1.2.
5 Equilibrium
When there is no energy transfer between different parts of the
mass of a fluid in a system, and if the mass of the fluid is isolated
from its surroundings e.g. if the thermodynamic properties
are constant, then the fluid is said to be in equilibrium.
•Thermal equilibrium: The system and its surroundings are at the
same temperature and there is no heat transfer across the boundary.
•Mechanical equilibrium: There is uniform pressure or balance of
forces between the system and its surroundings
•Chemical equilibrium: There is uniform chemical composition
between the system and its surroundings.
1.2.6 Process, state and property
•A process is the transformation of a system from one state to
another.
•The state of a substance completely describes how the substance
exists. It comprises the temperature, pressure, density and other
properties and by knowing these properties, the state of the
substance can be determined.
•The state of a system is the totality of its properties e.g. pressure,
temperature, density, specific energy etc.
•A property is an observable or calculable characteristic of a
system e.g. density, pressure, temperature, which depends not on
how the system changes state, but only on the final system state.
There are intensive properties and extensive properties.
–An extensive property depends on the size or extent of the system e.g. mass and volume.
–An intensive property is independent of the size of the system e.g. temperature.
An extensive property per unit mass e.g. specific volume (in m³/kg) is an intensive
property.
1.2.7 Pressure
Pressure is the normal component of force per unit area exerted by a system on its
boundary.
1.2.8 Temperature
Temperature is a measure of coldness or hotness of a body and is expressed in either
Fahrenheit (F) or Celsius (C).
1.2.9 Specific volume
Specific volume of a substance is the inverse of the density of that substance. Hence,
specific volume (v = V/m) is the volume per unit mass of a substance and is expressed in
units of ft³/lbm or m³/kg.
1.2.10 Cycle and path
If the initial and final states of a process are the same, then this process is a cycle. A cycle
implies a path - this is a succession of system states. Consider the cycle in figure 1: The
working fluid at state 1 is water. Mechanical work is put into the water in the pump and the
water is conveyed into the steam generator (or boiler) in state 2. In the boiler, the water is
vapourized into high-energy steam in state 3. This steam expands in the turbine where its
thermal energy is converted into mechanical work, and comes out in state 4 as low-energy
steam. This steam is then condensed in the condenser to convert it back into water in state
1.
1.2.11 Work
The work done on or by a system, W, may be expressed as the product of force and the
distance moved in the direction of force. In figure 3, a piston is moved from the same initial
state (p1,v1) to the same end/final state (p2,v2) via different paths, aand b. If the cross-
sectional area of the piston is Aand the distance the piston travels between state 1 and state
2 is denoted dl, then,
Sign convention:
Work done by a system on the surroundings is positive.
Work done by the surroundings on the system is negative
1.2.12 Heat
Heat is defined as the energy crossing a system’s boundary because of a
temperature gradient between the system and its surroundings. Heat is
represented by the symbol Q.
The interaction at the system boundary is only due to temperature
difference, where heat is transferred from the hot system to the cold one.
Heat is therefore a transfer of thermal energy, which crosses the boundary
of a system due to the difference of temperature between the system and its
surroundings.
Sign convention:
Heat transferred into a system is positive.
Heat transferred out of a system is negative.
Heat is a path function: it is a function of the method in which energy is
transferred between the system and the surroundings. A process in which
there is no heat flow across the boundary i.e. Q= 0, is termed adiabatic
1.3 The Zeroth Law of Thermodynamics
Consider two bodies that are in contact with each other; one is hot, the other
cold. Heat will be lost by the hot body and gained by the cold one until a
point of thermal equilibrium is reached when the temperatures of both bodies
will be equal. The zeroth law of thermodynamics gives the scientific
expression of bodies in the state of thermal equilibrium and states that, If a
system A is in thermal equilibrium with a system B such that TA=TB, and if
the system A is also in thermal equilibrium with a system C such that
TA=TC, then system B and system C must also be in thermal equilibrium, i.e.
TB=TC. It is therefore possible to compare the temperatures of two bodies by
use of a third body, typically a thermometer, without the two bodies being in
physical contact. The zeroth law of thermodynamics thus forms the basis for
temperature measurements
1.4 First Law of Thermodynamics
When a system undergoes a thermodynamics cycle then the net heat supplied
to the system from the surrounding is equals to the net work done by the
system on its surrounding.
