The lecture deals with

Introduction Areas of Application of Thermodynamics Different Approaches in the study of Thermodynamics SI Units

Introduction
The most of general sense of thermodynamics is the study of energy and its relationship to the properties of matter. All activities in nature involve some interaction between energy and matter. Thermodynamics is a science that governs the following: Energy and its transformation easibility of a process involving transformation of energy easibility of a process involving transfer of energy E!uilibrium processes

"ore specifically# thermodynamics deals with energy conversion# energy e$change and the direction of e$change.

Areas of Application of Thermodynamics:

All natural processes are governed by the principles of thermodynamics. %owever# the following engineering devices are typically designed based on the principles of thermodynamics. Automotive engines# Turbines# &ompressors# 'umps# ossil and (uclear 'ower 'lants# 'ropulsion systems for the Aircrafts# Separation and )i!uefication 'lant# *efrigeration# Air+conditioning and %eating Devices.

The principles of thermodynamics are summari,ed in the form of a set of a$ioms. These a$ioms are -nown as four thermodynamic laws:

The ,eroth law# the first law# the second law and the third law.

The .eroth )aw deals with thermal e!uilibrium and provides a means for measuring temperatures. The irst )aw deals with the conservation of energy and introduces the concept of internal energy. The Second )aw of thermodynamics provides with the guidelines on the conversion of internal energy of
matter into wor-. It also introduces the concept of entropy.

The Third )aw of thermodynamics defines the absolute ,ero of entropy. The entropy of a pure crystalline
substance at absolute ,ero temperature is ,ero.

Different Approaches in the Study of Thermodynamics

Thermodynamics can be studied through two different approaches: /a0 "acroscopic Approach and /b0 "icroscopic Approach

"acroscopic Approach &onsider a certain amount of gas in a cylindrical container. The volume /10 can be measured by measuring the diameter and the height of the cylinder. The pressure /'0 of the gas can be measured by a pressure gauge. The temperature /T0 of the gas can be measured using a thermometer. The state of the gas can be specified by the measured '# 1 and T . The values of these variables are space averaged characteristics of the properties of the gas under consideration. In classical thermodynamics# we often use this macroscopic approach. The macroscopic approach has the following features. The structure of the matter is not considered. A few variables are used to describe the state of the matter under consideration. The values of these variables are measurable following the available techni!ues of e$perimental physics.

"icroscopic Approach 2n the other hand# the gas can be considered as assemblage of a large number of particles each of which moves randomly with independent velocity. The state of each particle can be specified in terms of position coordinates / xi # yi # zi 0 and the momentum components / pxi # pyi # pzi 0. If we consider a gas occupying a volume of 3 cm4 at ambient temperature and pressure# the number of particles present in it is of the order of 3565 . The same number of position coordinates and momentum components are needed to specify the state of the gas. The microscopic approach can be summari,ed as: A -nowledge of the molecular structure of matter under consideration is essential. A large number of variables are needed for a complete specification of the state of the matter.

SI Units
SI is the abbreviation of Syst7me International d8 Unit9s. The SI units for mass# length# time and force are -ilogram# meter# second and newton respectively. The unit of length is meter# m# defined as 3 :;5 <:4.<4 wavelengths in vacuum of the radiation corresponding to the orange+red line of the spectrum of =rypton+>:. The unit of time is second# s. The second is defined as the duration of ? 3?6 :43 <<5 cycles of the radiation associated with a specified transition of the &esium 344 atom. The unit of mass is -ilogram# -g. It is e!ual to the mass of a particular cylinder of platinum+iridium alloy -ept at the International @ureau of Aeights and "easures. The amount of substance can also be e$pressed in terms of the mole /mol0. 2ne -ilomole of a substance is the amount of that substance in -ilograms numerically e!ual to its molecular weight. The number of -ilomoles of a substance# n # is obtained by dividing the mass /m0 in -ilograms by the moleculare weight /"0# in -gB -mol.

The unit for temperature is =elvin# = . 2ne = is the fraction 3B6<4.3: of the thermodynamic temperature of the triple point of water. Cuite often the &elsius# o& # is used to e$press the temperature of a substance. The SI unit of force# called the newton# ( is a secondary unit. The# ( # is the force re!uired to accelerate a mass of 3 -ilogram at the rate of 3 meter per /second06 . 3 ( D /3-g0 /3mBs6 0D 3-g mBs6 The smaller or bigger !uantities are e$pressed using the following prefi$es

Factor 1012 109 106 103 102

Prefix tera giga mega kilo hecto

Symbol T G M k h

Factor 10-2 10-3 10-6 10-9 10-12

Prefix centi milli micro nano pico

Symbol c m n p

SI Units
SI is the abbreviation of Syst7me International d8 Unit9s. The SI units for mass# length# time and force are -ilogram# meter# second and newton respectively. The unit of length is meter# m# defined as 3 :;5 <:4.<4 wavelengths in vacuum of the radiation corresponding to the orange+red line of the spectrum of =rypton+>:. The unit of time is second# s. The second is defined as the duration of ? 3?6 :43 <<5 cycles of the radiation associated with a specified transition of the &esium 344 atom. The unit of mass is -ilogram# -g. It is e!ual to the mass of a particular cylinder of platinum+iridium alloy -ept at the International @ureau of Aeights and "easures. The amount of substance can also be e$pressed in terms of the mole /mol0. 2ne -ilomole of a substance is the amount of that substance in -ilograms numerically e!ual to its molecular weight. The number of -ilomoles of a substance# n # is obtained by dividing the mass /m0 in -ilograms by the moleculare weight /"0# in -gB -mol.

The unit for temperature is =elvin# = . 2ne = is the fraction 3B6<4.3: of the thermodynamic temperature of the triple point of water. Cuite often the &elsius# o& # is used to e$press the temperature of a substance. The SI unit of force# called the newton# ( is a secondary unit. The# ( # is the force re!uired to accelerate a mass of 3 -ilogram at the rate of 3 meter per /second06 . 3 ( D /3-g0 /3mBs6 0D 3-g mBs6

The smaller or bigger !uantities are e$pressed using the following prefi$es

Factor 1012 109 106 103 102

Prefix tera giga mega kilo hecto

Symbol T G M k h

Factor 10-2 10-3 10-6 10-9 10-12

Prefix centi milli micro nano pico

Symbol c m n p

Pressure
'ressure is the normal force e$erted by a system against unit area of the boundary surface.

where EA approaches ,ero. The unit for pressure in SI is pacsal# 'a

1 Pa = 1 N/m2
Two other units are widely used

1 bar = 105 Pa = 100 kPa = 0 1 !Pa

and the standard atmosphere# where 3 atm D 353.46; -'a D 3.5346; bar D pressure e$erted by a columan of <:5 mm of %g

Energy
Energy is the capacity to e$ert a force through a distance. In SI# the unit of energy is (ewton+meter# ( m or Foule# F.

Power
The rate of energy transfer or storage is called 3 A D 3 FBs D 3 ( mBs and 3 re!uency# %ert, D %, D s+3 -A D 3555 A. Apart from these# the following units are used forElectric current# Ampere D A various parameters of Electric charge# &oulomb# & D As interest Electric potential# 1olt D 1 D ABA "agnetic flu$# Aeber# Ab D 1s "agnetic flu$ density# Tesla# T D AbBm6 power. The unit of power is watt# A.

The lecture deals with

System Surroundings Types of Systems Intensive and E$tensive 'roperties

System
A thermodynamic system is defined as a definite !uantity of matter or a region in space upon which attention is focussed in the analysis of a problem. Ae may want to study a !uantity of matter contained with in a closed rigid walled chambers# or we may want to consider something such as gas pipeline through which the matter flows. The composition of the matter inside the system may be fi$ed or may change through chemical and nuclear reactions. A system may be arbitrarily defined. It becomes important when e$change of energy between the system and the everything else outside the system is considered. The Gudgement on the energetics of this e$change is very important.

Surroundings
Everything e$ternal to the system is surroundings. The system is distinguished from its surroundings by a specified boundary which may be at rest or in motion. The interactions between a system and its surroundings# which ta-e place across the boundary# play an important role in thermodynamics. A system and its surroundings together comprise a universe.

