UNIT-1

Review of Fundamental Concepts and Definitions

DEFINITION OF THERMODYNAMICS

Thermodynamics may be defined as follows :

Thermodynamics is an axiomatic science which deals with the relations among heat, work and
properties of system which are in equilibrium. It describes state and changes in state of physical
systems. Or

Thermodynamics is the science of the regularities governing processes of energy conversion. Or

Thermodynamics is the science that deals with the interaction between energy and material systems.

Thermodynamic system, surrounding, universe and boundary

Thermodynamic system is basically defined as the finite quantity of matter or prescribed region
in space where thinking will be concentrated during analyzing a problem.
Whatever thing those are outside from the system will be termed as surrounding and system will
be separated by the surrounding with the help of a boundary which is termed as system
boundary.  System boundary might be fixed or movable.

System and surrounding together will be considered as universe.

Classes of thermodynamic system

There are basically three classes of a thermodynamic system as mentioned here
Closed system
In case of closed system in thermodynamics, there will not be any transfer of mass across the
system boundary. However energy may transfer across the system boundary. Therefore close
system in thermodynamics could be considered as fixed mass system also.
Open system
In case of open system in thermodynamics, mass transfer across the system boundary will take
place and energy may also transfer across the system boundary. You will see that maximum
engineering accessories or devices will follow the concept of open system.
Isolated system
In case of isolated system, there will not be any interaction in between system and it’s
surrounding or we can say that there will not be any transfer of mass or energy across the system
boundary in case of isolated system and therefore isolated system in thermodynamics could be
considered as fixed energy and fixed mass system.
Let us see one example of cooking rice in pressure cooker.
When we will go for cooking the rice in pressure cooker, what we will do? We will use rice and
water as contents for pressure cooker and will place over the gas stove. Now, pressure cooker
placed over the gas strove here will be considered as closed system if pressure cooker lid is
perfectly closed, safety valve is also perfectly closed and whistle is in position i.e. not blowing.
Adiabatic system
Adiabatic system will not permit the exchange of heat energy with its surrounding, however it
will permit to exchange the work energy with its surrounding.
Homogeneous system and heterogeneous system
Homogeneous system will consist single phase such as mixture of water vapor and air.
Heterogeneous system will consist two or more than two phases such as steam and water

Macroscopic and Microscopic approach

In macroscopic approach we fix our attention to certain quantity of matter
without considering the activities (or events) happening at molecular level.
In this approach we determine the properties (e.g. Pressure, Volume,
Temperature) which get affected by the systems interaction with the
surrounding.
There are some macroscopic properties which can be sensed by the
human and some cannot.
Even the macroscopic properties which cannot be sensed by
human can be related to the properties which can be sensed by the
humans.
In microscopic view we try to determine behavior of a system by the events
happening at molecular level.
We can easily find that macroscopic behavior is always related to
microscopic behavior because a matter is always comprised of molecules.
One can see that macroscopic behavior is an average of microscopic
behavior of large number of molecules over a considerable period of time.
For example:
Pressure is a macroscopic property it can be sensed but it too has a
microscopic explanation. Pressure can also be explained as the
change of momentum due to molecular collision.
Difference in Macroscopic and Microscopic views of
Thermodynamics
Table given below will help in understanding the differences in a better
way.

Sr.
No. Macroscopic Approach Microscopic approach

This approach is certain quantity

of matter without the events Events happening at molecular
01 happening at molecular level level is taken into account

Macroscopic approach deals with

the properties which can be
sensed by humans. Or which can A statistical approach is required
be obtained from mathematical for microscopic approach since
02 relations. number of molecules is very large

It is an averaged value of the

activities happening at molecular These are real values and hence
03 level difficult to measure

In order to describe a system

from macroscopic we need very
less number of properties like In order to describe a system from
pressure, volume, temperature microscopic approach we need a
04 etc.  very large number of variables.

CONCEPT OF CONTINUUM
In Macroscopic approach of thermodynamics the substance is considered to be continuous
whereas
every matter actually comprises of myriads of molecules with intermolecular spacing amongst
them.
For analyzing a substance in aggregate it shall be desired to use laws of motion for individual
molecules
and study at molecular level be put together statistically to get the influence upon aggregate. In
statistical
thermodynamics this microscopic approach is followed, although it is often too cumbersome for
practical
calculations.
In engineering thermodynamics where focus lies upon the gross behaviour of the system and
substance in it, the statistical approach is to be kept aside and classical thermodynamics approach
be
followed. In classical thermodynamics, for analysis the atomic structure of substance is
considered to
be continuous. For facilitating the analysis this concept of continuum is used in which the
substance is
treated free from any kind of discontinuity. As this is an assumed state of continuum in substance
so the
order of analysis or scale of analysis becomes very important. Thus, in case the scale of analysis
is large
enough and the discontinuities are of the order of intermolecular spacing or mean free path then
due to
relative order of discontinuity being negligible it may be treated continuous.
In the situations when scale of analysis is too small such that even the intermolecular spacing or
mean free path are not negligible i.e. the mean free path is of comparable size with smallest
significant
dimension in analysis then it can not be considered continuous and the microscopic approach for
analysis should be followed. For example, whenever one deals with highly rarefied gases such as
in
rocket flight at very high altitudes or electron tubes, the concept of continuum of classical
thermodynamics

should be dropped and statistical thermodynamics using microscopic approach should be

followed.
Thus, in general it can be said that the assumption of continuum is well suited for macroscopic
approach
where discontinuity at molecular level can be easily ignored as the scale of analysis is quite
large. The
concept of continuum is thus a convenient fiction which remains valid for most of engineering
problems
where only macroscopic or phenomenological informations are desired.
Thermodynamic Equilibrium Defined

Let us suppose that there are two bodies at different

temperatures, one hot and one cold. When these two bodies are
brought in physical contact with each other, temperature of both
the bodies will change. The hot body will tend to become colder
while the cold body will tend to become hotter. Eventually both the
bodies will achieve the same temperatures and they are said to
be in thermodynamic equilibrium with each other. In an isolated
system when there is no change in the macroscopic property of
the system like entropy, internal energy etc, it is said to be in
thermodynamic equilibrium. The state of the system which is in
thermodynamic equilibrium is determined by intensive properties
such as temperature, pressure, volume etc.