1.5 Second Law of Thermodynamics
The second law of thermodynamics takes into consideration the irreversibility
of any process. A machine can never be 100% efficient. The following
statements are considered:
1. Kelvin-Planck statement
It is impossible for any device that operate on a cycle to receive heat from a
single reservoir and produce a net amount of work
2. Clausius Statement
It is impossible to construct a device that operates in a cycle and produces no
effect other than the transfer of heat from a lower temperature body to a higher
temperature body.
2 ENERGY SOURCES
The world's energy resources must fulfill the needs of an increasing world population. The
world energy resources are generally divided into three categories, fossil fuels, nuclear fuels,
and green, renewable or alternative resources.
2.1 Fossil fuels
It consist of coal, oil and natural gas. Today, over 80% of the world's energy supply is from
fossil fuels, of which 60% is from oil and gas and the remaining 40% is from coal. Coal is pure
carbon and natural gas is primarily methane hence, both of these fuels can be used without
substantial processing. Petroleum, on the other hand, is found in the form of crude oil and
must be refined for various applications.
2.2 Nuclear fuels
According to Einstein's equation E=mc², the energy obtained from 1 kg of uranium is
equivalent to the burning of 3.4 thousand tons of coal. Similarly from the conversion of
mass to energy, we find that the energy equivalent of mass in a barrel of oil is over 2 billion
times more than the energy obtained by its combustion. The nuclear energy can be obtained
through two processes namely: Nuclear fusion and fission
2.3 Green or renewable energy sources
The sources include:
1. Hydro
2. Solar
3. Tidal
4. Wind
5. Geothermal
2.3.1 Hydropower plants
Consist of the following components:
Water reservoir, water conduit referred to as the penstock,turbine generator
which could be either ( Kaplan, Pelton or Francis type). The disadvantage of
hydropower plants includes a large initial investment and a need for large
bodies of water, with adverse effect on the rivers ecological system and
susceptibility to unfavorable weather conditions such as drought.
2.3.2 Solar power plants
Solar energy, in the form of electromagnetic radiation that reaches the earth,
by far surpasses all other sources of energy in magnitude. However, large
scale power production by direct conversion of solar radiation to electricity
by photovoltaic is still in the research and development stage. Disadvantages
require a lot of space.
2.3.3 Wind turbines
Wind turbines convert wind kinetic energy into electricity.
2.3.4 Tidal power
Power plants for harnessing tidal power are similar to hydroelectric plants,
but are in the sea instead of in a river beds. The motive power comes from
the fact that the moon's gravitational effect results in daily high and low
tides.
2.3.5 Geothermal power
The earth's core, due to the formation of the solar system is extremely hot.
Indeed at a depth of 40 km, temperature reaches as high as 1000℃.
Geothermal energy relies on this heat source for power production. The
negative aspects include:
1. unlike solar and wind, geothermal energy is not a 100% renewable
source, as long-term use of such sites would result in steam production at
lower pressures or eventual depletion of the source,
2. production of such gases as hydrogen sulfide (H2S), carbon dioxide
(CO2), and nitrogen oxide (NOx), albeit these byproduct gases are
produced in a much smaller scale compared to coal power plants
3. the removal of underground steam and water can potentially cause the
surface to subside
3 FIRST LAW OF THERMODYNAMICS
It is based on the law of conservation of energy which states that energy can neither
be created nor destroyed but it can be transformed from one form to another. In other
words the net work done by the system is equals to the net heat supplied to the
system.
First law of thermodynamics states that when a system undergoes a thermodynamics
cycle then the net heat supplied to the system from the surrounding is equals to the
net work done by the system on its surrounding.
where ∮ is the sum of a complete cycle.
Other statements of the first law of thermodynamics are:
1. Heat and work are mutually convertible but since energy can either be created nor
destroyed the total energy associated with an energy conversion remains constant.
2. No machine can produce energy without corresponding expenditure of energy ie it
is impossible to construct a perpetual motion machine of the first kind
3.1 Internal energy
It is the heat energy stored in a gas. If during heating of the gas the
temperature increases it is in essence the internal energy that has increased.
