ME8391 ENGINEERING THERMODYNAMICS LTPC

3204
OBJECTIVE:
 To familiarize the students to understand the fundamentals of thermodynamics and to
perform thermal analysis on their behavior and performance.
(Use of Standard and approved Steam Table, Mollier Chart, Compressibility Chart and
Psychrometric Chart permitted)
UNIT I BASIC CONCEPTS AND FIRST LAW 9+6
Basic concepts - concept of continuum, comparison of microscopic and macroscopic approach.
Path and point functions. Intensive and extensive, total and specific quantities. System and their
types. Thermodynamic Equilibrium State, path and process. Quasi-static, reversible and irreversible
processes. Heat and work transfer, definition and comparison, sign convention. Displacement work
and other modes of work .P-V diagram. Zeroth law of thermodynamics – concept of temperature
and thermal equilibrium– relationship between temperature scales –new temperature scales. First
law of thermodynamics –application to closed and open systems – steady and unsteady flow
processes.

UNIT II SECOND LAW AND AVAILABILITY ANALYSIS 9+6

Heat Reservoir, source and sink. Heat Engine, Refrigerator, Heat pump. Statements of second law
and its corollaries. Carnot cycle Reversed Carnot cycle, Performance. Clausius inequality. Concept
of entropy, T-s diagram, Tds Equations, entropy change for - pure substance, ideal gases - different
processes, principle of increase in entropy. Applications of II Law. High and low grade energy.
Available and non-available energy of a source and finite body. Energy and irreversibility.
Expressions for the energy of a closed system and open systems. Energy balance and entropy
generation. Irreversibility. I and II law Efficiency.

UNIT III PROPERTIES OF PURE SUBSTANCE AND STEAM POWER CYCLE 9+6
Formation of steam and its thermodynamic properties, p-v, p-T, T-v, T-s, h-s diagrams. p-v-T
surface. Use of Steam Table and Mollier Chart. Determination of dryness fraction. Application of I
and II law for pure substances. Ideal and actual Rankine cycles, Cycle Improvement Methods -
Reheat and Regenerative cycles, Economiser, preheater, Binary and Combined cycles.

UNIT IV IDEAL AND REAL GASES, THERMODYNAMIC RELATIONS 9+6

Properties of Ideal gas- Ideal and real gas comparison- Equations of state for ideal and real gases-
Reduced properties. Compressibility factor-.Principle of Corresponding states. -Generalised
Compressibility Chart and its use-. Maxwell relations, Tds Equations, Difference and ratio of heat
capacities, Energy equation, Joule-Thomson Coefficient, Clausius Clapeyron equation, Phase Change
Processes. Simple Calculations.

UNIT V GAS MIXTURES AND PSYCHROMETRY 9+6

Mole and Mass fraction, Dalton’s and Amagat’s Law. Properties of gas mixture – Molar mass, gas
constant, density, change in internal energy, enthalpy, entropy and Gibbs function. Psychrometric
properties, Psychrometric charts. Property calculations of air vapour mixtures by using chart and
expressions. Psychrometric process – adiabatic saturation, sensible heating and cooling,
humidification, dehumidification, evaporative cooling and adiabatic mixing. Simple Applications
TOTAL : 75 PERIODS
UNIT I BASIC CONCEPTS AND FIRST LAW
Basic concepts - concept of continuum, comparison of microscopic and macroscopic approach.
Path and point functions. Intensive and extensive, total and specific quantities. System and their
types. Thermodynamic Equilibrium State, path and process. Quasi-static, reversible and irreversible
processes. Heat and work transfer, definition and comparison, sign convention. Displacement work
and other modes of work .P-V diagram. Zeroth law of thermodynamics – concept of temperature
and thermal equilibrium– relationship between temperature scales –new temperature scales. First
law of thermodynamics –application to closed and open systems – steady and unsteady flow
processes.

BASIC CONCEPTS
Heat
Thermodynamics, then, is concerned with several properties of matter; foremost among these is
heat. Heat is energy transferred between substances or systems due to a temperature difference
between them, according to Energy Education. As a form of energy, heat is conserved, i.e., it cannot
be created or destroyed. It can, however, be transferred from one place to another. Heat can also be
converted to and from other forms of energy. For example, a steam turbine can convert heat to
kinetic energy to run a generator that converts kinetic energy to electrical energy. A light bulb can
convert this electrical energy to electromagnetic radiation (light), which, when absorbed by a
surface, is converted back into heat.
Temperature
Temperature is "a measure of the average kinetic energy of the particles in a sample of matter,
expressed in terms of units or degrees designated on a standard scale," according to the American
Heritage Dictionary. The most commonly used temperature scale is Celsius, which is based on the
freezing and boiling points of water, assigning respective values of 0 degrees C and 100 degrees C.
The Fahrenheit scale is also based on the freezing and boiling points of water which have assigned
values of 32 F and 212 F, respectively.
Specific heat
The amount of heat required to increase the temperature of a certain mass of a substance by a certain
amount is called specific heat, or specific heat capacity, according to Wolfram Research. The
conventional unit for this is calories per gram per kelvin. The calorie is defined as the amount of
heat energy required to raise the temperature of 1 gram of water at 4 C by 1 degree.
Thermal conductivity
Thermal conductivity (k) is “the rate at which heat passes through a specified material, expressed as
the amount of heat that flows per unit time through a unit area with a temperature gradient of one
degree per unit distance,” according to the Oxford Dictionary. The unit for k is watts (W) per meter
(m) per kelvin (K). Values of k for metals such as copper and silver are relatively high at 401 and
428 W/m·K, respectively. This property makes these materials useful for automobile radiators and
cooling fins for computer chips because they can carry away heat quickly and exchange it with the
environment. The highest value of k for any natural substance is diamond at 2,200 W/m·K.
Newton's Law of Cooling
In 1701, Sir Isaac Newton first stated his Law of Cooling in a short article titled "Scala graduum
Caloris" ("A Scale of the Degrees of Heat") in the Philosophical Transactions of the Royal Society.
Newton's statement of the law translates from the original Latin as, "the excess of the degrees of the
heat ... were in geometrical progression when the times are in an arithmetical
progression." Worcester Polytechnic Institute gives a more modern version of the law as "the rate of
change of temperature is proportional to the difference between the temperature of the object and
that of the surrounding environment."
Heat transfer
Heat can be transferred from one body to another or between a body and the environment by three
different means: conduction, convection and radiation. Conduction is the transfer of
energy through a solid material. Conduction between bodies occurs when they are in direct contact,
and molecules transfer their energy across the interface.
The Carnot cycle
In 1824, Nicolas Léonard Sadi Carnot proposed a model for a heat engine based on what has come
to be known as the Carnot cycle. The cycle exploits the relationships among pressure, volume and
temperature of gasses and how an input of energy can change form and do work outside the system.
Compressing a gas increases its temperature so it becomes hotter than its environment. Heat can
then be removed from the hot gas using a heat exchanger. Then, allowing it to expand causes it to
cool. This is the basic principle behind heat pumps used for heating, air conditioning and
refrigeration.

Conversely, heating a gas increases its pressure, causing it to expand. The expansive pressure can
then be used to drive a piston, thus converting heat energy into kinetic energy. This is the basic
principle behind heat engines.
Entropy
Entropy is also defined as "a measure of the disorder or randomness in a closed system," which also
inexorably increases. You can mix hot and cold water, but because a large cup of warm water is
more disordered than two smaller cups containing hot and cold water, you can never separate it back
into hot and cold without adding energy to the system. Put another way, you can’t unscramble an
egg or remove cream from your coffee. While some processes appear to be completely reversible, in
practice, none actually are. Entropy, therefore, provides us with an arrow of time: forward is the
direction of increasing entropy.
CONCEPT OF CONTINUUM
It is one of the most important topic of thermodynamics and it is actually the base of the engineering
thermodynamics. Concept of continuum is an assumed state in which we consider the substance free
from any type of discontinuity and treated as continuous. The scale of analysis is very important in
the concept of Continuum. If the scale is large, we can ignore the discontinuities like intermolecular
distances and mean free path but if the scale is small, we can't ignore the discontinuities and switch to
microscopic approach or statistical thermodynamics. So concept of continuum is best suited for
macroscopic approach where overall behavior is considered and individual molecular study is kept
aside.
COMPARISION OF MICROSCOPIC AND MACROSCOPIC APPROACH

PATH AND POINT FUNCTIONS

There are two types of functions defined in thermodynamics

1. Path function-depends upon the path at which system arrives at a given state.
Example,Work and Heat.
2. Point functions-which does not depend on path.Example, temperature, pressure,
density, mass, volume, entropy, internal energy.They are the properties of the
system.
Figure 4.1 shows the difference between point and path functions.