Types of systems
Two types of systems can be distinguished. These are referred to# respectively# as closed systems and open systems or control volumes. A closed system or a control mass refers to a fi$ed !uantity of matter# whereas a control volume is a region in space through which mass may flow. A special type of closed system that does not interact with its surroundings is called an Isolated system . Two types of e$change can occur between the system and its surroundings: 3.energy e$change /heat or wor-0 and 6.e$change of matter /movement of molecules across the boundary of the system and surroundings0. @ased on the types of e$change# one can define

isolated systems: no e$change of matter and energy closed systems: no e$change of matter but some e$change of energy open systems: e$change of both matter and energy
If the boundary does not allow heat /energy0 e$change to ta-e place it is called adiabatic boundary otherwise it is diathermal boundary.

Property
To describe a system and predict its behaviour re!uires a -nowledge of its properties and how those properties are related. 'roperties are macroscopic characteristics of a system such as mass# volume# energy# pressure and temperature to which numerical values can be assigned at a given time without -nowledge of the past history of the system. "any other properties are considered during the course of our study. The value of a property of a system is independent of the process or the path followed by the system in reaching a particular state.

The change in the value of the property depends only on the initial and the final states. The word state refers to the condition of a system as described by its properties. "athematically# if ' is a property of the system# then the change in the property in going from the initial state 3 to the final state 6 is given by

If ' D ' /$# y0 then#

where#

If

# then d' is said to be an e$act differential# and ' is a point function. A thermodynamic property

is a point function and not a path function. 'ressure# temperature# volume or molar volume are some of the !uantities which satisfy these re!uirements.

Intensive and Extensive Properties

There are certain properties which depend on the si,e or e$tent of the system# and there are certain properties which are independent of the si,e or e$tent of the system. The properties li-e volume# which depend on the si,e of the system are called e$tensive properties. The properties# li-e temperature and pressure which are independent of the mass of the system are called intensive properties. The test for an intensive property is to observe how it is affected when a given system is combined with some fraction of e$act replica of itself to create a new system differing only by si,e. Intensive properties are those which are unchanged by this process# whereas those properties whose values are increased or decreased in proportion to the enlargement or reduction of the system are called e$tensive properties. Assume two identical systems S3 and S6 as shown in igure 6.3 . @oth the systems are in identical states. )et S4 be the combined system. Is the value of property for S4 same as that for S3 /and S6 0H

igure !"#
If the answer is yes# then the property is intensive If the answer is no# then the property is e$tensive

The ratio of the e$tensive property to the mass is called the specific value of that property specific volume# v D 1Bm D 3B I / I is the density0 specific internal energy# u D UBm Similarly# the molar properties are defined as the ratios of the properties to the mole number /(0 of the substance "olar volume D D 1B( D UB(

"olar internal energy D

The lecture deals with

Energy "acroscopic modes of Energy "icroscopic modes of Energy Thermodynamic E!uilibrium 'rocess

Energy
Energy is often defined as the capacity to produce wor-. %owever# this JcapacityJ has a special significance. The capacity represents a combination of an effort and the change brought about by the effort. %owever# the effort is e$erted in overcoming resistance to a particular type of change. The effort involved is measured !uantitatively as a Jdriving forceJ in thermodynamics. A driving force is a property which causes and also controls the direction of change in another property. The !uantitative value of this change is called a JdisplacementJ. The product of a driving force and its associated displacement represents a !uantity of energy# but in thermodynamics this !uantity has meaning only in relation to a specifically defined system. *elative to a particular system there are generally two ways of locating a driving force and the displacement it produces. In one way# the driving force and the displacement are properties of the system and are located entirely within it. The energy calculated from their product represents a change in the internal energy of the system. Similarly# both the driving force and its displacement could be located entirely within the surroundings so that the calculated energy is then a change in the total energy of the surroundings. In another way# the displacement occurs within the system but the driving force is a property of the surroundings and is applied e$ternally at the system boundary. @y definition# the boundary of a system is a region of ,ero thic-ness containing no matter at all so that the energy calculated in this way is not a property of matter either in the system or in its surroundings but represents a !uantity of energy in transition between the two. In any !uantitative application of thermodynamics it is always important to ma-e a careful distinction between energy changes within a system or within its surroundings and energy in transition between them.

$acroscopic modes of energy

=inetic Energy /=E0

If a body is accelerated from its initial velocity the body is to final velocity # the total wor- done on

The wor- done on a body in accelerating it from its initial velocity to a final velocity # is e!ual to the change in the -inetic energy of the body. If the body is decelerated from a velocity to a velocity by the application of resisting force# the wor- done by the body is e!ual to decrease in its -inetic energy.

'otential Energy /'E0 A body of mass m is moved from an initial elevant .3 to a final elevation .6/ ig 4.30

igure %"#

The force on the body# D mg This force has moved a distance / .6 + .30 . Therefore# the wor- done on the body

The -inetic energy and potential energy are also called organi,ed form of energy that can be readily converted into wor-.

$icroscopic modes of energy

The microscopic modes of energy refer to the energy stored in the molecular and atomic structure of the system. The molecules are in random motion. A molecule possesses energy in several forms. Translational energy# *otational energy# 1ibrational energy. Electronic energy# &hemical energy# (uclear energy. If K represents energy of one molecule# then

If ( is the total number of molecules in the system# then the total amount of microscopic form of energy UD(K Ae may also call this as I(TE*(A) E(E*LM of the system. The internal energy# U is due to random motions or disorgani,ed motions of molecules. The internal energy cannot be readily converted into wor-. 2ne of the maGor tas-s involved in thermodynamics is devising means for converting disorgani,ed internal energy into useful or organi,ed wor-.

Thermodynamic E&uili'rium
Steady state Under the steady state condition# the properties of the system at any location are independent of time.

E!uilibrium At the state of e!uilibrium# the properties of the system are uniform and only one value can be assigned to it.

In thermodynamics# e!uilibrium refers to a state of e!uilibrium with respect to all possible changes# thermal# mechanical and chemical.

a Thermal e!uilibrium
A state of thermal e!uilibrium can be described as one in which the temperature of the system is uniform.

b "echanical e!uilibrium
"echanical e!uilibrium means there is no unbalanced force. In other words# there is no pressure gradient within the system.

c &hemical e!uilibrium
The criterian for chemical e!uilibrium is the e!uality of chemical potential

Superscripts A and @ refers to systems and subscript i refers to component

If Libbs function is given by L# L D U N '1 O TS

where ni is the number of moles of substance i . The composition of a system does not undergo any change because of chemical reaction

Process
In thermodynamics we are mainly concerned with the systems which are in a state of e!uilibrium. Ahenever a system undergoes a change in its condition# from one e!uilibrium state to another e!uilibrium state# the system is said to undergo a process. &onsider a certain amount of gas enclosed in a piston+cylinder assembly as our system. Suppose the piston moves under such a condition that the opposing force is always infinitesimally smaller than the force e$erted by the gas. The process followed by the system is reversible .

A process is said to be reversible if the system and its surroundings are restored to their respective initial states by reversing the direction of the process. A reversible process has to be !uasi+static# but a !uasi + static process is not necessarily !uasi+static.

igure %"!
The process is irreversible if it does not fulfil the criterion of reversibility. "any processes are characteri,ed by the fact that some property of the system remains constant. These processes are:

A process in which the volume remains constant

constant volume process. Also called isochoric process B isometric process

A process in which the pressure of the system remains constant.

constant pressure process. Also called isobaric process

A process in which the temperature of the system is constant.

constant temperature process. Also called isothermal process

A process in which the system is enclosed by adiabatic wall.

Adiabatic process

The lecture deals with

Aor Thermodynamic Definition of Aor %eat

(or)
Aor- is one of the basic modes of energy transfer. The wor- done by a system is a path function# and not a point function. Therefore# wor- is not a property of the system# and it cannot be said that the woris possessed by the system. It is an interaction across the boundary. Ahat is stored in the system is energy# but not wor-. A decrease in energy of the system appears as wor- done. Therefore# wor- is energy in transit and it can be indentified only when the system undergoes a process.