Whenever the system is in thermodynamic equilibrium, it tends to

remain in this state infinitely and will not change spontaneously.
Thus when the system is in thermodynamic equilibrium there
won’t be any spontaneous change in its macroscopic properties.
Conditions for Thermodynamic Equilibrium

The system is said to be in thermodynamic equilibrium if the

conditions for following three equilibrium is satisfied:

1. Mechanical equilibrium

2. Chemical equilibrium

3. Thermal equilibrium

4. Mechanical equilibrium: When there are no unbalanced

forces within the system and between the system and the
surrounding, the system is said to be under mechanical
equilibrium. The system is also said to be in mechanical
equilibrium when the pressure throughout the system and
between the system and surrounding is same. Whenever
some unbalance forces exist within the system, they will get
neutralized to attain the condition of equilibrium. Two
systems are said to be in mechanical equilibrium with each
other when their pressures are same.

5. Chemical equilibrium: The system is said to be in chemical

equilibrium when there are no chemical reactions going on
within the system or there is no transfer of matter from one
 part of the system to other due to diffusion. Two systems are
said to be in chemical equilibrium with each other when their
chemical potentials are same.

6. Thermal equilibrium: When the system is in mechanical and

chemical equilibrium and there is no spontaneous change in
any of its properties, the system is said to be in thermal
equilibrium. When the temperature of the system is uniform
and not changing throughout the system and also in the
surroundings, the system is said to be thermal equilibrium.
Two systems are said to be thermal equilibrium with each
other if their temperatures are same.

For the system to be thermodynamic equilibrium it is necessary

that it should be under mechanical, chemical and thermal
equilibrium. If any one of the above condition are not fulfilled, the
system is said to be in non-equilibrium.
thermodynamic state.
Thermodynamic state is basically defined as the condition of the system at any given point of
time as measured by the values of its properties. We can also express the thermodynamic state as
each unique condition of a thermodynamic system will be termed as thermodynamic state. State
of a thermodynamic system will provide the complete information about the system.

An operation will be termed as change of state if changing takes place in one or more than one
properties of the system. Let us see one example, let we have water 250 ml at a temperature of
30 degree Celsius in a pan and this is the state of the system. 

Now if we are changing one property say it temperature, let we have heated the water to raise the
temperature up to 80 degree Celsius now state of system changed as we have changed the value
of one property here i.e. temperature
Let us see the thermodynamic process
When a thermodynamic system passes through a change in state, succession of states passed will
be termed as path of the system or path of change of state. If path of change of state is
completely specified, path of change of state will be termed as thermodynamic process. 

In simple way we can say that thermodynamic process will occur, if a thermodynamic system is
undergoing through a series of change of states.
During a thermodynamic process, there will be change in one property of the system or more
than one property of the system or also possible that there will be change in all of the properties
of the system.
There are so many thermodynamic processes such as
1. Isothermal process
2. Isochoric process
3. Adiabatic process
4. Isobaric process
5. Isentropic process
6. Isenthalpic process
7. Reversible process
8. Irreversible process
9. Any thermodynamic process or series of processes will be termed as thermodynamic
cycle, when thermodynamic system undergoes through such changes of states that initial
state is similar with final state.
10.
11. Following figure indicates the thermodynamic cycle drawn between Pressure and
volume. System starts with condition 1 and reaches at condition 2 by following constant
pressure process. 

Again system reaches condition 3 by following constant volume process and finally
reaches to initial condition 1. So we may see here that final condition and initial condition
of the system are similar even system has completed processes 1 to 2 and 2 to 3 and
finally 3 to 1.

12.
13. Thermodynamic cycle
Exact and Inexact Differentials
Above we have seen that work depends on the process path. In the language of
mathematics this implies that the work for an infinitesimal step is not an exact
differential, and that is why a Greek delta (δ) is used to denote the work for an
infinitesimal change as δW . As will be seen in the next section, heat is path
dependent as well.
State properties like pressure, temperature, volume and energy describe the
momentary state of the system, or, for inhomogeneous states, the momentary
state in the local volume element. State properties have exact differentials for
which we write, e.g., dE and dV . The energy change E2 −E1 = [ dE and the
volume change V2 − V1 = [ 2 dV are independent of the path connecting the
states.
It is important to remember that work and heat, as path functions, only describe
property changes, not states. A state is characterized by state properties
(pressure, temperature, etc.), it does not possess work or heat.
Quasi-static (reversible) processes go through well defined equilibrium states, so
that the whole process path can be indicated in diagrams, e.g., the p-V-diagram.
Non-equilibrium (irreversible) processes, for which typically the states are
different in all volume elements, cannot be drawn into diagrams. Often
irreversible processes connect homogeneous equilibrium states which can be
indicated in the diagram. We shall use dashed lines to indicate non-equilibrium
processes that connect equilibrium states. As an example, Fig. 3.4 shows a p-V-
diagram of two processes, one reversible, one irreversible, between the same
equilibrium states 1 and 2. We emphasize that the dashed line does not refer to
actual states of the system. The corresponding work for the non equilibrium
process cannot be indicated as the area below the curve, since its computation
requires the knowledge of the—inhomogeneous!—pressures at the piston
surface at all times during the process.
Heat Transfer
Heat is the transfer of energy due to differences in temperature. Experience
shows that for systems in thermal contact the direction of heat transfer is
restricted:
Heat will always go from hot to cold by itself, but not vice versa.
This restriction of direction is an important difference to energy transfer by work
between systems in mechanical contact, which is not restricted.
Since heat flows only in response to a temperature difference, a quasi-static
(reversible) heat transfer process can only be realized in the limit of infinitesimal
temperature differences between the system and the system boundary, and for
infinitesimal temperature gradients within the system.
The main heat transfer mechanisms are: (a) Heat conduction, where thermal
energy is transmitted by microscopic energy exchange between neighboring
particles. (b) Convection, where fluid elements move to hotter or colder parts of
the system and then exchange energy with the new neighborhood.

