing the molecules closer together has no effect on internal energy
because, as long we have ideal gas behaviour, intermolecular forces can still be disregarded. For
gases that do not behave ideally internal energy may, in general, depend on both pressure and
temperature. We can state that for any ideal gas
𝑢2 − 𝑢1 = 𝑐(𝑇2 − 𝑇1 )
Where c is a gas property known as the specific heat that can be measured experimentally

Questions

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Heat is
A. The amount of thermal energy in an object; B. the energy that moves from a hotter object to a
colder object. C. a fluid-like substance that flows from a hotter object to a colder object; D. both A
and B; E. both B and C

Suppose you are an astronaut in space, hard at work in your sealed spacesuit. The only way that you
can transfer excess heat to the environment is by
A. conduction; B. radiation. C. convection; D. evaporation

The thermal behaviour of water is characterized by the value of its

A. heat density, B. heat constant, C. specific heat. D. Thermal index

Explain the difference between heat and thermal energy?

Compare and contrast between heat and work?
Explain why heat and work are not state functions?

A 40kW engine powers a car driving at a constant speed of 100 km/h. What is the
force resisting the motion of the car?
𝑊 𝑊̇ 40 × 103 𝑊 40 × 103 𝑊
𝑃𝑜𝑤𝑒𝑟 = 𝑊̇ = = 𝐹𝑣 ⟺ 𝐹 = = =
𝑡 𝑣 1 27.778 𝑚⁄𝑠
100 𝑘𝑚⁄ℎ × 103 𝑚⁄𝑘𝑚 ×
3600 𝑠⁄ℎ
Therefore, the force resisting the motion of the car is 1440.0N or 1.44kN

Soln.:
A ideal monatomic gas is taken through the process ABCDA as shown in below P-V diagram.
Calculate the Work done by gas
P 2P,V 2P,2V
B C

A D
P,V P,2V
V
Soln.: Work done by the gas from A to B = 0 (as volume constant and area enclosed by AB is zero);
Work done by the gas from B to C = 2PV (Area enclosed by line BC); Work done by the gas from C to
D = 0 (as volume constant and area enclosed by AB is zero); Work done by the gas from D to A = -PV
(Area enclosed by line BC and negative as volume is decreased)
Net Work Done = 2PV - PV = PV
An ideal gas undergoes cyclic process ABCDA as shown in given P-V diagram .The amount of work
done by the gas is
P
D C
2P0

P0 A B

V0 3V0 V

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Soln.: Work done by the gas from A to B = 2PV (Area enclosed by line AB); Work done by the gas
from B to C = 0 (as volume constant and area enclosed by BC is zero); Work done by the gas from C
to D = -4PV (Area enclosed by line CD and negative as volume is decreased); Work done by the gas
from D to A = 0 (as volume constant and area enclosed by DA is zero)
Net Work Done = 2PV - 4PV = -2PV

1.9 Laws of thermodynamics

Thermodynamic is basically is based on four principles (referred to as "Laws of thermodynamics").
These laws are not formulated; rather these are generalization deduced from our long experience in
nature:

0th law: defines/ introduces the concept of temperature (T) and thermodynamic equilibrium where
two objects attain the same temperature when brought in thermal contact.

1st law: mandates conservation of energy with its surroundings strictly by heat flow or work and
represents the relationship between heat and mechanical work. It defines Internal energy.

2nd law: Defines entropy (S). 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; and

3rd law: gives numerical value to entropy. It 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.

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 Chapter 2: THERMODYNAMIC CONCEPTS AND ZEROTH LAW OF THERMODYNAMICS

2.1 Thermodynamic Systems and control volume

A system is part of the universe of fixed mass chosen for observation, separately from the rest of the
universe. It is a specific portion of matter with a definite boundary on which the attention is to be
focussed. An example of a system is biological organism (Fig.)

Fig. Sketch of a universe composition and system interactions with the surroundings and Human
digestive system as an open system which exchanges food (matter) with the surrounding (body)

Everything outside that interacts with system; i.e. has a direct influence on the system behaviour; is
the surrounding. The system plus surroundings comprise a universe.

The boundary interface between a system and its surroundings is the system wall. The system
boundary may be real or imaginary, fixed or deformable.

If heat cannot pass through the system wall, that impermeable boundary to the heat flow is termed
an adiabatic or Adiathermal wall (e.g. walls of a vacuum flask), and the system is said to be
thermally isolated or thermally insulated.

If heat can pass through the wall, it is termed a diathermal wall. Two systems connected by a
diathermal wall are said to be in thermal contact.

The system, surroundings, and system boundary for a universe are shown for a potato-shaped
system in Fig. We allow two important interactions between the system and its surroundings as
shown in Fig.:
 Heat can cross into the system (our potato can get hot), and
 Work can cross out of the system (our potato can expand).

Systems classification
In terms of mass and energy exchange:
a. Isolated System – An isolated system cannot exchange both energy and mass with its
surroundings.

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No such system physically exists. Universe is the only example, which is perfectly isolated.

An existing sub-classification consists in system with adiabatic walls. Adiabatic System can only
exchange work and not heat with the surrounding. All adiabatic systems are thermally insulated
from their surroundings. For example, thermos flask containing a liquid

b. Closed System – Across the boundary of the closed system, the transfer of energy takes place but
the transfer of mass doesn’t take place.

Examples: Car battery: Electric supply takes place from and to the battery but there is no material
transfer. Tea kettle: Heat is supplied to the kettle but mass of water remain constant. Kitchen
refrigerator: No mass flow. Electricity is supplied to compressor motor and heat is lost to
atmosphere. Thermometer into the mouth: No mass flow. Heat is supplied from moth to
thermometer bulb. Pressure cooker: There is no mass exchange (neglecting small steam leakage).
Heat is supplied to the cooker and Water in tank, gas compression in the piston cylinder assembly.

c. open System also known as a control volume. – In an open system, the mass and energy both may
be transferred between the system and surroundings. A steam turbine is an example of an open
system.

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 Fig. Example of a control volume (open system) in engineering, biology and botany

Examples: Water Pump: Water enters at low level and pumped to a high level, pump being driven
by an electric motor. The mass (water) and energy (electricity) cross the boundary of the system
(pump and motor). Scooter engine: Air arid petrol enters and burnt gases leave the engine. The
engine delivers mechanical energy to the wheel. Boilers, turbines and heat exchanger: Fluid flow
through them and heat or work is taken out or supplied to them. Most of engineering machines are
open system. Ceiling fan: Air flows through the fan. Electricity is supplied to the fan. Air compressor:
Low pressure air enters and high pressure air leaves the compressor, electrical energy is supplied to
drive compressor motor. Carburettor: Petrol and air enter and mixture of both leaves the
carburettor. There is no change of energy. Radiator of an automobile: Hot water enters and cooled
water leaves the radiator. Heat energy is extracted by air flowing over the outer surface of radiator
tubes.
Interactions of thermodynamic systems
Types of system Mass flow Work Heat
Isolated system X X X
Open system √ √ √
Closed system X √ √
2. In terms of phase content:
A pure substance is one that has the same, distinct chemical composition everywhere: it may be a
pure element or chemical compound. Examples of pure substances are oxygen, nitrogen, water and
copper. A homogeneous substance has the same composition and properties throughout, but may
be a mixture of several pure substances. Air, which is mixture of several gases, is treated as a
homogeneous substance, as are metal alloys such as steel or brass. A solution of carbon dioxide
dissolved in water is a homogeneous substance (Fig. a), but if you shake the flask so that the carbon
dioxide comes out of solution and forms bubbles in the liquid (Fig. b), the system is no longer
homogeneous since its composition is not uniform throughout. Samples taken from different
locations in the flask will give different ratios of carbon dioxide and water and we call it a
heterogeneous substance.

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 Fig. Examples of (a) a homogeneous solution and (b) a heterogeneous mixture
Therefore;
a. Homogeneous system: A system which consists of a single phase. For example, Mixture of air and
water vapour, water plus nitric acid and octane plus heptane.

b. Heterogeneous system: A system which consists of two or more phases. For example water plus
steam, ice plus water and water plus oil.

2.2 Thermodynamic Functions

Two types of functions defined in thermodynamics are path and point functions.
Path function depends on history of the system (or path by which system arrived at a given state).
Examples for path functions are work and heat.
Point function does not depend on the history (or path) of the system. It only depends on the state
of the system. Examples of point functions are: temperature, pressure, density, mass, volume,
enthalpy, entropy, internal energy etc.
Path functions are not properties of the system, while point functions are properties of the system.
Change in point function can be obtained by from the initial and final values of the function, whereas
path has to be defined in order to evaluate path functions.

Fig. Difference between point and path functions

Processes A and B have same initial and final states, hence, the change in volume (DVA and DVB) for
both these processes is same (3m3), as volume is a point function, whereas the work transferred (WA
and WB) for the processes is different since work is a path function. It should also be noted that the
cyclic integrals of all point functions is zero, while the cyclic integrals of path functions may be or
may not be zero.

2.3 Thermodynamic process

A system undergoes a thermodynamic process when there is some sort of energetic change within
the system, generally associated with changes in pressure, volume, internal energy (i.e.
temperature), or any sort of heat transfer. We can depict a thermodynamic process on a two‐
dimensional graph by selecting two properties and showing how they vary during the process. For
example, pressure (P) and volume (V) are frequently used as axes to describe the compression or
expansion of a gas. The initial state (labelled 1) and final state (labelled 2) are defined by the
coordinates (P1, V1) and (P2, V2) in Fig. The process path is shown by the line connecting these two
points, which defines intermediate values of the two properties in going from the initial to final
state.

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Fig. A fixed mass of gas in a cylinder is compressed by a piston from initial state 1 to final state 2. The
process path shows the state of the system during the compression.

Often one or more properties are held constant during a thermodynamic process, and
specific names are given to such unique processes as follows:

(i) Isothermal process: The temperature of the system is constant. Slowly compressing gas in a
cylinder that is immersed in a very large bath of water closely approximates an isothermal process.
The gas will stay at the same temperature as the water, which we assume has such a large mass that
its temperature does not change significantly.
(ii) Isobaric process: The pressure of the system is constant. A gas being heated in a cylinder with a
freely moving piston undergoes isobaric expansion. The pressure inside the cylinder will always be
the same as that of the atmosphere outside, which we assume constant.
(iii) Isochoric process: The volume of the system is constant. Heating or cooling gases sealed in rigid
container are examples of isochoric processes. The terms isometric or isovolumetric are also used for
constant volume processes.
(iv) Adiabatic process: No heat is added to or removed from the system during the process. Any
surface that completely prevents the transmission of heat is known as an adiabatic wall.
In reality no surface is perfectly adiabatic, but many insulating materials can reduce heat transfer
to negligible amounts and are very good approximations of adiabatic walls. A system whose
boundaries are perfectly insulated will undergo an adiabatic process. Note that this is not the
same as an isothermal process. If a gas is placed in a well‐insulated cylinder and compressed,
its temperature will rise. The process is not isothermal, but it is adiabatic.

Fig . Water boiling isobarically in an open environment and an experiment in which heat is added
isobarically to water in a closed piston-cylinder arrangement

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 Fig. Process paths: Isothermal, Isobaric, isochoric and adiabatic process on a P-V diagram

2.3.1 Quasi-static Processes

In Quasi static process deviation of system from its thermodynamic equilibrium is infinitesimally
small. All the states through which system passed during a quasi-static process may be regarded as
equilibrium states.
Consider a system in which gas is contained in a cylinder fitted with a movable piston then if the
piston is pushed at infinitely slow rate, the system will be in quiescent all the time and the process
can be considered as quasi-static process.

Fig. (a) During rapid compression molecules cluster near the piston. (b) During rapid expansion there
are fewer molecules near the piston. (c) During quasi‐equilibrium compression molecules are
distributed uniformly.

Vanishingly slowness of the process is an essential feature of quasi-static process. Quasi static
process is an idealized concept and its conditions can never be rigorously satisfied in practice. In
practice, processes that are sufficiently slow and do not involve accelerated motion of the piston,
large temperature gradient, etc. are reasonably approximation to an ideal quasi-static process.

2 2 2
𝑊1−2 = ∫1 𝑑𝑤 = ∫1 𝑝𝑑𝑣 𝑄1−2 = ∫1 𝑇𝑑𝑆
Fig. Work and heat transfer during a quasi-static process

2.3.2 Cyclic Process

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In a cyclic process, the system returns to its initial state. If we integrate any property (X) over a cycle,
∮ 𝑋 = 0 since the value of the property depends only on the state of the system, not on its previous
history. For example, if the property is the x‐coordinate of the object in Fig., over the cycle,
𝑥2 𝑥3 𝑥4

∮ 𝑋 = ∫ 𝑑𝑥 + ∫ 𝑑𝑥 + ∫ 𝑑𝑥 = (𝑥2 − 𝑥1 ) + (𝑥3 − 𝑥2 ) + (𝑥1 − 𝑥3 ) = 0

𝑥1 𝑥2 𝑥3
However, the work done during the cycle will not be zero, since the work is not a property but
depends on the path taken during the cycle: 𝑊 = ∮ 𝐹𝑑𝑥 ≠ 0
Now since the system returns to its initial state, change in internal energy is zero (ΔU = 0). In this
process, total heat absorbed is equal total work done by the system; i.e. ΔQ=ΔWQ

Fig.: An object is moved from position 1, 2, 3 and finally returned to initial position 1 and P-V
diagrams for the Cyclic Process
A mass of gas contained in a piston–cylinder system is taken through four processes, which
constitute a cycle 1→2: Adiabatic compression, 2→3: Isochoric heating, 3→4: Adiabatic expansion,
4→1: Isochoric cooling. Integrating a property such as pressure (P) or volume (V) over the cycle gives

∮ 𝑑𝑃 = 0 𝑎𝑛𝑑 ∮ 𝑑𝑉 = 0

However, the total heat transfer (Q) and work done (W) done during the cycle are not zero. Analysis
of cycles is important in thermodynamics because any device that has to work continuously must
operate in a cycle. Typically, all heat engines, by definition, work in cycles.

2.4 State and Equilibrium

At a given state, all the properties of a system have fixed values. Thus, if the value of even one
property changes, the state will change to different one.

Properties of a System
Any characteristic of a system or attribute of matter, which can be evaluated quantitatively, is called
a property. That is thermodynamic variables which are experimentally measurable. Such variables
are macroscopic properties such as P, V, T, m, composition, viscosity etc. Independent properties:
two properties are independent if one property can be varied while the other one is held constant.
In classical thermodynamics, the substance is assumed to be a continuum, homogenous matter with
no microscopic holes. This assumption holds as long as the volumes, and length scales are large with
respect to the intermolecular spacing. A thermodynamic property point functions since they depends
only on the state of the system and is independent of the path by which the system arrived at the
given state.