Aor- must be regarded only as a type of energy in transition across a well defined# ,ero thic-ness# boundary of a system. &onse!uently wor-# is never a property or any !uantity contained within a system. Aor- is energy driven across by differences in the driving forces on either side of it. 1arious -inds of wor- are identified by the -ind of driving force involved and the characteristic e$tensive property change which accompanied it. Aor- is measured !uantitatively in the following way. Any driving force other than temperature# located outside the system on its e$ternal boundary# is multiplied by a transported e$tensive property change within the system which was transferred across the system boundary in response to this force. The result is the numerical value of the wor- associated with this system and driving force. In static E!uilibrium# D'A / ig P.30. The dQ is small so that ' does not change. The change in volume of the gas D AdQ. The elemental wor-# dAD dQD'AdQD'd1

igure *"#

$odule # : +ecture * : (or) and ,eat

Thermodynamic Definition of (or)

In thermodynamics# wor- done by a system on its surroundings during a process is defined as that interaction whose sole effect# e$ternal to the system# could be reduced as the raising of a mass through a distance against gravitational force. )et us consider the raising of mass m from an initial elevation ,3 to final elevation ,6 against gravitational force. To raise this mass# the force acting on the mass is given by D mg . The wor- done on the body is A D mg/ ,6 + ,3 0 An e$ternal agency is needed to act on the system It can be seen that e$pansion of the gas gets reduced to raising a mass against gravitational force / igure P.60

dW = F dX = P A dX = P dV

igure *"!

During this e$pansion process# the e$ternal pressure is always infinitesimally smaller than the gas pressure.

igure *"%
&ompare two systems shown in the figure P.4. )et the resistor be replaced by a motor drawing the same amount of current as the resistor. The motor can wind a string and thereby raise the mass which is suspended. As far as the battery is concerned# the situations are identical. So# according to thermodynamic definition of wor-# the interaction of a battery with a resistor is called wor-. @y manipulating the environment# that is e$ternal to the battery /system0# the effect can be reduced to raising of a mass against the gravitational force and that is the only effect on the surroundings. Ae can see that the thermodynamic definition of wor- is more general than that used in mechanics.

Situation in which ( - P d.

igure *"*

)et the initial volume be 13 and pressure '3 )et the final volume be 16 and pressure '6
Ahat should be the wor- done in this caseH Is it e!ual to R' d1 H

"' d1 D area under the curve indicating the process on '+1 diagram.
The e$pansion process may be carried out in steps as shown in figure P.P. It is possible to draw a smooth curve passing through the points 3bcde6 . Does the area under the curve /figure P.;0 represent wor- done by the systemH The answer is no# because the process is not reversible. The e$pansion of the gas is not restrained by an e!ual and opposing force at the moving boundary.

# " P dV

igure *"/
(o e$ternal force has moved through any distance in this case# the wor- done is ,ero. Therefore# we observe that A D R ' d1 only for reversible process A S R ' d1 for an irreversible process Another e$ceptional situation T The piston is held rigid using latches T / igure P.:0 d1 D 5 Aor- done on the gas is e!ual to the decrease in the potential energy of mass m

A situation where d1 D 5 and yet dA is not ,ero

such wor- can be done in one direction only. Aor- is done on the system by the surroundings

igure *"0

,eat
%eat is energy transfer which occurs by virtue of temperature difference across the boundary. %eat li-e wor-# is energy in transit. It can be identified only at the boundary of the system. %eat is not stored in the body but energy is stored in the body. %eat li-e wor-# is not a property of the system and hence its differential is not e$act. %eat and wor- are two different ways of transferring energy across the boundary of the system. The displacement wor- is given by /figure P.<0

igure *"1

It is valid for a !uasi+static or reversible process. The wor- transfer is e!ual to the integral of the

product of the intensive property ' and the differential change in the e$tensive property# d1 . Fust li-e displacement wor-# the heat transfer can also be written as

The !uantity dC is an ine$act differential.

dQ = TdX
Q is an e$tensive property and dQ is an e$act differential. The e$tensive property is yet to be defined. Ae shall see later that Q is nothing but the entropy# S of a system. It is possible to write

or#

where

is integrating factor.

The lecture deals with

Introduction to state postulate .eroth )aw of Thermodynamics Temperature Scale 'erfect Las Scale

Introduction to state postulate

Since every thermodynamic system contains some matter with energy in its various forms# the system can be completely described by specifying the following variables. The composition of the matter in terms of mole numbers of each constituent. The energy of the system. The volume of the system# and The measurable properties# such as pressure and temperature.

@y specifying these !uantities# the state of the system is defined. 2nce the system is in a given state# it possesses a uni!ue state of properties li-e pressure# ' # temperature# T # density# etc. All the properties of a system cannot be varied independently since they are interrelated through e$pressions of the following type or e$ample# the pressure# temperature and molar volume / 0 of an ideal gas are related by the e$pression ' D *T . %ere * is a constant. 2nly two of the three variables ' # and T can be varied independently. Cuestion is that for a given thermodynamics system# how many variables can be varied independently.

The State Postulate

As noted earlier# the state of a system is described by its properties. @ut we -now from e$perience that we do not need to specify all the properties in order to fi$ a state. 2nce a sufficient number of properties are specified# the rest of the properties assume certain values automatically. The number of properties re!uired to fi$ the state of a system is given by the state postulate: The state of a simple compressible system is completely specified by two independent properties. A system is called a simple compressible system in the absence of electrical# magnetic# gravitational# motion# and surface tension effects. These effects are due to e$ternal force fields and are negligible for most engineering problems. 2therwise# an additional property needs to be specified for each effect which is significant. If the gravitational effects are to be considered# for e$ample# the elevation , needs to be specified in addition to the two properties necessary to fi$ the state. The state postulate is also -nown as the two+property rule. The state postulate re!uires that the two properties specified be independent to fi$ the state. Two properties are independent if one property can be varied while the other one is held constant. Temperature and specific volume# for e$ample# are always independent properties# and together they can fi$ the state of a simple compressible system / ig. ;.30.

igure /"#
or a simple compressible substance /gas0# we need the following properties to fi$ the state of a system: I or 'T or T or u' or u . Ahy not u and TH They are closely related. or

ideal gas uDu/t0 Temperature and pressure are dependent properties for multi+phase systems. At sea level / ' D 3 atm0# water boils at 355o&# but on a mountain+top where the pressure is lower# water boils at a lower temperature. That is# T D f /'0 during a phase+change process# thus temperature and pressure are not sufficient to fi$ the state of a two+phase system. Therefore# by specifying any two properties we can specify all other state properties. )et us choose ' and Then

T D T/'# 0 u D u/'# 0 etc. &an we say A D A/p# 0

(o. Aor- is not a state property# nor is the heat added /C0 to the system.

2eroth +aw of Thermodynamics

Statement: If a body 3 is in thermal e!uilibrium with body 6 and body 4# then the body 6 and body 4 are also in thermal e!uilibrium with each other

igure /"!
Two systems 3 and 6 with independent variables / U3 # 13 # (3 0 and /U6 # 16 # (6 0 are brought into contact with each other through a diathermal wall /figure ;.60. )et the system 3 be hot and system 6 be cold. @ecause of interaction# the energies of both the systems# as well as their independent properties undergo a change. The hot body becomes cold and the cold body becomes hot. After sometime# the states of the two systems do not undergo any further change and they assume fi$ed values of all thermodynamic properties. These two systems are then said to be in a state of thermal e!uilibrium with each other. The two bodies which are in thermal e!uilibrium with each other have a common characteristic called temperature. Therefore temperature is a property which has the same value for all the bodies in thermal e!uilibrium. Suppose we have three systems 3# 6 and 4 placed in an adiabatic enclosure as shown in figure ;.4.

igure /"%

The systems 3 and 6 do not interact with each other but they interact separately with systems 4 through a diathermal wall. Then system 3 is in thermal e!uilibrium with system 4 and system 6 is also in thermal e!uilibrium with system 4. @y intuition we can say that though system 3 and 6 are not interacting# they are in thermal e!uilibrium with each other. Suppose system 3 and 6 are brought into contact with each other by replacing the adiabatic wall by a diathermal wall as shown in figure ;.4 /@0. urther they are isolated from system 4 by an adiabatic wall. Then one observes no change in the state of the systems 3 and 6.

