Basis

Thermodynamics &
ME211
Cycles
Mechanical
Unit 1
Engineering
Basic Concepts and Equations
Derived from the First Law

Department of Mechanical Engineering

PNG University of Technology

Semester I, 2023

Dr. Jack B Khallahle MIEAust

 Basis Thermodynamics & Cycles 2023

Contents
Unit Overview .................................................................................................................................. 2

Flow Chart ......................................................................................................................................... 3

1. Basic concepts and definitions ................................................................................. 4

Applied Thermodynamics ................................................................................................................... 4
Heat, Work and the System ................................................................................................................ 4
System ................................................................................................................................................... 5
Units ....................................................................................................................................................... 7
State of Working Fluid ......................................................................................................................... 9
Reversibility ......................................................................................................................................... 10

2. The First Law of Thermodynamics ........................................................................ 11

Working Fluid ...................................................................................................................................... 21
Reversible Non-flow Process ........................................................................................................... 24

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Unit Overview
ME211 Basic THERMODYNAMICS & CYCLES
Hours per week: 6
Objectives:
To introduce students to the subject of Thermodynamics and in particular to the First Law of
Thermodynamics, and to provide techniques necessary for analysis and design in later years. On
completion of the subject, students should be able to solve problems, which require them to apply:
1. Basic equations derived from the First Law;
2. Gas laws, and vapour tables and diagrams;
3. Gas mixture laws;
4. Basic principles of combustion;
5. Thermodynamic principles of heat engines and refrigeration systems.

Syllabus:
Basic concepts and definitions: intensive and extensive properties, system, reversibility, work, heat,
thermal equilibrium and Zeroth law of thermodynamics.

First law of thermodynamics: conservation of energy, non-flow and steady flow energy equations.

Working fluids: liquid, vapour, vapour tables and diagrams, perfect gas, gas laws, gas mixture laws.
Reversible processes: non-flow and steady flow.
*Fuels and combustion: basic chemistry, common fuels and their properties, combustion equations,
exhaust gas analysis.
Thermal systems: first law treatment of turbines, compressors, engines, and refrigeration systems.
Textbook:
Eastop, T.D. & McConkey, A., Applied Thermodynamics for Engineering Technologists, 5th Ed.,
Prentice Hall, 1993.
Reference:
Rogers, G.F.C., & Mayhew, Y.R., Thermodynamic and Transport Properties, 5th Ed., (Basil Blackwell,
1995)
Assessment:
Continuous assessment - 60%
Written Examination - 40% (1 x 2 hours)
Lecturer:
Dr. Jack B Khallahle MIEAust

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Flow Chart

Topic Key Issues Examples/Exercises/Assignments

Unit 1
Basic concepts and Heat
definitions Work

Properties of pure Temperature

substances, Units and Pressure
First Law of Specific volume
Thermodynamics Internal energy
Enthalpy
Entropy
State of Working fluid
Reversibility

Unit 2
Thermal System First Law treatment of
Heat Engines
Compressors
Refrigeration systems
Psychrometry and
cooling towers

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1. Basic concepts and definitions

Applied Thermodynamics
Applied thermodynamic is the science of the relationship between heat, work, and the
properties of systems. It is concerned with the means necessary to convert heat energy
from available sources such as chemical fuels or nuclear piles into mechanical work. A
HEAT ENGINE is the name given to a system which by operating in a cyclic manner
produces network from a supply of heat.

The laws of Thermodynamics are natural hypotheses based on observations of the world
in which we live. It is observed that heat and work are two mutually convertible forms of
energy, and this is the basis of the First Law of Thermodynamics. It is also observed that
heat never flows unaided from an object at a low temperature to one at a high
temperature, in the same way that a river never flows unaided uphill. This observation is
the basis of the Second Law of Thermodynamics, which can be used to show that a heat
engine cannot convert all the heat supplied to it into mechanical work but must always
reject some heat at a lower temperature.

Heat, Work and the System

Heat is a form of energy which is transferred from one body to another body at a lower
temperature as a result of temperature difference between the bodies.

It is related to the molecular motion or vibration. A molecule is the smallest particle in

which any substance can be broken down and still retain its chemical identity. As a
substance is warmed, molecules move more rapidly. As a substance is cooled, they slow
down. If all heat is removed from a substance, all molecule motion stops. In other words,
if a substance is warmed, heat is added, if cooled, heat is removed.

Heat transfer
Heat may be transferred from one body to another by one of the following methods;
 Radiation – The heat transfer in the form of a wave motion similar to light waves in
which the energy is transmitted from one body to another without the need for
intervening matter e.g., electric heater.
 Conduction –The flow of heat among parts of a substance. The flow can also be
from one substance to another substance in direct contact.