Factors that Contribute to Irreversibility

Friction
It is readily evident that friction makes a process irreversible. Consider a block and
inclined plane which make up a system. The block is pulled up the inclined plane by
weights at the other end. A certain amount of work is required for this to happen.
Some of the work required is used to overcome the friction between the block and
the plane, and some is used to increase the potential energy of the block. The block can
be restored to its initial position by removing some of the weights and thus allowing
the block to slide back down the plane. Some heat transfer from the surroundings
will be required to restore the block to its initial temperature. Friction has rendered the
process irreversible because the surroundings are not restored to their initial state at
the conclusion of the reverse process.
Unrestrained Expansion
The classic example of an unrestrained expansion, as shown in the following figure, is
a gas separated from a vacuum by a membrane. Consider what happens when the
membrane breaks and the gas fills the entire vessel. It can be shown that this is an
irreversible process by considering what would be necessary to restore the system to
its original state. The gas would have to be compressed and heat transferred from the
gas until its initial state is reached. Since the work and heat transfer involve a change
in the surroundings, the surroundings are not restored to their initial state, indicating
that the unrestrained expansion was an irreversible process.

In the reversible expansion of a gas, there must be only an infinitesimal difference

between the force exerted by the gas and the restraining force, so that the rate at
which the boundary moves will be infinitesimal. In accordance with the previous
definition, this is a quasi-equilibrium process. However, actual systems have a finite
difference in forces, which causes a finite rate of movement of the boundary, and
thus the processes are irreversible in some degree.

Heat Transfer through a Finite Temperature Difference

Consider as a system a high-temperature body and a low-temperature body, and
let heat be transferred from the high-temperature body to the low-temperature
body. The only way in which the system can be restored to its initial state is to
provide refrigeration, which requires work from the surroundings, and some heat
transfer to the surroundings. Because of the heat transfer and the work, the
surroundings are not restored to their original state, indicating that the process is
irreversible.

An interesting question is now posed. Heat is defined as energy that is transferred

through a temperature difference. It has just been shown that heat transfer through
a temperature difference is an irreversible process. Therefore, how can a reversible
process be attained? A heat-transfer process approaches a reversible process as the
temperature difference between the two bodies approaches zero. Therefore, a
reversible heat-transfer process is defined as one in which the heat is transferred
through an infinitesimal temperature difference. But of course, to transfer a finite
amount of heat through an infinitesimal temperature difference would require an
infinite amount of time or infinite area. Therefore, all actual heat transfers are
through a finite temperature difference and hence are irreversible, with the greater
the temperature difference, the greater the irreversibility. However, the concept of
reversible heat transfer is very useful in describing ideal processes.

Mixing of Two Different Substances

The figure below shows the process of mixing two different gases separated by a
membrane. When the membrane is broken, a homogeneous mixture of oxygen and
nitrogen fills the entire volume. This may be considered a special case of an
unrestrained expansion, for each gas undergoes an unrestrained expansion as it fills
the entire volume. A certain amount of work is necessary to separate the gases.
Thus, an air separation plant requires an input of work to accomplish the separation.

Other Factors
A number of other factors make processes irreversible. Hysteresis effects and
the i2R loss encountered in electrical circuits are both factors that make processes
irreversible. Ordinary combustion is also an irreversible process.

It is frequently advantageous to distinguish between internal and external

irreversibility. The following figure shows two identical systems to which heat is
transferred. Assuming each system to be a pure substance, the temperature remains
constant during the heat-transfer process. In one system the heat is transferred from
a reservoir at a temperature T + dT, and in the other the reservoir is at a much higher
temperature, T + ΔT, than the system. The first is a reversible heat-transfer process,
and the second is an irreversible heat-transfer process. However, as far as the
system itself is concerned, it passes through exactly the same states in both
processes, which are assumed reversible. Thus, it can be said for the second system
that the process is internally reversible but externally irreversible because the
irreversibility occurs outside the system.

In a reversible process, the deviation from equilibrium is infinitesimal, and therefore

it occurs at an infinitesimal rate. Since it is desirable that actual processes proceed at
a finite rate, the deviation from equilibrium must be finite, and therefore the actual
process is irreversible in some degree. The greater the deviation from equilibrium,
the greater the irreversibility, and the more rapidly the process will occur.
Energy and its forms:

We can define energy as the strength to do any kind of physical activity. Thus, they say,

“Energy is the ability to do work”

Physical or chemical resources are processed to generate energy which is further used to
provide light or heat for domestic or industrial purposes. We have also heard people
comparing two persons (A & B) and concluding that A has more energy than B. Thus, we
can conclude that different types of energy which can never be created nor destroyed.
Energy can only be transformed from one form to another.
There are two types of energy:

1. Kinetic energy (working)
2. Potential energy (static)

There are two forms of energy sources:

1. Renewable source of energy

2. Non-renewable source of energy

Following are the examples of types of energy based on their sources:

1. Renewable source:
1. Solar energy
2. Wind energy
3. Geothermal energy
2. Non-renewable source:
1. Natural gas
2. Coal
3. Petroleum products

Unit of Energy
The SI unit of energy is Joules (J) which is nothing but a term for Newton-meter.
When a certain amount of force (Newton) is applied to an object and it moved a certain
distance (meters), then the energy applied is said to be Joules (newton-meters).
Types of Energy
There are different forms of energy but the distinction between them is not always clear. As
Richard Feynman, a famous physicist once said, “The notions of potential and kinetic
energy depend on a notion of length scale.
For example, one can speak of macroscopic potential and kinetic energy, which do not
include thermal potential and kinetic energy. Also what is called chemical potential energy is
a macroscopic notion, and closer examination shows that it is really the sum of the potential
and kinetic energy on the atomic and subatomic scale. Similar remarks apply to nuclear
“potential” energy and most other forms of energy.”
Today we will discuss some important types of energy and their features –

 Kinetic Energy
The energy in motion is known as Kinetic Energy. For example a moving ball, flowing water,
etc.