Temperature Scale
@ased on ,eroth law of thermodynamics# the temperature of a group of bodies can be compared by bringing a particular body /a thermometer0 into contact with each of them in turn. To !uantify the measurement# the instrument should have thermometric properties. These properties include: The length of a mercury column in a capillary tube# the resistance /electrical0 of a wire# the pressure of a gas in a closed vessel# the emf generated at the Gunction of two dissimilar metal wires etc. are commonly used thermometric properties. To assign numerical values to the thermal state of a system# it is necessary to establish a temperature scale on which temperature of a system can be read. Therefore# the temperature scale is read by assigning numerical values to certain easily reproducible states. or this purpose# it is customary to use

a Ice 'oint: The e!uilibrium temperature of ice with air saturated water at standard
atmospheric pressure which is assigned a value of 5o&.

b Steam 'oint: The e!uilibrium temperature of pure water with its own vapor at standard
atmospheric pressure# which is assigned a value of 355o&. This scale is called the &elsius Scale named after Anders &elsius.

Perfect 3as Scale

An ideal gas obeys the relation ' D*T where * is the Universal Las &onstant / * D >.43P FBmol =0. This e!uation is only an appro$imation to the actual behavior of the gases. The behavior of all gases approaches the ideal gas limit at sufficiently low pressure /in the limit ' 50. The perfect gas temperature scale is based on the observation that the temperature of a

gas at constant volume increases monotonically with pressure. If the gas pressure is made to approach ,ero# the gas behavior follows the relation ' D*T

igure ;.P shows a constant volume gas thermometer. The bulb is placed in the system whose temperature is to be measured. The mercury column is so adGusted that the level of mercury stands at the reference mar- S . This ensures that the volume of the gas is held at a constant value. )et the pressure of the gas be read as '. )et a similar measurement be made when the gas bulb is maintained at the triple point of water# 'tp. Ae can obtain triple point by putting water and ice in an insulated chamber and evacuating air / which is then replaced by water vapour0.

igure /"*
The temperature of the triple point of water has been assigned a value of 6<4.3: =. Since for an ideal gas T varies as ' #

or#

where Ttp is the triple point temperature of water. Suppose a series of measurements with different amounts of gas in the bulb are made. The measured pressures at the triple point as well as at the system temperature change depending on the amount of gas in the bulb. A plot of the temperature Tcal # calculated from the e$pression T D 6<4.3: / 'B ' tp 0 as a function of the pressure at the triple point# results in a curve as shown in figure ;.;.

igure /"/
Ahen these curves are e$trapolated to ,ero pressure# all of them yield the same intercept. This behaviour can be e$pected since all gases behave li-e ideal gas when their pressure approaches ,ero. The correct temperature of

the system can be obtained only when the gas behaves li-e an ideal gas# and hence the value is to be calculated in limit 'tp 5. Therefore

# as

A constant pressure thermometer also can be used to measure the temperature. In that case# U when %ere 1tp is the volume of the gas at the triple point of water and 1 is the volume of the gas at the system temperature.

The lecture deals with

irst )aw of Thermodynamics

%eat is a 'ath unction Energy is a 'roperty of the System A 'erpetual "otion "achine of irst =ind Analysis of &losed Systems

irst +aw of Thermodynamics

A series of E$perimants carried out by Foule between 3>P4 and 3>P> from the basis for the irst )aw of Thermodyanmics The following are the observations during the 'addle Aheel e$periment shown in ig. :.3.

igure 0"#

Aor- done on the system by lowering the mass m through

Temperature of the system was found to increase System was brought into contact with a water bath

D change in 'E of m

System was allowed to come bac- to initial state Energy is transferred as heat from the system to the bath

The system thus e$ecutes a cycle which consists of wor- input to the system followed by the transfer of heat from the system. /:.3 0 Ahenever a system undergoes a cyclic change# however comple$ the cycle may be# the algebraic sum of the wortransfer is e!ual to the algebraic sum of the energy transfer as heat / I*ST )AA 2 T%E*"2DM(A"I&S0. Sign convention followed in this te$t:

Aor- done by a system on its surroundings is treated as a positive !uantity. Energy transfer as heat to a system from its surroundings is treated as a positive !uantity
/:.6 0 or#

,eat is Path unction

)ets us consider following two cycles: 3a6b3 and la6cl and apply the first law of thermodynamics E! /:.60 to get

igure 0"!
/:.4 0 or# /:.P 0 Subtracting E!. /:.P0 from E!. /:.40 /:.; 0 Since# wor- depends on the path

/:.: 0 Therefore# /:.< 0 Energy transfer as heat is not a point function# neither is it a property of the system. %eat interaction is a path function.

Energy is a Property of the System

*efer to igure :.6 again and consider E!. /:.;0

/:.> 0 and depend on path function followed by the system. The !uantity is the same for both the processes and connecting the states 6 and 3. The !uantity does not depend on path followed by the system# depends on the initial and final states. %ence is an e$act differential.

Differential of property of the system

This property is the internal energy of system# E /:.? 0

Energy of an Isolated System

An isolated system is one in which there is no interaction of the system with the surroundings. system /:.35 0 or an isolated

A Perpetual $otion $achine of irst 4ind

Thermodynamics originated as a result of man8s endeavour to convert the disorgani,ed form of energy /internal energy0 into organi,ed form of energy /wor-0. /:.33 0 An imaginary device which would produce wor- continuously without absorbing any energy from its surroundings is called a 'erpetual "otion "achine of the irst -ind# /'"" =0. A '"" = is a device which violates the first law of thermodynamics. It is impossible to devise a '"" = / igure :.40

igure 0"%
The converse of the above statement is also true# i.e.# there can be no machine which would continuously consume wor- without some other form of energy appearing simultaneously.

Analysis of 5losed System

)et us consider a system that refers to a definite !uantity of matter which remains constant while the system undergoes a change of state. Ae shall discuss the following elementary processes involving the closed systems.

&onstant 1olume 'rocess 2ur system is a gas confined in a rigid container of volume 1 /*efer to igure :.P0

igure 0"*
)et the system be brought into contact with a heat source. The energy is e$changed reversibly. The e$pansion wor- done /'d10 by the system is ,ero. Applying the first law of thermodynamics# we get /:.36 0 or# /:.34 0 %ence the heat interaction is e!ual to the change in the internal energy of the system.

&onstant 1olume Adiabatic 'rocess *efer to igure :.; where a change in the state of the system is brought about by performing paddle wheel wor- on the system.

igure 0"/
The process is irreversible. %owever# the first law gives /:.3P 0 or /:.3P 0

Interaction of heat and irreversible wor- with the system is same in nature. /+A0 represents the wordone on the system by the surroundings

Specific ,eat at 5onstant .olume

@y definition it is the amount of energy re!uired to change the temperature of a unit mass of the substance by one degree. /:.3: 0

Ahile the volume is held constant. or a constant volume process# first law of thermodynamics gives /:.3<

0 Therefore# /:.3> 0

Ahere

is the specific internal energy of the system. If

varies with temperature# one can use mean

specific heat at constant volume /:.3? 0 The total !uantity of energy transferred during a constant volume process when the system temperature changes from /:.65 0

The unit for

is -FB-g=. The unit of molar specific heat is -FB-mol=.

The lecture deals with

&onstant 'ressure 'rocess 3 &onstant 'ressure 'rocess 6 Specific %eat at &onstant 'ressure &onstant Temperature 'rocess Adiabatic 'rocess

5onstant Pressure Process6#

A gas in the piston+cylinder assembly is considered as the system of interest /figure <.30

igure 1"#
The pressure is maintained at a constant value by loading the system with a mass. The cylinder is brought into contact with a heat source.

Energy transfer as heat ta-es place reversibly. The wor- is done by system when it changes from the initial state /30 to the final state /60. /<.3 0 Applying the first law# we get /<.6 0 or /<.4 0

or
The !uantity /<.P 0 is -nown as enthalpy# % /a property0 of the system. The specific enthalpy his defined as /<.; 0 The molar enthalpy is # where ( is the mole number of the substance.

5onstant Pressure Process6!

)et us assume paddle wheel wor- is done on the system figure <.6. Also# consider adiabatic walls# so that

igure 1"!
(ow the application of first law enables us to write /<.: 0 or /<.< 0 or /<.> 0 Therefore# the increase in the enthalpy of the system is e!ual to the amount of shaft wor- done on the system.

Specific ,eat at 5onstant Pressure

)et us focus on igure <.4

igure 1"%
System changes its state from 3 to 6 following a constant pressure process.

There will be an accompanying change in temperature.