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 Convection – The moving of heat from one place to another by way of fluid or air
Some systems of heat transfer use a combination of these three methods for instance
Burner (conduction/water/convection).

Temperature
Temperature measures the heat intensity or heat level of a substance. Temperature
alone does not give the amount of heat in a substance. It indicates the degree of warmth
or how hot or cold a substance or body is. In other words, the kinetic energy of vibration
of the molecules of a substance is apparent to the touch and is experienced as a degree
of hotness which we call temperature.

Again, the molecules of a body at high temperatures are further are further apart than
when the body is at a lower temperature. Thus, a rise in temperature is, with certain
exceptions, accompanied by an expansion.

“Heat can never be contained in a body or possessed by a body”

System
A system may be defined as a collection of matter within prescribed and identifiable
boundaries (fig. 1.2). The boundaries are not necessarily inflexible; for instance, are the
fluid in the cylinder of a reciprocating engine during the expansion stroke may be defined
as a system whose boundaries are the cylinder walls and the piston crown. As the piston
moves so do the boundaries move (fig. 1.3).

Surroundings
Boundary

System

Fig. 1.2

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Surroundings
Boundary

Pis
to
System n

Boundary Boundary

Fig. 1.3

This type of system is known as a closed system. An open system is the one in which
there is a transfer of mass across the boundaries; for instance, the fluid in a turbine at
any instant may be defined as an open system whose boundaries are fixed.

The pressure of a system is the force exerted by the system on unit area of its
boundaries.

Surroundings

System
Gauge pressure

Fig. 1.5a

Units of pressure are, for example, N/m or bar; the symbol 𝑝 will be used for pressure.
Pressure as defined here is called absolute pressure. A gauge for measuring pressure
(e.g., as shown in fig. 1.5a records the pressure above atmospheric. This is called gauge
pressure, i.e., absolute pressure equals gauge pressure plus atmospheric pressure;
Absolute pressure gauge pressure atmospheric pressure
When the pressure of a system is below atmospheric, it is called vacuum pressure.

The gauges shown in fig. 1.5a and 1.5c measure gauge pressure in mm of a liquid of

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known specific gravity, and are called manometers.

The specific volume of a system is the volume occupied by unit mass of a system. The
symbol used is 𝑣 and the units are, for example, m ⁄kg. The symbol 𝑉 will be used for
volume, (Note that the specific volume is the reciprocal of density).

Surroundings

System
Vacuum pressure

Fig. 1.5c

Work is defined as the product of a force and the distance moved in the direction of the
force. When a boundary of a closed system moves in the direction of the force acting on
it, then the system does work on its surroundings. The units of work are, for example,
Nm. If work is done on unit mass of a fluid, then the work done per kg of fluid has units of
Nm/kg.

Work is observed to be energy in transition. It is never contained in a body or possessed

by a body.

Heat and Work are both transitory energies and must not be confused with the intrinsic
energy possessed by a system. For example, when a gas contained in a well-lagged
cylinder (fig. 1.6a) is compressed by moving the piston to the left, the pressure and
temperature of the gas are observed to increase, and hence the intrinsic energy of the
gas increases. Since the cylinder is well-lagged, no heat can flow into or out of the gas.
The increase in intrinsic energy of the gas has therefore been caused by the work done
by the piston on the gas.

Units
SI units will be used throughout this course. The International System of Units was
adopted by the General Conference of Weights and Measures in 1960 and subsequently
endorsed by the International Organisation for Standardisation.

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In SI units six physical quantities are arbitrarily are assigned unit value and hence all
other physical quantities are derived from these. The six quantities chosen and their
units are as follows:
Length (metre, m); mass (kilogram, kg); time (second, s); electric current (ampere, A);
thermodynamic temperature (degree Kelvin, K) etc.
Then, for example, velocity = length/time, has units of m/s; acceleration = velocity/time
squared has units of m/s²; volume = length x length x length, has units of m³; specific
volume = volume/mass has units m³/kg.

Force, Energy and Power

Newton’s second law may be written as force ∝ mass x acceleration, for a body of
constant mass;
i.e. 𝐹 𝑚𝑎
The SI unit of force is therefore kg m/s². This composite unit is called the Newton, N i.e.,
1 N is the force required to give a mass of 1 kg an acceleration of 1 m/s².

It follows that the SI unit of work (= force x distance) is the newton metre, Nm. As stated,
earlier heat and work are both forms of energy, and hence both can have the units of kg
m/s² or Nm. A general unit for energy is introduced by giving the Newton meter the name
Joule, J;
i.e. 1 Joule, J = 1 Newton x I metre
or 1 J = 1 Nm
The use of additional names for composite units is extended further by introducing the
Watt, W as the unit of power;
i.e. 1 Watt, W = 1 J/s = 1 Nm/s
Note also that: 1 Watt, W = 1 ampere, A x 1 volt, V

Pressure
The unit of pressure (force per unit area), is N/m² and this unit is sometimes called the
Pascal, Pa. For most cases occurring in Thermodynamics the pressure expressed in
Pascals would be a very small number; a new unit is defined as follows;
1 bar 10 N⁄m 10 Pa
Standard atmospheric pressure is exactly 1.01325 bar, it is convenient to express a
pressure as a head of a liquid;
i.e., Standard atmospheric pressure = 1.013 25 bar = 0.76 m H .