Processes A and B have same initial and final states, hence, the change in volume (DVA and
DVB) for both these processes is same (3 m3 ), as volume is a point function, whereas the
work transferred (WA and WB) for the processes is different since work is a path function

INTENSIVE AND EXTENSIVE PROPERTIES

Intensive properties
An intensive property is a physical quantity whose value does not depend on the amount of the substance for
which it is measured. For example, the temperature of a system in thermal equilibrium is the same as the
temperature of any part of it. If the system is divided, the temperature of each subsystem is identical. The
same applies to the density of a homogeneous system; if the system is divided in half, the mass and the
volume are both divided in half and the density remains unchanged. Additionally, the boiling point of a
substance is another example of an intensive property. For example, the boiling point of water is 100 °C at a
pressure of one atmosphere, which remains true regardless of quantity.
The distinction between intensive and extensive properties has some theoretical uses. For example, in
thermodynamics, according to the state postulate: "The state of a simple compressible system is completely
specified by two independent, intensive properties". Other intensive properties are derived from those two
variables.
Examples
Examples of intensive properties include
 chemical potential, μ
 concentration, c
 density, ρ (or specific gravity)
 magnetic permeability, μ
 melting point and boiling point[7]
 molality, m or b

Extensive properties
An extensive property is a physical quantity whose value is proportional to the size of the system it describes,
or to the quantity of matter in the system. For example, the mass of a sample is an extensive quantity; it
depends on the amount of substance. The related intensive quantity is density which is independent of the
amount. The density of water is approximately 1g/mL whether you consider a drop of water or a swimming
pool, but the mass is different in the two cases.
Dividing one extensive property by another extensive property generally gives an intensive value—for
example: mass (extensive) divided by volume(extensive) gives density (intensive).
Examples
Examples of extensive properties include:

 amount of substance, n
 energy, E
 enthalpy, H
 entropy, S
 Gibbs energy, G
 heat capacity, Cp
 Helmholtz energy, A or F
 internal energy, U
 mass, m
 volume, V

TOTAL AND SPECIFIC QUANTITIES

A particularly important type of intensive property is the specific property, which is
always given on a unit mass basis. An example is specific volume, which has units of
volume/mass, typically expressed as cubic feet per pound or cubic meters per
kilogram. Specific properties are intensive because they exist at a point. For instance,
specific volume is simply the reciprocal of density.

There is an important relationship between specific properties and extensive

properties. Consider the case where the intensive properties of a system are uniform,
meaning they are the same at each point within the system. The total volume V of the
system (say in cubic feet) could be calculated from the mass M of the system (in pounds)
and the specific volume v of the material comprising the system (in cubic feet per pound)
by:

V = vM

This equation only works if the specific volume is constant throughout the
system. Although this is not always true, it is often sufficiently accurate to assume
so. For instance, if you wanted to know the mass of air in your bedroom, you could
measure the volume of the room with a yardstick (to get V) and look up the specific
volume of air (v) at ambient conditions and calculate M from V/v. You would do this
even though the air near the ceiling has a slightly different density than the air near the
floor.

Notice that we used an upper case V to represent the extensive property volume and a
lower case v to represent the intensive property specific volume. We will continue to
follow this convention. Exceptions are temperature and pressure which are generally
represented by upper case letters T and P, even though they are intensive properties.

You might wonder why we need to be concerned with both intensive and extensive
properties. It is because the expressions for the first and second laws of thermodynamics
will be written in terms of extensive properties and the charts we use to look up property
values will contain intensive properties. So we will be using V=vM (and the analogous
equations for properties other than V) to convert the chart properties to extensive
variables for use in the equations
SYSTEM AND THEIR TYPES
THERMODYNAMIC EQUILIBRIUM STATE

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

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.
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.
PATH AND PROCESS
REVERSIBLE,IRREVERSIBLE PROCESS & QUASI STATIC PROCESS
HEAT AND WORK TRANSFER, DEFINITION AND COMPARISON, SIGN CONVENTION.
DISPLACEMENT WORK AND OTHER MODES OF WORK .P-V DIAGRAM.
ZEROTH LAW OF THERMODYNAMICS

.
CONCEPT OF TEMPERATURE AND THERMAL EQUILIBRIUM

RELATIONSHIP BETWEEN TEMPERATURE SCALES –NEW TEMPERATURE SCALES.

New temperature scale

FIRST LAW OF THERMODYNAMICS

The law of conservation of energy states that the total energy of an isolated system is constant; energy
can be transformed from one form to another, but can be neither created nor destroyed. The first law is
often formulated

It states that the change in the internal energy ΔU of a closed system is equal to the amount of heat Q
supplied to the system, minus the amount of work W done by the system on its surroundings. An equivalent
statement is that perpetual motion machines of the first kind are impossible.
APPLICATION TO CLOSED AND OPEN SYSTEMS
First Law of Thermodynamics for a Closed System
STEADY AND UNSTEADY FLOW PROCESSES.
UNSTEADY FLOW PROCESS
UNIT II SECOND LAW AND AVAILABILITY ANALYSIS
Heat Reservoir, source and sink. Heat Engine, Refrigerator, Heat pump. Statements of second law
and its corollaries. Carnot cycle Reversed Carnot cycle, Performance. Clausius inequality. Concept
of entropy, T-s diagram, Tds Equations, entropy change for - pure substance, ideal gases - different
processes, principle of increase in entropy. Applications of II Law. High and low grade energy.
Available and non-available energy of a source and finite body. Energy and irreversibility.
Expressions for the energy of a closed system and open systems. Energy balance and entropy
generation. Irreversibility. I and II law Efficiency.
HEAT RESERVOIR
A thermal energy reservoir (TER) is defined as a large body of infinite heat capacity,
which is capable of absorbing or rejecting an unlimited quantity of heat without suffering
appreciable changes in its thermodynamic coordinates. The changes that do take place in the large
body as heat enters or leaves are so very slow and so very minute that all processes within it are
quasi-static.

The thermal energy reservoir TER from which heat Q1 is transferred to the system operating in a
heat engine cycle is called the source. The thermal energy reservoir TER to which heat Q2 is
rejected from the system during a cycle is the sink.

A typical source is a constant temperature furnace where fuel is continuously burnt, and a typical
sink is a river or sea or the atmosphere itself.

A mechanical energy reservoir (MER) is a large body enclosed by an adiabatic impermeable wall
capable of storing work as postential energy (such as a raised weight or wound spring) or kinetic
energy (such as a rotating flywheel). All processes of interest within an MER are essentially quasi-
static. An MER receives and delivers mechanical energy quasi - statically.

Above figure show a cyclic heat engine exchanging heat with a source and a sink and delivering
W(net) in a cycle to an MER

SOURCE
A body of such a large mass and heat capacity, that it can reject an unlimited quantity of heat
without experiencing any appreciable change in temperature.