Specific heat at constant pressure is defined as the !uantity of energy re!uired to change the temperature of a unit mass of the substance by one degree during a constant pressure process. /<.? 0 The total heat interaction for a change in temperature from T3to T6 can be calculated from /<.35 0

The molar specific heat at constant pressure can be defined as /<.33 0

5onstant Temperature process

)et us refer to figure <.P

igure 1"*
The system is allowed to undergo an e$pansion process while in contact with constant temperature bath. During the e$pansion process# the opposing force is continuously reduced. System is in e!uilibrium at all times. Applying the first law# one can write /<.36 0 or an ideal gas# the desired property relations are and /<.34 0

Since the temperature is held constant# duD5 and CDA . Ae can also write /<.3P 0

Adia'atic Process

1 Irreversible Adiabatic 'rocess

A process in which there is no energy transfer as heat across the boundaries of the system# is called an adiabatic process. or an adiabatic process# CD5. 'addle wheel wor- is performed on the system / igure <.;0.

igure 1"/
Application of first law gives /<.3; 0 or /<.3: 0

2 *eversible Adiabatic /ISE(T*2'I&0 'rocess

&onsider a gas contained in the cylinder piston assembly as the system. The cylinder wall and the piston act as adiabatic walls. Suppose the gas is allowed to e$pand from the initial pressure ' 3 to the final pressure '6 and the opposing pressure is so adGusted that it is e!ual to inside gas pressure. or such a process# dAD'd1 The first+law of thermodynamics will give

)et us consider the system as an ideal gas which satisfies the relation -now that or .

and

. Also# we

/<.3< 0 or# /<.3> 0 or /<.3? 0 or or an ideal gas#

Therefore# /<.65 0

The ratio of specific heats is given by /<.63 0 or# /<.66 0

Thus# /<.64 0

Therefore when an ideal gas e$pands reversibly and adiabatically from the initial state state # the wor- done per mole of the gas is given by the above e$pression.

to final

The lecture contains

&haracterisation of *eversible Adiabatic 'rocess 'olytropic 'rocess Ideal Las "odel

The lecture contains

&haracterisation of *eversible Adiabatic 'rocess 'olytropic 'rocess Ideal Las "odel

5haracterisation of 7eversi'le Adia'atic Process

)et us find out the path followed by the system in reaching the final sate starting from the initial state. Ae have already seen that for an ideal gas />.3 0 or# />.6 0 or# />.4 0

or# />.P 0 or D constant Since# />.: 0 rom />.P0 and />.:0 we get />.; 0

/>.< 0 or#

/>.> 0

or# Dconstant />.? 0

Polytropic Process
Ideal gas undergoes a reversible+adiabatic processU the path followed by the system is given by Dconstant />.35 0

and the wor- done per -g of gas />.33 0

To generalise# />.36 0

n is polytropic inde$ /

is the property of the system# also it indicates reversible+adiabatic process0

n D 5# constant pressure process n D 3# constant temperature process n D # reversible adiabatic process nD #constant volume process

Ideal 3as $odel

 or many gases# the ideal gas assumption is valid and the using the ideal gas e!uation of state:

relationship can be simplified by

or an ideal gas# it has been mentioned that the specific internal energy temperature only# Accordingly# specific enthalpy is a function of temperature only# since 'hysically# a gas can be considered ideal only when the inter+molar forces are wea-. This usually happens in low pressure and high temperature ranges.

is a function of

/>.34 0 />.3P 0

$ Specific heat ratio

/>.3; 0 />.3: 0 or# />.3< 0 or# />.3> 0 In some cases# the temperature dependence of the specific heat can be written in polynomial form. 2therwise# ideal gas tables are also available. They are easier to use compared to the thermodynamic tables since temperature is the only parameter.

Thermodynamic Properties of fluids

"ost useful properties: 'roperties li-e pressure# volume and temperature which can be measured directly. Also viscosity# thermal conductivity# density etc can be measured. 'roperties li-e internal energy# enthalpy etc. which cannot be measured directly

Pure Su'stance
A pure substance is one which consists of a single chemical species.

5oncept of Phase
Substances can be found in different states of aggregation. Ice# water and steam are the three different physical states of the same species . @ased on the physical states of aggregation the

substances are generally classified into three states as a.Solid b.li!uid c.gas

The different states of aggregation in which a pure substance can e$ist# are called its phases. "i$tures also e$ist in different phases. or e$ample# a mi$ture of alcohal and water can e$ist in both li!uid and vapour phases. The chemical composition of the vapour phase is generally different from that of the li!uid phase.

Lenerali,ing the above observations# it can be said that a system which is uniform throughout both in chemical composition and physical state# is called a homogeneous substance or a phase.

All substances#+solids# li!uids and gases# change their specific volume depending on the range of applied pressure and temperature.

Ahen the changes in the specific volume is negligible as in the case of li!uids and solids# the substance may be treated as incompressible.

The isothermal compressibility of a substance % is defined as

The coefficient of volume e$pansion of a substance

is defined as

E&uations of State
E!uations that relate the pressure# temperature and specific volume or molar volume of a substance. They predict the relationship of a VgasW reasonably well within selected regions.

@oyle8s law:

at con&tant pre&&'re

or# &onstant at constant temperature

&harles8 )aw: At constant pressure

At constant volume

@oyle8s law and &harles8 law can be combined to yield

Ahere * is the characteristic gas constant. If the specific volume molar volume# then * is substituted by the universal gas constant#

is substituted by the >.43P -F B -mol =. Again# it

can be shown that for an ideal gas

In summary# the Ideal gas e!uation: where * is the specific constant # where is the universal gas constant />.43P -F B - mole =0 " is the molar

mass# defined as the mass of one mole of a substance. Ae can also write where is the molar volume.

E$ample: " D 6> -g B -mol for nitrogen /since its molar mass is 6>0 " D46 -g B -mol for o$ygen / 26 with a molar mass of 460

(ote: "any gases such as air# o$ygen can be treated as ideal gases. %owever# dense gases such as water vapor and refrigerant vapor should not be treated as ideal gas. Use property table instead.

Ideal 3as
The -inetic theory of gases model a gas as a collection of elastic particles. The statistical analysis of these with some assumptions results as the ideal gas law "ost gases deviate from ideal gas in the vicinity of the critical point and saturated vapour line . "ost gases behaves li-e ideal gas at high temperature and low pressure regions.

8oules Experiment
*efer to figure ?.3

igure 9"#
2ne of the vessels was filled in with air at 66 atm pressure and the other vessel was evacuated. The initial temperature of the water bath was measured. The valve was opened allowing air to occupy both the containers. The temperature of the water bath was measured again and it was found that the temperature did not change. The gas contained in both the vessels is our system. AD5 and CD5. Since the number of moles of the gas also remains constant# it follows that . The pressure and the volume of the gas changed and yet the internal energy did not change. %ence

So#

(9 1)

(9 2)
Since#

(9 3) (9 *)

.an der (aal:s e&uation of state:

The gases at low pressure and high temperatures follow ideal gas law. Lases that do not follow ideal gas law are re!uired to be represented by a similar set of mathematical relations. The first effort was from clausius.

&lausius 'roposed /?.; 0

1an der Aaals# by applying the laws of mechanics to individual molecules# introduced two correction terms in the e!uation of ideal gas. 1an der Aaals e!uation of state is given by. /?.: 0

The term the gas molecules.

accounts for the intermolecular forces and b accounts for the volume occupied by

Since 1an der Aaal8s e!uation ta-es into account the inter+molecular forces# it is e$pected to hold good for li!uid phase also. (ow a days# the 1an der Aaal8s e!uation is used to predict the phase e!uilibrium data. The constants and b are determined from e$perimental data. %owever# rearranging the 1an der Aaal8s e!uation# we get

/?.< 0

Therefore# a plot of ' versus T at constant volume gives a straight line with a slope intercept . An interesting feature can be obtained from the following form

and an

/?.> 0 or low temperature# three positive real roots e$ist for a certain range of pressure. As the temperature increases# the three real roots approach one another and at the critical temperature they become e!ual.

or only one real value of temperature of the gas.

e$ists.

three real values of

e$ists# where

is the critical

igure 9"!
*efer to ig ?.6. The curve A@DE is predicted by the 1an der Aaals e!uation of state. The curve A@DE is practically not reali,able. The physically feasible curve is the straight line path from A to . It can be shown that the straight line A is such that the area A@DA is e$actly e!ual to the area DE D for a stable system.