Hence, State variables are those 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 (μ). In a magnetic solid, these are

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 34

the magnetic field (H), the magnetization (M) and temperature (T). For a homogeneous system,
consisting of a single substance, the composition (μ) is fixed.
State variables can be intensive or extensive variables.
A property is called extensive if its value for an overall system is the sum of its values for the parts
into which the system is divided, i.e. they are additive. Extensive variables are macroscopic
parameters that are dependent on the mass, extent 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), enthalpy (H), entropy (S), mass (m), volume (V), length, heat capacity (C) etc. as shown in
Table.
Extensive properties per unit mass are called specific properties, e.g. specific volume (v=V/m). The
extensive properties of a system can change with time, and many thermodynamic analyses consist
mainly of carefully accounting for changes in extensive properties such as mass and energy as a
system interacts with its surroundings.

Fig. An object is divided into two equal parts: The intensive properties of the two portions
[temperature (T), specific volume (v), density (ρ)] are unchanged while the extensive properties
[mass (m), volume (V)] have half their original values.
System Intensive variable Extensive variable
Gas or fluid Pressure, p Volume, V
Film Surface tension (γ) Area, A
Cell E.m.f (ξ) Charge, Z

An intensive variable is discrete (local) in nature i.e., it is independent of mass or size of the system
(i.e. it is not additive where Its values may vary from place to place within the system at any
moment), but it is characteristic of the substance present in the system. Examples of such variables
are pressure, temperature, specific gravity, viscosity, density, magnetic induction, surface tension,
heat capacity, dielectric Volume, mass constant, etc.
Generally, uppercase letters are used to denote extensive properties (except mass m), and lower
case letters are used for intensive properties (except pressure P, temperature T). Intensive
properties may be functions of both position and time, whereas extensive properties can vary only
with time. To illustrate the difference between extensive and intensive properties, consider Fig.

Fig. amount of matter of uniform temperature that it is composed of several parts

The mass of the whole is the sum of the masses of the parts, and the overall volume is the sum of
the volumes of the parts. However, the temperature of the whole is not the sum of the

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temperatures of the parts; it is the same for each part. Mass and volume are extensive, but
temperature is intensive.

Steady State
A system, whose properties do not change with time, even though it is exchanging energy or mass
with its surroundings, is said to be at steady state. When we switch on power to an electric heater its
temperature begins to increase. The heater element loses heat to the surrounding air at a rate that
increases with its temperature. Eventually, when it is sufficiently hot, the rate of heat loss equals the
rate at which electrical energy is supplied. The heater temperature then stays constant and it is in a
steady state.
When we place an empty bucket under a running tap it fills with water until it is brimming over.
Then, if the tap continues to run, the rate at which water spills out equals the rate at which it flows
in and the system has reached steady state. The mass of water in the bucket remains constant even
though there is constant flow through it.

Equilibrium and exergy

All physical systems that are left isolated eventually reach a state of equilibrium where their
properties do not change with time. The opposite of an equilibrium state is a non‐equilibrium state,
where the properties of an isolated system change spontaneously.

Fig. A ball bounces until it comes to rest and reaches equilibrium. A heated metal rod in an insulated
box loses heat until it reaches equilibrium when the temperature everywhere in the box is uniform.

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;
i.e. there is no change in pressure at any point of the system. However, the pressure may vary within
the system due to gravitational effects.
Phase equilibrium: in a two phase system, when the mass of each phase reaches an equilibrium
level. Phase: Any portion including the whole of a system which is physically homogeneous within
itself and bounded by a surface so that it is mechanically separable from any other potions. Example,
Ice, water and steam are the three phases of water.
Since the change in phase of a substance is dependent mainly on P and T, phase diagrams are best
illustrated on P-T diagrams.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 36

 Fig. Hypothetical P-T projections of one-component system
(-) TP is the triple point i.e., the temperature (TTP) at which all the three phases (liquid, solid
and vapour) coexist. (--) Point C is the critical point i.e., where liquid and vapour are
indistinguishable. (---) Below pt C, the system exists in two phases (liquid and vapour), while beyond
C, (or temperature TC), the system is gaseous. At the triple point (TP), the solid and liquid are in
equilibrium. If the volume were held constant as heat is added to the system, the solid would melt.
The increased volume of the melt increases the pressure and temperature and as such, the
equilibrium between the solid and liquid shifts to a position of higher pressure and temperature i.e.,
towards pt B on curve IB. Similar projections can be worked out for solid-vapour and for liquid-
vapour systems at equilibrium
Equilibrium Conditions for Two Phases
In the example above, we saw that a single component such as water can exist in 3 phases (solid,
liquid and vapour) depending on the conditions of Pressure and temperature. We need to determine
the conditions under which any 2 phases e.g. solid and liquid can exist in equilibrium.
The conditions for thermodynamic equilibrium of any two phases of a system, is that the Gibbs
function for both phases (phases 1 and phase 2) should be minimum. Thus by Applying Gibbs
potential (G), it is possible to investigate the equilibrium between a liquid and its vapor or between
any two phases of a substance.
For example, consider a closed system containing a liquid in equilibrium with its saturated vapour.
For equilibrium conditions, the temperature and pressure are equal in both the phases and must
remain constant throughout the phases. The thermodynamic coordinate V, S, U and G will be equal
to the product of the specific value and the mass of the substance in that phases.
Suppose the phases have masses M1 and M2, where M1 + M2 = M (total mass) and Gl and G2 are
Gibbs functions for the two phases respectively. Then, for the whole system,
𝐺 = 𝑚1 𝐺1 + 𝑚2 𝐺2
NB: Gibbs free energy [𝐺 = 𝐻 − 𝑇𝑆 = 𝑈 − 𝑇𝑆 + 𝑃𝑉] is an extensive variable i.e., dependent on
system size. If a small quantity of the liquid changes into vapour, then the change in G is obtained by
differentiation and for equilibrium condition, dG = 0
𝑑𝐺 = 𝜕𝑚1 𝐺1 + 𝜕𝑚2 𝐺2 = 0
But since the system is closed, the total mass is constant i.e., m1 + m2 = M (total mass) or m1  m2
⇒ 𝐺1 = 𝐺2
This shows that the equilibrium condition for existence of 2 phases is that their specific Gibbs
functions (G) must be equal. This equation is applicable to the processes of evaporation, fusion and
sublimation.

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Chemical equilibrium: This means that there are no chemical reactions occurring within the system.
In other words, the chemical composition of a system does not change with time.
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.

Exergy
A system consists of gas contained in a cylinder that is initially at pressure P and temperature T while
the surroundings are at pressure P0 and temperature T0. The piston compressing the gas is released
and the system exchanges heat with the surroundings until it reaches equilibrium when the pressure
and temperature of the gas are the same as that outside. The system is now in a “dead state”,
where it cannot do any useful work.

If the pressure and temperature of the gas were initially higher than that of the surroundings it
could, in principle, have been used to do useful work such as lifting a weight. Instead all the energy
of the system was dissipated as heat or transferred as work to push back the surrounding air. Once
the system reaches equilibrium it cannot do any more work. According to the first law, energy
cannot be destroyed. However, something has been lost in this process, which is the ability of the
system to do useful work. To measure the magnitude of this loss we define a new property: Exergy
is the maximum amount of useful work a system can do before it reaches equilibrium with its
surroundings.
How much work could the system have done if we had used its expansion in a more efficient way?
This depends not only on the properties of the system, but also those of the surroundings. The
greater the difference between the initial pressures on the two faces of the piston, the farther it
could have moved.

Fig. Gas in a cylinder (a) initially at pressure P and temperature T then (b) comes to equilibrium with
the surroundings at pressure P0 and temperature T0.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 38

 Chapter 3: THERMAL EQUILIBRIUM AND ZERO’TH LAW OF THERMODYNAMICS

When the temperatures of two bodies are the same, thermal equilibrium is reached. The equality of
temperature is the only requirement for thermal equilibrium.

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 towards thermal equilibrium with its environment i.e., when its
temperature does not change over time. Therefore, two systems each in thermal equilibrium with a
third system are in thermal equilibrium to each other. "If body A and body C are each in thermal
equilibrium with a third body B, then, A is also in thermal equilibrium with C"

Fig. A steaming cup of coffee loosing heat to the surrounding as it approaches thermal equilibrium
and bodies in thermal equilibrium

The effect of Zeroth law is that body B acts as a thermometer for bodies A and C, as shown in Fig.

Thermal equilibrium by 0th law

Body A Body C

Thermal Thermal
equilibrium equilibrium
Body B

All these systems possess a common property called temperature, which determines the direction of
heat flow. Thus, the significance of Zeroth Law is that it introduces the concept of temperature and
provides a means of determining temperature –Through thermal equilibrium.

Temperature and Temperature scales

Temperature is a pointer for the direction of energy transfer as heat. 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.

Fig.: Heat transfer occurs in the direction of higher‐to‐lower‐temperature.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 39

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. 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 (mercury expands with temperature in a repeatable and
predictable way).

(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

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
𝑇𝑋 = 𝑎𝑋
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. We may thus write
𝑋
𝑇𝑋 = 273.16 ( )
𝑋𝑇𝑃
Which implies a zero of temperature i.e., T x= 0 at X = 0. We can now apply Eqn. above 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. gives
𝐿
𝑇𝑋 = 273.16 ( )
𝐿 𝑇𝑃
For a gas at constant pressure, X is the volume (V) of the gas, and Eqn … gives
𝑉
𝑇𝑉 = 273.16 ( )
𝑉𝑇𝑃
Likewise, for a platinum resistance thermometer, X is the electrical resistance (R) of the platinum
wire such that Eqn … gives
𝑅
𝑇𝑅 = 273.16 ( )
𝑅𝑇𝑃
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
𝑃
𝑇𝑔𝑎𝑠 = 273.16 ( )𝐾
𝑃𝑇𝑃
Where K, the Kelvin, is the unit of temperature on the ideal gas scale

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 𝑇(°𝑅) = 1.8𝑇(𝐾)
𝑇(°𝐶) = 𝑇(𝐾) − 273.15
𝑇(°𝐹) = 𝑇(°𝑅) − 459.67
{
𝑇(°𝐹) = 1.8𝑇(°𝐶) + 32
Commonly used Temperature Scales:
(i) The Kelvin, (K) is the unit of temperature
on the ideal gas scale. The temperature
between ice point and steam point is 100K

(ii) The Celsius 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 1000C.

(ii) Fahrenheit scale has a range of 180

equal parts with the ice point at 320F and
Steam point is 2120F.

Fig. Comparison of temperature scales.

The simple relationship between common scales:

𝑪 𝑭 − 𝟑𝟐 𝑲 − 𝟐𝟕𝟑
= =
𝟏𝟎𝟎 𝟏𝟖𝟎 𝟏𝟎𝟎

Fig. Liquid-in-glass, Electrical-resistance and Infrared-sensing ear thermometer

Questions
What was the original unit for measuring heat?
A. BTU, B. Watt, C. Joule, D. Pascal, E. Calorie.

What is the name of an ideal-gas process in which no heat is transferred?

A. Isochoric, B. Isentropic, C. Isothermal, D. Isobaric, E. Adiabatic.

Explain the difference between the following thermodynamic terms:

(i) Open and closed system
(ii) Diathermal and adiathermal wall
(iii) State variable and state function
(iv) Reversible and irreversible processes
(v) Intensive and extensive variables
Explain what is thermodynamic equilibrium?

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 41

A platinum resistance thermometer has a resistance R = 90.35  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 6.28.
𝑅 𝑅
Soln: 𝑇𝑅 = 273.16 (𝑅 ) = 273.16 (𝑅 ) = 280.6𝐾
𝑇𝑃 𝑇𝑃

The temperature of the surface of the sun is about 65000C. What is this temperature on the Kelvin
scale?
𝐶 𝐹−32
Soln: 100 = 180
⟺ 𝐾 = 6500 + 273 = 6773𝐾

The normal boiling point of liquid oxygen is -1830C. What is this temperature on the Kelvin scale?

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
𝑝1 𝑝2 𝑇2
= ⟹ 𝑝2 = 𝑝1 = 3.5𝑎𝑡𝑚.
𝑇1 𝑇2 𝑇1
Pressure gauges for automobile tires are usually calibrated to read overpressure i.e., excess above
atmospheric pressure. Thus the gauge would read 2.0atm in the morning and 2.5atms later in the
day

List the properties of an ideal gas?

State the three gas laws?
Starting from first principles, derive the equation of state?
Explain why a real gas deviates from the ideal gas behaviour?

Consider the LHS P-V diagram for an ideal gas, Draw the corresponding T-P diagram. Soln.: PV =
constant, so it means the temperature is constant. Thus, the RHS figure.

P 1 T

P=Constant/V 2 1

V P
Draw the corresponding P-V diagram for the given T-V LHS diagram. Soln.: Since TV diagram is a
straight line T/V =constant. It means Pressure is constant. Thus, the RHS figure
V B P

A B

T1 T2 V
Draw the corresponding P-V diagram for the given LHS T-V diagram. Soln.: Since T is constant PV
diagram should be isotherm. Soln.: As T is constant PV diagram should be isotherm, thus the RHS

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 42

 V A P B

B A

T V
Questions for Discussion

1. Explain why a real gas behaves like an ideal gas at low densities but not at high densities?

2. At the airport of La Paz, Bolivia, one of the highest in the world, pilots find it preferable to take off
early in the morning or late at night, when the air is very cold. Explain why?

3. The normal boiling point of liquid oxygen is -1830C. What is this temperature on the Kelvin scale?

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 43

 Chapter 4: FIRST LAW OF THERMODYNAMICS AND INTERNAL SYSTEM ENERGY

The law of conservation of energy states that “energy can neither be created nor destroyed but it is
transformed from one form to another form”. Therefore: “When a system undergoes a
thermodynamic cycle then the net heat supplied to the system from the surroundings is equal to
net work done by the system on its surroundings”. The cyclic integral of the heat is equal to the
cyclic integral of the work

∮ 𝒅𝑸 = ∮ 𝒅𝑾

2 processes: In the first process work is done

on the system by the paddle that turns as the
weight is lowered. Let this system return to its
initial state by transferring heat from the
system until the cycle has been completed.
When the amounts of work and heat are
Fig.: Example of a system undergoing a cycle compared it is found that they are equal.

For non-cyclic process; a more general new concept which involves a term called internal energy
fulfils this need.

A system undergoing a transformation from state A to state B. Assuming that the system is
macroscopically at rest in states A and B, energy conservation gives:

∆𝑈 = 𝑈𝐵 − 𝑈𝐴 = [𝐸𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑐𝑒𝑖𝑣𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝐴 𝑎𝑛𝑑 𝐵]

Remark: The energy received is an algebraic quantity: If ∆U is positive, the system receives energy. If
∆U is negative, the system gives away energy. The first law of Thermodynamics cannot be proved
analytically, but experimental evidence has repeatedly confirmed its validity, and since no
phenomenon has been shown to contradict it, the first law is accepted as a law of nature.