SINK
A body of such a large mass and heat capacity, that it can absorb an unlimited quantity of heat
without experiencing any appreciable change in temperature
HEAT ENGINE, REFRIGERATOR, HEAT PUMP
STATEMENTS OF SECOND LAW AND ITS COROLLARIES
CARNOT CYCLE REVERSED CARNOT CYCLE

CARNOT CYCLES
Sadi Carnot was a French physicist who proposed an “ideal” cycle for a
heat engine in 1824.
Historical note – the idea of an ideal cycle came about because engineers
were trying to develop a steam engine (a type of heat engine) where they
could reject (waste) a minimal amount of heat. This would produce the
best efficiency since  = 1 – (QL/QH).
Carnot proposed that a cycle comprised of completely (internally and
externally) reversible processes would give the maximum amount of net
work for a given heat input, since the work done by a system in a
reversible (ideal) process is always greater than that in an irreversible
(real) process.
THE CARNOT HEAT ENGINE CYCLE CONSISTS OF FOUR REVERSIBLE
PROCESSES IN A SEQUENCE:
1  2: Reversible isothermal expansion.
Heat transfer from HTR (+) and boundary work (+) occur in
closed system
2  3: Reversible adiabatic expansion
Work output (+), but no heat transfer
3  4: Reversible isothermal compression
Heat transfer (-) and boundary work (-) occur in closed system
4  1: Reversible adiabatic compression
Work input (-), but no heat transfer
AND Wout >>> Win
P-V DIAGRAM FOR CARNOT HEAT ENGINE CYCLE

P
1
2

4
3

Showing net work is POSITIVE. V

A useful example of an isothermal expansion is boiling (vaporization) at a
constant pressure in a device such as a piston-cylinder. Similarly, an
example of an isothermal compression is condensation at a constant
pressure in a piston-cylinder.
Also, heat transfer can only occur in processes 1  2 and 3 4.
1  2: since work is positive (expansion) and u is positive (e.g.,
boiling) then heat transfer is positive (input from HTR).
3  4: since work is negative (compression) and u is negative (e.g.,
condensation) then heat transfer is negative (output to LTR).
CARNOT PRINCIPLES FOR HEAT ENGINES
1. The efficiency of an irreversible (real) heat engine is always less than
the efficiency for a reversible (CARNOT) heat engine operating
between the same high and low temperature reservoirs, (regardless
of type of devices, working fluid, etc.)

2. The efficiencies of all reversible (CARNOT) heat engines operating

between the same high and low temperature reservoirs are always
equal, (regardless of type of devices, working fluid, etc.)
CARNOT REFRIGERATOR IS SIMPLY A REVERSED CARNOT HEAT ENGINE,
WITH A SEQUENCE OF FOUR REVERSIBLE PROCESSES
1  2: Reversible isothermal expansion
Heat transfer (+) and boundary work (+) occur in closed system
2  3: Reversible adiabatic compression

Work input (-), but no heat transfer

AND Win >>> Wout
3  4: Reversible isothermal compression
Heat transfer (-) and boundary work (-) occur in closed system
41 Reversible adiabatic expansion
Work output (+), but no heat transfer

P-V DIAGRAM FOR CARNOT REFRIGERATOR CYCLE

P
4
3

1
2
V

Showing network is NEGATIVE.

CARNOT PRINCIPLES APPLIED TO A REFRIGERATOR
1. The coefficient of performance (COP) of a refrigerator (or heat
pump) comprised of reversible processes (CARNOT) is always
greater than the COP for a sequence of irreversible (real) processes
 operating between the same high and low temperature reservoirs
(regardless of type of devices, working fluid, etc.).

2. The COP’s of all reversible (CARNOT) refrigerators or heat pumps

operating between the same high and low temperature reservoirs
are always equal, (regardless of type of devices, working fluid, etc.)
The second CARNOT principle states that the efficiency of a CARNOT heat
engine is a function of high and low temperature reservoir temperatures
(TH, TL) only when temperature is on an absolute scale (Kelvin). That is:
C  f (TH , TL )
then since  is by definition a function of the ratio QH/QL. For a model
system of three heat engines operating between the same reservoirs, as
shown in text figure 6-49, it can be proven that
for a reversible (CARNOT) heat engine:
 QH  T
   H
 QL  reversible TL
and
TL Q
C  1   1 L
TH QH

where TH and TL are ALWAYS in degrees Kelvin!

Similarly for CARNOT refrigerator/heat pump cycles:

1 1
COPCR  
 TH   QH 
  1   1
 TL   QL 
and
1 1
COPCHP  
 TL   Q L 
1   1  
 TH   Q H 
where TH and TL are ALWAYS in degrees Kelvin!
REVERSED CARNOT CYCLE
CLAUSIUS INEQUALITY & CONCEPT OF ENTROPY &T-S DIAGRAM
ENTROPY CHANGE FOR DIFFERENT PROCESSES - ideal gases -, principle of increase in entropy
ENTROPY OF PURE SUBSTANCE

ENTROPY CHANGE OF IDEAL GAS

Temperature entrophy diagram
PRINCIPLE OF INCREASE IN ENTROPY.

Increase in Entropy Principle

1. Non-flow Processes

We previously found from considerations of the Clausius Inequality that the following cyclic integral
is always less than or equal to zero, where the equality occurred for a reversible cycle.

This lead to the definition of the property Entropy (S). Consider now an irreversible cycle in which
process (1) > (2) follows an irreversible path, and process (2) > (1) a reversible path, as shown:
Thus the entropy change of an adiabatic process is always greater than or equal to zero, where the
equality applies to reversible processes. However not all processes are adiabatic. Nevertheless we can
always enclose a system in a surrounding environment which is adiabatic, thus considering the total
entropy change of both the system and surroundings we obtain:

Thus the Increase in Entropy Principle states that for any process the total change in entropy of a
system together with its enclosing adiabatic surroundings is always greater than or equal to zero.
This total change of entropy is denoted the Entropy Generated during the process (Sgen [kJ/K] or
sgen [kJ/kg.K]).
2. Flow Processes (Steady Flow)

We now consider the entropy generated during a steady flow process through a single-input/single-
output Control Volume (CV) enclosed in an adiabatic surroundings as shown:

Notice that for a steady flow system there can be no change of any of its property values with time,
thus the rate of increase of entropy can only be associated with the surroundings. Notice also that at
station (2) we are also dumping entropy from the control volume into the surroundings, and at
station (1) we are sucking entropy out of the surroundings, leading to

Surprisingly the form of the specific entropy generated function sgen for a control volume is identical
to that for a system.

For multiple-input, multiple-output control volumes under steady flow conditions, the entropy
generated function is extended to:

where the summations ( ) are taken over all the exit ports (e) and inlet ports (i).
TDS EQUATION
APPLICATIONS OF II LAW.

Applications of the second law of thermodynamics

1) According to the law, heat always flows from a body at a higher temperature to a body at the lower
temperature. This law is applicable to all types of heat engine cycles including Otto, Diesel, etc. for
all types of working fluids used in the engines.
The concept of the second law of thermodynamics applied to heat engine is equally applicable on the
internal combustion engines used in our cars, motorcycles, ships, airplanes, etc. In the internal
combustion engines the heat is generated by combustion of fuel inside the engine. The combustion of
fuel takes place due to generation of the spark (Spark Ignition or SI engines) as in case of the gasoline
engines or due to compression of the fuel (Compression Ignition or CI engines) as in case of the diesel
engines.
HIGH GRADE AND LOW GRADE ENERGY
Low-grade energy: Based on the thermodynamic concepts, an energy source can be called as high-
grade or low-grade, depending the ease with which it can be converted into other forms. Thus electrical
energy is called a high-grade energy, as it is very easy to convert almost all of it into other energy
forms such as thermal energy (say by using an electrical heater). Whereas, it is not possible to convert
thermal energy completely into electrical energy (typical efficiencies of thermal power plants are
around 30 percent), hence thermal energy is called a low-grade energy. Naturally, high-grade energy
sources are more expensive compared to low-grade energy sources.

AVAILABLE AND NON AVAILABLE ENERGY OF A SOURCE AND FINITE BODY

AVAILABILITY IN STEADY FLOW SYSTEMS

ENERGY AND IRREVERSIBILITY.

EXPRESSIONS FOR THE ENERGY OF A CLOSED SYSTEM AND OPEN SYSTEMS.

ENERGY BALANCE AND ENTROPY GENERATION

For certain simple transformations in systems of constant composition, the entropy changes are
given by simple formulas
Isothermal expansion or compression of an ideal gas

FIRST LAW AND SECOND LAW EFFICIENCY

IRREVERSIBLITY
UNIT III PROPERTIES OF PURE SUBSTANCE AND STEAM POWER CYCLE
Formation of steam and its thermodynamic properties, p-v, p-T, T-v, T-s, h-s diagrams. p-v-T surface. Use of
Steam Table and Mollier Chart. Determination of dryness fraction. Application of I and II law for pure
substances. Ideal and actual Rankine cycles, Cycle Improvement Methods - Reheat and Regenerative cycles,
Economiser, preheater, Binary and Combined cycles.