Joule's law of internal energy states that internal energy of a perfect gas is a
function of temperature only.
3.1.1 Closed system - Non-flow energy equation
For a general closed system, the first law of thermodynamics may be stated
as
that is, the sum of work and heat interactions in a closed system is equal to
the total change in energy in that system. Often, i.e.
changes in potential energy and kinetic energy respectively, are negligible in
closed systems as compared to ΔU(change in internal energy), and the first
law then reduces to;
Q-W= ΔU (4)
This equation is also called the non-flow energy equation. The units of
the energy terms are Joules (J), or more commonly kiloJoules (kJ). The
equation may be expressed in terms of intensive properties as
q-w=Δu (5)
mass m contained in the system). The units of the energy terms are now Joules per
kilogram (J/kg), or more commonly kiloJoules per kilogram (kJ/kg)
In terms of differential changes of a system
δQ −δW =dU or
δq −δw =du.
The use of delta δ for q and w, and the normal differential d for u, is to distinguish
between an interaction across a system boundary (δ) and a change of a property within
the system (d).
If the internal, potential and kinetic energies are restored to their initial values by the
heat and work interactions, then the right-hand side of equation (3) becomes zero.
Hence for a cycle, the total change in energy must be zero:
Q−W= 0 (6)
This is the statement of the first law of thermodynamics for a cycle
Example 1:
In a certain steam plant, the turbine develops 1000 kW. The net heat supplied
to the steam in the boiler is 2800 kJ/kg. The heat rejected to the cooling
water in the condenser is 2100 kJ/kg, and the feed pump work required to
pump the condense back to the boiler is 5 kW. Calculate the steam flow rate
round the cycle.
Exercise:
1. In the compression stroke of an internal-combustion engine, the heat rejected to
the cooling water is 45kJ/kg and the work input is 90kJ/kg. Calculate the change
in specific internal energy of the working fluid stating whether it is a gain or a
loss. [Ans=45kJ/kg,gain]
2. A closed system of constant volume experiences a temperature rise of 25℃ when
a certain process occurs. The heat transferred in the process is 30kJ. The specific
heat at constant volume for the pure substance comprising the system is
1.2kJ/kg℃, and this system contains 2.5 kg of this substance. Determine:
(a) The change in internal energy [75kJ]
(b) The work done [-45kJ]
3. The power developed by a turbine in a certain steam plant is 1200kW. The heat
supplied to the steam in the boiler is 3360 kJ/kg, the heat rejected by the system to
cooling water in the condenser is 2520 kJ/kg and the feed pump work required to
pump the condensate back into the boiler is 6kW. Determine the mass rate of flow
through the cycle.[1.421kg/s]
3.1.2 Open system - Steady flow energy equation
In an open system (not necessarily steady), energy is transferred into and out of the system
not only by heat and work but also by the fluid that crosses into and subsequently out of the
system, in the form of internal energy, gravitational potential energy, kinetic energy and
flow work. Some of the matter flowing through the system may also be retained by the
system, leading to accumulation.
The statement of the first law for such a general open system is: Energy entering a system
must equal the energy leaving the system plus any accumulation of energy within the
system.
In engineering, we often encounter problems concerning steady flow processes, i.e. the rate
at which the fluid flows through the machines or apparatus is constant and there is no
accumulation within the system. The following conditions are satisfied:
1. The mass rates of flow into and out of the system are equal and do not vary with time
2. The energy of the fluid both at the entrance and exit does not change with time
3. The rates of heat and/or work transfer across the system boundary do not vary with
time
Example:
In a gas turbine unit, the gases flow through the turbine is 15 kg/s and the power
developed by the turbine is 12000 kW. The enthalpies of gases at the inlet and outlet are
1260 kJ/kg and 400 kJ/kg respectively, and the velocity of gases at the inlet and outlet are
50 m/s and 110 m/s respectively. Calculate : (i) The rate at which heat is rejected to the
turbine, and (ii) The area of the inlet pipe given that the specific volume of the gases at the
inlet is 0.45 m3/kg.