Energy gains are classified into two categories, the work received W and the heat received
𝑈: 𝐼𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦
∆𝑼 = 𝑾 + 𝑸 𝑊: 𝑊𝑜𝑟𝑘 𝑟𝑒𝑐𝑒𝑖𝑣𝑒𝑑
𝑄: 𝐻𝑒𝑎𝑡 𝑟𝑒𝑐𝑒𝑖𝑣𝑒𝑑
The three quantities W, Q and ∆U can be positive, negative or zero.

 The work received W corresponds to the macroscopic energy exchanges; it should be

possible to determine it by measuring the various forces applied to the system. A work
received W occurs with the change of a macroscopic parameter of the system other than
energy. For example, the work of pressure forces comes with a change in volume; the work
of magnetic forces comes with a change of magnetisation, etc.
 The heat received Q corresponds to the spontaneous energy exchanges between two bodies
at different temperatures, either by contact (conduction), or at a distance (radiation), or by
means of a moving fluid (convection). These energy transfers occur at the microscopic level
and are sometimes difficult to determine with precision.

For an infinitesimally small transformation, we write

𝐵 𝐵 𝐵
𝑑𝑈 = 𝛿𝑊 + 𝛿𝑄 𝑤𝑖𝑡ℎ ∆𝑈 = ∫ 𝑑𝑈 , 𝑊 = ∫ 𝛿𝑊 𝑎𝑛𝑑 𝑄 = ∫ 𝛿𝑄
𝐴 𝐴 𝐴

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Note: (i) U is a state function, a property of the system. The quantity ∆U depends only on the states
A and B and does not depend on the intermediate states
(ii) W and Q are two properties of the transformation. They depend on A, B and all intermediate
states (i.e. the transformation path followed). They cannot be expressed as the difference of a
quantity taken in B and A. Similarly, δW and δQ are infinitesimal energy gains during a
transformation between two infinitely close states. They do not correspond to a difference.

Remark: Transformations without heat or work exchange are possible. The typical example is the
Joule expansion: a gas is in an adiabatic enclosure; a tap is opened which allows the gas to flow into
another adiabatic enclosure previously under vacuum. During the transformation the gas receives
neither heat (all the walls are adiabatic) nor work (there is no external force).

Hence; “Heat and work are mutually convertible but since energy can neither be created nor
destroyed, the total energy associated with an energy conversion remains constant” or
“No machine can produce energy without corresponding expenditure of energy, i.e., it is
impossible to construct a perpetual motion machine of first kind (PPM 1)”.
Q Q

ENGINE W MACHINE W

Fig. A PMM 1 is impossible for both reversal energy cross-flows

In other words, there is no machine continuously supplying mechanical work without simultaneous
disappearance of some form of energy. The converse fictitious machine does not exist, as well; i.e.,
there can be no machine which would continuously consume work without some other form of
energy appearing simultaneously.
Applying the First Law of Thermodynamics to the system, simply re-state it: “The change in the
energy of a system is the amount of energy added to the system minus the energy spent doing work”.
Or the change in stored energy of the system is numerically equal to the net heat interactions minus
the net Work interaction during the process.
2
𝐸2 − 𝐸1 = ∆𝐸 = 𝑄 − 𝑊 [𝑜𝑟 𝑄 = ∆𝐸 + 𝑊] ⟺ ∫ 𝑑(𝑄 − 𝑊) = ∆𝐸 = 𝐸2 − 𝐸1
1

Fig. First law of thermodynamics for an open system

The first law for this open system is given by:

𝑑𝐸 𝑉22 𝑉12
= 𝑚2 (ℎ2 + + 𝑔𝑧2 ) − 𝑚1 (ℎ1 + + 𝑔𝑧1 ) + 𝑊 − 𝑄
𝑑𝑡 2 1

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 45

Where (dE/dt) is the rate at which the total energy of the system changes and ‘g’ is the acceleration
due to gravity. For open system in steady state: the time rate of change of all the quantities is zero,
and mass is also conserved. Quantities q and 𝑤 are specific heat and work transfer rates
𝑉22 𝑉12
(ℎ2 + + 𝑔𝑧2 ) − (ℎ1 + + 𝑔𝑧1 ) = 𝑞 − 𝑤
2 1
For isolated systems, there are no system interactions with the surroundings. Therefore, the total
energy is always constant.
𝑑𝑄 = 0, 𝑑𝑊 = 0 ⟺ 𝑑𝐸 = 0 ∴ 𝐸 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
E represents the total internal energy. If the electric, magnetic and chemical energies are absent and
changes in potential and kinetic energy for a closed system are neglected, the above equation can be
written as
2
∫ 𝑑(𝑄 − 𝑊) = ∆𝑈 = 𝑈2 − 𝑈1 ⟺ 𝑄 − 𝑊 = ∆𝑈 = 𝑈2 − 𝑈1
1
Generally, when heat is added to a system its temperature raises and external work is performed
due to increase in volume of the system. The rise in temperature is an indication of increase of
internal energy.
From the first law of thermodynamics
2 2
∮ 𝛿𝑄 = ∮ 𝛿𝑊
1 1
Considering 2 separate processes two reversed paths:
2 1 2 1
∮ 𝛿𝑄𝐴 + ∮ 𝛿𝑄𝐵 = ∮ 𝛿𝑊𝐴 + ∮ 𝛿𝑊𝐵
1 2 1 2
2 1 2 1
∮ 𝛿𝑄𝐴 + ∮ 𝛿𝑄𝐶 = ∮ 𝛿𝑊𝐴 + ∮ 𝛿𝑊𝐶
1 2 1 2

Fig. A P-V diagram showing E as a thermodynamic property

Subtracting the second of these equations from the first and rearranging, we have
1 1 1 1 1 1
∮ 𝛿𝑄𝐵 − ∮ 𝛿𝑄𝐶 = ∮ 𝛿𝑊𝐵 − ∮ 𝛿𝑊𝐶 ⟺ ∮ (𝛿𝑄 − 𝛿𝑊)𝐵 = ∮ (𝛿𝑄 − 𝛿𝑊)𝐶
2 2 2 2 2 2
Since B and C represent arbitrary processes between states 1 and 2, the quantity 𝛿𝑄 − 𝛿𝑊 is the
same for all processes between state 1 and state 2. This property is the energy of the system and is
given the symbol E. The physical significance of the property E is that it represents all the energy
of the system in the given state. Usually we consider the bulk kinetic and potential energy separately
and then consider all the other energy of the system in a single property that we call the internal
energy, U. E = Internal Energy + Kinetic Energy + Potential Energy

Example
Five kilograms of gas are contained in a rigid cylinder. An impeller in the gas, driven by an electrical
motor, does 20kJ / kg of work on the gas. At the same time the gas loses 80kJ of heat to the
surrounding. What is the change in specific internal energy of the gas?

Soln.: Mass of gas m = 5kg, heat loss Q = –80kJ, work added per unit mass of gas w = 20kJ/kg.
Changes in kinetic and potential energy are negligible, ∆KE=0 and ∆PE=0.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 46

 𝑄 + 𝑊 = ∆𝑈 + ∆𝑃𝐸 + ∆𝐾𝐸 ⟺ ∆𝑈 = 𝑄 + 𝑊
𝑊 = 𝑚𝑤 = 5 × 20 = 100𝑘𝐽
∆𝑈 = −80 + 100 = 20𝑘𝐽
∆𝑈 20
∆𝑢 = = = 𝟒𝒌𝑱⁄𝒌𝒈
𝑚 5

Fig. An impeller does work on gas contained in a rigid cylinder

A gas initially at a pressure of 40kPa and a volume of 0.1 m3 is compressed until the pressure doubles
and its volume is 0.04 m3. The internal energy of the gas increases by 2.1kJ. During compression gas
pressure varies linearly with volume so that P = a + bV. What is the heat transfer during this process?

Soln.: Initial pressure P1 = 40 kPa, initial volume V1 = 0.1 m3, final pressure P2 = 80 kPa, final volume
V2 = 0.04 m3, change in internal energy ∆U = 2.1 kJ, during compression P = a + bV.
∆𝑈 = 𝑄 + 𝑊
𝑉2 𝑉2 𝑉
𝑏𝑉 2 2
𝑊 = − ∫ 𝑃𝑑𝑉 = − ∫ (𝑎 + 𝑏𝑉)𝑑𝑉 = − [𝑎𝑉 + ]
𝑉1 𝑉1 2 𝑉
1
𝑏
= −𝑎(𝑉2 − 𝑉1 ) − (𝑉22 − 𝑉12 )
2

Fig. A gas is compressed until the pressure doubles

To find the constants a and b; since P1 =a + bV1 and P2 = a+ bV2:

𝑃2 − 𝑃1 80 − 40
𝑏= = = −666.67 𝑘𝑃𝑎⁄𝑚3
𝑉2 − 𝑉1 0.04 − 0.1
𝑎 = 𝑃 − 𝑏𝑉 = 40 − (−666.67)(0.1) = 106.67𝑘𝑃𝑎
−666.67
𝑊 = −106.67(0.04 − 0.1) − (0.042 − 0.12 ) = 6.40 − 2.80 = 3.6𝑘𝐽
2
Work is positive since done on the system by the surroundings in compressing it, and

𝑄 = ∆𝑈 − 𝑊 = 2.10 − 3.60 = −𝟏. 𝟓𝟎𝒌𝑱

A gas is compressed by a piston in a cylinder from an initial pressure of 1.0bar and initial volume of
0.4m3, to a final pressure of 1.4bar. During the compression process, the product of the gas pressure
P and volume V remains constant. Determine the work done on the gas. If during the compression
the gas loses 8.1kJ of heat to the surroundings, determine the change in internal energy of the gas.

Soln.: Initial pressure P1 = 1bar, initial volume V1 = 0.4m3, final pressure P2 = 1.4bar, heat loss Q = –
8.1 kJ, during compression PV = constant.

𝑃1 𝑉1 1 × 0.4
𝑃1 𝑉1 = 𝑃2 𝑉2 = 𝐶 ⟺ 𝑉2 = =
𝑃2 1.4
3
= 0.28571𝑚
𝑉2 𝑉2
𝑑𝑉 𝑉1
𝑊 = − ∫ 𝑃𝑑𝑉 = −𝐶 ∫ = 𝐶 ln
𝑉1 𝑉1 𝑉 𝑉2

𝐶 = 𝑃1 𝑉1 = 1 × 105 × 0.4 = 0.4 × 105 𝑁𝑚

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 47

Fig. A gas is compressed by a piston in a cylinder
𝑉1 0.4
𝑊 = 𝐶 ln = 0.4 × 105 × 𝑙𝑛 = 13459.5𝐽 = 13.460𝑘𝐽
𝑉2 0.28571
∆𝑈 = 𝑄 + 𝑊 = −8.10𝑘𝐽 + 13.460𝑘𝐽 = 𝟓. 𝟑𝟔𝟎𝒌𝑱
3.1 Enthalpy
Water jets out of an outlet near the bottom of a full tank, driven by the pressure of the liquid, and
turns a turbine wheel. As the tank empties and the level of liquid becomes lower the pressure of the
water diminishes until it is trickling out and can no longer do any work. What property of a liquid
describes its capacity to do work?

Fig . (a) Water comes out of a full tank at high pressure and can be used to do work. (b) Water drips
out of a tank that is almost empty
The velocity of water inside the tank is very low so the difference in kinetic energy between liquid in
a full or almost empty tank is negligible. Water is at the same temperature throughout the process
and therefore has constant internal energy. The only property that changes as the water drains is its
pressure (P): a fluid can do more work as its pressure increases. But P alone does not establish the
amount of work that the fluid does: if two liquids are at the same pressure but have different
temperatures, we can extract more work from the higher temperature fluid. A fluid’s ability to do
work depends on some combination of its internal energy and pressure.

𝐻 ≡ 𝑈 + 𝑃𝑉
When fluid with specific internal energy (u) leaves a control volume, the system has to do flow work
on it (Pv per unit mass) and this energy is transported along with the fluid so that its energy per unit
mass becomes u + Pv. Thus, the Enthalpy H [J] measures the capacity of a fluid to do work.

Since U and PV are both extensive properties H, their sum, is also an extensive property. The
corresponding intensive property is the specific enthalpy [J/kg].
𝐻 𝑈 𝑉
ℎ= = + 𝑃 = 𝑢 + 𝑃𝑣
𝑚 𝑚 𝑚
Typical use of enthalpy is when we are studying heating of gases : by heating a constant‐volume
system its internal energy increases, which we observe as a rise in temperature and pressure. If the
system is free to expand part of the energy supplied is lost in doing work to push back the
surroundings. It therefore takes more energy to heat a system at constant pressure than at constant
volume. The difference can be important when gases are heated, because the work done by them
while expanding is a significant portion of the total energy required for heating.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 48

Fig. Heat (Q12) is transferred to a constant pressure system (equal to that of the surrounding
atmosphere) that does work (W12) on the surroundings as it expands from volume V1 to V2.

We can use the first law to calculate the expansion work. Assuming the piston to have negligible
mass, there is no change in potential or kinetic energy during the expansion process—only the
internal energy changes. Applying an energy balance,

𝑄12 + 𝑊12 = ∆𝑈 = 𝑈2 − 𝑈1 ⟺ 𝑄12 = (𝑈2 + 𝑃2 𝑉2 ) − (𝑈1 + 𝑃1 𝑉1 ) ⟺ 𝑄12 = 𝐻2 − 𝐻1

Where the work done during an isobaric expansion is given by 𝑊12 = 𝑃1 𝑉1 − 𝑃2 𝑉2; A mass in contact
with the atmosphere is an example of a system that is free to expand under constant pressure. The
heat required per unit mass of the system is
𝑄12 𝐻2 𝐻1
𝑞12 = = − = ℎ2 − ℎ1
𝑚 𝑚 𝑚
3.2 Specific Heats
There are no meters of two extensive properties, the internal energy (U) and the enthalpy (H). We
have to find a way of relating U and H to P, T and V, so by measuring the latter we can calculate the
former.
From experience, it is known that adding energy to a material increases its temperature.
How much the temperature rises for a given amount of heat is a property of the material: it takes
much more energy to heat 1 kg of water than 1 kg of air. We define the specific heat (c) as the
amount of energy required to raise the temperature of a unit mass of a substance by one degree. If
the temperature of a system with mass m (kg) increases by ∆T (°C) when Q (J) of heat are added to it,
the average specific heat of the system is
𝑄 𝑞
𝑐𝑎𝑣𝑔 = = [𝐽⁄𝑘𝑔° 𝐶 𝑜𝑟 𝐽⁄𝑘𝑔𝐾]
𝑚∆𝑇 ∆𝑇
Choice for temperature difference unit does not matter because ∆T = 1 °C is the same as ∆T = 1 K
The specific heat may vary with the temperature of the substance: the heat required to raise the
temperature of water from 0 to 1 °C is not exactly the same as that required to raise it from 99 to
100 °C. It is more accurate to define c as a function of temperature:
𝛿𝑞 𝛿𝑞
𝑐(𝑇) = lim =
∆𝑇→0 ∆𝑇 𝑑𝑇
This definition is still not complete because we have not specified how the material is heated. For a
material being heated in a rigid container, whose volume is constant, W = 0 and when the material is
heated at constant pressure. The heat added is change in internal energy and enthalpy, respectively.