FORMATION OF STEAM AND ITS THERMODYNAMIC PROPERTIES

P-V, P-T, T-V, T-S, H-S DIAGRAMS
PV Diagram

P-T DIAGRAM
T-s DIAGRAM
A T-s diagram is the type of diagram most frequently used to analyze energy transfer system
cycles. This is because the work done by or on the system and the heat added to or removed from the
system can be visualized on the T-s diagram.

H-S DIAGRAM
An enthalpy–entropy chart, also known as the H–S chart or Mollier diagram, plots the
total heat against entropy,[1] describing the enthalpy of a thermodynamic system.[2] A typical
chart covers a pressure range of 0.01–1000 bar, and temperatures up to 800
degrees Celsius.[3] It shows enthalpy Hin terms internal energy
P-V-T SURFACE.

PvT Surface for a Substance which Contracts Upon Freezing

The equilibrium states of a simple, compressible substance can be specified in terms of its pressure, volume
and temperature. If any two of these state variables is specified, the third is determined. This implies that the
states of the substance can be represented as a surface in a three dimensional PvT space. The PvT surface above
represents a substance which contracts upon freezing. Most substances do so, the notable exception being water
which expands upon freezing. A considerable amount of information about the phases of matter can be
illustrated with the PvT surface.

The solid, liquid and gas(vapor) phases can be represented by regions on the surface. Note that there are regions
on the surface which represent a single phase, and regions which are combinations of two phases. A point lying
on a line between a single-phase and a two-phase region represents a "saturation state". The line between the
liquid and the liquid-vapor regions is called the liquid-saturation line and any point on that line represents a
saturated-liquid state. A point on the boundary between the vapor and the liquid-vapor regions is called a
saturated-vapor state.

Note the critical state where the saturated-liquid and saturated-vapor lines meet. The state variables of this
unique point are denoted by Pc, vc and Tc. If a substance is above the critical temperature Tc, it cannot condense
into a liquid, no matter how high the pressure. This merging of the liquid and vapor states above the critical
temperature is a characteristic of all known substances. While a pure vapor state can exist at a pressure lower
than Pc, at pressures above Pc it is constrained to be a vapor. States with pressures above Pc are described as
"supercritical states".

The remarkable "triple state" of matter where solid, liquid and vapor are in equilibrium may be characterized
by a temperature called the triple point. The triple state is represented by a line parallel to the Pv plane with a
characteristic pressure for the substance but variable volume. The triple point temperature of water is assigned
the value 273.16 K and the triple state of water is used as the reference for establishing the Kelvin temperature
scale.

PvT surface for:

Substance which Ideal

expands upon freezing Gas

USE OF STEAM TABLE AND MOLLIER CHART

It is advisable to use Steam-tables or Mollier chart directly for easy and accurate estimation of the
properties of steam, such as pressure, temperature, specific volume, enthalpy, entropy etc., which we
have calculated by different relations for water/steam in different states under steam generation
section. The properties in Steam tables have been determined experimentally.

In the following discussion, the Steam tables and Mollier chart are used to demonstrate the use of
steam tables and Mollier chart to determine the properties of steam in different states.
Steam Tables
Extensive properties at saturated liquid and saturated vapor state
In steam tables, extensive properties at saturated liquid and at saturated vapor for 1 kg of
liquid/vapor are given as shown in Table 21.1(a) and Table 21.1(b). In Table 21.1(a) these properties
are listed with reference to saturation temperature and in Table 21.1(b) with reference to saturation
pressure. Therefore, it is more convenient to use Table 21.1(a) when temperature is given and Table
21.1(b) when pressure is given. In both the tables, the values of specific volume (vf), enthalpy (hf),
and entropy (sf) of water in saturated liquid state and values of specific volume (vg), enthalpy (hg),
and entropy (sg) of steam in saturated vapor state are directly noted down. The values of internal
energy (uf) of water in saturated liquid state and values of internal energy (ug) of steam in saturated
vapor state are calculated by using following relations.

uf = hf - pvf and ug = hg – pvg

Extensive properties of wet steam i.e. in the liquid + vapor region

Extensive properties in superheated vapor state (vapor region)

Mollier or Enthalpy-Entropy (h-s) diagram

Problem 21.1: Find the specific volume, enthalpy and internal energy of wet steam at 18 bar with
dryness fraction (x) = 0.85, by using Steam Tables and Mollier chart.
DETERMINATION OF DRYNESS FRACTION
APPLICATION OF I AND II LAW FOR PURE SUBSTANCES.
IDEAL AND ACTUAL RANKINE CYCLES
PROPERTIES OF IDEAL GAS – IDEAL AND REAL GAS COMPARISION

EQUATIONS OF STATE FOR IDEAL AND REAL GASSES – REDUCED PROPERTIES

 VAPOUR POWER CYCLES

1. CARNOT CYCLE
2. RANKINE CYCLE
3. REHEAT CYCLE
4. REGENERATIVE CYCLE
5. BINARY VAPOUR CYCLE
6. COMBINED CYCLES
7. ECONOMIZER
8. PREHEATER
CARNOT CYCLE
 THE RANKINE CYCLE EFFICIENCY CAN BE IMPROVED BY

1. Increasing the average temperature at which heat is supplied

2. Decreasing/reducing the temperature at which heat is rejected

This can be achieved by making suitable changes in the conditions of steam generation or condensation,
as discussed below:\
1. Increasing boiler pressure. It has been observed that by increasing the boiler pressure (other factors remaining
the same) the cycle tends to rise and reaches a maximum value at a boiler pressure of about 166 bar.
2. Superheating. All other factors remaining the same, if the steam is superheated before allowing it to expand the
Rankine cycle efficiency may be increased
The use of superheated steam also ensures longer turbine blade life because of the absence of erosion from
high velocity water particles that are suspended in wet vapour.
3. Reducing condenser pressure. The thermal efficiency of the cycle can be amply improved by reducing the
condenser pressure (hence by reducing the temperature at which heat is rejected), especially in high vacuums. But
the increase in efficiency is obtained at the increased cost of condensation apparatus.
REHEAT CYCLE

For attaining greater thermal efficiencies when the initial pressure of steam was raised beyond 42
bar it was found that resulting condition of steam after, expansion was increasingly wetter and
exceeded in the safe limit of 12 per cent condensation.

T-S DIAGRAM FOR REHEAT CYCLE

 Advantages of ‘Reheating’:
1. There is an increased output of the turbine.
2. Erosion and corrosion problems in the steam turbine are eliminated / avoided.
3. There is an improvement in the thermal efficiency of the turbines.
4. Final dryness fraction of steam is improved.
5. There is an increase in the nozzle and blade efficiencies.
Disadvantages :
1. Reheating requires more maintenance.
2. The increase in thermal efficiency is not appreciable in comparison to the expenditure incurred
in reheating.
REGENERATIVE CYCLE
The principle of regeneration can be practically utilized by extracting steam from the turbine at
several locations and supplying it to the regenerative heaters. The resulting cycle is known as
regenerative or bleeding cycle
 T-S DIAGRAM FOR REGENERATIVE CYCLE

Advantages of Regenerative cycle over Simple Rankine cycle:

1. The heating process in the boiler tends to become reversible.

2. The thermal stresses set up in the boiler are minimized. This is due to the fact that temperature
ranges in the boiler are reduced.
3. The thermal efficiency is improved because the average temperature of heat addition to the
cycle is increased.
4. Heat rate is reduced.

5. The blade height is less due to the reduced amount of steam passed through the low pressure
stages.
6. Due to many extractions there is an improvement in the turbine drainage and it reduces
erosion due to moisture.
7. A small size condenser is required.
Regenerative cycle: Disadvantages :
1. The plant becomes more complicated.
2. Because of addition of heaters greater maintenance is required.
 3. For given power a large capacity boiler is required.
4. The heaters are costly and the gain in thermal efficiency is not much in comparison to the
heavier costs.