Exercise:
1. In an air compressor, the compression takes place at constant internal energy and
50kJ of heat are rejected to the cooling water for every kg of air. Find the work
required for the compression stroke per kg of air. [50kJ/kg]
2. A steam turbine receives a steam flow of 1.35kg/s and delivers 500kW. The heat
loss from the casing is negligible.
i. Find the change of specific enthalpy across the turbine when the velocities at
entrance and exit and the difference in elevation at entrance and exit are
negligible. [370kJ/kg]
ii. Find the change of specific enthalpy across the turbine when the velocity at
entrance is 60m/s, the velocity at exit is 360m/s, and the inlet pipe is 3m above
the exhaust pipe. [433kJ/kg]
3. A turbine operating under steady flow conditions receives steam at the following
state; pressure 13.8 bar; specific volume 0.143m³/kg; internal energy 2590kJ/kg;
velocity 30m/s. The state of the steam leaving the turbine is: pressure 0.35 bar,
specific volume 4.37m³/kg, internal energy 2360kJ/kg, velocity 90m/s. Heat is
lost to the surroundings at the rate of 0.25kJ/s. If the rate of steam flow is
0.38kg/s, what is the power developed by the turbine? [102.8kW]
Assignment 1: Due 6th December,2024
1. Air flows steadily at the rate of 0.4kg/s through an air compressor, entering at 6m/s
with a pressure of 1 bar and specific volume of 0.85 m³/kg, and leaving at 4.5m/s
with a pressure of 6.9 bar and specific volume of 0.16m³/kg. The specific 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.
2. A mass of gas with an internal energy of 1500kJ is contained in a cylinder which
has perfect thermal insulation. The gas is allowed to expand behind a piston until
its internal energy is 1400kJ. Calculate the work done by the gas. If the expansion
follows a law pv² = constant, and the initial pressure and the volume of the gas are
28 bar and 0.06m³ respectively, calculate the final pressure and volume
4 THE SECOND LAW OF THERMODYNAMICS
According to the first law of thermodynamics, when a closed system
undergoes a complete cycle, then the net heat supplied to the system is equal
to the net work done by the system, Q−W= 0. This is based on the
conservation of energy and follows from the observation of natural events.
The second law of thermodynamics, which is also a natural law, indicates
that although the net heat supplied in a cycle is equal to the net work done,
the gross heat supplied must be greater than the net work done, meaning that
some heat must always be rejected by the system. We will consider a heat
engine.
4.1 The heat engine
The heat engine is a system operating in a complete cycle and which
converts heat input into work output. The piston-cylinder heat engine is the
most common heat engine.
The heat engine is a system operating in a complete cycle and
which converts heat input into work output. The piston-cylinder
heat engine is the most common heat engine.
The system for the piston-cylinder engine will be the air/gas
contained therein. We will assume the gas is ideal (or perfect) such
that it obeys the equation of state,
pv =RT
R is the gas constant and is calculated,
where Ru is the universal gas constant (8.314x 10³J/kmol K) and M
is the molecular weight of the gas (which is 29 for air). For air,
We will consider the system to be closed (no mass transfer across the
boundary). Let a hot plate supply heat to the gas in such a way that all the
heat goes into the gas and none is absorbed by the cylinder wall - refer to
figure 6 (a).
The system undergoes energy changes; the potential energy and kinetic
energy changes are however assumed small, compared to the internal energy
change.
When the gas is heated, it will expand and push against the piston. Let the
piston initially be restrained so that it does not rise. This causes the pressure
of the gas to increase between 1 and 2, figure 7. As the pressure reaches
point 2, the restraint is removed and the piston will rise thus lifting the
weight mg and doing work. As the piston does work, the process
could proceed in an infinite number of ways e.g. at constant pressure, 2-3a,
or it could be polytropic, = constant, where n is a polytropic index
(process 2-3b). The particular path taken affects the efficiency of the engine.
Let us assume the path taken is 2-3b. At point 3b the weight is taken off;
work has already been done in lifting the weight.
The piston will now be returned to its original state in two processes because
the pressure acting on it may be high: First, some heat is taken away from the
gas through a cold plate.
This is at constant volume, process 3b-4 (corresponding to figure 6 c). When
the pressure has come sufficiently down, at point 4, the piston can now move
down against the gas in the process 4-1 thus taking the system back to its
initial state
There is also an infinite number of possible paths for process 4-1, just like in
the process 2-3.