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Temperature
In thermodynamic an absolute Celsius scale is used by adding 273 to all temperatures
on the Celsius scale; this scale is called the Kelvin scale. The unit of temperature is the
degree Kelvin and is given the symbol ‘K’ (e.g., 20ºC = 293 K).

Multiples and sub-multiples

Multiples and sub-multiples of the basic units are formed by means of prefixes, and the
ones most commonly used are shown in the following table:
Multiplying factor Prefix Symbol
One million, 10 mega M
One thousand, 10 kilo k
One thousandth, 10 milli m
One millionth, 10 micro 𝜇
For example, power can be usually be satisfactorily expressed in either megawatts, MW,
or kilowatts, kW, or watts, W.

State of Working Fluid

In all problems of Applied Thermodynamics, we are concern with energy transfers to or
from a system. In practise the matter contained within the boundaries of a system can be
liquid, vapour or gas and is known as the working fluid. At any instant the state of the
working fluid may be defined by certain characteristic called its properties.

The thermodynamic properties introduced in this course are pressure, temperature,

specific volume, internal energy, enthalpy and entropy. For pure working fluid, only two
independent properties are necessary to define completely the state of the fluid and
represent the state of a system by a point situated on a diagram of properties.

𝑷 𝑷

1
1
 
2

2
 
Fig. 1.9a Fig. 1.9b

𝑽 𝑻

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𝑻
1

 

𝑽
Fig. 1.9c
For example, a cylinder containing a certain fluid at pressure 𝑝 and specific volume 𝑣 is
at state 1, defined by point 1 on a diagram of 𝑝 against 𝑣 (fig. 1.9a). Since the state is
defined, then the temperature of the fluid,𝑇, is fixed and the state point can be located on
a diagram of 𝑝 against 𝑇 and 𝑇 against 𝑣 (fig. 1.9b and c). At any other instant the piston
may be moved in the cylinder such that the pressure and specific volume are changed to
𝑝 and𝑣 . State 2 can then be marked on the diagrams. Diagrams of properties are used
continually in Applied Thermodynamics to plot state changes.

Reversibility
We have learnt and shown that the state of the fluid can be represented by a point
located on a diagram using two properties as coordinates. When a system changes state
in such a way that at any instant during the process the state point can be located on the
diagram, then the process is said to be reversible. The fluid undergoing the process
passes through a continuous series of equilibrium states. A reversible process between
two states can therefore be drawn as a line on any diagram of properties (fig. 1.10).

1


2

𝑽
Fig. 1.10

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A more rigorous definition of reversibility is: When a fluid undergoes a reversible
process, both the fluid and its surroundings can always be restored to their original state.
The criteria of reversibility are as follows:
a) The process must be frictionless
b) The difference in pressure between the fluid and its surroundings during the
process must be infinitely small
c) The difference in temperature between the fluid and its surroundings during the
process must be infinitely small

2. The First Law of Thermodynamics

Conservation of energy
The concept of energy and the hypothesis that it can be neither created nor destroyed
developed by scientists in the early part of the nineteenth century, and became known as
the Principle of the Conservation of Energy. The First Law of Thermodynamics is merely
one statement of this general principle with particular reference to heat energy and
mechanical energy (i.e., work). The First Law of Thermodynamics can be stated as
follows:
“When a system undergoes a thermodynamic cycle then the net heat supplied to the
system from its surroundings is equal to the net work done by the system on its
surroundings”. In symbols;
∑ 𝑑𝑄 ∑ 𝑑𝑊----------------------------------(2.1)
Where ∑ represents the sum for a complete cycle.

Example 1;

In a certain steam plant, the turbine develops 1000 kW. The heat supplied to the steam
in the boiler is 2800 KJ/kg, the heat rejected by the system to cooling water in the
condenser is 2100 KJ/kg and the feed pump work required to pump the condensate back
into the boiler is 5 kW. Calculate the steam flow round the cycle in kg/s. The cycle is
shown diagrammatically in fig. 2.1. A boundary is shown which encompasses the entire
plant.