The .an der (aals 5onstants

The constants of and

and

are different for different substances. Ae can get the estimates of a substance by -nowing the critical values of that substance.

@efore we proceed further# let us loo- at the mathematical function or the ma$imum value of $: or the minimum value of $: or the point of inflection# and and and

rom the igure ?.6 we can see that the critical point is a point of inflection. The critical isotherm must show a point of inflection at the critical point /35.3 0 /35.6 0 At the critical point# the 1an der Aaals e!uation is /35.4 0

2ne can solve the above three e!uations to obtain /35.P 0

Alternatively# one can calculate the 1an der Aaals constants constants.

and

in terms of critical

/35.; 0

The constants

and can be determined for any substance from the critical point data /Table 35+30 At the critical point# one can see that

/35.: 0

Ta'le #;"# Some typical values of .an der (aals constants

Gas

Constants
kPa (m3/ kmol)2

&onstants / m3/ kmol )

+ir
Ammonia /(%4 0

135 ,
P64.4

0 036*
5.54<4

-arbon-.ioxi.e(-/2 ) 1y.rogen (12 ) /xygen (/2 ) Nirtogen (N2 )

36* 3 2* 0 136 9 136 1

0 0*20 0 0265 0 0315 0 03,5

5ompressi'ility 5hart
To !uantify deviation of real behavior from the ideal gas behavior# we introduce a new term namely# the compressibility factor. The compressibility factor Z is defined as the ratio of the actual volume to the volume predicted by the ideal gas law at a given temperature and pressure.

Z D /Actual volume0 B /volume predicted by the ideal gas law0

/35.35 0 If the gas behaves li-e an ideal gas# Z D3 at all temperatures and pressures. A plot of Z as a function of temperature and pressure should reveal the e$tent of deviation from the ideal gas law. igure 35.3 shows a plot of Z as a function of temperature and pressure for N6.

igure #;"#
or each substance# a compressibility factor chart or compressibility chart is available.

igure #;"!
It would be very convenient if one chart could be used for all substances. The general shapes of the vapour dome and of the constant temperature lines on the plane are similar.

This similarity can be e$ploited by using dimensionless properties called reduced properties. The reduced pressure is the ratio of the e$isting pressure to the critical pressure of the substance and the same is followed for the reduced temperature and reduced volume. Then /35.33 0

At the same temperature and pressure# the molar volumes of different gases are different. %owever# it is found from e$perimental data that at the same reduced pressure and reduced temperature# the reduced volumes of different gases are appro$imately the same. Therefore for all substances /35.36 0 or# /35.34 0

Ahere is called critical compressibility factor. E$perimental values of for most substance fall with in a narrow range 5.6+5.4. Therefore from the above e!uation we can write /35.3P 0

Ahen Z is plotted as a function of reduced pressure and # a single plot# -nown as general compressibility chart / igure 35.60 is found to be satisfactory for a wide variety of substances. Although necessarily appro$imate# the plots are e$tremely useful in situations where detailed data on a particular gas are lac-ing but its critical properties are available.

The lecture deals with

Lraphical *epresentation of Specific internal energy and enthalpy Steam Tables

Data for 'ure Substances

There are certain situations when two phases of a pure substance coe$ist in e!uilibrium. As a commonly used substance water may be ta-en up to demonstrate the basic principles involved. %owever# all pure substances e$hibit the same general behaviour.

Ae shall remember the following definitions: Saturated State: A state at which a phase change begins or ends Saturation Temperature: Temperature at which phase change /li!uid+vapour0 begins or ends at a given pressure

Saturation 'ressure: It is the pressure at which phase change begins or ends at a specified temperature.

Saturated )i!uid: It is the substance at

which is fully li!uid /no+vapour0.

Saturated 1apour: It is the substance at

which is fully vapour /no+li!uid0.

Subcooled li!uid: If the temperature of the li!uid /T0 is less then cooled li!uid.

then the li!uid is called sub+

Superheated vapour: If the temperature of the vapour /T0 is greater than superheated vapour.

then the vapour is called

3raphical 7epresentation of

Data for Pure Su'stances

The commonly used thermodynamic diagrams are

a. 'ressure versus Temperature / P b. 'ressure versus 1olume / P c. Temperature versus 1olume /T X 0

T0

d. Temperature versus entropy / T X ! 0 e. Enthalpy versus entropy / h

!0

f. 'ressure versus enthalpy / P X h 0

<a= Pressure6Temperature Diagram

or water # at 355 -'a# the saturation temperature is ??.: 5&. Alternatively at ??.:5&# the saturation pressure is 355 -'a. Cuite often# the saturation pressure is called the vapour pressure.

igure ##"#

*efer to figure 33.3# The segment 3+T represents sublimation process during which solid and vapour phases coe$ist in e!uilibrium. The segment 6+T represents fusion process during which solid and li!uid phases coe$ist in e!uilibrium. The segment T+& represents vapouri,ation .

Sublimation curve 3+T separates solid and vapour. 6+T separates solid and li!uid and T+& separates li!uid and vapour. Three curves meet at T# which is called the triple+point# where all the three phases+ solid# li!uid and vapour coe$ist in e!uilibrium. At the triple point no thermodynamic property of the system can be varied independenty. The system is said to be invariant. Along# 3+T# or T+&# the system is univariant # that is only one thermodynamic property of the system can be varied independently. The system is bivariant in the single phases region. The curve 6+T can be e$tended indefinitely# the curve T+& terminates at point & which is called thecritical point . The critical point represents highest temperature phase andvapour phase can coe$ist in e!uilibrium. and pressure at which both the li!uid

At the critical point # the specific volumes and all other thermodynamic properties of the li!uid phase and the vapour phase are indentical.

and are called the critical temperature and critical pressure# respectively. If the substance e$ist as a li!uid on the curve TX"# it is called saturated li!uid# and if it e$ists as a vapour# it is called a saturated vapour. Under the constant pressure# the line abc indicates melting# + sublimation and + vapori,ation.

<'=

Diagram

*efer to the

diagram as shown in igure 33.6.

igure ##"!
The isotherm is at a temperature greater than the critical temperature . The isotherms and are at temperatures less than the critical temperature and they cross the phase boundary. The point & represents the critical point. The curve A& is called the saturated li!uid lineU and the curve &@ is called the saturated vapour line. The area under the curve A&@ is the two+phase region where both li!uid and vapour phase are present. )eft to the curve A& is the li!uid region. *egion to the right of curve &@ is the vapour region

The isotherm appears in three segments: DE# E and L. DE is almost vertical# because the change in the volume of li!uid is very small for a large change in pressure. The segment L is less steep because vapour is compressible. Segment E is hori,ontal# because the phase change from li!uid to vapour occurs at constant pressure and constant temperature for a pure substance. E represents all possible mi$tures of saturated li!uid and saturated vapour. The total volume of the mi$ture is the sum of the volumes of the li!uid and vapour phases. /33.3 0 Dividing by the total mass m of the mi$ture# m an average specific volume for mi$ture is obtained /33.6 0 Since the li!uid phase is a saturated li!uid and the vapour phase is a saturated vapour#

/33.4 0 so# /33.P 0 Introducing the definition of !uality or dryness fraction the above e$pression becomes and noting that

/33.; 0 The increase in specific volume due to vapori,ation is often denoted by /33.: 0 Again we can write /33.< 0 or# /33.> 0 or#

/33.? 0

=nown as lever rule. At the critical point# the specific volumes and all other thermodynamic properties of the li!uid phase and the vapour phase are identical.

<c=

Diagram

*efer to diagram shown in ig 33.4. )et us consider constant pressure heating of li!uid water in a cylinder+piston assembly. If the water is initially at state 3# on heating at constant pressure# the temperature and the specific volume of the water increase and follows the path 3+6 as shown in ig 33.4/a0.

igure ##"%
At point 6 vapori,ation starts. The vapori,ation process is represented by 6+4. During vapori,ation# temperature and pressure remain constant. The point 4 represents saturated vapour. urther heating produces super heated vapour# that is vapour above its saturation temperature at the specified pressure. If the constant pressure heating is done at several different pressures# the resulting temperature+volume diagram becomes as it is shown in ig 33.4 /b0. The curve A& represents saturated li!uid line and the curve @& represents the saturated vapour line.