•The work done by the system during process 2-3b is given as,
● Work done on the system in the process 4-1 is,
● In both cases, the relationship between p and v must be known for the
respective equations to be integrated. The essential point to note is
that the work done is proportional to the area under the curve on the
p-v plot.
● The heat input into the system, is represented by process 1-2 and is
calculated,
● The thermal efficiency is defined as the ratio of the net work
output to the heat input into the system. In this case,
A basic issue in heat engine design has always been: What is the best
path the processes should take, so as to produce the most efficient
engine? This is a central concern of the second law of thermodynamics
It is not possible to have an efficiency of 100% since some of the heat input
is always dissipated in such processes as overcoming friction. Nevertheless,
engineers have always tried to modify designs e.g. changing pressure ratios,
varying the load on the piston etc, to improve efficiency.
Two of the most common cycles (to be discussed later) are:
1. The Otto cycle: this describes the typical automobile internal combustion
(spark-ignition) engine
2. The Diesel cycle: typical for large vehicles such as trucks and buses that
use the compression-ignition engines
4.2 Reversibility
The heat engine already described does not have a thermal efficiency of
100%. For instance, some of the heat input is used to overcome friction.
Such factors lead to process irreversibilities. One way of simulating
reversibility is by pulling the piston a small amount to the right
so slowly that we do not cause any large-scale motion of the gas, figure
8(a).
The process can then be reversed, i.e., the piston may be pushed back to its
original position so that everything returns to the same state it started from.
Such an ideal work transfer is regarded a reversible work interaction,
where all properties are restored to their initial values after the pull-push
motion is complete. In this process, friction is assumed absent between the
cylinder and the piston (friction causes a process to be irreversible).
In reality, all processes are irreversible, but the concept of reversibility is central to
thermodynamic analysis. Reversibility implies that everything is infinitesimally close to
equilibrium at all times throughout the process.
As far as heat interaction is concerned, if the heat interaction occurs at virtually constant
temperature, with only an infinitesimal difference to provide the heat transfer in the
required direction, the heat interaction is reversible.
In figure 9 (a), if we heat the object a little and cool it a little, the heat will
flow first in one direction and then in the other direction in a reversible way.
In other words, to attain reversible heat transfer, we decrease the temperature
difference until in the limit, it is almost zero (infinitesimally small
difference). Heat transfer across a finite temperature difference as in figure 9
(b) is irreversible.
In summary, the concept of reversibility means that the system and its
surroundings are always infinitesimally close to equilibrium A reversible
process then is any process performed so that the system and all its
surroundings can be restored to their initial states by performing the process in
reverse.
4.3 Deriving the second law of thermodynamics
The essence of a heat engine is that it has a heat intake from a high temperature
source, and a heat rejection to a low-temperature sink. We will call these the
high and low temperature reservoirs respectively.
Consider figure 10 (a) showing heat input from a high temperature reservoir,
heat rejection to a low temperature reservoir and net work done on
surroundings. If the cycle were reversible, all the arrows of figure 10 (a) can be
reversed, as shown in figure 10 (b).A heat engine working in reverse is called a
heat pump, requiring work input to transfer heat from a low temperature to a
high temperature reservoir. If a heat pump is irreversible, it would be
represented by figure 10 (c).
Now consider the following steps:
•Let us place a reversible engine ER and an irreversible one E side by side, to operate between the
same hot and cold plates (TH and TC respectively) as shown in figure 11(a). The engines do work WR
and W respectively, while extracting the same amount of heat, QH.
•Let us reverse ER(figure 11 (b)) and use symbol ∃R for it. The engine now transfers heat QH to TH
while an amount of work WR is done on it. Since the heat QH rejected by ∃R to TH is the same
amount extracted by E from TH, then the reservoir TH becomes redundant.
Figure 10: (a)Schematic diagram of a heat engine.
Figure 10:(b)A reversible heat engine (c)A heat pump - a heat engine working as a
heat pump or refrigerator
Again, if we assume W is greater than WR, then E can run ∃R and
still have some work W−WR left over to do external work. This
situation is represented by figure 11 (c).