∑ 𝑑𝑄 2800 2100 700 kJ/kg

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Boundary

Q W
Boiler Turbine

Q
Condenser
Feed
Pump

W
Boundary

Fig. 2.1

Let the steam flow be 𝑚 kg/s;

∴ ∑ 𝑑𝑄 700𝑚 kJ/s

∑ 𝑑𝑊 1000 5 995 𝑘𝑊 995 kJ/s

Then, ∑ 𝑑𝑄 ∑ 𝑑𝑊

i.e., 700 𝑥 𝑚 995 ∴m 1.421 kg/s

i.e., Steam flow required = 1.421 kg/s.

 The non-flow equation

We now know that when a system possessing a certain intrinsic energy is
made to undergo a cycle by heat and work transfer, then the net heat
supplied is equal to the network output for a complete cycle where intrinsic
energy values are equal at both at initial and final state.

Now consider a process in which the intrinsic energy of the system is finally
greater than the initial intrinsic energy. The difference between the net heat
supplied and the network output has increased the intrinsic energy of the
system;

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i.e., Gain in intrinsic energy Net heat supplied – net work output

When the net effect is to transfer energy from the system, then there will be a
loss in the intrinsic energy of the system.

When a fluid is not in motion then its intrinsic energy is known as the internal
energy of the fluid and given the symbol 𝑢. The internal energy of a fluid
depends on its pressure and temperature, and itself a property. The internal
energy of mass, 𝑚, of a fluid is written as 𝑈, i.e., 𝑚𝑢 𝑈 in KJ.

Since internal energy is a property then a gain in internal energy in changing

from state 1 to state 2 is written as 𝑈 𝑈.

Also, gain in internal energy net heat supplied – net work output,

i.e. 𝑈 𝑈 ∑ 𝑑𝑄 ∑ 𝑑𝑊

This equation is true for a process or series of process between state 1 and
state 2 provided there is no flow of fluid into or out of the system. In any non-
flow process, there will be either heat supplied or heat rejected, but not both.
Similarly, there will be either work output or work input, but not both.

Heat supplied to the system is denoted positive

Work done by the system as positive

We have;

𝑈 𝑈 𝑄 𝑊 for a non-flow process

i.e. 𝑄 𝑈 𝑈 𝑊

or for 1 kg, 𝑄 𝑢 𝑢 𝑊 ---------------------- (2.2)

This equation is known as the non-flow energy equation.

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In differential form;
𝑑𝑄 𝑑𝑢 𝑑𝑊 -------------------------- (2.3)
Example 1
In the compression stroke of an internal-combustion engine the heat rejected
to the cooling water is 45 KJ/kg and the work input is 90 KJ/kg.

Calculate the change in internal energy of the working fluid stating whether it
is a gain or a loss.

𝑄 45kJ/kg

( ve sign since heat is rejected),

𝑊 90 kJ/kg

( ve sign since work is a work input to the system), Using equation 2.2,

𝑄 𝑢 𝑢 𝑊
∴ 45 𝑢 𝑢 90
𝑢 𝑢 90 45 45 kJ/kg

∴ Gain in internal energy 45 kJ/kg

Example 2
In the cylinder of an air motor the compressed air has an internal energy of
420 kJ/kg at the beginning of the expansion and an internal energy of 200
kJ/kg after expansion.

Calculate the heat flow to or from the cylinder when work done by the air
during the expansion is 100 kJ/kg.

From equation 2.2;

𝑄 𝑢 𝑢 𝑊

∴ 𝑄 200 420 100 220 100 120 kJ/kg

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i.e., Heat rejects by the air 120 kJ/kg

The equations;

∑ 𝑑𝑄 ∑ 𝑑𝑊 -----------------------------------------------------(2.1)

𝑄 𝑢 𝑢 𝑊 --------------------------------------------- (2.2)
𝑑𝑄 𝑑𝑢 𝑑𝑊 -------------------------------------------------- (2.3)

Are energy equations being true whether the process is reversible or not.

For a reversible non-flow process, we have from equation 1.2;

𝑊 𝑝 𝑑𝑣

or for small quantities, 𝑑𝑊 𝑝𝑑𝑣

Hence for any reversible non-flow process, substituting in equation 2.3

𝑑𝑊 𝑑𝑢 𝑝𝑑𝑣 ----------------------------- (2.4)

Or substituting in equation 2.2;

𝑄 𝑢 𝑢 𝑝𝑑𝑣 --------------------------(2.5)

Equations 2.4 and 2.5 can only be used for ideal reversible non-flow
processes.

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 The flow equation

𝒛𝟏
𝒛𝟐

Datum

In non-flow process, the internal energy of a fluid was said to be the intrinsic
energy of the fluid due to its thermodynamic properties.

In most practical problems the rate at which the fluid flows through a machine
or piece of apparatus is constant. This type of flow is called steady flow.