𝛿𝑞 = 𝑑𝑢 𝑎𝑛𝑑 𝛿𝑞 = 𝑑ℎ

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 49

 Thus, the specific heat at constant volume:
𝝏𝒖
𝒄𝒗 (𝑻) ≡ ( )
𝝏𝑻 𝒗
The specific heat at constant pressure:
𝝏𝒉
𝒄𝒑 (𝑻) ≡ ( )
𝝏𝑻 𝒑

Fig. Control mass being heated at (a) constant volume and (b) constant pressure

We can also define molar specific heats, using kmol rather than kg as a unit of mass. The units of
both are J / kmol °C or J / kmolK. The molar specific heat at constant volume and and the molar
specific heat at constant pressure are
𝜕𝑢̅
𝑐̅𝑣 = 𝑐𝑣 𝑀 = ( )
𝜕𝑇 𝑣
̅
𝜕ℎ
𝑐̅𝑝 = 𝑐𝑝 𝑀 = (𝜕𝑇 )
𝑝
3.2.1 Specific Heats of Ideal Gases
The internal energy (U) of an ideal gas is a function only of its temperature (T). If u = u(T) and not u =
u(T,P) we do not require the up-shown partial differential in Equation and can write
𝑑𝑢
𝑐𝑣 (𝑇) =
𝑑𝑇
For an ideal gas, 𝑃𝑣 = 𝑅𝑇, Its enthalpy ℎ = 𝑢 + 𝑃𝑣 = 𝑢 + 𝑅𝑇. Since specific internal energy (u) is a
function only of temperature and gas constant (R) is a constant, specific enthalpy (h) for an ideal gas
is also a function of temperature alone; therefore,
𝑑ℎ
𝑐𝑝 (𝑇) =
𝑑𝑇
Changes in internal energy and enthalpy by integrating, we obtain
𝑇2 𝑇2
∆𝑢 = 𝑢2 − 𝑢1 = ∫ 𝑐𝑣 (𝑇)𝑑𝑇 𝑎𝑛𝑑 ∆ℎ = ℎ2 − ℎ1 = ∫ 𝑐𝑝 (𝑇)𝑑𝑇
𝑇1 𝑇1

𝑑ℎ 𝑑𝑢
𝑐𝑝 (𝑇) = = + 𝑅 ⇔ 𝒄𝒑 = 𝒄𝒗 + 𝑹 𝑜𝑟 𝒄̅𝒑 = 𝒄̅𝒗 + 𝑹𝒖
𝑑𝑇 𝑑𝑇
For an ideal gas both cp and cv are constants that differ by R. We define a new property, the specific
heat ratio:
𝒄𝒑 𝒄̅𝒑
𝜸= =
𝒄𝒗 𝒄̅𝒗
For a monoatomic ideal gas; the internal energy, the specific internal energy and the specific
enthalpy
3 𝑈 3 5
𝑈 = 𝑁𝑅𝑢 𝑇 𝑎𝑛𝑑 𝑢 = = 𝑅𝑇 ⇔ ℎ = 𝑢 + 𝑃𝑣 = 𝑢 + 𝑅𝑇 = 𝑅𝑇
2 𝑚 2 2
Differentiating
𝑑𝑢 3 𝑑ℎ 5 𝑐𝑝 5
𝑐𝑣 = = 𝑅 𝑎𝑛𝑑 𝑐𝑝 (𝑇) = = 𝑅 ⇔ 𝜸 = = = 𝟏. 𝟔𝟔𝟕
𝑑𝑇 2 𝑑𝑇 2 𝑐𝑣 3
For other gases, with molecules consisting more than one atom, the value of γ is less than 1.667.
More sophisticated models of molecular motion, which account for molecular vibration and spin,
can be developed to predict these values as well.
Table: Specific heats of common gases evaluated at 25°C and 100kPa.
Gas Number R[kJ/kgK] cp[kJ/kgK] cv[kJ/kgK] γ=cp/cv

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 of atoms
Helium 1 2.0770 5.193 3.116 1.667
Argon 1 0.2081 0.520 0.312 1.667
Neon 1 0.4120 1.030 0.618 1.667
Hydrogen 2 4.1242 14.209 10.085 1.409
Carbon monoxide 2 0.2968 1.041 0.744 1.400
Nitrogen 2 0.2968 1.042 0.745 1.400
Oxygen 2 0.2598 0.922 0.662 1.393
Water (steam) 3 0.4615 1.872 1.410 1.327
Carbon dioxide 4 0.1889 0.842 0.653 1.289
Ammonia 4 0.4882 2.130 1.642 1.297
Air Mixture 0.2870 1.004 0.717 1.400

What if you are dealing with a process that is neither constant volume nor constant pressure? Which
specific heat should you use to determine changes in internal energy and enthalpy?
Energy and enthalpy are both properties and to calculate changes in their values during a process we
need to know only the initial and final states of the system – the path taken in going from one state
to another does not matter. Changes in internal energy also depend only on the initial and final
state, not the path followed. A gas is compressed at constant temperature from state 1 to 2 and
then expanded at constant pressure from state 2 to 3. Imagine a process in which we go directly
from 1 to 3 by heating the gas while holding it at constant volume.∆𝑢13 = 𝑐𝑣,𝑎𝑣𝑔 (𝑇3 − 𝑇1 )
Therefore, if we took the system
first from state 1 to 2 and then
to state 3, by a series of
processes that are not constant
volume, the change in internal
energy (Δu13) would still be the
same.

Fig. A box with mass m is lifted onto a table of height Δz following either path 1 or path 2. The
change in potential energy is ΔPE = mgΔz, irrespective of the path taken. System undergoing either a
constant temperature (1–2) followed by a constant pressure (2–3) process or a constant volume (1–
3) process.
We do not require that the volume or pressure remain constant during a process to use cv and cp
values to calculate changes in u and h. It is always true for an ideal gas undergoing any
thermodynamic process, even if it is not under constant volume or constant pressure conditions
that the change in specific internal energy and specific enthalpy are
𝑇2 𝑇2
∆𝑢 = 𝑢2 − 𝑢1 = ∫ 𝑐𝑣 (𝑇)𝑑𝑇 𝑎𝑛𝑑 ∆ℎ = ℎ2 − ℎ1 = ∫ 𝑐𝑝 (𝑇)𝑑𝑇
𝑇1 𝑇1
Examples:
Oxygen contained in a cylinder is compressed adiabatically by a piston from an initial state with V1 =
0.2 m3, P1 = 200 kPa and T1 = 25°C to a final temperature T2 = 200°C. Find the work done during this
process.
Properties from tables: Gas constant of oxygen is R = 0.2598kJ/kgK. As a first approximation, for
oxygen at 25°C, cv=0.662kJ/kgK. But we have more accurate information, where cv is given as a
function of temperature. The average temperature for the process is Tavg= (T1 + T2)/2 =
(25°C+200°C)/2=112.5°C= 385.65K. At 350 K, cv = 0.668 kJ/kgK and at 400K,cv=0.681kJ/kgK.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 51

We can do a linear interpolation between these values to get
𝑐𝑣,386.65𝐾 − 0.668 𝑘𝐽⁄𝑘𝑔𝐾 0.681 𝑘𝐽⁄𝑘𝑔𝐾 − 0.668 𝑘𝐽⁄𝑘𝑔𝐾
= ⇔ 𝑐𝑣,386.65𝐾 = 0.67727 𝑘𝐽⁄𝑘𝑔𝐾
385.65𝐾 − 350𝐾 400𝐾 − 350𝐾
We will use this number, but note that the difference from the value at 25°C is only about 2%.
For most engineering applications such a small difference does not matter. You will need to
exercise judgment as to whether it is necessary to interpolate values.

Soln.: Initial volume V1 = 0.2 m3, initial pressure P1 = 200 kPa, initial temperature T1 = 25°C(298.15K),
final temperature T2 = 200°C, adiabatic process so Q12 = 0.
𝑃1 𝑉1 200 × 103 × 0.2
𝑚= = = 0.51640𝑘𝑔
𝑅𝑇1 0.2598 × 298.15
𝑄
⏟12 + 𝑊12 = ∆𝑈12 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 )
=0

𝑊12 = 0.51640 × 0.67727 × (200 − 25) = 𝟔𝟏. 𝟐𝟎𝟓𝒌𝑱

Fig. Linear interpolation to calculate cv at a temperature of 386.65K

An ideal gas with cp=1.044kJ/kgK and cv=0.745kJ/kgK contained in acylinder–piston assembly initially
has a pressure of 150kPa, a temperature of 30°C, and a volume of 0.22m3. It is heated slowly at
constant volume (process 1–2) until the pressure is doubled. It is then expanded slowly at constant
pressure (process 2–3) until the volume is doubled. Determine the work done and heat added in the
combined process. Soln.:
Ideal gas, specific heats cp=1.044 kJ/kgK and cv=0.745kJ/kgK, initial volume
V1= 0.22m3, initial pressure P1 = 150 kPa, initial temperature T1 = 30°C, final
pressure P2=2P1, final volume V3 = 2V1.

𝑅 = 𝑐𝑝 − 𝑐𝑣 = 1.044 − 0.745 = 0.299 𝑘𝐽⁄𝑘𝑔𝐾

𝑃1 𝑉1 150 × 103 × 0.22

𝑚= = = 0.364070𝑘𝑔
𝑅𝑇1 0.299 × (273.15 + 30)
Fig.: An ideal gas being heated in a cylinder–piston assembly, first at constant volume (1–2) and then
at constant pressure (2–3)
𝑃2 𝑉3
𝑇2 = 𝑇1 = 303.15 × 2 = 606.300𝐾 𝑎𝑛𝑑 𝑇3 = 𝑇2 = 606.3 × 2 = 1212.60𝐾
𝑃1 𝑉2
𝑉2
𝑊12 = ∫ 𝑃𝑑𝑉 = 0
𝑉1
∴ 𝑄12 = ∆𝑈12 − 𝑊12 = ∆𝑈12 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) = 0.36407 × 0.745(606.3 − 303.15) = 82.2240𝑘𝐽
𝑉3
𝑊23 = − ∫ 𝑃𝑑𝑉 = −𝑃3 (𝑉3 − 𝑉2 ) = −(𝑃3 𝑉3 − 𝑃2 𝑉2 ) = −𝑚𝑅(𝑇3 − 𝑇2 )
𝑉2
𝑊23 = −0.36407 × 0.299(1212.6 − 606.3) = −66.0000𝑘𝐽
𝑄23 = ∆𝑈23 − 𝑊23 = 𝑚𝑐𝑣 (𝑇3 − 𝑇2 ) − 𝑊23
𝑊23 = −0.36407 × 0.745(1212.6 − 606.3) + 66 = 230.448𝑘𝐽
𝑊𝑡𝑜𝑡𝑎𝑙 = 𝑊12 + 𝑊23 = −𝟔𝟔𝒌𝑱
𝑄𝑡𝑜𝑡𝑎𝑙 = 𝑄12 + 𝑄23 = 82.224 + 230.448 = 𝟑𝟏𝟐. 𝟔𝟕𝟐𝒌𝑱

3.2.2 Gas Tables

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To evaluate changes in internal energy and enthalpy for ideal gases, we need to know how the
specific heats change with temperature. For monoatomic gases such as helium, argon and neon
cp=5R/2 is accurate over a very wide range of temperatures. For most other gases specific heats
increase with temperature and it is possible to fit a polynomial curve of the form
𝑐̅𝑝 = 𝑀𝑐𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3
Coefficients’ values for a, b, c and d for several gases valid for temperatures ranging from 300 to
1500 K have been approximated with a typical accuracy of ±1%.We can substitute this polynomial in
𝑇
Equation ∆ℎ = ℎ2 − ℎ1 = ∫𝑇 2 𝑐𝑝 (𝑇)𝑑𝑇 and integrate to evaluate changes in enthalpy.
1
If we assume that at an arbitrary reference temperature (Tref) the enthalpy of a gas is h(Tref), we can
𝑇
integrate Equation ∆ℎ = ℎ2 − ℎ1 = ∫𝑇 2 𝑐𝑝 (𝑇)𝑑𝑇
1
𝑇
ℎ(𝑇) − ℎ(𝑇𝑟𝑒𝑓 ) = ∫ 𝑐𝑝 (𝑇)𝑑𝑇
𝑇𝑟𝑒𝑓
If we are interested in changes in enthalpy, rather than absolute values, it does not matter what
reference temperature we choose since
𝑇2 𝑇1 𝑇2
∆ℎ = ℎ(𝑇2 ) − ℎ(𝑇1 ) = ∫ 𝑐𝑝 (𝑇)𝑑𝑇 − ∫ 𝑐𝑝 (𝑇)𝑑𝑇 = ∫ 𝑐𝑝 (𝑇)𝑑𝑇
𝑇𝑟𝑒𝑓 𝑇𝑟𝑒𝑓 𝑇1
It is conventional to pick Tref = 0 K and assume h = 0 at T = 0 K. Using this reference the values of h
𝑇
and u have been calculated by integrating Equation ∆ℎ = ℎ2 − ℎ1 = ∫𝑇 2 𝑐𝑝 (𝑇)𝑑𝑇 and are listed in
1
the ideal gas tables. Using these tables it is possible to directly read values of u and h as functions of
temperature.
Example: Air is heated from 300 to 500 K. Find the change in specific enthalpy using (a) cp evaluated
at 25°C, (b) cp evaluated at Tavg, (c) a function cp(T), (d) ideal gas tables.
Soln.: Initial temperature T1 = 300 K, final temperature T2 = 500 K.
(a) For air at 25°C, cp= 1.004 kJ/kgK(Table):
∆ℎ = 𝑐𝑝 (𝑇2 − 𝑇1 ) = 1.004 × (500 − 300) = 𝟐𝟎𝟎. 𝟖𝟎𝟎 𝒌𝑱⁄𝒌𝒈
𝑇2 +𝑇1 500+300
(b) The average temperature during the heating is 𝑇𝑎𝑣𝑔 = 2
= 2
= 400𝐾
For air at 400 K, cp= 1.013 kJ/kgK (table)
∆ℎ = 𝑐𝑝 (𝑇2 − 𝑇1 ) = 1.013 × (500 − 300) = 𝟐𝟎𝟐. 𝟔𝟎𝟎 𝒌𝑱⁄𝒌𝒈
(c) From Table, for air
𝑐̅𝑝 = 𝑀𝑐𝑝 = 28.11 + 0.1967 × 10−2 𝑇 + 0.4802 × 10−5 𝑇 2 − 1.966 × 10−9 𝑇 3 :
𝑇2 500𝐾
∆ℎ̅ = ∫ 𝑐̅𝑝 (𝑇)𝑑𝑇 = ∫ (28.11 + 0.1967 × 10−2 𝑇 + 0.4802 × 10−5 𝑇 2 − 1.966 × 10−9 𝑇 3 )𝑑𝑇
𝑇1 300𝐾