KineticEnergy=12m×v2
Where,
m = Mass of the object
v = Velocity of the object

 Potential Energy
This is the energy stored in an object and is measured by the amount of work done. For
example, a pen on a table, water in a lake, etc.

PotentialEnergy=m×g×h
Where,

 m = Mass of the object (in kilograms)

 g = Acceleration due to gravity
 h = Height in meters

 Mechanical Energy
It is the sum of potential energy and kinetic energy that is the energy associated with the
motion & position of an object is known as Mechanical energy. Thus, we can derive the
formula of mechanical energy as –
Mechanical Energy = Kinetic Energy + Potential Energy

MechanicalEnergy=12m×v2+m×g×h
  Solar Energy
The light and heat from the sun, harnessed using technologies like, solar heating,
photovoltaics, solar thermal energy, solar architecture, and artificial photosynthesis is
known as solar energy. It is the prime source of renewable energy.

 Wind Energy
It is one of the various forms of energy. The energy present in the flow of wind, used by
wind turbines is called wind energy. This energy is a major cheap source to produce
electricity. In this phenomena, the kinetic energy of the wind is converted into mechanical
power.

 Nuclear Energy
The energy present in the nucleus of an atom is known as nuclear energy. The particles of
an atom are tiny and need the energy to hold themselves. Nuclear energy is that enormous
energy in the bonds of an atom which helps to hold the atom together. Nuclear energy can
be used to make electricity.

 Geothermal Energy
The energy or heat present inside the Earth is known as geothermal energy. It is a cheap &
convenient heat and power resource and use of this energy don’t have a side effect like
greenhouse gas emission etc.

 Tidal Energy
Tidal energy or tidal power is a form of hydropower (energy present in water), which
converts the energy present in the tides to produce electricity.

 Biomass Energy
Biomass is organic matter obtained from living organisms. The energy produced from
biomass is called biomass energy.

 Electrical Energy
The energy caused by moving electric charges is known as electrical energy. Electric
energy is a type of kinetic energy as the electrical charges moves.

 Thermal Energy
As the name suggests, thermal energy is the energy obtained from heat. It is a microscopic,
disordered equivalent of mechanical energy.
There may be instances where an object posses more than one type of energy. For
example, boiling water, posses both kinetic and potential energy along with heat energy.

Law of Conservation of Energy

The law of conservation of energy is one of the basic laws in physics. It governs the
microscopic motion of individual atoms in a chemical reaction. The law of conservation of
energy states that “In a closed system, i.e., a system that isolated from its surroundings, the
total energy of the system is conserved.” According to the law, the total energy in a system
is conserved even though the transformation of energy occurs. Energy can neither be
created nor destroyed, it can only be converted from one form to another.
Work and heat (sign convention):

Heat and Work

Both heat and work refer to processes by which energy is transferred to or

from a substance.

Definition of Heat

When energy is exchanged between thermodynamic systems by thermal

interaction, the transfer of energy is called heat. The units of heat are
therefore the units of energy, or joules (J). Heat is transferred by conduction,
convection, and/or radiation.

Heat is transfer by conduction occurs when an object with high thermal energy
comes into contact with an object with low thermal energy. Heat transfer by
convection occurs through a medium. For example, when heat transfers from
the hot water at the bottom of the pot to the cooler water at the top of the pot.
Lastly, heat can also be transferred by radiation; a hot object can convey heat
to anything in its surroundings via electromagnetic radiation.

When a high temperature body is brought into contact with a low temperature
body, the temperatures equilibrate: there is heat flow from higher to lower
temperature, like water flowing downhill, until the temperatures of the
bodies are equivalent. The high temperature body loses thermal energy, and
the low temperature body acquires this same amount of thermal energy. The
system is then said to be at thermal equilibrium.
An illustration of thermal equilibrium : The can of cola and ice cube start at different
temperatures. When they come into contact, heat is transferred from the cola can to the ice
cube until both bodies reach thermal equilibrium.

Definition of Work

Work is the transfer of energy by any process other than heat. Like heat, the
unit measurement for work is joules (J). There are many forms of work,
including but not limited to mechanical, electrical, and gravitational work. For
our purposes, we are concerned with P-V work, which is the work done in an
enclosed chemical system. In this type of system, work is defined as the
change in the volume (V) in liters within the system multiplied by a pressure
(P). Assuming the system is at constant pressure, this equates to the
following:

W=PΔVW=PΔV

Most often, we are interested in the work done by expanding gases. Assuming
the gases are ideal, we can apply the ideal gas law to the above equation to
get the following:

W=PΔV=nRΔTW=PΔV=nRΔT

Relationship Between Heat and Work

Heat and work are related. Work can be completely converted into heat, but
the reverse is not true: heat energy cannot be wholly transformed into work
energy. Scientists and engineers have been able to exploit the principles of
thermochemistry to develop technologies ranging from hot/cold packs to
gasoline powered combustion engines.

For a closed system, the change in internal energy (∆U) is related to heat (Q)
and work (W) as follows:

ΔU=Q+WΔU=Q+W

This means that the total energy within a system is affected by the sum of two
possible energy transfers: heat and work.

Gas Laws:

The gas laws were developed at the end of the 18th century, when scientists began to
realize that relationships between pressure, volume and temperature of a sample
of gas could be obtained which would hold to approximation for all gases.

 Boyle's Law
 Charles' Law
 Gay-Lussac's Law
 Combined Gas Law
 Ideal Gas Law
The following table gives the Gas Law Formulas. Scroll down the page
for more examples and solutions on how to use the Boyle's Law,
Charles'Law, Gay-Lussac's Law, Combined Gas Law and Ideal Gas Law.