BINARY AND COMBINED CYCLE

Carnot cycle gives the highest thermal efficiency which is given by

[T1- T2 /T1]

To approach this cycle in an actual engine it is necessary that whole of heat must be
supplied at constant temperature T1 and rejected at T2. This can be achieved only by using a
vapour in the wet field but not in the superheated. The efficiency depends on temperature T1
since T2 is fixed by the natural sink to which heat is rejected. This means that T1 should be as
large as possible, consistent with the vapour being saturated.

 If we use steam as the working medium the temperature rise is accompanied by rise in
pressure and at critical temperature of 374.15°C the pressure is as high as 225 bar which
will create many difficulties in design, operation and control.
 It would be desirable to use some fluid other than steam which has more desirable
thermodynamic properties than water. An ideal fluid for this purpose should have a very
high critical temperature combined with low pressure.
 Mercury, diphenyl oxide and similar compounds, aluminium bromide and zinc
ammonium chloride are fluids which possess the required properties in varying degrees.
 Mercury is the only working fluid which has been successfully used in practice.
 It has high critical temperature (588.4°C) and correspondingly low critical pressure (21
bar abs.). The mercury alone cannot be used as its saturation temperature at atmospheric
pressure is high (357°C). Hence binary vapour cycle is generally used to increase the
overall efficiency of the plant. Two fluids (mercury and water) are
used in cascade in the binary cycle for production of power.
The few more properties required for an ideal binary fluid used in high temperature limit
are listed below:
1. It should have high critical temperature at reasonably low
pressure.
2. It should have high heat of vaporization to keep the weight of fluid in the cycle to
minimum.
3. Freezing temperature should be below room
temperature.
4. It should have chemical stability through the working
cycle.
5. It must be non-corrosive to the metals normally used in power
plants.
6. It must have an ability to wet the metal surfaces to promote the heat
transfer.
7. The vapour pressure at a desirable condensation temperature should be nearly
atmospheric which will eliminate requirement of power for maintenance of vacuum in the
condenser.
8. After expansion through the prime mover the vapour should be nearly saturated so that
desirable heats transfer co-efficient can be obtained which will reduce the size of the condenser
required.
9. It must be available in large quantities at reasonable
cost.
10. It should not be toxic and, therefore, dangerous to human
life.
Economizers
Economizers , or economisers , are mechanical devices intended to reduce energy consumption, or to
perform useful function such as preheating a fluid. The term economizer is used for other purposes as
well. Boiler, power plant, heating, Refrigeration, ventilating, and air conditioning uses are discussed in this
article. In simple terms, an economizer is a heat exchanger.

HVAC

A building's HVAC (heating, ventilating, and air conditioning) system can make use of an air-side
economizer to save energy in buildings by using cool outside air as a means of cooling the indoor space.
When the temperature of the outside air is less than the temperature of the recirculated air, conditioning
with the outside air is more energy efficient than conditioning with recirculated air. When the outside air is
both sufficiently cool and sufficiently dry (depending on the climate) the amount of enthalpy in the air is
acceptable and no additional conditioning of it is needed; this portion of the air-side economizer control
scheme is called free cooling.
Air-side economizers can reduce HVAC energy costs in cold and temperate climates while also potentially
improving indoor air quality, but are most often not appropriate in hot and humid climates. With the
appropriate controls, economizers can be used in climates which experience various weather systems. For
information on how economizers and other controls can affect energy efficiency and indoor air quality in
buildings, see the US Environmental Protection Agency report, "Energy Cost and IAQ Performance of
Ventilation Systems and Controls Study."
When the outside air's dry- and wet-bulb temperatures are low enough, a water-side economizer can use
water cooled by a wet cooling tower or a dry cooler (also called a fluid cooler) to cool buildings without
operating a chiller. They are historically known as the strainer cycle, but the water-side economizer is not
a true thermodynamic cycle. Also, instead of passing the cooling tower water through a strainer and then to
the cooling coils, which causes fouling, more often a plate-and-frame heat exchanger is inserted between
the cooling tower and chilled water loops.
Good controls, and valves or dampers, as well as maintenance, are needed to ensure proper operation of the
air- and water-side economizers.

Refrigeration
Cooler Economizer
A common form of refrigeration economizer is a "walk-in cooler economizer" or "outside air refrigeration
system". In such a system outside air that is cooler than the air inside a refrigerated space is brought into
that space and the same amount of warmer inside air is ducted outside. The resulting cooling supplements
or replaces the operation of a compressor-based refrigeration system. If the air inside a cooled space is only
about 5 °F warmer than the outside air that replaces it (that is, the ∆T>5 °F) this cooling effect is
accomplished more efficiently than the same amount of cooling resulting from a compressor based system.
If the outside air is not cold enough to overcome the refrigeration load of the space the compressor system
will need to also operate, or the temperature inside the space will rise.
Vapor-Compression Refrigeration

Another use of the term occurs in industrial refrigeration, specifically vapor-compression refrigeration. Normally, the
economizer concept is applied when a particular design or feature on the refrigeration cycle, allows a reduction either
in the amount of energy used from the power grid; in the size of the components (basically the gas
compressor’s nominal capacity) used to produce refrigeration, or both. For example, for a walk-in freezer that is kept
at −20 °F (−29 °C), the main refrigeration components would include: an evaporator coil (a dense arrangement of
pipes containing refrigerant and thin metal fins used to remove heat from inside the freezer), fans to blow air over the
coil and around the box, an air-cooled condensing unit sited outdoors, and valves and piping. The condensing unit
would include a compressor and a coil and fans to exchange heat with the ambient air.

An economizer display takes advantage of the fact that refrigeration systems have increasing efficiencies at increasing
pressures and temperatures. The power the gas compressor needs is strongly correlated to both the ratio and the
difference, between the discharge and the suction pressures (as well as to other features like the refrigerant’s heat
capacity and the type of compressor). Low temperature systems such as freezers move less fluid in same volumes.
That means the compressor’s pumping is less efficient on low temperature systems. This phenomenon is notorious
when taking in account that the evaporation temperature for a walk-in freezer at −20 °F (−29 °C) may be around
−35 °F (−37 °C). Systems with economizers aim to produce part of the refrigeration work on high pressures, condition
in which gas compressors are normally more efficient. Depending of the application, this technology either allows
smaller compression capacities to be able to supply enough pressure and flow for a system that normally would require
bigger compressors; increases the capacity of a system that without economizer would produce less refrigeration, or
allows the system to produce the same amount of refrigeration using less power.
Preheater

A Preheater is a device that is used to increase the temperature of petroleum liquids as well as natural gas before
feeding them into further processes. For example, fuel oil or furnace oil is heated to a certain temperature before it is
used as a feedstock in a boiler. Maintaining a certain amount of fuel temperature ensures its complete combustion
thereby reducing pollutants. Similarly, natural gas is heated to a certain temperature so that its pressure can be
increased and it can be easily transported to long distances in pipelines.
UNIT IV IDEAL AND REAL GASES, THERMODYNAMIC RELATIONS
Properties of Ideal gas- Ideal and real gas comparison- Equations of state for ideal and real gases-
Reduced properties. Compressibility factor-.Principle of Corresponding states. -Generalised
Compressibility Chart and its use-. Maxwell relations, Tds Equations, Difference and ratio of heat
capacities, Energy equation, Joule-Thomson Coefficient, Clausius Clapeyron equation, Phase
Change Processes. Simple Calculations.
INTRODUCTION TO IDEAL GAS

PROPERTIES OF IDEAL GAS

An ideal gas has a number of properties; real gases often exhibit behavior very close to ideal. The properties of an
ideal gas are:

1. An ideal gas consists of a large number of identical molecules.

2. The volume occupied by the molecules themselves is negligible compared to the volume occupied by
the gas.
3. The molecules obey Newton's laws of motion, and they move in random motion.
4. The molecules experience forces only during collisions; any collisions are completely elastic, and take a
negligible amount of time.
5. The Ideal Gas can not be liquefied since it has no inter-molecular attraction
and so that molecule will not condense.
 6. The coefficient of thermal expansion(ɑ) depends on temperature(T) of the
gas and does not depends on the nature of the gas.
7. The coefficient of compressibility(β) similarly depends on the Pressure(P) of
the gas and will be same for all gases.
8. When P is plotted against V, at constant temperature(T) a rectangular
hyperbola curve is obtained as demanded by Boyle's Low
IDEAL AND REAL GAS COMPARISON
EQUATIONS OF STATE FOR IDEAL AND REAL GASES
EQUATIONS OF STATE FOR IDEAL GASES
Let us start our discussion by considering the simplest possible macroscopic
system: i.e., an ideal gas. All of the thermodynamic properties of an ideal gas are
summed up in its equation of state, which determines the relationship between its
pressure, volume, and temperature. Unfortunately, classical thermodynamics is
unable to tell us what this equation of state is from first principles. In fact, classical
thermodynamics cannot tell us anything from first principles. We always have to
provide some information to begin with before classical thermodynamics can
generate any new results. This initial information may come from statistical physics
(i.e., from our knowledge of the microscopic structure of the system under
consideration), but, more usually, it is entirely empirical in nature (i.e., it is the result
of experiments). Of course, the ideal gas law was first discovered empirically by
Robert Boyle, but, nowadays, we can justify it from statistical arguments. Recall
(from Sect. 3.8), that the number of accessible states of a monotonic ideal gas varies
like
(265)

where is the number of atoms, and depends only on the energy of the gas
(and is independent of the volume). We obtained this result by integrating over the
volume of accessible phase-space. Since the energy of an ideal gas is independent of
the particle coordinates (because there are no interatomic forces), the integrals over
the coordinates just reduced to simultaneous volume integrals, giving
the factor in the above expression. The integrals over the particle momenta
were more complicated, but were clearly completely independent of , giving

the factor in the above expression. Now, we have a statistical rule which tells
us that
 (266)

[see Eq. (197)], where is the mean force conjugate to the external

parameter (i.e., ), and . For an ideal gas, the only

external parameter is the volume, and its conjugate force is the pressure

(since ). So, we can write

(267)

If we simply apply this rule to Eq. (265), we obtain

(268)

However, , where is the number of moles, and is Avagadro's

number. Also, , where is the ideal gas constant. This allows us to write
the equation of state in its usual form
(269)

The above derivation of the ideal gas equation of state is rather elegant. It is certainly
far easier to obtain the equation of state in this manner than to treat the atoms which
make up the gas as little billiard balls which continually bounce of the walls of a
container. The latter derivation is difficult to perform correctly because it is necessary
to average over all possible directions of atomic motion. It is clear, from the above
derivation, that the crucial element needed to obtain the ideal gas equation of state is
the absence of interatomic forces. This automatically gives rise to a variation of the
number of accessible states with and of the form (6.6), which, in turn, implies
the ideal gas law. So, the ideal gas law should also apply to polyatomic gases with no
interatomic forces. Polyatomic gases are more complicated that monatomic gases
because the molecules can rotate and vibrate, giving rise to extra degrees of freedom,
in addition to the translational degrees of freedom of a monatomic gas. In other

words, , in Eq. (265), becomes a lot more complicated in polyatomic gases.

However, as long as there are no interatomic forces, the volume dependence of is
still , and the ideal gas law should still hold true. In fact, we shall discover that
the extra degrees of freedom of polyatomic gases manifest themselves by increasing
the specific heat capacity.

There is one other conclusion we can draw from Eq. (265). The statistical definition of
temperature is [Eq. (187)]
(270)

It follows that

(271)

We can see that since is a function of the energy, but not the volume, then the
temperature must be a function of the energy, but not the volume. We can turn this
around and write

(272)

In other words, the internal energy of an ideal gas depends only on the temperature
of the gas, and is independent of the volume. This is pretty obvious, since if there are
no interatomic forces then increasing the volume, which effectively increases the
mean separation between molecules, is not going to affect the molecular energies in
any way. Hence, the energy of the whole gas is unaffected.

The volume independence of the internal energy can also be obtained directly from
the ideal gas equation of state. The internal energy of a gas can be considered as a
general function of the temperature and volume, so
(273)

It follows from mathematics that

(274)

where the subscript reminds us that the first partial derivative is taken at
constant volume, and the subscript reminds us that the second partial derivative
is taken at constant temperature. Thermodynamics tells us that for a quasi-static
change of parameters
(275)
The ideal gas law can be used to express the pressure in term of the volume and the
temperature in the above expression. Thus,

(276)

Using Eq. (6.15), this becomes

(277)

However, is the exact differential of a well-defined state function, . This

means that we can consider the entropy to be a function of temperature and

volume. Thus, , and mathematics immediately tells us that

(278)

The above expression is true for all small values of and , so a comparison
with Eq. (277) gives

(279)

(280)

One well-known property of partial differentials is the equality of second derivatives,

irrespective of the order of differentiation, so

(281)

This implies that

(282)

The above expression can be combined with Eqs. (279) and (280) to give

(283)
Since second derivatives are equivalent, irrespective of the order of differentiation,
the above relation reduces to

(284)

which implies that the internal energy is independent of the volume for any gas
obeying the ideal equation of state. This result was confirmed experimentally by
James Joule in the middle of the nineteenth century.
EQUATIONS OF STATE FOR REAL GASES
Real gas.
It is defined as a gas having the forces of attraction between molecules and the gas molecules
tend to be very small at reduced pressures and elevated temperatures.
Equation of state
The relation between the independent properties such as pressure, specific volume and temperature
for a pure substance is known as the equation of state.
Reduced properties
The ratios of pressure, temperature and specific volume of a real gas to the corresponding critical
values are called the reduced properties.
Vander Waal’s equation Vs ideal gas equation of state
The ideal gas equation pV=mRT has two important assumptions,
 There is little or no attraction between the molecules of the gas.
 The volume occupied by the molecules themselves is negligibly small compared to the volume
of the gas.
 This equation holds good for low pressure and high temperature ranges as the intermolecular
attraction and the volume of the molecules are not of much significance. As the pressure increases,
inter molecular forces of attraction and repulsion increases and the volume of the molecules are
not negligible. The real gas deviates considerably from the ideal gas equation [p+ (a/V2)] (V-
b)=RT
The assumptions made in Vander Waal’s equation of state
i. There is no inter molecular forces between particles.
ii. The volume of molecules is negligible in comparison with the gas.
Coefficient of volume expansion
The coefficient of volume expansion is defined as the change in volume with the change in
temperature per unit volume keeping the pressure constant.
Helmholtz function.
1. Helmholtz function is the property of a system and is given by subtracting the product of
absolute
temperature (T) and entropy (S) from the internal energy (U). Helmholtz function = U – TS
Thermodynamic properties
Thermodynamic properties are pressure (p), temperature (T), volume (V), internal energy (U),
enthalpy (H), entropy (S), Helmholtz function and Gibbs function.
Throttling process.
When a fluid expands through a minute orifice or slightly opened valve, the process is called
throttling
process. During this process, pressure and velocity are reduced.
compressibility factor
The compressibility factor of a gas at a given state is defined as a ratio between the product of
pressure
and specific volume of the gas and the product of characteristic gas constant and absolute
temperature
of the gas as that state.
, for real gas (PV/RT) is not equal to 1
Law of corresponding states.
If any two gases have equal values of reduced pressure and reduced temperature, then they
have
same values of reduced volume.
Generalized compressibility chart.
The general compressibility chart is plotted with Z versus Pr for various values of Tr. This is
constructed by plotting the known data of one of mole gases and can be used for any gas. This
chart gives best results for the regions well removed from the critical state for all gases.
The laws of perfect gas.
Boyle's Law states that volume of a given mass of a perfect gas varies inversely as the absolute
pressure when temperature is constant.

EQUATION OF STATE-REDUCED PROPERTIES

in thermodynamics, the reduced properties of a fluid are a set of state variables normalized by
the fluid's state properties at its critical point. These dimensionless thermodynamic coordinates,
taken together with a substance's compressibility factor, provide the basis for the simplest form
of the theorem of corresponding states.
Reduced properties are also used to define the Peng–Robinson equation of state, a model
designed to provide reasonable accuracy near the critical point.[2] They are also used to critical
exponents, which describe the behaviour of physical quantities near continuous phase transitions.