Consider now the energy entering and leaving the system. The energy
entering the system the system consists of the energy of the flowing fluid at

inlet as 𝑢 𝑍 𝑔 , the energy term 𝑝 𝑣 , and the heat supplied 𝑄. The

energy leaving the system consists of the energy of the flowing fluid at the

outlet section 𝑢 𝑍 𝑔 , the energy term𝑝 𝑣 , and the work done by the

fluid 𝑊. Since there is a steady flow of fluid into and out of the system, and
there are steady flows of heat and work, then the energy entering must
exactly equal the energy leaving.

𝑢 𝑍 𝑔 𝑝 𝑝 𝑄 𝑢 𝑍 𝑔 𝑝 𝑣 𝑊 ---------------- (2.6)

In nearly all problems in applied thermodynamic, changes in height are

negligible and the potential energy terms can be omitted from the equation.
The term𝑢 and 𝑝𝑣 occur on both sides of equation and always will do in flow

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process, since a fluid always possesses a certain internal energy, and the
term 𝑝𝑣 always occurs at inlet and outlet as seen in the above proof. The sum
of internal energy and 𝑝𝑣 term is given the symbol ℎ, and is called enthalpy,

i.e. Enthalpy, ℎ 𝑢 𝑝𝑣 ----------------------------------- (2.7)

The enthalpy of a fluid is a property of the fluid, since it consists of the sum of
a property and the product of the two properties. Since enthalpy is a property
like internal energy, pressure, specific volume and temperature, it can be
introduced into any problem whether the process is a flow process or a non-
flow process.

The enthalpy of mass, 𝑚, of a fluid can be written as 𝐻 (i.e.𝑚ℎ 𝐻). The

units of ℎ, are the same as those of internal energy.

Substituting equation 2.7 in equation 2.6;

ℎ 𝑄 ℎ 𝑊 ------------------------------------- (2.8)

Equation 2.8 is known as steady-flow energy equation.

In steady flow the rate of mass flow of fluid at any section is the same as at
any other section. Consider any section of cross-sectional area 𝐴, where the
fluid velocity is 𝐶, then the rate of volume flow past the section is 𝐶𝐴. Also,
since mass flow is volume flow divided by specific volume;

Mass flow rate, 𝑚 ---------------------------------------- (2.9)

(where 𝑣 specific volume at the section).

This equation (2.9) is known as the continuity of mass equation.

𝐶𝐴 𝐶 𝐴
𝑚
𝑣 𝑣

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Example 3
In the turbine of a gas turbine unit the gases flow through the turbine at 17
kg/s and the power developed by the turbine is14000 kW. The enthalpies of
the gases at inlet and outlet are 1200 kJ/kg and 360 kJ/kg respectively, and
the velocities of the gases at inlet and outlet are 60 m/s and 150 m/s
respectively. Calculate the rate at which heat is rejected from the turbine. Find
also the area of the inlet pipe given that the specific volume of the gases at
inlet is 0.5 m³/kg.

Boundary
Gases out

Gases in

Gas Turbine W

Q
Boundary

A diagrammatic representation of the turbine is shown above from equation

2.8, we have;

𝐶 𝐶
ℎ 𝑄 ℎ 𝑊
2 2

Kinetic energy at inlet m²/s² 1800 NM/kg 1.8 kJ/kg

Kinetic energy at outlet 11250 NM/kg 11.25 kJ/kg.

𝑊 kJ/kg 823.5 kJ/kg

Substituting in equation 2.8;

1200 1.8 𝑄 360 11.25 823.5

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∴ 𝑄 7.02 kJ/kg

i.e. Heat rejected + 7.02 kJ/kg 7.02 x 17 kJ/s 119.3 kW.

To find inlet area, use equation 2.9;

i.e. 𝑚 ∴𝐴

.
∴ 𝐼𝑛𝑙𝑒𝑡 𝑎𝑟𝑒𝑎, 𝐴 0.142 m²

Q1/A1 Air flows steadily at the rate of 0.4 kg/s through an air compressor, entering at 6 m/s
with a pressure of 1 bar and specific volume of 0.85 m³/kg, and leaving at 4.5 m/s with a
pressure of 6.9 bar and a specific volume of 0.16 m³/kg. The internal energy of the air
leaving is 88kJ/kg greater than that of the air entering. Cooling water in a jacket surrounding
the cylinder absorbs heat from the air at the rate of 59 kJ/s. Calculate the power required to
drive the compressor and the inlet and outlet pipe cross-sectional areas.

Note: write the flow equation as in equation (2.6) omitting the Z terms.

i.e. 𝑢 𝑝 𝑝 𝑄 𝑢 𝑝 𝑣 𝑊

A diagrammatic representation of the compressor is shown in drawing below;

J/kg 18 J/kg

. .
J/kg 10.1 J/kg

𝑝 𝑣 1 10 0.85 85 000 J/kg

𝑝 𝑣 6.9 10 0.16 110 400 J/kg

𝑢 𝑢 88 kJ/kg

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Air 1 Air
2

Water

Q
Air
Compressor
Water W

Boundary

Heat rejected 59 kJ/s 147.5 kJ/kg

.