<d= T6s diagram

)et us refer to the T+s diagram shown in igure 33.P

igure ##"*

/e0 Enthalopy+entropy diagram or "ollier diagram. *efer to figure 33.; which is -nown as h+s diagram.

%eat interaction in an isobaric process is e!ual to change in enthalpy of the system.

or a flow process /will be discussed later0 the wor- done by an adiabatic device is e!ual to the decrease in enthalpy of the flowing fluid.

A throttling process is an isenthalpic process. A throttling process is a process in which a fluid flows from a region of high pressure to a region of low pressure without e$changing energy as heat or wor-. A reversible adiabatic process is an isentropic process.

Specific internal energy and enthalpy

or# Yon a unit mass basisZ

or2
Yon per mole basisZ Data for specific internal energy# u and enthalpy# h can be calculated from the property tables in the same way as for specific volume.

/33.35 0

Increase in specific internal energy

is often denoted by

The specific enthallpy is /33.330

Increase in specific enthalpy

is often denoted by

Steam Ta'les
Two Saturated steam tables Saturated Steam 'ressure Table Saturated Steam Temperature Table Similar tables can e$ist for any pure substance /e.g. reon 360

Saturated Steam: Pressure Ta'le <)8>)g=

' T /m4B-g0 h /-FB-g0 s /-FB-g -0

(bar) 0 01 0 05 0 10
. . . . . .

(0c) 6 9, 32 90 *5 ,3

20

120 23

In this table pressure is selected as the independent variable.

Saturated Steam: Temperature Ta'le

T ' h s

( oc) 0 2

(bar) 6 1310-3

*
.

30* 15

221 2

Superheated Steam Ta'le

'/bar0 /5.60 355 /m4B-g0 h /-FB-g0 s /-FB-g -0 >.; 6:>: >.36: 655 455 Temperature /oc0 P55

The values for a given condition are to be evaluated through interpolation.

The lecture deals with

&onservation of "ass applied to a control volume &onservation of Energy applied to a &ontrol 1olume

5onservation of $ass applied to a control volume

)et us consider the law of conservation of mass as applied to the control volume.

igure #!"#
During a time interval # let the mass enter the control volume and the mass leave the control volume. )et represent the mass inside the control volume at time t# and represent the mass inside the control volume at time /tNdt0. The law of conservation of mass gives:

/36.3 0 /36.6 0

%ere the )%S gives the change in mass within the &1 during the time interval # while *%S gives the net mass flow into the &1 during the time . Dividing both sides of the e!uation by # we get /36.4 0

In the limiting case as

# we obtain /36.P 0

The )%S gives rate of accumulation of mass inside the &1 and the *%S has respective terms giving rate of mass entering the &1 and rate of mass leaving the &1. If the &1 has many inlet and e$it ports# the e!uation becomes /36.; 0

<'= 5onservation of Energy applied to a 5ontrol .olume

igure #!"!

)et

D total mass inside the &1 at time .

total mass inside the &1 at time

specific energy of matter inside the control volume at time t.

D specific energy of matter inside the control volume at time

and

D 'ressure at the inlet and e$it ports# respectively.

and

D low velocity at the inlet and e$it ports# respectively.

and

D specific volumes at the inlet and e$it ports respectively

and

D specific energy of the material at the inlet and e$it ports respectively.

D *ate of energy flow as heat into the control volume

D *ate of shaft wor- done by the control volume

The mass contained in the region A which enters the control volume during the time interval

The mass contained in the region @ which leaves the control volume during the time interval

rom the mass balance# we can write /36.: 0

where is the mass entering the control volume during the differential time . To accommodate this# the mass inside the control volume has to be compressed such that its volume decreases by the amount . This is accomplished by the pressure acting on the material entering the control volume. Therefore# the wor- done D

Since the mass

has to leave the control volume at the e$it port# the wor- done D

Energy of the system at time

Energy of the system at time

During the time interval

Ae may account for the following

Energy transferred as heat to the system D

Shaft wor- done by the system

Energy flow as heat into the control volume and the shaft wor- delivered by the control volume are ta-en as positive. @y applying the first law of thermodynamics# we get /36.< 0

or# /36.> 0

or#

/36.? 0

In the limiting case#

/36.35 0

Ahere# and

elevation of the e$it and inlet ports above the datum level. The above e$pression can now be rearranged as /36.33 0

*ate of energy accumulation D *ate of energy inflow + *ate of energy outflow

The lecture contains

Steady State low 'rocesses Application of Steady State low 'rocesses

Steady6state low Processes

"any of the engineering devices li-e turbines# compressors# pumps# no,,les# condensers# heat e$changers etc. operate at steady state conditions. The general e$pression developed for the control volume in the earlier lecture can be simplified if steady flow conditions are assumed. These are: The mass flows into the control volume at a constant rate and leaves the control volume at the same rate. Therefore# there is no accumulation of mass inside the control volume. Thus# . or# /34.3 0 The state of the matter at the inlet# e$it and at any given point inside the control volume does not change with respect to time. Therefore# /34.6 0 The rate of energy transfer as heat and wor- across the control surface is a constant. constant Aith these# the first law for the control volume reduces to the form /34.4 0 constantU

Application of Steady6state low Processes

/a0 Turbine: Turbine converts enthalpy into useful wor-. Steam or gas at high temperature and pressure is allowed to e$pand through a system of rotors.

igure #%"#
The change in -inetic and potential energy of steam or gas as it passes through the turbine can be ignored without introducing much error. urther# if the heat losses from the turbine are negligible# the first law for this steady state flow reduces to /34.P 0 Therefore# in an adiabatic turbine# the wor- done per unit mass of the fluid is e!ual to the decrease in the enthalpy of the fluid. %ere# is positiveU

<'= 5ompressor:
A compressor can be considered as a turbine operating in reverse. luid enters the compressor at a low pressure and emanates at a higher pressure. If the changes in the -inetic energy and potential energy are ignored# and the energy losses are negligible# then the first law for this flow process reduces to /34.; 0 In a compressor# is negative. @ecause the wor- is being done on the system# . The wor- done on the compressor per unit mass of the fluid is e!ual to the increase in enthalpy of the fluid. The compressors discharge the fluid with higher enthalpy# i.e# with higher pressure and temperature.

<c= ?o@@le:
A no,,le is primarily used to increase the flow velocity.

igure #%"!
The first law reduces to /34.: 0 or# /34.< 0 If the inlet velocity is negligible and then otherwise# .The velocity is

increased at the cost of drop in enthalpy. If an ideal gas is flowing through the no,,le# the e$it velocity can be e$pressed in terms of inlet and outlet pressure and temperatures by ma-ing use of the relations: Therefore# /34.> 0 and .

rom the relations governing adiabatic e$pansion#

/34.? 0

Ae get#

/34.35 0

<d= Diffuser:
A diffuser can be thought of as a no,,le in which the direction of flow is reversed.

igure #%"%
or an adiabatic diffuser# and are ,ero and the first law reduces to /34.33 0

The diffuser discharges fluid with higher enthalpy. The velocity of the fluid is reduced.

<e= ,eat Exchangers

igure #%"*
The figure 34.P e$plains the wor-ing of a simple heat e$changer. The governing e!uation may be modified for multiple entry and multiple e$it of the system as /34.36 0 /34.34 0 /34.3P 0 /34.3; 0

urther#

and /34.3: 0

is the mass flow rate of cold fluid and

is the mass flow rate of hot fluid.

The lecture contains

Throttling 'rocess Application of Throttling 'rocess

Throttling Process:

The porous plug e$periment was designed to measure temperature changes when a fluid flows steadily through a porous plug which is inserted in a thermally insulated# hori,ontal pipe. The apparatus used by Foule and Thomson is shown in igure 3P.3.

igure #*"#

A gas at pressure

and temperature

flows continuously through a porous plug in a tube . The device is thermally

and emerges into a space which is maintained at a constant pressure insulated and -ept hori,ontal. &onsider the dotted portion as control volume. This results in

Therefore# whenever a fluid e$pands from a region of high pressure to a region of low pressure through a porous plug# partially opened valve or some obstruction# without e$changing any energy as heat and wor- with the surrounding /neglecting# the changes in 'E and =E0# the enthalpy of the fluid remains constant# and the fluid is said to have undergone a throttling process. If the downstream pressure is held at several different values successively and at each of these is measured# we shall obtain a situation e$plained by igure 3P.6.

igure #*"!