∆ℎ̅ = [28.11𝑇 + 0.9835 × 10−3 𝑇 2 + 0.1601 × 10−5 𝑇 3 − 0.4915 × 10−9 𝑇 4 ]500𝐾

300𝐾
= 5933.58 𝑘𝐽⁄𝑘𝑚𝑜𝑙𝐾

∆ℎ̅ 5933.58 𝑘𝐽⁄𝑘𝑚𝑜𝑙𝐾

∆ℎ = = = 𝟐𝟎𝟒. 𝟖𝟏𝟖 𝒌𝑱⁄𝒌𝒈𝑲
𝑀 28.97 𝑘𝑔⁄𝑘𝑚𝑜𝑙
(d) From Table, h(300K) = 300.19kJ/kgK and h(500K) = 503.02kJ/kgK:
∆ℎ = ℎ(500𝐾) − ℎ(300𝐾) = 503.02 − 300.19 = 𝟐𝟎𝟐. 𝟖𝟑𝟎 𝒌𝑱⁄𝒌𝒈𝑲

3.2.3 Specific Heats of Liquids and Solids

The volume of liquids and solids changes very little when the pressure and temperature vary. To a
very good approximation, we can assume that they are incompressible substances, whose specific
volume remains constant. We cannot do compression or expansion work on an incompressible

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substance, since its volume does not change. The internal energy of an incompressible substance is
therefore a function of temperature alone:
𝑑𝑢
𝑢 = 𝑢(𝑇) ⇔ 𝑐𝑣 (𝑇) = ⇒ 𝑑𝑢 = 𝑐𝑣 (𝑇)𝑑𝑇
𝑑𝑇
Enthalpy is defined as ℎ = 𝑢 + 𝑃𝑣. Differentiating this expression,
𝑑ℎ = 𝑑𝑢 + 𝑃𝑑𝑣 + 𝑣𝑑𝑃
For incompressible substances dv = 0, Thus
𝑑ℎ = 𝑐𝑣 (𝑇)𝑑𝑇 + 𝑣𝑑𝑃
If we assume pressure is constant dP = 0 and
𝑑ℎ
𝑐𝑣 (𝑇) = ( )
𝑑𝑇 𝑝
The right hand side is the definition of cp(T). For an incompressible substance cp and cv are always
equal. We no longer need a subscript to differentiate between them, so that
𝑐𝑝 (𝑇) = 𝑐𝑣 (𝑇) = 𝑐(𝑇)
If the specific heat c is constant, independent of temperature, we can integrate 𝑑𝑢 = 𝑐𝑣 (𝑇)𝑑𝑇
𝑇2
∆𝑢 = 𝑢2 − 𝑢1 = 𝑐 ∫ 𝑑𝑇 = 𝑐(𝑇2 − 𝑇1 )
𝑇1
and integrate Equation 𝑑ℎ = 𝑐𝑣 (𝑇)𝑑𝑇 + 𝑣𝑑𝑃 to get
𝑇2 𝑃2
∆ℎ = ℎ2 − ℎ1 = 𝑐 ∫ 𝑑𝑇 + 𝑣 ∫ 𝑑𝑃 = 𝑐(𝑇2 − 𝑇1 ) + 𝑣(𝑃2 − 𝑃1 )
𝑇1 𝑃1
Example:
A 1cm diameter copper sphere heated to 300°C is dropped into a well‐insulated beaker containing
10ml of water at 25°C. What is the final temperature once the water and metal have come to
equilibrium?
Properties: Copper density and specific heat ρCu=8900 kg/m3 and CCu=0.386kJ/kg°C (Table), water
density and specific heat ρW=997kg/m3 and cW=4.18kJ/kg°C (Table).

Soln.: Initial temperature of copper T1,Cu=300°C, initial temperature of water T1,W=25°C, diameter of
copper sphere D = 0.01m, volume of water VW = 10ml=10–5m3. Water and copper are both
incompressible, there is no heat loss from the beaker so Q12 = 0.

Mass of copper sphere and water

𝜋𝐷 3 𝜋(0.01)3
𝑚𝑐𝑢 = 𝜌𝑐𝑢 = 8900 𝑘𝑔⁄𝑚3 ×
6 6
= 4.6600 × 10−3 𝑘𝑔

𝑚𝑊 = 𝜌𝑊 𝑉𝑊 = 997 × 105 = 9.97 × 103 𝑘𝑔

Fig. A heated copper sphere is dropped into a well‐insulated beaker filled with water
Since the system is incompressible, W12 = 0 so,
𝑄
⏟ 12 + 𝑊⏟ 12 = ∆𝑈12 = 0
=0 =0
∆𝑈12 = 𝑚𝑐𝑢 ∆𝑈12,𝑐𝑢 + 𝑚𝑊 ∆𝑈12,𝑊 = 𝑚𝑐𝑢 𝑐𝑐𝑢 (𝑇2 − 𝑇1,𝑐𝑢 ) + 𝑚𝑊 𝑐𝑊 (𝑇2 − 𝑇1,𝑊 )
Substituting into the energy balance,
∆𝑈12 = 4.66 × 103 × 0.386 × (𝑇2 − 300℃) + 9.97 × 103 × 4.18 × (𝑇2 − 25℃) = 0
⟹ 𝑻𝟐 = 𝟑𝟔. 𝟑𝟕𝟗℃

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 54

Types of process Features Stay constant Work Heat
Isothermal process ΔT = 0 T and pV 𝑊 = 𝑛𝑅𝑇𝑙𝑛(𝑉2 ⁄𝑉1 ) 𝛥𝑈 = 0
Isobar process Δp = 0 P and V/T 𝑊 = −𝑝𝛥𝑉 𝑄 = 𝑛𝑐𝑝 ∆𝑇
Isochoric process ΔV=0 V and p/T W=0 𝑄 = 𝑛𝑐𝑣 ∆𝑇
𝛾
Adiabatic process Q=0 𝑃𝑉 𝑊 = 𝛥𝑈 Q=0
All gases processes First law: ∆𝑈 = 𝑊 + 𝑄 = 𝑛𝑐𝑝 ∆𝑇 Ideal-gas law: 𝑝𝑉 = 𝑛𝑅𝑇
V/T=Constant : Volume increases as the temperature increases, so is p/T (linear functions)

Questions:

What quantities appear in the first law of thermodynamics?

A. force, mass, acceleration; B. inertia, torque, angular momentum; C. work, heat, thermal energy.
D. work, heat, entropy; E. enthalpy, entropy, heat

A gas cylinder and piston are covered with heavy insulation. The piston is pushed into the cylinder,
compressing the gas. In this process, the gas temperature

A. decreases; B. increases. C. doesn’t change; D. There’s not sufficient information to tell

Two processes are shown that take an ideal gas from state 1 to state 3. Compare the work done by
process A to the work done by process B.

A. WA > WB. B. WA < WB; C. WA = WB = 0; D. WA = WB but neither is zero

Which of the following processes involve heat?

A. The brakes in your car get hot when you stop; B. You push a rigid cylinder of gas across a
frictionless surface; C. A steel block is placed under a candle. D. You push a piston into a cylinder of
gas, increasing the temperature of the gas.

Which first-law bar chart describes the process shown in the pV diagram?

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Objects A and B are brought into close thermal contact with each other, but they are well isolated
from their surroundings. Initially TA = 0°C and TB= 100°C.

The specific heat of A is more than the specific heat of B. The two objects will soon reach a common
final temperature Tf. The final temperature is

A. Tf > 50°C; B. Tf < 50°C. C. Tf = 50°C

For the two processes shown, which of the following is true:

A. QA < QB; B. QA > QB. C. QA = QB

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 Chapter 5: SECOND LAW OF THERMODYNAMICS AND ENTROPY

4.1 Introduction
To operate a mechanical device such as a vehicle, we need to convert heat into mechanical
energy/work. Although it is easier to convert mechanical energy completely into heat (e.g., when
you step on the brakes of a car), it is impossible to convert heat (internal energy) completely into
mechanical energy. Heat engines (steam engines, automobile engines, jet engines etc.) are only
partly successful at converting internal energy (heat) into mechanical energy (work). A closely
related process occurs in the animal kingdom where food is ‘burned’ and partially converted into
mechanical energy when muscles are at work. The rest of the unused food is excreted. On the other
hand, refrigerators are partially successful in transporting heat from a cooler to hotter bodies
(environment). The reasons to these questions lie in the directions of thermodynamic processes
given by the 2nd law of thermodynamics.
The second law of thermodynamics deals with the direction in which natural processes occur. It is
often said that the second law gives a preferred direction to the “arrow of time”, teaching us that
systems naturally evolve with time in one direction but not in the other i.e., heat can only flow from
high temperature reservoir and not vice versa. The second law of thermodynamics also provides
specific guidelines for energy transfer and conversion processes by defining the thermal efficiency of
heat engines thereby imposing limitations on the efficiency of processes that convert heat energy
into mechanical energy and vice versa.

4.1.1 Necessity of the second law

The first law of thermodynamics (conservation of energy) sets limits on acceptable thermodynamic
transformations: for an isolated system, a transformation from state (a) to state (b) is possible only if
U(a) = U(b) or, in other terms, if ∆U = 0. According to the first law, if the transformation from (a) to (b)
is possible, then the reverse from (b) to (a) is also possible. However, experience shows that for each
system (and each choice of U, V, N, etc.) there exists only one well-defined equilibrium state, and
that any isolated system evolves spontaneously and irreversibly towards this equilibrium state.
Hence, the first law of thermodynamics is not sufficient to explain this observation, and a second law
is required to determine the equilibrium state.

Let us consider two examples of irreversible transformations: At equilibrium, each compartment

contains n/2 moles and has an energy U/2. By installing a valve on the pipe, an operator can
distribute as desired the n moles of the gas between the two compartments. As soon as the valve is
opened (which can be done without heat or work), the system spontaneously relaxes to the
equilibrium state; it is Joule’s expansion.

Fig. Joule’s expansion the reverse transformation cannot take place spontaneously and bodies in
thermal contact where the opposite heat flow is never observed whereas the first law does not
exclude that the cold body can give heat to the hot body.

A hot cup of coffee cools by virtue of heat transfer to the surroundings, but heat will not flow from
the cooler surroundings to the hotter cup of coffee.

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Furthermore, Conservation of mass and energy, by themselves, admit as possibilities phenomena
that are not observed in nature! For instance consider an isolated system composed of two equal
masses of liquid water.

As t → ∞:
• TA → 320 K, TB → 280 K. The thermal energy that is gained by A is lost by B, such that the net
energy is conserved and the first law is satisfied. This is never observed in nature.
• TA → 300 K, TB → 300 K. The thermal energy that is lost by A is gained by B, so once again the first
law is satisfied. This is always observed in nature. So mass conservation and the first law of
thermodynamics, both of which speak to this gedankenexperiment, are insufficient to guarantee
that we will predict what is observed in nature. We need another axiom!

Fig. Sketch of two scenarios, both of which satisfy mass and energy conservation

In a similar way, there are a variety of phenomena that may satisfy mass and energy conservation,
but are not observed in nature. Some include: (*) water running uphill without an external assist,
(**) CO2 and H2O that are reacting spontaneously to form CH4 and O2, and (***) air separating into
its constituents spontaneously.

4.2 The Second Law Statements and heat engine/pump

The second law is usually expressed in one of two forms. The first tells us when energy can be
fruitfully put to use. The second emphasises the observation that there is an arrow of time in the
macroscopic world: heat flows from hot to cold. They are usually stated as:

4.2.1 Kelvin-Plank or “Engine” statement of 2nd law: “No process is possible whose sole effect is to
extract heat from a hot reservoir and convert this entirely into work”.

A heat engine is any device that converts heat into a certain amount of net positive work through the
transfer of heat from a high-temperature and to a low-temperature body by means of a cyclic
process. Example of heat engines includes steam engines, automobile engines, or jet engines etc.

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 High temperature
reservoir at Th

Qh

E W

Qc
High temperature
reservoir at Tc
Fig. Operation of a heat Engine and a steam engine’s operation concept

In any heat engine, the working substance undergoes a cyclic process i.e., it must able to be returned
to its initial configuration at the end of each cycle, so that the process can be repeated all over again.
A good example is the steam in a steam engine.

During each cyclic process, a heat engine absorbs heat (Qh) from a high temperature heat reservoir
(at Th 0C) such as a boiler in the case of a steam engine or from the combustion of gasoline in the
case of an automobile engine. The engine then converts this heat partially into work (W) and ejects
the remainder as waste heat (Q2) into a low temperature reservoir (at Tc 0C) such as a condenser in
the case of steam engine or the exhaust of the automobile engine as depicted in Fig.

The second law asserts that a heat engine cannot convert all the heat it receives from a heat source
into work. Some of the heat received must be rejected into a heat sink. This is the law of nature: “If
you must eat, then you must shit”. This assertion is clearly stated in the “Kelvin-Plank’s statement” of
the second law: “it is impossible to construct a device which operating in a cycle produces no other
effect than extract heat from a high temperature reservoir and convert the heat completely into
mechanical work”.

There is zero possibility to manufacture a heat engine continuously producing work by fetching heat
from a single reservoir and ejecting nothing into low temperature sink, as shown in Fig. If the second
law were not true, we could power an automobile by simply cooling the surrounding air. Therefore,
a perpetual motion machine of the second kind (PPM2) does not exist. Example of a perpetual
machine would be a car without an exhaust or a cooling system as shown in Fig. or an animal that
does not shit. Such machine contradicts the Kelvin-Plank’s statement of the 2nd law.

Fig. A hypothetical heat engine NOT ALLOWED by Kelvin statement and a perpetual motion machine
showing a car without exhaust or cooling system which is naturally unrealistic.

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The 2nd law also provides a basis for us to define a criterion of performance for all heat engines –
Thermal efficiency.

Efficiency of heat engines

The “efficiency” or “effectiveness” of a heat engine is a measure of the extent to which a heat
engine is able to convert the heat supplied to it into work. In other words, it is the ratio of the work
output (i.e., what has been accomplished) to the heat input (i.e., what you pay for to get it done).
𝑾
𝜺=
𝑸𝒉
Where W = work performed and Qh = heat obtained from the hot reservoir. The work (W) done by a
heat engine can be obtained from the 1st law of thermodynamics (dW = dQ – dU). Since in such a
cyclic process, there is no change in the internal energy of the system (i.e., dU = 0), it follows that
dW = dQ i.e., the net heat input is converted to work output [Principle of heat engine].
𝑊 𝑄ℎ − 𝑄𝑐 𝑸𝒄
𝑊 = 𝑄ℎ − 𝑄𝑐 ∴ 𝜀 = = ⟺𝜺=𝟏−
𝑄ℎ 𝑄ℎ 𝑸𝒉
If the working substance is an ideal gas, then it can also be shown that
𝑄ℎ 𝑄𝑐 𝑻𝒉
= ∴ 𝜺=𝟏−
𝑇ℎ 𝑇𝑐 𝑻𝒄
Experimental evidence suggests that even under ideal conditions, QC  0 (never) and as such, it is
impossible to construct a heat engine with 100% thermal efficiency as stipulated in the 2nd law of
thermodynamics. This is because a heat engine always ejects substantial amount of heat (QC) into
the environment.