Now 𝑊 𝑢 𝑢 𝑝 𝑣 𝑝 𝑣 𝑄

i.e. 𝑊 88 85 110.4 0.018 0.0101 147.5 260.9 kJ/kg

i.e. Work input required 260.9kJ/kg
260.9 0.4 kJ/s
i.e. Work input required 260.9 0.4 kW

From equation;
𝐶𝐴
𝑚
𝑣
. .
i.e. 𝐴 𝑚² 0.057 m²

i.e. Inlet pipe cross-sectional area 0.057 m²

. .
Similarly, 𝐴 𝑚² 0.014 m²
.

i.e Inlet pipe cross-sectional area 0.014 m²

Note: Steady flow energy equation has been used despite the fact that compression is a
non- flow process and a closed system. The cycles repeated many times in a minute…and
average effect is flow through a machine…

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Working Fluid
Liquid, vapour and gas
NOTE: handouts given….
The use of vapour tables
The Perfect Gas
The characteristic equation of state
At temperatures that are considerably in excess of the critical temperature of a fluid,
and also at very low pressure, the vapour of fluid tends to obey the equation;

𝑝𝑣
𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑅
𝑇

No gases in practice obey this law rigidly, but many gases tend towards it. An
imaginary ideal gas which obeys the law is called a perfect gas, and the equation,

𝑅 is called the characteristic equation of state of a perfect gas. The constant, 𝑅, is

called the gas constant. The units of 𝑅 are Nm/kg K or kJ/kg K. Each perfect gas has a
different gas constant.

The characteristic equation is usually written as;

𝑝𝑣 𝑅𝑇
or for 𝑚 kg, occupying 𝑉 m³;
𝑝𝑉 𝑚𝑅𝑇

Another form of the characteristic equation can be derived using the kilogram-mole as
unit. The kilogram-mole is defined as a quantity of a gas equivalent to𝑀 kg of gas,
where 𝑀 is the molecular weight of the gas (e.g. since the molecular weight of oxygen
is 32, then 1 kg mole of oxygen is equivalent to 32 kg of oxygen).

From the definition of the kilogram-mole, for 𝑚 kg of a gas we have;

𝑚 𝑛𝑀
(where 𝑛 is the number of molecules),

Substituting for 𝑚 in the equation above gives;

𝑝𝑉
𝑝𝑉 𝑛𝑀𝑅𝑇 𝑜𝑟 𝑀𝑅
𝑛𝑇

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 Basis Thermodynamics & Cycles 2023
Now Avogadro’s hypothesis states that the volume of 1 mole of any gas is the same as
the volume of 1 mole of any other gas, when the gases are at the same temperature
and pressure. Therefore 𝑉 ⁄𝑛 is the same for all gases at the same vale of 𝑝 and 𝑇.
That is the quantity 𝑝𝑉 ⁄𝑛𝑇 is a constant for all gases. This constant is called the
universal gas constant, and is given the symbols, 𝑅 ;

i.e. 𝑝𝑉 𝑅 𝑜𝑟 𝑝𝑉 𝑛𝑅 𝑇

or since 𝑀𝑅 𝑅 then, 𝑅

Experiment has shown that the volume of 1 mole of any perfect gas at 1 bar and 0ºC is
approximately 22.71 m³. Therefore, from the equation;

.
𝑅 8314.3 Nm/mole K
.

From equation 𝑅 𝑅 ⁄𝑀 the gas constant for any gas can be found when the
molecular weight is known, e.g. for oxygen of molecular wright 32, the gas constant is;
𝑅 259.8 Nm/kg K

Example 1
A vessel of volume 0.2 m³ contains nitrogen at 1.013 bar and 15ºC. If 0.2 kg of nitrogen
is now pumped into the vessel, calculate the new pressure when the vessel has
returned to its initial temperature. The molecular weight of nitrogen is 28, and it may be
assumed to be a perfect gas.

From 𝑅 𝑅 ⁄𝑀;

Gas constant, 𝑅 296.9 Nm/kg K

From 𝑝𝑉 𝑚𝑅𝑇;
𝑝 𝑉 𝑚 𝑅𝑇
. .
∴𝑅 0.237 kg
.

(where 𝑇 15 273 288 𝐾 .

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 Basis Thermodynamics & Cycles 2023
0.2 kg of nitrogen are added, hence 𝑚 0.2 0.237 0.437 kg. Then from equation
𝑝𝑉 𝑚𝑅𝑇 for the final conditions;

𝑝 𝑉 𝑚 𝑅𝑇

But 𝑉 𝑉 and 𝑇 𝑇;
𝑚 𝑅𝑇 0.437 296.9 288
∴ 𝑝
𝑉 0.2

. .
i.e. 𝑝 1.87 bar
.