Boyle's Law

Boyle's Law states that volume of a given amount of gas held at a

constant temperature varies inversely the with pressure. The
relationship between pressure and volume of Boyle's Law is expressed
in mathematical terms as P1V1= P2V2.

Charles' Law
Charles' Law states that the volume of a given mass of a gas is directly
proportional to its Kelvin temperature at constant pressure. In
mathematical terms, the relationship between temperature and volume
is expressed as V1/T1=V2/T2.

Gay-Lussac's Law

Gay-Lussac's Law states that the pressure of a given mass of gas

varies directly with the Kelvin temperature when the volume remains
constant. Gay-Lussac's Law is expressed in a formula form as P 1/T1 =
P2/T2. When dealing with Gay-Lussac's Law, the unit of the temperature
should always be in Kelvin.

Combined Gas Law

The Combined Gas Law combines Charles' Law, Boyle's Law and Gay
Lussac's Law. The Combined Gas Law states that a gas' (pressure ×
volume)/temperature = constant.

Ideal Gas Law

The Ideal Gas Law mathematically relates the pressure, volume,

amount and temperature of a gas with the equation:
pressure × volume = moles × ideal gas constant × temperature;
PV = nRT.

The Ideal Gas Law is ideal because it ignores interactions between the
gas particles in order to simplify the equation. There is also a Real Gas
Law which is much more complicated and produces a result which,
under most circumstances, is almost identical to that predicted by the
Ideal Gas Law.

(https://www.onlinemathlearning.com/gas-laws-chemistry.html)

What Is the Zeroth Law of Thermodynamics?

The zeroth law of thermodynamics is one of the four laws of
thermodynamics, which states that if two systems are in thermal
equilibrium with a third system, then they are in thermal equilibrium
with one another. As seen from the above section on thermal
equilibrium, these three objects will approach the same temperature.

Applications of the Zeroth Law of Thermodynamics

The zeroth law of thermodynamics is seen in many everyday situations.

 The thermometer may be the most well-known example of the

zeroth law in action. For example, say the thermostat in your
bedroom reads 67 degrees Fahrenheit. This means that the
thermostat is in thermal equilibrium with your bedroom. However,
because of the zeroth law of the thermodynamics, you can assume
that both the room and other objects in the room (say, a clock
hanging in the wall) are also at 67 degrees Fahrenheit.
 Similar to the above example, if you take a glass of ice water and a
glass of hot water and place them on the kitchen countertop for a
few hours, they will eventually reach thermal equilibrium with the
room, with all 3 reaching the same temperature.
 If you place a package of meat in your freezer and leave it
overnight, you assume that the meat has reached the same
temperature as the freezer and the other items in the freezer.

Temperature Scale:

Temperature is a measure of the average kinetic energy of a

system. The most commonly used temperature scales are the
Fahrenheit and Celsius scales. The relationship between
these scales is
(2.2.1)TC=59(TF−32)
where TC and TF are temperatures in degrees Celsius and
degrees Fahrenheit, respectively.
Applications of the equations of state described in the
following require the use of absolute temperature scales.
Absolute temperature may be expressed in terms of degrees
Kelvin or degrees Rankine. The absolute temperature scale in
degrees Kelvin is related to the Celsius scale by
(2.2.2)TK=TC+273
where TK is temperature in degrees Kelvin. The absolute
temperature scale in degrees Rankine is related to the
Fahrenheit scale by
(2.2.3)TR=TF+460
where TR is temperature in degrees Rankine.

First Law of Thermodynamics

The increase in internal energy of a closed system is equal
to the heat supplied to the system minus work done by it.

∆Eint = Q – W
This is the First Law of Thermodynamics and it is the principle of conservation of
energy, meaning that energy can neither be created nor destroyed, but rather
transformed into various forms as the fluid within the control volume is being
studied.
It is the most important law for analysis of most systems and the one that quantifies
how thermal energy is transformed to other forms of energy. It follows, perpetual
motion machines of the first kind are impossible.
Differential form:
Differential form:
dEint = dQ  – dW
The internal energy Eint of a system tends to increase if energy is added as heat Q and
tends to decrease if energy is lost as work W done by the system.
First Law in Terms of Enthalpy dH = dQ + Vdp
The enthalpy is defined to be the sum of the internal energy E plus the product of
the pressure p and volume V. In many thermodynamic analyses the sum of the
internal energy U and the product of pressure p and volume V appears, therefore it
is convenient to give the combination a name, enthalpy, and a distinct symbol, H.

H = U + pV
The first law of thermodynamics in terms of enthalpy show us, why engineers use
the enthalpy in thermodynamic cycles (e.g. Brayton cycle or Rankine cycle).
The classical form of the law is the following equation:

dU = dQ   – dW
In this equation dW is equal to dW = pdV and is known as the boundary work.

The Energy Equation for Control Volumes

In this course we consider three types of Control Volume Systems - Steam Power
Plants, Refrigeration Systems, and Aircraft Jet Engines. Fortunately we will be able to
separately analyse each component of the system independent of the entire system,
which is typically represented as follows:

In addition to the energy flow across the control volume boundary in the form of heat
and work, we will also have mass flowing into and out of the control volume. We will
only consider Steady Flow conditions throughout, in which there is no energy or mass
accumulation in the control volume, thus we will find it convenient to derive the
energy equation in terms of power [kW] rather than energy [kJ]. Furthermore the term
Control Volume indicates that there is no boundary work done by the system, and
typically we have shaft work, such as with a turbine, compressor or pump.

Mass Flow

Consider an elemental mass dm flowing through an inlet or outlet port of a control

volume, having an area A, volume dV, length dx, and an average steady velocity  ,
as follows.

Thus finally the mass flow rate   can be determined as follows:

Flow Energy

The fluid mass flows through the inlet and exit ports of the control volume
accompanied by its energy. These include four types of energy - internal energy (u),
kinetic enegy (ke), potential energy (pe), and flow work (w flow). In order to evaluate
the flow work consider the following exit port schematic showing the fluid doing
work against the surroundings through an imaginary piston:
It is of interest that the specific flow work is simply defined by the pressure P
multiplied by the specific volume v. In the following section we can now develop the
complete energy equation for a control volume.