4.2.2. Clausius or “Refrigerator” statement: “No process is possible whose sole effect is the
transfer of heat from a colder to hotter body”. This transfer is done in heat pumps.
A heat pump is a heat engine operated in reverse i.e., it is an engine which requires work input in
order to transfer heat from a colder reservoir to a hot reservoir as shown in Fig. This is the principle
involved in refrigerators, heat pumps and air conditioners. Heat pumps are widely used to heat
buildings during the cold weather. They operate by transferring heat from the outside (which is at
lower temperature QC) to the insider which is at a higher temperature Qh. In comparison, a heat
pump is merely a refrigerator turned inside out so that its cold end is outdoors and its warm end
indoors.

Fig. Operation of Refrigerator and a Hypothetical Refrigerator: Clausius -NOT ALLOWED

As to Clausius; “No cyclic process can transfer heat from a cold reservoir to a hotter region with no
input of mechanical work”. This simply means: “For you to work, you must eat”.
Thus; the second law denies the possibility of reversing the natural for heat to flow from a hotter to
a colder body without external interference (in the form of work). The second law also allows us to

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define a criterion of performance of heat pumps. This criterion or the “effectiveness” of a heat pump
is called the coefficient of performance (COPHP) and is defined by
𝑄 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑟𝑒𝑑 𝑡𝑜 ℎ𝑖𝑔ℎ − 𝑡𝑒𝑚𝑝 𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟 𝑄ℎ 𝑄ℎ
𝐶𝑂𝑃𝐻𝑃 = = =
𝑊𝑜𝑟𝑘 𝑖𝑛𝑝𝑢𝑡 𝑊 𝑄ℎ − 𝑄𝑐
For heat pumps 𝐶𝑂𝑃𝐻𝑃 > 1 and it depends on the outside temperature. If the outside temperature
is say 40C or higher, 𝐶𝑂𝑃𝐻𝑃 ≈ 4 i.e., amount of energy transferred to the building is about 4 times
greater than the work done by the motor in the heat pump. However, as the outside temperature
decreases (TC  0), the heat delivered becomes equal to the work required and the COPHP can fall
below unit. Under such circumstances, it becomes difficult for the heat pump to extract sufficient
energy from the outside air and the heat pump has no economic advantage over electric heaters.
Under such circumstances, it would be cheaper to burn the original fuel directly for the heat, rather
than generate electricity to operate a heat pump.

Thus, the use of heat pumps that extract energy from the air is only satisfactory in moderate climate
but it is not appropriate in areas where cold (winter) temperatures are very low. An alternative is to
bury the external coils deep in the ground so that the energy is extracted from the ground, which is
warmer than the air above.
The statements by Kelvin and Clausius are equivalent. Suppose, for example, that we build a
machine that violates Kelvin’s statement by extracting heat from a hot reservoir and converting it
entirely into work. We can then use this work to power a fridge, extracting heat from a cold source
and depositing it back into a hot source. The combination of the two machines then violates
Clausius’s statement. It is not difficult to construct a similar argument to show that “not Clausius” ⟹
“not Kelvin”.

Fig. Equivalence machine for kelvin and Clausius statement

The Refrigerator
Practical refrigerators use gas and liquid Freon (dichlorodifluoromethane) as working fluid
(refrigerants) and their cycle differs from the Carnot cycle. Refrigerants (Freon etc.) have a boiling
point near room temperature when at high pressure, but a boiling point below at 00C when at low
pressure.
In each cycle, Liquid Freon at low pressure and low temperature enters the cooling coils in the
refrigerator box and absorbs heat while evaporating into Freon gas. This gas flows to the compressor
(outside the refrigerator box), where its pressure, temperature and density are increased by the
push of a piston. The high-pressure gas then circulates through the condenser coils, which are
exposed to the atmospheric air as the Freon gas loses its heat and condenses into a liquid. This high-
pressure liquid then passes through an expansion valve (a small orifice) where its pressure is
reduced to match the low pressure in the cooling coils. This return of the fluid to the cooling coils
completes the cycle.

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Fig. Principle of a mechanical refrigerant cycle, the coils on the back of a refrigerator transfer energy
by heat to the air outside and inside a refrigerator
𝑄 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑟𝑒𝑑 𝑓𝑟𝑜𝑚 𝑐𝑜𝑙𝑑 𝑟𝑒𝑠𝑒𝑟𝑣𝑜𝑖𝑟 𝑄𝑐 𝑄𝑐 𝑻𝒄
𝐶𝑂𝑃𝑅 = = = = ∴ 𝐶𝑂𝑃𝐻𝑃 = 1 + 𝐶𝑂𝑃𝑅
𝑊𝑜𝑟𝑘 𝑖𝑛𝑝𝑢𝑡 𝑊 𝑄ℎ − 𝑄𝑐 𝑻𝒉 − 𝑻𝒄
(Carnot refrigerator)

From an economic point of view, the best refrigerator is one that removes the greatest amount of
heat QC from the inside of refrigerator for the least amount of work (W). The value of COPR is  5.
However, if (Th–TC) or Th (the room temperature) is very high, then COPR  0 and more work will be
required to transfer a given quantity of heat from the refrigerator. However, if (Th–TC) or Th (the
room temperature) is very high, then COPR  0 and more work will be required to transfer a given
quantity of heat from the refrigerator.

Note also that the refrigerator supplies heat to the heat pump at the back of the refrigerator. The
function of such a heat pump is to deliver heat to some reservoir which is at a higher temperature
than its surrounding.

Example
1. Suppose that QC = 200J, W = 100J. Determine the COP of the refrigerator
Soln.: In this case, Qh = 200 + 100 = 300J
𝑄𝑐 200
𝐶𝑂𝑃𝑅 = = = 2 (𝑜𝑟 200%)
𝑄ℎ − 𝑄𝑐 100
Note: In the case of a heat engine, efficiency cannot be more than 100% but in the case of a
refrigerator, COPR can be higher than 100%.

2. In a refrigerator, the cooling chamber is maintained at 290K while the outside temperature is
305K. The motor (located outside) has compression cylinders operating at 320K and the expansion
coils inside the chamber operating at 280K. If the motor operates reversibly
(i) Give a schematic diagram illustrating the sequence of events
(ii) Calculate the efficiency of the motor
(iii) Calculate the COP of the refrigerator
(iv) How much work must be done for each transfer of 5,000J of heat from the chamber?

Soln.: In this case, the refrigerator is powered by the motor which supplies work to it as shown
below.

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(i)
(ii) The refrigerator is powered by the motor (E). Hence the efficiency of the motor is
𝑊 𝑄ℎ𝐸 − 𝑄𝑐𝐸 320 − 280
𝜀= = = = 12.5%
𝑄ℎ𝐸 𝑄ℎ𝐸 320
(iii) COP of the refrigerator
𝑄𝑐 𝑄𝑐 𝑇𝑐
𝐶𝑂𝑃𝑅 = = = = 19.3
𝑊 𝑄ℎ − 𝑄𝑐 𝑇ℎ − 𝑇𝑐
(iv) From
𝑄ℎ𝐸 𝑇ℎ𝐸 𝑇ℎ𝐸
= ⟺ 𝑄ℎ𝐸 = (5000) = 5.258𝐽 ∴ 𝑊 = 𝑄ℎ𝐸 − 𝑄𝑐𝐸 = 258.6𝐽
𝑄𝑐𝐸 𝑇𝑐𝐸 𝑇𝑐𝐸

The Air Conditioner

The air conditioner employs a similar refrigeration cycle but in this case, the refrigerator box
becomes a room or an entire building. The evaporator coils are inside, the condenser is outside, and
fans circulate air through these as shown in the fig.

Fig. An air conditioner working on the same principle as a refrigerator

The parameters of interest are the rate of heat removal (heat current H from the room) and the
power input P (=W/t) to the compressor. H is the heat removed per sec = (QC/t). Hence coefficient of
performance is
𝑄𝑐 𝐻𝑡 𝐻 𝑇𝑐
𝐶𝑂𝑃 𝐴𝐶 = = = =
𝑊 𝑃𝑡 𝑃 𝑇ℎ − 𝑇𝑐
A typical value of COPAC is about 2.5 and is dependent on the inside and outside temperatures.

The Carnot Engine

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Since the conversion of work to heat is an irreversible process, a heat engine only partly reverses this
process. For maximum efficiency, the thermodynamic process within the engine must be reversible
i.e., the engine can, in principle be operated in reverse converting work into heat at the same rate as
in the forward direction.
Thus, when the engine takes heat from the hot reservoir at Th, the working substance should also be
at Th i.e., no heat should be lost. Similarly, when the engine discards heat to the cold reservoir at TC,
the engine itself must be at TC. Thus, every process involving heat transfer must be isothermal at
either Th or TC. Conversely, for any process in which the working substance is intermediate between
Th and TC, there must be no heat transfer (adiabatic process) between the engine and either
reservoir otherwise; such a process could not be reversible. Additionally, thermal and mechanical
equilibrium must be maintained at all times.

The only engine with maximum possible efficiency is a hypothetical, idealized reversible heat engine
called the Carnot Engine.it is a hypothetical engine which is assumed to be reversible with no
dissipative effects such as turbulence and friction. The Carnot engine operates between two
reservoirs with an ideal gas as the working fluid enclosed in a cylinder with a piston.

Fig. Carnot power cycle executed by a gas in a piston–cylinder assembly

Take Note: It is important to emphasize that reversibility is a standard of perfection. In real life, no
process is totally reversible; reversibility is approached but it is never achieved in practice. A
reversible process is thus an abstraction because all natural processes result in energy loss in terms
of turbulence, friction or other dissipative effects. A reversible engine therefore represents the
perfect engine in the sense that it converts the highest fraction of heat into work.
The Carnot cycle consists of a sequence of 4 steps (with two isothermal and two adiabatic processes)

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 64

 Fig. The Carnot Cycle on a P-V diagram

Path a  b: Heat Qh enters the system and the gas expands isothermally (dT = 0) from volume V1 to
V2 doing work on the piston
Path b  c: Gas expands adiabatically (dQ =0) as temperature decreases from Th to TC.
Path c  d: Gas is compressed isothermally from volume V3 to V1 thereby ejecting heat (QC) into the
low temperature reservoir at TC.
Path d  a: Gas is compressed adiabatically from (V4, P4) to (P1, V1) as temperature rises from TC to
Th. The total done in the cycle is the area abcd.
𝑊 𝑄ℎ
𝜀= =
𝑄ℎ 𝑄ℎ − 𝑄𝑐
For the isothermal expansion a  b, dUab = 0 (since dT = 0). Hence we have that.
𝑉2 𝑉4 𝑉3
𝑄ℎ = 𝑑𝑊𝑎𝑏 = 𝑛𝑅𝑇ℎ ln ∴ 𝑄𝑐 = 𝑑𝑊𝑐𝑑 = −𝑛𝑅𝑇ℎ 𝑙𝑛 = 𝑛𝑅𝑇𝑐 𝑙𝑛
𝑉1 𝑉3 𝑉4
𝑉3
𝑄𝑐 𝑇𝑐 𝑙𝑛
𝑉4
𝜀 =1− =1−
𝑄ℎ 𝑉
𝑇ℎ 𝑙𝑛 𝑉2
1

For the two adiabatic processes b  c and d  a, we have

𝛾−1 𝛾−1
𝛾−1 𝛾−1 𝛾−1 𝛾−1 𝑉2 𝑉3 𝑉2 𝑉3
𝑇ℎ 𝑉2 = 𝑇𝑐 𝑉3 𝑎𝑛𝑑 𝑇ℎ 𝑉1 = 𝑇𝑐 𝑉4 ⟺ 𝛾−1 = 𝛾−1 𝑜𝑟 =
𝑉1 𝑉4 𝑉1 𝑉4
Therefore;
𝑄𝑐 𝑇𝑐
𝜀 =1− =1−
𝑄ℎ 𝑇ℎ
This is the Carnot efficiency for a heat engine and it is the maximum possible efficiency attained by
any engine operating between 2 reservoirs.

The efficiency () can only be = 1 (100%) iff TC = 0 K, which is not possible. No real engine can have a
thermal efficiency greater than the Carnot efficiency. This assertion is stated in the Carnot’s
theorem:

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 65

 All real (irreversible) heat engines operating between any two heat reservoirs are less efficient than
a Carnot’s engine operating between the same reservoirs.
 All reversible heat engines operating between the same two heat reservoirs have the same
efficiency (as a Carnot’s engine operating between the same reservoirs).

Example:
A man uses a Carnot engine operating in reverse as a heat pump to extract heat from the outside air
(at -100 C) and inject it into his house (at 200C). What is the amount of work that must be supplied to
pump 4.2 KJ of heat from the outside to the inside?
Soln.: 𝑇ℎ =20+273=293K, 𝑇𝑐 =-10+273=283K
𝑄𝑐 𝑇𝑐
= = 0.9 ⟺ 𝑄ℎ = 𝑄𝑐 ⁄0.9 = 𝟒. 𝟔𝟕𝒌𝑱
𝑄ℎ 𝑇ℎ
This is more economical heating method than the expenditure of 4.2 KJ of fuel in conventional
furnace or electric heater

Why the Carnot Efficiency is the best possible?

It assumes that there is no temperature difference between the heat reservoir and the working fluid,
so that the entropy gained by one exactly matches the entropy lost by the other, with no net change
in entropy for the system as a whole. This condition is of course an ideal one, and cannot be met in
practice by any real machine. Even theoretically; all real machines will be strictly worse than this.

The steam engine

The operation of a steam engine resembles the Carnot cycle but uses steam and water as working
fluid instead of an ideal gas.

Fig. A steam engine map and a steam-driven locomotive that used to run from Mombasa-Kisumu
In each cycle of operation, the high-pressure steam enters the cylinder and pushes against the piston
doing work. The low-pressure, spent steam is then exhausted from the cylinder and sent to
condenser where an external coolant (air or flowing water) condenses the steam into liquid water
which is pumped back to the boiler and the cycle is repeated.
𝑄𝑐 𝑇𝑐
𝜀𝑆𝑡𝑒𝑎𝑚 = 1 − =1−
𝑄ℎ 𝑇ℎ
Such simple steam engine has efficiencies of about 5-18%. To maximize the efficiency, the designer
must make the intake temperature Th as high as possible and TC as low as possible (= room
temperature of water). Th is limited by the mechanical strength of the boiler (since pressure
increases with temperature) and maximum value of Th possible is 5000C (pressure = 235atm in
present day steam boilers). Most modern steam engines employ a turbine wheel instead of the
cylinder and piston and can achieve efficiencies of up to 40%.