Reduced pressure
Reduced temperature

Reduced specific volume

The reduced specific volume (or "pseudo-reduced specific volume") of a fluid is computed from
the ideal gas law at the substance's critical pressure and temperature

This property is useful when the specific volume and either temperature or pressure are known, in
which case the missing third property can be computed directly.
COMPRESSIBILITY FACTOR
Compressibility factor, usually defined as Z = pV/RT, is unity for an ideal gas. It should not
be confused with the isothermal compressibility coefficient. In most engineering work, the
compressibility factor is used as a correction factor to ideal behavior. Thus, vreal = Z vid is used
to calculate the actual volume, vreal, as the product of the compressibility factor and the ideal
gas volume, all at the same pressure and temperature. Z is most commonly found from a
generalized compressibility factor chart as a function of the reduced pressure, p r = p/pc, and
the reduced temperature, Tτ = T/Tc where pr and Tr are the reduced variables and the
subscript 'c' refers to the critical point.
Figure 1 shows the essential features of a generalized compressibility factor chart. The most
widely-used compressibility factor charts are apparently those of Nelson and Obert (1954,
1955). These have been extended [see, e.g., Liley (1987)] to include the saturated liquid. A
three-parameter correlation Z = f(Pr, Tr, ω), where ω = acentric factor = −log10 pr (Tr = 0.7) −1,
involves the use of two compressibility factor charts so that Z = Z0(pr,Tr) + wZl(pr, Tr).
PRINCIPLE OF CORRESPONDING STATES

And

The formation of the van de Waal's equation of state in terms of the critical paramters in
Equation 16.4.416.4.4 is a universal equation for all gases. Although the actual pressures and
volumes may differ, two gases are said to be in corresponding states if their reduced pressure,
volume, and temperature are the same. What it says is that the behavior of all gases (and
liquids!!) is pretty much the same, except for a scaling factor that is related to the critical point
of the substance. (The value 3/8 is actually not in such good agreement with measurement, this
is why the more complicated Redlich-Kwong and Peng-Robertson expressions are better,
although the idea is the same.) Hence, all one needs to know to describe any fluid's behavior is
its critical point. For example, argon behaves much the same at 300K as ethane does at 600 K
because these temperatures correspond to twice their respective critical temperatures (150.72 K
and 305.4 K, respectively) so TR=2.0

Figure 16.4 Example of a generalized compressibility factor graph

We can rewrite the universal expression to express the compressibility Z in reduced
variables and plot measured values as Z versus the reduced pressure (see fig 16.10). As
you can see very different gases/liquids like nitrogen and water can be made to coincide
if their properties are plotted relative to there critical points rather than in absolute
terms. The compressibility factor Z can also be cast into the form of corresponding states showing
that Z also can be expressed as a universal function of VR and TR or any other two reduced
quantities:

Van der Waals did not stop here. He went on to describe the root cause of condensation of gases into
liquids at lower temperatures: the attractive interactions between the molecules.
GENERALISED COMPRESSIBILITY CHART AND ITS USE

Generalized compressibility factor graphs for pure gases

GENERALIZED COMPRESSIBILITY FACTOR DIAGRAM.

DEFINTION AND PHYSICAL SIGNIFICANCE
MAXWELL RELATIONS
TDS EQUATIONS
DIFFERENCE AND RATIO OF HEAT CAPACITIES

In thermodynamics, the heat capacity at constant volume CV,and the heat capacity at constant
pressure, CP are extensive properties that have the magnitude of energy divided by temperature.
Relations
The laws of thermodynamics imply the following relations between these two heat capacities

ENERGY EQUATION
JOULE-THOMSON COEFFICIENT
CLAUSIUS CLAPEYRON EQUATION
Phase change processes
A phase change, or transition, occurs when a substance undergoes a change in state on a molecular level. In most
substances, changes in temperature or pressure result in a substance phase change. There are several processes of
phase changes, including fusion, solidification, vaporization, condensation, sublimation and physical vapor
deposition
Fusion
Fusion occurs when a substance changes from a solid to a liquid. Prior to melting, strong intermolecular bonds or
attractions hold the atoms, molecules or ions that comprise a solid substance tightly together in the solid form.
Upon heating, the particles gain enough kinetic energy to overcome the bonds that are holding them together and
become mobile. This results in the fusion of the substance.
Solidification
Solidification occurs when a substance changes from a liquid to a solid. While in the liquid state, the particles in a
substance possess enough kinetic energy to move around in close proximity to each other. When a drop in
temperature occurs, the particles lose their kinetic energy and band together. Gradually, the particles settle into a
fixed position, causing the substance to take shape and become a solid.
Vaporization
Vaporization occurs when a substance changes from a liquid to a gas. The molecules in a liquid are in constant
motion while staying relatively close together due to intermolecular forces. When an increase in temperature
occurs, the molecules' kinetic energy also increases. This increase in temperature allows the molecules to gain
kinetic energy and overcome the intermolecular forces, resulting in the vaporization of the substance.
Condensation
Condensation occurs when a substance changes from a vapor to a liquid. In a vapor, there are molecules with high
and low kinetic energy that often collide with surfaces and each other. When molecules with low kinetic energy
collide, intermolecular forces cause them to stick together. As temperature decreases, the kinetic energy of the
molecules also decreases causing the molecules to stick together and resulting in condensation.
Sublimation
Sublimation occurs when a substance changes from a solid into a gas. Increases in temperature causes the kinetic
energy of particles to also increase. This allows the particles to overcome the intermolecular forces and become
mobile. Low pressure also increases the particles' kinetic energy. As the particles escape the solid and disperse as a
gas, sublimation occurs.
Physical Vapor Deposition
Physical vapor deposition occurs when a substance changes from a gas into a solid. In low-pressure situations, thin
films of vaporized materials develop on various surfaces due to plasma sputter bombardment or high-temperature
vacuum evaporation.
SIMPLE CALCULATIONS
UNIT V GAS MIXTURES AND PSYCHROMETRY
Mole and Mass fraction, Dalton’s and Amagat’s Law. Properties of gas mixture – Molar mass,
gas constant, density, change in internal energy, enthalpy, entropy and Gibbs function.
Psychrometric properties, Psychrometric charts. Property calculations of air vapour mixtures by
using chart and expressions. Psychrometric process – adiabatic saturation, sensible heating and
cooling, humidification, dehumidification, evaporative cooling and adiabatic mixing. Simple
Applications
MOLE AND MASS FRACTION
DALTON’S AND AMAGAT’S LAW
AMAGAT’S LAW

PROPERTIES OF GAS MIXTURE

Mixture of gases are common in many applications. Our most common example is air -
mainly consisting of nitrogen, oxygen and water vapor - as moist air. A combustion gas
with nitrogen, water vapor and carbon dioxide is an other example.

Special care must be taken for gas mixtures when using the ideal gas law, calculating the mass,
the individual gas constant or the density.

The Ideal Gas Law for a Gas Mixture

The Ideal Gas Law for a perfect or ideal gas adapted for a gas mixture:

p V = mm Rm T (1)

where

p = absolute pressure in the mixture (N/m2, lb/ft2)

V = volume of the mixture(m3, ft3)

mm = mass of the mixture (kg, lb)

Rm = the individual gas constant for the mixture (J/kg K, ft lb/slugs oR)

T = absolute temperature in the mixture (oK, oR)

The Mass of a Gas Mixture

The mass of a gas mixture can be expressed as:

mm = m1 + m2 + .. + mn (2)

where

m1 + m2 + .. + mn = the mass of each gas component in the mixture

The Individual Gas Constant of a Gas Mixture

The individual gas constant of a gas mixture can be calculated as:

Rm = (R1 m1 + R2 m2 + .. + Rn mn) / (m1 + m2 + .. + mn ) (3)

The Density of a Gas Mixture

The density of a gas mixture can be calculated as:

ρm = (ρ1 v1 + ρ2 v2 + .. + ρn vn) / (v1 + v2 + .. + vn ) (4)

where

ρm = density of the gas mixture (kg/m3, lb/ft3)

ρ1 .. ρn = density of each of the components (kg/m3, lb/ft3)

v1 + v2 + .. + vn = volume share of each of the components (m3, ft3)