The Complete Energy Equation for a Control Volume

Consider the control volume shown in the following figure. Under steady flow
conditions there is no mass or energy accumulation in the control volume thus the
mass flow rate  applies both to the inlet and outlet ports. Furthermore with a
constant mass flow rate, it is more convenient to develop the energy equation in terms
of power [kW] rather than energy [kJ] as was done previously.
The total power in due to heat and mass flow through the inlet port (1) must equal the
total power out due to work and mass flow through the outlet port (2), thus:

The specific energy e can include kinetic and potential energy, however will always
include the combination of internal energy (u) and flow work (Pv), thus we
conveniently combine these properties in terms of the property enthalpy (as was done
in Chapter 3a), as follows:

Note that z is the height of the port above some datum level [m] and g is the
acceleration due to gravity [9.81 m/s2]. Substituting for energy e in the above energy
equation and simplifying, we obtain the final form of the energy equation for a single-
inlet single-outlet steady flow control volume as follows:
Notice that enthalpy h is fundamental to the energy equation for a control volume.

STEADY FLOW PROCESSES

There are few definitions that can be used to describe a steady flow process.
First, a steady flow process has the fluid flowing through the CV steadily.
Since the fluid is flowing steadily, the mass flow value through the device
would be constant. Next a steady flow process has no intensive or extensive
properties that would change with time.
As fluid flows through a throttling valve it can be considered adiabatic since
the fluid flow through it is so fast there isn’t much time for heat transfer to
occur. Also no work is involved during the process and the potential energy
can be considered negligible.

Throttling Process:
 A throttling process is a process where, there will not be any change in
enthalpy between inlet state and outlet state of the
fluid and therefore throttling devices are also ...
 There will not any work energy transfer
during throttling process and hence we can say that they will provide
pressure drop without providing any work energy.
 Transfer of heat energy during throttling process is ignored as explained
above

What is steady flow engineering devices?

 Nozzles & Diffusers. Nozzles are steady flow engineering devices that
are used to increase a fluids velocity at the expense of pressure. For ...
 Turbines.
 Compressors.
 Throttling Valves.
 Types of Throttling Valves.

STEADY FLOW ENERGY EQUATION

FOR THROTTLING PROCESS
We were discussing various basic concepts of thermodynamics such as “Thermodynamic point and path
function” in our recent post. We have also discussed the “Flow work or flow energy in
thermodynamics” and also “Mass balance and energy balance for a steady flow process” in the field of
thermal engineering.

Today we will see here the steady flow energy equation for throttling devices with the help of this post.
Finally we will also see the applications of throttling devices. After this post, we will see the steady flow
energy equation for heat exchanger in our next post.

Let us first see here the basic concepts of throttling devices

When a fluid (gas or liquid) flows through a restricted passage, such as partially opened valve, significant
pressure reduction of the fluid will be secured over there. Such type of flow of fluid where significant
pressure reduction of fluid is secured by introducing a restriction in to its passage will be termed as
throttled flow.

Devices used for providing the restriction in the flow of fluid and simultaneously causing significant
pressure drops will be termed as throttling devices. There are many live examples of throttling devices
such as adjustable valves, porous plugs and capillary tubes etc.

Throttling devices
Let us see here the assumptions and law of throttling devices in order to analyse the energy equation for
throttling process.

1. Throttling devices are generally very small in size and hence there will not be much area for
transfer of heat energy. It must be noted here also that there will not be much time for transfer of heat
energy because pressure drop will take place rapidly. Therefore we can assume that transfer of heat
energy will be zero or Q = 0
2. There will not be any mechanism in throttling devices that will allow transferring of work energy
between system and surrounding i.e. there will not any work interaction between throttling devices and
surrounding. Therefore for a throttled process, we will have W =0
3. Throttling devices are generally very small in size and hence change in gravitational potential
energy will be assumed as zero. Therefore we will have ∆Z =0 and hence ∆PE =0
4. When fluid flows through a throttling device, change in kinetic energy will be assumed as zero as
we can neglect the small changes in kinetic energy of the fluid. Therefore, we will have ∆KE =0
Let us recall the steady flow energy equation

Let us implement here the assumptions made above in order to secure the energy equation for
throttling devices in quite simple terms.

H1  = H2

Where, H1 and H2 are the enthalpy of the fluid at inlet and outlet respectively.

Conclusion
So what we have noted here?

1. A throttling process is a process where, there will not be any change in enthalpy between inlet
state and outlet state of the fluid and therefore throttling devices are also termed as isenthalpic devices.
2. There will not any work energy transfer during throttling process and hence we can say that
they will provide pressure drop without providing any work energy.
3. Transfer of heat energy during throttling process is ignored as explained above
4. Change in potential energy is also ignored during the throttling process as explained above
5. Change in fluid velocity and hence change in kinetic energy is also ignored during throttling
process as explained above.

Unsteady-flow Processes

System and Control Volume. As against the system, a control volume has a
fixed boundary. Mass, momentum and energy are allowed to cross the
boundary. We perform a balance of mass, momentum and energy that flow
across the boundary and deduce the changes that could take place to
properties of flow within the control volume.

Also note that an unsteady-flow system may involve boundary work as well as
electrical and shaft work (Fig.). Although both the steady-flow and uniform-
flow processes are somewhat idealized, many actual processes can be
approximated reasonably well by one of these with satisfactory results.