Specific heats
The specific heat of a solid or liquid is usually defined as the heat required to raise unit
mass through one degree temperature rise. For small quantities, we have;

𝑑𝑄 𝑚𝑐𝑑𝑇

Where, m = mass, dT= increase in temperature, c = specific heat.

For a gas;
𝑐 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
𝑐 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

For a perfect gas the value of 𝑐 and 𝑐 are constant for any one gas at all pressures
and temperatures. Hence;

Heat flow in reversible constant pressure process 𝑚𝑐 𝑇 𝑇

Heat flow in reversible constant volume process 𝑚𝑐 𝑇 𝑇

For a real gas, 𝑐 and 𝑐 vary with temperature, but for most practical purposes a
suitable average value may be used.

Joule’s Law
Joule’s law states that the internal energy of a perfect gas is a function of the absolute
temperature, i.e., 𝑢 𝑓 𝑇 . To evaluate this function let 1 kg of a perfect gas be heated

Basic Concepts and Equations Derived from the First Law 23

 Basis Thermodynamics & Cycles 2023
at constant volume. From non-flow energy;

𝑑𝑄 𝑑𝑢 𝑑𝑊

Since volume remains constant then no work is done, i.e., 𝑑𝑊 0.

𝑑𝑄 𝑑𝑢

At constant volume for a perfect gas for 1 kg;

𝑑𝑄 𝑐 𝑑𝑇

Therefore, . 𝑑𝑄 𝑑𝑢 𝑐 𝑑𝑇, and integrating;

𝑢 𝑐 𝑇 𝐾,
where 𝐾 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

For a perfect gas it can be assumed that. 𝑢 0 when 𝑇 0, hence 𝐾 0;

i.e. Internal energy, 𝑢 𝑐 𝑇 for a perfect gas,

or for mass, 𝑚, of a perfect gas; Internal energy, 𝑈 𝑚𝑐 𝑇

Reversible Non-flow Process

Constant volume process

In a constant volume process the working substance is contained in a rigid vessel,
hence the boundaries of the system are immovable and no work can be done on or by
the system. It will be assumed that ‘constant volume’ implies zero work unless stated
otherwise.
𝑄 𝑢 𝑢 𝑊
Since no work is done, we therefore have;
𝑄 𝑢 𝑢
All the heat supplied in a constant volume process goes to increasing the in internal
energy.

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 Basis Thermodynamics & Cycles 2023

𝑷 𝑷

2
𝑃 2 𝑃

𝑃 𝑃
1 1

Fig.4.1a 𝑽 Fig.4.1b 𝑽
𝑣 𝑣 𝑣 𝑣
A constant volume process for a vapour is shown on a p-v diagram in fig.4.1a. The
initial and final states have been chosen to be in the wet region and superheat region
respectively. In fig.4.1b a constant volume process is shown on a p-v diagram for a
perfect gas. For a perfect gas we have from equation 3.13;
𝑄 𝑚𝑐 𝑇 𝑇

Constant Pressure Process

It can be seen from fig.4.1a and 4.1b that when the boundary of the system is inflexible
as in a constant volume process, then the pressure rises when heat is supplied. Hence
for a constant pressure process the boundary must move against an external
resistance as heat is supplied; for instance a fluid in a cylinder behind a piston can be
made to undergo a constant pressure process. Since the piston is pushed through a
certain distance by the force exerted by the fluid, then work is done by the fluid on its
surroundings.
From equation 1.2;

𝑊 𝑝𝑑 for any reversible process

𝑷 𝑷

1 2 𝑃 𝑃 1 2
𝑃 𝑃

Therefore, since 𝑝 is constant,

𝑣 𝑣 𝑽 𝑣 𝑣 𝑽

𝑊 𝑝 𝑑 𝑝 𝑣 𝑣

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 Basis Thermodynamics & Cycles 2023
From non-flow energy equation;
𝑄 𝑢 𝑢 𝑊
Hence for reversible constant pressure process;
𝑄 𝑢 𝑢 𝑝 𝑣 𝑣 𝑢 𝑝𝑣 𝑢 𝑝𝑣
Now from equation 2.7, enthalpy, ℎ 𝑢 𝑝𝑣, hence;
𝑄 ℎ ℎ
Or for mass, 𝑚, of a fluid;
𝑄 𝐻 𝐻
A constant pressure process for a vapour is shown on a 𝑝-𝑣 diagram in fig.4.2a. The
initial and final states have been chosen to be in the wet region and the superheat
region respectively. In fig. 4.2b a constant pressure process for a perfect gas is shown
on a 𝑝-𝑣 diagram. For a perfect gas we have from equation 3.12;
𝑄 𝑚𝑐 𝑇 𝑇

Note that in figs.4.2a and 4.2b the shaded areas represent the work done by the fluid,
𝑝 𝑣 𝑣 .