Such a system, though not violating the first law of
thermodynamics, still violates natural expectations: It does not
require a temperature difference and so requires no fuel to provide
a high-temperature source. If it could exist, all energy and
environmental problems would vanish! The first law is obeyed
thus,
Figure 11: (a)A reversible heat engine (ER) and an irreversible heat engine (E) both operating at the same temperature difference, and both
extracting the same amount of heat from TH (b)The reversible engine is now reversed (c)The high temperature source THis unnecessary,
and net work is produced by extracting heat from a low-temperature reservoir only.
Adding equations (12) and (13) gives equation (11). From equation (11),
QR−Q=W−WR, and because we have assumed W > WR, then QR> Q.
The flaw is in assuming W > WR, i.e., assuming that an irreversible engine can produce
more work than the reversible engine operating between the same hot and cold
reservoirs (figure 11 (a)). If we assume W < WR, then it is fine, but it would similarly
mean that QR< Q.
This would be a useless friction machine, that simply converts work into heat.
The second law must then be stated: It is impossible for any system to operate in a ther-
modynamic cycle and do net work on its surroundings, while receiving heat from a
single reservoir
There are many statements and corollaries of the second law that can be found in
thermodynamics literature. For example, two other statements are:
•Clausius statement: it is impossible to construct a device which operates in a cycle
and whose sole effect is to transfer heat from a cooler body to a hotter body.
•Kevin-Planck statement: it is impossible to construct a device which operates in a
cycle and produces no other effect than the production of work and exchange of heat
with a single reservoir
4.4 Entropy
The second law of thermodynamics gives rise to a property called entropy. Entropy
is a thermodynamic property (does not depend on the path taken). It is denoted by S
while specific entropy is denoted by s. The defining equation for entropy is;
This applies to all working [Link] statement of the second law is that in any
physical process, the total entropy never decreases. All natural processes are
regarded as irreversible and whenever energy is used, it is degraded. In an
irreversible process, entropy increases and the gain in entropy is regarded as a
measure of irreversibility. For reversible adiabatic processes, the entropy remains
constant. Such processes are called isentropic.
In other applications, entropy is regarded as a measure of randomness, e.g., in
statistical mechanics, the Universe is considered to have evolved from a more
ordered to a less ordered state and so entropy is deemed to have increased
4.5 The Carnot cycle
It can be shown from the second law that no heat engine can be more efficient than a
reversible heat engine working between the same temperature limits. Sadi Carnot, a
French engineer, showed that the most efficient possible cycle is one in which all the
heat supplied is supplied at a fixed upper temperature, and all the heat that is rejected
is rejected at a lower fixed temperature. The complete cycle consists of two
isothermal processes and two adiabatic processes. Since all the processes are
reversible, the adiabatic processes in the cycle are termed isentropic (reversible and
adiabatic). The processes are,
1-2: isothermal heat supply
2-3: isentropic expansion
3-4: isothermal heat rejection
4-1: isentropic compression
The Carnot engine and p-v cycle are shown in figure 12, while the T-s diagram is
shown on figure 13
The Carnot cycle efficiency is the highest that can be achieved
between any two fixed temperatures. All others must be less than
it.
EXAMPLE
What is the highest possible theoretical efficiency of a heat engine
operating with a hot reservoir of furnace gases at 2000℃ when the
cooling water available is at 10℃ ? [87.54%]
PROBLEM
A Carnot engine operates between a source temperature of 700℃
and a sink temperature of 20℃ . Assuming that the engine will
have a net output of 65hp, determine the thermal efficiency of the
engine, the heat supplied and the heat rejected. [69.9%; 69.37kJ;
20.88kJ]
To increase the Carnot efficiency, the temperature difference
TH−TC can be increased but there are limitations e.g., for a fixed
TC,TH can only be raised to as high a value as the metallurgical
capabilities of the material components of the engine.
Again, in practice, it is difficult to devise a system which can
receive heat at a constant temperature, and reject heat at a constant
temperature. A wet vapour is the only working substance which
can do this conveniently, since for a wet vapour the pressure and
temperature remain constant as the latent heat is supplied or
rejected. Such a cycle is shown in figure 14