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Example: A steam engine has a boiler that operates at 500 K. The cold reservoir’s temperature is
that of the outside air, approximately 300K. Determine the maximum thermal efficiency of this
steam engine.
Soln.:
𝑄𝑐 𝑇𝑐 300𝐾
𝜀𝑆𝑡𝑒𝑎𝑚 = 1 − =1− =1− = 0.4 𝑜𝑟 40%
𝑄ℎ 𝑇ℎ 500𝐾
This is the max possible (theoretical efficiency)

Internal Combustion Engines

Internal combustion engines are where the release of energy by combustion takes place within the
confines of the engine. Examples of such engines include cars; trucks etc. and they employ a fluid
which remains gaseous throughout. These engines can broadly be divided into two categories: (i)
Spark ignition or compression ignition types with either 2 or 4 stroke, (ii) Gas turbines.

(a) The Gasoline Engine (Otto Cycle)

In real engines, the cycles proceed rapidly with friction and turbulence with no quasi-static and the
cycles are irreversible. To discuss a real engine cycle, we replace it by an idealized model (called the
Otto cycle) in which the working substance is assumed to be an ideal gas and all processes are
assumed to be reversible.

Fig. The real cycles of a 4-stroke gasoline (petrol) engine

Intake Stroke, e  a: The intake valve opens and the mixture of air and gasoline vapour flows into
the cylinder as the piston descends. This is a quasi-static isobaric process (dP = 0) where the volume
increases from V1 to V2; with V2 = rV1 where r is the compression ratio.

Compression Stroke, a  b: Intake valve closes and the mixture is compressed, approximately
adiabatically from volume V2 to volume V1 as the temperature rises from Ta to Tb. This process can be
represented by the adiabatic expression;
𝛾−1 𝛾−1
𝑇𝑎 𝑉2 = 𝑇𝑏 𝑉3

Ignition and Power Stroke, b  c  d: Mixture is ignited by a spark plug (path b c) ejecting heat Qh
into the system. This process occurs in a very short period of time and is not one of the strokes of
the cycle. During this time, the temperature and pressure increases rapidly. However, the volume
remains approximately constant because of the short time interval and as a result; approximately no
work is done on the gas. The heat input along path b  c therefore occurs at constant volume
(isochoric) with
𝑄ℎ = 𝑐𝑣 (𝑇𝑐 − 𝑇𝑏 )

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During the power stroke (path c  d), the mixture expands approximately adiabatically back to
volume V2 pushing on the piston and doing some work. In this case, the temperature drops from Tc
to Td according to the adiabatic expression;
𝛾−1 𝛾−1
𝑇𝑎 𝑉2 = 𝑇𝑏 𝑉3
The work done in this process is the area under the curve cd.

Exhaust Stroke d  a e: Exhaust valve opens allowing the gas to cool at nearly constant volume
down to temperature Ta as the pressure drops. During this interval, the volume remains
approximately constant (isochoric) as heat Qc is ejected into the environment where
𝑄𝑐 = 𝑐𝑣 (𝑇𝑑 − 𝑇𝑎 )

Along path a e, the combustion products are pushed out (isobarically) as the volume decreases
from V2 to V1 leaving the cylinder for the next intake stroke.

Fig. P-V diagram of Otto Cycle Representing the Gasoline Engine Cycle and P-V diagram for a Diesel
Cycle

The thermal efficiency of this idealized engine is thus given by

𝑄𝑐 𝑐𝑣 (𝑇𝑑 − 𝑇𝑐 )
𝜀 =1− =1−
𝑄ℎ 𝑐𝑣 (𝑇𝑐 − 𝑇𝑏 )
But from compression and power stroke equations, we get

𝑉2 𝛾−1 (𝑇𝑐 − 𝑇𝑏 )
(𝑇𝑑 − 𝑇𝑎 )𝑉2𝛾−1 = (𝑇𝑐 − 𝑇𝑏 )𝑉1𝛾−1 ⟺ ( ) =
𝑉1 (𝑇𝑑 − 𝑇𝑎 )

𝑐𝑣 (𝑇𝑑 − 𝑇𝑐 ) 𝑉2 𝛾−1 1
𝜀 =1− =1−( ) = 1 − 𝛾−1
𝑐𝑣 (𝑇𝑐 − 𝑇𝑏 ) 𝑉1 𝑟𝑐

Where rc is the compression ratio. This efficiency in terms of temperature:

𝑉2 𝛾−1 𝑇𝑎 𝑇𝑑 𝑇𝑎 𝑇𝑑
( ) = = ∴𝜀 =1− =1−
𝑉1 𝑇𝑏 𝑇𝑐 𝑇𝑏 𝑇𝑐
NB. During the Otto cycle, the lowest temperature is Ta and the highest is Tc such that the efficiency
of the Carnot engine operating between these two temperatures will be given by 𝜀 = 1 − 𝑇𝑎 ⁄𝑇𝑐 .

This is greater than the efficiency of the Otto cycle given by previous Equation as expected.

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From Efficiency expression, the efficiency increases as the compression ratio (rC) increases. For
typical compression ratios of 8 (for most engines), and with γ =1.4 (for air), we predict the
theoretical efficiency of 1 − 1⁄80.4 = 56% for an engine operating in the idealized Otto cycle.

Although it is important to have a high compression as possible, it is noted that increasing the
compression ratio also increases the temperature during the adiabatic compression of the air-fuel
mixture causing the mixture to explode spontaneously during compression before ignition. This is
pre-ignition or detonation and causes “knocking”, damaging the engine. Pre-ignition lower the value
of rC to about 7 particularly for unleaded low octane petrol thereby lowering its efficiency.

Note: In real engines, the cycle proceeds rapidly with friction, turbulence and no quasi-static (hence
irreversible), loss of heat to cylinder walls and incomplete combustion of air-fuel mixtures leading to
low efficiency values (20 - 30%). Incomplete combustion occurs if the mixture has less gasoline
with the resulting products of CO and unburned hydrocarbons (air pollution) instead of CO2 and H2O.

(b) The Diesel Engine

It is similar to the petrol engine only that there is no fuel in the cylinder at the beginning of the
compression stroke. Instead, air is adiabatically compressed and just before the power stroke, the
injectors eject fuel directly into the cylinder. Due to the high temperature, this fuel ignites
spontaneously. No spark plugs are needed.

Note: Since no fuel is compressed, pre-ignition does not occur in diesel engines resulting in high
compression ratios and high efficiency values (r  15 – 20,   65 – 70%). Diesel engines are often
heavier and harder to start but they need no carburettor or ignition system. However, the fuel-
injection system requires expensive high-precision machining.

(c) Turbochargers and Intercoolers

The power output of an engine is proportional to the mass of air forced into the engine’s cylinder. In
turbocharged systems, air is compressed (nearly adiabatically with rise in temperature) before
entering the engine. This gives a greater mass of air per unit volume.

In intercoolers, the compressed air is cooled by passing through an internal cooling system where it
loses heat to the surrounding (at constant pressure), and then compressed further. Due to high T
and P values in these systems, turbochargers and intercoolers are more powerful than ordinary
engines.

Example: The compression ratio of a diesel engine is 15 to 1 i.e., air is compressed to 1/15 of its
initial volume. If the initial pressure and temperatures are 1.0  105 Pa and 270C (300K), Determine:
(a) The final pressure and temperature after compression (assume ideal gas conditions,  = 1.4)
(b) The work done by the gas if V1 = 1.0 litres (Cv = 20.8 J mol-1K-1).
Soln.:
(a) Since 𝑉1⁄𝑉2 = 15 ⇒ 𝑇2 = 𝑇1 (𝑉1⁄𝑉2 )𝛾−1 = 613℃
And 𝑃2 = 𝑃1 (𝑉1 ⁄𝑉2 )𝛾−1 = 11.8 × 105 𝑃𝑎 = 44𝑎𝑡𝑚
𝑃1 𝑉1
(b) Using 𝑃𝑉 = 𝑛𝑅𝑇 ⇒ 𝑛 = ( ) = 0.0405𝑚𝑜𝑙
𝑅𝑇1
1
⇒ 𝑊 = 𝑛𝑐𝑣 (𝑇2 − 𝑇1 ) = (𝑃 𝑉 − 𝑃2 𝑉2 ) = −494𝐽
𝛾−1 1 1
NB. –ve sign since compression

Explain why lead is usually added to petrol used in car engines?

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 Chapter 6: ENTROPY AND THIRD LAW OF THERMODYNAMICS

In our consideration of the first law, we initially stated the law in terms of a cycle, but then defined a
property, the internal energy, which enabled us to use the first law quantitatively for processes.
Similarly, we have stated the second law for a cycle, and we now find that the second law leads to a
property, entropy, which enables us to treat the second law quantitatively for processes. Entropy
(Rudolf Clausius, 1865 from Greek word transformation) is a quantitative measure of disorder. The
importance of Entropy is that it provides us with a criterion of reversibility and thereby enable us
determine the direction of naturally occurring processes.

Entropy: One-Way Process

All naturally occurring processes proceed in one direction only: They never, of their own accord,
proceed in the opposite direction.
Examples: (1) If you drop a stone, it falls to the ground. A stone resting on the ground never, of its
own accord, leaps up into the air; (2) If you put a drop of ink in a glass of water, the ink molecules
eventually spread out uniformly throughout the volume of water. They never, of their own accord,
regroup into a drop-shaped clump. Such spontaneous one-way processes are irreversible. You
cannot make them go backward by making any small change in their environment. Notably, it is not
the energy that controls the direction of irreversible processes; it is a property called Entropy (S) of
the system which is a measure of randomness or disorder of a system.

Fig. This professor’s room is untidy and disorderly. We say it has high entropy compared to his
assistant’s room which is orderly representing low entropy.

Entropy is a thermodynamic property that can be used to determine the energy not available for
useful work in a thermodynamic process, such as in energy conversion devices – engines and
machines. Such devices have a theoretical maximum efficiency when converting energy to work.
During this processes, entropy (or disorder) accumulates in the system, but has to be removed by
dissipation in the form of waste heat.

The air all around us possesses internal energy, so why not take heat from the atmosphere and use
that to power a car engine? The car will do work on the surrounding air while moving and thereby
return energy to it, satisfying the first law of thermodynamics.

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 If we can invent such an engine we will have limitless power at our disposal
and never need to refuel our car. This wonderful engine sounds too good to
be true, but there is nothing in the principle of energy conservation that
forbids it.

Fig. A proposed engine takes heat (Q) from the atmosphere and does an equal amount of work (W)
on the surroundings. Combustor heat transfer into gas work on the surroundings and gas heat loss
to the surroundings until original piston position

Why we cannot make an engine that runs without any fuel. How to transform heat into work: To use
the heat of a continuously fuel- supplied combustor maintaining constant TH to do work; it is brought
into contact with a cylinder containing gas that expands doing work in raising the piston (LHS Fig.).
The piston will rise until the gas in the cylinder is heated to TH, reaching thermal equilibrium after
which there will be no further heat transfer to the gas or movement of the piston. The system has
not run out of energy – the combustor can draw as much fuel as necessary – but by definition a
system at equilibrium cannot do work on its surroundings.

To use the gas in the cylinder to do more work we have to disrupt the equilibrium and restore the
piston to its original position. We can do this by separating the cylinder from the combustor and
letting the gas in it cool (RHS Fig.), dissipating QC joules of heat to the surrounding atmosphere. By
repeating this heating and cooling cycle we can continuously do work. An engine always operates
between a high temperature heat source and a low temperature heat sink, alternating between the
two so that it never stays at equilibrium.

If we reduce the temperature of the combustor the distance the piston moves will decrease and
therefore the amount of work done will be less. Conversely, if we increase the temperature of the
combustor the gas expands further and the piston rises higher, producing more work. The work
output of an engine depends not only on the amount of heat added to it but also the temperature at
which it is added, and in the limit that TH → TC the work goes to zero. The energy dissipated to the
atmosphere (QC) does not disappear but since it is at the temperature of the heat sink it is useless
for doing more work. Not all heat inputs are equal – the higher the temperature at which heat is
supplied, the more effectively it can be used to do work. Therefore, we need to describe not only the
quantity of heat that is added to the engine, but also its quality.

Hence by combining the two features, we get extensive property “entropy” that measures the
quality of the amount of heat. That property changes when heat is added to or removed from the
system. The magnitude of change is
𝐻𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑡
𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 =
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
The temperature we use to evaluate entropy is that of the system boundary across which heat
transfer occurs. Technically, when we add an infinitesimal amount of heat (δQ) to a closed system

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at temperature T, its internal energy increases by dU = δQ (assuming no work is done) and its
entropy, denoted by the symbol S, increases by
2 2
𝛿𝑄 𝛿𝑄
𝑑𝑆 = ⟺ ∆𝑆 = ∫ 𝑑𝑠 = ∫
𝑇 1 1 𝑇

When calculating entropy changes it is convenient to use the concept of a thermal reservoir (very
large masses such as the atmosphere or a lake or a combustor), which is a system whose
temperature remains constant and uniform in spite of heat transfer to or from it. The entropy change
of a thermal reservoir we at constant T and its rate can be couched as follows:

1 2 𝑄12 𝑄̇
𝑆= ∫ 𝛿𝑄 = 𝑎𝑛𝑑 𝑆̇ =
𝑇 1 𝑇 𝑇

Where 𝑄̇ [watts (W)], is the rate of heat transfer to or from a thermal reservoir and 𝑆̇ is its rate of
entropy change [W/K]. Entropy and energy are related properties, but there is one very important
difference between them: energy is conserved but entropy can be generated. If thermal reservoir A
at temperature T + ∆T loses Q joules of heat to thermal reservoir B at lower temperature T;

the entropy decrease of the hotter system A and the increase in entropy of
B are:
𝑄 𝑄
∆𝑆𝐴 = 𝑎𝑛𝑑 ∆𝑆𝐵 =
𝑇 + ∆𝑇 𝑇
For heat transfer to occur ∆T must be positive, so ∆SA < ∆SB. The entropy of
system B increases more than the entropy of system A decreases, implying
that every time we transfer heat we generate entropy:
∆𝑆𝑔𝑒𝑛 = ∆𝑆𝐵 − ∆𝑆𝐴
In the limit that ∆T → 0, Sgen→ 0: There is no entropy generated when heat
transfer takes place between two thermal reservoirs whose temperatures
differ by an infinitesimal amount.
Fig. Heat transfer from a thermal reservoir A to another thermal reservoir B

For Sgen to be negative we need ∆T < 0. Destruction of entropy requires that heat move from a cold
to a hot region, which cannot happen spontaneously. Entropy can be generated but not destroyed.

“In any closed system, the entropy of the system will either remain constant or increase.” It is
natural to characterize the equilibrium state as the state that maximizes “something”. This
“something” is entropy. Entropy production continues as long as temperature gradients exist in the
system and stops only when equilibrium is reached. The entropy of an isolated system increases until
it reaches equilibrium and then remains constant.