Each plotted point represents a state for which the enthalpy is e!ual to shall be able to obtain a constant enthalpy line /figure 3P.40.

. If we Goin all these points we

igure #*"%
Such a plot of ' versus yields may also be called isenthalpic curve. The slope of the isenthalpic curve

is called the Foule+Thomson coefficient and given by

The e$periments are conducted with different

and

in order to find out the isenthalpic

curves. A family of isenthalpic curves is shown in igure 3P.P which is typical of all real gases.

igure #*"*
The point at which curve. is called the inversion point. The locus of all the inversion points is the inversion

In the region left of the inversion curve# pressure

. In the throttling process the down stream . Therefore# whenever a real gas is

is always less than the upstream pressure

subGected to throttling# the temperature of the gas decreases if the initial state lies in the region to the left of the isenthalpic curve. This is e$plained by a process from to in igure 3P.P.

To the right of the inversion curve# . If the initial state of gas lies in the region to the right of the inversion curve# the temperature of the gas increase upon throttling. or almost all the gases# at ordinary range of pressures and temperature# and the ma$imum inversion temperature is above the room temperature. The e$ceptions are hydrogen# helium and neon. or hydrogen# the ma$imum inversion temperature is 655 = and for helium the ma$imum inversion temperature is 6P =. If hydrogen is throttled at room temperature# the temperature of the gas increases. To produce low temperature by throttling# the initial temperature of hydrogen should be below 655 =. This is usually accomplished by cooling with li!uid nitrogen. Similarly# in the production of li!uid helium by throttling# the initial temperature of helium should be below 6P =. %ence it is cooled by li!uid hydrogen prior to throttling.

Suppose an ideal gas is throttled. Since throttling process is isenthalpic# and for an ideal gas enthalpy is a function of temperature only# the temperature of an ideal gas does not change during a throttling process. %ence for an ideal gas.

Applications of Throttling
/a0 *efrigeration The wor-ing fluid /called refrigerant0 leaving the evaporator as vapour at state 3 undergoes an adiabatic compression in a compressor and leaves as saturated vapour at state 6. This compressed refrigerant enters a condenser where it reGects heat to the ambient atmosphere and leaves as a saturated li!uid at high pressure at state 4. Then the li!uid refrigerant at high pressure undergoes throttling and leaves as a mi$ture of li!uid and vapour at low pressure at state P. During throttling# the li!uid vapori,es partially and its temperature decreases. The cooled refrigerant then passes through an evaporator where it absorbs energy from the body to be cooled# and leaves as hot vapor at state 3. inally# the hot refrigerant vapour goes to the compressor# thus completing a cycle.

igure #*"/
Applying the first law of thermodynamics to each of the units /control volume0 the following relations are obtained:

&ompressor /adiabatic0 &ondenser /constant pressure cooling0 Throttling /isenthalpic0 Evaporator /constant pressure heat addition0 The coefficient of performance /&2'0 of the refrigerator is defined as the ratio of the energy absorbed at the evaporator to the energy re!uired to perform the tas-.

<'= +i&uefaction of 3ases

Ahen a real gas which is initially at a temperature lower than the ma$imum inversion temperature is throttled# its temperature decreases. This principle is used by )inde in the )i!uefaction of gases. *efer to figure 3P.: for understanding the operating cycle.

igure #*"0
The gas is compressed to a high pressure and then cooled at constant pressure in a counter current heat e$changer with the cold gas which comes from the separator. The cooled gas is throttled to a low pressure. Thus some amount of gas is converted into the li!uid phase. The two+phase mi$ture comes to the separator. The li!uid is withdrawn and the cold gas is fed to the heat e$changer. Then the gas enters the compressor along with a fresh stream of ma-e up gas for li!uefaction.

The lecture contains

Transient low 'rocesses &harging of a &ylinder / &ontrol 1olume Analysis0 Discharging of a cylinder /&ontrol 1olume Analysis0

Transient low Processes

During charging and discharging of cylindersBtan-s the condition of the fluid inside the cylindersBtan-s change with time. The rates of inflow and outflow of mass are not identical and there is accumulation of mass and energy inside the control volume.

igure #/"#
These processes are transient flow processes. The first law e$pression for a control volume is given by /3;.30

5harging of a 5ylinder <control .olume Analysis=

Ahile charging the cylinder from the supply mains# no gas leaves the control volume# and wor- is doneU . (o shaft

. )et us ignore the changes in the -inetic energy and potential energy of the gas during

charging operation. Then it is possible to write from the e!uation /3;.30 /3;.6 0 or# /3;.4 0

Ahere#

denotes the mass of the gas in the control volume and # denotes the specific internal energy . It is assumed that the state of the gas at any instant of

of the gas inside the control volume at time

time inside the control volume is uniform. The e$pression above can be integrated from the start of the charging operation to the end of the charging operation # to obtain /3;.P 0 The principle of conservation of mass for the charging process reduces to: /3;.; 0

*ate of increase of mass in

*ate of mass entry

Integration of the above e!uation over time gives the change of mass in the control volume during the charging operation /3;.: 0 (ow in the e!uation /3;.P0# the last term on the *%S can be evaluated as /3;.< 0 and /3;.> 0 Substituting /3;.:0# /3;.<0# and /3;.>0 in /3;.P0 we get /3;.? 0 If the cylinder is initially empty and the filling operation is carried out under adiabatic conditions the above e$pression reduces to /3;.350

If the gas is treated as ideal Then#

and

/3;.330 Ahere# is the final temperature of the gas in the cylinder and temperature of the gas in supply mains. is the ratio of the specific heats. is the

Discharging of a cylinder <control volume Analysis=

&onsider a tan- containing a gas at -nown conditions of temperature and pressure /figure 3;.60.

igure #/"!
The valve is opened# the gas escapes from the tan- and the properties of the gas in the tan- change with respect to time.

)et#

pressure of the gas inside the cylinder at

temperature of the gas inside the cylinder at

specific internal energy of the gas inside the cylinder at

and operation.

denote corresponding !uantities of the gas left in the cylinder after the discharging

velocity of the escaping gas. rom the first law# we can write /3;.36 0 (o material flows into the cylinder Then and the potential energy changes can be ignored.

/3;.34 0

or the discharging process# the conservation of mass gives /3;.3P 0

4ntegrating the abo5e e6'ation o5er time gi5e&

/3;.3; 0 Integration of the governing e!uation yields /3;.3: 0

(ow the term on the left hand side may be evaluated as

/3;.3< 0

Similarly# /3;.3> 0

and /3;.3? 0

inally invo-ing /3;.3<0# /3;.3>0 and /3;.3?0 in /3;.3:0 we get /3;.65 0

It is assumed that the gas escapes with a uniform velocity 1 and specific enthalpy h.

5ase of an Ideal 3as

&onsider a small amount of gas in the cylinder /confined in an imaginary envelope0 in the cylinder as a system.

igure #/"%
Imagine a situation when gas escapes the cylinder. The boundary of the system changes continuously and eventually occupies the entire volume of the cylinder. The gas which is left in the cylinder does not e$change energy in the form of heat with the surroundings. It undergoes an adiabatic e$pansion. Ae can prove that the gas undergoes a reversible adiabatic e$pansion.

The general e$pression is:

/3;.63 0

Ae can change the basis of analysis from a control mass to a control volume based analysis. Under such a situation# )et us consider the cylinder volume as the volume of interest. # and ignore the change in =E and 'E /3;.66 0 rom the principle of conservation of mass /3;.64 0 Therefore /3;.6P 0

or a perfect gas#

and

. Then e!uation /3;.6P0 can be rewritten as /3;.6; 0

or# /3;.6: 0 or# /3;.6< 0 or# /3;.6> 0 @y integration between final state and initial state /3;.6? 0 As /3;.45 0 or#

/3;.43 0 Ahere So# /3;.46 0 and /3;.44 0 is the characteristics gas constant

Invo-ing these relations# we get /3;.4P 0

or# /3;.4; 0 /3;.4: 0

Therefore the gas that remains in the tan- can be considered to have undergone a reversible adiabatic e$pansion from the initial pressure to the final pressure .