The energy content of a control volume changes with time during

an unsteady-flow process. The magnitude of change depends on the amount
of energy transfer across the system boundaries as heat and work as well as
on the amount of energy transported into and out of the control volume by
mass during the process
During an unsteady-flow process, the
mass in the control volume changes with
time. The mass balance for a system
undergoing any process, can be used for
control volume as

      

where
      i = inlet
      e = exit
      ΔmCV = mCV@final - mCV@initial
      mi = the mass flow into the control
volume
            through one inlet
      me = the mass flow out of the control
volume
              through one exit

Or in rate form

      
where
       i = the rate of mass flow into the
control
             volume through an inlet
       e = the rate of mass flow out of the
control
               volume through an exit

        = the rate of change of mass

within the
                      control volume

Also, the energy content of a control

volume changes with time during an
unsteady-flow process. The general
energy balance can be used for the
control volume as

      Ei - Ee = ΔECV

where
      Ei = the total energy transferred into
the control
             volume by heat, work, and mass
      Ee = the total energy transferred out
of the control
             volume by heat, work, and mass
      ΔECV = energy change in the control
volume in
                 forms of internal, kinetic,
potential, etc.,
                 energies

or in rate form

      

where

       = rate of energy transferred into

the control
               volume by by heat, work, and
mass

        = rate of energy transferred out

of the
                  control volume by heat, work,
and mass

        = rate of energy change in

the control
                      volume in forms of internal,
kinetic,
                      potential, etc., energies

Noting that the energy can be transferred

by heat, work, and mass only, the energy
balance can be rewritten as
      

where
      θ = h + v2/2 + gz , the total energy of
a flowing fluid per unit mass
      ΔECV = (ΔU + ΔKE + ΔPE)CV

    

Unform-flow Processes
   

Uniform-flow processes are special cases of

unsteady-flow processes. During a unform-flow
process, the state of the control volume changes with
time, but it does so uniformly. That is,

 At any instant during the process, the state of

the control volume is the same throughout.
Hence, at an instant, the state of the mass
leaving from the exit is the same as the state
of the mass in the control volume.
 The fluid flows at an opening is uniform and
Uniform-flow Processes steady. That is, the properties do not change
Click to View Movie (72 kB) with time or position over the cross section of
an inlet or exit. But they are different at
different openings.

With these identifications, the mass and energy

 balances for uniform-flow processes become

     

     

where
      2 = final state of the control volume
      1 = initial state of the control volume  
      i = inlet
      e = exit   
    
 When no mass is entering or leaving the control
volume, and the kinetic and potential energy changes
associated with the control volume are negligible, the
energy equation can be reduced to the first law
relation for closed system.

    m2 = m1= m
 

System Reduces to a Closed System when

all the Inlets and Exits are Closed

Limitations of first law of thermodynamics

First law of thermodynamics has explained that energy of a system will be conserved and will be
converted from one form of energy to another form of energy during a process and the complete
energy of the system before the process and after the process will be remaining constant.

But first law of thermodynamics has not provided the information about the direction of the
process. For example first law of thermodynamics has not provided the information about the
direction of flow of heat i.e. weather heat can flow from colder object to a hotter object or not.

Hence, this is the first limitation of the first law of thermodynamics that it does not provide any
restriction on the direction of the process.

Let us consider one example to understand it clearly. We have following figure as shown here.
Hot cup of tea is placed in a cold room and hot tea will be cooled after some time because heat
energy will be lost here by hot tea and same quantity of heat energy will be absorbed here by the
surrounding of cold room and hence first law of thermodynamics is applicable here.

Limitation 2nd
We have seen in first law of thermodynamics, energy transformation through the system will take place
in the form of heat energy or work energy. First law of thermodynamics has not provided the
information that how much quantity of complete energy of the system will be converted in to the work
energy.
According to first law of thermodynamics for a cyclic process, work energy will be converted completely
in heat energy and vice-versa i.e. heat energy will be converted completely in to work energy. 

Limitation 3rd
First law of thermodynamics has not provided any information about the conditions in which conversion
of heat energy in work energy is possible.

Perpetual Motion Machine of the First kind (PMM1)

 
The first law of thermodynamics states that the energy can neither be created
nor be destroyed. It can only gets transformed from one form to another form.
Perpetual Motion Machine is the machine which violates the law of
thermodynamics. A machine, which can supply mechanical work continuously
without consumption of any energy, violates the first law of thermodynamics.
Thus this machine is the Perpetual Motion Machine of the First kind (PMM1).
PMM-1: Perpetual motion machines of first class does work without intake of energy,
thus violate the first law of thermodynamics.

STEADY FLOW ENERGY EQUATION

I. First Law for a Control Volume (VW, S & B: Chapter 6)

A. Frequently (especially for flow processes) it is most useful to express

the First Law as a statement about rates of heat and work, for a
control volume.

1. Conservation of mass (VW, S & B: 6.1)

 
  

2. Conservation of Energy (First Law) (VW, S & B: 6.2)

Recall, dE = Q-W

For the control volume,

where

rate of energy transfer to the system as heat

rate of work done by the system

3. For steady-state (VW, S & B: 6.3)

so

 (units J/s)

or

Neglecting potential and chemical energy (PE and CE)

Where c is the speed of the fluid, and c 2/2 is the kinetic energy of
the fluid per unit mass relative to some coordinate system.

If we divide through by the mass flow and set the inlet of the
control volume as station 1, and the outlet as station 2, then

It is also more convenient to divide the work into two terms: 1)

the flow work done by the system which is p2v2-p1v1, and 2) any
additional work which we will term external work or shaft work,
ws. Then we have

or
 We will call this the steady flow energy equation.

For an ideal gas dh=cp dT so

4. Flow work and external work

Enthalpy is most useful for separating flow work from external work (as
might be produced by a shaft crossing the control volume boundary for
instance). In the figure shown below. Heat is added, a compressor is
doing work on the system, the flow entering the system does work on the
system (work = -p1V1), and work is done by the system through pushing
out the flow (work = +p2V2). The first law relates the change in energy
between states 1 and 2 to the difference between the heat added and the
work done by the system. Frequently, however, we are interested only in
the work that crosses the system boundary, not the volumetric or flow
work. In this case it is most convenient to work with enthalpy.

This also leads to a direct physical interpretation for enthalpy. In an

open flow system, enthalpy is the amount of energy that is transferred
across a system boundary by a moving flow. This energy is composed of
two parts: the internal energy of the fluid (u) and the flow work (pv)
associated with pushing the mass of fluid across the system boundary.