Another important difference between entropy and energy is that, according to our definition (𝑑𝑆 =
𝛿𝑄 ⁄𝑇), when we do work on a system its energy increases but its entropy remains the same
because entropy is a function of heat, not work. Doing work on a system does not increase its
entropy. When a mass is pushed up a frictionless ramp its entropy remains constant while its
potential energy increases. If, though, there is friction between the mass and the ramp part of the
work done on the system is converted to heat, which when dissipated to the surroundings creates
entropy.

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Example: A 10 kg mass of lead heated to 200°C is dropped into a lake at a temperature of 18°C. Find
the increase in entropy of the lake.

Soln.: Mass of lead m = 10 kg, initial temperature of lead T1 = 200°C, temperature of lake TC = 18°C.
Specific heat of lead c = 0.128 kJ/kg°C. It is to be assumed that Lead cools down to the temperature
of lake, so final temperature of lead T2 = 18 °C, temperature of lake remains constant. Heat lost by
lead while cooling is:

𝑄𝑐 = 𝑚𝑐(𝑇2 − 𝑇1 ) = 10 × 0.128(18 − 200) = −232.96𝑘𝐽

Heat gained by lake is 𝑄𝐻 = −𝑄𝑐 = 232.96𝑘𝐽, Then, the entropy increase of the lake is
𝛿𝑄𝐻 232.96
𝑑𝑆 = = = 0.80014 𝑘𝐽⁄𝐾
𝑇 273.15 + 18
Entropy and the 2nd law of Thermodynamics

The principle of increasing Entropy states categorically that “The Entropy of an irreversible processes
always increases; It never decreases”, since in such processes, there is an increase in disorder. The
fact that entropy increases cannot be derived from first principles: it is a consequence of the
observation that the direction of spontaneous heat transfer is from higher temperatures to lower
temperatures, but not the other way around. We therefore accept it as a postulate that cannot be
proven but we assume to be true. Thus, the second law of thermodynamics states that:
The entropy of an isolated system will increase until the system reaches a state of equilibrium.
The entropy of an isolated system in equilibrium remains constant.
Mathematically we can express this statement as:
𝑑𝑆𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 > 0 𝑛𝑜𝑡 𝑖𝑛 𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
{ 𝑑𝑆𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 = 0 𝑖𝑛 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
𝑑𝑆𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 < 0 𝑛𝑜𝑡 𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒
This statement can be written as
𝑑𝑆𝑖𝑟𝑟𝑒𝑣 > 0
On the other hand, for a reversible (adiabatic process, dQ = 0), the Total entropy change is always
zero i.e.,
𝑑𝑆𝑟𝑒𝑣 = 0
From these expressions, we can obtain the general statement for the definition of entropy as:

Irreversible

[For any cycle]

Reversible

But since
𝑑𝑄
𝑑𝑆 = ⟹ 𝑇𝑑𝑆 ≥ 𝑑𝑄 ≥ 0
𝑇
From this Equation, we see that the 2nd law limits the availability of energy and the way in which it
can be used and converted. It is the law of nature describing the direction of natural thermodynamic
processes. This equation gives the direction of transformation from one state to another and we see
that any such direction should be such as to increase the Entropy. This is the general form of the
Second Law of Thermodynamics.

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Thus the second law can be stated quantitatively in terms of entropy as follows: “No natural process
is possible in which the total entropy decreases when all systems taking part in the process are
included”. This is equivalent to the “Engine” and/or the “Refrigerator” statement of the 2nd law.

The above statement implies that heat will not flow from a colder body to a hotter body without the
application of work (the imposition of order) to the colder body. Secondly, it is impossible for any
device operating on a cycle to produce net work from a single temperature reservoir without
ejecting any heat to the colder reservoir. As a result, there is no possibility of a perpetual motion
system.

Finally, it follows from the second law of thermodynamics that the entropy of a system that is not
isolated may decrease. An air conditioner, for example, may cool the air in a room, thus reducing the
entropy of the air of that system. The heat expelled from the room (the system), involved in the
operation of the air conditioner, will always make a bigger contribution to the entropy of the
environment than will the decrease of the entropy of the air of that system. Thus, the total of
entropy of the room plus the entropy of the environment increases, in agreement with the second
law of thermodynamics.

Combining the 1ST and 2ND law of thermodynamics, we get the central equation of
Thermodynamics:
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
{ ∴ 𝑻𝒅𝑺 ≥ 𝒅𝑼 + 𝑷𝒅𝑽 [𝐹𝑜𝑟 𝑎𝑛𝑦 𝑝𝑟𝑜𝑐𝑒𝑠𝑠]
𝑇𝑑𝑆 ≥ 𝑑𝑄 ≥ 0
This equation holds for all processes (both reversible and irreversible) since all the functions in the
equation are state function.

From the Central Equation of thermodynamics, we can analyse Entropy and degradation of energy.
We have that,

𝒅𝑾 ≤ 𝑻𝒅𝒔 − 𝒅𝑼
This expression implies that the system does less work in an irreversible process (since TdS > 0).
Hence, of the available energy, some must go into increasing the Entropy (S) and hence the energy is
degraded in that it is less useful for doing work. The energy involved in the entropy change is tied up
in the random arrangement and thermal motion of the atoms, it is often referred to as unavailable
energy. For a reversible process, 𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = −𝑑𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 i.e., total entropy change in system +
surrounding is zero. More work is done in this case.

Examples
One kilogram of ice at 00C is melted and converted to water at 00C. Compute the change in Entropy.
Take the specific latent heat of fusion of ice (SLHF) as = 333624.2 JKg-1.
Soln.: Since the temperature remains constant,
1 𝑄 333624.2
∆𝑆 = 𝑆2 − 𝑆1 = ∫ 𝑑𝑄 = = = 1222.1𝐽𝐾 −1
𝑇 𝑇 273
1 kg of water at 00C is heated to 1000C. Compute the change in entropy
Soln.:
𝑇2 𝑇2
𝑑𝑄 𝑑𝑇 𝑇2
𝑑𝑄 = 𝑚𝑐𝑑𝑇 ∴ 𝑑𝑆 = ∫ = ∫ 𝑚𝑐 = 𝑚𝑐 ln = 1.31 × 103 𝐽𝐾 −1
𝑇1 𝑇 𝑇1 𝑇 𝑇1

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Compute the entropy change that occurs when 1kg of water at 1000C is mixed with 1kg of water at
00C.
Soln.: We shall assume the entropy of water is zero when it is in the liquid state at 00C.
(-)From the last example, the entropy of water at 1000C is 1310.85JK-1 and the entropy of 1kg of
water at 00C is zero.
⟹ Entropy of the system before mixing = 1310.85JK-1
(-) After the hot and cold water have been mixed, we have 2 Kg of water at 500C. The entropy of the
system is now:
323 323
𝑚𝑐𝑝 ln = 2 × 4200 × ln = 1412.72𝐽𝐾 −1
273 273
⟹ Total increase in entropy = 1412.72-1310.85 = 101.87JK-1.

Entropy and the performance of heat Engines: T-S Diagrams

We saw that thermodynamic changes in the state of a substance can be represented by plotting P-V
diagrams. Such changes can also be represented on Temperature – Entropy or (T – S) diagrams.

For the Carnot’s reversible cycle, the isothermal process ab in LHS figure is represented by a straight
line on a T-S diagram in RHS Fig. For the adiabatic process (dQ = 0) such that dS = 0. These processes
are represented by isentropic lines (dS = 0)

Fig.The Carnot Cycle on a P-V diagram and the T-S Diagram of a Carnot cycle
Along the isothermal expansion ab, the gain in entropy of a working substance is as couched below.
Along bc and along da, there is no change in Entropy, dS = 0. Along cd, loss in the entropy of the
working substance is as shown in the second formula
𝑑𝑆 = 𝑆2 − 𝑆1 = 𝑄ℎ ⁄𝑇ℎ
{ ∴ 𝑄ℎ − 𝑄𝑐 = (𝑇ℎ − 𝑇𝑐 )(𝑆2 − 𝑆1 )
𝑑𝑆 = 𝑆2 − 𝑆1 = 𝑄𝑐 ⁄𝑇𝑐
Where 𝑄ℎ − 𝑄𝑐 = external work done in the reversible cycle and (𝑇ℎ − 𝑇𝑐 )(𝑆2 − 𝑆1 ) = Area of
rectangle on T-S diagram. Thus, the net heat absorbed is area adcd = external work done in a
reversible Carnot’s cycle.

The efficiency of a Carnot engine can be obtained using a T-S diagram as follows
𝐸𝑥𝑡𝑒𝑟𝑛𝑎𝑙 𝑤𝑜𝑟𝑘 𝑖𝑛 𝑒𝑎𝑐ℎ 𝑐𝑦𝑐𝑙𝑒 𝑄ℎ − 𝑄𝑐 (𝑇ℎ − 𝑇𝑐 )(𝑆2 − 𝑆1 )
𝜀= = =
𝐻𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑓𝑟𝑜𝑚 𝑠𝑜𝑢𝑟𝑐𝑒 𝑄ℎ 𝑇ℎ (𝑆2 − 𝑆1 )
(𝑇ℎ − 𝑇𝑐 ) 𝑇𝑐
⟹𝜀= =1−
𝑇ℎ 𝑇ℎ
Examples

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1. A fridge working on the reversed Carnot cycle has a power requirement of 5kW. If the maximum
and minimum temperatures in the cycle are 400C and -100C respectively; Draw a T-S diagram and
determine

(i) The coefficient of performance

(ii) The rate of heat extracted from the cold space
(iii) The change in entropy for each of the processes in the cycle, given a refrigerant mass flow rate
of 0.32Kg/s

Soln.: Given W = - 5 kW, Th = 273.15 + 40 = 313.15 K, TC = 273.15 – 10 =263.15K

Fig . Reversed Carnot Cycle

𝑇
2
(a) 𝐶𝑂𝑃 = 𝑇 −𝑇 = 5.263
1 2

𝑄
(b) From 𝐶𝑂𝑃 = 𝑊 ⇒ 𝑄1 = 𝐶𝑂𝑃(𝑊𝑛𝑒𝑡 ) = 26.315𝑘𝑊
𝑛𝑒𝑡

𝑑𝑄
(c) From 2nd law 𝑑𝑠 = 𝑇

Along Process 1 2 and Along Process 3 4 (Along Process 2 3 and 41, it is isentropic TdS = 0)
2
𝑑𝑄 1 1 𝑄1 𝑄1
𝑑𝑆 = ∫ = ∫ 𝑑𝑄 = = = 0.3125 𝑘𝐽⁄𝑘𝑔𝐾
1 𝑇 𝑇1 1 𝑇1 𝑚𝑇1
𝑄2
𝑄2 = 𝑑𝑊 − 𝑄1 = −31.315𝑘𝑊 ∴ 𝑑𝑆 = = −0.3125 𝑘𝐽⁄𝑘𝑔𝐾
{ 𝑚𝑇2

Third Law of Thermodynamics

The third law of thermodynamics is concerned with the limiting behaviour of systems (or Entropy) as
temperatures approach absolute zero. All Statements of the 3rd law of thermodynamics (i.e., Plank’s
statement, Simon’s statement and The Nernst statement) point out that the entropy of a system
tends to zero at absolute zero of temperature.

The Nernst Statement

“The Entropy change in a process associated with a change in the external parameters (e.g., P and
T) tends to zero as temperatures approach absolute zero” i.e., dS  0 as T  0.

This means that as T 0, a strange behaviour is expected in materials i.e., an orderly arrangement
of molecules should occurs in materials. For example, ice is more orderly than water. The reason for
this orderly arrangement can be explained from a microscopic viewpoint (Quantum mechanics)
where is assumed that particles of a system can exist in different quantum states with different
discrete energies. However, as T0, all particles pack in the lowest energy levels (ground state) i.e.,

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assuming they are bosons. Since the ground state in nondegenerate, g = 1, and the number of ways
the particles can be arranged is 1. Hence, there is complete order and S =0.

In real cases however, the decrease in S depends in fact on the number of states per unit energy
range (density of states) with energy rather than just on the occupancy of the ground level as our
simple theorem suggest. In this case, S may not fall to zero as T 0 for both fermions and bosons
(refer to your statistical mechanics for details).

Some of the consequences of the 3rd law

As a consequence of dS  0 as T 0, certain measurable parameters vanish at the absolute zero of
temperature. Typical examples are:
(a) The Heat Capacity (CV) vanishes as T 0
𝑑𝑄 𝜕𝑆 𝜕𝑆
𝑐𝑉 = ( ) = 𝑇( ) = ( )
𝑑𝑇 𝑉 𝜕𝑇 𝑉 𝜕𝑙𝑛𝑇 𝑉

Thus, as T 0, dS  0 but d(lnT)  0 since lnT  . Hence, CV should 0 as T 0. Similar

arguments hold for other heat capacities.
(b) The Thermal expansion Coefficient  vanishes as T 0

The volume cubic expansivity (or isobaric expansivity),  is defined as the fractional increases in the
volume per unit temperature rise i.e., and by suing Maxwell’s relation, we get
1 𝑑𝑉 1 𝜕𝑆
𝛽= ( ) =− ( )
𝑉 𝑑𝑇 𝑃 𝑉 𝜕𝑃 𝑇

Thus, as T 0, dS  0 and   0
(c) Slope of phase boundary in 2nd order phase transition vanishes as T 0

The Slope of phase boundary in 2nd order phase transition is given by:
𝜕𝑃 𝜕𝑆
( )=( )
𝜕𝑇 𝜕𝑉
Thus, as T 0, dS  0 and or the slope  0; this is observed in shown in the figure below.

Fig. The phase boundary of liquid He as T 0

The Unattainability of Absolute Zero

The other statement of 3rd law says that: It is impossible to reduce any system to absolute zero even
on using a finite series of operations. This means that a perfectly efficient heat engine cannot be
created.

RP-IPRC/Kigali, Mechanical Engineering, MEE105: Engineering Thermodynamics Hand-outs 77

Although much progress has been made in recent years to reach extremely very low temperatures
e.g., the super fluid of 3He, the attainability of absolute zero is still elusive

Questions for Discussion

If a supersaturated sugar solution is allowed to evaporate slowly, sugar crystals form in the
container. Hence, sugar molecules go from a disordered form (in solution) to a highly ordered
crystalline form. Does this process violet the second law of thermodynamics? Explain.

Suppose your roommate is “Mr. Clean” and tidies up your messy room after a big party. Because
your roommate is creating more order, does this represent a violation of the second law of
thermodynamics?

“Energy is the mistress of the universe and Entropy is her shadow”. Writing for an audience of
general readers, argue for this statement with examples. Alternatively, argue for the view that
“Entropy is like a decisive hands-on executive instantly determining what will happen, while
energy is like a wretched back-office bookkeeper telling us how little we can afford”.

When we put cards together in a deck or put bricks together to build a house, for example, we
increase the order in the physical world. Does this violet the second law of thermodynamics?
Explain.

The first law of thermodynamics says that you can’t really win, and the second law says you
can’t even break even.” Explain how this statement applies to a particular device or process;
alternatively, argue against the statement.

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