MOLAR MASS, GAS CONSTANT

Molar Mass
The molar mass is the mass of all the atoms in a molecule in grams per mole. To
calculate the molar mass of a molecule, we first obtain the atomic weights from the individual
elements in a periodic table. We then count the number of atoms and multiply it by the individual
atomic masses.
In chemistry, the molar mass M is a physical property defined as the mass of a given substance
(chemical element or chemical compound) divided by the amount of substance.[1] The base SI
unit for molar mass is kg/mol. However, for historical reasons, molar masses are almost always
expressed in g/mol.
GAS CONSTANT
The gas constant is also known as the molar, universal, or ideal gas constant, denoted by the
symbol R or R and is equivalent to the Boltzmann constant, but expressed in units
of energy pertemperature increment per mole, i.e. the pressure–volume product, rather than energy
per temperature increment per particle. The constant is also a combination of the constants
from Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law. It is a physical
constant that is featured in many fundamental equations in the physical sciences, such as the ideal
gas law and the Nernst equation.
Physically, the gas constant is the constant of proportionality that happens to relate the energy
scale in physics to the temperature scale, when a mole of particles at the stated temperature is being
considered. Thus, the value of the gas constant ultimately derives from historical decisions and
accidents in the setting of the energy and temperature scales, plus similar historical setting of the
value of the molar scale used for the counting of particles. The last factor is not a consideration in
the value of the Boltzmann constant, which does a similar job of equating linear energy and
temperature scales.
DENSITY
Density is a characteristic property of a substance. The density of a substance is the relationship
between the mass of the substance and how much space it takes up (volume). The mass of atoms,
their size, and how they are arranged determine thedensity of a substance.
CHANGE IN INTERNAL ENERGY
In thermodynamics, the internal energy of a system is the total energy contained within the
system. It is the energy necessary to create or prepare the system in any given state, but does not
include thekinetic energy of motion of the system as a whole, nor the potential energy of the system
as a whole due to external force fields which includes the energy of displacement of the system's
surroundings. It keeps account of the gains and losses of energy of the system that are due to
changes in its internal state.[1][2]
The internal energy of a system can be increased by introduction of matter, by heat, or by
doingthermodynamic work on the system.[3] When matter transfer is prevented by impermeable
containing walls, the system is said to be closed and the first law of thermodynamics may be
regarded as defining the internal energy as the algebraic sum of the "heat added to" and "work
done by" the system on its surroundings. If the containing walls pass neither matter nor energy,
the system is said to be isolated and its internal energy cannot change.
The internal energy of a given state of a system cannot be directly measured and knowledge of all
components is rarely interesting. Thermodynamics is chiefly concerned only with changes in the
internal energy, not with its absolute value. Changes, relative to a reference state, are determined
from convenient chains of thermodynamic operations and thermodynamic processes by which a
given state can be prepared. Such a process can be described by certain extensive state variables
of the system, for example, entropy, mole numbers, or electric dipole moment. For practical
considerations in thermodynamics and engineering it is rarely necessary or convenient to consider
all energies belonging to the total intrinsic energy of a system, such as the energy given by the
equivalence of mass. Customarily, thermodynamic descriptions include only items relevant to the
processes under study.
The internal energy is one of the two cardinal state functions of the state variables, and its value
depends only on the current state of the system and not on the processes undergone to prepare it.
It is an extensive quantity. It is the one and only cardinal thermodynamic potential.[4] All other
thermodynamic potentials are formulated from the internal energy. In practical considerations in
thermodynamics it is rarely necessary, nor convenient, to consider all intrinsic energies of a
system, such as the energy given by the mass-energy equivalence. Conveniently, it can be
explained in microscopic terms by the random kinetic energy due to the microscopic motion of the
system's particles from translations, rotations, and vibrations, and by the potential energy
associated with microscopic forces, including chemical bonds. In statistical mechanics, internal
energy is the ensemble average of the sum of the microscopic kinetic and potential energies of the
system. For study of thermonuclear reactions, the static rest mass energy of the constituents of
matter are important.
ENTHALPY
Enthalpy /ˈɛnθəlpi/ ( listen), a property of a thermodynamic system, is equal to the
system's internal energy plus the product of its pressure and volume.[1][2] In a system enclosed so
as to prevent matter transfer, for processes at constant pressure, the heat absorbed or released
equals the change in enthalpy.
The unit of measurement for enthalpy in the International System of Units (SI) is the joule. Other
historical conventional units still in use include the British thermal unit (BTU) and the calorie.
Enthalpy comprises a system's internal energy, which is the energy required to create the system,
plus the amount of work required to make room for it by displacing its environment and
establishing its volume and pressure.[3]
Enthalpy is defined as a state function that depends only on the prevailing equilibrium state
identified by the system's internal energy, pressure, and volume. It is an extensive quantity.
Enthalpy is the preferred expression of system energy changes in many chemical, biological, and
physical measurements at constant pressure, because it simplifies the description of energy
transfer. In a system enclosed so as to prevent matter transfer, at constant pressure, the enthalpy
change equals the energy transferred from the environment through heat transfer or work other
than expansion work.
ENTROPY
In statistical mechanics, entropy is an extensive property of a thermodynamic system. It is closely
related to the number Ω of microscopic configurations (known as microstates) that are consistent
with the macroscopic quantities that characterize the system (such as its volume, pressure and
temperature). Under the assumption that each microstate is equally probable, the entropy S is
thenatural logarithm of the number of microstates, multiplied by the Boltzmann constant kB.
Formally (assuming equiprobable microstates),
The second law of thermodynamics states that the entropy of an isolated system never decreases.
Such systems spontaneously evolve towards thermodynamic equilibrium, the state with maximum
entropy. Non-isolated systems may lose entropy, provided their environment's entropy increases
by at least that amount so that the total entropy increases. Entropy is a function of the state of the
system, so the change in entropy of a system is determined by its initial and final states. In the
idealization that a process is reversible, the entropy does not change, while irreversible processes
always increase the total entropy.
Because it is determined by the number of random microstates, entropy is related to the amount of
additional information needed to specify the exact physical state of a system, given its macroscopic
specification. For this reason, it is often said that entropy is an expression of the disorder,
orrandomness of a system, or of the lack of information about it. The concept of entropy plays a
central role in information theory.
GIBBS FUNCTION

In thermodynamics, the Gibbs free energy (IUPAC recommended name: Gibbs energy or Gibbs
function; also known as free enthalpy[1] to distinguish it from Helmholtz free energy) is athermodynamic
potential that can be used to calculate the maximum of reversible work that may be performed by
a thermodynamic system at a constant temperature and pressure (isothermal, isobaric). The Gibbs free
energy (ΔGº = ΔHº – TΔSº; J in SI units) is the maximum amount of non-expansion work that can be
extracted from a thermodynamically closed system (one that can exchange heat and work with its
surroundings, but not matter); this maximum can be attained only in a completelyreversible process. When
a system transforms reversibly from an initial state to a final state, the decrease in Gibbs free energy equals
the work done by the system to its surroundings, minus the work of the pressure forces.[2]
The Gibbs energy (also referred to as G) is also the thermodynamic potential that is minimized when a
system reaches chemical equilibrium at constant pressure and temperature. Its derivative with respect to the
reaction coordinate of the system vanishes at the equilibrium point. As such, a reduction in G is a necessary
condition for the spontaneity of processes at constant pressure and temperature.
PSYCHROMETRIC PROPERTIES
PSYCHROMETRIC CHARTS
PROPERTY CALCULATIONS OF AIR VAPOUR MIXTURES BY USING CHART
AND EXPRESSIONS
PSYCHROMETRIC PROCESS
EVAPORATIVE COOLING
In principle - the basic evaporating cooling system use only water and a blower to cool
circulated air.

When warm, dry and unsaturated air is pulled through a water-saturated medium - water
evaporates from the medium to vapor in the air. The evaporation energy comes from the air
which is cooled down.

 air humidity increases - and air temperature is decreases

Evaporative cooling can be implemented with

 direct evaporative systems

 indirect evaporative systems
 hybrid systems with indirect and direct evaporative cooling units
ADIABATIC MIXING