 
 

Note that both of the following cases are also frequently encountered.
Heat addition, with no external work only flow work:

No heat addition, with external work and flow work:

 
  

B. Stagnation Temperature and Stagnation Enthalpy

Suppose that our steady flow control volume is a set of streamlines

describing the flow up to the nose of a blunt object.

The streamlines are stationary in space, so there is no external work done

on the fluid as it flows. If there is also no heat transferred to the flow
(adiabatic), then the steady flow energy equation becomes

1. The quantity that is conserved is called the stagnation

temperature.
 The stagnation temperature is the temperature that the fluid would
reach if it were brought to zero speed by a steady, adiabatic
process with no external work. Note that for any steady, adiabatic
flow with no external work, the stagnation temperature is
constant.

(The Mach number, M, is the ratio of the flow speed, c, to the

speed of sound, a. You will learn more about these quantities in
fluids, but it is interesting to see that M 2 measures the ratio of the
kinetic energy of the gas to its thermal energy.)

2. It is also convenient to define the stagnation enthalpy, hT

So we can write the Steady Flow Energy Equation in a

convenient form as

3. Note that for a quasi-static adiabatic process

so we can write 

and define the relationship between stagnation

pressure and static pressure as
 where, the stagnation pressure is the pressure that the fluid would
reach if it were brought to zero speed, via a steady, adiabatic,
quasi-static process with no external work.

4. Frame dependence of stagnation quantities

An area of common confusion is the frame dependence of

stagnation quantities.

The stagnation temperature and stagnation pressure are the

conditions the fluid would reach if it were brought to zero
speed relative to some reference frame, via a steady, adiabatic
process with no external work (add quasi-static for stagnation
pressure).

What if the body or reference frame is moving? We know from

looking at re-entry vehicles, that the skin temperature is much
hotter than the atmospheric temperature. If the atmosphere is
assumed still, and we stagnate a fluid particle on the nose of a
high speed vehicle (carrying it along with the vehicle and thus
essentially giving it kinetic energy) its stagnation temperature is
given by

where c is the vehicle speed. The temperature the skin reaches (to
first approximation) is the stagnation temperature. The
atmospheric temperature, T, is not frame dependent.

The confusion comes about because T is usually referred to as

the static temperature and in common language this has a similar
meaning as "stagnation". In fluid mechanics and
thermodynamics static is commonly used to label
the thermodynamic properties of the gas p, T, etc.–these are not
 frame dependent. Stagnation quantities are those the flow would
arrive at if brought to zero speed relative to some reference frame,
via a steady, adiabatic process with no external work (add quasi-
static for stagnation pressure). Stagnation quantities depend on the
frame of reference.

Thus for a re-entry vehicle, the stagnation temperature (vehicle

frame) is hotter than the atmospheric (static) temperature. And in
a still atmosphere, the static temperature is the same as the
stagnation temperature (atmospheric frame).

5. Example:

For the case shown below, a jet engine is sitting motionless on the
ground prior to take-off. Air is entrained into the engine by the
compressor. The inlet can be assumed to be frictionless and adiabatic.

Considering the state of the gas within the inlet, prior to passage into the
compressor, as state (1), and working in the reference frame of the
motionless airplane:

a) Is TT1 greater than, less than, or equal to Tatm?

 The stagnation temperature of the atmosphere, T Tatm, is equal to Tatm since
it is moving the same speed as the reference frame (the motionless
airplane). The steady flow energy equation tells us that if there is no heat
or shaft work (the case for our adiabatic inlet) the stagnation enthalpy
(and thus stagnation temperature for constant Cp) remains unchanged.
Thus TT1= TTatm = Tatm

b) Is T1 greater than, less than, or equal to Tatm?

If TT1= Tatm then T1< Tatm since the flow is moving at station 1 and

therefore some of the total energy is composed of kinetic energy (at the
expense of internal energy, thus lowering T 1)

c) Is pT1 greater than, less than, or equal to patm?

Equal, by the same argument as a).

d) Is p1 greater than, less than, or equal to patm?

Less than, by the same argument as b).

C. Example Applications of the Steady Flow Energy Equation (VW, S

& B: 6.4)

1. Flow through a rocket nozzle

A liquid bi-propellant rocket consists of a thrust chamber and

nozzle and some means for forcing the liquid propellants into the
chamber were they react, converting chemical energy to thermal
energy.

 
 

Once the rocket is operating we can assume that all of the flow

processes are steady, so it is appropriate to use the steady flow
energy equation. Also, for now we will assume that the gas
behaves as an ideal gas, though in general this is a poor
approximation. There is no external work, and we assume that the
flow is adiabatic.

Then we can write the First Law as

which becomes 

or

therefore

If we assume quasi-static, adiabatic expansion then

so
 Where Tc and pc are conditions in the combustion chamber (set by
propellants), and pe is the external static pressure.

2. Power to drive a gas turbine compressor

Consider for example the PW4084 pictured below. The engine is

designed to produce about 84,000 lbs of thrust at takeoff.

(drawing courtesy of Pratt and Whitney)

 
The engine is a two-spool design. The fan and low pressure
compressor are driven by the low pressure turbine. The high
pressure compressor is driven by the high pressure turbine.

f = total pressure ratio across the fan Å 1.4

c = total pressure ratio across the fan + compressor Å 45

Tinlet = 300K

Heat transfer from the gas streams is negligible so we write the

First Law (steady flow energy equation) as:

For this problem we must consider two streams, the fan stream
and the core stream, so

We obtain the temperature change by assuming that the

compression process is quasi-static and adiabatic. So

then 
= 91 x 106 Joules/sec

Note that 1 Hp = 745 watts

If a car engine Å 110Hp = 8.2x104 watts,

then the power needed to drive compressor is equivalent

to 1110 automobile engines.

All of this power is generated by the low pressure and high

pressure turbines.