Example 4.1
0.05 kg of a certain fluid is heated at a constant pressure of 2 bar until the volume
occupied is 0.0658 m .

Calculate the heat supplied and the work done,

a) When the fluid is steam, initially dry saturated.
b) When the fluid is dry saturated at 2 bar, hence,

a) Initially the steam is dry saturated at 2 bar, hence,

ℎ ℎ at 2 bar = 2707 kJ/kg

Finally the steam is at 2 bar and the specific volume is given by;

0.0658
𝑣 1.316 m /kg
0.05

Hence the steam is superheated finally. From superheat tables at 2 bar and 1.316
m /kg the temperature of the steam is 300ºC, and the enthalpy is ℎ 3072 kJ/kg.

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 Basis Thermodynamics & Cycles 2023
Then from equation 4.4;

𝑄 𝐻 𝐻 𝑚 ℎ ℎ 0.05 3072 2707

i.e. Heat supplied = 0.05 x 365 = 18.25 kJ

𝑷 N/m

1 2
2 x 10

fig.4.3
0.8856 1.316 𝑽 m /kg

The process is shown on the 𝑝-𝑣 diagram in fig.4.3. the work done is given by the
shaded area; i.e.,𝑊 𝑝 𝑣 𝑣 Nm/kg.

Now 𝑣 𝑣 at 2 bar 0.8856 , and 𝑣 1.316 m /kg

∴𝑊 2𝑥10 1.316 0.8856 2𝑥10 𝑥0.4304 𝑁𝑚/𝑘𝑔

i.e.
Work done by the total mass present 0.05 𝑥 2 𝑥10 𝑥 0.4304 𝑥 10 𝟒. 𝟑𝟎𝟒 kJ
b) Using equation 3.6;
𝑝 𝑉 2 𝑥 10 𝑥 0.0658
𝑇 𝟗𝟏𝟕 𝐊
𝑚𝑅 0.05 𝑥 0.287 𝑥 10

For a perfect gas undergoing a constant pressure process we have, from equation 3.12;

𝑄 𝑚𝑐 𝑇 𝑇

i.e. Heat supplied 0.05 𝑥 1.005 917 403

(where 𝑇 130 273 403 K)

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 Basis Thermodynamics & Cycles 2023
i.e. Heat supplied 0.05 𝑥 1.005 𝑥 514 25.83 kJ

The process is shown on the 𝑝-𝑣 diagram in fig.4.4. The work done is given by the shaded
area, i.e.,𝑊 𝑝 𝑣 𝑣 Nm/kg. From equation 3.5, 𝑝𝑣 𝑅𝑇;

∴ Work done 𝑅 𝑇 𝑇 0.287 917 403 kJ/kg

i.e. Work done by the mass of gas present 0.05 𝑥 0.287 𝑥 514 𝟕. 𝟑𝟖 kJ

𝑷 N/m

2 𝑥 10 1 2

Fig. 4.4
𝑽 m /kg

Constant Temperature or Isothermal Process

A process at constant temperature is called an isothermal process. When a fluid in a
cylinder behind a piston expands from a high pressure to a low pressure there is a
tendency for the temperature to fall. In an isothermal expansion heat must be added
continuously in order to keep the temperature at the initial value. Similarly in an
isothermal compression heat must be removed from the fluid continuously during the
process. An isothermal process for a vapour is shown on a 𝑝-𝑣 diagram in fig. 4.5. The
initial and final states have been chosen in the wet region and superheat region
respectively. From state 1 to state A the pressure remains at 𝑝 , since in the wet region
the pressure and temperature are the corresponding saturation values. It can be seen
therefore that an isothermal process for wet steam is also at constant pressure and
equations 4.3 and 4.4 can be used (e.g., heat supplied from state 1 to state A per kg of
steam ℎ ℎ ). In the superheat region the pressure falls to 𝑝 as shown in fig. 4.4
and the procedure is not so simple. When states 1 and 2 a fixed then the internal
energies 𝑢 and 𝑢 may be obtained from tables. The work done is given by the
shaded area in fig. 4.5. This can only be evaluated by plotting the process and

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 Basis Thermodynamics & Cycles 2023
measuring the area graphically. However, when the property entropy is introduced
later, a convenient way of evaluating the heat supplied will be shown. When the heat
flow is calculated the work done can then be obtained using the non- flow energy
equation 2.2;

𝑄 𝑢 𝑢 𝑊

𝑇 𝑇
𝑷

𝑃 1 𝐴

𝑃 2
𝑇 𝑇
Fig. 4.5
𝑽

Basic Concepts and Equations Derived from the First Law 29